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INTERNATIONAL ELEVENTH EDITION
Peter Atkins I Julio de Paula I James Keeler
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@Peter Atkins, Julio de Paula and James Keeler 2018
" PHYSICAL CHEMISTRY INTERNATIONAL ELEVENTH EDITION" was originally published in English in 2018. This
translation is published by arrangement with Oxford University Press. KYOBOBOOK CENTRE is solely responsible for this
translation from the original work and Oxford University Press shall have no liability for any errors, omissions or inaccuracies ot
ambiguities in such translation or for any losses caused by reliance thereon.
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Physical Chemistry international eleventh edition
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Peter Atkins, Julio de Paula, James Keeler
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E= 4¤4+ +oie] g+ Ezl44 zla$qree tsd6l.9 6J+. ?l^le+= 94 "l Hq+ql^j. EE "J4i= +4_o + B
+. ol E= EAg "Jfl4old z}¤4olzJ d* ddl E9t+.
^td, ^ll^Jel
,l s+qlH}+q 4fEolq, E4+Eg r +ql^lE qd"l 9i ++ql^Je+ a.ol "l rr+^l= BB
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elEol4. HI¤- +EEg
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r ^J4++. "lH ^l] +ql^J= *d zlz} +ol +7IqS.r,
6-J ol+. E "J+ 4¤¤ _H_+ z}^.|16l ,Je-l6J +E 9lr g+= a
¤44 " -e.r arqE chapter Eil{ql focus4E *¤3 "Jg q ¤ +E 9lg 4,o14. qB= z}gl rzl]= Esls+qlg a
^} "l
e" oI*.jL E4l_e '+B',g'^lel +E',s Hl-+E^l r Lll+ t6l-zl t*= qL^JEql4lE + B^JE ¤9 rI4zL E 4ol4r
g ttd z|,<llalzll^lE
rzfla|fla dlr4ls fe} zl^lg gs6J * ^J46J+.
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^J
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r ^J{qzl"J B4 z}¤r++ 45e r¤4r+= gr-l 6.h¤ 6J zl-=.zI+6J+. %r-Ell6J Eot9 E-el++¤. EzI^l Hq6l+ E
olzl$ $AzlH^J glol"F at} 4,E"14. + s+7t flg + s.+r 84ql+ g:e +E9 zl49 u}"l
= rxflq
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PREFACE
Ow Physical Chemistry is continuously evolving in response ')ustifications' that show how an equation is derived. Our
to users' comments and our own imagination. The principal intention has been to maintain the separation of the equation
change in this edition is the addition of a new co-author to the and its derivation so that review is made simple, but at the
team, and we are very pleased to welcome fames Keeler of the same time to acknowledge that mathematics is an integral
University of Cambridge. He is already an experienced author feature of learning. Thus, the text now sets up a question
and we are very huppy to have him on board. and the How is that donel section that immediately follows
As always, we strive to make the text helpful to students develops the relevant equation, which then flows into the
and usable by instructors. We developed the popular 'Topic' following text.
arrangement in the preceding edition, but have taken the The worked Examples are a crucially important part of the
concept further in this edition and have replaced chapters by learning experience. We have enhanced their presentation by
Focuses. Although that is principally no more than a change replacing the 'Method' by the more encouraging Collect your
of name, it does signal that groups of Topics treat related thoughts, where with this small change we acknowledge that
groups of concepts which might demand more than a single different approaches are possible but that students welcome
chapter in a conventional arrangement. We know that many guidance. The Brief illustratioms remain: they are intended
instructors welcome the flexibility that the Topic concept simply to show how an equation is implemented and give a
provides, because it makes the material easy to rearrange or sense of the order of magnitude of a property.
trim. It is inevitable that in an evolving subject, and with evolving
We also know that students welcome the Topic interests and approaches to teaching, some subjects wither
arrangement as it makes processing of the material they cover and die and are replaced by new growth. We listen carefully to
less daunting and more focused. With them in mind we have trends of this kind, and adjust our treatment accordingly. The
developed additional help with the manipulation of equations topical approach enables us to be more accommodating of
in the form of annotations, and The chemist's toolkits provide fading fashions because a Topic can so easily be omitted by an
further background at the point of use. As these Toolkits are instructor, but we have had to remove some subjects simply
often relevant to more than one Topic, they also appear in to keep the bulk of the text manageable and have used the web
consolidated and enhanced form on the website. Some of the to maintain the comprehensive character of the text without
material previously carried in the'Mathematical backgrounds' overburdening the presentation.
has been used in this enhancement. The web also provides This book is a living, evolving text. As such, it depends
a number of sections called A deeper look. As their name very much on input from users throughout the world, and we
suggests, these sections take the material in the text further welcome your advice and comments.
than we consider appropriate for the printed version but are
there for students and instructors who wish to extend their PWA
knowledge and see the details of more advanced calculations. ldeP
Another major change is the replacement of the JK
E,rll Ll|E 47l| v
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:dd rE4loe EgEl= 7t|LJo| r ut|e=
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qtq '^]9 +E' ¤g E6ll^l +trlBa zlEzioll" E E;l
Elqlg 016116}= rll seal ^l]Ea dg %LE9E +E6tg.trI. > "-IC TllLJ
r.aJz{|9 qHrl= g8;lcl
=
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?s. ^l^l
ol trEP zlill9 dE(EE 1A), E5 zlr{l EEloll^l tsE
^t|EE =61 47t|-d gE EEoll g
d.e Eq=-g +q^l 6t+E E4^+ +4,-HB.+. 4 trqE -d LHE= olE-ettl. stqtrle-| 8^] 60ll^1
e-l a +Eql r L|]+el +s^J, rflil +s-6J TllH9 ¤B6ll 46l.11 Etl.
+gtr, E +4¤ol "J"t"t B 'ZJ+6J EllAS ¤B="11 +9ttr1'
Err+dEg l
EE gE cl^l A,*Hql^le+ +ol 7ls- l9l4 d"l 849
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+q. ^F&ts Ag flql+. +Eol +lc q aJ44014.
r}E tr LtlE
f,^ll a++E '^tE a'ql=.?++ 4EE=, EllolEl E" :a4r 1
,\l9 xttl
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812
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4 E 845
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7ll'JE
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7llH# ill36l+ ql f+g 1o14.
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tr r. ^lE EeE Eal4 8Etl, + 844 =49-:844 C4-e
agsq.
a 2. Ee4 BEg 30*6lt 7l-F^d zlqg "J4 S4"l 'zJot^l=
vi .E llLll8^7ll
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=
49 ea+ +419 .lt¤¤ 6il44 ol aeg PEql
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gg gq.
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dwor=-4.6, Eillotl BdlIl= g lSell K dE /dx >
5
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r" +dgb zllHE4 +^l$- dzfial.b d¤zl"J %FBg ¤B
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,llEg ol nxllel 'S+'E Erlle+ a+ q qEJ+q, "JHlzl Er}.8.8 ¤4I
o e -H+ Q z|,<lla[4] Bg *]"t t4.g+ Hs9 E^llql ql Ezt eB ¤4lE EEL* +"Jg ++ts9 + fl=ql, olEg
+6llB:==9s4"J"+ g+fl4. "Spartan Student" iiEE?llqe+ *ol ilE-+
"J= aol{. rfl
4 "lE$ Harrree-Fock, 'JE HEI+ r?la MP2al&g ts +
cl^{El LflE 9t= e.= EB ¤41 +EE+llq= rlE ¤+. E ,tlolF www.
oup.com/uk/pcheml lexeE d+6}1 -H-otu}.
ol g{"J ¤-$ E j/xflel 'll¤¤ trQ 4rll ¤86I9s4, ul
3el trJBrloil7fl
EqEE dC!+ +^lql 6l'l]E ¤-E*d
zlzl-E=e ,J^l-=otlTll +ts += 9l+(^l-B +4-e=tr-= ++e-s olso B + fl+).
g +E+ r.E6l= +8, EqE¤ E4^F #q fxll9 "J*
Cg +zl6LE-+ l=q619trI. Ta 4=
"Jel ¤^le_E #g
ag +s*"i ¤dg+ 9lg 4o14.
EEIIIE =B4g ol ;r'2fl$ i}]q6J trl.E=g ¤+¤- ap ol$-Q-+ ?l+.¤i+
,J^l¤g ztsi. tlzlql ol nzfl r-ll+ql ++ $sle+ qlolEl E g A+61 www.oup.com/uk/pchemllexe9 "&E6Ia 46J+
s$ drll ++Bg + 9l+. ol$g zj$ {-{eE #r e o1 ¤zl-.ll trlq$ g+.
Erll du^'l
=ol
e.'xll $ol +l1lJE Peter Bolgar, Haydn Lloyd, Vlaimiras A^l-& Exll ¤ol +r^Jql= ¤# Exll b'e+ ai+ E^lloll q6J
ra]A |ames KeelerT} Al+8.+.
Oleinikovas, Stephanie Smith, Sd6J Eol r-ll+ol +=qq flcH"l nafl. i]]q6}= AÎ=
qtd+ E4l Eol elr^Jql= ¤# Exli 'a'e| 94 Exll"il 4-J gg+{o e +gtsg+ 9l+).
Sd6J¤ol LH+ol t=qq flq.
ilell ix
^fBll
E xix 2A.1 g, E, "J OllLlIl 32
El'-4rl.el .8^l (a) !84 trE= 32
)od
(b) Ert 99 Exh += a|1A 34
gîl-d L]lE ndi
q5! 2A.2 LH+ oflLl^lg g9 35
oci )odii (a) lllF ollLlrlE E^l += 6tl4 35
(b) lE^lel +4lat 36
dfil rl^l ollL1xl,3-E, "J Et+ 2A.3 tsA g 36

(a) E9 gHJ4 E,rl 37
(b) "Jg:d galoil "f^1= tsg
Efl,t 1 7**E ¤E 3
(c) zl9 ts8
37
38
(d) gd TlillelEl3 7l.E g8 39
-trE 14 EI 7lill 4
2A.4 Eg 39
1A.1 8EH E+
E="J
4 (a) 4lS 40
(a) S4 4
(b) EEAJ 40
(b) 8s' 5
7flLJ= 43
1A.2 gEH^l 7 =e.Et A.!E
43
(a) dE4 Ez1 7
=g:et
(b) 7li1l=-dE 9
-trq 28 glBtrl M
71lE= 10
=sEt 28.1 gt=trlE Eel 44
Eie.El 10 (a) fllBnl EtrleI EE olE 44
^l=
(b) E 4laJ 45
.tr.E 18 EXIEEPE 1'1
gEJ
28.2 glgtrlE .gEoll ttt= tstrI 46
1 B.1 EÎ.E¤i 1'l
(a) B¤ gajoil^1g EEBF 46
(a) Salzl E^t ++ 12
(b) EE-J= *41 47
(b) Maxwell-Boltzmann 4H Es 13
TtlLJE
^lolsl
48
(c) EErl 15 =g:d
18.2 E^f 48
16
==U.=. =sEt ^.!=
(a) 35 17
trE 2C Eiltrt 49
(b) Ea Be 17
2C.1 r= ?!=q Eat
^l+ 49
7flE= 18
=s-d (a) Eal4 Eetelglgtrl 49
18 (b) elqt EslE gl=Jtrl 50
=e.-d ^l=
(c) Hess9 Ez]
EE grll zlr{l
1C 19
51
2C.2 E= gd fl!=Jtrl 52
1C.1 ol84 dEE+E19 ol=J '19
2C.3 U3 glgtrlE 8E el= 53
(a) $= ?.!xl' 20
2C.4 d--J 7lE 54
(b) ulflg 44 20
(c) ExlS# 23
(a) ,t lil + l4l E4aJ 54
(b) Ea 4¤ E 4lB 55
1C.2 van der Waals AtEH^.l 23
.
7il8=
ll9 3E'JH
있다
55
상만
(a) 23 =sEt
(b) 24 4E 56
^lE =8 =g:d
mD
(c) rHB SEt|sl 34 26 EE 2D gEH e+9[ sd slE
과다
TllLJE w
L
m~ . 돈
27
57
=g:d j 2D.1 SE olEr+ESC EIE 57

om 27
=sEt ^t= 2D.2 L|l+ oilH^lE E+ 58
¤g Eril, E* . 28
(a) 3HJ4aE 58
Erll (b) g¤ g+ 6toll^lE Ltl+ ollLl^l Eql 59
.=.61x{
o lJ g,'ll 30
-r 2D.3 g!=JtrlE Etrt 61
2D.4 Joule-Thomson E4 62
EV1.\ 2 l$=l 31 (a) Joule-Thomson Er-tel B¤ 62
(b) Joule-Thomson Erl9 Exl'ffi o-H'S 63
E4 2A Lfl+ oilH^l 32
&
=s-d7flEE
x iEll
=sEl ^l=
Eq 2E .Jg Eet
@
65
열풍간 (a) Maxwell S4l^l
(b) Lt|+ oilq^lE +tr|oil r4E Haf
10'l
103
3E.2 Gibbs ollLl^lE ¤E 104
2EJ 8E H+ 65 (a) gHJ4 aE 104
2E.2 gaj E+ 66 (b) Gibbs ollLlrlelEEoll ttt= Est 105
EgEI7HE= 67 (c) Gibbs ollLl^lel"Jaloll nlE HEt 105
Ee,E! 67 SsEt 7[EE 107
^{E
108
¤B Erlt. E¤ 68 =e.Et ^l=
.=.et^{
O u
ErJl
.l-"ll 71
.gB ErlL EA 109
-l
E8l 112
844 3 2H=lrt 3H=l 73 =E'4
EZa 4 ++Et Etr9 HEt 113
EE 34 gleeul 74 =al4
3A.1 2E5l 74 EE 44 i4E! Egg g_trJtr raJ 114
3A.2 g!=esl9 g9 76 4A.1 8E $EE 114
(a) flc-a4q Eqqt4 Ee.l 76 (a) 89 # 114
(b) fle-eslslE4l gqqr'4 trE 77 (b) I d0l 114
3A.3 8E|l -Et+e^l9 ?!=+ul 78 (c) I ?JEsq Eqtrtq 7l= 115
(a) Carnot tS 78 4A.2 I ?AAl 116
(b) gE+4 e-E 81 (a) I EoEl +aJEE 116
(c) Clausius ++] 81 (b) I +2sl =d= 117
THEE 82 4A.3 7l^l EHs4 d|gB raJ 119
=gEt 83
^11
(a) ohlaFJ+ 119
=g'Et ^lE (b) E 119
EE 38 rlEEoll +HJEI= fl= enl Esl u (c) EE 120
3B.1 =8
ga 84 TllE= 121
38.2 I Eol 85 =sEl 121
38.3 7lE 86 =e.El ^lE
38.4 +-st rI8 86 -tr4 48 S Iolel gqet4 gA 122
EsEt 7[E= 87 48.1 ?JEEoll gEF= T= EZ 122
87 (a) 89 ?JEE9SE 9= 122
=eE! ^lE (b) +tsEoil olilts gzjg g-d 123
-trtr] 3c fllEetrlol +g 88 (c) 5zl gEioll Elil= E+ gf+E gB 124
3C.1 tlE+trlel E_4lg 88 48.2 g BXlst 9l^l 12s
=gE
3C.2 3H=] 89 (a) I SzlldE 7l?7l 125
(a) Nernst9 E 8el 89 (b) rill-Eillt,. ?e4l 125
(b) 3Erl glEetrl 90 (c) o4x1l-Ezl34l 126
(c) BJB fllBu-lE eE E= 91 (d)rr1l-=71 e^l 128
TllLJE 92 7llHE 128
=g'Et =sEt
92 128
중간
=sEl ^lE =sEt ^lE
Eiil 3D 4l fl+e LEt"! 8e
3D.1 Helmholtz qlqrlgl Gibbs
(a) xl'J¤oll cH-d 7l=
ollLl^l
93
93
93
¤B EIII, Eg
=U= =xlt
물화 129
130
7l'^l+E
(b) Helmhotz 0lulrlollS-zf H 94
EflAs E+Ed= 133
=lrtl E
(c) 94
Tlrl+E
1
(d) Gibbs ollLlrlq S-d E 95
g -trir_l 5A EgtEoll EH:d Eq+ 1U
(e) Hl-ts8
sA.1 E= g
96
=lctl9 134
3D.2 E= E Gibbs ollLl^l 96
(a) 8dGibbs ollLl^l 97
(a) EFul 134
(b) Born
(b) E= Gibbs ollLlrl 136
98
TllEE
^l (c) 'JP *E a[-qt E1EJI¤ 136
99 (d) Gibbs-Duhem 137
=sEt 100 ^l
sA.2 E-stE Eq-+ 138
=sEl ^lE (a) 9E 7li{lE EB Gibbs ollLl^l 138
EE 3E 1EE4 2H=]g EB 101
(b) TlEl EE' Eqqf4 Et+ 140
3E.t L|1+ o{Ll^lE dE 101
il'all xt
아
5A.3 Eillg et-qt tr1EJ!¤ 141 (b) Debye-Huckel g=.1 178
o|8 Eeq =-Lr
(a) 141 (c) *-d EElel+8 179
(b) ol84-=e Ee4 143 7flHE 180
144 =sEt 181
=g.El7llLJE
6eil 145 =e,El^lE
^lE ¤E EfiI, EA 182
tr.E 58 EEq dE 146 .=.tlx{
o u
ErJl
.I7'll 187
-l
5B.1 o4ill=-ctE 146
(a) o18 E-4 146 8714.6;ffi gg 189
(b) 4g Er'+e18+ Eo-4 147
sB.2 149 Etr] 64 tsE A+ 190
=gd
(a) AE 149
=Bd9 =C 6A.1 Gibbs ollLl^lel+4 190
/h\:r--r'xl
\v, 4iL
O=
E 4E 150
(a) UB Gibbs ollLl^l 190
(c) oltsE ull=J 152
(d)E6HE
"J-a|}drlg-^-"d u3
(b) 191
152
6A.2 gBel¤g 191
(e) 8F 153 (a) 9E TlillgE 191
155 (b) gHJ4 EJSsl 3+ 192
=sEl7il8= 't56 (c) ,J:d Ar+= tr41 195
=e'Et ^lE
Es.! sc 2¤E llsl atrJE zB: e4ill
(d) EE 8+9 ^l.o19
Erl-++ 6t|4 196
157
력
THEIE 197
tra 1I
-71 ola{ OO6 ---ral
}r{=d JE 157
JL. Oz I tl-- =gET
5C.2 3s-a'5 AtgE raJ 158
4E 197
=sEt
(a) 8EE:Lal ralTl 159 E4 68 EJtroil gElg + sg 198
(b) AEE raJq 6tl4 160
68.1 geq g-* 198
tr42 -= 161
Jr!.J OTf
68.2 eEE g-d 199
(a) E# EE 161
(a) van't Hoff 4l
=+el
(b) EE-83 =+ 161
199
(b) 8o SEoll^lsl KE'J 201
어
=EI'E l-el
(c) 41olxl *= o4ill 162
71lE= 201
sC.4 o_{ijl_EijlAIEErg 163 =eEt
202
(a) I Eal 163 =sEt ^lE
(b) "J4lEatl 8s. 164 Etrl 6C Elqr'Exl 203
(q) $fl{o+ #ol= o-4i1lel=+ 165
6C.1 U-HJ8rl-E= 203
(
=sEl7]lE=
167
6C.2 4= flrl 204
al= 167 (a) e4zJtr+ EjEJ]¤ 204
=e-d (b) dxl 7lE 204
EE sD 2gE 4lel atsa r.H: rill 168
6C.3 E^l tr1El¤ 20s
sD.1 #E-stE 168 (a) Nernst al 20s
sD.2 USZ| 169 gE atEtlg E^l
(b) 207
5D.3 Hl:-Jil=E 170
6c.4 Eq+4 -Bt+=9 207
71lE= 170
T}IEE
=¤
=sEt 209
=AE!
Eiif sE 3¤E 4lsl gtsE laJ 171 {E 209
<tr 27|a ,\lr{a
1I J-Ci -ral =eil
171
JL. C)OC'rE
EE 6D C+ tr1EJ!¤ 210
sE.2 388 4l 172
6D.1 E= tr1EJl¤ 210
(a) +E4o+ 4olE o4i1l= 172
(a) trxt 210
(b) 3dE 4laill 173 =¤
+8^l=9
(b) 212
EeE! TllE= 173
6D.2 r= qfl¤g ol8
=-ct
212
:
EilI 9r
+-
qtr ltlE_E
eo4 174
(a) Ezlel*4 ,t1E 212
(b) gEE 4l+9 213
5F.1 E0ll9 E-ss 174 =8
(tr1 EIEE (c) EE A+q 213
-Q.xlol
Jt.L O
=-i =Or
174 =8
(a) otg4-*= 175 SsEt 7llEE 214
(b) dr1lEtr =O 175 214
(c) E=J-EEoll "J4-Lf gEE =sEt ^]E
176
¤B EA 215
5F.3 8+ EEg B=E 176 =x1L
N
.=.tlx{ ErrJl
218
5F.4 0lgslg-EE 178 O E -I!.1-"ll
(a) EE E|EE 4l+ 178
2 2
-
xil iE{l
S.Zl,t 7 gfrp 221 EE 7F EII EE 267

7F.1 2^|fl AE 267
-tr4 7A gxtq-qtel 7lB 223 (a) Schrodinger 419 oll 269
7A.1 oilL1^lE etrlel 223 (b) 4EEaJE 2rÊ| 270
(a) E;1lEtl 223 7F.2 3xltltrlE 271
(b) gEeJ 226 (a) ufgg4O ollq^l 271
(c) flxl-"1 ExlE ru:le.g 227 (b) 4E=J 274
7 A.2 trtE_ggol 016:5 228 (c) 4rl eH 275
(a) Cxfzl-E,tlel ggold 228 7HE= 276
(b) g"Jo19 trl.#! 230 =s-d 276
THEE 231 =s-d ^l=
=sel 231
¤B E8L EA 277
=s-d ^!E Efll
g,'ll 282
=tlx{
o u -r
-trE 78 trF=-d+ 232
78.1 Schrodinger A.l 232 E71 8 flrl +6g}AElEaJ 83
78.2 Born o]|4 233
(a) 87at 234 -Etrf +A5 gÎ
8A 2U
(b) trl.E-st+oll 7fo=}|^l= 235
^1le+
8A.1 +4E fl^lE +6 284
(c) Bntel 236 (a) E#9 E4 284
7ilEE 236 (b) g^lE trlE u¤^l 285
=s-d 236 8A.2 g^l.flEgr'+et r ollulxl 287
=est ^l= (a) flEer#el E^l 287
-trul 7c Eu^let7l+t=B 237
(b) oilqrl=9.l 287
7CJ Et^l' 237 (c) ol8el qq^l 288
(a) r.8il "J8^.1 237 (d) E^l =Ar) +UE 289
(b) E^}xl u=71 238 (e) s tlE-d# 290
(c) Hermite Eti^l 239 (f) "J^tE EE sr'+ 291
(d) 4E8 240 (g) p +lls-gf 292
7C.2 TlE}|^l 241 (h) d +lE:Br+ 293
7C.3 =dr+ get 244 7llEE 294
=+gd 7l¤
7C.4 ztrlq+E 246 =eEt 294
7llEE 2M =sEt ^l=
=s-d _trsl 88 trfI^l flxl n5
4= 2M
=e.Et 8B.1 +lE-Er+ 295
Eiil 7n tflrl oE
L1 av oLj rlo 247
88.2 Pauli uHe|.=^lts
flal 296
7D.1 l ifg rl'+ ¤E 247 (a) 296
7D.2 1^l-floil^lE ++ aE 248 (b) Ê
Pauli 3al 297
(a) oIEEE a}l 249 88.3 +4 Eal 299
¤E
(b) trl'$:Bt+el 250 (a) EFq 7lalt 299
(c) 0lt-1x19 dtr 251 (b) Hund9 3+l 300
7D.3 2iffl ol.8oil^]e.| ++ EE 252 (c) flxt HJ^lErt olP uJ^l= 302
(a) ollHxl trtE-d+ 252 (d) 0 13tr1 ollLlxlel E^l' rlefE 303
(b) trlElE =+lel 254 8B.4 ef +llE-Et+ 304
7D.4 E1'J -d8 254 ^l'i1l-gg¤
TllE= 305
257 =s-d al= 305
=s-d7flts= 2s8 =sEl
=e'Et ^lE -tr.q 8C flTIAtsI.EH 306
Eiil-78 xl-E oE 259
8C.1 +AE g^1el
+a ,L UO l-:-O
4u1EaJ 306
7E.1 4Et Tt=^f 259 8C.2 tlfl^lflx1g Ê]EaJ 307
(a) 0lulxl=+l 260 (a) At=-Bf 307
'JB-dll
(b) trtEEr.+ 261 (b) E-flE e-'J 308
7E.2 5.E+ TIEÎE ,5E 263 (c) B zlE 311
(a) Earl 263 (d) Hund9 7rl 314
(b) E1'J E8 265 (e) C'i 7*l 314
TllE= 26 7llLJ= 315
=sEt 26 =s-d 315
=eil^+= =sEt ^lE
iE{l xiii
¤E EXL EA 316 ¤B Exlt, EA 359

.=.61x.{ Erfll r=fl|
o u -r g,'ll 318 =.61I{
o Ei -r [,'ll 361
E'7{4 9 Exl T= 319 844 10 Er[ E]|e 363
Erl E2f4 qa
10A 3M
E{l rl^l Born{ppenheimer 3Al 321 10A.1 EH8 Etlrt El1e e^ 364
10A.2 E^t=g EHe E+ 366
EE eA fl1t71-=g olE 322 (a)Cr, Ci, g C, 367
9A.1 2fl^l E^1. 322
=
(b) cn, cn, o! cnh t 367
eA.2 BE 324 (c) D, Dn6, Dn6 E 368
9A.3 trffl^lEx[ 324 (d) s"= 369
(a) 6+] 325 (C) E,JE 369
(b)=¤ 325 (f) gE ElEil 370
TllEE 328 10A.3 EllaE 4trT1e 370
=g'Et (a)*d =rl 370
328
=eil ^l= (b) 7l=Jd 370
EE 98 Ert fllE-d+ olE: #A Exl-ol3 329 7flEE 371
98.1 fl^l +lE-Er'+E de 329 =9':d
Efia e^
E#31El|8 371
(a) dE =-Et
u=71 329
=E|, EE 1OB E=
(b) +EEt+ 330 372
=-st
(c) HJ,l:d fl_E_d+ 332 108.1 372
98.2 +lE-et+ r^l 333 108.2
=Eelflal
:dal
rd 373
TllE= 334 (a) Ett9 EllEfl 373
=s-et (b) EE 374
334
=eEl ^J= (c) =q
zP+ sE 375
EE 9C Ert fllEEt+ olE: 2flxl Ert 33s (d) 375
=eI ^lE
9C.1 Ert Hllil 335 108.3 xlE'.E 376
(a) otlE-d#el rflE-*# 335 (a) flxl'?]lE-Bt+EE E11e 6 377
aE 4E
(b) 337 (b) dE Etle 378
(c) 24tl 2Ert E^l- 338
=_cr.+lE_Bl.+Eel
(c) xls. Eet trlEl'E = 379
=eq
9C.2 SEÎEBE 340 TllHE 380
7llLJ= 341
=sEt 380
=sEt
341
=e.il ^lE
=sEt ^lE .trE 10c EtlAg 3E 381
Eq 9D Ex| TJIEB+ ol=: 0l=6-{ 2flr} Exl u2 10C.1 AEEI= 4E 381
9D.1 ETlE¤lE 342 F -Bt+E EE 4E
(a) 381
9D.2 =d =-Brrl
EE BAI 343 (b) EEE E61| 383
(a) 'JE 344 10C.2 u^l +lE-Br+=oll tH-d 3E 384
(b) aflE c-3 346 (a) ills-d# EE 384
EsEt TlltsF_ 347 (b) Etla-48 CB 384
10c.3 cEi +41 =Et 385
BeEt 347
^+= SsEt TJIEE 386
trsl 9E Ert fllEB+ olE: trl"3xl E^t 348 386
9E.1 Hrickel Z,\l 348 =9,8l ÎE
(a) ol
'JE9 azfl 348 trB E8l, EA 387
(b) ol "JEoil^-l olEB= il=J 349
OE]
,t.-
OQ
oo 353 IEz1,t 1't Erf i}$g 391
(a) r-Erl otlLj^l 353
=Et
(b) HJ-*+ ?t8E .tr.E 114 EXIE8E9I gUE EE
354 393
eE.3 4tua+E1) al.+ 355 1 1A.1 +,\ldE E+el 'J= 393
(a) EJ-d-d4 ggrl#olEE gE 355 (a) xE4 +^t rt¤ 394
(b) "Js. H:d+ 0lE 356
^l'J4
(b) Ce4 ++lrf Eol Efl!E 395
(c) :49 E,ilH 357 (c) Beer-Lambert E4 395
357 11A.2 -tu4eal d* 397
=sEl7fiEE (a) DoPPler r1d 397
358
=sEl ^lE
xiv xE{l
(b) +B qa 398 11F.2 tr|fl^fE^l 440

1 1A.3 d:d 'JH 399 (a) d
--4 =tE 440
(a) E-,'.l BE 399 (b) n*<-n oJ r*<-n dol 442
/h\
\v,
-El,\l
s- 400 7[EE 43
^tr{Eal
(c) zJtltl
-.....I_E
402 =eEt 443
(d) E84lE 402 =sEt ^l=
7HH=
=+ q2 .trEl 11c #8Efl=EAB 444
=sEt 403 11G.1 EBI} ?]B 444
=sEt ^l= 11G.2 6l|elel d"=}|zl 446
Erf 118 Eld E¤|E 4M 11G.3 qlolxl 447
118.1 slE ollLlrl=+l 404 7flEE AA8
(a) 7E trlE^l 405 =g:et
(b) 4a flExl 406 ¤B EI1L EA 449
(c) CB qErl 408 Enl 454
(d) Ec "Jra1A 408 =Et4
118.2 olol=eq E8E 408 EA^ Q EAI EE_+ 457
(a) de4 #zl 409
(b) olo|=eE.[ -tu4e.fl9 Es 409 EE 12A Bottznrann ES, 458
11B.3 elfl Raman EBE 411
12A.1 ullilel+41 458
118.4 -"_{ EXls} trJE dEt| 413 (a) #zJ4 uflxl 458
TllE= 414 (b) aEtl 4E Es. 459
=sEt 415 (c) 8#E9'J 461
=sEt ^l= 12A.2 8Ell=E grtlq zHilt# 462
-trE 11C 2flrtE^lel IIEEIJE 416
7llLJE M3
1 1C.1 TIE A5 416 =g'Et
M3
11C.2 4Ed EBE 417 =sEt ^l=
1 1C.3 Hl4Eld 418 _trE 128 ExlEutl Er+ 4A
(a) Olulxl=+l=q +aJ 418 128.1 EH}| -Br+el=9.g 464
(b) Birge-Sponer Erl 419 128.2 EU|l -Br+oil EH-d 7lq 466
11C.4 tl5elE 44EaJ 420 (a) Et!EEE 7lq 466
(a) rurl=fl z[xl 420 (b) Elc SEel 7lq 468
(b) 421
=-cr ^l
"Jg (c) TIEEEg 7lq 471
11C.5 TIE Raman AgEaJ 422 (d) Erl dl.El1E 7lq 473
5g:et T]ILJE 423 TI|LJ= 474
424 =gEI 474
=sEt ^l= =sEt ^l=
-trE 11D trl-3^[ Erlel t]5 EB|E 425
-trEI 12C E^l,qlqrl 475
1 1D.1 7l= T.!E g^.1 425 12C.1 7lE^.1 475
11n? I{AlAl a.^ /\trllEa.l
ttv.z-nuHl---E 426 12C.2 71E85 g4=9 7lq 476
1D.3 T]E Raman An:lEg 427
1
(a) ET]EEg 7lq 476
71lE= 428 (b) elE8=9 7lq 476
=R-d 428 (c) IIEEEg 7lq 477
=sEt ^lE (d) c^l'c|Ellq 7lq 478
Errl 11tr
4: rl-=. /\iillEaJol rl.lil -tr^l 4n SEt|9 7lq
I tL t-jo -tlc, r.l_-
---E-l (e) 478
11E.l Et|eoll g4:d 7l= dE BJ lelE+ 429 ^rJ
7HE= 479
11E.2 T_t= trtEg+el E}led 431 =eil 479
(a) zl$ g^.|=el4Ed gd 431 =e.Et ^lE
(b) 7l='J^.1=9 Raman Ed 431 EEI 12D E= gA= 480
(c) ut|ef +.19 Elled 432 12D.1 g8=9 TtlLj 480
=71
7flE= 432 (a) rluH4 ut|il 481
=eil (b) aEtl +E EEoll^1E eE 481
-trg 1 1F d^f d:Ell EIEaJ 433
12D.2 419 gA ollLj^l 482
11F.1 2flrrExl 433
12D.3 8E ErlE ItlrE 482
:d
(a) zlE 433
12D.4 +trloll
=gq= oilL1^l HEI 483
(b) dE{ +'l 435
7HH= 4U
(c) T.lE Bl^Jl+^ 436 =g:d
(d) eld ol^11+4 4U
439 =eil ^lE
xle{l xv
EE 12E Lt|+ ollLlxlel glEetrl 485 529

12E.1 Lt|+ ollLlrl =e.Et ^lE
485
(a) Ut|F otlL1^lE 4l^t 485
¤B Exll, E6 530
ET]l
(b) gEeJ 486 o E -r u-,\ll
=6[:t{ 532
''rr.2 E=eul 486
(a) fls-aulel EUtl -Br'+ 487 -*71.\.14 UB 533
(b) ET.!B=E 7lq
^-E=
488
(c) eld tEE 7lq 489 EE 14A Eittri HJ3"l +E 53s
(d) rlE ¤EE 7tq 490 14A.1 HJSE Cil +4 535
(e) tF g1=eul 491 (a) EU4 ag 535
71lE= 492 (b) d-d Brg s36
=sEt 14A.2
=E:d
u39 *s. 537
492
=sEt ^lE (a) EJB +Eel Eol 537
Eq 12F *E Et+E 493 ,g+
^-E HElr+ +E
(b) 538
12Fj 8s. 493 (c) HJB rH s39
12F.2 gE g+ 495 (d) H4E s39
-+s. =8
(a) Kq EUt| Et+ *41 495 7llLJE 542
(b) 6[al irJE ^lolE =sEt
496 542
(c) EE 8+oll EH-d 7lq 497 =sEt ^l=
TllE= Eril 1,4A
+- rw
Xlu -^.E rfl*l 543
499 -1:
ld-
-+
=sEt 148.1 oit HJ8 543
499
=sEt ^l= 148.2 1^t u3 543
¤E EH, EA 500 148.3 2il HJ8 545
Erll 504 T]|EE 548
=-d4 =gET
548
844 13 Erl=el # 509 =ail4E
-trE 14C EJEe_e E=61.= HJB 549
5q 13A eJE zlillel AHJ ¤E 506 14C.1 EEo+ tr=61"= 1^l UB 549
13A.1 EgE4 s06 14C.2 SAH 550
^.lE THEE
13A.2 EU ¤tre.| 4aFlE1 508 s52
=g:et
(a) Stl1l# 509 552
(b) E Es-= 510
=e.El ^lE
(c) Eds 5'11
E.E 14D Anhenius 4.1 5s3
(d) EE 4s' 512 14D.1 U3+Eel8E EE 553
T]|LJ= 1 4D.2 Arrhenius qeF lElel 6H4 555
513
=g'Et
513
(a) HJSOISq6l.= ollLl^|g N s+ 55s
=sEl ^lE (b) gdtr| ollLlrloll olil= +ot|E E.r.t 556
EE 13B Erjl +ollîel Ert ¤-E 514 TtlEE 557
=gE}
138.1 d-d'jrt 514 557
(a) o4i11E 55 514 =Ret ^l=
(b) E6t|tr EsI 515
EEJ 14E U3 DllTlLl= ss8
"14E.1 AHJE ss8
138.2 olEE ol-ES. 516
't4E.2 E+4
(a) sF Aal 516 AHJE 559
(b) olEEelEtrtr 518 14E.3 8+gEtl s60
(c) Einstein EAh.l 519 14E.4 +E-e¤ =^1.
E4t 561
TllEE 520
14E.s 1E-uJE 562
=sEt 14E.6 u3+Eoll EI]EI^_EE4 "J gq-qr^l xlull 564
520
=s.Et ^lE SsEt 71lE= 5&
-trE 13C etti 521 5il
13C.1 EE+4 SE 521
=sEt ^lE
13C.2 +^l^l 523
Esl 14F HJ8 ollTlLl=q ql 565
(a) 'J# 4tt 523 14F.1 lErl'E U3 565
(b) cP q* s25 14F.2 HJBE +EE 566
=-ct
(c) 4tEl9 al| s25 (a) E4AIE-d s66
'13C.3
E4 q-qtq gtr 527 (b) E^1=-'J 568
7[EE s28
14F 3 EA-=o]1r'tE HJB 570
=sEt
xvt iEll
7HE= 573 1sD.4 dErl Zltio_++El Eg 614

=s-d (a) 84 g-drl Eal =r+
4E 573 614
=g.Et (b) flald "J u,J¤ trlEJl¤ ollLl^lEE 615
.l4G sJit-qr
-trtr1 574 (c) ?fxl$-*4 tal 0E 616
14G.1 Bst+ i-l-¤ s74 TI|LJE 617
14G.2 1^|.gr^[+=E 575 =s-d 617
14G.3 --E.JgB dEtlE A4 oil7tLl= 576 =s-d ^l=
14G.4 577 -trE 15E Eg4loilîol Ex[olE 618
14G.s êf
8E oilL1^l 0lE 579 1sE.1 +E E=.1
E^l olE 618
71'lE= 580 1sE.2 8^l.E E8E qg
E1'J 6'.19
=s-et 1sE.3 E^l- old +E 8+ 620
580
=e.il ^l= 1sE.4 olEq te4 a= 621
¤B E+ 581
7[E= 623
=8L
Erll
.=.61x{ 585 =s-d
o u -r ll,.il eeEt 4E 623
Ez1,t 1U HJB 587 ¤B EA 624

=81
=+-+ 627
-trE 1sA olE s88
=U= =x{
=E
1sA.1 U8d A= 588 844 16 rt7l=iB 629
(a) zF1l0l,\l9 588
(b) ollLlrl == -+s s89 -trE 164 gHJ flzl 630
(c) Bi1l4
ê
4,J 591 16A.1 E! 630
15A.2 RRK Eg s93 ^l'7lgB
(a) xt7 18 +oll,t'lel 6-!el ollLlrl 630
7HE= 594 (b) NMR EBAI 632
=s-d 16A.2 d^l8^l7ld 8B 633
594
=sEt ^l= (a) xlzlg+oil^1E E^lE oilH^l 633
-trEl 1sB +tt-^lHH u3 595 (b) EPR EB4I 634
1s8.1 ¤i-q +oil^1el U3 s95 TtlLJ= 635
(a) HJBE E+ 595 =gEI
4E 635
(b) +tlr[ HJ8 596 =s-d
158.2 Etr-EE s97 EE 168 NN/R ÊIIEH9I 636
(a) *r]dt
^,I
597 168.1 a[+4 olE
=8 636
(b) Etr-EE^.|g
"-fl
598 168.2 Tlalt Af+g 3e 638
71lE= 598 (a) 4xl4 zlq 638
=g:d Al= 599 (b) ?]tr71 7lq 639
=g:d (c) Eot| z lq 640
-trEl 15C Eol-d|'E}| olE 600 168.3 0l^'ll+4 641
15C.1 Eyring al 600 (a) rurl=aq qg 641
(a) *4et 600 (b) 8+9 f7l 643
(b) B¤Er=E Eal+E 601 (c) =Et
trJ-lnJ fl?l 644
9dai=E E-E
(c) 601 (d) =-del
-"1 645
(d) +E 8+ 602 -:"t
(e) .tllZl -"-{
646
1sc.2 Eq+4 rE 603 168.4 -ES rl¤=EtE 647
(a) BdelEfalolE'l 603 168.5 rill-8Etl NMR 648
(b) olE= HJB 60s TI|LJE @9
^lolE eq- =g:d
1sc.3 +EE4 Eflfl+ 606 650
71lE= 608 =s-d ^l=
=g:d 608 -trq 16C NMR0il^1el E4 zlg 651
=g.Et ^l= 16C.1 xlTlEt ulEl 651
EE 15D E^l Eq-qt 609 (3) fl{-ful+ Ert 6s2
=EE o!^}718E
15D.1 E^l'¤ 609 (b) dE+E9lEea 653
(a) !:'J SE 609 16C.2
^|il-Eq
Sst 654
(b) d:-J ÊJ
610 (a) $et trll7l'Ll= 655
15D.2 u}e,\{ *E
t-joci 6=
=rl 611 r,rt r2E +E
(b) 6s6
(a) oJSd =Jxl 612 16C.3 657
=EEUJB Eel+
Ê =-Et-EaJ
(b) $efl-dle1 612 1 6C.4 e4 Overhauser .Ez[ 657
15D.3 tr1EJ!¤ qlqxl EE 613
x]41 xvii
TllLJ= ffi 17D.3 +4t8 ig 704

=g.Et az19 tr-E
ffi (a) 704
=sEl ^l= (b) +HJE 707
-tr4 16D dxlSxfTld aB ^l'=
661 (c) S$! 'zJ^llig 708
16D.1 g'2J 661 17D.4 q-+4 dtr 708
16D.2 Eol^ll7a 662 (a) Eetl glE+tr| 708
(a) -'-{ gJ9 Ez} 662 (b) Etd 709
(b) McConnell 663 17D.s g4 dtr=:sFi1l 710
^l
(c) EE|^llSE,rtEE 664 TllLJ= 711
=g =sEt
TllLJ= 65 IE 711
=sEt =g:d
65
=s-d ^l= EE 17E rlill trEt 712
¤B EXI, E¤ 666 17Ej :=EO;c 712
.=.6lLl ETll
o u -r 9,.1t 669 (a) f;Sef 119 712
(b) oJEE 7'a3
84^ 17 8E r¤ 671 (c) Ezl2#
"4et 713
=\l7J 17E.2 trl¤r+8ill"+ 715
-trq 17A E^tel E7l4 dtr 673 (a)af! 8E4r'E 715
A.1 xJ.718=^l'EEIE (b) El¤ Ed 716
17 673
17A.2 rJ--S. 67s
(c) 25=-, E-4+, Lalr EIIqI 717
17A.3 EJ= 676 7iEF_ 719
trJl9 154 E= =s-et
(a) 677 4= 719
(b) E E= 678 =sEt
TllElE
¤B EIII, EA 720
680
r=T.ll
=s-d .=.51,x{
o u -r ll,'ll 723
680
=e-d ^lE
EEI 178 E^lE lolol 8A.fE 681 g4-\ 18 -r.i{l 725
't78.1 +.8 d6lE SEarE 681
^tolE
dal-8*xl
(a) 8E^tE 681 -trq 18A 'J8 +a 727
(b)
8=^t-gf=^l'.88^lE 682 18A.1 +7ld 4^l- 727
(c) 8*xt8g 8=xl8a4tE 685 18A.2 4rl'Eel
=8 729
(d) +"J ts=^l+g 8=^l'8E4+E 685
^lE
(a) Miller xlf 729
178.2 +A 686 (b) ?1tr #E-97J,1 730
=-st
17B.3 Eill gE^tE 687 7lEF_ 731
7[E= 89 =eEt 731
=eil 690 =eil^l=
=sEt¤ -tr4 1BB cltr 71ts 732
o-qill
-trE 17C 691 188.1 Xd 732
17C.1 o4ill +oil^lE E^ll ,sErlE 691 (a) =¤+
xd elE 732
(a) HJ,tlB EE -d+ 691 (b) Bragg9 E..l 733
(b) q(r)9 Ilt 692 (c) tlal glxt 734
(c) eqrll9 Eq-E4 ¤E 693 (d) drl'95. 735
17C.2 Eill-=7lXlE 694 (e)ia9'jtr 739
(a)sE BaJ 694 188.2 Er[ Atr 740
(b) +EE 695 =8^l-AtrI|
7[EE 741
(c) s-.tlltr:tE 696 =sEt 741
17C.3 EE E 697 =sil^+=
(a)sE S4 697 EEI 18C r,illoll^.lel 742
(b) EE=el Eq+ 698 =Et
18C.1 742
17C.4 700 =+
(a)5'"J S 742
-
TllElE (b)B+9 Ert+a
701 744
=9.:d 18C.2 ol8=El riil 746
701
=sEt ^l= (a)ia 746
-trE 17D rE^l 702 (b) oilLlrlE 747
17D.1 EE traJ 702 18C.3 A+=-d rillel Ert rill 750
17D.2 801:d
= +=g ?4 703 751
=gEAEF=-
xvilt ilzll
751 Eiil loFl

+a ,vu
6il,;rl
H--l
Elil
da 782
=sEt ^.1= 198.1 782
EE 18D r.illel q-qt4 ¤¤ 752 =At#l
(a) Langmuir #l 782
7flEl= 753 (b) fraJ EAt fllgul 784
=sEt 754 (c) BET #4 785
=s-d ^lE (d) Temkin 53^.14 Freundlich 5E^l 787
EE 188 rJlH E7l*1 8tr 755
198.2 E4l +Eq =J=l+s 788
18E.1 e+d Eill 755 (a) d"x1lAle}| 788
18E.2 trEillel HJs,all 756 (b) E^l ffioll^1 E 788
18E.3 EdEill 758 (c) .E.Eoll,r.lE olEoE =4r'rl =+ 790
TtlEIE 759 7ilLJ= 790
=gEI 759 =sEt 790
=sEt ^lE =e-d ^l=
Esl 18F lrr1lel xt7l4 ¤e 760 E.E 19C Hg +Otll'E 791
18F.1 xl'7lElE 760 19C.1 ffig +0HarEE 0llTlLl= 791
18F.2 g+ "J Pg 761 (a) lExtE UB 791
^PlsElE
18F.3 AEEillE ¤tr 762 (b) Langmuir-Hinshelwood 4lzlulE 792
^Pl4
SRET TtlEIE 763 (c) EleY-Rideal ollTlulE 792
763 't9c.2 EEoll,\lsl +Et| gd.E. 793
=sEt ^{E TllE= 794
.trirJ 18c rjllel gtrtr1 de 7U =sEt
Es-d 794
18G.1 E^lE 764 ^lE
'18G.2 UErll 765 EE 1eD d+oll^1 gqLE zElE 795
=4-4
(a) H9 765
=* 19D.1 tF--Eeq 4lE 795
(b) "JB trl.olgEet trfolec allolxl 766 1eD.2 E=oll^1E E+ gE 796
18G.3 Htde g+4 E8 766 (a) Butler-Volmer .l 796
7ilHlE 78 (b)Tafel .E,rl 800
=sEt 1eD.3 dg-d+ E 800
¤E Exil, E6 769
"19D.4 dTls=]l 803
Er.il 772
=alx{
O E -l rJ-"Il 19D.5 Galvani d^l 803
^lE
TllE= 804
g'4a 19 r.i{l E'EoilA1e.l EEI TT3 =sEl
EgET 804
ÎE
EE 19A rillEEE 47ll n4 ¤B Eril, E6 805
19A.1 EEE dA .=.tl,({ E:tfll
774 o u -r g,'Il 807
19A.2 EelEzlrt Elst=Al 775
19A.3 d-d 'JH 776 XIE tr
(a) EolS H 777
1loo-L /\[9. ritr 810
(b) ol8gl H 778
(c) Eltr E 779
2 EP{ 812
(d) E4r'4 =J4rE d-Ee++EE e8 780

3 E1l0lE1 813
4 E(=E) 843
781 ^lE
=sEl7ilHlE u7
Eefl 781 abte.zl
^+=
E x x
JJ.
l,
E 1A.1 galel E+l 4 8 6D.1 2e8Koll.,\lE E= trlEJl¤ 2t0
E 1B.1 (E) 7E{ 8+ t4 8 6D.2 ETIE[-+4 2t3

^1E
E 18.2 #EE4 L7 8 7E.1 Hermite trl-d -d+ H,,(y) 261
E 1C.l Hlalg Al*, alkm3mot-]) 2l 8,7F.1 7E aal g4 273

=&l
E 1C.2 7li{Eel g4l c|+ 23 E 8A.1 +4= flr|el ,J/.lE! ul.S-slf R,,(r) 286
E 1C.3 van der Waals 1l# 24 8 88.1 9E -4 #61,, Z"tt =Z-o 299
t 1c.4 g+ 8Ell^l= 25 E 88.2 ++ flAEe_l flrl.url:e, r/pm 302
E 2A.1 qa{ 7}rl=+el g 37 E 88.3 013 HJxIE, r/pm 303
E 8E ol=,
28.1
=
EEeJsl 8 8B.4 efi H Erll 0l8el0llLjrl 303
C,,^/(JK-1 mol-1) = a + bT + c/T2 47 E 8B.s drt TIE.IE E"/(Hmol-l) 3M

8 2C.1 dol -9E'0il 19 E= EE "J g!=Jtrl 50 E 9A.1 +1E-*+ 327
=g =8
82C.2 col "J u3 glgtrl 50 8 9C.1 +aE +JEg+= afl 4E 337
^t'olst
E 2C.3 *71 il.-dEel E= 8¤ g]=tr1 "J EA fll=tr] 8 9C.2 7{e|. 71n.l
=u =vl
339
(2e8Koll,\l) qlLlrl
51 E 9C.3 E-et a]lal 339
8 2C.4 +71 ElElEel E= gd t!gtrl(2e8K0t!^l) 52 E 9D.1 Pauling9 d7l#E 343

8 2C.5 +7| EtElEelE= 8c fl=Jtrl(2e8K0il^1) 52 E 10A.1 Etoll rllEt E^l 366
E 2D.1 2esKoll4el gA z{l#(a) "J SEs(rJ
- 60
E 108.1 cr, xlg g. 316
8 2D.2 ttd e-E(I), Eg ol#(rr)al
--:tsE(rb),
f.elr E 108.2 cg, xlg E 371
1 atmal298 Koll^lel Joule-Thomson 4l+(I1) 61
rlE E
E 108.3 c4 379
E 3B.1 88 dol e_Eoll^-lel E= I fl01 t!!=etrl("J EE), E 118.1 tr8 EEIE 4M
at,rs"/(J K-] mol-l) 85
E 11C.l 2flrt ErtE dtr 421
E 38.2 Ei{lel#tsEoll^1el E= fllgtrlel glEetrl 85
=g E 1 1F.l ,Jgl 4, I!#, .J ollLlrl 433
E 3C.1 E= 3E=l fllEEr;, 298Koll^1 90
E 1 1F.2 g+ flrl.JrlErtE 440
E 3D.1 E= 8¤ Gibbs ollLlrl, 298 Kollll 97 =g =c
E 11G.l 4olrl +^l.dE ol=el Et-*4 0!E 47
E 3E.1 Maxwell B4lA.! t02 =8ut
E 128.1 2flrl ExtE elE -gs 469
8 5A.1 298Koll,\lel Eoll E}|-d 7li{lEEel Henry E=l A+
K/(kPakg mol-r) IM E 128.2 ETEq EHE+ 471
E 58.1 q- Lll=J s+(Kf)et BtsE e= 8+(Kb) 151 E 128.3 2flrl Erhel EC tl5 473
-e.E
E 5F.1 179 t 13A.1 1 atm0l^19 zF{19 AU dtr 507
E 5F.2 179 E 13B.I 2e8 Koll^jel Ei{lE EdE 514
8 5F.3 gEEsl EE AteH: 9ef 180 E 138.2 2e8Kel 1E ol3 olEE 517
=oil
E 6C.1 7t=. X.l=
-to ri-r 203 E 138.3 298 Koll,\'lel qtl 4l+ D/(10-n m2s-1) 519
xxjE
E 148.1 lil u8oil g-d tJ8 +E=4 EllolEl 54 E 178.1 dE4la qfl¤ oilLlrl 68s
E 148.2 2it uSoll tr-d u3 +EE4 EllolEl 545 8 178.2 Lennard-Jones (12,6) tr1E!¤ OllLlrl trElElEl 688
E 208.3 I.l-E!El .4.E r+ti!

ll-t 547 E 17C.1 Ei{F=sl 2e3 KoilllE EE 8|aJ 694
-t*-l_: -+
E 14D.1 Arrhenius .trEltrlE1 553 E 17E.1 EE gg8ltrEltrlEloll nl= olg BE1|9I Etrt 717
E. 14G.1 Ekepf 45 574 E 18A.1 gE 728

=8rl
E 14G.2 HEJrl?l BEal-+4 r+Ef= 575 E 18C.1 g+ fl^=el 7^ 743
=E
E 14G.3 g+ +71t-E7H 80il EH-d RoE A 579 E 18C.2 Ol3 UII=:, r/pm 747
E 15A.1 7li{lt} HJSoll tll:d Arrhenius EElolEl 592 E 18C.3 Madelung 8* 748
E 158.1 EE +ot!^1E 7I-Eo[ S]| U-oil EtFd s. 18C.4 298 Kol[\lel4rl fl=tr1, LHL/(W mol-l) 749
Arrhenius EEFIEI 596 E 18F.1 2e8 Koil lE xPIilE 761
E 16A.1 -4E ¤=rl tr4_^trJ ?r^t+ 630 E 19A.1 glgtrlE ElEll +8i1, 2e8 K 775
=al =4t
=4 4E E
E 16A.2 dtr 631 19A.2 EtEt fl!=trl, L"dIl /(U mol-r), 298 K 775
=+
610:1 .=.it r-a{
E 16D.1 flrl=E AEIîl A+ atmr 6& E 19C.1 +l- t=-l o- 794
=-d
E 17A.1 8=Jt E E! E (t/)el E?s. T nl(a') 673 E 19D.1 EE d+ "JEet olE 4l+ 2e8K 799
ElEtrle-|8^| xxi
-9-l
I
+^lel /\I,\I
o-l
ilEtrlel 8*l r 2trt E+t 5 El¤txlel 8al to Euler9 L! 242
ElEtrle] 8Ll z qal Eillg gtr 6 ElEtrle.l AlAl

o-t
rl,z u{ltrl
-r
El 248
El=lrlel 8+l : .gEAE,T

rIOO- EI
Er ll E]trlrtel 84 ts Ld4 55+ LtErl 2s9
ElEtrlel 8*.! + I{tl

-tL t4 :ilEtrlsl 8*l tg fl58 rlE 267
ElElrle] 8+l s EIE 22 ElEtrte.l /\l^l

o-t
1^
zv 7t:.!
-tl.:-oo 268
ElEtrlsl 8*l 0 grt oilLJrl 33 it=lrlel ,\l^l

o-t
11
Al 7g -,-ttE 272
aFtrlsl 84 z ¤EUll flAI 35 aFlrle.l .,\t^l

Ci-i
11
ZZ HlltrJ G,\l
-r -l r-: L: 309
Erqrtgl 8+.1 s E6h d+, flaJ "J 0llLlrl 4l El¤lrlel ,\l^l

O-T
1a
LJ 8=J^l 346
ElElrlel 8*l g II{E6T.A

U+E I 42 ilElrle.l 8*l z+ B= 350
ElElrlsl 8^l r o ST EIE tw ilEtrlol ,\t^l

O_I
1(
LJ B== ol8-d TBil HJ8^l 352
=71
Et=lrtel 8*.1 rr
-EE E9l t39 EtElrle.l ,\l^l
o-i zu14. rl+ -Et+91Gauss :d* 398
ElEtrtel 8^l r z E+ E71l l5l E[Elxle.l lAl L,

o-t
17 Bd7ltrl 511
a]trtrtel 8*l r: ErPl=^l 223 ElEtrle.l /\l/\l

o-t
la
4u +Eg4E= ol8El4E 547
ElElrlel 8^l r + -H./\^

-al
233 ElEtrte.l 8^l zg g=rl"t! rt7lE| 639
tltl r.lrl
=l=trlsl
8+l r s -E
--iE 240 ElEfrle.l 8+l :o Fourier Hfl 654
xxii +J^lrd Ll|E
At,ttl-Lf uflE
Number Title
1 The Debye-H rlckel theory
2 The fugacity
3 Separation of variables
4 The energy of the bonding molecular orbital of Hj

5 Rotational selection rules
6 Vibrational selection rules
7 The van derWaals equation of state
8 The electric dipole-dipole interaction
9 The virial and the viria! equation of state
10 Establishing the relation between bulk and molecular properties
11 The random walk
12 The RRK model
13 The BET isotherm

EE xxiii
o{6F
OO
Number Focus Title
1 1 .. .on environmental science:The gas laws and the weather
2 1 .. .on astrophysics:The Sun as a ball of perfect gas
3 2 .. .on technology:Thermochemical aspects of fuels and foods
4 3 .. .on engineering: Refrigeration
5 3 .. .on materials science: Crystal defects
6 4 .. .on technology: Supercritical fl uids
7 5 .. .on biology: Osmosis in physiology and biochemistry
8 5 .. .on materials science: Liquid crystals
9 6 ...on biochemistry: Energy conversion in biological cells

10 6 .. .on chemical analysis: Species-selective electrodes
11 7 .. .on technology: Quantum computing
12 7 ...on nanoscience: Quantum dots

13 8 .. .on astrophysics: The spectroscopy of stars
14 9 .. .on biochemistry:The reactivity of O, N, and NO
15 9 .. .on biochemistry: Computational studies of biomolecules
16 11 .. .on astrophysics: Rotational and vibrational spectroscopy of interstellar species
17 11 .. .on environmental science: Climate change
18 12 ...on biochemistry:The helix-coil transition in polypeptides

19 13 ...on biochemistry: lon channels
20 14 .. .on biochemistry: Harvesting of light during plant photosynthesis
21 16 ...on medicine: Magnetic resonance imaging

22 16 .. .on biochemistry and nanoscience: Spin probes
23 17 ...on biology: Biological macromolecules

24 17 ...on medicine: Molecular recognition and drug design
25 18 .. .on biochemistry: Analysis of DNA by X-ray diffraction
26 18 .. .on nanoscience: Nanowires
27 19 ...on technology: Catalysis in the chemicalindustry

28 19 .. .on technology: Fuel cells
flfiI rlAI oilL1^|, EE, :2S sle+
-l..:l
gluJzlb e+Eql^J EzI +e HI*, rela zl4 ¤Bl l}{E +61-H zflzfl .$zle| ql"+ 9lHzl# ¤e^la + il+.
E4lE
g E6l-= 5. +E dHlql ¤g "lgq= +se} zllHol4. ¤ qlr} Eill= E]]t6l Be +E Ezle ol+q4 flsq, 4 +
zlrJ= +d qlqzlel +s6J ¤+4_oE czlal {o1 zl¤.$ qL + glrll gtrt. Htl, 9d, {1E",
=ag "]+El= =+lql
{, :z A++ Aele+ qtJql +6ll^l= *e*a ol lzfl dH}ql relr dzl t49l zl"J9E + 5Ael 9lHzl= *= Eztq
aa^l ¤B6l-rll ¤ Lol4. fE: tr-qlsl 'zflilli=:rp
++. 'l]++E E4E=9 4z] "ll
glHzlz} + ¤E|]E+EI trIE eq.tr. d{+q= ag b6}El Hzl c.4E ilzl6l.q, +3 qlLlzl tr4z} B++ itzl6l+ E
E Eq-qtg ol$-o|o| ++. gqqle 4+61 *e +fl tlzl+ zl izl +"i11+.Boltzmann EEql E"iE .llHzl t4 ep]
+zlE ol+qA ']]%L E^llql 4+¤+. olel6J d{+ql^lE ql ¤4 Ss Ttr s^lEl= ^JEllel 4lill+ N,7I tr+-s-r+ ?ol iq
Hzl9 .J4 +41= E-J 4ol gEqI t$zlolH, olE glHzl 414
E +^Jql *aflrl be} a,ol gEq| 2$zlol+.
ㅇ {uJ Eill$ olf zllzfl flxis] Ezl9 {lHzlE EaIelH
grt$-+g olEg =
M o< e-qlkT
ㅇ
,Jol9
ol$-r|o| 6J+ ol ol$ql E6l-H ol. "J
glHzlb gtzls]q"] gl+ g"J"lE
ol
^lql^J
kE Boltzmann t+=(:z Ag .s.zl "J +ql ++6il
eE"4 +Hg + +9I+)4r- +-=.= 6J 7lE tI++(EE A+q E"J.J {}g
"JCqI ql{¤ <i9 "ll'Jzl"Jg 714 + fleq ot+ "Jel ql *=trI). aA 2+; gr{I.<lel Boltzmann EE= ++U a
~
Hzl4
~ 4 zl4 += S+. ~ ol 6l+q= qlqzl <ig 9luJzl #
+l+r 6l+EJl ol Ba(*+g E+ +F), qa(HIl6J -=1EEl= 0llL1^l SEll=
… =+ls=g
E He+), rela 4I¤{A6J4 azl4 tl^Jol+ B6J)el 4l 7l-
zl+.rB r9l d¤4"J E4¤"] zld + 9l= ol ^ll ="F9
t
+F qlqzl tr-ql4 aTle+ rJ4g +EI,I$.+ trE K
=+l=q
a719 8zl 49ld= Hrl eFE 6l+ qlLlzl
5
a9 5
g+4ol4r =9lE"l
+ flg aEE zJ4ol rl]tr6l 6+
E- ole+ ql
44 0 + gz}+ Ezl +9 dzl-501 4= qqzl r
7J4ol4$6l =fl.g
=4.
+o+ql^J 7l* +g* zH'Jel 6i+"J Boltzmann EE= ol 7}li{+ --->
(a) 'JP 8s
LflXI
ou alE EXI' -:lEEl= qlq^l sEll=
1
100 K
5
6
(r
5J 7fli11+---->
(b) tsg 8E
=aJ
1 E^l.Ll-E^lEol 7lE + ?l= qaj oilL1^l grl1= ,J.
=zJ
2 (a) '*3 AEg| (b) 5= EEoll,\lE 8E|,|4 Boltzmann 7Hilt+ EE-
=+ol =?l=sl
"Jrll, ssz} Holdf E te
qlqxl d|49 4Alizl Gzlol r +g Ssqldg EdE"l EE qlq^l zlzl6}q
r *g ^J4e-1 zllAlizl:z"Jfi 4-adc}. Boltzmann EEql =+l#
+= EeE He + 914. olBl+ CA59 B rzl] delql a
el6IE 7l-* qlq4 tr-Ell. tr9 zfl4l+ Es= r ^J4EE ! E" P6lal ¤ 4,"14.
ceq ++6|ril +"J 44"lEl gEql E6ll^J eag4. q=J EillE ce4 gEE qgg olllapx| g uI= fl^ll
Boltzmann Es= gEE E.9E Brll all;;- E^lql sl+ 4 soltzmann E-EE g+ql +qo} 6J+. qlqzlel afi'$ ol
q Y*e .ll¤¤ olaflalf ql qC qgg ++. 9sz} *g 5ol Boltzmann +sql uI4 Eeq= ag 016ll*+= ag
"I
.I++E EzJ-=ol *e qlqzl 7l^1617l ul+ql p+ gqE, +4., rflI Elo+ HEI¤ olallap El zlt"l 84.
=+lE¤
*EE"l Eill+ rill ^JEHE.Szla|fl,<J +4]6J + gl+. r?-l
-#V1^. 11
zlr;llel ¤tr
zlill} 9¤ *zlql EI= a\g $d6l i|]+= Eeel fl

Ell+ ol E4^ql^J= zl^ll9 CAEqI +6I]^J ¤E6l4l q
B t c ggl 7l/il
Erll, ol 4¤-e. *eE ol ;tzfl dHlql aa ol+¤ 1"14. $d zlap E= zlzll$9 Ceg E6I= 94, :z
=tsd"I
¤e$g ol E4^ "lS9 olel Eqql Arl gqolql^l ol+
gr+. rBl'I +"-l ++lql fl='dzll zlill'E=$ 9d zlzll4 d
1A eJfl zli{l ¤"1 4sq, 146l¤ :z "lR9 ?l"J¤. 6l]B6l-r" Ezlt ql
q4 HlE49 a.rffi- 9d zlxllel CAq+ zlul.tl4"F atE
+d ol^&4 6Jf;$ aI}- zlill, + 9d zlzllql +6H^J ¤¤ 4o14. ¤xll zlillel .!.el$ E6ll^l +4= a*qp =H{o1
611,
"lq^J 9d zlill
^JEll^l(^JEH *cal)ol
qBal Boyte flH ¤+ EBol E4 îlg+ de4 p45g HI¤^lzlHrJ
E Hzl, Charles9 Bzl, :24=1L Avogadroel Er-l-tr- gEq= qBrll ,tllEslolzlE zlE _H_rll ¤ 4,"14.
¤qlzl Î¤$$ aaJa}{ E}EqziizlE ¤B$ 4o14. tC.t SEzli{l BEoe+qq 0l=J; tC.e van der Waals 8Etl^.l
ra.r 8ell E#; rn.z 8Ell^.1
g rl-E 0l rlEel Es.E?

1B Exl -E.g
== 9d zlzll Hlq et Ege HIf,- $zl $g"J "itl4 dill
z7l4 E4ElolE * +s-* 4zilE +4 ++lql^J "Jq+= ¤Col4 Eql^l "JqLl= ¤tli$ ¤+6I= cllr o13g ;
¤tr"# ¤Hg + 9l= E^tE qE E¤g *"Iqlb 1019. ?1,+. S6J tglrlt:zlxll BzlEol ,l^J+4 trtlg E6}b Ell
4. "lelq} $Cel a4l qlrl Hle Sd zl4lE Sor$lol ffi ol+g+. gtg zglrl + 7l;ll ExI ¤s" Eol Ell.J .-ll+e+ eg
AEI eE9 alE EzI(E= flzllE9 dt"l+r. ^J46I-r. a"JEg dt rflag E{+ ql aol4 o + "l+g+.
Bd^la +zI eE Eg"lB.4. ol Egg {+l zlill Hzl#
¤g*g +EI otq4 zlril +ql^l +E" 6l+ Ezl¤9 B+ +
44 ol +q9 eE q= dg ql+61+ rll ol$al + ?Ifl+.
s. ol E-¤g Boltzmann +s(d4l zl^l +r)e+ A-J^lvJ 4
4b tszl +qq Ese+ ol -$Ez[ E4 e%]r+ gEql E=
oJ+L ql+61+ qlE ol+B + 91fl+.
Î¤g
re.r .EE; 1B.2 Erl
==
c'l+ t lls6ll^lE +44^l ald1a['ter)ole}= H?9 4zl](focus)e]E Ea o e Ei+i= EL rll+Eql^l +4zBl +g Eq o e LIE fl4E -gqTl
fl4^l+a ilc+. q+ ^|-8-6IEJ
qlEJQl EBoJE{, ll1iel *16I +zl E}*+.
^lgg
E4 1A eJC 7li1l
E 1A.1 g+E =J+1,,

> ol EE_IE H|l+= ols
sc 7lillq gaJq=
^l=3
gqqr'el ",.ie 4- .?sal= zl* HA 4i at
7l Etl. g5 u lxll E4= !E-Lf d^ll Tlillel dE- ¤861.= pascal Pa lPa=lNm-2, lkgm-ts-z
1il bar bar=ldPa
=E-d =^ltf. bar I
atmosphere atm I atm=l0l.325kPa

> u-4d TllLJ
gilel g= g4-d SE 7lill 85]3 zlill9 g+01 00ll
torr Torr 116rl=(101 32517fi) Pa= 133.32... Pa
TWlAl_t=^ld=otl
tl g "J= -d H^loltl. millimetresofmercury mmHg l mmHg=113.322...Pa
=-d
pounds per square inch psi I psi=6.894 757 ...lfla
> =Jg-d qHl rl^l - Iqill= ggEI atol4
trtqrxlg 8r.l roll^1 eEEl HIq eol trl+lltlB g nfl= gut
E?l= clgXl +lEapxlg golot Eltl.. ElU olLlaf alE}^fe-l
8^l 2011,\1 gE-d gq, +tr|, EEaJ, "l 3Ee-l T}ILJ= gr 9l 7l+C Tlqg ="*6lt + +7lql + zlzll r.lErl .qflg
oloF zrrl. q=(rB 1A.1), *¤ "Jqg ,*Y zlAlzl zlqg Bq4q *
e "Jq9 zlzllE "J+rla+. rflH +e "Jqq zlill= *
rlqfl^l $4"1 Bqzlr *e SEE Tlill= "J+qE^J(+
7l7E Elr qq6l= ql IIIE 71¤4 -sag ffi.t1zlzl 9loll ,l AA) "Jqol g4z}tr}. relr trtaq + .Jqol po[!,tJ
zlillel Ceg C*4se +B^lz) $ezl 91fltr1- TlEol rl g= B4lql olE 4"14. ol;-1fl z|
^J= +d "l/J. ¤-zlolzl
(+e. r7^ll7le+ 18^llzl). ol46J CA.q E6H^l Eq lBql^l FC zlq(iilÊ) "J+e-l S4ol ?"izli. a4g + Tlill ^l-
HIe+ ag 71419 ¤.F E'Jol gd6}7l olE E+E BE 8El|4a 6Jq. EI+^l el *zl 4ql Ba zl
Î4L6IH+.
=61-=
iil7} +4'il= Elqe r ¤-zlg+ 7l+¤ Tlq¤- ="*6lt 4E
1A.1 8E]l E+ *zl 49 zlille+ qs+4 B¤g ol+a ?lbzl9 q+= +4
L1]= zlsT} g+
6J
^lE EAel =al4 8El{, . E?]4 zrJ?:z r.le9 E4 4zl9 E.q3 7l"J4l= zlzla_ +e*+. g4q 71"JAl
4 ^Je# zlzla_ Afl6J + 914. ; .<lEz| +ag 844 (Galileo9 z'llzlql TorricelliTl-gE6J)= i3"l Er-a +g 4+
CA# 7Ie ql=
t"J+ ^Jql= +44rll B+. alE ^J'ilE e ^llg 4e+,q :_ lJ.Eol ¤-6114 9i+.+e TlEol 4zls+
+4L11= trll gs* E+= r EeeJ r, Pq % Sq p,a4
r gE Tol+. (a )
+o
7[-=.,\'l
.loo
7lE
rL
o
H-
le{ \ t_lo ota{
'XL H-
(a) SH
(b)
z141zl +Ei.ll= EE ga?
$zlz| *zl9 zlqg #"J
zlzJl
oeu ota{
ESl6[ E- Eg:d gaj
s."l "]14ts ullrl s= a"l+. ol trllq= q+71 q+ "*zl oll
Eql Tlqe ¤e4-o-e. +Aee Cg tsal q:/ q+^l ,*A (c)
eg "Jqg Brll != a"l+. "Jq9 st +91"J uI^*(Pa, Llo

XL
ota{
H-
<- 5.o
EL
ole{
ts-
I pa=1Nm-2)3 Er+zlE ^}^l lql^J ¤86[9+. ol "]e.lql

q= q+l ++l=ol olz.lE LJq $olr. 9l+(E' 1A.1). I bar9 lal lA.l 71.# 7lE= /.l.ol0ll 53 "Jalel gE= Hg g'ajel gqrl
(a)el (c)ollllilaJ =:n ol! -dr*oe
sqg qlolElE H ilB trll ir= E= g+olq, ol4g=_ p"e Eal6H 7lE0l "Ja1=ole '2ioltt.
rajLl +=eE
g'eol e= q= 7lE0l 0lE6lrl g= Aolq'(b). 0l +^l'sl 6Z0l
s^lqL+. q+4 Ee
+ gq
^ptst âotq..
,o ga zFil 5
ElEtrte| 84 r gEr Et+l
E"-14 deq +c a4= +ile+ *+le+el *-e_E +4u s A.2ql +=.611 +9ttrI. ol= d+Î= qlarll rl-o=$ pol
rI 7
T.5,
^l-e"++.
Eflzt dp=fil x E?l 1nm= 10-em 1ps= lFr2s I pmol- 10r6mol
nEI^l +flEe ql+4 "Fi Bol fl+g + 9lq *6Ir" LI r

++lE Hf(zfl=,.f)= d+^le+ d+ÎE l-ad ++lql
+r" E +41^lvJ +:14. z46}q (844 "D/++14ts s 'r+ aol 4+Etrt qlE^J 1cm3=t (cm)3, :r-?-lA (10-z-;t
oJ)o14. qlE^l 1cm3.g 1c(m):ol olHg +Eolq+. +zl
^l= 5a+ E+lE +a+ +il(+-qucE =1015m3
=io14.
+ EillE A*g m-2.5ksol+ E+ mtks-2.5*a +EI.J 4l4}g g trllE r+44 zl6e +48 ,I++*e] fxl(n.nnn
+ gl+. ol Ezloll^l= e3J9 Bflzt l ksol^lEJ "JHI49 x 10,4 es_)E B"t4Fl alE 4.ol 7It "JA6IE|.
E= ZI+6'l ksE 4441 9ltrH+= ++l=E a+E +Î 7414 Sr zlE tglzl fleq, ol# z|=. ¤9 s e.:oll f
6ItrD.++l=ol z[=. ¤9 s A.lql ++qq 9lq. +6I +9t4. ol ole.lel EEl4 caEe F+ ol 7lE ++lE
d4l4 + sr ++l="Jg ^l-+61+ 4"1 ¤zl"J e_{ ++ E aElsE +4Utr1. qle^l 5bE(EEAI EA* EEq
o
o + Sr tglz} olrlfl.tlE H"-l q 7tr ++)= Eeaffi
^l-Sqr flE ++l=ol ^lEel +Ele 4b 4"
+^J, Ee=+
fl gl+. +^ll +"+ql ,rl,el E"]zl "JEg olBq4l(zlgqd) 4 4"19 F zlts- ++l= moldm{r} *ol ¤oJ* +E ++l
zJae +$Lllr(qAql A=*g m_o4), ++l$g Ef Eu} E +48 + 9t+. *e +E +E ++t# r++ Ea4
4l(zlflill) z1o e LtElUtrHqaE]] 4olE me-tr). zJo+ g;.Jrp.!lq.qlaql eg+E ++l hH, tN=lkB
+9,==g 109 4lt "JzlE +4ql= d+^l-= ol+ql^l + ms2.E_ +4urHzle_ ¤9 .s. A.4).
44zls. ++. zI* -tr¤4 o e ^F&q= a# z[+ ¤9
qql4 ¤Bg ol$ ull= ol zlF Hlqr-el oJ{ol rlzlzl ulzl ol :zxlloll,{= drAl 4EE eg g,<16p. +448.+.rs r
SqJ+ a+. q+^l +g zl5-el +ol= q+ E.eql Hlql 44 9^ll"l-+ SaI6l-= Au_zl +eq +qA gqql^J
E t
=
,*+r + 9l+.
E "J6lAl 8+61-zl glzl ollE"ll rls" alt Eaql ttI4^J gE4l
8zl 491 Eq fl. zlzll r.lEE
"Jqg Sqal= olf-aN.<J "t+ + 4d r}"l9l^lel e_Ezl ,r}olal +il= rtq$ + 9i
+Ad-=ql, "JqAl= "Jqql el=6t= ^deg ols-"ol-!. {rzl +. rel+ Tlillel *qg ol+6IE
^P"++ql +
6}ts TlillE
+. qlE^J Bayard-Alpert oJH 4Jolzl= ,lAl +ql 9l= Ez| +6J gd-7li{l 8E 4E= AEB + 9l+. "l $d-zlzll 9s
ol$slxlzla ol olgEq s$g "Jqel ++E 6ll46J 4E= EE-+4 tE 4Ee+ 5"J+ a,"Jol B'-4eeq(Eq
+. E 4ql^lH^ "Jq4l- acg d+q 46ll^l +olols.+ 3A), -1el6}q g}g-e-= ol +^tel Eag ,\J-$g}e--tr-Al Ea
ol "Jqql Ir].+ ¤'Jq4l qq?ltsrll, ol ¤6J-3 ol tlilel d e-l B¤¤ ulalaz]. ++.
,14 +e}9l ulzl= Er+= E6l]^l Eqq*trI. E HlEillql q gqql4 4E^JE gEE Ttr s^l6tq, oJHlzl_oE AHI
+^lE *qql 4.¤-6I7lE_ 6l+Ell, olEl6J HlEill= rill-^JEl] (K;'K7l-otqq)sE +4u4. gqql4 gEe+ d4gE
"Jq,llol zlE Eq}tlil(transducer)E o;a" alzlE {+. rt"l9lb +s +4171 Hgo}|l dB++.
(o) gs. TK=01"C+273.15 dul4s t8sll (1A.1)
ol +41= ¤xll dal 4E. E+ rehin 4tre eel

=zl9 I
gEql *aJ z}].Eg +EzlE t^-l 2ql azlla[fl4.
6I= aol+. "l 49 t'cg =94"J
gs.zlzi gEzl-e+
E4l"Jql^l=(zl#E ¤Bdql^J lKE A+= a
^F8-qr flzl"J) ¤.EE E g 9"la}zlE ++.
al TI*IE zJole]. +¤^laeq, ol gEzlz| $5 g*4 g
4 B¤g ol+r 9lg qe+ r?]r #= E!+ ¤Bg ol+r
q 1A1
9lg UIE ol TlEel ,Jol z.l¤ 100 ="$op, alxl b#9 og z]trJEt
E .E^l6l-H+. ole+ *ol Ct gE 4E7| drl e_E +E+. 2s.00'C= AHI *+lE ++U gE--E Hl^+71 9l"HrJ= te.t
6 1 7ldlel8tr
Ellg ¤tr
=i{lel
qle} qq ca=E #g B^l¤:e-Er^l ol +4IC+ gdf 6LE^J 8zl9 zlqr+ ffiafg,t1 a;g
^lE Eael 1'-El]E
Cgts + ?t+. olel* ^dAEql= q+r+,JZ aF.l 9l+. zlalzl qlEql a 7lH"l "J49 E.= aol+. "l += Hlsz}
aal m; ¤z116l-= EeE "&g +4Lll= ++(E+l: ?-E "JqI4-"e ql+61 +71 trllEql zlqql z16llzl= E, tr14^J
_:.fl, kg). sqg +aeg #g +4Ll]= a"l+. 4âg "J49 sr+
+71 y; ^lEz| zlz16l-= +aE a7l= +EI4= ++ 9lzllrJ u(lbar=10s pa)4 7ls(g"J4al 1 atm=101 32s pa)9
(t9' "J*"lel, m'). + ++lE E¤zl o e lrol=tr1], ol=g d¤4"J 4zl SB

rz; sxJlalg. Brl¤ z]lz]l(fl2l., EzL E= c}trr^l +
g +E}'}]E 4Eol+. glg Efl4 ¤dEol Sqql
^lEE
=tral e-l=6171 qlEql ol ce.E {}g sq 6Hl^lE <l
fl E)el +E +4LllE ++(t9l' E, mol). =e6J
s + H nalE 4ol +4. EE4 CA=el <tg ++4E rll
EA%F ,z(..5 f,z}l g:olzlE {+)g ,<le. oJgl -qgt= ¤+qr il= "Jqg E= g+ p" o e,<l g"Jo-ITll p"= I bar
Hrl¤ z]]illE +E +4,J+. 'EAe}'g *^l B4ol4,'s] ol+.
+"+' E= A+al 'oj'ol
qlq. I molS C*aizll rz g
el *i-12 +ql tsA szl-9 fol4. (201lLJql ol
^lEE ^JEI= Sd6IAl B^l6tElH :z .-cE rs_ -tr^l6ll
ql+. gE= 34{s_e= + ,lqg E
=qfl=
AE= qill6}zls p{al$.zl"J zors'JllzlE_ Hsl9zl 9+
"F ^lE= E-ds_C
611^l d+^lag q qlqzlz| $-tr,rJ EE_E
"J.&3 ac6l
9t+ ) I mol R9 211i11;5 Avogadrc +(No)qr at4, ¤4 + te gEE gEel
+"Jqr fl= <tg 6.022 x td3mol-'ol4(No= t9lE zlC =o e^Jd"l4. o--=_} ^le-sPrl *g ^lE +
{lHzlz} 4"lr}. gq+4 'cs.E zla. re_ s.
l}f"lq, ++6J fz\ olHS +e_l6l-ol4). .(16l.=r]l, olag 4]zl e-E= T=0o p += ¤trl] 4sol4.
ql EA9 E trB M* a E¤ t mol9 $lz|, -$zl., E|
r=0 old.9 3s= Kelvin 4E= zlzla_ +Eql= 4."1 zl
slql^]9 ¤*ol4(++l= *^l4e__E= E B e-erfl, +
tI -H-¤4oJEll, ol 4-Eql^J= gE +al= AHI(K)g +4U
kgmol-'olzlq} 96l gmol-'$ a.7lI; tI+). rl-e 491 Eol
4. r<elvin 4_Eql^l= EE ai6d(gg, E, :4:z ++1171
fl= 5e+ THillE Ea%lg r e+g olf-oll.<l q-q-r+ e 0lFL Sslg 273.r6KB -oE4(+= ++lE
ol +g + ^le ¤¤9
?14 E olTlql q= +eg 6}rll Elq ilEql 2us]cvl4
^lqq
m Exlal
zl ?+r fl= aE 9l+). rBlE t atmoll^le-l EE q-A(g
n=M = =ct gel +¤)ol AI+fE+ 0.0t KtrJ# *rll +4+q, q{^J
EE q=4?ztt.tsKT} g+.
EE gE 84 flzl-¤=J=ol+ Ezld%l(+"J flz}4 Ezl- 6l-z}.B4
E e* ++l ks)e g es}(gz}{ Ezl9 E B d=Jolrh ^lE= tr-+ +e.<lEs-tr ++9.+r ^lEE
+ C¤ol zl3 ^ls$ dillg ^deel -J4 Ae$(e%r$ A
++l ksmol-')4 tr|s+= Ag +96I¤4. flz}4 Ez].9 g ^de) "l ^dag 371 ¤trol+r ++ dqr"l4 +rile+
^JEH4 E e"*
M;mtmu! olzlE gz}*ol+ Ez}e}ol4
eg CdEol a7l 4d"14. ql¤ E4 ^lEe+ E= 4'-g ^l
-:1 g=;r g1z]".l1rn$ flzl-{ +zlE {elol:J, ru,E flzI
E.ql^l E"J+ itg +4q1= ^de-g dtrol4r qI
e=* {t+ s^l ?l {$ Hofe};, olag +-qflCE "}= ^1lz!
olq, +7il(Ei]ql 4I+61= 4. 3s+ "Jq4 ee ^ddE"l rllzl Cd"l4. ee} "JE
=lq)E "Iqq. p=mtv q^l E= 413 E4 .,(lEz| t-"J6J {tg ++
^lEe+
Eillql= gel pzl-++Et + ?tbEll, $qg r EAI 4oe rllzl C{olc|. rzJ ^dAg g Cee qb X*=xtn
q ^l.E
4L+61+ e F= ol eol zlollzlg gol AE +b aol+ ll- Ag E
^dd==g E+ ^ll7l ddol4.
(t9l; :lIÂ Paol4 1 Pa= I kgm-t s-2). zlill Ezk #"JS.
trl+r+ Bol ol-4" qfr|. 4l&Hql^J= E?-14 "J(gEe+ Ae)g +zl(2s.00)e+ +91
^.lg
(l.C)e+el -zrr e-8. E4f4alz}9
71y - (25.00 oC
) / "C + 27 3.1 5 = 25.00 + 27 3.L5 = 298.15 ^Jal 19 -H_ol-aD. 9lE ^l
e-l Efl r= #6ll+H r-2e8.t5Kz[ tJs-r1.
++l("1 a+q .c)Eol +ile+ ?"1 ^J4lg+E ag ++ "JHql
6Iq+. olq+ 4l4I ¤zl¤'+=d. 4l4}B'ol4l olft.rll, ol
,o ga zF{l 7
EE gE 8^l gq+4 gE eE tt9 oql gE= r=0o14

a_ )^71r=0K4I. ifzl g*=+. ol lE=. ¤4 gs 3sol4,
b+E ,J4& qBAl +]6l-= S4l$,ol soltril0?_l "Jqg H|+

ulÂ E E+l a7l7l9olz| qE +al$ol p=soltrI). i1q a IE 7
4 d4 zlE= ¤4 4szl otrlrl qlEql ot4r 4= a mi

6n
ol u|galQ.
in
d
0
1A.2 SE]IAI 0
1l+tr:l,1lv
g4fl +++ Eeq ^JEH: n, v, p, r4r 19 Zl53 zlzl lg 1A.3 gSEl eEoll^l sd 7li1lq gqE 1/v0il El,l6tl^1 -E^l6l-E 4.ld
EolTltrl. 0l c=g l/v=ooll,\l galol 0o+ elL'Er[.
r E^lE} f
?lxl"J dE4eE gsJTl HLql el6IH olE =01
,H"J "JE +E6Ijr" 4"lzl ql H+= zffix o + ¤A¤+.=!:

+ V=constantx T, "JCqi n, p414 (1A.3b)
Charlesgl E=l'
de ar+"ll el6IE 4 EeEe olE ql H+=-g tls +E^l p=constantxT, "JCdJ n, Voll,rl (1A.3c)
4++ 6L+E ol{^], $E]|^loe +48 + ?l+= 4o14. V=constantxn, oJC¤Lp, T9lrl (1A.3d)
= gH}4ql g-e
Avogadrc9 flal'
ol q+4 ae
^Jq4e ++'J + 9l+
Boyleel H{g p+oo1
Bzl4 Charles9 q= +EI tl4ql^l
p- f (T,V,n) 8Efl^lE gHJ4 g (1A.2)
g,J6}rll ¤B6l-= l-d H=lol{. qlEî TlillE BylzI d
"J
ol Ea.lE + Eeql 4t r, r, "l vel {t=g "J e4s v-aT+bp+cp24l E *=+H p-o"J +oJq^J=
^lql =A+ v-aT7l g+. "*g +44Eol p=OoJ trI"J B"J6IZJ ^dB6I
E "Jqol + a6lld lk9=_ ?*41g+= 4014. EaEe 44
r ztdE {l4{ " + r ^J4# +e}8 + glzl"J +471 zlq] C^J "J4(p= I bar)oll.<JE
^JB6l "Jg "J6Iq
p++ql^J
tlEH^lg gr 9l= Eee 4. zlzl "J g+. :z eI feoJ {lz} *H+l6}rll ols" qr fl+.
'Sd Tlill'$ tlE]]^l"Jql, ola,? p-nRTlv* *9 ge +q :.8 re.zE zlz-ll rl-E-$ "Jqol +e Helql q-+ H6l+ E
4l+. qzlrJ R3 zl^llel ++q ru+ ^J+trI. "}-g +4U 4,o14. ol :zflu 4 ?+ +dg fl +"J gEql q
9d zlll9 ol ^J44e'JHE ¤EB4# Aq+4î + t 4o14, 5.f;,!ol4l 4gr|. Boyre9 Bzlql 9al$ zl4l
eg aol+. E tgdg tl-+d(x/=constant4 E* y-constant/x-tr fa|
\ )E x9l 4oll^J E.^lg "ll +s= *d)"14. ol :-H 4tl
ql rH lmql^Je+ Eol "JBS (r/+q)ql ql6H^l rg +E
(a) tr84
=zt
z!$ zllzlle) Tlal B4==e. fl4. cnurles9 Bzlql q+ +i4z} $E.oil tr|4 d¤4 o +
q-.q_r+ a- "Jr glg aol+. H6|= Eo&g +4U 4ol :uH tA.4+. ol rBE di$ E
gdol?+r. ++.F"Jde "Je+ "Jq 6Iql^JE Ce E+=
Boylegl H=l: py=constant, oJC* n, Toll.rl (1A.3a)
\
p9
j
a. H
mi
l[-
6!
0
0 0 -9E 7
0
+n'l, v
fal t A.4 "J8-d gzl 6toll^1 gdaJg z lill9 +tr17|. SEoll EBI- Hdl.= Eg.
lg 1A.2 gEeJe-lSE 7li1l7l qq 8Eql^1 LIEILH= ga++q E=g4l 0l d- EF r=0, 4 0=-273.rs'colrl +nl7loo+ +alEq= ag T=
4 +d9 .s+.N(pv= 8#) o-e^l leE +Etr [. 6tGal.
-d0
8 1 7l{leldtr
TIEEI
v9 o. 8Etl=g| EE
a roi
mi 6r
6n
1
0 +rJ, V
0
8-E, r
feJ A.6 gEaJq SE
1 7 lill7 l" LlEtLt[= p, V, T 8E.9 Bq. 0I sEE 0 lF=
fg lA.s "J¤-d +tr| 6fo1l^1= g40l SEoll dB4o+ 9Eo|'H, r=0 tr=01 4l7t LlEl'g + ?1= +g-.J 8EH=01tr1'.
(-27 3.1st)oll,\1 0o e qdE+.
+EI,{= +dol+. rB rA.s= Sqel gEql q= d¤ Hs+

=EC-olA{
E +4U 4o14. ol reE dEe 5q.nlC, gA+ +jIl otlu
=
4q^lE Ce H+= +Eql= dE"l4. pY= constant
a V*T =+nl5
trtrJdE 8^l + "JE ÎolE +alE +ql6H tr48 olE rur
o-n
ol zldg q= E^lE qltr-= 4."\ zl* +trt. 4c

LIE|'l]rll
es+89 olBS +de e+el9 olBetr} gd B-zl6i7l
flzl ull$"ltrI.E^lrlg trI lCg +{Lllb !g += ae I
+il|, i
E?]slHl^J ¤l8-El= 6J 6=s6J fB"l4.
fal 1A.7 ral 1A.69 EE= g8-d8EE EES| Hlelal 1A.2el#
tA.:41 o + ee5X deEg +*r+ ?ol aI49 al
" + s- olq, g8-Ll gaJE EE=3 ral 1A.4E Egr'C, l4r "Jtr-Lf +tr19 EE
qlel + 914.
ral rR.s9 os+iild=o| Etrl'.
=3
pV=constantx nT
EE dE 8^l 'oltl zlill'4e +q= B¤4 o e "*ol Î
ol n4 r7l "JdEJ qlE Boyleel Bzlr+ gzl4q +6tr glzl"J'$d zlill'+r +s= {ol u}r}a}q. Eq
^13
(pV=constant), n4 vL* p +4 aI4zI "JC6I|I *zlp ullE sBql^J ¤EBJ utq ?ol Ae| BE 'oltr-4 g.JEql^J= AA,
Charles9 H!$ "Jzla}{(p n T, V n T), E p4 I7I "J¤6J BB, "i AB tl-szl¤¤ol E+ ?zl"J g¤4 o E 0ol Elzl:.
qiE Avogadro9 g?-l(v". n)el "Jul*+. ol Elql ti+ s ~ ?+}tri. $d zlill$g A+q= ol tl3r4l¤¤ol 5r+ E"J
Tlillql qlql^J 5"J6I+. o + E+:deeq E S"J olq4 E¤I ool E+.
= Îdol dE4
olag RE +4Lllr. 7li{l tt+4r +¤+ Ir}+î +lel 4e
q+4 B"l ¤ + 9lr olag gd 7li{l H4(+g $d zlil lg 1A.6E sEg "Je=+el 9d zlillE sqg lA.4^lql
4.q1a11olrE ei4. "I4: +'le+ gE+4 gEqlol Ell6H^l -E^l¤I 4o14. $dol
zlzllzl +4'J + 91. ^J4= EE$E tl{+ol+. +
pV -nRT lF ) lijl ts^l (1A.4)
ol
^lg 9E
zlxll9l ql6H^J+ 4+q=
^J=l4ol{, zl rB re.z, rA.+9 rqsE¤: ol .trEg E6]l^J zlE +H.ql
=^].4
illel *qol oql zlnlfllf) trl g"J6llTl+. E= aa 6}ql 6l]'J++(rB te.z).
ol g"J6tzl oJ+^lzl=. z14l= gd 7!i{l(E= ol^}
^J ^lg
zl4l)?+r qlq.grll 7li{lb r Sqol yfo}{ffi dd q S
d zlzllz]H BE4q, p - ooJ ++ql^J= 1A.4^lg g"J6l4l
ㅇ
GEf
qtr
tlg
gazn{r E=rEorE
t¤ql^J 100atm, 300Kel eA= PvlzI "J¤+
e
EI+^lzf,r]. zltll ^J+ Rel Ztg "Jqol ool q= +elqlrl(zl
ㅡ
*zl 491 Br sooKtr z|$q4. "l zlzllzl Sd zlille+
illz| ol.rJ-4 o + qf6}z]l 617l g16}| 4) zltll! pvtnT= +a 4.ol BE"el4H $"t"JaJ "Jqg 44441-4i
6l-q eg + 9l+
N Perfee 개념
,o gA zF{l e
r.4E .tlEf gsz[ $e[z[e-E BoyreelB4e E7'I {lH-e-e. ¤EB +E 9l+. 7\1)l ^\
"JHol tolzl?-]?+= A¤.
E= "J+6I{ t +q= H}e_s ¤olH ga ^lz} =t."J91 zl
+ 9l+. rfl+
qltr-E+ $d zlill Hzlg pvtnr-Re. utTl
e¤. qlzl= EzI fz| "J+qzl d-a+ H}]E +7}6tril qq
+r. -H-H, 4lE t4z} + ^llEE =d-e--+*El trI= ^'ll t 4a zlH9l "lzlE B+6.Jol F H]ls q= 4o14. 4e].î 7l
EE z4eE Hl¤ a+qlE pvtnry tfolzl qlEql ol
ille-l +ul7t HIe-e ¤H "Jqg E]|E qq, pwl gA6lrll +
+ ^llEel <lE"l trl+"+ eg'A* zl4l Hzl'ql u}el ¤a
gtrl-.
zlg+.Boyleel Bzl"l 7l4lE a"#"ll ++6lrll :r= zl4lgl
r+ 4+qt{*g "Jqql^l) 43 Ezl-E ^role-l ¤+ ,1"-l
PrVt PzVz g4l zI *g "Jq"il^J= ql*61 gq^J tr-gzlql ¤9 .F6t
frrTr- flzTz =Er
Tlill (lA.s) "lilzl
-l. rlE +B4se. &E"6I7l rllEol4. Charles9 B49 EzI
ol 49 ar]6}q
"lzlel "&pr)¤. 71^lE
o;e-E +4'J + +=ql^l ¤EoIE]H +zI9 ¤+ +qol gEql ul4 6zlaJ
gl4. zlzl EllolEl!$ olclle+ *"1 sqFal + 9l+. += Î¤9 "l*dlot *trt. &szl$4zl$ E{E=$ zlqr+
"lzle]
r,l zlf rqa q +49 +H^l +56Iq, q4^J 8zl9
n p V T =
zlqql q "Jqg EIrl+. ol +4lql 4EL C"*4"J ¤Hg
il+ qol
s.9 rnE =
lE_ol K
o=. 100 atm oe. 300
u-ola}.
3l+ .lE-o1
oe. ? .lE_ol
oa 500 K
ol aB. ,l4l BzlE oJHe-s+El +irle+ Ee+g (b) 7!i{l E-d=

=ol
t}4l^l7lfl(VfVz, :a41 nr=n o\l:E) q-q-J+ Ag + Tlill e*+g A*g 'I +d s+El= 4Z + dE zlzllE
4l= Eg + ?l+. ol ;lE9 d4 SEql $"tqlt zlq$ 6}=zl= oI= "Jol+.
Pr Pz E6JE(gl{ zl4l$"J "Iulz +E q¤ zlzllE u|{z}zl) $
r, T2
ql zlill Ie-l Hs4 p)E q-.q=r+ ?"1 49¤4.
olag q+!+ eol ra + + 9l+. =q9l=
h=\P +E gal t8e-ll (1A.6)
P,=ftxP, 9zlrl xlE 19 EA%Eg ^lE +ql Eq gl= Ezl¤9 6 5

ql"lElE Bq+H q-q=4 ag a4= Eg + 9l+. f no 4 +b ESE^J, C+ Iel E EEol4l 6JtrI.+
s00 K *r=* n=nA+nB+-.- EE tEgl (1A.7)
P, =:oo r x(100 atm)=l$/ 31* =
xlTlB71 1A1 ol \e zlz\lz} roo atm9 I+4716I+E Sg qlql= xr=0ol qq, E I Ezl¤"J"I 9l
"Jqg +4.llr1l g tril"t]=.!:lol Strl.x,oll *pL "l Aqql q+^l g.JEE
¤ gE= g"I4 EldL+?
」
)m6:-E e^dol qBE tr*fl"I x^+xB+...=1ol cB6Iq,4+^J +
E "Jqq 6Jg A4l qlqr+ tL+.
zlill ^Jq]^lg gqqlg t6ll^J ol+q= *H+l+ +

p r+ ps+... - (x o* xr+. -.)p-- p (1A.8)
9d
4l^l# +E6l^= ql ol+qrl qlEql EP]ElEql^J qlB6l ol +41= dzll zl4l4 $d zl4l "J+ql 4 B"l 4e" ¤trI.
u!s-6J zlol4.s"J olq4 "l qq z4 aloll lli zlzll E= + ael+ ++ "Jqg
TlillTI ol^J4"J tr]i=, lA.oal o
^lg
el C¤$$ 4l&61-= qlqlE ol+q= d+dg zlzll !l s.rJ -7 zlzllzl ++eE E"J+ gEq^'l d4l +ElE rlzla}
=
zlE 6I+. qls^l 2el.rs Ke+ I ba.(B"J6}rll 10s pa)e.l aa A+ql +ElB "Jq4 ?4. "l fl++E 4¤+'++ $q'ql
g E= dLl| EE.9[ $aJ(SATP: standard ambient temperature ++ E4E C9ol4. r4r olag q+4 *3 paltonE H
and pressure)ol{r 6l+EJl, ol a{4ffi^J Sd TlillE .5 + g.,¤el qflH 4"14.
=lel B4 =A7l
El, V.= Vln? 24.789 dm3 mol-,"I+= 4l+ er+= gg +
qd{E o 'Ce} 1 atm9 lt= c-Egt 94(STP: standard TlillEel gaJEol +4r]l= "Jqe
9l+.
temperature and pressure)ol{r AEiH,=tll, ol aao}ql^JE 4 C+ zlzlr,zl +5_q E *zl= zlzlB ullE
"Jq=E .Jr+ g+. Dalton9 ts4
10 7ldlel.str
olE4e Sd TlillEE gtJEql 41411,<-1uj dB6iq, q+^J %ig tr|.q=$ t"l ¤4

+E "Jgg AE6}E cll "l*E + S.trt. +E "Jgg ta.ozl
o + c99q, q¤ zlzll.ll ..ll6H^l+ dBqI+
D
r(N, ) =
u##^-, = #*mol =2.6e mol
w +E g4 4ttt
4fltlql^J aa+ +zlE A=* EEg adg qlAl4se
n(o,)
n(Ar)=
=
ffi-
1.3s
39.95g;"1-'
=
=
#k
1.3
&mol
mot= 0.7 25 mol
=0'033 mol
Nr: 75.5; C,2:23.2; Ar: 1.3014. di'll $H"l 1.20atmoJ q4
d+Eq ++ "Jqg 9"IzI qAL+? dill EA"*3 8 +ge +lql^l Ee 44e-l
3.45molol+.
EA# 3.45mol-tr ++q+E +s-iil" ol g- +g.q+ d
I-49 Al,El f E $qg tA.oal o e AEqq, "l rl9 ol 4 "Jq t.2oatm9 =,6tH ++ Sq# Eg + 9l+
+6IqH C+EE E +¤¤ "J"l"t 6J+. E E&3 te.z
^lo-e.
AEqq, d*"1 ltt,?! ,rl.E. +ql ?lE g e%D Mr N, o2 AI
"J +zI9 Ee"tg ry=m/M,7]-¤+= ^l+lg "l+61-H
g E+g 0.780 0.210 0.0096
4. 9 #e ^lEE dA e"*q1 ffio}{ trEIÎ ^lEel *E $B/aun: 0.936 0.252 0.012
""89 rooge-tr A6h= 401 ¤4alr*tol+zl 6lH e"J E

E¤e+qg +l4}"l ¤trD. Irlel^J NrE e*g r0og \l7l gJ| 1A2 ol4lsl+Ê rqEl q= e"J EEgol
=:9
75.5o/o,4 ZS.Sgol ¤4. 7s.s2(NJ, 23.rs(O), 1.28(Ar), rqr 0.0,r6(Co2)ol+. dill
"J4ol o.eooatm9 'I9 +E Sq# +6lq+.

Eol roog9 +zl +ql Eq ?lE Nr, 02, lEl-tr ArE ee} urle 1,2000'0''800'0'68I'0'¤01,'0 :E
* 7+?+ 25.5923.29, r4l t3gol4, trl+^l olEE Ee
T]ILJ=
=gET
l l. .,.le E?9 8Ell, EEl4 z49- r Eel4 C?E Is. E¤col+ r4s ^J"ll^l .J +"J gEql qlB.6l+ coltrI.
=al4 =
¤EgtrI. I6. Egcol+ r4s ^Jql^J 'J +"J "Jqql 6]l%I6}E coltrI.
a 2. qet4 gBe. ¤|.+61+ 7ls"d
'lqE "J4 "J4"1
z=I"IzlE 47. fi$ul,flol* r4s t'-.ll^l El *"J +ulql 6llB.6l-= dol4.
aaol4. I8. g5 zli{l* -Er= aaql^J $A Tlill H4g "J+^lzlE
r 3. geE *El]= Ae-ld+ E+# S+^14++ +41^lg Tlill+.
grfl*lolr+r qFI. tr9. Dalton9E4ql 96tE Tlill(S{; g6Jgol LIEIL11= "Jqg
A 4. Boyle9 Hzl"lut Charles9 H4g +A+ +6J tlEll(ol a+ 4 ¤E 7l4l7l tEo + 8zl dillE zlzloJ trI +Elr-l]rll El
p
- o)ql^J"J g"J6ral cB6l-= ?:d E=lol4. *.ltrI.
='JqEq
=s-d^l=
ce ^l
+4 al HE.
9s as.E ÎolE +41^l TIK=01'C+273.15 zzt.rs!- g"J6rr+ tA.1
$d zlnl B4 pV=nRT {xll zlzllip+oolld 4B rA.4
+E Sq h=\P E= Tlillql qql^l cB 1A.6
xr=nrln ;(-1 ol
'o
E BO -1 tA.7
E iEE
n=n^lns*.,.
E4 18 EIIffiE'g
Tlillel Erl !l.g(Ez} -$E"E(KMT: kinetic molecular

> ol EEE Hll+= ol8 -
theory)olepE *+)q^l - 7li'llel qlqzl= szl :a Ezl¤
q7l^ LllEe 4trt0{l^1 7lf,Ll;4,
6d4 ^7tl6t=
_Eeo.e+q ^lÊ61.=
8aJ4
El
=gEl
+=6llLfl= 7la.:l.
E BTI SEql zl"Jg+r ,LA++. "l #
EBg ql+61
=,J6[q ^l^]E ululo-J TLAE++q ,Jq* A=+4 +41^lg +E6]| U zler
s.il EEe 7lillE gE_t ¤¤(E4 rsA), 7li{ 84E HJt 4s
(EE lsA), :lal.r. +B]|Ef8(EE l9C)g ¤86tts EllE olt $E6Ir H,d Eq 3zlqtql^Jg s-qo14. t
Ert.
> q4fl TllLJ 1B.1 Erl#E=J

zlxllE +,\lB 8+e rl3 fTlE E^lEe ol+cl^l.r., 0l Ert
#"Jfr,= +ArE A5= 6lE^l rEqqte] E.loll 14= tszI ¤-$ -E Bg +f,.r+ ?3 ,tll zlzl zlzloll "J4qI 4"]14.
=01
=-:drt.
t. zlill= rdEqlE Hzlg I[}-=-H^J ¤+4"J +4LC +
> =J.g.-d qHl rl^l
8E6l= EiJlts 7l6ll^1ts Coll BIE{|6HA1 7l+EtlE Newton9
¤¤ 6l+ d=Jol .ol gzl.-tr_ qq 9lq.
2. ol E4¤g -4+ A?]ql El6ll
AEel g0l0F 6l-tr, !E 35801 H=Eq= aE ^Js +E Î"lql BotzlE
îl2E.l= qlE6l 4Lg ulE¤ zlzl:n_ gleq, olfl Hql^l f_ a_
"Jolot ElrHElEl^fe] 8^l 3). ^J
7l- +^l6J + 9l+ ol$g eA$ ?JE+.
oEalrl
rI C, ei&l
6l
E
¤+l4lE +lilel ,r.lz} HEI¤g ^+ol+r. t}trl. +lil olE P= mu CE AEZJ t8ell
E ^lzl Hsl¤r+ *41 ol+ BL6JS +4ql= 4ol A-,Eolq, ¤+!B=g %L6Jg 4=+s Hql^.i +E= Hl¤6I= 4,o14.
rq6}q ol+ +qol eq4E %I6.J"l 4sH +E7I +s rq6lq E"J+ e*el F"{lEol E"J+ 4H " e F"6t
4. ot=l] d:sl r.ll -EroJ tste+ aol +E= "lE %F6Jg 6J* E+
q4E %I6-J"l trlsH dB ¤+lB=ol 4e+.
+EE ^l+ HEl¤¤- 7ft.=E a4t ++. F" 4lE +qol
r+ql Irlg= u,, ut, o) u"9 {B# *=+. ol CEES
E6lE r ¤+l4lzl zfla+a "J"J+. +qol Eg+ +F
+E= *E+ qlAq /,=*Sms-'g +rE" 47I "Jel x$oj9 4+E r ¤¤' *'J"l HdlE q^l zl+q= aol+.Newron
g oFE"614 /,=-5ms-tg :7 Hlql H;6}e-tr- olE"6]+. 4,¤. el zfff:-
F-E rll2E4ql E6IE A=*"1 z"J S4lel
+4U+.ffi$1+q)E aolE PphagorasE Aqql E61l^l #4ql zt+61+ e Fql Hl4+4. +
f -u?,+4+u2o e +48 + 9l+.
F=ma ol
E
vZ
6J¤ zuE CB ¤t*oll. ats 4E9
^lZI HEI¤oloe
may g5=3,E Hrjl¤ol ¤tr}. trlz}^l Newron9 SE
^lA
^la {ffiolrp
v zllzB4S ee ¤+=*E Eh+q s¤Et
+E 91rt. Newton9 H4g zl+61+ qlr+ E"Jo3 grajs-tr
7l+ol gqt4E ag "J61+ 4"14. IrleI^J "Jg rBg
tTE} I
4lq E+ flol z|$alzl ?+9-H ol 4= TWEl^l9t=tr1. ol
l.dqs+fl ,]|Hg $tlzl "e. q+r+ *"1 C99= dE A q¤¤ EEPJ E=E El=lol4r 6}+.+ -ffi4]oil B"l zI
EEJp,= zlzla- +4U+. r
"llxlxl ?*sE +E*ol H6Izl ?+=+.
12 1 7l{E 8=l
3. ol +^l-=g +zI4"J *C +-
B "IEI tlE+¤¤ +
+. Et¤ #"lt +E=61+ + Ezl¤E + Hd gF ql .-JOI, A
Hzlz} +5 d+ql H6Izl ?*= # E++.
(a) Balzt Erl,++

x
EzI *E rr$g ol.e" 6].S ,]|+ ,J+6}fll zl{lel "Jq4 +ul
Fq = lv,LtlA
^t"lel +{= +4'll= {g +E6J + 9l+.
reJ 18.2 TlqoE+El u*Lt tltl gtoll ?1= E^1.= zl4E -dd]|,(l
-l
@ Exl E5 -e..JE 7l^la F tr-d 7 lill EE-g 39 at ollflolle- 7lEolls,.Jts aolq.
gfaj= LIEILH=
^l
qts +rJqrl4 $"J"lE Hle sfi+$ aj=op. 4"lzl tI
:B ts.tl} Ag H||gg ^J46Ir" ol +Al- u|4z} E+.
g g+¤ o.J¤ 4"lrr + af gq+= ¤+ +E=++
Î"lql
E4l 1 S=* H+el 44}+t 'rnNoAu*Ltlwl ¤tr}. EI+^l ol
^lz3
E"Jql "Jq+= + gF
,4rI Bqa}rll +E C+ u,$ zlzlt- olEo6lt {z} zoJ I {= H{+ trl.gr+ pol :i{fs{ -$F=} He} 2zu,e}g #r}
trJol7} e_E+ Tlqr+ +E=+ +gql q5l4 ullb:29 +FuJ zk)
Et.
(e*!+ +Ee+q +)ol += dE muF+El +E +e_l -ffiu,

EGlq *.JE gF) H+trI. trI+^l gE" "+E ,+ C+g ,I g5* H3r1.=
nN oAu,Lt x2mu,
2V
M
*E="I4 2mu, ".1* HtuilydE4 zdts3 H6Izl 9*=trI). nmN oAuzrLt nMAu2rLt
g|g Ezl¤ol Ar^lZI E"Jql Tlqr+ +E6rq, gf=*el + VV
HEI+ 4 EzI9 +E"t Hsl.ll+ a_ E"Jql Tlqql d
^l7J Ell 3 flel 4l4L
E4¤ *-+ A4 ?Jtr+.
=61^= Eg 44I6I4H "l ¤+l=# H+= ol HElzl "J"l+= ^lZI ar
=J412 S* H+el 4l4t -E +i. S" *el HEI¤$ +6llot +trI. +
^lz}
+E CEol u,oJ E4+ A, x49 u14 upr
^lA E?Iql
olf,alE_tr zl{eE}q ugt 44 ?}q Eq 9= Ezl¤g
"JE
+E"=*e-l
^lz}
HE+g =ry
Tlqg o}6ll^l grE"e- 4* "l
^la E"Jq
s+ 7lq+ +E
Newton9 F" E 412 B4ql el6IH ol +F*E ^lA Hq¤
ts a"lq:zB re.z). zlqel H"lE A+r ;IE e x /Arel + ol ul.tr ,fl"14.
"l 7lq +¤ 6J$q -$4g a+). r?-l6}q NoE Avogadro $ E/ll4 "JEl.el 4l+
i :-4r *vl v9 *zl qlq =qil= Ee=Sg zolzp a| ol fl(nn&{fitv)g *4ol z}"llzl} golla)E +b aol ?}q
ts Bzl "J"J"lf nJETI nNova qq, q+^l +q Au,Lt 4 ol+. rel$ H"lzt e}4lqr q^q-nl zJ!- 44zt +g+.
ql fl= "J"Jolel += @N6tv) x Augtzl ¤ 4"14.
=q ol7l
lr --1-
nMuz'
V
mvx E4s=.g E+7I E"J6J +zlol= ]!ol olt-lr:

+E= zlzla_
*-=. x{
6= Li
E d4lg +Cq= $e p= HIE flql^l 4l&+ "Jel B+il
((...)e. s,,tl)o14.*
n_nM(u'z,)
rV
=Et
6=T
,",rtr,") 49 B+ilEg E+ F"J6-Iq, E6J ti=u2+4+4

X# olo + (u1)= l(l)ol E+.
fg 1B.l zli1l9 gl+e r ErlEol TlErJ ullE
=4
qEoil aJ¤ EzI 44"1 aql EzI9 BE {E ++ u.,*9 rl-*
x*4 7lE"J Ed =E-g x* =
8,Jtr1. ErPl
"JEfol
#al-d
=-?J=tl. +EE AEP
HJ4e slxlPJy+rtz4 dEP H6trl
6tE
4 t"l eE++.
18 Erlffi.E-g 13
Qtz\rrz
/,,,,, = EE +al ttrEl (18.1) f (u) = yr-
( m'l + ruj + mtl zkr
1t
= l1r-
m'l r zxr
e-
m ) n kr
¤
ml *r
rz
= ^llE
r4H 9lel "Jqql ++ +E ¤+ +q? Q|)-"(r,)= ol KE K:KJgga Hl-+l 4E flu)_flu)flur)
^1 ^lg +g=r+ 4-ol
lr'*,,o1 qq, ,rl+^l ++4 ag A+= tsg + 9t+ flr)q *ol "Jf E6ll7I94. ¤zlrl,
pv =\nMul,,, g'al+ +tr| ltole.l E4l tKN/Tl (18.2)
f (u')= K'e-^':''r'
fli4fl2)E. ee EE +qA+.
ol !e E4 S +ss A4"l+. "J"J +{¤el
E_gel qI
.J4lzt+
B+ zllt +qol g-EqlEI q=+trlH "Ja* gE-ql^J= K, & "r &el ac
=
trl+4 a."1 9"1 Boyleel Bzlr+ E"J+ 4*ol g+. t}f rg +6IelH +zI7I --@<t/,x<@ gqr-ilE qtr + +E
E zt4ot 6Lq, tr+Q^l u,lk$, d{l zl-E"+ gqql AA^l 4
PY=constant E6tE dill q¤ lol +e+ot ++= ^l¤¤. "l+*+.=
ol4l ts "Jf. rs.z^lE +Hol nRr* e+= ag BqoF 6}}
4,o14.
I*ro,)du,=1
f44z}9 ^Jal aE zt$ g"-l$ ld-otel.) {zl"ll4,(2,)"ll *d
(b) Ir/anrvelHottzrnann AaJ Ega 4e Hq+E q++ ag ^lol r+gtrI.
Tlzllql^l} zflzf $zffiel +q"l Hg H+lql d4 +eqq 4E G.I
( 2nkr \'''
9lsq, +{¤ ^l-olE +¤E B"I"J"I ol +qE"J #"JS."l I = K,
f- e--l''r' du,= K,
l^ )
^J4"lE +
EzlE,<|ololl,<J xll$ullslr. 9l+. 6J 5^d Ezl-$
trl+^l K,-(ml2nkVtrzo, 44 Xu,'1zt trl-s-r+ i!-"1 ¤4.
E dql= +tre +E"a|4zI
Htst= 6lr +E ql+61
=+¤
uBt= +tr + 7l+g + glr" E _r. trI¤- +5ql^J +^l L4zl , ( ,
J@.)=lm .)"'1 "_^,1t2*r
(r8.3)
¤ +E il¤. 4o14. ¤+ xil# +qg +6iBjH "JEel +
= q¤ 4"14.
Aql 6J +qd +qg *= B4¤E Egg got"t *4. u-e. flu,)*flu,)ql q6il^JE eg 4"1
Pel u+du rl-ol9 gqql 59zl-E +qg 4. BzlE Eg
g gEel Hololl uJellaiq flu)du4t ¤ + gleq, "l lu)E eJAl3
flu,)flur)flu,)dudurdu,fl 4t tz14 4
44 Es -d++r +=+. ol +E EE Et+. +6171 fl6H
ezl¤ol d4 o e H4l eEE qlqzl"Jg *=+r ^J *el u,+du, xtslg4 +E= zl.{ ffi$ r+q-r} *"1 94.
^J=
46}jl" olq^J Boltzmann44 Eg 6Jf 0l+61"1 ol qlLl "-
^\'tr*n]*'1)tz*t
zlzl ¤4 Ezl¤"ll qg4 EEEI=zl= = f (u,)f (ur)f (r,)dudurdu"=(#)" ^- û! t z kr ^-

*rl n *r ^- *1 2117
^J46]]ot *trI.
e'ee 1
x du du
rdu,
@ +=JEE*+et BE (tt m \ t izkT
6r rdU dU,
\zn*r ) "-,rt
ol +E 4aE Boltzmann EE(g-E dxll zl^l ¤¤-
EoI4)ol+. =gdg ¤ zl rJ u2 - ul+ uj+ ulolcl.
E4! 1 BA +E "ilHzl9 +s E++

eJAl 4 t Ezlzl ,*el u+du
^tolel
+qg ztd gE9 4l+L
Boltzmann EEql 9]6IH t)y, t)y, u,oJ \E CEg *= +

6JEzlTI *.Jql zI¤
^J+S.ol uPEl u+du Îolel 449
zI9 Egg B4l +F 9lHzl9 zlfEr-+q Hl;ll6}q, +
q¤g +6}zl +l6]]^J +E CEg'$E- *7lql^lel ^ll 4l
^Jl
r= ulql rr-++.rqr Bd gE glHxlE + +44 EzL. +E *rJg r alE= (x, y, z) 4d"ll (u,
flu)--xra*rol4,
ol-4e+ +r+. u,, +4U+= dg ^lle-l6}H Ftr-zl"J gtZF+ +eg
u,)a
ceg 4.= aol+. r46}q ¤ltr-4 *rJql^J +irl a +7I
s= lmul + imul + !mu)
dxdydzolTol +E +aql^JE +q s-rE dudurdu,Tl ¤+.
tr|+^J dr+v+z- dxd/a,9 *4lE ol+6}q ol +g E|+E trl-g YJ4 +tql^J= +C o ++q r"J* gqA *ql 9l= +El
4 *"1 +48 + 9l+ ,q_AE d+ -JilE HlzlEol rolr. +4171dr?l T4(+4 4
d)el -pylzI ¤4."1 +r+4 +qE:z -tr84 4Tlrqlr+ r +
1t+ 1 Tldleldtr
EE 4nv2
vz
FAI, dV
ol
^lql^J flu)!
q^.q_r+ *"1 l4 + + 9t+
*(#)'' r'
I
f (u) = ^"''
/ "-
I
"'
4?ol ¤+91+
vx
3t2
M 2 -,\ri t2Rt'
f(u)= +n ztrtr ue
tr/axwell-BoltzmanEg[KN/T] (18.4)
f.al 18.3 -d ErPl uF.A u+dunl^|9 Bqq +alE 7lE qEE Tdl
alE HJII=O1 y=@!+ur2+u|1trzo1+ E.Eoll+ FAI dudurdu,E E-il g+fu)E Maxwell-BoltzmannAaJ Ee. Et++r +-+ E
SP 7z+ + olETloll ErPl fl= qEE ?dl'E Etrl.
^Jzl " += +-tr EL+ql^Je+
?J"l flu)i 9zl9l4 +d .ll
4l d¤ #* +rfarq "Ltlzlzla +E +Zlql^J HI

?Jtr+.
"1e} t 18.1 13 zlill 8*.
zlE"l uola +4171 du"J a7J9 +rl= 4nu2du7l g+(rH R
rB.3). HIE *9 flu)flur)fl/.)E a4 ++g u2oll"J 9
^lql^J I K-'msl-r
a_6}q, H}zlE uA A?J ?lql^J= qq^l+ e+. rqr EzI
8.3t4 47
8.205 74 x 10-2 dm3 atm K-rmol-l
Eol u+q u*du Î"lel +qg 714 .j.AlqEg ol a4 6J 8.314 47 x 10-2 dm3 bar K-rmol-r
914 tlzlEol yol-r. +4'71 duoJ ATJel +qE *6l]= aol 8.314 47 Pa mrK-rmol-r
4. "l 4¤¤lt/)dz4r s^l6IE trl-s_r+ ,J? 4+7l. ¤+.

62.3& dmr Torr K-rmol-r
r.987 2l cal K-rmol-r
. zl4l {}#E t+, l4a

f (u)d,u = nnu'dr(#)" ,--'''tzkr ¤zl,tl
R=NAkoltr, N6E Avogadro &E Boltzmann
^J+oltrl.
@H
4Ee +d "Jel HolE +61+ 40.14. ilf/(x)9 + ad x=a* t.h lu
t= \o, =ls(b)+C}-
\o \'/ ' vt ls@)+Cl
t6 \Y'l ' v'
x=b 4Eg zhl4 o e x4 ^c.9 *¤ 6x"J a4e-s t+ )^f(x)dx={g(x)+C}l 848
^lol"ll^-lE lO
+q 7tzlr. ol a4Eel qlg +61.= ae e^l lf orc, E s^l+ = s(b)- s@)
trHzl+ ,lE ,J4l 5o3 ac e^l gqE B sumg 9ol,*
J= sE 4E tr-+zl- S.qzl= ag +.E-61q4. ol nzlloll^J ^l-&q
+). a4+r+ +C4E# zle. ¤oil ++6H +9t+. olEg
tb =
E.6J ++ +E Egllq¤ ol+6}|^J 4l4ls + lltrl
[)t<Oa*=It3](r,)6x 4E lsell
$rl roll{ E + 9l= utq ?ol ol zleg + 4e t4l ae} b r}

ololl Egzl+ e+/"Jg Hols+ e+. zl# g El¤ trlH E}
++r *q. ts4e ^l¤e 6J ¤+9 zi+g "l+el 9ol ¤48

Î+lol+.
+ + fl+/E "l++ +sql r arl¤ zlEdlH +^l i.l
I Elfzt Llec(d+ Hfl Lflql^l). t(xl
4E +4lzt B^lg s ^lel 4Ee 84Eol4r. oJr+. zl, t4l

B^16rzl ?+e 4Ee +ErlEolelz6Jr+. +A4Eg t A4
=
zl dx)+coJ trllHc= tI+) El+rl Ag g'^l= 6rq 6ll=J6l+ I
EtE¤+g+ 91tr}.
a x
tlet 1
18 ErlEEi.E..g 15
^J +E gqg *6110} EE-14flE= *=tr}.

Maxwell-Boltzmann Ee o;ii= tr|s_r+ eg 5Ag zl5lt_
gl4t:zH 1B.4).
. 1B.4^l +ql= zl+ ++{ul 74lzl o e

+^161.= _s
¤6lH Gauss Bf)zI Eqgl+. e-r3 xzol 44 ql <l-
ol zl
;io'o
ql+61 arolzlE Ceg zlzl:il_ ileq, tr+?+î Hl
+ C++ -J"l Eqilge_E,'^-l ql+61 HBI= +qg 4

nl.]
b Ezlg Egol ql+61 zI"I41+. 44, v

. M/2Rrql u¤ Bd zlf Ez|q Ee%L Mol trll
v2
= =
AzlE-tr. zlf tzlt Mol #461111 0o e d f.g le.s
-d E^Pl u,FEi urDlr'lole= EEE ++= 71tr +EE 4ld6l
=trll :dtr|..
+ +ag +4+ ,I+ +qg z*zlzl 4 4E Es -Bt+E F -dzl
^lololl^"1
g +c gel 'Jolel-,Jtr(^4tr-Lf ?=).
5E6t|0F 0l 4E= + -d4l
^l0loll^1
=+trt. =
BtrI. #
. 9Ezl }$ tr|]= Hlq E47I +Qkl+.? olull5 fi
zl+ +E Mt2RTTl +e-q, q;+^J xlf oJzlt uzy ffi F(u,,u,)=
!:, f @)du (rB.s)
+rlElql q4 HlE4 Lrlal 0o e EqTIq. HI+l ol 4Eg f E uA oJ+E E^l* rufls eE Holol{(:.H
"JptH E3 Ssql^l= *3 gsql^JE+ q Fle lB.s), a+q= fo] +:ae9llq= 0l+6ll^l +a 4l&
Egel EzPIt$+qg TVlAl g 4oltrI. =B+
. zl+ szl.4ql ?lE a23 uzl oo e d=+ql ul4 o
H o.+ olag +61lot ++. Irlel^J u,9 ¤tzli rle=$ pol
o e 84. tr}?+^l 44ol ql+61 *g +ztel EgE

4l4lg + el+.
E.6J ql+61 *+. (u") - l* u'f (u)du (18.6)
. +"lxl +g gs 6Jr+ r *g 4r)3

qlzl¤-(18.4^l
+$$ di-ll +E ¤qq Aa 'J6lli At*zl tol
\61 n-28 +l+ 4# &E7l roJ E4¤E ¤+ all+ +q
<u'>g +4.ll4l ¤+.
94 qlag 4014.
(r,) -# EE rirE +ar tKMrl (18.7)
(c) trJEi!
oJB tvtaxwell-Boltzmann e +Eq "JE oo
tr14^J zlxll $z|e-l ¤t =
zll# +qC q-Sq B"l 84.
EE EL+E 7*,
el xll# ¤+g 4*6J 4Eg 6ll^l +ts + 9l+. qlErl z,P u, ,=(r')t''-(#), EE rllg +al lxvrJ (1B.8)
=
El z, ,rlolel ¤qql fl= EzlE Ege- q-g 4+¤. 0l+6l]^l
+6IE Btr| a, zVll Ezl9 B+ 4l# +qe gEE 4l#ql Hlqlo}
= qHlEll
r. E e=*q 4l++q ++. 1, e-_Ezl +ote++ E
L-[g gE EEL 4¤q ¤+ zllE- +qE +olzl-tr, d.+q4l gEql^J=
EE E^[ =
EAJ
+Ag E4-5ol TIqg E{s=E4 Lflrll +zle+.
rel+ +s+ aEg tB.8^lg lB.2^lql ql"J6tH pv--nRr
6il _?ca! xtat 7t +s=ql, ol ar+b ule 9d TlalE tr-EH^l"J 4."14. ol
s =ci
AE+ Exl ¤¤l Egg $d zl4lel E.B otr E + ?ltrI=

.9E EE L
<i
ag ?= aolq.
L+ .!L
;ib0 +"J6ll
+l
nl-l
GZf 7ri.tl ETIEBE+er 4rrr

0
0
Aai, v
zs tollrl N, EzI9 /..,eI ¤t +q u^*,& +6Lq+.
f.eJ 1B.4 E^l+alq EEel traJoll nf= EE" 716| +Eol tg +al(01
ual:g /.EI ¤t
= mol-t)l] T-2e8 KE
zll# +qg lB.8^lql M-28.02 g mol-r
=
EEol E+aloll 5H'J61.=)= 3E trB 'zJ+ql qal EE (4 o.ozso2 kg Bq+H +6J + 9l+.
sl+01 'JclTlrl. =7le.f = =7f6|01,
16 1 TldE -str
¤+ +qg qg 49 ol+dl^J +El+.

vmp = (2RTlll^1t2
,,,,,=ll rf @)du !! v.""n = (8RTlnM1t2
]-
q vrms = l3RTllVlllt2
¤zlrJ fldY lB3^lg ols"d4. "l 4¤+ f* +o_=911 H
N
q+ zlg eE g.= 4Eg "l+611^l E + ?14. r I= I kB E

=
sf
m's-'9 "l+ql+.
Eol B+ 41# +qe q+4 e+.

=
tl2
tt tx1s.r t+s]K-' mol-' )x(29sK) I (3t211t2 vl(2RTlM1t2

I l4lnl1t2
,t=
-ms = 5l5ms-r
f.g 18.6 P-E loll,\l traJol MoJ E^loll cH-d MaxwellEE l-o-e+El
u^*nZ trl-g zlBg oJ+6llî +++ ? = *3 +a4 u*un8 oE +al, LeE u,-,ts 3 rE
trl= 2JtE: u^r? )W
IllE +ajoltrl.
4E c.a
312
u^nn--*(#) t* ir-nlnnr du 21t2v
( tvt \ 3t2 v2
4rc t_t xI (#)'=( 8RT

nM
lznnr ) ( )
?
EilolEi# Bq+ts q--q-4 ae er+= eg + 9l+.
v2
o 21/2v
( gx(s.rt+slK-' mol-')x(298K) )
U^nn
\t7lg.7l1B.1
t,l
18.6^l o ts+q 1B.7^lg +6Iq4
= 475ms-r
fg
( )
18.7 7lill E^lE 8tt|4 EE +ejol EE ++rl'gZlE= AE6l
o
-HqT= raJ. ErlEol Eg gefo-e oE-g tt|l= 8t|14 EE +alol 001q,
,\1e EE--g ttll= 2roltl. gu4?l trJE EtL g:d3 +Eo++Elolq
=^l-=01
olttH= EE tr= 4s.u 1 21/2uolLl.0l Elrlof E= g-BFol 7|.8 ,-J=-=f "J
ts-71lB.lql^l BoJ uls+ ?ol Manvell-Boltzmann +E Eg
6J+E- ol+6IE zlill {fz}g trJE *aj u-",,,9 +g + gltr}. 6ltn r+af,(j EE tr= +el3 cHillB 2trzyTl E zig-a 7l4Erf. 0l ,Je Eq
g "JEr z luetrE +?]qfl trt.
l2 v2
8RT 8
EE +e [KN/r] (18.e)
u mean u r^,
7tM 3n
EE E'-+rl +4rll= ¤+?-lel 9lzl=flu)E u"ll $a11,<1 u1g ( 8rtl4 EE +al

,*,=[ akT \''' lt= *ffi
ffie,ffis (1B.11b)
"t, )
[EE 7li]ll
+ tr|S ol ults Ar+= 0ol qTll atts u9 ll@=ot]- u_*Z
4lq.J)¤. *eE o}4el ge 7Et *= +aJ u^pE +* +
el+.
z]trJEt ofl re.r
( znr\ tl2
7l.8 *3 +al [KN/r] (18.10) *ql^J +g Hl-e+ Aol(E.7l 1B.1) 2stql^J N2+zI9 2.,",
un1'=
[-r.] (1)''"*,,
(= ¤+ zll+ +q)Z +zs m s-'o14.tr|{^l lB.tlarloll 9
rB 18.69 ol p$$ sqr6,J Lol4. ullrJ olEE *.I4 ¤+ +qg q^q-r+ #ol ¤4.
E= 945 BzlTI tr|. tszlql d=fl-= B+
ols-" 6].fl 6J
u,"t= 2tt2 x(475 ms-' ) = 672 m s-'
+E, + 8Ell4 trJE +el u,"tE E6J AI4I6J + 9l+.
l)rrr:2'12
8rll4 En +al (1 B.11a)
EoJ E^1.= ,\fol]
U
^"^n [KN/T,
ol a+=-ftro1z1z}
^J'&61 9Bzl"J
rB 18.79 .E-E ola 1B,.2
g B+ts + 9lg 4"14. ?+?+ 4*ol meel ms?) + ^Jolt} =rt==
t.ll4 B+ +qe 494 +Ll. gd Tlill= #"Js.ol 8*-6I-E^J
tszl¤9 ^lE ¤¤E6I= Ezl¤E d
18 Erl- E.g 17
t"l4} AC4 z||H$ zlill $z| &FE EBql el6}|^J +ld E rB.2 # EE4-
c=J4"lE^J 7Js"t e EA6I9+.561 ol +E-E
^lE ^le o lnrP
" _+ *4= +zl¤ol +561-= els4Ezl +E Îolql Bt CuHu 0.88
4 o -=. 0l+61-= ,l4E 4l&g + glrll q H+
CO, 0.52
(a)EHJs He 0.21
N2 0.43
zlzll $x| ¤+Eql^J= E^l-# a4 aq-r. 7la6IB.zl"J .q *e a# 4E ¤ql ++6ll +9i+
¤zlrJE + tsÎE 6CE"l xl=ol+r 6l-= 4?-l d "J
=E
ql EqsH + Hq +E=E 4lt+4. +E zl# EzlE d
xll zlE4 zg! azl eE= ?*Ytr+(rlill +q a+ql= d7l +
zlr ++B + 9l+.
z[ zlfi.o] g+). Ez] ¤.E"E Egg ol+6]H Hls. z(e] uJ-=
=E - -ouaP [KrMr] (18.12b)
Ezlzl "JszlE +s=+= ol 6=-$ol "JqU /.ltctr. 4b "- kT =E
7t). alÎg + ei+. tB.l2aaloll el6lE "JA+ +q 6iql^l= ¤!= Hls.z}3s.
ql q4 +zlal=Ql, ol49 gszl-+olzlH 4+89 Exl¤
@ %=E#olE¤t=EEIE
^lol
fftr ol Q uulerll ¤+6}zl rllEol4. +g lB.l2b^lql E6lH "Je
zl# *
Ezl-= ^llel6J rl= E^l¤E +lil7| Eaqfltr}a ^J fl gEql^J= += qlszl-"Jqq Hleilq1+. "Jqol +ole+
z16lz| rflE ol + +zI7I Eqlql tr-q4 ¤+ + + ^lE 49 Ezlf uJETI g}"Izl4, Bl+ Ezl-=e-] ¤+ +
^t ^l7J qe H4zl ?+q+E ^JszlE += HIE= 4¤ 4o14.
4 ,,.,E zlzl:il- zlill f$ f,irlal 1ol4 +Eol "JgB ullzt
zl z)o\zl u,",Afol-tr +H4ol o= xd2oJ '+E gF'(tr}+^J +
3l z]'J:d q
-tlzl ou,"1lflg 4z}|l B Lol4(rfl 1B.8). ExI6Col 1B.2
ol +E gE +ql +lil+ czl t4 Ezl-E9 iE ol g=Lel 1.00 Eq 9t= N, Ezl9

atm(lol kPa)4 zs"cE.<l-e 491
+iil vql+ "JoJ"l f E.E. st=N/vE EdJ trou.aAfel a+(N ql
A+, A++ lB.lql 96IH u,eF672 m s-'o14. tr+4^J
g fl= dill Ezlf4). ol ffi 6s +b aol + lB.12b^lr+ g tg.z9 o =0.43 nm2(0.45x 10-t8 m2)$ ol$
^lE +ql
E HlEol+.ttl+^1, 6lH trl¤.4 Ae Ar+= Eg + 9l+.
6E [KtMr] (0.43x10-" m' 1x1672ms-' )x(1.01x10' Pa)

z = our"t7\r P.!s (1B.12a)
,
(1.38 1 xlo-zr J11-' )x (298 K)
= 7.1xlOe s-r
44"lq oE tsz}.el EE4ol4r +='I. "J+ dB4
.J <l# =E
s" 1B.2ql ;qafl +gt+.
trL+^J t
Ezl-b l=t:I+ * z x loe{g +E=++. ol"J6l
gd zlill ^JEll^]4 R=NekE olg6}E "J"Jol + "JEE + E zlill +ql^J "Jq+= ^l-a.E ,(l{ dl"tg lrE f
9lg aol4.
*4 ?ol "JEg zlzla- +qB + 9l+.
.^._N_rN^_ uNo _pNo_ p
"-v--T--iMTi-T7--W (b) rrJE r[* BE
ol 49 "l+6lE ¤E qls= trP=4 ztol zl4l9 "J49 zl-
IIJE r[* BE 2= * Ez]z] +E
^]olql
Bo[z]E ¤+ ,lel
"J"J t Ezlz} HIE zE zlzl:il_ #6lH
tr|. ol Ezlt +E
flLl'rJo vret.L,t Uz t-lzJ EqI zl-f, HlBg B aolq, 44^J (Uz)u,a
^Lolql
"J+q 44E BolA 4,o14. + ¤+ 4+ BEzl. ul--o-_a.1- 4-
ol ¤+.
d
I t, ==J L=4z EE
^l+
Be tKN/rl (18.13)
rJ0l, o 18.12b^le + ++ zE ol ^lql Bq +E q^.q-4 Ag Ar-l¤

.f.g 18.8 Tlill EII -=.'JE 0lE-"|6E HJEsI Zltt e4 g+.
=E-E
18 T ldPl 8tr
^kT
1l- _ EE
:"J_e
[eJE 7lill] (1B.14) 1B.14^lql SszI EqzI ?lzlts 6l-zlq| "JC +"lel rle.oll
oP î+ .Jqol roll Blql6}q EI+^l SszI94zlE r/p= E6t
^J=
"Jqg ts11s 6zlrlzlfl B# zI.* etr.= HlsE zl 9+a "JC6I+ EI+^l "JC +i{$ *zl"ll E991ts zlill
=+
zI+ qsTI gEql ++6I+. ¤lE HIB
^lBql^l= = ÎolE
4?-l= +qd +r4 +ql Eqfl= Ezl¤9 +ql E6H,\l 44
zI++ {l rs.rgl,qb zs'cql^l Nz tsz}9 fiS u,",=67r qq, rEE Hlq +qql= ++6I+.
m s'ola s ZI*$ {l rs.zglrl= "Jqol 1.00atmoJ rll aEzi o tr I atm, 2s'c 6Iql^J= dBzl"J 7lz-ll(N, g.= or)
z=7.4 x tOes-'4E Ar+= gfl+. olelq} ++aql^l= N, E E 500ms-'9 ¤t 44"-e. &rE"6l+ Ezl-E9 d+ol+
Ezl-9 ¤t zl-# Bezl trl-s-r+ ?ol S4. -1. B + 9l+. 4 E{-==$ aI l ns "lLflql +Eg 6Iq +=
Î
"lql E rd Ezl zlfi¤ B"tzI4.
671ms-r
L- ,Zxro%'' = 9.1x10-8m
+ ernmoJrll, olag +zI zlEE E to'ull"ll 6HR++.
=s-d7]lLJ=
f l. 7li{l Erlffi= -E'gql^J= zl4l tszl.9 "llHxlzl-ezl Ezt +qg *= E^l¤E +gg +6J+ 9l+.
5E Ell ¤+ qlLJzl9l zloJ6Jqr C4+trI. a 4. HJE=
"JC+ ^lrJ E?]ql +E6l_= El+=
6J ts1f71
=E
t t\zJ
I 2. 7li{l Ex} e¤= +q= "Jqql +6J ^14 tr-lE
strg-E+El
=
?ole +k- Alol4.
{|=l +alql +6J 49 +Eg + ?i+. r s. BE rl8 BE= Ezlz} +E ^Flql B"tzi= ¤+ 4?-1tri.
I 3. Maxwell-Boltzmann *al Eg -Bt+E ole"6l$ .$A gqE
=s-d^lE
oezl
,\-l --'lI +4 al {-a
$d zl^llg EzI Egs +Eq= "Jq
.gE" E pV =!nMu!^, 9d zlrll9 Ez| &E"E tB.2
Ma:rwell-Boltzmann 4H Eg ++ flu) = 4n(M I 2nRT)3

t 2
u2 e- Ll:l t 2Rr lB.4
u,^,--(3RTlNI)tt2 lB.8
=¤+4s+q
¤+ +q /-""n = (SRThtAttz rB.9
,ItL *e +q uô=(2RTllvftt2 18.10
t'-q4 ¤# +q u,"r=(SkTlnp)tt2 1B.l1b
p=momsl(me,tms)
6E el-s z=ourrlplkT, O =tldz lB.12b
¤t z[* 4s )"=ur"1lz 1B.13

r
lC grllTli{l
rI
+r- JII
-l
Eq ¤t gF +E7I q+ *o}4rl î-tr-

EE + glrtl q=
> ol EEIE u[+.ts ols
4o14.
ol=Hl'd^{ 7lill' alr ?e= a{|e 7li.ll= sE 7lill
=rllolts ol5
ts4l+ql 7l"Jq= Awl ¤e rE"g +dE E"Jql
e.l= trlEtrl-. olal gE Tlill .strE+ElE Hol'J= ¤tr{:Eo.Erl
ExlE SErtEe-l Etr= + ?Itrl. g +4+ ll+(rfl rc.D. Ezl-Eol +vl= x}^l6l-=-*g
=qq-= =
'Jq 6l-ql^J. +zl-=ol $f{ c + E"-l Eq4 ?lqrJ Ezl-
^toleJ
> "-4C
7]lts ZI Eol tre +s-6J q6Jg 6izl .F6I4, 44rl zlr1l5 o1,g-
TliJl E^lE ?.lal4 HJ"J= r,a16fE Tlillel #C= 7HC
4"J qf,-$ 614l B+. Ezl¤ol EzI zlEE + ufl {+_e p
:=f
+ ?lr r^lolel
"JZl dtrg l1a16H= + 9ltl. q4 flb +7J gEg %r-qql^J= "Jqol +gqg "Js_eI+.
> oJgEl qlHl rl^l ol A+ql= "Jqql E6ll^J Ezl¤"] B=g f ilzl ql+ql
0l Ei4e EE 1Ag ts9= Zl+6lr Cl8^lZtl'. q7l^l= DIE zlzllzl $d zlxllHq q d4 "J+g + 9lg 4.oe Tlqg
E6t|^1 +C9 E+E= *= +-+r1 ge6ftl(sl+^l9 4. Ezl¤ol ¤+4 " F zlztsl Bq ?l= +e sqql^l= HI
=
84 s).
^l^l0l
tsqol zlulllol{, oltrll= H}tsqol Ezl¤¤ "Jol4o + zl
ill= "J+\zlzl rRI+ El qq+lA 4.o e ,lqlgc}.
rB lc.2bql^J t]-ql Aql gl* zlril rltrE ga6J gEql^J
{xlJ zlzllts p-+0"J +qlollrJzl- o}qE 9d zlzll Bzl¤. g rlÊ_e_E Bq -+q "J+6iH(+rl= ¤olH) qBrll qa=
"J6IAI qszl ?+b+.=61 +g "Jq4 *g gE +61 Tlill 7l-=
^J46I¤ EzL. A +=ql^J +
TlillE sqol rflz-ll_tr Boyte
z| $zlltr. 9zl zlAe-l aa 6Iql^J= ol Hzl o egq el Hzlql Iq-+^J +7I++. rBl+ +q= sE Erlal 44zl
=.zll
Hq*+. ea^lzlH Boyleel H4-oE+q c6l4l H."l4zl ^lAt*+.
a cql^l=(oltlsl+Ael a+ !t ooatmgl 6ll'J.++) ol^J
1C.1 ol84 ¤EE+E{el ol=J 4 ¤d-"l de SqTI+. . {zlrJE $l4"1 cl ?zl.a].zl ?+
e$^l ElÊol Ellz+]4 ol +41= +¤d cDE-tr.
=q7l4.
{xll zli]l7} sd Tlill B4sE+q olRqE 4.3 Exl¤"l *zl +¤-a^t6fl -H-H
s^lEl=ql, cE ule
ffiql^l= .+ill
tlE4L¤¤ 6tzl trll+ol+. + zlzl Edflo} ts d3 E{¤ ,l-+4+q, + 7}]q ^Jol +A+ AAlHql E6ll^l E"]qq
E¤-ol 91, "Jqg.J+ql E+ol E
^l-"lE Hlgqg s+ql
+E aol4.
+Bqg Ezl¤"] 4E *+9ig qlq"J E4l7I ¤4. ol rI
gqe Ezl zlE 4E.ql^J -Bq4E t}szl*ol+(r UJ
d
=4q ---:
K
H rc.r). ol Col oliJfl ^JE4+olzl u1Eql Ezlzl 5
=4q
HlBe Ez|Eol ¤t4 + "Jdqq flg qlql"J +s.ts a
o
6
{ru
-El
ol+. "*e- +e_l Ezlzl +3 +i4E ilzl6l+ +g "Jq 6I E'
=
ql^J olBl+ .Jqe
^Js+r*ol +4+= 4o14. +¤ Ezla ?l +[t
HlI4 *44 ¤o14, +zI zl$9 fuH* q= Zqql^lztzl ^t*t+
0
¤6&9 ulTl+. trI+^J E!¤ol o1g E^fz zal
^Js "++zl ?+g C=.21
zlt\& |?-lql(rfl rc.rql^J +rJ {sfl
4q) +s6tal ¤ fB lc.l F E^tE trlEJl¤ oilLl^l= 0l= 71aloil el=Eltrl-. gE Ee
:fl4
Ezl¤ol q+ E4 Eq4 9lg ol=(rfl lc.lql tr1EJ!¤(ttlE6l 7WE 71alql^1)e 0l= ^lolsl
8E4tE0l d Ug AtEgE
4. ^l.0le.l
El= trEg Tialoll^l=
E4 sEE- e-_e.) "Jqol affi 44421 *{+ tszlt
LfEfL.!trl. tr]EJl¤ ollLl^l7f ?.!aj atEol xlut|
^J
=01 =a
40ltl'. E[|E6I gal(e.E.+o-a) Eq^1 ?1= ttll= trlEJ!¤ 01lL1rl7l001 qq,
tqg 9rz1 q1+61 *g qlqlE flzlaflzllr'll, olulli $z| E^lE
^l0loll
SEatEol g.trl-.
20 1 Tldlel¤tr
CHo
50'c
40'c N
21 nAof lT
v=-
\
E ( K 7
-E
o -oJ
\\ 20"c
^\ 60 ,([
1
I
6n Z platm
10
__h-h'i;;- 0.98
20
NH. 0 CrHo
NH
(a)
lTKvid
0 200 400 600 800
platm
gas
Tpvid + f.g lc.3 o'Coll^1 H 7l^l 7li1lE gf+ oJrl' Ztl Szlsll q=6F= EoJ. gE
zF1l9 e+oll= .E.= "Jaloll,\l Z=lolLt. p-+001 EIE 0l qC=o1 1E tr=
gas 617l= 6f^PJ 0l=E 7l?7l7l +eq= ri= T=6tqat.
E
o I
a- 60 20"c
g-d zlzllE g
ED c
El 1_ +rl= RT/polTJe z_pv^tRTtr +4,3 +E
A
91tri.+
20
(b) PV^ = RTZ (1C.2)

0 o_2 0.4 0.6
V-l(dm3 mol-1)
$d zlill9 a+qlb E= ad 6}ql^l Z=rol qq, qet^J z
fg 1C.2 (a) Gal
-eEoll,\l =¤-J 58{j.
ohlalEJ4el g4l 8E 31.04"C 9 reAqE olBg ol^J4 68rEo_e__tr.+el "lRqE AEE +
oll^1sl E¤Col gzl EE +C(A^4)o|tr|-. "Jz{ltroll EE= Eutl"-tl (b)
EEoll^l ¤B-st Hte|' e0l oJXltrrl r 0ldloll^1= 7lx1l7l 8*E.|q
=?ttrl'.
+Ed
4U+.
(cDE)oll qaf g'+Etl. "JZl g*E 01610ll^1= s= 53{!01 Cq E ee E= A zlz]1 Tlilloll E]]{L zel deil= rH
+$r]lfl+. 1c.3ql
e o|+clTl trdol Erl'. q+6l *e sqql^l= E= TliilEol Z=rg +4Lilq 4
9 ol^J4_" + BE"aI4.te Sqql^J= E.7l415ol Z>l
9l*g E + 9l+. +rl7} cE+El D= 7ia EE rJÊlql q "J Afg zlzl4, $d TlillE+ E +ul= 4=+. oltrll= HI
=
+ "liilE "Jol Eq*+. olag qÊg q "Jq B{s zl tsflol zlufllolr|.+7J CEE *qql^l= .]]+EE z\4lzl
illzl rEJ+ q f,4qq "t+fl xlalE- 44421 ?*zl ollg"l z<roJ <l¤. 4=tr11, olag "Jgol $,rllal.¤ -:. E- +yl7l +
+.d CDEqI^J= "lille+ +7171¤Bg ol+H^J ="=-6141 I d zlill9 E +qE+ }"I4ltrl= ^t¤g ++t]l= 4o14.
Ecll, oltrllel E.qg r de gEql^JE "4illel Ezl ?Jalol4
-a +E+.
a Eql^l= ^lE7I d+ .+ills ql ullEg ol oli-ll -EH g +El= V,i = 0.416
ql g6lal g+. r ol1t ei^lTlel$ ^JB6l s00Ke+ t0ObarollrJ $d zl^llE
^leE +{= dm3mol-'o14. Ag aaq^J oltlEl+Ê E +q=
= "Jqg z}6110} 6l+trJ1, ol z,|{o1 Eel 4l+ql #46}rll tr-+ v^=0.366dm3mol-1ol+. III.4^J 500 Kql^JY z7l trIs=r+
olt doe. Hl¤Elq fl4. re.+el re +ElE a+"J eA
6l]E sq¤- z4l ?zl^l4oF ++.
*ol ¤4.
^lzlell
Z=0.366dm3-mol-r, =0.880
0.4l6dm'mol-
(a)S= ?lrt
olE ++ ¤459 +4lE s4 etxt z. Ê
z<lol+= ^l.dg "lei+ aaql^Jb "J{ol HltsqE+
A"d=EI^l7l= a.
+^116}+= ag +4u+.
41"6]l EzI."J+ "JzI= a-71illE E *ul v,=vtn¤ ol zlx'll
e+ +"J+ "Jq4 ¤.E.q1.<1s11 gd zlillE g +rl y; o + +
b Hlol+.
y. dreal
= gas (o) ulalg 4l+
Z
v;
g+ E^ltEgl (1c.1)
E +vlzl at ¤.ETI t¤ Ell= d4l 7l^ll E"¤-dol $d zl
f
Ideal gas
:
lC ¤rll 7lill 21
E 1C.1 Hlelg Al*, a/km3mot-l)*

=rJ| RT B
P= V^ +
9-E v-
273K 600K
(S.3 las Jmol-r K-r ) x(100 K) l.975xl04m3mol-')
2.16x10-3 m3 mol-r
AI -2r.7 11.9
=3.50x10sPa, Et 350kPa
CO, -149.7 -t2.4
N2 2t.7
ol 44}ql,rl t Pa=11m.9 +4Ig 61fl+ $d zlxll t4
-10.5
Xe -153.7 -19.6
!$ ol*alfl ol Hl"-l"J {g ol+q{g trllE4 toyozl yf
. q ge (t59 zls ¤q ++6il +?tEI t9:sskpaol 4¤.4. ol+7ll 14 H.q4E "l ff h ol a
aq^l= Btv^=0.1o1 99 rql Hl6ll^J +^lts + flE <t
olzl ullffolQ.
5$d4 r|l 4ezl 9++. EAq olgg 9d zlill Hzl
zll
pv^=Rr7l +*4 ag drll 6J"Jg fl6J a40l7l trllE
^lE
"J¤-
g}^16l+ 4,"14.
¤xll zlillE ^JQ^lol p+g"J trll= 9d zlillE B!4 "J
pv^=RT(l+B'p+c'p'+-..) (1c.3a)
zl6izltrJ ol +oJqlrJ dxll TlillE E= ceol sd Tlillel
ol !g E?l+Eql^J E+q= AzlE t {l"Jrll, H+(qzl^l CAt+ "Jzl6l-= ag ol-q+. qlE^J "J+ "Jzl-E "Jqql E]]6}|
Ep)E q#+E'tqu 49 ElEq^'l r 4.411 6J"Jg +l6l-E
^l
E^l6J +dE z1&zl aztapq <t¤- ^J4all Ez(Elulx|$
lil-=^l^l?l ++ Hzl(q7l^J= pv^=RT)ol +g+. q+4 ^Jal s9
EEr+e+ trlEE 4lsE _H_oI?+). 9d zl4lE A+
*3 _erl ¤4ql al"l E4 r*"1 ol+9zls tL+. 41Y aztap=solzltrJ(EE "Jqql^J Z-1olu4), ¤zll TlillE
a+= rc3aaloll el6ll^l q-g+ aol ¤4.
pv^=Rr('.*.#. Hlalg gEH^l (1c.3b)
) Y B'+2Dc'+...+ B' *il
dpt- P+o"J (1C.aa)
ol + 49 t|"lql Hlalg 8EH^lol+., ol

soJ=e-tr_
'l-Elu ^l
I tc.z44 ulndl-H-H lGb^lE gE "JE 6Jol oJ+ oJzI rBl+ Yg 0ol 9zl ?*9 +E 9leq, ol4^J z9 pil 4tI
Dl ?Jtr+Y ag "J + ?t+. z\&zlb:2fl rc.+ql^l ts + gl= Hl-e+ Aol o(Sd zl4lql
rIqL A)"1 qzl ?+g + 9l= 4.o14. u}1!z[zl br-]ql q4 +
4l+ B, c, ... , #
Ssql q=6}4,zlrl E4l, d4l, ... Hl
alg 1l++r qI+(E lc.l); dall ul4"J 4l+= 1oltrl.E + gl* ee +4lE dBt4("l4+ ++E r.[49 +6]-48
ulzl dB4e <lg 7Le ql= ctvi(B/v-ol q=ql, olfl E glp+zlg
^}^l s= _H_oI4).
ql^l B *il ,jlzfl Hl4"J 4lf c= .JHI4eE E4 4l+ BE+

E +s6I+.TlillE Hl?-l"J 4+ AEe a7)ille-l "J+"JzlE #fu'u V', -+""oj u1] (1C.4b)
+a6lq aa++.
zlE!¤t q 1c.2
lc.3b^lg olgal.{(r6-}7}zlEJ) pyl o.zzsdm3oJ *zl 4

BoyleEE
q 5qflE o.toamol9 or(9zl 100Kql^J +44= $q N
K
g +6tElH *d:z E +ulE 4l+6llot t+. -ol
,K[
111l
6r
rlm-- V - 0.225drn3: =2.16dm3 mol-r =2.16x10-3 m3 mol-r
Hrl Lto _9E
flot o.lo4mol --'^"*"
+El x
'
rqr zlE- dE .tr lc.lqlî BE <lg *oI olgql4. 84, p
lal 1c.4 '*3 "J+!^l Z7l ]e F-6t^loJ 7lz7lTl qeEf. SE

"Ja$lll+=
ulill9 3+oll= a-7lz7l7l00lrloJ !^ll 7li1l9 e+q|= ?19 fs ?lr Bg
+4q$q. "l 4fE¤ e tr
f floq EEoll rlat,rjs qE+. Boyle EEoll,\l= 0l 7l37l7l00|q,
' Hlq"Jvkial)ol+= Eae 4Hqq oJq^J
'Jg gqg 6Z
q-E tlxlltl tl= SEg
61 82,83, ... Eo
444zlg t4. ttl101l Hl6t| 6101l^1 0184 "J- -Jtt.
22 1 Tldlsl8E
@Er=
qI trl= H+&4 ee EL+! zl&21
"lSP H+E ^l}ql
E EE 4o14.*f /(x)9 s.-et# dftdxb *44ee. r1g.
dzyld* <0 d2yld* = 0
4 ?ol eE¤q.
#=U*e*@ l^rE-s+rtrel
Y \
r$p+lq _HoJ HIel *"1 ol rtrrag 6Ji/(x)9 :.4ggl 4 dzyld* > 0
+ ql +qd , zloil^lg ddq z1&zl4r "I4B + 9l+.
ol rz| selizl-oJolH ol gtfzl- f-l+_e_E alap(xzl *zl
X
.Jql Trl+), ol rz| setfzl ¤.olE Hi'H+g 6J*+. ri} E tlsl2
6J+= ¤E^J f '(x)E +$rll7lE qI+. EL+E zil E*#
d'zftd*+ l^t Esl-+ f(i! E+++. +, dd
* sma.r = acosax bcosax=-asrnax
d'f ,,.__ f'(x+6x)-f'(x)
*=limr_______ d.
dX' 6x+0 OX
2i|E-er.+[Esl] . ln ax=-I
dxx
2iI Efl-+E_ ¤qt f"@)a 444zls- ++. tE* zgl E e-+Eol 4"J5I4l A*E]9g ullE rg;q cEql Irl+ 4
t HIeI *"1 ol zz| si14; #E +Eel ql"JCg +u| gl} Ae +zlg ol++trI.
uqa ql4g + 9l+. olE 2zI EEI+= *i lx1z| ue.";
g +$rIq, +E 2iI EEr+=- Elfzt nEoJoJg ++Utr}. d
(u+u) -
du du
dx d-r -dx
lit Efl-+9 Y oz| H6l+ t!{Sql,q + 2^l Effiz} sol d du du
. llU=tt--z- * U_-
gtrI. dx dx dx
.J+EE EEI+ trl-g'=r+ ,JE+. d u ldu udu
E6l
^l¤-{+ 5itlzlql dxu udx u'dx
d A+ql rr|{^J= x zlz,llsc|= x9 EtfE trl$6l+ 4ol S
& x =nx
n n-l
ele- UIE gl+. qlE^J trl¤-r+ eg Ei+E ^84611 Ezf.

9"*
dx = Ae* =-E
f(x)=r****
¤ zl,tl a, b, A P ^J+o]r4, aita*z]. oir-l 4 dfld(rlx)= +6J
dyldx = 0
Qr. a121. oltrll= *d y=Uxa +I ol EL+E f(y)-a+U
dyldx < 0
+ qP 94 Hl-$tr+. :aBlH,
Y
dyldx 0
!=a+2cv
dy/
yldx = 0
¤zlrJ y=11yollJ=- r+q_r+ ,J? 4+7I ¤+.
df
x
d(tlx) =u
*1
tlel t
Blq"J 4l+= gEql E=6fE*e_ qE 6J gEqlî= .Jq ,rJ BoylegEql^J= B,=0ol g+. r?]6}q
1c.3allgl E6IE
"l *4+ E Fulz} = trl] z7l 04 zl&zl= zlzlt_ l.tr. d= ol $Eollr.J= Hl?-l"J 1 q-gql _q= arq .J(= B'p)ol
^lql^J
ts + 9ig aol+(rH lc.4ql^Je} *ol). ol gEE Boyle t 0ol qA E Cf+ r H + rzlel 6}=0l +^lg + 9lg eE
-E rB4jL 6h=ql, ol $Eoll.!Ep-0ol Eql q4 d4l Tlill e 4zl trllEql += qE gEql^lB+ EJ Hg "Jq ¤qql
9 C{"l $d zli,llel Cel} "Jzl6l|l E+ rc.+azloll 9at 44^l pV^=RTBE S4lzl CBtJ+. g$$ Ts=22.64K;*21
H B'=0olH p-0ol Eql rrl?+ ZE zl&zl71 0ol Elq, r}+ E ru -346.8Ko14. ¤4 zlillql 46J ;I5g- s 1c.2ql ++
lC drll 7li{l 23
E 1c.2 71i.il=e.l g4l g+- (a) 4q 8E UE

p,latm V,l(crn3 mol-t) T,lK Z, TBIK ).D. van der WaalsTl- taz:Hgl zll"J,t} ol 43 E4qi4 o +E
AI 48.0 75.3 r50.7 0.292 411.5 A*6izl"J fqlorxg_e. +E6l7l- $fl-aj EzlJ. !+ql4"J
qlTI q= aol
CO, 72.9 94.0 304.2 0.274 7t4.8 ^J4sE eg + 9l='JBg Hq++ +e
He 2.26 s7.8 5.2 0.305 22.64 +.= ol + JE +g qloltri.
^lg'Eg
o2 50.14 78.0 154.8 0.308 4[.5.9
. q ".*e (}# 4s eql ++6tt +gltrl ran der Vlhals SE}l l"l ?tr
E{-E ^plql Hlg tlg4*ol "Jq+= 13 tszEol 4lxl
6l] +91+ "J ++qL +ae BE" 6t7l
qlE"l4l ^J4g + gl+. olilH
Ezlz} +i{$ zlzlAl9H olE +zI7I *e "J+= ;<lzl6}E
(c)BII 8+ -e ol5ol tr-E"6lt *1lE Pulzl-y 44lql v_nba
gll EE z.4r =qE
o + $"JolE z|d"l ilzl6}=
gE= Eeq 4E ¤qg EE EEI
6F= "lo} d4. ¤zlrl nbE 4xll4
gEs^J EeE ^JEll. E6l-= ql 4+ +s+ qgg dll +vltrl-. ol b?-lql trlszl$ Hlg 1i+ol 4*,$4. zl
^l7l= i-ll B 4 p _nRTtv¤ r-fqt=r+ pol llo} 6J+
=
++.= ?iB+ +61 a+"J *g s-EE E"S *dg glql^J
ol"l ¤Et ,J^lql 44 BE" 6J4. + +y]e+ "Jqql^-l nRT
=CqL
zlzllzl olillE ffiqq, ol + tr rl-ol9 Y- v -nb
i-
-trEol +q.441 B
.J+. rq+ ule [glrl "J+g
"J"J ^l7lH F t]g E?-l^l ol +ylE- 4l&6lEJH Hlzl=ol rolr. PqzI v_orec,re=
uJlzll
7l= sE"l +4+^l ?*eq, E"g +dE +¤ ++ * ¤ql f nt'oJ + ,Jill+ +zlE 4=d zl"-l= 2rola- q+^J :a u}]
rJ9 .+ylzl. *
d o e. .Ja4l+. ol dg Tlillel or4!Eol+r. +i{= tn(2r)3 4 8V.or..,r.ol ¤4E ^l-dg f E6110} fltri.
"Jaldql^JE "Jqq E +'l= zlzJ a_ EdE g4l g
6J+. ^ll
il Ezl'J ulJzllgE +yl= ol +qE HL + 4v-nr".,r"olr" Irl
4 p.4 g1l +tr1 %4r qI+. r4r p,,v,, q ?iE E +lJ b= 4V.or..ur.No7l g+.
r =
q^J EA9 "JZI 8+4r qI+(E. rc.z). +¤ "Jqe +47l rlq4 +E6l+ qlEe+ +Eg ollel .J
7.el r H+ te gEql^l=, .rlEzl-*zl9 dill +q= il- q q=++. ol e= H_lEe+ ".Jg E + ?lq tsa}*ol 4a
z16l-= +"J tr-g olE+. olEl* ^Jg
cEtlsE E trlt zlz11o1 ++ L.Lzlq, ral6}"l ^lE +ql E-q fl= tlg4}+ Ezh+
+.= "J4l gE ol^Jql^JE "_qill tr-ol ¤dgzl ?+=4. r>r, + ^lE +ql Eqfl= ExlE gBE ntv9llㅇ Hlell6t= aJg zI
ql^J +zlE +yl Aill= ilzl6l.= +"J tle +471dB4e
e ^J4q+ zlillB4 tg "JEE 444zls 6l+Ell olag
1
zla 4L+61+ 4o14. ole+ ?ol tE tlss+ Eg E trl "Jq
{ts4l+ql e]6]]^J eioFrE Sqg gr-"Ee-l zllfiql Hlql
iEg1l Bi{l4r +=4. all.{ 1t46}Al g+. ol "Jq a}iE a(ntr\zo e rtqB + 9t
Hlql tr-+ ai 4 Tlzllql r+* "JE ^J+4. "l Hlgq
#JEt q 1c.3 =ql,
4 eqE F a.!g relsll+H "I4e+ ?g- van derwaals 4.
4I4'E 941 8E-= lssKoJtrll, olBq t.g gEql^J= E. el^lg eg + 9l+
4$ zlzl-::. .+ill 4lA= "J= + H4. Szle-l dill +vl$ nRT n2
zlzl6rzl ?J:= qqi]l tr¤ tsgqH, + ol zlxll$ eqEBlzl P= v Van der waals A|E[|^l (1C.5a)
-nb-a v,
qH +d 7l4lel gE= ,5511oJo|tr qlfl +*ql l="g4
o e SGoll"F *4.
t}f a4 bE van der Waals 4l+4r 6hbql, aE ?14 {Fs
{+el ^1l7le=, :1;l-l- b= Ezla Hlg tr-o++g rllzlE 4
1C.2 van der Waals SeJlAl 4d+ "l 4l+Es ?+7+E Tlillql r++ <k* zlz\q gEql
++6I+(s 1c.3). a* bzl ¤qolll C99zl ?+g +Î ^de
Hl?-lg r
4l+E {t=¤ Bq+E A+6J ar+= +
^JEl]^.lg
$"lzl} 5Izl"J "J4l .$s., *zl "Jq, r4I +g tlBrle+
e}B + ll4. :_4+ +^ 'J ggd-q+E E= zl;{E Eg ?3 EzIrJ tr-g4+9 r.llzlE Hl¤61+ Efl4 ^dA4 ¤+
g+.
4 o + +l;ig + ?l= rlol frSE uils zl^? gl4.
24 1 Tldlel¤tr
E 1C.3 van der Waals 1l** 6
a/(anndm6mol-2) b/(10-2dm3mol-t) 4
Ar r.337 3.20
x
2
I
CO, 3.610 4.29 o
o 0
,/
o
He 0.0341 2.38
-2
/
Xe 4.137 s.16
. trl ".+g <f$g zlg ¤q ++6tl +9ttri 4

-6 0 0.1 0.2 x 0.3 0.4
lc.sa+ q+4 *ol E +iil v_ -vtn4 EL+E 44421

^l fH lc.s E7l 1c.1el voll Sel :xFlE r4s "JE 6t|.
E,*+.
RTa tg +61+ lol ¤4aI4.
rtl= v^-b v3 (1C.sb)
s. lc.3ql el6IH a-3.6lOdm6atmmol-2, r?]r
=01
b _4.29 x l0-2 dm3 mol-rol+. rela saql^l= +qd
RTtp-s.410dm3mol-,ol+. tr|4^J y_ql +* ol ^lE 4l+
E=g r+-Sr+ ?"1 ¤4.
Udql ql6H^l= a = 18.57 atmdm6mol-2(1.8s2 Pam6mol-2),
b = O.ll 93 dm3 mol-t( t. t93 x l0< m3 mol-' ), :7?-] tr r tL #
A b+RT lp=9.453dm3 mol-r
Edg 3s3Koltrl. 400Ke+p= l.oatmql^l Sd zlxlls 5-E a Ip = 3.61*1 o-2 (d6r mol-' )2
Hltl 6zlE E PvlzI v*-RTp-33dm3mol-,ol qq, q abl P=1.55 x l0-3(dm3 mol-' )'
+^l sd Tlill ^deql 'llEL 7l+ v^>b= EI+^]ZI+ "| 4

4\ alV2 =o.Ot7atmol 9brll, olag 1.0atm9 1.770 4loll "lq^] x-v^t(dm3mol-')olrp +gH E:qot6J 4"1
g+. r46}q ol gEe+ Sqql^J= fl{ zlillz} Sd

*4 *"1 84.
"J
Tlill ceE+q Ea aE9 olR"J ++a E + 9l+. x3 -0.453x2 + (3.61 x l0-2 )x -(1.55x 10-3 I = g
BotEB + 9lE *3 lc.s), trI4^l

x = 0.366(:aH
v^-0.36dm3mol-lol4. "lq+ aaq^J +d TlillE a
fflf van der waats 4E ol8Et
=
+tr| 4ltt +ql= E Bulz} o.41odm3mo1-'ol ¤tr}.
van der Waals 4lg ol+afl,<J s00K9* l00atmoll,rJ9 COrE
g PulE
xP! B7l 1C.1 100'C9l l00atmoll,<l Arq
E +qE 4l4I6Iq?+.
derWaals Tlill= z|{a}z Ah}6}q+.
"an
a.4E AIA lc.sb^]E van der Waals 49 +q^l g +El r-lotufuIP36z'0 tE
ql ++ ^lg +6110} ++.*d "l ^l "JHql

(y",-b)W^*
#611=tr}.
(b)
(Y- P= RTVS-(Y- -b)a
- b)V:",
^tE =d
y"'g g+ql Eofl $e=$ poJ
olzll ol vanderWaals t4al"l dxll zl4l9 B# qL AE
"lq^l pE ++r" qE+
E e ql+6r=zl ¤{trzle- 6I'|= zlzla-
a14. ++6J
s+. ^l
E= Eill9 +la} tr-E.ll^lol ¤ f ilzlE HI+= 49 ul#4
,;-(,.f),*.(;)* **=o q+4ql ^J4ol4. 7l4lql ++ eq+ Al&g 6tEjH Hl4"J
rl9 ol+6110} 6tq, ¤4 gs1ql^lE 4l+el aE¤ Ef,.il^J
37t Hla^lE 6Il= 4e+ E olag ql+61 + += glzl"J *ot ^^7, E 4l= fzl4-" + ql^t6llot ++. rEl+ vander
waals 49 61144"14 {xll zlr'llql +q} "JH}4?l AEg .
t}6t+ 6ll^lz1 617I + pealzl g*g a+ql= .JHI49
qB + glrll zlzl:il- ?14. ol tlEfl^lol g *
-e.
^l+
+EE?llq= ol+6ll^J r4E *Bse qlq4"J "ll=+= tldg
zl 9+g trll= +E tr-44(r+ "JpzI s. 1c.4ql ++qq gl
lc :!ql Tlill 25
E 1c.4 g+
(
d:E|lÎE
"J4l dL+
,\l
-1 +t}4- P" v" T,
nRT
9d zlzll rv
i:-
nRT 87: 3 a 8a
van der Waals 6-
Y- V-nb y2
n2a
,'- rrra- v? 2?P
3b nbR
-_-
nRT n2a t ( zrn\tt2 ( zo \tt2
z tt
Berthelot r V-nb P, =8li-:
3Vr-l TrV? alrr 3b
3[3DRJ
TVz )
nRTe-natRrv Tre2(r-ur,v,) a a
Dieterici Y- v-nb Pr= 2b
zvr-l 4eP 4bR
Virial ,=f{,.#.ry.}
.++,tlH+E!x,=Xtx,E CE6lq, X=p,V^,r?-li1 Tol4.ol
^JEH^lEgE+r] V_=Vtr&zlzla_ +QLllzlE6Jr}.
+)-3 L4r+, ^lls-g 49 "JE9 4EzL E-= Hl49 ^ls.tr. 7IE"¤¤+ ?l+.
9EolzI"F qlq.
vanderwaats llol 44ql= E"gd9:B lc.2ql +EU
F'J.l ,r.-fe ulf$ a_7lz 7Ie ql= vanderwaals
lc.sb^lE
a47l +4*+. ol arq 6Jg EzlE ¤+ qlqzle+ +
de ¤lg +dr+ Hlr4 _H-H
^lel
ol t"Jcg s+g + gl ^lE
I 4o14. 4l&6J "J+ E"gd#:ts
tc.@+ tc.7ql +4ql
8.4. olES "J4l gE "Jql^l +4+= llE E"J +¤¤ ^tl
e]6IE de Fgdr+ q+q g "*=+. van der vlhals r.el
?+r +e= ol aE ++g +H6l ul¤d4ol4. 91,*:"IE q
a.
zl9l ule.E q¤ aA d-"ll^l= "J4ol ?zl6J oll Pulz} 6 ff
a
zlolzl ullEol4. trI+^J ol Y Eg zl+lr{qr z}?-lql+ + r
¤dg ol-4 fl Holz} ?otzlrll rel B=+."lag Maxwe[
rlEH(l)ol4r qI+. s lc.3ql +e}U HIe+ eg van der
waats 4l+59 ol 4lf tgdol ¤¤ +dr+ "Jzl +nl, v
6lE+ A+ aolq. = ^l-e"t
lg 1C.6 van derWaals 4lo+ aEqts A4=E rE. 0l .trE Soll raJ
-=ol
o
=
rjnl
alvt 58C-=3 ral 1c.79 #oll Elte-6l"= 7is=e,\1, nIE T/T,,J= L[Elurt.
1
1.5
van derWaats tL4!E +g q-g=+ pol effi f a

el+.
=ag a 1
mr
a
l. $$ gEe+ g +irl 6Iql^J= +d Tlal :a"g +dol <J
= {il
eqd+.
0.8
s__E7l+¤ tril= RT7l4+61 r7l qlEoil lc.sb^lg ar{l .}
ol E {l 6}H+ q+61 44 + ?14. S"J o}q+ E P.tilz} 1 10
v. ) b7l H a tr e zE +E7l v^-b =vôl g+. olEl6J ?,! +n.l,, v^lv"

aaq^l= ol 9d zlzll tr.4^loJp:RTV^se ¤+. azJ 1c.7 q4 T/T,',J0ll,\i zlu-J van der Waals van der waals
^Jol Izl= "JU4o+ #oJ 4Co+ Hlfl=trl. "J4l -c. T/T,= 1(844)oll
2. +d g'r+e+ S4I c'47I ilBg olE trll. 94lg+ zl4l E¤{to|tr[.
-C?
^19
26 1 TldE dtr
zl{ tr-E Hlg 4l+ql 7ltl6l+ 1"11" Ezll 'Jg trs ql{
2.0
A}+ql 7loJ6l^= 4,"14.
0.8
3. "JAl ^J+=g van derwaals 4l+e+ +dB+. N \

k 0.6 tp 1.2 ) .EA
r< 7:"J ull= 4l4I+ E$dEol tl 6Iq, 7+7+ *Ad"ll "l
-oJ
f,
" A
. 4lE
q^J +4d9 zlt4. ol +(}Ee r-r.g
ql +B6Iq $oo
,.0]
ty' o sPrJ
T=T.oJ trll "Jil6trll g+. trI4^-l g4dql^-its E"S^Jol H 0.2 Lr-
o ollE!
+dg +rll g+(2). +dE ^J4q E6IE ri} E.sL+e+ 2iI 0
H+dol 44t4. tr14^l ol E
E-el.+z} e_+ o"J oll "lBl-J 0 1 2 34 5 6 7
Stl94, prp"
++# 44IqI q-gql "l# 00 + +eH "J4 tr-+#
+g + 9l+.=, "Jald.ilîE trl-g aa.ol "J+g+. fg 1c.8 Ettt E+= 0lE6H^j s.,tl-d r= 1c.3E Lll 7li1l=9 g+ ?]Ê.
d8E ]t.xl# oJ4l .9E T,=T/T,E LlEl'.!cl. S^J E+E ol8dlE Tlillsl
rllolEl- :d 80il LlElg + ?1r]-.
=C
"J++.
2
v'= p,
t T,
T
+r! E+ tEEl (1c.8)
vL P, T,
dp __ RT _2o _n
W^-- fv^-W - y; -" +& "Jqg gE p=p,p,z ol$-all.{ a_ 7lill9 dxll
Tlillel
d'p _ zRT _6o _n "Jqg dril 4l4IB + fleq, +{e+ gE-E u[]z[z] o]Hg-
M-v=W- E 4l4lg + 9l+. ol %l'Hg 7l¤. ^lE4 g van der waalsE
E"J+ +HI +ul y,.g zlz16l+ ¤xll zlillEol E"J+ ¤+Î e
ol EH(:z4I- lc.sb^lg ole" a|{ %e} ?:s*q p. E 44ql fl¤- EI= E+ tl"J6J +4I E.q p,g +48 a"lrt
^lE¤-
E +++) q-q-r+ ag ar+. eg + 9l+. r olq+ qltlg qalE Eq"*gl+(rB rc.s).
^J46I*.tr1.
ol rgg ¤4 zlitl$ "J+ tzlzl qel S+& gEql^l +4I
V-=3b
-c ,--
rc
o,- 8a (1C.6)
"- 27bR
27bz
"Jqq .q=6J+= 4,9 u-q+r 9l+. ol r4g= 5+& H+
ol +41= a4 bE g4l tl.+ itEegq +61+ ql ol+q= 4zl ?*r Hliq} zlEE E^l6J:zB rc.:4 u1:zall -HE
=
+B6l 'iltEl C*"Jg "J + 9l+.
E 6l+E BB o + ol$slzlE 6J+. "J4ld +=ql.rl van der
waals tlEll^lg "J+^lzl}. zl{le=$ E+ r g4l g+ ?lrl E"J6J ++& +i{e+ Fgfl Et& 3s 6}ql fl= {zll zlzll
Z,zl rp-4 ?ol 99o| ol-irll, olag z$ltol ^Jql^l¤- Eol t-"J+ ¤+tI g.qg qE}.ll= ol Î¤¤- ql8 gEl|sl flel
B+fl=a"l+. 4r. +q. ol gEl= a"J Sol4, 7¤ Ezle ¤ zl
^leql =^l4e
illql q6H^J= r.llill4 o e ¤- "*zl"J Ezlz} +Bol olqa+
+d"J ul= g *zl ?,I84
3
Z, _ P,V, _ (1C.7)
R7: 8
lc.s
z}trJEt 0ll
E 1c.2ql el6l$ El+ Z,<*=g.3zsolzl} olzlu3 qlillzl e e
ols+r+ olt}El+ael "J4l tfE"l s. lc.2q ++qq
9CaI4(0.3) r ¤iPI Hlj/4 4L+.
?14. "tg=-ol 23atm4 200Kql fl+H ¤+4I "Jqq +l r
(c) c]|B SEtlE fl4 &gE= +*4 e}"l s4.
zI¤ r++q^J qq qtlEg ^Ja5g ulnali fl zlzl fe 23atm 200K
P'= 48Jatm =o'48 7'=
rroJla =l'33
El HlBe E"J 6+E r++ 7lE de'J +9, q
=a59 olul "J4l ol{lirltsiT} ql+ r Sq$ 3rz1 c1-g-
Tlql "J46ll^J
^Jq4 zJE= 46l+ 4"14.+t]= ^Jqq fleElH
ttfE"l 7l4lel r+ql C4"14= ag "Jrll q$,eq, "l+ 4 ?ol 9ol"t B 4"14.
olE¤ zL"+48 4= zjE= "JE + gl+. r?]6}q q-¤.
^-l p=0.48x(72.9atm)=35atm T=1.33x304.2K=405K
4 trol {xfl g;g 611'}
"J4 ^}+E +E Ett E*59 s
1c grllTlfll 27
4E ol gE]E g"IzJ "J+^lzl+. +d

vanderwaals lc.sb ,r.la|fl(:2fl lc.7ql^l e]H6}r r*..ol) 9u]* zl^ll
Îdg
++& H+E r^l^J +EI.IE trl-g+ *ol ¤4. ql qlql^J+ +ee +dol +E}t3 4o14. olag'I*
^lg ^J=IE
gqe+ +eg {+ql E46Lq, q-4î van der waals tr"Efl^l
RT-T- a
P,P,=vifi-w g ol gele+ _5r+qzl g+=trtI Eg + 9l+.
rBl+ ol {ffi LJ+ 4E|]Bz}6t= ag A*olr}. :z z}$
olq^J lc.6^lg ols-"ol.{ "J4 tr-+# a*b4.J+E +4 g +E tlEll^lE(-*. 1c.4el 4.)E "l 4¤ tlEll g4E "J+
u+. xlzlzl ull$ol4. dzlls a* b4 qgg 61.= + zll9 vl4pl
ap, _8aT,l27b a q= 7|zlr. gl= tlqJ^lg qL 4ol4 E+ +& tr-q4eE
27b2- 3wv,-b 9b2V: H++^lvJ + fl+. A+ {xll zlillEol ol g4ql q=+= ¤
e ^L¤E+EI al.ilE_ EqE + 9l= AEg "Jqr+ HIts ^J
"JHql ztutaE +qI q-g c?]6IH q-q=r+ ag ^l"l +g+. o + +g +?+r,lElE +qe + 914=
s4l+ol 7+7+
p
87. 3
(1C.e)
=^14
4sol4. ol g?;. olE4 o + 4461-= 4o1 fe.l 43 ot
3V, -l v:
qq, q4 a" F9 zlillE ^d{g 6l+.el :aH o +(41d4 :B
^lg Efle-l !4 E"l Ezl"J lc3 ql4lql :H lc.8) ++g + ?lrll 6l= "JBol+=
ol zlzllql q+^J E4zlE tr
^ld
i a* bzl t'y44+. Ir|4^J ¤},tI H+= zlzl:i- E"¤-d¤- E ol +.q+ 4"14.
=s-d7llLJ=
D r. 9d zlrll cde+q9 olB9 s+ ?.!rlE zlzlt_ _s_o+* tr 5. {xll zlillel E-"J4 tl-ql^l " e^1,
van der \rilaals AEflAlg
+ el+. +zlE "Jqql 4s"61-b u}4"lel as+ Ezt Hlgql qt86l+
a 2. Hlalg Aq4e 9d zlzll

^JEI^lg
qtl^lA
dflalolq, tr ul-4"lel b= 7l^la_ +Elu 4"14.
B,* =a H9lql 44^1{xll zlzllel qFg sE6J + 9l+. ! 6. vanderwaals ^JEI4$ "JAl Ceg EaJa.J ¤zll zlll9 gHI4
I 3. {zll zlzllel E"8^J3 g4l dtr$ T]]H$ u1e_41 6}9trt. cagg s¤+tr}.
a 4. zlill= zl",I:"I9 "+s+^l7lqH : gE= Bz{l Es. ola}E a 7. ¤x]l 7l4lE Ceg E$l E+E zlzlt- +ElU dlq4se
qlel+qo} +tr].. :a" aS,rJzj
+ gltrI.
=s-d^l=
,rl
oe.zl --lI
7-.--1l
I 4Ha
oJ+ oJz} Z=V^lV,i ol
zlo-1 lc.1
Hl;-l"J t}4^l Pv = RT(l + Bl v *+ Cl v; + "') B, gEqI E=
C= 1C3b
^
van der Waals
^Jq^l p=nRTl(V-nb)-a(nlV)2 aE "JH, b= Hlgqql 4s" 6lt ulelolQ lC.5a
+& H+ x,=xlX. X=P, Y., E= T lc.8

28 1 7hlleldtr
li{l -ilol /\{II

d= =o
Ne
sJE zlxll
=4 1A
n= gxll
orn"r *E Sqol4= +qE ¤B6Ir, qrq^l Dalton9 Bzl"l +t B
다름99 ≈40
D1A.2 Boyleel Hzl, Ch.rl"r9 Bzl, of AvogadroE fl?-l= e6J6}ts qB

Or 0 254 ¤E6lq4.
zlqlzlE
.
0 251 ba .
사Oz ozz 3 bar
orzo ,ll sd zl4l lJ.r.Ial"l +Esl=zl ¤E6Iqe+.
Kon 64 0 nnnar r on 6 n on 5 nbar
o{-\
i
r -tl 3 42 bar 3 .38 atm
p ㅇ
.
ErA.r(a) 0.987barqzz'Cgl,tl9*zl9 "JE7l l.l,16kg miolfr.4. ol * 9d

El A.7(a) 4 t9 +ElE
zlzllE ¤,.g "J+^l 2.20 dm3 trJ¤! ,J^^lA+
z\zl (i) t}ê+ eaEJ-e--e slq
fl= a+e| (ii) l.00mol 709 tu¤ s6J6l r zl4l9 A+ $ql} Fulz} 44
Ar+ "l s.ubar4 +.0s dm3 o + s]fl+
r 9l= A+E z|{a}r. eê} 4}Ê E +gq ++ $qg 4t6}q4. ol zlillel ilg Sqg (i) bar, (ii) atm +9le +6Iq4.
EtA.l(b) 320mg9 ollE, tzsmg9 oI9*,o)22smg9 Hl8ce. ¤ zlrll E1A.7(b) 9d zlillE E" 3 "J4rl4 :29 +81= 1.80 dm3 uJ+ fiaz,lflr}
E-*Eol ?14. roo Kql^l qlgel f E $4ol s.sz kpaol4. ol gqlBq (i) a 41+ ol zl4l9 4l+ $qr+ *ulz} 44 r.gz bare* z.r+dm3o + Elfltr|
+4e+ (ii)
3 d4l "Jqg 4l,t}6lq+. ol zlillel il* Sqg (i) bar, (ii) rorr t+le +6Iq4.
354 m 24 986 kPa
ㅇ
.
E1A2(a) 9E zlill slE-EE "JE= 330Ke+zokpagl,9 ?da}grlui r.z: ElA.8(a) SszI -s'c"J Agql 4olqqlq $4"1 24lb in-,(1.00 atrn=14.7
1
9ztl *zlE Hfl+. ul*"l dq ^llzl 9+r +El7I H6Ixl ?*g
1
kg -""18.4. ol slql^gE E e+3 +6Iq4. 0
. 69gm 의 lb in-z;o1
E1A.2(b) oltr zl^ll9 E- a%¤ +4617l| gl6lq 250 cm3g ol zlal= * c.+ SszI :s "coJ q*q= $9ol B"le 94lr+i dxll"il 9lq^.t= q
tr +d.dg rqq +qo} 6IdL+? 30 lb n -
2
4 *zl9l Bfl+. zss K9lrJ $4ol r52 rorrfleq, +q a.q^5- HAoJ +
9 zl4l9 ¤=J"l 33.smgol9l+. ol 7li]lel g e"*g 9"lz}94]|.9+i E1A.8(b) 'tI+A zlxll ,<leel $4ol z:'c"il,rl l25kpag 4449.4. g-s
늑 nomg z| rr'c"J ullE S4ol 9"Ie 9dg+t
E1A.3(a) -85"C, O'C,:e.l:Z 100'Cq^lE +7lel "JE= 47: r.877 g dm-3,
r.294gdm-3, ',i 0.946gdmJol{. *7\71Charles9 Hlq rlE4l ztC ElA.e(a) Kql^l
122 255 mg9 r-llgol 3.00 dm39 +sl= ilzlql+. 9d zl
6l.a ol qlolEle+El rdLl zlEs eql gE <ig +6Iq+. 4lel d"4^lg r!^J "l zl4l9 $qg 4{i+q+. 004 m bar
E1A.3(b) oltr zl4l .+ulzl0"Cel r.omatrnoll,9 20.mdm3olflr}. ol zl{"ll,<l gf,tg9_e rH E"J9l +.oox rdr,r,9 d¤ 7la=
p
ErA.e(b)
^lEq "|tr
7l4lg +Elql EIql dB Ellolq= "Jc sq pql^l d4gE 0"11 46llî E ol Ag T!-Y +d6l oll* cHn"1g r gEe+ "Jqe zJzJ r.o
^l-*6JtrI.
…
,<la|flcJr-l tl$tlzl o.o74r dm3 "c'oJ zldol rl*tri. ol EllolElRlg Tizl atm4zo'col4. ol aAql^J ol ziÊ9d zl4le H n 7l1E A
^l-8:6J
a($d ,l4l Hzlg^l-S6lzl 'Jr) drAl 4.;e e4 ¤E=+6Iq+. +3 +6Iq4.
U J
+q7I zz.+ drn:"J 8zl 491 2.0mol9 Hre* t.0mol

ElA.a(a) 273.rs Kql^J ElA.lo(a) s00 "CeI g:.2 kPa"ll,q * 6z19 e%b gE= 3.710 kg m-3o14.
9 N,zt E-ol9l4 (i) 4 deSE E +-g, (ii) olEE +e Sq, rel-r. (iii) ol*l+ aaql^] %IE Ez}4e qB4 94Ls*i 3
olE.el d4 .Jqg 414IaIq?+. ElA.ro(b) r00 "ce+ r0.0 kPaoll^] eI ?zl9 a* "JEb 0.6388 kg nl-,o14.
q$rtl !Xl,s*i
"lelq} aaql^l "J9 Ezl{g
EtA.4(b) 273.tsKoll,rl$ulzlzz.+ dm3oJ -szl 491 t.5mol9 Hre|2.smol
9 N,zI5q9lq. (i) 4 C+Eq E +¤-, (ii) "lEE ++ "Jq, -r,el-r. (iii) ElA.l 1(a) t4
V
E7t eo %I "Jql Eq fl= *7lE
x"J ts aoo -' Pul9
olSE dal $qg 4l{}6}q+. ^"
8ETI 27'c9.q. ol %lEq fl+ iGzl\ A+3 4l,ti6l.q+. flE
"Jql
ElA.S(a) (i) 108 kPa-9 TorrF- (ii) 097s barE atm o E +4qq+. +E+ "JHI4 " + E+Elr gl= +¤"7lE ++ giq
oe^l ol gE
^Jqi
ElA.s(b) (i) 22.5kPaS atmF- (D TTororE pascal-E +4r-ilq4 ql^lE i6zl "J4("1 4*r.ambar)9 UISSE +4U+.
ElA.6(a) *qzI r.odm3oJ 8zl 4"ll r3rg9 z]lE 7l4l7lzs"c
ElA.il(b) t4 ^,E7I s3%(ol 4*Zsj mbar)oJ9 zsomrBvl9 %r" "Jql
=q9=
zlilli.lfl fl$.JQH 20 atrn9 oJqg +48 + ?ldL+? r+zl Eq fl= tTlE gETi 23'CHEI. ol %'-
"Jq Eq fl= iGzlq e%ig
"ll^-l Sd
4l&61q4.
e++H $uluJoJ Sqg +El{d,l-+?
ErA6(b) Pulzl l.s &n3oJ ¤.zl 491 5qfl= zs gg ol.-=.* zlxllzl 3o"c
ql^J Sd 7l{li-lfl dE"oJrl{ 2.0bar9 Sqg LIE|'J + gldL+? r+
zl ?++H 9ultlt $qg +Eqd-'+?
MO , i 1 bar
EA 2e
E4 18 EÎ
-E.'J
¤E Exll
DlB.1 He4 ?3 TIqg Tlill= al+ 471 +ql EErll o, 46Iq+.
=7.ll6lzlEJ
g=4
CO,, ol Nrel rJS +rl+ Tlill= "J+ BdEIH ¤'+6}rll bbt?lrll DIBJ zl^+ .!EE gE Sq, f-?]a zlzll $x| azlql EI+ E¤EE +
:z olf¤ Ezl ¤-F Egg ol+6tq ¤B6Iq4.
zI f Aql^l 6il46l _E-ole}.
DtB.2 Tlill Ezl ¤8"E9 zlEol gE zlc¤. +i]l4_e_s g,<1ap u. oll
cc^
Jrr
ElB.r(a) zo"cgl,,.l cor$z|$ ?l* *+ +q, ¤+ +q, rqr
B+ tI ErB.s(b) d+zl rskmoJ +olql^J9gzl 2rTKola- $tsol rz.r kpaolB.4.
ql+qg 4t4}4q4. mp men ree N, EzlE ¤t esE +6l.q4 (o =0.43 nm2).
zl-.ft
E18.1(b) zo'CglrJ H, EztE 7l* *e +q, ¤+ 44, :uzla B+ tlEil
E18.6(a) zO'C"llrl H, Ez}el Hg flz}e+9 (il ¤+ +q, :fzl:r (ii) ¤t
+qg 4lt6}q4. 조0 60 80
Brl +E qlqzlel Hl= 44 +6Iq4
ElB.2(a) 2s"C 1.00atm9 zlrll +ql^JE urEzI9 +E HIE= +6Iq4. EtB.6(b) zs t"llrl He flx}e| Hg flzlo*9 (i) B+ +q, relr (ii) B+
ElB.2(b) zst t.ooatm$ zli'll +q^lE o,ExI9 6¤ tls= +6I"i4 Erl ¤+ qlq^lE Hl= 44 +6}qel.
El B.3(a) *zl9 C+"J N, EzI9 +E zlBS 3es pmole. 1.0 atm4 2s "C E1B.7(a) zo tglrl H, +z}e+ o, Ezt9 g+ xI* +qg 4l{}6}q4.
=
9 *zl +ql^J ol Bzlg B+ +q, (ii) B+ zl-# Bg r4-r. (iii) +
(i) E1 8.7(b) 20 "cql^l co, Ez}el se flz}9 ¤ + xllt +qg 4lt}6}q +.
=
5 HIEE 4lÎ6Iq4. E18.8(a) Maxwell9+E Es^19 "l¤:a}q 400 K9 N, Exl ¤!"ilrJ zOO
E18.3(b) Cbol 7I* =-3 dBd+ tl+ Es= eI t nrorrel tlt9 "JE
tsel zto m s-' ¤qg +qg ,*= Exl¤E E+g +6rq4. fl-E, uel
+ 91tr|. 2s'Cql^J N, Exl9 +E zl+q=g 3e5 pm-tr_ z|{a}n ol +z}el
Î"lel +q¤- *= +zI9 8¤.3fl2)duE folzl{,f(u)y
u*du 1B.4^l
ol tl+ t}4q^l.el (i) B+ +q, (ii) Bf zI# Btr, f?]r (iii) +E HIE
o + ?9{4.
E 4lt6lq+. E18.8(b) Maxwell9+E +g.^19 ol-&a}¤ 400KE cor¤:z}691.,.1 aoo
ErB.4(a)20"cql^l r00cm39 8zl9l Eq il= olstE B+ aI.+ fls +.el +osm s-, ¤gg +q¤- r*= +zl¤q E-gg +6Iq?+. g+ E18.8(a)
zl t $zl! aTle+ "*Eg 4E7l qelE "Jqol g"}zl 9"1"F a}?lr+i I '6JEE etr6lq+.
o=o.36nm'9 +l6}q+.
zs'c9 7li'll +ql fl= Nre| urEzl¤
^l"lel {-q4 ¤+ +q
ElB.e(a)
EtB.4(b) 20'CqlC ols=$ ¤+ zl-+ BezI r gzl zldq l0EH zl$r+
g +6rq4.
"*Eg Aszl q= gr"qg 4l4I6Iq+. o=0.36 nm'9 A5Iq4. zs'c9 7l4l +ql 9lE orsl
EtB.e(b) N, EzlE ,tlol9 tlElzl ¤+ +q
El B.5(a) aSJl 20 kmoJ tolqlî S.Ezl 2r7 Kol:t oJH"l 0.0s atmol fl4 g +6Iq?+.
N, Ezl9 B# xl-# qs= +6}qq (o=0.43 nm2).
5
EE_r lC !^11 7llr11 =
"WA
Bb
I 6π
¤E E^jl
D1c.t "J4l t+Eq 9EE "5"I¤4. DtC.3 vanderwaals t44ol
Ceg "tBal ¤B6l+zl Et-5Iq"+.
"Jal
기로
patm
[ g tC.+"ll +ElU tl= *4^lEq
D1C.2 vanderWaals tl44g ¤B6I:1 Dlc.4 dzll Tlillg a+, "J+ oJzlz} oJq4 gE_ql q4 qBrll E6kzl
로 ()
6JelCg "J6ll Eole}.
> ¤86|r E olaol EzlzJ "Jqql *-J olrlel atrE +4Lil=alE ¤E
6}q?+.
a b
o{-\
r-ttl
P=
재
-
2
=3
b 2. 9 =
재
=기 K =
3b E
8a
태bR
Elc.l(a) qts9 oJ4l '!-+E p,=45.6 atm, %-98.7 cm3 mol-r, r4r E1C.1(b) qlBE g4l tr-+E P,=48.20atm, %= I48 cm3 mol-r, :1?-lI
I.=1e0.0 KoltrI. ol zlillel van der Waals tfE
4lt}ilE" ExI tlzlE¤ T,=30s.4Koltrl. ol zlillel van der Waals t}¤ 4l4}6}jr, +zI HlzlE¤
+4q4. +6lq+.
a o 351
=
= 0 . O49 적
30 TldE ,8E
zle ¤9 E lc3ql ++¤ giE van der waals ulr-|ulelE ol

E1c.2(a) ElC.6(a) van der Waals tf a=0.751atm dm6 mol-29| b=0.0226dm3 mol-r
+6Iq (i) giE Boyle 9E Ts=atRb* (ii) Cl2 Ezl-3 7¤ o -+ tr9lg trll I SI z1g +91(kg,m, s, r'i mol)-tr +Elqq4.
E HlzlE¤ 3rl-4 o e 4l4I6Iq4. E1C.6(b) van der Waals t}f a=1.32 atm dm6 mol-29| b=0.0436 dmr mol-r
E1c.2(b) zlE ¤9 .*. lc3oll ++g *q;O, van der waals ulalulrlS I Sr z1g +91(kg,m, s, 'i mol)-tr +4LIq+.
ols-oap ol zlill$ Boyle ¤-E Ts=atRb* (ii) Hrs ExJ-= +B9 +
111 E_
E1c.7(a) 2s0 Ke+ rs atmgl^l qE zlill9 E PulzI 9d zli-ll t4alee
9tg trilE HlzlBq <l# 3rI4 " e 4l,t}6}q4. 4lÎ¤I AE.q 12"/o;*"k4. ol 7l4lE (i) ol aaql^]E "J+ "Jzte+ (ii) E
E1C.3(a) 1.0 mol9 (i) NH3, (ii) Xe, (iii) Heol 2s "ce+ 1.0 atm a}9l ?lE r.o +ul= 4l4I6Iq+. .Jqr+ HItsq + qL {ol zluflzlol4l.g+l
mol9 HzeI rI+!= tl4ql flc."l$ Sq4 Sszi g"Ie}"t qdL+? KeI 12 atmgl^J q¤ zl^]l9 E Pslz} $d zlrll t4ll" +
E1c.7(b) 3s0
E1C.3(b) l.0mol9 (i) Hro,(ii) co2, (iii) Arol 2s'ce+ 1.0atm a}q] 9l= r.o 4liJ¤I *tr+ L2yo il4. ol zlillel (i) ol aaql^.lE "J+ oJxl4 (ii) E +
mol9 N,4 Ell*51= trflq fl9.el$ *q4 gEzl $"Ie|"t q4l,L+? El= 4l4}6lq+. "Jq4 Hlgq + qL {ol zlullz{ol4Lg+t
ElC.a(a) olts zl4lzlvan der Waak al9 EI+^l7l=E'll, a=0.50m6Pa mol-2 Etc.8(a) 'J ^JÎ r+Aql^l ei= 1.000 mrel "JA +ul 8zl9l -Jr s00 K
ol:L r E +irl= 2nKe+:.0 Mpaoll^l 5.00 x ltrr m3 mol-rol4. ol zlalg tr. zlpo|flef. ol zlzllel e'*g 92.+t<go1E4. van der Waals 49 ol+a}
ol+6}q van der waals ttf h= +6Iq4. ts.FE gEe+ E-qql^J ol 7l 9 soo KE +E gEql^l ol zlzllzl +ELil= +Î4 "Jqg 4l4}6iq4.
illg "J+ "Jzl-b g"tz} qae+? A}'q qfliJ= a=l.352dm6atm mol-2, b=0.0387 dm3mol-'o|4.
ElC.4(b) qE 7li{71- van der Waah !$ uJ$,<lzlirl\, a=0.76m6 Pa mol-2 E1c.8(b) "J+ Tlill dflqql= "JHlzl o + 200bar9 $4ol f u)lnlzl zl
oljE f E +E= 288 KeI +.0 Mpa9l^l 4.00 x 10-4 m3 mol-rol4. zl49 ill5 iflgq. ti$ a+, (i) 9d zlill ^JE{!$ (ii) van der waals tr-Ell^l
"l
ol*6}q van der waals tl# b= +4q4. EFg gEe+ oJqqlî ol 7l I "l*a}¤ ol sqr+ 2s'cq^Jg g +q= 4l4I6Iq+. 4}4ql Eil6ll^J=
illE "J+ "Jzl-L 9"lzl94jg+t a=I.364atm dm6 mol-2, b=3.19 x l0-2 dm3 mol-rol4.
E1C.5(a) 1.0 mol9 qFLol G) 273.ts Kql^l 22.414 dmr, (ii) 1000 Kq^l t00 cm3 mol9 c,HuG)E 2fcql4 4.860 dm3E *zl 491 Bfltrt. (i)
ElC.e(a) r0.0
q +4+rll ¤ Sqg van der waals zlill$ z].{a}r. zjl
E +ElE zlzlal 9d zl*ll$ (ii) van der Waals ^JEI^lg ol+6}q ol zli]lz| L|r}p Sq
tI6Iq4.zlt ¤9 E rc.3E E'llolEl= ^l-8'6}q4. g 4l+I6Iq4. ol el|s S+ "JzJ-= 4lÎ6Iq?+. ql*q qfl^l=
Âl^l
Elc.s(b) 1.0 mol9 H2s7l (i) 273.t5 Koll,tl ZZ.+r4 dm3, (ii) 500 Koll,tl tso a=5.507 dm6 atm mol-2, b=0.0651 dm3 mol-'o14.
cm'9 PulE zlxla3q +ELtrll B "Jqg van der waals zlillE 71461 Elc.e(b) 300Kel20atmoll.tl
"lH zlill9
o;4. olzizl0.86oltrl.(i) ol aA
a 4lt6}q4. alE ¤g s 1c3E qlolElE ^1.&6Iq4.
q^l ol zlzll s.zmmol9 +sle+ (ii) 300 Kql^l 2zl Hlel"J 4l+ BE
4l&4q4.
=^lil
=
-yvlLt Tlillel 8tr

Erlt
=_d4
1.1 Ell* CH4 +zl+ +E +E4ol o=0.46 nm2oJ i.B BzI4J, EolE B4l EzlE B+ ¤tl ¤.El "lluJzl+ trkr?l EtrI= +F +Hll g
eE" 6]^=
g+. trll$ Ezlz} Efl^ll6l-= g +rl$ 4l&6}q van der waals tf bg AI ElE 4*Cg eE6Iq4.
g +6Iq4.
t13 zl+ ?91 4zl9 +^JEg Bd &rE"r+ *41 eld g# 6l+ 2gz}
11.2 Maxwell-Boltzmann Eg4lo +'El gE Tql^J zlill $xlel Ezl-Eol4. 4zlg Hll ¤+ qlLlxl "JE7l 0.15 | cm-rol+E qd gF
zltl *g +qg +4Lll= =E6H
+E6l-¤4. olgd 3il_fl +aql^l zl_+ {lHzlE so.Jo.J d^ll ¤E qlLJzl $"tz}9flr{i
^lg "JE=
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166
¤e.21 *s +ql^J R ,ll %I=El= qlulzlE +9E- B6l= 2C EErqt
cll ol$al f gll, flTl +ql^J B *}l "J=q= qlq 4y z1
414 "Jg "JE # 9l-r, E p+E HI¤¤ E6ll^l dzl-B gE 'gsl+ql^l= HI* rlcql^-l "Jq+= tr9 oldg ¤*
slo+
. E6ll a-e.z]l aiE dzlzl "Jg "J. + gl+. +qL HI+= *tri. ol Eqql^J= $i44 4{ol4 slql EElql +Hl!= ql
6ql= 9014 "Jg g= + gl= a, oJ=q= g
cll ols" B Rq H+= 4l{r-"1+ ¤+61^= %r-Hq +4î ¤EB 4"14.
e til4r r ^Jc Eag g= ql "l+q= a, rr]a 4E
4Ag ol?= I Fol glq.qlqzl H¤|9 ¤+61-= EE-+ els; zc.a !E gH
I ol¤-a}]^J +4= olBl+ E= HI+E¤ CeJ4 oE ¤E

6J + ?lr E ++6J q+g 6J + 9l+.
2D 8Ell -Et+et sJc EIE
olTl^l= 4el q4 /J-olal
^da= ÎolE +al=
qB^14+
zA L]|+ ollLjrl =
gqEE +lqg Eq+lzl qI+. gqEE q+q fi+*
d +E 6|+E + ?16l+ ^J¤E <19 ol de+ ro+ +E
"l Eqql^l= 4l7l a ++le+ "llHzlE r+t6}= %r-^lql + ce# +a6}r ol +a ¤459 aBi+sEAl zld4e
6I^J _r.3olLzl. att-rll, ol *zlql= 4l7I 6La+ 4lq qql E. gg + 9ltrl= 1,"14. ol tr491^1 +E6l+ +4lEg 7l
zlE "J9 F6l. 4+,412[ r]l+rl+ g.+6t= gg 5{-- illel o+E+= E6Ir, E ^Jol¤L a{a}ol,<Jel gs" +=
^}"lel
4ol gl4. olBl+ rB¤ ¤!6l]^J 4lE + glHxloJ .LH+ ql e=+4 +al= +61_=Ell ole" ¤ +E gl+
uJzl'E AEg f gll, E rBg 4lel 'l]+ qqzlzl "J4 20.1 eJt BlErt EelI alg; Zo.Z Ltl+ ollHrl9 Eat; 2D.3 glBtrle-l
a}4l frzl¤+= gqE rB4g +E6J + glE 4,"14. Etrl; 2D.4 Joule-Thomson
='zl
ea.r ts, E, "J ollLlrl: za.z LH+ oil1-trlel ¤el; zn.s ga g: 2A.4 E
ot Eol
-t =H
2E EE EEI
ollHzlzl gs^l oldlzl ?+sH^J gq+= H+='+g'r+
28 flgtrl
col4r ++. ol e{oll.rJ= sd zl4lzl sq6}+ HE} *g
ol gz1;-E E4ll H +g+ z}]rjg'QlRrl'oJql, olag "JC ql aag *#lz} 6l+ql, -z olf* gEqlg ¤861"= Ell
{} "Jq 6}ql^J "JqL}= 844 Hs}+ +E Hs}ql +H}q: 561 zlt}o}Tl trll+o14.
gel 2E.1 EE fial; Ze.Z gal EEt
Ctlg + 9l= sl4l al+e| ee Egg 6I= +
e"6J ="Jg
d4ol4. 4* 9luJzl{ elgi{ H!+'¤ 4l*'ol?+r
a6F= "JBg ol a[{ dE4 " -+ +A++.
-q "
zs.r $tsrlq Eqi 2B.2 g.!=Jtrlel EEoil nl'= HEI g rl-E 0l rlEel EE=?
gqqlE + +E= gEe+ *zlzll ¤tr" 4+g +g
L.llel
=
^dag nxllel fl rI
6l-= Ell ?14. E-ee+ 4+E gqql4 ol
olE gt} tglrl ¤861fl+.
EE 2A Ll|+ ollLlrl
d+g 6l-zl g:_r. gl= B6Jal= rB4l4_r. qI4

> ol EEI= Hll+= 0l*
q-g= ts-|.= tll= EE+el 1E.lol a7l*)l
El¤toll^1 ollLl^lel
E+. Eal4 ESolLt tr++ HJ8oil^1 oilL1^le.l gg0ll-l EEoil
:d8 tHzsloe EgEl= 7HE0l r Hll3=
A.1 g, E, "J OIILIII
E6]I I r'=61'48
0l+11 Erl-. gqqr-ql^1. Hl+ z.l^14(= '"iq4) 4lql qlq} ++ e+=
+l#6lzl"J olE ++ er+E ?l"Jg $z| ;6q1,r1 'rj4rall!_
> ¤4C 7ilEl H :. olfl {Ez} *Jd trJ *+6}|¤ + 9l+.
a.g4lE ollLlrlts g86ttrl.
=
> qHl xl^l
EJ9.EI
(a) dE4 89=
0l EEg Tlillel ¤tr(EE 1A), EC 7lill EEloll^1 tsEEt gqEql^J 7lE4"J Eel4 cee "J"l+. ge Eil
^Fsq=
60ll^1 471|-d gq Egoll 94
LllE= 0l8-drl. eletrle_l 8^l =61 B6l+ eql *^J^J 6I= ¤+ol+(Elolzl9 tal ol. a+q}
6l'11 Etl. ql= +qql *^l^J +ril= E-q gal= aol+. "J"J g?-ltr-
qE El r+Ag ol$aN.! ++l qtrzl.9l ?i= +(+al)..q
gqqlql^J= ++= 4le+ r +fle+E + ? Eee. +b+. 4l zl4lzl *+6IE^l rlÊ-g "JqL+l= },"lulol ,lÊE e
ts *4zt 561 +dg *= ++q o3 -!-$g_e.^J, ola3 HI f,f ?leltr +E Eq ge + fl4. zla}S t6[^l d+E p-
I+zl"J +E 9lr" s SlC, ElqI dzl, rJEulzl ^lls s4l 6I= ElqI qI+E E6J "Jol4. ol43 ole]. E"J+ d+
+E 9l+. 4le-l Erll= ++{+r 6Iq, ol +ql^J 4l= =-"J
+A EEI= o a4l 6Iq += Eq ¤-g + glzl ullE"l4.
6}ril g+. 4l= r
41. +9e+ Er-l^l7lr 9l= aalE 5^d = =:al r
alE oilL1rl= 4lzl tJ + gl= "JE t.qr+ a+(+414
ql E+ ¤4 a"Ftr- ¤+6J + 9i+(rB ze.t). 4le+ ++l r ¤¤g Et4zl9 tral oS _H_ot+). el rfl4lql+ gg 6ll+
E +zl.tlzl_I fl= a4lE E6}l^l Eeol + 9lg ,I E(qlarll zlill= "J+rlzlEzl E= 4gg A=4Ez| 6Iq)
ol 4lE EaJ4l4a qlq. Eeol 4Al=="JB
Eo
46I^l *g ,I ol llel "Jg g + 9l= bqol +7I++. + {lel 9lHzlz} *
=r
E 4l= =J:d4l+a ql+. gfl4le+ Eql4l= r ++le+ ql 716l-= 4"14. 4lrl gg g trI=(qÊol "J4 4zl-4+
'I]
HzlE r.+g +E ?l+. qlg^l P{}41. ts+6}H^l r ++l Eol EB oll) 4lE glulzlzlzltola_q+^l 4lE "Jg6J+
ql 9l= +E Eq gB + 9leq, E ++lel $EzI *g trll=
fl= bqol aEq e^q}+.
4214t4 {lHzlE 4¤ +E lltrI +fle+ qql4 E= 94 dE A4ql el6t$ llel qlqzl= "J olelE trl= "JHql
Îol9 9s
el6H^JE Hsrl.^lvJ + 9l+. Ap+ +91 zlol trllE
q alel "llHxlzI H6J trll= qlqzlz| $er.l oldEls.+a "J
gE!4t
K
5
5
'J:'J4l
K
5
o
a r.EIl
++. Hl4ql Ela E(41)ql 6lEl= BrE ol alE gg g +
fl= t-qol f,zlaJr|. zlgg Ee & EE+ "Jg q t*ol R
f ilzl rflEol4. Ule+ r ++l Îol9l 3rz1zl 9lrl{E A
4lE F6ll^l qlLJzlzl oldo}zl *g +E 9l+ qlqzl. gE
rJ
"ld^la + il= 4Al= FE¤ol4z 6tq, old^l7l7l *
6F= A4lE EEdol+r ++.
(a) (b)
9lHzlE ++lql+ gE^J "J={+ $eg ttJE zftlol4r
(c)
lal 2A.1 r T?let ollLl^l "f, Etr= z*-* + 9itl. (b) =J-d
(a) EaJXIE 6J+. qle^J ¤i=
E4ol &Ae+ E*g rllE^l Hls"6l+ sl
xlts r++let ollLl^l= Ls:s + ?l^l"J EE= Ls-s + 9,tr1.. (c) l=Jzllts qL HI+o14. qle,rl trl+4 ee- 4+ 7l^ll cH4(d9 ¤iE
r T?lel ollLlxl= EE EtrE _a.sg + g.tr[.
2A Lll+ ollLlrl 33
ilEtrle.l 84 6 gEl oilL-lrl
Eillzl tr|]6}6l+ oJql "*^l olEo¤ ullE E(rv)ol o$a}]{Q. $x-ll .J++, *sl. rl.
Hfl olE^lzlzlzl q6ilzl-
E "l^t astutEl) EI=! 91611^l
"J9 "l-4s+ rJ4. o d Ep/dx<0

t{J
dwooor=-F'ds 86tlxl= "J t8gl
j
K dEr/dx >
=^llql 5
{zlrl F.ds= + EEI Fe+ dsq LvJ+ tol+ 6
= {ru
dEr/dx >0
F.ds=F dx+Frdy+Fdz 4e+ E tggl EJ
E- F F
4lr| "Jg 6Je-sAl Si 9lHzl d1"b Eillql Bdfltl .JE gE
9xl, x
alol s4.uI4rJ, SEI t
drry:F'ds Zloll "J":tlT] g iSEl

ElHr¤ glHzl* oJEJolTI 4= tr-g4+E ++ql q=6ls_E
l;<l-?l gF9 A+ql= dw-F*dx7| qq, tsol gFql *¤ olag 6L+E +FE o + +48 += S.tr}. zls$_e=e-*
^l
o11* r,.0ol+(= F,=_lF,l). a3 zj_egl ¤611^l
B6llll d4l elB"l hql ?l= e*l rn"J "J"Jolql Ell6]l^l= r +q qHI
"Jf- ol ^lg 4B{ 4o14, olql aE ^JE 4 dql^l r7t ¤ qlqzl$ ffi$ *ol 44H + 9l+.
"J6F+ a7l= Hp + 9l+= ag relafl +qo} +ui. eg Ep(h)=Eo(0) +mgh qEl¤ ollq^l
=q
+iHo +, 4?-lE trlqE fl6LH "Je-l ++l= ol-ellel *ol +
g0)ol g+. {zlrJ gE x}8'S} z}+-=4r d+ tr-+qG= +lilql E
ZI E=6Izl"J : s= Ztg 8=e.81m s-2o14). ol trlHl¤ ql
ll=1Nm=1kgm2s-2 Hzlg oag "JEE ,s.¤- + gleq, zlstsgl zlt\& "J"J"l
qLlrl= "Jg g + gl= tlqol+.relr r sr +g= "JE ql q6H^J= "JHI4 + E (0)=s eg +=+.
"
trgle+ ?ol T¤ol+. E qlqzl +E9
^lz}
HE+ge + d6I e,4 qzt rEE gq4 flg'ilE olEE ElHl¤
(P)ol+i1 6lq, elE(u_e. =iE qlLJzlzl r+q-!+ rJ"l 84.
+4u4.
1W=1ls-r F Q,Q,
D_=--;-- Coulomb tr-lEl¤ ollH^l
P 41t¤,r
"JoJoli Bd ¤-F glHzlg+ ElHl¤ qlqzle_l F a"FE zI {zlrl ee: *dEol+r t}+E^l d6} ^}olE "HeE ce
e + fl+ qI Eillel BT.l ollLlrl Ek= I Eillz} Htl ql el=++. d6l¤ rt"lzl 1l*"J ull= t+= TlE +d
¤+¤ 6-Je_e,Ri
-
4rll q= 9lHzl4.44 u-e. "l¤.6l-= a*
"l
t eoolrlI. 6'l+EJl, olqlE <,t3 a.ssax 10-12 r, c m-'o14.
rz?l E;ll{l E|]"]]^J=Q+4 ?"1 5}4.
*zl, E E= zlEr+ Ag += ,lle +q^t= +dgol ol
Eu=\muz EC AE ollLl^l [tre.]l tr+ q =.4. +dgg f,4rzl o + r+s-r+ *ol +l* +dg.
E Ell+e +4u+.
oJ¤ dB ¤+%rE a71+ p-muolol (Eq lBel +s+zlE
¤=¤,¤o +alg tSell
tl+l tl olae +s=4 ?ol 44H +E 9l+.
{zlrJ e.3 *4Hldq AE}l4 *dE(dql= +d t}++r
Ek L
2m
ETI a5 qtLl^t [gel] getulyolelr. tI+.
Ed e+ qlq^le+ trlHI¤ "llHzlE.J6l-E o3"3o1el di{l
EillE tr{E!¤ ollL1r! Ep(EE DEr. +lil ull+ql *rll q g+.+
qlqzl+. "J"Jolzt foltl +lilql^l ezl tr-EHql il¤- ult flL1rl7].
=
: E=Eu+Eo
"Jg r $ulo15 a*vl^l zl\ezl
ojulolzl 6J + ?l= cill ollLl^l tSe-ll
+l6llî 6]]+qoh *'J "J4 ,J"I"I -J+. dw*"=-p dxolo e "J"J"l9l el+ 6J"l 4L+6Izl ?*eE ol
ojulolel dill qlq
"l .ll¤¤ ollLjr!= H=el g=lol+a 6l+
dEr=-Fdxolq, q-4^J q+.r+ aol +Eg + 91tr}. zlzi oj{a].4.
dEp qEl¤ oilLl^l tEr+e-l alzll rll, olag E"]q}el +s6J Hzl"l4. trlHl¤
"ilulzls+
gE
D
-
^dx glHzlE zl-+Eril glzl"J ol=E dill qle
^JE H+IB +
xzl ftzlfioll tr+zl Eotl ftzlol$ 1,= +ol gtri(f,-9 x*6J9 e]+el g6}"l s.=.J "Je6I+.
34 1E=l
+ 9ltrI HzlE G7l^\zJ4.4lzl ++l= ,lg$ ull= 4le-l EzJ-5"1 ?

=
CHo(g) +2 Or(g) -+ COr(g) +2 HrO(l)
gl E4-5q ggt¤ g.ts:"]-zll 6J+(rB 2A.3).
qe4e+ gg +fe-l a44ql 35g- oJe"fli oll
ole+
E- ¤a Hl¤+ Egol4. gA !+Cql^J. SEzI 94zlzl Hzl oldol4(:B 2A.4). += gel +Ar+ ,-}|Bl= ql. +9
"J Fg^J *zl 491 9l= 4lE s*E?l 7lL+4H :. ++lE S4* a4slB %r-^l(91+ ot4E) o + olEdJ+. 4E"l ,J?
gtr + gEolztq r?]6Lq qlaql 2s.cql^JE ¤i4L g trI= EHE9 flzl¤ol +!4oJ olal
"e olE"6Ia E d+7I
ts + fl=
aolq-. :7Bl+ t¤
*zl qlql^J ¤^zI "Jq+E EE Ell= d+ +E dzl-E"l +zl4oJ tiJ-6}e--tr. olE"¤14. 4l
gs^l "J¤E ollHzlzl-*zl q]91 tsolqizll qq, $ETI g+ 7l "Jg 6J q= ++lql fl= gzl4 dzl# a4p+¤ HJ^l
zJ ifls tso}glrll E+. o + ol5ril qI+. u|$zlzlE 4lql gol Bqle ql= +E g
+E ++lE+El "llHzlE gs^J g4al-b !+Cg EE zt Bes 44zlEz} E= dzl-=ol EAzlEzI 6IH^l
zi-=ol
8"141 qFl.Eol ¤=B:"]-Y 4dol ¤-g 4Ae-l + qlol+. a4qlg *rl ",+ 9lHzlz} 4le oldgtrI.
q4+ s¤9 g q-6t61+
iilo}Tl +l6ll^J "JHI4 +
" Bg r+Aql^JE ql
Î"lE +E+ +glql^J eaEl= 4"14.
"Jr+
4zlzl ??l-e.'gE^l'oldqj4 gg r+aql^l= +flE+El +71 41 4+9 g¤# zHg + 9l+= .r-l.{ z}zll= g+
4le- olluJzlzl- $g.r.l oldg+r "J*4. ge qI4a rq+ "J rlol9 *$45 ++6J 4"14. "Je ++lql il= flzl¤9
olzl($_Ex} trIEql CzlE glulzl olA) dillT} olq4= a 444oJ ¤t¤ ol3-o alf. qlqzl oldola gg ++lel gg
g +E6izl *sH qI ¤+. FE 8zl "Jql^l Sg HI*ol "J df ol86p ql',lzl oldolrl. qls^J TlillE +g "J+61-=
q+E qlLlzlTI 4l oJse gs^J gel=q7}^J 4lE gszl a+q= "J+ 4+ ig "J"JolE-ol e^J4"J "J4eE Ll]4
+9lE gEe+ AZI ¤+. qlE F¤ *zl .Jql^J ts¤ t}*ol
"Jq+E glHzlzl ++lE gE^J ,J¤g+. t¤ *zl qlql^J
*5-g Hl+"I "Jq+E 41e) s-_Ezt 442E, Bg HI*ol "Jq I
,/+-l
u/ I
4E 8s7l =-l-VJ4. olaltJ Ee$$ t4 zA.2{rl ,qE6ll +
\t .----*
et+. oF \
xF
,//' /
/
gzt gel Ert \//
(o) tE a||4 a \ \
Ezl- i=q1,<-1 T}gol+ ++lE +a^l+ EzI ¤¤¤ ol
_H_E K
5
K
5
K
5
+61-= qlHzl oldolcl. Exl-59 +a^lq} ¤+¤ E¤Eol 6 6- o
K tt
+#
I
+r.J+. trJe ++lql fl= +zlE +aî6J E4 rI

419 Ezl¤ z}]6}q 4 ¤]ts:"i|l +4olzll ste-EAl 4lE ql
.f,g 2A.3 011L1^l7l E-e,'.i T?|E 0lEE nt|: +gloil ?l= flxlEol +E^1
-Lf EEE 611l Etrl. +ge+E1 ZIE 011L1^171. 0lE-g ttH= ++lsl EEEo1
0l8Ert.
t
l
I
;I
I
I
^l
l
i
+
I
I
l
A
oF I
I
xl-
l.
I
=g
rt8 "Jg rt8
=g
rt8 ulG:rti({
a= rt Ci 7'\ K
1
K
I
K
5 5 5
(a) (b) (c) (d) o o o
K
azJ 2A.2 (a) =JE Zl ?Jollll EaP[ "Jol'-J ttfl= ,_gE7l EqxE (b)
Etrt7f gol'J tt]|= 8E7l =E
EalrJtrl. (c) FE E7l +oll^1 EE EEtTf oJ
"JE
Gl-J tttl= T?l(.gEzl-gEotXl +^lElgJ_e+E1 0llLl^17[ Ee ] reJ 2A.4 AlTl z= g nll= ++lollî tr^l4oJ E¤iol golutrl. 0p/.1
N AVl EgEl8E= p^l6l-Zl EIH; (d) "JE EalTl gqLlE oflqxl7l =aj =o17f
Ee qTloll -EoJ flrl-=8 ga1=al7lts +9 g+g + 9ltl. -drJ '.lal6t.= +sl
,(l ffif^1Ll7l.q, -Lalotq 0l Ea[7f 584o+ gclLJtrt. fl^l=sl E^14 A=e 1loiltrl g= 6H=rl.
za ullF ollLlrl 35
"l 'J:z.q7]= q^- zlrjl E

at_e_e.r*l
olol olaflzlz]t], +4UtrI
z]-E9 ¤t +qg zl4rlZl4. :zflql 7li-ll E{-E=$
^Je ?
E¤-61-E_E _z &F "J.J"l + laslqq, +E a^14 Ext tE afl4
(a) UllF oilLJxlel
?l $-ffi 44 zlz)l Ezl¤9 geffi
=!+6tal 6lt e4rt g+.
^F- E{*b +ZI +ql^J olt aJ + 9l= }.q ('BTl & E'ol4r +
+), Eld, E= 4l#- 6J + 9l= gc+q ZI+EE zltl-n-
a.2 L|l+ ollLlrle.l gel gl4. EzlE 844 Cd"l't 3r+ql4 Cee 4 Y Eol
"lE e
E- "J^l"l += "ilHzlql q=*+. qlE^l qI s+q} e!+ql +
gqEql^J= AIE d4 qqzlE Ll|+ ollLlrl+r. B_=;' utr
*9 gluJ zlzl Aeqq doJ {ffi "Jezlfl -:- ABJoI #q
s.rlaJ4. ol ql+ 9lHzlE 419 CB "J"Jol(fl2[ ol$, EE
a + 9l+. ^lE9 gsz} ^J+6lq * qlqzl $Qlzl. $o|
Ezl)Eel dill gE "llHzle+ qfl¤ "llHzl4. qlaEfl zl+ zl$ : .I+ qlLl zlzl rtzlalrJ.
71 4"J ++lel +llE= tr+4 E= Ell +Hlq= sE qlHzle+ rdqqlE .+F tsHl] gfl,E El$xlel tl^l zgl 4zfla}g
,Jol 419 dill4ql +Eq 7l.Jq= a+ ee 8F ol.a" o|{
ql+ qlqzlql E6Jqzl ?+=+.= .ll+ qlqzl= 4l l'l]+E
"lluJzlts
=ql, ^Js-58 Ezl¤ d+el a+ql= ol g?-l=
,tI Ezl-el(= sd zlill $zlE^J
qlqzl"J aol+. AlTl Lil+ qlLlzl 14= *= 4+ t4 ie.* "Jzl -Er+E +^lB + glLJ
4 +5- u}alE"l dill qlqzlql z1016}= AEE ql+g +
El l-]l+ qlqzl ur= 7*y 4+ tr-4 rtr. Hts *IE ql',1
'il+ 91trI.
zl Sffi tr1*9"+ 4-o1 luE +4U+
LU=Ur- U, (2A.1) Lle.ftt 0ll 2A1
gqq} aalE 516l^l alel ce(^JEI EL+)g xE +E}9 ,l4l +ql fl= ?lzl+ 3il-g *zlq^l e#.J + ?ls
oll lx=Xr-x,E +Eg
q, qut^l r Bd ¤+l qqzlE 2ilolol zl{a1g a3
4o14. ^ll
^l-&ts + 7JE\+,
Ll]+ qlqzl= alE ¤zl] tr4ql"J E=6ir-z tr4z} 9B
al ol+qe.7}ql ql6}]^J= ru+ aEil g+4. ul+"l "5"I E o,. = i*r?,+ lmul+ lmul
E Ll]+ "llulzl= 419 ¤zll tL4. +44= deEg EI++.
+E +El] gqql el6IH olil 2zlole 7+7+ ¤+4s
"Jq4 ee- "Jelel 6J tr-El] H+E Hs+^l7lE q]+ "llHzlzl
trl4^J H+tr+. .I+ qlqzlzl t4 EL++- ql+61 + tr. +krel glHzlE ,lq+{. E|+^J ¤+ Bd g+ ql
Î¤g HzlE E,,.n,= 3x!kT-itcrzl g+. trt4^J E B4l +
eEI pqgg'l4rll!l g{(Eq 2D).
qlHzl} Al9 zzl ¤¤"lq(Eer}ql E+6t= d E qlHzl5 E,*.,,n =|kTxNo=]RTlI g+. 25 "Cql^J=
']l+ RT-2.48 k| mol-'olq, q4^l B4l gE+ r g LI+ qlLJ
a, Eq rnel rlolzlE tt-^l zE EoI4), +4 +9=
(tl=tks -, s-,). 419 Ll]+ qlqzlE: Ee"d=e-s +b=ol+
ag zlql+ 3.72k1mol-'9 TlqE 6J+.
E .ll+ qlLlzl u*4a +q-. I u^=utnol4.u,,g ^,117.| C
A(Ee"+ql roeL Cd)o14, EE g 'J Ae¤(kt mol-')_tr $d zlill E{fE ol+qd 4e-1 +i{= 4+ qlqzlql oi
EfEtr[el 8*l z E= EH}l flAI
BoltzmannEE^l(d4l zl^l ¤9 E"t?+)g ol+6lfl + + '2ilolE zlq'+ #=+E zll#ql ulfllap({lE^l Bd g

9rl Ssql^J ^lE "Jql gl= fl4.4 Ezl-=el 4I eE "J^l E qlqzlE A+ 4-ft2m;44219 t4 ol E ¤B +lilE
q
'ilq} B+
qqzl= 4l4}g f llxl"J, gd q A+6J zl +ElE H+lE 4l#ql Elql6l+(qs^l e6+ dE"zI9 qfl¤
Eag ol+6J +E gl+. gETI +E6l t"trl Bg 9lHzl9 4* Ep=+kfl 'Jg *6+. ol 314= 9s7194
9E"l d+B trll= q-q'-4=,ge G ols"g =
EH]l flal. + + E= glHzl *otrl7J4ol I]*g
=+lE Îol9 =gEol
fl= aol+. d+qE FE +E BHll gE]b H4l
aaql^J"J g"J6I+.
ol+ cld ¤¤' %'-^lq q6u^J 7l* * *=+. tlE"l4 dx}
gzl ¤Bg ol+r 9l= EE 2it alEol d
^lEql^J= tlEgql qlEL gHlzl + a 7J4Eol Ed"lut H{
ill qlqzlqlq B+zl " + +/crE 7lq= +4. =+l=e "
SE a+E.q +sq "l fl4z} g *zl 9+b+.
36 2 1H=.1
Ffl zl{r a1z1 ?*E+. 9d zlilql^l= EztZ} 1t.sar$ol + qqzlz| olz$alu(r=6olJ. w=Qolp +)E Î¤g ge+6J
S.sq, q+^l +{¤ rl-ol9 44zl qlLlzlql+ ot+fl ¤.J 4,olr}. ol 49 E6J4IE 4+ qlLlzl {fli Eol+ "JE^l
E +zl ?*zl ullEol+. 4A\= E"rl.ll EolztE "llHzl$ a+= ag "Jdfl=4. zt.z
=,
49 a=^J +Eg ilqql a o +^J, 4lql "Jol+ ¤_+,<1 q1q
$d zlillE .ll+ "llulxl* zl4\zl i|zl6l-= +ulql ro zlzl oldqH ** qy "Joli4 4ls+El qlLJzlTI m}44zlB
6I+
¤-ol 9zll +3t= e6J+.' Hh+q "J6IE "Jol4 gE^19 ql
g-qtr-g ol+r 9l= ^JE48 Ezl¤E ql+ "ilHzl9lE t Hzl qE¤ Alel ^l4ql^l HEJ= 4o14.
s++ i4H1¤ "llHxl 4 z\¤zl i;991+. rfl{ "JHI4 oe
ol zlqE a+61 6}+el o + +ElB += s+. rBzl"J ZEJEI ql2^2
^l
tszI i6ql^J ql zlzl fteql ^dee 4lel $szl g4eql q¤ dzl EqTI ull= lsk|A zl4l4 "Jg 6IE^l 2ktE
qq +F *4Eol dd q Hol Eq4 qq .I+ qlq gg ++lql+ "J=.J+H "l EEIE a'J .ll+ "llHzl H
"l+
zlzl rtzlt-lQy 4o14.
*zl ut--2kt-l5kf=-17ktol ¤+. E qlgg A¤- ql
1001E "Jg =IEql+ 6il +qor 6Izl"J lslE ¤"1 ?91
(b) l EElel +^lEI tr. EIrlA{-r.6IzL. rflfl ol ql$el ,ll+ "llHzl Eq+
dfl4str EF6]T1 Hlql EleH 4lel
4+ qlLJzl= ,llql+ "J L(J= l00l- 15J=a35;ol g+.
g 6H+4+ 4lE z|$aJeErAl H+^lvJ + 9l+. +"_l= qlq
zlzl qtr H}^lee old9Ezl-= + :lzl"J<?, +gql
^lBe-
4 +zl$4Ztlzl .llrlTt=zl. H7
"Jql E6il^J "llHzlz}
oldq*.EzlE g + 9ll" s ++lel 9*ol +9t=zl= H.;l EE gE 84.! AU7H"JHI4 o e Ar"J trllE) "JE A"J ull
gql E6]|d olluJ zlzl old!fr.tszlE q+= "J + ?l+) 4l s-olttlu9 +s=8q4.
ol4el ,J^lg *6J+E 1"14.4,
= "ld ^lE6lzl
94 "Jg 4lE qlq *H-E-olrl-. A.3 tsA g
zlE HoI^lzl| g5-g
4lE "Izl 944 zJg^ \"lq^J, + zlzl E":zH"J +e g)E tr-EllE trli Hgxqlaq trli+ gE HE+)e+
ql+os Boi^l olag {lHzlea,l E+¤}+i1 ^J46J + gl 'll+ "llulzl9
trl^ HsI du +e_E +E¤ E"]E ,Jq6J 4lt} *HE eol
4. de4-o e g'"-dTI E 6t+E ^l"gg 4lzl ?fle+El rB g?-lrll ¤+."J"J 4lql B6|]tl glol dwoll gs^J f,frg ql
qE qlHzlz| flalzl ?+=+= 4"14. ol 4¤¤ eo9q1
l,-lzl dqolH zt.z49= q-q=4 3ol ut+.1 ¤ + 9l+
'}]+
4ol ffi$ ee EE-+el lHElol+.
dU= dq+dw (2A.3)
rflg 4lE ,-ll+ 9luJzlE "Je6Iq Atq6.tol
d---
1r+txl
rts-
ol 49 ol+6LEjE aqo+ du,= +gql^J "Jq+= EEle+ ¤
4lE ol86l]^J "Jg+ + t."J qFB.+r ql^J
trl-g ol 4l= +^14 ¤+ 9l9o}6J+.
ola"l +^l z]¤.4 +?.¤- "Jg B + gl= g4el t'-EIe q +d +rl Hsl.ll zl"JElE "J, + gA g+E b9afl 4zI
E-oPlzl= g:='I. ol+l6J HtE.¤ zlE ++. "l3lq} ="#9 "JE^J= zlzllzl $1ta|fl,<J rllzl
^l.gg fltsad+ +A7l oJg
+ S 7l+f(flB+ += .llHzlfl$ +palzl ?+r 6J E "Jq.J 4l zlAlzl6l-= "Jr+ ?J? a* + gltrl."*g El
+ 9l= 7lADg "JE + S+= ^l-dol+. =
qI HI+qlrlE zlillTr B^Jq|+ +trqq(qlE^l +4IA+
"lelql
q¤¤¤ trl-s_r+ ?ol sqr"J + gl+. + zl+ 4lql E 9B6}l+ ++q ¤i), olBl+ HI¤¤ ++= gqqiql^l
46llzl= "J9 wF_ gE^J 4le oldq= qqzlE qE, :4 ^J¤qi zfillzl Eqe *tg UJE= trll gs+ "JS I
a 4+4 oE +4+= Ll]+ qq4 HEI¤ -s^l6IE
=
El6l]"t *+L 1o14. Ber "Jol4= +q +ql= *ulzl-*e
r+q-4 zJ?*AlzI CBEL+. ûtr
-e. Hal-b + "J+q= r+AE EEI^l4ot aJ4.
LU-q+w 1g^lE +4 EE QA.2)
ol g4 gE f,f,dg ee+6}a E" rfl4ql^J= Lll

I ".tg *qr nzllql,t]= "Jql 46J +"+g ^J"l6trll illq6}r. 914. a-, "lluJ
^lg ^l"ll zl$ +t/6ll^l ++lq+ gg 6il+E w>Oo ? +r 9i+.
2A LH+ ollLlrl 37
E9 EHJEI s,tl
(a) 8 2A.1 qal 7lx! "r.
=+"1
s+ "Jg 4l4I6IElH +ElzlE ^J'al 6ql +s= agE+q "Jel 6F dw +4 *+lt
g.dllo} 6l+ql, ql6-}6l+ eel +EE EEdlAl +qrllot ++.= iillociiL
-P"*dV a,.E 9P $H Pa
6r--lrlaz :d6ttTt
"J ttrell (2A.4)
dv= +El HEI m3
sE SaI ydo 7b.*H tB Nm-r

{zlrl *el +sE Eol= AZ AlTl qB .J lFlql "*^J^J doE H"l9 HEI m2
ql= += Hs+zI +Hlqzl ?+= + 4lE ql
'.iltr-Eg BqE ,(lzL
fdt /= tq N
+ qlq z\zl zltg+= Îdg 44421 916ll^l+. 4 dzzy oS
L,l O
dtg aolE H3rl m

ol$(zzl+zlalE *Eo ), du *ol 9l ql+ qlq \zl zlt
= dzl4 "J 4dQ oE d?l V
eFHze.r49 au= dq=0tl * ¤-ol E+).
da= d6I9 HE+ C
zl+ rH zn.s"llrJp-L ?"1 t + E9l d=J"l S,a, oI?
ol $.r" ++6ljr" H"lzt e"J 4 Eq*= ulÊol 9l= tF Qd0 d0= d+lil V
il$ ^846il EzL. e-l+ "Jqg p..41 al$ ol tlÊq qH Q= oldE d6I C
.
"JBJ4gE 4lq qdlzl= "Jg dw=-lFldzs] z;g Ee er19-'rll,
"ll pJ4E a7\9
aJol zle" g| 4"14. ol e]+ "J lFlE 'oJ
"J"J 4lzl- HIe+E'olr. &='"JHlsl H9'"14.
4 p",.oil *^-l^l 44 az EI+ "J+E 4lE dr= -p"Adz "J+9 'gE ++l= Jolc|.. rNm=ll, E IVC=llol4.
9ol Bdl{ 4o14.:zflrtl Adzy ++ $Cql^l Eq+ +irl
dye+ e+. q+^l 4l7l "Jq p.,.oll "*^J^-l av "JE S+6J H Lr4ezlr t/ azlq!, zlillz| oJi$ ql ++lrl g= qlLl
"ll
qoflzl= "Jg r+q=$ *ol ¤4. "JR + fl= +qg 44zlb +ql el6lt^l 4e44, ol
^1,=
4ol HLtr 41e old9= qlqzloJ 4o14.
dw--p,*dV "J (2A.5a)
"JB
+= ++el "J(qla4 dzl4 "J)e HI-"JB g E= +7lEl
Pulzt y,e+El yrE Hts uI q6ilzl= dill gg ol 49 il Eol4l 6l+Ell, olEE ulfaizll .rllzl ?]z}(qlaEil sq)e+
+ +ule+ 4+ +iil Îolql^l zlE6IH Eg + 9t+. r7l oJzH+ul HsDe+el i,1rj_e__e_'t4E + 9l+. H zlzl {lE
s.2A.rql Eo|ts?l+.421^l= 4l+6ll^J 419 +vl Eirlql +
,=-ln p,*dv (2A.sb)
Hlq= "J+ .J¤. q t+61r" E+ 2A.sb^l o q¤ a
"+Et
qÊql zl+61+ ¤ p._,qE ElÊol *+6J oI Eq gel
r+= fl}zls -H_71tr 6}4l'i.
=qt.flzll
+E +ap+ Eg6I+ HlqE zilz| oJf$ trll= ++lel + (b) g8:d gt+oil
=
zt 44zl= 44zl Elq qdq 2A.sb^lg lzll q=ql olul "j^l= "Ja
%< %7I E+. oltrllE 99 =zlE aa6l+ ae- q+ "J
dill *+ $eg E6H^J el+ "Jqol ${airp ^J46}z} ql
=
4"14E ^l-.gg +el6}7l HI++. ol er+= ¤.zl 4P9 zl^.ll -tr^J i4Êol EHTIE .Jqg E-r gl¤- tr]l= dill s+ 4e
7l "J+ql *dtr}= a+ "J*cg gE ai] g E6ll^J +eg $l{"l 4le"6}|l gtrl. olBl* rrJq siE4
^l-gg ^J46lE ql= ST zl$- *zl "J9l^J slql HI+ol "JqB qlel
"J ^8^d
Tlillel s+ol4. 2A.sb^lql^l "Jc+ "J4 p.,.E 4E zls Hl
o + 4E.llH dZl ol 4ltlg + 9i+.
E+ ^lg
otel D
H-, ,ex
w=-Pr* o, =-p,*(vr -v,)
Ii,
dz dV-=-trdz'
rrl4^J +q Hsl¤ LV=vr-v,41 r'g ffi$ Ag +AlE
Eg + el+.
oJai, p
w=-p"*LV ts8 g t"JEEl q+ gel (2A.6)
)
ol pffi 14 z/'.eoll :24=e +El.rll$.=ql, ol rH¤. 4B
:ral 2A.5 'J0l7l nlÊol tlzl dz trJ= E4lqLPlI dV=Adz'J=9
A?.!
e|F gal p",ts ulaEE +e= +9I
g Hole aH4B + gl+b olao6J ar+4. wl zzl
+tr|= LlzJEt. g¤loll Î+lg
=r.
*^l=:d3;r;= p"A7l ALl. =eeq, lrlE A+ +iile+ al+ +El r}"l9 +Bd p=po "J9 Hol
38 1E5l
+¤+ Fe(s)+2HCl(aq) *
P",
ol FeClr(aq)+Hr(g)olu e tmol
o. tJOl
E eE+el t mol9 HrTl ts^J++. tr|4^J n3 HI*d*
= p.,LV
Ei re flz}9 EA*4 A+. 6J¤ Fe9 E A=*g ss.8sg mol-r
6n
ol+.tr|.+^1,
vi +tr|, y vf 5og
w=- x(8.31451K-t rnol-t)x(298K)
55.U5gmol-',
->
l) P", =-z.zkl
I ol al(HI*- E-JE)= 4zlE "Jq4= 2.2kt4 "Jg 6J+.
.Lg 2A.6 7li1l7l "J!-Lf el+ "Jal p",oll "J,\iAi "JA-=f ttll 6l= oJg 0l xlll
q+E rETl +Eol LJolel' atrl-.
+4 el+ "Jqg 4+ ar+ql or+fl g6JE +xl ?*=+
"J4"1 *g++ zl4lzl il-xl6l+ Pulz} 44^l ol rffi
e+ e+. olBl6-J st} "Jg 41416l= ql ol+q= p,v leflg$ ol tr-49+.
zl.<f q+++r 6J+ olel6J E_.tr= JamesWattzl- Gzl zl$4
zff E.""xg 44421 +l6ll^J ;f$alzl TlTlg.71 ZA.1 "JA6J "Jgr+ 2s.cql^J sog9 Eg dzl
^l4L* Lo14. +611ts trll B6Hzl= *+ "Jg al^}4q4.
"+^l= trl]B
'Jol ¤"J *llE g+g rt? tsgol+r ++.
4 p,*=09 *ll gq+. S+ol+. oltrll= 2A.6^lql E6H^J +
DI oI-:E
*4 *ol g+.
w=O gSel g QA.7)

(c) z l,q
"J8
^l+
4 Alzl xl-+ *+g ts trll= "Jg 6tzl s=+. zl4lzl rl* + gE6l-ql^l 7tq H+4a 6t= 49 H+= ulâi4l Hs+^l
e_s ${-a3 oll olfl ++E Berol
"Jq*+. 4\ t H+= qHJ-6Js e "Jq+rll ts + fl= 4Ag "J+
+. "l7l^J 'Eli6l.7ll'4= "Jol *zJol q=ql, uluLoJ 4eql
6J r+AE Tl¤ HJBJol $uloje_+ Ht¤ + glqq, r4
E7l ?at 7li{l 8¤el g ^l=
sog9 ts9 zs'collrl (a) "Je6J +ElE Bo-J 8zl +ql^J, 6I"l "Jtr-^J++ql^l "+¤6}rll lr='7IE4'ol4E "J"l H"Jat
(b) gfl Hl4 +ql^l g4I4 HI+^]fl rect,(aq)s+ ,ll g+. ,Iq^del + qli. $szl EgoJ F 4l
zl fi ^lolel E4 B
zll= "J= $"llzlE "Jg al&6}q+. Eol4. ol + Al + qL 6J llE gE= ulâlztl *+H *e
"ll gEE 4lE qlq 471 old6tq, rrl4^J ol. + 4l ql
Îolel
uelfl AlEl +d +iil HElg eEE ++6Ir olol,<J ol Hzl(¤erJ) "ld9 z}94ol4. E 94 ¤Bg ol+r 9l=
4Col qBril "Jol4bzl= ac6llo} *+. +q HslTl q! qI 419 9s5 ulâ|rll *q+H rJ+ 4l.E+El 9lHzl
sg trll= H]+ol "J"l+rl+E sa} 9ol BaHzlzl ?*E ,I gfl+2J\ zl44 ¤¤ +E6l gd6J +4lrl 9l
^|olql-
L+. A1?l.JC{L el+ "Jq 6lql^l *+$ ullE za.ozl9 ol + ¤Bg ol+a 9l= 4l= t{l4s zl-9 HE}E "J_qA +
+6ll^1 4lzl al.b "J-e 4ltl6J + 9l+. ffi{rol zl4l_E H fl= aol+.
6|= 44fl "J{lzl $eg f,fl"Fel *slzt ^Jd!E zlzll xlli ul:-g9E zli]l= TIFI Br" el+ *q p.*E ee 9l
+iilql ulafl.<J +^l¤. + gtg atr e 4L+= 4,o14. Y Tlille-l "Jq pq ?JAl 6ll +*.+_L olz[. e]+ Sqg qL
Eol (a)9 a+ql= Pulz} Hg + S. o o e Sar "Jol 4 +e-E= ulâlzll HE+^lzlE *ulzl- r HlEll ulajeE ulr
6'14l H6IE_E olq6J 4lE:z +fle+ qqt4 BEg ol+r gl
6llzlzl $sq w=0o14. O)E a+ql= zlillzl. Ql
^J^dg
zl- "Jqqq tr}{^l s=-poLWI g+. oltrll= 4+ +rl +r E + 9l+. el+ Sqg ql+ "JqE4 "li="r"J+ +ril
6H +E zlzllzl E1! S+6J+. rfl+
(7l4l7l g^8EI +)71ql*61 7 rf + i.l¤. +"1= 5-;.lalr. "J.J el+ *49 "li
LV=vr-Vi =v--nRTlp*9 saE4. ¤zld n3 ^JdS H, %r++ *zltlzlB. zlAlTl "+7J "J+¤ 4o14. trI+î ol +
E Ee"+ol+. trI+^l 4Ag E+ gqol4 dzl.llrl 2194"14. qlgql e1+ "Je
ol ql+ "Jq4 q¤ 4lE p.,.E "lAeJ"J+ z]r,<lzlQ
=.Al
w--p,*LV =-P,*"ry=-nRT 4E ol4"l 4P gq olalE ¤"lzlxl ?+eq tr++^J r+ee]
P"*
*6}ol E6Izl *.+. olel+ aH +9e+ EqI4 ¤¤-3 ol.F
2A Lt|+ qHrl 3e
zl ?+r 9leq, ol s4.e. gEolzl o e ulz}94ol4. pi

P= nRTN
zlq4 S+g gezlBlH, 4 ts+ +4ql^J"t+ p",.E pe}
pr
a/l 6fl+"i"t *4. dzll4"-+ sllEe] +|1= dz}4_oE o.
e5Î4 "l ullEel *4lzl oJ o + LIIBJ+tr= E4 zlill9 mi
*4"1 +le. "Jq 94= Eol alt eZl qE+ Hs+^14+4

6n
"lel+ *l$ol
ol+qa + fl$ 1o14. ole+ Aol p"*=p9 4l
vi +tr.l, v vl
ts ze.sallol rl-e=$ *ol S4.
dw=-p,*dY --pdV 7lq tsg g (2A.8a) pi pl
'}]+ sqg
ol 4ql^J= 4lel z$):il_ sa} "J¤. s,<16|$.|rll,
olae 7lE4"Jol qdalq el+ "Jqg.++ "Jq4 aal + ]aJ zAJ gfl 7lg4o+
TlillTf "JdEr rfl olts
ge p=nRT/v
=S -c ge
"f,('i,\'l HlTf!{oe "Jd-g ttll 61.=
rJtrl-.
Eg-d 4= galoil
g + gl¤- trI+ol+. trI+^] z]¤- +q y,E+El 4+ +i4 % "Jsl 'J0ls[
5= tl T]6lXl:.zJ al,tl'4B +.Esl 'J0let'Jtrl'. 7|.q4 "Je H17|-q4 "Je,c1
E 7Lq s+g qlE aiil "Je +g=4 *ol ¤4. Itrt= z;g 44a$a|'.
w=-
Ii oo, (2A.8b)
s+6J trilzle 4+ +rl7l. zl¤. +qBtrI trI= 2A.e^lE
Se"l +rlql q$4l q+ 6;0l "JE Ztg 7*a_ tt+q^l w<0ol 84.= ol a+qlE Al
"l 4+g +6IejE e-"1 91ts zl4lE
E=61^=zlE goto} Eitrl. s4^ rglrl H}]¤: rll¤¤ 0lg6l- ,I ++lql+ gg 6Iq, r"J+ Ale-l rjl+ {lHzlz} ali,*+.
.l ee gl} zlillel ^JEll^lg "JH p. vE Et+s +48 + (+ql ¤EaL4lzl"J ol49 s_+6I= qlqzlz| $_e.^J +"Jq
gl:r, ol4^J ol 4Bg- +g + 9l+. q, q-+^J 9d zlillz| E"9 SAg ql= dXl4 o + tll+ ql
]qzlzl "Je6L4l +zlg+.) ol 49 E6J e3 +q H+4E
(d)gE 7lfllE 7lE ts8 olaol +g gEql^J oJqB++ q Be 9ol Bal]dq= a
- g +4U+. r-=e gEql^J= e-"i 9l= zlillE Sqol +r
9d zlzllTl Eg ,iq S+g q}+r ^84611 Ezt. 4l= +fl 7lE4 H+= gq+4 g "*^J= "JqE FFt 6Iq, q+^l
(9szl- "JAqI 6}g=e+ ee)e+ 94 ¤Bg f'zlzll 6lE^J
qdlzl= "J"l :_"J# 4zlE 4"14.
s+g ^l7lE Eog4-o-E s+"l "Jqg + gt+. TlillE ^Jql ol 4l4I e+= xl.r.l EEg zlzla_ +48 +E 9l+. 7lE
4? pv-nRTol= E zI "lA +4l.ll^J p-nRTlwi 84. ¤zl
,tl vE *tL +41q1^Jel +4ol+. E"8 BC9l^l= +E r7l 4 o e e6l]d "J9 =zlE 5g +d p=nRTtv "J9 Hols+
oJA6lsE olag 4E zls +Ie_E .llBB # ?14(n4 n=. gq(rH 2A.7). ol rHql= E "Jeql e-l+ $q(rtq 4c
ql^-l EgqE 4+ E.qr+ ,J+) d-ql^J HlTiq4e+ s+B
EI4l) trl+^l 9d zlillTl gE rql^J y,E+El yrE 7Iq F
ql gqzlb "Jg E7l]H.trll, 4Î4B Y Eol ¤zl9l 6}l'JaJ
g S+g "Jg +q-4 ?ol 84.
"I9 4. ol rB¤. _E_H HlTtq r+a"J qlE+! 7Lq r+e"J ql q
4E A.2
Be "Jg eg + glErll, olag 4 +alql^J el+ sqg .]]
w --nRrT+ --nRrh + "Jqql *+q=:_q-EAl 4lE trl= Cg a+E B;El^l7lzl
?*zl ullEol+. "Jg E+ $qg ulralzllrJE olB+ q rrll
vYL
5g 7lq "Jag 1eJ5 ztxill (2A.e)

= 6ll +ts 714171oJ+qq, qQ^l olE+ q Bg "Jg gg +
zlEtEt 0{l 2A3 S+. ol EEE+q eg + 9l= eEg p>p,*A ql= Al

=
zI 4ulE aJ9 E"IZlol 'Jul9E, ul4rJ H^lg i]+ tr-Eile+
t.00mol9 ar rl-EE $d zlillE H 7 ol ,r'l.E.z]. 20.0'Cql 4l+ tL4 H^lg aEE. r|4 zl¤61-= 4l= 7lE4
rJ ro.odm3-e-e+q 30.0dm3 o + Eg ,|q S+g. trll 6I ^l-olql^J
o + zlt¤ *ll 4l'llE "Jg 6}rll g+= 4014.
gg q-q_r+ ,JI:+.
=
il, =-(1.00 mol)x(8.314s lK-r mol-r)x(2 s3.2 K),"i:## A.l, Egl
=g
=_z.og kl
"JHI4-" + 4le-l ql+ "llHzl EsI= trl-q=r+ eol +48+
t+0 1E=.1
dU = dq+ dwr*o+ dw.66 (2A.10) sald s,Zl

tl^ +g+
"J dr* ole-lql q6llzl= HIOE
¤zlrl dw.dE s+ += "Jol+(e uoo
z[ hdd'E additional9 F.Jtr]). qlaEn d%oots d+E qs+

lle
E" rlrlvlz
4714 "J"l ¤ +E gt+ +iil= ga6lal 6]l c^,
4lE S+ "Jg 6J + S.gq, q-4^J dw.*p=0ol+. S"J otq
= 7l'g
4 ol 4lzl +E ++E "JE 6J + H+E(qlAq ol 4l= d E
zl4 EEle+ ¤Ag 3rI+ dzlTl-otrl+H) dw.aa=0olzlr a|

4. olfl+ aaql^J= trl¤. +4lzl Cflqlq.
reJ 2A.8 "J8+tr1 BJ- gaJ4L ECE E4 E3 E3 geg Z= + ?lE
dU -dq gtr +n-lfl^j E old (2A.1la) EEE Zzalop 0l raJol LI-EPJ 51115901 Egzl= 0l=trt. .LlgdE
6-jtrt.
+H6l.7l 9"=t|,\1 EaJZE E==J0ll -A.:+- 7: E4 Ezloll,\j 0l E 6=Jg ?rty

olag 6y=4qrzp.E_ +Elutrt. q7l^Je_l Ezl-b "Jc +iilE EaJAIE SEel'-d8 aol-rlE= 4tr:dtr|..
++UtrI. +eg + 9lg AEE HElql qdl^l= ol{$ ffi

4 *"1 ++U+. 4"1 94tl Esl¤ ol$afl.! g%FalE b+¤- *+l trl-.s=4
ge +4lE 0l+61-0l EBfl! 8+ c= +6flot.J+.
U,-U, 4v
4=CLT (2A.12)
I dU=
I dQ'
g*41 tr-+= g=*Al +E 6lElql+ dglzl Age-tr-+
olag q*4 pol eo-|s + 9l+. El d+ rz t tlzJ E"4^le o +Ai q+ ^d"J
+al= ol+4q
='"J
dzl4 c + +aB f 9l4t4ulz}9 t}4 sl.
A,U =4v (2A.11b)
q= It LQ (2A.13)
¤zlrl *aJ 4E Ar+= Lq4a 4zl ?*= 43 uetr=
dqoll
94 qzl tr-Ell EL+7I otqzl rllEol4.2{.nb^lg "JC-+i4 q?A4 V
zlEtE!
!lql+ gs^J +#q= "llulzlE +A6lE ule ol llE t-ll+
+4$= 44 12vq dge-E+el to.oa9 d+= 300s *oJ E4^la
9lulzl H+= "l,Jzizl"J$ ++U+ ge^l
trll {fiq= 9lHzl} 2A.13^lql el6ll^l tr+s=r+ e
ol ¤+.
(a) E z{tu
q = (10.0A) x (300s) x (12V) = 3.6 x lOaA V s= 36kl
Erl4 H++ 3rl+4 Hplz} "JqB q gsî oldq= qlq
zl= a^|61+ Lol E IFJolq, old9= qlLJzlE +e6h= +4lE ol+6IH ol Ar+
1A V s= I (C s-') V s= I C V= 119
tlil= EB{l$r ++.q,H44,! luE) +C6l+ Ell ir= E +49 + 9l+. "J"J "lull SszI s.sK g47t+H
z|$ _H-¤4"J tlzl= EE U3= ggll+(rH ze.s). 94 =E
g+41 tr"+= c=(r0kl)/(5.sr)=0.5k; rrol g+.
41t"l q= $e(e+ql HI*g +E 9l+)g "JA-+ul *zl"J
HI¤+ "Jql^l "Jq+41 6ijr, "l EI+F9 4Al7l gfl E 6
R +ql R=+. olE- tLTl dillT} g=J4ltrl. ol ge}4l zlill.=.
E+ Er6B +ql alrr" g"+41 "JE EE gEe+ HIA E-6l
g"*41
^}i c= AAd+ E + zlzl HlBg B¤*"1 94
4l Ee(e6l Hla&ol ol+¤+)E gce}g 4+= 4014.
Rg Eg gE= 4 *ol EqE]aIE^J + E +Rg gE.
ole+ eol 6Iq c= gal qH gE t}+g +e6H^l %I=g
E *4ta¤6l] ole+ eol 6IE g%F4ls+q +91(++
=+. gg ¤rll +g + il4.
%I)E 9ol g4 4zlzl ?+e4 tr+4^l +g gfd=Al?l qy A
ol+.
g"+4lel gE Enl Hl+ql^J ,J=El4+ B+q= g EEg
(b)
.tlHzlql Hlqlq}{. ^r= E¤9 SszI 94zlE r q+ {lHxlzl-+7}++. 6z}9i
"I{^J ^r= +C6IH qv= +dJ + 9la
"lq^J ûE. +g + 914. lre.Pq q,,E +6IE]E "llHzl a aE= 7}96l-= =aql trl4 4s4, {zl,!}.rlEr} "Ja +
2A L]|+ ollLlxl 41
alEtrle.l 8^l 8 d6f, d+, C+ "J ollLlrl
d6[E +A +fl= E+ col+. ITHE "Jtzt4 dz]z] 9e] q+^J "JAql 4*zl txlzJ E9I o=ts dfiqE {Hzlzl
6h= d6tE a7l, + 7l+ d6I* e= E l.6x lfr'eC"l+. d r+s-r+ *"1 ¤4.
6}el sE"J d+ rE i r* E+s E 444Erll, ol E+lE E=Pt=IILQ
bower w /S
"Jqq A4r *+. lA=lC r'o14. d6PI dzlel d6l+E d+E "JqlqE, d+l^l-= E-E+, r4I ^lAg ++ +El
(++ql^lel A+e+ Bol) 1 Ael d55 0xto,8zll9 d
z(topmol e-)9 s# +$Utrt
='J; 4E r A V s= 1(C s-') V s= 1C V= I fol slp + "llH zl= ¤
_e g4l 84. ol qlulzlE "Jol4(eq= Efl+) g(6lElE
d+l,(l A0(+A *fE EE V I v= 1l A-,)= je" 6ll^l "JC
E6]]^J)eî +#g + 9l+.gzt9 A+ql= +94 ?ol 4
+ d+ I7l-sE qE dqe "Hle+ *E+. E|tr + 91tr|
P=ILQ
q= ItN
..il9 8zl +ql Eqgl+r

^J4tI+ Lll+ qqzlE gEql ql q+ qlqzlq E}]+ Bd eE 7lq= inro14. q+ qlq
6H^J E^l6l-E rB zt.g* ge +dol +g + gl+. .JelE
zlql ql6J 7lq= ola +olEe u_(7)=;Rrolu|. El+^J
r
gEql^Jq ol +dE tl&zl$ $so|^Jq 4lE EEaJol
ze.r+^le-e.Pq r+q=r+ eg a+= g¤. + 91trI.
4r qlq-. g8-+tr101llel EEeJg cv-tr 8^l6hb ql Elg-r|
*ol *!4o+ ¤elg+gt'i. c,,*=${+nr}=*n
AU ol
cv "J¤ +trto1^1et EEaJ t6gl eA.14) <lg r2.47J K-' mol-'ol4
-dT )"
(¤EEl+e+ ¤zlrJ 7ls= 4alzl9 +^l eql ,qE6fl
^l-S+
+?t+.) ^lEg ql+ qqzl= : gEe+ +"lql lrl+ H6Izl ¤**¤. _ezl cdol4. qlE^l r00gg Eg rsg g_H-
EL qTl^J= +i{= g{6t|l +zl^l7lI, e(ez} ytr s^l) g
ri roouH9 g+=*g *=+(trI+^J gEZ +rJAl 94=
Eql EI= Hs+rI +s* 4ol4(:_B 2A.10). rll t00uH9 9lHzlz} gE^J ¤s-a1q). g8-+tr1 EEaJ
=
Cn.= Crln* I mol9 EAel 98aJ"14, r'llzl rdd"l4(s
LEEI OII 2A5 E E_r+g rllzl Cd"l4).s"E9l tr++^J= ^lEE g++g

r Af,+("JHI49+ :aH)o + Llb Hl EEB(A+61 'Hlg'ol
At+ q ze.rgl.<J -H-?J ule+ A"l rflzl 9d zlillE E
+r-E +=+) Cn,= Crlmol +s" g +E 9l+. dgql^l EE
f,
.--:
K uE 8Eoil nt=
B
5 Eol gc:d yoil^1 uE
6
f, lF cHil 71=-71
j
K - J
5
o
nl- A
-
J
EE, T
-9E 7
+tr|,
f.g 2A.e xlel Lt|+ oilLl^l= ?rt1=al-rJoil qal 0l rallq= fB 2A.10 0l rge.l E'Eoe LEP,! ul.et rJol 4lE Lt|+ ollLl^l= +trlel
4l= gd gq aol,r.1 7l-E:g nflsl EEI-= LlElL.! =7rdcl.
aol+. "Jgel SEoll l gEoil Elal- EEltrl'.
:d
+trloil^j Lfl+ oilL1^lel 8Eofl r4E Eai= rqt
0l +,soll EH-J trcel 7lz7l= r s-sql,il9 gtr +tr| E8eJolrf. qTlî =¤:d LlEl'J
EJ:d6l4l ral +C= 7l^la + ?tri. 0l +.Ue.l gEE -d Eoll^19
qlB Al0ll^1= EEBoI Aoll^1Etrl= Boll^j tr1 ftrf. 7 lz7 17 | H tE trJE-Er+{aUlaDy0 I
tr|..
=
t 2 1E=.1
@trJE-d+
y)* *ol ¤4 zll9 E¤ *= iI+9 trJEg+* ql
f(*, rel-r- ** yzl4 ?ol ul^ HEIE gea 4l+fzy trIs=4
H+- xll9al +"lxl H+s$ "Je6IAl +9Ig oll9 ol Er B"l Hel4.
+E r.J H+ql *{ zl¤zl4ttsl r). 6J H+ Hsl.ll tr+
df = 3ax2y dx + (axt + 2by) dy
4:z E]-fzl q$rll H6l|zl= +$qi= {ol $rs+olzJ
6lzlEl ol flra;-a=- ol+61-H qq H+Eol ulralzll zz| $e,Bag "lE +^Jql +*61+= ag q-s-r+ 4ol E
=
Hp trll :z elizl q$|l H6}}zl$ +48 + 9l+ fzl * "J + 9l+.
el19 srfolH, ** yzl dxq dy "JE Hg 4l/zltls cl+
4 *"1 H++.
[+rgl,).=
(*#"),=,*'
d/=(y),*.(#).*
[*(#).),= (*-'"),=,*'
zl='*rl zZ x* yz| E=dl-= H++r ^J46IzHqlE4 n y,
ldfldyl
(dfi0xl
") z= p,v,oA r4l
E + 9l+) rflH q+r+ eg- +4lE
"l dB6J+.
flx,yl +4 I zzl "J4* ad aHlrJ xz| EB rll,
(#),=(#),.(#).(#),
x
*41 z
dy
ssl r di - (0xtdy),
¤zlrJ ^l^.Sql zlc D(d Ell,tl ^l-&)E ¤-s.¤r+= ++rll +41 3
4, 9s9l Ee 84ts "JC6IAI *zlqE E+= +ElU+.

dfb fE trl=ol+. ¤ololzlE ¤1943 +^lE qBAl al (#).=-(#),(*).
s ¤4.4,
+41 2e+ +41 39 at}^l7lE q++ ?3 euerg tEt trz{l
*l"l 484
[+fYl,).=[*(#).),
qlE^J f =oly+bf(*o+ rgl srlt EL+)E groS;=c- (#),(#)"(#). =-' Euere +s szr^l
q^.q=r+ ,JLI.
fg)
\dx), ' f+l
-3*'y \dy)-
-ax3+2by
Hl g+"d=g * q.u r-1 r'o14. "JHl4eE g+"6}e gEql zl 4B++.

44zl$ zl"ITl+. :_44 dgol+:. olt
e-l=6}q, .$sz}
el 4Le gE ¤qql^J= gEql ql+ H+gol o]]* leq,
du =cvdT 7l.Eoil trlE Ltl+ oilLlrl Etrl tgE +trll (2A.15a)
Irl4^J +Î4.J +4q1^l= g+%rg gsq 5-galci-r.
.JA+ +qq^l 8= Hep ulao.l {.fl 9lHzl
_H-
= "lêl
"Is ¤4. Hsl¤ "Jezl{,:r- *izl Crol4. +rJ'Itl$.E ¤q
Elql
g+"*e "JA+:{ 419 q+ "|uJzl Hfl¤ gE EE+e+ g ql^J g+*ol $soll ++6IH trl+$ ?"1 ¤ + 9l+.
$rlzlE rjl ol$aJu}.4 ze.y^lql E6IH q+r+ ee +41

2A Ll|+ ollLlrl 43
olE "Jf, gE tr-^"4e1 ul (qutLT)= +6IE

or=ff cvdr=c,f dr=cvffi ^lEE "JA-+
ul E$-*"1 +eq. ¤s-"*ol r+L ae "JAqL+q{ g*
o + ¤.E7L
rElr ++EL gE HEI Arql el6]]^l tr+s-r| *ol -,?*aJ 4 =#+I9l ¤4zlzl *ELtrI= Fol ¤+(+ ^lEE
gql q+ *=Jol r+).
+ qlqzl Hp+ "JqW+.
LU =CvLT
^wl
7lEoil r+E L}l+ oilLl^l Ee+ I"Jtr +trll (2A.1sb)
v
zJttEt 0{l 2A.6
Ll]+ qlLJxl {rli .JC+ +i4 6}ql^l ;E:B gr} Ae_EE g4-+vl E¤ *zl +ql Eq?lE zl4l 491 sswe-l dg
(2L.Lrbal) +lE 49 q--q=4 ?ol ¤ + gl+. 7l= Ba l20s EoJ 4+9IEJr-1, zl^ll9 ¤.ETL s.0'c g
e+?^kL+. d¤zl 7I =o -o { gg (ss W) x (120 s) = 6.6 klol 4
qy =C.LT (2A.16)
(11= rw s), trl-4^J ge" =d=g trhq-r+ 4.ol ¤4.
ol ol+6LH a+6}rll +C6J + 9l+.
g+%hg ^lEg
^lg ^leg
+ gc*E gg ,r.l-e.91 zlaE(91d4 dzl4e+) ¤zlgl ., =ff*=r.3 kr K-r
7l"Jq= ¤.E tr-+g Eqq+ r-l+ql, gE^l zlal ollr{zle}
=sEtTHE=
tr1. ql-J6k 6'Jql E*^l^l ¤-zlolqE Eol gs6}+. qg Talali Ell ol-ao 9e1.
rl2. oilL1rt= gg E+ + 9l= bqol+. tr10. 1E4ql el6IE IBZIE rll+ qlqzl| {o}zl ?*l. "JA6t
tr3. ,JE zEle qlLJzlTI gE^l ,J=q= 4col4. +.
44. EE EElg qlHzlE gs^l tsE 4C"14. !u. Î+ S1H*ÎE "J4"1
0"J trllE Sal1e gg 6lzl *=+.
Ds. E3 9s iI ql$ql qlqzlTl oldsl= 4Col4. at2.
D6. $x1 ;6ql^J r,folzl$, "Jg ++lql fl= E^l¤E e^lzl + 9l= Hp+tr}.
oJ ¤+¤ 0l+61-= oldol,4 ge +glql il= s D13. 7fq tseFl "Jq+ElE 4 +4ql^l 9* S4"l 4lE Sq
"ilHxlg
zl¤9 +e^JoJ ¤+¤ 0l¤-61-= qlHzl "ld"l4. r+ ?ot"F ql4.
J7. Lll+ ollLlrl= 419 dill "lluJzle^l tlEll EL+ol+. D14. "JA +i4ql^] gE^l oldq= qlulxl= 4lE Lil+ "ilqzl
tr8. Lll+ qqzli $EzI94zlH +rI*+. EEle+ Aq.
tr9. E= EH]| flal= rd4 eE "J^lE .ll+ qlqzloll QlaJ zl tr15. E 4laJol+ oldq= gg +a6I= 1"14.
=s-d^l=
ca ^l
+^l al {s
¤9ql rH4 LU =q+w +E 21^.2
"J+ g dw--p,*dV 24.5a
gC+ e.1+ "Jqql *^l^l S+.J 1y't--pr*LV A*=0oJ rllE zI* ST 21^.6
"llE "J
7l4lE 7Iq S+ "J w=-nRTln(Vr/Vi) E"9, $d zli'll 21..9
4P "llHzl LU=ev "Je +El, El-S+ "J S,g 2A.1rb
4zl4 zltr q=IILQ 2/..13
"J4-+ul g+=* Cr=(dUldT)y CE 21^.t4

EEI 28 fll=El
E1]EI+Eolo + flBrlE s.s tr4 e+z} E+. += EE

> ol E4E uil+= 0lB 6J+Eq a+e+ u[4lz[xl_tr_ qB a¤- t]4e+ 4+
gEEt ?JE|E 6A gqLt= Eal4l HEILI'EIEI HJe-4 ee
610ll^1
^JEll ^]el
elgirl Hp] ol + HsI AEql
r+¤lEoll El6ll^1 EqqE tselg trll= fllgtrlE 7H'-J0l Îolql^lE ^Jq ^tolel
=e6ttt ^H=
5-gap|.
> e4d TI|LJ
Elgtrl EEt= g8pl grH 6toll^l Ee^l oldEl= 0llLjxlel,Jtrl: (a) t!=Jul EEtet Eel old
> gsEt qHl rl^l rlzs.roilrJ CqqI el$Eel + +sq} Al}= "JA+ Sq 6l
0l EEe q+ qL1^loll^l tselet LttE=EE 2A)E 0lE6lq, !E-d ql^J 4lql gE^l 716ll+ Hls QlBiil H3r+e+ a+=
"llHzlz}
sc 7li1l Tlille_l "J+ 1A)= olEettl. 4o14.
=d(tr.E
Alol fftr 28.1 fltgtrlet gg g4 6toil^l olcEl=

"Je+ sq 6}ql\ AlTl sa6}4+ ffi¤ ofls+ ?ol 419 E E4l^l
Pvlz} zlf+rll H* + 9lg Ell= ale-l rll+ qlqzl Hslzl ^lolE
gE^J 716l]= 9lHzle+ Bzl ?*4. olBl6J aaql^J:. 4lql ,I
q7l^le+ eol d¤4.J gqqzJ +E r+cql^l ol+q: ,*
all.i "llulzll$er.J)9 "JPzI SeI "JE^l ++ls qEgtrlq 5itr4ql *Bg +C q^J ^JeE AEE ilqle 444r "l
q^J 46J6J 74 adg zt6l-b 4o14.
(rB tr|+^J dUTl dqB+ z}eq,
28.1),
"l a+ql= "Ja gL
q 6Iql^J 7l-6ll= 9ol 419 elB."l+a 6l-= gqqt4
^daE E4l 1 HE CEE ol+4^l H+dH{l ++ ++.
olA+
^le
HEIe+ erll ¤+. 4l7l "JHlzl"J tlEil Hsl¤ + trll= UE U+dutr" pb
p+dptr- r"].l yt: v+dvE EElq, r46}q zs.r^19 C9
2B.1 tl=Jul9 8E q qq HE trl+4 ag aoe H+q.
H + dH = (U+ dU) + (p + dp)(V + dV)
s!=Jtrl H= tr}s=r+ *"1 cgg= ^d¤o14. = U + dU + pV + pdV + Vdp + dpdv
H -U + pV ?!=trt t8gl (28.1)
+ "lêlE #ol= + +^lel + 9l+. r?-lr +
Etzl"+ 6Jg
¤zlrJ p= alq $4"14 v= r +ul+.(J, p,4 v= E+ ^J Hql^l u+pv-H! +4lE "l+6lE olag q+4 eol +4
B + el+.
H+dH=H*dU+pdV+Vdp
tr}4^l
"Je,r1e1 ollLJxl
dH= dU + pdV + Vdp
Lu<q EJA|? dug C9 4+

E-e,t1
7f6tlTl +lel 6s-dq+dw9 S4lE Bq++.
ollLl^l ^lql+
dH=d,q+dw+pdV+Vdp
fal 28.1 ZlTl'gdEl geE HJr +tr17l.^lp=11 Eg + 9tg trfl= Etr^1

E4t 3 4il+ ++ aaE 4*
"J"J 4lz| "J4"1 p"J iflel Eo+zl ¤¤g ol? ]] E S+ g
Lt|+ 0l I
Ll r I EetT I 7 |""-1|Tl oll Lj I
( gE^1)Htrl ttrl-. Elg g 4lE dw= -pdvfrt ¤ + flg-q, q4^J tl+r+ Ag
^
ze fl!=Jrl 45
aq-= Eg + el+. 7F1],, e)l

dH= dq+ Vdp tl^
H Ig
"JcqI "Jq 6lql^l 7l-9,*+E 24. dp_09 4+6IH
olz-ll C'C'=
r+s_r+ ?J* AWI gtrr.
dH=dq("JC "Jq 6Iql^J, Hl-B+'Jol Sg "11)
"JC "Jqol+= ^llEg EzI pE +{rllq, r46}q +l

^lg :19 28.2 0l raJ4 e3 el-xl= 1)ll7l'JaJ B=EJ +oll =J= g8-gal
trl^g=r+¤oJ ¤+ 91trt.
E=gaJAltrl-. TlrlaJq EJ8== Erl.^l7lE^l E+= gll dlr, olrll9 8="
dH=dqo 4g] Ae= ELlElEltrl.
"JE g+oll^lel E olE [014 (28.2a)
ol llql el6LH +zl4 oJol 6}6llzlzl

?+=+E {Birl H+= HIH +46171 +16il^l= "Ja "Jqql^J 4lel gE HEI¤
"
"JC "Jq 4"ll^l 4l"ll ge^J 7t* qlq4e+ *tr+. Eqq6IE ¤+. "JA "Jq 6Iql^J "Jq+= 4eg E+61'=
ql 6t= g%h4l= 5g EaJ4l+r *q- tlzl= r t+*
c1AI4 4g$r|{ mE+++. ^Fs"
rllzl
SeE tg
geJql= 8zl 49 gE HEI
*zloJ'll, ol
$qE AEq + v+++ AlTl fÎolel +a 7l+i+
"JA
ql=
tr-E.il ie+
q+4 Eol 48d4. +c6IH HI*ql^J +s= gg s.qq6J + 9t+. ¤^ +
AEE Hq¤ "Jee flE ^lg =
tE a+ql= EE # EaJ4l= 0l+6l.01 4I^= ="#dl f
qlE
!a- L E^J "Je*E
^lE Eag Si^lAg ^rE
4 28.2). r+l+ flRq Hsl¤ +e6E 7l*
=CoJtrHr
4"JqI "JH3
J
dH = !,'0,
,tJz[ i,t]+J ¤*4I(DSC: differential scanning calorimeter)$ ol
dqE 4Ed A+= Lq{:t 4zl ?tE 4* qY He+= 94 tF +6|= a"Jql, Eq 2cql^l ¤H6J 4o14. elBirle| rI+ ql
4 E}fzI otr-lzl ql$ql Qr-QiY F9"laI4 q+^l 4+4 ulzl {fli E6J Hl-g4le}Bse+ +etr + 9i+(Eq 6c).
"J Ar+= ++4 ?ol ¤ + 9l+. +6IE E 6}+el "JBe Hl¤rF geJAl(Eq 2A)E
^HE q+ qqzl
6fl=Qt "Jg gfaloll^lg E old (28.2b)
ol+6tol flffi +e* tr|eo, AUel <teE+q
t=tr 7l-=-g trEsl Etrll +6t= 4o14. rill+ "+ill= E +rl7l +a olEE
^HE
pv^ztE zizl qlEql E qrBrle+ E. 4+ qlLlzlTl 4q ?J
Z|EJ=et q 2B.1 4(H,= (J^+pV^= U*). "I+^l
a4al+ lll"Jol +ol6k HI
+E A+ql= zlEol 4E 1ALl. E44 o + olel
Eql ¤g zt6}q #*.+. 12v dgsE+El
t.0atmoll.rJ ûel a++'-ql
^He+
+ Hq.ilrJE Pulzl-4+61 H6tzl g:eEE. alTI
o.so e9 d+- E4 E4 o e d+¤ z16}$. Erfirl :oos .Jg
olelal HI¤¤ E6ll^l ++lql 6t= +^lg + ilg eE
E"J E4^lAq! o.7e8g9 E"l 6E-"1-94. "lollE SIR E 4}eq, I[I4^J gs^J *#El= 4l "Jq
V
r+s-r+ Bol 84. "llHzlzl-d+ "l
"l HEI+ E4l q= 4014.
LII = Qp= ItA4 = (0.50A) x (300s) x (t2V)
tzl
= 0.50 x 300 x @ ^Hetû^lolel
gat
ol 4l4lql^Jb t A v s= l lel +4lE 0l+619+. 0.7e8 e9 a^LolE ¤-e gl= cacor(s)zt "l-E].a4olE Ee Hs+¤
Eg {, trIel E .ll+ qlqzl E+= +o.Zrktol+.
"l + rille_l g
(0.798 g)/( I 8.02 g mol-r ) = (0.7981 1 8.02) molol Irl.4^l
Hro9 g +g SIBEI= trl^s=r+ Aol ¤+. E= 2.719 cm-3(p,r}"lE)r} 2s3g cm-3(olepulol=;-o +
0.50x12x300| +r ol HEIzI r.obarollr-l gqB UIE flgul HsIe+ 4+
AH , = = +4lklmol-t qlqzl zl-= 4l4I6Lq+.
10J98/r8.02)mol
ÎolE
r.alg ol Al&g 6]BlE *d ol Eee-l flBvle+ r
^[B
.+l+ qqzl ,r.|o1E *4l(zs.r^l)= ol+6lloF ++. ol + "J
(b) E 4tg
E zl+ Sqr+ + E +rrlE ilE +49 + ?1e4, +zI
844 Bs++ slo,L4 Hq.ll +Hl!= flBrl HEI¤ g 4l=J
t+6 1H=]
4. tmol9 "&3 flf$ uI= Hh+q=+

A* tw+. t39 V
Lnr5=_ Avr-tr.
E rEE E "JE- pE*rl p-Mtv^* o1
4l4}g + gl+.
@
eo 6}o1
fll "l H+"1 "Jqg

qlE $REl H+= r+g=r+ ?JLI.
HI+ 2Hr(g)+Or(g) - 2HzO(l)ql^'1. 3mol9 zJzll-$ $xl.
A.Ff. = I{,, (aragonite) - H- (calcite) 5ol zmolE .4ill-d- Ezl-tr. E6Iq, q4^l Anr--lmqlol
= { U, (a)+ pY. (a)} -{U," (c)+ pV- (c)} a- Lvr--3ol ¤+. tr|4^l 298Kql^J= RT=2.51mol-lolil
=Au- +p{V.(a)-V-(c)} ol alql^l "Jq+= slBEl HEle+ .I+ qlqzl HE+
Îol
"l ^lql^l "=-
olep+olE= rqr cE *ÎolEE +4 ql= q¤r+ zJZ *4lz}
^dB++.
U4. v,"= Mtpg Hq+H q-q=r+ gol ¤c1. AH,, - AU- = (-3) x RT = 1.5k| mol-t
AH,,-AU
^=p*()-j-+)
' \p(a) plc) ) 94 "l il+ q{lql AE=tr E^l
!-71 2B.rql^le-l+
=
qfl¤¤ +e-l6}q+. flBq HEPI 4+ ql',lzl HE+E
El= B{fl" M= 100.09 g mol-'$ ol+6IE
trllol trl^s= r+ + +gEll, olag HI+ol "JqB oll ¤"1 4lEi+El uEI4+
ae ar+= eg + 9l+. zlzli 6rzl"J .-4illz} Bdg ql AITI ++qq +flE+El
otlHzlzl +^l g.ElE{ zlatlzl ullEol4.
AH- - AU,, = (1.0x 10s Pa) x(100.09 g mol-t )
'[#r- #r-)
=-2.8x10s Pacm3 mol-r =-0.28Pam3 mol-r
tr++,{J (1Pa m:: l JolIr e), AFI-- LU^=-Q.281 mot-tol =l

2B..2 S!=Slel 8E0l! rrl= EEt
ol <lg AU-{}E o.lvo Htoll * g+.
=ql, +EAE flBtl= 1e--E7l +"le+= 4zlE'll, r olf+
+4 ¤+tlE a+q= $E"l q*q koI^J P^y_g + q+ qlLJzlE a+e+ A+ Ezl¤ol +g qlqzl ^JEIe
=
q^l ?t= {, $Bi{e+ 4F 9lHzl Etrl^l ol=el dill qlq zlzl rtzlali 4"14. qlBrl +7lq
^]tr + Hg AET\
il-= gHI4e + +^l6llE g+= ag .J + 9lq. s--E +71rl-"19 +4lE aa(qlaql
"Ja $4014 E= "J
Î"lE
Tt7lB.7l2B.1 10.0bar9 oJq d-"ll^J t.0mo19 qq +4 A +vl)ql 4=} +s+.
(r41, nj=. s.zsg cm-3)ol ¤14 +4(.z41, IrJE 7.3r9 cm-3)
_e tr He. trilE zl¤ 4l&6}q+. (a)tsg g+oil^1sl EEaJ
^He+ û ÎolE
^l+ 4ol= z\e "JA "Jqol4. "l a4
[v'v-=nv-llv,E slqlql^l 7l* 6l
ql^l slgulE gsql q6}]^l E^l* r4Eq ddel zl&zl
r gEql^JE g8-g+ EEeJol4r +=r q-E E^l+
=
f,6 tr-Eol +q6F= 4AE4= 4azl "-+ zlzlJi-ol g +(rg 28.3). "l4g r+s'=4 pol fal_o + +4u+.
q6F= r+A$ql^l= Lll+ qlqzl Hslel qfg"l HsI$ {tE
AH
ol r4l q-= + il+ $EE Hel agql+ pv-nRr$ Bq+ ce "Jg_gq E E-J t¤e| (2B.s)
H Sd 7li-ilE slBq= +-q=4 ztol a_ 4+ qlq^le+ fl+

-dT ),
^la + fl+. "Je-"Jq g+=*e "Je +!l g+*(Eq 2N+ Hl+6J ^de
ol{
=.zl ^Jeql +.J+.
rqa g8-g+ E EEaJ e,*3
H -U + pV =U +nRT (28.3)
Ed rmol9 9*=Jol4 ,tllzl d3ol4.
ol ol+6IE zltll,zl
^]gtrl^s-r+ ^JCq4+ +qEJ= HI+el tlgul "JA-"Jfl g+a}g flRrl Esle+ gE Hs+ Îolel +AlE
H+= eol +48 + 9l+. ++,-H= rll ol*¤4. SEzL ulialzll HEJ trll= 2B.s^lg +
Al/el AU ,t.lglsl gzl
*4?ol ¤+9ttrI
A,H=LU+A,nrRT (28.4)
tEa 4tr, sE 7liltl
dH -cPdT ("Je 'Jqql^J) (2B.6a)
ol AnrE Hl+q +Hlq= Tlill Ea.el EA* HsI +d ql^J gE ¤qql^J g+elol "JA6IE ol +AlE +g-r+
^lql^l
28 t!=tr| 47
E 28.1 gEeJ9 eE q=, ce,^/(JK-r mol-l)= a+bT+c/T2*

= w~
B
a h/(ro-s16-t; c/(lffr3)
c(s,9¤) 16.86 4.77 -8.54
J.
--:
tt
Cor(g) M.22 8.79 -8.62
ilru
-dJ
LH+ 0llLl^1, u Hro0) 75.29 0 0
Nr(g) 28.58 3.77 -0.50

. zlE ¤ql q Be a}Sol ++9q 914
-QE T
a.e{-d N,9 g+=*e gEql q+ rrll H6}E=tr
f.H 28.3 8E0ll^1sl g8g+ EEaJS gtr-gele.l
-d Al9 ^}B
=8
fl=JtrlE EEoll rHaH,\l E,\l-d re}lsel trdsl 7l=7lel,=El. âql^]
T lillel 3+oll
2B.6b^lg
^le"6J
i s.r*("] 49 98=J"l gaB ql cB
:Lf
ts +oltl EEoll^l fll=tr| rH 8s. raflqsl 7lz7l7l Ltl+ ollq^l rH -es. trI+^l zB.6a^l9 rF$"ll"t 6Iq, ge" %tE gE E=
6Jtr|).
J.rfl:=o1 7l=7liltrl7ftr.|.Eq ral6lq cp,.ol cy,-H.tr|. 3tr1. g +E+'}]= 2B.8^lg Bg q^S9l :z A+= 2s'c(2e8K)+
el too"c(373K)vl^l 486il +qot qL+.
?ol ]?tt gE. Helq 4t ul
" + +48 + gl4.
EEtl + gE= r,(2e8K)r+ r2G73K)s +44zle.
=01
,vr=f,cpdr-rrff dr=cpffi *+.rqH gs+ 4+ol q+4 *"1 ¤4.
"l ^]3
q-q=4 *ol ¤*4?_l:=E 444zls ++. l;l'*-=l; (,*ur*fi)a,
LII=?ILT ("JA "Jq"ll^J) (28.6b) xle ¤9 4E e.r9 ol+6|H ol 4Bol trl^g-4 eol g+.
flgEl Hslt "JA "Jq 6lql^J ge^l }="d.ilHzls+ *g
Ir ts ol 4e q+r+ ae d+4?l Ee L+4.J + gl+.
H
^(T) -
H
^(Tr)
= a(7, -\ + |bQ] -r?) - c (+ +)
Qo-coLT (28.7) olq^J +il qlolEl$ Bq+H q-q=$ ++ 4+7]. +e+.
ol !g ola" a[fl ^lge] "JA g]q g+=]g +A$ + 9l+. H *(373K)= H- (298 K) + Z.Z0 kJ mol-t
+ "JC+ .Jq 6}ql^J(qlTlql L=qi zlf¤rll S+g +
9l= ^l.eql^le+ *ol) "JA=+el +¤B gg F=6].ts^J gE +4 g++3 "JA+rll 29.141K-rmol-rE -r-698(2s'C
q^J 28.8^lg 6lq ++ + SfBirl <l"l ErJ +E
dr-+g Eqq6IE q= aol+.
oleo <t)
gE Bg"l qlE gsql qsE g+-+E HF+E +^l z.rekl mol-19 zl-= +4U+.
=ig
B7t 2B..2 ql+61 *9 s-gql^l= rxllE ¤8*"1
zll)E a+ql= ol l.(|z]. q+61 ggo}4l e. "*=+. rBlL+ ^l7l Hlql6[q,
Trql Cp,^= a73ol4r ¤ + ll4. ol4+ Ege]
gEql 4.eL H+= ael6ll +qoh R trll= q-q-4 zJg zJ gEE 0+q r(Oql Tlvl& t-];.1nlzl 7IS6IH slRirlT}
¤oJ.=L^14 de4¤. ole" oJr{. B"I4 Hatdr4r
uJol='Hv,E
Co,^=a+br*+ (28.8)
¤zlrl
V
2B.1), ol
a, b, o) c: gEql ro¤l dE +4rrlElEolq(s
^lg dE 'llolElql "*+ol
zlflrl Aeg} + 9ttr|. (b)
부가설명
EAa.l= /\l,olel zJll
6lql^J TIge- *I ts+EL+. olq6J
@ EEq ulEfl!=Jrlst 'il+Ee] 4lE "JA+ "Jq
4l= ++lqlq- gg alE 4"14, EI4^J gE^J zlql olluJzlel
NrE 2s'C++q 100"c-e 7Ig6l-H E qlRulz} r=T}altl 9"I4
"JBzt ++lE qEotzlrl. ¤44 " E 419 8s: gA* +
H6l-4lL+i e ze.r9 g+=* trllolElE ol+61q4. rl 6lqlî TIgg ollB+ B g4+trI.gszl. a+ g+a+=
ag g+ttol =_4E Folq, q+^l Ell+EE a+ 4el "J
t+8 2 1H=l
C-"Jq g+*e "JC-+vl g+*tr4 r4.+ql Eq 2Dql tr+{^j 9d zlill9g+=ure gA +iilg trIE+ gA "Jq"J
"l F g+* rlol9l 4 sl K-r mol-, "J+ q 24. rflz} zlill9 "Je +
.rJ EoJllzl"J $d zlill9 a+q= o19 Zt"l qI
+4 Ag A++ +Al7l CB6Jr+. yl 9**"1 g-t mol-rols +(Eq 2A) o1 il+- ql*
"J ",R= r2l
^JE a+ql. +
6l 4014 HIEÎ rEj6l] +qot +trI.++
Co- Cu - np EEB= Un1 pgd zlxllJ eB.s) =
^l.otg Es" *ol 4*61 Bl+6tq, "JHI4_" e :1 il= +^lg + gl+.
=s-d7]lLJ=
tr l. "JC .Jqql^l alql gs^l olC9E qlLlzl= r 4lE t!= J 2. flgrl Ee+= gC Sq g*Ale +A6J + 9itr]".
trl HFJe+ e4.
=s-d^lE
,rl
ci zl
z,
I
--1 +i al Hs
tlBsl H=U+pV o--Ol
7-1
28.l
"JA SqqlîE g "ld dI7=dqo, +714 "J S.g ,11 28.2

LH=qo
AHe+ au rlol9 +41, s-E Tql^l LH= LU+ LneRT +q6F= ¤+t}Eg g +ylE +^lg + 9l+ E"g n+c 28.4
"JC-Sq e+e# Co=(dHldT)o a9 28.5
g++= Co-Cu=nfi 9d zl^,ll 28.9

Î"19 +41
EE 2c EEI+
AH= olfl +4 " + A=ql, olag il* Eer+ 4l

trl Etrl
> ol E4E Hll+ olB
+ Eeol .*= tEllql glrll q= HsI rlAql^lel elBrl H
EF+-qt= trl+ll^'l 0186l.= EE+E :d Eottrf. +al=
=s-d trfle+ ee aFt s}"l+.
Etr+-+4 tllolEl= 0lE6lG Eeul
^lEol
BJ&ll^l l|ets E= rll0 lElts E-d gqffi
+ ?,ttrl. gElEl4 Êg qE qI E^l¤ gEql^l + Eeq E=
El¤loil^l olEg qq|E "gEal oEErl. ru9<
$E}|= 1bar9 "Jq 6}ql^lel +++ t'-E1] H *auo
> "-qc 7tlE ol+.
HJB fl!=Jtrl= rl= gd rHg HJEofi Ee-d rllolEl= E=
=:d6tfl
+ 91trl..
ql+99 -E= tlEH= 2e8Ke+ lbarql
qls^J 2e8Kql^J .+ill
> =JsEt qHl rFl +++ Eill ql+golq, E sooKql^lel lxll ?9 -Ef
^Jel
fllgtrlel Selel Er4l olriol sEfl -*+(EE 2B)q +attr'l.=
:Ltrl-. HJ8 Êl= ++6J 8"14. +.+E A+ql= s
^JEll= sooKel lbaroll.$E
+rl6la ?lol0l tlgtrlE erE el=oll sEt rl'ets EgzJ
tlEilel 49zl H zt4EcHEq sE). e++Hl+ol+ Eq4
(EE 2B)0ll SEt xl^lg 0lE6ll0t Zltrl'. =
Esrl.ll 4qI s= $lgirl H+= E= ^JEllql fl= ^JcE=4
tr= ^Jqlql 9l= HI¤+=(E+ t"J+ B^lg gEql^lE)
4qL HI+ 4Aql^J gEî oldq= 9lHzlE ETalE EoF $lBi4 zlol+.
ÎolE
7I Est+ol+. gp+qle- gqqlE 6J EoF4r. tr.=rll, _r. ol E= SIgtrl H+el aj qler-l E# =o B {Bul A*pH"9
+ gl='ll, olag ++4 ,Jol rbar9 $q 6}ql il= ++qI =
r
+E Hl+ *zle+ ql¤¤ol 6ir+el 4lE "J=q EIE HI+
ql E6I^J ol 4le+ +gl rglHzl jl¤+ol "Jg+zl 4l a4illTl 1bar9 zlzllE +ts¤ 419 tmol * elBq HEI+
^l-"lql
Eol+. rq4q HI+ql^J +s4+ g+q= {lHzlE g al H2O(l) + HrO(g1 4"0 H"(373 K) = +40.66 k| mol-t
*H o + +C6Ir" ol EI*ol gAfl +q 6Iql^J "Jqg ql=
"l qE 'il+ qq^l He+e| eAl +r" E "JA+ "Je 6Lql^l
ol Ezl-E_ A Lq= ule+ Bol E= {Bulb qE gEql^Jel
"JqB q= flErl HEle+ ar| += 4"14. ole| $QlE HI &e-E+ ae-]ts + 91trI. rel+ ++ql q4 gqq4 qlolq
+q r]J+ oJE :z H}*ql^J gE^J +e= qlqzl 2e8.lsK(+ 2s.00'c)ql^19 {19 u;16}1 9lq. HEE fl
^r/+ ^H= = gs
e-l
"Jg ql+6J + 9ttrl-. #ol s,= eI ol ilzllel EE gqql4 qlolelE "l *+.
olnl trE 2Aql^J zl4+ Hl-e| eol ++l-tr. qlqzlTl g_tr ql 7l=+ 4"14.
gg H+ r4r i9_e9q gluJzlE E
î "J=q= H+=
E^J ¤+6I= HF+E gg H+{r ++. 9ol "J=¤+= EE gE g+l a,..Hql^Je+ zto\ zls- Aql+ dol 849
Ae 41E flE4 eA= *6LsE gg zE|e 4¤ EzlE. Eolb 4"1 al,tl +Eolzl"J ol4E 9l ++"J aa*
^H<o"J ol tsE-l
"l+. Hlqe 9ol g-+q$ $g{7t 6z|9= + rE|$ "l+qr il4. dzl¤ Hirle+ +AE Eq4 deql
aH>0"J r+Aol+ +
=E 4 Eoli aEqL E+E ++= ++qlE+ Eol=.r.11-E.g
+Eol ¤d rJ *4zlol4.
BE 4C, aH<0
S¤ 4C, aH>O
(a) Eal4 EEtsl g!=Jtrl
2C.1 E= g!=Jtr! EEI E"-14 t}=il Hslql +Hlq= s= flBul Hq¤ E= flol gl
+a 7 A,,.H.E g^l+trH*. 2C.1). E= s!=Jtrl
elgul HEI+ "JtI4-"_e. + ^llEE e+ "Jq+ z4 6Iql^J =4+r
anurH"E
=t+
:z eI ql+. E 6|+E ql= E= EE fl!=tr! A*H"
- qAE z$g zlzla_ H rql+. q++9 A+ql= E= fllg oJql, olag q+4 4-o1 lillz| o_{illE Hq¤ ulE E= $l
50 1H=l
E 2C.1 dol -cEoll,\lsl E= EE "J t!=Jtr|,, Eall= +d +&"1 "Jqqa olq^J +gq=
="J ^J^Jg "4iil7t
z*Al HEltr- e= 4o14.
TrtK ¤+ rbtK 6g
Ar 83.8r 1.188 87.29 6.506 HrO(s) -+ HrO(l) L"ff
Ius
CuHu 278.6r 10.59 353.2 30.8 H2O(l) + HrO(g) Arf

vaP
HrO 273.r5 6.008 373.15

40.6s6 (M.0r6 diil: HrO(s) + HrO(g) A"fusFf +A If vaP
2e8Kql^J)
He 3.5 0.021 4.22 0.084

"l zldzl aEE dillzl e4= 4d aEE ar}e+ 5-"J"il"t
" zlE eql trl "*g <tEol ++Elq 9lq 6IE-e. dAl4 SlRul Hs+E + a+el <lol ?"t"F 6}11r)
(5-"J+ gEql^l
"l 4aEol "JqB a+), ¤E4 + *
0
gtl EEI+ 4?"1 ++91+.
HrO(s) + HrO(l) Lru,H"(273 K) = +6.01 kl mol-t A-...H"
suD = L,..^H"
Ius + A-.^_H"
vaP
(2C.1)
ol A+qlrJq ?ol s= $gq H+= *# gsql^J S"J g
olq+ dol gEql^Jel <}g "JH ¤4g ollzl "*4. g3r}+ql AHe
I
ol+q= qq ++g slBq=¤ E 2c.2ql sE6il +?t+.
vap
1 LsuD.He
^l H
$gq= tlel EL+ol= + + tl'll ^l-olel flBq Hq+ + ilru

6i L.rus He
t4 r}"l9 Es+ agql ++6|4. olag Hsl¤ qBal .Je S
7l= i]+!+ al=. t4zl ?J7|EJ 6IE, Lffzl E"J6J 1I9= '* {tg 444, e q} EeE
trt4^1, ¤+ dpi{= .J^J
"JE
ag eltrla}sE gs++ql^J= trl]*61 +s6J cd"l +sl-QI*ul=.J^J +g $RqB+ r+(+qTI gEql^l).
=+=
+. qlaql Gzla H6l-= 4ce +g + 4eq qL H7I ^J4 .J++=
^l-¤E+q eg + ?lE
c. 6l-+el aE
'.Alzl
6I+s -H-olE ul$ zlzl 44zl E+= 1o14. ? dallE I g dHJ6J r+Aql 4* e= flg'] Hslzl-r Er+cql '}l+
i]lE+El *zlL 4d H6l+ s}4r _e= 4o14.
^" 44 =z\zl ztt +E"J g"+F *+= 4olQ(z):
HrO(s) + HrO(g) A,,oH" AH"(A + B) = -AH"(A e B) (2c.2)
82C.2 Eol g HJ8 g!=tr| B
=e
6Tr 4C 7IE*
I
dol ta-tF A,.rH
2
tr
ilru
AHe(A-+B) AHe(A<-B)
¤+ s-l An"H 6r
A
zHI l--g
oe. 4.oH
(+o A.ruH
qlsî 2e8Kql^le-l Ee-l +B Slg4E +44kI 661-'olF E ol
ô4
gE"ll^lE ¤¤ ?lB4E -++ kJ mol-Iol g+.
+iilE sql ++-g6J A-oH
_Q-zl ---. -Q.oll A*tH
+6ll o =. o ---r
(b)El+ Eate.l fl!=tr!
+sI X'(g).-X'(aq) AtraH
flzlEI 6(s, l, g) - ?zHg) A",H slE HI*q +Hlq= $g4 H+= # zlzl %lHeF +4H
olgE+ x(g)
-X*(g)+e-(g) A,nrH + 9l+. 6I+= sl+ HI+^14 4%r-6F= E= flRi{ H+=
dzl 95 x(g)+e-(g) --*x-(g) L*H a*^lzl trl^gq Ag EEI+ U$+1o1s4.
rll- 3-
L:O HI¤¤ -- ^J^dE Arr CH*(S) + zor(g) + COr(g) + 2 HrO(g) AH" = -890 kl
¤a sl6J$(s, l, g) + o2(g) -- Cor(g), Hro(I, g) L,H mfb q+4 p.ol sf ^JEH"fl 9l= Hl¤¤=E+q -E= t
^JC flA-+6JE E]]ql fl=
^JCE"I SrJ
ullE $]grl H++.
^fl
gcEI EI*E - grJq¤ A+H
E= ^J4ql^J E Jqzl ?+g +++ tlEllel Hl¤¤
* IUPAC +4. Etr-4ql +4oE: g6l dol Ezl-E aa*"11,'..l4 Aol AHql
4 E"lzlE, t4. - -E= ^JEIql^J EEtqxl ?+3 ++qL ^J4E dCE
2c EEIEI sl
+aI +ql^J "Jq+= olg HI¤-E A+= 4le_l6}E, s*r+ + olag 1mol9 c6Hno67l E= ad(2e8Kql^l)6}ql^J s
4ql +Hlq= $Brl H+= qI* zlzll9 qf$q Hsloll Hl6ll Ell 2808klel Eol B=¤+= 1¤. 9"14J4.9. zlzl
^J
+^lts+ 9lg atr+ 4+.qlE^l ,iltsg ¤^ HI+q a ^'g q+ alg s
Eeql 2c3ql ++6ll +9ttr1
*, ol .tr= <tg lbarql^J ++tI zlill $-tr ?1. tmolel CHn
7I lbarql^J ++eI zlzll p-e. ?lE zmol9 o,e| Sd6l HI+
at{ tbargl^l ++6J zlzll p-tr ?i= tmol9 Core} lbarql^J 8 2C.3 +7la[-d=sl E= 8¤ fllgtrl EA tlEJtrl(2e8Koll^l).
"J
+++ .lzll ^JEllE ?l* zmol9 H20-E q= HI+ql qlql a
ol+. +le-l +zl= zes.rsKql^JE EI+q qlql aol+. 참고 ? aru"/(gmol-t) A.rr'l(k;mol-t)
E 6l-+E %l$e sI+ HI+!g + q-Sql E= UB fll=Jtrl Hldl, cuHu(t) +49.0 -3268
++'ll= 4olu|. qlE^J ,|+E ¤4 HI¤¤ ++4 "ll*, cruulg; -84.7 -1560
^fr"=
?ol 44lll= aol+. r, CuH,rOu(s) -1274 -2808
=+79
"ll*, cnn1gl -74.8 -890
cHn(S) + zOr(il + COr(B) + 2HrO(l) A,H" = -890k1mol-t
ql+9, cH3oHo) -238.7 -72t
2A+B
- 3c+De+ eg EE HI+ql Eil6ll^l= -tr= ++ flR . zlE eql q Ele <tEol ++qq 914
ulz]. r-]-o-=4 Bol 99ot aJ d"14.
A,H" = {3H;(c) + al(o)} - t2H;(A) + afl(n)} (c) Hessol H=l

¤zld a,iol= +c gEql^lq + IE E= E flgq+.
triltL ¤4 s= HI+ $RE# ¤EI6IE +E + HI+E flB4
ol A,Fr"ol 'E B Ale-E -s^lq= ag E B {lRrlE E+= +B + 9l+. gqel rB49 "14 ?ol ¤s"t 49
^lql^J
zlzlt- 49 4141617l qlEql +4+= 4"14. 'E BP"l+
ol Hessel Efl"l4l ++
ae slE HI+4E e+o,L=d= Zl+= tr]] 6ll46Hot ql+. .,
=
+lE A3I"E 'E Bg'2mot9 A3,'lmol9 BBI '3mol + Hl¤¤ gdq qq c+ HI+e_E E6ll
^lql^J (f
u1, olE C+ Hl¤¤q _tr= HIg
E cB' E='1mol9 DBg E6J+. s= Hl+ flgvl= "JHI ^lag
trn
flgvl$$ q+6IE r dill HI+.el E= Hl

ol
4-o e +++ *ol 44U4.
U)
a
C)
s= uJ8
* elRulz} ¤+. I
(2C.3)
glErtrl ttrell
Products Reactants ol "Jdel eI¤¤"] ¤zlls "Jqg + 9l= aoJ g.q= S.+.
¤zlrJ 41 6}Eg +ql+=el E elpqql+ 6}J'J6l+ slE%h olEg 7l]|4 tI$"l+E +gEJl, +qL%I4 t¤g + "*"1"F
4lf v(*-qHldel "JE +)E #t 4"14. rBl+ ol *^14 *4. ol Bzle-] gqql4 <lol 3eq1 ffiafl
=4= ol+61-E
oF 6Jtr|= 4,o14. Hess9 Hlg ^fl"e-l
eE= E= g qlB'lel Aql;<l= "J + S.zl ,]lEql de4 4d +A6Lzl q
_o + ¤E7I s,+. 2c.2aql^J ol E4l= ++61-=
eje HI+ql ++ zl^lg +E HI¤¤9 zlzl9 ola" al.{ 7aj
"JBql +6il
¤E.J 4o14. + flllq, olBl6J Hql^J ol H4e +s+ qEE 4=+.
^J
s= HI+ qlRul +ql= 5E6J Har+ Fg *=
gl+. lJl"E=EtL glErll, ol
4,Eol qle.r.J EE EA t!=Jtrl E+
tri g gloJEol
@ Hesse-l H?sl olE
4? c, H, o-e *zl co, 7l^]le+ H2o o-4i-llE
ol;ll o+¤lE +d dz} el$q '|]+ t= HI* $BEl=
V
(r4r Nol Eq! s.aJqflg ul. N, zlills) Sdq tlgl¤
-124 kl mol-tolr|.
trllel E= HI* qf$ulol4.
CHr:6116H, (g) + H, (g) + CHTCHTCH, (g)
E ol-4 E-tr+q s4 HI+ql 46J s+ Hl* qlBq=

¤a HI-ffi trl+$ Aol +48 + 9l'l -2220 k| mol
tolr|.
=+7e-^9
CuH,rOu(s1 + 6Or(g) + 6COr(g) + 6H2O(1) CH3CH2CHT(g)+5 Or(g) + 3 COr(g)+4 H2O0)
4H" = -2808 kJ mol-t

rulI. Eel s= ^Jt tlgulE -ze6 kl mol-'olr|.
52 2 1E=l
Hr(g)+ jOr(g)+HrO(l)
6 C(s, graphite)+3 H, (g) + CuHu (l)
F+SIE -tr= E^ SIR4E 4l^l6}q+.

7l= tr-qlql il= gAE .tr.= ^JC elBEl= N,(g) - N,(dq
,J* 44ol HI+ql 4el 4olz1 ql$q EE gE"|d ool ¤
za{A q4 gs}q} H}+!$$ e.J6}q 6J +q4l qrB'lE g+= s.2c.4e+ 2c.sql ++4*.sq,
^}A +. E= ^JC
gslql HI+^lg "JE= }qg tsd^l4ot aJ4. +lel HI q Be qlolElE zle. ¤91 +E6H+?t+.
¤¤¤-(gs6tE 4E q}¤¤g EI4l) 6J6i-11 uBllr 611^J g +"1 +ql flE "lgel s= ^J^d elBi4E Aeld_= qlE
q+ HI¤¤ "JEq"t ++. rqa +? %r-^le + HI+ e]
"Jolg"J Eqgl= ¤-9"14 ¤-"13"J Eqfl= +".49 "JE
Bq=.E 6}6}r uulll a3q. + fl+= tzilE 5tr61 r46ll+qo} ql+. "l txllE ++6t
gs* ¤^ HI¤¤ trl++ e+ zl 91afl.r1, + 5A6J ol¤{++4 o e qq}+)E f^ "199
=ol E= ^JC $Byl= E. gEql^l 0o e +-z 9l+. +
CrHu (g) + | O, (g) --> 3 CO, (g) + 3 Hro(l)
ol HI¤+ tr}s=$
ArH"(H*,ag) = 0 E.-4 +el ol8 t7s+l (2C.4)
ag 6Je_E +ElE + 91tr|.
l5l"/(gmol-') zttrJEt q1rc.2
.-
CrHuQ)+Hr(g) CrHr(g) -t24 EloJ HBr(uq)9 ^JC qlBirlE dE 44zl -r22kl mol-r
olS.4H
"l Zt dill.
C.Hr(g)+s Or(g)-3 COr(g)+4 HrO0) -2220 {l$rl-tr -H-.a,
Br-'(aq)9 ^8C
HrO(l) * ur@)+ jOrQ) +286 AuFl"(Br-,aq)--t22kl mol-'o]4l 45- aol4. ol A+=
crHu(g)+]orG) qlaql
- ^Jd Slg:lle+ Aql6I¤ ArFI"(Ag*,uq)9
3 COr(g)+ 3 HrO0) -2058 AgBr(aq)el
Zlg +6IE,IJ, olfl o e al+6fl+a + 9l+. "l CEel
\l7l g71 2C.1 .lal udq s.= fl^ flBul(-:z6skl ^l
9-dg p:olzlS, olgEe-l dzll ,.J¤ Q]gul {tgi$ H*(aq)
mot-')g* .q4l
^l=-=.dl&el
s= g4 tlB4 (4e2okl el <ig zlf;oll.tl(oo + *:I) CEI+= 1"14.
mol-l)E ol+6lq eq4 Hl{lE +48} qlBqE 4l&6}q
4. 82c.4 +71 aElEelE= 8¤ fl!=Jul(2e8K0ll^1)-
r-lout DI90Z-:E
ara"/($mol t)
Hro0) -28s.83
2C.2 E= g¤ SIgtrl Hro(g) -241.82

NHr(g) -6.11
7l= ^JE.ilql flE cE flaEE+q ^JcE uI9 -s
pl6.JEol NrHn0) +50.63
HI+ qlB4= r slqlEE E= 8¤ fl!=Jtrl4r 6Iq Nor(g) +33.I8

= ^rrf
-tr. -tr^l++. NronG) +9.16
g^q 7l= 8Et|= E^lg gEe+ I bar9 Kt-rg?

NaCl(s) -411.15
"Jq 6Lql^J I zl*.Je+ \ i%60 KCI(s) -436.75

^J"4ol4.
. alE aql q P+e ilE"l ++Elq 9lq.
qlE^J 2e8Kql^J e^q 7l= tr-qlE N, EzlE 7lill, +93 E= 8¤ fl!=Jn!(zgaKqNr
olill +s-, +i= +9, r4r +^Jg g(a+) ol
iE 2c.s 371 ElEl=el
^J.4ol4.
"Jqlzl +Eql E}]+ + {l9z} "JeEla 9l+. + ?19 z16 ^J arH"/(kJmof')
Ell= +1 "Jg q6lr ?llull, ol =" A;lli TltI oI
"JAql -=3 cHnG) -74.81
.]zl"J 7l* dAl xH^Jg + glb gol+. s.=
^Jc flRq CuHuG) +49.0
6]|%r-+ql-=ol+ s+el^l(olg Ao} EloJEq a+)E p.'J C.H,r(l)
= s
-156
flBq= zlzla_ ++u+. qlE^l 2e8Kql^J .+al ur$lel cH3oH0) -238.66
e ^JC $gi4b q*q=+ eg HISql rll* 4, o +r.J r Ag cH3cH2oH0) -277.69
+49.0k} mol-'o14. . ztE ¤ql rl Y+3 alE"l ++qq 9l+,
2C EtrlEl 53
eI*"I* +¤¤$$ CE g++ $a]|ap ol

7}|Hr}-q-e
A,H" = AfI"(HrOr,l) + aArH"(N r,g) - 2A'H"(HN3,1)
q^l ol g^=E+q ^JcEg ^8c^l7l= aol4r E +E
- 2ArH"(NO,g)
?l+. dill4"J HI+q ql+ al9 "lel+ E6ll HI+r+
^fI"E
^JC HI+E
qlgul EEI= EIEI A+ a+. rflql E6ll HI*
g ^8^d HI¤-e-l qH}+oltr + E6l] r+cE flRq H+= ^J^d
2C.3 U3 fl!=Jtrle! -eS. q=
elBqE ¤.E at + g.I"F 6.J+(3). nl4^l EAEE q]
^JC
BrlE +E6l "J + 9l9H tr|g=4 eg +415- ole"a|.1 "J *g +s+ Hl¤¤9 s= HI+ tlgvlzl-¤4 ^Jolal gEql
e.lel Hl+E elg'l H+= +e + 9ltrI
^l +AqS.4.
:-44 ol4e} rll"lElT} S.g trll= g+=ut$ q
_- aJ 8s.q1,<1s1 Hl* fl8.,4E "l$alq "JEel gEql^Jel
Products r= u3 gl=Jtrl (2C.5a)
tr= Hl+ flBqE +B + ?l+(rB 2c.t). "*e a+ql g+
[^rxll tr^l-] rj' rllolrlzl HI+ $Bq qlolqEB+ aq6}+. :zr_la|{ z}
) vA,H=
Reactants
Es$ ol* zl-b¤ a+ql= ¤zlrJ ¤E6}BJ= *HS ol8
6H^l EE 44zl SP Ssql^J +C+ HI+ SIBqE+ q A
fl4
+g + 9lr+.
-t_
3 ---:
H HIO E
zB.6a4@H=CpdT)"ll E6LH qL Eeg T,E+EI rrtr- zlq_
ilru
-l A
Lio=
g trI r qlgq= H(r,)E+q q-g <ts-E H6J+.
a
H,\ig
oo=
H(Tz)-rtrS*ff,CpdT (2c.6)
4l 6-lE=g +=e_l qrBrlql+ 6l]'Jd+ EIE=*4 ,ll+E

^8^d
(q7l^J= ol gE ¤qql^] t EEIzI 9"l4xl ?*E4l zl-
*o} 4o14. ol AiF= 2cj^lel +^14"J 49= {zll{_e_tr
ol+6t= ez}+ trl^.q-r+ *"1 s]4=J4 4l+ Efldql 4:+J4 a6}fltrl.) ol 49 HI+ql +q6l-= _EL. E4E flBirlql 4
+ vr= EE6Lq +lE 49 a+ q ^ll¤g -+ 444zls +qq, q4^J E= HI+ Slgirl= Atrf(r,)tr.+El q-q=r+ e
6JtrT.
^l-o g zt_q-E H.J4.
Kirchhoff
A.H" = Ir,ArH"0) (2c.sb) L,H"(72) = a.H"(4,. Ji A,c;dT ol rllil
--lH --i
(2C.7a)
s++=Jzt += ^J^dEql 46l],<J| ojetr" ralr HI¤¤ql ql ¤zld A.cr"= ^J^dE4 HI¤¤E -$.A +ql^lE E g
6ll^lE geE +4U4. ole+ ?ol EqL=t4 fE PaZ zVl +eJ il-= 44 :llql H}*^lql +s=
^4
Elql=t4 4l+"J+4 ,I
4 ,r EE vo)E +4Utrl.. +¤ s+E=+4 4l+= E+ "Jolq +^lvJ trl-gql +l+ i}e+ 7Jr+.
=,
++614l vs 444r e^tE Eolxl ?*=+.
L,c|= I
Products
vc"o,^- I
Reactants
,ci,- (2C.7b)
zltlEt 0{l 2c.3
HI* zuNr(l)+2NO(g) g= HI+ el

- HrOr(l)+4Nr(g)9
Bq= zc.sa^]g 0l+6}q q^s=4 *ol zlt}ts + ?l+. AH/\I9 t,H"(Trl
oo=
I
A,H" = {ArH"(HrO,l) + +ArH"(N,g)}
H
- \zLfl"(HN3,l) + 2ArH"(NO,g)l
ilru
EJ H"( T1 HLO
!-io=
E
- l-r87.78 + +(0)) kJ mol-t
- {2(264.0) + 2(e0.2s)} kl mol-t

= -896.3kJmol-t T1 T2
-9.E T
2C.sb^lg ol+6IEl E, v(HNr) - -2, v(NO) = -2, rA 2c.1 Es.zl 86618 SdE4 Ul8Esl g!=Jtrl=o| trF
v(Hro;=*l, v(Nr)=+4-tr +=+.rElH q^-q=r+ ?"1 99 =7l6lrlu
r trE= e^l ts= + ?itrl-. 7+7:9 glgtrl EElts r EtrE9 E¤ieul el=
?J9AWI +gtrI -Lrtrl'. HJB glgtrlsl Eal.ts HIE 888"[ UEEE9 g!=tr| Eel-7|. Eltstrl=
,l= HJB6|.= a0lq.
54 1E=l
ol 49'Ig4 ztol 2c.5b 14 ge EE +e}4zls El+. 4g e*e1 ,,.je-oll 4EI +AE 7k6l]tl 4,"14.
L,C"o =!v,Ci,.(l) (2C.7c)

(d rffit +^l.al E4laJ
zC.7a4* Kirchhoff9 H=lol4a ++. gE- ¤9ol Hlr4 Alil +,\El EaJ4|(DSC: differential scanning calorimeter)E I
ㅡ
#g a+qlE 49? gEql ++6I+j1 zlzJo|lE #4. zllzH A* Sq E44 E= +E4 Hsl¤ "Jezlts ^1ts +
6|ql^J
E g+=*g gs-9l "L+ E6Iq+E ol.E zl^= gEql 4+ +El gE^l ml-zl4zlzl+ Eqs= qlqzl= +¤6F= Alz.l
Ezl f*Al E=qI+. rBl+ a+q El+î= zB.TaA;^ "l+6t +. "lzl.<J ',rlzf+= "Jg +^J $Cql^l 844 E'b ElE4
q g+.+g sE E=g aEl6]l azls qi+. L,co"zl l.E+ H+= "Jezlzl ?t= 7l= Eeq BE"4 Hljl.q! ^lEE q+
4 r, ^l-"lE ¤qql^J gEql 4el ++614 zc.za4 +q 4 g ++u+= Fe_E 1o14. r?]r.+Î^l,ol4E +
^F$QI
Eol (L- T,1L,,Co"zl gtri. tr++^1, q. ^lee+
7\= EAE gE= +44{ql\ Qzl,<lA+(+
^l-6J+)=
ag E6l+ 4"14.
4EE DSC= dzl4 o e "Jcql +E-E zlpa1173 zig F zll9
A.H"(T, ) = A.H"(4 I + A.Ci(f, -I )
=e..1
Kirchhof{
r+iil
(2C.7d) 4dE qqgl+.+^l-=,r.lzlalzl dq gEE rool4l 6LH,
CB +^l $Cel "Jele-l + ^14 f"ll^Jel gEE T-ro+at7l
H-
¤4. ez14 uE s-E +^l¤olr|. .<lE 4dr+ 7lZ 4!.E

@ Kirchhcrfel HE.|,E gE= e+qs dzl ¤49 aa6}q di{ E4 4ag E6ll
2e8Koll^J HrO(g)9 E.+ ^Jd dgqE. -24t.s2kl mol-'ol ,JAl6ll=4(r-4 zc.z).
^l
trt. si. ¤8*ol
"J{-"Jq HrO(g), 33.s81K-r mol-r; Hr(g), gE rql^J ,r.lazl844 4ulE slql4 HEI¤ oJe zlzl
28.U1K-rmol-r; Or(g), 29.37; K-l mol-'ol4H l00"Cql^J ?+g oI= gE^J oldg qlLJzlE qp-cp!T= 0l+6ll
^lH+
I iazlq .tr= ^8d qlE9E 9"1-7I q4lL+? g+"+
^l 4l4I.J +
gl+. ¤zl.,.l LT=T-4olq, Cp= gEe+ ++6|
g gEql ++6tqr. 7td6lq?+. 4t- zl46J+ T=To+atoJE + LT-ar7l- ¤+. stq}4 E=
zeiE AtB L,C;71 r,s+El ?, gEql^l gEql 844 Hs+zt "JqB ql= ^lEel gEE 7l=al S96}rll H
ÎolE
++6tH {+¤ E9 Kirchrhoff 41, 2c.7d4g ol+g + *44Azl g16ll^l qo+qo**#9 9ol #9"1"t *+.
= 4l+= a6J q¤-
gl4. olq^l +q Hl¤.^lg 47 slqt* hp."*y trl-s *"1 gE +Î 4aql^l +4+= ^l
^lql^le+
gl rllolrlE ol+611^J ah}++. eE eErl "JA-"J{ g+%I Ee(gegel Cp+ Cw.e)Z 7l
^,c;= zlr +4lllot *+.
ol HI¤+ Hr(g)+]Or(g) HrO(g)"I4. tr|+^1,
=ol -
t-
L,c; = ci,.(H2o,g) - {ci,*(Hr,g) + }c'r,,,{o/s)} -
-P'"* -Qp** - at -A
Ar -Qp,r* -Pr* (2C.8)
= -9.94| K-t mol-t

¤zlrl p,*=qr,,*tt-4¤r+ 7l+ E4 4dq gE= erll
^ltr-
tr++^J trl+4 Ae Ar+= Eg + 9t+. allfzl +l6ll^J gs,* "l+el dqol+.DSC-tr+El ce,*. rql
ql6}l^J E^l6J rBg eg + fl=ql olAg EEAE4I qI
L,H"(373K) = -24t 82 kJ mol-t + (75 K)
:2.476kl mol-t +(rB 2c.3). ol 4eql +Hlq= flBq H+= rl-q=4 *"1
x (-9.941K-t mol-t) -
\l7lg:12C.2 -s. zc.s9 qlolEle+ z[=_ ¤9 g+e* q]ol gcrtl
qE ols"6Iq 400Kql^JE gu,r(t)9 E=
^l=844I ^8 )l=
ㅡ
C tlEElE +6Iq4. ^le
r-lout IIegt- E
L_l i_l I
2C.4 gE 7lE dETl
aeJ 2c.2 lxl.+ 1.^l geJAL 7l= EEe zqzl gtflq 4doll
gslolq^J
^l-&g
ad4 tlil= ge}4l(Eq 2ê+ 2B)o1i;-. ^Lee[
trll*eE= tsq=q. .rall g + 4gE ._eE= =g-J
+^16171 9l6t| 1
rfl+ dE zl$sl aJtIeE + "J?]rts eE +'-ql ql q= =-r,
=Jg-d CaJ
Ê +-dtrl.
=JAl
2C Eeltri 55
9 +97 I
I
6
-) 7la le
E
E)l E7l
(-ro
3
x{ol
ea. f
45 60
tsi, e/'c
75 90
ts ulP
aeJ2c.4 58 4tr E llaJgoll^l 0lE6l.= 8xlE.E^lraJ.
f.al 2C.3 '-[H-IE +HlTlEJE
pH=2.4501,41q EEAE 0l '-1o4tr3 ef +5'C
Tlxl Eet|g +6= ?^l6ltrl7f Htl+l Etrl'= geZtrl. (8. Chowdhry
and S. LeHarne, J. Chem. Educ.
=E
74, 236 (1994e+EJ.)
(a
+4'J + 9t+. I (b)
LH = (2C.e) -:
Ir,c P,,*dT nll
Rj
g
¤zlrJ 14 L= zlzJ ol4C"l ^l4lq= gEe+ ¤+E gE
E Ll+U4. ol el6l-E Sl$rl H+= cpo 4 I +d g
^lql
el Holel A+.
^la
fal 2c.s (a) 4 #fl E4loll^l EE dal4 (b) 4E r+80.|1^1E Eo|E
(b) E8 48 E 4lH fl=Jtrl E+9 -d.
# 48 E llaJE(ITC: isothermal titration calorimetry)E- ^l

tr-E g4 H+= 71= EAE 94 HEIe+ ul:zoli {-}6floh tr 4,o14.
^li}^l
*H"14. ol ¤E 1t71= ae 2c.4ql +r}.}]fl+. +tr171 + gEil¤ *zlrlTlb ql gsql dqg trq+= + d¤4
"JHlCIqulEl AE?l El $ds. Szl{lE zl=EA4 + "Jrl "J A4= a4 zc.s{ +44fl+ + dq4
olag *B6J
7}96l+ T3trzlzl Eqgl+. E 6l+el ¤-zl 4"ilE ¤
e+E--tr rlt lrePrl ;H ,ll +E ,tJoll zlallf; ¤9 q,=plrE +41=
!l z|4E zlzla_ 9l= aEzt +"14 a3 ^lErI Eqgl+. +el4. ,H rll +E^l9 +"le-l +i4= y tllq}* ^l
olf-aH,<J
"l +zlqlE- dgzlzl E49l+. ¤Eg ^]4Lo.J ull + dEzl -E- AE E&" EE ci4.I. al-H ol +"Jql 96J
E" E
fl{g 66.o1
- 41 eqdlrll a=Jg Ezll ^lE(+rl7l E "JoJ"J?-lelEl) I ol H}so s_tr g^Jq!(EEvl.alci=ei7l g a
g+g) ¤*
E EI+ *zl 491 z16l]=4. r4a 71+ +71e1EBtI 9s ol+. ol "J- E-+ 6J6tB (Ac,9 -Jol Hl¤¤9 zlzl azl
il$ $zl.r.lzlts Ell g,qel dq¤. Eqq*+. gg q}Sol I Eo E41 .J
A+) HI+ql q6J "l<iol ¤41 6]l4e.
q+H d4ol 'J gs6FL gg HI+ol gq+E Y+e dqg + el+
^flE
=g-dT]ILJE
I l. E= dol tlgtrl= s= aaql,tJ {olz} "Jqg q "Jd+ LI4U4.
sq 6}ql^l gs^l oldq= 9lHzls+ rJ4. a 4. Hessg E4ql E6l-E 6J dill4"J Hi*g E.= elgrl Hp+
a 2. .J EAg ¤^lg ¤.Eql^lE E= 8E]|= rUarollrJ ol EI¤¤ rrl9= trti +s-= ^dE Hi¤¤E s= HI8 ql
=4q-= =
gsl53*+
++qI:r-E}l4. al} aq.
I 3. EEle u8^le ElqL Hia44 "le+ s+g ?lBirl Hsl¤ D s. s+ gtl fl!=Jtr!= 7l= tlqlql ?l= AeSg zlz]|:t-AE6Jrt
56 2 1E=l
I 6. Ei=g 7l= 8E]|= E^lg gEe+ rbargl^J TIAL ,Jr+.

=z116l+
.JC'tItl"..iltrI. r 8. HI* SlBul9 9s. E=g '+E4= 401 Kircnnor9 E=1"14.
J 7. E= u3 fl!=Jtrl= ^JCE!+ Hl¤¤E E= SC SIBq ilel
=sEl^l=
,r-lzl
d=,
AI
-1 +^l al Ha
E= Hl* EIg'l vA,H"- v,slqleJ4 4l^'
A.H"= !
Producb
f,
R@ctants
vl,H" 2C.s
A.H"=)v,A,H" v,: ($4.$ E"J)slE=J4 +

t<irchhotr9 Bzl A,H"(4) = A.H"( I + t: a,ci dT 2C.7a
a,ci =!v,cf,.0)
2C.7c
LJf Q) = Aff(Tr) + (Tz - r,)a,q L,qrt gEql 5-gals 2C.7d

E4 2D 8Ell Et+el-eJd E -t= E
> ol EE|g ull+.E ol8 )

Eqqte qil qgFgl dtrE *xlE 8Eg + flts eE ---: zgel
K
^|olE 5 (w*0,9
7l^la. ?Itr[. 0l Esloll^1= SEtl *+=01 gq6|.= *Xl^l- 6
zSEZ
= 0)
4s1.ts=sEt trxh= ¤Eg aolq. nl-

J lw*O,q+0)
> 64C T]ILJ
:Br+al| t
LH+ o{lLjrlet tl=Jtr|ts $Et| f¤e+E1 gq-qt4 gzl^l
fftr .Erl.
=01 8-E, r
+tr|, y
> Bg:e] qHl rl^.!
Lt|+qHxlsl S!=Jtr|ts SEtl :*+ah= +E6H0t 6}z(EE
^l-Al=
2Bel2C) gt+JE TtlLJ-E +rFr:u ?lolot:L]tr|-. EtrlEE 0lE6t= lal 2D.1 ZIE EEel.+tr17|. EEto[ nfzf Lll+ ollLlrlTl Eutrt. .JE 3E
g4l4EE 4rlts + el HF'JE ,Je= 47f 73e rzt 3.? 2-tr LfElLHfl=Ell, 4 3+ollqel r,v9,J
4 7lx1?.tErd 9tolof EtrHEl¤fxtE .8^l
2A).
3 +E^loJ AUg 'Je eE[.
^1e
^JEl]e+
Etzl"+
^JEll= 4e. rgl,rJs+ ?zl"J tg "J+ol
olu
CEl{
:S+=
AIE ¤{
^JE{{EI
el=6lr a +Aql= ru+ q= 4a, + r+a 2ql e-l6ll^J ol HEPI "Jq.J+r ^J461
d4"14. rl+ qlLlzle+ QlBvlzI ol*t+ tr"Elt 6J+E {l$ol zt i-lg- tlE1e+ Elzl"+ ^JEH= AE lql^Je+ Exl"J Bat"l t
g4ee "Jq+zl ?*=+ qlq
+. + ^JEIE Îolel aEql E=61_= E?]4 ceEg eE "lgr+ 4+E + tI4E 4+
Et++r ++. + ^JE}]g zlzlzlzl +l6]l^J 7}6]if "Jol4 ts zl= g.el cE rglrle+ e+(u= tlEl] ++olzl ullE). rq+
g aE E¤.J+9 415"14. El5A+ tl.EHql fl= = ol E4l $eql^J=
4l7I "J "ll'Jzl {,ol Ee^J 4le E"lzl-E, 41"il
ol+ gg zlzl:t_ 9l4r= "5olzl ?J:=+. olE 4 a+ql "J 6}qd "J il/g we\ztz1?+4 gr+ gg Ae Et+"J 4."14.
ol4 ge.^J old¤ 9luJzl= fq} aee+ +4lqq ¤ d.Etl AIZ Aeql q+ Hs+^lrlH(elar.l] zlgg 4q) u= u,e
zizlle$ +S6I+. Pel u,_e HR 4"14, :f dill HsI%Fg r-l-s-r+ 4-o1 ol {tr
gqqrE t alaS tlEll ++E +ql4 ce.g ^Jel E=
ula {Ep$ 6J+ a(4+)4 ?o}"t ++.
"l+6iq E
44 CeE ÎolE ds6J +Ali$ +E6J + 9tr" E. d-"1
9lzlzl g:9tH ¤+ +alE eg +E 9l+= 4o14. ¤xllE
AU=
I dU (2D.1)
+4= ^J"l* CAEe_l +A A+= A6Je-e__e..'^l += * + AUel Alg il¤- t}'l]e+ ulzl"J ^JEIql"J el=6l.r aBql=
e"*
^JaE {tg +ts + 9l= 4014. ++6I+ duel 4Eol oli]e AEql ro+ ag dLzI Sd
El$olzl uflf,,olr}l "J++. "JtI4 qH +
"_a "l$g 4E
gd trl=4=gE trl=
r
t d4z| !+r+ tlElt ÎolE aEql ru$ ql
3l+ zl$
2D.1 r tll$ol 8d olE"l4.
=
4lE z}¤e- EI gE^J oldq= dal qlqzlE: as^Jq
rB 2D.14 ee Hq¤ 6}b alE ^J4l6ll EzI. 4le-l a+ ^J E= dq^l 4 zlq# q+e} ar+ +El.+,
4E iol4, ol ^Jqql^J al$ q1+ qlLlzl= uiol+. ol 4lz| t
g4eE S+qE^l gg 6}-11 _u t4zl fE H*+r 6l-zl. q dq (2D.2)
ol .<llES tl-Ellql^Jel 4lel {+ I,,'",,,
"tlulzlE urol{, i+Pel re
7lY 4E t9l nl4 Alql B6l]A "J3 wol4. 'u= r}4 aJfol ol 2D.1^l ilol= +=-6Iq+. *d qE tr-4 ++
^lr+ ÎolE
-r. ,,= AB 6J+ol+'4= s¤g +=-6}014. trH.ql= zlg z| olr.ll E. gE^J 2}6llA glHzlE er-Q,* *3 Ee= +
58 2 1He
4g + S,zl ullE9l lq4l lrzl ?+914. u1-g-"= qE d4aJ 2D.2 Ll|+ ollLlrlE ElEt
?e{l E=6}E-E 4+ AEE E^l6ll +qoF 6J+(qlE^J tr
g aE d-ql^l= q=OoljL 5-"J* + ^J4 Hl-+g a "JA a^dq EaJ 4l(ol Eqql^J= olBldJ ¤.+E 4l"Jg ql
ÎolE
e ^Jql^1. q*1ol !"loF tI+). olel6J Ae el=^dZ dqzy ^J9-E
6J+)E tr}]^Jc-e 6Iq, du7l$d rllEql
"l+olzl +
ESd ElEolTl trll$ol+r EtL+. "JHI49E E$d "lE ++= ¤459 +d ¤E6I4l+. ,-ll+ qlqzl u= v, r, rr-l
g r zl+ 447| il¤-r+ 4+ ^J4 e-l¤61-= t p4 EL+E E + glErll, r}E}] "JA^l(Eq 1A)o1 ?lzl oll
ÎolE a_eql
+el^%Fol4. dqzl EeJd olEol4E 4g ,t46}7l 916l]^l Eql + H+E zlz]'a- 6l+= +Elg + 9l'i.trl{^J
'tolzl
trllB= olag dq+t )^7\E qFl u. ve+ T,p* r, E-= pe+ vel + +B H+= zlzll. 44
,ll5 + ^JEIE+EI trt= tlq-e HsI^lzlzl 9_1afl.<1 4lql 6}l E + 914 q7l^l= uE +rle+ gEE EL+e B= aol ¤
+E gE eq} qq+ aEE q6|e+ql "l+ +s+. qlE^J ?-16}tr|.
Hslzl. tE49*e "JqB EIel "Jg F¤4-"-+ "JqB qlel

"Jl} +s+. + dw= ESA "lEol+. olag ¤61 dw4l (a)tsU4 rd
ttzll; qI+.
L]]+ qlqzl= +rle+ gEq *folo + ol F Hfzl- H6iH
4+ qlqzlzf ffi$ aol Hql+.
Ef g,g,gLll+ottLlrl Htrlel altl
vlÊol gel 9l= ¤flq +ql $d zlzllzl Eq fl+r AU AU rel v01l nl= uel
6l-zl. ol 4lel a¤- tlE{. T, v,oll 4+

dU= dV+ dT Eol= LIEIL|.|= (2D.3)
^}4= T, yrol4. AV 7'
AT V
o tH [/\l
-i
olBl+ EEI+ ¤4 zlzl %IB_"_e. "Jsa + fle+ a_ *

=t-]
7|+ t*el ae q-* F zlz1o1ri. ol el6tfl a¤ol "Je6J E6JAlql^J= Lll+ ollulzlel ul
^lql
. 4a 1; 9* r Hslzl-+ule+ gEE "li Hs+ql ul4la}4, :z HlEll tF+
"JH"l oql ad{1,<1 ulz}$ zl-+ S+g. a
E? ?+?+g ¤s.gaq g+(rH 2D.2).
_e.4.
. 482;zl4 Ee *+g d-b aE+.
rll, ol x¤ +Ealzll olaN6l.^l *6IH gqEol qBr +9.
4 AEql 4* r, { I'l AUE 414}6l.q+. ol +EoJzl qe41 g+ qzlxl (dutaQ,,= olul _tr{ 2Aql
rl 4*'J 4ee.! "JA-+q g+%L Cuol4. e. aplel ul5i
a.{g ^l$dg *sq$ +d
gqqlql^J 4l4iel
^l¤IlEotzBl
gqe Exll9l^l s+61+ "#g 4lt}6}zl 4l+"J (aulaD# + EA9 qi+ qlLlzlzl 9C* gEqlî
=E
fe +E oJ=etr +44= %IHg *= aol sBol4. Eq r +ulq qBal 9=61-=zl= ++4= age.q gE+ql
zsglrJ ¤E+ Hte+ eol, $d zlrll9 4P {lulzl= e ezl ^J
+,q+ qe.g ++(re 2D.3). ol49 TTre +4ql
Ell+61
r gEq"J E=6I4, zl^-ll9 +vlql= ++61tr}. Irl4^J Erll, "lag "Je4 5."JqI qfldg *zl"J .rle oJ9 Ezl¤
="3 Hqql qql^J= AU=0o14. E+ *ql^J Ell+ HIe+
p"] 9eI4 o ? AU= e+wold,. trlE}^l ol -szllE ol +
g qB4 aEI6IL+.il gEigl+. +"]= s.4 zeoll^l ^lq f,
4 zlzl r+Aq^l fl"llzlE gg +6h= {$$ +E6I9e_ ---:
K
5 U
4 :4aI{ ol 4¤+ %l-Eg q6}H g+. 5
rl-
=!91^l -
J
AEql^J -tL+ Au=0olq, E LU=Q+wolt, + ol

+
=ol
H AEql^J4 q=-vvol4. zl-# S+ "Jg ool+(Eq 2Ê aU
U+ dV+ a U dr
zL.lq, w=0), trl+^l dE tql,qE- w=0 rr-l.I. q-0o'14. aV T aT V
ce. zql,<JE Eq 2A9 2A.e^lq E4^l wzl + E,T

(y/yi)olr, ='olzlq, +trl,
w - -nRT ln 44^J (v7v,;o1 14.
Q= nRT ln
\17|,$.712D.1 e]+ "Jqol sol olH "JC* <l"J A+E

ulzl-9 rE"g s+ql 4t
q, w "l lu9 <t# 4l^}6lq4. aeJ 2D.2 Vel T7l E+ EiI= nflE Usl Ei1l4E EEtTl duolrl. 2it trlE
g=OV'11yod-=u'1ynd=b :6 +^l6l-E uE Enl!?] Eil.= ,t E+=01 z[E4e_e E-g ttll$ Eal$ -Et
=
zf ?i4 e+.
zo 8e]l Et+elSC trlE 5e
f, HJgol
j
K n trr'0 ^lHll4,
5 U
o
f,
rl-
-
J
---:
K
$c 7li1l
5
6
lF
J qol
trrr 0 ^lHH4,
-9.8 7
+tr1 V
+tr|, v
aeJ 2D.4 EE
Tlilloll rl|6l|^1= LH+4 011L1^l7l +tr|oil ++5lrl(8E7|.
lB 2D.3 LH+4 S4 zrE ._eE I= gE6l-11 +^l:*= ttllE +tr| yoll tH-d "J8-g ?lzl Ar-]71^lutl4?l
trD. E^117li{sl A+oll= +tr17l.¤:7|--doll rq'af
uel7lz7ltrl. E^lEol EE4o+ gal EGI^lll rlo+ LH+ 0llLl^l7l LalLl
qal =7|---Jtr|.
E_tgol 4= 7li1l7l "J8:doll LH+ 01lLl^l7f AA-Jtr|.
^lHH4g
ul$ql iJzlE 4o14, ol ullE"ll LH+4 gal
ÎolE ^Js4r+
ol4r q}trt. 4, zr=0ol ¤+. rel+ loule9 deg g,J6}zl *6IB.9.+.
561 ol +^lE g+*ol ql+61 r7l ull+ql 7l4l7} d4lB
7Tr =
AU
LH+4 "Je ige_ll QD.4) Li44= zl3 Ss HEI¤ zlxlri E-+%Iqlq +cg cE
aV ), el g'J-g ulilzl *61-= 1o14. ¤44_" + ul$ loule*:29
cre+ n ffi olgafl.<l zo3zlg +*+ ?"1 ¤ + 9l+. dflg E6ll^] d^ll TlillT| +{ql= 4lg "lp.g Elzl61zl *
dU --ttrdV +CrdT Itxl"J TlAlE + ++ B4(Sd zlillE CA)g
(2D.s)
=t4"J =
"lU 4"14.
Eq. 3Dqlî ¤E6l4lzl"J rcr=0(1 ,ll+ qlqzlz| .rleel
+i4q ++6}+)0l+= ag tr-4^1ol pv* r"Jg elulalE_tr_ (b) gE ?J+ 6to{!^lE L]|+ ollLlrl EEt
9d zlale-l AE+r g + ?l4.Exl +=ql^.] "$"IzlH E
zffi- ,tlolql tls4l+ol S.ets 4+ qlqzlz|-$zf!1 Sro}43 4+61 f++ Cdol{, r- + "J+= Eq 2AE
^l-olE E]42I9 rJ4 q"ilrJ eo5A Ht 91tr1. ol=¤ :+6LAI olSe.
44q ru6tq, q-?+^l .r.lEzl. ,'tzl6l+ +"lql ++6141 q
+ ilal qH q+6izl ?*e gqq}4 ^deEg g "JEieAr+,
4 zr=sol g+. ojq $azi$ql dl$6i= v}4"lel azl- EEt 6fl46171 fl4+ E= +4617l +lS d¤Ee Hh+q +Elg
¤ ,a, der Waals ^J{!g tr|-c= 7li'llE A+ql= tsulz} 6
7I6IH EzIZI ¤t ,lQzl frzlol4, trI+^J ,-l]+ qlqzl. +
+ ?l+.
g aolQ(re 2D.4). ol 4¤¤ e
zltlz1r4. oltrll= zr > 0ol
qls^J +El 4t "Jeg gColzll *zlrlfl$ oll :z
Ale-l
4B 9l'lzlz| $Eql q$rll 9=6}izl¤ "Jl d+r 6lz}.
9 ro"llrJ qt6J + ilgq nr=natv2ol ¤+.
2D.s^19 "JHg drtr +b +gql, "Jc sqE aag +r+
|ames |ouleg TlillE 41+ +-e-e S+^la q ^Jzlts 9s
6Iq 4lHE duldrE @uor)ptr- +El.llE q+4 A¤-
H+= +¤Eie-Exl nr= +e.J + 9le?]+r ^J46I9+. ^l¤-
r= E6%I +ql EL= zz11e1 *4 *zlE zl\a- ol dEg 6I eg + el+.
fl.ql(rH 2D.s), r 6}+ql= E 22atm4 *z\E ill+r q
6L+= 4l+:_q_s 6]] +8.+. r= +zl. gq^l *zlzl 4
=
* +e-s S+g oll, Be%I 8zl9 Eel gE H+= +e6I Il.='
elr 6}ts+.rq+ r= o}+fl HslE ++6l.zl XlU+.
r-i O
r.S liil
ol ¤e ar+= E9el4seQ+r+ ee Fg *=+.+d
d+ +_q e S+q*.s'lzi o}#fl gE qqlzlzl ?*9tqq,
tr|+^l w=0o14. 6er *zl9 EE s-Ez[ {a}zl ggte_E_s
ol zll(zlrll) +se ¤ol S9zlzlE ?+9Ir mt4 4ztzlE 9+
ral 2D.s tlr.1ltl qE Ltl+ ollLlrl Eal.E +¤6171 q6lG
9t+.q4^J q=0o14. ril]flq ol dee-l C+E ollllq^J= Joureol ,\l.E-d
-
d-d Ehlel EE-
"JA-g
7l^1171=:+6lE g= g eE Etrloll
u=0o14. 4a zlAlz} 5g S+g 6J ull= u7l H6rzl 9*s Hlall6t|0F -drl-.
==JE
60 2 1E=l
E 2D.1 298 Koll^lel "JA 4|#(a) "J 5E "J*E(rr).

^J4 4* pv-rzRTol4. trl+^J,
d/(10-4K-t) rr/(10{bar-t)
=ol
pV=nRT pV=nRT
sq4
r (Dv\ t (| Drnnrl ot \
r'l- | nR nR nR I
HI4I t2.4 90.9
" v[a,
=
.,l
P
Y[\ aT /p)-v^ p-pv
' v
nRT T
EI
- 2.1 49.0
r.4 $sz} $olef 9d zlillel +{= gE Hirlql E "J

=
rloloL.lEc
I I lL- 0.030 0.185 e6l]d+.
L]
rl 0.861 2.18 xl7lB.7l2D.2 $d zlillE rE"g oJ+Eql ++ 49 +6I
.
^l.a eql
rl "*g ttEol ++Elq 9lq q+
d11=tt:71
AU 0v
=frT *Cu
AT AT
P P
e e+= Eal gr+.

olul zj4+ HIe+ 4"1 ¤9elql^lel 6J s{g ole] pol a
4L6]l^J ge +ql g "JBlTf EEI4 "$=ol 599l*zlE AU
=axrV *C, (2D.8)
^l a7
¤q= 4,"14. 9le1 ^l +HE ¤=.945 gE +7lql lrls= P
+ul Hsl¤(gC Sq 6}ql^l)"1+. "l "Jg r+q-4 Aol eel ol !e Sd6l .JHI4"J a"l+@lzl E-"igla aCol "JA+
q= ts811* aE Fsll^J ¤* Fq Ef,ql r (}ol ++qq t). "l !g .Je6J "Jq 6Iql^J E. Ee$el q+ qlLlzlzt
flsq, E4q}4e-q= s-E ^J+ql +Hlq= +j'lel ++ E g:r{l q$|l E+61-=zlE c"q a(]zq EEq dflg E6]|
ffiol g+. ^J
+Ag + 9ltrl-) r?]r zlzlr- +E},J 4o14. $d
n.,.$ zl
illql qql^l Y q+^J
r (Dy\ rcr=goltrl.
"-vlar ), "J8 Zt+ ttrEl (2D.6)

AU
CV (2D.e)
AT
7 a9 Ai3 : ^lEel *ulzl-gE Hclql rrll 9=6J+= p
1¤. 9"laJ4. s.2D.1ql a9 +Cil59 +=.6]] +gt+. r?-l

r. q¤.q" *"1 C99E E8 S*s. Kpl {t=E +41 +=.6l]
. sd 7lailE .Ja_+yl g+*e aelq.tr- .Jc +q +ql
ql+ qlqzl= gEql 46ll^J E.Îo} +dE zl$zlzluJ
^Je-l
+et+. $d zl;llE A+ql= ol Q,rzl u:oJ "Je "Jq 6}ql^'l .ll+ ql
I AV HzlE gEql EI6ll^J E^l6J +del zl&zlolzlE 6l+
K- =-- ,V dp
E3 U=s t8sll (2D.7)
2D.e4g ol+6IH 9d zlalql ql+ c,* cv +aE
T ÎolE
+ 9l+(EB zeglrJ ¤H6J utel *"1 Pulz} "JC
dril +g
Eg "J+E= Sqg 4+ +Hg rlel +ulE *B eorc¤ al4l *zl9zl ?tg trl= ge^l {fB qlqzlE
"JPzI ?fl
+4U+.:=".$ oJ+E= Afl6I= gE ? oz| +e-= 4 e. uBI4+t+).*d ol ;<l-= tr1.¤.4
*"1 34.
g ol KPI <lg o"te-tr "J=q +71^lql
+lofl^JoltrI. + "Jqol 6
cesl EE
Pulz} eA6Iq dwl+"l ggo}
2D.9^l
7}6lq dpz| oJ.o1
E trll=
6t7l trllEol+. AH AU
co-C' =
AT ), AT ),
@ 7wol)s*{+{tt olq^l H-u+pv-(J+nRTE arq .Jql Bq^J q+r+ Ag

9d zl4l9 S+ 4+ql ++49 +E6Iq4. +41= e=q.
rqp] S+ 4l+= 2D.6^lr+ *"1 C9g+ tr|4^l
zlSlE Êf
t'-Efl^l9.E+el v= rE F++E +6Iq ol49 ol
/ E(u+rnr) ) AU
+q Bq+H ¤4. :4r.2D.6^lel 4zlzl *d+ ql

Co-Cn =
[--=, ,l P AT p
nR (2D.10)
^l
E "Jq ps .JCaL4a E+. qE Eeql+ tr¤4-Le 4+q= A4= r-ls=4 Erltol S
2D 8E]l -Bt+stgd EIE 61
4l= E4 r- 3ql^l 4211o3 gqtrl 2$]g els" dloF +Eg + +4'J + 9t+.
9ltrl).
dH= (#),ar.(s),ar
a2TV
CP -cv Kr
(2D.11)
Eall ¤s6J+:- q"lq, 9zlrl 6llot 6J oJg (aHlap)rE 9E

$d zlillql ql6ll^JE a= UTe+ rr= 1/polu E "l
^lol
2D.10 oJol-B + gl= cde Hl-+ts 4o14.
"JoJ flgulz| salzl
+ E+. Eill+ ilillE a+, gs*E azl zlzl ollEql ?t=trlH dH=OolE, +lE alol ffi$ ?ol 94.
^lo
2D.11^lg Co=Cr?]a )^71 d^lEI "J+E KrE E6J zlzl oli
dru
Eoll a2lrl= ^J'J6l +E 914. ol7{? aAlTl S+6J olle+ dp
dp=-Codr "JA+ Hql^l
7J? 4+,4zlE "Jq'I= = ql= "Jg a+"J 6l] +qE qzl T
qI flzl+¤ r.Je. qlqEaE ql= tr-'J6l Bg "Jol ¤.q6J + olq^l oJHg dpe'|irq=+.
s glzl ullg"lq.
(#), --cP(#)" =-cp!
2s.cql^J Efl S+
al+e+ Ee S+EE -s. 2D.lql^J ¤zlrJ p= +94 'ZJol 8Eqq Joule-Thomson 4l+44
6J+.
e+ ?"1 zlz] z.tx 10-a K ,r+ 49.0x 10-6 barl(4.90x r0-t0
pa-')o14. rqr
ol gEql^J E9 E +q v^_MtpE (Dr\ Joule-Thomson Xl# [89] (2D.12)
trl+^l u=lai
18.1cm3 mol-t(1.81x10-s m3 mol-r)"]trt. 2D.1l^Jql ),
el6ll^l + E g+*e-l z'lft{y 441 y*g ^l-e"
6ll^J) trl+$
trl+^l
?"1 ¤4.
(2.lx10+K-r)2x(298K)x(1.81x10-sm'mol-') dH= -jtCpdp + CodT PEel "Jaloll r+= (2D.13)
r-,- _
-P,. - uy,m - ?lgu] Eet
= 0.485Pam3K-r mol-r = 0.4851K-'mol-'
Eql q6H^J= Cp,. =75.31 K-l mol-lolq, Irl4^J Cn_=

74.81 K-rmol-rol+. E4"ll u|4^l= + g+*ol 307o4
zttrJtt ql2D.2
El= il¤ +e}{zls 6J+.
= ec9 Joule-Thomson 4l+= 298K9+ latmoll^J +0.27K
bar-'ol4( e
2D.2). (pE,r-llzl C¤"14.) F-$Bq aaql
rl Tlzllel E-qg -r0bar "J+ HE+^lzlH :.gs.zl
"l 4
2D.3 TI=JtrI9I EEI *4 ?"1 H+4.
+lql^Je+ p3 a4rg tigrl H_u+pvE zlzl;+ ¤ + 611
LT = lt\p=+(0.27 K bar-')x(-10 bar) = -2.7K
ll4. u, p, q v= E+ ^Jel .J+Eolq, ir|+.tJ HE E6J t

4 e+oljL rq4q dH= $d ulB"l ¤+. "Jgg H3zI^l
vJ + 9lg oI= H7I ¤46J gqE4 aJfz} q=ql,
"l Î¤ 8 2D.2 HJd 8-E(rr), 8cl o1-(rf)ul LalI' 1 atmll
g oltrl AH= q(28.2b4)E E6l]^l A4q*.'J ,rl+ ==E(rb),
Î¤ol+. 298 K0ll,\jel Joule-Thomson rl6(t).
,<J HE pe+ rel EL+E sajl, 2D.24E EE= rqlE qsts
"JC +4 6Lql^JE HE gEql u}= Hqgg +EB + 9l+. TtlK Tt[K TblK p/(Katm-t)
Ar 723 83.8 87.3
galEl3E0il nl= fl=Jtrl Ha;.4 CO, 1500 r94.7 +1.10 +1.11,300 Kql^-l
He 40 4.2 4.22
"J¤ aCE BaJAIE ^J46]]t+. H= pq rq alfolIr + ol
-0.062
F HfzI trlieJ"Jfi Hts ull= ql$q Hirl¤ 4*4 ?.1

N2 621 63.3 77.4 +0.27
. zte ¤ql q "*e <lEol ++q{ fl4

62 2 1H=l
6e E=+E. ¤l6]l^J e=^la+.r4-r. q7l^l q?+E zlill

++qH^J ^l]tr Eqs= Tlzll= ts4^la+. ole+ ?ol B
4¤ ^lls Eqg zfillzl S+B trll= $ETI gt El Eqzl
E E7I8 xlgt 7lill =
4, "t3r]1= ++9E zlillTl ¤=E6l B4qq olaol .++q
trlEd
ilEol
*4l"ll rB:"I!l 84.
=
(a) Jouefmnrson EEtgl SA
Ioule4 Thomsonol ^l-s"6J tlil= trgg 6H tlzlql^l "Jq
r.gh Tlrll
+= r+e.ol +g 4Coi Elrll 61H4. ,J +alql^J B6]]tl
leJ 2D.6 Joule-Thomson azft ehl. 7lill= EE7 q-sr= 6l'= "Jg IA6|]_H-H qrl^l "Jq+= *^J"l Eg 4A"Jg tr"J
tE¤ ?.l"Jol= Eoll I "JdEq, Cill=861'=
6r'xl7l'Jgel'Elq?ltr|. EEollll ¤B-d + el+.
ulel eol 0l El-^l= tsA= gGlLlll -ertt. "J8oll 9dH^1 7l^1171
7 lEEl=^ |
=gl=Jtrldtr
!r='J4El=^l= el=:drl..
^zoil
zlillql zlallzlS eE Ha13 tg4es "Jq+se 4=0ol

LJ4EI 7li1l
r" q-{^J AU=wol4.
E4l 1 A{ "JE 4l&

EE+
l
(
oJqol p,olr s-_Ezl Ifl +g g'q +e_E+El +rlzl v,oJ
8^l I
"Ja%iel zl4lzl E=+= Ea}l 4zJ4_r. 2D.8).
I
\ I *g 43
$rq +e-E "Jq &rzl4, rBlI +
zlill= ol p,,
-4zl v& q*.+r 6Iz|. g+9 zlill= +oJq= zp\lzl ul:
^J46IzHr3
\ qill EE q6Jg 6Lq Fg "J+g+. oltrll9 'Jqgp,ol4 +4=

y,e+q 0_9--tr H6J4. trI4î 7liilql q6lizl= "Jg q+r+
"J+8il
,Jol 84.
aEJ2D.7 0lraJe Linde 'JEzlg gaE LlEl,-,! aolq.. zlillE {1+EElq,
r -?vl Ud e-E 016l?.lPt #Stl^1"JAE q .9E7t Ecldtrl.'-J4E wr=-p,(0-Vi)= PiV,
zlillts aoJ 7lill= ,-J4ll7lq, 'J4E ag 7l^1171"JaE q e_E7l r 016[E
q Eqdcl. r4r oldLH= eqql'E 7l71l7l EETE 5atl^1 Llell Etrl. ql¤ z}"+olel e$$ql^J= 4$"tzlts zlit)lzl qÊE E
gg 6Iq r?-l6lq S4 p,"ll "*^J^l zlzll,zl E"¤,(4E "JA+
2D.1, JouleThornson Eill
+gEl= g0l.^l=
|oule-Thomson 4lfE Tlillel EsIe+ +Eg +84 Ezllql^J ola{ Pu Vn T' o ta{
tl -i I} tl -i
tr|l+61 +s6I+. ol 4lf +cdlEJH E-slBq 4aql^J "J
q+= ¤.E E3r+e+ sq =Hp+ rlolg ul arlAffi 6J
=e6l]oF
4. Iames Ioule4 William Thomson(Fil Kelvin a)g flg"l=
frzlrlTl= zllE 6iql^J E-fllgtrl *+g "Jq+rll
"JC6l-rll
I H &
6I=.71_e.-g HlBg ^J46I4fl+. + ol=e "JC+ .Jq
I zlillE tr|+r-d ZIqolE ¤-6l] += "JA6J "J4 " + StL^l
7lH^J S+ql +Hlq= gr He]¤ Eqq6i9+(rH 2D.6).
t_l
I p( Vt Tr
;t-i
ol E-qlBq *+ql +Hlq= 8r golg Joule-Thomson E
zlzl:z 6J+. .f.al 2D.8 Joute-Thomson EJ¤i9 Eq-+4 tr14- +"JEl= 7l
=2. g+sl gtal-
illet LHEof^|5 u FilE LIEtL|1=Ell, 0l== E# 44
Linde tsEzlE loule-Thomson Effiol+6}q TlillE B4 g86lXl 8^l^|iltr|'. gdaJg 7lx1171?lgtrl Eah= +u-El'xl Lre itle
^l7l= tlil+(r4
zo.t). ol ltzloll.rJ= +e- "JqE 7141=- E# 5116l"= E4l- 0l raJE 9l+oe+EJ oEtl+o-e LHalTfE
,\1 LfElLHfltrl.
zo $e]|:Bt+$$t EIE 53
s_Eql^J) s+g ++. TlillE +qE 0_q_E+El yE H6Lq, -7Lcti

/l=.
trl+^J ol +4lql^J zlzllql qd]lzlb "Je q+r+ ?Jq.
wz=-Pr(Vr -0)=-psVl Itr 0

l-
ol zl4l9l B6llzl= dill "Jg ol + gg ++ 4I+ ?JLI.=, Lti
0ll
w = wt * w2= plVi- PtVr

p.o
q..4l2 4P "{lHzl H+ 414}
tr|+^l ol Tlrllz| t¤4o + ZIq"IE E"4¤ oll ,lAle-l
"l Bal, p
q+ qlqzl= q¤-rl {."1 EoJ4. aeJ zD.e Joule-Thomson 4l# g9 FEE 4zoll qal +e+. 8^{ gq
?JoilN= 0l Al+7|. g0lr, r
EJoil^l= 30lrl-. +clT] galoil^l 341d0il 6|l
Ur- Ur= w= PiVi- PrVr .J61.= r gajoll,t.lE HJE e-s.a1l:dtl. "Jalol +Glfig ttll= .9E=
8E=
olE ,J 016[e'*+GloF'J4 al6 E^loJ L1+'*+E SZld= LJll Elcl
Eal 3 4+r+ al+ {BulE 414} El^l 7|-E ErlE EZI Erl-. trJE 5A 6|0l^1 g'49 EolllalE q! -d
fl-aaprttli ol+atfl r+q=r+ A =fl]
^lg C?-l6Ir
+lel ^ldg coil rq.a[ llel 8Etl7l Ezttrl.. HJI 3-=, +c= 7lz)l
gtrt. =tr|
7l"Bo.E+E1 ge_e E6|! E- E=-d ?ioltrl-. =:fl]=tr| =dsl
e A+= e4l
U1+ p1V1= (J,+ prVr, 4 Ht= H, ol
fl
,lte
trl-z}^J ol s+g aREl= Hs+^l7lzl g:e-H^l "Jq+ 4"14.
I
40
LH2 I
o- Il/\
g}d zlzllql qlfll^l} p=6o14, ,rl4rJ $d zlzlli- )oule- tr
p>(
=r
ui
Thomson Stlg 6l]E gEzI H6lzl g=trI. ol 5¤3 loule- olr
200 L
n
rhomson tr4E a7171Ezlt 'JqE ¤olg ts=+= Ag-
-9.E
EB6trll ++'HE 4olci.
dx'll zl4lE A+9lE Joule-rhomson Al+7l0ol oLq4. :z
=6
0
0 200 400
4t zlillE =.s, oJq, EzLA "Jq4 HIEqE tr-'}]4 a7l, "JH, P
relr. ¤.E uI4:- *sz\ "Jol qzlLl *"1 ¤4(rB feJ 2D.10 tr4, +7S, g g$! U,gxll Tlill9 HJE Es.
=iql
ol 4lfz}
zD.e). "JolH dpzl *oJ ul ars. *"1 94, rr]6}
4 zl4lzl Stlg *lt B4¤+. rel+ ¤41 zlillel *q"l e Hltsllqlq= 49 9"lEI4. :z4a}{ Ezl-EE ¤+ +qg a}
AElql ItL4 r t}44ol $d TlillE t}44_"8 d=5t71=
erlzl= ag + TlillE ts4^lvlb a4 zJ? 4ol+. "J"J
6}zl+ foule-rhomson 4lfz} ¤¤4ge 0ol qzl- ?*-4.
tszl¤9 44ol *"t4^J ^JE oJqg "l44zl *6}r ^Js
ol Ali= ++4Al p,v,o) rql E¤6tzl ?+a E-J+ql 9=
¤¤zll ElE, B4g zlilli-ol ¤+qE 4o14.
6Lq, Eql^l Eq lcql^l Eel6J Call. Hli6}4l e
"l*l+ zlrll gz|9 4sz} Lelzl= ag +g +*e_E 'JAg ql
E-J+.
6J gE{l^J S+E oll zl-9 ElKp<g)E Lie},-}]= Tlill=
+4+= s.r+E zlzla-,tj{ollEz}. ="9 +lE g4eql q+
zl+E "Jq qlEql t 44ol :ueJzlH^J r ¤.F qlqzlzl ul
r gE= +g HJd EE r, ol6l.-e {el +ts tsrl a.r-11rro, fl¤ qlqzle. H¤|¤+. Eq rcql^J ¤E+ uls] pol {zll
+Elu+(E 2D.2e+:zB zo.ro). r+ 2D.10ql +4u Hte+
^lE "Jqg "lArHol ?lqol +qg
Tlillel Ezl¤9 otulzl
=
ztol zlillSe "JHl4eE E3 gE-s+ *3 ssg + Hld
"J
p4= ,JLD.,'}+^J zlxll $2ffi-ol ,tJ_tr Eqe 4l!. zl7
gEE- zlzlL !lu|.
E+El *"1¤4zI= tzjH :z 44ol LejzlTll g+. E4¤
g rllol+zlE
"lBzl
g:+ TlillE 4+^l7l7ltrJ 6lH
^JE =
(o).toleTlrornson Erlel Exl tE all4 B4¤ ÎolE ¤# 4 flzl rtzlalrll g 4"14. trI+^J zlal=i
Tlillel Ezl ¤.E"E(Eq lB)r+ +F BH]] gq(Eq 2AE s+ ts4^l7leJE, qlqzlz[ $_trri Eqzlzl ?+al ap zli]lE ts
slx}9 tl^l 7)L 4 ?ol Ezl¤e-l ¤+ ¤+ {lHzlzt Ss-gl *^171H gtrl. zl4lzl salEql ItI+ r E4-E=3.r.J_e E4 tr
6t+ 1E=l
qds +Al 7l+ *7J& ill+EJr aiq, ol 4eql^l ol* EzI ¤ + gl= aoj+. "Jq trs4g"l zluH4"J 44@<t, o1 z
5ol ulzl| qlq e_E+El Hq+zl g+eH ?I q= 4.o14. E t' tc.t4l, Z-v^lv;-o-E eEq= "J+ "JzDoll,tJ $zlfol
{¤ol E+ E?-l Eolzlzl +l6ll^J= "J+ B4l eF qlLJzlz} L4Al eE"6J + glal 4zl 9l"llrl= .Jqg ol44a ¤qA
ElHl¤ qlqzls H+qqoF 6IEtr. E?-l gqzlrll g++ + 6i!_-e. ts4 a4g>ogl 4*lz| +El+= 4o14. **
'tzt"t
zITl L-?-l4l ¤4. g¤el r+aE¤ z$la_ +4= ¤zll ts4*"1 zlufl4 "J eaql^l HZ>I) loule-Thomson sqql
"lel6J
zlzllzl Eg ts+6J trll ts4}El= |oule-Thomson s,r+=. ¤B6l] el6ll^J zlz)lzl q+lzl4 ¤trI ¤+.
=p<Ool
=s-d7]lLJ=
tr l. du= Sd nl$olzJuJ dw4 dq} Qld "l$ol "tr-14. tr s. sq4 gEql q= q+ qlLl'(lE HEI+ ql+4 sq4 g
z 2. .I+ qqzl flEli gE EEI9I sq Hsl¤ zlzla_ +48 +%hg zlzla- +E+E + gisq, ol ^r¤F+q g++=
Î
+ 91trt. olE +41^lg eg + 9l+.
tr 3. L]|+4 gale "JC gEql^J +4q trIE Lll+
"lluJzl9 E I 6. Joule-Thomson Ezlb zlzllzl E-el$ul S+g B ,I Ltq
E++. ulE zlzll9 gs. HE]4.
a 4. Jorte9 d:dg $d zlill9 rll+zl $Hol ooJg trq +Hq.
=g:dAl=
,({
da
zl ,r.l
--1 +4 al Hs
U(%Dg HE} au = (0 U I dV, dV+ @U taD t, dT ol7l z.,(l 2D.3
=.o!o
.ll+4 "Jq rcr=(dUldV)7 C9' $C zlillql 46H^l- ftt=o 2D.4
U(Y,DE H+ dU=trrdV+CydT olz-l z.,/.l 2D.s

=.o+ai
s+ 4t+ q=(tlV)(dVlADp AE 2D.6
E"g rc.,.=-(tlV)(dVldp), c9 2D.7

"J+E
g++= cr-c'':nP 9d zlill
^tolE +41
2D.10
Co-Cr.=972TV1rc7 2D.tl
foule-Thomson 4lf p=@Tdp)s ${ zli'lli-p=s 2D.t2
H(p,r)9 E:* 611=-ltCodp+CrdT olzl

e.olo
z.,^l 2D.t3
E4 2E EE HEI-
> ol EEl= Hll+= ol.f;. E8-d u

T 7,, 7,, V.
Eg rl8= # alEg -H.s6[q, Eqq 2E^]g

1
I
tse.l6l"= rll
0lEErl. t-
t-
ui
o
I
> ._{d TllLJ oU
f,
Tl
TrVt
> gg:d qHl xl^l
0l EEoll^j= Tlillel dtroll Il6H^l EeleJ L}|EgEtrl 1A),
g5 =61 vi +q, y
vt
zFll H=l= olEElt-l. :l.alr. g8-+tr1 EEaJ(EE 2A)el
g8-gaj gE¤ftEE 2B)8E, r.a|r-F g8Ef=^tolE SA(Eol lg 2E.1
:d
EEgl +tr|++El trl= -eEel-+qe 8Etl7l. E6l.= rl¤=
2D)E olEg aol+. F =JZ|g "JolUcl.a A EZloll,t.l= XlTt g¤-d EEoll^l
$r-tafls EJtr[.
=
gd6l.= aolq. 4PI SE 7li1le 0l+olfi= tt}|= 0l E4loll^1 Lt|+ qlq^P|.
Eotxl ?j= aolq. raLL Erll E4l= g8:d +tr| 610ll^1 4lsl e-E= LHaIT=
a0l+. Lt|+ 011L1^lol Ei{l EaPJe 0l + Ellel EEtaJ= -cf-d aal. e+.
zlz)lzl *g Selg g trllE(+E *zl qlql^J) SszI 4elA
4. "J"l B6l]zla 4l Ll]+E E3 Egzlzl $e_e-e Ll]+ ql
4zlzl E{zll, trl+^J 4E z1al9 gE-E E"l+14. EzI ^|olel
8s- zp1 HlEll++. $z|;6ql^J E oll B+ +F ql
ulzlE Toll ulzllalee gEql elafl,<-1uj 4+ qlLJzlTI HB
+=ql^l "f"Izl-ts "Jg E+q "14 Ezl¤e] eF glHzlzl tl
ullE : Hglelol Elqldlot 6J+ olelql q4^-l
a6}q, r a4e olEE ¤+ +qol lrralr. q+^J SszI ^rql ^84q1
E"lzl= 4,o14. 7Iq +g S+g 6l-= Sd zlal(+g *zl 491d9 zI9 ts
ael 9r Hqg arug + ?l= 4014.
2E.1 ES. Eat
@ 7lE EE "J=toil^1el E-=. Htrt=
$d zlillg gszl r,E+q TfE H6l-r r pulzl y,E+q LIEIL]{=
^l
vre Hg *llel .ll+ .tlHzl He+= + +419 e-e-e +4'J *zl "J*E Sqol + Bol poJ uI "Jq+= 7lE4 +g S+
f 9l4t:-B zp.r). +d, a +alql^l= ale.l gE. il+ <te g ^J4611 _H_zI. ,Lq r+Aql^J= "JHI4 o-e. HsI E+ql .Jq
_e "JCalzll *zlalE^J +"l"Jg Hsl.^la+.rflrll 9d zl 4 gszt E6ls-tr Eli* ad Hqg ^J461-= {ol {o}o}
illE Lil+ qlqzl= z EzEol zlxJaJi +rlql 5-galue. +. olst* +41# "++z}4.
(Eq 24) azll4"J ,-l]+ qlLJzl H+= E4ll +41, + "Jc +
El 6lql^Jel eE Eslql 7l"Jq= 4o14. tr+tr"l gEql +
Ell 1 gE H+e+ +sl HEI r}"l9 +41^l
dvtJ+ S+IR9 trll BollzlE "J3 dr=-pdvolQ. ol
zlz)lzl
+61+H ol 4+ qlqzl Hsl¤ +++ B"l 448 + 9l+.
49 +g HEI¤ EEL6J EE 7Iq Hsl.ll zJ+qq, r?]6}q
LU =(Tt -I,)Cv =CvLT +ill4 o dwâ--pdn4l ++. trI+î +g HEI-il 46ll^l
ol B+f. +g4olo + q=0ol ¤+. r4l. LU=q+wolu +
i dq=6ols + dU=dw.a("lA 48ql 4qL L(J=wâ9 tr41)
7I ¤+.
L(J-woa7I 9+. ¤zlrl az} hd= +g +a$ elulof,Q. ol
?l^lql Bq+H q+r+ ae +48 eg + 9l+.
9d
zlxllql ql6HrlE du=crdr(Eli 44ql rlloJ AU=
ûE cv^rE tr4)o14. tr|+^J olE du"ll ++ 4EE+q +¤-
w^6-CrLT Bg Htr+E g 195 zlxlll (2E.1)
49 eg + 9ltrI
$A zl4lzl +¤ S+g g Ell 6l-= "Jg i]grl al+ tlE]| CvdT =-pdV
=
66 1H=l
ol zJr.fJ= sd zlillolo + pE nRrNa uffil$$ + glq. r + gE= 2E.2azl9-e.BEl r+s-r+ a.ol ¤4.
4E c"ar--@RTvdwl qq, olag +*4 Bol 448
l/1.50 l
+ el+. 0.50 dm3
4 =(298 K ,( 1.00 dm3 =188K
CvdT nRdV
T V
"++î AT=-nOKolq, 2E.l^lql 96H^l +gr+ +? aal
.JAl2 ol {g zi$olq dAlzi H+= +$ql=
^19
++4. . eg + el+.
ol !g 4E6I7l +l6]]^J= ol "JEe-l 4+ 6J4l$$ r]]F
^l w^d= {(0.020mol) x (12.47 f K-rmol-t)} x (-110K)
6}111 6|]+"lo} aJ4. . wl %"J tr|] r= Iolr, Sarol g*g --271
trll y7I v,olL rE rf-e ¤+r +=+. l+lH, Sr Hep e*ql ++6IÎEJ "Jg e%Fql E+.J+= a
g +E6Iq+.
,"f,+=-"-l:,+
c\ts gEql ++61-+11 B+. olq^J 4E n.zE ol+6IE 9l
9 4E"l trI.94 ?ol ¤4.
2E.2 gal ElEt
c"tn\--nRhY: 4 zr.za= "l+6l.q 7Iq *g s+¤. 6l+ sd 7lîlE sq

g 4l4I6J + 9l+
EZt 3 4E
^19
aJg h(x/7)=-tn(ytx)oloe. 914"1 +gl} ?"1 Erl.. Boll^jel +trlq gal
s4l
^lolel
1,nT=^t $C zlal= qE ^Jq H{¤ "JeA4 zJ*4 fl+ z.}Ellql^J
olq^J CylnR-Cy,^lR-c1ts1" ln f -a ln 19 +4]E ol8 $d zlill B!g "J+llzls + pv_nRrz ol+g + gleq,
tr|{^J ++r+ ?"1 ¤ + 9l+.
*4.:24H,
PiVi
-Ti
ln PrVr Tr
?)'=,"#
:2fl rll 2E.2all 9l E 6l-H T|l T r (V f I V )t t' . oI +. trl-+^J,
uI4rJ (rrtr),-(vitvr)7| 44,
"li,g ¤q6IE ffi$ pol
llc llc+l
¤+. P,V, vf
vi
, trI+iJ P'
(+) =l
PrVr Pr
llc 8E E+
vi gE5 ztilt9 (2E.2a)
Tf Ti
vf
c-Cr,^lR 7l-E .JE +¤ $A Tl]illql q6H^J= Co,^-Cr,_ =Rol+(Eq 2B). rBl
"J8l
E+
+l czll# 611+E r-l-s-$ ag ^lol g+
^lel "JHg I , r_ l*c _R+Cr,. _Co,^ _^,
8E EAI
;-'- c - Cr- -C"--r
195 z1^119 (2E.2b)
V,Tf -Y,ry c-Cu.^lR 7lq EE "J8l uI4rJ,
ol llg pal VT.=constantoJ g_e. .q-E6-IzlE q!4. Pi

Pr
(+)'=,
ol 4¤- +s=r+ ?ol *48 +E gt+
0.020mo19 61o1 25'cql^J 0.50dm3o.tr.+El 1.00dm3o E gq H+ (2E.3)
t¤ zI9 S+g +qr 6lz}.olE.*9 gA-+q E g+ Ptv{ = P,v,Y [7|q EE EJd|. Sd 7l^11]
** D.qzl K-rmol-'ol4 trl+^J c=1.50101+. trI4^J 4l ol A4= -Bf, pvY=constant'9 Ee S-5171E q!+
2E .8El{ -Er+el.sJd trlE 67
fl zt9 a_Eql r]]qi ag aH zE2ql ++r]$.4. y> lolE-tr
EEd, P * 1lv +gd(p". li yy)g a- 7lg7l7| I *d(p* l/y)q A+E+

E"
EEC, P* 1lV rJ zlulErll LHEIZI+. olq* 7lol7l +4+= E?]qL4 0l+

E E"S S+ql^J= 4l L]]+E ollHzlzl-gE^l 4l+ gEl E
a
"lzlrJ r
mi
gE= "Jc6tril *zlrl7lq, lr-16}ol +g s+ql
6r
ullE"l4.
^JilH "J4"1 "*"1 tr{zlzl$zl
I
Fol, V ,.ttrJEt q 28.2
:19 2E.2 EEC= 7l^ll7l zl940e EE ts8-g ntlol +tr|oil nt= "J+ rogkpaollrJ ole=(/= -i) pulzl 2Hll-e. ¤ rllzlzl
^lE-
Eal.= LlElL.!tr|. EE rl.goil,\1ts Es.zf Eolxlo+ 0l rl.¤oil^l=
-
rl¤ zI94 o + rqI E t¤4-" + S+^lAg qlel al+ .J
oll^lHtl gHol trl E4dlll EqCq.
ee +-Sl} ?"1 Ect.
tgzl 9d zl4l9 A+ql= cr-=]Rol{(e4 ze), co,-=iR
o, =(+)", =(
;)"' x (r oo kPa) = 32 kPa
(Q,--cu*=R?9-e-), 4eI^J /=:ol+. E Eld¤ rlflz1 E
zlel A+9lE cr-=3Rolq(Ba4 EI4l Eldg g + ?izlq|
Pvlz} tg +eql^l 2Hl]E +7I6IE 4+ "Jqol sokraol
{5g tr-gql^J 44 zl¤zt $.4) cr,_=4R, ol4rJ y=*o14. gtrl.
tg Hclql '}|¤I *e ']] +E] +dg EEdol+r 6l+ql,
T}ILJ=
=s-d
tr r. 714]71+9 s+g El rllbt:z4r "Jg B tril) : s-E7I B a 2. trJECe +g 4Cq^l "Jqol +slql El4 qBzl H6l-=zl
qd+. E +4Lll= dol4.
=sEt^lE
,\lOE,
zl AI
'1
;z.---l1
I HE
^]
trIcd EIlZLol ol
L-: e. O Ci ----l
=
w"4=CyLT 9d zlill 2E.T
46 9e Tr=Ti(VilV)tt' 9d zl4l, rlq tseL 2E.2a
c=Cy^/R
V,T;=Ytry 2E.2b
rfod ,(l 2E.3

Li a L-l P{rr=P,v,T
y=Co,^/Cu^
68 2 1E=.1
E71
^2 1E=l
gEq t+ol flsE E= 7liilE-g ${ zliJlep z}{af:r gs}tr}zl qlolEl= zgs.rsrglrl9 a}5l1 e-o}e}.
tr4 2A LH+ ollLl^l
¤B E8I
D2A.r +"J"J +zl4 "J(HI-S+ "J)Eg "Joll sotal. D2A.4 E?-ls}+q^l '41'e+'tlq'+= gq +"J"J +EE ¤E6Ir +¤61
q4.
D2A2 zI9 Sat4 HlTIq S+g ++61q4.
qB4 "Jsa # flg+i D2A.s E?-l+olql^l g.!+ "J iI"lE ¤E6Ir" $z|;3q1^l olE
D2A.3 zl^ll9 s".g "J+g Îolel
9 "llulzl =91=el ,I4l+= tlzlt- ¤E6lq4.
G-\
JH
E2A.1(a) tts4"1 50cm2oJ qÊol Eil ¤-rl "Jqlc Elqr t}Sol "J"l iJ¤- +q 6}ql^l 7lq4 o s 3s6 K-tr 7ig6}fltrl. 3l+ s
^JElls+El "J4
t4. ol t}$"l oJqB_e__e,*-l ol ulÊ¤ l.0atm9 el+ *qql "*rl,tl 4,1u, q,")rE 4lt4q+.
l5cmE'Je1+7ttrt 4l7i ¤I .Jg AltI6Iq4.
E2.4(a) 310Kqlî a.sog9 q;g,r1ezi n1dm3E +qE ilzl6JE+. (i) ol
E2A.1(b) BEzlol 75.0cm2oJ ElÊol Bil ¤-zl "Jq^J q+ol Hi*ol .J
qwl. q+ $qql *^l^J zlzllzl200rorr9 "JAqI e.l+ $qql *^l^] Fulz} 3.3dm3 "3;'
ol HI*ol "JolBse.*l ol irlÊe 150kpa9 =qB
25cmE'Jel+Aq. 4lz\ oJ "Jg 4lt6lqel.
ri{,ttz]| Fg S+6J rll Bollxlb
"Jg 4lt6}¤4. tiil +Ag Sat"l zI9
V 4 o e "Jqg oI Bollxl} "J3 ¤"IzI !d,=+i
E2A.2(a) 20"Cq^l l.00mol9 Ar (i) 7tE4 o e, (ii) ol TlillE :a{¤, E2.4(b) 3osKql^l o.sog9 olE-* 18.5dm39 +slE ilzlb}trl. (i)
q+ ^l-e= ^1f,71
ol zli\lzl zjkPa4 "JC6J el+ Sqql
"Jq4 5g.J "JA "Jq 6}ql^1, f_?]r (iii1 z1-95;r1l(+, e.l+ $4"1 "*^l^J Pulzt 2.sdm3 "J+ EqB
o"J ull) 10.0dm3o e+q :o.oa-3o e Eo-Q- Satrld4. ol
^ll
!+aql q+ 4lzlzl rE"g s+6J tril ¤6llzl= "Jg 4lt}6}q4. (ii) qag Bat"l zI9
q, *,9. AU= 4l4i6iq4. 4 o + "Jqg 4 B"llzlb "J3 9t lzl EIA.L+?
E2A.2(b) o'Cql^l 2.00mo19 He rl.E.E (i) 7tq4 o e, (ii) ol zl{lel :r15:
E2A.5(a) J¤ Etsll ?l?]E ol+6l.q 2s"Cq^l zlrll {t_e_tr 9l= (i) rr, (ii)
"Jqr+ E.J'J "JA el+ "Jq 6|.ql^1, r41 (iiil 49r5.r11(+ el+ $4ol cH4, (iii) QHu9 g .I+ qlqzl= +6Iqq
oB 4l),s.0dm3o P+el zo.odm:o + ㅇ r="g. S+^l#.4.
"l 4Aql 46Jq,
^ll E2A.s(b) +F +Hll fl48 ol86}q 2s"Cql^l zl4l {te-s 9l= (i) O,, (ii)
*'1 auE alt6lq4
QHu, (iii) 4* "ilulzlE +6Iq4.
so,9 E
E2A.3(a) Cy..=+RoJ $A ,l4l l.00mol9p,=t.00atmr} Tr=300K9
^ltrzl-${ E2A.6(a) (i) *q, (2) gE (3) "J, (iv) tlBEl + qL 1"1 t4 6}+0l+?
{'-4e+q ge +q 6}q^l e-+ 400Ke. 7}96}s.+. 46 s
^l¤- E2A.6(b) (i) +sl, (2) g, (3) 4+ ollHzl, (iv) trJE + qL ?"1 t4 .Jf
4,1u, q9-w= 4l,t}6}q+. ol4l
$d zlill EzI
E2A.3(b) Cr.-=5,RoJ z.oo mol9 pr= I11 kPa4 T=277 K9
E4 28 gl=tr|
¤B E^ll
D28.1 qI EeE gA Sq g+*ol "JHI4ee r "JA-+ul g+zlE+ D28.2 6Jr+Aq EilqlLl]+qlLJzl H+e+qlgirl H3r}^tolg z}"lE¤B
olf¤ ¤B6Iq4. 6lq+.
=
G-\
Jrr
E2B.1(a) qE $d zl{l z.lEel "JA-%}q ¤*=}"1 cpl(J K ')= 20j7+ (ii) "Ja+ +q 6}ql^l 2s'c_E+El 100.c-e g4e 49 q, w, AU, "l
^1,
0.366s(r/K)q EI+gEq 9+6Jr+. "l zl4l9 gETI (i) "Je+ sq 6}ql 4lÎ6Iq4.
^H=
EA 6e
E2B.r(b) qts Sd zl4l g**ol "JA Eq 6lql^J 3.0mol9 e'G)"ll 2zelE gluJxlE ¤-E_,tl zlol
^lEE "Ja-Sq ry(lK-')=20.17+ E28.3(a)
0.4001(r/K)ql tII+ gEql 9=.J+. ol zl4l9 gETI (i) "Ja.J sq 6I flqq l1tr9 SszI 2.ssK "}fr g+7ttrt. ol zlz-flel "JA +qs+ "J
ol
qlî, (ii) "Ja6J+E 6}ql^l o.c_s+El 100.c-e. g4e 49 q, rry, AU, 'l C Sq E g*=*# 4l4}6}q+.
4lt}6}q4 E28.3(b) "JA Sq 6Iql^J l.emol9 zlill $zfoll 178lel 9luJzlE ge^J
^H= 7I6I9qq ol .r.le9 ¤sz} 1.78K n}fr g+Zttri. ol zlillg
E28.2(a) 3.0mol9 O2A 3.2s atm9 oJ86J oJq 6}ql^l z|$a|flrJul : $ "Jd-+ele+
E7I260K_tr+4 zssK_+. g4A+. o,9 "Ja-"Jq E g++g 2e.4t Kl 'Ja-"Jq E g+=68# 4lt}4q4.
mol-r-E *a q, AH "l AU= 4l4}6}q4. E2B.4(a) Nr(g)+3Hr(g)
- 2NH,(g)9 Hl*ol 2e8Kql^l "JqB qg
E28.2(b) 2.0 mol9 Co,E 1.25atm9 "JA6J 7}g6l9qq
Sq 6Iql^J aH,"-au-g <lg al&6}q+.
-r gE7]. 2soK-tr+El 277Ktr- g47ttl co29 "JA .Jq E g¤.+g E2B.4(b) cuH,rou(s)+60r(g) -- 6cor(g)+6H2o(l)e-l t}*ol 2e8 Kqî oJq
37.1U K ' mol-rB *a q, AH "l AU= 4lÎ6Iq+. B rlel aH--au-9 (Ig 4l4}6lq+.
EEf 2C EEI+
== =rll
ozc.r Elqr HsI+¤q +HIq= qlBul Hsl¤ +ae + fl= g al"*H ^l-*g$,+.'gd tlgvl:
r4n'="8 SlBsl'4ts S¤ol rl laJaf, ol.$
+ TizlE ¤B6Iq4. E ¤B6Iq+.
D2c.2 '$= tl4'e|'71= ^JEll'e.l ilol= "J6lir, olE.el +E= "5"1q4. D2c.4 dq #ol "J q= *ql^l= Eq 4^l 44.2?+g'Jq^l B"J a
'S4'¤lf4r'+gg'ol+= ,1-= Eg + 9l+. ol %}Hol -tr44oJ olf¤ ¤B6rq+.
D2ca -EBol +61 E E¤ql^J ¤'^J4 o +
G-\
Jtr
E2C.1 (a) CTHTOH(I) + 3Or(g) + 2COr(g) + 3HrO(g) HI*{l Elltll ^J= 2e8 Kql E2c.6(a) HCI(aq)9 -E= ^8d UBulzI -t67kl mol rol4r alH aff(cr,
,rl A,u"=-l373kf mol-rol4. 4n"g zl&6}q4. aq)9 7i3 9olzl9Alg+t
E2c.1 (b) 2C6H5COOH(S)+ lsor(g) -+ l4COr(g)+6Hro(g) HI*q q4^J= E2c.6(b) HI(aq)9 g= ^8C tlBslTI -sskl mol-rol4tr alH 4rf(r, aq)
298 Kql^J L,,(Je =-772.7kf mol-tol4. AiU"E 4l&6}q+. el <ig B"IzI941=*i
zlE ¤9 s. zC.+9 qlolEl= ol+6}q C(graphite)+H,O(g) -
E2C.2(a) E2c.7(a) 120mg9 LlsBfl, C,oHr(s)$ HI*F g*4ql $l fler17q
4.J (i) 2esKel (ii) 478Kql^19 4u"g| a.u"E al4}6l.q
co(g)+Hr(g)ql ! es.z13.0sK g+2t4. "l ¤*4lE g%+al ^J+E 4lt6lq4. +ee
4. ol &s gq"ll^J olE Eeq g++==g gEql ++6}trlr. 7IA6lq 3a 6l.ql^l ol g"*4lql r50mg9 El5 c6HsoH(09 Br ¤d^l7lE g
4. Ez| gulrJ 94z}4gr*? (AcFIe(CroHe, s) = -5 I 57 kl mol-r.)
,+E ¤el s. 2c34 2c.4E g^ tlgsle+ g+* rllolel$ ol$
E2c.2(b) E2C.7(b) 2.25mg4 "JE+dl, C,nH,o(s)$ HI+F g%i4ql $-l ga,<14q
+q qlH(ol^]lBfl)ol qlfl(qlBHl)o+ +^!f5l= HI*E 2e8Kq^lel r-l gszl 1.7sK g47ltrl. ol g"*4lE g+zl t'"+E 4l{}6}q+. +ae
Arr"e+A,u":a-l-tr 427Kq1^.]9 A#"= 4l&4q+. ol ss. gqql^] g aa 6}ql^l ol g%i4lql r25mg9 415 cuuroH(s)g'Jl gr,<l7lH g
++==g "Ja6iqr. 7}a6lq4. Ez| $ulu| 94z}4Lg4? (A&e(Cr4H ro, s) = -706 I kl mol-r.)
E2c.3(a) 2e8Kql^]el co(g)9s= ^Jc qlBq (l(xlE e)4 s 2B.lel E2c.8(a) oI4 HIg (1)rI (2)E ol*6lq 2e8Kql^l (i) HI* (3)q 4.J
gE-E= g+%r 4lolelEol*6lq c(graphite)+H,o(g) + cor(g) HI*91 Arr"el A,u"E, relr (ii) HCIG)9| Hro(g)oll 4t a,a"E +6lq+. (g
4aJ lfi"(sooK)= +6Iq4. E= A+ 2e8K-e. f 6}q4.)
E2c.3(b) 2esKql^lel NH,(e)9 Ee
^8¤ SIBEI A(zlE' e)r+ E zs.r9 (t) Hr(g)+Cl2(g)--+2HCl(g) A,He =-184.62klmol-r
gE_E= g+* EllolEl= ol+6}q N,(g)+Hr(g)-+NH,(g) HISq ql6J
a.He(7soK)E +6Iq4. (2) H2(g)+O2(g)-+2H2O(g) A,He =-483.64kJmol-r
(3) a HCI(g)+O2@) +2C12(g)+2 H2o(g)
A*#" =30.0k1mol-rol4. 2s0Ke+
Îgs+*^g +g tlBsl=
E2C.a(a)
rbargl^l 0.75mo19 CCt40)= +g^la oll9 q, w, LH "l AU= 4lti6}q+. E2c.8(b) oI4 HIg (1)r+ (2)E ol-&6iq 2e8 Kql^l (i) HIg (3)ql 4+
E2c.4(b) ql+gg +g SIBEI= 4"0H"=43.skl mol-'ol4. 260Ke+ lbar a,H"e+ a,u"=, r4a (ii) Hr(g)c+ Hro(g)oll 4t ArH"E +6Iq4. (¤.
glrJ r.zsmolel crHuoH(l)g 6"J^la 4lg q, w Nf,,l AUE 4l4l4q4 E* d+ 2e8K.e a6}q+.)
E2c.5(a) qlBHldlE s= (l) Hz(g)+Iz(s)+2HI(g)
^JC SIBE= -l2.skl mol-'ol4. .g= E+,
qI A.He =+52.96klmol-l
gsl= 4l&6}qq (2) 2 Hr(g) +o2G) + 2 Hro(g) ArHe =-483.54klmol-l
E2C.s(b) uil=el s+
^8c {lBul= -16s.0kI mol-,o14. -tr= ¤^
qlBEl (3) a HI(g)+02(il+zIr(s)+2 HzO(g)
4lr}6lq4.
=
70 1E=l
EEf 2D gEH Er-+el eJE EIE
*=
=xlt
D2D.1 ¤ld zlAlzl Hld 9s= *zl ?*b "lf¤ ¤E6Iq+. D2O.2 vanderWaals zlillel LI+ qlqzlTl gc6J gEql^l +qq IrI+
qB4 H6llo} al+zl ¤E6Iq4.
G^
I -tl
E2D.1(a) q¤ EillE Pulzl-tr]^gr+ aol gEql 44 H+tr}. ¤9 EllolqE "l+6}q 2e8Kql^JE a4ill udql
E2D.3(a) z|-e_ E}]+
cr,.-cv,,g g g+=* *+le +4qq4
E2D.3(b) zlE dE EllolEl= ol+6}q 2e8Kql^lel "-4!l q+gq
v = v'10.75+ 3.9 x l0-4(T/K) + 1.48 x l0<(T/K)21 EI6.J
cp,.-cv,,9 E g+=* t+ls +41ilq4

¤zl.,.l v'g 300Kql^lE +r14. :zoroll,rl ol .4iilE s+ 4l+ oE 4l&
6Iq4. E2D.4(a) ;6,21$ zli-llE Hl1 t.0obarel 400Kql^lE tll+
vanderWaals
E2D.l(b) qE "-qillE F:rlz} trl-*r+ aol
gEql 4+ H*+. 4 $q rr=atv,l* +6}qa}. 41'tlg t+s}6l7l +l6flî ol zlill$ 9d zl
ills 7tA6Ir. E +ul= +4q4.
V = V'10J7 + 3.7 x l0-4(T/K) + 1.52 x lOr(T/K)2) E2D.4(b) olt}e}+g vander1,y6n1s zli.ll-E H? I.00barel 298Kql^19 ql
¤zl,rl vg 2e8Kq^lE +rl+. :rorgl.,.J ol o+illE S+ 4l+ aE 4ltl

+zl sq rr=atv,l* +61q4. 4l4}g EI++6I71 +lB|l^-l ol zlzllE 9d
zlill-e. z|{op. E +tl= +6}q+.
6Iq4.
s"g.J+E rr.t: +.l6xl0-sarm-toltrl.EE E2D.5(a) vanderWaals zlzllgl q6il^]= rr=atV,lol
E2D.2(a) Zg:f"llr-]9 EE ^dBq}tr+. 298Kql^J
"J
44. zlAlzl 1.00dm3o ++El 20.00dm3o + Fg B+g B trltE AU.g
EE 0.rovo +71^l7laJfl $uiu3a3 "Jqg zl8rl4"F 6ld,e+?
E2D.2(b) zs:r"llr-19 SE E"g "J+E rc.,E2.21x10-6atm-,ol+.Bel 44i6}q+. E q* w41I9- +6Iq4.
E2D.5(b) 298Kql^l olg+ zlzllzl l.o0drnro +*q :O.OOamro + .:aog- $
"J
EE o.royo Qzl,<lzl4E g"|$al E-eg 4+^l4oh 614-+?
+g.Jtrl-. olstql q6fl^l g+ E2D.s(a)el 4l4}g l$ol 6Iq4.
.tr.4 2E EE EEI
¤E E^]t
D2E.t +g B+g +4,]l= g+*ol Solzl.b olf¤ ¤B6Iq4 D2E2 p¤ vql 46li^l E^lE} rll, B¤dol Fgdtr4 zl-sl= olf+ +9,
^lql ol+?
G--\
r -tl
E2E.1(a) Cv,-=20.81K-' mol-'?l 1.0mol9 9d zlill tsÎg $ rlezi z-l 6Iq4.
*91 a.zsatm4:oorcE LlElr4fltrI. ol zlz-ll$ 2.50atmol $ rllzlxl zlS E2E.3(b) 97.3Torroll,<'l 400cm3t ;6,1 /l-PE ,iq +94 o e S+^l
t94 " e S+^laq. !+ +El, !+ gE f4I 46lla "Jg ah}6}q A 4t Pulzl s.0dm3ol Elrll 6lHtrl. ol .r.l_8.9 3l+ sq¤- 4l&6}q4.
+. /= 1.39 fl61q4.
2.5mol9 9d zlill +zlg $ r.lRzl. zl
E2E.1(b) Cp,.=20.8f K-r mol-roJ
E2E.4(a) +F +Hl] fl?-lE- ol+6}q 714ltr-sELlo}e+
*"ll z+okpa4 32sK=.+ElrllfltrI ol zlrllg r50kpaol E rllztxl 7l.E t "lltsel y=c/cA
Alg qB6144. ol Al,tlg tlEel qlHzl9l q'J TlqE rel6l-Z E rel
¤4 o + 8+^lA+. !+ +ul, 4+ eE r4I d6ll{ "Jg 4lt6}q+. 617,l gir. 4l/J4q4. qL +ol 2s'cql^lE ¤ezlql 4 zl*A-42.
ol.tl3r}+^ zlzl6liQl, ol E2E.4(b) +FEE|| Ee]= ol+6}q qg6t
E2E.2(a) 27.0"Cq1^l Z.+Sg4
^1f,71500cm39
q4l 6}fltri. ol zlillz[ fl oJ
"lts+ts4g y=C/c,,g <tg-
,lE +94 o e s+^14 l.oodm,ol ¤4. ol 4lÎg AEel .ilHxl.ll qitiJ 7lo1$ r.el6iiz E r.el6}zl g:n
^lEE
g al4}6l.q?+. qL +ol 2s.cql^lel deilql Q zl$l)Lul?
4lÎ6Iq+.
E2E.2(b) 23.0"Cq1^-l 3.1299 ad ilzl6}=ql, ol rlEE
^l_R7I400cm39 ol E2E.s(a) 273.tsKql^l l.0dm3g i}^l6l+ 12.0g9 ols* zlq +g
,lq +94 o-e sJ+^14 z.oodmrol Elril 6}fl+ zlzllz| qI "Jg 4lÎ ^lE=
6Iq+. 4 oe. S+^14 3.0dm3ol slal 49trl.. ol .r.1tr9 4+ gEE 4l4l6}q+.
E2E.s(b) 2es.tsKqlî 500cm39 i}^l6l+ 16.099 ol&3r++^ 7Iq
^lEE
E2E.3(a) 67.4kpaql^J 0.s0dm3oJ olt3rl+^ ,IE +94 o + strI
^lEE t¤4 " e *+^la 2.0odm30l Elrll 6}fl+. ol .r.l-E-9 al¤' gE= 4l4l
.r.l{ z.odm3"l slal 4fl+. ol .rl-89 4+ $qg 4l,t}6l.q4. y=r.42 4 6'Iq4.
G-\
L:t= n,l
, t
EvILZ 1E5l
exlt
=*=
t2.t
aqilltI4 EE g ¤+*g JrI4 o + snol4. 3"6J4 ¤ixll lz.z9 z-l r"ll 9oll,rl qE4 ¤o.lg BEzl ^84611 _u"t4. Pylz}fzlal$ "Je +
g + E1g,ql,rl E"l "q4E dcg a+ E= HI* $g4= gE ^J+ql trl q¤E7I,t]l zl ]lLr-[ E= E6ll,(l Ae+?
u|4 6zla}4llt+ E= rJi6}4ls+i
tz.s tr4 6J+E 9lE ==,L ol5ol gq+ql^l Ell+61 +st qgg 6I:
t2.2 E.E zeel $$z[s] t4 eoll,t.l ffi$ Ae ++ E.J+E Cdg e ol+= ¤E6Iq+.
.J Hl ?l+.
12.6 E¤ ¤41 'JBg "l+6ll^l Ba1;4n1 gel+4 ca¤. =rlB
¤.zl
( , ral ) -t'a rqrl ) + ol*alq ql++El Sl*zlzl9 "Jr.h=ql El].J
9lr+. (a) 4u-e911olE
ay ( ax ), 4l4I6Iq4. ol {tg Alt6}e{H E} dB4 H}B(qls^l AMlolL}
).- [ (
ax ay,/.
I J, ^.n"8
HIH)¤- ol-&6}q CnHrn*,(g)9 _E=
^8c dBulE +6Ir E COr(g)
pM3
ol C44 ze.r+llg olo-"o|{ @Cvtawr=
u4 zzl E.E+.P +E}.ll-I. e+H,o0)ql ElloJ s= ^8c $lEElel dETlE 0l¤-6110} 6}+. o) eL^8"1
6utd14r +4lE +6Iq4. olq^l 9d zlzlloll 46ll^l= 4l&EI alg zlE. ¤9 s. zc.tq A#"eI ullalr" olq^l EzI e¤ ¤41
"l4,4 ÎolE ,o].BE 41e1r9l +6ll^l 5g
(acvlara r= ool E¤ -E-q +. "5oI{4 (c) Afie=6onstx{M/(gmol-'11'o1
6|= 6JAIE *op_r, conste| n9 #9 +6Iq4.
rz-3 Tli]lE g+* ul$ ol$al$ : zl4l +ql^19 f,$ c,=(yRTMlrrz=
AAg + ?ltrlr vy cSc,ola_ M? zlill9 E eelolq. IA(BA4 qd 12.7 8E= }.q¤ ql HI* tlBElTl +olzl=zl *"lzlEzlE Î^1l6J al
gFol gc"J)q^J (a) 2sx} gxl., (b) dB :sz} ExI, (c) ulcB aflx} 4}g 6|^l g:r.E ql+E + gisB se" 6J 4lz} zl-? gl+. dB gz|_e. E
+zlE ¤ Sd zl4l 491r.'le1 ¤+g +4ql= 49 +E6l¤4. zs"c9 7lillg ge g.q E g¤."*g *rI4 " + +RoliL tslCB +zle B zlill
ql ql6J ai3 +nol4. trhg Hi¤¤E e= HI+ SlBulzI9= f;zlq1 44
*71 +ql^lel ¤+g +61q4. zjralizl aa6}q 4.
t2.a ie} ÊellE^lE=-
ol*6}q ffi .$rll$ Eol4. (a) =:7161+zl
(a)
29sKql^J ÊE9llq+
l.0mol9 Co2@)zl. van derwaals trll^lg ElEqr u;r :z P 2Hr(g) + Or(g) -+ 2HrO(g)
e+q l.omro + Fg ,Iq s+B oll 6l-= "Jg 411I4q4.
:rlzl-r.0mro (b) CHn(g) + 2Or(g) -+ COr(g) + 2HrO(g)
(b) S+"1 7IE E"g4oli1$d 7l^ll"J q $qE Pul 9=szlu}4"lel (c) Nr(g) + 3Hr(g) -+ 2NHr(g)
E,la3
zH47l 3HEl
qE ¤tl-e z|fl{e_e. gq+r" E qH ae:B4 ?}+. a"ll"t 6J+. ¤ " =J"14, Eelzi HEI r+Aql^l gE^l "ldq
"143
ol -f9.qlzlz| rlEl{ E!trtE %16}.9 C6I + E 9lHzlE +A"lH EA=E qlEei4E A¤B + 9l+. E
^lltrg
zl ullE"l4. xl$4 HEI* :z {ffi
9e zlErll "Jg gs- * ol Eqg. EE6IH^-] .gEo+E lBzl'g E4l q='ll, ol4,
_tr 6}zl ?+= EsltrI. ¤zlrl 6l+ ¤- 49 o1 nxN -o e E¤Eel q+q *g 9rq,<1E Ce# "16119 + 9l
,J-a4oF
dElql a4^J .ztB¤,ol+dezloe olzlg + fla fla 4 qr EeE qle +q9 ¤.I {tg acg + 9lril B+.
+4lflol zt¤4 a6.&g't44= 4, o + "ll4"ll"F +qE a 3C.1 flEetrlel E xlg
=Eg;
3C.2 3Ea
ol4. 8943 z}ts4 HirIrI gq+= dzll 4sq +ql^l
Bg4"lE, zlB4 ,+C +.il= HE+ +E7t q+ Lel^l
=
(+ololE= +PEl +gsE H+Lq= A+e+ ?ol) dAzls 4l +!+E LlEl"! ¤¤
e HElzt "J "Jq+= {ol llzlE 6l-r. E. tZ}4-" +(7lzll qlE +r4= q^= q BE6l-= Exll= 4le+ ++lql^l gq+=
zl 4* +e_E "J+61-= A+e+ *ol) "JqLr= aE fl+.
H34¤ zllBzl_e_e. 4lÎElot 6J+= 4o14. ol E4l= ++6I
zl fl"ll,H 4ql+ q¤ +{f, {lffi zla[{.t] EE+ aol
.Gibbs ollHzl,4.+trrql^l gs+ EH+Ee_l gqElzl
44}ql
3A flleer; ol Gibbs "tlHzl Hsl.il +"Jdg Fa ql-E eq HaJ¤
^l=
4d +a6}xl ?+41 qfl4.
Hslel "J.Jg "llHzl4 E4q EEe+ +4lqq, zlB4 Hol 3D.'t Helmh6112 ollulrl9l GiOUs 0[L1rl; 3D.2 E= E Gibbs ollLlxl
zl-"J94H 6}tr-qluJzl4 s.= E¤"I ¤.&¤cl. zllHg
"l
c%Ls+6t71 E"Jq= aol dEEq+= ca"Jql,
+1611^J
ol CAg'gEeL9 z$zl'g trJE= ql +C q$g 6Li. a 1H=lEt 2Erlel eEt
ol4. :z4l ol 849 e-= zl-*4 Hsl¤ zlulld4.
3A.1 2gr.l; 3A.2 1=erlel 89; Sa.S .sEil A+tr^1e.| tlEeEl al64 " + rEzlzl zBzlg *41 #-9" e.rAl gqqlg E.a
E CAg E6}E ql eg g+|tr + glrll q= aol+.
=
3E.1 L}|+ ollHxl9 dE; 3E.2 Gibbs 0llLJrlsl 8E
38 El-8Eoll +uElg fl!= +rl EEI

=8
oJ ESolf,<JE $l=_eqE CE= olSa}¤ zlill9 Sar, t d"l, fl 0l rlEel E-E=?
r?-ll. E{e-l zI¤ E"4 Ae qq Ft'-4q1 Epl4 44=ql ^1._E
.<'lel sleeul HsI alg qBril 41416l+zl= Eg 4"14. EillE B4^l7l= qlTlr+ Hl+* t}il= sq}q} E=
=+E
$1lE ++4 qBg 6l+ 4 ol zgzlol4. ol .ilÎE E Î
se.r ts8 ; 38.2 I Eol; 38.3 7lE; 38.4 +il rtE
ol=ql azflal ¤'J a9 BF zlH"ll +El ¤¤¤ -p"tz}. ¤4
dz} xlltr Ee9 E+E +E= C*4ge EEd+ rllE Ql
-e +EJE ra6llo} ++. +rl= +aeie-EAl
fl!=eulel îgql^JE flE
=8 adEille ol+q= E4E +EE q*rll trJg + 9l=zl
zHzlg C*4 " + ,44421 9l6li^J= EAg $E eq= + ga} sql i7I6}gtrl.
=
EE 3A fl! E+trl
gq-+el Tlel E+7|. fl!tr-+tr1011 714= E )S

ElEloll^1 0lE6|t=
olcl. fleen|E ol8ofE ell olE E4 EEILI Elql HJ- EoluE
!E GIE aa ?l golLl=^l= ¤EEf + ?lrl-.
Zl9flle+q Ea|ts Zloll olEEl= Eg 0l86'|G ZhJ-Ef #

razlel rlg4?l rltr8 ?lE+tr| +HJelrl.
?,lrh
/
J
(' rT \ 411
=7t-=
:el
:lal 3A.1 El.=HfEJQlll1 Fl=t[-d Ealq ,J-Bt. U E ttfltrftl
g, g, '; LH+ 0lll,l^l0ll Et-gt t H^.l9 THLI= T.!+6l.11 gtr ?1ol =oll ^1"J4
89 ollLl^|9 g+7t o|.=Hl=Jel EEE-e-=, 46fqq, 0l 0llLjrl7lECEtrl.
0F etrl(trE 2A). 0l trEloil^1= 8tE 7liilq "Jg g(E'l 2A)= 71^14?.1 xlBoll^1 0l Ej-'Jz qo+ "JolLl^l g=tr|.
0lE6f:il. s. Str Tlille-| 7fq .JE "J8oil +tjJEl= +trlelSEol
EE|(trtrl 2E)E olEg aol+.
Eolzl"h ++(rH 3A.2). g"J olq+ gg¤ig ++aql g
E"Jrll H}6l]^J +ol Flq 94zl4H +q flzl-Eol E+ *
ololg o}6ll^J ¤.Eldl]o} qi+. olsl¤I +4Lc6Ir. +e^J+ +
zlg4 Hslq *6&9 sa11 ;3 Ag +E"J7F gEqI lBzl
ql E6LH ++q dill qlqzl= qE 4aql E6I]^JE. H6lzl ¤.ol 6J^lg e^J4ql ¤+e-E +zlp+94= AZ AE +"J
g:e-EE *e qlqzlE tr-48 qEJr 6h= al} zlg4 Hsl
6J
"JE^J d4 Ez}+al4a +^l6}]E g+.'
" -e
+4= ol+lq} ztts4 H3rlel oJEJql 4t 4*ole
%r-6FlL +Al7l s,ol"F ++. tr|+^J ol "J.Jg glHzle+ E¤ ^J4g
9 EU}] ,J44 +4lElqot aJ 4,o14. ol ^J4g gq+ 2Bzl
tlg + 9l+. + .llHzlE HlrlzlE H+ %L'J"J *sE q
aol4. Fl= +q HsI "J6JE "l g?-lE ¤Bg'1.+ +!E
-e-e. EH6|]zl-,L'SiE+El'4= ¤d9 sEgrs-EAl C*sl = g¤Eo_q_E i&q= 4,"14. eI
vlTl ol+qe+. "llHzlb trl-=HIEI flzl-=9
ql HJ6JE HEIzI Hlzrg4"J olf* glHzlzl +zlslqa u|.
qE_ Hl-fl+=
flzl¤9 +"J6J ¤Eo 4,"1 Ezl-be} "Jolzl rll
3A.1 2EEl Eol+.
E¤E E+ E4lqBJ= Ao.lg zlzlt- 914. zlxll= zlg4
"l^Fulqlql^J fl= *&
zlzla gluJzlel EAE +& qBJg o + +=.921 g+EEll ol+al q4H zl;ll Ezl-Eol r +4Lc
rj{ollHz}. +ol Flq sE rll"}4 : +ol7} ¤q=3r1, o1
¤Eo_q__e. "J"l*oI ¤zl9 a34 f-$e_e EelTlol t;17) 6171
4* ol gF qlqzlE "J+71 =o4 trl^FHlql +zl¤9 gg ulEol4. zlg4 s+e_E^l zlzll $z|
E qlqzl_e. E^J9zl rllEol+. zlg4 HirI$ "J6Jg tE ql "le]. Hlq %}6J ¤+g
E"l H +q= ,'lzldl.Elr. 6l-= Eeol q z4 Bt}q
Hzl dPzl *zl* trl-Ftsl-Eiel 4E ++r1q1 olEE Ezl¤
Ela 6l-==zlg4 44zl q= 4ol+.=
el +4^J+ g¤Eo e-E Etq=
^J4ql
ols. aol4(:ze
Eq-+E 2E=lg olel+ aE# H+ aq6}4l +4Lllq,
3A.1).
ql* Ei{E ^deel flql"l q= Ezl¤q q# E^l 9+=+.
,rle^+ z$xlap
qi'J *"1 Flq s_=
"|*Htq flql 7I"Jal
zl rl4tali "J3 Ea S4. *"1 Flq ee4fl a; "l B4g +4d 4ol r+s=4 tSret"in s¤ol+.
=E+
F$."JzlzI "JqLI"F +trI + +d a4lg I,l^*HlE+el g+F gg_oe+q gg ¤+6Ir ol gg d+ _a ezl "JE"J
qlulzl "JPzl-+ z]]9 49 Eill?l +ql +4qqo} aJ4. H+^l vlTl= r+Ae Bzl$.4I4.
"l
+Al q4H "l^Futsg ol-=L i$.ol *g g4¤E rlE ql
gz} +e_E gel
r "lrllul zlill 4q e&g 4|g g,8olEg e%Ie"J6l= ^lE ¤+?l Brown
ulzlzl m}4'+e+ +g ol? Hli/4 +Eql^l= gt 1ig +'/ + "lele} a^14.J ¤¤ol +4kltrl.
= ^+E
추가 열일 3A fllEetrl 75
t/ ,l
1t|
lr EE4g ga EE718 gfl
rl r lg
4
I tre^1 j
t oilLj^l \t ol
) ..:- =
-'
I
(b)
I
(a) (b)
Et +ifl
fal 3A.2 (a) ffi-g ul'+oll g+Gl9t= 8; 3rl-=3 al¤E-+ Ell-d H|.e[
(a)
:Lrtr[.
'JP EAAqT^l= LIE-)= (b) A0l Flcl a=a{E +4r8:d T.!E EE-g fal 3A.3 (a) Ezltre n:1& EfleE+E1 oilLl^t= Etr^ Eol-L|'|r 0lol^1
:g
"J+71 tr84?l EEo-e E6t|0F olzi-d
aolq'. E+e 0l 01lLl^19 g+= "J-e upa Ll'Blrl= rl Eg(E+iDolltrl qaE E|iltl.
,\ cHrL
oIAJL-I' -T- ^l-dd =ilaJ
=vl=
HtiLl.
(b) 2E..lslKelvin s-d8 g0l Sddl ge E6PloJ 6lr += EtrtTl.golLl^l
g= leJ z}¤3 E7ltsidltrlts 7ioltrl.
ole+ag 2$zl E¤g ¤zl*:zfl :n.l(a))"]+r al} "l1l

4 tlil$ zlz]t- ¤4-zJ o + EF+g + 9l+. ¤zl*.$ E4+
gg('r-gg)4 & gg('g-+4')E F gfl"-e qq ile {zlrJ S.,$ dill rfl4le-l dill tltrei{$ +4U+. +
q, + gg gs^l s.-e= qlqzlE g+E "JE E++ c 4^J 419 Ql-= +ulE
=
s, ++]el $lE-+irlE s,u,ol41 6IB
Îols
ggg ¤Afr lol4.Kelvin s¤e -r.-g
^lA + 9lE+ + 99ot ++. 2Bzlg ¤-s"g| oll 96l Ed6lloF
S,o,=S*S,,.ol
g"E+El gq="J gg $d6l "Js H++^lzlE ¤zl$9 ts a3 0l H4e dill4"J rBalel dill tlF +q= zla6l
"JE + H+= 4olrH:H :e.ro)).E= dxll9 ¤zl$Eg aolzl, +d 'l]^J alE fleeq= zla6l+ 4ol ol.,-l4:.
=
+ g +ill= 7l7la flg"F 6.JtrI.Kelvin .E.¤g glql^l olEl 4o14. trl-¤= ¤ql^l SIE+rlE CE6ljr" olag 9lHzlg+ E
EE6J ulg+ ?ol trl-*Hlqql azl6}_r. glH +ol a7 z}ts4 AE E& eE. +4.}]= 4tr+ 6ll46ljr" z)]tlzl EEQI
eE Flq a Ezl ?*.4= "Jt4"J aEg "JHl+^lzJ 4ol +A Îd$ ¤+^la aol+.
4.*ol +lE +lqs=+= a3 "l-Fulqel ¤ol "Je H+El ,q_qI"Izl-E r$zl* ,ll+ qlq \$ zlzlt- q+q= HEIzI
ag 9"1d4. 9H 4"JzlE B16l+4, zBzlS fltr+qE ol+6lq oleJoJ
=z$zl9
4E s 6I+E S.¤g r+q=r} B¤ nudolf Clausius -d+q= EEI¤ +ql^l qH 1,"1 zttszl HEI"JZIE EL-d=+
E s¤(rH :e.+1o1u1.
gg & EllE+El E4g Eille zi$4 "-e aezl .e$
grI
L t.
tr-+ E4+ Eills E"l oldElEJH B+rql^Jel ?-ol 4l9l

+ "Jg 6|]+qo} alE 4o14. Clausius E¤rl Kelvin .trBol EE4g +i]|
+ g+ EolzltlJ ol + E¤ol ts44 o + E"J6r+= ag
Eg + 9l+.
+d 4le+ r ++lE "I+e-l rB4lE E=Ell, "lag +++
-L "Jg +E 9l+. dzll 4le+ ++l Îolql^J "Jq+b qlq r
zl olde- ol 4rll6J rB4l "Jql^l "Jq+E 4o14, trl4^J
qlqzl= i-olezls- t*l 4zlzlE ?*=4. "lolrJ fl!=eq s
+I 6I= ^l]E+ tr-=I gL+E zlzl:t_ 2Bzlg r+s_4 *".l 4 T! Efl
4U+.
fg 3A.4Clausius9 2g.l E-d= 0llL1^l7l & Ege.-"+E1 *Ze E-
:zBAlzl ztg4 EEI¤ "JezlH :. 4Aql^J 419 Sl-= al¤e
+i}|E Ee,t1 0lE6t7ltrJ dF= oleJ Ut¤P E7l-=.-l-Ll'= A0l+. oleJ
gi{T} fzlollo} *+ AS,o,>0 qlLlrlTf HEE= e 1 g^lrl.= E+Elrl g=rl'.
을
76 2H=.lrl3H=.1 Sas Ds
f = Tifdorer
=
3A.2 fllEEElgI EgI tr|+ l L[J=Q+wolE.tr- Q=-w7l 99 q,.,=-w.""ol ¤.tr].

719 E"E S+ql^l eaflzl= "J3 ol"l Eq 2Aql^l 4l&
2Bzlg C%+4 " _+ f-s" * o + "JEzl 9loll
oJts rJ rl"Lz|
619+. E-e-a E Sl-=+iil Hsl+ AS--AS/ng 0l-$ofl,<J
^l
q4 +"JqI 4d=ql +qlq= qltr+ul Esrl¤ ael6l
^l= 4l&6J+.
a 4l4}g f ql{o} d4. 49= -zd4"J Aq Ez} i6
ol
E .F %LHg ol$-aJirll, olE9,{e _H_$4"J q6J¤. q}+. EOI s_Ez[ ${a}e_e 3A.lb^]ol r-l-o-$ ?"1 ¤4.
(a)S!=erlE Eq:qt4 gel

as=|Jta e,",=f
flE eulE gqqlzl celE EeejH Eq4 4zlE slEzl e.9 znoll el6lE rq"g s+ql^] flBllzlE zI94 "Jg
HElel a!+tr ^8zlE sls_+u1 HsI ds= d¤!4 " + ^J45il w,e,= -nRT ln( %/ yi) o q, qzl^j 4ro,= nRT ln(v I v )7 I g+.
I r
oF *trI-. ol eE= qlLJzlTI E&q= CEel Esl+ 9"I4 rEr "JHg rE ++ts trl+4Ae+48 E4l g+.
B:g qlqzlz| p-tr^l oldq=7}ql q¤6-J+= ^J4e_E+El
r"Y,
Llg aol+. olul tr_9 zegl! ¤Efr ulp* ?ol 9ol "ldE
trI= +fl flzl¤9 +a^J6J efol zH¤+. rfl+ "Je +
AS=
"nnl rr-l
7< AS-=ft
rtTl g7l3A1 "J{"#el $d zl4l9 "J4"1 p,EFEl p.a

+lq fl= gzl¤el +"J6J gf,$ zffi^l7lq El+^l Ql= + E"94eE He+ts 419 ql=-eel Esl¤ 4&6}q4.
q= H+^lzlzl ?+=4. "l
Hslz} +9.q zlolslLuf?
flE Pq. gqq}4ee aE6l= ql= +94 ?9 401
ER h+ bh Er?& hkf59- .B ltlYlt:(tdt'd)utuu=sv 'E
ol+¤+.
at:f flleeu; H+ tlell (3A.1a)

E +4U Qltrerl Hsl.ll +qI Cqql E6IE g
3A.1a4] o
E^l oldq= glHzlE at)g r4r ¤.E= 4{"e. u14
q7l^J q,*e ¤4 3s rql^J zI94 " e 4lql oldq= gol
4H fl=+q9 Eglzl. Jr-tg -tr^lg+. $Eeqb a7l d
+. + ^}4 ie+ f ÎolE +6J+ Hslql 46ll^l= ol {$ ffi 4o14. 8leeu15 EAB:se +b E ?lee.u1 s_=s/n3
4 ?ol 4EB + ?l+.
JK-'mst-' ++l= zlzl:il- ++u+. 8 tl=e4E rllzl c¤
dQ,,'
AS=
I T
(3A.1b) "l+.
:A.1a^19 AE. ol+6IH ++lel tlE +rl EEr As,,.ql
+ AlE "JEE + tl.ll
Îole-l
fl-E +iil zl¤ 4l&6t4ts ol +6J !g "J= + il4. zl# ulAal ¤ dq.",ol ++ls oldg
+ tF4 Î"lE 7lE4 AEE. *j4 olq^J ol A.E trg 4 "l Q-::. a121. ++l= "JA+ +qE ¤fl"e. qqfleq, :a?-l6l
+4lql^'1 gE^l #qE {lulzlE r qlE gEE ++q ¤ zt¤e,Rl ;7g .llHzlE ++lel 4+ qqzl H+ du*4
^zlzlt_ 4E6IE g+. 7JE+:.-H+ qqzl= tlEll Elioloe du,,,g $d
"l$ol4.
olag du,*ol HE+ aEq ++6Iq, 561 ol Bs+zl 7lE4
EEU Ed 7tdt7l
=e
gatEt uil9 ae=q E oe. oJq4d s= Hl7Lq4-o+ "Jq+a +4lH+= ag
E[ 4ht 9"le}4. "l ^l{g dU,,,I+ +gg dq.*qls r{-tr- 4+E+.
$d zl^ll ^leel *ulzl y,E+E yre Fg S+6J ollE EL+^l :A.la^19 C9E ols-"o].{ 'revol+= aa -E^l= trll
flE +q H+= 4l{}6l-q4. -:r. r-l-e-=q- ?"1 # fzl ?14.
zE{g
Êl
*d $l=.+ulE aE= ol+6}rlE +qd
il¤. t'-4el 3l+ tlEI ol HEIzI dxlle qtr a +9le-l g!EEtrl E+ (3A.2a)
Îolql^l ^r.=*
Eql q?+ "Jq+a +41$.ol T}qzi asql^l E+q= g
S"J otq+ qtr Hslz} "Jq'Ia +flE gE= "JA4q, q
g "JolLllo} 6J+. ol rl¤g ¤ig Hololo + r= tl-+E
4^l +6J* Hslql q6H^J='l+r+ ?"1 ¤ fz| 914.
+l+g + 9leq, 3A.lb^loll^l gE= zl+ zls q|e-E r.l]
_H-E + ?14. $}"J olq+ Sd zlillE 4+
"llHzl} :z
+ulql ++6tIrE(Eq 2A) o1 s+ql^J= AU=ool g+. z ol 4dgl ++l= "Jqol aE "Jc6I+r _u-otE 94, "l4l= dq** du*
+?JAI*+91trI.
34 slEtrtrl 77
AS,u, =
Q"u,
(3A.2b)
(b) fllEetrlel sal Eq-44 8el
4u.
gqql2Bzlr+ flE eqg aE= Ezl if;ql^J ql46].=
., 4lql T}q4ola HlzlEzJola qB HEIzI "Jq+a +al gdg d4l zl4 ¤ql^J izllt BoltzmannE EE" + gzl+ =
Sol, old$ gg:
Hslz} "JqU gE_E 4i4Azl"J 6IH Ezl¤g'9lulzl 4= 5A6J qlqzlEql"J EEE
++19 Ql-E +vl Hplz} Aru94. =+l'47
4E z11H"ltri. ol z|]Hql qsts $sz} gqalql ul4 E4¤
3A.2b^lg ol+6IH "JelE 4Cql +Hlq= ++lel Ql= + g q H3 .lluJzl tlq$$ ilzl6trll ¤+. Bottzmanng -"1+
:tl Eq¤ drll 4l&g + 9l+. qlE^J +g tsslel A+ql=
!= qlqzl ^Jql# 4+{-= E{¤E eEzL ffi$ pol
q,*=0o14, El+^l rl+r+ ?ol S4.
flE eEe+ +dg+r ^llq]6i9+.,
ASru. =0 BE E+ (3A.3)
S=klnW ?lE +trloll rllEl Bottzmann^.l (3A.4)
"l 49 ++lql rr=^l 9*rll Erle P+lzI 444x1 ?t= 6J {zl,tl kt: Boltzmann tf(k=1.381x10-23)IC')olg 1,1+ vl
HEIzI TlE{ola Hlzlq4olA q$rll "Jq4d t*S,"I +,+ dill qlq^l=
^lzl tlEHe-l "Je4zll *zlrlTlH^J 4le_l
CB+trI. ++)7l,ll4 ¤Bg $zlalzl$ 6IE CB6F= a Ezl# + 9l= "JBE ++ alE CA# +C6I
uflzl.lJvJ
=
ol+. rBl4 =tzl4 oe. Ez+ *ol sTlE +zl4 qlLJzlTI E +q4 6Lql^J AlrI d+g + 9l= r*3
g4I6Iq q+^J r"J+ Sl= +ulzl ¤zlal4l g+. ^4 "lrl4 d-El]
Eql aa ¤+il7|'tE}'t= 4,o14. "l^14 /J.'llE +q +EL
"lzHES'+A^l'+ E='Ee4 .ilulzlE +t'4 eg {ql
6Lr e^d4 zll'Jg zlzl:t_ ++HH flE+rl.= a=*4"J a
2e8.1sKEEfr rzf, 6Iql^J 1.00mo19 Hro(l)z| CE g^' o e Ht+li= 4o14. E¤Eol E+ +a^J6t4l eEq-r. E.
E+El ^JCE trll +Ei+=++lE Sl-Etrj4 H+= E-2c.4 9lHzlzl. q z4l EtI¤+= 13 "lrl4 tlelE iz| rl "*
9 ArH"--286k1mol-,9 oleo6f{ alt}g + gl+. gE^J ol.4l+= a4 "*E= 4,"14. Lll¤¤ Eq l2Eqlrl 'Bd zt
"l
,J=!E {lHxlE "J{ol "J{6lrll +zlEl= +flE {f, ¤Bg 4,o14.
^116l
qq, 4+d %u.= +286klol+. tr++^J 3A.4^lg Boltzmann 6Lq, ol ll9 + 4ltJ tls
^lol4I
trq= Eq:44 fllc-=ul+r 6J+. sE Ezl-501
+e
2.86x10s
4S,,,=Gil=+9601K-t
1
=4
g tlEllql glrll EIH EEzI eI zlzl EJ^l oE"J ol+qzlq
q{^J W -rolq, h l=Qolp + S=0ol ¤+. r+14 Ezl¤
ol ,J+Eg !+cq^J= ++lE glHzlzl- gs^J %r-=qs ol qEl qlqzl *Ellql +{IEl4. wzy Gzlola $E +tlE- trI
E ++lE 8l= eulzl6zlel4.
4.rJ ?zlt+. qlqzl tI454 zJ4ol Ar-olzlE q "*g tr-EH
Eol a+¤ + glo=+ ,w4*"1 4T]tri.¤-zl 491 eeil
olxlf ol Sls-eq 49zl Kelvin4 clausius9 2Bzl s¤E
* 714171 a- + qlqlql, +7171 4a++ ETI qlLlzl
=+l=
!+ +qlB+= ag Bqot B oflz| qH+. :aB le.:G)ql +
EiU tlzlql^J= E4$ pfl"E+q qlqzlz| Str^l mI4 ollLl^l /-=lEEl= 8E|'l=
ulzp.E ol ggfl QIE +rl= er1++. "Js^l oldq= ql
Hzlts fl_E +rl$ "JEzl * 6Iq, tr}+^l d^ll4 " + rflg

ol 4lE fleeu1= +^6J+ aJ¤ zBzlql qsH olel+ 4 (a)
33 zlB4ol ol.r-lq, EI4î :zB :e.:o)ql .H-"J tlil= "J oilqxl
I *Ezl * 6J+. clausius9 E¤9 A+qlE zB :e.+glrl /61E:-:l= 8Etl=

+ gg9-E+q E"It9 qlLJzlTI gE^J m[!u[z[ra ol
(b)
gge-l sltr+q= zJaa1z1u3, ol ¤ol E4+ g-+4.E Eq
rg
e ql= I 3A.s E7l7l (b)-e+Ei (a)e "J66lE 8^l' +oll ?l=
T lill E^l=el ET.l
Ql=+-4 Szlzl rI gfle-l E3r}=+ql "la+(e * EE ollLl^l ,J4ol Eot^lq,
e3 e-Eoll^l= rl "d3 E"E
E7l +71qlEql). q+^J dal4 o + flE +EzJ-ltcali p =+l=9
+ ?]tr|. qaN E"J ollLl^l= LIEIS + ?1= "Jgsl 4er17l
=+l=olralalq
=71.61'r
4zI 94 "l r+Ag 4ts4"1 olq+. fllE+tr17l.
=71-Zlrl.
: dzlle raE s=klogwzll. *9q ulq!49 eul"ll ,rH44 :14.

78 2E=El'38=.1
I
I
I al= 8Etl
I
a_
I I
I I I roi
I I I 6n
I I II
I I
al -t-o 9c
s, EL L!
(b) '*3 3q i1= 8Etl
-
- Erl=91tse qlqrl aEfle o6
.f.g 3A.6 4lollrl.0llH^l= Ee 1 7tEt|+E
6tq, qal^l tr1/.14 SEllE +71.=7l6fr. ,jl+4o+ fllE+trlE
E=erl =7lel+. +nl,v
ts3 PEg z{(a)01,t1ts 0lEl B3 A|'Ell=o1 ESElq ?i7l till
=71.=
Eoll 'fP SEel 4l(b)oll,t1-e.ct 4ttr1. fa 3A.7 Eq-sr'4 ++(il8 .8E|1++EI 4l= SEllE *cPl El^l
^13
8Efle EEoPls-)0ll^1= SEll -Et+9 E+7|'001 Etrl.
=
4 zJ4"l fr."itl4(rfl olAg "Jzl-E9 ¤4"1q Eq
3A.s; +Eg 4"14. 4+ 6IE ola-oe,4^] 4lE z]g4 4+ tlEHql
TDql^J +B6J 4,o14). zl4lzl S+trt{l v+el er 4 <k"l Gzl ,rl9 fl_= +ulE r Hs+ Asql ++61-ril e+= 4.ol EtE
6ii1 trI4^J fltr+-lzl rtzlalzll q=ull, olAS sl_E+rl9 zl rllEol4(re 3^.7). trI.g ar+= trol+H El= aol+.
gqo,L4 eEE+q qltr"q= e$e+ +6J¤+(_E_zl 3A.r).
=
dtl,ru
Ezt ffqrJ Ql= +q. 6l]46l] -H-H q4l^J 9l-= erl H - 0 (3A.s)
$or=$ T
olz| re.t^lql^le+ pol e--E-"ll qHlql 6h=zl. g + 9.14. t.
¤ziri ,is 9= tsa As +,?lel ^teg -sxlef4. "i qE
$sz} +g Zlql^J= Ezl¤ol gg +q qlqzl eg.ql E q^.q_+ ?"1 rll E4lE zlzl:il- +E6J + 9l+.
&¤+. 99 "ld-otr. llE 9lHzlE *zltlTlE q "te tI
4E"l dfrlzl"J ol"l d*g r. *rJ 3A.s^lol $S zlz)lz| +q6F= f,
"*zl trI+ql ulE d =tr+
f$(Camot
=+15"1
Efla4es *9 Ssel 4lql ++Dql ql6ll^J 4+g+. ag B"J+.
ir} Hl.$e *+(rH 3A.6). ole+
d3 rl 4e d+qq r44q t"J+ "J9 "llulzl 2. olq^l ol a4= LE Eaol qH aol 9H *4ls"l
oldql E6ll^l=+l.ol
d+El= ^J=}l+el +7I El¤.ol rJ +oixl4 r ^dB++= ag EoJ+.
?-l6}q wzl 4 e-41 ¤zl.l4. olqql !.el$ E"ll^J +al= :. EeE ol 44zl qts +++ql ql6I^J+ ¤B++= ag
E"J "Jel "llHzlz} Ttgql el6ll^J "ldgcJ4s & $rllE ol _H_"J+.
a¤ qE $E+rl HEIzI E4+ EillE oldg ulB+ q

rzl +4*+: ag g + ?l+(3A.rarl). (a) Carnot++
E_o _+ +E6llot .J dEol ll4. :z 6l+. flEEqq gq Carnot +fl3 o*^9 *+zt ol+g B a"J Sadi Carnotel
qL4 AelS- ole"6l.E dtresilel Hp+=*"Jg +e- + fl=ql EJI ol ++lql^J= q-q=4 +ol 7l4l(+E Ed)zI zI94 o +
Boltzmannel eelE ol+6|E 419 $l=.+qE ¤qlzl$ +$ *rlq4+ "J+q= q] +alE "l+qzlq(rH 3A.8), r-6
+ gl+= rldol4. +ql srlr-. 12ql^J sel TIol flz}4 E + *!lql^J= qlqzlz[ S-e.^.] E4+ gg-"e+fl old!
zlel +a4 Ceq qEZl S4l!Ezl= ¤B6J oll
"l ^ldg ALl + ¤fl_"_e oldg+.
q ¤E6I4ltrI. E 6I+= Boltzmannel 49 ++lql 4+^l7l rH re.qz ?+ +4lql^J glq4 Bvlzl- qBrll H6l+zlE.
zlzl fizl ?+4= rldol4. ++l= d¤4 o e q]B6I +d-6I +e}d 4olrl.
4'Wzl el',l. rle + S+. r. zli\lzl E4g Efl(8szl- 4)4 94 d+g al:'- ee
=
Pq ne.e1 7Iq Fg S+g 6J+. Alzl r-trgeE+
:d+E^'lel
3A.3 8E1l SIEEEI 4 qnEl#e-l 9luJzlE ¤E^J Beq, q+^l tlE+rlzt
QnlrnEI+ H+trt.
flE +i4= tr-Ell .J+cI. "lag +¤6IBJH dss.l 4Bol ?e 2. EA& ggqE d+ol #qzlr zl4lzl BE+E] ctr-zl
q1 5-$a|+= ag Bol"F 6J+. telzl +16ll^l= 3A.1arl9 q +g S+g qI+. alEoEl qlqxlz[ p-tr^l m]4+7]
"JEE +++q 44.\1 4E+ 44zl0ol 94. 49 s"lE zl ?tsq 4+^J QlE e'l Es+rI S.4. ol S+ 4eql^l
fl.lEEtrl 79
!!28 Efl
tT A
=J/14 4 E.q qq^1

1
oLL-i {
a.
a
nll
oll
41 3
T mi
6n
Eloq
L-i
,\{
= r-i 2
/12 3
rlE-+itl =ac
+fr] , v +nl, v
lal 3A.8 Carnot +El= 0lF= L1l trJzl=. U4l 1oll,t1ts 7li1l(+E EA7[ -14 3A.e Carnot +Sg 7lE +4" E4l 13 EE lholl^j golLt=
-
7lq "Jdoltl-. E4l 2E ZET! Ih-a+Ei 7:E Eol^l= 7lE =Jg tsetoltrl'.
E!23 Eflrl-E40+ E6lq, E4l 30il^1= rl Egll-traEt. 0l + Ezl=
E.8 rl80lEl-. .Jzl 2el4= EEal8olq, 7Fll= gfl-o_E+El Eolrl ?,ltr|.. EAI 33 Loll^l gclLl= E¤ 7|q g+01tr|.. raE, E!414= =Jg 7|q g=
01q., AlTl il8 SEllE El=olrJtrl'.
SszI 4s+El r,,4+ g-+illE gEE ¤q4lq-.

419 E4l 1+g S+"il^lel +ul H+
3. zlt\lzl + g-+ille+ gzl d+g 6lr. 4ql^J c-e+q D ,Iq +g $Aql^l= gEe+ +El vT,-constant9 S
Î"lql
E 7lq ¤-e "J+ol ¤+. rl g-+il]_e- qlqzlz| pe! AlTl BBd+(Eq 2E). IrI+^1,
o.F=qq,4l9 tl=+rt)zl q,tT,"J+ H6J+.¤zl^l q.ts
DE+EI Avl^lE Ae.(+41 4):voTi=voT'.
+E alg 4=+ BE+EI Cvl^\E A-tr-(+zj] 2): VsT',=VsTi
+. E-e-E & g-+ifle+E d+ol #{zl:s 4lE oe+rl e
-tr. 7Iq +g "J+qH^J Sszt rr.E ¤4214. ollHzlzl
ol a4l
^lql+
Ezil !g B6]]=trJ.. :r_qfl,
gE^l EqTIzl ?+sq q4^J flE +El H3fl+ 0ol+. v^vcTfT: =vovsTfT!
EI+^J ol +++ql +Hlq= dill d-=e.jil Hsl+ ffi$ {ol ol {g gE= tr-4]^lzll u19.4 ?ol C4g + 9l+.
ol$ ql +zJlEql^Jfl Esl¤ tiJ6J 44 ?Jt;+.
= vc Vo Vo
-
VB
$o'=+.+
EJAI2 + g ol{ z.}olel g{l
trl*- 6J "J¤. ol
^19
+Hql flE + 6JE Elol 9d Tlill.el TIg +ifl-tr ge^-l t+l4zlE "lluJzlE q-q-r+ {ol voe} Vg
49 ool Elq, q+^l 4qE ol zlzlloll ql6l]^JE flE +v]7t e+E ++E +4U+.
tlel EL+7I g+= 49 EolE 4."14.
7li{loll El|6l| j= SlE +tr17f

q, -nRT,l"
* = nRTc'"
f - -nRT,L"t
Sd
8El| et+olEt trl+^1,
+d ++a}]"t E 42 zl4 +g SlXf-H :e.q9 E4l zlql qn_ nRTrln(VulV) __ f,

E6l]^J 4lg gsTI 4E+El 7:-tr. E++E 4o14. olBl* S 4., -nRT,ln(Vu / Vo ) T,
+ql^l= VT.=constant9 +Al7l CB6Iq(Eq 2E), ol !g {zlrl snt' *olr(+ E4g g+l-q E+el Eol mt4+g+)
ols-"olol *+ dl} +fl +u1$$ ¤+^lvJ + 9l+. E 6I+
q.E oJolq(+ & gfl"e. Eol E"lz}4), oI4rJ olEel Hl
E ++$ dg qlqzlzl zl! r=".$ r+Aql EI+^l ¤e.r-1 o1 zl S"l EcI. q+4 ?"1 4r-1ts + 9l+.
"l ^le
dg+= aolq(+41 lrl 3), rr}4^l 9d zl;llql E}]6]l^J= +
Qn Q,
+r+ Aq *Alzl CB++. + 0 (3A.6)
4 T,
ual E4l
1 3
ol +¤+ql q+ "Jq+= dill flE+rl HEI+ QntTntq,tr,
q,=nRT,trf olo+ 3A.6^lql E"H^l sd Tlillql ql6ll^J= ol flE+E H
qn=nRTn
"f
80 2H=lr+38=.1
olz| oo1 g4
'' gnl
,_lqnl-lq,l =r_9,
lq' I
(3A.8)
ffi:d q 3A2 trl-4^J lq,ltlqnl=r,trn9+ Aol ++U :e.0a1 o ++q +¤-Jl.

Carnot +{+g E4-s gg-oe+El gE^l Bo}tr qlqzl ae a+= eg + el+.
el "J+= "Js Hl^+q+= gTlsql^J "Jq+= H+= + T.
,t=l- rn Carnot aE (3A.9)
4.fl= 4,"141 B + 9,14. c"-ot t{*ql lr}s= t trzl
+Iol soorel E4g ggse+q rool9 "llHzlE so}4
ol(qn=_rOOD a_ +
"J+= 9-tr ;r;r 4"lzlE:OOr9 & zrtrJEl oll 3A3
g-+iflql L|]r{H.+r 6tz}. te.6alql E6}H ge
rl+r+ *ol !"lo} ++.
'llr}1fl qH gdaql^J 300.c(71,=s73K)el rlg ffi71=
^l¤61-
-lL 20"C(?.=2e3K)el ++lq+ qgg Lll-H-U+. ol A+el
T. 300K olE4 ggg trl+4 eol gtrI.
4,=-en* q =-(-100 I)x sOOK
=+00 I
r?]6lq 40lol .Jg 6l-= Ell ol+E 4o14. n-rffi=0.48e

4 48.eo/ool+. d4lzleeE 7lAl4 "l-+ol4=zl elH-l"l
olzll. re.s4ol Sd Tlill gq} olq4 4E oluloJ Eeql zl9zl o + 4l+6lzl ?+=+. ql trIE +¤ol ?ItrI.
E 4+ ¤+b ag +Ee zleil+. r46l-q 9d ¤zl*9

EE ryE ^d4'aii exi.
olzll ol er+= iirll+. gE+ z$zl"ll E6IE
"JHIE+^la
¤6}lrl g w
aE zI9 zl*¤ "l¤ 4"14 :. 7a.il +4lflol Eg+ -E+g
q
EZ+ ggo ++Et ¤-++ g ttretl
(3A.7)
"l s¤ol g+= A& Hzl +l"H^J F zl]g z}g

lqn
7l4ov *4.
+s trllE9l ,.JzlE +*g q6}7l +l6ll^J ¤Eilzl +g 1...1= 7l+g Et/l A{16I¤ "lag E"J+ F gg +561-
^lolql^J
-tr9.9 E+
^F&61*.+. "Jel ,,k* zl4oF qI+. ol CEql Al ElEfl4::. a1z11rfl ln.tl). + zl+el 4r-5. Eeol+
^ll
E6IE E4g ggo ++El "JA¤I gg *,f*olrJ "Jg ".+ +4 +a= Sd6l "JE4ol+. +d zl+1 l-zl zl$ s-u-4 *
ol oJ+-g 7l+el a¤-e- +olTl+. ol zlgol "Js^J *=L61-= g ASg *=+J. 7lai;la; zl$ szl rI ¤fl_o e.+Ei qlq
9lHzlE E4+ ggoB+q tse g4 & g-+il]E Eel= zl q,* gE^J S"l-4rJ r-+ 9"tZI9
"lluJzlE ¤e_.<1
,=4
g4q ite+ ee-E-e(re 3A.10) 7l+E trge. rJ-o=$ ztol
gRI 7l-zlr. +EiB + gl+.
="JqI
EE4E Efl EE4e Efl

t I
r, f,'
'l g4E Eg
,K -qh
Ar
qh
5
-+w ,.tI Wv q"
B
vv*
v
15
q" fl g-+iH T rl E-+itl Tc
T
t! E-+ifl (a) (b)
fal3A.11 (a) EgEl Efl= 4tE6l-= E.= 7|.q 7|+E Etol

^l-ololl^l
leJ 3A.10 E7lsol !E718 gfl-e_A+E1 ollLl^l qr,(GE/1 20kJ)=
-ej Eg6lrlE r,iE e.olzl ?l-d oilLl^lE a=. (b) 0l rl8e-l t aq= rl g+itl=
Hgn, Tt E-+itlollrl q.(GlE^1 lskJ)= Lt|qalqr 6l^1. 0l E Tl$oll
slat|,'.l g6HT.l 33lqn l-lq.l(G|etj 20kJ - 15kJ=5kJ)01tr|.. s.fElE
=rl'tr|.
34 flEE.4 81
+ ggql 4+E+ "l eE.E 7l+g Eot7lril ElHzt zl* a (b) Esltrf4 g=E
E zl* BE+ +.g Egg *Eq-r z|{a19o p + zl* e zl# gEz]- Tn?i EZe ggq t-Ezf ToJ & g-+^11
E+El +s= "J9 d+zt "l 4c9l J\qslzl= 9*g 4o14, Îol
r]4rallEz|. rqH 3A.e^l
"llrl zI94 + 4}E-6l.= 7l+g
o
r +{zl= +e .Jg 6l-= Ell ol+¤ + 9tg 1o14. olBTll ql E6H^l q-g=+ zJzsAlzl-cB6J+.
qE e44e + 4I g?lql= o}+fl Hp+E "Jq'+zl g+-g-E
6}6]|zlr. E aggS Bultel qlqzl$ gal E+ T=(1-?)Tr, (3A.10)
^J "Je
ol ar}= Eol dp "JEEJ H+q= 4olo + zBzl{l *aJ
KelvinS "l 49. ol+6lq ¤zlS9 a'Sg zlzlt- Esl-+E
Kelvin9 e¤rt E+g+ oli]fl ol ¤Eol dzll ¤tr-r+ "+^l gE 4EE Ael6LB.+. zl+ E4e gge zlzl $r aloll
?*= ae zl* e.e+ z\* szl ^J"l+ ESg zld+= 4* zl gijr" & g-+il]= +c 4tL s-E 6l.ql 9i= qI ¤zl*9 "JE
c"l ulEol4. qel^l oldq. E4 8s
=-*.zl ^t"lel +41 H.+r 6tzl.. rBlE ol +zlE gE= ol Ezl*E -tr¤-3 +
E E+ 4r-+ EaE ++ql ++6llot 6Iq,,++^J :n.s^l¤ ol a6}q "J"IE + gl=. 4ol4.lGtvin 4E(gqqr-4 ¤-s es
¤ Eeg carnot 7l+ql ^l¤-61¤zl $4l$"l CB6ll"F ++. E EL A+ol+)= dL+A 6}ql fl= Eg E4e gg
"]tr 4."14 s
olzll ol +BE 4+ +4lE^J 7|q4 +++e =HEl : s-EE
o + ,rF&oE A+4Zl 2n.rcKq +a C+ 4ol
F o + + d+E carnot +++=e-l 6Je--tr ++'3 + 9l r)-4
=Î4 t.
+= ag sollz| ++.+d :zH re.rzql^le+ a.ol :zH9 i

* A, s, H cE9 drll Eellzl dd" e ++U +++r+ =Î4 (c) Ctausius +E+l
etr_?JAl qE+ ol=¤ e6J^lzl4."l5 zllzH i{}ql +H}q
olxll Q]_e +"lel A9zI zBzlr+ +.Jg+= 49 E"lA+
E fll= erl Hsl+ 0olq(+lql^J +E+ ute+ Bol), tr|+^l ^ll
++|=q1 46J QIe +qE 6JE ool 84. rq+ ol 6.Joll^J oJ
+d Hl-7;E4 aaql^JE_4E zl94 r?9lrl rJ f*3 "Jol
fl6il41+: Î¤¤. ttzlalzl BI*+. I ldw,",l > ldwlol4.
d ++|4 ="-ft9E aE tlE Sle+q S{=-=-o ^}All¤r-H"J .llHzlz} AE uu}4+zl$î "Jg + 4lb awg+ dr,.,ol *"lzl
d a_eEe ,<Je HI4 HJ6JolTl trllEql). tr+4^J dal4oJ + qlgql ol > _dwel egq, q+^J dw-dw,*) 0
¤+E Eqlql q= aEI zlle]6lr. EE tl= eul Hslz} ^J4l¤ ^l3. -d*,"u
r+ gg 4,o14. +E .-lt+ "llHzlE d".ll Et+olE_tr" 5g+
tri Trl-+^J dill4"J ++ {e.{l 4E q*/r9 a]r ool g+
+++=E 7H+. +*I=ol ullo}rll q= +6Jql^J= + tI4 ^lolql^J= Af,zl ulzl9zlold TlE4ola +als.
carnot
=4
+¤|=E t}4lqzl ?+= +Hol +illzl +¤+4 a+6I
ol Hp]%r"l a"I"t 6Iq, q+^J r+ql=4 ?"1 ¤ + 91trI.
,ll "Jzl6lrll ¤+. ol+Al 9E :e.s^l("JHI4 +++ Erllql a dU = dq+ dw - de,,, * dw,,u
4 dq,Jrq 4$)e] 44zl ¤4. ol ar+= dszf 96 trl+ol rr-l6lq g+. r4ts
dq,,u-dq=dw-dw,,,ol dw-dw,,, > 0ol
r q+^J szl-^J4 EL+"J$ 4,olr|. p qq, q+^J dQ,"u2dqzl fl4. :ar-la "J
+ d{,*-dq > Oo1
=61+
H9 rE. ++E dq,Jr>dqtrTl84. ¤zl^J tlEeqq g
a qql4 C9(as=aqJD= ol+61-E olag q+!+ Bol ¤ f
b
el+.
a. aS=f chusius +54 (3A.11)

a
mi
6r qI+. ol
a3
ol
^lg +E-4ol+r
Ctausius 49 El+ Hl+9 xI
ECg b6l-= ql ql+61 +e6].rll ol+gr+(Eq :o1.
ca
4l7t +fle+El rBqq flg 4E q=6ol qq, clausius
el +F^lol ffi$ ?"1 ¤4.
+-rLl, v
lg 3At2 trds_e s.t l-d ,JE= l1l Grnot +s A, & H Czl.trJE= HOl= dS >0 (3A.12)
Ealrl= drl- 0l= 7H7H ++oll rHat| lE glE+tr|

=/.l-4o+ =9oltl.
EalTl 00ltl. 'JE +-=(qllLl at-aq ]4r cr-ca)oll ttl= glE-etrl UalE r?-l6}q rlfl¤ 4lq^l} zlp4 H4zL gqg 4 {c-eu1
00lq, qatll "Je-19 -d ++9 +E(qTJLll at-az Lal-r. or-oo)oll r[g
glE_+trl EEI= 8^llEJtrl-. rq-af^1- Efl Ealloll n[= g]E_etrl E6t7l- 4 E¤g g^16}zl ?*r. +erll A96Iq= EEzt {t} folxlu.l ,t1|
^11+s=el
0ol Etl. trg=C¤I
Ael= olzl "J +StrI.
82 2E=lrt 3EEl
7lrJd|g' + fl+. "lae 2BzlE .ll¤¤ 444= 4,"14.

Clausius +F^lg E+ zlg4 r+Ag 9¤4 o + ulz19 4 Tn
s7]E gfl
C"lr]"t +4= 19 9"1{4. "l 4¤¤ qoJatzl +l6ll^J + dS=- dqllTn
4¤ql +ElEl= d4l $l=-erl +,J ^lql+ ol +t^lg qlE
^1494.
r4H, dq
2dq/T 4q/T
+- +
dS,o, dS,u. )0
=dS +
s
ol +E-g.= Hlrlq 4cql 4'J6I-2, ="$a.i z|$ T
*t E_+ifl 6g = +ldql/f
^lql^J
r+aq 6HBqi+. + zl-Bzl 48(ds.,>0)$ ulz19 4Col4.
ds,o,=0ol 9E zt9 r+a.3 qL- +_e__tr-E zlB4 HEizl "J leJ 3A.13 Egoe+E1 ollll^l7l E-eu1 u8f^1Ll7lE r Efl9
EETiE
"Jqu+.+ ¤B tr-elq il= aol+.

glE+Ill7l aa-drt. +e3 gel oilL1^l7l r] E-+il|e tr]
tlE+tr| Eel.7l-LfEfLJr[. qal,\] IillEoe 91=enlzf =q7[E 0l =
r|'801
clausius +=4lg fl=.eu]e1 eqE 2H44 ¤e^l4+= =7l.6|.q
xl.JEo= gcl'J + ?,lrl-. glEetrlE 8rtl4 EnF= al+lEel aTlE L|EILH
¤:,q+ Egg 6l+ glqls Ealzl-r ++l e.E-tr. c)lr I
=ts.4fl
ts4El= 4Col zlg4"l4= 49 s-q+= Hls ole"B f
gl4.8rz| rnoJ + 4l(Erls gg)e+q gETI 7i"J 4l(r}
g-+^}])E 9lHxlzl- $er.l
"ldq= a+- ^J4L6}i.BZI(r .l.fl rll dqn= -dq,ol tr|. q+^J,
B :n.r:;. E4g 9flee+q ldqlrl gel+a qlHr|4^l
An ,-A\ /-lo,,ci,,c
slh\v/, vrssrrsr -ti-l=
I o -t
lolI ,lc ) An lT.
sv 1sl1h, rhzl- slr] rll;rt-
| 1__: l.
lAnlzl
tsl t. I
--
tI g-+ilJ_s Eqa 4lE ctausius PF4ol dS > dq,tT,zl $
4(dq.>0). tr++^J d^114 o e q+r+ ?ol 94. ol +) El+^l ts4(Ezg
ag "Jol4(dq.>0ola Tn > 7.olu
q" + 4 *-e--a+q & *_g-sE gE old)g *4zI Aeql 96ll^J
ds> ot= Hte+ ?ol zl$4ol4.
7i T,
=g-dT]ILJE
tr1. tlees|= Îg4 Es+g ?8"1 E^l qBg 6JtrI. ++el tr 5 ¤zl*9 EEg gqq4 gE zlE= C9a}a Kekin 4E
zlzzlFl4.
^rg4 $Cql^l *zlt4.
qlE eul= ql^l6l-=
=
a2 QIE+v] E+b 7lE4 ¤9 "ldg zlz\:il- cel'J+. tr6. +E4e aBAl7l zlgzl H+= .Jea qlE qie
ctausius
tr3 Bottzmann 4g +zI# qlLJzl ^JEI=ql H]ltsdJ + 9l= Eulzt 6zlo14, r46tq Clausius 49zl zHzl4 +.Jgq
"JBE a3z$la_ AE.J+. "l H}lgg diil qlqzlzlE"J = ^l-gg
trq=+.
6}rll ol+q4o} aJq. a7 Îg4 7l4e ulzt9 4col4. Qle.eulz} E6ral ?+= r+
tr4. carnot +fl¤. ol-e" ol.fl Q]=.+u;21^JEH EL+"JS +E6J + Ae ¤Bg ol? 7 9l= tlEll+.
el+.
34 $lEEtrl 83
=s-d^l=
ce ^l
+4 al Ha
gqq+4 flE eul dS=d4.",/T ol
z-l
o-1 3A.1a
+9E tlEEul HP+ ASrur=4rrr/?i* 3A.zb
Boltzmann 4] S=klnW CE 31t.4
Carnot E¤ q=l-T,lTn 7Iq r+c 3A.9
¤9o14 8s 7=(t- 4)Tn 34.10
Clausius ++3-1 dS > dqlr 3A..11

E438 zE!=oll +UEI= fl! E+trl HEI-
=8
> ol EEg Hll+= ol3
3B.1 "JA
2EE!= A|qfoll E rl"8= E6H^l trtgEf 7|a Eal4
-61.= Etrt7l golUtt.
i1l¤oll +ElElE tle.eq
Eq 3A(+xll4 "-e. -E-zl 3A.1)E A4"tl E6tH +iil7} y,E
+El %E r="¤. s+6k sd zlillE dE eirl HsI= q^q=4
> qld T11L; ?Jtr+.
+uEl= tlEeq HF+= i1=

-d rEloil SEtlel El= 8Eil
7lE4 eE= 4ol^l zltlElrt. ^t0lel sE TlillE 3g "Jgoil
AS,., =mRh{- ttlE ?!eeq Eal (3B.2)
> gsEt qHl rl^l agolzl trIEql 4lE <lg a*r+ 4+

s7l "l ^J4E
gleeulel 8eJ(EE 3A), g, g, "J Lfl+ qqxloll s-d Ig4E ^JEH
aEql ru6l.q, E|+^J ol^s
4g tF4 HsIrI z}g4e
7i|E(EE 2A), -Lal-r. gEaJ(EE 2B)g E 9z ?lolo} e}trl. 0l Î"lel
Erloil^.i= g5 2F.il9 7[q4 Ee tsa 480il^1 "JolLl= gr] -e "Jq+d ulz}94 e--e. gq+a +4$.ol CBaJ4. fls
EE olE= LtEl4= 0l¤i6lfll E aolq. EElel +rlql $eL _Er.(4+) E= +41. rfl :n.roll +El
^l-
,-l]fr.+.
rq+ flE +ulel d4l uolg ol "Jar-oi qB4i "JqLt!
+ql q=.J+. qH 4eql^J+ 4ls+El gE^J nt44zlb
fl= +u.1 Hsl-ll rll6J gEE4 eE= 3A.l^l e e +qCq. 9lHzlE ++le E9zI4, trI+^J d4,,,=-dQol+. r=l a 7lE
q'- p= efl flol Eslql q6ll^J= q,,u=nRT ln(4lv')olq, r?-l6l-¤ q,u.=-nRT
dS=
T
AS=
I !9,-
T t89l
(38.1a)
ln(yrly,)olr, qE|^J q-q=$ eg ^lg gg + 91tr1.
{zlrJ ¤.E rql^J 4lql ,}q4_o_e gE^J ,}6lld qlq

Q,"u* AS,u,= -T--nnnf (38.3a)
zlol4, gqEql^J SIE erlel +flg al4}¤. 6l= ql Tleol
E4. CEE ++lql 4¤-^lzl4. y..zb^lol qirll, ola¤-
"l ol flEli 4lE HsIe+ .flsz} q}4"lq, ,rl-+^l AS,o,=so1 q
+^l 4E o}4e+ a+. Erll, "lag rlE 4aql ql6H^l x.l¤+El zl4*,'J 4eol4.
HlEql E"g S+ol zl.ffi4l "Jqts q:(TI+ +eEE S
4ru, +?lsl
^J 9"1 686}lzlxl ?*E4(w=0). oJ+ol :|g4olF + AU=O
AS.,, = (38.1b)
?iu, fl= enl Eol
olq, gEqlE lHzl lu= q+w4l .el6]]^J {=0ol g+. A+
{zlrJ {,u.3 4lql gE^l zl."llTl qlqzlolq, ?,,.g ++lel g qr
E|4Al Aqu.=ool ¤+. "Jol felqzl *E
4,*=0ol "l
E.+. ++lel QIE+rl Hq+ 4lql 4col zl-${-o + gq+
a Hlz}94_o e "Jq+a +4lHol E"J6l+. rBAl(ffi)E 4
d^ll fl= +ul Hq+ "t4e+ ,JE+.

3
AS,o, =AS+AS,'.
cill (3B.1c)
gl=-eq Etrl q
6 2
"J+ E-44 H34.il +Hlq= QIseEl Hffig +s

aI¤ ¤zl^J fl#oIBJr ++. Eq 3Aql^J ¤¤+=tr61
ute+ *ol
zits4 r+ag ulz}94"lq(gqq}4 +dql^l), AS,*=0ol I
!+Cg ¤Bg olf 4Col4. 0
= = 1 10
vl V I
20 30
feJ 38.1 EE TlillTl-- ga-g r4lts fl!=eultl +- Ef+ Ee Efttrl-.

38 zElSll*uJsl= g1=eul str[ 85
=E
Salq 'll6H^J= dll Ql=-+ul Hslz} E:n.ra1ol E+. +, B¤61 sl= +ulzl *eal"F 6l^= 4"14. rq+ 7g-1e {lH
zlzl g-s^J oldqg Eolzl-7l uHEql ++le-l flEBul= +
vf
AS,o,= nRln
\
(3B.3b) 7}d-q, dol $sql^l= F ^Jol ¤¤g ol1zl qlgql Sl= +
irlE dill EEIzI 0ol qqot ++ㅡE ^J dolzl Sg r+A.J
"lq+ ulzlg 4eq e+ql= glt*'J 49 AS,",>0ol+. ullH¤+olr+ +Ee- ole+ 4."1 4.,H>0), 4lg sI= +rl HsI
7l-"Jol qEql, olag 4l LH+ql^J Egol E^J9o + '*¤6J
¤4o14. oltrll= ++lel Ql= +ulzt ae oJ"J+ a}i6lq, +
qtr sd zl41o15 gc6J e.Eql^J r +q= Hl]E E?]ts ^ll4 " dill
e- qlE..tr.rl HEI+ ool g+.
ㅡ
v1tv,-2zl qq, Alq E $s eulzr q+r+ ?"1 HeI4. .g :s.rgl dol QlE +rlel dE 44¤ "JP azHaLHq. r
?-la E :e.z"ll H zlzl .lillE #=Aql^J9 s= +ts qlB
AS,, = (8.3145 | K-tmol-t) x ln2 = *5.76) K-t rnsl-r
qE a# z|,rllal rzfla}.fl4. ol -soll +Elt xl"lilb Ed
ol Hslz} zlEzloE .Jq+H ++lE Qlee.q H+zl
e E+e ++E "lxllEE *-= +ts $E +v.17J. ql4ls Hli6I
-5.761K mol-rol ¤uH{zl,{ 'mel-t'g ^lE 49 zlill E
r
4E rI¤"]+(E 8sl K-' mol-'). ol dE ^l-dg Troutong i}
z[ tmol r}9 9"laJ4). trt4^J d^]l fl-=+ul {o}5 so1
=lol+a 6J+. Trouton9 +zlol ^"ifl6l-= ol*+ qH
.+ill
¤4. zlr? S+g +tr}ts Tlzllel E Slc+4 EEI= rql E 6ts:"iq zlillE g uI 4zll.e. Hlid AEe-l Pul Hs*zI
a +s.761K-rmol-rolzl"J Q}E+.rll Hsl+ gola,
+flE
'i44zl ullE"l4. qlEql EE
ol o+illE=g Hl+ql _E= 6B
q+^l d4l HEI+ +s.76l.K-' mol-,o]4. Sj_EEulE zl.{ {olep zlEll$ + 9i+.
riouton9 +! o ++El rz]l H.q+= E!l=g Ezlz} tr
s++ol a6ll^l E4¤"] ++4ql e^J= ol=n ?lzl U}lE
ol4. olBl+ .-!ill7} +ts+ trll= $d6l +e^l+ a4illzl +g
3B..2 I Eol B trIB+ +e^J fluzl gl{ q r*ol fzlullot al.b 4o14.
EAol 94+ #A+ B trI +4+= Ee.g Bti4 "lgl
+Hlq= ollHzl Hsl+ Ezl¤ol SolE A^Je+ {lHzl i.zl
slE aE Es]¤ Hlg6l-= 4o14. q+^J tt dolrl "Jqg
E 3B.t 8tl Eo!
-gEoll,\'lsl
E= I dol t!=e4("J -gE), A,,,5"/
(JKlrnel-t1x
41ts Ql=e.rl HsIrI +Hlq= 4o14. qlaql 6J Eeol +
gElE zlrrJ6J gfdrol Hrll BtlE zlillE E6Iq, trl+^J ¤+(rr.1^l) 6g(rb"ll^l)
"l
Eeg d= +ulz1 =.zll ?zl6J 4 0.+ qltls+. :/Zllzl. $o[ olg*, Ar ra.rz (s:.sroll4) 74.s3 (87.3rollrJ)
g ullE r EaE glE+rlzl *zl.t4. (zzqrgl.!) (rs:rgl,q)
^l Ex,llE HIdL cuuu :s.oo sz.rq
zl# tatm9 "Jq 6}ql^l A\q ++l7I 8A dol ?i,,ql E, Hro 2z.oo (273.rsx"llrJ) 10e.0 (373.lsrglrJ)
-es.
;l 6}zt gE= ggE qlill
^l ¤¤g
olF 9l+r ol A+ E 4.8
BE, HC (8Ke+ 3obaroll.rJ; rq.s (+.zzroll,q)
$ tatmgl^l ¤¤g ol-== o"c(z73K)ola Eill EE A+ql . zlE ¤ql q "*e <iEol ++qq 9lq
E.tatm9 +7lel B¤g olf 100"C(373K)ol+. dol 9s
ql^J= Aq +$?I ¤Bg ol?=tr e F ,r.|ololl,<l
^J "llHzlz} 8 3B.2 o-qilPl B=Eoll^lel E'= flgtrlel fllc-erl*
gE^J old¤+B olag ,lE4ol+. "Je+ gr"q q-ql^l= =g
q=A,oHolo + 4lel E Ql= +.,il Hglz} trl+4 ?"1 ¤4., A*PH¤/(kJmol-r) ebrc a s"/
(|3-r moPrl
HI4] 30.8 80.1 87.2

8-col ?lEetrl
A,.rS=# Ilt,=oll,\l]
(38.4)
30 76.7 8s.8
Îgs+ed
30.1 80.7
t dolzl- Eg 4AolE(g trll+ F¤
ol]s+ ,J"l at..H<O), ^l=Edl& 85.1
419 Ql= +rl H+rI ¤."1 S4. l.z,ll ^Je]= qqill ^JElistrI
*q40 18.7 40.4 87.9
trll+
EJ e^J4olr E "_4ill ^JEH= zlzll rlrfl-H_+ q a^J4olo+ 8.r8 -r61.5 73.2
lf
1 EE zCglrJ ¤B6J uie| rJ"l /*H= lmol9 EA 'J qlBEl Hq.olq, tr} - 40.7 100.0 109.1
4^J d""sE E J "Jol g+. . zlE Eql q ge AEol ++F]q 9lE+

86 2EEl3l'3H=l
D
r + 9lz} EoJrll, Eol+g +g flE +E= 4= Ag Ezl 15
E Îolel +i e6Je_E .+illz} ^JR6J +aE zlzlrz ))zl 4

rll+ol4. +i
eoJg .4ill ^JEll9 EzlEg a4sla}q, :z 0
F-l6l-"1 ol E!¤g qlaq olil o3o14iE E^Hft 4o]-o1 q
H+)e+ ee aql Hl6ll^l *lc 'J +4La6J ^JEllq gial g+. N 6
El¤ "ll+E +ts flEEr4= ul8t4 o.a ar4. olpt rJol + 5
B Ql= +ulz} *3 ++zl"J olf* ol zlill zl-illel flE +rl

…
7l e+?J *zl ollgolQ(2e8rglri 1861 K mol-r; *2 44 6l
'
0
ql^J N,E dEEul= re2lrct mol-'ol4).Eq rrsglrJ ul]* 10 20 30
Tf T
,ll qdzl"J *g +C EHjEE Ezl¤-(cH,q ?3)"1 Hlr4 I
+e +^J E.HIEel Ezl¤N,e+ Ag)ql ula|l.<l ¤gql^J d feJ 38.2 -d EtrE fllE+tr|= gtrEf +trloll^.jLl gg g'el 6pll^j 7lE
:g q er -Ef+ 0l rBE +dtrll= c^/RA 'J=01 E,\lElol
+ 9lE sld tr"E{Eol q 4zl r|Eql *g +C -E.HIE ?lEtll, 0l ,Je 8.J-d
"==e
=7[-Llq.
EE BEoll,\1 oJ86ltl.. g8-+tr1 2sz0ll,\1=
=Et
E zl-zlE Ezl¤9 E Ql=-+tl7l. EZI4I+. C^= Cv,^ Lalr gE-gg Szollll= C. = Cr,.O ltrl.
ruil q 38.2 Troutongl ffi 19 rs.s^lql Bq+H +*4 ae +41= eg + 9ltri

"4ill EE3 +A aElg zlzlt- ?lzl ?*e4, +rl$ Brrzl
EzlolTl ql$ql ,l4l tr-qlql^l Elctr-zt flf,_$ 448 zt rr, CrdT EEoll r(E ElEeq EFI
s(?i)=s(4)+Jr -T- t"J¤ g+l
(38.6)
bdol s.+. E|+Al riouton9 itzlg ?Ic6lr 4+^la

+ :l+. e$$ sy.z"C"jii-l #=+. Trouton9 +îg tri¤ .{zlri Cp= Cve Hi#j+E "Jd-+"] a'f"iiri ifla'it
"l"l
4 ae EE +4L}l.z -e.EE E= E +g SIBEI= +6I g+. cpzl +d gE ¤q.il^J gEql ++6J ulE ol4
'1|tF
q4. g 4E zls Hlg-EqIEB + 9l+.
4,0H" = To x (85 J K{ mol-t)
s(?,)=s(4 1*c,f,,+=s(4)+ c,nf (38.7)
ol
^lql+
qlolEl$ Bq=+. rflH
"Je+ +rl 6Iql^J 7l-96l-= a+E 4s "19 Bl+61-+. flE
A,"oH" -(332.4K) x (85JK-tmol-t) Evlel s-Eql SaJ e:.-E= +41= rB 3B.2ql +$r-|]fl+.
: *2.8 x 104 J mol-r = *28k| mol-t
#J:d 0{l 38.3
+e il= +ze.4skl mol-, ol4.
2e8Kql^J EE "JA +rl E g+%tg 7s.3IK-t mol-'o]4.
20'c(2e3K)E+El s0"C(323K)tr- 7l-gg *ll9 E ql-E+ul
3B.3 7lE H+= ol gE gqql^l ¤¤-=J=ol "Jets a+ q-s=4 A
ol g+.
3B.ta4J oE ?9xlE qlE+ul Hql"ll +ql gE+4 CEE
ol+6IH e.-r r,q1,<-1E 4lE fl_EtrulE oJl, E ol 4lE g AS, = S-(323K) - S, (293K) = (75.3JK-'mol-'lxf nffi
EE HE}^lzlzl 9l6flî 716]] gg "J A+ql= +g =+7.341K-'mol-'
ole" 6f{
= ^lg
4ql^lel 4lE QlEeqE +e. + gltri.
s(rr)=s(4).[ + (38.s)
38.4 EEI
TISE *I glqol "Jc6izll *zlq=(q7ls 6l-qlds+ a-"1) =ET
Alql q6il^lE d{,."=dH7l qq, ol +alE ol+6-}H -H-¤4 "*g 44ql^l E ol^JE .il4"lel7I H+tri. qlE^l zlillel +
eE + + gl= g.ol g+ "Ja-"Jq g+=*E a9(28.s^1, qel rgs7l
^l* ^JEIe+ 4+ tr-EH"ll^l E +
trl-= f ?14. s
co-(dHldDrql el6lH dH=CrdT, tr|{^J d4,"u=CrdTolu|. o1
= ^J4 *fol=e a+ tr-El]E+q a]+ ^JElltr- zli zl!
rf8=oll+UEl= g1=+rl fle[ 87
=E
AsE q6}q Al&g + ?l+ qle^l As= + *altr ++ ol+6lq yr_E+El yfE ¤ig s+^l? ull9 $le
rs.z^19
H ¤"]g 1o14. f,-g S+e_s fl+ +q4zl zl4zJ 4
= -eq Hq¤ ++trt
+, "JA +q 6Iql^J zlgg 6lq 4+ gE_E zlzlzl! \o1
4. ol + $AE 7lq.6J6IE dx,ll Ql= e.rilzl ¤4. r)=nRhf
^s(+41
E$[ +d rgtoil E1E1 Eeer4 zlfi = 0.0201...moIx(8.3ta5 JK-' mol-' ) r"*#H
=*0.1t6...1K-'
Pulz| 0.s00dm3g_l *zl 4.11 Eqfl= 2s.CE 1.00bar9
o|=_* zli]l$ PulzI 1.000dm371- ¤ ollztzl S+^l7lE^J
gE= Loo"cvl^l gq+H4. fl=erl Hsl¤ 4l&6lq +q= "Je6l-zl +zl6tE^l r,E+q rfg 7}g6i= Eall
+4lql^lE QIs+u1 H+= 38.6^19 ols" c4.
+. "J¤ +ulqlîE E g++g ],RE A6Iq+.
za{H E+ql^l ¤H6J u}9+ ?"1 di-ll r+ag + + As(s4l 2)= nC,,^,r? = +nun+
^tE}
4lE +b+. + 4+ *vlztzl Eg "J+g t'lzl-il- olq^J
-- :w(0.0201...moI)x(S.3l45lK-' )h{5
mol-' rrr,
lllvl
+sl= ra^lv];a 4+ e-ezlzl7Ig++. a +4ql^lE
2^\V.V!vr...IrMrt^\U.JrTJrr\
29gK
qlEevl Bsl+ 3B.z4l.o + +B + ?lr" E ll +4lE H = +0.0564...1K-'
oli sr71 gEql ++614r. p;r rs.z^l(crE crs HJ^+ olE

q^J)g ol+*tr}. 4 a+ql Ee* m9 "Joloh d+ql ol + EEI=J¤- 6-JilH alE + tlE eul Hplz} 94.
4? azl dr-Eil$ rllolelE $d zl;ll tEI^l n-p,vitRr1{) AS = 0.116... IK-' + 0.0564... IK-' = r{.173lICt
Bq^l +6JtrI.
\t7l B7138.1 4l+611^J E"Jt az1 tIEHE ^lEE
Eol ol zlillel Ee"*$ q+r+ ?"1 *d4. 0.0s00dm3o e "J4,'.lzl$.! _2s"CE B4^lag qq Sl
(1.00x los Pa)x(o.5o0x 10-3 mr F ev.l E+= +61q4.
n= l45lK-' mol-' )x 298K
)
= 0.0201...mo1
(8.3 r-) Iero-'$
=s-d7t|E=
ll l. ${ zlx.llz} 5.$ S+g t'llE :z qlE +irlT} +7}q}+. -l 3. oJ E¤ol Tlgg 49 ql=+ul 6zlb r EeE g+-*g
a z. EI Eag tt4zl r dol gEql^l Hg trll +Hlq= QI= + zlzla_ +4,-J + 9l+.
El Hsrlt r dol dBrl= zlxla- +48 + 9t+.
=g:dAlE
zl
,r-l z^) al HE
oe, l
--1 t --1
e"g S+9 Sl-E eEl AS = nR ln(Y/Y,) 9d zlrll 3B..2
dol Q]g_eul 4,,S = A*H/f,., dol 9s9ld 3F..4
gEql ulE Q]=_=.tr] EEI S(4)=s(r')+Cln(I1r,) g+* cE gEql ++6fir. t}dolzl "J'i4zl ?+=+ "Ja-$e 3B..7
ql^l- c=co, "Jc-+Elql,rl= c= c,.ol4.
EE 3c fl! =+trlsl
=g
4-B+ +g gEql^Jel qlE +q= +g-q 2."1 ¤4.
> ol Etrl= utl+= olB
fllc.en1z1Eg4oJ ffiEt TllEola}= oEat4E ola= Ertxl aa
45g + ?lolot eE[. q7[J= ^l¤=
ol?i$ #6l.= E_ZIEH]3 ¤E ==
ni.ll 7l.E 9l= 4a1
g aolq-. 0l +¤ EqEel 3g4g 0186il^1 LtElt!tr|-. lTi Co,",(s,T') Arr.H

=qE s,"(7)=S.(o)+Jn
T
dT'+ Tf
> 6_!d TI1LJ *= Ertrl

o-liil qlEeltl
="J
SE ed utl9 ?lEe4= r=0oll^j ooltl. 7[E
(3C.2)
> EsE] qlHl

.t%+!dr,+ A""oH Tb
^l^]
fle-eup;e-E el=E LIEIL}|= 4q1 eSlpl6E Eol ElEeq= al= Es.zl'xl
olEXl Zld6l.5-^lE E 9r. 9,tGlo}:LltHEE rA). TJF glEtrtr|= =7l7lg_
tselol= t1l= glEeqql tr-d Boltzmann
0F Elr[.
3A)= 0lE6}|
^.I(trE .l; Co,^(g,T')
T
dT,
*d 'Ht -3E rqlel EEg ulalzl ?,16l]^,1 4E +el E+=

"JBe e +eg + gl+. -:. eI r'eg ++4S.4. ol +E s,"(0)g zlle]+ E= oJEg g-
ql Eeel sl-EEi4= + 7l7l
,JB3 ol Eqq +zllE^J gEE r=0o p*q +d ^l
^lEel 4l*B o-e +Cg + 9leq, e. 4EEg r4s "J^l o e +
4t gst4zl &AiY peal gg g-4l"d=H-oe +a6t
rlJ 6l-4+, E= 34ql e+^J "*"1 alts qE +6}al9 rllolel{l
aol+.2719 alol "l+qbrll, r 6I+= fl=eu1e-1 gs *E+ "J=q z$l:ilol trl6}^lg o]]!{-e_E zl$g +E gl
=
E=¤. +44= 3B.zal o +^J olag oFlloll +^l ++q]H+. +.r4s rH 3c.1ql ¤B6IH+.+ cp,.(r)/rE rql
%}89
46H^l rfl +d gE Hol= +61-ts g.q6J 4E"l
q-g-, f_
s(4)=s(4,.Ji ''{'o, ?!Eetrlel EE (3C.1a) g4 ++6J EAg zglt_ lbarql^l -trE +eg 6IH 4+4
E 6l-+= t-dolql el6J Tlol= ++LH= 38.4^loltr|.
as(I.,,= t+A d-Eot ?l=ert (3c.1b) o

oF
GO
010
rl,lo
11tu
-o
q)
o
11바
]-
¤zlrl A*.H(4*)g dol gE T,.,qlrJg d"l slBiil+. +=
안에
uo
E 6I+E %FBC Eq l2Eqlrl ¤EaI4l q.ql aru¤ q+
olgalr. BottzmannE E4l E+4 ull olrll
"lEl+ +"6IE4 trllolElE
)1x11
aq. ol+6lq flE +q. 4l&61+ 4,o14.

HtTb
(4 L.rus Hl Tl
3C.1 SIEEEI9I E-4laJ
=8EI
l.rjl o-4ill
:C.larloll E6IE + 4lel gE rql^J9 tle+4E r=091^J
7 lill
r.
9 tl=.+u1e+ ¤+qq, I=0 ol^JE ¤4 $sql^l ale-l g+
Tl
T
* cr= +a6ir 4Eg 6110} 6J+. relr E. T=04 +C ..ll fg 3C.1 I-aE CelT= SEoll E|,|6llA1 EÊ|q
=d "Jsl 'J0l(dl]=J61.=
SEzl'^l)= +61111qTlolltl rrllz|'^l gclu 8C0l g!=eul# cl6H+E
t e_E +t.tl^J "Jq+= 4 t-d"lEq $E +qE El Et 6tl=J SEoll,\l9 fl!=+tr17l. Etl. 0E,i1 ol'atl +C01l,\] l'aJEo+ .E IEJ
6il +qot +q. qlE^J +=dol liolr #+dol rb"J Eeg E= eul! ?l ra11uq;r1 lLq, T]-Lf taJ^{E H0 |e +olT.!tr|..
3c glE-Etrlol=E 89
o e E= fllEBtrl S"(7)7t +sq, "la¤- Ee=* r o e *i-

rr]6}q :c.la^19 ;rl.rl T=0ql^lel deeElel- tf aE
E E= E fl!-=-eul s"-(D -s"(l)tn <t"l 4¤:4. dTtr=dlnT zlzla_ ¤,E. rql.q9 QI= +q= 4l&g + ?l+. ol 4Eg
zI 9o + q,_(Dg hrql q6H^J E^lql +d eE HolE *
alH 9s rql^lE g+"6hsE +4U 4+71+sq, u++
6l]E g+.
.<J rllolelS ol$-all,<J E tle eq= 44Ig + 914.
gs+ 4+g +s=r+ rJr+.

z]=JEt ofl 3c.1 E= E Sj=+nl =ol
ot4 qlolelE aA Tlalel _E= E 4E a.t
"l¤-al-H zs"cql^lE
tlE+4E AhlB + 91', s.(7)= s-(0) . r+dr' =s-(0) * offG'
=s*(0) +)aT3 =s-(0)+ jcr,-(T)
s"-11;r-', mor')oflel zl {
Debye 9t r.92 ol pffi ol+6lq +gr+ ee A+= Eg + 9lr+.
4E tor+rl rs.otKvl^l 25.25
S* (4.2 K) = S- (0)+0. 14 J K-t mol-r
tdol, 3s.6tKql^J 6.43
r*rl $.rlKvl^l
xjTl g,7J 3C.1 ++9 A+q= 4zlzl E* g+e}
48, :s.ot 23.38
¤¤, 63.r+rol]rl tt.42

{ zlqE 6}= ql zlgq,<ji ol{ol rq El{++. +
cp*(r):brol4. zlgql^l tlE.tr-rlql 4+ zlq= +4.11
4E oE.t+r+el n.zzxt*zl 11.41
q4
zoq.,77.32Kq1^J 72.13
o)-'do+(o)-s=(l)'s .E
4E, zz szr+ul zgaJsrTtzl 39.20
TlillE uloltrrJ _H.{ 0.92
di{ r92.06
tr14 J, s".129g.15K)=S,,(O) +t92.U ICr66l-r. Debye 9t 3C.2 3E=l

Eg tsl-s ol4ql^l ¤BB 4o14.
r=091^JE -Er= g¤+ol gqBeq, Ed A¤ql^l= E=
flzlq olgE-ol +zl4"J rL= Hllgg ol+r 914. "J"JolE
"l ;tzlElqr
Sl-E rlE +44 +d¤ i;J 7l^l Ezlldg r=0 g¤+"1 s.q{+= 43 sl= +ulz} ool gr1
g++9 4$r;lzlz\ qBq= 4014. rrl ** =zlql^J g+=J ag 9"1t4. ol A$$ flE +ulql ++ Ezt ##E 6il
"11= =
of r3oil Blql*qa 7}4ts olE4 ileq 4(Eq 3A)rlE- +q+g+. 4 r=091^J= EE $2ffi-ol u1q
"Jql +Eql
=A7l
(Eq 7A=- -H_ol-+), ol1,"l ulE Debye elLtHe-l E1 gl- aol+. trl+^J T=0gl^JE w =rol4, s_ktn,w4l
^JEIql
=4?l g+.
aol+. ol %FBql^J= cp= 7l-L"* + *e s__uzlzl 1$ E6]]^J S=0ol
=
+ r+*, ar3 E4 +dg ¤zl"ll *+ *+4. olBzll aiE aE-
(a) ruernsE E ¤4
7ta6J+.
T=091^J Ezl-E"l +zl4"J ul]g¤. 6Iq I 9l=eulzl. o"l
gtri= eeSa 4.ol 4*4 ?9
^J4Lr+ +-Jsl= ¤e ar+.
GZE x{Eothlet Ele=rg z11g Nernst9 E 8al+.
qH ++ rillE "Jc_"Jg E g+"*ol +.2 rgld
E44ol'l Eiol4 E++ql +Hlq= flEs
0.431K-rmol-rol4. "l gEql^J ol lzllel E $E+tl5- irl Hsl+ ¤ql ¤tr+ d=Elql uI4 oo+
+6Iq4. {m
d=++.+ +flq= EeEol E+ $C+ gR0
zqE &szl ql+61

*21 trlEql g+*ol e^14 H]]gg olE+E T+ooJ 4l as+ool 2Uru
^lB
cr,^(T)-aT3ql lrl4 gEql qaq}+r 7tc6J + fleq, g+.
e0 2E=lr[ 3H=l
1- + a6Jol zJ 4"Jzlql +5l]^t= qL aEq ffi{r.Jol

rl%L¤1a)q +Îo}(B) rJ +ElE :z dol 9lg + 9l= aolq.
Îolel dol ?l-E
gE(36eK)ql^jel dol slBul(+ozlmol-')E 0l+6}l^1 4l
(b) 3H=.1 t!-=eul
+ el+.+,
Îg s(0)=sq1q *= qj= +rl= 3HEl E=+ul(EE zI+61 'ql
4,..5(369K) = S- (F,369K) - S,, (u,369K)
E +rl')4r *tr|. gE. rql^J -g= tr-Ellql fl= EAel 3Bzl
a* H 402f mol-'
7; 369K = l.09lK-tmol-' qlE eiil= E= (3H=l) fllceul4r 6tq s"(T)E er1ql4.
2e8Kql^Je-l <t#
s.3c.1ql +E-6Ifl+
+S 449 F Sle+ul= r-0*rl r=36eK Îolel g Eq 2cql^J E= HI+ qlB4E CEI{H
a4 ul.4!zlzl-tr.,
+=+# +A6Iq +ts +E ql4. "lBrll ++ {lE=* s. Hrl¤ gEql^J ++6J e4g ^JqlE 9l= ^JCE=J+ Hlg
(a,369 K) = S,,(a,O) + 37 | K-l mol-t4 S-(p,369 K) = S-(F,O)
+= $l= +iil zl-= E= HJ8 g1=+ul n,s"4l c9
+381K-rmol-rol4. A+= ol+6IH dol tlE+ul71 ^tol9
"l ++.+
q+r+ *ol ¤4.
s.= UJB fl!= +ul
4..5(369 K) = {S,,(F,0) + 38 } K-t mol-t} -
A.S"= I
Products
rSl- I
Reactants
,si tEell
(3C.3a)
{S-(a,o) + 37 | K-t mol-t}

ol 4.JEg 6ll$6l+ +o+=ur4 4l+"J+4 zl-69+.
= S-(0,0) - S-(a,o) + 1|K-t mol-r ^lql^J
a+ EJ ^llflg ',JBql^1. Eq 2Cql,<J dz]]t TlsE ol+6}
"l <tg Sql^l Eg Ar+e+ ultalH s_(8,0)-S'Il(o,0)=Q ¤ ol 4lg +q=4 *ol 44U4.
rrl rlrrJ
-l -r1 -l cd z-l=lol
-cj5{ olilrlt- 2:.ll,-zl c'lrl-
-!1=-.a+lt lt"1 .
= =^l
A,S"= Iy,Si 0) (3C.3b)
Nernst9 g C?-lql E6l-H, trJoi r=0ql^J

Sd+ aC tlEil {zl! v1b a}4*4 +E^J ^J^JEql {BH^J= +, H}¤¤ql
E 9l= gdq flE eEl <tg gEs 00 +eH -E-= sd
+
ae +¤.E-9 fl=+ulE_ T=0oll,<J ool S+(gI6JEE ^JCql
+Hlq= flE +ul Eq+ _tr= tF dolql^Je+ u|tiz}zlg ol t 3c.1 E= 3H=l g.!Eetrl, 298Koll,|t1.
gEql^l 0ol q7l ull$"l4). eEg q+r+ pol eof$
"l s;/0K-' mol-')
4o1 u]._+_ Eq+q 3fl?slol+. z4l:
E-= sd+ aa Eag dE eul= r=091^l 0ol+. 4¤, C(s) 5.7
qoq610l
d--- vH-
"r+tjil
4"l"IEg c(s) 2.4
¤8, C,rHrro,,(s) 360.2

gq+4 o +"J EE, ol tE {19 oo -+ += ag ¤E^}q
-0 a -=, Iz(s) 116.1
ACe 4"14. r*l+ $z|;5"llrJ Sl=+q= 6H4a]l-E-H
94:
T=0oll^lE ,r,l -1olse ElB6l S=0ol qolo} 6I= aol+.
qH A+ql= T=oql^l 1,r > lol qq ,rl4^l s(0)>0ol ¤ Hldl, cuHull; 173.3
E
4. olfl a+ql= ¤ql gEoil^l EA6J H]]6}.g *=ql q=
Hro0) 69.9
qLJzl zlzl fizl g+E+. qlE^J 2il4 +zl ABE a+, ... i3, Hg{t) 76.0
AB AB AB...el Hllile+ ...BA AB BA...9 u]]rl qlLlzl zl{l:

Îolql
Zl7l 44 sg + glsq, oltrll= 7=sollrlE ,rt>roll g+. "ilE cnngl 186.3
s(0)>0ol q= Eee TIF t!==ulE *=tria "J++. g* "l4I++4, Cor(g) 2t3.7
3:.+Jrc-rmol-r9 tF QI=-+ul= *=Ell, olag "JA E + fr, Hr1gl r30.7
zl¤ Hlig trll+ql +4+= 4"14. 4 t o

ÎolE +^ aql
BE, He(g) 126.2
fl4t 24],E s3 0-u aE+4 24E zl o...H Afifld g "JEqot, NHr(g) r92.4
zlc| paJap il=)g zltlt_ ?lzl"J q! + eElol #r q . zlE eql cl B9 <lEol ++qq 914
91=+ulol{! 91
qlql^J=- f .g= *=trI. H}*ql^l zl4lzl dd4g_e ^Jc gol eolzlr 9lq-. ol sl= eul9 <t"l ¤-ol4E ag "J^dzI
¤ qt= e= eI* SI= +ulz} oJol qA TlilJz| Arr$ trIg z| u1l +ql e^l= +E^lzlzl ull$ol?+I
3-o
^J46J + 9l+.
olaol *ol 9zl ¤trI
#JEt 0{l 3c.4
zlEtEt 0{l 3c.3 C1-(aq)9 S.= E tl=e.u1E +57 1K-r mol-'ol4,
xle ¤9 s. zc.s-e+El gs+ qlolEl= a4q zgsrql Mg'*("q)oll ql+ {lg _1281 K-' mol-'o14. 4 cl-(aq;
^l
HzG)+*o,(g)+Hro(t)9 E= HI* Sleeqg 4l4I+ E EE $Ieeu13 +s7l K-r mol-r-tr^J, E+E "JdzL
4. tr+ +g <k& zlz\qlolulE ++lql E9 *zl4 +4
E B fr$alzl ullgolQ), olql H}6ll^l Mgr*(rq)9 (}3
A.S" = s;(H2o,1) - {S}(Hlg) + }si(olg)}
l28f 6-t mol-'** *u11olulE ol olgE gg {a}e oJ
= 69.9| r
K mol-I - {t30.7 + }(205.1)} I K' mol-l 6ll^l +gl E +zlql+ q +zl4 +aE *tsalzl rIE
= -163.41K
rmol-r oltrD. =
Ql= +ylzl- ols+ztol zlt6|= ag + 7li"ll7l- qq+ .l
illg H6tzl rllEol4.
(c) HJE fllEEJTlE 8s. E=
Sl=.eu1e1 gE E¤g +4U {ol 3c.Ia^lolQ, ol{g ffi
EE gE 8^l gÊE -s= E flE eq= q+ pol oe
4 rJol E tl=.+ulE El¤ + 9l+.
E +sts "J ¤trl". *ql^l ol"l ¤Bt ulq ?"1 ol=9 il
g 0ol olqr+(r>og rll).
s-(4)=s.(4).J; 9fo,
Eq 2cql^J flR4e+ +¤49 *ol9ol "J EqflE "Jol
ol Hl*ql +qd+ _EE Eeq 4+qq, ulz|..rJ 3c3^l
^lg
ql E6il^] gE g= E= Hl* sls+q ul-e=$ pol
g"JE +"4e "J= + S.4. ag ¤H*=ql, +.1 +q 9l ^J"=
+E}s + et+.
. olgSE E.= E sls +iilE E+q H*olgel s= sl= +
trl=s.=gEql^J 0o + +=+qEql E46il^J +4UtrI +
Se(H*,aq)=0 E"_q +E 0t3 t+qrl (3c.4)
4s"(4)= A,s"(4).1; #0, (3c.5a)
9zlrl e= z4 6I"il^J
^JdE4 HI¤¤E E
g+*
ol +Eql ZtE¤ z|=. ¤9 E 2c.4ql ++6ll +9t+.,
"J4L6J zHEr+^.qg Lls= 3r|trI*zl 4l+"J* 7re\4^l)E +l
E+ql ilE ol99 Sl-= +i4= E+ql 9l= fr ol$$ zli
Hls"
^Jql
* 4"14.4,
"J"J +E gla g
o + qI t}'il4"J <lol7l qlEql ol <t=g
"JE qlE eirJ= r olgol E+E n* olge4

.J +E gltrI.
4q=>r,4*0 (3c.sb)
+3 E fltr+ul= 714q, *9 Ql= +ulE: olgol E+E I
H* olgEq *g E 8l= e"lE A=trlE Eol g+. olg {l :c.saal9 A.H"E gE E=g +4.11=Kirchhoff9 B4(Eq
= +4 <IEg "195"1 r ++lel E Ezl-= Ag^l7l= ¤E- 2c4 2c.7a4)4 Hl+61+. A.qol r,r} 4Îol9 3s gqql
q IIl+ ffi {_o + d6}*E 4}g olgg +
'lql¤+. +g ^l
gEql +se. 4lE rC.sa^lE 4+ol A,q b(r2trt)ol qq,
+19 E Ezls 4q+ +zl4"J g^JE +4441 6Iq, r?]6| q^.q-r+ ee a+= e4l ¤+.
q ++l a4=JE olgel a+E+ +.+g +e^JE q *
=
ol 4rar.lA+.++a4 +ql Eqgl= "J^JzI9 3Bzl g qlE a.s"(Tr)= a.s"(41+ a,{r"f (3C.5c)
-Erl eEll aig ol "Jdxlz} E+ql^J +E^l7l= +a EBg

zlzla_ 4l4l6J + glsq, qlllE -2rl r(t mol-'olel} q A
l Eq sa"ll,<'l E"Jg +q= ^F8-6lzlg +q +9 "199 dE eul= ¤41

4 e tsE t= euleE "ll"I +4. ol flE-eq at +q= olsol e4Be
0
eal ..Jzlb r ++l ¤.,ll Ezi9 a4 islzl E6Jqq9l7l rllE"l4.
92 2E=E+38=l
zlEtEt q 3c.5 = -9.94| K-t mel-t

Hr(g) + jor(g) + HI*ql 4 el zqs Kql^J el -s ol a.ci9 *¤- :c.scrl9l Bq+E 4E 9s, qlA4
HI* Slee.ulg -44.42;K-t mol-'o]{, ol= +zlq 373Kql^Je-l a,S"g +g + gl+
=
"JA-S4 g g+*g Hro(g): 33.s8JK-'mol-'; Hr(g)'
28.MJICI mol-r; Or(g)' 29371re1mol tol4. r}et^1, A,S"(373 K) = -44.+2lKt mol-t + (-9.94| K-t mol-t)
.
x ln
373K
L,C; = C;,*(H2o,g) - C!,*(Hr,g) - +C!,,"(or,g) rrtll
= 46.65f K-t mol-t
TI|LJ=
=s-d
Dl. gaE slE erl= x]gc--e+El +d 4{} gszt^lg g
-J T=0oll^l 0o14.
*+r+ ol gE +zlql^1g ^J. d"lE g-4laJB " e +C6l T s. rillel tl+ fllEBtrlE r=ozlzl ^l+q= +g^lql 7l"Jq
q AAql+. qlE eEl+.
=
22. Debye-.r3 E=l(Debye elt %LB)g T=0 *i-lgl^l Hl;r+ r. :l 6. 3HEl E=eqi s(0)=6q; "J4qFl.
nl9 $ls-eY1g;alali rll o16.¤4. -1 7. aE +E olgE E= SlEe4= EE gE_ql^J s"(H*,
tr3. Nemst9 E Ealq E6Lts E44 4zli slql4 EAt9l + aq)=091 ol4t+.
eE Efl+ SszI ¤4 oql zlzleJ{ffi sq1
HlEl= qlE ---l a
I u. E-, B[e.ollF=rfl
.EE L:6...:._.4tap
I co--u tl=l
u--t I_r E.-
^.-l-.iiL
A]ruol lul-ltril
o"1t--1 o oa"f
-Al>
iI-l-
d=++ H++ql +q6F= EdEol Sd{t A^JE ol#zl"J * Eq t'-EtiE El¤+=E tr= t'-qlql^lE g qlE+ul ^t
6IH T-+0oJ 4l ls+ool gtrI. e+ aq.
rJ4. gq-et 3EAql E6IE s= f}d AC EAq qlE+4=
=s-d^lE
oazl
,(-l -1I
z.Al
I--1 4Ha
g_41"*e_E +oJ E= E. QIE eE 3c.2^lg -H-or4. r=G?El +d q]{}grzlzlE dil 7lq 3C.2
s.= HI* flE +irl o't"=.to"3 --I"î u,EloI*4 4l+("J+) 3C.3
6,5"=)v,sl0) ur:44e*4 +(+E 9lg)
-tr= HI+ Qlgul9 9e. 93 A.s"1?i;= a,s1f I*ff 1d'fitrpr 3C.5a
A.s"14;= 1,s"14;+ t,Qmg,tr,1 L,cizl gEql +SEl trll 3C.5c

E4 3D AI +IT+ LIEILJ ¤E
(a) rl,J8oil EH-d 7l=

> ol E4E H|l+ts ol3
Elqfotl^J trC tH80l El= tH?EE HJ# gEEt AEe+ "Jal +d +rl 6}qlrJ9 z}9g ^J46il _H-z[. o1tr]l= Hl-*
"JC6J
6lollî golUtt. olal-el IA 6pll^1= EE+4 r+tr- 0l Enf at90l s-o o + dfiv-duolq, tr}+^"] trl+4 ag +4171 d
oll^l 47llB Gibbs ollLl^l= 7[xE ts"flot -gtcl. cibus 0lll-lxh
B+tr}.
I EE, ffi gg, :lalr gE ollLlrl+= tsE61.= 7l*7|-Etrl.
> "-qc 7]lE
ar-f =o
"l +f,ls zl$4 Hp+el 71=g s{
Gibbs gllLlrl= g!-J e-_Eel gelq^jel rlEl4 EslE edololq, 4lE tlel EL+="J
+ 91ts AEH Hl-98 g4 eq.
Hql^l +e6J ¤4"14. ol {g r+g=r+
Al7l6J
zlzla_ +4H+=
> E9.Ej qlHl rl^l ?ol r4¤+91+
0l Erloll,'.'l= Clausius +#l(EE 3A)= d7t|,\l7lq EE 2coll,(l
Tds > du (v zY "JA6II, +714 "Jol $.4) (3D.2)
¤B-d EE gElle+ HJ8 flBEl0il S-d xl^l= ol8g aolq.
Bom
^+3
ffEap Ejl= F E6l'AtolE Coutomb trlEl¤ ollLlxl= 4+ 9C6Iq du=gol g rlib ras >0ol !tsrll
qlLJzlz}
0lE6Fll Etl(EE 2Ael sl¤Irl-sl8^l 6). T>0olE + "lag dSu, > 0(e4¤3 gC+ z4* -E^l)ol
g+= 4*zl g+. a4= {94 Hsl.ll 4t zl39 4l
"l
el cerrJ 7Lzlr. ++r-H= 4"14. + +qe+ 4F 9lHzlz}
zl¤4 EEIq "J6Jg flE eq9 zl]Hg zlzlt_ "JCql 4l(qlaql rB 4l)qlrJ z}ts4 HElzt "Jqts q= sr
=t4e+
"Jg + ?lzlq| "l zl]'Jg ols-" olalts 4le+ r ++lE E+ a u +ulz} ?zlaJ4E 4"14.
"lag t44 + 2Hzlel 4+
o
^16lzl ?+eH "J

¤+. Eq 3Aql^J ¤EqI uig+ ?"1 ?fl 4 e3 4"14.
9 9i= +vl Hsl¤ 4l&6l.= 1"1 aJt ql+61 dzlb 6fzJuj "JA6J "Jq 6}ql^l
qlqzlzt gE^J oldqa s^J "J ol9
(AS,u.=4.u,/7,,,9 olf-all,!), ¤zlr-lE 9 4ztrJ f9l9 zl¤ E += "J"l Bdlzlzl 9*¤. oil= a4o=dH7l9H :o.rrlol +
z| 2ffi4 o + i.l4q= "JHg gd^lzltzl ql+ ol+al 6l *4 ?ol ¤+.
H 4lElg +]E_6tE qr, q+^l gqqig 4e" alzlTl a*a
slE gqqlg ++6}E
Tds > dH (pz| olzJaP , +714 "Jol S,4) (3D.3)
A+6HTItrI. E6J ol %r-Hg $.e-e. ql
ilq^J .J/J. zlEol El= 4,o14. .Jqr+ Sl$ylzl- gA$ ollE ol zlol rds > 0ol :.qa1q !L
>
ds 0ol q=rJl
"lag 6sur > Ool+a +48 + gl4. rq
3D.1 Helmholtz ollLlrlgl Gibbs ollLlrl aI{ z}ts4 r+eq]^J= "Jqol olzJap c. tBulTI "JC6|
zll #zlB trI 419 qlE tsrlzl fizlz;\ot ql4tolBl6J ++aql^l
olxll$E rql^j ++le+ g4 B¤9 "l$r ?l= 4lE ^84611 flE+rl Hplzl- 9l¤- + H= aolr+).
++lel
= ,r.lltr8 gqE4 6J+E E"J6IH +vle+ *4"1
-Hzt. 4lql^J EsPl "Jq+1 !le+ +fl ,tlololl,<J glHzlzl- F ,]]sl "J
gE^J
"ldg 4l* Ctausius PF^l(3A.tr^1, dS >dqtT)* 4 C6J trllE zltsCql ql6J 7l=g gd q ttr6}rll +49 +
94?ol ++9itrI. ll4. :_ 6l+= q-.q-4 rJ.l c99E Helmholtz ollLlrlAol+.
as-f >o (3D.1) A=l,l -TS Helmholtz ollLlll i8e-ll (3D.4a)
gq+= aaql ,r|4 + zl-zl t{("JC + rp-lr E 6l.q= +g-4 ?9 OiOOs ollu'lxl Gol+.
+lE {e Hs}rt
,l+ E= "JA g}q) o + dzH^le + 9l+. G=H-TS Gibbs ollLl^l IEEI (3D.4b)
ol= F eEql +s= 7l-o-Ee d+ 4lql 4aJ 1Eol4.

14 2g=lrl'38=l
gC+ -$Eql^J 419 {l4zr H6IH olE *+zl yl-$a\ z; (c) Elctl E
ol H*+.
Helmholtz qlq4 H+= zlts4 Hs+q 46J *E"J S"J ot
(a) dA=dU-TdS (b) dG=dH-TdS (3D.s) ol-4oll.! Eol| uts+ ?ol "JC+ 8s.q;,<1 4lE+q g
'14,
gA+ +rl o}"ll,tlts ras > du(3D.2^l)qlql, 919 (a)rl$ ol e + 9= =l'il gl} e4
e"6IE ol4"l dA < 0ol ¤+. rel:r' "JA.J
"Jq 6Iql^J=
Tds > dH(3D3^l)oJtrll, +lel (b)^lg ols-"6[H ol{ol dG < 0
zJAl
ol ¤+. "Ja4zl *zl9E E+= ezlE 44H +^J zlg ^plq
"
4 Hs+g 7l# dAg+ dG= trh-q=r+ ?"1 448 + gl+. 44 "Jg Helmholtz qlqzl H+= zl\a- +ElB + gl+
ag +E6I7l +i6ll^J *d clurrsius *F^1, ds > dqlr3
(a) dAr,, <0 (b) dc?,p <0 Eslel (3D.6)
=
Tds > dqs{. ?JZ E-tr ,* ,r olag l$zl, dU=dq+dwc| pa3
^1.94
rl.x.
/lE
^14
q-g-r+ eg !g "J=+
olE Eail z163 ElqI ge+ql^l +d q6Jg
+ 7le +q
dU<TdS+dw
6F= aEol+. qs^J sg HI+ql^J= Hzl ftzlt;L¤ aa>o
olzlEL HI¤:ol "JC6J giae+ Sq6iql^l zlB4e
"lq+ dq 4d9l r H+ e trJ rdsE B"l fzl qlgql
"JHl4-o
E "Jq+48 qI+ dwl *Hu_4 zI"IzlE 1ol4.ol= trl-e-r=4 a.ol I
^lg +^l
cz1 a}la11op E|+^J dG=dH-TdsolE
-e 4lel sle +ulz} 6zlai¤ rdsz| dHE+ azlul aLts ac a++el+.
7l gol g + 9l= aol+. r46lq gg HI¤+ 419 els
dw > dU-TdS
eul 6z17l +flE Sle_eu1 ali(als ¤ol g4EgzlrJ
ds,,,--dHlrrt E+)E -H-+6Ir. tssE "JqB + fl= aol 4+g tril slrIE ¤.ol 9t. d* ab+e g¤. +
trI+^J f,f-s71
+. gg HI¤+ 4sasolF + rdSzf aTll *ol 9zl ?*E EI 9l+.+ fils+El "JEAI eg + 9l= 4q "llHzl} zlq 4
col "J"lB ollol4, "l + gl4.
"J*4 " + dG<001 9s + xlg4 "-a "JqU+. 3lEil q-q=r+ u.ol 44L3
"Jg
dr*"* =dU-TdS
(o) rermnotz ollLJrlq +-d E Tlrl +E .JC6J gEq^J= dA=dU-TdSolE-+(3D.s^l) ol ll$ ffi
419 Hirlz} "JC+ s.Ee+ "Je6J +q 6Iql^J zlg4_oE "J rt ?"1 +4'J + 9l+.
q+48 dAr,,,< 0ol?+t ++. ol4+ 6Hl^Jel Hl+
= =a g
ol zlg4 o e "Jq+EJH Hetmholtz *izleiElqot 6J+. dw,,,r*=614 alEll (3D.7)
c*6-J"14 q"J.J 4Col E+ "Jq+zl ?+ril qE ¤¤ 4 zl

dAr,y=ool4.
=g ol +41 trIEql AE qlE='4lr]] "JoJ+', I:='"JEr-+',4a q!
7JZ dA=dU-rdse+ 0g q-q-$ Bol &* 6]]46t
dAr,v<
r+.1
7l fl+. . dATl ¤-ol 9zl 91a1.<-1= duE 4ol f,.ol slr.
q+ql^J +Aol 7ls"B CEq s"S HEIzI "JqB ql=
Al
rdsel alol olol g"l"F q}+r dl46}7l ¤+. + A7l +L4
3D.74ol w-"*- LAT! qq, 9zlrl AA=AU-mSol4. olE
+e-e- 4lz| "IE6IEJ= 19 "l-zl AlTl *+ 4P glHzl
= +41= r^sE +gql tr++.li+ qlqzlel HsI%L"l dP "Je
e++g QIE eElel t]-El]E qElr 6}zl ullEol+r 6l]461-zl ol+g + s.+= Bq=+. 419 Qi-= evlzl e^q
fl$ 1o14. rfl+ ol ^J4g ¤zll tgt$ 3* a]]4,* 4ol ^l-¤g = lu-rls7l AUtr-+
4 ezl AAIEI= A-Jg d4-"-e. +ill4 Ql-E+ElE tr-
i HEIzI "Jq+^l ras<ool E 4E +
EIE qeJ= A6J qlEql +s= 4"14. = e +el <ig +44rll qq q6[zl= fl4 "Jol 6y zlzll_H-Q
+ 471zlB.4oE zi"tti+. Hs*zI zlp4-o + "Jqg + gleelfl qlqzlel g
Hdl+ 42 t\"l ++lelE d4l {_= eirlE =" z}
Hle. 41eI
xlzlzl ull$olzl,a? {+ "llHzlE *41 6IE= At,J qE *zI ¤e^J mI4+TL Alql^J ,JAq= Sl_Eeq= +'J6lr
ol oI44. dAql ++ ulzl !lz| *e qlqzlel tsg e-tre +9lE qlE+El= ¤zlxl40t aJr-l-b 4014(:z
^13 ^J4. + H :o.r1. "1fl a+q]= 4+ 9lHzlE "JE ol+6l.ElH rll+
ot6|= a+ rJ? etlg +zl"J ol "Jtr-g g*¤ 4,olr*. as
4lel qlE_+ul Hplol:r, _dutrb ++lel tiE+rl HEI"I "llHzl+ .J+= z}¤qlq.r]l-Ir c-8. Hlaoh q^= ar+ ,Jc+a-
=
q(Pulz} .JCg rll), olE9 6Jol 3]El]7I qela alt 1ol4
t E"JolE oJS Rrbeit4-L al4, ol trllEq zla ul +*+
Xl ?lTe LIE1'.! 5tr 9s
daa1r14E- Ciil4 e-E= zlg4 4C"l g + 91tr1. nlEt^l
J 9"tz}9 qlqzl(r^sel Altr+ arg;zl +flE+q gq

q =q
e+^l "J9 "J+e Ht+l= lolrH:-H 3D.2). oltrll= z|flol ,t1l
aU <0 #g +|E6l+ a+rJqa ^J4g+ 9lrl..
aS <0 w AU
lS sur >0
E@ aEilTlEselzttt
25 "Cql 1.000 mol9 c6H 2o6(-f= +n-9-4)
r
o
I HI+ cuH
^-1 "ou(s)
E++^l
fal 3D.t AlTl+ge+Ei raJElol ?l^l ?J= ntl=:d6HTl "Ji1l'Lt|+ ollLl^l + 60r(g) + 6COr(g) + 6H2o(l)ql
"l4}s*Ere+ E
EatTl tl.= + 9ltrl'. 0l rzJE 480.|1^1= 4lel glEetrl7|' zJ46l'q, qalll E &+¤+. gzl"* a4q EsLH 2s'cs+ -E= aaql^l
0l r[¤01 ElTl +l6H^]ts ++lel lee{7f -Lrtrl. 0lae L,,U - -2808 kJ mol-t ol l lp= + 182.41 K-I mol-r ol +.
^l"J40l
4E+El 0ilL1^l7f Ee,'.1 T?lE1 S71^10t afE =7l6t|0F
qeN AUEq ar'8 "l ql
,Jsl golEolt!trt. =:dtrt. qzl He+ ?9 9"1¤ (a) "Jd Sq 6rql^l ptr" r?-li1
(b) "JE^l S"I B + 9l4ll+?
.a.e{:gAtB "Jc-sq +q^J "}=q= ge a

Hl+oJ + gt+. "Js^l z}+E;al + + gl= rll+ qlqzl ^Helrq
Â= r+ a-q-E-E nfl= A.uel {lg.E+q +6110} ++.
9 'JP"l4, A= Helmholtz zl+ qlqzl+r +s= AE "l
ullEol4. 6Iq +flB EE Tlill# ol^J-4ol+r z|{a}r. 2r..44
(AH= A.U+ AnlTtr )$ AfI= A.U+ AvsRTtr- r-6I ol+d
4lz| atE oJ4 Hetrnholtz glHzl ,r.|o1E +41= a+ q 4
4. "l 4CsE+q gg + 9l= slrl "Jg w^ *=uE
^J46ll E7l +l6ll^J "Jg ?91 flzl¤ol +"JeL ¤+¤ "J
ol
eTlE+ +#El= .llHzl+=
Îdg tzlalTl H|++. ., w*o= Ar E E-e- nl,<1 4l&6Jtrt.
A=(r-rsa|-u. 49 4el dal ql+ 9lHzle*Ei g¤+ qlLJ + LII= L,U=*2808k;mol-tol4. 4
(a) Av*:gol o
zlE^l zlt}¤ ++(rs)¤- u a"l Ae+ rJqa 6114g + gl= =Ol
4^l "J4+ "Jq 6}ql^l gs^-l gg + 9lE .llHzlE
4o14. + LeqI g¤+sE^J ^ltlg {lHzl} ++lql+ + 2808klmol'o14. $) T=2e8Kol Ir + A,Ael Atg q++ a+.
"J6J +E¤ 6l]+= Ell
ol+B izl- s.gH, ul4rJ +e^J6lal
zlt}¤ ++g 4le]+ u-Ts "J"l "Je d¤+¤ + 9l= Lol4. A,a4 - L,U - 7h,S = 1862k1mol-r
419 $l=.+iilE +7\^lzlH! Hslz} "Jq+H(= r^s>001 I[I4^J 1.000mo19 c6Hr2o6g ¤a^l7lE 4qE 2862k19
q= A+) trl g-9 al"l ¤4. olfl A "Jg eg + ?l+.
û-r^s7} ûtr-+314 =go1 nuE4 gq ^8
+ql= 4ls+El eg + 9t= =-4. +1 0l HI*ql^lE $e e s)zl frzlolTl qEql(+ts-4 0
46rH _si?l aile -H.olzlEJ ol4g 4l7I rBqq qlzl tJ: -E= EzlE+q Bg zlg +zlzl .<!zl7l ql+ol
17HE
ol "Jg B tr|] {lHzlz} gs^J 41tr_ gfl f ?lzl ullE =
=qa 4l 44e eg + 9l= "JE "Jol Lll+ 9lHzl H+Eq
ol4. olrll= 4lE qls+u1zf f;zloleE ++lE qlE+r]7I trl+^l ol fllE ++lE+q {lHzlE EqL|]q(Ir+E}
=4.
qlE eElE z]Âlzla) 9e d+u,la + 9l=
^l +g-lE
4,"14.
rPf B7l 3D.1 'J? 44 6lqî 1.000mo19 cHr(s)7t ¤
/-- q
tr1E 4l4}g EE"laI¤+. s. zcsq ql"lqE 0l+6}
^g
{4. zgsrql^] ol H}9" 91 4t a"sE ak? -zn} K-' mol-'
aU <0
oltr+.
aS >0
w> LU I>l¤r8= l*r l fiOO8= ldb I :.8
aS sur <0
+:d E 7lrl +9
(o) cioos ollLlxloll
feJ 3D.2 0l rlg0ll1l= ll9 fll=eul7l.=71.6|.q r+al^] ++lE tlE-etrl
7l g.=trl7J 34!qs saE.l-. +ge+El gol.rJE 0llL1^l7f Ee.t1 z1|s
++ dedql^J= "JHI4 o + "JC +4B+= "Je "Jq 6l
#71! + ?ttrl-.01
=
Esl oilLlx17l E-e qq T?|E El=o17l-= a0lq. qa|.^1 ql^l "Jq4= uqg rl r*"1 ++qot 617l uIE.q ElEql
:d6Hxl=
93 auecl + ?]tr|.
=
e6 2E=14 3Ee T
P /
dotdwtpdvtrofd
9lHzlE4 Gibbs 9lHxlTl q ^L+ 4r"J+. E"g Ec|"J
uermholtz ull=
+PU dT=0ol E+.
tr+{^J,
^Jts
dGr,p < o9 7\39 sl+ql+ szlH, "J4+ gEe+ glq 4"ll
HFu
dG -- dq+ dw + d(pV ) - TdS
rlE ciuus ollr,lzlz[ 446]b gta}e-e.9 44 H]-&ol z]ts4 dH =
ol44l "JB + gttrl. q+^l qts + HI+ol "Je+ "Jg4 cJ4lz H4zl 7lq4 +C"J A+
8r alq1rJ zlg4"Jzl9 q+E gElH r HI+ql +Hlq= zl94 o + HEIzI
LGda
"JqBTS 4lb dr=dw,",ol_tr- E dq-dQ,,,=
GFH
-
Gibbs qlLlzl H+= g.t"t ++. "J"J HI+ol dqqE 4 czy
aA6lH "l qI¤+ t}¤_Ee+q d^JE +e_e z}ts4 Ee+

rdsolE + 7Iq +g r+cql ql6il^J=
s + el+. dH Tds '1"¤.4
ae +41= E
=
sdXo
-
-
E "J_g-zl4r B 4o14. r4+ Gzl ftzlolE :. 9eI*"1

dofdwtpdu
xJ
Tds
=→
z| -
원
do
ts4o14. ge+ gEe+ DSc"J6J4
"Jqql^J = q,J.Jq qL +
dG = ffi + dr..u + d(pv) - TdS = d*,"u+ d(pv)
4eE zlg4 o e "Jol+zl ?*= ¤¤q 71++ dGrr=so14.
zlg4 gg HISol ¤zl]E + 9t+= ag ¤E6l]++ A E4l 3 tloloJ ++el
ol Gibbs .tlHzl9 q$ol+.여다
"JE
4, :z4atq 4l= z[$!9.E

olelq} H}+ql^l= Hzl ftzlol
.- 00n .
+g $84e1 tr-El]s ¤-4zE
"Jg saL "JrI += =E qI a"
4^l7l= 4zl4 "Jol+ E= "lill

F9 "J(qlAEH q e + dzl¤
7l5¤ gel+= Tdstdwftpdu $
rds¤l
"J)E ol
-
z|$!olu
dwtpdu
dH>001 E+. ol HI¤+ e an>ogollE H6IjE +qd+. ,Iq 4eql^J== StrL "Jol -pdvolq-. Ir++^l Hl-S
dc<0ol g"l"t qi+. olag 4lE sl_E +Elzl rtzglol Tdsel +"Jg dr.ooE 4441, d(pw-pdv*vdp4 +41- 0l+6}
do+E dHE ^J4l6Ia hI=+ H +lE q+4
Tds
dwaddtpdy
=
dut
1
atol ¤l+51 44^J dG=dH-rds ?"1 ¤r|.
P
F
= …
. ag 9"1t4. trl-{^J gg HI¤+ 419 tle +yl #z}9l

^lol
dw d(pv)
el6ll^J +dqq, ol QI=+ul H+= +9le] QI_Eeq +L(+
OI tl r-l cdrrl
r-l-"1
= -z-lr l-zl
uul ,1"1 nl rl::1.
/ l'-lr rl ol2 dl-=l^ll )J uosur_-srr/r,,
*1 L1,.l Jo lrrl.r,t AC-(-nAl/+Ar^, \-r- nrl 1/t-l/An-An t-l/An
-T1 e."l ""1
=-o rl=-ll,.l
…
^J4l6Ia
gg AEzI lolot 6J4. gg HI¤-$ srJ4 " e .JAl4
=
ztg4"JrJl, : olf+ dH<0olq rr-16}¤ raszf ¤^} gg A+
"J4"1 "J4,*
$ETI "Jeg S"J otq4 .J4"1 gAg 4E ap=gol El
zl+E olaol flBrl ,Ji= }.zl-6lzlEJ $}sE dc<gol q
ol dG=dw.aa,,.uol E+ tr+4^J "JA6J gEe+ $q 6}ql^l=
dw dwexpt dwadd
zl ulEol4.
ㅇ
= dw"a*,"u=dcol+.rBl+ ol 4Ag 7tq4ol=e q6}]d "Jg
4ltr]]zl= 444ot 6Iq, trl{^J
(e) Hl-ts8 g 다 'l+ ^lol ^dB6J+.
=lctl
pdvxdwadd
alq Hl-EJ8 g
AlTl * + 9l= altr]] "J¤- "JotH.'J {$ u}}z}zl
= -
[g¤-dr. P]
(3D.8)
ÂE+q
E Ac-e.+el=_ u1aa3 +rJl= "JolE + gl+. Herrnholu glH
dw".i6,-"* = dG
zl$ =lq "J4 ¤+^lAH a4 HI+qi Eel= ola" a[fl oj{

EL gEe+ 6Iql^JE cibbs
$E "llHzl Hplzt al'llel +714 +C'J + 9tg AEE +eI+ Hclql ql6l]^J= wadd.reu=Acol
"J(Hl-saL "J)r+ g+= ag B"J + gl+. ¤4. "l 4e ¤e dzl4 slqr dzl"llrJ ^JzlE 449 dzl
4 "Jg +61-= rll 561 f+6t+(Eq 6c).
rl EEIq AEll HI-EJ8 g
/\tolel zJ4l 3D.2 E= cibbs ollLlrl
H=U*pVoll du= dq+dwolEE gHI4 47J Hs+zI "J"l
=
g rI9 ql$tl= tr|s=$ 4l"1 HEI4.
E= HI+ QIE +vle+ s= HI* $BulE(E9 zcs+ 3cql^J
¤EtD A+6IE E= HJB cibbs ollLlrl Eg + 9t
dH = dq+dw+d(pV) rl 7- ^.G?
4. n,
r4r ole+
"*E= Gibbs qlqzl(G=H-rs)E HpI= +¤-4 s= UB Gibbs ollLl^l
+r+.
AG"=AH"-TAS"
rrr tEetl (3D.e)
dG = dH - dq+ dw + d(pV)-TdS-SdT
-TdS-SdT s= HI+ Gibbs "llHzlE B^lg g.5aoil^l E= ^JEHql fl=
^JCEI+ EI¤¤ ÎolE E6 ciUUs
EI! 1 $ETI "J4+ a+ 6llR HI+E glHzl zl-e+
3D 4l +l+E LlEl'1.! dtr 97
zhL
E t. E 3D.1 E.= 8¤ Gibbs ollLlrl, 298 Koll^'|.
Gibbs olluJzlE Ae{+ + "JBg g-4lelg ols-"61ft.{
arc"/(kJmort)
olr(AHts zJd, s= g-so olEg E BB
"*e-E+El). ^J+{E ulolotE5 c(s) +2.9
q 6A), dzlple}4 +c er+(Eq 6D), r4I 7lillg a+ql
Hl{I, cultr1t; +124.3
E%IE4 +A er+(Eq l2E)-tr+El +g + 91tr}.
= ,ilts, cHn1gl -50.7
ol&E++i,COr(g)
Etr@ u=EaqtHI-sasatj E, uroll;
-394.4
-237.1
37'C(eol9 3E-1E -E.= arJql^l 1.00mo19
r- $xlz| &p+qH {a q gt¤ frzlrlTl==+i9
qlq
"Jgr-lot, NHr(g) -16.5
gEl+EE,
=+
zlE Bul+ '}]+g + glaL+? s= ** sl-ee4.
NaCl(s) -384.1
. ztE ¤ql rl "*9 <lE"l ++qq 9lq
+182.41K-t mol-tol4.
a.a{:g ,t\}e "Ja+ gEe+ g}q 6}ql.<J qfe" 9_e_$El E

g + ?lE Hl-S+ "Je r HI+E E= Gibbs glHzl HEI Sd HI3.e +Aol **ol7l ql$ql gÊ$ s.= ^J
ÊE
C ciubs "tlHzl= 0ol+. H zlzl ir+.J$ql E|]6J Alg E 3D.1
A,G"e| ?4. "l1g 4l4l6lEJH HI+ Sf$irle-] gE el=
q +$u|]fl+. ++4 ?"1 olE Atg 4e6l p6J6IE + HI
g 5-,<lap g' 2C.4e+El A,rr"(37.C olqr 2s.C)g +
6Ir qlolEl;i$ A,G"= Afl"-TA,S"ql HgH ¤+. 8E e.= Hl* ciuus ollHzl= z}+61 4l&6J + ?l+
E= Hl+ flBll= -2808kJmol-'ol 9oe g= HI

A.G'=fvA,G'-)vA,G=
=ol Products Reactants
*ciuus "llulzlts
q-q=$ ?ol 94. E= UJB Gibbs ollLJ^l
(3D.10a)
tAA "Jts]
AS" =1808 k| mol-r - (310 K) x (182.41K-t mol-r)
=-2865kl mol-t Eq 2cql^-l ¤B'* zlc.E ol-4" 6l.{ ol
^-lg
q+r+ B"l ¤
,rl+^l 1mol9 3F=q^ Ezlz} ¤Ag qlE u.aa,."*= + el+.
-2865kJo14, ol EI¤¤ 0l+6ll^l gqB + 9lE slqlE A.G"=Iy,A,G"(]) (3D.10b)
Hl-SeL "J9 zsostyol4.
+4 ol pffi a+ q ¤e'+rll oloNalzl +l6ll^J rll6ol ¤zlrl ,lEeI4H}+^le] ++%!4 +(t +s=E"J)o14.
70ksoJ rl-B"l fzl _+ 3.0 m +ol= 9E= ql 2.1klE "J
"
¤- 6110} +qr ^J4dlBzI. "l"J+ "J¤- 6lElH 0.1399 E zEtEt 0{l 3D.1
ERol gs6}+(¤xllE= olE+ ¤{d q Bg "Jol gs ql6J
2s'Cql^J HI* Co(g)+*or(g)+Cor(g)9] -E= HI*
6t+).
Gibbs.llHzlL r+g-l} E"l 4l&al + 91trI.
xlTl B71 3D.2 2e8KE s.= ad 6rql^J l.00mot9
Ap" - - {ArG"(CO,g) + }A,G"(O,g)}
ArG"(CO2,g)
cHn(e)E trA^l7lfl flqs gtrt"Jql Hl-S+ "Jg Eg
+ gldL+? +, AJ"=-243llc'mol-'ol4. -194.4k1mol-t - {(-137.2) + }(o)} klmol-t
Irers,E = 157.2klmol-t
Eq 2cql^l ¤E6J ul.q ?ol E+E n*olg9 .E= ^Jd

(a) 8¤ Gibbs ollLlrl flgul= +Eql 44 ool4. s.6J Eq 3cql^le+ ?ol ¤-ol¤
s= HI+ Slgtle-l a+qlrls+ ?ol(Eq 2c) E= ,$d ol Eqgl= oJolgrrJel +.lg
"J "JE + $.sq, r"-16l.01
Gibbs ollLlrl A,G"g CeloIE ¤El6i+ -E= ^JC Gibbs oll Ag Er-lE E+E H*(aq)9 ¤4 tI= +irlE +"+.tl u|4 o
Hzl* 7l= ^JE}](E9 2cql^J ¤HEI)ql il= ¤ts gÊg ol+(+ A+ EF E= gEql^-l). olelqi +Ee ¤."18"1 -+
+q s+6JEol ,llel s= ++ Gibbs glHzle+ a+. fl fqzl ?+= "Jolgg HI= + s.zl ullEql g,qEt 4"lr+.+
^J^d¤
e8 2E=l3t 3E=l
-q- ol+_e_ H*(aq)9 s= sc Gibbs qlqzlE E= gEql^l +q AqI 4ol4). ol Eql +¤+ 4A ^Jql il= -ErE +4lEE
0o + Ea*4.4, tI* ciuus glH zlfi aJalH ool ¤+. nI+^J
ArGt(H*,aq)=0 Eo-4 +ol olE t+El (3D.11) ArGe(Cl-,aq)=1287kl mol-r+A*,"Go(H*)+A,o,u"e1Cl-)
,qa¤- "J6tzlH ol aE= u+(aq) olgE E= ^8d Gibbs oll Tlill^J olgE _E= rr trI4^J olg
^Jc Gibbs "ilHzl= =4
HzlE 0o + L,o_iL ol 7l=ql q+ += E= olg=q tF l]4 sl "ilulzls+ dxl rlE+Es Ellil6}jr, E H*E flBulel SIE
.J <tg e++b 4"14. e.gle.+Ei Gibbs "llulzlE g= 4Cql^J ^Jzl} ciUU' "llH
^lel
szl+ clol dzl-= q=61-= 4aql^l +^16}rll ^JzlE
Gibbs qlqzl sile+ 4-4lg+r 7IA++. trI4^J ol +¤ts
E+q tsE, 44-=-=-o-aql Er+6l'+ qzlrJ +rE--e-
'l-S Hl¤¤ ^J4611 E^|. =Î4"J
+se} d3 cr olg9 A¤" <lol clE da"Jql el6l]^l ac
lHr(g)+jClr(g)-+H.(aq)+Cl-(aq) A,Gt =-131.23klmol-l 9zl g}l +Aq all4, ol$s], "t ++ E9 zlq= EEI$Q
rBlH -tr= HI+ Gibbs qlqzlE zlzla- A.dg +g=4 e aol+.
=
ol ++91+
(b) Born Al
A,G": ArG"(H*,aq) + ArG"(Cl-,aq)
ols-5E Arfisl Gibbs
zflzfl
"ilHxlE +rH+= 44zlzl ^JA
slE4 gEq 9l= glE9 16"= 0olr].. r4r +Eq] E +44= E¤ql E46ll^l qH6J + 9l+
44 4C"(H*, aq)=golr' + 4d=ArG"(Cl-, aq)olq, q+
rl , ,-\e/^t r I ^ t
^-l AC, (Ll , aq/---IJI./.lK)mol

'ul ELf.
-t.-I
Eol|trl= L|EILH= 8flzlE1 E-d

ol EBql,{-u ol$nf ¤-ul]
^}olE ^}E4}¤¤ 44zl 4}+"
+"_4 +e-l ol9ol ^J^dq= r+eg gq+4 +¤+9 ol+ e +4U+. +d ol¤-¤- 6}ds 7E tr;r, +"H= ¤+4"J
6ll^J E4alH olEe_l qlqzl 4 z_zlql 7lq6} oHe(¤+4"J +d4l)e +{+q}4 ¤zl8 6llot g 6s-* r+
^JC ciubs
z-lli rp.r(e) ¤9 eq-= ol+6}q d* +el
,qoJE¤ "JotB + gl+. qlE^l E+ql^J crE -E= ^J "l¤-g +,}l +
= Gibbs qlqzl= o + old^l7l= oJol HItr ol olg9 +"l]3r} Gibbs
c ^J46}l Ezl-. +d ^Jc Hl+ *H,(e) + "llHzle}
KLG)+H+(aq)+Cl-(aq)9 rB :o.lql B.J "JHE +41=
g+= 49 }LolE 1o14. ol "Jg +.q +ql *b ol39 aI
ql q+ gqt+r ,.J4aJ4(ol :zB +el at==$ z|tr ¤tr- d ^l7l= "J4 tl+ +ql il= ee "lg¤. 6Id ^l7l= "Jr+
el il¤ +6IH 4ltlg+.
tr-q 2Ael rlgtzl9 4.^l 6ql E6IE +d¤. eoJ ,lla +ql
H.(g) +Cl(g) +e-

4 44 r"JE gq4 fl= + d d6t Qrl} Q,E Coulomb sl
+ 106 fl¤ qlqzl| ffi$ ?"1 i"ltl4.
-349
(o) +]cl,(s) +e H.( ) + Cl-( Q,Q.
V(r)=
4ner
() a.o,,Ge(Cl-)
---:
K
5
+1312
H.(g) + Cl-(aq)
ol tts4* glHzl} 44zl r"J *"ll q= A-d6l- e, trll
6
o Eql d-da} Qr9l ^Jzlb Coulomb trlEJ!¤ Q- 7l7la- uY
-o
-o
(, H(s) + ] Ct,(o) +E + 9t+. 0(r)g "l-4e+ ?"1 4rlB + 9ieq, q+^J
+218
A,o,uGe(H*) v(r)=Qo(r)ol gtrI.
+H,(s) + ]ct,(o) Q,
Q?)= 4ner
H.(aq) + Cl-(aq)
-{1,G"(H',aq) +A,Ge(Cl-,aq )}
44 e olElE, d6I Q,g .+(c)eE +448 trlHl¤ol
fg 3D.3 +a-E +oll^19 EEI 0l8el 8¤rt +alg Gibbs ollulÊ Eafzl
:Et+ol"e 0l
IC'ol g+.r?]r cEql el6tH 1lG'=1v(g.tr)olq q
fl:d Eq+4 +S. c= Ate||r4al ollLl^l
+Eoll Gibbs E6l.=
+^J 0E E= e +48 + 9l+.
-d6H+E 001 Etrl.
:o z{l ?rTE Ll'El''-.! 8E 99
trJ4l1 ,ile +E +¤ olgg 6}d^la qE olgg 11+- +e-E+el 8,l] +e-E old^lzl=
Ir+4^l rll
^l
Hlzlgol r,oltr 46171 Qql +(olg9 +ElLll=) sflql^jel +Hlqb 5 cibbs qlLl^l H+= ol + gE zte+ 7Jr+.=,
coulomb ElHl¤ Q+ T36171-+ +cql ¤-d6I tF4_+ glg
_"8\^ 44 _- zle'No zle'No
'I +Elrfl4l q= qfl¤$ F"J6l-+ q+^1, A*n,G"
8ntr, 8fieor, 8fi¤,¤or, 8n¤or,
QQ)=& ol +Hg 4a 47-l6lH r-]-s-=+ ?3 Born *l"l ¤4

^lE
ol+ql+ d6l-= dQ qI+ *zlxlzlE rll gs6J "J¤- o(r,)aQ"l A.olrG'
zle'N
Born 4l (3D.12a)
8n¤.rr,^ t,
+. trFr^J olgel d6I=Jg z,4a_ 6J A+, ol + 3 ol99 oP
4 z,enfz\ 6ld^l7l= Ell g-g+ dzll gg q-q-4 ?"1 ¤4.
++61J, 56] +g t}t]] +dge-l ,Ie +
* = J''' qo,)de =
#l:' ro, = ffi A.or,,G"<0"J9
ql Eqgl= 4Lg aTlE +g d6l¤ *E
"l3E A+ql=
6td ql gsql ol dzl4 gql+ Avogadrotf NoE A**G"ol *e-1 ?t& ?*Y+= aE +E-6Lq+. Eql ql6]]^J
^lzl= =
25'Cql! e,=78.s4o1q, E|+^J Born 4lol r-l-e-$ ?"1 S
#6lE olg¤. 6l-d ^lzlts rjl gs+ E cibus qluJzlE tszll =
g+. +.
aq-=+"lr+ d*ql zl+^l{14

tr,JAIz flel
ArnluG" _zi x6.86x104 kJmol-r (3D.12b)
ql¤ d+ 49 ol99 6Id r,l pm
^l7l= "Jg eealE #d¤
eS
d+ +dg so E
o Hh+q +eH g+. r7l-7 u1]e 49 olg-
g 6Id rlzlts gg +614 E e=a,eo o _F +98 Etri. e,3 uJ]
Ae-l tl4 frd$"l4. zs"cE E+ql^l cre+ rql ql* alE zl+ q+4 a
^-d
4. olE9 tlxl$$ zJzJ rsrpme+ 220pmoJr|.
-2o2 - -r ^r:---^ \ ,1,'
w(vacuum)=-:i"- w(medium)--
--
(t
' STceor, ' 8Tc¤,eor, r\
a*kc"(cl-) - A,.,,G" (I-) = - t___t
I rar 220 )
x 6.86 x 104 kf mol-'
E4! 3 olgE s""ll+ Gibbs "llHxlts ol olg9 tI+ +e_e

= -67klmol-'
+q +4 +_q e old^l7l= ql +Hlgts "Jr+ a+.
=s-d7HE=
_l l. clausius+E^lg rPJ4 EEtoll EH:d 7l=g 49 Ce="J f 4. "Je'J gEe+ "Jq 6lql^l ^rBzl r+col "JqLlelE Gibbs
o e Erlg= tr}"Jq} z4g zlzl:t_ E^lg + 9t¤¤ g6ll 9lHzlz} 1taaloi q1q.
ol zlE==g Helmholtz qlqxle+ Gibbs 9lHxlE zI rt s. qlqzl HEi*s oJt 8ss+ glq 6l.ql^l gq+= 4
Gibbs
=E+. =,
zlL s-oJ6J + 9= 1,o14. Cq^l eg + 9l= EIE[| Hl-tser'gr+ e+.
-1 2. .JA.J gEe+ +q 6}ql^l rlg4 3lSol gq+4B -l 6. E= 88 Gibbs oilL1rE ol+6tE E+ Hl* Gibbs qlHzl
Helmholz ollHzlz} rJtallo; Ar1. 4l&B + eltr}.
=
olg9
-1 3. Helmholtz qlqxl E3rlelg "JA s_Eql^l "Jq+= rlAql^l :t 7. E= ^Jc Gibbs 9lHzlb gqq}4 +F+4 Born 49
eg + 9l= EIE]| gr+ A+. ole" o[{ +.t}6J + 9l+.
1 00 2H?s.l3l3H=.1
=sEt^l=
,rl
oe.zI t'1 HE
-1
Î =/\i
^]
.
x}tsd9 zl# dsL'r.> o oI4 dzlt "JA6Ial #zl!i Ef
dsH,p > o
Helmholtz 9luJzl A=U-TS eel 3D.4a
Gibbs "llHzl G=H-IS c9 3D.4b
,(|94 Esi9 zlf (a) dAr,. (0 (b) dcrp < 0 F+E. ¤¤g +4utr} 3D.6
3]E}l "J dw,',r* = dA, w-.' -- AA "JA

gE 3D.7
zl4 ul Sat"J dr"o4."* = dG, w"aa,.* = AG V .JA gEel $q 3D.8
_E-= HI* Gibbs qlLl zl 4G"=Aff-farS"

A,G-=>yra,G"0)
: a9
l zl
e.e.--1
? _Q-E
O!
3D.9
3D.10b
8'l 49 ".l9 A,G"(H*,aq) = g V +qt 3D.11
Born A,,G"= -(zf e' N n I STIE or,)(l - 1 / e, ) SrllE ¤+4 uNill_tr_, olgg +E .+l# 3D.l2a
^]
EEf 3E lEElEl 2$4$
=-Et
A+q! %rzl "e. q+ H+4(du*ds,

du*dV). ol$ lr-lr
> ol EEE Hll+= olP al t** Hlql +4171 cB*4= ae uE se+ vel ++e
EE+e_l 1E^.li+ 2EEl3 Erll9 dEal Szlqq, ?al= 0l
rHaJ
g=l= _Hb aol 4dgg "J^l6l+ 4."14. ss+ yalr. EL+ +4ql
F rlE ufe-pu1 Eq+4 E^11= +ts rll 7El
Effi oe=EJ6l.=
olEg + ?t= e= + ?ltl. 9l= se+ p, E= re+ v E += + H+E zlzlt- uE +48
^lB
tE 9lzl"J 919 zlE^lE ZI+s E-+ eo} u(s,y)= q{=
> trId 7H'J 4") zl* =-4
Eqqt4 -Bt+=el nl4 Eelz|SC ElEolalts 0lE6lE
u= se+ yel Er-+E E+= ae +q4 o e duTl- ++4
rl'g:sf Eqtri4 dEE
^l¤=
Exl= E= + ?ltrl.
^lolel 2-ol dsel dytr -E^lg+= 4¤- 9"1d4.
> =Jg-J qlHl xl^l
8El|
:Bt+
U(EE 2A), H(EE zB), S(S.4 3A), -Lal-L Asl G(EE du =(#),ds.(#),0, (3E.2)
3D)sl 8e]= E Sl. ?loloF:Lltl. 0l EE9 + lEE PE6I= tllE

Erl 2Ael al+^lE 8^l eoll^l ¤E-Lr EEEt+el dE- ol F ¤gH-+(Eq 2Ael $qz}el tlal s)i "JA yql
^l+ ^lE
ol8otZl Ect.
^J
uel sql Eil6J E^lE zl&21, relr "Je sql^J uE vql
EIqI E^lel zl&219-i-. e.4. "l 4¤- rE.ralE gqq4 +41^l
gE+E tB4g du=d4+dw4:1 -E^lB + ?t+ aC"l "J 11-u1:lalJ_H_E atol "JAqI alql ql6]l^l r-l-s-r+ eg a+=
a+ B6J4lql^l 7IE4 HEIzI "JqLljL Hl-s+ "Jol ft}q Erll ¤+.
zl ?*g ullE dw,*--pdv, rqr dQ.,"u=TdsE *41(Qlg+u1
E dEe+q)zt ¤BqI+ ¤zlrl p= 4lq "J4"lr r= r
AU
-
ds
_T
(#) --p (3E.3)
gEtri. trI4^J gqral qlql^l 7lE4 Hslrl. "JqB ql= q+ v
+Al7l cB++ ol 6E arq !C gE. +d6l gqql4 "E AE6I= ^le

E^J, gE= acol "Ja6Ir Fulzl. gcql E6Jalel q]+ ql
dU --Tds-pdv 7lE^l (3E.1)
Hzl Es+(rBzl9 4l'J)e+ flE +rl Hp+(2H49 zHH)elE
rq+ dU= 9d "l$olo + a_ ?rX+ A_eql ++61+. trl4 Hle+ eq. olzll$Q 4lE CeE +41^l- +E6ll +
Îolel
d Hslz} Hlzlq4ee- "Jq+a 7Iq4 oe "Jq+a +41 7l4a 6].Lql, ¤qqlg ol+6LH eltr-+q *4lrlEol +g
$.ol 5?9 <iel du. grll S+. e44eE ol !g El-"J += 49 + "Jal g aol+.
* g"l fr}q4 ?*= Efl4lq E.= HsHz}g4ol{ ulz}$
4ol{){l zl+¤4. gqq} t$zl4 zB49 AoJ^14 F9 "l (a) tvta<wetl +41^l
4& z lEl4ol4-r.5-gO. 6Jifky)9 H+= df -gdx+hdya +48 f ?le4,g
"li
"l zltrlol zI9 Hsle+ ulz}9 Hsl"il 4 ?.ol 4+¤+= e+ h= E-F x4r9 BfEo]|r+ df zl$d
z]+ql= q?]E¤6IAl y441,"1rJ. 1 ol-$| z|$ "lB(z 4E"l d
^|dol eql ++d IrIE)ol E + 9t= ++4 zl#? trI¤-r+ ,J:L+.
HElfl A+ql"J TdSz} dq$ ?Ja- E- -pdw| drlze} ?zl oll$
ol+. HE+zl lulzf!4"J trI= TdS>dqol_r.(Ctausius +E!)
EaL -pdy >dwol4. aCol "JC6l7lEl alE dqq dw$ a;-o1
(#).=[*), (3E.4)
rdse+ -pdvq 6J4 e+.

olzl#3 Elqlz}9 ^Jal roql^l ¤86I4t4. zlBzlql :r.ral
g Sd t:lgol El= + dse+ dyql E6llzl= 6J+=(+
3E.1 LIl+ ollLlrlel ¤E ^lolo
r4 -p)E ol zlfr$ "J+^l4oF eI4. 4 ul" +4171"J+q
olot a.Jrl.
:E.rrloll el"IE B6JZI9 4+ qqzl= se+ y7| E.Jql "I+
102 2EElrt3E=]
ilEtrlel 84 ro Sd ElE
zl# d/5 q-q-$ B3 B4 oe +48 + 9l+r 6Ix|. a4l Iql +{l ¤r"-;-a5- s@il?_ r?]r E4l
^le_l ^lE /ql
df = g(x,/)dx+h(x,y)dy T+eL ¤rgtf h(x$e- +ElrllE ol
^lol
q-q=4 4ol 94.
=
ol df 7l $d plts"Jv\ olAol sd
"l+ol+E ol{$ ffi
4 eg Es Lt4g + 9l"lo} ++. =(4*2),
[+r*1,).=[*$r). [*(#). ),
,=(#) E rq4ei ^JAql fE .e+ ril St +lE + ¤+
,**(#),* Y
e-f,it=
el611^J
E"Jull"F tI+. ,rle[J,

ol F 49 ulnalH q-+ + +41= Eg + 9t+.
( dsk,y) dh(x,y)
(#), =g(x,v) (#). =h(x,v) t--D- ). --dy ),
ol
F^l"l "J+qH df =g(*,y)dx+h(x,y)drE Sd "l$ol
+E EE++E fl Ceql E6tH ¤ololzlE Eo.J+b "lE9
qlqE "J"J += Eelql el6ll^l df 7l s4 "l+"Jol "J4
+^l= q$ril 6IE g+.+ +.
ag ql= ol H E s.aJ# 6J+.
Îol9 +Al7l "J+9"lot
[+rgl,).=(*(#).),
AI :zf +?i+
AV (*)" tVaxwell trZl^l (3E.5)
olEal ga oI+ +4lE Hg a ag + "JE¤ ¤+^l GZE Ma,nrrrell gal^lel olE

^ls
zlE 4 6|Ll-= eH+. .s. rr.t9 Marwell +4149 "l*a}¤ 9d zl4l9 tl= e
+Et:e.salg Marweil tr41^le-l 6I++ ol 43 9l
HJ+ ulzl lnvql Hlql+4= a9=-, S=a*bhyql HlqlqI+E
t ql"l+= dg zlleJ6tfl Etr6l gul_Eg 1"1 * g a 49 u-qe1.
=
i]fl B"Jq. rezl"J ol A4= "le| uliq} Bd q ++
l'a{E ,t.l¤l Maxwell +41^l$. olgo}¤ Ezll5 +=
+ += s4lalEol E 9lg + 9l+: ^tdg "J^l6H++. ¤ =g
x.lls a, G, oi azl t4 oJfEol4E d3 $= eslzl "J¤ gEq^l +qql trl+ qB4l H6l+
Îdg "l+6IH :zH9 zlE E¤f E ulE 4lf (as/avhql ql+ +4149
Maxwel +rlllg q +Es + 9lg 1o14. + H, G, "i A= ^J46I
tlEH ++"lzl rllEql dH,dG, oi aaql +* 4.g :r.+al4
aol+. 4eg olql sa zl;ll ^J449 "l**4.
=
Hl*6J +4lE ol *4l{# -s:s.rgl Eot s. ts.t9 trl-f. ol*4.4.
"J4,r14"F.J4. =01 ^lg-
Ias) -f9a)
-
E 3E.t Maxwell zJZl l I ay,/, [. ar /,
trq El+ $d ulE Maxwell +414]

q-gq= $d zl4l tr-q^l p_nRTV* q-s +
"l¤-ollrl
4E e=+.
U dU= TdS-pdV (#),=-(*),
Iap) (E(nnrlv)) nR
H dH=TdS+ Vdp (#),=(#), [aTJ,= [---?7- ),= ,
rqB r+q-r+ ae +4lE gg + 9l+.
A dA=-pdV-SdT (#),=(#),
AS nR
G dG= Vdp-SdI
(av) _ (as)
--{.arJ,
N T
V
[?7J,
1E=.lIl2fl=lel 103
=-Bt
nlEI^J "JA6J gEq^J= +q_4 eg A4= Eg + gt+ @ gEEt4gzt^tet *E

9d zlAlql q6ll.Al|.zr=ool S4E 49 gq44 " +
dV
_T
dS=nR = rzRlnV+ constant
J J +B6tr, E vanderWaals TlAlql ql6J ol ilg +6Iq?+.
s}Hel 4.$$ S*constantolq, q-El^l g6l+ +g"l gt r.a{Et ¤9421 " e +H6t4E Ag d4e e gH}
^l,EI
gqq4
4o14. 4"J '*;r EzIg Ce, ql
Ar+e+ ^JE.ll^l=="Jg
xPl g7l3E.1 vanderwaals TlzllE qlEeul=+i4ql q d4 Ezlt "Jq ag 42 ,xz) E4= *ol+. 9d zlrll
Brll E=6IAL+? "l ql qlql^l= p=nRTtvol{, o14,9:e.0al9l4 ol+61-H E
fr "$Iq?+.
= teB tk{et[" 4. "l+lzlzlE E ll Ezllql^l= s. rC.a9 vanderWaals
^l
EtE+ *1-z h-g. loElv¤ *reR tatn [to(qu -a)q ua *S 'E
9:s.0al{4 "l$a}H g+.
$d 7liil"il qdl^J= trl¤-+417I cB++.
=01
(b) Lll+ oilL1rle.l +tr|oil nlE Eal pZ) _( }nRr tv')
_ ,R
Iar/,-[ ar ),-v
f
.ll+4 "JB zltr-9 zo"llrJ ¤E+)= rr-(dUtdnrs eelEl
q, alel Rulz} Eog4 oE H.Jql q+ 4+ q¤zl Et+^J 3E.6^lol ++4 ?"1 ¤4.
"llHzlz}
Hd+zlE Bqf E ao+^1, lH4g 0l+61+ ql 6ld E
6Jg *+. Maxruell +41^lg ol$all.<l /r¤ ¤-EE 6J (ipldl),= nRN p
"Jq4
+E +4'-J + gltrl.
,,='(n4) -p- (#) -P=o
v
?tr 3E.1 Eq-qtr1 sE|l^.lol 3tr q+4 g4

^lel E vanderWaals TlillE tl=ll^lg
3E.24lel g-EE v4g +6LH^J dvtr ++q +
"JHg "JA
nRT n n'
H SEEL+ (aulaDrql +6J 49 +6J + gi+. p-
V-nb
_n-
V'
=
Itr T -p
AU
{zlrJ a* tE gEql ++6I+. trl4^1,
a7 ),=(#),(#),.(# dp ) _f annrr(v-nb)\ - V-nb
nR
olq^J 3E.3^lel
+ +4le+ zroll *aJ AEE Bq+H 4g=4 AT l,-[ ar ) l/
ee 49 eg + el+.
tr|+^J :p.0al_e-p+El +¤-r+ ee +4lE Eg + gltrl.
",=r(#),-o p
nRT nRT nRT n' n'

"r- v-nb r- v-nb v:n6 -A-----=
V' =A------
V"
qq, relol.q q* A+= eg + 9l+.
# ++ Ar+ql E6LE van der waals zlz)lzl fr
ol argl
,,=r(#),-o Eqqt4 dErt^t (3E.6a) g S+g B rll= f Lll+ 9lHzlz} =" zlalql= @utat\r
>0), +7LqE CE= Eztt "Jqel aEE +4'l]= E|?+
trl+$ *"1 448 +E fleq, r?-l6}q ol
3E.6a^13 ulQ agl trE[^] trl-str]. E. Ez]t ¤+ ,l4q *E=
^lg
Eq-+q ge1*lol4r +trI. g+vl= o+* +4zJ ¤+= "Jqg 9"1614, trl4^l d
=
ill qlq zlzl4 4TI+.
o=,(#),-o, (3E.6b)
xlTl 871 3E.2 st;lttlz\E} EEL6I= Hlrl"J tlE1^l(s
1c.4)g "J+^l7lE TlillE zr= 4lt}6-}q4.
ol
^lg 4E qel gq+4 ceE¤ zgl:r_ "Jqg +4u i61n1ggg)r1t=tu:$
ulol4.
N
열풍간
10t, 2E=lal3E=l
3E.2 cibbs ollLjrl,el ¤tr Gibbs

ollLixl. G
uql ++ rlt^lql 4+^lA.c 44 +ee E4E cibbs ollH (a)

7lz)l -s
zl G-H- rsqlE 4+^lvJ + glq. rfl$ czy "Jq4 gE =
(b)
ql E+4 qB4 HalEzlE ++Lll= +41{$$ tsz| flEcll, 7l?7l = +V
ols=3 /J. dolel Eiqt HI¤¤ E6l-= Ell ol+q= +s6J
^l
Eol+.
( p
(a) tsHl4 rd
419 t4zl Hg ullE H, T, relr sz} E-F H6Fr E GE H :Ie 3E.1 Zl9 Gibbs ollqxlTl.(a) BEet gel 6toll^1 SEoll qa[, ]elI.
Elr+. (b) g¤Ef 8Eoll^1 galoll ttl'zl' E6lE g.g. gE e+E Ea|EP
LIEIL,! llE fllEetr|gl gri, +^l.e_l e?g 7|E-7|,= +trlq ecl. =-e.e
=,
dG= dH-d(TS) -dH- Tds-SdT
6J¤fr=U+pvolr+. qrq+ Eeql El]6llÎ+ s>OolE + Suzl g4zt
{r
tt
E ("JC+ "Jqr+ aC 6Iql^J) G7y6J^J-+i6J+. -

rlo
Rr
dH - dU+ d(pv) = dU+ pdv + Vdp (ac/aDp= sz| f,zlaJlq- q r4l g-"1 94, 4l rOl
il
trI+^J, 9 fl= + -4zl Z oll= cz1 q r4l ,Jaapop 6J+. nlil
dG = dlr+ pdV + Vdp - IdS -.SdT ,'|4rJ E flE+rl= zli zli:lla Eee_l Gibbs qlqzl
tg
Hl_sa} "Jg 6tzl ?+= B.Jzlql ql4^J= duE ,lE^l
eg Eeq .lzlltol+:/ill^Jel Gibbs qlqzlE+ gEql
=
gd q ql"J6}zl E=++(r4 n.21.
du= rds- pdvtr Hl-+q Bl r1g-rtr eg !g gg + 9l+.
Ezll !E u}{z}zlE 6114g + 9l+.
dG = TdS - pdV + pdV + Vdp - TdS - SdT qH Eeq ql6|]^J+ y>oolE+ Al9
"Jqg +
+HE t4l9r" r46}q Bl-S+ gg 6}zl ?+=
ql 6}=0l zlxlzlHtgss+ ac"l gcts uI) flîl+ G7l + {r
-
'lo
gA a^d9 gf,alql ql6H^J +gl} Ae +41^lg Erll g+. TIqI+. Rr
(EclEpl; vql E|4 4le-l +irlz} Eil il

'Ol
- SdT gqqr-sl 7lp^l =

Yczy sqql gt q ql"J6I+.
o[U
dG = Vdp (3E.7)
=rz}6iE-g
Gel Hslz} p4rel He+ql Hlql+q-= ol 49 cE pe+ 19
EL+E .E-= aol 4ltr-"Jg E6J+. ol gqqlg El+ql oJ Eeflzlilltlql^Jel 5 +ul= f,$ tr""J trllE+ =t:_E
^lg Tlill^J Eeg ._4;lltol4 rill^J Eds_tr| :9 c ztol s4
¤s"61-b ql +C4 qgg 617l trll$q q-+ Eqtrf9| 7lE^l
ol4a ¤L+. "JHI4e + +olql^JE Elq4 ¤-szl-aeg +
glE H+olzl rllEoll Gibus qlLl^l7r ql+61 +s+ 4,o14. 7l^11
H]-+q EJ:"IE c+ lB44 2H4g sl+ Erllql a- 4+

qE+ Ao-J6]] F3 4ol4r E + 9l+. =61
o
* 'JBg sd
---:
3E3^lg +E6l+ ql "lE dG=vdp-
K
5
^F.s" 6
sdrql 4+^lrlB +¤.4 ae +4149 Eg + 9ttrI o
-o
Erll
s lijl
o
(#),=-'(#),=, Gel rel poll rlE Eof (3E.8)
ol 4E=3 Gibbs glHzlzl gEe+ "Jqq Ir|+ qBrll Hd-= 3E, r

zlE Eq=4(rH 3E.1). fg 3E.2 Gibbs ollLirlq SEoll rt|Er Egl=3r. g!=+trloll eld|]^'t
Etl-. -d BEE z FIIAE rll9 fl!= +rE qilflg rfle.q fq, sE rrllSg tttl
=8
ol + 44 ^le r-l-q_r+ Ae 4¤¤ Rr 9lq.
îlg
4re-E-E Gibbs ollLl^l= Tlilldg ttll TlEl d6lXl E6lq, :. tr|te:ee
e4illdg nl1olr, 0lol,\1 rillg nl]sl+eE EqT.!tr|-.
3E 1E=lrt 2E=lel 105
=:Et
7 q=E LIEILII=
^l
(5
+d q¤4 ae +aHq ^l L++.
K
5 d(fg) / dx = f(dg I dx) + s(df / dx)
6
a ( aclr'1
-o
(9 Iar )P +(#),.Gf=+(#) ,-#
o4rll -1/T2
lijl =+{(#),-f}
ol21 n
tl-, P
.f.al 3E.3 Gibbs ollLl^lE gtajoll EHEI Esl-S= r,\|.E.E +trloll Edt|,\l olq^J ol +HE @GtaDp o}9l :e.q^lg Bq=+.
:Lf o-qi1Bg qsaq eq rillS.J tttl ^l
EtrE Tlilldg ttllel +El=
=88tr1-. (AG/aT\e= G - H)/T
+e_E_e(rfli{l{oe -"= Etrg 3g) Gibbs ollLJ^l= Tlillgg nll 7tg
îl9
d6Ell E6tq, I cfe:eE "-4ill8, rala r^1ldg nllolcf. -d E¤E e4ill8rl
rnHoll^1el +tr|= ul+6lE-e 0l + 89 Gibbs ollt_l^|9 geloll ttl= EEI (#),=+{(#), +} +{+f}=+t+}
EE ul+dltl'.
^je
ol {g A?-16l{ trl+r+ *3 CiOOs-Hetmhottz ^lol +gE|.
ql gt q ql"J6I+(rH 3E.3). (dctr \ a
Gibbs-Flelmhollz (3E'10)
[=, Jr=- r ^]
zlEtEt q 3E1
2e8Kql^l q4 EE e* "JEb 0.ee70scm-3014. sq"l Gibbs-Helmholtz 43 "JA+ "Jqql^J "Jq+= 844 ^J
o.lObartrE 94zl-H("J¤qL gEotl^l) ol EE E cibbs Eilel Hsl+ p+ql HISI+ eg HEI-ll 4+^l7l= r]]+61 +s
o|uJzlE trl¤+ *"1 Hd4.
Gibbs qllizl zl¤
^lol4.+ 4* ^JEIe+ola¤- ^Jq ^Lolg
eI
v^ AG=Gr-G,4-:r B A+, 4g Gp+ G,ql 4 ?ol 4+qs
E +¤-q- eg er+= eg + 9t+.
AG, = (+), ^P
=v^^P=
mx(o.r xlos Nm-,)
(| dtctr \ arl
=+0.18lmol-r
( ar ),- r'
_ I
-__ (3E.11)
"l ^lql E6lH HF+(=" Eol4 Hlg" 4 ag)= "J_o zll ?lE
(o) oioos ollLlrlE e-Eoll tr+= EEI 4lel flBrl Esl¤ 9E ctus "llHzlz| $Eq lrl+ qgrll
HolEzlE g + ?l+. +ql "Jrll qilzl"J ol zlalS slo,Lql
4lE BB a^dg r
4lel Gibbs "llHzl"ll q=6lEE ol ac rll+61 +s6}rll ol+q= zl9 at+ol4.
ol gEql q+ qBrll H6l+^1= "JEIH G7l gEql q4 q ^l
Erll H6l+zl= goiot 6J+. (c) cloos ollL-lrlE elqq u}= EFI
*d :E.s^lE a4 ^l (aG/aD p=_S7l ol Eelel =Bdol
84. ol 4* $= +ulfi zlzlL Gel gE 9+s.= +4U a 9g-zi "JAts 4*, tp,.z^19 dr=o o + *:l(dC= vdp) 4E
6IH ql sqql^J9 ciubs qlLJzl {tsE+q +E "JgE s
olzl"J Gel AEql s=(H- C,ff==- ol+6IH ol{$ ffi
"I4 qqlîel zlg +6J + 9l+.=
4 *ol SlBrl= zlzla_ +48 + 9ttri
/Dc) G-H G(p)=G(p,1+ !^,'vap (3E.12a)
(arl,- r
t_t-
ola¤. g oJ=e_tr_
+Elg +E gi+. .,
+ql Eq 6Aql^l Eol?lzltrJ Hl+g ¤B tL+= GBtrI=
Gtre+ +4lg+. ol +4lE g+ql +_r. 3E.eal9 ol*al¤ G^(p,) = G-(p,t.lj V^dp (3E.12b)
GtrTl gEql ,.1+ qBal H6l-=zlE "Jolttrt.

"l 4e. Ee"l q"lt tr-e_E gl= +4ls.ol 4*9zl"J, ol
106 2H=.lat3H=.1
g86ftrl-r.718:el ¤rll +tr|

+tr1 G^,r(p,) = G-., (p, ). fi V*rd p
E li ^lql^Jar(l] 49 u 4*
v_,r-v_,r=at.,y,x-e. +-tr
A*,G= G^,2-G*rS ++c}. :aEE,
H
nl-
A",G- (p, ) = A,,.G. (p ) * !:, A,..Y.dp

Lp
"l ^lql
gsql Ellolq= B-z 4l4}g 6IH Rg eg + 9l+
pi pt
Bal, p
Eol at..yn,= "Jqql ++6IE-a +lE 49 rlg=4 *"1
fg 3E.4 rrllLt Ei1l9 + "JaJoll 'lE Gibbs ollLl^l il.= raJoll LIEILJ lA -\ OIrL
e. -f ,\A"1
'Jolel eq-. olAP +4= gal EE]oll zlel 5.951trE
.
7|.¤!-d
^]^|'4eE
=rlolrl.. 8+
A*G.(p,) = A,,S-(p,1+ ffiJ',' dp =A,.,G,"(p,) + A,,,!^(p,- p,)
!9 +q y_ol "Jq"il q$4l el=61+zl$ g

"l86LBjH E
oloF 6J+. qlolElE Br, I Pam3= I Ig ol+ql+. :zBlH,
f,-4,r"r-e-l p. +rl= "J{ol H+q4E 4E H6I^l f*eq,
4,,G(3 Mbar) = 4.S(1 bar) + (1.0 x 10{ m3 mol-r)
q$^J y_g tl+ilfl fl#6l1 4E zls +r-e-s 4tr8 + x (3.0 x 10rrPa - 1.0 x lOs Pa)
gl4.:24ts, = A.S(1 bar) + 3.0 x 102 kJ mol-r
G^(P,)=G,(p,)+%J dp
Pr rPl EfTt 3E.3 -lo'Cqiî E+9 9:== etTkgm-3,j4.
P,
"Jqg t.0bare*ri z.obar-a +q+Hg oll9 c-9 HE]
7-
---t, 4l&6}q+.
= r_lotul0'Z+.8
E Gibbs ollLl^l
G^(pt) = G,(p, ) + (p,- p,)v^ lHl-gr+d
(3E.13)
=El
(p,-p)v^.Jq +4= rH 3E.4ql :-4loe +4rllfl+. Atr- TlillE E +rl= trl4^J 714lE Gibbs 9lHzlE s4
=.q,
4"J ¤e 4 z4 6l-ql^-l= (p,-p)vôl ql+61 +sq, +^l ql zrll fl+++. S"J +slr} "Jqql r|l E=6i!-
"tul+
g + 9l+. rq6}q "JHl4_o e rill+ .lalq Gibbs qlqzl e. 3E.r2b^lE 4+ql^J olag ^J+E ABg fz| S.4(rB
"Jqq ++6I+_r. ^J46llE s4. :el4 zl7 Eqq}4 E 3E.s).
=
z]e+ eg a+ql= zl+ 4+q .Jeol 4ql6}rl trIEql "Jq Sd zlillel A+qlb q--q=$ ?ol v,"= RnpZ "l 4E +ql
ol Gibbs 9lHzlgl trlil= ¤6}¤- +^]ts + strl. d¤4"J + Br rqH
7E:
^J+e+ ?ol il-=qi+.
ul Hslz} +48 AEel fl,qol z|s"¤ trll= Sdt:e.rz
alg *lot EI+. =
= nRTlp
EEil dot ctioosottLjrtEgEt %zttt
V
el r.illzl tl d"lE B trllE +El Hs$zl- "Jqql ++

6l-41 A,..V, = * 1.0 cm3 mol-lol +A 6tz[ rfl H "JH ol .--:
1.0 bar( 1.0 x 10s Pa)-tr Fel :.0 Mbar(3.O x lOt t Pa)-tr *z}lt9 H
rl-
,ilE tr-{ol Gibbs
"llHzli g"}4 H6}flL+?
lu o,
]!qg AEI 3E.12b^lg oJs-" als r.;llz]. dl 14 rJ z"J ull
9 ciuus "llHzlE zJzJrJ-e--a\+L+.
Pi Bal, p Pr
G,,,,(p, ) = G,,r (p, ) + r^.rOr1 f.g 3E.5 Ed 7li1l9 + g'ajoll,\lE Gibbs ollLl^l il.= raJoll LlElL.! Hlel'
Ioo' ,Jol EE 7lill-d trJel bulolel eE[.
1E=lEl2fl=lel 107
=-Et
4E n.z
G-(p,) = G-(p, ) + nrJ"'

io, =G,,(p,) + nrhf, (3E.14)
o
E
j
K
5
"l ^lql el6l-H ¤gql^J "J4"1 roul]E ¤zl6J trI= E Gibbs o
a
9lHzlzl ql# 6zlaJ4. roJ ol
RT lnl0=6klmol-1 e-l6} -o
s
^l.tl (,
H "J"J p,-p"(rbar9 E= "Jq)-o ? EagH Sq p{lrl9 I ollll
4 zlzllg ciuus "llH zlzl a s= tiEIql^JE al4 +94 e

ol s4lB+.
I* sal, p
lal 3E.6 "J8-deEoll^1= Sd TlillelE 0lH^lzlln poll HlalElq,

G.(p)=Gi+ nrnS E Gibbs ollLl^l
gEut Il (3E.1s)
E= SEHoll E=JEtrl.
p"oll,\l p-+Oe-tr" 7tE
Gibbs
Gibbs ollt-ixl7t 3o-+ +eEH7l
ISE z l^]1,
=
E= +edlqa[.
ZtJ:d 0{l 3E.2

#zl3 $d zlills _H-:r' r *qg 2e8Kql^J t.0barE* 3E.ls^l_o_+ 4t sz-
ql^JEl= E cibbs qlqzlel $lEq
4 z.obare E" I z}*^la+. 3E.ls^lql E6IH E Gibbs oll el= +Al= rB 3E.6ql +r}49.4. "l qlt6l +,q,* !e
4z1zl ++4 ?ol ¤4. $d zlillql 4+El= o + +g
^l"l+("JHI4 =Îol+).
G. (2.0bar) = Gi (t.OUar) + (8.3 1451K-' mol-' )
x(2e8K)x'"(#*#)
= Gi(t.obar) + 1.7 k) mol-'
¤+ tr-"ll ql.J E Gibbs "llHzl H+= E JF + ¤ql Er+

6Izl"J ,l4lql ql6J Alg lEB + vJEA"l+ Eq= Ag
+E-_6rcl4.
T]ILJ=
=gET
11 l. 7lE^.!g tH44 zBzl9 A6JdJ 4,o e.rJ 419 +Ele+ elE
=4= "J + 914.
sslE Hqql q=Lil+ qLJzl9 HEl¤ +EI.ll= rl"l4. :t s. t 4lE qlLlzl trlEg ol 6J+E. "Jq4 gEg 6J+E
Gibbs
-1 2. gqq}4 ¤e=- rl-"19 +414e ol ceEE eEqI4 E= aol 4/}"Jg '+ElUq.
^lr+
+4g aEI6Iq +e+. r 6. -J EAq Gibbs "llHzlts gE.9l q+ ei6}l, Sqql trl4
-l -r. Marwell tr1!4e gqo}4 CAE EBJ+S 6rl*trI.
^r"lel +4lE
+ELlt= "JHE gqqlzl CdEE Hplzl 9d 1 7. Gibbs_Hetmholtz elt}HGibbs
"lluJzl9
gEql q= H
^]SE^J, ^lq
EIEoI gE zlt¤ olg6ll^J +EqI rl5"l4. q+ SIgEle+ +Algq.
_1 -1. Maxwell +al^l# "l+6IH EE-+4 8E[^lg +Eg + I 8. r.ille+ EAle-] Gibbs "llHzlE "Jqql 4E 5-$a[4.
rBlLf
9leq, s,t Ed9 4P 9lHxlzl PE]"ll Eq qBrll E6] 7lillg A+= SqE ql+q |el dB4 o e 9¤rJ4.
1 08 2g=lat 3E=l
=s-d^lE
ce ,(l
-1 +^l al HE.
7lE^l dU= TdS-pdV +714 "J S.+ 3E.l
gq4q 7ltsrl dG= Vdp-SdI +714 "J $.9 3F,.7
GE EE} (dGldilr=V q (ECidI;n=-5

=c "Jc 3E.8
Gibbs-Helmholtz @(GlTlaTp=-Hlrz ec gc 3E.10

^l
c-9 "Jq E= G.(pr) = G,,(p,) * V,,(p r - p,) Hl-"J+c Ea 3E.13
G,,(p,) = G,,(pi) + RT ln(p/p,) 9d zli'll, E"9 3E.14
G,,(p) = Gl+ nTln(plp") 9C zlzll,59 3E.15

n 타ㅠ
E 3A Icb ) = EBB (a ] E 3 Bn ( a )
. 며
25c 1 atm → 125c 1 atn > 125c 5at에

정적 298 K → 500k
E+ loe
= 등압 등은
풀 = 재품
3
Co a R
α
=
.
다 m
Dsays ncln DSsys HRIn erer

.
forer
=
^3 2E4El-3HEl
=
E71 .
DSsys =
146 .
22 = =
-
zl 9
T = 390 만
최
MCIn 플다
작 2 50
E 3A 3 ( b) R 1n
.
105 JK - 1 95 Jk
bSsy =
-
써
=
E= TlillEg
$.eE -
trEq t#"1 oJK ${ zli-llep 7}46}r" g+q}4 qlolEl= 2e8.lsKql^19 a}Ee s_o}4.
0 vev
DStwt 0 자발 -
500
=
bssys
E 3A 4 cb )
E4가역3A 등
옵 fl!=+nl
Ds =
Torer
¤B E^11
250 K5
직
D3A.t
+ 2'+{}',4'+e^1',4=
n 3) T +q9 elel= zBzl4 +fl6}q E6}q4. D3A.3 .rj$ol s^86}rl +l"llri= ql+61 F*g +q +zl-EE azlol
(2o ^8ill
o:n.z EgqI2Bzlg +44= qet s¤ ,J^lE ^lolE +41= b6}q4. ^llE +ql Sqrlo} .JtrI. ¤ot9l= ^Jill 3zlE9 ^Jdol gE+ zHzlql
[ T)
25oKJ 9lul]q?L:*i ?E3 EBoIZI B.6|r atg=- Atseg + 9l= ZIÎ.J ¤
Bg 6Iq4.
[ 1 o
0 f3 ) T
G-^-
L-]rr
E3A.r(a) qE.J ¤zl*ol zzzx{ E4+ ¤fleegq l0.00kle-l

ol^J4 B Bqel.tl4 zsouel 9lulxlE gs^l zI9 E"¤-4 o + old
C ol
E3A.4(b)
¤9 g +zllE gE= $u]-fl}-u|? =
r+Ag (D zo"cel (ii) roo"cgl^]
*LoI3.00klE "Jg.Jtrl. T}
^l7l= ^J46il -uzl. 4?"1 "JqBqB
E3A.r(b) qts + ol*zl 9zl$9 & g-+iHE Sszt 0"coltrl. EAg E ol B Bq?-19 sleeslzl ¤"I4 H6IA!+?
V B¤- so} 3.00k19 "Jg b.JtrlH Eag ¤fl9 8s
g-e-e+q 10.00kJ9
ol4lol+^ Tlill=:OOr{lrj l.0dm3o ++el :.odm:o +
E3A.s(a) rSg9
E ¤u}4lg4i .rqog o}al^la qE ol zlillel {!= +E H+= 414}6}q4.
E3A.2(a) Ez+ gge.l Sszl l0o.colg & g +zHE gETi ro.coJ ol E3A.s(b) 4.0Ogs-l e4.E:OOfgl,,.l 500cm39-trTEl 750cmro + E"g "J+
t'-4 g 7l+el Agg glu}-olflLt{? ^la
qE ol zlillel Sle_+q H+= 4l&6}q+.
E3A.2(b) o.J oltl4 Bzl*g Ea$ g?lE $ETI40"Co14. .tr'gol 1070
E3A.6(a) 2e8Kql^] lag9 4r Tlill (i) E"3 zI94 o e S+6Iq,
zl r{zl 916ll^]= & g +{E $szl B"Izi 99oF dlAL+? ^lEzi
(ii) p..=o{l *^J^l E"8 ul-2}94 o + S+6Iq, r?-ln (iii) +g 7lE4
l
E3A.3(a) q tr + r+aql^l 419 s!= _+ -4zl rzsl r, EI# ¤=716Ir. +glE
tlE +q= l2sl rc' "37 z#¤I4. ol 4aol x]-$lolflLrJ?
_q.-e uJ+6l.4 : Pulz} ul]e g trIg 4le+ r +9lE flE+rl Hs| rq
r diil slE +sl Hq¤ 4l4l6lq+.
E3A.3(b) qE + 4aql^l 4lg ql= eslT} lOsl rc, EE eTvla_ +glE E3A.6(b) 2esKql^l z.sgq ots+ zlzll rlEz| (i) Fg 7IE4-o e s+6I
flE_erl= esl K ' El=- 44494. ol 4aol zlp{olflru}? q, (ii) p*=0oll '*^l^l ¤ig Hl-71-E4 o + S+6Iq, relr (iii) E¤ zI9
4 o e S+6Iq r F:4zI l.20dm3s-E-+rl +.oodmro e Gzlz'J trflg 4l
E3A.4(a) +4 BqElql+ looklE 9lHzlE- gE^l 719 E"e.49-E "l e+ r +9lel $e-eq Hsl r4l dill flE-ejIl Bq¤ 4lÎ6Iq4.
=
d^l7l* rlcg ^J46ll -ez}. ol 4c"l (i) o.ce+ (ii) s0.cql^l "JqB+E …
ol +4 Bq?-lE $ee.qz1 9014 E6Id!+? T> 거 RM비

Ui
T π) Cpin* ÷ T
iTT ) Cn
블
EEf, 38 zl-8=oll +HJEI= fl!=+4 EA|.
=8
¤E E^11
D38.1 14tr qtsg!+ Ag .-qillEol Trouton9 +!gs+El
E, fe-,
H.q+= ol¤¤ ¤E6iq4. olEel 6"J 8l= +ulz} asl IC' mol-'-84 l
41.!+, E= zlal.l-4t r olf¤ ¤B6Iq4.
G -.^-
JtJ
¤*ol 44 1.00k8"J + +?-l '"iqq 6 6I+E gETI s0"Cola gqq^l "Ja6I+n rla6lq+.
V
E3B.1(a) as,o,el +3iql +6ll^l "J:"I{4.
+= 6I+= 0"ctql, "lE¤. aBB ¤-zl(89 $ qLJql Br ¤ E3B.t(b) d=*"1 44 ro.or.g"J + ¤q4 + 6l+= gEzI roo.Col
^l +zltg9
Bg ol+r]l 6lB.+. + ¤qelg 3l+ eE ?+4E gleeul He+, rqr
="Jol r +e 6I+= 2s"coJEll, olE¤ rB¤ "J Ele_)ql B
Aq",$ 4l&6}q4. +?-lE Hl-g+*g 0.38s1K 'g-,olA ral Ell^J gE r B¤g ol+al 6i9trI. as.o,g 4l4i6}q4. ="Jol Hl-g¤'Pdig
^l 'dqelel
110 2E=lrt3E=l
o.MeU r' s-'ol:L l4 4t gE ¤qql^l "JA6I4I. 7IA6Iq4. As,* E3B.s(a) eel:=E-Eqlfl=.e-eE.E, cHCl,)E +g elBirlY a 7l+ #
E +gq +4^J "5"l.44. *d:r+.asroll,rl 2e.4kfmol-'o14. 11; ol $roll^l EEI=.E.Eql+E ="ts
$_Etr:4e+ (ii) ++lel qlE +El H+= 4ltld-q+.
\2s"ce}5.00atm9 V
E38.2(a) Co,-=*R?l 3.00mo19 7li]l=
t4.a Hs}^lag qE
TlzllE
25"Cel 1.00atm9 t}4.e+q
As(alq q.J)= 4&6}q+.
E3B.s(b) ,tl*gel +g S94b a 7l+ #E¤ 64.l"cq^l 35.27kf mol-'
ol+. (0 ol gEql^l
"il+99 ¤:ts {l=eEle} (i0 +9lE slE+rl Hs}
838.2(b) Cr,.=*R?_l 2.00mo19 25'Ce| l.50atm9 ^J4tr+El
4lt}6}q+.
13s'ce| 7.00atm9 t}4g HE|^la¤. 49 mt4lql E|].J)= al&6}q4. =
E38.6(a) "JAqI E.q 6}ql^l o,(d9 gEE 2e8K_?.+El 348K-e. +flg
E3B.3(a) _10.Cel B¤. rogg lbarg "JeqI g}q 6lql^l lls.o.cE t6 trll ol Tlille.l E tlE+itl* gulut ¤:71-6la'-.r+ o,9 E "Je-$q g+
zle. E*t,rlag q9 ol 4lE uE+vl H+= 4l&6I"14. g "Ja "Jq eJe Zg8rql^l29.3s51K t mol-'o]4.
g+"*3 cr,,(Hro(s)) =37.61K-r mol-I; cp,"(H2o0)) =75.316-t *61-t; 1t-l
r cp-(H2o(g))=33.61K-rmol-'oI4. rela Hro0)9 .*.= elBEl=
E38.6(b) "JA+ "Jq 6lql^l Nr(s)9 gE-=- 2e8K_e.+El 273K-? Ll]fl
,t0.7kf mol-" Hro(s)9 .tr.= +8 flg4} 6.01kf mol-tolq, olEg
=:g. -q.+ * I rll ol TlillE EtlE+sl= gtrl+ E6'Ifl'-.+? 2e8Kq^J cr,.(Nz)=
29.1251K-' mol-'o14.
¤ gEq^1el <lEol4.
E38.3(b) -12.0'cE 99 rs.ogg lbar9 "Je.J $q 6lq^l 10s.0'ce-l + qlg
^leel E ,Ig6l-fl+.
elg-eulY tre.zz1K-' mofroltr|. ol
V
E38.7(a) 29sKql^J
*zltr H¤+^lag q9 ol 419 slE+El H+= 4lt}6l.q+. *e-l s+9 .(l-85 "JAt +irl 6}ql^l s00K-=. ril+E "Jc +ul g g+
EllolEl= ol+6}q4. B¤ +RE. +16l.a ol ,r1tr9 sOOKql^JE E SleeulE 4lt}6}q4.
^lEel E tls_e:4=
E38.7(b) 2e8Kql^-l o].-e,* rs+.s+ I K-tmol-'olc|.
E3B.a(a) Thouton9 +zlg ole"o|{ {ldlel 7l= #*¤ so.t'Cql,q9 6
g $Bfl= qfl6lq4. 2soKq^l ol .rl-89 "JA-+tl E Slc-eu1E Altl61q4. ois*9 "JC-
+:4 E g+*e inol4.
E38.4(b) Tiouton9 +zlg ol+6}q 7l+ #=d sg.7"Cql^J
el +g SIBEIE qfl6lq+.
^l-=Edl4IE
EE 3C fl!=+trlel
=¤
¤B E^JI
o:c.r ¤.o-4 49 ol9E9 s= SIE+El7t olol slzlE 6tI gol qzls
6}l, E sol rlzlE ali o1.95 ¤B6Iq4.
G^
L-l El
E3c.',t(a)
E s=
V
2esKql^l lmol9 NHr(g)z[
HI* tl= +El= 4l4l6}q4.
rl+^]EIE gÊe+q q]c¤ trll
^Jej
s= Hl* fleeglE 4l4l6}q4.
(i) 2CH3CHO(g) + Or(g) -+ 2CH3COOH(I)
E3c.r(b) 2esKq^l lmol9 Nro(g)zl-zl+ tr-Ellg ?l^=e+El BCg trfl
(ii) 2AgCl(s) + Brr(l) -+ 2AgBr(s) + Clr(g)
I s+ HI* fle e"l= 4l&6}q4. (iii) HS(l) + Clr(g) -+ HgClr(s)
E3c.2(a) 4.2Kql^l eg(s)9 g+=*g 0.0l4sl K 'mol-'o]4. Debye Bzlol E3c.3(b) s. 2C3r+ 2c.49 EllolElE ol+6lq +g Hl¤¤ql q16J 2e8Kql
4*E4r zl.{a}-r. gql EI.J s_(4.2K)-s-(0)g ea6}q+

E3c.2(b) Ae(s)9 g+=*g Debye Hzl cp,.= aT34l qsq,
,r-lels.f HI* sl= +El= 4l&6}q4. V
^]gql^l (i) Zn(s) * arz*(a9) -s Zn2*(aq) + Cu(s)
a= r.e56x 10-4 I K-4 mol-' ol 4. gql q.J s-( l0 K) - S*(0)g A A 6H 4. (ii) sucrose [C,rHrrO,,(s)] + 12Or(g) + 12COr(g) + tt HrO(l)
E3c.3(a) s. 2c3r+ 2C.49 EllolqE ol¤-6}q q-g EI¤¤ql qlql2esKql
EE 3D 4l ?lTE LlEl'.! 8tr

¤E
=^11
D3D.1 41q CASq! zlzlr 419 zlBCg Ec + 9l= ae qqql a+ D3D.2 zlB4 Hqql ql6J 7l=o +^J dAr,,.<0, r,i dcrp<0olalE alEol
c|
"l
ulel ol.$oll,r.J ol u|? ol+!r 9l+. 4 zl+EE +4, e.lE, r4l +SCql *ullr] E6Iq4.
EA 111
G-\
Jtr
E3D.1(a) 2e8KE-s+ aaql^] qlE(cHJol ¤Êl= Se {2121-9111. n flB4= -e6eklmol-roltr, E. ol gEql^l r. E= E Sl-es4=
V
{xlEf,q Eg + 9l= l mol *9 314 Hl-s+ gg al4}6}q4. s.= ^JC cibbs glHxlE 4lt}
ol 103.s1K-' mol-'ol4. 2esKql^lE
E3D.1(b) 2e8Kel .*= aaql^J lE+TIC:Hr)ol ¤4q= $e. {2121 91 6Iq4. e^,*+ +6J¤E ¤^ ^JCES =+{EN,@)E 84.
trt. ol dzlE+q gg + 9l= lmol trJ9 3l'll Bl-s+
"Jg 4lÎ6lq4.
^JC flBsl sq Al#
E3D.4(a) zle- ¤9 -E= ol+6}q ¤6 s:c.:(a)
E3D.2(a) zlE ¤E .tr=
^JC Gibbs
ollLlzl {tg ol*6}q +g H}¤¤ql E HI¤¤q 4eI zgsxql^lE s= HI* elBq {lg 4l&61q4. rqa
4eI zrsrql,rlel -*.¤ ** ciuus qlqzlE 4l&6'Iq4. ol er+¤-E3c.:(a)oll,r.l olul 4l&e! s= HI* $E +ule+ aB-^la 2e8K
ql^lE olE HI+ql 4'* s+ HI8 ciuus ollulzlE +6lq?+.
(i) 2CH3CHO(g) + Or(g) -+ 2CH3COOH(l)
(ii) 2AgCl(s) + Brr(l) -+ 2AgBr(s) + Clr(g) E3D.4(b) zlE ¤E .E=
^8C SIBEI sE <l# "l*6}q
g+ E3c.3(b)
E H]¤¤q q6J 2e8Kql^19 s+ Hl$ Sl$sl <tg Al&6Iq4. rfll.
X
(iii) Hg(l) + Cl,(d -+ HgClr(s)
ol {ffi BC.3O)qlî olol zll4lal E= H}* qlE eEle+ ¤6Jrl4 zgsr
E3D.2(b) ¤9 s= ^8C Gibbs
zle ollH^l
<t9 "l*alq +g HI¤¤ql ql^lel olE HI*ql 4EI tr= Hl* ciuus qlHxlE +61q4.
q6J 2e8Kql,tlel s.E uJ* ciuus qlqzlE 4l&6}q+.
(i) Zn(s) + Cu2*(ag) --> Zn2*(aq) + Cu(s) E3D.5(a) ¤91 ++¤ s+ ^Jd $lEeulel flgilE
z|=. ole"6l.{
2esK
ql^lel HI* +Ht(d+o,(g)-+2I,(s)+2H,o(l)ql q.J E.= ++ cibbs ollH
(ii) sucrose [C,rHrrO,,(s)]+ 12Or(g) + l2COr(S) + ll H2O(l)
zl$ 4l&6}qe}.
E3D.3(a)2esKql^l o|.glE_t}glB(CH3COOC'H5)g -E= gi $Bq= E3D.s(b) zle ¤91 ++¤ s=
^8C
qlE+qe+ qlBq= olso6Iq 2e8K
-2231klmol-'ola E ol .$EQlrl :r E+ gi. qlE+tlYzso.+1K-rmol-r q^lE HI* co(g)+cH3cH2oH(l)-+cHrcH2cooH(l)q ql.J -se HI*
ol4. zssrqlrJ9 +6JEE E+ dC glHzl= 4lt}6}q+. Gbbs 9lLlzl= 4l&6}q4. B zqaxql^l cH3cH2cooHE s=
"l Gibbs ^JC $B
E3D.3(b) 2e8Kql^l a41 olulrrtl E= ¤ ulE -stotgmol-'olil, ol $E9ld g= E $lE +El= 19ap-tmol-'ol4.
=+{(NH2CH2COOH)E
CH 3Cooc2 H
5
+ 502 -
→
4 co 2 + 4 Hz0
우
②
3E 1E=lrlDrH
-
표준연소엔탄피
EEJ 2E=lel동 DFH
=
(J ) 정리해서 Dδ H ( (H 3 ( ooGHz ) 를 은항
=-Et
표준 몰 엔트로피 DMS= Dmso
0
DFS
=
[ [ H3 Cooc H5 ) = J
¤E E^ll 0 2
=
OrS glHzl9 zJkSm
qi+
(5 )
gluJ^l9 gEql qq} E=EE E4q*4 o +
D3E.'r Gibbs
=
"Jqq- E+E= E4q*4 " + ¤E6Iq4.
9 의
D3E.2 cibbs ¤¤6Iq+
DrG trH 0 TovS
G-A
Jrr
r^ll ^Jq COrzl ¤+g ull=:l EPslzI -1.6cm3mof' "E E

E3E.1(a) E3E.a(a) qE "JA g;q liAq qoJ Gibbs qlqzl Hs+zi
LGtl=
glq¤- lbar-trpel 1000barE +g¤. trllel E ¤¤ ciuus qlqzlg E
.Jtr}. -8s.40+36.s(7K)-e. +qA+. ol n+Aq 4t
as9 <ig 4ltl6}q+.
q¤ ga-sq 4aq qEl Gibbs qlLJzl HEIzI LGtt=
E+= +61q4.
E3E.1(b) rill rllE: EPqzI0.5cm3mol-t o.ffi soJ
tlEll Hldlol ¤¤-g
E3E.4(b)
-73.t+42.8(7K)-=.
V
+qd4. "l r+Aql qo.J 7}g 4lt61q4.
q. "Jqg lbar-a*rl 5000bar-tr- +fl9 rI9 ¤' ¤-& cibbs qlqzlel HeI ^sel
E3E.5(a) qH "JA g-q qdql qloJ Gibbs qlLJxl Hs+zl LGtl=
+61q4.
= -8s.40+36.5(T/K)-E +qd+. Gibbs-Helrnholtz 49 ol+6tq ol 4Aql
E3E.2(a) Sd 714le-l $qg 2e8Kql^J t.Oatmo EBrl too.oatmo e E8 4qi {tg 4l&61.q4.
I ^Hel qE
"J+^l7lH E Gibbs .llHzlz}
9"I4 H6IAL+? E3E.s(b) "JA g.q r+Aql 4el ciuus .llHxl Hslzl LG/I=
$d 'l4lE $qg sooKql^l s0.okpas+ei
E3E.2(b) roo.ot<pa-e. E"g s -73.1+42.8(T/K)E +qd4. Gibbs-Heknholtz 49 ol+6}q ol 4Aql ql
+^l7lE -r. g Gibbs qlqzlTl ¤"14 H6l4L,+? 6J Ag 4lt6}q4.
^Hel
E3E.3(a) 300Kql^l 2.5mmol9 9d zl4l Ezlzl42cm3el +4E zlzlaf,4. E3E.6(a) r.Odnt'9 "j4 +*ql 4*61+ "Jqg 1.0atm9-tr-$4 rOOatrno
ol zl4lE tulzl600cm3z| ¤ ullzlzl Eg S+^1d4. "l 4aql 4aJ ac tr fi2p,14+. Gibbs qlLlzlel HslPd.+ E Gibbs 9lHzl9 Hs}%lg +-t
E 4lt6lq4. q4. ++E eE*'JE= o.7o3gcm-'o14.
E3E.3(b) 2e8Kq^l 6.0 mmol9 Sd 7li]l7} 52cm39 +qE ilzlaJQ. ol E3E.6(b) l00cm39 Eql z}*6k "Jqg ae
→
-
l00kPaE+rl s0okPaE Gzltl
zl4lE *glzl. r2zcm3ol ¤ ullzlxl r="9 S+^1d4. ol 4dql q+ AcE d4. ciuu' 9lHzl9 H+*!+ E Gibus
"llulzl9 He+*g +6Iq?+. Eq
4l4l6lq+. ae}'JE= 0.997 g cm-3ol 4.
112 2E=lrt 3g=l
E71a s 2=47.1-3851 RTEltBP )

ET.ll
Vm =
ㅡ
4.6lxl
o u -r [/'ll
P
t:.t fql +EE+Jq+ ÊEllE^lEE ol*4q ffi $zll$ B6Iq4. (e) szl..r.lq 4l+{ol i4E g ,r1ol-cgl dfl t^ll+ 4* zE lro}4)E
(a) 298K9l,tJ lmol9 Cor(g)E 0.001m39E$q 0.010m,o + S+^lAg van der waals zli-lle.l +I& +ulgl E4-a +4LllJ, ol pffi 0.8 < y. < 3
trllE {l E e irl Eq¤ van der waals zl zll$ z}{ a}r. +6}q 4. gqql ea^J +l6J+Î.gEql 4ofl,rl E^l6Iq4.
gzl (ii) dB 4dzl, (iii) ul{q Elda}s g sd Tlill
(b) (i) oJ
^l-E-E
A +E 6lql^J r4I E "JA $q 6lql^l TISB rll9 t!= eEl HEI=
13.2 l.00molE +^le. ¤ zli'll ^lEel t4zlpV,=RT(t +BilE- -tr^l+I4.
ilgql 373KoJ zlz)lzf loule-Thomson S*9 aI¤ "J4"1 toOatmo +*El
-5a^l6lq4.
l.O0atm o E gqe+. Cr.,=*R, F=0.21K atm-r, B=-0.525(I(T)atm-'9 *
(c) ¤** gE e.l+g C=a*bT*clTzo+ +41+lr" {lE-+irl $ffi ol
E"l Exll9 gE ¤qql^l "JA6I+I. 7lC6lJ1 ol zlilloll 4oJ are| as
^ll
4l+Eq tolal *5c9 +E iig q+)ql 4dll^l E^l6lq+. E 4l&6lq+.
rilEEL+ @ct)p1,zy
(d) Gel oJqql q?+ qB4l
H6l+zl= 4e-a +4
4g "l {g ^J*.J Sq gqg erq^J E^l6lq+. (EG/Ep).pl Erlqlzl t3.: 8!e+v1E gqql4 AEe+ FAI gqo}4 AE
Î"19
+4lg b6I
EE= *9."14i q+.
looaty
3
n3 k : looatm- →
d
TCI→βP )
OS =n
Pm
다 어낱 Vm &
:
ㅡ
COo
VmRT ( H βP)
f
→
DS = n .
i 5 pin . .
To
00
=
-
n
-#Vl'\.4
#EtEtrol EtrJ
=el4
+9, ¤+, :z4l g¤oE+q qolol.$-E_Eel H+ ¤+ t-B g flolel EE-+4 ga
E-+7I Elol4 acE H9PI ++q4 g= tlE HEI+. +
++ E{el tF H+= gqtr+g e++.il ¤+fl+ ztat tt ol e$oll.<-l= l}-B"C :-H9l +El+E gqE
^Plel A4ldE
+ qlol4, olq+ rlaEol "Jc+ gEe+ "Jqql^l gq+ glile+ -s"Jg acq+ _sq]# aa++. ¤zlrl +E6l.b
^l
4H :z AIE Gibbs glH zlzl zl^.q"l"t 6J+= gEE # i==g EeE
=o zl
oJElol gEql ,rlEI qg4l H6Ir E. ft-flol
rl4"F ++. "Jqq ,44 qB4 H6IL-zl= +4U+.
48.1 eJ8.Eoll gEi= += 4a; qa.z I ealE glil
4A ++-d Etr$ A-"=E f.aJ

* Eeol zlt "Jc+ tlg olE + ?l= "Jq4 9=.E g g rt-E 0l rlE,el EE=?
q(+ rl+ *gGibbs .ilHzlql 6ll%Iqe._)g +EILI= rHg
t'-_¤B :flolep *+.tlE "JAEql ++ E9sl4 z16 ol4F++47l
="J4l +ill ^Jqlq^l
Lt4ql= ceg sq6}
I olgal$ .tr-+zl,ol+r 6F= q+q u_¤4ql 49 +E r ¤++ Elolzl E"-l %LBoll ol+qa fleq, Hl clE E-
pl. + ?lErJl, ol +zlg
^JEol ¤Bg
oli rll $sd ad cEE *Bg qla4l ++. ol ca+ ¤+g ol rzll E Î"l
=
fi$ s_o5g 4.o14. ol +zlg FIE qel tlql^J + + 9lE+ Eel ga} ooll tzga1g4.
zd$ "ltr-el 4lqlE 4+q= "JHI4"J Ee +$r|]Ela +
4. ol Eqql^l= E.6J e+4 9Hl¤"144 6l+ Ceg E"J
6}rll q=ql, ol ceg gqlEr+ +qL HI¤¤ E6l+trll ++
4 qgg 61al g+. olq^l ¤e4eg ee H TIzl dC¤
4lE9l tr--¤B rHg ¤B6IrzI EL+.
an.r 89 u8E; aa.e I eal; 4A.3 Tlrl EilEEI 8-Ba lH
îl
Eq t*A #-et=trol 8-8tr:zaJ
$d6l sqlq= + .lillE *"J d-¤- olE+.

> ol EEE B||+= ol.R
a-BE :BP EEill 80lEt 4Aq|^1 LlElLflE d# eqrpl
aolq, E-d aEq gqqhl olE c|olLt d:Eol 7Et ?J8 ffi:doll 4A1
=8:d
Elx l= LTEE}|T E ettr.L 0 lai-d a-BE ++-d Etrr+ gs++EE9 ++"le +g t"14. g¤+ grll
=aJ8 =EtE "I+"-l
sF9 B- ol6ll6lE t1l BEol Erl. z]]EEI tsotE *9 r}ol+. gg4 go1 gi$ ol+r 9l
=sEt
g trIE Hl+ + tr-E EEl4 4A1E IL^16I.717I "lBzl"J z
> e4fl TtlLJ
++-d E¤3 r trlqf trlEJ!¤o| ElrjTlEl= 8= ol+all -Lrtf.
$ /l1e - z) o +. Et}*fol cacorls) + cao(s) + cor(g)9
I
gB6llE "J o zl.z ?lE 4lE z4lE rill d'-(ts,t}e+I+ 4l

> "Jg:d qHl rl^l EIA+E + tDr+ 6l+E zlill $1oltF+Elleg Elq 9l
o q, p=3014.
0l EEe Gibbs ollLJxlTl gB e-Eet gqE rZ 610ll^1 golLl=
xl.J4 EelE eEol qg=:dtrlE Er}|-e g aol+.
^l-t=
+ ++ol ^Je Jolzl ?*g ql:- ztr

al. "JEa(p=2), .<)
EAol "Jqa + gl= E4zl ^JEll H+= 7l* rJ46lrll Ll- 6Fg
+rll= el zlzl ,JBe tr-¤¤ rflg 0l+6|= 4,o14. ol z}] -tr 4lg + 9tg trl]E
"JEq +"J-tr-4lE "JE + 9l
.¤e q-g E4^ s"llrJ EqlEg E6l+ Ql zl=zl g aol+. 4(p= 1). aAl e4gl r.zll ezf +ot gl= +aq(+ Eeg t"J
+ EJE)3 EzI 4E.ql^J t"J6I+. olfl +q 49lrJE e
flzlz| eflzls+ BgÎ-tr. EqAlq ileq, o}+al 4rll g+u
t A.1 gsl ?Jg=. rqlE +4u+.
.r.lEalE +.1 dillel a^"rg
gqqlg ^JE "JAEe+ H+13 E6l-r olo|alft.rll r+l+61 + E4Ie EaE a4 +ql +E * Eeol "JrJol4 *¤
6J
s6J E6Jg 6l-zlE| olag ols"6t4H +d {zlrJ ¤4-s EqTI ?lE 10 +.\l A^14 4Eql^l= tojolzlu3
^l-8-El= EI+^l ;..1_E_E
Ae-l# Sd6l ol6]|6[ot 6J+. 561 '^J, '+B CEI r?]I "l^14 4-Eql^J= +"J6lzl ?*4t:B 4A.l).
'zl+E'{= +q= 4. ol6116Hol ++ 4lrll g+.llE +++ AE + 4r9 "JzJ"lzI +lrl]d +E 9le
q, dill !le-l adg 44421 *ts +E 9l+. tr++^l ¤4Ig
+ ^Je__E "l+qd 4o14.
(a) 89 #
EeE ||"1* slql4 a{g EE 844 t4z} dill4_e-tr (b) I dol
t"J6.J EAE B4+. r?-l6lq +el= qi Eeq rill ^J, q4
ill ^J, "l zl4l t¤. "J:"Izlr a|:q s "J9 dg E" rille+ g +q{ "Jq 6}ql^J= q} Eeol dol EE r*41 al* t I
+6J gEql^J zl-g.4 o + +E: tr-e_E H++. ol dol gEql
E" c4l4 EE
+&A+E oI{I+olEe+ ,,J6]]4 6q+illEr+
ag qq lz,ll tIE¤ "J6}zls ++. ^JE + ^J"l
¤Bg ol+rll q=ql, "ltrll ol 4lg cibbs qlLJzl
zl \rzl ¤+.
EoJ gE 8^l Ei^ll= * gÊ +E6J EzI ¤4"14

zltrJEt 0{l 4A2
(qls^l o2e+ o3), rill+, .lill+ Ei zlxlloi + 9i+. trl^+
Bill= giLI plElEol "JE= qel rill +E a}4"l4. -gEzIo'C-B+ *g uI= 9¤-"1 Eq qlA6J tr'
ratmoll^l
^J
ol! 0.C ol^J"J ull= "+417I q "JA6I+. olag 0"C ot
4l 'Jql 5q9lb flq += Ps +4U4. zlzll4 Tlill^J s 4ql^l= 5ol p$s_E Hc. ql Gibbs qluJzlz| ai6I,L
qlEg +oJ ^Jolq(p= 1), 6.J EeE 44E +"J ^Jol_I, .E
4A ++-d Etrsl $-trJE f=J 1 15
q, q+î +olot$== +ge e qeJ= gqo}4 46i* 7l

r- zla glq.rel+ olelql E¤lol .Jq+eH El flzl¤9 9l
D- ilz[ {a[o] oltull, r.zll +qlî= olq+ r+4ol ql+61 te
+Aol Eztts Atr+ L4rll "Jq++ ¤
a O-
s_Eql^lzl-ol-ulE
I) a 0. B"il sE:"I^b +E= HI¤- +EE4 Eîlo]I SEEE H+l
Hq+= E^llol+. Tlill+ "+zll +ql^J= E4¤9 olEo E
(a) (b) =
zl qEql dolTi EUL= +Ee "J"l4zl"J _r.illql^-l=
fH =z) ^J.
4A.1 (a) adol ol4 4E 'so-e E"J-d'J"J .8 EEzl'(b) -d ¤EE gq+4 Eqle tr=}lz} gqBg + 9lE 4014. gq+4e
Bqol += ¤Esl 0Hi1l +oil HJd9l= Ettg xl.ol.
^l'olg E E"J¤61-H^JE +EE4 ttol]E BoI dolE "Jezlzl *
6ta 9l= ^Jg 8"141 *+ qlE^-l rlolo|-e-rE s_
=$8
0"c floll.q= g¤.ol Etr. HB ull ciuus qlLJzlTI +i6J * z4 6}ql^l Eiel ="JC
tol4.
+= ag E6l^= 4,ol4.Gibbs "llHzl9 +il= trl-g ++
+ qql^l ra6l-a+. 8 9JEE9 Eq+4 7l=
(c)
{zlrl ra6}= ql+e d+ Ee9 ciuu' qlqzl, 561 E

Gibbs.llHzl c*91 "J4qL 4ol4.ol gqql4 "Jgqal EI*
t dolts 6J^J d|l Bzl slzl ?+sq, + l.xll ,<|o1q1 nlEl¤"]4-IL *=:r pE ++4=ql, olag ol s4^c+ ol
=61
^l tL d"lz| "JqB
ql= bql -Holzl ?+"I^l a+6lzl= ?* 49 *"lzl ++ql^l ql+61 +9-o} qgg 6IZl El= oJol+.
4. dolzl "Jq+= Eqlql ,J=q4+ g+q= 99 ol*a} lCE 4lql ql6H^J='EGibbs "llHzl'4'ElqL 8HI¤'"1 54.
EE s!$g ol+6}q td"lE qz$alzlE 6J+. dolzl-
^J
g *9$ 7l^lq, tr|{^J I=G_ol 9xl"J ElqL qfl¤$ olB4
= gd q He *g 7|^lq q "JHI4eE eEgq= 4¤ _=.
Bg "J+g trll= ^lE= B4^l7lE^J :z e_EE Eqqg ql
zl+4"J gE 6PJ-ol B+l1l+(r4 +t.z). uffizl-zlE d"lz| 4 seq1,<-1 Hfl+rll g aol+.'++ ulHl¤'"]4ts olBS ne
gg **"J q= zl44 o + 7IS6IH {ol $roll.! 4"J Ba "E^J, 6J EeE pE 4l9lrJ H+= .Jq+rll g +
^lEE
gE ^J+ol H+rll ¤+. E g 4l*H(Eq 2c) fl. al4lq, + j4Hl¤el 4t;;l g+= ag "J4l B 1o14.
^lxt +^l^l
g ole" 6l.zlE op., E + rill *e-l +=71+= dg ol9-o 6| ol Ezlae+ E4^ so|rJE olaol + Eeel Efl4 H+=
xd qd(Eq r8B)E ol+g+. $ezlE fl.21]49 Hl¤{+ rll t zlzl"J E4^ 6ql^J= ol
= 6}tr-+
4eql EI]EL gqq}4 e4e+ r dol +E= +E p7t slq| +¤¤ "Jq+rll alE 4lzl]qol gtr|= 49 ul]+zll
6l +a6I= lol 6,q6[+. gqE4eE z[${o]r-}-z gl^J- B 4"14.
q= tF dolzl. 4xlltr_E +^]ts + ilg cEq -t-fl gre. ol Eqql^l +E6l+ ae ++r+ z;-ol E¤E ¤94 zB
"Jqg + 9l= 4"14. qlE^J trE gEe+ sq 6|ql^J= + zlql "J46J 4ol+(rB +R.:):
$ol clololEEB+ El *g E Gibbs "llHzlE zlzll g_o
¤¤ tlEIql^J= * Eaol H z]]9 r}g ol+a oT'
gt= t}+Hol plel qHl¤ol [60 Kl-]
^lE d^llE =l6l]^J

H0\
to
s4iil ts4
+"J6llot *trI
Lil+el +RCe -E-zl 9.16I¤ zl# qE + EeE sI+
"l
ulHl¤"] + +lzlql^J}p,oll E += o.J *ql^J=p,4I aI
1-
ui
0lt
Tt o-{ill
zl-. F +lil= Eg ^J +q flg +E ?lr, E ^JE += tr"
ol
=g +q flg +E 9l+. 6J 9lz.l-++El += +lzl-tr. dn "JE9 E
lxll 'J4
d=J"l "lEEl= A+, alel Gibbs o|HzlE Eeol 0l+6ll +
7I= +lil tgl.'^.l -!dn(4 dG = -G,,,,dn)trJE H6Ir" 0156l
t
EqTI= 9lil 2qlî +prdn(! dG = G,",rdn)trJ# H'J 4,o14.
g8 gqoll^1el LJ4
^17J, trI+^l dill Hs+%Lg dG=(ttz-tt,)dnol ¤+. "J"J eilil lql^l
azJ 4A.2 +d. +'J +.8= "Jg EolTl "JolLl=
s-s aleol Bf
Egtoil
^l7l
n|lEoltrl. dol=
^l44oe =
+ aqE 0l I slql ulHj¤"l fli.l 2ql^J -E-+ ts9 ullE "l4al Ed ol*
'J4 E= tr]lEoil rf= *= + ?ltrt.
116 4 ffil#9Eal4E+
gzttr
\
lrll o4rll
al+ qEJl¤ a-
=g-d mi 2-xl
U6E
6n
=)l
T3 Tc
-qE T
fal 4A.3 -d E¤E qal g=01 gBg olF;I 9t= nl|: r Etr(=-cf=oil
-d dE)sl al+ qEJ.l¤o| q! goil^1q e= gu olLlal4 g= LH+E fal 4A.4 0l gg:d raJP -Ir1l, e4i1l, g 7l^1171?J86l4l ErH-g + ?l=
^1= (= aIlE E Gibbs oilqxl= ,JEJ "Jalrl,eE Bq= LEtL.!trt. q|e^1 '*3
clE troil lE,Jtrl..
EEet te galoll^'l= rrllTl 7Et ?-t8-d 80lc].
ql qoe. ol HolL.zlB4_o-e "Jq+

E6H^J G7l *^16lz11
q q+ qB4 Eq-=zl= +Elu+. u|t}zl-zlE l.zl-f;zl r}
eJn 6J 4o14. FFpz9- A+q"J G7l Hoizl ?*eq, olel+ AA\Y rillel e=1 SaJE gE E=g +Eid+. gsz1
=71
A+q"J 4lrl-¤¤g ol+r 9lrfl g+. +otzlE "l* E4E*q gq4 'I.g + 9l= +E6J qlqzl
4= EzI fz| rlotzlrl qlEql qI EeE +71 "Jqe g
=
Eql trl+ 6zld4.
¤el 9zl| +.oll.rJ ti;r qltr- oldoll L+Al7ld iL] -r1
ou?Jl-=.
#?7]l4 s.= g ^JC ciUUs ollHzl
e.-r_l 'ol --1 -[,.] ---l ,.il= 6* -1 I rJ -i-ii , a"i,
2e8K(2s"C)ql^l
EillTl ++El +Bg + gltrt. rTlr 6zl $4"1 e-l+
E -zzgkl mol-'ol$ Ag gEql^l a44l Ee-l "l Alg -trH_o
trt+^l 2e8Kql^J #zlz[ eli]Je ffi sq4 aotulE gEql^J= "_4ill dillE E6I]^J +gol gq
-237k1mol-'o14.
g trll=Gibbs glHzlzl A46Iq, r?-l6lq ol $rofr.J(:. 44 6z17l +fla zlf.$rll tr14+e + fl+. ole+ &ol q4
ill di.llE ¤l6l]^J zI+ +tsol gq+= ¤tlg E="lrtl "J
4z rbarglrJ)E ffio1 zlg4ol4. 6iq, "+AlE +71 Sqol e-l+ Se4 potxl} gE= :_ S
Eql^lE E:=Eol+a ++ e]+ $4"1 tatmoJ 419
=61
#E 3s.= 88 roolr*.l. ql+. s= *qg tatmo
=EE
4A.2 I e4! -e-+El E!flg Cel6}4l 9fl4. "l
lbar-tr Hlfiql ul4 s=
gE= +71 sqol rbargl .E-BalE: 9rol4. lbart. latm-H
tlEol gqqr-4ee ql{6}rll + ErJ 49-E-e.(1.00bar=0.e87atm) .+illE E.= #=dg A
={g + ¤I+
6J EAel .1Bl 9l=
.Jer+ gEq ¤qg +4u rBg aBE raJol4r #=dtr+ EZI *tri. qlE^l EE C^J #=de 100"col
^J
(rH 4A.4). zlzl* ?Jz L .E# #=dg ee.6'col+.
Î¤^J "Jelel + ^ll7l ddtgse+
E9 seql^l= E E¤E. ^^"Jtr})¤- ol+g f ?lzl"J "l Eq
ql^J= "Jq4 e_EuJ-$ d=!4 o_=. ol+44+. t}*l¤ :zH
ql^J gqE
Îolel dE¤ I e4l(a"= +d)+a
6}=ql,
"l
d.e + ^Jol ¤Bg "l+H^l a" ¤¤ + 9lE pe+ rE <lg -71
o.
ote{
I d-,
+4U+. +"J tle tr-_¤B rH ^Jql^J H"lE E^lgtrl-. p
=)l
(a) I Eolel tralEE
=¤=
Bel *zl +ql Eqfl: ++6J orrill r.l-EE ^J46ll _HzI. E q4rll
^lle+
¤B¤. ol+r gl= +7lel "Jqg f EeE gaj rill
(Eq lcql^J ¤E* c¤, :zH 4A.s)ol+r 6J+ nl.+^l =71 =e
^J
¤B re tr-E "+ill-+zl * azl= "+illE +71 Sqol 8s ral 4A.s e4illLl rrllsl gfal= r ¤=dlrl'JE= 0l=? oJE eTvl
LfEfLH= "Jaloltrl-. =7I
4A ++-d 8-oJe ral 117
=tr9
zlEtEt 0{l 4A4
EE *649. zzll6KeI 6llPa(6.11mbar, a.ssTorr)oll 9l

il++. "l ole.lE q= qE gEe+ "Jq$ aaqlîE îl
t"l E"E¤ += S.trI. ol Al+del tsECe gqqt4 g
E 4E= CEaEql zlBol E4(tr-q 3A).
(a) (b) (c)

(b) a +=l
f.g 4A.6 (a) 6u Ei'JB= olF? ?1ts Ei{|. (b) "JEllE E7l +0il^1 o4i1l l.w Gibbs= e+q} gqe}9 olE * zl* *otel erlE 6I+
=
7lE6lE "JE= EillE gE= EA A^:dtr[. (c) old "JOA 749 +E6IS..91, ol +4e Beg ol? *E +
=
ㅡ
=7l8el
L]1= + tzty,=ol^lr =716lr
,\plsl llEol g.q^lzl El=E1|, 0l -d801
Srll
= :dtr|.. E과 Hs].^lzlzl $ets^J +84 o + Hp+^la + ?lb u}4"l
LlElLtE 8E= gzl EEafr
Ele-] +E +4'.ll= 4"14. ol
^J +43
gEq a¤g 4=
4lq zl-+E F, C+fl + c, r4I ¤Bg ol+I 9l= ^JE
ㅡ
gqg *zl ql{l^l= .-4illE z|¤atqE #^l ?+=

5f1ql f n.<1"1E gHl4 +a1= +E}l.ll= alol4. ol oJE=gq+4
4. olrllts &rzl g+eql ul4 6zl "Jq, q?+^J +71 "JE
ㅡ ㅡ ?"1 H"J6I7ll Aqq= q$ zlzl_1. !lrl.
7l gq?J+(rB 4A.6). ole+ t^lql .4ill7} BT9zl qlEql
:. trJEz| e.r++. r4a ¤Bg ol+r ?l= ^Jel ¤ HE|^lzlz]| 9*b tls. q1q1
"IaLH= +7\4 "JE7I Boi 9lE
~
._4illel
"JEe+ +A1
qa_ + tF
^tolE
EHol sqd+. ol s
ㅡ
~ s
,<J $fl{.g-tr EE}^lvJ + 9l=
^llzl ^dael +E
4lE rt
H"l S."lzlE 8s= r EAel g4l c-E z.4l .J+. "J4l 8E(E+)44 ++.
…
gEql^lE +rl "Jqg gfll g+ p.ol4-l elQ. 941 $se+ a

4l +ql E=0slE+E¤. 4lE E¤ol+r 6.J+.
…
=4]6t=
r ol^JE gEql^J= +"J+ +"J ^Jol SzlE zffi iN$r.
~
0
ElElzl o e +84"J 419 aCg ¤Eol4l fl4.
4lgol S.qzl=ql, ol4t ^Jg:EgAl f,i{4r1 ++ + "J 4l +ql Eq fl= -E= ^J=E aCg +41il=ql gs+
~
41 9s ol^Jql^J..-lzlltol ?+=+ ②
4i+q 584"J s}++(olgol+ +zDE +E 4lE ^.1 ㅡ
=z116}zl EE +(c)4r ++.

ㅡ
+qd "Jq 6}ql^l + Eeq .+ill^}J+ r.zlrlol ¤Bg ol ㅡ
+H^J +=$= gE= 6J+.Eee r4"l I

S{ola}l
ㅡ
z}trJEt q 4As
gEel +ae gEql^J 5zl ull$ql + Eeel +E¤4
=
qEEg +e+. *4ol ratmoJ qlE q= gE= 88 ol=E qlEgq Eq s'JEg + aCg *=+. girl+EEel
4, :a4r rbaroll^19 #g E= olEEol4l qL+. 'il++q ++e4g E Na* olg, rEl-L Cl- olgE ^'ll 4^dg zlzla
qlzlql cgg Egol+. r ol+b a6}7l +c"l 9zl 9l
a+ c^J q=d4 _E= q=a3 +^lg + 9lg 4EE iI
ol +ql S+. C^J q=dg EqI gg gfloJe}l-r 6Jq a11.tJ Na*eI CrE fz| E"J6lloi 617l rll$"l4.
qE * ea 6Hl^J= ^ll zlzl r.J.o16J ^&"JHI49

^llEel
s -I.ill, olill, *zDol +E1-41 a"¤olHrl ¤¤g olE +
I]l
9l+. 4l * 44lr\ EI+E dol Hte ol aa# q44=ql
4lE olF L E= aCEE e++ trlQ]¤g ol$all.<J ^J= ^l-
olql ol+qzl= ¤¤E adg qe6l= 4ol I +Elol+.
ol dg At=Eol4L +4.dI+dql^JE gE= 7,es +4
ㅡ ㅡ
u+. … ++EI Eaq a}+ag *4zI trI.gtrl]-e- eeB + He

q, Eaql q+ r+¤i.Jq4 gEql^J +4t+
…
@ 8#=t9*s
tH qe.qE+El "J + 9lE BIe+ ?ol c.==de ql EeE
N
^J +zlg $=.;121 9l6J
ztt| flg "JHg +d CE"l al{ ~
.l^ll tol + 9l= alx] "J49 ++U+. r.ill-olill d- +"J t++ a+ql 46H^J ^J46lr, ¤zlrJ gg ¤r+= "JE
=allts ol
ㅡ
4Al4 zl&zl7| rHql^lzle e-=3._e_E 7lgq4 flg E CE+= ?*Z A+ql 4+^l7l= Aol+.
Ell(_H_¤4.J A+)= AI+Aol o-!illz]. ¤z[$ + ?l= alz.l I
ㅡ EII 1 CEol 6ILr+qI +++ A+q 4+ r,g
E= +44zlE 6J+.
~
+ 6t+E tol ll9 trll=(p=l) pe} rel $$ 584 o-g E
~
p+^la i 9lo:, + F-271 g+. tI+9lE a4 F9 zzH9

ㅡ ^J
C :
정의를 위한 최소한
P 이
상의 수
118 4 ++EtEtre.tEq4ES
…
ol+r il= a+E ^J46HE+@_2). ol tE"l eI
ol B¤¤- p(a; p,T) = tt($; P,T) =''' P 7]]E tl-ql ql4^l
+qd "Jqr+ gEql^J ¤¤g ol+r glg trI= olE9 sle}
ㅡ
ulHl¤ol t"J6]|oF 6J+. 4 CE Iql q6ll^l olBl6J p-r{el 4"1 "J49q"} +4. A
ㅡ
ill cEE iE colIr + olq+ ++= c(p-t)471gtrI.

^lE
p(a; p,T) - tt(p; p,D olel+ !$g r 6].+6}+zl p(c-l)+27Hq
^Jlzl
H+ +E
6tr+= 584 e H6J + S,rll "J=+.
o qet^l d4l ZF+EE
ol pq r rEl6lq "Jq
^lg ^lolE +41= +4Ll]= 4,"14. += q-q_r+ ?ol 94.
ol Hts trl= "JHI4e + + ElHl¤Eol /J'ol+ c
^Jel EIE
_tr+ H6lq, lq6l¤ "lE9 {tg E"Ja}zll .frzl,r.lzl4H g F=P(C-1)+2-C(P-t)
ㅡ
Ez[ {flo} q}+ + /J."l ¤B¤ ol+EJE r4e1 H+"Jol o}4e+ e.*ciuu.zl.
= +Hg Aq4H $ra3 t'- +zlol E+.
ㅡ
"J9e ER + 9lsq, q+^l F= lol q= aol+. ㅡ
tCE 4lql^J 37HE t$ol ol$ trll= ol :zH9 F=C-P+Z 8+^l

^Je B¤g
(4A.1)
~ ㅡ
tE(o, 0, H y)9 +E irlQl¤Eol +oJ6llot +4.

~
p(a; p,T) - p(9; p,D= lt(y; p,T) 1^JB llql q6H^J= ol

^J +]ol +f.r+ ?ol 94.
ol aag {zll!9_e- p@; p,T)=p(P; p|I)e+ tt(F; pjl)=p(T; F=3-P Ar +^l[C=t] (4A.2)
p,1)4 + {g +$'|]q, +qlb ol gEfl + H ㅡ
^l=Elz)izl "Jqr+trll=
f"Jol Eq9iq. 4"1 Eol-r. E"J +g 6]]zt "l ^lE 4¤¤ tfl +t.t"]l _s"+:"t94. tol 6I+S"J ull= ㅡ
¤zH++(olag x+y:ryil, 3x-y=xyq + 4lol ¤B¤- oll= F=zolq tr-E += Hs+^lzlzl ?t= i|]-Epe+ r= +B4sE
ㅡ
r.-?o.J.,-?ol
Jt-L-1 )/-L-1
rlql
r-1 il 5U7l- 4.2.!ltl-t- A1l zl-c- 2olrlt
"ii' i r_-,.ii"-i L ,/i-i -e.:l- -./\.-i,'ti.
nl-;,l-,rl
"1'-i-'i HEIÎvJ + g.lr*. o1fl
ㅡ
,{= 27n9 z}+E= zlzlI. gltrt= E
$q$ $sz} *"J EHel Alg- 611E^J 7l^1o1 ++. + 4= e
_o + 2E# 1l4r 6J+. Bh+q "$"tE *g tle
^J¤B rB
4 o + "l H+E¤ qe. + flE zI*71 s.= 4,o14, tr+r+^J ^Jql^J ¤H_"E +48 + 9l+
27n4 ^Jol ¤Bg olE trll=e
…
F=0ol ¤+. F=1ol q=ql, olag gEE

0
+"J C+ 4lql^'l= 47He) tol ¤BS olE + S.4. : ol# Hfe qR U+ oJ4ol ',l+4E 4zl ?*E+= ag 9"lt
trIs-+ *9:211e1 F^lol CBaH"F olbrJl, ol+Al F.lts + 4. dzll-g ql +qd gEql^l= "-qillzt r++ +rl $qg
=
ulxlt(Pel +4U+. tr+4^J + tlE BBe tr-¤¤ :aB t}el d o e s.
D ^l-olql 37HE s4lalol dB".JtrI= -E+g a4 ~
zl s!21 rll$ol4(ulzl x+y-xy, 3x-y-xy, aQa_ 4x-y-2xf gE= q6l-=

'ild Sqg Hfe
qg +E 9l=ql,
^lg+.
ㅡ
9 ull a]lzl 4gzl 9+= ar+ ?Jr+). .=e+ gEql^JI,J F ^J"l ¤Bg ol+41 g+. Ir|
"ltrll= EI
+^J 6J +q1 "Jqql^J= q= d(E= += qE t d"l g
It(a; p,T) =p(0; p,T),Lt($; p,T) = lt(T, p,T),
E)ol "J¤EI C6lld gE.ql^l +4t+.
"l p(f p,T) =p(6; p,T)
37HE
^Jol
~
¤Bg olE ull= F=0ol qq +E+ AlTl gtrl.
ge|:oiz|fl lcB
A\(c=l)el A+qlE p=1"J trll F=2oli1
p=2oJ 4l F=1ol1 .E p=3"J trll F=0o14. ol pffi
…
' "JHI4
" + +Er+lH C=loJ rfl F=3-P7I g+.

…
8y Alc
o!
=JAlz "JE +E CE c= *= "JHI4 a+ 8o

a4ls "JE pe} e
ㅡ
+d E+E +++El ,<llolEzJ.. e gE r a. F=2, 8p

^ll7l P=1 P=4,
9 Eol 9l+. + ^JE adg +44= rllE c- 17H ^d+E E ㅡ
mi
;n
F=0,
X =/l
Eg"Jg HÎ6IB 84. ol4e g +gE $ol 1ol 99ot aI P=3
…
F 1,
Ir + o.l- + E +¤-9 zllel* 4"lzl E +¤-=="J E^l6lH P 2
86
+E6I7l ullt|ol4. zflrll tl"e-l += polE + g,q+ a^d H
ㅡ
+q dill +t p(c- 1)"1 94. trI+^J ol +4lql^J9 rilzl H azJ 4A.7 ldE girJE :aJg de4?l Eq=. d=p + ?.!tr gEol
+9 ++= P(c-r)+zzl gtrt.
ㅡ EEE olF? ?l= + fl= 5a= LEI-L,ItrI. E3 rzHg 8Al EB= 0l+E^1
¤B tl{ql^J} CE l9 p+ql iil$l¤"] "lE tl{l^J+ A"I 8=-:g + 9l= a*-d -d
^1lEE
6ZE LtElL.!trl. 47llE 8=Ol gB= ol+E^l
oF *+. . flrl.
=trg+=
4A ++El Etrel 8-EJE f=J 11e
olBl6J
~~ 5H+
?TJZ Eeql a+6J 5a6Jr"Jqql gEe+
zFJEt 0{l 4A6
rJ"J olFqe + fleq, *4 Hl¤ + S+. tr|{^J
다
rll zll9 tle t}¤e re
"l¤r|]E rH ae.s"ll^j AE ABCD¤- .t]4rallEz|. Aql^J= oltl3'l
^JE * d, + a}+dqlrJ"J B¤g *4zl7lal+. gEe+ "Jqg ae6}q Btr_ 71471-E ?zl
olE + 914. r= 9ol B f S,o oe rrJE 4lql^l= +tl4
7144 rill-+. gEE +q^l ctr-714714
^1fl+. sq4
…
tol EB9 olE + S+.

. olag Dil7l47LH zlillE =" sg4.
"4zll ^}ol ^Jcqq,
4A.3 lrl E}|E4 ABE:1H

^llT
ol,tlEl+^, E, ,,i g# ¤B :H9 qq g+ (b) E
4Utr}
^J
=a# :.fl +e.r. Eql ql* ^J¤B rHol+. rHql^l
ol a4ill +
71 441= EE +71 'Jqol gEql q+ qBal H6l+zl.
(a) oltElEJA LI4U+. ol a4lE c #b 9srl. gr-qql u|4 qBzl H6l
oltEl$^ql qlql tr-B¤ rflg rH +n.sql +4rlH+. q bzlE +4Ll]= AolTlE 6l-trr. + +71 sqol e]+ .J4r+
zltl i\c- +49 r4l-._4rll a4ldel zl&z\7} "Jel alg Eolzlb gE= 9l94zlx} 6IE q= 4"14. riil(g+_r)_
q¤4 H6l+zl= +
ㅡ
+4utrt= rl-d"Jrll(g+eE+q g=+e_e g4z}+), ql .qill u 4de q=dol sqql

. "|?+^J
E4= ao +^1, r ++
ㅡ
+EE EAol olBl6J zl&zl= +ElU+.ol zl$zli-r.ill o1 zl&zlY +=ag a+"J Esl^l7l
…
aJl allr ga+al "Jqol pealri* 19'J:"H=4. ol
… ㅡ
4iElEaE
ㅡ
+dol oJqol +ofat= tol.ll+= 4g x ~ = ~
6J+. g ql 7l^l i=oflot …
6J 49 At+dol tatmB+ +lql ?l +dg zkbaroll olE rllzlzl +el zl&zl= 444ErJl(g+9-
zl ullE.ll AtI4"J 4zl "Jq 6Iql^J= qttle} Ssql^JE ._q
~
E+El eE-a--e-E'|]elZI+), olag oJfl"l ¤zl6J trll +=d
~
illz| fzl]oJ + s.eq, aal oltlr++AE 4zl ¤=91 FotFH ol trqd+= ag *EI+.
~
…
aol+(.EQolofol.<'+E ol trilEql Efl olelal E¤6J flf,$ 6l-= fl"Jg g*"1 }$ rll Pulz} ¤
^"4QI4L
ㅡ
"lE+ …
4). .-4ill ol4lE++^. "JEqH "Jqg 4i6J 5.llatmo ts _7 r-46I¤ "J4"1 ¤-4zl-E r.illz| .-4ille H¤+El= 4ol ,:l
~~
zlafi +qo] ¤I+. "JH]4 + olt]s]+iE ¤flq +qlE a4
" +46llz17l ullEol4. olel6J +rl eJ:= g+E C6J ^d=3
…
ill+ "J+¤ zlillTl Eq gleq, zs.cglrJ a4ille+ zlzllzl g 7a{l 7l"J6J+. rH +e.roql tH-"J utq z:ol Hro Ez1¤9
e
ㅡ
4l ¤Bg oli r gleel H *zl S4"l 6Tatmol 9"loi 6J+. +a a6J qlEql .<le trq4 ?lzls 4r Eq?lzls olzlu3
o1 *zlzl rc=g +6]]^J E¤g QlE Ioute-rhomson _tr4 trll +
~
trll= olBlqL +A Aq+ +471ffizl o + $uJz{.<l o_{zll
~
Eql ts4ol Elq, 5al ratm9 Qlzl $eE E=g trll= r.-g z| lillE+ q arrJ6Hzlzl ull+ol4. ol cl +A aqlql zl"J
r
m ~ m
b7}+e+ ag rills +rE+. olts++a zl4lzl r"J 6l.ql 9E s.6I+E Hle^J4 Cae ~ E-e*q $xlE.r-l!-$|
'+Elg+= ae Hl+¤ oltlEl+l Exl¤ "J4l 8s "l "J4"1
gEe+ HlCtr4 e ++= rl-¤o14.
^-i "+¤I ^J Îolql ~~
"
E4+ Eol 48ql+= ag 9"1t4(E9 rze).
1012
o t7lxl XI
E'IIE
72.9
vilt vil
lill C o-{i1l
10e
s4xll
A
E 67
(o o 06
a B o-
D
5.11 E =71
fff 2-xl
u6E
6l 411 ffir
o,l 6n 103
rO
N 0q A N
+
o)
(o
Tc
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0 200 400 600 800
fg 4A.8 oltalEJlel d-d 3E-d r=J. f4=q eETl 3s., Zr
i*A- +sl
6[Qal. Al6tr= rHTl Sale.cl Et! tr1 Eg graloll ?lo=+ 884oJ 4Z fzJ 4A.e qal rilS- LtEtLH= Eq d--J AEe :r.aJ. 0l rnl 8-
6toll,\1ts o-4i11
0lttEtEJATl ?Jo.q, nlA-Lf 5.11atm9 "JaJ= 7l."-t| l, ll, ...e. LIEILHfltsEl;, lrll I 13 sEg g8oltrl. eE ABCD= ,J.J:il ql
=^l|dlxl
+cloF -Llcl. ee ABCD= ?J.J:il q/ 4A.60llA ¤Eolfltrl'. 4A.7oll^l ¤86l-Htrl'.
120 ,- ++ElEEq=EEEJ
100
a-Li1l
b
hcp
a
o4ill
He-l
10
I-N o,lljlxl
o
(o 디
"4xll
il o
-o He-ll
a (E+i{l)
mi B
6n C A
ral 4A.10 g3(g+l)

+4E g+. 4 tl4 3xl'trlc-f 2t11t,88=:Broe
0
c4xlEi
Ud
어
7lx1l
D
HgxlEal e:cEE, E Dll9 +A=Eto.-e 0l* ofl^lel 4E^ll
=:ct6l-q 0.01
uHgE 0l=n 9l+. 0 23 4 5 6
ZE, TIK
lal 4A.1t Efl'He)g AIEE raJ. ICe F oji1l80l EE= 0l= + ?l=
aZE g+ll= A+ill 801tr1. rrll CEE Ee.alg 20bar 0189
LlEl'LJtrl.
a4 4L.eql 96lB E9 "lilltr-g 6l+solxluJ aill^Jg gg= 7b-H0t:-Jtrl= 1= 4EalGal. Exl hcpel bccts flIlEel H g^.1
m
~ 0l trt= + lr1l8E LlElL.ltl. hcpE EJ "JE Eg= -l,zlI bccE illdBBJ
-HEel g*('gg-r) ole-lqlE qflol ll4. olE ;=ql= +g
~~
gEql^J += aE fl4. qlErl 9¤--vrrg l00.cglrJ 5zl
trJ zskbar ol^Jel E.qql^JEI 2006LJql 9*_xil4
=xH++.
KVz| -160'cql^J +eq$.zl"J "tzl ^J¤B rB ^Jq ¤q Eql^JE tl+g zlzlt_ Tlt¤ 6Iq aill ^JEils "lEBl
m
=
glzl *alzl ullEol4. till BE¤- "JEBJH "Jqg zla1l.<1 i1
3 "lC"l4. *zl, a4i-ll, "t 9*-I ol ="¤61* ~AL+A olelql
"lel Al+dol
gl4* 49 7qa].¤4. olE AL+A$ E+71 zl¤9 ^J.e +=q FI"t ++.
a …
5A+ gEE "Je4 gEql^J +4tr+. ggq riil^J=e

~ ~
++6J ¤E-+= +
m "+ill^Jg
714 + ?14. :.Bglrj He-r
"l ~
ㅡ
7+7+ E Ezl9 HHgol ql*61 +g .Jq 6Iql^J= _tr -E^lqI tr-g Atr-4"J "li,ll4g 4E"6Iq, += E 6t+E
^Jol6I+.
0
~~
+iaqlEol flEel H,o Ezl¤ol trolel H]lgg +4Ll]= ,t3.?l ne-rr= a3i{!"Jql, ol ^}g A^dg '}4421 g-1. cE
…
4o14. g+q olelal olBl ^J==g oJ6l-= d4l^lzlE flql"l 0 6l+ql, ol43 BE-+9
…
+.1 "+ill-"+ill-^J 4A1+ Idol+r

qzlE qlq. oJ6iE gElqlE l=zl *qI HI+l +lql g-"ill. g++g dol Ssql^J gEql q6l] E^l*g trllE E"J UIE
gge ql*61 +e Sqg gr1 9l= 4"14. ql Ee 84"14(:H ae.rz).
~
BE-:s. a+ill ^J'g 7l-zlr. 9l+ gE-39 += 4Col S
E 4C ran*H < o;o1 q El4^J(A6o.s=A6,.Htrfe+q) +E-d ql ㅡ
ZIEIE} 0{l 4,A.7 +ul7} rilltr-g aB+ trJ 1r-+=

^l
~ "-4i11^J9 Qls ~…
Eql^l Hl
t4 a.g ABCD= rJ4a]]ezl. Aql^JE Eol g
qe.gql^l
C^J4ol4.
+ vE +zlt+. E"J Ssql^J Sqg B-e +q+E g*
~
vrrrol ^Ja+. Cvl^l 7Ip6IH B9 vll"l ^Jzl:q "Jqg

Dvlzl *+E a\lzl +oI^J aqille g+. 40
-
tao
E
He-ll
(c) eLE T
Y20 He-l
-)
zlgql^J ,He4 nHe9 + g#+l gi= t}olel c¤9 Bol E
…
(lto
tsrll, : olf*
ci
E+ol.a 3Heg ull=uJe-olq^l Pauli9

…
nUeE
g4(tr-q sB)ql 44 d.olalTll a+6llot 617l ullEol4. rB
ae.ttg gE-4el tF¤B reol+. eE¤ Szt9 d*"1 H#
… ㅡ TIK 2 3
4L"L^J "l* flzl-E=4 trllt6l el:.I7,ll tr-s4¤¤ 6i7l qi+ql

~ fg 4A.12 .8Pi1l He-il9 EEzJe EEoll rq+ He-roe9 dOl
=7l,6tq,
*3 Ssql^J Elatl-4"J ¤eg +4U+ qlE^J gEE oI 3E0ll tr=Etoll qal 86:dtrl-. E^l-d Eg nflEoll 0l Eol= Idol
~
aE.6[q, a-'JE r=J=46t41 :dtrl-.
ㅡ
d|9 CE
+"] *+q +qE rilltlr+ zl;ll{rol a7 ¤Bg ol+zl ?*
…
^Colalr.
olae eE gz}Tl q+ zlBzl qlEql 4*61 *g e
=4.
ㅡ ~ 1 EE Eil a+ill eqilltlg zl4 i il= a Aq.
4A ++El=tre18¤tr ra n1
LtJ-d q 4Ag ¤6Lq DE 7l-47IH EUE-I, gE-rr, rela Gz14 ^ll tL

rB 4A.llql^l a_e. ABCD= ^J46ll-Bzl. Aql^l= BE"l 5ol .<JE ¤Bg ol? 4lz| 44tr4.
=
+7ls +4+trI. B-tr $4u.lzlE gE-rE Fqr" 4l+
afl.rJ szlzl B4^lzlE ¤E-rzl $2f,+. "Jer+ gEE a
=s-d7t|LJ=
r l. dol* EiE4 aCg EE E?-lzl {r4z} dill4 e_.E +"J+ a 4. A-BE =aJ3 {L ^}ol 7}tr-"Jt6tzll ¤zlltr + 914
LI E= tri= =e.J gEe+ "Jqg +
Eeel ¤4"14. ^JSq B¤g #xlg + 9l=
a 2. I Eol+ oJ ^Jol tr}= /d;e_e zlg4 o + E+lq= 4o14. Elu+.
tr 3. t'-g gEqL4 o -+ 61146l-= 4l zlE"l El= ae ¤¤ tell D s. a + 4le-1 tF-=. Î"lE ¤Bg gz1.r,1zlfl^J HEIÎ
qlî= -J Eeg :llol qfl¤ol .rl-E dill= Eql^J F"J6ll "4e
A + fl= H+E +E'rqU+.
of 6J+= rl-¤"14.
=s-d^l=
,\loe,
zl +^l HE
^l ^]
Elq qHr¤ ll=G^ ++d Eeq ql6il^J
+4 F=C-P*2
F= zt-ftE c= ¤Eq + 4A.1
^J relr p= tr-q +
EEJ t*B AEolel Eq-+4 gA
> ol EE= ull+= ols

tB.l PJ8-Eoll g:e}=+ 44
EEqt4 ts¤ EEt|^1 A-BE fBsl E?I= ¤BEr # ?la s
At Eololl ol^l= gteE Erl-= qHg ttr ?ltrl. E.-d qa'l zs2J +E6l *9 Ssql^l= r.ill{ro1 ,}+ *g s}+ trlHl¤9 zt
6loil^1 Et EtrE 8troil "Jtrlgre dEE ¤E-J f tr ?lrl.
zlq rr}44 zl* alaEl t"14. rBl+ tr"Eel slq} qfl¤ol
gEql E=6I= CE= ^J"ll ,rl+ 4sq(4 tlE.el E tlE
> u_4C 71lE -ErlTI 4=zl trll+), tr14^J gETI +oldql q+ +E ^&ql
BEg olF? ?t= d=el sl+ triE!¤oil 0lilts EEel gfeE aql += rill^J, Eillt}, E= 7li.ll^DE ElqL qflEol _,:.41
E{g 4 g=e_l s ?leeulsl E +tr|ofl el6H^l
=trErl.. E atr+ rl "J_"-=. qleJa + gl+. oltrllE tr d"lz[ z]ts4
> gg'El qHl rl^l "J + glj1 H}¤
4_Ezl4pa1z1"3 6IH d4l_E c. dolzl
"J
8- r alEl tr18!¤fl1 Egg trll BEE o|+q(EE 4A) s-d q+4 ¤tri
4 E Gibbs ollLJxl= r
E +qel glE-errpll sl=altrKE4
=trE
3E)ts fllEBtrl(EE 3B)e[ g5 z F1l
'i= s 9a ?1010 t eltrt d0 I rioltrl.
E=](Etrl IA)0llget +.lEs. flEg
(d 8q $EEsl =.-E el=
T=0 oltlql^lF E-= Eaql 46H^J s*>00lol.<'l 48.laal
ql E6IH -r-Ez[ g+A]ql II]4 ++q] EeE s]q] ElHl¤
g +, e+E irlHl¤g gEql Eil5H^J s^lal.fl :.
e^6JE+.
Eq 4Aoil^J ¤H+ ute+ ?ol tI B¤E gEqL4 zlA-o- z; zl&zl7t g+ss+El eE4"-e- 44114. "l zl&zlY
tlEq sI+ qHr¤ol E"J6}]ot 6J+= 4o14. l^JB 4l"ll Eil S-(s)>S*(1)ol7l trilEql .-4418+ 4*zl rJ zluls4.
TlillE
6ll^J=
^Jel slq} ulHl¤ol +iGibbs
glulzls+ rJq@=G_). relr 4E t4l+ s,,(l)>S_(s)olrl ullEql ol zl$zl| azll
Gibbs qlqzlTl gEe+ Sqql tr}+ q¤Al H6l-=zl= Eq ql^JE+ EillE 4*zl rJ zlEle4. olBl+ 54E¤ +4u
3Dql^J ¤H61"*,+.+, 4,ol :B 4B.1ol+.fl(l)g p(s)otl HI6H^J a- 71&7lzl zl-$e.
,lql+ql $sz} qL AE 94zt$ rl(l)ol p(s) olzll.E Eol
dG=-SdilJC *eql^l
+14. ol+ril EIH o_4i.ll7]. qlc+ t"l 91. r4lzl +=+. 7l
dG=VdP ore ¤-Eql^l
"lE ^lg EGibbs qlLlzl, q-f+^J

++ i4Q]¤qlE 4+¤4. "l
¤EoJ+ zlsE ol+6lq q-s-+ *ol ut4p +E 9l+.
=g Lxll
dyt
a7 )p| = -S", al+
qEl¤e-l roll nl= Eo1 t"Jtrzr pl (48.1a) qru
il.1
E ¤71
H
rlol
dtt y",
an
el-sr EIE!¤9 pCIl ttl= Eel t"Jtrzr rl (48.1b) 'tol
T zxjlzl Ei1l7l.
=7171
,+ * Sqgl= qI Eeq Elql ElHl¤E"l E"J6r+b
"Jql 8E, r
pE gEe+ Sqql tr+= H+= +4lll= +lE 484 fEJ 4B.1 :.J
EtrE -r.i1l, Ei{|, g 7li1l I il+ tr1EJ!¤=g EE E==
^l-gg +qc 8E0il^1= pzl al^'?.!
e.J^l7l$ ^J BB"l olE aa Eq.il qB4 4g"oltxlE
LIEILHE zt|ajE.(dxi|E=
d=01
=doltrl).
:.gEoll^1 7EI gr8-d ,301tr|.. IPI-Ib)4 e3
d|01
+48 + el+. =tstrolLl'g=E(4r:
Eol 8E= + 8sl ar+ qEJI¤oI ,Jol^l= 8so1c1.
48 I dolel EEet4 g8 123
4ltr"el slq} qfl¤g gsz} ¤-4aql 4+ #rJ6l-= 6l-str --.o

EL
ote{
H-
(7lill^Jel 5 tle +ulzI 4tral zz\ ullEql) olH 9s ol^J

ql^JE zlxll9 slqt qHf¤ol zll9 *ottl4. olullb z)i\lzl zl t-o o le{
o-qill
EL tl -i
tI .J4+ tol 94 .lill= zJ.${ g + +894.

e4iJl
a
qru lill
Er
E-
,lol
r-lo
,<E t-f o
,l0l o lan
tl -- o
tl
la{
-i
l00"Cql^J qA EE .s.= E {lEEul= 86.81IC' mol-'ol lrll

ir, eg .$Eql^l #z\4 ol llg K-' mol-'ol+.
1es.e8J
_+
tr++^l +E= 1.SKIrE gq+E e+ql EtHl¤Eol trl-s-r+ .QE T
(a) (b) EE, T
*ol HC4.
a4 48.2 El EEg 6lEl tr1EJ¤E gr+ o.|5_E= gg +trloll q=etCl..
At/(l) = -S-(|)AT = -87 | mol-l
= trlEJl¤o| clEll
0l raJg +d=g "Jal= e7l.^lA tq ri{le} E^1lE EI+
E6lL_^l= LtEILHq(drJE= dfll+doltrl), sE-d +*0ll El^l= gBE
Ap(g) = -S-(g)AT - -t96f mol-l
L[EIL}| Ecl. (a) 0l e+oll= nillTl Atg E +tr|= 7l^lq qal^l
o-4ill-Etrl
p(s)Ep(l)Ect 4t4l 0l rqEoll +=Eol galrJtrl'. (b) 0lrllts r.i]l7l'

rgg.cql^J5 + {lol E9+ irlql ElQl¤g zlzlt_ ¤Bg o-4i1|-Etrl
E +trl==71-dtr1.
7l^lq(Eo]l,\1 Elal^l
=nl e7roF
i1=J), p(s)Ep(l).E.ct
olE+. 101.0"cqlrJE ?zle+ E}q qflgo1 roo"c
q4i.llel
+ =
3E7l L|1al?.}tr|'.
ql^lE+ *zl"J +714 +tr} tr]Hl¤ol gd cl t*"1 a.4

++. +9 Ssql^l= *zlzl qlat t]-"lr q4^J +g
ol xlflzlo+ "Jqt+.
ts ¤+.EflE"l 4¤4 o + a"-lElzl 6IqH ee} gE=

(b) +Eotl Elxl= g+9 E:d kgm-3o+, E e+g kgmol-ro+, fq;1 lPam3=1lE
4B.lb^lql 96lH v*>0oluE +++ Eillqlq *Eg zlall +4.]lB g+.
fE : s+qi qfl¤ol ¤izld4.
'il++q a+
y_0)>v_(s)
Eg E e=+g 18.029 mol-'(1.802x10-2kg mol-')ol
olq, 4+^J Sqg tq+E alzll
^JE EIE ElHlgol lill =01
+. ,tl4^J Sqg l.00bar(t.00xtOsPa) "Je +71^la ql=
tlE sl+ ulHl¤_u+ rl 6zl+4. :.8 aB.2(a)gl -H"J HLe+ +gr+ ae ar+E eg + 9l+
aol "l*lq} A+ql= .Jqql E6ll^l += gETl E?J g+rJ
4. :44 Ee-l a+{l* v.1r)< v,n(s)olp + $4ol *zl-aiE Ap(ice)=
(1.802x1O-'? mol-')x(1.ooxtos Pa)
=*I.97 |mol-'
rill$ slql i'lHl¤ol .lillE e+E EIHI¤E+ El "*ol Gzl.t 917kgm
+. :a46}q q= SszI EZI LllBlA+(rH 4B.2(b)).

(1.802x10-2 mol-')x(t.ooxtos Pa)
A/l(water) =
999kgm
=+1.80lmol-'
GZEU flEt trja!¤ot Etit= sqE E,r
?!1 g+q E9 slE ulfl¤e+ q +4
EluI EIHI¤ol
0'cql^l ggr+ Eql zI+6I= SqS t.oobar-E*H at4 9-4214, ul44 ol=ol i.lgql tbaroll.rJ B¤9 "lF
2.00bar-tr ?zlt'l7lB olEE Elq ulBl¤ol qH ¤6.J¤-
r 91fi.+E 2bilql^J= ggol +sal= 46}-9 444"F
BAL+? ol aaql^J ggE gE= g.etz gcm-3oli4 E
ts 4o14.
el "JE= 0.999gcm-3o14.
r.e{$ il-v^dp ^lq E6}H Hl"J+d EeE s}+ TlTlB^71 4B..1 E 4*ol u.}smol-r?I ol&E}+^g E
^l¤t
qfl¤g "Jqg aptrJE HE+ÎA q Lp-v.ApEH H¤L rlEol ¤¤g ol= n ql4.
ille+ rill "l3ll 4L+61+ "J
+. tr|{^J ol Exll9 Rg gs=lfl Eel + ^JE E +iil= 49 "J;- *zlt'lAg.'I9
r.oouar ;1.flg 4l+IaI¤4. ol
"J"l"F +4. olag BEpe+ E 4* t t Î"19 v^_Mtp S "JE= zJzJ *5gcm-r4 2.5Ogcm-3o14.
4lE olSa]|^J +$ + 914 trl-e}^l Lp-MLptp 4;g ole" al. =el
hE Fv & 1z [Er :r-loru I 9/'I + = (s)&'r-lotu I /8'I + = (t)rly'E
12t+ 4 ++ElEtre]=al4EE
(c) Ezl gajq Eli!ts q+ g+sl B-d 7I E+. .+illql aruI*9 "J4ol q+e-+ ++6Iq p=p+LP
71 2 tril= +71 s4ol p(+6IEJ: <bzl E4.6zl "J491
++ ^Jq 4L+6I= Sqg zlAl4o e zlal fE glj4 Hlgc "l
zlillE "l+6H^J zlg f gl4r:H 48.3). *zI9 A+ql= * il= SqE ¤6Jg 4E6l Arzl rllEql o+
P+^P 6J
=Î4
+ tr-r+ B¤g olFr ?lE 6zlE ++ "J4"1 ?zl oJ4"l +E p= p.* ?J l ol 4Eq +r
^J6Jg p*+AP-tr F9 +
94, ol4& t EeE +E $ajol4l El4. ¤++Coll 9l+. "++î ?lel
^le +gl} ?ol 4EaJ + ?l+.
=71
Sqg zlalfl +71 $tqol 94714. olag olill^JeE+El RT u^(r)dP
Ezl¤"I zlzll f e-P "J+qq 4zlzl rllEol4. ol 3rffi $ J:Y= !'i..oo
9qr4 " + rge}e-sr^] 716l]zl= "J4 pe+ +71 "Jq p Îol (a4 4+ql^l zlEE H+= p4 p'& + ae "l 4EE tI+
e-l +41= +.J + 9l+ pe+g Et¤ '1617l +14^l+.)
EJAI4 4B +q
Tlg'EJ o4i{lel=71 saj= L[E}LI|=
^.1 "JHg RrE ++ir" aq ql^Jel g.9 "Jg H+lq^l "qillel
¤¤ql^l= a +7lE ++
.+ille+ . ElHl¤ol A.I"t qI+ E *ulz} "JCaI4l ,LAEI+. rflH
p(l)=p(g)z} q"l"t.J+. Ir++^l ¤Bg r4y4zl 3+= E4ql
4E n.t
qlql^'l= qE A+ql4p(l)9 HEl"*r+pG)9 Hsl%r"l e"I 4= A.2
6J+. frdP'- I p'+ AP

%(l) p'+AP
"t ++. 4, dtt(s)=dp(l)ole|"F JrT - RT J %(t )dP RT I

P.
dP
"Jq Hq.il zl.JE= 4+ sl{¤E H+

trJAl 1
zl+ alillql le" 6l+ "J4 rz1 ap "J=: H6J+E r qqillE
ol + 4Eg a+61 al&6}q +94 ee erlE Eg + 9l
p+qi qEl¤: dp(t)= v*(t)dptrJ# EqI+. r;]r 67iel p+qr- +.
ㅇ
qfl¤g dpG)=v-(g)dptrJfi H.JQ. ¤zl,<l dpTI Hle +4
7l-+6IEJ= +rl sE Hs+%+o14. ol *zlz $d zllle 7
ln P_
P* \P*
+6tE r E-+vl= v^(g)-RTtpe. ul^To].<J dp(g)= GTildp
d*=xq +al= 0l+6l.0l ol 4¤- 14 ++. l+lH,
e.¤+91+
Tldll= oJzl LPTy e7l
cJ4tz +7lq.44lE 4q qfl¤g t"J5t4 H++.
0
p - p* ev^(t)^PtR't' (48.2)
BaJ potl ol^l= E-d
dp(l)= v.(l)dPel- dp(s)= @TfldpS e4l +=4. -248,
"P=
y
@
(r)dp
s*alzl ?*E+ +Ed-q4.

¤zlrlE + 7l^l +aL+ Ezll= +^l6}q.=Ell :a 6l-+= ¤
ft{tol "-4ill"J ullE z}"J +¤¤ 6l+ 7\r\l7t *ol¤971^l *
dill $E ps+ ++ +71 "Jq pE +tlel Ceg EE+^lvJ + 9l+= 4"14. E 6i+= zli{! E
3 4g.+ 4+ +4E ol+q^.| ol ^J tsz}"ll 34 4zI E
EZI 4+_e_E El_84. El|trl $Cql E6ll^J eqill Ezlzl z1^ll
^lg
alillql qEE *4ol zr+6}^l gtg uI= p(.lillql 4s"6lt BlBg +E 9l+= 4o14.
S4)z| 4* *zl $4 p.g+ e+. q{.rJ p=p*oJ Qlb p=p*
#JEt qd4ts..z
olan A p
2s"cql^J EgzI 0.997 g cm-,oJ Eq g +i4= 18.lcm3
mol-'ol4.Eql +s"61+ Sqg tobar "J+ +71^la+r
=71 =71
r.al-r. Hlgd 6lz(= AP= t.0x to{Pa). lflfl,
7t94 7lx1l
trlÊ;
Ent^|7 P_ %(l)AP (1.81x10-sm'mol-')x(l.0x106Pa)
=71=
o4iJl= ln
ll
5af^l7l^l
olLrL
LEELI
P*- RT (8.3 145 l K-' mol-' )x (298K)
= 0.0073...
\--
(a) --.-
(b) +lel 44Iql^JE r I= 1pa -r9 *415 ols-" ol.9+. r?-16l-
fg 48.3 8=Af= 7l.J6l7l glatl,'.15 (a)
8=dE gr+,'.l7lzLl.(b) ul=Jd { p= 1.0073p*,4 0.73o/oz} ?z}*4.
7l.gt8 zlillE olEg + ?lr[. "Jal= 7l6lE 3+d9 galol 67lEltrl-.
=71
/,8 I Eolel EE-*4 gA
은
12s
tB.z g elPl ?lil 4 "tElz.j +l ^lg

chq-r} B"l 3 + 9t+
A.JdT= A.,VdP
+ ¤¤g ol+r a"=B trll= rEel sI+ ulHl¤ol ?
^Jol
oloi ++=
Îdg
ol-$all,<l +
^Jol
3"¤6lt .Jq4 g.E, ol !g rigl} ?ol l4 jr_I- Ctapeyron lol+r 6J4.
+ A4lE Cq+ +lilE *g +

^J 914. zl3 t ae+ BzI ¤ do
t A-S
trs
¤9 olF;r 9l+r 6tz} lflH, a7-rJ
- Cbpeyron 4] (48.4a)
p(a;p,T)= lt($;p,f1 (48.3)

ol Clapeyron al$ tr-
A4d tlel "JelE dql^JE dd9 zl
ol ¤q^l p= rE Ei+E +6lH tI aaldg +4.ltE &zl! +{tll= g"J+ ^l o +^J, q,qq} ++6J EeE tI¤
^lg
49 Eg + 9l+. ¤ql ql"H^l+ 4+84. ol al$ ol*6lfl gq+4 ql"lEl-
olso 6}0l
^J¤B :_H"l
q$rll +e}8 4"JzlE ql+6J + 9l
.r. E I E"&g o16]19 + 9l+. E d+4_q_E= ol
^lE "JH
g trIg-r+ eol E s + flflq q=dolLt #=dol "Jqql q
q¤ "Jq4 gEql^l + ^Jol ¤¤g ol+r 9l+
=c+
_r. 6IzI. rflfl + tr-E :+eL vlql¤ol E"Jg 4o14. z.l+ p
4 q¤rll H6l-=zl= ql+61-= rll ol$al + 9ltrI
e+ r= 4
e.ol ulialzll HE+^l7lH^l + tr-as+ FE 414 dT A.J 4.1 (4B.4b)
Clapeyron
6l]^l ¤¤ql ElErll *+r ol HEIzI "Jol4H ol @ A*.S
^J461-zI.
+ tFE.E +CI,} qHI¤e {a1z1u3 qd6l E"Jts 1ol4(r
H +e.+). trl+^J + tr-e-l p+ql qfl¤Eol +?J4l E611oF 6Lq
p(a) -- d yt(p) zt C B 6flot 6J+ g¤.ol
"lills B "IE E= dol +ule+ ql_E +sl
d
O"cql^J
+¤ :s.z^l(dc -vdp - sdT)otl E6lH 4 ^Jql 4="1"J Y 7+7+ -1.6cm3 mol-14 +22J K I mol-rol+. tr14^J ol g
dtt-v^dp-s-dr7} ^dgdlot +tr}. trl+^J dp(a)=111(p)E + Eql^l r.ill-alill ^J a4ld9 zl¤zl} tr}e=$ eol g+.
4lE ++4 ?ol 448 + 914
dT -1.6x10<m-'mol' K
V^(a)dp - S-(a)dT= V-(p)dp - S-(B)dT dp- 22IK-'mol-' = -7.3x10-' .
Im-'
= -7.3x10-t KPa-'
¤zlrJ S_(a)e* s,"(B)= + tlE E SlEEv]olq, v,"(a)el
Y,"(B)= r$fl g +{+. trl+^J, ol4g _7.3mK bar-'gl 6H'J6J+. qq^J l00bar= *zltl
7lH Eel q=dol 0.73K++.-llEJrJ+.
{s-(B) - S-(a)}dT= {V,"(F) - V^(a)}dp
¤zlrJ {s_(B)-s,"(a)}ts dolql +H}qE fle_eu1 HE}

^J|
A,,Sol4,
"l+Lzlzl-E {V,,(F)-v_(a)}=
g +r1 Hp+ Ao,vol
(b) r.i{t-Eilt g e4l
Eeol ¤+E uI= E $Rrl Es+ &"azt +Hlqq, gE r
ql^J +eE(+&) E- ¤¤ q!trtr-ylzl a,*Htr
8o "J+ HqFHE
b
9 :n1. rflr ^J Aald ^Jel d==g EF ¤Bg +E+qlq,
trI4^J 7= dol 9E T*,zI g+ olBl6J tr d"l9l E11dl^J=
a.
dp trl¤.!+ ?ol ¤4.
a Clapeyron
nll
^lol
o-n
ap
do L.H
aT = A4ldel 71E.:71
-r.i1l-o4ill (48.s)
dT
r ^f
8-=' {zlrl atu.v= += r+aql +Hiq= E +vl Hs}trt. ¤+ q]
a.al+8.4 +g0lEE= 0l=7 glHdoll,'.l) 4lollga-iE 7f6lE EEol.E'eJ gq= o3=ol{(He-3ol +"Jq} qle.l+), +q HEI.E "JH}4_q-
Erl. 0l Al= ?E7t EEroE/"r1 gEol El+qq leld}q gE|.|Tl.bE 0lEEIcl..
qal^1 gqolLl ?=ty E-g nll 419 EB= +^l^lzT= dpef dr E 4L7l= 6lzl"J "Jol+. q+^J tl A 4ldel zl&zl dp t dr+
lAl7l ?iE g + ?lrl.. ^l-ol9 Tl.ulsq .JHI4ee "Jol+(rB +n.s;.
=r|1:srrl=
126 4 ++EilE¤E Ea14 H+
aal=ffizl o++qTl+
Lill
u'0"*'o'lT!,1,,,--
p=r.0x10s n.* (27 _,-,.,
3K)x(-1.6x 10- m' mol-' )'
(T-7.)
a
ff = l.0xl0s Pa-1.4x l0' PaK-' (T-7.)
6n s4i1l
+
p lbar=I-140(T-7.)/K
-9E T
fal 4B.s ce4?l r.i1l-o-4i11 I ezlde 7\.le4l +lE EalrJtrl. 0l ¤zlrl T*-ZT3Kol+."1 ^lg:.fl +n.091
=_r1a19c1.
)lg7l= galol qal ?=tl gal'#= 101tr|.. r|]?Esl
0lilal :"J561.=til,
=71.-8r0il ==
E0l ;e--:-to1-d qlqcl.
=6lE 15
=tr=o1
o
An*Hg} An*wI Sqlt gEql 4E 5-$alr|-L zizgalH "l

L
1 0
(!
-o
gg + 9I4. "J401 p."J trIE +=49 r, r4r "Jqol p"J

a_
mi
6!
,}]9 +=Ag rn+r alH ol 4Eg'l+4 tol 3 + 9l+ 5
Elt!
A.2
^18
A.rH dT
lo dp-- T ry -0.1 -0.05 0 0.05 0.1
Jp' Atu.v I tE i[, lT -T*ltK
tr++^l r.ill-o-4ill a4ldql ql6J trl-e-Er+ eg g¤. ral 48.6 ?-t-J:il q/ 4B.40ll^1 xltt-d EE rill-Ei1l I 341(H
={l).
=Î^l¤- HlaE +4oe Eldloll ctl-et,iE LfElutlfltrt.
+ el+.
A"H.
p=p.+ A}rl, T.
T
(48.6)
(c)Eiil-=7l4Al
ol
gE Tql^lel +g 9lE ei4= L,^pHtrolq(*ql^Je+ z.ol t
^lg
Kelvin 49 ¤zll"J )amesThomsonol i-l¤.g-.tr. +E6t
9trI.
a4ld ^Jel d==g E+ ¤¤ ^JEllE +Ei4q, tr}4^J r= d
ol gE ?i*ol+. EI4^J .lill-?zl a4dql 46Jclapeyronal
T7l T"ql zVtE ullLtn(t +x)-v-;S+...9 ol-o"6|{(tr9
sB ElElz|s] tl^l l2E -H.oFD ol +E 6}9 d7l16} e +glt aol gtrI.
^l 'il+
jL a.J"Jg +lql+. dp _ A""oH
- T^V,J/ o4ill-671 azlcel 7lz7l (48.8)
dT
.In T .( T_T*\ T_T*
ln[l+ --fr-
T* = )= * +g elBq= ?folq Eql4"pvE "Jq ar-.I+. q-eI^J dptdr
= El]qI
9zl"J r.ill_oliil a4ldql aB+ gt ++ trl
IrI+^l = "Jol
44 dudpTl a4, A!+4-e.-tr- #=de q=dtr4 .Jqql
gd q r4l q+q}+.
p=p*.+#(r-r.) (48.7)
ol49 zlzl:il-pE Tql El]6l]^J EÎ6LE 7L+s zldol 44 @il EtsEortrrir=sa;Eer+

.3qre 4B.sql^le| e9. "J4 *zlz| EillE #=dql trlil= trr+9 dB4 a71E
+6Iq+.
ZtJ-d q /l8.4 r.a1E 48.8^lg ol+61-eJH +Hg +61loF ++. r
^tEI
6}0l 3B)7t g
o"cE tbaroll^J ggE ¤-& elR4E e.ooskf mol-'o1tr, #=dql^lY Urrttr Trouton9 ^}f(Eq
+a +q H+= -1.6cm3 mol-'o]4. q+^J r.ill-qill d. +. +¤ Tlillel 5 +rl= "+illE E +"lEQ Ql$al =zl
48 I Eolsl gE-+4 g8 127
Au"pV= V,,(g)- y',(l)= y.(g)olq, v*(g)E 9d zl4l

"llEql
E E +irls 5$ + 9l+(41^+ *e "Jqql^lLJ. ahl
o4rll
ql^J= 1l= 1 Pa m39 ol+6}q+.
o.
Trouton9 tl-+= 8sJ K ' mol-1o14, $d z]alE g mi

oll e)l
=01
+4= 1atm4 ¤g E 2sdm3 mol-,o|4. tr|4^J
=aq^J
y = 85lK-tmol-' = 3.4xlo3
J'= rv paK-,
dT - 2.5X10-2 m'mOl-' -
I sr 8s'' r
aeJ 48.7 CB4?l eqxlF=71 Af e4l. 0l ,J4lCe gal= g-Eoll EH6HÎ
ol atg E 6t'*4q, q+^l dTtdp-
0.034atm K-1011 s.^l-d a0lalr + ?lrl-. 0l af ezlc= =71
g4lEoil^l Eurl'.
=
2eK atm-Iol g+. trl+^J #bdg eI +t K trJ+ HE+^l7l
EIH +O.latmE $4 EElz}flqo} ++.
TlTlB7t 4e..2 -E 38.29 trllolEle+ v^(s)-RTpE +4lE ,"#=-o,fr'(+-+)

ols_" ol.{ a^J #=aql^JE Eg aza6 al&6}q4.
{zlrJ p.E Ss rql^l 4 *z) S4ol4, tE &sz}

t-tule )82 :18
T"J trll
4 *zl "Jqol+. q-eI^J,

L,^"H(l t )
Tli.llE E. +r1= .+ill"J oIE-4 gc q .fE_tr- Luôv
p-p*s-x x=
R [r r.) (48.10)
y_(g)4r + + gl+(-H-7l 48.2= _HoI+). E zlt\lzl -t-_-t

"l^J4t ol +s.ro^lol +44= +dol u|s rH 48.7E 4Al-=.zl 4
effi +qr zlAaIH v-(s)= RTpzl ¤4. "lE +
=^l-= 4ldol+. "J41 9s ol^Jql^J= .lill^Jol ?*zl ullE
ol+6IE clapeyron trI¤-4 aol g+. =7]16lzl
^lol ql ol +de gal 9r 4q1.<-1 ¤84.
lL
dT
A'"oH
T(RT t p)
PL,ôH
RT2
z}trJEt q 4B.s
ol dxtx_dtnxE +41= ols-"alol A?l6ifl +rl "JqE
^lg
gEql E+= H3tl¤ +44= Clausius-Clapeyrcn 49 Eg 4B.10^lg ols-" o|fl Atl #=dql^Jel +zl "Jq t.00atm
(rotkpa)¤- ol+4q q= "J99 $sql^Jel {tg +,9
+ el+.
+ 9l+. qlE^J Hlr$]el at} #=d3 so"c(3s3K)oltr_,
dlnp A'"oH
al (48.9) A,"oH"-30.8k1 mol-,o14(g 3B.2). 2O"C(293K)ql^l 4 *zl
Clauslus-Clapeyon
dT
"Jqg 4l4I6Iq _H-zt. rfl{,
RT2
"J{)r+ u|$zlzl-e. Chusius-Clapeyron 4(=

Clapeyron 4l(B
3.08x10+Jmol-'( 1 t )
Î ^])g tlBB
rfl$ EoJ,56l .lill-f"zl * 44le+ aill- 7(=
sonr", _o" I zs;f--:Slf J
*z\ * 4A1E glile+ -Eolg 016fl6l+ ql +,q6}q. d4lE =2.14...
ol !g +71 Sqol gEql E|4 q$4l H6E, E #.i-dol
olq^J
Sqql qq qBrll E6l-=zlE qlt}6}= rll ol-a"g-+ 91tr1. "l {tr}p*=10lkPag 48.10^lql Bq+H t2kPaol
+= Ar+E Eg + 9l+. dE a4= tokPaol4.
qlE^J
"J"J +g flgi4zt gsgl ++6IH "l ^lol q+r+
?ol 4R84.
4E A.I,
x= ln pE 4E n.t EE gE 8^l zlf 453 q]+ ql"J6}7l qlEql "l qlql
Ag +il 4l4hg B trI ++ +41 4l4}g alfld rir.]-e
ffi.*=A#m ^le|
"Jg "J al-b 401 ¤4.
nI4^J
1zB _ #El=trst=l4EEt
16) zi{!-E7ta4t dlnp 51.0x103 Jmol-'

(b) = 0.0823K-l
aAl-+71 * 441= Hl+6}al q¤ +
44le+ q{!l-Gz\ * dT (8.3 145 l K-r mol-r )x(27 3K)'z
9lsq, +ts SigqE +s+ SlB4 a*bHe u}+l Bzl"J 6i 3+dq^l h pE rql qlEl^J E^l6l-H a4l-+71 a4ldE
E g+. +EI elgyl= +E tl$ul_acl r_zl ull$gl(A.,uH= zl&zlzl9zll-6zl A4ldql^JE+ q zluleuts ag g
Affi+d*I{) Hl+*gE gq, qlaq ^"4*d!++E+C
ol EI+= +=ql^J s} *dg a# rJ zli'le zl&z1$ 4 + eltr}.
^"
qU+ ol + Aaldg 3+dql^J "J*+(rH 4B.8).
qrll
Ee-l 3+d(6.1mbar,273K)oll^J g¤-E ¤+ qlBqb q= .l'fil
Aqlî9 s= ¤+ flRq 6.008kJ mol-,4 4.el 7I7t S+. a.
ol gEql^19 =" E $grl= 4s.0kl mol-'ol4("Jqol lbar mi
6r
7I otu rll,rJ ets il-= +^l6IE). trI+^J +s+ flBi4E a)l
s1.0kl mol-'o14. trL+^l 3+dq^J9 (a) "4^ll-6zlel ol
azll-rtzl tI a4l=e-l zl&zl=? q¤r+ B"l ¤4. 8E, r
lg 48.8 -r.i1l_=71 Szldrl
o_4i11_7li1l
ezldol uLl"= Lf
(")+r - (8.3145145.0x103 |mol-'
K-r mol-r - o.o726K-I ?i1l-=71 =tr =i1loil^1=
34lcsl 7lz7l7l o-4i11-=71 Szldoll,\lErl tr] TltrteEl. 0l^P
)x(273K)'z
6Al flleJnlz|. ?l=tr!trr|. =71 rrll=0lrl.
=g
=s-d7HE=
I l. eI EeE EIE q$l¤$ Sszl-frlElql trl?+ ,Jd6t{, :z D 3. ¤+ tlql "Jqg 7I6IE a +7]|g.4ol gp++trI.
g
e^.gs QIE-eule+ a+. Z 4. Clapeyron 4e ^J A4ldE z\&zlF= +Eql= alol4.
a 2. f, EeE 3rlq qfl¤$ "Jflol fTloJql rI4 6zla}{, :z tr 5. Clausius-Clapeyron 4g F ^}4:z +zl ^l-ol9 a4dg
eTFgg E +trle+ aq. +44=
=Î^lol+.
=s-d^l=
zl
,d-l
oe, --1I +l 4Ha
p9 Ssql qE EEI (EplET)r=-5- lt:G^ 48.la
p9 "J4.ll tr+= Epi (dpldp)1=V^ 48.lb
6zl $4, e-l+ "Jq 4L+6J trlt p-p*rvn$LPtRr LP=P - p* 48.2
Clapeyron 4l dpldT=A,r,,S/At..Y 48.4a
Clausius-Clapeyron 4] dlnpldT=Lu^rHlRT2
v-(g)>>v*(l) E= vn (s), r4n Tlill= Sd
48.9
zlzlle zl$
EA ne
E71 ,\.4 #-d =IIO

d
- -
EE
J-
E
al I{
-t EtrJ
Etr,J 4A #-d=Eel AFEE reJ
== =xll
oae.r *9 C+ 4lq^l= +211E
^Jol BBg "l+zl * 6l-= "lf¤ ¤B oqn.: Etqi ElHl¤el zfluJol tI B¤E EqE qBrll t"Js+^la,Ezl ¤
61q4. E6Iq4. 어느것이 러 유리한지
D4A.2 EE ^lEE .J418 zlzl"l9lrl * u}+l E= Asql 4+ EB uI D4A.4 4l7I El-oJ+Col4E(+ Sqg 7I6llE tslzt E6lzl g:=+) EI
"JqLIrll El= H+= ¤E4q+. eL gHl¤ol q $qql trl+ H6l*zl E:"i¤4.
G^
Jrr
ㅇ
EaA.r(a) l^dB 4lq^J P=lol q= aAg tI ¤¤ rB
^Jql +EI4H H
ol, c, E= d +ql^l 9-
L}EIE ao+ ol pE qB + flaL+? {ig
4l 6ll^l.J f l,l.t+l 면 P
=
3
E4A.1(b)lc+ 3ag t-BB re

4lql^l P=271q= ^J"ll +44H H a o c
ol, C, E= A +ql^l ol- Ao.e +49 + ?lAL+i ol p9 <fg qB ilr o ilr
on a on
,ll 44B + 9lL+? 선 s P = Z 며 d
b
E4A2(a) rB
4A.89 etiz6}q4. V ¤I COr.tlEzl. (i) 200Ke+ z.satmglC, (ii) P = 2
V 300Kel +atmoll^1, (iii) 3l0Ke| s0atmoll^J "lH ^Jol+ ol+a-+?

^J#
d
E4A.2(b) rB
4A.eE *i16l-q4. 6J H2o .<1ez| (i) l00Ke+ ratmql^1, (ii)
300Kel l0atmoll^1, (iii) 273.16Ke* 0rr paoll^l qts tlol+ tE¤ ol+il- (a) 8-=. (b) P-=.
+?
lal 4.1 (a) E¤ aA3(a)4 (b) EA 4A.3(b)oll eEq= 8-EE r=J
ㅇ
E4A.3(a) :.8 E^l+ a-ddgl^JE q
+.ragl trEol +xll6laL+?
'}]E
E4A.3(b) rB 4.1bql s.^l+ a-ddgl^lE P 4el
^JE.ol SzllalLut? F = C P+2 = 2 p+2
-
-
W
E4A.a(a) EJ 4lg + gq
ㅇ El4 slHl¤ iITI +7.1kI mol-,o]4. BBg ol+E^l *+B + 9l= tl5e-l +=
ÎolE
0.10mmol9 E4g r 6} ¤E e__a+Et += ¤99-a old^le 4 cibbs
ㅇEcA.S(a) 2C+ fllql^l
^-lE
al4e Pol+? 4
qluJ zJz| E"I4 E6I4lt-.+? 0 n 1J .
E4A.s(b) 4C+ 4lq^l
^lE ¤Bg ol+E^j a"*B + 9l= tlEE +=
E4A.4(b) 6J 4lE + gq p+q+ El¤l¤ Tlzl
-83kf mot-tolr|. slr]le H"l4l
Î"19
0.15mmol9 Eeg I + gq o ++El 4E ¤9-q-e old^la rll ciUUs!
9lHzlzl 9uI4 H6IA!+?

1245 J
EE 48 8trolel Eq+4 gah

¤E E^11
RrB.l ++6'J EeE EIE ElHl¤ol $9"1 g4aql rlz| f;zlal; o1.i + 9iL+?
E E"-l+4_e_e ¤E6Iq+. g4aql 44 zJaap
D+8.: 644 Eeq slq sl¤l¤ol .$Ez[ o1.q
qe4l ol¤¤ ¤84q4.
^li} +^l-^l 9al%tB(DSC)ol ^J dolE ^lE6l+ E
D4B.2 Ell E?]o+4_e_e
G^
ilrr
ㅇ ggel e^J +=Br+ g'+ +=d
E48.1(a)
+=d.il^l Eq +8 glgq=
Î"lE
al-= +61q4. e^J
mol-rola, ¤+ E-+q H+=
Aq^l EE 69 dB4= N.7kl mol-'o]4.
6.008kI
ㅽ Los Angelesql,rl 0¤ +*ql Lllq 4ol= flHE Eq "JE=
EaB.2(a)
-l.6cm3 mol-'o14. l.2kw m-2014. Holzi 50m20J +g+ql ol qEol zld qlq 4H Eq
48.1(b) EE AtI #=dr+ s.= #=A Îolg il-= +4q4. e^J #=
130 4 t+Et#elEq4HEJ
al.I +g 4szl ts"I4 9dg+t "l $rt ollHzlzl d+ f;-+E4t_ zl E48.8(b) H]41 ,<1tr91 +86I='Jqg lookPaE*el toupa-e.
A6Iq+. EE +g dgtl= 44kf mol-'olr|. 7lE "l ^lEE slql qfl¤ol ="zltl
9"i* H6lll!+? HldlE eE* "JEE
848.2(b) zlEq +*ql 4Bl 301= aHq E4 "JszI 0.87kw m-2014 0.8765gm-3e-tr. +{6}q4.
r. 6IzI. 'Jolzl r.ohaoJ E+q^J Eel slEli eg +E= 9"t4 94.9+i
(1ha=104m2.) ol +^l qlHzlzl d+ ¤:+84_r. 7Ia6Iq+. Eq +g
8]g4= 44k} mol-'olc}.
α
E4B.e(a)
l.0baroJ trl
20'CE gq1
Eq 6zl "J43
q:ES zlzlt-
z.r+kpaol4.
$qg 7}6l.9tr1. T16llzl= S4"l
Eql zl-ollzl= sqol 2oMpaoJ
u]l.b : 6rl sqg ¤olz} qd,:+i EE g +rlb 2o.cql^J l8.1cm3
X
E48.3(a) tlizl5.0mx5.0mx3.0moJ 2s"CE dE¤ql^J 9fl 8zl9l E
g EI"i +9t+. ol $E9l,tl E9 6zl Sqg :.zkpaol4. +71 ,8-il7} gl
mol-'o14.
E4B.e(b)
2 -
n4 KPa
¤+E LlsB{lql EÊg zlzlt- $qg z}a}flr}. z}
es"cE
qH E¤ql Egltg rll *zl +e--a EqA EE A"6tg +6Iq+. Utl ollzlb $4ol l.ObaroJ EIt +sgfl9 *zl Sqg z.okpaol4.
"l Eallql
(671 sq l3.1kpa)4 iilazl s4 o.z:pa)g 7lzlr.
"l 4l^F3 9E"l Ti"llzl= 94"1 lsMpaoJ oll9 :6zl stsg 9"lz| El4LL+? ol gE
6I-q4. ql^l +gB{]9 e"* "JE= l.169 cm{olc}.
E48.3(b),rl4zl r.llfl ++ olaE SE.zI _s.cflj4 4zl 69 i.6.zl!
E+B.ro(a) qtr aill Eeq g +ElrI 1.00atrn4 3so.7sK(=+ d)ql^l
*E $B"l gjgkpatrJ* qel7t+E ol ,rJalzl. +sI6J + ?14!+? EE
+sl flgulE srg mol-'ol4. (flE +s.rorlg ol-&alq o1 g=.ollrl9
ㅇ
l61.0od mol-'o14. ol $s.e| "Jqql^J Eijl tl-Eltg
q=d"l
E- +sl= 163.3olt' mol-r
ggE 671 Sqg 44}6l.ir" p.e* 19 fiEe 3+dql^lel Al orrpa4 olr{. looatmel Sq 6|-ql^]= 3sl.26K-tr- H++. "l l^ll Egel
z73.r6K= ol+6lq+.
¤+ slBi4el ¤¤ QlE eul= +6|q+. 15 8 KJ 445
.
ba 가 × c 02 E4B.1o(b) qts r8l Eeg E *ulz} l.00ann4 427.rs K(++ a)ql^l

ㅇ
13
EaB.a(a) +gBHI +4.,l4r Eill tI4E +7]|"J

croH8g 80.2'cql^l I 42.0od mot-' o I 4. o I $re]
"Jq ^l E ill tI4 el E. +El= I 52.6crn3 mol-r
ql
H3 As.S tr자
"Cql ;.1 t.: kPao
I 19.3 "Cql 53 kPaol r{. Clausius-Clapeyron 4]
I
olr|. r.2Mpael sq 6iql^l= q=dol 42e.26Ktr E.J+. ol EeE rll
~
^l
(ii) c^J B=d, rel:r' (iii) #=aql^19 +
¤ "l.&a}¤ (i) +g qlBEl,
K
+& qlBgle+ ¤+ Sle eul-=
+6Iq4.
E tlE + 49 5488 k
ul= 4l4}6iq+. IODJ
E48.4(b) dl&g a^J #=a3 og.o.coltr|. (i) dl4iel eg flBqel (ii) ㅇ

E4B.r r(a) 24.1"Cq^l q=EEql+4 Gzl sqg s3.3kpaolq, ja +"J {
Bsl= 2B7kI mol-'o]4. 6zl $Eol zo.okpaol != gE= +6Iq4 304 K
2s"cq 60'cql^]9 +rl sqg +6Iq4. (fle: Trouton9 f4g 0l+6I
E4B.1'.t(b) 20.0"cq1^l qtr EgE +rl "Jqg s8.okpaolq, r +g dB
q+.)
-4Y zzjt<l mol-'ol4. 6zl S4ol 66.0kPaol q= gEE +6|q?+.
ㅇ
^l
ㅇ 6lql^lE ggE +dg 4l^l6}q4 ad
E48.5(a) sObar9
g*q gE= "Jq Eq "JE=
"* cm-rol+n +ol+.
o.rzg cm-3ol-za 1.009
ol a}9l
E48.12(a) 200Ke+ 260K
^lolel
gE gEql^l qE .4illE +rl sqg
ln(p/Torr)= L6.2ss-250r.8/(T/K)-e +qd+ ol o-4i]lE +g elBtlE +6l.
,d,d
,l ,I r l l^tlrI E^l
E.:l
66 atl-L--I
illEr,1E
1 -^^^ry 65 k
rnol -wlT. 273
r_t^lFl
=-E-,il.,]|^l
-6-_6- o.uroK,
ggE +Ag 4lt}6}q+. ol afl
.
q+ 20 8 K
5
Sq 6}ql^]E
.
E4B.s(b) rOMPa9 ol.

ql^J g*E EE= oJ O.ersg E48.12(b) 200Kel 260K gE gqql^l qtr "-qillel 6zl $H9
cm-3oltr Eel "JE= 0.ee8g cm-3ol4r F ^l-olel
In(p/Torr)=18.361-3036.8/(I/K)e. +qd+ ol Eillel +ts elg4E +6i
oI4. At'- +=dq^J Eq +& elBsl= 6.00skt mol-'ol4. q+.
Eill tlEll E9 .s+ E dE e4} osl K-r mol-tol
ㅇ
E48.6(a) 273.1sKql^J
r" Ag gEq^l ggE A++ 43f 11-t mol-'o]4. 3E= C^J +=eql
.rl lK Rl+ +q+ts "q4 En+ g-sel EiqL sl¤l¤ol BrI4 H6].4LL+?
ㅇ
E48.13(a) ro.Ce| 30"C
rorr)=7.e6s-1780t(T/K)-a
^lolE
gE gqql^l Hldlg 6zl $43 log(p/
+qdtr}. Hldlg (i) +g slBsle+ (ii) a^J #
65 4tt6lq?+. 341KJ ,3504 K
^li
gEql^J q¤
^Jol ¤9alzl
o e rl
"Jctzl olf¤ ¤B6Iq4. 43 =ag ls'Ce} 3s'C gE Bqql,<] 9H alillE 6zl $H9
E48.6(b) gE= l.sK EJ+ Lllel= a+¤ zlzla- ¤+ E4B.6(a)el altlg
E48.13(b)
ÎolE
log(p/rorr)=8.750-t62st(T/K)s +qd+. ol s4illE (i) +g tlgElel (ii)
EEol 6Iq4. ^ll
gEql^l {tr t"l gq+4 "E q "JC.Jzl olf¤ ¤ atl #=ag 4l4I6Iq+.
E6Iq?+
I rll : "JEzl 0.879gcm-'Pul
O E¤ zs"C-APel
EaB.7(a)
H6l4lL+? 2eSKql^l
gs"c-=. 7}g6t*.+. EE
._qill EE s'= E qlE pEl= 6e.el K-' mol-,o14. 099
s+q,L ulH!¤ol ts"I4
HoJtrl. -
E4B.14(a)
0.891g cm-3 o
Hl4lg Iatmrt s.s"Cql^J
+ E r *8 tBsl= 10.s9 kl mol-,ol4. l000atm
ql^JE Hldel q=eg zl4}6}q+.
ㅡ
E48.7(b) 39 too'ce.*el tso'cE- 7}g6lfr.+. e9 3tl+ qH!¤ol EsI

gqql^J si E4B.t4(b) E ¤elol 46.tgmol-'ol q¤ qillzl tbar4-3.6s"Cql^J g trll
+ H6IAL+? dill K-rmot-'(¤+
=s3t at)g fl6lq+. a- ,,Jr;7I 0]89gcrn-'PEl 0.80lgcm-39.'E 8.J4. E. r ¤+ tBq=
ㅇE48.8(a)
7lE
77] ,tl-eoll 4+6I= .Jqg l00kpa-trPq rotupae. *zlt-l
ol
^lEel +qL
slHl¤ol 9"I4 E6IA!+? +"-lE ¤* "Js=
8.68kImol-'o|4. ro0MPagl^lel ol EillE q=eg 4lt}6lq4.
8e60kgm-3sE, fl6}q4. nOJ
-*21t. O #Zf EEJ

=Eel =fl4
-A.6lxl E T.ll
o ti -r ll,'ll
t4.1* Goodwing 4BHld9 gqq}4 C¤g ts+6}r + ++ +dq + Ts= l78.l5Kolr|. zel-n "-4zll-?zl +dg q-s=r+ A+.
6J 4lg gg6IB.trHR.D. Goodwin,l. Phys. Chem. Ref. Data tB, ts6s (1989)).
r+ r.ill-alill *¤ +dg q¤4 zJ"l #"ltl4. ln(p/bar) = -rl.4r&ly +2r.t57-t5.996y + 14.0151-5.0120f + 4.7334(l-y)tto
p lbar = p rlbar+ 1000 x (5.60 + x

¤zlrJ y=TtT,=T/(se3.esK)o14. (a) -r.i-ll-olill 9 "4ill-¤:71 tI a4lc
11.7 27 x)
53 s-llalq4. G) 'llgtldlE s+ +eg +6Iq+. (c) ,|EHICI
¤zl,,.l x=TlTt- lolq, ++¤ "Jq$ gE= 7J7J pr=0.4362pbare]
EA 131
{xlxl ?*sq, q{^l +ol }'sEgllqe+ ?J? Ag "l8o}9 +il 4l,t} dEi.lltrl. olei6J ol+E qEql qolo|$EE zlal $ulxllE e+61-b &
9 ollol .Jtr1.) (d) ,llp{]r$lei s= #=dql^l9 s= +g $gEE 4l B E"t"ilrl H?-l "l+qr fltrl.. E*6lE 4ololEg= +¤r+ ae d
4}6lq+. E= #=dql^l Ezlle+ GTlel fi +r4= 44 o.nam3 mol-rnl 4 gg + 9t= tsi 5+i1e+El 6J^d6}7l7l qB+ oleloJ CdB eol
30.3dm3 mol-'o14. 7l fl6ll^l trf8-¤il-= ol¤.6IH 2s"cql^j +¤g clolo|:e-E_E Hitrlzl
t+.2 truld-e- oltrl:c{lel +ql^ll.J 84fl49_e^1, qBl +zl tlE I*
I rll $eal $qtzlg4 Eg-ol "JqLl=)g qH6J + 91trI. ol +49 +
ql 96il^l ?iae+B e^14 +a= zlzla_ fl= Eeol4. :elq qE 5 ¤_+4"]"IEE r+Aql 4oJ AcE 7}6li+qot 6L= Sqe.l 6J+E +44
HoJ trll= .=-?-ltsE-lE 4IJJ +z7l +4Ie ?"JE +
E +6}r, olq^l Gibbs ollHzlzl. $eE q= Sqg +6Iq= 1o14.
A6J ^lg sq el=g LlE}lll= trl^s 49 +E6Iq+.
qg+.=aEol
ol +a H3rl+ r+q} Xo1 gs.oil^l^hag
"Jq+= t dol4l E f
(a) "J4 g-E.ql^l
^.GE
E flsq, 44rl ol dol gE= ++ 8E- r^q 6ll%I6l-Erll -z 7[ol rt
¤ +E +^PJ t}E4}+q +e+ ^-llTlql al4 ¤:ztEI4. gqo+¤. ole"6I.{ (H),=vâ-vê,
+^ aql-e-_a *491= +cB ¤4fl4gzl +qa^l +z+c ?ge El
eE r.g ql+6J + ?Itr|. E4fl4gzl-wzll9 olulrE4}g zlzll g1o {zl,r] V,"*8 +Sq E+q, rell V_,ats +olo}EEE ggEl4. O) +l
=
H (w-+)zIE f+ ¤B"l BC¤ ull zltt B¤zt"J BEltel +d"J a-*d el ++=ql 9lq^tel tde y,nol "Jqql e-1+t4= 4.o14. ol 9
ol BcgtrI(Eq 17DE -E_oi4). ol ag!} "IzlE +IzlE zlf¤
^l¤9a"J+
^l¤.
+q_!+ Aol ++E gc1. l.cE .Jqel *+.E H ?, olAg q^.q-r+
,ll +{"J + 9lo t: +, (N-2)Zl9 *zlzl +Cg ElEr &E"l 4 =E=
ztol p=pe4],tl thylor dz.llE t4.
Eg + 914. ol4{} ,HHql oJ46ll^J ru>soJ E4flBgz} +qzl= +A
9 EciUUs "llHzl H+= +6IH trl-s-r+ ?ol ¤4. i-
-L
- p" ) ++(
A,nrnraG = (N - 4)Ai,tH - (N - 2) TAhbS
A,G(p) = A,G(p" ) + (
tU ),=,,
p
#)" o"(
p - p" )'
q7l^l Ar,uHe| ahbs= 44 E"-ltsElE "Jql^19 ft eqle-l E 6l]4 ?lg

qe+ qlE-eul4. (a) ¤B r+eE Gibbs olllzlE +Elq= fl49 4'Jcg ¤zl,tj EEL+Es p=p"ql^l {t$$ +6}r" z^16]"vl71trJ +l++. +l^lel
Er-6Iq+. + flgq 6Jr+ $lE-trul .Jg ql 7+7+ 1ru-+;4oael. (N-2)AhbS
aj AE (a)qlrl +EI 49 ol86}q +6F=ql g+El=p"ollrl9 (}g ^F*
tr -E^l6l+zl "5"144. O) r_g r-l-q_r+ rJol 448 + gi¤-g trq4.
a34. :zaf-u ool. BE aillE 5-g
"J+E rc,= -(UV)(dv tdp), E ol+6}q
ol
+++. cqEol.aoal{ gc SEql^l q-q_4rJgrlol cBt}gBq+.
_ _ (N-4)AhbH
'- - 11g-2)An$ aza.G _ d ,,,
= ;7(v.,0 - %* ) = - Kr,ov.,o + K,,*,Y.*
tr
(c) T,,/(A65H-/AhbS.)g s< N< zot 4*91 El6lt^l E^l6IqeI. NE <lol
9"IzI Elts NE +7}ql ulE r.E Hslzl 1o7o ulnJe-e. 94Lg*i
¤zlrl rr6e| xr,o* 44 Eg "J+Eol4. (c) olq^]
+ololEEe+ +¤E
Ar.l#
(a)el (b)9 (b)9 Bq+ts E= aaql^lel E
n.r ,ll$* A gel{ E¤olzl"J d¤ z}^9 ? C$ol"l^l qd6l ¤+ g "J+Ee+ E+q E 6J+s +C + il+. (d)^.G(p)=
^,G(p)ql I barei 2e8 Kql^l 4¤ + 4
4r}ol !n ?lq. Friend f,$ ,ll+9 gEql4 Ceql +.J fl+= Bslt olol-E-E dolgl qoJ A,cE 4e +2.8678 k| mol-'o14. "tell qlolElE ol
Friend, |.F. Ely, and H. Irgh*rr, /. Phys. Chem. Ref. Data 18,583 (1989)), +6H ol {olz} x}${-e-E .Jq+= Sqg qH6}q4. rc# "J{.ll F
r +ql= Eill-6zl ^J aal= Lt4.ll= trl-S4 rJg rJloleizl Eqilq.
=Ell@.G. +6].+r zlAdlolel.
TIK 100 r08 ll0 rtz ll4 r20 130 l(l() 150 160 t70 190 +¤ qolotEs
plMPa 0.034 0.074 0.088 0.104 0.t22 0.192 0.368 0.642 1.041 1.593 2.329 4.521 v,/(cm3g-') t baroll^l 0.444 0.284
q/kPaI 3.04x l0-8 0.187x l0-8

(a) tI a4ldg E^l6Iq4. O) q+E E= #=Ag +6Iq4.
qlzll-+zl
(c) ,11ts9 s+ =" B SlBul(s+ #=dql^l)= 4lt}6}q+. s= B=¤
ql^l t4.s 4¤. rllolEl= ol+6}q ddE al¤!a(36Torr, s.so"c)
"lille+ Gzl9 E +rl=
zJz] 3.80x10-rr+ 8.8edm3 mol-,o]4.
^l9l ^J*lB
rBg r44, Aru,H=t0.6kJ mol-r, A""pH=30.8kJ=ilql
mol-r,
n.q ts49 5^'i]l"J 4ololfiE= qr]al EetrElE ++6Ir =-3 E p(s)=0.89t I cm-3, p(l)=0.879g cm-3.
-#v145
E+ eor:
I I
-
LT=E,
--lr!
- -
-I
6
--
sElEe r 441-tr^J +"J otq+

ElEr HI+E Eeol sD 2tr8 4lE ABE f.aJ: a.fll
g+. =g
qq
¤e-ea] +84 Y Eol
3r}4el oJ
"l *E Eqql
ol sS{l,t.]= 4lE .lill tlr+ a^ll tr-g "J$s+^l7l= aaql +
ge Eelzl ¤el} "l Ce$$ eqqzl ¤
^l= sirl$E 4^l +e¤ dE ql¤# rill sqlEE t1-¤E rB o + qB
e$$ zlzla- +4,-ll= %r-Hql +611^l *+6}rll ¤ 4o14.
Zl eofolExl=="+6t41 g aolq.
sD.1 3E EEIEI; 5D.2 Ut Al; 5D.3 HlEil +g
5A EErEoil EH-el EEqt
ol tlel arq Eqql^J= +d slq} qfl¤q ,}]Hg gd^14 5E 3¤E 4tet ABE f H
olaol EE "Jol4r. +s.
^Je= +E 6L+"Jg s"J 4ol "*9 tlaz}l Ee544 Eeg sgt61q)g CE"l il oltol
4. olq^l E6JE +ql 5q9i= 6J EAE EiqL qHl¤$ zL 4. "l Eqql^l= tr"B¤ rgg qB4 3^d+ 4lql 4e"qE+
zlr.:z E6JEq E44 CAg Ll4'.ll= rlBql +6H^J ¤B
4zlrlzll. ol+al gg 34¤ tI¤B reg qg4 6ll46|izl
6EzI ql4. 9zl,rl EC6lloF e ?]4= BB¤- "l ql +6li^J r"P6I4l g Aol+.
qL =e4"J
: qfl¤ol E"J"ll
+i1 9l= +"1 {r-q EqglzJ s}qr" sr.r s4E ABE lB; 5E.2 3¤E Il
"t ql+= 4o14. Raoult9 Hzl"l4 Henry9 Hzl"l+r 6l
dB ^|¤g ol+6IH s-JE +ql Eqgi= ^dE EAEE
glF-
rrtL 6+ t-
-9.t-.
rr
=
ElqL Elqf¤g r E +gg zlxl:t_ +4'J + 9l+
=
slqt qfl¤9 {H$ ¤xll E!*E9l 4^$lzlzl 9la1l.<13'¤+E
5A.1 E= S; sn.z EEet; sA.3 o_{illel ilqt ElEl¤
=6Jel E',+a +s= +s tE= ol$aflo| ++. a+ql 4rI^J= g+5
E= +zla c.aars-" zlzla_ 6114g + 9l+. :. aJ +s.J ql
sB Ee4sl ¤E 7i d6Ha *.1"14. olElt +EEg olgE. ?J9 *4?-l tr-s4
ol e$oll,lJ= ElqI qQf¤e-l 7}]'Jg ol+6lq Sdol +.-4E g
+ "ll$ql "ltl4 +ol_e_e+El rrll H,qUq. ol s{oll,<J= #
q+4 CAql trlzl= a45 ¤B6J 4"14.+,HE 6zl "J¤ g "19 A+ql _E Jg trJ¤q^J olBl6J ol^J4 B+e_tr+q
-0-"
qlg, #Ed sE, qEd Lilg, "l AIFEI=,oI HIE olq+ gq

9 0lE9 qBrI +C6E1 E ol A+= q 4lql e" eq9l qg4l
E4 ^de3l+. ,g+ a_o4,olrp. +s= f, g6a3 ++E d +4^l7l=zlql +4^J *+6}|l ¤ 4o14.
,ll +"+ql ql6J E'J¤- Ll-E=jL E olEE d¤ol ol^J +.-qE C sF.1 E0llel tsEE; 5F.2 Eeg gEE; sF.3 E+ EEel E5s; sr.a
¤=e+q qBal olEfol*|.zlE="F6ial E aolq. ot.g.ot
-tL-
E,}EE
ao+t
-
58.1 Ei.ll EilE; Sa.z

=B¤
g r[-E 0l rlEe! EE=?
5C 2dE llel A'JE laJ: Ei{l ol Eq9 4*ol ++4 q6Jg 6lE ++ Eot= E]]+61 *
E6JEE ¤¤ CAg sqb6F= Ell tI¤¤ rBol olHfl6}rll 4 zl"J q7lî= r+ SE+4 4E4o,iq + +olql 46l]^l"J
"J4. ol Eqql^J=
.lills g 4lel tL-¤¤ rflg dÎ4 " + Azlla3 4,o14. g6} 7ql^l ii$ ¤^Jol ^Jill r ¤Eil=
^ll-trz}
rl 5*c 4.o + q.tL^lrJ 4"14. r4r
4lel Eill *a] *zl frzlal-b Ell qB4l ol+qEzlE 4"14. r?]r s*
^zl]B
^J# "JA+^l7l= eAql +6H^J +gg dE ,ll¤# *B 8ql^l= ^J¤¤ rflol *84_o_s +s+._4ill eCE ¤Ag
¤ :.g " + qB4 $$-oJft.zl. a"+61-7ll ¤ 4"14. ¤E6L= ql qB4l ol+Elr 9l=zl$ az]lp 4olc}.
sc.1 g+ atsE fa; sc.2 3E-5¤ aBa ra; sc.3
5c.4
=71
Ei{l-Eiil 8tse rc =F;
EEf 5A EH-d EE+
=-stE0ll
i$ Eflr }'} Exl¤9 ++"tl tr+{ Bqzlzl ullEol+. ol +

> 0l EtrJ= Ell+.= olP zlel qlql^J= ql+¤.ol q+ "*zl ulEql E= E +zI7I +
El¤loil^-its u8g + 9lb Es=g sEtrd H?l-d
^1E =s'=3
+lEElrl. qa[^1 871-\ 40ll^l Hll8 7HE-
++ qlEgs Eq4"J+ +++.Bql^Je+= gel gHI4s
=+E =EtE-
gHJtrl^lfl^1 +{#q?.8 Eil== +F-g + ?,lE= g gsTl ?ltrt -e. H2o Ezl#.<le. gc¤l aElq E=q += +A aqlel
"J^J +a7I ¤Cqzl ?*=tr+ 4449_e H2o Exl¤g eoJ

> 6_{c 7}lLJ 6}rll +olq +Elzl r4cm3 gl"ll +ztalzl * al^b 4ol+. E
+oll ffl?,.E Ei 8tr9 El¤l E1EJ¤3 r EoEol tI|+ :Br+tl. .JE +qlî +.J ul= E EzlTl 14cm3 +r-ql ilzldizl *61+
=Et=
4"14. l4cm3 mol-'9 ++tI qleg +ql^Jel E9 EE +
> ga.Et qHl rl^l ,]tr}. "JHI4 0 e -J gqlE +qlîe-l Ea Ael E +tr|=
0l EEoil^j= ++Et Etr= 7l^la s."JEl zfluJ(Eq 4A)= olE =
6fl^1 etqf ElEl¤E 7flts= +el EtroilE+ qg^l7l1l Etrl.
+rlel r sE.Egl4 r molg AE 71fl,9 "llE +El H++.
tlEEl{el Gibbs qq^|e| =dE el= EZI(EE 3E)el +E gr'aJ EqlEel a^Jol ++¤L AE+EI ++tI B-E HElql rq-+^J
-sE
E zHE(Erf rn)3 ol8oPil Etrl-. 0l EEa[ qe] EE EE- C+ Ezl¤E ++aol {a}q + ol=el +E +i{= aCql tr}
E6lG EE +9 EEE G4 Bg EflE LEIL}|T1I E ?iOItrI. 4 g4rl+. Hls ol EzI {+aE HE}e+ r qlEql a4q=
olE¤ a+al^fE 8r.| r 1q eq6'll
=9trt. Ezlz} CE Hsl ql$ql s.J$el gqql4 C{ol aCql tr}
4 H6I= Lol4. E4 ql+g4q sqlEg A+ 2s.cql^J
dill a^d ¤Eql aa ^dE=E EE +q= rH sA.lql +4
+de ElqL HI¤{E{ 6Aqlî A#6].{l g+)g 4Fzl flaJ ,.11fl+
a +41e.<J, ;.J-tr *s" 6}zl ?+. E6JE-$ fl#o}Elr 6J+. qE 6J .JHl4 aCql^l
^"jE fE EE +i4 yr= r-l-s=r+ e
+d + ^JE Ae+ B7I Ed.g ztr= +tr- +lE6J a ol aq¤+.
ol+. Eq rAql^J* dal Sqql zl¤alE =_s'=g
EI CEE ++ "J
qg Tlzlr zl;ll gajgE Ceg E$ 4"14. sEL+g E+ u,=(#,),,. EE +tr| [8E] (sA.l)
_H-¤4e + gq+4eE +IE6IEJH += qBl '+E ^de',E
E E.eI Eola1oP ++.
{zlrJ 4zl n'2 4E s= Ee9 "}g "Je6}rll +zlÎil+
=
*g ++U+.EE +4b "Jq, g.E-, "l I "199 4E -s
5A.1 EEg ¤BEE Ee%Eg "JA6Iril +zl^l7lHî EJEE di{
=
+E= Iel Ee=Jql 461^J E^l6J r4sq zl&zl+(rH
+E ^de +ql^l 7l.+ dal ^J46J + gl= ag.+E +El,"J sL.z). EE +q= E4 q+99 A+ql^Je+ z;ol zd,ql E
^lE +E t c+"l
ql, olae sqlE .r,l_e dll +qql ,lq
+6J+.
6l+ +rl+.
EE dE 8^l rupec9 +aql qsE EE ¤ee E ^J
(a)EFrl d x4 EEo6J E4zI 9lg trI"J xe +rl"U4. ele.r1 ;4-
"_4 +ql^lE Nacl9 Bli +rl= +._qE +irl
ye+ +E6Izl
2s"cql^l 4'llq}+qE ++6J E-g ^J4}all Ez[. ¤z]914
I mol9 +3 q 716]l +H r +tlz| 18cm3 trJ=i +7t6J+. ol +16]]^1 71NaCl, aq)e. +EtE + 91trt.
t8cm3 mol-rol4E "Jg ++El Eg E +rl+a ++. r4
,+ Aql6J +{E ++6J qltsgq+ rmol9 ES zlalH + sA.t^lel Celq E6[E AE dna uJfr- z[ap BE dns trJ*
ulz| tacm, +ql f,zlaixl ?*=+. ole+ Aol *vl ?zl7l L+ 7I6Iq EqlEel a¤g HE|^l7lE gqlEq aill B:ilzt 4
ol+- +qd +E E Ezlzl ilzl6l^= Pulz} ol E EzI *rt ?"1 Holl"t ++.
=
sa E-dEoll rH-d Eq-+ 13s
58 e"#el q++E +61-= 4,o14. "J+ ol e++= +6IH olag

E
so9.
ul$o}q "JEq +d qltl aCql^lE t z\$zl= +g +
8 91trt.
soI- rg
i "o ru0
H: -le
lFtr F rlu
E
o ,o 3
GZWE+qeE
olil
-" --t------"i""-"-
rulo
-i, <'
lJrJ
ofo
lu
so it
ol=
ulruf
s oil
l' BS eaJa}= E-qltrg +'-4el dill
2s'Cql^J 1.000ksE
14 +rl= +A6Iq +94 Ag +.J! o e. +4,ll$.+
0 0.2 0.4 0.6 0.8
+
순수물 ollEJgel
=EE,
x(c,H5oH )
순수에 탄올 u = 1002.93 54.66642 - 0.363 9422 + 0.028 25623
fA 5A.1 zstoll,tl Erl ollEJ=el EE +tr|. 4sz1 e^l Ll- +s-6ltH4 ¤zlrJ u=Vlcm3, z=nrlmol, r?]r nri 8"-4 +ql Eqgl=
(E= gr+01r, ollEJ=e 9=.+0|trf).
c,HsoHE E¤=Jol4. q]+¤.e-l +E +r4E ee6H+.
a.a1-g A[:d sA.t^]E eE. ol$aJirll, ngl +e] Eo.J+
E z"ll +6J E:6J+E Hl-+r ++l= rqE qE+.
Eol ql+gE EE +vl yE= +-q=r+ ?ol 84.
v(bl
(av1 (a(vtc.n'))
j
tr V(al
rF cm'
rK
dl "
=
[ di ) n.,.^,= [
aO;1,"O,J0,,,,,, m
=f
\dz
P) )0.r.",,
cm'mol-'
a b
trl.4^J
Jg nJ
=EaJ,
fg sA.2 -d E= +trl= +tr|= 4d0ll rtl6tl^j E^l-d
=Eslgu4o+ EEZJE
+dE 7lz7lel,Jtrt. ^lEEId = aelboll^1sl )lZ7Vl +ell ! = tn.uu64 - 2(0.363e4)z+ 3(0.028 256)2'1
LfEtLlEol 6doll qel EEltrl. boll^lel E= +E-l= 301 EE +86|.qal".

uI4rJ
raldltH 0l A= 7l5l"E +tr171-a^:Lrtrl.
^dql^j= ^lEel =
V./(cm3 mol-t) = 54.6664 - 0.727 882 + 0.084 76822
dv -(#),, (#),, (sA.2) "l sL+E r4s= rB sA.3ql +Q'}]fl+

.dno. n^d',
56
=Vodno+Vodn*
-!o
Ae+ B9 aC Bl¤-ol "Ja6}4l
fxlqts^l "lEel E¤=J"l C
ol -- 55
?zL94E ^l¤- roe] n39l +6H^l 4E6ll= + gl+. +, ol E
o
46J ¤AlCol f'zl9 trll= EE P4 vos+ vuTl "J46Iq, trl >-
4^l olE¤. 4E zls +r-e_E rllELl]r 4Eg 6lq q-e-Er+ H
ll- s+
ee ar+= eg + 9ltrl- olrll
lH
, = J; vodno+ ['" Vudnu=r^J;^ dno+V,

[i'0", (sA.3) 53
0 5 10
요
=Vxfre+Vunu z = nelmol
zllllzl F zltsol ¤4lg e rJzlall$zl"J(tlq4 aC fg sA.3 H7l sA.l oll^le| pp c1g4o e LEIL.! ollEtgel E= +tr|.
4.o
ol "JC6Izll #zl!E) wl tI4 .J+olE__tr sA3^lel 4+ 4 xpl 87[ 5A1 a"tstr- 507ooJ ql+g_E +EE "JE=
4E +'lg qB4 "J=a *4lH"l ^JB++. 2s.cql^l o.et4gcm-3o14. ol +.4q1^J Eq EE PqzI
r7.4qrf mol lol4$ ql+gE +5 +81= $"LzI qALLts
EE +4= 94 zl-zl*B-"e. +AR + 9l+. r qI "JH
g a^dql QsL +'l EEI¤ +a+ q+, +aB +q= E r_loru ¤rurg'?S B{e+lo Et-" talt :r-totu ¤tuf,r'gs E{e+lo Et-vg'VS:E
136 5 trh==:Et=
E +r4E 6J^J "JE *zl"J EE +qE :z$x1 gg

<t¤.
+E 9l+. qls^J Eql^JE MgSonel ++ gE *.,i](*-szt u(b)
?d4 o_e_ 0ol g trIE E. +El)= _l.4cm3 mol-'o]4, oI+ o

j
p(a)
4=JE Eqlq I mol9 MgSooE zt6IE t.4cm3 "J#E + K

5
^J
ulzl 1litlJtri. ols+ ?ol *ulz} ++q= 49 rvrgr*a| soi 6
o
-o
,l +e+ElE^l Eq Ca +aE 4lq Eel +== ffizl_oe ¤
(,
-"l$q +71 trll$oltrI.
a b
(b) EE Gibbs ollLlrl Jq
=EaJ,
nJ
Bg "JE ,]]Hg qH r7l Ce tr-4 .J+qlE +tl^lvJ + lal sA.4 El

=trel
it-E trlEJl¤3
=E}EE
Eill Gibbs ollLj^l= r Etrel
9l+. E'*E +E Eeql qldl^J= r EE Gibbs "tlHzlE:- EEaJoll Etl6tl^1 s,tlel +del TlZTlel eq. gg4o+ ElEl ulEJl¤3 ael'
boil^jE ,,J=01 Eol= Hlq eol Elal EElrl. 0l 3?0il= + a|,+
slql iflHl¤ol4r CE6J+. + trlEJl¤o| EF gE ,J= r*=tr[. ^doil
(ac\
al-+ trlEJ¤ [8sl] (sA.4)
''=[d4 )0,,.^,
4 ee sAlzl cB++
¤zl,rl 4zl n,* 4e _E_= g'JE ^"iEE olg "Je6lal +zl
+ "Jqr+
^la+= f$'l+U+. .JA6Lrll
gE
I rflr
+ ole-lel dr.oo,,n.* = Frdnr+ ptodnr+ (sA.8)
.E-= EpEE "Jfi$ -,?zlrlTlfl^J Gibbs qlLlzl

= z ul --!li!- 6!o
_i= -llol ::z rl ril*IrJI rl rrlerlr-
/ln :r:.d i;1j{"lll{i ui;q.l.:L
-rrlrlrl, -ii_r,-ii
,A"ia-. ^ll= rl
. ^Je fel Ee"*ql ql6fl^l E^l*g oll9 zl¤zlzl 4E l9 = "l__d-d
slE ElHl¤"]4(:B se.+y. ++6J Eeel a+ql= G=/t1G;,, r+ql dzlgl^J= F tr"lel +i(= + d+)ql^J p++ Hplzi
olja" se.+^lql 96ll^f pfcr_ol+. oltrll=sI+ trlHl¤ol E "Jq+a] qqgl+ 4zlzl +461+ 4zl4 "Jg HI¤¤E+
q a¤ Hg+e+q s= 4o14.
9 aeqlrl ^l-e" 6J a4 +? E cibbs "llH zle+ arll g+ ^J^JEol dzli
smlg gg "Ie+ qgg "l+6t$ 2CB EJEE
=48
d;ll ciuus glLlzl$ ffi$ aol +4.J + 9l+.
(c)'JE ElEt E1E!¤
=9
sl+ tr]fl¤e G7l acql q+ qBrll HaLEzlE E"l+=
G = nolto* ns[ta (5A.5)
ql rilzl ?+.+. G-U+qV-TSoj o + g=-pV+TS+Gol4,
{zlrl le$po5 ?old a^del EJEqI^JE +q} qHl¤E E|q^J aCol H6J + 9lb 4lE ulral 4+ qlqzl Sffi
oltrt.= + EEIE
^dEE s+CI,l
i{fl¤g E-JEe] dill Gibbs ++4 t"l 44'J + 9l+.
"llHzlgl 4qI:1 cEq Tlqol+. slq1} i4HI¤g a^J(r4_r.
%Lq4 gE)ql E=6IEE g6JE.e-l Gibbs ollulzl= ol= H dU= -pdv - Vdp + SdT+ TdS + dG
+E HEI-ll ,rl4 HB + glsq, rj$ol A, B, ..."J 4lql q6ll - -pdV - Vdp + SdT + TdS
+ (Vdp - SdT + 1t^dno+ ltrdnu+ ...)
3E.7^l(dG= Vdp-SdT)o1 q-q-4 ?ol ¤4.
^JE = -pdV + TclS + l,t odn e,+ 1tudn, + . ..
dG = vdp - SdT+ Fodno+trrodno + ...
olqr. gq-+el 7lE^l (sA.6) ol acol E6J + gl= 4ql 4+^lvJ + glE+ 3E.1^l
^lg
ol 49 trl-+ Eg-+q z!!|.{o14. ol uflEafL: E4 a (du=rds-pdflg "JH]E]rlZl 4ol+. 4le-1 +tle+ Sltr+El
^lol 7I oJeoJ ull=. ol zlol cJ-e=$ ?ol ¤4.
ql6t= ¤459 ol E{le+ +s Efl^ql^l EI+6I1 gd
rl? 4o14. dU - l-t odno+ ptudnu + ... (sA.e)
"JA+ "JE4 gEql^J= sA.6^lol trJ-s'=4 ?ol Zltqld4.
dG= LIxdnx+ptudzro+. (sA.7) ttI+^J
*e.l Eq 3Eql^l ¤E+ utel u.ol olel+ 6a 6lql^l= AU
llt a4 ),, (sA.10)
dG=dw.aa,*.,olrl. tr14^J ga6J gEe+ "Jq 6lql^J= ++ ,n
sA E-dEoll Ell-d Eq+ B7
slE Elfl¤g aCol Hg EI Gibbs "ilHzlz} q$4l trI{ olel* olil= += EE EE olqlE 4s"94. 9le.r.1 a3
=
HaiEzl¤ Hq¤ g"J otq+, '+l+ 9lHzlz| qBrll ,.++ E EEIE +E dESE +E +qEe q-q-4 Ae +4lE HI+
aflzJ-E Eot=+(Hs+ aag 4szl"J). .$ee "JHg ol* ql+.
^140h
6IE r-ls-,,r+ eg +Zl=E +EaJ + 9l+.
\n,dv,=o (5A.14a)
(a)tt,=[#) (b) t\= AA (sA.11)

S,p,n'
a4 T,V,N' 2cE 4lql ql6ll^J= ol +4lE trt*4 ?"1 449 + 9l+
¤=t prb gEtrI4 a71 44 U, H, A, 9. Czy a^dql qBrll
trlHl¤ol r+ril +s
d%= -hor^ (sA.14b)
el=61+71-= Eq=+. Elqlql^J slE
f, zt*$ ulE ol ullE"lrl. e."l E9 +E +qzl frzlz;! qi= qlBg
_zH se.rql^Je+
E EE -+ulz| 4itt}4.+"J olq4 se.r+u^lql el6|E :B
(O) OiOOs-Drrh,e,m l sA.rql^JE 444zl"J notnuTl ull= AE +g +jil7]. =+
2CE EJEg dill CiUUs glLJzlE se.s^l(G= nette*nstts) qI H6}]E Bel EE *vlzl- rrll=H++. rBl+ notnrzl $$
e + +qzl:z E E++ ElHl¤3 aSql 9=6|s_E 2tE 4l oll ole+ HI49 4*zl +El++. dzllE Gibbs-Duhem !3 z
E aCol ulaalz]l Bg trl= Gz| rls-=q- B"l H6J + 9lg C+ s6JEql^J oJ CEg Eg +'lE+El += CgE +g
4o14. +qE- +61+ ql ols" g+.
66, - 1t^dn^+ ltrdnr+ nodlto* nsd4ts

@ cibbs-Dr,hem^lEolE
r{Lt"JC+ "Jqr+ O@
g_Eql^J= Gibbs qlqzl Hslz} sA.74
oE +qTI+.G= tr-ql .J+olo + dcql 2e8Kql^J KrSon(aq)el EE +tl +e 44zl trls-$ gg
ol + 49
^l
4t o e +qd+.
E aop} 6Iq, q4^l ga+ gEe+ "Jq 6Iql^J= q¤.r+ ^l
zJgTtAlzl-CB"lloF ++. us=32.280+l8.2l6ztt2
nrdltn*rzrdPr=g (5A.12a) ¤zl'tl /s= vr,son/(cm3 mol-t1o14, zE K2so4E gBb

olag E +ilolr](z-blb"; 44219 ^&4 uS -H-ot+). Gibbs-
q^q=4 *3 Cioos-Duhem Alel 6J +EoJ a+ql 6]l
Duhem al$ ol$a}¤ ol +.]q]^lel EE E +y1= +e}
'&gtrl-. q3 !g +E6Iq?+.zerKql^l +++ Eel E +4=
}:dP,=O Gibbs-Duhem (5A.12b) 18.079cm3 mol to'ltr}.
I ^l
zs{g .t}EI A= e" u]l"J H2q lElr. B= +ee &sor4
Gibbs-Duhe- 43 gqlE9 + ^d+E Elq j4Hl¤g += -L 6IÎ. rq{ + dEE +E +iilql +s Gibbs-Duhem
c+Ee_l s+E ElHIg4 5-$alzl ?*sq, +B4eE HEI^la dzo= -@rlno)du,re+ &ol g + flgq, ule[,t] trl-s=r+
+ $.¤¤ F++. 2CE s6+EE A+ql= + EE "J"l 6zt ^13
*ol 4sa}{ ,oE +'J + gl4.
6tH += oJol q+ IrI+ a^dlot 6J+.
^dEE EE ^lql
ue=ui-li
dp,=-hdpo (sA.13)
ffu,,
4zlrl ui=vtt(cm3 mot-r)= +++ AE E +vl +zl"l
+. ,r|{^J
+d H+ usft z-btb"tr Hl^+jr" "lq^J +Hg
zltlEt q 5A1 z=0(#fd A)+El +c r.l]tr"EBE"Ezlzl 4E6lE ¤+.
+ g.J¤g aCol no-2nr7l9l s aCol a+ H6Iq B=KzSone +r E4lql^J ¤ rll"lEl-5- ol+61-E
Fe,7l4ro=*l I mol-' "Gl H6J qlE przl rl-gr+ *"1 H =ol
dusldz=e.r}$rtt2z} +g+. trl+^l gg+ 4$ol Q+$
"ilo} eI4. *ol ¤4.
Lltu=-2x(1| mol-' )= -2lmol-'
138 s tr!+=#
tbtbe nB y2
c H+= gq+4 0E +lfB + 9l'1. zlg4 E* 4aE
u^=ui-9.108J0
n.
z dz
+ qle^l= aJ 8zl +ql + Tlill= BHg ql gq+= 4a
g E + 9l+. ol gEL 4Ce zlB4olq EI+^J Gibbs oilH
eL¤ e(Hro)9 Ea%+g no-(rkg)/MAolr M^= E e%I zl! zltzt +Hlqqo} qI+.
olq. rala- notn64l +4+= nsl(tkg)E Be-l gBb-E b
e+ e+
압력이 변한다 =
혼합전 →
혼항후~
(a) eJE 7li{!sl c.bbs ollLjrl

=-Et
no= (l kg)/Mo n./(1 kg)= b zl+ gE Te+ "Jq pql^J nomolel 9d zl^lle} numol9 $d
6lzl{rfl se.0). "ltrll=
^lE +E $zl"tl 5q 9l+-L
nB ffs- flrM^ zl4lzl
nA (l kg)/Mo - lkg -bMo=zb'Mx * zlillel ElqL qfl¤"] +++ ^JE]lel <k* zlzl4, ,r|4,rJ
:f 3 혼합 후 Pd
trI+^l #=G,,9 e9= 3E.ts^l(G.(p)=Gf +nr h(p/p1)91 4+^14
n =ftRTI 에금 . al# eg + 9l+. uTtTal final
wow "l )
p P
혼합전( 1 bar에서 고수사기체 1
사
D >
u o" dz …
홀합전보다[J. )화학퍼텐셜과
보다 -
^=uX,-9.lo8MA 1b'b" "'''
변화 != lt-' +RIln 4 DA ㅇ B At β,
= uX - I Q.ro1 M )(b I b" )''' PK

> 1WTF -> 화학적 물리적 …
Dlbat
p Ibar Ibar Ibar [ 대괴압 )
^b" 능력 ↑ LT 의 성질을 혼합후 +-E trlEl¤9 "J+oll ttl= Eol [gttr 7lill] (5A.15a)
d
더 닮음 ] 요교준상태는 물질이 각각 bur 를띠고
qlolElE(Eg 5 4*
q-q-4 ,JZ 4+7I +e+.
Mn=1.802x10-2kgmol-'9 EEr-6Jl
¤zlrJ p"3 EE Ettrt trlEJ!$, + rbaroll^19 ++6J TlillE 있다는는
뜻
^l)g Bq+H slel ulHl¤oltrl.
vol(cm3 mol-') - tg.07g - o.rog4(b/b"1trz SA.rsa^]414 ptp"Z pE ++48 zls Eql^j *lt ¤?-l6J
1o14, ol tr+s_r+ ?ol ¤4.
ol +s. +ulE _E^lqI 4"1 :B sA.s+. ^lol
+RTlnp 증가는 PT = NrPtotal(sA.1sb)
11= 11"
40 18.079
dzll4-o-e ptp"*ptr. +4U+= agbar-tr +4Upel +il

isa
o
18.078 ++= 19 9"1+trI. CBEoI 4lolzl d9 dill Gibbs ql
as =
E
E
3- HzlE sA.s^lql el6ll^J trFq'=4 ?ol 84.
-O
:36 K2S04 E
5- Gi= neFe,t nslts- ne(lt"r+ RTlnp) + ns?t"B + RTlnp)
o
a (5A.16a)
\z
594 18.076
Eqlg q^S.ll= 7+ 7l;llel $4"1 p^9 przl qq, :z o}

5g
32 18.075
oJ po+przl pg} e4l ¤+. dill Gibbs .llHzlE cle=$ pol
0 0.05 0.1
t/(mol kg{} H++.
fal sA.s ByJEE +teqql^j dEEol LIElLflts EE +tr|. Gr= na(!fl + RTlnp ) + nuQ.tfi + RTlnpo) (sA.l6b)
xlTl B7l 5A*2 vrl(cm3 mol-t)- 6.218+5.r462-7.r47*oJ

g B= zlzltol 4ltlg qEol 6Iq4.
&6s80'0 + gygyg'o - 6/0'8I - (r-lou rur)7vn :6
fra,7, P
5A.2 Eg+
=ilq
Eq+Eq Gibbs glHzl= sA.s^lql^ls+ ?ol r acEql E= , Pa,Pg :1alI pa+ pa=
6Iq, E6J Eq 3Eql^l E_oJ HIe| ¤ol "J^d,* gEe+ "Jq 6I
ql^l 4l5e Gibbs qlHzlE *al 6IEl= ao&g 44u4.
"l
+l6J zl^lg ol+6|E + gAol 4l.J .ile+ B9 z}ts4"J a ral sA.6 F EE zEll9 E-c' Eq+4 Et+E 4llbl.= ¤B
5A E-st=oll EH-d Eqe 13e
@=EE+t
+r]]= A, :r-l_L +Ag Bql. 6l-z}. e-tEoE(tBl E.}. cr-tr-.tr. *s-
b^M.
DA
r+b*NIo
^l). +ql+a4 *aE EaaJ(E E+lE +4ug
+'-4E +q vE =qfl=
qb a"l+. 2. EEE. g4l
=g5Eet pola pqzl
ÎolelyoJ
nB
a* "JEzl +.1(g"HzI olH)E dill e
cB
V *? *-pvolr+. ol +tl +q +A Ez}el Ee=J
2 g+. rflr +A9l =qil=
Ae}g ms=nrMu-csVM,
"JHI4_o + 'Jel Ei(mol dm-3-8, E= E"J
oJuj rll,r.lulEt nu=coWl
7I g+. El+^J +r]|E A=*3 ffiA=ffi-m"-pv-csvMt=
* 4$"lzlql rlEl '"i g+mol L-rE +4U+.E}EE .E
(p-cuM)w} g+. rr-ll. EBE" Jats r+s-q eol g+.
+ ?t c"= t mol dm-3E Celall -oi 4.ol ¤El6L+.
Eqil= +e9 Ee"+(g ++l
EHL=E bB= +'+ +ql br=
frs_ _ cuV cs
E ++U)g +rflel dill A* zo(kg*o ? ++U)-o + +b m^ (p-rrMr)V - p-crM,

4"]r4.1, "l 4¤. 9 e
o sg $$.E$ Egt-qe LIE}u er+=
nB e4l g+.=,
br=
mA
brP
EgbEe+ E+ge gEql ++6Izl"J, ole+ qla4 ',-T+M
se EbE= gEql q=++. EBtEq E= <ig
b" =tmol kgtolr-f. 3. EE Al'olel tr41
=Eo-Eet =bBq ql'J
rsE44U 49 cuoll 4¤l ^lq Bq+H Bq t
1. EE E4l E= r E ESe +4,J rl"l 434.
=
==JtsEel z$la- ^!'olel
+"J +e$ 9l= +EE dill E4+g zolrla 6|
zl. +a Ez|9 Ee*9 n", at)a- r g E¤ xuzp a1g cB
xeP
xoMo+xrM,
olg z.|ololl ns=xsn\ 1!Alzl- ^dB6J+. :z4E $r]| EzL
el E +gg xe= I -xs7l qq, q4^J 8"ll EzI9 Ee=+g ¤zlrJ ra=1-rrol4, #g +.4E a+qlE xsMs(xoMoo'l
tla=y,on=(l-xu)rol ¤+. r4I +"llE A=*g +"]]E E 4.o}4rl,

¤+g Mool4;r 6tH ze= nnMe=(r-xr)nMorl ¤+. trl+
+efl EBE" EE q-q-4 Aol ¤4.
,,=(6).,
^J
xsft xB H 4zlrl xr( loJ-tr, trlu}^l .ra= lo'l B q= 9l al"l trl^-q=!+
bB -nu
mA
- (l-xr)nMo- CrrJM^
dol ¤4.
ol qe + 4H E B¤-g EBr-oE_tr +qu ar+E g p
^l¤.
Dp
,il¤+= mb cB=
M^
xR
bn
Gr-Gi= E-at CiObs ollLlr! A-oGol4, ol a*i*G=:

지 +gr+ p e A*i*G - nRT(x olnxo + xu lnxu)
g+. t Ear cioos oilLl^l [gT] 7liill (sA.17)
"l 마
E Egg a;6r r-tr4 4|e_E_s ol ^l +E r-il+Eg *ol I
A,ni*G = neRTln
+. noRThff (5A.16c)
q, q+^J A_i*G<0ol g+(rH sA.7).
"lE a^3q1.,tlulA-oG
zI ¤.ol g+= ol A4= $d zlillTl qtr Hlge4 ztts4
¤zlrJ n1Z x,n9=* u[f-r.(rz* Ae+ Be] A4 Ee*), E +E _o + g6Jg+= ag qql^]4+L+. XT
I
송 gas 일때 = 1 ,
sqr+ E E¤. rlolg +al(Eq rA, p,_x,p)= ol+6}q ?+ 4 )

자발적이라증명 )
.(
1
Eql ql6H^J p/p= x,-tr $efl 919 4ol trl+l} #"1 S4. 자발적 혼합 혼합은
( Dv19 대
G =
HA /A + HBIuB
( ]
( )) tnp ( Iu.tRTlapBp )
. 시에일
(1 RTInpA
A
G =
HA +
ET , BEonstamt]
-
DmTxG < o
( ) + MbluBo ( )
RTlaPB
=
거 AAo + HART ( nPA th β
GMAL
- I tnBI량)
다
=
DG =
HABTIn (PA ) thBRTIn ( BB )
혼합은실 자발적이다 .
( 기체 )
=
nxARTM ( PA3 + nYBRTIM ( PB )
=
MBT ( XAIn (β A ) + xB ) 어(P 3 )
G constantTiP
DTx G M R
담 NAlnxat Abl 서 N⑬ )
=
0 .J+=-d= DG DH =
[NS
-
1t 분자 상호작용 ×
]
ㅡ
∴ : DH = o [CanstanT P일때 HP =
N DHFo …
열발생 X
Ds =
( xAlu patt
-
nR ) pblncNb)) Dssur = o
0 DGKODs > ( 무질서해진다 ]

\ / trl-4^J il+ tr-E]]e-l Gibbs trl-s=4 ?ol
"llHxlE 84.
DStot 70
'
\
:
4.2 G, = (3.0 mol){p"(Ur) + RTln 3p}

t- \ + (1.0 mol){p"(Nr) + RTlnp}
AE
o 4.4
.a
E
ZlqlolE xll/o}q zlzllzl agBq + Hl|q +ElE ztzl6}
,ll gH trrzlE dill "Jqg zpzl+]4. a^9 ++ "Jqe
-0.6 ---__+E__- *pe- tr{zljr" +iE -f,E 3pe gq4l+. tr+4^J Gibbs gl
HzlE trl-s=r+ ?"1 H{4.
-0 0.5
AE xA
=EE, G6 = (3.0 mol){p"(H ,) + RTln}pl
fg sA.7 g¤:d aEe| galoil^1 + sE 7lillq !E= 018 E-4= trJE= + (l.omol)[r"(ttr) + RTln]p]
o-{i1(Eill ¤B-g7l-=Er'= rll9 ciuus ollH^l E+. =
IdolLl3ol slq, qa[A1 ga
Gibbs ollLl^|ts clcrJ
zFllts olE u|Eeul=-Et 4?.1tr1.
g* Gibbs {lHxl| ffi$ ?ol olE F "Je.l i}e+ a+.
^F+4ee
A.i,G = (3.0mol) Rr h*+ (1.0mol) RT h+
t7l sA3 Eet c*os ollLlrlE 4ltt = -(3.0mol)RT In 2 - (1.0mol)RT ln 2
+ *zlE E"J6J a-7lE + zls.tr. Erl^l{] trtg(rg = -(4.0mol)RTIn2 = - 6.9k}
sA.8), tI+ zlqlE zs"c9 Hr(g) 3.0 mol9 Ha += -J+

ollt zs'c9
+1 ol trzloll.,<J= A_i,,GE <tol F TlqE El$ e+. +
BH4. ZI"+ol= zll4ilg ql
Nr(e) 1.0mol9 gtl z}4le+ + 7lillg "J4"1 4+ "Jq zp? 4y HEl.il
el E_tiJ Gibbs .!lHzlE +6Iq+ ol zlzll# $d zl4l4 :91 f /lt'f"lT. "l E.: bIDDS Ylq^l \lrqE ^fE'd:
Al+I
-l ^J Î-l ^l
6 aI a.r i îl. 1-l rlJ+I :
-lul
,l AI
r.7IA6Iq+. -tr^le r= 6ll4alzl $zl$ HI*+.= ol a+qlb "Jq

ol H6Iq, Ed ac<09 Eg ¤.Ee+ $qql^J"J zlg^dE
d-o.21 q= aol+. 3.0mol9 Hrel 1.0mol9 NrE ag "J
mol H,
q 4ql^J 4lg ql= *zl9 Pulz} trl.+^J H6Iq Gibbs oll
qzl EEI+ -s.6klol ¤4. ol Zlg "JC+ "Jqr+ gEo|
ol qd6l zl
^lel Hslql 4+ alolq, <Iol ¤-ol4E ag
gdg 9"1d4.
3.0 mol H,
1'o mol N,
r;J7lE.7l5A3 2s"Cql^l 2.0atm9 H, 2.0moFt r.oatm9
2p g{}^la+.
N, 4.0mol9 olE
f,Hrl=$o ÎolE z}"-t"lE 4lA4q
p(Nr)=]r a-i*c¤-41&6Iq+.
A :p B: 3P Constout P * 이기에
없어 꼍
0tz'o-'6
ㅇ
DG
=
RTla (x z Iw. ) 불가
801-d geE TFllEol 부피 두 배
:
.LEJ sA.8 trllE Gibbs ollLlxl= 아 G= Gf - GT 써야하
4l.Lbl= 4Eoll^l _r.qd]|otrlts il8 =BE =-d
SElle+ a= 8Eil.
아
비력 2 p =
PA + PB ㅇ
( [동거 : ilw: :
독 nr flwif)
= -
어 Pi XT Pt =
.
3
( dw + RTmP ) [ 추 mTT ( 1.
폰의 압력이 다른때의 계산유로 =
독
n :f -
TRTLMP )
r,{Ef r.ffif ol + zlill= il+ql "J4"1 (b) TlEl EE+4 -d+
^le +EE--e. =Ef 자발판란 불가
sA.l7^Jg zld ol$-6J + Strl. +d E++ qfl¤g ol+ Eq 3Eql^J B"J utp* ?-"1 (aca7)p_-5olrr e E"J "JqE
"'lq a¤- t}'ilE Gibbs
qlHzlE 4l4}6ilot +tr}. 4l{}g
"l gd zlzllTl gEL¤ q. g* qlE +ul A.osz[ sA.l7^]ql E
6tBlB zJ zlzll$E Sqg $oI"F ++. eÊ $49p4 dlî trl-e-E+ ?."1 ¤4.
r ++. rflH +Ê Sqg 714 B4ql ,'I+ pE H1|+
E +48 + 9l+. q^q-ql= ZI4"IE zil49flg "IE 4lq A.xs = -(H), = -r*,r^lnxo + xulnxu )
Gibbs {lHzlE 4l4I++.
"lq 4 TlillE +ul= u||z} I E-d ?!e-+tr| [gd 7li1l. gtr-d rsf poll,q] (sA.l8)
q, q+^-l ++ $qe HIe-E aii++.
Sl eêl "Jqg p+a 6lH +ê1 "Jqe Tzl fl4. lnx<0olE E "itr a^3q1..rJr{ t_oS>OoltrillH se.g).
54 rtlEl Eq-+ 1t 1
(용질 + 용매 )
=-dEoll
0.8
5A.3 Ei{lel ElEf tr{E!¤
0.6 .+ill EaJEel ¤B Ceg !.oIElH .+illel Gibbs
"llHzlzl
t 4
ecql qB4l E=6l.zl. "Jolo} ++. ol E=^dg z1416I
6 0.4 EIH Eq 4Aql^l ¤E+ uts+ a.ol a4ille+ ¤Bg ol+r 9l
Y +71e1 clE ulHl¤"l "-4illel ElqL
qfl¤4 E"J6I+=
Î
0.2
4g ole" alfl gq.
T
\
0
0 0.5 (a) ol8 EE
+++ 5Ar+ +flq= "J=ql. ?l?xl-.E E"lzlE 6[^]. r
Ae.l xo
=Eg,
fg sA.9 g!:-J c_Egtgq dpl,\l + EE )lxll7l nHsl.F s4i1l7l qE +++ "lill AE ElqL EIfl¤gp.[B rP-]I ol ++6J A
=-BFEglE+nlE clttJ
018 EEE UE tttlel EB fll=eq(+oll ¤E).
=-E'Elol !E Ec 7lxll7l Tiol=e Tg-e E0l 0lEEl^l 7l .+ill4= 4.* ?t=t;J g,q7l fl¤- trI=pi(l)tr_ E^l*trI. ㅡ
=-cfEl=
^80ll,\'1Ll-=7|'6|.q,
Eeq rEhll ++lel geeults E6lxl g=tl'. qafll 0l rat|s= SC 7li1l7t +++ EillE +71 "Jqg pi olE + sA. t sb^lql 9dl^l =" 7l
ttllE Zlel'r T?letg Eill 9!-=-+ul= LIEILt|= A0l ElTlE *t. 5ill zl;lltr +l-=tj) E slq} ulHl¤epf +Rr lnpo
=-crE
E-d fll=+ul= E= Idoll,\l soloe e15 zlxllts clE uEeLl ^JEI]E ?lE etSd
^l.J4o+ (q7l^J poY potp")ol+. ¤Bql^J- ol + +qI qHl¤ol Bol
=EtErl. o| olE-e_ r-l-q=4 zJZ *Alzl- cB+trHr+ sA.10).
o-4rll e)l
#J:d o{l 5A2
(5A.20a)
p;(t) = p; (g) + RTlnpl
E"J EA*9 zl;llEol F.J Sqql^t g.Jg 4lE xe=rn
= iolH, Trl+^J, EAI +ql += dE, ? Sdol ,,1 ¤4]E qql= "lrll 49 e
A*iJ = -nRt+ln j+ jh]) = nRln2 E Elql qHl¤ol Feola a +71 glqg pool4. olullE f;zl
+'ll= ¤Bg ol+r
e+ ?lo , + Elo+ ElHl{$ ffi$ {ol
9zlaj ,?g 7l4lel + Ee*oltrt 4 +=ol 1mol4"J *ll
++E + el+.
I n_2motol4. tr}e}^.],
Iro(1) = ttf (g) + RTlnpo (sA.20b)
A.iJ = (2 mol) x Rln2 = +11.5 I K-l
4¤.ql= ge-l + 49 aq+6l.q TlillE s= E+oI trlHI¤
6.J 4¤: zlill +q a e4lElq E"lzlrl +A^J A
TlzllTt
Ezl z"zlfl qlE sl= e -4zl #zlqqot aLE 4.o14.
.JAEL *q4 gEE aa 6Iql^J + $d zlillzl sBB A(g)+ B(g)

qlel flgul Hsl, + g!=Jtrl A-*HE AG=AH- TASE ol Lt olg, pl
=-d
gl+. rslE sA.17^14 se.rs^l
+6I"1 4l4}e- + e_-E-pEl + il
*4 ae er+= Eg + 9l+. lo(l)

A(l) + B(l)
A,,.,,,FI=0 ?lqetrl [eJE zlxll. BEel re] poll,\jl (5A.19)
=-d
,l4l^JEJE Ezl¤ ^l-olql {ls48"l Sg ql= eltr-tr]]s
4lel g,* {lRulz} 0ol+. u}+^-1 ++lE QIE+q= H6}zl fa sA.10 Eeoll^1=
:d
EE Asl 7li1l8 slqt qEJ!¤"t glet
g:e-EE gqlg "JezlE gtqg d4 o + 4lel flEstrl tr1EJ!¤o1 ,Jtrt.
EEol
-del
ttllE 0l i+.lg Dl'TtTlxp dfl:eltrl'. SEI|E
=^H-g =71
+7}ql 7l"JE+. 9l= Ael alqr qEJl¤g:. FE g|.eloll e-l=dtse e4ill AE al* ulEJl¤g:
?E gal4 Es^l= + ?lrl.
142 s tr!+=EE
pt ill gta3
ceEg +471 Hli* +aI =g Raoult9 Hzl¤- 4+61 g
qE+(rB se.rz;. +++ AE+EI ++{} Bvl^lql ol=E
dill ac ¤qqlî "l Bzlg "J+^l7l= E_6J¤¤ ol8 EE
8
Bsl ol+l. qL+ 이붉은 T조유사 성분
,
flir
6!
tl tr otpi
TE H-i
pr 용액 ,
Av ~ BB
조건
Asl zttrJEt q 5A3 P PATP = NAP* tXBPB*
=
+E gal
+++ Hl4lel +rl "Jqg z5rorrolr ++.J rll
2o"Cql^J
Ael EE, xo BHltlg +rl "Jq ? zttorrol4. ol + EAq H gEl
=
lg sA.n Raoult9 E=]ql E6lE 0184 2dE 0lF= F ¤E
Eqlll= rb"n,.n*=r-ethyrbenzenw=+olq tr|4 J ol g*E +
+E graje dE=E E EEoll =--J-
laE Eill oJal q^l
ulall-dtr|'.
ql^Jel 4 C+EA Zzl "Jqe q-S+,J"1 ¤4.
q! -d
=el =71
dEg Hlell-dtr|..
= =Eoil pb.nr.n. = * x 75Torr - 37.5Torr
Pmethylbenzen. = * x 21 Torr = 10'5 Torr
ol g6JEE Aill +rl Sqg +8rorrol4. + ++ +71 "J

',-e. +E sqq cE(Eq lA)ql q4
qg Erll 9*.o
60
+71 +E 5 EgE=g trl-S4 ?"1 94.
t
o r11t
Eoo xvap,benzene -- Q7.5 Torr)/(48 Torr) = 0.78
mi
;n re] ,r
20
xvap,methylbenr.n. = (10.5 Torr)/(48 Torr) -- 0.22

0
0
oll=JEl{!e.l
=
EE, x(C6H5CH3) +71 +ql= B+ trJ fltsc?l cgHldDol 4 *ol +l9l+.
IWAdl ) =
fuA ( y )
fal sA.l2 Hl+-zr e4^11=?.! Elflzl oll=JElfl(=+g!)P Zel 0lAi4oe =
MA
0
(g> tRT MPA
Raoulfis law
-dE6lq, 0l=el a¤oll ttt= g+ EEI= 018 Es4el A+q Hl^dE[. =
/nAocg 3 tRTIn atp RTnAX *
PA =
/ APA
=71 ~
+.+q a+qE se.zrzl4 s/^.zzqql els}l^l +94
ol^J
*
/uA ( l ) =
a3 ^l"l cBqI+
p;(s)g aZAI+. I se..zoarlg pi6)=pf(l)-Rr t" pi{ ,J 혼합물의 조성과무관
ol l!.tl sA.2gb^lql -+q q+4 ee llg g=+. …
1lo(1)=p.i(l)+RTlnxo +-E trlEl¤ t018 Eo-{l (sA.23)
l,itsl
Po
ol {g +Eg ael6l+ Eil ol+q= ql$6l +s6J ^l
ol^J
#o(1) = p; (1) -RTlnpl + RTlnpo = pi (t) + RTln
p; oltl f-.4"1 ol o + aelq= 44zl qfl+)
"l+(El+^J ^l
Îd^J !3
ol ol^J4"J zJi.ll= zlC6izl g:e_E_E sA.z24E_
(sA.21)
+ q =-3 C9"14.
olxll ulzluJ'J4lE +rl "Jq4 +.J "_4alE ac4E Hlql gz1 ;6ql^l g rll Raoult9 Hzl"l CB6l^b ag +..4e1
¤e4 Îdg ol+++. ="6r.Ê sulqlzl Francois RaodtS rJ flE +tlql ElzlE +Ael -tr!+ ql+olc|. t*+ +r[ql^J=
tr_ tr]]+ Hl*6J .4i]E(qlE^l ud4 E+el)E gaJE¤ zI Ezl-$ol +A^JE zlzl4 olql 6]]R6I= tl_E eiil=
zl-n oJflE deg 6}*.sq, a 4+ 4 cEE ++ glqr+ =e6J
zlzlt- gl+. r4 a +71 "Jqg ol Ale+ Aflzl E3 QI_= +
++EI Eiilel +rl Erq49 Hl potpizl +qq +ql il= vlql .rg-:"lBl= a6}g +4.11= 4ol4l E + fl4. ¤-¤ol
AE E +94 *rl-4 + A+= 0 ga4H+.+ =q r= ¤zHts trI= +4LA6iAl t EzlE qg A+ a1ol ¤-,ll +
^l-¤g
*4zl zl# Raouttol E?slol+a +s= r+s=r+ Ag S4lE zlg+E 9la olH +E gleq Ir|4^J +"lc ++¤l +'Hql
ga6J 4"14. Hl6ll^J gd q +e^J6l+.ole+a."1 ¤-e49 flEeq7l++
용액 내
혼합후 혼합 전 .J +rHE eul-H-4 Hzl trl$ql +aqg +Eg ¤r6]l^J trJ
q1_=
pa= xapi Raoutt9 g^l [0lA E._q] (5A.22)
A 성분의 - -
순수물질의 증기압 tg tl_e +ElE zlzlal-:1 a1z1 ?*= aol+. HF+q '5"t8 ¤-
부분증기압 ol E!$ :H sA.pql ¤¤6I +gI4 .J+ +"1=, 561 j1 .-q
+E +,]|= ++6J Su]]tL4 6zl "J4ol *g Lo14.
이상용액의 홀합 자발적
DG =
MRTENAluxa t xBlnxby
용해 sA E-srEoll EH-d EEtrt 143
DH = o
DS = HRENAlaxA tdblnd∞ 3
500
5rll
400
0lar4 E3 E.4
orB6r=J^ (Henry)
300
I
o. pI
¤ mi
gi zoo
\_* 6n ,\tT.ll _QoH
=/'il o -
0l^{E
100 018 Eo-4
(Raoult)
/
0
0 olBaFJê-l x(CS,)
0 Bel EEE,X, 1
= =8,
lg sA.13 ul+6|'^l Lle o-qilF=3 01.8.8o8+El rll olEJ:.Jtf(o| rgP ral sA.14 -d !E{Ent|)o1 71E ++-g q= d$el=71 g+01 E E$oll r
q-).
HlelldE Hlell Ar+E pilg.l ?rl-(Raoult9 Hrl). 0l dEol AzJ ¤E(EE)
0 lgslEJêl 0 l.^1180il EI1EI a0 |
g nfl= a=71gqol qE6l E EEoll Hlalldf^ltrJ 0lnH= Blall di+7|.KBsl"
g^l).
'2Jcl(Henrysl
"J+ Raoult9 Hzl "tr.+El a{l H.qU+(rH

+E9
sA.13). fq+ ol B49 "J+^)717\ *61-= A+.tlE 4e}9.
-tr C$(+,ll)e 4E ++6t41 g++ ol Blg q I

=afl6t=
g EtEtrl. "l H4g +6J Bzlel E 6l-+E qlolq(ol7l^l= a t
xA+ 1ol E++ tlelszl +"td+), *"lol #qA++ +"1] .i Irt

q ¤ 4+s+. t
대체 I il
(b) 0t84-f;e EE 용질에서는 -
X 를 몰농도로 가동
I
-$¤E Sr|]e+ ulafzlzlE Raoult9 Bzlg I
"l^J +.+ql^J=
EIE+. rfl+ ¤Eel p}elzl- Wiltiam HenryE bszl- *g d
zll +.lE A+ +e 4 *zl g}4ol r g egql Hlql6ITl= fg sA.ls fr= E"4oll^1= Eot| ErlE(trPJ +)01 ++El EDHOll^1et 71E
Hl*-d E3 +oil ?+. ralLf Etr gtsol(Ea|.^4 ?=e ++-Lf Etrg nt|e[
6Izl"J r Blql *izl ++qI ^JEHqI^JE +71 "Jqal +71 Ed 80|-zf Se +oll 9l7.ll Etrl.
=
?*+= ag deg F6ll^J E}H+(rH se.t+). ol4g Henry
9 E=lol4z alQ rlg-a1 e.ol 448 + 9t+.
ㅇ Ps= xsKs Henry9 E^l t0184-EA E"-41 (sA.24)
g-¤ ExIzI +,]] tszlpi Hl+B ol. +eE Raoult9 B4g
ffi {olr}.
9zlrl xuE *¤9 g E8oll, KB: "J+9 ulql ^J+("Jq
E qHldg *=)-e^] s4 *zl "Jqg r E.Egql q6H^J E@ Raouttel E=lEtl-tenry H=.lE EIBC E,r[
E^lqI 44zl xr=0oll,<Jsrl de +dql dd"l qE+ +l6J a u *¤(o}^llE A)r+ tr- E
-e +(=EEsEt, c)r+el
=-ts-Eql
olr{. Henryel Bzlg tr}4^J xs-+0ol g++ 3 "*= +6J B ga,]Eol +4rllE 4 dEE +E "Jqg 3s'cql^l
=r7l
zl"J 1o14. XB CB] / 0 +a6}q q^q-4 ee ¤r-l¤ 8fl4
. Lotmlldm
= 3
+eg Henry9 Hlg qe-r +r1]= Raoult9 H4g trl x6 0 0.20 0.40 0.60 0.80
생략가능 0
1
s=.g6JEg 0lg4_# Eo4"l{l. qI+. *g r-"Eql^J + 는 psll<Pa

C
4.7 11 18.9 26.7 36.4
++= +Al-]. +{E "lelil Ce(+, zJzl Henryel Bzlr+ p^llfia 46.3 33.3 23.3 r2.3 4.9 0
Raoult9 Bzlg Els=)g *r]| EzEol ffal Eill +ql^J
!+%be-E CEg Raoult9 Hzlg E}+^l7lr. 4
g =z116l-=
C# Henry9 tszlg "J+^lAg +t6}q+. Henry
^l +a Ezl¤c *"l] Ezl-==e EqAlq
++6J ^Jqlql^JE
+Ia$ d-"i g+zlzl rll$ol+. ol ql$ql +,H= ++qI o+ill el Bzl t|+= +6Iq+.
e+ 49 Hl+6lzl qE6I^lRL +e EzF= 8oI EzLe+'l]+q 양하여
l.alg AfEi Raoult9 B44 Henry9 B4g E+7I Y E
ulfalzl g:c +, ++ql tlE}le+ d-.1
[ 위효로
tri= ]
¤5-g 6}rll gtrl. 용지 2
순수 . 여 용매
활동도 ( a. Er 3 )
용매에 대해 aA =
AANA 6 활동로
계수
질 aB =
NB CB )
G
14t, 5 E!+=# ←S )수
고몰동도
pure lL ) 계
pure Plpo Solute CoIc Solvent X ,
.
g =
E sA.t 2e8Koll^1sl E0ll 7lill=sl Henry E=l A+

+rl $qg g +gql q4^l E^lt r4sE Eg +E}
장수
Ell-d
K/(kPakg mol-1)*
Lil= aol+. trIul^-l ++ +71 "Jqg E. +gq q6il^J E
rl"llot +4. Raoutt9 Bzlg aÎ6IEJts 4 d+ql 4+ K/(kPakgmol-')
ol qlolEl= zlzl:t_
cEol r+"JsE r gE(+ CO, 3.01x 103
=^116l+
Sollg 4+61-b ¤q)ql^l 44. p,-76p."11 trIs=zlE u_ H2 1.28x lOs
H ¤+.E Henry B4g a l6IEl4. xzl *g ¤9,4:z N2 1.56x 10s
CBg *de'l-= + 9t= gqql^Jel PE 6zl $qql o2 7.92x104

4g dd"l q= h=x{tE +6ll tr-E ¤+. . zls eql q ++qq ?i+
"*e atEol
Eo! EllolEl# Raourt9 Hz.l dEr+ 6}4l rH sA.16ql
E^16I9+. Henry Hzl tl+= oI4lEE 4* Ko=z4.5kpa
d+ +4e_E= uenry9 Ezlg Se9 EgtE aE zlzl
ol{ pEE-r$E a+ &=23.5kpaol+. a pu=bu&4 Aol +4U4. ol +qEql "J4+ Henry Bzl ^J
50 +el "J+E E, sA.lql +E6I9+.olag ole"6ffl +ael E
p*(o
Eg4 a +Al= Eg + 9lg +"J "lq+
+71 "Jq ^LolE
40
p*( =\
7lillg 86flE(Tlillz| $pol+)q +il 4l4IE B + 9l+ e
ol
L
!
o
30
.4o14 zlo}el Tlillql 46J Henry Hzl
^J+ql ++
zl4g +
ou
a
K0l al S;5 614+ E"4I9 p "Ie+ ?ol t!}E ++ "J4"1
ul
Sro C^Jg a+9 sgg b6I44, zlzl[] u[;]zllE lt¤¤ EB
++=)
10 a+ql +.q6lal 4"J+.
Henry9l
0
0 EE, x(CHCl3) zttrJEt 0ll sA4
=ee+=e] =
lal 5A.16 SrTl 5A.4E tjlolEle+Ej rE! -=EEEEHEaI=EEEIIEJ) 2s"cql^J 6llHtl-"ll^19 ++ "J4"1 zrkpaol4. ol
{}êl
r| 01.^1lE{seiiJeJ g+ +c. _E710il^1 trE-d Hl.et
eol Eg E-49 =dEsl
+E
g+= slu6l'E
=71KE
'2JE +g + 91tr1.
tlÊ Eql ql+ E s"6}|E= +6IejH e$q tr|S {g
=71 4 4."1 Al^J ol+++.
4*1 x_tol4 x=0o EpEl a#"J Hq+E Raoult9 B u - Po, - 2lkPa o
bo': -,
= 2'9xlo{ molkg-'
44 Henry9 Bzl-qe.+q ral H.q*+= ag ++6I G= z9*ldkl,"k*-ol,
¤4. olBl6J H.qhlq +4^J= Eq sEql^l ¤B6Id+.
sEI +.-49 EBE"EE tr14^l 0.2emmolkr'ol4. ol t.
\l7lg.7l5A4 2s'cql^J +eq +ql gl= -EE- E-!-o E_e. ul-Tzl +16l]^l "l #g +._4el eeJ "JE=
=.q =sEtrllts
E +e "Jqg qq g +gql^J +C6Iq q-q',r+ +e 4 2s'Ce-l +++ E9 "Js p-o.eezkgdm-r+ de4 " e e
4= EH+. 4l zl-Ct+.rBlE teE +tsEzt trl-s-r+ B"l ¤4.
x 0.005 0.009 0.019 0.024
[O, ] = bo,p : (z.9xt}4 mol kg-' )x (0.997 kgd--' )
pll<Pa 27.3 48.4 101 126
=0.29mmoldm-'
Henry B4 tI¤+6lq+.
BdWS:E
T]ILJ=
=s-d
D l. .JEeE EE +tr|= ol Edol g6.JEE + C+"J trll dill a 2. trt-q tr1EJ!¤g f, EeE EE ciuus qlHzlolq, ol CEol
+i4q zlq6l+ +ElE +ElUrI. {zll Gibbs qlLJalql 71016l+ AEE +quq.
sA r]|El EE+ 1t+5
=-EtEoll
tr3. EI+ qHf¤g Eo.J ¤4 tr"lo.J edgl,tl gqql4 o$Eol E Eg Î"lE S4= +4utr1.
eCql qB4l E=61+zlE 444zlr t4. tr 8. ol8 EEe Aill
=C ¤qql^l Raoult9 H4g EI+^l7l=
-4. Gibbs-Duhem +E dEEE E++ ElHl¤ Esi +Eoltrl. d4l +e4E a+ql= slE+E g tsgol 1-e d=
^.l3 =qlE
7L qBrll
^Jssfl qizlE trq=q(q= E5 ^"iaqs. -J oll"J
^JB6l-b 3aJ Hzlol4.
+El] 4+gtrI). I e. Henryol Eee +eq ?zl $44 sElE +ql^19 E Eg
trs. 9d zlzll9 cibbs ollLlrl= E"J6J sqr+ gEql^l= rI"J9 +41= +ElU+. ol H49 ol^J4-Bg +Eg CE
:- (}"1 =-d
.$"14. 6E slzlr a3q.
=A7I
tr6. il¤+q sq"l +"JtI $d zlillEE s!=eu15 "3=o1 tr10. 0184-# EEg *3 r-"E9 +eql= Henry9 Hzlol 4
q, E:d g!=tr!= 0"14. =e
8qr" +rilql ql6li^]= Raoult9 Bzl"l CB6l-= +Eol+.
J7. Rao'.rltE EElg g6JE +ql 5qfl= C+E 6zl "J44:u
ㅡ
=s-d^l=
,(ide,
zl ,\l
-1 +^l 4Ha
( :
Eg +E] V,=(dVldn)p,r.,L AE 5A.l
slql slHI¤ p,=(dGldn) o,r,,L a9 5A..4
Ai-ll Gibbs "lluJzl G=nopo+nopu C 2c+ +.1 54.5
gqqE 7le^l dG= Vdp-SdT+ podno+ pudnu+ V sA.6
…
Gibbs-Duhem Z1np1t1=0 sA.12b
^l
zlillE +q EIHI¤ lt= p" +Rf h(plp") Sd zlzll 5A.15a
¤oJ cibbs qlqzl A-i*G= nRT(xoln xo+xu ln xu) $d zlill H ol^J4 g."1 51^.17
goJ QlE +El An.,r*S=-nR(xo In xo+xo Ir rr) V

9d zlSl "t "ltr4 ¤L9 5A.18
eql flBsl An',oH=0 ㄴ $d zlill H olt4 *"1 5A'.19
"l^J +Eql dolld, xo+ loj

Raoult9 Hzl Pe=xePi trllE +'J Hzl 54.22
C+9 El+ EIHI¤ 1"r(l)n=/.ri(l)+Rrln x^ oltr-+E 5/..23
Henry9 Bzl Pg=xttKs ol{'- +Eql 6J6ll^.], xu+08 trfle_l +* Hzl 54.24
gastgas
)
EEJ 58 EE"I ¤tr ( 용질 +
용매
¤zlrJ *= +++ EillE _E^l6J+. E-E.¤ +ql= 4 CEE

> ol E4E El|+ts ol* E ElqL qfl¤g 5B.rzl o + +ElH + ileq, q-4^l dill
E-dEr+ A.-49 FlElollll qel= 6[q, ol=e] Idol
=+4 -]rtsE Gibbs 9lHzlE trl-s=4 eol g+.
olLl oltsE4 aP EEe4 ¤troll olE gsg ol^|ts^lE olE
A0l 6s6ltl. AsqE El tt|trJol dtre dF?l?lt1l, r6 Gr= nnIti+ RIlnxo) + ns\ti+ RTlnxr) (sB.2b)
oll^lE 0l dE= 0l86fq rExlE =s:d
E tra.I3 e8g + 9,1q.= a
0|tr[. gEt cibbs qlHzl= ol F "JE 7le+ ?Je q, u}4^l q-s=r+
?ol S4.
> -e{C 7llLJ
Eg= +oll Eq?lts Et El-+ tr1El¤.3:ziol 4 A,,i*G - nRT(x alnxo + xu lnxs)
=trel =ol?l=
Soll^j 596l'rl. E-d Gibbs ollH^l iolS 8'-41 (s8.3)
> EJ.e.E:t qlHl rl^l 4zlrl n=nn*nuol4. rr|+^J Tlillel A+e+ u[]z[x]e + E
0l EEe_l 71571El= ,13 slqt qfl¤01 E Etrt trzlEtrlE ill9 oltt4 EEt ql-E +iil= ++4 ?"1 ¤4.
Raoult9 E4(EE sA)oltf. 0l g=lel 0lgg Gibbs-Helmhotz
l/Erl
---r\4---1 ?tr\?L a616[ rJE{A{oll
Jtt-l
nl+lL
-l,rlL
o}Alol
l=--l ="Le
sle nLe*rHI rle.rl
-lr-1.
A,,iJ - -nR(x olnro + xrlnxo)
- -tudvl
ol=J atl= g3 zlx1l9 tsEg trll olEqIE a4 Hl+il aE ?lEetrl [018 E"-q] (s8.4)
=*ct
=Et=
?lrHEE sA).
f4E A-i*G= A-i"H-TA-i*SolE-tr oltl-4 g.J elBtl
A*i*Ht- 0ol ¤+. el$ (aCldp)r= yolEe.(3E.8^l) A.ni*V=
(EA-oG/dp).o14.rq+ sB3^lel A,"i*G:. "Jqql ++6iE_tr_
gqqtg ol$fl1.<J
"lill gEIEE C49 olafltr + ilqq, + olael glqq S{ sgr+c.0ol g+. trI+^l A*i*v=Ool g+.
++ q zlzl zfitfi$ ols" 619 dill qL+ .I+g ¤:6J61]^l + sB3^14 sB.4^lg + Ed zlzllzl E JB *llE {4 +?Je
E+el+ q, qE|^J 9d zlillE a+ql gflH -EE eEE"l qzlql^J
E r4E- 4+g+. E6J flBul7]. 6olt: e ++lE Ql= e
=
5B.1 Ei{I EET= vl Hslz} 0ol qq q4^J EJq gFqol q= 43 "J"J"l
E-"1 5l4l"J ,IE fltr+ul 6zI ulE.J 4"14. rBl+ +qqe-l
{zlriE s-Er5ol4 +.-4 +ql Eqil= zlolT} fl+= ag
'1]¤+ "l^J4 ^d+ "ll.}^dl} zlzll9 "l^JC Îolql= E¤+
("171^l= I+r +eq 2
^JE4lql^J= I:- e E= Boltr|)sl
+E6llo} 6J+. + Sd Tlzllel a+ql= Ezl¤ ^l-olql ^Js4L
slql ElHl¤ pr olaol ++ts *llel Zlpf, :afll EqlE +ql
*ol S.xl"J "lt +._qql^J= tszl*"] glsq +"_{ql^JE
rJg E E¤ x,rlolsl trl-s +4l4sE+q drH6ll +
?J
"laq ¤* e-s ^}szi*ol + ++EI '-4illql^Jel ¤+ A-A I=i B-B
{ol'Ll.
^JE4L+r+ a.9 S"l+. Eql Gibbs 9lHzls+ QIE+qE =
triqf 4EJl¤ t018 Es4l (s8.1) cql tri= H+= Tlzllql EIql a4 ?4r:B sA.74 sA.e). ol
h= Hi +RTlnx,
+ rqsE qzlql qEol dfl+(rB sB.t4 rB sB.2).
(a) ol8 Eeq EE dE d|^l tr-+ s-¤4e +qoJ'oltl Tlzll' Elldql '$
d zl^,ll'48 +q= ^F&61+ ag HIE ilololEl6-J ullEol
+ a4i.llz} ol^J +Eg EIE trllE E_6J cibbs otlHzli i zlill zl*"1 olaol
4. "lt 8'lql^l= trs llxl"J de4sE
ql ql6J a(Eq sA)r+ +ae %FB " _+ ah}++. eq;llE"l s E= +E $}"14. 9d zlillql^lE {ta 4i
.Jgzl ,sE Gibbs glLlzl- tr]-s-r=4 e+. Îolql^l E"J6J
¤¤ trzl"J olL"l 15 ool4. r+lLI ol fet +Eg 6I
Gi= n,r4i + nRt-l| (sB.2a) 4= ÎH-E-ol
9"I S.4.
sB Ee40ldE 147
TO
G대
는
-
d ,ll EEElzl ?+a s6lEl Et Elq+61+ rll zl"J6l+ sl

0
d ^lE
E +rl HElr} ql$qTl aAl +z}6}4+ E-=
'1El*+. "J"J
-0.2 Ql-E+El7l H Aig ullH"J"JolEol zilHl]gqq a^J4 E
l- d¤e 9zl ullEql) gEL Gibbs qlqzlTl "Jol ¤ f :14. ol
I
E
o .=
-0.4 4Col e6lel zlB4 " e "Jq+q + .lill= 4lol
tr]]= E"-l
zl 9+=+.gg qlaE a^d ¤qql^J"J 4olb ?== E-etol
E
-0.6
\
"JqB +E gltrI
---/
I
-0.8 0
AE
0.5 (b) Elg :Et+st E+ E4
EE, xo
=
fal sB.l + Ei{l7l'=-BtElol 0lAf E-q= PJ= ttllel E-d Gibbs ollLl^1. d41 +.lE gq+4 ceg ztg :d+ rE z$l:t- +EtB
+ 914 4"J E'-++ dzllE E6J gEql-4 'J+e+ "l^J +.+
ql ql+ EJ gqq}4 Er+ ilol+. +
0.8
ÎolE
:Er+
XE = A,r1*X - A-,,,X'dt"l rlg tgqll (sB.s)
0.6
qlg^l rlB sl=eul sE= 5B.+zl o + folzlE A*i,sd"d9 {l
/ \
q
o.: o.a
I "l$a}"l Zl&g + 9l+. 4"J Qlgrle+ +rl} oltr-4"J
E a+q 0ol qq, Irl+^l ol 4"J EL+EE {te +cile+ a+.
re sB.3ql r+"J Erizl. adql E=61"= + q]= +4'll
=i
0.2
fl4. :B EJEqI E46J'llolqE
sB.3(a)* Hlr$l/^l=Edll1
++B 4"14. rfzl "Jel <t¤- ?*+ 4z a,"i*H>o¤- 9"la}
0
0 0.5 q, Eo.JEql^JE A-B tls4l+ol tffl E{l(++-J Hl4l4
Ael EE, xo
=
fg ^l.sdl&) +ql^J9 e-e$ B-B ^JszI+B+ E6I+= a
sB.2 + Ei1l7l.=-ctElcl 018 E-{= uE n}lE E-or glE Ptrl.
I 9"1t4. ril]l +dol qla E"&g +4'H= ag A-Ae+
B-B tlszl+9 ,t'llzlEol Hli6l-71 trll$ol4. :zB sB.3(b)=
zlElEt 0ll sB.1 ㅇ E E¤ol H

¤ql q+ H+g Bq+= 4o14. ^l=Eg+el
,ile{dg g trll= qlEilE+ +.llBol TI6l]Aql
Hl4l4 *r}4_o + "l,d. +._4¤- "J=+. 1.0mol "++ +449 +47l +
$ cunull)el 2.Omolel c6HscHr0)E g'Jfl+I. 6IzI. ol ralft.rll, olag^lp-a¤l+9 Ezl¤ol rBl +a ullEql +
DF
EoJEql l E x6.n .n,n = 933 o I a rmethyrbenzen* = 0.670 I 4 . 25oC 테
ql^l= RT=2.48k1mol-'ol4, ¤.* CiUUs "llLJzl4 Sl=+ A -
B<A -
A B B( -
양수)
irl= r+q=+ tr"] ¤4.
800
A A
-
)- %"
,
≈ B -
B ( 대칭
8
)
IT II
4
시데 7 시
t
A,^,
mlx-G I
n = (2.48kf mol-t; x (0. 33 ln 0. 33 + 0.67 ln 0.67) .i-
o
=-
!
Eo
1
= -1.6klmol-t E
-) +oo
E-q \ /
E
A-,J/z
mlx
_ -(8.3145 J K-r mol-r) x (0.33 ln 0.33 + 0.67In 0.67)
= *5.3 | K-t mol-t
I
-8 q
f
gq} $gyl} oolr(oltl +.49 zJ-{ap).
용해도 에너지 관점 DCH) 0
-120
< 부질서도관
0 0.5 0.5
(a) x(c6H5) (b) x(CrClo)
예측 DLS )
m
b
ral sB.3 2s"coll^1 alg Er+. (a) flltl/Êe-dltt Aloll cH:d HE;
=8-.J
LG
dxll ¤-.13 A-A, A-B, "l DHÎol9
e-e Ezl¤ TDS
{ta$$ol e
= -
0l rallE= 0l
=-stol =E
al8"J= LfElL.lrf(olar E-4oll rH6|1,\1= A,;*H=o
자발적 인 ㅅ olEe). (b) qEaF=E_eqlEJ//.l=EEJlEJ Zloll rH-d rl.g Ful VE; olre}ls=
+ ^Jol6t+. trl+^J "+iilE"l EqlB d
ql= flBqe+ +rl7t E
용해도 영양주는
ㅗ
EllEeF=trEollEJg EEol H= ntl= +tr| 'J47l'gclLlr" tsE 요인 q= +q ㅇ
sI+ g"J =
"tqr+ ¤I ++E Ez|5"1 +aq Aill t+ql +"J6I 분리는 무조건
)
e7 2 I "Jq U+ts ?,lE EGf c(0 18 E.-4oll{E A,i,, V= 0 0 = e). I
용심에
~
(
) 친한경도 용차용질
애용했황리
>
응응 8 orl
I 용많액
용질 000000 - 에
에+ DHztDH 3 =
. . .
(+ ) (+ 7 c 3
2
) 압력
임영 응용 용요응
가장 애니
잠양 작양 큰음
-
.
. → 00 O 0
O
@
ㅇ
DH 3
[ 큰 음수를 갖는다 .
3 ) 온도
@
0
00
⑥ . @
- > 용배- 용잘이 합쳐질 때
안경화β 그용체 -
용질 헨함 )
1 름이 물이 안는 .
7
이유 ㅇ . 물에 안욕응
기름끼리 뭉침
므 →
O
ㅇ ㅇ
148 s E!+==:# ㅇ D
" ㅇ
V
⑥
O
신녹은
⑧
0
물
상태 →
. 기
이 기름 표면적인 S 친물의 수 ↓
:
w ㅇ
은 SX . ㅇ
V
기름을 줄리싼 00
안녹을 때 가 P
∴
기름이 물에 물더 s
+al *olzl * 6Izl"J qlEeffi++9ltol zla1dq q+ +

ㅇ
+0.1
> 재발
{¤ol q il"J6trll +"J + glrll Elzl ull$"lr}.
ㅡ 3
u}{z}xlE 0
rll=rEe.eql+el E Egol * Ell= ,r.lp_e.sl+ol zlo|l 2.5
t- -0
4ql q+ +aIE tsulzt fzla}Erll, ol49 q|E;F-=.tr--tr.ql e 2
E Ezlzt 4E B46]]^l ++$ +q4 +ql^J= E44_o e + o-0.2
.!
olzl"J a?]= 4= Ttqldql ,rl+ E -tr44
E
-0.3
\ ---_=_ 1.5 //
= ^l=-e.¤l$ol
ㅡ
o + $olAl r{zl ull$ol4.
4.4
1
e-7el
"lBal-b eE= =-r 8.49
4"J Et+z| oo ulol
tlcE cEE'l4u+. olal6J Hql^l fs" 6J E¤ol q= al -0.5
0 0.5
ㅇ
z| ulE $+ E4oJrll, ol +Eg HE*oolzltrJ SE=6ol q=
x^
8._4o]4. 4+
+._qql^l= ^Js4¤¤ol ,rl_e. +sH^lE lg sB.s qa1 Atol-d 4efolEj
6'Joll^lsl E-d Gibbs ollt-l^|.
=,
+ ++E Ezlzl +zl{6}rll(oltr-+aqql^le+ *ol) +;r¤+.
4-J ++= a+ El C%+4 " + Eel6ITl +16}ol !+"J qlgrl ql 612! A+, 6J +4zl 991 zzH9 a|zlzl ++B
z[ r].e-=4 t"l aC9l E=ql+r zl-C6}l _H-z]. ㅇ +==4e
다
aol+. olag ¤rz"J a+ql= o1 Alzl "l + +idql
0gr' - n(RTxoxs (58.6)

6]l'J6l+ a^dq + +e_E zig!_e_tr_ +?]Hg g"lal* 4,
~
ol+. + ol E4z]. ololg+eEAl alel Gibbs glHzlz]. aiq

trmensond
…
ql6J A-BE tr-44q1 tls
¤zl^J 6= A-Ae+ B-B d-sz}+ql
noan -
~
=
aol+. Eq scql^J "l q ¤B6l-a+. d#
4I+ qlLJzlE ++q= +_qfldel ul4"lqq. (H'= E C
ㅡ
e."l/ I u-llt:9l n= "J gxT.) 5lr.o,:.i " .- /r.d"J yf-r-= __rE

,l^l-l .\ H^l-l ,lA- .-lzl+l +lA:
GZEU
-rln-r-l Î -al
trE EEou EHEI trElorEr
se.agl E,rlfl|rll, o14.3 rH sB.3(a)9 ¤E +d4 Hl+6I ^rE
2s.cql^l Hld4 ¤.'JE¤. Egsl6l-= ql 4
s
+. "J"J 6<oolE, Ed.g Bg4ol4⑤
~β~
e-s tl.szlSol e-es+
B-B tr-s4}+ql HI6I]^J EJ r+.*E 5>oolE gEL"l ¤:g4
^l==E4&E
-J6J ir}4"lEl 6el Ag "Jotqlr 5 E gql$g
".h=
,ilel
ol+. EEL flE +tl= C+ +a4ql 4* EaJ ciuus ollHzlE 4l&6}q+.

"l^J4 4I¤ zyzl', e
zalg ,t.l¤f rB sB.3(a)E trl +dol +qql^J +4111=
…
EoJ ciuus ollHzlz[ ffi$ ?ol 84.

{}g "J"l-u ffi ol{g E "*s_E +E}l]ljE olol,rJ sB.6
AH AS
mtx mtx
(Rrxp)* "l+++. E4 aEe a+ +E* zl
^l(n'=
A.oG = n¤RTx oxu -7[-nR(xo lnxo + xr lnxu )1 (s8.7) a6}a E goJ Gibbs qqzl= 5B.za1 o + fqtlctz zI
- nRT (x eln xo + x, ln xu + (x oxrr) a++.
rH {4
{lolal 6 <}ql^J a.,i*G7} eCql 4a} H6}
sB.s= dEzl= -; xA=xB zlnlolqrl *4zt 4444' :_
…
=ol
lIZ trl+^1,
E E"}.g +4U d"14. ol :floll.<l E + 9l= fl z$l rte
…
z ro1 mol-'oll 714tr+.
+0.5
2
상오작용E_- H' b RTxAxB -
7ol I mol-'
= 1.13
AA 안상 trl-?+^J + gaj Gibb' qlHzlE
+qd aCg +srll 61.=
t-
q 0
(A+ +q{"J a+) r+g=r+ ?"1 ¤4.
t 0
-1 L,^,-G/n
mlx.z = *RTln* + ]RTIn j + 70LI mol-t
= -RTln 2 + 70U mol-t
-0.5
= -l.72kl mol-t + 0.701 k] mol-t - -1.02k| mol-t
0 0.5
x.
fH sB.4 r.lg glEJtrlT l (xoxrOl H le1l6lts sBoll ttl'= tt]|E 'J= q4 80 l-d
rPl 87[ 5B.1 rB sB.3(a)9 :z4ue+=l r1^9-=* n*
EfalElEl 6 rJoll E]ld|{,\l LIE|L.! raJ.
용질 용매가 친할수록 잘녹음
-
sB EEol 8E 1t'9
{i# eg + el+.
*** olxll
x 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 lill
aEl(;mol-') 150 350 550 680 7N 690 600 500 280
qil --e7l
+d_*+ %r"B¤- "l¤-6}q ol ullolElE¤. rFtn=Ax(l_x) El
E'
gs +EB sn.o4 ag ge] qlq. ,o*r
^lql "*rll 'lol
hii {olator-lou I 05e=V *iv [oE *tr i" fzlt tE ol=E

L[l=J =
E
순수 용매에 용질이 들어가게 되면

Tf', Tt Tb
:
8E, r
용체의 성질이 변함 lal sB.6 E-q +oll e4illEot|sl it+ trlEJ!¤e ++-d o-4i1lq
eg
58.2 Etrf '-*El.'jll4o+
=qg,l=
Eollsln|qt qEl¤01 ri{lE0ll9 ar+ trlEJl¤rl,Jo|r|
=EJd 분자 이온
그변화 .
농도의존 g
ㅇ
Ef,|¤"I* +.+ +q
=zfl6k D
ㅇ
*d "J"Jolel +ql"J s]=61-
ts .g._E(cl=
E)= Eol.tlrl".
-ss.)zl.-*o[^lq,
o-4r119
!E
=7le)
'*01-T.l tr|.+ trlEJl¤g
017i3 C=01 oJLl= zJsTl LleT I r1Egltf.
El+ tr1EJ]¤rl",Jol.^l= gE(g=
E=EHrl q=troil rl
=
g-3F
-7 -r.D
="FqlE ruqI E7l4 Cdol4.+A qlEql +4+= =
tr l^l= t1l,
[용적 3 ㅇ F
D q=d 48,:41ㅇ
ㅇ +71 "Jq Ll]g, #=A sE,
c.F"JEol
ㅡ
인력압력시 olBlal #e ol ddol4. +"+ql^J= C¤Eol 8d 9"J"19 4., *d"l ¤{|ts trlE +'}]9 Sl=e{= q *zls1o+ G
q=6}r l ="Fqls +S6I+.
Tv ⇒ 압력 이+ql"J
zlE qEj= A6Jol r"JE *olzlE 4ol4(_ze ss.z). -24
했 {zlrJE 000
+rll= A-e, :7?-lr +ag Bs +44zle. t4.
억
XAPA ④
a- +7lE Elel= A6JoJ oliJfl *"Izl4 *zl "J4ol *"I
PA ( ]
rleury 3
=
*e-s Eel{-= r+Aql^J= + 7l^l 7l4i=_ 6}rll q=ql, l

0 ( )
PA 2 PA
zll :zelai"l #=dol $olzlrll ¤+. nl.$zlzl-tr +a4ql^J
= E
6I+= +e3 Hl+lgcolq^l ol.+fl zl{r

~
=tzl.ilE
a}zl
. Ezl¤E ++ACol +z1617l ql$ql gq= 443o1 $zll
"
?+=+= 4o14. E 6L+= +AE.e ri.ll $uli +_e_E +ol-=
e
4 zlzl ?+eq,터
=
El+^l 8.lol g ull= J.ill +EHtrJol 4=¤

¤q. r a4 rille+ +"+ Î"lql ¤¤ol "lFol,(lelE sszl
rJ 44z}"t 6Lq, q+^J \.|.{ol 442}ts 4o14.
4E zlCol+. ol Ezil T}eol oll* C+ a tzl"J olBl+ B
~ #=d s#r+ q=d 'ilHg c*49_e 4+= 7lt a+
g'JEql^J ¤xlle gqu4. +d-6J +4g olao 6[
^Jol ""19 3 latm 6lql^J qL ^&++qI*o]] 6zl+ E. ++6J llz-ll +
H olBl6J 7l-ag ts Eezl $.zl"J r++r ^l]E¤. 44zl ,|l)E ++ trlHl¤ol +"4 +E +,llE sl+ irlQl¤$ zlolzl
4sxlb ?*=+.
(
0
증기압 목분율 PA XAPA

: =
(a)trB¤9 B=+ 끓 어 :몰랄해도 (온와 무관해서 볼람동도사용

,
)
-E= ¤+^d3 Sdol Eill +,He_l ElqL qfl¤ 상투몰공로

ol yfolzlzl qlEql =zl]6Jstr/Al +"1(Eq sA9 Raoutt9 pI pA
'+E}U+. "l^J
Bzl p6-xop;ql trls=)E a+, *dol trI= ElqL El
Hl¤ol +++ +"nql 4EI #~
=4]-lJ
piE+El pf +Rr ln xo-tr. fr4 사
trt
III
rtlltttlt
r N
ITI
6tzl trllEql +4ki4(xo < lolEr + h x6E ¤-ol ¤4). +eg DSK
IIIIT DS IrI
Q
¤zl4 rill +ql EqTlzl g:e_!_s +219+. aillg e+E trlHl 사대적 ㅇ 상대적IJ
a
sn.oo ++q "J

¤q 4d4 " + ¤6Jg +zl= ?+=+. :aB 7
불안정 안장
…
+ 9l= Hte+ Aol $-,]]9 +qL qfl¤ol }}a++= a + (a) (b)
zl-aqill ¤Bol q +e gEql^l .Jq+r(q4^l #=dg fal sB.7 #-d

s4illsl gfajg 7 l?.lEl= +E,'.l ++lE
g+Z}+), -r.z-I-o-!i1l ¤¤c q *e gEql^l gqu+(= q +tr^1 #A,t p1g EB= LlElL.!tr|-. (a)="Jofl
=71 =7lel.
Gzl,i1ts Eillsl +4= q|E= 4^1.=
qlelt+)= 49 9"1'*4. 7ll.la_ 7tre E440+ LlElL}lHrl. (b) EE(TlEl LllE)o1 ntl=
8:+dpl ++:d Eilloll Hldt|^l +E ldlBl, rEl,\l =4-gSEHe
=aol
g.J qlgulzl. ooJ oltl+"lql^jE EiqL qHl¤ol 44zls
A'J6l +trî-zf
=71
Elel= 3EF0l 1UE ltolTltl.
-tr_, ol 44zlb g.Jg +e4 +q] 9"Jol5 L
Îols_l ^JA
!- ql$ol+I E + S+. ole+ *oJ alzj flolol tlRul s r rJ Tillzl o e ¤EalzlE slBul o.$z(olluJzlz| f$lE gB^l
"ldB
: PKO ATolq u ol g'Jg
= "l o e4 ++1E qlEeElTl H6l+ ErD "Lq4H 4lE EIE+'lql zlqlq=
$zl- + a
R¤61 QIE +irl tr44r -Boloi eI .a++r -Boloi 6J+.
현실 AIB 같이 있을때 중 기압에
F 이상용액
IAB 인력 ↓
U
A A 친한점도
.
AA
U
RA P, 친한쟁도
.
-
U
Pt =
AA 친한경도
l
BB 헨한정도
B 몽 " ~ 우개 더한과 BR , 현한쟁도 ~
-
1
BBD ㅡ
A B 이
0A
8
AB 친한정도
AB 친한정도
-
/B 의
x켜
양의편차 음의 편차
150 , EJ+=-B|E
A(s)
trX(g,p) +eg
dlnxo _ 1 d(A""oGlT)
dT -R d7
a
zt6l.q hxnE dlnx^ "J+ Hs|^lZl +qlE ¤B"l +
A*oH
RT2
zlqrll 617l fl6l]^l gE= trl-g ul-4 ar "J+ He+^14

l/A(l) ^lql
of 6J+.
A(l) + B
A"Id,
dlnx.
^=- RT'
fal sB.8 #=tr e- 4lt|g nlt= ++-d e7l1-
=^tl61"=
Aq Eq +sl
A
^l0lE
B-dE 8?l6|l0t EEl. q7l^1 A= E0l{0lr B= ulF-lgd Etrolcl. E4l 3 +lel 4+6Iq hroel 7 ÎolE +41= ++4.
^19
*.el 49 4E6I7l +l6ll^J, xe= lBEl, ? Inxo=0(r?-lr. 7-
ts g.E_E *b aol{. ol gEzl tslE ratmoll^J r} dolE "J ++6J Ael #=d"J re+q)+Et xot\zllgydol r7I q
s7l= ¤¤ gEolq, q4^J +"HE rH #Ed"l+ q 4E++. 4EE H+= 4+ A4 EEqzl flE$ lnxo
^l] ^l] =)h,/eo +, l?-]tr
¤4. E ffi 7'o + HlÊ+.+
=dol
(b)B#e= J'"'^
dlr,r; = -+J; 5467'
#= Ag ^J4g ullE ratmgl^l *,]| 6zle+ +._4 +E +r]| alEg 4E6LE tnxoTl9*rll olag h(l-ro)E +g + 9l
ol+qzl= E+g ¤¤g f E"}loF 6J+(rH sB.8). :1 +. +Hg 4Eg Ell= +g flgEl7l o169 9s ¤qql^J
^L"lql
4E .-,r* v4* trJ+^l7l= gtrql^J ol ¤eol ol+"lc4. olz-l*l.rl- -zl-z-l:^l-- z-ltJ -zl* rll-o= rUHlllrl
l'dvl!'-18/ l- n - -'11 'ilJ-1 .
=-O"l1JL/
pX (g) = pi (l) + RT lnxo (sB.8) 4E A.I

n= -28 rll
¤zl,tl pi(9E ++EI +714 +qL qfl¤ol+. Sqg dill \oH cTl
ln(1-x,,)= - ),.;rdT
4Cg E6l|^J latmolEE H^l6tzl ?+"*4. otqql^l -H-olA R
zl"J ol
4g e44 o _e *ull9 a^J #Edol ¤-47Ir, +61 :1BlE,
#e +e!el A+ql= ol g?+e"l +eE g Eg"ll Hlql++.
AuuoH
ln(1-xr) = R (+-+)
ol Al&g 6}i ql= +d +,HE slql qfl¤ol Eill =JAl4 #g +eqql r.ll6J
^J4 + =^l4l
7l * +ql^J E"J6lloI ++= ol.$aJr|(sB.s^l). olq olxll *¤el
"J"l trll+61 4lot^l x, ( 1ol q= A+E ^J46ll
^l-dg
+eg 7I*g trllE ol4ol E"JaIrll +zlqE+ 617l +16ll EzI. oltrll= ln(l-xu) =-xs7l44fElulzlE ^}^l 12) 9E ^l
^J ol cJ-e-$ *"1
gEE E"t4 Hs+^l4oF albzlfi a^|qi+. trl-g tr41 ¤4.
^l=
# tr++^l oleiql 4¤# +8.J4 4"rH
x
R (+-+)
E4l 1 ?ts ciuus ollHzlc| lnxo ^lolel +41
ss.s^19 ++4 rJol l4 + + 9l+ ¤-_L q #= gE= a+ +l-ql H6lzl g:e_E_E T=7*o14. 4
+^J,
lnxo =
p o
t) 11
RT
>t
4d
RT
I 1 T-T* T-T* A4
T* T:- TT* T*2=-T*'
¤zlrJ a,,pGE +++ +q](A)g 6* CrUs glHzl4.
EJAI2gE"ll 4E lnxoel Hq¤ +4r-ll= ¤zlrl Ar5=r-rolq-.relE *9 al"l trl+r+ Bol ¤4.
^1
+41 1E .JHg g=.91 +6il^J ul.Sap +HE e4ql
^lel
4 cibbs-uelmholtz 4(Eq 3E, (a(G/T)tdT)r--s1P)g 4+ ,,=A#.# (5B.9a)
^lA+.rflE
58 EEol 8tr 1s1
a
ol {g #=A s$r+ +eE E ege ^lE BIq++= a E sB.l q=E Lllal 8+(Kf)el.--:=E eE d|*(Ku).
g +"J6H=+.
K1l(Kkgmol-t) Kol(Kkgmol-')
E4l 5 C?-l H]{I 5.r2 2.53
^lE
Szlllzls) 44I A4ql E6lH +AE E ESol xu"J 4lE C 7LE
'E' = 40
tL #=Aol rEpq g4z}4, sB.ea^Jg EA A

?*+ATtr_ ql5 7.27 3.04
?-l6l.q ol +Al= q+4 ?ol 448 + 9l+ EI
서프 ) E 1.86 0.51
kbD
Tb
=
ㅇ .=# ㅇ
) . zl-e dgl El r,*-3- <i=ol ++Elq
mc용도 "J+.
Tv K5 A7i-Kr,
…
#: tr e= [otd EE] (sB.eb)
에
평라 ATo=Kob #=tr e= td-d^ll (sB.gc)
름 ( 용질부관
r {zlrJ Kb= dE4_o e d"H^J 4= +rllq E:- 9= 8+
sB.eb^le. +eE a" #ollE ++6}J E +gql"J e_l+6J+.
ol+lql q$ql #= A s$g +¤dol4l o.J4. ar9 <I +(g. sB.l).
^dA
g q¤61 +'l]E CAq el=6}q, #=Aol +3 +,ll"J++ zlElEt 0ll sB.2
#=d s-E Erl¤ +4,J+ Tiouton9 +4(Eq 3B)ql
= Eel #-d sE ++E o.sl K kg mol-lolq, trl4^J
96ll^l A,,pHlr= "Ja6I+ trI+^J sB.eb^lg AT". re+ e3
g-ol qq A,"oH zlillql= el=61-zl ?*=trI. BE g
0.10mol kg-'9 Eg}aEE +ee #=dg
Egg + =4161-=
0.051KI,J+ gel=trI. HfdE #=d sE r}+= tr"'J6l
- 0
olel EEr-"E 6ql ulfllale-E(Eq sa9 El4zI9
^}ll nS At'1 z.szK kg mol-,o]4 qq, q4^l 0.2s K"J+ g47tg
_H_oI+) sB.eb^lg ¤+4 o s or?-lle+ a.ol a,lrl ole" ¤I4.
4o14.
E+ E7}l
Flf /(x)E Taylor H-+= ol+6}q q+4 ztol x-a

x-I
=ilql ln(l +x) = x'+ *r'-... =it- D*' +
^lel ag
zlzlt_ +El.B + 9l+. n=l
olp ++= +61 lxl < loJ q= *rlzl_o + -of9 A o-J

r (x)= f (a,. (#), k-a). *[#) .(x-a)' +...
ol+ E {l 6.PtzlEJ f6llE 9zl 4lE9l ol -rfE ol+6tH
r,-oy' 4l4Fg ZI+61 tr + glq. qle^l lrl <l"J ql= q-q-r+ e
=; L({4) rayror E#
#"!\dr" ),, ol ¤ fz| ?14.
¤zld (. . .),= x=a414 7.J s.g4ol{, m!3 494 ?ol (1+x)-t=l-x

cEq= 4t+ol+. e.r= I *n
ln(l+x)=x
nt = n(n - lXn - 2)...1, 0! =I zt6
$61 a=0ql^Jel Thylor #+=

=-++r trlN/aclaurin 6J+ + #+q ++qE d*q+ql qEl ++t +A+
6Jol nol
*9 Maclaurin -"iE3 *e-E ol lz|el qBl *ql^l ol+ (tql d=6IH :z ++E +aJ*+r "Jeq. rq+ ++el
g+. Elol +.J+ +a <Is_E d=6}zl 9+g'I= gtl6Jtr}r E
6Jq. r?-l6}q (l+x)-rg lxl<1"J trll= +H6tq, lrl > r
(t+x)-' = t- x+ x2- ... =!{-r)"r" g trI= E4IEI4. +e q+= qel "JHsE +"JB + 9le
n=0
q, +ol n{|i$ $l.rlzl Hl++.
e'=1+x+|x'+.'.- $x'
Lnl n=0
152 s tr!+=g=
a
(c) olEtr ttlaJ (o) Ea[s

+c ql^J"l q= ¤¤e ++6J riil +ol] ee+ ¤-¤9
¤zlrJ +6|]EE gt:J6J {=$Ce olulzluJl+allE= +eE ++ql
E +gol xu?i 8o4 rlol9 ¤¤ol4r:B sn.s). q=dql^J rr++ E6lsgi), +lqlî
^l-s"6J
ar+ Hl++ ,JBg ol-a"a[fl
=
+ ^J +ql
=q
flE e9 slqi alHl¤E"l ?ot"F q!+. +, +eE galls.E +.J + 9l+. ri]l +eg Solls+ d+^l t
4 --eH *.-4"1 srl¤ qlt4zl ol lillz| +611¤ 4,o14. "l
/ti(s) =pi(l) + RTlnxo
0
(sB.10)
Efl E4q^l= +6119zl t*9 +44 +611¤ +e Îolql ¤
¤zlrl pi(s)E ++6J azll e9 ++ ElHl¤"I4.-"l ^lg + ¤"1 ol$qd+. oI4,tJ E+ +g +ql^l= t+6J rill +e
,le-l s+E ulHl¤ol rzllel sI+ slHl¤e HI+lq.+= d9 zll el ++ i4Hl¤ pi(s)s+ +aq +9 s9 s+ol trlHI¤ ttBTl ?eol
9l6IH *ql +S,-J 44 E"J6I+. EI+^l sB.eb^l o ++q + o| aJr{rH sr.ro;. pr= 8q4E E +gr+ps=Ilff(l)+RTln xu
g4 e3 a+= + HIE ¤ + 9l'f. e-l +alrl !|e u + pff(s)E q+4 Bol 448 + 9t+
RT*, qtstr Lflg

p[(s) =pil(l) + RTlnxu (sB.13)
Mr=l{'A, K'= A*H (s8.11)
4e * ¤ql^lE ¤E!4 As.q, +ofl AE+ltlql +e BE ol

¤zlrJ rb ++*.-4ill9 q.d, q=d 4H r-r +l#*+= d"Jol +e+ ol4ql^l Hl*qI ,JHg ol+6l.q
^4=
r?-lr Aru,HE +"He-l ¤+ flB44 ¤+ flR4z} *r + +6llEe+ s-L Îol9 +41^lg +E6|] Eolll+.
+e +,1]= q=A 4Hg +EU+. *'l"l 5¤
q= +aE g Egol= EB5E bql Hlql6l4, :_4alq +lE
=dol
4¤- "JHI4 o + r-l-s=4 a.ol 34.
¤zldh gE rql^J ¤¤g ol+r
9l= +"1 +e-l BE g +
O
LT, - ft,6 cl=tr Lt1=J [A-d^]l (se.tz) ¤-g 41416l+ 4."1 *4olr+. ttl+,rJ sB.134g rl-e_g pol
pl zlzla_
^l4l¤l+.
{zlrl K,= ¤e4"J oltsE Lt|aJ 8++(E sB.l).
pi(s)-pJ(l) _ At,G
In.tr, =
RT R7
zrtrJEt oll sB.3 ss.s^19 +Eltg olls+ a.ol ol ^lel "JHg roll $afl.<J o1
EE qEd .llH ^J+= 1.86K kg mol-'olq, q+^l E6Iq aC H+= gE H+e+ ¤S/.]il +¤-ql cibbs-
o.1o mor ks-,9 EBTEE +Ag q=dg Helmholtz 49 ols" ql4. olqrJ BE += ¤-E1xu= 1, El4^J
=46I=
0.leKrrJ+ rllEl=4. aiE=g qEa .llH tr-+= ^JB6l ln xu=6$ trll)+El +c rlltl gE(xB7J- OPel r ,rlol9 ll9
zlrl +or kg mol-'ol+ qq, Ir++^J 4.oKtrJ+ 4Eutg a zl4 $Dt|z'l 4+g 6H=+.
ol+.
J'""d1r,./r= iJ, ffor'
¤zl,rJ Aft*HE +Aq ¤¤ flBylol-r- t= r \-iflolQ.
olzlJ ulxluJe_e_ Bel ¤+ flg{r} +C tr|]tl gE ¤qql
t1A(l) B.7l
A(l)+ B lEn I olL
A
pi(s) pr(Eq4)
A(s) B(s)
p|(s)
.lal sB.e q54 L11aJ= 4lti-g n11=++-zf rrllg +9 Aet E_I 49 n

tolE -JE= Ia16t|0t -Lrtrl. q71,\1 A= E0t|0lr, B= rrJl Aoll=
=^l
?J= rg s8.10 EdlE= 4l+lg tr1l= ++:d rrll BeIEE +9 B
^tolel
Hg
8tr01tr|". EE= r.a{61ot EEl.
삼투압영향 요인 ) 농도 (몰농도)
" 58 EEol 8E 153
^J"JA6I+I 71186};. "lAg 4E zls

qB q¤4 ee ar+= Eg + 9t+.
+Le-E 48U4. : E +sE ztg4 o-aSqzt4= a6-}"l AF etlol+(rB 어
sB.t2). ol s." uJlel
+"Jg gd6l "_izl 9lall^l= +Eqlq "Jq
I +qot 6}=ql, ol E.qg r +.lq aFgi-/F+a
zlal] ㅇ El
_4,.Hf 1 t)
ln x ,_ 0184 tatls. +. tlFE 6,q+ qlE^J= q! .t'llE.-4E ol¤l ¤
R [T_T ) (s8.14)
^]lEtr+s
-e"
*, F4, r4r AF 4laJ, + dL+$ +eql el+ g 4* 4

cB # + 9l+.AlF Al=JBe rez} Eeq E e+g
rB ss.rroll E_r,la]] +9t+ ol rflql e-l6l$ gEzl ql = 4olr
+l
^lg ol4-g +6I= ts4 9l+.
+=d .llEJe++ BE +611E= zl+6J+4 o + ea :zH ss.r:ql +4u zI++ tlzlql^l= dlF zl-illql q6H^J
++ sr} "tul4 EE gEql^l= \i.{ol +r ¤¤- slByl ¤-.4 zl5-ol rJzlq, ol TlEol aL+= 9zllal-b sqg +E]-u
7l ¤.¤ol *g +6l]E= zlzlAl g+. rel* ol sB.l4^lg + + ol +"+ Tl*.el i"J"l +F"J4 *Eg rll ¤¤ol ol+
= q4l+.
+Eq "l^J^Jq ag +61 EC^*lg 7|eql
=zl6ll^J
+E "l tlil= ullz| +ol +e_E AL+6]] Eqe-e_e.Rj +
-ao
6J Aoltr + ol .11¤-p$ q+ d^l6}rll tsopq olol Eo]zl= aol +zllol+. r=l6}q ol f,rzlE4E Sr]]zI
^lq ElAd
g+. ol+lq} EL d4e "J6]]^J ol 49 +qlql gq EqTIzl ?*zll 6Iq }-EzI "JC6Izll .?xl!E tfl sn.n
^l= ?I =^l¤
++ ceg se,6}r. glzl ?*e4, ul4rl +eel $-aflrz| $ e+ ee tlzlE-.r= 4ol g +d-4+
"|]ql
tr}+ H6l-=
^l-dg 44421 t6la 9l+. alF= gqql4sE ++ElH ¤Bq^J= q}+"+q "J +
ql^l +rllE ++ i'lHl¤ol e.l"t ++= ols-" 6[fl E
^tdg
+ +,}|el e+trI EIHI¤$ +A q]+ql 9lolzlirll, "J49 zI
0.8
0.1 6IE +++ tr-4"J oI9 AeE qEolt4. {zlrJ f qdlot
Îd3 *.4o1 5-9 a+ +"lq "l q+E sq

x
6
6J T16llzl=
0.6
ofu
n|l [ 기준 다보
ol +"+ +q Eqfl= +49 E-'-" Eql Elull++E rtdol4.
고장액
olru
oI 0 .4
co
0.2
3 삼투압 A
p
등장액 +17
0.5 I
TIT*
++EI EO]l
저장에 90H
oa
fal sB.1l E6tlE(4trl'Ee{ +E 8tr9 EAg .9E el=. r= EtrE
=
q= 8E 4 +doll Eg s^l= Lfu,H/Rra,J0ltrl.
pllpl po@ + till
#JEt 0ll sB.4

'JBoil^] Eg
:el+oil
+sRqlE ¤+ dRul ts.sold mol-'4 ¤+A 3s4K= ol lal s8.12 ArFg r=
4lll6lalE U+Eol fl= gaj p9 f#-d
EolT Aet HJF"fE tt= +oll fl= "Jel p+ftg EE +oll +l ?l= ¤E a
e" 6I¤ sB.14^l e__tr+El 2o"Cql^l Hldql
+sgfl9
oltr4 +6liE= 4l&g + 9l+. =+ ^tolE
Ee= r.a16HoF -drl.
↓ 출높이
갖르는 압력
,rnxn"phth,r"," =
l.880x104Jmol-'( t
S:1ana6* [:Saf- -
t \
DR ) = -1.32... πI .Q.OH
o-
ArFgoil Hlail6f=
나
trI+,rl gtrI. ol g +gg 4.5mol kg-t 표
rnaphtharene=0.2601
게 =01
(1ksg Hld +q saog9 +sB{l)e_l EBE"Egl 6il8++ > -

확산압력 HI.E
L-T- trI
EOtl
물러동
압력이 같은때
8F용은 매확산
두
(e) = 상투압
fA s8.13 0l ,.FJ:dAtFgd-d EI^loll^.l==E-dgg E0t|7|E-4 4e-a
+4= E" 4^lzlzl"J +ee. E" 4rlTlxl *= HJFE¤- Î"lql +gxl= L]E|LI|Tl trl|Eoll HJF"f g=oll ?l= A= EEol
+r ++qI +,}|e+ +Eg Efl^lag ql ++6J *,]|zI f- =a1 =ol7f^l
ol+olctrl..
^l'ololl
π MRT
( 본도)
15/, 5 =J+S#
atFg.zlEEsl /.lolel EJ4l^] ol +Hql^J lnxaE ln(l-xr)_E Hh+q +-g + flsq,

--EEoE
^lel
e" r
sl+ qfl¤ol pi(p)ol4. 8"4o1 trH+61 #g a+qlts rn(r -xs)=-xs-E +g- + gl+(+
"Jqol poJ ++6J "ll +ql^JE
+E +q^J= +A rflEql +,]]E E ESol ls+El xeE I 4xl9 dFal pl. I[I4^J *Hol trl+r+ a.ol 84.
ol r irl+ trlHl¤ol *.I11+. rel+ +"-qql +g .Jq p+II -RTlnxo = -RT ln(l - xs)= RTx u
E z|"llfH A9 El+ trlHl¤"l +7}qlq. olBlqI Îr 4aql

El+^l 919 4ol q+r+ ?"1 84.
,'|+ 4¤- $ral;r1], *o4ol #zl rllEoll(xu< 1) Etq
=^l-
E +loll"F oJ+. RTxu=17Y^
Eal 1 +Qq +el 8"t9 ++ qfl¤g +4qE E.7114 #e +eqE +F"Jg +4.11=
^l ^l
BBql^l= Ael EIEI alHl¤ol "J+ +ql^l e.l"t d+. trltl^1, *.-4ol 5-g trI= xs=nslnôlq, q+^J RTnu=noZV-olr]. $
tti(g,)=ltt(xpp+n) tl olula| nov,"S *o}]9 dXl +rl ye+ ae-E-E RTnr=Jry
7I ¤+.¤_q_e nutvy +ge
Bel EE"E [B]"ltrl.E]+^J #g
*4"1 +{6J qlE 3rlol tr]fl¤g q.s=rl tol se.r^19 ol$-
+._qE alFglg ffi ! oe +qd+.
ㅇ
6Iq B5 *Bqe qE}E + ?Itr}.
11 = [B]RT van't Hoft 4.1 (58.16)
l-te(xp p + n) - pX@ + II) + RTlnxo
olE + 49 aq]6IE trl+r+ ae Eg + 9l+.

^l¤. llol4r al= ol +al^lg ol^J +"lql rll6}]^JEI
van't Hoff
tti(D - tt}|p +II) + RTlnxo CB6I= al"l4. rq+ AIF"JE E4... dzl +Ag + 9l
eq E zTl trllEql AIF 4l"tHg +E!4ol+ 6JC +6Jille+
tr++^l
eg r+zlE EÎpd=g e6l-= ql ,ll+ !_¤4 o e ol+g+.
tti@ + It)
- 11;(p) - RTlnxo olfl 44aJ EzlTI +6}lqB ¤-.1"1 ol^J4e ^dAg +4'.11
zl ?*gq, trl4^J vantHoff49 Hl4"J dzHzlE aAll 6}e__e.
t4l2 +"llel +q qd¤"ll "lzlE Sqel E4 ole" pl4.
5L= q--q-r+ Ag
"J4 aqg _r.3J6l7l +16ll^l :p.rzbrlg ol+6J+. tr+4î ^lg
7= [f]RT{l +Blll +... afF Hlalg EzH4 (s8.17)
G^(pr) = G^ (p, ) *
I:,v^dp
(ol BE qel +E_E L^l ?*71 +l6ll^J +eg IE r+
ol 4e q+r+ 4-ol ri ¤+ 914. ^lql^l=
4Ll]H+.) ol E4ll 6J ol^Jg ul"lt¤g -r.ej6ll +=
^lql^J
aJ¤o14. B= d¤4"J tr-+_e.^J AIF Hl4"J 4l++a ++.
pi| + IT ) - 11* tOl + li v^d p
Hl ol^JCql 4EI rEl= Bql 9+61-= 6}ztzltrJ +l6ta :z ol
{zlrJ ++++,ll Ael E +ulol+. ol 4q+ ptr@+A
y,"e. tI$ 'JEg +Îts + 9lg ull} alol cl-q_4 Bol H4. "l
=pi(p)-RTln xaE Bq= Q* p,[(p)= 4a6]E +-q-r+ e
g 7 = []lRT{t + Blll} E= nln = RT+ BRT[f] (s8.18)
^lg eg + 9l+. oltrll= :.H sn.r+aglrJ$ ,Jol ruU)E Ulql q6fl^l E^l6J +
-RTInxo =ll'uâ, (sB.ts)
44 zl&zl BRTE zlzlt_ AIF HlElg 4l+E 4l&6J + 9l+.
E4t 3 4+
)
4EE "Jq gq"l q+d 4"1^l +,]|E g +iil= "J¤6lrll
I
'lz7l: I IRT
+lB + ?l4r 6}zl-. relH ss.ts^lE +Eol trl*.q-r,+ TJol 7J -)
-.
E
r+1 o
+6ilT1+. F
n
Ii"^dP=v^l: dp=v^[r +- ). .t trl RT M
=
0 0-0
0
trI+^J (a) (b)
fA s8.14 AtF d:d (a) Etss.q (b) traJ

-EE=
0lE6lG s,tl-d
-RTlnxo =VÎI ela' =+=
=?|el =rl.
58 EEE Ctr 155
EEEil sF atgEt= otgEt r=rtE E Es c",,*/(gdrn-3) 1.00 2.w 4.00 7.w 9.00
a8 (Z/Pa)/(c,,"o/g&nt) 27 35 49.2 7t.4 87.2
zqsrglrJ +.J4 IE ++"lol rfe-$ ag tlF"Jg +El
,1l*.+. ol faJzllel Ee*g AC6lq+. ol qlolEl$ s.rlalH c,n"or=0.11^-1E +zl+ /d.9 ¤¤ol
q^s_r+ A4 Llg+.
c-.oy/(gdm-3) 1.00 2.00 4.00 7.w 9.00
IIIPa 27 70 r97 500 785 II lPa

19.8
c-"ol /(B dm-')
a.alfl AlBf ol EzlE sB.l8^lg 0l+61-= ]."J'll, EllolEl
71 4* bEtr- s.^lqq 91-o = e +C 49- {zl9l *z'll olag A?-l6lH trl-s-4 ?"1 ¤cl.
aao} ++. .Jflel e"* tE cgl^J d'-F"Jg +A+ + Illc-"r.,, = 19.8 Pag-t dm3
gql, iltE c"ll 4"ll^J E_^l6Iq lEzI9 E e=+g aa
al-b 4o14. +6Ji.ll IE E ¤=J:g Mol+r 6IE E.B ol A¤ 4I? artrvrt4 A+. III+^1,
"l
E tlle+ e* }-E c*,* =c^*lM! *4lz| CB RT _ RT
^l-olql= Ul "'^r_
- 19.8 P" g-' drn' -
+tr}. rfla 4,*+ E^lE 6IjJ" Me-l Atg fttrXc_,or=o 1.98x10-2 Pa g-' m'
ql^lg +4+ te-l ¤¤ e-E+El).
trI+^l
sB.l8^lql []l=c_.o/M$ Bq^l ol^lg eBi r-oE_tr lJ=lPamr
=ol
+4U4. ., _ (8.3145 I K-' mol-' )x(298 K)
r,r - l-98xto-, Pa g-t m3
1.25xl0sgmol-t
n/u) BRN)I
nM BRTc-"*,,
ol +'JAI$ p. e"+g trIEI^-I tzsksmd
'o14.
=RT+ M
Cn,r..,l
+4 "J* uol AAqE .E^l+ :aqlsE zlgzls.pq
olq^l "JHg Metr_ +btr+ 4l+ B= +B + ?14. ol 4l+= rB sB.14boil,tle+ B"l
BRTIMZOIq.
8trl +7lZ7l
v
x rPl B7r ffi.2 2s"cq^l ¤Elg3rlHlH(pvc)"1 +t lE
NRT /rnr\
C,n*J M
+
Iz'] C-*J *" q++IE SF"Jol q+n+ *E+.
c.,o/(gdm-) 0.50 1.00 1.50 2.m 2.50
Iuc^^,,,18 c-",,,yoil q6il,<i E- l6tE zldol
4".l 49
IIIPa 33.6 35.2 36.8 38.4 40.0
ac-...,r=0ql^lE +4+ tlE e¤ol n7ruol B 4"14.
ol-eH rrlc,".or #3 +q{ qloleltrPEl 4l$+ 4."14.
"l 6El4lE E A# +6Iq4.
t]p,lor8l{.u:E
T]ILJ=
=gET
tr l. + EillTt ol{'-4 ¤-Eg "JE trile-l Eel Gibbs ollL1x!= + !s. -5r= 5$Cg.lill +,llel E+4 El{l¤ol +Aol
={$es
$$ zlzllzl sq+¤ qe} +ae *B " e 4l&t}trl. a] *"tzlzl q$q +e}*.1.
a 2. "l^J4 +Eg E!=JEIE ool4 Gibbs glHzli d4 " + tr6. _4=d e=g +eq gg5s.ql Hlql6J+.
=g
E6J Qle evl"ll zl"Jg4. e7. q=E uaJE E6J +eE EBr-"Eql Hl4oJ+.
tr 3. StJ tle +q= ol^J +E!+ *zl"J gq+ tlBEz} oo1 o1g D8. HIFE$ 56ll^l +gq= $"ll$ q46}zl +16ll^l *"-4"11 zt
+"jg g+ EEo14r El4. 4+qo} ahb S4"l g+S"14.
a 4. 8d "J'J"19 f.il"J 9=4q r-¤+q= ++ tr9. dt-+"J4 +Aq EL" E Î"lel +41= van't t-{df Al o j7 +
=E¤e
614. olzl4, E e+g aa4= ql"J-J *B"l 94.
156 s trr!+E:#
=e.Et^lE
-Al
oe,zl -1 +4 al Hs.
Î
1
goJ Gibbs A.oG=nRT(xo lnxo+xu ln xu) ol^J +"_I 58.3
"lluJxl
g,* QIE esl A.oS=-nR(xn ln xo+x, ln xr) "l^J +.1 5B.4
eEl SlB4 A-pH=0 ol^J +.1

4"J t++ XE=A-irX-A-oXtdd ?ol
o --1 5B.5
c+ +.+ HE=n¤RTx#s E-Q; SE=0 5B.6
4L-zl
5L EI
O
+E = AT6=f(o! ¤84 Hl+lgc +e 58.9c
^1,
q=d LllH LT1=$b ¤e4 $eg::.ill $ulloll .J +=trt 58.r2
^1,
"lt}4 g6llE ln x, = (Atu,H/RX I I Tr - |I T)
"l^J +._4 58.14
vant Hoff ;7= [B]RT IBI-+o"J trl g"J 58.r6

^l
diF Hl4g Czllal rr= []lRT{l +Blll+...} dE zl 58.t7
^l
Lτ )
반트호프 인자
물에 주아 몇 개의 입자가 피려에 대한 인자
입자하나가
T2
ex ) vacl
>
caclz → i=3
1 진할수록 경우 ↑ )
묶을 수록 [ 정확
현실등 이론적 [ 보다 낮응 :
C
이유 ) 약간 붙어 있는 것에 대한
siiil
(
러
: : : 1 ,
;@ Drat ㅇ
O 8
!
cJ
j
l
(
~
,
vo …
: … :
Ng ;
: … .
… …
r
…
:
N
떤 떤
력시
차이아
해리 × 시 는 정확 이론과의
( 고정 )
ㅂ
고자 E타 > 분자 간 힘
( [ )
-
기체
E4sc ztr= 4lsl atsE reJ: Ei{l
16 증기압 불질으로
상평형 (
행분 (
압력Ietv ) 용질이 이알던
(
> ol EEE Hll.- olf;'
아닌지 pL
Ealalts g= a|¤t ttgoll^1 Ag,E! El rl^lloltrl. o-4rll
=tret
Eal*l?l=EtE=
Ealq =JeEl EH= sa6|a flts aol aBE :1B0lq,
qal^j olaE 61|461.= aol
=s6[tr1. 온도 (e -
v
a. )
roi
> EId 7llLJ (l -
l)
6r
pJ
q4ill =71
ABE reJ= BEE 0l?7 ?l= Exllel m
a¤E=E=E
e*E9.l
"Jq EF+= TII|I rBolEl. =7lel
s )<l-
rlOJ rlol
(l
LlEl-1.! - <l-
<l-i <H
> Elg.Et qHl rl^l O ASEEE,XO 1
ldE 8BE f.Br+ I?4(EE 4A)E E4tc6lts Aol stol E gel8

lal sc.l Raoutt9 ErlE oJ+^l7l= 288 Eo4el lfll
aolq. 0l Esle.l *HJ+oll^'l= Raoult9 H4(EE sA)rt +E .4i11+e-.1 Ag E EEoil q+ Ear.trl. =* =71
gtel(.E.of tA)g ?lE6t1l Etrl.
ol+r 9l= "-4illel +7lE adEol ?"I"t B

^Js EB¤.
g}E Eq +B¤ rHg =" -+6t94. 2^J+
4Aql^J 1CE4IE gs= S.s-q, tl44 " + d4i6llE +lg^d"J rdB"l Tlill^J
alel tr-BB rBe acol H+s^J Ezl rlEql a+ +d-6]i +q q r*"1 E9 9l"loh B Lol4. olag q+4 ?"1 q."J
TI4. rfl4 "l ^J¤¤ rfl=.$ "l^J4 ^J B¤ol+ E= d 6J + 914.*21 +ql EqflE CEEE E E¤¤ol
rolH
E4 o + Bled dxll 419 ^JBB$ ee+="]+
cll r|$al ffi 0E e E= B) olEE +E Sqe dzll "Jqg p4l- B A+
6I+ ol e$oll.<l= 2^JE
".lill gq+$-g + E|]tLe_E 6Iq, E pflp7l g+.EI+^J,
ill-aill Eq sDql^l ¤Bg lol'I.
=tlEg ,, -Po Yr-+ (sc.3)
'/A P
5C.1 atsE f.aJ gelEol oltl4"J ,ll= +E "Jq$ dill +71 "JqSp,oll
=71g+
-F+lgc EillE ¤ "lt} +EE 4 cEE 5¤ 6zl "Jqg SeI sc.r^14 dill +71 Sq p9l *t sc.2^lg oJe" o|{ ol
Raoult9 B4(Eq sA)ql El+^l r+q-r+ ?ol "-441 Eg.Ee1
ill +E E E-$g zlzlt_ +EiB + flsq, r46}q q+4
ad4 +4lg+. ag +4lE eg + el+.
Pe= x^Pi Ps= xsPi

q7l^l 4E +++ lg ¤zl "Jqoll xlE *aI +E Ie_l E +
$.o14. ol gtiJ$el dill +rl "Jq p=,'l+^l q-q=r+ ,Jq.
(5C.1)
ㅇ /
x.nrol6
A pi+@i-PX)xo
rH sc.2= pitpi>r"J {Bl <}ql^J *zl4
f s=l- f o
a^dg.-qillel a
q6ll^l E^l+ 1"14. pitpi>tolH qltlqlETo>x6ol4,
=7le.l
4g (5C.4)
xg=1-x^ ^dql
trtr} +lg^d"J c+ol alilltr_+= +71 +ql rJ "*ol
=q9l+.
P = Pd,* ps= xapi+ xsPi= p;+ Q;- pi)xa "J.J ael 4tt 9sq1,q nz| ulEfltsColq^J pil=09 trI= +
Tl^l
=71
sal (sc.2)
zl +ql Bzl $olzlzl ?*}.4(.ys=0).
ol 49 xoz| oe-tr-$el re H.Jql q+ dill *zl "J4"ltt
rCg gEql^J) pils+El p;vlzl a^Jql q+ d¤49-e H
++= ag +4S4r:zB sc.r).
158 s LEEEF=
000
I
0'8 0 .8
,"o *
a_
0xi 10 2
E-
nH o.o
0 .6
olru
ffii
4 6r 4
oI
< 0.4 K 0,4
Kl0
oI 10
{r r(
\ 0.2 -------- ------------- RJ
0.2
1(l0
100
0
0 0.2 0.4 0.6 0.8 0
0 0.2 0.4 0.6 0.8
.-4i11
+el Aq Et, xo
+E AE EZ,
= =71 =
Yo
leJ sc.2 288 018 E.-49 +oil +l9l= 8E Ael E EE= qz1 fal sc.3 ral sc.2oil^jq +ee AIA e7l grg= o|floil= sc.s^l= olE
=71 o4i1l
pi,/pd9'Joll^j sc.4^lE 0lE6G +oll^19 E EgE -et*-e 4hlE[ 6KI +sl AslE EEoll r|'|6|.|^l -E^l-d raJ. 4 c=el E^l= pX/pi ilz
raJ. A7l B-Etf el"J8?.1 4?1p1tp5>1)oll= gxll! ATl Eill-Ei
t1 + =71
LlElL.! aolq.
0ll trl =71
E+6tllElut|Etl.
zttrJEt 0l sc.r "l ^l¤. r+q=4 ?ol 1434.

20'cql^l ++* u4lr+ ,ilBHr4rg #z\ "Jqg 4
zl 75 Torr$ 2l Torrol+. Fg "+ill gqlE(rb.n,"n.=
rmalryrbenzene=+)r+ B¤g ol+I ?l= +7191 acg +s-J+
5Cr,rl1[9lo-] r oll 46]lloeBfl r]-$a1 71-g l-ga{g+
*"1 84.
el+.
r, _ *x(75 Torr)
/b",,un": 2l Torr +(Z5-zlTorr)x] =0'78 P=Pi+(pi-pi)xo=PJ .ffim
/methylbenzene = | - 0'7 I = 0'22
nlE}^l 4 dEE ++ +71 $qe q^.q=r+ &ol ¤4. "l !g q-q=$ ?ol lrl4.
p_
pipi+Qi- pi)piy^+(pipi)piy^
Pb"n,n = + x (75Torr) - 37.5Torr
PI +(P; - Pi)yo
Pmethylbenzen. = * x (21Torr) = 10'5Torr
ol= + <19 rJalfl dill
rflE =164 " + +*4 ag ^lg erll g+.
ㅇ
oJH +erorrol 494.
P;P; gfal
Y- pr*1r;-o;1n d^ll (sc.s)
=71
sc.2^lr+ sc.4^lg A6J6}H +._4el 4211 Zzl "J4¤ ?zl ol 49 E_^lql 4,ol :zH sc.3ol+.
9 a^Jg zlzlt- +4,J + gl+
Ale.l ?tr sc.l gajrl

E¤ g4l^l
2¤E Eo-4ol Ei{l
=71 =7lel SC.z tE-E¤ ABE r.aJ
^lolel
sc.4^l¤. _r.a ,!^-l xe=,ya9 44421 +l6}q +d ol Bfe e,_E-49 a'Ja raJqlî * 44ldg {4 gsql^l ¤Bg
pil+ (pi-pilxo= #6ll=4. :48 trl+4 ae "l-F= ^JEel eCg +${+("JEI4_"e. latm +ql^J). r
^le_l "JHq qL qlzl rH sc.a4. ol tr"¤¤ rgql^J= .lill^J ¤9ol oi
49 E=4.
4 ++ql +El*+= 49 ++aL¤4. gs-eC ^J¤B rH
Pi y
^+
Qi- P[) x o y o = x e, Pf,,
g ++E bg trl qC qEJg ++. o|4 Eelql^J EC6]]oF
olqî xe9 ¤# E-41 Eg+. ts Ae aqille+ a- +7lE ol+qTl Alzl zlffi^l vllEol g
fl dfluJ ?Iql Eqgll, ol ulÊg E6ll^J 4lel dill "Jq
"JE ratm4 eal g+= 4,"14. "l tlzlql^J= g
Ply o={Pi+@tr- pi)y^lx^ ol ++lE
5c 288 Xlel 8trJE :.H: o4i1l 15e
=71
349 4 tr-g ac(+¤ag gst+zlaq ql6il
^lEI
T2
oz)l
,rJ r.rl+r}. + #.=-d 2 7+7+ ru-- 14 xr=ooll.rl9 d"l
g+. ^=41=^.1=4 f4 +==+Jq= ole" afl,<J tl- aal
요
x. {
!o
l- rflq.
Lri T3 =
, trllolEl= rH sc.s9l s.r,la}fl+. +
^llEE d#
olr
a
o-qiilsl
fflx{
6LE
. e4xll
a4
=ol
trl-Sl} pol 4aJ4 a-tbz*c*+d*41*+fltrHqqi]] dg
z- x*o 4 6zl CS z=luo 4).
o AE E EE, yo $ill
1
xogl
C, 9l"C = t2s.422 - 22.9494x*+ 6.64602xfi
+
fg sc.4 ¤E nz; dE ae.q trl flgd?.] 01.8 t'49
1.32623x1n
raJ. =-^d aEE

sc.2troll,\1 ¤B-d Hle|. e0l 6.¤01 a,oJ e4x.|E E0lol^'t #0lr 34
Gzl 4, 0l"C= 125.485 - 11.9387y*- 12.5626yfi
EIALH ++:d A7f Lt8tl. + 9.36542y1n
^l7l-r.6lE -Elol
130
ElEg A^J #=dql^J qliile+ Gzlzl ¤¤g ol+r 9l+.

12
\-
(a)8ts8 :IaJ :1al7l
g449-E gE-aC tL¤¤ rgg CE *zl "J49 Ss (J
o
6
=71
fla-E= 4;l.6p. 4zll *z) $4"1 tatm(*d rlltr- el+ "J \

qq1 E+4 H6J + gl+)r+ a.olzlL gE- .JoIqH rg + 115
Eill a
?lzl"J oJHI4_qe= 4 gEql^J ¤Bg ol? E tlEq ac
q +EI ¤E qlolEl==-7l^la_ rfl+. 110
\_
0.2 0.4 0.6 0.8
++l "Jeol latmoJ ull= ++6J.lill dBql r.il+.+ilu+
0
xrH yu
,l ¤B¤. +4,]1. d=g r=E e^J #=-dol4. 'o_qill'4 fal sc.s E7l sc.1E gEJ1o)rl oll=J$l{!(M)rtel rH-d rll
. szlE de g6JEE dill ac gqq ea #=d(dill olEl= +de-e LEF.! E^l erl. =-stEoll
+71 $qol ratmoJ != gE)g +ElU4. :z4l'Gzl'4v

rlTl g7l 5C.1 7o"cql^l Ee dl{l4 B+ql Eilql ql"lEl
szlel de 4 ¤-Eql^J .liile+ ¤¤¤. ol+r gl= 67le_l
a^Jg +EId+. +lE belql.<J zllrf, uLs+ *"1 "ltl +Eq E7l7la_ +lE 6l]4-9 qE"l 6Iq+.
A+ql= +71 +ql flBd CEol rl ++6irll Eqgleq, EI ql(c) 6s 66 70 77 85 100

+^l "l +de g¤4eE E3 6zl "Jqg 4= +++ c xh"*-" 0 0.20 0.40 0.60 0.80 1
e +e-e + *¤: #=a +-e-E olE"6J4. .1y'h"**" 0 0.02 0.08 0.20 0.48 1
9')S Pr :6
GZ@ gE-Edaga=g=qTl 100
49 gsyarJ cllolq= t.ooatmgl^J ++(o)4 qlBHfd

64.6' + 79.OBy - 106.27f + I,, f/
90
(M)qE EqlE¤ zlzla- +A6J 4"14. ¤zlri xyg 981
49 uE E E¤-oll, lu* ¤¤g ol+a ?l= +rl +ql 'y-
P80 ----------t
^JE
E Bgol+. 6 /
elfc) 110.9 112.0 114.0 1r5.8 rr7.3 119.0 r2r.r 123.0
70
XH,
xM 0.908 0.795 0.615 0.527 0.408 0.300 0.203 0.097 {---- ---<
' 64. l3 + 4.63x + 14.09f + 1( i.20f
fm 0.923 0.836 0.698 0.624 0.527 0.410 0.297 0.1@ 60

0 0.2 o.4 oJ 0.6 0.8 1
X** /r,
M4 Oel #=dg zlzl r10.6"ce} 12s.6"col+. ol gE.E
rgg rel+. fg sc.6 el -dll(Hx)rl flEJ EH-d qlolEjE
9 $s-ad tr-¤B E^l ^t7
| E.71sc.1
=gEoll
=r[.
160 s tr!+=d=
(b) ABE raJE 6114 E a,oll.<1 EillTt #,71 ^l4l6lq, 7l+ql= "+g.d o + io1
zl= Hlql tr|4 aCol aioJ *zlq. ¤¤g olE+. ol 6zlE
u-zl sc.roll,rJ4 ?ol tl¤e rHel +¤+g'"+ill'dg 6]]4
e- trll E. +¤- rnE r4i1 '#zl'dg 6114g trI= E E¤- ro
B+ +lEc"J CE(B)g rj "*"1 EEI6Iq, 44^J "lill +el
BE aaqqzl+. ts= a4ill +ql= ezl !-r* q ++6Hzlq
. +4U+ + xoglrl9 f4dol 'Eill'Cr+ :zilalg 49
E*Eg ElEqAg qlE aC"il^J r eaJEol #=d"l+. r #=d ol aza olE" 614 aqille+ B¤¤. ol-T= L Gz14 zc
ol $roll.rJE +gdg ㅇ o,{=dol4r 6l+ql, ol "I*dol '5= * alo + Hqi+. 4l+6ll^J 7Ig6lH .4illE aCol ++6J A
+e-E q olf,.ai-a. #=aol uJ g4zltl *zlE acol aie
7l'iJ4 _il.zl.6l+ de ¤¤g ol+r gl= +71 t 49 ns]
E Eg roE 44{tr1. ol tL¤B rB9 +B +g znE 44
E HeL4. olq 4 ainlzl 94zlH "4al7t 4E 'l +gqr
L|]jr" +d 4tol '"4ill'dol4'*zl'$ol+ql 44 xo4 s.= Gzl9 a^dol EIIEE dill aC$ Aol+l4.gE7I q 94
zl$ frzlulol Brll sl4 : aCg xl¤-E ._qill aC4 a+.
/oE 6fl4ttrt.
419 9se+ dill aCol 'o-441'd4'*zl'4. r1"l9 gqql
+qd gEql^J ol tF¤¤ rHE 'Eill'd oI4 AEg g
aJEol rq #=d gl= *EIql 6l]R6J+. "J"J ++l 9lg trll= qI acq aqillTl-acol += +rle+ B¤¤. olF
"l-491
"J{ol latmol"lrJ :z gEql^J 4 ¤21 "JqE+ }$ trll=
r a"¤6I41 q=ql, ol + ^JE9 ¤z}]+9 ql+g + 9l+.
?J,4l 4lrl aqill ^JEHE ol+q xo= :z .+ale.l acg ++u
4. "le+ Hli6}rll +qA gEql^l dE"l ,Gzl,d +lE +q @rtz1t t=l
g trI= g.JEE #=dB+ &szl El +sq, +zl "Jqg ⑦
+zl +q
=qil=
e9 Ed*9 ne.v, r4ae
'4ill ^J +el
++. rBlI dill EaJEol GzlolA : aCg ?l
-
latm-H4 Ee+S no,rol4r 6IE타

AE di'll Ee=*g- nA=n.,L+nn,v7l
4 Eq+Eel a^d$ p+(E6JE 44lzl *z\e Hd o =e).
~
qir, BEzIel a+qlE u[]z[z]r]. relr e9 dill E +g

'o_4ill'd
^Jql Aol s4l
q= gEql^J= .+ille+ *zlzl 4d 2 .lill +ql fl= +zl¤e-l dill
zo=(n**no,)t(no+ns)o14.
I "l$zll 94, *zlel aCg qgd$'6zl'Col "J+= d EA*(Ae+ B)$ nr= ne.,rtnr,.olA, +71 +4 diil Ee"+g
9 at"l g+."1iil tt"l ul ?la+ ¤q4?zl t"l q "Jcqi ny=n6.y*ns,vol4. olE +41= +71 * +E E E&(ro)e]. .l
gq Hle'olill'dol4. :z
Îolql +4+= AArG+ *d)z} ill tr-+e_l E- E¤(xo)E zlz\a- +4'3 + gl+. r4q-q a4
4a'+7]|'d3 +7l4ql atrE zll*6l.41 g+. ill ^J +E AE EA"*g nrx^zl ¤4. ols+ Hl+6}rll +71 *
6J +q+l gEqlrl
"lE + CE ^tolel dEe +714"J +q Ael Ee"+3 nvln7l g+. tri4^J Aq dill Ea"*g +
aE- ++B f glErll, t4zl9l6ll^J= +¤+g.4ill+ + 94 Bol ¤+.
7lE a^dg qetrlE ++4= ae e Ezl g:r. ¤¤9 ol+
nA= nLxA* nvf t
a ?l= g.JEe-l d4l acg +EILHE 4 oe _H_ol"F ++.
146}0l e9 E Egol zo"J S*Eg 7I$6IH qB4 g a elE e+zlE dill E¤=J"l +94 el."I 448 +E 9l+.
oJzlE
^J46HE+. dill aCg 6g"l
g"lzl "Jq+a +41
nA= nzA= fir.Ze,+ nvzA
g{of pzJa}e_E ol 4l= f4 sc.t9 a"llrJ +4d
^14}El=
g,r].4 gqZI+. olEl6J +zldg E-a¤,Sol?+r +=+ " I F 4g +Al +98 nLx nvl a.= nLz nuz o7l I 4 o 49
I
^+ ^+
+*4 eg +41= eg + 9i+.
ㅡ
C46IE
l, lu
a4'
nr(z^-xo )= nr,(yo-zo)
a3
t- a rH sc.sql +4U uls+ *ol zo-xoY 4ol /.4 7Ja, yo-zo

aol /,,4 t4. rl-4rl +lE ag rl4l #=lg
Lri ^-71
0lr
O'I
+gr+
= zlol
^lC
+E|4= s4.
nrlr= nulu minv =
r 라 +4] (5C.6)
^lajl
0
zA a
+4g q4^ll-6zl ^J¤¤ re s"J olq4 += qrlaJ
^lell
rg sc.7 E=oll^1 ¤B-Lf gala¤ AE-d raJAt9 EE. oE 5r|.61.= ^J¤B reqlE 4+B+.
+^lN= S^dco + l dill zlel rtrEJ 48= LfElL.lrl.
5C 2¤E 4lel 8EJE :.aJ: o4i1l 161
+E-(a^dol o,)¤. zHzlEB .ll qts HElzt .Jq*EzlE ^J4

aN Ez|. ti¤¤ rflql el6l-H ol go.J$g 7,ql^-l #il
1flg
e7l dol rJ ^d$g eI* rl ++6}{l ssI6I= ad ai\ Gzl
= 1
t- nv nL E 4E_E4. ol +7]|= +Lolqlq ffir]7lE i]+ql +4+=
ui .lill olgE acol anTl84. ol +¤+ol olq4 4ztH 49
olt lv ~
L ++tI
- ezl-4s--r- eqal e
+ql= B"J BAI ¤+.
o-4i1| 0
EE =o++9 s¤9 oIEEE +E 7l^la- 444b'll, ol
olE+E += + +qd 6FEe+q +qd 3^JE H
68, g e=
tri1l z
rll PeaJ+g4Fq +E +41++.
…
reJ sc.8 xlall +.1. /vel /Lsl 71a:1= 0lE6lE E-d= olFn 9l=
ojillel EEB Hl= +:sf rlall ++.l0lall" +e= ag =7El'
gEq
+ ?ltrl'.
q 5C.3
^lall Zttr.Et
traJrl xlall gEo.e+E1 0l=zl^lE 7lzPl SII(mulu=p,_1r1s
=,Je
+olrlTl nllEoltrl.
rB sc.ea9l 44U eEel EqE
Etr Eel+el 6l-ElE
olg+el fz|:ol 99ot 6Lq, rH sc.ebE a+ql= 4I
el CEEoI ,rJ_tr Hl++ ++ +zl *qg z$lt- fl_9-q,
zlElEt q sc.2 EE ="++g olE+q fzl +zl qE+ "J5qoF ++.
rH sc.7ql^l= "*gC ai"llrl lu=Zltolt, 4 'lill tr- +ql
Eqgt= Ezl¤E E¤t+"] +71 * +q Eq?l= Ezl¤
el Ee"*s-+ E zullTl S+. rrl a o,E "Igdq^JbtutS
(b)
9 ulzt Zel +6Jqlolq, tr}+^j nrtnuE 4el ++4zI I =E-H=E}E
gzt"J H"J+. $szt ara &4zl-E lrllrE Bg .4illEol rB sc.4e+ ?3 0ltl.4 E"JE gE-a^J ^J
"l ?zlE
u1z1
* e.szy Elq q4^J nylny=o.tsz| qr Eill trrlg *E ¤B rH¤- +4'Hzl"J ollJ.C "e+q ¤z16l.rll H,q+=
q¤¤ 6I= .l4lE "*+. Ae+ B +4¤
E{¤9 E¤Zt"l +71 * +E Ea=JE E g.lsHll Elql ^Js++ trlE ÎolE
qa Eill= E 9l olE9 gEt$ol ol^Jzl <1tr4 *Z #zl "Jeg +QL}]r
"J ¤4. 9sz} anvlzl94zlH lutlr=ool
4"J tszll ¤+.
tr|+^l #i
9s7l &+?J uI= t|¤¤ reql *4zt +4E.
+ 9lq(rH sc.ro). oltrll= A-B tr-s. }+"I .-q41=- "JaEl^l
zl4. olBl6J a+ql= +oJ Gibbs "llHxl G'(Eq sB)z| $ol
trn2 g+(ol^J4"J trIB+E q g sB¤+). 6JE +4dg q+
rJlrrtJ ==
OTf
L]]= tI¤B rfl(re sc.ll)g gel$ol ol^J4"J A+E+
rB sc.+ql^J a^Jol aroJ "+illE 7I$6IE q$rll 9Ezl5 oJAdIzl *4q
re]6t"l e-e ^Jsz}¤-ol +Hts+= a¤. el
^J46I BzI.
ol goJEg gszl Tzoil sB:"lH #=+. _24 "l*+. olq6J 4el a+{lE crz; "Jolq(ol^J4"J a+Eq
H Eill= aCol arzl s)t(q+ ?Jtr+) +rl(g4"J +z}|6l+)
a^dol aio + ¤4. ol +71 +.ilE E+ trl +lgc"J(+ #
=
*gJ cE ezl trJ *+6141 5q ?14. ,,9 9]21-e.P
=dol
el ol #=dql^J 4 *zlel aCg "J + 9lg q arel ai! ") 2
b qgdq +lilE+Et .+iilE #=d(4)g gqB + 9l+. l-

Lrl'
0lr
\
(a) Et EE
=+el =+
.J+ =-Fql^J= SzlZ -uuooluflol,<J f,q,<]il4. ol
"JHg Hl+l
tsC *d"l+ aillE+q +lgC .-qill. E?-l6l-= trll ol+g+.
4d, x 0 x^l -
LO,
(b)
EE =-+ql^J: olel+ #_r. ¤-+q= 4Ag ¤BoI "Jq+rll a) ^
eI4. ol "JBe +lgC '-qill# +4^lzl* rll ol+¤+. .lH sc.e oIEEE t= +9 F dE= clE B^lE Eal SEtlE
=-B'= 0l raJql
7l^178 rll "Jg-d Ezlel +0|tr|.. -E?.! + Zl9 0lE.J *E (a) :rl
a4 sc.+ql^J aôlol ai"JGzlE ffi^1zlt, o1"lrJ ol * (b) 4El.
162 s trl+=-st=
GE < O
@
A a4 α~
oo'
x/\l
a; -71
o, lLO
~
~
-71 x,\1
O/t!O a2
"-4i1lel
t- l- ]1L O -
L.!
c5L
Lti
ui
oU
olr e4illsl a2
숍
a
]1L O r AB
cEL L!
안정도시 a3
반바ㄹ
a3
BB ABb AA a AA b
'a4
a
a
o AEEEE,xoilyo 1 o AE E Eg, xogl yo 1
f.eJ sc.10 ts= #tstrE,*ts EE-H EEIE ooJ E4E =o+6tE fg 5c.1t 'tP e-Eollll ."-:= EE-E= E-'JE. ZS¤01 a?.! Eo-48 EE =-E-
'J0l'?t= e4xllel 4¤01 b=:Br6H^l E6l'r r ^dol E6f^l ?i=tr|'.
olAio-eE 6lE =o+tr+oll^1 EEg 0l+ eTPl b+o-E olEot|^l g86lXl+^lEtl'.
g6Jol E .J ¤+), qr$vle+ qlE +rlel + s4zl 4z)41 zl (a)E¤+¤+.nl-+^l ol Etr =oE+- ?zl==_ EH #g ac
q=R+el+
"ltd o ++ElE olBol tr-¤¤ rB tlql +EH+ +i=
bTlzlul olE^l7lr q4^l =o ++ +trll7lE+El EE #¤- +
7l= LleAl fl+. ㅡ
+e}.u$ {trtr oJ^J r}s 43 otrlzl"J olqql a+ql= ="+
a4ql g6}0l +Elt+ qlE^J rH sc.l0oll.<J a{ az} zlEt! 0ll sc.4
=
+EHAE _qE+ql il= EillE ^J46ll Hzt ol E6JEol #g cr^ rn,^'Il r-1LrLrlI *]ruol ,r-lzl o- r L=Lrl-ll- .,tl= rlr- /^\
J-l) E Jv.r.v-ll "'l -r.!l u.1l--1 o = = .1 .1 .1lC. -ll -,.|c \a,,
_er-lptr+"ilElse.+gr+ 0) a&/E gq+E# 5 +

gl4. ol +7]|= sol.4E(ololrl Etr+ B4^la+) tsoI gl
?l+. gty$E EH-#+ goJ¤"Jcll, ol gd¤$ A"*e
'+ill +ql= 87| EJ ++6}rll Eqglrll qq, Eillel 6Cg s a^J 807o9 E¤ E,Er6tr. ilsq
=
qaql a,ol 9l ol a44le+ ¤Bg ol+r 9l= +zlE eC 108.6.Cq1^J #=+.
rg sc.tlql +4U BEHE ^ddg +EILH= qler.J} (c)
3 ajol 94. ol *zl= Sot4H #= "+illE a^jg an* 7J q+t/E4 (d) ql+g/E s'Jgg + 9l+. ql*94
3 d-" + olf,op., *zl4 a^Jg a;o 4 0156}rll g+. rr|+ =
DAn
통
Eg E!+Eg gol {a}g.E a%o E4 glg ,I 78"cE oJA
4 ="#zlAl+qH A7I ++qq +eql rl4 Bot gl= "-4iil ql gEql^J
el sCol 3 +o e olt 6llrJ+. -:.48 +a4E #=Ag g+
#b+.
zlt- 6,zl +ql= 44 Bzy ++6l]a+. ^d+ A. sg "J+ B
o[,tJ o-!i-l]el aCol b"ll EE:o]$ *zlel aCol ._4illel a¤
4 ?"tzlq, q-+^J +gol Al+6H^l "Jq+qqE aCel H #olrl ts= e4i{

(c)
g6JE-g EE-EE
Ê7lzl ?+=+. "l+rll E ?+= + .lillel ++E
e+71
¤o + +++ E4 ?ol ^lE 4olzl
r =-EtEol+
¤l+.1 EH g¤- E6JE aCql EE:"IH ¤+.-4e-l aCol
${a}lEz}. B¤ ^}4ql^J= ululal "J9 ez1 B +ql +o}91
EH #+ .lillel 4C4 2lotzlo + ++.6Iq4E + ali-ll _2, ol.&ztzle ulrgr9 ezt A +ql +ol.gleq, tr[+^J + +
z]. E49zl ?+=+. olol Es}slq 9l4r:H sc.12(a)). trl4^l
rH sc.lr.ll ^Je += dEEE
44t
4lE Eql EH #g gaJEolzluJ _r. ol g6JEE dill +71 "Jq 2 p=pi+pi4l zlnl& 4olr*. ol
ddol +s+ zl+ aCol a,?l aqill.tr-+El ^l+4q +E + +71 sqol 4zl "Jq4 ?Jolg 41z4zl gEE E¤#E #zl
;g(+4+ E"+g ifl+l^l -s$4g rril 6lq +4 +4 EdE"l +.lsE+e] *A 4z}4. :al
+ol-gl=
+)g Ea]] ge}7l+ +7lE aC Hsl¤
=E^t. ol ^14-610l
+ ^J4I6Iq + #= r+Aql^J serEol C6}rfl -n-HlqTl qlEql 4 CEE
"43 acol aioJ ¤zlz 4--6ts4. ol 6
arollrJ #71
^l+6}q e += ^Jg +s--tr- 4l+6H^J E3+qq EqTIq q+^l "lBl
7l= =ofr+.+ql^J $f!q Eg acE e!ill(a,-E -tr^l¤)E
tI +rj$ol zlf$ 4,"14. "lBl6J ¤^Jg + "+^llr} !d4
¤4. ol .+ill=aCol aioJ*21q. ¤¤g ol+41 gH, "l .ft etr d6llot "Jq+q, :zB sc.t2(b)e+ zJ? *zlql ol+lqi +
zl5 ="69 +e-l q +g *4zl ¤.4z}^l E.J qill .lillE Bl zl-9618 E"J gE_ql^J #zl ?*=+. Esl +aI
=^JE
t ¤{tr.i. azeotropeol4-Il alic1l, rd]^qE 'H+$.ol #=trI'{= "Jql e e.J+g qL + dtss+r q *3 gEql^J #41 6iq,
f4¤ 1o14.
,<l
sc 2¤E 4lel gtrJE :.aJ: o4ill 1 63
)r Tuc
P=1
x 1
=&l
!o
dE
lr]i 8el Id
l-
Lri
oU P=2
(a) (b) a"

a'
rg sc.12 1{01^l PJE (a) +'-4i]l9 E4E ¤E- (b) El.EoE

I
a
Tial ?JLla 849 + =+=
9,{oq, +-= "Jalol --J0l 9l+ "Jal4 ,Joltr 0 1
x_B
=+6|=
nll#=tr[.
lal sc.l3 Ae[ Betel E-gEoil EH-d EE-68 a-'J-d raJ. +,s "Jq Bq
Ei1l7l 27Hsl 8= tsd61.= 6drl3E= LIE[1.!tl. 9l "JZl EE 1.er;
=
44t *21 $4ol latmgl EE:"IE #Al g+. . ¤EEE + +g 5 o-{i{zl-olnlE} H|Ee+ #oJrl'.
=E0il115
7l "Jqol latmoll EBalzl dql #al q= a"l+."1 94=.
ol+ql zlol fri !
-=F?lull, "l "JBg
ol+6t$ gql E6l-r -zH sc.raql Eql AI9 a+ql= gEzl *4zlH + ^dEE
Eql +zl ?*= +71 Ee# r.E d^J #=dE+ *e E-J^dol *zlel4 El+^J
4 ^JEg ¤B ^Jqlql^l ^J4oJ "-q
gEql^J ="#^lvJ + ?14. ,JBE 6J Tlzl E3 ¤+o-qol
"l ill= q $ol Egr-a|rll qs F , I 7.zl +7I q= tL 4"il8 s
r ^dEEq *zl "Jqql Hlql6}= acg 7l^lq,,r}4^l +lg 7l q "*ol E"lzE E Bzl ftzl q= rr-+ql= Az| Q $ol
dol *3 zlE"l E|]+61 A*+ql {ezl ?+=+= 1"14. EqTIEE z*Al ¤9ol 44 ¤:sqlrJ olrl+ d
eg Hl+a}r zrJ gqE 4A1= r4E di{4"J tr-¤¤ r
==otAl4.
o Ol o .,'- olr}
5C.4 o4i{l-Ei{l c|BE :IaJ e]
trrE, E= I /\^-t.
qzlrlE E= ¤-Eql^l qEl+ Hl¤-s+ 4olxl ?*1, H4

oe #0!= .lill_tr- Alql ql¤L gE_aC ^J¤e rflql +6tl Etr@ o4i{t-o4i{t aBtr rg 6lt^1
q Esqlt}dl& Alzl tatmoll^l +44= {}¤¤ rHg

¤86t414. olelq} qlE^JE dl4F+ qtr +Hldlg E + 9l
^J
4. ol A+qlE q4ill-6zl tL¤¤ rHE 6|]4 HJ^lol rql-E rB sc.l4ql +41l]fl+. 2e0Kql^J so99 dltl(o.sgmol
4+s+ cuH,n)4 sog9 qE.EHldl(0.4lmol C6H5NOJE E6J+g
"JEH+.+ tlE q$rll qq, E olEel Hlge q
=Cg
grll EIAL+? e. t"J tLS ¤g4E EJEE gE=
(a) IEal "l
qts + gE- r'ql^J i*9 qill nE += .+ill 4ql zloN -H-
9"IE 94oI 6IAL+?
zI. rBlH ol4ol sd6l +6l]El"l
"l 2cE alrl +"J ^Jg
olE aol4. s= 4l+6ll^1 716ll +ts rl oltl. 8"l]9zl ?*ts P=1
+4lql ERR 1"14. "ltrll} ol AlTl + ^Jg 7l^1AllEcll, 294
6t+= Btr. sE+E Aolr += 6l"+= A-e. s.EI¤ ulrlel nol 292
290
4. :zB sc.l3E gE-a^d tl-¤B :-BglrJ dzlel aCg \z
l--
Io lp
4 a'o 4 g^lq]l +zt9 acg 4 a" o 4 -g^lg+. r?-l Lri

olr
P=2
r. + tlq tl'il4 zlql +zl o_+ +qTl+. B= 4l+
=4]r}g
6]l^J q 7I6IE p.zl t- +e-s qlZI *"i EqZl+.
"l + ^JE
¤¤ acg old6l a,al a,,olr4. 4l+6]l^l BE 716l] fH a4 273
azl eE +_e_E r-l olf,ap. Ela4 ezl t +e_E d+ +oi 0 0.2 0.4
qEeEldE E EE,
0.6 0.8
x"
Eolztrl Alzl 4tl +g tr-e_E !Eolt4. ¤zlrJ$ei} s
fal sC.14 t atmoll,\"l9 -dltirt LlEeU.lt! Zl9 .gs-ad AEJB
E q zlollE *olol #olzlzluJ 6p. alE +"J tFe-E EIE raJ. ",{E{j 8g tr=4 ZoEe E=oil^1 tsE:el a=01tr1'.
,il g+.
B¤g ol+I 9t= + ^Jel a^Jg gEql q+ g+tl+.
164 5 trJ+=-st=
¤Bg ol? r ?l= + tr-E ade gE= +

+0.1
a.elg 3
ÎEl
4rll= P*dol tr- a4e+ l;}6l^= d# -BH +el + 0
il+. :aqr ol + r}E Hlgg ^lql +zl(sc.6^l) o e + I -0

N.---- 2.5
q{+. ¤EEol $ad 40lE gE= +6}ElE Fadd t 2

o -0.2
g flE tr+uPt+ olAol tr} ¤9 o + EqTk gE= + .:
E
\ 1.5 //
sH g+. -0.3
dl4Fg HB rqr
1
+ -0.4
=01 'l=+HI4l¤. No ++rllir"

:zH sc.raE +r++.sql¤ +ql Eqfl= NE g +g -0 5
0 0.5
3 4. xN = 0.4111 T= 290 KoJ
x* = 0.41l(0.41 + 0.59) = 0.41 ol x^
d9 "l tr-¤B rHE 2tF ¤E"il +4U4.+B "I¤.de feJ sc.ls '*P EEoll,\l +Ef4oe #01= 2dEzlel EEoll tttE
=-ct
xN=035elxu=0.8391^l ^J a4le+ I;I6Iq, EI+^J olEol Gibbs ollLl^lE Eel. 0l= F Eol L|-EILI= 4? AlTt ol
+d9 F troll 6]186l'= =d= =oll^l =
+ dlo-e EalElTl ttHEoltl. 0l raJe
+ tl-E aCol ¤+. + t9 ae+ pE ++q]8 ol tlEg ral sB.sel
=SgEf 10|tr[. ^¤9
"JE ÎolE Hl= xl4 +4ql Ir++ Ael r,e+ r0el Hle+ a
E+.+ (xo lrxo+xu ln-rr+ ¤*o*), ¤zlrJ rs=l-ral9 nl$a}fl ffi
,, _L 0.83-0.4r 0.42 4 *"1 84.
nF- lo
=-0.41-0.3s 0.06
( Ea-*c )
+ dl&ol +7I q= 8"4"1 q-E +Hlr$l"l 7zl qb +q [-4,^ J,,,
el E 7Hl7l84. zszr_e. 7Ig6IH ol .r.lEz| ltr- gqs
=nRT
_+ EqZIQ. ol
^J-¤B :aflg ¤84_o.e "J= 4ol7l
trll T,p
gq ol^J4 4E ?J+Ag 7IC+ 4"1 "Ir-14. 4lql z}6ll - nRT {ln x^ + I - ln(1 - xo )- 1 + f ( l- 2x )l
zl= Sqol B+zlE g+T14.
"lE A!+E =,nr{m
ft*6X-r.^rl
rc.z 273Kq^J sog9 dl4}4 roog9 qEeHl
^l7lg^7l
dlg zlzlr. ol EzllE 9¤"1 61q4.
EI+^l Gibbs "llHzlE +g aag "J+^le EI ALzl9+.
XIOZ -trloe'1 : ffi[n r *o
l-x^ =- ((t-zx o)
1 h[o95'0 toSO'0=Nx '6 ln (sc.7)
(b) gZI E"]l e=E

ol !e gfl gel 6]]E *zl *61^= agEL+ ^19 6J qlol+.
"l ^lE {i)= fqr- +u=?lq=
"l](ol 4¤. "J+^l7l= ro9
+l g4l E-ll e-= 4.. ^J E4zI "JqB + 9l= 9re1 6aj olf-aN.<l +^l 4l&g 6l.4+ E=
6= Bi+l7lE^l a4l 6Jr+
olr+. olH+ }$ gEql^J= F rJ$ol Sd6l 4"J4. ol 9s Eall 6J¤- E_^l6Lq rildg +Ei.11= 6E *otr.l +6l]ot 6J
,l-+4+= g"J3 Ag Exl¤rl4 +A9lg trIE trlHI¤ qq +(rH sc.l6). olel6J *B " + +6J 6ll= sc.vql E^l r4
zl Hql^lel oldol ExI9 g+E" ql E6}l^l xll"Jgzl ullEol4.
6
:- aJ {lzt:-H sc.l4ql +4U q E +Hl4ydlt} alol+.
+l "J4l +6I gEE 99er-4 "-e re6iEjH g.J Gibbs
4
lnlx/(1 - x)I
qlHzle+ olaE gE E= +4lE -Holo} ++. Eq sBql^J 2
=1 2 4
E96J Hle+ ae z}+el E¤E d4l +"-q(+E6l c+ 8"1) 0

1-2xl
3:B sc.rsel Ag E"JE g.J Gibbs ollHzlE +4U+. -2
sB.6^l(Hu= n(RTxoxu)ql^J EE6J u}4rl4 ¤rl 2Hr+ a
7l"J 6lH ¤-Et Gibbs glH zlzl * +^d¤- +Elu+. tr|+ .I.i
gqB + gl+a -H_olo} d4. ol
^J ¤>2"J "llE tF E4zI
-6
o 0.4 x 0.6 0.2 0.8 1
zI+6J E¤el A+ql= DA_oGlExo=0ol q= aa¤. *sH

fal 5C.16 5c.7Ll= +ts l4E 'J^.1. 6<2"J trll= EilEol x=0oll^ltrJ
+idql 6I]R6l+ a^J¤- +e. + gl4. ss.zll[A.oG=nRT LlElUEl. 6>24 rllE zzgel dllTl'L|.E|.LJE[(5=39 tttlE 6}l= E^l6tl
=?ttl').
5C 28E llel SEJE :.aJ: o4ill 1 65
2 T
210
P=2
()
o
6
82.5 Lti
0lr
I 61
7,"
P=1
3
0.5
0 0,2 0.4 0.6 0.8 1
0 LlaElsl EE, x*
x^ =
fal sc.le Erf q?EJE tE-6d AE-d reJ. plel, olat| g4l Sezp
leJ sc.l7 .tr.E sBoll^1 s.B-d 6-nl.alolEJ EBoll "J46tl^1 Zl+i-d I SXle-l
E El LlElurh. Ei.llE E=2|==E ++a|.qal(E6l ol ra3
+til. 7 lgE /.lE0l tt|-"l 7i0 ltrt.
=E -es.).
619.+. EzlzJ 619 oJe6l+r.

^J46l$(tr++^l rfzl "JA6L ql^J= + tlg ol$+. :z t qlTr Er+ E4{lBot"J"l4(:
+) 69 zltzl gE +7lql 6llB6l+ql, ol rHq 96IH, 671- H sc.rs). olBl+ A+ql= + ++E Ezlz} *e gEql^l
el^6.+ql u+4 + +Adol d=61¤ 5=zq1,t1 6t+e Et
^ls qF* +Eg "JEzl ql$ql fi"lzl"J gEzl-+otzlg ol ffi
adq. ol +r]Elr + ++E Ezl-Eol 6Jq.
^11?+7]t+ilBJr
4lql q+^JE o}4e+ +lE + "J4l +6ll gE= 444zls
d4. olae +Eol +qqr ++ E6Jol ol+qd4z} E9
E7l sB.lql^J d4lr+ rltreal{le_+ ¤ 4lE ++fl¤. tril gEql^l E¤lE FE4 " + 4"1= qqillg a*"llrJg+ z.ol
i ¤=1.13o1q^l 2*Alp_ 7146}zl ?+9t$.trI. 4 dE 9s Ezl9 g¤+ql Eil gqlEq +"Js}rt "J"l4zl ullEol4.
ql^l + d$ol SAq s.JqH+. +alzl o e ffi {ol 7l* * gEJ4l ql= q=.fl4 E"lH, 6t'6e| 210'6 ,tloJoll,tJ
+"J 6ll xr=i* 7}xlq, ¤,E. Gibbs glHzlzl E"J +ail ++4 oE l"Jq(r? sc.tg).
E Lt4qq tE4zI .J"l4zl ?*=+.
mt'; H4o+ 40!= e4i{lg

(c)
+1.13(L-zxo)=o =+
!e $84-o + 40lHrl *e EH-#+ e.JE-g ¤^d6l-=
+ %IE aqzll= ^J4I6l] BzI. ol + CAg + ++E $zlz|.<J
4ql q+^J= ole|| g4l E6t| e_s. r,.5 zlzla- gleq, ol EE B?-l 6}tsl= A6Jg +44= 4olIr + "l*l6J eE¤ 6I
tr+ *g gEql^J. q¤ Hlgs+ 4lolr. ol-H_4 *g gs
._4ill
tlg ql+61 gd}tri. "ltrll= + a4illT} #zl d9l 9d
=
6l E6Jq= a+6}r" Sd Eqlol "Jq+71 dql #rll q=
P=1 e7l b1
1&l 8sl
x,\l
+o a2
]- Etrfl 8el 2
u x l
0lr P=2 4O
l- I
bro
U.
ol.r P=1 "-4i1|
i
r" P=1
o4i1l p
=2
I
0 0.2 0.4 0.6 0.8

:
o a1
Ealq=O[oJg E EE, x,
o B9EEE,x, 1
fEJ sc.l8 E-=.-ad arEE raJ. 0l xl= zgzx

cHzf
=rlEalqlEofuoll
oil,ll ol.at| oJ4l EE= LIE[1.!trf. SZIC= Gl'-EZl 6t|46lE^l ExE E/.l6t| fal sc.20GIE 680il^1L1. +l oJZl 8s.zl-BEEe.q '*3 2dE Zle-l
EOITL
5M-|. 8E.-a¤ AEE raJ. 0l HA EE-#E E-g|'EE trJEtrt.
=-c'EA
166 s trrl+
=EE
g[@ A,JEr.Het 6]l{

P=1 A7l
P=2
a4 sc.z2ql^J ac"l xs=0.e5(a,)"J gElEg #q^l r
e3
GzlE ffi;1a q "Jq+= H+= "5"l.44
t- a2
P=2
Lri 398
olr o4i1l 390
P=1 olrll P=2
b3 br"
a1
f sso a2
0
B9=EE,x, 1
Lti 330
oU 320
fg sc.21 + o-4i1l7l
Ed6l #0171 doll E7l 2¤E 4lsl e-s-4.5 0.
-rzl
,\tIII:oi JEt ^14ta1.=
ooo
b3
298
0.90 a1
0.95
* 4*zl9lg + 9l+. 0
BE
0.66
=
EE, X,
1
aA sc.20g .lillE"l #zl dql Sd6l E.Jq= a+E azJ sc.22 ral sc.20E AEB raJoll H7l sc.3oll^l EsFd EE
tl¤¤ rflol+. e^dol a,"J 8e!9 =" F6lH eCol b:J + olE^lElol9ltrl-.
zlzl t-1e4, ol +71= ffi,r.1718 sd gB +"J tF +.-4 b,
r.alg ol dol 9lilt} gqsB+El tr-q += "J +
¤+. rBl+ ol ffi +aqg br+ rJ? 2tr- ¤9 o + B4'-^l
+¤ "++d4 tr-a4lelE j/ilds
-ts ^lEl acg
7lE {r Eflzl "JqU+. olfl+ ¤tle !g + "Jgel -$+f
?l'I. "l tr-59
q6ll^J CB++.="FE 4l+6IH Hql Be
E +qzlA :z 1r.ll^l zl4l *4 o e +q4l+
"+ql "lillE aC =al+g
ol H6tjt,
^lE dillE =oBrla
q=gql ffi/.12.|fl ffio-!$ Eol z]+ ¤gde +"J tF 99"14. "lag zlga}E
a^dol a,B !EolA+. 3s0K(ar)oll^l #4, acol xs=o.ffi(4)"J +Etrt.
==zlE.ll
r4 sc.z13 +l "J4l 3s7l-S.= a+q ^J¤¤ rHol+. 4l+6ll^J #olts '-qi] +qE nz1 dd q *P"llzll, "t
acol 4,"J *olg ="F61.B acol b3?l ="# Q4ol +s-ql, zlE B= "q4l 'Jg(++d B)3 rsorollr-l =" B¤r}. tr|4
olag 2^J g6J$ol+. ol + 6J ^JE aC$ a;o1:z += 6J ol qill= 3s0-3ezK,tlololl,<l #=+.EI"J !+ +g
^J
t3 a;'"14. +71= sol-LllH r a{ol xr=Q.(sol ¤ aol+. ol i-l
=
r4 sc.zlql^l 3¤d e_r E^19= acg *= 4l= +
E" * GzlE B4l^lzl$ xu=0.66oJ Ea^ddg,rl+ rflel}
ultrS Ceg,+4U+. ol AlE e,9lrl + "+ill^Jg BC6Iq, +. r4o-lq qlAq 330Kql^J= adol xs=0.87oJ "lAhl
ol + /b}ol ,,9 #z$vl4 szlg4(rq+ Hl= H6J 4 a^dol ar-0.4eo1frzlE qJ" olEE {t-4zl Hl¤* r ,
=zl] 60l g+. 320Kql^J=,r.ll-tr.-g E4ltr-ol 44421

+).#=¤ql^J +g ol go.JE9 6zl} r aC e,ol 849 ^lz|6}q,
.lille+ esq(E$-#g gaJEol4), olag ffi,t17l$ i.l .<Jez| aJ ?zltl.r* + .lilltr-E 3t1-4lE 94. +
"qilltlE
s=+ Egt z^J e.oJgs S4.
"l
g"1¤g "Iil +g Eeil adg xs=Q.lQol-I +="4illtr-g xr=0.809-E_^l r Hlg
H ga+ gEql^l +gqjr" E. ++¤+. ol 0.s2: lol s4. 4l+611^J B4^l7lH ol Alzlz* gqe
e E9zI{, ze8K"ll^J + t}E adg 0.20r} 0.e0, :zzl-r.
ol=E tF ll4 "J* o.az : 1ol ¤4. 4l+6ll^l ="#9ol H
q EqsH ++"le-l diil4 ade BE dd ++6t41 s
Elo.l-rll g+. :a?-lI Elzl"+ "-q{lr} $f¤ trll= ^Jel aC
ol ilg$ Aril ¤+.
xlT l rJTl 5C.3 0.4er T -2e8K"J d ql^J+El LEl=
xs =
^l
H+= zlzlt- +le+ ee ¤Bg !Eola}¤4.
sc 2gE xlel gtrJE :.H: o4ill 167
T}ILJ=
=g:d
tr l. Raoult9 H4g + +lgC .lillE E 2CE 419 dz,ll 6zl I s. Eill s.J+g #olI ¤+^l7l= $Cg 9$ol "Jq+Al 6I
"Jqg 414}6l.= ql "l+g+. q CE$$ Ezl^l7l: ,JHg gg ffiz}a aJ4.
e 2. -gE-E¤ AgE ==J{l
L+4+= a4lde q+l gEq^J s n 6. EH-# Eil=e aCol H6tzl ?*r +Bol q= Eill s
.JEr+ ¤¤g ol+I 9l= tl$fl aCg +4U+. t*8"14.
tr 3. ¤eg olF r 9l= +7le+ ._4ill9 aCg ,,{EC ¤ql gil a 7. ffizlosr doli "lill= gszl +l g1l Eat| ps.u-+ *
OJtrT.
4Lr olell g4l E6tl ts.u-r1k¤- ql {} B"-l= gea+. ol
a 4. rlEll TElg ols-" 6[{ ¤¤g ol+I 9l= 4 tr"=E t'"'ltzl r+c=e a+ +E EBg zlzlt- EEB + 91tr1.
9l+.
=^l]#+E}+
=sEt^lE
,\loazl /\l
--1 +^J al Ha
Zzl9 zd f r= x e,pil lpi + (pi -pi)x^) "l^J +E sc.4
fs=L-/A,
d^ll 6zl "JH p = pipf t lpi + (pi -pi)re) oltl +"1 sc.s
zlql +4 nrlt=nul, (CIlzlle}6zl {l"l ¤¤g ol+I 9lg tril) "JHI4
oe, (t ael Bql ql4 n,lo= nplp) sC.6
E45D 2tr= 4lel A=JE raJ: zill
> ol EEI= H[+= 018

a1 V
s4ill
ri{l EdEE 8EE :laJg r]lE rl¤t, 0}e rlal-+, :r.alr. El=l P=1
8g0ll^1 qq 8EE adE e.E6l"= Ell 'Jal olEEz
=EtE
?leq, 0l- "=t|4 g + ?tts aol 6sdttrl'. l-
a3
o-Iill + A o-4i11
Lti + B
olr
①
> trqc T]ILJ
e2
a4
aBB raJg 4lej Atfll 7lE LIE-d dEtloil ?t= + ?l= I¤- l.ill
a-5 a-5
Ll-El'.! rHolrf. a_
b
P=2
> rJ.e-d qHl rl^l

0
BSI EE, X,
=
Eill-Eill aEBg 6t|46}a +4lel a0l fg sD.l zE ?J^lu EillarEHoll^1= sE6l #01=
Etgl E ?i0lrl(E4 sC). ^lell =sdg =A6|ts -r^llSEt|oll^+= 4101^l
2dE Xlel Ps-ad a'JE raJ. ral sc.21ll 3 l:Br'= fs-a[Qa[. srfr
5rl.-lts EadCg *E 4d, Ar1 6H=J:dtrl'.
= =#E =-c'=oll
ol Eqql^J= #=¤ ol6l-el s_Eql^l "_4illt}4 _l.ill{to1 ;r- s'JEg +4U+.2 +8- aCg *= ._4iil= +oJ gEql^J
alql +6ll^l rg4l p;rxl. ++. gq, rzll A+ lill nz| Bzl 4=9zl t*E+. +e a^dg
=6k aill= += qqe} =Cql^JE+E EJ *g gEql^J aCE
5D.1 EE=il= HsI S"l ++.rfl+ e,! e!$ql fl= "lzll gq++$ B
zJtlzlE nz1 4¤Elr, g+ql il= EJE-g ts4^lzlB 1.zl
zl+ rB sD.tql^l aCol a,oJ zCE .-4illE r]4ro[u21. o1 4=g+. rq+ +& Eq+E"Jg SCqL t"J gsqlî gq
4lr| B4B oll $ezl} He}== "- r+q=4 Aol 448 + 9l (++* a4 sE xlle]ap.), qL qI cBg dz}4-o-e. 4=^l
I4o14. Tlzl ?t=+.
dazlle elill9$.zl"J tsBe +B4ss +
al=ql e+^l
q+az.4lb'olill+B'o141 g^lql 2tL s9-o + g6$Eol4, ol49 A=+o tr eI 670/o4 +41+ To/o
,q6J +&
Eqt+. +++ -Lzll sz}8o4 " e+El mI4 +s 9 Bol E.J¤ lge.! +-+.Ae*es23yo183'Cql^l
zl .rl1}ap ts= +"lg AE q ++6}rll EE}6I
9 NaCt4 77o/o4 H2O-s B +& gqlEg -21.1'Coll^J +E
,il ¤+.
+.Fg aa 6iql^J ggql+ +?-lH(qa'H ,J+ a
a2+a3. q E+g -r.x-llzl. ¤Cqa, rille+ "-4illE ql A#g +fl+) -&sz} -21.t'c Êg
olt"J C*(:r4l +& a
tr-ql4 Ee_?*g(BB tr-Ellql^J) zlBil +zl(sc) o #
¤ol "l-7qzlfl) ol gEtEol HE4. *g aa flql^J gg
E d6fl4l4. "l +!lql^l= + d-E E?*ol 4zll # ql +BlE(qlg.<J -HgB +E g+ql+ +il
4 o + A+. rrl a B7l g+ 4=9zl oll$ql "+ ffi ^#g ^+g
'I) 9¤-"1 $!.rll,
oltrll. +eH^J 4"lzl g6}EE+q gg
illtl +qlE az1-Hz]B4 q *+6141+(r ac g+++.r?]4q 419 .$s7I LH4zI{, ++6J "Jel a+g
ol bro E +qd+)
zt6IH *& 9s7l\ $zqg + 9t+ t}B+el 2C+".E Al
a3+A4. ol B4lE Eql^l= Eillel oJol 43ql ?lg
7I +& g6J{-g ¤C6kEll, "l4t +& Etl$g:zill Ea
r
trllE+ A^6Iq, adg ezL
"l "l4l el El^ll +aHql^J qlB6l +,q61+ +& ac rill= Hl+
7l gH +++ ee] tr44 BeJ 2^J=.444.g+. 2
4l-e
2 +8¤ gqE eutecticol4tr 6l+rll, olag rq^qE 'd4l +e-+4=
rae so.rql^l E-aCd e,E # 4d,
=
Axl \i{$ "Jq^l +4 ¤ 4o14.
sD 288 zlel SiiJE :.aJ: 169
=.i11
8-e. 1000
e
800
OHiJI LHTI
o
a1 -/'ll -
(J "-4ill
o
BAE 6 600
dz
gg lrllal ui
oU 400 c
rill 'J4
200
x
.!O 1 a4
a
0
0 20 40 60 80 100
Ag9 trH "/"
-19 sD.2 rg sD.loll^1 EoJ 419 'J4 +d. a9 'J4 *sE o,
oll,\1 =IdC
A46fttll 0lAg Eo-{o.E+El Pl 4=El7l a:7[ aq ll0l
ttflEoltl.. lB sD.3 ,J.J:d ql sD.10ll^1 ?.!E-d gg:d ra
-el+4e-l
oll^1= E+ r^1ElE ttllzfxl 'J401 3tral B+olTltrl. 0lalEl
E=e =E E¤=EtEol
ad e01l^l 'Jtl. e= 'Jcld 4d(A7l E+-doll^1= =E
^lloJ
E=01 rl^l $oltlrl-. olal-d'J4 arEE reJ= uEts Ell ol8Erl.
=ca 5D.2 Ht34l
ul,tllfl Aas=E
¤ 4el +"J+ gaJEol4. ol + r*9 zr33 E6JE3 Hl¤¤ "Je4^l +.JEg "J=+. olEl
^J4lolzluJ
ul,<llal ¤A^J=g ¤"ldolr{ x_d El¤4 +C +z eCB
$ zlzla_ ^]trts + 9l+(E9 rse). HlEillE BC6l-= ++4lE E + 914. ol alE p+E+
GaAs
+& EE+ES "J"t4= ,lt} ¤4,tI "JHg ¤S 94014. 3 jlolzl"J caAs= Ga+As+GaAs HI*q E6H^J ¤CHzl
re sD.loll^J E" add a,¤- F6l] rll4zl= ts4 +EE S4 qlEql +B CEe E +ol+. ¤zlrlE
^dE Ae+ B7l-sI*E
6l] BH ol
'ilBel "l+Hg "J + glg aol+. "l olzllE a,ql cE +rq=a E ol?cz| e4 4* rala +& ERES Bd6|
~
E$4q B7I 4¤qzl .r.11ra3 qlt4xl +=61 ts4lg+(rg zlr alitrll, ol 4le+ +¤E q zlzl fl4E {$apz} $Q
sD.z). B7l-4¤q= a3 tsg 43"1q^J ts4¤- E+l-+s.E (re sD.4).
B4l +Ezl zllfl4. ol ts4 +E7l o)"lzl4z1 BoI llE 4*9 Bql+ A. 4q+E ce+ EIHI* B-tr ol+q4 A17l
"lillel ecol +& a^dql Eg6IH dill Îtr71 r.rllq¤ ql ¤4. "l ¤ 2C+ 4lE^J +& s"-J+g Hl= +
41= ce+ BE
nlzl $E l "Je6}zll -,?zl$4. ol "JC 9s ¤qg fr$ E glqr ^J4++ +&Ag z*Y t4 sD.r4el f a ilolde
Eol4l tl+.+"J ^lE7I ;<l¤+El +& 4d e. ztzlB * dill tI¤¤ rHol Ae+ BE ¤-*E(x*=0.sE^J re
=:-E.+
e¤ ¤9 o + *+qfl+= a
+¤q Eg$ 4t4z.l q^llzl-+=61 B4LEII, olqî dill ^l sD.4g c)4 ++¤i B
Îolel
-H.71 Lxllsl¤ 4t4zl EIE"J +& B+ol "Jq*+(+++ .l ol+. ol tr-B¤ rH¤- 61146}=
"JHg-zB so.rollrls+ ul*
illT} g ,Ie+ A+). 6l-+.= oJ :zfloll.<J Fa^dd aE uI4 ts4¤ ullE slaJE c
z| lzllE 4=qq,gsz| an ol-4E 44zlH ce+ Bs g +
zEtEt q 5D.1
lill{rol tsAl ¤tr}. +++ s}q}E c7} +e-H F"J6J a¤9
ㅅ
:zH sp.:e e/+4 4E tr-B¤ rHol+. gq.ql
2^JE
AtB - C
r *ql tLE¤ s.^16il +gt+. acol a?l q4;llE o4rll

,da
=4d-=
B4^lzlH argl^l +4ol +6llg :/ill ^Jql 9ol ddgzl P=1 a2
arollrJ rlez| sd6l rillE+¤4.

C
^l4I6Iq, t- a3
Lri
0lr a4 e
arll
dill acg
.a.rjl
,rl4^J tsL+q 7LE^l ts4 +dg Eqq6}ts P=2 P=2
tr-¤¤ rBq +471Bqd}ril +Eit+. fs7| ga1
=q4
b d=e+q= "qill-rill ^J AAIE +6J + 9l:r, zl* 7J * A
x l
!o
C
ㅇ B
+ H=:_q-E+q= +& a¤r+ ++a(+&d)¤. +g + r :14 sD.4 Ael B7l HJ36IG +-cfE C=ABE ed6F= Zle-l AtEe r=J.
el+. 0l rgE UJE;|E ral sD.1rl- ,Jol-crl-. c= EJ+-L| ol-u
Tlrf tr|-BrEolrl-.
=E+ =-ErEol
170 5 trr!+=-stE
"lillE qtsrll oleloJ +¤¤:dil ffiol+r ++ b.ro a.

io a Eilt
T1
P=1
:l
ii
ii
r :ijiL.-'-i'15=,
5D.3 Hl:dil +E r [riL\:,',95
,-I, rill
F,m Na,K + -I-i1l K
UJJ (aaJE NaTl EE[E)
+6JE c7t o-4iilE^J= E.JAts qE :14. :- ql ql= Na,K ui -,

oU
,,
I Eill + rill Na.K
olag rill ^JEll_e.^J"J
oJ^=!"Jrll, sp.s). a^d
T3
5 nill Na,K + Lill Na
1---t (4.aJE K7I.EilE)
=4++(rH T4
ol a,oJ Ezll. B4^la ql "Jq+= H+=
^J4l6]]EzI. P=2 m EliLT.:,!541 *"
a2)a3. NazI ++EI -LilJ $e{ol adqq +{zl K
P=2
NarK Na
r ariL..ixr#3
{r x l
.+41= dd r<= rJ t*ol sEL6IAl g+. -
,lo
ro
a,$ ule g. .,.1e2]. Sd6l arllE Btrt . Nazl- S

Rr
,l0l
fH sD.s r= sD.4oll LlEtL.! azl erl"J F 7l^l il'olE= LIEIL|I= d4l
il 4l(Ll-EErl' ,JE)g AIEB raJ. 6lLlts AB Et|tloll ArB0ll 6t|trJ6l.=
+6J rzll(A%iE K7I s+g)e+ .r.ill NarK_tr_ ${. nlru
AFBI= NarKT[
^tolEsl
$fltrtts ?iolr, s. aH-lE 0l A[--JEol r.i]|B,t.J"J
=Ifldl'r,
o-qilLB^1= ?J=tr|-= a0l+. 0l EIE|ES HlErxl #
ol{ql= b,g E" 461+ E-a^J dg Ez}. goztrl. =^t{6f^l =tstr011^l
^J4tall
b,+br. +*+HEIrI "J{ttzl ?*42| * 4Al b,

9l sE:"tH Nazl. *++ a4l 8e4ol 4=q7l br+bn.4l+6H^J B4^l7lE r.ill s|6JEq "Jol
^l
+++. rtz$l+zl- b4ql Eg6lH q44l7l- +& a^J* zl
++$ rill +"-4ol 4=qzl"J arql zlAl g+. .+41= K7l ++6J r^ll(4"+9 NazI
br-+br. Naz| "l
rl NarKzt ^J^Jsl= **"1 .Jqki+. ol +o.JEg s+g)e+ -r.ill NarrE- ¤ z1r lz1 go.J$s ¤+
r flzlz} r4l Na +e-E qtlqq Eolzld ¤C #
E+ ^JCg r4l=
tr+^l ztgol{ E"Jo.Jel +^ltr. Hsl-zl- "J9
br.ol aql^l= o_4ill, s+oJE NarK, rr]r

Na-*
#i U+. .lill Na,K|- olillE^J= E"J86I7] trllEql "lag qE
ffi +4lql^lE ,<!zlzl ?*=+. olal6J CAg Hl:dxl ffiole}l
+ ,.4l(A=J9 rczl EEL$q rll r}"l ^JE BB¤-
olE+. r^J ¤Bg ++ql= ++lcg Hldil 6]t'll, "l e+6JE"l +eH r zldE .lilltr-g "JEzl *6Ir
"l -t CEo-E E6]]gtrI.
I dol4l ++. "l tr4l"llrlE Nalr E4 sqlE
ol AelE lzll NarKe| ¤¤g ol+I ?lzlq} qq^ll
NarKi ^8zlzl *=+.
=s-d7]lE=
tr l. g36ql^l=._qill^Jol
eCE Es] S"l r.ild;e_s E+q. a 4. Hl:dil r+Aql^l= El6JE"l ¤+ElE^l r CE=E E
a 2. ^J¤B rH9 HFsFr!8 dql^]= EzH9 tE"l *lBg olEtrI 6rq, -
o_qi-lld;_e_s=
s=trI.
=x}l6}zl
tr 3. :dil +q^l= Eillg acol Li]l ga3gq- Eg* acg
4=trI.
EEJ sE 3¤E 4lel A=JE raJ
0
Aeq
lq
1
> ol EEE ull+= ol9 =rr

'2J=
g15;p 5 ge +dEl EE=E
)\71 0.2
^dE¤E ^1lattrl
8ff1 rllE rlEloil^1 qlq. Ars
E?zt #$flxlE^1 3AEAI
=s6]|rlr
Xc
0.4 .6
xA
/r\ =rr
> Eqfl 7flts 0.6 cE
0.4
aEB rBg Al9]?18=01 oltr 4a 6uE 7El ?JE6Pil =71
-g + ?l=r|= HqT= :lBolrl. =rl|
0.8 .2
> qHl rEl

=J.e'Et 0
2AE AEE -raJ(E4 scsl sD)el 6}|4 EIEII+ I ?+l(Erl 4A)E
o 0.2 o.o
,, o.u 0.8
'l
EAtr6l= aol Etol E aolq. q7h1 LlElLll= aBE faJEe

?+l(-Erl sC)= 0lE6]|^1 6}|46txl Etrl. reJ sE.l 388 4l= Ll-El-1fl= Eil ol8El= 34e 4tE 4 E=e 2aE 4l=
^lEll LlElLJtrl.trd a 89 e= E=A Cel BE E ffi Hl7l5g6ttrt.
dd a) tr-ql^J= +zld Aql 7vl+la++ Az[ gfo[zlzluj
d$ol ,t;l"J
c=3oJ 3 ¤E fllE ^J46|]EzI. ^J +zl(Eq B:Cg r-o E Hlgg H6Izl ?+=+. tr++^J 6J 4ql+ A= 7l-g
=
4A)g F=5-P7l g+. 4lE gEe+ "Jqg "Je6}rll -re^l7l ad H+= +444H 4zld ee.*q e49 2C+ 4l
qlel
H zz11E z|$Ez| S"lzlq q+^J zI+E= F"-3-p7l 4 E +4.11= BC ^JE dttzl 4dg r?_lH g+. CE 7l
^Z
+. EI"J 27Hq trol ¤xll6IE(P=2) F"=lol Elq \)zl ttll! 6IH^l rJzlE 3^JE 4lE ol {d tlE olHz}"| gtril ¤+.
zl+EE *=+. q+^J + CEe] Ee%¤ HEI^lrlE +{
ztEJEt 0l se.r
zl + CEel Ee*ol ad$ ^J¤¤ rH t'-"fl^J
H6J+. ol
HolE -s^l$trI. "J9 lz11E tEol F"=0ol 'lg d# rH sE.2ql +4rllfl+.
qr tr-¤B rH ^Jel ql dse s^l¤+.=z]]6l-H(p=3)
z-l
d xA xB xc
3^dE 4l tr"B¤ rH t}g ds=g 24lE ^Jol +=6J + 9l a 0.20 0.80 0
aag +4utrI. 2cE tL¤B rgql^Je+ ufilz]zl_tr $ b 0.42 0.26 0.32
= ol+a c 0.80 0.10 0.10

¤g 9l= + ¤eg+.
^J3 "**d_qe d 0.10 0.20 0.70
e 0.20 0.40 0.40
f
5E.1 3# atsE f.aJ
0.30 0.60 0.10
ol rHql^l d d, e,fY x6lxr=6.5s"1q + zlddql 9l+

3CB 4lel 4l ¤+E9 E ggg x^+xB+xc=lg q}4rl4"F ag ++-6Iq?+.
6J+.5.H 34¤etr ++U tl¤¤ rflg
ol aag zl+4 = 0 1
o_tr EJ+.rlzli.clJ,
"lag ol :48 "JE + $ttzl{ 44= 0.2
Eql 4r-4I ¤46}4l +A6H^J EL6}H lol qzl ullE"l4(:z
^ll
0 .4
H se.t;.
re sE.lg ol *4lz| dzlls 4. *L-+= 49 eq+a :l
Xc
0.6
xA
0.4
+. H nnE xc=0o14, += + Hql qlql^lE trI+7lzl +41
7l CB6J+. tr+ul^J Hg 7+7+ (A,B), (B,C), r4r (C,{)E 0.8
^ll
+4U+. 'H+9 d3 ril d+ol Ef f{lali alql 6il'}6J+.
qlE^J d p= xe=0.50, rs=0.10, r?-ll t=0.409 +QUtrI. 0 0.2 0.4 0.6 0.8 1
0
Xa
+zld As+El :z 4{ztzl= ¤4$= zld(:zfl sn.r9 fg sE.2 ,.tEEt q 5E.10ll,\1 EEEI E-=.
172 s E!+=#
. $d6l g6Jq= (E,w)e+ (E,r)E + tle. +"J ^J ¤qg

A .
¤dql+
A (w,r;4lt:489 gH)e 2tF ¤qg +4U+.
+
u
A :4¤9 "JHg 2^J+ tr-¤¤ rflel 6}+ql a]]B,*4. zt
ol
¤q ?le-l qgdEe ¤¤g olf + trE adg dql4
0lr
A o e +a6}r r ar+. tlBB rHql = E^loJ

ffi zl{-oe
A ¤e6}q ?=+.
2^"iE EJE Wrlq1q ++* "Jel EE 7I6J ull= +.J ^J
lg sE.3 8E= Efe s-st^le q= 34C Eal= Eg9 AEE raJol "l ¤Cg+. :.H sE.4el d aE uI4zlHrJ ol sffi ¤E6J
LlElutrl. 0l Eel=E -el .JEol gloil,\1 ¤E-d 348 ,s'JB reJql 6H.J:drf. + el+.
a,. AIY + tFe-P ol+qalq, ol

+ ^JE tL44
+++ 34¤ tr-B¤ rBe E7l+ zI+E + 6}+(qla'l] "J3 zl;ll +!g ol+6lq glq{+.
sE)7I <k* zl4 rI9 ¤¤g ++U't SszI 94 At)az. EE 71611+B o,r| +zld E= E= dg
=AqI
zl$ ¤¤ Cdol +_erll +4+q r?-l6}q 34¤ ^J¤B r trt4 olt++. a,9lrl +"+g qd6l f {tolzlu3
H"l B4Tlq. nt4^1 7+ 348 tF¤¤ rHg :.H sr.:4 ? rtl fto1^J"ll= EzI q "*3 wz1 E4zla(A ai',
¤- rzlg 3r+ !4ag 6J +¤ *Eol4r E + il= aol+. E E^lq=),w71+"J ^J 4ql+ q "*gTTlEq {r
7}=ql, olag + q44lel +6ll= Ezl $zl ullE"l 'lo
Rr
-l A}rdA
ol ol*Ltd c]--r-tL =-tLi
FF rafJt{ rll r-L
cE.L
^ J'dE 4l 1. -=lrl-
'"11 o-o o -zlrnl
' E-ii _i"i-r_i ij-u- L; i -1-;
,Dl
il
q= tr-+ql E+= wzl ftzl q= tF +ql q * nlru
3CE 4l tl¤¤ rfle ot+ol+ zller++ +otql^l 'J4 4 ol EqtrH=-- aiol dr'H4 +zld Eql EJ 7Wtr+).
olr 9l+. "l ^J*B rBol +d-6I71= 6IzlIrJ 2il-fl ^J¤ a2-) a3. ar9lrlE + tt-.I 6lzl"J r7l +
=: =41617l=
B rflr+ q+61 Hl+6J *H " + 446J + 9l+. "J tlg 94 e"J
o glrll ¤trHzlell +4ql 44).
a3+ a4. 4lql+ zl+6H^l E. 7I6lH +"Jtlol q
(s) ff!$eE #ol= o4i{l= ol anE 6J=o}I. ol Ag HqA+.
rH sE.4ql^J ^de w(E)e+ E(ql*t} o1-,r.11s.&)b Sd6l 4
ol{, re} T(E4=e eql+)E Sd6l 4olzl"J ws+ rE *
E4_o e 4l"J+. ol ql= 5-7oJ.,<J1tr"&i=+ + +=: 4l7I ¤gql
+4111= d¤o14.
E(rB sE.4E w)r+ zJzl xy1=0.404
^l =E-e.-nEi(T)ol
rr=0.60oJ Eql-Eql ol.,rlle,t}(E)= 7}6J+r. 6}z}. we} T
E tl.I4 Hl$.g "JA6Irll -,?2194 rr]6}q dill aCg
1 CH3COOH
+4ql= dg eH9 ,h=0.60otr+El o}'tlltrt} 4Adtl
0.2 zloll olei zld b$. ul-4 olE"*4. Z7l 44? 2tr- ¤q
0. 0.6
ql +lil6l-H,:zf fl tlg @* xpxr)=(0.05,0.9s,0)E ad
Xw
+ 9, :41 E- + ,(}g (xw xp xr.)=(0.88, 0.12, 0)91 e¤g
0.6 0.4 *=+. o|.r.llE_&¤- ++61 7I4q r E Egg 0.18-tr g
El+E 4lE (0.07, 0.82, 0.11)!+ (0.s7,0.20,0.23)"J + tlol
0.8 o.2
t:39 ul8-e. +44-= 2tF g9ol 84.
Hro 1
0cHct3
0 0.2 0.4 0.6 0.8 1
xf
feJ sE.4 ol^llEtl(E), E4=qtrollEJ(T), "J E(W)E 3dE 4l7l- g8-d

re sE.4qlrl p-tr. s^l¤ d¤: ¤E"l4l 6J+ ol dql
ol
^J= ¤¤g
olF + tlE
e-EE gelollî LIEIL[|= A}EB rA. 28 gq o-pll ",!Ad= H 7H"J L|EILH
= =Col E"J6Irll ¤4. Ag "J
fltl'. d a 89 trt=ll^1=Ezl=tr-+DllElrl'Ee-l?i=l="J-d ulEE 0lEr1. +E .J4ldol+. Eqtl 34¤ ^J¤¤ reE "JqI4 6114 "J
sE 3dE 4lol8trJE ral 173
/\ll
or-!o
ol xî /\lrol x^l
o4--.t .!o
rg sE.s 34e 8Ee raJE 6tl4. Lt|+el gEe 28 gEolq, -JEE lal sE.6 E, 3=, "! le.e E 3E0l LIEILI|= 3dE 4loll
0l+r ?t= + 89 ad= ={t tr=E +qcq-(",{Bce d:-J=
,,¤3d Eel lIilS{ -ral
rl.lo-l ol l ooorE. ^qlEal^
-rlU --
E6H^1
=trEcl).
B¤-:zB sE.sql ,qE6ll +9t+
(b) 3¤E 4l r.,t{l 44= E^l tr-¤B rflolr[. a[EiE=$ E Eg EH41ql

e=* EE¤. adg +ElU+. ^ll CE=ol roozozlzl zloll
:B s6.o9 3r+4 t1-B¤ rflg r,ll ztzl ++ A, B, -ur-l_L C
4 *llel 348 "Jql^lE dEe g Egg a "
7l qel ^Jolt acql^J trJE= d¤4oJ lill 'J+ql 4oJ =E4e+
tr"¤B:Hol4. 4r. 8zo9 NiE aCg +4U4. ol edg zlet E¤4
oJ .18_8
=dol+. d b"ll
4ql"Jp_l^ +A,el 6ll'J6l-= a
C3 ztt ¤qql +6Iq, r+ 6J t3 cr"lr" += 6J
^Jg.
rB sE.63 B, tE, "t qAE ¤ zJ¤"] 4 I-FeNiol+.
Êll"Jp-]^
T]ILJ=
=gEI
tr l. EH 34e"e 44H tr'¤B rHg xA+xB+xc=tol gE a 2. T=Eql^l= ¤¤g ol? + ^Jq aCol E"J6Irll BtrI.
=
C 49 zlFzi _o -e "J+^lrJ+.
Eii! rrr
+-l ng EFEE
=!o+
> ol E4E uil+ts ol* o^=h E0l,lE gEE t=¤l (sF.2)
018 EEg tsol=

=*# #
6lrlEJ dd EqqE
ol6[6[qE 0]84 g+-e.-eEHE="JEol7lts
0lg= tsE6|,3 olaE ExtJ +rHe_l ¤}E"EE +4Ll]= HIe+ aol a+E qqg
ol
+lErtEE Tlxla LIEIH + ?lopr ^lol
ettrt
4ol ot,-]+. + +,HE +rl "Jqg +C+ trFSql ol al$ ol
> u_Id TllLJ +6ll^J drll +6J + 9l= 1"14.
trl-+5e-l gEE f;.E 5E= 0lE6lE 0184 B#
?EE =
BEH= Hel^l7lxl Bl rct|e lll
=718
9tB zElEt 0ll 5F.1
^l-
4E^le fl+. +
=Er'Eoll
100 "Cql^l 0.s00 mol dm-3 KNOr(aq)el 3zl "Jqg
ee.e5kpaol:g ol gEql^J ++qt E4 3zl "Jqg 1.00arn
> =JgEt oflHl rl^l
0l E43 Raoult9 E=lrt Henry9 E^.|(E.E sA).e+El f;.E-d (totkna;ol+. trlul.^l ol $rol.<J ol +q +E EE gEoE
ElEl=EE gel
6-}El tr18!-5oll g4-d 7ioltl. :zl-L -tr4
sBoll^j-Eg:d 8t AE EEoe
^loll
g= 4EE 0lE6l'11 Etrl. =+q-4e4.
99.95 kPa
0A= :v.77V
rort<p
+e9 *ETI 0o + d=g++ E= +ol]:==g Raoult9 B

ol Eqql^l= Eq
+EqL 4E¤ ol^J^J o ++
sAe+ sBql^J
q H,q+= 4lql+ 4+^lrl= "JBql +6ll^l ¤E6IAq. ol
!g de q g "J+^lvlo + +rflg 9E" Eb xe.) loJ ql r
E Egr+ e4 g+. +
AIE q= qq Eqql^Je+ pol e" ufli AE, +Ag B-e., :a?-l
r aA+ xA, xe i 19 trl] (5F.3)
"JHI4 CEE¤- IE *21a3 4o14.
r+q=r+ eol g-EE Al+ F "l+4q ol +H +4lE +E|.ll
5F.1 Eu]lel =JE= Aol S?]6I+.
=
olt g5E
d^ll +"+ol4 +,Hql 4 ?ol 4+El= El+ ElQl¤el at=Taxxoi yo + 1, xe J l"J trl] Eotlg
zt+ tEell
(sF.4)
"JHII$ sA.2l^lolE+. + t_tx=tti+RT ln(potpilolQ, ¤zlrJ

pi: +++ t4 Gzl "J4ola poE *q4 +ql d ol +41= E= gEe+ "Jqql^J dBEL+. rqE ¤:"l]9 plol
=q9l=
ts AE +71 Sqol+. ol^J +"lE a+ql= dill tE H+lql iilQf¤g +s=r+ ?"1 448 + 9t+.
e8^J 8"llzl Raoult9 B4(Eq 5A, po-xopi)g "J+^lzlq pte= Fi+ RTlnxo + RTlnyo trlE!¤ (5F.5)
EotlE +trf
E+^J sL.n4(+ Ira=r,i+RT ho)g ols" ¤ + 9l+. 8.-4ol
Raoult9 HlsE+q H.qB ql= +19
^lg
q+r+ *"1 al +r|]E E= *4E u|+^J xe=14 tbar9 Sq 6lql fl= +
^J
:r- EoJ!3 rqlE +zlÎiltrI. ++ alill +,Hel t4zl ¤+.
Itt= I,ti+ RIln ao E0tlsl gEE t8e-ll (5F.1)
5F.2 EE9I EE=
q7l^J aoi. 49 g=E?+r 6}Ecll, olag "J+E '+E' E
E8ol4. +aE gEo E 4l+e+ E= ^JEll= Ael6l-= 4l Ezllz| qE a
.$44 oltr-+.lql 4 *"1 4+qq, ol !g
sF.t^lg ¤zll g +eol xB-+ 1(++6J +Aql 6}]'Jg ollzt o}.leJ xu-+0oJ
lre=fli+Rr tn(p^tpf1e] uJilal{ q+4 Ag +4lE gg + oll ol4ol oltr-4_#g 4HHenryq Bzl)g tl+b 4o14.
el+.
5F EJ-EE 175
(a)olggEE 9-s+q9 olBS d+ ++EE ar_E i-l?l¤trI. Is=Ii+Rr

ln(prlpff)9 +Al= qdd CBdizl"J q7l^l= p;=pfr-Rr
Henry9 Bzl(Eq sA)g "J+^l7l= +e s4 ?zl "Jqg
h(rr/pil)s+ ?3 ¤e Hl+l + snzal c-EPq q+4 a¤- +
ps=KB rsTI ¤4. KrE "J+E Hlql t}+rl. "l 4*9lE n9
s++ iqQl¤g tr]-e-l} Bol 4lE e4l gr}.
448 + 9l+.
lle
Pe= Kde I^ -
tts= pi-Rrln# . RTln nrhfr
Itr,= !i+RTln =trrf +RTln
K,,x,, K,,
- ui +RTl,, p; +RTlnx,, k=U;+
P; 'r'
I)
P;
(sF.6) ol sF.e^lr+ ul:za|fl ¤+EE auz| rf--$ 4ol 84.
^lg
Krel pt= EF +eql r+t} {tfEol{, ul4rl E ll 6}rl aB
Ps
Etrg g5E i+tr1 (sF.10)
KB
a4 'Jg Ei4l +q^l 6tqE 4l_+.S E= e+E EIH!¤ p;E
+EB + el+.+, +4q a+e+ e."1 ol a+qlE q-s=rl trol g.Es 4l+=
p|,-tt[+RTh$ (sF.7) EE{+ {ol u}r}a}rJ.
p;
as=Tsxs Etrel gEE 4l+ t8eil (sF.11)
tr+4^Jol^J4-#g +E +el +eel 3r+E Elfl¤e ++r+
?ol E Eg4 +al¤+. ole+eol 6tts ol^JceE+El9 olBol d+ gf¤lE Ali y,
+ql ALfl+. +aE Eo E7| oci,l zlllflzlfl +eol Henry9
=IIB + RTln xu (sF.8)
Bzlql qe4l 9o + E= g-Eel "Jqq^J q¤. +al7l CB
,us
*"4"1 "l^J4olfl Ks=pt(Raoult9 Hzllzl- 9-::., sr.z^lg R dr+.

Eal pi=pil-tr- ¤+. as)rs"iTs)\, xsio"Jtrll (5F.12)
+eE EoETI 0o + d=+ql q+ +ee olt}4 BE9E+

E7l sA.4oll^le+ zlol 2e8 Kql^l E-e+94 E4=.E rl H"l4zl $}rl1 ¤trt
E"llH.49 g.JEql ql6il^J= \,op"non. _24.5kpaolI
p|,op*o,,.=+6.3 kPaol+. tr+4^l Sr.Zal9g.*el "Lell4 t9 EW
ol-4 rllolq=
ialEEol itx{o
=o+-l -
F++er"trllE, e)"il
er+= eg + il+. "l+6}q 2s.Cql^J
H"J e4=-e=EqlH:(=s.aEEi, C)E gEEe+ 9E"E 4l
Ill,op"non" = /l].oounon. + nf f n
ffi += al&61-¤4. "l{$..$uN+ + H 7 +eEtr -tro}e|..
=flj,oo"non.+(g.3145 ) K-r mol-r)x(2gg x)xhffi xc 0
0.20 0.40 0.60 0.80 1
prllroa 0 4.7 11 18.9 26.7 36.4

tt* -1.58 k| mol-r
-- lapropanone polllPa 46.3 33.3 23.3 L2.3 4.9 0
EI+^JE= <ig +++ Eillql q+ a}4 -1.s8kl mol-'9 ra{EJ AtE} +olls^Jel gE" E(naoutt9 B
=_E_tr_EEi9ol$oll,!
il¤ +4u+. zl $EE)Y ac=pclpt* yr=arlxsE +6Ir, +
de.,<1E ll$E-(HenryE Hzl $E"E)Y a.-p./KcE ol+
4q +6Ia ol ^ll g-EiEE+q +}EE 4)i y.=o.txsz
(b) .,gd Etr +*+.
#g flflHenry$ B!)sE+q H.qU
dxll f-q4g "l1l4 I pt - 36.+kPaol tr Kc = 23.5 kPa(Erl sA.4 + +q ols )
4. "l a+E +aq slqL siHl¤g sp.s^l"ll4 rr4dql arE =0 c1g-r1-

e Ag EE "J. + 9l+. qlE,\f vr-Q.20ql^1.
Hq^J +4Utrt.= Raoult9 HzlE 4* rr=@.7l<Pa)l(36.4kPa)=6.13o1tr y.
=0.13/0.20=0.65014. ole+ Hl+6}al uenry9 HzlE a+ql
Hs= lti+RTlnau tEE trt-+ trlE!¤ l8ell (sF.e)
I as- (4.7 kPa)/(23.5 kPa; = 9.26o I Tc= 0.20 I 0.20 = l.0o l 4.

s= tr-4= olBrll 6Iq+E_ H6Izl ?+r lqEq, ol^Jc
176 5 tr!+=#
S-= {l p39 4=+. bu+0oJ 4E t +-oo

l mol kg-'oJ oll)
Raoult9 Bzlee9el(3e-ee;g +rl]s E 4l), '
7I Eg +.rE-61-qi+. olag *e4"1 #qe++ *¤ol "JA+
xc 0 0.20 0.40 0.60 0.80 1
g+= 19 9"1.J4. +aq_e__e+el "Izl4 s4q +eg 41
ac 0 0.13 0.30 0.52 0.73 1.00
0.6s 0.7s 0.87 0.92 1.00 461717I ql+61 qeJg ag Hls olEl+ gEE4 ar+ qlE
Tc
ol+.
Henry9 BzlsE+El(=seE=¤ *4-e E 4l)' olzJl g!ql^Je+ B"l +-qflCel $Eo E ase+ F-4HICE $
xc 0 0.20 0.40 0.60 0.80 l 'E"E 4l+ ruE EoJ6Iq q¤4 ?ol 44tseeal oltr-Ce
ac 0 0.20 0.47 0.80 1.r4 l.ss E+Elq Hqhlg rq61l + 9l+
Tc I 1.00 L.t7 r.34 1.42 1.55 =
bB
ol AE9 rH as=Ts
b'' 4 zlrl Tu+\. bu +0oj
ufl
sF.tql s.r,;4194. RaoultE Bag A+ql (sF.14)
E xc+l"J ull /c-+1ol 9zl"J uenry9 Bzlel a+q=

a.+o9 4l t.+ lol Eg +E6lq+.
ol +41=
"lrlt s_E+ sqql^lE cBqL+. E=
^J4= *
ql^le+ ?"1 ol $eql^l H6lzl BI-L :.{Eolq, ol^JCe +
2 +Etel jr= olBol d+ g.EoE 4l# y, +ql *f,4. :48
"JEE EBE"Eoll^Jel dxll *dq EI+ iilHl¤g q+r+ a
\ 0.8 1.6
ol +ElH + 9l+
<F
R
u
lJ0
il
0.6 1.2
Y
1
I lls= H"s+ RTlnau (sF.1s)
H
H o.o 08
qi
ni trtr Q
rJt rrJ
r{=
OII
-eoHol
C)-l-l
E}E E
H 0., 0.4 =6_t_
/
0 0 a+ +Eq z]H¤-(Eq sB) "l¤61-H Raoult9 Hzl oE+El
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 olBq= g"J4 rr]a "la4 BEoE 4l+
(b) +alE q
1
(a) E E3, xc E EE, xc

^l-olE
f 95F.1-=e_e_seJ0llll.E{EaF=e_EollEJ/sEtrJeJEEEg-EEgl 4rll #g + 91trI. r e+ +"-qql 'l]¤I r+"J QIB
g-EE 4l+el 4¤oll trt= EE|= (a) Raoult9 g=]q Eteh (b) Henry9 =Ede
rl(sB.6^l rf=n¤RTxexs)el olaE g.J Gibbs qlqzlql qlE
E^.loll qal LIEIL.! rB.
¤ 48(s8.74 An,i*G= nRTlxolnxo+xu lrxo+6roru))o14. ol
xPl B7l 5F.1 oIîlEE ¤+EEe+ BEoE 4l+E + +E Eg +.+ql "J46]|d ul4"lEl f= zlzla_ ++U g-rEoE_ al
q .'|+ alt}4q4. +ql +* 49 +E6J + 9t+
69' | =HL's6'0 - Hr :rg'0 = u/'0s'0 - ur fy h09'0 =
vx'
t-vE [b .E
OE
I'IOI Tr+
-i-l
(c) g4:d EEs.

ol^c- ¤:9"1 "JEqe qlel g.r] Gibbs ollHzlE ss.:^ls e +
E=Jts=oll qd+. +
-E= q$|l {A6|]E S*eq,
tF{= SA6l zl-fi+7ll ^l-& xslnxr}
+4ql z}1t {stap. E 4lel a^dg A +49 + glrll e6l. A-i*G - nRT{x in.rA +
zluJ al$ g+ sl+ql^J} +.-4el a^dg E +g {dql Eg 49" fl* Hl-ol^J +Eql r}|+ ^lg q*4 ?JE}
"laql
r-o LI4.ll= 4*zl B:e_q(Eq sAel e+E+z}g tL^J rr),
-E_ b_tr_
A-i*G = nRT{xelna.+ rrlnar}
trl+î irItrI qHl¤g q¤4 ?ol 444= aol ¤q6I+.
bB
ol
^-le
E E$ qdql $Eszl-EqA 49 uull$ ol^J4 s
lto-- !' o+ RTln b" (sF.l3) qlEq q+ 44 ee ,J^l_e_+ +E6L + 9t+. rq+ C+
+qql 46H^l= tr}s-!+ ,JZ sB.74ol CBt+.
¤zlrJ9 rri= *ql^J E"J+ E= <14 +str}. ¤zlrJel C
gql qs$ *39 slqt ulHl¤C Bq p.ts}-Ezl 6"o; trll(. A-oG=mRT{ro lnxo +rr lnrr+ ¤*o*rl
5F E'JEE 177
flel + ^lE "JB{-= ^l=gg

_H_"J + 9l+.+d 4 * 1.5
EoE#^lgyfiE HI+l B=+. 3
A-,*G : nRTlxlnxtTe+ xulnxulu)

: nRT{xeLnxA + xuln xr+ xo ln yo + xrlnyr} *<
a
a.
".tBqzl fl6ll^J= d4 e. rtElu F 6JE 6Jol 6rorue+ ?J {;
o 1.5
0.5
zJ $9H
"J
g+. ol$rll qEjE hyo= ¤*i,lnyu=Srorol 9q
"t +trt.
0
Exi Eri, I 0 0.5
Xe
* * * rlrrfi = 6* + (x ux'^ : ¤m =(
^ffi ^xf,
x ox u x ox u
ral sF.2 rtg gl=Jtrl7l (RTxoxs}ll Hlalldl== E:doll

rqfl C+ +'+el $EoE Alizl ++4 *ol !Eql, ol
^l
=-'J
"J+. d=el
^lE= 69
?Joltrt. olAf EE= =ZEl =-EtEsl
6=001 6t|'.16[q !d= Ll
6il01 gg nfl= ol8 Eo-4Hrl-te
=71
EIL|1GI Raoutt9 g^lrt "J^l-Lrtrl. gr+=,
¤ lr/argutes Alol4r EL+. gtHE LlEILJrl.
6rJ0l B"J n]l= 0lar'Eo_4e.c; 'JP
lnyo=(xfi lnyr=(xf, tr/argules 4.1 (5F.16)
Hzlql d¤4e+ d=61q, sF.ls^lE zlf alol ls d=+

+. 6JE xo ( 19 trI= sF.l8^lol rl-e-$ ?ol ¤4.
g"_4"1 +g A\+71eq6irll g+b ag ++6I
ullE g.EoE
.14. + xu--+OoJ 4lE fo+ lol qq, E xd)0"J trl]= Ts+r
Pt= P;,x*6 (sF.19)
ol ¤+. EaJ Ae+ B= g6J+g ol_T= E t++ CEEolq, * ol ,EpiY Ae-+rH Alql qq alol 4s4, olag tL
¤ol4 +rll- +Ellllzl ?+= += {=_ a-r--a1q4. ^lql^l
olzll Margules ols-" offl A9 g|E" EE +94 zJ"l 4 + KE --9H ol 4lol Henr[ Bzlr+ Ag go.| ¤tr].
^lg
4E + el+.
'/^=e ;xi
Eq sBE tr-71 sB.tql^l +6J uts+ ?"1 2s'cql^l d{l4
AA=y AXA=XA ei*i = rc'og6(l-*^ ): (sF.17) gqlEql q6fl^]Y ¤=l.13ol+. 6>ool=
^l-=Edl&4E
-e. ol EtJEel ?zl "JEg oltl4"J trHe_l {lB+ Z 4e
xs= 1 -
E 7lrligtrt. El-+^J ol g*Efl dill #zl$43 q-q=$
49. + 9ttrl-. eI¤ e9 ¤-E.E= +
au"ll 4al,rJE Hl+qI Bol 84.
.l +9 t4 Gzl'Jq$ ++fl Ael +71 glq+E Hlolq
t''3( l-x"'1o1'** )2
arptlpi), Et+^J tt-ff-4 ?"1 uI4E + 9l+.

)2
(sF.2^1, P= Plnun x,r"nrrn"g''t'('-rb'*" +Plaorr"r*.'.y.loh.r"r"e
(t-x' ): ol lg Pb".,,",,.: 10.0 kPar+ Plaon"o,,.= 10.4kPag

ol+6ll,rJ
p o= pix (5 F.1 8)
rB
oe6
sF3q E^J6tfl+.
ol 6J+E- E^lqi lol :zH sF.2olq, qg4 A"l aH4B f
gltr|. 14
12 9.--
. 6=0oJ trl ol^J +aq.J qt= pe=p,{xool{
=
Raoult9 Hzl4 gil++. L
(o
10
I
R rhexane
. ¤E ll"l "J"J trll.(gg g6J"lq, +e-+rH ^Jg {r

-v.
ilr
6n 6 ><
It$ol EJg "Jezlrl qB+) +71 "J4ol "ldl -
'lo
N
(o 4
Poun,
Rr
+.lql^JE+ ++. rlol
il 2
. *Hql 69 Ai"l +"J ul=(gg gB"lq, +e-+ nlil

0
x.Den2ene
ql {r-g4}+ol gELql 46J6}+) 6zl sq"l
"l/J.
ql
+"-qql^lE+ *+. feJ sF.3 ?-l.J-d sF.3oll,\l +E--J
^loll
rq.q Zl&-d zs.C0l,r.l Hldlat
l=E-dltrl-el | gtal +C.
sF.t8^lel s,tl pffig 4*zl xal tol Eql ulrt Raoult9

=-EtEel =7
178 s El+=BtE
sF.t* olEel EES. olzll ffi$ ?ol E4 "JRI49+ CE* "3E g-EE 4l+E
EE+4,
olgE /J-s+¤+ ql+dl tr]lEql ql+61 #e +
Î"lE =_71
.l(d4l ol$ |.Ezl- r mmol k51ol6[1 +ql^]7] otq E g.Eo E y*-1ytyJ)tt' s=P* e EE gEE Zl+t8e-ll (sF.2s)
E-Er-oE__tr +lB + S,eq, g"J* +zls

HI+IT= rBlr 4 "lgEel slql irlBl¤g trl+r+ 4.ol 44tJ4.
= =^l-=
tr.= HIEÎ gEE= alo} d4.
It,- ltld'^t + RTlny* (5F.26)
"Jolg M*E irl+ ElHl¤g F*8, r4a *"19 x-el slqt

tr]Hl¤gp-s +448, dzl4-o e +¤e +'+ +q Eqgl (b) Deb/eHud(el E=l
olgEE aill E Gibbs qlHzl= ol=- EE. "Jel ?'Jr+ ?Jr+. =:d
=
olel6J olgEg
olgE 4+61+ tLrl"l^dE tl r}azfff o1s-
ol^J +aqE Gibbs q-q_4 ,Jr+. Îolql =+
8q401 oltc o +Bq "lBq= +g"Jol{, uloltl-cq rll+
"lluJzlE
5ideal _pideal *pldeat (5F.20) += EE 7lq# oJEdJqr. ^J4B+. "lele1 ^J4tql "J4
¤zlri pio,*-ti+RT tnx,olr{. rfl+
E"J EgtEE M*e+
aN,tJ r923Eoll peter Debyee| Erich Hrickelg
"lg +aqql ++
Debye-HUcke! olES +E6t*.+. 4zlrl;- ol olEr+ a- +
19 dzll +Eq ql6H^J= Ft=ti+RTIna,, r4I a-yrxll
_,q_ aq-= e^d4esuJ tzlala+. e=*4"J +E 443 ol
Elq, :.46l-0l Ff ttid,n +RTtny,z} ¤+. trl+^l Gibbs qlqzl
rzfiql 4+ EÎolEE 'tlrllt 48 r¤ -H_ot{.
zf ffi4 ?ol Eri.
qlql d6IE ole.E=g
G-=ll* * lt_=pideal*pldeat+ RTlny*
^ls d.olB?Jtr+. 4i+4_o -+ +.1 +
+ RTlnT_ 9lrJ ¤."199 "J"lg ++lql Er-l_,r" HIq]E "Jolge. ¤-"1¤.
- 5idear + RTlny;y- (5F.21)
++lql E4rll ¤u(rfl sF.4). +ill4 " + +'+e dzl4 " +
rElE ohr,rJ s_E$q9 "lB"l d+ ol e. 6J +"ll EqTlrll 6Col^l"J qL + 5e ol¤- +flql= Hltr}]-olgElEll d6tel
E+.
olg)ol uJ "*ol +zflaial gr+. + ¤#61-H eI "18
^l7!4_o
+9lql^J= eI4 ol99 gag ffiol q +q q-+^J eI ol$
(a) trJEEE.g41+ ++lql= a3 ++9 0l8Ee+ HI'}l d6IE olgEol +4
_o _+ El
"*zl ol]Eql ql olg f+lE d6l-= ^lt ¤+6tH +
¤E4eE "Jolgq 9aJ zlqe+ *"lggl 9+ zl¤
r*T_Z B "JzH E"JE Hlql d6}7l ola¤- op f;917!+a
,JHe ^87]|:.ql,
_E B4^lvJ + 9t=
'JHe S+. dql4_o e sldel {}tr| +d olee r ol¤. E+l7le+ 44214 t}s4}¤¤ 6t7l
Hl"l^J^Jql q+ 4"Jg + ++E olg"il+ +gol +B^l7l
ql$ql rE qlqzl, trI{^J r slql uiHl¤"I rEJ+ *"Itl
aolq.r46l.q z]lzfl $f,E 4l+Eq 7l6IqL4 ¤t(rpel 4. ol *olzlE glHzlzl +efl E cibbs {lHzl G_4:z ol
=
yael zlal$4 ¤+g (xpya)rt(p+r)ol4)9'¤+ e}EoE Al+'E
tI4 7l G;,0.,4e1 ilE +++q, 4+al sr.zral9 nr h7*6J
flql+. l,l-dfleE a+q} p= L, q=lolq, TldI+4 ¤+ + ?JAl q= a"l+. sJ.Ezl¤ol a6le +.les+q olgg
g q-q=r+ +r+.
Y*= (Y*Y-)ttz (5F.22)

o o
e
rBlE 4 ol3E9 e++ ElHl¤g +¤-r+ Bol 448 + ?l+. e e
o
RTlny* RTlny* 3
p* - ltf"^t + lt- - p'i"^t + (5F.23)
Oo
ol + slql qHf¤g q+6IH *E sr.zrzl4 ,JAl qzl"J ¤zl o e
o
^J=
Hlol^Jcg 5?"1 EEL6LT 9l+. o
ol HlBg "J+gL^]4^J +.+ 4ql SotrJ pzH9 "Jolg4 {
,IE +olgg q1+= E ru4relE 4+^l?J + ?14.
oe e
"l "1¤- feJ sF.4 Debye-Htickel 0lEE Ht|A= ¤E6l-= 0l raJ= g018 ++loll
EE E Gibbs 9lHzl= 4s=r+ TJol 7+ "lgEE EE ciUus r.al-r..018 ++loil^l= g0l80l "JaE +Eol E=¤ Hq
^1= =01801,
{lHxl9 .Jr+ e+ A-Et gq= fl4 flo+ LlEtLl'|fltrl). 018=P GgB,ol
8Edtq, 0l=^14
=+(0la'l-zr
EE9 El #Jg
reJe ola'l-Lf LlElL.! aol+. 0l 0lE0l qE
G^-- plt*+ qlt-- 5idear +pRTln y*+ qRTlny- (5F.24) El= EE8 ol raJoll^lHrl Eu 11 Erl.
sF gEE 179
ed^le *.E= #4l 6h= 6J ol+= ol¤Eol ole+ ?ol

ql
:. ol3 S?lzle+ tlE4r-¤¤ ete-sal "JAqq= 49 ¤"1 kg' KCI(aq)e] ¤+ ¤]Eo E 4l+= +61-
2s"Cql^l 5.0mmo[
zl flafi,tJo14.
eJH +d 1:|(b*+b_)tb" -btb"g 0l+6ll^l olg 4l
olfl* Egg ols-"ol$ }-ET}4+fl *g A+el gFE qzld
^]l7lE-
t"ll"t ++. bb +"lE EgtEol4(b*= b_=b).
Al+= trl*4 *3 oeOye_HUckel H=l o _E 4lt6J +
rqH sF.27^ls_tr+El q+4 ae aq-= eg + 91trt.
=:d
9ltrl
logy*= -0.509 x (5.0 x10-3)r/2 = -0.03...
logyr= -Alz*z_ll't' Debye-Huckel g^l (5F.27)
=-d
ul4^J rx=0.e24. dEatg o.e27o1q.
2s.Cel ++.lq q6H^J= A=0.50eo1q, r= +ge] 0!8 AjlTl
s^J +*r+ ag + qfldE "Jol+.
t -iZri(bt tb" )
olgg EoETL ?]"J+EI qqE 5F.2t\oe 4l&+ $EoE
o18 ItTt tgs[ (sF.28)
Alizl ¤EA4 "*xl ?*eq HlHql b-+0e-tr. 9zl* alH
qq-J ¤-.j"lE + *71 qlEql ol Ezl'ol+r +
4zlrJ z,E o)S ,e-l d6}+(oJolgql ql6H^J= *, ¤.ol99l
q6H^l= ¤-)olr bE a EBr-"E+. ol¤- +"-tsg +t#B trll= q4 zlzl flzlz}-*Fe] gql ^lg'++
qlql gEE Alfel +a
ol$.rllzl7} 96l :z !l$='9_+4 E"tt6}rll ¤trt. {zlrl9 H
=+
ilE g' sF.2ql +E}.llfl+. r4r re sF.sql olE 7t9 "J
Ce +"q 491 ¤zl]6t= s= olgql Aa^J 6.J6l] +qot + gg lrtzgl 46ll^-l s.r.l6ftr, se.2749tr_ 4lt}+ olE4"J zl
4. + ++E ols_uJol r EB*:ETI b*q b_"J trl] d4 uln6ll +?t4. Eil+61 *g tE(d6il4 ++ql q+^J
=x}l6l-r
olg t'1/zlzl r}q=$ ?ol ¤4. lmmol kgtola].1ql^]b 4+61 g "*gq, r?]6lq olzl,<l 2.1
= +El -s-Bol 4Et6l+= ag flEa"ll +a fl4. rr-41| Eo E
1
- 4(b*zl + b-21)lb" (sF.2e)
z| oltr-r| 4zlE ol$fic.ePEl r4l Eqzl4, :.r-lalol ol
ol$,rllzli r +ql 4 "189 dat+ol E-q7Fr E
zJl==e_tr
=Î=
ql+61 *e }:Eql^JEI 4'J6|tr].= ag "J + 9l+.
ol-g d6L4 fea[Q. s. sF.tq] ol9 rllzle+ EB*E
=_z1z[
^lolE
+41= irzl ¤elolzl sE6]] +it+ (c) *:d E=lsl +8
+aIE olg ^ll7lz| to},tJ +qI Hzl"l CB6I^] 9*g ,I=
Q+$ gg +AEJ Debye-HUcket H=l(trllg= Truesdell-)ones
r. sF.l ol8lll7lel.E=JtsE t=kb/b"
alolrpE_ +¤+)e- al.<J $f,s. al+¤- +6J+.
k x- *- x3_ x4-
M+ I 3 6 10
tosy,--42?E! +88 Debye-Huckel Eal (5F.30a)
M2+ 3 4 l5 t2
M3* 6 l5 9 42
0
M4* r0 t2 42 16 cr
qE^l gB*:ETr DoJ M,&(-&o-4 +q4 M3*4 xr- olgg EJE=) *.-!9 ol
M gcl,
g rsbtb"ol4.
^.tl7l=
x fl a\
o-0.1
o
+2,-1\
blb" KCI CaCl,

+2,-2!-
0.001 0.966 0.888 -0.2
0 4 8 12 16
0.0r 0.902 0.732 10011,2
0.1 0.770 0.524 fg sF.s Debye-Huckel ?-d g.lsl !-dE qE. 018 -'Jr1
^1Pl7l/^lE
6l.711 E nllel+-J 7l=71= 0l=rl g "Jtstr|. nEl^l 0l
0lEJ6t^ltrJ /-+001
1.0 0.607 0.725
L*g ^13
¤-'J t1l0lE1= EaJ-tEe sH6l'= Ell olE-'J + 91tr1. =JE' +el +^l--3
. zlE ¤ql q ++qq flE| ol3el Colfcl.
".J:g aiE.ol
180 5 El+=EtE
0 A aa Iu2
logy *= - l+ BI't'
+CI Davies^l (5F.30b)
-0.02
+8E E il- {zlrl c= E 6}+E + qBl¤E t}++.tf r= "lgel =l
(Davies I 'l)
>3
or
\./ z4 A4= +Ei-q1- {olap 6114g +E glzl+ a¤+ y}
o -0.04
-6[ rr{
E
4"lels E= Aol(ce+ EL4l) ,ll"J ++. Davies ^lql E46ll
-0.06
-e
^J
rfl +dg rB sE6ql +E}4fl4. sr,:ob^lel grE"E al
fz| ttrql H+lE Eg *'+("Jkg'zlzl)ql 46H^l
o.t mol
g "*= ag lmolkSr*zlgl^l= qa6l g "*
-0.08 ^Ldolzl"J
0 4 8 12 16 zl *=+.
10011,2
$EoE 4l+=,J44 Atr+ +q+ ol$ol ol$
fal sF.6 Davies 4e -_--J E4e.c1 ,5|eJ6l gtsg-d $aJE_E Bqoll,\j d-d
E "J^l,J trl Ee 5Eoil^1= Gdal E "J^l ?j=rl'. q7h1 E?.! ag
qr=flql=
9l+. "l "lEql^J. +r]]g ¤*Eo E Alizl +¤E r-" E
=rlel
1:1 Ealltrql r[-d aolq.
ql q¤41 fl=atEzl$ +e}r]l= olE4 +6Ir, olq
^lg
,rJ Gibbs-Duhem l(Sn.tza 4, nodlto+ nrdltr-o)g ol+6}q
+e9 ¤*EoE 4l+E 4l4I++. "l *H-"-+ eg e4. E

0.1mol kr, oltl.9 Egr-" EE *= +aqel a+qlE ^J'J.61
¤zlrl B= +-q$lCq tl++. Bq q +¤6J 41t!9 rg:s Eg "J6I4, ultE4 Ag Eq+ g +q4g ++ tril ol+q
'Jql C. W DaviesT} zll"Jal trle=$ A9 Davies l"l4. a 9l+.
.E sF.3 =J=E9.l.EE tE]|: gE*
CE z4 -s=tlql BEoE +*
.z!l E=.-4ill tf, l bar a=I
Srll Raoult ++ql gull, r bar q=plp*, a=Tx y -)r, x-+ loJ trll(+++ +'ll)
-8-zl
oe. Henry f,faj +aE 7ru4 tlEll
(t) q=plK,a=Tx y +l,x+0"J 4l
E7l b"oJ +eq y +1, b+0"J 4l
'ItI4 tlql
(2) Egr-o a=yblb"
7l'4) #zlrl4' #f, rbarola $d zl;llz-lH BE4= rltl4 tI4 f=yP T )I,p+O"J 4l
. 4 A+ql p-ge+RTln a.
-
#z[,rl4E ol ilzH g^l-olEg .t[^ll+ 4* z,= -u"t4
=s-d7]lLJ=
D l. E== s}.tr} trlH]¤ql ++ ^le]
¤E|]= rqE $zltlzlzl tr s. EJE S=s. 4lt= olg +.lE Hl-oltr-c o e+ElE olBg
fl6H^J
^l-e"
6l-b "J+g fs
t:sol+. s. sF.3g -Hole]-. ololgr+ *ols9l4 +*Al e'Jql+.
. 2. "l^J4-#g +E +ql Eqgi= +eq El+ qHl¤* rtnry I 6. ols ffizl= +a4 +q^l oJ olg ++l= Eqatr 9l= HI
E Bzlql oJ46ll^l CEqI4. olgEE ¤+ +49 +4utrI.
'll d6I ^lrJ
tr 3. +e9 g5E= Henry9 Hzle-tr+el9 "lBg rEl6H+trI. a 7. DebyeHtjckel olE+ "ltrC o ++ElE olg. g"Jg olgol
a 4. Masules EB A+ +Eg CEEE 9EE= a- 4 r ++lql ¤Cq= ol$ tf]zls+ Cdzl4 tls4l¤¤ 617l
^l=e ol
g+^la=4. ullE"l4l84.
c4 ^lEs+El a+ +Eg cEEe] 6
,l "Jqg +{Lll= !g +Eg + 9l+. I 8. Debye-Huckel l-d E=lg 24lE ¤tr tI+= rJ ,tfS-all,tl
+t}^la + 91tr1.
5F EJE_E 191
=e-d^l=
zl
,A{
de, ,,.l
-1
Z.A)
I --1 al Ha
+']]E EIE i{Hl¤ le=/i+RTlnao e9 5F.1
+'|]el $EoE at=PtlPi as)xs, xo-+ loJ r}] sF.2
+,l]E g.EE 4l+ ae=T exe Te)1, xo+ loJ rJl 5F.4
+eE E+qL ElHl¤ lI, = lli + RTln au a9 5F.9
+AE gEE ar--PrlKo As-)xs, x,,-+0"i ul] sF.l0
+eE gE"E Al+ as=Tsxg /e4I, x',-+Ooj u]l 5F.11
Margules 8l h zl=-
Jro= 6ri, ln ys= ¤xi Oll -Q-oU
O--r sF.16
+71 sq po =pfxoef(r-',r)r ,(l.l

olt -AoU
o--1 5F.18
¤+ +l5E al+ y*= (y*t,y_,t)tr', s= p + q zl --1

o
ol sF.2s
Debye-Htickel la3 E=1 log y* = -Alz*z_llttz 1-+ ool B+=. g trJ 5F.27
olg .r-llzl 1=i\zig,tb") EE sF.28
Davies z] log y . = - 41, -, -lI''' I (l + BI'''1 ) + cl A, B, CE-g dc ^J+ sF.30b
213
확인
182 5 E!+==:EIE
E 71 ,\.5 E+=-Et=
Eq sA rH-Lf EE+
=El=oll
exlt
==
DsA.l F ++9 (¤zll) TlillTl zlB4 o e gQ*9xl ?+= DsA.4 EE "Jq *{ zH'JB ¤Bil}l, *eq EE C¤ol .$o1|9 Caql
oJ6ll =aol 9l4lExl E q+oJtrl=
^l+lg +B6Iq4.
Eo}u}.
DsA.2 gtlB
CEE sI+ ElHl¤g +44b rll Raoult9 Ba4 Henry9 DsA.s tsl-Sar "J"l 4lE aC E4ql qB4l +4lEl=zl$ gEq4sE
Hzlol qB4 ol$lbxl ¤E6Iq4. ¤B6rq4.
DsA.3 Raoult9 H44 Henry9 B4g Ez146q1^l ¤H6l.q4.
G^
Jtr
mw = nollglmd Mw
=
923 glmol
ㅇ
E5A.t(a)zo"coll4 Hl{lel 6zl $¤* rokpaolr'ilBHldel +7l$qg
z.skpaol4. ol f zlijlzi ag ¤*o e g6JE9 Gzl.Jqg Bolzl
71 419 Eql q.J
EsA.6(b) ollH t"l9 tzl
+$UE +6Iq 4.
¤-611E (gpr-o E-e
Eqfl= eAe| &^9 E +ge ?+?+ E
491
^l?l
ㅡ
941,9*i n kpa 6 o.zs4 0.2lol+. 2s.cql^l gfl E4^r "Jel E+q +Ill= olS zlrll
EsA.t(b) so.cglr.l r,z-4"llEHld9 6zl $qg zokpaola r,:-4"llEHl E EgtsEE +61q4.
dl9 6zl$89 rskprol4. ol + 7l4l7l Ag e"*-9.-e d"J E_tlEg + E5A.7(a) e&+E "JE= zlAlzl zlc+oe
^l*5lr ?i4. "l 7l4l=
a
7l ol-=H o olnlzl trl ,l r-r k?
' I E f L e
mw = 5868g 1mol
I
M B 9g 어gimal co,E Sqg s.oatmtlzl +q=q. ol zl4l-=.*El +s= ts&+ +E

EsA.2(a) u-tr.*8(o}^llE)4 e elpee4l*(=-tr-tr.EE)rlel +a4ql^J co,9 EE"EE +61-q4.
cnctr9 E ESol o.+09:oJ rll, olE9 +E +tl= 44 rulucm3 mol-r EsA.7(b) *9 g+ql.<-l +4I+ xlla ltzl$ qI E"J ^l^s6}*,qq
4 so.z:scm3 mol-rol4. ol +"+ t.oookg9 Pslzl 9"14 94l,s4i ^zllfl
ol tlile.l oJqol 2.oatm_o E Bqe+. oJ 4floll,rl qlEolzlb +Î+ +
EsA.2(b) + .-qiil e4 sel9 +Eql^J e9 E E80l o.:zr:"J rli, ol59 9 co,E E.bEE 4lt}6'1q4.
엠 (* -)
+E +sl= 7+7+ t8l:cm3 mol-r4 t76:4cm3 mol-'o]4. ol 8"4 1.000kg E5A.8(a) Ael BelE zc+ gQIEE dill+El +4 4*zl trl+4 ge +
el +ulzt B"I4 qdL+? e4 s9 E e"Jg zJzJ 24r.tg mol-'$
198.2gmol-rol4.
6J^lo _+ s^194.
in ( xz ) =
+ 35.6774x -
e%Lge soy,t ql+g_E
u = 987 .93 0.45923x2 + 0.017 325x3
E5A.3(a) f.Eq "JE= zs"Cgl,rl 0.el4g cm-J
ol+. ol +q
+9 EE eg +El= t7.4cm3 mol-t-E
+q= 4lt5lq4.
EsA.3(b) eeJ-g-g ql+g E +"-qq "JE= 2o'Cql^l e68.7kg m-3
20%ooJ
+r q+gg +E q7l^l
+61+
EsA.8(b)
u=Vlcm3, x=nulmol,
49 +s.o1q4.
fell nuE 89 5d*".l4.
eg se+9 2c+ g,dtBE dill+irl +4 Aalzl trlg4 eg +

시발
(7Bq EE +ul=
ol4. ol +"-4 +9 ql*gE +E +ulE 52.2cm3 mol-r.P +':z E9 +g 6J^lo-=. s^l¤+.
+El= zlt6}q4.
300Kql^l@
Oe cecl4-&E +9 Hclel *E 6zl oJq(+ HCI f;zlel
u= 77 8.55 - 22.57 49 x + 0.568 92x2 + 0.0 1 0 23x3 + 0.002 341
ㅇ
E5A.a(a)
++ "Jq)g q^s=4
6400
aq. 6408 6400 ¤zlrJ u=Vlcm3, x=nslmol, r4I nsb 89 Ederol4. Bel +g +ElE
rHcr 0.005 0.012 0.019 +61^b 4¤- +E6Iq4.
p116/kPa 32.0 76.9 121.8 E5A.e(a) 2s"Cql^l NaCt i&qqE +ul= "J¤E EB}E bql^l +A6J
ol +Ee
3o0Kql^Jel Henry Bzl
ol A
g Eg gEq^l
tL+E 4l4I6Iq+.
Henry9 H4q 4=q-= ag
Eolr., 4*, t *slz} u=1003+ r6.62x +t.7dt2+o.tzf4 Ag de^lq qg+
Ag .JAl 51fltr1. ¤zl,tl u=Vtcm3, y= l.000kgq +3 EEI6I= 8E
=
el +rl, lEIr x=btb"ol4. +"lE gg+E7l 0.100mot kg-,"J trIe] 4
EsA.4(b) 3loKqlî o-4z]l n +ql +o}?l= Ee Bq +E 671 Sqg q-g
4 ?Jtr+. cE=e-l +g +slE +4q+.
EsA.e(b) r8"cql^J t.000kg9 Eql +oJ MgSo, +AEg diil Pulz}
xB 0.010 0.0r5 0.020 u= r00t.2t +34.69(x-0.070)2r+ Ag de^lql qE+. {zlrl u=Vtcm3,
pslkPa 82.0 r22.0 t6.l x=blb"o\4. *"-49 EBtE7l0.050molkg-'"J rllg ol g4 +rHE +g
ol *"lg ol E Eg ¤qq^l Henry9 Hzlq lrlEtrlb {$ Holl, +4E +6}q4.
3loKq^19 Henry g4 tr"+E 4l4I6Iq+. ㅇ
E5A.10(a) zlf, no=0.10 nrol-I, ErJe-l ad Hsiz}
+t2f mol-'ElB H+qr aJ4.psE 9oI4 H6lA!+?
^Jzlts
poTI 6lro=
1 2
*zl9l t=B Hldlql -*6llEl= e^g g +6IE= 4l
-
E5A.5(a) 2s"cql^J .
EsA.lo(b) 4|fi no=e.22 nsola- ErJg aC Bqlz} pAzI6llA=-ls

4i6}q4. *71+E e^q ++ .Jqe Eq IAE -E-7l lA.2ql^l 4l4i6}f, ^8zlH
ㅗ l mol-'uJfr E¤I+r el4.psE 9"I4 S6'ldt-.+?
+.
fldq g E5A.11(a) s.Odm3E SzlE Pulzl *Al + rJ-q E +4^lA+. g+ ,Jql
4eI
"il+el +6llE= a1,$6lq+.
~
EsA.s(b) 2s.cql^J r.ouare.l
E5A.6(a) Henry9 Bzlr+ .E sA.lE qlolElE ole-"oJ.{ 2s"Cql^l E +ql AA= 2s.Cql^l l.0atmol Elrll i||+J" 9E+ rJql= +r= ,J3 .$g
=
s+ *4ol q4 il]fl.4. zJ*olE zllrlltg o1l9 E_6J $Eer]e]. Gibbs gl
+oI 9l= ol&EltsiE Y E Sqol (i) 0.l0atm4 (ii) t.00atmoJ oll9 ol
DmxG nRT IM 2
D
=
용해도 미5 25
=
-
3515
N2 Hz
25 c 25c amrxs =
11795
lontmioatm
E¤r[ Erll 183
HxlE 4l{i6}qE}. zl4lE$ 9d zl4l4r z}CaHE}. sel "J4"1 Elrll zfl*ttr}. zJ"-l"lE xllAfl,g trltE gtl SlEs:qq Gibbs
EsA.r1(b) 250cm3g ¤.zl= pulzl *41 + rJ_q_e +?-l^1a4. g+ 7Jql qLJzl$ 4l4l6}q+. zlillEg ${ zliJlap ztA6}q4.
- ole=¤. o.cq^l rookpaol Elril il]+r" e-=4 ,Jq= Lll8g ag g
EE sB Ee4"l ¤tr
¤B E8I
DsB.l Er+ {tlel #=e *izl4E olfiE ¤B6J + 9= E.ae +t DsB.4 #ce *e9
++ql= ++6}tr1. :-flrll *F 41"*Be qB41
ol4i +eq E e+g ea6l+ Ell ol+E + 9lL+?
DsB.2 -$ullel q=a *#zl #=e *+E+ gHlzl o + t ol+= ¤B oss.s c* *"-4ol *q."Jzl ¤E6rq4. dzll ¤.9ol a+ *"1+ trI= +
6Iq4. 714"J Ceg g6}q4.
osa.g ir-F ¤tlE +l"J¤- gq+4s8, relr E g6J¤E Ezl ceg DsB.6 e-qlxle+ Be_E r+"J goJ +q= *"1 q4L+ E= ¤61 EIlIILF
zlzl:t- ¤E4q+. DsB.7 #cE Eqql4 t?lg ¤E6Iq+.
G^ PHce ( kPa ) = 6 41 × 103 X PHa -

0 .
0
미
Jrr .
H = 20 8 K5 TF = 리
M
D
.
Y
ㅇ
E58.1(a) oli-ll GeCLql
+6Hg HCIE EBFszt
B 6zl .Jqg 4l&61q4. gsoJ EllolEl= ¤#
0.10mol kg-,"14. HCIE
ese.s(a)E BoEl. i 33 9 2s"cq Hldql 4t olt4
ㅡ +611E= +61q4
E58.8(a) "JE4{19 +S tlgET} 28.8k1mol-rol-tr \ifrol zr7"Colq.
EsB.8(b) B*:zz"Cql,rl hl" r +¤- elBEl=
.
EsB.l(b) ¤# ese.ao)E +Eq1.r1 e 4ql *6li¤ ^J+ Bel EgbE 5.2k| mol-'ol+. 280.Cel
zl o.2smol kSrolr|. BE ++ +71 "Jqg 4l,l}6}q4. Ag E ap*g HI.\+Eql r.I+ Bg ol^J4 +6llE= +6iq+.
mol-'olr{.
74.1g
MW
=
n8 이 6 ESB.e(a) EEol \$ #g +aqg oltr-4-#$ +Er+ Aol
6rl $qge 53.3kpaoJql,ㅇ
60.6"Cq1^l&
Îgs+tsAq]
Q ++{ +rl Sqg 2e8Kql^l 33.85Torrol4. E Brr9 b
E58.2(a) Hldlel soog9 {dlql+ 4E6J+. Ccl4el
El+lgC +eg +flqq a +7]|gr-qolㅇ
-
rr.og9 sr.skPa-tr Eqa+. ol E= E E$g L}EI,"$ rllel Henry Bzl tI+= 122.36Torro14. srr9 E E
Sol o.osooJ *IE 4 CEq 6zl $4, dill Sq, 4 6zlt9 aCg 4l&
sltlEE E e+3
EsB.2(b) 2-8.+sgel
4l,i}6}q4.
+rl sq¤: 338.8'Cql^l S0.00kpaoJrll, ZSO99 Z-g
n0 .
604 6iqe}. ol :-" soll.rl ol^Jzj-#g +.lel adol "J+g+r 7IA6Iq4.
++EI sq^ll AE 6zl *43 zo"cglr'l zrkPaola
EsB.e(b) olill
A+ql^l
gqeq. "l +.JEE E A+g 4l&6}q4. Ezl ^J+= z:kpaol4. Bq E E¤ol 0.0669 "llE 4 CE9
Bel Henry
6zl $8, dill glq, "l acg 4lt6}q+. ol $.Eollrl ol*4_
tE5B.3(a) qtr EI6JE r00g9 zsog9 ccLql \B.rl{ ccrnE q=Aol
ro.sr ".h* L{e*+. "l siq}Eel g e+g alt6iq4.
EsB.3(b) qtr elElE s.00gg zsog9 +sB{lql +flqq .l +"He-l q= E58.10(a)
=:zlt}g
Bg +Eel 47Jol "J+gqr zle6|q4.
e0"Cql^l ,ilEHldlel +rl Sqg 53.3kpaolr, l,2-qqlgudl
dol 0.780K "J+ qEut4. ol E*!]EE g e"d:g 4l4I6Iq+. 4 ?zl "Jqg zo.0kPaol4. 9P $Hol o.soatm"J trll + .+illg g'*Eol
eO.cql^l #=+H r a,rJol qB4 94Lg+i E oltrll +e= ¤zl9 z
ㅇESB.a(a) 200cm39 E9l z.se9 ¤%Ig +e +E9 q=dg :FaI44. "l q$rll qd!+?
+.lg ol{t{ ol a}a r}A6Lq 4. 273 08 K .
^de
EsB.lo(b) eo'cql^J l,2-qollBHl4l9 6zl Seg zokpaola lJ-qEilE
EsB.4(b) 200cm39 Eq z.sgs-] ge+LlEE¤- +t *sIE q=dg +6|q
U4!E +rl "Jqg rskpaol4. q+ "Jqol lekpaoJ trll +.+illE gilB
4. ol 899 oldt{olep.7tA6}q4. ol eo"Coll,rl #=triB -r a^dol qBr]l 911,:+i E oltrll +g= ?7lE
E5B.5(a) 300Kq^l qH ++qE AlFS"lㅇ
X tz0kPaol9.4. ol +EE q= 4ce qg4l El4le+?
dg al&6}q+. Eill AE +rl sqg 76.7toaol:t ++EI sI
300Kql^l ++6J
EsB.s(b) 288Kql^l qtr ++.-q9 ++sol gs.okpaolfr.trI. ol +EE q=
E5B.11(a)
ag 4î6}q+.
ill Bel
+rl Sqg + CEe ol^J4 .lill "l Tlill *.-4
sz.okpaol4. ol=.
g "J=+. BB ^JEIq 4 *zl +9 AE g- Egol 03s0oJ +._qg "Jtrfl
ㅇ
E58.6(a) 298Kq^l 0.50mo19 CuH,n(dl4I)4 z.oomol9 CrH,u(flt)g g
*^lag qE g6J Gibbs glLlzl, fl=eul, q flBslE al4l6].q4. ol*
48, : dzll 6zl Sqg $"iz| Elq, E Eill *Eg 4Ce q$rll slXl
u*a
+'49 zld6lq+. -
3 . 1 KJ 10J 0 EsB.ll(b) 2e3Kqî ++6J .4ill A9 6zl "J93 68.8kpaola +++ E
EsB.6(b) 2e8Kql^J 1.00mo19 coH,n(dl4})4 r.OOmol9 c,H,o(flB)g ¤. ill Bel +rl "Jqg sz.rkpaol4. ol + slql-Es olt4 .-4ijl "l Tlijl +"-I
d.^lag qE gEl cibbs ollHzl, slEeul, 'l Q!Bq= 2l&a}{4. "lt 3 "JE4. B¤ tlEllq 4 ¤zl49 e9 E ESol 0.6r2oJ f..lg "JEfr.
+"-qg ztd6}q+. 48, : 1]l)l3zl Sqg 9rlz} slq, E .-Iill +Efl aCg qB4 qA
t-t--tz
어
E58.7(a)dlt4 fl+E EB $le+slE aqle Elrll 6IelH (i) olEg g
…
Egr+ (ii) e%I +¤-g qg4 +lollot alds+t 박 6IElts (i) olE E5B.12(a) Ael BE ZcE s"-4ol ,o=0.6s8e"J ull AS"Cql^l #=r+. ol gE
EsB.7(b) qBfldlq st} fle_eulE 44e q4l
Hldlr+ ql^l ++5J Ael Bel 6zl s43 47+ r27.6tip:a4 so.eokpaolr+. (i) ol +
el g Egr+ (ii) e%L Egg q$rll +lollot 6IAL+? ._49 oltr.4ol+? (ii) ol {_o_!etr_gEl +s= il¤- 6zlg 3c3 qgrll
94Lg+i
184 5 trJ+==:EtE
EsB.l2(b) ae+ g9 zCS 8.-4ol xe=0.42r7"J trI 96'Cql^J #=+. ol gE I (ii) ol *9 o _e+El z,l¤- 6z19 =ce. "iBrll El
q^l "l*4"1+? '+s=
+++ ec+ s9 6rl Sqg 44 lro.tkpa!} 76.skpaol4. (i) "l +aI ?lg+t
EE sc 2tr5j" Zlel AFE:d rH: qqill

grll
==
osc.r EE =" Fo|^J +16l= eEE B"]E 6h= ql gstl olEi ++¤ A qlqtr EAEoI f{lap. ol$ol Eill"Jzl, E= zl4l"Jal= +{qq+.
e6l+ s"Jg F9"l4i Dsc.3 + alill gt+Eol gg BE_#g g*Eol !*xl E= *g gH-
D5C.2 xr=Q.::r"ll,tl EH #g go}+g ¤C6E" Sd6l goJHE zCE #¤- g6JEol q=zlE ec6h= +xI cag +Eol+?
41E -o-E-iC "-4ill-671 tlBB rBg rel+. ol ^JBB rHE gEE
G /^-
r -tl
9E5C.1(a)
5$
EllE4
z.esg9 +g
Eg Hlol^J4
gq+6ll+E
+ B+^.i
"+ill
g'*Eg RI=tr1- 60"Cql^J
.-4ill^Jol
¤dqE'll, ^J5E
z3zg4 4l g zlzla_ +AEJ 4"14. ¤zlri xE "_4ill +q^JE E +golr" /E B¤
g ol+n 9lb +71 +ql^19 E E¤o14.
sll5 g +gg gd¤ +E qlEel dill "l
0.042e|0.16roltrI. (i) ol g E&g
o
15 4lt}6}q4. (ii) zlql +z1g ol+6}q + ^JE ^J'll4 Ee+3 +6Iq4. 0l"c r25 r30 135 140 145 150
Esc.l(b) olHil c6HsNH2r+ dl4} cuu,re 0g.r"cglrl +tfzlo + 4olE xA 0.91 0.65 0.45 0.30 0.18 0.098
.+ill-Eill g6J+3
"J=4. 67.s"cql^l +2.899 oLHa4 zs.zgg dl4}g lt 0.99 0.9i 0.77 0.5i 0.45 0.25
g*6ll+H + Eill^}ol ¤Cqb.ll, ol ^JEel olBfl g ggg 0.30sr+
0.61801r+. (i) ol gd.E 49
Aet BE #=Ag 7+7+ r24"Cs+ lss"Col+. ol^J*E g'il¤el gE-ac
"I8ilg dill E- B¤-g 4lÎ6Iq+. (ii) z1e1; rHg rela}. (i) xo=e.5s3-1- G) xr=s.33t a^dE "li-lle+ *Bg ol+I
+zlg ol+6}q + ^Je_l dlEI4 Eg+g +6Iq4
9lE 6z19 4Cg +6Iq+.
Esc.2(a) etF+ r+¤+a +4*? zz.zo"6 olofoll.! +E ¤-6l]dg +4
u4. ol g "J4l ¤.Eql^jel "J4l e^Je. x(CuF,r)=s.3ssoltrl. 22.0"cq1
ㅡ
E5c.4(a) :rB s.t3 ++!4 o + 4"lE F "-qzll9 tlBB Ll+U a rBg

ol-,=E + +'-49 aCg 44 x(cuF,o)=0.24* 0.4sol+. r4r
ㅡ olA-3- E(A)r+ 2-trilB-r-o+*¤tnl 4ql EilqI g +E 9l 4ol4l
^l B¤g
"Jrll,
zr.s"c{rl= ol E +gol o.zze4.0.s1olr}.^}B¤ rHg rq4. (i) 23.C 4.xa=0.8oJ~
aCE +t+¤-g 7Ig6J tril "JqLI= H+= ¤86}a" "|g+l
4 +4q^l BBg olf +, aC, "t tlEll4 "#9 "Jdtq+.
ㅡ
eI (ii) 22"cql^l "Ja"tel etqq ir+E-=+a edl,t}S zlal qt "Jq+= tr-

= ^JEel
H+= ¤E6lqe+.
B9 + .-qill= s2.4"c olaloll.<J ++ ¤-6il^d¤- 4484. ol
Esc.2(b) Ae+
+i "J4l gEql^lE "J4l e^.ig x6=0.zlr!ols|. 40.0"Cq1^l B¤¤. ol?=
+ +"+q ace. 44 xo=0.22e| xo=Q.gsolc|. ral-:1 +z.s"cql,<l* ol E
Egol 0.24e+ 0.4801+.tI¤¤ reg rel4.r4r (i) 48"cel (ii) s2.4.c
T1
O
ql^J .Ja%+el Aqlq B= 7IE- trI "JqLI=
^JHsl¤ ¤B6Iq4. l-
Esc.3(a) tr]-g- gE/ac 9lolq= r.ooatmoll^l +ts(o)r| Lti

"llgHldl(M)r+ 01J
9 g6JE-9 zlzlt_ +aoJ 1o14. q7l^l xb o4ill +ql^19 E. sgolr"

/E ¤¤g ol+r 9l= +71 +ql^Jel E +gol+.
qtoc 110.9 112.0 l 14.0 1r5.8 rr7.3 l r9.0 t2r.t 123.0
xM 0.908 0.795 0.615 0.527 0.408 0.300 0.203 0.097 0 0.2 0.4 0.6 0.8
Bel EE, xa
lu 0.923 0.836 0.698 0.624 0.527 0.410 0.297 0.164 =
Mrl oel #=dg 44 rro.o"ce| 12s.6'col4. "l ¤-6JEE gr-a,.3 t} lal s.l FEEs_e +o|: + Eillsl Al"Jts r=J
¤¤ reg r.14. (i) xr=s.256r+ (ii) xo=0.2500J acE q4el BBg
ol+a 9l= +7lel ac¤- +4q+. Esc.4(b) :B s.rg +^l d-J.6[44.aCol rs=0.3oJ g.JE-g ,]¤g trll
Esc.3(b) tr]-8-gE/ac rllolel= r.O0atmgl^l + .-4ill Ae+ Be+el gB-B 4 +4ql^l tlEe.l +, aC, rel:il ^Jq4 "J# s^l6iq+.
=zl]6l+
EA4 Er.ll 18s
EE sD 2tr8 Zlel AFE:d raJ: r.^11
== =xil
DsD.r El+il +¤¤ 9szlE 3rHlE ln,E BC6l-= zCE 419 8E-a BC6l| zCE 419 gE-e¤
oso.z aJil ts-$¤ $ezl5 3rl'El$ ABE
{ lrfl-o4z1l t¤¤ rHg rel4. r.ill-r.4l +6llE= Ael +^lg + 9l r.ill_Eill t}BB rHg re14.
+6llE= ,lE +^lg + gl+
-r.itl_r.^.ll
tr|. ol tlBB rBE gE=ql qts E.4Eol ¤z116}r olE"l r,alloJzl, E=
E4l"Jzl= +44q+.
G^
l -tl
reJ s.+9 1lB¤ r=Jqlq uloJil +Eg +QLll= $XS
E5D.1(a) ㅡ e E5D.2(a)rB s.4el tBB rBql^l EaCd ae+ bgl q.J B4 +Cg
g6JEE 4cg 9"Iol4, E. r +=49 gEI*r rel+.
^l6iq4. +s EsD2(b) :B s.s9 tlB¤ rBql^l E"aCC ael bol
'll-J B4 +C¤-
500 ab rq+.
E5D.3(a) rH sD3E tI¤B rflg olgoN.r] (i) 800"Cql^l +4ql rll+
400 g9 *diE gql rflal Ag,Snel +6llE r?-ln
(ii) 460'Cq^l (iii) 300"Cql
0 r.l eg,Sn9 gql rll+ +6ilE= "j="I{4.
(J
o
6 300 EsD.3(b) :B so.+9 tl$¤ reg ol.$6ll^J (i) soo"Cql^l e.il s4t
ui E *6llE (ii) 3eo"cql^l Aql ql6'J AB,el *"lls, (iii) 300"cql^l Bql Eil+
0lt 200 ㅇ AB2e-l e" 6llEE Et-8H4.
E5D.4(a) qBEI B2H6(B)= o3-21 55flo1 r:sx"J oI
'ilBqlBqlqlq(A)e+
100 6J+g ol 4l= + +&dg 444E'll, 6I+= szl zsmol%o -Eaj
"JEtrl.
B trI$ 123Kolr" u. 6I+= nz]. eomol% EEl¤ o19 to+rolq.+++
I I
0
0 0.2 0.4 0.6 0.8
Bel EE, xa Ae+ BE +=d-3- 47+ lBrKq rrorol4.
"l 4l"ll q-J tBB rBg r
= el4. a4l-a^ll +6llE= +^loJ aE4a 7l-c6H4.
fg s.4 Ei eso.t (a), E5D.2(a), '! EsD.3(b)ollll tssl-d Pe-ad AEE EsD.4(b) NHr/N2H4 4lql .]l.J dI¤B rBg rel+.
"l Ea=g ^ls e-l-
-ral
JE. qIE-g o}=zl ?+=4. "Je_qo1s _zs"collr-i, jr_?-]r N2H4= +2'cql^l t
tr}. N2H49 g ¤¤"1 0.07oJ +& 4Col 94, -8o'Cql^l +=tr}
'll "143
'llts(+=e elK)rl +ril+(+=d 8eK)=
EtlE?rl¤-+e
EsD.l(b) :H s.s9 tlBe rflqlq uloJzl +dg +4,11= 5c9 s E5D.5(a)
ill +"+g "J¤zl ?*eq, "lill 5+4 o + 4i"J4 o-qi-ll^JE
-a
^l6}q4. +&
g6JE9 aCg 9o}"l4, E r ++d3 $"iu}? ^JEllql^l=
E-6JE-
E +l "J4l Soll 9s= x(cFr)=e.43ql^J e4Kolir, +&dg x(cFo;=s.ffiq1
84Kol4. 86Kql^l cFo ** *"lr+ ¤B¤- ol+:r' 9l= tlg aill "ll+
^l
b a -g.s+El cHn*.+ "-qill +"loe H6Jtrl. ol $roll,tl ^ls BB¤- ol-T=-?
9t= + .lill +Eg dcF,;=s.1srl dcrn;=6.80o1+. t}BB rB¤- rel
T1 4.
EsD.s(b) 4.0mol9 B2H6(+=A 13lK)e+ 1.0mol9 CHIOCH3(+=B
l- l3sK)elE "lill gtlE-3 l40K-s+El e0K-tr B4^le q "Jq+= tr' H
Lti
oU
T2 n+E EJ6lq4. Ee=g 3rI*E (CH3)2oB2H6E oJg=rll, ol slaJE
"l qf,$
T3
I r::xq,t1 a3z1
"JgrJrl. r?-l.I. x(BrHu;=6.2sel lrK, r?-lI
x(BrHu;=s.9s4 lo4Kql^l *41 +tr}.
I I E5D.6(a) ¤6 ssp.s(a)9 zl-EE ol+6}q {cFr7} (i) 0.10, (ii) 0.30, (iii)
0 0.2 0.4 0.6 0.8 1 0.50, (iv) o.so, -ze-]-L (v) o.esoJ e4ill g*Eql
q6J B4 +cg relEI.
BE EE, X, EsD.6(b) fl# rso.s(b)el zle= ol+6}q x\BrH)zl (i) 0.10, (ii) 0.30, (iii)
= gqlEq 4t
lg s.s E6 rso.r (b)st EsD.2(b)oll^l EE-d e-e.-a¤ 8=Je r=J.
0.50, (iv) 0.80, fe,l-tr (v) 0.e5oJ
"4ill ts4 +Cg:144.
Eiil JL(tr \/OL

? ltr 'Tlol
ll-l
,\IE{:oi
() O (-
lal
-I--l -LE
¤E E^1t
'il+ tlEB rBql^l cE s

DsE.l -]B sE.6ql '+ElU ,Jeql DsE2 3CE 4lql^l ¤Bg $xlalE,tJ + 9l= t''el ++ al
^ql"Jql^ ^]8 =zllB
dE aCg'5"144 4lE $ulzi qaLLF
^l5l=
186 s E!+=-#
Dsil 3CB 4lql^Js- zlql +zlol ¤g6IL+? osE.4 ^d47+B* "l*"|]rl +CE Alel ^deg +48 + flA!+?
G-^-
l -tl
E5E.1(a) rB S.Se- NH4CV(NH4)2SO4/H'O ECE 419 ZS"Cglrl9 tlB¤ EsE.2(a) rB s.s¤ +r6lq 2s"Cq Eq +4El= (i) NHlCl, (ii) (NH4)2So4
:zB"l4.4Col (i) (0.2, 0.4,0.4), (ii) (0.4, 0.4,0.2), (iii) (0.2,0.1,0.7), (iv) (0.4, elg *6flE= +6Iq4.
0.16, 0.44)oJ g-6++= 4oll ¤4alE t'-Eq +E +6l.q4. Bs + +zlE EsE.2(b) (i) E +ql NH4Clol +"*_e_E +^116l-= sgl +gql (NH4)2So4E
g E- +¤-g ilqlqlE +Elu 1"14. TI6J trll, (ii) 2sg9 NH4clr+ 7sg9 (NHe)2so4e+E gd:Eql E¤- zlEt ull
^ll cEE
(NH4CI' (NH4)2SO4' H2O)
oltr EEIzI "J{4EzlE ¤EBiq+.
.1 H2O E5E.3(a) rlg tiEI#:4¤ ais.ll .s^l6}q+ (0 d (0.2, 0.2, 0.6), (ii)
d 0.8), (iii)
(0, 0.2, g- +g-=ol E"J.J d.
^ll
0.2 EsE.3(b) trl^g tlEilE¤ 34¤ 4s.ql s.^l6}q+ (i) A (0.6, 0.2, 0.2), (ii)
d (0.8,0.2,0), (iii) e (0.25,0.25,0.50).
0 0.6
E5E.4(a) NaClA.larSo4.l0H2o/H2o 3^J+ alel t}¤B rgql+ +g d=
9 Sr.1a1q+ (i) e*otr. 25vo4 NaCl,257o9 NarSOn.lOH2O,:1el-tr -L
0.6 0.4
4"lxlb + gel ^J.114 acg rJxl"J, E9 *"1 H6l-= d.
E, (ii)
EsE.4(b) NaCI/Na,SO4.I0H2O/H'O 3c+ 4lel t*B rBqq q-* aE
0.8 o.2 9 e^14q+ (i) e*o + 33Voq Nacl, 33709 NarSon.loHrq :a4l :r
4"lxl= E, (ii) + gE tlql4 acg rJzl"J, E9 *"1 H6F= C.
g (NHo)rSOo
E5E.5(a) :? sr.+9 3CE4l
^J¤¤ rHg +r6}qzl. z.tsg E,e.2g4
NHo'ct1
0 0.2 0.4 0.6 0.8
lelr:.rg9 ol^]lEts--tr g g*Eg E zH9 t9 ol+q,
1
f.B s.8 NH4CI/(NH4)2SO4/H2O 38E 4lsl 2s"Coll^1el8EE raJ 4 tlEel 4cr+ tI.I4 EA%!g qBal qg+i e. ol 4loll4 (i) E, (ii)
=+++Ei,
o}^jlEll¤ 7I6IH qE Esl¤ol oJq+41.-+?
EsE.s(b) rB sE.+9 3Ce4l
EsE.r(b) rB s.8g Al.I.6iq aCol (i) (0.4, 0.1,0.s), (ii) (0.8, 0.1,0.1), (iii) ^J¤¤ r?g +r6}q+. ss.0g9 E, s.sg
p E gtsE+ H z}l9 tig oi+
(0, 0.3, 0.7), (iv) (0.33, 0.33, 0.34)oJ gtl$E +q ¤^|]6l^= *EE +E + e-l rqr ng4 ol-^llEto
6Iq4. +IE + +il5g (NH4CI' (NH4)2SO4' H'O) cBE E +¤-3 il q,4 =+"+E:, 4CrI *El]4 Ea%ig qBril q!+? E ol 4lql+ (i) E,
^J5E
fllElle LtqU 4,"14.
^ll (ii) o}^llEd-s 7I6IE qE Esl¤ol "JqqAlL+?
Eii! J!trtr EFEE

+ <-r-
-l -
¤E E^ll
DsF.1 ddA SEql *d oebye-Hiickel olEE "JHI4 +Ag ¤E6Iq4. DsF.4 dzll +'-qE +rl "Jqg +4..HelH Raoult9 Bag qB4l .a4o}
6IL+?
DsF.2 +zlB Debye-Hrickel +¤I Bzl^lq +EI+= +7l4.Jg qB4l
dBatflExl g6}q4. DsF.s SEEE +CB + ?l= %IHg sE6llî 'J:"l.¤4.
DsF3 ¤+Eo Eel E" E il+ +9. q+q ¤E6rq+. DsF.6 +s4 +9 olSE *Eo E 4lizl 1r+ q= olf+ +9ol+? Bg +
^l-ol9 ^JzlbzlE .+ +ql4 ol Aol tB+ 4e ol+= *9.o1*i
G^
l-u
E5F.1(a) KCI(aq)91 +611^l 0.10mol kg-'o1tr, CuSOr(aq)oll +5ll^J E5F.3(a) 2s"Cql^l Caclroll +6ll^J 0.010mol kg-'ol-L NaF(aq)9l +6il^l
0.20mol ks-'fl +Eg ol$,tilzl$ 4lt6lq4. 0.030mo1Kg-'"J ++"-4 49 cact,laq)el B+ olg ¤tEE 4l+e+ ¤tFE
EsF.l(b) Kr[Fe(CN)o](aq)91 +dl^J 0.040mol kg-r, KCI(aq)"ll Sullr.l +6Iq+.
0.030molkg-,, .z4l
NaBr(aq)oll Sollri 0.050moIkg-,"J +"4e] ol3 4lzl =
EsF.3(b) NaCloll +6||^l 0.020mol kg-'ol-r, Ca(No,)r(aq)il +6]]^J
E 4ltI6H+ 0.035mo1 ks-'oJ +&E 49 Nact(aq)E ¤+ ol9 **E" E 4l+el **EEE
E5F.2(a) s0099 SrllzI Eq9l= 0.150mol kg-'KNo,("q) *'-4.114 (i) +6iq+.

ca(No3)24, r4r H+ e (ii) Nacl¤ g"luHa%t) 716ll +qot *.49 "l E5F.4(a) 2s"cqlî #g HBr f89E ¤+ gEE 4l+= 0.e30
? 4lzlzl0.2s0o + 9dg+r (5.0mmol kg-'ql^J), 0.907(t0.0mmol kg-'911.]), r4n 0.879 (20.0mmol kg-'
EsF.2(b) s00g$ *o}|zl Eqgl= 0.ll0mol kg-' KNo,(aq) 8'-4"114 (i) ql^J)oltr|. Davis al9 B <tg +6lqe}.
KNO3el, :14:Z Etr + (ii) Ba(NOr)rE 9"}.rI zlali ?ol"t +EE olg EsF.4(b) 2s.cql^l #.$ KCI +*"_qE B+ gFE 4l+= 0.e27
^ll
zlzl t.6o e qd!+? (5.0mmol kg-'ql^l), 0.902(10.0mmol kg-'91,9), r4r 0.816 (50.0mmol kg-'
"ll,rl)"14. Davis BAI$ +6Iq+.

^19
EAEI Er]l 187
E5F.5(a) 2o'Cql^l a&e+ ssl #.14 Gzl sqg l.38lkpaoljl" ol E5F.7(a) 57.z"Cs+ t.ooatm9l^J E-e+¤{P)-'llEg(M) .lille+
+"jq +
gEql^l ++6JE9 6zl Sqg 2.33e3kpaoltrt oI *"-qoll^l Eq gEoE zl1l ,r.1o1E B¤g *CalflrlL-l .yp=0.sr69 4l xr=0.40001S.+. Raoult
E +6Iq4. E Hzl.ll "J46ll^J ol *.+fl + C+q rIoJ $FEe+ gFE 4l+¤ 4l
EsF.s(b) too'Ce* tatmoll^l qts g +&'le-l 6rl $qg so.0okPaol4.
&6}qel. ol $E.9lrl ++6J ¤+5E +rl Sqg 44 p;=r0skPaei
ol *qq^l Eel gi.rE"E= +6Iq4. pr,t=73.5kpaol4. (xp= "-441 +ql^-]9 E E&"la yo= 671 +ql^lE g
Egol+.)
E5F.6(a) Eg Ael B= sF +lgC o4xllE^l pi=300Torr,pi=250Torr, qE + +"lE "-qille+ *zl *E
^tolel ¤
EsF.7(b) 30"Ce| r.o0atmgl^l
relI. Ks=200Torr(*-EE 5 Ege g.^l6J trll)ol+. xe=0.90oJ 4l Bg +a6}fi.rlul ./e=0.314oJ 4l xe=0.220"1S.+. Raoult9 Bzlq "J46ll
pe=250Torr,ral;l pn=25Torroltr|. Ae+ BE grE"E= 4l&6}q+. E e ol +.jel + C+q ql{} gEEe} gEE al+= 4lt}61-q+. ol e_E
^-l
89 a:il, E. Aoll 4ollrlE Raoult9 Bzlql "J46ll^1, r4r Bql ql4^l ql^l ++6J CB=E 6zl "J49 zJz] p*=7J.0kpa$p;=gz.rkpaol4.(xe
i Henry9 B4ql "J46ll^l A9 BE" E 4l+¤ 4&61q4 Eill +ql^19 E Egol:r, ye:- Gzl +ql^]g E E9ol4.)
EsF.6(b) 2e3Kql^l 0.e20kgE E9l o.rzztgq HlflgC 84(M=24rg mol-') =
g +"J +alel ++ +71 *qg E5F.8(a) qts qI ?l*4 a+ +sIE 4* ¤=r.qo, pi=l5.okpar*
p(HrO) =0.02239atmo14, p*(HrO)=
pil = I l.6kPaol fr.+. rg sF.3!+ BlioJ tL¤ B rB g rei +.
0.02308armo14. ol +.1 +9 EE gfEelgFE 4l+¤ 4l{}6.lq4. EsF.8(b) qE .J 711*4 A+ +'+E 4+ ¤=-1.40, pi= l5.0kPari
pfi= ll.6kPaolfr,+. rH sF3r| El+oJ t'-BB rflg rei4.
Ez1,t 5 E+=-BIE
-4.6lxl orll
o tl -t ll/'ll
E.r F4e 4q EÎql 43 Ezlzl a6Jq= Ag ¤+61-= ql ol-oo 6J + ol9 e.Jg a^loJ + 9lr}. l.O0pmol dm-3E DNA +&E ,r.l_EE zlzla-
ql4. olqqi qlE^]= 6'^q A6Jg 9xllE, DNAqI A6Jg 6J^JEA, l 4'+q EBql Eil6ll^l +49 6}9tr1. "I4 ql"lEl= EBg dill r-oE [EB]/
4a + Ez}ql A6Jg +g +zlql 9'* EE.ol4 9xll z,I+ 5 + gl @mol dm-3)ql q6il^l ?3 1o14.
=¤"Jel aE
4."14."1 qBrll 7F.o6J^lE- olflalzl +1611^-l zl+ F4 +qq
z| M9 E.tsE= [M], -fE-l-r. arg Ez] Ael di-ll t.EE [A]i"ol4r. 6]z]. DNAzI s= + 0.042 0.0e2 0.204 0.526 1.150
ol dill bE=+4 *4E A9 EoE [A]a*e] aq]¤ A9 LoE [A]u"*ae] DNAzI 9l= + 0.2e2 0.se0 1.204 2.531 4.1 50
el qF| Aq. BBq^lEp^,m"=Iro,o,,olH, trI{^l +"tq "J+l"ll^] Ae-l !l ol rllolrl-$ zlz]ra- Scatchard E^l= 6Iq EeC *¤ ^J+ 65 fap. E
-FE.4l+E 'JLla BE [A]f*=[A]*,7t E+. tr]4^l +qq q'-9 +sq +
q 5qfl= A9l t.E= +A6lH ag4- *"1 +E +?-l tr-Eli A9 E"EE DNA +zI * + a.J zlel+E +61q4. a.J zlel= .E."J6Ia 5ts4o1
"J + 9lr+. lelr [A]m-[A]n*=[A].-[A].,E+Ei a6Jg A9 t:EE + 4r ^8461-=
olsBol ol e6J"ll 4El6J aolA,-+?
6J + 91tr1. olxll floll.le+ ee ¤¤ rl,¤91 4'J a?*4 a+=
^84d1
E ts.2 +xll rs.lql^l Scatchard 4g r+zlz| f,f,a|:z +84"J e6J
zI. (a) Mezlql Aqlg A+zt9 ¤+ + vi Qs--q- zJol ¤4. 7lA&'ll"J^l-soJ
4+84. .E+6izl ?*e eB- zlelql q4^]=
^lelE =84
Scatchard al"l ul*4 ,J"l 84.
.,- [A]*,", - [A],,-[AL*
"_JMT-_-TMT_ vc" \- N,K,
aqlg A+aIe| SaJgzl ?** eszl-b M+A -- MAE ¤Bg ol+r gl IrI;; + l.IqAL-Jc
sq, "J"J s+ql +aql^] EHflazl"J "l BB9 BB ^J+¤ rl-e_a| zjol v/[A]E 4¤- A+Eql Eil6ll^.1 E^16]q4.(a) 9E -aa + +z]7i 4
+4'J + 9l+. ,|lq +84"J a6J zlel$ zlzla_ ll=Ell ol$el ee4 A6J .!-+=
K=r.0x l0?ol+. 0) +zI * 0zH9 A6J zI4E zl,.la_ 9l= +6Jill7l9ltr+.
K_ IMA]c" olfr +zllzl t¤6}q Ba4 ¤q* tfzl rxlsoltrI. *"lzl F zlzl9 ¤
IM];III; 6J
^J-++ 2x l06oltrl.
+lE Lll¤¤ ols-"o|{ ffi $z]z} dB.Jg t!-"14.
ts3 6IdE tu4¤"1 ++Eqq (NH4)2so4e| Ag gg a%t
=iqfl=6zlaJ4. ol+l6J Bflg 9* a44I eL
z}6ll+E +EAe-l -$ollsz}
"=ffo; 4. zq4 +.*E ¤9 ztalE *"1o ++El +Eeol 4=qq '-Fg cE
e EEaE ¤:ollszt eiB + 9ttri. ol ¤tlg g^l E+4r 6l+Ell, d
o) r.ez} ulQ Nzllel t+6lr +84"J 4t} z[4E *=+H jl+zl-s s+qlzlE=_$ g6l
"l ¤tlg 0l+6ll^] tEeg +46l7lE 6lr. A41617l
z.lu}4 NT}lel +?]g r+4. EE4 zJol 4Ealq, 4 A* zlel= zl"I4 s. oJ4.p&(s) 3 p"+(aq)+vX-(aq)9 ¤Bg ^J44gz}.P'+i dalzl- v+
F"J6J KE Ag '*=+. u|4rl 4 4* zl4 'J A+zl9 ¤tfE v/Nol ?l tr]6! "Jolg EuId"ll" r= I tl.q "lg"l4. rr chatelier9 fl?]c+
¤ct. ol a+q= q-sr+ ?3 Scatchard zl"l cB.Jg trq+. Debye-HtickelE +6J Hzlel dHA"l != E4oi4 gP-l= ol¤-Ell^J ol g
vc" + Er+e+ ¤4 a4g EzI f ft91^l ¤E6Iq+.
EI;; = KN-Ky aÊ tF 4l++-Z A9l++. r=xBlxâ A--rr, Gibbs-
15.4 Q=-(xolx") ln
qlE^l sB3rlqlqE{r)rl DNAE #g EE alg ol+a}q {}*6J ad¤qq aa +g 49 "le"6t4 BE *+

Duhem
(c) Scatchard
^lel
¤+ Îol EE= Aq 95tr e+Et 4l4I6J + 9l¤¤ trq4.
el a6J¤. ^J46ll _H_z|. u5'5p,1qEg ol=Bl =td-oJolu}-rl 61-= r+a
r
ql E6H^l "Jolgol "Jd6l+ DNA g7ll8. ÎolE 4qEqrJ
HJ[6J+,H
tnll=o-
+. ¤B +^l ¤CBg "l-&dtE E_{q1r151EB)r+ DNAe.l 6]-e EE ^} o@). [:\\,
188 '..!+=Ei=
rs.s dzll +.-qE AlF"Jg lrv=-RT ln ao.E +qd¤- Bq4.olq^l +e co,9 +6la co29 BE" E 4l
^l=sdl4}.g +qlîel Bzl ^J+=
Henry
9 L" E7I *¤. trlt= ol ,16r=4RflBl gE gj4 trI+^l +F 4l+ 0E +E 4l,t}6}q?+.
^lol
+F4l%rHes +'J + 9l¤¤ trq+. ts.e opll qlolEl= tggkpaoll.r.j gie| tie g gql$E "4i{-6zl ¤B
E= s0'cql^l a e trql+(r)4 o|.!lEtglE(E)rlE g*Eol
ts.6 trl--$ a¤g +e}U 7"14.
+El-4= fzl $4"1trI. + CEq gEo E 4l+= (a) Raoult9 Hzlql ,l=
6Iq, O) a a trql*g 8¤e tr;r Henry9 B]q 7l=6lq +6Iq4 TtK 77.3 78 80 82 84 86 88 90.2
lO0x(Or) 0 l0 34 s4 70 82 92 100
xt 0 0.0579 0.1095 0.1918 0.2353 0.3718 looflor)o2ll 22 35 52 73 100
prlkPa 0 3.73 7.03 rr.7 14.05 20.72 p*(Or)/Torr 154 l7l 225 294 377 479 601 760
p./kPa 37.38 35.48 33.64 30.85 29.44 2s.0s
ol rllolel-e.Prl &s-ac tI¤B rBg rela
"lq^] 4 a^dq^l o,
xt 0.5478 0.6349 0.82s3 0.9093 1.0000 9 gE"E 41+E 4l&*-e-s,,^l +"-4ol ol^J+aIE Caq olL Cs.zl
"l
p,lkPa 28.44 31.88 39.s8 43.00 47.t2
zl "*=zl oJolgolal.
prlkPa 19.23 r6.39 8.88 s.09 0 ts.to -gulloll \i zlxjlel +6llE c= 4ltslel$, Henry ttf r= "l*q}
a-l c=Kffi 0l¤.61-= aol Eel6ltrI. 4olBqlrle} zJol .He .J4
gtl-Eql EH6J oI4 ?zl $4 rllolQ$ E.
rs.7 tldl(B)q- o|,<JlE-,ixA)r+el ^+t{
6}qlî *zl$ Eg6tH +6il9 eÊ }.EzI +7li;lAl ¤4. dael +ail
so'cql^] "l gqlgq 4* 6zl s4rard +cg E.rlr|{z}. ol Eq +o} Henry Hzl tI+= o.I8pg/(g H2o atm)olr|. 4.0atm4 2o"Cql^l
^16lr,
ol! Raoult9 Hz.l4 Henry9 HzlE"l 44 4EI+ gqq^] ¤B6l-=zl *7\e sslg E r00g9l* a*-e-e 9uI4 9i ¤dzl *otlq4Lr+i ol
E +"J+q4. Raoutt9 Ezlq "J46ti^l CEEE gEEe+ 9FE 4l+, ar+= r.gatmoll^l +7ls sElg E t00sq +"ilq:44 u1lalq{. (+
lelr B= +4ls tr?tg oll9 : gEEe+ gFE 4l+E Henry9 Hzlql zl +ql= 78.08mo1 o/o! $tzl5q9l+.) ,lHJ a4 +ql= dlzl E9l
"J46ll^l +6Iq4. ¤o e ol rllolel H+lq^l r+"J g6J Gibbs glulzlE q ++8, $4"1 ratmo etsq 4atmo 4 ?TFJ rll zl%r
^lB+ 4tsllL|. L"Eb
+6Iq4. 44 +E ¤c E"t+ ¤:71-614}-+?
xE 0.0160 0.0439 0.0835 0.1 1 38 0.17 t4 ts.l1 ¤.eelol M"J +rllel $-EoETIa^"J d4l 8e4ol ?l4.ol +.+el q
prlkPa 0.484 0.967 1.53s 1.89 2.45
qBe q-S +4lE EI+^l?g Hq+.
=¤
pulkPa 35.05 34.29 33.28 32.64 30.90 dlnao _ _ M
d(Ar) k;
xt 0.2973 0.3696 0.5834 0.6604 0.8437 0.9931
pr.lkPa 3.31 3.83 4.84 5.36 6.76 7.29 +gE BE"EE ar le)a- r gB+E=br4l 6IE ciUUs-Duhem
pulkPa 28.16 26.08 20.42 18.01 10.0 0.47 E+El trhsr+ eg gqdg trq4. ^19
^lol
dlna.
w
I
r5.8 Chenr| Lee=
^l=sdltlg4 9. zlzl zli'lle+g "-4ill-*zl BBg + d(^-D
g $qql^l A^t6IS,trH|.-T. Chen and M.-1. l*e I. Chen. Eng Data 4r,339
(1996)). olEE H ,r +q= 3e3.rsKq^l ¤o e Debye-Htickelg +6J Hzlg al^-l AIF Al<1il71 Q=t-i,q'Dl 4
^l=sdl^lg9 *zl* +9 E g Eol4. ¤zlrl A'=2.303A01:1, l=blb"ol4.
880)4 .-4illtr"+el g E8(x)9 geg ,LL+s +4U trl-gI+ ge' ql
olelzl-=qflq.
plbar 10.0 20.0 30.0 40.0 60.0 80.0
/,y, 0.0267 0.0149 0.01l2 0.00947 0.00835 0.00921

xcyc 0.9741 0.9464 0.9204 0.892 0.836 0.773
-*vla6
trl--+=JE
Elol HI*e "JHI4ee ^JCE4 q}¤¤ol E+ +Z116IB^1, E4l 6}= zl$4 Hl¤¤ ol+6}i 4ol ¤4. dzl9 dzl4 ul
olEol H ol1t H6l-zl ?+= E4 ¤¤g
4lq++. a
6J,6||^J Hl¤¤::z tI* qlqzle+ +4lqq, qie|^J gEqL4
Gibbs "J=
+q tI|4^J= ¤¤ gq+E +E gi= g Aed+ 421*z\Z ol$oflolqlQ.
^J^"iEel +Ezl B"I
HI*B=el r-oE-H-r+ "Js4-"e E+ot^l ol ql*ol Sd6l 4l 6C.1 u-u8zl dt; 6c.2 4= drl; 6c.3 Erl tr{E!¤; 6c.4 Eqq4
:et+Eq
e6l9+r _H_ol-E ¤ ollzl 9l+. rq+ tr-B+E 6:,tal HI e¤
+ql^J= B¤ HI+ EEIE +q Hl¤¤4 ddEol E+ ^J
'J* "JeE =q gl+.
6D E= tr1EJI¤
Czlflqi$ gqql4 /|H$ s|+ ¤¤ql+ ¤+61+ ql¤ E6J
6A BE A+ 4qlzl¤ Hql^JE q+61 +s6}rll ¤¤¤+. 4E ¤94 EoF
ql^Je+ u[!z[zl_E {z]r.lE dzlE}qr4 qlolqE z.lpa}zll u ;'
ol sa{ol.<J= +E qfl¤E ,]]Hg gd^lzla, o149 ol¤-
6llot 6[g:zH o eA] olag d4lB H]*E z[94 %}6]3 ql+
6Lq q$rll Elqt Hl*E ¤B aCg ¤$ts glEzl= _H_ f aJ4HzL BB tr-+= 41416]-= E e++4str +s+ +zllql q
"J 4o14. ¤¤ aC"l* Gibbs "llHzlE HI* Tl4Eql r.116ll
941 ole" alizlE "J9loi 6l= 4o14.
,<l r.rlflg trll +++= +azlql^JE ac"l+. ol +idg
6D.1 S= 4E!¤; 6D.2 E= ,ElE!¤el olt
+9.E ¤¤ 1}+e+ s= Hl+ Gibbs "ilHzl Îol9 +al= +
6J + ?ltrt.
6A.1 Gibbs ollLlrlel *a; oa.z gEE ¤B

fl rlE 0! rlEel EE=?
zlg4 HI+ql E|]6J gE+4 ¤*4 " +4 olE4 o+
^le
58 BAq g:eF= +ts e?l Sszt ql+61 g*+. r+ 6|+= ^Js+qL4 4Aql^J HI+ol
i'J
+E HI¤¤ "Jq+= ¤tlg +Ed-=ql ol+alt 4"14t¤
¤¤g gqql4 ^le + +4qH aa=E Hsl.il 9dl,rJ ^Jzl oJ e). qlarll *4zl ¤-^lg EeH frzl oe 6J Eaol 4I
E aqg. 8*4 " + +49 + 9l+. ¤¤9 + rll*61 6s6J e+qfl^-l Bu}dol q+^"iq= /.a+ rJZ Elzlg4 HI¤¤ .Jq
,Alzlo oh=lolrL c-
QcoLTvo
E:I- z-z)o
, .r_1 ri?ilrlTloFrrl - i-dHo
Ii
Lirll qlq= a¤- Eg- + ?l= 4"14. E 6l+= dTlp+qr-zi
-O -6
o =- H --l-l = rlfl,.l.IfJ:,,,1 =
a¤6J+ 9l+.4"14.
44ol d+ EeE 5s-91 EIl+61 ql"J6lrll E=6Iq, 5E6l-
68.1 gElE EE; Oa.Z 8EE gA ,ll r.?Ig d+ol E4q qBrll ol¤-9Ezls-olola3 + glril
g+= 4olr|1guj ro).
6c El-+ drl
"*e Hl¤¤ql^l= 4zlzl "ldqq, "l= HI¤¤ E+6I71 g16l]
^JE
d+ol 9l= dzlE ol.&61"1 q+ qe= E6H^J d4¤ s
A+ B > C
EEJ6A =J:d 8+
> ol EIIJE ufi+ts 01f;.

"J4Hol D-"J+Ug e H6l-= +8 E + 9lq. #
zl# AE "lAeJ d¤7lBs H++E Ael EE+elg dno--66
EE A+ts +:+oll^'l CBrl 7JeE,, gq-qtal gtr trl+ 7l e)a BE Hslals dnr-a467| ¤ 4"14. ¤Y HJB [!4E
^tolE
0lolT= + trEol E)7lE Eltrt. HJSE dE= 0l6t|6Pl ?161|4=
BE 8+7t olgXl LlElLt=rL f.a|r.r,JEol gqqt4 ¤trE=e +-n 6l-=r], Ee"d:el qHrcg Tvlq E+E +Elu+. HI
olgXl dEE=xlE 0|6}|6}l0F -dfl. I 114E7l. +qL+ oJ AflJ# EB trl]E Ael
=4%lol
,ao,oe
-e.+El no.o-L{.A g9 rfla E$ei ¤zHaJol ,rr,oo nr,r+Af

> EIC 7[E H¤}+. "JHI49E ^JE fE stlql=J4 +(^JCES "JE
-tr-
gtrEl EE9I gqoll^l ,JB ade
=ElEe.l
Gibbs 01lLl^l7l
<ig, HI¤¤e gE <tg *=tr})E u,4r B ,il IE Ee*
+471E nt|zl^l Eel6l-a1r. EEl.
I uflf"J# H++. qlE^J azlql 2.0mol9 A7I +z}]6}l,
qHl rEl
8J9.E! L¤-+r.smolol B ollztzl ,l+fl+E 0.5mol9 A7t Bal g
>
0l EEoll^j tse-ldlE Ll|te Eefg g-Btol 4lel 4"14.^J^"ig BE "Jg l.5molol g aol+.
=E ^|.94
Gibbs ollLlxl= 7[x|I E^lEEl= zlolcfie4 3D). 0l r]¤l0ll Gibbs "llHzlE HI+ tl4Eql 46H^l E^lql r4sE 7lg
HJBE$ sl-+ tr-ifl!¤rlolrie.l BELI gajq q-d e]= *11=
^l
ZlE HJ8 cibbs 0llL1r!4-r. eE6ln A.G-E -tr^l6J+. +
0lE6l'11 Etl(EE sA). +8-== Cx{l Gibbs ollHrl=
=-EtEq g0t0F:dtrl(Eq sA).
4 dEEq +q qEJ¤= 7f^lr. LlEl'J
= o't=(#)r, uJB cioos ollLl^l t¤sll (6A'1)
olul tr_g 3Dql^J u}q 3"1 "Jee} gEel *q 6Hl

oJHI4_"+ ZIEE il-= +44zl"J ¤zlrJ9 a= GE ¤
¤¤+ ^= s.q65
zl$4 Hfl+ Gibbs "llHxl Gzl \ofzl= +o +
ql +6J z1&21"J +4U+. rq+ ol AE "JHl4
^l "Jq+= olA& Hzl +16|.q {l*"1
"J +Hr+ 6-4 ffialzl= f+gEll,
"Jq\t+. "l zllH¤. Sd6l _H_¤4oJ aoE^J, ol Eqql^l=
d6EJ+ {q6}9+a Ezl.. re]H ciubs .tlHzlz} 4
"l zllH$ EE]]E e+E Hl¤¤ EB 1,"1+. EI* sEtEg r *4 ?ol HB a"l+.
^J4El]
s_6.JEq Gibbs qlqzlz| {czlql ER6J 4l7lzl +¤¤ ge
zlirll, ol d.4zl. Elqi ¤B ^JEIq 6I]REI+ ol ¤¤e eHl dG = ltodno+gudnu = -ltod| + t-tsdl = fitu -po)d(
¤-r+ qH}+ol eg +E_e- Tl¤61+ t4"J 4,o14. gqEg ol q-q-r+ ?"1 ¤ + iltr}
¤+6J ull= flzll+ zl$4o|+= ag 46J-9 9"la}4, tI* ^lg
4s.E-4e+ g q Aolol 9l+a 6]]E d^ll-e- q}*ol "Jq+ (Dc\
-- Llr.- ll,',
zl ?+g +E 9l= 4"14. IaF,J,,
7-
-1
5A.1 Gibbs ollLlrle,! =-4
A,G =/Ie -ga (6A.2)
HI+ gqlE9 cibbs 9lHzlE 41416l-r "la"l 3l++ g rI9 ols+ ?ol a,Gy Hl-& gElEel ¤4 ac Hl¤¤
ecg "Jol-48 r HI* E6JEE B¤ 6C¤- +g + 9t+ r+ slq} qfl¤(EE Gibbs
^JEllql^JE
qlq^l)el z}4r
^J^d+= ^l-olE
6114g + 9i= 4014.
(a) UB cibbs ollLlrl El+ qHi¤e a¤ql trl.4 H6IE_-e. Gibbs qlLJzlE HI*
*d e--Be+ eg ¤¤g ^84i6H Ezt. ol qI*"1 4f3zl d4Eql ulE zl9zl= HI*ol dqElql qq H++. zlg4
olfl ++E HI* ql= "*tr]-. {lerJ $
Sz]l EolTl= o}zltrJ HI+g G7I 4-A{+ *aJ" +(., G= 6"11 4afld -E^l*g
gol z-ullEPBs-e Hd+ olCAill+ HI*ol4EzI EE r-- *llE .llrl"+ "J.J) tlB++. trl+^J A+B Hl+g iun>ps"J
6A tsa 8+ n1
AG<0
r
o
j
K
5
6
o
-o
s A t G>0
o 0[lJ
010
NJ
'hl ilol 0[U

<l- <l- {0
<H G=0 <H -0
o HJB
fzJ 6A.2 + += raJql^lel eol Ee6|'E +718 +71 7lq,3 += ul-
T14=,6
rl'J4 tjJ:die-e 7l1l :Ltct. Ei{|4-o-e E q= 0l zl¤01 xlig4oltl'. 0l +ts
fg 6A.l HJ30l T]4EJoil qa[, = 3?l
U3 t]4E e7l r4at HJ8 F el-E HJSolltrl Hl+-g # ?lrh =-rctl =.zll 8oJ U3¤ AcTf EJ
Eill Gibbs ollH^lE ¤4 =
7l?7l7l =7t-er}ll
E-Lrtl. E-dA ol 7lz)l7l0ol HJ- Hl_rlilJ= HJ-*e_e
=-cfEE =olrJrl..
Elcl Gibbs ollH^l7l a|A7|. El= tro|tr].
+rll g + ?l+ aJE a.G>O"J Hl¤+ ts-4=..5014r ++.

trll gq+jr" pe>pAg ullE.: qe}*ol zlB4e
zlg4_e-tr. olBle} HI¤¤e qlaq E9 dzl E6]]p ole+ *"1 "Jg 6]]
tr. "Jqtr|. :-41 trIg+ ztS zzzf,ol CBg trll= ol zl¤ zlg4 ^J^d HI¤¤ "Jq+rll 6J + 9l= aol+.
zlzl ool qq, ++ol qL +e__+E. zlB4 "e. "J94zl t* =:_e-eal
¤B tr-Ellq 9lril gtri. zlEt:d ofl 6A1
=
A.G=0 EEE (6A.3) gAqI gEe+ Sqql^J qH + HI*el Hl* ciuus
^Z "llulzl
ol aagps=peoJ rll olF"l{+(rH 6e..1). EI{^l ps=tte zl -zwkl mol-'olq^l g-^JtlC"ll, zl'J.6J tlil(qlAql
zI q= HI+ sElEel aCg +"l{fl raol Hts ¤¤g SE dzl)E olSatH 1mol9 ql*ol "JqB uil"I4 200k1
ol+r ?l= HI* gqlEq acol g+. Etqt sifl[tro] olxll I 4zl4 "Jg +srll B + ?14. A,G-+200k1 mol-'ol I
qHI¤+ oj_+pdolq, ol ql¤¤ .Jq+rll 6lEiE 3l
:_ Bdol *al-b Hl-= +4Ll]B.eq, "1E- trlHl¤ol t¤¤. "l =
a 200kJel "Jg 6H+qot *r+.
E ull ¤¤"1 ol+q{+.
(b)g-8rl¤ut g-Êd u3
"Je+ EEe+ ttq 6l-ql^lE H]+el zpgCg tr|s-r+ 4-"1 ql 6A.2 BEq ¤B
* cibbs qlqzl= zlzla_ +q"E + gl+
olxllzlxl Ul]S zl49 H]]? o + alol olzll! itlq| ¤Bp- gE
a,G<gol$ erJ6JE HI+ol zl$4ol4
a,G>golfl q"J6}el q}*ol z}ts4"l4
44"+tr]-=+gtrlqH+.
/.G=0oJE HI*ol BB tlEllql fl+
(a) Sd 7li{l BE
A,G 10.J +¤¤ E_gtt¤"I +r 6J+(g ol_tr. exergonicnf. Ae| rz[ Sd 7li]lg tr]]= sA.tsall0r:p"+RTln p/p")$ ol8
a¤.'g-^J^d'ol+= r4^qql^J +49 lolu|).
6l+tr11, ol
o|{ ffi4Ae+alE gg+ 914.
olElq} HI¤+ zlB4olo + ol ¤4ol FalE ule+ e."1 4E
p+ql EI¤¤
"Jq+|l 614+ E= Hl-ts+ gg aJi rll ol$ A.G = I,ts- tte= (pi + RTln pl -0ri * nrrn p)
ts + fl4. ol +41= EE4 oE Hl+ql {ol }e-e. ¤eq}
qI tlE +r+(rH 6A.2). +z+ +7I BqzlEî zl4& +zl = 4G" +nrhf (6A.4)
+B g.qEq Hl= aE +4qH flE 4e q¤r+ aol g+.

A6;olzlt:J "14"1 q +4e +e+ ¤AE oEal fle g4zl-
aol+. ^Jill ^llE oJoil^Jb E;q¤e.l tlqi t}*ol +4e A.G = A,G'+ RT In Q a __ P, (6A.s)
=
+e+ eg 4¤¤ alol olultr.t}_e-tr_+El +Eag
Po
^J^d6|4
+, +8¤ 4l+^lvl4L+, E. q ¤tF E" rl eg HI¤¤ .Jq ol e= .J+E 'EI+ zffiuJ'e}l g + glEril, + trtr| Cle
1e2 5 El+ EJtr
s Ce-lo}rll ¤ 1"14. olag ps=goJ 49 of+++ A)-o +

-tlo
*rl po=s"J ullel ++'ll(+++ B) ÎolE zrE-g 7Ie + 9l -H=
+,\l-g nfl
,160
+. E= Hl+ Gibbs "llHx1 A,c"1E9 :p)= HI¤¤4 ^JCE () H0

---:
E E-= E Gibbs qlHzl9 ile+ eq. ol4rl, K
5 o 6r.:
EH=
6 zal-g ttfl
A.G"= Gi (B) _ G; (A) = pi -pi (6A.6)
o
_o
-o 0
(9
A.G"el aelql^l= A,,zl t et}4"J aelr}]s '^JdE-HI¤-

E',E il-= +4U+. g-E tr.q rooll,rl E" pd: uls+ e."1 ^J
cE4 HI¤¤el tr= E Gibbs gluJxl il+ r=E .E= ^JC 0 Hlo
t_lo
rli.lE
Lj--r,
,r
5
Gibbs 9lHzl ilel esq, 4+^J dzll4-oe ffi ul$ ol$ lg 6A.3 813=r[ 8¤Ee.] EEt= +^l6l'E Gibbs ollLl^l=
^13'J(++:d
6Iq AI4I6J+. u13.31o_a+q r
A='J(++-d gdaTl^l d-d4e_e E6|.q, )_ 7lz7l?
^.G? a,G"4,='cl-. ralq gdEol gzoll qal ol=ol r]l TloJdt.= Gibbs
AS" = A'G"(B) - A'G"(A) (6A.7) .+ 7lqg :d3
ollLJ^lel 7lq("Jsl +c)71' LfElu+. ralr 0l=-crEl=
Ll-EILH=ql, 0l ,Je IlE E:d 6}lB-dtrl'.
=ail=
BBql^J= A,G=6ol+. rflr ¤Bql^lE ++ SqEE ^doll
El, + 7l-+Hl e= KE +4$trt. rflts 6A.s^lol Q-o-$ pol ol4(rB 6A.3). rBl+ flE+q- reJotH sA.17^l(A_i*G=
g+. nRT(xo ln xo+x, ln xr)) o E +q zl= Tlol$ Gibbs "llH zl9l
0= A,G" + RTln K
zlQ E"J.g +E4= 4o14. :rH 0e.rql^J _H_= utp* ?ol
oli Al o rl_q_;rL zlol - a) )e .:-._ olrL
-u -lEt*1 E l+"1 I /4A-1.
"i zic'jzi *a;H:te4 txji ciuus qiui zlzy 6zj +izi5
++'Hq, ol +idol ol HI+ saJEq ¤¤ ac¤. +44ril
RrtnK= -4G" .=f +)
\ Pe /.quiriu,ir.
(6A.8) gtrl-.
6A.8^10l utel ?ol A,G")0"J trll= K< tol{, t
+4rll=
ol +4149 slol gqqtql^l 7I* +sL6J 6I+4. "l al
^19 El6I"l ¤¤ql^J= AE ++ "JE"l Bel ++ SqEq
=.4.
olag B¤ql^J HI¤¤ Azl-+^lle'g F6J+. 6J¤ a,c"<ooJ
o + tL+, K(+ A^l o e +^l Aq6J 4,"14)E rllE r> tolq, 44^l ¤¤"1 ol+qeg ql Bel +E $4"1
=:s+.¤¤
+61+ rll ll.ol| *4lalol4. Ae] ++ *qg bztalzll gtrl. + oltrll= ¤Bql^l {CE s
zl- $,<llalQ.
zEtEt 0ll 6A-2
2e8Kql^l {lEol z-ollB +Bes 9E olCAill3r+ H}* E.EgE 8{ {zl,tl Az]|ts ^}^lg'A,G"<golH e}*ol
CH3(CH2)rCHr(g) -+ (CH,)TCHCH2CHT(g))9 E+ HI+ zlBzlol4+= aol+. rBl+ adql4 q}¤-ol zI
=4oJ
Gibbs"llHzlE -6.7k1mol-'91 7l*tr+(o|#g ^J^d "Jgvl B4"Jzl otuzlE L,G"zl olq+a,Gql 96ll^l eag+=
{tg acq} a}o14, olae-l dxll {te 44fl21 t* dol4. e<K"J trll= C%l-6J +*ol z|$zlolr(a,G<0), Hl
=4s
+). E|+^J ol EI+"ll .lle} ¤¤ tI+= trFq=4 ?ol 84. Eql e>r("J ullE gt}*"l z}ts4ol4. A.G" <tE +sE K
zl r-tr4 zIg-+E +E}U4r 6l^16l-= 1"1 ¤t 4
v _ ^- (-6.7xtoi l mol-r y( 8.3 tl5 I K-r mol-r )x( 298K ) _ o2.7... _ 1 q.
=-+
l\ _L
+trt.
Ex1-;6ql^l E rll A,G=oql dlB6I= Gibbs "llHzl +r

,I +El+= ag F Tlillel sEL Gibbs glHzlql ¤+*+. HI (b) gHJ4 HJSel 4?
* e-+B= T|zlr ol gELq qg-g ^J4L6H Ezt. "J"J elgul 6A.8^19 +EqtH E4= "JHI4"J HI+ql'I +4 4+^la
tlol 6s_b++H H tr+4^l c= ++s Hl¤¤ tl={E Ae_E + ?Itrt. +d EE HI¤+ slqr-*4 += 7l7la_ +48 + 9t
+El ++6J dCE t'-'l]E ake_e C¤4str. H6J aol+. r ++
46Iq dill qI+ *Alql 44^l ol {dE zl&zl}- "Je6}z
a,G"e+ ag aolq r4s ^Jql +Adol +El4zl t*¤. 4 o =)v,l 6l-qruJ3^l t7 IEE^ll (6A.9)
6A trJe 8+ 1e3
¤zlrl I= El+6¤ +4.Iq, ulE 4trI HI*^l +ql +4+= Q= floi' uJ8 7l-6Hl [8E] (6A.10)
+q1-+ I9 slqL%}4 +E^1, ^JCEql 46ll^l= "J9 <i"l E.l
r" HI¤¤ql qlql^J= 99 <l"l g+. qlE^l 2A+B+3G+D HI¤¤-E=3 +E slq}=*4 += zlzly + ^JCES +ill4s
HI+ql J. +.ol uA=-2, uB=-l, vs=*3,
ol uo=*l r4r s +e}9 trll= olEol $E_e. +4+q rn-l6}ol qI* zl-6ul
ol+. ,I +*4 rJol E4.
ol+lq} u}]¤¤ BC6IE
"Jq Hl+ *Alql^J HI* ciuus ql
qÎ(A.G)E oi4e+ zlol 6A.12^l o + ,+4'J + 9l+. ^_ ^JCEE9 ¤}+E
v-ffi HJ8 T|-eHl tgHJE (6A.11)
=l
u3 ciuus o{lLlrte} u3 7}=Hl {zlrl ¤+E"EE 4 +Eq ag s+q}*4 +E}+4 zl-6*g

6ll^'l ffl 4,o14.
+¤¤ p++=684 f uy$ tlzlt_ ^J46]] EzI. +*ol d6 "J+ rqE HI+ Gibbs ollHzlql ++ trI¤-4 Bol ara|
{q6}H H}¤¤4 ^}^d$el E4*"1 dn,_vfl( E}# H++ ^lol
¤+.
EI+^J "Je6J gEe+ "Jqql^JE Gibbs qlqzlel Irli H4t-
r-l-g-r+ 4lol ¤4. ge] Ezloil^]g
A.G= A,G"+RTlnQ BJB Cioos ollq^l (6A.12)
65=!/,d n,=\1t,vd(= \t dc
'',
z].JEt q 6A3
tr|+^l
HI+ 24+38+C+2DE ^J4r-ql ExI. ¤zldE uA=-2,
o,"=(ff),,=4,,u, uB=-3, u6=*1, r?-]r vo=*24. r?-]6}q ** zl-6ulE
trIg+ trol E4.
EAI 1 $EoEtr +4U +El Elfl¤
sE.e^l(I/)=pi+RTln a1)9 oJ$-all.<J slqt+ Iel EIE trlHl¤g Q=ao'ai'a.o?r=4
aras
+4.I8 ol ^19 gt'E= zlzlt_ ++E + gt+. ol +al
E +lel Bq+E ++4 ee ar+E eg + 9l+.
=
^,Gql
Eq 3Dql^Je+ 2-ol E¤ HI* ciUu' "lluJzl= trl¤. 4l
A,G" ^ls+
4I++
A,G= Zr,ti +RT)v,lna,
RT\v,ln a,= A.G'+ RT!

A,G" = -
= A.G'+ tn ai'' ot*rOr"" o"t,,.rArG"
BJ8 CiOos ollLl^l t¤^11 zltl (6A.13a)
{zlrl yE$ 4= sl-q}=J4 4l++.

"Jel Z}g ol
^lC
Btr|.
++. ,J46l4l Q+$ *"1 448 +E 9l+.
A.G'= )v,l,G"(l)
)lnx, =1n fI,, "JS Gibbs ollLl^l trJ=zf -d^ll (6A.13b)
¤zl,rJ zlc. rr:. Fltr+e.E -JE9 +g +qH+(.Jdg +e} ¤zl4 elql*4 +E^l +sE *=+.
u1E9
qE ri]e ++). r4H 919 ciuus ollLlzlql +6J alol ffi ¤¤ql^JE cg tl&zlz| 0o14. f A.G=ool+. oluil= +}
4 *"1 tarlg+. EoEEol BBql^JE <k* zlz14,
"l4rJ
q-s=r+ ?"1 ¤f
gltrI.
A,G= ArG"+RTl"flri
,.=[a,r,, E-d 8+ t6sll (6A.14)
cJ71l2 tI* z}6!Hlel EE ) equilibrium
olzlrl +94 aC Hl+ 7l-+HlE eEqI+
ol
^l¤.
Qe+ F-"Jol ?zlq} ¤¤ g.E" E5 zlzlr 4lt}6l]oh +
194 6 ElEttrJE
+. olzll+elts'equilibriumol4= Azl-= Eolzl ?+A+. EE EL+^J HI+g6JEE ¤¤ adg ql+¤ f ?lzl u|Eql q
^Je-E _BoL^J K= ¤B <tg, _z4r Q= * SAqI HI* + +61 +s6J e+E gqq} +al^l"ltrl.
4lql^lel Ztg ++U+= ag ++olAzl HI++. $EE(E
E *zirlEl)= zlzla_ 'IEIU ¤B ^J+ K= EEet4 =JE A
+4r ++. ¤}E" Eb +-qHlCE folo e gqqt4 ¤¤ ^J
E@ stru+Eahl
sEqolE tlc HI* NzG)+3Hr(g)+2NH3(s)ql qloJ
+E Eql +-qflc"Jg +=-6|q4. aH *4lel ++q^J= 2esKoll^JE g¤ t'-+= +61q4 r?]a Aill Sqol *
6A.14^lE gEE=S6l trl¤-4 z!$z"leg 4ill6l]î ++. o|,<l zlill= oltl4_" + +lfrg + 9lg Ql.} rz| 4 HI*
+=E BB +E "Jqr+ qB4l *4l9ExlE u-q4.

d}ET
ot
d *rlzl ar Cel
-E=,}]-E r.elEJ AIB 6A.13^19 ol+6l.q s= HI+ Gibbs qlqzl
_Q-zl
oe. e. o!
=.
blbi b" -- lmolkgt
Fr-E
lIUc" c" = l moldm-3 E aru+ +gql 6A.rs^lg r&l^l BB tI+= 4ltI¤I+. B
=o+
Tlill^J +E $e p/P" P" = lbar B tr"+= 6A.14^1¤. "l+6ll^l +48 + flsq, zlzll$ol
++6J rill, I (g"J6}trl) ol{}{ols + +z}^lElEg plp"a 4ille+ + gl+. ¤zlrJ
"lill p,Y ¤ IE +E "J4"14.
Eol ol HI+E g.= HI+ Gibbs .llHzlE trl+4 ,Jq.
++EL .-qillel rillel {}E"E} lolq, olE Edol slql^lqE
r}44zl"J aqp ol$ zl{E_ 6}z1 9+=+. a6}H O AS" = 2arG"(NH:,g) - {ArG"(N,g) + 3arc"(Hz,g)}
=^}il=
e+ Kql +* 4+4E ¤4. 4,"1d6l] ol+l6J
= 2arG"(NHr,g) = 2 x (-L6.45kJ mol-t)
:- olf+=Î4oJ=^l¤ol
qlqlqlql,
e +qql 46]]^J= Ell+61 #g +"-4
=61
ql^J r:lE¤}EE Alizl "i4î
14zAl 4gzl trllEoltrKEE sr;
rrr^t/ _
2x(-L.645x104 |mol-') _ 2xl.645xl0a _ Lr'L'
z]trJEt q 64.4
t^
- -13314n11-,-o1-1.^129l3K; - g3145x2% - ,, "
H"J HI+ CaCOg(s)--CaO(s)+COr(g)ql ql+ ¤B tl-+
q^q=$ ?Jt:+. El+^J K=5.8x tosoltrl. ol ar+E gq+4s-s B"J6I+
= ql$ ol Hl*ql EilEL gq+4 ¤B tl-+E trl-s-r+ rJE+.
:
K= 4Jco,r,)4c"o(r4co,( rr=w = acor{s) K_ ifo,-
o*ro'r,
-- 1
olÎe++Ê ol^J. zlzlltr a#6J + 9lg ull= ol4"l 4

ol KE HIE +lq^J 4l4I6J atg *=+. dal "Jq"l *g
ql= +71-^lqE p/p"E Hh+q ¤ + fleq, ¤¤ {'-+=
94 ?ol 94. e 448 +
'l-Sr+ Ag 9lEl.
K -- pro,lp"
=Î^lo
tr- (P*r,lP1'
er+4 "E "l a+ql= ¤B tr-+z| ol{lE}f,cel B¤ +
^- -n;tr
-Pln,P"'
7l "Jq(+il)ol ¤+. ^Jp1qH,1o"f

rPI g7l 641 2e8Kqlî NronG)+2Nor(g) HI*ql ql
6J BB t'"+E +6}qe}.
st.o=y.E
¤¤ql^JE 6A.12^lql,<J A,G=ool qq QE re- HF+q +
qo} +4. rElH trl+r+ ,J? 4i+z} +g+.
A,G" = -RTlnK Eq+4 EE g+ (6A.1s) GZEEil tsEol^ls! 6flalEattr

4qE aE Eall¤ HI¤¤E Egol+. tI"J =zl Ee%i
ol 49 g"J+ rlol4, E+ ol 319 ols-"6|E gqq}4 'llol ol noJ q}¤¤"l ¤Bql E.gltg ql Bg E¤*ol n"q4
El str.+q gelel HI+q ql* ¤B tF+= 4lrlg + 9lr
5A trJe 8+ 1es
r 6tE d=(n-n*)tno\ gtrl. 6flEl ** HrO(S)+Hr(g)+ *4 a=(2ttz19zrt=0.0205o1L1.+ * zyo{ Eol E6]]g+.

*or(e)"ll 4+ s.= tI* ciubs glHzl= 2300 Kql^J
+118.08kJ mol-'o14. nooKe+ 1.00barollrl HrO9 61lqE EE ¤E 8^l Ezll= ++ +Aql^l E"J+ 3l
=^PI
L
r- Qduhlz
ts I t. + Bl} s-ilzl ?J:bzlE + +t611o;,Jtrl. ol A+ql=
a< 1ol4 ttirJ^l E4 zlC4 "Jilq}+.
ze{g /.tB BB t}+E 6A.1s^Jg ol$all.<J E.= ++
Gibbs qlLJzlE+q Eg + fleq, q4^J ¤zlrJ E} "Jg
61lF-lE ae+ rc rlol9 +41= .JotLl]a r +ilE +6]^L a
rlTl B7I 64.2 ol Bzloll.! t++ Hl+E E= HI*
Gibbs qlHulzI 2000Kql^l +l-35.2k| mol-tolrl-. 200kPa9
olr|. f-,$ ¤B a¤g a= Tlz.la_ +ElU trh$ql oi-= r(ql
+6ll^l ++. E= H]* Gibbs qlHzl= =;r ololp + 6L
#zlz ol gEE #E + +-e--e E"rlrla+. Fr+6li
49 4oe qltr-qq, nFL^l a(1ol ¤ 4"14. ol ^l-¤
+s= #zl +ql EqflE o,el E +sg 4l&6lq+.
# ol*al{ r.rl4 oE +il= +g + 9t+ IZZ00'0.8
Eol 6A.1s^lg ol+6IH BB t'-+z[ r]--o--q- *f.

-s^lg+.
=e (c) oJE 8+= S4!
^lolel
9E"EE zlzl:t- ++U ¤B tF+= g"J6lzl"J ol5g. ;-
, ,, a.G" l.l8o8xlo'|mol-'
RT (8.31451K-'mol-')x(23ooK) Ee+ ¤+rl4oi 6J uilzl "*+. r?]flq g44se= Q}E
1.1808x105
E 4l+E +6Ir1Eq sF), olq^J af Tt\4 a,-y,b/b"+ E=
= - 83r45v<2300 = -6'17 "' a,-y{l)tc"& ol$ollo} ++. {zlrl x1E E Eg, br= gBt
rq6l.q K=2.08x 10-3ol g+. ¤e acg q+4 4-3 s E ralr. ul= E-bEol+. qlE^l +a4 +ql^l +e=- Îolql
A+B .-- C+oe| eg ¤¤ol "lFoldg uI g-g5EE "l+
E ElEq^l a9 ElfE ++g + ?l+.
all.<J arJg rI44oF 6J+a 6IzI. rBlH KE q^q=r+ ?"] al
HrO -+ H2 + iO, of qFl.
Ee"* n
a7l
¤¤ol "l+qzl=- -dn
"+ag'H+
0
+an
0
+ ion
K-m=ffi"ffi=K,Ko (6A.16)
BBql^.tE
szr"j 0- o)n an lo,
dil Ea* ol ¤*EoE 41+= HI* CEE"I ¤¤9
"lFflg ,IE <lg
e,e.d 1t+ta)n +6ll"t +tr]{qlE^J EE 5Fel Debye-Hrickel ll¤- ol*6}l^J +
E E&, xr
l-a d la * {t). r+l+ ol ¤}5E Al++ olul ¤B aCg 9a ?l"lot
r+ la I+ta t+ta +g + 9l o o _+ 4l+I"l +d-61ril g+. =E +alE al4}ql^J
*E "JB pr
(t- a)p ap lop 4 E= dxll Ezll"ll^J EI+H o + bEE 4l&61-= a tr4ql
t+la + ia + Ia ,rJ!. g|:a"E 4l+Eol E_+ loll zllloltl Ky=rE- # + ?l
¤zld E=E 4l4Iq^JE p,-x1ytlA.6^l) ols" 6t9tr|. 4 4E Eg + 9lr, ,r+4C EBE"E(EE EE"E). 0l+6ll^l
+^l ¤e t+= tr}s-r+ ?ol H4. BB E4l= Eg + 9lril g+
y= P''P'll _ a''' p''' a+ql q+^J= Tlill^J Hl+E ¤B tF+E gqqt4 ¤B
Paro
- (r-a)(2+a)''' tl+oil^Je+= 94 ++ Sq 'H4lql 5u" E= zlzl:n_ +44
of 6J ollzl- ?14. zlill!;ol 9d zlill"J a+ql= K+el pyE [J
ol +q pE ptp"E zI+61 +4u 4"14. *rl-4 o e
^l RTtr. H}E + 9I4. :48,
a< lol4A aIts t- a=t,2+d=2olq, Qe},rl trl-s=r+ e
g a+= eg + 91trI.
x=floi'' = Il (#)' =flrrl'(F)'
*=# il T ]'' * I] (F).
I I
ol Hzl 4 Z4 6Iql^J=p =1.00baroltrl-(+, plp"-1.00). tr|
196 6 EltrttrJB
(*Cql^l= tzll+ o.lffioJlz} zlbal4, qlaql abcdef* A B A B
abcxdef] *"1 448 + 9l+.) rfll- q+4 Ae +-qHI

cE ¤e tF+ K.= ols"+4.
tu
lrl \'' : j
K. =l,l[FJ
-/ 7l^ld uSoll EttEI K" tael] 6^17) 5
5
K
Boltzmann
Boltzmann o
Eg
trl-4^l
7t|i{l+, P 7lli1l+, P
K=K,,|I(#)' (6A.18a)
(a) (b)
lg 6A.4 + ++= Ael BE ollLl^l Boltzmann THill+ E=- o1

rB0ll^l= UB R-+az[ =+l8el
(a) F aEEEol ul*-zf ollLlxl gE=
olq^l u(rJCE) - u(HI¤¤)9 Au=ErrrE 4448 zlrllt H] =Eoltl'.Ae_l =91
LtElL.!r[. rH?=E 7Hi1lt= EEqq qa[^j EBoilN= 0l
+ql ql+ Ke+ & Î"lel +4lE tr1e-4 4.ol 448 + 9l+ = =9loll
Extl-dtr|. (b) oJB n ->B7l GEal eEo17l= 6l'^loJ Bsl
=01 ^lutl4oe
ollLl^l "JE7l'Ael "JEoll Hl6ll^l E[|E6I a7l q=oll BE
ilrE|.==+l =9lBl6H l a+. qaW
7t|i{+71 AE aoll =Pl=
EBoll^j= 87[ xlufi{oe
K=K,"(#)^' zlr1l8 HJSoll rtlul

Kej K,,\tolel E4l
(6A.18b) =rtl:dtr1.
+il 4l&g E tril= p"tc"R$ 12.03K= ol+6J+ + 9l+. * fl4-==g Boltzmann EE Hzlql q+71q. + ^ll
EE ql"lzl
=+lql
EE¤+(rB 0n.+). tr|4^J ¤.szt iq
*jr-u|l xittf t+/ f TErTH rr-iiu f?:
.-It+I ArÎI H--1 rI rl^l
--r
-l-l-l-l
u-f'cf^l --A:l
^l\r - -A+l -l.-I -
zlEtEt ofl 0n s HIg- s.Jgol +q+rll ¤+.

^J^dE4 t}*Eol E+
HI* Nr(g) + 3Hr(g) + 2NHr(g)ql Lv = 2 - 3 - 1 = -2o I 4. ol rHql^J ¤E6J u}q e.ol Hl
u|4rJ,
^J = qlqzl Hl]¤g zld tril= *e qlqzl
*aJ EzI
E= *= :zlel=lol ¤B HI* E6JE +ql zlHH4 o =+l
=+l ^Jl
+
K=K,"("k),=c"(u#u)' 614l g+(rB 6A.a(a)). rel+ ¤B tr-+= +Elql= =zl]
+
^l
"ll cmus "llHzlzt +4t+= ^ldg glulzle+ aJ4 +ul $=
ze1.rsKql^l= ol *4lzl-Q+r+ tol S4. E q6Jg ++= 4¤- 9"laJ4. ol q6Jg aA ee.q= eL
6J
_r.6H^l ol6llg + ?l+. a4 6L.4o)ql^J B9 qlqzl E9lEol
K=K,"(ffi)'=#t n9 9lulzl tzlE 6lzlt} tJd rJ ++61 Rqql
qlEql=+lEE4
r=el *
^}El61 Azla_ ¤B E}+ E
4. "1 zl]z.]lf7t
tr+q^J K,_6r4.2 Kz} g+. Ke+ 4= E+ +-q{d"Jg 6JE +qlE nz1 zlul]! o +zlzl f4l$ +E 914. ++6J ZI
+rE-,61qel..
4el qlqzl
=fl=
t9
tl=+ule+ +flflq(Eq nD a4
at{ "l a+ql= QIE Prl s4z} qlqzl s.q¤ ol{r-flr zl
Hl]4 o e ¤4. olqql + g+ azJ +41= H}¤^l7l-r.
(d) BE A+q Erl tG ail4 ^l-olel
fl= aol 6A.ts4l"Jql, +d A,G"=Af1"-TA.S"$ ol+6}q
HI¤¤4 gCEe ol+qd 419 Ezl¤ol BoltzmannEE H ¤¤ tr-+E trl-q=4 ?"1 444 BzI.
zlql q4 r 6l+ ^JEHE qBzl Ee9EzlE ^J46ll
Îolql _ a-a,a"lRr aa,s"/R
EE(A{ xl^l ¤ +a) ¤¤ tl+e.] EEE E4 4ol
(6A.19)
ol6ll6J + ?l+. sl+ HI*ql^Je+ ?ol=94

"
flzl-Eol rz Aql ^J4 Hl+ flBulz} "JolH B¤ L"tTl+= ag "J + 9l *izl
. HI¤ + 9lg ull S{BJ + 9l= sI++.$ flzl-Eol ¤et +(=, gg HI¤¤ qI¤¤"I *,rllel ¤B acg *=+).rEt
at¤ ol-?E Hi¤¤+ ol
^JcEEol4. F +++Ee
7+7+ a_
+ HI+ fl=+vlz} "Jg a+q= H}*ol gg^J"J a+qlE
E r+E qlqzl ^llEE *^l"J
Boltzmann +s Hzlg
dcE"l *rilel BB ac"l +El.g + 9l+.
=+lr=
ol$.llEql S4lflol qlqzl
dillE +E¤
=flE "Jg
6A iiJE 8+ 197
zl.JEt o{l 6A6 I
K _ g- Ge.zzxro' I mol- )/( s.3 145 l K-r mol-r )x( 298 K )
zlE ¤9 qlolElql E6tH HI* Nr(g)+3H,(g)*2NHr(g) X e(-198.s

IK-t mol-t y(8.3145f K-r mol-r )
ql ql6ll^J }. ZqS Kql^J A.G" _ -32.9 k) mol-r, A,H " - =g37.2... Xe-23.9...
-92.2k1mol-r, r4I AJ"=-198.8J K r mol-1o14. tr|+^J HI+ol Bgoloe ^J^dEg 4zl4l6llot 6IzlE}(++lE qr
r(ql El]6J TlqE q+r+ 4.ol ¤4.
al
^JzlE
qlE +El evi q$ql ^J{EE ^J^Jg 9xll*4.
T]ILJ=
=gET
tr l. UB cibbs ollLlrl a.G=.Gibbs 9lHzl5 +8 ll4Eql ql6l tr 3. u3 7l=Hl= ¤ tr.49 HI* ciuus 9lHzlE 44421 9"ll
+dE
E^l6J zl$zle\ z;q. 6l+ $EEEE ¤*"14.
^l ^J ^|eo
a 2. a,G<00J +¤+ g-8tj¤ola a.G>oe Hl¤+ g-^-scol . 4. BE A+b ¤¤ tr"EIql^J$ HI* 7l+HlE <tol4.
+.
=s-d^l=
,^-lzl
o=. -1I +4 al {a
HI* ciuus qlqzl A.G=(dG/E()r., ael 6A.1
HI* ciuus "llHzl {G= {Ge+RTlnQ,1 Q=fI o,"'

"Jel HI-& +4lql^J +* 61^.r2
s.= +* Gibbs qluJzl a.G"- ) vA,Ge- )

Produc Reactants
vA,Ge uE *9 i u1b *sz| ll¤ 64'.13
)v ,ArG"( I)
BB ^}+ 1 K- fl,i'
equilibrim
a9 64.t4
gEol4 ¤¤ tr'+ A.Ge=-RTlnK 6A..15
Ke+ K.
^l"lE +Zl
K=K,(c"RTlp1^' zlzll^J tI* 9d zl^ll 6,4.18b
Eiif 58 =J:doll gEF=+ts9?l
?+E+. tr++^J Hlg^d Tlill= 716ll^1 7I.J6l-= as_E= alel

> 0l EEE Ell+ ol*,
¤¤ e^dql "t# ¤6JE +zl *6Jr+(zlzllzl "l^J4"J oJ).
elqtrtLl trIqt A8= ¤4161.= Eiffiiqtx]i BEol galolLl .eE
?E TlzllE +vl= S+^14^l) 4lel "Jqg ftzlt'12;
EE[e] &TJEEloll olEz| I tHSo:l=rl= g0l0t eEh 8E0ll =q^l(+
qe= HEI= HJB fllgtrlet tlc_eu|E =6:1
gHol 5)7lE +E 9l+. ole+ gol 6IE ++ "JqEol SalzJuJ olpq Hl
Eltrl.
=861.=
. E6t^l ?+=+(rfl6|q ¤¤ ^J+r| "JC+ aolq). qls
^J
$d Tlill ¤B A(g)+zB(g)E ^J46ll _H-zI. ol HI*g B
> E{c TllEl
B tF+= trl++ ?ol 84.
"JEoll ?l= Zlts r.elg EXI EIE r ]aaJg Erl= ---4trI^l7lz1=
3:Br= LEIL,lrl.
K_ P3-
PoP*
> Ele'Et qHl rl^l
0l EEg EB Ar+el E= EJB Gibbs ollLJxl SZI ol
^lel
+He po{ *zl*ps9 4lE4 *zlzl tl4lg qlql"J
^lolelGibbs-
"JA+ <ig frzl{}4.:-4a}¤ po=pugl ulal^J q #46}rll
(Etrl 6A)= TlHJ-e.e Etq. KE 8E el== LlEfLllalE
Helmholtz^.1(EE 3E)= EE6Hot etct.
f;zla11o1 6l=ql, ol+rll qElH *l¤ a¤ol Bz| sqzlr. A
7i +e-s ol-sal]o| 6J+. *7lE +rl7l eiBql
trI4=q+= =
A¤:zl.el += +7i4q :. *B "Jqe +++ +q H+
ql 7l"Jq= aE+ q #461-zll *zlaflot 6J+(rH 68.1).
HI¤-E BB t1-+E +"H+ n-^(^Ji] p-^)E ¤6J-9 Bzl ?* olilH A(g)+28(g) B¤ql^J "J+g e. A+zl+7} 6
Eq l4Fe+ lecql^J zl..<llal ¤HaI4,zl"J +,H= ¤¤ql ']]
=trI. zlala- BEZI+7I Aa6F= e^Je: o*^q :*qrzl Henri Le
Egq= +Eqlg #zlxl? s"lq ¤B +lilql= ¤6"E9 +
chatelierTl zll"Je} q-s-4 ?9 t-e Chateliergl fl*E *
순수고체역합는
zl ?+=+. rfl+ tl$ ¤tlql^J= t}*Eol EJq= +E F =E
qBi e.JE EIEqI HI+g 4^ll4-" e ¤¤9lztzl r$r121 tI qlol+.
zl ?+=trI=
^}dg +=-6llot
q!+. ¤¤ tr-+= "Jqql ++6I 병화
zl"J r++r ¤¤ z\nlzl "JEql ++6l.trt= *¤.
"Ir-14. ¤Bql 9l= 4l7I j/+g tsrll slH 4l= o.[
0)-
¤¤ ^J+= EH6l gEql 9=61q, r E= "J4e s= HI r .u* .gr+= lro]l17leJ= HI¤¤ "J o=ru
-HoFl
+ ?lg4E+q ql+g + 9i4. o a+. -C
ol gr-lql el6l-E ¤¤ql 9l= /lqlq Sqg zl6IE ol *zl

5B.1 gajq g:d
¤¤ ++E 6J s= "Jqql^J C$g A.G"9 ftg
zlzlt_ /l
&6J+ A.G"9 {t qr+^J Kel {tg ¤¤ol d4le olFolzlE
$qql ++6l.tr| Hh+q "5"i8 +qd gEql^l= K7l *+ o
e
ol+.
gieel ar+. *qg qBrll 7}6tL+ql q4 +strI HI+ e o
¤:zl 49 "Jqe r "Jql+ Hlgd TlillE +"J^lzlE 6zI*
o'o
o
o
+. rBl+ zl;115o1 "l^J4"J trll= oli.lH Tlill$ zloll iolE
o o o
o o
qI* zlzllel 59 SEg H6I^l ?+=+.+d Tlxllel 5-g o;- (a) (b)
49 : zl4lzl ++eE a *71 4"ll Bo}glg *ll ++421 fg 6B.t Eeoll ?1= UBZI= gr'+^l7lE(o_e+81 69 zF1l8 E^l-el +=
q= "Jqolq, 4E zlzllz| fxllaiq+E ot+fl ¤5;t9 Bzl ?J^)l7l= ,J8o I "Jq'JtrKO I e+oll= E=E ?E=E s^l-d 0 l:BFi1l7 I SrJtl').
68 trJBoll E:el= T= s?] 1ee
g "Jqg Hs+zI "Jq'PF ++. ol+41 qEjH zlAld'-

=ol= 00
49 "J"8ol fzl 4li9olot otErll, olAg A(g)-2BG)9I
1
0.8
eg Hclql 6|]'"6JtrI.
ol .J+ -s.!l¤- C=J4eE 4*zl +lflq Ael ile-- Ee=J 0 .6
\
10
-o- ,olrp alz(BE S,a). ¤¤ tl4q1.q ez| B_tr. SllEl= Ltj
il 0.4
-
,to
Z zanol ¤+. E|+^J ¤B tr-elql.<J f{]ap E Eg=g 0.2

\ 1
trl-S4 ?ol ¤4. 0.1

0
0 4 8 12 16
n^ (l-a)n l-a 2a *e1, plp"
no- n,o,. - (L-u)n+2an - I+a ^B =-l+a
fg 68.2 A(g)+28(g) HJSoll EH-d EE dt|alE a9 "Jal q= S4E qai
r4r 80|-d EE A+'J(de-l E^l)oll^1 LlEl'-.! lE. a=03 ++-d Aoll 6||'J6[H,
¤¤ tr-+* q-q=4 #"1 ¤4. a=1? ++:d Boll 6tl'J:dtr1.
68,.2 gEol gE
{zlrl p=: dill sqol+. ol 49 q=q=4 ?ol 44.3 + gl
trI.
LeChatelier9 fl4.11 E{.H ¤¤ tr-Ellql fl= 4l=gE.g
eJ+H ¤.g +e--+ ¤¤"1 olE"+trl. ol+rll 99oh E
oJ6-J
s.! zlall{l otlHzlz} ¤+qr gE ^}+ol qzilg 1,"14. e}

a- (,)
v2
(68.1)
\t++ptxp" ) Hql gEs. *+q+E Bg ,J6J +e-s ¤Bol ol:z"oizll $
4o14. olBrll 9ol"F ollHzlzl-%r-=Elq zlalg- 9xllts $r
ol 96lE ulg Ki "Jqql ++6}zlr* es+ n9 EA* 4"14. ol AEE$ q=q_r+ ?ol eef6J + ?l+.
^lql
g sqql E=6J+(r4 ol el6lE g.9ol *zlz,J
's.z). ^lql gg HI* s--Etlg4rlH HI¤¤+e-E ¤B"l ols"aJu|.
ql trl4 qzl zltoftql, ol/.s; I-e Chatelierel gp-le+ +*q
E ¤4o14. gg HI* +trrl$4zl-H ^JCE+e-E ¤Bol olE"d4.
#JEl q 68.1
(a) wnt Hoff A.l
"Jer-loI'JC +* Nr(g)+3Hr(g)=zNHr(g)oll,<l ¤B a ¤B ^J+(+ill4 o + lnK)= gEql 46H^J E^lqI r4s9

ol z1&zl3 +r}.11= 49 +E6tH gEql 4+ e¤¤ C=J4
Coll "lzl= Sq +7lE ar-]$ rgoIElE HI+.il E
6H^J Tlzll +zlE fzl zlL6J4=.ras o El 2E)
^l-¤g
a "e¤9+9i+.
EI6IH 94. El+^J Le Chatelie'9 fl4ql el6il^J Sqg
@ gE el=E
*zlt'lrlfl {CE +ol +716}rll g+. ol **E BB tr- hKel LIEILH=
^.1
+= r+q=r+ ?J:u+. ++4 ?ol 44U en.rszl(A.G"=-RTInK)$ zlzlr, tl4r

++.
y = P?*rP"' - *?u ,Pr'P"r' - *ilrP"', - "x''
K,
P*rP'r, **r"rrPn x*rx'nrPz "4 Pz
lnK=_+?1
¤zlrJ K,= ^JCEI+ Hl¤¤9 *lB E ESg ;aoJd-=
BB tl+g "J+ol4tre1g R4 r; ¤B tF+zI olq EIl 1 lnl(q ** 49 "lE
q-). rr}4^l 919 mrql +ql 49 sgql +6ll^l "l+q}4. r4H,
"Jqg ulle f;z|^l7lH x,zl +ulltr_ ¤!7I6]]oF K
9 #ol "JC6I4 +zlg+. dlnK t d 1 A.G"/T;
dT RdT
ol a4= ++4 ?"1 r4 3 + 9l+
200 5 altrloJB
d( AG?r) n dlnK BA
----aT = -^ -27-
I B
Ke{ A,G"g gEql"J .el=6}a sqql= el=6lzl s:e-E-tr.

ol
"lEE* 9d "ltsol+(+ Sralfzl oI'141.
*. \
tr,Jz{rl2 Gibbs-Helmhoftz af fl olg K
5
6
s.el 4¤- rJ {zfl^lTlelH ++!+ z.9 +4u Gibbs_ -9.c 'fP Es,
Helmholtz
=.e
d(GlT)ldT=-HlT2)$ ol$-allot
6ru 6ru
, EI+. ,0ln l-ru
^J(3E.10^l
d( A,G"/T) 4H" 2A > 2B + c

K 12
dT T. (a) 7H111+, P (b) )H^11+' P
¤zlrJ Afr"g gE rql^Jel s= $* Btc → Ai

Slgsl4. ol 의 + fal 68.3 El+'JEoll trlilE EE ErlE ¤EdlalE Boltzmann EE9
^lg SEoll r4E Eal'ef r0ll ntE 7tli.ll+ EE, Eel Ert= -HoloF -dtrt.
4l r"ilrJ ee 44 aEl6IH q-q=r+ ee 49 eg + gl+. =EE
(a) EE USoll^1ts 8E 860ll ttlzl BE tll^1!#tl A= +LHE^1
Btc … K 1 =7[-Jtrt.
AE
①
(b) "JE HJ8oil/(]= 0lef UEH7l.Etrl-.
,,dlnK _ 4H"
D → 2 BtE
…
③ K2
ol trl-s=$ ?ol ut+l + + 9l+, ^J'llE zllillf5ol r"J# e46J+. "l+AI
qE rgql^le+
^13
dlnK
2A + 2 ㆍ → C XD
디르
aol BEzlql ¤+q= tr"E]lEE zlAlizl AEzIq zflx1;¤-
L,HU
ㅋ van,l Hofl 4.1 (68.2) +{H^J +7lt;lAl g+. q+^l B ^JEHEfl + zllz]lf| f;z[
dT RT2 K2
2
X 19② - 6}jr, ¤B Eq+E 4"ll sz| q ++6l]Tl+. ole+ HlEll.tr. Hl*
ol gg"J trll="(rH 6B.3b) gE ^J+ql E6ll^l A ^JEilE(+g
68.2^1¤. van't Hoff lol4r +trt ol ^lql E6IH _tr= a .llHzl9lrl ,Hz,ll+= B
^JqEq zll;1;g- +LilE
a 6lql^J gg HI*9 A+(4fl".0)ql= d lnK/dr<O(tr}+ .<J
^1461^=)el
f,zlap H}¤.Eol q ¤.+61111+.
.{ dKdr<0)ol ¤+. ol raJfzt ¤-ol4= 4,3 gszl. ¤-4
e ql ltrjlKTl ed6}r. Irl4^J K zI4lE ei6J+. ag F+
+. trl{^l Le Chatelier9 fl491^le+ ?ol BE H]+E a+ql
EEil E=HJerlstrtet +E
olell rlloJEl= HI+ AgrCOr(s)-_ AgrO(s)+COz(S)9 ¤¤
¤Bd"l xJcEE+El EqzlE +e_e olE*trI. sg HI
= uI.
+"J HlEil A4rI ++U+.
*izl gEql q4 H6l+ 49 -u"1=4. "l +6ll HI+E
ol+l6J tdol +++= gqql4 g"Jg olallalel$ A.G" E= HI* etBqE 4{}6}q4.
-AfI"- fA,S" ^19 -4.C" 1T--LJ1"/T+A.S"-E- +J. -H-= A TIK 3s0 400 450 500
ol ++. gg HI+"J Eil= -Lfl" trTI HI+4 +9le-l flE eq K 3.98 x 104 1.41 x 10-2 1.86 x 10-t 1.48
*zl3 ++qlq, r?-16l.0l ^JCEol ¤Cqril 6]l=+. e_Ezl

94zlE -Lfi"tr7| Ai6l.ir, q4^l ++lel qlE+irl *zlzl za{g A}Ef vant Hoff 4s zldg +E}+41 rlt Ee
ail= 4,"1 ¤4. rflo}q dltntdT=-llT2oll EBll^J
g+. gg Hl+"J Ell= HI*419 Ql= + -4 Gzlzl HI*E +s dr=-T2d(l/T)ol g+= "l+*+. rElH 68.2^10l
^h¤g
+4lqol qqo} aJ4. "lull= sszl 94zl-E ++ql E4qI q.q=i,+ ?ol ¤4.
g6&3 ++ ++19 fl=+ul s4z} ei6}q(+ _Lfl"tr7l
dlnK 4H"
$"tTl+), trEl^J ^JCEol ^JzlE+e_s tlSol "JqU+. R
$z|;5ql^J g "I +lE 4¤¤ol z]f+ ol+E tsxl-! Ir|4^J HI¤. $rB.vlzl gsql el=61-zl ?+g rlli -rnr=
"l zF& qlqzl =+l ^Jq Boltzmann +E= 44421 ullEol l/rql q4î E^lr],$ u\ zlgzlzl afl?nql zldol 4e+
+(A4l zl^-l Ag -H-ot+). gtr HI8"J A+E "JHI4?I qlq oF 6J+. dxllets
zl Hl]gg lH os.:aql +ElLHf;.Ecll, gE= gEJ+H -lnKE l/(r/K)ql 4"llrl +q{Ide-l E
=+l 6lq A#"/Rg (71&7lxr0e+ rt-rll t+.
Egzl HI+iq Tl]ill+ Eezl reql^Je+ ?"1 H
Boltzmann ^lE
El+.+ $s qlqzl ^JEllel zflrllfflol f;zlap *3 "llHzl Eo! +d q+r+ ag sE El=4.
58 tsEoll g:el= T= s?l 201
(b) tlo!:d e,_Eoll,\lel Kqil

TIK 350 400 450 500
(103K)/T 2.86 2.50 2.22 2.00
qL 6J 8s r,ql^JE ¤B ^J+ aI 6,9: ole" o|"1 +E e'E
-ln K 7.83 4.26 1.68 4.392 r,ql^lel ¤¤ tF+= +6tElH 68.2^1¤. ol= + g=. .'.1o1q1
^J
4+6LH g+.=,
ol dE¤ E^l6J 4ol :zB 0s.+4. ol :r.4F9 zlgzlE
+ e.6x rdol4, q4^l ?l&7lx K) = A#"/R_tr_+El q-q_.,,+
as aq¤ Eg+ fl4.

lnK,-tnK,= |JiSo, (68.3)
A,H" = (+9.6 x 10: K) x R - +80 kl mol-t

rej 4tlE gE H+lql^J Afr"ol gEql a#+ql 9=6}zl
t+E+E olag 4ts zls +r-e-E ¤qB + 9l+ r4H +l
r+g=4 eg aq¤ gg + 9ltrl
8
.2 e-l
^los+El
6
4EA.I,
o= -2
,/
V
T
c 4
tnK,-tnK,= $-Fr,*'
U q+^l
2
//
0
rnK,-rnK,=-+(+ +) KE EE E= (68.4)
2 2.2 2.4 2.6 2.8 3

(103 Kyr
feJ 68.4 E= UB g!=Jtrl7l'gtEoll rlaf Ee Eatxl gE trll= -ln K=
r/r0ll Ell6llÎ E/.l6l'E 7lz7l7t ttf tpl4.lcol LletoF:g aolq. olae
HJB glgtrl= +E6lE Hl-gXlaJ4 HJgoltrt. E^loll EllolElts ZrJ:d 0ll 68.2
?i0|tr[. ^l.EEl
!l7l6BjtE
oJEqoI .JC EI*ql ql6J s0OKql^JE ¤B t+= 2e8K
rPl B7l 68.1 HI+ 2so2G)+o'(g)32SO'(g)el ¤¤ tL qlîel ¤B tl+{H}¤¤ N,(s)+3H,(g)+2NH,(g)e} ?ol
its looKql^J 4.oxrPa,500Kql^J 2.5x1010, rela 700K +48 "ll 0.rxld)-e+El 4l^1617l +l6}q s= HI* $B
ql^l ul AfI"=2ArH"(NHr, g)E z[=. ¤9 s. 2C.4++El +6]
3.0x l04ol+. sooKql^JE HI* qfBElE +4q+.
g ol 7|"1 ol gE gEql^l oJC6I4r zl{6Jq.rBlH
r-loutft 002-.11
Lfi"=-92.2kf mol-,ol qq, q4^l 68.4^l e-tr+El q-q=4
?9 445 tsg + el4.
¤¤ tr-+9 9-=. el= +41= ole" 6[fl Hl-g4l*4
^rr"g (-g.zz*toolmol-') / I I \
*B o + +B + ?14. "l %r"BE BAe HI+ flBulz} ¤xll lnKr= ln(6.1x10s)- | ' lvl
soor 298K
I
I s.rr+s1x-'mol-' ./^( )
ql ilq^l= gEql E=4q, 44^J E^l er+7} Sd6J zld
---
= -1.7
g +EI,]]zl *++= 1"l4.ral+ q++el A+, ol gE
E=E= Ellt6l zreq, EI+^J ol E,rl 44zl HIi/4 +g trI?+^J Kz=0.18o1 g+. ol Ag 2e8Kql^Jel AE+ 4Le
zldg +4U+. dzllql ilq^J ol *Bol 4+61 g"J6J ¤e 4, ol tse HI*q q4^J qlt}lH,H qEt}.
olulzl"J ol '*B groll ol-a"aJ+ S= 4*zl ".*ol 9l+.
T]ILJ=
=s-d
tr r. gEq4 ¤¤ tI+= +,llE ¤^1l+ "Jqql +S6r+. tr 3. ¤B ^J+9 gE- E=E= van't Hoff Alge ?olzl4, zl-8.
A 2. LrJ $WI aCql Elil= ¤6Jg Le Chatetier9 flalE zl- {IEI]E t}9 ExI tssE zlxl:t- ¤B6J + 914.
zlr -sqldJ + 91trf.
202 6 fl+BA
=s-d^l=
ce ,r.I
--1 +4 al Ha
vant ftoff d ln K/dT= L,If lRT2 68.2
^l
d ln l(/d(l/O=-A.FflR trI= E"J
B¤ tF+E 8s q= l" & - ln 6, = -(1.H" I R)(u T2- | I T ) a,rf= {r-+e+ z}r}t zlg 68.4
E45c trt+drl
C^l7j 4z1zl7l}$ +4.ll|l 6ll=+ eHU drl= r Azl

> ol E4E Hfl+ts ol8
0l EEoll^1ts ElEtErl Lloll^'l "JolLl-= 0l|+ 7lEE10lr, 7l¤E
.Jql^J
"Jq+= zlg4 HISql 96ll^1 4+71CzlE sltr|d
0lr, E 38151 EETI EtlEol
zl+. 6J¤ Eafl Exl= e]+ dgE d+= ol+6ll^l ul-z}ts
HJ8E tllAro-e 6Fll Etl.
ETlEtet4 gEE =
0lE6l.E =sEl
tr1El¤ iHE$= EllEdI 8"J6tXl zl HI¤¤ "Jq+rll 6k e+qldzl+.
+Eg + fleq tl.E SEo+ +Eg + Sts Eq+4 dH
861.= t1l olEg + ?ltl.
5C.1 U-HJEEI E=
> E4C 7llLJ
gEEf SEel "Jal 6toll^l U30l +:dg + ?tE d7l4 gg UB
.JHI ++ql^l tsllfl,4lzl"J ttEl* 6J +o ++q dzlz} E"l
Gi bbs 0ll Llr let r;ltl'. 4 +zl= Hslr" 6J +ql 4zlzl zl-aNz15 Hp++.
=!Elol*
r4r tltrl-flfl HJBS 6J ao eg+q += =o e_E_ {z}z} ol
> Ea,Et qHl rl^l dq= HI*ol+. flx}{ olSol oldq= a+ ?J+ ¤{r-fl +
Hl-gH
Hlqq 4zlzl oldg +E glzlq} ¤ a4 Eql,tJi ol{E
0l Erlq|;.jts Gibbs oilHrlel trzl(EE 3D)=
gd^le Aolq. E7l tr1El¤ il= E6=]|^'l ^tolE
d6lE olE^l7l= gE
olExl zlsltsrl= g0l0} atCt(EE 2A). ",.*= AEol EJ8 7l#lel dz}9 oldolq, tr14^J giEq t0pr1 H6J+. 44 Atl
BB A+E 8EE olEoFll EcHErl 6A). E ElEl{l4r 6}q, dz} tszllE t}Etl{!+r 6J+. t}s}-+Hl
EI¤+ qL aol+ + ++?l u-HJaE ilE LlElg + fl+. +
?l HI-HI¤+ dzl¤ ¤E zH'Jtr9 e}Sol+. &E+-+Hl HI-s-
trt-+drl= olg dEill"J d6]|tr(+.1, .lill E= rill) +ql ol olH HI+E + ++g HI Hl*E iis +48 + ?lE ?*zI
+ d=(#+ dri1lg B= aol+. ql d+4 r dqleg 6I 9l+. + HI HI+ql^J ++?l¤ EA+ &+g Eeg &e+-+|g
+el E= 4gg "J=+. rBl+ a+q El+^J= F d*ol tl"l4l oJ+. "JHI4 " + St-i+fl 89 ovneas* tol 4
6l+E 4¤g ="f'6lt +E 9i+. qBl ++E di¤¤ s r" dlB6I= +Hl ql-E}+g +*4 ++U'+.
ec.t"ll sE6ll +9t+. olzl"ll 6J4l E^lg 'El=+^d ++'Eo
Ox+ye--+Red
dz|9 *agol+ +i]]E^JEI 4}+6la +q] qg ol^Je-l q
(6C.1)
gg 6tzl ?+b aEol+. Aa1]pol l;.olal ql= + 4dg- g

cfalE ¤a^l?J + 9l+ g+4= rl+ d6t]e +.-4(qle^l zrtrJE! ofl 6c.1
6Ja er-l 49 rcr)ol +"]+"14 dzl9 q_a= s Sffio1 Eq +4q= HEI Agcl(s)+Ag*(as)+Cr(aq)E
=qfl= {Ie+-+|+l Hl¤+ olt--lzJuJ r+s=r+ ge + ++tl HI-HIf,-E
ite +48 + 9l+.
8 6c.1 4= E= AgCl(s) + e- + Ag(s) + Cl-(aq)
d+ ++ 7li,- 4I4-
+g r^d}
*-HI8 eg*(ag)+e-+Ag(s)
-*t M s) M* aq M+/M M*(aq) +e- -+ M(s) { zl r-l &p+-+}fl *Z +4 AgcuAg,cl-c} Ag+/AgolQ.

fl
-/\ o ls
-,
E=
717ll n(s)l&G)lr(aq) r/& r(aq)+e--+j&(g)

Pt(s)l&G)lr(aq) xrtr in(9+e-+X-(aq) A+ 4¤E aCg :z II-HI*9 HI* 7l-6Bl QE zlzll-
-,*.t
El a/ M(s)lMx(s) lr(aq) M)vM,x- +44= 4ol ¤4a14. ol zffiul= dill4 HI*ql 'l]6J ar+
Ha{lod
='o c' E 5'if(:;.x_(aq) Hl+6IAl C99zl"Jttr4 6,t, q=flai,) dzl-b 44421 t*
ft(s)lM.(aq),M2*(aq) M2+/M+ M2*(aq)+c-+M*(aq) t-r+
Ll.
I
ÎE+-+g
20t, 6 a|trttrJB
¤ ¤
or(g)+aH+(aq)+4e-+ 2Hro(l)q HI+ 7l-+Hl= q-'q= 4e rl'8¤
"l Er_il&C +aq +ql^l o,7l H2o_tr +I?lq= HI HI* ). E7l
0l-E +al
atr,o
Y ,l.oo,=af,-po,
o= P'
BTOIE (il)EE
-e.oH
o-
E {l F^lqî= Eq ++:E"E= 3.t}{_etr tE +9le_q

(+Eol #-e--E-tr-), &4= 9d zlzlle+ B"l qf++a E fB 6c.2 Daniell CxlE g=. +al d=ol ol'E E+01 g=oltl.
a-as,=po,lp"oe+9t+. E^l'- ol'E E+= E"=HA1 d^l tr+o-e =+olr,
ffil^{Llef +4 C=¤ Stl^1 E^l
q=olr-lrl.
^_e.e
Eleldzl{l^l* dill4 RI¤¤ "l? +|?l $CI+ {IsI 4 e e *= aoluk:zH 0c.r4 ee). rq+ a+ql El4^J=
=
dol E4¤ *zI +ql^l "Jqu+. + ql d+ 4¤ql^J=,rI d+E¤ tolt d6fle +.1q1 BzI"F oJ uHzI 9l+. qlE^J
*zl, r?-JI trl= d+ 4¤"ll^J= ttflol "Jqt+. HI*ol 'Daniell dzl'"llrJ* 6J d+ql^lE tlsl ¤|fl alol Cu2+/Cuol
tlzlElfl El d+E &+ HI* Red, -+Ox,*ue-oll^J +g dzl. r +E d+ql^Jel *Z zn'*tznol4(r* 0c.21. dalltr tss.
7l el+ qs$ Fr+6lr olq^J += d+g E" 6I¤ dzl 4 i| flx|q1.<1= + 4+ 4¤"1 daileel }.E"J ^Je += g
o + cl,rl
=qz}+.
ol {z}z} SqztE d+ql^J= +}g H}¤- 4{zl} +g+. E d+ drlql^]= d* zt4lEol ^]
Oxr+ue-+Redrz[ "JqU+. t}s]r] "Jq+= d=¤ g=, :1 olal |.EE *Erll, olag=Ei[
ol {zlz} $9"1 tr"lal F zlrll-
?-lr +l.flol "Jq+= d+¤- ffio1+_7 El+. aul.-l dzl.ll d+o + ol+qrlAL+ EE LoEz[ {tolal + oPJe(+g +
g+ol osErf * qfl¤g *=+. "lae +]?19 "J ol) d+e-e
^J= "l+qzlzl ull$olr|.
_g-TlE t oxrzl r d+(re 6c.rE ¤-+) o s*q dzl¤ s
olqll ol d+ql+ "Jd6l¤ B4 tzl ollEol'Itu|4rl dzl (a)
"42 E+ tr1E!¤
ulQl¤"I ++).qI¤ "J+ql^J= tF+zI "Jq+^l I dao +
Daniell dzlql^le+ rJol F t"l6.J dqle *"lol d6l-r gl=
47171oldqq, q4^l ol d+ol /J.44 " + ¤.d6l¤ *rll
dzl"llrlE + +"+q alE Îolql qfl¤ +7ltr- q .+
E+(*e i4fl¤ql 6]]%1-). ^l7l
4{Ecll, "l trlHl¤ ^l¤ EZj E+ tr{E!¤ E,i4l aJ4. "14
6J a"#9 E 6t+el qle^J= tr"lal }.EE F g&
6C.2 ¤Erl +4+= d+ trlHl¤g E + 9l+. ol d+Eqlî: "lE^d"l
Î"lql
H* olgol E+ #g +o+ +_q_E +&6il Eq7lq, r Fl=

zltv t*,* ¤!E dzlE F d*ol 6}+el d6il49 +F =
u|4 Bulzl-* cr olgol _,-fl +E__e_ +&E+. ol qlEql d
+Hg Îolql Fr iilHltr ^Jzlq, +
olq^J
"l "lgE
^l7l
ol F"J6J +EE +tB + 9l= "JA+ Zi$ *zla}4l g+.
E^l-
dqiA EoEil dzl= alt "lEl6J .47! d+g 7[lq,4+
oF-
o-
O-
E- tEiI dzlE "lag *zl ?*E4.
+ d6ila +a4g g+?-l(rH 6c.3)= E6ll^J gA^lzlB "-4
a d+ qHr¤g ¤q ¤ + gltrHE I rllzl 2my atr +). g
44zl d+ qfl¤g s,"l] f L ol+= g+el "J e.ql^Je-l
q4A d+ ulHl¤ol + #e +a!E tEql ,lel ++6lq
$trl Efl ^J
e- 49 tr4llzl ullE"l4.
fal 6c.1 ,JulLl Erl oJoll^l rl,J4 HJSol gcl-J rll= drl-=ol El d=
(^l+7t gqLlE g-f)oe +l7ln 0l d^lsl rt= d<Egol golLl'= (o) E{ zlE
,.ltt. trt4^'l ¤E Tr+7[ Szla 0laE goll 0lE-g + ?Itrt.
ff--;oe olEatl
++E= d^t7l d^l $o-e Eo171"= C=¤ s/.lolE ,i014 -+A= dzl"llriE ol;lle+ *3 zls# ^FS*+.
-E
E^Pl E^l= ffilriLt7lts d- E/.Fsttrl.
6c ElEl flrl 205
o{
E al ?l HI-HI¤¤ Bq=q(+ g+ A+ql^l 4le+7} "Jqt+r E
Zn 14 cu I*
a"l+) a+ql q4î= + HI-HI*ql^.lE dz} fE t"J
=
6lrll qE+ *+q +qot ++.
zEtEt 0ll 6c.4

{zl Zn(s) lZnSon(a9)llCuSor(aq) lCu(s)ql^-l= + d+4
ZnSOo(ao) CuSOo(ao)
r {lg t}-t}$"l trl-g-r+ ,Jl-+.
9-E+d+ Cu2+(aQ+ 2t ->Cu(s)
fg 6c.3 E4 SEtlE E-Es4ol iHgTl uxtg= )1+=. Ar| g+ d+ Z*+(aq)+2r +Zn(s)
ae E+aE -E ^llE
Zel 8^tlElE HJEH U-BF9 + o4?J tr+ I4EJ!¤= +=tl-.
^1e 4 Eg+ +E dzl-Eol +q++. ol$el
EI-HI+ql^] iI
f6LH d4l4ql dxl eI*"1 +g+.
=
* 4Al Cu2+(aq)+ 2t - Zn2+(aq)- 2e- + Cu(s)-Zn(s)
"+a d+
d+ iqQl¤"I ^llZqS.4r "Jizl= 4lE 9zlrl zr= d-41^l7lr. c"-l= 6IH trl*-i+ +2 4wl
+e+.
Cu2+(aQ + Zn(s) -+ Cu(s) + Zfi*(aq)
zlEtEt q 6c.3
F d*"1 5"J+ ddlag +.+6I= Czl:
Pt(s) lH, ( s) lHCl(aq) lAgCl(s) lAg(s)

(a) l..lernst 4
4zlzl slo.t ¤¤91 Ep:"izl ?*9tg trll= dzl HI+q E6H^J
:zB 0c.29 dzl:
4zlzl q+ qs5 t6ll^J E =41 qa qQ^J 4zlzl 4zl4
Zn(s) lZnSO, (aq) :CuSOn (aq) lCu(s) "Jg B + ?l+ +qd "J9 dz} oldql E6H^J 4ollzlE "J
:uH ec.:9 dxl: E "Je F d+ Îolel irlHl¤ ihql el=6J4. ol iilHl¤ z|71
ull= + d+ r|"lE olt6l-= "JA+$ 4zlzl "te "JE
Zn(s) lZnSon (aq) lCuSO,, (aq) lCu(s)
|
=
.lzl4 "Jg B + ileq, iilHl¤ zIzI 4Lg q= ee +q d
zlzl rsg "J"Jg g + 9l+. dill dzl eI*"I ¤¤9 "l-+
EzI d+ ulHl¤ol zl14!9+r rl-C+ a+fl d6HA +
Ez} {zl9 6J 91, r 9l= dxlb "Jg e + fleq olull= trlHl¤ zlzl-ool $Q.
Eq 3Dql^J ¤$il ule+ ?"1 "Je.J s*Ee+ "Jq 61q^l
Pt(s) lHr(g) lHCl(aq,b,) llHcllaq,b,) lHr(g) lPt(s) Alzl6J + 9l= al4E Hl-S+ "J3 Eo.all(il/.ad*o=AG) o +
+qd+. dzl siqlql^J= Hl-sar "Jol 4214 "J4 E"J6|
q, al= dzloll, E AG= dxl tI*9 cibbs qlqzl a.GeI
5C.3 dr! qEJI¤ Ar+. rqr alrll 93 Hplz} zI94 " E "Jqg ql B6]|zl
F4 g + 9l= "J¤- +a6l.q dzl9 gEqi4 ^de
T3^]|7I
,JHlq dzl9lrJ +s= Cft dzl g +6IE]H:z dzlE 7iq4_"s 4L+^14 al'}| gol u]er
"JglrJ "Jq+= zlg4
Hl+ ull$q da+. Er! HJ- dzl9 9E{ d*ol **ol + 6llot qI++i"J olq+ Eq 6Aql^J ¤E,tI uls+ Aol HI*
94 ol d+ 4¤ql^J +|?l q}*ol zl$4 o e "Jolti4l zl Gibbs 9lHzl= RrlnQ=: F4q HI+ g6JEe-l a^dql E=
C6Ir +4U 4o14. s-E+ d*ol dzllE *+"J trll= s^l 6I= Cdol4. EI+^l a.GE +e6iElE B^lg "Je acql
¤ rqlE9 dzl t}*ol zl$4 eI*"I ¤4. zfl+ 9-l+ A rJ dzlE zI94 o + 4LE^14"t eI4. ol+l6J + arJg
+ol ¤-+ol E trI= q "J.Jel dzl e}*ol z|${olQ. =+
rlzl4H dzl slHl¤g rltB dge-l ElHl¤r+ +¤g ol+rll
44| Tlg.l 6ll'J6I= dzl tI¤¤ +4.+lElH +d e_E+ 6IE^J dzl *¤¤ zI94 o + "Jq+rll 6tol a^dg "JA6I
HI_HI¤¤ +fl Hls"sE ++. olq^J ola-oe+El g+ S+ zll #zlrlTlr d+E_ 49 _6=zl 9+7ll 6l]0} 6J+. _,qaE]] d
206 6 Elet EJE
zl Hl$"l gq$ Eil^-llolxl"J dzllzl o +E "JqLlzl ?+rll 6l-

aol+. "l+7ll +a6J qfl¤ zl¤ drl qEJ!¤ol+r 6Lq E>0
= A,G<O
E.rE +4U4 (9
---:
K
5
EE ¤ .$Al dq]i dzl slHl¤$ zldH(ernf elecrrcmotive 6
a
E<0
force)ol4r EHoq, olzlEl-J?-l :1Brll +gr 91tr}. ¤
(9 0lrll AG>O
rupAcql^l= ElHl¤ ilzf oJol otr-l+= ql+ql 'dzl r
010
rJ E=0
Îd ,bJ .lG=0
ulHl¤'ol4E Eag P-zl=- 6lH.+ <l-
{H
t
o HJ8 d4E, 6
ol{re_tr z}+61 -EroJ Htel. a."1 dzlE H}+ Gibbs qlqzl
lg 6c.4 U8e Gibbs ollLl^l7l,JAEI= gBoe golutrt. E^l
s} dzl slQl¤ rlol"llE "Jd+ $Alzl CBaJ+. ol +41= trlEJltr E
^t"J4
7[xl-r. Il"J4 EA]E LlElg ttr 91tr1. E g+
'J:3F= "il>0018 qHJ
e-e+El "il= gclLlr, E"rr<001E r
EE6I{I +e}']ejfl +d 4zlzl R + 9iE dzlzl "Jg a gg:e_e.-tr9EII HJBoI
^l"Jqo=
$01 xpjloe "Jclutrl. c^l tr1EJltrol 0g nflts d^l u30l 'JB= ol=trl.
+6llot +r}.
Erl qEJ¤rl HJB cibbs 0llLlxl ol 4z)4 +A ar+e| gq+4 Ceg EA^lA +Y
^]g
sJxl^l +s+ S4lal-"-e.<l $|ee. +s: qEl EE !+Aq zlzzl
^l0lel g aol+.
dzlE + HI+ aCql^J *8ol ulôlzll d6 EJfri- Tl4g
rJ4"llEzI. :.48 Eq 6Ael A,G= 6C.249 oJ.a"6l.fl H^lg a^dqlîE HI+ Gibbs ollHzl.tr.
^JzlE c9 Uqg
oll
Pel :. aCql^]el dzl u]El¤_g "J + 9,lr+ EI+ cibbs 4l
@GD7raqi els'liî trj¤4 zJ"i ¤ + ?itri(giti sgei g'
qql^l). Hzl9 <tol 9ol"lrl dzl t}*ol zl$4 o + "Jqg + lig
trI= dzl trlH}¤el 6fol olol ¤g ++6iq4. dzl"ll s¤
dG = LSd'r E d"J4l7l "Jel Atg +48 trll= eE+ d+ol +d+ol g
E|+^J "JdEl gEe+ Sq 6}qlrl q}*ol d6 "Gi 4lzJg *I +(dzlE ET]B "ils+ "ttzlzltr- dzlE dzlle qB4 +'J
ol H]*"1 B + il= aEl]E Hl-S+ 'J(= 4zlr4 "J)e q-g +4lS+). 6c.2^lE Ll]¤¤ ^l4g Hl-+q -H-H dzl9 +dq
4 *ol ¤+. (= dzlE "J bq)e Gibbs qlqzlel HI+ T14E9l 4eI zl
dw,-- LSdE
9zl9l ulzlloJQr. E + 9l+. ¤B o e+el g4 trqd(IrI+
7lg717t zlule) HI¤-oJ+E d{¤ 9P fl-a= E6ll g
^l
"l "Jg ulA6f{, "l HE}z} "Jq+= E"Jql 4lE aCg ¤
"tLH4= ao}"l ^ll!l +49 aol+(rg 6c.4). E
ol zl&zl
d4_" + "JC6Irll +zl¤+. z| ooll zlt4& trll(+ dzl t}*ol ¤¤ 4l zltV trll)= dzl u]
zl= ol q}*ol d6 "J+ t14g 4l udf "J+E dzlzi "J
Hl¤ol 4L.tTf+.
+_oE+El ¤.+eE olsollo| +qr ^J46|zl-. {zlrJ ,
dzl HI¤¤ +¤61+ HI-HI+el slql=*4 4l++ rflfl
=
ol Hslz} .JqB q + d+ eqlg dill d6i%Fe zElEt q 6c.s
Îolql^J
-veN^d(zi g+(dxlE
"Jol E+.tr. vdfla- dx} r mol9 d 6c.2^lg 6lE 4zl4 ,JBg 0l+6}0l "JEE Hl+ E
ole"
alft--eNoolI, e). u}4^J Faraday tF+ F=eNeE ole" olH g qlE acql^Jql^lE HI* Gibbs .llHzlE +ats + 9t+.
Hlg d4l d6}"*g -vFd(zl ¤+. *¤ "li d6l=J -vFd(zl + t+61 dzl ulHl¤¤- +e4q a.Gs Hh+q +71"J 6I
oJ+_e-tr+El ¤'+_e-E oJrEo 6J trll
B6llzl= "J3 ol d6l-=J4 H g+. Hlrlls 5c+ e^Jql^lE <lg .JH dzl El
^.G
irlHl¤ iI r."49 *4 e+(s. 2A.tqr,<l dw-Qde). H1¤g *.* #zl il+. qlE,<l A,G=-1.0x 102k] mot-'r*
=, y= loJ trll= +.q-r+ ?ol 5}4.
d*r= -VFEr"rrd(
ol "Jg glg 4(dw.=A.Gdg4 a4l +eE {l4E *4 E __ 4G __ (-t.oxto5lmol-')
d¤71
- - vF -- Xg.O4g5xlon Cmol-5= l'0V
Lceu
9:z u1-g-q- Ae +g+.

^lol
-vFE..,, = ArG E^t trlg!¤ (6c.2) olTlî= 1l= I cv= "l+6tg.+
6c trlEl trl 207
HI* CiUUs 9lH zlb oR.rz4l(a.G=a,G'+R7lna)ql el6ll^J
HI+ g.J¤g a^d+ +4lgtrl. ol ++r" E.tt='.".',-4#''q

^lel "JHg -vFE_
A,,Gl(-vfl=E.u9 +4lE ole" 6.|.fl trl+r+ *ol 5|4. tr+4^J u=1?l HI+E a+q= qz| rou]le f,zialH {zl
irlfl¤g 5e.2mY "J+ eA++.
E"rr=-#-#,ro
+HE a4 o-Jg tr1+4 pol ir;' olag E= dr! qEJ!¤ol
+r +r+. s= d^l qfl¤E + +s+ EAe dzl r}*"il q+ +
qL ,JC^lg qE qL fzl olzluj;- #dl +qr {a}zl $f5
E"..
Lcell = -4q EE E^r trjE!¤ (6c.3) q= a"l+. + ol f^l "Jzl7I s+ HI+ ciuus "llHzlE +
- VF
tltlzlTl= 6}zl+ oldq= dz}9 +E E+ eg "JzI"J#
+ E= dzl q¤l¤e qHI¤ iHEs ++l)E +E}u s= HI 6z}g4, rP-l6l.q 6c3^lql el4^J Ei"g <iol .Jcatzl +^l
* ciuus qlHzle+ g+. trI?+^J q= a"l+. ¤¤4"J e!+Eal dzl trld¤e dzl9 Er-14
rzlql ++6I+ Hl-+l glol-H dzl qHf¤g,tllzl ddol4.
ro RT-
E.",=EIr-#mq Nernst4l (6C.4)
dzl i4Hl¤g aCg zlzlt- ++U ol !g Nernst

(b) tsE SE]lol dxl
^lol4l
oJ+. ol o + qltr-q= dzl ulHl¤gl aC 9= +41E r Nernst ll3 dzl E+qtql^J ql+61 +s6lq, Eq 6Aql^l E
^l
B 0c.s"il sE6fl +gt+. BBl} ¤*9zls +r}. zl+ dzl qI*"] B¤ql EB
elEI
HI*E-4 ^JdEE"l s= t'-Elql flg trll= -Er= gE
-Er= *+a c46IzI. rqH Q7l 471HI+g ¤B /J.+ Ke+ AAl
EzI loll. tr+"+^l e=tol 9ol lne=gol qq, u}4^l 6C.441 99 e=rczt Etrl- rfl+ ¤¤ tr-Ellql^l= EI+ HI*ol gg
ql E6ll^J
"lBl+ tF4ql^JE dzl ulHl¤ol ule _*i dzl ts + s.sq q+^l aHLq dzl9 d+tr i4Hl¤ zI
Îolql
4Hl¤"1 ¤4. :4+ g.= dzl qHl¤g s= q!$ cibbs oll tl .<!zlz.l9+=+. trI4^J Nernst
^lql^J
E.u=0 rel.I. Q=KE
Hzlg +E ql rltrql Er+6I.+= rl"s(0c3zl)g g+ql + La-tr
Q-ooatr eg Ar+= g¤. + 91tr|.
a ol3-o alloF -J+.
13* =4Ihr E:d g+elE= tr^l trlEl¤ (6c.s)
z]trJEt o{l 6c.6 ol trl]+61 +96J A.G"=-RTIn KE 6C34lql B

^l(64.1s41,
2s'Cql^l= RTIF= 25.7 myolE_tr ol gEql^J= Nernst 4l q^J EJ d4 gg +E gltrt)g ole" alH ]L= dzl qfl¤g
g r+g=4 ?ol d*4"J ge +48 + 9l+. +c6ll^J ¤¤ *+= +g + 914.
ffifl q 6C.7
8
dzl *8 Cu2+(aq) + Zn(s) + Cu(s) +Zn2+(aq)z} "Jq+=
Daniell dzl9 E= trlHl¤3 zqsKql^J +l.lovolq, tr}4
6
4
l ^J
ol HI¤-e_l BB tr-+E(v=2) K=1.5x103701+. tr+4^l
o}flql E+ +E]E zl+ HI¤+ de4 o tr saB 4lt4z1
C
r-2
t
Fo 4lB+4. qI rv9 dzl ul¤l¤e d4 +col 9zl"J "l"ll
trJ v 61l$6l+ ¤B tL+E zld e+tr+ E4S 6Iq +46171=
{-z
4 Ezl-L" ¤ 4o14.
-6
-8
-3 -2 -1 0 2 3
log O
fal 6c.s v9 'J(olIEl= E^l.E +)01 801-d E^l HJ-g e+, HJB
6C.t, Eqtrf4:d+=ol
TleHlel 'Joll tq+ E^l tr1El¤o1 Edl= E.g. 2esKoll,\l= RT/F=25.69mV =8
0lq, EEl,\l +^l+9 EE= 0l ,J9 Hll¤ LfEtL.!trl. dzlg .tr= trlHr¤g 6c.3^l(-uFE"."x=A.G1ql
"I+ .s+ HI
208 6 ElEltrJE
* ciubs qlHzl4 +41¤trt. ul4rl E?"9 +a4H ol s6 GZEU drl qEJt¤et c-E EtEzl+olE
HI* ciuus glHzlE gl+. rqH Eq 3Dql^J
+g + ¤E
ql +E, A,G"(H*, aq)=09 ol+ql^J ol fi9-EPq ol&el
{zl Pt(s) lHr(e) lHBr(aq) lAgBr(s) lAg(s)9 s= "lHl¤g
"Je6J gE Sqql^J +e6}ol r e4E+El trl-s=4 ag
^J
c ciuus qlLJ zl= +6J + gl+. efl+
+6J4g
ffi:d oll 6c.8 Efu,/v = o.o7 | 3t - 4.99x 10{(T/K - 29s)
-3.45x 10{(7K -298)2

+¤-4 Ag dzlE_ ^J46l] EzL.
Pt($lHr(s)lH.(aq)l$g.(aq)lAg(s) EL= +{.7ee6Y

dxl tI¤¤ AgBr(s) +iHr(g) + Ag(s) + HBr(aq)o {, u = l o l l
4. zgaKql^]el E= HI* Gibbs glHxl, dBvl, H fl=e

ol Czl HI¤+ q^q=r+ Ag aol+. q= +4q+.
eg*(ag) +]Hr(g) + H*(aq) + Ag(s) a.al_g AIEI ol HI-&E s= Gibbs glHzlb zgsKql^Jel
A.G" = -ArG"(Ag*,aq) rL= +6J r-l¤-"il oc.rll4 I vc= I IE +41= 0l+6ll^l
+6J + gltr|. s= HI* Sl= +ul= +lel tr}.J4g rql +
trI4^l v= r-E. +r +94 Ae e+= eg + 9i+ 6ll^J trlB+ r\$ 7-2e8K-e. +.-r.6c.6ll¤-
"l*all^l +¤.
A'G"(Ag*'"t'Idf*jff + 91trI. r4r s.= HI* tlB4= .E'= Gibbs ollHzl4
mor-,) x (0 7ee6v) flE eq al# aoJ4^J +'J + gltrt
T -2e8Kqî= E?ar=0.02131 vol+. Et+^J,

ol2_9
- i-A-u zle 3ol
---.,.E rl-i LiZ 1.
Lv.a-1Aol 7V;tL
u^--l
rUrl=l
-I L, 'l aL uL-
i< r_
2:rlr_l-
-l .
=ol
=. =*1
A.G" = -vFf^
x lOaCmol-t) x (0.07131V)
= -(1) x (9.6485
= -6.880 x l03CVmol-t
E= dzl qHl¤E 3s "lE 4l+ dE:.u/dr=: dzl HI* = -6.880kf mol-t
E s= QlE+rl Hglzl. E+. . Eq 3Eql^J +E+ gq+
E. ol dzl ulHI¤9 gs "lE alf r-l-q_r,+ rJu+.
4 +al^l (aG/aDp=-Se+ 6c3^lg aEI6iE trlg=4 ag + =
4lrlol +g+. ffi."., _
-4.99 xtO-n V K-' - 2(3.45xt0-6 XT / K- 298) V K-'
dT
q_4{ 'tr= rl^l trlEJl¤g Ps olE zl+ (6c'6) T=29BK"J trll= ol alg +gq
dT vF q-q=r+ 4.3 <iol +g+.
A,G"4 uffizlzltr_ E?.rg .Jqql ++6t71 qlEql ol raJf
: Sd trlE 4l++. r+4^J dzls+44 ,JBg olga|{ _tr6 + = -4.eexro*vK-'
Hl* $lse.q. eg + 9lr E trJ
'|"tzy +E +E "lg. trl+^J 6c.6^lg ol+4q E= HI+ $tr+4E +6J +
9 Qi_= +vl= +ts + 9l+. gltrl.
E_9.E zlfillzl! ¤45s- p6J61]^J ol+6|H s= Hl+
flB4E +6J + 9t+
= 4s"=vr$
= (t) x (9.6485x lOaCmol-r) x (-4.99x 10-aVK-t)
A,H" = A,G" +TA,S" =-rr(r;, -T4qLdT ) (6C.7)
= -48.1 | ICr mql-r
"l ^lg A,H"¤ +C6Ir" -E A.H"(H+, aq)=09 +Eg E"]]

*9 +s= "J* "l*E dzl el+ql\ zl4lzl ^llrlEl
<tol
zl rllgol4.rflr E= HI+ tl$rlE q+r+ ?"1 ¤4.
+"_4 49 ol9E E= ^JC SfBul. +e6l+(Eq 2c)
^J
Hl-g4l%t4 *H"l q= aol+.
6C aFt Erl 20e
A.H"= A,G'+TA,S" +A171S,"l B"lE trqqzl de=¤ s+^14 += gq

= -6.880 k| mol-' + (298 K ) x (-0.048 1 kJK-' mol-' ) oI9 ?"14"J bqg u-q += + q+a E + 9i+.
=-2l.2klmol-'
rlTl B7l 6C.1 gEqL4 EllolEl s++El 303Kql^lE
+4 ol tt}Be-l t zlzl tfig dzl d9l9 9s ulE 4l Harned dzl, n(s) lHr(g) lHcl(aq) lagCttrl lngtOE .tr= i4
f <l"l 4zl ulEql olag e+4ril =$xlzlzt qB+= Hl¤g +6|q+.

4o14. :afl+ olag 1j.zl4 +C Ar+= AE;];oil ol$ ttZZZZ'O+:E
T]ILJ=
=s-d
D r. tt:el-Eg UBe + +Ifl U-UBE ilE LlElU4. HI-HI¤¤ 4+E dxl 8Hl¤"1 "J"l ¤tr}.
* ?+?+ &a}-+l^?lt[ " Ag.Jr]. tr s. Nernst
^lg
dzl iilHl¤4 Hi+ gqlEg ac Î"19 +41
a 2. eHu dr!= d4a t:EiI dzlq a+ tEir dzl_a E LIEIL}I= rl"l4.
=
+B + eltr}. tr 6. E= drl qE!¤g d4 eI89 ¤¤ ^J+= ahl6kql ol+
tr 3. EZJ tr+ tr1EJ!¤g + d4e +.-4E d+q E ^Ja+. g + el4.
. 4. crl EIE!¤g zlg =a 6lql^l +a+ d+ ElHl¤g zI+. a 7. dzl ulHI¤9 9s. "l+ 4l+= ol+6IE dzlgc Ea=E
dSalql s= + d+(dzl E^lHql t'|4)ol +d+-o e Ll gqq+4 Ce# + el4.
=CB
=s-d^l=
zl
,A-l
OE I
--1 +4 :l Ha
dxl alHl¤r+ HI+ Gibbs qlHzl -uFE.1=ArG "JC gse+ "Jq 6C.2
E= dzl El¤l¤ E"r"rr=-LrG" lvF CE 6C.3
Nernst 4] E"r=E'."u-(RT/uDln Q 6C.4
dzl HI*9 ¤¤ tI+ 8"..u= (RT/uOln K 6C.s
dzl qfl¤9 gsa "lE zlf dE"*n/dT=A,Stvf 6C.6

E+ 6D fl= tr1EJ!¤
E 6D.1 298 Koll^lel E= tr1EJ!¤.

> ol EEfE ull+ ol8
E= drl qfl¤= 3Hata, 7J.j6la, E EE4oe
LtElLllts &4-++l }dF E" lv
oiEEl= ".He zJ flry=glqEI¤3 olE":l= aol+. d+ trlE!¤3 Cea*(aq) +e-+Ce3*(aq) +1.61
E+a$h1 tt+EfB 8E t}aH4 EgalE IIJTl6lr sE 8E 8+
Cu2*(aq) +2e---+Cu(s) +0.34
Ee-l Eq-+4 dEg +861.ts tll 'Jal 0ltEtl.
Agcl(s) + e- + Ag(s) + Cf(aq) +0.22
> EC 71lE! H*(aq)+e-++HrG) 0
ErlE F E+3 44 drl EIE!¤0ilrt rgEl 7lq= ElrE Znz*(aq)*2e +Zn(s) -0.76
849 + ?Itr}. d+ trtE!¤ot H= rt+Elfl ae # qE!¤g Na*(aq) +e--+Na(s) -2.71
tt+E!fl ¤tE flB SEIS LtElurl.
^l7la1= . zlE eql rl E}3 rtE"l ++Elq 9l+
> =JsEt qHl r!^l
0l EEloll^-l= trE 6csl TllLlg gE,(le 7i0lq, qal^l E^l
qE!¤rl E= Exl qE!¤E zt|uJ(Erl 6c)E ¤ 0|6t.|6tl0F :drl-.
g+ d+ol I :r-lr s= + d+¤. R"J dzl LIIRE E=
ra!7 ,t|1erl 6C)E 0l3r-ll0t:Sl. g= trlE!tr= #Jdl= dzl clHl¤e r+q=$ *"1 F _E= qQl¤el ztE +qd+.
Nlernst
rllts Debye-HUckel9 --El E4(EE sF)= 0lEoPll Ett.
LllR E.".,,-- E"(R) - E"(L) E= E^l tr18!¤ (6D.3)
.tr 6D.lql 2e8Kql^JE s,= trlBl¤g ++6l] +9t+ z|tr- ¤

Eq 6cql^J ¤E+ ?ol Sulr-l dzlE + d+g eq+
ute+ ql q e}e qHl¤ alEol EEIBI+e-g ++qq9l+
^14^J "JE
a,olq, zl d*"1 dzl ulfl¤ql+ r+q} 7lq
s ql+r Hl+ + +"J d+9 0l TlqE
^84g + 9l+. =e zElEt 0ll 6D.1
617l= $zJ-i:alzl"J qL 6J d+E qH]¤g 0o + aeldlr
{zl Ag(s) lAgcl(s) eg +
lucl(aq) lor(g) lpt(s)= q-q-r+
"l z16"ll nI+ += E= d+ql q+ <lg e6ll = += 9l+. d+_q_E "l+qd 4ol4r E + 914. "l d=¤E s=
i{fl¤e zlg Aql ++g <lEol4.
5D.1 E= tr1EJl¤
d+ HI-Hl-& E= ul{¤
olBlqI +4-9--tr. de¤ d*ol +94 eg E= t4 d= R Pt(s)lOr(g)lH*(aq) Or(g) +4H+(aq) +ae- +t.23V
(SHE: standard hydrogen electrode; o
I
r|. -2HrO(l)
L: Ag(s)lAgcl(s)lcl-(aq) AgCl(s) +c +0.22V
Pt(rlH2(g)lH.(aq) E' = 0(EE gEqlî) (aq)
-Ag(s)+Cl
s= tr1E!¤ [+e+] (6D.1)
{",,= +1.01V
_*.= tr-Ell= "JEEtE f+ olgE glt-E= 1(f, pH=o)tr 6I
l' +i 7li'llE 'Jq(q C+6}rll= #zlrlEl)g lbar-tr 6}]+q
of 6Jq.1 += ts}-+|g tL xE E= d+l r"(x)g ol %Ig s (a) trit
94 d+"1 qril 6}l. -E= +d d+g g+ d+ol q4l "J =8
s= q¤l¤g +A6l+ ¤il-= e/gsle d+g qlg Eq^J
Azlel trlHl¤4 ?Jtr+.
!
= ¤HB + gl+. olag r-l-q=rl. u-3
.Harned
dzl,E zlzla_
pt(rlH,(s)lH.(aq)llx E"(x) = Ei.,, "tJ{,?* 6D.2) c++.
r I'JaI4l "J6tE zlill{l EI+ $FE.J #zlrl4$ ts +olo} 6J+(ol jL Pt(s) lH2 (s) lHCl(aq, b) lAgCl(s) lAg(s)
zllg fl|,r.l-o1eE t4l* rll+2= -u_ol-4). ¤zlrli +d:6}zl ?+Al 6}rl +16ll
oJq+ SzlrlQz| E.J6[r1l 9i $dzli]lE z]Catfl4. I Hr(g) + AgCl($ -+ HCI(aq) + Ag(s)
^l
6D d= EIEJ!¤ 211
E".,, -- E"(Agcl/Ag,cl-) - E"(SHE) dig +tr}. rqE &'/2=0oll^19 ¤¤ol gJg3'lg d+E E"ol
=E"(Agcl/Ag,cl-),v=1 ¤4. rJ g"J+ +49_s= btt26J--e- 4E " + *zlt_ qtlg
Debye-Htid<el H4(Eq sF)el ri} BC .Jg +Hql +E+.
ol Azlql 4t N.rrst !g trl+r+ ,Jq.
EEil ssffitrlE!¤+ot7r
E..r = r"legcveg,cr- I - T^ff 2S'Coll,q Harned 4zlzl q^q-r+ eg dzl ElHl¤g +Etll
ii tl\lzi tbar9 "Jq"J ullts an,=t"l S4. r?-ll. AgCV *+.

As,Cl-d*E .E= qfl¤g a+61 E" o ts +44H +lE bt(to-zb") 3.215 5.619 9.138 25.63
^l
ol ffi$ ?"1 ¤4. E"ar/V 0.520 53 0.492 57 0.468 60
0.418 24
g/gelg d+9 s= slfl¤g +6Iq+.

E = r" -
$r" AH,act-
a.a{g I.tEl t$ql^J ¤E+ ute} B"l l=En,*QRTtn
"rr
ol 4l +el g|E" E=g Eq sFql^J ++ an_= Trbtb" :_41 ln (btbl= +6lq (btU)raql 4EI^J E^l6IjL b=0 o 4 9
ar,=Txblb"g ol*ot¤ HCI(aq)E Egr-"E bE 7l^1A- +ElU r*t+.
4.:-48, ol dzlE s= trlHl¤g aa6l7l +l6}q q-q'=r+ e
=ol
g EE vol r}).
E.u=*-f,"# "JEtrH2Rr/F= o.o513e
bl(to-tb") 3.zts s.6tg 9.138 25.6i

=E"-j,{t#-ffrnr, {bt(ttrt6"7yrrz r.793 2.370 3.ozi 5.063
EatN 0.520 53 0.492 57 0.468 60 0.418 24

IIl.+^J yN 0.225 6 0.226 3 0.227 3 0.229 9
ol ullolq= rH oo.roll s.rlalfl+. elr*¤. a].fl E"=

Ea, +
T^#=E"- ffrnr, +0.2232Yr1 +gtrHEJlolElE css= $zlalzl +16ll^l d
t,t-doll¤E A+ Debye-Htickel9 ++ Hzl(sF.274, log /+ =
¤ 4zlB e eg o <lol4).
-Alz*z-lltt')ql el6l-H b-+09 uI= trl-S SA17l ^dB.J+. 0.2300
02290
logy*= -Alz*z-lltt2 - -A(b/be)tt2 6-
a
a 0.2280
El+^l ln x=ln l0logx$ 0l+6l{ ol tls=$ B"l 84. E /

^lol O) o.2270
cf)
{ -{
lny*=ln l0logy+ =-(AIn l0) (b/b"1t2 tr)
o o.2260
o
+
ol-= +41= oJe" 6l.8 E*loll ** z]ol q+r+ 4-ol ¤4. D
o.2250
0. 2240
* zRT. b b
v2
F l"U" ==8"+2ARIlnt0[ b+ooJ 4l 0. 2

t."rr
f ( b" 23 4 5
lbl10-3belz
{zld 84 " + +E}U i'J¤¤- Ctr E^16}H "l alol rl-e-$ fal 6D.1 r= Exl nlEJ!¤el ¤-d,J= +-g trll olEEl= E,\le+ Ed
UE. b,rz= ooll^'lE trEo I rl",,o 1c1.
3ol 84.
Tlfi-Tlxx rlTl rgTr 6D.1 olell rlJolq= dxl ptlHr(g) 2s"C"llrJ I
v
HBr(aq, b) lAgBr(s) lAg(s)E zlzla- Eg a"l+. ol dxl9
8n{
t/2
E,,* T^# -;, + cx

b
a"
(6D.4)
E= dzl ElHl¤g ae6iq4.
ol c= ^J+4. ol (btb"1uzs- rE 448 4* y_ bl(ro-lbe) 4.Mz 8.444 37.t9
^lql^J ^lg ol E*|IY 0.469 42 0.436 36
¤¤+ zl&zlxrel eg Eol+. !g olo-" 6].elg alpg- "l 036t 73
4 EBL"EqI^J +A6Iq W2oll Ell6l]^J s,<16p. b=0oP g zt IZO'O '-E

212 6 El=l Bg
(o) *8x!=el v.E"(c) = y.E"(a) - vbE"(b) E= rqE!¤=e.l e-st (6D.5)

=:d
s oo.r9 E=ElHl¤# eq+6IH ol Ell ++Elzl ?+e & ¤zlrl v,z7+ HI-HI+qI^J9 dzl¤q qlqlEI+*4 al+q.
s}-+t?l %IEE Zlg +6J + 91tri. rfl+ olfl A+ql= 4Ie+-
¤|fl r^Jol q-= a+ "ldq= &zlizl *ol6.J + gl+= Î 6D.2 E= tr{EJ!¤el olE
¤g +el6ilot 6J+. "l 4¤¤ q-q ETlql^l ¤B6IA+.
dzlg qql¤$- ol_a" ols HI+ql +Hl!= ¤B tl+e+ Gibbs
qqzl H+ elBvl HsI, "l 8l-= eirl HEI E9
GZEE =E=trtE!¤E+q
q=6ptq zt=+ 'll"lEl. E
g + ?14 ¤ztl-tr oleiql ¤e.el E= Ae "JHI4 o e ol
-"l71
Cu2*/Cuel Cu+/Cu tlEE s.= i4HlE+ r+?+ +0.:+ov4 fl+ *H "E +6flzlr. 9i+.
+o.s22y ol 4. r"(cu2+/cu+)E +6iq +.
,*6ll¤ +
(a) dzlgt-+4
a.B{E Al¤l +d H}* Gibbs ollulzlts 91tr}= ^1E
+ &+-+|g $ oxr/Redrr-| Ox*/Red* ar-1tr olE=E g trl'g
^l"gg.fe-Sr-flHess9
849 ol+Bll^J HI* flgr4= +
dzlE Ezt
d-= ar+ *L+). :an-l6lq 6c.341(-yFE"=A,G)g olso 6I ^J46ll
¤ r" A=¤. A,G" al=.e ulg ffi 4¤61 q+4 +J" + OxriRed, ll Ox*/Redp
L ll R =
6c3^lg ol+6}q ol +4lzi A,G"g ?]6l+ E" o + ut Ox*+ ye- -> Red* Oxr* ve- + RedL dxl +qr (6D.6a)
^l
+q oli]fl *QZt+ azlg 61"= ag + "Jrll Ei.u=8"(R)-8"(L)
=+.q1zl. rE ^lel
9dxlq} t4l9zl"J yts "JHI4eE ^J4lqzl ?+ zlzl El-9-9 r-Lsr] zlol
ollutuvutHtLtstat 4 + qlr]
7l tr+lEol+.
R - L: Red. + Ox* -+ Ox,. + Redp (6D.6b)
a+ HI-Hl¤¤g trl-q-4 e+
=ot
(a) Cu2*(ag) +2e- E?=u>0"1H, + E"(L)<r"(R)olH K>1ol ¤4. ol dzl Hl*91
-) Cu(s)
rJ* +
f"(a) = +0.340V, tr+4^J A,G"(.) = -2(0.340V)F Redrol o**g +]"g^lzly 'l¤-!+ ?ol ¤EB + 9l+.
(b) Cu*(aq) + e- + Cu(s) E"(L)<8"1R;o1E R.d.o1 OxpE +fl^l7lEJ= gqolzl
E"(b) =+{.522V, tr++^J A,G"(b) =-(0.522V)F Aolg ?*Yr:+(=, /Glol+).
rel:z gs.e HI¤e q-q=4 Aq t+61 s-"f"iE *e a"l +e Ag +|fl^lA+.

s ++ g^5(+^= -troJ+)E ¤Hlqg ++aq +
6D.2=
(c) Cu2*(a9) + s- -+ Cu*(aq) E"(.) = -A,G"(c)/F ql^lE s= qHI¤g 7|zlr. +A4q +^JqlE +4U ae
trl+^l (c)=(a)-(b)olF e HI* (c)9 .s.= HI+ Gibbs glH E^l ol4=," dz lE[-+4 ,tlgoJ=]1. t]+. s.= trlHl¤ol *3
zl| r-l.e=$ eol ¤4. ++e s= jrlHl¤ol * ++E olgg {}+l^la + 9l+.
ol A$-g CC4"J 4olzlu.! $|oll,tJ ¤EqL ,JHg
"l+6IE
- -(0.680v)F- (-o.5z2Y)F A%14"J <iKE +6J + 9l+. "I4 A+6J {lg z}zll o14
A.G"(c) = A,G"(a) A,G"(b) =
= (_0.158V)F g ¤E6IH+
E"(.) = -^.G"(c)/F= +0.158V.
"|4rJ
:,"JTl6D.2 E"(Fe3+, Fe)91 E"(Fd+, Fe)_tr*el E"1Fe3*, z]=JEt q 6D.2
^l7l
Fe'*)E +61-q4. ol-¤g a 471 slq4 rlpol u|:zQlf,E_+ +lql 9lsq,
nsz'o+ :-E tr++î olE¤. ++"1 49 "l-uHl# "lsg +|g^lvJ +
S.+.¤l¤ +Ê ^lgg oI¤EtrI +lql fleq, EI+^J ol-
Eg +^ olgg +}fl^lvJ + il4. :4+ gqq4-o +
7lg"d q}$"l4s HI$ +EEZJ s-oJ qEq e}*"l 4E
}=7l 6D.2E Ahlg +g-4 ?ol "Jtls+rla + 9l+. 6l L?-lrll "Jqg += 9lr+.
6D d= trlEJl¤ 213
E 6D.2 dTEl-+4 llG*
4r* el.J +gq _H-71 6D.19 rllolEl

+qlY b-9.138x 10-3b"oJ 4l E..u=
* (AuYAu) 0.,168 60V+= rI Eq ilr+. 2RTF=0.051 3evol.tr,
qlol El
E+ (Pt'zYP0 E ol _H-7lql^J E?.u=0.2232V4= 44zl 4*9EE ol

I (agYes) EBE"Eoll^J Bt g4EoE 4l+= trl+r+ ?"1 ¤4.
+e (HsryHs)
tryr=W -h(9.r38xroi) = -0.0799...
+fl (Cu2*/Cu)
+4. (HYHr)
rr}4^l h=0.92324.
f! 15rrz+75rr;
qe (Ni,.ari)
e (FdYFe) 8+"!
(c) =JE
olfl (Zn2*lZn) =8
tr= qHl¤E +g +E= "Jelel + d+g A6J6I]^J trJ=
(Cfr/Cr)
='E dzl9 s= iilHl¤¤. ah}6lr" olq^J dzl t}¤-el ¤¤ tr-+
"JF"IE (At3.iAl)
+qJ-= 4o14. 4 Eiarff(R)_r(L)g oJE=iL, Eq 6CE
ufzullf, =
:. u- (RT I vF) ln KE ln K= uFE ?.rlnrs+ ?o I l4
(Mg2*/Mg)
6c.s^l (E )g ^J
+EE (Na+A.{a) 0l+{-= 4o14.
z)ft (Ca2*lCa)
aE (K./K) zttrJEt 0ll 6D.4

TIlr d sgq
t 6"1 4IslE qr. ++gE q= HI¤¤ Bilr=" El HI+
. q SA6J zlE ¤E -* 6D.1_os+El gg + 914 ol+r ++.
^lgg 2e8Kql^l BilE"s+ HI* zcu*("q)+cu(s)+
cu2+(aq)S rJ4-ollEzl +16il^J q¤r+ gg + HI-HI¤¤ A
oJ6Iq Eq.
(b) 4l+el
=l-EE =8 R Cu(s)lCu+(aq) Cu+(aq)*e-+Cu(s) f"(R)=+0.52V
"Jt dzl +e-l + d+E E.= qfl¤g "JE + "lg"l 5c L: Pt(s)lCu2*(aq), Cu*(aq) Cu2*(aq) *e-+Cu+(s) r"1R)=+0.16v
+ r-oEe. Eqflg u1l9 Czl ElHl¤g : ol$
=Afliss.*l
el ¤+ gEoE al+E +e. + fl+.qlE^J 6D.1¤ql^l a# trI4^l dzl ql¤¤ 2cu+(aq)+cu(s)+cfi+(aq)zl qr s
* Harned dzlglrJ Egtgz]. e"J HCt +&E +ql Eqgl d4 qfl¤e q*q-4 ?"1 84.
=
oleEE B+ gt.E 4l+- q+ +4lE olf-aH,! +6J+. Ei"u = 0.52V
= -0.16V=+0.36V
olag ol+6IE ol dzl Hlg" 9 ¤B t'-+= 4l&g + 9l
E.u* T^#=E'-ffrnr, 4.= 6c.s^lql^l ,-1oltr RT/F=0.025 693volE+ trl+
r+ ae Ar+= Eg + 9ltrt
ol {g A"I6IH q+r+ ?"1 84.
tny,=m-r"# (6D.7)
rnK=##k=r4.0..
r46}q K=t.2x 1o60l E4
214 6 ElEl trJE
TI|LJ=
=s-d
tr l. + +l?l r5-ol 9.E4 d+ol qr" g+ d+ol s= + n 3. dxl qfl¤4 -u s=zle+el xl-= "l+6ll^J dzlg¤ olgS
4 ^lEl
d+-e-E g dzl9 ElHl¤S ol {r}-ffi t}el E= tr18! g gE" E al+E +c6J + 91tr}.
.$olep aJQ. Z 4. -tr= d+ rqH]¤g ol+6il^l -tr= dzl EiHI¤g al&6}n,
- 2. dTElat4 #+=g +?l bqg ++.4 +ql^JE E olq^l dzl tI*9 BB tr-+E 4l4}g + 9lrl.
ElHl¤g^jEg
ol$all.! ac6}q xlqlE Ltg+ 4o14. <iol
=
*g aol +e ag +|fl^la+.
=s-d^l=
,(l
oe.zl l.l
-1 +î 4 HE.
s= dzl qfl¤ f*=9"1P;-E"(L) dzl: LllR 6D.3
-tr= EIHI¤E aB v!," (c1=v^P"(a) - roe"O) 6D.s

EA 215
E71
^6 trl-+ =JE
Eq 6A "=:d Ah+
efl
==
D6A.r BB tI+-= +EI4= ^l +ql ++6J aqill+ r.zllz| eEt9zl ?*E D6A.2 HI¤¤-r+
^JCEE s6Jol BB tI+E 9lilql 9¤ aqg "lzl=
ol*E ¤H6Iq4. zl ¤B6Iq4.
G-\
r -tl
1.00baroJ rql g6JE 4oll o.zqmol9 czi gqlElq fl+g "J9l+. (i) *l¤
g olFa gl= 4 +=E E +g- (ii) Kq (iii) 4l4}6}q4.
E6A.l(a) Pn(s)+6Hr(g)=aPH,(g) HI*ql 46J B¤ tI+E,t^14. 7l^l|qag ^,GPg
Sd 7lz]l+r, zl{ai{4. E6A.8(a) s03Kql^J H =qlg CroHrTOHTI ollH ELllseE 9i zlzll{t o1
HI*"ll 4.J B¤ tI+= rl
E6A.1(b) CHn(g)+3Clr(s)=CHCIr(l)+3HCl(s) deillsl Hi8el E= Hl* Gibbs ollLlzl= +e.4kl mol-'ol4.0.l5mol9 -H-
4. zlillE* gd zlall{r. zl{a}¤4. eqlgr+ 0.30mo19 ol+H aull$$E g6JEol 600To119 dil "Jqg +
E6A2(a) zlg ¤e.l Ell"lq= ol-$6tq q-* Hla * gr {ol zrsKgl,rl
4B trilel HI* ciuus qlLJzlE 4l&6}q+.
E6A.8(b) s0oKql^l r.i-ll +?+-Eir+ +43r}+4b uH,(s)ol ¤¤¤. ol+a
K>rol 9E lqlzl ee6}q+ (i) 2cH3cHo(g)+or(g)=2cH,cooH(t),
(ii) 2AgClG) + Brr(l) + 2AgBr(s) + Clr(g) ilg ,I Hrq SB $4"1 r3epaol4. sooKql^J UHr(s)9 .trf ..8C ciuus
E6A.2(b) zlB qg Hl* + qL aol 2e8K
qlolq= ol+6}q 9lHzlE +6Iq4.
¤9
q^l r(< lol q= a,"Jxl aa6lq+ (i) He(l)+clr(g)
= Hgct,(s),
(ii) E6A.e(a) NHr(g)9 E=
^8d Gibbs
ollLlal= 2eSKql^l -l6.skJ mol-'o14.
Zn(s) + Cu2*(aq) Zn2*(aq)+ Cu(s) N2, H2, "l NH3E Y E *Eol zJzJ 3.0bar,1.0bar, rrlr 4.obaroJ trll(E+
=
E6A.3(a) .J HISel s.+ HI8 Gibbs ollHzl= 300Kql^l -320k1mol-'olr, Sd Tlill_e. BEI)9 HI8 Gibbs ollHzlE ¤"Izl EIA!+? "l a+E HI*
4E e.6J HI*E s.= tsJB cibbs ollH^l= gg gE"q^] -sskl mol-rol 9 xls4 Hs+ H"L6Jg qL +ol+?
E6A.9(b) pHr(g)9 s= glulzl= 2e8Kql^l +13.4k1mol-,ol4.
+. 300Kql^J ol + HI*E E¤ tI+ HIE +61q4. ^Jd Gibbs
H2el PH3(-EL+ sd zlzll-+. E+)q f E $Eol 44 r.ouare+ 0.60baroJ
E6A.3(b) 6J HISel E= Hi* Gibbs glLJzl= 300Kql^l -200k1 mol-'oll-
trIel HI¤. Gibbs qlHzl* ts"].zt sld!+? ol a+q BJ8E zlgzl Hcl
4E s 6J HISE E= Hl* Gibbs glHzl= gg gEql^J +30k1mol-'ol ,.L"Je. 4: +"1+t
+. 300Kql^l ol + HI*el BB tl+ HIE +6Iq4.
E6A.4(a) HI* N,(s)+3Hr(g)-+2NH,(g)9 -s= HI* Gibbs ollHzlE zqsr
E6A.l0(a) CaFr(s)
= Ca2*(aq)+2F-(aq) HI*el ¤B ^J+= 2s"Cql^l
oilri -:z.qt| mol-'olq. Q7I (i) 0.010, (ii) 1.0, (iii) 10.0, (iv) 100 000, (v) K=3.9x10-ttolA CaFr(s)9 g.= ^JC Gibbs ollLlzl* -rrOZty mol-,o]4.
caF,(aq)9 .tr= ^Jt cibbs glHzlE 4l4}6lq4.
I 000 000oJ ullE A,G (lg 41416}¤4. {zlrl +E} <t# L}ld6}q r(9
#g +6lqal. dxll l(el <lg 9"Ir*i
E6A.1o(b) Pblr(s)
= Pb2*(aq)+2l-(aq) Hl+$ ¤e tI+:
2s"Cql^l
HJ* zNOrlg)+N,On(g)9 s= HI* CiUUs qlqzl= 2esKql^l K= 1.4x l0-8ola pblr(s)9 E.= ^8C Gibbs 9lHzl= -rz:.6+tl mol-,o]4.
E6A.4(b)
Pbl,(aq)$ -E= ollulzlg 4l4i6}q4.
-4.73k1mol-'o14. Q7i (i) 0.10, (ii) 1.0, (iii) 10.0, (iv) l00oJ trllE A.G ag ^8C Gibbs
alt6lq+. ¤zlrl +qI *# 411-.I¤ Kel <tg +6Iq4. dxll 19 <l E6A.1t(a) HI8 A-+28= ^845llEzl.. agqli r.somolel ArrJ +46}1 B
L
o Qiuhlz
d I t! SflEl. HJ* tllEz} o.oomol"J rlle-l Ael B9 EA+g +6}qq.
=
E6A.11(b) HI* ze-+BE zlgql 1.75mo19 A4 O.rzmol9 B
E6A.5(a) 22s7Ke+ dill *q 6}q^l 2HrO(g) =2Hr(g)+Or(g) HJ
l.00bar9 ^846llEz}.
,I 9I9,tI. Hl* tl4Ez} o.:omoloj trllE Ae+ BE Ee%r3 +6I"14.
g"ql q+
BBql^l t.7zvoA E"l 6ll4gs1. ol gEgl^lE K= 41416l"l+.
E6A.s(b) N,onG)
=2No,(g)9 BBg
ol+I *E rltlplolAÊ 6ll;lE E6A.12(a) H!* a-+zsz| o.tomolEJt A4Hg rll(4, A6=+0.10mo19
ab 6lq^-l 0.20lol+. 298Kql^-l KE 4lt6}q?+. trI) 4le1 Gibbs ollH zlzl -6.4klmor-tu.!-=- 86}9tr+.
2e8K, l.00bar "l Hl¤- +4lql^lE HI
HI* srco(g)-t_Co(g)+Hr(g)oll tll.J Ke+ K.
* cibbs 9luJzlE 9n}4t
Îolel +41= +61
E6A.6(a)
E6A.12(b) HI* ze-+sz| o.ostmolEl# 114fl9 ull(4, A6=+0.0slmoloJ
q4.
tril) 4lel Gibbs ollH zlzl -2.4rkf mol-'Hlfi Halg.+. ol Hl* +4lqîE
ql6J Ke+ K.
HI*:Nr(g)+Hr(g)=2HN.(g)oll
^lol9 +41= +6I HI* ciuu' qlqzlE g"t+i
E6A.6(b)
q4.
zlill^J HI* ze+g=3C+2D9l,rl t.oomol9 A,2.00mo19 B, l
E6A.l3(a) 2e8KE s.= aa 6}ql^] ,l= ^JEllE +lAEE+El ,lltsol ^8
cEl= Hlsg "J-^8tc"l?lL+ Ei $-+17c"l4lg*i
E6A.7(a)
a-l-L r.oomolE E¤g ol+zl 6}g.qq dill sq
D= gt+6}q 2s'cql^J
E6A.13(b) 2e8K9 -s= ea 6Iql^J tEl]g fl^=s+q Eill Hldl
ol r.oobaroJ trll g'JE 491 o.qomol9 cz| gqlElq "JSg "Jilr|. (i) B g_^Jtlcola!+ 'l=
ol E= oJ_^rid"l4l,-4i
¤¤. "lFl ?l= 4 +EE g +9, (ii) K "l (iii) Adg 4l4}6}q+. ^gcq= "J¤_3_
E6A.7(b) Tlxll^J HI* e+g=c+zpollrJ 2.00mo19 A, l.00mol9 B, l4 E6A.14(a) A+2B-+3Cql rllEi tI*
zl-6ulE r^lel.
r 3.00mol9 D= g6J6I4 zs"c"llrl ¤Bg ol+al dl-flqq dill "Jqol E6A.14(b) 2A+B-->2C+Ogl 46J HI* zl-6ulE r^]+
216 6 El¤ftrJE
Eq 68 =J-doll B:rf=+e.?]
== =xll
ooa.r 19 gE E¤ql q|6J van't Hotralg $z} i6q1^J ¤B6Iq4. D6B.3 Le Chatelier9 ?lel$ gq+4 oJ¤ Tlzll ++4q+. "l gflg
{l9z} ¤46J f 9i1l,s+i
¤9oI4 ¤B ^J+ql "lil= g.er+ gE HelE E'r+71 ++ sq
oos.z
oe +4U BB Elzl= Er+6Ir. qB4 4Ezl ¤B6Iq+.
^J+ql
G-^
Jti
E68.1(a) CaCo,(s,[]all4)z] CO:(g)g} CaO(s)s E6llEl= H]*E ¤B t]+ ,rJ .*.3 HI* cibbs "llulzl= +33k1mol-'ol4. ¤B t}fzl r_ts-ri zlzlS
zl. gE= +6I.q4. pco.= I barE 7LA6Iq4.
rol El= gE= +6Iq+.
E68.1(b) Hl8 cusor.5Hro-+CuSor(s)+5Hro(g)9 Be
^J+rI lol q= E6B.s(b) 800K+El Iso0KztzlE gE gqql^l qE 6J HI¤-ql EI6J s=
gEE +6Iq eI. PH,o= l barE 7Ia6Iq 4. HI-&$lBirl= +l2skl mol-'o14. E, lr20Kq^J .tre Hl* ciUUs "llHzl*
+22k1mol-rol4. EE t}fzl lE+ 4 zl= gEE +6Iq4.
E6B.2(a) ¤ a,s(s)=Ar(g)+B(e)9 .114 +rl $qg:6lcglrl 208kPaol
zluf, qE s4ztoatr 6zlaJ4. 422"cq1,\ ol 6114 H}SE (i) BB
47fezl E68.6(a) Hl* zC,su(g)=C2Ha(s)+CnHr(d9 BB tI+E 300Kel 600K
^J+, (ii) .*e HI* cibbs ollHzl, (iii) s+ HI8 qlBul, "i (ir) s= 6llel rlol9 gE ¤qq^l ltr;,K=A+BtT+C/T2-E +qd+. ¤zl,tl A=-r.04,
H]8 $l= eulE +6Iq4. ol 6zl= olt}4 " + eE6Iq, A.Fr"el a,s'= B=-1088K, :IE:il. C=l.5lxros K2ol4. 400Kql^Jel .tr= HI* SIBEIe+
ol gE ¤qql^l gseql ++6.t+-7 7la6}q4. s= Hl8 dE +E= 4lt6}q4
E68.2(b) lr.ill gEloJE-E:"l HI* NHrCI(s)+ NH,(g)+Hcl(g)oll trl+ 6114 E68.6(b) 400Ke+ s00K gE ¤qql^J qE + HI¤'E ¤B ^J+
^lolE
¤+. NH4clE e71"Jqg +zfc414 ooskPaolzltrJ 4se"c7l9H rrrskpa lnK=A+ BIT+C1T3o 4 +qd4. ¤zlrl A=-2.04, B=-tt76K,lql
-e. 67t6Jr+. 427"cql^l ol 6114 EIgg (i) B¤ tr.+, (ii) .*.? HIg cibus
=
C=z.rx 107 K3ol4. 4sgKql^lel -tr= Hl$ elBirlel s.= Hl* de_eu1g
qlqzl, (iii) E+ Hl8 QlBEl, H (iv) s= HI* $lg-gElE TaI¤4. ol 6 4r+q4.
7l=g oltr4 o + BE6lq, Atrr"e} AJ"= ol .gE gqql^l gEql ro
E6B.7(a) H,co(g)=co(g)+Hr(s) El84l9 dill $qg "JA6J gEql^l
6IElr ,IA6Iq+.
r.obar-tr.Pel 2.0barE+71^\d,4. "l HI*419 &= 9 "/"+ H6I4l!+?
E68.3(a) ri4]E]"le^,= N,Oo(g)=2NO,(g)9 B¤g ol+q 2s.Ce+ E6B.7(b) CH,oH(g)+Nocl(g)=HCl(g)+CH,No,(g) HIS4|el dill Sq
r.oobargl,rl 18.460/o71 6}lqgtrI. (i) 2s.ce} (ii) loo.cql! ol $$el r$ g "Je¤I gEql^l l.0bar-trPel 2.0bar-tr ?zltl?4. ol HI*419 r,=
A,He= +s6.2kl mol-r-E +r
4ltl6}q4. Q zo4 H6ld!+?
E68.3(b) E-$ $zlz| Brr(g)=2Br(g)9 BBg ol+q t600Ke+ t.o0bargl
E6B.8(a) E eLllg Cr0H,7oH7I ol^H eqlgs E6l. Tlill^J olCAillq}
4 zqyozl6lt4¤trI. (i) 1600Ke+ (ii) 2000Kql^J ol HI+E K$ A,He= *n2
HI+g ¤B dI+= 8zl 4"ll
so3Kqlî 0.l06oltrl.s.0dm3E e
7.50gel u
kl mol-'-tr +-7 al4i6}q3+. Lllgr+ r+.0g9 ollH eLll¤¤ Er s03K_tr 7ig6iq B¤¤- ol+rll 619
E6B.a(a) zl$¤g qlolEjE ol+6lq HI$ pbo(s, red)+Co(g)= trI. BBg ol$r gl* ol + gAel g +-$g 4l4}6lq4.
pb(s)+co,(e)91 4aJ -*.= HI* Gibbs glHzle+
¤B ^J+¤ (i) 2e8KeI (ii) E6B.8(b) N,(g)+o,(s)=2No(g) BJ84l9 B¤ ^J+= 2300Kq^l
400Kq^J 4ltl6}q?+. g= BJ+ tlgul= gEql +*6}rl-z zl{6}q4. l.6ex l0-3o14. r.0dm39 8zl 491 s.og9 Aie+ z.og9 t4= Hr
E68.4(b) xlE ¤E qlolEl= "l*6lq HI* CH,1g)+3C1,(g) 2300K-e 7l-g6lq BB¤. ol+41 619+. BBg ol+r 9l= Nog E +
=CHCl,(l)+
3Hcl(g)oll r]loJs.= HI* ctubs glulzlc+ BB tr-+E (i) 2s.Ce+ (ii) so"C Sg 4l.t}6}q+.
ql k| mol- r, -a 3l -7 A,H"
^l 4lî6}¤ 4.
zgs. r s Kql Afc "(CHCI30)) = -7
E6B.e(a) gEE 2e8K-e+El 10K EJ+ +flg
3.7
"ll ¤B *izl
^l (i) 2H}ls El
mol'olr|.
Hlg" r+ (ii) js EIE HI¤:g s+ HI* tlBulE +6Iq4.
(CHCI3fl)) =-134.1 kf
E68.5(a) e20K+El l280K4zlel gE ¤Eql^l HI* Zn(s)+H,o(g)-+ =

E6B.e(b) gEE 3loK_tr+El lsK trE +qg ql ¤B *izl (i) 2Hlls El
ZnO(s)+Hr(g)ql rI.J S,= Hl* flBul= +z24kl mol-,o]4. E t280Kql Hls" r+ (ii) +_tr. 5l= Hl*E s= HI¤' flgqE +6HE|.
=
EE-,1 6C Al+ CII

¤B E8I
D6c.1 94"-lel Eg¤- ¤84q4. D6c.g Azl ElHl¤g d+E 6e7ll 6IH^l +A4H "itr zl¤Eol ^8zl
D6c2 dzl qfl¤g qr,ll^l 0-d+ aaql^J 6lbzl ¤B+qE ¤¤6lq+.
=zl
=a4"t
EA 217
w4 t}sl-¤¤ HI*ol "IH tI¤¤"I dFE ^Jzlzll

6l+ E] ol+g + oocs uJut{ dzl$ CoilCzlE q$rtl 4Ezl ¤E6Iq4.
9lE ol-?E ¤E6iq+.
o4,\
l.jtr
"J+ Bg g7l 96Il^.1= EE 6Dg zlEE olf,-ollof oJQ, s= dzl qfl¤g 4lt}6'Iq+
E6C.1(a) eg(s)lAgBr(s)lKBr(aq,0.050molkg-r)llcd(Nor)r(aq,0.010molkg-') (i) Zn(s) lZnSo.(aq)llAgNo.(aq)lAg(s)
lca(s) dzl9 2s"Cql^-lE ElHl¤g Debye-Hrickelel +oJ Hzl4 Nernst 4 (ii) Cd(s)lCdclr(aq)llHNo,(aq)lH,(g)lPt(s)
I4r'l 4lt6l.q+ (iii) Pt(s)lK.IFe(CN)u] (aq),KnIFe(CN)o] (aq)llCrClr(aq)lCr(s)
E6c.1(b) dzl HISol zegCtls; + H,(g) -+ 2Ag(s) + zHCl(aq)"J dzl
Pt(s) lHr(g, pe) lHCl(aq) lAgcl(s) leg(r)E ^846ll -H.zI. z5"Cel 0.010mol E6c.4(b) ffi {zl$q qlq} dxl H}s" 4 d+ R}-Hl¤¤ I.1t 4 dzlE9
kg-'9 HCI ggbEql^l 8.,,=*0.465sVoI+. (i) ol {xl H}*"il .I+ s.+ dzl ElHl¤g 4lt6}q4.
Nernst 4¤. (ii) ol d^l H}¤.E a,GE 411}6}014. 1c) ol }E.oll,rl
'{14. (i) ft(s)lcl,(s)l Hcl(aq)ll\cro,(aq)$srCroo(s)lAg(s)
Debye-Htickelel +tl Hzlol dB.J4l H ? E"(AgCUAg,Cl-)$ 4lt61q
4. (ii) Pt(s)lFd*(aq),Fe2*(aq)llSn+(aq),Sn2*(aq)lPt(s)
(iii) Cu(s) lCu'*("q) llMrr*(aq),H*(aq) lMnO, (s) lPt(s)
E6C.2(a) dzl t}Sol Zn(s)+Cu2+(aq) -+Zn2*(aq)+Cu(s)oJ Daniel dzl9
-s.= dzl qfl¤g 2s.cql^l l.lovol+. q¤-d+ -tr= Hl¤: cibbs glHzl E6c5(a) ffi qlgol "Jq+= dzl= E_t-_=r ?+?+E s= dzl ElHl¤g
4l4}6l-q+. 4&6Iq4.
=
E6C.2(b)'Bunsen dzl',9 dzl tI83 Zn(s)+2NO;(aq)+4H*(aq) -+Zn2* (i) Zn(s) + CuSOr(aq) --> ZnSOn(aq) + Cu(s)
(aq)+2H,o(l)+2Nor(g)ol+. 2s'Cql^l ol d^lE -tr= d^l qfl¤g zs"c (ii) 2Agcl(s) + Hr(g) -+ 2HCl(aq) + 2Ag(s)
ollrJ _o.o+ov"lE|.
"l 4zlzl6J + gl= 4zl4 "J¤- alt6}q+. (iii) 2Hr(g) + OzG) + 2HrO(l)
E6C3(a) 2e8Kql^l v=2oJ +¤:q 4el qz} roE9 lE ei6IE dzl ul E6cs(b) ffi ql$ol "Jq+E dxlE ,J==i 7+4E -*.= dzl ElHl¤g
Hl¤ol E"t{ H6IflL+? 4l,l}6}q4.
E6c3(b) 2e8Kql^l y=3t HJ*ql 4eI qzl5ulle f;zlalE dxl ulHl¤"]
(i) 2 Na(s) + 2 HrO(l) -+ 2 NaOH(aq) + Hr(g)
E"tu} E6l4lL+?
(ii) Hr(g) + Ir(g) -+ 2 HI(aq)
E6C.a(a) ffi {xl$ql 4-J dzl H}s" 4 d+ H} H}¤¤ tt ;s zJ dxlE9 (iii) HrO*(aq) + OH-(aq) -+ 2 HrO(l)
E4 6D C= tr1EJI¤
== =xll
D6D.1 +S"19 pHE +Aa}E Ell +"-l d+g olf¤ ¤E5Iq D6D2 tle+-+I?l "dlg -E+ ElHl¤g AA6h= %1-Bg ¤E6Iot+.
^l-&61-b
4.
G^
Jtl
E6D.1(a) 2s'cql^] dzl Ag(s)legt19lAgl(aq;leg(s)9 -s= dzl jrld¤g E6D3(a) .g= aa9 +t"l¤ ++a! +q^l f 3ol o|$ f,$$ EIE +
+0.es0evol4.eer(99 +6ll H]¤.ql ql.J BB tI+¤. 4lt6lq4. 9lae+?
86D.1(b) 2s'Cql^l {zl Bi(s)lsirSr(s)lnirsr(aq)lsi(s)g s= dzl ElHl¤ E6D3(b) E+ aaE ¤zl *eI +ql^l $a zlillz[ E¤ +]ne &e+^la
I +o.g0vol+. Birsj(s)E *6ll ,J3ql rll6J BB + ?l4lL+?
^J+= 4lÎ6Iq4.
E6D2(a) (i) xlE. ael EllolEl=
"l8o}¤ 2s"Cql^l {zl Ag(s)lAgNOr(aq) E6D.ah) s= ElHl¤ qolEE olc"6l.{ trl-s H}¤¤9 zs"cq1.,<1el BB
llcu(No.),(aq)lcu(s)9 -tr= dzl qHI¤+ ol dzl Hl*el s.f Gibbs gl ^J+E 4ltl4q4.
ulzlq ggirl5 Zlt+qq. (ii) 3s.Cql^]9 1,c"9 *g Alt6'Iq+. (i) Sn(s) + Sna*(aq)
zle dE qlolqE ol+6}q = 2Sn2*(aq)
E6D2(b) 2s"Cql^l dzl pt(s)lcystine(aq), (ii) Sn(s) + 2AgCl(s)
= SnClr(aq) + 2Ag(s)
rysteine(aq)llH*("q)lo,(g)lPt(s)9 -s.= dzl EIH!¤4 ol dzl Hl*E s= E6D.4(b) e= iElH!¤ EllolElE
"l¤.6lq
q-g HI¤¤9 zs"cq1,r19 ¤¤
Gibbs oll LJ zl= 41416l¤ 4. rystine(aq) + 2H+(a q) + 2e -+ 2cysteine(aq)oll 4 *+= 4l,l}6}q4.
oJ Ee=-0.34V= ol+61q4. (i) Sn(s) + CuSOn(aq)
= Cu(s) + SnSOn(aq)
(ii) Cu2*(aq) + Cu(s) +2Cu+(aq)
218 6 al+BE
s,lzll. U trf+ EE
-E.o-lxl E T.ll
o tl -lL/'ll
16.1 oI4 qlolEl= Pd(s) lHr(g, I bar) IBH(aq, &), B(aq, b) lAgcl(s) lng(r) C trI. tI Elill oJBql^J= *Eag +E +ql^J 46JqI dz} ?zll
zlel slH!¤ +e ar+= seF"J Lol4. ol +azlEg sF gsl2-olulE el Hl*^l7l= aolq. relE Îs+¤Nernst +E +q Eqfl= EE +E
tl4qEi(BH)r+ 2-o}trl]r-q4B(B)E EoEE A4l +l6}t1 93 4"14.
"l
g BB EoE r4r dz} izl]g 7)^\^1,*+ qfl¤¤: ol*6li^J +Eag
EllolElE.g 2s"cql^J9 <tEol4, Ee=0.2225rvolr+. ol rllolQ$ 0l+6} tr= qHI¤g eA6J + 9l+. EIEIA ^lEae-c$ zlzla- ol %r-Bg ¤
¤ "l tI9 2s"cql^19 pK"E eA6Er" BHq ¤+ ++EE 4lf(2.)E EB B4Aq. .rlE-7.$c, cytel 2,0-4=egoJEull$, D^lolel tdzl El¤¤
E"E(D)e| ol$ ,r.llzl(fE 6J+s +6Iq4. A=0.50elol_r. Be+ C= olgql cyto*+D."d cytred+D(,-g +ElB f glErll, olE Hl +=¤- g.+ 4Iol trI
rlal ¤C9* E|4"lq5ol+r H i, Davies 4l(sF.30b^l)9 ol*a}{4. ea g_f =Êlegol ,u-ol6}7l ql+ql ¤-*q]4oe ¤rll +ztg + gt
4 dzt bx'el'red'E 4?: +e+ t4el g+] dlEI= +4utrI. (a) rlE=.E
b/(molkg') 0.01 0.02 0.03 0.04 0.05 ca+ DE s.= ElEl¤g 7+7+ E:ne+ r?,41 6IzI. ¤B tqlql^J In([D,-]*/
E,|'(Z''C)/V 0.74452 0.72853 0.7t928 0.7r3r4 0.70 809 [D...].q)E ln([cyt".]*/[cyr.al",i)oll Ell6||^] E^l 6]H zl$t\zl ol J. y-p¤ol 1
F(Ee.y,-E"D)/RTt zlcol Ll¤¤ trqei. {zl,rl BB *EE= ¤B E-ts

b/(molkg_') 0.06 0.07 0.08 0.09 0.10 EE +il_a EI+l=trI. (b) "I4 rll"lEl= 2e8Kql^l pH 6.5 +I+ +E +qI
E 0.70380 0.70059 0.69790 0.69571 0.69338 ^J
4tElg ^lF=Eca++Igg D Îol9 HI¤¤ zlzl_t_ E3 aol+. [D*]*
"il(25'C)/V /[D,.a]*4 [cyt,-l*/[cyt*].q= te+g Îtr=fl,c9+ +]gg D7] +
dE +qL +EE?llq+ î'ql_E^lEE ol¤:a}¤4. =qfl=
4. olE qlolElel D9 s.= ElHl¤ 0.237ve+q zqsre+ pH 6.sollrl9 rl
|62 ol EzllE ¤zl dgl E :lz|lg EÎolE g6J eE g.l7l HI++. pH= Eas-cE -tr+ qd¤g ea6fq4.
7.0113l0Kql,rJ erp 7l++6li 901 eope. qE HI*ol "J-^Jtlc"J
Îd
I Ez[ +=ql^] c4oilex]. (a) Arp z[ffia]l **ol .J ^J&c.J ++21 [D,,"]"q/[D,".r].q 0.00279 0.00843 0.0257 0.0497 0.0748 0.238 0.534
"J
olf+ trl+ oJtrlel ,L+ e4 HI-&ql El]6J Ee Hl¤: {l= +ulz} "Jol
zl ull$ol4. At"J& zlTf oloJtlzle+ fltlzl s_71+ B6llB qq flEsul [cyt,].'/[cytrl"o 0.0106 0.0230 0.0894 0.197 0.335 0.809 1.39
7l G.7l6lY olf+ +9.o1+? o) E"J+ aa 6lql^l= H4Arpel Msspz-

(Mg,* olgr* Arp4- olg zl¤)E 7I++4 cibbs glHzlzl erp* 16.7 b}+g EAI ^.i+flql^l "Jq+= clog ol6J4lsl HI+g ol zlqg
Îolel c6J 444 e+ rteg "Je7l= rll feal qe.g 6lt 4_o e "Jqdq.
9 zti+oll Gibbs ollLlzlB+'J *"14. ol ^l¤g "Jd ql&zlE ^lolE
442]|4 qlgol Arp zlf g6ll HI*el "J-^JtCg 4+61+ eI s-"1o;4 "I?jl ¤e ^J+=2clo(g)-+(cto),(g) HI*ql
EH.J+a ?4014.
TIAS ?Ea6l+ +Ae ol*qr gl4. ol ,IAql illoJ olEzl
= =A¤ TIK 233 248 2s8 268 273 280
+EI4r ¤e4 GAzl olAg qBrll 3ts461-=^l ¤H6Iq+. olE- a
4214 a4zl- "l HI*E .J-^8,t}^dg 4l+6}'= AcFrLi aJoll zl ¤E. 6|11]-_ K 4.13 x lff 5.00 x 107 1.45 x t07 537 x 106 3.20 x 106 9.62 x 10s
+? f,E Ms11pz- +Eqlî Md- "134 ATP4- olg zzlle-1 zrg-

TtK 288 29s
ol BCgtrI. r 6I+* ertr-9 "JE oJ{lzlql +{+ ^lolql=
303
so sj=. 6IAg ,|!t
z[ i!{61.= 1o]1" += 6}+= erp*9 "Jt "Jt}zlql "Jdq} "Jtzloll K 4.28 x L}s 1.67 x 10s 6.02 x 104
+61-= *s-e s}dg tl^zl gq6l+ 4,o14.

(a) ol HI*ql 4oJ a,ru"4 a,s"el ag +6Iq4. (b) a,H"(clo,g)=
!63 ol E4lE .E7l dql t l4lg EÎolE g6} eE glzl ut*4. ol E +l0l.8kl mol-'r* s".1clo,g;= 226.61K-' mol-tg ol+6}q (Clo)rE -tr=
zll=
^J3r++4
r+cg oJezlE ArpE bH"l eaq E4^J qH flErle+ s.= E qlE +r.lE 4lt6lolq.
^-llEE ^g^d
g6&3 BExIE -H-71 96J 4014. ArpTI ADp-tr 7|+eql ¤ qE e=
16.8 Thorn 53 CtrOlg)= %ldzl olgslB o e 3Î6}g.trl-(/.Phys.Chem.
HI8 ciUUs "llHzlE 37"C9+ pH=7.0, r4.I. ATB ADB "f l,- 5r5o1 E-
100, 14178 (lee6)). olSol H n6J +e e4ql E6l-E AfH"(CI2O)=*77.2
F t.0mmol dm'?-l++Aql^]g] HI* ciuus "llHzlg+ ulaal¤4. olSg ol +a a+= HI* ctrolg)+H,o(g)-+2Hocl(dql
kl mol 'olr|.
t6.4 ol +zll= grl dql ts:l4]9 fl^l-o1e g6J e= 9.lrl Hl++. ^J +6J E¤tg gq+4 E'ilolEl"J K=8.2x l0-'q A,Se=+16.38J K-r mol-t,
E+zJ -E= sAql^l szlC sge el Ezl.9 a.= Sd te} rqr +GJl{l +.J gqq'-4 qlolEle+ ad.6}q ag +
4ill4e_-+- 387HE Arp +^l-= ElEtrI. =+i(a) dEuI4 -*+ 44 6lqq. ol alg Al4}6lq sor$. 4zld9 AtEg ^fHe(Hocl)g
E+ 2e8Kql^lel <lE
^l7lE^J
ql^l EzlC ggE Egg 4 uozy 9g+i (b) ¤o}9l=
^llit *ql^lE oltr+.
pgo, = 5.3 x 10-2 atm, Po, = 0. 132 atm, [glucose] = 5.6 pmol dm-3, [ATP] = [ADP] =
[Pi]=0.I0mmol dm-3, pH=7.4, T=310K9 ^}Eql-zl Z4ol dB+tr]. gt
!6.9 25"cq],<l Daniell dzl9 dzl uJ8 Zn(s)+Cu2*(aq)-+zn2*(aq)+Cu(s)
q qdl^J= L,Ge =-2t2.7kf mol-tol4. b(CuSOr)= 1.0x 10-3mol kg-'4
EE EL" E9 f^le
ts9 + 9l+11 zl$alt- ol ^Jijl aaql^J s.zlC E
sg ggg 4lt6}q4. (c) d¤4"J qA fl4lg ?.=873Kel Tn=re23K b(ZnSOo)=3.0x 10-3mol +.qEq ol$ .<Jlzl, (b) 4 4¤E
kg-'"J ?*, (a)
ziF6}rq, r tr.gg olE4 6J4lil (l-?:/Th)el E 7solool+(Eq *# "19 +lEE 4lf, (c) tI* zl-6u1, (d) .*.+ Azl qfl¤, "i (e) dzl
^plql^l EIHI¤g 4l4i6}q?+. (4 4¤ql^] T*=T-=T,4a tso}4. Debye-Htickel
3AE so}4) AB4"J qe qldE E¤-3 etr-zt"J ^J4l aaql^JE E
7lc g.g:E trgr+ ullal¤4. ^8ill "Jql^Jg qlLJal d+l."l q¤ qltl "J E +6J Hlg ol+6}q4.)
q^lE glulzl d+tr4 E¤-ol trIâ q +e ol+b 5-qolflLL+i t6.to dzl HlSol HgrClr(s)+Zn(s)+2Hg(l)+2Cl-(aq)+Zn2*(aq)?I d
t6.s iTlc qtrlla.lo}9l,rJE tl gol a /-71 olu E}= +zI.J +
zl Zn(s) lznclr(o.oos0 mol kg-') I HgrClr(s) I Hg1t)z1 9l+. E "(zn *,
glsq, 4l+ az} EzllE orz| o1g +g=+? zn)=-9.7628Y, Ee(Hgrclr, Hg)= +0.2676v, r?-lr dzl ulHl¤"1
EZI"J + gltrI. tL
+r.2272vo14. (a) ol dzl"ll 46J Nernst ,r^14. r4I- O) s.= d
ql{ql ql*s=/e4}g "d}g Eil^} qlqalflo_+ 01¤.6l-= =+?e_^/o,
qtrll4o}z} 49
zl EIHI¤, (c) ol {zl H}¤-el a.G, a,Ge, q^lg
K (d) dzl slHl¤ +ails
+ 9lALLr?
*el ZnClr9 ¤t ol8 gEEe+ gEE 4l+, "t (e) Debye-Htickel9 *
16.6 +Eeg d+ sEql^l Hlgo6J oll : zl¤ +ae+ 7l* szl ollE 6'J H4_oe*q zncl,9 ¤+ ol¤. gEoE 4l+E +6I"14 (0 (aE.ll/aDp
ql ol Tql^J ¤HEI %lg5f. olg_allzr.l : s.? ElHl¤g ee.J fzl S. =-4.52x10-4V K 'oJ A+e] AJel AiFIE 4lt6}q4.
E+ 21e
16.l I Azl Pt I Hr(g, p") | NaOH(aq, 0.0100 mol kgt), NaCl(aq, 0.01125 mol t6.12 dzl Ag(s) lAeX(s) lMx(b,) lM,Hg IMX(b,) lngX(s) leg(s)c+ ag
ks-') lAscl(s) I eg(99 dxl ulHI¤g +E ,J4 +A+ Aalzl Hn qq 9l ++9 dxl9 sl$!¤g +A6Iq qg!+ zJ$ rll"lel$ 9fl4.,-=¤zlr.J
r|. ol rllolel +E "J++ trIs-+ Aq. M,rrgb "I,JA"lq d4ee qIEHI +6il9 Liclol+. E"J
tEqlîE ++EE 4l+E +6Ir" ol =?-l=ql ag al^l 4= tEq^]E BE.E
el"c 20.0 25.0 30.0
4+=¤ olE dzl qfl¤ +a ar+E+q 4l+6}qe|. Davies ^l(sF.3ob
Edrlv t.M774 1.04864 r.04942 ll)¤ a=1.461, B= 1.70, c=0.20, lal-tr l=blb"9 +r. ol¤-6}qzl. E.
bz= O.09l4l mol kg- t o 1 c;".
ol$ gEqlrlg pK.E 4lt6l-r" E 2s.0.cql^-lE EE xii-ll o"t'rJx[ ol{
s= Qlg'le| $!E +q-= 4ll}6}qe+.
HI*ql 4eI b,/(molkg-') 0.0555 0.09141 0.1652 0.2t71 1.040 1.350*
Etv -0.0220 0.0000 0.0263 0.0379 0.1 156 0.1336
-#V1,,\.7
gfr l'=
+ trI= flzi4 ¤¤¤ rssac Newtonoll 9

o}flzl- "J"JolE9
7C Ettrlel 7[zJ=aJ
o1l.r.J lTrllzl"ll s"J¤'ld9q}'el B4# Al^l +48 +
9lg asE ^J46I9.4. :z rd-^lzizl= ol ld9qrol rJ¤l zI* *.qt
"JzlEel r}+l+"d¤ +4
zlzl:il_
=ag's&zlE
+HE Ei1+ +Cfl +f,$$ ql*61 ^"it4e-e. ¤B6tg LI= aol+.+ ol ¤tlzlzt I +eo¤-e-srAl r +ql
zl rll$ol4.rfl+ dzl4, fl2}4, +zt Eel qdf +EI.ll -tr6JS CE=;;3afl{} 4,"14. oJ e$oll.<-lE ¤t}zl¤ 9¤
eJH '"Jz}9qt-'ol4r +e= tlol+ ++q 94"1 g,q6l. ,il trJ¤q^J 6l+.zlql +6}l^l ¤Bts 1"14. 6I
^l-s-o "lE¤- ^l-s"
4. "l tlql^l= ol oJzlEqlg iz|]E 1"Jrll, ol4g *e-s H'E+AC gel'. ¤zll 9irll, ol fl4E "Jzlqqlol ad9
"l 4 dqlql eaî
ol¤-¤ 4,o14. Eqe+El 14 qq+= gelE 6I++.
7C.1 Etlrl;7C.2 TlEllil; 7C.3 EqEd flal; 7C.4 grlqEtE
7E =au[
7A grl-qetel 71fl
rs.{llzl "Jztxl9l+48 ¤84 +rlql E6}E d{$ ,JZ 4 7D BT! AE
e "J"Jolql qlql^J= rdqolol 4*gzl ?*b+. a# q
+zll4 oE "J6ll^J ^ll"J+ de er+ql el6LE "J"JolE$ "J
*a +ql^JE s"J Hd eH "ts^lqolql^J +l#61+ t zl
EE qlq 4Z zl4 + S.eq, "J"8olel rl*ql +,ti rd4

E4 ¤E}]e-l Sol4. "JzlEql
el6IH +.JqI +zI ¤q "Jql
z|JHE"l Fl4i"lTl+. ol Eqql^l} zotllzl aql olBl6J ++ ^lEI
+H ts + glrll 4lEB "J"JolEe ${a3 r+JE" C+=4
rql ElJs"6]+ 9luJzlE"J9 zl4 i 9l+. + schrodinger 49
a!l-=-_tr tj El qBzl ¤49o}9 zl]H4 a¤419 zl]'jE"l
Sp:"l\l !fl-izlE ¤E+ 4o14.
+r 47lql 716l]zl= azJ ullEql "JzlE+7I zlszl o + +4+
7A.1 0llLlrl grlgh 7A.2 EIE-gEJol ol=¤ :. aolq. ol ^lE afl! ojujolE qq Hlrd4 5c, r.7g
E?-lE4e e -"1¤¤ + S= gq +qE oJJolTr =6-1
Eqzl.44
E" 116}|
4zlE Elts ¤^J4 eg $^"ig + ¤B6H=+.
7D.1 1itfl rl8 EE; 7D.21il-fl011^lel 74 ¤E; 7D.3 2itg 0l80ll^t
78 trl-=:d+ el ++ #; to.a EtE fla
"Jzlqq}"ll^J= alE E= ca# Erwin Schrodingerz| x]lgq}
^lg
+q^l EolzlE rlE"¤+E zlzla- +4U4. ol Efloll.<l .rtr
tL xl-=.
uo
o-=.
llo
rl-tr.o6'J+= qBrll all!al.=.._zlql +6il^-l r?]r +61 olaol
=
"J"J"l9 +lzlql +6H^J +Eg 444EzlE ul*zll ¤ 4o14. oJ e$oll.<l= E^t tlt¤ 44421 +l6I^J ole" 9E ZI+6IH
78.1 Schrodinger Ali 7B.2 Born all4
r.Jr rll$al +sq} E¤"J {f;{of +5H^l ¤¤6}rz} E}
=s|
4 tl5-z}9 "llHzli "JzlElqq, _lr.dqqql^J -"13-" qzl ?+=
g Eql^J 4lE" zlz| + 9l+.
7E.1 5il flErt; =z}]g
LiI dEriel ¤E
7E.2
7F EId EE fl rlE 0l rlEel EE=?
2Z1¤r+ 3il¤ql^J Eld6k "J"Jolel I zlallzl$-lr$ gr'j uoll^J= "Jzlqolol ¤+6J 4el fte_e slzl ?lollrJ
6d_o e "J"l.J.l Eld 9"Jol9 glHzl= oJzlslg4. s"J oL gsql "*9 EzI# ?t4611 +9t+. +it 4lE Be ^J4=
,14 ol
"llHzl} 4$[t=*+ *4lgzl tril$.il Eld "J"J"l$ 4
g E^14 o-tr. 4l4I6J + gl= 'oJzl. e+ts',¤. 6J + ?its a
gE"elE eqI5C63 {}="Jg zlgi gl+.4¤E"%F9 "Jzl-Er a+ e+Elel zl4"H e+ 'rlk r+qPg lnm-tr-*
^]| ^llql$
b gzi "J9 dz}4 sld6l+ EzlE q*6l +s* ol4.54 5 el roonmvl^|4 a7l. *= +lz}4 EzI El6JillEql +6J S
¤"14. +s^J 'ulrL *+ql^lE olq+ qqlill= tlil +q dqB
zrtfl
7F.1
'{IJ;
tr.Z 3iEl cld ¤+= ++. gt'j r2oll^J= +r= .z71 q6JillE ^d¤ol :
=
zzl"ll qgrll E=61-=zl= "Jzlqql4se B+61-=q]¤¤
i7||6}fl+.
Eiif 7A gfrlq-+e! 71lfl
dE a;}ig tsa6l7l ^14619.+. olEg EeE Ceql +

> ol E4E u||+ ol+'
+ dHlzl"J T}]HS Hl.+J. r.dq+ 4tlql grlq-+ol4=
iltrtoll,(l ¤861.= LHE- zel t+71 zr^lEoil "Jr__.161-7 ?,Itrt.
ol$g gd^lrlrll Elfl+.
flx|e+ Exl-E +4, eltrt e*, ralr. ¤tr= 0I6I|6E1E
gqrlEol gs6ltrl'. =trE
7A.1 ollL-lrle.l grÊt
> E4C T1LJ
d-d4 E6lE 0llLlxl=EE+4 ge_eoJ olEqq, goJolst ol Aql^l= 44!¤e 4q+ qlqzlTl E¤+4 "JcEr.J
tr-d rE4 TtlLJ=3
trlEoil =71oll fl#?lrl= g4l Erl.. trJ old¤+r HAI "JE le^llzl g.ql ol+ol+l rll zlzl ¤E
=E=
> Ele'Et qHI rl^l Îds$zi|44o+ ¤E6I4l+.
zEq+g 7lE flal, Eol EfEtxfg 8^l 3(EE 1Bel)rh 6(EE
2A$0ll^'l ¤BEt EFJ
:d,
.f.alr ollLlrlE 7H'J- +^l6Er. ,, qi{ E=Al
?1ol0F Eltrl-. ai'llel gEEf= tsE6l'= tll= EE 2Ael L}lE- Elulz}9 C-^l r3ql -TdqEql E4qI 4zlzl +^l-9 71ts
efrJ er'aaHgF f,1tl.
eg ¤B6l] +9t+ E= Eill= gEql qq tI'&6J TIEr =
+ ¤qE dzl-71 +^l-= gAqI ,<llzl_tr "J=qI+. r +g ql
r7^ll7loll Newtonql el6ll^J tsdg -adqqlg "J^J4?l rlltl ,I zlg6}E !gql= e$e Hg ql+4zl zl$s-=
^]"+ql=
Eol+ ai]el ¤t¤ ql+61 ^d+4_oB ¤E6H=+. rBl+ 4l+6IE'E4%Pg'll+= ¤tol 4.
leîl7l +Hlql "*e 4+4-=g _adq+e_e ¤Eqxl 9*E E4g EAITI HJ={+ olel* +^l-= z}zll 5a3
=i{lE
ElEtrtel 8rl rg 9;lT l H-1[
Arltl4 zlzl$o\ ii+-E"r+ Hl+6IZl diil iil+g "Jd ¤+?-15 trEI 2s +

dxPlE-^}E dE ÎolE 44= +Elql=
q= ¤tr-"14. dz}Tl +Îel ol + dEE .!e z.ljl 4g + 9l+(Âlil 2). $zlzl +Î= 3ql q4U A
"l+g ^4lil¤- + 9l= dz}
6lq dr} %r-.Jql ql6ll^J fzl"lcH^4lil r). {z}zl +^l-+ xlB iiltlg zlzl:il_ ++El+. ,r.l.$ ieE
4l* +q^J ts+olr}r +s= "JA+ +q c= zfzll o1 zl +Î"J H3 +zonm(tr+4 H)+E] 700nm($${ q)
= ^}
E"6l*41, ol g"J6I4l 2.997 924 58x108m s-,o14.
<ie. olel iiltlg 4=+. 4zlzl +^l-= v* Tlz.la_ t!# r
gl=rll, {l#* gA =
AE{ nP ^dg ++'3 + ^l+ E"JE Tlffi
Etr[qts S-Br ;1 ,<lzJ9_tr qt. a_o E^J ++l= 6ll= 2, Hz(ull=. 1415,
rHz=l st)o14. H9 zrorHz(-H-44 q)+q 430THz(*g
=
xl'718
4 q) r}"l9 ¤qq EqTl= 41ffi *=+.
1
E718
^fllil afllil 2
22t, 7 ?fIl,E
trl.8 )lm
o N
o @ N @ o
Y
o
I
o I
o
I
r
o
F
o
I
o I
o
I
o
I
o
F
I
o I
o
I
o I
o
I
o
E E E E E
E
E ! o c
F 5
H
H ru
rl
{i {l 4 {J {l + 4
KF oFl d' d q. *eE
11 o
! Rr
rU
kr N K
xI
J. Kl-
OF
H
arllil 3
dzlTl +Îriel r|+r+ 1l5+

Îolql=
E+!-_rI ag.+4lrl
+6lzl= *q^lE 1!+ol 4oiaEx:alzl 4). $g a+¤
¤B++. tr,J A.dol4jr.6lq, +ztE a++ t[4] z3,go1z]=. dJ4.
'BzJ 'zJdol 'Jol+= gq{^l= ufe1 +7}6}r" {i
c=),v 1E +01^19 trra4.!E+ 87, ,Jd
^llzlTl
^totg 4l ¤qq^lE +E ^ll7l7l Ai6Jq. EIE AAe r+9
dzlTl +^[r+: E6J'P-r],J.1 CgEl= trl+ r,= 7la1i1 as"ll 9lE TIzllg zl+7t +^]v]E sI+4 Hl+g qi 7ilil
u14t.1zls. tJ4. ql E6ll^l .Jq+= trdolEi. s00nm AEq rl+g r*e *
tlE+g+aql 9'l'
- r E=
n=i -v
-. n='i trl+'aetl
E6ll^l Eld
++= "ltlE 9fol4, qL +qd zJol 491 5qil= ++

el ++r E + 91trI.*Iqql^l= +4ql q+ EE ol vl
+E qdelulrl(cm-,)s +Elu+. El+^l 7I^lc¤. *izl
14 000cm-'(B¤4 9+El 24 000cm-'(B+4 H)ztzl9 sl
tl7l 7l^-l
+= *= 4zlzl +^lq 6I'J+4. 4<> L-: tl
EoJ 415+(trI4^J +"J +*)4 &zltl +Î- +"J 49

+qqq, r46}q Eqdol4r ++.q^q+e dtfzl ¤
44_"E H6I= 4zlzl +Îs ol+BlTl {e+,<j CE+^}
5E .<llzlz| A$fq q+ +e4. af^ll ad
irl-E:E t a++ cee adg "Jsa+= aol+.
^ltr. îllil4
+ + uI9 H9lzI oJ4zlL *"ll^J= TI+ol Azla_ Hflzl
+ glrt. gill= E= rltE +^l-dg HJ-=6I7IE 6Ir ¤+6I 9 4lzlz| nffi 8zl 4*9 ol +Îdql zl.Jq: qlLJ^l7I
7lE *+. 7l* qill= "Jcql gEe +zlElr gl= r--l
fH.
=Î+
ul!;Sol Efl qPzI Hlq fl= +zl4(.zH ze.r;. ol +B ol *zl 'll+E d4l qlqzl$ 8zl9 +uls +b Zlg oilLl
_q-E gillE +Î 94 ¤.sql^J +4u a xl "J= E(D+a ++.gE_ rql^J tq 7+ dA 4zlzl
^lJq+e= îl71= ^l-olE
ol re 7A.2Ll. ol rB E 4 gE rql^J +^L alqlE +^Hl ,l"Jq= "llHzl "JE= dzql Hlqle-aol= + ola¤-
^ll7l7t
q= rltl 7^ *71=zil6}q, ol 2_"_4 r rl-ol"ll:- wienol d-d p&t)dA.e ++LHr, p&t)E ollLlrl trJ-E+r. ql+.
Ê4EaJ
glHzlzl ++= ag ,J+
H=l"l ^JB++ 7q 1+ dt Îolel +tr-4 +¤g
614tI 2s+ gE- r"llrl glHxl "Jgzl-.+r Eql
).n u,T =2.9x 10-3 m K Wien9 Eal (7A.1)
+ qlqzl .<EEH ÊEH
,|tr-ql ea^J q+ql+H(+
"JEE diJl
olE gsql^J+,,J=q= +Îel q 4E6IH) qlqzl oJszl +$tri.
^llzl=.ri^Jol 4."ldql =,
p-X= U154zI +zlaJql ol
"14) #46ral eA6J+. $,r.,|,rll rQ) - l* o()",r)dl (7A.2)
7l= +ill *zl 4PE qqzl= +44E 4" +rl ol +rld
7A zr^lqetel 71fl 225
8-E 19 Eu I
)1=9
E=O F
Rayleigh-Jeans
=^l u{il
Ela
Lri
Eru
il0
HI=?B nrI
Er /\l3.l 7l:rl-
=E =!l
<l
K
5
6
leJ 7A.l +^1.= SE6l "Jtr1E ET lE Hi57B= Eotl,\l ?,ig
=i1l ^tlLl9=
qal
E7l Uoll^1 8E Iel 7lq+ ?f6l E U^lEl -tll$, 1
=8Zrtl. ^t|LleE =^lE Hflfnroe lllGlLl-g=
E,\l Eq EE= olErt. E_ l.= LH+el +/.tel.
E7l
Eg:d
lB 7A.3 ollLjrl "JEol !=ilet Rayleigh-Jeans9 Eal(7A.44.1)01
=d='+=tr|. LIEILH= 0lE4 ÊIEEHlt- 0lE4 qalE ollLl^l
ÊEg "JE=
=rlstsl =rloll
=Jtrl.uJoil j +-dEHe Eq, qzh^1 ollLl^l "Jtrtr +ElEtle Eq.
=
F psl +rll
ql ++\i aol a Elel(9|e TI#)ql^J= A *zlq} 9l
HIe+
"JE(nIi+^l "J=q= +ÎE gE)= ulatol

Lri
orll
-QE
Hzl
il0
LL =71.
O.l
êlEH
S"Idql ul4 fzlalzluJ alr. +E|]dg 44421 *=+. A
llJI
{ B!g "J+^lzlzl { ali

Blg
Er
<l Rayleigh-Jeans9 wien9
K
5 4,o14. EqI ze.+^-l"tl E6IH Eltlol trll+61 5}"tzlH +^l ^ll
6
zltl rtzftlt- vl^J"l 0 o + d=6Jql trl+ +Î ,tllzlz| iAl
tr|-$,,1 qlE +7}6}lot q}tr}. ole+ &"1 s9 ulalql +Î7l- d+q=
g.Eoll,(lel ¤tl¤- rleld nlEolala +s-rll, ol ¤tr-g rd E?-l+el
aeJ7A.2 H 7l^l E7l +g ollLl^l "JE pE7l. gg4"J ¤4o14.
qal qlLl^l ru:]egE =i1l ÊtlEaJ
E+alzl Etrl'8 +e-e 0lE6l.r, EHJ4o+
=oltroll 1e00Eql Max planckt. dzlzlu| d:E"zI9 9lHzlz} Eg+
P| l-:Br= LEf L,! trf .
=7
4"J A}E"Jg zltlrll z[4a1H +i]l +^l-E .rllzl g=.ql +
^1l'7
6J de 44zl g ¤BE + 9ltrI= ag

E(T)4 ++l= oJ%r"lEl 'J m-3)o]|4, pQ,T).el Bfl= "JZl El9.+. E6l
=.0
I m-olrl. ¤e er+ql E6lH "lluJzl "JE= r,ql trl+ E6I
Ec]l "149 Setan-Boltzmann E=lol4r. qL+ fu]]"ll 6]]%'-6k "lluJzl"J$ 4=+r 7tA6I*.+.
E(T)=constantx T4 Sefan-Boltzmann Erl (7A.3) E=nhv n=0,1,2,... (7A.s)
ol Hlql 7.567x10-'61 m-3 K-aol4.

{zlrl h= zl+ ptanck g++a +s= el zlts ^J++ qlLl
^lel ^J+= zlzl E¤44 {tE"Jg 714 + 9t+= 49 otlLlrl eIr}Et+
rB 7A.rE SzlePri +s= +^t= zlq Ee +E d6i
ir. 6J+. ol zl{gl "J46|]^J plancki q-q=$ Ag qlLJzl 1
ql E6H^l dzITl1}E Tlfol{r ^J4$ + 9l+. rd
== EEH "JEql +6J !g +E6iq.=trll ol !9 planck EE^l
E4Eq el6IE EE llE"zl-ts + ilsq, +F EHI] g ol4i1 +ri.
=¤
?](Eq zael E|$x|9 t^l aql E6l]^J 4 tltzF=3 r d
olBleI d4l 6Iql^J EflEzI Rayleigh ?3 Iames Jeans9 _E8 oe,n=nffiln Planck EE4 (7A.6a)
g a+ gq^l RayleighJeansel El=lol+r +s= +*4 ol aH ze..+91 E^la}*Erll _E= ul*oll.<J {fl rllol
ee 4¤- f,s.a1-94. ^lg
rll+61 g ol olEql^l=
Ele+ *=+. ft= "lC +4"lElq.e
PQ,D=Y Rayleigh-JeansEa.l QA.4)
4, zR.6azl"l ¤E a4e+ 7l* * "*rll ¤ 4lr4z1 H+^l7l
E^J r Ag AeB + 9l$trI. ¤x]] ¤."Jqr fl= hq *Z
6.626x10-3nl sol4.
¤zlrJ kE Boltzmann *f(k= 1.381x 10-231 K ')"1+.
Rayleigh-feans9 H4g d+ A4e+ "*xl 9*84. tH ze.: 4^Jol 4"g tril= hct)*T>rolq, 2'+0ol q- aE+ mls
226 7 zil'E
tr|+^J
0. 8
p(450nm,298K) _ [ zooxto- m ']'',. .0"
()
So.o F0oonmTes0-[ 4,oxro-t;,J ^.'- -,1
F
-Y 9.1 1x(2.30x10-'' ) = 2.10x10-'6
Eo.+
a.
dgql^J= *++ +ÎE ul$ol +^le} + flg Ctr+
0. 2
z|# "J + gttr|.
0.5 1 1.5 2
AkTlhc
aeJ t xq Planckel EE^l(7A.6a^l)e ¤E4 o + EB + t Es9 E'

Rayreigh9 %rHol drllol.a phnck9 7l4ol ct+ olf+
"J=trt. 0l 8tr18 gqoll,\l Rayleigh-Jeans
=i1l
EE^llt,JZl Etrl. + 6I++. f 4 tlEzITl-1l¤+q +4lflol E"J6J
planck=
^l= qlHzl5 4=+a ^J46tzl g-L noltzmann Eetdal zlal
¤g }ro].+)= ol+4q *e d¤+9 rlE"zl(++alE +Î
¤+. trl+^l 2-+0o ts Eq rri4 p-+gol E
Al dtut)k'r)""-e.
. Lll+=)= *e dt+q cEzlE4 4al E=+r ^J4tl
+. ,'|+^J qlHzl "JE= #g +*ql^J 0o + d= 4,"14. rl#zl ql+61 * a+ql=.Eal 6F= rll p,qel
6Lq, q+^J ^trlEfl
planck9 49 z}9d uEg "Jezlzl ?*=+. "I
,J ely nc6*T<tol{, planck EE! 49 E_sE trl-S
fliE 9lHzlzl tr|]+61 4rl dE"zlTI dq is- + S= a
^Jol ole+ rJol 4t6l +g t1t+E tlEzle+el9 zl¤E
"l+.
4 301 Eh+q ¤ + 9l+(Eq snel E|$z1el t}^l 12= .Bol +^l6Jetr^J 4qd rEg "+3 aol+.
q).
-l r
a+ql E|4^l= planck Es4¤- {Iffi zlzlt_ L+4rll=
_1 _ 1+ hc + hc 1"l ¤4aI4. :z4E Ss. rql^J v* v+dv rlol9 T]Ff=
"hctAkr Ttr -l= m *: dz|71 +Îql gal glulzl ,JEE pQ,r)dvtr +4'J +
9)\ p(u,t)= q-q=r+ ?ol ¤4.
ol 7A.6a4ql Bq+E +E Hzlol Rayleigh- planck
=^l¤
leans B S4. Planck EE49 Elts6l.E +
zlql ze.+al11' ?JAl p(v,T)--#iDT15+-+ LtEtLJ pranckel Es4 (7A.6b)
qlql^lE +tls +g + gisq Ln *r=tfz]. +s=ql, ola
g EIe. wien9 Ezlol+. r4-l. "l4oJ "J4g-E +g ti+ (b) EAH
E zt hctsky dE4 o + ee6J <i4 "Jil+tr}. + ql
=-e+
uJzl trjE_.= ++4s 9zl ?*e4, trl-94 z.ol ¤4.
6JEillql+ qlHzl= gs^J 7l6l]+E t &Ezl g4,J+. t
E¤ qlqzl4 gs tr-+ ^l"lE Hlql *izl gg"+(Eq 2A)
Sntk' ol+. A C_dqtdTolq, .J4+ +rl 6H]^JE Cu,_=(au^ta'Dv
Ee ) --
I; Tffi )d )"= ar .
o
{ zl rl l5(hc)'
(7A.7)
olQ. terllzl9l ol+qd de ¤4ql 961-H I*:!- l?lÎ r.ill
olAg Stefan-Boltzmann eg 4cg.! ^J+e-l el g. g+=3=g dgql^J af :n"]q-. Rg zli.ll ^J++., rel+
,tttzl cq6l-4l ^l(7A.3^l)r+
ql+61+ ar++. gt *¤: gEql^lb E= lgz} rillE E g8*ol :RE4
arolzlq, gszl- 0_o + d=Etql 44 o_o + d=6J+= Î¤
LltrJtt q 7A1 g grll Elfl+
T= 298 Koll4 l"r= 450nm(d44)e+ h=7c0rurr(44)"J a+
rd E4q}e=e_= E*Zr"l ell gEql q=61+,.1. ¤E
ql 46ll^J zA.6aal9 ar+= r-gqlts+. :zqE, R fzl fifl+. rd4 ,HHql 96IH .lill= r gzl¤ol r
A¤ A ++lql^l Tl# 6lq, dF flzlEg E"J6I4I ¤
hc (6.626x10-" 1s;x12.998x108 *r-')
= =lo7 '2"
TJcT
f+Al dE"6lt Nz]]E flxlg g rzll= u=3Nkr9 "llHzl
hc (6.626x10-'n;s;x1z.ll8xl08ms-') 7l^lq, q+^l g+=*g cu=(dutdT)v=3Nkzt H4. :4
)"rkT - (700x10-e m)x(1.381x10-" f K-')x(298K) - 68.9. =
I zlill tl-+= trr+ zlB4.J Boltzmann *izl R=Nek-E Etlqq +ElU
lolo e rille+ +46l.q +EiB + 9l= 4.o14.
7A ?frlE-+sl 71fl 227
E g+*.g 3N^k7l El=ql, Nok=RolE + E= g-srql^J

_r. ,ll gtrt. ol
¤*zi"J Ar+E E4oI4 "lf+ &szt *"txlE
3Rol s+. le0sEql rinsteinS planck9 7I¤g ole" 6|{ tI fl4Eg 4lE^la "J+9 "llHzlzl-arolzlTl qEol4. 9s
E6l+ fl4s=g zJzJ nhvq qlulzl= zl4 A"le|-L z[3a1 z| golzlfl E*3 dE"zl¤ol +e gluJzl ^J4E + gt
9+. qzl\ nZ Cfoll vE ll5fr|. Einsteing 4l+6ll^l q^l rd4t g+. -
^"ieg +EI44l
Boltzmann Es= ol+6}q zl]zl] tl+zl-=ol +g qlqzl ^J re 7A.s= Einstein ^l o + +qzl= g+e}9 gE 9= +
4E EETI= eEq *e gEql^l= EE= rlEzlzl d-d 4lE +r}U aol+. ol :zH9 Einstein gE9 alg ae4q
g e- Tlolap
^J46i9+. ¤44 " + tlt4¤* # + S dE qlolEle+ g *Al 6J 4"14. +del "JHi4 E"Jg +zl
7l qlgql $*=J"l 0ol g+a ^J4I6Ifl+. Einstein3 olBl+ ul fzlrjs-E= + *zl ?*=+. ole+ eol g
"J "*E "l#b
d4=¤. trIg=r+ e.ol c*4sE'I4.l1$.4tzi4l{} 4lte E= g4¤ol +eg +g {ffi zlzl_t_ tlE" aJ4E z}c
-tr.q 12E= EoI4). ullEol4. Peter DebyeE: Tl*zl-=ol o+El 6J +trilztzloll ol
a= Bqq dffi \rtl 6Je=l^l E+ Cr* {g +E6I
C,,,*(T) = 3R/u(T), (+)' 94. ol+rll ge !g gd EJ + *sq, rfl6lq qql4"J
f,(T)=
[#{)' gfol+ 4zlzl +^rz| "Jzl3r} gtrI= elC6J + Srll
Einstein 4.1 (7A.8a) Î¤g
6lHtrl-.
{zlrJ 4E Einstein 3E4l 6}q, 1r=hvlkol4
E9 gsql^J=-(r> aETl q=) /.+E zlf a;i;5 e{=l + (c) flxl'J Erle! Ar4=a
x + ... E:-tr. flzllap -lLi}6J:=-e- +^le. + 9i+(Eq sBe-l e+
qlqzl rlq+ *4zl q= ae Eeol ¤+6i
"Jzl-sl.el TiAF
4xI9 ^}4 tzl. r-BlH,
4+ HJ=6IA+ E= &+^l7l= dzl-71 +^l-= 45aia E
l+e.- l2T +... 461-= EBH-q--e+El +eq. Ezl¤ F46I4+ olaql el
f,(r)=(+)' (l+0, lT+..-)-r ]'=(+)'t,+]'=' 6l]^J t}*qb qE rllzlE al¤+(v)4, r+^J(2)"1+ E= rl
(7A.8b)
ie=vtq il'$zlq tl^l l3g Eol.4)el EI+E 7l++ ag
6J+.
trIuI^J H9 gsql^JE -r.d4 drXcr_=3R)71+g+. r<k ^nttEaJol+r
7I q= *3 geql^l} eo,rrrlolQ. trl+^j, dBzt"J gx} .trltrHg aH zt.eql, lEla dB4.J E
zi:-tr1=.Hg re TA.7qt +EqS.4."l + EE
^dlEeel
f,G)=(+)' (#)' = (+)' e-oE
r (7A.8c)
6J 5Cg gflE E¤+4"J rl#ql^J +Îdol "J¤qzl
LI g+¤+= 4,o14. ol
^ldg ¤B617l +16l]^l= flz}4 E
zlE qlqzlz} 9H tsS+4 #E"Jg 714 + fleq, -z46l
qzl^J ++4al +416|= zlf a;rag yr27l +qlqlE g4l
6|= 4E+ q uu|trzil 0o + d=61q, r?-16}0l T+0ol 9H q qlqzl$ E¤+4"J oJ_q_e^JtrJ ,ll+4+ ¤+6J+a E
/r+oo1 qq g+*JE I[I+/.J o_o + d=6lq dE e4e+ a
++ql H+r -E_oio} aJ4(:zB 7A.8). r?]4q "J"J gzlE
qlqzlTl LE "J+ elalH ol glHzlzi -u,tlu].tr. 99 4zL
Erll, ol +ÎE 1lt+ vs+ qlHzl H+
^L"lql=
++r+ ge
3
o Bohr Tl.=+ 4zol "J+qqo} +4.
o
l
2
tr
E
J K
o
,(llu
nU
0
0 0.5 1.5 2
TleE 415 420
u[$, //nm
f.al 7A.s EEeJg 0l=01 LIEILII=
-eE
9=E
^lEoll,\i =¤ilel'Einstein galq EE+E trl-g
Einstein 8E 9^-E= 886l E LfEtLH^ltrJ -s= Bqoll^l Ll+ a4 7A.6 tr flrl7l LH
^l(7A.8^.0=
arP rJ= Ll.EfL,!tr[.
== =:= =^l ^tr4EaJa
t:g= Tl#)9 E-^|C=E ol+ol^l ?lrl'.
228 7 zr^tE
alE dol ol
"llulzl il^= {4
z}zl *B " e +4,"J + fl+. qlE
AJ Avogadro tr-+= z..6IB gz} lmol %+9 {lHzl t4
203k1mol-'oJ 49Erll, olag E+ Elqlai'J qqzle+ *

\ T]E EO E= <tol+.
ilo
,l0l!
TÎ.AIEH
d^l8Ell
E0l
l0l 7A.2 trl=-gf,Jol ol=c
200 240 280 320
nfg, ,unm _ad E?-lo,t-ql^l ul-E.ol4r ^J461-= ?J.zlz]| +^r7| oJ"J"l
^JE +4U+= 4g Bolts dB 4¤¤ *e_tr ¤EB 4ol
:drl.
aeJ 7A.7 ErlE 8Et|7l EdlalE Tl5+el E^l.C= Ero*|lot
0l .rul=go. ol^talB(soz) E^lE =8El
drl, Tl5 'l aE 8Et|7l trll
+.r4r -ad E?-lqql,<J ojujols ffi6l-= 4zlzl vls-^J
a[! .ru4=aJq g+= aol+. EE+4 I$EaJ -
dEol =+
LlElLl=
LlEtL.!
E +4U+= ag trq= 4E s 6l+e-l ¤eql +q]^JE
ae Expl'EE+4?l oilL1^lu= 7lE + ?ltrl-= e7Fl.
¤Bg 4o14. $EC$ T,J"ICS Fl$q+= ol trhE--SJ
0! ol=cg Hts oJzlqq}g 4dol q= a"l+.
E3
hl,= E.- E,
E2
(a)dxlzltJts! goJolc
IJJ
hv= Ez-
+ill +Îql ++ planck9 olEoe_ "J"l$oI 119-fzl. vQJ
-: Et
K
T 4zlzl +^l= o, hv;Zhv, . E qlqzlE"Jg ?14. + 9l+=
hv = Er-
6l.rll Els,4. ol oJzlq¤-Hh+q
6 E.,
ol 4ldfe_l
^J4¤- ^J46IE
+^L= 9lHxl hv9 Ql"Jol 0, l, z, ... zllg- ol+qd 4ol4l
E
E +E ?14. "l4* dz}Tl +^l-"J"J"l# zl+g tsxlulr
+¤+. rp]6}"l t]t+ vg tlt.zlzl ,14 EE tr-4E E=E
f.al 7A.8 ral 7A.60ll -E?.1 Hlel ea EB+4 E0l7l golLl'= 'iE ¤8 E ol tldfE %rz} aJ zflz| fz|la|:4 "J"J Eall s== tr-EllE
6E1E 3rt(!E= E^D7l EE+4?l # ollLlrl ,_J=
tt]lEolell=E+4e
ollLl^l EPle E6|,E^l E^[7] E^l-= g=61'71 =+|E+Ej
E=EH *zlzl
27114 fl4.4 +zl-7| E¤+4oJ r-
8?-16t|0[ -Lrtrl..
=zl]q}+.
ollLl^l Eatzf rE te Tl#E HJ=Etrl'. ral 7A.7oll E?] ,tr] EEBS Lll+= ag gzt4 Ezlzl LE_hvoJ a7l4 qlqzl
=^[dol
eg Eo|ts E^KSE= fl^|)7l rjqlt_l^l rollt_jrl E9e E6lE^l
=+lE+El
E sJzlErJ 4$zl ull$ol4r C4¤ + 9l+.
+^1.= qlEolall. ¤EEf + 91tr1.
=+dl'71
W tsrtst +attl
LE - hv Bohr [!E+ 6A (7A.9)
100wel*rq¤.ol 1.0s EoJ9l %r-=61+ $2145 al4}6}q
oltrll ol EzIzI oJezlE tr-E.l] H3rl¤ EleEt4 d0l4r.6l+ 4.+^q HE +tls 560nmE +16}I. 1007o9 g.¤g zlC
6Iq+.
ql, oltrll= HJ= d$f vq ql"JdJ B*4zI 44
^sltrHql
u+. 3a1$| /.l$ z]]z}]9 ++zl¤3 ftv9 9lHxl$ zl-zltr+ q1
uJzlE EtrJA 4--e44 EthvzllE *zlzl B-eap4. ol +

zl.J:d qil7A'.z 4lE olSaI4E +Îdfl {$f(v= ctLa+El)el ol
"l E
+EE flzl* 5e0nm9 +^l-dg %I¤EteErl q-^4 q("J
ol 4--b dill ++. dill qlqzl= ¤q
qlLJzl= "Jolot
^lA4ol E-(E=p 04 e+
(R e+E ++lE)4 Eol 4Tl
P zleE)g LI4U4. ol "J=¤- gezlE E"Jqlzl dol
(tr-q 2Ae-l +q4E tL^] 8¤. Eoiel-).
E ze.q^l_e + +qzl= qlHzl ,J4E dz} "llHzl
=+1.
ql 7l"JEl= 4o14. 4, *zl-ibffial oe 4l&ql+.
=o!
u-ly-f- (6.626xr0-'n J s;x 12.998 x 108 - r-'
590x10-e m
)
N
E PAt
hv h(cl L)
LPAI
hc
,,I
=3.37x10-
7A Uf^lq-qtsl 71fl 22e
LJzIE 7l-Tl "J"Jol+^t ulo$zllz| dzle+ eE6t7l uIEq

¤zl9lct gsql EllolEl= u+q :zBlE, 'J.
=+. ]j,zlzl Flq+g 4"148 ,Jqi "J^lE 6k 4o14. "J"J ol
,_ .
(s.60x10-lT)x(l00ls-')x(1.0s)
=2.8x1020
ulq4lzl-hv9 9lHzlE 4= ¤-ztolr{vE BÎdE 4l#),
(6.626x10-'n I s) x (2.998x I 08 m s-' ) Flq+e= dztE ¤+ qlLlzlz| E*ol_r" Ed
zl¤ qlq4= rll gsql 9luJzl(g 5t+7}r=f+-qE+q
++)= @?+a
EE gE 8^l "JHlzleE ^lÎeoJol4 zl4 +iltlE 4E qlqzl _E_¤ H4ql E6ll^J trIg=r+ zJggAlzl-CB6]]oF
sil¤ q+71 +l6fl^'l= +d 'I+qtzl +^l lltlg 6].q aJ4(:zB 7A.10).
BlLtel 4+ +"J ^lg Eg q-gq] +zl= dqB= aol
?l* +:-| +"J olq+ 6I+E 44 e4= dill= ++6ll hv=Ex+Q Ets Er=hv-@ rJd a+ (7A.10)
414}6}zl ?+r q= *ql

^l ^l-*g + 9ltrl-. ol euj$ ol+6lE +lql^J ee5a dE Îdg g ¤Eg
^.il
+ el4.
xlTl$.7t 7x1 e{"l
mWoltr vI^J"l t000nmoJ B4
t
(+g +ii}+) 4e_ld 4"-141= o.1s Eo.Igl H zl]9 *zl¤ EI"J hv<oolEl}zt9 qlLJzlTI +E6Izl *6}zl ql$ql
*=614L+? 4zlzl +l"lqezl *6J 4"14.
rr0lx9:E Flq+s= dz}9 +F qlLlzl= qE d#ql q-4^J
+71*+.
zlfiTlzl! "Jzl¤ 7I^J4 o=l fl+1{g gol+. ol=ol ¤ *zlzl dzle+ +E=6IE r
qlqzl= g^lql d+ .ll+q,
tr|{^-l ol qlq 4zl *E6l uI= +=ol $olrlzlulz|
zll-tr. ¤zl]q}+= ¤e4 *A+ Bd EztE Flq+s* dzl.
=
e.l qlqzl= +a+ a4E+q +*+.%rd a4+ #+ql+ + 4^l7l Flq+9.4l gtrI.
zle.ld¤. 3q+fl¤- ull dzl-z} Flq+s= ¤t"Jrll, ol E4 r4 te..gE zl&z\Y E+ F"Jalzl holq, trl+^l
dEq
+-q-r+ ge +^Jg *=+= 101 dE4 0e. Blde+ ze.roalS planck9 tr-+E ae6F= rll {xll_E "l+¤+.
= *dzl9 qlLJzl, gEL+ r4I qel "J# dIlE=E(ev)
4q+= HE rl#717+ ++ql r+ql qts Eq #g
LJqolzl rBzl ?*sE oi+?-l tl Hg aq+qE. dzl- += trEe] qlqzl tr9l.tr- E6l +4d+. levb czl ^}4g
dzHdolzl -e)zl L4=rve-l qfl¤ il¤ F"ll^l 7l+q. B
7l flq+szl ?+=trI.
d.$$ "llHzls+ R4. ol Hd gF {lHxl} eApol(, E|+^l
Flq+s= dxl9 eF qlqzl= aqf qe1 4154
ql q+ d¤4se *zl-a}4 :. {Jzlql= =
5+6}+. "l4e+ ?ol ¤4.
tl¤lfz} Eq <lg Hq^J7lEI 6tE qE ,rllzlzl "f.lq Eu= eN = O.602x l0-1eC) x I V = 1.602 x 10-reCV = 1 eV
+E dzlzl fzlz4o e Flq +g+. e dzl¤ee+ ¤ g"l ¤+.
l cv= I |oJs +41= tr]-q=r+
^l-olE
a.a[e+ E4l $^dg +4U 4,ol :B 7A9E+.
1eV= 1.602x 10-'el
oleloJ ¤E ^Lde dzFS;f+ +e__E 4*zlql +e+ ql
Rb KNa
Ek
r.! 2.30 eV
--:
K tlJ
5 2.25 eY ---:
K
6
2.09 eV
5
Uo 6
oE
oI hv @ hv @
K
RJ
Ho
g -sr+sl
=7l' (a) (b)
"J^l-=ltc9 T.!5*, v
BE ArlE ¤B6f7l 9ldHî= "J^l'=^ldol rE TIE+oil
.r.al 7A.10
:stcl.
lal 7A.e Bd a4q1 96H^1 -d I^1.= FlGlLleZl olzlE :r Hlall6l= oilqxlsl
BxlE Elol?ltrt.I' 8r-161|0t (a) Brl'E ollLl^l7f
=+o_++EJ sq+qot 6fq, olttl{ Llg=
I-r#E.4t-e tlE+elE-^lC= o._e+El Erl.= gtr+ 6.Ealrl Eq.. (b) B^l.e_l 011L1^l7t E^1.= =+
=+oilr+-d ollLj^l= gÎ=^ldsl =01.9
LllEIE Heq, 0l qEq qlLl^l7l Bdrlsl EEi ollLlr|e LfElurl.
BE^lsl3E T]E+oil n[a[ !fl{o+
=7l-drl.
230 7 2trlE
trIEEJ
@ #t=q E"'EtitEtt trEfzttl
ul^Jol 305nmoJ +^ld *zlzl t.zzevE g
=r+9-E+4
HJ=^lZl4. ol E^l'g
E "llulzl= 714 dzl¤ ++e-s+El d
4-= Flq4s_zll 6J + 9l= +ÎdE slql +tlg al4I6L
q4.
r.alg AIA: za.toal9 @=hv-Exg} *ol LzlL v-cl7
E +4le+ +qd qlolEl= ol+6}q ol ++el oJ6J+E- Ni
=g
4l&'J+. %rd a4g Eq qlq ^1, + 4zlzl qBE qq
r*^l ?*r 4+ fl{4e-zl"J 6l+ Ell gs+ qlq^l fA 7A.1't Davisson-Germer t:d. qe eEo-e+q EII g= LletllTlE
^l= f, gepll qat^j Eaqol LlEl'Ll-7lE
E y-in= <Dlho14(Erc=0). ol {=+ <}¤- ol+atE r}dz}
17l-Eltr !:doil
6E,^1V!E S^llElcl =+-d =d,
LfEfL[7lE 61.=
= LlElL.lcl. ^1P?l
,J¤ql gs+ 4q iiltlg 4l&'J + 9l+. =8=
HJ=ql gsq! trts-$ ?JLI. SJol$ trl"E+l
=,li d5$5
(b)
=ol "JdzI qel r+¤ olEol s*E"J t+qq *e+ {ol $u}ole q
v=c/).
o hv-Eu c Ek B.trt= ^84E .J Li*H 43 olulq :zzl +^lEl*.g S"l
v min
T ---- 7,- h
*+. rq+ oJEJolTI rl*- + Hli6trt= ^J4g aJ 4elzlE
tr}{^l "&%'-=g "JsA + fl= alql ++s rl-e=$ pol flfl'}. r+zl"J le2s{ql ¤6}|Tl ¤eg Î%IE=E 4q+ ol
gtrl Eril t4lg *B6iz]l Eol¤olzl ?*g + Srll "JEB.r+. +,
Clinton Davisson4 Lester GermerTl "l ae4"J ¤Eg 619
hû
v.in
c c
- clA- Eklh- IIA- Enlhc
olEe 44 4rlE+Et 4^l7l q¤g+= dE ar+=
=ql,
gflH rlal rrqlî ¤¤.J HIe+
4,o14(-zH 7A.11). Ei+zl9
+qd
olîl qlolEl= Bq=4. dz}9 ¤-F qlqzl= + ?ol fltre EIe-] AE ^J.ll 9l= Eillql q6H^J "Jq+= t
94 eq d ¤^Jol4. Davisson4 Germer9 d¤9 qg9 A+iolfl=
trll, :f olf+ +E6l gE= +q q^+ac^d
Er. = 1 .77 eY x(\.602x10-'e Iev-' ) = 2.83...x10-'' I ^leel ^lEE
g*lfl6J 44zl qq AE¤ flzlflEol +++rll 9r ol E
tr|4^J E-ol E]¤BE q6Jg al*.zl ull¤iolfl4. oavisson4 Germer
+= "JoJol, +i Ezl, r4r +CzI)g 7l-zl
Ek 2.83...x10-'e J
= 1.42...x10tm-r =ntr "J"J"lE(a
Tc (6.626xt0j4 J s)x (2.998 x I 08 * r-' ) ¤e¤. HI+61fl=Ell, ol o3-u3ol$E ffi--l$rl. ceg +
qU+= e+= gfl'}. ole+ 4el Hl+ql El{l c.p. rhomson
E dz} ¤"1 S3 +H-Ig Fr+6IE sl¤ ¤+= gA
E- ll 7=U305nm= 3.27. .. x 106 m-tol+. tr14^1, ^tdg
619+
Lû= = 5.40X10-7m
olq+ ffi-ojujol ol6C3 olul de Broglieoll E6ll^jE q
L AE {A qflH+ aY Pz+Eql d¤ ¤¤* p=mu(mZ
? sa0nmoJ4. "J"Jol9 ?*, :24 a_ uY r +q). zlzla- *4olE "J"Jol
olzl+ql oI,_14 qE $"JolE rl-94 *3 oe Brogtie E
xlTlg7l TN2 ut*ol t65nmoJ z}9dg qB =,.+ql 4 =
z{l^loe. +qzl. +t}g 714 4o1+r gE6}Hr+.
q+B.trlr-l r.z+rvrm s-,9 449 *= 4zlzl Flq+Sq.
ul^Jol 265nmoJ irltlq +ÎCg "l+*g oI Hq+s= ^h
)"- -p
de Broslie SZIÎ (7A.11)
dzlE +qg 4l4I6Iq?+.
[DIS¤/.8
dB +Eed¤ Ttzla ¤+6I= "J"JolE 5}g t+*s
r_s
= =
*=+E 4"14. A^14 EiilEg q+ +F+9 z*zl qlB
=
ql(rEel e* qEql) L?-lrll ¤+g qlqlE Eltlol e r
=
+ $.9 etr + 4eq tr|4^l qÊ+Î ^deg 44421
=g
7A g[fq:*el 7lg 231
?+E+ ol A=-+bC ql+ql rl{E+e 44i= zl{ zllE Broglie +41^l b-htpL*q q-q=4 ag +48 Eg + 9l+.
4^14 E41E ^dAg ¤H6l-= Ell ol¤¤ ti$.'J 1o14. f
"Jzlq4g flzi+ tsz}e+ ee azlol 4g "l^14 alql ql6H L-
h
(2m,eL,Q)'t'
^J"J
4+^le 'Js7I 9l= Lol4.
¤zl.ll4 gs* qlolEle+ 7lE
^J+{szl "J+)E Bq +
E@ deBrosrierlElqeE
H q.q=+ eg #ol +9trt.
C^l¤ dzl9l4 40kvE iilHl¤ il-= +q 7l+^l7lH ol
4zlzl g"Itl* ulAlg z)fluul? L
6.626x10-34 )s
{2 x (9. 109 x I 0-3' kg) x (1.602 x I 0-'e c) x (4.0 x I 0n V)}"'
r.elE AIB de Broglie +4149 ol+6tglH dz}9 d
=6.1x10-'2 m
B e5+g "J3I"F oJ4. ol4g 4lt}6lq$ qfl¤ iI
zl+= dzl-br dq= e*t g a+ e^0 "JE-9 ^0gl l1.tPmol+.
=
HzlE E=trI= ^L¤g ol+6lloh +4. r4r 7l+ol ¤-
# olqql *4 " e 7l-+g dzl-L dxl- q¤Hee
^J
\} ^ldql^J= Eg "ilHzlzt d+ +5- "llHzl E*_!m!/_ gtlg ilillE
Etrl4 ,llel e4+ e.= -trE +z= 44
flzm,tr qq, u}4^J 01 fnm,* eLQe+ gz11 51. d¤ {+ Ell(EB tse)
s=JpE +g + ?14. *ql^le+ eol qlolElE dolBzl "l+¤4.
aql +4 4l&g + ++. ++1# ilulg qlE rvc=ll TlTlBT|7A3 (a) 300K91^J kTe+ E"J6J Hd ¤-F qlLJ
4 t I= l kg *' s-'9 S4lE ol+6J4. zl= *= +cxlE rle}4 o) 80km h-'-e. Bol"zlE ¤eJ
ol sTgoJ Ellq4*el Eltlg 4l4}4q+.
y44, rle|,tJ
f l2m,-etO= ¤H p-(2m"eg)'''zl de rr¤-olXz'g (q) 'urdgzt (B) :-E
=01
T}ILJ=
=9'-d
tr1. E'_i{l= E= E}+9 +^l-dg H}=6}7lE a}r $;61zls. a} a 4. tsd ag= _zd E4alql^l El-trror+ a4l d4llrl {z}zl
Eilltrl-. +^l¤ ojulol($z})s +C¤ 4.o e }|ZI "JEflt}.
= g
J2. * +qd d54E dzizlzJ$ ollulzl$ E¤+{9a"J - s. dz} 4¤g rd E4qq14 ojujole ,J+lR'J dzl¤ oe
+6J+. Broslie +qxl= u}t}e-l u}s+ rJol -EZI "J=fltrt
Ez{l*lo e
tr3. flzI 4 Bzl .¤lEHg gÎ+ *zlzl 9lHzlE ES+4 tr 6. trI.+SJol o|fr¤g "J"J"le+ t+tE F zHH"l g6Jg+=
o}_e-_trtrJ
+t'J + gl¤¤ Bq=q. TI]HS .J^l6l-= 1o14.
=g,Ej^l=
,(lzl
oe. ,\l
'1 +4 4Ha
Wien9 B zl trn,**T = 2,9xlo-3 mK 7A.r
Stefan-Boltzmann Hz] ¤(T)=constant xT4 7/'.3

gill +^l 71'6
Planck EE4 p(7,7) = Snhc l{Lt (e"'/1t7 -l)}
p(v,T) = 8nhv3 /{c3(e/"''tl -l)}
jlill g+*q SqI Einstein 4l C,..(T)= 3Rl,(T) Einstein $-E-: 0E = hvlk 7A.8
fr.(T) = (eF lrl 1e0''2r /(eer-/r -1))2
Bohr9 d54 aa LE=hv 7/..9
%td a4 Eu= hv- (D @= "J q++ 74.t0

de Broglie +al^l ), = hlp ,t= c¤ gE*olpoJ "J"Jolg Elt 7A.tl
EEJ lo 6l^.
7B tr, t-E E!
@ schrodinger lrt de Brostie zJ4lllel

> ol E4= u[+.= ol8 otatA{
fl^lelExl ?Joil ?l= E^lel d¤ 0l6t|dlE r1l =Jg'El
tr|,=-Br'+ otlo
TIEEE 7l* x1l86lq, tr-l+ olEe-l Etrl. zl.+Erll ¤+61-= g"JolE ulHl¤ qlqzl= qq^J+ 0ol+.
^l^lg =C0l
> TllLJ
I V(x)=0olq, q+^l Schrodinger ^l(zn.t^l)ol 4*4 ?"1
".4C
Zlel E= Eq-qt4 dEg Schrodinger g8{= gclll= ¤+
trlE-sr+ +oll Eol?,trl. =clAJ
d
tv 2mE
dx' tt' V
> gg.:d qHl rl^l
2lrlEg L|e4l -d rEq-+e_l EEg g0l0t EIILHEE 7A). E4l 1 xffi oJulolql ql+ schrtidinge. +19 4
ol 6|]E v=cos kxol4, olag qqlgl + 9ttri
^lE "t4e} ?"1
d'rl, d2 cosf,x
d;r' d-r'
k2 coskx - -k'V
rdq+ql^l= "Ja+ 4s
oJEJolTI ?llEE ula| ol=" aJ
=
+. "JzlqEql^l= +.a ^JEllel g"J"lE trl.E_:*+ l/(sÎ
tr14^l -k2=-2mElffolq, u|4,tJ tr+s'=r+ ?ol ¤4
ol)s E^l6l+Ell, ol13 +zlEI 9zl t*l d +rJql q4gl
4. "J"J"19 glile+ gE%F ¤-el E-qqLA AE7l ol rl-E 6J+
o=(T)"
+ql EEtqq fl+.
el¤ ol A+q 9lHzlE Bd qlqzl+olq, ol "J"Jol9 d¤
e**r+ p-ft2m(=.9 zn9 EI4zI9 t4 elE $4lE zlzl
78.1 SclT rodinger Al p + cl* +417I CB{L+.
1926LJql Erwin SchrodingerE"Jel9 alE ,l-Eoe-+E +61- zm(p'?lzm)
U2
_P
k-
+ 9l= +,JA49 zll"Jalflq. + ^ltql q4 H6l-zl ?+= h2 -h
(qaq *ulzt "J¤61rfl #zl9E) 4l "Jql^J olluJzl EE7l7l
ul4rJ C¤ $F%IS p= khzl qr4.
r lzJ_fl ¤+¤ 6I= a=d: rz"J "J"Jolql ,}]6J trl_S4 Ag AI
Z-+tr Schrtrdi nger (HJE)49 xll "Jal94
EJAI} ut+e-E q^++
Schrodinger l (78.1) EHB+ 7zll4 o + '4slu|';r- +qL4 oE sineo14 cosin 6Jf
##+ve)ry=Ev ^lrJ-+g
-+ ++B + 9l+ r?-l6}q cos kxE. kxzl2nvJrt 6zlB ull"I
9zlrJ h=hl2n(h-crossEE h-barqr 9l=tri)= "JzlqEql 4 Azlz| SEq: +4r E + 9l+.+ele q4^l kt-2n
ol+q= H¤E Planck tfol4, v(x)ts 9l 7I Elq, El+^J k_2nt7ol4. :z4a}.l d¤ g+=*g rL5.o6L
^l ¤Elolal trel
rl x9l^19 "J"Jol9 ElHl¤ glHxl4. trlH]¤ qlLlzle+ Etl +E +eI4 qg-q ?ol *41S4.
9lHxlE .J6IH dill qlqzlz[ s]tr + "l dafl a]9 "l 2nhh
^lE P=klt= )"^2n-
"J"JolE Bll ¤jE"4 ¤+qzl ?*sE ?] ¤+(+ql Hil+rll
v
7
¤ aol+). Schrodinser !g "JzlE+E el zlts z|{ola}r olag ulE de Broglie +41^lol+. irl-+,tJ Schrodinger !3
E. + ?lErJL ot4ql^J zl+ ¤t¤ oli ojujolE a+ ol
^l de Broglie +4144 6Jilq= "llE *=qr E + 9ltrl
oJ de Broglie +41^l(EB ze;4
"Jil6J+= ag EAI 9E :
EIRC¤ ++g + 9lg 4"14.
78 trl.E-:# 233
7B,,2 Elorn 6J|4 qE - lvl'dx

lvl
+ql= "J,Jol9 +lzlql +EL AET} qs
=lqq}4
qq fl+. 6J gEql^J9 dzlzl +Î+9 T1+E zll#g r
+^l+E rilzls+ a+= +Îrlql +* r+*- olE4 +^t6}rll
t
Max Bornc ol
^ll#ol("JzlE4
oe
"J6l]^l) z ¤qql^J
zl-= EaB +Eg 444oF oJ+r S4I6Ifl+. :-41. :zE
tr}g-4 4rol all!a|.fl+.
,J
u x x+dx
I
Born aH4:
"+tEL+9 fa 78.1 trlE:Er+ yE t trEt|ilsl xllBlrv EE lyrl2)ol *E "J-=.zl
Elqot --ltrl= Eoll^l qE I!=olal'r E + ?Itr|. +l^l xOl glts dx gE Zloll^l
"J"Jol9 ffi¤.fzl "JEel qI d x"ll^J vil+ 4k {- g"Jol='JA-g qEe lrlrl'zdxotl Hlell:dtr|. 0l qE "JE= ol r=Joll s7ll,t'l
* zlzlfl re+ x+dx,tl-ololl,tj :z oJuiolS gAg 'loC LlElLJ nl +el EgtE Tlxla- LlElLHflrf.
rdr{l ulullafQ(:zB zs.r). o ^49
=|g-ol I rlrl
c0
¤zl,tl lrylr=VlVE +i+71 H 7l-bCg rEl6J A4

V7l zoll 9=_ol-4, :_4al-¤ y(rle 444"t ++ r?]a Born oll
4rglqzlel t4 14= Eolr{) ffio;47} ¤6.J+(coskxe} t 49 q-q-l} *ol 444"F oJ4(rB 78.2).
g)olH I rlzl '- vlol g+.
q¤(+qBid9)"lo e I trl'Z l/aolel qHlC "J"Jolg +E6J+71- "JEg 6J d rql^J v/e +qd o}], ,
I yl'?dxzl
g *= +E "JE+(lzl-fl 4el a+). u]'sr" g-* rtr z;illE 4
ql ?l= +i{ dt=dxd)dz +ql^l r !|ujolrl ge¤
"li
q¤C I vzl'dt9l Blql6JEi.
g 1=olep +E+. 3zl¤ql^J zlf_E.rll ¤s"g + gl= "J
u3o11{1tr^J q +99 dz}19 A+ql= ul-=." g$zl 4& *,y, ol A+ lwlr? yAol,9 q{idg T}xlq rH.6J+ zlill=
ttTJol3t2E qflCg zrur{m-3t2e)r 7v-e- ++l).
Born9 6]]4 "JBg vtTl *4 Lkg ,*+ 4*(:-41 "JHlzl
-E.,\'A o + E^+7I q= a+)= gEjg ¤szl s.+. + -E= *ql
-+J
.<J lvl'Z ¤+olr Ea 9"1 9zl ?*zl ollE"l4.

+ii= +g_r+ eg "JH}^l
oE_ +ElE + ?14.
7I *q tkE= +^+)g +=+a 6il^l qH 4dz1"J 9"1
z-x*v *= 49 otul+.v+E++el ¤rlilE zll#"J "J9 <t"Jol
=
{zlrJ i=\-lol+.¤f ,E'24 4i +E'g ++4q zld4"J 9"lE 7}zlq, ul^=."grfz} 3".|4 "J"J g
E?-lqt4
Re(z)tr.-*^lq}+. ols] ulfalal ¤+ lP.'24 -olf 5-g'g 93 s-5 oJIIJolTt tsag +Eol +g gg"lr*(:_H zn.l1.
+44q Im(z)-tr- -E^l6J+. z9 8o4 E=^+ rY r4-o--4 rf rel+ "J4 +E ¤qg 7Ld +.iq tolt flzI
o
ol iE -i_tr HIE 4,o14. $$ ffiorl Îolql EA Adol+ t1-41 Adg "Jq+4 g

z*=x-if
f ?lzl trIEql q+61 +9-+ rJ44"J gelE 7*v,-L+.
aI4 olt9 zld"ll,tl sol g + !lsq, "l+loJ
ze+ d9i-E #g e _E^l6lA z9 xtp trEfiil+r.
I zl2o *ql^l} q¤- I=JE S,tl 6ol g+. relr+ irl-trro 6L-A7I 0ol q
.J+. zel rq C9 :_41 i2=_19 ole" 6|fl q+4 ag
Aalzl +g+. z
l"l' = z*z = (x + ty)(x - ry) = x' + y'
4lB e{^lE dfolq, "Je-l fzl-S4. ol EE]|ilts lzle dz

-tr. -E^l6Iq 4+4 ?"1 #"ttl4. r
dY
t' (x'
l
zl= (z* z)t = + y' )t''
x Y
+^+ql ++ q Î^ll+ rll¤+ Eq Tcel 4ttz}9 ^&al a4 78.2 3il-fl 8?-Oll,t'l ffig4g Born9 ,JEe-+ 6t|46lE, gEq E
169 E-olel. ,oll 9l^l-d +tr| e^ dx=dxdydz +oll^j SJol= "JZ-g +# r flr0L'.j9
I r4l'?0lcl dtE E-d'Joll u all:d4'.
I
234 7 zfl'E
+^1 qel +lilql^J= qsE+q ao EH! Eqd dql^l

ol-
tr|5-Bt+ =I
Eq Ag a7l4 +ul +q4 rjzlzl gag ffiol 7H]]+

q ++= ag +E_,6]-q4. g_e_E 6}dg dzl-b oje-tr
6}dg qq Eqq, nlEl^J 4 zlztslql^l Ea$ ffiol
q *4"14.
xl7lE7l7B.1 alxl .llHzl d-qq ?lb H.*olg+q d
zlel Ef="El+= s-zrtaofl Hl46J4. ol ol89 zlzlt fl$
lg 78.3 tr|.=-Er+E +E= Eal+4 9ol=,*^l E=tr|.. 0l trI.= 4l4}g slEolal{4. ol A4= q$rll ^J46}L+?
-Ef+sl gE gErlgE Bqe ^ltrE?l
_E= 5g-sr q= Es= LfEfL.lrH+E
yp.l IF= o_e +olrlq q7 |î= BgtE gtr + LlElLHfltrf).
=E= hleEs h {ziaA-$b: ss'E
*(qltr-^J +d flzl-9 qe.g+q E4 ¤qd *)r+ ola (a) ETet

=
ol 0g Er+61+ d3 4g+= ag aAl +Eollot t4. ol 9zlql4 gelel ^J
"J"J ,/E Schrodinger 49 ¤l 6114r alE
FzlE olrle{-L +trI-. uf^s." a}fz} 0¤. ]eo 46}zl ?*98^l 0 o + Ng #t
rurar E+ 6H7I 84. "lel+ ++4 C¤3 zn.t
E d=6I= *9 aizl g|=tr}. rEl4q
"l-4r+r +9 E= 6}ql v7l Eqflzl rll+ql qB tr-+ qlzlolE
cos kxE kxTl hE $ C+H|]E !E *ql^J tllq5 {zltltvl
^l
E+ ^J4lg + ?lzl ollEol+. ole+ aol iil-5.6J+E gEq
EElfzI Gg E" r+6J+), 4-E" *f rk| trtq$ 4zl ?*e4, z;lf .JzluJfr zfffirll HEIÎvJ + 9l+= ag +E "JEE
x-+-ol Eql q4 0o + B tso14. ulellql-rll 5-+ EH4loll ltA2al 7Jt+a g + glEg
lrnl2oll ,f,
E+Et 8+ Ng +6H^J Bg + 9l+= 19 9"le}4.

@ olEB+Ea[^{ C+sl tr-+= +6IEjH +d oJtrJolz} d.r ¤qql^J ga¤
=lzl 9lHzl ^JEHql flb +A flz}9 dzlql 4t
q--e"61 +Eg c+3rlg Nr= ole"6[{ (Nry'XNy)dxe +
^tdg f E6}]oF ++(NC Aizl ¤+). rzlr
i- {'rouql Hlrll++. ¤zlrl ao3 tfolr rg qoE+ qdq= ol
Elel 4 44. tu) q +d4 o) q o +Pq oo"J ,l4ql fl= q¤g dal +tql ea^l q+6}l +E rol qqo} ql+(+'J"J
Pul 6y=1.0pm3ol +¤. ¤q +ql^J ol {z}z} E-aB ti olzl
"lHz}"ll 9lg +Eol rol 9"lot ++)= ^tdg
ol+6J
ql4 +Bg 4l&61q4. ol +rl= flzI 4s t'-e_sE trll +. + fqr4-oE.'lg4 ?"1 !"loi qI+.
+ 4Le +q+.
,'l*r *rydx-r (78.2)
r.{p| +C 'lltl- gqe flxI 4s tle-sE tr11+
^l¤l
zlzl qlEoil ol gq ?lqlqE. yzy H6Izl ?t=+r H - trI4^l
ol dql^lel +E "JE:(v/71 ¤folo+ l)q+ rE6l+
P4 av E #6LH +E P"ll Hlqld-= {}g Eg + 9t+. N I -* ql/2
(78.3)
1 P* l6Vo1O yP * cz'raolrJ. (J -'.'t'd')

trI+^J ol 4E"l +++ zl(E'-+E 'xll# 4Erol)¤. *E+H
+ A+ql EF 6V= l.0pm:olr{. (a) QqlrJi r=0ol
A++ ^J+ Ng +61-r" r?-l6}q +
=ol
q, trI+^], A+gIÎ4
ll4. ol4l+El=.trq} flBol H. +, flzll4 le C+s+¤
P". e0 x (1.0p-') = I x (1.0pm3) = 1.0pm3 6lzll g+. ol{l*flE ol Elql $fz| oJul
^Fs" =
rlr49l ErJElq q'g'=l} z;$ zzl$ EI+^lZl+r eJ4aJ4(t
o) ++El "JgE
q_o HJr6Je-e. r=ao oJz trqC dql^J il-flel 4$.
trIgq ?ol ¤4.
=
Pn e2 x (1.0pm3) =0.14... x (1.0pm3) =0.14pm3 ll*v.v a* -' (78.4a)
,r|4rJ + +EE ulE r.olo.l4=7.1o14. 3il-tlE A+ql= +S aag "J+^lrJ trll ul-=."srfzl C+EI
g+.
78 trl.E--d+ 235
dxdvd'z=r (7B.4b) "JEE +d Sqq Aaî zl+6llot qlq. rald}q riHl 4l

J -J* I--r*tv ql q6ll^-l= xla] x' oJ"J"lE g-ag $E pzl rl-g-
^Lolql^l
ol aae +¤-4 ztol zlpolAl +Ei471E qI+. 4 B"l B+.
Jr", dr= I (78.4c) r= lo,'fu(*)l'a,

Ef= [r^|fl Bq] (7B.s)
{zlrJ dtE 46Jd +q a +olq, 4+g dill +z}ql aa

4"14. E@ qE 76t71
E7l E uls+ 4"lzl Lil +4 +L+_E_ +g 3l
78.2q]]J
@ trhE-B+el tr'+trI
dz}9 A+El (2tL)tt2sn(rcxtl)olr+.
^-l-"llqzl
+4 qr.+s= +i+ g se +Hl dflqE^1, zlE+ y-y4e\ x=Lt2 dzl¤ ga6J qgg +6rq4.
lnmel znm rl-olol:q {olE f ufol= +"lElol+. Îololl^l
t+q1
a.fl-g zs.s^lr+ C+3tl v+f,-*+E ol+6ll^J +C
EBg ol+6IH ol {rrf,_E-9 alz]-9lHzl dzl-b
gEql^l^l¤l
u1tr.o6}
f sin(rxlt)-tr. +r}8 + fleq, tg +]=+89 2olol4. dzl¤ gag qEg'I44"F ++. gs+ 4
e+El +6Iq4.
# zlE dS ol8a}ts g+.
r.al-g ,l.lEI ol ul-=" grf} lz|flolu + 7B.4ael 4+ Eol 7B.s^lql el6ll^J ol sE*q+4abl +48 + 91trI.
^l
ol lolslzll 6l-= o3z| Ng +6IH S4. ol irlE" qI+E d+ 4E T.2
fol= + vr=Vo1r+.g,qoJ 4Eg zlE ¤g ol+6}q4. e=l !" ,in'tn* t L) dx

A+3rl ^J+ Ng oleo op N sin(rxlt)-tr
=ol
+4d+. 4E El4= +E9 z3ol {ill"il ¤i"} 6tE_E rElH C++ trl+r+ {."1 ¤4.
x=O*El x=Lttzlzl Btrl. :aBlH,
,=?( *_sn(2rwlr)\"'_z(L L r\
4ET.2 '=Tlz )1,^= r[.z- 8
- o+ 4n
)=o'4oe
IV.','o'=''F4; =1N'L +4 0l ¤qoil^-l dzl¤ gaEt q¤e * +sozl g+.

s}=."grfz} C+EI qElH ol 4$ol lol qqot TlTl 87178.3 zlzl $zl7B.2ql^l zl4+ ule] pol oJ
6JtrI. +
iNzL_tol qqo} ++. EI+^J, +l=Ftr E¤e] dzlql q1g $g=etr +g qlq4
=+lel
A+El (2ll)tt2sn(nxlL)olr+. y-714e+. x-LlT Al
,= (;)"' olql^-l dzl¤ gd$ q$g +6Iq4.
sz'o.E
tr++^J A+El trl-Sr+ e+.
,=(?)''"i.7 (b) trl.=-d+oil Tlollx!= EIE

+ql Born9 "l4$g B"l¤"lzl floll.<J| ffi
rl-.=ro6J+ql
+4 + r/pl q$Idg 1/Aol',rol4,
1ol zjololE trI+^l .J+qlq g4{} z}a1lop q}+ *d :z 4xll {l*$ u}
^llEg
lE qUC9 v4olz| 9"1 lil-fl SE Eqe.^l zlB6I
EE}fzI + +tL+ ¤qql^J +,t}tr}]s 9zl ?*ot"t sorn oll
+. alol ¤-ql¤+= Aol+. ol 64 o + "J6ll^J schrodinge, ll9
\l7lB7t7B.2 +ge +Eq E/q.tr- +g qqzl +flql r*9 zl-e" d 6l]Eol ^lle.lg+. . ++4 o _e 7l!" 6J 6llEE tF
'll+
ul-FE++= sn(2nxtL)olr+. ol El+¤- c+E+ 6lq+. B+= +6JEllE g&6}q, f46}q E"]qL4?l Eql^J olE
zn(Ilz)=N:E
g Eol-="J + S= aol+. schrodinge' rl9 6]lE 6ql= q
L + Aql^J E ol^JE lvtl'4k* +r}.11= aE flg + 9t
$- 1"14. "J"JolE qE dql^l tsA$ ffiol f zlzl ol,tj-
++6J +zI gqql^l zlE gaB +Eg 4l.rI6I3JH +E el {}g +48 f S.o t, + Born oH4ts"l 4BaI4E
"l4el
236 7 erÊ
Et+Ee B"h=g + Strt {tAE 4 dql^J +"J {tg zl4"l

qL+= ol allEg r}s"gL+= +"J-ft"l"+"t 6J+a "J6J+.
q) q)
schrttdinger 49:z zlzllzl qlql+ elzJ9 +qL4 xlle|$ zffi
+. + ol !g 24t.9 trl+ HIA^lols +1q-=" g-;4 zzl E6J+ (a) (b)
ql q+++= dql^J) ol zlol qq^l+ cB6lelE d2ttid*o)

EHdIrll C99"l"F 6J+. 2zI Ee-+7I EE6I4] Cqqel
w tl.t
E rz} se+z} E4"let"t 6J+. 4 Er.+zI ?l++6llot +4. .
aJfz} ¤+4"J trIEI r lzl. se].+z} EE6Lr| AE g + 9l (c) (d)
aol+. 4 Et+zI ql"J+ H+= +4qlH * g+. aal7B.4 E4El aZE trJ=1171= trlE:Bt+="J -:1EEtrt. (a) P-d-d EE
=
dill4 " + zlaflz1= 4lEg +T4 ?.ol se+ E== +4:d61.tr|'. (b) 171 -Bt+71. o[t-loe P4:g[l-cl'. (c)
0ll,\1 +UrEHTl
o
E+40 I [r-l e +4:d6ltl'. @) r- ) lZ7 17 | EE+40 lge +496El'.
0
B + flc(:zB 78.4).
+++ gqql^l +,*EllE Elzl g*"I"F 6J+. u!

ool zlzl gHI4 oE "JEel {}E
al9
B"J<l"l 9olot 6J+. <[- R 9-]afl,<J Schrodinger
"il=g
6o:u
"llulzl EE 714 + H+.
¤44"1ts+"t +4. W< Hh+q "J6iE "J"Jol==g 5e6J ql
J-
H ,lo
lil E-¤.+(zl$zl)zl ¤+4olF+r +tr|. R Ll^l"Jg 714 + ileq, r+zl ?+g ufl= :z ul^="g$$ol
E?-lolzl " + -d+B + s.+ =_-,
trlHl¤ +4.J +-Jql +olel EEg +r}8 trll=(E
"llHzlz}
I zo"llrl ¤Bg t}z}4 "J"Jol EBql^Je+ eg) +lel E ultfll+ql zlaHzl| zllffi ql+ql $,JolE qlq al= "J
^ll zL*L qlrL
TllEol 4*qzl ?*=+. ''l
-
-L-:-1.
¤4 a"FE gFql 46J schrodinger al9 El, +lql^J g4

(c) BillEt 6J 6llE¤ dq6rH 6l+q= qlHzl#
^llEg ffi,r.171=
Hle +lql^l Azllel xllo$l$ ql+61 g46lq, oli$ ¤+^l +6J + gltrl.
T]ILJ=
=s-d
tr r. 6J4lE EIEoB+= r 4lq +* E= qq4 C!-E zlzla- D s. ulst",$fz[ EtEt *g trI= r ^]l+el 4E"l tol qqot
el= +q}4 q+++. 6J+.
A 2. Schrodinger alg ulEC++E 4lt}6l-= r'll ol*9E z tr 6. atg ¤4ol?+o} 6}jr" gLzlel +6J6J g
17F+t
^13
zt
"lE *441"14. E.ll^-l .?tI4zI 9zl ?J:ot"F 6'Iq, E.6J ¤+4oJ zlgTl=
tr 3. BornE 6fl4q1 qsE + Aq^Jel +E "JE= r dql^lE zt4"t d4.
tFE" C+E zll#ql Hlqla.J+. a 7. olluJzlz[ "]z]e+ q= ae- u]s." g4z[ "J4rl4o] 6l+ ++
A 4. uttrl= s|=r"gr-fz| oS zl{Y dol4. ad ullgol4.
=s-d^l=
.Al
oEzl ,.l
-1 +^l 4tra
rJ-+S Schr<idinger zl -(h2 I 2m)(d2 Vl I di) + V(x) ry = Eyr ril-?l 41. 7B,T
^l
A+EI !v.v dr=, a *rJql aa 4+ 7B.k
xra\ x, oJ,J"l$ g-4o3 ffi r=J-'l.t,{rN'd, lil-fl ¤q 7F..5

^Plql
. +zlg 4l:. eE 7D,7F:r-qr se"llr.l +E aolq
Eq 7c Etlr1g1 7l'zJ=aJ
¤&zI H= "Jzlqqlql^J 5tr6J E6Jg olEull, le^ll7l

> ol EEE ull+,= ol.F
trl-EEr+= gE6l 611461-48 olaoe+q 5qtrtE gE= Eot
9 f*zl. William Hamilton9 ol+g ulrJ namilton EtFl
i4 4l *E4. rd9q}g +4 ¤4= gd^lA=
uamiltong
'J + llolot Etrt ?$|sqtE q|,$A r.EqqtE q|,$$ trlE
ql, olae +q "Jzlqqr-g +4p+61.= q 4qlql 4.o1s.4.
# 9lgq, ol*lEt itol= flrtLl-Exl-e_l 76et ¤tr= 0l6t|6l= ql
rJ+rEolrl". hamilton ¤&z|. 4lE ¤+ qlqzle+ trlHI¤ 9lHzls+9 Et
?l diil qlHzlql qls"6|= ¤&z|4. 7c.rb^l +HE Ezll -J
> EqC 7ilLJ
trlEEt+ +oll Lt|*E Eq-qf^l EHts hermite E+t^lsl Tlrtlil=
e ElHl¤ qqzlolu _+ aa]] 6J{2i} Ea.J+ql Hlell6}= 6Dg
Zlti-etoeul + ?ltl. HA-et {lHzl{l q+$u ¤tzlzt lolot B aol+.
"JHI4 " e. + EL+ql fltzlz} zle" 6IH /iltr_S E}+zI Lt
=ol'J
> =Je.il qHl rl^l g+.+
Al9 SEtl= rlEB#e SC6l T\AE + ?{eq(E4 za1, qg
gEts tr|.=-Br'+el xiltsi 3710il Hleilettl= ag +^l6t|0t e+tl. (¤4]z].)taJf)=(^]l ++)
A+ql q+^Ji ol nfzl Eflel Et+q tr-+E #6J a
Î
r+ gg + 9t+. olal6J ^deg +4.11= StlzIeI El+e+e-l
r+¤.Et+: "J"Jol9 t-qql4 Ce(qAql r ojujolel +l7l eEle "JzlEEql^J ElJ*61 ¤:s6I+.
+ 3-5%+)ql +6J s.= ¤EE LllE6Ir. fl4. :_4-tr Born9
6]l4B(E9 ze)g ol.o" 6[S r f]zlql ++ ctrE Eg + gl zttrJEt oll 7c.1
zlEJ rlÊ.o6J++:z ol99 eEtr LllE6Ir_ 919q, ol$$ qlE^J ¤+Izl-d/&= illtle-= EI+= x"il *dlrJ IrIE6I
¤q4= "JB$$ ol Eqql^J ="+6}rll g 1o14. 4= *"Jql, ol $tlzITI oJ+ sin argl 4L+B o113,r.lltr.S
Eif a cos axTl +g+. rBl+ dldxzl e-*ql ¤ÎB trI]=
7C.1 Etlxl -a r*71+s=ql, "lag Bql EL+q+ tl.i -aE #*
/.a+ rJtr+.
Schrodinger !$ qL a"l+ tr|q=$ eg ZIA6J g-s ++g
+ ?t+.
(a) a+rl tJ8^l
ftv =nV, Etl^lE9 ScnroOinser (7C.1a)
^l 49 trl+4 ag
zC.1a^19 Schrodinger E-tr- +48 + 9l_q.
ol 4¤- +¤.4 a.3 rz}91 Schroding.r 44 ul:zaH E4. H, ol19 r+il ,J8+l"l4l +r+.
(¤tlzt)(El.+)=(+zl "JzDx(t4 6-J+) oC.za)
##+vl)rtr-Ev
r+il "JC^lql^lL ¤&zl¤ EL+q ++^lzl4 t.J+ql
rBlH r-].o-4 ag e+= erll g+(ril-gel a+) + ^J+E ++ Arlrl-+gtrI. "JHl4e + ¤&zl¤ Oe't4
Ll]r tr-+ flxl¤ are +E]-r-llE a+il *crlol q-g=4 e3
H--##+v(x) Hamillon Etl^l (7C.1b)
'ZJa+:=E 84.
A1q1o1z1-d=+r gl=tr1)= ElxpJql, ¤41zlt 6J+ql+ r+^l U84
QV =rrl, (7c.2b)
++4 ¤&g +q6}ril al= 4"14. ol a+E s4}g y4 z
z| ro}a5- a6}r ¤zlgl4 _rtzDmg #qI +s a_ 41+E vl olq+ +4]^l.tl^J= EL+ ,t= ¤tlz} lzg-l l*A++I +=
ei v1r1etre1 #ql+ Elal;E dol4. q, a)= r r+EL+e+ g+g r+il+a +++. olqil +q
238 7 zrÊ
ql qsH
'l¤4 E"l ¤ + 9l+.
7c.2a4* dqqlel +41= 0l+6ll^l ol HA qqzlE lz.lgq A+
(¤{}zD (r+EL+) = (r+71 ) x (l+a;-; (7C.2c)
E*-finm4 4ol de +E=JE ++e +4U+. qTlql+
7c3^Jel &ql 46J ¤&4¤ Bq=q.r+lH
¤&zl-E a+.J+oll a[$
tr++^J 7C.1a^19 yrz| hamilton i, b,
aftzlzl Eql a+il trC4"l4. El+^l Schrodinger 49 E | (h d )f4 d ')__ fr' d'
i"k-_ 2rn[ (7c.s)
q= ag'4lql ql+ hamitton ¤tlz}9 r+ile+ a+EL+= i d, d*)\i )- 2mdx,
+6l"= 7.'+ +r+. dill qlqzlql q+ gÎzL 4

tr+{^J hamilton $.llzl; ffi
d¤ +Et+"14 {zl ffiz} EHIEe+ +Z +d 7ls"t 4l 4 B"l ¤+.
e] CAE¤ 7Et+aJol+r 6}=rll, + qqzlql q¤-61+
¤.tlzlzl 9lF"l 4E z}*++=q 4s" 6lt ¤&xI
hamilton n=iu+v - ##+v(r) Hamilton Etl^|. 0C.6)
EE 9l+. 7+7+E olBl* S&zlg2ql qalrJ hv-roy*?J?
a+zl B{al"l ¤zHaI{ q^q=r+ +e EE= *=+. ¤zlrl v(r)= 4'Jq! gE EIHI¤ qlqzlql 46J ¤,tlzi4
=E
uJêo alfzf z].$aaJ= f/oll tr}]86IE fltxl-lz9 ]L+EL+
"J rql= r ll+E'-+ql q¤-61-+
j1+ilzf ulE ^da oq W 7et+Jq zt=E
+d er+e+ A+ ul-=."grfzl (a) rlx) -dk e+ (b) fir)=ekoJ zffi ojujolst
dB eF"*g +6|q4.
"Jzlqqr-3 +rJ 4tr- 7I+=%Fql 4s" 6l+ ¤&4E "JEr
olq^J r ¤{Iz}el r+il= ar|.$eE^J d+ ¤4= ql+ r.al-g ,/"ll+ d¤ e*=*ql 4+61+ fl4}zH7c.3
^l:d
r.l\e ftlrLrl=l-:r -r 2-l= -z rl*LrI n.l.ol tJ=ll(1l slE*L
. -Lr a tyl_1 -1 .6-yj
ali ol$olQ. ._1
)¤ -r-1'L1'.1./ | t' t -={E ::-:'.lyl"1
+ql+ AF+E EEI Ar+7I +s-E(+ z+il ,Jd^lol q
(o) Etxl UETl H), ol *izl rl++*E <lol S4.
"Jzlqqr-ql^l= 6J 7lE Tlaql q+^J +qd ,I++"Jql q Eol @) vli-ek"J 4l'
f,.{+ ¤&zl-3 "JE7ll gti zBil

7t+++3 +4r]l= g&z}= r+q-rl ag dB +
+lzle+ i.v -+*=+#=4xi,t.* -ffiv
=J ¤&xlE zlzl:il_ "JE+.
E"
ol r.+il7} +ttfioJ -a+il Bla^lol+. ¤Eo "d¤-+c

x= xx ^ hd E^l (7c.3)
^lg
6[H &=+kfioJ Z]ol ul-g 4"14.
P -id-r Etl^le_l
(b) yfix)-qk9 4l'
xq tI9 +lilql 4+61+ ¤tlzl-b xE #al'b a(irl^trio6l
=, l.8il
+ql+)oljr" x+ql Eq+ dB +F%Lql qs" 6l-= s&zl-b
dV
htie+x9l *t s-stf1ulÊe-;E)e+e-1 #4 a+ ^fi
P,V=T d.r _- Ld"-'u
i drc = |x(-ik).-* - frw
7G^lE cEE ol+6IH += ++ 7l++%FEql q6J g
&zl¤ EIE + gl+. qlE^J trlHl¤ "ilHzlz} v(x)=t11,p+ rJ
ol A+ql= r+ilzl -knolq, trI+^J p,_+trrtzl S4. (a)
e irlQ]¤ .llHzl.ll 4El ¤&zlz| p,9aiQl 6l-z} q E A+q= +FEJol "JE <I& zlzl4 "J"Jolzl +xft9=
=E
7l^1 t# tl+tr}(+ql Hl]+al 94zl"J ol qfl¤e Ezl +ql
o.J6Ir O)E A+qlE "J"JolzI t144g- 6;ql+.
rJg flxl¤q 1]t¤ +4.11= 4,o14). x"il 4t ¤4}zlt x +4 "JzlEqq + 5de +E +ÊL+=
#61-= a,olt= e, fql ql6J ¤&zl* xE *aE olol.<l E +l6IE ¤+- %'-6.J:g Hl-E+= 4"14. rq4q ul^=."$fz|
=
xE #6l+ 4olo + t¤. #61-= A+ rJE+ trI+^l +krt'ql q ¤d+olB(cos kxel e3) t"+ +4+7I E"J,*
so6lt Stlzlt q+4 ?ol ¤4. 7l qq eFel d4l %r-'Jol s.4l g+.
V(x)-!k,x'x (7c.4) \l7lg.717C.1 cos k*-E 7l+E]= "J"JolE H

Tl S 9lHxlE +6Iq4.
dzll"ll ilq^J= #C +s= ^J*-oE #d oE olaNap ,t].
w71S1r4=,tg:6
s"q}4. EIE BTI qlHzl.fl 4eL S&zl-=
"JEEIH *d L
7C Etlrtel TtE=uJ 23e
r-o 7= S
EL
-=,
tse ET.l EE oilH^l <i
,to-0
UO
=- H
<l- Eor",
fio
,-*e +E,
W
*e
L
H Ed 3E ollLl^ t{
Ek
---:
K
5
6 V
x
x
feJ 7C.1 "J"Jolsl "JE ET.! 3E ollLl^l= trlE:Br+sl gE
=EE+E1
AAfEf + ?tr|. 0l raJql^l= + trlEEf+= L[ElLHfl=ql, ql4-Lf +=sl feJ 7C.3 trlEJl¤ ollL1Il7f QE++E -BFd[| l #{qq g=ia-e-e. oJ86l"Zl
q.EEr+= qlA-d Tiec;Ee Ed ollLj^l= LlElL.lrI.
= A= "Jts "J"Jolel trI5:Er+. Eill ollLlrl= g86tqe ETI ollLl^l EK= 9E
5.-o-e ola= rulE T.!5 qalAl u|Efl+el $$ EaH:.Jtr;.
=7[6ltsEil, =EE
BTI qlqzl tstxl-3 +4.11: 7c.s^lg schrodinger
^lel E"*fE 6l]46}r:z Eo"hB ql+6}= ql +l+q} ?d.olz]. ¤
+ +s6J dg +44r 9l+. ++ql^J ,*'J+q 2il E6J+
rE'-+9 +E CEE: +EiU+. 4 271E6J+zl r+L +.qlE^J d4 qqzl= "JC6tzl"J qfl¤ qlq4zl x4 G
= ,Iql Ir++ ai6}= "J"Jol9 rl.'"6JfE rj{a}lEzf. "ltrllE
ag q?-l6}rll EL+. E*+(rH zc.r). trt+^l ql
#qzl.
ir+*.J+= +e BA qlLlzloll all$rli Loll, E-V=E.7I g+9e+El 9E3- s_E A++ ?zLat{, uI4
"l+ +¤el j4¤6J+= xzl frzl$q qq q ql46J ++3 7}4ot qI
{$ qEel rl-Er6}-AL- *g Hd qqzloll afl$ap 4ol4 ^J
r. E + 9l+. +(rB 7c.3). r4r r
+1Lg B{ "llulzlql ql6J A^14 7l
yId-EL+el +Eg
"JHI49E +lxlql tr}+ Hfl+(re
olz[ f,z[$f$ er^q]+. E]+^J
"l r]-E"E]+= reql +4
ql4+ +¤g *= *ol$ qq^Jq B4l
7c.2). ul^s."si-fzl H 6J+e+ Hl+4Al B"J aolq, dxlle z}^llq} 4hlg 6l]BH
gF qlqxlql 7lq= 6lr" ul^sr"st-fzL *g qeg + 9l+.
"llHxlzI dill = "14"1 Îd"Jg
+E¤ *= *ql^J= dill eE qlqzlql 4Ig 7lol. +tr+.
++q= "J"Jolg et- qlq 4z 7+ ¤q_oE+qE E_= + (c) nermite Ettrt
f, qlq 44 21"1. B+EI 4o14. tr++^J B+ + 7}++"d=ql El]8d-= olzlqq4 ¤4}4¤g E+ q]+61
Eol +eE gtl}olTl-}f BTf qq 4E zl4 4,"141 ,.J4 6J ++4 ol=* hermite $4lzlep=E
^deg zlzl:n- flbql,
a3
6J + 9l+. Bd qqzlql qlql +zl4el zl¤E
"J"J +E 9i 4. hermite EttrlE q^q=r+ eg +4lE uJf;lzl| ¤4IzI+.
r +E 9lzl"J({$ol - u"J fE ?ll" s *,4 n
g"J oJ,
"J +E glzl ull5"ll) r ¤+g

6J^J
"JE #g *=+. lv: ov, ar -{!v,. oty, d,r}. ol = E I
E d iEEl (7c.7)
+3 +Eol t+ BA qlqzloll afl$afu olB]6J +41= r]

Eq TBql^J ¤HqI ute+ *"1 J...at* dal +¤ *a H+E
dill +zI gqql 444 4E6l+ 4"14.
ts= ETI 3E oilLl^l 9lzl ¤+lz(xx)E A+ql= q-S Aol ul4$ q+
)lq ^lql^Je+
+ +E qlzl¤9 +^l= trl-g4E Hl-E + ?l_o t: e "l ¤tI
zF= qlstrlECol4.
S
<F
!w: *v, ac - !w1xty,"M={Jw,. *ry, ar][.

,rbo
W
H |_JA
ETI EE oilLlxl
)lq trIzl"+ +!g QFy- rr9 S4lE ole"d AI++. dB gF%F
¤tlzlel a+ql= Irl+6110}.J ++E +^lE zl*6l Hl¤ +
x Hzl rllEql olaol ql=IrlE^dol4= a¤. +E6lElH a+
aal7c.2 d=El= g'Jolel E{] oilLl^l= 5 7lq= +4-6I+.
qlal-J =r.loll =T.!tr|"5-Er+el
EJE^lotlr|- 7lq=
'JE-d 10lrl. Bq= 0l tse Et] otlLl^l=
=Eq
6tq, 'Jg BqP 4e 7lq= -Lrrl.
=Eol
2t 0 7 ?rIE
Alol ?tr 7C.1 cE ffiaJ Etlxle! oll=ElE¤

ot"Jflri. zc.t44 oll=ul=,!el AEE ol*al¤ "lE9 I
*aJfz} ¤++= ag +E6J + 9l+
¤zlrJ B "Je q-g +41= 6E6l-= 4"14.
Jvi i.v'a, ={!r; i,v,drY

-.tr{
oo
9zlrl fi.z tc.z49 ¤tlzt4. ol +41. +E6IaJH r+s=rl *d E9s}4l +a "lEi3 Y* :
,r,n+ r4;E wE 4484.
ee Y E 4EB(ElquIel t^] rs)g "l*uilo} ++. 4H zc.zalol ffi$ ?ol ¤4.
dg/dx
av,a'=?f-A%:* tw. o,yar={Jw. ovarl

Jw:
0
q+ql= vrl fl*zl g2E l+61+011 azl a r.+il+r.
df/dx
olzll ol +41= f^lel
fg L--, ^J46Jtrt. a ory=rvdr_ ^J46J+.
fr
= I. -^_
ly .* ll/.
-
-irfiry-* s_E3_r+ g+E + 4+ql+ 4+^lzl4. :24H,
E¤: 4-E.6J+59 1= *oo$ q4+ VIWi7Y x=aoo9l. x=-@ Jw. ,rya, ={lv. ,,,ar}.
ql^J E"J {,te--e +e6IE-E ol a4 6J3 ool s4. uI
^]el r+zl= 4E zls +e-E 4tr8 + 9l= tr"++. ,'I4^1,
!w: i.w, a, = -? L-w,

!# d, = {? !:-v; ff a.l. , lw. yd,r ={a lw.,,,at} = a* Iw.a,
-az| tsErll, ol?g. ar
q e.
=$'; i'v'd'I zE
4Eg {l4lrlz14.
A^qE af
,I ¤+"Jg +44= 4"14.
ol ar+= HtE agql +E"lElH aol+. trIzl"+ F^lql^Jb
Ql)*= y,&|. i*=-iel +41= ol+619.+. (d) EIaC
wiwiZ d tzlql aa^l 4++ 4*zl q+r+ Aol 0ol q
hermite Stzl= r J.+zlzt .J^J df"lzl tr{+ql,
+
= H Vt* yizl EIE*+a EqI+.
af =ap17l trllEql "Jzlq+ql^J "JB f $."1 +s_6I+. +17,1
+, ¤+=Jol4, "llulxlE 4if4 alfzl B + s.o o + E lW:W,ar=0, i*/oJ 4l ^lizd
t8ell (7c.8)
E zls+"*g +a6IE dfzl 84. zls=.JE +a e4=

allZl S4}ztq a+il +9 6}Ltoltrtr olE l#^l= d++ + ^llEE EL+Eol ¤+Elq$.l "l + "Jelel ; aJfz[ .<J
ilEtrlel 8*l ts tl tl r{tl

TE.-E
"JzlE+q^l= + trolal E}+ /(x)e} h@)e 4 ff{l.)td/)a* !f as= fs-lsaf

EE 4Eol zh+ +48+. ol+l+ 4Ee h@)E 4E 'J+
g(r)9E*+tr. H7, th(x1-4g1x)ldxtr H;r +6I+ 9l+. qe^J xe-o*A 4+g $4roflez1. o1 a+ql= f(x)-xol
qlE^l ft(x)=aolg glx)-!fol4. :4H ol 4Eg +E 4 4, ul4rJ df(x)ldx-tolI dglx)ldx-e-*o14, ul4rJ g@)-
EEg ol+6lq +ts + 9l+. -(rla)e-*o14. :z4a}¤,
99
f dgldx f --? fr-- arrax
Ir#0.=*-!sffa. r-\
xe-* dx = x
A
-er-e I ld-x
J aJa
HlBg +H9 4E"l g+9 4Es-4 flrll +B + *q
"l =-xe-^ I xe-* e-N
, *aJ e-^dx=- aa'
n
- - , *COnStant
"t ol+g + ?l+. ol 'rlHC Eal rl-q=4 ,J"l se+6ll^l +
4E + 91tr1.
7c Eurlel'7l"zJ=eJ 241
e qts ol Er.+E¤ 4EE+il AllE?+r 6J+.hermite

zl:za3
ol 99"F qFI. ol ul^="gtfi-s- t"l* 9luJxlgl q*6I
S&zls=3 +-q-lt ag +,qq} CAg ++U+. ol grfz} zlj/Elg +"J6Lqq
E aEol+. + uf-=."
îE
hermite ¤tial-el tolel r+ilql ql*6}= ol-s=o aL-r'=- o
zli16J4.
^l-+- + WiVt-stn(2nxlL)sn(nxlL)g d *Aq AA^J zl
=9
ol Ceg qls"lE^del 4412c.t4) C9E ol+4q +Bg
+ iltrt. $El x=+*tlzl 4Eg 6110} 6l-zlEJ x=0r} x=r Îol9 B
q +r-ql^lE ul-s."grfz| sol Eltr + ol gq "J"ll^J"J 4+
g 6IH g+. gs+ 4+Eg xle. ¤.il +e+ 9l+.
@ hernrite EtFlq r?-d+q 4E¤
s*zloE r+Ei+olr :a a-+7171 ,j(+, hw- @ivi), Eol ol 4ts+ x[tr- ¤9 4E r.sE o]$a[r. 6=)ntfi\
wzl
b-ntL* g+.+
r4il y/,+ tol6J r+il al,E a+EL+(a, hty,-o);t{;, a;* +l6l-E
a)4_t 6|zI. rqE 7c.74oJ +e-$ ?"1 84. sin (3nxl[)lt

J'rir,
(znx I L)sin (nrll) *=W#1,',, --z@tD-ll, -0
[v: ,,w, at ={[vi ,,,y,dr].
ol 4l4}ql^lE sin nnTl n=0, !1, +2,..."J oll O"l ¤+E
r+zl= r}iolo+ 4E zls +le-e qlBE + 9l+. gEI 4¤- ole" a|94. ol + EL+= trl+^] .r.Je zlL*4.
olq+ olEg ¤+olqftermite ¤&ÎE -a+ilols e) ul4
TlTl Tc7t 7C.2 cl*ge +g El¤.e-+= l//3=
ai=ar,ol4. trI+^J, =+19
^f sn (3nxtl)ol+. V =srn(nxlt)* W=sin(3nxlt)q + ++
,, lvi v 1dr = ,,{!r; ,tr, drf z| r.JE 4jr++= ag +"J61q4.
g=xp(1 1 nt)urs (z I rue )*. ,g
rl
++q= {lr;w,dr| =lw,v:dr9 *4lzt dB6}E-tr +l^l
ql ol +41= ol**+.
ot,[Vi V 1 dr = r,tV ivi dr, r[r].<J @) i - at)[Wi V, dr =o 7C.2 TlEIlrl

=dul
rflql + r+il= ezl g:9 rlE vi-@i+0o14 Trl+^l
tzLgql^J gt$= zI-+ g"Jolol hamilton ¤tl{* o}4e+
lvtvfr-ool qqoF 6J+. 1*4zl +E6IEIH ule] pol ol
+L+.
+ a+E}++ zlj/6Jr+
H---##
¤&xl-b hermite ¤t}z}4("lag ,l++eJ"J ql
hamilton
ol $ulol3 ElHl¤E zllEg tszl ?*z SE" 6}zl Ell$ql 'zI
Hzloll 4s"6LE ¤tlzlolxlql hamilton fl&zt9 ql_etrlEC
e Ee4 o.e +Eol S+). trl4^l + r+++z1 t"lel ql # "J"Jol'+a 6}q, v@)_0ol+. ol ¤tlz}g l#elfzt
pr(x)=cos /cr+L ag drll q"Jg + 9t+
Hzl"ll El]+61+ 4,"148 ol + l*etfz| zl:zal"p rJ+ zl
r^dg ol+6IH 4lt $eql^l gg +e-l 4Ei$ ,ll4^14
HwQ) = -!$.ort = t-Lrorlr*
f = e ol ceg "Jzl-qqql^J rllt6.l +e6l-+. E zlj/^Jg zm ox zm
EI+ AELE(E4^ e)+¤.7Jq\E4^ il)ql^l +d4 qBg
ol ul^="s+ql 4+61-= qlqzl Ph22m2 r+il glC^19 I
++. + +H6l4l cEEl= ai"l4. rq+ r+zl g:9 zt
$z1o1p
++%FE 9lg + 9l+ trl-S 9lb cos k7l dB ¤+* ¤&zt
slEdq el r+6J+zl-"tH¤- Eq+= 4,"14.
=fl
xf& 44 ,=04 x=1 ,tlololl,<J olf,olE-$ zllEg ts
. h dul ft dcoskr kfi
- "J"Jolql Eil+ 7l^bql +EEL+sy vr=sin(nrlr)4 i.V@)=i*=i- =-isinkx (7C.e)
ryr--sn(2nxlL)o1qlc}. gE *ql^l= ol Yl-tr'o6J+=ol 0

"l ol alf(sin kn)e| 4lHq Etf(cos kx)zl
49 +Hg ^Je.
+
2t+2 7 gtrlE
ElEtrtel 8*l to Eulerg!

^l
+4+ z=x + i/= E-ABElol4r +s= ¤ts{}fl d o e "l +41= ol+6tH z-r(cos4+isin/)E q+4 ?"1 448
+48 + gl4. ol BEq^1ts Re(z)E r+ tlql, relr rm(z) + ?l+.
=
F tr-"ll +4utril^rllil 1). rBql +4u utq Eol ,4 z= reio
/= del +4+S= +4tllq, Et x-rcos/e| y-r stn4olo
-E ol q-+fE trl+4 ?ol *=Is +48 + gt+. El¤ sio = cos(-o)+ isin(-4i)=6os/ -isin/el +41= "l+6}q
=E trl*r+ eg + +*+ +41^lg eg + 9l+
z-r(cos|+isin@)
cos@ - ](eio + s-io; sin@ = -*i(e'o - e-io)
?+
0y ,gI *"1 ol-T= L 4s_er.l z9 trJlol4r *4. yt*
=tarl@olIr + q-S +4lE ol+6}q +rls gg +EI'j + 4+Ag +als gs +4'}]H tl+ ¤&g 6].= ql ¤461
el+. 7il ol+6J + 91trI. qls^J +4lsB +4u + +^+E #g
q^q=+ ?"1 ¤4.
,=(*t + y')''' =lzl Q=arctanl
o ))
z rz, = (rre'o' )( rreio' ) = r{2ei(@t+
lx,iyl ol *dg +iBHq +4U z)ol t-fl171 2"14.

N
r
-E
f.,f,
0
N
,+0
Re(z) -E
r1
^flli! o,
4a;3 ol+* TI1L +++ ^.lE 6I+= trh.q'=r+ ¤9 Euter 0
Re(z)
^lol+. Lrll*|2
eio=cos0+isin@
eE+ :/+il ,Je^lol olq+. ol +eq 9"l=- "JoJol9 +++g qBl H H}+6ll^J +aiR
"J"Jole-li+EElfz} t ¤&zlE a$aJfz} olB oll= g trl +e q+9 HI3 oJEJolTI p*-+kh\ (lg +4Ll]r +
r g&zlql E}]s"6l^= d¤ol +eg *g ?*21 *8I4. :24 "lzl t}g p,=-khq <Ig +48 4ol4:. 1o14. ¤zlriE
4 cosine e'kg[ e='k9]9 dE e-Et: cos kx=](eik e'ke| eikTl d¤ aoJql+ f,f,6J Tlol$ 617l qlgql + #E
+e-ikr)e-tr +48 + 9l9qf44z}9 zl4 t09 EoI4),1 trl +tehzl E"J6lrll +Ei+= 4,ol4.d¤ sejoll $a]],<1 q5
q^J gE=Je Sd6l EgC"l
"lq+. H7l Tcrql^J -BoJ Ht E4 cos krcE+El gg + 9l= .ll¤+ oJEJolTf +x %}a}4 -r
4 2lol ol + zl+ 6J+= zJzJ ag^l7l +khq _khoJ i,E a HJ-6Je-_tr
AEe-E+E_ol e+= AE.SoltrI.
fre].fE"l+. q+^l olEg eB6Izl"J <lol tol6J +F* qL ¤tzl.q r+.J+Eq d¤ a6Je__e. +4u +E6J+
ql Eilg" 6r= o$Eol4 ultEt+ cos krE 24le) qJEio d-+ dkx qL 1"14 ole+ gg *4 " + 6]l46J + 9l+. ++i6L^
=
4 e-tu9 Edol4a 6Iq, olag q+4 ?ol 44t4. i "JHI4 o-e +q=4 eg dB aaJs-tr. +49 + 9t+.
+ikx
V=e +e-tu
V=c,V,*czVz*...=LrrVr r+Er+Eg CE eEr (7C.10)
dE g5aJol dE EEAJOI
+knE goJol -kIrE goJol
¤zlrJ ciE fz1(+A+el T]ft-Col 9l=) 4lfoll_
'/o=
+
c 4tI ,l++elql 4+61*= ¤tlz} gzE tloltl a+6-J+E
r gH}4ee d¤ ¤El"lt'6J'E+ cl "JII4"J +qq. CB a'*e ol+. "Jelel EL+= {tr 4olE vlo$E 5q paJe_e. +4.J
gE 7l-6 Bdg "J6tq, $ol4
ax+by+.'.(q7l^J a4 b, ...8 t[+)e+ A.$
I 6l+ 42 a=b=.. .= toJ d¤ a*o14. + flsq, olfl Eql^J ol qL 6Jf rlro# eJd AllE+
^llEE
7c E+lxlel TlEJ=aJ 243
r.6J+. rE6Lq +lE 'll¤¤ "Jzlqo|4 " e 'l¤rl ?"1 "J +zlql 4s"6|b ul¤.6J+Eolrtr- zljr'6}q, q+^l +He-l
6J fz| ?14. ,!lrlle+ 9lrll 4¤+ 0ol+. trl+^j,
¤&zI 7I+++g * tH"J +A4

sz.tl a1]'J'alt (O) = lrrl,ar+lcrl2a,
E 6Aq Tlqq+ qL 6J
va9 r.+zlzl-484.
{r
ol
rlo
9"lE "JflE +Aql^J ,}]H +AaJ 4lul-4 ar,ol4
gHq +Cg E6]l^J qL 6J 5A+ a-+^l7l Rr ^lE
razl {gzl"J aaol +48 +=g lc, l2oll razl 44.f- 4
+48 q¤e
rlol
dB a6J +9 6I'J 4lf9 z]* il

nlru
Eg I crlrol g+= 4o14. trI=+^l ¤+ilb ol + r+zl=
( lcf l)q1 Hlql6J+. olE"l gHE dflql^J +48 +E"J+4 zffiafi.q o.J6J 4
eLzI*="J o= ql+61 qq H +eg 1ug trlE B+il= ol ¤+.+
¤tz} oE7lEHil+r.61-q, @)e -E^l*tri. a+El +E.o6l B+il=(alol +48 ffi)xa1
+ vE ¤ ull= oE zBlzlE ++r+ ee 4E-e-E 41&++ + (razl +48 ffi)xar,
Tltll^l [E+trlE (7C.11)

rq6}q zlqlil=,llfl +C6J qlE r+il= "JHE +4 4
(o)--
lv.ovar trl.E-st+. !e.ll ffi zlzlul-+ ¤++ a ?Jr+. olag HLtr 7c.11^lr+ E
.Jfl L]]+oltrl-.
ol eel= ul^=."gtfz} ¤&zl- Oq + l-?gi#ola u1-5:at--^
zI ¤&ztel a+EL+EE +e.J q+ ¤B+tr}.

E@ TtEnitet aht
@ Et}xtel TlEtlil= LIEILtlts
^l
z)o\zl r"J rzl-fl
^JÎ +ql 9i= dz\Tl 44 =+lq 9lg
ollg q-sr" 6l*e+p+)= r}x} 4glrJ y v_(2tL)U2 sin(nxll)
¤&zI lzE l+-J+ V/71 a-+71 c,E zl4 trlt=, + eV= rV oll rlz| +'!l^J= 0ol+. ol dzl-9 +l^lel ¤+z.l= 4l&
"J trll= zlr)lzlzl r+q- r+ ?J:LI.
4q+.
av oE 8+ vE 87efE ,l
rtalg flilel B+il= +lzlql 4*61+ 9&x}(x
(o)=
!v. ov dr --
!w. aw d T =(t) [w.va T =A)
^lB
E *:6l+ a)E TlEllTle+ 84. (r)9 +6IEIE zc.rralg
h=i=xxB saa 4Bg +dJ]oF 6J+
ol
^lel
9"lE Ce 32= +e6l$ +5.e-+7I sz9 r+oJ+
olTl trll$q +¤ts oll"I4E"J6J ollL+eq q4^J H "lel +6l-4= +lzl9 Tlqil= tr|s=r+ ?JE+.
++q{g ullel B+zls- 6/l g+= 4,"14.

=ol
zl+ (c++¤) ii+JE"E'-+= stlzl lzg + r.+6J+E dB <*>=Jiv.irydx ¤zlrl ,=('r)'''ri"T * i--xx
a.J* 4,"141 ^J46IzI.rElE trigr+ ge ar+= eg +
gltr+. ol4Eg r=04 x=I ^lolql^l +61-H 9r}. ol gq H+ql
Eltifl-r-z} oo1r.1. z|=. ¤9 4E rn9 ol+4q+.
^l=
1o7 = J krW r+ c rry )* i)Q1y, + c,ry r)dr relH q-q=r+ ae a+= gg + fl+.
atVt o\vz
4Er.r 1
)* c,QV, + c, {)ty dr
= ltrrv,tc,v ,
<.>=1@=il=r,
r) dt
= !GrV,*crV r)*(c,@,V,+cria,;y
+1 ol p=|i dz}9 +lil= q+61 F*e q+ql aa^l
+C6IE r B+<lol tlz}g +Col gtrl= 4,9 9"1d4.
= cl cro), !V; W,dt +c\ ,ra, IV! V rdr rfl+ ol ul^=" $fi ,"ll 4s" 6lt ¤4}zlel l**fzt
^}olE tr"lt <19
0 0
olrlzl uIEq +¤6J ol1"t4 0<x<L
+cf c! cra,, J V * V dr +Elg 4"14.
crro,
IWi W rAt +
\l7lg.717c.3 "l dz}9 ¤t zll# +lil ¤)g +6Iq
zIzH9 ul^s."gifz|{+e+qol ?lzl ull$ql +HE a+ + 4 +.zlE ¤9 zlB r.t27l gse. 4"14.
tsg -s+ lol gtrl. E v,* r42t hermite ¤4IzI9 /J-olal r.
zTLtZ'\= lr4 - i).2 '6
244 7 zr^l,E
l^LAq^J g'Jole_l Bt Btl qlHzlts 7c.srl o + +qzl

E 9&zI9 zl'|]il+. trl-{î +*4 B"l ¤ + 9l+.
(r- ) =l],r * intyd,x
=- #Lr # * (7C.12) S
<l-
;ibo
yl-s.o¤'+4 zl&zlql +* B#ile+
"l e4= H4l qlqzlTl W
H g"J0lel
e+= *ql^JE a!+E q.J^14++ 4o14. 4 u}s."s}+z| +lil
qlqal q¤g ,*a(+ d2vldiol r+) E aJf zli-llz| fl uf^=."
Zl(tr}4î vrE a-L+)g *= ¤ge H4i qq 4 +1Ezlql glil, x

TlqE 6J+. = aal7c.4 glil7l.BE{6lXl EEEI= goJoIE trl.E-:B}+= g"Jolsl +liloll^1u
qaldtll+= Tl+= 2;aa 0lslel*ol^1= T.!+01 001 Etrl.
7C.3 flal
=E#¤
ul-=." gtfz]- y=e'k}. p,9 l+"J+g^l :a r+il} +kftol4. 4,9 "J"J"lzI$dal i.zls}q= ag 9"1t4. ols+ ?-ol
"J
olA+E oJtrJolTI
"JC+ CB +F"d¤ 7|zlr.
ulolz[Sdfl +zlc]qzl= 6]zlq] r +Fe"]ql +{} Atr=
9l¤¤ +QU+ rBl+ "JoJolel +lzl= ol4 "Jzii +E 'JE SA6l Srll ¤+.= +F+9 +C6tH +Aq= +++ 4t
+ VrVAI Hlzll6}q, q+^J 9"dolE eik-E 7l+6IE EL+ +E qL 6}+ql Eilg"6l+ ai"l 44+al El=tr]l, q¤
q¤ I]JE= (sifr-r;*.i,LI-e-iAxeikr- e-ift.{+iLr- e0= I gl Hl elld-trI-. Hl. lol 44BzlE ql+g +E fl+. tr|4î "J"J"l9 +lilE 4
ll4 q+
gETl--EFxZFll ql6ll^J +96I+. + g"Jol
"5"1-H
q6l "J a+qE(++61 *g +E* r+-J+# 6a^1il
E 9lzl= Sd6l {l+ol "J q= 4o14. -sqI6l-z}E "J"Jol9 9"1t4) r gF+3 dq ql+6J + flril E+
&F*"1 g"J6ir| "J+ flqH glil= el+++ fl+ r ol pffi a%r4 oE +4u {ol ffi zlol4.
ol Lll¤+ trls=4 ?3 Heisenberso! E+88 flal9 * ql
A,prA,q>-)tt Heisenbers9 E+trd 3al (7C.13a)
_E_^J,
"l fl?-l= "Jzlq+el ,Itr-+Eql 4+ +E 6I++.
¤zlrJ 4+ql ¤fl+ dB gF=+9 'E+dd'olr., A4
LprY
P{0
g k0_ ol + tr-ql^Jel +lzlE Eqcc"ltrt. ol 'E+a^d'Ee- z
"J"J"l9 ¤+.d:4 +lzl. E+ F^14 o+
=
E"l-Ezl Cq6}rll E^l6J += S+. Effi#, B+ilE+qel Bt 4l# Eilolq r+q=4 ?ol H"J6lzl
o-
Tol =
C9q= 45o14.
E+A^d gel= ral ojulolel +lil. g"J6irll .J trll= +E Lpq= lQi> - (pr)'l''' Lq - {(q') - (q)'}''' (7c.13b)
%Fg A-d g + H+= Ag .ft6J+. ol E+ 4¤-$ "l-r_Ie+ e

ol ¤Eg + 9ttr1.
"J"J "J"Jolzl-q-C¤ +lilE. ilzlg ullt.:z ffialf| :
*ql^l"J 7.11 :7- e.lel xqlrJb ool 9"loF ql+(rH 7c.4).
olfl+ ylE.6J+= "tg Et
+E aE+ ++(sine cosine EL+) 2
+e^lvlAv+, E.= Ag q+olzl"J Bg e*x 6J+=- +e \

= e) "JE
5
,tlfl,tJ(dk=cos + 9l+. HI+l "f"IH
k;r + isin k*ollr <F
,16o
21
'*3 tl-ol+ dB s=JE qEEL+- d¤ ¤ql rlzlH 9l W
H
46trll +zlc].¤ tr|.+ol{r. +s= + 9l+.

"JE
A+E aEI EL+= +A^l7lH eI ¤qql aa qd v]-trro 6L
fz| 49+(rH 7c.s). r4+ +eq: izl ¤ ?lxl, x

7I6IH ol$ zllzfl i4+Eq "JE gq+ ¤.el ¤E= :ral 7c.s 9lil7l0t|E|l6l-zl EgEl= g¤Jolel trl-=--Ef+= Tl1el "JE
îolql =rl'E
EtrI $d6J tdol "JqB + glq^J gd q ql?-l6J u}4"l trl'8E trlE-tsf+7|'Ee tdrl"8^ll ,Jd= Ee.z;55
=EE
aolal-r +
=
gltrl'. q-e.l +{+coil E?] +^D7l q
+lil= gEbl-zl El^l"J
+g + 9lq. r?-l6Lq +6J61 gg +E CE.slE"sriE "l r =aE|=
EtlTIE =7|."-lE
SJoIE FJol +8+61'xl Etrl'. tEdl +^l+E SJol9 trtE
!P+6J +4d EoJE ulaol ufegul1, o1 :st+E'J=alE
+6IE ++61 ?t6l
trt="..JP ¤E^l4ot:"E1..
=+
7C Etlrlgl TJ3J+_J 2t+5
"J"J"l9 Sd6l qC4oJS(Aq= 0) 7C.r3a.lql E6ll

+17171 QrQrV * {)rQrty 7ls+B=el .sEd QC.14)
xl Lpu-*rl. q= ++ql s.eq, i+4^-l ¤.E.rlol sd6l E
q¤6iTl+. HlqlE + +q *le+ +F+g g"J6l-ril "J ull= g+ 6&g hr7 Hz.l S,tI^lvla_ olq^J r
Ar+qlq O,g ¤
(Lpr-o) ol + ^J9 flilT} sd6l Eq¤6ll4o} ++(A4=*). 4}^l7l= aoll. e=4 aJ$ olsl Rlql +e-E g4lg rlzl4
zc.13a^19 p* qY +'J +Z} "J6Jql 4+ aol+. u|4rJ , aolr+ F ¤tl4-= ¤44 o _e 4I+^lzf, Ertlzl rEq +
=
+ ^J9 +lile+ ol +ql ¤flqL eE=Je Eqac fl49 ztl ^Jql
E=B trll=(ol ^lql^Je+ ?ol) olEol Tlaol olq+r
Eg Bzl"J x* t9 +lile+/+olLi z+ql ¤B.J +FE F "J6J+. O,rl orE ^J"leL +^JE 4L+^lag.
ql
^J"lq! ¤4
+ag xllEg *zl g:E4. 7| +s= a45 +q=4 u."1 C99= EErh= zlzlr. 44
^14
u+.
@ =qacratqoe
t.o 99 A+g 4= 6J HlqillE +qg l pm sr H+l *.ll lQ,Qrl= Qr{2r- hrh, -a.#xl t8e-ll (7C.15)
^J "J
+ glqr 6IzI. ol ulalzllel $lilE EqCCg al4 +lzle+d¤ g5-%Fql ql+ CEE ol+6IH ol rQlzlE Bq
tr $ulz| qbzl 4l4I6Lq+. 6J <lg +g + 91tri.
a.e{g J.l¤l ApE +qE Eqcc Luz ole" 6}{ mAu

E+q +.J+. r?-lI. zC.13a^19 Lp\q-lh¤ A,q=t7160 uel EElrt
g E-e EL+q^l +l7lg 4i E+ac 7,*4. rl3
lkg -, s-rE ol8d4. ^q= +lzle+ eE"d=ql 46.J ¤tlzEol zlilol "iLl+= ag(r4
6Iq ^JB4 E+4= a¤-) oJolETl +16l-0l *4 ifi,1it. E
+lilE 4^ B+cce q+4 +r+. &^la e4ql+ xE #6J4)= rl-5.o 6P- rrgl ¤^}rl4EzI.
=ot
tt
Lq= hdw
z*Lu xPxVl =xx1 *
_ 1.055x10-r4ls _ _
2x(1.0x10" kg;xltxlo* ms-') ""^"
=5x10_26m
q-Sql= ii. p$ u1-5.or-^ql g&^lz) pffi E4(? rE
# ¤4lzl +4lq^JE g$ACg Sdfl +^16ll
_Et= ++ A4qlq p,= ¤4I^l{+)
E ¤+. rq+ ¤elol dz} c.sael a"J qlb +qE Eq d(fg)ldx =(df /dx)g+f (dg/dx)
As_zl ?.rl4s +lzlel E+aE7I flz}9 zle=Br+E ¤ h d(xw\

d q + 914(ee *4 " -e 4l&6IH Lq-60mzl fl
=
P_xV = T-d- i('..#)
+).
E4 49 aail EB6l r+eq, EI+^J ol + E&zl^b zI
r;l7l8.7l7C..4 z)olzl 2rooJ 1zl-fl gq +q 9l= dzl ^lr+
+Iol olq+. ol + il¤ 7a[-BH olg :ffi]z[E deg
al4+ $"I"JuJ +qel EqCCg zlzlflyul? as? 016]]B + 9lg 4o14.
^lE
=
sohr Hlxlg sz.spm-=.^1, zooi *Î49 e +A gz}9 zl
E4A+. li,i)yt = ii,V - i,iw =-!, =ittV, trI4^l li,i,lV =rttrtr
ol +Al= q{ u1^="o-t-:- rr"ll 4rtl4+ CB6l-q, E}+^J ol

r-suqo0E:E
jr¤+zl-L q+4 Bol 44'J + 9l+.
HeisenbergE E+AC g?-l= 7c.t3a^l-B+= +Jd q gHI li,i)-rt, 9l^lel EEB Ec^tel -a.sxl (7c.16)
4"J aolq. ol 49 gH4 7El=aJol4r +s= E= 7l+

+=* tlql 4+B+. ^JE4 7}++elg r=q ¤tlzl.g c¤
zc.rorl9 n+lzl-L "J4qEr+ adqql zI
$ zlzlt- Cqg+. +ill4-e-E "J5lH, F zlS+* o,+ o, ^l-olE =84
ol$ +Elull'- Aol+r. B + ?lg Ctre E|]+61 +s6J
z| 1te4ol q4E olE9 ¤tzlzt q+ +4lE q}4rl4ot ^l
ol+.
"l n+tzl-L "JzlEqLg z|{olrp B + gls
El+. ^r¤/J.
4, zc.l^lql^le+ ag +lile} dB gF=Jq qlEI s&zlE d
246 7 gtrtE
4ol alr"+alcli ag "J+61= ql ol+qr gl+. ql ilE trli +El &-dxdydz "Jql^J "J"JolzI gag q¤-e.
rdqqlql^l= "J"Jol9 +l^le+ aF%83 Erl4 o + gut lr4l'zdt9l HlqlEI+.
aq-6}ril ++H + gl+r g* ^J46Ig+.rq+ "Jzt q+q= g"r'' -d+q= lTlelo} 6Ir,
=zl u|=" ¤+4
qq}_e_s oJ6ll^l +lile+ +E*g ^JB4ol+= ^ldg "Jrll 6IjI" +o-J6J *t
¤Eql^J +,tlrflE g4}qxl ?+"I"F
"lr+ot
q$.eq, +lil$ Erlai4fl S+9 q^J^l4oi 6IiE Hlql 6E" E6J ¤+zl"J zl¤zlE 7l4o! ++.
E eE+g H^l6IBlH +l,(lE sl^J^l4oF ahY 4"14.
7l-El+e& 7I++aJ k
7C34q +lile+ ¤+"d= g41z|_8. trJ
E hermite ¤tlz} lze ++E + 9l+.

7C.t, gFlE-qtel 7E!
+Crl zlQlil: gt}zl oe. srlg= 7I+++g 6JH +C6I
gtzlE9 g4- +q=r+ *ol "Jfl9 zlCEs eo;g + 9l H oE r+zl +q 6t+7I Ll-g 4o14. ul^=." g$zi lzel I
o q, ol=g *e_E ol i4 dElql aa s}+ql^l olso 6I=
#Eifzl-"IqE ",te irl+E +Cg lRg trlE ¤tol Tlqlil
oJzlqolE zlzzl ¤ 4o14. (o)(zc.tl^l o + Ael¤)e+ aril ¤+.
ul.=" g-,,-.EL+= 419 jLE EEqL4 AEE Llls
4lE u+rE" : HeisenbergEq4¤ 94: "J"JolE +lzle+ gF=J, q "JHI4
611 9l=Ell, ol EL+= 4lql ql6J Schrodinger 49 ¤q^J E o-tr IrJdil^l 7}+ol 9zl ?*E ¤&z}ql 7i+=%FE
'l]+61+
g + 9l= +qi4 ++tri. el ,^J¤. 5.t'l{e-tr B"tEzl eq4rll E^l6J += fl+.
Born 44' "JoJol9 vlE.E:+zI qH d r"il^l y,clE, ol d
T]ILJ=
=s-d
tr1. 78i! ,JE*1"14.
Schrodinger 6ILIE tr8. ^ls 416I= A+sI 6J+=g ^]lE= EIE -Bt+
^lg ^llE4r.
-2. Ettxl= 6J EI+ql +qi4 ¤&g 6IE+ 6Jtr1. eI+.
D3. Hamilton E+trt= AIE Btl eE qlqzle+ ElHl¤ .llHxlE tr9. 419 {t4lz} aJ ¤&zl-el r+*+s z169z1 9*9 oll} ol
alg dill qlLJxl{l 48al-b ¤{Iz}tr|.

'JoJ 4el l9g4=9 Edo e +4'g + 9i+.
44. qlLj^lql 4s"61* hamilton ¤&ztq l' trr0. "JflE ++ Ar+E ¤til= 6ilB'61-= fltlxt9 Tlrflils +
=AoJ qdq.
a-d++.
trs. tolal + Et+E 4s{d +rJql ¤tl)ol o"lfl ol + ¤-+= In. E48¤ fla|: ^JE4 zt++%Lg H^l6raLI +C6J + 9l
r.!E6JtrI. CqEql el4lz} 9l¤¤ "J5il=+.
=
D6. Etlxl= d+ r.+ilEr+ zlj/ I+EL+E¤ *=+.
Hermite at2. zlS**Eql q86l* ¤&xl-5"1 {E z}S}ol otB ull}:z
47. 7hE+Jg hermite ¤&zls *.,tlE4 z}*==*Eol $H4oltrl.
=s-d^.!=
,\-lzl
c, e.
/\l
-1 +^l HE
^]
r+xl ,JC
ov=''l' y.a+EL+ ro -L$zl 7C.zb
^l
oll a ule ,tJ
w i o,y, ar ={l v i nr,or}.
Hermite ¤tlzl-= d r+ilel zin lga$g z1-= 7C.7
! +.
z]r^"i
lw:w,ar=o' ,*i"J trll d,z"aqlaa 4+ 7C.8
zlEllz.l (o)=[y.Arydr t9: {7r1 \,= 714 7C.rr

HeisenbergE E9CC gEl LpNr- +n flzle+ g.rE" qfl^J 7C.r3a
"*ql
F ¤&zI9 r{+zl. 1{),,{)rl= OrOr-OrA V1,g,l*o"J trllb 7t++*ol tlE4"J 7C.tS
4*7i,i,,1=n 7C.r6
=E{}
Eiil 7n
+-l rv Hxl
OIj
9E
tIO
Vr(x)=Ae'h +Be-'k
> ol EE|E H[+= olg
g^l=- Etl E¤;oll 4E^laetr"q g^|.e]E 71301 HJaÊ 9zlrl k, A,o) B= t}+Eol+. ol w@)zl7D.l^lel 6ll"JzlE
EE E1'J ESolLl-0E olll_l^lel ee Hl r.c4 +l0l sFdfi'rf. 0lE
+.J6IEJE, ol19 ol 4+Hql Ba E6J+E- + q-gql
E7l+sl zli{le} e3 xFdE +trlE E7l +oil^l rl+ EE ^lE
^l{Ets
61ts fl^let E^lE dtrg ts61.= tll
t 44zl +Hr| Ag a"Jxl$ tr-E S4. det*/dx= * Ae!*
=e6ltl. ol= + 3|Hg q-.q_4 eol gr}.
> EqC T;1LJ ryoS)
g-d-d arJ Bqql ,Jd9lts sJolel Et! oilLl^l #.{= gf^|.tr}
fi' d'
slq, +et EAolNts 0l goJolTl-aflS.E a8qrl ?=re gq -MG (Ae'* +Be-ik;: - $ UOol'etk + B(-ik )2 e-ikr )
+e.e FzEl ++ 91tr1.

Ek
ryr(x)
> qHl rEl

rJ.e.Et kttl'
(Ae'".+Be-'h
trlEg4. Schrodinser Ll9 afiolfi(Etrf, 78) Eal+4 ¤trEB : 2m )
7t*+aJq q36k Etlxl.= ol$olQ trl$Et+E+El ?61.=

trl+^J alEol (^J+)xy1,@)zl q=rll, a^qss +4u
Eflfrl(EE 7c)E E 9l ?lolot eltl. ^J+
7l Ee+ 5g6l-7lq] alfl ol al{ol +H4 AZI g+. "llulzl
Ag k<Hl E=6igs g-e-e EE EhE 444zle +q. r?-l
6Lq zl+ "J"Jol9 ul.E"EL+e+ ++4 e."1 84.
*+g E"d SF"J Bt! eF* 7lE4 eF ,J^lel 6t+4. "llHzlzl
ol Hrl ¤#"Jzlq+ql el6IE gg+4 9lHzl"Jg zt¤
Be-tu ,r-+
trlE-er+el
oilq^l
(7D.2)
+ 9l+tr7l. E= rd4 o + + S= gEg +r++q Vrk)=Aek + [1
^l-g]
HzI alE Elad4 +Jg +4U+
=4g
7D.244 ¤+Colq, E= *ql^J ¤44 zl9
7D.1 1il'flr}f,EE zlft tlzlt- 17|ola +6Jqls gtl6tzl ?*=tr}.tr14^J ol +
to-J+= E= /6o]l ql6I^J .l+E+./c= "JelE (}g AR +
zI+ "J"Jol= qq+ qfl¤E TllEE Ezl ?*e4, ol ulHl
lle + glHzlb cg EEL6J EE "JE ,"k3 zl4 + 9l+.
¤g EE *ql^l 00 + +3 + 9l+. lzl-gql^l= qq^l+ zl-.ft g"Jolel B4l ¤¤l qqzl= "JzlElqzl 9J:.=4
v(x)=so1q, q+^J schrodinger "|+^J
++!+ ?ol ¤4(Eq
^lol r agg + 91tri.
7B).
Eq Tcql^l ¤B6J HHI E6tH "Jqlzl " -e ul¤.6J+= 6J
tstzl9 r+'J+.q c¤ a.Jg +49 + 9l+. 7D.24

-*W-h{(x) 1^l-goil^jg
^l.3
8E (7D.1)
E u+JE"gL+= r.+il7\ lkhoJ d¤ ¤+=J ¤&zlE a+EL
+="J etikxE d¤ e6J"Jg ++6.|.71 Hl+trHEq 7C). ol +
"lB "Je^lg += ,}tF t++ BB3
ol t+ql zAlE ol4
r+EL+59 q-q=$ ?"1 H$t dB +B=*E tr-rflq ql+
+ ++E ,JA^lel g "JeT1 gE 6li$ fl* trl-gql ol allzf al-b 4,Eol4.
7D.1^lg e'JE "J+^lzlizlE q"J6l] E= aol+.
V xQ)= Ae*'b +B e-'k
6h= gtsolol EH-d +/<h9
-YJ
dE EEaJ -khq detEeJ
Sclrpodinger Algl 6ll
gg0l g"Jol
=,J= =,J=
zo.r44 zJ9- zAl4 trlE %'-C^lg q-q-r+ eg "JHI6il= r* Eq Tcql^lE ¤Bql q-qE 4lE ^JEllz[ u]^s."a;-; vx@)a
l- rl 7l¤¤ ql= eE+9 Elgol +eg a+ A'zql Hlql 6l+ q
-T.
2t 8 7 gfl'E
E-tr +kft(oJE8ol7} "J9 ,4 Bt6Je-tr- 015-6l+) <i"l 444 7D.2 1il'floll^lel 7+EE
-r. E Brq HIEII:I-g sEe -kh(ojuiolzl ¤-9 x+ HJ6J9_a
0l:36l+) {tE Li+B aol+
^}+ A4 nzl o"J
ulli "J"Jol + Hl-Fr+^d zl{ ,r.1o1E +6J6J +A gqq e-d il= a=+
zl -kh4 +ktt{ +B.J gF="I <ig *al g+. ol .8rt ?Jel SJol ExllE ^J46l] -H-z|. {rz}
nroJ "JtrJ"J,
.Jql^l= "J"J"l9 qfl¤ qLlzlTl-6olzluJ x=09 x-_L! zl
qql^l #46}zl +oJ4E 7l+E+(rH zo.r). guJ"lz| F
zl{ ,r101ql ilg 4lE schrodinger ll"l z}f "J"Jolql 4e}
a(7D.r^l)l} eeq, q+^l 7D.24E "JHI6llE st ?4. ol
zl$-zlxll oJ9 ,4 B-6Jse. ^he$q-. olBl6J 9"Jol9 -q=g etiLr=cos kx + i sin k E +4lE(Eq TCel Els+zlE tL
+qzlq, r ¤E" +"1 Bq6I4l "J

7D.zlo + al r0) olf-all.<l +q'=4 ?ol li 4"1 E4aI4.
q *q B-6}oltr + B=0ol g+. r?-l_:r qlqzl{l *oJ zo.z _ rtsikx 1B.-ikx
V*@)
49 ra^l kq +El + +4ul]E trl¤4 ?ol S4.
^l-o = A(cos kx + isinkx) + B(cos kx - isinkx)
U2 = (A + B)cos kx + i(A - B)sin kx
l -l.
)"' _ f 2x(9.r09xt0-3' kg)x(l.6xI0-'' l) )
2m,Er
k- h2
l
= 5.1 x 10e m-r t_ _t
? S.t nm-'ol4(l nm= 10-em). tr14^l Vli- j
n.s.trvnmols|. K
5
6
{il
EJ
E
zl?-zlzli oJ"d"l7l x4 tl-e-EtrJ ¤5"6J+r ^J46lq.+.
"JHI4-" e dB ¤+*g Eqolq, "J'JolE ¤jF"J".&g "-J
++(+E+zl.el t}^l l7g 5.ol4) El+^J p-khola_, dlqE ?lil, x
aTlY p-kholL+. ol ulEl 4 ,l +tlE CE+ pq-kqholq zJ fg 7D.1 lilfl df^l-?Jsl g"Jololl EHZ| tr18!¤ ollLl^|. trlEJ!¤ ollLl^l=
C+q qq} s+-E"oJ+E e*,rgl ulflla}-1.(¤zlAf q_y, y,E_+ x=Ollx=L ,\lolo1lllts oola 0l gq EJoll l= +-LrttlE il*=tl'. 'jllEoe
z), 44l4ql ag ¤4.' 0l F Bq J'Al= g"Jol= Erf^l7l^l ?J= 8q0l El= 101tr1-.
"i(k'x+k,r+k"zrl
^lolel
ElElr[e,l 84 rz EE1
Eq= aTle+ "J6J1g zlzlt_ lql +4 gl= "Jol4. ^JE E 4E ulrlEol4.

^4lil
U Eq ul x, y, ") zq tl-ql 44 4E uo rr H uft zlzlt-
il=ql, ol c+Eg "J"J +E ?lr +g +E gltrI. qE^l vz
?Jol 2.9
-1.0
/,=-f Eq u4 xG d+g -*q *4 zzlzt t.oql d
.QolH +1.
"l+. EEl9 ezlts u EE lulE -tr^l6}q

q+4 TJol +
q4l+.
u - (u|+ u] + u:)'/'
f46}q f4I u,=*l.l"J EEI= a7171
u,=-1.0, ur=+2.5, AilIiI 1
z.szl qq, lrllzlE Lilalql +4u 4+ rJz r}'J-g +Elu

+. +Ee+ ¤+=+g E+ ElElol+. rqr +E ulel9 =_zl
ol lzll +=ql g,q+ EEI ¤4l$(trJ6}zl, #6l.71 E)* e
+qol4r ++ C q^l ulrl"l4. rell $t\ztfi zltl 9 sc9 Elqzlel *\ 22= .H-ot4.
=
r ol dill4 :zJ4 E-o + +4LllE eit'ol4

7D ETI 2t*9
-
t+ i(A-B)e+A+B- Cgl DE +r ol "JHlailE ffi$ pol 3 trl-* ol ffi$f9 zllfi¤ d {tzlql 44\ 4+.J 4,ol t
+El.llE g+. ol Elrll ++ ol t+=.6J+=0<x<t gE +ql^JE0ol qq
-e. ol gq ?Iql^J"J 4Eg 6lot qL+.
Vu@)= Csinkx + Dcosk* (7D.3)
trlQl¤ .llHxlz} FaJ4zt 9E zlq +E ¤qqlî= oJ"J"l 4ET.2
zl- ¤xl]E i
$. o Ire. ul^s." gt+zt o"l 99oF 6J+. + [iw'a*=N'J' ,in
nTcx
L
d-r=N2 **=r, ? N= (?)'''
W@)=0, r<04 r>[t ¤Eql^J 0D.4)
qq+ E4l 3 4s"9ts "llHzl *zl

ol /r9 <lol zllEE Ezl g:eq, E= 471
^ldql^J= 7D.24ql eloll^J Ex-llhzl2molz]"J ki nnlL\(n-r,2, ...)
-"1+g+.
*E"J 714 + ?lo t,.tr qlqzlE +gr+ ag ztE"J zl4ot
++.
(a) -"1EEl= 6]|
grfzl "J+^l4ot ts 44 +E 6t+. "laol ¤+4ol k'h' (nrl Ll(hl2n)'z n'h'

"k- 2m - 2m - gmL2
u}=."
?+"t ++= 4o14. rr-lflq x<09 trll=(trl{l¤

"llHzlz} *
f,4z} q= *) ul-s."grfz} ool 9o + irlql¤ olltJzlz1. $aJ olx-fl a BI+I rl-trro6J+eI "llHzls Ezl= Hl^*
ezl kZ no
qE il+= doJ x=Ooll^l ul-s.o 6J+E 0ol qqoh 6JtrI. ut&z} ol^J rir,(r)q E,9 4 +4Ll]= 4"1 etBlal-4. tr|4^l -"1+q
xlE x>roJ trll= El-Ei6'L-Az[ oo1 qs + EtHl¤ "llHzlz] *+ e++ El-E.6J+e} {lHzlE +-$q ?ol 448 + 9ttri.
=
4E zl+= doJ x=t9l^J tl-EoE-++- 0ol qqot ++ + ol
E + a4& ol ul-="ffiolJ zlo1lz13 z./'l?E7col+. tr}+^1, v,,(x)=(1)"
""(ry)
. E,,=# n=t,2, ..
1if3 df^f oJel "J'JOl (7D.6)

11/k(Q) = 0l+ V*(L) =0 ?e4l Tzl (7D.s)
olxll uf-="gtf7} olE 4Al

=dg "J+^lzlzl 9la1l.<1= +A rol "J9 A+"Jg 714 + 9i+= tz|g ^JzI .J9
el u1-=r"g-*=".tol 6l+q4, "J"Jol9 glulzlE atE Îde
=aq} "Jzlsl¤ qlHzl"Jg 714 + gl+= 4¤- 9"1-J4.
oJtrJolT}
"J9 zI4oF ¤ItrIE Ag Eqot 6J+.
olale} oJzlsl+ v/71"J+^14"F ts a Al z4 ul$ql Ltg+.
olag "JH}4'J ¤gs-e^J q'¤.4 ?"1 448 + 9l+ .
7+ ErJoll el6}|^'l g^1.+
LlEIuEl =?l=ol 44 44¤: "J+^lzlzl glat^JE +4 E+EEl+=Elol q+
qq, rrlur^-l 7l+.+c¤ol Eg+4 <tE"Jg zlzlAl ¤4.
"J*rlge+q ¤E:"lq ++ aaEol 7}6]]ag qle-l e4 qlqzle+ -szlE ^l-.*¤ 4i "? 'oJzI+'E 6J
+6llot ++. qlol+. "JHI4es grÎ+= cfol4, alE t}4E- +4'l]=
=
E4l 1 ++ aa zft;lzl -Ezlr+(Eq ss"llrJ 4szl"J Hle+"J ullE glr}). lz'lg ^J
x=OolldE V*e)=C sin 0+D cos 0=DzI g+(sin 0=0oll z| "J9 "J"J"lgl ql6J :"1+q= q.E.EL+= T t6l "*sq, "J
cos0=lolzl trI$ql). ]! zzl9 al4zi r41(0)=0olq, q4
n
,<l D=Ool 9ol"t ++. 100 10
x=ril^J} V*(L)=C sin krol+. E{ a4l z$e W(L)_o N
-J
rE40 + aEq= ollLl^l
olq q4^l sin kl=Ool 9"lol 6Jr+ olBrll ElelE kL_nnol a 81 9
a n=r,2, ...7I qqot 6J+. n_0& ulzlloJ 4?, ol4.ol k=0 tt 64 8

r{i
g *4q q+^J s- *ql^l v*(x)=0ol q*(sin 0=solt: lu 49 7
E) 6l+¤ + S= 4*zl 9zl ull+ol+. +¤ ,9 Zlol g' D

.--: 36 6
K
"J ag sin kt9 +sE HI+q¤
golQ(sin (_o):_sin gol 5 25 5
6 16
EF). trI4^J + 4A\ 44¤^ 4
"J+^l7l= 'l-tr.o6J+:. vr@)-- 9
41
C sn(nnxlt)olq, $zl,tJ n=1,2,. . . rq-tr. k-nnlLol4.
EJAI2 4++
]aJ 7D.2 8^l- gfel g'Jo17l. 7E + 91= oilL1^l
rtal-=7f6|.q, ,\lolE 7J7l? gl^+71.67fg+E =+1.
01lLl^l 5?1ts n20ll
zT]rl-. zE4o-+E
A+EIÎzlzl glafl,<J= ol19 Lr srn (nnxtL)g + g¤Jol7l =91 + LlEl-'.! Hlel.,J0 p=
Eqo | E+4oJ,J- 7lE + 9ltrl-.
^4=-d
250 7 zFtE
54 2
tl =1
!-
(a) 11 =2
n-
>
11 =1
<F !-
;ib0
0 L -1"
Uo
4
(b)
H
n=2
i
{-, Lt
\' f)=
L,t
q! aal 7D.4 (a) gxl- ?J g"Jolg i13 + trl.=gf+, (b) Et|36l.= +E Es,
fal 7D.3 gxl-?_fE g,Jololl EH-d i1= E?trt trlE--J+. ollLlxlTf
r.elr. (c) BSE )l^la- LlEl'.! qE "J-Ee-lr^l'
Etal trElol Elol^lq, g!ttl'= trl'Eo:d+= HJ trEl^ l tri eqd+.
=TEloll Êle
8^l' tr|.=Et+7 I oo E I.
"Joll^1ts I
e+. 44^J x=04 x-Ll2 Îolel gqql^l n=1oJ oJ'Jol

zlf n9 r +E 6J +C Eil^J r+-E"6J+= S.^16]] ,l EaB +Eg r+s-$ *c+.
oJz|+= =+(re
olile *zl +4-q-+ .rol=
e-lqlE ^Jql r 41E r.2
7D.2).2
ql 6]]'J6l-= EllqlE ol+g+(7D.6b^l).
"lluJxl= 4l&61-= r^'(ff)a. =i
e - !''',t l d* =?, !:' l;-*"*(+)],"
(b) trh=:Et+el dE 0
lil-g ttz]- "J9 "J"B"l9l q+ "J+ re 7D3ql 2 L1- _l

T 4- ,* rsnn -2
+44S.+ q-q=+ ee ceg +E-6Iq4.

. EH¤+59 -E.f sine a$!-E.! ++g r.le 4EzluJ q¤-IrJE= x-Lt2 +9E 4?olzl ql+ql ol {$i $$
oJtrJolTl-gag q
r 4,"1 * ¤4.x=04 x-Ll2,tlololl,<J
tl+E-=g d++"J6I4.+tls ,?ol f,zlp,f$ 1141+.
. ul^Jol solzlE u1^="9-1E ¤+ ffiol 4x14, trt+^l Eg'JSol x=09 x=r rlol"ll,r'l $uiolz| Ea¤ +E"J
+F qlq \zl
QzlalYlltz} "J{l^J= y=ool r9 Hlol 9"loF alt 4,"14.
"J"J"l9
tr + qlqzl= d4-o + +F qlqzl +ol+).
. nol +TLEiql
"14 "t4 4 izl6zla\4,
q¤r6J+ l/,,g
nol Qzl$ffl dd q E4zl= T1# +^l6IH +E "J
n-t\ll trtqE *=+. E wl? 7ol f,zlgroll trl+ trl +"J6l]tl+(rH 7D.s). "Jzl-+
lil-fl ,g.xt "J9 "J"Jololl ql+ +E "JE= q^q=r+ ?ol I 71 4+61 . oIE +E "JE= 7d4t 44, 7)q
= ^l"l=
zlql q+ qeq *trt 7t+ 6IE^J +=61+ gI]JolTL B+4-" e -Et= +l7lql
iHl6}al El= a4e+ aril E+. oli-lH t.g
^l E"J* ^la¤.
v:k)-lsin'(ry) (7D.7)
,ol lreE q¤ gEel Hl-+"JI;7l q c6il4lr+(r4 n.+).

E+E: EJETI +4"J *g oJEJolTI Eag q¤ol 7l+ +g L
+lil+. x
]
zttrJEt q 7D.2
Eq TBql^l ¤B+ ?"1 5c.J ¤qql^'l oJtrJolTI
ute+
BaB dill q¤e ylx),dxz:. ¤qq aa 4+* a+
z qE" tlf zl *zl qql^J= E¤A"lzl trlt+"tl Eq 7BE zllgtadg trJ4 lg 7D.s grl+71'= rllE EE "JE f(x). (n=sog tttlE 8^{ dE n=1
tril+ql 4+el g Fg Crt HIE6t|
tttlE nol z1Eoll tttzl EE tr1 Ealrl= alEel
6}zl ?*=E+. "lE ulHl¤"llHzlzl +46lal +elqle H6I7l ^4 =?ttrl).
El^ll+a= +^16l'r r4l HE += "JE7l EE q EgoHTltrl'.
+ fl= EE qloltrt
7D BTI ffi 251
"JzL+ql^-l "Jzlq+4 4*zl rdqq}g e4e+ eAl q= "Jzl-+zr nal n+ r"J F "Jd6l-= qlLlzl
=+l ÎolE
,J4
ag El{8 fla!4r fl4E "Jzl-+71-tolzlH
EI+. ol "JzlE e ++r+ a+.
q}e_E+q adqqt"l +g+= ag g6H+= 4o14.
(7D.l0)
(c) qlulxlel dtr ole4g *zl9 z)olzl ?7I6J+E 4otzlq, ¤-zl7l 4^14
1tzl 4 "J"J"l9 kxb dB gE=J ¤&z}9 _r.
sin
a71.7re q= ol 7J4ol tr}]+61 AI.tTl+ zl$ ,t1o1E 4
trll$ql ol ojulolel dB ¤+=Jg E+6}|l
4zI #ELq.e g ql= ++l zJ4"l ool 84. tr14^-1 ¤E¤
-.$ Etfz}
"tulzl
C99zl ?+=+. rfl+ sin kx=(.*-.-*)/2iolt: + +Eq +7lql Eq 9l= gzl-4 ExI9 a+ql= rEE
E trl+4 ?ol ¤ + 9l+. = oJzte+qzl
qlLJzlTt g+.
Hd ?+= aaH a#6|]E
v.k) =(1)'1r(?) = +(?)" 7"'n*'' -"-innx L) (7D.8)

El-el^J dB F" "#g 4l++e6IH dill q+el *$+nnh[& Ef =+usel
+B
+QL|]r 'l-"lzl *Z -nnhllg +49 1o14. "lp* ?"1 tI4 p-7lEEl(l)e c¤ ¤4tloe.\ zzt\ gzts ¤
Î+ +i
,J.J.el &Fol qe,g +!$ zlzlt_ +QLi= A* z1q g tr++ lozflel Elg A.Jq 117HE 2rt $z;3ol H3"t +4
^lol=
¤+61 f*+7I+6IB^j +qd \rJrJ44 HI-e-g+¤6F"1-b \i+. 4 c_c ¤6J aol= 140pm_tr +l6t$ ol p_z|_e.Hl E
¤+{1, r4r 4olzl Hlg s# 6J6l+ ¤¤.ll
"l+61-= ^J 4¤ Aolzl L:2.e+nmt ^Jzltr. B + fltrI. Hlql- tlqlE
zl ?l "JoJ"l9 Ld4 ,}]Hg ""klqq|4_" + 444= Aol+. ol $zlzl- {$ $f61q r-P-- e-e *3 E=E qal
^}E|]E
n9 ool g + seIr_+ oJEJolTr 71?_ + gl= 4z] qlLJ^l H ¤+61+ Hel sltlol glulzl. 9dg+r
0ol olr-ll(_zdq+ql^]= ezl ^JQel "J"J"l qlLlzlzl 0
=
ol !E a4'|]a4oltrI) q+r+ ?ol ¤4.
t2
D- n
otr oilL1^l (7D.e)
L,_
' SmIi 1 p-zteE!
ol Bq 4 q?J + S= alx]9 qlHzlE 0E 0[L1r!4r 5-g z4-* ga 9l- HIe+ e-"1 E

"JHlEItrI¤- E6ll^J ¤-
+.0d {lHzl9 g?-l+4 g"Jg +7lz.le 6114g+ 9l+. ^lB
i g4-E=g 44 n-+-llggrfoll p d4¤ 1z]l4 7lq6l+ql,
. Heisenberg9 E4AC g;lql E6IE LpAx > +hol+. ^J 4 tr4"t4 27lE 4zlzl Eqa + 9l+. zo.rorl9 ol*
zI "Jql eqfl= LxTl +++ al9 zlxl4 trl-4^J Lp,zl 6Lq 3l-Z d+ 4lzl Hl-d+ ,J49=- Al
=+l ÎolE
0ol Elzl ?*"I"Fzl :Bzl ?*eH ol g4ql q*wt.Irl
=+le+
&61r" ol qlqzlg BohrE 4l#
s4l(ze.s4,, LE_hv)$
+^J Brl ¤.F qqzlz[ so1 g + H= ao]+. ol+6|q rltle-E H]-E+.
-E= *ql^J 0ol 9zl t*"t"t 617l qEql ol uf="g}+= =ol

t"l ^l+4\ zzt11E cgz}z} 9l+ 4 flzI "I4 "il
Hzl E9l{14 tz11E p dzl¤ zl{a}e=tr. n=rwlzl4 ,+
HIEÎ ++g 7l4ol dlq, ffiaJfzl- +$-g *=+=
2414E dzlE a+¤+. Elq tr-Eflsl dz} at4
ae H{ ¤+ ollulzlE *=+= 49 9"1il4. =glEol
zl n-tte.Prl n-r2E g+ZI tlql 9lHzl ,J49.
^l"lE
#JEt q 7D.3
q-q_r+ ,Jtr+.
l00nm 4ol9 gE ?Iql dxl.9 alzl "llHxlE AE=E,r-8,,

zo.olln=l-e.
=qfl=
+3)e + +qd+. =(2xlr*tl
: 1.60. .x 10-'e
. J
,,= =6.02x10-z4l
8x(9. l09x t0'' kg)x(100x 10-e m)
? o.rooal"l+. Ir}4^l Bohr9 4lH 44(LE=hv)91 9dl
ol 4l&q^JE rl=1kg ol dolE gezlE ql gs+ +^lE 4lt+=
"l ollHzl=-
m2 s-29 "l+619+. r-l-q-!+
^J
6.02 yJzl ErH I fl = rtr'n D. *"1 ¤4.
2s2 7 zflE
.solB, ol 4¤- ¤q^J Lie=

t'00"'xto-l'l "l ^lg *crl"lq,
v=P-
h 6.626x10-'" I s
=2.42xr0ta s-l re+ yE + H+E si+E^J v(x$e +49 + 9i+.
=
sltlql qlB
242Tru(1THz- 10t2ttz;o1q , )"=r24fn]m,E (a) 0lu1xl trl"=:d+
=
++.+4 a+= 603Tr1z(1-4e7nriol4, dzlzl lEE -d+q=
=+lst
r+s"gL+e+
H9 zlrl gq +Î"ll 6ll'&+4. "llHzlE +617]1 fl6H^J= 2zl-g Schro-
dinger ^rg ol+6l-jL H+ E4H9 olSat¤ ol 49 zzgE
# EBol 4eq^l aq+ <lg zl4B f
=
gzlql { +B¤ tzl-fl + +?]6110} ¤I+.
^l-o
4l4l6J ule}"l -d+ *41 "Jql
îlE =qz}+.
Tj7lpj.7j7D-1 z)olzl flx}49 zlfllxl0-rsm, + tfrn) @ 2iEr grl ?J soloil EH-d trl.=El+
AEE ril-fl r}x} 491 ee 9l= ar{ H 5F "JCzI9 q7l^l ¤H6Ia ols" B 'H+ E4 ,JH'g oJzlq+qlrJ ¤ el
{lHzlE {zl-e= e.(l eY =1.602 x = l0eeV) E
10-teJ; I GeV
a+ql "l+qa fl+.
fls 4l4}*e-Ell,l dB4e q qlqzl= +4I61-q4.
=5
Aaog.o.E
EAI 1 H+ +"1 *89 "18
tr}g + ¤tzlb zlz] x4 /"JE El+ql 4l+61^= 4Eol4.
H
tt' A' Hv
h'a'
2m dx' 2m dy'
7D.3 2iEl olgo{l^1el 7+
- r4r zo.ttalg +94 ?ol 4rl +trt.
olzll x4 49 z)olz} o4 L, tol, _24-z /+ *el 7)ol7l o
4 L, zl^].4¤ 2ilg gEg

^J46l] EzI. ol gq "J H Hy
ÎoloJ
ql^l= triQi¤ "ilHzlzl-gola Hql^J +qlqls zl+=r}(rfl tt' a'
- 2*eF ,-##v=Ev
7D.6).lil-?lel a+e+ uffizlzlE ol gEel Eql^J|{x=0r}
Lp f=04 tr) ul-=.o al-:-'z| ool 9"lot B L"1q, ¤q +l-ql^JE tr}4^l
0ol qqot 6JtrI. 7lq oJtrJolTI ** y + rJ.Jel
H
Îolql^1.
d +tql "J"lsg gE qlq zls zlzlq, q+^l Schrodinger H,V+H,V=EV
4??+?:q + HJ-Jql 6l+4 24lE ¤+ qlqzl 6.19 714"1
++. r?-lal¤ d=J"l m"J "J"Jolql 4t S.hrodinger 49 +
+E'J+ fl=6}= *f x(x)e} y"ll"J E=6I
raE x9l"J
EI+ y(r)49 EeE +48 + glqr 7l^3614. +
*4¤"1 ¤+?ltrl =
vlx,y)-x(x)Y(y)4t- zlsalzy. ol zt43 ol +71 *89 ol8
ts + 9lb flCol q= a izltlJ ol zlz$ol sE ¤ul$ %Ld
#(#.#)=,, (7D.l1)
^lql^l
CB6l+ 43 oI,-.|4. ol 7l4ol9zlrJ dB++= a
g +"J6|]oF 6J+. zl{$ ols-"al$ 919 4"1 u|g-4 ?"1
"l
V
t- g+.
-I A
ol
l. -l
I
u -x(*)Y(y)+ H,X(x)Y(y)= rXk)Y(y)
rBlH H,= x(x)91 ¤&91(xql ++ 2zI E6J+¤- +l6J+),

goJ0l7l.
++Elol
ulalzJ-zlE u; y(y)91 ¤4IqF + "l 49 q+r+ ?ol 44
o lL c!{
Y H + 91tr|.
Y (y)H,X(x) + X(x)H,Y (y) = rXk)Y (y)
x
aaJ 7D.6 2ifEl Llls.

+gql= "JHg x(x)Y(y)tr ++a r aq¤ C?]6tH trl¤.
?E. x=01[ x=11, -].al? y=04 y=[20111 trlEJ]¤
r+ ae +wl +g+.
o1lLlrl7l +-dq-e
Êrl"J
r Ltoll^1= 00lE[. SJol= Hl-Frl8 Eo+
L{g Eoll ,Jdglrl-. =
=ail^loJ
7D Btl 253
-
xolloJ E= yolltrJ el=

,^.}
d-T-
*o-Lr'-*,*, + {g';,r1 - E
ol I7i H6Its ar,ll 6J"J H6tr += + 6}9 H6l-zl

^lql^J
?+.t"F 6IE_E a4l o.lE *izl99"t ++. ul$zlzltr yzl
H4q?+E Exil 6}g H6Izl ?+= *izlqqot 6J+. El+^l
olE + tr-+E zqzJ E*4 E"E qe}L]]ts trl+r+ Ae A+=
erll g+ (a) (b)
l^
fi,, ,x(x)= E*, ,rI{,rJ H rx(x)= Exx(x)
l^
T(1H rv1Y)= Er, 44^l H,Y(Y)= ErY(Y)
rEl-r. E*+Er--E7l- gtri. 44 ¤"lE "Jc^l¤-
"lBlqI "JBql
7+?+ xe+r.ll *tI 24]9 tr"lE "J84se Br-lEI 4,"14.
tr,J71l2 F ^J"lE %1449 481 (c) (d)
ol= + 43*zI 'J9 "JoJol"ll 4oJ schrodinser 44
tz1-g
a4 7D.7 sEql ?Ja ?l= g,Jolofl EH:d trlE:d+el trEt|il=
EoJaJcll, 6I+= x4gs ol+6J 4.oll, +E 6I+= ralEE ExlCoe ^l-48
LIEIL[|*tr[.
(a) n,=1, n2=1; (b) n,=1, nr=2; (c) nr=2, Dz.=1;
ol+e} 4,"14. 4Al 44e=E E+ ti"J61+(+ rl-5.o 6L-A7I E r.ell. (d) n,=2, nz=24 lxl ollLlxldEll.
q1,t-1 ool 99"t.J+). tr++^l F ^lE 6]lE rl*.+ *"1 44
B + 91trI.
zFJEt 0{l 7D.4
x,,(x)= (+)"",(T) E*n,=# HE ,Jolzl (L,=Lz=L)oJ LllE=-

ol dztg
¤Hq e-dgtE dzlE
q¤ "JE= r+q_r+
"JzI+71- nt=r, nz=2o]|4.
v,.til=(
+)"'^(ry) E,n-# ?"1 44'3 + ?l+.
nr\ n2E 4?+ +44 s E 1, 2, ...4 {l# zI¤ i ?14. (+)

vl.,(x, y) = $ sn'(
T).t'
Ell 3 SA+
O<x<L,r| o<y<L2oJ ^Jzt q}9l^l= 4taJfzl + 6J+E ttl+^l 41rJ] +E +lil= snz(nxlL)-t tri sin2(znylL)-1o3
* e +q4l+. ^Jzt HlourJ
X,,(x)Y,,(.y)o14, olzll 7D.12a41 o trll, + (*, y)=(L12, Ll4)e+ (Ll2,3Ll4)ol+. r;lr. :?lz'l E+E
E u1^=." g--'-z]. Ool4. rall. qlq zli. Ex,n,+ Er,n,ol+. + "JzI f-lil(Elg:Ef+z} od$ 46tE trlq)E tzl-49 qE
E"
"J
fE ,, =1, 2, ...* nr=t, 2, ...o]trt. tr|4^J dzllzl -o -e. ++4 E-z| ool q= *e-e\ y-LtzoJ dql 6l]R6J+.
?ol 448 + 9l+.
3zl-fl /J.z} 49 gu3olE. Hl+c EBs+ trl^= + ?14. "l
v ^,...(x, y) =
o#*( T),^(ry)
qEEr+
u]l!- u.l-sr" orz-'zl # o + 9:r, 9lul zlr :2fl$ 8"9-_tr ¤
ttl{
[2^l.g] (7D.12a)
4. ]4r *ql^Je+ ztol z16}e- rz}+lql ql+ aq +Î6Iq,
h' uFE"EL+= tris=$
En,'n,--(+.8) 8m
ollLl^l [2^l-fl] (7D.12b) dill4"J ?ol 5|4.
=?l
Vu',,.,u,(x'Y'z)
"',*
"JP q^="94=el
=:TI+dg
rB
zo.z4l L].EI.IS.EI. olE = (;r) (
T )'^(+)'' T ) (
rflg aA zo.zql +4U ul^s.o 6P-'E 2il-g gol+. lzl¤ql trl-E-Bt+ [sx|91 (7D.'t3a)
^J=
tl'trro 6pA7t
"Jgol rdg 415 #9t1, 2zl+lql^J
rA¤ =4 ¤zlrJ 0(x < 1,, 0( / aLr,ol z1 L,
¤ol qls_ *9 TlE"rI *9i+.
=
254 7 gfl'=
/ z z z\ rz
En,,r,,rr=[? *?*?)#^ oilq^l
=?l
[sx1g1
(7D.13b)
"Jzh+ r?]a nrEg EF "Jgl df t, 2, ... e-e-lJ

n1r n2t rEo
SBzl o e H6J + gl4. ol 4lg od ollHzlE 8,,,,,o1+. I
(o) slels
"J"8olz} e-"i gl=
gEol a"JBg trlls._, 1L,=Iz=IoJ 4l (a) (b)
* tzl. 4 g"Jolql qq} 6l]7t 5tr+ Cag +El-U+.

zz1i1 feJ 7D.8 4l l4B sEoll ,.l"1?l= gg0loll tH-d F trtEEf+ (a) n,=2,
olfl a+ollb q^=" g4nt "llHzlz} trIs_$ ?ol ¤4. nz= 1 (b) nr=1, nr=2.01 gr+=-e E"J-d OllLllloll t[|36|'ff trlsfElq flq.
=
e0' eldoll e]6}l^l -Ll tr1.5-Bt+7l. trt= trlE-tsf+e ESEI= a= +e6M4.
trltr|.= g^11+ EHSE e4B LlElurl.
V n,.,,(x,Y)= ?'-(ry)''(ry)
¤zlrJ 0< x < I, 0 < y lL trl5--J+ l8^l.4Bl eD.14a)
h'
E. -=(12 *7'\'SmIi, -50h2-
V,,.,.(x,y)-0 txl- ll{lrJ "t SmIi
h' nt=7, nz=r"J 5.J6J *=u}. tr++^l

8,,,.,. = (ni +n,)
g;f ollt_l^l
=91
lE,\t'z-+-dl (7D.14b)
=flE abql"tlHzlE
soh2tsmL2el qlLJzl z+eE qglqq il¤.
=+l=
g "J + 9l+ rBl+ A+ql El+^J= +E6l 4d"l oI
*d ,, =1, nz=2oJ A+9+ nt=Z, nz=l"J a+E ^J1t6|]
}!-zL.
q4'+94'9-E q+q= tr4E"l 9lg +E 9l+. ql
h' : 5h2
-tr^J =5, nz=s"J ^Jql7I HIE "lBl6-J qloJq, "llHzlzl-
v,z=?'-(T) '^(+) Er.,=(12 +22)
8mL2 8mL2
nr
s1h2tsmL2ol+. tr14^J ol dd4 o e 3+o _E. qE+

2 . (znx\
Vz.t=Zt-[-T ) .r(?) E,,-(22*r\#=# qq 9l+.+¤4 qq+ +^ =+l=
flzlql^JE 444Erll(Eq
8A), ol.:=s- dPzI abql 9zl t*E'+4d' 4?C"| zl
"l$g tolal zlz)u] rEel ollulzlE 5g6ttrl.

"J¤+.
qlq^lzl E"J6IE^JE jilt..J+E"l trolel olBlel ^JEHE
g q5lqfl+a "J+trI "l a+ql= qlqzl 5h2t8mL24l 'll*
al* t4zl z+p_e qslqflqr "J++. "Je}4qe E"J6J 7D.t* E1'J Etl
{lHzl"ll NTHE ffialfzl 4g"g ull5'l'r+_" + 948 ^J
ql=+r *+. 8zl9 ,lq Lil+oll.<l oJulol9 ulHI¤ qlqzlzl frlo]-rll +
9slz} "Jq+= ag 4lE 'il44 +4lg+. + qs| EL+ 6J4e zl*zl ?+g *l=,\lltrs "JzlEqL4 +Elt+
=c"l
qfl¤
v,,z* w.,4 Fild trsE rB zo.sql +44S.4. tzlzl (rH 7D.e). trlHl¤ qlHzlzl. OoJ ¤E 9lHzl
^tolql
aÎ4¤olo e 90'el sldql el6ll^J oJ uJ-=.o ol--,.-'zl. rlg ffi z| $a3a3 {l %_"E ¤-4zl-E ^}Hol gl= a+= re6IJ E
EL+E H-J+ 114."1 E"l C*¤"1 "IrlE e0" qdq EEI zf. $ujolel qlqzl= %H+ 4+r ,Ieil+. $"J"l7l g
olel6J tt-g H¤+ol Ezl#6}q, 44rl oltrll= v,,z* w,,ol
9s]9zl ?+=tr]- "JHJill ^JzI9 A+qlE +e¤. E4ri tlqt
qElql 4+¤trI. olBlqL trlsiE gl5"l "Jzlqql4 alql vo
=9
rl "*ol 44+Erll(qle^J +a gzl, Eq 8A), ol=g E.+ >
4le-l .Ia^dql^J r g"Jg +g + 9l+.

<l-
,to*0
Uo
H
0 x
H9 ,J"Jzlr.J D.lfl CÎ4B ttzl49 g.I]Jol7} nt=r, aal 7D.9 trlEl¤ 8q= "JLl= g'JolE trl'=-Bt+. 8E0l 7t6l +aÊ ,.el?
nz=7oJ tr-Elql fl¤. trIE qlHzlb q+r+ rJtr+. ?j= nll= itl$:Bf+7|0o+ ElIl Lle.E,\l g=ia_o.tr uul^1LfrJc|.
tsxl-=.
7D EI! 2ss
-
+g-E+El ol tlqg 6J6llî g u}]= oJEJolTI dt: ul^trro 6.P- +q e_=+ql^lE oJEJolT| ef4oguJ gf,alq q4^l
7l^la_ ?lzl"J +q qlql Eq7|H ul-si" grfzl tlE-6l-zl ?* dk 6J"Jol TlqE ++. olag oJel ¤.F%Eg *= "J"Jol9l
=
a A!9{ zlH"l Hzl ?+g trll} ,l^trro 6P-zl zlr$ {+¤ 4t <tol4.
tlzlt- ++ql +Elg 4o14. ol7l6J 4E trllEql oJEJolzI ol g+oE+El oJÎq= "J'Jolq qlql sd6J r++Er-+=
+eg E"4e. +Eg -zdge}4_e_E= ool gzl"J "Jzlq+ q-q=r+ eg aE=E ol+q{rHrH 7D.10).
4e + o"l gzl g*=+. ole+ ?ol r.d4 e + #zlg gq¤- g,tls|1aekE "JE gF%hg +4U4);
eF6Ir- 5r+6]1 4zlE ¤{}¤- El'J Esol4r ++
^JHeegEl HI^tqE ul(Be-'k +q +E+g
Schrodinge' 49 4r|4¤E trlH]¤
ol+61-H Holz} wql =
qlqzl tlE o-tr. g+s-e+q Eqs= e* .oj glulolel +e}rflq, g+-e-EE ¤Eol4); {r
tlq ,{+9lrl zlf r'4{ e s H6l-= Afl.zo.tz -
,to
=r+ +E¤ 4lÎc- + 9l+. tlqel 94(x<0)ql^l= rl-t.6r- Rr

al);
fzl v-og "l]e-l 4+ rJeq, zo.z4ql Ir|+ 'l-+4 ?"1 ¤ il
'l0l
+Eg C+4s-e- Er+6 +(Elts Btlss) s 0|ru
+.
E+ee A+6H7i= "J"JolE +4.llb ll*iil
pp = (2mE)ttz (7D.18^l).
V=Aeik**3a-ikx
qJ+oll^'1el trlE-er+
8q (7A.1s)
rq-l q¤l¤ qlqzlrl "JC+ {t %g 4= t}E gq "JoJolTI tlq

g4(x<o)ql,rl +x4(e=+)g 6}6ll Bol-
,Jol a +Ee lAl,ql Hlql6}q, z}q s_E4(x>v149lrJ s-E+
(0 < x < t)ql^J. Schrodinge' !$'l*Sq 448 + 9i+. g 6J:.]] BotS +Bg lA'lrql Hlql+r+. ol5 + ffiel ul
ln'lrtlAl,= oJtrJolTl-tr-qg F+4= q¤g +r1.4= a

-#W+vorv(x)--Evk) (7D.16)
o +rl FEI q= r+_r. o.J+.
E. %ol7l"J 6l-E zo.t'A"l trig+ ae "JHI6HE *41 g+ A1+ A, B, C, "i DEE Ate. tl'trro6l-r-E "JHI4"J -d¤- z16
¤. ol+al]^l +ts + gt+. "l+qE E+.="EL+: zJ.$ p(r=o
\I = Ce*' + De-** *51 - l2m(Vo - E)l''' 4 r= v0ql^J ¤+ol?+F +tr}. +
8q Eoll^le] trlE-Bt+ VD.17)
ol 6ll= 7D.r64 3+Hql BqHH ola"l 6]lg9 +eg + gl

r=gollr-l: A+B=C+D
x = I4lolllJ: Ce*w + De-"w - A'eikw (7D.19a)
4. ¤zlrl f E6llot tr. +s+ 5ae 7D.r74E + zl+EI+
7I doJ+ol{, v=0"J ¤qql^J 4lt6}= +++zl-"tq4=
tlq ¤ql^J= iil^tr.o6J+84 zl&2\(olEE lil- E6J+)E E
4o14. v=ooJ +q s= fl.x> vflql^l c].,t1 r1g- aJ ¤4ol4"F +4t:zB 7D.11).
4 *ol g+.
a = 6olfAJ: ikA - ikB = rcC - rcD
LfE e=+E r = Vlr9lll: rcCe*w - - (7D.leb)

{ = {'sikx p7
- (2mE)tt2
trl.EBr+
(7D.l8) rcDe-*w ikA'eikw
g^ltrl
''l
<F >
fir F]IEJ trl <l-
UO --------------) ,to-D
H
W
H
UÎE trI.
x
x
fal 7D.10 g"Jol7l e!+o++E1 Eqoll g/.lE n}| trlE-J+= 0l+=
dES 95=-e.e.9 CE FJ= L|EILH= trlEo, e!+o-eq FJ= LlEl .ral 7D.1 ul5-ef*et r- 7 lZ7l= Aq g Eoll,\l E+0 lato t :dtl. 0 I E+
t
Llits HJ^tEl= 8Ei, 8E Lt|+oll^j Tl- ?J atxlU E6ll7F= ¤El, r.alr IZoe "Jtrlgol All gqq qE-Er+=o| E=qq, r46lq Schrodinger
8E HJtHtroll^l9E.* qEoltl.. atloll LlElLl= Zl+= +41= EE + ?]tl'.
"J-BFelAEE +EILH= (q-d) ^lel ^lolsl
256 7 Ztrt=
0.5 ----r----
7lq3 g'Jol
0.4 0.8 T-T
]- <F
- 0.3 0.6
+7lE g,Jol
;ibo
qu
2 UO
,Dll 10 H
fr o.z
tjlF
0.1 0.2 x
4
1o lg 7D.13 +7]E g"Jolel trl"E:Er+= 8E LH+oll^1 7|.qE g'J019 trJ-
0.2 0.4 0.6 0.8 2 4 5-d#e.+ uulE 4-=_e AdEq-. 7|qE g{Jol7l E1'J Erle AE= Frl--g
(a) gll 01lL1xl, E/%
1
(b) g,Af ollLl^|, E/% ,tg 0l q$olt[.

=JEol t||trJ6l
=
aal 7D.12 4]{[48 AE= EI[6}| Ll7l,= Fil q= L +riJ += g^l-
Eltsg'JolE ollLlrl= 8E EolE uH#e LtE[1.!trt. +d 8E
W(2mVo)1/2/hel 'JOltrl'. (a) E < Vo; (b) E > Vo.
^lE= g atr+ dAI tlqg EIH ¤tlsE E"46]|43 + glr(rfl
7D.r3). Elts ¤tle- dzl+ #¤{m,, =2O7m,oJ rfl$oll r1la1l
olE +z}]9 7D.le^lEql q6J zl+6t41 a +^l il4E 6l]+H ^J=

rll+61 +,q6l.q, oldzHz
r=rg\om,)ql
q6il^l= A +t
_tre +s_6}l. EtrJolTI +4+le++'J +s6fltl+.
q+4 ee Fr+ +E^lg Bg + 9l+.
slqrql^l= *czlz} +"JczlB+ Elts +r+= d4l "Js
F4 qE
vJ + 9leq, olE oJaJ {4 aqSol gqt4. "JCz} "ld
T_ { [xlr [7t:ol xl.rffl (7D.2oa)
HI*el mI= ¤¤ trEg Boi+r- {lz! u}e "Jdz}z} t}qg
t
unlezil Er+6J + ?lr -Z46l-0l
"Jdzlzl &e=e+q ¤zlE
¤zlrle=Etvool4. "l oJ+E aH zo.tzoll rrlal*.Erll, uufEzll old6I= ¤t"I4. 414 gzl .r.1o1e1 "JdxL Elts F4
E>%ql a+E Fq +EE 6J4l +4r11fl+.+r+ +Ee + EeI
"J+ o+-+tr]] HI+ "llrl-q.E ql+61 6,96J
*4ag^de#*=+. =
olzlE.6I+. =e
qlqzlz| 1t$el 5ol

T=0, E<%"J oll; "J"Jolel
E+ ql*61 4r-efl ++71+^lg + 9lg Atre z]trltt q 7D.6
z++ 4I¤ +r gzl9 "JCzl-b +ol7} 2.000evola aol

rzl vr4l Tlvlfldql q+ rzl ftzlt;f,r4., "J"Jol9 zl. toopme fle +ql e-d?l+r g + ?14. "llHzlzl-
glHzlzl tlqE +olql "*Eg aEs +oldql afl'}lql *Cz}71 ol 4}ce+El uH].
r.ees ev(0.3le5al{l
Elt-J +r+ ffiol +ot{+ # Ar+?J q¤¤ 7D.20a41_o + 4l,tlg + ilc-q, e=EtVo=
"|+
E, %g r= lql d=6}zl"J u d= +Ez|
oll trll ,.Ei
t.995eV/2.000 ey _ 0.997501 q, V s_ E _0.005 eV(8.0 x Lo-zz I
*61 L?-14. ol49 Alqql^l HI^l+l ffio1 9r4 ffi
ql 4%L)ol+. +C rE zo.tz^l o + +++
ag 9olalEql rdq+4 e-E= $ujolSol
=
Sd6l tlgg'J"lzl"h al-b 4,"1'L
.- _ {zx(\.67 xt0-27 kg)x (8.0 x Lo-" l)Y'
1.055x10-34 |s
rd4_o _+ qltq= u}q e.ol E>%g qlE r= r =L.54...x10'o m-r
olch $"JolE qlqzlz[ f,t$5_+ +td trI= t]
= trl+î
{ol golzl ?*=+.
rcW = (1.54... x 1010m-') x (100x 10-12m) =1.54...
ol ++61141+. olq^J D.2oa4g^

"l+6l-q
q^g er+= g=q.
T = t6e(t - ¤)sa*vv g/+4B tr1E!¤ gH; rw>r (7D.20b) r.-r 1"r.s+..._.-r.sr...12 I

T_ ' ' I6x0.9975x(1-0.9975)
I
=q- $Eg +qE +4le| mlt2oll I[I-EL^J zl+c+4_eE ai = 1.97x10-3
¤lr(rz} mtt2all Blqlq}Q). ule|,<J ¤*ol 4rg $"Jolzl 1A
7D BTI 257
-
j
K t1 =2
5
o
{il
5 <F
,to-0
Er {il W
H' El H
n=1
9il, x ?lil, x
fal 7D.14 R-Lf-Ll e0lel tr1EJl¤ +=. rg 7D.1s ral 7Dt4al #e qEJl¤ +E +oll '25"1?l= g'Jol7l'Ll.EfLH=
F El^1=+leltrl=:ct+=.
EIH ¤tr-4 +fl$ t EzllE +*6J 4ol9 HIE--,"E trl z| $aJa|4. olqql ^JE{$$ +4.-ll= "J"J"l= qlill_e. +
Hl¤(rH 7D.t4) +ql il= "J"J"l9l *aJ 4ol+. +E "Jql E +ql e-d?l_e-Ftr. ++ 8E]|+r. ++ "lel+ +allql 46J
ElHl¤ 9lulzlzl- solq irl-E.o6I-4'- +el6l 49 d-zl + Schrodinger !9 zl-,<llal r+6]] -H-H gHl4 o e ++ t}flel
^l=
"J"Jol9 a+ql^le+ ?."1 tlE"d4.*Ez|"ll^J= qfl¤ ql += trIs=4 ?9 ru9 *!i e'1.
Hzlz|+++ {t %eE ^}+.J+.E.%"J rllE zlE +s
E aFElql rlQ u1-=" at-''r} qlqzl tlq oJeE EqA qli-l N-1<9Y.* (7D.21)
e +4EI+. ,FE" ++= EIH]¤ tlgg bflg qle+ Ag "J^l

o + +il + glsq, ul$zlzls r zl$zlE_ ol qfl¤ Eql {zlrJ %= +89 4oloJl. rg r +ol+. +Eol 4r -Jq
A++ ++ tl4el fzt "*"t{+. r4 a z}olzl +aJtrllE El
¤+4ol?+ot 6J+. ol$rll 7t alzl qlqzl a|]# :H
^J H "l"l ol EqE * +ql^l flEJ tzl-qI 9"J"19 A+e+
TD.rsql +4'ilfl+. gol 7g tr"Q]E +E +sE}|_a E+.
9lHzlzl vo[cl *g uI= irl¤.-J+el +(+ dr-qE +)
=9.-d7]|LJ=
trr. z|$ ojulolel gE 9lHxlE "JÎ3rlqzl ?+=+. 47. zzlfl. ol^Jg trzl4 oJEJolTI
*= qlLl^lE zz11
"l^J9 rzt
rJ2. ++ EAg "J+^14 Ql tr]1= $C.J r|E6J+=Elol -{8q g t}^l4 9"J"19 qlLJ^l= Et6J ar+ eq.
q q+^l ,t++*g E¤+4 il# zlzlzil E4. tr8. Nzflel tolal ol 5"J qlLl^lql q¤¤ q= qlq
tr3. gxt+= cfolq(c+ql q4^J= Hla+) 4lel tlEilql ql ^l =.fl7l
N=e.E ElEtgtrI.
eI s.z1z1 gr1. tr9. Elq+ alel qla ql+ql +Elt+.
rJ4. d-z} 4 "J"JolE 0E ollLlrlE zlzl4, ol qlqzl= q ol^J Dr0. EIE E80lt rd4g-e= d=.J + s.= +zlg ¤q +
zll|qzl ?+=trI. o + ojujolzl E4zlA+ F!+61-= ¤rlol4.
trs. ql8 8El| flelq e-l6IE "Jzl-+7I t¤ trI= oJzlE+ol r trlr. qts Fr+ +=e qHI¤ tlgE +ol7} +Jl6la_ +ol Hq
dqql4 E"Jqldq. e++ *oI+14.
tr6. zzl-fl "l^JE t}zl 4 "J'Jolql qlql qE6J+= tzl-fl ^J.z} at2. Trqg g"J"lE +4+ o3ujol_H_4 tlqg dzll F4.J ^
+ "J,Jolql q6J el *+ e+. el+.
2s8 7 gtrtE
=s-d^l=
,rlzl
cie, .,.l
-l +î al HE
zffi oJulolel E+JE" E+e+ .llHzl
V* = Adk + Be-tu E* = k'h'l2m EE t alol al+¤ 7D.2
tl.zl 4 "J"Jol
1il+l
ty (21 L)''' sin(nnx I L), 0< x < L n = 1,2, 7D.6
=
^(x)
V,(x)=0, x<o 4 ,>r
9lH zl E,=n'h'lSmL'
zzlil
irF" EL+ V,, nr(x, y) = V,rk)V,,(f) flp /l.t= 1,2, .. . 7D.t2a
V,,(x)=(2lLr)''' sin(nrttx I L,), o<x<1,
V,r(Y) = (2 I Lr)''' sin(nrnY I Lr), o1 Y
1 l,
"lluJzl E n, n, = (ni I t, + n) t L'r1h' lam 7D.r2b
rzltl
V nr.,. n.(x, Y,z) =V,,(x)tY,,(Y)V,,,(z) frp fr2, nr= 1,2, . 7D.l3a
9lHzl E n,,, n, = 1ni t Li + nit t, + nl I t )h'z Bm

7D.13b
F4qE 1= {1 +(e'h' -e-**,\' ! l5¤(t-e)}-' {Î4¤ slHI¤ tr-q 7D.20a
T= l6e(1 - e)e2*w +r" Hg {Î4B x.q 7D.20b

Eiil .rtr
+-l ,E rtE
ljo
OE
LO
-
+zl-+ _aal +E ¤el"l dtlqr .J+Elr flqzlE 4aql

> E4E ull+ ol8
ol
r
rJ flzls=g B+ +lzl ++lql^J TlE¤ ql+. ol*l6J ++
Erl Tl# gEg(EE 2Aet r2E)!+ e3 Eqqt4 ¤trr| tr|qt
HJt +E(EE l sc)= 6tl{6k q 6rd q-g= etct Erl d=el E ef,-$ +r}.11= TI1I ++6J Eeg'=sI +Ee'?l u|, ol tr.
qql^J olag zl.,{lal r+6ll H _nz} *tr}.
TIE+#+6114g 4e-lC #(EE l1cel1lD)E 7l6ol7lE
6lcl-.
> E4C 71lE!

7E.1 4â[ I.!=rt
Tl5 ESel oilLlxl= g^ltrlElol ?Itrt.
rdqqr-ql^J 5Et c=rt= ¤¤ dg-tr.+qE
H+l rgl Hl4l
> ge.Et qHl rl^l 6l-= ++lqg ts= 4*."J "J"Jol4. EI+zI9 rsoll,! t4
trJEl¤ -Bt+7|. +olxlfl Schrodinger ¤+ ?lolot Ettt. ¤Eql ulq ?"1 tl+zt "J"JolE dt+ v.717)a_r+*
trtffi .FrKEq 7 D)el 7 lg+Ef el^]3
7llEE E
El,-J
Sz ?lolot
T rlli l(EE l 7c)oll tr:d ¤¤ a ++lql^J 4l+ #
6Iq, ++4 ee qfl¤ qlq
Ettrl-.
zlE AbtrI.
V(x) - *k,*' g=C:d trlEj¤ ollLl^l 7EJ)
ElElrle] 84 re r.d4 4-at Tl=rl

4*ol .ol oJuloJz['Hooke Ha'e-] B= # zI9 4 1lt+E a_(klm)rzoltrI.
E"
a$ {5ol4r ++. ol $;lQ$ "J"Jol9 =aflqg trlHI¤ 9lHzl ye} ql

¤Bdg_e + Î"lql}.
F=-dvtdxE +4lr| ^dB
EIE H+lq Hlqld-= 8"14. lil-fl 4ql q6H^J= olag tr} 6lq(Eq 2Ael ++zlE t:l o), Et+^-l iilHl¤ qlHzlts
s-rt ?ol +48 + 9t+. Hooke9 Ba +lql} q+q tol *41¤4.
Fr= -k{ V(x)=lk,x'

tr+?+^J Newton9 SE flilE+el E"lzlH r +F glHzl, + +q
4l2Hzl(F= ma-m(d2xldP), Eq 18 oJEJolTl-¤B
9 4tlz}9 tal sg _H-oteD= "l+6l-q olag q+r+
a ol fr4oJrl.. r4r HI+t dol+r aJi fizlxl e{ oJujol
ol +48 + 914 z[ {z]ap _EE qqzlz} flHl¤ qq4E HaJtrt rBlH
ox
t2 "JoJ"lE BB dg 6J5ll^J +^l 7l^+qq BB dg Er+6I
m*=- krx ,il gtrl. HI+L a +="ll^l= gEJolTI 7l* y44l ¤+i6t il
E_o + ol *ql^l g"J"lE tsag. +Eiol 4qE B+.
r=091^J x=0ol4$ ol 6ll= trl*-r+ *ol S4(+l
^lE ^lql lA4 dFzI9 *+| A x*Y t E]¤l¤ .llHzl *kt"\ 4
Bq^J q"Jg + 9l+) ill qlqzlel qlE o|44, A"IA +lil+.
x(t)-- A sinznvt
"--*(*)" *,r=r(T)'''
ol 6llql 96tH "J"J"l9 +lil= 41t+ v(B+lEHz)$ zlzl
4iI dfl= Hl++ dg dzll Bq{q. rdzl o + .s
zlzl frzlolfl
-11 sine *fgl ,r}+)g tl+ 4lE"^1.9 44154 "llul
B6IzlE tlz}9 eE d+olr{ ¤*aql ,||gfl e=*fl Hfl
y a=2nv(++l= a'J; +q"J)o14. trl-4^J ad4 asl {
zI6zlt4ts 4,"14.
260 7 zfl.=
8
t @ a
7
tr1.J1¤ ollLlll
r- 6 I
j t{J
K j \ 5 I
5 K
5 4
6
6
qrlj ha 3
JU
El
H tr' 2
0o
'15' 1
Y=0
L-
0
E9t, x H9t, x
lal 7E.t rsl.CErlel E=CE trlEl¤ ollLlxl Vr.(x)=ik,x2. xts E trJ-d
aal7E.2 aEl't!5rl.9 ollLlxl )J7:ol A"Jdl-Xl hofrlLl. q7l^j
o_e+Elel E+|trI. a af+ kfTl714J+= +.N01 Tfnle_a. 'J0l7l Eol.Tltrl. =g=g
6=(k,/m)1/2olEl. arl SEt|oll,(lE T.lEIlE ollLlll= 0-8tr[
=tr|..
¤zlrJ &E E $+E^J rllzlE +4{q(rfl zr,.r), u|4,rJ glHxl #glE=e zJ4ol +"J6}rll ha"J rI44Eg ol
=#lEq qfl¤ qlqzlE
+91= "lEl 'J hH(Nm-,)ol+. "lElq} E+(r+ 7E.2).qlHzl ?J4 hc,E qltl EillTI 4^14.J trI=
=9
'eE^d i{ql¤ "llHzl'E='E'EdB qfl¤ qqzl'4r + (= a%L) +^lB + glg atr + 4zl"J flzle+ Hl+ql a+g
trl+^l tl*4ql 4qI scnrodinger 4g ++4 *ol ¤ 7IA ql= ^J'J."] {lol Etrl.
=+. = q-q=4 ,Je <kg
+ et+ 314 y=soll.(jE-
"llHzl= *=+.
=+l
h' d'ry(x) Eo- ltta oE oilq^l (7E.s)
- 2m-{ + }k,xzty(x) - Erlr(x) Schrodinser
^l
(7E.2)
0A qlq \zl !zN{+ E4*4 ol.,?E {lzl qI oJEJol(Eq

a= +""oll.! trlHl¤ 9lHzlE +qlqle zl*zl q$ql ol*ql 7D)q A+e+ Zt4. "J"Jol= e-d ?ll- : 9lzlz} Sd6l E
oo1 9"1ot ++. rfl+ qQf¤ 9lHzlE {l
^J= +¤ifl'Azi q.Col ofrlF + r +t-%F, EI+^J r ¤+ qlHzlE d+6lal
zI "J "J"Jol9 a+ql^le+. gel #4"Irll il+zl gi-l- S"J
0ol E + H= 4"14. ad4 o e ol od "llHxlE 6ll46tz}
6}rll +El4e. +ztalq, q4^J ul^s." g].+z} s4l $"JaI4l
H "Jzl C*tzl-=. ea $d6l czl9zl g:eq r?-l4q ¤+
0o + d=6Jtr1. rEl+ rlt-)=Ool4E zzJA 9"lE 2641
q+^J {lHzlE *ril ¤+= Lol4.$}"J olr-14 "l +5g ¤B d

Schrodinger 49 "J+ 6H"Jol -"]+qr {5x1g qlq ql^J iilHl¤ "llulzlE SA61 4 ol+alzl ?+eq E|?+^l i4Hl
zlTI oJzlslqqo} ++= 1,"14.
¤ qqzlzlool 9zl ?*E4.
oJtrJolTI EEd¤ Elfl¤ql^J {f6l+ E¤g zflz} EzI
(a) 0!u1x!
=+l A-Bel dE ef;$ ¤B6l+ ql ol+gutt4flz} Ezlotls C
78.24+ 6J E= E9 ul$ *{alolQ r 6lzt +q'-4 "e g n6}4l 4+^lA+, Eq 11D). ol A+ql= F flzI
^lolE A
"JBi4 gl+., q+q= qlqzl +s=r+ *9 4Eol4. El"l t*qr "J+sll a1g,r1 F flzlz} ¤+6Iq, Irl4^l a
=gEe
B,-(u+!)ha a=(k,l*)''' oilq^l (7E.3)
* *Z trl+4 eg 8E traJ p-e. 444ot qI+.
=+1
u =0,1,2, ... ffinffia
ll= mA+mB PE traJ [29^lE^l] ?E.6)
¤zlrJ uE TJE ?Ir!.++. ol qlqzl=g dll E=61q, a.E
ad TIE" zI9 4{sfe+ E.J6l-41 e%hr+ 6J tl+ql el=6}
flz| Az| BE-trI +ltl +rlg ull* E:r 44 ms* +^lg +
tl^l l8g s.oleD, aJ {tfzl =;,
d=Jol zl-"I
9lsq, +tr A*g tt=ms7l99 ziHS flxt9 e*r+ eAl
=ql($+zlE
e++ 4A+= ag +E_,6I¤4. ol E6IH qld ¤4. olqql a+qlE zlH¤ flzluJol TlE6Ir *zl8 flzI
^lql =+15
,J4e rJ-q=r+ ?ol ygl +s6irll E"J6l-+. Hl-9lz-lH Czlatrll g+.
^tolE
=
E,,+t- E,,=ha (7E.4)
z]trJEt q 7E.1
I jl+ Î^llq}
.11¤+ z-izl+iol *f Molecularquantummechanics, Oxford
+g. A"*g q-q=4 A+
University Press, Oxford (ZOt t)S -9"I4. 'H3sclE
7E T.l= 261
-
-fr.7EJ Hermite tr|.:d -Et+
*,ô 9929',)*!?4'?68812 H,,U)*
,,- mH+mct= ffi=o'9796m"
)
{1
a H'v)
0 I
"lag "JczI9 4=++ Hl+61tr}. A.JE E tf+ r, I 2y
=5r6.3N m-'o14. q4^l 7fi^lql^l m* pE HL+q Br
2 4f -2
1 N=lkg - s-2E ol*olH q+r+ ag ¤r+= Eg + gl
3 8f - rzy
+.
4 r6y'-4qt+D
(
7.r-rlr-r_l
k,\''' ( sl6.3Nm-' )
U2
5 32y'-rcOf+tZOy
=5.634x10t4 s-r
(p i Io.rzrox1l.660s4xro"' kg) ) 6 6qf-4801 +72qP-n0
* Hermite trl6} 6J+= rig4 rJS
"lE "Jt^19 6l]ol4.
a eg.azrHz(2ntr ++q fH)zI g+. tr|E+^J
"Jd ++l Hil - zyHi + 2uH,,= s
5 ^LolE ?J4i., r+g=4 ?ol ¤4(78.44). {zlrl E4"Jg oleg _*rlaJ4. ol 4o} E}+= q+r} Ae ?lb} +al49
"J+^lAE+.
E,*r - E,= (1.05457 x 10141s) x (5.634 x l0r4 s-r) H,.n, - 2yH,, + 2uH,._, = 0
- 5.94L x l0-2ol +¤. 4Eg {i 6.e-6J S4lrlol4.

1 sg.+tzl, o+ 0.37eVo14. ol {luJ 71 7J4e 36kJ mol-'oll !* H,,.H,"-''' dv=
0 u'*u g trll
xt''2'ul. u'=u "J

"+
oll
all$afe__e Elol4 ql+61 atoltrI. :r_elr 7E.s^lql
=
el6ll^-l ol Ezt 4lE"ztg 0a qlq4= E ze.7rzlzl gErll, 9zlrl H,(y)+ Hermite cFd :*#e^l ol +.Jgi+=E
olag 0.1eeV + t8kl mol-'ol g+.
^dA "J+E E 7E.1ql +=_6ll +?t+ a*
p zJlel Hermite=-r+
4
6J 6J+= trl]E6l ++6I+. qla'H Ho(i= loli4 H,(y)_2y4.
Hermite trl6J 6J+=

r5g B+4r +s=.J+#ql +
=lA.
(b) trl.E-:Et+ ol caE
'JBEI +s6J ^Jeg zlzl:t_ flsq,
aJu|. olp_o_
n.24E E+ 6}lEe. E+ q=q-r+ B¤- Eol g+. $ ols-" alB "Jzlqq}4 414]¤¤ Elr4 drll e. + gl+.
u=goJ Blq tlEllE ii}{iEl+= q-q-r+ ?"1 S4.
12(x)=Nx (xoll ** +-J EI+)x (ao EoJ Gauss Et+)
qzl^l Ng A+g} tr-++. Gauss Er-+= +-E"J gg ++ VnQ)= |rln.-r''rz: Nue-.' "o' HI.J dEl.l trlE-el.+ (7E.8a)
e-r ol4(lfl zs.:). Aq+ gel irFE" gt+= trl-s,,r} *+. r;ll 4q" 6l-b q¤ trJE_E q+4 ?Jtr+.
- N ,,H Y'tz q-E:sf+ (7E.7) qE "JE

V ,Q) ,(/)e- v'r7)= Nn'e-,'' - Nn2.-*'ra' of=i 8E[l (7E.8b)
y-* "=(h)''^ ol ffi[$s] E4¤. trJEE rB 7E.4ql +E].1]fltr+. g¤ EE

¤zrrr
E ¤¤ +lil"J x=0oll^l al4zlE *zl"J "l +lil ++lE i44
0.8
AK\
Il \
\\
x
0 .6
iui
<l-Efl
il ,\\
/t
I
6 o.+ $*
\\
0.2
0
4-2024
fi.A, Y = xla
-2 -1 0 2
x
=eJ
7E.4 asl- T]Exlq A^l ollLl^l SE]|oll EH-d E+et trf5-Br+et Bot
lg 7E.3 Gauss a# f(x)=e-t'elraflq o+ ulElt! +E EE
262 7 eFlE
=-1t I a')ry o+ Q2 I an )ty o
ol 44 7/-(hzlmk,)','& 7E.24ql Eil"J6lE q+4 eg

"J: ur
. rl.l Ar+= e4l gtrt
{l-;ru
i!i3 se (h/2)(k,/m7r,z kr/2
H,pt,
v2
h2 *k, f1, mk,
Vo--2m x2ty o+\k,x'V,,= EVo
2m It' h2
4 -2 0 2 4 E|4^J (a 4 6Jg trI+zlH^J ),

YA, Y= xla
azJ 7E.s cE^l.el Irfl gE|loil rH-d g+sl uF=:Br+sl E"Je-e

^s+ =E vo- \k,*'vu+ 1 k'x'rs. =Evo
LIEIL.! *E EC" +(*)"
r4H eÎ 6.J="] ^J4lqa +¤-r+ *+ 4+rl-+g+.
ll4. olE +del +Ee +E qlqzlz]. ool o].{ ,\l.¤g aJzl
q= A$olq, Eld"l 44+= Ae irlHl¤ {lHzl q^l 0ol
olqq^J 0d qlqzl= *=+= -JilEl= ¤4"14. +(*)" v'=Evo
Îdr+
ap+ {t-z}E arq t]"El], 4 u= l.J ^}qlql ril+ u+E
=.E r46}q rg.3 9lH zlzl r,-ih(lqlm|rzol ae| {:E" z}ql ql
++= trl+4 ?ol ¤4.
* sctfodinger 94, od 9lHzl9l s* zs.salr+ +B
qlrl^]ol
E Tr
-+Jrllrn EE --lu zi;rlzl
ult- a*l ' | -Ll-l .
(
v,Q)= N,2ye-Y"'- N,'\a1)*r-"''' ) AlEt| tr|s-sf+ (7E.e)
\t7l B7l 7E.1 7E.e^lel 78.244 6il"J9 +

"Iq= 7l^]|4, q¤- ?16lr- :a qlq zl= aa6}q ?+.
of g}+t- ss+l(x=0)ql^J r,JE_l x_ * a
ql^J +trl]= +qu+(re zs.s). a7t =,g.ht"[e .E
@ schrodinger al9 d]|Tl trl'Ed+g= Efl

E}EL rl-E.o e-+(7E.8all)zt Schrodinger 4]p..z4)q gg u;=.o or--^-g E"Jag a4 7L.6ql +44i1, 6l]R6l+ +
^JEll "}l
"Jg q"J6Iq4.
!.el-g AIB 78.8a^l oe +qzl= +EoJ+E 7E24ql E,
6
4"J6E alEol ol +H4 polzllxlE B+. 7E.74ql
Ehr,t
^l
ee-l6J o= ol+*+.+HE I +-6llzl= oJzl *ha \ 5
^l
71 78.s4+ ?JAl9izlE +.J++. \
Zho ) 4
q+r+ a"l Hlqtlq u|:a"ffiE zz| rfla5- 74
=ol
tr+. lhat \ 3
rlO[l
Uo
H 2
No.-'"' * = - *,(#)"-
r''"'
*
I
x ihat 0
rzo'- !--
#*t-" N
a' ,
-1 01
d(fg) / dx = f dg / dx + g df / dx Eg1, y = xta
aeJ7E.6 4.6+ t!E^l'E x1= gE

A|'Etl= L|EILH= tr+El trfE:sr'+=. ol.tl
\.-,',,o' . r, (# .- .',,o' #tl uil'JEe=_ +E-6fqat. u7l$#oJ trl'5:et+=e l=0oll g6ll,\i EH8olq,
)' :Ef+
Ae UqaglEl. trtE-Br+EE-e. trlEJl¤ ollLl^l ?l0ll lZ l
=+g
LlElLHfloE{, 4 trlE-Bt+oll EH:d +'J+=3 6t|EJ ollL1^loll *+ol =d
=?ttr|.
7E Il= 263
-
y-atsE- E^lElq !lst=+ ol 4+E dx-adyA S4lE

20
0l+6}0l )E 717)a_ 444oF ++. gs,* 4¤+ _* 7E.1
ql +e+ 91tr1.
15
E0! C++^lA t+JE" oJ+= ++4 A+.

10
V,,G)=H,,(y)e-"''
5
trlz}^l -s zr,.r9 4¤¤ "l+610l trl*S Ar+E Eg + 9ltrl-

0
-1 01 Ilv :w, o x = a t* vXw,, a y = o [1H], ( y)r- d y= an''' 2'' ul
4g,, y= xla "
azJ7E.7 u=0,5,10, 15, "; 200J 4-elTlEXl-AIE[lOll rH-d qE "JE El-r ¤zlrl ut=u(u-r)(u-2)...1(0! = l)olr.|. tr|{^J
+E gEE gqol u7l qal rI4 EEg HJgtr +e-e olS-EIE
=71:d0ll
+-P_6tqal. v2
N, =(
1
AnD2'rI 8+a[ a+ (7E.10)
E "JEE t4 q¤ EJ_:r= "Jzh7r

tp..t4l +El-4H.4. olE
trl=+= ag +96Iq+.
N,zl z9 ZI9l ntzl
k"Idql II|4 slql +E gzlTl-_7a4ql eFq Hlgd +_q-
s olrEo6Jg Bq=tr}(4qztg rlal reg _H-oI+). olBle} c \l7lg7l7E.2 w4 w,"l zlr+¤. 4¤¤ 4l&*o_e,rJ
ae te "Jzl-+"il^l= "J4qqL4 ces+q rd4 ca +"J6Iq4.
ol +E+*+= tr]]+
^J4
gflel E 6}+el ql.J aolq. h6a go = rp,r/ifd*l U*+[o Es{y 15r.az r .E
as]- dEz| ul-=.o ar''-'t- q=q=r+ ae. +4u+.
=e¤-
EL+: qL +_e_tr_4 H9lzl-+rlElql q+
Gauss
4+61 B6}111 0o e B"lzlq, qE+^J Hglz} 7E-2 5ÂlflErtel ¤E

oll= ulsr" g-^7I
=.
oe-e d=++. Eglzl *ql^J
oJtrJolTL = E?-14 ^da.el ¤+il= "llB ¤tlz}4 zlqlil(7c.ll^1, e+
4e_1 ?+=+.
= it} ir+-="EI+= ol+* qe-[v.ay dr)E +61]^J 414]$ +
ra4
ul-="9-;==* =z116]-zl
HI+td
Îolql^J= 4lt-6}zl il+.as} +l5zl9 a+ql= +*4 Ag ¤49 4Eg +6ll
"J HI+AS'Jq^JH 4l=¤ 6l.zl *:r. e^l6J+. #
f x(mk)t/2ql HlEll4q, 44^J d=Jol fi oF *+.
^l+ f+
,Jg+e(+gqol
.=-tr ^.EBol r}f,-El
=+E) ffi ({)),=[_V:OW,a* (7E.tl)
izl cl #+6}rll +^lg+.
uzl ftzla)oll .r+zl Hermite +6J e+= Hglz} trll rr++EL+# +ill4_q_s --Jq+H 4E"l +d-6]] Bolzl"J
rl zlzlH(,ruql q-ED, trl+r^J =
z/l z"zlol Hermite 46J.J+E ^dAg ,I+ A+61|T]+.
"l+61-H
4zI ca,,s e+ qlEql o o + Bqdq. a44sE
uzl frzlt;]q] Ir+cl H rjl ul tlrx:B zeo). (a) Barl
zE.rralg ol+6}q ol d5zl-7t oJzl+ u"J t4"ll glg *IE
@ r.Ef [FoxttrlEg+el E+tr] ¤+ H+l G)el ¤r zll# H+l G)g +6J + 9l+.
=e| {="
z} e+E} tr-+. +6l.q4.
-r.49 A+EIoIEJH lwl'* d +tql
@ rflT]5xlotl EH-dxefxzo; tsaxl
44^l
^lEl
zle* q+ql 7Bs4 N=tt{Vf rydr),t2* olgall.<j G)eI (l)g 4l&61+ trJl g,q* 4Bg 4l&61+ rllE ol E
A++ qlzl¤ +6LH ¤+. fBlH A+sI rl-E.e-+7\-Nrr 4lE 'lleC4 Hermite trt6} 6J+e-l $Cg "l+61-= A"l zJ
e+ A4 84. ol lzl-g +xllql^J* +rl a +zl raolt \ S6}trl..
E3 --PQ +*nl\4. ol t+E"EI+= +-qfldg H+ E4l 1 ¤+ H+lE +6}zl +l+ rla EE

264 7 2FIE
tlE"zL9 q¤ "JE= 0d 4-+s 4?"171 ql.Eq ¤+ H9l 0

(r)E 0ol E 4.o e q^J¤+. oJE H+le+ *E H9l7l +
ot+ EIE-E +4+= 4,o14.
= =a'Nju(u- r)J- a, a ,,-re-Y dl
0
=JAl2 gs+489 a l¤F+A4+"J

nt/22n vt
Cal " + x9 Btul, ? 19 TlEllzl= trFq-4 eol +EI'J + + a'N"' (u + +)J- a,H,s- t'' d7 + |a'N i, J* u,,u,.re- )' dy
el+.
= a'N,' (u + !)n', 2'' ur.
(*), =
Ilrg : *v,,a*= Ni J: t a,,r- "'' x (H,,e- t'
t 2
*r
¤zlrJ ^ll 4+Eg +r+ *:ntg olf-all.<J +iRrl "l e4
) 1
x=W dx=ady oll4 zp.roE N,,. Bq=q

.!=. t[.^
a'(u+i)n'''2''u! _
= u'N: |1vfru,,"-"'')' dv (*'),,=
Afir,r2'' lll
(u + i)u'
ol 4Eg y)-yoJ g .J++(zlj# .J9 r

oll Pszi H6Fr-E gg-E s2 =(h2lmk,)t''2 Bq=+
7I EEIE -H oz} H6I^l ?+=+). g 6J+. dAl 4a ¤q.il
444 4+6lB gE4eE 0ol ¤tr}. tr14^l (*'),,=(r.ilfiy EE I]IE EPI VE.12b)
(*),=0 EEugl qlql^J EE E9t ?E.12a)
EI! 3 ¤+ 4l* H+l 4+ a4ql el6lE tlExl-b x=09 al+ q.- +q^J
(x),"il
rvl / ltfl^lY-l -6U ^-llt. Uil= fs{'e"l
1Î
-l-il:l^l -l.- -rI-
rrlAlr *1 .'t-t
-IÎ qqE' -r XiT.
.l-lrrI I
^l.-l + 5gql CEE ga¤ + 9l+(r1d4"J alEz}qlrl9+. *
"l). +S
(l),"t| ql6J Ar+ql E6iH ¤ai zll$ H+l= uzl *
(*') Ni,
J*
(,,,r- 1x' 1H,,e-
rz
1dx ziaJfe 44r+ "lag t4 zs1! q¤ "JE= -BolE EB
"= "'' "
6Iq, 4*zlzl E+ q E¤.++ rd4 otr at +ol *zlal
x=Gf dx=ady
ar+ ?JZ 4al7t ¤+.
= olxll
=a3N,' I* (',,'-
"'' ) Y' (H,'.--
"'' )dY tlsz}el ¤+ trlHl¤ qlHzl, ! v=L,ke*g tr}]*61 d
ol ,I 4l4I6J + glal qfl+.
^l 44
yu,, "Jzl¤ s. 7E.1el flts +4149= yH,,=uH,,_t
+*H,,*,Etr- r4^l 0l+6l.ol dz}]e}4. rfl +q ol /. ^lq] (V), = !(k,*t), =]k,. (*'),=r(r*,)n( *)"
#6}]=tl-.
y'Hr= ufHr,-t * !fH,,*t rr l-

+L
ol +1ts +41^l* yH,_,4 yH,*,41 4+^lzf,r-l(u$ u-r,

olz-fl (v),,=i(r+i)n, EE tr18!¤ olLl^l (7E.13a)
EE u+ l-q +-r-).
qI¤ "Jzl-+zl uoJ tlelg di.ll qlqzli @+i)fra)olE+ ol
fH,_t- (u - l)Hr_t* *H,, a+= +gr+ ?ol 448 +E ?ItrI.
/H,*r- (u + l)H,, + lH,u
(v),=iE, EE tr1El¤ ollLl^l (7E.13b)
r4E ++4 zJ**AlzI +e+.
dill glulzl= slQl¤ qqzle+ &E {lHzlE *d 4,o14, ?
Y'Hr,= u/Hr-r* 'r/Hr,*r- u{(u - I)H,,t+ +H,,i E,=(V),+ (ru),o14, 44^J 4lfzl-$ ¤+ gF.ilHzlE 4
+ t{@ + l)H,,+ iH,*rl
94 *ol ¤tr}.
= u(u - l)H,--z+ (u + +)u, + iH,*z
(Eu),,= E,-(v>,,=E,-iE,=iE,, EE aE oilL1xl (7E.13c)
ol prffi +lel 4Eql Bq=+.
B+ tr]Hl¤ qqzle+ ¤+ ¤+ qqxlz| f,$alzll
TIEzI-el
fu"
qHq+^J E E+71d4l qlqzlE qlr+ ?Jt:+) "l altr.3 4
f
(*' ),,: a' N j tu,,r-
l* "'' ) {u@ - l)H,-, + (u + t) u, * i H,*r} e- '' dy *4 ee Hlalg Salel el5E6J ?*"14.
7E T!= 265
-
v=d4 ae gq i4Hl¤ 9lHzlE zle q=
oJtrSolz}
*E 4E P= r 4+H+= y-xtae- +4,-ll= lol S4
r ¤t qfl¤ 9lHzl$ ¤+ s- "llHzl r["1"]l trl-g'=l1 614, a= (h2tmtq|rtol+. ol H{1-9 6}I_ E E,-(u+i)hoE
zJ* *{lzt CB6J+. ol+6IH H+dol +q-r+ *ol ¤4.
2(E) - 51Yy Hlalg ael 0El4) U2

1r1=1krlmll
x6 I z(, ++)aar I
as+ 4lEzlg a+glE b=2olE-tr- +lql^J gg HIe+ eol
(2u+l)tt2
(E*)= (v),zl q= aol+. Hl?-lg A"-l= g:g f_o"+ A4ql

/ro= a
1-]T, I
E-p-oJi zlfiizjolq g}e-B zl-f .tl-e"olal B 4olu1*ld4 alzl "llrJzl dlQl(u=g)ql^l=/,p=1o14, ol A q"lq^lE
Eq 8A).
e+E:ol trl^-q=,,+ B"l ¤4.
dx = ady
(b) E1'Jfl8 r=!-.wid* -a [i wiav="No'J-e-r'd7

"JzI {f{f v>Ee gE +ql^JE EaB + 9l=Ell, _trd
E+4 "E olq+ ¤Ee g+ qlqzlzl. $ol 9o + -"laq ¤ zlrl
g+=+. vj+ tlEo 4t rd4 o + +zlg H9l +e_E 20=l;0! ='l
^l =,
SqzlE qts ¤tl¤- "JezlE 4"14. 5-.71 7EsqJ.! .Boli
ule+ *ol 4z] qlqzl tqel ao] 4l=" zlzf l{4 o + :=-a1
''=(r,+'oi)"' (#)"'
¤ ¤qql^J tsag +Ee "* szo4 ¤+.rd4 +41 "l^Je
-+ oJ+¤ q¤-E- "* szo4 ¤tr}. olElEI qts Fr+ q.E-g dt. tri4^J
zI9 o] tF++ e"+ql +S6|+.
EEil a=rlE q.-J+ul EE 4nt

EEI
Hl-ql
^Jql eo} Tlt-zlzl a$4
o e -l*9zl ?+= ¤qql ol zi$g #s* +u=?Iq= ol+6}q +il 4l4}g 6IH
qtrg 4lr}6l-q+. o.r3e. . .71¤trI. 4a p-o.o7e7l ¤+.
^l EaB
zalE +E qlqzJzJ- g{olzl= rd4 E}*}d x,rE
^lEI aEI
+4 "JÎ+ z_0oJ t}4el dE" zl¤ zlzlt_ Erg q+ql
+4.11= 4e TlE"zI9 ElHl¤ 9lH4E 4lE di'll aa +g6IH:z Gz.go/ozl rdzJoe +zl¤ 41+ ¤E
olluJzls+ e4l +e-r=eE,Rl *g + ?l+. AE"zlzl Hfl ,* q^J gaB + gltr+= 4o14. rd4_o e +zlB +el ¤
q"ls dtlq= ag tsat-; e+Eg 4o4 +6Jql ¤q q "Jql^J gag q¤.s +"J61-+. rrFI^J rd4 o + +
Î
fl= zJ4 ax "Jql^l ol {E"zl¤ gA6J+= ld¤ zl¤ ¤q(^l+4 "J.41 oJe-E As"zlzl EIB-+!+B dill
"lql
"l gq di,il"il aa^l qql+ *al+L+.2, +Eg * roo/ozl g+.
r=!*.w\dx
xl7lg.7l7E.3 "J^h+7I u=toJ tlE{el as} dEzlzl a
d4".e +zlB gq "Jql^l ga¤ qEg 4l&4q4.
qaCg rqo}ts -r*4
^lol9
*
rdzi o e +zlg ¤ f4 +se+JqE ol+6il^J zlEg +Elot ¤- aol+.
qq^-l $"JolE gA'J q¤.E ole+ F"J6l4. gEo.o=a ¤
Eol rdqqql 96lH d*zlE HI+d &g:a S.il
4zlzl0ol g qE +lil"l4, "11,3 f_ EIHI¤ qlHzl +/qt' -r.d4 e + +zlg gqql^l tlE"zl¤ EaE +Eg uzl ¤
ol TlE"zI9 d4l qqzl rp+?"tzlts d"14. ol qlLizlE 7I.Jql q+ #+6l.rll ei4q, 4¤- fl4e+El d LEl= Ht
q+q= <k E,+E q. 6I+E- q6lH t}*d"l trl+r+ 4 ?ol zz| SaJqlE d=6IH o"l gtrI. 4^14 tlFzHrl4l
¤"1 84. +e+ eg)= ql+61 +g "Jzl-^Jqlq 6il86].4, ,rI4rJ ld
4 o e E-"]EI= ¤q"il^l olEol ga¤ qtrg Sd6l +^l
E, - !k,xz* Ir+et,<J ..= *(?) g + fl4. :44 E4-==e "JHlzl " + BlqI Tl+ ^JEHql 9l
sq, ol.ql ql6il^J= ol *Eol tr-'J6l ++.
266 7 gtrl,=
=sElTHEI=
tr l. =F] 4]s"xlel qlHzl zI49 9 qlHzlE zlzlr 9i4.
=+lEeEg trlB ^ltr}4E.g "1E4.
e 2. 3a| 4].:eox|el irl^s,o¤"At- Hermite E+el C.auss -d# a 4. ad4oe +zlg gq.Jql^l .Jzlqq}4 3o|4]s"2ffi-$
(ao EoJ El+)e+g +oltrI. ag +=g Htq t}E t}4(u=0)gl^l= t}B6l tzl"J "}z}
D 3. "Jzlqq4 35| 4l-:4" {f. 0E ollL1rl, * xllzl9zl ?t= 3li fzy ?zl${l trI+;+61fl1 zJtt4.
=sEt^lE
,\-lzl
o=. AI
-1 +4 rl Hs
9lHzl 3?l t,,=(u+))ho 61=(k, I m)''' u =0, 1,2, ... 7E.3
od glHzl Eo=;ha 7F,.5
u|.si" g-< V,,(x)=N",H,,(y)e-t''' l=xl a a=(h' lmk,)''o u=0,1,2,... 7E.7
¤+E+ tl+ N,, = (l I a,n't2 2' ul)'t

2
7F,.r0
¤r Hfl (r), =o 7E.l2a
EE xll* H?l (x' ),= (u + |)h t 1mk, 1''' 7E.rzb

HI4.J C?-l 2<E) = uv> V=a* 7F,.t4
EEf 7F Eldffi
> ol E4E ull+

ol8'
4#aJE T1|E3 flrlel ExtE dxt ?E= dB6t? s Exl
rEe.B9.ee}= ¤861ts Ell=C EgE elq'.
> 64C 7]lE

azJtF.t xy E8oll.tl HJXIE r?.1 ?E zSEE rtal'E= g'Jol.
qEill9 oilLJrl, 4EEleJ :1alr 4AEPJel H|IBS ?r^F_lEtrl.
> ge'Et qHl rlal _ h' d'rlt(Q)

= nv@) (7F.3a)
2mrz d0'
?f^gEe_f Th8rl ?3Al 4.7c.9 qg= +xl6lr. 9,lolot e}tKEq
7Ce+ 7D). clE EE4 olag LlEtLHts E1l olEEIts stE.zloil EEt 9zlrl ¤s91$ Sd sgr+_+ Bh+q +ElU 49 HfzI
¤Eq H}leg E+-trl-E 84 s,20 o) zroil^j ¤gB 7l01tr1.
0 a}4$"lzl oll$oltrl. E mf? 4lE +^d .EHIE+a +=
r
4 r= mPtr +4U+(El4zI9 dtal zo). u++^J Schrodinger

flzI "Jqlrl dzl-E=g q ++l= E.q"Jzlqq}4 rld"llrJ)
!e ++r+ *"1 ¤4. "llHzlE tr1.S4 ?"1 449 + 9l+.
E _r. zlti9 + ++lE zldg 617l ull+ql "*e- p+q} ceE fr' d'tlt(Q) Schr6dinger 4-l
2r Ery a
fr.ald|-E gBoll
(7F.3b)
"l sld ¤"F4 +d¤+. EzlE=E cldg 6J+. sld ^JEIE do,
^lolE dolE *I48lEH

EoJql ¤.Jg +q, "l# drq
¤te_s,r^l Ez| +aql +6J +l+6J zlEE gg + 9l+. @fl=ert*
?l5B qag *.
4ql q6H^l- q-q',r+ eg flEE rlE
7F.1 2il-fl EIE r, O,o) rg ols-" 6lE 4".l altolfi:-zllzl t).
*y BHql^J qlzlE r"J fl¤ AeE q4 +E" 6IE+ ++q x-rcosQ Y=rsinp
qfl= ?=Jol rz"J "J"JolE ^J4611 -pzH:B 7F.l). ol C* r4r
qlb qq^J+ v=0o E +{e- + ileq, Irl.4^J dill qlHzl
Q(7(oo 03Q<2n -oo(21+*
gF qlqzle+ ?Jl-+.rr]6}q Schrodinger 4g q-q_4 A
=
ol ¤+ +E -s-d. tls-4 eol gt}.
9i+.
dr = rdrdQdz
#(*.#)r,x,v)=Ev'",v) (7F.1)
H tl-ql^Jg ¤.E-el a+ql= z=}ola_ +Es_^= q-q_r+
,J"l ¤4
g"Jol= g¤+ qlzlE r9 4s tlql ++99 glo ',e 4
dr * rdrd|
acg ol$alzl +l6ll^J .fl88, 3IEE ,r.f$o|:z z=0 o p ts
a"l ¤4a[4r4o]z[9 /d.:l rg). ?]E¤ 4]EE ol+6]H
=
trl¤-+417| cBqI+.
z
a' a' a' IE I E,
__1 (7F.2)
rdr'r'dO'
rq+ aEq tlzlEol lcslzl qlEql ,ql ++ E6J+(a x o
v
+ -tr^l6J)= 0ol ¤+. r?-la 7F.244 rrlzl"+ 'J"J d-"t

^49 arilil 1
H-e-EE Schnidinger 4g trL'q-r+ gol g+.

268 7 gtrE
ElEtrtel 8^l 20 2loeE}

-lL:-OO
44 ^lrJ H01gg 4L=E+-r. 6l-q, a)E E^lql4. "149 {zlrJ p= "JE +z}q^-tel rr-Hoilrl9 d¤ 4s"*E =
+fl= = 44fi*d s-')ol+. + qd.$ 2n radolq, "IBl 71q. I,>09 'll= gql^J il4*g ql gEJolTI ^l4l "JoJe
=ot-
ollA lqdg Zn rad s-,o14. rq+ Eqt} 'radg trll1 E Eld6I4, L<og trll= HI^l4l %'-6JE 3qdg ++. gg
^J
4+E= s-'sEI +4U+ trlu| 4E 44 + qd6l+ $"J"lE LErll S6}i. Eg
"
+= 4 ^daEq Ell,* ^lEE dB gfql Eils" 6I= ^lql eB=q gulolE_4 +e 4¤¤-%hg *b+. nFl^l +g 4
+^l-617]l +4utrHE4 re9 44219 t}al rl. r;l6}q 4 S# 4= "J"Jol(+CHITle+ Ae)E # H+rll 6I
FJ 14 a7l /= d¤ ++=+E zzllp-11u)e] $rla1z11 qH allEq(r}+ Er)g z}4+qo} +tr}. =
trl++ zJ"l 44U4.
Jz >0
I =Ia p
<0
{zlr-l r= g"Jolg tr¤.EE!E{. +C e.HIEb qd4l9
qd Hqq q'J 4'Jg +4.11= A o e^1, "J"J"l9
tL=I 4,ilx12
CB +F tF{ HEl.ll 4t xl.J$ +44= e*ql Hl+q 4ff;=J ElEl ;zt "JelE ts]]olg +4H trll= q-q=r+ eg C
ts cd"l+. qd +zlE a+q= r +c EEIE= q^q=r+ Eg *b+.
?"1 C9aJ4.
Ir: fPr- zPy Iy= zPr- xP, Ir= xPy- yP*
1=l1n,r!
¤zlrl p,= "J.el +rJql^J.el CB gF*9
CEol4, ,%I¤t
{zl,r-l m,= gz} rE e*olr" r,= Eld+e_s+ElE +zl uftzl-zftr pr94. pF 6|]'J "J.Jg CE=ol+. 4¤-F=* Eq
44trt(^4lzl r). tlzl6 rE gg tr+El qd4+ eg="1 rQl 9 =-zl9 zil#g q^q-r+ eq.
edE cld+ql ++ +¤ -gHIE= +q-.r+ A"l AE¤q. f=11+lj+l!
I-mf
dB +E%Lql +6J A(E*=i*f -ft2m)4 +Îs}rll qdill
+{ EEIE.9 sEfl= Ir}e}^l kg -rol4, 4s"*E sl++l el .$E
"tlHzlE
trl-s-r+ *ol ¤4.
qel^'l kg -'s-'o14.
= I2
Eu=ilr'=h
mA 0
A
I=tneta2+m.rr2+morrz
+C EHlETl +qeg ql= +e 4eF*"1 k3 B{ ql
Hzl"ll 49"6J4. qd qlLlzle_l B+l= flrI q"J
.J =oolq,
mB
+ fl9 4o14.
B B{1r+ Eld .$FE a+ql 46J rn4I
^}ol,
u* o ^lol, l
mo \ 4t-p9t ^lolE +^l +4F==3 4#
"JE4+ 7lq6l 4=
trll ¤?-16I+. olBl+ +Î +41fi$ ,qEq +9t+.
"l-eilql
allil 1
Brl irld
4grE" "*g aTle+ %L6Jg ,l4l EEloltrilEq 7Dq +q ce 9"1 ,\Jlzl
de, 9rl
4E t}^l l7). 3ztgq^JE EldE a+q= 4¤.E" *ol /o 4*,m Ele-l Erlql +d EHIg I HI.=H e(E
=)ql
ql6J 4a} 4t
I* o)
rel ^ll
C# *=tr}. z+ ++lqlrJ ql4E ,el ?lB A
44, z +lil EElg
^16*
4*a 4Eq H+&
d¤ ¤E" p: mu 4¤8"+E azl,1= 1q'1
9"8o194F""* EEI= ezl z4JS 6J=olq(44lil 2), + a7l p "tel I
gr+ eg +g+ C¤¤ *=trI. BTI F*= rmti qa ¤+ glHzl, Ey= )toi = I2t2t
qlqzl,4 ^
=firtzm Ek
I,= lPr
7F EIE 26e
-
(a) Scfrrtfinger AIE 6ll .\I,,\
=-T-
-:1+
zL
"lE "Ja^lql zlzl9 "JHI6H=
q6J +*ql q6J olaol
<l-
+d6l Schrodinge. 49 "J+^l7l=zlE q?l6l-= Lol4. ol 0
"lrl ol 6flql+ +fl a 4l r+6ll^l -"1+q= 6]]e| qlq

zlE +61-= 4o14. ^rJg
rel
(a)
\?Y
@ +lel goJol'lEH:dschrodinser
6}|
^lel >
7F3b^19 6}]= trl+.$ ?Jq. <l-
0
V(Q)=e'"'o
{zlrJ mft ol4Jll,.l= "JEel +-qfldq ^}++1ol zlgi (b)

+ql ¤E6}4l g 4ol4). ol 6llb zl-ar ES4ql 6l]= olqq, 7F.2 -I.al ?l= E= g'Jololl cH:d Schrodinger + 6t|. flE4l=
y(p)-,+e*,0.1r,s-im,Qol q _B¤4ql 6l]7I ¤ +E glzluJ {zl
=zJ ^19
4do+ Heq, qal-^ Q=04 zn0ll19 Ee Eg-d 10ltl. (a)9 ot| eto=
^l= +lE olltr^J +E6I+. cosQ + isin@E -d Hl+1=

-Er Ll
SgPt'JE ulelqo+ EolEg + 9l
6l]0lt[. (b)g 6}l e0'sr0- cos(0.90)+ isin(0.90)= ¤+s[ a{f 55 E+71
=
Ell 1 ol oilzl trl+ %Ic^l¤.
"J+^l7lEzl9 sq] @=0Il2noll^l erl geq, EIal' l "JolEg + Ei.trl.
v40>zl6ll"Jg q"J6I7l +l6ll^J +d trl-$ 49 +E-6IzI.
uA2A: u
E4! 3 4++ffi9^
î^,0_ tt^ \oimrQ_ (imr)zgi^,a __mier^,o =_miW +*ql= 7834 (N:(J: v*vdr)-''')g e folzlE a+s+ ^J
do" dq\""t t'
+ Ng +61l^J l;<l-fl a++^l4ot *'Hl_tr). o1
Ir|+^l a+ql= ffis+zt 4 0{"J E+6}q 4+ ¤93 0=0+
y) znt\z)z} ¤+. tr+4^J e+s} ^J+E trIgr+ ?"1 S4.
h' d'w h2 . m,'h'
- rI d;'=-n?miv)=tv I
N
olag'd.fx yr'Eolq, E|+^J 7Ia6J +¤61 6l]

ol4, 4s" 6}ts 9luJzlts nittrtztolrl.
!Al2 4B+ ?AAl z4 r+6tzl C+oI uFE" E|+e+ 49" 6Ib .llHzl{lts 4i *,4 -szlE E
oltsrll, ol cfzl "Jz]+q Eeg aFb 1"14.Ir]4^J,
ffis+z| tzlr-1o} 6J+= ae ++8 ?3Al d7J9_ "J+^14
oF ++= {9 9ula}4, :z4alq Sd6l + sldg + trl-S
ql i]g tr-EllE qEotT}ot ++. V^,(Q)=# u4 glE g"Jololl
v^0+2n)=vlLlzl dB6l] tH-Lr trl5gr.+e| (7F.4)
o| aJc|(:24 zr.z1.7LAqI 6llqlq=ol azJg Bq+H ++r+ *lt' ollLl^l
E^, ffit=o, +1, +2,.
?J* 4+rI +g+. 2I
y (Q +2n) - - rimfi ,2tcim1

"im1(Q+2r\
= \r (O)er",^, _ V (Q)(e," )r-,
qlLlzlTI ,?4ql E=6tE-tr. + m/t$t4 -1)ol 5"J+ "llulzl
<lg +444, r4o|{ r,,=0"J zlle-l6l-H 44e-l qq
?Je 44zl- ¤+ =+lE
E+ 2+oE qsl¤+
sin=-1olF ts "l ^lg trl-94 zl
=flEol
y(Q+2n)= (-l)'"'r[(Q)
EE dE 8^.1 mt9 4k& qI+B 4lE ol4ol oJ9 <tg trI
++L a Al z4 V(O+2n)- tt/@)ql - lol qqo} E6IH Ft1z,^ +E +-c.E Eq+= 4"1 ¤4. A mFlol4l Âzl I'JI
6l-!-_E 2*& "J"l+ +E 4I A+(Gg EJ6J)?+oF qI+ t??,=1lole|tr &= aol +tr|.
270 7 zrÊ
(b) 4F-Jel ?frtEt me E¤+4"J (}Ee- 6JC9,, + 4gF*E z4 CEe "J

g¤ aE ++lE sld6l+ "J"JolE zld^J z}itlgtrl. rz,ol ololg 4I$E=*E z+ CEol "Jol g+("Jql
ad4 0 + g uil
o e ¤+aJf ojulolzt dB gE-+g *F"l '4¤.F%l'+= ?* ^J
*g oll rl4l HJ'JE sld). rz,ol $olH 4¤+=Jq zq c
4-Bg Eol 9ol g+("Jql^t *g *ll HI^l4l oJ6Jq sld).
t}^l zo). "Jt}4_o_tr. t{!E IEJ6J
=+(+qulE rCd ++1E.
"l 4+E-"d,e 4q /s Li4Lilzl"J *tE 6J zl'zfzl Eg A!+=E +s+
=Ag
q-q=r+ pol sefQl
6l+ "J"Jol9 4¤-E-"*9 ,E +4utrt. 4¤+=J3 _1.4
¤-E" + 91tr1.
919 "J"Jol= E6J* "Jzlq+4 4lql^JE +4+=ql, t =_
mpl Ain+ot 617l qlEql 9lHzlE "JzI+¤+
zlE E¤44 {t=E} zl4 i ?Itr}= ag E"J + 9l+.
zrol 4lfio + *4+= ag fld qqzlzl 4d
*6&.,9 +s)ql ++6Jg 9"1t4. olag E4
@ 4-eJot grtEt 44"+ qltlq=ar++.
Eq Tcql^J ¤H+ uls+ ?ol qI CAg +e6IE 6]]'J ¤& 2,ol OoJ 4lq6IH E-= qlqzl f;.f-l$ol z
^JEHE
zlE a+.J+E zl4zl +el qL 6I+e+ ee alol +e4 +e-E trlelg+. + +"J6J 9lHxlE *E fldol
trI4^l a +alql^J= 4\eF-+ql ql86l+ ¤îztE Elel 4 gt= 4,o14.
^l4l ',J6J"14+ Hl^l4l 'J-Jg + {r
*:z l-+xl= +61+ Lol4. od glulzlzl. s o q, sld SE-ol 4zl¤ + 91tr1. -
rlo
m,o\ rtzlaloll ,r+4

Rr
trl 5|.g vlet$ zl-
1 4¤+'=&ql 4+ Stlz} +t;l7l
,l0l
EA! il
q+.<l ffiol 6r}EL+. olag g
^ll. {5:6}q
rlrll
"J"Jolb x7-Eoll ffsl;a :z aI&F*z z+ql 4?+"t 6Is

_e. ol C+"Jg rq6IH ¤4. 44x}el t^l zo{ 9aLE +J F qq 44 *zlql 6llB6J+(re 7F.3).
egl zncllr,l zl!61-
't --lL_: BI-aL zlol Ea6}+ol
-t+Lj i r_ trIEd_I
E 4L¤+*E z+ ^JE+ trIgr+ a+. +1 tu [ | -i-i E-i -i o E
+= ¤+. r}.&g r
+4']]q, *"_! El-E6J+= H}
lr= xPy- lP, q ,J.JE +E¤ +El-U+ mp\l ra1<0oJ ffi
¤zlrJ .q F +lilE 444:r" pfi p,+ S"J"l9 dB + EL+E$ ^Je +EEL+ql ql'J6|4, tr|{^l ^JE
E+ ^dB=ol+. olE"ll 4s" 6lt
¤4Izl-E=3 x, /, px, 4 py HI'}l oJ6J9 e# *+
olEE ¤tzte il+L6J 4"14(E4 zc; Q_qx t4t_ itr_
= tAts q-q=$ *2
(hti)\tdq, ¤zlrl q=x') y). 4r+7I +$trI.
7F.44E ul-oEer+.tr. qltl-q= q¤ trJE= trFq-4 ?ol I
ej tr-ql^J "JC6I+.
i,=+(.*-r*) ¤Eoil
zloqZEOl
- rl- O 6-i
rl1Ef
a;<
4-'1
E&^l-
(7F.5a)
gF 4IEE ol+6iE olaol q-s4 ?ol ¤4rrlElzl9 tral

le).
:tt
I
d
(7F.sb)
'l -_
L- .
-
dA
m 0
EJAI2 ol uf g4}xlE r+il"Jg+q]++
"ffiz}4¤¤L=J=
zr.q44 ffiaJfz} L9 r+Et+"Jzl$ Ezl fl6ll^J ol ¤&
zffi; ul^sio ot--'-'ql ¤Î^lrJE+.
v n,,
i,, =1
^, fr""'r
:l i^,fr = *,r,,y ^,
lm,l= 1 lm,l = 2
¤;t afrt;lzl 4S=*E r+EL+"Jg -

"l mrhoJ
aeJ7F.3 ral ?l= E= g'JolE trl.EEr+el d+ +E. oflLl^l7f
+"J6J 4."14. ol pffi trl+r+ Aol 9E6]]^J L+48 + 9t+ otrl +el' !-$s qal^1 =7l6lfl
=7l'-dr-|..
i,V = m,ltty ffit=0,+1,+2,... lel I.+-gt+ (7F.6)

^,(Q) ^,(Q)
7F EIE 271
-
(
e'^,0 \. f ei^,o ) (l) ?Ie-l rdzl¤ Sezll 6h= ql g-g* al^g
*
V tlll v^,=l@)lW) CrnH,,, ql
H4E 4l4l6}q+.r4E *zl# Hldql^JE +^-+^
( e-'ô )f e'^& ) I
aq+ aolE 3uflol.q dzl-==$ EÎ E4ql ++qq fl+
==-
{zn)"'
[ )ltzn)''' ) 2n
r.7IA6Iq+.
4gE=3=4 4E= ^JE4 7l-++e} rlolq(E{ zcgl,<J C9
,EL zllHel), ol
E¤. E^l4se g"IEzl Aq6}rll +46J +
s.+= ae E+a¤ g".lE E 6l+el gl"l4. q7l^J= 4g
E"
*9 z+ ¤W 4+614l g + ?lzl"J(.,h), g"JolE 14
tlq +lil= Sd6l "lzl tr4+(+"J+ q¤ I,JE_7} olag
HI¤+trD.
1 TeLJ! (*3 qgl Eg a.a!)
r-lour I¤8'8 ?T lzwtg1=gg
W ral-+l-sJol E'gol ol8 '[vHeth tbloP 6Et+=rw [afp;;g+='z :6
r4-91-"J"Jol Egg + {Bzl"J rfl$ *q4 EzI 4lE
¤H6l+ *4_o + ol+qr il+. Hld9 zrdzl¤ +^ g
zlE ¤ gB ael ^Jql^l 4-+E4l ¤.rE" 6l+ oJtrJolE E
-r. ol ndzl¤ r==EAl 6l-= trll g-g6J =qa 9lHrlE 4l& 7F,2 3xl-fl EId
4q+ Hl{lql^l +A-tsA Aql aol= l4gpmolr|. olHql= HlzlEol r"J *Htg q'- *_e_tr_4 4-fi+7il olE
r.el$ ,t.[:d 4 Ea flz]"]4 17flel ndzl¤ LH+o o ts + fl= e"*olrzoJ "J"J"]E ^J46ll EzI.
trol *.lAlql^JE 0211E 4zlzl a"-l E4IE e+++.
4 tt4"L4 27llE 4zlzl E-q7Iqa ffit=g, +1, oi -r rJ (a) ul.5:er#et qlLlrl
4E"J"l d+¤trHEE Ee qsl ^JEItrI). tr++^l
=.Eb
ql gsQl alAE 9lulzlE 1j,zlzl rzr=+l(E} -l)E+El + trHql^J= qq^l+ "J"Jol9 EIHI¤ glHxlzl E"J6Iq,
olag 0 o + $oIE ¤+. tr|+^J Schrodinger 49 q-gl} A
%F+2(EY -2)E ^J4E dolqE ql gs6J zlolrJ. zF.4
ol ¤ + 9l+.
rl4 dzlE eqrg ol+6Lq ol= tlqlel 9lHzlE 4l4I6J
+. 64BE ql EE ,Jole| E"J+ Hlzl$q flg ^J4Elr"
64¤9 ol gql 4r$ ^laq-. -*o', -Ev (7F.7a)
zp.+491 E6IH mF*14 m7+2 tr-El]= ql ¤zlrl V'(g xlla}l olep 9.1=+)g 37Hel zz| sq4E 6J¤.
=01zJ4ol ul-e=$ ^t"lE
lzl *ol ¤4. +4111= rll 4ol.| zlE+.<l 'taptace ¤tlzlr4l EItrI.
F1
v" -
a' a' a' Laplace E^l^t VF.7b)
LE=E*r-E*, =(4-r)" *+ af* aZ
ol Ezll9 qaCE
=9.35x10-te I "ldg ol$alzl ?lEl^l +H +a+E=
ole" olft. 4"1 ElBal-4fal+zl9 ,tal zr). ol als.E 4H
trt+^l dzl¤ EE4 6Ib ql gs+ 4l4el oiluJzlE laplace ¤4lzPI q-q=4 B"l 94.
0.935a1, +9 s0Etcl mol-lol g+. ol ?J4e 1410THz
"llHzl
(1THz=10t2Hz)E dsf, trl-{^J 213nm9 ultlE gi+e+
rdr' r*)N
o'=++ t
"*Eb+. ol dolql ql+ d¤ilE z6onmol+. ol4+ a
t* e-B o e ul-il-4 g "*E ar+r} +g+= 43 -15 4zlrl q+lE ael %L+14 /q +tL s.sl+= q-q-+ ?ol ,t,
4"14.
oJ9-tr EqTI ?l=ql, olag'legendre ¤tlzlr4l oJ+.
xlTl EJT| 7F.1 14-+l-"Ju3ol E_8¤- "l*aI,<J =trufl n'=j,r-#*##'*'#

272 7 zflE
7E +4lE
+ qag *= 4l(gz}e+ egql q6J +qe 7E +EtE 0
(^4lil 1)= ol+*gsxl zz]l E+6llzl= 4*zl r*rh ol

3}s4q^l= gA e_E+Elel 4?]GlzlE) a g?lE a a-qa_
0
%L+14 /5 alg:e ol+*4. olE alEq ¤qg 0 < r ( +"",
2n
0 < 0< r, 0 ( Q <zn"1t4f?+EE ++l= 4q"J"l+. 2)
^7)1z1
fi
z Lrilx|2
f sin 0 ddedf
dr r+g_r+ zJ? sAlz}
e rllzlE__E_ 4l-Ee+ +4+s
Îolq= ^dB
r ql+
r si n ed+
x=r sin0 cos0 /=r sin0 sin0 z=r cos9
v
x
rllz|-e =. 3+s4lql^l= +rl a +7I &=dxdydzola +3Is
Zlql^J= trl.q-r+ *r+.
1
dT=r' sing drd0d@
^rllil
"JelE +.J+/(r,0,Q)4 d +Aql etf 4+ol Q-e-=$ pol
g+.
I t a, = 1-_,,! ,=,li,r e ,o ,Q)r2 sin o drdod@
{zlr-lE ,"1 .JA+ A+= C4$= lolo + laplace fltlz}

"Jel ,.ll +6J E6J+= +^lg + gleq A,/l
6JEI ¤-"Ikr-=
+. trI+^l Schrodinger aJ9 q-s=4 *"1 # + 9l+.

\
trt 1
0
- 2m7 tfv(e,Q)=EV(e,0)
+E +E 6*2 "J"Jol9 +C sHlE /olq, ul4rJ

mr2
Schrodinget 4lol q-q-r+ ?ol ¤4
aal 7F.4 7 EESoll ?l= ggolE ul=:Bt+E F ++8 ,JZl 4Z= U+
Schrodinger 4.1
6lq, 0l tttlEoll 43EaJ SEt|oll S-d + g^l+71-L[8tr|'.
-* n'rrl,Q)-Etg(0,Q) t+E 8E g'Joll
(7F.8)
^17{0f
"l ^lE ull5 22119 ++ AAI ^49 "J+^14"F ¤I4. a+ *19 *s. zr.s 7E 89 SJol0ll EH-d Schrodinger
6I+= 2il-?lE A+q q.J a4 E"J6J ao-+^J,
6t|
Y ?+ /-tr_ E^lq. 4E= 6J HI+l E=r 4rl il¤. Zle-E E- ^lsl
olzt"t ++= 4ol4.Ea}] aaE Hli6J ao +^1, + +¤- +E 5El B+4r 6lt Yr.,(9,0)(s 7F.1)= r+s-r+ Ag
^lE
E"116}=- +lE 6J Ht+l EI +E?l es -E^l) ul-¤r6r ollol4, +qlzlqlal ¤- "JEl{ Et++.,
^Je--E
izl zl* af e_E EoITl-oF ++E 4,"14. ol + 47J& a4 1\' Yt.^, (0,Q) = - l(l + t)Y,.^, (e,o)
7F.4ql +E'}]fi.4. olE z4& "J+^lTlElH olluJzlq 4gE
l=0,1,2, ... ffir=0,+1, ..., t/ (7F.9)
*ol "JzlEI q"iot {}+.
r "]fl tsg +H aE| 6J+¤. BE zt,rllel E+ BelHg ol .rrxll fl.<[o1_e
E t}4l+ 48:9 4g ¤g _u-o}4.
7F EIE 273
-
8 7F.1 7E aa1B4 s-qFolxlH Y,,^(0,0)= +H^J9 I'J"l9l 4t schrodinger
6l]olq, 4so 6lt ollHxlE trls=r+ ,JLI.
fi|1 Y,_,(o,Q) ^]9
0 0 (+)"' n,,^,-l(l+l{ /=0, l, 2...9+ ffir=0,+1,... t/
oilL1^l t+E gsl g"Joll (7F.10)
0 (*)"'*,, =?l
''
t1 =(*)
sinoe'''
C+ /r+ zp olzl "Jzl^+e+ ?JA) 4 4"lcl-. t* ?llE 4
J 2}rl+jr" np \l7l gr[++. qlqz]ql== -s.,(l / 6]+
2 0 (#)"'(3 cos'g-t)
?+7+4 /*ql 2t+r\l) mfrkol zl+." 6|E_E_ {
"Jg Eoltsrll,
+1 *(i*)"'.",gsinge"'u qlqzl i?1"I4 Qt+t)*ge qs+94. _z4l 44el u+t
oJ+Eg Lel l+Et+olq, q+^J E+¤L ,,k *,hZ 7*y 7+
x2 (#)"sinroe':io EE=j= z+ ^d$ql '}]*61-=:z+EL++.
:-fl zF.sE /=0*H 4vl^1, r4r mr=ooJ oll9 +U aa+
(#)"'(5 cossg-3coso)
6J+=¤ +E}d 4ol4.^J.olei +sE t"lt 4
a
J 0
+1 (s cosrg-r)sin ge''' +
" 44U ag 4lE "tq(iil-8.61-A7l cg zl+s +lil)E +l
=(#)"' zl= rla6t7l +l+ 4,"14.++.]]¤¤¤ ++al¤4
"
+2 (#) sin'ocosoe"''
mFooJ 4E "t4z} S,4.
z+ +flql
t3 l=0, mt=O?l +E as+ EL+: d-d "I4 E ,*^l
=(#)"'sinraego
?*Ecll, olag + x.EE _urE eliloll,<J 'u|'z[ oj {-
e6J Zlg *zl oll$ol+. -'lo
Rr
olfl alfS + +s+ mr=loJ ql6J 4IE trlq
tE l4 ?rl. "LQ
"J+^l7lq, lE a+slqq ^Jqq
,01
4A1 44ge il
#zl ¤zl.*ql q+ tlE"EL+= q 4q4^l +E o[lt
el+.
ol +7I6Iq, q+^J "J"Jol9 &F qlLJ \zl rtzl
E4l 1 *tr aq-EI+= Schrtidinge. al9 4 {}+.
7F.8^lg ols-" o[fl +gl} ?J+ 4471-+g+.
-l(l +t)Yt.nt E
zr.rozl9 q-s=+ ae ql¤¤ Ela ?l+
-*Fi -laa = ttt+e)Yt ^,(e,o)
Ei+^l +E aEI EL+i- E_t(l+r)h2t2roJ Schrodinger
"llHzlz}
6ll+. qlqzl} /ql"J E=6la ra19lE roElg +E-6Lq
^lE
4.
'lAI z ol ul.Erd:+= 4S=#E z+ ¤+E .z${}folzJ l= 0, mt= 0 l= 1, mr= 0

E 6I+
4ISFe3E ,4. CEql qlq! ¤tlzl* i,=(h6)dDooltrI. -E 7F.l
ql E6IE 7E arl EI+E9 E+ v,.., (0,Q)=eu'Pl(0) gol+.
r46}q ++4 ag A!+= eg + 9t+.
\.
Y.
t,frt
@,a) l=2, m,=0 l=3, mr=O l=4, m,=0
f @-l-!*r"'f
t,y,,^,10,Ey=t,fr /\ (o)=m,hxeu'ef (0) :leJ 7F.s +E ?loll ?l= "J"Jolel trl.E-Et+E zjg. ofclE LtEfL[l] ral
tde
raJ. raJq B"J= rl$Er'+ol 801-Lf +E= LlEl'.!t[. E^{r[ El^! ts=Je
=m,ttxY,,^,(0,0)
801-d +Ee-l rl-sEr+E LfEtL,!trl. trl-trlel t= /el ,Jol 7ltrt=
+=6[fiat. 0l trl$-tsr+=o- EF mr=Q?.! A=0|tr|. +sl +41-d z+=71-BrE
ffl!
nl-e[,<J ym,(Aq)E a.gilzl mk"Jlg l+a+.Jg "J + gl+. ee=g E[tr]= ?J=rl-.
^lLfTfrl
274 7 glrE
. /g "JE C+"J¤ zlzlq, q4^J qlLJzlz} "JzlE+. r-l+4 eg rlzl

2.60x10-22 Jo1q, d#ql 611B6J+
¤+.
' qlq 42 mfrIql ru¤Iql, olae qlqzlzl sld Hz
{r
gfel ++6t71 rllEol4.
HJ6Jql -
'lo ,_*h _ 6.626x10-'" = 3.92xt0,,p = 392GHz
Z.eOxrc-r_rl
. qlqzlzl 59q} zt+tzflE trolel 7J mt

Rr
il
'Dl
Js
*ql rll6il^J al44)z} glg + ?le o E, "t^l+71 0lru

+4 ol {t+E +^l+ dz}zlu} 4EEH9 u}ol=e
/oJ ++l= (21+ r)6e-tr- qslg4 gqq +6Iq, rq6lq EzI Eldg ¤+61"= rll| ulol
. 0A 9lHzlz} S,9-q, Eo,=0o14. ¤4tB"l olffic(Eq rrs). ol aol 4l=+= +
=_evl
^d
EHIEqI el=6tq, df,f= q+61 4'J6l7tl +48
f ?lzl trIE.ll ulol=._tru} +*Bg ¤EI ,JolE aad+
@ fldqlLjxl
=+t
ol8 Ell+61 g"J+ %'-Bol+.
+ts1'-E g"Jolts zi)zl EzI9 Eldg t4H= eg
tr. ¤. + gl+. tHt27r Eztg eld¤. czl tt-4E rgz} #
xlTl g.71 7F.2 +zlE alxl F qd qqzl
2Ht27r
=fl
(aB 4olE rH127r Ez}e+
+lE +i ilzlzl cld6lû {ee- solr{rflz}z} elgal ÎolE {ol 4l¤*= +6}q+.
#421 trIEql *zlolzl ?+=+r ,ICfltr}). A6J p"lE a+.)
zggget :E
160pmolQ. tHt27r EzI9 9l alzl Eld qlqzl i$lel olluJ
zle+ r q+E= +6Iq+. alzl F old qlqzl
g dol Tlffi+6}q+. =+l ^lol
(b)4EFJ
r.aiCi ,ri':g +i E{iEts i= mr,R'oia- R= i50pmoj4.
qdd-= "J"Jol9 "ilHzlts rdzl o e r
qd qlqzlE zp.ro^lee +qd+. EzI$ Eld "llHzl 4+FeJ /E ol+
++lE +49 uI= 4eE%r oJzl+=. / 44lql /E +4u
6ll^J +444 I+ r+
Er=/r/2/ol+(+ElzlE ^J4 zo). {zlrJ
q. qslE= El+^J 2t+t(2t+ lx.lH)ol 94. F Eld ef=*el a7lq.olag 7F.10^lr+ ulnalfl zlS$e[! zz]
=+l el zll+g t(t+r)h2zl qq, q+^J 4s*9 zz\z]. rl-o--4
E ÎolE doli Bohr TI¤+ aa(Eq 7A, hv=LE) o e
+qzlE TI#g *4¤ EJ=6I4+ E+¤-sEr&l eq *"1 84.
g + el+. 4t+E=+el a71 = {l(l + t)lttzh I = 0, !,2 . ..
trl+4 ?Jr+.
a7l (7F.il) 4EEaJe.l
Eol +d .ErHltr=
7H aq 6J+E Lel l+++o14, :z agzlzl q¤rl Aq.
R2
''n
I = (1.67 5 xt o-" 2
kg ; x 1 1.60 x I 0-' m)2 = 4.29 xl 0*' kg m' 4¤8" *E z+ 4+= rntt ffit=0, +1, ... +/
4AAaJg zG dE QF.12)
trI4^J r46}q 4¤jF%lE a71e+ z+ CEol E+ "JzlE+¤trI.
tt' (l.o55xlo-" lr)'
n=ffi=1'3ox1o-221 z]trJEt oll 7F.1
3zlgql^l +E" 6l+ Tl]illE qL aol+ :z +zflel alzl I

l o.rtozlolQ. olxll r+s-4 Ag E= oJE=tr]I, qzlî E
d qq 4 l, 2, 3oJ 4E"lcl-. rl_14 7F.r24
tr-fE E6lq gg
zp.r
7+7+E qlqxlgl4 Avogadro =fl71l=0,
"lluJzlE g ols-" 6|H
"L4e+ Ag sE "J-= + 9i+.
4o14.
I Elzl E/(Imol-') q+E , 4eF=&E azlh q$E 4S*e.l
z-1lds.tn
0 0 0 I
0 0 I 0
I 0.260 r56
2 0.780 470
3
5
I 2rt2 3 0, tl
) 6rt2 5 0, +1, 12
3 1.56 939 7
3 121t2 7 0, !1, +), B
+ slxj qd qHzl0=0r+ 1) qlqzl ,J4e
^l"lE
7F Eld EE 275
+2
frt= -1 mt
*"1-
t ffi,Y
+1
ffir= *2 +1
-"tIi" J
ffir= 0 -1 -1
-2
m (a) (b)
-2
frr= *1
aeJ7F.7 (a) ral 7t.6el9E. (b) EEIE'J+1401 qEE + gto-s-+ q7l
eol flg afE "Jgsl g9l4oiltrl EEj= HH:d^l7l= aol q
^lq =+.
gE=J CEql 46J rd4 sdg 6llBF "Jzlqq}4 Ed o +
aa]7F.6 /=28 61EEl= 4$EBel HH-d. 0l tr1E19 EJ?l ufl-d(z= Tfl
ttfl
E Eld?je 01tr .8Et|olq qal^1 0l raJ= xlLl^lll q840lal.= a= gtll H++^laî +Ee. + 914. olE r.ll ¤&zl-5 q=q=r+
^l-olql=
E aolrl-. t3 zl-it +417I
^dBaJ+
li,, i,)=rlti, lir,i,l-ihi. li,, i,)-iti,

e'J
(c) ulel
4eEaJ _agxl QF.14)
l9 Alol +qAg 4l *r #ol 0, r1,... +/E zlltlgq= A olE ¤&4E=e zl-¤lol "Iulzl qEql olEg tr-84 zI+
4= 4eE=+q r+ t+rol + +9E d^ll Eld 4s*ql ^ll
++=ol+(Eq zc). ule{,<1 6J ^J+g E+ zl.^116l .J++ trt
4,* zlq)ol 2t+r/14 {iE"Jg 714 + 9l+b ag Eq}4. + cEE EqAE= r"J# q 4rl+ 4eE=#E * C
+ "J"JolE 4+F*¤ ?"lzl {l(t+1)},/rql ulele -tr^lql+ =
EElg Cq6Ir1 B^lB + flsq, rflotq LE g"J6l-Al B
H ol ElElel ,+ ^dEE z)olzlm,ol rls.$ ufio]slolo] 6]q, uI= tP+ t,E E^lB + fl+.
r.d4 Eldillel+ 94 S+4"J ul]a}g 6I^l g:r. 2t+r7l1E ^lB
g + gl+= 4¤ 9"1*4(rH ol{$ tI¤ 4gf=d4 =-zl9 zll{..ll 4fl ¤tl{-b trl-gr+ ,JL+.
tsll6}"Jg 7F.6). ffi
r+ ee ts+e
^ldg F6l+ 4014. i' -i| *i; *i1 4AEaJ a)lg
^llEoil
rHzr E||^l (7F.'ts)
sldille-l *a El].Jol "Jzls|¤+ ol ¤&zl^b

^ll
cE ¤&zl-==4 z}¤lol4.5
EldalTl qE + ¤^lg +(qlaql gl+ql^j zlaflzl5 4zl* 4E5aJ E&^lEel

1t' , ir1-o Q= x, y,o) z -as^l
(7F.16)
olu{ z}zlz}E
"}.})ql
ql6H^J
"JelE H]]a.}.g flg + S.+E
olsi+ "J4qq}4 er+= gzj BIxt=t+l +4
4¤+*E =zls}+ Cgfti-4 e4 z+ d+)E
Qe|.<J z1l{i
zllnlzl 4¤+*4 z+ cBql
t4!6Ir("J
=+ S+i4
46H^J"J
5$ g"J6LAl H^l6J + 9t+ ral6}q aA TF.7(a)Ql s"_I¤
EE + C¤,_e-_e^J "tr. z+eE _E^l6J+), *44 y+ :B 2r.03',Iil r+ ^J+4;.4CEol H^l¤ + 9l= \rJz
'(J$(zgl +4q} + + tr"el CE)ql El]6llî= d:.i ^J46Izl r*¤ olag g
"Jtr-g +E]..]leJH t,7l +qB^g 4+, t.
*gt+.r ol+= 7F.5a9+ ?3 E=E 44 s^lq= ^ll ^dEE =+.
e| r= B^lB + S.+= HI¤^la ilq"h -J4. f
ql q.J Etzl# 4,tloll_H-H "J + 919 4o14.2 ^l-gg
4gE"d=q ElEl E'g¤ zH 7F.7(b)eI ?9 :zB9 0l
t.=+(, dza 'dya\ I
+++. ol :zfloll.! tlgE +H aol= 4IgEUi9 =-zl
--ry- ) {l(/+t)}'/2 E+lql Hlql6J+. 4 flgg(z+ ^}el Fgol "Jd,
a a rnr9 B9l) "JA+ z+ CEg +4ql=ql, ol43 AIE g"J
i,=+(, dx E 4EEaJ EC^l (7F.13)
6J /. Atg +qq= iol4. rfl+ tfi
t,+ "leol+. 4rgF
i,=+(. dy a a %I ^Jel= ++ql= ElEt= r Eol g¤. +¤-"l +lE "Je-lel
v di
glilql e-E.+ F¤ ql4r g+. ol *Alql^J= olzl
^J461-E
ol$ 4l ¤tzls=$ zlzJ 7F.5aql^Je+ E"J6J uJ$se, ?+ ol ulelz| ?lgg u|4 Eolt+r .J ¤4. ol Eg
^J4t6|H
= 9 ol+l+ 5Ae -$.{l ol reql+ EJ *g A-u-= +q^la
z olEg rqpe+e-l Eq E l=rxpoll^l ,+ p= aHB ¤tlzl-E=e Ht+l +g
aE ¤eEoltrl. trI ¤E6trll g aolq(E4 sn, sC).
27 6 7 ?rÊ
. +Hel {olE 12'l2ol+(12v2hq a7l= +4U+).

. z+ ,!.E Fg ol +2zl ¤rH+zh9 z+ CEg +4U
H :_ 4gE=Jg trl-s=r} ag gBs +48 + 9l+ rD.
=g-dT]ILJE
tr1. 2ilgolLI 3ilgqlî EId6l+ g"Jol9 qlqzle+ 4+E%t D6. az er^lEl* E.ldillTr q¤ 6J B^lg +ql rll6ll^J "JgE
g "JzlElg4. "l o3=z1rlg- ul^=i" gfz| +Et AZI EZg trJ qd6J + S.trI= "J4qql4 ¤4o14.
zJutr_
+^l7jot 617l qEql ^8zlb 4,o14. J7. 4+E=$9 ^ll CEEe.<lgz} ^Jtr4 z[*=e]"14.
42. 2il-?lql^J Eld6I= oJ"Jol9 "llHzl= =lxl D8. 4¤+*E CEg ++Llt= S4}xls=g zl**ol olq o + 4
=.9(mFo)z
xllelap rL+ qElEtrI.
2+_q_E. ¤+*E aTle+:z aJ dE "J$- E^14 o s H^l6J + 91trt.
D3. qdq+ "J"Bolts od glulzlzl S.4. tr9. 4gE=Jg gg E"Jg Hlel ed-" e +48 f giEcll, "l
44. oJ"Jol9 4¤+"d,r} gzl= Erl4 " + g"J6rAl H^lB + ggel +E zJol* {/(/+ r;1t'zo1a_ zq tt-E +g aTli yn,ol
strt. gq. 4eE* ulEl= ol gg ^Jq^J +lzl7l- i]]
= "lCtr-Ell"J
trs. 3zlgql^l Eld6l-= $"Jolgl E|]6]|^]= ++l A4aAql E6l1 -E :. go1 gE- "J+E.J,6.Jtr}.
a- zq CE"l "JÎs+g+.
^l 4¤+%89 =zl4
=e-d^l=
,A-lzl
OE, ,\l
-1 +^l al Hs.
r;-l ¤.+
+l "J"J"i9 sFE"
V,,,(Q) = s""to I (zn)'''
ffir=0,+1,+2,... 7F.4
rP] +l 9"Jol9 qlqzl E,,,, =miht l2l nt=0,+1,+2,... I = ml 7F.4
rEl el 9"Jol9 4tr5=Jq z4 4+ m1h frr =0,+1,+2,... 7F.6
+E +l "J"8"19 EI.E"EL+ W@,Q)=Y,.,,,,(o,Q) y- +E ar+++(E 7F.t)

+E ?l "J"Jol9 9lHzl E,,,,, =l(l+l)h2 l2I l=0,1,2,... 7F. l0
4SEtr9 =zl U(/ + l))"rIr l=0,1,2,... 7F.l I
4¤+'*E z+^JE mfi frt=0,+1, +2,... +/ 7F.r2
4¤+E}E Ce5 ^plel ,I+ +41 1i,, i,1=ini, 7F.t4
1i,, i,1= r1,i,
1i,, i,1= i7,i,

7F.16
ti', il= o, q=*, y,") z
EA 277
E4 7A gF^|q+ql 71fl
¤E ETI
"1.f:C9 9"14 A+= ¤B+q4.
D7R.r u1^="-"JoJ"l Eola|flizl ¤E6Iq+.
Dt^z "JxlqtrIg E"J6l4l EI= +aE¤ eelslq+. D7A.4 Einsteing "JzI llHg zlzlt_ *g gEql^lq g+* ceg qB
D7A.3 PlanckT} +41 +ÎE Ceg ¤E6I7l +l6}q olal TllHg qBrll
,ll ¤Bgf 9lflExl ¤E6Iq+.
G^
r-'tl
E7A.1(a) dqr"l 5.0goJ BrJ f+"1 o.row9 B3 H(esonm)g 414 "-a l0eHz)oll.rJ r gEE 414i6}q4.
3-l.{fl+. ol Eall= +illE z}zJa}a
+%r-¤- oJ=6ll^l i++=+. ol Hg zI# tzJ"ll^l 4+b+H ro¤ +.ll ol
E7A.8(a) 2egKql^l Einstein gszl 2000KoJ tflx} ul34 riJlE E g*
trqlE{go} 9l+E) EEI"J+ zl*g 4l:4i
E7A.1(b) ¤*ol rO.Okg{ icol
%rz} ?el -," r.sotw9 u}lr zzsnmel 4 %hg 4lti6}q+. 4l^l arl=:n9 ulliE ++LHq4.
ol Hg zI+ trJql^l ql+btr} E7A.8(b) sooKq^l Einstein 3E7t 300KoJ 1tl4 Hl;f+ rillel E g+"J
Îdg d4 o e +"Jg 6&5ll^1 4r-:-4.
g 4l&6lq+. 4lt} e!+= 3Rel H]l+tr.+E}Lllq4.
E ro.ouJ +q ++de $"IqlB
ol zl$9fL:+r
E7A.e(a) 0 azlzl r.ofsoJ dz| tlEo, 0i azlzl rofsoJ EzI tlEo, "l (iii)
E7A2(al 4zlzl l00pm9 de Broglie 7l^lAl6}eiH :z 449 9pl
tr_71+^l4o| a|flrulr 9"t"J=I-9 7l^+ siHl¤ zizi ge6}Xl,g4i ?zlzl r.0soJ tlzl¤ 5e.zll 6l+ ql +qd-= "Jz}el a7l= 4l&6}q4.
ol pffi 14 mol B kts'lEqlq4.
E7A.2(b) "JCzlzI l00pm$ de Broglie Eltlg 7l^]r4t 6lelE r +qg g
E7A.e(b) (1) ?zlzl z.sofsoJ dz} tlE", (ii) ?zlzl2.21fsoJ Exl dE, "l
ule zl$.r.lflo| a[{le4i gu}"J=|9 zl4 qHI¤ i}7} gs6}aL+?
(n) Azlzl l.omsoJ +B HIflE 6l+ ql +q6l-= "JzlE a7l*
E7A.3(a) 4zlzl3.0cm9 de Broglie 7l7l4l6IEIE : 489 9"I 4t6}q+. ol pffi 14 mol B ue. =E7ll
'1E}1ilq4.
-e 7l+^l4o}6l4L--+?
0(a) EI^J"I (i) 600 nm( 4 ), (ii) ssO nm(*14 ), (iii; 4s0 run( a4 "J,J
E7A.3(b) %tCxtzl 3.0cm9 de Broglie ++g 7t^14t6]ElH r +qg g E7A.1
zI9 zflt+ ollulxlp* lmol B .llHzlE 4l&6}q4.
^q
)
trle 71"+^l4ot 6i1l'-+?

E7A.tg(b) s}ltol (i) 200nm(z}elC), (ii) lsopm(Xd), (iii) l.00cm1ulol=.
E7A.4(a) 'ul,<ll+e ^J+', e= Eag +a= Br-61= ql +g.J qe¤-.Jtrt. trt})"J *zI9 ,|]B qlqxle| rmol B {lHzl$ 4l,|!6}qq
r 4qD4"J 1I* rtrtzol+. *+E= cs 44H 4l actr- eE" d+ dz}9 E7A.11(a) ¤6
sze.to(a)9l,tl 44q *z]-E¤ A^l *qg +4 g
de Broglie +6Iq4. zITl
^l-.s6J
¤+qL+$ $uluJoJ 44ge 7l+El4L,-+?
E7A.4(b) y}eiol Bxl9 d¤ gE%Eg 4l,t}6}q4. fA gzlz|
350nm?I
E7A.11(b) s6 sze.too)ql^l 4r-]4 *zl# 8zl d.49 aHe
fl
olelfl d¤ ¤+%l¤ zlzlflE a-^-E7l9rI4 99"t a}]lt+i ^l*s"6J
zHA* 4.a026m,)71g+tl+E gtrFrJdJ 44 " e zl+qA-+?
E7A.5(a) (i) l.0cm stE olFol*. 4=3 t.Og9 "J"8ol, (ii) 100km s-rE ol
E7A.t2(a) +EE F3:.2314 H (ssonm)g 4+brt. ol H"l (i) r.OW (ii)
E6l-b ag a"*9 g"Jol, (iii) r000mr-tg ol=o6l-!-ue flzHdgql,tj roowoJ ull ,Ia H zH49 *zlzl HJ=Elll!+?
ol flz}9 dB4'J +q)el de Broglie tlalg 4l4I6Iq4.
E7A.12(b) CD= 9.1= eilolzlTl EI^J"I 700nmoJ 5-g^! H¤- ql+=4.
E7A.s(b) 11 roov (ii) l.Okv (iii) 100kv9 ElHl¤ il-= F61l^l czl t4e "l
Hol (i) 0.10W (ii) t.owoJ trI ,lla H zH49 *zlzl rJ=qAL+?
Pq zl49= dzlE r+tlg 4l4I5Iq+.
de Broglie
E7A.13(a) ++ oJ¤-+= 2.14eVo14. ol ++ql (i) 700nm, (ii)
E7A.6(a) 2e8Kql^l +xilzt tlt+= rllzl9 +^ldE Eltlr+ d#- ^ll+E
=14 300nm9 H9 aq7fl¤- ,I HqLls= dz}9 gE qlqalel +qg 4l
4l&6iq4.
E7A.6(b) 2.7Kql^l +illz} 4+= al4 ,rllzl9 +ÎcE Eltlr+ 11ffi t6lq4.
E7A.13(b) -Ir4 -+HIEe_l oJd-++ z.0eevol4. ol ++ql (i) 650nm, (ii)
4l&5}q+. re5nm9 H9 aq+flg trl Flq+eE dz|9 *F "llHzlel +qg 4l
E7A.7(a)¤I EillE+El HJ=qE +ÎCq 4\7171zooocm-'glrl 4l'llH+. 4l6}q3I.
olEillE +i-lle z|{ap. r gEE 4lt}6|.q4.
E7A.7(bt qI Ei-lls+El "J=q= +ÎcE 417171 2\2GHz(rGHz=
278 7 gtrlE
-Eq 78 trl=-Er+
*= gxil
D7B.t BornE fl+ 7l+. El-Eo¤-+ql 716l+ xll"J$ ¤E6Iq+. D7m q¤ 4l+, q¤ "JE r4J. ffi.tlo1s4 +41= ¤E6Iq4.
D7a.z ul*l'*fz| 4lE q+zl Ceg qBr]l ¤B6Ir e ol4qI CeE
g qB4l ql+61-=zlE ¤E6Iqg}.
G-\
erJ
E78.1(a)g Eell$ uI4 xlfr$fl ¤+61+ oJtrJol7l"9lqr 6}zl. ol g ,t'l a>Oolr|.
"J"lql e+¤ + ?l= EIE'EI+= tr]^g 6 "|tr lol*? (i) r4(x)=t', (1i; E7B.5(a) +g el+E +ql^l A+sl¤ + 9l= ae q! lolt*(eE ?*,
V@)=t/a (iii) V(x)= e-r. ,9 ¤93 *PH *Tlzlola- a* "J9 ++tr}). (i) g#, (ii) r-. ol5 +
E7B.r(b) rilfl x g"Jol(rel fl9 oJ,8ol)719)
zlf+41 gE6F=
^Jql^l
c|-::, a121. ol llujolsrl zJsE s^lB + 91tr1. trl^g
ol- g4zl- 6l+¤ + 9t= ul^=" $fol4lr-ula
+lil=
ÎolE
0-27r
E7B.s(b) trlg El+E +ql^l A+e+E + ?l= ae qL a.oluHsE ?
+ qE aol 6l+qr "J El=zl ol+E ¤H6lq+. (i) cos @, (ii) sin @, (iii) *, 19 gqg --*el -zlzJola a:- "J9 ^J+4). (i) sin(a;r), (ii) cos(ax)
e-'. olE + qL ilfzl E*¤ + 9l= ul-E EI+olA'-+?
cos (0.9@).
E78.2(al ¤# Ezs.:(a)ql^l ol+6J e+, 9tr xtx¤¤ <lE.)ql^l 3l

419
878.6(a) ¤+ E78.3(a)ollrl ¤HqI 4lE a+, x=Lt2 +lilel d.r ¤qql^l
ql +E "JszI +4'+4lL+? EIE"EL+ EqilqE r 9]il=
491
1jxlzl ga¤ +Eg $"Izi 9dg+i
qB4l 9ds+i x=0PEl y=rllzl! ¤E"J "I4zI reJ6IH gtrI.
E78.6(b) ¤# ezn.1b)ql^l ¤E6J 419 a+, x=Lt6 +lile-l dr gqq^l
E78.2(b) ¤# pzn3o)q^] ol-&q} 419 a+, qtr x<I(qe rtE)q^t al
4^l7l tsa¤ +Ee ¤"tzl q4l!+?
'li +E "JEzI LIr}+A!+3 u1-5r** 491 "I4zI5q"^]r}H r $lil=
+ld-!l rl-rlr , L. aHrl r-I-lal rrlalnt rlrl r?D?r-r .^- rDal_\.,I| ,_l ,{-lrd*Lrllol 2O .-_rttOL__rl,r flalfl
.,1
641 q'i:"r,. x=ttEl x-L//f^l:1 '6--Ll .rL
--1l+Inl
-r:.1 t-1. cto.tlot ^lLl'tl /D.J\dr-ll"l e. Oil ai-1 -67, i=Lii4 i:Lia "t"'i"i Z-lzLzL
ij-f/ i
z)olzl IoJ(+x=G?El v=1rtlzl1
gag +Ee golzl EIA]L+?
E78.3(a) ¤E +E {lzlql ql6JEl^trlo¤:
E7B.7(b) fl6 zs.:(u)ql^l ¤EtI 4lel a+, x=0rl x=Ll3
fE sin(2nxlr)"1+. olg+$ e+r+^la?-xl-e).
ul-=" Îolql^l dz}
zI gAB +=g 9"lz}94Ls4t
E78.3(b) 7Jo17l r?l gE 49 dx}"ll q6J rl¤i¤r-- sin(3nxlr)olr|. ol
e+_" EI+-=¤ A+EIÎ 4 EH Ie.). E78.8(a) xel y oJ*o}-e--a zl^fif'4| .$+fl+ oJ"J"l9 s15,1I+: qB
qflCg 7)7,l'-t+?.
E7B.a(a) --(.x<- gqql^l uIEEI+ V=e-o& C+sI^]4?+(lE).q
E78.8(b) x=04 r=r ,r.|ololl^J zlrq+i7ll ¤+61+ "J"Jol9 El¤:Q+++
zl.r.l a>oolQ. g-g-+
4E+ z|=. ¤g _H_olel. (2tL)ttzsn(tatr)oltrI. ol ffifl4- TlEilqsq qfld¤. 7.)+^l q.J6Iq4.
E78.4(b) 0<x<- ¤9oll^l ElEq++ V=tu& A++^lA?+(t-+,). {zl
EE 7c Et^lel 7l=J=aJ
¤B E8I
D7c.1 "Jxlqs+ql^l gîx}e+ 7i++* +4lE ¤B6Iq4. ¤B6Iqa}.
Îolel
D7c.2 +lzle+ d¤ eE%L ^lolE E+a¤ +41= s}+el cag z$la- D7c.3 ElÊioaJ+E +Eg qB4l 6ll4.J.+ gl4lEzl ¤BollE"Iet
ol^
Jti
E7c.r(a) Eg tr|{ ¤+61-= EI gtrJol(_r.E +le_l gESol)7I ?14-a alx}. 9 G)E 4l&6[q 4.
y(x) = (21 L)t/2sin(rxll)oJ 4l
ol ojujolsrl ?lzl:0_27E zf zlz]|a- +ElB + gltrl. ol 4ql
u15gJ-- ÎolE oz E7c.3(a) z)olzl roJ lzlg ¤q .Jql fl= dzlq a+sl ffi$fi x=0
4+ V^,(Q)=e^,ogolq, m& A+LI. m-*14 +2ol ul^=o g--'-
{f,Elg g{e(flg (e.)*=s-i,ol{, E eo=cos x+isin xol4.) fr x=L^lolql^J y@)=(2lL)tt2sn(2nxll)tr- +49 + 914. ol ¤q qFll,tJ
=
E7C.1(b) ¤# szC.t(a)"ll^J ol+* 4le-l a+ mF*t+ -2oJ + tFE"gr-+ 'IEEI+7IOoltrI. dz}9 gE%bE zlqzl= 7C.rra1o e +qzlq, ol
=
A+ql= r+q=r+ zJ"l ¤4.
zlf,Elg _E_q+.
= ^JE
E7c.2(a) 7Jo\71r.J gE ?Iq flE dz}9 A+cl x=0* x=L ( p,) =
! !' rrntz* t L)i, ff !' sin{znx / r $ sin (ztrx I L)dx
sin(2nx I L) dx = )
+49 + ?Itrt. ol ¤q +Iql^l= ElEr

y@)=(2ll)ttzsn(2nxtL)tr
Îolq^J
oJfz}golE|. (x)E 4l&alq4. gs.J 4Bg zlB eg _H-ot+. ol
^l
+E r.Q|;g ++ trlg zlEg +t+e--B,*] (p)= 4l&6H+. gs
87c.2(b) ¤+ E7c.2(a)ollrJ ol+oJ ar+ F"J.J 4lE A+ ffif,$z}
6J 4Eg ^rE eg -H_ote}.
EA 27e
E7C.3(b) ¤6 pzC.:(a)"ll,H ol*.J ar+ E"J*'r?-l +lE "J"8ol' 4le-l a c9 o.ooroyo ojg-,Ja,<,]?lqH +lilel E+acg 9"I* 6l*6ilot 514
9 ¤tlx} C+3tl ul-=.o!$fz| y(x)=(2tL)tt?sn(trxtL)tr- +qe a+el (p) utla
E 4l4i6H+. E7C.7(at ElHl¤ qlLlzlTl v($=!4;o1"J'J"19 qH!¤ qlHxl ¤tzl¤
E7c.4(a) S# rzc.r(a)oll^l ol+oJ a4 E"J.J 4lel a+, Etiz} gze e +6Iq4.hE tr"++.
Bq= oJ9 zl4zl= trl¤$ Aol +q{q. E7C.7(b) ElHl¤ ollHzlzl V(x)=p,11-e-*FoJ "JoJol9 EIHI¤ .llHzl E
?2fr
&4¤ +6Iq4. Dfi ov t45ol4.
4,=lo vl,@)av-,@)dQ E7c.8(a) q+ EL+$ 6 qe 1ol ¤{!zi d/drfl l$aJfolxlL*; (i)
¤zl,tl W^,(Q)Y A+El *+ V^{Q)=Olzr)t/2e'mrdolq
:r+JE" , me A+tr+.7+ cos(kx); (ii) dk', (iii) kr, (rv) e-*. fEl.I. ql$6l^= 6J+EE r+il$ ++
E OE +4U +lzlE TlEllzl= mr=*loJ A+e+ 'JHI4.J 4# mff, fl$ '-l]q4.
E 7l^lr al&4q+. E7c.8(b) trlg El+= ¤! q! 4ol S4izl d,td*g r+EI+olAL+ (i)
E7c.4(b) ¤+. pzc.+(a)ql^l ¤E* 4lE a+, gt}zl (hh)dtdoL s¤El= cos(kx), (ii) dr', (iii) kx, (iv) e-*. r;l.I. qitJ6l+ el+EE I'+zl= t++
4gE=*E 7l4il= ,4FtroJ A+e+ SEI4"J 4i mPJ a+¤ zlzla- ,-ilq"+.
4l&6}q4. E7C.9(a) sin(nnxllX¤zlt') n=r,2,3,. . ) gE B+Eg 7Jol7l I(x=O$
E7c.s(a) 41t soog9 +ol ot+ HJ"J"I ¤9 t.opm gq 4ql ?l4E :z x=LÎol) "J ¤q "Jql fl= 9"Jol9 q-Eoe-+q. n=lrl z"J F
+qol 4A+ g"l"JE:g E+ac¤. +d,L+? s.ogg e%ig *= +"J b ^lE zll-E+g -E-q4. g-g* 4Eg z|*. ¤9 -E-ole}. (flE nol Cf
ol 3s0.00001ms-'el 3s0.00000ms r^lolE +qg r*btrIE f 9lilE B g qtE sin(nr)=ool gr1;
+ACe 4^* g"Izt EIA!+? E7c.e(b) g+ E7C.e(a)91,9 ol+* a4 E"J+ 4le-l a+, n=24 4oJ +
E7c.s(b) flz}9 zl$ {EoJ * roopm9l 6il*61-= ril-g ¤q 4{l dx} zljtEtg Jrq+.
^ls
7l ?Jd ?14. ol dzl-b 6ldoJ 9"}".lfr9 +lile| +qel B+AC$ +A
t-rlz E7C.10(a) cos(rnxlt)(¤z]rAl n=I,3,5,. . .)++Eg x=-Ll2* x=+Ll2
gq ?lq ++qq9l= "J"Jol9 =9 ,+.E.¤.+ EgE ol-so6J + 914.
qE .J "JCzI9 44ol 0.4sMms-rol4. ol "JCzI9 ¤rE"=*el ^lolE
ol EL+g 4¤g -Lt2+El +r/2rlol9 gq +q^l= 0ol qs+ ol ¤E
E7C.6(a)
Ep}A¤g 0.0100o/o trJ# zJ+r,1z1qg flilel g+ACg ts"|.4 61*6I .Iql +'J61l,rl Boll"t aJQ. n= 14 :oJ + r+¤s++ zlr.6Jg Bq
qa!+? ^ls
of 4. gsoJ 4¤e z|=. ¤9 _H-oFl.
E7c.6(b) qE + dzlE 4901 qgskms-'olq. ol dzlel gEo=*E E+c E7c.ro(b) fl6 rzc.ro(a)91,(i ol++ ar+ Eg.J 4lE a+, n=:rl 5oJ
+ irlE"*+:,<le {:tEl$ Hq+.
EEJ 7D ET]-
== =xll
D7D.1 "Jzlq+4 qH ¤tE E?-lqI4 ?l"Jg b6}q+. EIH ¤,!1-ol d D7D.2 rzffl {tz}oll eq^l gE6l-= "J"Jol9 qlLJxlT} "Jz}s}51= EEI
z| ol{olu} oJCz].old r+A ,llz}ul=i9l,tl:- ee + C+A + BC(A, B, l +4 g"Jql*"llrl E6iq+.
el-r. c= Ezl ,l)e| ag slEzl Tlel old HI* ,ilrlq=q^ltrr} ,g D7D.3 til-fl trzl4 "J"Jol 6IE qtr EaEol 2il-flr+ 3il-?l tzl + "J
C cl =
3 7lq= 6hb olff *9.ol4i
= "Jolel 4q +4+=zl ¤E6Iq4.
qE T}]Hol +zlql"J 489.2 rzl-?l
tzL9l= 48921 ?*g+i
G.^
l-u
E7D.1(a) z)olzl r"J *zl +ql fl= 9"8o1"il ql6J qlLJ^l E g ar, nF2 a!a- nz=23 7Ie ql 41.il +E "JEE +4lll= 9lil(E= +lzl=)
olq^l trz}9 7Jol7ll.lr-a +7l.fl9 4l(4 rovo e7l)9 =91 qlqzl ++) E'n +6l-q4. rql ul-=:" $fz| trlqE zlzla- ?l4E r 9lil= ol4zt 9
g r^l+. *zlzl Eq+= ql 7l.JEl= qqzl +7i Eg (E',-E,)tE,g Al4J =
dg+i
6].q,}. E7D.3(b) H9 zJolz} r"J zlÎ4B /J.z} 4.ll 9l= "J"Jolg slJE.o¤-+z}
E7D.1(b) s# rzo.t(a)ql^J 6.J ahFg olHqlE H9 zJolz| I"J -J%'-41 ,1r=1, -14tr nz=3* 7Ie ql 4lEil +E gEE +Elrll* +lil(E= f-lil
^J
^le+?Jol7l0.eroJ(+
txl-= zl\a- g¤ol 6Iq4.
r}voZdt) "JrJill =JE +6Iq4. :-41ul^=."$fzi trlqE Tvla- 9ltrIB r gil= ol4zl
slaL+?
E7D2(at z)olzl roJ lil-?l tzt 4"| Eqflb ?*ol ln"J "J"Jol9 oJd
glHzl zJ4ol E+ ge+ .ilHzlt*ne+ rJolxly rg {tg +4Ltl E7D.a(a) + HE z)olzl7)7+ LI-LJ+ L2-2L"J zl^r4¤ tz}49 9"8"1
=fl
+6}qel. 2e8Kql^l z)olzl lcmoJ ^JrI +ql Eqfl= ¤E gÎ 7l n,=nr-)g trlE qslq= ^JEIE +6Iq4. (fle zg.,r3ol 9i4r ^J
= ^lg
E a+q= ol n9 fiol gulz| !?Lg+i 4!= n,al n,*.* 7l^1a- ^leg alltrolel). ol =lElEz| 4ar+ +d!fl
z)olzl roJ lzl+l Eqil= ollH t- ula
87D.2(b)
^JÎ +ql d=Jol rn
"J "J"Jol9
geE olluJzl(*rDe+ ,Jolal= n9(lg Ll4rll= 4¤- + E7D.4(b) + HE
'J"lzl
zlz] 1,=7fi h=2LoJ 4Î4¤
^JzI +E
oJ"J"l
^l =+)71B+ z)olzl0.1cm?l 7l n,=2, rz=8oJ qE qclEl= ^JE-llE +6Iq+. L,=l)] L,=,1Lof, \xl
6Iq4. 2e8Kq^l trzl4"ll Eqil= ole+ flz}9 ?*
ql= ol ,9 {lol 9"}z} qaL+? 4B tr-x}49 "J"JolE qelEE zlzlil-4t I ol+E ¤B6Iqa}.
E7D.3(a) E9
'Jolz} roJ
zlÎ4B ^Jzl +ql fl= "J"8olel ul^s."Sfz| E7D.5(a) "J%Ii]l "Jql + oJEJolTi Eqfl+. alxl .llHzl-E.c|:u11e1 glHzl
280 7 zr^l,E
E r*= El+E= 9"Izlqdr*r E7D.il(b) z)olzl r"J ^JzI

+q fl= g:"Jolel trellzi (i) rlz,4 (ii) rlzr"J ull
E7D.s(b)=9le.l
"JoJ4l "Jq E}
g-trJol7i Eq9lq. alzl .llHzlE4 +Ellg qlq 0.6s/4 0.67r gEql^l ol $ulolz| gag ++g 4l4i4q+. ¤
Îol9
zlE z*E qslE= g"Izi qXLg+i # rzo.rr(a)ql^JE 7l4g r4e 6144.
=flE ^l-s"
E7D.6(a) + HlEill ÎolE d*+= Eolzl2.0evolr 7Jol7l100pmol $ E7D.r2(a) z)olzl r"J + g-EJolTl alzl .tlHul flg e+E
6J+¤.'.4lil6l.R F"J 3rlH t}"ll 6ll%I El¤ trJtrtr Lt+lflq4. "IE
^Jz| ^JEllql
H o e +ElB + ?lqr olzl.. r.sev9 qlqzl= z)! $zlzl ol elHg F 19 zl4
4e+# 4lt6}q4. ilTl ell Ltzzl lolol6l-=^lE 4E¤ 6lal g:-r. ¤86H4.
E7D.6(b) & EzI +q Aqgl= +i flz}9 "Jdxl* tolTl 2.0ev E7D.12(b) 7Jol7l roJ
^Jzl- 4 "J$"lzt
n=2oJ t}Eilql flg tril ol $ulol
ola Aolz| t00pmQl *B o + eqglqa
ÎC g + 9lr}. 1.5ev9 .llHzlE zl glqo} 6J q¤ol zltl t-g x9 zl4zlE 4E¤ 6}zl g:r. "J61q4. r
z*E
"JCzlzI &c-e.FEl Hul-4+e + fl= q# 414I6'Iq?+. ol.I?¤ "J6lq4. (flE ¤+ E7D.t2(a)ollr.J ol+oJ %IBg
^J4611
_trolzl.)
E7D.7(a) eke| k=:nm-'tr- -tr^lsl= dzlE dB ¤+"*r+

xF+ E7D.t3(a) z)olzl r"J {iz} + gEJolT} n=toJ *4ql ilg trIE s}-E"*+
Brl "llulzl$ +6iq4. E"J 3rlH ti"tl 6IB +E gtrtr Ll4rilq4. ol El-¤.d:+
E7D.7(b) e-tuq k=Snm-rE -E^l5l= zl-Pr "Jczlg cB ¤+* = ^7llil6}a
e-l a+, f! zlcllz)zl4l Qtz)rol .J 9bzlE 4Bg 6'I^l g:r. ¤B6lq
4 Brl qlLJxl= +6Iq+. +.
^J{ql flg rIE uF="6Jf
z)olzl t"J
E7D.8(a) d=o}"I 2.0goJ gu3olzl20lE ¤+ ollulzlE zlzla- 94qe "l
E7D.13(b) ^Jzl4 "J"EolzI n=roJ
IrJtrE
rl+¤:+E,ril4. E ^4lzl6}jL E"J elE trq 6lt'J +E: +4rllq4.ol ule"g$
E.6J trlle-l
E7D.B(b) E%tol r.og"J g-trJol7l lom s-'9 +E-tr 9$4_o + "lFg el A+, lel zlrflzlzl xg zlr]lzlts-Q E= 49zlE ¤H6Iq EoI
trll
4 =zl
el ffia]ffi ala|.
E7D.r4(a)z)olzl r"J qlE_+E +q 4zlzl eqfl+. ol dzl9 0A qq
z)o\zl
^Jzl + dz}9
1.0 nmoJ (1) n=2el n= l, (ii) n-g$ n=5
E7D.9(a)
++lE ^|olel qlqzl ?J4i= f, k| mol-r, eVcm-,E 4l4i6}q+.
zlzl r_9 e tI4 d*
^l ullt"l4l "llH
zl m"c+ ,J"tzlE trz}9 zJol= 9"I4 I
41,9+? Compton ol-b s}4"14 ).,=L,1*"c= 7l^laol Bg
7Jol7l1.50
E7D.9(b) nmoJ tz} 4 dz}9 (i) n=34 n=2, (i) n=74 n=6
9lul zl ?J4¤^ kl mol-', ey cm-rE 4lî5}q4.
+4.llqq
=gE ^lolel J,
E7D.t4(b) 6} Hol roJ "J%r-ill dr.z} elql Eqfl= "J"JolE zlzl_z ¤#
E7D.10(a)
^JzI +ql Eqfl* "JoJol.el
lil+l El.E"gr-+ v,4 wY
^le
zl E7D.la(a)E 9¤ol 6Iq4.
-il.6J9 E_q+. gs6J 4+g zlE. ¤g -Bolel. E7D.15(a) z)olzl r"J + gEJolTl n=3oJ t}4q flg ql ol $ujolz|
E7D.10(b) liig
^Jzi +q EqglL "J"Jol9
^J^l.
v,4 w* ^le zl
glqoF $ ffio1 zltl k.3 aIA= +6iq4. E q¤ "JE7I0ol q= +l
jI.Er¤- sq+. g.e-6J 4¤+ ziE ¤¤ Eoi4.
il= qqd=+i
E7D.11(a) zsolzl r"J
+ql fl= "J"8"19 1t4z| (i) r/,4 (ii) vzr"J ull
^Jz| E7D.ls(b) z)olzl roJ {}z} + oJEJolz} n=5oJ ^}4q flg ql ol oJEJol
0.4el.!+ 0.slr gEql^l ol ojulolz]. gag q¤¤ 4tlat{4. zl flqo} 6J q¤.ol ,ttl }.$ *^= +6Iq4. E q¤ "JszI alaoJ +l
"l
gE qlql^l= ^l-olel
u+-"El+zl "JA6lq,4+^J ffio; uld*E +qdqa -H. zl= qqflL+?
olz|.
Eitl 7tr
rL xlE
uo ?E
Lo
-r--t
¤E E^11
D7E.1 0e +lE "llHzlzl ¤rHal-b ol-I9¤ "Jzlqq}4 94e ¤B6Iq+. D7E3 3sI tltlz}9l +oJ "JxlEeL4 zl¤"1 "J^l+7t k¤ trll qH oJ^l
o + jldqe}4 zl¤+ zJzll q=zl ¤B6lq4.
D7E.2 #+ tlE1lE"zI9 qlul^l
=91
?J49_ d=d'4 e
^J+q q4 qB
4 H6l+zl ¤86H4.
G^
L-'u
E7E.1(a) (i) u=3 (ii) u=4oJ arf {f,2} u}-=-"9-:-r,- H zll9

"}4zt E{ E7E.4(b) ¤=Jol 5.16x l0r6kgolr E *izl285N m-'oJ g"3o1e ¤3
9laL+? sI tlEz}g oA qlLJ,q= 4lt6lq4.
E7E1(b) (i) u=5 (ii) y=35oJ
=a| {521 H zll9 "I4z} E E7E.5(a) #a B%+ol 1.33x10-2skg'J aEl ds"zI9 'Jd6l-=+ qlqzl
"lflal:+i =
"l tl5zlE C-+E- Zl^l61q4.
+P,l7l a.szzlolr]. 6J
+;| .+s qlqzl
E7E.2(a) u=20J 4!521 EFE"EI+q "tq +lzlE +6Iq4. (8919 ETEs(b) ¤*ol 2.88x 10-2skg"J as} 4lFz}el "Jd6F= F
=
al*_tr
'+Elrllq4.) 9li}7l 3.t7zlolr]. ol tlEx}9 e ^J+E 4l1I6Iq4.
=l[ {$z} "}q 9]ilE +6}qa}.
E7E.2(b) u=3oJ El-Er6J+E
E7E.6(a) *s. 423'o1 "JCztq 7eA0.ao78m") 6J ttfzt s55N m-'oJ ael
E7E.3(a) z=lt arf {$z}q a].ll q¤-"JE_el H9lE 4l^}6}q4. tFzI9 F td ^plql,r] {olzi "Jq+rll
6}elH 9"1-"JoJ ii}t}E
E7E.3(b) u=3oJ {f,2}E 4l'lt qE gEel H9lE 4l,t}6l.q4. *zlzl gs_4AL+? =91
=l| E7E.6(b) s.E. ¤eaiol tI^ gzle+ tao,ee4em,) e *izl s44N m-'t
87E.4(a) d*"1 233x 10-26kgolr B *izl l55N m-toJ g-EJol-+- g a+
+ "Jd 6}eJH g"}q}e} E}
dE"xI9 0e qlLlxlE 4l,l}6lq?+ =;[ {]f,2}elgs_6IA'-+? =+l ^}olql,rl {olz} "Jq+41
t9 *zlzl
EA 281
u=04 loJ 3El tlEz}9 4EB+ EoJg

E7L7(al "Jzl-+zi *qa_ z[{a}r. o] +^}E 0d llE "llHxlE +6tq4. Eq 2gz} +z}el
+. qla EEE F6ll^l ol f ul^=" $fz| zl:il.ali olf.fl4+g
^4lil6}q
6}zl ?+ +tr e*g dzll e*E HI"II rn('4N)- 14.0031,,?,ol+.
r) ¤B6Iq+. ETEe(a) aa| {f,2}E rdqq}4 H}+}Ag E! olluJzlri qfl¤ "ilHzl
u=r4 2oJ aEf tlEz}9 Els"El+ Eo&3
E Ele-, ! E,,=!lqx2rol q* H+lql^J +4u+. ¤*"1 muoli E ,d.fzl
87E.7(b) "Jzl^+z}
4. .fl{ bEE E6ll^J ol + r|Ee"*+z} zlloli ol.9¤(3+g
^4lil6'Iq
6lzl ?+
r) ¤H6Iq4. kr=1000N m-roJ oJEJolTl u=0?l tlEliql^l *i qluJzlE 4l&aI:J" :4
6Lq jrdq+4 Hi$A ÎolE 44==_ +6H4.kr=100N --toJ 4!$xl$
E7E.8(a) "Ct, +zl9 {l# E *fz} &=32eN m-'oJ Z9+ tlEz}e+ 'J zlzla- ol 4l$g qEol 6Iq4.
qr. 7la6l-n ol BzI9 0d TIE qlHzlE +6Iq4. Eq 2gz} EzI9 E7E.e(b) u=10J A4l 5E ^JEli=
zlzla- ¤# rzE.ela)9 4lt3 9¤ol
+.E. e*g di{ e*E uJolI m(35C1)=34.e688rn,olrJ. 6H4. r4I H]+d A"-lE dB4 ¤oJ rJ"loJ ll0pmel EESE +4
E7E.8(b) '4N2 ¤-zlE tl# aJ tt+z} ki=22e3.8N --to3 ar* dEzl.e+ Lllq4.
EEJ 7F trlEEE;
¤E Erll
D7F.1 "Jzlq+ql^J 0l¤'61= 4¤+*el EEI E_gg ¤B6Iq+. ol Eg olf¤ ¤B6H+.
ql^l +Elrll= +Ag "5"194.
*E 9lE E= 9"Jol9 6lql +E+= nzl +l "J"d"l 619 +ag
ozr.g
D7F.2 a4 ++lE qe} ¤+61: "J"Jolg qlqzlTl "JzlslEl= E4+4 ¤E6Iq4. +zlql= 4+ .J qr. dz}.il"J 4+q= 4l,Jg +l.ol+?
G-\
JtJ
E7F.1(a) (i) /= l, ffit=tl, (ii) I=2, ,nr=QoJ ^Je|$ EEI E.B rB o + t+4 rel ^Jqld &E6l-= "J"J"l9 rl "B+= Ncos(rrp)el Eol+.
E7F.7(bl
,-ll"14. q7l^l m& $+tr+ A+s+
^}i Ng aA6Iq+.
E7F.1(b) r=6oJ 9"J"19 q+E]= tl-4Eg qel -sB lB o + ++Lilq n4 9l oJ"J"l9l 4t u1-=og-^-9 4E [l'v:,,w-,.dffi o]eoo1
ETFa(a)
4.
E{4. 4zlr] m1 *miol4. "Jz|+ m,ol {rola.3'u5=+ti:qc ^lg zJ
olE =
E7F2(a) +E =.3tl
Qlf rr.o3 H zll9 4E. "tHE zlzla- 9leq, E nElg +.J6Iq4.
ol +4+= ael {I=g 9"}*i E7F.8(b) aEl 9l oJ"8"l9l EI6J EISE|+ cos(m1Q)* cos(mil)9 4E
:zB zr.s9 %I^lq el6IE +H aEl *+
E7F2(b) y..og H zll9 4r uI l'n
ror*,qcosmiQ dQZ 0l+6}= +all4. ¤zl,rl m1*m',olrJ. cos(m1Q)
4E zld f :lg+i E 0=0ql^l trIq7l ?l?l,guli * cos(m',q)g 4jl'+g q"J6Iq4. (dE' 4+41^lg trll +C
^lE.
E7F3(a) +E agl E}+ Y,.*,9 d+ ++¤ rS4ollBzi. qtr @#ql^J 4 cosAcosB= +{(A +B) +cos(A-B)}= 0l*6}4.)
olE 4E
-=.
"l4zi L+El+ae+? "t4E BHe.-E +49 + gltr+. 6ll'J E7F.e(a)
'J r¤A ++lql^l tlzlE 100pmel gg
tr|4 E= "Jcz}el al
EE 9lilE r+41{q"+(qlE^J @=0"J 4E "}4ExzE"l4). 4+ ++g 4 E-E..ilHzl(u}q tEIe+ arll EE ^J4 ^|"lE qlqzl iDE 4lt}s}q
zlzla-+Ae 4Ag lEol 6lq?+. 4.
^84o1lBz}. "itr pilq1,r1 4
E7F.3(b) +E gL+ vr,.rq d+ ++g glel g+ E^llq^l ¤HoJ 419
=EI
E nlqT} Li4'+dL+? 6il8 E9 gzlE +Ellilq+. 6l+ ++g zlzlt-
E7F.e(b)
"llHzlz} zs"cglrlE :1d4 ¤
+ qlqzl(+kT)el ?JAl El= I mtl lk9 4lt6}q4.
+ae 4Ag gEol 6Iq+.
E7F.10(a) CH4eZlg sc s{l= Y S.ZZxlo*'kg m2ol4. ol Ezl-= qa
E7F.4(a) /=3oJ ^J4ql^l qd6l^= "J"Jol9 trle+EE AA6Iq4. tlzlzl peoJ gtrl+ qaL+?
=la 9lHzl=
rJl
E7F.4(b) I=4oJ
^JEHql^l
qd6l+ 9"8o19 q+EE ea6}q4. ^l4}6h=
E7F.10(b) SF6ezlel +¤ EHIE= 3.07x l0-4skg m2ol4. ol +zl-= sld^l
rll peal 41/t qlqzl= gEt+ 94Lg+t
E7F.5(a) +zlE qde +E t'-ql^lE gdE eEsE +48 + 9l+. 7l7l
^14t6l.=
/= roJ 419 4eE=Jq a-7lel z+ $E r C+g 4l,t}6}q+. 4lt aq.g E7F.11(a) ¤6 pzr.ro(a)E qlolElE ol+6}q cH,$zlg- /=l"J t4EP
ftel Hllie +4qq+. rl I=2oJ ^JEll.a -=E.rll 6l+ ql gs6J qlLl^lE 4l+6}q4.
E7F.s(b) Ezl9 qde +H tlq^lel aeE ¤t_o.e +49 + gi+. E7F.1r(b) g+ E7F.lo(b)el cllolq= ol+6].q sF6+xl¤ I=2"J d}4s*q
/=29 419 4¤+=Jq 3-7le+ z+ *E r CE¤ 4l{}6}q4. 4l4I er+E 6l= ql gs6'JqlHxlE 4lt6lq4.
/=3oJ
^JElle EErll
hE tsIie +4Ll]q+
E7F.12(a) CH4EZIT} 44 qLlzl$ zlzlt- qd6J ullE
E7F.6(a) A?-l +lE oJ"8"J9 A+, (i) mF04 (ii) m,=13o1 tlttrroE-+E d
"l BzlE 4gE
$ azlty B"IzI qAL+?
+ ++r+ fl+ ++ql+ ?+7-+ H zll9 "I4zt ElqTI 9l+ E7F.12(b) sF6¤-zI7I+li qqzl$-zlxlL cldB rllE ol ExI9 4¤+%i
E , qB4l qAL+?
O<Ie
={]6IAL+?
a7l7lg"tz} 941,:41
E7F.6(b) -I.?-l 9e-l go8ol9 a+, (i) mF*r4 (i) m,=a2of,
+ ++r+ 6l+ ++ql= 4?+ H zll9 "I4zl Szllalfl:u|? Elqz} ?ltrt E7F.13(a) (i) l=1, ffit=-L,0, +1, (ii) l=2* -E= 7l+'6J n,"J t4E¤ *4
H, @Ag "le4 9ds*t q= rBg rB 7F.7(a)e+ Hli6}4l rel4.
E7F.t3(a) (i) /=0, (ii) /=34 EE zl-b+ z1"J t4# +Ellil= rBg r
E7F.7lal rq *"ll^l ¤+61+ 9"Jol9 Nd',09 gol4. A+ Hl*61r1 reJ4.
ts zp.z(a)e+
sI t+ Ng A46Iq4.
282 7 grE
4¤+*ol tola z+ d+ol mF+t(4 r :iq-r,il)oJ EEle| z+

E7F.14(a) A¤+elol lolit- z+ dE"l mF+loJ dlEteI z+ ÎolE 4EE
E7F.r4(b)
Îol9 4EE +4'l]E 49 +E6I{4. r=tql q6J "l 4Ee+ r=s9l 4 ++rll} ^lg +E6I¤4. /"1 4+61 4zl} +qlql^J ol 4E= 9"IzI
eI "l 4sE 9"IzI q!+? El?Le+? q7l^J ge ar+= q¤- tlEl] gp-l= 0l+611^] ¤B6lq+.
-*vllt S^lE
-=.6lxl ETll
z'1;
Ou-t 't
t7.1 Imol9 $d zl4l Ezl¤ d*z} "J%IAI {tz}9 "ii4 qlLlzl 3.flE (a) CH.Q)+C(4¤) + 2Hr(g)91 4t
8s Tql^lE a,G"ql +.J 49 +
ilxltJq! 7I46Iq4. (a) ^Jz}el +El= HElrlzlqE g"I"Jd E6Iq?+. olq^l zle ¤9 rllolel s.-e+El 2e8Kql^lel AJfe| A,.fE
"Jg fl+qo| a[fl!*? o) E{¤"] d+^ytrJE.
n*1?l tl48 z]zlq]{H ol {_r. o1q,q ol cllolrl s++q g+HgEql 4+ H6}zl ?+=+
*g
gel "Jol B4zld-*? (c) o1 a4b EE 2Aql^J ¤Bt s+ "Jql +6J r 7la)g ol¤-6}q olE H++g "Je_l.el s-Eqlîq a_q_E H++^14+.
4q qBAI g+qdL+? (d) +g S+r| +& S+ ÎolE ++g "JoI (b) g"l gEq^l a,G"el fiol oJ=e-e EldL+? (+aq=
oltl'el
^lEg
E + 9IAE+? oil4zJe-E Er-lzl *9.q, q+^l fe} +ue+Jq= ol$all,tJ +il 4lt}
17.2 (a) ?olzl LoJ tr-x} +9 g"Jole+ (b) ael d¤:z}9l 4Ei ¤. 6}rl+ r4s E^lE 6Iq4) r000K_H-4 g{ q te gEql^l= ,ll
Ax=((f)- (x)2)'24 tp,=((fi)-<p)2)tt2 A$$ +6Iq+. ol$ {ffi $ Eol ¤4El + Strl= +tlg 4zld eg er+E q"Jg f ?l4lg4? (c)
qAC g4e+ ¤*rlzjrl E6Iq+. l000Kql^l ol E"l +illel ,J"l qEqI+J. 7}a6tr. ol Ee+q %I=q
3lr{ ,r-il219 +^}el ++¤- 4lt}6}q+. (d) ol po1 HB + 9lselE ol
17.3 Ezll r7.2E oJRI4?I "JzI tl4ql *E (a) oJBol("Jxlf n) =
gel qqzl "JEel g"I"JaJ ESol 7I^l ¤q(420nmel700nm E+
^JzI49 Î"lel
e+ ol aEI 4lEo zHoJzl+ u)= 7l7la- 9Eol 4q4. }r) +q eil!{"t 6IdLLHol +tI gE A,tq arq^J Planck9 Es H
49 o + p(Lr)M,E AB + 9l+a z}{oJQ)?
17.4+ Kulkarni # q+ zlI. z1z191rJ H}zlolzl *61-=.J Eg gA4H =rI4
u(science 1478 (less)).
"l ÎtsEg "l EE ^flEflq ,ilt"] +4tj+ t7.s 7)^14 Ei-llql^l +E++zl ?*xl"J 4L"lel zlEE
=.zloll! +4+=
_r. trn6}fl=Ell, ol EAg 1000K ol^Jg gEql^l= +46}zl ?+=trI-. oI ¤B6Iq4.
gel EHJ fldql 64 a4g zlz];t- 414I+ Hlq e-l6IE ol EE =eg
"lil= 17.6 dtzi * goJolq 4e| {:="2171""}z}EE}4 4lq 46J -rq+-6J sEol
e%Le +tE qt zoullz} Etrl. ol E¤ xl*ztzl "Jag H 6ql^l 7l*
7Fg A^B ellC"J 1o e ezr¤+. ^l 9E olf¤ ¤H6Iq+. ol gs o + +EI"$ + 9l= glEI4 " + +eEI 4l
E qtr 401*i
E,la8
flrl'7zEgl'^tr1 EaJ
ol gzlr-ql^J= flz}9 'dzl- 14'+ gzlq +qel dzl- ul]

8c flr1^tr4EH
ilE. ¤E6l+ Eil "JzlEqI"l qB4 "l*9Ezl. ¤g6}al
g Aol+. "l4e} z}]HS flzle+ Ez}el +a q "lE9 tI$ 4dz} flx}9 +^ gÎE a+E+ ¤4-6IzlEJ a
g 016116l+ rll "}|* +s6}q q+^l slql4 " + *s.zl H4. g gfl. ^qEHg
zlzlt- rfl+ olull= dzl-E
¤Bg + 9t+.
Îolel
44214 ^JcAL+I+ zlzl rlc.z}S q$ql qlqzl iPl +oJ=ot
zll *445_r]1, roj zlE'E zlzlt_ sE6ll^-l +48 + 9l
"lES
8A +AE flr} 4. "lE zlaE 4dz} flzt9 dill +llE 4eF%14 43
^g dol
Eo*9 +4Ll]= szlel Egg affi EeL olE9 Ejr*q}4
ol Eqql^lE. .g"4^ zollrl 3" P* "JzlEqlel fl?-lE olao ol. E-zlHli6l+ dq +4¤- +4rll= ull olf-$r[.
q '+iE flzl-l gzl. Hg z9 rdzl flz}4 "1859 dx} 8C.1 +AE flrt.el Ê4EH;8C.2 qdrl flrtel ^r4EH
= rE9
+aE ¤Hg 4o14.+49 flzlts Schrodinger alol
g,J6IZl gqzll s 4dzl. flz}q +zl.el +aE ¤B6le
ql gsq} + zH'Jg o14," ++q E¤. f ?lzl qlE g rl-E 0l rlEel EE=?
^JIEE
ql +s6I+. flzI "Jql Eqfl= t dz}9l 4.J scnrodinger
+= ql= ir+tEt+= 4= 5-gO %FÎB ++e-_n E4 ¤* rr"il,rl= gzl. #+g ol+* gE ¤+ql 6dg +9.
^lg
rl4"F 6Lq, ols+ Bol 6Iq E= rltEl++ +AE flx}9 EE ÊEHS 846}ts HE
trI. Bl¤ ="4 ??l zl4lg a
'flzl tllEElf'al r 6I= ql+61 +sql 1"14. Cg AAB + ?lil, r g;"lzl tFqE 5ag AAg + ?l+.
8A.1 +48 flrlel +5; 8A.2 flrl +lEa+el f oilL1rl
88 qdrl flrl
'4dz} flzP* 27ll old-el dzl¤ 4= gz}+ olgEol4. qle
! u oJelel E= ?4 i;lzl {zl"tl s+$tr}.trp}^l 4zlzl
E g"J HeflzlE 4dz} fl2}4. oJ e{oll.<-l= +48 flz} +ll
Edf$. olaoalcl 4dz} flz}9 +aE ¤BB L"14.ol"ld
}g'el z}|.¤4'Pauliel u}|4 fl49} AEt^14 flxI C¤9 fzl
C4fzl8s9 +aE ¤Bg 4o14.
flEet+
88.1 88.2 pauri ullEi flal; 8B.3 +I' flq; 88.4 rti{l-
=llg;
gB¤ 8 t{lEg+
E48A +^=flrl
> ol EEE u[+= ol*

+A flzt9 nvOOers 8+4r PeErjl, ¤84_" + Br-qT]
+4 fl^lE 7I= 0l6]|6lE ?i= trlE -E= flrh +7]E E, :ral-I
016116l.= Ell 6-4C01 Eq. ralr q7l^'l sagq= Eolel
#9 toq 677cm-tol4.
=Et= ErlE9 76= ¤861.= ql 7E7t Ett.
T[|LJ-
8A.1 +A= flrlE +5
> E4C TllLJ
E^l flE-Er+= 2l^+=e E^[= E0l=t11, 0l== t^ Brlel gz} Hs= 2olzlu] dzl-= aI4"J zlzla_ gl= gzt4
"1¤.
E^P l,*= ollq^lel ^11
4EE+J= LIE|LH= a0 l+. g +aE flrlelr El+ +i ?lzlE qTlql +61+ + qlol
r4z- loJ). gz} H-c.z1z"J, El+^l q d6}7l zeoJ ia== fl
> gg.et qHl rl^l
zI "Jql .qfl= dzlE'tg!+ ?9 coutomb ulH!¤ 9lHzl
trloEt+E TllLJ(Eq 7B)= gr. a7jE^ 6fl48+ 9lolot -Ltcl. E-d
Schrddinger ?.Al E?J=01 r 6110ll olgXl x1l9E E 4=+.
7161.=^l go]ot^lE ^ll+I
Elrt(EE 7D).
vo--ffi (8A.2)
f4 zlzll +ql^l dzlE %r-d^lzlE uz$zl¤"I ql4Elir, ^J qzlrJ r9 4o ++q A4vl^lE 44E, rBla s"3 tl*
C¤ .E "llHzl9 HgzITI E¤+4 tl5fE Hg "&=61 *d¤."14. trl4^l dx}q ¤=Jol rzNoJ 4 o e. ol+qd flzI
q, "J¤q 'dE's ¤ ltrlEeg +4utrHre 8A.l).
dillql 4t hamilton ¤tl4^b +94 ?ol ¤4.
el fi!:$qlz[ ]ohannes Rydberg} ol r.,E E H dSol d+^+llHl
trtS
+ ee ^lq q=+= ^l-dg g.t4fltrH18e0H). A=6u,",".,,nn*iu.n,.,",,+y(r) +4= glloll
LH-J=Hu'ltton (8A'3)
__ h' vr_
''
t' vl._
-' zr'
2*, 2m* 4n¤ur
V=R, (+ +) +^fl^lq
ÊEaJN
(8A.1)
{zlrJ v'ql E"J ?zt ee+ Ng 44 Cz}4 qE 4}Eql +.J

¤zld n,3 t(tyman 4l¤), 2(Balmer 4lg), 3(Paschen 4lg)
"l$g s.^l+rl.
(a) H#9 Eal
7t^lBq
oo ut$, tr/nm
E"-lE4 dzlglrJ 4e4e-e ^J4q= Ag Sd+ schrtdinser
o ooo o oooooo
o
(\l ooo o oootoNo
r@(O
llll
tO sfF)N
trtttt 49 flzI dillel +t4"J +F3 +44= +E+ dzi9 4
+g eE¤ +4r]l= +89 EE E?]^lu + 9l"lot g a
llil ol+= 4"14. q +flqld9 dzlE ,]l+ +El.rll. #
Balmer Lyman Schrodinget {3 q-q-+ t"l 5}4.'
hz Ze'
I
,to
Paschen
- -"
,u''' - 4"rrrv - Ev
+aE fl^loil rl]-d (8A.4)
Brackett
111 Schrodinger al
me
I
ll mN
fal 8A.1 t^ 3^lE .rEleB.

=EE ûlegalolri=
4IEEE
E6]|-d a= LElL}|flc|. Balmer
=dEl=LfEtLJtr[=
4lE9 dE= Tl l gqql^j
r ol Hf E?.le.l {rll {r,rlloJ 4ag ol jL4E E^l.olE ,!.rlltJ 4+3E a
Ag +s-61qal. Hrq ¤g A.a6lr. se.oalql ol.E= 4l& r+Cg Eall d ¤9 tr"I4.
8A +4= flrl 28s
¤zlrJ9 ul+g qql 'ilq} dzl.9 tr-.]14 ay*91 ** 4"14. 0

l*0
rqr pts stl traJol+. ol +& e*e dz}9 e=+4 49
erll q=rJl, _7 vlge eE e=J ur.rol dz}9 ¤*E+.Elt s
j
4 =-zl qlEql rlpl=rlrn,7} Ela q4^l tt=m"7l9zl ollEol K

5
6
+. r?-l6}q 4E6l ¤"J'J +4ol olB trll= +HI AeJ 'l]d {ru /=0
E]
oll -.E,r.l$4E +B6I+. H
trlHl¤ .llHzlE +C 4aq1{=.91 +++)olFe r}E"E} ,ld
oF
+= +44= 4e q-q_4 ztol zlE E= ++4 "JÎB +

Ee-E q +?-l^lvJ +:19 4"14. HJXIE, r
lal 8A.2 t^ fl^l +oil ?{= d^l-el +E trJEJ!¤ oilL1^|. ?{E 4EE+Jo|
t{(r,o,Q) =R(r)Y(0,0) (8A.s)
ffA qEJl¤ 0llL1rl7[ Coutomb tr]EJl¤ ollLl^lel ,Jtr|.. d^l'71 ilE
0"J trll=
43EaJ= 7ttr ttl|= flC+ ErtTl gg 7lq= 6h=tll, Tl.zlol0ll^1= 0l
:.-{
¤zld R(r)E g/.l'E trl.=:d+ r4-r- y@,il+ 4E tr!.=-il+ ErfTf tHtrJal 3t|.. /=04' /*0?.! trlE:Br+= -q c]E Tioe
4l tlrt. r4H Schrodinger zl-sa +elqr, I rllEl TlEHEEl-.
=i1oll^1 =.zll
+ 7l¤21 qg-4 a3 + 6117} ¤+.

^lE
.,t'y=-/(/+t)y (8A.6a)
oJ9 zlol l/lql ul{lz} Coulomb .J9 zlq(t/roll HlEil)E+
d,R q #+6t4l 0s F d=6I71 uflE"tl Hl*6}rll ¤+.

h' 2 dR ^lE "++
V"uR = ER
4 t=0+ t+ 0?l + A+9 4= q r4l +szlE}
_J___
(8A.6b)
21t f,72'rdr
=ilql^l=
H *ql^l= HliB 4e 4 d4e + 9l'i
¤zlrJ uJÎB ir+J=" e+= r+q_ 4 eg + +,q+ 549 ztzll. gl4.
v,u?)=-ffi*ryF (8A.6c)
4 zlzttslql^J= HJÎB u|"=." o-Jfz| rroll Hlql6}q,
+llE 4¤+*"1 4e++ 4zlzl Bag q¤"I {r
8A.6aal3 6Cd ++l= zl+E4l g*4= "J"Jolql ql6J
,lo
*"i11+(rB 8A.3). Rr-
Scluodinger {4 E"J6I{, olol Eq TFql^J A+6I9cI. ol ll

rlol
qsE+El E4 EqzlE E= %r-^l-¤ uf-=."alfz]. il

el 6ll= +H aEl E4<s 7F.r;o1q, ""tzl.+ l4 *,& zlzJl $ zJ+-6J+4oe gql d=*4.
ilru
se.eu^lg BJÎE tr!.= (98)+l"l4l *4. ol %r

^l+ + ?14. ,Ja^lE 6|]E zr^]16l
yl*'rJA^lg i4Ql¤ {lHzlz} %ft(r).J li]+l ¤9 0<r<"" dîl EA ¤Eq 44rl oJ^lB r]-$
ÎB
"&11 9l= eeJ"] p"J "J"Jolel ¤# +4.11= alol4. _E_H q r'E9 o}+zt H 4=l ¤qql^l zl
zlzlololl,<lE 6l]"J
i-*f4 " + e4lq= Et+e+ +6Jg+. r4r ol + ¤qq]
ul^tr.o 6I^,- q-q=l} ?ol r9l ++ rI6J Ei+E Seg+.
uÊI trl= rJ8^l
(b)
^lel
%*(dE Eolg g4a||-HH BrI¤ u|="alfz} +4.11- E"J a4 qoefel E
E 549 qL AE ql+g + 9l+. aA.6czl9 a4l 6Jg q rlull4
=i1oil^j Et+g g ¤g Ee
lalq^1 rlu[1
9 dzlat +ql^J 4,.lzl *E qfl¤ qlqzlq. r
couromb R?) -7 x(r9l +6J +6J Et+) x (e^l6IE r9 zl+EL+)
?]r E4 6Jg 4 ++l= E= dzlE 4eF* qlEql +EI (8A.7)
+= r.d4 zl]H9 gCqq 7l"Jq= 1o14. /=0oJ "ll= d rfl6}q ol Ae gol g+.
zpl zqgS-=JS 4zl ?+eq, q+^l r +E slQl¤ 9lulzlts ^lg Q+4
R(r) = r'L1r1e-'
.EE tlzlEql^l "Jqg ++q. +++ coulomb -J"Jg +
,ll g4(rfl ee.z). eI¤ I + goJ ull= gdq olol +3i ElHl¤ ol qq tr-+$ol gaJ!{, 1(r)3 *Fl + E}+E ¤A
^lql=
9luJzl9l4 "J9 zlq= 6Iq, $al dzITI q zVttsl d=6}tr ^J7l=
4L¤¤ 6|= {oJ EI++. 4 zllts1olJ.<-l|-(r=0) +6J
(r=0) Ufql Hlql6|= ElE.Jol l/rql Hlqlq-= edzl4 "JE Etfz} *izl 4a e-,= 1ol qq EI+^J R(r)* r,ol ¤4. 49
olg "JEaI{ dz}zl- 4 o e+q H}tsq=- a4r} +Ei*+. E+q E9zlH +6J El+ qlq zltsI4 olol a-t-,ql Hlql6}q
/=ooJ oll4 I + ooJ oll9 qlqzl= q zlzlololl,<J (qzl^J n3 tf) rr]6}q /&ql ++614l EE +q 4
"l + slHl¤ "r*4
ac4-9.E rrll +s4. :zel4 Eq Bqd *ql^J= fldq ul+.++71 rn-te-'9l Hlqlol.rll 4l zlf 6r+4-9-tr. 0-o-+ +
286 8 flrl'749|.4+EaJ
E 8A.1 +AE flxtel U IE trl-$-gtf R,,(r)

-0 n R*r(r)
,1
z\'''
0
\a ) "-,''
<F
i(+)" (2-
;ibo
2 0 P)e-P'2
W
E1
2 1
fi(!)''' 0,,,
3 0
| (
tt
z\''' (6-6p+ p'1s-o''
HJAIE, r z+l''' \ a )
fA 8A.3 EI 7l'zlololl,\1ts/=1?l +lE-Er'+7l,oll H1416l'r, l=2oJ flEEt+ 3 I

| ( z\''' (4- p)ps-ot'1
tt
/0ll Hl4l6l'r, !E /=38 ql= Foll H|B{l:dtrl'. /01 Elal -4 +80"'( a J
= Exl.7l trE E1 HHrllEtrl. /=0?.! +lE:Er'+=
=7|':doll =iloll^l
91^loll,\'l 001 olLJ *ElEl
3t2
"19
,$dt, (1
= 3 2 p'e Pt2
2lo-
ti^=
2lef
:<L-1.
I
¤zlrl p=(2Ztna)r, rBlr a=4tah2tpdol4. +"J61 +|g 4(E= ol"ll

4E4rxlf *f
e*ts.Jtr-*+qI Hi r_u_4 zltsHzlol+) =+
4rr ^J4ts + 9E q)ql 46il^l Y p=^,, r4I at: Bohr tlzlE ,o* ,J4.
aflfi zf,\lal trH ol ollzl ++E + gleBlH +6J'J+ +E
(o171,<J +B +alsel +q a +e+El g aol+. Eq
lg
nlkol "Je-l a+ zJ& zl4"F 6J4. 4 n=r,2,...4"F d4. "l
zrel sltlzlE t}^l 2l). +^ll4 o + 8A.10^lE 4¤¤ trl+!+
+= E+ trl-* ^lql ")el:d+q= qlqzl= +$LllzlE. +4. aol 6114g + fltr]..
F lren . Z'
E,=-;;_r^r*tx ++.sE[lE ollLlxl
_, (8A.8) ol qlEql qo ++q H ,l4ql^J
)L n Eoll tt
^l+ "JzI
^lel6L-AzI
t}tr.o Ogg d=++.
ol{r9E,rl "JH}4"J Eq "}^}¤ ?S.4. olzll =
pt "J4 trllEql(/>oolzl"J 6tH) qE +lilql^J +
'+JE"E'-+-
ol 6J+=ol q4 zlE q$4l E
^J+E$ all$ flzL Hsql FE4zl r=091^l 0ol q= 49 EIEEL #
¤alEzlE Ei-do} p z};ll+. +d "l -J+# +-qHICel ^tr¤+.
fz| oS E"4fl* 4."1 o},-l7l trll$.ll(¤ 9"1 ¤ *ti
H+ p= olf-aH.<l trl+4 ?ol tt4al +4,Jrl- + fl+) ,J^te u|4zl-olq+. 49 E"4a}l 4zl ffi
2Zr m n--
4nenh2 E "I4E E+ 4E E|qq-.
6- ___:_
60- (8A.e)
$-Laguerre rlaj- ++= oJel ate-E+El +E {t
Ao
'nA 11 ffi*¤
2
o + 1lE6Lq, ol ql$ql
"J^tB "Iq7I +4++.
^J+s^J r Alg
q7l^J aoE Bohr UIIEol4a +s=
s2.epmolr]-. ol 843 olBlt tr-+zt Bohr9 azl +4' g "JÎB -E 8A.lql ++'l]fr.eq, rH se.+
"J+=
zl E$"tlrl alxl qlqzl +llEel tlzl$$ +44= Ell qlE ++'HH+. a+ HJ^l¤ u1^s."r49 Eol ECES-g/.]
^l^.S
9flzl qlEql +g aol4. ¤zll4 o-tr= ffi,KmNolE +(tr} {z1l ul-=."4;4 8A.s^lol ufe_$ eol Sd6l B^l¤+.
4tl mJp=r) a4 aoZ 4E 7l7l S.eq EI+^J eE flzl-5
ql El]+ pg cggl.rJ a6E ,\JgollE s#+(,Hql^J azlE V n.t.^,(r,0 ,Q) - P,.,(r)Y,-,(0 ,Q) (8A.12)
a-r.0m5aool4). 7zll4 " + "*^l+71nrt /"J dzlql tril.J

"J z]trJEt q 8A1
^t¤
r{-5.o6J+= q^q-r+ ag d.J++.
n=r, l=0, mFyoJ dzi9 qql^Jel +E "JEE alt6l-el
R,,, ( r) = N,,., p' L,,.,t p)r-''' "J7.lE trl-$-Ef+ (8A.10)
H f-{ r=091^Jel r3 +al]o} ++.
6J+. ol "
9zl4 L,,{dZ $Lagueme +6} E}+4r e-+= 7l ty,.r.r(0,0,Q) = R,,o ( 0 ) Yo .r(0,Q) = r(*)"' ( +
zlill+El +4 q EJ$l -BolzlEI t, p, 2- p4 Ag A++ a )
-o.
ol4("1 ++E "J+= E 8A.lql^J sotB + gl+). oJf N,,, rBlH E+E 'JErI +¤-4 a.ol ¤4.
e +¤-r+ ?ol *rlB a+s+^lzl= tf"l4.
vl,o,o(o,e,Q)=#
(8A.11)
Jf &,,,tr)'r2d,r=r ol llg Z=r! ull z.tsx l0{ pm-:ol ¤tr1"
ea #aE flrl 287
8A.2 flrl i{lEB+e[ f ollL-lxl rlEI+= 49 a{al.q4.
t +q Eqil= dzlq ql+ rdz} '}FEI+E flxl +l

flzL (b) ollLjrl
E-d+$r. 6Iq, +Ê flzl-.ll qldl^l= 8A.12^l o + E^lg =+l
8A.8^lol +Qr]]= qlqzl f;.?l= rH sR.sql +E}rllfl4. "l
53 *=+. +ig flzI +llsEl+= n, t, o) m,! ttll oJzI+ E qluJxle+ E+ r ,lr-lb zrql Hlql6tq,
"Jd
7l^la_ AE6J+. 1j.zlzl se.rz^]9 + rl=.oe-+_e. Tleg qeI^J He+(Z-2)! =9E- Î"lE
= H(z-l)ql^l!-+ 4HH+ trJ HTtl
ullE- ol 4zlzl: +llE.fl-ag d+EI+r gEItrI qle! q5 =+l.g
-Jf ,/,,o,oE 7l¤q= dzl^= n=1, l=0,4 mr=goJ +llEa.J+ Eqt]trHrqr H}E}tr-El]g "llulzlE 4HH+ q 4+). 8A.8^l
ol +4ql= oilHzl= E+ gol+. olae czl rJ49 +
d+++r E6J+.
+61 E?-l gq4 il= dzle+ fl$ zli_e--+ illl.zl
^JE
ullE"l4
=
(oltrllg qlulzl= 0o e +gt+). tr++^l +tJ SEl|ql gl= dzl-
(a) +lls-d#el B^l E qlqzl= osr+ 4tZl 94. Schrodinge, 49 dlz} "J9 .llH
oJzl+E 44 +JEJ+9 tr.oltl dAg ++Uq-. zl= 4= tr|E 9l+. "lag gzl Lil+9 dzlzl _::."llHzl f,-=
^-11
. +?Fl+, ng +llEslfE qlLJzlfi $llalq(se.s^19 ol4 *zlql el6fl^l $lzl. greE t$ qlqzl$ zlzlL Flq'I
E
g trIel Hl+H+ SE}|ql 6ll$q}+. Hl+qF dz}9 ollulzl| ofzl.
6ll^J), n=t,2,3,...E #g *=+. piqzl ?+eq, qlEql +lrlE Ea g+.
, ilE 4EEE-J zr^h, /e. dzlE 4+E" "* zzl {t(t+r)lyrrr "l ^J4zI +E}+rll
8A.8^13 trl+4 a."l ri ¤ + gl+.
E +4rll= a9EAJ, /= O,1,2, ..., n_ 19 AI9 4=+.
' xlT l ?Ft+ me,+#*A z+ 4E mfi$ +4L}]: a
n
L
o +,\l, ffit=o, +I, +2,. . ., +/E ztg *E-+. hcZ'fr.* pe'

oilL1^l
Ln-
n
2 ,ft*
8$ +HJ dE|1 (8A.13)
+"J4-+ nz t4 3l'llil= ,ql+61q, E tg mtlk9 HglE xll
2 0.1 5
0.8
0.6 t_
1 5
S
q 0
(!o
N n=1,.1 =0 ? 0.4
n=2, l=0 $
N n=2, l=1
N
L
0.,
c
t E t
0.05
0.5
0
0
0
0 1 zrrrr2 3
-0.2
0 5 zrrro 10 15 0 5
zrru]o
15
0.4 0.1 0.05
0.3 0.04
\
s
(! o.z
n=3,/=0
N
9-o
0. 05
n=3, l=1 0 .03

n= 3, l=2
N o G
N N
Eo, c C 0.02
t 0 E
0 0.01
-0.1 0 7.5 15 22.--0.

05
0 7.5 15 22.5
0
7.5znao 15 22.5
Zrlao Zrlao 0
r=J 8A.4 flrl EaTl zoJ +4C 8^lol EH:-J dfll=E EJÎC qE-el+ I=oE ?lEag+= "l0ll^]
i.1B E 001 ouq f,EE UI= zJ=qE AE +q6lqzt
+B 4E714 3?DlEl qe+ + glrl+7f +694; -"joe+B Bla4 Eal oJrL
=
288 I flrl'7=gl4E5aJ
G-A
L-:
-
(c) ole,_5it ollLlrl
H'+ e- n
0 ¤ gÊ ol$trl ollLJrl IY TlilltlE alzl "]lH^l ^J4(+ HIEI
-hcRrl9 3
^JE{)ql ?lE :z
gÊ aj glz}E$el dz} 6}+= qlqLfi=
l{I -hcHrt4 2
j r1f $.gt 4i qlLlxl+. ++E HlElt}4Y n-tql rJ4olq,
K
5
6
;rx{x{o
su-. = r qlqzlE E,=-/rcrtrrol4.4zlzl r=-gl 4'J6l-= 6glg
aEqts
o[L1^l EEH ?)zlzl olg3l+qq(rH 8A.s= _E-oI+), trl4^l q++
Ae qlqzlz[ llo]ot ++.
-hcR,
I -hcrtu (8A.1s)
fB 8A.s +A fl^l'9 ollLlrl 0l 'Je ExE[ gd^l7l P-dal Eal IE (lg z.rzgalol$(ral=10-,81), olag r3.60evoll 6|]%I6J+.
=?1.
EolTl illE E^l6lr. gl= AiE}|= T|=oe fl-d aolq.
Etr+ dt g^l olg+ "flHzlE qtr-= olg4 4fl¤ol4

rtr 6l+.ql ol13 "*zl t*iqlE 96l ,^;r 9,14. olfl +q
sEq= E"J+4 ++E olg_+ Elfl¤e d49 EtHl¤ {lHzl$ olge+
ol 8A.ral o + er+e+ PaJ94, flzI =
^lg qlqzlel alolzls+ Es+^lzlzl f.loll,rl dz]-= Eon+^l4oI
ql ql¤L Rydberg
^J+= +*r+ ?ol *"Jall =+. al-b dzlzJq ElHl¤ il-= +El,]]b 4 o +,t1, E9lE E=E
4 7l slqoi't}trt. +d9 olgs] "llulzlE r3.60evol4, :a ol
; ffi"¤
K:- Rydberg 8# (8A.14) gs+ qfl¤g rr.oovol4.
Selh'c
gzl,..J pi flztg +41 aeJolq, R*= Rydberg g*4.Rn,

g SCQI flxl-N(dlz]- o1.-r!)ql ql6J Rydberg ttf9 <i"l Hz!84.t ole_Et oilL1rlE EgEl4
q, qlaql N¤- H_tr_ Hl-+r pE 4l}aial q6}E +r $z}gl =¤
flzI t4 +A= r-l-s=!+ ee %r-= dE¤ +4
rll6J ,lB tI+.E (}g n,ql Bq+E +^ g ol$g ^dlEH
n=2,3,... FE +g tlEHe+El E.+ F"J
^J+71-¤+. 4}rll,
qql ¤e e4e+ 49 g"J6}rll "Jxl6l-= <tol 434. + *g tr4s d"l9E 4Eolch 82 2se, e7 4e2, r02 824,
^Lql
ol EAE E"Jzl= Hl alollî +^l6J r}s 292, 106 632, r07 440cm-'. 3lz-l ^J{E olgs+ qlqzl
^JqlC Schrodinger ^Jrll
C E-Ag 6l]+zl ?*zl oll+"ll ,.JzlE 4"14. ag +4q?+.
oe +461-ElH
zE{El Al'El "lgE+ "llHzlE Hr'q}4
zEtEt q 8A2
ÊEH dS9 +E +{},4 dE"l +Hqq ¤+ gq
fuE {}g gzl LllEql +e+ fleq, r Zlg rle 737cm-l "l +4+= +g *"t"F ++. -hit tn2* +g qlqzl ^J
ol4. mp=1.672 62x lF27kg, m,-9.109 38x 10-3tkgols + ql4r a1H
=lxl
oflHzl 1l4 Eo*.E d"l¤ Ell q-q_4 e
+a gzl9 ++Î e=*e ol.4e+ a+. e ++e-l *zlzl %r-=¤trI.
I = -Eo*",
U='
memo
_ (9.109 38x 10-3' kg)x(r.672 62x 10-2'z kg)
' m.+mP (9. 09 38 x I 0-3t l<g)+ (1.67 2 62xlT-'1? kg)
1 Rn- E,o*",
& +
I
n' E
)
n hc
=9.10442x10-3' kg
tr}4î
trl+^J EI¤ ttnzgl 4allrJ EÎ6IE zl$zlzl _Rrolr_
¤¤"1 lhcoJzldol +e+"t 6Jtr1. A+q+ 4l&71= ol+
6ll^J ol qlolEl= ali zl+$"il tr+{ zlel6tfl ol qlolEl
9'104 42x10-:r !.8
xfi9
fl,,
'- 9.109 38x10-'' kg
737cm-'= r09 6T7cm-l
E A"JE7I-Rlgg a+= eg + il+.
ul4rl dzl9 u}$tl4l(n=l) {lHzl| ffi$ ?"1 ¤4. q-+E-e- un24l q4^J E^l+ 4ol rH 8A.60l+.
Er=-hcLr=-(6.626 08x10-34 ls)x(2.997 945x1010 cm s-') =ol
ala zJ+B.ll E6J ¤¤g lthc=r1e 67ecm-,olq, q+^J
x (109 677 cm-t )= -2.17 8 70x 10-'8 | ols_s+ qqzlb q-q-$ Bol ¤4.
2.178 70alolu1. ol qlq zlts -t:.se8eVel ,Jul. I=hcx(I}9 679cm-t)
=
8A +4= flrI 28e
110
l- 0 t234 5 6
+aEe.l E^l
s p d f g h i
-100
\ +Ag flz}4 4dx} flzi9l,rJ E"J+ +44E +llE.J+=
E
o \ g EF +"JtI qlHxlE *=+. ol zl-aEg /=3 ol+ql= "J
o
trIBl +^-ls ololdr(i* jzl7E9xl ?*E fl{2| glzl
l> "ll$
90
ql j= 4le-l++) :zH se.zg +ee# EB6Irll +4'J +
?lE+ rH se.s= H¤rlzl Lol4. /g O+El n-tttzlel zt
\ * zl4 f glo,_s +i^l+7| ,"J eaql= nzllg +44
80
0 0.1 0.2
1td "l glrll gtrt. dz} ee +e_l +llEEt+Eq +^dg :aB se.s
.r.g 8A.6 g^l'E 0|Ea|. ollLl^l= 76lE t1l 0lEE E7l 8A.19 EllolE'l E I
ql +4.+1fl+. .JHI4se +t^l+7} n"J ed +qlY n tll
(q7l^l= Holl r|1-d ag). E ?JE6J+7I.q 9lsq, q+^J +^g flzt9 a+ql= 4
4d"l nzfeE. trlslElq il+.
0
= (6.626 08 x I 0-34 | s)x (2.997 945 x 1 0r cm s-' ) x (1 09 67 9 cm-t )
=2.178 7xl0-t8 | l9 {lE /=goJ + 6t+e-l Fdd"l

7l+61q, "l +eA
n =
l z.tts Talol 9brll olag 1312.1kJ mol '91 6ll'J*trHE I ,n,=s19"J6}rll -"1+q. rnr9 {})"J ills.o}ffi- 6I+"J
E gE alg ++t {l se.zgl,q 414}*tr}). *=+. n-2oJ 4lE +zgq +llE'*+71- ilal q=ql, olEg
rPl g7[ 8A1 6+i fl4* rJ-q=n+ gg %1-= ]dlEH
C.=g +EI.{=Ell, ol==9 n=3,4,... 5.el +g d}49+El n
@
S d t
E+ +g* *g ^Jqe #zlb 4Eoluh ts 238,20 s7t, 4
3
ffi-ffi--ffi
23 039,24 38Ocm-'. (a) alzl t1-EI9 olg3r+ ollHxl, b) Ht 3sl 3p t3l 3d [5]
"llHzl, relr (c) 6"Jcz}q e+g +

2
El tlE]]el ol¤-E} 2s[1] 2pt3l
zlzlt- Rydberg
"Lq?+(dz}el +"JCzle+9 +4I e%Lg
K
5
tr-¤ '+4U +g +"J¤zI9 e"Jql +6]|^l +4). 6
'ht"EP &--Uia EEh lbog 6r"otxe'z (r)

'r-loru I>1y'ZI¤1 (g) 'r-lou ft t'eZe (e) ..4
ts [1]
ral 8A.7 +Atr4 ?+ +AA +oll +191= TllE-Er+E f(Ba +sl +)71
(d) drt,4trEt +,4tr E^lE +a= ErlE oilLl^l -d aE +oll tr= flEEf+=o|
=+1. =q?l=
,9 il"] +llE6J+E=-q- flx}9 + Atrg olE+I "J Eg:er ollLJ^l= ?*=tr[.
=."J+
gzlE
qL+. +^ a+ql= 5"J eeql +61+, 4 ,9 {}ol
E"J-J E= +llEet+zt Eg+ 9lHzlE 4=+. "l AeEg Hr47,l
--r- EJ
=
+¤-4 ?ol z}qlq-e. EzlE +4U+. s p d
n- I 2 3 4. MAE, n=3
EÎ ZtrgI EÎ
KLMN +lE Et+
qle^l n_2oJ 444 +llEEr-+E=g E+ r flzl9 L449_ LZH, n=2
BC6J+.
-
Rru
+E n9 atg *zl"J /9 zl"l +E +JE.++=g a 44E Nn

K
K Ae, r1= 1
+aEg olE+r ge}+ +ee5e "JHI4eE trl-.q=r+ e RJ
g +zte ++u+ fg - ZE(noe E/.lEl=)E Elts flE-tst+

8A.8 +ZJEUE r,\lEl=)ri
(g L1lg) +d.
290 8 zlrl.+4gl^FEaJ
s +Ae(/=0)ql Eqfl= ur=0oJ +llEe++ 6l+e+ /=l?l z

z
+44 +ql Eq?IE.,=6, 9l +lel ^ll ?llEEl+Eoltr|.

n-3! 4l= sz11s-1 +llEEI+(l=ooJ a 6l+ /=loJ 4, C, :
4-r. /=zoJ 4.4]i-lzl glrll 84.
x Y
(e) s fllEB# x Y
HlEltI4.llî= r= loJ +ll:ae+z} d+g+(E|4^J /=0,

(a) 1s
mr=0o14. n=r"J oll zl-L" t olzl4;- ol <,Ls=+-ol+). s. 8A.1
(b) 2s
4 Yo,o= Ol4n)tt2(E 7F.l)tr+El ol flJsaJ+{Z=r)* r+q-4 e oJ++ LtElL.!)= 7l^la- LlElL.! (a) 1s "!
feJ 8A.10 dxl "JE(Egr-e,l (b)
ol ¤+ 9l+. 2s #48 fl^l'fllE-'J+ E,^l.
1 _,-
(8A.16)
V=
1fiyr-''^ z
"l v+rE"¤.+= 4Eql ++6IE_tr "JA+ elzlE^J9 E= d

ql^J eg 4I9= ?*y+. + ls fllr.6-;.;= '+¤ ql{'olQ(n= I
"J s +]lE.E+, "l "JHI4o-tr zs). ol Tlsg-a= qE f il

al.lla Lt(rd)Uz+=- LI4Lllr zl+-EL+498 e^l
(r=0)oll.rl
+ ol tr-E+lel 4^Y7l E|aB q¤e q zfillel +lzlqi^j
x
,,,.',s\
+tr}.
TIaF ++.
Y Y
gzlE trlQl¤ "lluJzl$ Bd qlqzle+el dzll gluJzlql 4 fg 8A.1t Cxlzl gZE qEol eu/ooJ BE= s flls-*#9 ?3419.
=ejul=
6J 7lq= _H-E olel6.J Htqtr-ql gHI4 E -?E s +lE:Bt+= +E eZlE='J=tr|.
^J4o1l
9 "lall$ + flg 4,"14. 4zlzl ¤fli4 " + qql ,lr|+14+
+ r ¤+ slHl¤ qlqzl= *old+(q ¤+). olqq} E r]l*6fl^l dzt9 ¤+ i{Q]¤ qlqzlz| $olot B 4"14. ¤xll
=
*Al7l LIei+EJB slHf¤ glHzlzl- 4lzls q= qE +lzl el ElEltlE|] :il-E.et/-r- ol= + +qlol ¤+g A++. +
= "l
oll.r.l u1-=" a'u-71 tl+g 7*a a ole.lE E= *ql^J= 0ol qoe+El qL aEvlTl+ q4+rlq(rzl6lq
= 8A.e). r*l+ olBl*
9"lot E 4"14(rH -ELoJol qeJE yI i4ql¤ 9lHzl5 Aall a+ql^Je+ 2tol *zl ?+a r. qlB6l
E"E}fzI 4+61 +e ¤+ +Eg tl{oY 6}t:E Htl glHzl +zlE ?++) 4'J6l *e ¤+ +Eg *=+(trI4^J eE ql
zl q o ++q H ,l4rlzl qal+e 4,"14 ololl Hzl9 zlr\zlz14+61 *zlE ?+r E ar}l a+ql^JzlH +
zlE g*+).
dz}9 q¤ I,JE_= ++u]]= qI "JBg rHE E"JS zlzl
trlEltr oilLl^l= '*r t lwl'g +44= aol+(rH 8A.10). q A+* %rB3 ol
3Eo1lL1^l=
=E.l q¤: ,JEq 4+E("JHI4 0 + "j qovo)g fs" 6l-b e7flEg
<i 4l^'lsl Eill oilLixl ++LH. 4014. rs TllE*fE a+ql= t AalHe eg +
,lolJ
UO
de + 6l+ +trI(rH 8A.11).
ri
eEqlLlxl='*r
b
trlEJl¤ ojlLl^l= tsrl.
EEEU +ttEs+st Bauxeaht
+AE: rs ?.IE6Jfq ¤+ tlzlEg 4l&6}q+.
BJIIE, T
r.alg lg ol ¤f elzlE-g +g-+ zt! zlcllzl"l4.
:19 8A.e +4E fl^l-g Hl.JgE|l +6= EE ollLl^lel trlEJI¤ oilLl^lel
EB= 7l^la- ¤EEr + 9ltrl'. (a) EP +4tr18 ?{lE-Br+= Ee EA at =Jrfyl' dt
8E oilLl^lel'*e BE qEJ!¤ oilLl^l==EE ii-E EE ollLl^l='J^lu
Q)= ty.ry
'J=tr|-. (b)
trlEJltr ollLl^l7l 0t|+ 4tr61'^l ".Jtl". (c) 4=J-d EE ollLl^lel 4-c':d tr1EJ!¤
tr|+^J e. se.t9 EIE6J+9} d:t=f drsin0 dediltrq TF
oilLJ^l7f tr=E
=rEl'.
8A +a= flrl 2e1
9 44zlE t4 2l)E olf-all.<l ol 4ts¤- +6llot oJ+.

ol ul-e"oJfel 4E-E= +E(_tr 7F.1)g r-Lq=$ *ol Cf
P
Elqq 9lq !
>
*
>
sin o do d'q =1
!,=Ji,l', ^l' *1,,
,loll
++ zl$e x|tr ¤oll +el gl+.

,"ll
Eol V=RY* ?9 Ee i!ts Bt tlzlE"ll

+6 4gol Q*o=g *ol ¤c(a4_q_E qq{ 4s. Hf EJIIE, T
ql AA 4Ee loltrl). rzJ 8A.12 gE-+trl C^[-AB =Jd(lt= gBFi{l)e -49 +l^lollî Eltl,|'JE
7l=61.r, r olelE *oll,(]ts Etrl- 4t3 ,JE 7lE-g aol+. Eg urlEsl
fl8oll^1= +'Jg'J- LIEIH aolq. s tlE-dfts +EHeolq'.
(r) =
[ J, fi. ,4.,1y, .-,1' 12 d.r sinl ae aq - l* ,' 4,,d,
R,,ots r+g_+
lwl'?- 4E "Js(qHld' l/+tr])olq, {zlql+ +d 'Itr-+
ls ?llE6Jfg a+.
rl= +6H+H q¤(+-4Hl{lol g+. zl+ dzl-= *zl$ f
*,"=r(*)''' ,-"'^ ?lr +rl7| dtoJ Heg +ig gzlE q olE.
^l
=aql^l
a +tr+r ^J4dlEz|. +iE flxl.9 Hl-EI^JEIql^lE q¤
"JE= gzzrtaoll ul{la}Ee ol E}ag qL + HJF^} HJts6}9-E
Ir}4^J
4= E.3
ol$^]4 4214. zl+-E|+4 o + eA6l= <l"l 444zl"J
4zt -i 4zt . 3!
(r)= -{ ), r'e "'
3 _2zrta^
"o t
d,r= xozcT=rt
3ao
o "JC tlzlEE +HtF.tl^J= ol Eleol "Ja6J <tg +48 a

ol+(rH 8A.12).
I;l7lg.7t 8A2 3s fllEflfE ¤+ tlzl# z]d zlB6il
q+ql= qlzlEol rola +4t.71 droJ A4ft 4A) +ql^J
^l +6Iq+. dzl¤ gaB e¤¤ {4}6}l Bz}. ol a+ql= ReE A+
zzfotz:E
+q. +r+e1+rl"J 4rfd4o14g + E.E Hol 4ntqlr+ r
+41 d¤ -',6J 4,rI e+)4 eAl 6l]0} ++(rB 8A.13). f,rzl
EE s +llEJ+59 +-qla"lzl"J "JÎB "|qel izl 4 6I= +q= q o ++q Hqa++ ¤=zla}q fleJ flil r=0
e+. qls^J ls,2s, r4r 3s ?llE*fEe zlzJ 0, t, tqtz ql^l= 0ol B+= 4g ++6|q4. +4E "J+ sH$ EI
"l
zll9 ut4# *=tr}. "JHI49-e. rzs TllEEtfE n-lzflel u| A sH ^plql^l 4zlzl gag +=e *xl$ rql^JE +E
q= *=+.+qd +gq ++g Ed6l-= +B a4lEE HI "JEql+ ReE +4= #e A, 4 ly4rllzx4nr2dr4 *oloh
zl# 4ol f;zlgroll tr++ 6zlaJ4. ++. ol 4¤. rl-q_r+ ?"1 cgg= ptrlg ol-a"alol p(r)dre
0.6
zs +llE,*f +6J q++ glz}(s 8A.1)7I 0ol q

Laguerre aa
\
*ql^J lrtqE 4=tr1. ol a+ql= ol of,zlzl a+6}rll S
q o.o
=p-zolq, q4^J p_21ltl
+(rB 8A.4).
"I4zI +4++. zs Tlls*fg
a+q= p=Z-rtaoolq q?+^J Etq= r-2adZql^l +4ts
<F
fio
BI
n|l 0.2
;iuo
I
{
ry
io
0
0 2 3 4
alxlf.Zr/ao
(f) rJ lE Es -Et+
fal 8A.19 'Jll.E Es -Er+ p(r)= BJ^l= fl +?f +oll^l Erl.= "Ja-g
I vl'q Atg E61l^J "Jelel +zI zlAql^l dzl¤
+E¤ L|.ElLJtt. 519 xlillE d¤ +r-+E +tr|tr|.. +4E 1s E^[9
P(r)drolE,
0l P(r)E r0l Bohr EJÎE aoal'Je= q alqTl Ecl. P(r)9 'J? +?1
BaB g¤¤ "J:"]] olul Eq TBql^] ¤H¤I ul-s+ trol '2J+
E.gq =JAol r HJÎ=E Est^l7lEî 9]= il4 eq.
=+.
292 I flrt+=gtl+arEaJ
++r+. EEEU atEnEl=ElrtEE4lrr

P(r)-4nr'zlry(r) l' (8A.17a) flzI HAzl Zof, +AE gzl-E ls fllra5 dzlq ..il+ 4l
]il=*,Efiifl q += H}zlE r_¤ +6Ir" He+El Nee*oll ol=.E ldz}
Eif prrlg g^l¤l EE -d++r el+(olag s lllEalfqluj +¤"ll 4t
<l# s+ trJEqer.
ol
4e" gtrD. T 4?"1 ol-H fllE*+qlE zl+!ts e_+ "JHlzl
r.E{g ,t.tB dPldr=O9 gH +iE ts TllE*fE "}^}
9l 6-J+E +Eg + gltrl.
¤ Ee Elfz} +q <tg'f44= qlzl# +E+ + 9l+.
?tr g/.tfl
*4 atol ¤4 z1| Ll-g ql= alEil d+ql ql-$6}i ag q
^lel
8A1 Et+ol gHJE Eg +r+.
=E
grfzl rlr=Ry"J dzl-$ +rl g+ dt49l^J tsAg +=
ul^=."
q4^l
g lRyl2dtol-,L +4 -s-Ab dr-fdr singd0 dLa +q{+. Eol "J^lB +E E++E 8A.18^ln+ A+.
ol *$-g tlzl$ rg * Etsq a!^J 4+6lE "JcaJ *zl dP qz'( 2r__
2Zr2
+(, -
I
^ = ^
Or- ( *),-,,,,
EE 'JEE 4E tr-ql^J dxl¤ gAts dill q¤ P(r)drol +
o'o Ao
),u,,,
e+. + "lag gs "Jq o}"l oB q1 ool gr+. qu}^l r=O"J trllE

zllEat{ q+r+ *"1 ¤4.
P(r)dr =J"
J'^
*(r)' y,.,,,,)t rz d,r sinl de dQ
ao
7H aq 6J+= ls C+3rlqq il-o l,-tr(-H-zl 8A.2ql^le+ r*,
Z
u."1 d4"+ 44U 4E+ 1ol+) 4+4_oE r-l.s_4 eg rr++^l ao=52.epmE 0l+6ll^l al{}6}E slEll ffi qlzl$
e1+7149tri. E"l rls=4 &ol ¤4.
uu
Htrl.:ol 6I-^.
P(r) = r'R(r)' o,.t o [+
rorutxl Eohl
EI
(8A.17b) H He+ Li2* Be3-- B4I C* Ns 07* F8+ Ne*
L=t- rcjl
r^plpm 52.9 26.5 17.6 13.2 10.6 8.82 7.56 6.61 5.88 5.29
p(dg %r-^tB Es EI+4r 6l^= "J+q +E-r,JEolq, ol +^1 qE d6}zl rtzliloll "l+ rs fllEBfE q +s
E'-+ql+ d¤ #'tI 4Z A4zl roJ *ql fl= *41 arq azl
E EEja+E ag "J + 9l+. +"+Eql oleB "l 4ql
"*4 zlq Îolql^J dzl¤ EAg g¤g ++U+. rs T.IE* ffi $zl-eol 0.58p- BI9l ?I q=ql, olag +i gz}
+e-l A+"llE ol4o1 ffi$ *ol ¤4. E a+ql Hl6ll^J "J utoo CE.ql Er+6I+.(qlaEil Hql^J
r-r=l0cm4B uql^J= r-p=lmmzl. E 4".l4.) r4+
ol pffi Ell+61 +|e flzL.ll zl+^la ql=
P(r) -4r'r-"''^
a[
(8A.18)
^JqC tr
r+= aq4 +qo} 6Iq 4Î"l +t6ll4ltrI.
ol !g r-fq=4 trol afl4ts + 9ltrI TlTlg^Tl8A3 +d= flzlollrl zs dxl-e| q al
Î"lE
ril $E 4"-lE +6Iq+.
qql^J= r2-0olE + P(0)=0oJ+. r=0oJ +r+E
htoE i{eSG EE *ht}r?& 1z{zB tatr tbElz
Pulzt oolq, r}{^J ol +4 "Jqlî dzl-$ Bd 9 {ztzhtt" to{zB -o{2 [o Zfryz's=zfo1r,,s+e) .E
g +=e 001+.
r+".ol$ zl+ oJ trIEql p?)+ool g+. 4_oe.
+El oI+ g?] trq4! *ql^J= ffishz[ soe #
(g) p ?llE-d+
E"lzlq, +?+4 +q= zzl"J r "Jq^J d4¤ # 37llE 2p ?llEdJfE=3 -E+/=tolq, tt}4î 4¤+=J a7171
Bag +=e 00t+. ffi E+ e+. "l=.c mrll* zlzl:t_ +E+ + fl=ql, ol ztE=g
,r4 *zl* zl+ eAE oJzlE ?1611^lPY +7J "Jelel + +(F^J49E ,+) ^Jel ^dEg +4U+ qla4
4qql^J +Eildg 44U'HzB se.rr). + ol + m-loJ +llEEL++ z+ +qE 4&Eelol ool4. o)aE ?+
qldql^J= dzl¤ ga.J + 9l= el-E:ol %F6Jql Eql q= Hsl+ +H sslEl+ Y,rB +49 f glEcll, ol4,
5-ga[{] ,}t} ttr}. 3 cosgoll ulrllaJc|(* 7F.tg -H_ol-eD. q+^J r q¤ "JE=
8A +4= flrl 2e3
cos2ooll Hlell6}r. zG(,0=04 lso.ql^J cos20-1)ql tr}4 qE qdql 6ll'J6}q, sidE H}^lal ,J6J Eldql 6ll'J+4. ol gL+
"J+ql^l +'1]il= +4U+. +xll4 otr. m-\oJ 2p TJlEtJf E3 e=04 r}0.(z+ ^Jql^l :z +l*ol 0ol qa 0=90",1xy
el +8.6J+= r+g=+ rJr+. Hql^l r Tl+ol 4qg 84. "l 'J+Eg 9q}4_oe. C#vle
+4U4 olEl+ 94 " + r+q-r+ ag dB aEtg +l++.
=R,,, (r)y,,, @,il r cos g r- Zr t2ao
v z,r,o =
#(*)" (8A.19a)
eio+e-io=2cos0
=r cos9 f (r) V ro, = r,r,.,-V r,r,-r)=rsln ?cosQf(r)-x f(r)

fr{w
(8A.21)
¤zlrJ fOZ r"J9 ori"l4.+E +alEql^l= z=rcosfl(E
eio_e-io- 2i sin 0
i
I zp9 44219 dlal zt;ol=e ol u|:a"gl+= r;s=4 ?"1 Vrr,= ,*(Vr.r..' *Ur.'.-, ) -r sinOsin@/(r)= y f (r)
+ +E 9l+. oldB e.JEg _E_+ z+C-9 ¤a 4gF=J ^d$g ,*^l ?*
yrr.r.o=zf (r) (8A.19b)
A+rlolq, tr1lq= +"J z*4 *F ol+qd 4Eol4.p,
=
mr=}oJ p +]lsE}fE$ q+ olelq} Ee-l 7*^ltrJ 7llrfl$L p, TtlEE}fe| EoJg tzl"J x4 ^}.ll ?1e4, p,
f(r)? n9 #91 el=¤r+.ol +llEEI+9 "l4t+21 *^l ql E rrl-+7|zll yl tr-ql 9i+(re sA.l4). + ed9 p +llEEL
Eql p, +llEaJ4rqE H4"l +4qfr.4. ol TllE6J+9 AAI += qL 4"14 x, y, Ey ze+ "J^l-¤ otf lrgl 9=6I=)e+
Eg rH 8A.14ql +El']lfi.4. ol z-loJ ryHt9 E teE ++g + 91tr]-.
EE dq^l 0ol qq, E|+^l ol rTHg ol fllE.aJfE EItrl E
ol g+. ol ul-="grf7l ol HE ++e--E+q tr|= +_q_E H (n) o ?{E-d+
qA oll= a 7 ozl H++. {i q 2ol+. r?]flq
rz=3oJ l=0, l, "1 4¤9 rz11E es Tll
ffit=trQl 2p+llEEL+.9 q-="9-* q+r+ eg EEr-+, 37HE 3p ?JlE6Ji ralr sTl]E 3d +llE6J+r==E ol
=-oltrl.
+q4l+. oJzI+ ffit=+2, +r,0, -1, -2el zl$g ,+?+ z1 +
V z.r*t= Rr, (r)Y,,", (0,il= *#( *)t' r sin0et'o ,-Zrt2% 919 t"lal 4+F* CEg +4U+. p +tls*fql^Je+ a
^JHlq= d +llEEL+E(trI+,\l z+ ++lel
(8A.20) o1 mr AIE +s7l-
1
=T
rtnr
sin0e*'o/(r) g5ol +ql ',J-Jol ¤+;$ + tI 4 Ao.JotE 4+471 N7l
Eql, ol.9 A4E sEg:7H 8A.lsql +4,119.4. ol d¤
Eq TDql^l ¤E+ uls+ e."1 ¤rE" 6I= "J"J"]E +A.J+"J
rl'tr.o ¤-+tr 71+g + 9l+. 919 u1=-" g-*==* Hq+ zq ++l
A.J=g +*r+ ee gel dEFzI EJq, .J+/(r)$ roll 9
E 4+E+g *=+. 4 e*',4bEJe-E+q Rg ql HJ6J
^l4l
=++.
Q=
=Q
*
d" d,L/
p, Zt p, p
0l
&'
lal qqE EJ16l.q, 4 +lE-Br'+sl
8A.14 2p tls-d*EE 3XlE. Eltrl Ee d xy d yz d zx
+ +'EE'Jat--Etl. "Jg Eq+ q- gEP trl-E-Bt+sl Pazl
"Ega= q0l:dtl. +E +:slE AIE 4EEE LfEfLtlfltl. p +Jls-d#-=3
E6l'= ral 8A.1s 3d +llE-Bt+E ?AAl1. Tl-d Bq+ 6fl Bqe q'=:Br+sl HJLH
tr+ q7l E?.! a4 'J= ?3Al sEE ?t=tr|-. +E Bq= LEIL.!E|. d ?1lE-Bt+=e trF olel ,J? ?d/l sEE +=tl.
29t+ 8 tU174"t4+EE
va,= xlf (r) va,= lzf (r) va^= zxf (r) "+ 44t4. az +llE++= xlle-ld}E 4I d¤ a6J:==g +
(8A.22) 4s utulE zlzlt_ 44lE +Bg Eo&3 olE+. + +llEEL+
vo,,-,, = i(x' - y') f(r),tro", -*(lz' -r') f1r1 b + u}qzl-qla4^J e+gE zI9 zzl¤ ++r+ gg
Eo&$ +e}+rll 6JtI.
=
ol= dE Aqlg +E6l7l +l6llî d +llEEI+# do do E
=e-d7HE=
tr1. +AE- flz}"ll 4t scrfodinger
^]g
4E E= 44 %r-^]B 47. ,9 <tol E"J+ +llEEt+Eg flrt Atrg ol+q, o\ 44
al9 E-e EEI¤tr}. 49 I {tol E"JEJ 7llE6J+=g +EEg olEE}.
42. 4 zlzlol"il^l= %1-ÎB ul^=."oJfz| r,"ll Hlqlql4. qo e+ tr8. +^g flx}"ll{E E.J AaE +llE6J+Eol E+ E"J-J ql
q E?-l EqzlB E= +ig ffialfz| zl+6J+4s e 0 HzlE *=trI. -g.= ¤4E flzlqlrJ qL Aeql +dl+ E"J
ql d=.J4. el +Aag +llE6.J+r==g E+ gEl¤trI.
tr3. flrl ilE:d+= aJ flzl .Jq] EqilE oJ dzt"ll 4fl tdzl tr9. s ilE:Er+E- +¤ 44olq qql^lE $E "Jgzl ool oI44.
4EgI++. trr0. g^lEl EE:d+= dz} EE= qe-s+qE 4?-lE EL+E
44. +lz} +llEE-+= gflff n, t, A rz5e. ErlflQ. +ElU g¤-IrJE+.
trs. +Eg +rg gÎel olluJzlE -ztn241Hl4*+. trlr. + +eA +ql= :zH9 p fllE6t+7I- 9leq, olE=g zJz] |
tr6. flAE oltEt ollLlrl= Htqr-tlqlql ilE : ga oJ flzl-s 7]]E 4E Elq= *=trI.
Pq dz}6i+= 41461-= rll {9-e} 4r "llHzl4. atz. + +44 +ql= sT}lq d +lEatfz} ilsq, olEg zJzJ 2
zll! zJE "tq$ *=trI.
=sEt^l=
ai=
,\l z-lJ al Ha
ÎZI --1 I --'l
+^' ?lz}9 ^tr1=H9 ++ i=fr.n\tnl -rtn1) R"= +A flz}9l 4lt Rvdbere 8A.1
tI+=(++E +ElU)
Hlzl*
sohr ao= futoht lm,ez ao= 529 Pm 8A.9
+ig flz}9 V nt = R, r(r)Y -,(0,Q)

Yr,,,9 *H aq r;'; 8A.12
^,(r,0,E1
1
+Ê flx}9 qlLJzl E,=-hcZ' fr* I n', i^- =pea t 8elch' ft*=R*, Rydberg t}f; 8A.13
p = m"my1l(mr+ m*)
,JÎ¤ eE EL+ P(r)= r'R(r)' s ?llEtJf{l qtll^l pe)-_4nr2y, 8A.17b
E4 8B trlErl flrl
> ol EEE Hfl+ts ol8

re
trlgffiE +6 ¤Eolq, ol=el trtqr
trlExl flrl.= EE
dq6[= sEfE] -E= d¤ 0l6tl6Pl 9l6tlî= ol=E=:doll
drf 4lel qqzlql q+ hamilton ¤tlzlzl q-q=4 2-o1 {z} 14
=JE
?zEEi golot ettt gEJ olLlaf 0l ?Ioll SEt dtr= 0lE6tq
3z| zgl E+ + zlqE ql, + ft=f,,+f,,trol+qd+r. ^J
+TlEEel olzige sEsl= _EE LflEE ¤E-g+ ?lrl..
4ra|l Hz|. d^ll flzH¤E flz}q ee)E a+ql= + d4¤
> Eqd 7tlE ql$6l-= a"t.lr/r,r9l Hlql6}=, r,rE F dzt
Î"lE ^Js4l+ql
dxl== pautig HllEI flal= Hgl ?.toil^1 ax1 oilq^|g
^l-"lE 441"1
E glqot *+. 6IzlEI q7l^J= olag +^l
fllEEr+- it^Fdrl. =+^l7l=
El+
> EJe.il qHl rl4l H
H2
0l EEoll^1= +AE SxlE 74.(EE 8A), a 4e 74'=

dE6PI 9lEl ol=oll ETiErtl.
=61 ff__h' nr_ 2r' _h' nr_ ze2 - ,'
Lt-
2mr't fieor, zm"'2 4fitorr'4fi¤,r,
+tlE++ 6Jg +^lq}+. rqH olzll

=^lBql^-l= "tzlEl
+flrl flrl= olltE d4¤ zlxla- gl= gz}4. 4dx}
22fl +El 6J "Jg "J"J Vlr,)* qlLlzlT} E,"J H,E Lfrg}foll.
flzlql 4q! schrodinger 43 lt= dzl¤ Îolel tl-s4l¤¤ E v(r)E "llHzlzl EzoJ frz4:/+EL+48 v1r,, rz)=vlr)
reJoll +qot 617l trll$ql q+61 +d-6I+. ol+lq} {ts4l+ v(r)* 5B hamilton fl{!z} He-l r+.J+7} ¤+= 49 -u-
E 6-J 6,q6J er+E 4dzl. flxtg a+ql nol 7gA+E_ /<l olE a"l+.rq6lq q-q=r+ ?.ol a]t4.
ol {rolafH :. +llEE}+Eol qEiqzl g|=+= 4ol4.S"J
olq+ * zz11E dzl-= zlzl:ilfl= gE9 A+q azlE +ll HVlrr,rr) = (4, +u.1ry(rr)ry(rr)
EEt+e+ oilulzloil +6J 6l]4 gg fzl- S.eq y(r.)H,y(r ) VU.)Hly(rt)
,!Azl *eE g+. ^lg =ÎHg ?______-^_

= H,V (r,)rtr
.;________--^-
(rr) + H rry (r,)V Qr)
"J
Er !r(rr ) Ery(rr)
-;+ '^ "-
8B.1 +llEE'+=AtE = V (rr) H,V ?r) + rlr (rr) H ,Vr (rr)
= V(rr) Ery4rr) + yt\rr) Ery4rr)

4dz| flz}9 E= dzl-=el als_E E E}l+61 +
= (E,* Er)V4rr)U4rr)
alfl EL+o]4, v(r1, f2, .. .) -e. rt44"t ts 4."14. 4z)\ ,' = Ey(rr,rr)
qsE+q dz} ivl^\el ElElol+(+dz} rH.6J+= oJ
=
HI4 o + qEzI ys +q{trI). rfl+ +{Ept+
¤zlrJ E=Et+Erol+. ol Ar+= 9zl,ti +E6IEI'J 4"14.
=^}Eql^J ?+r+9 hamilton ¤tlxlzl zl-4lel l"J ¤4I¤+= a
L rzl 3.rle.! zJ $zlzl zI4lE ?JlraJ+5- ilzl6J+r ^J g +rz_6lq+ "J"J dzl¤ol tlE4I¤¤ 6}E(¤allql^lcl e
46la g"JaL uls" g--:- ql{q q+4 eg ++.
=^l¤ ol) UrI,6Jol 4q ol +Bol *zl g:rll EtrI. q+^l
=q7l"F
Y(r r,r r,...; = t(r,) U4r r) .. ?llE-t+ (88.1) ol EzlE Er+6J 4olzlrl gzl9 slE4 deg E6I
=/.l =^Lql
E rll= +3 Egolq, E* gzt +a= Er+ ar6Lal +F+
+llEEI+=g +4g. gzt +JE6J+e+ *Ela ^J46I
zllzlJ9
slzlE ++
4zl flf,
+"J e d6l"d=g ol flzI +q qe dxFS trIEql +c =gdol
=ql,
g 6H^l alot d4. dzl-dxl-tlE4i¤¤ +^l6IH ol
f*ol ¤4.
=Î. +llEJ+ ol-4"a[fl flz]9 dzt iaE r A+B
=ÎHg
+IIEEI+(EE E}qL^JE}|= ol$alzluJ rflzl ?*olE +o}6t
296 8 flIt+4q^r#.aJ
4
+)= +$L}]= dxl HflilE- Tlz.la_ +48 + 1l+. $]E,tl rs
+llEEL+ql dz| aI4zI 5q9l= +i¤- flzl9 H}qL^JEI d
z| ullzl| lsr(bne-ess-one'o E 9l=+)g ++U+
gE gzl-= 27llE dzl¤ zlzlt- fl+ Ar{l d4^b ls fc
g +llEEL+= z.lzl6tzlt:J Z=2olg e +4 gzlql^l B+ q
ql E-i zlttsl B=EJ 9l+ E ll dzl-b ls +llEgr-+ql
M (b)
6J+qq, r?]6}q Heg Hlgtrll {zf=qz}

ullzl -]
^l a.al dzls+
ts ts'21 94. (a)
(c)
zttrJEt q 88.1 fg 88.1 (a) Stern-Gerlach9 !--J at^lE rHe xl718= U=

trl'. (b)rE4o+ ql8E'Jll', (c)= flÊl= g^t*=-gEl
ttflE SAE,,Jat
+llE6J+ E6tE ue9 zi dzl^b Eq 8Aql^J +
=ÎHql
4U ++9 +Ê rs 7lls.r;3=5 d+ql+. dzl¤* dxll
qd6} zeE4Y +-tr qAal z"pA g6&9 ts=+r 6J zlTltlg Er+ELql r|4 ol fl{¤$ e]+el zlzllt$ flz|
^84
B + ileq(+ill4 o-=. *"ll Eol4,zl"J Z=24 4 zrzy z}44el ^Jrll4 tsH.Jql tr}?+ ¤6J99"F B aolq.
olqr rcee4) nt4^l ol flzl9 244 a{{g=e.E dzt 4SF"*, tr}+^J ol"ll "J"l"Jg z}49
'l+r+
A"l I 4."14. gelel Hll6}.3 ol+a flg 4o14. r4a 4 flzl¤9 uHa}9l
Y,,r(r.') ryrr(rr) tr|4 +C6J zJEtr E-Jg 4o14, Sxl-99 zlzl** uul4+
o3l2
L"q
oll2
L"tr
g trI Hg trl -Eroje e ¤4!g{"h.J 1,"14. rflql oleli
r!! / -- .. \ -7,.-rla^ - . --Zar,lr,\
4a4_"s "Jz|.qq}4 o_tr= 43t.u*, Er4^-l ¤xt ziqg
23"fr B¤+4oJ H}l6&rJs ol+qoh -J+(EE 7F). -felr. olE ull
-- noi"^-zn1rr*rr)too HJ-6Jse ¤olqq, q4^J fl4"93 flzl
'Jg zil47l +e6J
.I+e_l dzl¤9 ^J.olel 4eE=J Hl]olql 4+6ll^J 9 zl]9 9l
ol z4zl I+6ll^l= i-=E oltl-g 4oJ S,4. ol
qe A+riot 6Jtr|.
a+qlE "lag + dzl.ll 4t 4 " e+qE |49 zlf "Jql
g"l+. Stern4 GerlachE: a4H dE"llîE rd4 q+ Ar+= +
E++g
oJa11;;. 4 rJ? Ar+= Efl+. rel+ fl2|9 49 4 flzI
5ol .<JE +E-6I7l qlEql ulzl P{I4^J deol q4fl,4. "l
Eg *g rllzl9 flz|$$ zlzl:t- deg !E"l + eq{E
8B..2 Fbuli H]|EI flal zlzl +$$ ea^le +4 o +) E¤+4 q= tsa6}9eq
rp-l6}q "JztEqI4 ql+ er+E +"J6I9+. :zflcll Stern4
gq
^J46lE flzl- Hozl Z=3,4, ...,E 4l+!=(+ ZTllE 4
zl-= *E) fl159 flzl.9 {z} ullrl} 1sz7} p 4"14:z ^J
GerlachE 2714 eg Szl
"lz\ 44U+= ag Ea*+. "JzI
Eq E6LE 4e+4=ol 4lE zl+ITHE ullolol zlft'al-EE
/oJ
zJolzl d4. :44 "l+z] 9xlE ?*=+ r
olf+ 4zlzl olBloJ 44zl +seJH /=+ol qolo} 6l+tr11, olag /ol e+
'^g'g zlzlt- 91+= a4, EqI Eil+61 TltzloJ'pauli9 fl ?+"t ++= "J4qql4 aEr+ E+q= AilH _H_t+. ol E
?-l'= trlr+ot 6J+= + 7l^1ol+ trll$oltrl.
+¤ 6ilA4zl 96Iq e flz}9 ol 4+F=Jol CzlE 4 +
9l Eldql 7l"Jq= +llE 4¤.E=Jol o},l4 dz}9 zlc +E
(a) ql 7l"Jq= 4+E=*"J 4."14E q9.4. dz|9
Ê ^J4g 6|41
dzl-Ê3 "J^lEql4 ¤AE^J 4zlzl4= Ee4 ¤4"1 ol Ea4"J 4+ElB¤.r-g,ol4tr ++.
4, tqztH"ll otto Stern4 waltherGerlach9 de9+ E+ed zl-tlE + +91- zld6l+ dzl9 6J +dd +91=
4o14. olE=3 $f"J+ zlzl** F6]]^J g tlzl-tlg BÎfl, qdd+ ^fle
4+^l?,'J 44 qee441 44¤. "J+
"J"J"]"il
4(l.H 88.1). "l ¤e¤- 6}rll g EzlE fl4¤g ,+r+ !4 ^lv1^l
g*¤. Lolq, El4^J r-s 4+E%Iq ql+
"Jzl-+E ^J
aJ dzl4 4gfffizlzl{(+E"{+ d6}.} ztzl^}$ q}E ol6J ++9 zll*9 El"r"t e- aol+. ol 4eF%hq +ll
a 4+ 4L+F=* Eqel HJ6Je--tr. CEg 4tg "+
7l ql$ql) ^ssE(/4 ul.$zlxl
E 4+t.%F4 +E6l-71 g-l6ll,rJ atrJ gill+
4 zI44 Bol BE"E 4o14ts ^J4olH4.flzl¤ol $7g e "JE {lol4), r4-7 z+ ^JEql ql.J 4E rpl zFr+.
8B El.d^lgrl 2e7
m,s +E+urI. 4+F*E a71Y {s(s+ 1)}'/27olQ, r z

ol 4gF"*ol I
g.ttxl0-3sl sol4.
^fl
+ CE m,hY ms= s, s- l, . . ., -s9] 2s+ 12fl9] zl4 + 9l
611^l= (i),2ft =0.866h,
'"I"J z+ *4 CEg m,ho14, "J"Jol"tl ql6ll^J= ++fr,
4. Stern4 Gerlach9 ¤e Ar+= ¤HE + ?lsalH s=*4 ft +5.27x10-3sl sol4.
^fl-+
m,= !*ole}"t +tr}.
EE ¤E 841 "Jz}-+ ,n,trildql sE $;r, 5= +joJe}l" lf

ag tq g + 9l+. olag *zl ?*e4, tt] ul$zlzlE Hlc+E *= "J'Jol= tril=Ele.ol4r +_e 7 c+
= ^gg
(09 eg-r11^l)el *= g,Jol= E=olEp 5¤4. :z
sE ¤7 ¤-ol E + s,9.q, ^fl 4&E=J9
=zlE +EI'il ^flg
aol+. z+ ^dE+,a,E 444oI6J+. Ela}ol dz|$ "JCzl-b ull=ul$ola olzl-= E=ol+. Ea
= g +c6l+ E= ql-e.ul$olr HlEql qlqul¤-=
z}^]161 6l]4617l= El]+ +d-614, olL¤-
^Bztzl
g a6J^l7l= o.Jq +4l!= zlg ojulolzl sF _H=ol+=
"JoJol9
^gg
dzll4"J xld ¤-Fol4r EH e7 .J g+ '^fl'g d=J"l zLgE d4ol4. qle^l BzlE 6IAE "J
Îde 4+61 Ae
+ d6}e+ eg Ea4e c¤-e eopt "tB+4 dzl¤e "l "Jol# a6J^l7l= dz}7l4 .Jg dii+^]il+. El+^l Ee
L aolL} F"J+ a_7lq 4gE:*9 zlzl4,:r. =.71= Hl ol* E=ol +44= oJql el6}l^-l +491=. qls"lgEE d
R fzl S= aol+. rflq
^g zld ¤+E 7]]H o + 4= Elill"J 4"14.
^¤g
ae. ¤?-le. qlE ?l=Ell, olH trll= +E. 6]l^J ,l^lo}++. 4
eE=Jg +44= Eq E¤(Eq 7F)ql^l= + ^Jol+ (b) Fburi flal
^sol
H]Jolg ol+r1l ¤+(re 8B.2). _z aJ Eflole m,-++ql qlB6I olzll l¤ THHol qBqfl.o o+ flzl-=9 dzt +aE +^l
aolr(ol ^JqlE gal a EE 1-e e^1ql+), += 6ILI=
"lq^-1 ¤E6I4l+. b3il 4E+ 3419 Czl-$
= zlzlz 914.
rn,=_igl 6I'J6l+ 4olrilol ^JEH- p Eb I e e,,.1a3q1. i]g + dzl= ls ?Jls.o;+5 zlzl6l-=tr11, ol He 4E4 4*
dzle+ u[.$z[z]E EE iB4¤g 44 r+6J Ee4 4 q +e d6F= zlzla- ?lzl ullEql ol dzls=g qql q Bol
S 4+F"d¤ T|zlr 9l+. qlerJ "JCzI$ 6Czl^b E+ E47l rq+ il+ + dzlzlH r, +llE6}
,jlrll dzl-b
g_+
"J"JolEolq(4 s=*), E"J+ 4¤+%hg zlx):il_ EHE
^ ?14.
ol13 dzt uflilz| +¤.4 ?3 Rauti
+E- il-zl6l.zl ?*Erll,
e5g ++. "Jdzls+ 6td{t dzlH4 gd q 4 u]|El flelE ullgol4.
^¤ =o ^llEg $olo|-olzl
ffi zlzJH^JE E"J+ ^S 4g+"d¤ zlzltr p rd4
s ^Jz,Lts uil "lE$ dzl$4 gl$ q L4rll z}dg 6110} + 37}lold;$ 4zlzl qI +llEEL+E zlzlts += Ss tr
5il
+. -J¤ 4e a=-rz| +"J "J+ +zlz|3_ :-ul_r "J"Jol(+, 4, E + 44716J TllEe-+¤- ilzlal ull= rEq 5 oFl
s=l)oJq, "J+ gztqE olEl+ 4¤-r "J"Jol4 +"-lqlrll + lflol {t9 olFol"t ql4. E
_s6J "J"JolE BzI4. "Jz]- lflg ts+lEql^l ,-s ,d.g ol+r gl= dzlq 4gt-*e. 6J dz}9
^g_r
,il ol+¤+= q =:,q6i
q
d9 eq nAql^l ¤H6J 4,"14. ^gol
zlzl *E9l^-1 ol+g+(Eq 16A). ^fle +E dzlE E6l]^l tr"4lq7l qlEql 0ol qq, olE¤-
^gql
1l-e s.^l+tr+.2|,tllal "$lzl$ o-J dzl-b m,=*!* E 6r+
zlEEt ql 88.2
9 dzlE m,=-I& zlzlt- 7+7+4 gE tr-ql H]]6Jqq +
S"l o¤- 4484f:-B as.:). "l Hl]q ?]4= +d-6J flzl.9
^
4+E=JE zzlt trI= 4+E+=r+ u|4lzlzlE +7, Elqt4 azlc, r4il Ezl- +a ¤¤ ¤E6l+ rll zlts
^fl
{s(s+1)}'/2hol+. dx}B"J o}q+ E= r-g-+
oJ"Jolql 4
4"J qg}g ol g?]= rgz+Egl wotfg*g pautiz| Qg
++
"J+ CSol +4Llzl ?*E "l.ftE ¤B6lrl 916|]
^qlEHql
zlloJ* 1o14. l= I +ql olE4"J ol
"J46|]^J
^J =4ql
94= ql+61 gHl4?l E_e. +E6I*.+.
t
*,= -* pauli9 tsll4 gE= Fbuli flel4r- +s= +¤-r+ ag "JHI
4 ?l4E ,tt 5E6J a+ql 6ll'"qlq.
mr= +* (
/
fal 88.2 E^l E9 slEl E L flg9 +E eolts 3ttz12 clSlolZ zC 89
Fge t ] rtflcl.
298 tlrt+4gt -tn+.aJ
+zl+ 4i4l 4flo1 6l]'&EL+. 4+

\ -/ =),ol ^g(47li trl+4^J4q=)ql
mr=+* I
^-l
alE dill ?ol +lls6t+ ++4 Lll
^g tr'{ +$ qL 6}+e+el #ol B 4,o14.
:
i
:
a(2)
:
:
ln s 1
z yt\r)yt\z) a(r) \4Dtt42)9(1)B(2)

'-/
(88'4)
7
V4r)W2)o-(t,2)
yr(t)yt\2)o*(r,2)
I
Pauli fl4ql E6iH q+q= dzl¤ r+I*g ql
fB 88.3 AtT]
ElElts^rJel
E^lEol LIEILH= Ê! 4¤EaJ3 Oolcl..
qTol _EoJ flE.gg Elqg fliloil ?l1l El=r1|, -d ulElTl
0l- t *nzl BI+l= 4."1e]"F ++. +lel q] lî= E
LI'EILIi= +
BgS9 ol! Et 9lE trllts tl= -d tslE'l7l r HJEH
** Eill
xl 1r+ 2E r+e} 4* yltl ll2) ++3 v42)v^r)"1 9Erll,
"J:Bt=
olae f,,luJo1 g4eg golr .ll¤+ zJg aEol
Êloll
4FJ0l00l Etrl.
=!dE
rl. olfl dql^lE o(1)a(2)e+ p(1)p(2)E u|{z}zlQ. q+^l
ylr)ylz)a(r)a(2) r4r
v4r)v12)P(1)p(2)= Pszl- H6l-zl 9+
"JEe-l t-=".6J F ullsulgE EzlE ^JE
HI+q
e t: + -{+g + $.= 4Eol4. -trzl7} Hp ql o*(1, 2)t:4
il
+E ditj PszL H++. r4+ .Jel oP'J
*4 ?ol HEL+
E d,="* + _H-=el szl= !e uJgq +ts di-ll l
o
o_
PszI H6izl g:=r+. o*(2,1) =(i)*(2)B(r) + 0(2)a(r))= o*(1,2)
'di-ll ylÊogr+'* $"Jolel E6J6l+ dAl4"J rFE"gI

^Sg ol4g o*E +^JE Hh+q --9 491 g46t+. tr|+^J Cxll
+= el',lql+. H ql+E 6l+E + $.= 4ol4,zE s_+_ o_(r, 2)!.q¤r+ e
Pauli9 fl4zl g?]= LllE+4= 49 uz1
Pauli9 Hl]E} g-1
ol ¤+.
6.Iq 2dzl-ql ql6.J y\r,z)= pauli9 fl
^J46ll Ezl.
4ql 96IE szl 14 zzl Et+ +E qL 9i1.il 9la +4H
(r\
ol olfi$
^lE
Hl+q +ts z$i1l q^="*-9 PszI H6llot
o_(2,1) =
lt')
(r
{a(z)0(t) - F(z)a(t)}
alE 4ol xlgE +p-lol+(*'ll^d olEql Ir++^J _t_ {CI(1)B(2) - 9(t)a(z)} = -o_(1,2)
| )v2
=46J+)
"lag EE6l +s= HIE+(+ 'Hl.ll?'ol4). trl+^J
Y(2,t) --Y(r,2) (8B.2)
qI gz} +9 + .J,zlzl F"J+ +llEEL+ vr= d+++r ^J4 o3u3olz|

vlr)vlz)o-(1, 2)= I.+|E ull H oz| HI+lq rel6t
6tH, +llEEL+ ol + dzlE dill4ol u|-=.oat--'-' ¤ ol43 6l+q= uF"g+olQ.
=^LBql^J= ee|:olx|fl pauti fl491 E6H^J ql ,lJE 7l++ ^Jql +ql^J
7l v(Dv(De q"lo} 6Izl"J pauti fl4E 4s"^lTlEJE 1g
ol EElg dx11 u1-="q45 +i#aflot qI{.+d + 4¤E a+ szl 6t+"Jol -.1*¤+E ag "J4 qfl+. ol + t4E a^
EF uzl9E a(1)a(2), + E+ gr+ B^flol ,]^dlg olE aol+. olag 4E olH pauli9 Hl]4
= ^J46IH +
p7L q= ^¤ol ^¤ol
p(1)p(2), rzlr 6l-+= aoltr trl= 6I+= p7I q= fl4z} "jloI+ 4*o14. d{¤ol 1iolt fllErJf=-o x o
a(t)P(z)E= d(2)p(1)E ^J45ol zl:." afci. +"-l= o'l¤ dz1 g trli= ts|]E| +149 Ezl ?*s4, :z4atq + 4zlzl
zlts|]=
zl aolt- E qB 4zlzl poJzlE EtB f s. o = + ol rjlrll F"J+ 4g¤- 7l4E 84. t_44 "lEl.J A+qlE di.ll rl+
H tlEH= r+q_4 eg d¤ a.Jg zlzla_ 444ot ++.' 6J+= dill4_e__tr Hlr]]aole}"t 6}{ pauli gq=
"J+^l7l
zl ?teH "J g+.
o*(1,2) =(i)*(r)p(2) + p(1)d(2)) olzll 4E flzlE 9Eolzl-EzI. Li(z=3)q a+qlE rs +ll
(88.3) E6J+7I ill+14 ?lzl ullEql ,jlrll 4zlzl ol +llEs}+ql Eq
g(r)a(z)) ?J + $.4. ola$- +"]= K$A@_rql +llE6Ji Eq 8A)ol
o-(1,2) =(#)r"(r)B(2) -
SCqS.{r "5"I4 E + 4zlzl =J:d Etrg "JEfl+41
ol+Zl 6LH 6J aoltr += 6i+= 5"J +89 PzI ¤ E IrJ6JtrI. olel¤i Bql eeg ue flzl-ql r+ql 4olzl ollE
^fl$
+ *E ae ¤B 6l]Bl6l-a(42fl :-.9o1 t4lqzl t* ql olag [He]_tr s^l6Jtrl-. dlxll dzl-L Kaeql Eolztzl *
^gql 6lq r rl¤ge -{+q= n-2oJ +llEq++= zlzlaNop qlq.
r "lele} d¤ aBE¤ q6I+ rlq+ olf+ olEol dill 1g ¤4lz} s,4
s.sl r+Et+ql 6llB'6t71 trllEoltrHMs=O, 14tr 7+7J s= 14 o"J rll). + ol d4-b Leaql +4 rBl+:r_ ols"* + gl
=qrlot
88 q.trl flrl 2ee
=
+llEo-J+zl 2s +llEEL+qlzl 2p ?llE.J+?lzl= oJoloF ol
flzt9 alzl "llHxl dz} ullilz]. [He]2s'oJzl E= [He]2p'oJzl
n
E acg+ el+.
il
o-
<F
\
il
,rb0
gB.3 *= flal
*l
nl.l 3p
\
\\l I
F0
io ,"/ [
+AE flzloll,<le.li B"l +dx} flz}9l,rJE zse+ zp TJIE¤-
+E("JHI4 o + 6J 44 +9 -EE +e¤)ol E"J+ qlqzl
. ?*^1?+=+ .
0
0
rx/ 4
V 812
a)xlfl,Zr/ao
16 20
ral 8B.s s flE-*#(G7l^l= 3s flE-d#)E Exl= 'J? l?d$g p fl-=.

(a) EFel TElt -cr+E !xl-l|El -4 TPTlolollu\l "JA= q=ol 5rf(3s +llE-sl+el 718 Lt|+
4dz} flzI 4"ll^J * dxl^L 4"lzl 4E g= dzloll 9.J E+el7lr=0?.! *oll ?l= -.joll gtrfLI TlDl?Ê +E-dpla[). rq'al,(l s d^|'ts
p Exlerl Tlzlt Ezlel gEFg Eg.q q{oll trl ?J:"lAl E=alll Etl.
44214 Hlgqg E=+. t dzlzl q_oE+El r HIE Eol =
4 9tg trll= HlzlE ,4 A "Jql EqglE e= dzl¤.ll elEl
+tsqg tsal q=E1, ol Hlg.qe ol += EE Azl¤"1 q
E flilql flql zleflg *ll +44rll g Hlgqr+ ?Jr+(r- 9a Z fllEi++ Zefr
B an.+1. ol +E d-d6IE a45 "l dz}9 E= +lilql + He 2 ls t.6875
6ll^J ¤+6IE eel '+_8. d6taJ'ol Ze**el Z"o"E +iEl= C 6 1s 5.6727
trll, ol Z"F. *E E4-d6lelr ++. olag +?]= $zlzl zl 2s 3.2166
a1T.! q d6IE ¤'&g ts=q-r I]J6lq, nl z,fte+4 zl¤ oe. 2p 3.1358
+4qlr olag TraE g+4r- ++ + . zLE ¤ql El

"*g <iEol ++qq ilq
Z,ff= Z- o "iel Tlalt (8B.5)
q+) +d
dz|Eol eE A 4zl4 "JEg ¤¤zl " + Ed6l z}Ej"+zl 'l]tr-dz}9 +lil7l "JE= + "Jql il= dzl¤"J
ol zl4s sr+E- 444s_+ s dxl* p dzttr-4 7|?-lg sr}
?*=+. 7I4+ tI+= eE "Jq+ dzl¤9 Hlgq!+g 6J
= . E BE-r+ ¤44q-a eFe+ ,l?_l¤-E a" 6J4 _Ar+ql E6H
aa e4= flxI 6cq +"J d6I7I 9l+a Br +E}Ll]=
6J %FH"J ,<J s dxlE ++44 49 p dzlB4 q ++6lrll qql E=4
4o14.
s dzie+ p dzlt +e HJ^|B +EE zlzl:t- gleq flrll g+. 2e- ol^le d dzl-= rJ9-44E pdzl-.H4 E e+
^J.tr.
rzloiol eg gzt .JE += dzl¤.ll 46J **ol .<Jtr 4 all Eolz}4(d +llE¤+E 4E"e+= l9l trl-Er H6Lq, pTJlE6J
s+(re 8B.s). s dzl-b p dxlH4 4+ edg rl + eF +=,.11 qzl H6J+), :1r-l6toi q 7lfl9 o!9. g{l gtrI.
=
oJ flzl-+ql -qil= qfl ++el dz|E{l ql6J 7|r-l+
aI] Solzlq e tsa¤ ffiol E"J edg p dzlE
=ilql^J t+= Schrodinger ll9 +zlqlE+El gg u.l-='"grffi zlzJ
4 zuHp llr{riE qql^l
"tqz} 't4*4= 19 zl9a}
r Al&6J + 9l+(E 8B.l). ol gollr.l -H-= HLe+ ?ol "JeI4
_o-tr gz}Tl_44 s d4t p dzlE4 +e +E q_d6IE ¤
6&9 ts=+(ErJfl
ol= E6l= ^lz| :19 + 9lzl"J).
¤Erfzl gtrf
zlEtEt 0{l 88.3
-"-4oll ?1= trEotet

Ba fl49 1., 2s, +E qd6F= 44
"i zp Az]-E=Jql q6J
E=zf tErl. s.6727, 3.216, r?-l-I. 3.13s8o1+. ol$ fllraJ[fE o}^l-¤
Eeg4lsq ae15 (r)-fR(r)2* olao 6p +e. + 9l-,r"

,ral 88.4 q4-e.-e+El rUB Eolxl ?l= dÎts HJrl= rsl + +l?l=
gtoll
R(d= -tr 8A.1ql ++qq gl+. ,,JÎ¤
E= EÊe+q Ugel= E=r1L 0l HJgzlg 0l E^|.=el Eijl d6lts0l -._{ "J^l-B ^,ll
+liloll ?l= ttt| LIEILH4I E B¤Hlt +'Jtr|. 0l E{61' ttllEoll -4el +E E6Pf Eea55. rB 8B.6ql E^16i9trt. ol rHql^J B + gl=
ZeEflrl ZafE '2JAEtl.
300 8 flrti4q^r#.aJ
3.5 ,Jt361 "5"IzlE ol +a gel= flzI H_:rzl zof, tr4+ol q

3
I
g S4I6tr "lq^l olel +llEJ+ql+ zlrile_ ztll) dz]¤
2.5 \ illgl -J=+= Aol+. iHglzl= +^-l= +.q_J+ esq zi +lls
\, S 6J++ dxl-$ zTllvl^\trJ +¤-6J + 9t4.
Go2 0
( r.s
l-
\ 0
ls 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s
1
\
0.5
\ 2s
,i-
- 2 3 4 5 2=6014 67]lel dzl¤ zlzla- 9l= *A flzl¤ c46llE
ilao -
zl. zz\zl ls fllE¤-¤- i]|*1" Ez\lzl2s +llE*¤ ill
fal 88.6 ,.tE-d ql 8B.3oilll Zltl-d EJ^ fl^t glq E^l=ll B^l'E ill+rll ¤+. rf]
EE
_g+
EH-d
*:q r?-la +"lzl 27i71 zp *449
6Lq ce-l Hlq^JEll {z} ullzli rs22*2p22} ¤+. ol4.g a
A6IZI lHe)2s22p2tr +44zlE 6l+ull, {zl.rJ [He]9 ¤
HIe+ q qq^14 -_3) s ?llE6JfE p
A0l(561 EE rs2 4C*"14.
=il"il^l
flEq++tr+ aFE rl B:"1 6.J4.zse+ zp flleefSq ¤
E B+ 44zl TJls¤foll uloll,<l q u+. :zHollE- 2s

zp
+i gÎ9 dzl Hl]il= +++ ql 8B.4ql^l tr+ a+ q
fllEEfzI q *e glHzlE ,*Y a? B+ ,l?-lE+ e+ ¤+6ial +El-g + 9l+. 4+ t 4zlzl tolt zp TtlrdJf
4Erl q +s6I+= a¤. "J6ll f aolq. c o- il-zl*L o rrl F olxl rll r *L.A e
= 7-l O xL rrll r-l r-l- r.l =- r--l
=
EEI trqzl4l qq tlE HlEg tr 6lrll g + ?19 4"lr}. 9l
aq 6i+= 2p.Z rElr += 6t+= zpy¤ r,Izl++I ^J4
olBi6J aFe+ 7l?-l¤- 4dz} flz|qldE *d
E4 trllE9l 6J + 9l9q(q 714 x, y, ,4 Ezl=
"J9ol4, +A.J+ g.E
¤5(n9 4k? '/Ja <l"l t}olaJ)9 qlqzlTl "JHI4oe
/9 +llEEI+E + +E 9l+), tr+4^l ol flz}e] alzJ "llHzl ^JEll
s(p(d<fe+ gg +^l= ?*+_;r+ ,* +ee +E +llEEL+E- {z} uff zli lHe)2s22plzp)"1g+. 6J +44 +E tr13r} +llEg}
(/e-l {te z-zlrl mtq 4ko1+=)e E+ HJÎB $rJol :."J6I
fSol df, zl=" ¤ trll= t4l+ "l+l6J +zlol 4+g+. "|4
q d-"J6J +s q-d6l-el ¤.Jg Bzl ull$ql E+ qslElq
4f2 949 E 6l-+el +!g ++r+ ?ol tsB + 9t+.
eI+.
of xlf Li9 + glrll qfl+ n=2oJ 44
{z} ullzlg
"t+46J
dzl¤$ +q 4 +A44 4 +llEoJ+ql 6I+41 ifl+l
6J
e qolqzl ?*g 27lE +44, + 2se+ zp *4¤E qq 9l { q-gq Eal dzl¤ol i]]+ld+.
-oH, 2s +eeE "llHzlz} zp *$Ae-l qlqzle+ *+. "+ qls^l 4a:(z-7)E [He]2s22p]2p)2p19 uflzlE z[z]{, {lA
l-}^l rjlall dzl^L 2s fllra;ag ilzl6}Al ¤+. r?-lafol zzfl
(z=8)ql "lsBlo| ulEa 2p ?llE6Jf7l 2+etr a+Elq
9 r' 4zlzl +c qg EBlrAla 9l= gEg 44g=- sc6} [He]2s22p]zp)zp',9 zl E +4U+.
H1]
jL Eql= EJ Eltl zs 4zlzl EBuAlr glt rs2zs,E Hlq^J.

-r.
dzl¤ol 1l"le} ?llEEL+i$ 6I+4 d+g ull= ++4
4 uHzlE ol$+.HtqtlEllE flz}9lrl 4lel4q *= dzl¤ *3 Hunoel EIE}| trl'=E TElg ol+6lril ¤tr}.
3:z flzt9 slql4 eq+el ffl"Jol 94, ol trI+ql ol5g.
fltTl drlelr. +E+(s4l- eqlî ¤Eg'fl;tzi'E ¤eI u
-__
g ¤CR + 91. flz19 bq$ +fl). qAql ri9 flltzt d Hl-E'-^Jqlql fl= flzlE l^Jg ol-+zl ?+= dz}9 ,Kl 'Kl
[F
zJft-2s dzl-"lq q-E + azF= qd+ql +ql+. fz\ !4e q= dz]. Hl]il= zlzlfla- oJ+.
{u
Erc
iLl
(b) Hundel +El Hund9 +4g ¤H6IelH 4+ vlr+*zl"J ol +4g AE

H, He, rela Liel +a= ¤E6i= rll ol-o" q! EBg q"t}^l 8S gll+r 6l+ oJzlEq4 Cag Hlg6l+ 4"14. sd
vJ4g +E flel+a 6l+ Eil(E= +"Jqe'+=+'= F"J $ "f"Ixlfl ¤4$ trll= flz}7l C ffilq, r?-16}
Aufbau gq+rE +4) "JEI+ql 4eql^l BH+= 48014.
^flE"I
¤ dxFq t}szl*ol g"J6llTl+. 444 o + uIqtEl]E +
8B EtExlflrl 301
:r gzlql^l= 2rllel zp&zlzl F"J N flzl{lrJE:zll E4 "I*zlzle SCg ed+ H}?ptl s dÎ 6t'-l¤ zlzl:t-
4 zp&zlzl E+ E"J ^99,
rqa o flx}9lrl= ^Jolq} +ll gl4.
^¤9, "lal+ 6114 A$s+El +4= ElE4 +?l$E =gg
E6J+Eq F 2p.J.zlzl5g :trg z*=,cl\2p,+llE6J+el + +g + glrl El9r4. rd$e qH 7}lE dzte Sdqq q+
dz}ts aJg olFqot eI4). ol E4= pauti9 grl= zlzla_ t) z-3(Li)oJ g4- Z=ll(Na)"J gie+ ^d4ol Hl+61ot 6J
¤Eg + 9l= HI, ¤q *= Aal¤g ^le. EqzlEJ= 4. "I&zlzlaBe(Z=4)3 Z_r2(MB)e+ Hl+6l]o} 6lq, ol4oJ
a6&9 +4Ll]r
^fl$
E Hlg6I= arlB _H_"JtrI= 4"14. *Al7l Bl+|C 7l4l"J He(Z-2), Ne(Z=10), q /\r(Z=t8)oll o1
^Js
=7lvl^l cB++.
@ ÊgEJE4let
fl?t 2f,ft(Z= l9)oll.<-13 +¤- ilBllE d+ +llE+fzt +sol4.
ol fllsgt+= eFe+ 714g^ Eq ul$ql 3d "J_o + .llajs
zl+ dx} 13 trl-tro6.1-A v,?,)E grl9= +llEEl-+ aE Zl^l
,ll ¤ 4o14, r?-16}01 Hlq tlEll uflzlzl- [Ar]+s'o1 g+. ++
6}I E 4z} zE ul-s-o ar-r. w?r)E -E^lEl= +llE6J+ b= 1l
(z=20)E- eg E+e-tr- [Ar]as27l- ¤+. ol +4lqlrJE szH9
zl¤L+r 6}zl. rqH ?llEgi+ 0l+61-o.l ol dzl-E
=ÎHg 3d +llEEL+E"l A+g z}{lzl"J fl*?l ee ,-H+9 dzl-E
elF.J¤ t9l v -yo@r)w?)1+EiB
olEE
zl"JEE glHzl HsI trilEql .Ezilr} +d-
+ qt+ r*l+ +?]= dzl-$ Fl+g + S=trllE ts+6}r ^l-olel ^Js4L+ql
allzlq, 4F 4lHJCg grll E+
ol +g "]tr dzlTt qE fllraJ-;g zlxlal-|zlE EE6tril =E+"-e=
es.+¤qlrJ ¤Eg ++9 4l4ig 6|]-H-H oI¤
:d+E
"J^l6l+ 4olo + ol Eo Et + H= 4"lrl. ^+E+El
ttzlg flzlEgl trl]6l]^J= 3d +JE++E qlq 471 4s 44
"JzlE+ql el6IH c+* q+ +
5q AF^dqlE g+a|_L as ?llE6-J+el qlrlzluQ o3
qL 4+zI 99"t ++.
( t \ ^J *+= rel+ E+r-qI4 +A e4ql E6|E ScE [Ar]3d3ol
Y==l -.^ l{w,(rr)Vo?r) + rlro?)V,?r)l 4 [Ar]3d24s'ol o]H [Ar]3d'4s29 dz] Hl]il= 44d4. "14
\2"' )'' 6J eq¤ olalla[flH :as+ +s"ll^]g dz]_dzt tis H]g c
fl4ql el6iH y.b "J"JolE r¤+ql +6ll^J qlaolIr +,
pauri
eg rel6ll+q"F +trt. 3d dzl-= q o.e+qE 4'll +E 4
"laql= Hlr]]a ^g 6J+(o_E -s^lq=)E- #6ll+"lot eI lzl as dzl-H-4 6}eq, u|4rl F ra dzl¤ ^t"lE qlgg
q. olae
^sol
,d.9
"lF;, gl= ^JEllql 6llR6J+. aJ¤ r_ F +s dzl¤ ^l-"lel *Bg+ -a{, r?-16}q 3dre+ 3d3ol Bq
H}4aolq, q4^J olaql= ^{ 4a ^}E.ll +E
qL 6flzl= 4.olr}. ol trll$ql Sc* [Ar]3d'4s2el {x} ullil$ ol5-
= ^g
6}rl¤ #dl+qo} qI+ ol '}la ^JEIES dzl¤ol ¤fl
^ll -r. 3d +llE++ql^J.el zJeI dz|-dz} HlBg +as}^lvl+
4= ^JEHql ql'J't}4(ol Aq ++ ¤Ee Eq 8c= ol+. 14610l +g glulzlg a5 fllraJfE 4,.ltl EqTIq ^
^flg
-u-"14). +E gzl-E dill "ilHzlzl-+i+ g + gltrl{re 8B.7). {zl
+ 4zlzl +E dztql d=61fi r,=rr7l E uI + El+
ol4l
y,7l qB4 qtszlE ^J46l] Hzl-. 444_0tr. r_E ool I ?-l4q ol=el {z} uflil==$ [Ar]3d,4s2(^Z]Eel n= l+el o]
ola3 ¤q *= + 4zlzl +t +E E"JqI d ¤9 ,r= rcllzllzl ¤4. c.4 Grl qle-l4qe 44 [Ar]3ds4s'
q ilg q¤"I ^sg g"lalb 4,o14. ols+ qa4eE
=Ell
4 [Ar]3d'04s'E *=4. AEql^J= olq+ +1r-^dol $olzlL
ÊEg
%= + 4zlzl *zI +e] E"J+ dql 9lg oll aEqzl *= *g fzlql^Je+ +ag *al "e. +a 94= 4+^la + 9l
+ F dz|9 ¤qol+ "Iq+ql q4^J "ls+ ?ol F
^Sol
dzlt tolt ^J'H4 *t Es= ++.-Hq, q?+^l olEel a
1j.zl4 ts4t*ol R{^lq r?-l6}q ol + t4z]. tolel 9l
HzlE 7l^lAl q= aol+. 4 ls-¤B ,d.4z} tI
EllE+ *e qqzl. ^fl-4}d
*=+. K
5
6
Z=r}oJ Llle+ lHe)2s22p69 uHzlE zlzl4 r44& SC^l

il4. ol gfl ed uHzlE [Ne]e + E^l6J+tr]1, ol43 +4
?l^=9 ed+ qtsg ++ 4* d4*:s +llE*fqt .q fal 88.7 Sc flrl7|. [Ar]3d24s1(9--) Hl|^l t[|t!0tl [Ar]3d14s2(8!+) Hll^l
+/l EIE 3d fllE-Et+= eEl E^l-Irt HJ"Jol + alE+. B lE E
z|,<J ,r.11 449=- zl]*zl 6fq, r46l-q Z=rtoJ Nafl = ^l-0lel
^l+6Hoh 3 o1lLl^le.l as ?llE-d#oll dxlTlEqTlE dill ollLl^l= [Ar]3d'4s2 Ht|xlTl
xfb [Ne]3s'9 H}liIE Tlz.lAl E+ L+EFS [He]2s'9 4 tr1
'*+.
=
302 . flxli4q^rEH
4. {zlrl} +sg+ +p *44o1 ilz}z|-449 ol+q, rBE (c) flxt ur!=El olE HJIIE
ql^l r azlzl ¤t+. olq+
"l+ql* "le+ eol r8z|lel 4 6J flaE flrl Url=g 1z]14(cue+ ee) E= Hl++A 4
zlzl rt +7Hl +q6lq azl& s ^J"ll^l A'*azl'71 Lle+
+ql= F4 EzkH,4 s,e+ eg)ql^J "Jd flz]¤9 +d Î
*tr1-. olel 4"-lel Hl$ g+. s 88.2e+ rB 8B.8ql ++U HIe+ e
"l *Alttzl= +i}4?l eeE +llE*fEol ilell_ts d+ ol ?zl¤ s9 * +71 tr-ql^Jb g+e--E+El eEa- e-e e
9zl ull$ql dz} uflzlz| Azl4 +Î^dg ++.llS.+. ol +a ++ ?lz} Hlzl$ol ei6}q, 6J +ql^J= "J o + .llee++
4 AzlC o + ola|l.rl +7lE Eel +a7I +4t+r B + 9l 411+. xJ #21 ^Jql^lel Ai= q A6[z[ 67[6[01 4 zlnl
4. lzl& EE +zl tS 4ol4l at{ r*el rszlzl9 fe ole dxl¤ EolBzlTl trIE"l+a E + gl4. 4dat9 6zI
Li4u+. r4r az1& Eq 9l+= 4=e +714a 6l-=ql, zl &zw *zls "J+ tr-Îqzli alzluj dzls=g *|-z} gE
?zl Hs= flttz} 44E + "Jzl-+e+ t."J6I+. ql +tlqq ?lzl oll+ql EI 4zlzl EI +9lE q d6F= Sd
+7lgE= flzl9 {zi ul]zlE sc^lzli u}zl* 4zlzl 6iq, r46lq q d6lel Gzlzl 4¤¤ 6l
^Lql6}zl *
6l
qL +AAql uI4 s, p, d, "i fel ql
,ll gtrI 6J¤ 6J +ql^J "Je+ e++ flzt qlzl$ol =
=q7tL+ql ==e_E f;zla|
++6J+. d ?liE(+ill4 o + d E-+E :-tt 49 fla agq d6l7| 6zlal-b rlls ¤+6Ia) gltrlE ?zl9 fl
=.+ =
E)e dol E+oJrpE EI4. rB+ fl^-(+e__a +Eqzl *zl 44ol +g + "Jzl+ql 6l]B6}zl ullEol4. +, gltr|=
?*=)e Ll{+ dot qI+. f E+E fl¤(6+71)e
=+ol+r.E +7lY "JrlE "tEl= +il H ^JEE Erl4+ ",ln|= ?lzl 4
aJEI 6Iq, oI*¤(7+70+ qrEE qlq.
=ol4a =ol+r dol rl49r ¤.+= 4ql 6ll%Iq}+
az)& E9 s, p, oi d E+ ?lA.E "Jolg9 dzl Hl]zl. +g tr++ 4qzlBrJ +7161+ eolol 6?zlql^l= E4zl
;tC flz}el HiEI^J4 dx} uflzl_e.*el r+f, zlqlEfltr dz} q, d fl4-==4 illrlsE p EE flzl¤9 $zlfii-ol {-$
E "jj-j4H Eg + 9i+ + +tl flzizi-p tjxi¤ qiq{r" =+
olq^J flxlz|_s dxl¤ qlqLHr, f4a ¤_o + g,qqi EI+ g 88.2 fl}Eq flrl HJrl= r/pm*
-
el d dzl-= 414^l7l= aol+. El¤ p EE g^=E ¤.ol9
Li Be B C N o F
9 dzl HHzl= 6d flxlql+ Hl$d zl^ll9 dzl H]]zlz} ol 157 tt2 88 77 74 66 64
+qe 4lllzl 4a fl4q q+ dzl-E 4l+6H^J rJ zlali f Na Mg AI Si P S CI

191 160 r43 lt8 ll0 104 99
H eg + el+.
K Ca Ga Ge As Se Br
235 197 r53 t22 t2t tt7 tt4
Rb Sr In Sn Sb Te
zrtrJEt o{l 8B.s 250 2t5 r67 158 l4l 137 133
Hlr+Ee_l {z} uflzli \p* "JolgE dx] ul]

[tu]3d34s2olq, Cs Ba TI Pb Bi Po
t7t r82 r67
il= tArl3d3ol+. 9lHzl Hql^J .B+ e+^J"J as dzlzt ¤ 272 224 175
. zlE eq q "*e dlEol ++Elqflq

"14 4zlE^-l "Jolgg EIE= 4,ol EI44"J a eg
ol
ql, q4l^J Scgl F-dz| uflzloJ [Ar]3d'4e71"Jqr [Ar]3d3
ol gtszl= EB6lzl gJ:+. 4l{} a4ql E6IH [Ar]3d3r+ 300
lArl3d'4s2 qlqzl aE z"al q=EI+. z,ozl ftzl Cs

ÎolE Rb
cq ,rl4 qs .J.zlzl3d +llEs}+.g s7l= 4"1 cl +qql K
zl=ql, olag *ZI4 " + agal4l ill+lzl= 3d +llEEr-+ E 200 -+---_-1
o- Eu
9 d4-==4 q ÎolE tr-sz++ "J4ol dx}-dzl Hlgg Na Ac
!l!
_E_ttaflf;'+ Bzl oll$ol4. dxlla Z"nzy +E6l zlzlfl K
ll
Li
-al3
z
lArl:a:ol [Ar]3d'4s2-H-4 rJ *e. qlq 4= ?*Al S4. "14 kofr 100
el ol* qlEql W*= [Ar]3d3E HlliIE 7l4Al 94, s.P

Am
d Znt4zl9 s= yz+ olol$ol [Ar]4s03d,E uflzJ$ z[z] F
,ll q= 4014.
0
20 40 60 80 100
flÎ EE, Z
feJ 88.8 flrl u^lEE +7lEE 8oilîel EAt 6+7le.l aJEJ + q8oil=
(+EllE Lu 0lF+1 HJ^l=o1 +=¤g T=6lGal..
ea cl"Exl flxl 303
,l44ql Sqzl dzl-Eol += dzi.=4 Hlgg alzl ulls.ol

q e d6PI -E-+6}|^l ¤ ?ztalzl gf c_E_E T3,zlzl q +e
Lr(4) Bd.(4) B*(4) N3- o'(6) F(6)
-e tqg El Ezl ?+eq r46iq ¤.ol¤"1 s+6k 4,"14.
59 27 t2 t7r 140 133
*ol9 HlzlEE 6d flzt+ "Jolgr+ Hl+* EEI a6Jg +
p3- cl
Na.(6) rvrd.tol Al*(6) s'(6) (6)
+4q, 7l* ++ *ol8E3 izl&s ^J"ll^J $aq e zl7/l
r02 72 53 212 184 181
olql fl+(_E 88.3).
K.(6) ca2*(6) Ga*(6) As!(6) sd-(6) Br-(6)
138 100 62 222 198 196
ztEtE! 0{l 88.6
Rb.(6) sf.(6) In*(6) Te2-(6) r(6)
t49 116 79 22r 220 caz*, K*, cr olsES E-+ r {z} uflzl7l- Eg6.|.7ll
Iri
Cs.(6) Bah(6) T1*(6) tArlol+. rel+ olEg q d6PI 4.olafzl ql+ql r EI

t67 136 88 xlEEol ^J.ola}4. ca2+olgg:. 4 d6p} 4l"J zE :z
.gE .Jg +zl= ollB ol8 ++lql 9l= ole +(qla'|l ,(}4 ol9, +,ll E 46Lq dzl¤ 7l-+
^llrll
E{BzlTl ql$ql qlzl$ol z|1t
z})g +4. HH9l+= 44421 ?}g oleq ql+ <te +&+ 4"14. rJ "*9 4I+. crolg¤. olE olg + q d6p} 7l* 4ee ,r|
^.ll
<tE"l zle d"ll +e+ 9l+.
+^J r tlzlE"l 7l* aq.
uI+ {EJA q 7lqlq. {"JB rzl ?+tr}. r olf+ 6+71

ql^l= f +llEE}+r=ol a+q= +e qEol4r g + gl4. (d) drt r!trlE
oEal.ollLlxlel
+ f dzl-b q d6l¤ zl-4+= sr+z} ql+61 E+B6lqeJ a}ffi El94b
^JEilq il= +dz} szle+q {z}
Tlzll cll
,J6J *zls} +4q=
^l- "l+ ull$ql), E+ flzI H_:r7l La+ gsql fliE glHxlE r giel eril ol_e+ oilL1r!+r 6I
4 ru7lz16z|.J{l ui=t flzL qlzlgol ^J'J6l ffislzl ull$ q r,-tr- ++U+. rr]r E4}l dzl-=(+"J d6}el oJ=ol$-q E
olu|. ufglrl a Egol +^l
^lAtElE^J
z/\ ftzlt;] q d6I +El) qqr{= rJl g,q+ 4AE {lHzlE Erll ol_ctr} oilL1rl
7l * zJ-eJzlzl t*ol-?fl dzl¤$ ¤q'&4 flzlzl "J+g+.
L4t_ *tr} lall olgp] 9lHzlzl. fzlssrlql^J qBrtl H
+TlgEqlrJ ol ¤qq gl= gzl¤(rrprl pb4-zl)g ol "Jq 6l-=zlE rH 8B.eql +E}'}]s.sq, "J+ zl# E 8B.4ql +
4E7l C6}rtl +Eq4^J z4l "Jdqq 9l+. *ej +7le+
E] el¤tLÎ4^l ql+q= A+Bri elzlEol olil4 aAl + 8 88.4 Ar|l "J oleel ollLlrl,.
=rll
i{-= Ar+E aJEJ= t*ol4l 6J+. 9a I,/(klmol-t) Irl(kJmol-t)
* fllel 0!E HJrlEg "lg eoJ ralql^l "JB "l$E r| H t3t2
olel z4q ol olgs] 7lq= +4uq.+ "Jd6l-=
oJ
'}lEl He 2372 525t
olg4 ¤-olsg +c 4"]= + olg tlzlEg TlqE Mg 738
ÎolE 1451
.J¤I a+ ?4. ole+ ztol ,zl¤,9
=zl= CE6IH Eqo}zl Na 496 4562
7t ?+tr}. r46lq + s,r"F4 "JHql^J= o.E ol8 HlzlES . zlE ¤ql cl

"*9 ulEol ++qq gl+
140pm-tr +.I. 9l=Ell, += 4Etr ?lo o e ol5g. EE"61zl
9+E+ +E6]]ot E|+. ol8 *zl$$ t4 ol$(Hl$ d6}el) 30
++lE +ql II|4^JE B?+e + gl=ql, ol lxlloll.<lE 02119 He
t4 olg¤. zlzl:i_ BA+ AiE¤- ,r.J-s-" ap !lQ. Ne
t flzlzl-6i+ E. r ol^Jq d{¤ Sr "Jolgol B trll >20

o
+\ Ar
olgE a7l7l E4E +C gzlB+ 4"I4f+. q --: I
= ^JdEl= gl9s,ol r qul
K
5 Xe
4^J "Jolgg flzlE4 4+. qlE.<J {zf ull 6 Hg Rn
iiil 10
ilTl [Ne]3sroJ Na9 flz] q]zlEg lelpmolzl"J dz] ullzlz[ olr
o
lNelgl Na*9 ols tlxlEg E4 rozpmol4(E 8B.3). flzt eI Li 8@
N aK Rb
zlE4 uftlzfzlE "Jolgs fzl¤sE lrl4 q]EJTLH^J t.g 0
Cs
r 0 20 40 60 80 i00
+"Jzh+E 44g=_ 7l^\6l71trIEql *zlE"l 4Tl+. ?\ a-s-, z
*"199 tlzlEg :_ olEl gz}tr_+ r olf+ flli fal 8B.e B^l-HEoll rtld|1,(l s,ilet fl^=sl 1[t| 0|8a|. ollLl^1.
=ql,
30/* 8 flrt74q.^r+aJ
E 8B.5 dxt tltr,tE E"/(Umol-])* 4zlzl sc¤ flttzl- 44E Hl +Bg iH+= a4 eeq,
E¤l qr+9 4+E r7l ull+"I+.gol8{l dzlzl 4zl
^Jq
CI 349
q. eol) PJ4g-a gg
ae(o-s+El o2-zl Bce qe+
F 322
Colq, trI+^J E,^71*o14. + Eqe= 4zlzl olul fzll6|
H 73
d6lql E6H^l Hlgq= 4,o14. xx]. {a}r= "JH}4 o +
o o- =}eq,
4zlzl 4 0 e+q EEI trqtl +JE".J+ql
141 -844
. q "*e ZtEol ++Elq =qr}4

zL.E Aql 914 +(+4¤- "JrJ?-_l ++ g^ql^le+ ?"1) E.E pauli gel qlE
ql qzls +llE'J+ql Eqe q1y1rs4 Tlillql^Je+ 3ol)
^1]
4.IfltrI. gE alg zld fs 914.
dxt tlEls. E,= 4zlzl zlillt flz}ql ?zl-El Ell "J=q=
qlqzlu(s 8B.s). B¤49 oltlzl"J E:3.4olg^l .J?-14"J 88.4 rli{l-gEJ¤ g +llE-d+
+Eql $sE 4zlzl ?lzlql 3zl+l oll "ll'-lzlz} B=!H A
zI rlElszl- "J9 Ztg *=r+.. E".>o"J trll= dzt dzl-E zl]=nfxl EE{} 4dz} +=E {z} ullzli +*¤} dzl--dz}
BB4ol4. ^Js4L¤¤ _lr.Bj6}zl ?*¤. =Î4"J 4"14. rel+
gHlsl+ql^J a uHfl.ll,zl"J olSE] qlqzle+ dz} rlsrls e+ qlqzlql +6J 6|]E tl$6l 4ltrlg +=sg. +g + ?l=
E .u.+ +7]14e=- +ElU+. $9 4ol q +zl4olzl ull+ql 4lt} HJBoI EdElS.4. ol "JBg D.R. Harrreeql E6l]^J ^lg
¤zlrlE olag d+4se. ¤E6IA+. 4E+ *g ol9s} AT}]ElflI(e+Elzl tJezl d) olq^l V Fockz} pauliel ullrJ
"llHzlE *E.rll,
olae- oJ uta 4zlzl ed+ dzt"il 9all ?l4E r.El6tr. T1]eoJ 4,o14. ol *Hg- Hartree-Fockel rl
"i g tiqA;1o1,<.j(Z=3 rlFEtJe fl(HF-SLF) UEolc+I 'of=Lll Ltl^1l.ijJE uffr-rt
oju<juj Z,r=t3ul+) +j4i trq4 + !!!
^-!-!
lJ
-L?!
.ri.tl . t-l
-
-i i -rl -rI -tl-'I
^ --
-I
A *I
?J + ?lzl ullEol+. Hll4Ee=4)9 olgsl zJol ¤E6J + gl+

"llHzlE ul =zl
"J +4E
olgs+ qlHzl* tsilBEE+ z}gcll, olag +iE *c +a g?-lql q-+ gz} 7a.11 +¤l qL cEq =^l
44?+ 4zlzl2p ?{lE6JfE itzl6l.r glqî olaol zs dz} 4 zHH¤. zlzla_ ^] L¤I+. qlE^l Ne {lzl;. +E
E qflg EllE+ E ,J6t7ll e.Jqq glzl ullEolrJ.. $r_e. qd6F= 714. +L= flzl- +llEtrt+¤ zlzlt_ =^}4"J
1s22s22p6-tr +
+El aivl^\+ olgs+ {lHzlz} f:7}61+ql, ol43 q d6t +'J + ?14. "lzll eI zp dzl-E,g{a}lEz}. q_oE+EIE ?l
zl rtzfilzl rllEol4.rq+ olgnl 9lHzl= {}+61 44 r4r +]lEoJ+ql +sg 4"lzl Xzl.$_aPH
qte-E qltlq= Ar+= B?-lÎaE =^l-4 ,l"JEl= ,lHl¤
*+. "l "l fi 2p ?llEsi+ 4 442]14 Hlgq 9lHzlE zlzla- ol dz}
z| i-l$-9-E 2+e 4 d+qq, dz}-dzt ^Jc = Hlgol a4 + ql r]l{} schrodinger 4g ¤ + gl4.
"l ^13 El+ zp dz}oll
Tlql^J z}+61 e]d-e-e. qltlq. Atr+ gt q rzl utlEol 4aJ 4olzJuJ ol !e Hlg44 ol flzI 49 += E= d+
+. +"J "Iq7+ zp 4zlzl ml4+zlH HI"J il]g.l{ +ee(N g fllE.J+Eel ffiarlql E+6J4. al$ Ezl +l6flî E_
"l
ql^Je+ zJg-)ol ¤cEl=ql, ol19 *g qlLlzl9 dz} ullzlol . +E +llE.J+E =Î4
q+
+16117}zlr. ol 2p
q, 4+^J o*+e-9 qlLJzl= ql^J.}LtrI *a olSE] qlHzls ?.llEoJ+ql ql+ schrodinge, 4g ++. olq^J rset zs +llEEr
r"J# *olzlE 4o14. (trI-s azlq p4 s +Eql ql6l]^JE "le+ Hl+¤l 4l4lg 6I=+ olBlal "JflE zl
Îolql^Jb 4 4
.ll4zlbrll, olag olE.E +llEEL+7L q q&qq glzl oll 4lg 6l.ts 2p,2s,4 ts 7lls6J+E- EAI F]=rll, "JHI4g=s ol
"l
+ol+.) o, E "l Ne"il 46J <t=g qlzil4 os E"J zld+ql +llEEI+rq= ,rla"ll "
^l-s"
q! aE$ ffi {olrf. ol TlldE +ll
+EI+q, oli-E olgslolluJzl ?zly qel d6}7lq 44^) E++ îlEE zlzlt_ *ql^Je+ ae 4l4ig qE"lalH z^le
alel4 dzl-$ q E¤zl ullEol4. ,Hdg +llEEL+ 9lHzlE Eg + ql4. olBlql ++
^llrll ^llEe+
4=#(z=rr)oll,<J5 ale]4 4zlzl3sol4. ol {z}i fl9 e+g ^}]e E= +llEEI+e+ qlHxlz} 4E H6Izl ?*9 ullzt
E+q Er" E+ "Jd¤ tr-4E s¤g qlgE ec+ dzl¤ zl 4l+6ll olBrll gg 6l]7I zlill-"J+^J 6]]"lq
=+. "lBlql
ol qg 714+a 9)4 Z,tr=z.szl ¤4. ol qlEql Nael o1951- A+el 6]|E^J +¤-aE ?14.
"lluJzlE Ne(Z= to, 2,6=s.8)-H-+
gd *+. rel+ ¤zlrJ* 4l1l el}s gg HJ^l¤ Ee E'-+= +a gfle
HF-scF
EIY +714 ++|ol +^l ^l+qq Hli6J +?]E zlzll o1g ql^Jlt'J ul-q a.ol $xl IE-E7I ?dEe +Bl. olE+. tr+4
+ qlqzl9 HrlE ¤H6ll + 9l+ ol scr 4l4I A4= eiq}4 +7lCql +6J g}q ¤C4 ¤
=
_e zfzJololl,tJ al4zl El.ql, olag
^J
dzf 4lEfs-b B"l *E+= ag !Baql=4.s"J olq+ ol HJHg +ill
=+9
8B ElErt Erl 30s
4"J u1-="a;-*O Cql6J glHzlE- +az) ql+ql "l4aJ cd

4 ¤Eq +¤ Hq= + 9t+
=g-d71lLJ=
Il. +lEB+ =Jffiql^l Z 7+ dzl¤"t4 zttl9 ElEio er+E zl tr8. qI flrE flrl Url=g -r,414 EB Ez].ll^l qldq+ g
¤qq, 4dz} flzl9 +ill4 ol E*'6J+EE zl¤E +d
ÎolE aElE Hlr| e+.
*o e +EI,-J + gltrI. tr9. tI fl19 018 HJrl=g olg eal r.illql^l "Jd olgE rt
42. flÎel Crl H]|il= d+¤ +llEgL+E -s.\lal 4o14. ol9 44ql ql6J 7lq+.
tr3. pauli fl49 6J 5g+ a+ql 6ll*6]+ r%uli ulle[ flalb 6J trr0. AU ol-gEl ollLlrk zlz,ll tr 49 4dx} gals+q lTHq
+qd +llEEL+= d+61^= dz[9 fE E_a 41,{}'Jtr}. dzl¤ ^1146l+ rJl ps-al =]4' ollHxl4.
44. 4dzl g^rql^l= czl-59 Fq Er+e+ 7l4a+7|.Er+ trliE trll. Eill 0l=+ ollLlrl= +"J d6lE o3'ol$e-tr-Bel rz11E 3
oll s +lls*f9 ollHzlzl E"J 444 p +Jls$lfEtrI *trI. zl-= 4lZ6l+ rll peal Bli qlLJzl4.
trs. +5 flel= flzl9 H[q%]EI {z} uflzl$ q+61+ EJI ol+ at2. drl r!5lE= Tlill ^J gzlql+ {x} a}ffi +4}^la ql t.ll
B+ el4. --i 9lHzl4.
tr6. + +q4r +eaql^J= tr-ol.J +llE6}+=ol az} lzfl{ o+ D13. flzI qlzlE, olgsl qlHzl, r7-lr 321 llElr* izlg E.
4+l4f q-gqlqL +?llEq++ql flzlz/lzl EqrJ4. ^Jql^j frzlzie-e E.J+.

rJ7. HtqtlE1| flzl* 4-9 "l$zl ?+e d49 fz| fl4e 9b !14. 4dzt fl2}.il 46J schrodinger !g +il4 "JEg ^rill-"J
{x} ullzl$ olE+. +C 6ll= ?9 ullztxl !E"l o.JtI.
=qo}
=s-d^l=
de ^l
+^l al H-a
+llEEL+ Y(rpr2, ...1 = yt(rr)yr\rr) ... 88.l
=ÎH
+s. qd6t Z"t=Z-o ddl-= ol +qq e= +6J 1o14. 8B.5
E48c flrl IEEaJ
dq +{g -H-4 Cals e +444H flz}g i]g tlEfle+ 3l

> ol EEJE u!l+= ol* ql6J rl-Eo*+¤. +44 oe ilal6Hol6J+
+ tr"4ql
flrl ^-0ll d^lEE ollLlxloll g-d xFIg ge Elqt4
¤E4 qgl =q?l=
eilE 016}|6l= Ell rJ+4olEl.
fftr 8C.1 tEH ++lol
^lE =pJ
> E4d
dolE AEe6h= rd4 ,HHql qe.E gz}4 E
TtlLJ
E
fl^Pl Exl'Col= go.= ttt| LH=ZL| E+61'= +^ldel C#et "IqL4
tr|.+= 0lE6lq g^l=el Erf ollL1^l SEtloll g-d trH= E= + zlzl $zl7l*+ tr-Ez|¤¤ 6Iq d¤+ 19 %Izl¤ ¤+6La
olrI 4 4-."eHE ol flztut *zlzl aliql +44 " +4s ol tl
#e-l ,3-gz]$ zlzla_ 9l9ot +tr}. olfl* ^J4e-e+Et +
> =Jg-et qHl rl^l e= a4g +S B4lql^J *olEzl-e eI4.
0l EEoll^jE +aE gxtE ollLixl=?.|(EE sA)el trld^l flrlel
Exl uflx(-e4 8B)= oJEB aolq. a?4 qal^-lb 4aEPJe_l EZI 1 {ol ffiz} EdEq ++
^l
¤E(EE 7F)E ?lEg aolq-. *21944 o + ol dol ,t6qxlf. cl-e-_!- z;ol zzl ^JElle+ al
+ t1-4 r]."i9 dol g=rl eE!= ttnz zlzla +EI.J + gt
tr|.,
flzt pxrBg flBa6l-= "JHI4 zH.d¤ e+61+ +
dE{*=ol+ g+ qL +olEJe flz}E dz} Eezl-EolE
ÊEH un= lwi iv,dt (8c.1)
"Je4 glHzlz} ar "E H6tjr, 4ltfz} ,=lgllhol4L+ q ¤zlrJ fiE 4214+zI EHIE ¤&zI+. rdzl ilzloll,<Ji ol
izl i=ltBltt r"J "Jzl-3 t=6I4+ ¤+6].71 ql$ql +4+= aol -erE +qd4. rZ x+, F, "A z+ ^JE# 7l{ Eq
lol'I. Ei*Bql^J= dolTl + 6J¤. ^lolql^J "rqt+r "J6J ol4, p 4t'l w=-ex, lty---ey, o) lr,=-r""J CBg 4= ElEl
+. HC Fe_E "JbiE a}g flzl-9 9lHzl ++l= +E il= g +. "J"J {ol rffiz} u.{!-=.7} 0olH d"lzt al$9zl g*=4.
olzl"J ol Eqg gleH^J r $d,t}*"1 Eq-6ll¤ 1"14. olaol 0ol olH ull"J dolzl
"l+¤+.
!Al2 +E =51El+E- +4U 4+
8c.1 +4= flrlel Ê4EaJ ol dol 4"+z| EHIEE +6171 fl6]]^J 4I
^dB# zlqls
r$a]lez].. qlE^l z+ CE+ trl¤4 ?ol ¤4.
EE Tl+-6.J 6JE
^l-olE
dolzl "Jq+= 4* "].,14. dol=
"JezlE {s=3 *lE4 d"lz} 6{E!= 4oll" r+zl ?+ !r.ti=-¤ J V i ztl/ d T
e aEe $|*ul4 o e 4,o14. 9E dolSol -"1+q
=rlg +E +=IEql^l= z=r cos aol+(Eq 7FE El4zlE ^Jal zt
+44= ag dE4 +=lolaE ++.
=zlE
ol +!g +Ag flzl¤9 dolE l$aJeE/d EI¤ + 9l g Eol-eD. -t-4H -9. zr.r"ll E6H^-l s-(4rt3)t/2ry\so1¤+. r
4 olzl-b s= loll 5l]%r-6F= E-¤4 4e¤-"d'g zlzl:il_ gl+(E qH il¤.r+ 6l+ tl4=ql ql6J ul-=." $fz| &/r)yr.,@,0)E
I sny. dolzl "JqB Q= dill 4l+F%hol E=qqot 6lq, 9 flzt +llEEi+Eol g+(EB sey. ol- Bq+H +lE 4
E|4^Jdzt9 4¤+*e *zlzl zlzl:n_ L+rJ ?+#*"J+ go1 ffi$ tol ¤4.
g H+6J + glE+ Hollot 6J+. rfl6}q d +llE++1t=21!
Ivior,ar=
4zlzl s ?llsEL4{/=0)E dol9EJE o}^}7} qzloll allr5tap tyi
z
V, dr
4}.gFe}g zlzlt- L+?J + S.zl ullEql ol dolE oi*9zl
?+= aol4. uftzlzl_e. s dzlzl += s +llE6J+E olE6|Ej
[J,'J, &-il( +)",r,,ft*[ r2drsin? ded|
H dzl-E 4¤¤itr"l H6Izl g:g_rr-E *zlzlzlzlt-L+rJ ?+
r ac.r^19 zi^lle} +E:. zizlfol qu E7.l+qt azll Quanta matter, and
eE%hg E+g f s, o o + olfl dolE -d+Elzl ?+=+. oI change (20 I 4)-= -U-"I-ei.
8c flxl4l4Eal 307
ffi 4+g rll "Jzl-9 E!_q_E Elqfleq, + /oll +qL zl+
w
ol spd
: S
: p :d S p d
6i+e+ 4Eql *t zz11E 4EEe-l e-E- qqflsq r+s=r+

Aol +g +
-aH
}GC
9l+.
15 328 H)
JV
zvl dt= 20 571
02 824 23 039 H4
v2
4 lt 97 492 24 380 H;)
r'R,.,drj,, ^ ,,;,,, ,Y,,oY,,.,,,,singdgd@ 259
3 Jr-&,,,, J.
E4t 3 4E E= 4+E 4l4I Lyman Balmer Paschen

+ts a016}+q deq qsE +-Sr+ ee 4E+ t,-t, + 1
4 mu=m1.,+mol9zl g*E eI3 ool4. fal 8C.t t.^ gIl-E ^4EaJq Eg4 r 6[|4 gEE 9.E6J Grotrian
++. dolollEf trf+(cm-r)= Eq
=?El-.
,= J" E" r,:,^,,Y,,^Y,,,^,.,sinodod@
+ql"J E=6I^l ?+r dzl¤ îolE ^J_E++qlE E=6171
¤zlrJE /=14 m-0& ^J4I6I= 4olo + 4E E= 4E + qlEql :f
{ol r$=-z} EHlEq z+ ^dEg A/= + 1$ Arz,=sol qzl ?+ ^.ElE eg #+E__E +d-6l]41+.
EI 0ol+. olae dq +!9 "Jp"l4. x+ CE4 /+ql

=
ql6}|^JE. Hl++ a4lg 6|]+E trlg4 gg Sd+ +
(a) Ets:dzlA=B
^llEE
dq +4g Eg + 9l+. $zl zzllS zfzla- ?lE He flz}9 qlqzl ,tj4ta]]Ez|.
=+1.
ol flx}9 HtqI^Jq {z} ullzl} olul ojr ?l= H}e+ 2-ol ls2
A/ = +1 Lm,- 0, *l +49 B^1.=0il (8c.2) olq,:z EE tr-El]= ol+E qL * TJ,zlzl zs Tlls*ftr g
rlj-d d.l +^l
4zI rstzs,9 dzl Hl]zl"J 4olr}. ol 5E tlEl]ql^Jb + dz}
+ "Jzl-+ n* 4#=*4 zld +alqzl $eu--+ dolql Ell
zI tl.olt +llEEI+Eg il-zl6iE_tr olEol e}g lzl ?*ots
* a/ <tl} +-Jq7l"J 6IE q¤ aLe-sg Hg + 9t+.
84. Hunde-l +zlql e-l6IH 4gol ¤q+ flz19 tr4z1 ^
Sol eI$ 11 91. tl{tr+ 9lHxlz} *trI(Eq 8B). o1 ;
ZlEJ=et q 8c.1 ^J4= E+ -"1+94 flzI ÊEBql ,lqts + 9t+.
¤e4 q]¤4(4ITI)E + HI]SS rEE diil 4
4d 4^l7l qH +llEq++E +îc dolE gea + fl= ^g ^g
*Falol trl-s+. 4I4 a+ql= + 4+F%Fol ^J
zlE gElH, /E <lg q"J6J trl-e.ql ol "Jzl-+ql ++
+d ^gel ^fl
4lqq ds ^g Aol 0ol ¤4t-zH 8c.2(a)91 44HEoll.
dq +zlg 4+^l4oF o-J4. /=2olF + 46 +-llra;45
/= lol4 3ol qqo} qr+. tr}4^l dzl-b 44 glraJfEH
ol tI4= pauri fl4E. ¤E6J trll +*'J o_ol4(Eq
8B).=
^fl
4 np TlralfE(Lm,=s, + tg :e+^l7lH^J) EE mf ?ll
EEL+e(ee dq +4) dol¤ + 9l+. rBl+ += +J
o_(1,2; = {cx(t)F(z)-B(1)G(2)} (8C.3a)
E6J+EL d"lz| "J qq, r?-l6lq rs *llE*f+ +E 2v2
,?d +llE6J+89 dolE #zlg+.

Bq A+ql= + 4}+F+3 qH} dAl {l
ÊE
oJ sol otq4, rB ^{
sc.zo)ql +Eld HIe+ eol
^g
zlzl ul]$
^ll
*alol 719"6t4. olE ^ll ^J4E9 e.q 8Bql^l
cq +44 flzI 9lHzl 4 ^JEll=E g-41 oJs-" olH ule+ ?.ol qla eq+o14.+^tr ^zHt
=+lE
.tlHzl4 olg ,tfolel -d+ dolE 9qtafl.<1 +4U Grotrian
trrrel +aE ¤Hts + gl+(rH sc.r). ol rHql^l rl+ d u(r)u(2)
old"Jf E ^JtrH4 oE ti +El-U+. o*(1,2) = (8C.3b)
^trlEHg (+)tortD,I+B(r).,(2)l
B(1)B(2)
8C.2 +Erl flrlel ^'lEeJ
+ 4471 4-g ol+,. 8C.3a^l o e olEE ^gg +F+E
dz|g +7I +zl.6Joll tr++ g^19 ollLJzl
=95
qlg +IEEI i 9.lt He gzlel ^J4E Elga dq+J. 5J+ /.gEol B
308 8 flrl.i4gt^r+.aJ
15 1P rD 1F 35 3P 3D 3F
0
)-An <Gete -X.Zqne

-il \
Ms= +1
^/
o)
ilil
llll51.56
....,e-Toet
tr llll52.22
-10
Lil53.71
-|
i
K il sa.qa
i
5 l
,c 6
-20
I
I
I
Ms= -1 I
Ms= o
(a) S=0 (b) S= 1 fg 8c.3 cE fl^l-E LlElLlE g+ dol=. E^|ts colE trl+
(L}ltr ÊlEHoll
LEIL.!)= LlElt!tr
:leJ 8c.2 (a) uiT.!ÊE I^l- 4FJ0l 00lEl(s=0). 0l- q7l I E1-e 1.
LlElt!3E 8E 0lq8 ?lil= ^rJ EEle LIEIS + 9l=rll, -d EE17l

^l^16l'= =
0l flg 89 ol- -zt +lil= it^l5lE LlBl^l EEl= HJEH g-dE ?lil= il-rl
6[0{ 4EEB0l ool Ect. b) + E^Pl.E"J ÎiJ= 7lE nll= z\trJ
ol+ iI+6J ^JqE
^l-"le.l
d"l"ll 7l"Jq= l4EHg +4
4FJ0l= ^trJ001 olLltrils=1). 0l lll Tlxl B lo+ LlElLl=rll, =ola=
=rl.=
q7|r1 slEl e:elo_e LEfLflfltrl. + qtfl
*zl"J ol + ^JEH. Îolel dol"il 7loJ6l+ 43 44421
g"J6l.Xl E="Jdt^l g$$ +=6[Qaf.
^rJe trq6lXl UE:dol^lU + Eg ?J:=+. r?-l6}q gE¤ EjoJ+4_oE + ^Jol6J +ilH qE
Ê!3 gEql 4ql Grotrian trl+E rH 8c.3ql +4q$.=ql,
"}+.
ol +sollE + 4"121+4+ 9l+.
6Jolr 8c3b^lE qL 6I+-a +4H + gl= ^JEll= 3=-d ^llEE
c|E}|4r el4. He flzt9 1s'2s' {zf ullrlz} +44= 3+6} (b) AtrJ_fllE
rLrlIr'rl rl*t] Arl ull.B O HLiilxU
'd Y] i -o "o' -t "n
ull(dl-tr'l rJlrj-zlzl rlOrJI rrl
tl-d "o "ll T --1 vllvl/\l/ I x,E"llr - =E
trIE{l rJzlE z}zl EHIE= *=Q. u}}z}zlE
|
=.=- = dzl^b
^tdg +4=
He flzl.9 lsr2sr {z} ullzl +ql^J a}+6} *4 ^g
zI +"JoJ ^JEHtr+ *3 qqzl$ *=+I "J+4. "l 4¤+ ?JE 4eE+g *= dzH/>ooJ ?llEEr+E dzI)E ¤az]
o + ++ d+e+ eeq EI+^l ol +]lE 4gE%}"il zl.J9E
"JHI4"J ¤Eol4 += gzI(E= Ez})olls zl+¤tr}. zl-zl E{lE.4=4. ol afl z}zl EHIEe+ +llE 4¤+*
dzl. uHilTl-FoJqI ^J4.E A+q= oJeI4 o e_ aI+t'J q E,* zlzl*49 ^JgAL¤¤
r Û-+lE =:d(^Jsz}+)ol4
tullzl- E"J6J ^JElls+ *e qlq zlE 4.=+ . ol e6Jq rllzlg+ ol4,ol
6Jtrl. flz}9 qlqzl Ggl.il "lzl
qlqzl zlzl $zli gqlg *ql^J Hl-El^Jql {z} u}lzl c.4. xlzl E.HlEe+ TllE zl-zl EHIE9 tt44 ul]
"lBl¤I = ^$4l¤+*$
^J44 ts]].Jql e]=+q(rfl
oJ, tr1"4^J + ac.a).
ql ql6J Hund9 +zlql^J =o-+6J ulg]. ?"1 tL+ *Al7l
^¤
dz]-E Îolel 44214 ^JE4t+ql ¤6Jg u)7lzl ulEol4 ^Js4L¤+ ^g z-I¤+eJ4 +llE 4g+=*E tr-
^g-+llE
(Eq 8B). qL flzi 4"ll 9l= dzl¤ 44 uHaJql E=614, ol E= +41= Lie}4= + "JHe d
Îolel 44214 tr-E4
¤+ tL=J6l A6lq e E9 dz|ts]]ilel +.J6J tl{e+ Al+6J
.llHzl ilzl 4t6l + gl'1. qlE^j H.9 d*
^J4 ÎolE =
9lE rs'zs'e-l +"J6J ^JEllel iF+6J ^JEll ^l-olE qlq zl ):lzl I
642rcm-t(0.80evgl 6l]'J "J+E il¤ 44U+. ELI r-lo ;

AE,,
gEE gzl. fi9 flzI ulal],<l $ S
ÊEHol ÊEHql
*6171= 6}E^JE. r-}s-r} eg + ++.J $eg zlzlL glc}. \
r 6I+= aEl ql^J"l q= E= dz} ullzlz| e4 ls'n/' s
ol4= 4o14. 4^l aI4"J"l E=+= 4.o14. ztll) $zl
=
E-+ E=E4l 6iq$ ol flz}9 olgE+ .tlqzlg+ q ql
l-O
EL
r.-lo
x- a
ollLJrl oilLl^l
= = (a) (b)
lzlzl gs6lq 44^J 2*oE flztzl .<!zlzl $-r. He+
olgol =E :reJ sC.4 4fl-fllE ,J-cte rul IfTl EEIE9}fllE xl.7l _=.flIE z'.lole.l xl-71
B^dg+. ol Eqel
s-41 $ae
+HI+ql^J ¤¤614
8E4r'E01tr|.. AE trl-AIE= 4EEaJq UBt= LlEfLHq, + 4 fl+tE=
zl"J d"l E+ql= + dz]. ullalol HB + s ESE EE]Eel
^{,J:$= LlElL.!tr|'. (a)oll,t1q rJol
+ 4FJol Eil"J tt}l
^flq ^Jql4 ^l7l
zl qlEql +"J6J ^J4el AL+.J tr-Eil dolE "Jol4zl + EElETl utl-dE dfEHolEf. -l.a1Ll (b)oll^l^1al HJEH g-d
^l-"lel =
g tttt=^Pl
+zFd tElB=
=al6l1l
LlEt'.!tr|'. 0 | x P | fct rtl$l I -d E^ l t|^ qq
?+-4= 4o14. + +"J6J ^JE]](HIqI tlEilE E6J6}i^J)= ^|
u 17 l"
,Jal.ilrl. =+|a
88 flxl 309
ÊIEH
S=
_1
@
-2 (a) d'ri-(&) s' {z} uflzlzl zl4 + 9l= +"J61-
elfl /E {lg "Jot{l olq^l iel <tg =+l#
+6110}*4. (a)
l=2 l=2
.tr d dzlql qBH^l= /=2o14, ol dzt HI]TI= j-2+t-19+
t -z .a
t-,-i4 2
j=2-i-lel + 714 + 91tr+. (b) s dzl-91 ql4^l=
=+l=
/=0ol 4, /=]9 + zlg.afQ.
=+lqlol
f.EJ 8C.s d E^[(/=2)sl
Ê 4EEB?} +llE 4ffiF01 eat=J nll= E^l
9 illE 48Eerel 8EH4 Htl:doll q4 j7lz7lla?":z 71tr + ?lrl".
Êal a+"J +a= 6IE A6Jol
^fl-+llE
il= Erl¤ +e + fl+. =+lEe-l "tlHzl"ll "l
zlel dztl 4¤+*, + +llE 4gF*E ElEl 6Jg +
4.ll= 4"14.
^¤4
+llEel + 4+F=J9 uHaJ"l ¤4q1 zt gaar.E 0llLlxl= L[El
zl-g trll= dill ^s4
^trJ_?llE
4¤+=Jol 24, ol + 4gE%Eol HI'll "J-J Ltl=
^]
"J tril= diil 4eE=Jol zl4. zlzl* ,8 +ql^l= xlzl E {lE p4 qjq zlz} olE
_r.44 e +
dz}9 di] 4eE-*g "J^l-+ i4 m,tr- +49 f ?l=rll,
6l+q= jel ae /+1014+(+ 4&E*ol ee "J6J"J trll) E -tt.@ 84. "14 tali$ u|4zlfl
EE /-lolr(olE"l Hlql ,J6Jg Ell, :zB sc.s). qI +q 4 4X t}s++ qlHzlql E]]tI 49 Eal g+. BlElql +6J^fl-+llE
ê?+fi
+4 zl
4= +qlzlE /&^l 22ql .qE6}l +gt+.
el /ql qltil^J +4+= {4 t"lt {tE i= qlqzl 6}E
r+r ++. l=0oJ trlli-l=+"Jol *{+g+(ol gzl- ?Iql= 4g
=+.|
E4l 1 tlEz}+ "llHzl"tl ql+
^l
4}+El"*+olq 4+rl olaol dill 43¤.qr"l4)./=r"J ull zlzl$ol dzt9 +llE 4gf%bq ¤+B trll= ol4ol ,ql Hlzll
E jrl iolzl4(^s4 +llE 4+E-"d=ol ee "J-J) E= +ol+ qL+. E. ztzl LHle pzl dzl.
^sql ¤+g q= oll,ol s"ll
1194 +llE 4gEed=ol ^Jtr Hlq ',J'J). Hlql*+. trl{^l ol rlczl* ollulzl} LvJ+ # s.,91 Hl4l
il+. +
tlE4r+ qlLl zl __lt. cBn s.t
EEI EtT
3zlgql^J ulel u(C$-ol u*, ,r, A u,)* u(CEEol u*, ur, tI EEle+ r zhl$el ,-vJ+ #9: EIEIE
^ll*
rTle+ eq.
oi u.)E +94 Ag EE +48 + ?l+
u.u --
"1+
q,* u2 -- u2
u--u*i+ ur) + urk u=u*i+ uri + urk

(b) + HlElg HlEl ,==3 trI.q=r+ ?ol c9¤4.
{zlri j,A k+ 7+7+ "J9 ,, y,9 z+ "}6}9 6F"}E E?l
i,
ElEl(=zlz| roJ ulrll"l4. EEIE 'td4 Ed rqa #C ,lK
aJ4. uxu-- u. u., u-
E ¤&g trl^gq ?ol
u, u), u,
r.'lc
u+u - (u,* u)i + (ur+ ur)i + (u,+ u,)k -uu\i-fuu
=(uu
zy'yz 'xz -uu\i+fuu
zx'r 'xy -uu\k
yx'
,
L. UBI ,(-ll
E.E (qg4q +4^lb Eq eDE 4ElzL9 rlal zrql^l ¤Eg
u - u = (ur- u,)i + (u,,- ur,)i + @,- ur)k 4014.) F ulqzl- *+l ElEl iet jE cqq= E tlql flg
z
J. -7,(ll trll= olEel EEI +g ++l dlEl ke+ B4-J %}6.19 6}:"Izll
}J E]
(a) F ulrl ue} u! ,,.:;7}Eg +94 ?"1 C9¤4. s4.

u-I,,=uu +uu +uu
310 8 flxl+491'^+EaJ
cJalz {rl
=.21tr. +4U
E 6H'J6l-= 9lHzl53 rB sc.oql +4.11fr.+. qlLJ zlzl i
diil 438"+e +llE 4¤5*4 Âq 4+F*q dlEl q}4
^g hcA{ r}4z} +zll, :.flt--+hcAoJ t4zt z7\q, dill ++l
tE+ ol EE] j4 aTlz rl¤. +4ls+q al4}
=j=l+sol4. Eel '+7]1 +C' +lzl= H6lzl ?+=+= ag +E-6lq+.
6J + 9l+
j' 12 s2
r-fl-+llE AqlE rllzlE qdo}ql E=6J+ r ol+=-+llE

ili =1t+s).(l+s) -ii *il + zs.l
Ir++^J e5g 6l+ dzlql g44r 6}dg 4"1 _z +fl= E= a

zl?r yllril q= A+E
^J^J6H -HH(4"Jol
*;r zl= a4
j'=l'+s2+2s'l
{.ol) dr.ll olailg + 9lg 4o14. ol+rll 9E zl-t$ a?-l d
--1
7-
+E +Cql il= 44zl ¤ aol+. q d6|71-4a++ ol d
sl=ili'-l'-r'l $s.;.1fx1q E ol qlEql ^JzlE zlzl$E- ^llt+. dzt9
S zlzl EHIEE ol +llE zlzl*4 tls4i¤¤ 6IE-e. q d
^
+lel 4e rq+ rdqqlzJ ar|+. 4e++
6171
^Js+¤¤ 4zlAl ¤ 4,"14. "l ^J
^s-?llE
Eq+s flz1. Haql rr] EaaJe(z*ql el+++).+4 ?l
EAI 3 r.d4 Aq¤ "J.zlqo+4 ^l o.=. H+6pl
+lE arl¤ "Jxlqqlzl?l ¤4e +Hq 9l= E=
Hl-+ElE zte+ eg A+ql= ol A6Jg 4e-l +^l6]]E Elzl"J(9lHzl
. r+s-4 *ol oJzlqq}4 bIEg11+l)ft" Eo4 eg g)E
zl\a1loy 0.4cm-r Atr+ olF^la+) 94 Ag +4
=9=
HI+J+qot 6J+(Eq 7F). I flzlglrJ= ol ¤etol q+61 ,lT]+(+d.'n-, CEel olf
g "Jsa+).
s. I = i ljlj +1)-l(i+l)-s(s+t)iR'? s== dzl. tr-E]lE grJ4 ++ gzl-4 p 4zlz} *g s TllE
ol pffi tt-Ezf+ 9lHzlql +6J B,g "l9rl

6J+s trqe 4E 22119
ÊEH
Col 444Erll, 6I+=
Hlql^J¤ hc,qlrio e eEr g+
^l(E".s.I)oJl
+l6LE "Jzl-+e+
j-l zfltr+q trqzl= dololl +E 6I+= E"Jel ul]zl
a(g*4-" + +4U+)E zlzla- Ê_fllE
+4U tr|e-,rrl Ag 4 j=+
=+lE+q
B"lzlE dolgl 9+ 4,"14. "l +
Ê
ollulxlgl ++ erll g+. _trH dg e6J qlEql +4+. El^{l +
^lg ^g-fllE ûlEH
E,,,,j= lhcA{j(j + l) - /(l + l) - s(s + 1)} _=fl(zl-trFol olslq} aEol+)¤. _E_E ol4t "],ril +471
4E-fllE +E6trll ++*+. q7l^J +s= 58enm(* 17 000cm-')
dlaAf8 oilLi^l
(8C.4) =
sl +^qd$ d{lsE z6 d"14, s8e.z6nm(16 e56.2cm-')e|
58e.l6nm(r6 e73.4cm-')9 F d-oe. ol+qAl 1"14.o\ 2+
q dE ^dE5ol ol 'DdEs',ol+(re 8C.7). nl-4^l

z]trJEt 8c.3 ÊEeE Aliql E6H^J glHzlzl rTcm-l
+EE9 A+ql=
Htq^Jqql il= "JA4 ++ gz} +E
dzl-b /=0014, g ^g-+llE
B=+
"J+el g6J-9
tr++^J .r=*o14.
"l ^JEll"ll^J= +llE 4+F%Fol oolIr*
tr-g4+ otlHxlzl 0ol ¤+(8c.4^lql7=se[ /=0
^g-+llE
g. Bq^l +qlg + 9l+). ol .flzlz| /=toJ +llE6J+s E
+tncA
j=tr
EH +llE 4gF%hg 7l^l4l 9L :.r-la}¤ :z lgr+ t}
E+¤-e- B + ?lE xlzlal-$ +El{trt olq* H11il= 4
2
K
dzl+.r=*ol4 Ei;=;o14, olE qlqzl= trI 5 8El.l=
6
= =+]el
*4 *"1 ¤4.
-hcA
- I x 2 -i j=*
+ncA{lx * " i}
E,,,r,r,r,r= = lhcA
f.al 8c.6 TloJEl= 2P' -Bf H8-i

Er.r,r,r,r.= +hcA{*x } - L x 2 -} x ;} = -hcA Ê-+llE =:cr'oll =+l=. =+171"#-i
CPI E o + LHaIA= +edlGal. g^l+7l i"J SEtlt 2i + 1 oltt.
=?lsl =
8c fl^llEleg 31 1
,P,,,
ill 1¤, dill +llE 4eF=+, rfll
+ill4 4¤+* Fq 'll
16 973 ¤¤ +ld q rJlt;lrll +EB + 914.
17 cma
2P
aJi zlc.E trl-Sl} eg zlzl {tr-g +4U+
16 956 1t2 ^ll
T
E D1 D2
aJi zlo9 EzHqlAql p+ D F)=:z flz}9 dill +llE
o
l> 4gE=J "Jzl-+ rg +4UtrI.
IL E E
a3- 21c.9 g+ tr-ezHglaEl] ,pr2q 2)= 6}el rl¤lEE
H C c
(o
l.\
o;
(o
o;
++u+.
@
r.r)
@
rr) ,S,,, a3zlEg s-E+ 4ezHqlarll 2rr,,gl,rlel *)= dill 4
uff, v ----+ +F=J "Jzl^+ /g {t4 6}E szl= +E}U+.
=91
olB.l+ r]l+el i$:B rH 8c.8ql sqE6H --3 "llHzlq ql
fg 8c.7 Ll.EEsl DCol :d¤El= ,i= tr861.= oilLl^l rg. 0l zl¤# zlzla- ¤EB + 9l+.
EI
CeJ :,Jald(l7cm-1)E 2P -atel eald= LfEfLH==+l
aolq.
ÊEaJ =q {4 z}]9 4zlzl 9tg ull= olEel zllzl f.llE 4gd.=}"1
qErI Ei4zl=zl g.= ^J4gixlE *+6l]0} qi+. q
^Je
6|= ol di{ ?JE 4+E=+E a71+ fli{l ?{lE 4-eJ grl
GZEU 4E!-ttE e*lg+el aElEHEg
+ rg zlzla- +4L}]=ql {r(r+ Dl't'ttzl Sr}. "l 4+F%}3
re 8c.79 r+EE ?lzt +4+= DdEq g 0, * r, . . . t L *E Hl]6}-S 444ErlJ, ol uflaj$ +44= a
ÊtrHql rE=E dz} uflzloll,tJel
"Jg +4d 4"14 +EE flz}9 ol olzlf M.oltrI. dill ?llE 4grEe} "Jzl-+zl tof, z)&
e6J ^J+= 4l4I6Iq+ =
*ele 2L+r/l! Hl]6&g +ElB + gl+. ole+ Hl++ +Al7l
^g-+llE
a.alg AlEl :aB sc.zql el6IH ol :-trle.Hd e4ag di{l 4E grt+ se} oJzl-+ M, ^}olql, z4l E 4
grt+ =i{14
==
ts}]ilel j=141=*
=.91=- ^l-olE
"llulzl
?J44 ?Jt+. FJ /s+ "Jzl-+ M, xlolqlE CBqI+.
ol ZI4g 8c.4^lg ol+6fl^l ng zlzla_ +49 + gltrl. rsl <t(+ol olH e+)g cbbsch-Gordan #E$ olf-afl.<J
z}lzl]9 ?llE 4grE+g A'J^l4^J e=+.
Eol + trl-g rzltrJ+ A+d+. =
=fl=
Af
L=lr+l.,,lr*lr- 1,..., l/1- /,1 clebsch-Gordan #E (8c.5)
= (E,,,,, - E,,+.r) t h, = i A{+ ( + * r
) - + (; + r)} = i r{
+a il= r7.2cm-tol+. trI?+^J /,-l,ql+ ¤E]]il z)sZ Efl ag tol +ol E + S.zl 4E
oltrl. tol
=lEil7,|
t,+t,g +4,11= a$- + +llE 4¤+*ol E
A=1 x (l7.2cm-t1: l1.5cm-r .J aJ¤ ollol4. olSol HlEll oJ6Jl9 6}ts trll= 3l
"J.J1g ^Je
AZt I t,-trl 7I +e}t4. ol E ?"IE+ + 4t¤+
+^1 +E 'JA"] ++ gzlql r.il+ Al+ d4E t i' ^lol9 +rJ
0.23cm-1, K: 38.5cm-1, Rb: l58cm-r, re].a Cx: 370cm-'ol+.
*el t}'il4 uHalol a+7J"J +Elt+(re 8c.e). .Fp d
"I
zH/,=L=t)9 a+q= L=2,1,0o1+.+llEEI+= s,p, d, f, ...
a= gz} HEql 44 ?zlElg +Eq-qiKrBl+ 4dx}
flzl{l,tJE r el=Ezl za\l E+ atr+ a+ *+).
xlTl Bz[ ec.1 +H]Eg Htqd]EI +19 +g Erl Hl.|xl p' ,AEI xlrl T lxl
=E
tqql^J ... +p6sd'$ dz} uHzl5 *Eql, ol E11;<l= 83J SAI
oLi. l-
25 7m.56cm-'e+ 2s 703.52cm-'E + ++lE *=+. ol E +llE xlx{ 7lx{

xlo
E-rr
OLi, l-
3P 1P
tr-4ql^19 A6J t'-+b 9"tz| 94r4r

= ^S-+llE r-ur8I'I'E
D P S
xt7l4 ^trJ-+lE
l=.^l-Q.
Cr--O
3P 3P ,l 3P
(c):d 7la 2
z\]zlzl! '/=loJ 2+olE j=l 1?)'e+ eg s¤g ,rls+. fa 8c.8 g^l'sl ollLl^l=+l= ?Jtl^v1l6l= qal 8E'4tE. 7|-q8
fl^l(L*3 zdoll^l= =+E zdoll^1: 0l
atE\lEol 4rl"J +18 g^|{tsg
,pr,r4Ezt E.= rDrs+ eg -d 7la= o+ d ^l7l
^l-*6IH +i-ll4 a0 I ¤E7 14 884+E(E6FEaDE r| +^1161.tr1'.
312 8 urr|,74gl^r#.aJ
l=1 olE=g +7+ G, E D, B S 6}ql

"]]$qlq 0) + p dzl- z|lel
l=1 e.l a4 H eElql^l= sli7}ol lr_r l=0ol4.III4^J,
-1
L' = l+ 1, 1 + 1 - 1,..., 0 --2, 1,0
l=2 l=2 l=2 olq^l /r= tS L,=2* AoJ^l7lH, L=3, 2, 1ol +$tri.
L,=tl A6J^lvlB. L=2, t, 0ol +g_tr, E_ L, =04 aEt^l
'L=1 zl$ r=1ol +g+. 4+^J d^ll4"J e4= 494 ?"1
L=3 -2
g+
lal 8C.9 p C^let d C^letg Eill tlE 4ffi9 L=3,2, H t o1 El=E1|,
0lAg + 48g-aJ9 ut|-dol A101617l tttlEoltrl. L= 3,2,2, l, l, 1, 0
r46tol F6J 6|+ D6J E, p6J d, rela 5oo} alulz| +g+.

rao s_E _s^l6J A+ +ol r 6tE Ezleol g^l6l+tr11, olullts
Tl7lE.J7lrc.z (a) f'd'4 O) d, Hl]il= zlzla- 919 Ezl
rlg4 t"l 4Ez]$ aloi 6J4., E 9¤ol 6I"l+
L 0 I 2 3 4 5 6 s a¤'cs'J7'D¤'Hz'l (0 :d 'c 'J 'D'H (e) :-E
S P D F G H I
trl+^J p, HHz.l= D B "l s 6J-p$ +e_rll g+ ?14. dzl¤ {4 dzl¤ 146l] +qot g trI= dTll
z}]9 4¤+
g tlol+ tz} Hl]oJa3 +44r ¤44 o _+ ol= HIE aJ olzl+ s(oJE e+ E= HIA+)E +6l]0} ++ ^fl ol a+
^l-ol9
E B+e f ?lzl qlEql 6}=el qlHzlE qlE 4 dzl"I4 s=+ol+=
^lE +_=.+. Îd¤. Ec6Ir +¤-r+ eol
ciebsch-Gorcian +!Ig oj$aii,,.j s Aig ei6g + 9i+.
Eo+ dE g^l
flzl-¤-,JHg bq6l+ rll +98] de d
ill oJ^l+E. +4.11:olgqill se+ 6J zlaE +4rll= S = r, + s2, sl * s, - l, ..., ls, - srl (SC.6)
^¤ gE6IE
-trtrtill sE "J E+= 4"14. z7l4 dz}9 A+ql= S= 1, 0ol E+(re 8C.10). dztzl ,}l
"J ullE 4g + 4+ s a}.E ?+?+ql+ dlrll A

g6J egql^J= E= +llE 4¤:FelE 'Jol
7}l7}] 0ol EJs q+^14^J dill ^flql
4s-%Eg g=q. rqE s=*4 s=*ol
^flg
s E6J 444 +llE 4¤+eJ9 ool ¤+. tr+4^J 6J E4lE g+. ^g
trl= trllE 'J il]+ltl 44 +E dzl-5"Jg ^J4I6IE Btrl d 2s+ 19 El=is.4r *+. S=OoJ ull={E6J ee
{}g 6JE
z[ a[u[z[ E.fl ee B]?ql fl= a+ql= rE z]ol /9 <t4 ls,ql^le+ ?ol) dzl¤"I d+ tlg ol+q dE 6ol
esq, Ei+^J [Ne]3s'9 HHzl= s6]+ol+. ^gol
eg +96}0l ¤+. +"J dzt9 c*
s4. ol a+qlE ,se+
ollE S=s=+olq, q4^l [Ne]3s'4 &9 uflzlE 2+6t rSzt ¤

H7l8r..2 dr} Htlilel Ei{l illE 4FJ 4lt} 4. olg+ u]-1!z[zle [Ne]3p' HIITI= 2+6t rpz] ¤4. 24lel t[
(a) d,e} (b) p, dz} Hl]iltr+Et 'l-g + 9l= oJ# +6Iq IolFzl ?+g AzITl 9lg QlE s=lolq, q{^J 25+t=3ol
4. EF 3DeI 4.3 r6a3-ol ¤+.E"J6F+ AL+.Jq qlq
^Jq4
I.aiE Al:d Clebsch-Gordan +gg ^l¤-6}7lql *^J, +
d tE 4lail= ++trHrelg ol +gq E+: *9 "J + "=*
?l+). tr-E4}¤-s ahb dzlzl t4 oltr- glg ullE ol f¤ S= 1
g s+4 0 e ol+*trI. + +d + dzl-= aq+^171a- ol S=

q^J 4419 aBJ¤ tl4q+ dxil dzl¤ eq+^14 u+rJc+. "=*
-0
Eol (a) aliatS ltr-trl - lz-zl =0 ol+. tr|+^1,
L = 2 + 2,2 + 2 - 1,..., 0 = 4, 3, 2, l, 0 (a) "=* (b)
lal 8c.10 !x(5=]ojzl-E"J nllE cill 4E d:Et|7l EtrJ a¤Er(5=0, 1).

EJE:aOltrl-. (b) 5=1?.! 8Et|=
(a) 5=0?J A|EH= Msel 'J0l 6l'LtS0lq(Ms=0)
2 +.llE6J+E-q +EI4= rll 4¤:zl-= r,.;r, ¤ill4 ^JEHE t+Elr+i= rll 4E lll Ms 'J(+1, O, -1) 6e-l Gl! 6lLh= 7E + fleq Ar6-8r0ltl. E"JBfrl
zl-= 4= +Eg gzI"I"J =*6.Jqzl ?+r E"JqL dill= ¤l6l]^J ¤+9tr1. ar6:8r 8E|]E EEl E/.l= ral 8c.2oll L|EIL[|HEI.
8C flrl4EEal 313
zl= ol Eq ++ql^J ¤86].fls4, olE9 "ilHzlE tol

*
,* flztzt {z} uHzlzt 2p'"J =E a+ql= 2p6ol u)zl
tr-++41 sr+ ql$ql trlsrt. =+a
^g ^JE +l+ Hl xlelE E"J "J"J"]E f#c+.
olul {$o} ul.s+ ?"1 "Jz}+i= +"J dz}9 1S 4gE
eJ4 ?llE 4¤+%iE
^JEH4
H}]6JS +ElU+. 4zlzl {4 zl] (a) Na9 dz} uflzli [Ne]3s'o14, ,r]4rl 3sdz]
=01
ilg qlqlE
"lBl6J
qeg +FJ etrt+ /(.JE C "J ^J46LE g+. oltrll= L=l=0olr E S=s=+olE-E
=i{!E l-j-s=lulol -"1+¤+. EI4^l a; zla.E'S,,rol4. 0) F
+ E= *dflz} +B.J+. E.J ee El?pll B aL49 dzl
7t glg qlY I=j7I Elq, /+*ol4 l/-+ lel q! 6J Zlg 4= 9 dz} H]]il= lHel2s2}psqlql, ol49 [r.re]zp-,E H r z,l
Q. [Ne]:s' Hl]ilql^J=- 7=io1q(/=0r+ ,=1olu-E_), :7716]0l ?-l6J + gl4(zp-,g zp 4zl a}*zt Hlq gl+g +4ql=
2s6}g +.J zlzl4 'S,,,E +4U+. [Ne]3p' ullzloll,<J zloo141. EI{^J L=t_lol qr g_5=]ol qq, r46}q
=+lZ
* /=1olq, q4^J j=i4 +ol+. tr|+^l 2p6}g rp,,rr| ,pr,r4 1-1e\ I-tr, iol 6l+¤+. tr|+^] ol + 6J 7l_s.
=$el
+ *=+. F ol zlzl $e++ trIE L'Pr,r4 2Prl2ol+. (c) olag \:lr- 14 s,=sz=joJ 24^l
ql =+l=
qqzlz|.rJE +s+.
=+l= ^g-+llE +41+. trl-?+^J L=2, 1, 0r+ S= t, 0014. trI+^l 6Jf- 3Del
Efl ee HLA"ll ¤4 zll9 4zlzl 9tg trliE E= 4 lD 3P9I tB:a4r,S9+,Sol+.3D"J trll= L=2, S:1olI,E
^¤
¤+=d=4 E= +llE 4++=J4E eElg _r.eJ6llot eL4. ol4 I=3,2,loljL trtzt,rJ 3D3,3D2,
"i ,p,ol4. tDg ql=
=+l3- goltrt 3pel 3+6J
e ,}]+ +d.6}zluJ ¤elol "+g a+(pg flzI H I=2, S=0olq, lela}cl ol 'D2
^g-?llE
s9 flzl-E)ql= Russell-Saunderc Eilol+='J^19 ol* =fl=
4 'poolH, 'PE +gt} +fl= tl,olr{. 3SoJ
3P2, 3Pr,
6I^l t+6I7I il4ts iz| gl4. ol ,J^lql E6tH

=+l=
ollE rS, $ols e) E +96}g ,Sool4.
^s-+llE =+]+olr0=|
a6Jol a+ts a+ql= E= TllE 4eF=J=ol 6}t-6lc 4t*g +4 Pauli9 g4ql E6IE E'J +llEEL+E + dzlt ¤
4t9 a4g ^J46IE ¤+= 4o14.+ E.= ?.llE 4gF*= 68 ¤g 714 + Setr-+ ...zpr4 E= ...3pr4 eg d
qB dill<l rol qjr, E -E=
ol 6J6I]4^J uftzlzl zluNzli zp'3p'rl eg dzluilzl_H-4 oJ9 fz| 44.
^gEE
tr_ r?vl4 Et6ll4^J qE di,ll * sz1-g q-sq
"14
"l + dill + a+q +4+= oJ¤¤ E46}q41|*t4zl + atr+
4+"F*Eol ttaltSql el6ll^l ]3,ll lzl g+r ¤{ q z},rllal la-ol 9s_a14.
^S-+lls
B= aol+. r?,la *d+q=
/el ag clebsch-Gordan +gql
\t7lB718C.3 (a) 2st2pt, (b) 2pt3dt u|lilzl- +4ull= 6J
96H^J trl+4 ?ol f9t}4.
#r{+.
I=L+ S, L +S- 1,...,1t- Sl (8c.7) tdr 'od,
"d, "d, "c, "([, "(1, "c, "J,
j'd, "dr "d, (e)
qlE^l [Ne]2p13p' H}lilE. 4= 3Do]E A+ql= -"]+E]= /E "Jr "Jr 'udr (q) 'ode :-E
3Dr,3Dr,
4'P,9 T|zlzll g+. trszl*ol . trll=(z7l +49 flzl-$9 A+)
^ll =fl= ^S-+]E =
?JAl g+. qlE^l ,p *d
"J"J rsolfl +{=Ee+
> Russell_Saunders ¤6Jol ^dB6lzl ?+=+. "ltrll= d z}]zJ|
=fl+71
6J(I= 1> S= i)* ,pr,r4 ,p,,r9 + :.=l-L 3p6J {¤fl r-fl z.l¤+*r+ +llE 4¤+=+g AEt^lAtl 4lt[9 j
=+lE,
(L=2>S= l)3 3D:, 'Dr, oi 'D,9
^-il =+lE
*=+. rel+ t alg +6HoF +rI. rr]r "l jE¤- clebsch-Gordan f¤¤. ol
<soJ qE qlE^l zs6o}(L=0<S=i)*
"14 ?"1 9zl *=+. +6H^J e6J6ll^l +ill4oJ /= +6liot +tr}. ol a6J %'-^lgii-
'S,,r9 + *=+. 6J+. qls^l prts|]zlql^-]= 4 dzl¤91 4il z]]zH
=+l"Jg =Elol+r r,4
9;9 Zte +oltrI. 4 dz}9 .S4
4+d-*"1 rllzll ?llE
GZEE -d7tEEntr A6Jg tr1= 4 dzl# 4¤Ealol l=iol+ E= +oJ "JoJ"l
(a) Na flxle+ 0) F flzt9 HI-'+^JEH H}lile+ (c) c9 5E s !-. 4"1 ¤4. rel{ olii zflzllE dill ¤+.?d¤ol ++
rs22s22pt3p' H}|ilql E1]qI .J zlc.E al4. 4 tol A.J¤+.
r.alg B6J ql+ qg +^16}r dzl. H}lil. ++. i, i, I
^lEl
+llE 4gE=JEg AqlÎ4\ L2 +6tr, E e 3,2, 1,0
^g#
3 3
2
6J^14^l s= +++. trl-sq ol Lil+ s= a*^14^l r= + 3 I 2,1

2 2
6Jtri. ralE zs+t1l),91 trl?+^l 6J 7ls.= ¤ + flg aol+. I 3 2,1

2 2
I
2
I
2
1,0
31t+ B flrt+4q^F+.aJ
##-et li ol+zlg :rdq+4eE E tr]] + 4471"J"J E"J %l6JE

++-zt ssel l-Sa nde r ?j-at 776t
Ru u
sldg 6Iq uliE ol dzl¤ol +g ?ll
^Js E"-l trqri 9lg
=H
+ +
tSo E 4gEq9=_ ?*71 ullEolct. olEol E4 ulaJ=ee sld6lE
e,il ,<Je uJuirll gtrI. trI?+^J oaJS F"J rl-6Eq s6}tr-+ qlq
R
,D, zlzt *3 4o14.
5 t+,+l
o 3. dz} 44$_q}ttzl zll*zl ?+3 gz}el A++ 4l4el / <l
g *= ??)zl alxl9 9lHzlE *=+.HI "lt"l il]+ltl
t+,+l 444 A+ql= I 6kol all"J ql qlqzlz[ .a{x]e $c}.
CSiGe Sn Pb
+71
ol+4g ^g-+llE e'Jg rej6}q +g aol+. I ?"kol
=
feJ 8c.11 2dr[ zlg g+ gE|lflll EllEI gg gzl tr#. -"= g^t-== *e tiE|]ql^l= +llE 4etf*r| 4¤.E=+E ,J6Jol ^J
g ArtTl'$zl$aq ++-d/i-'2J-g +oll Tlrl9lTltrl'.
^s
Hlqq, 49"6lt zlzl EHIEE=E Hlolol ^JHIE+ ldg$
='J ^l'ol0ll =ol=E11,
4e + "$"IzlH + ^l7l EHIETI t}¤¤o194 aJ$el N*
ol +E 6}+e-l s+ql ?lq\ tsIa}q= zl-qlqzl
+A+ SzI9 A+ql= olEe-l qlqzlE
jj-A6Jol ^JB6l+ ^JEH= "l+
aol+.
olBl6J
"Jzh+# zlzlt_ b"llo} ++ =
+A+ flz}9 {lHzlE aC6l"= Ell+ jj-46J9 0l+6110}
dE4 fr*l (e)
6lzl"J:z aJ zloE qA6l fi Russell-Saunders paSg zlz.l][
E.* ag ole"aJQ. olBrll 6ilE 4'J+ olf+ flzI t49 q"l+ flzI /J.4+ E qule} E%IoI4 dol4E a; z1-aE
*7lql q+ qBAl E6l-= 'l-&or"J ?^l.i -r xrs. .llE^l LfEE.: %rÎ
qjLlziTf - l A -l .l J ,l:l
()l¤:11(rE
I
^l--l
-t!-- rl - I
^l
sl rrl .17 tl,-.rl
eoJel - -
^fl-+{E
zlE AEaN_H_H "J + 914. "lel.J 8E E}l trEz[ u[E :z
^1171
sc.zgl u-"J)¤ +44= dolE q+r+ ?ol 449 + 9l+.
H sc.lol+. oJ Es.g EH *g tlE4L+(Russell- 3pr rPur+ 3st 2S,,, 3pr rPr,r+ 3st 2S,,,
Saundersad-) HJ^l ar+e+ +g ^S-+llE tlg. }¤{/_aqh
"J^l ar+el+ ^lg
^fl_TllE
ql+ol qq, q{^J Russell-Saunders %l-^l te qlLlzlE 6Jg *g a}L4 Hzl 4= aol +Eol+.IrI
9 ol$ull^] +E+ -trzl= jj-poJ r}^lq q+ +g tl{.E +^l +lE qlql 4'J6l-= g++ ,prn?,S,,r4 2p,,r+,S,,, o p
s.zle ols"B + 9l= 4"14. +4U+( dzl. ull zl $ ^8 4:"194).
sc.r¤9lrl olul ull$ ute+ ?ol Cq +zlg dol 4C{lr.J
(o) HunoE 7+l 4+Eelol E=qr E6J %IzlE lol+=
Îd
qlEql
^g"l
+4U+. trI4^l o3' zlEE flzl¤9 4S*g +448 a
¤B+ HIe+ t"l t +qd {z} uflzlE+El +g 6}=
olul
olo + olag zlzla- dq +zlg +E]"'J + gl+. z[,r]lq] all
ol4E dzl¤9 4+Felol t44se 4=;, r?-l6}q +
er+ql E6Its trl¤$ ee dq +zlol +g+.
z] lrzl ^Jol6}7l
trIEql r
qlqzl=ol ¤-"J6lzl g+. qI ^l
flz}9 tsrqt}q {z}uflzlE$q L}g'}Eg(dz} HllilT} E AS=0,
"J6l;<l ?*g tr}|= 4lelezl + gqzlzlql) Hundg ffi$ o1 AI. = Q, +1, A/ - +1,
+4q qlqzl +7I +e-E +48 + 9l=EJl, olae q+4 A/:0, tt :_44/= eJ+ /= 0 ?rlql EllEf dEl +4 (8C.8)
*"1 *91 +9*H .ll¤# ee5A 4o14.
0
r.+qTl {z} ullxloll qfl^l= ffi,tzl al'{"J a}"1 =lz] qzlal zlg.+-1+E +zl dol= +4u+ +6J +zl(d
ill ^sql
zld
*=+ E6lzl s..+)g H"l ¤.J9 #zl
"llHzlE ^Sg
*6J+= Îd++E] +g aol+. E
^Sql+ +qI +zle
tr-4 ssoll^J ¤B6'J uls+ *ol ol +4g dzl r'-+ +41 ^rr+ ^/ql
^fl zllzll $zlE +llE 4$f,:*e HIEÎ H6|]ot 6lzlEJ(^/- + l),
9 tl5"l{, E"J H]|a-Jel dzl¤ol ^Js E?] trq4 fleeJ= 4g+%rel dill4"J Hel¤ $ezlz]l q=zlel
"14,"1 TllE
49 +4U "Jzlqof4 a6;ol+. q+= a,J %l^lql el=++
2. +q4 q+E-9 a+ql= 19 <l"l zltv +g o;"l alzl +19 dq +49 Russell-Saunders polol CBg 4l@zl *
qlqzl. *=+. 3 zlHS g^ql^J) 4+g+.+|+ flz}{l4,De+ Ag.J
8C fl^lÊal 315
TlsE r4E E¤ izl= 6Ixl"J flxI H-qzl Gzl.*ql q 4+ gz} 49 dztTl r*Y dxll 4¤E"d¤ gHlerll +r}.11
+ ai}4 o + s4 r9 44zI +4-J6llzll :a 441 li ¤aJ zl *+trI. olel6J ol+ uIE9l ztHS flzlqlrl= "Jqts +
ol {oJallzlTl qlEql +lE dq +zlol *zl g+ril str} +lql s= +"J6JF tr-Elle]. ++6J ^Jql ^1"19 {ol(AS= + rol qLJ
¤E6J uls+ &ol +4+ flzl9 a3- zle,E ¤Etr-Russelt 7l +A& flzlollrl q+q= 4o14.
^J
_Saunders 6J z16 + +4U aql Er+6I+. 4 oJE zl_sE #
=s-d71lLJ=
tr1. 4gol ,d.g ol= !8. 7Iq+ flx}9 dill 4¤+'eJ3 Russell-Saunders 3-dg ol
"lY = + dzl+ EgB ^JEll= "184. ^
Bol ¤B"J trl= g=A tlEll= "1E4. s" 6I¤ 4ltI6}J" +4+ flx}"J tril= jj-e-dg olo-" oJr{.
42. +llE 4¤+elr+ ^fl 4¤+"d=g zlzl4Jo + ^Js+¤-q 6J+. n9. ;qq1 ffisq olol =lzl "llulxl /J.4"14.
tr3. tl.ol'* "llHzl ++l .}-: "J=tr}. trr0. r46'uzl +qeg 4b ralol !r"J ;3-o1 alx] 9lHzlE 4
Ê-+{lE =Etg
44. ul.r'll f=z} LIEI+= ag .Je.l tr"le} #9= 4U+.
ÊlEHel
r}"l9 d"lz\ "Jolqzl ullE"l4. Dll. dxld{"l qlol zll$lzlzl t*9 flz}9lr]} l9 <iol alz"l"J
Ds. -d 7lE= gz}9 4+E%+ tlq]= +ElUtrI. alx] olluJzl= *=4. ad"l * "l,d. i]l+l4l gzr9
=+l7l
16. ctebsch-crordan #E9 4eE"+=g ¤6Jql^] d a+ql=lg <i"l slrq_l 9luJ^lE *=+.
^l-*6}o1 =+)71alz.l
ill ilg E=r+. at2. 7Iq+ flz}9l rIf, dq +4e {2fl:-go1 E6tzl ?+=+=
27. 6JE El=E= 2s+ 19 alol4. rlls6}r. 9l+.
^rdg
=s-d^l=
.^lzl
oe, ,Al
--1 +^l al H-g
tlEAI+ qlLJzl EL"j=*hcali(j+ 1) - I(/+ l) - s(s+ l)) 8C.4
^g-+llE
Clebsch-Gordan i¤ I = jrt jr, h+ jz - 1,..., I j, - j) /,j= "JelE ++g 8C.s
4¤+*olq-
Cq +21 AS=0, 7Iq+ gÎ 8C.8
AI = 0, *1, [/ = *1,
A/ = 0, +t, :244 / = 0 <-l+/ = 0
316 B flrt+4et^+flEE
E71 ,\.8 flIl7ASl EaJ

^,fl
E4 8A +A=fl^l-
== =xll
D8A.1 +ag szlql 4"ll,rJ (a) ?4184 o) HJÎ¤ EE 6J+q EE= g ¤B6lq+.
¤B6Iq4. D8A.3 +ag flz}9 4+ tr-EilE B^16l-= ql ge¤I "JaI.+# ga6}
D8A2 *rJql^l zFs ¤.E¤ 6l+ +ig flzi"ll 4*q= H+ E?-l %}H r, rEg EelE ¤B6Lq4.
G^
l -tl
E8A.l(a) +ig gzle-l 3s fllEdJfz} 444.} uJÎB

"I49 flil= + B"I4? (i) 4d, (ii) 2p, (iii) tp 4 4*9 %r-^lB "I4f4 4s "I4iE "J
6Iq4. 6lq4
E8A.1(b) +Ê flz}9 +p fllr*fz| 444E *rlB oI49 +lzl= + E8A.7(a) ilz[ {az} zoJ +LE flx}9 zp +Jle*fE ?+49 %rr}B
6Iq +. 8A. I 0^l ql Ln.,( p) * 20 - ro p + f o|q, p= ! Zr laoo I 4. qEel +lzlE +4..ilq4. "t
^J
E8A2(a) 6J d +llE6J+el ul-=.ool':-'zl singcos/oll Hlqlq}4. H E8A.7(b) flxI HszI zoJ +Lg flz}9 3d +llEEL+E 4?f9 %Irl¤ "t
cos?
"I4
"l q¤ 4Eql^J +4+dL+? q5q +lil= +4,"ilq4.
E8A.2(b) 6J d +llEg}+9 u15q-*zl uldlaJr}. ulrl sol
qg arroll^J +4LlA-+?
cos2e sin2qroll
E8A.8(a) (a) -hiR , (b) rrhcrtr, rqrl (c) --lcftr9 .iiHziE 4-= +f
flz| GflE$ 9"89 EIE}E= ,*4)y42.
r8A.3(a) flzl HazI zoJ +ig flz}g 2s dalql qi,* \LI^}B +s q++ -lel-7 -lcn*(s)9 gluJzlE
E8A.8(b) (a) -+hcR,u(z), (b) -thcR*(4), *= +
E , ;, ol {z}z} gaB ffiol 7}t} +g t}zlEg +6}q4. tJE, fo} AE +l^Hg-s +e- z)E +91= B"E9 E]slE= ?*l)yL+?
+rrEgJq= ol+61q4.
E8A.3(b) flzI {sz} zoJ +rE flz}9 :s dz}gl q+ "J^}B BE 6J+
E8A.e(a) Hlqtl-EllqlflE +A flx}9 Ne-'/%o14. ol ffi*f
E A+sI ^J+E 4lt6}q4.
E 4lr ol {z}z[ ga¤ ffio] 7]t] +g t]zlE¤ +4q7}. ,f,E fq] E8A.9(b) zs ,(}Qloll 9l= +A SzI9 N(2-rlao)r'rz",ol4. ol sl
rrEEgJqE "l+6lqq.
fl.+E A+sI tl+E 4lt6}{ +.
rE"
E8A.4(a) flzI HszI zoJ +48 flzt9 zp dz}9l rl]6J %r-ÎB Bs 6J+
E8A.lO(a) n=2,1=0, r1r=0t dzl9 q flilq^lE +E "JE=+6}qq
E jf ? ol {z}z} gag ffiol 7it} .kg e}zlE¤ +6}q+. EBA.to(b) n=3,t=0, nr=0oJ dz}9 q +lilq^le-l +E "JEE +6Iq4.
E8A.4(b) flxI Hszi zoJ +ig flxl9 :p dx}9l 4aJ *rI¤ +s q++
E ,^ ,r ol {x}z} gag ffio1 7l-t} te t}xlE¤ +6}q4. f,E: fo} E8Ar1(a) 2s *Î¤ E+E1++¤
"l+6}q "l e+zt + +AAg *=trI=
+EE?]lq= "186}q4. 4¤- eoll" E r +idq +lil= +6Iq4
Maeql^l= qE +Aa4lllEE'+E "l+oJ + 9l!+?
E8A.l1(b) :s uJrlQ rl.e"gI+E trl+o}q ol alfz].
^ll
+4Ag r*=+=
E8A.s(a)
E8A.s(b) Neaql^l= qE +ae4 alsq++= ol+g + 9lL+? ag Bola E r +AAE gil= +6lq+.
E8A.6(a) (i) ls, (ii) 3s, (iii) 3d fllra;ig zizl6l+ dz|9 tllE 4¤+%t
E8A.12(a) H$xt{lrl 4zlzl ga$ ffio1 r al'llilE 51o/oii.9E r9
azl@9 ts1|te +4U= Buluf? 4 4+4 4E "lq+e+ %lîB trIq+ ilg 4lt6|q4.
E8A.12(b) Blq tl{ql fl= Hgz].g %'-îB Es 6J+7I r 4q{}el (i)
g4q+.
= so%e| (n) Tsvos 95 r9 {tg +6}q+.
E8A.6(b) q-q=!+'J9 alrg4g ilzl6l+ dz}9 rllE 4¤-F=J zzlE
E4 88 rld^l fl^l
¤E ETI
D88.1 z}4l-"J+^d at
"lEg "l+6}q 4dz| flzl.9 *rlB irl*lE'-+e| D88.3 Q{z} flzi9 {zi uflzl$ ol=9 +71& -s tl-el +lil= zlzlt- p
qLlzl= +fl-= "JBg ¤B6Iq4 E6Iq+.
D8B2 r|{x} ?]zt9 s}*.e}+q Eilq} +{E++ *^}H¤- ¤Ba}44. ol D88.4 a4 s ol¤EI 9lHzlz} 7z\& *q 2+71^J"ll,rl qB4l H6I=
.J4l= +Eol+? xl ¤g6}q4. 3+71 ^J"ll^]E 5"J6I4l H6IflL+?
=ÎHE
EA Y7
G^
drr
E8B.t(a) o[$z]zloll ols= d ++q tsiE]^]4 {z} uflil$ *l E88.3(b) +71& tr t}g 3+71 giE9 Szl¤ ^J4"llezl. alzl Ez{l ol
+. ^rJE+El 8s+ 9lulzlE *= ?14= qL aol+?
E8B.r(b) olEE+q zlzE|zl4ql ol-e.E d ++q Hlqt}q {z} ullzl$
E88.4(a) {x} ullzlz} tsr2s'oJ E=E Heflz}g t+¤:6}l- = E}=q+. rs dz}
.|q4.
ql ql4^J= Z"n=2, Zs dzt"ll Ell6ll^l= Z"n=r* ole"6t¤4.
E88.2(a) NF* ol39 {z} uNzl$ alrJ. E88.4(b) {x} ullzlz} ls,3sroJ EE Hesz}el ii}EE}+¤ ".}=q+. rs d^}
E8B2(b) O. olg9 dz} EllilE-r^.l4. q Eil6il^l= Z"n=Z,:s dztgl 46li^l= Z"rr& ol+6lq+.
E88.3(a) ?zl& s +q 2+71 gi=9 flzl-E ^Jrl-6liEz}. =lzl d,zll "l E8B.5(a) /=3oJ Pddql= H tll! {,zlzl + 9lA!+?
ge+ qlqzl= *= g^= qL aol+? EBB.s(b) I=5oJ +e¤ql= 9 zH9 4zlzl =qA
EqA f fld,g4l
EEJ 8C fl^l
ÊIEH
gxll
==
D8c.1 ,J6J
^J-+7I
gz} Hsq 14 E=61^= olf+ *9.olr-Ii D8c.3 (a) +48 gzle+ (b) +dxt flz}9 dololl ql.J dq +49 B^l
^g-+llE 6}l -r. olf¤ ¤B6Iq4.
D8c.2 +^ flzl9 HJ=
"Jd9 dEE +EI+= g"Jg ¤B
6}014. rH sc.lql E"J ÊEH"I
4 4lgr+ +¤q= 4zlzl gEg 96I D8c.4r-fl-+llE e6Jel ¤Eflr ol4,ol EoJq qtr g
q4. ÊEH 6J¤ Elzl=zl ¤H6Iq+.=gg ÊEH
ol^
l-ti
E8c.1(a) (i) d dzlel (ii) f dzlql -"1+El=jel {tg 4lt6}q+. E8C.8(a) (i) Li [He]2s', (ii) Na [Ne]3p'91 46J 7l+'6J 6] 7ls#.*14.
E8c.1(b) 1i) p dxlet(ii) h dzlql -d*El=jE ag 4ru6H4. E8C.8(b) (i) Sc [Ar]3dr04s2, (ii) Br [Ar]:d'0+s2+ptql qloJ T|boJ 6] 7lE-
al+.
E8c.2(a) t dzlz| flzl9 + tt-"I+ tr-Eilq *¤- q j=i+ +el "Jxl-+
6.J
E ,*=4 ?+ A+el di.ll fllE 4gErd' o"txl4;. gu}*? E8c.e(a) d,dz} ts}|zlE + 6}0l Aq+ q+q +448 ollulzl ol
E8c.2(b) /r=5el/z=3t +!+4lri 714 + 9l= -"1+q= +xll4 4¤+=*
ol445
# al&4q+. ^fl-+llE
grrlut? E8c.e(b) AÎ d}lilE + 6J"l
f1 e6J qlEql ++4= "llHzl "l
H 4l&6}q+. ^{-+llE
E8c.3(a) 6* 7le7l 'D2= ?lzlE 4gfelql +* qE AB= +4.J +
9l!+? E8c.10(a) 4dz} +lÎel ct dzl.-tr4 %I= lEEHql^J 6i+q=.JE.
E8c.3(b) 6* 7lL7l3F4= +lzlE 4¤¤%iq ++ qts atrE +4.9 + rlol9 dolE qE aol+; (i) 3Dz-3p,, (ii) rpz-rSo, (iii) 3Fn-:pr?
?lg*i E8c.to(b) 4dzl flz}9 e*-dlE]l dz} *=:uleflo1l,r1 6l+El=.JE
zlzlt- Aol= qE aol+;(i)rptrz--- rS,/2, (ii) 3Po- rS,, (iii) rDr-'P,?
E8c.4(a) 9tr Szlz} t"l6.J ?llEQ++ql g) zzl\, (ii) rzH9 dzl-E ÎolE
gl4. aill "Jxl+ s9 zl-E"al 7tE3 9oi4r -E olE 4 A+E +6l E8c.11(a) Lyman 4lgql^l 7l**aE 7l* a s}*g d=g oltr d"l
Es
*L aCtrh-t?
e I t.
^g q 9+ 7.ol+r
E8c.4(b)
"lH flzlzt ^J"IEI +llEqf+q (i) 47H, (ii) szll9 tzlE zl\t_ E8C.1l(b) ptund 4¤g n,=golr[. ptund 4lgql^] 7]t] sa E 7l* 7J
,':-ql olzlf s9 zlÊ" oJ ilEg 9"I4i E olE 4 a+E q-6
?Itrt. dill
"+tlE CEe 9¤ dol9l Eo'J aol+?
s,E BuI4i
E8C.12(a) He+oll.,tl n=)--sn=t dol9 +z}, 4l#, rell ++= 4l+6t
E8C.5(a) Ni2*olgql q+ d^ll "Jzl+ Se+ MsE Tl+.6.J alE* 9"I qe+.
+? ^fl E8c.t2(b) LF*ql^l n=S+n=+ dol9 ,l'+, tlE^, rqa 4l^16l
E8C.s(b) Vz*ol¤oll qil ai]l /-fl o}zlf se} MrE 7lL"d atEg 9"} q+
4i E8c.l3(a) +^'g Szt9 {zi +++= al* t"lE
5ulE-Hql trl-g +
eaC.6(a) {z} ullzl nsrrzdrS qH 6JE3 *AL+? qlLlzlz} alxl"J o}g q! aol+? (i) 2s - ls, (ii) 2p
- ls, (iii) 3d
- 2p.
qL aol+? E8c.13(b) +^,E ?]xI9 {x} -ru.ltreq +++= ai* dolL trl^g +
E8C.6(b) dÎ tsllil nptndtg qts .JEg ?*AyL+?.qlLJzlTI alzloJ a}e qL aol+? (i) sd - 2s, (ii) 5p - 3s, (iii) 6p - 46.
qL aol+?
E8c.14(a) p' dzluHzl9 ++l# +Elr.ilq+.
E8C.7(a) (i) 'S, (ii) (iii) 3P 6"1-=01 714 +
9l= /E <tEg ¤Eiql 4 E E8c.l4(b) f' dzlEllilg LIE}'}lq4.
91"14 H zH9 ^JEI= +El'J
'?B
+ 9l4l!+(? ^}"le} "JaI+ ry <kE +)? =gl#
E8C.7(b) (i) 3D (ii) nD, (iii) 2c 6}=01 714 + gl= /E alSg gulrli 4
H zl]9 tlEil= +ElE + flA!+(? tol6-J oJzl^+ ry 4194
=?1"14
+x
318 ?rrt+4gt -u4=aJ
Ez1,t 3 flIl+49|{EEH
-4.6lxl trrT.ll
o tl -1 d-l\ll
t8.1 Hlqtt-Eil He*olg *9 dzizl n=4,1=r,

tnt=+rol olzl4el ^J4E +g a4# _H-olet), r4I "lgs} qlqzlE alt}s}q+. 1c; ol Rydberg
dolE "JerJtrt. TlsE-zlzla-
(a) 6J: ol dol= +Ei4q4. (b) ol {olE flzl* += gz}elE g4 +Eq el6ll^] oleslEl4L-+i (a) "l +E¤
rlt[, tlt+, "l E}+E zlt6]q4. (c) ol {o1ql E6ll^] dz}g B+ H}zl al-.Y flzl-b a^6'J qe AEq +EE 714"16IAL+? (e) l00s-T.ll.EE!
E"l 9"14 H6tL+? +48 AIEEI+g ¤+ HlzlE+ q-g=r+ zJol ?ol +ql 46J HJÎB r+s"t.J++ qtr EolA!+?
Tltrl.
ra.: flzl+}9 Stern-Gerlach ,J4d3 zlgq, olag ++6lelE
zl&z1$ ol+6IaLI ol$all"t o.J{. ?llE 4¤5*ol =goJ^l7l*
gzl
= ^l4g
't.rm,=*{*+l' P]} $(H+ eg)9 fl"lxlE =-zlE x=x(paL2l4Eu)daldztr- iolzl5rll, q7l^l
ts= Bohr ulrull$, 13 zI49 ?ol, EuE flx}^Jg ol+ ?zl¤9 Bt
=
Btl "llulzl, :r-l-r. d$tdz+ flzl-9"11 44 zlzl* 7l&7lq.l000KE s
r8.2+ol E= szIS k-g + "Jzl+E dzl-E zlzla- ?14. ol+l.J
Rydberg sxlb 5,or5J ceg z$lt- flgq, aiil E4qI EoFglS iE +q^J 50cm zjolel Î^Jg ^l-S6lq eg flzfJg l.00mm "JB flqzlzll
I tsl ?14. (a) 19 tlol = +^ flz].9 qlqzl +91 t4g +Elr]lE ^l d^= ql gs6J zlzl* zl&zl= 4l4I6Iq4.
g +E6].q4. O) rz=100oJ trllE ,J4g alt6}q+ E ¤+ qlzlEt*"il
-#v149
Erl 7a
g}E E41 aotlrl gd^lzJ zllH, +61 +llEBJ+9 zHHS E ec Exl +lE-d+ olE: 5-4 2flrl Erl
zI9 dzt +aE E5L= ql EtL^lvJ + ?lcl.. EzI9 dzl 7
aql ** "Jzlqq}4 olE¤ ual EE'l-E + gl+.r + g +A Ezl_ol¤.= zlzlt_ "J= g?-lE¤- += s"q zflzl EzIe+
*zl-AxJ olE$ t+ AzLadF9 zHH9l +Ag +r 9l+. r ol:gql qt}^la+ +¤ i}"ldg E= flttzt 44 flzl +llEEL
?-lr EzI +llEEI+ gE flzlqql a t= HIEÎ ss}^lz q 'I"J* +p-lE Ez[ 11so;a5- "J-+
"lEg dz]-=."I Ez}el
a^l EE¤4r ^J4*+. aol+.ralr flz}"ll zl+^la'J +a ?lelE $z| flrga
=
qlE 4+^14 EzI4 ols_E AzI +a= ql+5}='ll ol**4
aol4.
=
Efil rlAl Born-Oppenheimer 9C.1 Erl Bilil; 9C.2 gtrt Egig
=,\f
{zlri EE6}+ olEE4 $x}+4 er+(E4^ lr)E 6]]46].
zl gullrJE *d 'Born-Oppenheimer *^PPel rlardl"F 6l-= 9D Erl ?llE-Et+ olE: 0!=-e4 zflxl Ert
Ell, ol 7l4z EzI qlql^l q4 dxl¤9
^J'H4 +¤¤ B?-l
+t#e + il+= 4"14.
olao4 zflz}+zlE $z| 7lsa5 "lEql^J= + gztE gz}
^la^J
?llE¤fz} EzL fllE6J+q1+ d-.]q} zlq= R zl-b^dg:24
6H=+.olBzl 9H EzI9 +¤g dzl ¤-Cs9 zllHg zlzlt_
9A fl*7t-=-Bt olE +4'J + 9l+.ol s{oll.!= tr-olQ} flz} llrg45ol Aee

E ^871= Ezl +{E6J+E Er+ r 9lHzlE Alti6k ql "Jz}
ol EqE +-g+ zli.de ="fr dzl4l-ql El]tI EltEL+. q¤ gq}"l qBrll ol*9EzlE E"J 4.o14.
,ll +44i1 "lq^J "la¤. z$l:il_ +"f* EzI +aE¤- qB 9D.1 e:c'at E7l E8E; 9D.2 EE Aal
=¤
,ll ¤B6lt ¤ + 9lEzt"l4 itlolql^J E4 o¤EI4
Î-SEE
n¤*, +41, q E^d t9 z}]HES ol olE9 tfEEol4.
9A.1 2flxt Erl; 9A.2 EE; gn.e Etgrf Exl eE Erl illEef+ olE: trlflIl Erl
'll++E +zk ffix| Ez}"lq, "l=el dz} +aE ¤
trl-z}^J
He- + il"l"F *4. azl"ll=- tnicta ol.o"alol $H

eB Erl fllEg+ 0l=: +4 Erl-olE =ÎB'g
,'JBg
+q4 ¤4S19 dz| +a= ¤86ifl+. ol doJ +^l-=
ol-$a|flxlql r4E q Cil+ %r-Bel ,}]4 qtsg al$.4.
EzI +llsfl? ol$.$ flzl{l 4s"^ldH flz} fllrffi$ zflS "l
9Ezl+9 E= flzl-5o]I aA u+JE"C+ql 4+^la + 9lE+ Cr+ *Bol BdB_e_pr l ga+a s_** olE ElqL tlg
=
ol tsdolq E4 d?9 qlA6l.= C.ud 4lt_1"-g g + flal El
qt}^la aol+. ol e{oll,!= +A $z}_ol¤+8 {$afz1 .r.1
4L6Iq -H-+ +d-ElEzl¤9 tvtoE ¤Eo}rll ¤ 4"14. fr.4.o1 Eqql^J. ol+l6J 4ltl# 6l+ ""LHql +6ll^J ZI*61
9B.1 fl^l +llE:d+el cE ,lB; 9B.2 +ll-E-d# *,xl ¤Eg 4"14.
9E.1 Hucket l; gr.z 3E; 9E.3 llt(rJ+E1) Altrt
=
fl rl-E 0! rlEel EE=?
"l tlql^l azflal; ,llH=g s+E dHlq AA ol*94, ol

-nxH dillq aa +g+. q7l^1. + 7l^l ^JplE4 Lll¤¤
rzfla3 4o14. + ¤6J r+glrl= ^Jill qql^J "Jq+= +e
Ezl-E9 HI+^dg ¤E"l-= t+q} zflujo1r1. rell gt} ts
ql^J= al& s++"1
^JEqI4_o
+ 6=s6J "J-!- Ezl-59 gq
EzJ "t Hiqi4 CAg ¤B6I= ql qtr zlol= 6l-=zl=
A+61 4,o14.
^711B
Efil rlAl Born-Oppenheimer =Jl
E= +zI +a "lEg q y aol4 ^-lgql= E+ +g

ql 4l^q} z|{afl ^l+++. +^ gz}el A+ql
=^l¤
E Schrodinger alol B"J6iAl E4zl"J, Ezt9 4*"118 "I
+"-l a+e} 4ol4s :zHg-l "J"Jol(+ q4 eI dzl)e I K
5
q ?lop-+.:. B"J+ 61]= +g + S,4. ol tr1gq Born-
Oppenheimer =Jlgg gzlqg
ol+olEcll, ol 3r}{l^J= 0
a4z1 z1tl, R
:z ¤=Jol dzl-"ll Hl6ll^l ql$ rzl qEql dxlB4 ,ll+ E
617ll +rE" 614, :4aI{ dz|$ol $f,ap E?}ql qr==g 4 -hcD"
9 CzlS ^J4ql 9l+a z}¤fl4.:z4a}¤ 4Eol "JEe-l +l E^l trlEJ!¤ ollLl^l +d. E-d eo|.! A^l 0llL1^1011^1ol ,J0ltrl-
ilql aAqq 9l+r ^J46Ir, Schrodinger !$ Eolrl dzl- =-st
E "Jql 4+ jrl*++= +qlq.

Born-oppenheimer z$z| Ezlql 4+^lzl4E * 4 "JBg ol.$all.<l) trJE 301("1 +dE :a{z]rlql 6llB.
=^lHg Laj4 ol 6l+ qZI 7)4) R.e+ 6fla! qHrl
=-sr
hcbog "J + gl+. D,
d ezl 4r-lE + zlse da6H t4.llrJ9 dzlgl
qlqzl$ =:d
46J schrodinger !g Eq^l 4l&,*4. :za1l o1 3 ++61 94 Bq4 9i= czl ^}4 flzl¤9 9lHzl= zl
4zJ 4ElE- +e4l +16lB^l Hliql 4l&g 9Eolal 'tz}+ aJ 4o14, trlHl¤ qlLlzl +dE +E 4ol h'4e+ g
olq6J ,J^lql rI4 Ezl-9 z.lTl 46J 4"l"ll trl{ qB4l =e-E
"lluJ d6lrll +Alg+. 4flz} Exl-9 A+ ArJ ?ol4 4*?+ E 2
Hd+zl= +4.11= Erl qElE qHrl eg + 9l+ zl] ol^J.9 BzI ++"lqE EEIÎzlE ulHl¤ 9lHzl Eg E
(AL+= s_"1-4). ol +dg ElHl¤ qlHzl=dg =4lolep +s= 7il qq, ol H9 +^Bg Ezl-E dill4ql ¤¤
^J4 E"&g
aC e+ tr-{ eE +F qqzlz| solzl ull$ol4. "Jt
"l ++u+.
+dg 4lt614+ +A6iE(E4^ rr"|rJ ¤E6I= E%r"+
EEI 9A fl*7 l-=-Et ol=
Y(r,2)= yA(l) tyr(2) + VoQ)rru(r) Ht#"* (eA.2)

> ol E4= Hfl+= ols
flItTF,l:st 0l==E-tl4 s.EE qA Eol- a|elEH-toll oldB e.JE qlLlzlzl E?]g flzl¤"ll rllfl q-="tl--^+ f,-
=^{^1,
87l El¤lEE dE4 Et- E6F= Ell 'Jal 0lEElr.gltl. +sel de e'JE+ *g ol+= Ve!)VsQ)e + -E^lqE
=61
ulf +9zl VoQ)rgr(l)o e E^lq= ir+* +9e+ eZI ¤q
> -e!g T11L; ql^l HrJ zld¤- aI{ ol ¤Eql^J dzt9 q¤ trJE7l. +o}
-d E^lel B^l +l|gAr+E trP61.= E^Pl r9 qE E^19
Bxl'115:g;5 tr361.= Ixl9 ^rJ=
0l= zl zl rll$olr+(rfl eA.t).
ttll
'JEfol Ed
Erl. ^rJ?lqt=
z]trJEt oll 9A1
> "JgEt qHl rl^l
flxl-+lE-Er+(EE 8A)el g;+sl g 4.ladg zt|E(E4 7C)g
eA.2^lE ul^=."$fz1 76r{e_e 5lolAzl"J "lag t+
6J zl+¤-+E zlz\a_ ++'3 + gl+. r?_l6}q E4 se
g0l0F zrrl-. 0l trEoll^1ts pauli9 flal(tr.4 8B)E o|Eelt|-.
ql^J Hls ?llE6J+Q= l)ql rll* ]IIEEL+E 0l+6}
H
=
*zlE# ?+?+E q o ++q E 44 rE +ElB a+
O rl tl-zl rLrll -:.. l- rr ,lol 2:xLO -iL*Lo = rrj olzl-zl, zl
-r.Ll-illl..|-d5l-r,rr2-|1,.1-1-=E.=,,-=Ij--,,,|.1-):,|--=
^Jl
6J ol$(VBol$el ¤Bg ,tl4rapz[ 6J+. rr]I olzl,<l ,t1
Y(1,2)E r+g-+ B"l *4'J + 9t+.
olg
'Iflzl $zl. :_r-ll
s" q} zlB ,ilHg E= 2gzl- Ezle+ tyo(l ) tyr(2)
Eql+ 4+^lrJtrl.. I rs.l au

Y(r,21= g-r,rr/ao,
@P GrTtr "-
gA.1 zfl\l Erl ryro(2) ryr(l )
I
-l-
' (noi)''' e-'utq r
rol gz}
1fu"-"""
^JE
E4 trq4 fl= + uflz}9 4*,4zl
ql+61
R9 Hrs flzI +llsE}+ql +6ta szl zzl flzI s9 urs flzI -
)/as )lao
= -l- 1a-ru'+rr' 1a-(re:+rnr
+{Eflt+ql +g C* "l + gz| ?+r+ql +61+ {z}e-l ffi
1
lla;
6J+= +94 Bol 44'J + 9l+.
{zlrJ re,g 4 ne+q $zl rzlzlel zlq, 5¤ +4u+
Y(\,2) = Wr_r,,.(r, )W",,,(r, ) (e4.1)
ol ffifliffiA*61 y\r,2)=we(l)r/e(2)+a ¤ aol+. F

?lzlzl .<le_ zyny+lzlH Aql fl= 4zlzl toJzl E= 2oJzl E
z3g izl HtrI. Q+rJ dz} zzl flxl Aql +6l-z {z} rol fl
z[ Boll +q]qr *g qlE v0,2)=ve(2)vs(l)E + wofilw"Ql wol2lwrlll
?ol 4B¤I 4o14. "Jzlqql4 "lEql el6IH ul-=.o at-
izl 4H,"J 'll= 419 tlal ^J4E ol= EI'J+ "+.="

EI+Eq
+eg zlzlt- 444oI aI4(E4 7c), q - d} rl--tro ++E ]A
wolllv"Ql + volzlv/Bfil 6z,E Exl'"Js
a.H-+L olEe-l de Aq+ Y\r,2)=

We( *Q)V/B(1) l)r/sQ) + ry
rB eA.l ?*71-'Jd trlE:Br+ts 27HE ErlE Erl4e-a
= 7l7la_ Ezl LI+Lll= aol ++. ol +ql^l ++s tt}|Eolll=Joe f.ajLl olag
LEfLHot 6l.71
^JqE LtEtLHTlTl E}|E6I olaJq. aol Hle 0l

=
E d¤ AoJol *g qlqzl :f46I¤ H, EziE d rBoltrf. E^l 1sl fl^l +llE-Br+= -H.al"^{o+, laE ^|E.-"t
E^l'2el +|E-EF+=
^Jqlolq, LalI. 9=.+ ag
glt7l-46J 8^qee ++LHHtrf. 3r* :aJP yn(1)rlrs(2)=,
4¤ql ql6J +¤.4 e3 4ol g+. Vn(2)Vs(1)E LtEl'Jt[. 0l + 7lq7[ 0l TlqE ildol golL8
.-44 gEel c^l "JE7l =dElE ^plel
=71'-dtr1.
eA flIt7F=-st ol= 323
EsE oz!-dol?+7 6J
eA2^le] iil-tr.o6J+s _E^lq= dzl.
4. o¤6J3 qA ¤AG ffle ?lF¤ qlag ol+q, ol +
ql 44^J *g trI ulzl s +llEEt+E d4*J4 ulfa].ll Eol
a
1 I O
7l ullEql olBzl +e. 4olr|(oE sgl aHBalE r"]4 E

zlol4).
4*4:=3 ol"l *fI- ?B"l ¤¤g trll= g^l-+llE.J+E
ol aSzlErl + dxiE e}g "lEqa ^J4619fl+.
o
iI a
ol+lql ,-gel ^sol

qgg ol?-]]ql^l _Bol= ute+ ?ol e.z^19 u1^5,
fg eA.2 darsl F p +llE-d*7f ail^lE^l 4E0l 4r= xloE^1
aJfz|
^JHlq= ^flE
dxl-ld. ll el6l]^J"J BcE f ?lzl oll
o,J-dol ="J
EdErl.
Eq +48+.
@ vBolEoil^1el flrFdfe.t BaH +

0ttlE
+
Paulifl4ql E6]-H + dzlel l¤¤. EEI-6J +al4 ii+*.E}+ 6A7l q2l^
-u
ud-
dzl¤9 szlE ^Js r+ts oll .flsz} H6|]ot 6J+(Eq

=
8B). + dz}{l tr|].J +ill4 vB rrl-t 6J+. +g4 ,J+
Y(r,2) = { r/o(t) % (2) + ry oQ)r4o(t)}o(1,2)
{zlrJ oE ol
:19 eA.3 ,\JE 4Eoe tr=61ts F p flls-d#7|'atrJE E^lo.E^l Ai{
C+oJu}. Ezl 14 zE r}s rlE r,J-dol :ddEtrl.. 0l
^fl
r+6IE ol u|=" grfT} trl¤.$ 2rol ¤4. 3zl^1 ?ltr|.
27HE +E E"Jol Eltrl E= ,\lololl Tn
=-cfe
Y(2,r) = {rlroQ)Wu(l) + ry
o0) ryu(z)io(2, t)
= { t/ro(t) tgo (2) + ry
^(2)vr(1)}o(2,
1)
tql ol +llEEL+E dzls=g.J44^l 27H4 n3il9
"J=+.
Pauli fl4ql qqot 6Iq, ol+41
e-l6IE y(2,r)--y(t,2)7} ru¤6J3 iE o + +*61 d={+ F p ?lls6Jf9 dz|5"1
qElH o(2,1)=-o(1,2)9 aaol "J+qq"t ++. F 4gol 4rzl$e_e_rAl ¤^dg+(rB eA.3). ol Bae qa fl
^fl¤. uI4
olq+ ceg +44BJE trl+4 rJol ¤Eiq"l"t *tri. AA+ "l a'Jg E trll olaol p +llsE}f9 dzl-xlzlB
_Hol7l qlEql sd4(nE pgl oHRaL= r4^ Eztol+).l
I
o_(1,2) =
,* {u(l)p(2) -
p(1)o(2)}
N,ql= 27n4 n¤*ol 9l+. 6i+= + qld6l+ zp, TJIEB
olag elTl dzt 6l]'J.+trHE4 an). q4^l *e qq += Îolql^l E 6t+= + "Jd 2pl ?llEEI+E.<|olof,<l z-
^sql flol 4.¤. zl¤-oEAl ¤cg+. Ir+.4^J N,E dal4"J a.J
zl tlEH(slq! aql.l B^dqs-)= dz} 4Ig zlqo} +
Ett+r aEg+ 9l+ ^gEol
4}ag ol4 o e e+^l s=+
+aE 6l+E oEB4 F n¤aJe-tr ol+qd 4 "e.^l(re
^¤ 9A.4), Lewis *t:N=N,9I P*S4.
H,ql ql+vB ol# += Eq 2gz} EzlqlE 4*^la

+ 9t+. qE^J N,ql q+ bq= 4 gzlel ?)*zl {z} ullzl +
2s22p,t2prr2p,rolt+. SHI4g-tr. eZI Se+¤ z+9E q6I= ft

4."1 $HlE, n].+î + gÎel zp. +llEe}fTl qe edzl1 2p,
+ N + +
+llEEI+e+ r.lE ulf v;'(:.8 eL.z),2ne+ zp, TllEEliES 1

o
i
+
+46}+r ^84r++ rBlE r.JE uff BE 2p, ?llE
ol +ql
ll
N
EL+E + dzlT]. 4rzl$e_eal o¤6J9 "J=+. "luli

^Sg
E +A u+.s" Er+= 9A.zaq o e +qzlq, r1rsE i 2p,Al Veel
EEL+= +4U+. lg 9A.4 o'J-dll F n'j-erqe olFcltl tr4 ExlE +r- +oll ¤B
=-d
qA= olEtl.
4"lzl Nzp fllr*iEep.*2pr)Z qzl ¤A+ql +qI fl 6lrJlrl$ Er|. "JE= -._!rJ
=-J+
+$|oll ?E-d
EB '4ag +$'}|zl fje-Er odQ]S BCB + S+ t. 4 r r¤*3 4*-J u}]aJg olf d +llE.J+E.<|ololl^JE ¤C¤rI.
=
32t, Erl+r
9A.2 EB B g^dq 7lol6k 4ELaJ CEE +QH+r 6]]46J + lltrI
vBolE_q E slqlql -5aoJg E 6I+E +q= 8g"l+. *Eol

+ E"J+ q +4ql d4¤ol ^Jol6|41 BEg + 9lg oll ol eA3^l_e + +4U aqlg rJ4"llBzI. 4l& A+ql el6IE
59 q-e" a;-** +a^lzJ 4"]|4. ol "Jol ++ *oJzlE ol tr = 0.1"J *ll glHzlzl 4++ qq, IrleI^J ol $zli ffi
6ll6lElH ++qI -ao+ ad-_e-_tr_
"lFoitl uct E4-=vs ol Bf y= P.o,,r.nt*0.lyio,,i.o + ++U +B +egl AtJg
Ee-E q$4l ¤E6l-=zl= BE +Eg 4,o14. zl; Hts +ll *=+. ol q-E¤l+= ol $zfz| ="+d4 olgdg +El
EEL+¤ Vra, r4a CBp TJIEEI+E Vse +4r-llts Yn-cr p ffiol 100:19 ul$10.r2=0.01)oJg 9"lal"L 4,"14.
=ve(1)r/rsQ)+tyoQ)yB(1)ol+r ¤ + qlg 4o14. rq+ ol
7l+g E=]ol4 o + f*ol "J ¤+. + ol49 dzt 1ol Hfl
zl ^Jql qlg dz} zzl ctflzl tr-ql fl+r trr.l+ 49 :_ I gA.3 trElrl Ert
ol != ag +4U+. rEl+ + 4zlzl clgÎ tr-ql 914+
(7u.cr=vr(r)vs(2), H*Cl-9 +4U+), E= dzlol UflzI r} 4flzl-Ez} 49 4 o¤6J3 +fl qA ¤A+ ++ls gEB
q flg +E( ya-ct. =r/ra(l)Vne),7kCol *g H-Ct*g +4 'Ha.J
gzl-?llE.J+=q dxl¤"1 4r-d_q_sAl ¤^d
^fl¤-
U+) 9l4.ol EzI9 q +rtl zl+6IEiE ="-ft d 94. n¤6JE uttlz[z]tr_ 4.Jq]']]ael gzl-+llE6]+E il-
6J^J+ olg A6.JCS +A^l4ot 6Iq, :.=lal.{lzl+-Col * z16l+ dxl-E"l 4Lg zl¤.e_Er] ¤Cgtrt.
g H-Cl*g +^16lr-) vsct=ys_cr+1"rr..,-4tr alot tr 4
ol+. q7l^J I= +il al+4. olag "JqI4 o + q-o_$ pol
, I , r'l-I
Try\!.{.
-l
H2O=v3 ol$e-tr "I4e+ eol +Elu+. +d o gz}
g fl*zt {z} uflzli 2s22p*22pr'2p.,o'14. ozp fllr*igl
Y = Y-^..^,^-.+ LY,^_,^ (9A.3)
covalent lonlc
Eqfl= + 4.zlzl ?*3 d{-==$ 44 urs +llEJ+E d
{zJrJ y.nua"*E
"l eE}E +++ ="#dEt B4ql q6J 2d z}e+4zl"l oaq}¤ B^J+tr}(4 Aq}"}+ aHr* oH 4
?J ga+ql +6li^l flEB qla"l+). 2p,q zp" +llE*f
z| ffiarr'q, flonrg "l e6.JE olgaq} ¤EHql Eil6J 2dz|
Ezlql^l= * +z7l ++¤I ="*¤6Jolr E
. ol 5g ^lg 90"= ol-= 7 !l9p + ol + o¤RE .<l_tr 90'E
6I+= ++qL olg a6Jolq, olfl ag olE+J-=B¤ EB"l ol+41 ¤trHrH eA.s). EI+^J H2o ¤:zl+ ?+E= *=+
+r 6J+.AB tr=ol+r +e= olfl ^lel r}E.et+= ol r qltl$ + fl9-q ¤41str r++. r*l+ ol olEql E
g A-J +aCol dill +zI +eql4 rrql Hlql6h= 7lq= 6I ql 2oJ4g eg.olzlEJ dzll ¤4J43 tg4.s"olr+.
-'- {olap 6H4B + gt+. f?-16}q },2<1olE ++Aq}^d
ol zlufl{ola }",>lolH ol$¤o-JC"l zlH]]4ol B+.tH H1s
z Exl¤ol EE6l.= ag +44b 4"1 otq4 q

7lo16l-=
H1s
4 zl{al-b +aEE g+oltr].. "lag ol EztE {la} ul-=."or
+=- e zl* zl4rll Lt+u +qL4 ++"J s"14, ol O2p_ o
1
=^l4e
t- q! t"J zlq +a5$. +e1.4= 49
"|t14. gZpv
).sl <lg ill4l4"e. +6IE]E Eq ecql^J ¤E6J trl-s4
ge HE flflE olf-allo| ++. fg eA.s flIt7l'=:st olEE 0lE6tl,\1 3rl4oe LEF.! HrOE
F oE-dE 7471 Hts ills-d#q o2p flE*# =:sr".
6lLt7[ e^l^1^]
ol+cltl aolq. =E
6J rl-t.e:+¤- gluizlE 7atts :z il
"Je-1e-1 ofl
^l¤-6H^J
alol rlal qlqzlE+ 4a +^l ?++. ll-r
n-r
+¤e 4fl4 +zl¤ sttzl-¤.J oJ$e_tr up5r1l fe

ol gE.el IEE tr!.=:d+4r t4. "l ?l;lq q qI qgg 6Jq *¤ z]]HS oleo6J rlAL +Bf, qlE 6l-+E
HfdE d*"J'll, {zlr-l} "l Ezi9 F Kelort6*
Erll sl$1u1-="arq qlq} hamilton ¤AIzlE TlqlilE + +A.J +a= +$ql= +dzl ?d_o _+ +4U
=
d-q) :. 19 alol al^J9 aolq, trrg olg^J ul-='"9+zl- $
rI 7-
T.5,
eA fl5t71-=-st olE 325
v=v(O)+y(O) (eA.4) zrtrJE! oll 9A4

s&9 sru"ll^]el 4-o1 0zll9 Aqlg
9zl9l Tlqq-= + +a= F"J6J qlq "JE_tril'E++g sflill').
e +e] Htqtr-ql {x}ullzl} [Ne]3s23p4olo + ol aoJ _EL"Jol
zl$ zlzJQ, ,q-+^J ol=e +Aql+ E
EIEIE rs dz} "t+e+:p dz} aI4zI "l* +
"J.J 7lq= *4. ol *H(ol a+ "J+
1
=+lE ^Jol
eI :a +llE*+tr. +{qq +t}4oJ [Ne]:s13p33d2el dz]
^J"l6J ?llEJ+q fl;tz} flzl ez\lzl
H}lzl= oJFl1, ol=-
E.= +A-+a edJE ?olp* rllzlE t+6lrll "JE= s.r+E-
+E}U+ +Hg dzl-E¤ E+ *g qlqzl ^J4E EsqE dB 0211E rflzlz} 4-a* dzl:=4 A6Jg ¤dB + gl
zll 99ot 6J+.
+ 6i7l trll+q $e"o-Jfz| zlld¤4. ol+Al +4U glHzl zJ
6l-= ol Ezt9 EB ?J8EI+7 6tErll, olag HJ6J+ aÂzl
ul-ct4 o tr. "JaEE *E +gqlol gE aol+. +H (b)
g 6}tr- .llHzlE= *+q, 7l"16l+ +aEol Hli6J qlHxlE =c
*ql^l ¤Ef, qlE+H cH4(+-q.JzI Ezl-$ E¤-6J)el e6J
,lgi= 9lHzlz} EJ gol *olrl4. Hlr$lql+ (2)e+ ** + 6:zl]E ^Jaol B9 o?Et(Hlsel-c2p +llEEt+E+q ^Ja)
4+ zlnlaJeEal olsd-*+c ¤LBg ola +qzl 6l+b ¤¤ol *"lt o¤Er(Hlse} czs +llE6J+
^-
6l+6IH Hldel u|=."grfz} a=l rl zHdgg
2
tr+q cZll"lr-lo} 6Iq ,r|4c +lE ¤Ee sd6}zl *61tr1.
qlqzl 4lt} alol a+ q 4ele + 9l+. ol f,!4l. 6llA6|71 +l6}"i +4lg flz}glrJE C2s4 c2p Tll
+{E-*+zl gtlt_ gzl
ÎolE Adq E6H^J =C
E6J+=
(a)6T! E.g ol EC +llEq++E¤ ilzl¤rs trrd E= ?llE¤.+Eol
vs olE9 azl tsd 4Cql^J +4t Ede +^ gzi4 +zl F"Jql dz} 'JsE e4l g+= ^J4g 6lrll E1fr.4. "l g^d
(+z]l9 e*g ¤^d'J+ 9l= bq)= ¤Hg + fr+= a"l e EI eq +Cg E +211E flzL +llsaJfE"l ulzl ul':$21fl
9+. CE Htqldrql {z} uflzli 2s22p,t2pr'E^l ol olgql el gqq q4 tr"4l4 E= _E_rJ4 adg alq +zl]9 rl]e.+ E
olg
alH Ea flzFb zt\lq A'J +Fql ¤Ce + S= 4014. "JEqqb a"l4r ^J4B + 9l+.
ol +dg ++6i= d"l *t!9 7H'Eol4. trl"l+ + 47Hq f,-.:a"e} EC Alra;65 "JE= d¤ ¤aJg +
=+6J
3 qlqzlg +JEEL+E 4zlzl g+71= 49 gt}trI. szfl u1a3g. ^J46IH Eg + 9l+.
=Irl
qls^J +a gzl-ql^J= zs 4zlzl zp fllr*fE +tlqq
2st2p*t2pr'2p,'4 {z} "JEH^J 47llel 4z1zlr ?+g d
ullzJ$ 4Ei1l +llE-d+=el Eg
zlz| ,tJE += fllEEL+i$ ilzl6}Tll gqa {z}t4. ol +
=¤
+H;ll eq} 6I+61+= +fl "J"Jille-l fl..Jql+(3). +d 4
zH9 dzl-L += gz}.il +61+ 4\lE glrofi{cHnE A+ gC +lE++= h-as*b,p,+brpr+b,pr* 33 g-e + + gl
.llE +21e1 Hrs TllEgtfl9 dzlp* 41-g zl¤-e_Eal +z}|9 o rla ,$4a;21 "JHlille-l (1,1,1) ?lE.J6l+ gc h,E a+ql
aqlg BCg + 9lg 4o14. dzl¤ +d^lzlE ullE .llHzl b ^'ll p +ll-r.E47l E+ H4al 7lq= 6llot 6Iq, ol-4,r1
zl- $ealzl"J zzH9 a.J+r-ql "JE + H= gz}r} +Tlql e-l
aFi bEg 37171^JE + ,Jy+a o n ht=as+ b(p,+pr+p,)tl
o1l,<J +zflel a6J¤- BC6Ial EIH F"Jg glulzlE E_tr-6ir.E_
_r. ¤+ ¤cEs t-"J* a^Jg *zl"JteF 5'
91trI. += ^ll
tsg AEfl {lHzlz} +s-+= 4,"14.
F+e f,alz1u3 *t +s+) h,a+ zl_u.agop +tr}. ol 4r¤
Hl]olol
+414 rql rr}= 471i,4 eqle El gzlel 6J ol
e d4l4 a^dg eAl +r p +.llsEtfEE +s= +s4l +l
=A"Jql
4* t +d qlqxlzt 4tal zlzl qlEql 7l!"6J d"14.¤= 6H^l +6[ot 6J+. qle^l hz=as*b(-p,-py+p,)= q6lq zlj/
TI qlqzlz| olrlfl *e 4? z' dz} al47l Hlqgt= zp ?ll
0,0,1)
EEL+E EqrJe-Ea-l zfeE d+qflg EIE dx} dxl. tI
Eg +Axlzlzl ql+ol+r ^J4g+ rq+ ilzlzl qBal 1,1,11
all.<J[z] EE-r. olq^l A'Jg ¤C++=
"l +{E ,l]Hg
'dxll'4col olq+= ag +96110} d+. . olae +"J a 3
l+,+,+l
El"l ¤d¤ ql gqLlE +ill4.J qqxl Sffi ¤E6l-zl fl

il zlt4 ,H'l.J goltr|. (1,0,0)
0,0.0)
(0,1,0)
326 e Er[+I
=flg, 4+^14 E+
f-48, A H
Il,",nrar=J{as+b(n, *p, *p. )}{as+b(-p, -p, +p,)}dz
I -Yr\,
C
I
,|
00
= a' J s' dt -b' I p',dr -...- ab Jsp. dr-. ..-u' ! v,v,dr+..
=A'-bt -b'+b'=a'-b'=o
ol= 4+ <te gzL +llEEL+Eol A+s+qr zlr6J
^JE
+= Îds+El +g+(Eq 7c). El-+^J a_b7l fl$@_-b
E 6H7l-9xlq} olae p +lls*fql q+ ¤Ell fltl-"J +s
azJeA.T ?:7:a sf Eg illE-Br+ 4gil+^lEoil +lil-sl H1s ilEp|#el'
,ll flql 44zl g+), ol + gdg hr=s+p,*pt*p,, a4 eij^1ll o'l-SS "JEtl. 0l ego = cH4sl Lll ¤BEtl'.
a hr=s-px- p),+p,71 g+ ht=as+b(-p,+p/-p,)+
E= --d =Efol
hn--as+b(p*-pl-p.)qlE Hl++ EEg 4+^lvJ + flgq, aJfzl ¤^dqEJH +¤g + 4rl7l4

Hrql^le+ Bol "l ul-="
rq6}q d;llzl " + 'l-g-4 ae e+= EAI E+. 9 ol${oi 6J+. 7+7+E sp3 EC +llEEt+- E+ E"J{L =
pr*
h, = s + pr*p, hr=s- pr- pr*p, dS zlzlo + 4714 o¤*3 +A HI]6J"J trl-= S E+ t-"J
aLcH:zH eA.7).
hr=s- pr* pr-p, hn=s*p,- pr-p ;E=88 .
(eA s)
sC +llEEL+= flrJ ¤qql^J s +llE++e+ p +ile6Jf9

"Jq + ? E Îolql ErJ tdol "J94zl trilEql ez} gq
a+ ^jE +tiE6J+E- îolel ,JE A1+17+ s¤ +llEEF+ ql^l +3 d+¤- +Elu+. ol*lq! er+e at;J 4l7l7l s4 p
e 4Eillel tlE 6F"Ib + EoJol ¤4t:zH eA.6). g^d +llEEL+ ++"J trllE+ rJ6l]zl= 4o14. :aElr "l 6zl-9E
= =
+llE++EE + ÎolE 4IE= arccos(j) =r0e.47"o1+. 4l g. a6} ^ll7l7l +4 9lulzlE E J6l] += E 6t+el ,q"Jol q
C +llEEt+E=g tzl]E s ?llEdJfq 3ZlE p +llE6J+E ol+ 7lE +4.
o14l 4olo + olAg sp, E¤ flEg++r +=+. NTHE gzl +llEEl+==f- o}rj- luzfl9 g^d +llE.J+5g "J
olxll E{9 fl*zl 4tJ +z7I qxll^l 44lE F" *
"1ts E=ql, ol=g d+ e6Jg ¤ôi6}7lE 6l.I E a_ + tI tlel
c_H a6J¤- *b aHxll Ezle 9*zlE drll 016}]g + gtril 4zlzl a.Jg 6}zl g:-r. IaJ drl$e_-tr. tsol{Ez} E"J"ll g
qfl+.+ +11¤ cgzlE 4 Ec fllraJa* 4z1zl ?+e d 6&9 ¤ + 9l+) 9tg +E 9l+.
zl-= 6l+$ zlzla_ glsq, urs dztzl ol54 qrg zlol +E
ill %r-6J19 6F"lt o¤6J9 ¤cdlrll g+. qlE^J gc +llE6J zElEt q eAs
i TllE*fE+q ^JA o¤6J9 r+JE" EI+= q+4
t ,r+ lso vsol$e--tr Hrozl ol+r ?Its ro+.s"g aoJ4}g ¤B6I
*"1 ¤4(A++ 9zl t*9). 7l +l6ll^J= &i9 2sg+:zH9 p +lls*f7l gcg+r
^J
4dlo} El4. *rI4 o e 44E 5+6J sp3 ¤C +llsetfzl
Y (t,2) - h,(t)v _(2)+ h,( 2 )r4r, (1) (eA.6)
ar _
Bd¤qr ^J46il EzI. rBlH 47t1E 4zlzl atg olFB

g^d +llEE zlzl6l.q rq6}q + rg dz]-^d."] ¤
^l +
4. :41 4"lzl dz} Eol Hflzl¤g + dzle+ 4-g "l
+r + o-H ¤*ol 10e.s.= olE+. ¤xll9 ¤*43 +H
Al 4r+ Aqa}rll oJzl6|zl ?+eq, rflalq ¤xll9 gd
3 ¤zlrl ¤H+ ar+ EzI /J."lal4.
109.47" E^JE ,]]Hg ol+otfl EqI qlHI EzL H2C=CH2e-l +a
* z+ e.Jel HI$-B Azl^dg ¤Eg- + 9l+. .llHl E4-L
¤HBol{, HCHe+ ucc EaJ4Eol rzo."1l 7l4L+. ol o¤6J
fg eA.6 -d fl^19 s fllE-d*el'p ills-d#Eol EdE sp3 Ed +z7l +4+BJE 4I +A gzl¤ol 2s'2p3 ullzl-e. ¤=dqol"t
=dElcl
flE--J+. 0l
=d
+lE:Br+= 47llq,7J7: E 4Eiile_l +l= -d:drl.. Ei1l4?.! tL+.rfl+ ol $zloll.<J= ol 471],4 +llE.J+ 4*zl g^d +ll
E^l "JE= 7 4A= +rl:dtrl'.
eA flIt7l-=-Bt glE 327
\
I
t
\
120" L.-
(a) (b)
.f.g 9A.10 ollElel 3= 76. r'zj-dEtrJE LfEfLHfitrl. tr^l "JE=
Erll4oe Ex[ + T?l-e =Et
flEB rl,|d sBE olErl.
fg eA.8 (a) El sflE-Er'+et F pfllE-d#E ol+olt! 37HE e¤
?{lEsr-+E3 EE 34EE +xlE=E BF:dtr|.. (b) ?Jl--d
'Jol.?]E p
tlE:-J+= illEgt+Eol Eoll +^l:srtrl..
=¤Elxl hr-s+p, hr=s-p , sp Ed +jlE-cr.+ (9A.8)
=d =?l
ol + sc +llEEL+= t'-ql +"J+.r4r ol ?J
e+ ¤a+
r$;g trJEE ql ol+qzl ?+eq, 6}+e-l s +.lsEtfe} F EEL+el dzl¤$ 4E cflz}$ gC ?llE6J++ Hrs ?llEdJ
pTllE6J+uJe-tr ol+q{ sd Ed +llE:d+7} B¤E+.
fg dzls+ 4Lg 1=+. 4 fl2}.il tsoigl= F p +llsEt+E
hr= S * 2rt2Pt +zl +ql +461q r dzl¤ol + f{ r46J9 "J=+(re
eA.lo).
hr=s+(+)"'p, -(+)'''v, sp2 Ed flE:Et+ (9A.7)
+E gC +q6i= EC ,J^lg
,J^1, 561 d +llEEt+7I
ht= s -(i)''' p--(+)'''v, ol+alfl qq q= zl6l-ql4 Ezl *aE ¤Eg + 914(s
ol g^d ?llEEI+=¤- ¤E^Jql^J 120.8 ol+r EE Alz,F eA.1).
^-il
¤9 Eltdg 6Je}+(rg eA.8). +trlzl eI zp +llEEL+(2p.) ffiElq eA6
E^delql +q6l.zl ?+eq, :a +ol gc +llEEr-+=.ol + sF6+ sHill Ezl¤ ^J46]l tr-zr. +++ ql eA.4ql^l
?3
= H}I6JE+. g^d +llEEt+. +q 4l+.E=g tL
"J Hql +zl6irll 4 ?"1 *9 d4¤ol +dqg olq^J sp3d2 Ec o e c
olq} Y o.E zld o ea] {t"le} +e gqqlî Hr} z}dg .J 8flill$ +{dg o}6l+ 67]]E 5'="{ g^d ?llEE+¤ "J
q+al aI¤ :H"ll^le+ B¤ s."39 +4U+. sp'EC cflz} -=T.
ErI
+= cflz}9 ¤.C +llE6J++ Et.Hls glraJ.fe|

=
g 4Lzl¤.e_EAl :41e1 o¤*¤. "J=+. EI+^J oE43 C-H ^fl E eA.r fllE-st+
=¤
s+ c_c od6JEol ,rJe r20"E olE+. F cHrzlr| F"JH tr" ufl+l+ -e."J ec
ql +"J trll. EcElqzl ?+g p +Jlr.JfEE + 4zlzl 42
2 d¤ sp, pd, sd
zl"l n¤6J¤- "J=+(rB qe.g). ol rpaJol ¤cqH ¤H H]] Hlde sd
il E4 " + raqq, cH, zlSol !-tr qd6IBlE n¤*ol J :4 ¤H sp2,p'd
qIElqol"I +trt(+ EzI9
"llHzlz} f,zla11o1++). Hlqa ¤E spd
d¤ Ezt"J qlH HC=GHj Hli6irll ¤E6J f glEcll, ol
ull} cflzl-Eol ffi$ B* sp ol+q, ol gC flzl- :4 ul4"t pd'
=,$9
+llEE'+E. ols-" 6|{ oae.=¤ "J=tr}.
4 C+Hzll sp3, sd3
+Ezll spd2, p3d, dp3
zlTl
--l --l
-dIJd
o Li p2d2, sp2d
5 ?7L 0=
J1 Lg sp3d, spds
^
+4 ul4"t sp2d2, sd{, pd', p'd'

s4 ¤E P,d,
6 aHill sp'd'
3?J g4A spda, pds
3?+ E?Jfl. s?]6 p'd'

.f.eJ 9A.9 ollEJsl 2e,JaJ 7I; nrJ:doJE LfElLl1flrl.
328 Erl-+r
=e-d7HE=
! l. aJ flzlql +61-= flz[ flsaJ+q .J.zlzl += +]4q +6t - 4. nZ!-dg qzj ga +ql +zlo}zfl p +lls.*fel ul*el 4?
ga} +llE6J+el dzte+ r5g l{g e}zlg rli 4*ol ol .+El+= A*"]4.
=
Bdgtri. D s. T3.zlzl Hl +llEEL+s ErJal +714.J a6Jg BCg + 9l
Z 2. o?!EI3 qrJ ¤A + +9lE qag +4'dr}. 4ts zllH^}9 #6401e-p t4.
tr 3. q HIgg gz1 g|e-{rl ^Jolt {z} ullilz} +e_E+ +a tr 6. 46J+ zlo.}^dg 4/l 6Iq +7lA Aag gsa + 9lE+
Eol 6aq= ¤tr-g ggolr+r,*4. oJ gzlE flzt +llsE+Eol s{}q= ag
qL+.
=d(s+)"14r
=s-d^l=
.dlTl
a, +^l al Hs
=. ^l
flttz|-¤EI y = vo1)rysQ) + ty^(2)ryuQ) lfl"l 49 olFolo} tL+ 9/..2
JI.Id
od Y= lYioni.
Y.ou,1"n,* olg4-t+atJC +B 94.3
g^J h = as + W + ... E"J flzI {t9 e= gzl +]EEI+ 9A.5,9A.7, "l ge.g
z}^1l6J o=3 -$E *e,
r 5g zl¤E o_(1,2) = +{o(l)p(2) - p(r)cr1z;1o14.

EEgB 0l=: t^ 13
=rlTllE-Et+ =rl-0
E 1"14.
> 0l E4E uH?= ole
4 iM=EVr-=_ Eq^l ?ts tdzt YIEdJ+E¤
Schrodinge,
Erl-+lE-d+ 0l# 7fl7fl Elrlel.r.i{l # EB:d 4E sE EtEt
eEtg 7l=61= 7l*71IflLl.
Er[ ?{lEE+{Mo)+r. 6J+. Ex} +]ls+f rr= lvl'*r"k
I 6l-{ Ez} Lli+ql^Je-l dz} EE. +Q$tr} Ez} +llse}
E"
> E{C TllE += gz} +llE-J+e+ Hl*6IzlEJ Ezt dz,llql ea^J q4 ?l

Erf ?llEg+= Erl'el -EE flrl'illl e8^1 nld ffi:gr'fol$, +
EEJ4oe g^l +lE-Bt+EE dE Satoe LlElUtl.
> gsEt qHl rEl (a) dE E!=71

=:d
flrl'fllE-Bt+E E$(EE 8A)rl 4"8:d+e+q qLlxl= olg Hr*oll qlql^J= a]|44 oe. Eflzl"J(Born-
Schrodinger
4l ZltbltsrlAE=f 7C) +xl6l-r. ?lolot Uttrl. q7|^1 EE6l.= ^lol
oppenheimer J,<l- H+l "Jql^l) ol+rll ¤q^J 9= u1-="a;-*
Lll# EF Born-oppenheimer =JHol -trfl.tol E{l rl^.l tr)
el H+ Lroll=qlr.!tr|-.
tr}]tdl ffia3 B+g gqq ol 4= 4flzt 4lql+ 4+
= a+ l;,[!o]zl"J += +zl¤ql+ d
^le +tr S.+. "14^J
al qt}^lvJ + ?lE a+ EJ ZI+EL "JHg ¤ BszL ?14.
+lE-Et+ olE(Mo ol$)ql^J= dx|$ol A.Jql lr qI"J + 4zlzl gzl. noil +6I=- flz| +llsE}+e+ E6J gz}
=rl =A
9+r dill Ezlql ¤! sld+r E+ ol ol#vB ol +61+ flzt flls6J+E qL +qlîL+ tsAg + gleel
49zl Bql
E(Eq eA)E+ q y*ol gd6}g.sq, ¤zlrJ +g +q H +Al4oJ ,l-E.o6L.Ae q-q_r+ ?ol "l + gz} ?]lEgI+Eg
=lt
Eg e.Jg ¤ql4eE b6l+ ql ts"-l ol+qr 9l+. *E 68"+ 444oF*+.
Eq sAql^l= rdzl-4lql H flzJ-= zlzl_t_ flzL i.a olEg
dE (98.2)
Ed^la +gql r eq¤ tsdrl4 44zl flzlg +aE ¤ %=N.(WotVru) ?^1.+lE-Er.+=el
=-ct
E6Iq+. :.s] ullaj rl$ql uI4 Ezl +llE-J+ ol-a_$ izfl {zlds+ Aol Hr*el A+ql= WoeI VsTl zJzJ $zl Ae+ Bel
g + ?lErll, {zlrJts 7}A} A++ Ez}"J +i Ez}-olg H2* flzI +{se].+o14, N.3 A++ "Jz}o14. e8.241+ eg gE
5 ols-" 6]-q a.JE ,lE ¤H6Ijr" ol pffi olo-" 6l.{ 6eg flxt ?llEil+9 dE linear combination of
=ag
q +tlq} alE +a= ¤¤B 4o14. =:EI(LCAO:
atomic orbitalslol4l. el4. r?]a flzL +llsE}+q d¤ aq+
e e o15"1+l olBl{IEzt fllra;tag. LCAO-MO4
rY =^}4"J
98.1 flrtillE:#ECE =+.*4zl
¤zlrJ EE6l-= EzI +llE++e+ *"1 4Z}
=:d ¤a + ++ls ?lE¤ 4ag ?*+ a? o+llE:d#4l 5-g
ur*91 Eqil= E}"J dzl.9 hamilton ¤t4-E +g!+ A+ 4. "lae +ql q+^J Egl¤. uI s TllE6JfeI ulfalzll Eol
q, q eq.6l "JolzlB 4+ ¤a + ++lE +.IE 4s*ol
fi=-+Yi+v I I r\
0ol7l ql$ql Bg 84"14.
"=-*( (e8.1)
I
fo',' fu, R )
--r---
¤zlri ro,4 rr,3 F q Ae+ BE+Ei e

GEEUE+'IEB+Ea;I+
f",
szlnlzl! 44"1q(l) R¤: F q ^Fl fo, +llss}f rrr.E e+El 6Iq 4.
eB.2^lE Ezl-
E 4?-l+. yql +tl ^lql^J gs "JE zqEt Al=t Wvdr-lol q4l 6l-= "J+ Ng +6110} 6L
zl¤. + aJ¤- dzls+ q
Î"lE ^Js+ 4, ol 4Ee d +zlql 44^1 6]10} el+. ol 4eqlq *
1
+ql EqL "Jqg +4'll=.,il4"leloll 4"lzl .&g q ^l-ol el LCAG= Hir" gzt +llEEL+=ol zHH4_oE a+slq
Hlg tr.g4}¤¤ +4q= 4o14. ^J+EE Az,J Et+naol
e_]
q fl+= ol+6J+.
*es ol tlql^J 4+ +4+Erll, olag a+a,rreE LIEI ^ldg
330 Er[+r
7l^la- Hl+* llthg fl Ar+= rH eB3ql +r}.11fl+
(a) (b)
r4eB.1 (a) #EIFole-E eEtErt+lEe+7tF ¤E:Sl"= Eoll^j

2
LlEtLllts T.!g.* (b) 0l [!E_E
-siE raJ.
Bq +ts El+r+ ae a4= eg +

=ot
glEI.
1l 5
ryE
* +z v
[w.vdc -N] ! v'â, !,yiac I ^v,dt =2(l+S)Ni
¤zlr-l Ag gt 4491 9¤tcHol

S=Jrynrgrdrolq, :a
'Aa 4e'e +q q+dl +s+ qgg B 4,"14). ,'+¤| feJ 982 t^ Exl-ole-el nlso-g+ rg.zf t-B[ufli FT]+ sEe4lE Eg.
^l C+sL "Jzl*
q-q-+ A+
I
"N-* - {z{t*5;1" +
Hr*9 a+qE S=0.5eo14 lr+et^l N+-0.56o1 g+.

471 EP] sl.t
eB.2^lel v_= C+e+^l7l-L s-o.se"J ql
el N-= +61q4.
0I'I = ,lrl fvtatr'.r,{(S- t)z}/t =ltrt:E

feJ eB.3 f Exl-olEE trls-Et+ y_z[ upfutl! BT]+ EEIZIE sg.
^
rH eB.tg eB.2^lE SzI flIEEL+ %q ql+ E" -t!* CS
+ElU 4."14. olel* rfl=g ^lS J-sEflq= ol+6t{ (b) e-d ilErt+
dril rg + gl+. ol 4l4}g ql+61 a*6}q, F gz} +llEE+
Borndl4Bql 96tH Hi +9 4 dql^lE dzlE q¤ "JE
+E +^19 Eq^lzlz1t:16}E 4l4I 4+?l +e+. r ul^="fl-;e] 4l+ql Hlql++. eB.2^lE V/*ql
=
q*q+ +E-I'JE= q-q-q Bol ¤4.
olrNl + Hr'+llrg4=. 0l+6lo1 4l4I+ gA d+ H59 tyl* Vri+ Vi+2VtVs
=ElqE
"JE (9B.3)
rHeB.2q ++.11fl+.
ol *E "JE= rB + gzt fllsalfz[
eB.4ql s.r1a1qt:cll,
v^=d7o-rrtlq vz=
I
e-'sr
/'o Hli+ d+¤ *= qz} gqg a^l6fl _H_H ,* +sEl
1*1y g +H6lzll "l"llp + 9lg 4,o14. eB3^lql E6IH dill=4
q
{zlrl re,4 rs,E EB4ol o}rl4(l), gz} Aq E4d ql E "JE= q+r+ Ag -J=E .Jql tslql+q.
z|=-E 3lS= ol+g 4l(2) r^, _ {xi + f + /yr,, ol ,r, = l*
+ f + (z- plyytrze+ e"l +4lqq, Rg Aq+ zJololc[. rr_E
- vi, 44zl flzL e9 +llEE++ql +6Jqr ^J4*
g qlE 4-E "Js-
eB Erl ?{lE-g+ ol=: +A ErFolE 331
. vr{, 4zlzl flzt s9 +llEEL+ql 4aJ4l ^J4qH, {r

aIfl?lg "l dz} +4"il S+g +E 9lr "le+ +H¤ Zld
g trIE q¤ trJE. -
'lo 4e gfl"J +E 9l+.
. 2VoVu, + gzt +llEEL+ql el6J q+el +E "JE
Rr
il
'bl "J+ ¤B*oflls*fE A+q9g + fl4¤ A*^lvl
ql
7lq. r[u elr 6Iq, olBl* flIEEL+= fllE-*+41 +4. r"lr.
=-et
oTllE¤fE d+6h= dzl¤ oflIp}l +sq, ol{oJ $z}
ol ulzluJ7lq= erJ ¤Eql^J dzl¤ gag +EE ?zl=
+"il +"Jt dzt"lE(Hlq +qq H,*"ll^JeI ?ol)
+4'll= 444"J EBg 6Iq AE Es+r.6J+. ol *89 =461== uflzlg
ol EzIg {z} to,E +4u+.
*zYY + gz| +llEsL+7I u_234 o + 7ld6lzl trI+q +4 ofll.sa*iE qlqzl Eo* r+q-r+ *"1 ¤4.,
\i+ ol ul-s-"9t+==-o- ez} ¤qql^J "J9 a+g 714q,
= di] 1l+g 4zlzl qL qI flz| +JsEt+ql +*
ol qlEql Eo:Er,.*+-# flEEl+E ofiLi^l (e8.4)
=-d
g trIH+ q 4^l= aol4. "lBl6J e4. q+4 ?"1 se}
g+ el+ qzld Er,,ts Hrs flliaef9 "llHzl, jJRi. + q
gzl99 ^plE Hl
B ElHl¤ qlq40;e A+n¤o{ eI4 tlzla}4z|), -:.
gzr +.llsaeliE-"l aa4^l BzJ4_o + tdol "Jq+=
4r s, j,k+ q-q-r} ag A+ltr}.
*ql^J= {z} ujEzl izlalzl trl$ql egtol BCg'}.
++4"J ¤Eql qsH + qel 6a sqqî {z} ujrz} s-Jr/orlu ar={r*f.u(*)'}"--'* (eB.sa)
+olzl4H dz}Tl "*+ q4 ^llr] tls4}¤¤ 614l q= +lil

E e+ol +trt. rBlH zJ 1j.zlzl +"J q6Ir"J ,r-llz.ll tlEzl* yi"!#a,=f,{r-(,.*)"'""} (eB.sb)
g 6t= +"]¤ flzlollr.JB4 4zlzl + q4 tls4¤¤ 6l.L

Ezi9lrJ glHzlzl q *rll ¤trI. rq+ dxlE qz} gqe k=i"lry ar:tn^(t**)""" (eB.Sc)
e. olErlTleJH r qfl¤ 9lHzlzt +7|"ll"r 617l trllE"ll "l

++4 ¤Eg +E6tzl *6I+. + +++ LCAo uJ;EuJq E qzl,tl jJa"? trl-s=r+ gg aolq.
ol +E6l ¤Bg + s.eq E+ ¤'H4"J ¤B"l _ ez _ e' ,rtm"e' = ffir¤o ZhcR*
= Îdg io
%-4IE¤"rt- 41t%^-ff-W
(eB.sd)
9,aap4. 4^l7l ez} B9 o + &AzlY a4 E^lql g
= j+$+r ¤Ealt lolqqd6l tc El]^J
zI TllEEt+zl
olzl"J). ol +llEEL+ ffi_o + "J"l"JoI dzlg+ q {z|e=s-E +4U +il= 27.2tevol4.*E ^,ll 4E
2hcR*9
Îolel "J
qol r4l ?zla}¤ eZI ¤9 o e 4zlzl ol:a"oli.rll t'+= "J #:zB ss.s"ll E^16t9=Ell, olf$'l+r+ ?"1 "ll46J f
eltr}.
q eiE ^J^ll6lr blsq, r"]6}q d¤4 "-+ qfl¤ qq
=Al *"t+I4. 4eql^l {fol H5}q d
zlzl ol
zlE 3¤- qlLlzlE H6tzl"J ol &F qqzl H+= EIHI¤
qlqzl Hq.il "JEg atre ++.*e_e= 4l+6ll^J El+ a
*E ^llzl GzlS ea gqql^Jel dz} "Js +4 qEq+r 1
¤EB 4"14. HiE t +d-6J Ez}"ilrl glHzlzl *"tzlE +l 0.8

\ 0.8
\
0.6
\ \
g-'0.6
o \
o.4 \ o(
s 0.4
\ \ i
0.2 0.2 --------l-
k
0
// o246810 0 2 46 810
(a) Ha, (b) Hro
feJ eB.s Hioll rll-el 4E (a) s, (b)jel k= q4z 714a --J#e xltl-d
=4.
fal eB.4 rg eB.2= "JE= E1l olE-d trtE-Bt+E x1ffi Tlxla 4ltl-d
E^1. "JE qq7J gqq E^t "JE7l-Ht^lr ?l=¤ +p-6lqzt. r sr.+^19 +E= "l t4l"ll qq} E^t"lEel ,!.4+ 4*n= e_otel.
332 e Erl+5.
olE 4Ee E+ "J"lq, qz} A4zl 4dql

^ll
uI4 o o + d=dJtrHse+ /c- zl+6} trllEolg j= qq
d2l 7t^-l
40 Uts O-
l/R oJzI ullEol4). zl+ s= Eq ecqJurJ Q z|,r-lJ {r
6l ¤Hg 4o14. -
rlo
Rr-
4E/= 6J qr+ += qt}9 dz]. "JE

^l-olel ^J
,bl
i[
gzl+ AEE +qU+. nlfl
/c= qr+ ae.il zl"Jqi ez} 999 4"J dz}

"Js_.r.1o1E ttAzl* 4EE +4,J+.
aeJ gB.t F Hrs ?1lE-tsf+71.e^{^111 3-d ofls-d*E U= nll golLl-=
H7J 7JE.
L]trlEt o{l s.2
4l4I Arl.il E6IE(¤:E trl-S A E"E 6tg R=2.4eaooll^J
zl zlr$trHrB eB.7). rel+ 44zl HF 4olzlE d
4zJ
4^rl ¤4. ol eA 44ql^l= trI-e-,,r+ ae a+= gg + z| ujEz[ *zl.* o]q+ eA
el+. "J6J +Aol Bzl ?]=tr]. +"J
"l trltEql Se qz} ,lElql^j
t*g-(r/Rql Hlql6l-=)E Adc|.
n.+1,-' n' Ezl +llE.J+el 9lHzlzl 6zla}4, r?-l6}q qd¤ qlq

,= r., = 0.46 =
{t* zl +dol z;ol hcb"! +Adg +4U+. H2*ql q+ al& a
r+ql E6IH. R.= 2.49a0-l32pme| hcb"-r.Z6ey(r7l kJ mol-')
i= lff I - 3.4e ea.s, | - o.3e i o r ao
"lq, de Ar+= 106pme] z.6evol4. trI+^J $zloll rflaJ
ol
*=
!ro+ 2.49)e-,ns = 0.29 i o I ao ol ++q] LCAo-Moz| xJ$alzl= Ezlqj d-"1 Q+q S=
tr}{^l ag otHg "J + 1l+.

jJoo:zz.zl eVE Bq+H j=10.7 eyet k:7.9ey71
g+. a6J Moe+ Hls flzl. +llEEl+ ^tolE qlqzl il"=
(c) U3-d fllE-d+
Eo-En,.=-1.76eV7I ¤trI
eB.2^lE dB aq+ v_y v*ql BI6]]^J +e qlqzl= +Eiu
4. "l fllralfE 9rl o+lls6.t-fol7l qlEql o*E E^l6J+.
ol +llE6J+= qA +ql +zl6}jr" Woel v/Bzl Cq-6irll
zB ge.6g +?-l¤ fl4-S9 "llHzl= zlfreg 6J E"E il ^J4l
g 44 n9 6-J+tr- E^lql 4"14. ng 3 aIsE+El ei^l q= e-J 6adql^l "Iq Hg +4u+(rH gs.sr+ eB.e).
q¤ I'JE= +g.r+ 4.ol ¤4.
4 .ll4zlH + gz} .7llEEI+ ^l-olE Ert TJdol .=!7t6}q
ea gqql^J dz} "Jszl rtzl-tlu1-e. o?llE6Jf9 9lulzl qE gE
V?* Vi,+ Vi- 2VoVu HJ=-sr (98.6)
ol -2rrovs6} nllEql + q rlol9 q¤ r,JEzl- e}id4(rB

eB.10). E4qL4eE "J6IE + flzI +llEs'-+7} Aazl= g
Eto
o o'(o ,) qql^l t}4l zld"l gq+= 4."14.o.+llEEr-+= HJe-s ill
IU
i 0.1 E-S+g + ql"Jql, ol +llE6J+rl d+qE + flz|,tp1e]
I
'b0 *d4"1 E6llzlr. EzI9 qlLlzlT} E"] t49 flzl¤ql Hl

Ftrl+.
lU
$l (on) 6il^l
g' \
.--:
K o. Hl¤6J +llEEr+el gluJzl EdE trlgr+ TJLI;
5 \
6-0 ; j-k
Eo.=8",,*t-i- 98.7)
-0.1
0 2 46 8 10
"l ^lql +4+= 4E s, j,a4a kE

¤;!7J )1?.:|,, Rtao qs.s^l o-e +qzl= a
fg eB.6 t^ "J Ej=-sr fllE-st+9 Exl tr1El¤

E^l-ol8oll tH-d Eol+. Rql trtE Eo.9 H+= rB eB.6ql +EI'Hfl=ql, *
ollLlrl= Est^l7lE^1 ZllbG ge +C.
=-Er'
ollLjrl EoE oflE
:Er'+g =-Er' =01=
ollHllolr, Eo*E o*flE:*#g 0llL1^ltr[. E?] 7lE ge+ uoll tt|6}|,\'l= 2 ol p$i ol -u4l g^t"lEel tl^ll'* 4*a9 "JBg "l*a}¤ gg aol
+oll ¤Bdtdtt trt.
eB Erl fllE-Et+ olE: *+ ErFolS 333
/\l. qq
o+l ll 7[/\l
Litl oa
(a)
(b)
feJ eB.lt 'J*lt U=Er Erlg +E4?l ¤8. (a)

floJoll B-d +lE
-cr+oll,\its -.jZ gEoll =-dHJ=EI
-"-4- Eol'JAq'. (b)
C^l "JE7l
=7|.6lq
fllE--J+ollll= "_!rJ gq HEt +oll dxl.
lal 98.8 F H1s +llE-Br+7l.ail^lll HJ=E|-o illEtrr-+E "J= nfl "JGlLt= "Jrz1=7l6tq Hle +o_e -"_{=01
Llztrf.
8^llrJd. =al
#JEt q eB.3
e.J qlLl zlzl +)++ q= dql^J Y R=2.4e40o1r, E ++

/ + q 9B.2ql el6IH 5=0.46, j=r0.7 eY, rfll k=7.9eVo14.
r+zl^l ol 4?lql^l= Hlaq+ +llEEL+el qlqzle+ +i g
'l \
zl.el ls +llEEL+E qlHzls+9 ilz[ u]-e-=q-?ol ¤4.
(a) (b) (Eo. -EH,,) t eY =# -ffiff = t.,

lal 98.9 (a) #4 Exf-o|go| HJ=-st E^l fllE-sf+7| F qq= s-El6l.=
Eol[t.l LIEILI|E T!rE-* (b) 0l C+ol=^lC rH. trlz ofE]7f 9,tgg +E-6lq$.
r46lq ol qA Zqql^l= +A'J +llE6J+zI AE+ +llE
"J+ q t4l +lil6J4.
oJ+H+ (s.7+1.76)ey-7.5ey
¤-J dz}q E"JAo+ Er+zI g +4+ 914. ol4fl aqg

+El.I. ++4oJ olf-b 4zlzl gt ¤q "E+El E.e+
uI? 491 Eelzl ollEolr*. ol sr+ ull$
^l +E Aq+ ¤9 9B..2 +llE:d+ E'rl
ql e.J 4z.lzl + qg .q Bq+=ql H}6ll^l {l¤al dzl
rllq+E+(rB e8.11). ol rHe +ql ¤Bg E.
.F 4¤- E4 zgzl Ez}(qldtrl] N,e| ?"1 E.J gêl ; gz|tr E
=
6I+E +ag +4U+. lEo.-Er,,l ) lEo-En,,le+ eg Ezl¤)E A+q=:a Ezl-+llEe.+ql+ ud E|la¤g s^l
+4U+.+ HIA.J=,+llEEL+zI ++'H= HlAq+ s4 atE 4"1 f+61+. Eld 4aol* Ezl ?JlraJ4E Ezt 6
=eg
E Aq+ +llEEI+7]-+4.1t= A6J sr+B+ q =.4. ol c(aq+rll= Hld +c, Eq r0A)g E6llî Hld^lag ql
=!s
+ 449 ++4"J g"Je e-q H}tsg;n;ol + Ezt +lEsL E ^d¤g +41+l= Aol+. qlaEH ¤6J oTllE'J+ t}g "JE
+e-l qqzl= +q+zl ullEol4. el ag
^J46tr,
olq^l ol a o ++rl Ezt +dg E" rl,6}¤
Elql¤ql ?l= 5144 Aql^JE jil^tr.oo-l_AE +s= aÎ++
(re eB.r2). +"J ol fllralfzl E"J +EE 7I¤ trll= E HJ
I
E¤g Tlar+a B:"tE orqlrlsi u-"l EzI gE E¤=4GE
,JE 6d
:x os o
\
fg 9B.12 Exlsl EHe UEoll e.l6}|,\l fllE-Bt+7|. E6l^l

geE r =C= =-Lf
+lE-Br+= st UEd(g)= 7l^lq, U"J trlE-Er+9 Paz|. Hl+lE
leJ eB.tg ral eB.e= UE= r1l ol$-d trfEEr+E /N-d E^[ Ud8(u)E ,Jtstl. ol=tr! 2g^lE^lts Ejd ,Jrl oJe-E-+ g, u E*
^llfi6|.q = =C=
"JE -.-qZ Bqel C^l. "JE7l4ol^l= a= ++6tGal.. sl'F+61'tr1.
334 ErlTT
4Lg *61-= +.Jq geradeoll,tl +48). qI¤ Hle6J o.lllE* ol Hld

']]a Eft 6Cg *zl $|g ol+q 2gz} E
Hld
+ql+ ?Je =.4¤^ 4+H +llEEI+el d+e ?zl"J pszl xHcoe| z.ol F tr"le! giE flzls=E ¤ zflz} BzDqlE
HlqE gq. oltrll= Udd(ungeradeollrl +?-il)g Tlflr+a 4+^la + s+.
=
"J6Iq, o,ql^le} 4z]. uE Eq=+.
T]ILJE
=gET
I l. Er[ fllEet+= flz] +llsBfEE dB A*g z[z]r q1=
^l ^Ja+.
+. J 4. o?{Ed*E qrJ ¤A + ++lE ?lE¤ 44"1H, ol + +
3 2. EEt flEA+= "Jd gÎ +{E6J+5E Br} Aaql 9611^J +19 +llE 4e5"3=ol ool+.
^844. tr s. ¤.q 2?lz} +zlE $z| 745q63 f Eld El|ACqI lt+¤l4

I 3. HJ=-ef ?{lE:d+= "Jd gz} ?llE6J+E9 t}4i aeql E61l (g) EE ¤(u) HldC -trzlE Et4.
=e-d^l=
,A-lzI
o=, --1I +l 4 H-a
gz} ?{EE d¤ eoJ Wt =Nt(Vre t Vrr) 5q 2gal. Ezt 98.2
F rs +llEslfE "l+qd o?llE6Jf9 Eo = Er,,+ iolR-(j+ k) / (l +s) 9B..4
9lulzl Eo. = Er,, +iolR-(j- k)/ (l -S) 98.7
E4ql +t 4+ s=lyoyrdt, 9B.5a
j= jrlgr'^lrr)dr 9B.sb
k= jol(VoVrlrr)dr 9B.5c
EEgC 0l=: Zfl\l-EIl
=Il+llE-tst+ =-4
(a) otl-E-d+st rutlE-d*
> ol EEE Hl{+E ol*.
Elet4o+ Erl# 7.lelE+7t 27il 01.8E Erl.= 7[xl]L ,I+ zI+qI 4dz} zi)zl EzI"J HrE ^Jzl6llBz}. 4 HgzL
?io.q,
=sEl
qelll 0l=9 Exl Hll^lTl olgxl trJEolrlE_rl golot:drt ts rs ?llEEt+= zl{a}{(H2*ql^Je+ ?-ol), e_9 ssql^l ¤H
0l EEoll^1ts E^1.= 27}l 0l,S'J= Ertollq Exf ilE-Et+ 0l=g 6J HIe| eol ol$E+rl oe+ o.flls.g,;r} BCg + 914. B
B qt zl"-lql^l ol +llEe-+Es:zH sc.tr+ *3 "llHzlE
olE4l 4E^lTlbrlq 96fl^'i ¤Eg aolq.
> -._Id TllLJ *=tri ol rHg Ert +llE:*+ oilLJrl faJo14-l BE

=+{
4 Erh +llE-et+ drl.= z7\nl^la-l +EEt f 9,,{o4, olE Exlel 4.zzl4 flzI +llsEL+E+q* zz11E Ezt flIEEL+ "J.l "J
Hrq 8Et|ts r drl Hl1ilTf arl qlLlxl= 7l+! nfloltrt. ag ++6l.q+. "J*zl " + N4lE flz} flls*
=q{+=
+E+El= NTHE +zI +llEEL+zI "JEq+l4.
> =JgEl qlHl xl^l
HJa-J= 0l+ 4?le dzlE Eolq, olEg pauti9 s4z} s+d+ q.tr.
EE eBoll^1 ¤EEt "J fl^f fllEB+el dE
,JEFal g^l-ilil rHei=Et flal(s.g 8B)= (Eq 8BE flz}qlrJs+ Aol) 4zl*HrJ ofllsElfgl
4a +^l6ll0t EEI. ^¤g
Eqt+. Elr+^J Hl-Eltlq {z} ullzli orol4, ol a6-J oillE
Ei+e-l {zl{re_e. Ao.Jol ol+q4lq. ol %}Bq Eflts + A
+ig flz}9 +llE6J+e+ +a fl45 ole" 6|{ 4dx} flz]. oJ EzI +llEEL+qlE al46J + tlel 4zlzl a + 9l=
E Htq^J4 dz} ullz'l$ +qL a4 u}{z}zltr s.4 gsglrl ql, olag slql a.Jql *eL Le*is9 ¤84 ag =qr-il+ol+.
¤¤+ rdzt +i Ezl-"lgql 4+ EzI +llEEi+e+ E9 ss ol EHg ol+6LE BEol q4l^J zi)zl Ezl¤
"J=zl ?*
ql^l ¤B+ +a g4= gd^14 44zl zi)zl $zls] ols- ¤Eg + il+. gE gzls=g zlzl rs fllE*+E Lll
=zl=
9 dz} HI]ZIE ¤Eg + 9l+. +eq, 44^J oe+ o* $z| glrg';3 "JE + ql4. "lE fll
s.fl$E Hrel aE4 tr-^]l6irll= rt=21u3 r "JHI4 EoJg
gc.1 drl Hl|il aeq, Ir+4^l e¤4_e_EE. ol qlqzl rBg 0l*6ll^l
=9
eEg E$ + 9l+ ifl+ld dzlE Ei +zflol{, "16t E3 o
zedzl Ezl¤('l olgE)gl 4¤I EzI +llsErf olg(MoolE) +llEEt+ql E{zE" "11"1 4 z|?lzlE +"lzl Eol o.tllE
E ol¤- zl+-d flz| llega= aoJ6Lq Ezl +{s EL+ql E"lzl"t ++(rH eC.2). E|+^l H.r9 ut${l4 dz}
=ga3
6J+¤. Hl]il: oz o"271E+.o.E E4E flzl-E=eq qlqzlz| $9
"JE= 4.o14. "JE EzI +llEEI+= "JEB flz}ql zl
+^la'J ar+ Hl++ +a g?]= ol$a|{(trq 88) H}E} t} {, .z CE= o9 9lLJzlz} {o}zJ}- z$+u+ E+ q r+.
4 dzt Hl]il= +E}8 + 9t+. ol qlEql He, Ezlt z}]zl]9 flzl¤-E 9lg trllB+ E"JA6}
+
flzl¤ol .ll+= dzl-E9 pauli9 H]]E} ?l?-lql 4
4 qI +llEEI+ql a zllnlzlE} i]]+lzlrll 6IH^l(r^J o*
g "l-+sE) di] "ilHzlz} 44zl qE+ 4 +JE
EI+q+ zl]?l4zt= 4o14. il
otj
gzlql^le+ ul.4lzlxl_tr 94 zl]9 qp|¤ +llE++ xi
r(l-
H1s H1s
zl ?19 tr1]= 4 +llEEL+ql+ Er+ 6I+4 i]]+ ,bJ
r q^J ffi {zffii ifl+l g ql dz}- U

6 o
dz} tl$ol !az| Er+).

=+(ol+al k
nl-j
fg ec.1 Hls flE-d#=o| A8^1^1 'J=oltl fls.g45ql q-d Erl
Hund9 41q1 ffir +4(Eq "l-4 dzl-E
8B)ql
+lEEl+ ollLixl raJ. 7J?:? EE ,'Jololl^lg ,Joll
=fl
"l tol* qgl ?llEEI+=g il-zlts ull= olEol =91= ^lol9 =-Bt
6]lEJElc.l-. H2E HFJ8E[| d^l'Ht|^l= aFl E^l +llE-cr+(=Et +lEEr+)oll 27ile.l
al'}|q ¤B ++t-HAl ullzloJQ. Exl'7l.it|gT.! 10|tr|'.

^¤g
336 e
=rl+6
2s 2s
o*
p, 2p,
K He1 s He1 s
5
6 A B
o fg ec.3 E^l-+lE-Et+ olEoll E6lE otllEE#E 4-st-d Etl8E ?=

-"= gxl +]lE:Br'+E 7l^la_ u=tr|-. 0la= 2+7lg Ea{ 2fl^l.E^loil^j=
fal ec.2 7l-84 4E^t El^l Her9 utefAteH d^l' E|lil= 27HA'Jil E^lel 2tll9 zs flE*+sl ztll1 2p, ?llE-tsr+7|' 0lEEtrlts ,l= 90l-eltrl'. 0l tll
27llg dJ,Jd d^1.= +=r1.. olae EalE fl^F=Etrl ollLl^l= 7[^lq, ?llE-Br+e+E|47ll1 Elrl'?lEtrr'+E "J= + ?!q.
rel6lcl E?t¤61-tl'.
=e
zlfill{; ¤B+ ,}]Hg Eq 2?lz} +zlql "JHl4e_e 4+ E + 9lzl"J). 2p, Tll.E 6JfEql q6]l^lE- u|t}z}zlol+. trl.4
¤+. q7l^J ^l¤-+ +H4 HJtsql^J= flttz} 444 +llEEt ^J
ol$ + !
^]lEel +llE6J+-g Vrz, Vsz,$ Vxzp, Vwp,
x
+5"J¤. ol+6ll^J gz[ 1]sa;45- "JEqE +86]q, r?] g-ol E+. ¤zl.r.J +_tr aqlsl= a=.g a6J +llE¤:+=-, :z=-l
6lq 2+71 flaEe. ¤ Ezl¤ql 46Hql^J= 2se+ zp flzI ?Jl -a --s a,*q= aEe HI A'J Tlls-a;4E +4U+
E-J+EEI ^g46IE g+. $z[ ?]lEE]+= E+ +ill4q1 x1l=_"11 tr]4 EÎts trll
olxll
MoolEE gHI4 g4= trl-e_r+ *ol 449 + 9l+. 7l E)fl4. :z44ol a4-e. ?llE.J+5914 se} u9 EzlE E
q^J Hld qla(Eq eBql^l ¤HqDg +4u+. olq^J Hld
46J6J'l] ag *= ?]lE6J+Ee d*zl- Ezl- +lls.J+ql
zlol= ql-+.
4?ol F"JEi TllEEi+E ^llEE ?+?+qlq +il. Rq=+.
r?-16}01 2s TllEEtf_A+El Bcg o?Jl=.45= 1or, .ael-tr
¤a+ql +6H^J gE¤ qlag *= lt= flzl-

:1?-l6}q qZI ag +llE6J+s+q ¤cg o. Tlls.gtl5 louE. +4.d+
+llEJ+# dB a6J^l7lH oTllE6J#5ol ElEqd4. "l qA fle +ql tr}4 Hflo-lg * 2p, fllEEl+EE El1+61
qt +l1ra;49 UI ?llE6Jfol+(r
flzl-9 zs Tllsstfe+ 2p. Al flil{, ol dd"l tr.a4 oE "Jq+L+ E= ^J414 o +
^-ll
B qc.r; 4 fl4¤{ zq"l qe ¤e+ ^Jql fleq, "Jd g "Jq+L+ql tr}+ '+r: 4* r.= Hle6J o+llE6J+7l. Bc
4 4*.J"Jtrl). trI{^J ¤Cg + 9t= o+.llEsl+el "JHI4 ¤4t:B ec.4). zp flzI +llEEL+= 2s flz| llraJftr_+ qI
gg +94 ?ol ¤4. lqzlzl
^J'Jt61 t-zl
ullEql olE + o+llE6J+E=g lo*el 1o,
-H.+ qlqzlz[ $9-{ r46l.q zJzJ 2or* 2o,-E -tr^l6Jtrt. "J
(ec.1)
V= cezrVezr* cszrVszr* corp,V nzp.* cszp,Vzzp. ol +llEEI+9 *zl^b qlqzl *zl i\ql qsq,
HI4 "s ^J
4lf c9 {}# olE +z}l9 flzi fllra]
4¤6}111 4eLe-Eal
qaq
ol6J +llEJ+E-g Etr + *zl-3 E"JtrI= 4g ++
+E+El o449 z*Y +tll{ EzI +llsEL+E EI= + ?l+. 4q+
q-gql= gzlel 2p,* zp, +JlEetfE ol=
4 flzi9 zse* 2p9 F fllra;-a5 qlqzl iJ-= ?*71 ql 4r- ^J46l] BzI.
=
Eql ol=¤ +716ll^l +l#ts + gl+r {4r-+tr}(+ql ol 7} e qa ¤e +q +zl6}q + flz}7} d=6IH 4Eoe a
col 9s flrll g 4"141. + ril o?Jls_a;.ag- o+ + a + flul. "l aag HrJ tdol olqE t1-41 1.,Eo1a -u4
=î4 6I"l eEL E= Hle6J 7r+llEe-+E- "J=+(rH rc.s). r?llE
r1= + *irbrll, :. t ^llE=
trIs=$ a3 EE F zs ?llEoJ
f + ol+{tl 4o14.
* cnz.Wsz,
ffiffiI
V= ce.zrVe,z. (9C'2a)
rall E 6t+E
^]lEb
trl++ eg E9 F 2p,+llE++s
2o
ol+qd aol+.
++
V= cnzp,Vtzp,+ cezp,Vlzp, (9c'2b)
2o
Eq 2gz} Ez}glrlE A?lzIeI B?lzlEq 2s TllE*+ qlq
zli.!E Aq. q+^l 4lfEs ,!e. ?olo} qlq{+E= tr} fg ec.4 p *lE-d*zl' 4^{^1,\1 U=GlT.l "; HJ=Ef o fllEB#Eol
=Er
+d= Ell4oe LEF.! raJ.
ec fllEg+ olE: EE4 2flrl Exl 337
=xl
Hlxl
r-iLl -/\l
6o a
+ + + +
I
(a) (b)
TI
s
lt U
lg eC.6 (a) F +llE:*#zl gal "Jcl^1 ?l= fl^l5oll +-g ttt|= 0l fl^lEol
Ai1^l= gEoll,\l tr|.E:Br+7|. a]g.q, cqel,\l s7[ atEl. (b) 5 fl^l'71. TlDlol
.l.g 9c.5 n=Et "l HJe-st Exl'?llE-Er+=E HJcd. tr=-g nt|= 0l=01 ,Jxirl= Eqoll^l + +llE-tsf+7|-8.J-Lf Tl+= 7[rlq,
qatll s7l 10ll tr=g + 9ltrl'. -LzlLl F fl^t7l- qTloll LIEII! 7i-Ec1 11
Tlzlol tr=6lE p fls-*#9 89 Tl+01 s flE-*f9 ge-l T.!+rl2J^1^l7l
++9 7ls.= flz}9 p fllraJfei ulSall.tJ +g aqlEll, ol s7f trl^l ?4^5171^l+Eltl. raldlc{ + ?^lE 6d0l "Jilalzll
^1461'E.E
EIE S=001 EE.[.
ag EzI +ql EI+^J eE n?llE6Jfzl. p TJlEEFzlfl Eol
_r. E qz} sa + +flE 6J ++lE +]]E 4}+F*+ 7l^l7l
ullEol4. * AilE eEi q HIA6J zr,TllE*
2p, +llE6J+7I
E ec.l +4= TllE-Et+= ,\lolel AA 4E
izl ^}zlt- E + zp, illraJfTl flilfl + zll9 ry7llE*f fllE{}+ aa 4g
7l NrJLl.Tr,eI nr46J fllEgl+ss trlEElq ?l4."lEE HI
,={,* ^^
Aq+ 4IEvl4E uffizlzlol+. rH ec.sql^J _Hql Bte+ gol
ls, ls
t.+(#)'}.
¤B ru+lls"}+Ee g Hld^d(u)g zlzl4 Hlee+ r?Js*i
s=e 4.HldcG)g *=+.rr-l6l.q *e qlqzlE + 2+ tr) 2s,2s , =
{,
*
#. +(+)' . *(+)' }.-^".
s+ +llEEL+Eg lnu.E 4441" +g qqzlg trls+ Hla.J
?llEEL+Eg lnr-tr ++Utrt.
2pr,2p, (n) , =
{,
*
#. *(+| . *(+)'}..'"*
(b) afl 4E
2pr 2p, (o) , = -{, * # *
*(+)' - *(#)' *(#)'i"-'^''o
+i Ezl--olgg ¤Hl{g uls+ rJ"l + "Jd flzi +]sE}+
i. Îolel -HrJ rJdql 7l"Jq. "llHzl zla(:zel-r. tl"4l ZI 0. 8
dql 7l"JqE qlqzl t+)= +llE6J+=q Aa eE. +q (4
uq. Eq eBql^J ¤E+ uls+ *ol + gzl. +JEgL+7I a,(l rH 0.6

kr 2s,2s
eE= +94 tol c99= aa 4E se. +Elu+ ,t<0
\
= Rn 0.4
S=
Jrtriyo dr ed 4E t89l (ec.3)
0.2
1s,1
\
qI.J eflz}9 flxI +llE6J+ VoTl4r sflx}g Vuzl zH(E 0
r
HI'I"J ull), ol=-9 #"1 qq^J+ 4Ie4, olE +E qI 0 4 812
647J 717l,ZRtao
16 20
=
C"J Ad 4Es 4Lg aol+(rg ec.6). El"J vr^4 vsTl 4 1
tr +<I gEql^J 4 ?ol trll= ol gq "JE E= Aql^l s \)n )n lt\
E <k* zl4 + gt+ ="J"J + d+slg flxI +llsl*izl \

= 0.5
EF6IE(qaq +"JtL 49 rs +llEEL+E) s=1o1 g+ a
(o)
o -----+-------------l
+ql q4^J= Ad zJ+ol ++6J +q zlz)E_ d-q(s n|l

0
I
ec.r) olag re ec.7ql +E|49+.

=E Rr
(0
0
6H7l 71; tl TRle
1 0 15 2
ru
olHql= s illEdJfz} toltr gzlE p, Tlls6Jf9 +Hr+ 1
-0.5
aazl= Hllgg ^J46]] E4(re ec.8). F ?JE.J+=E #
"l "J"J ¤Eql^JE 4E+ F +llE6J+89 #"1 gfl gEql -1
^lel 484 e+6lrll tr-4qq, 4+^J

s=0ol ¤4.
"I4rJ , aeJp(..7 + +AE tlE-Bt+ tolE 'JE \si 5= -.jZ 7lal9 -et#e LIEIL.!
+JEEL+e+ p +Jlre+7l ol4tl ul]¤g 6} a+q]= ds a raJ. Sq ,Jol E tttl= -d 2p +lls-d#sl gel Bq4 clE 2p +lE-Er+ol
g+. gqzlsl =01
aE0l +:e_zy EgEl + Bq ,la= 571'61'11 El=
flol ool =E
.-!rJ TlalollF 3^Pl ^l.019
?l^1617l ttllEoltrt.
338 r 7-
=rl.
d2l
!o E^f fl^l
=^l
+
2p
a{l
q=
1
r.al ec.8 0l raJql^1el' eg Htlepll rEl p +fE-Er+7|'s fllE-Bt+sl eE
E= q4A Zalqlî !a aa 4E0l 001 Ec[(5=0). 2s
tr"lel ++g +{EE}+5 ^l-olE aa aEE +4,11= a lg ec.10 E-"j 2g^l.E^toll rt|-d E^1,+]|EEl+ oilLl^l raJ.
0ll 9l= C=A flrl +lE-Er+EE AAoll sl6H^l ¤71= E^t fllEEr+=9
=fl =g
a 4¤+ a6J B^Jql zl¤aFb eE= Lt44= 4ol4r E ollLl^l= LlElL,lEl. ?l_e Eaps+e qlLl^l7l.Eol.Tlrl EEoll,\l ul.et
+ ?lxlEl rslLl ol 4E ahg +E6H,(J ol$aflo} *+. rq eol 0l rEE Oz(rH9 Exl'Bt|xl)el F20ll E|'|6t|^1 /.l'E6t|0F:dc]..
^14-d
al-¤ zp,4 2pl TllEsL+Eel He +Eql qq} aa 4E+

2p, T11.E*fE r}"l9 4Ee+ dB4 " + -a{, ogaJol ru
E ui4zlE^J +^J7l H++(rH sc.rl). +Tl¤-stlql^J N,
a6JB+ qI6I+= ag gr-Î,*trt. rq+ q Îol gE4 +
vl7ly a4 ec.tzel +^J7I 4+qq, ore| Frql qlql^JE r
tlql^Jg H?t 4d9 o tr-s++ +ol El aq ol4ol ?EI"ll
trlil= ar+= +ill4 AA AEtrq q +s6l.4 ol e4E B qc.rog +^17| 4+g+. ol ^Jql4 +^J= flz}g zs ?llE
Er-+e+ zp fllre+ r}"l9 ,J4ql "14 4+¤4. "l ,J4+
1n"4 rru, TJIE6JfE 7J4ol E"J EzI u-o}el zore| zo,
-fllrL$r:-;-=
<rr-:l I F
^Lolel
/Jz={5.q q¤ 4" + ^84{lq. ryef^l ul
,r.r^f .r-l .,l A -,I
^
-- !rl-l-l-l rl .I fzl9g."llrJ f+e-E ?J++ ?zla}4 "l trllEql N, +=ql
^f.l:
-l-,l -I-I
.rj tn,el zor9 tr-ql4 +^l7I Hl^fltr]-.

+llEEL+=E {r-'Izl 9luJzlE re ec.eql Hql A+ +e
= ruill=_6-;-;5 ol4 ?ol EzI +llse$ glHzl rflol e6fleo E e
4, d+61+ dzl-==g ,J* p +llEE}+ja+q + =9
E_$ olllEo]ffi A+61+ dzl-E=E4 A.Jol E s44ol4. 4aqi fg dzl¤ 4a fl4ql lr+4^l +JEEI+Eq Bq+
H Ezl¤q Hlq%r-4 dzl. El]iIE eg + :14.¤.olg ¤{4
&3rI ole or-e+ eg)g "lol 6c fl21tr4 q Be dzl¤
(c) z+z I 5-eI z?r.,l Ert ill+lot 6Iq, "Jolg +(o,*e| ag)g E il]+E B+
2+71 Eq 2gz} Ezl¤ql 4q} ExI +llEEL+ 9lHzl f;91 102flfl fl;tz} d4¤ 7l-Tl N,E ^J46l] EzI. + dzl-= 4I
rHg +61-ElE 87Hel fl*zl ea +]IEEI+E(4I flzlE+q I "JEq ror+llre+q EqTI^J olag iH+i1 r+S + d
+zl]4)E+q sz11E Ezi +llsEL+E "JEq"t +tr}. 44 4 zl-!. ro,,illra;4$ iflgtrI. r46lq 67flel 4zlzl BAI q=
tr + d1}q= +^1. rB gc.roql +4.11*.=ql, ol49 zsq rJJ, ffiel ln"?llE*fE 27HolE + 016. 4117| ol# zlle
2p, TllEtJfTl lr+ {lolal
^llEel Ezl +-lls6J+E- EI=+a 4. "Izls| F dzl-= 2oF EqzI+. tr14^J N,9 HIEI ^J4
zf{ail ge Aol+. dzll.ll flq^J= "l= ql Slx} fllroJf {z} u[z]i 10r210,,2hcu420!zl ¤+. trllEE H]¤q] +llEEt+ql
E+71 qZI ¤a + ++lE E"J6J qag 717]|4, rr-l6lq trE= EolE 4ol ¤4ts ullzl. 9is4, olezl 6IEIE ol d
d-Eo e--tr 47],tr,4 o?lls*iql TlqE 6Iq, rr-l6}q "l glHzl
+.\171q-r+ ag oLq+ zL^]* 4l4i a+ql el6lH 2+71 Li Bu, Bz C2 N2 02 F2
2o u
2ou
1n 2o
s
U
2o s
1n
s
K
5 K
5
6 o
1l
u
1n
2o"
s
1o u
2o s
1o 1o u
I
fal 9C.9 EPollll ¤B-d Ble| ?Jol 1n,el 1nn ?llE-st+= /.l.olel z1zlol os
E"J E^l.89 zonel2o, fllE*#E /.l'olsl zSz-j.E:l zfE zioe 84qq,
q7l E?] Hl-g.l ee Al44 ollLlrl= LfElLJrf. rg ec.1t zitl 2B^l-Exlsl +llE-Ef+ ollHxl Etrl.
=q!
ec E^l fllEEt+ olE: #4 2flrl 33e
=rl
fl^l' E^l- ?^l F2 Ezl+ 02 E^tE4 zzll4 d4¤ Q zlzlr- glsq, Ir|4
^J
r {z} ullzJe+ Aq} il+= tor2lo;22oltn!rn!a* b= 1ol
+. Er+^l 9z16}= +"J e.J Ezl4. zl-t
F2E Lewis +ae+
2p
4oJ Ne, Ezl= 2719 dzlE r.l zlzlH, q+^J {z}u1zl}
tojto;2zoltnltn;4zo;2oll b=0o14. ol aEt ih+r- Lllgel
rgzl EzI de4 3 *E ¤4"14.
trB 2145 ¤aJ 4"lg+ A6J ^ll7l6l.i1 +flqq, eElel
2s EE6l+ ql 4+ f-s"+ y].4"1q+ + {t9 fl{¤ r].
=
^Jg
olql BCq= AqlE zl+= q-q=4 Ae îeg ++U+.
feJ eC.l2 5oq 2flrl E^toll ct|el sr 6tL|el E^l-+lEE|+ ollLl^l raJ.
=g N2
?le EapJ+e qlLlrlTl tsoltltrl. EEoll^l
^14-d
Hlel ,Jol 0l raJe + g4¤ ^].olE aq+ zL+71=++ ol flzlf .r.[ {r
-
rlo
nl^lg 2flrl-E^loll rt|d|1,'.l xggcf(N2g Ht|^l= E^l6fl tsgttrt). olE aEtol #"ta+. Rr
rl0l
eal il-+zl !f) aEL

^-llTlzl
ftz|t;]\ m
q{tt
z| zl$ rojroj2rrlza!tr-
't440t ++.
ulf
2fl4 EzL{lrJ9 ds e.Jel a7l+ trl¤4 eg il 2fl^l Exls+ 4flz} EzL9 d¤4.J A6J ?ol59
.g ec.2ql
=:Et
# ue. +r1U+ ++4H+. a6JE rllzl= fl4# +6J61 E4 rllq-ai rll
gs+ eq+ ql',l^l hcDo"l+ E= trlHI¤ +E 4ol hcD"=
b= ](N- N*) t5gl (eC.4) "H?-l
=-BI ^l+ +aq-=Ell olE Îolql- hcbo=76p"-+h(tA +4171- ^d
zlz)a_
{zlrJ Ng a6J +llEE}+ "J9 dzlfoll H}eE} +llE B++ s emql ol hc^4 ¤e7l g+. ++ql +9t+.
^rE
'J+ ?Iel dzlf"l4.
89c.2 eoF
z]trJEt q 9c.1 =:st
aEl il+ R"/pm
e.J 4 dzl-tl$ ¤{} 2145 r"J? gq+
+llEE'-+ "JE HH I 74.r4
r" Hla.J ?llEEI+E 4 dzl4l-g aE r"JE a}^^la+. NN J r09.76
Hrel a+qlts b=r"Jql, olag + gzt H-H *g HCI t t27.45
^l-ol9
AElql 6ll'ol++. He,9lrlE &=0014, ¤B"l BCHzI 9* CH I 114
CC I 154
ql ql.J Lewis fa(:N=N')el *q+9E A4ol+. 2 134
3 120
. trl Be {,t5ol zlE ¤ql

r27ll9 fl;tz} d4-= *E o,e1 HiEltr-4 {z} ullzl} t. 6J ¤+i|E+.
++qq :14. "lBqill iz}= 4flzlBalql Ell
e ec.loql "J46ll^J +6IoF 6Iq rc2;olzor2tnftnr2(Eb

s, ec.3 eA 6]|el qLlIl*
rojro;2zolrn(rn[r)zt Etr]-. tr]4^J p$ i14'- b=+(8-4)-2
ol+. rq+ +a gr-lql E6IH 24lE rru, dzl-b
^Jol+ +ll aql il+ NAhcr,/(kJ mol-')
E++= zlzlaJQ. + 6I+= lnr*oll, rp-lI E. 6l+= rrrr"ll HH I 432.1
EqrJ+. olEg olilH troli +llE6.J+ql il]+lzlEe NN 3 94r.7

^g
Eol ¤qol?+ot 6Jr+ q+^J C)2 Ezl+ s=19 ds r-fl 4 HCI I 427.7
eF+g 7l^1q, Eq 8cq1.<1 ezllf, +qq q4 eL+6J tl CH I 43s

CC I
4o14. dzl 4fl3 zlzl EHlEel ?l"Jol qq, 4+^J o, E
368
zli zlzl+ +ql^l E4zlb t}zlzlcg ++E 4o1u|(E4 2
3
720
962
18c= _E_oI+). ol qltlg y3 ol$qe.+q= +szl ?*zl"J
. q y+e atE"l zle ¤"ll ++qq flcl. olBqill *zI* 4flzl-+4q 4
dE4"e qqlol Elfl+. tI B+iltrl.
340 e Exl7I
zFJEt ql sc.2 ll-e
rH ec.l2ql E6tH NreI Nr*9 {z} uflrle} p!} 214-

q-q=4 ?Jtr+
Bfl
-
rzlr }l2
N2 lollofz ln!2o2, b = 3
N; lo!lolzLn!2or, b=2i 4=71
trd714
848^l
"Jolgg aql i}+zl. zl-ee-E "laE 4q qlq 4zl 4 +
zlg 4"14. ql4 qlqzle-l ¤ElZlg NzTI e4skl mol-'ola

NizI 842k1mol-1o14. ral ec.14 BE^l'E841= 018trt +^l'C 3(UPSoll^l= CE gE$olr
xpsoll,\l= xd fl), 81714 FE47l', -Lalr F^l ?J=7 |e Elcl gltrl-. El$71
oll E6t| 1 CÎ Hl-.J z4?71+lcl^l= ¤E= CrlE +aJoll rqal qE+.
9C.2 EJEII#JH
A6Ia E. vE 9H ole-g+ 9luJzlE +6J + 9l+. "Jd^l n
fl-ot EzI +llsE}f5.g +d6l ol-azl o e u3s
zlftztlz) EEHg Koopmans9 olEol+r +s= ,^,1^l 6l]4
=^J-=
q+ql, "l olEql,<Ju ol$E| qlqzl 4E Flq+s=
lol*.Erll, olE9 flBa4= ¤e4 +Az S94t dztE
=4= ,Jqa 7Ia6J+(=,ri=-¤). + ol¤-+ ql
tsdrl #E(PES: photoelectron spectroscopy)g "llHzlTl "J +llEEL+ "llHxls+
4tl 'J4¤ szlq ¤+^14 tolal +llEe.+rE=spq dzl. HzlE 4zlzl Flq+g +llEEL+E 9lHzl4r -H-= 4o14.
g Elo.lrlorl zzl.-L;r +1 -.1
a-7) ol
-i olE
o ol9_6lzL olo.lr]-d uloL olL- z]z.LEol ]Izl-I
',.ii 6il9 nllol
..ii-i ol 9-61 crlr_lzl9
--ir--- ''i _i,.1 -i.i=L -iL-, -H
'1!_+z rHt;L
Ti -i-i --1 o"|-l- d i e.--i--l'rj E''i ,*u L,..t
=-1
rli_l
= ^ê =
a$E+Et EzI +lls$f .lluJzl= "J"I4= +%IBol4. += Îdg +^16l+ 4olo + E$qI 4o14.
olg+ =Îql
"llHzlb HIAE fl*zl dzi"J A+qE
*zlzl ,r.l-EE olgs+^la qlqlE 9luJzlE e=99"t aI +zlE ,J
F e, "JÎ ¤'zlel qqzl hvts
^lEE
olgE| qlqzl re+ Flq f dzP=ez| rls + z}fld gq.q u}^Jol 200nm ol6I"J H
+g dz| BdItE +F 9lHzlE oJ6J al} e"FF ++ g +Îd fl o e rl-$ollot ++. gE "Jd+g F6]|^l L+s
(rB ec.l3).= qg olf-afl.<J E}g ¤+7I ol+qzlbrjl, ol Hg 58.43nm
= =
el rltlg (rs'zp'--+ 1s2)el He(I) o F^-1, allrlali
*E d $zl.
hv-!m,vz+I (9C.5)
E qq z1Y zt.zzeYzl ¤cl. olEl+ %l?lg 4= *IBol &
ol * zlzl HJ^_l_oE EJ c"J+ ^la + 9l+ +d oldzl gld tsdfl HH(UPS: ultraviolet photoelectron spectroscopy)
^l1?
q4 t}olt +JEE++E 6el qL 6I+E+q +g + 9l
ol+. qd* dzl¤ ¤+6IBIH g^J q +e qqzlE *z}
=oq, 4rJ *olEI olgE1 goE +rt. trt4^J E AloF qI+ r?-16}0l xdol lrol=Ell, "lBl+ E"Ig ¤+=
"llHzlE "JA
xJs=g zlzJ hv=lm"u2+I,E "J+^l7l= 9fl9 ^Jole} # xPS+r +q
{lulxlE g4l E+. ¤zlrl r,E +llEEL+,E+El dzlzl +l"l *dz|9 S qlLlzl= .J+4 442114 ¤6J 1tzlE "1$-
'tg'IE olgE+ "|Hzl4. tr|+^J "*dz}9 # qlqzl$ + "lag + 6}dg ;-/.[o]e %rd
6H^J +ed+ql(rB ect4),
zl-= F4^14 a AeE +lrll 6l= +zl+. 421*4
^,ll7lE
X* + e-(HJEEI=, E,.) a¤6IH t"le} +q, ^Jol6J 3E "llulzl9 dzl.71 4e
hv- l. zl9l EE=o14, :-4aI¤=dz} ++3 +A6la olag AE ql
LJzlql r.ll6ll^J -Er^l6IE *dz} gg + 9l+(rfl
X* + e-(Erl A}E[l)
ec.ls).
^slEflg
I
h
zrEtEt q ec.3
He(I) +Îdg ol+6IE ea Ezte+El s.63ev9 9E
qlqzlE old4¤ +9-Al g +
"tlHzlE 4= 4r S
flE-st+ i X
feJ 9C.13 g^1.= hv9 Olt-lxlE Tlxla g^lEtrl. +lE-Er+ rEFel d^1.= gl4. He(I) +Îdg 21.22ev9 qlH zl$ zlzlq, trI4^J
EglLt|ts EilE /,E ollLl^l7l "J9'6lq, LEIÎ ollLlrl= dxlTl EE 011L1^Le
Tlrl? Lle+.
ec Erl +llEg+ olE: EFI 2flrl Erl 341
2t.22ey=5.63eV+d,ul4rl Ii=15.59eVo14. ol olgp+ ql

LJzl= N, EzI9 4lr qlqzlE A+¤ +llEEL+ 4 2oe
46-3 fll=s}+tr.Pq dzlE qlqLil= ql g,q6J qlqzl+.
4.53ev9 $.dzlg E6J e¤El=ql, olag 16.7evsl ols-
'lol
p] +s= ?J
"ilujzlql 4'*614 rn,+llEEl+.tr.+fl 4,"14.
17
*4zlzl ,J=qE tlt: tl-=.l]e-l oJ=olgol
¤ru-zr o + r==E 16 18
0l8Et ollLlxl,l/eV
19 20
^Jaq trolel TIE tr"'l]9 "l¤-9 =E4l alt rll* tolel lg ec.ls He(l) E,\lC= 0l86|.q Nrsl BE^t ruJl=a
{lHzlzl- g,q6}q, q+^-l oldzl-5"] {t"lfl gE qlqzl$
=8El
zlzla_ flq+e+. ol trilEql dE

"lrll +z7l +E++q, E llE El^ll +a= rH sc.rsql E?l NrE %ldz}
zlE df+ql 6llR6I= TIsf ?J44 dEol 44tI4. ol ^sltrH9
16.7 eY9} 18eV,<l-ololl,tJ +EI+r 9l+.
T]ILJ=
=g-et
tr1. $x| Tlro;i} 46JqI E|]ag z*b e= $*zl fllE6J+E "l i]]+lTlEl.
I d¤ " e eel6}q "J=r+. tr 6. dxl¤ol trol't} +llEQI+E¤ a+g ql= rEE ¤
42. 3rl4 o + o+llsE}f:. flliz} s +llgaJfel p +llge}+s q"J q qlq,.lzl;E+.g ¤4. ^g"l
+El Ezl6ll^l "JEEI. a 7. E"J+ + gzlE g Ext+ ol¤e r i[+7[ a
tr3. rfllEfl+= p +llsg$Eol +H o + 444^1lJzJ 4o14. Elol 5|.rJoltrr.
=E =++
tr4. afl 4Ee ?JEEI+7I Azl= AE= +ElU+. tr 8. tsdxl EBES $z| 1lso315 ¤+d+ dz}9 qlH4E
!s. += g4ql 961-E pauli9 E.l]4 g?-19 -'1¤- oJs LHq^l + aad+ ql ols" gtr|.
9lHxlz| :i,li+ qE+ 7l+.e EzI +llsE}+ql dzl¤
^ll4
=sEl^l=
,\{zl
oe. AI
-1 +l al Ha
aa 4E 5 =Jrpirgrdz d +rJql aa 4+ 9C.3
a6J iI+ b=*(N-/!ft) rvr| rv.= ,+?+ 4*+ HIAEI ?JleEiig d+61-= dzlf4. 9C.4
SdzI E+B ly=!m;?+I rE l,e }fl fllsgf,E+qE "lgcl9lHzlE LI$Utrl- 9C.s

E49D 0l=: 0l=-4 ZflTl'Erl'
=rl-?llE-tsl+
zfl*l Exlql ql6J ,*H(Eq ec)¤- rqlE 4H q=Ell, +EI

> ol EE_.]= H|l+E 0l*
+ gzl¤9 .lluJzle+ *A EETI tolts +ol+.
tH?Eg E^l-=P 0l=tr40|q, qal^l 0lEel C^l 7471
+^d a.Jg trJE- d{¤S +f,-!+ ee Eel aq+ +zl-
3+el olExl tleq, 0l itol= 8aJ4oe ++E'JE= =-4ql
goloF
Eltl. +llEEL+= il^l6J+.
> V= ceVt+ crr{n tr;E-Br+ (9D.1)

"_4d
T]{LJ
=¤ =-s'E
o|=eq 23xl E^lel E^l flEB+= f + I7l g¤E7f Erl
=Et ¤zlrJ + 4l+= Bxl t*4. flzI +llEEL+ wo9 ¤6J91 46J
Ee flrlsl fl^l ilE-Et+=B 0l+clrl ?ltl. HJ=-sf fllE-Bt+=3
0let HJIHolrf.
71q, + dz}9 +lzl= zlzla_ E "]l ol4.ol flz[ eollrl tsd
=t 4Eg |tol'oll, VuA zl{E lcu;2ol+. Hl+C t+ e'J"J
> Ee.,Et qHl rFl trll= lcAl2=lcal2o14, E ++*
"lg aEL"J trll= * 4lfzl- ool
EEI 2flrt E^ le-l E^ l fl lEEr'+(EE x)el 63EEt sladel 7}lE
+(qflQl 6*3-ql^J= cA=0, rel-l. cs= 1ol4). *g 'ilH zl9
(EE 7C)e golot:ettrl. 0l EEoll^1ts BB^l(ElEtIlE Ar^l 23)r+ gzl +JEEL+= ¤.J EzL +llE6J+q1=- zlqE 4q, Hlqls
EIEE +EIE{EE lcelElEtxtelS^.1 s)g o|Eelq.
HIAqI EzI +llsE}+ql= +g qqzlg gzt +llse}+z} 3
TlqE ++.
ol*4 zi)zl EzlE ="f-?6Jgl^J= dzl¤"1 + gzlql 4a A.J +9 +E d6I EE= "JHL4 oe. +¤q= gÊel
4 0 + EEqzl ?+=+. o14,3 dzl4l-ol qL + flxI 4e E7l #E xE zlzll- +4U+. {zl $rJrE flx}z} ol-a;-
s zl+44 fl= aol qlqzl Eql^J +46171 olEol'I. olg+ Eg ¤¤6J oll zlzl +e-E dxl¤ E9BzlE bqg ++.+l
?"1 dzl6tol F flz}{l el6]]^J +E"6t7ll ="*9zl ?*E *# E ui4ulrlg,! Linus paulinggl E6ll^J EEqflQ. pauting9
6J+. qlE^J HFql^l= =" # dzlalol ol dzl g^dE= flztzl-?aJ zHHql q4 aq+ ql4 qlqzl
Aqlg
=C =-Erol$r
rflx} zllloltr_ =47l ql4. olg+ ?ol dzBlol FgÎ +ql hrq* zlzla- +ilE CEg + 9l+r 7l46la- + gz}9
EEJ 9,lzl 9E rflz}7l gEL +d6l¤ qzl q=cJl, ola¤- + dzl ¤.¤s il¤-rJp--r+ ?9 4_" e 't44fl't
E +eli? 6--e. -s..<le}4. Hflzl* tr-84"J +-E lxo- xJ= thcbo(AB) - + lhcbo(AA) +hcbo(w)lluz7.u
=d6f+r
sd6l6+E trlrll E+(:B gp.t). Pauling9 E7l itrgl (9D.2)
=¤E
gD.l +¤ cTlE¤S ¤zlrl hcq(xy)= x-y ¤6Jq 6l]?-l qlqzl+. ol 43 dzl
=:Etul ¤.CEE il-= ++4zl"J, pauling* 4 glql+ eD.2^lel
EzI +llso}+ olEg ole-"6[o] +^d e6Jg +E].]]B]E Eq e4e+ g +6Jq= ,IE4e ¤4 Zlg C6H+fl+ ol 4E
ql "J4¤I dzl *CsE tlaulingel E7l #-Eqr +q(s
eD.r). zl*
4zl g^de gAEg .+e-e zlttsl4l 914(rs
4 zlzll$ zlls.lair.). 471¤-cE zlzl7;4 e6}"l q +
=
Cg *rll g+. qlE,<l upgl,tl= ol ilz[ 1.3o1q, 4e] Hl+
6+ 6- dol4l H= c-H aqlql^J= ol ilzf 0.4+.
z}trJ:d ol 90.r
feJ 9D.1 Erl gEoll,\l ¤861.= "JEo+ Zltl-d HFExl.sl tr^l "JE 8ol-.J
+i, gi, r?]r Hq;oU AB 44 9lHzlts 44
4.52eY,2.51eV 'A 4.4zeV+. tr++^J gp.zzloll elofl,<'1 r-1-g.
88714 trlEJI¤el dA C6tsl EE= LIEILH=c1|, 8^44
EE, rle|.^1
^4EP
alEl'lsl +-E gE6l ggg, Lalr E7J^4= AEtl9 +E BE6l'gE= LlEl'.! 4 Ae Aq-= Eg + el+.
r|'.
lZp"ulnr(H) - Zo"u,,nr(Cl)l= {4-47 - +(4.52 + 2.51)ltt2 = 0.98 = 1.0
qo Exl +lls-gt* olE: 0l=-4 2flrl E^l 343
E 9D.1 Paulingel E7lBdE*

fla Xp
a+.J+
"JelE EL+= eL Ez}q Cq6J hamilton ¤4IzlE
H 2.2
.9 dB ¤6Jstr 444BxI. 9zl^1. e+0| r,lrg u15
C 2.6
6J+= dB a,* Voi^r=lc,ry,-E. +El{a rf,E9 CfEl9l,
N 3.0
o 3.4 ,rie {_nd4r
F 4.0
^J46J+.
EZI 1 {4I+.ilH4e+ d4l qlq4
^Flel {¤ +4{t= ^l
CI 3.2
Cs 0.79
C+EI ^le 6J+E +qzlE {lulzl! r-l-o-=$ +Z 71r4V\71
.q '*e atEol 4E ¤ql ++qq 914 s+.
¤4[+xI R.S. MuilikenS a=l 4e B4 " + dzl +dsE E=

lVi,,",HV,,',,dr
ol alel tlat alzl qlHzlts vrr.ll 4*6t= r+71 roolr{.
ae-l6l-tstr1. fE te olgs+ qlHzltdzl¤ flrll Ll]+zl ?J:= ol
+)e+ HP dz} rlslE(qlqzl Hql^l d{¤ fl41 eg + 9l + qlqzlel ffi$ eg iF= ^J46]]HzI.
tt)= *= ?147I$.$ dzl *CsE *=+r ^J416I9"q,
q^.q_4 ?ol C99E Muliken d7l A96ig+.
=CEE E- Eo=
lv!,,.,ftyr,n",
d?- Eo
JWL,y ,n", dr
X= iQ + E..)/eV lr/ullikeng E7l 38E [trg] (9D.3) =!v i,,^,urlr,n^rdt - ! v,LaEou,na d?
¤zld /E gAE "lgE+ glHzll, E"= r dz} rlg+Etri. =Jril,, (H-Eo)r/,,"rd?

Mulliken9 +CE <iol zlA++ ol flzlz| a6J.el dz} Ee J L,;v; ) (H-Eo )( \',,v,, dr
ql EJ Tlol= 6l+ 4o14. ¤zlrl qI zlzl +qB 4.3 qo.:
=
re+E.E 6|=ol dalg:*+4 tr-E1q 4q1 4"1 olq+ =Zt:t,'lv *i (H-E,)rlt,,dr
^]E n,n'
flzl-E9 +trf,'flf,tz} ^JEH'ql 4* 4,"1+= Îd"l+. q c1Alz

oltr ¤-S* ,-]]+ ¤Eg ol {Egld ril?l+. Mu[iken9 4 4l4+
^l.el
Hli6}q, + 4E lVi firf ",e - E,,!ViV,,dt o I a E lvi EoV,,dr -E$fIU,,dr o I u e
Ee]. Pauling 4E= 4E ql
^J.tr. ^l-olql= +lE 4¤. r+s=r+ ?"1 ¤+ gttrI.
xll4 o + +q_4 zJ:-.5*AlzI
^dB++.
lwl @ -e,)y,,d,t =(E,, -E)tyiy,,dt
X v ng = t'3 5 X,{i"r ik"n - 1'3 7 (eD.4)
ût
nI+^J
n'= n OlE 1
9D.2 EE flEI olLlE o
E- Eo=\c:c,,tf ,,- Eo) JWIW ,,at

aqlE +dg a+ q zll4l4 o + b6lr E EzI +llEEi+E
EIEE ql ol+q= dB aqlql^Je-l 4l+E 2il414 0 e +aI
zl +l6fl^J= trl¤$ Ae EE fla!7} ol+¤+. EII 3 3l+^lE E^l
r+6J+Ee. zljr.6l-!.-E 9l n,=nElol ol *ql 7lq= 6Lq,
il E- 7+ r+EL+= A+Elqq glc-E + g.olgr-= a;g tol E
"JelE rls"*+E Al^J qlqzlE al&61-H, z <iol oFj
trI. tr+{^J,
+lat qlHzlE+ ¤qs zlrll +ezl ?+=r+. ll]
s-.1
>0 >0
E-E.=TtG5=o
ol ?]4= +E6l-eJE "JEel '^lE+ "JEq^l ol
e++.il q]+61-= qlLJzlTI ¤xll 9lHzlB+ 4zl ?*4(Ag + cfc,Z B¤4 " e ¤folfi, 0E+ aAu+ oolq, E6J E.g 4l
E ?l+)= 49 EolH ¤+. z.l qlqxlolu+ E.-E.l; 0E+ aAu+ ooltrl. tr+4^l +Hq
+ 6JE B* ou_ui aAu+ 0ol+. trI+^J E > Eool qq, +E
aI4'J AaYl +*+.
344 e Erl+I
HE gal= sltl ezi +e 4l4lel zl=o1r-1-. ol grl

_E.E
QA de p
ql qeH +E al+E e¤^l7lH^J 3l + cl + c ocu o,

"J"J ^lE+ = r'^ I W^H V odr tyruryrdr lW Wra,
qlq 4zl FlAl6lE(+ hamilton gtlzlel Tlqlil. arc+ B
^l
e Er l) ol5 4l+71 sldol g+. EE q +s+ $el u|-=r" o+ +cAcB
lWrltWoa,
+E ^|+6}H(qle^l 7+ flz].9 flzI +]sEL+E {4 zll4 d6' ae'"t B= a* ftql ¤E6J aolrx"lEg E+ .ilq4+).
d¤ a'J6H^J) q *e oilHzlE Eg + ?lzl"J q4. de hamilton g4}zl^= hermite EI+(Eq 7c)o171 qlEql ,jlr,lle+
g 7lx1 4ls9 flzl-+llrEL+=)s+q +6J +
^{lE(+q{ 't4l zl$g 5"J6I+. tr|+^1,
9lE 4ldel(4lzl 9luJzl9) EzI +llsEL+E ol *Ho_e E
g + fl= a"l+. lw u,y a, = c'oa o+ cf,ar+Zc ocrB
rel{ Eql +6J 4o1 r-p-=$ Eol ¤4.

(a) 'JE
HE tlr-lE dzllE olaoalft."JHg qn.r^19 ^lE+ iiF="EI- t, _c'â
- ^+cf,ar+Zc ^crp
c'z^+c'znzc
+= 7lz.la ¤Hg + 9l+. ol ^lE 4lfE"l ^lE+ EL+. ^cBS
ae6l+ 4,"14. =,JAl2 {lHxl9 +i+

olxll E9 Atg flle 6]|+= ^lE+ EI+ +E 4l+ 7,[$$ +
eFI. olag r-l--s- aa o EI+^l7l= 4l+E ¤qo} 6}=ql s
ol=-4 2?\l E^loil EH-d E= flalel
x{-e.
-to 3 ul4E¤. "l*ullot oJ+.
gp.r^lel u+.="gI+E d_aJ#olzluJ ol *zjlqlr.Ji :z AE AE
4lfEol "JEE
^lE+
atg zld + ?lsq, tr}?+^l olzlg e+sl
a- _U 4,,
_U
9zl e** 4ol4l E- + gt+. dE}+olo+ vr_v4t # trlBel +zlE(Eq rcE ElElzI9
^Jal sE 4+^lzlJ- qzl
+ gl+. olag a+s} ^lTlBlH N= rt(Jyryar1,2= #6ll+q E +! zlfl= 6lH +*4 ?J* 4+7I +g+.
of oJ+. El+^J olzll*rl V,t$fd|zg 6J+E d
^lE+ ^l-s" EE _ 2{(a^ -E)co +(0-SE)c.}
4. :z4r tr|g +415-9 tr1.E+ Er^ - c'^+cl+2c^crS
EZI 1 .llHzl{l 'il+ ^l aE _2{(ao - E)co +(B-SE)c^

at-
}
c'o+c!+2cocrS
hamitton s+IzlE 7lql,(l"J qlLJxl= a++g ¤ ^lE+ +
ffi ol-o" olq q-.q=r+ tol 44U4. ol gaJ$ol 6ol qEJE ?r4 e Ll4u Exl-E"l 0ol
" qqot
a|{ :zrla}q +gr+ ee. gLJ ,J8^1,"1 +g+.
ryHryd,r
E_ (eD.s)
v/'dr (ao-E)co+(B-SE)c*=6 (9D.6a)
(ar-E)c*+ (B-SE)cn = 0 BLJ g¤^l (eD.6b)
"l ^lel +E= +gr+ ?ol ¤4.
tv' d, = lG ow o+ cory u)' dt ¤H "JC^l 49 ao, d,s, B, 'l s= trls_r,+ gg aEol+.

5
u^=[V^HV^dr ar=lWuHvrdr Coulomb
x{H
(9D.7a)
aI
= + ci wia, * vovrdr
I v'^dr
r'^ zc
J ^cr! fr=[woHwudr :lv,Hvodr -;f EH x{ tl
o d --iI=
(eD.7b)
=r'^+ti+2c^crS s= 7{il --Erl (9D.7c)

lvovr*dr tr Ei -xl
z|]z]]9 flzt +llsE}f$$ C+E+Elq 9l:s s rjl4l 4Ee A {zlrl aE Coulomb 4Eol+I +s= u}4"144. ol43
a 4+ S=JrgorrrdrolTl trllEql +g er++. rqr E4+ + 4zlzl A= ilzl6tzl4(ao9 4? B$ zlzl$ ul](au9 a+)
94 *ol 84.
rry a, crry r) H (c ory o+ crry
t ¤H9 $ol seculari LJ+ E= ^llql+¤ E6F= r+flqql^l Llg goltrI.
w = ! t, ort, o* r)d.r
"l HX$ AE+g F6ll^l Eqg 1e e.r1, olel +Î6J ^lol !4rll +zJq
!
68C T.llEE +Cg ?l+61-= rll ao1r1.
=
eD Exl +llEE* olE: ol=E! 2flrl Erl 34s
*= qlqzl+I 6|]46J + flsq, gel #g *=trl.Eq 29 0 X*+e-

4 Ezlql^1ts an=ouol4. p= AB rtEol4r +eHrd (x)
4"J "lf, qlE-ql) ul4"lrl4. TllEEI+r=ol ailzl ?+g q= K
5
olaol 0ol qq, ¤¤ e6J zJol9lrJE "JHI4_o_e *9 #g 6
+4U+. Ae 4+ s= olEl Eq ecql^l E"Jqq ¤Eql a -(x) X

Eea'(X)
ol+. -(x)- E""(x) X_
,JA^lg Eq^J 4l+=¤- +6IE]E lllroJfq ollul :19 eD.2 0l8+ o1lLl^lel E^lTlalE=
"l ¤H 71"^|-I. +tr61.= Coulomb 4E.
zl EE "J.I"t r alg eD.6^lql Bq+qot eI+.
"lrlal ¤B
,Je^l r"llc_oll,<lE u[4!z[zlolzl"J ol ¤,J *e^]Eg t 41
iE=B ol+qd qB^lql EE =d=l4ol 0ol Elqoh 6JtrH++ * = ) (a o+ u r)+ (a o- rr,
zlE t}^l n).. ffi 6flo1 u34$ qlql"J
E i
{,.
(
#O)' l"
"llE *=+. aa= 0o+ ts?,t= trt|el (9D.9c)
do-E
=^l
B-SE
p-SE dr-E = (d
^-
E)(ar- E)- (p- SE)'? Coulomb 4E aê] osb q.q=$ pol 7{aJ + 91tr}. Ez} 4
9 flzI xzl tzl7lq+ dz}"ll ql+ ¤.Jqg g= +*4"J
(l - + - (ao+ %)Ir
=
a+ql= x*71 qr" A.J ^J'11e+ dzptlg 556trll t+B
s2)E2 IzpS
+ (aeas- F1=o (eD.8)
ollE xz1 Elr" E eo-Jg olT + dzl-= FF zlullg + gl
=
ai+bx+c=0oJ Eel 2iI *C4olq trls-4 Ag 6ll=- *=4 zl g 4lE x-21 ¤ 4"14. "J"J x*= qlqzl OeF +lalH x
b -(x)ql +lil6l4l 9l s x-= -{(X)+E*(x)}ql +lil6}rll
-b!@'z -4ac)'t' g Aol+. ¤zlrJ /L_olgE| "llHzloll" E*= dz} aElEol+
la
(a4 go.z).+zr 4 dz}9 dxll "lluJzlE olE9 +Z&l H A
ol A+ql= a=t-52,b=ZPS- (ao+as), oi c=a,Ao,B-p,o14,
olq, +ill4"J CHrl Sg qlL olE=9 alzlzl9 elzlzl 44
q4î 6l](+ qlHzl)z} +¤-4 e.ol ¤4. 7J <k,4 -*{r(x)+E*(x)}7} ¤+r B= Aol q}B¤. 4,o14.
"l
, _ d o* aB-zBS+l(zBs-(a o+d, ))'-4(l-S'z )(a oar- F')l''' "J3 tvtuliken9 dz] ar]E(+sE:/El6]zl ?*9"J 4o14.
z(l-J /
(9D.9a)
ffifl011 s.2
ol5g HE flqql E6ll^l + +qzl: g9 eD.ral o
^lE+ HF= ^J46}] EzI. "JHI4"J EzI +llEEl+=
EL+Eql ql+ qlLlzls^J tlal .llHzlql TitL Tlvl& =-el
=^lil v:cts.vH+crrgpol+ qzlrJ yrE Hls TllEE++r l//eE
4. ol53 + gz} +llEEt+s+Et +sE aq+ "t Hla.J + F2p, ?JlE*ftrHdB Ezt9l ql+ +Eql 4+ zfi$ tflz]
4lE6J+el qlqzlEol4. ge+ql +lil++). gs6J qlolEls=g trl+$ ,JE+.
Î
eD.eaalS q +++ E + 9l+. Fq zfl^l tszlE a+ql
E 0o=0r=aol4, q-q-4 ?ol ¤4. IleY Etev -ilt + E^lleY
lzyzas)' H 13.6 0.75 -7.2

v2
2a-2 + ( -2a)' -4(r-s'? )(a'-
2
) F t7.4 3.34 -10.4
Er=
2(1-S
(1 +5Xl -5) tr+4,\-l de=dH=-7.ZeV os-aF=-10.4eVE +=+. E
_ a-0st( l-us) _ (at0Xt+s) F=-t.0eV(dB4 o _+ +16l-=
{l)tr }--r. S=o_o-tr. +=+.
(1+S)(l-s) - (1+S)(1-s) olE <tg gD.ec^lql Bq+E q-g_r+ ?JZ 4+rl-+g+.
=
, _a+0
t* , _d-0
= l+S ,_ = lL E"-I 2ts^l E^t (9D.9b)
E* I eY = ! (-7 .2-10.4) !+ (-7 .2+10.4)
= -8.8*1.9 = -10.7 ,1, -6.9
8.0"J 41E r*21 *3 "lluJzlql
6]]B*trI.
ol+q 2fl^l Exl-9 a+ql= 3rl4_o e S=0o ts -oEtr1 ael fllEalfz} -ro.zevql^J, rqr Hle'J +llEEL+
=
("]]E A+6}rtl +48 +4 oE). f-BlH, zl -e.seyql^J +4+q, olag rB eD3ql +4q]Htr|.
3t+6 EII+ZS
0t8a[ -d4t E*=do,-#^ E-=d, #" (eD.1o)
c) o ol u}q *ol, qlHzl iI

:aH sp.aE r4sql^l -H_ts
o o)
\o n ^lEg
lao-urlzl {tal ql= ^J^dq= EzI +llE6J+EE qlq
N o) o
f- d
= zlel a+Eiql zlzl tJzl
0.96r4r,. - 0.28tyrr, zlzJ- flz| +llEq}+el
"ilH ?*e4, :
Hls el6Lq A* Er+e+ HIAEI dpl ++= 49 9"la}4l S+.
+,
F2p
0.28ry^.,"+ 0.96r4rro
Tlqd-= + +llEEL+z| ,rJE Hli+ qlHzlE zl-4
fg eD.3 HFE flrl.?]lE"r+flil EH-d +g oilL1^lel 0l=ol uE= E^1.
ql= aq} tr4e+ Hlaq+ E47r 7l* aAl +4u
<F
,p-o
Kl-l
n
+lE-ct+. rJu
F\
+.
ElEfrlel 8^l 23 B=JÎ ec+ +llEoJ+Eol aqlql 7lq= 6l.zl *61+ aE qc+
+llEEL+e+ ?)*zl ?llE6J+7I qlqzl zJ-= zlzlzl allEol
2x2 BBzlg q-q=r+ eg "Jol+. =
q qI flz}g ec+ +llEEL+7I trl= flz}g ec+ +llEEI+
ab 2x2
e+ Hl+6J e'JE I ?zl"J 4c
qlqzlE zlzla_ 9lq
^llzl
= ad-bc "J=41
cd +_eC+ ^JE4r-¤+ d4¤ol qql LJ+ B+qq 9l
,+7+q
q lB l.e- E olE zlzl ullEql +^lg
3x3 4B:lg tr|s-r+ zlol2x2 flprl " + dzflollrJ +814. ÎolE ttsz}S"l 4+
+ 9tg C++ zl+. Eq ecql^J Fq 2g^L Ezl¤ .!.R trll
sel p.zt ?+r+ +44 o e o ¤6J BCql zlq*+r 714q} 4
ab
def
c
=,1; t,l,l'r t,l,l'r ;l E Ego.J E+e-P ¤Hol g+.

gh i ¤'J Bg4e-E+El gg + 9lHxlE ol..$oll.<l s'J *c
= a(ei- ft) - b(di- fg) + c(dh- eg) sxs -d=J^l 49 EH eD.l^lel dB Aq+9 4l+ <l# +g + 9l+.=
*g qlqzl r*-tsPq= aq+ EzI +JsEI+E 4l+-=, :14
az| gg trlel HAot Hltl4= ag. Te.-61qr{ol r
Y dzH +g qlqzl E_E+E]= Hlaq+ EzI +JEEL+E 4l+#
q^l bel Y az} goltrl). qp^lel 6J +s* ¤eg "Jel
+g + fl4. :244 ol ¤'Jal-"-e+qE zl 4*"1+ 4l+=
E + 4"14 + g¤. i+L*g ull t. q¤4E H ozl Ht 9 ulzi gqd+. rfl{q gD.6a^19 a4 gLJ^l (ao-E)co
qE aol+.+ +(B-ES)cu=0 o P*El= trl^Sr+ ,Je 4+7I +g+.
cC
_il.+ b a
=bc-ad =-(ad-bc)=-
a b
cB--
(
|
a^-E\
^ lr (eD.11)
=, d d
c c
I B-ES /'^
q -il++.
cd cb -da (ad bc
a b
ab c d 6
4
"l ar+E + 4E^lql^l "Jgel + 4"1+ ¤"1 t-9B uI
S
r 4p4ol 0ol ¤+E 49 9"1*4. +2
= @
Io
6 E
_2
E:
(b) 6ilel
=a 4
sD.ec^]9 + +sq} tlEzt+ gzl- +llEEt+= ^tolel
=ag
qlqzl 7l luo-arlzl rtzf;)ffl e.J4 Hle'J ELtlzl z; -6 0 2 46 8 10
lao-arl/lao+orsl
A6J+= 4"14(:_B eD.4). qlE^l lau-aol >zlB I "J tr1]=
(t+d',r2- 1+-,ax9 snE ElElzI9 tral tz= u-oi fal 9D.4 7lq6l= fllE-Er+=el ollLl^l iloll Elal. E^l' ?ll_E-Ef+=E
=Î^](Eq ollqrlTl EZItrl'. 0lE/.l(Eal"^$E0=-leVoll E|'|il a0lEl. rala 8^q d=e
+)g ol-o" 6l-{ ++!+ ae a4= eg + 9l+.
HE rtt16=6)E ollLl^|0il EH-d 10|tr[.
=-Br0l
eD Erl+jlE-d+ olE: ol=6j 2flrt=rl 347
945* E+ A+EI !"lo} 6J+. oluJ $olJ,tJ }!-"J HIe+

u|=t" ol+q 2fl4Ezlq a+q=s=0o? E6tr eD.ec^lo+ +q
TJol
lvt'dr-r'o+cf,+2coc"solg-tr A+s+71- qqH q'q-r+ e zl= 4qlq} E=Ex{ 4g ole" olH +g A+= Eg + 9l+.
g +4lr| "J499oh 6JtrI
I
c
c'o+c!*2cocuS=l (eD.12) ^-{,.( %f)'}''' aE= oo-=.
(9D.1s)
7l-8-d
=rt
*ql^J B3 sp.1^lg ol Bq+H +g=r+ ee +ZlE
^lql
eg + el+. rq$ so.rr^1$ ol+6}q cr$ 4lt$ + 9l+.
(eD.13)
{'.(ffi)'-,'(ffi)}"' 4,,.1HrE ^J4611 HzL. *E ZI++ qql^l ds=-7.Zey,
or=-10.4eV F--t 0ev rell s=0o-E- str E*=
qD.ea^lollî +eI 4.Jql E=E_{ Zl9 Bzl"J 6lH ol
-r0.7evel E_--6.eevE 9fl94. "l <tE9 go.rs^loll H
go.rr^l e-EPrl
"l Alf# +ei.11= 49 gg + 9l+.^lr+ q+H q-q-r} ae zl+# +e + 9l+.
*ql^Je+ ?"1 ¤zl^J {46}= + a+ql= ol alol EC
?J46l4l gtrt. +d E4 2gz} Ezt9 A+ql= 0.6=us=& E*= -10.7 eY V*= o.Z8ryn+ o.96VrF
e+ eD.eb^l o + fqzlE 4q+* E,9 <tsE+q q-.q=4 e E_ = -6.9 eV ty_= 0.96tyr- 0.28ty,
e a!+E Eg + 91tri.
*g qlq^l(-10.7ev"J 4) nt+^l dzl gcEE fll
*
I
E+ _a+ B
- ce = cs=ca E6l 2?^l (9D.14a) rgL+E Hts-Et4 Fzp TJI=EI+9 zl¤z| rl ={, +g ql
1+S 121'*5;rrz E^l
Hzl9 +AC+ +llEEl+qlrlE:z eI4zL ¤u}= ag ++
_ a-A _
I
cs=-cx 6Iq4.
I_s
'
P ? (eD.14b)
"_ -
"o -_
1211_s;1,,,
=s-d7]lLJ=
I 1. +¤ $dg +zI +llE6J+zI qL flzt 491 4 B"l 4+9?l z 4. EE flal= ^lE+ 3l4s+^l7l= zl?* xllE"oJ
uIEql
dzlE 4,o14. +.
J 2. flÊ d7l ECE= 'J Aqlql^] i+zlzl z[.1] $etr dzl D s. 7l^.1 llE= E1l flEe+E "JE= a3 ,rllE9 flzI +llsEt
Arolzz= eEE +EU+. +E trJoJ4.

=
D 3. A6J fllEaJ+E dzl+g dzl *Cs7I dl gz} +q^l g ! 6. a.Jr+ HIAa} s.q¤.-e- 7lq6h= gzr +llE6J+7t Hli6J ql
44zl er" Hla.J ?llEEL+el dzltig re+ +qlol+. HzlE zl4 rll 7l* aq.
=9:etAl=
,\-lzl
oz. ,.l
-1 +4 al Ha
SzI +lleE4 V = c1rVnt csVs 9D.l
Pauting9 dzl ,,sdg Wo - Xul= {t rfro(N) - *lt 'b,(*) + nco,(BB))Itt2tev

9D.2
9D.3
Mulliken9 dzl -s^d5- 7=1Q + E-)ley
Coulomb 4E a^=ly^Hry^dt CE 9D.7a
+B ZIE p=ly^Hryrd,t CE 9D.7b
EE E?-] n= IWI^HV,n^dr I lyi^ry *'dr ; a E I Ac =O

EiiJ gE 0l=: trlflrlErl.
=rl?llE-Et+
E q=-E +lzlE-4"F"lzll H+^l7lH^l Bz}el dill qlqzl
> ol EEE ull+= olP E 4l&6}a "lq^J alzj "]lH^lql oflRahb EzI e4E *ol
59et 0ll+EE E^1.= rl-Erl Erlq, qal^j olEel crl
El¤loll^'l
E E gJq= ole" of| 4,ol ald
"lBl+ 4lÎg 3l^l ^
oF ++.
?I= Eg + ?lolot ettl. E^H= 0lE4 4ltl HJgol Eal olE
Eln ?l^ltrJ olaE 0Fll6l.= qlts q7l,t1 ¤861.= Et!*zl gts olzl"J _H_rJ + H 4"J
"JHg ol$alrl4E +?lz} EzI9 d
oeFH 0l=ol olgxl gEElol fr=rl= 0|-= aol -Etol a z| +a= ¤+61r.6114ts fzl- ?14.
=
0lrl.
4flzl-SzI{ldE ^JE q-$fl} 449 flzI +llEEL+E
q}"l d44d Ezt +llEEL+ql 7lq.6Iq, q4^J +gz]. +
> EIg TllE
zI9 EzI fllro-;i;5- "JE= Ell= 4?ol 6d qoJg 614l
Ext ?ltEB+b 4El,Et EllSE += E= fl^t flE-Bt+=E dB
3de-e LEIUcI. ¤+. ol qla sAg $d6l bE6IejH Eq 10, tocql
¤E{+ rl$g ol+flot ++ rfl+ +qq =61 slq+E
^-l =?lql
> Bs.Et qHl xl^l .9 ¤Hd4 ae 4+4"J qlag L+4.11= A+E fl4. ol
0l EElofl^1= EEI eDoil^l ¤E-d 0l=E4 zfxl Erlofi rtrd E!8, q?rJ + B"l"JoI EzI9 0trd-4 n¤* zl-= +
BE BH^14 gE B84E TtlEE +tll^lZtrl. q7N " "l ^lolel
=61
6l= ^lE
+ct H.Hg gE H{6!¤},I!el 8 l 24e+ 2s)o!trt +tr} +6J + 9lsq, r?]6}q o¤*9 zlzla- EzL9 ++el
=e-d E-o"t-g +{t]lr E rH4"J Hl$ql rI4 n¤*9 Et$ zI
=4
ArrE9llolE o]tolts gE +xl Il{:toll 5,4alEE helAp} Ettl'.
zll o1 +zI9 ¤eg ¤E6l+ 4,"1r|.
9E.1 HUcke! =Jl

ffiz[ +z]el +z] fllE¤l+=g zflz] EzHeq eo)oll,r-1etr
+eg *4 " e "J= + flsq, +"J q B:g gz} +llEEt+ Erich Hrckelol tgrtHgl zll"JoJ ol+6tB *ol 2+
59 ^;Sdl"t 64E 4ol ffi $}ol+. zflzl +zlql^le} e =ÎHg
dt} EzI9 nExI tllEEL+ qlqzl ++l rBg "JE + 9l+.
ol 4flz} +ztel EzI flls'J+=g Ezl d^]l9l A4^l El41 ol L;loll.<l= 7r+llE*+"tl zlqd+ flzl +llsq}+Eql .ll+
4. "14* Ezt TllE++=e- 9HI4 " _e q^s=+ ,J+ E* ?* EE Coulomb 4E aE EoJalzll EaE4(Eq eD). {le.! o1
r- rL
"JBg ols-" o|{ qlHrg {$apz} olbrll, o¤6JEg aaq
j="1 .
q gl+r 7[c6[r, rd6J4 rH]?6J Ez] +llse+E9 qlq

V=L,,V, gu4 LCAO-|VO (9E.1)
zl= 4ld6l-= 4"14.
=el
¤zld vrE flzI ?llE++olq, 'i.Ce EzI +ql Eol?lE e (a) ol UEel aztl
gzl¤9 flttzl +llE++ql Aa 4"14. 4l+r==g zflzl
=
Ezt{lrle+ +Ag *4 " + ¤'J %LC!$ "JEl" ol4 o + EzI Ho| +z16}rll +q9l= czp fll=-*fEE LCAo= Tlzl
+El qlLJzlE ++trHEq eD). "l rlaql^l= g'-J eB4¤. r TrfllEdJ+# ++U+. qE^J qlHlql^l= olag q-q-4
RISI "l BBalol ool 9z.ll aLb {lHzl= +ql ffi olfi oll *"1 44U+.
HzlE ¤'J %r-A^lql Hq^l 4 EzI +llE6J+ 49 flzI +.ll V= ctVd,+ crVs (eE.2)
EEL+EE 4l+= +6}ril g+.
zi)zl Ezle+ 4flz} $x| ,r.1o1el +g 7l"ldg Ezl-=ol ¤zlrJ WeE flzL e9 VrsE flzI s9 C2p +llEEl+olul.. ffi
*l,d tr}"}* Hgq Eo}g 714 + 9l+= 4."14. + 2fl^l ql= Eq spglrJ ¤EqL HE ?14= ole" oll.<J 4'J+ 4l+e+
Ezl-E CB"J ++ql S.zl"J qlaql :flzt EzI"J 6|q?+E "llulzlE +tl+. + g,-J qg4g olag o_o e Fg
^ll+l^l
dB"J +E 9lr, E r.+6J AEL4E HldB"J +E 9l+.+ r-l¤. olag ¤q^J glHzlE ++. qlflE A+ql= ol g'J^l
flxt EzlE Eolg +44= 4.J 4ol4 e.J4=-g +6}el ol ae=ae=a,9 +g + flgq q++ *ol 84.
eE ErlillE#olE: trIEFlErl 34e
a-E p-ES EBI+{I qlq. ol A4l +llEEL+= Bz}el +E4 "t $$E
-0 (eE.3)
B-ES u-E 4 C¤ql ¤.&g +71 trIEql ql+61 +s6}r+.
=
3l4l 4l4}Hql^l= -EE tE 484 Aa 4Eg d+ alt}6}
zlEl trl-e-_4 *¤. Huckel =Jl-= ol+6IH EzI +lls
=^14"J
aJf 9luJzl 691 _zHg El]t6l dril eg+ 9l+. Htickel9 qfl9 n**tr 5E qlLlzl, f 1n9
=^lqql^l
ZnE-e=EZl 6l*= trll gsel qlqzl= zlqlTlg4.
d4¤
-e= d? 4Eg 00 + +=+. ol dolE qI ao 000cm-rE,<l s.oevoll 6il8++. tr++^l E
tfll
Hl-"Jd fl4¤
ÎolE +H 4Eg Ef so + +* g "J+BE #g -2.5eY(-240k1 mol-')ol+.
l-r'l o
t
O
-T. I
*"lzl E= +E 4E* + AAI(E+BE) +=trI.
ol zl{s=$ EH6Irll ql+61 d6J =.^l¤olzl"J ol* ol# (b) o! HJEoll^l olEE!= -J=!
6IE sliel +rE zlzlt_ EzI +llsEL+ qlqzl "JHI
4 /lHS ts$ fz| 914. ol 7l4;-o ole"6l-S =+lE
¤H ¤Ezl"l "lEg = Ezlql flrll 4+^la + glal 6LEIH ol =
Hrickel
r}^l 24)* zlz]t_ +Elg + ilq"t +
q-q=4 ,J* +42 zlzl4l gtrt ÎBg flEtEL$zlE
+. Eq eDqlc "l+q zi)zl 4lql ql6ll^.1 ++ ¤'J "Jc^l
. -EE r}]4d fll: a-E t}+q ^l4I*+.
. "Jd fl{¤ ^l-olel Hlql4d flr,0
(P- fs;cu = g
. tr}=E-Efli0 (ae - E)co +
(B-ES)co+(%-E)cu=s
ol el6]]î eE.3^lol trl+$ ?"1 84.
=^lql ol !g "JHlEl^]4 *str. 4l+B|]^l a,-Hy(I=A, E.= B),
o2-b2=(a+b)(a-b) F=Hor,r4r Ae 4E sE sAB(+4lq= fl4# szltr-
A_E B
=(a-E)'- 0' (a-E+ B)@-E- B)=s (eE.4) g.J Aa 4E)E
^]-e"*
4ol4.r4r qa +48,,1 Bzl
B a-E 916ll^l arg4=4 EE. Esrr-tr +4U+(srb rol4). r4H I
ol 688!9 Eq eDE El$zl9 ^Jal r"ll^l ¤E+ qE d E + 401 4*4 ?ol S4.
zH6Iq.+. ol
^19
lg
E_u tB oltrl. ¤zlr] +zlzE EB (Hoo - ESoo)co + (Hes - ESou)cu = 0
i1E6J+ql ql'J6iq1Bz} *ol'I), _ zlsE HIA6J T{EE}+ql (Huo - ESuo)co + (Hss - ESur)cu = 0
6]]rd-6J+(rH lE.r;.
+A gzl¤e r4lgl4 dzl-= 6l-+4 Ll]+!_E +
zJzJ o\ ¤zl9l E 6l+E 4lf qE E AHI el=5}q,
7l3L 4e+7I 9lr+.
e ?lalql u|4 ol BztE {z} uflzl}_ tn2zl ¤q. qlflql^J "l+^J En(n=l E= 2)-tr E^lq. + 9lrJzlql 49"61-E F
jElr E* Erl fllE-Et+, HoMo(highest occupied MO) qFI.rqr 4+= c,,rE {4ql=ql, ¤zlrJ
= ^llE= +E6llo}
zl rn ?.llEEI+q, rlxJ Hltrf;. Ex[ +{lE:d*, tuuo(lowest n= t("llLl zlzl Er! 4l r,,oel c,,s)ol4 2(qlq ,.17l F29J 4l rr,n
unoccupied MO)= zn ?llE6Jitrl(trllE= olag 27r. +llEEl-+ el'.r)o14. olelq} HslE zlsfi$ ol+6lfl +lel + rl"l 4
al-l e.r1a34). olE + +.llEEL+. elSrl "l EzI9 e4l fll *4 tol H4.
(Hoo - E,Soo)c,,o * (Ho, - E,Sor)c,,s = 0 (9E.5a)
(Hro - E,Sro)r,,o + (Hss - E,Srr)c,,g = 0 (eE.sb)

2r a-B
{zlrJ n-r+ 2zl s)olot 6}E-tr. dill4 e + 47HE rl"l 84.
5
K
6
c2p c2p rfll 4 tlel !$$ q+r+ ee EE flE_e +4U+.
1n a+0 (, ^^-E,soo HAB-E,sAr )[,r,,^ )= o (9E.5c)
IHuo-E,Suo HBB-E,SB, )lr",u )
leJ 9E.1 ollEJlg Hiickel E^l'+llE-tsr+ ollLl^l + t^l= 'JP r+llE
ol pffi q.J5lelE qBE¤ #6]]^J
-st+E =+1. eE.sae_I eE.sbE + ^l
^t^l-dtrf.
3s0 e Erl+E
ElEtrlel 84 za =d=J
6JE!3 6J +el gr+.C.J f9 rlg$ ++

¤E"l #6ll¤ + ?lealfl eB A +E gE +e+ B +E
do+
qel +e+ =AqI
gel += t"lB + 9l+. Br+ ge r,2, ...-tr H B9 fz}5"J6il"F ++. q{^J BE +e+ ¤9 fzl E"J{I
g-E Eq -E^l6lq, =dE e+E +lil. 6ll¤. B4 gE +E AÎ4¤ BEg 4{Idol E"J6J A(., E E+71- nxn)E
s.zlE Eq^J +4U+. r;l6}q e ,r+ I cgl +lil{} q¤ vl4"J *-6]le + fl+. ABe+ BA!. g¤4 " + Eg6tzl *
a + Mg M,,tr_ E7l*+. qlE^J 3x3 BB$ u-l-e-$ pol oq, qE #cg "JHI4 " + Hl-7}+Ioltrl-.
"I4c
s.zlo34. nx I SB(6J gql nzll flLzt Eqil= qE)e E 4E1+
r qI+. ol ElEl= nxn $,<14¤ ¤84 #"H+E Q$4 g
M,, M,, M,, ol ;llE$ ¤ ulrlzl
M_ M,, M 22 M 2l ^Ja+
M,, M,,, M 33
'I4C 9-AEE
qlg EEllol.r(trace)+r 6[{ rr Me-tr. +
4U4. +lE EB9 a+qE q+4 *ol ¤4.
i] [t :r'::r':].[ ?]
Tr M = Mrr* Mrr* M*
ol F g EEI= r B="Jg s.^l6ll +H Elq, p9 fliE*
r}g-r+ e+
'll4d eriol lolA r ole-lE _E-= _a ooJ BEg
p,=\A*8,
^5ol
E+l =d=J"l4l ++. :x3 BE9 A+ql= +gr+ *? 4 n
^ r-l
"lT. lxm BE(+ eq nzl{ fliz} 4B)e 6J ulEl+
=qq=
_::. +4. "l EEIE- nxn $xlzJ¤ 4Er+ E-6ll+H 'I¤-4 a
l-
['rl] ol .\l_e.S B ulelzl
^Ja+
( o,, A,, A,, )
+ BBe-l 4* s_^=¤ qql+E ol + BBg tl* Ertzt (P, P, Pr)=(B, B, Br) *l A,, A,, A,, I
g+. qlE^J BE ap+ BE R6J e+= s=A+B-tr +4'llE

I e,, A,, A,, )
qB sE _s_^59 q+r+ ?ol H4.
Pel gi'==g "JHI4
o e r+q=r+ tol 448 + 9i+
Src_Arc+B rc
P,=\8,A,,
olAg E"JEI q{]del BEE"J"I rJafid + fl+= ag n
9"1*4. g ElEl= AÎ4IB qpg g+_o_E+El +6]|+r" q ulEl
F BBg #g + 9leq, r ar+= P-AB4a aiE P9 e-EE- e-E+El t6llzl= Ag +E-6Lq+.

= qg AE q=dEgA-'E
a +Eg trl-g=4 *"1 5|4. 444Erll, olag AA-t-lE +
ZIE "J+^lzlg 4"14. {zlrJ 1.$ Ae+ E"J q{fCg 4E
1r:\A,,8,, ++l ElEl4.
ol +s=zl= EH ¤tr} +*ql= ol-4e+ a3 namitton Etl HAA-E,SAA Hou-E,Sou

Fr-E,,S =
rt =d=J II4 B=J s, r?-ln qlqzl E,q q+6F= g q HBA-E,SBA Hrr-E,Sm
=e
Bg EOJ6J+.
Hoo Hou Soo S AB

H_ s- cr= (eE.6) (If - E,S)c,= 0 E= Hrr= Sc,E, (9E.7)
Hro Huu Suo S,, [l:,)
rB]H
ol$ +
^llEE 4@=14
2)g r+s=+ Ag Eel +"J lsE
sr Ex[ +]lE-Bt+ olE: trfElrl.Erl. 351
+g+ fltr}. 4E r= ql4d flÊol E,"J ql4d BBolq, :azlof{ ol

4e a+ rrE Ell4d BEs Hl^+q+E c'Hc H+Ig *.I4
Hc - ScE (eE.8)
H qlqzl$ +ts + 9l+= ag "$]]=trI. ol =:4'"9 =d=l E]|
9zlrl ce+ r= q-q-r+ ag qgEoltr|. 4del,z}l. EI+. ol ql4dffi ol o 7l= qg c9 EEe zl
cr,n 4 rll-= + ol+q= +llEEI+Eg Alizl qq q+^J EzL +J
) ,=(? ;)
cz,e,
c= (c, cr.) =
cr,s cz,s
(eE.e) EEL+e] adg eal gq
GZf BE! En4cElol eFdErt+{lE-d+=E

Hrickel ol+6l.q +4qfl(l)E 7r+llEe-+E-+6t
gs.s^leE qr.s^l"ll -Jq+H =ÎHg
qg=q
AEq= 4Eg 4¤.4 u.ol
^lg
EI=r a_49 gq+.
g+. =
H 5 cE 4/
(Hu H^r)(r,,^ cr,o) (Soo Sor)(r,.o cr.o)(E, o ) 1 Butadiene
Ir* ,* ,J[r,,, ,,,, J=[s,^ s,, J[t,, r,,r.,J[o E,)
slHE BCe q++ rJtr+. r.a1B ol +fl2] alql q+ BHg 4i[flo1 E+.
^[:df
Hiicker9 714+ s|4"lel a* F ol+6tq qB H= EJ
(H* Hor')(r,,o rr,o')_ ( H ooc,.n*H^nc,.n H*cr,^+H^rcr,r') = El¤fl_qE ol HE
Irro Hr, ,/[r,,, ,r,, ) [Hror,,o+.Frrrc,,, Hu^cr.o+Hrrcr., )
E"loF*+. 9t ol hamitton flBg
ql4ds+ rlzl} qe c= +61+tri1, ol ulzluJ +41= +
relr +HE +Cg q-q-+ +E| c| +u=?llq= ol+EI+. z}^ll+'lt¤+ $olxl9 *al
zs9l +4B,zl"J :ael+ 6J TLzl +E-6llot g
cr,e ^ldg "J.J
(i; *)( cr,s
cz,r
H-d,t+MolA Mol Hl-d¤ BE"l4E sc-rlc= a,c-tc-d,r
cz,s
)(:' ;)=[i- i;)[.,,i, :,:;t) qlEql Mg ql4d3l+^l7l= BE c= qB 4"1*
E,S_r^c,,^ +8,S.*nc,,,, ErS*cr,o+ErSo.cr,, "J ^l-d
E,Sroc,,o+E,Srrc,,u ErSrocr,o+ErSuucr,,
alg Hs+^lzlzl f;:es, trI4^J H9 Aill4 44CEl¤- ol
+zl 9.16]]^l= ezl M"Jg 44dolrlzlH g4= 1o14.
4E 6J¤(34 "e ,+4U aE)¤. ul;ra|fl 47l]el ¤E
4-"1 cgzlql A, B, c, Ei oel szls-E"lH hamilton B
4?+ ,#gl ql6l]^l 2414) eE.sarl4 eE.sb^lol +g+. =01
wl
A r+s-l1 ?ol ¤4.
,r0oo
Htickel tBql JE H*=grB=a, Haa=Hse= a4a 4 (a B o o)
=g,r.lalr. s=l-E sab4(¤21,<1 13 B, qB-e.^J, H.*o Hon H^., H.r,, -at "
*t,
a 4Eg ++l
ql4d ^Jel gi= d* toll, r ole-lE dP o"l q= 4E ,I Hro HBB r{r. Hro
H.o H$ H., H., ---+
+l- lp a p ol
lo p d pl
ol+).rBlH Hoo Hm HDc Ho, [o o p ")
a B
H_
p a )'=[;:)
ol BBg r-l-s_$ ?ol *4tfl4
s= +fl 4Bolo e ol4,g n'.6lt 43 "l-*fl .ar+
M
:r-El.l.
E- 444x1 gE+. u++^l eE.8^lg trl^g=r+ ¤"1 ¤ + 9l+. (o r o o)
H =al+ I
lr o r ol
Hc= cE lo l o rl
q-sql= ol g+_q_E+El qqE c-rg *6il=+. rq Io o t o)
^lql+
E r'c=lol 9p e q+4 Ag ¤+= Erll ¤r+. ql4de+^lzlfl1au=+llq= ol+6ll^J) B¤ u"l trl+4
BoI 84.
rtHc - E (9E.10)
352 e Erl+ZS
( +t.oz 0 0 o) B=J= olE:d r.Bil g8^.1

lo +0.62 0 ol HJE^lol+r ++.
=71
0 -0.62 ol 'l+4 ae Eq 4¤- ugil

[: 0 0 -r.0, ) Mx - )t r+^l gE^l (1a)
tr|4^l q4dE+ hamilton Bgg +94 ?ol 99ot g a ¤zlrl ^vt9 nB4 ,¤E ¤ C^l-48 Bg, I= r8il4
"1trI. a 6I= ^J+ relr xE r*trlElol+. r+ulEl= r+il
a+r.62p 0 0 o)
,Je^lE zTJg
"J+^lzli nxl g qBolq, +¤.4 a¤-
p- 0 a+0.628 0 ol gol+.
0 0 u-0.628 ol
0 0 0 a-r.62p
) .[:::]
rqI ol E]]4CE|= z}4s= qpe q-q=r+ ge aol+.
0.372 0.602 0.602 0.372 "JqI4 .a i=1, 2, ..., n oJ n4l4 r+ EEI lDql 4go 6l]^J
o
c
0.602 0.372 -0.372 -0.602 ntllq r+il )yti)71 ra^13 r+g-r+ *ol l7q ¤
0.602 4.372 4.372 0.602 =4]qI+.
0.372 4.602 0.602
+ 91trI.
-0.372
(M- Lt)x-} (1b)
cdzl r-l zl-
l' l"l -l
filOLo rll9xlt- tl zL :llE6L^..oI
-ll O "l r- L!-"1 l'1l4El
rllal 9lzL :llc
I ll -il a-l t-:-'l l'tl+
EL+=E Alizl ¤+. trl4^J "ilHzle} BzI +]lEE}+= 9zlrl 13 nxn Egl ¤E"lg rx-x7l ¤4. "l 49 B¤
M-l,rel 4lfEe E flE{ lM-l,.l lol ool g trl"J 4E
q-q-r+ *ol ¤4.
4=+. q+^] ntHA a+il= r+s'=r+ gg gLJ "J5^lE
Er= d+ t'62P V1= 0.372ryo+ 0.602ryu+ 0.602ryr+ 0.372ry, 6llE+El +6J + 9l+.
Er= G+ 0'628 V2= 0.602ryo+ 0372Vt8- 0.372ryr- 0.602ryo
Er= a- 0'62P Vr= 0.602tyo- 0.372ryr- 0.372ryr+ 0.602V1D lM-Ltl-o (2)
G- rczP
Eo= Va= 0.372ryo- 0.602ryu+ 0.602ryr- 0.372tyo ol ¤E %l4^lg +q^J -ft rzllel -7+ile ols.aLfl ql
{zJrJ vr, ..., yrnb c2p +llEE}+Eol+. ol fllc.*f.:=-q- 861-= a+ EEI= +g + ?14. ole+ eol 6IqE +d
,rJe zl-il.6}q, d?"1 +^lqi1 A+s+qfl+= ag +d n xn B¤ x=
^8zl6ll"t
6l+ql ol BBq gEg EE r
6lq+. +ilql r+ EIEIE "l+qd 4"14. :zr-la|{ ol
49" 6l-=
-a$zl$o'l I,, L, . . .ol_,L 4s" 6k r+ ElElz| ffi;4 4'
fl Vr, ...,v/n= +4qtl9 lr, ...4Tc $z]. fllrolfz| r{-L a14.
Eg +E-61-q4.
rPl B7l 9E.1 "Jg 4qA .CH2-CH=CH2E zlzll. fl ,I" xl n)
9 EzlE flEol 6}q4. 4 +A= sp,ECg ol$Qr z[
l[:l][
*t" *t"' (3a)
.tr(')
a6tjr" zlzle;.J 4 E+ flz}g zp flleEt+ + dtLHEg

trl+). zlzle +l*+ *:" xl'
n)
ohOOS'O
+'rh LO L' O - = rh.') th LO L' O -' ='h
¤
rqE ¤E xz1 trlg=4 *"1 gg"t ++.

rh LO L' O
'rhOOS'O
'rrh009'0 + rth tO t' O + rri00s'0 = tth :dtt' | - D' n'dw' I + n = I iE
x;'(r) x;(21 x;
(n)
*t"
X=(r"'x(').-.r('')= (3b)
(l)
x; xl 2) xl'
n)
eE Erl f lE-Et+ ol=: tl+lrl'=rl 353
ols+
gAgol d+
"t*zlzltr_
ql4c g^'Eol r+il
7JZ nx, BB aE
i.Eolr 4"121
4n
a - 1.628
G-s
ooJ +q=r+
^J4dl E+.
Lro 0 K c2p
5
3r
a - 0.62p
6@
A_
01, 0
(4)
6
2x
o + 0.62p
@
;; ;, 1n
a + 1.62p 6668
+gql= E= r+il ole^l Mll=)"lD=.-i-e--* ?ol B azJ 9E.2 +ElrlglE Hrtcket E^l- +lE-Bt+ ollLl^l dllB6l.=
=?lErl27Hel
rflE*#EE azH9 pExl(CE+E1 6lLl{ l '*3
"JBB4"e+4U+. =EE)=
Â.E..0l ?1lE-Bf+=e Hl+^lEl Elcl 9l-
nfllE-S#E it^l:dtr|. +e-16l-qal.
MX= XA (s)
EeE xel qq¤ r,¤- "JEJ" "lag'|gr+ 2-ol s49l ^lY tn'Zn'o14.
+ g+-q-+ E6H=+. +4qelel A4l 1IEEI+= 27r ?llEE!+e| rzr +llEEI
x-tMx- x-lxA- A (6)
++. sE ae HoMoE^l +s aqlcolq, +z|=
LUMoE^J T-=. elEaJC ol 4.
I,-'Mxe+ ee EE +a= 8Î HEtol4r ++. ¤zldi '+4 ?5JC'ol* "J3 "l +llE*+7} qq ="F9 "Jd +llE
H+1- rtMxTl *r*
AzJC BEe "JE4(azI 'l14d 6J+Erl eq+ "t Hla6J
^Jg L¤¤ 6Izl"J AEt^d atlzl zl
^JÎ
egolF +). tr14^l x-,tvtx$ 44}dp+^lzli eB x= "J
EH4ol+= F"14. u|4lzlzltr_ ,+tr *ao-J^J,ol* "Jg HIA
+ glsH E^ll7I +rl= 4o14. . ole+ pol a]1.<J +g']] EI^dE47I zlul]4ol+= *ol+.
4d eBg 6ol olr.-l +"JEI a Ê r+^lE 7l^]|4, ol H
+ElqflE 4 ndz}9 qlqzl$ 6J6J Aiil n-dl[ trAt q!
¤19 zt4s= Ell ol+g BE x= r Bql ql+61+ r+ Llrl= 4l&+ ffi olTig qlflql^J +6J 4r+ Hlnoll HB
ulEl= ++q4l gr+. ¤zilql flq^lL ++
olf,-all.<J ll+ilel 11+ EEIE +ti+ ÊEfllq=
-J qlqzlz| ffi4 ,JEI.
En=2(a+ 0) -2a+28
otr, 9.e.
r4r
I LtZ C) C)
+4qQlql^l= ol Ttol +¤-r+ ?ol ¤4.
Hiickel Hl+ +61 +H4olzl= 6fzluj ol4¤- ol¤- En=2(a+ t.628) +2(a+ 0.628) -4a,+ 4.48P
=ÎBol
6iol +.-q E4flol +ei111= "J+ CAg ¤E6J + 9ltrl
tr|+^J +Elqfl EzlE glHzlE F r45J qlqzl$ a;-uQE
0.488(0+ llskl mol-t) ql+ *+. *qq 2+ 46J4lzL *E "l*l
(a) n-dxl ollLlrl
g
=-Et
u-zl en.roll^l E u}q
"lEE "JeE. Hl=rlEl otlLlrl+_r. +¤+.
*"1 +4qflql rllq} 441E LCAo-Mo qHtrl, Euo ? nE*ol
"le+ "Jd+ "Jol n-a=J A¤ ^JC
9lHzlts q-q=4 e+ g tril +s= qlqzlq.EzI9 A+qlE u4 zlqE gzlql^l
a.t t.eZB, u+ 0.62F e+ asq, nE6J qlqxl= r4lx} e.J qlqzlE+q +
E = (eE.11) ^JC
g +41. 0186}"l +e + 91tr|.
olS fllralfe] r qlqzl= rB eE.2ql +44*.=ql, q^g
E."-E -Nâ n-3il 8d ollLl^l [8E] (eE.12)
ce-+q-6}q+. DT'TL
. 4A trlqE fz| t*ole++ r fllEaJ+E qlqzlz} H ¤zlrl N.E +zI +ql Eqfl= +^ gzlel ++. qlE^J +
"I1ltrt. 4qflql^J9 n¤6J ^J^d qqzl= 4.48Bol+.
. t I B + 9l= dzl-b 47Holq, q+^J Bl-EI^Jql dz} ull
35/* Erl+r
EEEEf,J H!=rplouLjrlet att

n?llse-iel qqzl$ Hrickel \
^l=s+4q$E
s +61-,r" olq^J Hl+zl+ {luJzlE +6Iq+. =^l-Be
7-
I
H
C
IalEt +E]q$ql^.le] *3 olrlq rr]4 ¤.d ¤B
^[B
rl9 tlg+ql, oltrll= As+ oz| td++= ag +E6]lot
¤l+. trl-Sq ¤H eE4E Er dill r¤B "llHzlE
=g
ol
+++. diil rE6J qlLJzl_tr.+El F n&zl aq+ qlqzl
E uu]|+H ullzlE] qlqzl$ Eg + 9ttrI. fal eE.3 flltlE oE4P Csp2 Ed +llE-t+=o| A^1^1^l BdE ?ioltrt.
0l ?1lE-Br+=e fl=aJol g.0l gr_+E ullEoil r+
hamilton qgg q^g=+ 4.ol 84. =ol"J=tr|..
=o!
(" P o P ?JlraJagol* +ê+ aa4î a+4I¤E flzt ul]gg +
4Uq(rH qe.:). A+4Bg ql4e 120"olE+ sp2 Ed Tll
H_ lpapo
lo pap E6J+E olelql ¤4E o¤6J¤. IrJE= trll *C"++olq, :f
Io oBd ?-l6lq fldE +48 E"Jol r--Eql"Jol S.E o¤aJg olF
(o r o r Efl4dE} (zoo 0
401+.
= q-$ql=
lr0l0 looo 0 Ezl-+lls6l+ olEetr ¤Ballot g ++g ^J4I
=al+ F
lorol looo 0 all Ezl.. 67llel c2p TllE6Jfs=3 aa4^l a?-l dill Eellql
[, o r o
Io o o -2 ulzlE n+llE++E "J=+. 4+4 ?3 hamitton 4¤9 4zI
dEi6IE Hrickel H+l ?lql^19 "lE9 9lHzlE +ts +
"l Beg q4dE+61-H +llE++=el qlqzlz| u|-o+.+ =Î
el+.
E=d,+29,a.d"a-28
a B0 0 0B
448 4zlzl z]l?l4o} ++. 24171 alzj +llEEI+t"llHxl BUB o o o
zl a+21il)= ilzl6}q E Eg 2+eE qE|¤ +llEEL+ 0 BaB 0 0
H_
(qq z\zl a"J)ql Eqa+. E|+^J dill qlq 4z qa+4p 0 0 BaB 0
71 ¤4. 27lE aB¤ n¤*9 M++94 9lHzlE 7l^lq, 0 0 0 pa B
trI+^J ol A+ql= HI+zlEl qlHzlz}0ol+. B 0 0 0 Ba
rPl B7[ 9E.2 ddfg zlz]r:ilol 414]9 9E"lol-¤"-HA
EE?Jq= ol+6}q+). 0r0001 2 00 0 00
taloE EF,rv +ta 'E 101000 cll4CEl 0100 00
010100 0010 00
-at+ 0 001010 000-l 00
00010r 000 0 -l 0
/r-,) ult}4. olr{E
\lJ/ o ci -r rj o+ 100010 000 0 0-2
$Ert ?]AEE ++Lll. ul{zls}9 zltr ¤{t ql= Hldl ol BgE 7#ils=9
ols+ ?"1 7d nao g]uJzl, + q-q=r+
4 "l Hldl +a= 4= HJ6J+ Ezl-5o14. Hl4l4 %ra}4 Ezl- ,Jr+.
s6l fl*zl aq+ olE4 EzI +llE6J+ olE¤. g.+6l]^J +
=
4U+. + d¤4-o e oE4ql rll6[^J= fl*zl ¤* "lE$ E= a,t2B, at B, at B, (eE.13)
fllralf olEg ^l-8-6ll^J ¤E+trI.

,<f$ap ndzl¤$ $zl.
+d gliTl 46J +++El ^J46}] BzI. 67HE cflzlt sp' "lag +4U 4"1 .zH eE.4oJtrll, {zlrJ +llEE}+E"tl E"J
E^Jg ol+r gieq, 44 e^Jqxl ?+3 +zl6J zp fllrEl+
44 szlES tr-g rosgl^J ¤Eg 4.o14. alzl-9lHzl +llE
6J+= E= ol* flzl-= all-9lHzl
6i+49 *=+r ^J4{+. 4 Bn flz}"llE 17HE HgzIzI ÎolE e.J¤- 444:r"
(cspr,Hls) daql el6ll^J aqlqq flr" +I}lzl zzl]9 Ec
fllro]f} 4L "Jd flzl*J
^Lolel
Hleqlg +4U+ E_ a-
qE Exl fl]E-Et+ olE: trl-flrt Erl. 355
+
a, ao\+(g.zl eE.zE -Bol4). C4H4EzlE +2119 n3
brn +
\/ + zl$ zlzla 9lsq, ul4rl dill n-dzl. a6-J "llHxlE
+ 2(a+2il+2a=4(a+p)o1tr}. + +zls} r-4E19 qlHxl
e 2u Y +@+F)ol+. E|+^J Hl-+zls+ qlqzlE oolq, ol E
+
4^= %r.6JC9 *zl ?*=+. t¤ cru42*Ez} olgE A+
K
5 {lE zrdzlzl zzll$olq, ,rl+^J dill r-dzl aEt glHzl
6
8,n \--^rr
Y z(u + zF) = 2a + 49o u|. t zfl el +zl El r- ¤9]9 "ll H zl ts
I
2(a+B)olq, q+^l Hl-+zlg+ qlqzl= 2pola- ol $z| ol

+ +
+
+
+
gg %F'Jcg 4b+.
+ +
dru
+ +
+
:IaJ eE.4 El{lel Hgcket +llE-Ef+el,ct|SolE oflLl^l q7loil ,\$-d 9E.3 4lt(U+El) ElEf
qe EÊ3 -trE 1oBoil^l ¤E6lx,!rt. Hl+^lel-fllEEf+=sl=fl. dEal.
U=-J ¤tr3 g^lE tolel Eltl+ef gZlEtrt. BtfgEt|oll^1=
=Ef
+llE-J+ +"J"J Tflgqq $Efr zlcg aI
=-'J =4ql= ^_EE?llqEol
=oJoltrffEtrl-. E.Htickel %r-Hg ols-" alzl ?*olE EzI +llsEt+el E"J4 ql
Hzl fflE 4l&6J + 9lg +"J otq4 EzL9 E"Jl} HI8
+zI +llEJ+Ee ?ld tlE rt"l9 e*, Hle6J q Hle.J
.<)7lzlE
^J'J.61 aq6.}rll
ql+g 6J + glrll qs.4. EzI9
ol sgt¤ ag +qql- ?l+. dzi fa$ Sd6l il?-l6l-= ,JHe +qlzl¤el zlqlq} +d
olzll ol r4lql+ +a flEl= 4+^14 Ezl. 67HE &zHzJ g ¤Eil slql ¤+E ++= ol+rll qfl+. r+l+ al&
=jr"
ol zlulzl|l +d.6|¤,
cgzlE+q 6I+4)z| zHg4oF 6Is_+ 37Hel 3lz.l fllEg}+ "l¤91^l= A*EI "JE eEuJ$ rzfl
E(ar,e} 2+oE qp+g ersa6t.)ol Sd6l ifl+14^] a2r"elr9 HI 6IEir Elq., r44q {zlrJE H,,e} H,,$ eg 4+# ^}
qr"rlEll ullilz[ +4+r]l ¤+. ¤zlrJ 6J 7[zl +s,* d3 d i a*pE +zl+ sa6l +^l6Hril4zl ?*l olE¤- 414}6l.4
#B Ezt +JEEL+=ol d+ A6JCS +4U+= aol+(E ,l +C6l+ "JHql +6llî dzflts 4o14.
9 onq,<'1 ¤BEl N, Ezlql^Jel tl e-Jr+ +^l61trL). flzl-g a+ql ol+guH zl-ill_"J+c e:(scF) HJB(Eq 88)
ql^Je+ *ol eE Schrodinger !$ zlxll-"J+Cg ++LJ]E+
Hltlel ndzl {lulzli q-q=$ {."1 84.
+++ zl4IH ++. r?]6Lq *d tszt "Jql 5qilb s=
o e.
En= 2(a + 2A + 4(a + F) = 6a + 8B dzl¤91 4el EzI +llEJ+# LCAoE ++trI. r?]r r
+ qI Ezi +llE6J+E da6}r +qzlEg 0l+6}0l dag
"l EzI9 ul;tzlffi .f,(lall ol Ezlzl :zH9 L
EI"J
+llE.J+fl dz}9 ElHl¤ qlqzlql Eil6J !g 4le+. r4I
B¤ r?*g *.r}l ^J46lH :. ndzlE9 9lHzlE olBz]l
"JE scnrodinger 49 +zl 4l4}e-E Eq^J dAg E
3(2a+29)-tu+6871 qolo} e. a"l+. q4^J ultzlsl 9l zI +llE¤-+¤-Etrl +rll "JEI :z "llHzlE g=4. ol olB
HzlE 2g=-a80klmol-'olq, +4qflql Hl6ll^J ^JB6l =.4. g E= +zl-+JEEL+EqI Eil6ll^J HI+6II" EzI9 dill qlq
Hrdel n¤* ^Jd qlqzl= 8B7i 94. zl$ 4lt6F=ql "l+ql+.relr "l "JBg qlqzlzl "Je6l
ol^Jel 3.E= E6lol ,J6J+ o+'JEE ?]A^dg + 7Vl 71
al q¤ 4lzlzl Hl+qI+.
qq s+¤qr E + fl+. a?ql= e+4¤ +a7i cl o¤6J
BCql "J^d*601+= 4,"14. Hlde-l oE43 a#E +
= (a)u-d:d4 ,JHE[ +01=4 HJH
4z| S4E 4o14. Exlls= dzl¤ol il]+lzl= r?lls+fE
ol E+ A-J +llEEl+=olq, q+^J Hl+zlE+ qlqzlTl r+ u_g:d4 r*Hql^JE tr-B+E 4Eg +%l+4 cllolQu| E
s "lg3r+ 9luJzl$ eg E"-14 CeE+El +68, "JAE +
= Î¤oltr|. 4-=¤ ol.$oll,<J "J+ 5e.J 4+g 0o + +e_r+. _=_9 qo9
ZI+6J 9l gp.rolld 4E aE,tI flz}9 olg+ ollulzle] {z}
ExtE gB+ ¤E EIE
ztEEt 0ll 9E.2
ql qlqzl= E-d, +
^l=++QqflE Ezt +llEEL+E 2P,
r z|,tlle} ql= A=fl zl^ll+ ¤Eg oxfordgl^l ¤rJ-J physical Chemistry:
Quanta, matter, and change(2014)E- S-"I4.
3s6 e Erl75,
rlsiEE e6J6ll^l 'I44S.tscll ol BHe. ulE ol HI-de4

,JHel + H 4 ¤4o14. il¤ #01E4 g$(ab initio method)
(+rtl^1il)
ql^l= Aa 4Eg sslal E= 4E- 4l&6J+. olE + G1
\
G1G2
,J^le gaE .JE 4l4I=¤ 6ilot +r+. 4l4}g 6Hot 6t= zJ

i
+ +ql= 4 flz}4"ll +61.= flz| fllEaf,fE -tr6J^14"t at x G2
aE fl+. +rJ ,}le-l "tg gz} +llEEL+. olf-a|l,tJ $z|

= gE 4Eg +6l]ot
+llEEL+E- "J= trll= i "J z}]9
ol+l+
e}4(zlzlE olf flzI +llsetfg +9 4zll#q qq zl+
=
4 tllizl ?zla}4, u|4rl toflz} EzI ¤ 9H tonz119 4E x
Ahlg 6flot qI+). rq6}q "J+el "JHEol

pealr|. .f.B 9E.s AolEl Aq F Gauss --J+E BP + 7lG Gauss -Br+ /.l-ololl
=Î F 7lq=C
z7l olE E+qiql^l ol+g * ++4"J cNDo =Col
91tr1. Et+3ll Hl6H^l ol=E Ee 4E= qcH^lAtrl.
=^|Hg ol
(complete neglect of di:fferential overlap)+f d+ a"Jql, *
Bql^J= voe| rlr,71 F"Jqi qql +Cg E E"J +llse+ol (o) g-= E-Et+ olE
-7 E VceI VoE rflB A+. ^lle.l6J
q=q=r| ag Efl E=
EzI 4E9 oo e -aE4 L}trJ:d q 9E.3
f*+ 4.g EE Gauss EI¤ zlzlt_ +lil 0r+ Rql +lil6}

i, ! ! w Jn)v,?,)
lv..v,)v o?,)dt,dr, t: ti141 'Eo 4' 4l= ^Jzl6ilEz}. rElE +61lot El -J zlg
¤"its$ 4+=e qlLlzl fflEol dflzle+ gzl6J $lnlzl +q +s=r+ ae E9 o}"l Eqz}rll E+.
E: 9}6JEE ^JC erE.jIl Al.J^l7l deile+ g "*g rq|,ttzl y *' o1x - R)2 z ax2 + 2 axR-a R2
r)ty r(rr) -- g- -
a¤6]]=+. 4e q 4l-=.3 Hl-dE4 "JHq^l= 0-o + zl?-.1 ^(r "- "'
g 4Eg olilH 4614l E44zlE 9*zl"J ol HIBE$ s+ .*4 -ufx- !R)2 - -2ax' + 2axR- }atro1 e1. q+^J,
a7l cNDo Bql^J +49 1E"14. g-zoG-an'f -aR2t2 - a-24('r-R/2
):
,-aR2tz
Vt oQrW s!r)-
+-01E4 ,JHql 4+q. il+.
ÊEg.llqEE ^l+qr olag + q r=+Rql +dg E +"J
¤zl,tl E4l7I != ag F dxl- ÎolE Coulomb tlE4I+ ^rolel +A +lil,
ql 7l"Jq= +le+ ee gE 4E fd z|]E 7]$-6J 6J Er+4 Gauss .J+(449 .Dql Bl ql++.
o _tr
+6l]o| ol-i-rll, ol 4Es=3 4 flzI +llE++Eol ^Jol
t flz}9l 5.Cg E ol= Hl'4+d 4$'ol ¤ zl*C$ l4
6llot*+. Gauss ¤ TllEEL+r=E d¤ e'Jg ol6-6tg ol "J s+rl ExI +aE 4l+61+ rll zl-tt ts4 ol+qr gl
=4ql
"l gd t¤6fld+. Gauss E +llE:d+(GTO: Gaussian type = "JBE 6I+s zl-48 E6lr fl= ag "JE H-d+ ol=
(DFT: density tunctional theory)o1r1. ol %FHE tr-dg 4l& U
orbital)t: {ra+ eg Eq 6-rfol4. aq+ +llEoJ+(+iE
olf+ qg Eq+r, e+q rj + a H-r, E d #+ z1¤4
4lql^J= e-'ql Hlql+q) ql^lql ol Gro= ^l}ol
^l-s6l-=
F Gauss #g q^l Gauss grfol{, + ^dE.J+EE
'J+el
+z 4+ += "JB o e eg ats+ d¤ ar+e+ q 3 "*=
+rJql fl,.l*+= old qlEol+(rH eE.s). ol *BS "1¤. ar+= Eg + 9l+= 4014.
alfl "lel ?Je 4+4 4Eol trfq_$ gg gE 2+4 4Es_ DFr= vE-+= dz} "JE p9l ad9 "*+r 9I+.
.HEI+'+L Eaol Eqe ++4"J ol#b tsz}g qlqzlTi
-+ ¤tr|.
dz1 "JsE EL+, l Elp)olt_ E dz} gE= r z}4lol flil
i,lIrt ,tlvo,)dr,dr, E 6J+ p?)olzl rllEol4 Et+E Et+E ++ql^J 'HEI+',+
J- Y dzt I,JE= d+ +llEEL+E¤ "l+6}0l ffi al o
x* =+.
s+q "JE=tr]l, ol a+ +llEEL+Eg Kohn-Sham Al"l4
{zlrJ Vovrql q1+6}= Gauss B +llEoJ+"]q, v=
Vcynoll 4s"6lt Gauss ¤ +llEtrL+ol+. ol46J {-E 4Eg r 6l+ +Ag e4E Schrodinger rl# +q^l +++.
B4E 4+4 4El-+ gd q dr rutE 4l +71 4lt"l 84.
flzI +llsg+=. ^lEqlolc6lTl +l6ll,rJ=- rl gg Gro# P?)= I lv^?)l' c^[ qE gE (eE.14)
m,occupied
6110} olzlu3 dill4 e_E= Al4J +_sz| E44l+.
^l-s-o
eE E^l +{lEel+ olE: cfflxl.E^l- 3s7
I^l
t,
I ? l=
(a)
lg
(b) (c)
9E.6 qal E,\l S4oe LlEl'.! ollEJgE 5B-=. rE: (a) gill4 ES
l.
E^l
71nl
(b) +E EE -Egh (c) "Jd sS. =ti
aPJ gE.t elpot rfloe LEF.! ollEJg EE. 0l EII'= :aJ gr.6ollllel
E"J-d uH-Btoltrf. 4^{g 8rH4oe 3E EIEJ!¤ gg=, ralr E^49 8q4
Kohn-sham 49 qzlHql tr}+ ztzil "J+Cg 44 Eq"t o+ s?] tr1E!¤ gE= LfEILJ+(6-O-H&01ll1e[ 'J0l).
oJ+. . +d dz} "JE= d4e_E C6L=ql, ol a +4lql^J
E "JHl4 o .tr. flz}9 dzt "Js.E +A^lvJ 4g "le" d4. 4 E9 EoJ-e--tr eE.6). rHql^l !-ol ule{ pol
g.ql= Kohn_sham g-qc lzl-4 o _e 6J ol *"JE sHg =qBq(rB
^lg- ^llEg +llEJ+ "Jal4 E_oJ, +e+ "+EilEoote-tr 44U EzI
E E=+. rqr "l + ^llEE +llEEL+. olo-"6|{ a+ q . +¤6trll Bq+= _EoJ, r4r "Jt E"J + "l+l ztzl "J
+g dz} EJEE +6F=ql, ol al4l r+ag z$z| pre| olluJ ^le
F +qB + 914. ole+ +¤g E 6}+q s^l Br-Bg E
zlzt "J4¤ "Jql Atg +ElE ri|;tzl Hl+61= 4,o14. ul|-Hs EEloJql, olag *ol] Ezl¤ +_tr ^J46Ir. ol +
7L Efl+H + 9l= EzL Etsg
"l +E +d +lz'l$ zlzla-
(c)
=afli=.
E UE +4U $zl. eolo1r1.
4lt} Eot s}+.ll^J zltr ¤zl6J Bdg t E"t9 6I+= E EzI9 zl6l-q1-4 E"Jq *zl?+rll trJ +,q+ 4,3 Ez[ s
zI +llEBJ+e+ dzl. "JsE :r-4F + +4'J + 9l= Etlfl A6I EE4. olag 5ttr-4_o + 86z14 tr1EJ!¤ EE
"JBoltr|. .J dqlîel ?l*4 "Jd6I Q
EzI +== 41416I= a r+Ag zl EzI +{E.J+ql
('elpotsE')g zlzl:il- +4u+
=q7}= ,I +El{= iilQl¤ "|uJzl Ep. ol d6te+ BzlE dill qE
ilx| llra;45E 4l+E4 olE EzI +llE.J+el 9lulzl <l
¤- +Elql= gH|gi= r'JE= 1o14.$zlr 1lra65 ree
4 dzt "jE.oll 7l"Jq= d6l ^tolE tlE4L¤¤ r.el6}r 4l
E _E¤6tzl f-la1l,t15 zlz.l ,tlls$ "JC "J^l.el r+ _E-oJ_g-_tr. &6J + gl+. r?]-r1 ol dql^lE 4zl4 ElHl¤g o+r 6tE
Er=e@9e + "l trlHl¤ qlqzl= El¤lfe afl4apg 46JC
4441, "lq^l olEel a_71= d¤ AR +q 4l+ql "*rll
ae6l PszI t"l* t"lal {$ z}zll u}
0+e}8 + 9l+(r4 ge.z). dÎ-++ gqg "JHI49
-+
^4
4U+.
=+ E gE alHl¤oll" dzI-¤B gEe "JE tr]Hl¤g 4=+.
¤zlrl ¤¤6J E^l HIBE$ q4 Eoi9lrl {+fl +s6|
"J+ 4l+# "Jrll EIH qE +llEE}+zI E+q*.EzlE
H;r oli. fllEEt+$9 zll$S fl6iq EzI "Jqd9 dz} "J 4l Aql+. qlE^J BzlE dx} dE gq¤. "Jotrll^l trL= E
E$ fallo} ++. rqH olgl a-ol 7+ q^=" g-*=e-l "Je-lE zt9 dzl ++ gq+ Elq+lEzI olael *49 Eg + 9t
zI4= *. aol4. olBl6J e4= +,q-ql EE E?-l Eq
dql^Je-l xll*el 6Jol HIE r aql^JE dill dz} EsTi ¤ =
4"14. olalql a4= EEs. EE, + "JC6J * dz} gE s . EL-dqlE ql zzil ol$qr fl+.
=s-d71lLJ=
tr1. HUcket gEql^l= "Jd6}zl t*9 flzl¤ r}"l9 aar+ tlE -7. HidlE"JaE= r.e-le-l Tl6talzJ +ae| b3 ul+zlgi qlq
4I¤¤ +^l'tltrI. zl qEql
^84q.
rJ2. oJ Ezlg ar d+ ?.llE,*+(HoMo)e+ alx] Hld+ +llE6J tr8. Et-d-d4 4]tl gHql^J=
¤e4 rilolelE 0l+6ll^l
+(LUMO)=: EzI9 e4 ?{lE-d++r oJq. -oe 4ts¤ +6Iq, #olE
t'Jgql^l= E= 4+#=Î4 +il
tr3. Hrickel HJHg flBg ol_c"a|.{ ,JpalAl +4.J + 9l+. 4l&'J+.
o4. n-3ej 8C ollLlrli r¤Bol ^JCg q %I=q= {lHzl4. tr9. "JE H-d+ 0l=g r zlill rlltql dz} Es"ll "J
trs. n-dll eEf ollLirl= 4 rdzt9 ollul zl9 6Jolr+. 4-J
^lg
ol$oJtrI.
tr6. H|frIH qlLlr!= ndxl qlqzle+ +xl3r} nd6J¤ *E E.J !10. rqs TlBql^l= 4zl :?z 4l& Ar+ql g4+ 4"&* s
+zI9 qlqzl rlol9 Îe+ a+. B¤ ril4.
358 ErtTI
=g:dAl=
oe,
ÎZI -1I +^l ul Ha
LCAO-MO v =Lr,ry, ya= gz} flIEEI+ 9E.1
Htickel 4l Hc= ScE Hrickel ?ld E (l¤ zllE6rB 98.8

=^h
H4s=0;S=1. ÎolE
Ell4CE} ctHc = E 9E.10
n-dzl ¤El9lHzl Erc=n dzl9 qqal qI -Zl

o-1 ol
n_¤6J rJC qlHxl Ear= En- N.g C9; N. tsa, flx}9 f 9F,.t2
=
n-ul{zlsl ollHzl Ed"lo.=Er-N.(o+B)
E6 3se
E71
^9 =rl 7a
EEI eA flIt7l-=-BF 0lE
¤E E^11
DeA.r qel B{E gC ?llErJ+se ¤g611 olEol "JrJ gAL grJg DeA.3 +Bol +4rll= a4= +.9."l4i
¤c6l+ rll 9Bz]l olS9bzlE ¤E6Iq4. E "J{l cHr=Q=6srql^J +
DeA.4 Ezt ulHI¤ qlHzl +dol+ s.Eg +6F= flztz}-d6J Alt"I^-l
cH,zlzl +zlBql FolE ol*E gcg zlzla_ ¤E6Iq4. Born-Oppenheimer *rl9 q6Jg ¤E6iq 4.
osn.z ?B"l ¤CE trll 4¤- "lFE "l*¤ ¤E5Iq4. ol zllHg osn.s fl1171-41g' olEql^l +41+ gcel ,llHg 0l+61.= ol*¤ ¤¤
flztzl a6-J olEr+ ExI ^Sol olEg
+lls'Jf zlzlt_ ¤B6Iq+.
6Iq+.
c{--\
Ll tl
EeA.l(a) A4.zl NH4*ql^le| ztol 4z\ e6Jg BC'J + 9l= ol-,?E ¤B EeA.S(a) sp'EC +llEEt+ h=s+2ttzp= A+3rl^14+. q7l^l se} p flls
6Iq+. EL+E* zlz] rtr- A+elqq fl4.
EeA.l(b) oJol pFsql^le+ rJol szl] ¤tl¤ BCg + 9l= olf¤ ¤E6lq EeA.s(b) 9# Ege.a(b)E dB A6Jg 4++^l7i+. ¤zlrl sel p +llsit
+. +Ee zJzJ rE A+EIElq 914.
EeA.2(a) gC fllEE++= zlzlt- r,r-F449!e] Allg ¤B6Iq4. EeA.6(a) HFel *"J A,Etq 4oJ flltzl a6J sl-trroaJ+¤ r^.1+.
EeA.2(b) gC +llEt++E zlzla- r,:-$44tlel AElg ¤B6lq4. EeA.6(b) N,9 rA A*ql 4.J fl*zl-A!+tlÊoe-+¤ r{'14.
EeA.3(a) gC flIEEL+E zlzlt- +g g^dill HF*H*F-H-F*qI 4aJ fl,tz}-¤d-ul-Eoe-+E
"llpol"J Cn,NHr9 e'*g ¤E6Iq4. EeA.7(a)
EeA.3(b) ec flleqlag z$la- vlElg c,u,N$ aElg ¤¤6lq+. ,{rk4 +aE /J."l* 7lq= Es" 6}q+).
EeA.7(b) E.J6J qlLlxlE +B gC4l Nz*N*N-eN2-N2+ql 4t g1t
E9A.a(a) d¤ A.J ht=s+px+py+p"4 hz=s-p,-py+p,i ,tlg zlLEl$
7l-4q*
e¤4. 'IEel+E 44.
EeA.4(b) dB e'J h,=(sin ()s+(cos ()pe} hz=(cos ()s-(sin Elpg -uE {} EeA.8(a) ?ZtzFdt* olEg ol+6l-q p,ExI9 +aE ¤Eaiq4. ExI
E (ql ql4^J ^ls ^lB 4rEl¤-
trq4. t}4ql^l pnz| er-E-c| q "Ja.J ol*+ +Eol+?
EeA.8(b) sltzl-¤ll ols-g ol+6}q so2el so3g +aE-¤B6lq+.
Eq eB E^l+llE-Br+ 0!E: t^ E^l 018

¤E E^11
DeB.l aq+ ¤Cg "JqL|rll ol-E EzI fllEfl+ olEel 5Ag ¤E6Iq+. DeB.3 .+zI qHI¤ qlqzl +dol+ _s.Eg +61^= EzI-+llsE}+ al4iql
r.l Born-oppenheimer z^1716}= q6Jg ¤B6Iq+.
DeB.2 eql"l at} Bcg +44E H¤4 Saol 9E olf* Fl
^g+llEE!+ olEE "Jtlq^-l ¤B6IqaD?
olLk+Î
G^
Li tl
EeB.r(a) 4?J 4471RoJ H,*9 9lulzl= eB.4^l_ee +qdq. ¤zl"tl zl ¤ zlrl jo = 27.2 eY, ao = 52.9 pm, oi En,, = -tool4.
q6l+ {tE¤ oFlql L}El-l]fltr}. Bz} qfl¤ qlqzl +dg rE-Ijr, e.J EeB.l(b) ¤6 pqs.t(a)ollrJ9 EllolEl= ol¤'6IE Hlad. +llEEL+ql qq}
6fl4 qlq^l(ev*glg)e} E¤ At} ?olE +6lq+. +rI irl{l¤ "lluJxl +dg ss.z^19 ol+6}q 4tg + 9t+. ol +Cg E
^l6}q4.
Rlao I
0 2 J 4
EeB.2(a) p flzI flIEEI+7i +Ee=e ++61 A4^l q
^JCg A'* HIA
jtj o 1.000 0.729 0.472 0.330 0.250
kljo
tI n+llsE}f9 e'I u Cd9 LI+4qz}.
EeB.2(b) d gzl +JEq++7I Hnl4 "*qn 44.9
1.000 0.736 0.406 0.1 99 0.092
s 1.000 0.858 0.587 0.349 0.1 89
^JCg e,* "t Hleq+ 6
+llEEt+E e4 C49 +4,{q4.
"
360 e Exl+4.
EeB.3(a) EÎ fllE6J+ V=Ve+)"VeE ul4"lel l"e+ Aa 4E S= Tlzl-r. EeB.a(a) +iz} flIEBJ+zl0.l4sA+0.s44se+ eg g(C+s+qzl g*ge i
A+sI^144. vro4 vrsE lE A+3r+9*ql. 7IA6iq+. q4lq. ol Tllralfo{ z]rdl-= +llE6J+ Ae} Bel cB a'*g +6}+. r
EeB.3(b) ¤# rss.:(a)g CB A6Jql+ CB Ael +9 4 flxl9 +.llEEL qr + dB e6JE C+e+ ^J+E s=0.2509 ol*6ll^J +6lq+.
+E¤ rJ *{ir.1z1H r +^l-= trl g ¤E6J + 9lg 4,"14. +z} +llE6J EeB.4(b) +zI +llE6J+(HI-A+e+)71 o.zztt+o.144Be+ rJg Ee +q{
|. y=ryo+Lryr+)"'tys'Z u|4"14 trel tr' f-fla aa 4+ S=-7lzlJ. A +. ol flIEEI+e+ zljt6l+ illE.-I+ Ae| Bq Ce e6Jg +614 r4I
+e+^14+. Vrrel-rrn'$ Szl e9 {.il6l= +llE .J+8"1tr|.
^ls F C¤ a$el A+ql ^J+= s=0.1r79 0l+6ll^l +6Iq4.
EE ec E^l+llEEt+ 0l=: 2fl^lE^l

=-e4
== =xlt
Dec.l Fq zflz} EzI9l 4eI +a g4E +zlg "++6Iq+. ox.t fllE Aee Aql ^llTlql qL aEg ¤.J.3 +L+? olaol q'-
Dec.2 s flzI +{sE}ie} p flz} +llsEtfzi Ez} flls,Eri9l r}er}-e zl dtr + 1la. +4q=zlE +4qq4.
q6F= ol+= ¤B6Iq4. Dec.4 oJd6l+ flzl¤9 p +Jls*fe} d fllEgl+7} Aql 't t}?tl EzI
+llEq++¤ ¤¤6J + glE+ B}]6JEI= qel s"#g jfg_o + LlEt.]]q4.
G /^-
IE
Eec.l(a) 7+ 2+7l|E4 zflz} Ezl9 e6J Zl+E +EiLIq4 Eec.a(a) i) Li2, (ii) Be2, oi (iii) crE Hlqtl-Ell {z} ullzle} ¤B z14g q-u
qq4.
"18 xiq x;9 ¤,$ +EI4q+
Eec.l(b) 4 2+7\ Eq 2gzt tszI 2145-
g+.Eec.l(b)ql^l Eec.4(b) (i) F , (ii) N, oi (iii) or-el Hlq^JEfl dzl-H11zlE Lt+qiq4
Eec.2(a) "J*qI +E 6q^l "]ts Ezl fllr6.J+5o1
?+
Houool4i Eec.S(a) 8,4 cr9 EiqtlEl] {z} ullzl$
"l+4q ol +9 qL Aol q
Eec.2(b) ¤+i Eec.l(b)qlî "J+6J 4 *E 6q^l qts Exl ?llEci+r= .t a{} 6ilel qLJ zlz zl4 4r]zlE ql+6}q4.
ol r_uuool4? lEec.s(b) Lire| Be,el Hlq^JEH {zf ullzl$ "l+6}q ol 6q qL aol
q a6J oil4 qlHzl$ zl4 aoJ^l= q+6iqe}.
Eec.3(a) uletol r00nmoJ +Îsle-l *zlql 96ll^l olgsl ollHzlzl 12.0ev =
"J TllEQ++e+q *Ag "JdxI9 +qg 4,t}6lq?+. Eec.6(a) F2el F2* 6qlî oll4 9lulzlz]. rJ +g Ag q! aol+?
Eec.3(b) qlqzlzl2levoJ +ÎCq EAIÎ EzIg olgsl9lHzlzI tzev EeC.6(b) O2*, 02, Or, O1- f,$$ dit ?"lz} +7161-= +-9-s +g6}q4.
9l +llEE++-a+El *4zlzl %I=El=ql r +qe gotz} EldL+?
-tr4 eD E^l-+llE-sr+ olE: 0l=oI 2?^l E^l

¤B E^1t
DeD.l coulomb 4E I +E zlBq E4qzt elE= +9,o1+? DeD.3 Exl +a 44}ql ol¤.q= +lzl ?.llEdi+r=9 qluJzlE ea6l-=
D9D.2 Pauling4 Mulliken9 dzl $Cg 4E= ¤B6Iq4. ol$ol
Ell dz} tlElrE 4 rJol "l¤.61+ ol+= ¤B6rq4.
olgE+ 9lHxle+
f,t1.
4 o e v +zl "*= ilol= +4ql= olf+ +9ol+? DeD.4 HB ?14= ol*6}q +z}.el {lHxl$ 4l4i6l+ Ell +qq= *{
!i$ E6Iq+. q¤ zlCol gqq:*t
G^
Itr
EeD.l(a) No-e+ No*E {z} ullrlE+E "l 6: qL lol cl ** 4* ,J Mulliken9 dzl *ts 4E
EeD.2(b) Pauling4
ÎolE H+t'g ^JB6l 4l
r*A=zl q+alq{. +4U 4,"1 go.+^lolr[. z]E ¤9 s go.r9 olga[{ o] S
trlE "J 6lrll
"l= qe 4ol rJ A-g A6J rJol
EeD.1(b) So-elSo*E d7I. E|]iletsel ol EFl"l 3+71 gÊql 46ll^l g"I4 t "*Ezl 4^16ll -BoI4.
E *4lbzl q+6}q+. ==
EeD.3(a) HClg $zi llrga¤- alt6l-bEll ol-o-oaj +llE6J+ qlHzl#
EeD.2(a) Pauting4 dzl *¤g 4E Îolel H¤lg ^J=J6l C
Mulliken9 +6Iq+. g!-6J EllolEl= e. ss.+q ae.sE ol+6}q+. 0=-l.00evE ?l
slg {ol so.+rlol+. z}e ¤9 s. eD.tg olg-a}{ ol {
EI 6lrll +ElU 6Iq4.
*al"l 2+71 flLEql ql6ll^J g"I4 e- *Ezl a^l.4 Eot4. EeD.3(b) HBr9 -+zI fllIaE"+¤- 4lt}6l-=Ell ol+E ?.]IEEI+ qlulzl#
E= 361
+6Iq4. gs6} rllolel* *. ss.4e+ sn.sE ol¤:otq4. 0=-1.00ev8 ?l EeD.s(b) s=0.20o ? +r s+ EeD.4(b)E El=ol 6Iq+.
6Iq4.
EeD.6(a) (i) co, (ii) Nq 4 tiiil cN-el Hlq^JEll {z} ullzl$ +4,{q+.
EeD.a(a) ¤# Ego.r(a)oll,9 4l,tHI <,tE¤- ol+6}q HCIE Ezl fllE.Eli EeD.6(b) (i) xeB (ii) pN, 9l (iii) so-E HlqitEI {z} uflzl$ +E}.ilq+.
"llHzlE +6Iq4.s=0o E FI4. EeD.7(a) xeFgl 4qI EzI +llEEI+ "llHzl rHg r4J" r Hlq{}
EeD.4(b) ¤f
rgp.r(b)ql^J 4l{l+ aE¤- ol+6}q HBr9 +zt +llEts+
4 dz} E}]zIE
+6|q+. XeFzl XeF+-H-cl. q=+l
*g ¤* ,J"lE *A!+?
9lHzlE +6l-qe+. s=0o ? FI4. EeD.7(b) IFql rll+ Ezt +llE.E+ qlHzl fBg rErr" r Elqtl"Eil
EeD.s(a) s=0.20o ? 5l S# EeD.a(a)E 9Eol 6iq4. {x} uff zl$ +6}q4. mz} 14 rF+-H-tr} trl =+l
4.g EoJ ,J"lE ?*il!-+?.
EE eE E^lTllE-Er+ olE: tlfl^l E^l

¤E E^11
DeE.l zli-ll-"J+c + olEe-a dz} +aE 4lÎ6J rll ol89= 4l4I r+A olEHEol q$rll 4Ezl ¤B{qq
g "+a5}q4. ^ls
DeE.4 Hiickel %LHel zlZzl9E zlC9 Hfl, e4, f-elr o.J4lE bel6}
DeE2 7\^1^llEoll^J GaussB fllrg.4g +^'g +llE*+-B+ H Caal q+
+ olfi¤ ¤B6Iq4. DeE.s Hl+zlE[ ol]uJzl, rdz] aq+ qq4, :feltr n¤tt ^Jc qlqzl
olq zF= ¤B6Iq4. ^]
oges dz} +aE ed6lt HI-dE4 *8, f-"1E4 *H, "JE H*+
G-\
Jrr
EeE.l(a) Hiickel +ÎHq q4^l :1r-lr EzlEgl,tl B.qs czp fllEEtf EeE.2(a) fu| +ue?IqE "l¤.6}q Hiickel EI+^l (i) .JE+tl
# zlzl e iq^l (i) "JE+{l(r)4 (ii) qltE4d(2)E ¤E 4B^lg (r)l} (ii) =ÎHql
olltsz+tttz)9 r-dzt A6J qlq zlg +{}a}4z}.
^lle q+^J (i) ol-=flI(3)
.,^-l+. EeE.2(b) fq} +:negJqE ol+6}q Hiickel
+ (ii) ot^]l+EB{l(4)el r-dz} ¤t} qHxlE=ÎBq
+4}6}q4.
EeE.3(a) HeHngl 4aJ dz} tlell hamitton ¤{}zl-E 44.
EeE.3(b) LiH2*ql 4aJ dz} t4 hamilton ¤tzlE Al4.
EeE.4(a) Hiickel 4+^l (i) cB H, EzIe| (ii) ael¤ H3 Ezlql
1 ?JEalc! 2 qluEet,!!
=ÎHql
4+ ¤E B¤4g r{4.
EeE.4(b) Hrickel q-r}^-l (i) d¤ H4 +z}e+ (ii) r"_lB H, SzI9l
EeE.1(b) Hiickel *^tHql rl4,<l lqr EzlE"ll,tl HqB czp 71ls*f q.J gtr =Îtsql
Eg{g,*l+.
E9 zlz1 rll= + ,^l^l (i) 0l-641(3)4 (ii) o}^ll+iaBHl(4)el ¤'J 4¤4g
,rq+. EeE.5(a) (i) Hldl¤.o194 (ii) tldl "}"lgE {z} ullil$ ql+6}r, Ee} rr
dx} ¤!* qlLJ^lE +6Iq+.
EeE.s(b) (i) "J?_ ?+qa .cH2cHCHrel (ii) qH,* "Jol+
^l=e+4qgl,
9 dz} ts||zl= ql+6}r, st ndzl e6J qlLJzlE +6Iq4.
EeE.6(a) (i) fld *olg4 (ii) HItl "J"lgE Hl-+alEI qlq ale+ r¤,* B
3 0l=il1 4 olAllLtuEJH! C "tlHzlE +6Iq4.
(i) "Jg 4qA!+ (ii)
EeE.6(b) ul-+zlsl .tlHzl
^l=s+4qt! "Jolg9
4rE6J BC "{Hzl= +6H4.
g,lx 9 E^l 7a
=U= =xll
te.l EzlE dz} +a oJBg ol*ql^l Tlill^J Ezl¤9 .s'+ ^Jc tlBirl 9 (a)91î +e 4 EAEoil q4^l s= ^8C flBulq 4lÎile} de,l
^tolg ^J'llzl
sil-= 4l^}6}q4. (.) BE*44 qlolEl Hllol^ +ql* E=
^JC tlgrlel deilql 46J E+AE.= EBJ6IT 9l: AE 9l+. detl
ol+6}q Tlill^J qlfl, dl^tEe.lfl, "i +$qlEeielel .E= ^JC
+4qfl,
tlgirlE zltl6rq4. o) g3rlql4 qlolElel ql"lEl EllolÊ ataol¤ * el E+CE= O)ql^l al&.J t'il e4e| ulaafir, C¤ gc]$
=E$e]
362 Erl+E
zJ Ce¤- +6171 +16il^l q}^Jol caqi HI-¤el4 'JHE tlqEql +6ll^l tg.sHE flq= Exloil,,.lc+ uffizlzltr flzI 491 Eqfl= d4-E9 si
E6Iq+. E1I+E "JE= clls ol$$ + 9l+. xl* rf,.,a=N(d)entg +4 gr+E
ls ?llEafql qlt irl^trroEl+g ol$aJQ-r. {r+6I !_z}. qzl^J N(d)
re.2&El-gg r,*9 s'= d+l= flxh "18, $$ $zlz| azl¤ gol¤"J ^lE
ts A+EI ^J+olr oE a¤* u}4"lelol4 trl-g *Azl CBEI$ trq
+ 9l= gEqlzl Aa,Jq CE= ++{= {"lr(e$ 6D). S+ A4ql E 4.
olg ruuo qlLJzle+ %l,a}+ +++Eel s.= dg
^lolql= tl++4lzi
?l+. s+d9l} ruuo qlLJzlzl A^6Jql rl4 fzlrlfle+ EE e^ E(a)=y_2,,(+)"
6ldL+? ol+E ¤B6Iq4.
e^]- +Jetlf 4l&g ol+61tr ^JE+zi dz} "ld Hl+ql +q6l+
re,3 q7l^l e= 7lE d6}olI. p= Hgz}el ¤tt} dzloltrI. ol ul-E:oE-+eI
+lEol4 ee *q Et} Ezl-E9 s= d9l9 46;19 ql+g + g*q= 3l^ qlq^lE +6Iq+. ^lE
0 e LUMOq qlqzlfi z]A,<lzlE : Ezlzi LUMO-=. dz}
9+. =+Hlr+
"JHI4
E Htrl^="J + 9lE bqol golzlr, Ez|.9 .s.= dgl ilol ."rBoI6zI re.6 gf,t7}-¤tt olE4 +zI fllEE+ olEel +qr==g Bss+ *zl glt+
6t+r "J"lzll il4. s"J olq+ FJ:e ¤+ e4ql el6IE %r.6$+ +++ -E.g EE trll .JHI4ss dq^J ol+¤}tr}. qdg 4e6}r1l gcg cH2+
49 ruuo qq^lel +l+l d9l ^lolqlE CB +4lrl 94. (a) ,tlB-ili+ cH E.IrJe--e. ^JCE]fl4= tzql oJ461l^l ExI +llEi++ qlqal +91 r
1,4-tla+l+(6)ol 6ll'J. ,r-ll"l+]ts +q+ gol$g.e. 9E rdzt ¤+?l Hi* H9 r44.
ql q.J pH 7ql^lel s= A+l= trl*g-r+ Aq.
re.7 qzl^JE EEAqI^l olul}t4}# ¤A^l7l-r. r BE BEIIE ?]C^l
7l= EqE Tl7ql *o'J Ezt flIEEL+ olEg:fl+6}qrJ4. +414 o
& R3 Rs R6 trtv s'J6lE flqE BE +48 "J4e+^l7l= s-oJg ^d46ilEq= a
H H H H 0.078 ol4. (a) "JHI El+'lE
r+Ag E6ll^l olul ullflflxl"J tsqE 7lE ¤ts +a
CH, H H H 0.023 EA rqr. da flx;5ql aa r¤ilEol tBql 9ollrl Bl+zl
CH, H CH, H 4.067 =.tI^.
E}qzl trIEol+r ¤B6J + 914.
CH, CH, CH, H -0.165
CH, CH, CH, CH -0.260 :o:
o
,?it+; )i [lt*)1**'" .ll.-
R6 R2
I ,BLI- /l
Rs R3
rr++^l q c, ',i N flzl¤9 Hql +zl'J 2p fllEi++# zlzlt- LCAo-
6
rvroE El=q^J +zl flIEEI+ ol$ql oJ4oJ flqE= bg + 91u}. +
+.q',l} Ae Eq CB At}g EI=+.
^'ll
4^J zldolLt r+71- dc+ aL$ %IHGI ¤e14 %r-8, +-olE4 %IH, Vr= ar[o+ bty.+ cty* r[r= dryo- ety* Vr=fVo- gV.+ hty*
gE H!++ olE olH)¤. ol¤-6}q \$zlzl Eqa 1,4-H!3fl8 44
E LUMO9I "llulxl E,r"oE 4l&6}r" ol ErunaoE E"ql q4^l E^l6Iq ¤zlrJ a*el tttyzlE 4l+E=g e.+ "Jq <tol4. Vv Vz, rel.z rf,$ l4l
4. EI^JE 4^} a+r} E rroel E" ÎolE CB +4lE trJ+^l7l'-+? O) z16}r" olSol e$, Hleq+, E= Hlas ez} fllEtr+tzlE *+6Iq4.
R =R3=cH3, fqr r,a-tlaflb9 gg 4C dzt Stl oJ
RrR6-ocHroJ HIA{} Ez} +llsE}fql^]= E! t}E 4zlzl +e.6J flx}91 +61-= illEi+
I ^l¤E
qI C+oJ +Hl+lEg zltl6J s¤"14. ol +lbel ELUMo= +6l. +q qEE^l Ai} BCql Es +q6l.zl ?*=+. (b) ole1a3 "JBe EE
-a olq^l $9 (a)oll^j gg a!+= ol+6lq olEg .s.= d+lE +6lq+. +aq EqE a*"il"J +tl¤+= a¤. Bq4. (c) ol .$z| alsq++EE
(c) Rr=Rr=flr=CHrolI- &=HoJ I,4-{la+ltse +}t}c r+a dz} old HJ¤. tlrll4 "llulxlE lB o e ++LHr" ol +lE'fl-+EE d+ tr"4E +4.t1
^l+e] * C+"J 4tI+ EEol4. ol +lEE ELUMoE + "14. fl=_ Eat fllE¤-+¤- ^lolql nzll! $zlz} Bs¤4r ^846Iq?+.
=q.E+lE'el
6E olq^l *9 (a)oll,rl Eg ar+= ol+6}q ol=el .*.+ d+lE +6Iq (d) ol{ql= ozpe} czp flls.E}fE¤ o, c, ',i N tlzl¤ Holl fz1r1z1"3
4. +HlflEql Hl6ll^l ,tlslHol q +4!+ E= LiE4, N2pflIEEI+: ol E flql 9lA1 q= HI-EH +aE ^J46ll -H-Î. oltrllel
Ltlz=4^tr-?l* LCAO-MO= trl-s-r]. rJ"l ¤4.
te.4 HI-dE4 %r'8, t-"lEzl *H, :41
DFr %IBq "J4+ Ezl +ll Vr= atYo + btY. Vs = eVN Vu = fVo - gVc
EEL+ 4ltlg 6lE t.l
As Ezlel e*+zj Ceg *+uJ Htickel ol
E¤- ol+6J qE4 4+ q +4 +4.J + gl+. (a) qrJ z|4lolul. _u.f Hls 9]ql^14 ,Jol ol +zI fllEi++# olEol ¤tl, ul-E
7l dAoJ 4lt1 %IHGI_¤Ezi *H, t_"lEzi %r.H, E= "JE Hil+ %I q+, E= ^4lil6lr.
HleE. EzI +llE6J+"JzlE ++.Iq4 E. olluJzl rHg
B)g ol+6}q qlH!, +4qQL dlÎEelt!, 't ++qltr?+{el HoMoe} rqr =+l
ol +llEil+Eel e+ tr-EIE +4']]q4. (e) ol $lx| fllEe++¤.q
LUMS rlol "llHzl ,J4+ 4l&6}q4. O) HoMo-LuMo qlLl^l 7J4* uflilz| Hl-sH +aE flElE aE}J+ +tlElL+? (0 BH +aE
"lall,H
olE +zlql r. e n zI9C g+ tl5f(44 esoo,46080, sqzso "i
4t At} MoTI BI-BE +aq AE-Moe+ F"J+ qlulxlE TlzlA-+? "J"J
32e00cm-')91 q4^l E^l6lq4. fq} +:re+llq= ol+6}q ol cllolQoll olq4ts q! a{} Moz} q *g qlHzl= 7l(lil'-Ll? Bl-a6J Moe} H}
7l* * "*= +6}^1¤. +6Iq4. (c) *9 o)q^l Ee 46J4¤. "l*alol ai+ MoE 7l^la_ ol glg gEol 61q4.(g) 9lg (a)prl (lvl?i|ql4
s"ll^l 4l{}oJ HOMO_LUMO qlLlzl 'J4 e_a+El qlTI¤lE}qlE ff+lt a^l ee ar+s+El BE e_69 flqE at}.I 4'J6I+= +6¤. qE
z}elC g+ {ffi +6}q4. (d) *E O)ql^lE rlC 4Col gse ol ole|.
f¤ ¤B6Iq4.
E,14 10
tlr
E l-Ell x,o I
ol ez1xq1^Jb'EoJ='ql +d zllH¤. z|ffiol,tJ 'qa'ql ++ rllilol oa

-il c)-t o o
CE= 4E 1"14. "lBZl e,e-e,Rl qar+ r Aq¤ Al4l4
oE f-u6}a d44 e +zr +ae+:z d49 ql+6}r E
" +Eg ol.e"afs qtr 4e=ol g¤4 o + J.EgEzlE q+=
4$= rlq6J ++g e4l g 4"14. ++g + il= t+q1 zl?* Eg- + ql4. r Et +s+ ¤+
ql= + gz} ?llE6J+E. o"l I
ÎolE dd 4Eol B¤4p_e
++61-.1 r46Lq olH flzl-+llEe+E"l Ezl-?llE6J
=zlEzl"lp glEzl$
10A .E.gEl E||a fql + ++B + 9l= 4olr|. E* 4ag +
zl-E q +4ol ol7 L 4aql ts" 6k flzl- +llE6J+=q C¤
ol e$oll,r-lb qqEI Exl¤olE r qaql ,r+El ++B + 9l aqlg +"J61+ rll"llr ole" slrf. ¤-e_E 4Eg qa ^dag j1
+= ag E"J aol4. olel{ E+E s}rll qH +44o e q6Jo trAl E"J+4 C"lE zlullali dq +4g +E6J +E
+^l7l {zl {-{z} EHIE= zlzlt_ !lizl$(u}e},rJ +¤"J gl'l
zl){l4ap sdEz}z} zlBd9 *EzlE q+B+ 9l+.
10A.1 Et|A Euat rt|A e,4; 10A.2 ExlEel rt|a EF: 104.3 clleel
xlx.lx{ol 7i:tl
-U-L- =!l
108
==
qag 4l4lzlg_eE6-lb aol '+goltrt.+Eg ol*otE 4x
¤+xqdol+ RI^telegJE ar+= qgg ol+4^l 'IElg +
?14. ol 4C"l +s+ olf+ "J+ qa ¤4Fg +E +qg +
glrll qE olag fstzl-" e il?-l= g + 9l+= 4014. ol E
Eql^J='zl*. -trrl]. d+ q$d +s+ z}|H$ czllols.._rJl,
"l ag+E-¤.ffizl e
ol+6h= o rll EEal +s6t+.
108.1 flal; 108.2 gE Efl; 108.3 xlt' E
==sl
EE lOA EgZI EH8
cs c2
> ol EEIE H}l+= 013
cfla tsEb Exl dEg *44oe u--bl.= r1l olEg + ?lrt.
: fl Elz{lE Erf=e-l 4eg 0lol^1 0l- E+o:|ts a
0ltrt
^JEo-l'r t
> ETd 7H'J
Exl#fE qA e.A= 0lE6U eeEEFg+ 9ltt. (a) (b)
fg 10A.2 (a) NH, Exl.= 35s{CJ=, :.alz (b) H2O E^1.= z6E(cz)B
7[rlr ?,,Itrt. 0l- trl= ct|e .9 7[^lr ?l+.
0l EEoll += rl= LHE# ?]E6l^|ts E^lu "JuJ alol Tl¤oll^1 =E
H[3 qe1 +gElE^le[ olE=elEg= glr ?l-g-E Ealg aol+
Ez]-5"1q¤ +q +4-=zl. g4l qH olEE ^dAg tr$
61 3ql+g+91+.
qE Eill= 4E aE+'q 444'o14. qle^l 79 oJdrzll
B+ q 444o14, +Cg E"II6IE "JelE zl$ql 44 "I 10A.1 E]|A Et}zl EllA e^
gqE Eld^lzlrlelE *3 ¤e -H-"J+. "JHlill= +,
=AqIe0',
qlAql tlt+ s= + Eel +Cp$ Er+61-= +ql q+^J qtr-Eq+ q¤ + a4lg .il+fl$ ull :_ 4tE"l i-lgr+
r a4}g c!|a Etlol+a ++ dB4"J 4a
E_*A\ _EolE
+ 2,10"8Eld^le q"J E.J.J Eo"Eg 44U'|t:H roe.r). ¤Îe] qlE^J= Eld, HI^L rela Hldg + ?l+. 4 '}|
Hli+ qls^l NH3 E4-= rH l0A.2ql ++u + ++lE =
a ¤/r!g rql EI¤-6-l= E[a 94= zlzla_ fl4. "l*l6J s
120"+ 240"2 sld^la ql E"J+ -5tolg +4Lilq, E E4= +e^J= d, d, ",{ E=¤ + gl=rll, ol$ a S6l]^J
= ^ql
qla gtlg 6l.ril q= 4"14. qlE^J sld(4a ¤4I)e +
180"=i qd^la q"J +Ag rro&$ +4U+. NH3 E
"l-4,tJ
zl-|. Hro Ezttr4'q qa4',ol+. (4a s +) ++lE Eej+= a4ol+. E4s=g 5gaj ,$1tr
ol s$oll,<l= olBl+ {+4 z}|HS trtrI ill4l4 zl=$ zl 9 qla s-aE¤ ,*+ Avl"-l +q^J t-o e E+++ rel6l-
zl:/ ++rll ¤+. rp-l6lq +zl¤g tzl zlzlt- ?l= qlaql 4 tJ ¤H¤E BF,4 col-71ql +-o + ¤+sla Hld¤ +
"J HrO(='g B)e+ ClFr(tz| B)zI +E * to
IrI4 +=rjl, {lE,<J 4Ei-ll 6"J CUnel SO42-- 6J +e__tr" 34 + ¤+¤+.
q4"lg *oJ Nu,4 solg +E + +e-s +=+. eg + r= EIE(a4)3 r,= Et|dE C,(4s"6lt e +) i?le- 360"tn
9 Ezl-==3 SA{I E"-14 Ce# rof'614, trl+î "Jdq
4. mH, Ezl-b 6I+E 3G+ qg 7l^la 9leq, ol +r+ +
c2 flq= 24lq 36t sld a4lol 7]}:6I+. r20"E ^l4l HJ-J
ca = Cr44 +H611^l
Eldr+ 120'el HI^l4l %t-6J Eldol zl+."alc|.
6I+9 2+ sld"Jol zft.aJql, olag
= ^lal %r-6J+ HI^l4l
o}6J=el 180. al{ol E"J+ st_l-"lzl 4Eol4.s4Bgcr+g
c4
zlzlt- fleq, ol +4 +fl¤ 27llE 72" o)$1t'l4l %r-6}r+ HI
zl$.o|+. + Hq g+4c, sldql ql+61+c3
^l4l "J6Dol
Eld+E zl*trll, ol a4g z.lzJl ulajgtr- rM"¤ sld^l7l
fal 10A.1 qe a^ g+. 26+, 3F, g 4=+E 554 zlE a4 HI^l4l HJ.6Je_e. tM"= sld^l7l= ¤t}el i zlzlzl
e EÊIHtrI.
"JHJ^1|E =
71s"6t4. r4I.
"J',J^ll= 37HE Cna,44lE Cr4, 67llEC21
10A -Egtrl E}|A 36s
g *=tr}. rq+ += ole+ q rtrE qlag zlzl{, E[

zlg" fl A+E n ?t& 4= EIa+g ++61 H:ol zl-zlr. 9l+.
+zt7| 94 z]|9 sl{+¤ 7rA trl= rt"l4l"J +g
"4 =
?+ol+r +¤+. Hl4l EzlE ++e 64 rEltsq +zl6J 6 .-J
ffio1r11l). alr 7,kA n3 4= itld+ol E "ltr- 9lg oll ol
t' \
¤! 6ILl^= ++e_e tlr dg uli =lre H:e +9 flzl= od 6d od
E"r}6lt +g qts +E 9lir" E ¤E EzL"J trIHqlE^J +
sB{ql^l= :211E c,+g 7l lal 10A.4 284-# zlEE(oa)P +=oil +4:dcr+= 4E 5E
^l'ol9
zla 9lq-, 2) +zI Hql +zl a|'tl.
ql +g q6J +E 9l+. L
1 rr-ilTil. c^H^
o
bb UE 6C, ,
L- e
t- t
oh
L
C;
=!
Y\
.r'(a,-l
I-
c;'
.f.al 1oA.s Sgsrl|= uE

=c0l=
7|'^lr ?Itr[.
tlol4. H,o4 NH3 ts:zl+ Hld +d$ zlzla_ ?lzl ?*zl"J

2 Ul-jfeta1,c.,oH,
++ "Jolill= ol4s=_ zlzla 9lq. E Hldl$ Agflll(re
10A.s)E Rld +d$ zlzlt- ilzl"J aÎBale+ cH4 Ezl+
ZEE o(s+1q1^lel HJ^K¤4I)=EzlE # sElg+ olag z$l:t_ glzl ?*4.
E 9lr" E-= ++ql +4ts +E 9l+. 4¤-H"1 +<.ql ¤6J rE EId-HJ I + s,('{a a +) ++lE n5 elE-U K¤t})
g EllE olag +4 A&Eol4l p=;, o_tr. s^lq}+. H2o + ¤+ H+sE ol+qzl= ¤{lol+. + Hz] 360'/,?9
E + +4 rla 4¤.H¤. zlzlt_ gisq(rH 10A.3), NH3= 3 =
sld^lzla o1q^J ol qd+ql +4+ H¤. E6H^J HIÎ^l7l
zll$ zlzlt- 91tr1 F c,+ 4i¤- 5.E6l+ +4 4¤-H E ¤&o14. qF 6J ^"ie a4ltrJ_e.E= 4a ¤+"1 "J g +
Îole-l
(re 10A.4)g '2E7+ EH',ol4A = _= - oo-tr- ErlaJu|. U
Eo
E 9l+. CH4 +:zl+ 37l]el S4+¤- zlzl:t- 9leq' flefl BEl]
448"1 ¤4 +zl"J ullE "lag'+¤ 4¤E'ol+r +e E qtsg s6+¤. zlzlt- 914t:-H 104.6).
-tr on-E s.^l6J+. Hltl E{b c6#+ +¤ Zg.Eg. zlzl 4tlEqq oI+ aE "J qlf a"l EE Etl 14. "l E
r 9l+(+s 4a s_4rq=4 Et41). =
4lql 4+d+ qla s-a= d4l 4tlEol ¤+.E= qltr-Ee
Elle i(q +15 E"+ ud(¤&)g r]]tr-E +q E= a oi$ a{E 6ll+zl ?*98 l-oE E6}al ?J:s ss qB qlt}
=c
9 EzI 6C o + E4^14 +']]¤ +_e-E tZ A?-l"J+ +r}
,ll 6l= St"l4. 4 4@, y, z)E 4(x, -y, -4a -H-t}]= ¤
ffi
J sb
c6
6.n
oj
frT
I
U (a)
o
.l.al 10A.6 (a) cHo E^1.= 46 HJ^l-elt+(Sr= 7l.Ê ?ltr|. 0l E^lE
e0"= alE^lrJ rl-=oll +EEE sll^1 u^l-^l7lE ee
= ralLl
LlEtur[.
rg 10A.3 H2O E^1.= + 71EE= 7l^la_ ?lrl'. 0l=3 E+ +4E(++Ee 0l =ol
E$01 qgle_ets EH8 Ettol El^l ts=rf. (b) l,JaJ
:dEHE
oilEJ=
E.:.SI.E-)O|q, f.alolq o,9|. o',9-e. E Fdtrl'.
=
60" elco1l 0l= BJ,\IE ol+Gl^l= s6 7l^lr ?ltr[.
=E
366 qa
=rl
Eol= EF ol rlla S3E 7l7la_ F

E 10A.1 E=oll ctlEls.,'tl*
?14. olelq} qla a+E +ol a ci T
4o1l"t 6l-= 6J olf+ E4ql q+ c, m

ola ole]E += qla s 4Cu
^J=(3) cr c2 2 C33 c4 6
4= ol+ \u z1z1 ?*zl oll$ol cb Zmm Cr, 3trt Cnu 4mnt Cu, 6mm
Br
+. crn 2lm Crr, 6 C4l, 4lm Cur, 6lm
3 CBrClFl
D2 222 D3 32 D4 422 D6 622
Drn mmm Drn 62nt Dnn 4lnmun Dun 6lmmm
Du 42m Dra 3nr s4 4Su 3
T23 Td 43m Th trr3
+EB{l ExHz)9 qla 3 E¤ q"J6}=.r.}6.}==$ offi o 432 q, m3m

q,JE+.
* zlEE 44, Hermann-Mauguin({zll xllE)= d't{o14. Hermann-
Shoenflies
4E e= Ezlq^le+ ?ol "l EzlE 5+ a + E= Mauguin 4lEq^l= nfr t$ fzl n9g_ g,tlo|-L, agHg Ezf m og g^l
+4. E 'I4C /g rla+q +zltl 4gEg +E}utr}. ae ++E qa s
zlzll.9l4. 4ols.rlE /J.ol'* +q +6I= S_t# +E6lE+ ?9ollot 6J4. qe4 3
zfl$ drof oJ +E a¤.E¤. zlzlE 4tmmmo E s^l6JE+.iz} +lql "_lq EE
34lE 2+ e)4+c2# zlz\t- 91+ 6I+E +zI
= E"J ag a- s-t7l Hldr+ a+g ag LlElu4. ol s.ollE olEBl eaq+4
Hql +{6tr" += Ee EzlE flq fl+. d+ol{r 6t= +EEig d$.trI.
EzI Hql +zl6Jc,ElA+g ?+e-E q9lg ql, +
+ql +4+ 4gE onzl. a1u1 fleq, # s*6t
E zz11E +4 A& H o,z| 914.
Ez}el 6dfig 5r+61+ HIA +d i7l ilE+.ol +C
e + aE= ¤Ad+ c-c A6J +"Jql ?lzlt Ezt
27H ol.se.l
6ddol4. n>2?
10A.2 EIla E+
=rl=el
Ezl-=ol zlzla- 9lE qa a +ql 44 Ez]# +o E tF
6J + 9t+. 4a gt} EH^Jql+ r.lla S4Ig oI :z 4 nol ZlaTl Ej=C
"l]+Hg =
d86l-r' qoll +rl-Lf
tl +E 4^* + +EAol EE+Elzl ?+r hr-= a+ql. Et nc27l ?l=^l= Etrl.
39 olFrll E+. ol7l6J ++e_l Eila s_ib Q\ zlzlzl o) N N
+. AA(E9 tse)9 A+ql= *Ag 56ll olF^la ql +El Y
+}. qaE -r.EJ6]|ot aI4, olfl {dzlzl EgIÎ1 q e94 N

N
N
"J Bzjfl$ ^J46]]oF
6J+. N
E"JqI îlEE qla si= ,*z sE EztEe d+ E Y

g+ d+ql +4q, +E Eae :z 4a si zlzl
^]E.
r cql+. 9H]4_o + * zlzl 4lEE Hag .rf$al-=rlJ(*. Y
N
104.1), r 6l+= EzI9

'lla¤- b6l^=
cll -E-¤4 o e ol+q
E eg Bag ++)r E 6L+= A
Schoenflies rilE(Cn"e+ N
Ce] 'llag b6l+ ql ,lE ++4 "E "l+q= Hermann-

N
Mausuin r1lE, qfl NIE(z,mmq eg Hag ++)+.

=
Schoenflies xllE9l ,ri4 EzlE d+g !p6l+ trll= e+fl fal 10A.7 E^|-9 trEE 4olLH= EE +s +EH7|+E1 4 EIE-E
="J6ltH
ql 10A.2oll1j
+9 EEoll SEJettl(Y="*t[, N=olLlEt)' qaJCg '2Jft-d
-zH roe.ze-l EE tr-se+:H roe.sg E."J!g ole"a|fl Btri. Ej-d 3ert.
E2trl'Etl8 367
n=
AtrdO
2 3 4 5 6 @
t-
cp= C-H-
,^ 55
Cn v
L
rili*--+ t# -i'-
Fei
D
L a
3 rA,i E o og
ta oa
c
IiAiT
5 trllEd!, Fe(Cp),
(E= 8Efl)
cnn
D nn I:AII (a)c,, c,, oJ c,

=
rit t I
qs E=-:-H-rgg .^r ---
s4 # s^"Jg 4= +zI: c,tql Ba
Dno
o +*+ H ,q-ê+ Hld s +"Jg *= cr
Ezl-bc,+ql +61q, r;lI. t*: s_ê+ ci
440+
E
E,i
srn
il,,+-* 4gE "Jg *= Ezl¤gc.+ql +++. c. E,o
feJ 10Aa A0 Fd trESll 6tl=.16l.=-?$=. 0 I raJE= 0 l8dl'E .lal 10A7E LlttEt 0ll 10A3
8^l'Jts= qeIlgl-EExlill olE 91tr1.
cBrclFrE^H3)= szl ¤*i s-^"Jg 7tzlq, r?-l6t
=oll+61.!-^l= ^lE:g+
q c,+ql +++.
zlEEt q 10A2
ql^-Ele # s-ie+ Hld 3.4= zlzlt-
+qlr=tl +zH4)7I +61"= d+g q"J6I7l +l6l]^J +d ql
ilsq, r?-l6}q c,+ql +++.
a -9-i=¤ q.J6Ir:aB 10A.7el EE Es=-ole"aJr{.
ol Ezl+ s+ qd+g zlz)4, RuE E"46Ecr+ql
+{+ 5T]|E 2++g zlzlr. 914.
cr+ql +46}r RuE E" 46lt ,l¤: E onz| fxll{r1.
tff;=.
t
Y-
-Ll-rz
5TIJE #e E+61'= o"7I ol=g zJzJ t;j -5$ri-;"

=zll*r+.
14 tlE + cg{¤ zl+ Hlq E9 c-c A'JE +
dg -34++. ol HEg 7+7+ zG+ 6ILl-= sElQl+.
o;;-
6 ollA-e1=ElEtj,
HOOCCH(OH)CH(OH)COOH
:zH 10A.7ql^J {EE dd"e.444fl4. ol
zl+ot 6}
?lEfl(7)g (E, o) -s-^=g 714q, r"-l6}q CJql
ddg D,n9lrl E+bql, ol $zlz| sffi *zl o1g"ll
Dsh+ql +6|rll ¤+. qlEd(s)ql^Je+ tol F l4zI 9.t +++.
g trll= +¤ |g$"l $,9zll r r{dql + +g f,$6}
+ 2q?J s" EH oaTI Lt4t4. rB ron.Tql^J 4qlEI A
_E= Er+ 44zlE dJ D,atol +g+.
L N
C J CP = C5H5
L
7 TIEC!, CaHTN
Ru
I
(b) q, G,, oJ c,n E
4 +Ell!.{.!, Ru(Cp), ,?6 qla+g *= E4-= c,+ql ++4. zle_ c,2 4a a +,
368 Erl48
r|]a ¤4L ",t +3 s^l6l+ xll zlzl qgg *trlt 4g +E

6Iq4. ¤+ e +e+ c,+ ole-lql ntll{ +zl HIÎH o,E *E
E4^= c^+ql +ql+. t+ s_ê+ n* a+ olelql +-4 A
g E o6E 4E Ezlt c,h+ql +++ a+ql q+^l= qB
qla s Eol ¤z}]t4E 4ol 4E qE .]]a er$el fzll
E 9"lB trllE 9l+. qlE^l crr,toll^J G4 on ¤t}=g 6JE oh
o e Hld s i7I 19 9"lt}

={]6J+= qla aÊI
gel
Ba 4436 +(rH loA.e). -trql=
ol Er.lqq glr, 4a ¤4}g E6Jqq lal toA.e 2e AC+zf +r-J 71=E0l gr4l rflE -r Ert +oil HJE
C,, E, C, =^Hg
6Col=1116[1] Erl'.
c* E,c*nou qlzl t**9r]]a+=-6Iq+' qlE^J c'Eld+
Crr, E, C* O6
Z 2t114 ¤{}g +srll d.+(+r2oo
e+ pld).
-120"
o.n I
OH
ztE!¤t q 10A.4
. H2O2+ZH8)= O-O A6J +e-s rlle+

+ O-H -H-H
eoJol .<JE lls"E 4¤- "lE4."l Ezlt qla a+
Ee+c,E TVlq rEl6lq Cr+ql +6Jtrt
10 B(OH)3
'C^
-z
..tTt
1
-.
H
(c) D, , Dnh, D* E
8 rt+ltrf+A, H2O2
n* a4,+ c,ql +zl6J zl]9 z+ +* *= EzI= rg
n
H2o¤:zl+ qa eA 8,C2, uf zo,E zlzl4 t4-+^l roA.7ql q+^l D,+ql +el+. olBl+ Ezlzl +B 49 tsg
cr"+q +6J+. E- zlzlH D,h+ql ++tri EeI OCOs+ HCCHe+ eg dB
NH3 ¤:zJ+: Eila a E, C3, H ro,E 7v1q II|4^J Ezl-501+ t"J6J g# D-h+ql BA qlaa+
^ +qI+ D,9 qa 9-48 olelolJ D, E, C,u nCi
cr,+q +++. nzfl
HCE+ zJ3 olt4 zflz} +zI9 A+ql= qla+ + I zHzJ r="+

4gH oaE *E Ez[ Dnt
Dnd
E' Cn' nCi'
E, Cn, nCl, noa
o'n
+lE EE Eld4 ol q$ s*61+ E= Eql^lE HI E3 o,o+ql +++.

qla s4l"l qq, E|+^J ol E4+ c_,+ql +
Î7I
++. ocse+ ee dB EzI+ flBs c_,+ql ++4. z]tr'Et oll 10A"5
trans_CHCI=CHCI Ezl-b qla g E, e, "l ong zl. ¤H /$4¤9 BF, Ezl-b qla
+ E, c3,3cr(zlzqE
a
zlq(e), r46lq c2h+ql +++. ^ B-F A*ql S6ll^J C2+ol 6l+4), H on. zlzlt_ ))
B(oH)3 gz(ro)4 ae ¤H ¤E]l= *= Ezl+ c' o q, q+^l D3h*oll +*trHlt).
44 or,HS zlzl4 trFt^l crnt"ll +*4. F
o.n
CI
c2
11 E al=+o ael EA, BF3

CI
Hltl +zl+ qa -a E, c6, 3c2, 3c;, of on, relr
9 frans-CHCI=91-161 ^
ol ec$ol f4lal oll zl+.4_e e q= +
=z]1614l
E H ,]]E qla s-i=¤ zlzlt- 9leq, 146I{ Dur,
10A -EgEl E]|A 369
+ql +++. udlql^lE rz11E c,+ol c-c aqlg E

E6Iq, 4e lzfl' ol ezlq Bi u44z} tlg}- 0zt
Bg +zld=¤. E"r+*+. 3ciql Eql l'+"J E^lb
olE :zH9 zffio14E 12119 zG+*
^Jola}4ts 4,
g +4u+. (a) (b) (c)
Nrel ?9 s= E4 2?lz} EzI9lrlE ExI9 6J
=:s lg 10A.10 .r.[Eill E^h (b) ggrll Exh (c) g"Jill9'trd,\l71,\l ral
E+q += zE etr9 r80" qdr+ +
131
+= 20Ei1l eg. oEg 44 g"J= T6, 06, Lalr /holl +:Lttrl.

e-trE Hl^h r?-la +zl-+ ++lE=-e-E+q
:11E
E= qldol ql
a s&"Iq, q-+^J olE Ezl^b D_h+ql +6J+. I
D,n69 qls^l Pcls(l2)¤. E + gl+.

c3
c2
c2
oh
(a) (b) G
fal 10A.11 (a) tr= Iel,(b) tr= Ooll 6t|=J61.= E.g. 8^l0l =JaJ iiJ^l-Eg
12 EJ!Elgel?1, PCls (4h) IaLlOr,9 El1aol 0l E=E=e E+.
='Zt1=I}l6l-E
* flzl¤$ Eql +{614 +q
cu,zy r+?+ L+qzl
gl= sE+q$(g{L l3)g Drd+ql +*tr}. (e) S'JE
C; C; "te ql+61 ¤!s6J Ezl-5"1 ¤el z]]9 +19 zlzll. 914.
olEg guE, +ql^lE r AtEi{l z T, To, oi Th(rH
gEi{l =61
loA.l0a)Eol+ E.= E o, "l on(:B 10A.l0b)ql +
qI+. H zH t}qzl"J 20Ei{! +6t= 2oEill Ez}(:zH
c2, s4 =ql
10A.10c)E ?14.
L
t3 E-eu|rlg!, (4d)
rd+al-q+g zqzq $$Eille+ ¤gHillE
=o]c}.
qtlE
C3H4 ol ,<|sillu[ gHi]lE Eld 6]+E
'ila"Jg zlzla_ H]^]Eg
*zl 9*¤ 4lb e+ ++.J n* o +ql +EI+(rB 10A.rl).
rh+g r+9 Ella ,q-i= EE Hld +$vl^lE zl-zlr. ?lb
(o) s,= +ol+(re roe.rz).
zlfrnlzl izlt qL + a|qlE +6tzl ?*sH^J ITHE s,+ qaa^
g 4= ExlE=g s,+ql +6J+. s,te c,+4 Aeq rE6I BA
T 8,4C3,3C2
¤ ol4al E4==e olul $oll,<l ct_e ++qfl¤-g +E-6Iq a E,3C2,4C3, 3S4, 6od
BA qlaa^ 4. qlEqqlHqlBtr4)g s4d Th E,3C2, 4C3, i,4Su, 3on

o E,3C4, 4C3,6C2
S, E, S,, Sql^l E+q +ql +61{, rz >4oJ S,+ql + oh E, 3S+, 3C4,6C2,4S6, 4C3, 3f6,6o6, i
7l o-L
"l IEL
e- alt EzlE EE+. I E,6Cs,1oC3, l5C2
th E, 6516' 10s6, 6cs, 10c3,15c2,Lfu, i
z]trJEt q 10A.6
S;
t . cHne+ sF6 +xlE=g zqzl ToZ4 oh+ql +qlr+.
1 4 rll-= afql -J oll EJ, c( cu ). (q)

370 Erl qa
. 2oEill + /oil +61+ Ezlql= g+ B+ Ezl¤4 ¤

qfl!, c*+zkls)7} 9l+.
1
,)
fg 10A.12 rh Eoll+61.= q'lAr=elEg
15 C6o (/)
=a-1fl!,
. -r.fl roe.rr9 'lltlEg ?+?+ T++ o*ql +6Jtr1. zI sHl=.E *EtrIH Hldql E6il^J r ulalol Hlqls ¤ a
olF + ol Ezl^b q_t- graJ=e_tr+ /5qzl EHIEE 714 +
H+.
ol+l* r+Eel Al}s ge AEg gg + 9t+.
(f) sd ild= r-l-q=r+
E= 7l-eoq! n4k4 Eld+g ++61 B:ol T|zl_r. 9l= tr}ltr"E cu, c,,,, q c, +ql +61-= ExJ-E"Jol ¤+ {zl ffixf E
e gd trld= R3(33 ril-fl qdg 9"1*4)91 +Ei+. +¤ HIEE rle + ?l+.
4tEol4 flzl¤ol R3+ql +6izl+, {zl"ll +61+ Ez}E c,t] c*4 A+ql= )*=7171'Ia+ql ,'|4 so].4"h d4,
$,4.R, qlael Ar+= trI4 E= ag gzl-ql+ E}]a olEg
4+ri7i= EfiEfal 5=eoj %lfloi E +U ol-r-l+ +liE 4$ts
zttrJil oll 10A7
Ba qlas^ =*ql +.J ol$g ^]]Eg 4Eql^l
d=61+ *Hs ¤+ HldB"Js= o3=c2,=ql +614 +^dol+.
Rr E, *C2, -Cr, ...
d¤ol{d D_r,t9l +61-= Co2= Hl-+^Jol+.
qlE4qlpoilEf t+)* s4=ql +614 Hl-+^dol+.
10A.3 EllBeI r.!EI4e trut
EzlE d+g .Jrll qE ol4 o ++El : EzI9 CAg qL
aE "Jg + ?l+. (o) zl=d
zltlel 4¤-^J4 ETI]A + S.= Ezl¤ TlaJ qlq
(d +¤ =rl-ela
(chiral9 +g E6l+ q*qqlî +4qB.q). zltE 4gtl
Erl= %+ 47]| {fx} EHIE. zlzla- il+(qlE^J 4 ez]]d + 9l= EzlE Hl-71=J Erlalr {}q. zlB Ezl^b
=¤
HCl, 03, "i NH'). d+z} EHIE= +zl-E cdolq, EzI9 ¤"*Eg Eld^lvJ + 9t= tsg¤ Ezi+. t zlg Ezl-e+ z
ceg qla a4Lql E6ll^J H6l+ {ol o}uls + 4-:r-x} e-Hl 4gt} Ezl+ EL4l 4.=8 ol¤Ei{l 8Ig olf olEg ¤
=41,
qd^l{+.
E(EqE s^lq=)= qq+'ila azlql E6]iÎE g6J-g "JEg,<Je_ EI4
HJ-6Jo_tr. ?Je a7PJe4
tszl ?*ot"t ++. ru>loJ c,+ql +61+ Ezlz} qla+ql + zl=Jcg ++LHjr
zl¤l qL 6} HJtoJetr 4qzl$ 4=trIH 4a+E qdql E
Exlzl- H}^l--sld+ s,,3 4zl ?*"1-"t
6]]^Jol .l5t-+zlE oJi'lol H6llot 6-j {ols + qla+q +zlE} 'JgCol E+.
,'5h+z} EHIE= ++4= d6l tsEE 714 + s4. :44 s, H}^l-_sld+g 4= ^Jol'J Hag zlzla_ glg +E gla
qa+ql ¤Bf, 4qzli Eldel ¤6&9 gzl g|-9-se f-xtl E tri.q r.ila a +E "Jrl"Jot rll+4ee sElqq 9l¤. +E
g + gl+. qltr-! H,oqlrlS ffizlzt EzlHql^l HoH a 9l+. elE^J c,h +ql +61-= EzlE=g c,4 ong 7}zlr. 9l=
E.g "J+6l+ oJ.J, + cr+el "J6J1g oJ::op gl4. olp-l- "ItI trll, olE=g HIÎ-sld+el + c+olq. El+^J ol=g ,ll¤+r-
zlzla 49 Hg *E Ezlz}. {F=-z} EBIE= 4=+H H}^} s,g zl-zl-z il= Aol+. e. H}d 6C ,'= Cr* onzl g+6]]^l
ql el6ll^J r ulolol Hl4E ¤ aols + ol Hql +4* ,'8.+ .Jq+= 44 a-q-E-E Hld +d E 7l^1a- 9l= Ezl= s
z| E{=.8 zl4 + Htr} E+ qla +cg 4= Ez}zi ffi + s,= zlzlt- 9lq(re 10A.13). g"J olq4 4gH3 s,r+
Eztrl qA 371
COOH
H
CH,
16 L-gal!, NH2CH(CH3)COOH
fg 10A.13 E{},e[ s2= EHdill9 Eoll EttE ttfl 8jd6l E"J-d e'rt= . olel 4a4 o + 49 {$ z}zll. !l_e-
L[E[Lfloe 0l+ 9 ts EEEI a0l+. { ul-zlgr3o1r1. =q4l(17)g
t4(:00" eldql olq HI^}. 44^l 4g-gol+ qd HlÎ + COOH

$zl,.la- ?lsq q+^J ul-zl$.tJolc|.
H
o H
N H2
zlEEt 0ll 10A'8
. olulL{}"J "J4U(16)e H}d +col+ 4¤-Eg * 17 NH2CH2COOH
zl f*sq q+^l zlB^dol4. =alC,
EllE+qHqE}(t4)e. s,+ql +6Jtr1. ol Ezhb eld
+col+ 4gBg 4zl e*zl"J 3rld_HIÎ +(sJg *
,l qEql Hl-7lB¤olr+.
T]ILJ=
=.e'E}
-l l. r]|fl Etol+.J '|]tl$q{ r ¤4Ig 4+fl9 trI ilgr+ -l -r. EzlTl-lsol sl4Ht:z4r ttg qlacg *4 t*gqBl
E"Jol qAol -H-ol= ¤4}oltrl. c,, c* q tql +6l]ot d+
1 2. E]|e 94= qa g4}g 6ll+= d, d, $ flolQ. I 5. Ezlzi 7!=¤g TrzleiE cld-HIÎ + s,g Axl t*"}"t *
-l 3. BÎe+ rillql "JqI4sE Î+q= E==el 7la= E +.
10A.1ql sEqq glE|.
E]|A Etlzl El|e e^

qla a+
'ila s& 7\E
n6 4d cn ,6 sld+
Hl^l o agH
Hld i qla +c
nf Hlrt-9d s, ,x6 HBi-Eld 4
EE
oo E dill qlt}E
EE lOB
==
> 0l Etrl= Hli+= 0l+ GZEU Erur cn-d Etta Et# G or=trl.
e# qeoll g-d tr¤4 Ti|LJ= #et4e.e LE|.q{= zloe 1 d+cr"= g,t} {8, cr,o, o',}q q*6F= qa F+ {E,cr,
BE+l6lr q?iEl E^1lql xjllEoe + ?ltl !E-d o, o',)-tr ol+qd4. "l g41,tlltrE +Ezl flzloll,<J 3ol
Elqt Iuoll 38 g --g =EE
E^l E^l +lE6++flll E^l= rt=
^l.EEl= E9 u-q4.
Etc.l.
=7171ElTlE
a.4E E+I=E 4EI"l +lq^l Ct z164 "*Ezl
> qld TllLj ^lEt
E E+. ol +ql +61+ Hrooll E|Jfl ¤4]$$ e.9 roeoll
qa Et:!g 7l^1011 ttl-d:d=JelEzl'= 7l^la- LIEIB + 9ltrl
-zB roe.zq roe.: o e ¤E6ll +9ttr}.
^l E^l6}gsq,
> geEt qlHl Eol
^l^l
Eol toAoll^l ATtlEI tHA EtF+ qe a^g BEtlEoll tr"=tl^l . qa g4I d+ +qlE # ¤{HE)ol EEEIq fle
g0l0F Elrl. 0l trEoll^l= -trE eEel Elqfxfe.l 8^l 240il^1 47]|
se zl31ol ffi$Q.
-d BJEE H+qr, =.J=E EC_e g0l 0lE6l.Zl Erl.
=61 . zJ a+ql ¤Îg r zf,llol q s&"1 gp + zl# z
z| fa--$q. r?-1614 z+ qTrg + H] S4:"1ts 4
t.el 6l+ aol
g E¤. ¤4}]+ ?JEI lcrcr_Bolq ole+ uffizlzlE
'ilag ill4l4 +EE *:e Ll]+
e__+
e qtl$q qlaql ==ol+.

+oJ tl,llg ee5X 4o14. rfl+ +Eol + HI^le+ g5 zlr.llE r++.
illal4olTl qEql r +zl.g +HlE 7lAl4 HJ^l o + ¤+ . + ¤4}ql olq 4= ¤{Fg 6il+E ql 94} +9 qL
g+. Eil++el a+ +Eg flÊ lltlg zlzla_ f+¤I AE "I+eI Aeq, 4+^J
zlf sol #g+. qle^J 2+
Eld c,q olq^l HBI-o¤ 6il+= ae t H9 HlÎ
{l _saB:"lt rJ*6}a 4d4"J HJBS zll*61-q, olzl.r.J o1e1
+ Hg ?t6oJ 4,o14. 4= Ell+b a+ 'ZJtrNrH tos.t).+, o,G=o',ol4.

EE qa ¤&E E: RR'ql q4^l olElql BHg "18
rtts ol-efle+ Ag + #C E= t,J= + 9l+. olell s
108.1 fla! q E6LH q
==sl '+?+E EE=g += + ¤&r+ ¤l"J6Iq
+qlql^l z$l zlag "J+^lzl= H++el d+g "JqI
ql +^J +E s_a¤. "J+^la+.
=e
tr}. + H++# R, trr,...(Eq l0Aql^l ol+* HI^L 4d 501
RJ R'-+ E c2 ov o'"
+l. ^J46J + gl+) o e +r18 d*, olSol ffi aa5g. E E c2 ov o',
ffi,(1zlH "l d*e +g Bc6-J4l'Jd4. c2 c2 E o'" ov
ov oY oi E c2
t. H*lE 6fl 6I+E f-f(ot+ aE qI 4+= {)"lr-Io} o'" o'" oY c2 E
++.
2. 4 H+| Rql q+ q E+ R-'ol ol dB +ql Eqflq"t . ¤4Ig qH +^]s *L6IH ?J* 4+zl 4s_ue zl
tl+. ol q H{+3 RR-,(E+ R-'ql olq^J H+l Rg +tr}) A "J+g+. 4 (o,4)C, =CzCz=Eol-Z o"(o'"Cr)=
+S-
ol f,-:="4 B"tzlE H¤t"14. o,o,_6oJq, q$. _E= AE+"ll qlfl^JE u[[z[z] g
3. RR' afiH+I R'ql olq^l H+ Rg ++)e ol d+ 6E 4lrl-cB++.
qL QI *g H++4 ?Jt;+. \l7lB7l108.1 Qnt$ 4a a + {8,C2, L or,}E TVlq
4. R(R'R") Aq+, + H+ (R'R")ql olq^l H+ R¤- 6l+ a trI+^J 6il'J6l+ ¤4-1"1 {E,C, r,or,}o14.+ +C .trE trJ
g (RR')R", + E+ R"ql olq^l (RR')E 6ll+= ¤tI4 Eq ol40l +"Jg q"J6Iq+.
?Jtr+. hE+* [o*[z et..E
108 EE 373
2
o
cJ
o'1
a' a" o' a"
c 3+
o- c 3
)-r
Zr
(a) 3 4 (b) 4
C;
o"lxzl o', (vz)
lE TlxE q'Cio, E+ Et= B6tE 1 -+ 2 -+ 3 -+ 4 -tr
.f.al 108.3 (a) tr
olE:dcl(o;'e o,ef ee EzD. c; 'JE Et(EOg trrE +-e olE^l7lq,
lg 108.1 26 trlE qoll 0lol,\1 uJr[ o"E 6HT= a3 U I o,E e] E ;t|
Etal^l cjet c;E ee Eoltrl.. (b) (Cj)-'o,Ci E+ Ete E 1E 4e olE
+= a4,Jtrl'. ((ci;tg C;el ?3 Erl), 017i3 o; 'Jg El(Ed)4'Jtr|. qa[^l
^l7lqoi8
o,el ee A0lq'.
g.E"alzl flg d 6}r|=,rl?-l +B61 614=ql, +g "JE= -r.e 10B.3(a)ollrJ gelel + A lol qel E4l={l 96H^l q
Bill= qla s++= ^L¤ol+.Elqlql ++6J ullE ol s_i$ BTll BE"6l+zl$ a$gr-e-sa] ros.r^lg olso6I¤ cr*qct
ol 4E .Jtl Eila s&ol E+. rq+ Eq loAql^J ¤B6J zlc,,J9 Eg #ql +*+= ag +"JBJ + 9l+. +C
'lltl
u}q ?ol '4a ¤4!g 'qla s +sq, qa ¤4lg El H¤+go;rcr*o,S&o14. d tS zlz\a- ol ¤tlg
^1416llB+.
^'e|
d+, HIÎE 5:ql +BH^J 6ll+- ¤&ol+. zE e--8. 'e +'4= ¤& oi ol dg 2E ol5^lv11a- oJq^J Cr*g ol dg 3 o +
+q= BEel $A-J +lilql fl= +E +{ql= EllE rôJ+ olf^lA+. q-HIÎ= HIÎ zlille+ E"J6rq, ? o;,=ouol{,
ag +E611oF oJ+. +, +E a +, qla I ^, r4r qB El+^J ol gtlg
= g56tzl "l d¤. 4_tr _H_u+. oJ rgql qe.B d rql
-0-a= "JoI"t oJ+. c;E ¤t}^lzlH ol d9 +e. -E-d+. I[I4^J o;rcr+ou=6;o1
qla ¤1h="1 E"J+ +¤olr(qlaq qd) +q Eila s 4, :2461¤ c,*elc;E +d6l Eg #ql +E!+.
4lql E6l],<l !E H¤IB + 9lg rllE "lEol E"J.J Eql +
++ qle^l c,,+el + 3+ Eld+g HIÎql el6l]^l H+ ^ls zi.JEt 0{l 108.1
94, :_4aI¤ "153 Egfl fql +qI+(rH 108.2). E tzll
9 Hlrl-==s 3+ irldql elq^l ^le. H+q7l qlEql olEE C3,+E o"el o',ol E"J #ql +6rE 49 u-21 +16ll^l
+ 5g* #ql ++trt. + ¤tl Rr+ R'ol E"J #ql +6IEIH (ci)-'o"ci H{]-g d46il u.z}.c;ts ci9 9ols + ol H
ol$ol eg += + e+ sgl E6ll^J q^.q-l} *"1 HilB +gc;o,cr*el rJL| gEq d t"ll 4eL "l ¤+ E4IE a
=e] r+= rBl0B.3o)ql +E+.llH+. 4+ glzl aE H,tI o,,gl
f gl"l"h ++. olaol +q C^l ee_l+.
tE+El g +E 919q, q{^J
el6li^J Cro,Cr+=6',o14. r
R'= S-IRS Ael e^7f El= aZ (108.1)
46Iq o"et o',9 +"J +q +++.
¤zld s'g sel q H$oi4.
108,.2 ilE EE
zllllzl ¤BEL ,llH^Jel ^J4¤. qB B4E +E¤ zlzlt_
+4r]]4l qE +Eol +lqg ++'HXl g+.Bgql +6J 7l=
C;
zl4g Eq eEE +qx}el *4 uz -H_ol-el..
(a) Ett9 rllgfl

:-B ros.+4cr, EzI"J Sor9 s7J] p +llEEl+ ¤&
^llE7l-o,
rB 108.2 Eg:el Eq E|,|e Ett=e :l E9 Et|e Etoil 96}l^1 AtE
q el6ll^l olE ar+= 444Ezl 6}l'&61-= qla
^J4t6il -HzI.
ESE +7|.?ltrl-. 0l raJq {l 71=83 3¤i ElEoll E6ll^1, lzlr 0l raJsl ,q_d= +zI Hql +46}r sgzl¤ E"46IE 4¤ Hol4. ol
+ elEg o,E9 HJ,t.toll 96}|11 8E' ESEtrl. HIÎql el6]]^J p,e} p.= g6}9 Bzl ?*e4, prE Ps.zt Hat
374 Erl qa
+ -l 00 o o)
0 10 o ol
S
T
+B
p,
*P, D(oi)- 0 01 o ol (10B.2c)
+ + p" 0 00 -rol
A
I 0 00 0 -r)
T
B
L +
+ A
+ ¤&g Tlzlql+ ol+ Hs+E +zl t*e4, Ir|4^J _t 4
pA =+
Eflg tr}g=4 *3 sxs +?l BBol ¤4.
fA 108.4 C2, E^l'(SOr)ollAi ='J=l EE= EJE: gE= EE"-I.= Ell olE (toooo)
El= trl'! p flE-dfE(B fl^toll +dl'= 371el 71tlôll +6|.= 17t|q).
loroool
D(E)= loorool (1oB.2d)
a Hl-fltr}. ol gffi looo r ol

Io o o o ,)
poel pBE (po-py, po ps, pe)e(p,"
^J-tr
Prpo Pa,Ps)4tr ¤ + ?14. "l H+lg r+s-4 eg qe gC
$ ols-" afl.<J +48 + 9l+. (b) Efl
D(o") =el
(t o o o o') +E E= ¤4Ig +r}'}l= 4B.9 ^llE= ddg zlzl9l 4
6J ol +q B= EEol+r 6Iq rE s^l+4. q7lî Er.
lo-roool
(p,-prp. ps pe) = (p, p/ p, pA pB) lo o r ool fl= ql.|^l3 sz11E zl4zl fleq, -E¤ol sz}fl(sxs BE-e
ln o oo,l ¤ sB)ol+. E¤el qB==g r- +EILH= ¤tF+ +a
Io o o i; ) 3 *4 o + ^JE +-6l]tl4. :z4alq "Jelel + ¤& Rr] R'o1
= (P, PyP,P6pB) D(o") (10B.2a) RR,=R,,ol g a+ql= D(R)D(R,)=D(R,,)oI ¤4.
ol BE D(o")E qla Et} o,9 c}lEfl"l4l +E+. ol ql z].JEt q 108.2
sgg 71r|(+llEEL+Eel ^llE)E q6l+ ql trl+ gol B r +ql^J 2+ Eldql ol3 ag Eql^Jel HI^l-= + H
c2"
4d+ zlEE A+qlE zl4zl B ulEl (p,,pyp,,pn,pJol4. zl |g
Eql^JE HIÎe+ *L\+ o,,cz=o,ol+. 108.2^lql
qB D= olaol 4+"1-b zlxl el+E s-ql +4'l"t + E^l+ Ellslgg ?ol 84.
^J Î-S6IH 'l+r+
+= ag +q-6}qEl-.
00 00 -l 0 00
5-"JEI ,JHg ol+6}q += 'ila ¤+g +s4l q+ e
0
10 00 0-1 0 00
B5g *g + 9l+. qlE4 c, ¤4Ig (p*,-py, p., -ps, -pe) D(o( )D(C,)= 01 00 00 I 00
+(p, py,po pe,pJ9 s.r+E "Jgzl{,:z QE'gg q^-q-q e
ol g+. Il 0
00 -l 0
00 0-1
000
00
00
0
0
0-l
-1 0
(t ooo o -1 000
0 0 100 =D(o, )
l0 -1
I
0
o
010 001
Il
0
D(C,)-_ (1oB.2b)
l0 000-l o
0 010
l0 0 0-1
[0 o
qlE ol #de + #c Ee+ ae ar++. E.= Ell
qltr-E}
Eg tlE +cE :l.J+ +alE "J+^l7lq, q4^J ql B
gEe +E E¤ol ¤trI.
<- (p, py,pe pe, ps)olq, 4Ii +llEEL+s" +eg Eql r4
tr- ;+z1uj t *ezl H++. ol gtlel rll$gg ffi$ pol
+E qE -E¤ *Bol tsdE o +,il 4a ¤4Ig 7la q4I
s+. q +E ols-" 6[{ 4f449g q-= + ?l/l ¤ 4o14. ol4
eg ¤aE t6]|^J +Eol s+qtql^l Eg gfl6J + glrtl
=
¤ 4o14.
108 375
=E
(c) zlE EE B
+
B
+
ql-E+l59 gqBE olEol E+ +s=4 ee E+E]|#9
A A
+E}8+. + T + -
(t o o o o)
loroool f.al 108.s ral 10B40ll.E1?.!ta + EHe-43 d-d
7l^1 +lE-Er.+EE
D_ loorool (10B.3) g+A Pr=Pa+Paolr. 9E+ Pz=Pe-PsOltrl'. + dE
=Er:
4?-l 1^lfl
==_LH4E
looorrl 7lE EEoll 0Ee.l El|e=o1 .8ola|.4. =EtA
Io o o r.)
=^{^lq,
4sgE"l olelaJE+-Eil4¤g +El.ll= agc,,9 ql 4+6ll^l (ps+pa)e- (pa+ps)z} ¤tr}. ole+

'lla ¤ "I&zlzla
&=ql e_l6ll^l p,,py,9p,zl Ei4l gq+9zl ?*e4, olE ^ll +ll (-pr)<-(pJ"ll ql+611^J (pu-po)e(pn-ps)7\- ¤trI. Ir|4^J ol
sg+Eol poe| PB6].I_E g6'Jqzl ?+zl"J pae| pets g E A4e+ += ¤&ql q]* +Î* A4E+q zl4 @, pJ"il
^lE
.Jg+= 4,9 -uqr= 4o14. trI4^J ol zl^li q1 ffie-_e sdol trl¤4 ?ol 84.
^lE
e4 +g + 9lr+. /ilr| + tlig
+ s ^Jq zlzll p +llEoJ+
zI (pe,ps)E ¤ 9lall +Ee=tr. Afl+g + 9l+= 49 9"1 D(E) =
I
D(Cr) = -1 0
0 :) 01
++. ol azfl9 lil-g Tlzlql qlfl E¤g tr}e=$ ?ol 448
+ eltr}. D( =(:
0
D(oi) = -1 0
"J -l 0-1
p,9l 4eI D(E) = 1 D(Cr) --r D(o")= 1 D(oi)=-1
nr9l 4a} D@) = 1 D(Cr) =-l D(o,) = -1 D(o',) = | ot q*?l=s E+ E+-'H4¤otq, ol

^tt =* )", [i :
p,oll 4eI D(E) = 1 D(Cr)=I D(o,)=1 D(oi)=1 r" + dB aqlol +E qq+ ¤&q E6]]^JE 4lolzl
^lE
?+=+. Irl4^J rol + tzl-fl -E¤el zlB-e-E qE+¤+.= 6I
olE¤Eg zlzl y{r), f(2), lr-]tr NrolrE. +s_r+. 4"lzl F
4E p,ol zlzlzl q= 4+4 E3 tz1-g -s.¤ol+.
Tlxl EL+E 4 (po, ps)E trl-.q_4 ?ol ElF4 o + 2ilg -tr¤
rql qlfl zl4zl¤rt. D(E)-1 D(Cr)=-1 D(o,)=1 D(oi)=-l
0) 0-1 olAg p,{l 9aflr.l 44zlE rilfl *fl ltrq- +Ag 4o14.
,Gl=l D(Cr) _
E 6}+el d¤ a'J prE 4s=4 eg s¤ql AaTI+
[0 r) -l 0
D( = D(o',) = -1 0 D(E)-1 D(Cr)=1 D(o,)=-l D(oi)=-1
"", [: ;) 0-1
ola q^l ,(ll_trs rzl-fl s¤olq f(4)s g^lqlr+. oldrgEr.j
EqE sil-tl s¤ol sel zllzfl p flgaJiql el61]^J 4izlE g4q -s.¤ol trl*q=4 4ol szfl9 E¤o e E+¤+
37llE ril-fl s¤4 (p^, pr)olJ E6H^l ¤lzlE zzl-fl s.¤r+
el 'zld 6Jo e EEqB.+r "J+tr}. olElql EEg trl+4 f = 2f (r) 1|- (z) 1|- (r) 1f (+)
zlol zln a +4U+.,

(o) xls
-Bt
|--|.(1)af(z)a|-(:)a|-'
^1tr
(108.4)
5A6J BE Edql^l + g4lE qsgE 'll4d -s-Ê¤ q
ol lx|fl Sql fltr, f(2), lEJtr;(:)-a- rJ ol4. Egqzl ?tgq, 6ll= ag ¤4I9 r rlE+r
6Iq, xE +ElU+. r?-l6lq
olag ol +g 7gt Ed('irrep)olr+I +E+ 2^led E¤ f' E{fl 214 @* py,po pe, pe)ql^Jb qg?l=E zlsTl +*
g + +llEEL+E dB A.J pr=pe*prel pz=pe-psE HlTl 4 tol 8u}.
zlzlaetB roe.s) E+E+ + 9l+. o,ts poel pB= ^Js H¤+
^la+. *
(ps, pe)<-(p^, pr)z} qrll ++. uI4rJ (p,)e(p,)
r ullEE 4d l}g trEq Hc+ +ts6171 9l6ll^J zlE @E ulrlLflzls- a|

o
l
trll= rog.+^1 ¤. r= r(') @ r(2) @ 13) @ r9=E 444 "t qI4.
=rll,
37 6 E]la
=rl
R E c2
I dl =l' +12 +12 +12 -4
D(R) (roooo) 0 0 0
TIEIL¤, i
lnroool -l 0 0
loo r ool 0 I 0 dxllE ol +fl '}]a ¤1ie 9l$ol4
looorol
IoooorJ It 0
0
0
0 -l
0
tl zttrJEt oll 108.3
x@) 5 -l qla ¤Î"l {8, 2C3,3o"}oJ Cr"tqlts 37J]el ¤t} *ol ?l
R ov o'" 4. :z4al¤ lzll9 7lE E¤ol ¤x[tr+. +E it+=
D(R) (r o o o o) -1 00 0 t+z+3=6o14, r?-l6}q + qla +Eol riffio145 4*
lo-roool 0 l0 0 olul oj!|9fl tr+ 12+d]-6, nI+^J dr=2ola=- +"lzl f,
lo o r ool 0 0l 0
lo o oorl 00 zlqt s¤3 2zlflo1 qqot o.J+.
1l
0 -1
Io o o r oJ 0 00 0
xR) -l
ril-fl r4sfl9 zl-trts uf-a Qls,fl _z zlale+ A+. r4r 108.3 rlE, E.
zlo-| s.¤Eq zls.E .Je E?-ll s¤g zlsq a+(EEg
o.|.fl fluol + H +4+E-g f =2l1r)+f(2)+f(3)+pt+roJrJ. f, +E E= ¤t}=g zlE= +4U 49 xls Eqr 614, ol
zll+Ei ol4g e+4 oE q ¤E6I4l4.zls s' Eel ¤E=3
R E c2 ov oi +9 4a ¤&9 -Ezl.ol+. SHI4"J 7lE E¤g zlc. pro
7(R): I-(')oll .lle} -l I -l E szls 6IzlEJ sltrIql^l= 4 .*.¤E 4? *E¤ ezl
^l-o_o
7(R): I-(')oll rllt -l I -l A, B, E, q rE

^l-&6Lq t"lq}
zl* S,¤# +E6H^J ++
X(R): I-(2)oll
q.J -l -l I u+.
7(R): ft3loll t}lt I I I A: lil-fl zlaf -E¤, +-Eld+ql ++ S{}E zlez| +t
X(R): fraroll q-J I -l -l B: lil-fl 7lE s.d, +-sld+ql +-J a4}el zlez[ -r
6J: I-ql Eil6J 5 -l I -l E: 2zl-?l 7lE E¤
T 3il-?l zl* -tr¤

E¤$$ tsfr.Ecll, 4¤
"ltl 9lg q= ezl-= Bq^J ol#
tlIaLH Cr,+el 7la+
"lg+ ?"1
LJI
5gt zle| E¤ol E
c,,+E 7lE s¤Eol "l= s"Jzl-l rt¤ ol +9 7lE s¤g
+E6J+. rEl6}q Alg E= ¤&q 4el zl.*'z| loJ ag +
olE gol+.
"l ^l-¤g +Eel aol_eg olge_Esq +Eg 4u+(gd EHe 7H EEol4a 6}+). A,E +_Eldql EilEl
+ gl= Et I .ll¤¤ q-q_r+ eol +Eig + gl+. .<li lolzl"J H}^lql Eilafl^l= _lt ag +4U+. B qa+
zloJ _x,¤9 +=#e-l + 7lE EEg + (10B.s) 91 3zl¤ B"lE 4al4 ,JBe S.sq, q4^l ,u-ol*
+q +g xls -EE "Js" B trI= +E6il^J ^J-8-6|]ot ++.=i.ls
c,"+"ll= #ol gleq(zls -Eql +44E +211E g), trI
47HE
E r0B.1g Ltl qlaAzle+ -s.e)4:9 Lll ge-l 4a ¤{}E
E|^J 7lE E¤g gl sol4. gql^J olul $olt aE"l ol + _tr_ g Cr"+el zlE Eol4. r?]r -tr 108.2= Cr"+el zls. _E.
E +"Jfl zlqt *95o14. ol+. gi==g E,ZC3, "l :o,z|:. ul"-lql +EI+q, 4 ¤+=ql
+E9 E 6}'+el ,Jq6J ar+E ++6J sld + c,(n>2)&
E6J* jt= +ql 4+q= a o +^J, E= 7lE E¤ r(05E jE 108.1 rlE E*
C2,
il¤ 4E xil+g 6J¤L ar| EI]a ¤4lE d;1;5 +4ql= +
e-l il+ h Cy",2mm E C2 o,(ru) oibz) h=4
+4lE +E}.11= 4o14.
^l-olel Ar I I I 1 i,f,i
I
I
7l*E¤,,
dl=h
^fgll-^f+
(108.6)
A2
Br
1
1 -l
1 -1
I I x
ry
zx
B2 1 -1 -1 I v yz
c,,el zlE .x.¤.3 4+7l til¤ol+. tr|+C,
. rl
"*9 zls E7I zlE ¤ql +qqq 9l+
108 377
=E
E 108.2 Cr" XIE. E* $zlrJ qlde +E Aql aA a"lq,N(c)= # c glel ¤&

C3u,3m E 2C, b* h=6
sl+= 444r, h= +E ¤4I=E +(zl-+)= +4.d+.
Ar I I z l,f+f
A2 I -l zlEJFd oll 108.4
E 2 0 (x, y) (*y,i - f), (yz, zx) qa ,q^7l lE, Zcr, 3o,lola h=6oJ d+ c3"qld= _*.
. rl
"** zls s7I zle ¤91 ++Elq 9lq zl erlzlETl {r, t, -l})e} E(xlEz} {2, -r,O})ql ql6ll^l=
c2 10B.7^l"l +94 p-"1 84.
|{1xlx2 + 2x1x(-1) + 3x(-I)x0} =0
+
+ 7lE s.¤ol rrF EolH tos.z^19 6Jol q-q=r+ z.ol 84.
Z
Y e I ltx2x2+ 2x (-1)x(-1) + 3x0x0] = 1
ol lvzl
I
+ 7lE -E¤ol E+ A,"J 41E tos.z^lel .Jol ++4 e"l
o"lxzl g+
fB 108.6 Cr" E^lollll fl^lsl p, tlEgf#el 0l qe9.A=
=C =el |{lx1x1+ 2xlxl + 3x(-l)x(-t)}=t
E6llrt+= 4 # +cgE +E LI4U+. +++ ql roB3ql

d4ll{?lzlrl ol +ql= 37HE 44 6"1 ileq, r+ 6t+
(a)flxt ?llE--t+Eel El|e
^J =
zl*= *= e)E B+ qta ¤t}
2il-fl(E)ol+. ri}fl zlel E¤(A +e BE
= zlE r
sql Eqfl= "J+ qlolEl= ;+g E gq 915 xls* 6ll%L ¤&ql elEL +llEEL+el e# +
-tr9+ "J
zllEql q+ c6}:il "J= aolq, daEI q.ol =¤+ol]ulle. trI 4U+. rp-l6lq tg fllEgl+7]. EE"J9, r?-lr -tg +.llE
^lel .J+E Pszl H'Jg +4U+.EI+^J 4 ¤&ql E6H^l +llE.
zls sql H^l6l trt= "J+ +)ql oleJoJ ollull
= gle{ :-4a|q=+.c,,(H
trq-^J^ll6}rll .]]a ¤&g B^lB gs ++ql "Jq+= Hsl¤ ul:16|-r. olq^J ¤zlrl =49ts tol
C"l
71 9l+. +ilnq alol 3 C,+)g 4E elel S,"l z+
"J6:J"l 4 -rS +H d+el zl**E eE <tE$ ulral$ +ll_=.*f
q4 A+4. :24't EI'J +z|7l $H"lH ol Exl-3 yz44l E qla szl= "J + 9l+ +Eq trr"+ zlE -E¤E=g -trtltill
+olZl fl+(rfl 108.69 7l=6ll^J). rBlH o'"2 yzBql^Jel Ql$zl{4,oI+ Ep+ eg)E s,zl= R"l:g olEol 4+q= ?ll
HIÎ7I qq, ,.|+^l o',(yz)E g^l++. r4r o"!- xzBollrl EEI+ES gg +4u+(r46}q 'ila+
Êzl-E =zle f
9 H}rlzt qq, trI4AJ o"(xz)B _E^l6J+. A,E +llE6J+= a, ?Jl.E6Jf4L
=O,.
zlqt -E¤E=e.<le zli/oltrll, ol4g zJE rllErt q 4El
e ¤ce}4l H r c-ol6J zl* s¤oil ql+61+ r EqEq zFJEt q 108.s
:zH d= cr"ql +6I= H2o ¤:4¤ ^J4ql -H-zI.

ros.oe-l
++Elq ?lErll, "lag + EEle+ r zl^l4E Bol I
ol g+= 19 9"1*4.^lE zlnap c++gê4 ElEt=¤ zl
&iE 2p, TllE*fts C,ql E611,<J tsgz]. E6Iq, q-+^l
zlez| -1ol gtrl. E HI^l- a4 o',(yz)E t"JqL a$$ U
I-A+E+B 4ol4l "J*4. "l 4¤¤ trls-r+ ?ol Cal " -+
44o+ -lol E+. ole+ 4a4e + o,(xz)Y +llE++ql
+ElUtri o}+fl golE +zl g+eq EI4^l zlsz| lol+.t+ g4l
o i* j"J ,ll s. "I&z}xlE zlgzl. ro1 E+. El+^t StI {E, C, o, o'ul
i:r,t, )(r" (c) x'"',.,=
{
I i- j"J ull e1 zls.53 {1,-1,1,-1}ol+. +¤ cr,zl$' g.(-*. 10B.1)ql E
6tE u,-I,l,-llg qa + B,ql Eil* zlEEolq, EI+^J +ll
EEsl
EEL+= r *zl7l b,"l ¤4. o2py- zlzl:t_ ul$zlzl 4
Tlqr (108.7)
^ljr-tr+ol
z ol E4E +89 .rll zlilC gzl,E itloltrl. xlzlE9 Molecualr zrg 6l]+E zlsE"l qla + Brql ql6J {1,-1,-1,1}ol g+.
quantummechanics(2ott)¤ +r6l.q4. ol Eqql^l= zls.# d+E +l+
6Jtr}.
378 Er[ E]le
trl-4^l 2p, TllECf9 szlE brTI ¤4. 4}Ê 2p,e+ 2sE sA
E trI a,ol4.
2il-fl ol^JE 7lE -s.¤ql 4+ zl.tr s9 qql +e zls=

(A¤4t Ee+ r ole-lql 4.t 1ttzl) z11z11 zlxl 1l=945E sc S^6
f, adlq +llEQl+ +el 6t+7I qa az}{l el6]|^J H6Lzl gir. fal 108.8 NHre[ egCr, E^lel qe-43 CB PjE= tll 0l8q=
=ErE
4E a}*zl HB ullH:zH 108.7) zlgz| X=r-l=0ol ¤4. lll H1s illE-Er'+.
+C gzl9 ', p, "l d +llEEl+=ol +zl9 qla azlq E

611^l ++q= H+L dee Eil+61 fs_alzl trflEql zlg' s.gl
E "JHlzl_o + ol ?llEqI+EE qa +ol s^lqq il+. + .J+ fl= aol+. ol dB aoJe ol +E c, qdol+ ^ll +
olBl+ qa+ szlb zls -s.9 sfq +e+ 9l= x, /, E) z 4 HIÎE qL aq E4^lE H6lzl g+eq, q+^J t_ xls.
el qa+g jrrr EoJ+. qlE^l s. toB.2ql^Jel z9 flzlts 5ol rl-e_$ 4.ol 84.
p"(4?)41 ul{lolû_)z} c3"ql^l= qla+ A'ql +6}ir" e}¤ p,
* pr?JrJ xfo)q yf@ql Hlqld-L._)= 6-J-E.e_tr qla+ Eql + X@)=r y(cr)-r x(o")-L
++= ag- +q$trI. dE *ole E.¤6}zlH, p,4 prE -J+ ol pffiC3, zl-S. S.e+ Elrafl -H-H W,ol A, 44t"ll" uI4
e tr qla+ s9 zl* s.¤ql 4t zlzlzl ¤4. +d flz}9 s Ezl at¤^T*Al E+.
^J
+llE,*+= EE qa a+ql qlql^J EHolzl qEql flzll+
sdEI qlag *E zle+ E¤q zlzlzl ¤+.c,,ql^l= qla
+ A,q +++. GZEE +lEs+etEne=48
+ ?e +E +C d lllEffi=g zls. s9 **ql r/-e s. C2, No2 tszlE ?llEQ|+ V=Ve-Vsel 4a+g 'JoI4q
4. vÊ + o?lz}el o2p* +llE*+olr(Ezl Hql +zl+)
^lqq ?lErll, x/= d,/Ee_-tr
714?JL+.rq6}q cr,ql^l= +d
flx}9 drq d,._r.ol d-Eo s9 zlz]z| ¤4E a¤. + -bql rrsE 4E oflz}9 4014.
"J + 9l+. Ialg y +E g +E= %E +szl v^9 +se+

^lB
HIEI4= ag *++. ol d¤ Aqlol +el 4 qla azlql
(b) cE illE:d+=ol Etla q$rll H6h=zl$ H 7, :z xl-859 +lql^Je+ e
el6ll^J
=-d = ol 11, -1, E= 0ol+r ++. oleal 6il^J Eg zlsEg
zlfillzls{ %r-ts$ "l+6IE +]]EEI+EE dB A'Jel qa
ol d+ql q1o3 zls. sE 4 q=4 ultalfl qa +¤ "J
+g g.IE + 9l+. qlA4 c* EzI"J NH3el .r'll Hls +llEq+
+arB 10B.8)el dB aql v4=sA+sB+s.9 qa+g "J"I + 9lg 4o14.
ol d¤ Ailg :.8 ros.sq LI44fl4. vrb c, El
=ol
dql E6ll^J E6Izl ?*eq, q?+^J zlsz| lol g+. o,(ra)
+
+ Hl^lq E4^l= + fllE++7} +o-= tr+ Hl^+q, EI+^J

+ V+-V7l 9ol xlsz| -tol $4. fl(yz) Hl^lql el6ll^JE
+ V+-V7l 94, *I4rl ol S+Iql q* zlstr -1ol g+.
r?-l6}q zlEgol q^q=r+ *ol ¤4.
ilE) = |
- | f,o"(xz)) - -t )c@'"(yz)) - -t
y\cr)
ol AEg & .{a+9 zlse+ Asq, q+^J ol yrel s{
feJ 108.7 q7l

* arzl ¤+.
LfEl.L.! + ?{1e:g+= 7.1=E= E-d U,'.toll E}l6tl^|
^1e
trl= ¤E= LlElt!tr|.. 6'l'Ll'= +E= Hl"+r(-l9 sE 6lLl= ul.+xl
g=tr11+t E rlE).
= ^lE)
1oB tE 379
E 108.3 C4 rlE jE*

z
YN L
+ C4r 4 E 2Co C2 h=4
x
o A 1 I 1 L *,i+f
o +
I ) B 1 -1 1 xy,i-f
E 2 0 I (*, y) 0z zx)
. trl y+g zlE s7t zte ¤.ll d"l 9ltrI

lal roB.e c2, No2 Exloll^1 O2p, flE-d#Eg -d qe-43 dE
=Er'.
rPl 87[ 108.2 ptcl4'z- 49 ct 4AE]==g Dnr,, dt9 + q-g=n} *ol H¤L¤4.
4¤ BE Ellgg olEtrill). dB AEI ve-vs+vc-vo7l E: (Vr,zq,r) + (Vr,rq,r) Ct, (Vr,zVr,,,)+ (Vr,r-Vr,r)
qts qa +ql +6}dr+t ol +ql^l c,+g x¤4 F
ci, (vr,rvr,r) + FW,, vr,r) cr, (vr,rvr,r) + ?vr,r-vr,r)
6Ir gzl6}q, o,HEg *2P,4 yz{ olt_ "Jilq}+. 4?+4
E +lEF46l-=x44 ftg dA6Iq4. qf;-6|= qE s¤e q-gr+ ?JL+.
1
D(E) =
0 t) D(C; ) =
Ir t)
D(C;) _
0-l D(C,) _
1 10 [; :,)
"s,E r4:r' zJEE q-q-r+ A+
X(E)=2 XGt)=o X(C) -0 X(Cr)=-2
(c) xls Esl qialE -s ron.:9 zls-s(sld flÎc1e+q= ee +ql +6}-q 2c,
Eq TDql,rJ zl4t ule+ zlol tlolel E+-" gL+E"l +"J,* ql szl ¤91 +EI++)= -H-H abql ol zlz]zl 4dt Eg zle+
LJzIE ,Ie qlel qsl+ 4a4 +Hqq, 6J qlqzl s.¤"ll aa gl+g "J + gltrI. += Ez 2+ trlEl
=+lql =gl,E=E
ufilzfzl{,3* qE+(E= tr] *.g)= ol 4lq sq. EE}c_=
4s"6Jt irls"gl+Eol qla ¤4(ulle p- +E$ e0. el{.t1
7l= ar+ ae)ql E6Hî tls E+|g + gleE ol "ilul qlb zl+zl-: o12.3-o3 zloJ sflol s.+= 4g ++al¤4. ol
^l =
9lz} sls]¤ 1"14.r461q ol+6IE EE6l qq¤ + ++,ll¤e q+r+ ag "JEI +4g trq++ 4,o14.
=Eg
"J.IB + glg 4014. 6J *ql Eqgl= alr zl-+9 zle+ s¤3 r +E alql
zlalqr{ c + E trI LllE +E¤. c_+ql +6}q(re ros.ro
trlirlE zl-+e+ rvtr+.
r+ s. r0B.3), c,qd(so" qd)q E6l]^l xzl ytr- H6Iq r
9E. "l-t}7[lq.3 e.9 zooll^J ¤E.J Hl-e+ eol + iil^trro 6-l- r46}q *
+ql 7lE s¤ Ez]. f4l;fB alEl] 9ElEzt zol
i Vr,, - (2lL)sin(nrll)sin(2nylL) o) Vr., - (2lL)sin(2nxlL) +. E +ql zlE Ed rzf fzllalH alq 4Elsz} rol ¤4.
sin(nytL)+ E + qlqzl sh2tsmL2¤71^1q, q+^l ol +ql ttl{^l= q $.$ il+9 zlel sdg 714 + fleq, q
2+eE trlglg 4,"14. +E ¤4Ig ol+6IE ol= i. =+l=
.J+= +g il+el trlElETt 9ig + 9t+. $}"J olq{ 55 fl4iE
zlE= a"rrJl E¤E il-+e+ ae_!_s 3lq q+E= zls' *fl
c4 eq 6lEil x(E)E <19 e;-, "JoiB + 9l+.
c2
zt'J:d ql 108.6
0
x rrr4 Ag ¤H 348 EzlE rel d+ol Drnola,
ol +q zls E(zlE 4)zl r 4X ++ ?*4 9*zl oll
L
Eql 3+ tr14 +JE.g1'= ,14 + s.+.
fal 108.10 716l+5?.! LllE gEg +Elg +
C4Z{E,2CouC2)oe ?]tr|-.
oll+ Ezl-b +Ezll d+ eq +6Ia ol +g r qa
: E cl +t+ +g c," E= D4hE
^l-s6}+
q EJ_q_-eE ++61 qacg 9 zle+ s¤9 *zl ollE{l 16 gE+ +llEarag- zlp
s¤g + iltrI.
380 Ex[ EllA
+ flzls ¤ +Hill p4ql ql6fl^lE +eg

iltr+. 47HE . ¤Bl{l +z}c609 d zoHxll d+(rh)ql +6}q, ol +z}
E?-l7I 4+qq, ol E4*:.61 qnl fllra;a= *= 9 zls E(ztE ¤)q E4H 7lE s¤E 4q iLg+
TI1F +Eql Ezl4. solr tr14î s+ qsl fllra;a5- rle + fl+.
=
T]|LJE
=g:et
tr1. +qlql^l Eol* ol Eq
^l4L
? Eq1.q tzllq}'ll zl# IrJ Ds. +E St}=ql qql qB r]lsgEE dqlg =dal EEol?+n
+^l7l= H*I=g d6Jg "J*r+. 6J4.
42. qla s4I9 ¤

+9 il++r +r+ !6. rlE E= +E -Er= zlsl E.¤9 xls.5o1 zlxH¤ -s"14.
tr3. qa ¤4I a45 '+EI.ll= 4gg
zl^lql ql"J E}|Efl =d=J 47. qe +E 7lE s¤91 rlloJ szlolQ.
ol4r eI+. tr8. +E =e
zlE ed9 4r il-g ++-:r. +E r +E alEl] qirl
u4. gtlg +El.tl= qE qlsgE ql4C a +E !+g rlEqr Ee+ aq.
++.
=g=etAl=
,(-lzI
o=. l.l
-1 +4 ^l
{E
+E +Cfl R = S-rRS +E E= rla s_4= 108.1
zlel*¤9 f zle+ s.¤9 + = +E + l0B.s

zlsE il-tlr+ il-+ =o 108.6
=el A!: trt
+L
E -f-
IL
zl"J s¤9 lrC f prvtclzn" 1c1xd" 1cy, +ql aa {} r0B.7
0: ,+loll 4dl
r: i= jq qlql
EEJ 10C Elleol 3E
> ol EEI= HH+= olP

E- Erl TllEEt+= "JEz E E8trt4 dE4 +..19 EIE= tll + +
olEqE
=s-dsa?q. -1 s o{cl
I{tr o-1 ,(iH qq
O
-rl- -
> Eld TllLJ

+
4E0l 001 Elxl goalE ErlE E}l8 Ha+oil E6H^1 :1 4E0l
E6[xl ?-iotot:Lttl.
(a) (b)
E4 t0A0ll^1ts E^lE9 Exl- ilA

t|'|E e^011 gr+6t|^1 fg 10c.1 nl-49 -Er+7lE(Gzl^=crE 4 4e ELlollsl6H^l Edl'^l
(a)
E+61ts "JE= 47t|6ffi=ul, 0l Eitloll^l= 0l LHE- ri gE *erg tttl"J +,tlE Bqq 4E0l 001 El^l ?j=tr|. (b) trl-48 :Bt+Tl Etloll
!E trE 1080il^1 ¤E-d Eel ¤tr- 3xl sl6l1,\l 4:e-t1 E6lE : 4Eo I "J840 e 00 | Etrl.
^l7la, ^lEel ^lE
?lE--J a0lrl qr',8=3 c0l 8+^l EfllE(EE BC)= EEt-d
",_j= 2r^g+4 ¤EEEE qEAt+ 8q aEoil el=zrrl'=
?i=
7C)01
q lrc.l
z]trJEt
$t0lo t -"tt[
gdq +cg E EH +4¤ E?F{rB ¤qql 10c.2)E
aA^l q;1-xy! {$+ Atlzlool q=zlel q+= "J
+¤+ slqql^l EzI +]lEE}+= "JEr E E*q}4 dq + EIH +d ol eolol c,+q +++= ag g.I"F ++. ol
zlg +E6l]4= ¤- +"J"J EzllE¤ 4A6l]+= ql+61
'Jq +9 zlE sq E6l4 *yY zl* -Ed Eql Aa?lE zlzl9
6J ++ol+. 7^dfl"14. ol irl4+ EI+= A,ql aazl.$ {g$ z}zl
r ?lzl ?+71 trll$ql ol EL+el 4$ol 0ol qqoF +tr}.
10c.1 4E
ÊEI= L/
qI EL+/(r)zI qI-44olold f?x)=-f(i7l e qE x=0 f?l
+
el qta gqql^lE ol ".J+el 4E rzy flxll4 001 ¤+. Et+
f(x,y)41 ql6J 2il-fl 4E(4a gq ^Jql^Jel)e r 4E Hol
7I qla ¤tr+ +4lg+(-z-H roc.r). "J"J ol El]a ¤$= +
el qL 6i+ql el6l]^J f@ilq Yazl H6iH ¤& d ¤qE
z)4zl S4I +q +4+= zlqe+ tl+llqq, rr-l6}q zl$ol
0ol ¤+. 4$ol qzl ?+eeJE 4EE $oJ soj=ql g6J
0ol
g += 4t r]]a ¤&ql E6H^J 11 4E tJizl EHolaI"t tL fg 10c.2 -*i f=xy1 34e gqg C3e-Doll et! 4# 0
=C(qegp A+oll=
+(E= alr+ gH"J 4. al4zl :aoJqqot EI+). "l '-ll¤¤ 01tr|.. 0l e+ts
=e-e
qrn rJEEI^loJ r=l^l
===
olE
gE + ?ltl. dEE r-JP 0l -Et+E 3xffl Egoltrl.
6H^1 eg
+Eql^l= r+s=4 pol *flt;!Q. =zlE
6J*A ¤qql eA 4Eol 6o1 9zl e*e4H : El4B

q++(EE 7lq6l+ E+lzI d+e-l sd qx zlql s¤ (a)F et+el Eg 4E
!+ Aa il{ot +tr}. +C qltl 4E"l + 'J+ f ,4 f,4 Bg dill +t4 dill +
sd qla zlqr sflol* g= zlEz| rol q= a_e-E^J dB fl H+.ql ea("Jzlqqlql^J= B¤L dtE Erl) aol4r
6}xl.
4-oe A' 4{ 6ol+.
382 Erl Ell8
t-tf,f,ac (10c.1) A,"l ¤tr]- ? r,rxfu)ts i=j"J 4l* a,g EEL++.

til-fl zlef s.¤9 a+ql= zlEz[ 1 o]qH -tol4, fli)e] fu)
qlE^J f t+ trol* flzl-E9 flxI +llstlfola rE ol=
fr+
E Aa 4Eg + gl+."J"J ol zlEol ool4{ "14,9 olE
I zlsT} e¤. ql("J+ol E+ 1ol4+ "J4ol E+ -1) "J
zfx. ro'l +g+. qlE^l Cr,A+ql^l A,xA,, ArxAr, B,xB,,
+ +llEaJ+Eol Aazlzl ?*zl ullEql EzI +llsel#zt ^Jzl
El-eI^J ,l-48 EL+.J f ,.f ,zl +
BrxBrEg += E= A.Jg zlle-lalr. E-f a,o1 s4. zzl-i1
^l ?+9t¤¤ 9"laFb 4o14. ol^Jel s¤ql ol 4+^lTlelH a+ q +a= dlo}
aag
zI dt9 qL +'Ia g&ql EBll^J EHolr rEl4q g
6Lq, loc.lba E +Eql olag ¤B6ll +gI+.
d qla zllt -tr¤("JHI4 o + -szl e,9 41 a" )oll aa ?l tr14^J f ,4 f,zy t"le} qla +"J ulE olEel #e sa ql
gtrl"= +lql^JE zlzl4 *ts ¤4"14.
"l"F"J 4Eol o"l "J 4 zl* E¤-o + H$+slzl ?+sq r?]4q f fiE 4Ee g
f lrzl EE6l A,ql ail= ag q"J6l-71 9l6ll^J= ?+?+ tr114
¤4_"e.0ol ¤+. +¤ F E|fzl-E+ F"J6J qla =o_e__trr l
+ql eail=/,4rE !EE$ "J=q u-"I"t +trI. ol ¤zt
H+|g utlE olE9 #"1 Sd 'ila zl* -sfle +Al H+qq
E trl+4 ?ol *4L3 + 9ltrl-.
(+= qla =o_e=tr +Elel TlqE 7ls"¤ + 9ltrl) : 4eol
+E qa fl4}g g Elr_lE ali _EE "J=+ BE4_" e 0ol qzl= ?+=+.
a4l qq=/,"11 96}]^J ¤821ts.]la +q zlgE 4} 6J Ttzl +el6llot e. +s+ dg ol.e" als zlBol fl
+. E4 qql= rql el61]^J aazl= qla +9 zlE= =Eg

xll sol 99oF 6l-=zl= "Jg + 919 Sol4E 4o14. +E
^J
zlb+. e_E= 0ol oJ q=qlE qla$ ru+ ol+ ull$ql ool !ts f
F qE += g trt+ *6ll=+. ol+7ll s}|^l 49 +=el E gl= 4,o14. qlaql "Jeqot"il^] N_H aq}.l q+ aq^J
4ltr7l f f,ql el6}l^J aa zl= s¤9 zlEz| g+. r +llE++Eolq+ g4 Eq4 9l¤ 4E (sN,s,*sr*s3) d
d 4gol 0ol g+(qzl4 f ,? N9 zs lllErlfolr, r= t
ztElEt q 10c.2 gEI rlla+E ,ql u$zl9 ls TllEaJfEq a.Jol+).
cr"d+q^J /,9 qa + A,= 7l^lq,rE qla + s,9 4 q=q=r+ ae EE 4EE
"Jzlq+ql^J s6l +48+.
zlg _Eoll 96tH ol$ + +E zls.= 4
=+a ^J46IzI. t= f,frf ,a, (10c.2)
4 1,1,-1,-14 1,-1,1,-tol4. ul+ l ol + +E 4d ar¤. !
q-9. s.otl^Jq Bol g+. r?-l6iq ol 4$ol txll 9¤4etr 0ol qEzlE ot} 4.s
+e6I+. qlE^J dol .'3+z| e.fls(Eq 8c)= 4l&6l+ ql
E c2 o"(n) olbz)
A2 I -1 -1
"lEl+ zl$"l +Elt+. + EL+ql ++ 4$ql^Je+ eol ^ll
6J+q *flJ,A 4grzy 0ol qzl ?+eElH ol t}+g Ei
1
Br I -l I -1 ^ll
zl4
-1 u E
ol Sd 44 zlet s¤q Aa]. + ol s.Eoll ailE C#
u 1 -l -l 1
zlzlt_ gl"lot *4. "lerll 9=zl= BEIH "l zlE s¤

ol ulzle] qe1 zlsE qla ^ll
+ B2E zls."Jg +rJ "J + d+E zlss$ +lql^j ¤g¤I +zlql^le+ ee HJ^l o + E
9ltrt tr+"+^l ol zld #ql} A,"l E{ ?lzl |*eq 4+^J o]lEolo| ++.
f 1,4 d *Aql atl 4Eg ool qqo} *+.
rxJE4eE ool El= 4EE trJltt

zld +g q-q'=r+ +++ 5Ag zlxlz gl4.
?JZ o+7Jel E@
cr,EzIg a+ 4EI(d,,)x(d,)drzl4Esltszl -H-olEl.
. $d 41 zlq *¤4 += E¤rlE zld #e Eall -s r.E{-g A}EI Cr" zlE. s.E ol+6lq 3*-l(d,,+llEEr-+E
¤ ztillPi ?Jr+.= A, x f (;)= f ti)oJu|. zlE# *=+. r?-l
E), x, "i rr9l ¤izlE zlqt E¤9
Arel zlEEg E+71 lolq, q+^l 01Lo-e #6l]zlE r(0el a 3+ zld gql q+ s= "J.q ¤4zlE rla + +ql
zJs.E H6Izl BIa:24e. B=+. rq-4^l roc.r49 qL + e,ol egr-rl=zl= g"Lt+.
aJfz} A,i]H H6IH += .J+z| e,o1 9zl t*E aJ 4Bol
cr, zl.s' .sql el6IE ++ rr,
"l-4rJ +llEEL+
drE
^gg
4014. =ol
Arel ?ol , *? A,4 ?"1, l?]tr xE B,4 B"l E¤lEg
. + zle+ s.¤9 zld ='J3 ol + zlgt .tr¤ol F"J+ oll"J
EHAeI- 383
q+r+ Ag sE El¤ + {zlrl fE +c 4t} s.¤9 qla +, h= +q xlf 1rD1g

zlq}
"J + 9l+. tr14^J 914.
6il8 zle+ e¤91 q+ g4IE # c= +^d61.= 7tfl9 zl
= :ael-lL
E Cz o,(tcz) oi|z) -s, x(c)E E6l]B s¤9 6llB. zlE+. qlcg ¤4IE
A2 I -1 -l f, = d*y # dz]ql aa agg +E_,d-q+ xls sglrl 4 +ql
Br -l I -1 fz= x 9l= ¤4}el f rv(c)= g "l4ql +e+ il+. qa + A,el s
=q
Ar I I fr=d; d qla zlqr s¤g zlE=g dp rol4, El-+^J l0c.3a^l E
1
4AB -1 -1 I
cql ql6ll^J ,te,)(c)-lE r-6 sE trl+4 ag er+= EAI
=
g+.
Etq flel zlEES A,ol o1q+ Brq a$ol{. rle|,<l o1
4# 9¤zl " + 001 ¤+.

n(A, )=
f ;rvfc )xG) A.ol LfEfLl= al+ (10c.3b)
+4 6ilBg +d E9HH e,y,ql 4+)e 3+ zld +
Aq.ll ¤illg +zl ?+eq(+lql^] ¤EBJ a4l E
=aq
611^l), rle|,rJ E q Eeql $e}^l fr$ fr? F"Joll"t olE zlEltt 0{l 10c.3
e] zld+ol s,ol 49"t t}trt. rfl+ ol Ezl9 A+qlE cr"+el zlE Eql^J gEE qfl= E,2c3,4 3o,ol{,
ol=ol ?zl S4 trI+^l 4L +E +Cg +E-9 44 r, 2, o) 3olL, hE
rPl B7l 1rc.1 C2" Bztg a+ 4+ I(a_)r(pJatTI g r+2+3=60l g+. A,"l Cr,+ql^l zJ.E. {4,1,0}"J gtr +ql
¤zls+ +EI+= sl+= q-q-r+ *ol ¤4.
ÊqaL+? hE ia'E n(A,)=+{1 xilE)+2xX(Cr) +3x X@,)l
=+{1 x4+2xl+3x0} =1
(o) g'eel E61| trl+^l +6IE 6IH A,ol 6JH +E}t4
A+ql tr+4^J= zld #ol E"J *ol olH qfl rila +=
I ql"J + gltrI. qls^J c,,el a+ zld # ExEel zlsEg
{4,1,0}014, olES +-q-4 ?ol A,, Ar,
oi E_tr_ E6]lB + gl+. roc.lagl^l +tI+ ?ol * z1E s.¤E zld tol A,
uls+
ol q4H * z)E E¤ol F"J6llot 6JtrI ol Ll]¤+ ol-Elle+
E 2C, b, "l
eol loc.3b^lg "J+"H^l +E6J + gl+.
Ar I I
A2 I I
E 2 I 0
ql eJC E1{a TlE EEol
6L
ll 4 I 0
EEt fl=rl= Ef?l6l= 7l=
ol E6}|
7lE E¤ pri)e| fu)E zld tg zlsSpq ^J46]l
.E-zI. zld
e+= x E=A,+Ar+Eep +4$tr1.,
E
+q Eqfl= ¤Î=q #E FE¤g zle
zl-sE 7lq6l+
A++ ag 6Jbql jnr E6llp + 9l+ rfl+ +Eg ol E9 toltrl. + f(c)_"trr{it(c)1rtrr(c;z} qEull, ,rto161;. zlet
+61-E E¤E zlEE ol.e"6l.{ E4qq +s= 7lE s.¤el s.E r(,)el fr Cql ¤&E zlsolq, 1r{'r1C1E ole+
qla +E-3 illal4_e tr. "J.l'J + gltrI. zloJ g.¤ r7I +Et+ =qil=
Hli+ 1014. 10c.3bE +qzl= zld-+ E¤ +ql sd ql
El+ n(r)=- r+s-r+ ag +E_e_E+q qBal +E* gHI
= 7lzlr. d zlel s.¤ol +4+= q+= r+s-r+ ?ol ?q+14.
^l¤.
+B + 9l+.,
n(A, ) =
|>lorc ) N,"' (c) N,"' (c)
n(f )=
*Irr.l
C
N,"(c)NG) E-de.l E6H (1oC.3a)
(^l 108.7).
I Eq l6Bql^J ¤E6J HIe+ Aol zld Bg tr|tr.= O.tr" r4n

zld #g
o i*j
trll.E= a.=. qquq. ol zlEE E@E=A, oAr@E
i' 'Jrll
z
"l+alH
ol E4E q-4f, Ae.ltr+El +g+. x-lzl-E9 Molecularquantum f,\N <c) xr"' 161 xr' 1., =
{
I i=j grI
mechanics(2ol1)g +.I.6IqE. ol Eqoil^-l= d+e q6}S.trl.
^ls$$
384 Erl4A
nl+^J
Eol czs Tllsa*ft' Td+E A,ql aazlq, u+4^J ola
n(A, ) =
o i*i "J,I 3 urs +llEEL+E9 A, d¤ A.Jr+ 444 f :19 4ol
1 ;=7oJ 4l
Hl^+q g:"tH zlE s¤ol F.J r]]a +ql +g uIqI F

a + flsq, El+^l rllc2p +llEJ+=.9 d-rEo s_tr ag *4
"l el H+lg *4.4 0lE3 Hls fllE*fEE r, dB At}
zllr E¤fl zld + +q n,"ll ¤4zl= CE"l Eqil4. "l
e4= 7lE E¤E iL+ql 5-galQ. 4 aAe + ?14. E (xy,yzxz) +llEq++Eg r,oll 43zl
q, q+^J du do ',i d_ +llE*+s=E uftlzlxlE Trql e
izlq, rq6].q Hh TllE*+59 r, dB aq}J+ 444
+ 9lg 4"14. 4"lzl + d +llEEL+Eg s"il d4zlq q
10C.2 Erl illE:Er+=oll EH'EI 3E elrj R,ol+ r, Hts ?llE*fErt 444 + S.a HIA6J
fllEEI+E ts"} glzll ¤+. tr14^J "ll*ql= (C2s, Hts)-d
flql^J ¤E+ +{s$ ol+6IE {B flzI +llEo-J+E"l +
?9 u, fllEJ+e+ (c2p, Hts)-dd9 t, +llsE}fz} ¤zllt
^lql^l ¤s aag +48 + glEzl drll ++6J + 9l+. +
4.c:a +llEEI++ +^lql t, +llEEL+ql 7lq= 6J + 9lg
gg ole-" 6[E 4ag *= flz] +JEQ++5E dB e
=ae]
6JlLCAo)g EIE= 4,ol4.alxl {lulzl dz} H]]il= ulz|,<J altlzl qq E=
ezl¤ "J"IE + 9l+.
A-J +llEEI+rI A+q= 4,o14.
(a) fllsB# Efl g,71 1OC.2 gHillE:zlql^lb se-l +llEEL+

sF6
^l7l
El} +CE s?lzl¤ a.t:ol.-a 9l= 4 Fgz}el 2p +llE6J
flzL +llself v,* y, rlol9 trFq-r+ ag 4E sE aa 4+ 4zl 44411 4etol {zl4 p9x}9 ol +lls.E}#E9
ol+r 6J+.
A,r+Er+T,"ql a44I+. sE qE +llEoJ+zl. dezl o +
s-lviv,dt ae 4E (10c.4) aAzlAL+? Hlq+^JE]] {z}uflzli gH 4ol 94ts4r
fa"jr8|e :(3g;1;'zp6;rt'pe)'(''I)d¤'(u'V)t¤,11
roc.ral4 +¤6H^J ¤BeI utq 4.ol ol 4tse + +llE6J+
7I E"J¤L qla+ql ae ulltl ?*E+ ol*g q¤4
eol +48 +E 9l+.
Êqzl (b) E]l8-44 CE
=il
E"J Ella +el +llEoJ+rqqlol tElzl ?*b ¤E Ae eg rosoll^J= .a+ El]a +-o .e^J H++s.l= ?lzl- TllEsL+
g ++B + glsq(s + 0), trI4^l olE TllEEL+EElol E9 dB aqlg "JE + 9l= ,JHg ¤H6I9+. "lBlq} d
a6JElq aq] q Hlaq+ +llEE++E "JE + 9l+ B AElg Et|e-43 CE symmetry-adapted linear
=-d(SALC:
combinatior)9 6J ql"Jrll, ol46J d¤ a'Jg .lla
LCAO B_o+ tszI +llE6J+=- "JE= rll ?loirl Eil+61 6,q g *= F"EI flzl-E9 +llEgl+=E "J.qc +llEEL++. =C+
+ a +41= îE AAe + 9l= gzl fllEEI+p$ TIBlLll 5ALC= 4d"l 5-"J6J += +llEEt+E 6irEI A4A + 9l
aol+.
"lag EzI +llEEL+= "JE= trll ,l]+ f+q} 4o14.
oF+
=
SALC. "JE= "JHg +E¤- olf-aH,! +Eg + il-g.q,
EZ@7 =Elou
TrqE + ?r= flE-d+=E
^rE! FE Etlxl fl)= ol$allo| ++. F¤ fl&zl-b 4*4 ?ol
,lltEzlql^J= Hl Hrs +llEEL+zl-A,+Trql eagl+ zlxl flIEEL+= q6}q olag F¤6}]^J 4a+ re g SALC
c2s4czp flzl-+tlEE+9 qL a4 olEol d4zl4l:=
+? EI"J cflz}9 d +]EEL+E ol+g + 9l+H qtr + = "J=+
?14 flflol zft.al-dg+i p(r)-iIr''',oro v"'= p'"v, +E Etl^l (10c.s)
R
zalE Al¤l rd zls E(zlE ¤)= +r.E 6[{ e,ol4 r,

.ll ¤421ts s,p, oi d flIEEL+$$ +E+. zls s. 9-E ¤zlrl vE Tlzl +llE6J+el 6I+q l.)= '{a+ rilfl H+|
9ts serc(E ol^J 9ig + ?l4lolr|. .JCg +
+ql dEl fl= 4ql6J 7|ql^l"J EI+= *oI^J 'l]a += g4(#ol ^l+71hoJ
qgr+ rl¤
g lpts + 9l+= ttzlt;lzl BI*+. E ol-H)ql aa ebl4. "l +zlg ?ol
Îdg 4 o e. ¤Bg
+E 9l+.
EtlA9 3E 385
. +el 4 Eila ¤& n"il 48alt g$- +gel *.5 "j= q EClqovoio'J
Ecll, 4 g "]?-lql 4a S&g't4U+. 4
S4lql ql+ 1 4eI a4
sloll sA sB SC SA sc sB
¤9 "JgE 4,o14 #ql 'l]+ trg "Jg= 4"1 "t'14. 2 Eql 4{L 4s 2-l -1 0 0 0
. 714.J+- CA6i_,4 4 g&"1 ol 71x] alfoll ulrl I 4 t4zel9 El 2so {B -sc
E a.r}$ +6J+. ol Ar+s gqzl*.J+#
rfla 4 sr9l 4eL sr+ SB SC SA sc sB SA
4 ¤& eql 4=+. s ¤ 4e+ 2el9 + 2ss -sc -sA
. ++ Bql= +C 4tI qla +E zlsr xtD(R)g +ElU4. 0 s6oll 4EI a4 SC SA SB sB sA sc
. g& ,+?+q\ ql6}l^J *E + B9 q]¤¤g +611=+. z Bo4ze+9+! 2sc -sA -sB
. ol pg$g 6J6J q+q +E zl-+E ++q

=4. tolt zlzl *fql +¤ ¤&4¤ ¤4I^l7lE ^Jolq} SALCE
ol +grl(3, 5, r,i 768).
z]trJEt ofl 10c.4
d+cr"ql +d"L NorEzI9 *

o2p.tllEEi{rH roc.l; *(2sa-sr-s.) *(2ss-s.-so) *(2s.-so-su)
. 7l^)a_B, SArC= "JEzl g16ll^l trl-g= 4 eg s= "J=+.
r4q olE serce-l qL 6L+= += EE 6-Je-tr +48 +
9ltrH+ "l dg dB +B"l a4e+ E4le+el xl+ +
ol-'141.
E C2 o,(xz) olyz)
(so-su)z| ¤+. ola4 4rll f(2s.-so-ss)b d¤4 o e +B¤
peoll 4* .a4 Pe -Ps Ps -Pn
SALCTI qq $zlr flrrJ+=.',JEb Ell ol+,* + 9l+.
e,ql 4t zle 1 -l I -l ^}l
4flzt EzIg Ezt +lls6J+¤- trJE= ar+ +Ha[{ E9
IB4 2BI+E + Pn Ps Ps Pn eEql^J E9+ uI4 *"1 E"J qlaE +llEEt+vl4+ 444
gl+. +E_e_s ol
tll-zlE BE -Jg +.el ih+(h= )tr_ +b+. rBlE tfBJ=+ ^l EzI ?1116]49- "JE + ^l-gg ++.ll
H 5"J 4a+E sArcEEJ"l ¤.E Aeg "Jsa + glsq,
(Po+ Pr)71g+.
EzL +lls*f"tl zlqg + 9l+. qlE^J NH,el ?* EzI +ll
z
Egr-+E=g trl^q_rl ag g-g 7l4Al E 1"14.
t<, +
-/ V@)= c"rSN+ c.r(so +su+s. )
B
VG,)= c"rPu, + c,r(2sr-se-ss)
+
Vt
(e
r)= c.rpNy + c.r(so -su )
A
I
+Eg zlzla- ol sI+ +el 4+Ee ACoJ + $.+. ol5g-
fal 10C.3 NO2E^Htr=C2,)E + O2p, flE-*fE 7l^1e- 0l86|'q
trJE SALC.
aefleJ$ Eq eEql^l tT|]aJ "JHg 0l+6110} ++.
10c.3 cE4 +El

zlxl a;-;q1 44zlz1 g:g 4* zlzl-:1 sercE "JE
'}] ffio-Jfzl- vr,"J a7l ^JEl]g+ i4-E.e-+7[ w"J a]+ ^]Ell ^]ol
E ool g+. qls^J A, qla +{EE}+E +¤g z}zlr. 919
9 Ezl dolzl-+EI{= 1EEH dE lllzl= dol .'!+xI
t++ qlql^le]. ae EE "JE+ts E q BE zlx5o1 4 EHIE(d714) rcql 9¤EI4(Eq 8c). o1 ElElel q4 dB(q
P rol ¤ lolq, trI4^J a4l 44 Er(]] qE #9 "JEE
Pa -Ps+Ps-Pe=ool B 4,"14.
S
zzl-fl ol^JE qla+E SALC= EIE= ae +lE +zlql
E6ll^J SALC=q oJol ,rjzlIr+ dzl ?++. qlE^J a+c3,ql o', o
+{-= NH,9 flzI +llsEl+Ee_l SALC# r,JE= A+= ^J
4raN Ezf. ol Ezl-e+ +llEEI+E¤:zH roc.4ql +4q]H+. sc SB
r?-l.I. S4, Ss, "l scoll4 xtqlE +g gtlzl¤ 4r-+^14 tila o

+ Eel SALC# +ezl 6t= -trrl¤ egl zl+6tts+. fA 10C.4 NH3(HCa,)9lll H1s fl^l +lE-ct+- SALCE UEts 7F1e
0lEEf + ?lrl..
386 Erl qa
I x, Y, Ets z)3 tl+4 ?"1 C9¤4.

-trel eE+ql del 91tri.
ll,1.r)= -e J Vi qv,dr do I g+^l E ElE ttrgl (1 oC.6) n, TllE'EtfE Broll 4ilj4 p,= Arql AilE + g9-
=01
+ zld #¤ e, y r(a) a BrTl 5l4. ¤ zlrl rtqrb x, y, El z
¤zlrJ -e= dzlel a6lol+. ol d"l EHIE= fff,4 4+ el qa +Eoltrl. zld #e qH +^lE +61-= tl+"l $.
4 Ag g-olu(10c.2^l). trl-4^l E qlaa" 4 ¤tI oq, q+,^l A,xBr-B2olE e A,xlta)vBr=f(a)vBr7t ¤
zI"J "JAl qH +Eg ols-" o|{ ol dol9l ..ilE} dq +zlg
4. ol zld Bg fldzl Br"J olql +611^J I y4 qa+"J
"JE + gltrI
qlql +6ll^l A,4 a"taq. q+^l q-yolH ol 4gol ool
qI !r tr++^J dolzl 6l+9+.
EZ@ dE4t*tE*E
c* 4?9 *= p/l 6l+q= d7l {qz} +4 ol HI= dolq +qq| {z}zl
+zl-ollrl pr+ "ll4"l *61.= $.<}
d"l4sttt -r. dzl ulrl9 ^d+ol /*6}0l+= 4,o14.
=
3e1El ,t'l,EI pqpyTl Arqlail=zlE a.rlollop ++(q7l xPf g7[ 1rc.3 qlag *= Ez]qr-l (a) p,J p,a
C,"
qE x, y, E= zol4).py, p, "i q'll Ellt E}]a 5g zls, Er O) p,J p"7l6l+q= d7l '!'=-zl. dololAu+?
^l :1a5{o (e) .E
h6g-ts tzx=b 1qy
=s-d7HE=
r t. zls. s.E ol+6lE el zlB"l B¤zl " e ool qizlE q+ i E"J qa+el ?llEEL+E"Jol o"l ol{ aag ++E +
E ++g + 91trI. el4.
- I zJ+ol ?+selH ul 4+ E+zl-+ill4 4{ zl"J r. E]le-43 CE ea(selc)e EE"6J flzl-E=e+El "J= gzl
^gqzl
g.¤(A,)ql q16J 7l^l7l q= cEg s¤-6tr. 9l"l"t *ct. +llEEt+Eg de aqlolq Sc6.J qag r*=+.
=s-d^l=
,(lzl
oa .Al
'1 +4 4Ha
tr¤E e6]l *IN(c)z'" (c)xq)
n(I-)= df zls. 10C.3a
'I4+= q+ df
E61]a'J a +ql A,ol r(A,)=lir,,tclrtcl zlE. 10c.3b
A A 4E s=Jvrirlr,dr ol
7]o-1 10c.4
F¤ ¤&X} P,,,=|D,.,(R)R V/''' =P''trl/,9 "JE+ 10c.s
4!ol ffiz[ sH]E u,.^=-rjr;Qv,dr q-4d8, Q=x,/g=.z 10c.6
.
"JBJ49E zls: qA+ <I& zl4 + 9l+. ol jl^l]ql^]:. ¤+ <IE"J +*tr+.
E= 387
E71 xto Ell8

=rl
e4 1oA Egrl qe
BatTI *e}4e_a ¤.C"1 g + 9I- 4? zl# ¤86H4. D10A.3 e+q .Ia s{}+ 6ll'J6l-= 4a s.Ê¤ +g6}q4.
BzlE d+-3- qBril e6l+zl ¤86I"14. D10A.4 Ezlzl +col ¤ + gl= qa 7l=g ¤86|q4.
G^
rl tl
El0A.1(a) r|*ezl¤q rla _s-A= +96rr olEol +61-= e+q Ea Er0A.3(a) ffi.$xlf,+ql^l +C"J + 9lb ag qL a,ol*i (i) sl?.lH,
g +44q4. (il NOz, (ii) PFs, (iii) CHCI3, (iv) 1,4-qE+9-aHld (ii) qE+ql* (iii) zl4ltrBeHr(dB), (rv) BrHo.
Er0A.r ror cl-* Ezlf9 qa -s-Ê +96}r olEol +6|= A+E Ba E10A.3(b) ffi gzlf 6q^J +C"J + flE ag qL 4"1*i (i) CF3H,
g +Elr{q+. (i) +E}(t), (ii) y-4E(2), (iii) 1,2,s-e elEeeHl4l. (ii) PCl5, (iii) E*^-q¤+a eqlfl, (iv) r,2,4-E Elq E e$dl.
o o O
E10A.4(a) q=E-e+sB{lE E= olce4Eol +61^= e.3=¤ 44
Ele+.
E10A.4(b)
e4.
q:=-eoJE4dq E= olca4Eol +61-= at¤¤ ?+r+ *
1 +aJ 2 Y-qaJ E10A.5(a) or'4 49crn d*91 +61'= ExJs=$ TlgCold-*i : ol.?
¤H6Iq+.
EroA.2(a) 11; /.l:.,_QpE-e.qlflr+ (ii) E*^-q=-eeqlflg e=g a6I ErOA.s(b) Th+ qg Ta d*91 +61+ E4E=3 zlgCold'*i -:. o19
=
q?+.
¤B6Iq+.
E10A.2(b) ffi gzls=el a+g c6}q+. (i) HE (ii) rF?(s4¤ tr-g, (iii) =
cmr(rxlB), (iv) Fer(co)r(3), (v) tHI crHr, (vi) qlE+5+gs+HI E10A.6(a) CH3CI Ezl-ECr, A+q +d+. ol +E qla s-Êg +96l
c8H4F4(4). a olEol ExI4gl,<l i}^l6l+ +lil= lB o e +Ellilq+.

E10A.6(b) BF3E4-= Drn dt9l +oJ+. ol +E qla s-Êg +g6ljr,
o H
olEol ExI4qd ilzl6l+ +l^lE rB o + +E+qq4.
CO E10A.7(a) LtEB-{l +^l7l +61-= t¤ "J.}.llJ, +zl-= r4n qa 3-
$lzlE +4.Iq4.
o I êl
E10A.7(b) E+^-qs=+s=tr9lHl Ezlzl +6k E¤ "JolLlliE Ezl¤ r
?]r 4a eÊ 9lil= Li44q4.
F E10A.8(a) +s qtlE"l +61+ d+g "Joi'-Hq+. (i) +, (ii) zFH t4
¤, EH lJi4B, (iv) Qzl ?+.g gEB ¤9.
(iii)
810A.8(b) q-g qldlEol +6k a+g "J"ILIq4. (i) 4ls gE¤ gg,
3 4
(ii) +B +E4E {}^L (iii) ¤d-"lzt gfl 4El
"l:_ & (iv) 3g(44 +ill
g BE s*) iEeg4, (v) 3g.?+7: HlEfl g "Jal E"J) ]Iteg+.
_7=
l'E
¤E E^11
D108.1 xls -trE trJs= B!+ L1l¤¤ ¤B6Iq4. 9E ¤B6Iq4.

D]08.2 s.eg 7lE gBEE 4A EIe-e E+6JtrI= 4.ol *9."Jzl ¤B D]oB.4 tol +9,qlzl ¤E6Iq4.
6H+.
DloB.s +Eql^-l (a) 4s.fl4 O) s.eol +9,9 F6l.bzl ¤E6Iq4.
D10B.3 zlE s.¤E qa +g -*.^16l+ Ell ol+q= E^lel A4¤q E
388
=rlE]la
G.\
Jrr
EloB.l(a) BF,E4q Eqfl= 4 flx}9 zp, fll=ElfE9 zlzl q}e-l g4I E]oB.4(b) D4,el zl-tr-trE¤4u 'r N(cN)i-E 6d flzlNit'-ql +lil6J
ohelc3E 4E s.¤¤- ol+6}q or,c,.E+rl +s= ¤4F+:' 4sfl9 7 4s,4p, "l ra qE.g'apel qa 6¤ "J6Iq+.
6Iq+.2i$ Hz| Eql +z1614l a6}q+. zJ4ll4.
El08.1(b) BFr+zlq Eqfl= 4 sz}9 2p, +llE*+EA zlzl "Jel ttl
E108.5(a) ea +ql 8ts41 +B +ql + go301z[ ol
g,E"l g irl-Eio fl--AE =q9l=
alq qElE= +6Iq4.
ohe+c,9 eg s¤¤. "l¤.6}q c,or,E+el Lts= ¤4IrI _z 4.s's9 7
6Iq?+. c,el rlls?lg +6iq4. 2i$ H z| Eql +zl6rrtl +l6F{+.
EloB.s(b) c-2oHal *:. gu3o1 +q + oJEJolTl eq9l+. ol oJulolel
al{ EI+EE +6Iq4.
E10B.2(a) D,n *9
^llcrstlg 4*zl5gt +q +.Jtr}= 1¤.
Eq4.
El08.2(b) D,r, t9 rll o"¤&3 dBzI F"Jt +ql +'JtrI= ag trq+.
El08.6(a) tldl! fll=gag-ol zl4 + 9l= =lElle 7l+oJ qelE= +6i
q4.
EroB.3(a) dtCrnql.<1 ol +q 7lE-E¤59 10B.7el aqq IrI4E.+ 4 El08.6(b) 1,4-q=e+Hldlel fllEt}+Eol zl4 + 9l= 4l4e 7P"d
nQlg -E-q+. El+E= +61q4.
E]oB.3(b) d+ D,hql^J zlef s¤ Eg l0B.7E aEql rlzi zloJ s¤ A;, 10B.7(a) BF3e^|ql +tll= 4 flzl9 zp, fll.rQlf# 7l4e- 6l-= s
A;,"i E"gl zljzElg trq4.
& onrl Eils?lg +6Iq?+. zffi $zl- Hq +46}zll +{6}q4.
E10B.4(a) D3l,9 zls. s.E ¤qerr sr9 ¤:C flzI At t'-ql flxl,t}:p4 108.7(b) BF3¤:aloll Eqfl= 4 ?zI9 zp, TJlrElf# zlzle- 6l+ g
3d +llEE++EE rla +g "J6|q+. /Jc,el qlEgg +6Iq4. 6$ $zl Eql +zl6lril i{6}q4.
EE 10c qeg88
gxll
==
qaql +* EelTI +xI fllEd'+=- "JE=
Dloc.1 Ell qB4 Dl0c.2 zls. s,9 r-ll zlzl ¤.EE +4,Iq4.
"l*9321
¤B6Iq4.
o1^
Jrr
Eloc.](a) D,6J9ld= EI+ ,/= qa 6 B'rE 7149= Bq4. {} +^lq q=)"J cn" +el 7IE sd"il aadq. olag {¤ zl"J .s'¤ql
El0c.1(b) 4h+ql^l= tI+ xyzTl qld*,\E Eqa}. ¤4zld'*i
'Ieg Eroc.s(b) 6J zl4 *izl zls. 6, -2, 0, 0(zlE ¤ zlE E ^Jel ¤{i
El0c.2(a) cr"ql +61+ oF2¤-zl-= i84oilext ol +xl+rHt}q +q9l ^llEE
a- z-+ol cr+r+ 44. r?-l6}q 49 H o',9 yzBola- o"E xzHoltrl. F +^lql q=q)"J 4+q zle+ sBql e-{tr}. olae qtr zle} s¤ql
pSxI9 p,(A)+p,(B) C¤ Aqlg Arq ¤ilr, + FgzlE p,(A)-p.(B) d aazld!.+?
B eqle B,ql ail4l gtrI. +d o+lÎel fl;tzl fllEaJfzl. psxi9 ol ErOC.6(a) + zlzl t;jlzl t
zl-*. 4,0,0,2,0,0,0,4,2,01{E ¤ zl.s. -s.
cB ai+4 444 + 91ts aol 9laL+i ra +llr.o3-;g ol+E+ + ?l el gtl +^lql^]lEg]
trI=).J D4h +E zlo+ s.¤oll Aad+. olAg qE zlql
=
b sr,E A+qlE qBrll 9dg+i s.f,ql ¤izldg+i
E]0c.2(b) ¤# eroc.z(a)q ,J3 4+E.t!ffi$z|. n (A)+pr(B) CB e a3,qc.9 zlz) $fzl xl-s. 6,0,0,2,2,0,0,0,4,2(zlE. ¤ zl.s. s.
ElOC.6(b) t}
*4 pr(A)-n (B) d¤ A*ql E6ll^l ¤ixlE 7lE Ed- +4q4. + E S& +^lql u|=)"J q +E ziel *.¤q aA{+. "lag gE zle} s
d ogzlq flulz| fll-Ei++E^l Fgz}el olE c¤ aEF+ 444 + 9l= ¤oll ¤4zl4lL.+i
Aol 9ldL+? E10c.7(a) (i) +gB{lg H}qt}Ell(SA qa)e+q dzl 18+
HlCl4 (ii)
EzI No2E ^J4ollEzI. + Ogx}el(xzl lzl Eq +4)
El0c.3(a) C2, zI d"l9l 96ll^l q¤ tlElle EEA-+?
d¤ e*g A,ql ead+.+rJ Ngx}el fl*zl flEql+s
p,(A)-p,(B) Eloc.7(b) (i) "JE4dl4 (ii) ++HI(s)e HLqt}Ell(Sd qla)E+el dzl
^l fllE¤:+E d¤ aElrl 444 + 9l= lol ?ldg4i
o sa flEt}+ ,l3+zJ. d"loll elfl^l qtr tl-Elle E*d,-+?
E ol*e+ + 9l= so,E a+ql= qB4 9d,v4i
E10c.3(b) d* o,ngl +61-= BF3g ^Jr]-dl!-zl. F fltz} +llEfl-++El trJ
SALC]==+ Ar"4 E"ilH H+¤trt.6d BgxlE gltTi ills.Ei+erl
=
ol sArcE4 Aae + flb dol ?ifl.g4i ra +IEEL+¤
"l*6J + 9l=
M,9 a+e+ qB4l 4sA-+?
E',r0c.4(a) NO2el Hlqtl'elEcr" +q A,ol4. ol E4-E {zl ffiz} {o1
q el6ll^l qtrE¤ + fleq, qB ¤%I9 qo1 $!_a]"4Lg+i
tlEll-e
E10c.4(b) clorBzHc2" +ql 4+4)zl rll +ql eq 9lq. ol Ez}el Hl
qt'-el= B,4ag 4=4. y4 *a}e_e. E45}ril (oo +ql BB) ¤=JE 5 a_+LJ]
Hql 96ll^l ol +zI= g.3 dz} t4e. E=+. ol EE tI4E qag "J
5iq4 El0C.s(a) cr, 4ag '*= +zHl^l 4e lp.zp,&zl9¤zl " e 0ol qq
E10c.5(a) qI zl4 *izl zl-*. 5, 1, 1, 3, l(alE ¤ zls. g tlel ¤
o| alizlel q+E 4a ceg 0l*6ll^l a46}q4.
^-llEg
EA 38e
Eloc.8(b) D,, 449 *= ezlql^J 4E [p,zp"drzl9S4 o-e 0ol E]q 7l A^l d"l{l
oI6l+^lel q+= qa Ceg 0l+6ll^l AC6lq4. E10c.(b) Dur, 449 7t= +Î9 {zl {fr2} dol9 a+ql A,g-+82" d
olz|;l-zl Aol+?
Eloc.e(a) c,, qa¤- ,*= +^lE z$zl 6t-lz| d"l9 a+ql e, -+e, dol
g,la 11
ErIH r+{
t=
EzlTI +4LH= g"Je B49 9lHzlz} HE 11C zflTI ErIgI TIE EBH
ÊEBCE9
4l %rzlzy %'-=q4+ g+qrl+ E= 4}+qzl ulEol4.E
xI #}tr+ol flzI #Jq(Eq ac)r+ += de BzlE gluJzl 7E)=aE_zl?l zflzlEzlE d+EgE jyl
=E|4]:="z(e.q
zt dxI-^J4 dols"J olq4 4lE tr-El]e+ sld t}el Hq.ll }. oIzlEI dxll Ezl-b 6E| {:e"z}s.l CeE+q H,q4=-e ol
E6ll^lE Hg + gt+= 4o14. 44^J EzI gz} ag rEl6il +qoF t4. zl-I BzlE dE a¤i
,.-gleflE{ ¤d q +d-6I4. rfl+ E4 ^slEHg ^dlEHq=
+ql= #ql +Hlq= 9d dolzl+Hlqq +4++.
q "*g awl ol¤¤. ^qlEH 11C.1 Tl5 #; r 1C.2 5leld Eag; 11C.3 ul-5Etd; 11C.4 flE-ElE
?ls4 611î6IH 4a3,qlzl, ?B
?ol, :24 a_
=q
Qa;]z; Fe-l Atg gg + gl+. g"J olqq ol 4 ÊEaJ; 11C.5 dE Raman
ÊEE
EEH$ +zlel ;!q-,z]- -e{les+ gg qq zlzl $x[ CAg
e4q"= fg"l 9zls +r+.
11D +flrl 1= EEJH
=rlel
11A ErlEBHel gU4 trl+lz} +xl.==E d# ulil tJ
=8 ^]pE +B4ql =E| 41.:="x19-
-E ol+q4l aaH ^84ts + fleq q.el^] zflzl Ezlq^Je+

ol Eqql^J= +^tel ¤+e+ *=
"lE$ F4^J ÊEH{ +4e *Hg ffiz[ Ezlot] 4+^la + 9l+.
Eel +g- aad+
^ll7le+
s_qlEql +611^l ¤Ee 4"14. "l 11D.1 7l= tlE HJ+l; trO.Z 49C E+ AEIEH; rtD.3 tlE Raman 4
q^l He dH ¤qql aa +^lE #, "Je't 4I*9 e IilIEEI
--E
qq6h= Ell ol+q= TvlEE +4E ¤EEl1"14.

rra.r E l9 e+q sE; r1A.2 ^tslEal cE; 11A.3 gE uJg
11E TI= Ê4EaJg El|e E4
118 EId EEJH trl+lzt Ezl-Eol d¤lEt oI9 flxl H+l=: EzI9 'iladql E
zltll^l ++Q}+ 9l+.ol fS$ oI+6tH ts{rq4 o + 4 IoJ
ol e{ofl.tJEz$21+z}e+ffi2}+z}E Eld glHzl Ag+r} + 9l=a#acts+ 91tr1.
q$ril $ro1.u.21 ¤BB aolq. $zl,rJE rd$fl
'}]= !g 11E.1 Eileql gr-El zl= TIE g^le] il$; 1re.Z dE tr1.=B+el Efle¤
4¤. "l¤-ollzrJ olluJzlc] 4¤¤l=&11 +"J 4¤. Ee q-s "lag
6ll'J61+ "JÎE+zl El+,- ?vt 4e4"J %'-Bg
^le_e ^l-&El
i,ol4. ol E{q.r]=Ez}E cld tr"EI"Jel HEt qlE #e El
d qd Raman 6il4q +6]]^J d+g a
ÊEHI+
ol+.dil Aqql E6IH q ÊEHE zloJq= qla ++'I
^flE =zHql
Pll EE E4+l Eld t'-el- d+ d+6}xl ?+s=4.
11B.1 EIE qqrl E+l; r18.2 0lol=eEl Egg; 118.3 ilE Raman E
BH; t 18.4 E{ Ellet Eld SEtl
11F drl clEl| atr|EaJ fl rl-E ol rlEel Es.=?
ol a. dalE E"d E9 rlcql^1, dz} dolts q9 +lilE
t4 EzI EBlo+g a4 E"]E+r+ +A r++q^lE ¤ie-6}?]l ol+
ol r{g ^Jqlql^l "JqtQa
7l{+r+. ol 5{oll,<JE SC z ¤trI. B* r6ql^l= ^dz} +zlq^J gaqE +4¤q a4l
flzL Ezl9 dxl-t4 +6ll^l ¤B6Ir olq^l Tlal E E|61= Ell :aEE Eldr+ TI*IÊEH"I 984 ol*qb
ÊEHql
t"ll^-l= dz} tI{ dololl +Hlqq {54 4d dolzt E" ^14 zl= ¤E++.E S* rTql^JE +^l 4+_e H E4 4zl
-e-E gqts + 9l+= ag ¤EB 40.14. trl+lz} Ezl9 dz} I zl+zl qB4 4zl CEEE nE dAq E=61+zl=
tr"ql +{ql +6ll^lE ¤¤g 4"14. ¤E++.
11F.1
ÊEHE
2flrl Erh 11F.2 +flrl Erl
11G 8E]l=9I EB
=E=
.BoJol4,"J"Jr+
ol e$ol,<J= +d Ag ¤tr-g s¤:* EzI
EE zlg4 +^l *=g aa4 E 4"14. olq^J EE tIEllE
ol ul-E_.r.[ e[a]E 6[ts^J .z ollHzlE ++].il+ gE i ,ll+4+
EzI all4$ ge{ + ?l+= L9 ="861-41 ¤ 4"l4.EE tr-
4g zl4 +^l a4= qlolz.l zr*4 +Hg +s+ 4c"14.
11c.1 gBrl ?lB; r 1c.2 6llalel c6Hal; 11c.3 zll0lr'l
E4 11A gHJ4
=rI.PJHgI =8
tsC4 "-+ &+¤trI(9luJxl9 He+ Sol). olag Rayleish tl
> ol EE= Hll.?.ts ol3 aJol+r 6J+. * rorzH + 6r+el "J^t +zl7| Hl+^d :e=¤-
#+lEt tlgFd E^f EBltso_e+E1 g= tllolE1E 6H46E1E EE
EEEI= ¤E4 H 0lE4 dH 0|6ll6tl0F EEI'. "JsA+(qluJ zl {o}z} +H}g+). +zl.7} :29 9lul zl.J+E
î4EaJtrll
^l.E-
Ez}ql Wzl.a EA *e dffi
Lt4+= ag zlzla_
> EqC 7[LJ stokes tleJol4r 6Jq. +E ol +E 4Cql^J $zlz| $z|
-d H3 ollL1^l 8EH++E| olL -d +3 aFEt|E E0l7l golLlalE tr+El 9luJzlE Elol^J E7! +g 1]ffi zlzla- +4+}-
crtT I +^1.= E+6lal xl+ "J0 t0 t
:ztcl. gE
=3
H3 ,sE|le+Ei
a9 Hj_Stokes ttEJol+r aJ4(:B 11A.1). "l 4l+ +Îd
SEt|Esl Eol= rlg4(=^l^zt ,J=oil geDolz.lr_[ E_^toil sl-d
xEoll elotl^l "JolUtl.
E 1]ffi E46l-H +zl.el qlqzl ++ eB. Eg
=+lql
+ 9l+.Raman ¤;ilJB9 ol$all.! tszl9 tlF4 sld tr-Ell=
> =Jg:d qHl IlAl E+g + eltr}.
ErlollLlxlE gxtsl(EE TEel 7F)g EBEoll^1e-.| dE4 +EIel
TllE(Etrl 8C)E +xl6lr ?1010f Elr.l. 11L1 rJlfl$
=+$g=
sld qqzl ?J4(4+ EzIg d$ AE=0.0r
=+l= ^LolE
g= E+JHql^l= +^l7l * qlqzl ^JqE+El *e qlq zI,E 0.01kJ mol-'91 6l]'Jg dE qlLlzl +4
=9lE ^l-olE
zl ^J4E dol¤ oll Ezlz} HJ=6I= 4zlzl +^l¤ A=6Lr (M= 1021, oj l0kJ mol-'ql ql'J)E+ +9q, E +zl+ dzt
r {f,f. +4*trt. flE # $!f|gql^J= "JC 1lf,f ¤ qlqzl
^lolE
zll(tn=o.l_l al, * 102_103k} mol-l
=+l=
EE +Îdg,,.l_E_gl E"4rl7lH^J r dE ¤+ +Îdg _E ql 61lR)-H-q ++. q+^J Bohr9 ll54 z4 v=LEthql q+
qEl6J+. dE g++L s¤ " jr= ol.g ;.1e."114 Hg a ol$ trolal ++E col"il sqd-= *zI9 d=+=g sld
=
.l+H Hg g+6I= 4Ar+ "J=6I= 4{ol 4 ?ol 6J + E A+ $ to'oHz, tl59 a+ E 1013H2, "l dz} d"l9 ?
qa 4l#ql^l 4+qq, a=71= ol=el ilql 5l]'J'6i= ¤ * 10'n- to'sHzol4 E|4^J 3tld, 4ld-, r4I dz} *41 dol
Z 7+7_+ ulol=+u|, 4eld, rflr zl{$tzl^ld +^|= f;:
ql E6]l^J &+q= +Îdq ll.E+=¤ a.<l.aJeEAl +4I +6lz + HJ=6J s E^J "Jq\l+
r+cq +Hlq= EzL ^JEHE H+= ACql+. "lElql Eelql
^l= "J=q4q
g+q. qEl +^Ld=E 5¤¤ tl# v,
ulf I =ylc, E= +zJ ?v-clv t(tr.q iAq Elq+z}9 tl.al t:
uJ-Stokes
S BoI4)g Tlzla- +4U+.
+lel 4 4*"l.4 +Îdol ,J¤qrl+ ¤-+q= ag +zl- K Rayleigh
A 7l^la- 6]]46J + 9l+. Ezlzl *g qlLJzl ^JEll Er4 + 5 "J,\l-
6
Stokes
e qLlzl ^JEll E, Îolqld dolE "Jsa ql 4+4+ f,+ =^lc
6I= rlzlE qlq zl hE Bohr d# aa(Eq 7AE 7A.e4
hv=Eu-Er)e+ +q4r+(vE *¤9zl+ g+q= +ÎdE
llF-i). ,J= "t s+ PlHg dz} tlql, 1]5, +C sld ql lg 11A.1 Raman E8Holl,\i= g,\f 3l^Pl E^toll elot|,\j tteJE+. EH+
HzlE9 qlqzl rJ4ql
++ F"J+ C-HE +q.+lq, ¤
zllE qtr =q
a-lofolizl=
"JBg dx{4 aaql el6ll^l aag taJEq. "J+ B^l= E^tolltrl ollLl^l "J.+= lllTl-r. Stokes
=llCo+11
LlSt|.. :E 3F Bxl.= ollLl^l= EolTl^lr. HJ-Stokes Ll8tl.
+. 0E taJe ErlEol r gfl9 =,\ldo+,\]
SEtle+q SEtlE(5=Jqe LlElL.!)
Raman #Bql^J= ^lE. B^q +^ld, + E"Jt glHzl ^1= == 0l rtEE oilL1^l ilE
olcl^l El= 8EtlE Eol-7F= rlgoil E6il^1 gGlutrl'.
9 "Jzl-91 rL=^lzJ4. ol *zlzl ^lE EzIe+ "J+E 4f Eol B^l7l w7l71Ll )l^la_ Lt7l.= aolq.
39t+ EIt#.lE
(a) xl'=-,zl rFJ4 rEl tr++^J

=/.l
AlberrEinstein$ ^J4E Î"19 dol} ^,ll zlzl Tlqe
ol+q pe)=*. (11A.2b)
Tltrl= ag E+it+ +d rl.=} + tlElel qlqzl fo+rr,-
=+q^l=
ilql 6]]Brd+ 415+ vE zlzlr TIrE" 6l+ dzl-zlz}"ll E6ll rBl+ ol ¤¤ ,Hill+-E uli.Boltzmann
^rg EI+^lzlzl ?*
^J
4-qlqzl trfl |e+q qL + +g qlLJzl tlEil uEel d eH "J
gu(g nzflel d{ zl^l ¤r+ Eq l2Aqlî B^lqD.
olz} "Jolt4(hv_Eu-81). olq+ ¤qlE d"l 4sE EÎ +
;.|el ,<llzlql Hlql++. + "J^l-+^}dg rlg+E dol = a-,, "-E)tkr =
tkr
s-hv (11A.3)
^llTlTl
7l-mlE +tr + +Eg+. ol dol +E= E+ *g tr"qql ?l
ffi
E +xI + NrqlE 9=61+tr11, "143 oleldJ tr"=l]E EzI f n|+^J B¤ tr-Ellql^J= olluJzl 4EEH oJEzI rl=q=4 Bol
z| u$$f$ oJ^l ¤-zl7| +==B zls)zl +otzlzl ull$olQ. z[ Etr}.
+ g,r}q 4E tr"-3 rr|4^l 4++ *ol 448 + 9i+. tI
g.l3.1 +r}*+. Pl)-=,Hf,.,iil (1rA.4)
Wu*r=8,,N,p(v) EB +E (11A.1a)
^1-a E+ ¤eql^J= ol +Î "JE7I +i-lle+ ¤¤g ol7 planck
q7l^l pe)y "ilHzl =
Estr..,.J p(v)dvE v-tr.*el
ÊEH
ÎolE {5f
v+dv gqql^Jel +^l-qlqzl 'JE= +ElU+.
lc'
r4r B,r= Einstein xE # 4l++r 6l+ ^J++. P!)--g/dj
Snhvt
Planck E-II (11A.s)
+Îde se} EzITI +e. ^JelE+El *e ^J4E dol qL+/.-l

q= ag +ts^lzlQ :zr-lalq {t+
19 o}z}E Lil+al 6J
cp tinsteing rJ4alfi.4. "l $Cg rF+ g=olrp alf
trll ol HJ= +E= +g gl= EzI + N"el ol d
o,,=($)4, "t q,,=Bur (11A.6a)
== =+lql
^J46}jr" +E.
ol {¤+q +^l.del .rllzl9l 9a6-J4l ol
ol 4=g +z}e+ +rI^J"l ¤¤g olr n glq= zfz$ ap1,<1
11A.1a^14 4.9 trI+4 eol +E|4fl+
=e +Eg 4Eolzl"J ol +41!Eg Ezl zl-del C{s$ +4
W,i-,=4,,N,p(v) L]]= aEolzl $;lu|9 lelefl Ee= +4.11= 43 otr-l
xl+ HJE 4s (11A.1b)
q(+ +illol= otq- ++6lr+) q+^J qE qlqzl "Jroil
q7l^l 4,"8 rFl HJ= 4l++.
Einstein ql4^l+ rre.rzl¤- ole" e. + 91trI.
Einstein$ olq^J Ezl¤$ +ÎdE zl+¤- $zl g}l_s_ z]. zlg4 *=l} zE "J=49 +E Hlts tlA.lb, llA.lc, H
94 0 e *e qlqzl tr-4E dolqHrl "ilulzlE sE zIts 1tA.6a 4E9 A*Bll^J +Et + glsq q-q=r+ ?ol S4.
4 *=g gsa + 9lg 4ol4r ^J46I94.r?]a ol x[
,J4 S=E dol 4sE q+4 ?ol +4'ilfltrI-. W(-,_ A,,u _8nhv3 (11A.6b)
W,!-,- Br.,PQ) c'p(v)
W'jl, =A,,,N, gr= +E (11A.1c)
^[94 ol E6IE .J +qd "Jssl 4* zl$zl ,J=
¤zld trf Ar,,E Einstein rl'J4 tt= Al++. EI+^l 7]F4
^-lql ÊEH r|4 6zlalq, q
^J'H4 +s^dol d"l 41t.+el ^ll4l#ql
el
%r-=4 z}ts4 ,J=e_l Eg + rEl6J di] HJ¤ 4r5 r1-9. +^J ql+61 +g d#ql^J= ol4ol 4tfl +s6t+. Hlql
4?ol ¤+91+. E *g {ol {5fql^J= z}94 %r-=g +^lg + ilsq,
oltrI= dol9
^ll7l=
z|] ,J¤r+ $=t"Jg zlzlt_ Ets +
Wu_,r=4,,N,p(v)+A,,,N, Eill g= +E (11A.1d)
el+.
Ezle+ +^pl 94 ¤Bg olE trll= rrA.1a^14 llA.ld^lol
eopt 6Lq, Tflill+ Nioe+ N;q7l- ¤¤ Atg 444oF +4 trl zlEtE! q 11A1
+^J, zleld_L E+q zlrl +^PJe + ol+Elql q+ a¤+E

gt roouHe_ ?zla}q q+^J zlB4 HJ= +E9 zH +r¤
B,,,Niqp( v) = 4,,Niop( v ) + A,,,Niq (1'lA.2a)
+Eql qdJ Bl= E"J gEE a+ 106ts]]s +71-
^trlEH
11A Erl#EgEJ4=8 3es
(c) Aeer-Lambert E=l

+trI. olel6J #4+ +zI trllE{l dzt dl4 d"li g6l ',J
¤ F}H o + EulEl bIzlEL dE E%lBql^l= ¤+I + dE ar+q E6LH .qlzJ rooJ 4zlzl +ÎCg z)olzl tolr
%r-Hg ols-"6[{ z}84 %'-=g +^l+4. g+ + I7I g*:E UIE Eqfl= Er+^lzl$ xllzlzl r ^lBql
q-q-r+ eg
"J $rld"l F4qq 4etsrll,
ol ,rllzlp
Îolql
Beer-Lambert H=lol d B++.
(b) dE4 +ElEl Eol EEIE
1= Io10-s{llt Beer-Lambert tszl (11A.8)
dq +4e dolTt -,lggtszl E.= #zlq=4E +44=
{ol4(EB ecy. ol +zlE zlE"l 9E z]]H.$ +^l7l 4zl*
tI {lez}¤¤ 6Iq dE+ 19 *{¤ ¤+614+ 4--e4B {zlrJ e3 E 4l+4r aJr(qdfl 'ig 4l+'+I +e
ol .$zlz| 4qE r+E4_e_s+"t ol 41ffi tlzlt_ TlE6l- =B
zlE ql+) 5 S+r 4l+- EÎ +^l-dE d5fql 9=6Iq,
A7l nt---zJ$ 7l4o| 6J+E 4o.l4. ol dol a3-==-zl$ oJ TlaI g+q= x54oll,rJ 4lqlil= *=+. olA9 qHl
= ^1al
zL9eI4 e__+=: q.q_r+ ?"1 *4 v,4 w Î"lE Eol .g=1_r[ C3 t/(:-"-=.xpol)o1q, "JHI4 o + dm3mol-rcm-r-E- +4.11
-EEIE rrnE zlzl:i_ +48 + 914. aol ¤?-16I+. Sr zlg ++lql^J= m2mol-rol g+. e9 0l
=
++1= eol E g+ +H44 e+L ag *614, :-4alq +
r^:lwi uV,dr do| 8=^l EEIE [¤e-ll (11A.7)
#J tB4"l .++ "J^L +Îd9 rilzl7l q aAl ^l
zlel
¤zl,tJ ttY 4z]| 4+zI EHle. ¤tlz}+. dol ,'8+zl94 zzl +g+= 49 +4U4. neer-Lambert B4g dE4 o e E
dolql +Hlq= d6t z]]Btsl]el cEE +4u+r. E + 3 1"14. rBl+ ol Hzlg trl-g ?Bql^J Eol= uls+ ?ol
=
:14. ol d6I zllBuflzl. ffiC"J oll"J d"lz} g^d(+ %r4-3 drll ++ol q= Bzloltr+.
HJ=6I4+ g+qI+)"J + gl= aolq:H rrA.2). d"l tt
+zl-EHl=zI ool olp trll"J d"lz| +$UtrI. ,rl rt H=lq EFJ¤
ÊEHql
4^J dq +zlg gEjH Fn* ool 9E z4* *"I"F +4. s4 ¤e 4ryilB ^lE= ula6-J +41 :=¤ol +"J 4"141
Ezlzl +qd a"F9 44421 +14^l 7l4ol ,t34o1fex(rfl 11A.3). zJ azJ! F4l= dr4l 6lzl.
d+ "JHI4 d4g B^l+ 4o1 ^slEflg
gi{14 dE4 TElol+. qlE^l
+dx
Eq llBoll,rl u_olE ule+ ?ol EzlE g+ d7l 4qzl. rHI x
ES zlz.lot Eld IEEHS +4u+. ol +zlr+ += +¤E t- dt
^117|,,
dol{ls zl+q= ole| ulfal +zl# +flq= Eq$ql ^1V

, I
EHIE= z|,$lal a^l6l-H "Jzh+ HEI¤

^l ¤86144. dol
zlzla- -dg dolE +E+8 + glrll gE'll, olag 7i{14 d
E4
tElol+r.6J+.
,JOI, L
lg uA.3 Beer-LambertllE +6Pl916]|,(1 /.lE= ?f6l "'jP

tsflqr' 84eltrl. -d e.l-d ,J^ts ol 6ofl g^tEl= ==e
=oil ^1171 ^117|(gel =-
,,
I
E4l 1 4zlzl +^PI*a4gEq4[949 r]lzl HEL4|^]
-+ zlzl g.r.[7] + z7+s- E" r]ds 4lg :_ r.llzl HEI dr;' 47+
E +41, ¤r* + Iel E.BE r"]r a- z7+E +l^lql^lel "J
\ +ÎcE ^llzl /q Hl4lB 4"14. 4 dr* lllrdxTl ¤ 4,"1
^1"
(a) (b) +. dr= ¤-olo e(¤+ ql+oll ,rllzlzt *i) ol +41= rl-q_r+
fB 11A.2 st ts E^t7l2s E^ltr E tr1= Ealzf ?aoe 015:Lltrt. 0l
(a) Bol 44,.g + 9l+.
E6f 0l$ll= 8=^t sfllE7l EtHdt^l g=tr|'. qat^j 0l dol= d7l-8=^t
Eol0lr't. (b) 0let Et|^4e-e 1s E^lzl2p Erltr E q= d6l'0lEoll 67 = _()lldx
=xl
+UElol 8+^l'7l E:Lttrt 0l dol= AE dololtrl.
3e6 Exl'gEI
9zlrl r= Hlql tl+trI "l zl3 tr|s=4 ?"1 448 +E 9l+ E ++"lg aol t.0mm9 ,tle.*oll $-L zsonm E|+E
+^ldg E+^laq,J ol +ÎdE 4lzlzl zl* 1k4 s+oro
f =-"uu' e. A46lfltrI(r-0.54). 280nmgl^J9 EBE+9 9%+E
ol ¤"l9zli 4 +ql 4+g+. e+ E F* 4l+= 4l+I6Iq4. +4l7l2.ommoJ
^lg ^l.E¤g
re"+ FJ+EE 4l4l6lq+.
lAl 2 ¤olqzlE =4# s+ Ertils qE d{l ^ll7l
H+ IHEI tB A--logT-sullolEE r= AllllLol+. -H-
tr+4î o3,r.| ,tllzlz}/o"J H"l F4l r"J rlEE 86il rl-g rlel + +4+ rle*oil ql+ Fr+E= 4l4I6IelH A--losr=
8l7l= olBl6J ¤+4 HE+el g-e_E +48 + 9lg 4"14. dnt4 4l4I6J e9 ol*alq ¤:+IEE 4I4I6I-L olq^l
¤+- +E E-r-"E= +"J6Lq "JC6Iqr _H_olE ¤+. r?-lI T_ 10_Ê
"l+oJr+.
++61 4Lg ="+Eq qlg 4Er+ ,Jtr+. trI4^1, Eol ¤4-E-= A=-log 0.54=0.27"1q, q+^J E. ¤+I 4l
4EA.2 4= A.1 += trl+r+ ,Jq.
*Urfii ¤- (5.0x -log 0.54 _ 5.4x102 dm'mol-' mm-'
tr:-,.J'ura, 1o{ mol dm-' )x (l.0mm)
U1g86ttt
tr|+^l olE *flL 4"121 4l4}g alt'll EqEFKr4{ ol 4
4i s.+x 1ddm3 mol-r cm-r-E- ++tHrl.+ 5.4x 1dm2 mol-r
,n* = -rtllr E +44qE_ g+). rela z)olzl2.OmmoJ
^l.eE ¤+
E5 ufe,.$ +Ll.
lnx=(ln l0)logx9 S4lE ol+5ll^J ol 4f ^J+ql+e
Hr
:F.4 e=r/ln l09F il+6IH "l :l"l trl-s-r+=B"l ¤4. 4 : (5.4 x 102 dm3 mol-r mm-r) x (5.0 x l0-a mol dm-3)
x (2.0 mm)
- 9.54
I
log
Io
=-elilL trI+^l olql= +rlE7I T= l0-A - 10-0.s4 -O.2e7l ¤tr}.
ol q-=irE +l6IE Beer-Lamberr Bzl(11A.8^l)o e \l7l E.7j 11A1 *ETI 0.1mmol dm-3"J olulu{! Q-tr
d +3-"_qg 4ol s.omm9 +C *zl"ll gr1 zaonrn qrl
^le-l
¤+.
dE +B-EE +C5l9qul o.t+94. "l ul*ql^lE Fls
+%I+zl +q4l 4154oll,rJel Fr+E rE 7l {]el E st$ 4l+e+ +"+fl ¤+E= 4l4I6IqE|. z)olzl
^lEE =de l.OmmoJ +C *zlE g"I$.dr,-tr
zlr +4UtrI. ^l-S*+ts 54;ez| .sg'o y.E
Lg-|=t.r_urf,r_lorr¤rupo0I x /.I =
I
T= Io, Flts. t6gl (tlA.9a)
E= olag EBs A= Tlz.la- 444zls +trI.

^lEel
a=logt
I
EBE tdEl (11A.eb) E ¤4- 4l+el 4lqil dol9 r-llzlE 44u4. :el
4,,"*E
+ "JHI4 e-+ ¤4.e- tr-*6J ul+ gqql aa El4 glE trl
+lE + "JE Î"lqE A=-loBr(^J+ .fl+gg +E6Iq4)E s +4+q q4^J + +g ++9 FJ 4lf"Jg-e +lz| d
*4lz| dB6Iq, Beer-Lambert H4ol r+q=r+ *ol 84. ol ,!lzl$ +4'3 += S.+. 4E 4l+ AY q +el -u.E
=ts
++E #} al+E rlal 4 0 e^l(rH llA.4), E # 4l+
A=e[ilL (11A.9c)
++q1 ql4^l E_^l6J +d gE Hol"ll 6il'J+tr|.+
=
* q= elllt9
^lgel +44
Hs+l EH+.
A:!o" ot(i)dn 4E EB At+ t¤El (11A.10)
E@ z##Eaa Hli* +¤ *= ,rlE A+ql= 4B

q Hlq++. 11A.10^lg E* qE "lFE zllzl] dEqlE zl+
*I 4l+z} ul9 kol
olulu& eflE$o'l o.sommoldm-3E r-oE-E +6il51q91
g+ dEe 7l6ltrI4"J Se Col olt-lq +¤ 7I
ÊEHE
11A Erl#EgHJ4E-A 397
49 q$rll +drlzlfi, rJ 't"LzI "l qdg gsq qBAl

/ \ +¤^l? 4"JxlE ojo[flo]o] 6l-= 4"14.
q.)
IL
K @ Doppter triE= LIEILI|=
^{
fio tJol
rlofi
x.{ti
=
E;t!
-'1 s HO
Ezt &F "llHzlE Bzl"tl u|4 ulzl4, ol trl
Boltzmann Es
dS ooppler olfgl E6J trld4 ¤+^l4ot 6J+.
olru
4l#,.a
Ezl 1 ++q= {#e}+x}+q 4"lE +41

trl'8 v Boltzmann EE Bzl(E rzl]E d4l zl^l ¤9 B"I4)q1 I
6iE gE71- rol zli-ll .tle +e-l e=tol 7olt,44"l s?l flzI
fal 11A.4 -d dolel 4E
=g
alf
==
# zl+E g^l-+^l.cel trt+oil
Etl6|{^1 E^lEl +d eE LJole[
eE[. 4 Ezlzt B4l +F qlqzl E*=!rn** zI¤ *83 e-,?d/2&rql
Hl;il,*+. s( coJ trll= *flE olE" 6l-b +zl¤ql QlaJ Doppler
zla glq. 4lH ol# l1A.llbal o + +48 + gl+. tr|4^l ¤+q
TIH9+ {la} {54 ^}"lql= vob.-?o= +vos/c9 oltol
=
11A.2 Ê4EaJ d+ ++\i+. "l +41= q-q=4 *ol 4?-lB + 9l+
s=*c(voo, -vo)lvo
dEe 94 4454 zlqE oJ6tl^J d+¤ *rtl
ÊEH9
g+ fiixl4l zlillel qzlql "l d*"ll ¤6}-9 ¤ +E gl:r" rl EJAI2 44 Es"ll zl"Jq= {¤+ Es
v"6.91^19 4o1 .<1lzl r!-vo5.9 Hg 4+44 g4alE Ezl¤
Eq 4aql 7l?lEl= g6:lE ?14. +zl4 zlq= dE
=Hl
44i= Hs+^14 o eA] alro1.<1vJ + glzlt} $z| z[;-lJel E gAg +Eq Hlelltl+. "lel* Ezl-b +lE +q4=
^les
e4 Ceql 9+ TlqEg q¤ + S+. +qg 714 1olq :.46I¤ soltzmann EE H4ql e-1611^J
q-.q-l} ,J+ 4+71 $BaJ 4,"14.
(a) Doppbr nid /(voo, )o. e-
msztzkT
=a-"'{'*-'o)'tzul*r
zlill ,tl-E9l^J d+g ftzltlzli + +s+ s"Jg Doppler E ol Gauss EI+e+ Ag Eol4. olelal ++= +-+olql
44. olae %r"gol $fizlE$rl E"lzl44 zlttflg ull :. ^13
tl5fzt +4+= Er++. {f,f v! $zlzl +^|dg
r1e4l ^Jel
d+ 6voo,z| "JHlzl " e ++4 aol ¤trH44x19 ^Jal
zo2 Eol4).
,,J=61+ 4d-Eol s+zls+q +q ¤-7}zlr. +E"e. ull=
ol +Îdel d{+zl S*z}9lzll= q-q-+ ?ol 1lzl¤4.
6r.0,=? (ztcTnz)''' Doppler nlE (11A.12a)
( r-slc\''' 1l+s/r \"'

v,...ding =[ tEE,J Vo vapproaching =[ lf]7,
)
"
Doppler 0lE (11A.11a)
¤zlrJ cE H9 +E+. Hl-tlEll$4 44(s<c)9 A+ql=

ol rl5"l q-q_r+ ?"1 tE6|]Tl+
Tt3
yreceding
=(l-s I c)vo vapproaching =(1+s/c)v, (11A.11b) \
<F
zlillql^J= Ezlzl s-=- ulaje_tr_ ql*61 +qg 714 + ,loE
= T
9lsq, r?-l6l"i ¤xl t4 *+xl* Doppler ol*ql 7l"Jq
¤Ee_l 4]t+=g *xlaizil g+. qE Ezl¤e **4_E /// 3r
=
6J6Lr E qE ae r HI4+3 6J6Iq, qE ag mlez]l E \\
IlE.^.
uot
qtr 4g L?-lAl +E6J 4,o14.+Aq= ^sl=HCg ol4
f,al llA.s Doppler qEaJd qd sge ¤C EEoll^1el
* EE Doppler olEql 7l"Jq= gf s= HJ= E"&g *L ^lee]
Etl
EE ollq^lE Boltzmann EII= HJE6H += a0lcl. .gsz; EalTlE dol
+. "1zl^-l Bflflb Ezll= d qAr+ zl4l Ezl¤E +E trl tri 'JolE= +=6|Ga|-.
3e8 1^r Ert#El
gETI tolzlH Bzl¤9 44"1 Etrl Hrll trlA o + gE ElEtx[el 8^l 26 xl+ g+9lC.auss *#
+q+H Dopple. sld"l +71-++. Hlqls gE= *+q
= d+ol EqL Doppler C+g d#q Elql6| Ae EE EL+= rl+ B+4r.6J+
+E +s=r+
=q=+,
q, q+^J +a6I= 4lE+7I totd++ Doppler uldol 6
f (x)-- ae-b'
^l+
-st+
s6}4l ¤+.
ol gL+E r=0oll^19 <i"l a7l E)a- x-+*71 E9l ul-4 o
9.e e^l6J+. b7l e 4lE ol zJ\zl mls+. ol st+=
Coe+ eg Ezlql Efl6il^l= T=3OOKoll^'l d+ aldol 4 ys_*71$q 44 #+6}|l +6Jqls 6z}fl4. 1
^4lzl
94 ?"1 ¤trHl I= I kg m, s-rol4). I E"teI.
6roo. _ z( zkTlnz\'''
,, -Vl mr" ) 0 ]-l--rt-t
---t-----f----t-+ -1
2
2.998x108 m s-'
I
I
G
--ffii-- j
v2
( zx(u,.lsoxro-" l K-' )x(3oo K)xln2 ) 7
X
tl G 6
x 5
=2.34x10< 4
3 e-'
COq 4eld :.trleg_oE+El$ zrsocm-,9 dol ]4 2 - gx2
Hz)oll 6ll'J'6}q q4^J d*ol

-
iE 0+.+THz(1 THz=10'2 1
151MH4 4 s.Ox 10-3cm-rol g+. 4 -3 -2 -1 0r1 2 345

1
^fllil
Eld"ll zl"Jq=
Gauss Ei++ r "JHI4 g-o1 rJ-e-= $ pr|.
Doppler d+g tr+s=r+ eol EI+
a Tvla_ +ElE +E 9l+. ^{EH f (x)- Ae-(x-b)2t2o2 Gaussian
:att
zlo ( z*rnz\''' ol *+= x-LE +d os + E"Jg 'llag +4qq, +

6t uu!
-. = c[ * DooolertriE ('l1A'12b)
) d aql^J alqlil azl ¤4.o1 6}+E tl-tol.llrJel alg
=-olep. 6l+ql, r 7}g 6r:2o(2lnZ)rtrolL+. ozl- pffi
(b) +B tr1d ol HI-+ol +ol 4Tlr|. b=0oJ 4i9 C",rsr ,*iE ,'-zlJil 1
ql +4,-l]fl+.
E{* + +Aq $ef, ^J4. ilzl6}zlEJ r ^Jqlql
"JelE
+6J61 e4 "l$zl= * 6J+. qlE^J Ezl¤$ tls +f;$
atq "l +Aql^J 1l4Eol Hg + 9l+. E +¤e_E= ztB
zlEtE! 0ll 11A3
4 "J= +Cq 96H^J *zl-E HJ=6IE^j *e qlLJzl ++lE
¤qdq. Ezl-Eol z.Iz16I= tr4E"l 9"t4 xl4l}zlE Ezl-59 dz} ,!.4E E6l +g ztg4 *E 4s.=-zl-zl
olE r+Ael +Eql el=6}q, *B tE zlzlt_ +48 + 9l+. 4 :4alq +E"l ql+61 sg + 91r+. dB4.J +¤e
10ns7| g + ilgq, UQnx 10 x tO-es) =l6MHz EE.S.:
rtlzJ E"J 4E tlEll= Schrodinger 4l o + Eq E
=+q-
B l. ql',lzl eEE E+CCS +4U+., tr|
x lo+cm{el zI¤ d+g +4+rll *+.*E zl++ qql
gl}- uI$ ?ol Doppler d++ ¤rC-4 o e zl-
^l +?]g +
=.q7l6E=htr
4^l ol4t t4zl. +qEl= E-ilJ+4 dolE 6Eth=U2m4
g4 d+E+ gt q H+.
E_el C+g +4Lflrll 84.
"ltl+ $Cg *B nlEolQa 6J
4. "l 4C"l Ezl-+E=4 eg el+ s"Jol otH zl-E.4 r+8
ql 96H^J "JqB q= qzl4l zl"JEl= d+g xlE4 d+ol
Ezl¤ ÎolE +Eg "JtI4 oe qd qlLJzl+ {E qlq
+a ++.
E44e e Hsl^lvJ + 9].eq, r?-l6l.q "l5E +
t ^l= =E
ol *414E !.EE z-lzl-59 Molecularquantummechanics (2011)
B t.o,9 +eg + 9l= + +g 'JBg olag ol=E +=
g BoI+. =ile+
Ira Erl#el gu4=8 3ee
4i u* eAl += 1o14. 4 +EaJ qlul.

HIE(Eq lB)E
ct 4d"14 41+ tIEHE HEÎA+H olE
^J49 fBg t..,
BflO I
-+- A$ + fl-9.q, r?-16l-0l ¤+q= d+g 6Eth= y2nr,o,- lle T-
F[4-
zt2n7l ¤ 4o14.
+ol+r 6J+. ^trlEfl
d=Jol zJzJ
d+ql 4tlJ ol TlqE f5..5 C
mag+. usoJ + Ezl
Îol9 +E-
BflO h
EIE= 1B.12b^lql el"ll^J tr|94 eol +48 + 9l+ Ils^
uoI
zEr
E4 8il
r#ffi")
v2
8kT
,-_ry,q7t^r U rrl= fB 11A.6 EE40J EB4lsl +4" Bfle_e+E1g
-E^ltrlE le.oll 54
"t, 0lol^l 57tE +^ltrl-= TIE+q| Eta|. EB^|7|L 41154e]
^|iltr|.
?a=7\e. ^1171=
+¤Ettrl..
+= qlE 44^J d*ol "Jqq HlEilEl¤. ++alol
^trlEH
4. ol qlgql +=q 7l"Jq= C+g g+ d+olzpr aJ
+. d+ql 4* "l zl{* zl*+ E} "Jqg *+q+E al e+ tlile +4++. g+4es ^lE= zlzlt_
rBl+ $l4"1 *"|zlfl +Îdg g-+ qI H zl$op., olq^l EI=J +4 o + rlE S.ol ^4EHg
lelEflg
^lv) + 9l+.
As+
B EzI iz| 49zlo + ¤+ ^llzls at^{4. "Jq qdg zl+++. rflH ol + zlillql zl"J
ÊEHfl ÎE+EI ^lE
Doppler illa4= 4a4 o + {ol {dfql ++6}+. 9zl t*E g+= zlladJ + 9l+.
zlEtEt q 11A4 (a) +^t zJfl

rbar4 2esKoll^J oll* zl;llE "Jq
d+q zl"Jq= +^| I}ge + dFf= +Ces 6F= ql+61 69 gEql
Ê
"J+d l$ zlzlt_ +ag + ?l eA +4*Solzl+ g.= He dEf gqql art q^q+
EH d+g HIE- *ql^J
4. "l ^lql^l 5,E +84 oE 0.46nm2o14.*o4 mu|- E gel qL 6L++ ulol=.-tru} ¤qql^J= d54 EIC 4.il
+ qlE tszl9 a=J=olq, y,dE 888m s,ol4. ul4rl, + E= qq aill ^JEH tlzlS ols-"olq tr"';lql d54 gE
ql aa Ea^lvJ + gl= *4%Ig
"J=+. "J+ qlol4e+ "J-
'---ouraP
kT uj6 Qo1 q =(LED: light emining diode)= ol+6lq 4e.ld+
_ (0.46x10-'8 m2)x(888 m s-' )x(1x10s N m') q z}e_ldql "l=zltlzlel +4"d.g BE rll ol.$slzlE .J+.
(1.381x 10-zr J 11-' )x (300 K)
E4g EillE+El +s= trt^4 +ill +Îd(Eq zelg o1g
=9.9x10e s-' 6J +E gl4. olel+ qlE^J= 4g + "JE f g olr
"6r"gel
(35 - 200 cm-r ), Nernst g4{E9+ 3eu}1200
rr}4^l d+g ? 0.0s3cm-'o14. ZI+* ql
zl2n=r.6ctrz - 4000 cm-' ), f-
1lA.2ql^J +a* HlE. 4qd gqql^lE dolgl 4,* ?-lr 4 g-B^fl-Btr-* q u(320-2500nm) # + 9l+.
7l4l %Ld Bs= z}$dr+ z].^l gqql^JE f,ttl4 =
Doppler d+ol ls0MHzflErll "l <19 "l ET]E aaql +rflol
^J
+AqI "Jq d+B+ zI4. dol Tl¤+7lFlzlts +.s ll+: %Ld flsql^J= dzl "Jd_" E= r^llE flzlzl
+
=ld
Doppler iilag dffq r|4 ?zlalzl"J Sq qag H6i z}e_ld +^l-= oJ+6J+. 6fa flEql^J= E5 o,gzlzl E
zl ?*sq, q+^J Doppler uldol zlull{ o _+ +4t+. E dz} tlE.llel Dgzl-s ql4qr ol flzlz| 200-400nmE tl
+^].i{¤-"J=*+.
C=es.= xl{ils.e$q +s= ^JTEE5- 4rtdg ol
861+ A+E ql4. d==aEE z]t}+¤- EEllzl fuq ,lel¤'
11A.3 ¤E HJEI El= gg tr++ Er 9l= dzl+E qq ?i+. g # 6l-=
dzlE o}tr-{tCg'J6I= 6J_o + zl+qqot r aE= H,q
+J}Hql^J= *E4str. flz}q +z|7l {i*^17141+
_E_=
4zl s:e4, "I4rJ ol dzl-alol +Îdg r]i+rl] g+(rB
HJ=6I4+ sE g+fl+ +ÎE 5^dg- e=6I= elzl"J E
11A.7). '{=+==- +^}d',g 4qd+El xdql ols= Hg
+41= ol8++. rB nA.6g S+ ¤rJ4le-l "JHI4"J +a 41t+ gqq +4 +^[dolQ. u[olr+rl ¤qg zlle]6tH
. +4U 4o14. 46J6J o3fl_" ++El +sE +^l_= ,,.ltroll
^JTEEE +Îdg zll4^l ="rflEe+q E= a=H4 :.
4q='le=, +r+qq +s= +^l-= E4I tlzlE 41 q
Ff Ee E%I^la+. r?-la7: T154q +Î =qEq
4qI+ ^1l7lE
^ll7)71*lls ^llr+.
400 Erl#l
la
UO IE{4]
dEd
0lE^l 7lE, M,
7l-+8il
Hl^l
i= E. )l
E6ll Af^l â
77
ar/ 7
30m
t 712, M,
I
lr Om
EJA I'
=^lc I ?r=At
daeEE
Erl ¤ fg 11A.9 Michelson 7JtrAl. ";¤ EalTlts gll H¤= EE Ed}l,^l7lq,
u1E n'ltq ?lil= 0lE^l7lE^1 0l=ol80l-d rJe^|.E 7l^l4l -dc[. e,5215
lal 11A.7 !===e, rl8+. d:d 7l+719[ t/^ !=+ego+951 + "!g0l 5g-d +zll9 EtrE E+6l.xl 6l-71 gl-d aolq. + ';gP 7E
g{o+ nlEqe, +ElLllflrl. olEe 8ol:d q.8= LIEIL}|Î ?Jtstr|..
+ +o-e +gE Erl.= +oil^l tse +alo+ 71.+8tr[. +d eEafg
^1gs
E^1.= 7l^++= Eeq 7l+E E6lE C^l7l ollLlrl= ,J=:Lrtl.
z}| aflEHg e={r 6}]461+ trll 'Fourier E+ ol$'9 "l

/1.,\ ,,\i1{lEei -El,\{
61tr gl+. (Eq l6CE Elslz}9
^Jal m"tl,<J Fourier HS
\r.,, tg -l so
--l-E
+^l Hg-E d54, y++ E= yltlg E46l+ Ftr-4 tlil ql +6H^l ¤zlrJ "J+61-= a old-e-_a x[.rl]al czlla[q{Q.)
El¤goJEll, ol4i.5 zlY g=ol * Fourier H++ E%Ialql^J dtr- qgg 6I= ag Michelson ZI
= ^l]aTl +4+ ^Jl4"l
ql+ HI^l-& $F"l}$ "Jel 1o14. zl-rl gEql d4?_lql, "l uld4l= ^le e+q +s= d^ll tls +ql .q
^trlEfl9
g# "j roo0nm(71^) gq qt}4 Bl*6J t gl= 1545-9- ts461+ tliltrt. Michelson Ad4l= ,,.1_E9l
^J ^l-8-6tEjH
4ol4) zlletr_ *4. "l fl¤ts$ r EEql^l HI^lEl= q ,<l r}g_E BlAL_g o}+q] rJ¤, oli$
"l tlzl9 tola,I ?-s
E Îolql zJd"l "Jq+4 6lq, ^FS6l.= +^ldE 4l#ql q^*ql zd-+zlqlî +^l q+4d+(re llA.e). +
el=6l+ 5¤6J 4_E_ql^l Hrt 7J4ol "Jq+al 6J+. r?]6} =je"4^la
qgg 49 M,ql^1, += 6ILI= Mrql^J Hlr}qbql, M,g ol
q 4 +tlE Hol a+6J "Jolg o}:"Izll ++(rH llA.8). E E^l7lH^J + Htol aE,.F= *rll 6ll¤ + gl+.
EFlql^J= ¤*g E6l]î +tI gqE +îd *d zJtr6l ol zldalqlq rlt} rE B^q"J' Hgg E"4rl
^4fl =.e =.e
g 5r+^14 A-4zlql EgAl ¤I+ qe$g TJqa qgE 4e pzl ool$ + H¤ol H
"JÎ +Îdlt sl ^J46]] EzI. + ^l
a +Îdql +4+ q ++le qd^lzlH t"le} iilt}el El¤ ,J Zldg "Jga 4,o14, p7l +*4 Cful]oJ 1., 2),,,3X, ...
H¤ol A*zlql fl.6J+. S+ olelql ,,J^l oE {I "J trllE
?JZ 4+71 4 4,o14. E pzl irltlel EI"J trll= tr-41
^trlEfle
Hql eI$e r+tl ¤Eg *"l4zlAl ¤4. 4^qCg "l+61+ zldg "Jsa 1"14, p7l HFltlE g+ulloJ 7,"12,3)'"12, s?,"12,
tlilql^l= ¤4ol Egs_6tr. oL4qlî ¤B6l+ A+ rJ* ..."J trllE ,J? 4+71 !- 1o14. r46}q M,9 olf^]4 zl
ts[g^l ds]zlE
"l+6lq He gqel +t[s EÎ4 + + E + qd.ol szJl{e + E= t}cl4 o _+ t;Jol qH^J ++
o
4tltrt. 4p* Eal-71. HeoL +4+41 g 4,"14, ,Jzll3 dE tl

4e.lc4 4qdql^J ^l-*qz 4E -E= *I4ls=g E sE t +cos(2npll.), + 1+cos(2npr)ql rr|4 HaJ 4.o14(rH
=
2
z3-ttl7l
oll L tlI,\I
rrl\l *
= =l
-^:
J. 5
= o_
(H
s9
o
o
L
O
+
tsl
=lx-{HI 0. 5
==
0
01234
lal ip
1 1A.8 tl^{ "f¤3 Altrgoll E6[|,t.1 l1l dE trtB trr, lr, "! },ro + 5g
Elrl. 0l raJoil,\l= ).rel Ee Erl6l-q zrtTloll s..5dcl. fH t 1A.10 ral t 1A.9oll H.?l ,JdXloll,tl 3ex|. pE EEt,t lTlE l
Eltrgg trc fl =,\l'd"Jol =e=
Soll LlEl'.! ahls t8:do..+ trltr,\l7lE I,r[ trrE ztrl7l0ll ge ,JdraJ. 0l !E= Eg t!E+ dEPJ= 7[rlq, qal^1 0l raflE=
-==J,r.lrJ + ?lrl-. 1+ cos(Zntp)E E,t.l7l Etrt.
11A ErlPJEel gu4 401
=a
l1A.10).
B"Jl deql^JE /J.olel yi+4 îl7lel +rldE"l sq+

g q+g E*4q E"rl^lzlzll 84. :z4H 4 $rldE"t A A .l_ A A A
4 t+cos(2npt)41 Hl4l6l} Ad +9= +e}8 4o14, olE (-o.

el .Ja 44zl a¤AlE dp- + ++B 4"14. trI+^J 4l7l7l j
r\.
I(r,)olr. vlfzl 4"J +^tdEE g EJ q¤ol walql "J

ol.E !].ol ?ulzl9l 448 lolri.
ÎEIE
i p1 -\t(v, ){t +cos (2ni,p)l
1
(11A.13)
4E_ 2JOl p
^l,
ol /(p)=p9l 4ald E^l6J 49 zJ¤=aJol+a ++.Ezll. fg 11A.11 Htl ttn.z9 EllolEl=+El 4ltl:d ACraJ.
ol &)E +4qlzl gs+ + rl+ql qE ^ll7l HsI 6
^trlEH,
/(r)_tr Hl-+-'1- "JolcL. ol 4c¤. Fourier H*+ol4r 6l+ +qi
5
el .g= Ezllolq, ++4 ag 4Eg +6IoF +tr}.
4
l>
\i) - +ll {itol-ii1o;}.ot (znip)dp Fourier Es (11A.14) .--:
t\ 3
d4l4-q E= (p)9 +447l4zlpE] qq +*Alq .{tlg 2
e+qql zl+qr olq^J Fourier E+Ig ++. 1
I -^nll Iln^^ nll ll l1 flInn

10
!t.7l11N2 ,,\it{lEa{?I 7} {-raH
rj E:r4El
--t-Er-l
ad4lE EqztE glol ufe_$ ae +dg *b ^11
+^H fg 11A.12 ral 11A.11oll E?.! ,JdraJ9 Fourier Ef. T.!E
r*e_E ol+q{ 4"]41 ,.J4ollBz}. EgP ral rrR.r19 i}l+161.= HJ^.l q=oil 84q.. Etr-l E
z4e-zJol +e_e ^lE=
q86ll^1 ill+l6lE d50l flolrla E+al=01
i,lcm-t 150 250 450
^f
tr1 qloJoHTltrl'.
\i,) 1 3 6
rPl B7I 11x2 rrE <l¤. 550cm-'-E uffietrr{ +^}C
¤zlrl9 rllzlE$ ar<]| H 6}$ zlf;e_e + t}r.il4 ;t= 9 ,rll ¤+E ++= H+^lag qq zld:zts{ trlil=
ol+. ol
"I'Jl6t= zldz+g E^l6Iq4.
olq^J g6;9 gqEoFI.
ol ^lsqFourier H+|g 4l&6la E^16|q?+.
Adre9 SI.VII ET.E
zE{:g ol= H¤e ol+qzl= tEql q4^J=
^tEl ^ll
1A.13^lg zld ole"B + ?l+. Hl+ ol A+<ifilz| *+ /1 /\ A A A. I f\ I
6l AL4EL+EE 'J"l+)ollts rourie. ES r(r)= Cq6lAl
41{l$ f
9,lzl"J oJHI4 e-E= fsi +ue?{q= 0l+6} o.
\//1 fl A IA
q+il 4l4}g ++. j
N
t\t/l \v/
=ol
+q{ qlolElql E6}E zJd:ztsol q-q=4 ?"1 84. //\! t\/11 V
ll I
\yt
\] t/ \/ \] V\/
i(il=(1+ cos2ni,p) +:x(t + cos2nirp) + 6x(l + cos2nirp) V
= 10 + cos2nirp +3 cos2nfrrp + 6 cos2nirp 7JE ?)Ol71, p
ol gLffi rH
lrR.rroll E^l6t*.+. rp-lr Fourier HS f.g 1 1A.13 E7l
^Pl7Jdril(8^q)
1 1A.2el E1l0lE'l++El Xlt:d zJdrHE ol
Ee +{olls7}|^1 LlEllllfltrl.
el +zl 4l&+ A4= rB rre.rzoll E^16t9+. E7l
^liilql^1
t02 Ext#!ts
Bsr >
,\lE :l.eJ 11A.14 Raman EgEoll,\l .E.rJ4oe 0lEEl= ullil. allolrl q^tCol il.!^=
Erlrt cl.=oil +u^tE= 7l{] 71EE 4P 0l x¤e r4alq,
trJ^4al gil tEJ 71=oil E6H^] HJ^lElcl
-Erlzttrl. ^|e=
"8=ola= E^q+ 8:^lLl'1d4|e E4
E+Erl..
ce=
#nl7l
I
ZdZl 6tzl =^[de
Etl.
(c) 4rlzl ccDE ol+6IE +^4El tlils+q +e= He gqE EltF

g E^14 o + +A6J + 9leq, rul6tq ,llH + +g +tI
F}4lel zjr:l7l= "JÎ +Îdg 4zl4 d6e HF+q^l +
4.ll= tlil+. olBl+ ?ElzlE +"J +Îd-++ a ^+ ol-f.
gEE qg
^fl71=
+c6}zl ?*ols g+
q4l aE fll s tzl-?lol4 2xJ-flo + H11S6J qq zlg s
45E "]+qd AE 91tr+. (d)PJZIE=+
ulol=._tr.u]- aulzl=- dB4_oe ts181 B"l tlsille+ d 4¤6J ¤+IAl= de6iH g+¤jillB o + EzI9 dz} tr-4,
6tr 9l= clol c ¤Col4. q
fl= 4e]d $l}4lql 4lE, r4r sld dolE BzlB + gl+. :zH rrn.e3 "JHI4
^l+qa
7I* E¤4 o + ol+qa 9i= eulTlY +7J 4qd gg¤- +%I4lE +a"Jql, ola¤- a+ 7l]d6IH q=6J ds= e=6I
"J+6lrll e=EI+. *-zldC +ilql^J= d+lilzt 49d u rll ¤ + 9l+. qlE,rJ uloJ=+r+ ¤%lals 4d dolE B
ql"J6lal ergt+. z4z1+ilql^J= dzl g*"1 gs =zlalzl
drll 617l +l6I]^J= +r+g +Îcq qlqzl rl
=q
ql .E dTltLe_E HEIÎ4zl44 Ha^]4 =+l=
t
"Je6lq 4eldg "JA6Iril A=++. ^ll7l= ++^1il
z}qd4 7].^lc ¤qql^l _H_¤4_e__s "l+q= dulzl= 4. "l stark HaEq1,t1Y 4lzlzl 10sv m-'(1kv cm-') Crol
*d +*+(PMT: photomultipier tube)"Jr.ll, ol4,g =o}d E4 r dt+zl r0 4zl dzl^}g ,r.l_eoll }+^la+.
100 kHzoJ
(Eq 7A). "l+61-q 442]|= qlal= qel 4l7lql HIql6l+ d¤4oJ Raman 5.lJ deql^l= +^! ellolzj dg ^lE s.
4zl4 tE= E}.qql= e+ tlzl+. pMr qleo s tr zlEzl Hql^J u$*^l/ zlzla- EqEl{}+(rH ltA.r4). E^} +^}
+ *zl"J "JHI4_o e Aol= ?ylzlE g_rlol q _c4. ol43 d fl"e. qlolzlE 4= ae t}* +^lE ^ll7l. e7l^lvl7l
4-*zl EAql *zlzl +E=6IE %I-+E dzt old q}Sol "J +l6[^Jtrl Bll"l4 +Îdg rE +g +^4C trIEql "JÎ +Î
q+^J olF^d d6I gHlal(*d6lE dz}4 "Jd6|E '+B') de_l {5fe+ +61 efi+t-q iplzl 4xl 9t= 4I* +Îdg
zl $zl7l trll$ql 4zlzl dEq= aTll ^JE1] dzt ^Jzl4. +A6l+ tll 4*6I+. olel+ +g Efl}. trilEql Raman E*I
d6'l-aEl +il(CCD: charge-coupled device)t: +EIrJ THII He sld dolE ++61+ trll f+6t+.
zlql ole= 49 gr4ole=_E 2il-?lo + H}l¤+ 4o14. ol =61
7]lts=
=eEl
Dl. g= EBEqI^l= Ezlzl t3 9lHzl ^JelE+El *e qLJ tr6. r}] $$g dol {E+E zlzl:il- 1lf6l-= dzlat{ E6|]^l
xl
^J4E d"l¤ +e=
trli 4zlzl +^[r}= e={}tr}. *e qlqzl ^JEllE+q qL 6J +g qlqzl tr4e d"l9
12. # 5ggql^J= ^lEE E"461l- +s= +Îillg ¤E g E 4Col4. "l 4CE +E= ffizlo + Einstein rFl $,$
+= Eqqql+. 4+ql Eoll^J AAg+.
tr3. Raman !$gql^J= +zlz| 4}+^lzli B,tl¤ tsrjdJe-_tr_ 47. rF+ g=g dol tl5fE zlzlt- rlE6l+ dzl*91 galirl
al Ezl
^J4E Hq¤ B4+tr1. ke qlLJ^l ^Jqs+El *g glHzl ^JEllE d"lz| .Jq+=
44. tl¤lfz} H6I^l 9+n t+q= rlzl-= Rayleigh EJFlr.6J 4C"14. "l 4C9 +E= ffizlo + Einstein rF+ U= 4l
4 +ql 96il^J ea¤q.
trs. Stol<es SJql^l= Pzlzl rE qlqzl "J+= +zlqlq ql= I8. += qEl.J +^r+E ++44 H3 oilulxl
^J.4e
4. HJ_Stor<es rJl."il^l= *zlzl +ÎE+Ei .llHxl= ¤i +El *e "ilHzl
,t}4e=^Hql
gq+= dolE rl,J4 "JE"l4l
tr}. aJ4. zlg4 ,J=e dol tl#9 llzll#"ll rI4 6zlalH,
11A ErlBEel gu4=8 403
{ol aldfzl }zl$}z ^}ql4 ¤:scol 6rl-e}q.

tr+4^l aolq.
tr e. dE4 +=lg #zlzl q} +q d =" F9 }E E Bg +E+ tr10. dEg qBe +Eql E+ +E t+91 zl
=i{14 ^8lEHol /j{$ =E¤ Elql6}q, ol qlEql
471 f.l6|^l ++^l7jo} 6l+ .JHI4 z4+ +qBq. e¤ "J¤trI. "Jqq S4 uld"l4
7i114 dE4 74e "Jzl-+ HEiE zlzla- -"18 d"lE +4U ntr *+.
=s-d4=
l-Zl
oE .,.l
--1
Z.
t-
f HE
^]
zlg4 "l xl{ HJ=E Einstein 4l+ Hl A,."=(8fihv3 lc')8,' BuJ=4,, 11A.6a
{ol ffizl. EHIE P,,=lwi i.i,dr {zl {l{x} {ol ttA.7
Beer-Lambert Hz] 1= d,1g-etllr 3ga3.rlE 11A..8
g.%}Eg+ F"JE A=log(Iol/)=-1or1 zlo ---1

ol 11A.9b
4E*I 4l+ A= ln^,oe(i)di

ilol
o-1 114.10
Doppler u'l{ 6von, = ( 2vn / c )(2k'l' ln2 I m)t

| 2
11A.12a
+B sld 6E/h=ll2nr tE tI49 f¤

EEJ 118 EldEEJE
I = 3mex'e+ 3mrxf;
> ol EE= HH+= ol+
elC -r":1eaJg 0lE6lG 7El I Ertel ,J01, ,Jal7:,8=xl
-E.E!Eel Etl'-bl 8*-el e- g + 9ltl.=g m
> "-{d 7}lLJ
gleq, olaoe+Ej E^lel eo|9} ,J*?:= +g + !lrt.

=:Et
> "Jg-et qHl rl^l

Ell 85el r.E4 ¤B(EE 7F9 ++^l-el 84 20), 4FJ
el sxltrt(-tr.4 tF1, Erl EEEsl gu4 gal(_tr.E 11A), -Lalr lal 118.1 s¤ qEl=el 8el. 0l E^toll,\1ts traJol mo?J 3zH9 5g-zf
Pauli9 Bzl(-trE 8B)= +xl6fz ?loloF:Lttl'. . fl^l'=01 Bfl^loll Eol 9l.l. !E trBtol mr?J rlE flrlEol Cfl^toll
^llEg-d
Ecl ?Itr|. BB^l'el cg^l-= 5rl.6l.= + +qq $¤ EEIE= 0l +o.e+EJ
AflxlErl^lsl +^l Tlal xeel Dfl^17ll'^19 +4 71q xo0l 9Ezrrl.
Exi9 sid tr--4 Esi".ig +4+= sld $$rjS ziili 6qi

.<luJ ol-4" gl + 9l+. xllEqlE s-f6}r eilA E"6r-Bg E 11B'1 B¤ EE!E.
"lelq}
+z}el ¤aJ?ol 46J7+, ui ,'[r]z} :rtlEe+ eg g}g zl^lg
r. zflz} Ezl
zll=" *4.
-oll5ll-u I=ltR' p=Y#
118.1 EIE ollLlrl
=+l z. tflzl CB 9dz}
+ + q(=x, y,z)= 6C + qd6l-= Ezrel qlLJzl= -r.d
o
I=moR'+m.R"
4 0.=. trl+4 ?ol fqa+(Eq TFel 4qzrg tal zo). _(m^R-mrR')2
m
Er-IIral (118.1) I= 2mxR2
¤zlrJ ory ffi +9lE ,++E rqa /q= qls"6l+ +C E

Hlsol4.EzI9 e%L +dg zl+= 3rld+ +flg E8 EE! :. 4d Eldz}
= /E r+s=r| tol ?{{+(rfl 118.1).
It=2m^fr(0)R'
1-\y,xl Bd sE!= t8ell (118.2)
R It =m^f,(0)R'
q7l^J mt? 44e-e- -H-= gzl i9 delolr ,,8 i4d+-oe R
*fft^,**)f,@)p'
Pel flzI ivlz.1s4 +4 4q+. "JHI4 o + olr]al +zI= r *fflQ*^+m,)R'
sld Ceg z116l-= 3z]]q + +flE E¤ EEIE Iq= +6m^R[\
^JE f,(0)]"']R'
zlzlt- +48 + ?l+. dB EzlE a+ql= qzl ¤a+ +
+lE +C EHI-=zl. sol{(:tE flzl$llzl9 x,=oolE+) + Ir=2m^f,(0)R'
"lzl F +^J EHIE= ^lE *otrJ t+61 /E +4u+. "J+

R
I r=mof,(0)R'
44 E{¤el +¤ s_Hlsoil +6J !i$ *. lrB.rql +4.11 mA
fl+. + +^J EHIEE3 "JHI4SE 1o, Is, H I.e. ++'ll=ql,

118 eld EIJE 40s
I,=4mrR'
EEU ErlEtr¤sulErttt
It=2m^R'+2m.R'2
H2o ts:zlql^J HoH 49 E"+61+ 2==(l)ql +qI +C
R m
m mB m
EHIE.4l&6}q+.HoH A'J4g lo4.s"olq, ¤* rJol
R
E os.zpmolQ. ra('H)= 1.0078 mu= "l+6}q+.
R
xH
1
4 +B Eldzl ra{g ,t.lE} 118.2^lg EHIEE Ah}$

ola-" o}al
"l +t
m
8
m R,
+ 9l+. ol ^l"ll^.1 xE 4 gzlE+q fld+zlzlE +zl
44"14, olag +4e+= ol+6}q AEl4r+ A* ,Jol
-l
e+El 4l&Et + 9l+.

R
Eol 11B.2^l e-E+El trl-S gg + 9l+.
A
^lg
1
-lJn, *? = mnxlt + 0 + mrxz^ = 2mrxtr
m
I= 4mxR2 +z}el at}49 h t4t oH at} 4olE R-tr- +ElrllH

u$4'*+ +4q el6ll^J rH=R sin tp 7l gtrt EI+^J,
m m,
I - 2mrR2sin2;@
R
mA ¤21.il4 Eilolq= Bq+E q+4 ee ar+= Eg +

A gltrI.
I=2x(1.007s x 1.6605 x t0-27kg) x(9.57 x 10-rrm)2

x sin2(] x 104.5o)
.f(a)=r-cos0, f,(0)=1a2cos0; EE a+ql m3 Ezt9 dill ee*ol4 = L.92 x lo{7kgm2
Hg^pI + ++lE qd6J trll og^h= ¤.zlolxl g:e_!-E

1. ) Is > r,7l qzl ++. ogzlg a"#e ol qd %r-^lel +c EHlEql o}+fl zl{
E 6lxl ?+L,_+.
EE gE 84 +d -EHIEE 4lt}6l+ EllE gaE E e xl7lg.7l118.1 cH3sct3 +ztE c-6<-(c-H aBg EEL
rsol ol{ dzll flzl A+3 .J+ E ¤** flzI
^l-8-6flot 6l+) ++lel +c -ErHlE= 4l4}qq4. c-cl dEl zJ"lts
e=* tL+ m,E ols-6[^l ¤41 ee*e_a HIE + 9l+.
tZpmof J. HCCI 7J* tofol+. E' m(3scl)-34.97 m,olQ.
.u 8r1 ,rOt xO57 ¤
^ll
+ ifle. zl-+ sldg 6l-= Eille-l 9lHzl5 q-q-$ e+
7E eldrl
(118.3)
P - ll.co'z, + |I rol + |1,a'z, (a)
adEql"tl 96IH q+ +fl4 4gE=*g lr=Iraro)+. tr|E+ cH,4 sFu4 ee +¤ 9dzl^b ^ll +C gHIezI E+ eq
,rl, ol= +d EHIEE {19 l+r. 6iE ad4 qlqzl
^lol
ffi
4 *ol g+
E=+.+. I:
21,
old oilL1^l [-zEq+4] (118.4)
ti+ I',+ I: _ J'
_21
E_ 2I (118.s)
{zlrJ f$ zJ35-* zll*o14. ol ge

=-zl9 ^lql+'l+!+
I,06 EIIP.E
16J zJ4ol +oid+.

=+lE ÎolE
15
K
5 14
o
13
#J:dq 118.1
12 '2c3sc14= {46}q
ol Ez}9 c-o A6J
.E.z}. -s. 118.11?+
11
4o'l(R._.r: rTTpm)$ 3sCl qel A*Oq.gz,z,).tr-*rl SC
10
I EHIEE +*+.
8
7 4
34.97 nt u
6 3
5 2
1
0 1=1m(3s Cl)(_., = $x(5.807x10-'u kg)x(1.77x10-'o m)2
0
fB llB.2 CE !E= +ts elE^l'g AE ollLl^l oJtr 0llLl^l =4.85...x10*t kg-'

=9. =91=
^l.olE
ollLl^l )J?4? tzl $ty:g7e 7l1trl.
r4r uB.7^lg ol+6}q q+ Ar+= E=+.
kg mrs 2
"JzlqolL4 4¤. Bq=+.

E
1.05457x10-" is
12 -+ IU + t)h'z I = o, 1,2, ... 4nx(2.998x108 ms-' ;x14.85... x 10-' kgm2 )
=5.77 m-t=0.0577 cm-l

{zld /= 4¤.F"+ "Jz}+4. _z4ai.l +B 4dzl-b ++r+
*ol aJCE
"llHzl *="Jg zle + 9l+. /=0r| /=t Îol9 9lHzl t4
trl-+^J 1r8.10^lql e-l6ll^J
3 Ff rI-Ff o)=2B-0.r154cm-t7} q=Ell oIag 3.a6GHzoil
n, - 111+t)\ I =0,r,2,... +E alE^l-g ollLi^l (118.6) 6|]BoJtrl-.
ole+?ol +C Î+?] E"Jg "llHzl rB uB.2ql

+4.+l*.r*. ol glHzlE =fl$$
+4ql= Ell= "JHI4e + q-s=r+ a
e EZLE Eld 8+ rr++1. olso*4. (b) EllA qdrl
- fr2 tr
4X qdzlql^J= +^J EHlETt Eg îe azltrJ 4"lzl aI
hcB=i nl-+^J B- EIE d+ ttrsll (118.7)
+. trl-s+ +EE s¤g oJ$als(E9 roe) olsl+ Eld
4ficI
zE n* sld +g 7*=.4(/.>2). Eila Eldzl{cH3cl, NH3, tri
rqE qlqzl +il trIg=4 aol ¤4 c6H6e+ eg)el qrq-q} +g ol 74. ++lE +^J E
=9lql ^lol
Hlezl-4E rllE -o14.
ol 4dzl¤ 'J4t
Et= hcBI(/ + 1)=rfr;i$f
I = 0, 1,2, .. (118 8)
=-H-+ =
tso!(CuHuel a.
e sE E"J)e- ts+6J+ r4+ # +qE +C EHltrzt
++6J Eld E*Bql^l= qd tI+E dffi zlzlt_ 44 +E EB+ 4LsE ![= tsol(z]C"lut CH3Clr,+ ?ele ++
alE 4ol E46I+ r4d-q B-ht4nrE eE6tl. glHzlE q}'i.F"J+ + +d EHiE(r,e+,)= /r-tr- +4rlljEl,E /rrs
E.-hBIU+I)E +4U+. + sld tr+
^l-olqlE
B=cB9 *41 +4U+. rfl$ llB.4^lol rl-e=$ ¤"1 84.
71 48.J4.
qd tr-EllE ollHzlE "JHI4es aE:d pae E^l6l-Lql,
olag 11B.8^lE "JHg hc-tr 4b 4ee.! iil+el qUCg (118.11)
,*i;tr+. + ol
^lg f _fi+fi+rg ols" 6Jl.<J rlê_g rJol 448 +E gl+.
FU) -BtU +t) +E ell^lE alE-Bt (118.9)
sld 6Jg {ffg

+4'}]4E r=cFg o1g6t$ ¤+. "Jd
qc ++lE r}"l9 ?J4+ r-l.s=4 z.ol 84.
,=#.+=+.(+-+) I: (118.12)
olag "Jzlqq}4 er+s Hr+elE :/aq+4"J ,, trll4lql

F(l+r) -Ftll-EU +r)(l+D-EtU+l)= zBU +r) (r1B.1o)
IU+Drt29= Bq +H g+. "JzlE4 o + 4gFe}{E4 zr1q1
sld ^J+= lql HlHlglldlE_tr_ Ezlzl 44++ qd qlqzl E6IE "JgE + ++lE 4+E=* ^dEe Khzl 94, r= o,
118 trld EE-E t+07
J Eol -s. llB.rE '}]a qA4ql ++ Erql -o=

1.0078 m,), rns= 14.0031 mu, o) ^lqltrl -+
R= 101.2pm, e- 106.7E
J
q+H .tt'4 1r= 2.8059x 10-a7kg -'
llt= 4.4t28x 10-a7kg
7t +gr+. rqH rre.l3b^l9e+El A=6.344cm-,oi
B=e.e77cm-,g Eg + gl+. r?]I 1lB.l3aalgl e_lql^J
K=0 K=J q=q-4 a3 ar+E eg + 9l+
(a) (b)
lg 118.3 g^l+ ,of E. (a) K=08 q= T= +9lsl 4FJ0l 0 FU,x)lr -t

=9.977l(/+r) -3.633K2
^lLlE
0lrl. 0lnll= ErlTl ++oll +^.1-d + ++lE alE-dcl-. 0la8 lnal++El
rnelB 71.= Eldolrl.. b) l(71' aEH,J J01l )IDE_ nll= E^Pl +e ++ ++l= ¤zl.ll4 cE *all?H F0, n7l 4lt+q *9lE *=
FU, n7l g+.
eldofzll Ecl.
F (1, K) I GHz =299.1 I U +l)- 108.9K2

tl, . . . , +tq <k& r*=+. (K= ffql CEg +q'}l ql6J
E 4ol=
ql oJzl+ol+. ME 94 " + ee-lq= +r}el C /=loJ A+ql +4¤ +E a_ ¤ ++lE(K:t, Eld^l
zlE rll gg+ "lluJzlE r6.32cm-r(48e.3GHz)olzl"J tr-
Eg +l61l^J hr"!E+.) rrl6t4 rr-lU+Dh2 a{a_ E-Kh,
o + ul-Tq=+. :zqH qd 6}0l trIg=4 ?ol ¤4. alE EolzlH^l qdB q={K=O) r qlqzJzl- re.escm-'
(se8.1GHz;o1 g+.
r[7! g7] 128.2 Bz].= C-Cl A6J ,Jol7]

r2CrH33sCl
F 17,- x1 E)x'
fi,J(l+ r )+(.4 - qe elE^lel
ald -Bf
(1 1 8.13a) 178pm, C-H a,* z)olzl lupm, rflI HCH 4ol 110.5'
I=0,1,2,... K=0, !1,...,+1 ol+. ol Exlzl-Bz+ sol"Jzl !84 sol"JzlE golrlliE
¤zlrl olq^J Eld .ilHzl 4l4}6rq+. 'Jg
+ (t + I)l wV'g =,-tu:7(y'1){
-h-fi z>I9S'V
-4- --::-
4nclu B- 4ncl,
(118.13b) :I-IJ(JJOLW'O={ rrtttSLZO'S = Y:["& &-m
.ur 81 ,pOI x g9s'g - '.- 8r1r* ol x zgz'g -

llr rE 'l
-
11B.r3a^13+z|q Eld qlq 4 +fl71+ +c _E-uEql el
aa+ {olrJi.
^J44 +q}q= 4o14. 4, qdziq qlqzl= "Jzl-+ /e+ K.il E=qI+. Ke+ _K
'ila
el glHzlE zlzls= K=0oJ ullE zllgalE
K=goJ u1= ffi ++lE 4.$F=+ CEol 0ol El ^JE.l]Ee ti"J6J
,+ +?l7l z*e_a qclqq il4. ol olelql E^19 4+E*
iz"qlqzl /,_oll"J Ea¤lr+(rB rrs.:a).
=+l= g e]+4ql ¤E¤4-" + dcq= + tr-E cEg *=+. ol
K= t/oJ trI= 4g¤.*ol 4E d+ ffi +flE
qdq zl"J6IAl qq, qlqzl e+l= +s r,ql el +_cE+ trzlE* g"l u,at *"Jg 714 + fleq, MF\,
# tr, . . . , tl-e.^l 4* zt+tzllzl94t:zH llB.4). oSzl| M,
a6Jq{rB rrn.:U; fi
r(el +s=
qlLJzlql ¤6Jg +zl g+=Ell, olag ffi
z
Hlq +E9 KE *= +z|7l c)4+ +g= HIEI] J MJ
qd6lq, qlqxlE qd
=zlzl e4l
HJ"6Jo_E
%r-
6}ql ++6}zl rllEol4.

MJ -0
EEE7 EneflErlgaruqHrt
=et
ltt]
'tN'H3 +zI= ¤Et 4olzl tot.zpmoltr HNH aEt4lol
106.7'oJ 44 oldz}4. ol EztE qd 6Jg +4q4. (a) (b) (c)
r.a1*
Êl
*d s llB.lE 49 ol86ll^J +C EHIE ral 118.4 gfih MrTl xlLl= *. (a) M?l alrH'J"J J}ll 7WE tt[= ElxPf
E ++trt. rr-l.r- 1lB.13a^l9 rAl^J qd 6Jg +6J+. Eld +E d--Jd4 z+ +91= elc:dtr|. b) u,A 8Et| ,J. (c) M;=08 r}lts
z= #?19 4EEgol 001trf. 0l raJg =rJ EF K=oE SEt|oll 6tl=J6l=
^J+Eg llB.l3b^l$- r^l^J +6J+ a=01tr1-. l( il01 =Jal^lE 7l7l0ll rtE
^11
rgg r= + 9l=rll, ol 3.?oll=
43EtJ0l Exl-el++oll El16ll^1 arol-d 4E= LlElL.!E[.
408 1 : EIIEBE!
qlqzlE +EI.ll= +4+zl ?*zl"J 4dz}9 lJ.4

= ^lql=
r46lq qd6F= EzlE
ql gs6i+.
E Sd6}al B^16l+ 91,\lal
-E-
2/+r u1loJ's- .E.+ E"J.J qlqzl. *=+ trl+^J '}]a old 7

zt
=+l=
K+ oql a+ql. 2(21+ l)+e-tr, r4r K=o"J 4l
Y QI+ 1)6o + trlEl¤+. L \-
\J(
+B Eldz|-|. lr=l,rzt 91. trI+^J A=Bzl El= El]a qd
z|+l {4¤. + gl+. "Jzl-+ K= q46]1 2t+ rzH ?g gg f.g 118.s aEol Erloil Elil= a4. elEoil 7l?.!61.= flce8 ,Jet?:=
EaE qrz t!8^lz E^1.= tralccgcl.. ola1El ErlE E^l.el g8
"ltrlq} alg 4H ru
6J (}g 714 + glzlt| .llHzlE xzl EEIE==-s'=
A7l^l7la. qal^1r elE 8+E A^^liltrl-.
6l+. trI+^J ol Eldzl-E *7l H]]6J ql$ql
^JzlE QI+t)*
qE+E= zld s"J olq+ +zl zlillg "Jelel +ql +qI Hl]
oJrqzlr rel6}q +c E-BIET| H++(rB llB.s). zfl^l
6J qlEqlE QI+t)+e 4 qs}¤tr|. El+^l oJzl+7} /.J +¤
EzlE A+q= ?lcqql el6l|^J ?_.-J ,Jo17t 5q+q tr}?+
fldzl} dill4e e QI+t)24 trlslE$ 4Zl g+. ol trlE+E +^"i EHIEzI+7I++. d44_"e. ol gd "J:z4d ollE
! I7l +r}o}ql "I4 #46}z11 6zl$4. 146}0l /=tgoJ 4l ^l
ql 3rld *izlar"Izll r?-l6}q qlqzl rtol9 t4
qAe 9lHxl9 tr4z} Mr4lL+ 9lril g+ ol ,J{l-qdzl 4 =+1. ol
= "-a+El e]{lq= aE4 6"Itl4. Er+
trl+r+ aol qlqzl. e^^l7l= ¤ezl"J 6Jg frzl-al].<1
(c) CE elExl' =
r.el6l+ 4"1 "Jtlzlol4.
dB ag)e] a+ql= e#
irldzJ{co2, HCl, E= c2H2s}
9r4E9 g-dE
FU)=nlU+t)-b,lU+t)' ?d ra{zt (118.1s)
¤d_"e. E a+ flzlE E= dql +zl-J + +gle"J sld alE-d
ol gq+q, ffi ++lel 4eE=Je ool ¤4. 146}0l d¤ gzlrJ D/= flC grelE 8+4r +++. zi)4 Ez}el g
Eldz}9 # ++)E 4gE.=J C+g oolq, rrB.l3arloll^l
d "J:z4d tr-+= trfq-r+ ?ol 3rI4 o + eqlE d5, ++
r=0o14.4+^J d¤ Ezlq qd 6JC q-q=$ Aol g+. rlol{$ e{
rlcql^J ¤B4azl"J e-JE azlc eE=
FU) - BIU +t) I = 0,1,2,. .
. c-d alE^lsl olE-Br (118.14) +4U+)e+ +4lg+.
"l 4g rrs.s^lr+
?J7l:- 6Izl"J ?g
"JBg ral r+s+.+ b,=+
'v' flC grala A+ (118.16)
qzlrJ= K=0-o ? +r g9zl"J +¤ sldz}9 a+ql*
a=rol4. d¤ gdzlE ¤B¤4 +ql Ell6ll^l 2/+ tzlel ;'Jg 4l+qr trl4^J 4i5 4izl *g
qltlrllE drll A6Je +g
* zl4 + 9leq, ,'|4rl r qs+E= +B sldz}9 et+t)2 gd grea ^J+= 4=+
el qElE tr}]tq 2/+ rol 94.
zlEtEt 0ll 118.3
ztEJEt q 118.2
t2Ct6OE
4* 8=1.931 cm-roll- t, -Zt70cm-tol4. trl+^J,
+B sldzlE "Jd glHzl rlol9 ,J4g L+ +x(t.g3tcm-l)3

=+1=. bt. - =6.116x10*cm-,
4ql= rrs.ro^lg d¤ :zldz}9ls 4+qq, El+^J (2l70cm-t)2
i,(t) - p(z)= oro I 4.' H3sClE A +ql= i,(, - F@= 63.56 cm- I
r7lr D,<ao1 ve- 7l
4zlzl dql= "Jreld gc
oJQ :ze-la|¤ 6B=63.56cm-r, 4 E=I0.59cm-rol+. trI+^J,
ol qlHxl f$lql ql+61 Le g6}9 Elrl+./=20olfl
r_ h 1.05457x10-'nls b,FT+r)2= 1.08 cm-t7l g+(32GHzgl 6Jl'J
'--*'E-
-2.643x10*'kg*'
(d)flC grBld 118.2 slol=EEI #lEI

xl=Ellzli Ezl¤¤ ,Jill qdzle -H-?14. rq+ qd6l+ 4Lg Ezl¤ql 46J 3rld tF+ 8E dB4 <tg 0.1_10cm-1
EzI9 flzl¤g gdqg ts4l qq +Îel 7l6IqL4 +z7l ol+. qlsî NF3ql ql6H^J= 0.3s6cm-,, Hclql ql6l|^J-
118 ElcEBiEl t+09
B^t
rg 118.6 ExE|'a ?1= tr=^toll4|E AE6|-ts

=d
E^Pl C^1718=
LIE- I= + 9l= tlg 8=xl^1al HoJt|(=8oll,\lts r E_frtle 84Ef + 9ltrl-).
F --->
0l 7tT'Je eld E0loll rH-d ErlE C+ +rlsl aE4

=7lLl.
fg 1 18.7 Exp I Bxl.= q= 0 |E Eill 4lE 4EE--Jo I -Ee=qolo t
:dtr|.. =+-g E"J-d g:dtoB aEg El= I7l r ut
"Jg E^l7l0l B^l.g
10.5ecm-1ol+. EI+^J 4d dolE ulol=+u| ¤qq +î7I ¤i71614l Etrl'.
ÊJ]I
g+El4+ "J=q= ag Eqq4= ulola._e.u} E"*Eg
ol$-all,{ a^l-6llo} alt 1o14.
l¤-r "J"J"I"J *xlzl-#El4+ "J=¤ 'il 4
gE*ol B=q7l +ldl^J= I7l olEl-* Hp+"Jg {r-
-
(a) dE4 7=l rlo
"Je4ot al-b 4"14(rH tB.7). Rr
¤.B.Bql^l= "JHI4 + +¤ dol ,6qz} EBIEE rEloJ

o il
'lol
o -+Al dq +4g qc6lot ++. zlîl* 4hI %r-Bg ol r

*zlzl.c+ ¤+q4+ "J=g qlqlE
HldJe_E
0llIJ
4AE.*q H= ullEq) Mll Hsl+ + 9l+.

z11E g^l"l=ql rzflt r}^fl+ 48 s= _H-oL+. 9zlri9 ¤
'l]+ EE 7ls" * $z|

$ql 96IH ++6J 4d dolzl-+$+EJE Ezlz} ¤+4 d El4 "J6Jql ullrJg- r.7j6}r.
"JzI9
71 ry+^l EHIEE 4"I"t 6J+= +ill4 dq +zlol
"J+q dol eHIEE +ql-H-H /+ 1e+/9 dill dol ^1l7l7l +gr|
9"t aJ4. ol +zlg rd4 o + 6ll46IH *C Ezl-b fldg ae "Jql Hlrll++.
ull ,+3+zlz[ e:a" a[zl"J Hl+C Ezl-b z$z] *o.[+= a"l
q(re 118.6). EzI9 97 r5t-:z--,21ft- 421*3 +l4q+= a _( /+t ) p|,
ll t+t,t
1,
| -lrrd ) (118.18)
T1|qr B + 9l+(#J r+Cql^l= Hlq-e dzlerol aj-i{g

pld^la+) q7l^J p"9 Ezl.el ¤+ {zl ffiz} eq1_=ol+. ol rllzl}
g+ d7l 4+zI EHIEE 4l+ql Hlql6}q, q?+^J tl +c
ztJEt q 118.4 E4t q6J +c ExlB+ g{
q d 34d dE¤
ÊEH
+4U+.
Eq zilzl Ezt$ Hl+C 4flzl EzL, qlAql co2, qta sldzls{ rtq ++lel qCe d+zlE H11aJql o1+fl
CHr=CH, Ezls=$ qd
CuHu Hlg¤".|4. ole+ Elqlg
HelE +zl ?*=4. "lqq} sldzlE dE"6l* ffizf$ {zl
ocs, H2o= +colq uloJr-Eul +4u+.
ÊEHS gie_Ire +^ldr+ tr-E+¤¤ 6tzl *6IH, _24-tq lc/I E
rElr. +¤ Eld4+ qd ¤.Eq E6H^l "J:4zlzl ?+
+ {zl ffi^l= 7*^l ?+eq, r46}q $tr+ a+. += gevJ + S,+. trI+^J qa irldxlql q6ll^J= dq +
= zlol ffi$¤"] S4.
,llel6}H qd Hlg^dolu|. ffi4 e_Hltr_E gg atrE
?41 "Jrqa + gl= +B qaz}g qlE^J= sil{48 E AJ=+1 LM,=Q,*I AK=0
oll dEl +4 B.1e)
ile old^l (11
+ gl=ql, ol E4* I=to aEq qd +Fql E6ll^J E

83pD9 'd+zt E.HIE= E=trkHclq 4d+zl EHIE= ac Ez}ql4 dzltlg 4L+^l7lH "Jzh+ Ml++ql^lE
r.r ool4 "la4= HlrTI $ g+. $zl. rtl:z-z| EHIE9+ 9d ul]a}$ +Qql=)e+ +dq= qe+E7I +84_o + xll4
r +9lql +611^J= Eq l7Aql^J ¤H6}dri). ¤4tre 118.8). ols+ e.ol 419 ^J.4zl dzlet9l E6il^l e+
4= ¤^Jg stark E$ap 6J+. ol qlqzl {E}= g+ ,d+
ql4 Ar+q el6IH dB Ez}e] a+.il= +gr+ z| Efle- #,ql E=6Iq, q-Q^J qd Stark s.r+
zl.,<1o.3 e ,3+zI ^slEflfl
g aa=ol ffislzl ?+= ql dol EHIEzIAg¤trI. E ar.1a1fl dzl EHIEe-l a-71= +g + 9l+.
Ll -+1 LM,-0,*1 qlE dq +41: dE qld^l- (118.17) (o) olol=erl lE:;EHel -Egf
A/=*1 dolEg;Bq 4R6IiE LI=-r d"lE"J#ll 6ilR*+. dB :4dzlE qlqzl +* ^l(r1B.14^l)ql "14.J
d4
=+lql
t+10 11 EIIEBE
,^.
O M,J
+1
L2 K q
t3 5 4
!4 5
x1.9.
d= 1
7Ao qt 0
A= t5
otF #
t6 ., N xl-E-\
uot
N 1 (f)
rfJ
(v)
ur-l $
+
+7 mF lo
.fal rB.8 +¤ dE trlErlE J=7A ollLl^l Elil= E7l8E E4. Ton

MF03 xllE:d tr= 2=o.E EltrtElcl =9loll
?ltrl'. ***
=+l=01
fA 118.9 dE elE^l'9 alE ollq^l dEq fr=.1 6"1=+101 -0186l.=
=9|,
EoL -Lala. EEEIoJ ++ trlE E+ qEaJ(^lE= F46|.| LlTl=
=/.l.d=
r{$ 591E T|1ill+ EEst
7l^la_ LlElL|1fltrl). cE 4 d0loil^1 Eol
zl-ol
E I
*9rI
I L t. 8|=^l E.fllEel
^1171=
HJE:dtrl-.
^ll7l=
i(l +r+ I) -F;U+l)-F(/) -zEU +t) I =0,r,2,...
68, ... E"J "Jdg dEe qq ilsq E+ +eg zJ4 za
Ad E0lE n[#: dE aldrl (11B.20a)
* 7l^la- 91+= 4"14. E|+^J dE ÎolE 'J4g +C6lH
flc g:eldg rBl6ll ¤ trI= llB.ls^lg ol+6}q ole+ "* B= +g + ?lr ol{etrgq +z}E ¤q +4+ +^d E
E= trl+4 ae 49 +g+ 914. Hie l.g +B + gl+. trl+^J gzl¤E e*g "Jl 11o ,, +
zat-r t^r: Eg ,i" lE E4l E"lE -r xuf. __rq T \JUJT
E-l-l al -r+l 7l^l- Il-r'l f,rlrrI A I ann. I
+b,tl+t)'
âl,l Î-l --1,
i(l+te/)= zEU+t)- (118.20b)
NH,s+ Ag +gz} EzI9 A+q= ol *H o + I, 6I4EI9
rBl+ olE II 'Jg d¤zl " e a4l 6;ql Hloll^J q+
^lel
Eg + ilzl uIEq + ,l]E aq} 4"lE go}444(ocsq
al 4zl qEql .n"Jg 1rB.20a4l o e +4U ar+ a+) E= a.J 4ole+ aq+49 got4zlzHNH,9 a+) q
q+fl Hli6}r+.ûlEHE B+.
ol ExllE 6llA6F= ilE Ez}4el # + %IHe
EEU qEÊTEHEEgq+ =flflA
0l+61-= 1o14. ¤-?l fla zlil EzI9 ¤!l ?ol
^dlEHg
e+ A'J4ol F+lgA il+E golg Bzl ?*bQl zlzgalg
14NH3E
4d lE=.H E"Jg ql+6}qEr. ol Ezlt Bzl
44 Sol 4dx}4 B_e.ez7cm-,ol+. ol Ezl-E 7+7+ol +4.lJ= +^d E{l_Eel rllolrlE ol tolel
r.E{a J.E} Eld 6}g 11B.13xal o e +qd+. A/= t 14 +6Iq ¤.J zJols+ A.J4g ++6ll .J + fl4. ol ,JBel +
AK-001u + 9d d"l9 ++q ++ 4g r1B.20a^14 ¤ +g qlTI ocs +zI+. F9l fldE il+6llE a6J aolTl H
6lzl ?+=4E zI43 6l-+E f,.^lql Er+a}zlql ol f;lzf Ql
-9-q Bql"J ge+q.
++E a+qlE g *=4.891 g^ql III+ H6l+ q
l+r<-l dololl qfl^l trl+r++gE=".I=+ 9l+. (Eq 16A)E E+ r-+Eb Eld E"Jql ¤6&9^fl
=ol ûlEHE
10r23... +Eql, r_vlgz 4gol 4¤-El%hg +4+rll al.q ol4,ol E
ilcm-t 19.95 39.91 59.86 79.82 zl. zfzllel qa4 aElg + flq^J qd qlqzl g.J
=+lql
vlGHz 598.2 1196 1795 2393 * Azl ullgol4.
4EEH d$el r]lzlE yl ?zltJ{l ,r++ ftzlalrJz} +Eil
d ZI4g 1e.e5cm-t(se8.1 cHz)oltrI. rllzlE zlLt trl-^l ¤q=+. olBlq} 44 4lzlzl- 444E zlr*
rP! B7l 118.3 CH33sCtg zlzltol E4lE qEol aI olf+ sld zl]4lf +ql7l ++B + 9l7l rllEol
= Boltzmann9 =fl9
{e}. f-0.444cm-tolE}. 4. EE Bzl(E l49 d4l xl4 ¤r+ Eq 12A
(zttC g'qZ)r_rrD888'0 EiZ E, :E
EotEDql e-l6l-H 4 ^J4=9 z1li1a3 /el <lol ?zI6Jf
= zl+E}+4_o +
+ A^l6Izl"J e+l=E qe+E= ?zlot4,
118.20a^l o+ e]{lq+ E.olg:B nB.eql + ol trqlq= + A6J
"ll+q
qq{ \lz)llzl\rflE4
ÊEflE
4r4fltrI. ol ,^.EEH9 zI^J +sEI ulfzl 28,48, =+lel
t]-4Er+b 94) +trll= +4rI= 1o14. *;il4 o e. "5"1-H
=Ag
11B a|cE]ElE 411
qA qlqzl /9 2fli163 trl-g=rl B.$ sottzmann ^l o +

=fl graia
+qaq.
Nr * N&e-t"o' E
¤zlrl Ng ^le- +9 dill Ezl-fr srE 6+l /e-l qslE+ /

E g+4"J Efe tr__7 ol /ql +dH^J trlEqL +¤-ql r (a) (b)
^l¤-
er+= 0 o e -aeg ol !g +E|]E "JEq += /el <tg +g fal 118.10 E7l8= atE^l7lE E^Pl gre1^ lq Brail Exl'= 8=rl
+ 9i+. d¤ 4dzl-9 A+ql= ol 44zl tr|g=$ rJol S4. EfllE= roJE q 7$l4l Etrl-(Eafl Hl=¤E E^lE). rJ+E= 801
(a) .=^l=oll EB6l'Xl at8Ef rqlel'(b) +^1611l atEEr r]|(EU4o+ E^toll
v2 8E|14 "J-dol +e1l at8-g nfl)
EH6[1Î rl.= + ?lEl-. olal-d 4? t
T- KT I 4111 uflill#el eld (118.21) Erl'= Hl=]lJ¤ trJ=E=,*E+a ^lE
"Jdtrl-.
,, mu
2h& 2
dE ald^l =91
dB4"J EzHglaql ocs;E a+ deql^J=

B-o.2cm-'?I zlr alQ. ol oJBg r-srlEEl o + E7I
"l+6IE ulol=_+u|
kTl2hcB=500o1q, EI+^l I^*=2221 $ct. r4+ {zlrJ 4 s"+ *g Ezl# s+6J cH,4 sFuel ?3
+ 9l+.rq+
zl$a11op 6J "Jg 4 dol 4+zI EHIEzL /el *ql e]=4q
+B sldzl-= Eld Raman g"J olqe[ ufo]=+E]qlE Hlg.
(11B.18^l), E +^l-= zL+ tl}+g "JeA i 9lo o-e(Eq
C"14. Eld Elf}Col+r aN.! $z|71e=E Eld ^JEllql flg
11A) {o1ql +q6F= + THill+ i}qlE E=*+
=+l ^}olE + HrI= 43 "LrJ4 BzI +E=g olBl+ dB #zl9 xile}
aol+ trI4^l ^ll7l7l7\t| d dql qs" 61.= l9 zlol tlg I Exl ?+eq, E+4^J Ezl-==g ^JgAE +=ql 9dlrJ "lul
= 7l*
^l /lz)llzl B:3 'll+ P ?t+ oJzlgg"F 6l+ qI qd t4s zlzlts + 9t+.
=+lql
43 olr]4. f,_.,.jzl og dq +4¤- qB^lTlEJH {ol ffiz} eql=
E -::.qo1oh 6J4 olag Sd6l al{!6|EJE E J.z|] fl.tlo1e
118.3 Eld Raman #JE el ldl^ll6J 48s9 *la11o1 6Izl"J r A4"J "Js" 6IE Eld
Raman "-EEHql^lE +^ll4 Cq +zlg qg4 ,JY+.
Raman &*(Eq llA) q^l pld dol9l E6il^J +49 + 9l
+. Eld Raman d"l9 +xll4 dq +!g EzPI EIE*zi dB 4dzh LJ -0,+2
o + ¤* g + g"lot +q+ 4o14. ol zlfr$ olal]alzl $l elE Roman
4X ::ldzh A/=0, +1,+2 CE{ +4 (r 18.23)
6llî= 4zl* "Jql^l EzIzI 9:_4zlE AE= rE E+E AK= 0

cr(Eq l7A)ql el6]]^J ACg+= 49 "Jot"t ql+ aA q
zl-^116l ¤86|zlp tllzlzl s"J 4zl* +ql^J= Ezlzt ¤7 +++ :zld-R"-* E+qlql^Jb a7=s"J dolzl 4I+ r*rlE
,6qz} EHI_E olelql q.s=4 eg +g rd+zl _E_UEE q 1IE+¤- H+l^l7lzl ?+llq, Ir}4^J H"lqzl ?*:- nayte'sh +
*trHR"yLish +^1, Eq 1lA). _zdgq}4 EEE
EAt g+ ^l-= +sal
Eo6H^J
""tztqql4 44I A4E E"-14 E+ig+ 9l+.
!= alE (118.22)
fl4* E E*ol ¤+. + dzl^Jol qg ulaJ:ee_ zl

E"J4_o
n CE_I +*l
trIE}
Eloo I ^,flEaJel
+6IH qee Atr+ "JrElTl+. +B qd4E ¤+E q^l
EoJ4"ltrI. r+l+ El+B Eldzl.9 ts+EE *"1 Ez}q q 4F#zl ar,"J dzl.Tl +Îr+el dTle} rts cl-94 ee- EzL
H HJ-6Jss zle"6}L4ql 44^J ¤*ol 4_=|l +{Uq(r ffizlEHIEE+E^laq.
H rrs.ro). qle^J H,9 dz1EE= 9P ^Jol e.J+ql +4
= an(t) - a,(Ecos (tJrt
61711 4r-s"g qtB+ ¤46}rll zls"oJ q q 3
Iri,,d
"J:zHe + 9l
q.= a1>a1ol4. ol $zlz[ 4-t1H a)nE E]46]H 9P *SxtqlrllE ¤+
trtr
^lAql E={-= aile -Holq(ol4ol
EE dB Ezle+ zflzl +zl(Fq"ld "ltqolzJ +41fl ul="*ColH), ol'
ol)= HItHJ^"r ¤+EE zlzlt_ ?lgq El4^l qd_Raman q= +4lE q+!+ eol +4H + 9l+.
9^"1"14. olag 9d naman r-trleHol +g ol+ol
=!g6J a= Go+ Aacos2at*f
t+12 1r ErtEBts
9zlrJ La_at-atol4, ats +^l7l Eld6l-= Ell trl?+ ao+La J

Bel ao-Aa ,tlololl,<J H++ ol 2a*ol +4+= ag :
^lql K
5
EI Eldg E o1l"I4 ¤+E7I ilg AIe--E + H Eolszl ull 6-
4
E"lr+(re rrs.rl). ol
^lg +9,'8+^l
e.Hlegl ,1
'il+ ^lql 0
-+q+E q+r+ ?J+ 4r+7I +g+. li. )t)-
Pind = (00 + Aacos 2a*t) x (e cos qf) ,lol
- 0o6cos ait + lEAacos (Uc.itcos2aut <.J
cos x cos y T.!E+ #

= ]1cos(x +y) + cos(x -y)l
lal 118.12 CE alExlE Ad ollLl^l Raman CEj N=+28
=?lsl :BtAl
"+lLEl-Ltlfltrl.
= u^lEcos(UJ.t
t, I
+ jc Aa{cos(a,+ 2ao) f + cos(q - Za*)tI -=1EElts tol=. Ee4g 6lE Raman -e.28
ÊjlEaJ
Rayleigh d- 0l raJoll LIEILJ 7le,q EU tl l1l7'll Ll-EfUtl.
,'de-,zl+
"l er+ql E6tE +9 EÎ tlt+ql^J T156l-= C
E(Rayleigh +^l-= g^J^l7l=)g ++tilq, EqI Raman v(l +2+ I)=i,-lF(l +2) -F(/)l stokes
EEHdg olf^lzl= + ^"j+g ai+ 216.,^ci'l^l +4U4. "l _,,-28(2t+3)
-; 1E1",$i
tttB.24a)
dEg La* 0"J trll+ ++*+ trl+^J ¤+E7l E+Fa}loF

Raman 44ti4. olag qd Raman E *H LI=-2'J dEE A+ql= 4l* +^Ld"l t l +g uI
H}-stokes
ql rll6J ÊEHd$"l
+ill4 dq +zlol+. += +444 ol "l¤.ol FA-F,U-z)zl Eee.q ol +ÎdE
ol ffi$ *ol ¤4.
HJ-Stokes
r. iU -z<- D=i,+{F(/) -FU -zll cE9 nl#: (118.24b)
=i,+zEQI -t) C-d eld^l
a
r. 0 E
stokescEe- "JÎ +ÎduQ {547l. *gq, I=0, r,2, . . .
ql 46H^J is+El 68, 108, r4B, .. ."Jt4 1l¤+7I *ol+l

I zrn
dtt
In
4. H}-stokes ^¤lF B ds=3 "J^l +Î^JB+ tg 154 +
E d o + 68, l0B, 148,..."J+40=2,3,4,...qI 4aH^J; LI=-24
lt
d, J.
dq +4 d"l= oJ-o-7lE^J
6Iql^J= I=271alzJ ^}ell"l+)
+Elt}+. stokes d4 Hl-stokes dE9 ,J4¤ 4 tol 4Bolq,
"la¤- +c6lE r_,= +B + glr +^l
ola_os+E ulol=.
leJ 1 18.1 1 ETlHl Extoll P"JEI= ErzlEr- 180elIoJ 6tE e"l E:,J+ql^Je} +aol ¤aJ aolE cq6}al +g + fl+.
^fe-g_e
tr=E= x13 'JcE El=0l7l1l -dtl(qal^1 :d E Adql + E l). AE
^
Raman E8goll c[:$ tr"t=+2 dEi +4]e 0l qEoll Ll8 a0l+.
EEU Rnr,rgs=qsgG
"JrI dzltlql e_l6H^J +gq= Ezlel "J:24d3 rso"s] v|^J"l T6.732mn"J Ellolz-lE +^q %Idg B=l.eecm-'gl
dg 6lH il+ {te-E qEott4(tr}4^J * H qdql + H '4N2ql agg
rI qE EE Eld naman Atrl=Hol *s1l
4)."14,"1 ld4"J +ill4 dq +4 a,l_+29 :zl ql+"Iol+.
=4ol+.
zE{El ol E4E rz?]s+q rz?-lEE zl]iHzl El
qd qLlzl dq +zl a,t=+2= 4+^lzlfl ^l¤f
^lql+ dql E6ll^J a-i+EfI Haqo+ 4d g^Jol+.
dB Eldz}9 =fl
naman
Raman E""t-9 qlr}g + 9l+(rB stokes d4 Hl-stokes dEg 11B.24^lg,r{^J 414}g + gl+.
118.12).
^4EH
d=E A+ql= ++ +^ldol E^l
LI=+24 Stokes
uI^J"l 336.732nm?l +^Ldg ii=29 697.2crrtql 6|]
+Îd v,EtrI *e ++= +4U+ ol ++ olFg i;U+z)* =Ol trI4^J rrB:aa^]4 g
'JqI+. nB.24b^lql sl6ll^J +,q=l}
FOq iHF0+2)-F0))e+ Aeq trl-e-,rl1 eol
+4*+. ÊEHdE-ol e dEel gzlT} +e+.

118 ElE *lE t+13
I 0 I 2 3
Stokesd +
ilcm-t 29685.3 29677.3 29669.3 2966r.4

)Jnm 336.867 336.958 337.048 337.139 J=0 J=1 J=2
I 0r23 fal 1 1B.13 alfl q"E-Et+7| 180' trlCE ttllel EIC tr15gt+g E11d(rJEAr
2i|fl alE^lE 0lE6l'HtDe J'Joll 9=Ettrt. J7[ qt+?] tr|.=:sr+ts +E=
HI-Stokesd ul+^l Eeq, Jtl:sa a3 +E= ul-Etr|..
ilcm-r 29709.1 297r7.r
AJnm 336.597 336.507
ol r.trlE 42 ne.z32nm9 tl +Cdol ,"J ,r 1 o3=99-E

tllzlzl d^t4 e Qzlz;lQz} AAd-= "JAel dEE ol
"
+qd+(olqe} glTl EE= 4ol E_BlEe+ tr-ql IrJE r.
,+ql ¤+'Jq). d4l EE H$l= 4+61 6c-
ÊEHel
4, u}4r] 7trel B^q %+dg E^L^l4oF d4.
XlTl BTl 11 B.4 3sC12(i=0 .9252cm-t)el Eld Raman ^¤l
EHg 4l+I6Lq+.
:.-u) 0' L0 L 62, t' t 0 L 6(, :p7 sa:lorg-ih
' ru) g' 6 L9 6Z' s', t gg 6Z' V' Lgg 5Z' e' 169 6Z.k salols :E TIE+ -----|
f.g 118.14 27HE 5=Pl trJ-+ qlo'e E 2B^[ Exlq AE
=4
Raman ÊEaJe -4 EZI nflEoll ^1l7l7t fleol E6lts AE]EHC-
LlEfL.IEl. Rayleigh N=e 0l rBoll LlElL.! 7ie.c1 EU q l'll4l LIE[lq,
0l C- ,'.14*1o+ g LlElL}lTl 9l6tl11 E6l'Xl LIEILJ aol+.
118.1 -eq Eld 8E]|
=IIsl
C,uorel 9d ^trlEHg 6]]461-}. cll llB.2all$ ol$
nu-an B trll= t{l+ q F!l= rEj6ll +qot ++.rfl+ q
6IE d t4_e__E+q +qI Eld tl+71-+e HlBse +a.J ol sol olH trll= +AlqL Cd"l 44421 ull$ql ol*lq} ral ^g
c_o a* rJolg} oJildl.zl ?+=+. ol pffiol "Jil6lBlH ol 4 44zl c'uo,el 4+4H flxll4 ZI++ 49 "iul4. oltrll
Ezlzl # H ^Jflql fl-::. :z4apl 5+_3, 3e- 1, Eol zlle_lg 4}+q I Tte=a+ +Elq= 94 /J."l* ^J'H4 4 lg u1F3=
2+0,4<-2, F9 Stokes dE"Jol +QU+r z[{allop q}4. = g+E ulFlsol zlg.
4 / <tE4 +.Jq= ^J.olt olBl
Pauli fl4(Eq 8B)e+
'60gzlqol -B=(boson)ol aJ 4o14. qlE^J zTllE f,:=" 6J ^fl
49 zlzla gl= 'H2
^¤-oE g?lg ¤ ^fl-+
"15 +e|+zl ?+= ad.$
+= ^ldg ol+61-E
4 'rF,9 a+ql= "I4 +Eoll.! Eol= Hte+ pol ¤f 7el
Eg + 914. Pauli H]|q g?-l= qE 5e+ {z} ltrfl$ ullxll t4z} +4+= *Hol zl+ /"J aql Hl6il^J 3uH+ qq, uI
R S"J olq+ qE EzI qd tr-E]]E -ds"6lzl *E 4^l olEel sld nu-an :-trleHq]= 4lzlzl3:1oJ dE"l H
=A+
4. pauli ?l4q el6LE + F"+ _E-=g -il.+B A+ql dill4 ,J"I +El\I+(rB tB. 14).
1
oJ y]-8.6lA-
*e7lzl -EEI6}|^J Hp+E 44421 ?* "l+fl
olo} ql+. ct6o, Ezlzl180" Ela6IE + tJEl6J r6sflol
r¤+S=61 qq, ,r|+^J ol +zlE dill4ol ulL=.oat-:''
@ -q=ltet Ert'^lg
^Js ^JqE ,H qg
H6I^l ?+.t"t,*+. rfl4 "l ExI9 Eld ir+-E" EL+. gtrl czle+ u|{z}zl_+ ull=ulgolQ, pauri ?l?]ql E6H^l
=
-trH(flx}9 p +llEC+E4 uffizlxlE 4Eql 9=6J+) ol
r +ill4 oJtrJolTl
ttc. :zE1g oll *szl Hqlot
',
EI+= olelal qdql E6H^J t #szl (-1y EI# {aJr(:rr-r +r+. rq4 ,H, +zl-= 180'ol{;.la ql= ++61 49 szl
118.13). n++^l c16o2ql ql6l]^J= 4+E I #E"Jol
:"]+qq, . Hl-+= A tr + t+6}zl ?*r+(rB uB.ls).
¤44 " + Raman Cg 6L+4 4sH^l ++\i+ dxll4-oe 44lE q lg ul^s." gtizl ¤zllal-btrll, I + rjl
Pauri
^trlEHg
fl4ql ¤+qq 4d t4zt dq4 0 " d+q= a ¤-dill /tot,r=1(= ¤¤ fil.L 4,olz, 4"lzl aI
^Sol ^fl,
g -"4 EIl4a qI+ sldql 9aHrl t+.6J 45ol ^JE i+} 4E r,",a=6(a+Tl îrJ, tJl.L 4.o14. /tota=loJ ^ll
414 11 Erl#
oo +lE EE er+ql E6iE ¤+ Aq /Er+ A6JE + 9i= q
e o +
180"
---f----
el8
l-1lL '<""-
s u]-=." a;-1 371171
.rg u]-=." o;"; atqgol4.
q= ,JBE
=z]]6}q,
q
^gol
uB.2s^lol +4q=
4Ig llr il=
eol
tsIe+
q
IHJ'J6JolE *+ Pl +e+ zI+ I7l ElY "JHE +e+el Hl=

J+a sat 3:1014. "JHI4 " E q /oJ 4_o + ¤ Fq zflzl EzI
g+/E olr "JBe_l^fl"I
+e+ 4++ /= ol= L "JHE +e+el
+a Enl
o o =
HlTl- r-l¤"r+
g+ /= ol? ,JBE +
=
z-ol ¤4.
lB 18.1s =
4+ rE "lF "JHE +
F Efleol$ o40l 8A E$EE 5ill4 trl==-Ef+E
PEzl
--dYa EElts +,! ExlE elE^lTlr, olq^l
E:dtrl'. 0l trl= "l EZt:
= 23^l E^l (11B.2s)
-.j= 7l^la_ E/.l)= .3E -ag6l.= + EX|e ^18Ll'+cl = 1 (I+ 1)// H]-e+ A+ ="r
^riJ(dol-J ^4E
gqLJqz ,g4-g + ?Itr[. =.j=o I EJEB uJE 7lE ritl= 0l Etrfl E4lollAl
I
I t(r+ r) C+
^flE
A+
trlE:Br+E 7a7l E:dtr|.. ^flE
/=1?_l 'H2ql qlql^J= ol ulzJ. 3:1olH, r=loJ '4N2ql
qlql^l=
ol ulz| r:2oltrl. Eztel 4zl *Azt Sd 44"1 otH 4lHoz
a(A)a(B), a(A)FG) + a(B) 0(A), "l B(A) p(B)
ol I zJzl lvlr= + r,
ql q6ll^Je+ ?ol, Eq lrF) E4lzl +d-6H41+.
-loltrl. ol a+ +471180'= Eld$ tr}]= -Ezl Ae+
0, -f?-l_tr
q Eal= E IB "le]el Eot{ls ¤6&9 "lA+. t"lal t
nz[ {rc. HEf9z]"J ol= d4l4-o -e H6l-zl ?t
^ll
5'"414 ffig,:-n1 f rz} H6I4H:z Eld E+*:
ql4 e ^¤ Hl]6JE=g tlEaql qlB6l !4rll HslElq, q
=+.II14^J
.J+q PszI H6l]ot alq, g+ <iE /EEJ -d+g+. 4^J ¤q q *b ,H, Ezl^= sfl ^lrJol gflE zltl
"l4,rJ .-i
=l! -, -!^¤g
t^fjef -l-E"l tT. .6.8 vi -tE
6 ?!r
<i
r-l-lrr!
if,J i:t
-p.lÎ
r'!rl -.J;r'l nl r r] O ul'zl A A
/,o,a=0ol.a Mr=OoJ EL+= a(e)p(g)-o(B)p(e)ol
9lril t+-E" -t=
eae+^, r4a 4tTI e 714 +i= qal-t^
+. Ezl Ae+ szl tt-g Hg ql= q ^fl u1^5rg-*9 *szl H = ^gg
etl f a_=E-f +E/=O"J tlEl]= +48 i s,_o Ire
6J+. 4 a(e)p1B) - a(B)9(A) + a(B)9(a) -a(e)p(B) = -{a(A) =+. gsql^JE qdg
g+. ,rl4^l ol a+.il= +ill4 ,lÊ.o6lA ^J'J6l *3 4l+6lq +E qd 0d qlq
F(B)-a(B)p(A))7I
zl. r*E+.
9 Po.zl- H6t*1ts r sld ul-Fdi+el ? ozl H6tzl ?*o}"t
=e.-d7HE=
trr. ZFll ElCrl.= Eld *qg E-r*E "J:uelzlzl ?+= Eill4. ol zl8g+.
42. ol{zJi 55+ + +C EHIE9 +ql 44 +d, EllA,
zlzl a 7. Exlz} 4d-Ra-a,, ++Col qelB HIEU¤ aJ4"l z}+.6110}
CA, r?-]r Hl-EHe fldrl.=tr E+¤+. cltrl.

I3. qe qErl= !H+ +gill sole+ B4I E}fl^ll i,JolE ¤+ tr 8. 9d-Raman ¤%IHq 7t{14 dE4 i+*lg (i) C¤ Eld
q1.3
qlq.
Îel
A+ A.I=0, +2, (ii) 44 EldzlE a+ LI=g, *r, *2;
24. fld ts=aid9 ExI9 E"&3 Hsl^l7l= 6J trIEql ^JAq. AK=0o14.
trs. cE4 96tE +xt7r ++ sla ÊtrBg +EI D e. Eld lulE-HE E"Je -.-4 E4lel ¤6Jg B=ql, ol q E4l
=ill4 "*lql ql4.
.ilElE +^J"lE+"t pauti fl491 S+Elq 4d tr4z} Cq4-9s A+q=
tr6. ulol=.Eu} +"*Hql Ell-J 7i114 cE4 +4g A.r= t1,

=
¤tr-g "J++.
L,M;o, +rolH,4? qdxlql qdl^l= +7l4ee AK=O
11B ad# 415
=e-d4=
,^-lzl
oz. ,\l
-1 +4 al Ha
+¤ Ed= 1=l1n,xl x,E old+o +Pq $zl iTlzl94 11B.2
+4 zl?-l
+Bol+ d¤ qdzlq qd.J F(I)=BIU +T) I = 0, 1,2,... 11B.9, l1B.14

E=hl4ncl
44 fldztq Eld.J F 11,x1= fi] 1l +D+(A- E)x' I=0,1,2,... llB.13a
K=0, +1,..., +,I
A=hl4ncltt 118.13b
B=hl4nclt
fld ts:4d F0=EIU *t1-b,l'U +t)' +B EE dB Eldz} 11B.15
fld 9:z4A tI+ fit=+E'ti' 11B.16
9d d"l9 vlf i(I+t+l)=zEU+t) / = o, 1, z, ...; C¤ z}4l Eldzt 118.20a
al4 z[216 *= E]d t[EI J^-=(kT lZhril)''' -* d¤ Eldz} 11B.21
d¤ 4dzlE sld Raman r-4EHql^JE (i) i(J+z<-17=i,-zEQI+t) (i) / = 0, l, 2, ... IlB.24a

(i) Stokes "l (ii) *-Stokes dEE EI+ (ii) i$ -z<-71=i,+zfi1z7-t1 (ii) / = 2,3, 4, ... 11B.24b
EJII 11
+-l
--I c 2fl^l-Exl-el TI=PJH
> ol EE= Hll+= ol+ s=d 6[lal
E^l'el TlE Eol C5+= +86t8 erlSE t

-g + ?lrl'. zlill g 2gxl ExtE +ga eoE +galts=8
,lB^'llTlel
=-sfel qt =
.--:
K
olEg + 91trt. 5
6
{tx
dJJ
> e{d T]ILJ E-
K
2gxl Erl-E cE 6|1461"= rll= 4El TlExl -e.93 nE
0186l'r, ÊEB=6llalel qlc "l c5 aEe-l

E 0l Eg=
=:st
trB-g + 91E+ +86}|^'l oltotTlE
:Lltrt. =-d=
0 E?t, x
> qHl xl^l fg 1 +ca :. "JuFf

1C.1 E^1. trlEJ!¤ ollLlÎ i4ee EEcrl.
te =
=Jg'E! =ijoll^j
"rl 115x1-e.ts(EE 7E)r+ 'Jx]| clC^l EE(EE
,Jtrt. sEd:d tr1EJ¤e Il-
"JolLlzl eltrl. 0ilL1^10{l^l=
SEoll trEl
s=! ÊI
E gr "Jeq(++alol qtdltrl), 6flal =E Ca
ÊI "f^l
118)= +xl6lr. 9lol0l 6lE, EBEE "JHIE 'Aal(EE 11A)-E olLrl, =/.l7[ =-Lf =i]oll,\j=
g gr ?loloF:Lltt.
L=ELI.
e
"l4rJ *rI4 " Ezl-
ulfl¤ qlqzl +dg trIg!+ ?ol s
2+lzrel + Lll4 +E ,J^le qrJ 44zl lzl4o tr Efl+ Ed Eol E4.
6l-= TlEol+. ol e+, r4r q+q=
=fl+ dolE e_9 zpoll^l +l#6J 44 ,JZ ar*"JzL
&5¤
^JEllE-
zI V(x)=lk,x' x=R-R" s=CE trlEl¤ ollLj^l (11C.2a)
Î"lel
zlr ¤Bg + 9l+. $zld /q+ efiIel ,JE= +E|'|]= B A++.
11C.l t!=- kf
d,V
dx 6l
E O
l-^.
I
l'X{Ol"l
LO-'II
(1 1C.2b)
rH 2fl4 Ezl-9 dB4"J trlHl¤ qlqzl +dg +

11c.19 +Ad +=ql^J trlHl¤ qlqzl +dol TIrl-= uilE t61o1 z
4U 1ol4(ol rflg *ts4_o e Eq 7Eq t4 tr1$ zJ? r aEtol ,J6I+.HItr}JE qfl¤ qlqzl +dol Hr EsH kf
4,ol4l. ¤¤ dqe+qq Hfl= x=R-R.E +48 a+, q <iol 4rld4l 4l+¤u}(rfl 11c.2).
A6Jol
fl¤ qlLlzl= trl-e-=$ *ol ra/or-rf(E4 snel E|gz|el tL derol m,4 m2oJ l flzlzl EEd¤ i4H1¤ "llHzl= *a
a1 rzE -H-ol-4)E ol+6}oJ 4lizl +glql^J dzl]rla + gl
+.
d\,/ d'y )
v(x)--Y(0) + x++ x- +... (11C.1a)
dx dx t
j
¤zlrJ 7ln (..)09 x=091^J9 E++ <iolr*. y(0)g "JEs K

5
0o + ag + :l:r v9 rzl. r{.a5 +idql^J 0ol s+. o
tru
ktq
=71
rl4rJ ¤olh+= aal 6Jg HglE z]+-q Hlql6J+.r?]a H ulr
E-
?)zl 4& rllE s= ri]. 6&E-e- +^16}r qHr¤ "lluJzlE

q-.q=4 ?ol 44'J + gltrI. 0 E?t, x
d2v fal 11c.2 E-d eol +=oll^lE trlEJ!¤ ollqxl -d 8+sl

V(x)=!
E x (11C.1b)
7{3}\
edl,
=-Ef
37loll sl=-dtr|.. k?l a ,JZ 7E rtl= r.lEJ!¤ ?EE =C9 =Ee
=01 =o|-Tltrt(e-d
11c 2flrlErlel [15EBE 417
tF llzl .$5$ 6|u a+sl Schrodinger 49 r+g_+ ?ol 84. ?.!E!tt q 11C.1
(11C.3a)
nct Ezlql^l a6Jq 6J c-+= s16N m-,oJtrll, "lag +
*#+!k,x2ty-Ev "J Aqlql qlel tr-'J6l dB4"J <lol+. 'H3sclg +-E
9zlrl m"ft ++4 ?ol cEq= fta traJ"l4. eelg 1.63xl0-rkgolr{(ol ae}g +4 gz}E a=*"J
r.67xto-rkgoil r,ll+ Tlvl+q, ,r}+^l Hflzlzt ¤zl t4
mtm)
m-=-
crr mr+m, +E treJ tgell (t 1C.3b) 9 cl?lxlql ql6ll^J llE6l-= 4+ rJL+). tr++^J 1l+ +F
el 4l++= r+g-+ ¤"1 S4.
"l lEg H+ Er-lHS ol86[^l(E rallE fl.r,[o1= t^]l+ kg m s-2
4* rg _H-oI4) +z| dillel ¤Eo e-tr+el fl4¤q tiql4

a-
( srcfr--' )
l_t
v2
¤# +El^14 e3 4014. I r.orxro-" ke )

=5.63x10t4 s-r
tro+ dE c|^l +E ef*r+ +& e"*e ?zl ?*4. +s e r4r ololl aNclali El+= trP-r+ ?ol E4
- a =#=2.99x103cm-t
V=^ 5.63x10t4 s-t
r i+41 e*g ,ll+ #
rJEll4 d4l4 BrfgF+ EE-l l|lc 2nx(2.998x10'"cms-' )
^l7l= 4eq^J +e= 4ol4.zflzt E^lE a+ql= ol E
ol $palzl"J 4?]zI Ez}ql Ell6ll^J= "JHI4_oe ,Jzl ?*
+. rqLI ge a+ql ol E9 +E6Izl ?+I'++tI d=fol
*4.
11C.2 4eld PJE
4-r.
TIE dolql q6J +iI4 q +iil4 dq +4g F^J4es
+E 4elol EqzI 49 zllqalH r1c.3a^19 Schrodinger dzl d"l ,'d+zl EHjEfl ^deg r.BJ6tJ. +A.J+.t l{
49 a+ 1$ zlzlt- a+ aEg alft- ojulolq ql6J 78.24 e-l fl;.1o1_= rj.^11+ {+ 6ql ,I^11+ 44I a4z[ Azflslo] !l
4 +A+. trl4^J zE.24E 44= ol+6}q, q+qE 4lF ql o q, r AEg q-gr+ Aol i4lp
+ 91tr|.
Hzl f;?l$ {i Bls trl+r+ ,Jo| # + ?l+.
+^tCg ¤+614+ %l=6tts^l {F ^J4 HEIzI gqg
n,=(u+!)ha r--(*)''' t)=0, t, 2,... + glselE flzl¤ol .rJE E+lE "Jea 4 EzI9 dzl
T.lEoilL1^l [29^f E^l] (11c.4a)
ffi4 EHI=zl- Ho1l"F ¤Itrl= +ill4 Cq +4g EI+
=g.l rl4"t qI+.
++E +4U d+ tlEIel "ilqzl?l d=:dg G@)E +4.11
olel+ {f,$ 4sld E¤ol4a 6J+. ol +zlg Id4 o +
a-2nv* i=ylc=attznp
ErJl, E,-hcG(u)ol+. E++^-l oleo
6]]46IH 11t- ,d+zl+ {zfffi B^8^l7ljL ol4El dz}]i}
6lq dF aJ G(z)E q-q-rl *"1 449 + gl+.
el rl5. dzl^Je rlt- d7l as-q4$ E^J^la+.
G(r)-(u+\)i n- | ( k' \''' {zl,tJ +flg d9 Ez}7} g+ {fzl$ z}d ¤,qE S

" - 2fic\*"u ) oq, ol dq +zlol s+61+ a¤. ,d+zl. EHIEzl. {a}zl
alE-d [29^l E^l] (11c.4b)
"J 6LH ¤+= 4,"14. 4lEq El+^J= EÎq
,'d+zlql B
a}g ?zl ?+= aol fleq(qlaql ¤.q 2il^l EzIg d+ e
tlE ,FE" 6J+= e9 Eq¤l ao] 4ls" zls] +r+.
zpgl^J
Tl+ 6Jg EzIg difl e"+ql el=6tzl ?+l- +s. ezlql t.) E|+^l "lEloJ a5+ +Îdg ¤+6}rl+ q+zl ?*=+
olBlal rl5+ 4Ed ullfsolep oJ+. qEl +L Ee +ql
E=++. olag E4q}4ee B q aJ4zl"J ?4ol+. +
"J"J flzI 1ol
gz} 284 ql+61 +49 trll= +tr d*ol zI ef, E4 zfl^l +^l7l q++ 4qd dolE "JezlTlE *trI.
qlE^l r_ill c60 +ql 9l= u, Ezlt Eqlg c60 ¤:zt
4S flzlE 4=* m,* *rL4 o e A4l ¤+. "lull= 7lq+ =q7I
e+ q6J vanderwaals tl-E+¤¤ al.{ .rr6t-=_z} EHIE=. Ttzl
flzlzt +rl+ flz}"ll Ell"H^J {f,$ {f er+7} ¤+. 54 z
flzI Ez|el a+q} ffir=tltzo];q +1r ee}g dill A+e-l HI 4, ol u|Eql ++g CEel 4e]d +$Utrt.
dol -gHlEql ++ 44 as+ dEzL
ûlEflg I +qL 4E
ol g+. ! m,6_*mol ¤+.
Cag ol+6IE r+s=$ ee {F dol"ll +fl +zll4 dq
I+18 EIIP.E
+zlg Eg + 9t+.
Lu _*r +nl4 dq 7=.1 [4e] t!5^fl (11c.s) i

Az=*loJ dolb g+ql 6il8d+ 4,"11Au=-13 "J="il 6il j
K
5
B6l+ 4,"14. El+^l -d+El= 4lE dolE u++= u+r+u o
d"loll q+'Jg a6,*,E +4.J a+ q+4 aol 94.
{ll
m.l
E'
AG ,u= G1r+D - G@) -i TIEÎ- (11C.6)

^+
ol rl+ dolg uI+E 4zlz1 +ÎElel zleld gqql Eq 0
E9t, x
zlqtr TlE dol= 4e.ld ¤qE +Îdg ¤+614+ 4+ feJ 11c.3 ErlE 6llel qLlxl hcDo= tr1El¤ oilLi^l +Eg 4ol hc4el
:--.
r- rL exl ?jeq, e-crel 0E IIE ollLl^l oJ= qeq.
dgql^l= kTthc=200cm-101q,ril++el dF ++=
200cm-t-H+ *ld
=4. rEl6l.q Boltzmann EE Bzlql E6fl
ql++9 Ezlz} a¤-ql= Hlq 1IE ^}EHq
v(x) -hcb"1t-e-*l' u- 14
2hcD"
U2
Irzlorse
trlEl¤
ollLl^l
(11C.7)
^J "lEel 9l"loh
6J+.trI+^l zlH]l4"J dolE 1e0 "J 7lE dolol
ÊEH r=0olldE v(0)=0ol+. Hglz| trI]- v(x)zl hco,e- d=t}
4. olBl,* e4e +"J ¤-+do e ¤ 448 4," =
cl(:zH 1rc.3). +Eq +Â +=ql^J= H+lql 4E v9 H
e 7l'Ig+. rfl+ H,+Fr-+2HF*e|^trlEHol
eg HI¤¤ E6Iq plzt eEdg B=+(zl+6Jg {2flo1.t1 ,A4 t'.]zlzl1} Aq}
=
44zl gtrD. Hglzl- 4a q= EEdq a+e+= gEl 6l]4
,l +E+B + 9l+$=ql^J). arl 4l=¤ ,IAg a*"llE "l 7i Eq\fcj'. Morse ElEl¤¤ oi+6'l-E Schrodinger ,lloi ¤9
d=ol E+ E"J6J af+ql^l +4+q +"J d zlq qlq 4 ?ol ¤4.
ol g+. rfl+ asl 415.9 ztCol +q¤^{EHE
q= EA t"lt =471'1-94
d#=q,rJ {olz} "Jq+q, r?]6}q 44 zl| G1r7 - (u + ))n - (u + l)' x "i
ÊEHql
9 d5ol +4t+. u=0,1,2,...ruû TIE-BI [tr/orse tr]H!¤ ollLJ^ll (11C.8)
x
a'tt n
11C.3 HlrElt! 2m"r,a 4D
lrc.4b^lel Tl5 6Je dal-ulHl¤ qlqzl +d {{ql ¤zlrJ "Jel +-qflC ++ulr] x.E HlIEttl 8++r +4
"J s$d +dg ol$-all.<J fe} 4olzl ql$ql er+
=^}4 Morse llEzlE dE qlqzl
=+l
ib:H 11c.4ql ++U
ql E46t+. sEdB trlHl¤$ e'J 6H4= "JeA =^14"J uls+ pol +6J6Itr| ol G"ll +6J E .ll 6Jg uzl 4e++
+ He ^lel
zlt,\7lq, :ael6lq t-g "JzL+ql^l
q, q+^l :lE H+lql^l "*= lol ot'14. tl5ol k4l Erl a4l -Jg q =.zll =
rJ flxl-=ol ¤B 4a3 zjolE+q E4zlzl(aq,q 'J:"IH uI
E"6JfzI qzl= S9ztzl) +e ql= EzI9 trlHl¤ qlLJzl
EEd_o + *r}^la + S.eq, Vg Taylor d4rlA 6J= +
=
(rrC.larl)g +7ls s+^l4ot t4. "ltrll= e#qol rJ ol Q,
o
ulellalzl ?+sq E|+^J llt-ol Hl4E[4o e gr+. s
^J H+lql +
dzll ulHl¤$ e$del a+ql BI6IH ++qol ofo|{ :zr-l

K
5
6Iq t|l :==E tl{ql^J= 9lHxl #flEol 4 zl*Al ed!
I ql"lot g aol+.
6
{ru
dJJ
E'
I v=0
(a) 0lu1xl ffi5ol +aJ
0
-1 0
E?1, ax
2 3 4 E
ulaF}J"J trlle-] qlqzl 4l{l6i=.J rJBg dal flHI lg 11C.4 Morse tr'lEJl¤ ollLlxl=de E^|. tr18!¤ ollL]^lsl gU4 eSS
=+1.
¤g q 7W4l +4Ll] A + fl= 6J+= 4= aol+. "lBlql g LlEfL.!El'. 0l llE Schrodinger alol ollLl^l ,J- +g
=,S= =o1Il^j
Eraz} rl-94 ?3 rrrtorse tr1EJlE ollLlrlolr+. + ?]Et. +Bf SE[|E ollLjxl=+l= a+)19:Lf6ltrl'.
11c 2flxtExlel Tl=EIJE t+1e
+l +H^l7l= aol+. ol ElHl¤ +E9 4"1ts h'b,o|q,

+ !g 2i -6x,ioltrI. trt{^J +qd ql"lEl= 0l+6}
4zl {t: ,dl4(u=o)s+ flzl-=ol -s.aJal trq4 glg ufle+el H ZZl.gcm-r = i -2x"it, f ?-lI 1535.3 cm-r = 2i - 6x,iol
7l hib|+ dflal qlHxlT] E+. .zB rrc.rglrJ g + gt= H]e]
4. "l + Ar+= Aq+EIq @ -2x"n)-+(2n -6x"i)=x,i*
?ol ol + "J= Îolql= D"=Do+Gtol9 +Al7l CB++. lE zll4+4. l4H x.n =773.8cm-1- * x
Morse d5zlz} olE4_o + ,ll+ ¤46}zluJ {zllB= trlg
"JEq^J
1535.3cm-r=6.15cm-,zI 84. ol x.n9 Zk$_ Zn.ecm-r=
4 Ag "Jelrlol go1 r.oll. !]4. l, -2x,n9ll Bq+E i -773.8cm-t +2x"i -773.8cm-t +2 x
G1r1-(u+ln -@*i)' x"i +(r**)' y,i +... (11c.ea) 6. 15 cm-r =786.1cm-rzl EtrI. trl4^J,
{zl,tJ x",t",. . . s$ ez}oll r+* +-qddE dE4 t}+ x-i 6.l5cm-'

x-=4===.
ol=¤. ole" 6|{ ol
" v 786.1cm , =7.82x10-3
^lg dE qlolEle} "*+:/ EzlE
=.o14,
6il"-l qlqzl= +EI+. ol a+qlb au=+roJ dolg *izl rfTl 87[ 11C.1 ol Ezt9 z]lz ull{f.el iit+E +^}6}
trl-s_4 *ol ¤4. q+.
- G@)--i-z(u+1)x.i +"'
-UI:S'7SZZtE\
A6,,** = G@+1) (1lc.eb)
ol el6IB x. >0ols + uzl

^lqlolE"4.4.
ftzlt;)]-+d"lz| *g u++
+e-g (o) Bigesponer E,\l
tl zlE d9 t e0 ol99lE z<-0, 3e0, . . . 6H'J6l^=
"+$ ++dEol +4U+. olg {olz} ae+ TlEoz}ql^l= +

=:ql ¤4 z}l9 TI+ dolTl-BzlB ullb airge-sponer elgHol+
zl {olzluJ HlaE+Cg aal6]| fH "-*:"}rll -{+¤+. 2<-0d r- 6F= r4s "JHg ol+6ll^J A'Jel al4 .llulzlE +6J
ol$ fih HllI!=, iz4r reodol=. fi!2 u1115 F"l+r + + gl+ ol e_ltBql^l= "Jd qlLl 71 7J4 a6,*,(^l llc.eb)
+. zlll H]]d+E ++= trIg=r+ Bol ?ola14. 9 z=0o_p+El 6llq --*t\zl +.i}4 " + 6.J6ll +E qi4 ql
Hzl oozl-+g.4= 1"14.?
G@+z)-G@)-2i-2(2u+3)x"i +... (11c.10)
bo= LG,,r+ LGr,r+ . . .- IA6^+ (11c.11)
H]|tlfol +EI+= ol+= dq +zlol ao] 4lEozl- rl-tr.o61,A
ol+6H^l +Eg 4oll ulas].fol +4H. rlli olaol olae zletlE E 4q= d+ qt4E
= = Î+?-lE "Jd Îol
,r.l-4etr.trJ cBqzl dq +4g 6tL].e_l
ullEol+. dill ^144 E"lzI El= 44 ?* olzl+(rB 11c.s). rH
=
ql zl+zl g+= a"l+. ulae]. TlE" z}9l Ell6l]^J= qrl+ =Î
<t9 1rc.6ql^Je+ z;ol LG,*,F ,+iql qlql^J E^l6IE +d eel
LuE 4 al+9zlrrJ HlaF+^dol ef$ qlE au>loJ dolEol H"lzI +H$ +C, tr|{^l Drr+ ¤"Itl4. ula4d tf ,.
"+6}ril +4*+ d¤4ee 4lr u}]+l*g rilzlE 7lt llF "J9 146ll= trll} ¤ololzlE 6}=0l d¤4_oE ai6}q,
E E toE9 t ¤s-Hloll "J gtrI. +eol "J q= ++e e.lrJBg rl^l +B + 9l'I.
^4EH
rBl+']]++el {zll r.rl A4E zH nc.6oll +4d a4
E@ HtoEts+et +E ?ol d¤ s,tl pffi 44421 ?*sq r?-l6iq ol %l$_o e
3sct'eFql El]* Hl4E+^d tf x.E +c6}q+. zlB dolg+
xllt u]l{dt9 ,}i== " z}z} 78.84 ts:s.Ecm-rol4. bo
r.alE z]E dol l<-09 t]+ql +* 4.3 ltc.eb

^[B
ru=OoE +r ol$all.<j +6l.I, 4ll H]]TIti 2+04
^19 LGrr+46**..
Ei+ql !g 11c.10^lg u=0o F +r ol+6ll^J +$
++ 2
+ 9l+. relr ol + ^lg ¤q^l vel x,v3 +6Ir" q4 1
.rJ x"E +6J + ?l+.

llc.eb^le-e-+El zlt dolE ,++ql +el 4g
0
=ol
i-2x"itola, 11c.10^l9E+El xllr ullTlEE ++q + feJ 11c.s T.!E ollLl^l
=9|=
,\l019 71e-l= 6t|al +-Loll 0l= ttllrtxl :ct6l'E
6l|al qlLl^|7[ Ll9=r]1, 0laS Elal tso171-r zleSE ,J4E -cf:sl
,J? ^l'0lel
T,i.al aoll HlSg + ?1tr1..
420 '1 1 Err#
gol = a(, TlTl g.7t 11C.2 HgHE dE -,,4612]1 +B6Iq,

=fl=
E+ +?l ?J4e D$.7(re0 dolgl q*), e6s.6, 632.4,
c-d slar'
') r7zcnr'ol4.E. 6il8-l 9lHxlE +6Iq4.
+ r-lou I{9'9¤ :E
() gril
\ -r.,\l
-
t--
\
11C,t, tlE-Elfl Ê4EaJ
3
222
v++ Tlill^J ol+q 2fl^l +zlE llt 7tr+ +6116}
fg 11C.6 AG,*18 dE zf^l+oll Etl6llAI E,\l-d +c "J9 'Jol= E^[9
ÊEeg
q HH 4 dE"l Be'Jdg c+E=E ol+q4 flulrrH
qlLlxlsl eq. 0l ?.ltr ollLj^l ifz[ {fl{o+ 00ll tr=:Lrtrtr 7l¤61'=
6Hal
11c.8). ol qlEql EzI E6l nl .ru4EaJol4r +
7i0l Birge-Sponer ELrHq ûlEe¤-
=7171flcl. E+. cEE Îol9 ,J42 10cm-r ol"Jolq, ol nl +== a
+ aolq +Hlqq 4d d"lz} "J94zl rilEol4a g + 9i
Ee Doe d4l <t.e+ rrll +g+. 4. -r.d4e + E rll, 4l+ dolzl "JqB ql= e6J z)olzl i
7J4o + 6}s.e. fldol BR"t Halb 4ol
E@7 BirgesponergEH ol8
=q*+ =fl+
4r ^J46J + ?ItrI. ulil r-zllol= dfzl-gg e Ir 4E sld
Hr*9 dE qlLJzl ,J49- 1e-0, 2<-r,. .. Fql ql6l] +s-zl ts4zll" g¤. vlE LeJzl= 44 rJ"!EÎ slds. tl
=91
E dolql el"]|^J zl\s)zlu 6ia A+lzls alE 4"14.
^l +e6J ¤4(cm-,)+ 4r+
2r9r,206/^, r94r, r82r, r7o5,
1591,1479, 1368, 1257,1145, 1033, 918, 800, 677,548,41101
4. "l EzI9 "H?-l qlqzl$ ee6}ol+. (a) 1"4=aJ 7l^l

a.alfl /.lEI ol A4g /++ql qlfl^] E^16}l. +¤4$ llE"rl 4d"l 5114"+ H6l+ dolE "Jztqql4o+ zI
z|-=.E $t*zl eltg 6J+. rr-lr +d gE HolE +o} 6ll46H EE zflzl Ezt9 tl¤- dolql +HI4^J "Jq+
^1161
E gtrI. qd d"lqlrJE "Jzl-+ I7l lIuJ+ E*+= ag "J +
= EzITl
?14. + +flE 4¤.F=Jg E 714 qlL-, 9ld4 dxt
d5g :zH uc.7ql s;.lol"fleq de e.lr* +
ol
=ol
+e a4de-a +e}.11fl+. ol +C eE Hol(+48
tzlzld EzI NoTl dz} +llE 4I&E=#r+ e
ullzlzl-. . . n,?_l
e + ++lel 4eE*E 7Ie q= A/=OE E+ 6i+¤+.
E Hol= +61-= 4g "l*614+ LJI-EL zlE +E d4)
zflzt +zlE df-qd 1EEH EoJe q-g=r+ ee AE
2160l+. + qlE ZI3 toocm-'ql 6llB6}q(+zl+el zl
= qd 'J gg zlzlr ¤Eg + 914.
EE Eot+), tr}4^l 44 qlq 4Y zt 600cm-rzl ¤trI
(2s8 kl mol-t "ll 6il%I++). S@,1)-G@)+FU) (11c.12a)
K
r\
T o
tr R7l^l P7l^l
Q1 50
-l* 1H35Cl
ni
'9, 000 fio
,loE
1H37Cl
500
I
0
13
22 ,*l 3050 3000 2950 2900 2850 2800 2750 2700
tr[#,7/cm-1
aal fiC.7 E7l11C.2E Birge-Sponer E,\l ?J4. 'Jolb "Joll 9,1=
LllsrJE ¤ lllzLl gE= 44 34Ee-J g ={!
{('Jo;=}x"JExtsol)E
lal l lc.8 HC|E r+E5 LIFEIE Cfll 8= 0l=7 fl= aa
'Jol :Btr{l=xH6l'71 ^trllEB.
H3sCl4 H37Cl0l ttllEoltrt(0|=E ulE E : 10lc[). Q7l^l7l
4^1?e|.trt =Il1
$ L[EtLf= a3 0l E^19 39 A/=0ol -:l8El^l ,.$71 ttl]EolEl.
11c 2flxl Erlel Tl= PJE 421
8
7
s Elq flq.
TIF dolE pTlzle+ R7l-zlql +4+= 4 ?J4+ +c.lH
6
5
8E &g +e. + 9l9-q, E|+^J ++qI qd trIolr++

4
il 3
2 Ê
1 EH(Eq rrn)g ?+q+E dal ?ol= +ts + ?l
oJ$al-zJ
4.:44 ufol=+u| 41E+= 4qd {d$s4 gd q a

8
?lzl trIEql ++il qd lEEeol gd

f
6
5
4
+61-rll +ag
o I
I
I I
J q c+6J ar+E
2
1
=+.
o
,rll'l lrr fi rrlll'l r, zEtE! q 11c.2
{.!5# ---+
'H8'B¤ zlelCg ¤+6Iq u=goll^J ^lz+q= Rzlzl 41g.
lal 11c.9 tlFsld ru:l-=,aJ9 P, A '; R7l^l 8,8. d=E lllTl= ilE +4U+. t1C.13c^14 s ttc.t9 EllolEl= ols-"a|fl 7=z
9=9 47 | dlEt| THill+el Eol EE1EE a7l= HJgeltrl. = .J qd tr-4E+q +s= slfzlq-q=r+ e
ol g+. ÊEH^J9
Hla+c4 gd4 "Jrqdg +^l6IH, +Hel a.zll 6J
aGtu)ql4 rrc.+url9 Br E Erll -J FOqt+ rrs.g^]9 ,+ i *(2) =i + 6E = 2648.98cm-' + 6x (8.465 cm-' )
q^l q-e-=4 ae a!+= eg + 9l+. =2699.77cm-l
S(r,D=(u+i)i+EtU +t) (11C.12b)

E 11C.1 Zflxl Erlel dE*
olag a# q CE6Irll +Qr]]ElH sld ++ 8= {E tlEI
ilcm-t R"/pm blcmt klNm-') DJ\ff cm-t)
ql E=6Ial 6ll +a- tr,,s +44oh si4.
,H, M00 74 60.86 575 3.61
u*rer9 TIE dolzl "JqB 4l* lz| +t "J* H6Lq rH3sCl 299t 127 10.59 516 3.58
a+ql q+^l= H6tzl *g tr11(^/=0)E ll4. :z46}q g lHl27J 2308 161 6.51 3t4 2.46
+ +elel TlrlE ++q a_ + p7[r!= ,tcl, s60 r99 0.2M 323 2.00
^trlEBg ^ll =+.
LI=-roJ E= dolEe ol+qAq. . zlE ¤ql q "*e alE"l ++qq
= 9lE+
i r(D= S(u+1,/-1) - S@, I) =i -2BI

P7f^l Eol (11C.l3a)
I =1,2,3,...
(b) il ,JH
zlzli ulfzl
v-28, i-48,. . "J
=-d
ol CEE ol+ 9d "l.rll +a= _H-Q z1,t16l 6]]4qL ar+q E6lH AE "J
oizltsull, dEE 4lzl EsE sld ^trlEH
zH;llis+ I -t+l
=91E9
zlf uzl6zla,I"ll q+ qd *izl rJi6J+. ol rr4el
dol sHle! az)ql E6H^J eag+(rB rrc.q). elE ozl gqle ElHl¤ +EE HlaelCql E6H^J AE qlqzl9 *tl =ts
rlt a/=o"J E= dol9 d=.e. ol+q{ 4o14, _ErE / a}ql ql rr|+ B+ aq+ z)olzl f;zlalEE 1/R2el B+il7I ai6t
rll6l]^J :a ++r=ol ffi$ a.ol ¤-"JaI4.
7l trll$ol+. as} {EE a+ql= u4 *zl4l tr|4 RE ¤+
zl= "J H6llE l/R2E ¤+il= Eg + ?l o o + 4d d:fzl
ta (/) = S(u+1,/) -S@, D -i 07f^l dol (11c.l3b)
H6J + 9l+. d¤4 o + B,g Ag Bo9 ile4 r-zvozl zttrl.
ol {olz} trll=Noql^Je+ *ol) ol zlzlT} 4lF dol r,9 #3 ro9 <le4 4zl trllEql Qzlzl(+4+= A+)*
"l+¤
ul# r"llrJ +4*+. rH lrc.aqldE qzlzlzl +4'I.t g "JflE "JdS dE=E ol+q^lr, R7t^lE dEg yl ¤zlal
zl4zl Hlq il=E]I 014,3 Hcr Ezlzl + dzl qt f99 q qq EA4 +e6}q, E Pzlzlel CEg EzI4 g4l+trt.
4¤-F.J EHIE. ol
4zl ?*otrl dolE "Jezlzl {a}zl u}] tr14^J 11c.12b^lql+ I qtq B,= Bq^J '1+4 ?J? 4+
Eol+.¤o + RTIrl= Lt-*t"J d=E ol+qd aol+.
=
. Bg + el4.
v* (/) = S@ +r, I+1) - S@, I) =i +zEU +t) i ou) - i -(8,+ E) l + G, - E) |
| =0,1,2,... RTfIl Eol (11C.13c)
va(/) -i+(8,-E)lU +t) (11C.14)
ol zlzl| ,E+ k.g r|+ +9_E i +28, i +48, 9dE i*(/) = i+(8, +4)(l+t)+(8, -E X/+t)'
422 11 Erl'E!.ltl
J+1 11C.5 t.!= Rarnan

^'lEaJ
J v=1
E,
J-1
tlF Raman +ill4 "t +ill4 dq +4g FtI
d"lgl El]+
*)I
F
+ ) E
) o
4_oe. 4o-J6J {ol ffi{ s{le_E rel6].q +ets + 9l
+. z1^ll* lll¤+ E ;lzflel fl.r.l.o]= ,$^llf, Lll+ 6ql 4711
E G r> l>
r) l>
J+1 qqgl+. ¤zlrJ aE"Jg a7]]6lH dF Raman dolql Eil
EI +iil4 dq +4e Ezlzt dE" ¤ q ¤+E7I Hoxot +
J v=0
Eo J-1 q-= aol+. tlE Raman +%IHql^l ¤+E= rEl6ll +qot
.r.g 11c.10 UEe -d gfE E0l7l El A= 7l^la ?l+=
olE:dtrl-.=-'J
^l =91=
6l-b o1.,9 L Bl+^d
"JzI-Ezl-+¤¤ 6l+-Îolql d+ E.E:
^t!= ol "Jq+zl glafl.<j5 Ezlzl EÎ +Îdql 961t.<J a Ir a;4
+ Eld ^J+= zHH4_etr. 446171 +l6}q 6lt il + Eq*q 6}zl ?+sH "J 9zl rll$ol4. Ee "t 01;14 z
"JB
ol rl
UHol4. ol '*Bql^l= 6I+E +F tr"Ell_tr dol
^Fs"
flzI Ezl-b TIE"B ull Ezlzl-+Eqeq q =4d4 ollo| a[
=El
q= r++r=g ilql ++ !e=- ol+7ll aN.! u}.e| F + $z[ ¤+E7] E6'tq, Ir]4^J ol + a" F9 Ezl-==g tl
^ll++ql, F Raman +Cg ++U+ +¤ as+^dg aqB ql= TIE
+= tl-EllE CAEql"J d4 o + E=6J+.
^13
t-B rrc.roql +4u utp* zlol i*u-l) dole+ rru+l) d Raman dol"ll qlql +ill4 dq +!ol 4e.ld dolql^Je+ trt
ol= 6}+el t.g ll5- 717]|4, trI+^l +F $zl\e Lu- * lol g+.
^JEl]= :I.Eo _qE
o + 80ql E¤6J Lo14l Tlqlg + gl+. ol rHql el6iE E^l +ÎdE te 1l¤+ 4o + +4+= H}-Stokes d5
iRU -D-i'p(/+t)=S(0,/+t)-S Q, I -D7l g+. +H9 ttC.tzU
* Au=-lq Eil+ 4oll, *g df,f +e_E +4+E Stokes
.3'=g Au= i lql q'l6J 4."14. t}-Stokcs dEl} Stokes d=el
s(r, rE 0l+6l],<111 4dql BoE +r) +Elq]H trl-94
^19 ,rllzl} d"lgl +qq= dE t1-4E9 Boltzman z|1i11;ql r
ae e+= Eg + el+
,ll el=-J+. tr|{^J H!-stokes d$g {lE ^J{e-l Tflill+
i RU -t)-io(/+t) = qBoU + i) (11C.l5a) 7l- trH+61 zlzl rli$ql "Jq}4e-tr-
==
^1l7l7l "+6I+.
ol e6J rl¤ /+joll ql6ll^l E^]6IH z1&z\z} 4pooll p$ zlill ^J {t i$q +H}qq Eld dolz}
^trlEflql^J=
(+zl + tlE)ol oql zldol +e+"t *+. ir}4^l zl$211fl Erl4 " + "J94zl ql+ql stokes cEr+ H}-stokes dEql 7I
zl ]vzl4e}u-4r:zB rrc.il). dq +4g al=o, t2(++
El 4E ag +R + 914. gd "Jr44ol ¤S"l
qI Eld Raman HBql^le+ Aol)o14, ozlxl(Ll--2), Q7l
0o++q H."l4zl"J zld s_"3q1= tr g6}¤-=4]6lH
+zl ?+=+.
rl(ry= s;, STlIl(a/= +2)71 ++t+
,n0) dolq np7) dolE +¤lse 6J *g {t- ^}4
E aga14, :4al-¤ olEq Aq+ zl+ r,9l el+++. *
ql^Je+ u|+z}zl_e -:.H 1 1c.1oe-tr.+El i*(],7_i,111=
S(t,/+t)-S(t,/-t)71 L+s-q, rul6lq q+4 ,J? 4+7lt+ 8
7
e+ 6
5
4
i*(/) -ioU)-qE,U+I) (11C.1sb) il 3

2
1
8
z]=JEl oll 11c.3 7
6
5
sld t1-+ 4e+ B,E <lg A+9 d"lE"Jg zlzlr +6}| o
I
4
3
I
E+'H3sclel a+ql= rn(o)- v p(2) -62.6cm-tol4, :24 2
1
a}q rrC.lsa49l E6ll^l /=1?l 4* Bo=62.6t4(r+i)cm-l

rll:tr ffi rtll'r r,
0
= 10.4cm-,zt S4. ole+ Hl+6}zll ,R(1)-rp(t)=60.8cm-l

olq, r46}q 1lc.1sb^loll 94^l /= loJ 4+ +_ tial TIE+
=^l.de_l
8r60.814(I+i)cm-r= 10.1 cm-tzl ¤+ q *g dol# fal 1C.1 CB trlflIl'slLlFAd Raman rujEgl5,okesd)oll LtElLl=
ol+6|H 4=1s.44ocm-,el ir=10.136cm-rol +g+. + q o, a "! s7frl. T.!E+ Lg 11c.eoll^1el UEH-e LEILI 9l=r]1, olag
*oilLlxl -ol
E0l(e=+)71-g^l.uide_e+El rl tsg oilL1^l= g0l'LHol "J^f
d ++Ee 4<lE $ to70 +ql +szl ?+gg "J + 914. BCsl TIE+E HZI 6l{+71 tr]|Eg= +=6|.qal.
1lc 2flrlErfq IlE EBE t+23
ioU)=ii-i+48(l-il I=2,3,4,-.- o7l^l d0l

naU)=ii-i 07f^l Eol (11c.16)
ir(D-i,-i+4ntl -1'l J =0,1,2,... STlrl E0l o o S
¤zlrJ ,i= EÎ +^tdE yl++. 4e1d #t$ql^le+= g

q EE dB Ezlql EH6ll^J qzlzlzl +Elt4 qlE^J coel
r1c.12ql r+4..}]fl=ql, 11c.16^lq elo}ts a
^trlEHg:zB
zlzlzl tB d o + +r}Lt"t 6lzl"J ¤zll_tr= Hg -E_oJe_-tr
2000 A?/cm_l 21oo
+4ttr1. ol ** tr-6} TIE tIEIE qd tr"+z| r|$rll zloJ
q= q z1] dEol 6d9zl qlEql +4+= 4"14. f.eJ 1tC.t2 g^tEl-EJAel tl5 Raman ,tE=fl(StokesC)O| LfElLl=
+4. O, Q, "! SzlxlTl e+ LtEfuEt. +E +3 g,\l
dE Raman EBE9 Eq zt)zl Exl¤ ¤+61+ rllr o;
T.!E
ÊEaJdE
,|!al E^ld l'olel trl+xl= L[ElL.!tr[. olE StokesC=E e+oll=
+6J + flgq, trI4^J {F Rarnan .^tr]=Hs-e.+q g= A =;rlC4
+lal +/.|-d=el ril+(E^|.oil '-Jzrlts 0llLJ^l= L|EILH= trfE4l)7l'
^lel"
-tr= 4e-ld ¤4rH + E= AB= -HSElr+. ol
o lal 1 C.l oil,tlel- e0l g+e.e [6lr gl+.
1 1
=7
êlEB3
c ,t+ 6il"-l qqzl, "i dEl aolE zlzla_ ql4g + gl9.
4, ¤zl^j g= atr-E "JFzI E llc.lql ++Elqfl+.
=eil7}lLJ=
DI zflzl szl¤
=E] {ls.-z}g -tr9t9
qlg a+ "llHzl u=3?u=0, E).
:d =91=
A+ k(A6JE AE= L}$tllb 4E)e+ llEE 8E traJ 47. -EllE "l+6t{ 2iJ:l EzlE e6J 611"-l qlq
Birge-Sponer
ql E=t+. xl= aaB + ?l+.
fJ2. zle_ld f,i{!4 dE4+r{g Ez}g flzl¤ol tr8. Tlill-.Lr-ql^J= TItl dolzl "J"lB trll Eld dolzl-E^l4e
t44 "ÊEeq1,r1E
+ H+lg r1l Exl9 d7l l6t^]z} EHI=zI E"ll"t E trl+ "J94zl qEq dE dolT} p, R 7lr! +aE *=
.'J+= dolq. trI. E "JP E4-H OTlrl ;16= zlzluxlQ.
tr3. 4qd fi{14 dE$+Elg(ar} ¤¤¤ z}C !9. tl5ol Raman g$ol qqfl Ezlz} dE"6J trll ¤+E7l HI
^4EHq,rlel
6J trll) Lu=-t- I ol+. =^l H6llo} +trI.
e4. Morse tr1E!¤ ollLlr! il+= ular],tJ g# 444b rll ol trr0. tlE Raman gl6j fil!4 dE4 +=lgap+ ¤+
+e + el4. I zlC6J 4l)^trlEHq
Au= + rol4.
trs. zl$ zSxl4eld dol} 7!E dol+(u=t+u=0). Drr. ,lal-^J Raman Stokesel Hl-Stokes CEol O, Q,
tr6. u1-aelrJ qE.ql sFeI Hl|T.lE EolTI "J"lt4(u=2+u=0, STlrl?EE ?*+LlÊEHql}
tzt, Ert#l
=s-d^l=
.rlzl
o=. --'tI +4 rl {E
llE 6J G@) = (u + l)i,i = (l I 2nc)(k, I m"u)''' 2fl71gz[, aot 4E zl4 1tc.4b
mcfr= mtm2l (mr*mr)
4elc AGr,**,=i 2gx} Exh as} {E zl-C 11C.6

ûlEH(rlE)
Morse ElHl¤ 9luJzl V(x1=ftcD"1l-e "'1' trc.7
a-(m",,at l2hcb)'''
a5 aj(zflzt tsz}) G@) = (u + \)i -(u +j)'x"i,. *, =i I 4b" Morse stHI¤ .llHxl 11c.8
4e_ld LG ,=;-2(v+l)x,.v+"'
.r_
HI-aE+ d$zt 11C.9b
ÊEH(4jE)
G{u + D - G@) = 2i - Z(Zu + 3)x,i +. . .
4IlHllAE 1lc.r0
6il4 EI+ Do =A6,,, +A6r,, *...=IA6,..+ Birge-Sponer E I 11C.11
dE_qa 6J{2gz} Ez}) S1r,,r;= p+!1i+EIe+t) d+ql a.Jg sld llc.12b
4e.ld ioU) =S(u+t,/-t) - S@, l) = i -2EI P7l^l (A/ = -1) 1lC.13a

ÊEH(TlE-Eld) I =l'2,3' ...
io{/) = S(v+t,/) - 31r, 1 1 = 7 Qzlxl (A/ = 0) r lc.13b
i* (/) = S(v+ t, /+ t) - S{r, 7; = i +zit(t +t) RTIxl (A/ = +I) 1lC.l3c

I =0,1,2, ...
i*(/-l)- vo(/+l) = +8"(l+)) a"-J iI 11c.15
i*(/)- iuU)=sB,U+*)
Raman in{/;= i,-i++811 -i) I =2,3, 4,... o7l^l (LI = -2) 1lc.l6
ÊEe({F-sid)
iu{l) = i,-i ezlzl (A/ = 0)
v,(/)= v,-v-+B(l +i) /=0, 1, 2,... Szlzl (67 = a2;
EE 11D trlflrlErlel 1=5zJH
Hl-d¤ EzI9 A+ql= aEe+ +lE + CE q= *.J +9

> ol EEE Hll+= 0l*
t lill 8rl qflrl 9 ExI uflalE g:6J +EtLl]ot 6FrE 37}]el 4s-zl g,q6}q
T!5 A Erlel 8^llel ?zsoll
(rB 11D.lb). trI{^] d¤ BzlE a+ql= 3N-:zJl * z4l4
^trlEH?
T]El8E= E= +
-
?1= E4 fEe.e 'Jal olEqa ?lcl.
4+ E+l= .+l+ sld EgE +4.llq, Hl-d¤ EzlE A+
> tr{d 7]lE 9lE rN- 34t + 37H= 4+ qd H+l= ++d+. rP-l6tol
+flrl Erl-el TlE Erlel 7l= c5 ,J^l= )l^la_ rN-s(d¤), E= 3N-6(HldB)zHzl flzl¤9 Hl-sld t..ll+
gltt. ^s4EaJ,=
E4-et + H+l= +4utrt. olE=g 11t- %l-^l"J aol4 trt+^J 4lE,'J
+= r-l-q-r+ Ag +e-l +H4"J {E ,J^lg +=trI.
> EleEt qHl rFl ^lE
5El I!E-X[(E4 7E), E#e] gHJ4 flal(e4 11A),l"alr TlE
.E#loll^'lE 5e4 7al(11c)E +116lr. 9lolot
dB Ezh lv",u = 3N- s 1!EU49 + (11D.1)
4eldI+ Raman
Hl-d¤ Ezh lv,,r = 3N- 6
Etrl..
2il4 Ezl-= A6Jol azl4o+ {+q= + 6}+9 tlE "J

^l"Jg
*=+ rBl+ 4flzl. Ex}"llrlb E= a6J 4olq+ ¤
ei4l"1 Hg + ?lzl ullEql Eil+61 "*g TIE *4Eol 44
(b)
B + 9l-9-q, d+ 4*61 +d-61+. :z$zlq! ol
ÊEH"I
+d-dE ',71# {1¤. "J^1',9 zllHg ol+6}E ^}B6l anlE
+ el4.
(a)
110.1 7l= t!= u^.! fal 11D.l (a) d-d E^lg B|1:BF= LIE[Ha1E 2tll!213 E^l6|{0t Ltrl.. (b)
Hlde E^lg Hl1*= B^|6E1E 37Hel '-+01 "J9.6l.tr1..
4flzl. Ezl-9 {l# ¤4d+ a +41= dill +lE ,}4E

+E 4lt}6l+ 4014.
zElEt q 11D.1
xlE HlAlOl .^ E Bzt H2ob HldB Ezlol4, N=3olil, ulr+^l 3N-6

uo o -r-!I
=:zH9 dE ,J^lg zlzlt_ gl+. 6J¤ d¤ rflz} EzI"J

Nzl ilzlel +lil= H^l6IeJH E+ 6J6}l^J 3Nzflel alszt B
co2= 3N-5=47HE dE "J^lg zlzla- 9l+. E rllBHldg
s6i+. ?+ flzlE zl-tlE 37HE 4E(a y, ") z)Z HEI^le
=
oEal +lil= lszfle1 flzlE qqileq, 3e7HE {$ %F^lg zlzll. !lr-|.
HtE + ?lo o + olfzl-=."al aill H+lel +
E lruz11z1 ¤4. ol H+].e.J44"J Er]E4 ,J^lql 44
H +4e +g + fl+. qa4 EzI9 A+ +CE 9ilE E
^16l-=
trll :zHq alEzt gs4q, r?-l6tol 3Nzfl H9 +:zll {5 "&^l¤ zl* a+6}al 7l¤61+ ,JEg '71# oJ^l'g
zI Ez]. {zlle.<Jel E4l gElql 6l]B6Jtr}. +"lzl 3N-t H+l 0l+61-= 4,"14. 7l= I!= u4olri EzI9 e* +dol re
53 Eztq 4+ SF "JrlEol4. 9g uHalol saizl ?*1, szl¤"I t ^14 s + &E" alt EzI
+zlql^l d¤ Exl9 U}]aJS +4q48 zzlel zlEzl 9 tl5ol4. EI TIE *zl"l E¤ trl= 4lE qlLl zlzl a Tlt- ,,J
,q6I4. 4 ¤xll4e + EzI 4.oJ afioli "J6&g 444E 'll algl Botilo'loi 6Iq, eg Bzl-9 += 7l# 4E %ral"E
+lEe+ AEE Srlalloy aFb 4ol+(rH 11D.ta). rq+ oldElzl ?+"1"F dJ+.
=
426 '1 1 ErlEEts
v2 (2349 cm-1)
v, (1388 cm-])
v, (3652 cm-l) v, (1595 cm-l) v. (3756 cm-l)
fal 11D.3 HrO9 ll 7l= g l=. 7l= HJ^l vrE Efl +l+01q, qE Sll
Hl6t|,l1 '-JA 4+E LfEfLJtl.
v. (667 cm-1) v. (667 cm-1)
fg 11D.2 co2el Lll T.!5

?*=trl'.
g^.1. + E-d T.!E(v3)g 5g-d CE 8-=e.l ol 9lizl q= *4(vJ3 4E + t+ +l+ "JÎEE+ *e
Tl5+E
Tlffi AEtrI= ag +E-6Iq4. gHI4es Eql d59
,tl4 TIE"!_+ *e Affi *=+ eL zlzl +E$ 4e 71
zl= {* %1-^l E4g o}elts Elfl¤ qqzlzf s.Ed B

=
H;^lol f,fo.J t+ol+ ++tI B-Jg 5E+ A+(co, E
(a5+ +l+z}qlrJe+ ?ol, Eq llc)ol+J. zl.¤6llolEJ 7P" 6t z}e]. eg)gl"J zl-bat4E 4o14. gHl4eE ,l= rl¤.
"J^l
4. dxlle ElHl¤ {lHzl} s.EC ¤ol oltlq, Hl dgg 3 A*E t+r+ B¤ol 5rl4_o + gq+= 4"6J4 *F"l
aEl4(Eq rrc;o1Ir + trl+^l 7l= 4lE "J^]Eg sd6l + ql
+. +qn 7l= HJ^lql^lE gHI4 oE +4e flzl^b zlH
B4"l otqq. r{E 7l+ 4E %L^l E4* 4flz} EzI9 g gzlE+ E ¤-4"J+
4l# ¤B6l+ +e 9E 1"14. 4flz} EÎel T1+ tr-4= 7+ 7l? %r-^lq ql+ TIt- "JzI
:zB ilD.2= co,9=gd"l ql TIE
"J^lg +E}u 4o14. tlE
,J i urZ zlzla- E^l++. qlE^J 37HE 418 "J^lg *= E +
^l
v,9 E|le t!+_q_ErJ cxl t}=llE +a gzl-= +c o E + zlel a+ql= dE
^JqE (u1,1t2, u)a -E^l6J+. tr|+î HrO
gzlz]. f,.r.14 o + Eq*+ +7t+ 6l+ 4lEoltrl-. 4lt- Ez].g Elq dE tlEll= (0, o. o1o1q, (0, 1. 0)g a4le+ rjlall
Îa
*^l v,i HJEHfl t!*-e-ed F,$a ?)zlzl6}tleg olo-}e E HlqI t4oll" E ll= axl E= ^JEIql gt+= ag +EI
-tr ¤-Eo6E +i gz}Tl J- HlEll HJ6Je-tr- +rE"d-+. ¤-q + u4.
+ E:d TlE ,,ol ?l:.rll, ¤zldE F &a i)zlzl qA ¤e
+ql +zl6i7ll + Br6Je_E +a gzl+ r Hlql B-6J9_E_ + 11D.2 {eld # ÊEaJ
E++. ol BE d$g ^JE +zlq= Htlql,<J {="aJQ. ol
E E= {F "J^lql^J= A"* +CE +lile+ $z[ ul]o]"] 4l 4e]d g^d"il +iil4 dq +4g 2fl4 +zlql 'il+ g
'il6J
E r+Cql^J H6Izl *=+. HI4 +! o ++q z1d +g 4,o14(EE rrc).
aE+Cg 7IC6IE 7+ 7li*4qzl +B4tl aq 4lEozI
ilH g*6lq, "Jzl-+ urq 4t gluJzlE *=trl-. olag +
,l= %F^l$ql Ells"6l+ .$f;f {zl ffiz} EHlEel H
E+= +HI6l+ aola|"i ¤I+.
+E +{L]]H tr}s=r+ eg 6}=0l g+.
olfl C¤ol ilEzlel q+E ,tlbql H r oJolp + fl= a
Gr{r) -(ur+!)i, uq=0,1,2,... i" q-= :-(&t)"' +E 9l+. qle^l co,9 A+ 'lla d+e 4+zI s.EjEE
Zficl*, )
Hs+^lzlzl $eq(oglrJ; rH nD.2- -H_oleD, ul4,rl ol d
7l= u4Eq TIE-* t^+dl (11D.2)
t. r}4g 4e.ld Hlg^dol+.rel+ HI'l]a d+e dE"e- tril
¤zlrJ rrE +l='- *! q9 EI+E^J, ol {f "J^lql 4qI C Exl¤ Hl44 " + "JEzl ql+ql {---z} EHjEE Hs|.^lzl
*+ tf| e+ *a 4* *q4l el=+tr]-. ¤elol z"}6}.a +.E e q, EI+^l ol %F^lg 4e_ld QlC"14. ol A+ql= /C+zl E
.Jol argE ulfzt t'ol7l-r. El4^l Tlt+71- +ol.4l+. 4lF Hlezl+<,ql ¤B6l-rll E6lq, ol 'i*^lql 7l"Jq= dolEtrJ
,J^lel +E e%Fe Tlfql^l gEo 6t= e*E a7l= +4.11
B nl + #.J "J^lEg e_5 4qd g^Jol+.
q "JHI4 o_E gzl¤E a+=ol a-Jg 4o14. qlE^J co, ÊEHoltr|.
"l=g #+ql +4+ 4+zI HEI¤ "Jezl4, -:.r-lal.{ ol5
E Eila +a gz}Tl 4zl t4"lq, +s e*+e ol ${sl-t- dolE+El El :-fl=9o14.
e*ql"J E=6J+. rq+ Hlr]]a t+4 Ec
^l+ql^J=
F &a gzlel
dtql^J= ^ll gzITI E+ ¤-zlolq, El+^J ^ll $|zlfol Ef E@ 4qd gBHol clt-et Ei{t4 dE+ r.ret
0tE
+tr 4elql zlqE ++(7lq CE=ol trolalQ).
HrO9 tll zlz 415 'J4g rH rlD3ql +4.+1fl+. E.J 4* Ezl-E +ql^J 4eld gC"J ag "J6I{4, N,o,
110 trlEfl.Erlel TI= E!-E t 27
olzt "Jo]B trll= qd tr4 dolzl 5-^l4 o tr ololu[,<-1 i4

OCS, H2O, CH2=CHz.
+ TIE dol9 +"J g+d trHdql q 448+.
r'e{Ef 4eld gC"J EzlE=$ AE r+¤ql^l H+ de +?lz} EzL9 2H4
ÊEH"I u[!z[zJ-e.
^lEl Ezlqlde+
E "Jgzl- 4-ia--lz} EHIE= 7l4ol +r+. IrluI^J Bzr Hl zlzl ]aS +e}U+ ^4Eee-
Hl-d¤ EzlE A+q= Eld ul^'ll +
a 4-izf EHIE= Hs+^lzlizJlo9-E$Elel H+ az| ullf- +d-6}q ts46r717| qB+.r+61 +d-6}zl ?+g +
=Hol
E.+6ll^l)el q+= ++6110} El+ z}4r 6Lq+E {fl 7\+ 4t r}alol flq q4 419
z119
=
Eol c¤ EzI Nrocl ocs= E + ¤+ d7l 4-:a--z} E_ zlB dol, "*3 ullal*-, r4r g:g a.J d=ol +48 + 9l
HIE= 714q, ol s-HIEE=g 9ult ¤B"l 4. olES ,+r+ s)4 ul.rll fae] ¤+qr" r46}q ^JR6l
E++.+"J otqq qz} ¤a +ql +{f, #oJg r %r-o}
^]+qq+E g{-a3 4e.ld
ÊEHS
+4d+.
¤+ t}(.lill, +a4, E= r.ill) +ql^l
^lEg 49ld ^trlE
el d-:z-lzl¤ E++^l ol + E{^= 4e-ld $C
^Szlzll ++.
olu|. Hro EzlE ¤+ rd-:a--,,z} EEIE= 7l^lq, aqle-l tI Hg +4618 olqa3 $f,l¤"] zll4¤+(E= alA* aL+6J
+ol+ Aq+4E Hqql E6ll^J ol ,u6r-:a-z| Ed=zt H++. q). Eal +ql^J= Ezlzl ztf+r]l qd4zl *6Iq Hl]6}ol
r?-l6}q oJ $zlE zleld gCol+. CHr=CH, +zl+ ¤ a+ H6l-+71 E+e +zL==r+ +Eg *+. olfl p$tr. oJxll
7 ,{-=_1z} EHIEE 4zl t*zl"Jt4a +d¤. zlz]|t_ ?l+) +ql^J= qd tlE{E f$ol rfl+61 5}eq, rq6}q +Hq
qlaq fl Ea flzI 1l9 F c-u Aogol 4ltlqg^J rE" qlLJzlel +ol Hqd+(Eq rre;. oli.lH += +E= qE
^l =
1st: r-tolq, q+^l r- tOo/o7l +zlE qd
ql 4E +i gzt tlel + c-H a6Jol "J+q= 4 Ae ^J4= HE+Î4 ¤
4l5ol "JqqE 44"1 AAqr ,nr-=_z[ EHIEzt ¤C¤ + gl+H +H Eld s4z} lcm-'E *E 1"14. "l4e} a
+ 9ttrl-. 4 ql$q dE sld +z7l *4lzl4, trl{^l ¤+
t EzI9 4EC ^trlEflfl
"JeI4_"_s sld +arl +4+
# eE rrpo|^] 6J 41F %'-^lol zleld g¤q] 4E q oF B ÊEH3
¤Eql Hrll Eltl dEol +4+q, z$l ]4
+E AAq+ tEql "J4* iil4lzl ¤zlql +611^l ¤EEt ÊEH
4,"14.
. r+4rllzl ?+=+
4e-ld slqt deql^J El^J4ss ol+9Erll,
qiils ÊlEeg
^lE. +E +q E4l E4}^lvlA+ se riil +ql
Tl7lB.7l11D.1 CH,=CH, EzIg 4qd Hl=ld 7l+ %F
49 ^lH6Iq4. +tl^l<14. ol+Al 6H^J E= $al =zl 9*e B

ElrI Ê=Hql= olBl+
tvf. *p &E_ s i{e hfi[o$ h69 lo5&P s-c *a .E 4e-l a+qlE "*g ¤-+ +EI+q, +,s.6J
=aplvt ,J!g ^trlE
HS zlf {E zlzla- 6[4ts + H+ rqq Ezlzl-
qlt6l a+qlE. +lE +zI +ql fl=
ap+ {t¤ 7].¤6J 4*
Lrn- + roJ +ill4 dq +zlg "J
= z}=-H-H zl4
zl$ol({lE,r-l ^trlEHql=
NH, zll 44 r+* =q
v}+ ¤q
+^l4o} 6J+. ol z|{oll,<"1= qI Ex}e+ 6-J o}z}qE dFs++ ql^-l ¤+E "Jezlzl ul$ql f+6}rtl ols"* + 9l+. r46i
ql^l + 6t+E g^d ,J^lE "Jzl,+7I H6J + gltrl. 6J EzlE q ql+61 Be +E ts4¤ql q6} zl$sla ol
,}^le] +ge-E +e qlq 4 ÊtrHEol
- qlolElE olo-" 6fol /J-olt TlEol +48 q^J ¤-+ +izl
^JE]]E+q $efr {E
Htq
+lse_l dolE 7lE d0l4r .J+. qlE^l H,oql^J= 34lel
=
++g ql"lq s7I "JEqeq. ulzl $zlt{ E}q} H}+ ^JCE
7l= %I^l 7+7+g
=Erll
aFb lzH9 olr]6J zlE dolEol 9l E +dg ol- qlolEl se+ ultdi 4ol "lzl +
g + 9l+. + (1,0,0) e (0,0,0), (0,1,0) e (0,0,0), (0,0,1) <- (0,0,0) ^trlEH
4q eill= 90t4E 4*A1?l ¤ + 9l+.
9 rll zl$ dolSol gqts + 9l+.
Hl-eglcql E6I^l 2zll o14-e1 E+: %IZI7I +q6I= a
olr z|;.6ttrt. olBl6J dolE H]|TI=ol4_1. tl4. H2oql
11D.3 tlE Raman
^4EeJ
,<J (0,0,2)e(0,0,0)rl ?f. d"l5 {h H;1T!=ol+r 6}q, zi)zl +zlE ?* EzI4 zlf dt"J^l=g ¤+E HElzl
?9 d"lE
(0,0,3)e(0,0,0)ri rll2 ufl{lsolr+I 6J+. Hl
v3E ft}9ol"t Raman 9C"14. qaql "J46ll^l ,l= "J^lE 4
aE+/doJ ${la}H (1,1,0)+(0,0,0)4 eg Aolql^Je+ z)ol 2 e.ld4 Raman 9C q+= E+ 9g6|rll E46I]-H-E trl-94
7]] ol^Jq 7l='rJ4lol 5r^lzl o + s=EE dolgl 4s"61^b Zl ag HI|EI +Elg Eg + 9t+.
A q7]. +49 +E 9l+. qa +dg 4e]d4 Raman9 oJ+
zlzla_ 9l= +zl-=
ÊEHql
2fl71EzlE a+ql.(E4 rrc) TrF d ol E+ gC"J 7l= 4E
=fl= Îolql^J "J^lg rte + S.+. H;1E; +4
t28 Erl.#
*alol "l Eql E+ Hlg^d"J + gl+.) tlE ,J^l

(7]|= tl5-
0E ++g
"l EzI 4+zI EHIE. Hs+^lzlbzlE zl+4 /\
f 9lgt, + ol +zlg ol+6IH Raman grd"l "IH z16 B "J,\l
49 4tr6J + 914 =^l'c

{,
lL
ztEEt q 11D.2
co,9 qla t+eEzF=+Erll iI+ as"+=4 9I+6I taJ

g.q
=zlfi H+^lzlg +
tr++^J ¤+E.E HElalu_e ol t/ =^l-d
%L4g 9^d"14. CO2E rla +cg zlzla_ gl o Ir
Raman U
e. u}|4 fl4z} zi+qq, EI+^J 41+ AE %F4e 4qd lB I 1D.4 Raman lEJoll^l EB-6t|4 uI
¤ g^lsl'= t1l 0lEEl= E=E
s^d"l g + H+. HI-'l]a 4l+r+ + EEg 4qd gc
x{ol
o---1.
oJ{, u}z},rJ Raman ul¤}rdol4.

ql ¤qolrll 4}*qq +s= Raman C9 rllzlE 4Catl ol
q^l +z16}zl t}*5.]= d9 rilzlE +a6l]ot ql+ ¤%lqzl
Raman {E %r-^lE¤ zlA6I= ql5 4l*
?*g Hol 4}*qq +eH ol + tllzlzl eg-q pzl r4l zlll
"JE ¤+ ÊEH{=E
tlEI= E= aol E¤.ol g+. "JÎ +^ldE ¤%}
,qlzl 1r4 Bfl6}ril ¤%}g 4l
+ld+. t+olol il+el ¤r}g rqle *zlalE rr=0ol qtr
Hql +z16l-rll ¤%IE
Î*"JE trI{^l p=0 ol 5l4. pzy 0.7sql ,lqA4 :z ol^J"J dg E
+%Iq ,rlJzl r,,ul= EB-6ltA HlE}a +er p_tr. E.^lq}+(r
F-I rr.r l\
-d rLtL).'r). 7-1 ts-6llA$ d o e, r?]a p<0.75oJ dg Etsg d o + ++
+trt. Sd6J'lla dF"Jol "Jrl-+Îdq ¤*g rqe +zl
p
IL iiJB-6l.l4 ul [tre]l (11D.3)
ql +srll 6J+. rflr Sd ql4"l 1+E A "tH
/,,
^l+"*g
+ql. "J^l +Îdol +4
oJ.Jel +Îdg +s_ril g+ 9l
ol ¤ +d6IEJH ¤"* BqE olf-oll.{ "J^} *cE ¤'}H sq EI+^J E%l-6l]i +4utr1
ÊEBCg
=g-dT]ILJE
I r. 7!= IIE HJ^le EzLg e=* 6dr+ E}]6}-3 Ec}^lzlzl ?* I 3. 7l+ 4E *alol ¤+Eq H+= +HI6IE Raman E¤"|
e i]iE .Jq+= flxl-=9 5ag H+lol+. aE* +15¤ zI +. +Al4 dq +!g Luu= + lol+.
c6IE 7l= %'-^lEg rJg 5Bzl"l4. a 4. ?4q] 96]E "J"J Ez[z[ '}|a 6Cg zlzlfl qE T]
H[|EI
2. zl# *alol dzl 4+zI EHIEE Hq¤ +HI6IH 4eld E %I^lE 4eld4 Raman "J+E BC"l e + S+.
=
Ed"l4. +814 dq +zlg Lur= ! 1014. I s. Raman E= dSol "JÎ +ÎdE ¤+g. +
ÊEHql^J=
,q6}q, Sd r.ila dfq $dl^l "Jqt{.
=sEt^l=
AIZI
oe. ,\l
'1 +4 HE
^]
7l= %I^lE + Nuib=3N-5(dB) a!| {5o14 EBzl' Ng g^l-+ I lD.1
Nuib=3N-6(HldB)
7l= BI^19 4lE 6.J
Gr@r)=(ur+t)ir, aet tlE ztC rrD.2
i r= (l I 2nc)(k,., I mr)"'
¤+ 6114 Hl P=IrlIu ¤+ 6ll^ 4; pzlo.7sql 7W4L+ f- olt 11D.3
¤"*g )J; p<0.75
EEf llE C= Îrfl EaJs Ell O -EL\{
=l L-I
> ol EEE ull+.= ol8 GtrEil ruoq 7 l= d= r*^#==or qe 4Er

=
ExlE rl{g, 7l= T.!E g^1, Lalr. dol= xlHH6l.= dE4 +El c,, +ql +61+ H,o9 7l= tlE *^lEE qia +E¤-
^l
gXlE 0l6ll6tE I!5 qIEH= E46l= tll Etol gtl. E6Lq+.
^tolE
> EqC 7[E I'a{p|Al',E} *d ol Bx}E:+E¤
^lp6}r" "lq^l
E||a
Erlel Tl= g^13 Erlel rH8oil qal^1 E+-g + ?rl. ¤t+ ol=9 zl-tr91 4t zl.tr .E= *=trHzle polld).
ae #E g4}=e E+ E"JA zlEE zlzltrl+ 4 #E
> "JgEt qlHI xl^.! Ella ¤4I 6lLtElg reJ6l-E ¤4. (c,, +ql= 4 #e] ql
qflrl E^le.l TIE Atr4EaJ(EE 11D), -Lalr 8714.109 qe
i1a|= +^16lr. glolot altl.
4 E&"1 qz}'l a}+sol4.) olq^-l glql^l ¤B+ trIc
+4lE e,.l¤ E|=+. zlE -EE ol-o" ol.{ e_E+ gql +
e+ 9l= Ha4 sldE
'Ia +#
"J"tu+.
+gz} EzI9 zl? 4* r}4g z EzI9 4aq E46I^l ol EzlÊ yz_q t}"ll gtr" z+ol HoH A.J4g E
ggalH ,l]+ zI+61 4e-ld ¤f^d'Jzl $$ px,oan ¤]C"J^l =ol
ts6Jtr1-. 4 flz}g H+l EqE¤. rB lrr,.roil +4.llH
^ll
el+g + el+. 4. cr" +E zlg Eql E6lts rlla ¤{l^==g E, c2, ou(xz),
=
r?-l-r. oi(yz)"|tr+. eTHE H+] ElEl= qu 4+E ¤& r
11E.1 E]|Aq g4'-d 7l= T.!=tJ^le! E+ E ¤6Jg gzl S|ee__e. lB)-eo!q. q Eldg Hg4¤
E e-= H+l Eq= += +lile olEo lzl{, r}Q,<l ol5
?+ 7l+ %r-4=g Ezl d*9 zle+ _s¤9 qL,* qla +ql E zlEE dB ool4. o?lzlE x* y H+l ElElEg *sz|
+$= 4,-o -e E+$ + 91tr1. ol tiFE q-q=r+ eg ¤z.lql H6IEE zlzJ -to]' 5i.t, Hfl EEI= ¤olg $zl $ee.
trt=4. tr +rol E+ tr+El4 7\cr1--t-1+1=-tol4.¤4Io"(xz)
1. zlzl fl45 4 gzlql 4t rll H+l EEI (*, y,o) z)o14. Hg4¤E E= H+l EqE += flilE ols,<lzl{, o
=
wszI EzI9l qlql^J= 3Nzllel "lBl+ zlz] a;'17I glrll flz19 / Hfl ElE]= FszI E6tl. *4 z E+l ElEl=e
¤tr]-. ¤6&9 tszl ?*E+.trt?+^J X\o,)-+t-1+l=+tol4. S4}
2. 7E g4I=4 ?+ # cql 4t zls x\c)Y r *9 6J ¤& o:,(yz)z 5 Hflzt9 , H?l Eqq +s= H+^lzla- y*
s.rl¤- rel6}q +61111 lErll, ¤tlql E6H^l H6lzl ?t z H$l ElElEe g6&3 gzl ?+=+. ogÎ9l 4"1lrJ=,
+ Tlzl 'J+ql 46ll^l= l, :zr-11 714 oJ+9 *sz| H H+l BIEIE .flsz| E6Ir y* z Efl EEIES g'Jg *
ol-H _r, rEr olaol 4E Hfle H6tE 0o e +=+. zl ?+=+. q+^J t\o)- - 1- 1+ 1+ 1+ 1+ 1-1* 1+ 1=3ol
3. d44 " + +g s¤g zlo_I s¤ o + E+6tr" fE +. tr|+^J .g¤E zlg.t' 9, -1, 1, 3ol+. t0C.3a4-l$ ol$
^dE
6Iq E+6IH 7tE *.¤g qa + 3Ar+Ar+2Br+3B2ql
+¤ zl-s.se+ r0c3arl9 6}4l 6iq f)(ge L++u+. "l
aal+. E4l +F9 4a + 81, 82, "l e'9 7l^lq' qd g
^l-s-o
n(f ) =
ilrt.l N," (c) tcq) H qla 6 B,,Br, 'i Ar= +=+. IIt4^l ol- rllTl^l
zls 2A,+82717l= dE"'iJ^l=E^J tsEtr}. qlt}d qle 3
¤zlrJ h= +E il+, r?]a N(c)= +ce-l ¤4IE ++. zl4 z1? *rl5ol
4. x, /,o) z(E4loll tll+61-L-)ql ql86l+ r-l]a +4 x, /,8) z =zH++.
+flE Eld(&, & "f RF s^l)ql qls"6l^='lla +-
zlla++. olEE 4a +=g zl* Egl ++qq 9l+.
s. 4olzl qla +Ee 7\= 4E r}^lql q+6J+.
430 11 Erl#
c6
-zl o"'(yzl 3 n-r AElg galop. EzI Eql +z16}+. on$.$ Ezl-
E t}"ll ilsq, E6J s3+g Cr+4 gil++.
o,(xzl *d sflzlE E+l EIEIE ^J46il EzI. ol flzl-b ?+
dr-oll !lo
s + zHfl ElEl= 6Ji zAH H+qqo| alQ zl
X
2
E sql E6ll^l '{a + Nr,E *=tr}. u}$z}zJ-E ,e} r H
Y
+l 4ElEe E E+ E'i'lH H++¤+.
q-Sql= rflzl¤9 ezi H+l EEl#
^J46]l E+. 5
5 ¤tlg ot+ HEIE "J .Jgzlo* dD=eol4. c, ¤
fg lE.l
1 H2OE fl^l E?let 4ltbl.= r1l olEEl= qa -e-A=
tlg E= H+l BlElz| galp e. xQ)=0o14. qI EA{I
^lE=
B-F a'* ++lE c, gtlg a.J %r-o&g 6J6lt H+l BlEl
+4 rH rro.3(Eq llD)ql^J u,4 v2b 4d e,g zlzl q= ¤'3-g +zl ?tzl"J trt= + EEIE3 +E= Hl-+4
4, ,re qa Br= *E+. v,al v2Y E trl. ol +el "lult ++. 4E rflzl¤E H+l ElqEe ol# t+. tr+4^l
¤tlql 9ullrJs H6Izl ?*eq q{^l zl+5o1 FF tol
dcr)=l-l-l=-1ol+. oh9l 96ll^JE 4 rflz}9 zHgl ul
99 "l A,9 adg "J+^lvloe ol u114g BH+ aol Elel +Ezl- Hot{trJ ** y EEIE$ ¤o-lg ts4 e*Eq.
4. "le} 4a4_" + vr9 ?+ql= cre+ o"oll 9dl^l H+l rrl+^l zls= x\on)-3r(-1+t+1)=3o]4. Srgl 4t xl-s
ulrlzl H6Iq, zlEE-oJ 1, -1, -1, 1ol gg BrE H.llaq=
c,ql q6J ar+ E"J6Iq q+^l ls:)=0ol+. + +A
4o14. =
t s-r a6}g E+61+ Eql^JE o,HlrlE a.J + HJ.J
\l7l$.7l 11E.1 C2, +{ +6hb ,tl+g HrC=o$ zJf; el E+l Elqq ¤o}-3 +zl ?*e4, zEfl EElqlE ¤6.19
TIE %}^]=el E-l]a +E¤-
^_lB4q+(Hrooll^Je+
aol +zl ?+=+. r+l+ +E ElEl= +aE H+^lzl+. qe}
CHrzl|= yz-$ t}"ll +=+) 1+l-l = 1014. EI+^J 7lE E¤el TlsEg e, 0,
^) z\o,)_
zflz+'B+tYg:6 -1, 3, 0, 1ol+. ol zte+ s-¤ ^llEE FgzI tlel E+i EEI
Eql q+ Ai+Al+zE'+Ai'+E"E EEÎA+.sflz}9 H
+l ElEl= Ar',+VAH H+qq,,r|4rl $dEI qla + ^ll
Hro9 7li 4E oJ!==g 4*zl A+ Bolq q4^J Hl-q EE Ai + e i+ 3E' + 2Ai' +8" o1CY.
sl+ +ql= 2zl?l oltlE zloJ -s¤"1 s.eq q-4^J 4l
c,,
zlE -s.91 E6IH ,Y t;'xlH H+tslq, *q yE 6J4l p'
E trl+= 4zlzl9+E+. qq+ rl-S ezlql^J ¤E6l+ HIe+ q aa+. z+ +flg Eld &= AiTlH H¤+Elq, xel y+
ttol 41s7I +g tsz}{l,tJ +48+.
E ++lel qd (&, &)b z-J4l E"^)H H++¤+ +]"il^J E
g sd ol# zllzd}E Ai+2E'+A;'71 4E
EEtr7 BF3E 7t= rl= g^t=et Erte
= ^lE
^.ll-Ee+El
HJÎEE 44 6:E=e^l ts=+.:.H 11E.2ql olE zlE tl
BF3E 71# 4* %]-^lEel q]a+E¤-
^lE6Iq4.
ol Ezi F "J4# ++'Hfl+.
BE +4¤ +a= 7l^14 D,n d*"ll +++
=
a.al= dHI4?l ezl+ H7l lE.rql^Je+ ?zlr} "l
^l¤I
Ezl+ zzlfl zlE s¤(E'el r)g zlzla_ ?lE Drn A+ql
+6J+. rr]6iq z+oE tr]sl¤ 7l= 4E *4 ,'d.9 ¤xll
v(A,) v
q 4ql^J 4lag alot *4. B?lzI t}el H+l Eq= F?l
zl¤q a.g El]a ¤^Jql E6H^l tlE H+Lslzl $e_sE
olEe ¤.r-j6l^l +l#6J + gl+. ol+ril +?]^lrlE al&
ol a+611414. ol Ezl-b 44lE flzlzl Bl-d¤ o + aq+¤
4olo e 67HE 7l= 4+ r}^lg ,*+r+. v(Ar"l v(E') v(E')
cr+ol f 4olq z*6}01 84. ol EzlE rr-H {.ll lg 11E.2 BF3e.l 7l= E= ,J lE.
=ol
?14. rzle1 Cr+r==g B-F A*g Er+6Iq, 37l]E o"HE +4 E'qla +E=g 2i|flolt,+ qg"qt rl= AE %r-
11tr
t rL
xl-=.
UO
/\ii{lEa{ol rllil
-l1O
_E!-,\{
LL-I
t..11I
Tv
--Et-]
q a4l E= ^JEll(u=l)E9 dol+. "l"l "J4Alul ur=0"J ^J

4Ee z+oE qslqqgl+.+lg E^l a4q ulqE zzH
Ell. Sd 4{ zle} -EtrrJH H+}qq, uq=r"J t4E all'}
9 r qa +=ol fzlla|{, "lE* ^J"l6J + 2+ flsI zl
zl= TIE'J44 F"J+'I]ag *=+.
A5 %t"^lq 49"d4. Elel^J Ai+2E,+A|,tr_ *'^lq=
= 1Cq +49 4g6h= ql ol+g= zlE
Tj41 71+ TIE %r-^lE +E r+2x2+1=6o14. E4l
rPl B7l 11E.2 C3, +ql +61+ "JEqo[ Nure] zlf; uq=04 uq=t
^LolE
dolzl cl$9}zl$ q+= aA6L7l +l
6ll^lE w4 v, EHlc u*=lvi uryodt&
4lE *^lEE qla +# 4H6lq+. ÎolE 4lol St---z|
+6llot eI+(Eq trA). 4+zl- .E.HIE ¤tlzlE x, y, Ey z7)
az+'YZ,E
H H++¤+(Eq 10c). Eq l0cql^J .H-"J Hl-e| eol ol 4E
e q4E EI+ viiw,Tl Sd 4a zlE s¤q ¤e olql +
Eslzl ?+=+.
11E.2 T.l= trl"=:d+el Elle¤ .JAI2 sl4EEI+q 94^] AA4=']la +E
^lB
tl4E *iwf iw.9 'Ha+g W,it, H rrroE9 44ql
lilg d5z|9 u}q rlrll ffia;4(z=0)i e--cl2s'?ql Hl
=sl- ,<J dazlE qla +=q zld+g a6}ol *g + gltrl-(Eq
E6]]
Ell+4 ¤zlrJ rE ¤¤ +lilE+q9 Hg"ljr, aE tr-++

roC). rlro9 Sd qla zloJ -E¤i]H HS+EItra vii,/,E ql
(tr-q 7E). u-rql lzll EE tlEflel ,rrl2a'zql Hleil
++.+"J+ -E-+ +d.+ EzI9 7l+ 4E %r4 q aql ¤6Jg +zl *e_Es WttE'Ha"Jg rEl6IB ¤+. E
qlE 4+^le + fl=ql, oltrI= E zl? TlF 9 rocglrl _B"J HIe| R"l ol vttt"\ Sd qta 7lE EBql
'J4ql ql+ dlzlb 6J olflg vtq ttTl ,JZ r{a +ql aArqo} qL+.
6l-= H+lEel aB.?l 7l= rlE QsE Hl^+qo} ++. qls^J
Hh+q "J6lH VlTl x,y,E= ze| E"J+ t]|a6¤ zlz{o} a}
corel 'Ia c+9 a+qli zl# alEz} zs,1-zs.2ol4. ¤zl aol+.
^J
&A gz} r9 z-Hgl4.
2o,,ts =
Hl_trlE+ ,l= {+ %rzl zlft alsql 4+ gEE
'Ia ¤&
g4= +_Hsl.l4r4 z146110} +E= Hs+^l7l= eE4.ul- +le-l +4 44= q+4 t3 f4oe eeYg + 9l+.
+q "5iH E= zlEz| 1 EE -loltrl. H1EI tl4 7l= 4lE *alol 4e.ld gcol qqB r qla ¤Eol a
+ 7l= sIsE zll#el aJfol{, u}4rl 'ila ¤4}ql el6il^J
/, E'i z * 4Y 6}+el qa 4"4 E"J"il"FqI +4.
Q+ +Qq7l q= E= Qr+-qrz| q= +4lH"l qq= g
a;rg ?zl ?+=+. E|+^J af{l 4aj zl_s= Ef rol{, :zr-l ngdoil gEt qe
^^|'
6}0l HIEI ii+E"Ei++ d4_"E 4? zl* s¤ol+(dB
^JEl]
40+A,). z]=JE! q 11E1
axll E=E ^Jql j'F="++= q6+ 6Dql E=61+ +El} BF,(dt Drr,)9 71= 4* *4.g +Ai'E qa
Ai+28'
qql Hl;ll6l+ .Jzls+9 +oltrI. olul $oll,tl E HIe+ ?Jolr QA +g *=+(H7l 11E.2). zl* -E.gl E6tH ,y t',z)H E
e sd 4x zlel s,Bzle H+|qq Qq+ 711 TrE 'J44 +qq, @,ii a;-so9-tr- E'aH H+¤+.r++^l Ai' z1?
t"J+ qla +g 4=+. Sd rlla zllt E¤4 "JEE qla TIE "J^lr+ 241E zf 9El E' 71= tlF EJ4Ee 4qd
a"rl9 zldE=g +zlql golg +zl ?*qq, q+^J a4 EE ¤l¤"lct. 7l= at. HJ^le ulg.col4.
*4 q^=" g--.E {ag 71+ 4E "J^lE 'ilar| t"J6I+. î
g^lEsl 4eld gd
(a) z l=
(o) zl= HJA1=q Raman =Jd
"J+ 7l+ 4lE',J^l.el qla¤. g-4 qH r {+ "}^l
=C qlag a^l-6IH 7l= {f ,J^lE zl$ $olzl-Raman &*g
9 zlE d"lzl-61+q= aqlxl nl-+^l 4e-lC g.C"Jzl9 ¤
444tszl9 q+E ill4l4"J "JB o E AAts + 9l+. 4 zl
+= 6l]B zlE EE ol9-o 6Iq drll ee.J + 9l+.
TlF'J^lel Raman ¤}d q+= +*g + 9ltrl-. ol HlBg
=
4qd ¤+^dg ea6l+ ar+ Hl+6Izl"J xr-=_x| -e_Hle ¤41
7l= HJ^lol !fl5 =Jd zl qtql ¤+E ¤&z}q qlag f E6110} +tr}. 94}4¤
=8 "l
+ 7l+ 4E Balol 7lE dol= Hlq tlql(u=0)E* 3 zzla"r- 3(f,xy fi9E<J zls. .E.ql +e+91tr1-)4 E"J'J ,J
=e]*
432 ErtE#
4eg H++qq, qg4 ae +zlg Ll-s-41 qi+. (c) u1el +ElE q1A¤
=4
{5 HJÎE 44*ol 2zfa3; gE 4a+4 * 11D3eq H}]4 +4e qla ^ddg "l*6}q +EE + 9l+.
"J"J zl3
"J6llot:z {f *ll"l Raman BCol4. Ezlzl qla +dg zlzlt- gleH r H+lE9 qta +e d
+ Hld CAql 44 g4 uzt ¤4. ol Hld ¤&ql 4A z1*zf
RamanS¤oll *-zl 4e 4 [
"Jolq^l E+l+ HflEol s&ql el6ll^J H6Izl g*¤. ollts zl

*zl szl qq, 6J¤ xlsz| ¤-ol"lrJ H+l+ H+lEg Y 6zl-
zlElEt 0{l 11E2
H6J trll= xlEzl- uzl- ¤4.
BFr(d* Drn)9 7l= 4l+ "J^lEg Ai+2E'+A;'el qa *f ,, y, ") z(4ol {}:a-z} E{]Eql +4+=)= H}dql el
+g *=+(!-71 11E.2). zls. -s-gl E6IE i, )?,4 l3 E- 611^l E+ *szl H6Iq, EI+^J
"lEg uszlE 4a +q El]
F eir+ E"J6Irll EQ+qq, (*-f , 2xie E-rEo e--tr E'zJ *ollot f,+. ole+ rlla4gF 2ito} E(Raman gCg zlufla|
H H+E+. tr|+^J Ai 7l= ll¤l 'J44 + 2+ sl3r}s', zl 4*zl Eldql E6l]^l E6Izl ?*eq q+î -szl gE
{lE %r-^lEg Raman ¤.col+. A;'& olul6} 2z}a3. g =)Eg qlE^J xzoll
*=+. 4aI Hld s4+ Fx)(-z)-xz\ H¤tol
=
E_ ol
'.il4+¤-9 {zl $ee.e ¤}c"l "tqq. E,
HJÎE g+.
g 4eld ¤*^dolzlE 6}l Raman g,golzlE. 6I+. + E +d Eilag 4= Ezl9 "Je-lel 7lG 4E rJ43 g4 u9
zF= qla +cg {zl gee.E uI4 fl42} 4ggzl t* qla +ql 4s" 6J4. "J"J zlf {f HJ^lo1 x,y, E.= ze+ +"J
7l? tlt- HJ43 l]trel qla Eg 4l:i u}^ls fl 4a 6* zlzlfl -:. C-$$ 4e-ld $C"l{, -z *!3
=+. î
g,<J EE B-F AuJEol E^lq 4l+g+. "llB6l+
11
?+"t 6J+.
"J"J 7l= 4E Bal"l 2zl6J Er+ ee 4a +g
Raman
S%r-ol ¤ 1-"E ,lqg+. rq+ E'r}^lg zlzl$, _z Alf,$ Raman $Coll" g?+t qI+. 7l= {f HJ
^trlEH=g
43 ge} u9 "J +ol + E + Set: + 4qd g5olgrl E
-rt I riF A I -t-rI -t -t
-t<t -t
.<loll Raman $C"l ¤ += S+.
=s-d71lLJ=
f l. ]tI z16 4lE %r"^lE 4{ ¤:ol x,y,EY z9 4? +r+ E"J a 2. el z16 rlE "J4lE 4{ 6ol zz}6} g9 Eila ¤:4 +"Jtr
g trfl= a 711*rlol 4qd gcol4. ulli: zl¤ *llol Raman i}^doltrI.
EEJ llF CII-8EJ| ^tr4EH
> ol EiiJE Hll+= ol*

Erlg 801-d Cxt SEll= EBqt4 dol= s^lo-lE Erlel q
E^t +4011 gEt tllolEl= ^tolel
Eg + 91r, ralopl ESlz ui
TIE r!5+el eil eolE Esg +=gE
?ltrl-.
i{0
=^10il -E ,08
(a)
> .4C TllE
d^l-gEfl dol= grl gEflE e4 6toil^.| golutrl. 500 550 600 650
=4 u[f,,Unm
> EsEt qHl rl^l

EBq(.tr.E 1 1A)g gU4 8tr, CE+ +41(EE 8C, 1 B, 'J 1 1C) 1
g g^|q+4 f.al-tr Tl=aE .ÊEaJ(]1C)= +^16[r. ui

8c)5. gr 9leE E80l E ?i
=.fl, -d 7|E(EE
?lolot Elrl. fl^lel fio
,08
0lrl.
(b)
400 500 600 700

rf}, Tlnm
dz| {l4 EzlE dz} 9lulzl rl-"19 dol
fal
^trlEflg
qlEql +4'Jtrl. olE dolE dE qqzlg=+15. 11F.l 7l",(l BqE 8x154
^4EaJ. 131 zlill I l2ol ^4EeJoll=
E^14 Hsl¤ + Eot|E TIE +azl E?.!tr[. (b) E-4 +011,l.1 7l=-d E=Asl ÊjEaJoll=
+zlE a+"ilE olBl*
Hl6ITlE 6Jtr|. 7l4l tr-4r-g E6[|EI^| ?J= 'Je qoJ E.?.!tr|.. (EzJE Ats Er] t t n0l^j ¤861.Htr1.)
ÊEB
E 54¤. E6llts f qlzl"J(rB 11F.1a) .+ill+ lrlloll| zfl
zfl afltrH dE"l I'Jqq 4E +471 S.= H3 qe q
E ltF.t ,Jel 44, I!#, g ollLlrl-
4++(rB 11F.1b). ,\tl
-1 )"lnm vl(l0ta llz) E/(klmol t)
Ezl¤g dzl. EeE Hs+^171:- ql gstl ollulzli + d
4eld >1000 <3.0 <120
zl¤E 4E7l ¤+(l eVE aI sooocm-' E= t00kl mol-,91 6ll UBITL
e-o 700 4.3 t70
'&6J+). tr++^l
ol*lal HEIzI "Jqg'll ¤+q4+ "J=q
t-e-}
+o 580 5.2 210
%IzI= zI^1 994 z}fld ¤q9 +flq(E
=
11F.1).
^qEflql r|%l- 470 6.4 250
zl.e-ld <400 >7.5 >300
. trl Ele <iEol zle ¤"il

11F.1 2flrl Erl ++qq fl+
Eq 8cql^l= qBrll flzi

a3-z1a.E olf-all.<J
^J-4E +4.11 dE i",E¤ aJd 4"14.4,
¤¤619+. zflz} tsz].9 dx} rJ4s 6* 7lcg=_7l^l
=zlE A= Lr+ )"r+ ... (11F.1)
r +ElLHLtrll, I f s rlolS flzl9 $d + qa qltql e
fl¤lB 4ag ^l-8-6110} +trIE 4o14. oBzl-+llE.J+{gF¤ qa)ql Eqfl= t"J dz}ql ql6ll^l
^l + ++lE
i l.=0o14. qc} n+llsaJf t} + qL 6I+9 dz}9l ql6H^J
(a) -d zla E l.= +1ol+. Ezl oJ zloe /el <lg q-q-r+ pol :zalr-
qlEzls +el.U+.
zeazl Ez}q a+ql= dill ?llE 4gt-=d=el ez} + cE"J
g B^l.J + gl+ ol dBql rI6J oJzl+= /E
'+4u4. "l l^l 0 1 2
"Jz|+E 1k+_ r+ dzt9 ?llE 4gE*e-l ez} ¤A + t}el t fI A

t*3t EItE!.lE
olE Ezl= L=0, flzl-E"ll q6J 6J zl-E S,

1, 2, . . . "J tl-EllE gxg=g uXu=g uxg-u (11F.2)
B D, . . e+ +^t6J 4,o14. dB Ez}e] dill flz}{lrJ

^gg (ol= +4g gE +rtr" rela ,rE -lE 6l]46iH rl-g + 9l
e+ eg rlBeE E^lqI+. flzI aJ TlEql^Je+ uffizlxJe ro}
4.) ol+rll Eg HldC E^l s EE uE 6J zl_s. 9-ffioll !z[
E tr}+E= L+EIrll= 25+ 19 <ig 6* zl-:2,91 g+ ^Ja^lE q r(= {zl{|etr
-a E"J+. A+ +lls.Jfz} A.+E) Ez}
E?l+.
dzl¤ol {iS ol$a 9l= or4 nre| eg dz} uflzli 5=s =
a++E d!f$
zlzlt:e d4l4"J Hld{ol' ezl!9"t tL
r+ I[I4^J oleiql ¤-4 zflz} EzI9l ql6J 6J zlsE 'rrol.+.
ol4. ol4al dzl Hllil= dill +llE 4ef"*ql zl{!i aixl
?*=ql, r-vl¤l-e- dz|5"1 -E-f l,=0"1 q4+ E= l.=+1oJ
zltlEt 0ll 11F.2
dzlfs+ -rql dzl-fzf ztz\ ullEol4. lor,9 {z} uflzl$ {
:- urE HIEI ^JEH a3- zl-e.E q4^l 'zzl ¤4. dzl u]lzlz| 2fl^l EzI NrE {z} ullzli 1or21o,21ru4zorzo1q A+¤ +ll
rofro"2rrjzol9] Nr9 H}q} ^}qlE u}4!z}zlg 'r7} ¤+. Eo}+Eg q i]]?14 9l+. H,e+ F,9 ?*s u|-alzlzlr|.
El+^l ol=. EzI9 6J 7lir.= ,r*ol+.
^ll
He2*9 {z} uflzl} tor2ro;o14.24E dz}E il]+ld e
zttrJEt oll 11F.l
fllE++ Hheql l7llel rJ,zlzl flsq ol +llE*+9 HI
q]
HiE HIEI tlq {z}
ullzl.} rojo14. E9 odzl.E }.=0ol
dCg uol4. trI+^l S=*4,,1=00]4 ajt zlE5. r:,ol+.
q q+î z1=0o14. 4zlzl6}+g9 ull=. s=+olq, IrI?+ Hlqtl-q o,9 dzt Hllil= ...rnjo1q-. 7r8+llEd:+=.ol E
25+1=2014. rle|,<J o3- zl-aE ,zz| ¤41'ffiE z al
^l trt +"J dzlsill+Jzlzl.| alx1u3 olf,i flfsulfE + d
:zrrl,4l- $lE+). zlt gHlddol{, tr|e}^j d4l4"J HldCg gxg=go]4.
NoE Htq tr-{ {z} uflzl} ...trc'o1q, ¤zlrJ ...9 s+ trI+ i ol llzl- uflzl"ll zlglqF 6"1-E=9rI,. 3Io, :44-A
,rq oL+ zlqE 6}z1 9+= SCg +llE++= +4U+. ^ll
qzlrJ *"J dzl-= 9g+ n+Js+fq qL 6ILl¤ zlz16} 'Arol4(z}++ {l rrr.r9 _H_ol-eD.
q trl4^l z1=*1olzl4 -r"l+. r?]r S=*o14. u++^J

o3- zl-a.E,nzl ¤r*1'ffiE 2 rlol'4r 9l=+).
z?)zl E4¤gE_= C¤ Ezl# _trs'-6H^J) eA Ee+
or9 utq ^J4 dz} Hl]iJ= ...lzrrzo1q-. + Az|71- E"J
t r7.llsQlfE ilzlt}E n =(+t)+(+t) -+2olr+(E= HI_a$¤- ol Eql^lE HIÎql 46}l^J 44"14. {z} uflzlel
1=(-1)+(-1)=-2). ol uflzloll^l= dz| 4flEol zl9 oJ diil4 'ileg +617]1 +l"}]^J= E|]a +JEJ+el dzlgl +19,
+qo} 6Iq q4^J S=0o14. nlEl-^l o3- zlc= ,az| Eul- re]r HI^HI el6}lî +.g.= El-+= ?]Eq}+q dzl-gl -rg
3^6Jg ¤B *= + 4*71 qL + n+lls,*iE Eolg olq^J _5r= dzl-=ql 4EI olE t= E6IH E+. ql
^fl$
ilzlollop 617l trllE"ll Ezl^L" aI4. dzl-=ol *"lt zr?llE g,<J Hri HIEI tr-Ellql^l + 4zlzl o+lls*fE E+6lq q
Et+= ilzldlE 1=(+1)+(-r;=so1 g+. olfl ullzloll,<J 4^l di-ll4"J r|]ag (+l) x (+r;=+rol4. +zloE ojt zlE
Eg ,l.4+ ¤BB + ileq tr}4^J s=0o14 ffq l}dzle Eq=+.=,rJs E^l6J+. dzl¤ol o?llE
= ^gol
S-1ol ¤tr|. tr+4^J ?zl4_o e + 6J':e1 :rrt rJzlzll ¤ EL+E"J d+6I:/ glE ullzlE qL Aol+ g¤zl o + +9
4. "l +zlel + 'Jg dill ^ll 6J +ql^l alxl9 olluJzl * Aill4 Eld qlag 7l4El. qlE^l H.i9 HI-EI ^JE]]H++$
4zl-¤4. {l ttr.z) 'z,lol+.
qsl tlg ruEzl fllraJfzl HI^Hl^j +44= Cee g
,'d +d-6I+. :.H 11F.2ql -H-oJ H].e+ *ol aJ fllEg'f= y o
Eq eBql^J ¤Eqi ute+ ?ol 5q 2g E4-= 'Ia +dg zI H6lzl"J +E 6l-+= H6Izl S=trI olel+ ^d¤ol 44
714q, olEE TJls.g}4E HIA^d(EHa +Cg F* HldE C
'l]= ar+= nTllE6Jfq ++4 B4e+ fllEaJf$ol l
ol
e)ql q4^J s EE uel ex15 +rll gtri. ol Hld^d .Ezl=
H rrr.:E zfE Q4l qBAl el+61-=zl= r.g+e-EAl EI4
co2+ HC=cHe+ ag +c .lla d¤ 4flzl EzIqlE 4+
uNzloil +t} aill
^le + 9l+. +dz} Eq 2fl^l tsxl-9 {x} "rq Hg zlzl4, "J4 99 Bol "l H9 tr-6lql +
4?1 Hldde 4 d+¤ +llEEL+e.l HldC4 ffi $zjl$ ol ^l(yzB)
4ttr1. ol +llEsl+= xzflgl^19 EIÎql E6ll^J HElqzl 9*
+6Lq *t z]|z]] dzl¤9 Hld^dg zlzl:il- +g + 9l+.
=+.
aJ¤
&E sin/91 Hleila}q, E|+^l p_s!l^l(xzE) "Le
11F drl8El| 43s
ÊEaJ
L
+
+
+
s
+
A
v
tz
-
:4= E:d61.=
fg 1F.2 E^l-+lE-Br+71-+
1 Eoll^1 HJ^lflg ttt| F67l- Eef
El=^ le-l q+oll tq a|. E^ I +]lE:Er.+E rt|d(+) !E= H l- qe(-) o + +E:Lttrl. lal 11F.4 dB E^toll^lsl ÊJrl flE 4EEaE ,t.|.019 qIrJ E=
=-ct:
+ gE=$ol.El=Ert.
HJ I
/1=
-lO
E
trI+^J +A qÊo6J+E rflaol?+ot s+.r46}q zlqloJ
4E++= y *(t,2) - n *(r r)n _(r.r) + n *(r r)n _( r, ) o I 4. HIÎql
E61l^l ol gL+= n-(rr)n*(rr)+n-(rr)n*(r,) o + Hd+ql ol
43 +p*(t,z;o14. ol gL+= ol HIÎql +6ll^J 44o14,
fal F.3 Erlel E^f +llE-er+ts g?14 sl=Eltrf. )lZ Eoll,\lsl q+^J 6J zla.oll Eq^.] ,r;r\ ¤+.
^JEzl +E
It C:-J ,0oll
HJ^l= +E= Eo+ +161.= zâl Atr,f.
09
Eol 44*4. "l ?llEEr+= xzEql^j9 H}^rql el6ll^-l +s. flzl9 a+e+ uf{z}zlE a+q II}+^l= tJEe+
7| H6Jtrl. ol + +llEE|+= trlslqq glir, tri4^l ol=E d Tlol= o-JTl di-ll 4tef*4 aJ9 tolfl'=+l'i.$ ^gE
B^l6J
B a.JE 6l+q= u|="alfol4. :z4at¤ ¤zldE *o + Bszl. 9l+. dB Ezlql^l= qA ¤e + ++19 dzll dzi
7r+=cos/*isin4i=si@g+ n-=cos/-isin Q-e-'04 + d¤ A6Jg 4++*"Jol EEdI4l AEqq, olag oJzh+ oE $;.14
+llE6J+E olso 6l+ql, ol==3 7+7+ ?'t=+14 l.=-l 49" 6t7l tri. pa;.ol q++ zlqe EzlE A+ql= + ++lE
qEql ¤46i+. rB r1F3ql +4U uls+ *"1 xzHgl^19 HI ^¤-+llr
+{E 4+E* dB(aq AD4 + +99 dz} f CE
el6]lrl cos/E H+Elzl ?*zl"Jsino. a i ozl H+q g6J6IH oE Aol +g+(rH rrr.+). ol dzl^s9 ^¤E
^lql ^d+g
tr14î ol HlÎ= r*el r_E ts E+^lA+. ,E Lr4qlq, S- 1, S- 2, . . ., -Sol+.' +,
Hlq t4q o,8...1ni9 dz} HllzlE 4=+. ol .$zlel 3=! '=S,
6J d-4(s= r)i {zfzt ¤eq} 1¤g *J1 lJ-o143 +llEE}+E
Q=A+2 (11F.3)
,'lzl6llot atE alzl ollHzl9 tr-E{+. 3+6} $=-"a;43 ol l32lE Zlg 6J Tlsel _q$ffql 6iezlE Eq^J(gzlql^l
^9
+ dzlel tlE H¤+ql +6H^J qaolq(^g tr4z} a(t)a(z)), /E sr.lal*) ^Jol+ +4u+. ol flz}ql
EI+^l pauri9 Hl]4 g4(tr.q 8B)ql el6}l^l *Zl rl:"gL+= 44 "I&zlzle-
=+l# =+l.g
eq+ qlEql qlq zlzl ,<1tr- +s+
ol tts Hsl.ll +6ll^l Hlqaol?+ot f,+. eI dzlzi n*+llE ^g-+llE
6J+=- d+6}a += 6|+zl n_3 d+6I= ol*l+ zlEEt 0ll 11F.4
E v-(r,z) =n+(rt)n-(rr)-n*(rr)r-(r,)o14. 4&
Hql^JE HI^t NOq Htqd}4 {z} ullzl=...1n'o14, q+^l z1=tlr}
ql E6H^J ol +5.*+= n-(r,)n*(rr)-n-(rr)n*(r,)=- Y+(r,2)
s=1, trI44 ,_ r+ol qq 6J zlc.E 2rrol+. EI+^J 6JE
7l ¤+. + 3+.J tr-49 +z} EL+E 4¤- Eql^JE HIÎ
"+.E" o= r+r+ t+E Eolq, oJi zloE'il,,r4'ilr,rol4.
ql +6H^J H}'l]aolq, q4^J 6J zls.E Eql tdzl_= E¤ =+l
4 ++lEe z+eE qslqq fl4f929 HI4 +pql q+
.xl tz;zl ¤u}
6Il^J).Noql^Jb rftr,rol r[r,rE4 "-]t "Jol4.
zlElti 0ll 11F.3
q7l^J= +g qlqzl 7+l
^Jqlel o,= ^84allEz|. {z}
ullzl (b) CE4
+ alel4 4zlzl trlEtrlE r+llE.el+E ilzl6}zlEJ ol Eziel dzt olts d"lE"l +4H- a"Jzl= xll
= ^slEHql^l
EE 49 olE4(,te 6D.o(t)PQ)-u(z)9(l)ql Hl q+61+ dq +4e
"14 4lzl 91trI. d¤ +zlE 4+E-=#E
^¤Eol
ql6l-= j/++q +6ll^J Hlqlaol+.
^Jql= dzl. tr-c.
^fl r Cziill zla. >el 7)&7l|^11 zln E Aq6[7ll TBoliot ,*4,
436 11 E^tgHEl
Hsl=Q+4 eg dq +zlel zllEg ts=+

7
Azt=0,11 AS=0 Af=0 AO=0,*1
d-d E^le-l E^l 8E|,|
ÊlEaJoll
uffizlzlE(Eq sc) o1-=
ttl-Lf CEI +1 (11F.4)
I h -,
(
flz}9 A+e+ +4e dol 4CQl

î 4gFr3=ol
_H.¤q"lot 6lr. +xlq 4¤ol lol+= ^ld
qlEql
^Jaq
ol + dq +zle oF{e+ ?ol 4?ql "J46fl^J +Eg +
gltrI. fg 11F.s d-d Eol= s-9 Eololl 6t|B6l'71 ttll=oll HJE¤-=rl Coltrl.
-La1+ Erl'CE.3 E^lel HJE Et|eg q'49 + fleq, rel6tG{ s, u EiF7|.
4EEl^l ?Jll Etrl-. E|18 6C0l S.ol^lE TlE-E^l.E0l7l'"Jol-J + 91trt.
@ Etlaql g4:dcE4;+=.1
¤iCt4 o + dq +zlg qe^la ql= Eq scql^J E"J+ d 7l +Hlq= {ol$uJol q+gtr}= 4"14. ?,
zl-tfizl dol eHlE tt,t=JW! iVdrE ^Jeg rEJ6k E
6d r]]4 EzI9l r}]6}]^1, u+gel gJu d"l"Jol -d+g
ol
^lql 4E"l
Agqzl ?*zl +16ll^l= rl4+ Etfz} Ez|9
E= r{a az}ql 46}l^J EH"l?+"t q}+= _r.EJ6llo}
+. Laporte CEI +4
^l.¤E
++(Eq loc). #zl g+g dolr-|.-Er rB nF.sql -HoJ HteI zJ"I ul4? tlF
4+zI .gHIE ¤&zl-E z4 CE(Ez| +ql ¤ee} ^d+) ql E6ll^J 4a +dol sqe ql= d"lz| -"1+E + 9l+. 4
g HtE x - r dolE "JezlE p9 CBol4(ol +ql +4 a +dol s.qzlE g-se} ,,+,., dolT} Hldc-+zl dolel
eI p9 += CE+ rEilag 7Vl4 ol dolql TlqE 6}zl xllEg Ezl ?*zll 44, olE dolzl-qf:"Illl -"1+g+. olfl*
* ¤l+). I p9 z+ ^dEe qA e6J +¤ s6J6J+ Hqlî Hlqa 4t5- EllEql +++= dx} d"lE T!=_drl flot+r
e-l H]Îql +6H^l (+) qa¤. 4=+. trI+^J (+) .- (-) dol tJ ErL
r-ra.
el a+ql= {ol ffiz} EHlEq dill4 4?"1 (+) x (+) x
(-)=(-)olq, qqo} +tri. EEt^l r+ * u- q
"|+^l 4E¤- 0ol zElEt 11F.s
dolg -"1*9zl ?*=+ r+ - r*e} r- * :- dol9l qlEl rl or9 dx} ^Jq ,tlJ zlS.oJ d"l
'>; e'E;,
4E .J+E-¤. zlzJ ft)x (+)x (+)= (+)eI (_) x (+) x (_)= (+) ÊEHql^J
e TJE qL aol -d+q= 4"Jzl=
e+ B"l H+g+ tr|+^J 4E"l aElzl ?*g + fleq +
T; - 'q,'I; "Jot
rllzl dq +zlg +r6lq +s=r+ ?8 s
9la1l,<1 rrr.+:19
dolb E+ -"1+¤+. E "JE + 9l+.#zl!= A=e BzJ a4_" + +4.11fl+.
tt*izl. EHIE ¤tlzlE ^ll ^J+g x, /, 4 ze+ +ag ,J^l
eE H++qq, E+?+^J +d '}]a Ezl{lrJ5 E-f uolrJ. u1 AS AA )}eli H}dCE
H+
4rJ e+g dololl 46ll^J= .{48dill4 tldd"l
EL+E 3I; e 3I; 0 0 D<-r- geu 6l*
gxuxg=uol{, r?-l+q 4E"l 0ol qqot ++ u|{z}zl-e.
u+u dol"tl qldl^JE dill4 HldCol uxuxu=uol4, l4
'r; - '4 +l -2 48921
olg
Ld Et
g<-g +zl
aI¤ ol A+qlE 4$ol 0ol gtrl. E|+^J Hld^dE Esl¤ + 3E; e 3Ii 0 0 f-eI* geu +^l
Hla}zl ?+= dol= #zlB+. s - u d"l9 a+ql= q4B
tJizl gxuxu=g$ Ag %r-^l_o _+ H¤|qq tr}4,tj flolz|
-.1+g+. (c) cE El^1l 75
ExI9 dx} /J.=}l dolzl "Jqg ql= BzlE rlE -d.4zl t-
91 61149 ag ++e +g-r+ Eol ,qef6J + 9t+. o _+
"Jqg + gleq rfl6}q TlE o!,t11 7
^14 ÊEHql
:a}9l EI6]]^l: Ir * z-el t- ColSqlol -dl+¤trt
E7l-+48 + 9i+ #J A+ql= ul-q dzl-tr
-:- ^4EeE
4E+q9 dolzl "Jq+q, d¤4-" + ol ^JEllE HIEI TIE
E4 +Ee +d-qla EzHCB +ztg"J olq+ Hld +C u" =oo|+E d+qr 9lq a+ql q+^J= uL$ dz}
g *= +zDql 4t Laporte dE4 txro +^1, Hlddel HEI =+1,
,*4 y"=0o +Prl * dzl. {r-49 u'=09_P9 4".)71 7l
11F trl gEll 437
ÊE=J
HJ+E
8rl $EH -.j) E EE x{TL
L L-i,\l
D' E^l =
K u a. J' ==
8Etl
8Ell
5
6
{il K
EiJ
E'
Hl.f c^t 5
:
8El,|
o Hl=f E^1.
K
ll] 8Etl
a.]
JJaaaa Il 8El1 -"i
:.J7J
71e:|,, R
(a) (b)
fg 11F.6 Franck-Condon flaloll el6lE Hl'J CE AIEII++Ej r +^.1 a4ztr zltl, R a4>tr t1tl, R
a+g t]E SEllE T.!E:d^l E017l 7l-8 gclLJtrl.. 0l +^l d019
-4=01 =!!=
,J^l7l:d= Eol- TIE
^Jl4l
3E¤ "Jea+. Elal^l E^l ad fiF.7 (a) ul'J E^l .SEt|oll,\jLl E^| 8Et|01111 gE ,JoVl
=71-e ge zalTl
afElloll^lel Ll"= E^l.sElloil^]g usEol Etrt rt= LIE
^13E
59a;'q, +^.1 Eololl sl6H^l
==
E^19 T.!E AtEHTl =-ct
l ?i=tr|.. (b) tsE Erl'
+ ?l^lu a e+6ttr1.
=+l+tr $E|]oll,'r'l Ee 2Jol7l cl Z tttl= +^l d017f "J=E
=E! AtEfloll,\l ELlq
- ^1l7l7l =-Bf
TlE:ol-=!E4l Ert.
=-J
+ ^llzl "Jq+r" -l- ^'4EHdol u'9 +7]p11

"++
ql"J6l.rll
+i++. r e-lE a+q= ^J'J+
r.llzl9 dolzl. rr'691 Bg dolzl ¤+= +rJql qEe qd6l Czl t49l^J +g dzl-
+ Ll-4+4(rH r rp.ra).
e-E tlE]|el +S+dq EB:"Izll 94.
Franck_Condon flalE ole" o[fl Ez]-E9 dz]
^}4 lul Franck-condon galE "Jzlqq}4 o -tr 6ll46lH +lql^J ¤
EHql +4+= tlf "lrll +aE ¤H6J + ?l+. H+ ,]l¤¤ E+ ^Jlflqril ¤B6J + 91tr|. + dol Etr-ql^J
qEol 4l +lzlql 4zlal] 914i1 "51+ 4dql qEol 4+E
fl{4$ dzl-"ll Hl6ll^J r eelol ql+61 r7l q$ql d
E4 ciEIE *zld4l E6J+. oJzlE+ql^J. E4 tr"EIE
zltr-Ell dol=4"l "lil 4.s"5I7l dql EBlsTll "Jqt+ qÊ.o
++-tr- +{tflq, q{^J ol 'Jg dz| dl4 {ol rr}oll.<l
Pranck-Condon flzl qq ol flalzl ?*=+= "Jr+ eg 4,o14. d
gfl$ =
oJ aoilE Ezlzl ¤B e-J ?ol al9_tr_ + EoJg ol+r gl
ol EqqL4 ?ol ¤H.J + 9l+. + d
ol-Elle+
z| {olz} .Jq+H =4fi

ez} ?}E {]sg ¤qql dz} 'Js7l A HIEI dzl
^JE]]el
alzl tlf ++lql glr(rfl 11F.8). {ol
=
El= q ^JEHE ol i]¤- ulEgt+e+ 7It+ Hl*+ tltr
46}rtl += *ql^J= Î4e + flq. rd4 o + ^J 6L nl^trro
=q+r
46IH, ol qlE-ql E4+ E+: r+Aql^J Eli] H6lzl *6|r +E 7lz'la- fl= aolzlo} ¤L+. r ol++ ol ffis471 4
Eq 4rlql fl= @Eol E46l-rll ,rll-tr_¤ eg tsrll Elq d
d +qE 6I= rl=¤ ^l4L6IZl ¤tr}. r4a i]g dz} tt4
ql^JE eA ,1"-l= fl+ dz} ^J491^]el e4 q!{}Col ¤4. drl-
ol Hqt rH r1F.6ql^l +zldg 44 ¤.4zI= dol4r =E
8Etl
^J xt9
4-g+ 9l+.qEE +471r,lzl Hslqzl ?+g ifl-P d ler*=

olzl "Jq*+r =4 trllEql olsl+ dz} d"lE
^J46I7l +r.l d K
5
ol+r +¤+. o ul=f E^l
olzll rH 11F.7a9 + tr]fl¤ qLJzl +dg 8Etl
^J46]l -H.=tr1],
¤zlr-lE B¤ a.J z)olzl E.J6Iq il¤-qlE +^l7l 4lE6i
zl ?t=+. +zl dol} "JE +dE fli d o ++El "Jq+ (a) (b)
jE qEE +lil= H6lzl ?tjr, +l +de-l 4^ dql^J ¤++. a4ztr zltl, R a1>j tltl, R
q-*ql= rH uF.7b.el a+= EEql, q7l^J= +
^J4I6I] feJ tlF.8 (a) ul? E^l .SEHolll1Ll E^l'.8Et|oll,\i EB
g d-Eilel ¤B ¤ql z)olzl HlqI tr-q]qlrJtr4 q aq, z.l¤- ==
Eg6fE u"=0a! u'=0A. q.E-cr+Eol Hl+6|'q, Erlg dE $E[|= Eet
=-sDJolTl
ql= +zt7l 4lE" 6}zl g:r gl+. aol 4aql^l 4zJ 44zl g= C0lTl gq'J +E0l 7l¤ ELl. (b) tsE SE[|E gE ,Jol7l
^l7lrl
Bl-trf AtEt|0ll^1-H.trf tr1 e qE HFJ SE}|el T|ZI .Jg qE-ct+_e E!!41 =-c'
frzllB +{+ +zldg tr+{ g4t+. qe lgql *zlol trl= E0l-=E qbPll gol'-Jtr|.. ttretoll,\l Eq 359
Ecl..
LIE trl'E-Er'+
zl g+gq, dol stlqlrJs szlolzl .rl4talzl ?*9q, E|+^J LfE[Hq, E^4 ^1l7l7l
+C3 Ee Exl gEllg aol+.
^'lB
=
438 11 Ert#
ol 4aql^l al^_E H6l+ qE E4 ^JEIq 6l]B'6171 trll+ol 9zlrl &,, nE dzl- ^Jq Hslql 7l?lqE 4zl-t
+. 4+4 0 -+ ol 4+ ji+-" EL+= i]g +-EoJ 6r+E 9lil +^J. dol E{=o14. + ol a}9 dz}A 4zlzl t}4E tr-E
zlnlololltl ++4. *= iilfq++7} qqot +4= ag 4¤¤ ++tll= 4"14. s(u6, a,)l: "l EzlE ;<lg dÎ ^JEI
g + 91tr}. =Eq TEql^J ¤E+ uts| ?ol 4lE oJzl+zl. ool ql^JE 4l+ u,$ ulzlq dz} t49l^Je-l dF ur
=+l =+l ^l
olH
"ltr, {di u1^=."a-t-z-el alrH ¤+4=
qfl¤q ¤+Bql olE Ad 48"14.
^l +4+q, 4+^J
rd4 ¤Eql^Je+ u|4lzlzltr olslq} { dol9 ,rllzlE {ol ffiz} ESIEE ¤q]ilE zll+.il HIql
rE {Iq]E d"lzl-
"Jq+"t E 4o14. rq+ ¤4 zllg tlE 6Iq, r46}q S(us, u,)el ,ll#ql Hlql{q +ill4ee. +48
t{Eol Eli* $lilql^J + ++"-l= 44421 ql$ql 6J ¤ + el+.
EE 4lE ^JEHql^J d"lz| "JqE 4,"141 s_o}"h 6lq, :a4
6Iq +* dz} ^}49 ¤4 ^}"l¤I rlE tt4eel "Jdg T.! s(u, ,u,)l' =(!w:.,w,,, dr* Franck-Condon ?_!Il (11F.5)
)
E=g +El-U4. d¤4"J rlE d+ql^J= +4 4ol7l 7l
=
* ^llrll +{\itr|.. llF.s^lE +Hel 4Ee + 4lE ÎolE d4 4Eol
Franck-Condon g4=
"JzlE+4 I tr- 6114617l eil61^l=
4. ol dd"l Pffi14 + d5 ol ".t"1 S¤++)
+ dz} t}4 Îol9 dol"llrJ dol 4"+zI EHI=zt 11¤- 4o1 ,r-flzlE 44E+.
=
+lql ,r|+ qBrll E{+zl. -r.el6]]oF qlq
don flalel EaJ4 E,\l

E@ zltt
Franck{ondon ?lr}E
46J 4ol7| &"J * dz} tr"EilE+El 4q lo\zt 4"J 4
{zl.<JE {zl ffiz]- dol sHIg9 CAg aal6pot q}+. + dzt tr-qE d"lz| gqL}=ql, a,*9 El {'-+= H
=
^8461-zl u"=04 u'-\oJ O-O dol"ll 4t
d dzl ffizf EEIE fl4}zl-= trt*$ t"l Ezi *9 E= 6;J-zl g:E+r.
44 dzl-5ql ea *ol4b {$;4-51q4. Franck-Condon oJzJ¤ 4l&6}jr" dol 4lzl= ol + BB

ar-J 7Jol7t E"Jg oll al4zl Eg E.q+.
i=-rD,+r\2,R,
r.e{gAl,Ef +H}q^}el dEE+d-E}+^}ol9 ae 4E
¤zlrJ Elq=E ?ldg Ezi9 d6| +c, ,'= dzlql 4,[] e s(0,0)E 44}ql q-Sq r 4l+g +l+tr+. z=09 a+ql=
zl, :.r-]-r.l¤ 4"ll 4el s.214. Born-oppenheimer
ÎolE ^l7l A9 $.sq,
sEle+ uJaE| d5: u1-="9-*=
=^Hdzl-
+F+ TIF ¤+E E?-1, g4L s9 d4l zl^l ¤g u-oleD H El-+^l 3+ {5 irl*EL+"Jg g+.
^F$-6IE
+l "Jql^J= EzlE dill4.J tr-El]= A *z\zl. E= dzl. tr v+t!E}+= q+r+ a+
Eol {zlrl rl^8"11"t ts +d
49 zl¤e} u9 EzITl E= TIE tlEl]g TlqE ++B + gi (Eq 7E).
+. E|+^J {ol r$=-xf rrHIE= q-q=$ ?ol E4B + 9l+
(t)t/2/r\"'-,,,,,,,
,/.=[,,,- ,-r''"' v[=lon-r) e-'"rza'
Fn= Jv!.,tY: ,{-r> +r)Z'R'}v,.,rt,, .d, )
= - rZI w !.rr,v,., ar, J v L, v,,,, d ?* {zlrJ x=R-&$ /=R-(, rq.I. o- th2lltlt)'/4ol+. trl-
4^J Ae zJEe q+4 ¤"1 ¤4.

0
+ e\z * ! w!.,w,.,a r" Jrfl,,RNH,,i drN s(o,o)=

!]v;v,aa= # I:r-tx2
+x'2 )rza2
4,
¤ zl,rl trl-$ .ll¤# ol+6J+.

¤zlrJ dt.E Szl algoil ATI 4+g +44iE dt** q alE
ql aa 4Eg +Elu+. + tr-"I+ dz} /J.4E zlra1q1o15 x'+x" =(R-&)'+(R-Rl)'z
g +"J6J hamilton ¤&zI-E r+tr-El]Eolzl"J l.$zlz[ lJ;o] =zR'+ 4 +R:'z-2R(& +R:)
6t+) rr-l6}q a{E 4E+ 0ol qa ffi f Eol u,l=+. = 2{R-}(& +R:)}' +}(& -R:)'
llr,tr 5(vs,v,) ol !g az=R-i(R.+4)E +16}r A"-l= 6lH +94 e

ol ¤+.
tt,, = - rZ J V ! .rr,V,,,
dt, ! w 1.,V,,,i d ?N = 1t u .,rs(u,, u,)
1lF trl8E|l EEaJ n9
(d) EIE El^ll +4

+x" _ _, , (R.-R:)'
x=
-Zn--" - 4d dzl t4 d"lgl dtr+ 4d dolzl E+ E"HIE +E 9l+.
r?-].ll. dR=adzol4. ol 4¤{$ ole" ol$ Q+4 ,J+ 4 E|4^J 4lt. El^ll +a r-+6]it. ts4'B oE
^trlEHd=¤
a^l6l-H Eq llcql^J ¤B+ Eq B Q, ,,i R TIzlE ¤ EId
+= eg + el+.
El^ll +E= E + ll4 dzt r}4 # tlE tlEll"Jol #
4E G.], nr'2
qlql Hl6ll^J dEt 4"lE gd q t*"1 H3r+rlzlq, tr14^l sl
S(o,o;=$.-(&-&)'rao' J- .-" dz- e-(&-&)1
t4d1 4. zlzl4 +471 dE" -4d E+ gt q +*
6I+ ÊEBql^l
r?-l6l-q Franck-Condon "Jzlzt tl-g=4 ?ol ¤4. zl+ Hlq+ dz} t4s+ E= dzl t}=llel qa tF+# 44r"
ne+ B'ol4l relH ^l++ 4+
6|zI.
^JEllel
sld 6+lEol
S(0,0)'=e-(&-&)'rzo'
q-q=+ Bol 84.
ol oll rol Elq, ¤B ¤aJ ?ol 7l7l 44
"Jzlt 4=&"J
++ aa L"tTl+(rB llF.e). FU)=ElU+t) FU)=E'l'U'+t) (11F.6)
LI=-r"J dolz} "Jq+H dzl t4 dol9 tlf CE ri+=

,s+q +g <IsE ol.rE" qI+.
i+ E' U -t)l - EI U +D=i -(E' + E)l +(E' - bf
q ol {olz} pz}zlE- ol+Al q=
o
(a
0.5 aol+(Eq tlcql^Je+ + t
ol1. qzlzlet nzlzlql 6llR6l+ dolEs 9leq, r E|+EE
Hl+6J Bal
" + 4l4I¤ + 9l+.
olE Tlz.l=
^ll ffi$ pol
0
'l4E + 9l+.
4
0 2
(R.- R.llZ', a PTl="l (A/=-t): ir(l-i-(E' +E)l +(E' -E)f (11F.7a)
-
fg I 1 F.9 H7 I 1 1F.1 oll,\i ts--J uflE0ll rH:et Franck-Condon ?.!^[. QTlzl (A/=0): ir(l)-i+G'-blu+t) (11F.7b)
7eBr24
A+ql= R,=228pmolr +g 1l4oll^J3 4= R zlzl (A/ = + ) : i *( fi = i + G' + bU
1 +1 )+ (E' -.6X /+ t )'
266pmofr.|. {E ++E 250cm-'-E +16}E a2-3.42x10-23 (11F.7c)
m2ol 9I trI+^l S(0, 0)2=6.7x t0-tool g+. ,r|{,rj O-0 d

olel ,glzl| trlHI¤ +dol z]d Bl-e +lql S+r TlAi$, @ drt gEtl
ÊEH..E+E'|
+EEl= sld
g qql ulall.r.J 6.7x10-'0 H]] +r-ql 9zl t*"I 49 s*9zl 8+
?t=+.
63cu2Holl
4ei 'rerr* dzl. ^}4 dol9 0-0 EJql +g
4 Ag 4d dolzl ++H+ i*121=23347.6ecm-t, vo13;=
ItTl B7l 11F.1 TIE ,hE" EL+E¤ *rI4 o e ¤B A
23298.85c*-', oi ir(s1=23275.77 cm-t. B'4 BE Ai5g- +
i] 4"l"ll +Cg E, + we+ wE zlÎ4B .J+Qr ^J e6Iq4.
46Iq?+(rB r1F.l0). + +Col 6Jilq:il. w'<w"J trllE
Franck- Condon qlzl¤ +6lqq
r.4g AIEI 4= d"lE 6]14617l +l6ll^J E
+EL t'-EI=
4rrcoll,tl ¤B+'A*il, "JBg "l+++. 4 uF.7azl4
ilE7c49 ol+6l.q n*A-roo)q n*U- 1)-rp0+ l)el zI
W' +4Ll]-tr, ol"lrl
"l4gol+6}q +qd ++E,El
=
Eld t'-+ vr+ BE 4l1I++.
<i
6o
W
H w Eol r1F.7a^14 1lF.7c^le_e.*El trl+4 ag arl¤ E
g+ el+.
E9, x f* (/) - i,(D - (E' + B)U+r) + (E' - E)(l +r)'
:IH 11F.10 olE:dEfl ffi-_B}4. - {-(E + E)l + (E' - E\fl = qE' U + +)
^l7lg7l11F.10ll,\'l
1Al,ful=eS:E
trt 0 ExlEa.lE
i* (/-l) - v,(/+t) = (E' + E) I + (B' - E) f P R P R
- l-@'+E)(/+r) + (E'-r)(/+t)'l
= 4EU ++)
(ol 4Eg 11C.14^14 Hli6l-+.) +qd qlolqE q-q_4

?"1 ol8¤ + 9l+
23347.69 - 23298.85
/=3"11 4oll, iR(3)-ip(3):m cmj =r4fr'
23347.69 -23275.77
tlE+, v --* T.!E+, v +
GIE,<E IIIE,>E
/=aoll 4dl, iR(3)-ip( il=fficm-' =18.6
fal 11F.l1 (a) RzlxPl ElDjalTl g<BoJ ttfl Ll'ElUtrl. b) P7f^le.l ttlDlal=
r4olq E -3.48ecm-,rl E-3.ee6cm-,9 gg + *+. P>B! 14 Ll-El-Url'. Sp + 7|.^lel CEsl trt+71. nlqele+q
tr1^1+A= -Eq=q.
^{ =d=e
xlTlg.Tl 11F.2 RhNq rl+e'I,* dz} tlEI dolql q¤
4 Ag 4d d"JzI +4H+ iR$)42387.06cm-', ir(s1=
22376.87cm-', oi ir1t7-22373.95cm-t. f+ B9l <f# + 11F.2 trl-flrl Er[
cs}q+.
u}flzl +zl-el a+ql g:+5.]= *zl-b E6l r EzI9 qi 4I
,_rul llQg.Q=g
,,_*r Z,egv.0=,{ ,E
g flzltql +61+ dzl-* s=E4l 6J+ qls^J EzI 4"ll

zle-!jH,zl(i=o)zl Eq glg trl= "JHI4es !r 2eOnmgl
/
EE dz} tlEHql^lE ¤aJ ?"17I HlqI^J4ql^JB+ a+ ^l E+7I "Jqkt+ EE f e+EI +lil=:a +z}el &q +
r. ^J46|]BzI. rBlE y<rola q+^l B -B<0ol ¤+. ol+l EE Ceql q4 eE4 E*+. "l*lql ¤;ilJ +^dB zltl fl
+ A+qlE nz1z1e1 dEol yl 7zl*41 tr++ igalq, /zI zlEg ,Jl4Eol4r +s=tr]], "l g^q+=(E 11F.2) tr]lEql
+E6l 4zlfl trq.7c ^l +el (/+r;zaj-1gE At)ol "J9 0+r) EdEol r+oJ +49 + ?l+
6*9 "JE6}l r-trlEfl dEE *izl ERot *olxlTl
^q#
^14
qI+. qal. +4U+(rH ttr.tta).
+ R7l^l7l ttl (a) o 4t=
ul*l4zl-+4+= /E zlg RTlzl dq ++7I alql"J ollol =+
+ul tlEil flz|gl,rJE 6} ea +E 4& a ?llEEL+="I d+
4 at,"9tr161:0ol q=/ql zlr4& cf
¤4. ol al'll7l= <tol qElqq 9l+. d-++ +Eql^l= d #+ gzlel ule gfllz|
I^*=(E-38)tz(B'-r)ol+. EE tlEllql^Jel ¤.J 4ol7l HI +B {ag +44^l ?+eq, r?]6lq d +llEEI+=ol d+
qltr-Ellql^JE+ sg trli= B >nolr q4^J E -E >0ol g+.
9sl9zl ?*sq 4xlzl oJS ,tlololl! dolE "Js7lH^l ql
ol A+qlE rz1z1s4 dE"l fB9zl
^l4}6lq,
rH uF.llb HzlE ¤+6J + 9l+
ql +4U ute+ ?ol I^*=(E'+btzG'-E)ql^l ul"l4zI 4 xlfr [ri(oHr)u]'*(l)4 *9 aHrll +rE"l +Ei.ll= olBl6J
+r+. A+Afl g"Jg AslEzl +l"}|^J 67HE 4tg= gE d d
6tE F i] olEol +c olgE d dzl# gqu+r ^J46I
zltrJEt oll 11F.6

E 11F.2 g+ flrlEal Erlel #J
E7l ¤E+ d"l9 a+qE r<r"14, trl+
rrE.2q^J =d,,
.tl nzlzJoll ul"l4z}+4Lt"t gl aol+. Zl- 44il= + flztt vlcm-r lJron e**/(dm3mol-rcm-r)
EIB <le q+4 4.ol ¤4.
"ilE =^14"J C{ (n*sr) 61 000 t63 ls000
C4 (n*3n) 35000-37000 270-290 10-20
3.996cm-t-3x3.489cm-' . ^^
tI
E
= =-lE: _
û= re -A= z(l.as@
= o'rd HrO 60000 167 7000
. q "*g ilEol zle ¤gl ++qq *4. e"*e: 4l+(EE rre). El

zlz! zlll$ A+ Ag /=6014. E: s%I
+s+ slele 3lr.ll g-*ql^.|9 <i5ol4.
11F Cxf dEH IE4EaJ 441
zHrB olel6J Hlg. trllE-ql TllEq++Eol F +qs

11F.12).
I
{HEcll, 6I+= 44!= +lil= zld 6J-"IE d,-,,e} d,,el E o
olJ, trl= + +q= rE-Îol- 6}:"'lt do d, f.r-l-11 d",el
,jlol4. sg + fllra;65 d+61-= dzl¤$ flE ^] ?]E
EL+E iizl6l+ dzl¤.ll Hl6ll^J +g qfl¤ "tluJ zl$ zlzl
7il qq, d +llE.J+7I (2)ql^lg+ *"1 Ao9
"ilHzl il-= 4= egz' d. d..
x'-Y'
F rll=+ e+d+. dr,d, r7]r d,? ol+qzl= 3+ trl

p+^llE= t2s +llEgL+E 444:J" d,-4st d.,E ol+olzl:.
+ q+ ^llE= e, ?llE6Jf4l er.]p4("lE 41 szl= e
z I il
I ros9l.! E96l-qq). rll t,, ?llEEL+= F e* ?llEEL+ gql
+l,(l6}q r
qlq 4 rJ4e AoE g,<lap.(dzl o= 8Hill, +
trn d,, d Yz d
octahedral 4ag E6J+), olag alzlE-E| 4elolE1
=aEl
4z Y 4tg t! A4dg ?]zlEe+ +d ++ flzI ri -19 11F.12 sEiJl fleq^1E d ?llE-Bt+Eel EE.. fl=3 67HE (tr E6l')
=4.
olE +ill4 +E4r+ ql"l^lE * royo# 84. +Hrll 4¤ql alZE= Ll-El'LJtrl.
,<ls. d fllra;i; F +?]e. p4zlzl"J ol a+ql= e ?llE

e+5ol t, +IIEEL+EB+ "Jql f-lzl6iq(4tsill +Eg Hld
+dg \xl g:eEE g, u Er-lz} ?I BtrI) ol=e-l ZI49 4e.
-*.^l6J+.
_ls*
HrO
UI
e fio
s
ioE
Ti
9A
50
T d Ao
_zL
50 10 20 30
,/(103 cm-l)
2
fg 1 1F.l3 +t'4 +oll,(l [Ti(oH2)J3.7|' LhEIL}|E drt 8Et| EB E
1 [Ti(OHr)6]3. EH.
r}"19 d"l
A"+ At= E-F
=zl S|9-{, + ?llEE}+ ^llE=
d¤4 o + 7l-^l ¤q "Jqt+. d ++ zl=E +zl(llF.lb)ql el6IE 8Bill atEql^J= a-a dolzl
Laporte
=
Ee] r+6J
ÊEHql^l
4E=3 "JHl4 " e olel+ dol qEql +El-B+ g-)g d"l(rl z}^,lJ6l "5"IH eset2s dol)91 6llEt6IE--E Hld
C-#zlol+. rfl4 :H llF.sql _Bfl ar+ 2oJ d-d dol*
Hl4a dEql ¤aJqzl qlEql dE_dzl-{ole,rJ "f"tzll -d
+q= 4"14.
lTi(OHr6l'*(l)E 24 000cm-r (s00nm) d -o4 +Eg ?]zlEE+q +d flz}9 d +llEEI+_tr. d
=Aql^Jel ÊE zlz| ol{Elzl+ r qr+e"l "JqB qlqlE +^}dg g+6J
H9 :B 11F.l3ql +44fl-Ell, ol49 a dz} a[+zl tze
?llEEr+s+e.l fllE.alf.E Ellzl tr}lEq +4+E a
"e
+ gl+. "lq+ d6r-old dolql^J= 4zlzl ^J'J6l H 44
o + oll4g4. ol +ql ¤-+ z}?_le-l EI+e, El 4l&6IH E olE"6IEql, olag {ol ffiz} EtlEzl =;r g+cq ^ll
Lo=24 000cm-1ol q=ql olag qI t.oev9l 6il'J.+4. zlE nl"+^1 4d + 9l¤¤ 9"1t4. 4'JZI& olg Mno;oll
^J=
dzlz[ 6fl2[E+E] Mn 6C gzte oldq= d dol
ql +HlqE {z} xllullzl_tr_ oJ6H^J 475_575nr1¤Eel tl+ _u-
44ol ++UtrI. qzlEe+El ++ oJ.$e-tr Tp,zlzl *Azl
t+t+z Ext#l
ol4t dolE elz!E-=+ d6l-0ld Eo|(LMCT:ligandto

=
metal charge transfer transition)+r ++. {.zlzl Hlql %r-6}9
E old6l-= E6l-0ld dol(MLCT: metal to ligand +
=+alzlE
"JqB + 9ttrI. olfl* qlE^J= d
chargetransfertransition)E
4zlzl oJ6J+ 4ZI=s-1 HIA.J rillEElig old6|b ag lrx
+ 9l+. "lBZl all.<J .<lzl| EE tr-E]]olld dz|Tl qq fldl= 1l
lg I 1F.14 C=C 016 "J^{Eel AIEE -Lltrf. 0la0l Eezp

aElql H4l Hl+zlp+qq qA oIE ol tlel +Eol ^J =-cffl =g-sf
E0lE dlLl= 0l raJoll .HoJ n* <-n d0l?.!c11, q71,\1= E^l7l"n*lEBfE
=.E ge1 cfigolE HJeEt +lE-Er+e
Rq aqa + il+. -q.
4E dol9l^JE:zBxl"J d6}-old dolel ^ll7l= dol /d.
+zI EHIEE xll#ql Elql+4. dol EHIE= 4zlzl ++s
E+q ?-ltE_B, E= r 9_o + olE"¤ oll9 :_ ol+ 4?-le-l +
aE= +Eql= 4,"14r g + gleq, r4q-q olE 44zI <_

7 III4^J f+%I ,$lzlE 44+a
=E dol tl=-x| EHl=zl =
E + gl+.rq+ dol ,nr-:z-z| EHIEE arug ql q4+ EI"
n
fix
;5 zl$$ fl+ vl-tL6L-AE fiql ulzllalg_+ ol + z,Jizl fA 11F.ls zl=.H-J7l(C=O)71 "JgEc-e 4r'E61.= g+ 3g= $49
E"J+ +t gq +ql^J 0ol ol{ <i9 zl-zlfl ool 9zl ?*E
Hl=Et -r.al E^t8fol BJ=E|'co r*flE-**e' EE71nil=o|trt. 0l dol=
fi*<-noP E,\l:dtrl'.
r+. qe}î olf 44tl d g%r"g +48 f ilxlql ++4
=
4zj=zl E4 BolxlE z-l¤-4 al+ irl-trio6L-Ael ad"l e.4
ularl
-1 l, I r-}nlzl
6;r-l. rll-zl-zl
-tEro"lt, .A olrl .
(rg llEls) E*<-n EolE "JeA + 9l+ d¤4ol gf q1
^-le.-T_,Â'1
HxlE * +.t ev(2e0nm)ol+. vleEgTl9 n-en dolE 4
(O) ru*en "J r*e n dol 4_#zl dololq, ¤:oJ"l E6l.rll "Jq*+. ole+ 4a49.E
zl=-Epzl9 r.er dolb C=C 2* aq+el n 4zlzl EE=
C=c 2* ¤*ol +Îdg ¤+6IE n&zlzl +¤q+ ru.?llEEt
g+t+(rH rrr.r+1. tr++^J E^4 4o14, 44zl " + -d+qq r46}q Eln4 t] g*9 +4
+E EtrI Tc*?n
=+CE= u+.
Eol('n-trPel r Ese9 dol'41 gl+)ql 7l"J6l+ L"14.
Hl-*aq ol+ Aq+"J trll= ol dol ollHxlzl * 6.e.yolq
"l
+^J z}e]d 999 rsonmqlî ¤+ol "Jq++.2+ AoJol
+"1 ^F+el .J+"J trll= Ezl TllEJ+=9 glulzlz|.rJE rJ z}trJEI 0ll 11F.8
r46}q n*e nfl"lzl thrl1r +_L E 0l+6]-r" * CHrCH=CHCHO+zI+ z}e]d ¤qq 46 e50cm-1(zt:nm)
=d4q
a4 4l7I +Efl a
"I= 7l^l ¤ lg ezyzlE
o|Eo 6J+. ql^l o+*
CI ¤i+. 4441, 30 000cm-1(330nm)ql^JE
zle_E_H El.J¤ql^J ¤=lg "Jezl= d"lL {}4 gzlql
++E +4U+. $}E ag Hl+zlE+ n/l e,=e,-C=oel S
+61.= -1.fl {zJ-4ql fl+El= 4o14. Lewis THH$ 'rB d d¤ r.erdol4. ul=fzlft C=O Tc*+rdol ¤99 e
z}5ug Ez| +llse'f olEql el6IH AEt B^Jql= S-q6}zl + *e El+ Etrl a Eltlsg H-d=+. 9zl* zle*H-
9+r +E qi gzlql +6]]91= ?llEEL+e-l dzlt"l4. ol dzi =
H B^q+$ +¤g r*en{olr-|-.
AdlE 6l-+zl zlEHHzl9 Hl zr* +llEgL+E
=iq =q7IE^l
11F drl .8Ell 443
ÊEaJ
=g:d7HE=
Dl. d¤ EzI9 :d 7lE= qA ¤A+ ++lE qe 4¤+*E q+= Eld "tlulzl Es+ql zl.Jq= 1o14.
4? szlE Lf+U+.
el CEr+ oJ4l ole+ +flq= D6. Tlillt} ^lEE a+ql= 9d "l,rll 7aoil ElElalTI +49
rl2. Laporte CE4 +=lg 6C-qla EzlE d$ u+ge} g+u d + el+.
ol"Jol 6l+E+= ag +4U 4o14. 47. d ++ 4¤ql^l= 4zJ=E +4lE .J611^] d ?llE6J+EE
tr3. Frank-Condon flal} e=E g4ol Eitiqzl ?*eE^l d slc+sz| $,olzll olE ^l-ol9 d-d T!= d0l7} 6l+9trt.
^l-^JEH
d"lz} "JqU+r e+. tr8. EEI-olE Eolql^l= d¤4c-g "lrJEe+ 6d #4 flxt
rJ4. 115 El,tll +r= d^l ^JEH dolgl +Hlqq "J Îolql^l 1j,zlzl
olE" d4.
^trlEHE
q+: dE qlLlzl Eslql TloJEl= 1o14. tr9. g4Ee ¤-"J trl= ++4= +lz}+oltrl.
=a.J
trs. 4trlEHE 615 olril 74= dxl tr}l dolql +Hiqq .J
=sEl^l=
,\-lzl AI Z.A)
o=' -1 I --1 HE
^]
Cq +4(49E""*) AA =0,tI; As=0; AI=0;Ag2=0,*1 c¤ Ezl 11F.4
',s(u,,u,)' = (J,lr,:,,r,, or*

Franck-Condon oJzI )' r lF.5
dx} tl4 s13 ul,tll fa i r(l) = i -G' + bl + (E' - E) l' P7l^l(LI=-r) 11F.7a
ÊEHE
(2?]Z} EZD
vo{/)=i+G'-blU+t) e7l^l(A/=0) 11F.7b
io(/) = i + G' + DU+r) + (r',-r)(/+r)' RTlzl(A/= +1) IlF.7c

EE 1lG EB
==8EH=9I
> ol EEE Hll+= 0l+

E^lel I^l.afEll7l +^ld= LH=e.E^l HIEIA|EHE EoPJ ols-}
uo
=E
trtl gr=61.= B^1.= 0lE6lE r Extel I^t +60ll *pt A.J-el
8E= g= + flrf. ole'lEt an= Etrlee q=-t6l ellol^1 --:

r\
oilE 0lEEl-r. ?lrl. =s-d
r(fl1
io
-ol.I+
> -._Id TI|LJ OO
EE E^l8EflE E^1E3 r=el zlg oilL1^l= C^Pl g=

6l^Ll, +9-l01lEtge^l Lll+71Lh =^lE
sE= EEe.e st|ElT1Ll'Ltrt
)'lzJ, t
> E.e,E:t qHl rl^l fg 11G.1 EB"l.oJB a-d4(+Eoil g4:d #3 gg aol

ExtE drt ¤Ell Eo|(EE 11F), EJIE a=rl rE HJ= gfl= ^tolE
rll4^l7l^fol'^l AEEI= r1l usG +^1.= t =E
tllzlTl Hl.il.4 j^l6l
,\[ole] i]ol(EE 't1A), :lal-r. EtsHE ^lEl4 gHJ4 dtr(Etrl 11A) #Êq.= 7i0|tr[.
+xl6li1 ?lolot etr|. trrIJBul a=-d iHEE 8c)sl

=
Fra n c k-Co n d on 9lfl
al (-E.o-f 1 1 F)-E9l^tolE
o
:p
?.lotlcl.
I
4E :H
ag E"Jol E 4o14. ol E= Ezl^= +
tlc.3ael
?l Ezlel +$$ 614l qr" relo}ol qlqzl= Hl+^l "J!e
Ezlz} r 9lHxlE rJzlE 'H+= 4Cg +^l.aF^l r.El E grll 9=+ TIF qlqxl 4ltg,rI+ 44z}rl EE
=#:
ol+a ¤I+(Eq 11A). s== tlEllE ceql 44 4ae B dzl tt49 alzl {E
=9EE6Irll ¤+. rel+ ++l E
"l =+l"tl
%r-"1+ oJ¤._q__p ++¤4. dzi tlEl]zl E= EzlE tr+ q ztzl tsol¤ol. qlqzl= 4fl tzl $zl ull$q 5= +zl^=
FtF4"J +Be HFJI Ad"Jql q7l^J= 5E qlqzlzl ol ut$ dz} *Aet|zl 44zlzl *6J+. E|+^J ol $zli z|.
* +zlE tlf, qd, "i Bd qqxJe o1484. "l 94 4 g4 %l=g "Jea qlnlzl ol ^J'ilql
qE+rI tse E
6l+ $s qlLJzl. Sd6l ++lel '¤SF'e_tr H+^l7lY A ==
E qlqzl= +Îdo +^J "J=6lrll ¤4. ol aloJ: {z} {tell
ol4. E=E ExlE E 611?]q4+ sl+ HI+g "Jsa +E gl dolE f{ "e gq+q Franck-Condon g4ql q_e--r.(Eq
q(tr-q 14G). ==E tlqlel zJ4 HJ=g oleo 6J 4ol 4l"lzl 4I 11F), n}+^l B%r-lEEHql= *e dz} ^J4E r+e TIt-
8o14. +471+Elu+(rH r1c.3b).
o-o g;e} ¤* dolTl E^l"tl +El-*4fl(ol izls=g =l
11G.1 Egzl gEJ
Etse E+| qlLJzlfl"l 4l4qr +^J + +r= a olqql ^l Hl-=^f a^l

E7I ++4E zlgzl +^l HJ=ol+(rH 11G.1). rq+ ?lB
g t}^la t-"J zl+E + qlb zlg4 B=ol4(9 rltal zl j
K
5
+¤ +E ?lzl"J trf,$ H a+ E= r ol6}tri). olelfl zlol o
{ru
a?+
cict
Hl'*
O=
¤+g H"l B= qlLJzl_tr + E+Elq +s= 1"1 ¤* Er

E- 9g
=
ola E g+E qlqzlTl qtr %ral_oe z.ltlElfl4z} K
HO
nl'.l
^J^J6l
Lls= Tlol ol$ol4= ag "J^l6l-= 4,o14.
^llq
rH uc.2= +E +ql^J E!¤ol +e}.11= ¤%Ie] +zI4 t4z1t1tl, R
"J 4e# +4U 1"14. a 4Aql^l= EZITI

qg ¤+6i .f.al 11G2 E-4 +9ExPl BBE LtEl-Ltl=+^|4 cJZl. gGlU
r Es1 dz} rJ4s gq7l+ "J"J g+ EqEl{l ^1e-sl=Bol ,J^l=
rlBoll Ee T.!E 8E}|7l ++l E^lolltrl. ollLl^l= Lt|+E^1 Hl=^|.
ÊEeg geilrt. 0 lcl,\l tsg E^|- atEHE H tf T.!E-3Elle+Ei E_ l't! E0 17 |.
gGl'-Jtrl-.
11G 8Etl=el tB 445
==
(a) (b) A
\
-.I-l fi a!+
oo
EO d'l
(0,0)
j
r.\
9/l
:oJ-tr}
tsO oo
fal 11G.4 EE11= BB lEleaJq qiE ErJ l"lEaJoll rt|Et +l^lel

tr18,,1 # +ell 6tt=+ ?ttrt. eJ+oll^l= E0tl(El-flB)7|.Ht'J E^l SEt|oll r+Ej H[|EE
0l=n ?Its SEHoll^l +^l.d= E+-.Jtf. -r.al+ E=Jol LfElLfTl doll Eot|
fal 11G.3 ÊlEaJ(E^4, a))g te d^l dlEtloll r.B_d T.!5 +a E^1.=.3 UHEE ol+q, 0l Ht|EoI ++ Eol rl-8011^l
LlElLJtl. =+
r4l eB b)3 'fg dxlSEt|oll r+-.J T.lE ^llEE ^|1E8 =^l
-r"c|.|e +^lEtrl.
=
+4= ^4EaJ(Ha|.Î,
LfElL.lrf. 0l !E-d '*3 cE+ I+e-e 0|56|.q(0-0 c0l=
+tlJ401tr1.) E+ ^trlEg=
71t,8= LIE|LHTIE -drl.
ÊlEeJg LI= dq^J +."J+ 7l6IqI4 +e= 4=+. El+^l + d^l-
+ "t 7l+ tr-E}]el tlE "Jzl+ up! u,E +r}u+) olag + E tlg +q751:r-lai¤ Jte+q tteE E+|g g
^¤
e7l=) "ll7iq=ol 6l-H ol $zlz| z{lZ!.EiKISC:
¤E "JzltrI.¤-+ 0e0, l<-0, 2<-0, sl d1l4
^trlEHg =xH6I7l"J
o + t.olzl= ++(4 solxl= iiltl)el dol.ll E6H^J +4 + ^Jol+ trl=:E ^JEli= rlol9 Hl-+^l-
intersystem crossing),
+q, 4 ¤+4EE ^ll7l= Franck-condon gr-lql 96ll^l e d dol$ .Je4 3+6J ^JqlE 'Jqg + fl'}. flz| :-alc_fl
6]]4l+. +¤ ¤* 0+0, 0+ 1, .. 6I6J dol"ll 9 ql ++ EEql^Je+ B"l(e9 8c) :-g-TllE Aql"l ?lg trll
ÊEH3
6H^J +4kitr+. 0-0 g.+s+ B"J ¤+elE=$,Jfr" g"J6l4l +"J6J-3+6J dolzl gq$ + fl=ql, ola.$ Ez|ql^JE.
"J =
uftzlzlol4 Ez| +ql 4'J6l +4+ gz(sel ?gz} Eq
zl6tzl= ?*tsrll, olag +,l]e+ ¤-¤ol Hl-EltL4e+ EE tlEil
{lrJ *zl ?+al tls4l¤¤ 617l ull$ol+(qlE^J +4 e6J gleE aoJol r7l ulEoll olEl+ zlzl _nzlzl "J
^fl-+llE
q+41 g+.
E"Jol trl^= + gl+). *rI Ezl-E dolzl "Jq+= E,qlql x}l
H]]il= gea"J+ .E EZIT| g+ 3+6J ^J4E H"lzlE ++lql+ qlqxl
^l+g {zl {a}Ee s+= +'}]Eig
Hl.
EltlE}lq r+6J ++a 6Iql^J "Jq+zl"J B%i dolb +rHsi E 4l+"11^J ',J=++. rq+ ¤zlrlE 3+6}q 4lE qlqzl
¤ EE tl4q r+d ++A 6iql^J gqt+(rH rrc.+). + +414 44ztrJ HlqI 4lt Eg++. ol 3+
=+lE
.J =+lql
glHzlz} *+(Eq 8Bel
¤'&e 4t5t qlqzlE "J+71 ++lE q_gql +e_al
"ldg ^JEH=
6l]'J-61= B"J6J
^JEl]Etr|
9o + r 415+8. EÎ +^l-dg 1]¤+E+ *+. ¤%l gE Hund9 +4). r4r +rl]= "l al+4 " + Bg dzi E
qlqxl o}{¤ gf6171 *6iq, E =
el Ble eflzl{ol+ a+4e "Jt4+ql^J E f 91ts ol4 E dol trilEql
^g-+xl
+ o'+9 {lEol4. ol gE EzlE=g x}9dol4 e^q gEE 4rI *4 e H}qI^Jq]E qE.opl-zlE * oJ4 r+lq 4l{}
o
Hg ¤+6J trl-gql zl^l ¤qE ¤IJg L}]+= 4o1e. Et

"l B%l "ll7}q+ql el6IE ¤oJ rllzlE s" o]] Ezlz} dz} 9l S
qzl "JzIe+ {F qlqzl "Jzl¤ 9"1-4 g *g f ?l}zl"ll
E=6Iot ++. dxil-tr. d+qlqzl zJ4ol Hg *ol] K
T
=+lEq 5
(qaE|] E)= dzl-qlLlzl oJ{¤ Eg + fleq 146}"l o ol.zl
lo
=
¤'J¤- iE^l7l='irJ a.45 +E|.J + ?l+. += Ezlql
{ru e!l
-6i HO
E-
e_l6H^l ¤*ol A"Jq= +E= E+ rI+61 +l+6J HI¤- +E K
nl-t
E4 Atrol+(Eq 14G).
rH rlc.s= +"J6* Hlqr-^JEl](So)9 Ez}zl- "Jrlg +4l3 a4z1 zltl, R
rll tzl.4 oe "Jezl3 4C- +4d 4."14. a +41= ¤
s=E E"J6J tlql(s,)el qlqzl lal 11G.s oJBol LfEfLf= +il-= 3zl=. q7l,\l Ezl= ^trJ-+llE
%tql^Je+ tzl"J "J%Iql^J= =g-Lf ZlrJ rr[(lsc)
ilql 9i= EE:5ap ^J4(r,)zl +sEL qgg EI+. ol B"J = =Etoll 0l
.J4l0ltrl.
sldt|,(J Eg-Br ArEt|(Sr).e+E1 3=-Bt AIEt|(T,)-e
3=-Bf arEl]++Ej ul.JArEl]e q=olTlE
Edl'=
'i.. 4E-=^l017l nl1
6F+ 3+6JE E=
^JEl]=.¤-
r=.q slHl¤ "llHzl +dol + Eoll 0l 3=-Bf 8E||= +^lC= B=6lE^j HltrJ SEH-e EEoIA+.
^l^'16l
446 11 ExlP.E
35
+ --f,- :_
so o{_a
L-i
-
dtlel El4l
30
I
.--:
E25 K
o 5
P20 5
{ru
t'. 15 El
<F E'
E- ro K
lll
6
0 a4z1 t1tl, R
:IeJ 11G.6 Jablonski tr+(L|-sEJflloll E[|EI)= E^l-sl E^l.01lLJ^l

fal r 1G.7 Ee Er|' SE}|E Ei++ SEt|-e E^Pl
Plil= 8cll40+ Ll.El.L.! raloltrl. +olI] d^f dfEHTl LIE[Ltl= qa] =91
dE 6t|alElI E+=+7.,gclLl^1
EJ=aJol Ll-EfUtrl. 6Hal -d4l 0l-at|oll,\l= =!!E
d^l ,tu!l=flo1
8El1=el d6[ ?lil= Tfxla- Lfefuflflosi(7lE Ege.e),0l )l- tr84?] TIE +6= LlElLJtrl.
=fl=A
lolE +.8 71zl7l -"-{rJ TleE LLE|LI|= a= o[ltrt. 4 ETI SEI|EE HEl
LIE 8Et|= 8trH48 d6l ?l^l7l8El6l-Il"J r 9lE LE AIE[|= 5.4{-o-+
Ll-El'1.! aql Erl6l'tr1. (lC= Ltl+ EEIE, lSCts 4ll r.^1"= LfElLJEl.)
oizlb 6]|alr+(rB rrc.z). sllElE
^lgdg ¤+ ^srrEeql
^J
+azl E+= {sf$ _H_E "J + 9i+. ol a|le!
trlel TIE
l-zl¤ "JeaH ta+¤--e- dq +z1g Esl^l7l El4l +lql^J= +zl-e"JEol "Jz}e-l.!zl ?*r BTI gf,$ 6i
^fl-+llE
7l qlEql ol +Îc dolzt sd6l #zlq= 43 "I.14. r 7l qlEql ¤+4"J ¤-+ rlzl 44+= aol+. 61]F-l 6JalE
46Iq EzFb A¤-E E= tlEl]gl E.E:olr. +^J+El s*5. +lzlE *"tLil= a3 a6J 6ll?-l qlqzl= ec6l+ +16+ *
oLrnl zl? -rl'l' r-lil 7l-4-z-l o tlrl^l o u}3*Lrl trl al rl
'rJ"ll.
r-l ll
="1
'l "l ''l--l = -
--1 'l
L-1 o e L'-1.
=
ol
"llz11163 $fi-
qlqzlzf ulil rfl h#E ,14 4* qB A+ql= At +^71 $."14.421 "JÎ +ÎdE tl5-
rql ef, ailH Eol= ¤E Îdg e. ¤H6l]=+. E ol "lI izl4 +olzlfl +^l ++t+. "lel+ ¤tlg daflal4l +
7}q+ql el6tE ql"Jg _I.i]l ++q +g ull :z 4lzlzl s=trj|, ol4g rH uc.8ql _Hql a4 ag EzI Elfl¤ qlq
^lH
7l* Aot' +q(¤e4_o + + q"JE]9+). oltrll= olluJzl {ol zl +dg zlzla_ ¤Eg + 9ltrI +^l7l +e. dÎ
^J'llE
qI
zL E44-o + "Jq+zl t 6}l, 5-s +"JaJ t4z} r Tlt +g dE EEH r dzl-=ol xllullzllflrJ d-"J+ tri
"ilH
zl= gr rxldg 46J+ 4l rlzlol afl+ ol "llzl-rl
re" =+lE
6EE += dzl-^JqE HI+Î^J H+|g "JeA f ilbcll
6ql E6lE "Jr*g 4*61 +4& gzl-(^fl-+llE A.Jol tl) "lag LH+ HElt(lC: internal conversion)o;+a ++. olBlql
9 ¤4]*qlE s4lq=rll ol4E ¤E Îd4 "J,.l*tr}. L]]+ H+Le + +zI trl$l¤ +de-l r.iLAql^J ,l-tl flrll "J
EzI qlql^J .Jq+= Hl_+Î dolu| +Î dol= E+ r ol{Erll, r ol+E ol lzldgl^J + tr4z} t"J+ 4 uflzl
fl ttc.o9l +ElU 44 *Z a"#9 Jablonski EEE zlzlt- E zlzlzl ullEol4. Ezlzl H+IEIq Eqzl-E ^JEll= 6]1"-lc
+49 + el+. "J fz| ilsq, r-46}0l nil-d +tiE} +E
=z]E ^JE{=g
LtEEt q 11G.1
6flel zfzl
"JflE cl-.JE +s$fl, t-3tr-E4gg{1, l-tr +tr+sg-
Hl, :4I. 1- a q{EBHlql^l B* Egg +i6ir. oJr} K
5 oq.^
agg +zl+ gzts il¤+6}
+zlEl+. Hg^l-= "t,rl+ El 6
L-i
-
H S, egrl t,.o +9 A\TJ azl7}6}tiqq, BoJ arffi-

o {ru
El
z]4,<la+. Tle_tr+el soo +9 +Îc dolE +49 g E-
K
zl¤ql el6ll^l .J^Jqr rq6}q "J* a$g Qzlt1z1rl. ll-J
a4z3 t1tl, R
lal ilG.8 0l r=JE fl+Eoll^li1al 6Hald SEtl=o1 ++ ArEt|=al r^l
11G.2 6}|a!e[ CaHal
E tttl= 0l iÎtr E^l7l 6Hal= + ?ltl. 0l al"E= C6t|ala|I
=^lE ==
61.=tll, 0la= TIE +azl ,\lal*+7l. g,\l E-,\ldel T.!E+7f
5E dzl {t4l tsztE qi +,qoJ slE4 g$g ¤.JE"l # ÊllEaro{l,\1LfEfLl=
tsol^lE cE Tazl'trf^l a= H7 "Jol'J + 9lrl.
11G # SEll=el8E t+47
& zlzlzl uflEql ol$el E 11G.l allolxl EJl.dsl

"llHzlzt 9g6r|l C99zl ?+=trr
=44
olEel Et-44 olE
(+B trld, Eq 11A). ol ql.Eql olq* rild ¤- JaA old ol+
=aql^J= -1 0
+ Pqlrl+. "JÎq* rlzlel qlHzlzl ++61 7l L-o +A--1 E|r*zI r+A E"}H
ÊEH"I
ol j/7}dtr+ gd q te TrE
rL
+^l7l # tr]]=
=
^J *2 4Zzl t+ *Ez67l
q+ H+ol "Jq+zl t*=+(oltrll= qE"l E.JqI 716I+4
=:?l-=.
k3 &* rllzl Raman ¤%rB(Eg rrg_
llD)
+a= olE + S+). E|+^J qlqzl EBolrll AE r],(u/(l
L-: -- O *E?-l+ ¤+E
=+lEg
El= qlq^lql +qlq-= EB* tlE C4g El*4l qq, q+ dq I}E}E4 ¤+(Eq 14c)
^JEH
HI8 EqEi(Eq lsD)
qlq uJ"lel a_41E+ +ql^l d +a7l +^l +
^l +qlaH ¤esl H¤ zf, le zl]*B *s
z)ol
El+rll E+. dB-4I+ S* zk Raman E+trXEq
r 1B-11D)
g^ B Cq.J# HI¤:(Eq
utst= r+G, rsc;
^lA
zrtr'Et oll 11c.2 SEXEE 14c)
qlq4 old(Eq r4G)
o2+zl+ xte-ld +^l-= g4q-q 'r; olq dz} ^J4eP
rl ,H i-E tlqe d"lslEgl, ol E+ ^J4= oll4d ,n,
t'-EIe+ ollHzlzl 49 *r+. ol A+ql= d6fl?-l s$zl-#
q 44421 qBq. ql4lql H l-+^l
++ rlF-3rld +a I0l
^dgq
4l+ +azl-$dal S,9zlzl ?*r Elzlzl"J aJ4. Sq^l
s+ Bol ol uldol +4+= ol¤+ ++g dx} r}q
t B
=E
e+ 6lqc EE tr-48 +Elr]]= + +dq rila 5
K rrJgtr 410l^l
=i.lql 6 E0l
^J
EE d+ tl{Efl +Eol Szl ollE"l4.
X
fa 1lc.e 4=?l allol^1oil^l golLl'= Eol=. a1l0l^1 col= 8Etl(A)

ELlq, Asl-B 7tli1l+ qde UFJ gEHTl == a4l
x?l d0loil^lEq
11G.3 Ellolrl 0il^1
gqLJtrl. ^tolel
^F qlolz](laser)r{:-r 4"J
EE rJ=ql el6]]^J .llHzlE +^tdfl +
^JEI7!
zlzll R + 9t+. "J3ryfrt amplification by r-tr EIIZI 6l-=rll, olaol rE
qlqzl g+= Hl-+Î "J^-le
stimulated emission of radiatio"9
"l 43zl-E
trl^J
"J= E^d q E 4t+148^J(qlAEil ++le-] TIE +Fql ql=+) *e t4 s
4 zH "J¤(Eq llA)ol+ EE ^J4zL Bzl¤ "J=6IaJH _ts Hel+. r=lr B7i *g qlqzl Ae E.oITl.= qlol4
^JEll
ol ,JzIe+ E"J+ {d$E +îdql 9aflrl zffilolot f,+. dolzl "Jq++. dxll4 oe 44t9 #9lEol *olals.E olel
tr++^l *zltl g}¤++EJ=ol .Jq$ffiol +olAq. + "J^lg 4=+l ElloF1+r. 6JrI. ol HJ49 tlde- ee+ s=.
ellolzl +^l= ¤4 ¤xl+ zlzl:t- ?14(s 11G.1). fl.E ,Hal+ qdg "Jq+al a|b 4,ol HtqI tlE|] zllzlaS-
=^dg
ol $rJE=g zJzJ(Ey += a4 e-rEo _e-_+.) EElglqlql^l + azll o1175- aE+ *ola}4E 4ol4.xE+El rEel dolts
Elgl= 7lEl=. gq+9l+. Raman #JH(Eq rrn-o)g ellol df Hg aÎ^lA^J "Jq+rll q+ql(S+ol+ Cgg ol+),
!E+El ,Jql tr^4o} trlEql uZl gd6|g.sq, EilolzJTl Lll "l 4Cg gugolr}a sq Esee z^ll} 49lrJ9 dzl
+3 + fl= aB^lz} g1 trIEql gE-a 4zlE olE-ZTl Bd"l4 4= ellolz.lel Hg zlzl:i- g_e-Aq
zlel
^lrJ 4Eql^J "Jq+=
HI+g s+g + glrll qfl+.
Ellolzl ++E * g a +ag ¤-^14 ,J=g "Jq+al g + Z]tr.ttt q 11c.3
gl9 c++ a +¤¤. zlzl:il_ + 9l= EE Llleq+ qlolzlt- +fgl rill-^Jql qlolzlE 9¤=o14(:_
gl"lot HJ==nl9lg g.I} =?JE
8Ell7} 6J+. E 4+ ^ll7l7| ^ll7lE "JE6I H rrc.ro;. ol qlolzJu olq$ "J"Its 4+4gAG, +i-ll4
zl 9lo1l.<13 tl'}lE
=?la 7l|i{[+
oJtrJol+7} *g qlLlzl t4 "J"J -q-E= yrAt o,r) +ql EqflE a?*9 Ndr* olgg=tr trJ
ol+E+ g:otzlE Ed"l "JqB f ?1"]"t e]r+. ra E 4"Jrll Nd:yAG q1o1z-lrp 6J4. ol ellolzl= 4e-ld ¤
llc.e= +A tlEil r= ol¤:6}],rJ zJ{{eE zflill+ qdg "J qel qq +tl=o 4--ts rll zltr E¤4sE ol+q}
e7J= 6J rlBg ¤BoJ 4o14. q7l^l= BzI+ fl4¤ /J.4
ttg
=rl'#l
qlolzJE q]+Ee azll-^JEll Ellolzl="JEll, Eq
Elals 1064nmo14, o1L3 Nd3* ol.$el nF {r.EllE+El ,r
=!soJ
l8cql^J olE¤ ¤E.J 4,"14.
e9 dz} tl4 d"l.ll 6]]R6J+.
4F
t E
K l
5 EgE (o
q
6
4l
G 7l',\I
oll
=
.fg 11G.10 L1lgtrlE allol^l01l,\'l "JolLl-= I0l=.
TI|LJ=
=s-d
tr1. EBg 5g+ trH=EE *= "Jq+= +Î
tlEll=,tlololl.<J rJ7. ddflal= 6l]El ql4lql sB.atzl dql +4+= 6liqEr++.
,J+l"lrl- ¤%le E-El +^l-= 6+61.= Sqd+. tr8. 40111 4tAg zHill+ qd$- ol+I 9l= tlElt= ,l[olo]l,tj
=^lE
42. ?.!tsg tr"lt rl¤:EE *= tlel= rlol9 4r]. zJ+1"14 zJ{4 o + *=q= +6J^d +^}trt.
g.H +^'l-= x1j,,iai_L 4rig euiiE+ zlqgr+. tr9. +?JE gEli= zl+ %r=oi Eqs qizixj 4 +BZ ,;
tr3. 4lz E'il= t}olal trH:E ^JqleE Hl-+^rc dsFltr}. tr-Ell4.
= =E qde
44. Jablonski E-E= EzI "Jql^l "Jq+= EI-+ÎC4 +ÎC tr10. zlfi{l* be tr-El]E ztlitll}zl +ag *9 t49 z1l
dol ¤4E +ei{= E!4 rHolr+. ill+tr.4 "*g eaol+.
trs. s=E dz} ,t}4 dol9 E 6Ir+E +"Jg 6[alq. trll. Eixtrg Cl E+ +^lC fl9 zl-+".+ 7}li'll+ 9dol "Jol
tr6. Ll{+ ElEtg 5g ffir tL4E9 Hl-+Î H++oltrl. +|l 6|= 4C"lrl.
E# 44e
?4: qzl¤E e+g zte dE s, o.zgl ++6ll +ittrI.
EE 11A EÎPJHg! gU4

=8
gxll
==
Dl1A.1 g+, %Ie oj Raman ¤+Hq^l ¤f,J4-oe ^l-SEl= zlB de Dl1A.3 g+ H HJ¤.BlEBql +El'l= C+E E"-14 +l"Jg ¤E6Iq
tlil tsIg¤- ¤E6Iq?+. 4. ffiIr+ zli-ll$s--E fl= +ql 4eI zl¤z| F"J6}AL+?
DlrA.2 Cq +zlel E"-lq4 ?l"JgF9,ol4i
G-\
L-i tl
El1A.l(a) 60kmh-'-tr d*6I= 44(6s0nm) tls. H3 ts"1"J;.9 cm-,o14.

"l *e"l +I gt= +._qg 6.50mm ?ol9 ^l.e ¤.zlql Bl ol
Doppler ol# 6IdL+? Eltlel ,il$ Er+^laqq 48.3yo9 {ol S+E{9.4. "l AeE B$EE
El1A.1(b) E"I"J'* +qgE d=6IE 4^4(680nm) d-s. 4ol ?4 +6Iq4.
(530nm) o + BolA!+? g-E-=:-ol rl-E.E
Et1A.8(a)
Îgql+iql eI Ae-aol 2.0mmoJ 43
EltA.2(a) (i) 0.20cm-'el (ii) 2.0cm-'9 +B d+¤ +Ei.Ie{H t'-EllE + *zl9l Br Hg F!+^lA er+ E+gr+ ag qlolE]= EflE+. {zl,tJ ,t1-g-
$ol $lulz| 99"t {aL+? "J
irltlg lt¤. *]lel ol gEq E ¤:"J 4l+= +6}q4.
El1A.2(b) (i) 200MHzel (ii) 2.45cm-'E +¤ d+¤ +4.llElH tlEllel + 0.0050 0.0100
$ol $ulz[ 9"]ot 6]AL+? ldyel/(moldm-r) 0.0010 0.0500
T/(per cent) 8I.4 35.6 12.7 3.0 x l0-:
"liil +q^l ei Exlz} trlla l.Ox t0'3H +# oJ+. (i) "ll +E"I
E1tA.3(a)
qlBddql 6.J gs= +"J
4 EzI9 EE {f tr4zl dAElr, (ii) r00H +EB ull"I4 + H4 dA EilA.B(b) 4e.-23o1 2.50mmoJ +A *
^lE=qlolEl=
¤+a 6lz}. ol +7171+4rll= 4lE dol.el c*(cm-'-E)g 4l&6}q4. 7lq Hr Er¤. r+^lvJ 4+ trl-g_r+ a3
rao gfltr+. ¤zlrJ
^F.s*
EltA.3(b) Tlill +ql^l 6'J ExlTI uJl= r.0x l0e{ A-.J+. (i) ,ll *E=ot Eltlg {ig ol gEE E g+ 4l+E +6}q4.
"Iel
4 EzI9 5= eld t4zl dAqjr, (ii) 10H +E=6J ull"l4 6J H4 de ldyel/(moldm-s) 0.0010 0.00s0 0.0100
g+r alz|. ol Ezlzl LIEi{]= fld d"l9 d*(hertze.)g 4l&6}q4. 0.0500
I/(per cent) 68 18 3.7 1.03 x lO-s

EilA.4(a) trl^g +tE dol"ll 4t alr Hl= 4l+I6lqeh (i) 70.8pm XC,
(ii) 500nm 7l^l %I, (iii) 3000cm-'el 4e-lC +î. E'r1A.e(a) 2.0mm9 +A ^le+qlq {ldl¤- Hl¤+C ¤:,|l91 +q^l H9
El1A.4(b) trl-¤- +cE dolgl 4oJalr Bl= 4lt}6}q+ (i) s00MHzg d
zlu|, (ii) 3.0cm9 ulol=eu|$,t1..
+. Hldlel t.E= 0.0t0mol dm-3olq.r +Îdq +a.¤- 2s6nmflfiol u|
tq^l ¤:"Jol =l4e ¤trI) +r+g Hel ^ll7l= "J^l*iel a8olo84. ol 4.
E1A.5(a)qtq *6ll¤ qI EeE E g-xl Al#zl z00nmoll^l 723dm3 ^Jqld t]41e1 E. E:r} 4l+= 4l&6}q4. +ae
ir}+ql^l 4.0mm +a
^l
4. t.gzl 4.25 mmol dm-r"J ¤.o-qg 4 g ?Jol ll 2.50 mmoJ rl
mol-' cm-r ol etrg ^l-e" 6J q19 5Xt=_E 9"lz| EIAL+?
E11A.e(b) 5.00mm9 +A g-E- 8"-49 Bfl+. ¤E9 L"E
E +7lql Bl ol 4tlE Hg F4^l7lH ,r,llzlz\ H yo+ a^6}4]l.-+? ^le+ql+ EI
E1lA.s(b) dltql +6il9 .J EeE E $:.=} alizl zg0nmoll^l 227dm3 E: r8.smmol dm-3olg.+.F4¤ qE ,rllzlz[ "J^]%]9 zg"/"94H ol rit]
ql^J ol gEE E ¤+I4l++ g"Iold-+? ryJq ++ql^l 2.50mm 4
mol-r cm- r o
l4. *gz| 2.52 mmol dm-, "J +.49 4 g ?Jol7l 2.00 mm ol r.l
trIel 5-rol5aE 9"Iz[ q4]L+?
E +7lql Hl ol E]-*el BIg ¤i4^1719 ,rllzlz| P y"4 ad6}d'-+? C
^lil+g ^l-8:B
q++lr]+. 7l^l ¤qql^l
Er1A.6(a)
"lxlel ^!ill ^1tr. CEol +6fl¤ *.lg 4E
7Jol7l l.00cmoJ Er1A.10(a) a-++71-
'Jril a.+¤. 6'IE ++l7I
g:%l Bflqq 320nm9 "J^l.+lel t8.ro/o7l Fr+qflq. ol rl-E_ Bl*Eel E+ g ¤+ 4l+71 6.2x10-3dm3 mol-rcm-,oJ u]l ol $f5-z|
^lB+ql 9"t"J3 4ols 44zlH (i) 4Hql^-19 ,rllzl9 Hl, (ii) qiHql^lel rllzl9
CE-g t:szl 0.13e mmoldm"ol4H E gr} A\izl $ulolflLu|?
El1A.6(b) qg g+61-= +eE *ETI 0.717 mmoldm-'ql +E +o e El l/lot Hg Brll EIAL+? *r'ill +EE t0mmol drn-3-=. +:ole+.
e-ol 400nmE Hg 2.50mm ,Jolqlt E"4^l? ullel F+I ults&ol ot.sy" El1A.'r0(b) zl=-H-B zl$ zlzla- 9lE +zl.el 3l'll E g'J 4l+= 280nm
ol+. ol ++ql^lel +Ael g g+ 4l+= 4lt6}J- r Bg cm2mol-rE 30dm3 mol-r cm-roltr|. +4'71 g"lzi qE Fr+¤ HE
=4q^.1
x1\tlzl il¤. +Îc9 rllzl9 (i) HL ^lEE
(ii) 1/10-=, 9d:+i
LlEl4q4
E11A.7(a)54nm9 tltlql^l qtr oJ+AE g¤tI Alizl386dm3mol-' E.t1A.11(a) qE El +a* dol4 +flq= ¤+r-"1 220nmoll,r.l
^lz}6}q
cm-,o14."1 ¤.dol +oI gl=+Eg 5.00mm 2"19 +7lql Bl ol 270nmoll.rJ d"JaJ ++4= 44442I:o0nmgl^l ¤U+. alEilE Eg
^lE
" e z}{a}r.
E"r|^laqq ol %I 4l+{}g 2.2txro4dm3 mol-rcm-'o14. d s"+g ,d,4B
+elE Hg. 38.52o9 Hol ¤+qfr.4. +e9 +bEE ol dol9 4+ ¤+ 4l+¤ +6lq+.
+61q4.
El1A.7(b) aaOnm9 irltlq^J qE 6J +eel g B* Alizl423dm3mol-' El1A.1t(b) qH tlJ d"le+ +flEl= g$ol r0znm9lrl
=AoJ ^l4}6lq
450 11 ErlP-E
200nmql^l ql"Jt} #+?]E 44442[ zsonmglrJ EU+. 6l4E E g ¤max e{fl = e.",{1 - k(n- 7.",)2}
"J 4l+<lg 4+e ^llg EEd
3.35x l04dm3 mol-r cm-'o14. C s"&g o
_e 7}186lr. ol dol9 4+ g+ 4l+E +6}q7kfB rr.r).
El1A.12(a) mor9 +^ gzlqî 821nm9 dzt dol9 Doppler-u.l{ { q)
gg gul-z| EldL+?
1L
El1A.12(b) 400K9 tgtzloll.tJ 2308cm-'9 tlE dolel Doppler-uld d* K
g 9"Izl"qflL+? i]o
,bln
0ru
vmax
s+#, v
fal n.t Ef rr 1A.11(b)oll^l rai-d sEdE EBd s.J
EE 118 altrEEJH
gxll
==
Dr1B.1 Eld Raman E%IHq^lE +i-ll4 Cq +4ql 4.J gel+4 ?l"J Dl1B.s qel B4E qdzlel Eld Els+Ee.l ol.?¤ ¤Bal{4. "lE
,JAl
g ¤E6lq4. ol zlz.ll{g z*zl e}E4ts qE41 9d,s4i
D118.2 BereF2E o =ee| ul4 Eg f,E (a) BeFrel zla]- D118.6 ?ld "Jreleg "Jd Eld .llHzl ,J4g *i^l7l
=rll6la!+?
qI4 s"&9 ea6}r" 6) e=gq e flol ulleulg"Jzl H+"Jzl= AC6I Îolel =flE
Ae+ E.= +zt^lvlilLL+?
q+.
ts l qla "Jolc+!E+
D1tB.7 E|]a sJol il¤ ¤86}J.449 ql
q Îolel
Dl18.3 tHr2C:r2CrH, rHr3C=r3CrH, rrj 2Hr2C:t2C2H 9 qlulzl a # rl]4 Eq4
+q^l q ¤lalE Egg ¤B6Iq+. q =9]
EllolEl: s r6A.2E-_E_oI4.
^fl D11B.8 ulol= +u| E+IHq q6J +iJlzl Cq +4E E?]EI4 g"Jg ¤
Dr1B.4 +zltlEll +^ql^J 0a qd ++l7l +4]q-= ol¤¤ ¤B6Lq+. B6Iq4.
G^
l -tl
ElrB.l(a) r4Nr6oE ++ qA lEEBql +4+= l=3<-2 dol9 1lFf EuB.6(a) Raman +%IAlql^l
^l-.8.oJ
flrl BrlCq tl+= 2o487cm-l
e+EI+E 4l&6l-q4. ¤B A6J ?olE il5pmolr|. Sd "J:qAg rill fi,4. 'nNr9 I=2+-0 dolql E||6J &+ Stokes +^lCE ¤"I41
6[H 1]5+zl ftzlalfl-+ s:. rJ46]4L+? B +olel. .
= 1.9982 cm-'_e
El1B.r(b) r2cr6oq ++ qd +4+b l=2<-l dol9 tl++ 8118.6(b) Raman e%lalql^l
^l.soJ "JÎ +ÎdE ++=
20623cm-l
eI ++s. 4l&6}q+. ¤e A6J ÊEHql
?olE lr2.8tpmolr|. ?ld oJrfld$ l 8.4. ''o,e] I=4<-2 dolql 'll6J stokes +îcE tl++ ¤"I4i
eJ6IE +l$fz} f;zla|l,lr{ E= Aa6i4lg+i B=t.M57cm-'e }:olel. ^}+
EilB.2(a) rHsscl-s- zlxll o]{z}s EgIg 4l I=3<-z sld dolel E}+b EltB.7(a) "Clrg-l 4d Raman 4dlEHg 0.9752cm-t ?J4E Stokes CEr+
63.56cm-'ol+. H-Ct ¤!* rJol= +6lq4. oJe| ulfo.l "Jdel H}-stokes Cs$ +4{tr1. ol BztE ¤Q* ,JolE 4l,ii
El18.2(b) 'H8'B¤ zo}4l al{zf.=. E?l¤: 4l /=r<-0 qd dolg ir}+= 6lq+.
l6.e3cm-'o14. H-sr A6J ,Jol= +4q4. E118.7(b) 'eF2E sld Raman 3.5312cm-t?JAE Stokes d5rl
Hl+qI "Jdel H}-Stokes ^4EHg
d# +4U+. ol +Îel ¤!* ?"lE 4l{}
ElrB.3(a) 27AI'HE ulol=+u| lulefloll,<l dE 7J4ol "JA6I4I "lel
ÎolE 6Iq+.
l2.6Mcm-tol4. ol EzI9 +d EdEe+ eEI4olE 4l4I6Iq4.
E1 I8.3(b) 3scl'eFg uiol=trul d= Îol9 7J4ol ga6l4l El 18.8(a) 3scl2ql 4* e F4 aqql 7lqlsl= +41 Hlsg +
^4EHql^J 'liill+5E
r.033cm-rol4. ol EzI9 +C sHIEe]. a6J rJol= 4l.t}6}q4. 61q4.
8118.8(b) q+ e 54 Er+ql TloJq= THill+5g +al Hlsg
cl,$
ElrB.4(a) (i) 2s'Cel (ii) lO0"cqlî z1lr11;zl zl* +g sld +91= '2C32S2ql
r2c-s r3cs ilQ+6}ts q¤ s4zl +E}+AL+? q qolq
qL aol+? B=olMcm-,E }olul. +6Iq4
E 16A.2= _H-ol.4. ^g
E118.4(b) (a) zs"cs+ (b) l0o"cql^J Br,e-l zfl{azl zl* tg qd =
qL aol+? 8=0.0809cm-'-e- +ilel. =91= EllB.e(a) '603+zlE Cr+(OOO4g H6]+) +919 +C _EHI-E9| ql
so 6lt sld t]'+E
4lÎ6lq?+(4*?f l1l, ooe* pol t2spm).
E118.5(a) ffi $xlf +ql^l ++qI 3tld Ra-a', ++B + E1tB.e(b) ,'p,HrEzI9 q<36 EIa+) +9l9l +C EHIEe+ 4s"6lt
fl= ag'5Iq4. ^dlEHg
(i) Hz, (ii) HCl, (iii) cH4, (iv) cHrcl.
sld tr-+E al{i6}q?+(4*+ e3.s', pHee} z)o\ r+2pm}
EuB.s(b) trl-*-Ezl¤ +ql^J ++6J 4d Raman EEH9 +48 +
il= ag E:"194. (i) cH2cl2, (ii) cH3cH3, (iii) sF6, (iv) Nro. E118.10(a) 4X sl4"lE Sol s"J +zl AB4(-* 11B.1)E at} eolEg
Ee 451
E"J6lzlEl a*4e7Ie0-4.+El a{xll {e-e +7H trllel ++c EHl-tr se32.lMHzoltri. ol +ztel co aB4 cs aBE 301# 4lÎ6Iq+.
E +4r+l= +6Iq+.
^lg
EllB.lo(b) 44 {.S f =o.stlcm-rol-I1 7 =2308cm-'o14. ol Sz}9 S
Et 18.13(a) rHr2TIel
*ol s"J EzI AB3(-tr lrB.l)E 0= 4Hill 44 aal"J c "Jrqa t'-+E +6Iq4. 'Hg 2H-tr ilF+6IE ol ^JfzI t+s gE|
A_Ba6J 7Jol7l H6J trllg + +c EHIE= +E}.11= 49 +6Iq4. f,E
p=R'en/RnsE tt-]r, G 2g+El lE HslÎ7j7I4.
+ E6td!+?
E118.13(b) TeBCtBrgl A+ B=0.0s09cm-tol-tr i=323.2cm-tol+. ol EzI
E118.11(a) rl^* sldzl-E¤ 5al.{4. (i) o" (ii) cH3cH3, (iii) Xeon, (iv) E gC "JrelA ^J+E +61qa}. TeBrg 8rBr9-E il++6lB ol t4z} "J
FeCpr(CpE;.13e.{144 oll B zl, CrHr). ftr gEI+ H6Id'-+?
rl+ flAxlf$ 5a|$4. (i) Cur=6112, (ii) (iii)
E1B.l4(a) trl¤. +zl-E-6ql^l ++6J 61X ulolzsul g+ 4EEH
El18.11(b) SO3, ClF3,
(iv) NrO.
g +4,3 + 9l= 19 "5"I¤4. (i) Hz, (ii) HCl, (iii) cH4' (iv) cHrcl, (v)
E11B.t2(a) HCN9I cld tI+E B(t!1tz6tr5;=M.3t6 GHz, B(2Hr2Cr4N)= cH2cl2.
36.208GHzol4. ol Ez}el HC eqlr+ CN aElE 'Jol# alt6}qel. El18.14(b) ffi $xfg +ql^l ++ql qd trFlr_e.ir} ¤+ r.ulEHg
EllB.12(b) OCS9I qd fr-++ B(r6Ot2C32S)=6081.5 MHz, B(t6Or2C34S)- LIEIB + gl= a¤- "J5Iq4 (i) Hrq (ii) H2o2' (iii) NH} (iv) N'o.
EE l1c 2A^l Exlel C=E.zJH

¤E E^11
D1tc.t 2gzl Ez}el Eld ^J+q ulil=

$$el s.r+E ¤B6Iq4. {f D1lc.3 F9l Se il+ql EaH^l +zlE Eldr+ 4lE
*4oe H.J+gla,L+? ^4EHEol "lE
Dilc.2 eld-AE Er*Bql^l cld tI+E aA6l+ ql A'*Î *Bol "l
B2l ol85l-+? Dr1c.4 2g^l EzI9 tlal iEl{l¤ {lHzl +d {tql s$d 6J+e+
Morse Er+E ol+6IE qE tld+ xlloJol rlgxlEzl ¤B6Iq+.
G-\
l -tl
El1C.l(a) Be41A14a9 zl$ {5 r+++ 4l4l.3cm-r('H"F); 2e88.ecm-r 491dg ¤+6IE u= 0o +Pq R71zltr EE4. /=z
El'1C.5(a) rHr2TIr--
(
tH3scl); 2649.7 cm-t (' H8' Br); 2309.5 cm-t (
I
H' 2zI; o
1
r1. +r-6JgA Aql= "J Eld tlEls+q ¤g:"iE d9 ++E +6Iq+. fls -*. 1lc.rE Ellol
e.l e tr'+E 4l&6}q4. rlE "l*a}¤4.
Euc.1(b) g+ Ellc.l(a)9 4lolEE ols"4q 6J.gAlEl++i9 zlE tl E1lC.s(b) rHsrBrq- 49dg g4alB u= 0o ?*el pzlzle- EF;4.l=2
5 El+= +6Iq4. .J cld t}EllE+El cE rl+-= +6Iq+ tJs *. llc.lg Ellol
elE ol*a}{4. =g6l+
Erlc.2(a) (i) 2e8K, (ii) sooKql^l Hlq-dE ^JE]le+ a4u -=E ^J4ql ?l
E clr$z(r= 55e.7cm-')9 tl'flzl += 4l4}6tol4. E1rc.6(a) r+¤ql 'ilgg 4=3 roog9 E4l7l2.0H24 11f,$g tl#
El1c.2(b) (i) 2e8K, (ii) 800Kql^J E4llHr+ a4lH EE 118 t'-EIq fl= i'J4.
"l r+=q e tr-+= 4lt}6lq4.
Br,$z(r= 32lcm-')9 ^Jq4 +E 4l4i6rq4. E.nc.6(b) ¤+eq 4gg 3=3 r.og9 Eillz} r0.0Hz9 tlBfe tl#
EtlC.3(a) t6o2ql 4* u=1e0, 2+0, H :<-0 dolgl LG 4lZ rf?]

*4. "l ¤+eE El tl+E 4l4}6lq4.
1556.22,3088.28, oi +sge.ztcm-'".l4.y.8 0ol+r z|{a}r. 19} x.E 4l& EllC.7(a) 23Na35clq- 8Na37cl-a-
a¤. E tI+E z*l dEelQL zlaai
6Iq4. q+. olEel 7lE {lE H yo9 zl-= +Ei'Hds+i ,Na9 a.d=g
Er1c.3(b) '4N2ql 4oJ r=l<-0, 2<-0, "i :<-0 dolg LG 4I9. rJ?J 22.9898m"o|fr.
2345j5, 46rl.q, oi ogg:.zlcm-'o14. f"E 0ol4I z|{a}r. 19} x.E 414} E11C.7(b) 'H35Cl4 2H37Cle- ag .J tl-+E *A dE"6J4r. 7IA6iq4.
6Iq+. olEE 7lg tF sl+= H y"9 il-= +El.ll4LL+?
El1c.4(a) HCIE ilg +C 4lF qlLl^l ++l= 1481.86, 4367.s0,714e.04, E11C.8(a) ,'CLq qi'J 7lE tlE dolg 564.ecm-'o14. a*E e
e826.8, ol tZSqg.Acm-'o14. ol +zI9 "ll4 "llHxlEcm-tqevE 4lt6} tI+E 4lÎ6lq+.
q4. El1c.8(b) TeBf'Brgl qlEi 7lE tlF dolel EI+= 323.2cm-to1+. a6J9
El I c.4(b) HIg ilg q& qlq 4 +91= 11,t4.83, 3374.e0, ss2s.sr, 7s96.6, Eltr4E 4l&6}q4.
H ssss.:s cm-, ol 4. ol +x}el oll 4 "ll
uJ zl E cm-'el evs 4l&a}¤ 4.
t52 11 Erl.#!
E4 l1D rlfl^l E^lsl cEEZJE

¤B E^11
D1lD.r dE Raman E"*tsql 4+ +414 Cq +zl9 E?-lo+4 A"Jg DnD.3 4qd E"&Bql ql'J+814 Cq +zlel E4+4 g"Jg ¤E6I
¤B6Iq4. q4.
D11D.2 cor4 Ag CB Hl+C Ezlzl Raman IEEH¤- +4qAL+?
G^
Jrr
E11D.1(a) c7J NC-(C = C-C = C-)roCN E4t P zll9
+Eqc a=g E1tD.4(a) Hl{l -zal= +"J6l/l S+^l7l= {f HJ^lg C4oll-u-21. o1
dE %1-^l¤. glaL+?
zfzla_ *alol (i) Raman ¤lc"l4lL+ E= (ii) 4e.lc Bd"l4lg+l
EllD.1(b) ca +¤ql^l a=g NC-(c=c-c=c-)8cN Bzl+ H zll9 E11D.4(b) {ldl aelg H E B o + B6l= tlE %}4g .t}ffi5!_z}. ol u}
4E %I^lg zfzlt- 9lg*i (i) Raman $dol4Lg* E= (ii) zJeld 9dolXL-4i
^lol
El1D.2(a) H,o9 Hlq dE r}qq q6J {lE "Jg +E}.{= 4]g 7l+ %L El1D.5(a) u]l4 fl4z} H,oql 4+q!+?
sI+E zlzla_ +4.Iq+. 11D.2^lq^14 zJ"l ul-asfrjg +^16I Et lD.s(b) u1|4 fl42[ eHr9l zt+E]L+?
^lEel
q+.
Er1D.6(a) ffi $z].$ 6ql^l zJelC ¤:f L}+.J + fl= a
ElrD.2(b) so,el ulq dE {l.Ellql q* {E
6}¤- +4.11= 7l= %r. ^dl=Hg
g g6}q+. (i) Hz, (ii) HCl, (iii) co2, (iv) Hro.
4Eg sI+= zlzla_ ^lg +^16I
++'Hq+. 11D.2^lql^l4 rJ"l ul-arlcg
q+. EltD.6(b) ffi $zlf +ql^J zield g+ r-ulEBg +48 + fl= a
g "J6Iq4. (i) cH3cH3, (ii) cH4' (iii) cH3cl' (iv) Nr.
ElrD.3(a) AB,ezITl (i) HldB"J trll, (ii) c¤"J tr]i
^ll
tlE +E q! a El1D.7(a) cf$ $zf$$ zl+ Tlt H.,l-^lg 9ol4 zlzla_ oJ{lL4; (i)
ol qqtl gaSol_/ lL (}l: {ol Kaman r5¤"J^l "Jdfqcf.
Hro, (ii) H2o2, (iii) qH4?
ElrD.3(b) AB3 e49 ¤Eg Hq+= dF %I4e 4e-lc gc"Jzl e= E|rD.7(b) ffi gxfpg z\? tl¤: %'-^lg H"l4 zlzlt_ 9l4lg4; (i)
Raman gC"Jzl g61q4.
CuH" (ii) C6H'CH3, (iii) HC = C-C = CH?
Eiil 11tr
+-t I lL xlE
ljo -,\trllEajol rll^l u^l
L-l
-llo
--l-E-l
gxll
==
D1r E.l 7li]l^J Hldlg t1E ,JÎEE +A6IE1a o'J+. ol
g+ ^lEE
=t$$E3 E= aol q4î +sq}
4e.1d Raman
zl dB6Iq+.^4EH4 ^'4EeE
G-\
l-tr
qE zlf %l4={¤+ zlEd BCol4i s
El1E.l(a) CHrClel
gC"J AEg oltr 4.Eolqi
EllE.3a)ol El1E.2(b) (i) H2O, (ii) HrCOel
"lE zl3 tlE'Jalol Raman 9C"l4l
Raman
E11E.3(a) CH2ct2ezlE., C,, d+ql +t+ szl¤9 H+l= 5A'+2Ar+
"ttr 7lf %}^lE{g+
El1E.1(b)ols*++Ê EllE.3b)ol 4e.ld ¤|dol
gC.J aEg 48,+4B2ql aaq 7l=4* %i^lEel qla 6¤+4qe}.
4i e. Raman
"]tr dE"l*i El1E.3(b)ol+El*^ E4^= D* dt9l ++trt ,r'll flxl-S9 Hglts A,g+
El1E.2(a) (i) Hzo, (ii) H2coel 9¤ z16 tl* *al"l 4e-ld BCol4t A,,+Arr+2E,,+E,roll aaq. 7\A 4E %I^l5el qla 6¤ +6Iq4.
Eg 4s3
E4 l1F tr^l 8EH

^trlEH
== =xil
Dl 1F.1 gEE FE He+^l7l^l ?*l :-
e+6JE ="
q 416}111 6}qr Dr 1F.3 2gz} &a EzI9 Hlqt}Ell 6* 7\Erl,>;zl q=
+gg ¤B6lq4.
6l+Ell, ol $-E.E ol ,J4l ^q"Jg q4lL+ E= *Al
E4slol4. (a) 6110}
^lgg
oilot al4.-+? (b) ole+ rJol ,Jol= HslrlzlH Hezl +4.11= 4ol B
Dl1F.4 Franck-Condon 949 Tltg ¤E6l-r E 4lF Azzl qB4l 6ll
,Jr+ 4%}E qL +_9__q ol$o|llLl+? ^l
+4+=zl= ¤B6Iq+.
DllF.s P7|zle+ RTIzlel Irl qe4 ^8zlg*t qzlzlE trl "i"-lE
ol¤9 ffio1 d-d dz} t4 dolE Ll4B + 9l4l-+?
Dt'tF.2 Zn2* r "lEE
olf¤ EL41 ¤H6Iq+. +4LilAL+?
D11F.6 +zi7| qB4 4¤- +Elr.il=xl ¤B6Iq4.
G^
Jtr
El1F.1(a) 6Jlilg 4ql^l gq+= d6}-old d"lE +EILH= E¤ o e 'EJ -'>J, (iii) r* ++ n.
x=0oll +dg +r +ol a"J Gaussfl ir+J="6J+E 4zlzl q.o1 ]aol-r.6
,<l
Hlqltr'El] ul-=r"sfz[ tlE E]EE]+ w=No¤&tzc
d +lil7} x=0oJ 4E Gausss dolqE ?ol4a {4+4. d
E11F.7(a)
"]tr EzIg
ol EHIE E +qA+. ryi=Noe-,{,-rd2rzo3 AE ^}49 dol ¤ ullel Franck-Condon
ly,xtydx==_ +6Iq+. 6J.E 4 "+EEL+E
l.tr. A+3r+
^171+
a oJzl¤ 4lt}6}q4. ¤+sl t++ TE.roal o + +q{q.
I4zl "Jolzl. Hlqt}E}] +Eo6'J+7I tlE E}rE"t++ w=No{&t29
Et'tF.1b) qL rzltl 4l"llr.l .JqLI= d6}-old dolE Ll4rll= E¤oe
Et1F.7(b)
"l¤ tszl9 rll9 Franck_condon
e +qd+.vi=Ntxe-o(x-r0)2/2oJ {E ^}Elig tol B
.rl x=09l +Cg +r
+ol aoJ Gauss$ irl"Eo6J+.e+rl *ol al2ola*4
trf= TE.toal o e +q{q.
+lilz} x=0?I 4E GarssB dolq= aol+r S4d4. dol "Jxl¤ al&6lq+. C+EI
sslE ly,xtydxS +6lq+. f,E 4 le a+cl ^l7l= ag E'tlF.8(a) q¤ EzI9 Elql dE tI4= tr.z} 4 9"Jol9 uls"Et+ vro =
^84612I. {zlrl 0 x roll -f 9

*zl elolel. (21L1'tz sin(rrll)-tr +48 + ?lqr < <
E1 F.2(a) z,:-4 ull E-z-+Hl(4)rI 2,s-4 rll E-2,+-dlr}4 $l(s)el + eltl+g

E *ql^l= rl-E e.+r} goltrl. EIEEL+ y,= (2tL)v2sin{n(x -Lt4)tLlE_ +
1
qxl={q7l^li Lt+<x<5Ll4ola r elE *ql^'l= uf-s:"gl-fz} 0ol+) 4l
zlEC g* 4EEH$ Tlzln rlpo}Elr oJ+. o} sltl$ol tg2nmoll^l
alql g+g +4qr += 6l+= z+3nmoll^l 4ql grJg 4elu4. ol al E tl.4e d"l ¤ rll9 Franck-Condon "Jzl-= 4l4}6}q4.
E11F.8(b) qtr +z}el Hlq dE tlqlE tz]. 4 "J"J"l9 ule"$f yo=
ql ¤rJ¤¤ El6JESr+ 4¤-^l7l-r. -z olf¤ ¤B6Iq+.
(21L1''' sin(rxll)-tr +48 + 9lqa
^846IxI. ¤zlrJ s
<, <loll 1 9
9 *ql^l= ul^='" gfzJ. 0ol+. EiEEI+ y' = (2tL)U2 sin{rc(x -Lt2)tLlE_
+qzlHqTl^l= Lt2 <x<3Ltzol:t r e.lE *ql^l= ul^s."$fz| 0olE|)
>< 4lE tlqs Aol g rll9 Franck_Condon "J^l-= 4lt6[q4
EllF.e(a) r1F.7a^19 ol+6lq p{ol z}zlel tll
4 2,3-trl0llg-2-+EJl 5 2,5-rlE1l=-2,4--dl^frlt! "14 9l^lq 4B6l^= lil
g +a4q+.
ElrF.e(b) r1F.7c^19 p{ol zizlel q q?-l 9lzlql qi%}61"= l#
E11F.2(b) 3-+Hl-2-g(6)3 2t3nmql^l tl #J4 320nmoll^l trtr| "+6J ¤- g +A6iq4. "l+6}q
%Ig .JerJ4. zI9C g=J dolE ts]]AatJ" r olf¤ "5"194.
E11F.10(a) trl-8.g SnO9 u}q dz} t}4e+ E-= dz}
^J4E +EI.l]= rI
o 4rlelE"lrl-.8=0.35,10cm-r, E=0.3I0lcm-r. olE qE dol 7I^l
Îol9l
,I q qel= +444tL+? qtr Xt.llrl olaol +4Ll]1l!+?
)--/ E11F.10(b) +¤e BeH9 ul-$ dz} tlEle+ E= dz}
^J4= +4t11= sl
zl"lrlEolrh B=10.308cm-r, R=10.470cm-'. ol=i qE dol TIzl
6 3-+EJl-2-g Îol9l
,I trl l}lel= LIEIqdL+? ol¤ /*q^J olaol 444d=*l
E'rlF.l'r(a) Hz9 'fru<-'EJ dolE R7t^l= /=loJ rll+61 *g <lql^l trl
E11F.3(a) Hiq Hrel 56|r+ o} zl-e.E +EtL{q"+.
HlqtI4E Eld tI+= 60.80cm-'ol+. ke ^JEl]el sld
"lelE +4u+.
^JE1]
El1F.3(b) Hr9 aJ =lzl 5E tr-Ellel o3-zlEE rruoltrt. ol 6-J 7ls.= qE
tlEll Hllilql 4g"al?ls+i
tl-+= 9"|zI 9dt4i ol {ololl,r-l e6J rJolT} ¤=7}6]-d!.+ E= ,JA
== 44L+?
Elq dz| ,'J4"11 4'J $d.J oJ zlEE +$,-ilqe1. El'rF.I1(b) CdHg 2rr+2>+ dol9 PTlzl=/=2s91^l trl
"l?-l= +4U+.
El1F.4(a) Li2+E
ElrF.4(b) otE Hlq dz} tr'E+lql q.J 6}el +E,-Hq4. Hlqt}4g qd t'-++ s.437cm-tol+. k¤. tr-qE qd rr-+= E"lzl-I
=+lE¤ dL+? ol {ololl,rj 4* 7)ol7l ¤:71-6}a'-.+ E= 446l.4lL+?
E11F.5(a) C, ExlE 'J EE ^J4el $lzlz|-{z} tsll^l= ro!ro"2rr!rn;olQ.
6}el El+Eel Hldcg +El.Iq4. El1F.12(a) +olg dx] tr4 gi=J IEEB{=
[Fe(oH,)u]3*9 zcnnmoll^]
ErlF.s(b) c, Exl9 += 6J EE HJl^l= to!ro,2ln,2 ffiel
+Ell7I Li4kttrl. ol
^JEllE flxlz]--{x} {t¤- +46}qe}.
rr!o1q-. 6JE trl¤:Ee+ Hldc¤- +4.Iq+. ô9 dz] t4 g;g- :-dleBq=
El1F.12(b) +"lg [Fe(CN)u]]9 3osnmgl^l
El1F.6(a) trl-g + z$zl-{.gz} 6l+ dol= qL aol+? (i) rn .-- 2fr, (ii) +Efl7t +4k14. ol zlEE <l.g +a6lq+.
^"E
rE <-+ rE, (iii) E <+ A, (iv) E+ <+ E-, (v) I+ ++ E+. EilF.13(a) t ril-fl 4lql^l "Jq+= d6}-old dolE +El-.ll= E¤ o e
El1F.6(b) trl-g + d7l-,'d+zl al+ dolE qL aol+? (i) ,E; * rEu*, (ii) .tJ 0 <x <a %qql^l 0ol Elzl ?+= qlEg irltrQ++7} *o<* <b gqql
454 11 Ert#
9zl ?*= trt¤ LJIEE rlÊoer+s dol9i 1,ol4l ^J4qIq. d

0ol ,rl 0 <x <a ¤99l,rJ ool gzl ?+= qlE.E uhEio 6J+9 4zlzl ca <x <a 1,
^J
ol r-SlE [y,xrydxg +6]q+. @<b4a- 7]4+q+.) f,E: 4 qq^J(0<c<1)ol 9zl g*= +E LIIEE irl-EoE+e dol9Y 1,"141
E r-=, {+sl rlzlE 49 "izl "Jolel. C4.JtrI. {ol sEe ly,xrydxf=_ +6}n olAE cgl 4q} q=EE +6}q
El1F.13(b) q} rzlg 4lq^J gqLI= d6}-"ld dolE +E']l= EB o e flc 4 El-E:o6J-Ae le A++ g..I4.
4. ^l7lb 19 "izl
E4 11G 8E
==ArEH=el
¤E E^ll
4+= g.4 E4E ++"_4¤. ^J46il jrz}. ol Ssqql DlrG.4 B!o}q qlTIqAg ¤H6Iq4. B%I qE tsql^l 6llrd.
Dl1G.1
'J.J ¤olg ÊEHg
o e E6l olg-g zI6IH ol ts^q EeE oJ* s.8ol 6zl*lxl E= eAg 6l+ E+ A++ zlgtr-.] *6}:+?
517'l
zl "J="l.¤4. ÊEHE
Dllc.s a)EoJ, 6) QI* "tlzl-t-l#9] +'J "JHI4 ¤Eq +EI6aE g6I
D1rG.2 c"ll4zl +E¤- +c6J # 9l4l---4i q4.
^lzlEl=
D1rG.3 4=9-] ellolalE gflE ¤¤6Iq?+.
G/^-
Jrr
Ellc.t(a) t4 EzlE r:; olq dz} ^J4s+q zlqdg g+6}q dl4
? -ll" TEfl:4f olX?J jl ul r'.l: -=i'd trtll- t_!"ltt{. fi-r "1.c- "l-u-¤ t-
!! .!- ,r-rr^t .rl l:l -rlr I.rl^l rr ,I-lI- ,lÎrl-l * a *lr rr]-d
d+¤ +4LI=q r E"Jg ¤B+q+.

El1G.1(b) +d szl+'EJ oiq dz} t}4e?El zlEcg ¤+6lq 6llel N B
c tlEllel Hl++ 9lulxl9 r=== tr-qs dol¤4. g+ q= Hlr4

,E,*
d+g +4q=ql r g"Jg ¤B6Iot4 = ,({ll

to
A
El1G.2(a) rfl rr.sglrJ nE Erlal dg *g SEql^l HlaufSol Eo1
fl= q*gE rill SEqq 360nm9 H9 a.<1,l149 q +4+= ¤%I
l.,dleflo1rl. ol $zlz| (i) BtqI dz} t}4el (ii) 5= dzl t49l flg
"I 20 25
zle-ts-H g^q+g AF qlLJzl ++lql +6ll^l qtr
15
^l,¤g "Jg + 9l4le 7/(1000 cm-t)
4i qs=fl!+
El1G.2(b) +=Bfllql 360nm9 H9 a"lE pol g?=lzl *zlEl +sB fal 11.5 fllaEiltsE Bg|' ElEEllts"te-l EEtEol
^qEaJ(A)rt
Hl4 U3qE49 ql+¤- rill(gfl) +"4e:zH rr.sglrl B+r -tr^loJ L|EILH= ?.!B
^trlEa.'(B).
?l%I r46}q ulsBdoe+Eig ¤"J cBg a
ÊEHdg,.ll+=tri.
+ 9t4. "l ++ a4-= ¤E6lq4.
=B
EZ1,t't 't EII frlzJfl

-4.61-xl ET.ll
o tl [/\ll
-1
t11.1 +Eg r{]^l tr}g dol 6! qL aol {zlffix} al¤-"JzlE E4

6l.q4. (a) ollHloll,rl9 n*<_n dol, 0) c,, +a +ql fl= 7Itr_H-H7lE lCrr
n*<-n {ol.
Y
*,.
N
r11.2 Ezl (ll)= eEdq E.qfl= ts^4t9 E+^ ¤4 sB o e

I
H
"l-&
eI4. "l EBql^l: "Jczis+¤ schitr gTlE a4 gÎq a6JElq ?l= 11
4lH zlzl +EIag il++6Er. 914. (a) +zl l7-B ¤41 +ue?llqe+ 4l&
HIH(r+7i zlaqDg ol¤6l.q (ll)9 HoMoe+ LUMo qlHzl zJ
^]."19
49 4lt6}q+. O) (ll)el rr-rla ¤EllE zlzl:t- ol 4ltlg E.lEol 6Iq ,,''., g;6.ffi $ffia= Le+ HI¤-6Lq ++3 EJs=Ell, 4zlrl d6}-old
4. (c) 4^J9 (a)cl o)ql .I.J 4lt} A+q "J46ll^J (il)el E*^ B4e_l dzl^J4 dolzl gqLI= 4,o14. 4 Bq4a= dz| azlla:.al-z r,b
n*?Tc 7l-^l gq dql $.!"'- {t+7I tt-rl} BEI{ qi.J aEq +d* {z} $2flE. ++.J+. 9. zlzl Ea14o-,, +Eql qoJ ol d6}-old dol
zl EE *4,YxlE +*6Iq4. 9 olluJzl hv."*ts Els-r+ 44.
E+ 4ss
rl{l ?IE4d
c"'ao
EE++E HIdI HlsllB +gEfl] UII*EHl
hvûleY 4.t84 3.654 3.452 3.288 2989 2.890
7 I
*apaE HoMo(d6}-old dololl^l dzl-= 4+=)E qlulxle| ftv."_
rlololl tl++4lr| 9ltrI= z}¤¤ arlt}{4. ol=-+!i|.+Êg HoMo
.llHxlE eB gs.ll^l ¤H.JqL o.J rl$g ol+6lq AA6|q+.
!1r.4 s4l- ro9 JEgl^l ¤Bo.J +qql qsE i¤ sldzl-= "JHJ A
+ol'+ zoHzll B+q +q+ Ezloll" qla qdzl+ 3l^+ 3+ qa+
----
ttUvv
¤- += Ezlolr_ r4r Hl4a qd4-b 3+(E= q rilE) +ol $,= I 10
Ezlol4. dB Ezl-b C¤ sldzlolr|-. ffi +{¤ol +¤, qla, dB, E rrr.a d¤ 6JEA!++e{r) B^l-=q sd sHleE 4+61 ol$ol
b HIEl]a 4dztoJzl E+6la +Eql "J46ll^l Bel 6J=J-^dg ¤g6}q +ElLll= dE Raman oT}zle| STIxl-r-- Eld
=.Q,
+aE 49 +
eh (a) CH4, O) CH3CN, (c) COr, (d) CH3OH, (e) Hl4ll, (0 slelH.
+ zlzlel ¤-+4= q-oJg i= 9loq, olag
44zl ?+=tr}. .:Bzl"JÊEBel
rrr.s *491 ol$ol czJ rH¤, rela +d, Ec, "t d%r¤9 4zl
Hr+ 0l+6ll^l ol +zl-=g sla tr-+¤- +aB + ?I+(R.I.H. clark and D.M.
+q^l tsaqflq. B4I Eila 801"J H,.9 9d qlq^l gd oJr Rippon, J. +Eil ^'tlTlql qlB6l
Chem. Soc. Faraday Soc. II, 69,1496 (1973)).
el4 F9 Er4E +^lg 4+ A rllt crt EqrJ llB.l3aal =91=o e +qA / <tg 9E oz1z1otr s7l-7.1E ¤+elE ÎolE TJ4ol placzek-Teller *
+. aE eld ^J+E dezl= i(E',)=252L6cm-r, B=43.55cm-" :a41 =

4l^l = ltzBkrhc),/2o
s + E^lB¤. Hq4. ol $Eql^J "Iellel ,J* 7J4
o ololrl
e=20.7rcm-'o14. (a) Higl eg Hld¤ BE +zlql Eil6ll^J= \t=2rLzl e E,^.^'1 .
Eg Bq+. deile+ =.zl Eqxl= olf+ rrs.r:^lql,q +^l+ oJzl-= HgCl, HgBr, HgI,
ullEol4. o) H3*ql^le-l u-s EB zJ"lE 3rI4 o + 4ltl6}q+. (c) I.B. el"c 282 292 292
Anderson(f. chem. Phys.96, 3702(199r))"1 oJxlE+4 o e Ee. 4cE & 6/cm-r 23.8 15.2 tt.4
11i- sz.zzpmol+. ol A+= ol+6}q fld ^J+ Be+ e= 4lt}6}q4. (d)
D3*ql^lE 716}+zl +ae+ E ttfzl Hiql^le+ *r+a zlzJap D,*9 E ol e'* ?olE 4lt6}q+.
+zl¤.E
^-ll
%Iq.4 ^J+# 4hI6Iq+. D3+ Bxl olgg l.T. Shy Hphys.Rev. rrtt.45, 11l.e 10cm zjolo; ,l4l +4 gzl 4"ll EqflE ol&E++i(2.17o)e| g
s3s (1e80))ol il¤.e-.e. zlelC }elE-floll{ vr(E') trlE *
^lloJa}fl-9-{, Eel gEi zlzllzl l.00bare| 2esKql^l trls-r+ gg ¤i%IE A(r)= zlzla_
*6194. 234ecm-'91 6dg E rR g+ 48 +4UtrI.
tl1.6 dzt +a= ¤A6l^= 4¤.J rEEgllqE ol+6}q q}^Jolq r+
a.
zi CAqI zlx1 ,<-llEE zlz\:t- H,o4 Co,ql +6J al4}g 6Iq4. (a) 4 E etil=
zl¤ql EItI Hlql^J4 glHzl, ¤¤ +a Bql, dE +EI+¤ 4l{}5lq+. uort;y l+ ar(i -au
(b) H,oE ffiz| E{le- a71¤ 4l&6}q4. ¤eil= Lss4Doltr}. (c) 4l

¤zlr-l Zl+Eg ar=0.932, az=0.005 050cm2, at=2333cm-r, 4r= 1.564,
t'J aE¤- ¤eile+ ullal-_r, zlTI gl+E I ol+= ¤B6ll -H-olu}. 4s=0.015 2tcm2, ao=2362cm-'o14. (a) A(l)cl s(r)E r4g$:-44. ol
+E4g "J+ +4+ #ql^J o,E adt6}r, gHI6l-=
rrr.z ollull4Efl trle+IIl+¤ +e_al d^= +Eol+? ol trlE al* d"le+ +zl dol
qBg el4. +Ee EzLL zlzJ 2t\g Fd+ olSg zlzla- gleq, qE AEol+? (b) B+ =gg as] {e"q- z}ill E:l{z} sBg olf-a}{ ol
"l "l =
ul9 dol ++e+ ¤]JEE 4lt6lr" r er+E ¤¤
+ olgol 7lvPl +lzl6}q E:Ese 6ILIE 02 +zl¤ aq+.Jtr}. tlca+g Hlj/6}q
6ll"ll4Efl9 Fero, zl|. 49 +4'il4 soonmoll^l dz} ^J4 g+ t4E 4. co eB ,Jol= l16.2pmolQ. (c) rllTlE ol4lolsrzi zl*e+q *
ûlEH!+
++UtrI. ol Bzl-= s00nm9 qlolx.l_e. E-Er]l 6}E +g Raman ol trlE Sd6l E+g + ilsel$ 5ol hz| $ufzlzl g4z}"t ai
Qzl aucm-,ql^l +4LI=ql, ol lrl= aqlg ,uo,9 0-o d+ 4!E ÊEH%I^l
=!=
ae+? 4zl 49 cor9 s=+¤-g 3.3x l0-4olr, 10km ol6}ql^J= T/K
q E+ 4 o + ^84grl. (a) 844cm-' ulz} ¤tl¤ or+_q_-e.+q qg+= =288-0.006s(h/m)olQ. ol trle-l 4zl FJ+EE +"le+ u|+E .J+s +E}
+4= 'uO, 44loll "Orrl g6Jg 6llrll4Efl ^lEE zlzlt- ¤E¤- 6IE Lllb EH fgg rEl4.
Eg + ll9 1014. "orE zl?-l6J 6llrll?-lEfl ^lE7l +E|'J '80-'80 {l 11r.10 EoJAEI 4qA9 dz} g= +e "Jts +e-l 5I+
+ *^lel 7lE tl¤' sI+E ql+6il -H_olzl. (b) oa o;(:a4tE} ¤."lg), f flcE
^JEll
¤+$= ril "1884. ÊEHS ol elc 4E $d
qr or-(r+4}ElgolgJ9 o-o {+ H}^lql 4lE} zlE dF ++Eg 4 =
61 J}qes qqflsq, cN 5 "*e +qrJEE ^{EfleEq9lq. dl
^dlEflg
4 tsss,1107, lEl-r. 878cm-'o14. ol Hs+ A6J=9 Or, O1, "l O1E 321
C9 ol {qa$e :_ 9"1 s}6}+=ol Sxl9d ^slEHol ¤qel EH"J +ÎCg g
+aE zlzlt_ ¤B6lq+. (f,9 s_E ec= Bolu|.) o,, oi, "t ol-el a +6171 qEq ^JzJ 1o14. r +ql olEg a +t}g q"J oldq gql^l
6J 7l+=g 9"I4t (c) glglrl Ellolqql ollull4e.flg Fe,o,
5r-lrJ ¤"&g 4+rll 84. Hae-sopp dld(C/lesol)g ^dleflol =4
71= 7l* g ¤8611= + gl= = qe aola-+?: Fe22*o2,
+g +g +=4611^l ql tlB6J +cg E*.Erll, qle^l 40J 6doe+rl Hel E9+l Hare-
Fd+Fe3+Ot, Fej*Orh. Bql E|]+ olf¤ ¤E6lq4. (d) r0gtsgq g-{lg 6ll
Bopp dlC9 dflcoma) +ql ?l= cNel ¤* fl+E E + 9l
"ll;lEilel *B Raman Aqlg t}^q o-o d+ HJ^lql ,lt ÊEH
+(R.M Wagner and D.G. Schleicher (Science 275,1918(1997)). ol
q= + q= ++U4. ÊEH* ol+6}q oI4 ql +z(7_to) 6ql^l ÎBE
"l ¤E e c+ +ql^lE cNel +t +sel ^Jc +EE +e?'}fltrt (H) rlE q=
6llrll?-1Efl9 Fe, zlr;q1 a6-J¤^l-gg
{}re,rl 4q+6lzl ?+g aE¤ qB4 g olaq q=
3s7.6nmoll 6d¤- +r ,"Joq, 0.1+Ioll "J "+"J (1-t) trl
+B + fl4lEzl ¤E6ll _H_olel. ^ll717l
4s6 11 Er[#
z|:ao.+nmoll 6cg +a 9lq. (0-0)r+ (l-l)ql 4Ei ul-ol4E 44 rss.: 40

4 +zt.onmoltrI. olE EllolEl= ol+6}q Hlq^JEll SoE 7l=ss llg'I
el 5E s,^JEllel qlqzl, ol +
^JEllel tl¤i ++e+ dE ++E
iL re]r.
s,^J4el u=04 u= I tlE *'llzl ,I4l+E- E
+6Iq4. EE s, T
gEE +4q+. s,^JElle-l 87ll sld

tlEilq flb +zl¤9 *a =91E-e1
E
o lltl,, ,
d+g+r 6]-=ql, ol 4*"1 s,^JqE +s. gEe+ +6JEl= rld"l4t =95"Jol Lo t/ ll ,l
trr.rr zl9 +zI9 "lluizl efle+ +'J eE= zleld

E
I 'rrIuulll It,
t
+71
E E H_q=E+q Eg + 9l+. ^JB6J {E +a= ,*= 'J
^
qls !
E
tl
I
il
rH rr.0.ll 44U zs"c9 zlijl ^dlEHq
IEEHS E
qJ
-+ I
^J so,el {z} tr4 d"l

00
^l [h
+ 91tri. ol dolql 4e} 4E ¤,JJ 4l+E +6I."1+. ol c," EzFts 4zl-ltl. 1,r
r(_ 'lllll \
+zI dolql E6li^J A, HIR ^J4e+El ol¤ dz} t}4-+. d"l¤ + ilaL
*i 200 240 280 320
A/nm
-fg 11.6 SO29 UV -ru:l-=E

=+
12
=vla
I-
o A EE-qt
+E-
¤t4 gE+e EAel trl^14 d44 A^14 CA ^FlE jr* Eqql^']b'A= "Jtlg¤ "l¤dq olag geltle-e q$4l
qgg ++. 541 gEo+g E I +ae+ #&o+zl qlolEls+ ¤Bsll= f lltszlE -H-ola ol flH$ q$rll "l$el + 9l=
El gq+4 caE¤ 4l+}5]+ %1-Bg 4l3"6tiL E slq}4 c zlql +HldEE= aol4.
eel BzI +=ql^JE geg $$6tz]l ++. rzo.r B8Ei9 zllE; 12D.2AlE BA qLlrl; 12D.3 8E Eg ErtE ril
Ig; 12D.4 +trloll trt= ollqrl E+
12A Boltzmann EE 12E Lt|+ ollLlrlel fllE +tr|

g4 ¤¤ql il= 4I"il^JE tr-eEE zllill+ EE= ql+6k
ol+q=
oltlel +E .ll¤+ $z|. $u[fl6 ol+4q gqqE F zlE
Ell Boltzmann +E4g r+qql^l zl8 u:gd ^l o +
Ehql 4P "llHzle+ qlE-E4E qBrll 4l4}6l+zlE Hol=
^l tlq$el
zfli1f +4U+. olae E s-Eel dAg 5
=' 4ol4.tleeul= Boltzmannol EE* al$ zlzJ;tq AEe|
,il *+.
12A.1 Hlfilel +Al. 12A.2 aEfiEE 8rll4 Tlli{l+
+ rI= ]l olag.E4l4 slE.Ei4'4r ++.
12E.1 Lll+ oilL1rl; 12E.2 tlE-EEl
128 Er} EH]l B+ 12F f,s. -d+=

Boltzmann EE '¤rr[ ¤+oll¤FJ+s+fot4 zllH
q+ qqxlei ql= +slE ¤+^l7l= 49 ol8
g eg+ gl4."l^l-e-E+El
Eqoilî=¤xli ql¤ qB4l 61l46rjr, E q
EHll B+e+
olH Helrnholtz 9lHzl* Gibbs "llHzl4 Ag +E gq+zi
Bl z]+6J a+pll Eil+ 4l^.Ig q$4l til+zl$ Eg aol+.
128.1 EUll Er+e_l Eg¤; 128..2 EUll B+oil cilE! 7lq 'J+# gg + il4. "lol^l "J+Gibbs qlHzl= EsH 4l
¤:zi o e +ae+ E%Iol4 rlloleltrPq Elq4 o -tr +s*
B¤t'-+-= 4l4lg + 9l+.
12C Ert qLlr! 12F.1 3E; 12F.2 gE 8+
+H]|El+E irlf{}+e+ Ag q6Jg d+ gqo+zl $+s^J

4ql +* :rE gqtrl4 C-tr= qlE6}r. ?14. ol Eqql^J= g rl-E 0l xlEel EE=?
EU}| d.f ol.$6}q
tlE-+B +zl¤E d$ol 444E zl
= E4lgqo+e ^JElulql^l qlE6l r*ol *¤:qr ?14. 4zlr]
E ¤-El %r"^lEel ¤+ilE qBrll 4l4l6l+zlE trg 4o14.
1rc,.1 TlELl: 12C.2 7lE ¤E t'J41Eq 7lq EHH ¤.+q 7l* 4d4 " e +Alq= q+ 6I'l-= da
=
6I*.+ + g* raqlrlE +4BEIEE +c 7gr+ EF c
12D g= gg= eE Egg ¤¤+trI.
Ezl¤$ BE6l ^ls tr-szl¤¤ aI{, "14+ ^Jsz+¤¤ ^lg

oll?zl *6|H ¤'4l gqolg +d6l+r B + SS 4o14.
"l
EEJ 1A Boltzmann Eg.
> 0l EElg ull+= ol*

1A.1 Hl|ilet+41
Bottzmann H. H4tr #l?lEt EI¤+= 016il61ts BA0l Etrt ?t!
4 qL aol+ g, ¤1,. . .E "llHzl ^JEHq ilg +
Ezl-E=g
srE gEtrt4 dH 0l H=.!¤ TFlr 6fl49+ fleq, qE,tl gl+. +ql "Jril 94lxl"J ol qlqzl.g 314 qqzl s0¤- 9l
EE g+Lt HlB +E7l eEoil E=6k 01ff= 6fl49 + ?lb
aolq. 0l E?qg Eil,esE 7ilEE "J6l7lE E!r.t. ElEtoil^-l qzl gB e-s A6Ir" 4 q=0o + +r ol49 zlf s_s a}]
olHrl trJ Elg T]lEe flE aoltrl. ol ql+ql 419 ¤zll q+ qqzlE ee
=eEt î +4U 4Eol4.
4E "l zl=ql E|4 4l&e} 4E qlqzlql+ "Je6J ^J+E
> "-4d TtlLJ
q4 +qo} *+ qE^J 4E qqzlql ql6J rlE zl¤E I
Erhill ,+:a I atE|= 0llLlxl e^{ LEI
El6ll ¤ 4lE 4lE"zl¤E dill od {lHzlE zlollTzl $eH
q= =trEl7+EEs.aE =?{oll
61ts Lrg qaElEloll q=il|.
AEfl +E Ests
?I q= 4014.
> gsEl qHl xl^.|
Ex|Ee ggEt EE+4
qat^1=
oilL1rl
=910ilU
+ flo.q(EE
9,tg 1r1 i7fi uflrl
7A), s.Et e+q 27t| SEll=o| Eg oll|_l^l=
0l.8e.l
-*EL{E
,LL Fll I I r lO
^r#E Euruf ?ILr.

Ahl^l :lFl
qE Ef "JEel +z-lg S46Its,
^l-e
+qlE q,"J ollulzl tl
4"tl lvrzil9 Ezlzl, e,"J t49l N,rHE Ezlzl,. . . Eq ilg
4"l4.No+N,+. . . =N3 Al ?Iql dill EzI izl14
olel+ =qfl=
zfli.ll+ +E' No,N,, . . .#
ol e{oll.<l ++q"F B Exll= $z} f5q1 +4lflol "JEel 9"F EL4. {No,N,, . . .}e+
gEql^J qtr ¤+ *^lql
'il61t^]+ 4+qE
zflill+ +EE *9 g-tr- H^l6tr. olag 4lel +t4 H|lil+r. +E+. EzI
41416l+ "J"luI. {zlrJ gs+ +"J6J 74 z4e. Ezl¤ol AE Q59l zflrllfEol f.r.ltr H6Fr_E 49 +A
= ^tolE
t}E +B4"lel"t'J+= a"Jql, olag 4el + qlqzlTl 7l] 4 ul]il= ^lzlql q+ s#. ++
zl| E{¤g qlqzlE qF+ eq= 9"14. dzll 4lglrJ= EzI +deg= ^J4Eol E"J6J
qlqzl. 4=+r ^J4+tr1.
E ^lolE ,(J.s4*"1 4l dillE qlHzl"il 7lqts +E glzlE| rflp E-= EllilEE qlqzlzt F"J6IQ r4a}¤ ruzfl9 E
ol +Alql^J= r 7l^b^dg -r.el6}zl t*9 lol4.rqr d:d ^l+ 9. zlzl4 tl{E"| ll"lo} qlq= ^llEg S,qa ^J4
4 EE qEq flalE- 0l+6141 9=.u]l, ol g?]= E= qlq ++. olzll t*9 f9 {tolQl fzl uflzlfi$ ^J46ll t+. + ql
zl EETI E+ +gg T}+dg tlzla- +ElB f gl4ts zi g,<J -EE Ezlzl alz] 9lulzl ^&4ql gl|l q. {M o, 0, . . .}
C"14. dtr4(a priori)o145 ag '+?-lz| "tE +"il 9lq^J t H]lzIE glg + gll" s 2414 +zIzI arq == ^JEllql 9l
s"l4E EZI e-E+ "J"14. gzl B¤g ol+r 9l= EzI {N-2, 2, 0, 0, . . .}"J ulilE 7ls" 6}4. ol +z}E ullzl$ z}
=
d+9 4+, qIAE}] + 4Hzl9 dE t'-qql fl= + 4s= "JHq += dx}9 HJ.BE4 rJ B:_9_EE ol 949
=A+
zt +E +"J+ "|Hzl$ 4= fld tl=|Js-l EzI +e+ E"J6t H]]il= E¤4 o e q ¤ +48 + 9l+. + {N, 0, 0, . . .}Hllzl
zl e}ot"t B 5 z|{9E %l-Hg t z}zl *91 Szl"J {N-2, z, o,0,. . .}Hl]
"l*zl-S.+= 4o14. ilE 7I4e_:-"J83 +N(N- l)ol g+. ^JE.lt rE $olz3 ;
o}r|| 6ll4ss+El u1s-zll q= 6}+el ql+61 +e+ AE
.9E,4= + =
¤. tlEilE "JE4"J slEll +Eg 9l= +H9 += Nol+. E4l H +-H.= tsoI 9lE (N- ryol
'll4l+ EszI I o e dill dq ,JB3 N(N- 1)ol gr+. rq+ (rJ-=-, a+)
I u}4"lqq e]=+trI= 4"14. olel* bEE F6il^J +rl
E $s.s-l ,H'Jg ts21 16ql^l +B^lA + 9lr ol +46J 4 (rJ+, A5;g ?g ull$olo + ols$ .!e. EZIB fz| $.
ceg qL aEBe+ il= 4"14. + trI+^l dill dq %IE zlE HlElol +zlg + 9l= uHEol
q, EzI 7P" d Ai.ll %LBE += +N(N- l)ol g+. "J"J +=
el a4E 4l7I {M 0, 0, . . .}H.|]zle+ {N-2, 2, 0, .. .}Hl]il
^}ol
ql^J s¤¤ tItrtE Nol q+61 . a+ E4l Hl]ilr} +49
12A Boltznann EE 459
N= 18
_l N=20o14ts 4g ++6}ts gr+. o!=1o14. tr14^J +rll=
rl+4 ?ol Er*.
=. =, =?9-1, =.,.= 9.31 x 108

" =- I!0!3!5!10!1!-
'lr1)
3!
llilil lllil
6! 5! 4l
HlliIE +4l
Îilli!-r+s "lael
dol e4 q ¤48 ollzl "*4.4,
zI¤ ql+
=
rn 1,1/= L+
fal 12A.1 187HE E^1.= qflg E7l(+rldo+ Es,\lTl=rJl,

lrllETloll 37H, HJE9I
"EeDoll
E&lE7loll67H,5e_E EEEI= 7Fo:d f E rAtolcl. ln(x/y)= lnx- lny
.=ts 3!sl rlolq,
-r.ajLl I4lETlollEl-:z6q E^|=
ETloll 67Hq E^lE 'E= 6!el 'JEEE. E+
E+)l
"JEg
-o-d =rll
0161 oltl7l^loltl.
trrttl=lr^6ffi =ln N!-ln No lNr !N2 !...
--6l],
qalAj EzJ 7t!-Lf Ht|il HJEfl #E t8!/3!6!s!4!0|tr|. 0l
'JE 9q EgH-4oJ
0lLlErl. lnxy=16x+lny
=ln N!-ln No !-ln N, !-ln Nr!- ...=ln N! - )trr^ntl,t

ffiol q .H¤- 4ol4.HL+q "5.tH ol + ullzl ,r..1-ol$ z|.s tn,tt= ole-" al-!. ol+ +9 6I+= Pzlzl d+E a
Erll +E]-E + !l+H 4el dzlse ol E ll ullilzl. 4lel ^d =^til= o B
ol+. 561 4l+g q^.q=r+ B3 stirting=Î^l ZI45|,r.14
eg AAB dol4.
trl-g B4lqlî= {No, N,, . . .}e} Ag gH}4 Hflilz} +49
+ ?l+.,
ol t= ol Hl]zlg +7.il+r r;14 w
"JHE += d46llB+. lnx! = xtnx- x t''lfg
fr^t o2^.2)
E ++u+.
rr-16l."j "l +al= *rl-4 oe +¤-4 aol ++g + gltri
*E 1?A1 Hl,lilol +zl InW ={N ln N-N}-I{lf, ln N, -N,}
^lel
NTHE ++g qq +ql aqi= "JBE +"= ^J4611 Ezl-. =Nln N-N-IN, ln N,+N t I,ru,=7yol s 91
d4l ="3 N{E tt"lel BH "e qB + 9leq, E4 *g
=N ln N-Iru, ln N,
'l"lzl * 6qlî N-rzfle_l trolel *H + qe. + gljr" E
o (12A.3)
r=o s-E. q.J
+ 9l+.q+^J +9 q4 zlqq Es^lzlz\ 4
6l]^J qB + 9l= #b r,(rs-1)...1=Mol B aol+.
%r'HE (b) ilEll += Es
rq+ so"J ,Jql NorHq +¤"1 A+ql= Ag += olul {$aJ u}s+ ?"1 {N_2, 2,0,.. .}el HJ]zl= {M 0,0,. . .}
=q7L=
g Nolrllel dlolal %rB "e q6J + llg 4"14(re 12A.1).
ul.$zlzltr_ s, -Ezlel z}ql SqzI= N,rHg ++9 q6F= ql
I uflzl_H_+ +^Jl6L4.
"lasE trl+q E- q "l + uflzl_H_
trt gl$ q +^]+ 49 uflzlr 9tg + qlg 4o14. {xlltr N
qlE N,! "J+el *B"l gl9 4o14, olal- uffizlzlol+. ,r|4
ol q+61 r'll= qtr fl H}|iIE Hl+ol 4+fl Alzl "l 4\
N,THE 7¤9, e,*"ll N,rHq 7¤¤, #ss +¤ =
^J a*"ll fl uHzlE 7l4e+ glril ¤+. rq6lq alel ce
g +^Jql +4lsol EE^l7l= EZI 7l-bql rlBE ++= + ^J=|lqlEl
g ol zlu]]4 Hflilql r+{
<lg +49 aoltrt ol zl
*4 tol g aol+. ufl{ uf=E6l
zl} t/4 <kg altr||E "JEq +=N,E <ti$ *"}
,,=M#r- ut|^lel +Zl (12A.1)
,lt$ Eg + 9lg 1o14. r,l| -tr=N,E aJfolt: + N,. H
El^l7lH\ aw_0ol qTll 6l-= <t¤- *eH oJ zJufl! Hllil=
Eg + fl$ 1"14("lae Et+fl +qlzl= *=,JHl} e
9 4ol4).ttq +Ellil .I{ql hWE +{il= *ots "}&
zlzlo1c1. rqLI tnl,lY E=Nrq el=6}E__tr_ ullzlz| H6l-r
lr,zllr,+dr,E Hts ullE tn Wl lntt)+dlnWL Hd+ql, ol
2041E FE"* 4t}+g t, 0, 3, s, 10, lE tsll¤E Eg.<l
dtnwY q-g=r+ a."1 g"l"F qL+.
7l= %t-HE +E 4lt6I4H uflrl} {1, 0, 3, s, 10, Uol.:r.
I 3l+ gg-J [nx!=ln(2n)''' +(x+ j)lnx-xol4.
=î!g
460 1? lEqEt
=
'w7t
. ^llE adgl ^J+= E+ trl-s tqlel H+ ^lql TLqI+.
';lLlloJLll
. HfEol d+ +84"J ailH +l+6J+.
atnqil=L(#)* 0 (12A.4)
. 4lÎel 'Julglrl tr-+# +qL+.
{zld E++ alur.eilaNbN,z} Hg ull t" Wl qeAl H6} E4I 1 T+E EE
+{Utrt1N,71dN,"E H6LH tn@l @ tn,rilDN) a{ol Eolo + crs} -fl¤-E +s= ,i6}ts +q ¤46}
zlloJ
=zl=
xdN,"E H*trI. rq4q hu)E + HEI+ E= olEel H 4)el + ^J+= +16}r q-q_r+ ee g=+.
^l¤-
ffi {-43 4"1 99"t 6J+. r*l+ r+Cql= f z}zl Szll "l Ealle.l
^.1
+ {lE oilLlrl
rllef
7| trl-g+.
zl'zlzli e-E ^JEllEol Egqr qlqzl= ^J4 *=+r I(H)*,*"tE-pt;t
6l$.trI. ol4l ol zllEg t+l4ot 6Iq, "JA6J ¤rl¤, dill qlq
r I
zl 6[9 *= H]]il="Jg relollot aJ4. ol 4lE trll$q $|g -. f( dln't'l )*"-Pe']ar'r'
=)
ullzli-ol ael q^J"ll^l ,,lle]g + 9l+. qE^J {M 0,0, . . .} 1lffi
=0, al4 zlql^l
+ {N-2, 2,0, .. .}E + tsllil= "tlHzlzl- ?zl ?*eq(sor} s,
el qlqzlz[ f,ola[zl 9+3 +), tr]4^J E"Je] tBA1zl ol + H+#+84"J 4Ee +l+
=,J4t2
ts]]il= E+ r+48 + fl+. tr|4^J slql +rllE ullzl| ffi olxlf dN;E +B4ol4I. a#++. rqH dtn,(,1=0¤.
"J+
r+ eg 44E "J+^l4oF
aJ4. rlB* z}]zllg ,ql 46H^J ffi aflol ql+q= +Elql
^l7l=
llqt
ollLl^l (12A.5a)
s+.
)N,e, =E tg6-d Eill ollr,l^ll
rlcll trt}1l tH-zf Ia
¤zlrl E= 4lE dill qqzlol+. trL+^J N,rI dN,HI+ Hg (H) +a-Be=o 02A.7)
trll dill trI4^1,

"llulzlb E6l-zl ?t t"t ++.
)e,dN, =o oilL1^l
^1lqr
(12A.sb) zl=-otlzl zl+6}rll ol {g +E6l$.=ril, +41= "lffi
^l
.il4 t"%r"ll ++ tza:49 Bq+= 4"14. r4E lnq,rE
E ll xllEg {ill gu3ol izl c6H4 glo o +(wz]]) _tr= {} N,ql +6H^l I,lB6l+ 44zl +g+.
Ell=.E "J"J"l fEol t.rl4 " e H.qle H6J + $.+E aol
+. qls^l 6J tl-qlel $"J"liE a}tJ f;zf.<lzl4fl trl-= +
@ h'uPls.-sr#
/J.EIg
"J"d"lizt 6I+ ali9"l"F ++. Ir|4^J +s_r+ eg
z&vl7\E "J+^la + 9t= 1,19 4)Ellzl= +6tlo} 6l+ aol ol al&g 6izl fl61]^J rze.:zl$ q^.q=4 ?ol tl49 ¤d9 i
q4l.il j_q Hl-+= 4.ol ¤4aI+. +
+.
Exf # xlls+ (12A.6a) ln'l,l = N lnN- ) lu, ln iv,

IN,=w tg8-et Eill E^l+l
ul+^l N,7I dN,"E HB trll ol ojulol + oJE E6Izl 9+"t t +

6J+. nlBI,rJ, ln'l,l =Nlnw-lw, t"N,
Idw, =o E^l+ (12A.6b) ole+ ?ol alfl "lE H+N,el ,E Elflel ,e| EE" 6J ¤4zI $.
^1lqr
qdq ol !g EIE6IH q^q=4 zJol ¤4.
zl++El ollot E "J3 "l + ,llqx++ z4) 6}ql^Jel 44
x{t B E{I B
+rll Hflilql 4B$= r2A.4^lg Eqot a}b 4"14.
dln'l,l a(N hN) a(Nj lnNj )
-a^r, EN, EN,
@ xPfâat6}Tl
aag +6I= %LBgpseph-touistagrangegl E6ll^l r EAI 1 a4 'J 4l4I
îlE +He-l a4l 6Jg trL-q-q E"l ¤ + 9l+.
?Iqflgq, ola¤.'ul{ f,f H'ol4l ++.
12A Boltrnann EE t*61
dfgldx=fdgldx+gdfldx r2A.74:=_ ol¤-6IH ol

^lol
trlgr+ B"l ¤4
D(N ln N)
---ar\ (#),,.,(H) -r.,f +a - fr¤,=o
q¤4 q=N, uI4^J,
eI¤ q+ +Al7l cB6l+ql, ol13 ztol
'E
N+ql E 6I+"J 599lzl u|E"l4. Ni (12A.8)
= N
eo-a''
Eiv a
* ...)= I
dN, dN,
(N, +N, ol 44= Boltzmann EE4r+ 'll+dl Hli6I+.
-I-
q-q +4lE CH6]]oF +trt
d ln yldx = (1/yldy/dx
(c) tl#EE ut
olzll +* !!$ ++-6}zt.
ElnN laN I
aN, -NrJ\ -N Itr = IN, = !Ne"-f¤, = Nec le-ljs,
ol + +41= ols-" 6f{ r *E 4ol 4*4 ?"1 gr}. "JEql^J Ng ++4 eg ^lg eg + 9i+.
^46IH
a(N hN) 1 (12A.e)
EN, -,'
- ''lN+ I eo
,-F;
tr,J7,l2
E { '} 414} EI+^l
E4l .Jel EEI+= ++4 ?"1 449 + ?l+ gei e-
Dr,
i
-"tt". - Boltzmann E-S. (12A.10a)
dfgldx=fdg/dx+ gdfldx
*=a"-r. ,-F;
a(N lnN ol 4gBottzmann E={olq, g6l q.gr+ z.ol 44d4.
i
DN,
?{(#)'"n.n(H)} r\I
rri ^-
L
Dt,
N- tf
Bottzmann EE^l (12A.10b)
d ln y/dx = (1 /y)dy/dx
{zlrJ yi 4¤-r} ?J+ ae_E^l EHll et+4r ++

i {[H)'*.[#)] ,i=\e-Pq EH11-BI+ tgell (12A.11)
=I{*r,.,}(H)
ol +Zlql^J= ol Ets}| 6J+E..JCg +44= ZI¤+ ^J++
E-Nj= -s-g{oltr + trlE aN//aN,ql^l=/=ioJ 6'}¤- zlle_16} atr+"J + 6114g glzl"J olaol ¤qolzl
= ^de¤- ELzl
E E+ 0ol g+. ? aru,lan,= lol g+. r46lq, 9qi4 " e 6]]461-= trll +d q'Jg 6J+- 19 e_q 12Bql
HH+4 E 1,"14.
a(lr, hlr, ) ^J
= lnN + t2A.ro^lg 419 4q e+Ei z]]rllf t4zl-+"J r++"lEl B
Ni
.i
gEe+ +41¤+= ag ,Jq6lrll
"il 96H^J a++Elq, "l Fl
E4l 3 +6}tlil7l .J^lqlq. p AI= Cal + +E6}EJE +lE Botrzmann BI.^l
"
a4e+ E ll 6J-ig 6J6]]+E trlgl} ?ol E4 I ol*alq Sd zlill tr-ql^lg +E6llo} 6i=ql(Eq r2E
6l E-71 l2F,lql^J +E_+trI), ol +E= a{_H_H Bq ++4 =
g
dln'lrl
-a]\r, = lnN+ 1- (lnN, + 1) 3 +4lE Eg + el+.
I
7-
--1
B -iT 02^12)
dln'lrl N,
-A^J, -- ln ll ¤zlrl 7E gqol4 s-EolA kE Boltzmann ^}f4. ol 4+
t+62 12 EAIEE:qI
g tr+s=$ ?"1 ul^tq E^l$ + ?l+. 9lHzl ^Jql4 ,Hal+= rzelop.zl ts "ll=
qs+-E=
=flE
IBJ6H +qot 6J+. r;la}ol glHzl e,4 fflz} &6",+ I
94 *BS olFr ?l= 4lel ffiol ,l.a-+g ,Hill+ tl slqq 9lg ull}(+ ol &7l]E tt4z} fzllaJQ) olluJ
4b s-4 gEql E611^J eAE+ =+lql
zl dill tI44 zfli1;g ffi al o e 444oF tL+.
=91=9
Boltzmann 7H^ll+ Hl
(12A.13b)
tg4 E-9. qalEl
6J +xlE F E4zI S.oklmot ,E qq4 iL= +4uqa
6l-zH+g Ezl{l qlfl^-l= 8.3zlol{, rzl_lyzrlol+). r
".l6lq
¤qi A= qlqzl 0"J d-4ql ilr" Bq Bb e-B.3zt trld 8Et|=01 SE}|4 7t|i{l+ 4lt}
ql +lil+trt. IrI4^l 2o"C(2e3K)ql^l 12A.10a^19 EE.= 2s'cql^l Hclel I=r4 /=0 Eld tr-EH=E tlql4 'H4l+
trl+r+ &"1 ¤4. +olq4. B= 1o.5e1cm-'o14.
k
=
Ig-e, = L+ e-,t = l -.,u a-(8.3xto-2r
I )i(t.38txt0{r, r-' )r( zs:x )
= 1.12. . . r.a{g Ard H}qtr-4= 9n}9zl
?*itzl"J /= loJ
=+l=
3+_q-E qEiqq flcHM,=s, * 1): "Jzl^+7| /"J t}4e-l ql
Irler^-l ol gEql^] B4 Bql gl= +x}q Hlgg +g_r+
Hzl* erhiistg+t)ol+(Eq nB). 2e8.tsKql^JE + +
B"l 84. ol4.
+ql +Al= kTl hc - 2ot .22 cm-t
NB _
-
e-(8'3x10'try(l.3sr"1g-z:;6-r
)x(293K)
I=r4 /=0"J t}=ll$ rl"l9 qlqzl ?J4e ¤t-¤o=
N t.r2* =0'11 =ol
2hcBtr+.7= 1o]tr. M,^Jql +q qL 6t+"J t]-EllE /=OoJ
^ll
l trvo{ Ezlz} ol ¤E1e +"J t}4ql 'll¤L T}lill+ Hl= trl?+^J r-1-9-,=4 Bol ¤4.
=z116J+.
yJ1y1
No
- ^-zhcBp
1A.2 gE!|=el clE]|4 71|iil+ tg tlEflel 3+ q+E= rq6l$ ol qlqzl

^JE]]el ^Jql
4 zH^llfz| ffi4 *ol S4.
12A.10b^lg 6l.{ tr-rl]=-el ^}rH4 ,]]i.ll+"J¤. -ILEj6J ql
ol-4"
EH}] EL+= +g g,q7| S.+. Hlgg +ts trll= ol EU]] sr

=
fz| t+ll9zl rllgol4. fr= 3r-zhcb,
N e-Pt'
r?]6}q -_hc$kr = (10.591 cm-t) l(207.22 cm-,)
hcEB -
-FG'-e Boltzmann 7Hill+ Hl
- .-& -'
)
(12A.13a)
N, tE4 EE] 0.0sll ... "J #g Bq+H q-q=4 +2 4+r] +gtr].
ol E6rH ollHzl 7J4ol +qag ull zH;lli ul r,r,/n63 = 3.-2xoosrr"' =2.708

^lql
fizl *zl*q EizxgEzl. {o1a+-a_) r=0(44^l ai++ *
B=oo)ql^J= HtqI^J4ql^JEI z\l4lizl

=zl]6}q
q-4î ol Hl +4 /= loJ
=+l= =+lE+
/=091 9lHzlz} kzlt} 3+
zl. E+.
oo1 +H+lfl 4E ¤tlg
l2A.t3a^13 ola11alb El e + qelEl"l ilzl qEql tllzlllzl q B:+. ol Ezloll.{
ga+rtl +s6}q, ol ol+q=
^lg f,!*4eE
Boltzmann E= HIel ztol z] t1-e1.9 tr-'H4 2fl2115. +61^= 4"J
Es!r+ E"J6J ¤E|]u(qlE^j Eq ltAql^l B*eI4 dol zl E= .tlHzl 4=)E tl'llzl 2fl2115- 7
rllzl$ !.g uI ol+O. ol =+l(qE+E=
96lE + ¤49 tr44 z\^ll 6l*= a"JzlE +E6l-41 +E6]]ot EI+
^lql
+= rE-el qlqzl iHl rl4 zlf nf4 oe. eA++. xl7lB.7l 1?A1 u.9 .gs.ql^J Hclel I=24 /=loJ
q7l^J f.:z_a1lop 6J +g6J d3 soltzmann +E= qlLJzl =.?l
olL]4 +{EE E9 zfiillf Hl= +6rq4.
=llzlz|l9 ^J.I4 z)12115 +4U+= 4,"14. 69¤'I :.8
94 t4E"l Eg+ qlLlzl= 714 + flsq, z}|z]| tt
EIEE t[{lizl12A.13a4l o e +qd+. t{-4^J 11"4 trHdql
12A Boftznann EE 463
T]ILJ=
=s-d
! l. dBq flal=
El=el E-= qlqzl $Ez},+ElB zl+C I 3. Bottzmann EE^lg gEE s-Eql^l Al9 4 ^J4E'9 Ezt
- 7lC6l+
ol Eg6I+l 4o14. += +4U+.
J z. Nz]lE Exts g 4lE +Z!4 B]lil+ qlqzl G9 a,e,,. ..9 Z 4. q"ll^l7y ot{ qlLlal ql+ Aq4 7}li{l+=
^Jqlql =+lEql
THill+ N6, N1, . . .g +445 g,rllE= H^lqI dol4. qlLJal qE+EE rElsfl+qot *trl..
=+lE
=e-d^l=
.r-lzl
o= AI
-1 +4 4Ha
Bolzmann Eg^] N,lN =e-P'' lq F=Ukr 12A.l0b
EU]l AJi o=)" s.9 rznE -H-otei 12A.11
Boltzmann 4Al+ Hl N, lN, =(g t I g1;.-r(''-';r sp sF qs+E 124.13b

EE'l2B EIIEH11 Et+
> ol EEE H|l+= ol*

"l *Cg zflzfl $z| ^Jqql *el 4"1 "Iqq 9luJzl ++l(E
qlqzl= 4= tr-Ell=el aJc"ltrI. Eq l2A
Ed gqtrt3 Eutl ff+= Eoll^j 4lttolLl'#se 7:d Erl'
"J6J ^llE)ql *eI
ql^J ,Ja+ Hle+ ?".l alz"l -"1+ qlqzlE ool4, eo = 0014.
¤E= BEE TllEE EEht gqqt4 8tr4 E=6t|Etrl. r4al^l
0l E]trlE LflE3 ?¤ Ert=el dE= 7l^la 7..|^14?l Ealsl4
Ltlrl= ElEt4 d¤ 0l61|6l.b tll B#fl 7la7lflLl. zlEfEt q 128.1
Hl-qcl olluJzl 0, a2a. . .ql ++qqfl= +z|7l 9)

> tr.{d 7flE =fl
Eufl gt+= 4luolLl Ets-4floe ftE-d ErlE dE= 0lE6t|^j up a1z11t4 tzs..l). ol a+E EzI EH}| q++= q^q=r+
8EEttr|. eol g+.
> =Jg-e! qlHl xl^l { =l+ e-& + e-rk +...- I + e-k + (e-&;2 + ..
:"lE oilHrl
BolEmann ExIEE# #.l tlel =l4 EEE qE
LlEtL.Irl= ag g0t0} EttrHEtrl 12A). EHll Et+E TtlEg sE
EEoll^'l aTllolHo.q q7[1 q gE^le aolq. Exl'E trldz]
T!= LIEILII= l l Bel rr D)al 8xl + gtsolel
=91-
qlLlrl=91= LtElL|lts
^l(EE
7D)E=E gr ?lolot etcl.
^.|(.trE $e
:
3e
EHJI *+ {-Ie-ft9 Eq t2Aql^J Boltzmann EE^l 2e
t
(12A.10b^l , p,=e-k,l{, ¤zl p,- N,/N)el EEql +++= ^J
^) 0
EH=ql +qI qld-e--e^J t+61 EoJqflzl* r Eel=
fg t2B.t ,aF+E Xld6l"= r.ll 0lEE
+,q6I+. qls^J $u1l g;3 ^Jg.-qB o3u3ol$_E ¤ 4lE
=ld EiHH
=7J?:4+-Lf6l
".J= ollLl^l
Itrl' tlE^ 17 I 0 lel'J= oll Ll I
EllEaJ= LfEf L.! E.l'.
4^14 Ceg al&6}= ql gs-6J e= A-E-= LtlE6Ir. 9l =+l=. ^ =91
4. "lBt,tI Eql^J "Jzlqqlql^J ,l-E.o6L-Azl zllzll Ezl¤ql ql lxlcr"J trll= zl6F"f t+x+i +...9 Eol 1/(t-x)ol E
6l]^1 6J 44 Hli6J qg¤. ,/l A^14 4lql ql6ll^J qlqa E +.tr|4^J 99 EU}] 6J+= q^q=4 ?ol ¤4.
+ gl+. olfl Hql^l EH}] e.+= "J+q pzl ffiou-"J a q-.
I
ol+. l-e -tir
ol giffi E^lql 4"1 :H 12B.2ol+(p=UkT).
:Et+ol
128.1 EHJ|
10
=gd
:d+=
Erl=H|{ +¤-r+ a+
'.-
,i =\e-re' E^l EB[| -Et+ tle-ll (128.1a) <l-
5
states 'to-0
!
rl.l
¤zld g-Ukrol+. Eq l2Aql^J ,JaqL uls+ ?ol 9zl9 aJ
gg ^JEl]ql aa 4olE, 9luJzl9l ¤rl 4ol olq+.&71lel ^J
ol+ tlqEol E+ {lHzl eE 448 tr|]}{+ ol ql''lzl
zl g,fteE q+Elq 9l+)
=+l 0
"lag r}q=4 ?"1 5 +E 9l+.

0 5 10
?E, krlt
ral
,/
I
levels
8ie
- 0¤, EII $|H1|
#- gEEa-q
Et+ t
(128.1b)
aal tzB.2
ol-^ O.l
-1L
rze.roil H?.! Al(Ê+ T.!E^l')oil rH-d EHtl E#9 8s.
128 Exl EH]l -d+ 46s
LIO -QE r-.O O- 1.4 2

XL L+ EL LI
--+----
's-
#,, 1.5
-I
nLr
!lJ
Br. 3.0 1.0 0.7 0.3

'[i 1.05 1.58 1.99 3.86 0 0.5
1
?E, krle ?E-, trte

:18 1 28.3 qal e-Eoll,\l :fal 2B.1 oll Ll-ElL.! 4lel ollq^ I
1 I zHill#el
o + Z t-sf 6 =J E [l :Er+g ZI. = / kToJZ +el =f.l=o lg :d#e
1 2 B.2 a l l ll
0
H 6 CIl
1 al-. 128.4 EE9 +EF,! 2=+l 4lelEHH 3J+. 0lrallE=g I-+0
"Jul,ity 1e tr=6E !E r-+-oJ il Etl2-e tr=61| ,iE HG+zl +16[q
^
._gE+9 4E= trlBll +61-fitr1-.
+]E +++ qlel e4= 7J40]| n=7,11 e"J rI44 -EroJE
^Jq5ql 4el EUI EI+. LtEIrll= 6-,q* 4"14. q$al zfl;llfi-ol po=r\ pr=0ol qjr, EH|] $+= {=rol
=
q=zl ++6}0l+.rfl+ r)*(B)o)e qH +E Tflzll+
{ =;;:w
1
EHI| EI+ (128.2a)
tEgef
^f+atl Eol ?"}^la(?o-+,pFi) {-2(+ t4z} df'B4)zl. E+
ol +sCg + 6]]4g
^lg "l+610l EtsI EI+E E?]+4
9l+. +d Boltzmann Esql el6IH ol qlqzl ull$oll,tJ= ql gE 8^l r=-oJ trll= ZlE +^l7l d+ glHzl * t4
4z)zl qql ^Jqlql il= Ezi9 E¤ p,=N,/Nol trI-s-E4 eol ql ilg 1"14r 2+r+617]| eq. rel+ r28.4^lol LtEq=
g+= ule| ?"] r--) oo-E. qE t'-EI=! zllzllltl Botal4. ol a
Î¤g 4= +=+1419 A+qlE ulafzlzl-tr. ^JB6JtrI. 1r-+*
e -k, +E 7Hill+ s EIE E= t}qlE"l E"JqI THill+E- zl-xlz.ll ¤4.
(l-e-e;s-e' (12B.2b)
P,
f tE"J-Lf
^f+ell
ol
/,rl gEql q= Hq¤ -r.H 12B.3.il +EI4S.+. ql+61 fl65 gzlsE d3 zl-L"d tIEl]EE +
"lzll +4=.$ufl
*3 $s.(3 pq1,<-1} qzl 9l Tlvl+e 4el {+Ee-l +zIzI +4U+= AEg "JHlEl ^la + gF+.rrl0oll zl-z|.flzl
= u}4"lq
alzl t4ql 9l+= ag g + 9l+ gEzl-g+e+E slzt E Pl .f*4-e d=++. :z4610l f= ¤Eq+ q+
tl']]el Ezlfzl }f tFqE EzlfEol ¤d +7t+tr1. d +q ^llel+

E= o}.ol x+ -"J 419 *e+ 7J+
6J 6Jg
E, ole+ =r
EI4l +Hl] EI+q aIE l_tr+el ?zlaLbql, ol4.g E ¤ol qtr + 0ol E+. ol gl4z} q= + a}g a = OoJ rJ"Jrll
zl¤ol qEl tr-Efls EEE$ 9"latE 4ol4.4b di{ Ez} k0+e-e- q3rlqHg ql= 9lHzlz} OoJ gozll$ ^JEI]E), ola
izl zJ ^JeEq AA^l q$rll Eu]]HEzl= Ll447l trli$ 9 9sz} 9"Izl Elgog sEI+) $4l$"l atkr = sol Elzl
oll .EuH oJ+,+I. +E= 1o]4.
,l
t4z} so=04 e,=eoJ E+.J |++) 4l'ql 46llrJE ol al Po

g r+s-r+ ?"1 449 + gltrl.
{=l+e-k EUH Er+ t2=91 Ztl

(128.3a) c\
Po
<F
ftu 0.s -----0
e-k' e-k' +E Tl,lill+
A
fi- (12B.3b) Pt
{ - l+e-&
-_- nl]
t2=9 Zl, i=0. 1l
?t
q+^J + rllill+= ++4 *"1 ¤4
^JelE ++-
t e-ft
0
0 0.5
0
0 5 10
Po=;;:F Pr=;;F (128.4)
?r, kTte ?s-, *rte
:.H 128.4+ gEql rrIE EHll .J+9 Ho1g., :.4_l :.H fal 128.s 2=91 Zlel + SE}|sl 5p u tlilt#(l2B.4^l)ts e-Eoll qal E:Lltrt.
?=t1+-dEtle tr=6tE + SEt|sl 5.E ztlill#7| ,J^l Eg(trt A0l o.s_e
12B.s= +E z1]illizl {Erll H6I=zl= +q'd+. r=Oql^l tr=-l t=auaf.
t+66 1? lgq-+
=
ullEol4. T=0oJ trI= {} o}"Jol ¤o}k}gq r {te-goolo +
trl+r+ ?"1 ¤ + 9i= 4,o14. =,
-_ -T q q _R _V .E
1-cl tl EH|]ET+E ?.!+ Edt| (128.6)
l,'\, -- s,
ols+ ?ol
"Ji E"llz} zl*al$ 4 zlq# EB4e_a 71;
4 r=o"ll^J= EH]] Etfz} Htqtr-4el trl3rlEe+ Bol-ticH"J 6J + gtrll E+. "JHl4 " e EHI e,+= AE4rll 6114 6J+
*4 o + rol !zl"J gg4e+ rfl ag olqq). E ++'J + S+ r4+ eg + 9l= A+7I "*e
olHqlE rzl- trllBol +o}î qld +e-l 4.JE Be,=g,tftr=s =Î^lg
q, p+qt ¤tr-E¤ ola|loprll ql+61 +s6}rll
"1¤-¤4. "lE
ol El= a+= r!4tallEzl.. x=ooJ 419 e-'= lolE + q+4el g trl-* .lBl ¤ql^J +E6t_r. Eq i Eql^J ol=. "l "l-zl"+
4 oJEol tol ¤4. tr+4^J 6JCg EzI tl{Eel +e+ r'-rll g E.Jg 1"14.
q.ql, oJEI4 eE- "lag +tql+. +,
(a) BI! F-E 7lq
l*r-* z)olzl xoJ ril-fl ¤-zl 491^J zhq¤;al &F6l+ ag=o1 rz"J
.JP ol^Jzl A+ql= +zlE tr.4fz} +*4q, q4 *xJ:^ zJ4ol ql+61 +-11
z +zlq 4oJ EUl] EI+= Îolel
419 A+ql^J E EIe+ 4ol {l49 +e+ e4 =+lE
=fl E tr-gql^JE "*g t4E"l d+g+= ^l-dg ol+6}q +
+lel 4+g r+g=4 pol Peffi + 9l+. R+el+
EzI EUll EL+- +qd gEql^J 4lz| ¤4 oe d=6J
+ el= t4Eel +E +4U+. @ BTIEHH:d+^.1"1 ?E
,l q= +i--ol= ¤gd= l^rc. T^f qv-l H-'B(Jl:rl ,llq^l=
-! !!.\ A--t! +!rl ,lA ,-IAt rI-I r
^l ^l-rl^l^1
.tl-l-l-
+44= 2D.64(8,=nzh2t8mL2)o14. 4olzl yo1*zl 491 5

128.2 EH]|:Et+oil E]|-d 7lq qflE ¤*,2'J BzlE qlqzl q-q=4 ?"1 ¤4.
=+l=e
rB¤ tsz}9 {lulzlE ¤4 tol,q} +F r}4EA z|q. q "tt
t4
--
n'h'
t 1o14.4,
8mx2
E4l 1 rzB.laal9 {}C

t.tlttl= ¤f+ eB+ eY + eF (128.s)
alxl #?l(n=1)9 "llHzlE h2tsmYolq, trI4^J ol f9lE zl
9zlrJ r= Bd, n3 sld, v= tlEo, -74-11 E= dxl t4E * *ql4 "llHzl q-q,=4 ?ol ¤4.
=e-E =91=
4 zlq= +4UrI. Ezl-E ,Jel ^JgAI¤¤ EEL^lrlH t}'J En=(n2 - l)e e-h2l\mXz
Eq dill= E6H^J ol4g +^l6tH+.+
6l +d-6Hzl=e ol
Et+^J +6]]oF fl+ ElCg trP=$ ?"1 ¤4.
Ezl¤g ^Js'+H4'ol4l E+. dx| tt4 7lq= da4
eE.g5 "J^l,el 7lq=
"lag 421"il E+^l7l= oir-lzluJ q; =i'-<*-'ta'
rt=l
4ol ¤4a14. rzn.saloll^Je+ eg.JE E4= ¤+,,J^15."1
sd6l 584"1 olr-ls +($Tl ¤.E¤ xtJelap) a tr,JAIz ElCg 4E-e-E ul'Tzl
=Î4"J
ql E46rzl"J q ? Eq A+ql=
"J+^H+. Ezlz} EqflE *zlzl dedql^J EF jrE *zl9 ?Je a
Ezl-9 qlHzlzl-+lql^Je+ ?ol EB4.J zlqEE 6Je-E zl9 !,ol=lfl "l BTI $1 qlqzl tr]|$fl
=+l5ol
gleq, El+^l +lE q+ce. q+4 poJ !$s-E El-+q =dElq
+qzlH EHl] Etfz} trP=r+ ¤ol "Jf E6llg+. ¤
+ el+.
I ).i
i(all states )
n>>l
i( translational ) i( rotational ) i( vibrational ) i(electronic ) qj = l* ,-a'utr' dn= l* e-"kdn

.t
= (,,,.,t".,,'-*t
) [,,.;.,,' ) [,,,,,*.",,'-*' )
ol4EE 6I6J¤- n=0 o E q.q6}r nr-t& n2o 1 Hl".+q +
q+E 4l4I e4ql= 4E ¤6Jg +zl ?+zl"J ol 4E"l s
'[,,.,;...,t-*t ) E¤o+ g+.
128 ErlEu1.; -sr+ 467
E4t 3
4eel 4t4I xyz+ 8zl9 +q ye+ a+ q?+^J
f --n2Be4 H+ H¤|g 6p- dn= dxllBsltn-e- ol-e"ol$ ol 4
Eol trl$$ ?ol ¤4. lf TV
-/' ETI EH;1 -Et+ [3^1g] (128.10b)
4Ec.t t = h2/8mX2 olzlrl tY t28.7^lql^J Aelq} qs+. tiJ-flel 4*s+

nr/2/2 "I1!
zlzla EHl] ++= 4* *zl.ll 4eXrzilql 4+) f4r +
o;=(i)"'ffi =(#)'''+ (#)", ,lel +rl +7lql qr-llvoll trI+) 6zlaJ4. r4r +qd e
p=!kr$ Bl "l ^lg +.q-r+ ?ol 448 + 9l+ =JJ+ +rlql^l= +tsl] EI+7I
gEql ol.?-Hrilql q+) 6zl_d
4 ++ oiq+ e-E7l +z}+ql trl.+ d= 7k6J flE]]e-l +
-r _x h
r-
'l*- A A-
(2nmkT)''' Etl EUll -g+ (128.7)
+6Jqltr. qtr e r-+ ooE. Eql q+ q+ aE E+. ^Jgql
,<l a7|E- 100cm3 8zl 49 4IAE 4+ ,f =2x 1028014 g+.
/= aolE qfldg 7l^\q, +zl-el E4 trElol4r *r_{.9 ztEEt q 128.2

4 +z}ol+ria ++). 94 .,;ltls ea}$ Sszl
de Broglie
r141tlEl4. ol 4e q+4 eg q¤¤ +Elt+.
2s'cql^J 100cm39 8zl 491 Eq 9l= H2Bzlql ql* H
6zloJ9l
a EH]] ++= Al4}d-q EzI. m-2.ot6mu= ole" qI4. +
HTI +Eql 46J $u1l g-t= *zl9 p"le| "J"J 4 ,,t -h\(znmkT)tt23 +6J+.
olE eB=ql q+^J f;zlal-irll, o1L3 glHzl 6 kgm2s2
+l$el zJ4ol 6ot4^J q Be g4s # A

6.626x10-30 f s
=flEol
d= zl\-t;llzlzl rll5ol4
U2
-tr. 2nx(2.01 6xl .6605 x I 0'? kg ) 1.3g1x10-23 J K-t x(2e8K)

Hi
2
kgm2s
=7.12...x10-" m
zl &szl +716J(Fi ++)ql 44 *zLaFLEll, ol
ag q Bg tr-ql=ol d= zp-"t\lzlzl ullEolcl-. trI+^J,
3iFgql^J zlf¤;4l +rE"6I= EzlE dill qlqzl| Q"e-=$ -r _ 1.00x10-a

i'=ffi=2.77x1026
ml
?"1 rll "J6Jel BTf ef,. 9lHzlE q}+ al} ?Jtr+.

ol zlHS Ezl^b drll gEql^JE eI roruzllE "Jzl. ^Jql
e,,nrnr= el') +el'r) *tl?' (128.8) zlzlg + 9l+= 44zl g+. g4 u|^Jt"l A+ql=
=
{zlrJ np t72,,i ,r¤ zJzJ x, y,9 z ".}6}E gFql ql+ oJz}
71.2pm)ol *zl9 =zlH4 4Lg Ell= gg tr-EllEol d+
r|-o-$ pol
¤+.
fE"l4. ntz}^l 4+b+c-4tr!dol.t, + +H1] ++=
.J+ E6ll¤tr}.
T -k:i'-k:i'-ki1' _ k::' e- k',:'

r2B.rob^lg *zl 4ql^lE "J"Jolf,; ,tlolel ,J4 d= 4i
{ >. all rr
Ie-es:l'
all n
e-
zlzla- 6l]4g + 9l+. ,rb ol+ 7ls" dill tlEH+olI, + q!t
+zI B "l.$ zl-L" q! ¤+ d-EIl+= /lno1q-. ol Atol a7l q
=[]."
)[].")[]." )
I
6ll^l= ,/> lol qzl +l6H^J= vlNA3 > tol 9"lot 6Jq. r
7- t
flql y/Ng Ezlzl ilzl6l+ P:4ol4, tr|+^J oJrJolE-^L
--1 I
olE ¤+ ,J49_ d_(vtNv'ol+. trI+^l 6J +z|7I ¤+4e

{.-T _{i{i
_
{;
-'t' -T -'t' (l2B.e) -E ole"g + 9l= tIE}lE fz| "*otzlzl floNtly frttr> 1,
128.74? r*6J B4l +Fql ql6J +H]] s}+trt. += + HJ6.J

I a>/z} qqo} ++. + t2B.lgbzlol elBal4{ "J"JolE
rJ4ol I g4 iiltl:n+ Bt EJ 4oF aJr{. rbar
ql q6J ag xE yqzE Hl+7lrrJ 6IH +g+. ,.|4^l 3il-g ^l-olel 4+
e+ 2e8Kql^l HrEzl¤ rl-"19 *l+ ZI4g :nmoJrll, ol {lg
ql^Jel eFql 4* EU]] 6J+= q+4 ?ol ¤4.
olEE g4 +*(71.2pm)-H+
^J'J6l =.4.
r2B.lob^lel 4Bce +E ,JBe + ++g +E gi+. +
f =(#)''' *rr-@TL*r, (12B.10a)
t+68
=zlEqqf
"*e ^JelEol d+qH ol 4¤- +sril + F+B6t+= 4

=^l7l
ag ++61.= a.Jrll, olAZ vtrt'ol 4oF eFl= 4o14. 4
tzl *zle1 7s.oll Hl6llî 4eH q= aolr+. qlE^J zs.c9 3
H,E A+9lE a=ztpmoJrll, olag *4zl ^J4g + 91. 5

r\
olule} +71(zllgrt"ls9 f,}ol+ +E +p$
,Ol
-
U 2
zil9t) E+E 4Le aol+. o,e| gg={Eql=

+4+ EzI9 a+ql E,
6-
ts-
E A=rspmgl Er+61-trI
(b) trld ffiE 7lq 0

0123 456 78910
g^l+, J
d¤ EldzlE qlqzl erhcBlu+1)olq, {zl,<-l 7=s,
r,2, ...ol+(Eq llB).
=+l5g .fal 128.6 HCt E^lE ad a5 EUt| g+ql rH-d 2s.Coll^.lE
alz-l 9lulzl ^JEll= 9lHzlzl- 0o14, IrI
+^J ol o + f"lzlE {lHzl59 z\1* ea6J $sz} S. (4 zflrllp1l Hl4l6l=-)3 Erl6l.=E11, LtElLlE
^l
r+.?+
=+lEe
!+vll! qp+ tlEll5.g gl+. ,rl+
"l+q4 7;.?=9.1E =rl1^l=
TIPH SqlEg 7llill+ts 114:gr+4ee A46|! uJfloll
=EHdol
5fl9 r
El+E=/oll q+ e7l-ol7l rll=oltrl'.
^J
HlEila (AB) dB 9dzt9 $uf 945 trl¤4 ?-ol ¤4.
9t tJ
,i^=\ffi"-aiilt"1-i (128.11)
¤gql^l= "*g Ezl¤9 eld ^J+=
kTthc=200cm-'ol+.
QI lcm-tolq(s. 11C.1), olE+ 4''g ullE *+(t}|+61 7l-qg
f* 44j Air6ieiE Elr qiqzi +flej +dzlol ^lqi urtfzlt +9,t! qle.lE^l B =60.ecm-,o14). tr+4^J tr-¤l g
BjL oJg$ +il4 e s 6J6ll+H g+. (rI4 EzI A,ql q6l] Eql^l *e fld fflEol d+¤+. olqdJ A+ql= Eld E
^J= +ql ¤B'J 1,"14)
H}l 6J+E. BEEL 4 o + +e}8 + 9l+
C¤ sldzl-= ^J46ll!_z}. g!3 sld tr-EllEol flSslL /cr

@ qd=utlg+el EB:d^t aht 7t "Jd ,J HL| gd q uI. ol $full aJf
ÎolE
=+1. e + 4Ege Eflillg +=9l+. +
2s.cql^J ,H3sclg qd EHll El+E 4lt}6lq4. B= el 6JCg
=Î4
10.591cm-'o14.
o" - !* tzl +l1e-Fn'ilu*tt 4,
za{E l:B.r 6]59 6]'+4 al&6l^l +6110[
^[A
6J+. 298JsKq^J=
^]E
kTlhc -207.224cm-tol+. +o,L + E E
ol zlts+ y- BhcBJ(J+l) H+ H{+9 6la_ dxtdt= BhcB(2|+t)
9JqE ol-$all.! dal EtCg +B +E E+. z Ql+t)dt=dxt0hi3.P -o9E al&ol a+6HTlr+. :.4H, ol
6J¤E zlq= 44421 +l6}|^J hcvkr-o.osrrr9
4E"l Q+$ ?ol ¤4.
=ol
ol+6}q r+g_J} ag s= "JE+(rB rzn.e). lEe't:
'I
10123410 , I r* ^ d'x= I
(zJ + t)e4.osur/(/+ I)1 2.71 3.69 3.79 3.24 0.09
,l ^ =viiJo t --. pirt
r2B.u rl"ll ,.+4 HCg 6il+H(ol Efl Er{l BEE .J) 7-
-l I
re.e7l qq, qe}^l ol $Eoll.!E/=le.eol+. IE so7yz1

A6l-H f=te.eot7| gtrl. o* =kT=
ol! EU;1 gf+
(128.12a)
' hcB IHtL|]a N-d E^t]
Hld¤ Ez|{l ql6H^J= rl+ Ai+ "JBg el+

zlzl:il_ ?lzl"J olag 4
=+lEol
(zt+ t)69 qElE_E * ^|8-6[ot
7J trll$oltrI.
@ HlcBEx[el EtdEHtl :d+^lBE
\l7lic47l 128.1 g.Cql^J 'H3scte] Eld EU}l 6J+E 4l{}
6|q+. 44 fldz(Eq 118)E qlLlzl5 trl+4 rJr+.
sz.grE
12B EHtl -tst+ 469
=rl
::::
ot-t ofi-to' l,q >>l r}|+E -c'lEE ,Joll Etl6ll
d oi oi r.i
K=-J K K=+J J--l( NF'-FN
rtrtorrrr
-'r': ll ) ->
J =l
I
+
NF
- --) litrt*ry-nep,ttt+rt61--*--,Ur-,"pEr((ir(l*r)
,-nc0itx2
rto++ -F6l hcBB
J IIIil[
YYYYY
5
4 o
ol pffi +al 2E /ql ++ 4+ql Bq=+
3 o 4E G.1
2 oaaoa a
I A-s)x2
O* =
' r-r,cr,ilx2
1
hcPB [* *e-h,a< ; OE
1**e-n'lAx'dK
0
(a) (b)
| ( Tc
tt \'/2
azJ 128.7 elE EUtl -Et+E Zluqlî= Jel Ka E= 7l-=el A--J=
- hcpBlnrpA
)
(?e.e .E,t.l$el 7lq= EEr^lztrl'. 0l Ef¤= (a) J=0, 1,2,...= +l6tr
0lcl^1 4 Joll El16]l^1 K= JE+E1 -filxl +l6lzLf (b) K= --FE1 *ztl^l ol !g q+4 ?"1 C"-lB + 914
-=186l-r, ?: K}ll E[|s}|,/\l J= lt<|, l( + 1, ... , -E +13 #E. 9lrt. rB (a)oll
1E Sg l4g J=2011 cH-d K=-2Pe'l +22llIl9 -JElq=, l4l (b)otl,tlg lt
'il2
{ - (hcp)'''
TE
sg 4.44 K=-2EH:d J=2,3,...011eTl -EIEE LtElL.lEl.

- )"'=(#)"'( AB,
AB' -
37lel +c E-HIE= *=
Hlqla sldzl9 a+ql= B +E
6tLl-= aEl Hl-+l+q"t 6lH, rqH ag +gtrI.
E,,*,*, = hcEI U +t)+hc(A- E)x' 'l+4 ^lol
a_fla M;1, I-1, ..., -lol ol! gf+
¤zlrJ I=0, 1,2,..., K=1, I-1, ..., -1, ,.=(#)'''(#)''' EU;1
[utN:d E^l]
(128.12b)
+. gq5-$- ol+41 z$= 'il41q1

K= _-+El azlzl 6l+61
/=
a- ?: Kql ql6ll^l lKl , rl + 1, ... , @-E- xllt6llE ?J* 4
I
4zI E aolq(rfl w.t1. zlEtEt o{l 128.3
EAI 1 {lHzl +qq aa Bcg +4.11= 2s"Cql^l'H3sclel a+ql= kTlhc - 207.224cm-rol 4,

^l
"llHzlE M/ql ru6}q, 4 <k / <lql 46ll^l MF 2t+r2il4 E = 10.591cm-,o14. l461dl,
9 zlzls + ?+?+E I <k? 2t+t*eE qslg+. Irl4^l ol E kT
7-* - hrt--207.224cm-t -ro <7
El] 6J+=- q-q=r+ ?ol 448 +E gl+. lo.59lcm-t -L''J'
6ll ol<le g"J6}al 4l++ zl(1e.e03)r+ ql+61 ¤ "*eq g
l=oK=-lM,=-J d +rE ¤ 6Lr eg *ol+.
olag q++ a."1 44qlE. ¤+.
r2B.r2a44 128.12b^lol cB6l+ +g gE9 zl#ol I
{=if *rlr-,,Et x'vt= Eld tE 0*= hcBtkoltr+. rq6}q 't.g gE'=
r u'
ot i ir, I +r)e-aE' aol
laK=-I K=--l:K =
r> pRq_l
=c
-$E= 9"lal4, olEl* aa 4ql^J= d¤ EzI9
i .-n.r,r-u,*' itz I *t)s-h,r,lt tt *n
sld EUl] Etfzl-A+61 T/eRol g+. "J+ d¤4"J e*9 #
tiK
EJAI2 qlc.g zl+_e_E tsl^+71 o + teq q{^l "l EzL9l ql6]]^J= =^l¤ + "ll 561 +
dB Eztel U +ql^lg+ ?ol Sszl tl$6l +oI^J q Bl tr"Ell elaflot +trI Hre| eg E|]a
Ezl9l Ell6ll^J r2B.l2a^19 ^l-&
a+El,r" r?-la}¤ ol 6Jdg e e 4+_q_s ul-+
=ol =Î4 r, 12B.1 2flxl Exlel ild 8s*
q= + 9l+r ,LaEl+. f-BlE,
OR/K
*'
{ [*-"-
o' o,
^-
u,
l**,{, I
* l)g- h' I Br t r *r t
d I d K ,H, 87.6
rH3sCl 15.2
E4t 3 4E 4t& ,NN, 2.88

,tcl,
9l^l 6ql^l /ql ++ 4Ee +.J+el EEL+E 4E+ a4 0.351
eg aolqrJ ol d-+ zlillTl g+. trI4^l . altr- ¤E s llc.lql q "*g ilEol ++Elq 9l+
t70 12 EAIEq-{
e. trl]= ol +E r+e¤- al+611^J glolot ++. ,l I (21+r)e BhcBt l+l

+f )(zl+r)e-PhcFrt(t+t)
^lE 4
.},
ol t4l"llrJ 'JHI4 eEg +94 tol "JB + 9l+.
g+-/ 4+-t +rllE A=+(rH
4t Ir|4^l qt ^JEll= ^JE}]E+ tzn.s;.
+C -E.HIETI EzH+ sld ^J+zl =
=
5¤ $szl *3)b qd eH11 e+. *E+.
= .l
<tE ,fZ +4a Ezlql^l= irld f?lEol "Jdqq 9l g=-tr-H,
=e-q(krql Hl6l]^l) trI4^J
= ]/
tr-gql^JE "*g d.?9"1 6
=+lEol I
el+E ag *qI+ f\
,l0J
tr-q q++E +61-= 6Jd¤-.J *]t qd ^JEHzI 44alal E LI

6 4al.-H,
4zlzl 9*E+ +96l]ot ++. qldql 2gz} Ezl+ qla
CE
ts-
=-4
d¤ EzHcorq Et: HC=CH)9 A+ql= r80'E sld^l7l
E +A EbE t4zt LIe}Btr} tr1"4^J 94 " + d* z;baJ
0 1 ald grl.+
tlEl]g t= 180" sldq E6H^l Et zktl tr"l* *4zL 4 lg 128.8 Qe=- "! qaFHrE 3:1 E-dEq EEEHt|:Er'+oll tH-d
4+= "l+q zflzl Ezl.9 a+q tlol 9"1ot 6J+. trl4^J (2J+11s-n.B.tu+tt g5E 7lq. ol Bt- E+ Er'-d ,lol EHtl -Et+olrl'.
4a d¤ +ztel A+= rJ-q=4 *"1 44L]]ot *4. ?=ty EE q= s.=.1'J9 -Bt- HJel fl6tq q6H+E E^l4oe
EU|J --J+sl- ,J{l Ac;l.ola'l-d -ctAE *dse LE|,L}|fltrl.
kT T
q_R_
--zlnE-rf
eld EHll -Et+
tqa dB atd^tl
(128.12a) rflql +ElE uls+ ?ol ?+?+4 /"J=ol 6JCql+ r a^J4
"J {lE H}4¤- 7lq6J a eeH
qill4 oE Hl+q} ztel E
tsz}9 ErJ Et- u]la;o-1 iE: Bzl-",1 4A+ o4r ol+ql, %Fflld= /l'l^1lt=v4 W)/ f L-E- -(JlL+. H.:{ 1'=t'^f
-.tl
trlT
:I I /-i_ -ri-rl I F
î
:i\-l - l A
-l
.l--l ?
^l ^l
rl A
-
!l
olag ol+6tH 44 Ezl-ql El]+ Hl'l]a Ez}"il 4tI =

^14 4 0 e +*4 2tol s$ + 9l+= Lol4.
49 trl*r+ ?ol at49 zl " + +g + 9l+.
* an'il *'1
,t = lZQ I +t1s-
rt
_R_ T ad EUtl -Bi+ (12B.12b)

'l -oF, tdB old^ll aJ9 fz| "*g trI(gE7l $$ ull, T>A*)- ol l.tlz| rll$
ol+q zfl^l EzI9l r]l6l]^J= o=1olq, ¤-q 2fl4 tsz}4 6l A "*=+. ol*l6J Ssql^J= -JCg 4Ee_E Hh+q t3
rlladB Ez}.ll ql6l]^J= o_2 ol4. ol +4¤. pauli fl49 t2B.r2a49=_ gg + 9l+. tr|4^J ol +"JzI qlEql *
gz}el ^lE
q.Jg ols" 619 +¤ts +E 9t+. ¤.Eql^l '_E_¤i', +^' sld EUl] er-+= rzB.12a^l9lî
e+ ?ol "l zIE qlol 9E 4"14.
EHA+el
=fl sldq 9allrl jz+El= d¤ E
^Js 5_="eI 5-f(boson)ol
pauri fl4ql E6lH "J+ *4==g A+g + H+. qlE^J E
z|(co,el eg)9 a+qlE eg +¤e-l E4E 4+^lvJ +
4 rrs"llrl ¤H+ uI$ ?ol tH2¤:zI+ rg q ^Sol 4Ig
,lr gig trll= 4t+ /el Eld tr-E}l"Jg d+ts + glr(rl+- fl+. Eq llBql^l zl46J uts+ ?ol _H-=9 q lsol OolE
+a), q lsol ¤B"J trI= g+,r9 *4"J9 A+.J + gl 4+-t *4E"Jol 6l+¤+. tr14^J sld tr-elE9 eI"J"l d
c|1S_ee-+i).eaE-Hzel a+qY 119 al"t4 37l]el *90+ 4d Eull EL+= E= ztE yl zlq6}= H.cel HI
q tt4z} Bq q-^fl ^J4zI ?lzl ull$ 4 A4(rH rzs.g).
^S =z|]6J+(37]]E
ql). ++-H,q a+ql= 4 /e-l ai"i+ 17HE q tl4"J += +¤el qla EzI{l ql6|^lE ulalzlzl i]4= 6]] +q
^fl "h
6Lq HldB EzI9l E|]6}|^J= trl+$ 2t"1 S4.
=îlql+
"JHI4tl EzI tlE}l +Ê qd gufl olf5. "JEr pauti fl r( KT
.ro=o|..
3t2 v2
TC trld EUll -Bf+
?-1. relofl+alH ol $zfz| -:;}4-11.rU7l 4+"J sld hc lHldB olE^l-l
(1 28.14)
^JEll"J ABC
ol d+q=) 6J ++4 e= E_HzUz| $4ql Eld t4rlol
g g.JEol4=
ffiee d¤4"J rHa+E ztE + .J+E -*. 12B.2ql ++L}lfltr}. +
^Ld¤. f E6l]oF
d+q=) ,r11 {}tr}.
trI+^J aJ Ezlq 'll+ ¤+ Etsl] ¤.+= trl-¤-4 ?"1 84. Eg ol+6H^l 4a+E "Jot4E "JBq +6ll^J= a" 6J4 E
4l I12.rg -Holzh oi4 A++ qlql^J ¤Eotflrl.
12B ETIEH1 At+ 471
J
#t
F BE D FC
E CD BC AB
6 C D B A
f.\
'DJ
U h B DA CC D
6
(E
n A EF DD F E
t\-
E E F
r E CF A E B
F BA B D C
ad g^l'+ ,A
lal 128.e cor9 trlE EUtl -et+oll 7lq6l= 7tl7|l :g=9 ,JE. 4r+J'JE
,+= gE|.|=trJo| -:1EEE|-. ddg 4 zHill*E Et|rlaJll oJE4o+ fal 128.10 Elfl E^l'= ++-d AEoll E6H^l lDllg E¤ utl-BE
LlEl'"! aol+. =gl=el LlElg + 9,leq, ral6lq E|1e+7|. 1201trt. 67l|E s3 E= aE
^q=
lTl-r. -E?tE trll 64Bel "JE= Ll-El.LJ 10|tr|..
ElzB.z Erl=el EHa+- (c) T.!E 7lq

-el
o EzL9 llE EHll E+++ dE qlqxl 14 44==_ ruE
=+19
,H, 2 cE +ql Br q6H+H +E + 9l+. rq+ TIH aEI
IH2H I tlt:"l4l 7lats + glsH ol4ol ,El,'d t+6lltl4. olullE
NH, 3 tl$ .llulzl 7J4 hcv\ +"J6J rI44E"l !tsril
=+l=al
(Eq 789+ 11C), ol{_o- Z}++ r4
CuHu t2
q1 rzn.roll^l +l+Itjr"
. zle ¤9 s. rrc.r"ll q ple <i5ol ++Elq
a_ DB.2a4"ll s_epg Ar+ +eg 4*"14. r46lq e =hci
914.
"J er+$
ola-" a}$ trI*$ ,J* 4l/-7I Lig+.
v1 7l8l
I =1;-m; tlE EHtl -Et+ tôl tl5 (12B.1s)
zFJEt ql12ts,.4
ol gL+E E_^l+ 4"1 :zH 128.1lolu}(olag ¤zll4 o + :r.
o(HrO1-2= ol Exl¤ H-O-HE s"E4 ++ls 180' El H rzs.rr+ eg 4"1+). r4r
4 tr-{E zlli115 t2B.2b4
dz.l4 trll, + EZI Effizfz[ r]E r+¤+s ag +4 -"+44.J+gl+.
U+.E NH3 ¤-zlql^l= (r)ql E"J + ++lql 3z]lel Et
Rb uflalol ¤z]]el4. cH4qlî= 444 c-H A6-J f?le_
120' fl{;lrJ oll"}4 E+ gb t4z} +4qq(2), tr}4
qla+= 3x4=tzzl $r:r. 10
^J
ca
D
B <F
A 6o
5
B E
C c n|]
2
fldql^J= EzI Hql +zlql + +fle-l {& u[.}ol EA 1
0
0 10
¤.b tr-El]olq(rB 128.10), F^lql +zlH,UFql 9l= 67HE ?E, kflh6
5
+(rzl]L c-H A6Jql ¤q6}r +4^l d!9 c-u Aqlg leJ 128.11 EEI TIEE 7l¤il= ttllE Exl'el TIE EHt|
:Bt+.
8E7l EE tt1
E"+++) +9lE 180" al{ol EZ} fi-b t}4= +E}U+. (f > gv)= EUH -Bt+7 I .gEoll CE o + H I
allEt= +E6lclal..
t 72 EEtrl
=zl
zttrJEt o{l 12B.s +4 = Bzl +ql= 7l+ 4+ B4Eol glE6l g:sq,

zel.tsKql^J r, +zl.el TIF EE]] 6J+=- +t;171 +lat¤ -s Hl+ 4 B4E"l a++}ql E.Ezl ?*otE aillzl_e_e= ol
rlc.rE 415 ++ 2r4.6cm-tE "l++4. zgs.rsrglrlts 5Eol t'-BEl AEzl g + 9l+. qE.{ rozH9 flz}E
=
g Hld¤ Ezl^b 3N-6=24zIl4 zl? *4g zlzl{(tr{
kT I hc = 207 .224 cm- | ol +. trl+^1,
11D). tr|4î t zlf %'-^.lE llE BHll e}+ql q+ <l=ol
2l4.6cm-t
l.lEJ qqE dill4"J aE EHl] ¤-f
.=I.035...
'Bhci=ry=
kl 207.244cm-' * qu =(r.1)2a=!.9
=
n}+^l 128.1s^lql el6H^l aE EH]l aJfzl-rl-gr+ ?ol ¤ "l+ qq, Hro4 eg z+g EzI9 a+.il EI6IH ^J'J6l
rl-F E*.ol+r E + 9l= aol+.
+ =
., I xlTl g71 128.2 *9 *sql^J co, Ezlq q+ 4lÎ
I - y_"-rrrt- - = 1.55 g q+ol6lq+. {EE El.+E l388cm-I, 667.4cm-t,9
Hlqltr-El]e+ arq EE trq"Jol ral d+g+r ++g + 234ecm-toll" ol +ql^J E lle-l EEI ll5l %L4g 2+o3
el+. Eslqq 914.

etg,ft
4flz} EzI9 a+ql} zJ zl? {f HJ^l(Eq ilD)Sol

zltlg EU|] aJfE *.+(Bl-asl^dol ql+61 4o1,! zli +zlE a+ dE ++= ql+61 +o}^l phcv> lol E
E*g
olzl"l tr-E +84"J trll) r?]6].q +ill4 115g"fi zllzll
+.qls^J cHn9 alzl tlE"slfE l306cm-rolq q+^J dg
HU a}5g9l +ol gltdtr rl-v--v(l\_-vr?\ olr} olzllJ..Y(tO qjî=
rL ll EI I e-l Et I -t 7 \^/rl \!/r. . . i-i. i'i i .i \L\i
Bhcv=6.3oj+. C-H tj+ ij5"ti+= "j"tizl o + zaso
Krll ,l= "J^19 +Hl] E}+olq, ts+}q}4
o e. +C+
Pq zgeocm-' Îololq, q-+4 Bhri,= l4oltr+. olel6J A+ql
= zld q61l^J
=+l
aL$++. Y{uq EE +ql Eq 9l= e-phaolOql 4+ zlzt*4(41d4
=
e-63=0.002), r46}q +"J Tlt %r-^lel 4lt EHl] EL+= lql
@ TlEEHrtg+et 4ttt uNi zltlflAYql?hci=63oJ oll= 4u= t.002ol+) "14,9 o
H2O BzI9 rll 7]l3 4E rJ^lg El+E +E}44.7+7+ d +E a+g+.4g g"lt4.
3656.7 cm-r, 1594.8cm-', oi 3755.8cm-'o14. 1500 Kqlllgl
=9l"Jol
olHql= a6Jol ql*61 E6H^l Bhcn<1?l a+E ^J46ll
{E +6}qq.
+ts]] EL+= aaol "J+¤ trll= BH}] EL+e-l zlfaJffi {zfl
-H-z|. o1e-l6J
r.E{E A}E} 7+ 71= r}^lql+ l2B.ls^l¤: zl+^la rJ+, o|{(e= l* x *...) tr}+r+ ag tsg. + 91tri.
=^}4g
rll zlq-el +g +6J4. rsoorql^l= kThc-r042.6cm-l
oltr}.
q -,
t-e 4hi - r-0- Bhci +. . .)
4 4lt %r'^lE 7lq= trq+E q^q-r+ Ag s= + +e gEql^l= qF* e6JE 4* EU]| oJfz} tr|$q a
=ol ol E+.
"J=+.
{ ,,
kT
7l+ *4 I 2 3
hcv TIE EBH a+a [l8oil^1g
=^l]
(128.16)
¤B6l+ gE=
ilcm-t 3656.7 1594.8 37s5.8
128.16^10l eE 8E Au= hcvtkZ zl
hcitkr 3.s07 1.s30 3.@2
=C
zlr +49 + gl+(E 128.3). H,ql ql+ 4k6ttzK)ol Hlc
.l 1.031 t.276 r.028
^J4sE +e ae ol flzlz| qlE6l TIEI q4^J ll5-ol

trl+^J dill4?l 4l¤' +Ell e+= trl-s-+ 4.ol 94. uulEzl ullEol4. tlF 9s= zlzlt- +EI.+]E '+g *s'zl
T>0\'= 9"1614, "ltrll= 128.16^10l "J+qq ,fu =Tl0v7l
{v - r.o3! x 1.27 6x t.028 - t.352
EtrI(Eldql +6J +^16l-+).
Hro9
^11
71e dE %'-^lg r ulfE"l ql+51 +eq ^lr+
rsooKqlîE 49 EE EZLTI Hlg 41¤l t]-Ell"I 9l+.
rze ETIEHIi Et+ t73
E 128.3 2flrl Errq d5 3E*

=d ol + glHzlE 7J4 Evz=04 Eyz=eol4r ats EU.|| *
ev lK fz| upa--q- ?ol ¤4.
,H, 6332
,, = e'k, -2+2e-k
'H3sCl
,NN,
4304
3393
,Af
,tcl, 80s
ol EH]l q++= -zH rzs.raoll T=oglrlb 26
=_,r1o19tr1.
. zl.E. eE .s lrc.lq q E*¤- ttEol ++qq 9lq
s qolg Hlqtlq"Jol d+g f 9lo oE f=2zl fl
4. :4r F9 $sql^lE Lll ,g.E11Eol s+ e+g + 9t
E + = 4e. d=++. 2s'cql^J=
-o f f =3.10]14.
(d) drt SEI|S 7lq
4
dz| "llHzl ,J4z 9EI4 o + trl]+61 lq, q

=+lE ^lolE
+^J trH++e_l A+ql Htq ^J4"Jol d+qq r?]6}0l f _t
ol4. ¤zlql q+ qlels^J +s,* ae HLqI dzl-rJ4zI 4 U
\r
slg flzls+ EzL9 ?*"1{, :z qs+EE s'+r ts a+ <F

3
I
'to-o
f -*zl g+. qlaql "Ja4 #4 flxl¤9 z+eE qsls HI

-t
n|]
qr-tr"Eil= zlzl:t- ile4(olE9 dzt + H]|6J$ ++B

^Sol
+ 91tr|), trI+^J f=2o14.
2
5 10
LttrJEt q 128.6
0
?E, krle
r.B 128.13 NO E^lE Erl EHH aJ+7l8Eoll qal Edl= Eg.

flx}q Ezl-"ll tr|"+^J= qgl BlqI dzl. rJ4E zlzl4, 5 0l +de 2=91 4l0ll cHel zi(:al rzs.+)r+ Hl*5|'^lu ?=ty tso|.^lE
s t4zl- H}EI +qql ql+61 7l*L+.:z t qlz]. NooJrll, 2(He qEE)e+q 4(Eill 8Et|+)E
=qq =7rdtrl.
ol +4+ ...r,Eg {z} uflilfi zlzl:t_ gl+(Eq 11F). +ll
E 4S*r+ ^S 4SF*ol ¤4qL + q+ ^Jql('ftu
'Jg +4U+. rB lCIBr2)y olEol .<Je *Bqfl +E
+ qe+ tr-ql('fl,,, 'Jg ++U+)E+ EzI +g qlLlzlE
4E+. AEI qlEql +++= ol "lluJ 71 7J4+
^g-+llE
121cm-lllql "J ¤+.
T
E
o
-
F
N
L
,ilr,, L
fal 128.12 NOsl 25 trlsl Hl=f d^l AlEl| +9E

4FJn+ +lE 4EFJoI UEtl
=g(E^l=
g:ePjel2=e-e HalE Ad ^rJ
=-= =+l
(^rJ 4ffirt illE 4E=aJol E"J:d. E= dEoll^lE g4
oe EE 7F-6',|.tr[. =+.1=ol
474 54 gq-+
=s-d71lLJ=
tr l. ErlEull E+=8=rq1.q ¤40+ d=ts+91=t}Elel a 4. el EzI9 tlE EHll :d+= eEt 4l*zl¤ ZIc+ z] zl? 4.
+E s^l*tr+. E %}^197lq= +6Iq eg aolq.
a 2. Er}9] qHr|} ¤4 trolal eF %r-^lE zl¤59 Bol4, tr s. dx}9 glHzl #fl ,J4+ Elq^JElls+El "JHI4e_e 'I+
tr+4^l EztEull ElfE olE qBl 7lq=E Elol BtrI. 6l ral gq4 fleq, r?]6l.q q+EE a+ drltlEtl E
:d+= utq
! 3. Ezt9 qe+= qaC Ezlz| +4.||= ErJ BL"+ uH6J= Hfl dzt {.4E qslEe+ aq.
I += relo.J 4"14.
=sEl^t=
ce ^l
+^l 4Hs
Ezl EU]] *f ,=,*:-*' 4E, t}E EB Ez} 128.1a
,=,I 8,"-k' CE, {}E EB tsz} r28.lb

+"J { =ll(l-e-& ) l2B.2a
ÎtrI?-l
z6.fl Al {=l+e-& l2B.3a
g4 ultl A=hl(2nmkT)'t' T28.7
%{l {' =v lrt 128.10b
sld {" =kT lohcE T>> oR, dB cldzl I2B.I3a
{R =Ot o)(kr thclu'lntAEey''' T>> 0R, Hl-d¤ fldz| e*=hc*tk,*=A,a,g=e tzB.t4

zIIE aEl {lE zl4, eu =hcitk r2B.rs
L-: O
{u =ll(l-e-9'd )
EEI 12C EIl,ollLlrl
{zlrJ p=ykrol4. ol !q+ q+r+ ee +4149 ol*s

> ol EEE H|t+= ol8 tr|.
gE+= olEdElE EHt| Et+e+q Eqqt4 8E=
=11g0l'Eltrl'. =olH d
= ¤i¤-p¤, __ 0¤'
rF e
> E4C 7]lE
relfl $E +ol {EJi= EE}61-= o + "JE +
SE
=aJ
Erl EE +el El ErlE BE oilLixl= Erl E{|l -d+"J ^lg +gr+ ^l
)vla.4lt-g + ?,trl. el+.
> =Jg':d qHl rl4l

Zltle.ELf EB-+4e_e EB qlolE1= 7lÊ E^l EBt| -tst+E ur=-!r4h"-*'=-;h*=-;Yu (12c3)
zl+tg + glol0t 6|q(Erl 128), lEEl 0l EHt| Er+7l. E= 7l-E-El

SEtl9 +E LfElL,_!tl= elel= g:a 9,lolot -srtl. 0l EE0ll^l= +fl¤ 9 zlzl +e-lB d"l il4. a4lE s0=0
r2csqa+
Exlel eldrf TjE ollt-Jrl= LIEILH= ll=EE 118-11D)E ?]E olE+(E= "llulzlE 4z-l fflg zlf;c_E 444zlB;Ifl
g aolq.
o F +) (e)E HlEltL4E zlfreg * tlEH4 ¤+ qlq 4 <k
ol+. "J"J EzI9 al4
"ll'Jzlz[ oo]
o]qr e*4H {zl- ¤
EAI gqqr9 tsul] Ei++ "JzlqEg r+-" s}+e+ Eli+ E + qlqzlE %+(a)"1 9"1"t 6J+. qlE^J ao| 4l:="x1E A
gg 6l+ 1o14. u]-=."g$z} 4lq +6J E= qq4 ets- +ql= q*9 od qlqzl *hcnL Eol"h d4. E {ls EEl| E}+
zlzlt_ 9l= ar+ u[!zfz]E Ets]] E]+= 4lg s= Eqtrt4 gE += H+(qaq +irl)qE E=6Iq, fr]6}
"le.lE
=
q 12C3^l +9 pq st E-g45 dxll"tl 9lq^l- += H
eEE qlE6}r. gl+. "Jzlq+ql^Je+ u|$zlzle eE=-
qB + 9l= rl$g "J"I"t 6J+. 7l-tv A+6J gq+4 ^"rA
=- +E¤ "Ja4rll -aE'¤E6Jji4= aol+. E|+^l EzL EUll
.J+e+ * Ezl.el ¤+ qlqzl
I 6I+= B+ qlqxlol4, TI1I A+6J !s=$ tr-E-584 Îol9 $a+ +4149
qs_r+
gtrJolE_tr
"l+qd llql +{ Aol+. ?"1 ¤4.
(e)=r* tl#), nE E^t olLr^t {12c.4a)

12C.1 TlEAl
l¤¤ 6tzl ?+= Nz]lel EzI d+g ol 4g dxtx=dlnx9 +4lE Al^-l trl-e-=r+ ?"1 448 +E
^JE tls.
ol
^846llg+. gltrI.
d+9 eEE * +zl^= q?l ^Jql ,ql ilg + ?14. "l 9lHzl
=
4z1 ql',lzl ^JqlE zlfree qI 4o14. * Ez}el ¤+ ql (e)=e* - -aT
dlnq
EE E^l oilq^l (12c.4b)
"tlHzl r
ulzl@1utqI^JEllE zlfreE 6J)g ol dtr dillel V
E d*fl Ezl-fe +b zlol+.+, r?-l6lq +Hll EL+(gEE EI+)"J "JE ¤+ 9lHzlE 4l&
ts + 9ltrI
<'>= # = #rr,, (12C.1)
{zl,tJ N,= ^}4 Eq 12Aql^l -tr?l H}e+ aol

,e-l T]lzll++. zrtrJE! oll 12c.1
gE Tel d+ql^l +48 844 " e zlet 4¤iol +g EE +^l7l ol+g. + gl= qqzl efl7l E +"Jql, .t4= o
^JEH= Boltzmann +s.41, l2A.l0b^l N, 1y -(yq)e-&,

o + olr += 6I+= ¤"14H +E]] sl+z[ ffi4 ?"1 ¤4.
+qTl+. El+^J, =
{= | + e-a'
py=L\e,e-k, (12C.2)
476 ': -EllE+f
A=8+*g''',xE8+
trI+^l ss rq,q olE. +zI dEE B+ qlqzl= trl-e-,=r+
B"l ¤4. ('r):-(Y) ( Ehl.onstantxp-'/') )

(.8./
x X
I d(t+e-o'1 ee-o' ¤
(e)=-
l+;:E;- -- 4F-= 1*p;=;n11 --[E.l( a1f,1.onstant)+ In B-vz ;'1
"lag :-H l2c.lol+. *g t}4"Jol d+q

E^l6J 4"1 (a1lmp))
5. T:0oll^l= ¤+ "llHzlz} 0ol qq, T+ --E qq + -1---ar).-rF r
+?lzl F" d c tr e d+s]H jse--+ +7I++.

0.4
=,
(el)=+tr EE grl qtq^l t1^tgl (12c.5a)
3ilgql^l zl-fi+7il ¤.F6l+ +zl.el a+qlE +eg al&g

tr)
g + 914. :4H,
G /
-:
K
5
0.2
t,/ I
o (er)-)kr EE BTI ollLl^l [ex;91 (12c.sb)
1
(b)trlE-E 7lq
?E, krle ?E, krle CB Ez}el ¤+ fld qlqzl= fld Ets]| q++^l(r2B.Il)Ei
lg t2c.t e._Eel B#e qElH 2=+l 4le.l Bil oilLJrl. g+ rfle "l+6ll^.1 +B + 9l+.
He 9-E gqoil^] ollLl^l7t o-e.trFEl Ealztz ?l- Eq +=
EiL f=0oll^+= 0l :4sE 7l37l7t 0oltrt. 9-
^1^16l
raJg f-+-E E I4l, f -ZQI*t)s-ntu,U*D
I
F SEllE zt|ill#zl,=lotx1^j o.sB EE-tst= -H.q
=q gETl +zl s¤. trllHr< eR-hiilk) +gg + 6J4 6J6ll
"l
+qot 6Iq, ol+4 z&^l ez}+ Hl_qa dB +zlql q6il^J
b ol f¤"I r+g_+ aol g+.
12C.2 7l= EEi tJ^l=el 7lq {* =L+ 3e-2
PhcB
+ 5e-4 Ph'B +'''
ol EqE 4"lzl +Eql^J=,!l zlzl ¤E||E ,lB gF %L^l trLel^l
E B4l(r), sld(R), rP-lr Tlfly;ql q+ %r-^l5o1 4+ rR

= Yu- +. . .)
+6Ir, olq^l EzlE dzl. /d.4 7lq(E)e+ dzt9 d'11 --ncn(6e-'o"s+30e*Fh'6
^l=¤-
fl t'-Eil 7lq(s)E q¤4 E6J^l7l=zlql +4^l ¤E$ aol ^
qZ vq1 5-$alq, q4î SEEL+E 9d sq++e Hl^+S.
+. tr|{^l B+ qlqzl= trl¤.$ *"1 84.
+.)
(a) BL! 7!q hch16s-' o"E +3oe* Fh'E +. . .)
-E (,.)=-i% =
1*3"-zohcB +5e*on'8 +. ..
z)olzl xql lil-fl i
f*_xt {oli4 A_h(2nmtByuz
41"il 46il^l
olr-l{Eq l2B9 'gc +iil r='"Ja 4ol xE Bl^+fl+). nI EE ald oilLl^l IHlqe cE E^l] (12C.6a)
4î ,i= t]-+q+ F,,E +EL a4 eeq, rEldLq q^s=r+ ol Bgoll -H_ol= EL+= tA
tzc.zoll s.r.la}ts4. E9 Ss
ae a!+= Eg + 9l+. (7> OR)qlrli tze.t3b4l(rx= Tlo1R)g f=rloBhcBq El
Hh+q^l +E}u4. o164 zflzt Ezlql rlloll.rJ|. 6= 1
lg
ol+. Et+^J +gr+ ee A+= e4 ¤+.
12c ErlollLlrl 477
1.5
d(l/f )dx = -(1/f z)df /dx
IQ
()
q d I hcie-fffi
E
o dp dB r-;w l--
(l-e-r*u'r'
(12C.7)
K
5 tr++^l
6
rFro.5
HO
0
0 1 2
G' ) = -
* ff =o -,-
Fno
)
f "-
*tf
hcie-fn't
8-E,zeR =1;-F*
aeJ 12c.2 tEe.l B#e +EILJ Hl-4e dE 6ldrl'sl gE slE 0llL1^1.
aEOl^lHI> 0R) 0l ollq^Pl EEoll CEoe Hlallo|4 t= EHt| gqsl trI{^J Exls+ EEql+ ew! +6ll+H q+r} ee aq-=
gil:dtrl-.
Eg + et+.
hci 7ftr] (12C.8)
(eu )= EE Tl5 ollLl^l [ôf T.!E
;qi-
-1/p'
ol gd qlq \ ihct? 71611 +H 4zl 6?l(o
u$u ^lE +Eqq
(,- ) = -
i# = -oo*u h(#)= -
e
=+l)
E{tql oS zl6e-tr. + Bt qlLlzl= Erll g+.
ol ¤+ qlqzlE gEql t[l= HE+= rB 12c.3ql +qrll
tr++^l
fl4. Sszl. go[,rJ T> eY,1 Bhcv<tg u]l=(Eq lsBql
@")-|-P7 "JE trlE ollLl^l (12C.6b) 4 ?v=hcntk4 +4lE gfl+) +]^lel zlf o.;i;= {zlla}r.
[cE E^l-. r>0*]
(e{=l+x +. ) E ll 6}z}zltrJ f6J + :14.
"lel* =^l-= +l
6IE +l r1-9-_* ?ol ¤4.
B:3 sld t4E"l d+g trI +E+ rgql^lE a+= +F ^l"l
eHl] gEl(_trq 2Ae-l Elqz}9 4lal zls+ "Jzlq}+. d¤ q . \., \/r/- e+Bhci+...)_t-
/c'\---
hci I
EE dE qq^t
g --kT (12C.e)
dz}9 {lHzl} rd4 + En_\rrto!+ irrarfol{, F zzpj-E
o
lr > 0'l
TlolE (A6J+ ++lE Elde S+) ti|{^J +F
"l+qd+. ol a4b -zd4ql +F EHl] gEle| "Jil6J+. ol g?-lq el
EHll g4ql 9t B+ qd 9lHzlE 2 x lkr=krz| ¤+. 6IH lil-fl +lExI9 qluJzlE p=lmu|+iku*o1q, olE 2iI
6;el ¤7^l+ ?+4 +kTr+. r+l+ r> avE aaol CB6l+
zlElEt q 1rc.2 a++ EE+= ag ¤c6iq4.
lg q}4lql^J Hl-d¤ EzlE ¤t qlHzl$ +6IE]E
r fld gE qll,lzlzt(sld qlLJzlql ql+ +gfl 7lq)
- |I,aj + !I6al+ il,co?"}* ol+6IH g+. 2zlt;] zl{
10
En
z| rjlol + ¤+ Eld ¤+: gluJ zl! |krolr" E ¤t ql

Hzli inrzy ¤4. zs"cql^J ol 7lq= 3.7k1mol-,olq, ol r6
ExI9 dll {luJ zl t.+kl mol-'oll4 H A +E+ E"JoJ zl (^)
qE ++. lgz} zlill= Eld gF zl{z} $.4. 5

j
K
5
o
rFr
H0
[!E
(c) 7lq
-q TBE,7e'
5 10
1l+ Etsll EI+b as+ dEg 7LA6J 4+ l2B.ls^l

lB 12c.3 6El-TlE¤ 7l-8:9I= ttllol Exlol EE C= ollqÊ EEol
({u -u(r-e-Phci))sE +qd+. ol ruts +qql ++6l.E-tr -cf#-e LtElL.! raJ. E"= 8E (T> 0v)oll,(l= 0l 01lLl^l7l EEoll C-do+
trl-g +41= eg + 9l+. HlallolH il= EHt| fl4q "J^l-Jtl.
t*78 Eq+
=7il
zlEtEt 0{l 12C.3 2s'Cql^19 kTlhc-207.224cm-t(* g.zl qI+)=

"l+6lq
zel.tsKql^J r,Ezt9 ¤+ TfE +E qlqzl= 4l&6|= +.
rll pgal ol tsz}9 llt- ++= 2t4.6cm-tol{, 2e8.lsKql
\Y *f t ttc= 207 .224cm-, o I 4. rfl 6Iq, rfq-r+ *ol ¤4.
- hci 2l4.6cm-l =1.035...
'llhcv- k*I =----------------
--4ee-&
207.244cm-'
(et)=- 1 q__ 1d
I dp- *;;"frQ++e-k)
j
Bhci,,=evlTY lE+ =.zl gf osE(+ rzl evql HI6H^J
zzl Q|e-e-E) EU}] +t fl4$ ol-e-" ai + S+ 44^J 4ee-k

2+4e-k
¤
+l
12c.8^lg olf-allo| 4q El-e-=r+ gg Ar+= gril g+. *etr
++tr- +Elu ¤+ qlqzlb (e')/ftc=(vE;olc|.

(e' ) t hc =Tg+ = I I 8.1 cm-r
e= hci
0d qlr,lz\(ixzra.6cm-1)E q6H+E ol 7,}ol 2l5.4cm-t9
6zlaJ4.
(f')=
w v
EllolqE Bq+H,
aE+ dF9E A#R + 9l= 7lZ 4+ *!E"l 44 z}]
glg trI= +ill4 +Hl] .J+zl tnt]d EUH 6-J+EE +!4 ee

\l7l EJ! 12C.1 3+sE qs+¤ Hlq^Jele+ rtr.4
400cm-r flql 7+e-E ElsI¤ tIEIE zlzl:il- 9lE. gzl-=
(o) txt ctEilE 7!q zlzlt- +lel 4hlg lgol 4q+.
q= flz}q EzI9 dzt /dF4ts trl]+61 r-urlI0I :E
'l]++el +d 4^J.l
+ol Heq, ulqr dz} ^Jq"Jol E+¤+. s= qlLJzl= z,I *
Hlqltr-4$ zlf;s__e +a6lEtr_ r+q=4 z."1 ¤ + gt+.
^lg (e) 4E 8Etl"l 7!q
(et)=o EE d^l 8El] ollLl^l (12C.10) xlz\*,8 +ql^l= dz} zlzl "JzI+ ra,-tr s,,\l9E. uH
6}ql q+ F ^go1
qE a+ql= +d gEql^J g4e_+ "lluJzl ^JEllE +4.J + 9l+.
ol olluJzl| ffi
tr|]^J d=g + 9l= 4 ?"1 +48 + 9l+.
t4E"l gl4. ol*l+ A+ql= d= 7k zld
^JEllql +6H^l
-Jdg aI{ dzt tr4 EU|] 6J+= 4l&6J + ?leq q+^J En,,= grPoBm, 8^l qlq^l (12c.11)
Ê
r ¤+ "llHzlE +g + il+. trl+ _H_7lql^l tr= HIe+ eol
olBlqL 6J+ {zlrJ psE Bohr u}:uJl5lolr(* gzl oJ+) g"E 2.0023o1q.
a+ql= flq}szl lltszl$ A$oF ol= qlqzl= Eq r6Aql^J _H_+ zt^ll6l ¤B6t4l+. *e
^J
4E /n,=-+olq, q+^l 4zlzl oleo 9 + gt= F 9lul ^l +
@ dxtgEltEoilLlrt 7tq
9lE e-,7r= 04 ¤*uz=g,tts@4!o= 0?-l +Eql q4) q+^J 1
qL gzlT} 2+e-a eslg uI$ dzl- fi"4e+ r H+ 600cm-r
(=e/hc=r) 9lql 4+e_a qslg E== 7|zlr. 9l+.
{ EH]] E}++ q-.q=$ ?ol ¤4.
^JEHE-
2s.cql^JE B+ dzltr-Ell qqzl= ++e g"lzt El4.L ,'=Z;-*-' -1*"-Bs'urB
4i
zE{g gE r(8tr. +4u)q^19 Eull 6J+ 49 } r;-lr ¤il qlqzl= trl+.4 ?ol 84.
^l¤l ÊE
-L, 12c.3^]9 ol$alq ¤+ {lHzlE +QL]]=
^lg + -g"P'qg-Pg"ue'B
*+. t)=- -ls g: =-;;-o;6trP

ol r+cql^J EH]l e'+= p9l saHr.J ul$alo| ++. rd (l+e-os'r'e,
(e
¤-9--a +qd EllolElE Bq=+. e=hci, (e')--hc(i')4 q dB
12c Erl qlHrl 47e
-
g"lluck-PeuuB
zttrJE! q 12C.4
1a"-9s,ura
2s'cql^l + +"lE +qAg 2.srE zlzl^J"ll k=^la+
Ezlpi EEql+ #6IE ol al6zl " + trl+r+ (T= ztTlar9 rllz'l teslaol4). f'o'lr+.
"es,u,a= ^lol Hs=9.274x10-2al
trol ¤4. lelH,
/^s\-
\c 8,[LrE
/-Js;,\l *JE 4E oilLl^l (12C.13) g"pBts -2.0023x(9.274x 10-24JT-t) x2.5T=4.6... x 10-231
pr,U*U- =0.011...
ol sL+= ae Dc.tql E^lqI ar+
=t4
o + *9 1"14.
ule[.<J ¤+ "llHxl= trl¤$ +tr+.
(r')=*## =2.3xro-2tl
ol ollHzlE. 141 mot-'oll otqq).

"11'&+trHa-E=ol
=s-d7}lLl=
r l. gt Ert 0[L1x!= Ez[ Eu]l E]+E+E] Zl4]E + 914. I 3. .r1g ++ql^l= ¤t -$zl. olluJxlE+El tsg ¤4zI +F
a 2. 4 +E *zlEol B.* +zI "llHxl"ll 7lq6l-= aE= +a EUl] gEel a!+e+ eal ¤+.
EU]] ElfE ols-" fl.rl Al&6J + 91trI.
=9.-d^l=
,(l-zl
ci e. --1
z--A)
I --1 al Ha
^l
1l+ Ezt 9lHxl \e)= e ,,-(rl{)(dq ld P)" F = tlkT r}c.4a
rLA rt61 11
-'1 E E-1 '-
(e )=er, -(3lnq ldB)u tzc.4b
Hrl (* = +kr dzL?lql^], d=r,2,3 rac.s
sla (e")=kr cE EzI, T >> 0R rzc.6b
rlE (e')=hril(euta -r) a=f {f, z}{ 12c.8
(eu)=kT T>>ev TzC,9
.r- liil (es ) = g,llucB I (eqs' t'Bo + l) zlzl* 49 dz} tzc.r3

E4 12D g=gg=
> ol EtrJE Hll+= ol8

Er-! l2Bel 12coll^,.| 8E-qaJ Exl- tl'+g,rltrJ gxlloll ?lol
N,
Erl-fl| 86rtE= etc|.. qa|.^j q7|^1 flEal= Lll_¤e I
^-|ts
gril 7li.ll, e4i1l, :Ialr ErtJ .sEqtE¤ + lg + fl= gelel V 7 I 10
A^?,'
T 2 3
zloll rfl-d Egg EJE= rll TlEol Er[.
> E4d 7]lE N,

17 18
19
V 16
dE Ex|fl E 4l= eE EU}| -Bt¤ 7lxE1 LIEIH + .oJoq, T 1
1A
15
=g olBlEt 4lq gq+4 dtr-=ol'J + ?ItrI.
olao++El 11
fg e"E 8= gAt=. g^ll zlel

12D.1 N =20?l E+71 )14
> EsEt qlHl rlal SgEt sdrl +q='*=tl. ol=e !E
=tEe
E4 tr+g afa gloo+ ,
q7l^.1= xl+lE3 EE 12Aoil^1el e3 LHEolEl. Es.z1 E-e,'.j Ara o15g f 9l-cE-e r
tr+ ,Jtr[. 0l= ,\l-ololl= 01lL1rl7f ^1-e
q^l =E4{e_e
Bt ollLlxlE Altl EE 12c0ll^1et tE4oe Eg6lq, oilL1^l= A^l grl-. rai+ 0l 207Hsl +^jl=q Eill ollLl^l= g8=ol E^{
q7l^'l xt{Fd Zlttg El=01 6lxl ?Jg aolq. 4o+ r=JElol ?l-eEe ggaEl.
dxll zlill+ .+ille+ eg ^JszI* ¤ 4l= +l#g

goJolE_a ol g4 9l+. + A]$
ÎolE EdE"l ="Jg + fleq,
rq
trll gs6J 444 z]]Hg'oJtB'ol+. Be 4+4 +qE4 6Iq 4 4lE a¤ol e=" a3. f qlzl"J r sltrI ElHl¤(Eq sA)
uflzlzlE "l +qE "Jtr-4"J ^J+ g-olzl"J ++4_oE= g E+ E"J6I+ ol "J^JE# trl+$ pol ee|$ + 9l+.
g"JqI Fg *= ¤q6IrE
^llEg +q+ oL,(l--H-
ooE /(loe.
z'l
,-,
d cie.
Eli a=
12D.1 gg=el TI|LJ 14EN
z)7-
o Ll- 14 IN
"Jtr-Eg "J=elE +d +yl, aC, "l $szl ¤^l¤ BaJ 4l
Ell4= vrv
E ^846Ir" olq^J olBlal 4lE llzflu3= $x]laflo},t!+(rB
12D.1). ol E.= F"JQI E6J 4lEg g4eE d+qq "li e= "J^Jgg Eq l2Ael ¤H r+eql^l gFql E zl.3
^ls ol+. qlA= .J^JE$ *ill4 o + r.El6}zl g*9 4"14.
9lq tr-gz}ql qlqzlE r¤}g + 9l+i1 ^J4r++. -E= 4lE
e-l Cill ollHzlbrol4, ol 4l.g g4eE d+qq ilzl oll "J^JEg zhlzl +zllE9 {aJols + r +^dgq +. g
Eql E+ +ee ¤'E 7E *=+ r47 ol "J^Jg +dg=
6l.L El]E 9"1-Ezl ts + gleq, a+ql trl.+^l= N¤.
=ril
E +i4= E+ Fg6}jr" Ezl-EqI "l+ElE qlqzl ++qle qrll 6J +E 9l+. qlLJzlzl E,oJ ^J4ql fl= "J^J
fCfl"I4 Fg6rq, q-+^J 46H41 f9 E{¤ol 4=+l=E 4lql^l E +^J?lE +E &-tr- +448, olag ol+6H^J "JtlB9 u11
EEg+. olBlq} *E 8r. *= +xll AIEE 7litJ4 d+g il(Eq l2Aql^J

^Fs"
* 419 u]]zlg+ Hl+g f ll4le+ ulzl
8= g8=ol+r qL+. 'c6'ol4E 7l¤g E +al, Hl]zl {NoN,,...}E olE + gl= r}Hel + 1,rz vl
"Jg'¤! A6l]d =
EqI+ 4'J + 914. ¤zl^l NE /w| o1A +4lE H+= ag +E
6lo14.Ng dzll ,ll +ql .q gl= EzlE +jr, Ng +xllq}
"J*Eql= ol e.lql * zlz]1 +s6J 4,ol rJ gltrI. tr|]t 8=
8AEE a+ql= "Jtr-Eg oli 4lEol E+ E"J* Ss. 4lEE ¤ +4utri. .qe+,diE tr1-¤-4 ?Jcl.
r*^l $!l :z g"J6I4l=E.J+ .llHzl# *=tr}. Ne ¤7ll 4l +ql Eq il= ExI9 +r" "J^Jgg ,+ +4
= ']]4lql
ol*l6J 4lEC r 6I+6I+zI aHqq 9i+ EtlE= g8=ql fl +E gz|. folzlE 6t4.
E+ E.J6J +yle+ gE= 4a glzl"J ,ll5 TE E= +CgEq ;5 grolr|.
^J. 4 4l=ol
12D tE g8= 481
E= "JtlBg + +¤g(Ezl {zll ollulzlQ

'oJ)el
ry= qHzlzl E,oJ+^ll AEE ++.
EE dill "J^JBe-l + "llHzl4.
N= +^ll 4lE ++r+(oJ^JgE +^dgE +)
.rib uilrl {N.N,,...}el +rll4
K
5
a
-T--
-J'3,
8Etl+
(a) xlut|4 u]|il
tr.9 rzegl^le+ u}T!z[zl-P a= "]d]89 uHzlE +E q¤ 12D.2 ollLl^l gE]| "JE= El OllLl^l gq +oil arEll+E r
ae +E aEtr+ g{ q = $# zl4 4p14. qleî A
=eJ =olgl=
BEE Ho|e Ll.=,Jolrl.
al qlq\ Ezl oJ 4lql"J +4qq ul]il {M0,0,...}z} +4+=
A++ Ae_l "Jq+zl g+g 4,o14.e.9 rzeoll^J ^l-&'il'J a
r+ Hl++ brlql uI4 zlufl4 tsl]il$ ol +
^J41+ + ileq, SEtlSI
Et=
"J 3l'il ffi
ullzlfi ol$all.<J "J^JBq +* ¤tilE fl6}q 8Etl9I
gEqlzl Ceg +e + il9 4o14. rv+ *zI 9E EE-+4 oilLl^19

ol zlull{ u}lzlz} oJE4e + 4l']] +E"l 9H ol -9.t+
=ilql^J=
lol 4lg ^"ieg 4E sa6l zlHH++.
C=J4"J
=E "JBg Eq t2AE a+s+ qeeq
ql4lq wr+ N,¤ 4z1uj 6IE ¤+. +d HHzl {N0,fr,, ^ril+N,
. . .}9
+Al q,/+ q¤r+ *ol ¤4. ollLl^l -------)
fal 12D.3 d= ga== 0l+= +¤3=el EE= oilLl^l -*#e up1

il= No!Nr!...
=
N=l
+zt (12D.1) LH4E ggsl -d +¤flo1 +cltl oilL1^l gEt|oil fl= qE(l2D.2^l)0il+ r
qlLjrlql cfl$ol.E SEtlsl +(E46l.Zl 866|.= EI+)E E6t|0F -dtr|. olel
:ct+= :sr+=
eol + E6H^1 Lfe EA ollLl^lol|tl H+-d E+alE LlEtLtlll
"Jtlg dillE "llHzlz| Etr oJa6}zll f.zlgl diil +cgE El=E1l, 0la8 71E s= +8301 0l Ea oilLl^l= ,f=tr|-= ,tE e,op z1
fz| aaq= ++ 44 q-ql^J "l Fz)lz} alrlls q= 0lrl..
Hllil=^re-e
q-q-4 g3 E= EE^le + +qdq
.NI, e-au,
q=I.-r', g5 (12D.2)
6z|t}4. El+^J "JtlBE + +Cgol +t+ 6J qlqzl
N- a. =g zll
(.4+ tr4z} olu)= z|{ ffi$ +4+ a}i E}+oJ rzo.z
¤zlrJ9 .JCg E= "J^JE +^dfl=ql ad !*Col4. q= ol ql4(rg
gEE er.+olq 8= trr++r +s4, F=Vrr"l4. E ^lql+ fr4+ +71 ++= #ql 4ol !"lo} qlEl6J
=H|{ ol 12D.3). trI+^l dill4t +E. q¤ + 9lHzl <Hl^J
zI Etsl] EL+e+ u|{z}zlE e= +H}] E}+ .Jql= CE B +qlil= +El-44l g+. aE4 0 + "Jtr-gE 4++E +^d
zffi-,rlo1E drc.{re"z}zl 4lql +$ -tr= gq+4 A ge ¤+ glulzlgl ulll zlllg glHzlE *=qr AEg +
=ajq}
BZt.q914.
eI+
(b) slE]| +E EEoll^1el s= zE!¤t q 12D.1

rzo.z44 Cf Ee 6J+= EB6l 4E qlqzlz| zlfs+! *Z nol nt"J trll #46141 *zlt;14, e-*E nol 3 (}"J
o + alA6l-= EI+"J Sol4. Boltzmann EE4ol E"J EzI =
qlLJzlzl E,"J *
ull #461111 1ta{4. ol + EI+= ,*ol t4q ^J-ol6IEl
^J=Is-l d+E 444=ol A= Eeo;4;. 4E ==q
-lzl sF "JzlqE+ c++^la+.
"J ^J4 ,el +Cflol +48 q¤g +ElU+ :flrll dxll4
ee Ael 5"J+ 9luJzlE 4= tlEllpel += tr}|+61 g}+. f (x)=e" x'e-"'
qle^l Tlillel A+, Cal qlqzl= H6Izl $!sE^J L4rll I
olag E^l6J 4ol :zH tzo.+4. ol +fl $-$ 4ol +71oJ
E" 6IE
tsz}q ml-e_41 +F6l+ +z}el 4Alzl BIE + gl+. q tr++ ei6Jtri
r?]6}q sEll gE .6J qlqzl gqE tr-El]+= r BqE
t 82 EE-+
=zl
12D.3 8E r]lrE
==J =rlel
0.8
llt Ezl-=ol ^JE_584"J trI= qE Ezt EUl] Bf re 448
llt 10
+ et+= ag trg + 9l+.
0.6
f(xl
0.4
il, 50
IzJ4l
0.2 I + 7l^l +.qo-J A+E ^J4t6H"t 6J-=Ell, 6l-+= 419 $"J"lE

"l B+ |s"¤I A+oll(r.illql^lilfl $ujolE"l IA¤ fl
0
00.5
/ I 11.5x22.53
ilE-^lzl6t= ?*oll), E 6I+= Tlillql^Js+ pol oiulolfi
:Br+el
"l +lzl$ HIE + fl. +A BbE d*o14.
azJ 12D.4 ,-f.J:d ql 2D.1 ollilj ol$-d F EE 8o l-d n,JE
1
111
1
E4l r&E +B4olr BZI zlE+ +zl=E 4l

7l^l-r. LfEfLHflrl.
NT]]el g
^Js 5B +zlE d+fl dTll
qlqzl= 4 +zl¤E
glHzlE 6J+ a+ e+. q+^J qlq
^Jql ,ql 9l= 4lel dill
zl= trl-e-=4 ?"1 448 + 9l+.
12D.2 llsl tsE ollLlrl
E, = ¤,(1) + e,(2) + "' + g(N)
EzI EI+= olf-aN.<J EzICAE ¤+zl= Al&*H a

EH}| ¤zlrl e(r)* 4lrl tL4 ,ql flg oll9 EzI 19
"llHzloljr,
4 "t&zlzle A= BH]] e-+E ol+6l$ Ezl¤s ol+q4l 4Q)* ZITI E"J6Irrl tlEH ,ql 9.lg trl]E Ezl- z9 4ltl7l, a
Al(Ezl¤ol trszl¤¤ 6La "J 6Ia tl+$,ol) d^llE ¤+ a-ll olal uftzlzlol+. rBlH C= EHll EI+z| ufe-=q- 4-o1
{lHzlE 4ltg + 9l+. olel {."l Q;- 4lzy tls EB "J"J E+.
ol=E d6Jol4: 714* de 6}zl g:e_EE {Hq ¤d rl
"JHlsIg i"14. E|+^J a= Ezlz} ts4rg"l +s+ qg g (r )-ps,(2)-" -p¤i(N)
= )e-e,
g 6l+ $irlolrf dzll zlzllE ^Jeg Eel6l+ ql f-s" 6ItrI.
"JtlgE dill qlqzlE E, rn]r +CgE ;5 fi-4r a| Ezl-EolEt zl$.6l$(oLqql^J ¤B6t= 9"191 ,r+4) 4lE
E +CgE B+ qlqzl= G) =Etwl g+. qlqzlzl r,"J ^} t}4ql ++ Eld#^ ,+ Ezl¤ol s+ rE zl]zl]9 tlelEg
4 "JtlE +CgE
;"J E&i,= l2A.l0b4l(p,-"-\''q ¤zlrJ ztzlE + glril a3e eal +g + gt+ "t4^J 4lel ^J4 ,ql
/i = N,/N)4 Hli6}rll trl-s s. +ElE + gl+. ++.JCg ap73 q4lql gz[ rgl 46J -E= ,HE4 t]Ell I
^l_o
pE,
Eql +6J 6Jd, gzl. zgl 4+ s= t}'l] lEql +6J 6JC, Eoe
^-
rin =- q (12D.3) E ++E + 9l+. ol+rll HF+q +4'l1H +lE QE q-q=4
*ol ¤ + 9t+.
Ir}+^J
,t .t ,t
(E) =
1i,r,= {;r,.-r,,
(12D.4)
n=[]"^)[].') [r;.')
nC.aa4 ((s) - -(U q)(d B),, q 7l ^J ¤e. = 0 )S E Hg
qId ul e+
tr14^J e=/ol g+
ee,JBql q-+ +g-r+ ee ar+= eg + 9l+.
EJAI2 I}E +H4q] BZ} EE EZ}EE 41
(E)= zlel (12D.s) Ezl-5ol E+ t-"J6}r E z}+Erll olt.g + gtqE qL

+(#),=-(+F), EiloilLl^l
+zl7t qL +zl-tzl Ezlol "J ¤ 4"14, Q={o1"*zl ?*zll
E+. qlsrl Ezl- r"l tl4 a,Ezlzzl *4 b,Ezl aol tI4 c
¤t +zI qlHzl9 a+ql^le+ zJ"l d^ll 4lE HlEltF4 qq ql glqr 6LH "J^Jg +fl qL ql +Cgol E= e*¤6*¤,4
zlz| so1 otl-lE olag ol rJa|+qot ++.
^lql glHzlE zl4 4"]14. r*l+ ol +Cgg $z| 1ol ^Jq b, E
zl zzl t4 gz1 :ol t4 a9l 9l= +^Jflol+ E= ole+
',
120 trE g8= 483
Hl*6trll zl+g += qE +CgEr+ Ezlol "J g+ olBlqI 61"= +vlql E=6}rll ¤trI olelq} +El E= +Zl= dxll zl
il¤+g FF ozflolq, "JHI4 o _e NrTHol+. 44^l oli]H + ill(Eq lc)E E6l+ ql 561 +s6I+.
zI +b.Ezl¤9 a+ql= "J^JE9 +Cgql ++ -Jdg E "JA gEql^l +rlql q= alel qlqzl 9= +41= r+61
zI tl4ql +oJ 6Jd o + ul-Tq += 4eql^l 5ee t4zi EIE (aG) Dv)E +6110} 6Jtr|(Eq zpq:sglrJ ol "J3 zl
q H4 ++ 4ltq= AqrI +g+. 1Q={ol4r #o-+ Alel '4+4 "Jq'+ zta-nF +r}U+= ag H]]S,+).r?-l
al ez} r+Ell+al 41lgtrI r46}q eql ¤_trH+ qL AE ai{ "l E6J+ql+ rzo.srl9 Bq=+.
* ¤:E.ql^J= l/ME "Jzl¤ E6ll^l Q=//Nt o + ql+qot
a(E) a DlnQ
qI+. -dr ),=-[ AV T (12D.7)
v T
Ell 3 +{}4 Ar+

9d zlill9 a+, BA F"4 Lil+ gF'J^l(Eld 8E"r+ a
fl9 a4gg ++4 Aol 6aJB + glri
g)q qlql EEll E¤ q+a 6J uI A= +tsl] C+- Q=flN
+7J 7H tt-g +B Ezl9 C*, e=d (12D.6a) olr*. zlillTl l?lzt e4.J trI= Bd gE %rrl"J Sxllals
+e Et- tr-E_+B Ez}q a+: Q=d/Nt (12D.6b)
9,i = V t,,t' (421,<1 71 - h I (znmkT)trz; o E-E Q = 1A/z13NN! o I g
l
:*# z
4. Exlt tsar$ol fxflts QlE rplmg ?lil EU}|
E7l7l +e E*.ol qqE Ezl¤ol eg a"Fzlot *tr}. ql _tr Hh+qot *+. ol zE Ezlt trlHl¤ql 9a*+(E9 rc
g.<l Arflzp Neflzl-e+ +zlol g + s.+. rq4 olfl c
"J I .J+ "JzIq gtid}zl tsol.4). ral6}q olull= Q7l trl¤-
ijlrrJ Tlzlr Ezlg EJg-+= s.+. qlE^J ec 4zI 491 ul] rt *ol g+
gqq il= Fg ++E EzlE=9 r alEE zlzlt- r+r+q\
Z (12D.8)
+ EzlE E.l ¤ + 9l+. trl-4^l 4zI 4.ll +=EJ 9t= E Q=
xl¤e ++71eq+E a 44 zl4zl ee 7l+-"lzl qE9l ^3F
trI4^1,
+tol Elq, q4^J r2D.6a^1¤. ^l¤-6HoF 6J+ rq+ E"J
t ++E Ezl-e ¤ zlzll9 a+ql= E4¤9 ol +461H^J
4Eg f sg_o e olE¤ +zlg fzl s.4. olfl a+q= (y),=-[#(*s4),),
12D.6b^l g ++. p
--[.a7(.-W ), )_f ar'1
^l-8-6llot __( a (d".Z') [pr,(r/^")) )
aB ), ,J,-1 ),
Ll'JEt q 12D..2 ii r/ a xdy = a2 fnya x E[l| A(E^0011 cll6ll,\j

0
N4lEE+ +b Ezttr. ¤ zliJel a+qlb Q=flMol+.
a ( otn(u,1,') )
q+^J ol trllE 9lHzl* q-q-r+ *"1 94.
AV
a
(Y),), aF [---?v-,1 ,]
(,) = _[ ?Egry! =
_[ *4#r, = _( qfr),
), ), dln yldx = (1 /yldy1)la
=-,(Y),=,,,, ={#(+,u),) (12D.e)

T [#][#),),
+ ol 7lzll9 ¤+ qqzl= + EzI9 B+ qlqzlE tvu]| rjl4l ¤ql^J +iilql ++6Iq tr. +iilql ++ E6J+zt ool
e+ a+. ^=
s+.
flzls=e ¤ dxll zlzll($zla ^Jg4+ol E"HJ;col+)el a
+ql= zl EE flzl¤ ^lolE tr-E4L+E diil EIHI¤ qlq
12D.t* +trlol! rrlE ollL-lrl EEr zl E 4 s4lqErll, o14,3 -E-$ oiulolEE tlql4 +lilql el
r+g=r+ ¤ol ¤cI.
Ezl-=-"I t}g4¤¤ ts trll= Ezl-d+E qlqzlz| $zJ-p.r.].
=6iq
olE Bfli 4?lql el+6].q, q{^l e6llTl f9 Exl-$ol zlzl z- fi!"-o'.' dt,dr,... drn 9l^l EHll Et+ (12D.10)
tgt, ',
=zlgq-+
ol d4E gz| igl r]i6J +iil ,q_iolq, ol 4E* -5L

^lql^J
+ql^l zl flzl-$9 ufl¤ol ++E + 9l= $$ol

27X4
,9 j
=o
= ^lE K
5
Boltzmann +rte +qzl7l trll$ol{, zlfES r EEEgI o
6ll%r-61-= q fl¤ qlr-l zl4. {ru
u'l
H'
E^lz zal
zElEt 0{l 12D.3 )e
s= 21x-l
=ct
Ep=ool q= Sd Tlill= ,lle.lolfl Ezlt slHI¤"] 4E
fg 12D.s ¤I1l Tlillel E^l'rJ tEAtA qEJ!¤ ollLl^l= van der Waals
6l ZI+qL A+qlE 12D.10^lg +617l|71dxllzl g_.e
4t qeFlE'l o0l ulallol"E gg flal8 +Eoll Eaill?.! gq bq ?J^11-7 EtrJE ^19
q qB+.Sd zlill$ a+ql=
^l+*+=ol E+ rolq LlElg + ?Itr|. E=oll^1 ¤E-Lf BIq eol 0l -=.Boll g4:d 8= EUt| -Er+=
tr|4^J q-s=4 ?"1 ¤4. 0lE6}|,(j Xltl-d van der Waals 1C)eI gil:Lrtrl'.
=rt= ^]9 =4(EE
, = #Jo r,dt,... dr, = #(Jor). = H qzld rg *rl

v+ql Eqgl= Ezl9 Ed=J"lQ, aE ol
trlHl¤E "Jq ++ "JE Holql Hlql6l+ tF+4. e9 aEel
ol a4= 9d zlillql Eil6}l^l ,lqlifl'J ar++
Ezl zr.z4l^l +q= van derWaals ^JEll^l-oE+El Sd6l E
9fl al(nr=an2tV4 o=E)9 +EeI HI 9l+. {zlrJ *4zI
"Je "Jq¤ qHI¤ *E-e EEIAI"J ,Jill ++ql 'll+ qHf 49 + fl= eE+ zlz{ -szf{i ^}olq qlq ^Js4}+ol gl
-J "ll "f ^l= ,o,-f"ll r( ,fr LZU.)) "l 4l'ila.
.ll allrjzlrfl -rl 6aIIrz-=l i^nF\ r] -ll ,16
LllY. <>l Hzl-:l'J
-llrl:I r
$- trll= z)4lzl r="9 S+6J ull ollHzlzl fzlaJQ| zJol
="dof',|
r Ar+"Jg +41]1H tr|94 ?ol ¤4(E:2x11 fl .tlo1ee1 +( (aG)/d7;r>0o14 G)E +rlql se} zlgzJz| olole e;.
tl^1+ H*29 -H_ot4). Ezl¤ Îolel ¤+ 4 4zl Z ull= Ezl¤ol trfl4rffi a]i
gq "Jql Srtl ql$ql glHzlzt tI+6J+.
"lE7l
( a<e>\ on'
Eal qil¤
[;, ,J,= v (12D.11)
=s-etTllE=
tr r. E= gdEe dzll 44 +Fq= gE= z*Y zlll9"J + CflE +trI
:d+E ol+6t
4l alEg dqlot4. r 3. .JtlEE +C+lEq ¤+ qqal= g= EHll
. 2. 8= Es= B^lg dill qlqzlE r*= 4q +E "J{}B + q zl$6J + 914.
=e-d^.!=
.^{zI
oe. ,\l
-1
z-.)f,
I --'l al Ha
a= +E1] *+ Q- I"-'o' CE rzD.2
c= +s ry llu=
"-P''tQ
r2D.2
B+ qlqzl (E) = - (l/qXaq/ap ;, = - lElnQ/Ep), t2D.5
C= EEl] E}+ Q= Zlfr 12D.8

EHI,(I ,(}f7.l!-
9lzl ="z} 4E 7= 1t t N )l r-Bo' dr, dr, . ..dr, OOO O+-1 O 12D.10
¤t 9lHzlE +Eql q"= HE| (D(r;73v;, =an'tv' t4 rzo.se E^l¤ i4Hl¤ 9lHzl l2D.1l
EEI 12E LH+ ollLlrlel fl! =+ul
> ol EE= Hl|+= ol* u (D--u(o)+ N(e) = u(o) -+(#),

q7l^l tsel"-|.= LHEP Eqqr4 gE= Erf ffioll^l #l + Lli+ oilLl^l [ga_=g E^t] (t2E.2a)
?{= LHEolTl nilEoil ot|+ 6s6lrl.
ge a+, -trq rzcglrJ 4 gE "J^l=ql qql^J qc+
> -e{C T1LJ (e)91 ++ 4# ol+g + 9lsq, oJ+ A^l 4l4}g 6t
Eufl fl4; SEIE= Eq+4 8H= L}|E6E fleq, EB
Xloll A+E zllelol-H r.ll *El ^lg +^l +E6J 9s_21 g-o-
qtal gq-qf t6lE flaJ qg=:dtl.. =
4o14. qlE^J Eq l2cql^l ao+ dEzlE ¤+ "lluJzlb
> -JgEl qlHl rl^l (e' -hri
) -l)(l2c.8zl)ol H+ "l+,<1
I (s1n'i 41.:=o zJ-==-tr- g 4l
+44 EllolEj= 0lE6tQ Exi EHt| -Br¤ qE4 Zl||6l.=^l= el E ql+ qlqzl.| rl-e-=$ Bol ¤4.
g0t0F trrrl(EE 128). Lt|+ oilr-1xl(eq 2A)elgleeul(-trq rn)
N ohci
9 erl. 0l EEoilî= -trE 12c0il^j ¤B-d
zHEs. +116lr. flqoF u] 1r; = yJ (o)*
JETJ
BE E^l-oilHxlE Ahl BEE 0lE6Pil flr|..
ffiilq 12E1
trBx}9 4lE 4+ 2r4.6cm-tolr|. 2e8.1sKq^l= kTlhc

EH]] ¤-+E "J+ "Jrll 9H e-5 gqql4 EL+# +6J + = 2oz.224cm-r l4 a- hd = 4.26... 21014. ol= Alg ol+
il4. gqql4 ^JAE +ql^J 4+ qlqzl ue+ qltr+tr] sq 6Iq q-g--q ee alg eg + 9l+.
Eg 561 +sEI 7lE Ce"l+. g+ olE + ^Jeg 41416l-
,ll EIH olEE+El Gibbs qlqzl(Eq rzrl + slEzl +d ql 214'6cm-L
Kt- 207.224cm-'
-=1.035...
'Bnrn=4.'!
^}ol
rlE +s.* ^da# +Eg + 9l+.
E .ll+ qlHzl9l q]+ TI5- +Fq 7lq= q-s=r+
Elz}^l
?ol ¤4.
12E.1 Lll+ oilL1rl
ul1rl=YJfol*
+-d EUll 6J+ F ol+4q alE 1-ll+ qlLlzlql +qI 49 q e""--"'-l
BZI +E6l'=zlE B"J o -+al "l q4 +s-Cg Br-614t+. =uJ(o)+t.4lklmol-'
(a) Ut|F ollLlrle.l 4ltl

t2g.2a4i_ tr}S4 ?ol 'I4B +E 9l+
Eq l2cq1,r-1 s_oJ ule+ *ol tr-E-+B EzI d*E ¤+ ql
HzlE q-q-r+ ?ol EzI EH]] EL+e+ +al¤q.
u(r)=uro)-N(
w), rsETqTJ'Elil
(12E.2b)
u,---+(#), (12E.l)
tlEzl+ Bzl¤E ¤ 4lqlE ole+ qEq Bl*d rl"l ol*¤

{zlrJ g =ykr4.q+^J wz|] Ezt-e. g 4lel d;ll 9lHzlts 4. ol a+q= a= Etsl] 'J+ Q= ol-4"6|{(tr! rzpl r-19-
N(e)o14. ol dill qlLJzl= HIEI
^J4= zlfreE + aolq 4 4-ol 444oF t}trl.
(F uo= 0 o e +Eq tr|+ 4l1I+ 4."14), tr++^J 4+
6l-=
dlnQ LlJ+ o1lLl^l
9lHzlb u(r)=u(o)+N(e)ol ¤+. ¤zlrl u(o)E HlqI tlql U(r) = U(0) - aB [8sArE E^l]
(12E.2c)
"Jol d*g|g ull, tr++^J r=091^lel

q+ 9lHzl4. 4+^l v
lll+ qqzl= trl-s-r=4 Bol Ezl +Hl] EL+e+ +4lE+.

t+86 12 E4IEE-+
(b) EEZJ trl+^'l

.JA-+sl =*3 Cr_(dUtdT)r"ltrHEB ze). :.r_lap ao|
Ee" .l 12E.1
dE"zI Al9 ¤+ 4lE qlqzl(r2C.84,(eu)=hritlsa^d -t))=

dE 5^d 3E av= hcrtk= ol+4q q^s'=r+ gol +48 +
c,=-kr'(#)" --Nkp(H) NkB'[-*t),
V
91tr|. ggal (12E.s)
<r'>=#j 9s.21+E ,J^l ME 5d gE-H-+ ^JB6l tot^J r> 0M

"J tr]IHTIE"J trl= 0v =hcr,lk, sld"J ullE a* -hi,lk) iE
trI+^J "Ja-+iil g g+elq .{+ dE eE4 zlq= q-S
+H]] g?]= ol+6lq gl$ q a+6}ril ci= +B + 914. ol
4 ?"1 g+. trl]= gC"J {f ,J^lel += r}^l$el ¤t E qlLl
^llr, 4
d(1 lf )/dx = -(1lf '))df
ldx zlE *Rrg Hl]+e +16}r, olq^l ol qlqzlE gEql +6ll^J
U.(D = U-{0)+ No (ev) FE
ÎE ul$$e-e.^l E.J+ Hll+el +Rg gg + ?14. zl;ilql^1.
^ll
dl ETI +5- Balol 6}tl{}{"lq, trI{^J g g+=*ql+ a,RE
CJ ,m
%P=Rg' dT ,e'rr -r- R t+) G"-''{r
"eutr
TlqE qI+. ¤t^Je 4A gF "J^le-l 15.vR*r-[a 6tE(tr]+
.trE9 gEql^J= dB EzI"J uI vR*=2oljr" uldB EzI
^J
ol 4]g .e''rr -1.gut2r)2I +41= "l+6lq q*q=4 ?ol li¤ "J q= 3ol+) Eld ¤.P jyR.Rel TlqE 6Jtrt.
gszl *E
+ 91trI. al $-o|,<J vv*z]]9 +15 *zl"l ¤+cg trll= TIE ¤+ol E g
tzr +%Fql+ rr*R9 7lq=: 6J+. ril++q a+ql= vv*=ool+.
av f (T\ ( et' )'r ,-eu
)
vV,nr - Dt(T\ J \t I --
*l-lrl;
q-ql.] :6. ^.ir.)rL6
E-6-id.i t^r^l " .- -la.l-l ,1-^l r'l-l
/1. l-;d"
\. /
-.y T -rl7lA- T-rrft ¤"1 i1T.
t
)
cy.oil LI1EI Tl5 7lq (12E.3)
Cr.^=*(:+yR*+zt/*)R EilI EEAJ (12E.6)
[r > 0"]
-:.H rzE.rel +Ce r]t g+*9 9s E+ +41= +4U
4o14. &szl av+ls a+EI $.4zls g+**e +-F EH11 zlEtEt q 1PrE.z
tlElE +qzl= <kql 7lvlfltl4. rze.3^lg eYTl Einstein 5 Hro9 tlE 5C gE=(HlgH6Iq) s300K, 2300K, I'i
c gs gu-tr u1g aillel g+*ql +ql ^l(7A.8aal)rl 4+^l 373Kql^J= ol tlffi"l S=
=84 s400Kolq,
" + *4. +.J6J zl+ tlfol rillgl^J 3i}+le + "Jqt+ =Ezl
4.r'tl sld'J^lE ?ts 9s= 4oK,ztK, l3KoJq, q
q
aol+.
= 4^l ol ¤.t¤g Bd .&E"r+ u|4|zlzl_tr Sd6l E=E4.
a+q 44^l= gEql ** "1ts9
trl+4 aI3 *4lE ol
e"619 g=UkT4l +6J trl+e_tr El+-r- 4ol ¤4aI4.
cgi¤ qd -gEE EqL D.st K-' mol-'9 7lq. ++.
d dB d r d tri+^J 251 s-r mol-'91 zltl-! Sol ,l4g+. dEzl=
dT dr dB kT: dp -oB'h (12E.4)
26.t1Klmol-rol4. "lE"l gilEtzl ?+= ol+E 9d zl
ill 6BrEo e--e.+el9 trll*g 4o14.
"lE
q
E
oS
to 0.5 12E.2 S!=.eu!
do
6ru
01ru
5l4l gq+ql^J TI1L +H6J+e-l 6|+"J flE +Elql +6J
^l
'Boltzmann^l'g slEerle+ 314 +E HJlilql rll* +zl
^tol
0 E +zlE +6IoJ eg + 9l+.
0 0.5
8E,I/EV
fe t2E.l aEt cEE zfloE rzr.:48 olEdt|î Zlugl E^lel Tl5 E-d Boltmann 4lg ?tr
EEgsl .9E sl=8. ?tty evilLl tsol,^lE EEaJol rd4oJ ,J4 tjoto
0lLH-e tr=-ef= +E6gef. "l +E r+AE =E¤eLil+ qlqzlql +,tl 4 u1r;=u(0)+
12E L}|+ otlLlxlel S!-Eerl 487
N(e)o14, ¤zlrl (e)=(l/N)> iv,e,ol4. * ol +41= +g +AlE rJE6Lal

"J^l6J+.
u(r)-u(o)+)N,e, S=klnful g1=+rlCIl S:af gottzmann 4.1 02E.7)
^lE
+E "JHg r.d4ql gqtrlg ols-"a[{ dSe} du.r1o1 ol ql+61 +s6J al¤- sls+rlql ++ Bottzmann lol4r
e_l +41= +B6tr" olq^l ol +alE ole" ol.{ du= 31'.l] q
oJ4. ol r,tY AIE 4']] +E u]]il$ +A]+(EB rze
E HHilg +rllE zlzlt- +4ql= 1o14. ^lql^J
ql^J Eq+ HIe+ ag).
EZI 1 du(Dq ++ s^l
^lE
u(Del H+= 4lE qlLJ ++l7l H6I4 41¤,zy q+ds,-E) E (a) fl!=+trlsl EH]| El+
^\
7fli-ll+ HEilN,rlN,+dN,s) trI+ql .J
= ^Jaq. 4+^J TI1I EE4_qE+q 4l4I6J ¤LAI gq44 Slee_vl=
Boltzmann
HI4?l HqE q+r+ *ol 4elB + 9tr}.
eE+4 ql-E +irle+ Sd6l qee CAg +ElU+. qlE^J
d u(7) = du1ol+)rv,ae, + )e,dN, 419 9s7I rllBlTIE dill 9lHzl"ll +6Jq. Hl]ilel izl zJ
,tlq ZL tr+4^l sel {}ol 4' ,*+ T+0ol El= +
914l z ds.{l ++ ^lE s^l ^6Is=+
qlq^J= u(T)=u(g)ql +qlq= uflzlz| + 6l-+g0lE +(E=
"JC-+slql^J fllE TIgg trl= qlq 4 ?+eq EzPI zlzl qqzl 9l+) ,W=rol9l u|4rJ tn,til=o
=+)71H6izl uI:
(re nu.z), r46}q zI9 ol99 4E H:*zl Sg + =+lql
ol g+. q+^J r+0olH s+oo1 q=ql,
"lag E= sdq}
EE ,jl4l 6J(a4)"J Br| gq. gqq}4 +41^1, +i|4_e_-tr AAel SlEEq= r-+0ol Eq qq E+ t."J6J <l_e_-p d
3E. I (dU= TdS-pdl4ql E 6IE ol El+ aaql du= TdS :c)= gEqr-el 3Hzl4 "Jzl6l= Ar+'I.
^l ^l =
7| g+. trl-4^1, =qlr}(E4
"lxll B 99 sorumann Es4g Etsll Et+e+ ¤SrlzlE
r,*, "J"14.
ot=
+ =
+ I, = kple,dN,
E4l 3 uE zlzlt- +4U

ds=
^l
alql +E H]]iIE Hs}(ola"J aEl6lfl g+)= 12A.74 ^l.olel
tr41
(d(lnvr4ldN,+ a -&, = 0)9-" +qd+. trEI^J 7q=dQnqADNt
tlE-+B +A-71+ EzlE g Zle+ ^JE-+B Et-Rb EzI
+crola, 419 EzlfTI aAqq ?19 rrF r+q=4 *Z 4t+ tr. g Zl= + +Ee-e. ++q^J 414}6110} 6J+. tr-s4l¤¤
eg+ el+. g]4e F Zl+61 rel6ll= +E 9l+.
=
dln'w'
Dln tt /?N,+ a _L E4l 1 +E_+B +7J_7H EzlE ¤ 4le+el +41 +E
-7;:;- g
as=kI ffiaN, =oI[#JaN,*t"TdN, =k(dt n,til) NTHel Et z]$.el E{s=E Alql ql6}]^J= tnq,r$ r2As4
(ln,tl= NlnN- rNilnN,)9-tr +48 + 9l+.w= ?N,E F
9.B ol alol r]=o-$ u."1 S4.
I
EN
ln,t/ =fr r" N-)N,lnN,
=IN,hru-)N,lnN,
ot
,l=Lo{
-?
=1
= )ru,1lnw-lnN, )=-IN,,"*
E_
t r*lH r2E.7^l(S= klnt4o1trI+4 ?.ol Eui.
I
ts
(a) (b)
- s=-kIN,,, F
-
aeJ 12E.2 (a) 4lE 7lB9l_ tttl= ollqxl E6't^l gxl$ r=9 THill
+71 E:dtr|.. (b) 4loll oJol
B6t|^|E
=?|Ee
ollLlrl=+l xl-dl7l Eetcl. q7l^lel
44 +E EEql^JE AL/NE {,t9 soltzmann EE.ll N,/N
EE TDel 1ilg Ar^l + g'Jololl tt|-Lr a0l+. o| ffi59 E7lE ztloll =?l =e-k,1rA+qd4. ,rl4rJ,
-E=61q, ETlsl ?JolTl rJ+ap ztrzlol trl EolT.!tr|-.
488 Eq-+
=4
h += In s-&, -ln { = - F t, -ln {

l2E.sb^lg ol$-a]lo| ++. +lil HE].e+ ro+ += ¤-F "J^l
.ql 46ll^JH+7114 o E R, V "l E) +rll= MEI* zlL,<lzl
nl+^J zl ?+olE 94 rzn.saal9 4E ¤+.
N(e)
s= tp ! N,e, + k! N ,ln ,i =N/cBe + Nk ln 4 #JEt 0{l 12E.3
t4zl qluJzlz| 04 e9 E+"J 4ql qt||rJ} eB rzs

¤o + N(e)= u(T)-u(o) EB =Ukr=^ ol+61-H +¤,4 e3 e+ r2cql E6IH EHll ++e+ B+ qlq zlY {=t+e-& 4
44zl +e+ (e)=e t(etu +t)ol+. trI{^l E qlE+rlts t/r=kBtr- +a
q+r+ ?ol ¤4.
. U(T)-U(0)
s=T-+Nkln4 ?!=eul
tgE-==J. ErJ-71ts Eîl
(12E.8a) s,,=R{#-+ntr+e-e)}
eJAl2 tlE-+B Ez}-+ts Ezls ¤ 4le+el +41 +E ol ¤-Soll -H_ol=E^l+ 4ol :H l2mol{. T+ oo
{g
N4E EzI-Rb +zl-E g alE +l+ts ull= +Zl tlE tnrn G B-0)E Eql tr}+ E qltr+slE ntnzql d*fl-$- +
E eAÎ4"F'J4. olag ^JEll= NrExl¤E + +6Iq+.
^l-olql^Jel
¤]ol 5"J ^JEH.44421 rll$ol4. rfl6I"J tnr,/e+ Ql=+
ulzl Et zJg"6J ilB+ klnMrrE 4ol4ot ++.:_al_L lu
ol E|]+61 E + Stirling9 lnNt=Nln N-Ng olso B
=
=^L = -1
f 9l o + t2E.8a4lol cJ-o=g ?ol sl"lot ql+.

o q
o
j
E
ln N! 0.5 T-
q(D#q+Nk H
s(r)= ln i - /,6 lrt:E rU
ml
-
6;J
=4!#Q+rukhft+kru
olru
olq^J kNg kNlnee+ ee__E_e ol +¤-4 ?ol ul^+"1=. 0

5 100 0.5
^l¤- ?g.-, *flt ?E_, kTte
+ el+
f,g 12E3 e-Eoll ttl= 2=+l Xl E'J9 E flc-au; fl!-e-en;5 R=Nak9
u(r)-u(o) 9l= 7a; Hilte LEtLllfltrl. r-+-E Eoll q4 + 8Etl7l EgatXl E+Eq s.e
s- r +N/chff tdg-q-J, EzJ-EE E^ll R h2e. tr=:dtrI.
(12E.8b)
E4l 3 tlE4+ E'zlllzl rEl+ "JHIÎ

^JE4-+ Ezlql
ql+ a+zlzl eaJS SdeI !3 EzL EU}] (b) Br! ffig 7lq
.J+ qldql +ol 4+ eI+E ol$all.<J +6Hot
+-qI=4 EU}l flql^J +E,* SltrEulql ++ 43 *4zI eltlflH Hte+ e
qL+ ol E4-SE 6l+
^JqlEq ¤rl 44lf EE CEE +4U+.
r=41#Q+klne 9l= 4a1
(12E.8C)
lfl;<]- 9d zlzllel E Qls +qql ++ +E6Je-E^J ol !g
t8E AtE E^ll 6I]49 ¤H6LA+.
etrl
128.8a^13 +B +zI A+9 8l= evl= Lll+ qlulxl
^Js Or-
z F{l0l c}l-gl t!J=
^lel
pt EzI +tsfi sI+E +r}d alol4. rel+ Ezt9 {luJzlb Tr.r--
B4l(r), qa(R), 4lF(v), r4-r- dz} ^Jql(E) ¤lel 7lq=E tr-s 5B erJ B+flxl. dtql EI]EI l2E.8b4+Ei ^l4r-6}q,
Bol4, EHI e:+= zJ zlq=E #o + "J+ +6l]94. ol4 ol N=nNeE -.-!-4. NoE Avogadroel t$oJ;t ,3
^lql^J
qI al}E QIF +tlE E{ zflzfl 7lq=E 6Jol g+. 7l4lql^l Ee"*(E +)ol+. 7li{ ^Jql flzi9 gE "}^le Hrl s!
+zl¤ol +lil= flal HI¤ + fleq, :a46lq ols=$ E
=
zlol 9zl ?*=+. E|+^J QIE +'lq 'IqI Hd eE! 7lq= (12B.10b^l),,tE gzl Yltlol+. trI+^J,
12E LH+ ollLlrlel fl!=_er; 48e
]nRT }-
^l-,+lg ^Jz|6IE
Cd"l ol"llzl ¤ 4"14.
olel6J
E +irlz} EzL +ql .qilzl ull$ql E qlE +ul

nR
u(r)-u(o)
S
T
+mNok nffi;=irn+ffit"#
+ Tlille-l 5 +v].il 44 ?zls4. +71= 4L
ln e3'2
=
%t. }=rRt,, %t"] e +zlq A+B+ qlqzl 14ol .,e
=rn{i*r, Nof :r4a}¤ + =f1.9
E4 " d=6J + 9l= t4i."1 rl
t' Notr J 4 {r
y++= -
Îdg ^J46lH +lql^Je} ?3
ol*-e. ol 'lo
¤zlrl V^=Vln* ol zl;llel E+i{"lq, ,ag tu.rrzg El-+$. Rr
trl "JHg no 1 ++q+H +++ ?3 Sact<ur-Tetrode al ceg dBg + el+. ,Ol

il
g e4t ¤+. zE7l EzI +ql E"l?lzl 4lE9l(24 u[{z}z] nlfl
_e. ,,1e1 EEql 5 8l= +irl= s-Eql El

Sackur-Tetrode 4]
=qfl+)
4 f,tzlel4. olBl+ ddol +4+= olrq+-gE
S,, = Rln
tffi) [1 3^l sJE 7li]ll
(12E.9a)
zI94*fE El Bg t4E"l A+B f ?lzl 4l
Eoltr|.
{zlrJ /= g4 r}t}, ht(2nmkT)r/2ol+. _E= E SIE+El=
+6IeJ 4. V^= p71 l?-]tr p= p" 9 HI+q+E g+. Sackur-Tetrode 49 e6l +gr+ ?* Ee +4U4.
O,
V"t''
R/N o= 2 S=nR ,n
"' =nR ln ov. o-i: -
nN ort" nN otf
si=R,"(r-#) _R ,,(ffi) (12E.eb)
ol E6l-E rflzl-$d zlillTl yt_tr.+El yE E"g s+g
^lql
ts tril= la sl= +ulz| uJ-e-=4 *ol HaJ4.
ol 4s=g +3 Ss.ql^"lel ++E "l*el lol EUI]
=^t4ql
4, :z4a}"l "*.$ 6flE"1 A+g+a zi{a}:u gg aol+. AS=nR Ln aV,-nRln aV,
EI+^l rzl ogl rll+61 zYt\& rllE ol*al + S+. +trloll trfE ?l=+tr| E+ (12E.10)
-nnlnfr 195 zti1t. 5A 4gl
Zttr!trt q 1?E4 ol 49 +rlel ¤qq}4 cE(Eq :s)e+q

QIE
^l46llE
ArgzlE er}g m=3e.95m,o1+. 2s"Cql^J= ¤4 u|^Jol E"J A4rI +g+.
16.0pmolr kT-4.r2x10-ztJo1r1. q+^l ol $Eollr.'l Arel
E Sle +El= trl-g'=r+ ?Jtr+. (c)eld--E 7lq
( Ezt Eull 6J+= "JH E qlE +Elql EI.J sld gE9 zl¤
si =Rt.{ @.Lzxto-2,D".'1_l
} s#g Al.r}ts + 9l+. d¤ Ez}q a+ql= /E :zg ++ol
=18.6R=1551K-' mol-' kTohcBol-I-(128.13b41, d= Tlo?R, ¤zlrJ eR -hcwk), !E +
+2 44ql^l= d* zl^L"o.J Btl t4z} +4e flztB4 F EHl] gelql tr+4 E ql+ qlqzlql q6J sld eE 7lq=
RroltrI. rr|{^l rzE.8a^loll El+ q-q_r+ ?3 4rtE gg +
TIqg EzlE 4*zl q 4"lot aJ4E 7l=q^J d46IH
Ne4 ae q TIqg flz}9 s= E Ql= +ulz} Arql 4+ el4.
attr+ +.t"t 6Iq, dzlls r {Ig 2esKql^J 17.60Ro1+.

RT
kT/ohcB
r*=%g)#,!E+ntnf
olE 49 E4qrztg_e q^q=4 2rol 414a3 + 9l+ r?-ll- tf .$gql^JE 7lq- +f-4 eol B+.
tszI e%L"l +zlql E"lglzl rll+"il(a"]l= Blrql sl=n{r+^#} ad 889 7lq (12E.1 1a)
Eqil+) +4+ +ÎE g Ed Tlillel E Sle+ lde E^|- r'3(r > ao)]
ulE a4ol eg 4* zI4S gzlE ¤ sd zliil sld +d gEE oJs-" op ol4g q-q=r+ aol +4.J +E
E AItr-+ z+ +zL + ++1. A "J"JolE qlLJzl gltr|.
4"] ziHS flzls=B4 +4+ flzl¤ol 4 zYJt_
r46}q g4e_tr d=ts + gl. ^JEI]FI rJ "tt} sl=n{r+t,#} elE .3E9 7lq (128.1 b)
[dB E^l LP(r > po)]
1
4e0 57il Eq-4
3 12E.4ql ++L}lS.4. ol rHg ?oRol Ell4lE 19

_H.E a4
6LH gg6J e. "*=4= ag "J + gt+.
=^l^lol ^lr+
E 2
(,)-
j
F
(d) [!E Eq 7lq
H
ru
urI
E de +rlql qiql dF s4 zl¤ sJ= EzI EUl] q++ql
a =^f ql6J 4l(128.t541, U(t-s-Fncn1= 1/(1 - e*), e-hcv)$ 4
{Y -
g
01ru
olol
E=
+ qlqzlql 4El ^l(12c.8^1, (eu ) =et(ek - 1))g 4.J6il^J
g + el+.+,
0
0 2 3
3E, I/OB No(r') R
lal 18=
12E.4 dE Exl(o=l)E tlEeqql
zElolr Eg arl g"J6l'41 ?3J=20n'.r.D
EH-d trld EE9 7lq=
e-Eoll ttt= Eel.
r; =%gire+R h {" =y++n r,1_!
=rlEE ,7rp
ol $ffi a4 nB.4ql E,<lols.c}. ol ^.lg q+4 Bol al]4 =*{*-e=-rnrr-e-&t}

g+ el+.
7-
. qlE_+ylq q+ Eld eF 7lq= gEql q+ +
-1
zf6f^!.c-ll, olag q Bg sld tlEIEol d*9zl sx--a{ffi-h(r-e-rr"v} E ?!=euloll

{r Eflel (12E.12a)
-
,lO TIE 85 7lq
4lEol4. Rr
. nzl zl"IzlE qd¤.Fq zlcd,t! f;zli;l-urrl, ol4.

,lol
il ol
^l
q^l 4lE .g_E 0v -ha,tk$ zlzlrt- trIs=+ ?ol 4
nlru
=-d
e Eld qlqzl f9lEol zlll!)zl7l trll$olQ. +rll= 4"1 ¤4aI4.
s;=^{#+-m{r-e"'')} E fl!=euloll
r?-l6Lq = ;l +49 +$= tlseulql+ sld g'F zl¤
Efl-d
(12E.12b)
= alE 8E 7lq
E 6J+. olEll ,J*+ qlql^J -Holdzl"J 3scl29 E flE evl
ql q+ Eld +F 7lq= s8.61 K-lmol-rolzlql H,ql El]qI a ol $ffi lHrzs.sq ++Lllfl4. ol r4s= $lalg,<1 o1
2 rz.zl Ic'mol-'Hlql "J E+.t +qd gEql^J Cl2:-H2 ^lg

6ll46IE E¤.ol ¤ 4o14.
E+ q Be eld ^J4= d+ g}trI= Hqlî cl2= H,B4 4 T-+0ol E.ll trI+ gE +el + 6}01 0ol qq, q
d4 0 + q +e^j6l-+r. E + il= a"14. e|..rJ T=oql^J= ol S!= eulz| ool4.
e-Ez| 94zlH q *e dE tr-el="] d+¤ +
zttrJE! q12E.5 gEql EI{ +7}qlr+. #
+ E fl= +tr]=
?l o r:
2s"cql^J "clrE eld S
TlqE 4l4}6}qts EE zS +4+ flx}* "+* fl rr-+= *= Ezl+ TIqg Hi
z| gzlof zl ql$ql o =28_ +"t"t 6.Iq B= 0.2441cm-l SzI4 t! E tr"¤ *= Ezlql ulolirJ Eg 9s ffi
(24.41m-'oll dl*l"l4. ol EzlE cld +d gE= trl-s=r+ ql^JE 5 fle.eqz} cl t+. olae *9 a*zt
aol g+. -g.zlofl.{tr_u} 4lE qqzl zJ4"l ¤o}^l g4
nR (6.626x10-" Js)x(z.gg8xt08 ms-';x124.41 m-') o e d* zlg" * tr4iz} =-eil
rl f*otzlzl ollE"l4.
u = i:rstitorriK:i ^^
=,r.i5i il
zEtEt q!12E.6
Irl+^]
LE {E ++= 2l4.5cm-1-s^1, 2.r45xrffm-'91 6llB6}q,
- 2e8K l =7.05R=58.6;K-'mol-'
l+lnr<o3sr :. tl*i 5^J Ss= 30eK+. trFt^l
trle}^l 2s.Cql^j+ +
s* =R
$l g4 ee a+= eg + 91tr1.
gs.ql^J(r> aR) *= rlol4. pld gF rl

r2B.rl^lg t.g s,l =R {
rm,?5{(=Uga
_l - Irn( l - s-r
i,e Ky(2es K)
) =1.0lR
I e(30eKY(2e8K)
4 zlq= *e $uzyz1 aÎ6lElE $d+ E9 sld EUll
=8.381K-'mol-'
El+E ol+61lot +trilEq l2B). o1q ?ol 7t ar+E rH
12E Lll+ ollLjrlel S!=er:l t*91
I tr-"I¤I ullg %IHol z*ol B Lolo +(4 Ezlul.+ + Hll6J +

4
f
E qL 6I'l-= ++E ?lzl trI$ql) +ee {HzlE 44
tr 3
+rll 6l+ + "JHE iE ,t/-z"ol ¤4. IrI4^l SI_E +q=
(4E
4+4 Eol 84.
fz
ml S= kln2N= Nkln 2 - nRln2 (12E.13a)
6J
olru
1 r=0oll^l + H]]6J+E qL 6I+E +ElE + gl= Ezls=E
¤ ral= R ln2=5.8; 6-t mol-'9 TIF Ql= +qE 4440F
5 10
aJ 4014. "J9 szflel uflalol 7k6t+H ++ E flE eEl=
gE, I/EV
++4 ?ol 99ot ++.
feJ 12E.s trEE E fle-eu|1R=Nak9 utl#e LEh!)9 g.E.oll
^slT]E-^[
tttE Etrl. 0lE glEeults r-+oolE 0oll tr3ata r-+-olE +-dqe Eq. S-(0) - Rlns 11g 91= eul (12E.13b)
coE 4+, &F 9l= +iilE +¤zlE sl K-' mol-'oJql, olA

g ... co co oc co oc oc ...e+ ag EE +4Ia +ag
(e) IJF fllEEtrl ql qltr-q: R h2ql zv\& atol4.
tle+u1-._- E%lEzJ EllolEi$ AhI* +E 9l_r. E
ols-"oll.<J trq q +*+ a+ql 46ll^JE Hl+qL ^J4g 6il= + 9l
dE4 " +Cg +E 9t+(Eq 3c). F $l= +E ile
+ ol 4. wz11E H2o +zle B g* ^lEE S4"lltrzl. 4 t}i g
'I++el 4+ 4 "*zl"J {}+ ¤Elilzl AlszlE+ zle a+
zl-b +zll9
^LHill
sflzlE EBlrAlq gl=ql, Eg *g
ull$
E 91tr1. :z t olf+ dC 4Aql^J ^J dolE Hrzl6}zl *6I o¤81.il E61l^l Eqglr q= E3 7J +^ Aelql E4^J E
flzl ullE"J + gleq(rr]4q A*H/ro"7l qldql^J B+¤ q glr*{rH rzr.0y. r44q z*419 Hgzls=3 zJzl i zl
+), E eL ol-,9+ T=0?l rillql^lE g"IzI9 +e^Jzl z4 p-l
+q qL 6ILl^Ha4 np..7ql^Je+ ?ol oflzl4l zlt\&
g + ?lzl f
4"14. r=ooll^J {le eylzt o_H-4 z}4"lrl+ H zlel +E qL 6I+) ilzltr + fleq, ol+
"llEol+=
z 4*zl ?ltsrll olag tl+ flleeul+r +E+. 4 z^zll4 ullzlz[ z|E"6]+. rel+ ol ullzl$ol d+ -d¤¤
&+ QI=.+ulzl 444E fl?lr+ a a7\. ¤B617l f-l6l + $.+. = + ogzl ++lq 47I,4 Hflzl¤ ullzlali uls
4 zzl7| Hl+* + gzi Ae+ Be. ¤ es +zlE aag ^94 E + 2a-16 +ql^J 24lY *t zzl3 d oH zJ"lE 4E u11
all Exl.({lE^l Ell+61 qF* dzl ,3-+z} EtlE=i 4E co ilel f 62fl$|o1q "la,E"J"l :d+¤trHag 1.2r..7). trl4
q+q= = Eflilel
+zI).olull=... AB AB AB AB ..., ... AB BA BA AB ..., Ei ^J
* W_22N(*)N=(;)""1 !ol"F.J+. tr+
7lE+ +4C uHEEol qlq^l zl +El{zl ullEgl r+^l TI+ qlEeEl= S(0)=kln(+)N=kNln(]1ol 9:r, r ¤i
ilill =i6JHflolg = il9 s(o)=R In(}) -3.41K-r mol-rol gtrI. ol Ag dezl"J
+
^JEllllrJ tszl-Eol +4LA6Iz]I +48 + 9l
I 4o14. olel+ +e^lE TI+ q+ql ^Jzl} tl_EErl. 3.4J 11-t mol-,rt q+61 e. *.trt rq+ ol 4l& Egg E
Boltzmannal S=k lnl,l= al^J al&g + 9l+. zl# ol + + ,ll "Jd a6Jr+ rfll E -L trl-g "Jd a'Jol +zl4 Ao} tsll
zI Hll6}ol ¤-E" 6|al +E+H- + glr E lvztlE gz1
^lE 4.ll
7I 6IzI rBlH E"J6J qlHzlE +F+]g + 9l=
=q9l+r
fg 128.6 g3 HB^PI=C oflrl++loil rEl-g+ ?l= 7l'=-d

=doil^] ?+ :et
9lil= E^q ?E LtElLflfl+. 'J1J 8E Et fl^Pl
6fq, F Hfl^|.= ogr]0{l Tlnlol, LaLL trl= ^Bl4lE
F fl^|.= og^[e+E1^1116110}
Eal aal 12E.7 ral 12E.6oll E I-d Hfl^l=el 67frl H|lg g^1. E+E
Êl=
+l^l6t|0t -dcl. a^4 +E, Lal-r. E+Elrl ?Je E4 +e LtEtr-flfltrl.
Êl=
t+92 E4 Eq:+
ilql g6Ja3 + glE zl^L"

^dg +^l6}s.zl "llEql
g"J6L+
=
-r. g + s+.
=g-d7]lLJ=
I l. alfl Lll+ oilL1rft +Hl| 6J+E 'I+9 gEql +6J E6J+ I 3. E4 Eget4 fllEE'EI= Boltzmann ^lql e-l6ll^l eEqq
q Hlql-J+. Ezl EU]l EL+= zlzla_ gl+.
+Eig +E
. 2. EzI t}4 EeE Ei{ EEaJg 4 +E %}^lEE 7lq= E} a4. IIF Sle-erlb r= oql^l eal=E +A^lql zl'J9i Qle
oJ aol+. .e.ul+.
=s-et^l=
ce ^1
+4 al Ha
4S "llHzl u(r) = u(0) - (N/d (UN) u= u(0) - N(a h qtafi , TE-EB Ez} tZE.2a
cC-Q_"]
=o ai Cv = Nk12(&lnqldp2), tlE-+B eÎ tzE.5
Cv-=j(3+vR*+2/*)R T>>EM tzF,.6
6ll F rlr,ll ;rL*L o^t+--^-- .-,Ll o-r-1- dr) z.l 6l

'dt
L! - =- -,1 -ll E i_l rrurLzrrrdrul l)-,\llt vv LLD./
flE +ul S= { U(7) - U(o)}/T+Ivk ln4 EzJ-zl-b Ezt 12E.8a
S= { U(7) - U(0)}/r+rvk ln (qel N) EZJ-Eb EZT 128.8b
Sackur-Tetrode 4] s. =R ln(v.et/'/Nnzl3) lgÎ9d zl4l9 E QlE +rrl lZE.9a
t+ 5 QlE +ul S,.,(0)=P6t s= ¤*r6J ts}|olE + 12E.l3b

EE 12F ftS. E+=
trIg gqE4 4ltq+ A+

> ol trE= Hll+= 018 ^lolql tsar*ol 919 CAg
qlE ols" g + 9l+= oldol 9,lzl rll$ol4.
EE-+= 0lE6tE tEFl +E -Er+E glEJtrlstGibbs ollLjrl=
8salg + fl.g.q, olH Eoll^1 gqql3
=61
Ee-d a= 7lfi,r|I
E + ?]tl'. qal^l 0l- Eufl -gtag +^4 dEal'Etr 12F.1 B=
=dH^1
aol
^l7l= =e.o-frf.
Helmholtz glHzl AY A=U-Tstr- CEg+. ol AEql trls
> "_{d T|{LJ ol
E a1o;= u(o;o1 94, +4ql+ u(De+ s(Del +Zl= Bq
Eufl -gt4; EB+4 +54 tllolEl= EE-+q qa1 3E -Bt+=
BB 8+sl Ee^l7l= q-E'E Eltl'. +H +gr+ ae ql+61 zI+6J 49 eg + 9l+.
=61
> =Je.Et qHI xl^l Ae)= A(o) (+F)

0l E4oll^-|= Ll|+ ollLlxlel Eee{(-trrl 12E)E EE= ,Jd ;,{-oB(+F),.o*n}
aol+. 0|E ¤tr4 fllgtrl(EE 28) ralr = A(0) -kT lnQ
^l4LpJ =x|Ee
Helmholtz "J Gibbs 0llLlrl(En-,r 3D) tolel g4l= goiot elq.
trlrlE troll^Jb E= HJB Gibbs ollLlxEl BE 8+(EE on) 7-
--.I r
gA|E 0|E6[Xl Etl-. 0l E= EUll -EI+{EE 12D)=

^tolE
7l^la- ^+-
-s= 88oll^'l= Exl-Eiufl fll'+= 0lEat1l A(T) =A(0) - kTln Q Hetmhottz ollLl^l 02F.2)
^TllslrltrJ
EtrI.
adSol .ftae3=og Hg trlt.}- Helmholtz qlLJzlzL
611=-pdv-SdT "JE H+trk"] 49 eg :Eoll^l +E+ dG
ql ql.J 38.74, dG=vdp-sdrel +^16|+). E|+^-l gA{} g
rC gqEql^l= q+l +E EI+=¤ %IH+l6lrll ols"eI4.
qlE^l gnlqiql^J= flBEE d+4og o19-o6[_r, ga* E 6Lql^J= "Jq4 Helmholtz qlqzl p=-(dAtdr/)fl
^l-"lql
+A\71^dB++.EI+^J l2F.zal e+q +,q_4 ag 4¤- +
o
"Jq4 gEql^J "Jq+= HI¤¤ E6J tr}]= Gibbs qlqzlE
EB + 9t+.
d64 o e ols" ¤I4. ol ^"je5g E+ Lil+ "ilulzls+ ti= +
qs+q +Eqq, Fzl¤g trl+r+ ?ol EUl] 6J+E zlxla_
P=or(q#), grel (12F.3)
++'J + 9t+.
ol +al= Sd6l gqlzl"J 4" +^l Sd ,lale+ {zll zlz.ll,
u(r)=u(0) (Q$-), gzlrl p=# Ll+ ortLl^t (12F.ra)
r?]I Eill= sElq1 E= Eeq 4+E+. a= "JHI4-" +
+tr1, gE q Ea"+g 6.rfolq Ir+;}^J 12F3^lg Eq lAe+
s(r)= Yg+9+krne 3Eql^J Eq6J a" F9 t44 ol4.
=-oP(H),+trnQ ?!Eeq (12F.1b)

8Ell^lol fttr
{zlrJ c= +tsl] E}+(Eq L2D)71ut44xl"J olag +EJ+l ^JE-+B "J"J"l Tlzllel "Jqg +4q]= ^l¤- +E6Iq+.
g gs= s4. dxll-tr ol Eq.il^J= EzI BHll E+(r, eq r.a{-g /.}:d: $4"1 9d zl;]l BzleE folzlEzl= E
12B)= ol3-" olft. a+"Jg +l#6ial ¤4. rzr.r^lg tr-E-+B olot B 4"14. tr-E +B4e EZI-+} Ezls=E ¤ zlxll
EzI d+ql ql+ +al= +4LllE zlB+ "JB"J Solq, trel ¤ 12F3^lql Bq^J zll4l4 o + +6IH ¤tr}. Ha E
s-58 EzI d+"J A+ Ez}-zlt Ezl{l qdl^Jb a=/9, Hll EL+Elol +qql E=4q, q-+^J +zlE 4+ +F
"J
EA-Et. Ezl-=(Tlillql^Je+ ae)ql 4611^J= Q=flNrg jr ^lq '.il+
$ufl fl43 E*^lzlzl $ols_ g+.
E ¤+. ¤ 4= olf+ +Eq= 4Eol z}+6llzli4 E4¤
4e4 12 EAIEE:+
zlilloil qail^J} q-flN! +qiql^J zlat 6,q-q} gqE4 6J+ +E 6l-+= Gibbs gl
tlE +84"J EzI59
=ol
ol \, f zl G=H_TSol+. ol 49 G_U+pv-TS+r ¤ +E gl-9.
- v t,,t3 ol4. nlE}ll q tr}4^J G-A+pwl qzls 6J+ G(o)=41s)olq, ol Eg
DlnQ Eln(,/N /lgl)
u(o)e+ a¤¤ +.rE_6Lq+. Gibbs qlLJ^lE ae+pgl +EL4=
P KT
dv T
KT
dv g Ao-JoIH q=q,=$ 1lol EU}| 6J+=. zlzl:t_ +EB + 9i+.
T
( a(nq* -lnN!)') ( dlNtn,i-lnN!)')

=kT
[-----av-.1 T
=kT
[-----"v .l T
G(r) = G(o) -krrne+*-(H), Gibbs ollulxl (12F.6)
^Jg 5B zlill $zlE A+qlE G=A+ pv4 44 pv? nRr

=*r(Y),-*,(.#), _e. HI+l¤ + gle =e 4g r+s=4 z;ol z$slg+.
"l
dlnf /dx= (1/f) dfldx G(T) = G(0) - kTln Q+ rRT (12F.7)
NKT ( 9L\ q uiolz|.{ Tlill ^}qlel EA-B+ "J,Jolql Eiloll^JE Q=

q l-avJ,
,f tN.ol o-e- lrQ=Nln4-lnMolq, q4^l Stirlirg9
Nok= R
(lnN!=NlnN-r$g ol+6i{ flE
=^l4l
cJ-o=$ {.ol 84.
_ ivkr ( av _ _nNt,tl) rutr nRT ^lol
:-l
vtlf\ av ), v v^kT V nNok= nR Nln N-N
G(T)= 519)- NkT ln q+ kT ln N ! +nRT

"l 4l& a4ql E6lE tlg +84"J "J"Joltr ¤ Tlz.llE
zlill Hzlol g+. G(0)-zRT ln q + kT(N ln N- N )+ nRT
^JE]|^lg $d
=
7{ 495i,(1 ?*g i}ltr. tso}ilqE +

12F.1^lq^J firl
=G(o)-nRrh4+ffihru
nRT
ae 4l&g +q6}ts p=Ntlwl'Ie+. ol E4zI $d

Tlill Hzl"l 9zl +l6}l^J= Eq l2A-l2Eql^J qlt}6}r
Î =G(o)-nRrrnS (12F.8)
e" ¤I
4E g=ykrzl9"lo} ++. olag Bql ++ ¤^l +
Hol4. El*d %l"Bg ol+6IE van der Waats ol ol+6IH 9lHzlE += 4Eql^J 6l]46J + 9l
^lg +Eg
Gibbs
^l¤-
+E ?l+. rxllE t
EÎolE t}^ll+ 4829 _H-oI4. t+.=, ,i ¤49_e d=,_g + 9lE tl{el ¤t+olr E N
rPl 87[ 12F.1 a-lrM"J 3 Ezl^fol=+ G(D-G(g)e el Ezlz} g¤+eE d=B
^lEE t]-E}l^lg +E6Lq+. + 9l= ¤+ ^JEI+el 'H+ql Hlql*q. ol Bt+7I eÊr-ql
{=vtA3ola_ F +qql el3_61+ *+4. ul4 ciUUs ollHzl= 4l+oll.! frti6l.q G(0) olo].tr_ g+. r
r(Agfute)f l+ A/Jdu = d:E
=lflq Gibbs "llHzlE *+el} gq+4 A6Je g4eE d
T]+.ql +E +'ilsl
^171.
?alol4E a¤- "J + 91tri.
+lql^J ¤e
pql +6J ru_u+pv* H(0)=
us+ y1s) = -Et++r
^l=4 r+q=4 ¤zlrl {^=dn* E EHl| Cel6l-btrll(E9l*mol-'
E Cel= ol+6lE ?rBq Hql +6J ae 49 gg oljJ, n=N/NA) g-e-tr- ola¤- ¤46l.rll ol+6tzl E4.z4E
+ 91tr1. Gibbs qlLJzlTl- q-q=r+ eol g+.
H(D=H(o) (+F), .orr[#), ?l=tr| 02F.4)
G(r)= G(0) -nar.-ft Gibbs ollq^l (12F.9a)
tEzJ-=ts 8E-==J E^ll
ol # +e-6l] _H_ol= dsE _H_ol qlg]4= zlE c4

^lol ol G(01= u(o)g s= EZITI HlEr-^JEIql flg "lel 4l
^lql^l
g qlqzl Eo4 F"J.J 4,o14. E= Gibbs glHzlE 41416|el
4I ++"J 4o14. tls +B "J"JolEe ¤ zlrll9l ql6[î= r s= ^J4ql^lE 4l {"êE +:oi"t oJ+. ol
E EUH EL+E
U(T)-U(o)-|nRI r4a pV=nRTol+. ,t|?+^l olelql zli'lJ
ql ql6ll^J= trl-s=$ Ae
#e HTI +F Tlqqlî
^l^.S6I=
5 +r1= s.= E +vle+
^lol ^dB+{. zt/l Vf -RTlp"tr- -aa EE {"^=(V;lA3),f,7vo1 9olo} ++.
H(T) - H(0) -]nRT (12F.s) E= p. Gibbs {lHzli olEl6J il++g 6|I oloJ.! no + 4
12F ftE:El+= t+95
E a"l+.+ Nxr{^(Hr)^(Or),/r/,,l(HrO)},
-&0,m_rr,-
_AD r\r r'
¤ .tr= Gibbs ollLl^l lf" (Hr){* (or)r, t{R (Hro)l
vt^r,,
{^
G|(r;=5i(o)-nrh N^ =
tE'J-E=,
(12F.eb)
ArE-=aJ E^ll olzll QlolrlE¤ Bq=+. E- qlLJzl iHaql oil4

"llHzl
G;(0) =EoJng 41E E HtE-tr-ql qlLJzl+. kl mol-r-E- +r}U+)= r+s-r+ Aol g+.
¤zlrl =
492-a28=-920 436 497
@ Eu]l pt4g .IEEI EE sc Gibbs oilL1rl Mo,- = ilGpl- ffi -+ ffi) = -236 kt mol-r
E 4ht
q-*q= 4d EUH + ,RlE g Ctr + g
E++= f,.Î^le
2s"cql^l H,o(g)9 s= ^8d Gibbs glHzl= 4l4I6Iq+.
E7I +Eal sSzlE "JoI EoJoF ++.
ra{E AIEI ^JC H}¤. E}q}4g 4Ai, olq^J 4 Ezl-59
Gibbs 9lHzlE zlzl:i_ E= qlqzlql ql+ 4¤- HrO HrO Hp H,
^Jc Gibbs 02
+4. r4r olE ciuus glHzlE 4L +=E ezl EE11 EL i/cm-r, 27.877 r4.5t2 9.285 60.864 r.M57
X=A,B,.gL=C
4 zlzla +4u+. 2s.coll^J= EzI dFol EEzl g+
g aols e EzI {tlq zlq= +^l++. H,9 sld tr-+ OR/K ,!0.1 20.9 13.4 87.5 2.1
E 0o.a64cm-t, 0291 tl|+ <lg L4457cm-', :aEltr HrO(g) pffi

q 4+ {}Eg 27.877, r4.s12, r4r 9.285cm-'ol+. 3rld ol *4ql zlll$$, tQ
.H-E 2e8Kql^J= uruJol
olq H,ql qldi^J= sdEI sld EUll ++= 40t d4. 4
EHH q}+q Lzl dql 9s7l-?+61 tgzlE
=Î^l* E aEql q6il^J= +lql^l ?_ls" d + + 9l+. :a
++6]lot 6Iq, gETI +zl e*¤. qlE sdt EUl] EL+ =^L4g
^l elH,
I alo} ++.Eo_9 AEg _s. effE A6J flgul$ ol$-
611, g"J+ 4lt}"l gs6IH A.J qlqzl(r=Oql^Jel)E = 71.21pm ,,1(Or) - pm (H2O) 23.82pm
z1(H2) 17.87 -
ol.$aflo[ q]4. Eq t2BE trl-* !g ol+6]q4.
qR(Hr) = 1.88 qR(Or) = 71.60 f R(HrO; = 42.13
dE EII. EI E¤ ETI,
o=2 o=2 trI+^l
v2
KT
,,) r^=*(#)"'( ABC
TI
q. 2.48 kJ mol-1
ô=O#*ry 2hcB
A,G' =-236klmol-' - [i mo.oz 9t= -222 klmol-'
E0l sI+ HI¤+ Hr(g)+joz(s) +Hro(g)ol4. trl?+^J, z|tr ¤9 .s 2c.6el trllolEi= -22857moI 'o14.
ArG" - G",,(HrO,g) - G"_(H r,g) - +G"_(O2,g) rPl g7[ 12F.2 2s.Cql^J NHr(g)9 S.= d^d Gibbs gl
HzlE Al4l6}q4.NH,q fld tl+=g B=10.001cm-,rl
4.Sq- ,+ + /E s.= E EEl] EI+= zlzlt_ s.= E A-6.449cm-Iol4.
Gibbs qlqzl= +4U+ r-loul{ gt-:E
G; 0)= Eo,- 0)-nr,r#, f'^0)=,il' 0r^ 0= ffi {" 0)

Ir}4^J, 12F.2 tsE g+
a,c" = . (H,o)-R.,.dfiQ}-{* .,r, l-o.r,ffi ¤zlrlE zlxlltl-HI*q +ql^l 44{-elr 6l+ql, oltrll= ¤
{r, }
¤ ++E HI¤¤4 ^JtEq ++'Jq$ z$la- +ElE +
-+{r,,-to.r^rrrffi} el+.
,[^(H2OllNA
{y: /N^ A(H,O)3 | q* (H,O)

=Mo.r, -RIln (a) r¤t EH]| g+ lAl
{v: (H, ) {v:/NA^(o
/N^
^(H,
)3}4R
')'l{"(o.) t"' ^tolsl
,i^(H2)lN 1
It ^Jg. +H Ezls=E ¤ zl;ll9 Gibbs qlHzlE l2F.e^lql el6ll
4^(or)/No
^J
SHll 6Ji q^_qtru_o e+q +B + 9l+. 6J¤ ¤¤ r ^Jf
t 96 EZIEq-+
s= Hl+ Gibbs glHzle+ +4lg+ qzl.<J 6l-r.zt 6I= "J

=
g ol + +4lE A6J6Iol ¤¤ tI+= Hl$$$ e-ar&/R7 E-d d+ (12F.10b)
^J^dEel E '={.,(ffi) }
zI EU|| 6J+E zJ-xlLufrlq= aol+.
:tsI¤ 7
@ Eull d+ lxlaLtEtL.! trJE 1
+ *EE _E= E Gibbs qlqzl Gtn4l ++ 49 olo-" 6|{ -s NAhc4(u8E)

HI¤- Gibbs qlLJzlql +qI 49 +6ll"t 6Jtrt. ralr 6A.1s
NohcQ(8dE)
= lnK)$- ol+61q ¤B tL+E +++. AE-
^l(a,Ge=-RT rU
Ell 1 a,ffql ++
^l
l2F.eb^lql el6ll^l aA+bB+cC+dD HI+ql s= E qI+ fg 12F.1 E:d Afoel trsl. BJEE=
A+ llltoll "J9.-Lf 7ltl4o+
3^F=e 6Hal^l7lr 0l= fl^lB+El 8dE¤ U=trl.
Gibbs qlLJzl HEI+ trhq=r+ *ol ¤4.
A.G" = cc](c) + dG".(D) - tac:(A) + bG"-(B)l (b) 6[al trJE

= cG-,(c,0) + ric;,,(D,0) - {aG',,(A,0) + l.,G;,,(8,0)} r2F.10a^19 ¤+61+ qlE^J zfl^l Ezl xrzl z-J-$ flzle all
fe.-¤eel elEl='l+4 eg ¤Bg _H_zI.
-nr{crnffi +drnff -arn
ff -r,.ff I
^J4t6H
p'.
qlqzls| p9Ir-E, 4 G,,0,0)= X,(g)--2X(g) K-
G*(/,0)= +P Hlq
^JEl] E P*,P"
Eo,.(/)olo B ol +He-l a4l 6&44)9 q-.q=4 aol g+.
^l r2F.r0a^lql 9al$ "l ¤B tr-+= +94 ?ol ¤4(a=r,
cEo,.(C,0) + dEo,",,(D,0) - {aEr,,,(A,0) + bE,,,(B,0)} = A,Eo b=0, c=2, fel]l- d=0).
rBlH alnx-lnlr4lnx+ln y-lnxy{ +al# ol+d}"l +le-l

qgr+ aol ¤ + ?l+. * -({"\.^lN )' e-^.80/Rr - V1)' e-^,80/Rr (12F.11a)
^-d= {"*,.^lNo /;,,-No
A,G.= A,Eo _nr n (r.8,- /N^ )' ( rE,*llu^ )1 { zl rJ,

(q"o.* lN o)'(qi.^lN
^10 A.Eo = 2E0,-(x,0) - 80,-(x2,0) = NehcDo(x-x) (12F.11b)
(fZ,- lw^)'(/8,*lir,ro)'
=-RT I_o,r,
RT -r-
"" (ri'o.^tN)'({i.*lN)o
I
I I q7l^l NAhcDo(x-x)E x-x a,EtE E 6114 "lluJzl4. {}E ?l
zI xE s= g tsHll ¤:+= q-q-r+ B"l 44'g + gltrl-.
EJAI? K.ll ++
^l
ol 4f =-RrlnKel ultal.{ q-q=4 ag Kql ++ ^l V = RT/o
^lg
g eg+
.T
el+. V"m
,e
gx X 8*RT
,l x ,m
7I
l,rt<:-4&""ffi ¤zlrJ &= xel
P" A:*
Hlqr- dzl. trl+E4. zflzl E^L xr= E

^JEH
ol qrll+E a6lr cel6IH ol zlol +¤.4 z.ol 84. qA$ 15 z|$rE zlzlt- 9leq, q-4^J r s.= E EE}l
^lel
EL+E +.q=r+ ¤ol ¤4.
Ee g+ (12F.10a)
,
y'x,,r=8x,
V; R' g-.RTYf,Y-J.
A1 't*,'t*.=
ol A,.Eog g qlqzl zl-=
S^JE$ Hl¤¤el H|qI^J4
^lql^J utq dzt ^J4 trl4E+. trI+^l'
+4'ile +=E A6J 6l]r.l "ilHzlepq AI4I6J + gl+(rg olTl^J g.,= x2E
-
12F.1). Eq 2cql^l E"JqI s|+%F4 += ol+alH ol B¤ tr'
Q*RT tP'11*)'
+E trI*4 ?ol 448 + 9l+. " --
v
g*,N^RTyl, ,il.tp" ,ti., '
o-N.hcD.(x-xyRr
12F ?+ -d+= t+97
R=Nak P
g'zxkr Ai R
e-r'cA(x-xyftr (12F.12)
g*,P" ftr,d,Alt
ol +9 "J==g E+ +%lqlzl qlolElE zlzlt_ 4l4IE+ +

^l
el+.
A,Eo
!l7112F.3 iiJ'B
8+ol 4ltl
1000 Kql^J9 Na,(e) + 2Na(g) a]le-l HI+E B¤ tr-+ lal 12F.2 R(HJ-)rl.p(8¤AE oilLl^l H|]E. Beoil^1= _?=
=.9l
Zlsl 8B Ad8
=?l
Al&6Iq+. b-0.t547crrr-r, t= t59.2cil1-r, NahcDo= tr= 7lE6lq(r 8E7l' 8Eoil g=:elrl), Eill4oJ
=01
=
70.4klmol-'9 tll"lrl= ol 6Iq4.
Boltzmann ttt=tt. Af,ool zl!4q R0l xlufl{o+
=soll =r[l6t4l
Etrf.
"
r.alE Al:d olul oj_r. 9l= BIe+ 4-ol Na:. 26 Hlq^Jql
7l-zlr. 9l+(6J Eq l2Boil^J g
71g 2Su). 12F.12^lr+ P
=-
g EU1] Et+ql +6J
^lg
ols"d4. olq6J 2gz} +|+ R
Ezlql ql6ll^J= 9d EUll ++E *r}^l + 4E aol

"
¤4("1 4= aol g+col lltszl *q]al+ 4ol
=^l-=
++). r4r Fq 2?lz} +zlql ql4^]= o=2o14.
44Iq1 g,q6J eHl] Ei+e+ 7lE olE=g'l+4 a+.
=01
A(Nar) = 8.l4pm zl(Na) = l1.5pm
4R(Naz) =2246 4v(Naz) = 4.885 lB 12F.3 E^]=E d|Ell "JE= r.a16l.= a0l p7f R-E.trt ollLl^l
(Na) = 2 g(Nar) = 1
Eoll^l Eq4E{+ LEoTl g+) E= 7l=o:d Pel =961-trt.
8Et|7l ".J71 ttflEoll
ncrt*r = 8.47... +oll Sl ?!E Pel Eill THillt= ".jll Etr}. r.E EE+4o+ rE6[^lE
=-ctE
EB= ,g4-g trl|= glgtrlet El4l fllEetrE .gr_l6ll0t 6|.= a0l+.
g}e Eld t4Eol A+qq, El4^l /(Na,)91 ql+
4g AIE g+. rBlH tzr.tz{ e-E+El trl-s-r+ ?J2 =Î
4+
. Eg+ et+ tI4EE zflz1a5 Boltzmann9 Ees +qzlq, +qA tlEl]
z| ngl +6IL+ E= pql +4L+ql= ++6I+. ttI4^J +
kg m2 s-2
f 6-r )x(1000K)x(8.14x10-rz rn;: .. ^llEel

9luJzl +EB p.qz} $.ol ol5 dzll
_z'x(l.38lxt0-rr =+1.
++ +"J Boltzmann +EE ^J46IH g+. r?]6lq=+l=ql
u ,aa -8.42
^: "J"J n
=2.45
kg m 1s-2
4 pE gluJzl i9] {{ol Hl*61-r_(rfl 12F.2ql^Je+ gol) p
zI n_H_4 +l.tl 9lg trll= rflql^le+ eol ¤B EuJE 491 n
rlTl g.71 12F.3 rso0Kql^J9 r= +4q+. *aJ B"l

ol zlu;l{ o + E+. rq4
pzl +g t}E]] "JEE z}
=xl]6l-rll ge
ol a[e-]z[ g.g H]+"Jg +$qL+? A "I(rH 4"1 f"ltl
t2Fioll^Je+ gluJzl gE
+ql +
9 tr.4z} Eq flg q)= P7I RB+ 53 od qlqrlE *q
h&r :zs:E
4E Beql^l= P7I +4l6}ril ¤tr]".
¤Bql^J REzIe+ PBzt9 Ezl^+ HJE: Boltzmannq EE4
4 Bli6J ^l o + +q4l+= ag ¤41 Bg + g+.
(c) Btr 8+oll EH:d 7lq
¤¤ t}+q E?]qr4
olxll ola]lalzl +l6Il^J a+61 @ trJtr g+et dtEt{ 7t{i{l+ tol Etll
=4=
R +p Tlill^J- ¤¤g c46}l sz(R3 HI¤¤#=, r4r p
^lo
C^ll Ezlfz[ nol +q]4 (R,p)E a+, t]E]l ;9 zllzl;5 10,
^JCE- +4U+).
= a4 =y1g-k,qol+ .lzlr.J Ng drll Ezlf4
DF.2ql + qlLlzl +Elqfl=tr1], eI ^ll
Eb
^llEel
Rql +61-=
=+l=-
aoJr += tI ^llE= pql +6I= 4"l4.zJ E4l 1 Rr+ P Bzl¤E += +4L|l=
^l
4es 12 EAIEq-qt
R+^lfl ++:
+6J419 zfl4liE Rql +61-= ^JflEql
(R,P) P
^JEllEg ,g 9.(16|-1
aa 'J+ 44 ol rJtr+. qlLJzl= q,E
s.^l6J+. E pBzteJ ++= pql +61+ ^J4Eql ea^l q R
qI a4 *4. ol pE s,,rlop 9luJzli ers 44U

^J4Eg
+(E+"Jg E.J olf* + ¤B6I4i+).+
¤.
AEo
N*=)d. =IZ:-*, No=y, =I+ *t
RE tlEHql qle- z EUIJ elf r*4 eeq, El+^J

aa azJ 12F.4 ollLl^l ztrz3.1} dE]| gETl.Bfloll El^|ts g:ef= rAfo-l7l +l6tl^j
Np=N7p/4"14. p9 tr-Ellql ++ !+E e.ei EUI eLfzlEI ol gL e9 8Et| gE7l8-J6l E
E&ll^j EtrJ. Af00l r[6]
=rl
nllts
,I: qlqzlE 4aJ4l diilE uI4^J4, + Rel u}qlr}4E zl P7l
^l.Eel
xlHt|4o+ Ecl.
+6ll^J +46J 4,ol4.rel4 od qlHzls+9 zJ4*
r 6IE io-eo+A,qol sltr e q-s-4 eg ar+= Erll^sool4
¤+. 6}z}(re DF.4). olelq} Hflgql 4t EU11 6J+= ++el ql
4lt}+ utq ?ol ,/_U(t-e-ps)ol+. ol
rzn.rgl,rJ IrJ
'r=#?'
0le, 1.!trr
'=#(?'") "-furo - N{o
f "-wo dqq flg EI=(4 e<kr) agE ++ql^J q=krt*l 44 =+lEol
N{' IRT (Eq r2B). ol4ql e.BE 419 A+qlE ¤B t}+z[ qg-4
-
{ "-o,', ?ol E4.
9E ^lql\ HFC ag EzI +flel qlq
zlE ^¤ntkrE ÊJRrtr- (1)F 14\
E E+]E qlt lzlE Eg^lvJ U+r+.
EJAIZ ¤E t}+q ql+^l A,.Eo"l 4t6l ull= zlfo-lol zlu]]4ol 9o+ K<tol q
zfl*llf Hl= r-JP-r=4 ?ol 84. r" q+^J pE =
¤B EoETl- 4E ool ¤4. aprol 4rzl| alzl
$ ou_r4 A+ql= kyezl4^J 4!. zl+ o-lg ++61 "JE
=
ts + ?lzl uliEql KE 6101 19 Hq¤ + 9ttrI. oltrll. pzl t
NP {p
- o-t,eotar
NR
el te
fp.
qlEql ¤¤ +
^JEH "JE ^J4ql^J "JE4 " Elotzlq,
t¤ n +p HI*g ¤¤ ^J+E ol + ++9 Ezl-f9 ule+ ol
^tdg Hlgfl+ lol 19 a71+.*3 gEqlî= K< I
+L+. ir|+^J, olq, al= d4 o + nqls_tr ol+qTl+. te gsql,rl= zl
Y-fr-r-o'h'*'
f E51zl- gl Tlvlflzlq zl+ *zI4 oJ^l kTlol z+. tr}+
fn
EE Ar+ (12F.13)
tl vzl zlull{ol g+. A+ "l g-g H}*ql^J=(pz} n_H_4 I
oll glo oe ¤:gol+) gszl-94ziH d3 zl#EI pE
R+P *lBql^]=EHl] 6J+ ?]E vfoJzlSol ^J4lqq, q ^JEll
7l ql+61 *olzlTl ullEql pE ¤¤ bEzl ¤zlt;lAl ¤4.o1
4\ q"E rE Hl-#olE E+. !-+'JHlzl"J +f,-el A+ql= 13 e.q 6Bql^l 4rl4 " -e t 484 "Jil6l-= ar+4.
K +q +sb pE: E{+E HF?.-r- 4Cql^J q7l q"E Ht+lrll ol EBg EEI ¤¤ +lil= aaql T= aol qr{^J elg
¤+. ulz| olr-ll Gibbs "llHzlz} !"loF 6l+zl= ¤E6ll
zl{a}i $z} +
12F.13^lol *61+ uffi olaJl6IEJE ol =L+.
^lql 4 3rlq+=9 tr-'Izl qlqzle+ EL4l :a /J.4 "JE(El+^l ql
I 5Cg a+ r+tL6I^J {46]l _H-= aol +4. :z4a}{ n E eiil)zl- Tflill+ +E. ffi61q q{^J ¤¤ tr"+el Zlg
g qlqzl 6I+"J zlzlt- 9lq^J 4*=1olep E
^J46]| 4l+{+ 4o14.
z|. :_=l-r.=+l=
p= #+ eo7J4 e9 E*3 zlzlt_ gl+r
=+l=
12F ?tr -Br+= t+99
=s-d7HE=:d+
tr 1. EE-+4 A, p, H, :tQa_ C+ A= Eq EI+E zlzla_ tr 3. Tlill ^J 2gÎ EzlE 6l]4 ¤¤ ^J+= E%Iq4 qlolElE ol
41&6J + 914. +6il^l 4l&g + 91trI.
D 2. gE a+= EUll ¤-+E- zlzl:il_ +48 + 91trI. a 4. Eltri BBoll tr:d Ealtri4 qq^l ,J44 tr-ql
=4=
,JE.<1o1E A^8¤. zlzla- ¤E6.J =9
+ 91trt.
=e-d^l=
.A-lzI ,^l z.^f al Hs
o=. -1 I --'t
Helmholtz qq al A(7)=A(0)-kTln q tzE.2

ol-d
ll -i p=ftT(ElnQ/Ev), TzF,3
elBul H(7) =
p1e;-(3lnQ/Ep), + kTV(Eln qt av)r rzE.4
Gibbs 9lH zl G(r) = G(o)-kTlnQ+klV(dlnQ/OV), rzE.6
G(T) = 516; - nRT ln(q^ I N

^)
sd Tlill lZF.9a
¤¤ tI+ = /N^ )t $d Tlill 12F.10b

" {fltri- }e-o,*,"
s00
=ZlEq-qt
E71 xt2 Eq-+

=711
pr $r.121- $.= 6J E-= Tliil= ${ zlxllr. rilolqEg zgs 19 a# z}3a}¤4
EE 12A Bol2rnann EE
n= gxll
Dl2A.t gE+ +Eol+? Dl2A.3 zll4lf, tsllzl, H +rll ÎolE +4lE ¤E6lq4. a1'11 +E tsIlilel
Dt2A2 +4ql^J9 Boltzmann +E9 EBg ge+51q4. 9E= +Eol+?

D12A.4 CH4 # +=9 9E= ¤E6Iq+.
G^
Jrr
El2A.'r(a) .llHzl 2J4"1400cm-'oJ z=+l 419 * tlEli zflrllfz| {$ Et2A.4(a) l6zH9.lltt-"l o, t,2,3, 8,0,0, 0, 0, 2-E +-EElflg trl]g Hllil9
r}4 zllxllfq 3EE rol 9E gEE +6Iq4. +rllE 4l.t}6}q4.
Er2A.r(b) qlqzl zf,lol300cm-'oJ z+9 419 +g tr-q z|lillfz| $$ Et2A.4(b) 2tllE 4t}"1 6, 0, 5, 0, 4, 0, 3,0,2,0, 0, lg EEqflg q]E
r}4l zflxllf9 tlol q= gE= +4q+. HIilg +alE 4&4q+.
El2A.2(a) zssrollr.l dB fldz}9 /=04 /=5oJ tr44 zH^]l Et2A.5(a) stg (i) g'JoJ +, (ii) Stirling +^l-41 tzA.z4, rql (iii)
=flql^lE Stirling trq CqeI
^lo
xt=(2n)tt2ftrl2e-reol+6}q 41416'1q4.
+= 4l4I6Lg4. B =2.7lcm-rol4.
Et2A.2(b) zssroll,q 7B sldzl9 /=04 /=50J +flql^JE ^}44 zH4l E12A.s(b) rolg (i) =Î^l
g"JoJ (ii) Stirling tz1'zq, relJ. (iii)
g}E ¤+ql^J ^lo+,
Stirling Eq eq6-J =Î^l
ol+6}q 4lt6}q4.
+E 4l{!6l-q+. B =2.7lcm-rol4. ^l-8-6J =Î^lg
El2A.3(a) .lE EzI9 Hlfl+ EE dl4z} Hl$sI Hlq tlE{E4 s40cm-' Er2A.6(a) gETI +6.JEllE qE 2=91 4lel t}4Eq tlEil4 zlliil+Eg
"J+ +lq +l,'16}r. ?1E}. E= ^JEilq ro"z.9 Ezlz} glrll ¤ gEE +4q qBrll 9dg+e
E12A.6(b) gETl-O-e--e ,s=6IE 2=+l 4lel
+. ^J4EE ^J.ll4 7Hi-ll+5-a-
qtr EzI9 2¤eE qslg EE t4z} Hlq+ Htqt}EltrtrI
E12A.3(b) qB4l 9d,:+i
^Jqq l5%o9 Ezlzl9lrll gE
360cm-,ElB 9lql 9-lz16}r. 91tr1. g
E +6Iq4. =E
EEf 128 EÎ EH H -Br+

gxll
==
D12B.l .PEl] d-+¤- 4lt}6l= rll rll{ffi dqu+qot 6l+ olrSe+ r ^l
D128.2 EUll aJf9 E"lq4 99E ¤E6Iq+.
,lE "5Iq4. D128.3 '^J4'e+'qlLlzl ++l'= qBAl {eLts +Eg q4l^l +96ILF
"l
G^
r -tl
El2B.1(a) CO9 Eld tl-+= r.e3lcm-'ol+ Eld BHl] 6J+¤ Bq6lrll + ol Aol Srlal_o + Zl&.J 4k4 syo ol4z} !dg+i 6JE: +6I +ue?ll
6}n(t^l¤ , zl ?tn), a-<Ig gEE EL+s E^l6}qel. qtr gEql^l q+ ^
o ell _c.<lEE ol+q-q q.
ol (}ol l2B.l2all o -+ 4ltl6,J 414 sy" olLllE "*4Lg*i flE: fo} +E E
El2B.2(a) cnr9 Eld tI+= 5.241cm-'ol+. sld +ul] dr+E- Bq6lrll
9llq+ ^ Eql E E-= ol+6}q4.
^l +6}r.(+^l¤ Âxl *zltrJ e ¤l4E E6Jg +^lq}4), a<Ig gEel EI
E128.1(b) HIE sld tr'+= 6.511cm-'ol+. Eld EHil d'+¤- Bq6}rll + f + E^l6Lq4. qE gEql^l ol aol DB.r2aqo4 4l4I+ lt9 szo o1
6}r.(t^l¤ r ?+n),
^l
r
ag gEq q++s E^16[q+. qH gEql^] 4z[ 9d=+? flE +q] 4EE9lq+.<:aellc.rlEE ol+6]q?+.
EA 501
E128.2(b) CCln9 eld tl'+E 0.0572cm-rol+. sld +E|l ¤.+¤- Bq6}rll E128.7(b) s00Kql^19 cr4E dF +uI ¤+= 4ltI6IqzI. tlE +*
+6}r,(+^l¤ r^^l szlE} e E4e_l q.Jg +^l*+, r <l¤. gEq EL l78cm-'(4d ,tl+, Hl-g+), 90cm-'(HB, 26 trl+), 555cm-r(HB, 36 trl
fe. s-r1a1q4. qE gEq^J ol *ol *r}^lo -e 4l&.J Al9 s,zo ol4 ED, :z4l 125cm-r(HB, 3+ trlED"l+.
zI 9 dL+? fl =' fo} + rr = 91]o1 4,,l- ir ell E E -=- ol+6}q +.
^l El28.8(a) qtr {} flz}z} 4*o e qe+E Htq}tl-Eil, 2500cm-'9 BlEls} E-
Er2B.3(a) trlg 4 Exl¤g
'lla+¤ +El4q4. (i) cq (ii) o" (iii) H2s, dzr ^J4, l4J. 3500cm-'g 26 Els+ dz} tiEll= zlzlL gl4.
(iv) siHn, rElj1 (v) cHClr. =
reooKq^lE "l flz}g dzl tr4 +Ell ++¤_ =E4lt6}q+. 1e00Kql^j 4
E128.3(b) trls 4 +zl¤el .|]ag +4qlq4. (i) COz, (ii) O,, (iii) So,, (iv) eglEe.l tI44 2fl21115 9"IzI9d,g4i
sF6' ja7-l-7. (v) AlrCIu. El28.8(b) qtr + flzlz}36s_tr trlsl¤ Blq alEH, 850cm-'9 BlElsI E
qd tI+E$ i=a.828cm-r, B=1.0012cm-t, rall dz} ^J4, l4I l100cm-'9 sf q+ EE dzl ^J4= ztzlL ll4.
E12B.a(a) "tlHlE =
2000Kql^lel ol= d^t ^J4EE +ts]] 6J+=- 4l4I6Iq?+. 2000Kql^-l 4
e=0.8282cm-'o14. qa+= -r.el6}l 2s"cql^lE sld EUll Ei+E +6I
q+. +91=q ^J.44 4lill+E g"lz} g4ls+i
E1 28.4(b) irl E C'H5NE sl d ^J+Eg .l = 0.20 14 cm-t, .B = 0. 1936 cm-r, El2B.e(al 1.00cm39 +r4 +q Eq flE. E S%rol 1509 mol-'oJ EÎel
rqI. "l
e=0.0e87cm-,"1tr1. 4at= .I.el6tr. 2s.cql^19 4d EU]] oJf (i) 94 itltr+ (ii) Btl eF Ets}] El+¤- 300Ke+ 3000Kql^l 4lt6}q4.
+6Iq4. El2B.e(b) aJ Hol l.00cmoJ oJ%Iill *zI4gl 5q fl= Ne flx}9 (i) ¤
= 4 ir|+$ (ii) BA g+ +tsll 6J+E 300 Ke+ 3000 Kql^] 4l1!6lq+.
E128.5(a) srr9 tl5 323.2cm-tol+. 4lE EHI e+¤ EE6Irll +
6}J(=^l¤-4zl ?*r), r ag gEel 6Jie E^l6iq+. qtr *Eql^l El28.10(a) E"J6J gEel +irlql^] Hrel He9 Btl ¤.F EU}] E}+9 ulE
ol fr"] l2B.r0{ o + 4l,i}+ ll4 svo ol4z} 94lg4i 4l4I6Iq4.
El2B.s(b) IrE dE ++= 214.5cm-'oltrI. tlE EHI] 6J+= BB6[rll +
812B.10(b) E.Jt gEe+ +qqlî Ar4 NeE Ha ¤+ Eull Etf9 ulE
6}n(=^l¤- jrzl ?+r), r *¤- gEq 6J+E E^l6lq+. qE gEql^l 44I6Iq4.
ol atol t2B.rozl o e al4I.J AI4 s,to ol4zI 941,9+t El28.11(a) Oz9 e* Aol= l20.75pmolr|.300KqI^l ol EzlE qd +
E128.6(a) so0Kql^lE csrE d5 +tsll ¤r+E- alt6}q?+. {E u}*
H]] 6J+E ag ol+6ll^1 4l&6}qe}.
=^l-= rJol=
658cm-'(4? d+), sszcm-'(#E,2+ El+), rr-l.a. 1535cm-'(ultHa t
El2B.11(b) N2E ¤.J r0e.75pmolr|. 300Kql^l "l e4E Eld +
aol+.
tsl] *+= rg ol*"ll^] al&6}q4.
=^l¤
E128.6(b) e00Kql^Jel HCNe-l tlF BE]] 6J+E 4l{}6}q+. AE ++= El28.12(a) NOF EzlE BIEIa $zle^] r stld ^J++ 3.r752cm-t,
33l1cm-'(Qla 712cm-'(Saj, 26 Ele+), r4n 2097cm-t(ultila tl 0.3951cm-r, 1?-]-a 0.3505cm-rol+. (i) 25"C91(ii) 100'Cql^l ol Ezl9 fl
+)"lr+. ^l+), d Euil *+E 4lt6iq+.
E',r28.12(b) HrO Ezl=' Hlqla $zle,rJ r Eld
E128.7(a) s0oKql^lE ccl4el TIE +ts]l El+= 4l.t}6}q4. aF r|+E ^J+= 27.877cm-t,
14.512cm-r, r?]r 9.285cm-'o14. (i) ZS"C9+ (ii) lo0"cql^J ol EzI9 gl
4S9cm-t(4{ d+, Hl-q3r+), 217cm-'(HB, Z¤: ul*), ZZecm-'(HB, 3+
14l:r+cm-'(H¤, :{i 9sD"l4. d EU}] EL+E 4l&6lq+.
9310,
EE 12C E^l ollLl^l
¤B E^11
Dl2c.1 2efls ¤ zlel Bt 9lHzlE g=91 q4 qBril H6l-=zl ¤B D12c.2 +F eEll g4-tr. qla5l= ilol Eull 6J+E ol+6}q 4l4I.J At
6Iq4. n+ "Jil6l+ 449=_ "5Iq+
G.-\
Jrr
E12C.1(a) fg} ,\EqlE^lE-q ole"a|{ Brr9 ¤J. dE ql E ol*6lq+.
6JC¤. 6lq +6ls r Ag gEq 6J+s E^l6lq4.
HzlE Bq6}ril^sE9lqq E12c.2(b) +ue9llqL} '^'EellE^lE-= ol*6lq HCN9 ¤+ llE
fql
qtr gEql^J +F EUll fl4tr. 4l4I'J fi"I ol 414 s,ro "ILIE "*41=+r "ilulzlE Bqalr| tldg 6iq +6E, rlk&
gEel *fe E^l6lol+.
v= 323.2 cm-,= ol +6lq el. qH gsq^l +F EUH fl4tr. AltI'J {}ol ol *4 sy" ol4s "*AL+?
E12c.1(b) f*
+se9Jq+ ]uzllcrleE "l+at¤ r,E ¤+ dt: ql uli :l t t cm-'(ql a 4+), z tz cm-' (EC, 2+ trl sD, 2097 cm-' ul q a {+) (
HzlE B+6}ill 6J¤g 6Iq +6|r" r gEE

<tg EI+s E^l6Iq4. E ol+6}q+.
qB gEql^j +F EU}l fl4e 41}q} <l"l ol 419 svo oll+ls "*11,:4t E'.r2c.3(a) ccl4el E+ TIE
"llHzlE B+6Ial
qldg a1q 7a1a:. fi
i = 214.5 cm-,= I $-olq 4.
" g gEg ++e E^l6Iq+. qtr gEq^l +F +tsl] g4-E. 4lt}'* <i"l
E12C.2(a) ++ ol+6}q CSrg B+ dF ql ol ltq 57o ol4E "*Ae+? ulf +sqcm-,(qa d+, Hl-Els),2t7crn-l
qldg 6}q +6}l, I <lg gEq EL+E E^l6Iq4.
HzlE B+6}{lÊE+lq+,:.EEllE^lE_=_ (EB, 26 =.lo|), zz6 cm-'( HB, T), 3 l4cm-r(HB, 3,u: qei)= ol+6}q 4.
qts gE.ql^J +F +El] gEl-tr. 4lt¤I ilol ol *4 svo ollllE *lLg+t E12c.3(b) cI4E B+ {E .llHzlE H+6l.rll 6JCg 6}q +6}r" r <tg
slf osgcm-'(qla Ca, 397cm-'(BttJ,2+ 9c+), ts:scm-'(Hl41 d4) gEg '*fe E^l6Iq+. qE gEql^l +F edl] gE]s Al,i}+ <iol ol
502 1?
=AlgE-4
4k4 syo olqE "*41:+i ulf rzscm-,(rjla {+

Hl-qs+), eocm-r(E¤, flCO;= 1.931cm-toltr|.
26 ge+), 555cm-'(HB, 3+ q+), 125cm-'(H¤, 3+ El3tDE ol+61q4. ++ AEE9JqLI /-EellE^lE= ol+6}q m$ fl{ olluJ
E12c.6(b)
6Iq +6Ir, f <Ig gEE Et+e E^l6Iq+. q
EI2C.a(a) fl+'12B.12(a)oll E^lE gal.g ¤ ^lEel leo0Kql^Je-l dzl tt ^lE E+6I4 tlCg
4 qlHzl.ll Ellfl E+ TlqE 4l&6}q+.
f(Hl)=O.Sttcm-'o14.
El2c.4(b) 9# rzs.rz(b)ql B^lg szls g ^l.E-el
2000Kq^]E dz},.J
4 9lHzl"il ql6.J ¤+ TlqE 4ltl6}q+. E12C.7(al fa]. +u=glq+ ^rEEil_E^lEE
ol+6lq CH49 B+ lrld
"llHzlE B+6trll r ([g gEE q4e. E^14q4.
qlCg 6Iq +6ti4
.ilHxl zJ4ol500cm-'?l2=9 4lE
E12c.5(a) 2e8Kql^Jel ¤+ qlqzl= q¤ gEq^l +F EUll 94e alÎ'J <lol ol 414 syo ol4s *dg+i
4l&6}q4. Blcttn1 = 5.24 I cm-' o I 4.
El2c.s(b) qlHzl zJ4ol600cm-'oJ 239 419 400Kql^19 B+ qLlzlE
4l4}6}q+.
El2c.7(b) fql +ueglqLl :ufllr.rlEE ol+6}q CCLe_l ¤+ Eld
9lHzlE ¤q6}rll ElCg 6lq +6E" a 4I¤ .gEel *fe E^l6rq+.
f* +uegllq+ /-EqlE^lE= ol+6}q COg ¤t 3rld
El2c.6(a) qH Ssql^J +F BHl] Ee]E 4lîEI <tol ol 114 svo oll+lE "*ae+?
glHxlE Hq5}rll qlCg 6lq +6ir, r 3Ig gEel Elie E^l6lq Elccln; = g.g572cm-t ol 4.
4. qH eEql^J +F BE|l g4e 4l^}+ <l"l Ai9 57o olqE *aL+?
E4 12D g= gAh=
*= gxll
D12D.1 "J^JB"] +9.9 9ulol4 olaol 541

gqqqztl e{ ffiq}zl .g Dl2D: 'gq+4 .J4l'* +tg F6lL+?
dxlcdel
o-l l-1.
D"tzD.4 ¤+ "JtlE9 zllHol ell g-9-6Jzl "J6Iq?+.
D12D.2 q¤ A+q f,s" 6J "JBolEol Et z|bal4i
G^
L-l t=
E12D.1(a) QE 4tr ul-fft.rll tlm9 oJzl¤ s.gr.rlflo| 6l= 4l= +g 6: El2D.1(b) G qe uffii.rll I/NIE oJxl¤ Eci^l4ot aJÊ al= +8-q^l
9¤ {Eol+? (i) !48 zlzll .r.le_, (ii) "J&e++A Tli.lle_l (iii) gtsl q¤ aE"Jzl g6}q+. (i) ol4}s++i 7l^ll (ii) +¤E (iii) +
^lB ^lB Îtr"
+AE rill ^lg (iv) f6zl. olo[gE,tlB (iv) 98.
E4 "t2E LH+ ollLl^lel fl!=+ul

¤E Exll
Dr2E.'r Sle-eu1q1 +'J gqq}4 4Ee+ F4l ggEI4 AE ^l."lel *41 D12E.4 t+ tlE eulE +g¤. ¤H6lq+.
E E6Iq4. g+* a7l= eC+=
ExlC Eee] "JA-+sl E
D12E.s +zI 5Ag
D12E.2 ea-7lb "J"JolE {lEEqql 4t Eull E}+ +rJ Bb g dB6rq4.
q+ il¤ Ll44q4. ^lr+
"Jolql ^l ÎolE eEE +4r.lt= Îs4 aFe^l uwl rEEl9l cl 4¤tzlE
D12E.6
D12E.3 sa 7l4l QltrtrEl7} gEe| +rl.ll q=61+ ol+E Boltzmann ¤E6Iq4.
EEE zlzla- ¤B6Iqr+.
E6 503
ol^
r -tl
E12E.1(a) 2e8Kql^J (i) He zlxll, (ii) Xe ,l4lE s= E flE eqE 4l^16| E12E.6(a) +5i +tsll g?]5 ol+6iq 2s'Cql^l zlrfl ,rlrlle 9l= (i) rr, (ii)
q+. cH4, (iii) cuHu9 ga-+irl E. g++g +61q4.
E12E.1(b) 2e8Kql^l (i) HrO(g), (ii) CO,(g)9 .tr= g qlE +ulql 4+ B E12E.6(b) +E EEl] EelE ol+6}q 2s.cql^l zlill tr4l_+. ?l= (i) o" (ii)
4l ¤+ zlqE 4l+i6}q+. QH" (iii) co2E "JA-+sl E g++3 +4q4.
E12E.2(a) BEq .E= E $le +slz} 2e8KE s llEE 4k+ *Al ElE g El2E.7(a) Tlzll "JEq"Ie+ rilEql 4¤l y=Co-/Cv,.$ 7lg +6Iq+.
^JEll
EE +6Iq4. {qI {EE TlqE rellRg tr]le+ rel$ al qtg qq 4l4l-g 6l
ollulzl.ll
E12E.2(b) Co,(g)9 -s.= E tlc-eEq rll6J B4l ¤+E 71q71zqsx9 q4. 2s'cq^l qL qol +Ail9l ¤ zlZ|?l.-+? flE Sd Tlillql 46ll
H,o(g)9 bk+ ?JAl q= gEE +6Iq +. Cp_-Cv_=RolEl.
^lb oltls+eAq
y=C*_/Cu_el {}¤- +6Iq4. .lluJzloll q.J
E12E.3(a) 2e8 Kql^]E Hro9 gld EUl] El+E 4l4}6lq+. ol ezig sl
E12E.7(b) 4t
ol TIE" el TlqE relE "J ltg elel 414F9 6lq+. 2s.cq^l q
reiilg ulle+
d tr'+= 27.878cm-t,14.509cm-r, o) 9.287cm-'o14.
AJ+E "l86}q
7lq= 4l4i6}q4. L +ol +Ailql 4 z%Ayt+.. flE $d Tlillql q6]]^l= Cr*-Gv_ =Ro1
2s.cql^19 a6,zl! E Qle_eqq El]qI Eld ¤+E tr}.
El2E.3(b) 2e8Kql^lg so,g qd EEll EI+E 4l4}6}qe}. ol ExI9 9d
tL+= 2.02736cm-t,o.3M lTcm-r, R)0.293s35cm-1o14. ol pffi 0l+6} Clgx].g Hlq
E12E.8(a) 2p3l2olq, ol 881cm-rgloll ,pl/'
q 2s.cq49 oltlEl¤r9 E {lE erlql q.J Eld +Eel TlqE 4l&6',} ?+)71 9l+. (i) s00Ke| =+l=
(ii) eooKq^l clg^lel=+l.E-+
g+=*ql ql+ dzl tr-ql
q4. zlq= 4t6lq+.
OrE A4l EE Azl tIE}]E 'Asolq, 3:;oJ tr4z} Elq/J.qEq
E12E.8(b)
E12E.4(a) CoSOr.THrO +ql fl= Co2* ol99 Hlq d-Ell= alroolr|. lK
ol6IE gEql^l= oj aalel tlE +vl7} d4 7er8.rcm-'9lq fl+. 400Kq^J o,E g+=*q ql* Azl tr"q zlqE 4l
"_a dx} 4¤.ll E6ll^l ^J 4i6lq4.
zJ4. ol -aillel ol gE gqql^lel E- {lEeirlE 414}6}q4.
E12E.4(b) s=*?_l d ++ 4¤ rzll lS9 zl¤ ao] {e"21 d+9 E- g++g u0Y4 E}+e Erla}:L o}41
^lEq E tle.+ulql 4+
El2E.e(a)
E 4l4l6}q+. gflE (i) 2e8Ke| (ii) sooKql^lE At g++g ql+6lq+. 7l+ 4E
oJq+= ++(g.g. ?I3 qsls)E 0rz1z;, 72e(2), 1e74,3287, e)
4*^HEE+, HCOOH)9] E= g ql
E12E.5(a) (i) 2e8Ke| (ii) s00Koll^l
%talol
:374cm-tol4.
Feq= ql+6fl -E-o}zl. 7l= {5 *zlol "Jq+= +++ 3s70,2e43, El2E.e(b) r:{ {$x} e+9 E $= +sl= rt7Yg g"fs E^16}a o}^1l
1770, 1387, 1229, 1105,625, 1033, O:8cm-tol4.
E't2E.s(b) (i) 2e8Ke+ (ii) sooKq^l qlH(o}^-llBql)EE+ g qlE+rl eflq (a) 2e8KeI (b) sooKql^Jel .E= E flE eqE ql+6lot+. qlolEl
E qltr-stt _ts-o}4. zl= 4lE *zlol .Jq'+= EI+($.c ?}g Elq+E)= *el ¤+el 49 "l*a}¤4.
=
612(2),729(2), 1974, 3287, tri 337acm-to1c1.
EE "t2F PS. Er'+=

¤B E^jt
BB t}+q E4l gq+{ $!o1 BB t}+el ¤-E el+ +4lE
Dr2F.1 D12F.3+ HI+el ¤B *+e+ r Hl*el HI¤¤4 {CEE etsl] ++E
qBal ¤¤61-=zl g6}q+. +zl= E4p]4 o + 611!6ll _E_otzl.
^lolE
o12F.2 .Jq4EuI],*f +41=EElq4se dl46l _H-ole}.
Î"19
G^
-t=
E12F.1(a) rrq ++ oI4 qlolElE ol+6llî 1000Kql^19 r,(g)+zr(g) ¤ FE 7lq= 4lt6}q+.
Bql q+ E¤ tI+= 4l&6l.q4. Q e E flx}9 Hlq ^JEll= 2p3t2tr^1 4 E12F.2(b) Or= HldB Ezltr.^l a7l+ 415 El+= tltocrn-r,705cm-r, H
+ qEiEE zlzl l- 9ltl. i = 14.36 cm-t, = 0.0373 cm- r, hcb,= t.5422 eY.
2 .D l042cm-toltrI. ol EzI9 qd tr-+= 3.553cm-r, O.4452qrrt, oi 0.39+8cm-'
Er2F.r(b) zlAlt} F9 fla j/{+ H}* 27eBr8rBr)+7eBleBr+8rBC'Broil 46J olcf. 2esKgl,r-l E cibus glHzlgl 'll-J sldr+ 4l+ ¤+E TlqE 41416l
2e8Kq^-lel gB t'-+E 4l4I6Iq4. Ex|E=$ flE}flzl ?+3 HI-q dxi q?+.
"l
tr-4"J 7*a a += dz} rlelE z*zl ?*E4. TeBc'Brg 7lE tlE
*i zzz.ztcm-'E=ilql
+4E 6ll^1 4l4l6}q+.
El2F.3(a) ¤6 srzr,.s(a)9 xI-E.E ol*6l-q (i) s0oKel (ii) eo0Kq^l clg
ollLlzlql qfl dÎ tI4 7lq= al{l6}q4.
^lE E
Gibbs
E12F.2(a) CO2= d¤ Ezle^J r dE ++= 1388.2cm-r, 2349.2crrrt,E) El2F.3(b) ¤+. ZI-EE ol+6}q 400Kql^l Or9 E
E12E.8(b)el Cibbs glH
67.4cm-to1+. ol + r,IZlE 4*z+oe qelqq ?14. ol +zI9 sld xlql 4+ AaI tlq TlqE 4lt6}q+.
.llHzl9l ql6J eldn+ 4lF g
^J+= 0.3e02cm-rol4. zgsroll,,.l E ciuus
s04 r2 E}lEEel
-*v1Lrz Eq-+
=Zl
-=.61-x{ E
g,'llT.ll
o tl -t
rrz.r H,9 sld E. g+*g gE-21 oo e+q ¤-4zlrl r.d4"J a Rql It2.2 +*4 Ez'll II2.lql^Je+ ag 4ltlg ol¤-6lq g+*ql ql{l 4l+
d=6}q "Jaq7l dql ol aEq q k4 94zl= 5eg 44u4. olal ¤+l zlqB egE ^].olE E+¤ 0l+6ll^l +46Ir" 4l4I ar+= rts
aJ
^ddol o+$LlE ag
g+"*g fl+q= d"l9 '*oll zl tz.t4 eg ge LIEI,{q+.
=+lE ÎolE
"JEl= L + A+g f ?lzl ullE"l4. r46}q c¤ qdzlql EilEI trl-g
t12.3 qa+E Zt¤- c4es +6l.= ,JHg 611B. Ez}el qd +++
r+ gg 6JHg
^J46ll rlz}. (55 eae| eld si"Js_tr "JE)9 i}+(s_iE +) o= B= aol
4. H,O9 qd +++g {E,C,}olH, Iq-4^l o=2o]|4. NH3E Eld +
E@ = +>Le( /)-e( /'))
2
g(J' )s-
,,.t I t'e t r' il
++g {E,2C3}olq, q+^l o=3014. "l %}B¤. ol+6}E $$r'J $zi
'/ t,t
I 'lla+= drll *g + 914. cH,9 eld +++g 7 xlEEs+El
¤zl,,.J dr= sld qlqxl rEe-l gElEol4. g+=*e ol
{E,8C3,3C2{ol4' u}4rl o=r2ol4. E HICIg a+ql= Dun9 4d +++
=9-lolir,8(/)ts
4lgg ol+6}q q^.q_I+ Aol +qeg }rq{. ol [E,2C6,2C3,q3c2'3c;]olq' q-+^l o=l2ol4. (a) 25"Coll,tl qlflg eld
BHJ| 6J+E +6Iq 4. .l = 4.828 cm- r, B= 1.00 I 2 cm-', l4 tr b= 0.8282 crn-' o l
c=+NkF,¤(F) tr|. (b) dgq^l sl?-lB csHsNE 9d EUl] El+¤ +6JqeHA=0.2014cm-r,
= 0. 1936 cm- r, e= 0.0987 cm-').
olq^l d¤ 3rldxlE g+=*q qo.J dill 7lq= 0-+ l, 0--+2, r--+2,1--+3 .B
F9 dolql 7l"JEl= 7lqi$ {}aJ 4.ol4a E + 9l¤¤ r4s *alg

s Eq4. olfl B4 oe dB EzI9 qd g++g rB 12.1r+ rJe Ee
+Elr.ilq+
1.2
E
-e 0.8
b
I
S
()
to o.o
do
8ru I \
t/ z
olru
0.+
\</ ",'
0.2
l /-\ - \r,z 1 3
_0,3
0
0 23 4 5
8E,I/ER
-
:19 12.1 E^11 tl2.1oll^j 4l+!Ei g8-+rl EEEJe-l EEoll ntE
EEI..
=Er4 =
g,l^13
EII-=ol 95
"l *9lrJb Ea4 E?-14 Ca(qlqzl4 &Fg 5;ol zlill 13C qtt
Lt "_4i.ll +ql^J qB4 + *sE+Ei += *o e se}q=zl
reql v ,rz[ ++ +44 qq E?-14 CAE q&e a4ill +ql^l "JqLI='|]+
= q +,q* 4C"14. bE6L7l flql^-l EzI gf,$ "Jq
"l#
LlAl 6I= 'gqE4 6r'014= z]|'J$ E"J++. "l H$aJ E
13A eJd 7lfllel EU¤tr I ol*a}¤ .$4"1 ^lzlql ttl$ qBAl qzl}zlE +4,]1=
'q& rJa^l'g q&ql +El 4E e. 6I+E E
^llg + 9lq.
Eer+ E"-14 CAE +Hle ^]s "Jd+ +4lql 9l= ¤I îl rgg ffi{ e¤¤ 0l¤-61-= 4"14.
EE ¤E4eE +48 + gl+. zlzil"il q"l^J= e_4 regl 13C.1 Eqq4 rg; 13C.2 *t!rl; 13C.3 E4q+4 rg
_e-Bg olf-all.<J "JE- "lE
î ¤HqI EzI SE" Eql "J4d olH$
ololl$ + lig 4"14. ol zlzl:il_ +tl +E
^lg drll
g dE +E dcs" rela E= F E"-14 ^da5E eHl¤. fl rlE 0l xleel EE=?
Ezt 3E" E9l zl"J9i "JEr+ ¤+^14 +E+.J + 9l+
13A.1 fl8E4 4E; 13A.2 eU ¤g EElolEl
slE, ++ oo4, r4r ^JE+E tF J +Eg {4 a"FE ,}l
i]lE Ee} Ez].g+ olgEE olt! :-q4 +419tr} ga'J: rrilrl
138 Ei{lotNe! Erl- =
$al"+g E6J olgEg "l¤¤ 6H461-= cll {E5. +aol
q¤al ol*qExlE ¤B*+.
.4ill +ql^JE Ezl-z} u)uzl az)
"Jq"l ^J'J6l 7 tr, trTE
ql +zI e*'ol 7li-ilel a+e+ trl-s4. olBl+ 4lql^Jg OE
ffi-
g Eqq4= + "JBe dqa +eq 4zl4 zJ6Jg 4Î
op ol ar+= olg=E dzl^Jql 'I* qI¤¤ zlzl:t E^l
alt 4014.
138.1 ga rge.z olEE olEs
=al;
EEf 13A eJE 7lz.ilel EU ¤tr
> ol EEfE ull+E ol8

13A.1 EgE4
^l=
"'-jg Eal4 48=A Eal4 dEol -et gEe_e+E'l tlE EEe_e '¤tr-E4 zl'ol* ¤e4 +a er+= 9e5a a o +^J, -:. c
oldEo.E^j golLlq, 7lill ErlEol I trl+ HJ-
^_Eoil
=E61.=
el=eEt. 0l EEoil^1= 3r1l +oil^j gclLl= HJ8oil 4a ¤9 fl"J"I q= +zl. 4A¤- olaflalzl *6Ir +E+ al"l4.
Et= +i1t 4toil^-tE gEJ4 til g8E ¤Bg aotq. "l^ll. ¤+g oll "lqt al"l gHI4 o E ol+gtr]r.
'l]t} ¤¤9 "1t- +E= :. C¤"I fol4l ^lzl F
qI +c
"Jql +qd H"lE Eg

E"46lt "&g I rlt t44 H"l
> E4C 7llLJ
E +b <lol4, "lag :_ ceg aal Fla +q. Eeol q
EtrolLl ExlE c}|illE EE Beoll 6H361"= 7lalel Ar-E
q
qal ¤E- $HJ:eltl.^l+ = trlls+&ql^le+ ?ol) o}| B%rnlels+ o|]
=tr Ezl^fE
=6t|^1 HIC(+, E= Ee* m-2s-t;g *= *Bg zlzlL 44
=tr
> rJafl qHl rl^l U+. E E_e.E d¤ol qlqzl"J trilE{gdEql^Je+ gol) oil
0l EEe 7li{ Exf SEAEE tB)oll EZ6E E olag +8 Llrl +aJg o|] ¤*"14e+ ,l] a* ¤e-l ++10 mrs-')-tr 44
zJoloe E^te.l BA +ajq S-d +rl6il0l6lr, 5E qq, += ca"J rls olg+ Hli6I+. Lt 5"Jql Holz}
^171ts ^l- ^l7J
tjE! /\i'fr t5.!=4 ul^= H"= "+-Lkt4liJ?I 'J EI
r
d- +u-^l AL-{ AIArF ?L AL- Al^r^l
X,it4uf
+*ql+ ol H"le+
^l-l^l ^l-F^rl -l:l
A"J Hg F46l+ ^"ip$e-l dill "Jg

-16
:Lltrl-. =:iljt
7J4g BqI I llAttzl S4. +*g "J"J +E 9lr" g
^l?J "l
"J +E 9lsq, "l Y oel 9"lE ol4ql^J ¤Eg 4,o14.
eHI ce=ql ++ dE e4ql el6tH "JHI4_"_e. qI
E¤ol+ lEE +E=tr+ ag Eeq $rJol ollillE ¤16ll^l qI ^de
*sE+q 4e *o + +Hlq= r+eg au ¤trolap aJ I +*e: ca4 +d¤ +E * ceq rr| EBfq Hlell
qF4 qlE^J z+ql ¤e4rll q4}q= Ee +"Jg'lgr+ a
tri. "JHI4e.e eHI +EE de4 +A'l]¤¤ ee5a dE4
ol }-Eel lil Er.J+ql Hlql{}+.
E¤ zl-zlr LtE}u4. olE 49 E= ++el ce4 4eql
4*Elq, zlillg eHI Ceg b6l+ EllE 4+^la + 9l+. /(Ee) *# Fickg qtt xtt1H^l (13A.2)
ol a+qlY 7lril EzI gFEg ol+61-q olE
^daE eHl
t--Ezl gEe+ "Jqq el=++= ag H"J + 91trI. Eq lB ¤zlrl are,ll "J*"lel(mr) B 4]f9 ++ls +4u "J"Jol
ql^J Bd.tlzll ol Eq dHlql 44 ole"al-Zl q= EzI g f Es.r1. EA fr*"I E" E Tl$zloll ulellali ol *4lE ncr
E"E9 zltr +,qt 4¤+ ¤* zl-# qs L +rl7l +E E +tl {l1g=lol4r- ti4. "l Hzlql el6l-E bE7} +lzlql
¤+ 4 44. rs.ra^lql E6lE=8s. re+ Sq rr}4 ++614l He- trll= tlETl 4E +"Jg qlql El6l^"1 qt
^Lolql "lE6I=
p"tl,<J l.= r+s=r+ e+. "JqU+. rula bszl +"JB 4l(dl'rtaz=0)=
o1 uule.4l d
s +*"1 0ol ¤trI. ols] ufi[ztzls ¤ds. +E(g+E" 4 +
^kT
A-_ EE=]
op EE
^l+
tse [E^l (13A.1a)
fl¤ qlqzlel +%I)= trFq=4 u."1 ¤.s zl&zl4l HlEil6Jtrt.
ol
^lql^J
tr84 o +^J, +^l7l +E- 4aql
oE tsz}9 +E /(gg+ qlLJzl) *# qLl^t +BF (13A.3)
^l +e}.11=
s4 Hol9 CE= +4U+. "l ^lel +E r+A
4 sialql4 6ll4ql +6ll^J= Eq lB= _Bolel. Ezl &E"E +* vl zlg 7Ie ull= ol f.*"1 +z 4* oJ:"Ig pI
"Jel
ql^l E 6}+el 6s+ cee lB.e^lg EzIg Bt +qolq, gE (}g 7lA ql= ol +*ol -z 4 6fq}+. Eee BE zl
gzlE tr++ +E7t +¤- *e-E+q *3 *e_e g444zl
ExI ?trol aaol:1 Ssz| T"J trll +gr+ ?ol iqtl4.
E+ dy\rtdzT|+"J ql pl "J"l g+(rB 13A.1). trt+^J BA.2
/ 8RT \,,, Hlq tF+= ¤-ol 9oloF 6Iq, rq6}q
/,.un =[.
iM )
EE +al [E^l.85E] (13A.1b)
^lel "la¤. -D4r
.tArl 7
:rT. --,
13A sd 7lrlle] EEI dtr 507
/(Ed)= -off u,il*rl[t%= (13A.4)

E 13A.1 1 atm0l,\jel Tlillsl tHJ dE*
r/(mWK-t6-r; tll$Pr
ol pE +tt Al+zp pE4. old9 sr tglE-,s,oI4. 9l
273K 273K 293K
HzlE 9r zl¤zlE tr++ geluil4q "l+^l +le+ +Ae +
?-lql 96H^l trL,q-r+ zJ"l 44.3 + 9l+. Ar 16.3 2r0 223
CO, t4.5 136 t47
/(gsE gluJzl) =-*ff He
N2
rM.2
24.0
t87
t6
196
176
gEtrtr Zl#e LlEl'J ollLl^l +aJ (13A.5)
. zl.E. eql rl *9 AlE"l ++qq ";4
¤zlrJ rcE Edtrtr 4l++. ol rc9 SI ++l= )K-t6-ts-1o14. t I pP = l0-7kg m-r s-r.
E. 1 I s-r= 1 Wol
E + olag W rC' m-r-E_ rI4B +E 914. d
ezlE "J+E E 13A.1ql f+4 +9i+. dCE= d¤ +5-=*el +=j= u4g.q +EIt3+. ol E rl-"19
+4lE +617]| +l6]]^J Newton E= tr-El]. ++'H= +ill=
zrEtEl o{l 134.1 ^J4L6ll
Ezt olEl.rJ +ill= "JflE +# ol+q 6 == aol
+ ++ *92491 6I+= z=0oll E 6L+=
+z16}111
4r ^J4ts + 9l+(rH r:e.z;. 8zl9 Tlqr+ dq} +e C
zl
z=*l.0cmoll Eoa E4l +9 gE= d.xll *g+ IoKIrE ^J4olq, "rltrIe= +EE +E= zlqo__+PEIE zl?-lql
tr|4 d¤4 o _+ E++. Ezl¤g ol +fi-
+4 6t9ula a121. + + Îol9 gs zl¤rl= trl¤-r+ g ^plql^J #"J$."1
j/+qq, trzl *9 +Eql q4 +E"6J oll zldH ,+ gta}
ol ¤+.
CEg rqe zlzlt- g+. r46hq L?-lrll 015-6l+ +el E
dT lOK r j+ l.Ox103Km-' zl¤g,*6J ¤rE"*ol *zl oll$ql ol :o_e_-tr+El s= "J"J
dz 1.0 x l0-'m
olEg + +E= L?-lZl 6JE uultrzll 0l=16}=:o s
"}| =+.
+ + Îolql= $zlQ<=24.1mw 6-t*-t)7l. Eq il+. r s+q s= Ezl-= + +E= 7l+^la+. ole+ eg s4 ull
qE qlq^l +*e qer+ ?"1 ¤4. E"ll rJzl* ds zl¤ a,4zl ule Szllel dC"l4.
ol zlill _s.r+= +c 6E::o s_tr oldq= d¤ +
'iltl-E
,= -*# = - (24.tmwK-r m-' ;x1t.0xt0r Km-r )
t%Ie] x4 dE9 =zlql E=61q, q+^l ddg x4 $t%I
ril|6Je_EE +=Jql E=++. ol ,r+ ¤+=J CEE
- ^dEE z+
= 24W m-2
ol +elol ¤-ol gE 4* z_*l.0cmoll gl=+e_s rgE

B + 9l+. .lz\tl uE ;q uJ6JE 4roJ4.
!-el z=091 gl= zITIg +e-E qlHzlzl olaqq -z *6J
o + 6azl qlEolr+.q4^l 1.0h(3600s) F"Jql 1.0cm29
I@flC++8"+) =-rt*
+ + ^tol= E"+ qlqzl +tlg q++ ?ol ¤4.
oll ul zl o d
l = ll lAtt - (24W m-r) x (1.0 x 10{ m2) x (3600 s)
EdE 4l+e L+EIE eEts 3B (13A.6)
=9.61
r-lo o e2p r-o oE=t

x u
r\
XL
IlEf
rLOo EL
IlEt
rl-OO
N -l I I
I
dN
0
I
dz
r
z
trt
J>0 fA 13A.2 +illE Ede Cts ffi9 AU q=oll 8A+. 0l raJq^l=

+i1l7lxHJ:de_e Newton E=E LlEtLHq, g'J0l=3 iigg 8E--J= Tlxla
fg t3A.t EE 7lZ7l= qal. LH47f= g"Jole-l 8aJ. Fick9 l1llg^loll
E6l.E EtrE *aJA r tr01^1sl EE 7lE7l0{l Hlall:drl.. '*PxdE EEaJg 7l^la-SteE 5E A+^liltrt.
508 13 .=rl=E
-
{zlrJ ulfll ^Jf rE Eds. II+(E.E A+El 'd^dE')+I #=g 4,o14. I[F+^J "l ^lt Eg}ql "Jq+= d^ll += +
El+. ol4E t+l= ks--,s-,oJrll, eol=(p)4E ul_sr tgl 4+= ¤ 4"14.
NAugtzl
7l ol+¤+. I p= to-rkg--,s-,o14. ¤eilel "J*E s tr,J4lz +E gqE rq
^l+
++6lt +gttrI
4E u,E +q=4 *9 tn.r4el +E BEe +qzl= gE9
13A.1ql
Le +Bg E"6J E¤q q+"J EEg q^F+ ql+61 TLzt
<lg *=4.
3 rd?olzl"J H"J6IAI olag SE} Caol E
"J6H^J "Iq+.
+E= E ae} u9 zll#3q EBlql 6I=Ell, ol 7lE4"J f (u
r'
.) =(#)'''._- û1''
=
¤84 e+= eo5a 4,ol cranam9 E H=lol+.
{zlrl flr,)drE u*91 u,+du, r}ol9 +E C+g 4= +z}
13A.2 au ¤trel 4alElEl
ql a{^l ol u,7l "JqB +=E}fl 7l*^1/zlzla_ q+4= a
"ltrH"Je-l +E C# *= +zl¤"Jol +d 4:}
zl4l EzI ¤.E"Eg ol+6IH $d zliilql q6J q4I caql zlqr+ +
++ 4# +ER + 9l+. ol 4=3 4*zl BB(2") # E6Lzl trIE).+
ol4r d+ taq 9=61-=ql, ol +5 +*e "Ja+
^la *Ef = $r,tul* r,f (u,)du,
$"Jql +q{ Hol9 _EE(ol H3 zlzlltr-+9 ,}{t4 H.J
+E 9la zlqE "J+g +E 9l+)ql +E=61-= Ezl+= r +E- +%+e ol Ae+ +b aol+. Irl4^J
7J41+ HolE +b <te_E4 Z*E ++u+. ol +*E =¤+¤. ^rtr
^l7J Z* N !* u.f (u,)du,
$4 pe} gE rql q6J e]= +415- EzI &E" E9 ols-" 61.{ =
Tr I-:*L
o olrl
' =. -r
^. ,\A"-1 .
Elt 3 4+ 4l4L
ol
^l
+E zlBg s= zlB_e_s^l trl¤.r+ B"l 84.
4EG.2
,c+ql +zl.J Hol AE TlE¤- ^J41-6ll !_zHrB 1343). $d
Tlill ^J44 pv-nRTZ ole" 6[fl Ezl^+ ,jr ar4 "JH rtol !- u . f .)
(u dt,* = (#)''' @1;. (#)''' =
E +41= I,t"=NtV- nNotV=nNoptnRT=plkT* tol r-I4B tr}4^l

+ 9l+ "l-zl"J E!ql^l= R=Nek9 +4lE ol$affle{, k
91= p/kT
b Boltzm*n9 ^J++ U2 U2
KT KT
Z ,r( 2nm P
KT 2nm
lv,a
trl+^1,
'JOI, A
v
Lw-
P sHoe q+u (13A.7a)
(2nmkT)'t2 lsd 7l^1ll== "H
cJ4l4 ¤+ +qg zlzlt_ 4e4l +r}U
Ftrl = lrAiA ^l
¤# +qg q_q=r+ eol l3A.lb^le e +qd+
x
fg 13A.3 7lq-o-e+E'l v$t 7)el ?Joll Pl 9l= E^1.= TlEg:d"-H^1 R=Nrk M=Nofit
e- 7 lqoll Eg:g 40 ltrl-. / 8RT \"' (
--g 3? lr-tloll \''' KT\ v2
at o BkT ;z-
u^nn =l"f
l"* ) = Iu^"^n
--1 I
) 2nm )
E4! 1 7lq4+E=6.1++x1+ q+^J Z*= y{(kr t2nm)',9= q-q-r+ gol +4tr + 9l+.
Ezlz} /, > OoJ +E ^d+g zle q}{+ +xr*6J_9-E ¤s" g
ull) zlqsE+Ei uy'r olr11q 4e-lq ?lE Ezl¤ol ar rlzJ Z* = f, 7r[u^"^n +aJ teJE 7lill (13A.7b)
g}ql TlqJ+ +E6Ial ¤+. ul4,rl pq Au,^r tlgl ==
ile
H^J "J.el +E= *. =q
E4s=g EF ar ^lrJ E?Iql zlB4
13A gd 7li{lqgJ cE soe
l3A.7a^lollel6IE +E +=*g "Jqql ,'|4 fztaltql, ol Ell 1 4 B;6-Je_eE +=c1g +4q= 4l

ag "Jqol f,zlalH "J"Jol f EszL +7li;la_ El+^J +E 9lzl zollrl9 "J"J"l + "JE= N44a 6IH z=l.9ld9 g."8
fzl rt2ft;lzl ull$ol4. E ?5 +*g EzL ealol f;zla|fl ol + "JsE/(x) =,f(0) + (dfldx)ox+ ...e+ ag E9 Taylor zl
ead-=ql, ol4¤- +4+. EzITl-Ttqg EztB4 !;l4l ol g Eail 6}zl"zltlJ +latlrJ q+4 Eol 448 + glr(Eq sB
+6i71 ull$ol4. rq+ gEE qgg 61146l^= rllE f9zl 9 El4xtE tl^l rz5 BoI4).
¤s_a1r}. +Eql ruzol Egllzl qtEql += +*ol ¤-E
=
Gzl4l 4+ eLA++r1 C4L6IH ql g+. 4lE .}ulzl- e\reD= sf(o).
"Jg ^(g),
.JA{H "J4"1 gEql ul4 6zlal{(p* I), 44^J fr-E +
** rtTrz- rt/2oll Hlell6l.q gEql rl4 ?zI-Jr|(EzIzI q u[lz[z]E z=-tr91^19 "J"J"l + "JE= trltg-r+ rJ"l 448
uule.4l 8{ ol zl ullE"l4). + 91tr1.
dN
zJElEt q 13A2 NeD= 9v'(0)- L
dz ),
m=MlNr r4r M-32.a0lmol-rgl orEzl.el +E +=*g
Hol a9 7l.i4 ¤Eq A, Îolql B"l-eE Bt "J"8ol +=
2s"cE r.oobaroll^J trl^s-4 *ol ¤4. z*LLtolr]. z*Y +E +"d:o14. nI+^J g+_e_e+El s=+
kg m-l 5-z
o +9 +=+, + g+ql fl= +4¤e-l +Eql ,l"Jq= +%+
t.00xt0'il /(r-R)g ol f 7J4+ Hole +t. <lol g+.
Z*: y2 = ^17J
,n *
ffi x(1.381x10-zr J11-, )x(298K) Z*=f,Nu^""n
=2.70x1027 m-2 s-r I&-+R)=# ! Tt[(-h)u^" ^
ol +%Lg 0.45molcm-2s,"ll 6Jl'&++. ,JE= Ezl¤"l +E6L7l dql

"J"Jol +
=g6J
z_-?v *,.
ql^Jel al"l4.e_=E__ e__e.+q g+-e_E9 Ezl ++E rBl6ll
+qoh eI4. ol A+ql Bols= ExlE=g z=+),gl^J
(a) *tl 1l+ =Eol+
4E"lE, ol*ql^lel "J"Jol + "JE= n(I)ol+. trI+^J,
ar+E ols-"oft.a41 qlE^J LoE z\&zlql zl"J
r3A.7b^lE
q= Eztg ¤a +=Jg +4r]l= al¤- *s6I E7l_tr_ ql+. /(LeR) =f,9[(4.)u^" ^
cJAl2 dE+"#E 414I

@ gE Ba.I= LIE|LH=
=trel ^l tr++^J g+e-E+El sEa- e=s9 dA +*g r}e=$ pol
:H t:e.+ql +EiU Hl]zl. rj4tallEzl-. z=09lrl 5ol aE F +48 + et+.
46I= EzES Hle 4dE +E. "l+ ¤+4e-tr- eI zI*
1_= l(L-+ R)- /(L<-R)
68E lr,J+el 4 ?-lE Bo}e+ot qI+.
=t/-""n lN(-L)- lf Q)l
H N-^l = i,-.,n - - g),]]
Lri
trru
,(0)
N+71 {[rro ^(#). ] [rr,r,. ^(
z 'JOI, A
<F
o
ul4rl,
EO
6ru
I,=-iu^"^"^[g), ¤E BaJ (13A.8)
1
0 ol
^lg f.*"1 +EE
li} E6J+ql Hl4Etg +4'il=ql
olae Fick9 Hzlgl rre.z44 *= a4+.
fa 13A.4 Tlillel qc +E= zltjdElE z1 f;lxltl Eil4o+ ).'J=
ol#ql^J 13A.8^14 13A.4^lg ul:zoll_H_H q& 4+9 Atg
Eoltl TJal++Ei el,\l 'JolAsl EE Erl6l.= tE ?aJ= Ie16|10t -dtl.
gg + flg A ?JE+.+ D=!)uu^"*¤- E¤- + 9l¤. A +L+.
510 13 ErF=el-
Ezl9 ¤+ xI-Pr qE= r

+E tH4ol ea6}
E ere. Ez|71 EzlE4 -g +&
==7I6IEE =
4l+= *=+.
*'g Hlg
(+^1"61 E=)
Z HIg (b) E d-EE
(E=
=E)
+F EHll fl4(Eq zael Elolz|el t}^l 7)ql E6LH zl]zH E
lg 13A.s E+El PE zl¤0ll^1 ra16[rl
^ltS =tjJtro|
do-e zl¤3 e=vkrg ¤t qlqzl. zlqr glq. gzlrl y= EzI
+E1el .$e.E= StrlzlE $Dl^l:d=qIE
$oJ= ,-Jol-7toF ol.E 3?E
"llHzl9l 7lq6l+ 2iI6J-a-
^lC|al LiE}'}]= {} x].H.fe] ++. 37]lel
?l= + ?lqq, r46lq Hl=.J E=oil trt= E^lef 6Eg qEol Etrl-.
Bd eF zI+E= *= gzlel a+q= v=iol4. * Ezlz}
7l*4 +g tr+g ullb ol4ol "l ¤+ qlqzl$ +HI*+.
rfl+ D! zzl CEE qet=
ol al&e q+61 ed.6]|^J qtlE A+q ol+iflH 44 Hl+qI EEE oJo" ol.{ ol +g
ql+ ¤ + 9lg AEQL 4* zlqoflot eFt. qzl.tj ulzl a
E6J qlqzl gtlg EEg + 9l+
4al]#zl *+ 6J ^t¤¤.:18 l3A.sql +4U ulo{ pol $zl-
HI+ + Hls 448 BotTIot
'J E fltrtroll EJEI
+ 9l= 4*zl =Eflq+E
=ol E++ =ilql^J
+q 9ttrl= 4"14. r?-l6l-q +ql E ^l
4617]| aql q= EzIe+ +E=6Iq +oil Eg6tzl * e. + fl {zl,rlE g"Jol f Es-= +"J6J.zl"J ts4.9 ¤f "ilHxlE
4ol+. ol 3rffi IEJ6|] +ElH "*g +rE 6]lot 6Izl"J +44= gE= +"J61-^l ?++r ,tCfltri. EzF=$ g+el
= EtrI E48 gqql^J Etzl"+ +E¤ 6Ir. _H-+ +g qlqzlE
4+ 44= ++g +e *+q f aol4. :z4alq 4+4
eE q& 4l+E'l+4 ?ol 448 = eg +g *lt zlfr qEE Bots+rl E+6J+. E6J e=+e_l
+ 9l+
_H.+ il.Ttg ¤q e_s+El B+ zI+ es-= Eol-e= +4E
D=! A,u^"un q^l zt+ (13A.e) E 9l+.
E4l 1 C%I'J4 Hlql %I-J. f_rf tr ¤E +%hg +4.11=
z]trJEt q 13A3 ^.1
9zl z9l 9l= EzlE ¤+ 9luJzlE dd4a 6lE + tlHlq
Eq lBel +t+ {l ts.:9 Ar+q E6}H l.oatm4 2s'C ='*.JE
9lHzl +%r3 r+s-4 e'.ol 448 + gl+
el zl;-llofl,<'1 N,+zI9 ¤t zlf. Be.= etnmr|.6J¤ eg
zw zw
Eqq lB.lql^lel 4lt} e4ql el6IH NrEzIg ¤t
_E_71
t&-+n;=ffij e?t) /(L<-R) =lfrjr1t1
+qe 475msec'o14. trl4^J olelel aa6}ql^J N2¤.zI
E +Î al+E trlg+ d"l ¤4. "I4rl dE +rj$ trl.$$ B"l ¤4.
_= l(L-+R) - /(LeR)
D= I x (91 x 10-em) x (475ms-r) = l.4x 10-sm2s-r
1
= I u,,,",n9f le(- 1)- e(l)l

¤Ezl= l.5x to-sm2 s-'o]4.
e(z) = e(0) + z(dt/dz)o, z = +7
*,..""r{[e(o) - -
l3A.e^lg 7l-zl f 6llot B rll¤¤ zl-zll gl4. ^[#), ] [',r,. ^(#), ]]
^ll =
=-*u*"^nhr(#),
¤t zI* 68tr I= "JEol *zlalB e^61r.
(t3A.Iaal), o|4rJ D= "Jqol eAd-q,
tr:JAI2 qq4 8s zlgzltr s^l6Pl
zl&zl==_
=!7I6lE qlq^lE +lzlql qe zl&zl| $E zl$zlS.
Ar+4eE zlill $z|4 q Lzlrll +,tI¤+. #
s=yt<folt:e
¤t +q /-..n3 Sszl- 94zlB +7l:"la- zlzl:t- detdz=vk(dTtdz)4 ?"1 449 + 9l+. El-4î,
Hi
DE gETl ¤'4zlE 6zlaJ4. r?-16} ffi
(13A.1b^l),
q E4+,,.1e_ 49 E4-b i}4g r.le fe-l $z| I, = - i u ^"^ 1N(#),= - r,0r",.""^,( # ),
E-+ ml=rll +4Ig+(*E zl&zl7l ?Jg a+). ol E6lE "llHzl +=*g zlEll6l+ qlE gE z1&zl4\
^lql
13A elE 7li1le.l EHJ ¤E sl1
Hlql*q. *q^Je+ Et+7l.zltr a HIB a-e-el a+E llq6li

x [UIE
3E g-6ll= ri$ ol {9 r:e.srl4 ulnal$ q+4 AC
^J
¤4= Eg + el+ L-al xo
-Lj
K = \vkun"o,rAN E E-=-= (13A.10a)
$tsol f Es= $tI "J"Jol I9 +bE j). Tlz.la_ e\t=

z
nN^tv = ll]Noq ,Jol 448 + gl+. E vkN6E TlillE "JA 1
+".] g- trf-*"14. r?]flq vkNori E qlqzlzl 9l tr}4 0
cu,,, = (au-/aT)ugl 9oHr.J cy,n,=NovkTt ¤+. ol +41=

-A
^J q8 Ee.e+El EE4oe
rll"J6l$ t3A.l0a^lol rl-o-$ R"l 5}4. fal 13A.6 7li1Pl EdE= XlltolalE l.al
EE =deoJ= EGITI uul= L-al $o-ePq SUElol 9ts dE x4
FJ ^13
SEE4,tl6llot:dtr|. =rl
K = ]/n,..,ntrU]C,,,,, E trs_= (13A.10b)
ol4g s e1_ptkTe+ l3A.e^lg D= ol.a" o|{ tr}*4 ?ol 4

¤ d+ +rI $qql ++6J EqE4 olf+ qlqzl= +HI6I
4E +E el+. dtrtrzl fizlz;! \ ztz\uj ,zlfz} rlolzlH ¤+ zL+
=
gtl= plkT D= J /.r,.".n
BEzI 4to|4^J Ezl-5"1 "ilHzlE H4t4z1 +HI6Izl *qI
r=Ivkun"unlg\f lrvku^"
vpD
E I-=.s. (13A.10c)
q. rq6l{ ol + sr+7]- tr-41¤+. dE Ar+^}sEE gd
^),fr T
EE= oJfl"l E]]+61 *otrJ rc*p7l B trll$ rlle-lolfl Tqql
++6t+. ole4l *e *qql^l= x7l *7lE il+84 =-4,
zltrJEt 0ll 13A4
qlqzlTl +Hlq:. aEE z)olzl¤-zl9 zl+ql E6l]^J ae
ZI++ {l re":oll^l +* HHI E6}H zs'cE r.0atmoll,<J 9a 4e Ez}{l el6ll^J ,,J6]|E *zl t*E4. :_4alq +=Jg
NrExI9 +& 4l+= D=!.4x10-sm2 sec-'o]4. 13A.l0c4l old6l gqlillE +ql HlElla}xluJ $olz}= ,l?]= Iql ++6I
I ol.&ollri N2EzIel g dEEE 4lt}ts + gl=Ell oltrll= ,l qlEql r* [l] tr]+^J rc*p7l q= aol4.
v=E f"ll"F trH:4lg BTI ¤+ rJ44 24lE qd S
*rl"l fleq, ol +++ Ez}gl q4^J= 4lE ¤+ *alol (c) E¤s
ul_B^d"14). trl¤I^l 1.0baroll,rJ= trl+4 eol S+.
-23 rre.0ql^J g¤"u- e=tr_+q(mr= +gB+q L+l :o e_E)
J m-3
olE"6lt E4-= z-04lll-+.S +q+ mu,()i4 +F+g g
.- _ |x(l.0lxlos il)*(r.+rl0-'m2 s-') E g+-e--tr+El s= Ezl+ ol +ql+ mu.(-)i4 &
^ - 298K HI6Ijr"
E%hg +HI6J+. ol z]]'JS ol+6IH dCE 4+ql ++
= 1.2x10-2 |I(-r6-1 5-r ^lg
+EB + 9l+.
l tzmw ICrm-'o14. ¤ezl= 26 mw K 'm-'ol4
@ E¤Eott EJEt^let +E
13A.10^lg 61146l+ ql= q-g 4¤-i$ +.e-6J g,qrr 9l+, +E ,JHC giel a+e+ ?zl"J {zlrJb eH}El= Cd"l
4+E d¤ eF=J"14.
¤J: zI* .Jqql Hlulql6lzl"J
6}-tr- I= "JoJol E4! 1 4 %16'Je_s.el +=*4 ¤E +=*q 4+
+ ,,JE ne "Jqql Hl4lel4(sr= ptkT).Er+^l ^l=
sE=- e--e.+q s= E{-E=$ +q'.r+ Ag gf+g eHl6J+.
13A.l0a^19 ),nE "Jqql ru6iq, g d-tr-tr q #
^l "Jq"ll ++dIQ. ,.Ei
mu,(t)=mu.(o).*^(*),
E8=*"1 +sH +qtl Ss zl¤zlz| * "llH ffi
zl zl$zlql 6flR6lzl ull$el +e g+*9 zlzll
¤ dF_5.E *=+(13A.lob^l). +t+.
==
512 13 ErF=elEE
mu,(- 7) = ffiu,(0) - il"

dr, ddszl Sqql roql E?-l+4 olf+ dtrtrE ?*e+ "L
dz
TJzlzlol+. + cE=6Eg +HI6J + gt= EzI9 iz| "*"tdf
trl+^l x* ¤** C+E z*6J {E +=Jg +*4 Eol 84. + B+ zI+ esTI 5]"oI4^J eqlg 4rll 6J+. ddszt I
Eql q+ 67|6I. olf+ sg gEql^J= E4¤ol tsEl _$
(r) .,^ ( # zlol4, trI{^J +E=*el frur"l 4zlzl rllEol4. Eq l3Bql
I, = r u
^,^nN{[,,. ror - ^^(*). -
[," ]]
] ),
^J
¤E6l4{zl"J .lillql^J= Sszl kole++ 44uzy z;
=-ir^,nh**(*), AqI+. olag .-441
Ezlzl $llzf, "Jqg ol44o} olE6J +
ilzl oll$ol4.
tr.JA|2 dcE 4l+ +e
ol +=Jg ¤tlg4 eg gojee {4
zl$Tlql Elql+ 4r (d) E*s
4. ol 49 rrt0^lr+ Hlit6}j4 E EE %Irl4e 3¤. #6ll + EzI9 B+ +qe. Muzoll HlEleil6IEE olEol ++g +4
H +gr+ ae ar+= ezl g+. ag Holql +E6l= +_tr tr EaJ 14r'zq1 HlHlql6|q, Graham
el E= B!g "J+^1il4. :4+ +E +*ql *qL 49
"l
11 = \1,,,,,,,).mN EdE (13A.11a)
+61-H E= +Eql +{} El zl.rlle} 49 +Eg + 9lr +¤
trllolEl= q s.J+4 s _e. ¤E6I= rll ol-o" gf + 91tr1.
ol
^lg
trl^.q=4 ?J+ + zlzl gtr_ 444zls aJQ(mNa =M4 "J4 pel- gE rE 714171E* SzlE d+|- +ql +r zls
13A.9^l ! D-\)uu.on$ ol$afl,<J). +Bg Eflg oll zlill $xlz| "l +Bg Fall {zl} +E=
rrn[rl
-ii:- tttultl /r. A r<r-\
tlJ^.l lU/
trts_r+ e."1
"l +471 ol +BEl+ H"l9l +E6l+ +E +
+E +-Jq+ +BE Hol Ao. #+ a4 7JE|.,
n r oMD
,t_
- RT (13A.11c)
m=M/Ne,k=RlN^
¤zlrl gl= ,l^ll EzI IE ¤ibEolL, M3 E e%hol+. 4-LE-z

^-
PAo PArNo
r.!-
= --r4- Lv'Atl
- (2nMRT)'t2
zlEa q 13As E= 4.E. (13A.12)
*E zI++ q 13A.3ql^J 4l&EI HHI el6IE 2s"cql ol E= +E= Mtt2all qulzlloLq, Graham9 Hzl4 "Jzl6J+.
Nr+z}q +tI al+= D-t. xlo-sm2 s-'o14. tr|4^l ol r-UzE olzlz[ Eqglq +-ETl¤.42]H E= 4E.z]
^J ^lql
M=28.02 gmol-'olu e 13A.1rcll9l E6ll^J q^g=r+ *+ 4 .-BJtl+r ++6its q] E+. glrl-"l.H p".7olrr_E E= +E
4= eg+ el+. r'l2ql HlEll6lq gEql 44 6zl+4.
Î¤^J
= l3A.l2^le
J m-3 sd 6zl $4"1 rll*61 *3 -Li14 Eillel +
( 1.0 I x t 0' Pa;x 128.02x t0-3 kg mol-' )x (1.4x t0-' m' s-' ) 7l "Jqg +A6F= Knudsen flA zlzzl u)zlE- +4. + 6
q_
(8.3 145 JK-' mol-' )x(298K) 7l E.qol p"J 4Ig +Bol *fl +F +ql Bflg a+
^l-E-=
= 1.6x10-5 kgm-tr-' r e*E A^ +EEp{l Hlell6J+.
4 t:oplol+. de 4Y vt VPol+
GtrEU EaJ el^= o l8:et gej altl
=7
I
r3A.rlaal3 +94 ?ol "H4B + 9ltrl-. r'll6(m.p. 29"C, b.p. 686"C)9 Szlql l-Jr s00"C-tr 7Ig
6i9trI. ol $-21"fl4 zlE"l l.0mmgl +Eg tfltrlq
g dtrtrqlî ol"l ¤E,tluts+B"l Lee-p"il *
r.00h(3600s) F"J9l 8a.amg9 ee} eA?l NAL+. s00'C
+6I+. tr+{^l E drqs+ "I&zlzlE ACEE {r ql^19 Eill
-
rlo ^ll+4 Gzl "Jqg Al&4q4.
"Jqql ++61+.
/,n._*Trl2olE+ "J4 +u]ql^l= ry".7'lrol ¤4
Rr
rlol r.el-g /.[:d 8zl "J9l^J= +zl¤ol B=qq \zlE- E
il g{oirll *zl$
("JA "Jqql^J= nnTyr). * zlzll9 dcE= g ulrll 4+ "lillT} 6zlE E+^l7loe "JQol
Eql tr|+ 6zld4.
13A gc 7li{lel aHJ ¤E s13
+. ,'|4^l E¤ +E= "JC6Iq 13A.12^l_e + +EI.J + ( \"' am

p=[znnr
M
9l+. += +EE e+eg +4,llelH +=99 utztb )tW
Exlf9l4 4 Ezl9 e=+g *6tH g+. M=t32.e8mol-'9 HIE* qlolq# Bq +E q¤+ a
g ar}= Eg +
Îolq +Elt e"* +}'
Ar Lm|- ol +H H"lE "l 91tr1.
=olE"Jql +==+ E4-+ql+ EzI A+g ++ ar+ a
^lz}
+. ( Znx$.1l451K-' mol-')x(773K) ) U2
A.l t3A.12
P
t.l X
84.4x10-3
P1:).-',, ; xArxrn rux(0.50x10 m) x(3600s)
= l.6xlOa Pa 4 l6kPa
Lm=E¤ 4.rax a,txm= (2n.\1111
.^
)'
:-
rPl B7[ 13A.1 200mg9 gz]zl v-z;z e-E_e_E
9zl,r-l A0e: +Bel Hololr Mg E aelol+. ol 43p îl+
ql +6J o e Bh+q +E}8 + 9l+. +q E=qq 4zI4E g"}EI¤L ^ltol a4A-+?-'
^l tlV'ZE s¤0I x S'g'E
T]ILJ=
=9-d
D l. BaJe +qd ^lrJ E"Jql +qd H"l9 Hg Fr+61+ + rl4. EdE= s--E zl$zl= trI4 olEtll 44zlb 9lHzl ol5"l
d 'ltt} CeE olg I ,r.lzJ zll$ H"le +b 6to.|4. 4 r glulzl +*g s--Ezl$zlql Hlql.J4.
a 2. q,l:le Eeol \E zl$zl= trI4 oltl6ll 44zl= Btt trs. ECe 4l;. z|&zl$ tr[?+ 0156l-= d¤ e5=*olq ol d
oltrI. B eE%F +"Je \u zlgzlql Hlqlqi+.
tr 3. Fickg q5 Ellg4ql E6IH Eeq +*g:-"E- zl$zloll tr6.
Blql6J+. 47. Eoll E-d Graham9 E=l.ll el6tE ts¤ +E= Ee%hE
4l#ql EHlrll¤Itrl
=s-d^l=
Z.A]
.Alzl
oe. Î
-1 I --1 4 H-a
Fick9 g-& rlll$zl I = -NNldz 134.4
ge+ qlLJzlg +%I I =-rdT ldz 13A.5
"*9 x* CE fr*
¤E" 1=-1du,ldz 13A.6
$dzlill9 qt} 4l+ D = !Lu^nn KMT* 13A.9
$dzl;ll9 ¤ d=+ 41; r = !u-- LllfCu.^ KMTg+ +F EEll r3A.10b
Bdzlx{9 dCE.4l+ rl = !u^*,),mN KMT 13A.1la
+=+E 4E * llMttz Graham9 Hzl 13A.r2
. KMT= zl;'ll -Szf Sftskinetictheoryofgases)oll oJzjrj u}4t4

^l$g
EEI 138 Ei{l +oll^lel E^l--
^Jel
dB +F%LE +=J=4 4s zl9zl .<[o1E H]ql tr-++
> 0! EE= Ell+ ol+' +,
".jg qqi HJ30l
qqill+oll,t.1 golLlq, qat^1 0l-
EE6l 016]|
6l4E E¤ Erte.} 013fl1 olelEt Etz +oil^.i olExl 0lE6[=
xlE gopt elq. /,(gFeJ9 x4 C+) =-ry* (138.1)
> flfl TllLJ d^JEE SI++l= kg--'s-'olzlEL "le+ ¤-.ra"+ ++l"J Pas (vI
o|eflil 7l6flrlts E7l4 aol EoflE E¤oil 7l?151ts rlBqat t-zt z)e 444zls ++. Hl-SI++lql _:EoI3 pe+ dEl-E
ilEE 0l+11 EIE 018=01=i+E= 7l-^l1l EEl. olZ cpzl olzlE pal l|oll ?lErJl, 1p=10-tpa sol-l- uI4
> EJe'Et o{!Hl rl^l
.<l tcP=tmPa sol4. a4illEql 4aJ ry At$fl "J+= -E- l3B.l
EB t3Aoll^'l A7t|:d EdE 4l+el 89= Tlrla EdE= Eol-u ql +E6IH+.
I
aolq. g+ 4ltlollî= trl+xlE 8^l 27011î ¤861"= Tlal +ql^Je+E 94 .lill +ql^J +^l7l olt6IBlE ol*
^Ff-g
EETlqrE xl^.l= 0lE6tzl Erl. Ezl-EePEl Eut4+s7l fl6J 4l^6JE 9lHzlE Boloh t
+(Eq l4Dql^le-l s'B ,J^lql qsE 'g^de+ qlLJzl E"').
Boltzmann +E Bzlql E6IH 6J Ezl-z} 44+ E E qlqzl
"lg4 tszl-9 qqill +ql^JE +E¤ aÎ6tE ._qiilg ca4
E zl4 q¤g e-elnrq1 Hlell6}q, ot4,tJ qqill +ql^J9 EzI
r +ql^l "Jq+= HI+E oJtr-g ol6fl+ + 9l+. ol e5g s e1 ol:ao E= ol zl+6.J+
¤^lel gE E=EE "1"+"t ql+
{4 z}zl ¤E H}H o + a^}g + gl'}. qls^J dcEe+ ol gsz} g4+q ,.|4 E4¤e olf;alzlTl q fl9214 dc
49 9-r e-l=EE +A6L"l "lE g*9 Egg "JE= trll ol Adi{. d¤s ryE olfEql HlHlql6IEe'l+4 Ag
ols"B + 9l+ a+ q
^llfl¤ +=e-l ¤eq^J= NMR(-tr_ +4lz1CB6|]ot ts aol+.
q t6c)r+ EpRql E6J Sp+ gB
^ltg +C6Iol Ezl-5ol
,] 3rld6}=zl= gol4zls 6J+. qlE^l +g d^JE +41 + 4 - ?oeu''*' trdE(o-4^11)el 8E 9= (13B.2)
ql^l Ezl-==3 "Jdel 4Lg sld E4l(E s")E
"++
qc
= (zl+el Pszl- +"Jg ++-61-0lr* "lag d^dEz| ol:a"Eoll
6Izl"J dC"l S= +ill +ql^J= 49 Ezl¤ol EH"ll eI r
qHlqla}Tl rll$olr}.)
radian(57.)ol+ El= sld EEg ++ E 6}+el +s+,*B "l ^lql E6[E A^JE= $Ezl rtzl
3 HIEJf|taJHolr}. ol ¤eql^1. +d^171.-qill q4 #+6irll #aagop ++. dB4ql dcq gcsl ql
.Jql
^l
=Crh
E= t$$ ql e4+ g= {lHzlE ole"6|{ .<JE $u}olst HzlE Ezlt B+ tls4+ qlqzle| ulfa|4. r:e.z^lq E
et¤ alllalzlE +tr+. 6IE dCg &E +7lql trlel #46}rll AioJtrl. Hlr4 +g
gE gEql^lb "lelq1 q= +41= ¤84-"e +?lg + 9l
138.1 g-d'Jal +(rg 138.1). Ezl-ZI tgzl+ol E,E a71= a}$a1z1tj g
alill +ql^J9 Ezt gf,$ ¤+61-= Ell= + zlzl,:tfl4, olfl E 138.1 2e8 Koll^lel Eillel E¤E*
ol ol$sl-r. 9l+. r 6J
"JBg BCEs+ r gE 9=s_5 4
4/(10-3kgm-tst)
c6l+ 4,oll, E 6L+9 'JHg 4zl*Z ol+6i"1 +rl] +ql
olgg d."L ¤-q EzI¤-E¤ z|,<Jlalzll +?]6l= 4o14. HldI 0.601
^Jel ,\o
-T:- 1.55
{l+ 0.224
(a)
"4i{19 E¤ E+
E* 0.891
dCE 4l+ rrb Eq l3Aql^J ¤Eql HLql E6lH +Al +ql . zle eql q *e *E"l ++Elq flq.
t l cp= l0-3 kgm-r s-r ol q, EE ¤ ^J E: 0.891 cpgl ElBrJtrl
138 Eill +oll^lel Erl- s15
2
I (b) t6tlE E4
1.6
ol9Eol +I9l= +E +q EL= F d+ d+lil¤ +
I
ch
Îolql
I
E H ol ol¤.EE ol5-ql g."1"J3 &+zl s=+. olel+ +._4

J
o) .2
E +g 4z)4 dAg zloj RQlcll, ol xJajg I o o + 44
o
lc'
I
0 .8 Br{to= v s). z16} Eltlql zl6}E E+.J L1E c1=17p;
u \...--- . 4= 4ol ¤4al-4. Eg¤-(o-l)g lilrzo e--tr mho{-,1 ',

<0
RE
0 ,4 -.-__ q$g-Lt
"lxllE zlQl^(siemens)4E: SI E^l= ^l*s" 6ltql,
1S=1 O-1= 1 C V-l s-'o14. d+= "Jqq AE +$rll}-ql,
0
0 20 40 60 80 100
I A=t C s,ol{, 44^l 1S= t A V-tol+.
?E, efc
¤E er+ql E6LH EI EeE dE= r aol /ql trl?+ aI^
fB 138.1 Eel trdE7l e-Eoll 9=ap ¤:d 8s.z1EofE+= tr1 6Ir. +H4 Aql I4-+ +7I++.
".J3 EII=01 r 0l=E01 "JE= trlEJl¤ +=E+El uutrl Lf,J + ?les-e
=71.
Eill7l tl +E4o+ Etl. A

G=K EE ttre.ll (138.3)
T
Hlql
^J+ rc¤ 4zl dtrtrE}I +=+. dEE
zlfl:. +, r.?-l
tr-g4+ql 7l"Jq= qHi¤ glHxlE z|{ap
zffi-.r.|o1E _7
'JolE
trlElE +448 rc9 Sr ++l= Sm-lol E+. dtr tr
ol <tg 4l&6lzl= ql+61 eEq qlal4 o + ol-zlg
"lqlA EAE ^de"J e}Eql dE= EAq t zzlql E=dtr+.
=
tr-44 dE-E= ^lE +fl d6I +Hl!l9 E" Eql E=6tq, EI+^J +
94 ?"1 4Eq= dtrtr A^+ "JHI4 " + 6I= aol
q = ^l-a-o
zltrJEt 138.1 *44"14.
2s"C9I s0'Cql^J EE dCIi!
zlzq 0.8e0mpa sel 0.s47
An
K
E 5trtr ttrgl (13B.4)
mpa soltrI. 13B.2^lql E6H^l Ezlz} olE" 6lE trll g,qq} {}
c
qqzl= +g 6l]e+ ?Jr+. {zlrJ c= d6le9 +t-"Eol+. E dtrtrE sr +

7}6ll
^"jEl ^lE =
+lE sm2mol-rolq,: d¤4"J alg l0mSm2mol-1014
1Qr)
-p(E"/RXr/r-r/r) (1 mS= 10-3S).
nQ)-'
dB A!+ql el6IE g ,$EE= +Eql tr}+ H++. :. eI
"JHE r|]+= +l6ln A46iH +*r+ t9 prffi Eg ol+= +.4 +q ol¤+71- a6lleE +Eql uleilalzl ?+g +
+ 91trt. gl+= a"lc}. qlE^J E d6]]e +Eql^J= ol¤.E E" E7I ¤
,_
ua-
Rln{4(r,)ttlil l} aE +Eql 4+61 +tlqi *4-" + el=6l.q, +aE LoEE
llT_llT ullE f;z|^l4E ol¤f7| HIJE ?+=+.E-all ohq+ ole-
(r.r rn, l"-' mol-' )ln{(0.547 mPa s)/(0.890mPa s)} =zl
U (323K)-1l(2e8K) Eol trstq d ^JE{¤¤ 6}zl Ell$ql +"_4el d=.ry o1
= 1.56x104 )mol-t
e +ql g"J6l-7ll Hlqlaizl ?*=+= 1"14.
le^]l7l9l Friedrich Kohlrausch= E ds-rg tlH+l6l-Zl
? 15.6klmol-'ol+. ol {le. +A A6Jq Hl*6}+ =
^]lzle+ csl.q E ar+ d d6l]eel #e +.+el E- ds.r_5'l+r+
?ol :z LoE9 4l#ql d¤ o + e-l=++= ^l-¤g "Jal q
dCE +e Ar+= 6]]46|= ql 9iq^Jq f, zlzl f,izll| fl+.
EillTI TIgqH :z ujs_zl. H6tol d^dEe.l 9r ua1gq14
E4l
+Eqd 7lol. ++= 4,o14. r46}q ga+ +q 6Iql^J
,1- = rli, -Ktt'' ttuhtrausch (138.5)
=
d^dE9 Ss 4=E7l "JA "Jq 6Iql^J B+ "JCq! ,J ol +4lE Kohlrauschel $=lol4i1 ++. r= E r-o E71 oql
Eql^J gld 4}+. *9 gsql^l= Eq dcET} "Jq ol #zl zlztlflzly +qlql^lE E- dtrtr.J E dtrtr /;ol 4l
g++ AAel+. olag +a e.Jol #q4^J olEol ?l"lxl zHs-J ol$iE+ElE TlqE ol+qa+=
=:d
zl rllE-"l4.
ÎdE "Jot4*+.
ol +4lE olEel 0!=e! H=l"lzE +e.=tr1l, oJolg
==JE
E ++ E dEEE. l.*, rr-l-tr *"l$9l 'l]+ ag I_+r 6I
516 13 ExF=el-
H ol Blg tr|94 ?3 al
"_e. ++E + 9l+. 138.2 oltel olES.
4 = v*).*+v_)._ ol8Eel qg4 0l5e-l ga.l (138.6) olg.q E- ziv+zl olgql uI4 c.ol* ol+E
+a4 +ql^J
¤zlrJ v*e| v_E gE ElqL^l +9 R ololgr+ 9o199 +trI. oloflalel{ dzl^}9 4}¤¤ ts. E^lql ac qleq EqAt
"189 e#
qle^J HCl, Nacl, 4 cuson9l 4"]|r.l} v*=v_=loljl, MgCL ql fifla1lop 6J+.
el a+q= v+= 1 r4I v_-24.
(a) EF Aal
EtrEU --:dEd.=ss1 g6 dt +ql^J= olgol dzl^J9l E6ll^J zffslzlu3 ac +g
2s"Cql^-1 KCl(aq)9 dEE= c= 1.0000mmol dm-3 49 "199 ++6}{ Eflr+r 9= +,11. trila +e+"t 6I
g
"I 14.668 mS m-tol a, c= 5.0000 mmol dm-39 4l
r, + HJ6llE *.+. ol sffi
Ed xli{+r ++. "l3ol d
7r.74omS m-tol4. ++ !i- dtr tr ,1jr+ Kohlrausch tf t, 7l1/E g-&g Er. z1-4gq q4 d^d zlillE- f,zla[{ u}fl
E al- +6Iq4. .il a+ ^J=IE +qql Eg6t4l qirll, ol +q¤- E+ +al
ol+r ++. s+ +qe + tlHlq= 6Jg tB +al
r.E{A AtB 138.4^lg ol+6}q F L"EollrJ9 E ds ^le_o
E= +6Ir" olq^J l3B.s^lg ol+6}q ol= + AtE iI +g + et+
A^(cr) - n-(c,) - Kklt' - c)t')g +6Jr}. ol{9trPrl tE
E+ +ajql EJEI fftr
+611 4l+6ll^l r:s5^19 E. dEEE ole" olcl /r;g + ^.lol
++. 4r-l Hl+ trq4 fl= + ¤H d+ rl-"19 q¤l¤il.7l.
^0ol
EOi c= i.Lru0Ommoi <im-3(oid3 i.uurumoi m-3J] ,j+) E ol + d= ,r.rolel +"'l +el "lg=g +"J6J nzlo) \z\
"J ull= KCI(aq)9 E dtr trz| rl4.r4 4.ol ¤4. $ r,=tcp//el $o3g- tsrll ¤+= Cdzlel9 Ar+= zlzla-
ol +E rleg ol dill=
l4'688mSm-t ^l4}ql+. ¤zlrJE EE ¤ =16ll^l
IIr- l.0000molm-'
= l4.688msm' mol-' +4.Cg '16}zl +l6]|^J d6l+E +s= +^lB 4o14.
^
uffizlzl-e c=5.0000mmo1 dm-3oJ trI= g dEETl 14.349
E4! 1 dzl^J"l olg.ll "lil= el
ms m2 mol-rol g+. Elel-^J, 4zl* e 4"llrl A6LzI ze"J ol33 zen\ Cg *=+(++
xlE r}^l 279 u-ol-BD. r.I4^J +94 Ae eg B=+.
t\-_
,u A^(rr)-zl-(c,)
_ct:,
_ (14.34s-14.688)mSm'mol-'
zeL^Q
ctl,
4,..,.,. --T-
= 8.698 mS m' mol-'/(mol dm-' )'/'
(ol ++lEg +gg 1y3/zs m7l2 mol-3/2 o + Ht¤ +E gl cJAI2 dC zl4l7}ol8"ll Elil=tl
zl"J + q44 BqE otzlg rEllE 4= aol ¤461tr1.)
:"llilr +e q= +qql HlEll{+ Ele zl r
"lg"l *o]]E
olxJl c_1.0000mmoldm*ql q6J qlolrl= *+ zlqg gr| ¤+. qlxlEol aola 44ol s?l 7B "J"Jol9
"le"al¤
dE-EE +g+ 9ttr1. ?*, ol zlxlqg stokesol H=lo + #qzlE trll, ol H4c
¤+4 +ill +¤ E" 4flt +ql Eil.J gqql4 aeg E6H^J
*?1,
4,= L4.6g8mSm' mol-' + 8.698 r*sIl I
(mol dm-')"' +EBJ 4,"14.
x (1.0000 x 1 0-3 moldm-t lrrz - I 4.963mSm' mol-' Fvlsco usJ-fs f= 6nna Srokes tsal (138.7)
+4 (E alg rll"lel"il *+q +s +zl Hl zl4ztTl + {zlrJ ryE d^ds4. ol !e EzL 4Eql^J 4+¤+= ag
II,zl"J A+EE ol¤7)l7lzl E^lg g_s= s+. z|{ail +Eq} 4o14, de4 +Atr-+ ACE =.zl CE.E
\t7l 871 1 38. 1 25"Coll.r1 KClo4(aq) E dEE ¤ "*41 +4U+
E c- 1.0000mmol dm-39 41 8.780 mS m-lo] 11, c= E4l 3 + qlel *¤-o e +4LtE E+ +q
5.0000mmo1 dm{"J ull 0z.o+smS m-1o14. +E} $. dtr tr ol + Eg HItrll HJ6Jstr_ 4l+6iq, ol + aJol fQ$ ol
^JE
a,ir+ Kohlrausdr tlf t9 <t59 +6Iq4. E trll *a-E g+ 44 s"tl sE:"tz]l g+ +,6:zeg! 4l
=
,-tou rtu 5ur 980'? I = V' r,( r-.rP lotu)7,_1our .tu Stu I 6tr'5 = )tr :E +¤ol ol+qdq.+,
138 o4i{l +oll^-lel 517
=rl -
J_
zelE
-T E+ +aJ (t3B.8a) itEtrtel 84 zt 8d7ltrl
d6I Q,(++l c)E coutomb fleif ,p(++l gE, Ds

=*,trlH]¤
13B.8a^19 olgE EF 44"1 dzlat9 Hlql++= ^Jzlzll
qL4. ol t'-q^J Ezll d6I aE ElHl¤ qq
^llTlql
49 s.q=+.+ zl(++l A,Lt I=lv C)= q-q=r+ ?ol f"l+14.
s = utE olEE t¤El (t3B.8b) Eo= -Q9
olgel 0l=E4I +++. dzlz}9 rll ril-?lel 4*,

dz lEl l'll7l, ¤(*+l "lq B Eq v m-r)b
¤zlrl HlEll
^J+ 'lE
zlE ulEi 'J Ee(vm-')E, r?]r s+ +q9 aR "lrl dzl ulQl¤,pel e=.9 zl¤7le+?Jt:+.
(ms-')-E +E|.llH u9 tflE +d-a.lAlm' v-'r'ol S4 (F__'d6
=: dx
I7lglll7l
(m'V-t rrxV m-r=ms-'ol Eg ++aI¤4). 'J+ E+ +q
I Ag -8, 13B.2ql +449trI. +le.l + ulral$ q+r+ ^lg
3,.l-flel A+ql= dzl^Jol ulel"lq r+q=4 ?ol f"ltl4.
ee 49 eg + 9l+. rE = -YQ
f = 6nna /"J+ trq4 il= + ¤q + r}"l9 ElHl¤ ilTt trll
ol + ¤q + ^09
q+4 ?ol ?9
ÎolE dzl^J$ +"J4q
ze ze
u
T - 6n4a (138.e)
rl+.
¤zld "ld- 4l+/E stokes Hzl aks_e Bq+H+ n=-LQ
ul
z}=J:d q 138.2
d6i a= r +lilql^J9 dzl^J rllzl"ll Hlql6F= .Jg ts41
g+.+,
olE" E9 zzl zJEE szl fl6]]^J z-ta +r E aE f4
olgeld¤4 elzlEql 130pm fl6ll E+. 2s"cql^l E 4lecrric =W
= relE uzl cl$a] zE
el dCE- o.ecB 4 o.smPa sol4. qfl¤e rlqql ,rl4 HB trll"J.Jg trlzl4l gtrI.
ol g+.
JV-,
4_
1.6x10-'ee
= 7'3xt0-t m'v-ts-' E +-tr tlxlE"let"F 617l rllEol4l ¤Eg + gl+. Ie
6rx(0.9x10{ pas)x(t30xl0-r2 m; olg.=e olgql Hl6H^l q ,J+ zJz)*¤ ElEq(HlzlE r
=
ql + gEql^JE T3zl*? ztf4l Elslld-q, q+^l elzlE"l
J m-3
ol #g I cm {o19 +E ^}"lql r v9 EIHI¤ il¤ +S.g 4"|e++ 421*9 t)lzlzl +7I++), tr|+^J 1t3 "l-ool
ql(q4^l E=l00vm-') olg9 g+ +qol E 7.3pmsr olgB+ q rf]4q ztg ol¤-9 +E +g =
=.zll +Elg+.
7I gtrt} 49 9"1+trr. olaol !r EzIEI olEo ¤ rll g}g s" oll Ezl# gr +q u + ;| +ill qqL4
=4 EBxIE
Ez1 ;5qî _H_E t ol9"l ra rLolgl * ronz119 gr11 qlzl$$ *=+. rfl+ +slg H2o Ezl+ Q]+61 4l+-HsI
Ezl-= E"aldlot 6l+ +qol+. Col{, NMRII Efl fla ¤+ ar+ql e-l6IH olgE ++ ¤
E 138.2 298 Kol Eoll,\lel o18 ol=E*
t3B.e^lql 96IH olEoEE +._4E A^dEe+ olgel
"lgg ul(loarrf V-r s-r)
aTlTl rlA++ aLi6J+. Bvlz} olg(&N*+ RCo;s+ ? ui(10{m2 V-t s-t)
=
$)ql q6H^J= ol {ltol de e$e+ ¤ *zl"J zl3 ol9"1l H+ 36.23 oH- 20.64
46ll^J= e- "*zl ?+=+ qe^J "JeEl ++ olge_l a+ Li. Li* 4.01 F 5.70
Na* cl- 7.9r
-tr.+q Rb+-e. #4zlql 44 ol9 HlzlE"l 6zLatE4lE E
5.19
K- 7.62 Br- 8.09
+6tr r olt:Ezl rtzlxf,Q(s l3B.2). "lBl+ E+E g.Jg Rb* 7.92 soi- 8.29
Stokes
^l
+q HlzlEol olgE gi{l E-+4 urlE(stokes H} . zlE Aql q "*e atEol ++Elq
zl$olrlrE qI+), +slg H2o ¤:zl¤ d+ qql= olg 9lE+.
=
s18 13 ExF=q-
ol I 0 I 'JOI, A
O/1O.1Oa\O
I 991
:lal 138.2
o o o
0
gd^lel dE
c oo
015 arF= EqT= 7trel s.44
sAt
--lal
Jo.
=oll,\19 fal 138.3 E+= Zltlg ttfl, +al se olEalE ol8Ee,\l s^t9
7-lal gtoll ?1= o|E=e trF 'J0l AE 6tE Ert-zrrl'(= sAArE +trl
+E 0t8=J.
q4 +"llE Eill
Îolql^J
H2o +7171q+61 uu|trzil r+q
r 9l+. ',JAIZ +g Er+tl}+ A5I*r+ d+E 4lt}
"Jdxl-b tr}|+61 lgqlE 4+61 = ol:ao E$ zlzla gl4 7+ al.Z +g E46I= d6iE
ze9 d6I= 4=,,-tr-
(s 138.2) "JdzI g+ er+ql E6lE .J^d
NMRJ+ l7O-NMR g+. Faraday tf f=eNaE
zaA,tAvcNoTl "l+6}q "lag
zlz| aJ Ezle$el += Ezl-tr- +lol *zlts ql a4E zsLtAvcFE- ++E +E 9i+. d+ I= d6}el E"rt 4Eolq,
^l+
ol E t.5ps-tr.rJ, ol Hl+C +Czl- 4I+e-E Er.:"iTl HI ol a+ql= E"4* d6l-%hg rlt are- +b zt4 e+. q+
^l+g
ql el6IE E Ezl-7I e+ r44"J9 E-ol7l^l zllHl]gq= ql 4 ,\f F7l ¤+.
I - zsLt A vcF I Lt = zsA vc
sgl= ^lt(t 4zl 2ps)4 Hli6I4. Grotthuss rllTl'LEql E

6IE, + +qE E +{¤
EZI 3 dE. dq+. 't E dFtrql +* ^lE
¤aJEol x|lullpgl o +41
ot,Hzlol lIe-rr-6 ol5-ol
Îolql^J
ololt-l-:\I olrL:r *l-rlr-=-l r:n r\ -=-l
dzl dsE G=lLchE- +qzlq, Arp= +a4ql aa qHI¤ zI
o o 'i io I d. tu. A-l- -l \+E
1-1 LJD.L). avl
-l
+ dzil qlzlq#g otzlE olEol g+. .14 "JEqoI +ql^J "l+.trI{^J,

NHn+ ole-el olEE 9rl ula^J4gE uul-Erll, olaE Hliql
I zsAvcF
L0 LO
ollzltl=.ll E6ll^J .J 4"14.
dtr tr= +94 a+.
(b) ol=Eg Etrtr Gl zsAvcFl zsvcFl
'- A LQA LQ
olgE ++ !i dE.s_= de4eg +Col z|$.6}q, olgel
olE" EE +r}]E 5|46I= +E Eg$ zlxla_ fl?-ltr- 4lt}"l rPlr +qi E ol$ {EE}:'1"¤.4 a4
7|}6t+. r46lq olE + ^dA +41= +6J + ?l+ ^)_ K zsvcFl zsFl
^LolE
'v- vc-i\f--Ef
018 ol=E9,t dtrtr Al0lol ol$ ol:=" E
tr4t =:d = 5.1414
¤zlrJ LQilg dzlt9 ,rJlzlolL str.=. olEo E us+ ?48 Î
Z}+61-rll TlsE g;.lalzl +l6}]^JE44 ceSE +s= + ¤g ol*t}4.rBlE,
llap r eTlnJg ^J46flE+. E*szI c"J da}l¤ +.+g
rj{ollEz}. ol d6lJAe. + E}o+^l +flE+El d6}z} z*eoJ s=ulE
*ol9 y*7fle]. d6IzI z_eoJ *ol9 v_\lzl ^Jzlb 4oJrJI ai ^

L=
zsFl zsF
= zuF
ol89 olEiEE (138.10)
zi. rflE olE olgE EoEzL vcz[ s1u11r =!+ EE v_), "J"J Lo ,E E Eg-=
LIEI'J
ol + tlJE= N =vcNaTI ¤+.

138.10^lg "J"lg4 ¤-"l9gl 4 rJol 4+¤+ 4 si+^l +
E4l 1 T}tlzi +g El}dl+ olg5el + +lE+El v* "Jolgr} y_ golgol +s= dqleql q6|]^J=
:7H t3B.3g +r.e. 6tH, 44 s-tr "156l-= o-J =" +9 olg 138.641 o EPq A;=v*}.*+ v_?"_tl ¤+. tr++^1,
ol Hol AE 7|$4 +E¤ F"Jql 5461+ ++ 4

^l7J 0IEEE LtElu
^t q+^J P:4 sArA +ql E t\= (z*u*v** z_u_v_)F
+-d dtrtr
(13B.11a)
4 Eq 9l= +e+ eeq,
sAr "Jql
=
q fl= +e| e+. q{^J ol E"Jql +g r+61+ olg rE"
^lzJ
E += $t'sLtAv =sAfAvcNng+ eq.
138 o4ill +oll^jel sle
=rt -
rilaBE zz 1361t4(qls^l Z*=7_=zoJ cuso.)ql q6H^l= ol qt} 4l+(d^dF-ql 9ul4l)z} trll olSEzl. ++= ae +
=
zlol 4¤-4 ?ol t+Bl]Tltri 4 Ezlzl fl41 ol56J + 914= Eol+. EE +ql gszl E
qfl+r 6ll^J olg9 olEoEzl 9s +71-ql q+ ai6J+r
,l?.- z(u*+ u_)F (138.11b)
e6ll6tE * gtrl Ezl +E q& 4l+7I ¤.E zlzllEr| $E
ql q ral q¤6}s-E uEgE +7]rql rl46ztaJ4.
z].JE! oll 138.3
zI++ {l r:n.zgl,rl 741d HHI E6}E dBzl"J "19 ol q

Eo EE 7.3x 10-8mz y-t r-tolq,
zl'JEt 138.4
E+^l "J"l$-r+ f-olg-ol
Ef z-l"J A+ql= dB4t ++E- dEtrzlQs--alz; s. 13B.2ql E6tE ++.1 +ql^l SOf- o1s-el olEE=
ol 99oh ++. 8.29x 10-8m2 V-' s-'o14. trI+^J 13B.1341(D _uRTlzDgE
.+ei zs.cql^-l ol olgE +& 4l++ r+q=4 *ol ¤4.
)"=lx(7.3 x 10-8m2V-rs-r) x (9.649 x lOaCmol-t)
_ 7.0 x 10-3 m2 V-l s-r C mol-r (8.zlx to{ m' V-' s-' )x(8.3 1451K-' mol-r )x (298K)
D_
2x(9.649x10n Cmol-')
lV C ' s=lSol4 trl+^J ol Ag 7.0mS m2 mol-lol ¤+. J v-r
K*(aq)oll q+ dE= 7.4ms m2 mol-'o]4. = 1.06x10-e m2 s-r
(c) grstein trz{l+l +41^lg ol+6tfl 6J d6|]¤E E {E_EE:z ol

Einstein
s+ +q4 421* ^ll7l Îolq +Al= +E}rll= l3B.8a^l e=el q4l 4l+e+ ¤a^l?J + ?l+. +d 13B.r0^lr+ 13B.r3
(s-zeatfl? Eq 13C(13C.s^l)ql^J +E6J +*!+ ¤3 u-+ 49 ol¤-6lq 4 olgE +El E ds.s.E trl-94 ?ol 44
gHl4e qL u+.
C*o14.
^lel =EqI
DF
,- RT +o1 Zl+e ++LJ E+ +aJ (138.12) u = zDF/RT
olgg E4^l7l= c(olge-l E z'DF'

¤zlrl rE dd 4a +e--E )" - zuF
RT
(138.14)
B)"IH, D|
o1g6EE +& 4l+trHE 138.3). 4zl*
^1l7l7l
e"J ¤-"1 +ql^J 6J olgE ]r+ +qg s=u¤ol4(13B.8b) 4I olqî Ai=v*)"*+v-1.-E ol+6tE ++ E dEqql +6J trI
ol¤+ ezEq -J¤. ts=+. trl4^J lEel olgql zlaNzlS a; +4 eg Nernst-Einstein A.!g gg + 9t+.
$ Noezeol{, Nor=FE +41= ol+61-E zFsl S4. "l ss+
Ao^__(v*z1D*+v_zlD)# Nernsr-Einsrein
^l
(138.15)
rel + +4lE 13B.12^lql B-l. eE tt4lal+E ++4 Ae
trIl^lg grll ¤c}.
"l ^lg dq r +A Ar+.
Einstein ole" of{ ol$.el +4} 4l+E a
u- zDF Einsrein EZIÎ (138.13) a6h= rll "1¤-¤4. :_42 olg q& _Eg¤. oleo 6J dtr tr
RT
4+qlg ol+84.
E 138.3 298 Koll,(lel +tt 4l+ D/(to-n m2s-r) *

941 *9 Ezt +*E 49 ol9
dltl +q r, 4.05 K* t.96 Br- 2.08
Hl4l +q r, 2.r3 H* 9.3r cl- 2.03
E +E 1.055 Na* 1.33 I_ 2.05

=?-l4I
E +E H,O 2.26 oH- s.03
g ,(lE+
e. -4.o1
--1 -1 0.52t6
=O
. zlE Aql rl V*9 il5ol ++Elq 9lq

s20 13
=xF=q
ffi
=s-d7]lLJ=
D r. .-I^llE d^JE= gE t}+ql q?+ a}i.Jtr}. tr s. olgE *i{l q-{4 HJrl+ +'l]s}E ?16ll^l :1 716}q}4 H}
a 2. Kohlrauschel E4q E6IE tl d6le9 5 dEtrE'r-oia xlEE_4
=4.
9 xll#*ql tr+.+ E++. tr 6. E+ql^Jq oJCzI9 te. olE"s= Grctthuss 0llTlLl=_e__e.
tr 3. ol8el ollel H=lq E6IE }.szl 0ol q= +qlql ¤HB + el+.
g ==J4tr= 4 ols59 7lq= il6J ar+ gq.
^lE dtr - 7. olgE ol-EE= r +qI E dtr trel ¤+qq, Einstein s4l
a 4. EE +49 TJzl4 zl+qq Ele ^lalqol "*EZl g trilg 49 E6ll^J :a qÎ 4l+e+ s+gtrI.
44o14.
=e-d^l=
,A-lzl
ci e. ,\l
-1 +4 4Ha
;f o 9_E
"qitlg acE fl = flugf^tRr llL L+
oC cC
o--'l T3B.,2
dq-q rc=GllA, G= l/R ol

zlai ---1 138.3
E d++ A^= rclc zlo-1

ol 13B.4
KohlrauschE Hzl A = A" -K c''' d'H^l 13B.5

olgg +84 olfel Hzl A",,= v). + v-)"- ++ Hzl r38.6
Stokes9 Bzl F'ir.ou, =fs,f =67qa r3B..7
s+ +q s=ulE uE C9 13B.8b
ol¤. olEo E u= zel6fi4a Stokes9 Bzl zlC 138.9
dF-E-e+ olEE ). = zuF 138.10
E dEEe+ olEE A"n = (z*u*v*+ z-u-v-)F 138.11a
s+ +e s= Df IRT r:. "JHlpkEB) 6J L3B.t2

Einstein +4141 u= zDF IRT 138.13
Nernst-Einstein $414 Ai,= Q _zjD _ + v _z.D -XF7RI) 138.15

E4 13C trJ$
zlg4 4c¤. g.t"lq, "l +e +zI I molol qÎ r+

+ae_l
> ol EEJE u[+= olB
dql^l 6|= Hl-sa "Je- +eq slE trlHl¤ Hsrle+ ?JE+.=
Elet HJt E7l, 8i.ll l1EE, :1alr. Eil7l + 5el ar-loll,'.l gclLl.=
dw--4pol+. fl¤ x* x+dx EIE iilQl¤ {+ +
E+tr|=E +tle ?Je flqt H-ttE +E= ^lolql^lE
=8:drl. *4 ?ol +e}8 + ?l+.
> 84fl 7[E o1t
ExtLl olEEe qr{^-l Eg-d EE= LIE}4a1r e}cl. d1t= 1t(x + dr) - lt(x) - dx dx
T,P
> gs,Et qHl rEl trl+^l dr"JA olF6I= 4dql +Hlq= E J alEll ++
"Jg
0l EEoil^1= PH(EE 13A)r+ EE 13Bofl^l ¤EEl E+ +q
4 ?"1 'i4H + 9l+.
tralE Ee_l= eEg aolq. 0l Er_10il^1= EEI El¤l tr18!¤E
T]ILJE 0l8-lq rHl4 HslE HJEI= E-g a0lq(EE sA). olrlE d1t
dw dx
troil^JtsEE 17D0il^l ¤Eg%r8 ?gE gtrrt*HE E4l4 Ax T,P
E9s ol8g Aolq.

ql-J e(qzl^l= olag .rE +4U+)g EsH^l d-r"JE ol
E"¤ 4l B6|]zl= oJ$ dw*=-rdrol4. dwgl +6J ol +
ulna|fl sI+ qfl¤E +lilql ++ z!&z!Y lmol9 +zlql
^lg
rill +ql,rJ *¤ol q4IqBlE- cee. ^ll
zlill, elzll, :z4l
TIzl +dqlî rag + 9l+. a4e gqqlzi +dq^l= g 4Ls" 6I= +s. e4 'Jr+a 6il4$ + flsq, r7l6}q "l E
qqlE z$zl9 ol-e"+:ilE +71 Alr3g E-Z+ E=
6l.{ SIE E+4 gg r}s=4 ?"1 44Ur|.
gEe+ "J4"1 "JCR ?* ciuus glHzl +i= E= aol+.
d1t
E {l %}H* 44l$g E"46}E E¤9 +r}-g ^J46Je_e&] dx T,P
gE-+4 e t8e{l (13c.2)
* ¤99 E"E HEI¤ +4q= "lE HIA^lg "JE= 4"14.
,jlrl %IHe +^lg "J¤E Ie +4C olE" E4l-q el6ll^l tszl¤ p++ ElHf¤E ulB ot4E ,Jq +E dzll Eg EE
+zfl6}zl ?+=tr+. E{¤"] +qI qfl¤E HlRg ul4 44zI
"Jqt+r H= Hq E4lqs+4 r+A"lq. ol ¤tr-g zllzBzlgl g6ll^J QlEEirlTl-3lqlE EIBJ= a
ol Eqql^J. l3Aoll^J ¤B+ Fick9 +&ql St zllr$zl
=
6J qlEql +EI+= zl-¤4 EEql E46L+.
g ols-"olq qel 4E¤ +E6I4l q=ql ol H4g ¤Et1"
rf.<l Azflalfl r-l-q=r+ ?JL+. +AE ¤*EszI a"J *q4 +ql^J= El+ slql¤ol F=
p"+RT lnaol4. *.4"1 t"J6}r(l ?*g
"|]= 9E"EzI +lilql
/(g"Jol i)--off ricxg rlt1H^t tg"Jot +l (13c.1a) E=,6Frs ol gq+4 6Jg'I¤-r+ z-"1 448 + ?14.
ol
^lql^l
ne- g-EJol f
"J+;, Ds e}& 4l++. +*g ,cI
(dp /dx)r,p=d(p" +RTln o)ldx
tql +z}q Ea=Jolq cE 444E aol E4B rllz} R7

/ DIna \ (13C.3a)
=r-"E
El4. t:c.taalg Avogadro ^J+s ++H trl+4 ?"1 ¤4. '={#')
\ ,t T,p [-r,J,,
:-off Fickg ritlH4l
*"4"1 ol^J4"J Ell= aZ E E6E c/c.B HI¤ + flgq, 4q
/(EAe}1 tEtraJl (13c.1b)
ol 6-Jg r+s=r+ ?"1 448 + gl+.
^J
dln y/dx= (1ly)($16r1
13C.1 Eqtrt4 +E ( Rrr &\

lF=-RT t_l atn(rtr") ) (13C.3b)
\.dx) ' Ia;,J,,,
"JA+ gEe+ Sq 6lqlrJ zlg4 4¤q q4 B6flzl= 3l
T,p
4 ul_s+ "J3 ciuus .llHzl EE+e+ etrHEq 3D). ol 4+, ol

^lql^J
cE E*lEolr" c"E sf Eo E(l mol dm-:)olr1.
522 13 Exl=E-
GE@ EqErqflEaht
+efl E7t c=co*crroll tr].?+^l dl dB4 o e HeL4
Eo xtTl E.71 13C.1 +e9 *:E.zl c(x)-cod,//91 trl+ s=
r. ^J46lzI. coE x=0oll^19 tEtrI. flzl rollrlE gq 4o + zl+Et+4 + alt*+. o gqql4 eg +44=
q4 E-$ +4.11= !g +6tr" x=04 x=1.0cmgl^J9 4¤- +6}ot+.
ll.Id=! th
"l Eg 4lÎ6lq4. T=298Kql^J co= 1.0mol dm-3olir"
cr - l0mol dm-3 m-tol4.
rHEArEr ol Eg l3c3b^Jg "l+611^l +6lloF olq, E+ gEqt4 ee qq Hql^J dxll E44 'J4 Hli6}rll 4L+
r],t1 4-5 aclar+El +61lot oJ+.
fll EtE z\&zl}- trl-s,=r+ +L+. ill zt+ol ol dA4 Cr+ +¤g ol+q "IaLH 8d Ezlz}
"JCtl A+ tF4E '$.+ +q'g +4+rll q= aol+. ol d
(#),,=(ry),.=o a4 e4 dd zlE 4L+ e Îolel +Bg rEj6lq Fickg
9& xllr$zlg +EB + fleq, +,|l 4l+= ,llillE Ce$
tr+4^J 13c3b^lql E6ll^J gEqL4 ,fl9 r+s-l} ?"1 ¤4. g+^la + fl+.
(dcldxlro= q, c = co+ d,x
aRT
"=-+(*) T,P
cn ax @ Fck9qtfl1H=t
x - oollrlE,
5s zlg.z14l zl"JE_l= +?*e gol 49 aLB ar ^lA Eg}ql
E46l+ EA=J¤ :z ulole+ ^lA zf,le tr Llb a"l
Ezl-.el
(l0moldm-' m-' )x(8.3 145 |K-' mol-' )x(298K) 4. ol +=Jg Eq t3AE zlillE +4}ql^l ^l-e"¤I a4 +ÎqI
lIr-"ld- "
,JBq q+ E+ 44 se+ +fl^le + 9l+.
N
= -2.5x100 I--' mol-' E4l 1 E# 44 o e olsooli EzlE +%hg 44q= ^l

+qE+El 4E qlql fl= Ezl¤g ar rl1l Eqlql "l +
sa,t
+ -25kN mol-1o14. x= 1.0cm= 1.0x to-2moll ql6il^JE HI g. d+ Eltr6J 4,o14. + +i{ sArA ?lgl Eqil= E4_E=3
++ 4l4}g alH -z:kN mol-rol +g+. C}- "l +g f,tr+6J A"l4?lillql^Je+= 94 "l Egql^l=
# gq +ErI +4+= 4e. Bol 94e_-e{-r4e_-tr) _E= +e Ezlzl t:s zl9zl. tr+E+ olE6l] LlleJTl-"s q
+s"ql{- *"Jull, olag LoETl gEz- etr ?zlal{ ui ,'l+C ol +g E"4d}} *¤ tsziE E
"J6JE +=+g Htrt)
+^l +eol ol 7l|}4 Eql el6ll,<J $geE olE"6[48 a*(++l= E)g sLtAcTl gtrt. +*g ol tE a4 are 4
a6&g 44421 trllEol+. ln(c/cJ9 tl&21 l ut(co+ax) b aol+.
e-E{e--e e++ z}"Izloe.(rfl 13C.1) ol gEqL4 (E4*)=sc
=
E9 =zl* xzl frzlz;$a ea++.
cJAl2 E+ +qg +4q= ^l
tsE, c 8¤ Eztql 4L+61-= da4 +Fq(E'J)g 'F--(Rrtc)dctdx
olQ(13c.3b^l). +a EzlE r +qql Hlql6l+ d¤ zlaJq
gE:st
olol g grll ¤4. zl'Jqg E +98 ++rliB Nr6olq,F trl]
o-
)l=)l "l
eq q+ B4zl* dl+E^J 'trla ^Jir+a +q. ol + eol
+¤g olE trll, ¤-4 Ezl-b jL+ +qg zlzlt- szlolzll ¤
Kil
{0
Q{Gatx.l al rr
d--- Er, +.E14^1,
glil, x
No.r, = -+s ot4rJ, -# = L* = -+Y*
:dE gel PszI +4+= 4,* EzlE +
fal 13C.1 gqq4 Jlnc/dx=-(1/c)dc/dxoll Hle{Elct trfzl^l ol RINo=;6o1+.
ol E. t,-5.7l3 gqee+H EET| gg gse_eE^l- olE^l7lq, ^lql^-l
EET l |'g+-e. a7 17 l 4to ldtrt.
E *.Jr+ +E+7!*alol !e $Qlolzl ollE"l4.
=7
13C +tl 523
E4t 3 +4EAB
ol s+
+ E s00kN mol-1014. "l gqq4 6Jg +qE ¤4 uHzI
+qql +qL 49 +%Lql ++ ^lql Bq+E q-94 94, ol q+ql +d"l az}Exl *b aol+.
ee 49 Eril g+.
1Ed=J)=sc=- +*,---+Y* 13C.2 +tl^l

ol {g Fick9 x-llrHzl, l3c.lb^14 +ag Eolq, +elol +
E_ 7]$-71"il Hlql6J+. ol kTfy q& 4l+ oe+ F"JaJ +&e +e(E= E"-14 de)el H"J* bE EEE S.ol]
^lE #4. ¤zl^l= Ezl-el +tlg zlzl:t- ¤B6Izl"J "l$"l4 I
a oE^J olag ule. Stokes-Einstein E4l4lol+.
Ee+ Ag 844 CeE$ +tlqlE H]+6IAI 4+^lA + 9l
KT
D_ -r Stokes-Einstein$Zl4 (13C.4a) trI.
(a) Et q+t
*41^l +E /= AC zlillql t* Stokes S
+iilel da¤. Eq 6l-= ql ol+q= 7l* +e6J ^lel 6I+
Stokes-Einstein
4(Eq l3B)ol4r d+ +ill qq}4 e+= 0l+6}0l +ae. t qtHg qL +E +E ^l+ Hr4gg- E+.J *E= zlzla_
+ gltrI ol Hzlql E6Its HlzlE a9 7¤ 9"Jol9 a+ d +4.11= alol4. e. 4zl ?*zl"J ol 4¤-'Fick9 I
C zlaJ{9 =-zlE f-6nrtaolH, ol4& nc.qaal.ll Bq+B =4ql=
& xllzBzl'ol=|trE qL{. "l q&!.$ Fick9 xllrHzlsE+
+*4 ,J8 Stokes-Einstein gAI ¤+.
^lg El +Eg + 9l+.
o-!- 6TEna
Stokes-Einsteinal (13C.4b)
ol 49 qt} 41+e+ +i{Eq}4 H}zlEol aoJ dCE ^t t9 +4149 Holz} Aola r+q x+/ rlol9 +41= *ts B]il al
olE +!lE +4']]= Dzl n{l HlHlqlEtg qql^14 E s=g ¤*e_E Eqzl-E "J"J"l9 ¤s *=J¤.,rj4rall Ez|
^l_oE^l
(re 13C.2).
=+.
qg g}& 4l+e+ gEqL4 6Jel ++E ++ql= al s=-(D/c) +D,'l, Al oa! vl,
-rrct
'JOI, A
dctdx= gg + gl4. ol +E E" E zl¤zlts l3c.:b^lg HI A=J J.-
^l
+q ,{^J dcldx=-cfllRTtr +qg + fl-g-q, r46}q ol g
+ +qol rl-e=$ *"1 5|4.
r Dn
-RT
c (13C.5)
x+ I
- x
ol llg ol+6IH gi+ +q4 +4I Al+el +A aIlE+q
gqql4 eg +Ag + 9l+. lg 13C.2 Efe EEJo_eq !E +aJe # tsEE gq(g+)
g_sg
o_a+Ei Fe-Fr+'*a Bg(g-)oe LI7l"= +B?tE
ilet,Jtrl..=o19=
zt=JEt q 13C.1
qlolzl ¤ql E4l 1 SS o}+e_E+q Eqs= g"J"IE"il zlqlq= ¤

a4 2s.cql^J +& awz| s.ox16-e^zr-rol
Ezlg g+ +qol r.opms,*.tr}. l3c.s^lg r-sRTtD
+ ?IE dE +E Hq¤
E g+q ++qE ++g /rol4r 6IH ¤+ql Eqs= "J"Jol
_E Hh+q^J ol+6lH 6llB6l+ gq+4 flol rle=$ pol
g+. 9 4s= IAol4.:a?-l6}q g+e_E+qel +=*ql 7l"Jq=
¤* "JE E-bE 6zl-&3 trl^.ql=4 tr"] 84.
(1.0x10-6 ms-' ;x18.3 145 JK-r mol-'
F--
5.0x1 m s
)x(298K)
(ar)= I,A=Tt,
N [A',J, N
= 5.0xl0s f m-'mol-' _q- +Eg E6ll^J. oJ ojujolzl g44z}4, ol +¤. ¤L6]|
52t* 13 .=rF=elEE
4zl.ts +*3 /ôl4a 6l-E ae bp-.lql E6l]^l +¤.

^l"l c tr]TtrI
Bg aol+.
(a.) Io oAl
--
Iaj-
E---{
o - =
ui
jo itlf
*E +E= ol +*g *-E= Ala^lzlzl ullE"l+. q-+^l B Tlrl
+ "JE ds t-=- Sffi-o- trig4 *"1 ¤4.
ge.l +E
(#)..( dt ). - Ir- I*
dc dc
dt ?lil, x
EJ/rlz +*r+ rg 13c.3 q{t^loll E6tE Ee g5E E+el(71=717|'3?.! B9)= q^8,

zl97l
Îol9 *.r
+41 trllE x7lE7l7l94Prt =Je iilg^lalr ul.trl-.
Fick9 411Bzl(4 r:c.lb)ql el6IE z,I +=*g +& al+e+ ¤
+ Eql^lel }-E z1&zl$ zlzlt_ +ElE + 914. 6lrll H6J+. ol 4+=¤ 7zll4 o + r+-q-r+ pol se|$ f
J= -D(dc/dx)
el+.
I'- I R_ ,(*) . "(*). =,{(#).-(*),} ol {$ol "J"J *ql^JHre 13ffq1^l rI"J *)

EoE9 trIE H3rl7I "J"l qq, ql"J *ol
^lzlql -{r
¤+ g+ zl&zl(+Eq I tE iH?Jzlrll 94. 'lo
¤zlrJ (DciEx)1g Hql^Jel Rr
6J¤ +¤-ol ¤-"J *(*g *)"il^l= *.Eg
¤* S_=4 Eql^lel \-+ zl$z\
rlol
zL Ee+)olr. (DclDx)*.$
^lrJql -
IU
tr+= HsIrI$"I 94, +g *ol q4+A+. olrlj
4. ol + Eql^JE +E z)&zl:- ¤+ +dql^JE *iE 7l-g

zl (dctdx),4 *E zl&zl9 tz} E++(*:EE 2zI E-6J+) {$ol 0olE *.sz} ^lz}ql tr}+ H6}zl ?*=+.
d2ctd*z zlzla- +ElB + gt+. ¤+ +ceEPq Hzlzl9
4"-l= +/olq, E+4^J ++r+ ?9 al"l ^JBqL+. +&^le +E EEe] f$$g S."ll4E zI¤4 A6Jg +61
4= {+4 z||'JS +^l++ 4"14r E + 9l+.
('). - (#),
{(*),. +#}
= -
{( *), - i*,} =,#
ol +4lE +?d= il¤ +EI.ll= Bq+H q+r+ ae
g tsrtl ¤+.
^lql ^l *ETI +a ¤qql^l d¤4sE H++H
=-e =
c-co-axo14. &cld*=Ool 9:J" l3c.64lql 4+^l }cldt-}
"l g+. oltrI= tL+ elg F"ll^J gqEqs= "J4 +=

(d c lO x)
- (d c /0 xl, = I (02 c ld x2\
^
I,_ I
d'c
= DI 12
+ +¤- F6ll^l ¤44zlE "Jol eoI^J ol gqg *-Ezl
"Je6}rll +zlgtrH:.fl r:C.+a). "JB E7l- c-cr-if\l
R
ox Eo
,'l+ Hg {lE PclEt' _-Fl gq ,'l+^J dctdt=-Dpl 4

E4l 3 dg +%F.il +$ {4 +Esl ^lZI .el=g +qq=
4-lr+E A* 4. olullE ¤44zl= "Jol Eqe_= oJE4 tlzl qEql
(rH l3c.4b) B+ "JE Eo E7I Ai++.
99 "Izl"J !g }-E Hflgg +e}'|]= ^lql -+q= rhS I
g ^Jdl^lzlfl rJ-o-=4 ee +tj^lg Eg + ?l+.
*=o# +1t^l (13C.6) u

Jo
ol qtlql el6l-ts }-E Hq¤g EoE9 4?-lql Ell6J +E

(a) (b)
(4+61 "J6tH 2zI E6J+)ql Hlql6J+ uJoj :-oEzf aJ f,ta 9{il

e+q += tr-dE ;!46}4l E6iH *-EzI ^laql q-+ #4 rB 3c.41 ,.Et:d q 1 3c20ll^1 +{EEt F U?' (a) dE EE 7l37l,
(b) E=dE Ei7lz7l.
13C EJtl 525
(b) E]l+ +tt ZttrJ-d 0{l 13C.3

E!l+= +ill ¤EE 4^14 ¤+"14. "l 4CC Ezl-Eol f,4l bEzt +g +ZI gqql^l= c=co-crxgl lrl4 d¤4s
$$ zflp4 o + olf6|= E&r+= E}|s4olr+. rel+ tr. A4'6I¤ DclDx= -azl ¤trt. 4FzI $E- u-tr aE+
'11+
"ll zl"Jfli +=*e +&4 Hli+ %rB_" e 6114$ + 9i+. E t3c.s^lql el6ll^l dctdt-au7l B a"lq. "lqE ¤+
e-l g+ Hg 86il^J g=lE"lzlE olol eE+ +g E
EE.EE EEI. 6il^l gel4zlE "JE+ g|-tr, +E7l d¤4etr H6I
g.E 4&ql^le+ 4-ol Ar E"Jql AE E"46L=: "J,Jolg HoJ
{ $&"1 Szl oll$ql ¤+ ?}E }-ETl G.7l6J+. "J"J
a-0.010mo1 dm-3 m-rolA, u=*1.0mm rrol+H +q-r+
++3 ^J4aFbrll, {zlrJE "l **ol 4E u-tr_
_6== 4+
?Je 4+71Lfg 4o14.
sEol+.
EI! 1 EE Hq¤g ¤E +%hg zlzlt- +4U4. $ = tO.OrOmoldm-3 m-r)x(1.0x10-3 ms-r)
q&^lg +ElRg trlle+ eol 49. rl"l CB6J+. = 1.0x10-s moldm-'s-'
Dc _ ,lr,.onu- /*,.onu I vo E7l 10 pmoldm-3 s-19 +E--e. +rI++.

dt- I
q7l^J /'.on,4 /*,.onuS ?+?+ tri1+ql e-l6ll^J ¤+e] g+gE

EqTI= +=J4 sE4e-e +s- +=J"ltrl. q.4I44+zt'J"l "J"lB uI= 6J ¤qql^lE AiI t-E
tr,JAIZdE +*E 4l4I H+= + s4E 6Je-e. +48 + 9leq, olag +4U a
ol +94 ag guEl +tl^lol+.
ar E"Jgl 44 ult'Jql 9ir El+^J +4 AuLt qlql fl= "J
tsolEe d+ ¤+q Eg E"46J4 6I%r. Eql^lE +bEE Dc - d'c dc
-<- = l)=----; -l.t=- guJ+ qtl^l (13C.e)
alfl :z Hg Fr+61+ Ee+g cAuLtol4. 'q+ +=+' dt dx" dx
'4I
g ol Ee+g B+Hq H"lq rlt are. +b zl"l+. +qI4"J Hql^l r.el6}]o} 6J E t ztzl +,qo.J 4¤¤ "J"J
olE +E7t HI* trIEql E6J + 9l+= 4014. r3c.e^lql+
t _ cAuLt
/.on,,= _
cu tt|+¤ +aJ (13C.7)
ALt =
HI¤¤ _E6J^l7lE(Eq lsBql^l ¤¤+ 4,o14) HI*4 E+4I
¤+q g+ Hql^19 E"E(cJeI e_=+ql^J9 bE(c*)= ¤ 4 .11+= El4l "Je7l= 4lql 4+^l?J + 9l= "]|+ _a44
oJ ulE ,JA^lg gg + gl4.
s +dql^Jg EoE cog= zlzlr, +49 + gl+. "lqql 49 slo,i +t}el HI+
E=. ¤al6l4+ E= ^Jill gs"6|= EB¤.
^lls 49 4-flg
cn=co.*,(#) ct=co-*,(*) ,JE= ql g+g+.
¤zlrl li} E*+= ¤+ +Cql^JE ate-s ++B + 9l+. (c) 4$*l$ 6}|
tr+{^J 13c.7^lql e-l6]|^J q-q-l} ee Ar+= Eg + 9itr1.
4tlzl(r:c.6)g taq Sal]rJ 2zloll ^ltql +6ll^J rii?l
Hlczlol4. Et+^J
J=ct
"l+ "l ^lel 6l]E +6IelH +a E=ql
/a,.on" - /o..onu = (ca - c* r, = -,(*)},- {,,- +,( *)}, ++ a Al v4 24le+ ^lz}E=ql +6J zzl zz3 rzHz| 9e
{.. 6I+.
=-[P), qlE^J Htqel Holz} Aol:r' ql+61 +g Hl49l E"l R
\oxl r
4 qlr" Hlqlql ¤B +ol 9l4r ^J46IZI. utqlsE+El
EIl 3
bEE ¤n Hqg 9 EolE rE 44Bc|. r=0oJ trll N,rllel dill +e oJEJolzl-
ol pffi
+al lql^J +E6J r-o E Hq¤-ql +qI -+q+ x=OoJ +lilel yz$(dol Ael)ql glqr ^J461.=tr11, olag HL
^lql E z4olzls_ ¤14. :aqr + aAl z?Jz (1) -b-E= q
H '-l¤4 Ae Ar+= Eg + 9l+. =zl
L *ql^lr+ +6J6]]ot 6Iq E (2) dill "J'Jol EeeJ(E +)c
Dc IEc) 6Jd; rzo(= No/Na)ol g"l"t ++= + gqH +
0t
= -[a;J' LH+ (13C.8)
=a_e_E+q
gl4. olel6J aa 6lql^J= +4}^lel 6]17I q+4 a.ol s4.
526 13 Erl==el-
9l+. E ol6]]i$ ol+6lq ge+ *t

^lz} Fq}91 ¤-¤ol
2.5
0.05
6l] +A B+ H+lE AI4I6J +E 9l+
2
0.1
3, 5 ot ^l2J =)l q trJE Egl 4ltt

c
E
Ltj
0.3
l-
E9 x9 ¤+,<l (x)E 4l4I6LejH trc.toal9 ol*at{ "J"J
lo
olE re_I x+dx,<|ololl,<J ga6J q¤ gE_ p(x)E ++'H=
1.0
^l
0.5
g +6}loF qI+. +,
0
0.5 (x) = xr
0 1
71e,l,x/xo
1.5 2
Jf k)dx
f.al 13C.s Etrol qtqTl^1461.=EE ?l+sl te reg. *doil Dt,J E4l 1 qE I'JEE +4.{E ^l
I E,t.lElol ?19q, x6= {4 Dt}'/20 ltrf.
=0 flzl xoil,! HolzlAolr +4171dr"J ¤+Pul aar+ql E
q gl= $zl4= ol +rlqlq-r +lile+ pil^J9 bE c
^lrJ
c(x,t)= q^l (13C.10)
e| Avogadro tF#E EaJ 4oltrt. - N(ar)=c(ar)lsoadxol4.
#i""-/t4Dt ^|fl
1
ol flzle+ Eo EE 13C.10^l o +
^l4ql^JE +48 + 9l+. tr+
olag *q zld Bq _HE olaol 6}l"Jg q-oJg + ?l 4^J dill E¤*ol no"J 4*, ol B+ "Jql^l "J"JolE Bd
^lql or el^=$ trfe-Erl aq.
4.:zH 13c.s= ¤4 tol* ^l4ql^JE EoE EE E"&3 +
4U a-" +.<J, |:Ez| El4^l +"J6Ir1l q4b aolg EE6I n9
-t.. o\ _
L\^,.'- ^-x2/4}t
,ll+{L]]r 9l+. A(nDt)l:.
q& "JA!$ E 6l+e-l 3z]-fl 611= +eol zzl"ll Azls] P(x)dx =

Noc(x,f )Adx Ano
Noflo - nu A(nDt)t,)
a-r:l+ord,
¤ L"EE +Ei.ll= a++(qle^J +q}6l ¤:+4=.ql +g I
ifl+r r +.tl ¤%I Bq?-1. tr]]go} La$=4*). oltrllE +E
1/J
-. Dr ,
ox
(nDt)'tz -
EE. + trl]dolq, qlzlE r"J *gl^l= trl"gr+ e}ol ¤4.
EJAIZ ziEE 4lt}
c(r,t)=
#'',nr-"t4Dt
3^l? Crt (13C.11) ¤+ H+l= trI-34 Ag 4tsol+.
gHI4 Ag ElqL4_oE(E6J E4+4 4Ec.z
^Jill"+g Edq E" 6J
o +) gulEs ¤^JE
'l-= + ?lzlr} 4++E d* :z
alzl
I; . Gh r-*' ôt d*=
#r[ re-x') ôt o* - ,(+)"
g{ q +d-6}+.
q&^lE a]]g ole" al{ ql} 4l+= ¤e4 o e ACp + +, ¤+ E+1. +4,11. 49 ri+4 eg Aol ¤+.
fl4. s-ltItr BEql^J= qI ¤ol gfl E_^ll+ +q +.+g B
q^J "*g "Jel +,]| +ql He'l+ g
^lq +H^l -E^ll+ + k>=r(+) gE E9l [1^t.8] (13C.12)
E t.E Hs4¤ EqEl6t= 4,o14. oltrll= *d"l Eîl+E g
fl EgE+q +4199 4zlEtrll, :a +E= 4¤+ 44l LrJ
$ zlzlt_ qt}4g Eq^J ,ll4}B + glsq r46}q D= 4 +* H+lE Hl+o.J 4l{Is_E +6J + 9l
c6J + 9l+. E 4E 'JHql^J= aA^lA +4 4"+ "J+ql _o q, r+s=r+
=-¤t-!Ifrl
^]17+ql
¤ol ¤4.
I zloi? +._q4 +r}lE L,6r_ 4"_19 s.,<1gg- E6l]^l *&ol (xz)rtz=(2Dt)uz ;-r3E-xllE E?l [1xl-g] (13C.13a)
"JqLlrll 6J+. relr LoEE E_qq6}_r. ol A+9 q4i^lE
qle+ ¤a^l7lH q& 4+. +B + 9l+. qr} 4l+= E* ol49 ojujol$ol gaeE+q "J+ HJr6Je__tr. +4I6J + 9l
qlolzl &*Br+ NMR$ olga|1.! +Cg +E 9l+(Eq
"j'
g trll olEel q& aEE +44= +s+ rlol4(ololl= i'J
16C). t (r)= 0ol+). d¤zJe q& 4lf(D=5x t0-r0mrs-,)E *E
+&^lE 6ll= ol+6IH gelE +l,.lql.<Jel ojulol +E(E gEJolzI
"l${+ =-¤+-41#-E+l= rH r3c.6ql +$Q]
5 -e-E7| H.J* 419 gss+ eg E?-14 ^de)E +g + S.4. "l r4s= 4&ol ql+61 Lfl 4Aol?+= 49 -uq=
13C EJtt s27
-T_-T
U a¤-E Hl]6J HIB ++ sE4e=aq N_ a-sE +e+ g+_q_E
9 rt=ru-N* 4g.9 += qd+ %LBE +e+ e+ +
-2
<-1mm
? tAt _
N! N!
s-4 " - Arrtlrh!-lNl;nNJ
X
!-o
o + esJL+ Ezl-b 94o14 s=3__e_e 4214, q+^l 7l+-
-8 el A+ +gq ++= 2Nol g+. tr++^J !+ H+l ndZ ol*
<- 1nm ,il E *E P@A= ++!+ ?ol ¤4.
lLrs + ims 1s th 1d 1y
-10
-10 -6 -20 2 6 W N!
log(t/s)
P(nd) - - (N- N* )!NR !2N
2N
leJ 13c.6 D=5x10-10m2s-]E grJOlsl +EE-x1lE E?1. +tl -^s.u tr,J4lz stirling$ ol++ ol ZI44
1
golLl LeJ^l= ++d|frat.

=^l-= ^lq
ol
^lE
+Êl¤ +16ll^l *d :2.{+= +l++.
lnP = lnN!
+(+Eg 4q += ae 4+ql el6l]^l s6Jg "JezjTl +) - {ln(N - N* )!+ lnNo !+ lnzN }
+ aol4). ol q*q=r+ B3 stirung9 *,<l-=:4+^lA+

3zIgql^JE zll#-H+l= q+r+ ee g+. ^lql+
=-B+ ^lol
ln x! = ln(2n)tn + (x + *) ln x -x
(r2>u2
- (6Dt)rrz 3-u33-xilE E?l [3il-g] (r 3c.13b)
:1BlE r]-q=r+ ag ar+71-+g+.
I2N 2 E7JI qB}I{ I,}r{ lnp = -ln(zn)'t'zN + (N+ +lf" _i/tv

I rl\rrrf CD 7 ll t-: E
-l - -l r
+& qlT}q+g !+4 o E s-zl$ oiujolpol g eg-4 .l

+iv-r,rffi-]hN*
Bl H +zlolH^l ag +lilE+el dz}4 o-s ul4 4zlE ¤
ol +4lq^J ++4 Ag y++ulel pE E"J6l+ trll, :a olf+
{l"l4.r46}q "JuJolEol zl4 aE H}rll rrlt"l efl+ + grll E 4o14.
r ^846Iq BzI.rBlH t^l7J E"Jql +zl7l olrE"6l+ 44
Y tdtrzl E 4"14. rfl+ oJtrJolTt gfie++q "l"J# tr ,=*-+
qd 1l4ztlzl zli 4+ 4a otLltrl-. +l= %r-6}g :zullul-4
+ss.E "lag r.q6}H^l ¤s *4i 4q=,rh4ot 6J+.
rflE t-Nx/N=j-p r4r N*/N=]+p7I g+. oli$ Bq
E4lE ZI+61 6}zl +16]].<J $ulolE.g zld(x+) iH mpql ++ zlol 4¤-4 ?"1 14 prtrJq a E^lg+. d
^JqlrJXI ill e+ +E E Hlg e-E+ d9014, q+^J ol pE ql+61
gE6ir, epgolul g+e-E 6J Hql +l= Z4E E?ol a
r};. .$4a14. olal6J EBg lilll +4tE E3"l4l 6J+ 44. pzl olzlH zlzl ullEq q+r+ zt! $zllzi zl#a}4.
oJtrJolTi gae++El EA+
44q 7}9lg +Ee E4l+ ln p = -tn(Zn)tt
2
2N - (N+ 1) ln(* - lt) + N(p + *) ln(* - p)
4 $dg ol alol Al&g + 91tr1.,
-"
- N(p + *)ln(tr + +) - *lnN(p + *)
*E 13c.s 1ilfl ++E E4! 3 4f9 dzil

E]|EI
=J= EE
^lel ==oil 94"14 A¤¤ 7o+ ffi$ EoJ6IE_tr_, "*g e
s=E-- e__tr.
9E4oE Noel, g+ge NrE], -E-.J Nslel agg +ls{ ¤¤ +llRg s-trE Ag {21 q;5
trll e-=3--,
"-} t}"1 E a
Qa a121. El+^J gaeE+qel H+l= (Nn-Nr)dol4, ol+. . \/N=;ol g aol+. tr|4^J F < lol g 4o1g+ Q
n =Nn_ALqr. +sH ol Hglz} ndzl f]q. gq eg Bf dzHE ala 1it;lllzluJ TlollE ¤tr+.
E4l 1 +qd 4+ HflE olits +E9 4l4I ln(}t H):-lnz ! 2lt-2lt'+"'
+qd H+lE "Jszli agE Hll.J HlHe ql+61 ol.=-
"*ci.
ol4+ zJ4.6Ia +4 e4E 6iE(g^l-olEE t}îl+ q+
r Ed +qli]lel +zi¤ +d +aE E6l+ rilqE +ae Egg "lgts + ng Hoi+) rlg4 eC er+E eg + 9ltrl-.
fl+(Eq l7D).
s2s 13 ExF=E-
lnP = -ln(2rN)t'' zr +ln2N*' - z(N - l) 1t'z

+ D= Elt zjol de+ EE .<l{ 7afI. ¤+^lvJ + ?l+. rq
H +94 ?9 Einstein-Smoluchowski 4lg Eg + 9t+.
"JHq qE_rE f6LiE" N> 19 ol++4. :zElH,
2
N+r
e-2(
N-l )Il2 Ur-Zlt't-r)tt'? 2e-2N
p', D=* Einstein-Smoluchowskl l (13C.15)
P_ - -
2* 1znN1', (2nN)'/2 12nylrrz
zttrJEt ofl 13c.4

cJAl4 $Eg 4 agq ql+ ^l+g zlzlt- +4U+.
ol
zlf Np'zg +94 ?ol 4rl + + ?itri
sof ols-"I i
8.+ +ql^l olEg ql qI Hql rel zlE"J
s00pmtrJ#49 Ee+6J4-::. a;z;. rfl H D= 1.1 x 10.em2 rr
n=NR-N. olF +(tr_9 r:s9 oltiE +as-g +E_E) 13c.1s^l o e
/r = Ns/N-1/2
(2NR-N)'z _ (NR-NL)' n
2 +El 4+4 eg er+= eg + 9i+.
Np' 4N 4N 4N
T=-d'
(5ooxlo-'' m)'
gd o ++ElE al+ ol*. 448 ,= ndola,t^l7J Eqlql +l
" 2D m's-') ""
=l.lXl0-roS
2x(1.lxlo-n
+ egfl f|- N= tlrolg 4 Np'= n2l4l,l=r*l4td2ol ¤4. "l a r -Itopsolu|. rE t H EqI:"Is ql A4= .r.l{olp +
m{ Np'z9 pql +{} Bq+E +s=4 Ae ^l"l +g+. r s E"Jql= ol ol9ol * r x 10'0H EeHL4.
^lql
v2
2t
P( x t
fit
e
- x2 t l2td2
t^lg +AtE eB (13c.14)
Einstein-smoluchowski *41^1.9
"l^14"J Ezl
gt¤ q
r'l-l zI rI-zl rlzl-I rrt-zl rl-r] 7-|- rllr.|.+l zr)*L
,il!r if./1131=
-l-r.llrIr- ./1/\1,.1 -d'={ -r_1.=.,.1 /1 1-= al *Llul -6 '- ".1
13C.10^l(1i}+l +tlql +qI)4 13c.14^lol ,r]l-!-{ o + 4; rlol4. ol 49 E6J + HIfl qE.olzlrl Eq l3Aql^J ¤H
tr"lt 4g ol 4ltlql^l= oJEJolTI gd_o ++q qL +9- + g.d zlillE Ceg +q.llzlr ajc1. ! dtr? qt}q=
_trr{ ol=oot- + gljr" E zld^}E ¤+4"J E= dol o}H a tszl-9 B+ +E u,""*ol4a H n E EEE ?ol dE ¤t
EI+ gqd E¤+4 +lilql^J"J Ba¤ + 9l+r EllTl trtl zI+ qge+ e+r ^J46IH Einstein-Smoluchowski 4l D =
Eol+. ol + zlol "19+ pol $^.l.ai+= ^l-dg EÎg ql+ Id(dlt) = iLu^"unol zlx]l EzI gEE-9=tr+El gg
^l(Eq
6l $:3 +E Agol ++A HJ6Je__E #4xlE a44r 6|]4 13Ael 13A.e^1, D=!?tu^,*)r+ sd6l 9z16}Tll g+. + sd
g + 9l*g oJ^l{+ Lol4. Tlillel q{!e ¤t {r? fle"Jfi fl +ALe E*"141 a]]
13C.10^lr} 13C.14^lE + zl+# ul;lal.{ ol^ll +& 4l 4B + el+.
=s-d7t|E=
tr l. Eq-44 -d9 Ezl-E"l gqtrl 2$zlql q?+ 4l'il Qlesirl tr 3. Ettl l(rick9 4lzHzl)* t"E7l-+"J6I4l qal= 4¤4 A
ql EB6I3I= 6J¤- +4o e +Elu Lol4l E + gl+.
Îg4 aalg +eiL]]= 1o14.
A 2. EF +alg dC xl'Jflol gqql4 er+ rllf6fle q +Et A 4. El|+= 6e=+ill gEq QeJ96o14.
ttrI. tr 5. s& sB " oJ"JolEol .JdE AIe- E.+ = +48
=8ql
el6ll^l :a fld o e+El dal.4 o -s Elzl+ztE ¤^Jol4.
13C sj^t 529
=e-d^t=
,t-lzl
oe. ,r.l
-1 =^l
I --1 4Ha
Fick9 xlltHzl /(Ee*) =-Ddctdx 13C.1b
ae. ccalzl
---t -1 -1 6l
E
q=
-(dpldx)r., zl ol
'o--1 13C.2
Stokes-Einstein *4141 D =kTlf F= Ele xl6*q 13C.4a
s+ +q s=Df IRT 13C.s
+4I4 0cl0t = Dd'cldx2 lil-fl 13C.6
"JHlEl
q4l^l dc ldt = Ddl cldx' - udc ldx rzl-+l 13C.9
¤+ E+l x = Z(Dt ln)''2 lil-g q& t3c.t2

3-¤r-zilE H9l (l)''' = (2Dt)tt2 rzlg qÎ 13C.13a
(rz)trz - (6Dt)tt2 3il-+lE& 13C.13b
H9]E +E P(x,t) = (2t lnt)t') e-rrr"rail lil-fl +z+a a+ 13C.r4

Einstein- Smoluchowski 4] D=d2l2r lzl-?l+4IC Ag- 13C.1s
a
530 13 ErF=elffi
e4 13A gJET l^[el AU ¤E

== =ril
D13A.1 q-4I 4l+e+ dcszt gE "Jq, rqr zlrll $zl. zzl9l E+6I D13A2 7l4l ezlel :-"E_ zl$zls+q qBrll Fick9
^llrEzlol +9-:-zl
ol+= ez} f ¤E6lq4 ¤B4q+.
= =ql^l
Cd-\
a-i rr
Er3A.r(a)E d*ol l00g mol-'ol Lill oloJg-o 8zl.ll Bl aoo'CE- zl El3A.6(a) 298Kql^-l olg=-(Cv-=12.51K-' mol-r, o-0.36nm2)9 g dE
g6}flr}. ol ¤'zlgl4 zl$ 0.s0mm9 7H9 *flqq aoos*gl ¤*ol E= 4lt}6lq4.
285mg zJAalH4.ol e+6JEq +oo"c"ll,tl9
6rl $qg 4lt6lq4. Et3A.6(b) 298Kql^J ¤l1cu.*=20.8f 6-t mol-r, o-0.43nm2)9 ¤ dq.;
El3A.r(b) E d*ol 2009 mol-'oJ aill elql+q 8zl"ll Hl :oo"cE zI E 4lt}+q+.
¤6l.fl4. "l 8zl"tl4 zlB 0.s0mm9 +Bg Eflqq s00s+ql dz}"l l3A.l)E ol+6}q NeflzI
227 mg e^6|*.tr1 ol +oJE9 300"Cq^19 +zl Sqg 4{i6}q+.
813A.7(a) 273Kql^] Ne9 ¤ dtrtr +ail(s
: G \a\1^l= -rorLlq.
t'ld,tA
^l;- ---l^t-!
E13A2(a) +e $q4ql ¤ag *zl9l zl*9 E13A7(b) 278Kql^l N,9 ¤ dtrtr +cil(s l3A.l)= ol+6}q
"lzl9 zlAlzl E9 9lEr]l, N2Ez|
ar* ul-= +B¤- ¤i6l]^l ol tlt)lzl s2s ¤.?l ,r}iolqztrl! sq4E +ol I +5 YtE4g +6Iq+.
zl zscmil*el socmE ,-l1el7itr|. Qi (M=28.02g mol-')$ zlzla- +eg
¤Bg 95ol alflrlul ee Sq ztelzl +Ei+= cll +2szl3H,4. "l "l
El3A.8(a) ¤t gETl280KoJ Ar +ql^l &E z1&zl7I l0.sK m-'oJ
zl zlxllel g g"tg 4lÎ6Iq4. fle gqol E6IH fql u|+ E¤ +E
qel qqzl ++3 4l4I6Iq4. g ^l-E. dtrtr= 41416l^= ql gs+ qlolEl=
E EoJrl. rfl+ ol + a+ HElz}g+= {e;-q-5}{4. ¤6 Etra.:(a)'ll 44?14.
El3A-s(b) Bt eszt 2eOKoJ +i zl$zlz| 8.sK m-r
Er3A2(b) +e $q4q ¤?¤ *zl"ll 4+ *g $qE Ai'zl Eq 9l ^lE +ql^J $E
trlle-l qlqrl ++g 4l+l5lq4. I d-rE= 414}6l+ rjl $_e¤I qlolEl
brll, zl3 Bl¤ +Bg F6ll^l ol tlillzl l8.ss Eq},r}]ol4zlrl.l sq4l "J
E g+ Er3A.3O)ql +e+91tr1.
9 t"lzl 65.1cm_tr.BEl 42.rcmtr_.ilelr^t+. TlillE zlzla
+ee ¤Eg 9¤ol al$.rlq eg Eq =+9.-a+i
,J6t7t +4+= a23szl EH
ril El3A.e(a) 7J4ol l.0cmoJ 2+ +4* g X+ +z| 24mW K-r m-r
Îolql trlÊr.6-J
Q. ol ggq ee^g g e+g 4l4I6Iq+. "J 7l4l7| Sqgl+. 1.0m29 ol +g ¤l4^l %l-(zs"c)o e+El &
ulp(-r5"c)o e dEg9 4zl= 99 old +EE +6}qe+. ol g+¤g
E13A.3(a) 4* *ulz}3.0m3?l ? idol +^14 +E=6lq uJzlB 0.t0mm
-H_+^l 71 4 E ts"I"J.J el 4g-z]'zl gs6l4 - +?
E +Hol ^J44. "l ? iC "JE tl^ g-4ol sokpaolr .gETl2e8KfltrI Et3A.e(b) zJ4ol5.00cmoJ=q + +4+ N, zlzllz| 2.00m2
E eg gEql^l "l oJq"l 70kpaE BqzlE rll .<lzJol 9"I4 eqaL ^lolql
g ol s¤ F61l^l Iq-E/.6J +Izo.c)c-e_+El =qilq-.
4t
& *(0"c)otr dEqg 4zl
Er3A3(b) 4P *ulzi 22.0m3oJ *zl9l tlzlE 0.050mm9 +B"l ^8Ar+.
E gq old +EE +6Iq4. gs't} qlolEl= zlE. ¤ql^l aL"iHol-al
ol *zl ?I9 ¤e $4ol a¤-ql rzzkpaoln SszI2e3K9+E Ae g Et3A10(a) (i) 273K (ii) 2e8K, (iii) 1000Kql! *zl9 dCE= A1t4q4.
-E_ollrl ol $qol loskpatr BolzlE Ell
^lrJol 9"I4 ¤44lg4r o = 0.40nm2olJl M=29.0g mol-t-E +oI4.
E13A.r0(b) (i) 273K (ii) 2e8K, (iii) l000Kql,<l Hld 3zl4 dcEE alt}
E13A4(a) $4ol goPaol.::. S.E-zI sooKoJ ArTlllql+ 2.5mmx3.0-* H 6IqeI. o = 0.88nmz o e
olsl rzll s.Eg r-6^la+. lss f,Qloll ol s.E4 +=61+ er Ezl iE F-otel.
4l&6}q+. Et3A.t1(a) 273Kol],<l Ne9 A^JE Al+ +eil(s. t3A.l)= ol.$oll,r.l Nefl
$4"1 1u Paola e-Ezl. lsooKoJ ¤E zlill"ll4 3.5cmx4.0cm
El344(b) zlE +E +H4g +6l-o14.
Hol9 t4l s.E¤ L=^lA+. r0 s Eo.l9l ol .s.Erl +E6l+ He flzl-f El3A.11(b) 273Kql^l eiE dCE al+ +Ail(E l3A.I)¤: "l+ollrl "l
4l4i6}q+. EzlE += +H4g +6Iq+.
=
E13A.5(a) gETl 2o'Coltr ?Iqol (i) l.00Pa, (ii) lo0kPa, (iii) 10.0Mpa E13A.12(a) qtr e=*zl"ll 2.50mm zl$el E.r*+B"l E4 ll4. ol
'J n'9 +tI 4l+E 4lt}6}q4. o=0.36nm2o + *olz}. ulols +ql^l ¤-zl 491 E deJ:"I 260 g mol-,oll" +oorql\4 ?zl $E"l 0.835 paoJ
r.0bar m-,9 "J4 zl$zlzl9i+E +{lq E6'J zlillE E$$ 9olz} 941 az)lzl Eqfl+.z.ooh p9l ol azllel d*"1 9"l.4 ea6IA'-+?
urla El3A.t2(b) qH +=*zl.ll 3.00mm zlEE Eolt+Bol *4 ll4. ol
El3A"s(b) .gETI 20.Cola
$4ol (i) 100.0pa, (ii) loOkpa, (iii) 20.0Mpa 8zl 491 E EaJ"l 300 g mol-rolz 4soKql44 3zl $Hol 0.224PaoJ
"J eÊ +& 4l+E 4l&6}qa-}. oi=0.43run2o e F-oFI. ulols +q^J -r1illz[5qfl4.24.00h +q] ol ri-llg ¤=]ol 9"]4 ai6]a'-+?
r.20bar m-'9 $4 zl$zlzl!l+H +tlq EtiJ 7l4lE EE+ 9"IzI I
z.{ t-r}z
E+ s31
E4 138 o-4fl +oil^1q Exl

-
exll
==
D138.1 Eql^lE "Jczl ds qlzl'l¤¤ ¤B6I¤aI. ol 'll7}q+g qB D138.2 olgel +ill qq}4 tlzlE4 olg Hlzl+ ^]."19 il-= ¤B6Iq4.
,il +B6J f flel,g4r ql +ql^]= ge e .I.le++ olg Hlzl+ol zlxlirjl r +ill q+4 H]
zl$ol 44 + 9lE
"lf¤ ¤E6Iq4.
G^
L-l tl
El38.1(a) ZSrc"llrj Li*, Na*, "l K+gl +i olg dE-E= zJzJ 3.57 mS m2 mol-r, olQ. 2s"c9 Eql^19 r qt 4+¤ +6lq+.
5.0ImS m2 mol-r, P z.:smS m2 mol-'ol4. ol=iE olEoEE +6}qel Er3B.4(b) 2s"Cel++.1 +ql^l CH.COt "lg9 olEo EE 4.24x 10.8m2 s'
El38.1(b) ZS'C"llrl F, Cl-, 4 gr-9 E "l¤ dE-E= 7+7J S.vms m2 mol-r, v-'o14. 2s.cel Eql^lel r qÎ al+= +6Iq+.
7.635mS m2 mol-r, "l z.stmS m2 mol-'ol4. oIEEE +6Iq+.
"lEgl El38.5(a) EE dCE= 2o'Cql^l r.002cpola 3o'cql^] 0.797scpol4. d
Er3B.2(a) 2s"c4 ++"-4 +ql^J Epl ols9 oIFEE +A6iflqq CEql q"J gC+ qLJzl= +6Iq4.
7.e1 v-'o]fl4. E ol3 dE-E-E 4l{}6}q 4.
x l0-8 m2 s-' El3B.s(b) ++q ecE= 2o"Cql^l l.554cpolr 4o'Cql^l r.450cPol4.
E13B.2(b) 2s'Cel ++E +ql^-l ol..r'll-E{I olgE olEo EE 4.24x 10-8m2s-r acE.ql qlEl gcarlqlHzlE +6Iq4
v-,olB.+. g olg dtr tr= 4l&61q4.
Et3B.6(a) NaI, NaNOr, o{ AgNOr9 ?qi E dEE= zJzJ 12.69
Er3B.3(a) 2s'Cel ++._q +q^l nU. ol89 olSE= 7.9}xta-$m2s-r V-r "i tf.f+mS m2 mol-tol4(25'Cq,tl). ol
mS m2 mol-r, 12.16mS m2 mol-r,
ol4. ol +"1 +ql fl= + d+ zs.ovfl4. ol + d+ ¤--Erql^l Agrg E63 g dFtr= 9"1-*i 6JE 44E +6J E dE_E=
^lolE d+lzl-b
Tlelz| z.omm4H Ru. olgE *F 44"1 9"Izl 94lg+i
Î olg dtr trel
"19 F. qle__a +qd4.
8138.3(b) 2s'CE ++.+ +ql^-l Lr ol8'el oltiE= 4.01x 10-8m2 s-r V-r
ol$.trl. ol +"4 +ql fl= + d+ r}"l9 d9lil+ z+.0vfl4. ol + d+ E138.6(b) KF, KCH3COT' oi Mg(CH3COr)r9 ** g dEE= 44
l2.89mS m2 mol-r, 11.44mS m2 mol-r, oi tg.zsmS m2 mol-rolrk25"Cql,(-]).
Îol9 44zl5.0mm4$ "l "lgE s+ +qol
gulzl El4lL+?
ol -$E.9lrl MsF,9 +el E ,sEE= 9"t*?
El38.4(a) 2s'CE +8'-4 +ql^J NO; ols-$ olEo EE 7.40x 10-8m2 s-t V-r
E4 13C +tl
¤E Eîl
Dr3c.1 q1!4E gol qs= ol-,9¤ Efl+4se ¤¤6Iq+. Dr3c2 gEqI4 +lE *gg ¤B6Iq4. olag 4y zlsttzl dzll E
o+Efllg4r
G^
Jtr
El3C.1(a) Hld +ql^l Q Q E +xlE q& 4f 2.13x10-em2 rtol+. ol E13c.3(b) 2s"Cel +6ql^l Hro9 +& 4l+= 2.26xLa-em2 s-'o14. 3F
Ezlzl aJ EzI zIHHA ¤+ql^l E .J A*el= ,Jol)g Hq H= 'll= ? Q
^. +Î7I l.0cm9 *-¤#-x-ll*-H9l= 6l+ rll aq= ^lag +a6I
$"IzI%i9 g_s_614- +? q4.
^l*ol CCI4E q&
fle
El3C.1(b) +ql^l 4ltL 3.17x10-em, s-,o14. ol $zlz| E13C.4(a) H"lzi 5.0cm2oJ *a- t +lE E
s.Hql 20.0g9 ¤%lg ;r =4
* EzI zlE<Btl gFql^J E + a*E ?ol)9 Hq H= 4lE ¤"tz}* e Hfl+. ^ltol (i) l0s, (ii) 24h g4q
eH $l-8. ro cm
9 rlt"l gs-6}a-+? fl+q acE 4l+= o.386cpol4.
trlt ¤%I
qE ^l*g
*ql^19 ¤'J EalE E-r-" E= gulz} 9d:4i q^}g +Hl ,+aql
E13C2(a) 2s.Cel Hldl +ql^l QQ E Ezlz} l.Os Etloll olE6l-= el6il^]"J "Jqts+n 7iA6Iq, D=5.2r6x10-em2 s-'ol-tr E +9 aol=
+-zll*.-zl?le| zs"c9 E +ql^l ¤* Eztz} l.Os EoJQI olF6I= =-B +oJqs +l6}qq
+-zll#-4q= +6Iq+. =-¤ El3C.4(b) H"lzt r0.0cm2oJ .s,Hql ro.og9 a a E= I =zll aa r +l=
Er3C2(b) s6 sr:c.z(a)9l,tl ol
$fzlfol (i) 1.0mm, (ii) dl&_q_s 10s, (ii) 24h zl*g trll g4E Q Q E sE +l
'cfltrI. rlzJol (i)
r.0cmoJ zl$tlzl s+61+eel= ^lrJg=geg-tr.+q
Bt4 o e 9"14 941:*i
Ell -tr 5.0cm q= *ql^19 s q _= ExI9 5BE= 9"IzI qde+? +{}g
gH] r+aql el4^l"J "rqk}qr 7la6}q, D=4.05x10-em2 s'g ?lat¤
E13c.3(a) 2s'Cel ++ql^l qt 4l+= 6.73x l0=r0m2 srol
=+?9^9
3 *zlzl5.0mm9 +. dltl e9 4"lE FEI4e +l6}q+.
trI. ]-¤t-xll# H+lE 6F= ql eel= ^lrJ
=+3e
g +A6Iq+.
532 13 ExF=el-
E13C.5(a) .&eel +ETl ¤-zl9

'Jolql t6ll^J c(x)=60-or*ql
q4 de ql^J +co-e-tr Eqa+. l8'cg rll ro.ocm 4Eql^l +eql 4*6]+ ¤E
9-E AA6J+. coE:x=091^le.l tEol+.2s'CoJ ull rocm 4elql^] LoETI tr14 Bg +6Iq4.
*',8 E9d4E tocmei zocmglî *Aql ++6I= gq+4 E3 E"I El3C.7(a) 2s"Cel flE +ql^l CCl49 +& 4l+= 3.17x 10-em2 s-'o14.
7I El=zl {t6}q4 f,E +C sE 74144. cc[ $z[z[ 5.0 mme] *-¤J-zllB H+lE 6leJts g"]"Jt e?-]fl
El3c.s(b) +eq Eo E7I 8zl9 ?ol"il ¤6ll^.1 c(x)=co- Br*ltql q?+ ai L ^lrJol
tla
aJ4. colx=ooll^J9 +Eol+.2s"CoJ rll x=15cm aelql^l \,rzllcoe-
Bqd+E 8cm4 r6cmgl^l ¤:aq 4L+61-= gqq}4 6Jg gtrr7} El=
E13c.7(b) 2s"CE dl'$ +ql^l Irel +4I 4l+= 4.05x 10-em2 r' ol4. o c
zl 4l&6iq+. 6JE +d pE +6lq+. E +zl7| t.0cm9 6IqE g"I"Jql aqa!
=-¤+-4E-H9]E ^lrJol
*r
E13C.6(a) *¤9 *ETI 8z]9 ,Jolql ¤ullrl Gauss EE c(x)=6og-4"q1
E13C.8(a) 25"C4 +6ql^l ¤Zr EzI9 44I 4lt= 5.2x 10-t0m2 s' ola
tr14 H.JcI. coE x=091îE tEol+. 2o'Cql^l x=5.0cm 714ql^J tE EE 4CEE: t.00cpol4. ¤?Ezl9 +E HlzlE¤ +4I6Iq+.
zl )cooa trqd+E s.0cmgl^J +eq ++61-= ¤E+4 E3 gotz} Et3c.g(b) 2s'ce-l +6:q^l ExI9 q4I 4l+= 1.055x10-em2rt
94lr*r olr" EE ACE= r.00cpol4. =el4l EzI9 +_tr Hlzl+g +,tl6}q4.
E13C.6(b) ¤+ E13C.6(a)qrJe| E"J6J aAql^J +e9 *:ETI x= l0.0cm =E-lt
Ez1,t 1, EIlEel 3E
-=.6lxl ET.ll
o tl ---'l g/'ll
t13.1 ol +allq^]= +ql arEEgJqE Elql^.l trl +q 4I^ t13.2 Eq r4Dql^J E-olazl"J eltrl HI¤.el gcs| 9lHzlb "JHl^l
^F8.6Iq
7l- tr"+ +_e-E eHlEl= Egg aÎ6Il H ?zI 6Jtrl-. (a) .+CtEql S+ E,=RP(d lnk,/dr)-E +qd+. ar3s.oll rll6J 13B.2^ls_a+El gca+ qlq
v.7l ") 4Al 44=o\ 7+7+ c(x,f)=6(491=c^. (0<x<co). lfl1 c(0.f)=c.. al= g|.qLI* r-llqls .FSEI 4¤. 0l¤-E + ?ttrI= ag q."J6Ir, olq^l
(0<r<"")s +qe q(crei c,= r}+)"14. *tl!(r3c.6^l)g ¤q^l tE
"l 4¤- "l+6}q EE acEz[ ffia1- ee de]^l "e +q¤ qlel Eel
c(x,t)zl r+-sr+ ?"1 ?qtlg Eq4. gCa+ qLlzl$ gtr_ 9=g Lt44= {g +E6H4.
c(x,t) =co + (c, -- erf(6)}
co){1 ,to8 n - 1.3272(20-e t"C)-0.001053(20 -e t"C)2
n, Al"e + id5
q7lî {=xt(4Dt)l2olr+. ol erf(oE s-i} 6J+. relI. .r-oE c(x,f)
b 7lill,*e__e+El +i+tl_e_s^lql^l
+ol ¤+g ulle+ rJ"l gaql tE9 rzH ol gCsl ollulzlE gEq Q++E E^16Iq4.r,9 3s q=^dg ¤¤61
ss+El +tqq Eggzl qlEq +Elt+. 0) trzi Els+q EIE q trole1.
E E6|l^l eaI +ss Eqzlb aql Elr.B"JqI +t4 aE_ql rI4rJ
¤4 tolal ^lrJg da6}r 2e8Kql^l tlczl E+es +tq= a+
(D=2.10x 10-em2 s-')9 }.E u+gg :14o-e rel4. co=09-F- E c,E
tIAE Eql q6J *olls. 2.9x 10-{mol dm-34 ,JLla *o}4.
14
=vla
HJ8^-,E=
ol E4^ql^l='HI* +EE_: + Hl+ +E_ql +e ?lelE a dill Hl+ 4cq rIql ¤B ^J+E ztt} ollzl-q+g a
511^J
fll6J+. ElqI HI*e-l +E= *4zl a¤tr + 9l= aar==, ql "J6J4

q"J.J Hl* +E
^J+=4 ¤+^l7l= +L" ql dE4
aq "Jq, gE rql +rllel Eql E=61q, ol5 aa +4lE R^qts + 9l+.
=zll
$$ 4eq a¤6JsEr{l H}¤¤ 4.J+ +Eq "Jq+Zl 6J rac.r EEoe E=6h= ri] E!E; 14c.2 SEIE
+ 91tr1.
ll*D Anlrenius Al
1A s+-et HJSel 4s. rll+BE A+ H}SE +E tF+= Sszl-+olzlH ?zlaJ4.
ol Eqql^J= HI+ +EE CEql +6H^J ¤E6li1 r +A ol Eqql^J= dE4eE A46J + 9lE + + zll9 u}4"l
qE ol¤-6ll^J ol gE q= +41= +4.-ll= Arrhenius
%IH$$ 4zflop.z} ++. olq+ +A Ar+"il e-l6IE HI* + ^l',g
-E= Hl¤-E(A+ql q4^J= t'9.<J$7lzl)el r-" Ee+ 6ll%r- HI+ 42fla3 4o14.
ql a+q}'$E ,J{g +4.11 14D.1 HJE gE E=; 14D.2 Arrhenius EtalolElE 6ll^1
.gE ^Jfql E=++. "lBl6J e-l= ^_EE
a"l B4'ol4l +s= "lE Hla^lol+.

=
raa.r E!89 tlB *4; 14A.2 UEE +E
1t.;- HJB 0ll7[L!=
HI* +EE ¤+6tB HI+el 'ollzlt-16'g 01611614l qI, E

1I.B 4E4g HEI 6J ol 61]4 4eql^J HI+ !+Aql^l
"JqLt= "Jfle-l iHl*
+E H4g +44E ul+'Jd^le] 6ll='48 4+ Bzl',ol e"J +41 EI+)=¤ dzle. + ?t+ ol Eqql^J= ol zl-tr
q¤4l +E H4g
4a +4. ol H4e HI*ol ^14¤ +E "JE ^l4ql^Jel HI "ll7}q=e_E+q "l=qg + 9l= "JB
¤+=e-l +E= ql+61+ Ell ol+g f :lr, +E ^J+E +
g E"J 4o14. aHI¤-E=e +++ +E B4s-e. +49 +
A6l+ %lBg ++U+. ol Eqql^lE ol tL dllql Aa^l flsq, Hl+E '+.E- aA +41'9 zHH9 E"J6l4t+ E='A
+4+= ++6IzlEI ql+61 +++ 4E +E Hzl# J.+ + ^Jel zl{'ol+'Îd BB'E qL 6Iq¤ ol-$all.<J
ol aHI¤# aEl6iq d4l4"J +E Bzlg =xHE
B 4"14. "JE + gl+
14E.1 au8; 14E.2 E+4 rae.S ¤F-8Ell 14E.4 +5.-
148.1 Oif UE; tae.e til HJE; 148.3 2it UJE
=î;
eE cJIl; 14E.5 rE! BE; ÛE;
1'1E.6 HJE +Eoll EllE! +EEr{ g EqEt
rl rluil
lt9 "3Boe tr=ol.= HJB

14F U3 trllTtLl=g ql
"Jql4 "-e. +E H4e cHI+4 EHI¤¤ + rel6il+qot
4q, E. ol+Zl e.ssrl eHI+ +Ee+ qHI+ l];7l e"|e ol Eqql^J= qI+ ql7}q=:E ,rll zJ-zl qE¤ _r.pa|_zzi
oI
"lF"lzl= BBg ¤E6J + ?ttrt. ol4q} 6l]4 r+Cg E oJ+. a4 ql= ,lal {r-+ql^J H}¤¤-= rl-ol9 6Eql E=
6l-= .E6J +el Hi*ql S* 4"1trt. Eail q= +qtillel
=" %r-Hel tlzzlflzlr qI+.
ol.E Hl+ r+Col q¤rll +6JillE C =
14c.1 gElEt lt8; r 4c.2l.il grt *E;
^J^d $Cg ¤{a
14G.3 EE Eg:d SEllel ?J
0llTtLl=. 4g; BB ollLlrl olE
eql ¤.}-g ulzllxJg !-= aol+. ljlril= ^gEE4 +,H"J
41 14G.4 14c.5
-Ei7I 4l+fl-= "JHl4 trllrlq+$ El+ol+.

14F.1 lErlE HJ8; rar.Z Utg +EE; 14F.3 a^+utlrt8 E!3
=El
fl rlE 0l xlsol EE=?
a+, :aqtr g+ +Ell"-l"I= %r"¤.cg 6L= elzl, ^ll
1t*G =JEl'+ ^lE, =
s +q +E ts4-= 6JCB +4e-trol+q= 7L^l gqr+
'"Je++g qql el6l]^l q}*o14. ol Eqql^l= rJ gq +^h= ¤+61+ tlil. tsd^]d4. ¤aJ zo"ll
^lgq= =-4eld
zl-=.¤+6H^l {z] E=E dzl. tt4 tsz}9 +"J9 lr}4tr_rll ^l
+¤q. HI+ +41#
^7}]61-9+.
g+. 7lso6J qI +'Jg += Ezlq qlqzlE rll+= 4,o14.
ol r+ag 561 ez]. .JE 5c zl5 ÎolE 44==_ +e6L
=
Eq 1l*A tr5+ HJSol ^-,E
g fl+. rflo}q a¤+ S+ "JBg oJe" al.{ ** zl

6ll"h
> ol E4-= u||+ts 018 itlE roK Atr+ *+zls 6J+. .+ill^Jl} r4ltlql^JE ¤+
HJ3E01 A.olrlr gdEol g7l= +Eoil EEI E+= E6H^l
+16ll^l= + "lill+ * zl4lE HI* *zl ffls -o =zll a].
+el= -d Et8 IIJeq +E= ql=g + ?Itrl. =
gEJ ofLlal EJt=-ErEol
=.=J6|.ts
+Eel E+= 85fl^1 ?al= ut¤01 8¤Ee
q E]]*61 *3 gsE tszlE- 6J+ A+ql ,++^J= E4 e
E6l"= Ex|46 fl8= 8^11611l LlEl.H + ?ltt. E(4K ¤+)ol+ "4ill eiQTK ¤+)
=7lql^Jel i[+l1l =aql^lE
e+ee B4+ aqillzl- Btr f-zl +ql Hi+ *zlE B
> E4C 7fl8 tzlE qlq. Hl-E"94 *Bol ol+qzlE- qL+. 9ler.J 4u1
HJB +E= HJ3-3elEE= 7lÊ +aloe LEH + fleq, & EE+9 z]* +Be *"J ^lEel gEE ^J^l6l gej+E
3+oll qal^1= 8dEE oltofTlE -dtl.
^J
+ gltrI.
de6.J
> EsEt qHl rl^l eI* qlzlq=g ¤+61*= rll $$$ol -JEl ol+qr ile
0l eEe E+El= L|IEEE 7lE0l q= ao.E,(l ilEoll q, HI+ EJE +el qL Ee(s{ ol alu|1ol +C zls"6J 4
^-lE4
gotot g E+qeJ4 +(EE zc)9 EErI. 88trt4 5E gqql^l cl r+ ¤+E "JezlE a+ql $al a$!ol
HJg9^lB3 Îd
3A 4eg Erf 11A= d.z-oPl HIAE+. +. qlE^l H,(s)+Brr(s)+2HBr(g) HI¤+ BEol ¤+61= zI
^JEil= +46J + 9t
,rllzlE +aEleEAl :a dq
^l%ldel
+. HI*ql E6H^J +.1 +q olgE fLl ="#zI B
g trfl= +Ee-l dEEE EqEl6Iq =z116l+
^-EEg HI+E +EE S+61+ Eot4. ¤e Ar+q
HJ8 el
HI*g +4ts + *tr]-.
6lH HI+ +E= r+6J *al_o + EI¤¤(E= ^JCE)g + (CH3)3CCI(aq) + HrO(l) + (CHr)rCOH(aq) + H*(aq) + Cl-(aq) *
Eql E=6I4 ol +al='$E Hzl'ol?+a 6l+ "lE %r{zl *ql^Je+ *ol 6C Ez.lTl ol9 dCEe il+Iqfl {-++z}
"e.448 + gttrI. #461-rll H6}rll g+.+i olgol ^JCq|+ tqg trI= +
'-49 pHE Eqqq-q HI¤¤ +48 + 9l'1.
14/..1 UEel dB +4 Hl+ EJE9 a^dg +4d+ 4E *H o +^l= *¤ E+r-
H(Eq 11F), e"+ E4H, zlzll q 471 +
=EulEr4qB,
HI¤¤ +EE4-oE- 61146l-= a B4l= q}+9 s+trI"JEg EH(Eq l6Be+ 16c), :a4r dzl tzlzl¤ tBB(44a."1
+46Ir E^l +q}+ol glEzlE g"itll= "Jol4. "lq^J HI 4 trzlzlc d #+ olgol gqali HI* Eq r6D) #
+ +EEql^l gs.J zlp cllolEl. HI+ol ^lgg +E qE =
+ 9l+. HI+ C+E 4qE 6}+zl. zlzllol A+, Hl¤'"l "Je
^ldql^Jel HI¤¤r+ ^8cEel +E=oltri. +vl 6iql^J "Jq+H "Jq HEIrI +qlqq, q+^J "Jq Hsl
E ^lrJel oJ+E 7l+6IE Hi+E dq 4cg +46J + 9l+.
(a) 9U4 a.d
4+EE A+ iz].+ HI+g +E= gEql ,I+ "J+6lq(Eq EZEU
g^l7l=
dflt salEE[=uB=q +¤sq4g
r+o"llrl ¤He. 4,o14), tr+4^J aE4ql ¤eql^J= dill qI 8El
+ r+Cg F6]l^J HI+ s6JE9 8s= "JA6l4l +zl^14 ? gE= "Ja6}al frzlrla g¤ Bq 8zl +E "Jqg +
4. "l4t s_7 azJ ullEql de 4zlq_lol :zqlfi vltr++Al A6Iq Nrorz| Nror(g)+2Nor(g)+*or(g) Ea]l qI¤¤ s
q= aol+. qls^l Tlill^J HI¤-E=g g6l tL'J6l a+ B Eq 9lr r
= 'lEl6}q.+. a*ql= N2OsEl "Jqol poolB.
q"-le+ d6ir gl= +71 +ql^l
"Je4ot 6Iq, E sE HI+ Erll, :. + "JE ^ltql dill "J4"1 p7l 5].L+. ^ll slql+el
¤. EE}6J .lill^J Hl¤+ a¤+9 olga +qlî "Jezl^l ?* ++ sqg po4 pg zlzlt- +4,llqq
9-E "J gtrI ++q CzI +E +ql^l "Jq+= HI+r+ As
zE{p|^l¤} 9d zlill flf,$ 7].46}q, q+^J 7l^ll9 +
6+e-l zlgql^J "Jq+= HI¤¤ s+61-= trll= 5tr+ r=q
536 14 u34-E=
0lE^l
+ g.qg EA=Jql HIEtl*+I ^J4++. "JA"*E Nro,z}
=6l,\l
xol J EBZI
+flqq :z BE $4ol pos-E$q po-LpE trqAr+r. -T- tl
Ill,\E
6lz|. lmol9 NrorzJ- EElldtE 2mol9 NOrzl^)l7l
Ê7la
:z *ts "J4"1 o_e--tr.+El 2Lptr_ ¤+. 8^l9l orel +E "J Eqrol
qE.0-e-tr.+el *^ps ¤+. sqlBE d41el sq3 ol ETJ4I
^ll
cBe] +E aJd 4"14.
"Jqg fal 14A.1 g-Lf UJB
^-E E+ 8xL UBB3
gE:Lf +E-e E-Jd
=AEoll qa[^1 HJB
+oll +g-Lrtl. EIJAIE 9liloll 3rl 86t|t.ltrl.
+94 ag E= "J=+ ^l,Jol
=ol
pNror) p(Nor) p(or) p
ESl,\l
ilg Po 0 0 Po
I
x.ol
ETZIE Po- N 2Lp inp Po+ iLP
-T- tl ExlE
tr1Ê tr1,\E
44 ipo - lp *(p- p) I@ - po)
EH]OI
"J "Jel B-9 p=po+iLpE Lp-,ap-po)E HIE
q-gql +l EBZI
E qq -+g aol+. reJ 14A.2 8rl-==JEoll^1= UEE= 7lg^l +^l'71= 0l86|.q
=Efgoll
+g^lz ct.: EE9
+4 0l ar+= +"J6lBlE N,o,zt d+ Rlaflg ql uulE As_e
^la
E-6E= -ELlEl-dff.
r H E $qg 0ol qq, I tpo-'rpn,a=0ol !r q+,rl

pna=trpool 9EzlE _H-olo} EI+. olag 1mol9 NrOrz|
ol$alzlTl q qB+.
+dg "16l+ *H"l 8rl-=aJ
olElql
2mol9 Norel imolg or-E ui-1i Ar+q. ui4xi Ciii Ee
H"Jr{, ol HJHqI^J. H1=+ qltlql +^1717} gfl +e H}8
*3 tmol-E$el 2*molE qq Sqol 21=tulltr f;zlalzll
d +ql^l HI¤¤E¤ rllBdl uuiEzll g6-J^lzl+(fH r4A.2).
94.
EEql E6]]^J tlÊg flE "Jq+ B+lzla g6J +E +ql
\l7l 14A1 2NoBr(g)+2No(g)+Brr(s)ql q6il^J ol
8.71 rJ q}*ol zl+g+. q}+e zl9d_z|^ld rr-lr ¤* rJ=
4l41g q+ol6}q4. i]* Sq prg NoBrtrI9l E'J a.J fel +*Eg ols-" olq +Aqi{. ol HlHg ol+olfl "Jfla
I ztdat¤4. ,so'd
+ a ++lql^J "Jq'tE H]*g ¤+ts + 9l+ "l *89 a
elq zlE HI¤¤ +e6J f glg
,od .d
-dll=z,sd -d =o"d +-"d l-
<od :E o + ^J++4 r, HI
^lEzl- "J
¤¤ ¤+6}7lql 4EL6Iq, +EAel dEol4 F-^ ++E Hl
+,llrlq+g ¤+61-b trll ts4 ol$-9'l *+.
(b) g:d gH q+d UHI= HI¤+ cts s]lHg
+ 9l= 0l+al]^J ¤+6J
=EEt ql, ol
'*Bql^JE 4B6l 5].e ^lA Eq] d%r"ql rr¤
,tl_EE
Lo EE
+461+ 'JBg Sq6l+ e+Ea" 4 tE HslE +E HI*g ^lg^la r+q=, yli++ flE+ aEq^j .Jq+
ql EI+î +strI. tF J+E HI¤-==g + B 4zlE + ^14
^lA 4 b HI¤¤ Eqq6F= du} t}4 B+ E= %r-= #*H, 4E
ql gE+4 ¤¤ql ER6Iq q4 zlzl "JBg ol$all,tj :z
d S+ E*8, E.t Raman &* PlBg ol+6iq *zl 1
tE EF+E +46J + 9l+ g-^lzl E4Hql^J= HI¤¤ rl E Ee# Eqq*+. :zB l4A3ql -H"J tl,.lql^J= tl s
q^l7lE^J H}¤-4le-l ecg E4+trt. ol "JBql^l= ielE
3- Ellol4 ¤: +'Bs' g^ql e-l6]]^l gz]. AE E= dz}
^lE. $i.otql4L} E= dill- zlzlt_ EqEl++. tr4 e.e EErll ol-Erll, ol A*E *zl-3 ,J=6t4+("JoJ"l
Hl¤+=ol gajle gq Eqe ql EJE+
=eJgql^J. + ¤'JeE) E. += + Be+ Hl+6lot +Zlill ABE "J= 4
(rB 144.1). Sd6l gqlg +.-qe H}]¤+g E6}l^J ¤.Bl +
zlErll ol ,r.l.ololl t}+"l 4l+6H^J oJq+E_E Hll=+E qBl
* ololrJ
^J^dE c-tr ¤+. +
+l^lql^J +.lq a^Jg aÎ6IE iE--6J +E 94 tolel rl4 A+hv + A* (E=oJ
ql^l HI+ s{}+9 a^}* 4+ ,Je a+= eg + ?14. z]l A*+A (ttl6.1
?.il^l gHBel +de E*e +qE *._4"1 9s_a1c1-=. 4o14.
A*+B+AB+C (*9")
BulE HI+q a+q= f4¤ uule4l 6[^] H]¤¤ Ell=+
=61
e-l dill ,J"l"ll ¤-rJ "Jq+rll 6110} 6}zl qEql ol ,JEg q+l +EE
^J¤ +Eq +E= HI* r+Cql^1$ ^lEE
^tr
1/.A trltrl HJ=el+E 537
,J=71 1l+A.2 UEE -,4S.

E^4lal-6t^l
allolll
tr-lAf
-d 8xl HI*+E= Hl* EqlE9 9re+ a^dql el+{L+. '}S qq
¤ql^l "lBl6J ¤E aqSg z[,r]lal girlEaq.
e1l^ al^ E7l
^lE
(a) HJB +EE ¤e-l
E+tr|
g8 8it t E.EI 6t^l
4]o I1Plx=011
dL
-et
E
A+28+3c+De+ eg E$ *¤¤ S46]] Bzl-. "Jel9 #zJ
^"ie IE }-EE []E +e}r11t t]$AlE +iil}
.l.eJ 14A.3 dB E6t|gg Ht|ilEoll^l E^4EI EE gêl E+tr-l "J8 + ql^lel HI+
'o-41{'B =JB "J4= UE=Ell ee a1l0lx1 "JA= /.t8alHtrf. EEel =Jd
"JA6L+I 6}zl- + HI¤+ol +trsl4+ + ^J¤Eol CC!
"J4
^lolE ^|il
il'=
^tr-=f
+ 9ltl'.
+71 ^-E= r
+-EE. ^lzlql ql6ll^J E^l6J r?]lgE d
= zl$Tlel+r+("JE
d9 &e-E +4U).8|4^l q- ql ^14
¤16I
^la_el= He+ +EE Eqqdl.q AC6J+. *
q HI¤¤q +z
^tr ^-,E= -dlRl/drol+(Rg
Au| n;. o1
^trlEHE
ol Eqq= q4 tolal e+ z."l +4u Hlg 4s= .Jel ag 4=trHrH r+e.a;. a
4lolzl $^ +e_l
^l4}ql E^4%IE
o+* g^('Be 4I+'g^)=
^lEql
E"4^14^J EL+. gê+ ¤ qL 6J SCE(C Ei. DE^'l P-tr .8^l6JtrI)E ^J^d +E=
E 'E^q'rlg s3 Eilolzl gÊ rtyl"lq+ E= E"l4 rI alpllarol4(Pszl. +Eg +E-61-ol4). ol +trtr E+ "J9
¤plB^z} Ela *zl9l d+^l7lH Hg d# H+lE H+ ztg 4=trI
ol q.eu ol= Ht E+4 "Jtsol4r 6l+ ¤tlg olf-all,<J zl HI* e+zB+3C+Dql El]6J clE=*4 +al. S46IE trl
d EIE+. tl Ellolî Ele+'E4'%+ gÊ qL + H¤ol rl $4 ee +Al7l CB6l-q, q-+î ol HI*E +E= {4 z}
E9l EB:"lt 4?-lE a¤6IH F H¤ol ;.le.9l EB6I= zle +EiE + 9l+.
^l
zI9 t"la}4l a¤B + 91tr1. qlE^J + H¤el 4+ A?-l iI dtDl _ dtAl _ ,dlBl
zl Ld-: mmoJfl + H¤ rlol9 rlt zl4l7l Lt=Ldlc=rlps -il-r _,dlcl
d, ---&---1 dt
7t 9+. ¤zlrJ c= rJ+"14. :H 14A3ql^l='E4'oJ q¤-
g d*4
ql Hl;-E HI* +EE q;l zlzle qs4l +49 axl= S,
de ,lg g.qg _Hqlq F HtE ^Jql4 Hl o|lzl glall.r-1 u3 T.!4E {E ol+61+ql, ol H}* a4EE ol
=ql
q 44E a¤6Jtr1.
¤^la +4Bql^Je+b g"-l E=Hql^l= Hl¤¤ "Ja ^lt
+6IE HI+E -tr= slq}+ IE E-4eJ Ho]. dnlE ffi$ pol
+ElE + 9i+.
E"J "Jq+al 6J +gql r HI¤¤ czlrlTl4+.Ea'^1il+.
r?]r Aa6l r a^dg +46l.q A+ql q4^J= HI+ +A dn,=vd( HJBe-l Tl-d 6E t5qll (14A.1)
ill= Eq6}| *zlg ++. ol HJB$ EA^l7l= E"Jql HI-$ol
4E "Jq+^l ?+g Atr+ **ol L4rll "JqLI"F 4+^la {zlrl v;5 6 Iel :l}+=}4 4lfolq(Eq 2c; H}*E'J trI=
+ 9itr1. Ettrt4 E= HI¤¤# gBBql^le+
=aJgql^J=
Hl++ %rB_"-e. EEt^lzlzluj Hl+ g.JEol ull$$$ $all
gC 4?-lE Er+ql +91 tol+ gTlel ++ triE (a) EC, BJB 4c. = 7lZ7
^J ^1"+g E
*¤¤ Ee^lZl4. u]]=*g E"* f4¤ aA6IH

ol$all.<J
HI+ Hs+^lvJ + 9t+. siql4 E4 g-eHg ols" 6IE
^l{g 5 (b) Ed, EJB 4.s = _zlfltl
czl gBBql^le+= 94 Er*+4 zlE¤ oJ$alzl s:IE ui
-tlo
Hi¤¤4 ^J¤EE bE. E4g fz| 914. ole+ *ol qI 01ru
=
*"1 "JB 5Ag q-Sql= '.-il'E4B, qlArll e* E4H
ol+ TgufEl4qe+ eg "JB o e HI¤¤ +E¤- +4e. HLO
JO=
E
+ 9l+.E'J E=gql^l= HI+ Eq+E9 9s= E4a ol4 t

^17J,
E sg ^le E"Jql +461 BqEEj^l HI¤¤ Fa^lvJtr+.a aeJ 14A.4 ,\l?-loll ulE (a) AdE, (b) BJ3E9
.tE EAIE LEILH=
4I. Hl¤¤, +7JAl, r4r ^J^JE-=e-l Eo EE ts%+44 o e =Coll
trdel 7lz7vl (+,JEj8 4=c;-. 7lz)l7l Bg nil= +E= qr7,g rql
rH-d
+E= Hl.+Gl^1 UJB +E7l -dA gol Elll Ettl-.

+a++.
538 14 E]84-EE
¤-"l_,t ^J^"iEg trll= "Jol+), "l HI¤- ll4EE $ffi zlxl z= k,[A][B] (14A.4)
_1. UB +-E uE +s=4 ?"1 "J94sE CEql+.

4=E 8++r +e=ql,
HlEll
^J+ /r,g "lag bEql= ++
6lzl"J gEql 9=EI+. ¤84 " -+ a¤q= olel+ ++E
u=vI E
d¤ UJB 4s t8e-ll (14A.2)
HI*9 *=. Eflol4r H Cal-9-e s¤6l.zlH +
^lg =4.
¤zlri v= H}+4lel +"1+. "Jelel + fql ql6l]^J dt-dnlvt E B4g "Jgel EI+HI+^] +E E
olq, q+^l +lE tr}e=r+ *"1 ¤ + 9ttr1.
^lzlql^jE HI+ +EE
3rlqI+(^JCEg -IL6J¤DEE t-Eel 6J+E +4d alol4.
^lg =
I ldn, +
u- (14A.3a)
\xv d,t =fl[A],[B], ...)
tsEE LtElL.! +E g^l (14A.5a)
ru l-o_.lHt^l
Ldu-
a^tl
o-l
"JC-+q zlql^l "Jq+= +"J Ei*e-l a+qlE Pul vE ul

E 7ls oJ-e-E 7l4rJ + glsq u)-n/vq +4lE 0l+610l +oJ Tlill HI+9 A+ql=pr=Rrlll9 +41. ++ Sq *.
ol Hl¤. +E= trl-g_r+ a.ol 44u4. $ ol$-all.<J +E H4g +4d4. :4ai¤ elE a+ql=
ol
HI* 4srl-+g.4 2-o1 +r.l$Q.
u=
I dul (144.3b)
v, d't +E gqee qqLJ 4E
u = f(p o,pu, ...) ts41 (14A.sb)
#.J HI*g a+q= v 4d9l +=ol ilzl6]+-*.H4 e

5 ol$ap oFnlAE ole" o[{ H}+ +E= tr]-sl=r+ zrol 4 HI+e]+E H4g ¤84 0 + aaqq, "JtI4 "e.= HI+
4Utrl-.
ql+g+ s+ qle^l +Ae+_H_$,r.1o1E Hl¤+
^l_oe+q
tAn
+E*49 e.ts Hz(g)+ Brr(g) + 2HBr(g)e| tol {}+6}zl"J
,- r,^ .._dr |
(14A.3c) I +E H{$ tri-:z-=4 zgoj q6ioicj-.
"lell Ete-.erl _EE Hl¤{H}*ll" + s,zla3q1 q+ +"J H} .. _ k"IH.][B.r]"'

'/ - [Br]T+TJHBil (14A.6)
I +EE +ElB + 9t= 4,o14. E-BEE "JHJ %iql^ltrlEl

E+tr" rflI ^lAg
+e +QL}]H tg HI+el ** 4szl- +E Bzl"l q}Sel +E=J4 +4lE +4.|]= a+E ?lzltl
mol dm-3 s-'+ .E.= ole+ +fl¤ +flE s^lgtr+. 4zl 49lrl olag +¤E "Jilol4+ EE qI+ ql7}q+el 6J
=84"J
"JqLl= /.t+ ,J* Tlill^J HI+ql EI6]]Î= Eo EE g6l "J"J 5Ag Hlg^l7l= aol+(Eq 14E= _Bot+).
cl4"l4 z+ tszl-fE +Elg rllzl gleq olullb tl+ 4szl
molecule cm-3 s-rE -s^lg+. Hg HI*ql 46H^J= HI* + Etr+ gE 8^l SHI4"J +E ^J+=
/c.s +4qlq
EE mol m-2 sr{ E= ole+ +fl$ EflE Boltzmann ^J+ /ce+ +E+4. "J* :zzll"ll^J= glE ag k
'+4U+.
E, :zal-L +xl¤ k E 444r. 9l+. 14A.6^lr+ ?9 -u_c1
zlEtEt q 14A.1 +sEI +E Hzlq^l= +E 4i+= k", h r=o e_tr L}EIB a
oltrl.
^8C 4gz}
2NoBr(g)+2No(g)+Brr(g) H}+ql^l NoE
0.16mmol dm-3 s-lolfl+. fqH vNo= +2olg=- u=
+dtNOl/df =0.080mmo1 dm-3 s-t7I g+. ¤I¤ ?Nos,= -2 +E ^J+ k.9 ++l= alt 4s Hzl"l r-o E HEI¤- ^lae
ol = e. / = +dlNOl/dro1trI. trl4^l d[NOBr]/ dt:-2u- -e. +b 44zl qE+ tE=E +g He+^la + flrll q6]]
of *+. qlE^J +E Hzlol r+A.4^14 eg gE +qzlr +
-0.16mmol dm-3 s-rolL+. 4, NOBr9 +Il $Ei 0.l6mmol
dm-3 s-1, EE g.6x lOr6molecules cm-3 s'ol
EE mol dm-3 o + E^lB ullts. t.9 Eglz} drrrr rnol-t .-tol
S4.
9olo} +E Bzlol rl-e_$ ag ++l= ,Izlrll ¤+.
kt tAl tBl
(o) +s. H=lEl4s.8+

dm' mol-' s-' x moldm-'x moldm-t = moldm-'' s-'
HI+ +E= 96l HI¤¤9 E"EE H zll-".,* "Jql Hlql6JtrI.
qlE^J HI* +E= ++4 ?ol F HI¤¤ AeI Bg L" Eoll Bl "J"J E$ 1cm3 B Ezlfg g,t l6p HI+ +EE molecules
r-"
Ellg + 9l+ cm-3 s-r-E- ++4H +E

^J+=cm3 molecule*rs-rE 444"t
14A alEt u¤ig 4-E 539
6J+. zlftt\zl ¤Eql %r-Hg ol+6IH

"Jelel gE +E Hzl ol+.
e-E+El +E tI+E ++l= aag + 9l+. HI*9 il+E 4izl "J q= a+E ileq r*3 zl^lltr
t}*ol olfl a+ql ql'J;g+. qlE^] +s=r+ eg +E Bzlg
zlEtEt o{l 14,4.2 trisE HI¤¤. Aql +6ll^l +iL Bql +6ll^J lil r?]l di-ll4
o + 2+E rilzl ¤4.
HI* o1g1+o,(s)+2o,(e)91 'il+ 4s- 145 2e8Kql^J
9.0 x 16_rsoo3 molecule_r s,ol4. ol +E tL+= dm3 mol_r
u= k.[A]'/'[B] (14A.8)
s-'g ++.llrlE lcm =10-'dmg ole"oll,{ +i{= Hh+q
of 6Jtr}.
zrtrJEt oll 14A3
('ro-'dm)3 zl 4lt1- HI$ HzG) + Br,(g) -+ 2HBr(g)ql q6fl^l +Afl +E
kr = 8.0 x 10-rs cm' molecule-r s-r B4-9 +El.ol HI¤+ Hrq +oilrlE ril-olzl
14A.6^14
= 8.0 x 10-rsdm3molecule-ls-r "J Br,et nsr9l +6H^l= ¤q6}zl ?*eq, di-ll HI+
il+
E B+6}rll E6J + S+.
"lag I mol*9 Ezl-f"J Avogadro tt-+E 4h"ld EzL
+= E¤"*e-s Hh+q +4U+. rflE tr}g=r+ +2 4
,|= E4 g+. tl¤-ol OiI +E B4g lrts= a+E ?lbrll, olBl+ HI
8E HIA +E= *.Eql ++61+(e}¤¤ol 9"1-t ¤zllalE
k r = 8.0x l0-l8dm3 molecule-r s-r
+). qlE^l r"JE sr-.g(pH,)ol E4g B^Hl +El] E.Eql
= 8.0 x 10-rad*,"(
'ImJ
l=Tolttde \ -l s-l
^J
E6]lg ull= +.q_+ eg +E Bzl¤- Ir+=+.
= 8.0 x 10-18 x 6.022x 1023 dm3 mol-' s-'
u=k (14A.e)
= 4.8 x 105 dm3 mol-' s-'
PH3g,lel + Hqe rii,4zl"JA+ +-tr + E6H¤+.
zI++ {l r+a.rgl^l E utq *ol +E Hzlol r+A.7al4
"J+ +E Hzl4 +E t}+q (}g 9rll qH HI¤- EqlE eg +g 44421 ?+eH dill HI* il+E "J¤ + S.sq
el 3C-e-E+Et HI+ +EE ql+g + ?l+ +"J olq+ E 4 CEEqI +6ll^JE HI+ zh+7} Hq6}zl ?+g + 9l't.
I r+sglrl ¤Eatflzl"J +E Bzlg "l+6lH e}*ol "Jc "lfl+ q|==g +elqlal ,<ll zlxl +!1. "J4
=+.
HI+ E6JEE adg qltr-+ + 9l+.
^lz} E"J "Jqt +E dE qlolElS 4s Hzlg aa6tr E +E
oJ_o" 6l.g
^J
ol${etr.E ol +E Hzlol H}* rll7}q=g "Jo}L}l= ,J* +q ag d+
+61+ Eall. "l tlql^J= ¤zl9l +6ll^.1
olE so1,--91, olAg ++¤ +E Hzl¤. "J+^lzlE 4e + ¤86|4+.
"llzlrl
-"1+¤ i glzl ullEol4. ¤21.il +6ll^J. e4 rasoll +E tr-+Zlg Al4I6Lit, olEE s-E el= dg- ¤Bq+
="Jol
q
^l ¤B6l4t+. +41. dzll *H3 Eq r4Dql^J ¤B6}1ltrt.
+E Bzl4 +qlq= HI* ,ll7lq+g *= Exll. zl^ll6J
(c) HJE xl+ ¤Ee Eq r4Eql^J ¤H6IA'I.
E+e HI¤¤ol ffi$ ae gE +E Hzlg trlEtrI.
(o) +s E4s! e8
u -k,[Al'lB]b...
+E Hzlg drll ec.J + 91. + rlBe lialsolrp al.
(14A.7)
olBlql ="F9 +E B4ql^J HI+

^dEE(^JCE E= Hl+ *B?lql, ol "JHql^J= HI¤¤=e_l t-E= 6J TIzlEJ z-lle-l
=
E)el E"Eql 4l#q= E+= HI¤¤q HI+ il++r1 + r 6tr E+ ql+61 rr.ll +l.J+.+, +elBg ol*alq +E B
+. qlaql t+e.+al4 eg +E B4g *= HI¤+ Aql +4 zlE + Hl¤¤ql 4,q} 9=s= 6}+4 z}qle AC6}i1(+=
.<l rzloll Bql +6ll^lE rzlo14. E= CE=g HI* z14g _E= ^d+el "&g 4"*_e_e flql^J) ulzluJee ol$ pffi
6J6J A, qlar.H 14A.7^lql4 o+b +...9 :z HI+E Ei.ll UB t+il= 4014.
i}+4r qFl. El+^J r+e.+al9 +E H4g dill4 _o+ z^l Hl¤¤ ez} 4"*-o-+ rllb "149 E"E7I dill HI*
=zfl$
s40 14 u8+EE
4eql^J "JA6l-rll *zl$4l -uotE +g aol+. rBlH "J log(xy)= logx+ logy
eI 4la} +E Bzl9- u_k,lAllBIr"l+H, [B]E [B]oo + gi3- (14A.11b)

lo'9uo= log (k.,"6[A][ ) = logk.,"u + log [A][
f glo ', + +E H4g q-q=4 *ol 449 + gl+
log f = alogx
u= k,."nlA], q 7l J k,.,n=/r,[B]3
+^l 1^1. EJ8, (144.10a)
B7l'rlgg tril =logk,,"u+alog [A]o
ol +E H4g +EE "Je6I+;z zlzJap ulzl tiloJ

Bel ol
^]g 4dg ++LH=
al"l4. 4,
ai.lH EJ=_ aol E _+ */.l 1it 4_,E H=l"l4l 6Iq, k,.oE B
7l!7lxx
el *-E= ra^lag qel .P6. +E ct++a ++ ol q^l
v ^{iil
=u
ql AE tE. r+"*_q e +l6}q log uo - log k,,"r * alog [A]o (144.11c)

^J+ilH +l#B + 9l¤- trI=
E4el 4s Bzlol q-q=$ pol tisl¤trt. trl?+^-l "JflE a7l HI-a-ql+E A! zzl
+E= +c6}"l r
u= ki,"o[B)', I z] d ki*n=k,[A]o 3^l 2^l ff8. (14A.10b) tEE rll+q 4aHrJ E^l6tH zl&zlzl aoJ zldol +e+"h
A7l rfBg nll
6lq, ol zl$zl| Ae-l HI8 )tl+7194.
ol +.^l 2it HJ8 +E EEI q^l sd+ +E H4 u_r1 3211
+"Jg + 9l+. Hl+ il+e+ +E +E ^J+= A+ Bel q._ @ *zl*s.t'.lEEolE
a¤: 4"*sE q+ g4e + fl+= ag +E-6I
,7l6}L+ql ots+ Tlill +ql,<J e q r flzlzl 4le6Jq. HI¤¤ a
Hl*tl *B " + oiL"J Hlso E +qlB + gt+. ++a4 + Z7l +E- *H " + r HI* il+E fa|:zz[ 6J+.
"14. Î6Iq
"fl"l 6lrrlr l.t-
.Jl?J r^[1 ril
l- ritr'l- 2", rrl.o ol ,LLr-I.^. l- Alzllz-l o;r 1- o rL
=."1'1 Tl-O -1 o'O-T-E
=."11 - - L Tf"f 2l(g)+nr(g)+ir(g)+ar(g) ug" 9 Zzl ,i=-Ezi -+s,=ii Zri+
lit+ +^l 2iI HI¤-g + 9l+. qls^l +']l"J Eol HI*ql ei
[I]or(10{moldm+) 1.0 2.0 4.0 6.0
zol(moldmis-t) (a) S.70 x lOa 3.48 x tO-3 t.ag x 10-2 3.13 x 10-2
aol+. (b) 4.35 x l0-3 t.74xtO1 6.96 x l0-2 1.57 x 10-t

=E7l 4-E g6l (c) g.0g x 10-3 3.47 x l0-2 138 x 10-r 3.13 x 10rI
"JHol +"]H!+'J4l ^l-S6l+ql, "l %rB9l
E.EE
^l= +¤¤4
azl ¤4 {t"lal A9E Qa|fl,<j azl ole*9 }-E= (a) 1.0x10-3mol dm-3, (b) 5.0x tO-3mol
E H}* +E- +C++. E}"J EE]ÎA A9] EE LO EE Hl] EO
dm-3, rr-l.]1 (c) 1.0x10=2mol dm-3o1fl+. gq E9+ ola

E 6ll+fl9 trI a7l HI-a- 4sz} Hl]E B+H "l Hl¤¤. Aql
+ gzlg tEql +6J H]g il+e+ +E ^J+. +6Iq4.
+6ll^J lilolq, trJ"J =71 HI8 +Ez[ +ufltr E+H Aql +E]
.<l zzyzy g+. tr+ 7^ll4 + +E Hzlol E4rlzl eE 5
" @E + HI¤¤E +EElol H6l-= trJlolEl ^llEE
^lEl
Eql u}+ tr|gr+ *ol E4_n.6IzI. *"tutrxqla4 "Ja+ tArlql 'll* 4 49 'll"lrl). olBl
6.J qlolqs+q Hl¤- il+E.
"J"t4zl fEl^l= 144.1lc
u = k,[A)u
49 ol*a}{ +qd Arel +Eql^J =zl HI¤- +EE qt
rElH 471 HI-a- fE u69 A4 =zl *:E= zlzl:i- q-q=4 e +E H}¤_g(ol a+ r)9 E" E9 'I+ql 4611^l E^l6llo}
ol ++E + 9t+. ++. r44q "JA6J [Ar],ql^Jel Iel tEe+ H]* +EE
E ql+= s+ "J=4. "l E^lE z)&zlY tllql +6J El+
uo-k,,"ulA)i axl uJ39 azl UJB 4s (14A.11a) iI+=, r?-la log [I]o=0ql^JE ¤¤g tolal [Ar]oql^]
9 loe k..E +4U+. ol ulS e + g= +E +E tI+=
olaE (^J+)r]l+'=. +l6IH trl++ ?ol 84.
&,.r=k,[Ar]8"1q, k,q b= EEqlrle] ?ol 4
=q.IEJH
+E A4oF *+.+
czr+
' q+(bgarithm)i +g-r+ zJol t*4f4 zt¤4i9 F %I4sE a logk,,.o= logk. + blog [Ar]o
elg+.
a=tdolH b=loga k".¤ loglArlooll q4î -5a^l6IH zl$zltr-f,q h= g.I.
c=/olfl. d=lnc log [Ar]o=oql^JE ¤E-e-E+el log k g eg + 9l+.
trl+^l logl=ln1=0o14. rel.I. + q+ ^Flql=log7=logeln79
*4lz|
CBttr|.
14A EltrI u8E ^-E 541
+q{l EllolElE+El E^l"ll gs6J dfi$ +6Jtr}. 0

=ol
log([I]/moldm*) -s.00 4.70 4.& 4.22
'i,
5
log(uolmoldm-3s-t) (a) -3.060 1.458 o
-t.857 -1.504 a -1 -'1 --O
(b) 1.362 -t.759 -t.t57 -{.804
I
E
(c) 4.Mt -1.460 -{.860 -{.504
! JY.-
E
tArle "JadIxlEI ulTI E6l+ a+q ol qlolEl= E^l+

E
----' _l
7.93
6o 7.64
4,"J :zH t+A.saol4. CEfl zl&zlY 2olq, Qz|,<l ol HI -r/ 6.94
¤+ r.ll +6ll^l D,lzl g+. r?-lr +E +E tr-+ k,"e -3 -t--/
q-q=r+ Aol ¤trI. (a)

4.8 -4.6 4.4 4.2 4
log([]o/mol dm-3)
8
[Ar]rt(moldm-3) 1.0 x 10-3 5.0 x 10-3 1.0 x 104
log([Ar]o/moldm-3) -3.00 1.30 -2.00
o
I
log(k""6/dm3 mol-r s-r ) 6.94 7.& 7.93

!
o
rH t+e.sb}. log{k".n/(dm3 mol-l s-')}g log{[Ar]o/(mol E
E
d-* ))ql ql6ll^J E^l+ ar+= +4u 4"14. zl&zl=. t E
to
9.91
olq, lr-16}{ b= tolq ol H}¤¤ Arql +6]|.<i rztz} ¤4. .r<
o)
Y
o -,,. U
log{[Ar]/(mol dm-3)] = oollrl 9 e¤g log{k."6/(dm3 mol-r ;R
rr}+\ k,-B;xl0edm6 mol-2 s-Iol4. 44

s-t))=9.91o1q, 6.5
,<l lazl){E B4g u=k lll3[Ar]ool4.
-2.8 -2.6 -2.4 -2.2 -2
log([Ar]dlmol dm-3)
:rg 14A.s H7l 14A.28 E1l0lE1 E4. (a) loll tr-d EJB r14g +51"=
-trE gESAl x.xxxr0'(n<10) g"J +E t'-+ tll+E -EAl. lo9 [l]o=00ll,'.'lel trtrJE 9- Eoll d.J6H ts9ttr|.. (b) Aroll S-d
HJB if+q +E 8+ I(,= +61.= E\1. log [Ar]o=OOlr1E trtrJ= 9-
i+A Eoll gB6tlts9ttrl.

r.23xl0a=4.0e0o1tr1). SE += tgel q+"J +ol
4.t}4e y.yyyq {lS 9-er= +E +^171,<'ll zlr-lol
4(ql-e.^J ros.678 - 4.7 6x rosol 4).
?ol E¤ 19 L"E"ll E=.J+
[J]ot(10-3moldmr) 5.0 r0.2 17 30
ud$f moldm-3st) 3.6 9.6 4 130
Iql +oJ Hl+ ih+e+ 4s.449 +6Iq4.

r_s r_lorrr¤rlrp z_0I x9.I .Z :S
z7l ++ %rH "_e. Sdql +E Hlg +g + S= A+ ql= qltl+ +E H49 o1¤-6ll^l "Jgel
^ltql^JE 4 ^dE
E fl=ql, I olf+ ddE"l +eE ol4"l HI+ql +q6I EE tE= ql+EI trl¤.ql a_49 ¤E rll"lqs+ Hlj/6k "J
.l HI+ql ¤6&9 +71 trllE"lq. qlE^J H2e+ Br,^|olE Hlg sg ol_o_" aj + gltrI. {zlgl +E} "}Hg Eq l4Bql^l ¤Bg
I A+ 14A.6^lql e-16l.H gd+ +E B4e ^JCE HBr9 4o14. +E H4¤. ^lflal] Bzl +16l]^l= ^J^dEg AzlalA
t.Eql E=6Jtri. ol+l+ ++g iil"telH HI+E d 4eql a + E. zlztl-^J HI+g a+ql= eI* *zlE sE Etl +vl Hl=
a^J eg qlolElql+ +E H4g "*+qo} 6J+. a+q} a+ H4^l7lE^J HI* +E7l H6l-=zlE q+E B7lE ¤l+.
5t+2 14 HJ34_E=
TI|LJ=
=s-d
tr r. Elql Hl+q +E= HIg g.J¤ +ql Eqil= +=q -r-"E tr 3. u8el +E= relg EiE+E4= ++61ril HI* aE= 7i
Eqq6l+ %LHg oleo6}q +a6Jq. olBl6J ¤E 'JB
= ,*H4
^lr +4utr1.
E 6ql= d-^lzj ,JH4 HJH, E= SIFE= a 4. +E g4e +ill4 EIE HlAq +Ei+= +EE E"EE zI
==
*H,:-4l. CB5aIIH Eol 91trI.
^ln +4u Hl¤- +E^lol+.
a 2. HI¤¤E +I]e} ^JCEE ^JCq
ql+ Hi+E +zl
^-E= D s. UE9 il+r- +E Hzlql +EI+= e+q. "l q+=9 !t
Eo EE E}]6li^l E^l+ rellsel 44 zl&zl4("Jfzl g $i{14 UB i!+7} gtri.
^lrJql
qAl Ll4Uq).
=sEl^.1=
.^-lzl
oe. ,,.1
1 +4 al Ha
uL-g
LIO
-4.c
-!
u= (tlv)(dUdt) a9 r4/'.2
y = (rly,)(dlil/dt)
"JC +4 4l l4A.3b
+E Hzl("J+ a+) u = k,lA)'lBlb... a, b,... Hl* zl-f; a+b +...' dzJl ilî 144.7
'
=71 HI-a- +E
HJB loguo = log k,.",., + a log [A]o E?]g H]¤¤ e l4A,.l lc
EEJ lt,,B 4E*= E{il
t= -l
> ol EE-.IE u[+ ol8'

HJt E*.EtEol EBoll tr=61.= 48oll,tjel :1 adg ql*6ElE
4E^_E gElol ggdttrt oPie^_E g=]4^_Eah¤ o
r1loilE ol8qq, ola1Et eE!= HJSel 0ll7l-LlEE=861E
4E +
k,el
=71
=6H^1
9lrt
> E4C 7ilE!

+E Eeg 4E6lE Et8Erl gA=q EE7l qal olBfll
^l?-]oll
EolExl= golH + ?ltr}. 0
0 t -->
^17J,
> gg:d o{lHlrEl fg 148.1 0^lHJ301ll1= HJ-01 C-do+ #^lEJrt.
+s. E=1, HJ8 ih, f.alr +E 8+E zt|uJ(E4 14A)g +xl6lr
?lolot ettrt 6H40J 4E BH(rle trq E= 4HU gE ?.Et-d
+E H4E IEfg + ?ltrt

"l 49 1=[A]/(gl^J H]¤¤ol d+ s.q4^J [A]7] 0ol E
ollzlxl C Bo-J+(rH r+n.r;.
UrB.z 1it UB
+E B4(Eq r4A)g "lE %t¤al"lc|.EoEE ^lAe] 6J+
E +444H ol +E Hzlg 4B6110} ++. +At+ +E H rz}4E Hlg trt+r+ gg golr1.
!e d|l +il 6]|= +B + 9l+. rfl+ 'H++E +*+ a
+ql= "JE 4E +E H=lol+r +e= 614 6l]= flril +e- # = - k, [A] (148'2a)
+ 9l+. ¤zlrJ olBlal t+q} a+ q TV|E aÎ6l-IzI *

"l !g 4+6IE Ael
:-oEzl-^ltql qB4l Hal-tszl$
+ "I4
-u.ol=+.
148.1 oil u3 @ 1-IEE+EHEI

A+P E9 oz1 HI*e-l Hl+ +E= q-q-$ aol "J46|tr]1Hl *d t+s.zazl$ +-q-l4 ?ol l4 2!-r+.
¤¤"1 ts"t91= +)
dlAl
dtAl K' lAI =- kdt
dt =-
1
q4^] AE tE Hq+.r +q +E(. -k,)ql+

ol {g k,ol ^l{ql +++ tfolo e zld 4Eg fzl- ll4.
Hl¤.ol Cq xi¤-.tlHr=ooJ ull) Ael Eo E7I [A]0ola rltol f trJ+ zlH
g
^leg *6J a4 eq-. g rllE +EE [A]olq, q+^J olE¤. zJE *al-e +1"]H 4
[A]-[A].=-k,t *4eol ++91+.
"l ^lql^J tAl=rglrJg eg EE"lit.

ol !g ++4 ?ol ul-#q +ElU+
[A]09 ng <.zl EE+. IIH =-k,fodt
rtx= 4+6IH Qnx+const)7} qE + ol 4IHg +'gr+

^lel
[A] = [A]o - k,r EE oxf +E g4l (148.1)
*ol 84.
54t, 14 HJ=|A-EE
48A.2 E7l 4* <t9 H}e-E ?b rll e4= a,|zt7l r,,rE B

^17J, =
aol+. lil Hl+E a+ql= A9 :-o E-zL [A]o-q-E+El ][A]o
Ilffi=h =,, tA]-ln [A]o=hffi =o e
[A]+constantllll.
++. Ell a?-l= ^lt¤- 14B.2$4f o ++q ++r+ ,Jol 4l
&6J + ?lrl..
k,t,,r=-h#=-h* -ln2
A 4E txf
ln
FI; = - k,t, [A] = [A]oe-&' _aE rflil
tl --
(148.2b)
-r trI4^l
ln2
E^lg 49 r
t4B.2b^lql el6IH ln(tAl/tAlo)E foll Ell6ll^l
t,l2
T atrz;tl [1^1. uJ8] (148.3)
it HI¤¤ zl$zlzl -k.oJ 4dg 444ot o-J+. ol *H +

" (ln2=0.6e3o14.) f E6llot ¤- +,qq} d¤- rz1 q1
"l e4ql^J
++ q zgl r7l Hl¤:el +E ^J+ <t9 s r4B.rql +4.11fl +q a+ HI¤¤e] **7\71 a ilg bEql +S6l-+= aol
+. E. l4B.2b^lE EZll e]6IH lil- HI*el a+q= HI+ qE
^lql +. nI4^J "JEel HI* +4ql^lel Ael bEzl- tAl
"J"J
EE }.Ez| xlaa;44 _e alA6l=ql, f +E= k,ql el6il
o
4H ^ltol (ln2)/k, "Jfrl rl zl*g ull :z Eo EzI +tAlE trq
^l AC¤+(re zlrll g+. "JP e}1lzlE s r4B.rql +44fl+.
ruB.z).
e + Pql uI4 p9 tE +7I= Ael bE Aê+ ?eg
E 14B.2b^lE 4E +E El4g ^JcE rel $rg- o1g
6I]^J +EI.fl7lE ++. + HI+
=zlql
pz| lizJ *?t+H @il lituJgot 6n4
olzullrl-o
-| '-ll -r_f-L arJ \-r arJ /4\ rLJ frJ /^\r\r r-toll rrl-tl- t:
lpl= [A]0- tAlTl- Elq, q4^l tAl= [A]o- [p]71- g+. Aq +¤]
\-rr3rr2\,rr3\b/, r/var3vri3\E,l--^r2\$l-ai .'i-i E
"l 49 r4B.2b^lql Bq+H +gr+ ee ^lg eg + 9t+.

6l]Etrt. 600Kql^J cH3N2CH'9 *B "Jqg ^lz} EI-+s
+46Iq +¤'r+ Ag a+= efl+. ol E6I] q13-ol ola
ln lAl, -[P] ,ll*ql +6H^l lzl."Jg q"J6l-r. 600 Kql^lE +E tr'+ <t
lAt;- =- k,t, [P]= [A]o(1-.-&') (1aB.2c)
g +61-q4.
li} HI+el +E= A+6LA] q"J6l-= 6J %r-Hg H]¤¤E ;- tls 0 1000 2000 3000 4000
plPa 10.9 7.63 5.32 3.71 2.59
E 148.1 1il USoll E:et UB +E=4 EllolEl*
g
rjl.
LIO
,\L
d el"C knls-t tu, r.a{g AtEf ol H}+ol lil.oJ¤. q-"J6}EJB ln([A]/[A]0)
2N2Os + 4NO, + O, g 25 3.38 x 10-s s.70h E ^laq 4qlc E^lflg ull zldol 'le+"t 6JtrI. Tlillel
Brr(l)oil'(-l 25 4.27 x l0-5 4.sl h
+E "Jqg I E" Eo| ul{la}E_E(Ed zlzlltr E + 9lg
CzHe + 2CH3 g 700 5.36 x l0+ 2l.6min
ln(p/a)= r"ll ql4^] s/laJlE u[lz[z]oltr]. zlCol
oll) 4
* zlE Aq q "*g {tEol ++slq ";q sE r z1&zl7l-k,+ B4.olq^l 14B.3^lg ol+6}q k,
E+q tlzJzl= al&++.

_l
Eol po= l0.epag "l+alq +*4 ag E= "J=+
1
0.8
tls 0 1000 2000 3000 4000
PlPo I 0.700 0.488 0.340 0.0238

0.6
-. kr,sm ln(plpo) 0 4.357 4.717 -1.078 -1.437
3 0.4
h(ptpo)Z roll q6ll^l E^l+ 4ol :B 14B.3ol+. ol E,<l
0.2
ar+= zldolq, Irl+^J li} HI¤:"Jg qee. + ?lr r
zl&zlY -3.6x lg-4oltrl. tr+4^J k,=3.6xrO+ stol4. :a4
0
0 1 2 3 -L l4B.3^lql el6ll^J t}*zlE trl+$ Aol ¤+.
&.".",,t
lnZ
fg 148.2 1^l'HJloil,t.1sl HJ-sl ,J41. 4s ,g+71- t,,.=
tt: ----iri..= l.9xl0rs
rl uul= ^l+--J+4
rJ^lEtrl-. q7|,\i= krru,s"=3kr,.alto|rl. =+= 3.6x 10-' s-'
^_E_=,
148 a{E
^_E EEI 545
0 I I I
_-r .""**1,^, =
I lAl '
[A]- m
\ r4r +Hg k,tzlgc:y. tr14^J,
-0.5
a 4E rrl.xl
zxl
a
c #-fr=k''' tAl=l*ffi.,; 4E
-!
tj-
(148.4b)
-1
\
14B.4b^lql 96H^J 2zl-HI¤¤ Utal= r"ll ql6]l
^lE6lEJE
1,"1 zldg
r.rlf, zld9 zl
+r}1il|zl. Eoloh 6J+. ol
-1.5
0 1 2 3 4 ,<.1
Y(103 s)
gzlb kr+ eq. ol BB o + aaql +E
fg 148.3 1^l HJBsl ^-E 8+ lntAl(E= q7[Jef '&llnplpo)E ^J+E "J+= E
=tr.
E/.l6l-E 7lz7l7l -k,E Ll8trl. E^l6lE rll 0lEE r4B.2ql ++alfl4. ol rA 4E q}Sol ^l4g + "Jq
toll rl]all,\l
^lcol ^lg
Ello lElts .H.7 I 1 48.1 el rio l+. rl4 r{lrJ A9 L" EE +g + ?14. azl HI* +E7l ?Jg 4
+ql= Ae-l :-oE-zI tz} HI+ql^J H+ q LelTll 0o + d=+
\l7l E7t 148.1 ¤Eql^J a4i] EE
6J +e_l 4(:-B 148.4).
=EEL
E7I ++r+ ?"1 rlz}q tr|+ H6I9+
NrOr9 Eo
lzt H1*ql^le+ eol 14B.4bal3 e_+p El+ql^l [A]=[A]0
tls 0 200 400 600 1000 -pel plq}*4 +al= ols-"alol ^}cE pE-7l-zlr +48 +
[NrOr]/(moldm') 0.110 0.073 0.048 0.032 0.014 9l+.+ ol +AE Br EAel 44= 6IH +94 Ae !g
ol HI*ol Nro."ll +6ll^J li}"J¤- q"J6ljr" r +E tF+ eg + el+
+6}014.
= ,-sr-0I xI'Z=5/ :E
tPl _=k,t'
t. k,rIA]3
(14B.4c)
[P]= l+[A]ok.r
ITI[1DF;
E 148.2 2il u30ll B:d u3 +EE4 EJlolE{*

148.3 2it u3 HI. g
r-1 O $ el"C k"z(dm3mol-ts-t)
q-s=r+ ag EE 2zl ^.--E B4g lz} HI+ql q6l]^Je+ +"J 2NOBr -+ 2NO + Br, g 10 0.80
t BB ".+ +g + 9l+. 2I-+I, g Z3 7xl}e

. zlE aql cl ++qq 9lq
"*9 atEol
#=-k,[A]' (14B'4a)
e*l
0.8
raB.aaÎg 4+6171 +l6ll^J trl=q=r+ ?"1 a4 ++.
0.6
\\
dtAl
kr,small
ff=-k'dt 0.4
\\
A9 L" EE r=0gl^l [A]0olr. ttlzJ +ql= [A]"Itr]. El-+^J
0.2
48A.1
0
m
0 2 3
=k'fodt k..-",,IA]ot
.fg 148.4 2xl HJ¤Oll,\l uJ8E E-E9 ll?-pll t4= Est trl^4 de Eg:d
ol g+E 4Ee q-Slt ?ol ¤4. E7l UB +E= ,*ts t^l HJ8oll^JE tsE A4= LtElLJtrl. qTl^l=
^lE
kr1u,n"= 3krr.a10 ltl'.
5t+6 14 u8^_EE
r4B.4b^lql4 r= \n4 [A]=+[A]09 Bq iH ez1 2il- H]*

ql El4 g *lle-l Hlezvl4e-4 ?ol 94. # = u,,tolo-x)([B]o-x)
^ EJAI2 +E Bzlel zi+
1
ajzgtl t2^l uJBl
t
ilrl; (14B.s)
zzl zzl9 r=gql^J x=0olq, EI4^l +*r+ ag 4Eg 6]]
of 6Jtr1.
tr|+^] li} H}+ql^le+= q4
271HI*q Hltzli zzl voE
ql rr}+ HEI+. r+4^l 2il-Hls" 9l ,r|4 BllEl= +A"J+ ++ =t'J,ar
L t]aF#B[-,
a +6]l EAol ¤zl9l EE'-E+)el HlzJzlE BEzl-*"re+
+HE 4Be A+61 k,tzl 4r4 alHq 4+e +94 ae
4 z)olzlzl trilEql olelql +Eg *g *-Eql^J sqEt}
= +E E+q +4lE ol$aJtrl.(E}$x}el t}^.1 28r+ ztE¤E 4
+¤+. "JHl4o + A-+P E9 mz| Hl¤{r>l)el A+ql= H}
ts E= -H-ol-4).
r
zlzlzl +E t}+e+ A9
=zl Eql
L" r+q=4 Bol 9¤d4.
4EA.3
2n-'-l
#L -'#L}
rrz -
(n-t)k,[A];-' il?J7l [nxf uJ3. n> r ] (148.6)
[ @-#rBr=, = rBrJr.r;{''
E + Tlzl +Bq 2zt HI¤+ + HI¤¤ eel s9 4}4ql * + {+.Jg.JilE tr|.q=r+ tol E4
6ll^l lzloJ 4o14.4
m, ill,-r - r,,
E-t;- =,n#-r"fr
lBlo
l;-
[AJo
tBl
ol+lql +E H4¤- *= qlE e+s+pol4. ol +E B4g I 1
4E6tE tA]el tBlE ^lzlql Ir+= HEI¤ +B + 9t+

ln
EilT[ -ln IB-MBI;
lBl/[B]o
=ln
IA]7TEI;
@ A+ B-Poll EH-d 2it EE +E H=.1
E4t 3 4+ a4
1aB.7aal9 4+6teJE B9 bszl Ael bEe+ qB4l +4lEl
919 "l ¤459 A!+6IE trl+4 Ag Ar+= eg + 9l+.
go]."t 6l"b'll, ol +41= HI+E p+qt=JE4 * zzl
=zlE
E" E
[A]oe] [B]og zlzlt- +Eig + 9l+ {zlrli [A]Oe] [B]0
ln lBl/[B], = -
ol ?zl ?*41 c4++ FilT[ ( [B]o [A]o )k,r
E4t 1 HI-& +q*Eg aq'J +E B4 4E 4s E^l [[A]o * [B]o?.J (148.7b)

A+B+P2x[uJa]"
HI* slE*Eql trl4 AE *szl [A]o-x_tr. B"lzlE Bel *:
Ets [B]o-xtr EolTl+(A7l-6]+ S.qzlE eE. ai4 S.9zl
."F). trI{^J raB.7arl$ rls=4 Aol l4 ¤ + 9l+ al{g r{l QaHrJ -Ea^16}H zld"l +sq, a- 71&7)
tr+{^J
E+El k.g +g + 9l+ oH A++ qlql^l -Bol= Hte+ e
# = - k. ([A]o -x)([B]o -x) ol+E tF+= + + +a qlolElB+El dal aeB + 914.
lAl=[A]o-xoltr+ dlAl/dr=-dnldtolq, E]4^] ol +E Hzl +. zl+E HI¤¤ql ql6ll^lE. ole] ulfal 4l&g 5IH 4
e +gr+ zJ"l ¤4. + +E Hzlg +e. + flg.q, r "JYE. E 14B3ql +E6H
+et4.
1{'B 4= +E E=l 5t*7
E]+rtel 8^l 28 .+¤ E+E= ol8:d 4E

+E +ql^J gqL+= A+B+p ¤9 2iI HI+g ^J4
++4 ee EE 4Eg ^946l]
EzI.
=z1 +EE [A]o=0.075mo1
oll EzI. HI-F+=e] dm-3
el6j6-4a. olz, [B]o=0.050mol dm-3ol+. t.0h +ql BE t:E7]
lBl=0.020moldm-3ol El9.+. ol H}Sqlrlts e9 EoE H
¤zlrJ a* bY a * boJ ^J+Eol+. 6}=el #d EE +q Elzl- e9 E"E H4el Ae_rr.E ol E.JE t-E HEI ^la
zl= ¤+(ol ,]48 Ei+9 E-s.e+ ee)b += #Hg trl-s_+ ,JL+.
6}e_tr_ +4'J + 9l+ + ol iil4+ EL =
"l+6}q ++Efl r = (0.050 -
¤ q-.q_r+ *ol 44U4. 0.020) moldm-: = 0.030moldm-r
1 r( I 1\ _ l
trlu}^J 1.0h +E Ael }lE= q-q-r+ ?"1 ¤4.
(a- x)(b- x)- b-ala-x b-, )
_r _ _
[A] = [A]o - y; - (0.075 - 0.030) mol dm-s = 0.045 mol dm-r

r4-r- +HE 4 6JEg 4E+trt. rqE +¤-r+ ?J* 4
tBl= flql^-l H|e+ ztol 0.020moI dm-3ol+. q+^l
r+= eg + 9l+ =
14B.7b^lg ol+6IE q++ rJg 445 eg + 9l+.
x{E!. I{E.
-g
4.2
-g
4.2
,_ L r-0.020/0.050
''r ((0.050-0.075)mol dm-3)x(3600 s) ^'^ 0.04510.075
I
t- 6-a I*_I 64 dx
= 4.5x10-3 dm'mol-'s-'
I 1
- b-a ln +constant
'"*- b-x
8 208.3 4EEJ +E H=l
HI* ih+ uls

t-l O +E B4r+ f 483 trtz
0 A-+P u=k, lA)ot2k,

k,= [P], 0 < [P] < [A]ooJ trll
lAl = [A]o -k,t,O < [A] < [A]o"J ull
A-+P u = k,lA) (ln2)lk,
t,, = mH, [A]= [A],,e-r,,, Ip]= [Al0(l-e-t,')

2 A-+P u = k,lA)) 1/k.[A]o
u,,=ffillpD, [A]=,.frnr, tPl=m
A+B-+P u = k.[A][B]
t., = I ,_ [A],,([B],j-[P])
K'I
IBL-[AL 'n(AI=Fl[-Bl;
h
fAri!l{+ = ( rBlo - rAl,, )k,r, rot =
lt#}fffi
A+2B-+P / = hlAllBI
)t",
k''=1sfr6;rn lAlo([B]o-2[P])
([A].-[P]) B
,trJ-ffi
,-., [A]oIB]o 1l -e(lBb-zteto
-
J A+2B+P u = k.[A][B]r
2[P] * I tAl,,(tBl,,-2tPl)
/(,r =
m tr1o1.-1u4;'n 1141:
lPlt.:z4s*4ol4 +zl al&e-E +qlq.

2"-'-l
n>2 A-+P u= k,IA)' (r-1)k,tAlf'
l[ r r I\
'!r'
l" t :
tz-l l([AIo-[PI)'-'- tA[-,-l
-)
zr > 3 oJ trll=tPlql +'J- rJ++ "JtFl"l S4
. u = dlPVdt
s48 14 HJ8+E=
T]ILJ=
=gET
tr r. 4E +E gElg t}¤¤ol4 ^JCEg
EoEE
^l+9 EL+s tr 3. 4+ +E H4g "l¤-6ll^l de ql"lq= 6ll46[E gE +
+4U rloluils 148.3). 4lql^le-l H}¤4le_l 3cg ql+6}a, +E H4g q-"J6}r.,
Z 2. HI¤¤g UATH r |,.E2| xl+ ilE qI-e-_E ecq= ql E +E tI+E acel + 9ltrt
A?-l= rlzJol4.
=sEt^l=
z.Af
.A-lzl
OE, ,,.l
--1 I --1 al Es
zl tr
--1 r.!- .^-E tilil ozle-+P
-+u -1 lAl = [A]o -hr 14B.1
zl tl -AE r+lil ln([A]/[A],) = -ht, E= 1i|, A -+ p r4B.2b

--1t!- lJ-1
-+ [A] = [A]oe-ft.t
*+71 tr2= (ln})lk, 1i|, A -+ p 148.3
zl u
--1 Ll- 4E
tfl;Rl s= A -s p
lJ
-+
---1 1/[A] - 1/[A]0 = ke [A] = [A]/(l +krlAI0) 271, l4B.4b
*rJ7l t112= lllqlA)n ZzLA+p 148.5
tt,-- (z'nt - l)l(n - 1),h[A]6-' nzl,n>r 148.6

;(-l
--"l
ti
r-!- -.!
r$il
u ---'! ln{([B]/[B]0)/([A]/[A]o)] = ([B]o - [A],)k f 27.1,A+B-+P t4B.7b
Ê
E4 lt*C tsEo+ tr=6lE U3
ol ri[ t:l$u]C^lE 6ll} r].gq *4("lE¤ 6]q q.Jp +

> ol E4E H||+ts olB
9l'l-).
EE HJt# EB +e.-e Ha'lH, rtal^1 BE a¤ql F.61ts rl¤
ollA,lel Hsl6l= ad$ LlEt'J + g,tE ,l0l fisflcL 0l llrJ E=CE
E46tE 4-E 8+e+ BE 8+ # l7l Llttrl. (14C.4)

^tolel=s-d
> tr{c 7]lH! ol +44= E= +41=:.H r+c.rq +4qlfl+
tr=6lE ?t= ¤86l.7l +l6H^l= HJB rt8oll 8E_t8rt
oJtse-E ^lol ^lt
tlzJ tzl +qlqlE 9E rac.+rl9 zlfalol solF_lr }-E=
EHJ8E + eol -r,a1dtl +GloF Ejtrl. ol ul-o-fl-ee ¤B <lql Eg+tri.
> =JgEt qHl xl^l k:IA], k.IA]n

+E H4l, UB
^h, "l
4_E 8+q zl|uJ(E4 14A), aE +E B4.l tAl ,r- kr+ki , [B].0 = [A]o - [A].0 =
riq (14C.s)
(E4 148)uh lala Ee 8+(EE 6A)= +116lr. 9lGloF -drl.

EE l4Boll,\isl ErdTf^lE *H40J 4E gE"J gE ?.FJ-d 4-E tri+^l ol Hl+e-l ¤¤ tr-+E rl-s-l} p.ol ¤4
E=l= 6atg + !ltl.
qL _k,
K
lAl* -k: (14C.6)
dzll4 o + HI+ 4¤g g+6t= ']]+Eel H}¤-r==g ¤¤g. (Eq 6Aql^J ¤H+ uls+ ?ol ol Alzl "l.!.4ol4H e|E" E
e+q g4 gq4 glrl+ ^JcEel *-szt ql*61 *olrJ I E EL"EE +ilE +48 + 9l+.) ¤eql^J= AHI+ +E
HI¤¤ ral$ BszI S= aEol+. rq+ ¤B e+ qHI+ 4szl *o}"t ++= ol$aflE q ,J+61
^JCEol E*"tzlo
+ qHI¤¤ 146]] fgoh oJ+ =aql^J= ^l¤g
ole| +43 a+= eg + 9l+.
=,
14C.1 BEoe tr=61.= 1it UB k [A]"0 = kl[B]"0 (14C.7)
AE+EI B7t ^J^dq= eHI*r+ r qq}*ol +94 Bol e ol49 A46lE 14C.6^lol E+. 14c.6^lg gEqI4 oJ"J ¤
+ til-oJ H}¤{qla']] olCAill3t} H}+)g r}4tallEz}. ¤ tl+f; HI+ +E ^J+e+ ¤A^14 ++ olE4 o + 4+61
6,qal 4o14. ol ,llg ol+6IH +E ^J+.6I+"J +A6l-H
A+B #=-k,[A] B¤ tI+E +A Ar+E ol+6}q r}= fl +E ^J+E Bg
(14C.1)
B+A #=kilBl
A
AE bE= AHI+ql el6l]^J k,[A]el +L+ E qH]
=q=r
+ql el6]]^J kitBlel +E_+ tr+g+. trI{^l oJqE Hl* +
0.8
l
4lql^l r- da He+ +E= trl-s-r+ e+ _.0.6
l
-)
(14C.2) - 0.4
#=-k,[A]+/citnl
0.2
"J"J Ael 4* E" EzI [A]0, :a4r Bel i]g bez] 001s.+r
6IH tAl + [B] = [A]oE +Al?l 6]tr- C BaJ 4.o14. E]+^l 0
0 2 3
lk, + k,'lt
#=-k lAl+ki([A],-tAl) (14c.3) fg 14C.1 g+o.-e liFlz k,=2kioJ UB A=Boll l HJ-sl EET!
=-(k,+/ci)tAl+ki[A]o 14c.4^.loll Elal EBoll d=61.= Eg.
550 1/- HJ=^-E=
f ?lzl qlEql ol 4e d+4 o.+ 4+61 +,qq} 4o14.

14c.6^lg CHls" 4 qH}*ol tolal HI$ 2145 ?*Y 4+ A= EB+
qlE cB6Izl"J, oltrll= ++1. +el6llot ++ qlE^J Hl*
A+B +Czl 4u3oj9EE zzlola E%F.JgEE rzlg o11.- -Bf+4 Eal
3 ^l+
B¤ adol k,[Al.qlBJ.o=ki[c].ool4, sd6]rll +4u +-qHl Ltj
jo
dE ¤¤ ^J+= +g=4 ?ol 84. +- i7l I E{a
- +, OO
T1 T2
t
^17J,
aal 14c.2 8E rrollll Ee= 0l=;' ?tE Alolltrl.SE= r2E
ado+9 golutl. =E,\lz
EEI ITIE 8'8 Sa|.7|'
El-zl"+ *9 c"= l mot dm-3 trllEgl tr?lzl z-zl t*¤- 2zI HI¤- ^t|ES
r+ li| HI+ +E ^J+EE HlTl +-qHldq oJe_E q= Aol
+.
^J
rgE= Hs+^l714 4l7l dt¤+. gEE E46lrll EsI^l
7l= 6J ttJ$g .,.lgo|4 ?zt"I¤ $zl$ dEts +
"lgg
q
LIE!¤} 14C.1
glrll El r-l¤. r +ql^l d+= "Ja^lvlAt+ E= Ellolzl4
26Jills+ HI*E AHJ6J4 q*6}q HI+ +EY ?+7+ ulol=+ffi ol+61-= 4,o14. dzl *d¤- ol*al-H e+ lps
8.0x 108dm3 mol-r s-t(zi|;e] 2.0x 106s-t(tz|;o1+ trIQ^J F"Jql s 4zl l0Kel 9r
r.qtg "Jq+4 'J + :14. :-41
ol zrJzllo] EI$.ll qfql BB tL+= trl-e-=+ a4 g^ qlolT,iE "llulzl r ol 86IR qi.ll .r.1fl9 9s=
=qg
+La olqlql ro 4zl 30Kvl^\ EE^la + gl+.
a'ox t-old-Ti-m9l-' s-'
- 2.0x 10" s-
x 1 moldm-3 = 4.0x 102 gE #^J+ql qts Hl¤¤ 444EzlE A',J
46H^J AlTl
"
^J+9 Ss. 93
6J4 q,J6J HI+ql ql6J +E H!$ +E
cg 7}zlr. E4g + 9l+
q "JHI4"J HI*ql q6H^J= trtg=4 *"1 tI* {lzlrl#9
sE +rJ +Al=e-l +E ^J+E zlzla_ +ill4 ¤B tr-+=
+4H + ?l+. +c 4 HJ6Jes lzI"J ++6J A+B ¤Bg -I.elap olo.l
+ rrlola qHJ6JgE zzI"J A+B+C ¤¤g r
^l aHJ6Jo
K_
k^
X
kb
X +E 8+=_+ L|EILJ EE A+ (14C.8) + A+ql E+ gEE;^J+rlzl$ +E ^J+Eol t
ElaJtrl-
tr 4
4E Zte-e+q ^llse gEql^Jel <t k,t\ kio + Hot=cll,
q7l^J k,*r+ +AlEql qlql+E tfSol4,ki+ ql* qHI ¤-E EE 4+ Ae+ BE *E= EE dq ¤¤ Ztg rqE
+ql +E tr-+Eol+. AHls" r+ qHl+E zlzll. 914.
'|]oJ ^l+7|tol$
trli= 4 .Jz]¤{l4 4*EI E+E fg Bq+"lot drl. (a) A--B ¤B(CHls" 4 9e}*ol -e.+ liD
gE EE zl+ql= AlTl -4¤9 "l$zl ?*r ?leq, k.[A]"q
1t C.2 tlEtH =ki[B].oE "J+^lzl],r}|Eg ¤B zte_-tr. H6l]a 4o14. :z
4l "l ^l] ¤¤ql EB6t= +E= ^]] +E ^J+ql g=+
ssl+= +q= B¤ ^JE}IE ESolt4E E_q_E ^l¤-
4l7t 4. zl# [A]7] ^]| ¤¤ +lzlE+El x"JE olgqq 9lq^J
++. HI+ +EEql^J= e]+.il^J 4e" * S*"1 HI*E ¤¤ lAl=[A].q+r4 [B]=[BI.q- xzl fl4a- 6tzt. r4B Ae] *lE
+lil5 -',461.41 ol5^lag- ql lfltr3 ad{l r+el ¤¤ a zl-+f,-$ *ol Hts 4,o14.
Cg +ElrllE+ el$"l ae!= ag EoJ+(rH r4c.z).
dlA
gEE #H^lag q HI* +E7l o\ c-E EEql qBrll a -4. = - k,[A]+ /cf[B]
+61+zl$ ^J46]] -BzI. Eq 6Bql^l ¤B+ ule+ *"1 HI* = - k,([A]"0 +x)+ ki([B]",, -x)
el ¤B adg gEql 93ai4tafr"ol 0ol otH A+), tr].+ gÎ
- - k IA].., + A.:IR],. - (k,+ki)x

14c EJEo+ F.alE UJB 551
c1AIZ ¤B tL¤ ol+* ¤B -"9 *z.l

=_(k,+ki)x
ol HI$-E ¤¤ tr-+= ol^J +.lg zie4fl r+q=r+ *"1 4
dlAl/dr= dxldto]'v-+ ol 43 tz1 EIE ILI-Azlol4, r 6llb EIE + 9l+.
14B2b^14 eg 84. ¤-s EE zl+9l BBg-s+qE
=.ol
olBg xoolep alfl q+ lc") _[B]*[c]*
xts q+r+ ?Jol Hts 1"1 -_
([B]"0/ceX[c].q
+.
^l7Jql ^-@-tALf-
x= xoe
'-
I -?E
L!
Eol T--ol
r-
(14C.9a) HI+ e+q*Eql el6ll^l Be+ cE Eo EE ?oloh {}+ +
k,+ki Set [1^l 8J3]
o
(b) A+B+c ¤¤(cHI# rilol7 qHI#: ziD IB]"0 =[C]"0 = 1K1Al.rce)'/'
*E +E 4eql^le+ aol gE EE 4+E aH BB ^JEll r4I ^lt ^J++ q-q=4 *ol ErI.
7L otq4, k,[A].q=kilBl.qlcl.qE
"J+^l7l= ^llEg ¤¤ <]g
-tr Hql?- 4o14. r=lr ol ¤Bql EB4= +E= ^}l +
^ll l=0,+2aki=u:(h.r,)
E *+ql el=ql+. zlfr [A]z] BB +lilE+q x"J? ol
^ll
Eqq qq^l [A]=[A].q+r4-7 6]z] r4H H]+ ir]E"+E E4t 3HI+g ¤B t+
ql el6JJ^l [B] = [B].0- xzl 9a_ E. tcl -lc),r- x7] gtr] ol Ht+ +E
^J+E El= ,tll-e.S
gEql^-lE ¤¤
^J+e+ A
trI= 49 "J + fl$ 4"14. z|,<116l izfl6lzlfl ¤¤ql^l=
E4l 1 HI+ +E^lr+ f 4
gEql^l A9 E"Eb trl+4 ?ol H*4. 4* *4lzl-^dBtI+
^l]
[B]*JC]'
k,[A]"0 =kl[B].q[c].0, l7]-tr- K=
# = -k,[A]+kitBrtcl IA].,r"
= -k.([A].q +x) + k:([B]., -x)([C]., -x) u|4rj,
0 +^l k, _ [B]"q[C].q _
= - {k, + ki([B]"' + [C]"n )]x- k,[A]* + ki[u]* [C]", + kix' ---lrt- Kce
:1461q,
= - {k,+ ki([B]"' + [C]., )]x
*ql^le+ 4-ol dtAJtdt-dxtdtolr+. ol trlE %t-¤^19 oll} e=r, l: ki&r" *zo)

ql Hlrllall^J zl+ *f4
" + +46l+ zlol ¤4. {zl,rl rE ,9 rlt
q-q,=r+ rJ* tt-++.
tr|+^J E+E7l 'Ig4 ?ol ¤4
^17J
1
x=xoe "' +-_
_tl?
I
= k,+ ki([B]"' +[C]"0 )
'- ki(Kco +za)
i
8E EE +E S+ (14C.eb)
a=1K[A]"oce)'/2 t=-stE il+g HJSI
552 14 u8^-E=
TI|LJ=
=g-el
tr l. * Hl¤:ql Eflql gEqL4 ^de"J ¤¤ tr-+: a,J6J:rI q%I . 2. HI¤¤ +EE4 e-e ql46l-= SElEql^l= HI*g ¤¤ I
olE +E tr"+g HIe+ eq(o}4 +e_6J 4# _tro}+). ilE U^l #46tZl ol*^lzll. olq,<1
^l]
aaql r++ ^H
¤B aC " + 4l a¤92il 6I=+.
=s-d^l=
,A{21
o=. AI
-1 +4 4Ha
B¤ ^J+e+ +E ^J+ K=k^lkixko/kix... 4,*g trl fE -+=q 14C.8
gEEE+¤Ba+s99s+ x= xoe
-tlt 4 EJr6Je_E lir l4C.9a
t=ll(k,+ki)
Eq ll*D Arrhenius /\I-I
lnA
> ol EE|= Hll+E olB
HJBE +Ets .gEoll E+Eltl. 0l E=dE a,'.lete.E/{ ?al=
HJ8 E^|.il| ,(jE ",_l-J= nfi golLl,= rl^lrel q+l= 016l{61r. Eel
oltrfi^1 HJ#el dEol gd-E!= 7l=71= -E lR
4aql^-l .Y
'a
xl= tll =gEr

Etol 0l== =¤Et C
PIE= 0l6t|6lts Elts EJE + ?Its Aolq.
> 64C TI|LJ

HJB +EE 8E 9= gzl= e.Edl.= aol gdsl 0llLJxl?.!ql,
ola= U-=01 trtl U- golLlll El.b cjl =Js-zt
Elêl oilL1^lrf. =E?I= 1tT
lal 14D.1 U30l Arrhenius 1l(14D.11I)= "J+lle q= lnk,9 1/I0ll

> EJ.e.Et qHI rl^l E|1EI E,rl7[ 4.ld= LtElL.!trl. 4Cg )E)E -EJRoll l/T=0Ol^'19 trrJe
ElEt HJSq .8¤ Tlxla LIEIH + ?lrlE ri= g0t0l lnATl Etrl.
:d!f(EE ^_E= ^_5i
14A).
E 14D.1 Arrhenius trElElEl*
(t) tz| q16- tI A/st E"/(klmol-r)
&szl94zi$ "JHI4 " e Elo+ HI+ol uul=zll "Jq*q. F* CH3NC + CH,CN 714l 3.98 x l0t3 160
g HI¤¤ql qlql ¤e] A4ql el6IE l"/r,g urgl 4ollrJ s 2NzOs+4NOr+O, 71111 4.94 x l0t3 t03.4
zl¤z\E z*i zld"l Llg+. olAf. yrTl *L

^l6IH 99
(2) 2iI Hl¤- t Ai(dmsmol-ts-t) E"/(kJmol-t)
6IH(= &g-;l94zlH) lnk,E ?zl, trl+^J kol ?zld4= OH+HzJHrO+H 7l4l 8.0 x 10to 42
49 9"laJ4. NaCrHrO + CHrI qlEg 2.42 x lDtl 81.6

+Eq^l
14D.1 U8^-,Eq-q= .xlseq q "*e *E"l t=qq 9lq.
Hl¤:q] r+q} gE E=^dg "JHI4ee + ulrlulrl$ zlzl

r +{{bEll, ol :i}4ulq$g Ink,g l/Tql 46ll^J E^l6I GZ@ Affienus,ElolE|E=¤
olrlle$rllqE(ql+"J cH3cHo)g zzl E6llHI* +E-
t Arrhenius ErlE 6Iq +s= z.ldE A¤4 zl$zlolq. 7a0_1000Kq1^J +a6J ar+ q-sl]4 ag +E r1-+ 6tg
Arrhenius +q=4 Bol 449 + gl+. gfl+.E"sl AE +61q4.
^.lg
lnk,-f"a-ft Arrhenius
^.1
(14D.1) TIK 7A0 n0 760 790 810 840 910 1000
kJ 0.011 0.035 0.10s 0.343 0.789 2.17 20.0 r45
u14"lel A. ol zldE l/T=ooll^J9 ¤¤o +^l(rfl 14D.1) (dm3mol-t 5-t;
{+ g}z}4 qIzI.EE Els. ?lrlelr EI+ rela y}4"l4 r,

ol 4dg zl$zl(-E^/R)E+El ¤qzlE 1o +,rJ gctrl I.4E ,tl¤f 14D.1^lql q-q In(k/dm3 mol-r s-,)- U(T1K)
=
qLlr!4r. +=4. ol E¤ 5¤q^J Arrhenius trBttrlEl+_r. + E= q ¤?-l5}4l (r0'Kyrql q4^l E^l6Iq 4dg g
6J+(E 14D.1).
ol.<J r1o1El= 6il46}8 9u}. !lCs+ qq4= +-qUC
E zlc9 zl¤zl -E^tR-71&7lt*fls+q **4. ¤zl
ss4 14 u8+E=
lnk,,r-lnk,,, =-h++
g+. rlT=oql^Jel ¤Eg h(A/dm3 mol-rs-')ol+. 4a
zl+Bg ol+6}q E^lqL ar+E+q u}4"lq= ec6J
ol 4g trl+4 ?9 Ee HI+l +48 + 9l+.
+. hk=+(+ +) (14D.2)
Eol +d r+s-r+ e-3- sE "J=+

(ldKyr L$ L37 r.32 r.27 1.23 1.19 1.10 1.00
ln(,Udm3mol-'s{) -4.51 -3.35 1.25 4.24 0J7 3.00 4.98 s^d3r+glHzlzl 50kl mol-,"J HI*E a+, gE= 2s"c1
-1.07
*el tz'ce gel+fl$ trIb trl¤-+alzy CBEL+.
ol EE zlzla_ hkg (103K)/rq q4^l E^l*4(rB
Lr- 50x103|mol-' ll
r4D.2). 44' zl*H o e +s TlgzlY -zz.7olq ¤¤g. ln
k,,, - 8.3l4slK- mol- 298I( - 310K
271olq.q.el^]
50x103/ I I \
= 8314s -Tfr
Izoe )=o'781"'
E^= -(12.7) x (8.3145 J ICt mol-t) x (103 K) = 189 kl mol-r
olaE $-zlgqlag a6IE k,.z-2.r8k,ol 494.:a46l
A - e27'7 dm3mol-r s-r - 1.1 x l0t2dm3mol-r s-l
{ ss-= 2e8K-++rl 310K-e gBl+H +E *izl * z
A= kr+ E"Jql *+lE *=+= 4g ++6Iq4, ulle *zlel4.
i
\ lnk.g l/rql zldE zl$zlzl EE +qd+
EH6ll^J E_^l+
al,
I ae eEE¤ eg + fltrI.
o
E = ^l"¤e+q 'l-¤-4
0
$¤El qlLl^l7l ++= ag +E *izl gEql

E
E
.Y \ \o-
L 741 g+ql+= ag FqI+. {r
\ EI"J gr-Csl9lHzlzf oolfl HI* 4szl gEql +
-'lo
kr
\ +6I+. rOl
-5
1 1.1 1.2 il
g^dEl 9lHzlzt ¤-"J trllE gl=ull, olag sszl
1.3 1.4 olil
(1ff Kyr
lB 14D2 -E'7l 14D.1el EllolEl= olEEt Arrhenius -EAl. g+a++ HI+ +E7L e^,*+= ag LFIU+.
xlTlg.Tl14D.1 q*- qlolElE+El Ae+ E"= +4qq. a+q q+^J- ln/c. l/rql q4^J E^l6llE ndol +e
zl e+g rllzl gl}ql
iryK 300 350 400 450 500 "l4el 9s ++ +41='uJ-Arrhenius4'
ft1(dm'mol-rst) z.9xtff 3.0x107 7.9xt07 l.7xld 3.2xtff ol4r ql+ "lullqlE SA{I gEql^J9 ¤}dsl "llHzlE 4
r_lour ft ¤Z
,r_s
r_lour ¤rup or0l x g :rE 94 ?"1 eelE}+.
d0lTl/dT= -1/T2
"J* HI+el gc+ qlqzl$ g4l qH gE r,ql^19 k.,

E^ _ dlnk. dlnk.
_
- d(l/T) -,
R 'dT
<ls-e.+q += gE 4ql^lE k,2akg fl41 q+g + ?l+.
*d "lBl* +4 oE t4D.14g'l+4 ?ol a] _H.zI. tr|4^1,
FE^
lnk,,=ha-ft ltk,r=lnA-fr E^=Rr'(#) gd+ oilLl^t [gsl] (14D.3)
a4 49 E il
^lql^-l
uBIl=+.
"l 4g +}d+ qlqzlE a^l ael"l+. g.dp* "ilulzlzl &
Eql ++g ullE ol 49zl *E a(21d9 zl¤7Dal e.td
14D Anhenirc .l 555
14. ul-Arrhenius4 Ceg HI8"ll^J "Jzlq+4 El.-J ¤t\E tlzlE 6Izl"J ol H1]g tIE11E E46IH BS4 "_e
^JCEg
I zoy"1
=
E¤-g 617l ullEql +4H- +E 9l+. E ^JE+oI q= aol+.
4 H}+ql^l= oi7} +a H+= ge4^J r zl|.ol E6llTl
eag +E 914. EE dE 811 '9do1g.'g-'dol t4'= eg Ee-E lr=
4*zl *zl"J ¤zl,tJ* ol$$ +E6ll +gt+. $,tjatg-e-
11D.2 Arrhenius trlalElElel 6l|4 i}C+ qlLJzlz} +4E q= gqq^JE flzl¤9 sl* t'-E||
ol4, dol q
^J4= a#"J "Jrq4E 9¤4 + ^JCE
o
ol e{oll,<Jts Arrhenius u}r}ulelz} 4s tl-+el gE el= + -e- Ho]zlb gd3tl {t4 flzl-59 ufltsol4.
zlE +4ql= ++6J de4 oje_tr E aol+.*.4L rsql^J

ol# E+ ^llflq4l 6l]49 1o14. +lql^J
=el+t-ll+e-l
AEg'1.S4 eol +48 + 9t+.
gCEl qlHzlE q}¤¤ol +l6ll^J zl4o!
^8C+g "JEzl
(a) U30l +q6F= ollLlrlsl e s+ 6l-= 4li9 "llHzl4.
E E 6114617l +.16|]î Ezt es+ EzI e r}"l9 +rE=E
^l4r-El qlE^J Tlill^J Hl*qlî= ,lla +Y*g ¤:E.ol "J"l4zl"J
EIE Hl* 4eqld EzI trlHl¤ glHzlz} qBrll H6l+zl r +q +61 "Jp"J"l HI¤-g "Jea + qg aEg ¤+q
=
^J46I]HZHrH 14D.3). Hl+ql^J= ¤xll.E olq+ + g 7l7la- 9l+. EE+ eE qlqzl= 4= +EE +g
= 'lal
Eol "J"l*+.+._4ql^l= 4-d=el glHzlE TIT] =
"JBol
q +q]E sqel4r u_ot"F 6J+. q}*ol dqElql=dul4 ae+ I Boltzmann9 EE Ezl(d4l zl^l ¤4 Eq 12A)ql el
B= g:z4zJ:g olq^l fl4¤ il+t614+ ril
6ll,rl s-ainrE +q{4. ol 6114g +g!+ B3 Ee +4U
^Je EBIE_,]" Arrhenius 4l o + q q."J6J + gltr|.
6}rll g+. ole+ ?ol q}¤¤e+El
"]|+ ^JCEol BCq=
ql 4d4
"e. +Hq= flzlzJ ,14+ eq}4E Hp+e+ ag k,= Ae-EJRr Arrhenius tfl-dl (14D.4)
^l
¤¤¤¤ 6I+E +q^J U3 ats+r ++. GI* als.= ts-
d4 " e 716I+4 zl]Hol4 HI+ C4Ee+ d-"1 +s+.) qHr
ol {g r+p.r49 "JHE q-+ rE +l6IH +e4. *i{ _e_
g H}+4lql ql6J Boltzmann +E Egg

¤ qlq^l: +q4 *at4zl EE5l4, ol +Eil gq ^J46llE-H "l ^lql
=ilql^J Ela 4¤¤ "16llB + 9tg 4"14.
9 flzl¤E sl.JillE ECElE"l+r 6J+.
ol +qil= zl+H flElg flzEol z|-ts}|gqflî qfl¤
qluJzlz[ a]46[r1l qr ^J^dEql 6llB16]= r+qi ate_E tr @ Anr*'',*=qrl+?Ix1a14
qA+. HI+E Aeg olT= trlHI¤ ++4zt HI*el alql -"1+q= qlqxl tg+ 7J4 e4 i* z*
"l "l aFl
+}CEl "llHzl r."J 4ol'I. ol tlqql^l= + tI* ExIzI r}] =+lEg
t+o.+). i:0,t,2, ...oltrl-.
^J46IzHrH {zl,<1
+i;l 7l*4l d=61-¤ "Jzrlzlq, aaEI q "JrBlzlH dc =+r
E +e_s 'JqzI+. ol ec4 ul]g tr-Eli= HI¤-e-l dol gEl|
qr 6J+. dol ^JE{q s.B¤} Ex}9 9pz} H}¤¤.E qEet o-EmtnlkT
v
K Emrn
5
6
u t|xil#
K Ea
5 HLO E 2e
6 Jo=
e
{ru 0
=t
UJ
E-
H
H {P zflr1l+
ooe
fg 14D.4 0l -q.J HJSXI= Eg-d 7J719 oilLl^l '*=tr[. E=oil^j
¤B-d Hle+ eol e,,in9 ollLlxl= += E^l=E EEe=gl=
e-t-,./kroltrl.
HJ8 4g,
lal 14D.3 "Jg HJ8oll^1E tr18!¤ oilLlrl g-eE. U8Ert gdE /.lolel
ol 4lql qlal Boltzmann EE= +94 *r+.
trlEl¤ dq E0l7l r u$E gtget 0ilL1^1tr1.
s56 14 HJ8+EE
N, e-ie0
(l-e-'o;.-i'o
N { E(+Etl Hl-1t8) E"(+0l.l afE)
{zlrl N,b ^}EI ,q fl= Ez}f, Ng dill Ezl^f, p=UkT,
rr]a EE1] EL+ qY tzs.za^l o e +qd+. .tlHzlzl- ,",i,.,p|
K
5
HLO E
L-]o=
6
A4 t "ltI"J ^JEHql fl= +zl¤E ++=
q^q=+ ?"1 ¤4. {J
EJ
E'
N = (N/,i1e-ie0
i*,, -l
ir,=i,,- )ru
,=Lnn i=0 i={
I
N_ {'}'"-*,
d' Lt
HJ¤ TIE
88=
;l
N
N
I/-/ e
-r0
), leJ 14D.s +0t|= olEalE '*A gdst ollLlrlE eE= olEg + 9l+. r
{ i=o ,l4e HJ8 +E= qr_ _aeEur q
=7lllztrt.
ol 4 +9 d4ge +El-u qlcg +++ zl6|f,f 1+ r
+f +...o]q, r=e-'fol4. olelql ++el n-rzll 6JE qlg Boltl4. ol "Jxl-b +E"I4 q}*ol gq+. +*t]-
tr++^J
(t-f)t(r-r)oltrI. trl+^J a^qE 6-lg q^s-r+ a.ol ¤4. qql^Jg +E
^J++r E + 9l+ zlf qlzl s-ElRrL HI¤¤
$-ezlzJql +EqI 9lHzlE *= +=9 E¤"] 94, u}4rl
'I',"-")'==# +E tr-+= AE+EI fls-E"rnrg z]"txlE 4"14.
1/(1-e'e\=,i (b) gCEt ollL1rloll Elil= +Et|el Ert

={ (l - e-i"eo ; Arrhenius 96IH +E tl-+E *zltlzlzl f-lo1l.<l= gE
^lql
trI{^l rmin=i.,ne oltE qlqzl$ *= ^JEllql fl= +ziel E geJ+4+ g^d+ 9lHzlE *+olo} oJ+. HI+ E6JEE
Egg +s=r+ ?ol 9"1 r+o.+zl4 ?3 Eol ¤+. gE= HE+^lzlzlY fl+ g^d+ qqzlfi; yf75 ag e=
"Jolzl"J 4'J* 4ull ¤zll 6Iql^J ql*"I "Jqg ull= ol4ol
*,*, N
,_!,.
{
q(l-e-i^*'0'1 7H6I+. +rH. HI¤¤ 7]+^lvl7ltrJ op z].419 ds slqt
g-e nntkT
HI¤¤ "Jezlzl g:= Ee"l+. +,H= Hl+ g.csl ollHzlzl
= l-(l-g-i-,'0 - e-i*i,ef =
)
qg;.]l.E-g HI* as= "J5qrl HI*"l ul-tul] HI+el L
fl +E-e¤ +41= H.zl g+r] 6ll=+(rB rap.s).
z}trJEt 0ll 14D.2

olt9 {lHzlE *!. s-e.*/krg iz'q zEfEl q 14D.3
e-,, +zle-l Egg
zlq, r-in4 kql+ Avogadro t}f NoE t6l-r, Nnr-i, s.A= ^JAl +rflolr+. zl# qI o+z| HI+el g^dEl qlLl
${ar}
= Tlzla "llHzl
E+= ^l-dg "l+6IH +F "Iq^l E^ zle+ zl+ *zI4
"Jzl¤ rou}lE ea^la+r 6IzI.gcsl
"Jq+= EzI +EE +gol f-s-r.tar7l g+. "llHzlzI 80kl mol-,s+El 8kl mol-'-E trqzlH 14D.4^.1
=
E,:50k1 mol-I=5.0x lOaf mol-tola T=298KoJ trl-g q el6il^J 2e8Kql^J9 4s ulzl trl-g-r+ Bol ¤4.
"I= ^J#
4ee A1i$442I +g+.
o-r*oa-t*'*'*l== -(E*ura-E ,*rrp.a
ro{' mol-r y(8'3tls JK-r mol-r 298K )
_k,otayr"a
- for*u
k,un."tay."a A*."t"rys.de-Ea*Dlv*d/RT Aur,."t"ly*d
a
)/Rf
;[ = a-(s'o " " = 1.7 X I 0-9
1
., -80xl0rlmol-r y(e.rt+slx-' mol-r )x(298K)
ol akg 44 rog +e_l 2oll 6il'&++. --m^'^-(8xl0r
Jmol-t
=4.2xl0tl
ol 4lÎ Ar+q el6l$ g^dol

"llHzl9 ali= eg zlq
+l¤s} 9lHzlz} golfl +zl-=ol +E=g oll"I4 tI*"] "J"l
f9 zlf *zL4 olzl. ata!_tr} g,'d q
=
¤o}g trlri+.
44, e.rhenius ^lql E6H^l HI+ +E= xl+ *z}?-l "Jzie+
14D Anhenius l 557
T]ILJ=
=9.-d
D l. Elctrt ollLlxl E"E Anheniusal9 ,tl ul4"lelolq, HI* B D 3. rl+ grEl ?!rt= qlHzlql ++5}r1l EE ¤:E=trI4 t}¤-"l
rll ge¤I4lAE
^l¤ol ++^l HI+g "Jc-zlE "lluJzl4. "Jqq= +-J tlqlql^lel +E ^J+trt.
a 2. gdsl ollHzlzl 4E- t4z1gs.gl r-l
"JzJal4. J 4. +E]l= HI*E gCE+ 9lHzlE *+q
=++ =+.
=sEt^.!=
,Alzl
oe. '1
Î +4 al Ha
Arrhenius 4] lnk,=lnA-EÎRT 14D.1
gCEl9luJxl E" = RT'(dln k, tdT)
olHLz-l
L-l --I
zld --'l
ol 14D.3
=.
Arrhenius 4] k,= 1,g-E"tRr E¤¤ g r4D.4

EEJ ltrE HJ8 trI 7 I L -E - r
+6L7lE 6}l E qE += ++E HI¤¤ "Jc-zlTlE +tr}.

> ol EEfE ull.+ ol*' tI+ Ezls4 HI8 2145 ++61+ 4"1 4E6l ¤:s6tr+.
+il4 EzlE¤ qel golLl.= u8E +E Ezs{= olg4l olEol
LH=xl= g0l0t ohts o1p U30l gol'J r{lE Erl #oll^jel . HJ8 il+,- dE4oJ oJe_E^] ¤e4ql +E Hzle+
l}88 + ?l= gE_t ol.Llat g6lE 8¤E9 +Eg El4sl e= 4014.
+Et
+ =arE
9l7l qlEolq. . Er[E= 7]¤6J "llz]ul6gl E6J¤ z]]zH t4lt A
HJ8
Ê
> 6jC TllLJ Hl*ql rIqI cdol4.
Lrg aEt BJ3E3 Eololrl= E+zr.JAlEoll qal go1+q, 0l l+zlE A+*E +E Hzl$: HI¤¤ql +6}|^J 1^lol+.
EZF=el+E H4= qal Ttrl=^1.= 0lE6|q cill4oJ
g4= =e6|E +,
+E E= + ?lrl.
> gsEt qHl rFl A-+P 1E^lE luJS (14E.1)

#=-k.[A]
+E E=lel u|luJ(Erl 14A)rl 0l E..lE 418 HJE(EE 14Bel
14C)E +116]|0[ E_,tcl-. sE HJE
^-Eoll
Elil= AEq E$$ t-81- ¤zlrl p= ^JCE"l+(q4 tolal *Eol ^JCg + 9l+). 1
:iEf.
,-tiE Aniieniiis -rj(EEl i4D)5. +xlEln 9,10'10f E7.IE "J+3- *Lg ^lrJ E"Jql +qq= AEÎel fzl 84
g + 9l= +zi +ql Hl?il6l.7l qEq lil. HI+ol B+. qls
iJ+ql l000zHE Ezlzl 4lb toozflz| fxll$ ull!-
^l =zl]B
+ ee ^lrJ E?lq1 roufl9 B4zI "Jqg + 9l= 4"14. ul
HI* +E=. ¤+6IH HI* ullTlLl+g ol6l]6J + glrll sl-r, 4^j Ael +6ll +E= _z Eeo Eql Hlqlqi+.
ol5-g 6H46I"l +iL4 0 tr gq+= +41# "J +
^HI+ zBzlE AHI*E +E B4g 2^t+. =
:14. ol +418e ++6J +E B4q lrl4 "Jq+q
^Hl*
ol$$ H z}]9 zlAql E|4 a6J6lH dill HI+el +E BzI A+B+P 2E^lE ABJS $4E.2)
g eg + #=-k,[A][B]
9ttr|.
z$zlE t}*ol 27lzl 9E "l¤-b Hl+ +Ezi HI+ +zl¤
llrE.l AUB qlsql Hlell6}r" E ol HIE= r.el L"Eql Hl
^l-olE 6E
Ell61zl ollg"l4. tr14^l q]*"1 +"J +419 zBzl 4Col4
ql++el d+E Ezl4 ol$ol HI+{-= ol$u| A
HISE=$ -a "Jqa ql= +E H4* run.zalql 44 +El-E.+le¤ +
u35e-l +;(I4 4eq1 "++ "Jqt+. d¤4"J + fl4t:4l- de4eE q"J++).
gr+ ^HI¤+
eg 4014.
H+ Br, + HBr+ Br
*e +"J HI¤-ol z$zlE gal 4"1+r Eqd
iH}+ql {Ei slql H}*!ql= slE+Eel ^Jg s^l6tzl ?+ ^Hl+ql olqlillpl
+. qla4 q^s=r+ ae "Jalr+ q$E Hl*"I ol
o q, ol HI*{g zllzll $zli;ol +4111. r++ 4Ag +
4aJ t}*o14.
{Utrl-. qls^J ol 6J H?lzI7I aJ
dt46J.q Brz$zl¤ qi
^lg
HBrEz[e] aJ srflzl¤ E]Eqql= ag +4U+. CHrI(alc) + CHTCHTO-(a1c) + CHTOCHTCHT(aIc) + I-(alc)
AHI¤¤ EL4l .Jezl| $2145. r iHI+g UA ErlE.
(q7l^J alc'* "J7¤- +"+¤- E6Jtri) ¤e e4ql el6lH
+-Z 6J+. 1=rtE USqlî= t Ezlzi ++e-tr 47llzl/
u1 ,!l-e.¤ flzI u]]¤9 olE+. qle^l s+¤l
ol Hl+el
"1zlq=g'l+4 ee +g +41 ^HI+ol+.
^l=_+E+$ol
e F q= olCeills+ HI¤¤ E + ?14. z=xlE U8ql^l= CH3I + CHTCHTO- CH3OCHTCHT+ I-
-
6J /*E Ezlzl +E-6lol qlq zl+ flx}4, E= gz}+g iil.
14E HJ8 trllTlLl= 559
ol
"llzlrl# trl+$ Ae ¤84 " + 9"14I +E H4r+ # = k"tAl- kolll (l4E.3b)
+.Jg+.
B p= r9 l+zlE +rl HI¤-ql el6ll^l ^JaE|. +
=-q ^JcE
u - k,lCH3Il[CH3CH2O-]
#=totIl t14E.3c)
+* ¤ql^J= gflel ++ *41$$ q¤rll e6J6lq EllTI

** azl9lE e"Jol =,xfla}r rullel "l t.EE [A]0ol+1
q==_q_E_ +44r E 6llBt6l+ dill4 +E H4g +Eg +
otE raE.:"r]9 lzt +E B4g 4B6}q(tr.g r+soll,qe+ e
ol) ffig eg Arl^= eg + 9l+
glbzl"il +6H^J ¤Hg 4o14. r3l+ ¤zlrJ +d +s+
Î
¤e +++ 2+zlE iHI+ 44 0 e "JqLl+ HI# 2iI HI [A]= [A]oe-t"' (14E.4a)
8"1 9zl"J +E5'zl o e ziloJ Hl# +*+ HI+g + gl

rft {olrf da} "]lz}ul#¤ e46}BJH Hi+zl= ^ll"J4zl ol pffi t4E.3b^lql Br EZIeI erl.6lH r-]-s-_r+ Ag ^l
a^|6}q HI* $Aoll,rJ 5-19"1+ +ti.llz} +s_=zl$ E g erll E+.
"Ior *+.
qA4 H,(e)+I,(s)+2HI(g)e+ ee HI¤+
olBl+ =4ql
aÎql E6H^J trl]E6l +d-6J eI*"148 kblll= hlAlo.-e'
e+î
^ll,J6J #.
"Jrll El*.4. ol HI¤+ +$ql 96H^J A6J ^J-Ell7I r.
^l-gg s= Eolq,
+q= B+6J 2+ziE HI$ H,+rr-+Hr+Hrel +g _H_zl4L "l "lE %r-a^lg [r]o=0ol+r +eH(a7lql=
+Et r* ++Elq *fl+ +.?J4l7l HtrD 6117l. trlp-r=4 ?ol E4(k + ku"J 4l).
k^
11E.2 E+4 4U3

lll = T-E (e-*"'- e-0" )[A], (14E.4b)
6J¤, txll+ [A]+[r]+[p]=[A]o"lr+.tr]4^J r+s-rleg ar+

"J+ HI¤¤e q-S ¤+4 rBzls Hl+ql^le+ *ol +zlill Eeg+el+
(r)7I B^Jq.4Ag A4^l "Jq\l+.
lPl= ,.u*t+L) lAlo (t4E.4c)

e515p
+zlill= HI+ +4lql^l +44zl"J d4l HI+ e+pollE 4 +tzll ;ijr.{l E.Bgl4z} o o e eA*+(rB
rel t.5a=
44zl ?+=+= ag +E-6I¤4. {zl^J= qH}+9 zl*C r4E.1). 31+
^JCE P9 EE 0e
L" ++q frzfilzl
^lzld-q
g 5_rlap r46l-q EE ez| d+ Ps qr + +E ¤B lAloTlzl ER6J+.
g6.JEol "JEqzlzl ?;:=+r TIAqFl. olEl6J HI+ qls^J
+-q-4 ag "J^l^d .J+q +r.1. E + gl+.
=
,r, g
$ rr, 1g,''"o",i rr pu 0.8 _+
P
(^lzlE=g *4lzlE +Elutrl-.) 4 3rlo.I+=9 ¤a E"E H4 o

0 .6
---]---------t--
¤¤- LI+LllE +E Bzl# "J-r olE¤ 4.J* %rHpe -)
E-J6IE ol+lql a" F9 Hl*E +Jg Ea.J + 9lg 4"14. ui 0.4

Jo
+d AE lBzlE E6]] HI¤+ q*4 eg +EE +qqr 0.2

e*9zl ?*=+. A
0
0 5 10 15 20 25 30
#=-k,[A] (1aE.3a)
^17J,
k"t
feJ 14E.1 E+ HJB A-->l-+Poll,\1sl A,

"! P=el tsE. 0l +d=3
l,
+rJ^llr= As+q ^JCqzl"J(/c"tAlel +E_tr.) ptr. +qs+ ku= lOkuE Err. 14E.4a-cLlE¤ E,(l-d A0l+. l7l fldl'= 88=g ttll
(kulrl9 +_tr +). El+^J rE dE +E= q-s4 a+.
^J^d E r Eszl Eîl die E|=rl= g0t0t etcl. e7l
=?,1^11
r+r.rE e,oEl-.
560 14 u8^-EE
EZ@ E+HJB'IE4 *s-zl 4g &

Steady-StateApproximation)9lriE +?JAI 19
q
9 frzlaJ4t zl4++. +ill4 o-tr HI+ol *.zl ?tr 7l
="+q^J Hlliloatch)H_".tr. RE Els"z.l4^-l rScE I
E].trI
zg zl+H E. +?J4l rel t:E_7t 0_o e+El +7I4q, +-,q-
= "JEElr d+ql, ol rts Ege_6J c-e 4l4dirJ
Hl*ol "Jq+. E.Jql= ol |.Ez| 4E H6Izl ?*=+a 7l
ÎE"J
E6ilg+. 4 *AlE HI¤-==g tzlo14. ^JCE I7t 4qE
caJ4r:te 148.2). +
bE= ++{lE ^l4g +dlq+.
za{E rEt IE *:E= 14E.4b^lql e-l6ll^l
$=o E+-dE|l (14E.s)
^l+ql E=6J =^l
4. atrllarE 4l&'J trl¤. olag 0 o + saa 76IE ¤+.
ol+6IE HI*
Eol l4E.4b^lg ElE6tH trl-s=r} ?ol 84.
ol
=^|=qls^l "ll?lLlf& b96}zl7} ¤lt +l
+l4l+. *q g+ lit Hl+ql+ ol =^l-= 48rl
dtII _ _ k"(k"e-&'-kbe-h')[A]o zlE zop.3b^lE du)tdt7l 0oe. slq r46l.q ol 4ol
dt - ko-k^ k lAl-kulrl=so1 E+.rqE
ol fg-;} t^^*f ?-]A k"e-k ",* -/coe-kn'-., "J trll 0ol g+
t=
rl=h A (14E.6)
"l ^19 "JEE zI¤

ql+. +l6IH q-q=$ *"1 ¤4.
ln( -(r.,* = lnko-kof-u* C+-^J=il +AillE tEz}HI¤¤=E E"E9l
6|eJH
=^l¤
*r k. <ko7l 49oF EI4 14E.6^lql E6l-E
Hl6H^l trl]t6l
olag ++r+ t"l C?-]ts + 9l+. +aillel Eo EE AE
tE Hplql q4^l E6Izl"J k"/kb < 101
ln (k./ko) E+ 4el H6Izl ?+=+.trI+î +ZlzllE EoETI gfoJo| ap
tI*"I Lejot 6F= e+-*Elle_l + aa"l ++s+. 148.6^l
fiE -m = ftuf*u* - kof,u* = (k" - kb )f*u*
E tllE atg r+s.:crloll Bq+H "l cl-e-$ ?ol ¤4.
trI4^l ^lol
f."*=#rf [] = (kulko)[Al
dtPl (14E.7)
dr
=kn[] k, IA]
ulr rel f
a}Aq= ^laq +71++. rBlE pE ^JC +__,Ezl Ael e^l +E(l4E.3aal)e} F"J6I4I
= =ol qq, + 4¤"1 E+ +E ^J+ k q zlH]]= B=+ Ar+4s
ItA Erl| uE.1 IE slql bEE 41416Ir +4E 4*ol
q"J6Iq+. _e HI¤¤ A= HI* r+eql^J rE +4qzl ?*r zld r_e q
^l+loJzl
("tt -qr)t\t t',(\ll"rfi o[V]/*"'[I] :E a4 eal gq. ru8.749 6I]E tAlql 'il{} 6HoJ r4E.4aalql
= =
=
Br 4E6IE +g + 91u}.+
1t*E.3 ¤+8Ell =Jt

HLO
-
AH/\IP
do=
L-o=
zl=-ozlzl) 4l4}ql^J= ,-vl^l *{tH HI$,llrlq

^l"go]zltrJ
=ol :t4l "l^Jolrl+ qHI¤¤ -r.El6l]ot g trI=
+4 z"i?-l7\
-)
;-+EE ¤.d.6llc4 qq +4lE g HI+E a+q= 6H44 ui
"J 6il. !-zlzl zl9 Ezkaiq, :a461-q += 6]]B9 *xl ?*
lo
eH "J g+. r 6J TIzl 'JH3 +E H4E 6llE +zl 4l4}6t

aolq. E. + zlzl *83 SrlH o +...1, olag ,JE.J +
= ol+atTl qEql =rJill
4¤- 4l+"l]^J u-ta1 aolr fl= a"l+. t
8+8E]| A+ tr-ele+ +¤-6}71 fla1l,<1 o14 ^lt,
=^lH(Tlz{- fH 14E.2 g+gE]l tsE= Are ,J= +^16l.q
g +^l C+_tLq ts?] 8fl4; essA(euasi_ ,JB 48= 71E
=^lEE
E6l^l -erEqr
=71. =ZJillq
T|.81EI.
=ÎB"l4r Edt|^'l
14E HJ8 DllTfLl= 561
T-T
A P
e 49 4fqr4g-e Eq^J +AillE bE= +4'}]= ^l
0.8 E¤ +6Jr+. ¤-9_E "l 4=¤ ols-"o[{ Nror9 di]14?l
0.6 ^tr +EE +EI'H= ^lg +6J+.
+Aal= Noe+ Norolq, olEE dE E" E H+g
_o
a o.q =ol
Lti
JO
0.2
0
# = knlNo' llNo,I - [No] [N'o.1 = s k,
0
k"t
2 3 qI= = [N ,o. - kl tNo [No, - [No
k, ] ,I ] kr, ,] [xo. ] =o
^17J,
f.g 14E.3 E+ HJB9 +E 8+E ko=2}k"E ts9tE ttllel .EE- g"J

ol- + sB *a^l(44)el 6ll:-tr]ê-r=r+ gq.
6|Zl ?-d 8+ 8Et| 0lE6H^l +A HIE-d raJ.
(tAloll tH-d=ltst E6t^l *Pl=tr|".) =r|(Ed)=
=^1.=
=Cg 1ruOrJoil Ell:d
^lE
olE
lNo,t=effi5 rNor=&lffiHP - (ki+k)k,

k^ko
t
[A] = [A]oe-k 4EE.t
rqH Nror9 ¤E EoE {ffiol r+s=+ 4.ol ¤4
I''olnl =J, clota t- k"[A],
J'.-0"'dr
tr++^l
ry = -k"[N,o,] + ki[No,] [No,] - k tNol [N,o,]
[P]= [A]o(l-e-L')
(14E.8)
= -k"[N,o,l * Sff ffi - ,*,o,1
_ _ 2k kb[Nros]
olag *ql^J 7* *zl"J A+-+EH
t+r,.+c^l(ku > /r""J ki+ ko
"I)l}
Tl49= rAlî ¤d dal +il dol4.-LB r4E.3g olel ?ol 7
d]|E *qlî +q! gg6J 6lle+ Hljzfl aol+. kbTl k^
N2os= lzt +E B4ql q+ E6llElq, +E tr-+= r
qL =
=Î
B+ qlt6l =.zl ?*olE ol *H " + ^JR6l C+ql Aq¤
k^,kt^, "i hql 9fa121"3 k q= el=6}zl ?+=+.
eg + 9l+g "J + 9t4. xlTl g'71 14E.2 e-=q E61l HI+ 20,(g)+30r(d9l 4
oJ +E Bzl¤. trl¤, qlT}q=q g45ll^l +E6Lq+.
@f, E+-gqt=Jtq olE OriOr+O ka
trH. Or+O+O, k'a

Nro'E 2Nror(g) -+4No,(g)+or(g)oll
"i4 +6]]g+ O+Or-->Or+O,
4 Ag qlrlq+3
kb
ol-a" 6pl +E H4g +E6Iq+.
q:t
( [to] + [to]l{)1, [¤olq rt"tz- = rpl [¤o ]
p :-E
NrO, + NO, + NO, k^
NO, + NO, + NrO, k:

NOr+NOr+NOr+Or+NO kb
NO + NrO, + NO, + NO, + NO, k, 14E.4 +E-tr8 E4l
trE ¤E g^l ql6J H}+^lql^]= E= +# A+I+P H!*91^l /,.<ko"J qlE A+-11-El] TIaol CB6IE
^HI*ql
zllpzl_e-_e. *44"t 6J+. qla4 e-+28tr +EI4zl t* AE .bE zltzl P9 Lo E Gzl* zJ4. Azl.<J fg-5116t 6J
Î
-tr A+B+B-tr- +ElU+. d9 e+rel r+p +4lEE 4uzl e+= 4"14.+ Ie-l +
sz| e9 *.Eql Hl6ll^J 4+61 *zl ollEql /c. <ku?.lls E
a.al-g +d +AillE zI44-7 olEE dE ^J¤ + +6Ir E4l t4lE +E kbUlTI aail +4lE +E /c.tAle+ A
^tEI
E= +44= ++. olq^l a+-t}4 0l+6} ,ll !b 1o14.
^]g =^l-=
{ olE9 da Hqgg 0e -+ +=+. q-gql*
"lBll e
562 14 HJ8+EE
r|]e+ + 9l+(6J^J r+zl= ?t+). "J"J Hl+ "llzlul69 4.

+4171 +E ee +4lolH FltrIs= E4l=ol Ql$al mlE
Al oJq+!-E 4 +.rJ^1\7l. $zlzlutzl E ^JdEe H6Izl trll
= xlo llru
Eql a +4lE HI+ +EzI dill HI*E +EE aeo}rll E
0lrll L
010
-L
{0
-n
lJ <v
b +. s"J olq+ +E. ea +al= +E ^J+zl zl* 4Ie HI+
xlo l/ 4{ol= e +E eA E4l= $CE+ {lHzlzl ,ItL +e HI+
=k I
E4lol+. "Jt ol alqg HeE +tîlEol ^JcEe +++

(c)
A44l ¤4t:B r4E.s).
fg 14E.4 0l= HJB 7t|g raJoll,\l tP arug ffil= EZI= -Lell 7f=
El+l= LaJ E4l= LtElL.!trl. (a) lull cJ)1171+E E4ltrl'. (b) Etrl| trj4lTl ztJE! 0{l 14E2
+E =8
Ezltl'. (c) lal =JAl7l fl71= 6l"rlPJ olaE +tr161.= uu[= 3e7l
=8
?l7l nilEoil 0l lal Ezlts +E trj4lTt ?l Erl-. NOz[ NO2-tr 2NO(g)+Or(g)+2NOr(g) H]¤+
=tr
r+s=rl Ag qlrlq=q
^}s].qL ,r++ gq$c}.
NO + NO + NrO, k^
EE #E 8^l 'a +41= LqI
+AH uul-s7]l "Jq E {l
NrO, + NO + NO k:
+^l a +4r7t +E-ea +zl',+r g615 g*tr}. rel+
olag Efl ,.J4olq, + +4lE +E= E"J6Iir" +E S+ NrO, + O, -> NO, + NO, kb
7I r-l¤- Sol4.
r7lr +E B4e 4+r+ aq
r? r r
o -a eJz{!(RDS; rate-determirirg step)E d dlNorl _ -^ ^
Zrc"rcblNUJ-tuzJ
"JHI4 ^-E =8 dt kj+ko[O,]
4l HISel +E= aI+6]+ HI* tril7}q=el +4|+(olzl.rJ o3
eo 6Ia il= qql^J= /c,(/c. < ku)91 el6ll^J zlH]]q= azil +al Hl* gql'E 49 o,E 5ETI qg;61 4t1 x:<hlo,l"J trI
+).+E eA Eal= ^JdEol ^J^Jq= 444"J *Eol4, E ol +E H4ol rl-e_$ u.ol zltoll+I4.
4Ig +E tr-+$ HI$"J$ oti..lr+. "Jg +E ^J+= *=
= qP=2k"[No]'
+= HI¤-ql E61]^JE ^J^dEol ^8a ql= 4Ig +E tr-+E
E4l= ul4zl-ul4zll 9l "Jq(rB AE.4). A+ql q+^J= olAg a4 +4lE N,o,9
rz| t]-!-ol zt:l Hls"4 a^J4eE "Jqg ql= HI¤ 4s zl ^JC +4171 +E AC +41"J
¤. +4u+. d4lzl HI+.il ql+ +E B4e zI+61 +E
69 tzyqL 6J +41)e+ +Î ri} +E ^J+(+= 6J +41) +
AA +4E +E HzlolEe A+o.l ol qlzltl4 H;,
E ^J'H4 a7l7l 4g ol$allo| 6J+. ol$rll 6IB tile+ 2
= +E Bzlg 4El¤ +E ?l+.
7I HI¤¤ Hlj/oJ + 9lg 4o14. +¤- t+6J qlql^J "l ag
¤Eg 4o14.
+E ae +41. *= HI¤+ abql r +E H4g dril
1/rE.s I.d-BE
++6}rll izl4_o +"J "Jq+= ¤+ HI+ trl]4lql "lzll 6zI
i-ll r7I q+4 ?"1 el¤¤ Ae+ 86I-r. ¤Bql EE6l= q +
alq},llrlq=q HI¤¤ ^J4L6]l -H-zI.
K
5
6
A+B+I ko
>p
^td-EE
(14E.e)
{ru
xt-9.
EJ
E'
-L
-4.E
=L
.4.E
=L
.4.E
ol
"llzl-r]¤ql^J: 6zfzllzl
qI¤¤$ ¤¤g ol?
= ^ld-trJ
8+ Eol ${¤i4. olel6J ^}d-¤¤e ^8C¤ +7J^ll7l +^l H}+
-A -!
-I
.\l.,\
d-T-
/\I/\
ci-r
RDS --l
\-/ 'r\) Es qEolz}ts 4E7l olaol ^JdEe H6I= +E_84 *1
u8el t]"J d rl HBI-= trll ol+q4l+. . ÎA-¤¤ol gq+4$ t;) ko
la 14E.s I EZ|Tl'+E E4l(RDS)?l ollTlLl=oll rH-d uJ8 UPEJ. ?+"t 6J+. ole+ tol A, B, q r7I ¤Bg olE+a zlAoi$
=¤
14E u3 0llTlLl= s63
trl-g-4 ++sAl7t cBq}tr}(Eq l4c)

r7l ^JdEs H6l-= +E t}+zt HI¤¤e qEolzlt 4
/kl
E tF+E+ g{ z}"}^J h <k,""J rll=: ol 14E.1244
K = kuc ^Jol
a4 ¤q.
K_ II]c" q tu=s A
IettB-I
B
f rorrur (14E.10)
rtTl B7l 14E.3 2A--r(K)q olq^l r+B-+p(h)7} "Jq
+= Îd-¤¤ ollzlr]69 HI¤+ dill4_e_tr. :il. tl$ol
ol rzl pE- El= Ei+ 4E7l ql*61 LEJÎ
^lql^J= ^|d-B ES s-q4.
B¤- zllq?-lzl ?*=+r z|{a;}Q1ol-4 EzlE -H-o}+). tr}4^J lsl.[v]("rDI?) =ry/[a]P .E
Pel ^Jc +EE
trl-.q_r+ ?ol ¤ + gltri.
tll = (kalkltAItBl {zlrl +E-6llo} ts q} 5ae rup,.rz4

+E 4 +E ^}+.
3 gsql rI4 ?zlalzl"J k,e r+^l ?+g + gltr|- 4o14.
#=0,", r,f retrnr (14E.11)
rq6}o1 "J"J +E ttf t;.1 k.kbel =,,Etr| q uu|trzll +7161
E k =kkotk:^? &E ?zl9l IrI4 AA6II q+,<J s--rzl. $
ol +E B4g rl+r+ ?ol 4'J +E {l+= zvv 271 4-E 4ztfl qI*"] trJ LEIAq-. olag fqr4 " + ol +Et HI¤+
Hzlol4. 'gel ¤+cEI qqzl'. *=+r "Jg + ilg 4o14. qlE^l
o,=ff r+p..rz4 +E+E ^J+.ol ArrheniusB(tr4 t4D)E g
?+
#=k,tAl[B], $zl.ri (14E.r2)
E 9= +41- +4U+a 6IzI. relH Arrhenius^l(t+o.a^1,
k -A.-'.'^lql e-l6H^J ++4 eg Ar+= gg + 9t+.
ol
Îd_¤B
,ll7}q6ql^J= t4l r +pzl +E ae
"IzlE
+4171g+. r d *4lE +ti]lE bE= c+ t}4s a¤ e'*r = e'd
6]| += 4ol4a g + 9t+. ex-Y = ex/d
AÂo )/RT
!^-rr,.+Q5-Q,
GZEil B+gq =Jl= otEEt .* A^,
^tt-trJtrq
A+_^JE4 ols_"a|{ r+r.g^l9l _E_ql H}+ r}Cg + trl-+^l Hl+E ¤E g^Je+ 9lHzlz} trls=4 ?"1 84.
=^l_=
46iq4.
Ea _Ea,a +E,_E
a,D
(14E. 13)
Hs+ +EE j|ir' ol

a,a
l!.a19 Al¤l +d
pe+ 19 ds +r
q^J +ai] rql Eil6l]^l c+ tl4 4+^lzl4. "lH l.46}"l E^,^+E^,o>E,.,olE ++C+ qlqzlTl- "Jol qr(rH
=^l-= E^.u,)E,.+E",uolE gol gq(rB 14E.6b).
41 6H^J Eg ols-" al.{
^lg
pE Hs} +E= +e}+ tE 14E.6a), ¤zld E
g + 9l= 6}+el +st} eE¤ qq +4E ol+qzl. EI
Pe+ rel dg- HirI +E= +s=4 ,JL+
=ol
#=0,", 8+-8Efl =Jt
# =ttoltBl- /citll- /cbtll 0

Ea,a Ea,a'
E ll ^lg +E trl+r+ ?J+ 4+rI +$trI. 5

K (a
6
{ru
rrr=HP ulJ
E' EA,D
b
olag pel q-s eq¤ e

^Jd 4s.91 ++ ^]"il HsE
g + el+. U3 4T
fa 14E.6 l^lE-Eeol ol+Gl^l= u8oil^lE 37Hq gdal oilLl^l=
# =oot,1 =r,
ffi =k lAl[B], {zl..l k,--
ffi r.a16H+ol0t:dtrl-. 0|= Ee
ol^l"f Exloil E|]et aol+. 0l^|.c-EBel
qrl8oll
ggEl-oilqÊsl gEH4
aolq, Lltrl^l 6lLl'=
EHzf
1710il qa[^l Exfl4
gdal o]lLlrlT|- (a) S0lElulLl (b) g0l E|ts a0lq..
564 14 tt84_EE
*ql ql6H^J= HI* +E.ql 4o-J gE a4g EuJ trll ,ll+ C + +q4l HI* +4lqlî(B¤ql sBalzl dE) F ^JdE"l
Hl¤-g + HI* +E9 Hl, trl4^J + +E tr-+
+6]10} ¤Itr|= ?,o14. ^JzlE tlql4
E HIE aag+.+
^-,E=4 "J Eg+4

1tE.6 HJE E]IEI lP,l _k,.,
rIH]I
^-,Eoll
iP-j
=
E; +EE4 rl,lt (14E'14)
ulz| +-EE4 rIHllE E.g trliel 4+u+.=

a+ql El+^l= r}¤¤Eol +"&qi ^JcEg "JE + 9l+. el "lag ^Jc+=E
¤¤ql +tl gEoI4 aSol "Iu tlql4 HI+ +EE rEJ6l
e.,tJ t"J-zl¤*zlE *= Hl{lg a4l3l+^la ql= ol rlQfzlel
zl6}^dql el6ll^J Q eE-, 44-, q ++-^l++
q +g ¤4"14. frzl:+el ¤eql^J= s6l g6}b ^JC+g
^JCEol +"J g "JE= A.eql +?]6IE+ HI¤+g dd6t= 4ol BE"J
el ul¤E ^J4B + 9l+
zl;! r-1-9-E4 ?JZ 4rB HI+ql E6ll
rll ol4* ,tl$
^l F ^J^dE
p,$ erz| ^JA+r 6lzl "l4q} 4sE4 zlHl] ^deg abJ6J 4o14.
Hl¤¤ Bdttzl Ttrll 6tH ^J^dEel ulg"l gqq}4 CAql
A+BjP, a(P,) = k.,r [A][B] E6H^l AAqq, _Er= HI*=-4 ^J^dE-=g s= HI+ Gibbs
A+B )P, u(Pr) = k.,r[A1[BJ .ilHzlql E6ll^l ol ul$ol aa¤+.
TI|LJ=
=gEt
x l. Hl+el E{!7lL!=g H}¤+g s¤E+_ "JE= +itzl iH}* tr s. 8+88fl =JHl^l= jr= HI¤- ¤trJillSE t,szl- dill H]
+4lEol+. ¤-r+Cg E6H^J 49 Aes .Je6lrll +zlgqr ,IAqI+.
a 2. al!89 ErE= Hi¤¤ 6171 9l6}|^J eol} Ezl¤E +trI. D 6. ,\ld-B$g 6zlzllzl HI¤¤r+ ¤¤g ol== tr4"l4, "l
tr 3. r$zle li} HI* +EE 4441 zBxlE AHI* 4zlzllzl ^JCHI "llol HI¤¤e qEoITl-= +E
tr-E1]=
^,HI¤+
gzzy HI* +E= +4U+. E"l rJCEe q= +tr Htrl g,'s Etsl-= trll "Jquq-.
a 4. ^_,E_=g
811= dill HI*el +EE zluflalNl gb zlt: A 7. *8"1 ¤Bql ES:olzl dql= AA HISE ^8CE"l +E=
fl HI8 qlT}q= +al+. 40e Etrg+.
=e.-d^l=
ce ^l
+^J al Ea
lEzlE Hl* dlAl/dr = - &,[A] A+P 14E.1
2+zlE Hl* dlAl/dr = - k,[A][B] A+B+P t4F,.2

od.^.? EI- s t" tt' T4E.4
L-l --1 --1 L-: o IA]=[A]oe-a' A--+I--+P
[I] = (k" / (ku - &" ))(e-t ' -e-tb' ) [A]o
Ip] = {r+((e-tb' - kbe-qt )/(ko - k" )} [A],
a+_^JEl] dlll/dr =o r= +tiJ 14E.5
=^t
E4 It*F HJ8 EllTlLl=sl ql
A
> ol EE= ull+= o!+
g+ 6s-Lf HJ-A ollTlLl== )l^la- fleq qaf^1
=E-d ^lel=
6t|0F
=E'-d
-dtl. ralolq olal qlTlLl=oll E-EIE HJB
EZI=9 8tH4 UB +Eoll zJ-d 7l¤g clgXl 6l|0F 6fts^l=
g0t0t -Lltl.
6 A*
> .4C 7llH! A

7l-trZf ollTlt-l=oil cHet 4s E=l= fttr61.= rll tr.+diE}|
?^l7l olEEtrl. =6',1 lg 14F.1 lErlE HJ8oll E:d Lindemann-Hinshelwood oll7l'Ll=.
AE^PI trlE AErlel-6E6G 0l AE^[(A*)= trl= As| 6E=olrH
=!!_r, ==
> Ee.Et qHl rl^l TlSElzLl--EE= 1E^lE rl¤oll r4alErlElol SdEe Eq-.
+E E4(Eq t+n)q T}|LJ= +^l6ll0F olH sE ¤+8E|l

=^l
(EE 14E)= 0lE6|'q cill HJ8 +E H?s]= olEXl PsaF=-xl=
gopl eltt.
E=E4l g+(rB t4F.t). +
A+A + A*+A #= k"[A]' (t4F.1a)
B.e HI¤¤ol qEl +4ls ol+qTl ,Irlq=ql q+ olBrll EE EZHA,I)= r+s=4 ?ol 4E EzIe+ ¤lE=6lq r
^Hl*
"Jqt+. olE 4 A+ql qlfl^-l 4.J+,ilztr]6¤ z|{a}r. gg +E 914.
"ilHzlE
a+_^JEH 714& ol+d-q +E B4g +E6l] E + 9l+.
A+A* + A+A #=-kjlAllA-l (r4F.1b)
ltF.1 l=rlE UB
E ol qldq Eg Ezlzl Ezl 4.414.\14c8 p= EI5 +E
e*¤- zlzllt q]¤¤"1 1^l-HI+q +E Hzlql q=+. 9led z.l 9l+. + olaol r$zlE 86il HI¤¤ "JeA + 9l= 4,o14.
F-Psol lr + sl-q-s 4E olcdille+ qI¤¤ E + 9l+. +
=-tr
cyclo-CrH,,(g) -+ CHrCH=CUr(S) u = k,lcyclo-CrHoJ A*+p d[#|.=-kulA*l (r4F.1c)
"J9 ol lEztE tI*E4lzl-+E-AA +Al7l Atrs -

lil-+E H49 6]1461"= ql glq^lE Erlldg Ezlz} HI+ g
I "JezlBJH gA 4= EzIc+ +E6]]^J gs+ {lHzl$ ¤ elril "Jq+H dill Hl¤+ li} Hl+ol qq dql ar+e+ AZI
olot aJ4E 4"14. rfl+ ol+l+ +E=g +++ z+z} 4C g+. olag Hq6l]l +B6171 916ll A.el ¤E r35 $s.91
olq q4^J qB4l rz14s Hzl"l +g f 9ltszl 9dol E + c+_tlEl 4+^14 E+.
4. rz} zlill^J HI*g E6l 'l¤.xls. q1e;ol+a +=7lE 6| =ÎBg
Erll, olag HI¤¤ Ezl-i."] dc$e Efl+ +eq rEzI $=k"[A],-k;tAllA"l-ko[A*]=s 04F.2)
E iHI+ 4C"l +01617l u1lgol4. trlfl^l ol +q-

^FSg ol trl+"+ ?"1 C"]$ + 9l+.
ull= +ill4
"]l7}q={lE r$zls 4C4 E|rll 2+zlE !+e ^lg
E .q ?l o ', + +9E 6l]0} 6JtrI.
l+zl-.E HI¤+ tqztHoll il¤-g__e Frederick Lindemannoll
lA*l=#fu (14F3)
E6H^J C*4 0 + ¤EqB.gq, olq^l cyril Hinshelwoodgl r?-ld-q P7I d^Jg= +E H4e q+r+ e."1 ¤4.
el6ll^l trhFq4.4. ol Lindemann-Hinshelwood flTlLlEql
el6lH HI* +zl A= += AEzIe+ +rE=d-q qlqzl Hql^l #=kolA*l=m (14F.4)
566 14 u3 4-E=
ol +4lql^J= ol +E H 40) t^l7| ot'.]+. rq+ (A., A) +

k,,z=2.t}x lQ-ss-tol4. ol ollzlt-l6ql^l gr-C+ E4lq 4
Eql e-lf, Tle +E7I ^J^d$ol rJzlE r+zlE HI+E+ tr|]
el +E *+ ft"E Alt}6l.ol4
+61 ts+^J /c'JAllA.l >krlA*l7l E)4+
=(tA.lE ^J4l^l7l
r.) /c'JAl )kJl4E r+r.+49 EE-gl^J kuE r.alg AIB 14F.8^lg olf,-aN.<J Uk,,2-rtk,,tg +EI4=
+^lg + 9lr
r46lq +s-4 eg 49 eg + 9l+ !g +6t4, olag k,q qlql ^l_o + zllz$;lap, olq^J
tril"lElE Bq=q
dlPl k^ko
dt
k.[A],9zlrJ k,= -{ E0l 14F.8^lg ol$all,<-l trl+ 4¤- +6Jtr+.
Lindemann-Hinshelwood +E E^l (14F.5)
r 1 _t___t
t( 1 I \
k,,z k,,,- ku[[A], tA],
t4F.s^lg g6F= BIe+ eg lil-+E Ezl"l4. J
"llztr--l6ol *= a"Jzl=
ol Lindemann-Hinshelwood q"J tr}4^J
6l-ElE ol
"llzlul=:ql^J
T}aql qE Ael EoETl eA¤ ull(+
l/[A],-ll[A],
AE ? E SEol eA¤ ql) ol tl*"] +ill4 2z| $$s_+ sl k,=
U k,,?-U k,.l
trE ¤+. + k'JAllA.l (kolA.l"J ull <[A.]E 1 / (4.8 1 x 10* moldm-' )-t I (s.ztx l0-' moldm-' )
=io}z}=zl.
^J^ll^l7la) k;tAl <ko7l- I rll r+r.+alel +E Bzlol trl¤-4 t/(2.10x10* s-' )-tl(2.50x10{ s-' )
?oI 4EZIE trE ¤+. -- 4.72dm'mol-'s-'
dtPl
dt
k,IA]' (14F.6) TlTl Pi.71 14F.1 TlAltL A+P BL+g Lindemann-Hin-
shel',rcod qlrlq=ql tr+qq, -7 +r +E tl-+=
[A]=
HI+ z.l+z} ols+ ?ol EaLb E4+4 ol+= *g Sqql^l 4.37 x mol dm-34 1.00 x l0-s mol dm-3oll^J 7+7+
10-a
r
E A*21 ¤I^ds+ 9luJzlE Sts 4dol e.z} SdEe q= r.70x10-3 s-'e} 2.20x10-4r'ol+. ol oil7}q=ql^J g-cEI
+E_H-+ +^lg + 9l¤. ctr+ 9zl ollEol+. olgzl qH
qI+,llrlul#ol ts+4"J zt4l q}*ol q4, a t4l(zEzlE
*4ql ql+ +E tF+= 4l4I6Lq+.
r-sr-lotu¤urP IVZ,E
44)zl +s-44 +Alrl g aol+. rar.+zl9 Sd6J +E E
zl¤- +g_r+ e.ol al EzI.
#=k,[A],¤zlrJ 4=ffi (14F.7) 1tF.2

=EI
Ht39l +E=
ol
^lE
+E +E ^J+ k.g trls_4 ?ol lg + +E gl+. +6J r+Cg rrll + ++E LIE + flg.q, ^JcEq ¤+ E-
d*"1 ^ltql ,ri+ $$+ o}^loe H+q. cJfl!^l
1_ k:, I +E+_Edf+ =:Btql^J
tr-m - t,1n1 [Lindemann-Hinshelwood ollTtLl=]
(14F.8) HI* E6JE +ql !;q fl. "Jelel + ++lillzl "I+ oll+
=
A6Jg + 9lqq, +q+4E Ctlg ol"l BCq:il 9l=
^l+ql
trI?+^J
"l Hl$ trllrlq= olEol *={ts Uk,g l/tAlql ql6fl "J +6JElzl ?+=+(rH ruF.2). trI4^l ol !+Aq^J= ++lill
E^l6J rI zld"l +el.t 6J+. *3 t:Eql^J olBl+ ,I Hl* aTlql S.olzlq, + ¤Hat4l,zl"J ^JCEg B+ E
^J ^l-d
ol z|+ BdEzl"J LoETI +olzlfl olgq= aol B¤!olr|.
d*ol ^ltql "I4 6zlEl4. qL¤ E^tl E= t+l
tr-q lsAql^J tI'"}+ Eo Ee| "Jq Hgl.il ed dE ¤459 zll 1v1ol += ++lill= +46Iq ral} =-s'ql^J=
e.J6J trl-$, olq^J
¤E6||¤ + 9i= "il7|q=g Ed^14 BAI+. olaol += ++lillE e. *461+ r+Ag AI+6HA+. 146I
q ++lillEg ^dt}6l= eAl ,<J.<Jal i.r¤
^l+ql e.J¤e
E@ Lindernann-HinsheMrcod ullTILl=¤ olE +(rB 14F.3). g4l +qlql^J. qel ++lillE ol+q{ +q}
El E'llolEl E4 illTl. uul-Erll ¤^"iqq, HI+
^lzlg a4l +ts +qlillg ¤
6l]
300Kql^J Tlill^J A+P Hl¤e Lindemann-Hirxhelwood 4lzi + E efl=ol o|q+ f +!f."1 6zl-t4.
q=ql rrlgq, r+g.4rr3a5 [A]r=5.2txl0-amol dm-3
glrl k., =2.50x 10-4s-lol-tr, [A]z=4.81x t0-6mol dm-3{lli (a) Ez{l*l
=Et
+41^l +6Je ¤+4 e _e. 4 +4lqlrl"I4 4Lg tszI("JHI
14F u3 D{l7lLl=el ql 567
+(+zl+ zllzl HI*"] S"l .Jq\i+) qlE^J EflqlÊlls=

6l=+^l& Ho-R-CooHz| +Al4sE ¤6JE oeAl ^Ja
4,o14:z E + ?14. "lBl* +9lillE+El ¤elql^qlezl rJ
C+a C46IE, r CC +E= el*ol tl¤Elg^l -cooH
zl(Ae_ s^lql+)el *:E-zl-ei6|E_E ola9 *:EE zlzlt_
+a+ + 9l+. ++ Hi¤+ "JEel +E ++lillE g Ezl¤
^Plql^J "JqB f ?l o I] + HI+ g!+E +ql^J= z)olzl4
+ il+.
= "*e ^l+Eol ^Ja aAql^J ol
+trH71 ?+= +q+ HI¤+ r-l-o_$ pol
=^l]6l.zl
-oHeI -cooH(= A)7lE bEql +6]]^J dill4sE 2^l7l
Elfl+r ^8419 + 9l+
dlA
-4, = -k,[OH][A] (14F.9a)
aeJ 14F.2 E4l^l gelel =J?lx1(8^$ g-=e+Ej d8ol ,\lltqq
=:doll^1=
r4dtq u3 rl¤ cill= Ep-t|^1
^l|E8 ^l¤esa^{)o
| 8¤El7l
^lAt=dtr|.
rEl+ -oH7l= 6I+E -COOHTlql ql6ll^J 6I+4 glo o
_tr ol 43 +94 eol AIE_ ¤+.
dtAl
k.IA]' (14F.eb)
dt
ol +6J HI*E +E tF+71 ^l+ rJolql ++61+ts dal HI

+ 4Ag E6H^J k."l "Je t}+e H"l"t *+. relH ol +
o E- EzlE 6l]= l4B.4bAJ o + +qzlq, q-¤-4 eol E+.
o
o rAr=rH"; (14F.10)
o Ei+^J rlzlol r"J+ zl*g ,I +qlg -cooHzlE Sg p=

o trP-r+Bol ¤+91+.
o
[AJ= tA)o/(1 + k,t[A)o)
lAl,,-[A] k,rIA],, +-cfE Tlel EE

fal14F.3 E^t| rl-8. 4 .J?lill(8^4)=
p
lAl- - 1+k,f[A]o tEzl^l 6-s'l
(14F.11)
=-arE ^t=(89uJ^4)=01 ^t|EE

EEc_e4 dg6l.zl Ecl.
^l+ol 66Jill t EzI +q Eqil= ++lill *z)E ¤++E
=-Et
E4r 6}=ql, olxll olag 4l&6H _H_ol4l+.A9 =zl :-"s.
4_q-.tr- H2o)71 xll4q= HJBqI el6]lî {49+ +"J
E [A]0, r4a "Jel ^l4ql^JE ,Jtzl9 E"EE [A]4-r.6]
=-d E +-Jill +zttrl-+ 6I+E A7l!=_ zlzl:il_ 9l o s + ol +EtE
to04 eg EalolulcTl olal6J +al^l ,llrlqfr:ql el6ll^J
[A],/[A]e+ A4 qlE^J ,llaoll r0002]lel A7171 9lflH a
^Ja+. + =
ol +d ql^J rozfl +ql Bzl g.*+H 41.921"111
^1491
H2N(CH2).NH, + HOOC(CHr).COOH -+ ¤+4e + 100 ++lE ?olE 7l4olh qI+. tAlel ,"1& p3 zy
H2N(CH2)6NHCO(CH2)4COOH + HrO zlr +ElE + 9lo4(r+r.rrrl9 a F^l), El+^J +qlill {}
EzI R ¤t ,J"l GOg trl+r+ ?ol ¤4.
4l+6ll^l ^l-+
+ H- [HN(CH2)6NHCO(CH2)4CO],-OH (N)=#=+ 6El.E t34l^l 6-srl (14F.12a)
g"-lql^qlse+ E4*4lBc. ole+ Hl** *4 ol pffi aH AF.4ql +El-,-llfl+. qrlql4 +E

" e. "J=qd ^J+ k,_tr
569 14 rt8^_EE
25 q+q, E6l 4qe g4l 4dql E6l]^J "Jqt+ "l 66J Hl

+ql^J= g^ds+g ++l^ll"I+ zlz] al$el +Elill EBI
20 ^l+g
sal ^dz}^la+. qlE^J qlfl, ,llE_rllE}olrgEllolE, H
3
j15 qaE +6J q}¤:ql^l= rl..q=4 eg e7l +*ol +q6J+ ^
o
\ru
4,0 -CH2CHX+ CH,=Q11X + -CH2CHXCH2CHX

fFl
EO
5 g4l Hl¤+ H z]]9 r+6J +!lE zlzlt- 9i+. +d s'C
0
44*"1 BCq= tll^l cJAlzt ¤zHal^bEll olag q^Sq a
0 0.2 0.4 0.6 0.8 ol +48 + 9l+.
EE, P
=EIE
fA 14F.4 BJ$-L| trJ?lillfl EE(pp LlElL.! gE l= Z0l. l¤ol In + R.+ R.
=-sFillE
aq^lalE p7l10ll0t|+ 7Pl1fl^l0t -Br.= +E6Ual.
M+ R.+.M,
+et$ p(r4F.ll^lel Eall F^l)E Bq +E q^gr+ ?ol E4 ¤zl,tl Ing 7H^lill, R.= Inol trJE= 4qe r4r.M,g +
+lill 4qAolq-. q7l^J= 44tol ^Jzlb HI¤¤ ql_E ES.
(N) = 1+k.r[A]o
+E d+.+ LIEILJ
(4F]2b) zl"J +q+ Hl+q q-4^J= 7I]^l +4lql^J olg,rl-f $$xllz|
e-slE-tp4l^l 6Al
$zlzlE_ 6Jtr}. ol 2fl.<l *4ql olq^J ¤41 HI+ol 4l+q=
¤+ ^l¤ polb ^ltql q+ d¤4e + +zr6}q, 44^l + +s=r+ ag drl EJAlTl F]tr+E+.
4l^l +uJ q]*ol s?-ll {fl6J+$ ^JCEel ¤+ E d=Jol
,l1l+. M +.M, + .M,
M +.M, + .M,
ZttrJEt q 1/F.1
M +.M,_, J .M,
*al4 rta + ¤cE o +6-Jz.llE {{allEz}. k,=1.00dm3
mol-rstoll- azl Bf-l*ll +E= [A]o=4.00x t0-3mol dm-3 ¤zlrl M,¤. ntlq E+l-e ol+qTi +Eiillolrl. +q+ HI¤¤.
olr]. r= l.5x 1oas9l^lel +6JEE 14F.l2b^lg 4. zlzl HJ^lql qr+ +Aqq, +94 ee ql. + 9l+.
"l+6lq + =
*4 *"1 +48 + 9l+. o - ZA.
AVF,
o'=,. .Mnmn+m
+.M +M
(N) = I + (1.00dm:mol-ts-r) x (1.5 x 10as) Ht:4' +.M +M +HM
.HMnmnm
x (4.00 x 10-: mol dm-3) = 61
,tlfol{: M+.Mnn+.M+M
Ir++^l 1aF12a^l9l e-lql^l +qlE E¤.p= q+r+ e.ol E
+.
t|E + ^d+61-= 4q* ^l+ol A6Jqlr+. E
HJBqI^l=
==
tEoEl utql E+ +a +4lql^J= +i gzlT} * ^l+s+
a_ \ (N)-l 61-1 El += ol{a}icll, H}¤¤ Atll4 4}E}e+ *zl|9
r- (N) 6r =0.99 ^la=E "l
¤+?lq q+oJr+.^t= old UBql^J= 6I+9 Ctlfl+ ^l¤
ol S.qzll .tll_e$ ol
^l+ol 4L+6Izl ^l4g+. "llzltlfE
g + 9ole} lAol EAzl"J A+-tlEll ol$oll.<J Q
(o) glrt =^l-=
=-d re6l] E + 914.
zlill_^J Hlg"l} .+ill
+-J HI¤¤ol EAfl HjSol
^J*+E ^J
+. g4l Hl+ql^J= + +4lql^l ^Jc¤ HI¤. +aiil7} r +
g +4lql^l 6zli.llE "J.jL olq^J ol +Aill= E. r rl¤.
¤^ll 6!+ $Cg +EE4s-tr z)1.r1, dt|, +A +41i$
+zlill. "JEr .]-=. 4 "-e olq4l+. ¤cl ++ql^lq +z} p+.
",{
iilE¤ E4 AHJi{l4r ++ aEle E^ll USql^J= ¤41 e -rre6flot
rl;llEol +qa(s dzl¤ *= +)="14. Ell 1 7H^l +4lE ++ +E

¤41 +-Jg ct}"l+ +EJillql ++li.ll7} EzlH "e.r^l .J ,]]^l B4lE Q-g=4 pol zl-{r.J + 9l+
t4F HJB ollTlll=g ql s6e
In+ R.+R. u,=([In] +41 2ql^J q.B".J ule+ ?ol Cill4"J +6J Hl8 +Eb Arl
M+R.J.Mr +41 +Ee+E"J6LtrI. 4 uo-t7lrvrlt.rvrlo114.
"l ^lqlq t.Mlql
g4l dul +4lel +E tl+7}6+61 rE ol + +41 + a4l Ell6J c+_^JEil Bq+H +-s_r+ ?J* 44rI +g+.
^l-$
+Al7l diil4.J +q+ 4cE +E-ea +4171 qq 7H^l +
4l +E= /,e+ eotd+.
/o =ko[.M][M]= o,(+)" lrnr'/'[M]
+4q 4+ ^l
F..71t2 dEI trI{î dal4Ql +R HI$ +E= 7H^lill In9 :-oE9 xll$=
^l+ol ++fl = dr+ +E7l ^l+
trll rTlq ++6t+r 7I ql tslqlq-q, r+q-r+ ?ol i9C4.
Ad-H dEI +E urE uls_4 ?ol tt4g + gl+.
a, = kr[MJ[.Ml u=k,lrn)'''[M], q 7l^l k,= u,(+)"' =-uff?$,= (14F.13)
¤zlrJ .Mg "J9 4ol9 fqlzllE +4Btr1. tr+4^J r+¤ lql

¤EEl Hlql q+ 4qaq di] E"E +7I +Et. q-q=4 +$lillE f4 z|rl
+!lql^J ^JCg +q+ +e+E
^J ^q¤
B"l 448 + 9l+. ulg +_,EEE e0l4r 6Iq lE +4U+. +
^l=
r drMl) rEq= ++lillel +
t dr 1
\ / production
=Zfk,lln) A- gc+g +ce-l +
^J^dq=
¤zlrl /= ^l¤ +qlg c*4sE ^lB^l7lE 4qa R.el E +E=4 eol t8g] (14F.14a)
^[=
9"14. o)zl zzl Solzl-E A* ,+ rlts t4lp}4 zz11e1 4q
*ol Bd9zl ull$ol4. trI4^J +E_E4rl¤ 'J"lb d z|Jrlill +qaql E6ll^l ^J^d
g
E4! 3 +A +41 ^l¤ +E B+ E4^f4r ^J4e + 9i+. +Er=4 ^l¤
,JolE +lE +E^li$ zlzla_ +48 + 9l+. olelo-J Ar+.
¤zlrJE ^J:r +a"Jol gq1}qa 7Ie6J+. "J"J "l +4* E9EJH +d ++lill= a
7Ia6IE +4 +AlE + ^l-+el d+ +Ee+ E"J6J +EE
alE +E7l
^re 4ol9l ++5|.+l -tr¤+= Î¤g ol+*+. :zElH,
E Hzlol ffi$ ?ol B 4,o14
1- ^|=el dy} 4E.
u, = k,['M]2
+q*9 C^J 4s
EqI ol r+cq E+ +q*9 E"E HsI +Ez[ r]-e-$ pol EJSAse q+$ 4=.E4 eol (14F.14b)
^l=
B 4o14. 7l4g ol+6lq 4qaE ^Jc +EE elqeE
a+_^JEH
^
E +Ee+ ¤7ll -aEtrl(+lql^J EEaJ t4l +1. Et+^l +EE
(#).",,e,ion -2k,.Mr'z
4 ^l+ 2"loll ++ ?"1 ¤ + 9l+.
^lg +.q-4
¤zlrl o3zl. zE 4 ig HI+ql^lEI4 zzle1 +qaol s,gzl ,l_
fv-
k,[.M][M]
r
kPlMl
zl ull$ol4. 2k,l.Ml'z -2k,[.M]
',JAl4 4++q rldg 4+ 9zlgl4 t.Mlql 46J c+ tr"Ell^l [.M]= (fk/h),,run1,,,9 B9

.u9 da
^J^J +EE
q¤4 ?"1 448 + 914. +H ol a;o1 ffi$ gol g+.
AH
oo l /\ tll
r=
dt.Ml
/. = k,[M][In]-"', ¤zlrJ k,=kr(4ft,k,)-'''
l- =2fk,Un)- 2k, ['M]' = o
4==4 tE^fl 6-s'l (14F.14c)
^l= 'Jol
8+8Efl= t
^Js +A +4lql^J ARg +qlill eI EzI +ql Eqil=

trI4C ol +qe
^L=E C+-tr-4 *.E=
trIg=4 a-"l 94. ¤+ trflill + (1Dg A.J!= + +6Jal +E *+lill ^l¤
+E 6J6J A+'Jr+. rflql 7+ ê +E ¤t ++li] fE,l
rMr= (+)"rL'1"' tri.nI+^J,
s70 14 u8+EE
6},\l EI',\I
(N)= 2L - 2k,IMl [I.r]-"' eE'E tE4 eE'l (14F.1s) =o =o S
1l
^lal ^tal
¤zlrJ kg qsq.rq6}q rl¤9 z]|
l4F.l4c^lql^l Celq} E E
+41 ^_Ezl *g+E-(= zll.rlill$ EoETI *g++ r?.lr

^l
7H^l +41 +E t}+z| $$ffi) +EE4 rl¤ ,J"l= ,Jq rl-=^let oHt xlEl.
-rr=
- E
zlg tr14^J +oJillel ¤+ E d=J"l +oltl+. oi,,\l
=-q SE
14F.3 6^+E[4tE UE feJ 14F.6 71tr01 6^ql gd 1= ¤86l= F E:d.

^l=^l-
E^l q:doil^1= gd
Êloll =EJ6l.=
7lE0l dtE4?.! 3^l-B +4= 7l^la_ 9,lol^l
Êle|
fl^l xt|ut|ilTl gf golLlE qt "I1l Eq.r 84Ertl'. +g 4Ef sE
+u]]= HI¤¤ 7l+^lvl7)trJ ap zl1413 da :zlel HEIzI 4 oil^1= 71tr01 g8
=ol7l
EE|1= 0la1-el+g
EEl.^llrl'.gclLtE 71tr01 EatTl
zl ?+E Eeol+(Eq r+o). +,]l= HI+ gCsl qlHzlz} * =|dtrl
xlaloll
ÊlE
+ +l"JZl Etrl'.
g 4lEs HI+ asE "JEq^J H}*"1 ul-+o]l HI+E Lfl
+E-ac *41= H.zl t*zll 6ll=+(rB r+r.s). E ^JEqI Ag 4-EtEEg zlzlaJiQl, ol s¤ql^J= Tleol g.^J zlq
=
4 +"J +,]]E^l q+q} dq^dg TVlq "lael zI¤¤ ts= E ¤E]]E Aq}o]] zlq}6}rll H+^lvJrla ^J4tl+. olelfl+B
HI*ql ¤zlal g6J13 Ela+. qlE^J zlBrfolzll tr.A= 2e8K HEIrI gqL+"F zldol drll ¤+^d zlEql 4,"14.
Ei9 =q<}+L
ql^J HI¤¤ 10'2HH-tr_ 7l-+^laq. HI* +EE-g de4ee S+d-= "JHI4 "JBe
F-+7I ql*61*g }-tr+ Eqil= +.-4 +ql^J S^d$ol ^J
trJ+ aq+g 6p olag ^JcEs H6Izl 6I= Eeg ++. zl! =zl HI8 +EE EqEl6l-= Lol4. s.i= ql+61 qr+
*.-tlarl rlr .T
+Jr.! -.t"n.11^l
".1 tl
I nlll-zlz!nlzInL
"f ,J/ rî " i/\i itj- v' i ¤'ij-i ,'.i E - 'o-'oE-=
,rl 6l-f-1 itl. zl=lt- l.UAIE O
4"J +nll"l.q zldel +a+"1 laE +r-ql t q= t.;ql^l
u.!$ ffiql= 849 tl4-e qEolt+. Y*e sa=g +-tr E HI¤¤ z4l zl4^la+.
+EAe ol+q4 9leq, r+ qH 4ql^J= B^d z}4"ll * "*9 s+-+,]|$+ HI¤¤e q+4 ag +,q 549 zlzl
zl4 #zl H + qlz}z} aEle}+. r*i+ RNA EzlE EEA :z 91tr|.
g "J=q ^JE+4 E + ?l+ +tr]]z} 7)44 Z7l +E- [s]nol +qe¤- ql= aTlE ^JCE
BC zl-48 ol{ol $s-"ali H}*ql r+* +a= zlzlt-
^8
C 45-zl- d4l e'+e-1 r-oE [E],ql Hlrll,*+.
9leq, 7l4E zlzl *44 o e fr ?e."14, 44214 tls +qzlr *g
lElool [s]oE <]ol trll=
^8cEE ^J^"i +
4}+ol+ EE van der waals tls l-s" 4 eg Ezla tls4} szl [s]ooll Hlqlq]+.
+ql e-l6H^l ¤+c ^l?-lql ++g+ re 14F.6e zl{ol ar lElnol +qzlr [s]nE <]"1 }$ Ell= +
el gc zlqql a6J6l^= ag + E'Jg ol$rll.! ,+4u a ^JCEE ^JC
sz| [S]ooll ++6iq AEll ^-,E u*,*91 EB++.
ol+. r+ rl=Al-E^l .Eeql^JE g.^d zL4 * zlaol 3il-g
E tr'tr4 +a= zlzla- 9lq^J flz| zlluflzlzl qI "Jq+E "lBl6J 5A#
A ¤¤6l]f L 4"1 Michaelis-Menten 417[
q rq+ ulE"l4. ol "llzl-rl¤ql^l= tr_t-zla +6JEol a +4lql^J
EqTL "*rll ¤+r ^J46Jtrt. ¤e a4=
=qlE BdHl "lq^J 7\4ol A* ^J']]'}|_E trq4 +eA+ H¤
"l ¤ q-gq ^JdEe ¤+r ^J4¤I+. +,
E"(=ott g.= nfl)

u+s cfi Bg
N/ichaelis-lVenten
E (+0ll ArE) kn
DllTlLl=
ES > P+E
K
5 HLO
Jo=
E
6 ol ullzlr-lf;r A+ tlq ol-$all.<J E461lg + 9t+
{ru
u.l =^l-=
H
H {9
enten tl
oo=
Michaelis-Menten ,llrlq=ql e-l6iH
^JCEE ^J^d +E= +
HJ8
ÎE, *4 tol +49 + 9ltrI
fal t4F.s +D}|= 0lt6l.E '-*3 gdEl. ollLl^lsl 4E= 0lEg + ?lq. r
,Jile 8HJa:ala qU8)E As.z 1 lEltrl'.
=7
14F u3 ollT[Ll=ol ql 571
z = ku[ES]
{zld oilot E "Jg +aill Fsel }E= +{-= 1"14.

trlel^l
E4l 1 4#&q
il
4+ \
E
o+-zle +qlE9=ÎEE"EE trl-s=r+ Bol c#

^J4 *rl-3 "l ui
{r
+ql^J +g + 9l+. 010
ll
# = htEllsl- k:tEsl- ko[ts1= s
0
tr+t+^] 0
71tr ts;-E, [s]o
azJ 14F.7 E -+0H UBsl 7lE EEIoll ttt= HJB -Ê Michaelis-
rssr=tH Menten ollTlLl=E =E
0lE6[E tsloTl flE ttfl elE[| E=J6|! ag
.A
-aE u-",oll
,\iEHal -T- Olrl
=d=
alq
^^Ll.
¤zl! tEle+ tsl= 44I +?-l tlelE flE zl44 +E+.

tr,JAI2 Esq q*^19 ZI4+
lsln>Kr"J uI= HI* ^-Ezl alril {}ql EE-"t4 [S],ql
olxll rl-e=$ ?3 uicnaefis 8#E EEe]+.
++61-r| ¤4'
,
AM = _n_
ki+ko
u^ *= kb[E]o (14F.17b)
("1 qfldg 4=+.) +E H4g 716ll= d ol 2,,,o9 AqE l4F.l6^loil Bq+H q+r+ ag 49 Eril
^J+= E-bEel gtrl.
lElo=[E]+[ES], +4lE ole"aJr[. o] [E];i

tEl=[E]o-tESl"J uû
= ,,
z= - t*rr?lS-1. (14Fl8a)
tEslql ql+ e+-tr-E{ :z+lfl,
^lq Bq=+.
{g qlolEl= d¤ 9zl E^JBql E61l^] 61146lzl ¤nl6}
ol
rEsl=G4#l E$ ?ol la ¤ + 9l+.
r-]-o-_3_1-
s"J ol-ul+ zleg g+4 0 + 6-+ql Hl6ll^l qe*-e--tr- a6I 11

_-_r (rc") r
l, r*
u U*u
I Lineweaver-Burk -E-.\l (14F.18b)
zl ql$ql +fl tr"q 714 L"EE e + !* zld }-E .llsl;
=Î4
4 z.41 u ;r [S]= [s]0o + Fg + gl+. rqH tEslql q* rluq ql* E^lE Lineweaver-Burk E \l+r 6l+Ell,
1/[s]0ql
ll"l r-ls_4 e.ol 84. 14F.18b^lql el6IH ol E,<li zl&zlzl Krtuû ¤¤"1
ut)ô, r?]r x4 ¤¤ol -llKMoJ zldg 444oF ¤I+(rB
rsst=*,rffi=o#^-r r4F.8). K"9 <13 zl¤7le+ y+¤¤q ul$ zlzlr +g +E
E4l 3 +E Hzlq ql* ^l

ol [ES19l +q] 49 u=kulEsloll Bq+H Michaelis-Menten
l o ol o -,'-- olrl
Ee. I ,\A-1.
-t=
k.IE]" 4l 71371= K*lv^",

- t+KM /[SJo
tr/ichaetis_tr/enten (14F.16)
-'UKM 1lvmax
14F.r6^lg tr|g_$ Ag de Î¤rl g "*=trHafl ruF.z).
. [S]o (Kr"J oI= H]8 4-I;7l tsl,ql Hl4ld4' o vlslo
fal14F.8 Michaelis-Menten ollTtLl=oll qal golLl= E +0ll U3E

, =
fr-tsl.ttl, (14F.17a)
E46l= Lineweaver-Burk E\L L4r 0l E,\l +Cg trtr+ 7l=7lAÊ..
572 14 u8^-EE
9l+. rqB F ¤¤4 l4F.17bal o ++q /roel {tg gg +

40
9l+. rBl4 "l E^l ar+e+q r"9l +qI 4oll eel¤ zll /
^l
zllE +E tr-+ ke+ k:el #e +g + S.4. olES +6IEIH
i30
eB rae¤oll^J ¤Bo.J Czl-eHBg 0l+6I^l q *g qlol ?
o
elE- ?"lo} 6J+.+ ol "JHg ole"olol p-+e+ rlag E

E
^Jg a20
ffi oli-9 Eo E HEI¤ Eqq6}q F +-zla +qlillE ^J^d E
E
+E= +"ll"F ++. :aBlH k E g + 9ll" ol"l^J ol arl-= >-
Fro -(
he+ K"E <t=4 A6J6Iq /,:E <tg +g + 9l+. ./
0
0 0.2 0.4 0.6 0.8
@ unerrcarer-&rrk .E,tl= oltEt E{olEl 1/([COrl/mmol dm{)
E!1.1
feJ 14F.9 H7l14F.2E EllolE'l= 0l8-d Lineweaver-Burk E l.
+4I B+ sa= 4e+ ^llE

+oil^J co2= +El^la +4I
f + ol¤.¤. ^Jzlzll 6l+ +rll zl¤¤ ¤L+ Cor(e)+H,oo)
2n.sK r4r E+ }.E EE gE 8^.! tl$zl$ e¤g #-4{lCol4. g= :
-HCol(aq)+H+(aq).pH=7.ra+
2.3nmol dm{ql^l ol ++q q6il q^q=r+ 4-S rll"lelE g 4E= ++6J +E 7l7la- E,tlollo[ 4311.
fltrI.
Tj7l E^7J 14F.2 s.t cr-zlFEB{i9 efi f E +llt}ql
lCOrl/(mmoldm-3) 1.25 2.s s 20
olul:rtlE
^l EHlqq, 5A6J Îolql BC¤ flElE
u/(mmol dm-3s-') 2.78x 10-2 5.00 x 1012 8.33 x tO-2 1.67 x lO-t
A
.Jg_ Brlg
l.r=+F+g_r_4lB"J4H_p_Ll =
#L,_I. 1r3-
ol HI*E alql +Ee+ r}+= +6Iq+.
Michaelis qBl +.lg EIEJ"
_=.olHelEz} ^Jol+.r-oE_e.
:!4Et rlEf Lineweaver-Burk E^l= 6}r dB alzl S:j *9 =qfl=
a=+9 a-zl./ efltlg 4 +"4q1+ 716|9+. relr
B o + Kr4 2-o9 <tg +++. rJdEol dzl} a7l +E. +e6}q q-q-r+ ?3 rllolrl
Efl+.
fll ol rllolQ$ zlzlt_ trl+4 eg s= "J=+. =
lSli(mmoldm-3) 0.334 0.450 0.67 1.00 1.33 t.67
l/([COr]/(mmoldm-)) 0.800 0.400 0.200 0.0500 u/(mmoldm-3 s-') 0.r50 0.199 0.28s 0.406 0.516 0.619
l/(u/(mmol dm's-')) 36.0 20.0 12.0 6.0
ol Hl*el 4lEil +Ee+ Michaelis tt-+= AC6lq?+.
ol cllolQg zlzlt- Lineweaver-Burk E^l= eI ¤r+z} f-B *n :6
w)',-s
¤-urp IouJLu 68'S = r-urp purur 69'7 -
14F.e+. 7l&7]r+ 40.0olr /+ e¤g 4.0001+. trI+^J
u.* /(mmoldm-' r-' )=

# = # = 0.250 naE +¤+ E+ EAql E6Hî ++4 o_tr 9zllB + 9l
Eril "1fl Eag o4!frolep 6JtrI. 9x.ilE$ FE!= f+
I u*u=0.250mmol dm-3srol4. :24l,
EA"J +E gljr" E. ^lls +ql zI¤4 o e aA ql
=zl]6].q
,Iq=ql +q6}7lr6J+. 9zllE$ d¤4os $C zI4E
K, /(mmoldm-3, =
H = +# = lo.o
+41 614+ E= 9C x}4zr olH =q1 ffiqq n.+4 z1
4 Kll= 10.0mmol dm-3ol+. 6lE4 +a= Hp+^14î ¤|C zl4zl 7l4g=- +¤-6J + Hal
ollfzls ++.,
1 qxil+g +EE4 +Eql q4 q4 ++-q E+g + 9leq, ¤21.il $
6ll zl-=el Physida dremistry for the life-sciences(20 I 2) $ eo |.4.
^l = ^l
14F HJ8 rllTl.Ll=g q s73
=s-d71lE=
trr. l+ztE Hi*ql *t tinOemann-Hinshelwood rllTtLl=g trs. ^_E=4/.t= eoI= +qg ++lillg fg+ zllrl *4ql^J ^J
9P zlilltql^l 'Jq+= ri} Hl¤¤ ¤86il=+. C¤ +qeq +elg ulol4
fJ2. trJ1!^l HI8 selE +ql Eq fl= "JEE + + tr6. EA= +"J ^Jill +rll+.
gillzt =Efql^l=
ol+ rll+ A¤.g + 914. 47. EA Hl+ql +e} Michaelis-tvlenten rllTtLl=g eI* 4sz}
tr3. +41^l +El"l ,'al o'qH+=. ^8^JEg *+ E- 4a}"l zl 7]|4+ E-+9 L"Egl E=61^= ol+= ¤Hdl=+.
114. tr8. Lineweaver-Burk E,(l= "l+6IE Michaelis-Menten EllTIL-l
44. Eîl E= ++lillTl += +9lillE *46Iq fa +4+= ul4"lrl# adg + 91trt.
=-dql^l= =ql
4 e6J*+.
=s-d^l=
/(l;(l
ct e, --1I +^l H-g
^l
Lindemann-Hinshelwood 4E H 4 dlPUdr=k,[A] q7l^l k,=k^ko I ki k:[A]>>kb T4F.7
+E +E r}+ I I k,=k'^ I k"kb +1/ k" [A] Lindemann-Hinshelwood Eil 7rq 14F.8
=
+6Jg Tlel Eg p=k,tlAloI(1+k t[A]o) t4l^t 6* 14F.11
6OJE (N)= 1/(l-p)= l+&rlAh +al^l 66J t4F.t2
=aL
oll--1
4.E
+ rl = /q[In]'/2[M] s4 6q+ 14F.13
4s.=4 ^l¤.Aol | = ([M][Inl-''' , k,= kr(4fk,k,)''' g4l 6rI t4E.tk

+6JE (N) = 2k,IM][Inj-"' ¤41 +E] 14F.15
Michaelis-Menten 4] u=uôl(l+Ky/[SJJ l4F.18a
Lineweaver-Burk Erl Uu = llu,.,,o+ (K*lu^*)(li [S]o) l4F.l8b

Eq ll*G zJE1-+
E 14G.1 BEt-qt rl8

> ol EEfg u1$,i ols
BEt¤rl al8¤ set:el "dg Et-44 "J 8stqt4 48E3 4C gHI^l }7l
^14
dxlTl E+geer{ Etal^j ol*lE} Ezl5g olg+ A*+A++e- NO* -+ NO+ + e-
=^lE
4-E H=loll ^lgErl.
sEt^l4ot 6lE Aolq. olBl:d 48- 8*4oe dz} old A*+B+A*+B- Ru(bpy)3.. + Feh -+ nu(bpy)]. + Fd*
54alE 0l= rElel oll7l-Ll=E + 9lrl. EEA +B*
=qq = 6ilr-l A*+B+C Oi-+Or+O
> 64C 7llE A*+B-C+ Hg*+CHo-+Hg+CHr+H
"LJ3 gElqr. HJ39 0llTlLl=o_e+EJ HlE4 .J+et +E H^.101 A+B+C
Llgq, ol *E H^lo.E+E1
^-E.ga= +Eg # ?,1-L !E
E_Al 4zl A"+A*+B
0llLl^l7f cl! EEel EE¤ 7l'^|I HJ- 8"J lTltsr|= EaJ /
H.H-Y /
/\^
'tolcditl
'!uE "
40+ LlEl'J + ?irl'. A*+B+AB Hg*+HzrHgH+H

qrl HI* A*+B{-> Hg* + CH3-H -+ Hg{H, +H
> EAfl qHl rl^l A_B+C
EtgB4 r=B SEllE zfluJ(Erl 11F), EJI Erlel g4(EBolLl ol^JAills} A* _> A, *
?jB, EE i iG), Exi--sEll *iE(EE l iF)e.l 7liE, falr. 4l?J r=
qlTfLEoll EtFd +E EEl9 +lsl 8EI(EE t+D # +^16t!. zI4*a
?lolot:dtrl.
. EE
^J4
r4G.2). trI4^J %Islqr-4 qlTl.q=:ql +¤l

¤¤ql *^J E= ^J
Hl¤¤ +ql^J 7l* +e6J Ag 4"Jel +^l qlqzl= gol-= rflzf ,rlzlL E ol4ol tlcq= rlzJ 4EE ;zpallEi {ol
rJ++ HI*oltrI. ol4q} HI¤¤ +ql= +Aql z}9d g
"l= +-e-6Ir+.
qE +Îrj$ $451q
'|]zlg
z|$ali aE glr, E +6J¤ z}e]d4 ¤E +^19 E-+"il ,l"Jq= dzl. t4 dol
7].^l
$eql^J 7l^loldg ¤+61+ aE 91trI. %Islql HI*"I H+ E 10-,u_10-rss olqlql "JqWf.u|4rJ l^l-=J'slqt4 HI+E
H ol ^lltlg ulzlfop. "ll"IE Hr+lEs"J d"14. +E tl+ql qlfl tr-+$ * lgtos-tol ¤ 4o14. B"3.g g4I
B+ Lflq d¤4"J +Eol l0-,2- rO{sol4. tr}+^J E= +
1t*G.1 EJie,ltrI zEI "J.J tI4= fltr+(I0-,ts)Pel !l?+(10-t2s)zlzlE ^l7J 4
^lg^lvJ + ?14. "14
Eql^l tr]]+61 UBI= %r-slq}4 Hl¤¤
E¤4 0 _e EI¤# L-3 +:=ir.4 HI+g qlE^l= oJq
^l4r+ *6JCql^J a +41_e
.E. 14c.19 "Jq+E %IslE 9qI6H
4o14. %Islql 4Ag 4^qI HI+ E-JE +g + dB"l B += Îag . + ?14 rll+ d*(rc: internal conversion)3 E
r1g- g4g}eeA] EEqlîE ,==E ^J4E ql ztE TI5- "llHzl ,J=r+ Eliql
^lgE4. rx1 ^lt 4Eql^J "Jq+4 :24
¤¤e+rl zld S^d$ol ^J^"j94. "l*l+ qlg^l= Bo&E a|{ 1s-tzs ol49l gqt+. +7]|Ez}9 a+ d¤4"J 4l
= Eq
9 ttcl4 "J"+el cis-trans *-"lCeille+ HI+g. + 914. z t J.iHISC: intersystem crossing, 11G)
^lt4 "JtJ ^lt
il EElql^lE E=E tI{E H}*ge+q zld ^JCg +rJal| z r+7+ 10-12_ 10-n se+ 10-6_ r0-1sol4. olqql a +H qlEql
,I ^JCE$ "J=trt. s=fl ,J6H4ql E6H^J ^JZl tla flztgl "J'J iE HI
s=5 :5a3; tF4= %rqr4 + +96I+. dzlle
"
ql+. ¤* d¤4?_l Hlg" B+ "t4 z}4f "Ja LqTl qlEql
^lgq= &+^"i 4C"l "l*l+
96]]^J zlar
^J^d+g "JEqLll='JsI+4 4Ar+ A^Jg "Jezl= 4 EE:6a3-d-Ellql fl= +g d{e 4lllzl +E Hl+ Ez].e|
ql+61 "*e q+E +Eg ++
"J.E4qI4 ,+A.ol+(s
ol E= olBl
^JEll= dA^l7l=
1/.G ts=elEt 575
-n 14c.2 -H.E40J g=al-+4 El-8=

"l ^lE Ezle+ tsE= F+ Îaol gqkl \z] zlle-e_ +
hE rzt olx|;5gg +94 *ol 4rl.-frts rz1 ^Lag g
1Î ¤+; S+hy-+S*
r"+x| 94,r1lzl r"o,_E +b a4 ,Je 4+71 ¤+.
r===
tl-Ell g+ S* + hv -+ S** ^8 +E=
T*+hv+T**
B'J *= S*+S+/rv a
+E
r+Ael u
S*+hv +S+2hv ¤rz} *+ +E /ub,

^H "J=
j/^krsc)
AlrJ S*+T* rldol gclLlE +EE LIEILJ i^l gî +=E (14G.1b)
HJ= T*+S+ftv
"J*o
L]] HE+(IC) S*+S
+5-+g "J=
+E da
S*+M+S+M+hv
S*+M+S+M
E@ 1ir?frlffiEah]
T*+M--rS+M a55g +c6l+ 6J ¤Bql^J * g
%IElo| HI*e-l olz|
dzl tr4 "llHzl d"l + Eeg 1.00w %+fl " -e.9El +s= 4e0nm Eltlg qql
+"JoJ_+oJ6J S*+S+S+S* 2700s E9] t==^laqq "J^l;lE 600/o7l g+q9.4. ol
l.L+61_^L=aL T*+T-+T+T*
EO O
EÎ"i BC
EO O
S*+S+(SS). L=9 A4.e. 3.44mmolE "J g+ Eeol E6l]qfl4. tz1
qlLl zl qql ofz]. 1559 e¤6l.q4.
+"J6J_ +"J6J S*+S*-+S**+S
/(L+61-,(I+61
EIO O EIO O T*+T*+T**+T IalEr *d t+c.taal 49 6JEg 414}6110} ++. 'J
^!¤l g+g *zl f
^taq fts N*.nt=Ndoo-po,.aol4.
.= E=
EI+4
^JeiE, S: t"JtJ TE r6ia.g-tlEll$, rfla Mg,rll3E .J
"Jol'E +El-UEt.
^JEllE,
N.b,g 4l&6171 +16ll^l= trl-g.I¤¤ ol+4oF oJ+.
. g+g glHzlE E5_Jpf.ol4. p= "JÎ Eq,
.r.l-Egl
,= t=¤ ^\7J, rfla "Jzt /E ++q= Hel Hlg
zttrJEt q 14G.1 (ol a+ql=l=s.6r)ol+.
4.J* {dE d+ EAol H}¤¤E EE +"J6} ^}ql"J ' E"b, 9ll E"u,=N.5,hv=N.5,l1cllq1 4+ g+g +lzlf
xl E}. 3+6J t4.JxlE +E6lzl +l6ll^J %'-= +Bg + N"u,{l 9=d4. {zlrJ hcllb-,4atol r"J =}z} a}4
¤ El+ HI+E t}*zls+ ulaoJl E+. xl+ +E *#zl 9 9lHzl4.
k,=r.7xt04s-r, trl-{^J *r}7l7l41psoJ l$zlE "&3l+o+ HI
g+¤ 9lHzlE ++4= +lE + +alE ol+.Its ¤
¤¤ ^J46ilEzL. ol Hl¤¤el B"* +E +eilE r.onse+ zll N.u,g +B + gl+. Ir|4^l li[ o]z[ f5Ee p=
"J"& +B +47171 t.omsol4.
El+^J EE +9o3i tlql= Na.-***6/N"6u¤ ol-$oll,<J +{}+.
i$"l Ll+ 5|.oI^J ol HI+el +
^JCE
gg + S+. f,
B+g "ilHzlql 46J + 4sE+q r+g +alE E
¤ ult4 fB"l a EE 3+6J tl-EH= C+ EeE ETlql =ol
L.+.
+E6I+.
fPt=r,r,(+)
1tG.2 lilg5tffi tr|+^J Nus, =/Pr,\/ hcol4. q+ql= taG. lazl$ 0lf-61-0l +
!$$+e-4?ol 44t4.
'JEl+ H}+ql^l= -E== tr-EHz| $^|5ol+ Hl+Îdol+, s
Eiqlzl 4aql el6l]^l aeqq, 4Ie +Eql "++ ^J^d r Nd..o-po."d Nd".o-por.ahc
= .JeqL
a N"b. fPth
Eq ++*"1 ¤c¤+. E"Jgl rz} dcEg qI
^la
E= rlE4qi4 E= %Ip++4
^laE += Ae ^lz} E"Jql {zloll x 10-3mol) x (6.022 x 1023mol-t)
Nd..on,po,.d - (3.44
Ezl-Eol g++ *zI9 +E +b #,rE 1iI 2frl t==ol =2.07... x 102r, P= 1.00w = 1.00]s-" , =2700s, r1 =
4r 6J+.+ 490nm =4.90 x t0-7m, a4a-f -0.609 Bq+E q-s=r+
ae a4= Eg + 9l'1.
a Îag + -
-g+g
N"u.nt.
+rzif N"b,
, (2.02 .. .x102' )x(6.626xt0j4 1s)x(2.998x108 ms-')
1^f g^f +=E t8e-11 (1aG.1a) Y- 0.60x(l.00Js-')x(2700s)x(4.90x10-7m)
576 14 u34-EE
=0.52
14G.3 # Eg:dSE]lel a4 qlTlLl=
+ g+¤ "JzI9 eI Hlol
'JE6ilE
ge_214. s+q}Hl+"l .J"l4zl ?+= ^JEilql^l trl-¤.4 eg r==E +"J6J
14G.1 * *Elo+ HI+e-l ofz[ 155-¤. +c6] tr,4E ^JC4 e^.]E- .${allEx}.
^l7lg.71 g+'
=
¤ii"il^J * ¤+ Eg9 az.smw *ge-E+El +eE lJ o' S+hv->S*
r u.-L
aDs aDs
320nm Holl 38min F?I L¤^la+. E^l-¤ H9 o.:sz| B*' S*+S+hv, ar=kr[S*]
Fr+qq +Ssq, 0.324mmole1 *I Eeol E6flqH+. 4* H¤t' S* + S utc=krc[S.]
rit oJzI +-g ac6}q+. 41zi A)<l: S* + T* /rsc = krsc[S*]
eo.o=d.E
q7l^l s= Erle s.= -e *"J'J tl-Ell, T,-= E:E 3+.J ^J
4, :4r hv1* huE 7+7+ oJ^l *zle+ ¤"J olz}"l+. Eq
E= tr-El]g E4t g¤4 oe ElqltlqE 44zlzl4 * l4Eql^J E_oJ+ *Hg ol+{q s*E ^J^d +Ee+ dill e!
+E4 ^J¤Eg "JEqot ++. trt+^J qÎ r+C, Hl+^t ,+ +E= q+r+ aol '+EB + 9l+.
¤, :z4r *ElqL4 HI+ql E6}l^l dCq= z$xll ¤-445 q
S.9l ^JC 4E = I"u,
$ 9461a ^JA dill E== +q f4 *ot"t ++. r?-l6lq
_E= *E?-lqI4 "t 'J+qL4 ^ta 4oJ rzl. f55 r.U
;91 s. E e{ 4E = kF[s.] + k'r.[S*l + k,.[s*l
6Jg E= t4z}+q6I= HI+E ;q1 a$a|.zll rol 9"lot = (k, * k,r. * krc)[S.]
++. + E|+^J E=E tlqzl *l +E rl{ql tr|+ A4l6Iq, r?]6}q

Hg lzH s*e-l r-o EzI fql nI+ q^g=!+ e.ol Ht4.
1r,=1*=*I,',=' (14G'2a) ^lzl.
[S.](r) = [S*]os-t/r" (14G.3a)

rrI4^J r+c.rualg tli-v,tr^6,8- Hh+q^l q-q=4 eg g
^l¤-
g+ el+. ¤zlrl rog d H4e s== +oJ6J tI4E E+ +Bolq +
94 rJol +qd4
,,-#, (14G.2b)
I E"J-d SEtlel (14G.3b)
t0 -
k, +k,*. +k,. g+ +E t8etl
==
Et+^l EE Hlg-cgl^l7l= _E= 3JE?-l+4 "t %r"sl
^JEll=
qlzl 4cE d+ HI+ +trtr+q 5a 449 17I olzl +=-
ol !g ol+6IH S,IA{E 4e_e4 o + +461-"1 Bo}fl "J
zl- f E g +44= 49 +g + 9l+.
Eg aa6J + 9l+. =
+.JoJ t4zl *EelE4 r+Cql 9aHrJ"J B"J, '.ll+
=E r4r
d+1, .J%I r+Ag
"J9A+E q-s=r+ zJ? *Alzl-CB
6l]"t *+. q++e_l ¤%I +A ¤Eql^l3 Hlj/4 #g ^leql+ g+4
"J d z|.r.15o1u1 zle]d q¤g
+e6J+ trl+^J 4)ol7l7la_
Qr+ Qrr* 0o =I ls,-l= 4r- "Je6I4, -2461¤ ¤zlqq A+-tLq
=^HEq
14E)= ol+6J + 914.
¤zlrl "l 0r= 7+7+ 4*, rll+ E¤}, rBla "J"*"il ql
Qo Qrc,
6J oJzl ff$olQ(+"J6J ^JElle+q 3+%L ^JEl]Eel 4l+
ril^= opql sglg+). ¤%I4 .J%r-ql el6J rJrJ= ofz| ;5. Y = rub. - kr[S*]- k,sc[S*]- k,.[S*]
E3 0.-,,,ion=0r*0pol{ r-H-4 ++. "JtJ E= +"Ja} *42} = r.b, - (k, + k,r. + k,. )[S*] = 0
E6J lz} %r-EI+ HI*q alol6l-r I oJz]- +.Eg o.olr-E

4eI^J
6IH +*4 ?"1 ¤4.
I"o. = (k, + k,r. + k,. )[S*]
0r+0,.+0r+Q,=l
¤%I ,J= fE ueE kr[s.1o1q, q4^J l4c.lb^]ql E6H^l e
14G EJgl=l 577
"Jzt f
o*el Eol trl-¤-r+ ?ol s4.
= @ EB s^l #Eo1 Elil= aEJîlet
k'IS*] Ezt
n.r.r=
ll - (kr+k,r.+k,.)[S.] a$xllzl-=^l]g trll= e+-tlEH ol.$aH,<J [s,,]= r-l*-
ls.l= A46IH "l rl"l ++4 ?ol tE6HTI+. =^l¤

4 ?ol +EI'J + 9t+.
kF
Q, 'o-
kr+k,r.+k,. # = - (k,, + k,r. + k,. + [e])[S.] = o
r,b, ko
14c3b^19 ¤'J +Eql q6J 49 ol*alE ol al"l rl¤.4 r4I ¤%l "JzI +=¤-q q^q=4 ?ol 448 + 9l+
?ol 94.
),- kF
gBq g^l +=E eF- kF +kr.sc +krc +ka[e]

Qr.u=krro (14G.4)
A"Jzllzl s¤. trIe+ ilg trIE olz|;55.E Hl= r+q=4 e

ol ¤+.
B"J +Eg dE4 "e. g^ Ellol4 zl$g ol+"H^l +Ag.
+ gl+. + +d .r.le sgl ?t6lAl g+q= vltlE 613 eilol Qr.o
-
kF .. kr+k,r.+k,.+ko[QJ
zl gÊ zlzla- EEAI qi+ rela E^ +q ¤%I
7\_
Q, kr+k,r.+k,. kts
^lE=
rllzl9 zl+o}+4 e!= ELlq++.
zlEtEt q 14c.2 ka
=l+ k, +k,r. +(. tal
.5e+ zlzlt- ++.+ +9 EBtr+el ¤* "J
+tlg
zI +=¤4 ¤'J +Hg +A6I9qLl 7+?+ 0no=0.20r?+ ol l4c.3b^lE t/(k.+k,r.+k,.)=roE -+q+H Stern-
^lql+
ro=2.6 nsol*.4. EI+^J 14c.4^lql E6]]^-l ¤%+ +E tI+ Volmer lol 4g-4.
kF= tr}s=4 *ol ¤4.
{1*--r+zokolel Stern-Votmer 4l (14G.5)
, 0.20
"t --Qr,o
ro - z"exro =7.Txlyi s-l
"
Stern-Volmerll9l EEll^J 0r,/0.8 [alql Efl6ll^l E^l6lH
zl&zlz| rokqoJ zldol 4s+ot *+. olBl6J _sa^lE stern-
E,tl{a dk-tll(rfl tac.t;, ol E,tl| ol+ "JHI4"J
Volmer
llr0.l, Ats *Hol{ "J"* "J=E AolqlE "l+B + 9i+.
r+C.+ll9 k =rpr,o/ro o E _L! a-l:---L _H_H ¤%IE +E ^J
^J4E +H"l += *9 ¤xI
E=E ++q= 4* *. qEql
ts(E= aplolrfl +4. A'Je 9lHzl4 dz} "ldr+ ge
u|$211fl 4eg +E glr E g6l= %r"s+E 4ce-l "JzL
ffi¤ trqEfl= gil ?+= +HI+"J +E 9l+.ôJ a-4
%Islql4 HI+ql +olq= EE ^JEIIE+EI +s= "J=g 7lZ7l = roko
=
EqEl6Iq
g
"J"lB + 9l+.
o
g
i!}zll QE EztalE s,-z1 tlcs]=q+4 ?3 c.6I+E

41zl g4Zl g+.
t%I' S*+Q+S+Q /a=ka[Q][S.]
o aBrll BE, [o]
a$xllz} Hg ,Ie+ 9lg trIE ¤%I "J^l +=¤ 0no4 4r9
=; fB 14G.1 Stern-Volmer -E,\l 84.1. 0l E IE 7l37l= 4B 4-=.8+el
A Ar+= EE" E talE zlzla_ +48 + 9l+. 4BIllTl fl= ttllE E= BB +EE Tlxla- 6H4-g + 91tr1.
^*4lq
578 ,i El8 A-EE
1
f, rl4! B"J HI*E +E(¤=J ^llzlE eA6I=)= "Jzl-+

E-aol EE-l6l+. :aelH ol trl-s_r+ eol Btrila^4g
HlqloJg .J + 9l+. ul= /oo/1r9 ule+ ^lol
-.il "l+rl 0r,/0r9 +-qHld).
,J4. 4zl^J /no= r{rxllz} flg trilel ¤* r]lzloll" IrE r
%rzllzt 9lg ,IE B* Bli6tZl r+c.+al$ ro=cfp,stkp 11+ nrol d*-')}
^ll7l+. (10ri rT(tn=t= a {kalQl/(10'
E ra .'^l+r _H-H B* +Eg "JzI += Eql Hlql6}q, tt}
x (10-2 mol dm-3 )
rJ.<J rolr(q7l^J rE i%l4lz]. ll9 Ellel +B)g E6J Q.olAr
ql Hlell.J+. Stern-Volmer EÎts 4/ro+ Eb rolrE il}xll oJg"il 10-7sE +6H+E ol zlol q=q=4 ?ol ¤4
*.Eql q4^J E.^lg +E 9l+. ol zl$zle+ ¤¤g 14c.s^l
ql Eiltll^l Eql a4 a+. I 10-'s
r/(10-
: s)= --j*
ro
ko x(10-2 mol dm-')x(10-? s)
x IQ]/(10-'moldnr r)
@ ats+Es+Eea rqa E^lq ¤El6lrll i'JE¤ q=q=r+ ?"1 cqql+.

Ezl-= Ru2* ole-4 4lgg "J=+. +
2,2'-Hl-4?-lE(1, bpy)
v rdtJ 7lz7l
E Rulupy)r'*(2, +EllHu)-e =.lr-'-(2,2'-Elvl Elg)g 450nm
ll
r/(10-'s)=-*
ql^J tl ++-4tg d6l old(MLCT: metal-to-ligand (ko x10a mol dm-'s)
r,/(10-'s)
charge transfer) dolE .J9A+(E9 t tr). x
-
x [Q]/(10-'moldm-')
rr l\l et'.
<x={,.[
zldej zl$zlY z1&zl=hx 10-emol dln-3 solE e h=21
&zl x10edm3 mol-r s-,o14. [Q] = [Fe(OHr).]:+g :--a ffi
r-N N-
L,XJ il--) r+ ae s= "J=+.
1 2,2'-Bipyridine (bpy) 2 [Ru(bpy).]2* [[Fe(oHr)u]3*l/(to'moldm-3) 0 1.6 4.7 7.0 9.4
l/(r/10-?s) 0.167 0.247 0.297 0.338 0.46r
E=E *[Ru(bpy)r]'*3 &C +q4 +ql^J Fd+ olg(+ olg rB lac.2+ rl(rl(r0-7 s)E [[Fe(OHr6]3+l/(10-2mol dm-3)
[Fe(OHr)u]3*_tr fixJlaJg.)ql E6ll^J r 4%] + q ql6I^J E^l+ d4"14. ol {dg z1&zl=. 0.02eolq,
^¤F9Erll, Eqq4s.
EE ooonmql^lel g%r"+Eg +aq+e_EAl trt+ J kq=2.9 x t07dm3mol-r s-,o14.
+. r++ qlolEl= ole" o[{ o] H}*ql 4q} +"3 +E t}+
0.5
aad-q+. o
=
[[Fe(oHr)u1'*l/{10-'moldm-3) 0 1.6 4.7 7.0 9.4 0 ,4
r/(10-?s) 6.00 4.05 3.37 2.96 2.17 a

o
o
I
0 .3 (J
r.alg AlEl Stern-Volmer fB tjl"lrlE ol F"
^l(t+G.s^l)g
+g + glzl 18 ++. olq^J ol qlolEl= zldql *=+ 0.2
{
-?
EOI l4c.s^lel on/oroll r/rz'-+r a?-l6lH q+r+ a
g +g+.
0.1
0 2,5 5 7.5 10
^lol [[Fe(OHr)u13.]/( 1 0{ mol dm-3)
i={*tolol f.g 14G.2 H71 14G.29 tllolEJ= olE-Ll Stern-Volmer E t l.
E^]ts +
++qI +E +Elr11o[ a[eE ol o + rllol +4 %I= +Hg +A6IE h= zld tsg f ?lzl oIE
BB"l t*"1 "l*E+. %F= r.llzl4 olzl;559
^]
El ql4g 6t7l dql +flE Br il?-lql+qot +4. rfl ql ol
6Iq ol !g E^lql Efl+ EE +4421 9lollrJ al$ 46il^J Eg +E ?lzlE} oltrll= ro¤- Eq e E
=
"l =a6iloF
EllolElq "*+q ttoa-? s)e+ tal/(10-2mol dm-r)s +44 rI+.
14G Sglet 579
r. 14G.3 g+ +7|l-tjJ7fl ¤l0ll EH-d Roel ?"1*

rpl E7t 1&.2 ++"{ +ql^l _EBE+ ¤*.1 +619
o,7l4loll Eql^l 4,9 ilsn-E g'& +Bg + az\+ EzII R"hm
^gqb
cq+sE/l u.qEl6t94. otell qlolEl= ol+61q ol 4c +sgHl Damyl 2.2
ql 4+ 4s tI+= +61q4. D*ryl ODR 4.3
^* E]HI
I.5-I AEDANS
7"tfl
FITC
3.9
4.9
[Oz]/(10-2moldm-3) 0 2.3 s.5 8 10.8 EBE+ 1.5-I AEDANS 2.2
r/ns 2.6 1.5 0.92 0.7L 0.57 -=BE+ e(4^) 2.9
r_sr-loru¤ruPo,ot x ¤'t :$ . tr-l o*g AiE"l ).R. Lacowicz, Principlesof fluorescencespectroscopy, Kluwer
AcademidPlenum, New York (1999)oll ++qq fl4.
+ "Jg,
Dansyl 5-dimethylamino- -naphthalenesulfonic acid
s=E E"J-J(E= 3+6D
^JEHel 5rJ4oJ
2+zlE dg HI I
FITC: fluorescein 5-isothioryanate
+ q-*r+ *3 rll 7l^]1tr+. 1.5-l AEDANS: 5-(((2-iodoacetyl)amino)ethyl)amino)naphthalene-1-sulfonic acid (3)

"ilrlq+g ODR: octaderyl-rhodamine
?Ed tlC' S*+Q+S+Q

tH qqzl old' s* + Q -+ S + Q*
oldg trl-s=$ ?Je A+ql Er+4_o + "Jqt+.
dzlold, S*+Q+S*/-*Q-r+
il} +E tf z|41= Ag ,ll7}q+g B16l= trll E E* . qlqzl iz]]el $zll .tp1q 44=.4u"lel 4EE s].g
44o14.
oltr, ol{ol S*E+q qlqzl= gg ffi olol^J ol . E=E tlElg ?z}lE+q %L=¤ ol4* Ezl]e zld ¤-+
"llHzl g+
gE^J HLq^JEHe e^lq= a+q= E 91trI.
".F¤6IEÎ
= !lql^l= E=E=61
44olQ. Ez1 l4c.2e-l [Ru(bpy)r],*9 tr4z] ftill-$/lz| E".$ AoJol+ +EA'E4'o + tt6}rll +q9l
Fe3+.8 dx.l¤ 469-eal Arlol qErll, A$ rllolq- ol AIE A+ql= olluJzl old sg 4{l 4* al"tlr]s+ ?ol
"il
Tlqf9=_ +H6Izl * 6J+. = nol
44 e4Elql rl46zlelr|.
14G.5 ollLlrl old Rf +7|]-p7t| )la,ll LlElu

(14G.7)
4r oilLj^l 0lE Et
=B Rf +Ru
{lHzl old 4C S*+Q+S+Q*t: trP',$ 2.ol rJzlallg +

¤zlrl &e 4I #z}]-tszl] tr-ql r+t} 44"lEl(4?-le-l +fl
9i+. "JÎq= 4,.lzl +^19 41t- d7l*e sE 4lE d7l
a}*zl EHIE= frBrlil+. sel tsrq^Jqle+ E *E)o14. "14g^ atll_*zfl Îolql^J s0%o -8.99 "llHzl
dzl. ^J old"l gq+= fz]]-tszll
4 rlol9 qlqzl 7l.zl- lrrolr"
==
"J"J "J^t +Îd9 tiffzl- ^tolE Z?-l+r E + il= aol
4(r+c.zzloll R=&9 Bq^J q"Jg + gl+). 14c.7^lg ¤E
v-LEsthTl-B trI= EÎ +^|dol s9l E6ll^l g+g 4,o14
(q7l^J hE Planck9 {lfol4). olae $rld"l ++g + 9l
4 o + qeElfl.sq, 'J+ +7fl-Bzll t"ll r]lQ} &E Zl9 "l
ad'ol4(E44_" + Bohr9 41E+ aa.J 7A.e^lol
eo 6J
# gl+(s 14G.3).
='+E ezlel "J= "t E+ ultl gEql aa9t
+). rqE sE Tlt- 45q4^= aEzlql eqlElqil= ^trlEH3 ^JBqI
q, Forster olEq Eail aaol ++qrl 9l6fl^l= ?z]] EzI
=aE
dz}.il ¤6&9 +q dE ffi4 -E.HIE= +g^lzJ4. *g s -o
E ,J= Ezll9 ¤+ :-tr1=.e4 tr-'J+ CEE A

E T1+ 4+zI EHIE9 1l=+z} v-LEqth(MqE Qel HLq ^trlEBol
44ot EI+ "l 44zlt gEql^J Atllzl HJ=61-= olzl+ *
tr-Efle+ tF4E qlqzl ilol)e+ E"JB A+ql= ezl sE+
E==
zllz| E+g + gt= 4EL6J glHzlE *=+(rB 14c.3).
q qqzlg g461al g 4o14. + dol EHlEq t}o+¤^_q_
glHzl old E¤- rr9+ qlq4 AtIl- $2fl .r.p1e1 4?-l R
sql 9+ *zlzl QE #q= %Izl j/+e_q ZI+g + 9l+. Î
olE el= +41= ol+6}q ,J4$- +
+E qqzl9 old -a¤ ryrE tr}s=r+ ?"1 39{4. ^JEqL4 4lEql^J 4
C6I= Ets AB qLJrl O|fl(FRET: fluorescence resonance
u_I _1
= L_ _7-
Q, gE ollLlxlsl olE EE ttrell (14G.6) energytransfer) tlJHE zl=zl El= aol 14c.7^lol+. d¤4
' Qr,o
"J rnEr ¤Eql^J= ^J+.Ji]l+ ^llE"+el z}4ql+
glHxl ?
+H qlqzl oldql +.J Forster oEql el6iH *E 9lHzl 7]|E a"+ AR4 szl= Eoll 4E e. 6t+fl zl?-lql= ql
580 14 u3 ^-EE
S-E
EJ= 4ro[Ez[. EEt +Eae] sE o]ElL&q+qlqzl +
ÊEH zll r.s-r AEDANS(3)g 3"* a'J4 -trzlE Eq+E ol E
oel zlel ¤oJ ofzl-;E¤-ol aqa r1_^14_qlElBtalgl g
=-\
Ei-T- ^14
6J ar} z}+"tl E61l^l g.7s_e.+El 0.68-E eAoJ+. trI+^l
N ÊEH
14c.6^lg "l+611^J 4l&6IH 4r= r- (0.68/0.75) = s.ee3ol
94, t+c.7^)a+ l.s-I ATDANS/I1-^l^-Ellqg ,'dl Îol9
&=5.4nmo ++q R=7.9nmE +B + 9l+. trI?+î ol B
Ee E.HaI tt-.,.1r--qlElg Îolel 4"-l= 7.enm4-r. E
T.!Ef, v
+ el+.
fA 14G.3 Forster olEoll eldl'E 8Et|oll ?l= E^l S*-=+El ABxil
E^l-QEel ollLlll olc +E= S*sl==
HJ= ,\ElEaJol OE
=+ ÊlEgrl
,J^{rlts +^l.tlE+(ilei a= qg B$0il^1 slrl1sl ,JE,*=r1..
H
o
qzl BT]]E *+ AElzl szl= E"J+. a+ql ule[,tJ;- oiu]

Sos-
]=4l 7l+, H + "JxI+,49 s+ 7]|4+ Ag 4lel a¤4 C HO
3 1.5-I AEDANS 4 11-/.l'^-allElL-J
E"l izl]* tszHzI 9zls 6J+. rqH + Ezl rlol9 44
+ TlzlE & lkt] r+c.zal¤- "1¤:6li^l +g + gl+. ol FREr
"JBg l-enm ^lol9 ?J49=_ +e6l+ ql +!-" 6l-+= 4"1 I
q +4e+ sTii E^j¤oi ¤-.+ 4oi,-] Tjijl t +ql/.i +tI¤
^lE e4E *qe+.
+ glg ull= olEol ¤-E=6t= ^Lolql olE6l-= -gf,- 44zl
zttrJE! q 14c.3 alAairll 9y + Forster "lEql el6IE qlqzl oldql 9* a
qlE^J +EA E54lql +6J E+g * s¤ol f,zla11op qI+. 4, Stern-Volmer 4l o + qltlq= Er
FREr "JBel ¤E ^J
4 ?"1 ir* E¤-g rrrJxllE E" Egl u|4 ?zle}4.
=s-d7]lLJ=
tr r. "JEl+ HI*E 1il ?f^l+,-g ¤+El: Bzl aI4 B 5a ¤+61| EJI ol+5}4.
* rz} ^J^J+g I,JE= tI* EzI9 +e+ gq. z 4. +=c 4lc, dzt ol{, f.al-r. *¤ "llulzl old 4c5-g E
a 2. de e4ql E6rH 5= tr-Ele-l trdE +Be oJx| 455 tr"4e B%+ i%I4CE"l4.
6Ia gIJ +E +4lg+.
tr-+e+ tr s. *¤ "llHzl "ld9 Egg ?z}]e+ tszl] Ezl¤ ^lolE 4el
tr 3. Stern-Volmer E,,UE +E +ql^lE B"J i"JE +* r+Cg 7l +7lz'J;z el4q14.
=s-d^l=
,Alzl
oe. l.l
--1 +4 HE
^]
ril "JzI +#- Q=u I lô, 14G.lb
5= tlEll +H t,,=l l(kr+k,.,. +k,.- ) a*^ll flg trI 14G.3b
¤"*el olz145g. Qp,= kpl(kp + k,r. + k16) = kpro i=}7ll flg trl r4G.4
Stern-Volmer 4.1
Qr.olQ,,= t+roko[Ql I4G.5
t¤ qqzl old sS 4, =l-Qrl Q,.o AE 14G.6
4, =Ri7(Rf +R.) Forster oiE t4G.7

E+ 581
E. 71 ,\.1 4 HJ8+E=
E4 14A Af+ HJSel *=

¤E E^11
D14A.1 fl= *ilE g6lq4.
HI* i145 LIEIB + D14A.3 Hl¤alq ac¤. EqEl6l-= ql ol+B + 9l= de eil¤¤ s
D14A.2 HI¤:E iI+E "JE qtr oldol glL+? "+6Iq+.
D14A.4 ozi, ril 2al,,) +^t li} Hl¤¤9 5ag e"f"lq+.
oi-\
L-.rr
E14A.1(a) A+28-+3C+o HI89 4szl2.7moldmr s-'o14. 4 HI* C E14A.6(a) "JdE dflg E"ll^l +E Hzl y=(k,,[A][B])/(k.r+k..[B]'/2)-a
+Efl ^8C +Ee+
+t7 4EE +{tilq4. gfltr}. (i) Aql +.J HI* il+, (ii) Bql *t Hl* il-+, rEr (iii) dill HI
E14A.1(b) A+38-+C+zO tI*9 a-Ezl2jmol dm-3 rrol4 4 HI8 C * z14g "JoiH + ?l= 44;^ 9o1494.
EEE iJC 4se+ +Er 4EE +4I.Iq+. E14A.6(b) A-+Pe| Ag gE 7li]l-^J HJ*ql 4+ +E Bzlol u=k^lctlAlz
/(h+/cJel)el zJg Eol9.4. e}^Jol B^l'J + ?l= qBl aaql,rJ egl *
El4A.2(a) 2A+B-+2C+:O Hl*oll^J Cel rJC 4gzl- 2jmol dm-3 s-rol
6J if+¤ 4El|]q4.
+. Hi* +Eel O9 ^Jc Et
A, B, I,i +EE Ll4r+q?+.
A+38-+ C+ZO uJ*"tld B$ + q +-Ezl 2.7 moldm-3
^17
E14A2(b) s-'oltrl-. E14A.7(a) 400Kql^l eL zlall e+6JEfl E6ll +E7i t0% HI* 9oll g.zr
HI¤. *sp+ A, c, ,,i Del Et, +q
+E= +4rlq4. pa s-t*.a 20vo ** S9l z.ozpas-'94. ol Hl*E zl+= "J"l.Iq4
^8^d
Et4A.7(b) 3sgKql^l eI zlill o+.JEE Eoll 4sz} t07o Hl* +{l ro.or pa
El4A.3(a) 9f st+e.t(a)9 HI${l
'lio} +E ts49 u=k,[e][B]c],J4. s-'fi.a 20%o HJ* 991 s.e0pa s-'fl4. ol HI*E il+¤ "J"tr]lq+.
tEE mol dm-3-E +ElE 'l k 9 t+l= qB4l 941:+i +E H4g (i)
cel ^Jd +Ee+ (ii) Ael +p $s.E LlEqlq4. El4A.8(a) gA +qE 8zl 4"ll,rJ Tli]lt HI* zrcl@)+H,(g)-+r,(g)+
814A.3(b) ¤6 sr+.r(u)E HI*q 4qI +E B4S l/=hlAllBl'?e| 44. t. 2Hcr(g)zl "Jq+= E+q dill t{ol q$|l H6l-=zl ql+6}q4. Hl*
E-E mol dm-3-tr. +E|'J trll k.E *+lE qB4l 941,9+l +E Bzlg (i) c :aTlq Hi¤+=el ++ "Jqe Eg6}ir ^JcEe ?*=+.
E14A.8(b) ge +Elg gzl 4glrl Tlill^J HI* N,(g)+3Hr(g)_+2NH,(g)
=7116}zl
^tr +tr +4.llq+
E ^JC +Ee| (ii) A9 E
,I .Jq+= E+ql dill Sqol qe4 E6I.=zl ql+6lq+. HI*
E14A.4(a) ¤# sr+a.z(a)9 HI*91 ql6J +E Hzlg dlcl/df=k,lA]tBltcl =zl9l
H2e+ N2E ++ Sqg 34lolr" ?*=+.
e+ aq. ol +E B4g HI* +E uE 7l7la_ +E}..Iq4. EEE mol dm-3 ^8CEg =416}zl
e +49 ull hE +91= qB4l Elll!+? Er4A.e(a) 2NOBr(g)+2NO(g)+Br,(g) H}*ql trl-+ NOTI ^8CEl= Hl+
E14A.4(b) ¤+ 814A.2(b)el HISql .I6.J +E H4g d[C]/dr=1,1a1131 qI +A Ad 6}ql^l dlNOl/dr=0.24mmol dm{ s 'fl4. grr9 Sd
^-Ezl
lcl-'r+ ,J4. "l +E Bzlg HI-& +E u= 7l^la- LtEi4q4. tEE +E= B"|z| 9{lg+i
mol dm-3E L|+.3 trll k el +91= qB4 911:+l E14A.e(b) 2CH,(g)-+CH,CH,(g) HI*ql trl4cH,4qAE g+E He++
E14A.5(a) +E B4g (i) mol dm-3 ++lel +Ee+ (ii) kpa B9lE $H e.
+4 Z4 6}ql^l dfCFtrl/dr=-l.2mmol
-Ez| aj dm-3 s-,*.4. CH3CH39
L}4qlE 2zl0\ tzl +E r}+E ++l= q¤41 qAL+?

" CC 4s= 9"IzI94lg+i
El4A.s(b) +E B4g (i) molecule m-3 Egl9 LoEq (ii) Pa ++lel Se
o e 4448 zzle+ 3zI +E
^J+E +flE
q$fl !AL+?
E4 148 4E4s E^l

¤E E^11
D14B.r HI¤¤ +^hile| +^|2zlE +B6l+ +ge +8ol+? ol HI* D148.3 +E Bzlg aa6h= ql ol+El= E+¤- dE HIHEE +
Hi*el
zl-+-L qtr aaql^J "Jq+L+? +dg s¤:6-J + 5a¤- ¤E6Iq+ +ElB, 371 HI¤: +EE, :_4-L rll
olElE 4+ +E Bzlql "*+E H.
D14B2 trl-g 4Eq 4s"61-L 44q +E B49 *lzl' (a) [A]= [A]o-k.f,
(b) ln([A]/[A]o) =-k,r, r4r (c) [A]= [A]0/(l + k,r[A]o).
582 14 u8+E=
G-\
r-u
E148.1(a) 2A+p HI*g 271 a-E H4q q4^J +qlqq, r +E ^J+ E148.4(a) slS"Coll^l zJS S4ol 363TorroJ 7l^ll^J o|,tlleojrllal= ^l.E.
E. k,=4.39r 10-4 dmr mol-r s-'o14. AE +E7I O.ZtOmol dm-39EPrl el +6ll HlzJzlb 4t0sola, $4ol t6eTorroJ 419 tlzJzlE 880solfl4.
0.0t0mol dm-3 o -e H6I^L Ell eq=
^lrJg 4lt6l-q4. "l HI*E zl.+¤ +6Iq+.
E148.1(b) 2A-+P HI¤e 3xt +E- Ezlq r}4rl +4qq, r +E ^J+ 400Kql^l z]9 $Eol 55.5kpaoJ 6J Tlillt}3rHlEE +6ll Hla
E148.4(b)
E k,= 6.50x l0-4 dm6 mol-2 s-rol+. A9l }.ETt 0.067moldm-39E*el zli:aosol94. .Jtsol 28.ekpaoJ rll9 tlzJzlE l78solfl4. ol tI89
0.015mo1dm-30e. E6l+
aal= ^lag 4&6Iq+.
r-ll il+E- +6Iq4
E14B.2(a) A+B-+p HISol Ae+ Bql +6ll^l E_+ tiloltrI. AE EE7I E14B.5(a) NrO.9 li} +6ll Hl¤: 2N2Os(g)-+aNOr(g)+Or(g)oll Ell+ +E
0.080mo1dm-34 BE tETi 0.060mo1dm-3oJ +"-4 +ql^J ol Hl+g "Jq
^J++ 2s"Cq^J &=3.38x10-ss-'o14. NrOr9 tlzJzlE g"l4? H}* azl
+rll 6}flqul r.orr +ql BE bEzl0.030mot dm-3o + Ar4f,+. (i) + g ++ $qg 500ron4-lt alB *gol rlzl¤zl (i) sOs +el (ii) 20min
r .;$5 4lt}4q4. (ii) HI¤'+=9 uJzJzlE +6Iq4 +ql= y E $4ol ¤"Izl !d:+t
El4B.2(b) A+2B-+P Eg 2il HI¤¤ AE *:ETl0.050mo1dm-3rl BE t. El4B.s(b) 2A+p H}*ql^l e+6J¤ A9 lil
E6llHI* +E tr-++ 2s.cql
E710.030mo1dmroJ +sq +q^J "Jq+rll 6}flqq l.Oh +ql Ael *.E k =:.sox r0.7s-'o14. Ag HlaTl= g"I*i
H}* azl9 A9 +E Sq
^J
z| o.o+0mol dm-3o + Ai6I9trI. (i) +E ^J+= 4l4I6Iq4. (ii) HI¤¤ I :r.o kpaol4r atB H}*"1 rlzl¤zl (i) 50s -+s+ trl 20min +ql= +
E9 tlzJzlE +6Iq4. E $H"l B"Izt q]l.L+?
E148.3(a) riJl "Jq+= Plg Hl¤¤ol HI¤¤ql Sullrl o
+Ell ^Jql^l E1aB.6(a) CHjCoOC2H.(aq) + OH-(aq) -+ CHTCOl(aq) + CHTCHTOH(aq)
zloltrI. r qI q7i
Ea+ ts^Hl 9lql^l "Jq+= "JsqotE B6|] HI¤- H]*q 4eI zz| +E tI+: 0.ll dm3mol-'s-'oltrt. olllEt9lE4 +Î
olE+. r .J ¤¤q^] slLlEE¤ Z7l *-E7l 44
"JEqolg ? E "J4"1 zzos rlololl zrtpa-s*q [NaOU]=0.060mo1 dm-r4 [CH3COOC2H']
lOkpa_=. e^6}9.trI. (i) ol 0zl Hl¤:el 4E- 149 +6Iq4 (ii) d^ll "Js 4lgH (i) 20s +el (ii) 15min +ql= qllEls
=0.ll0moldm-3ol Elrll
.lolzl trI Hls" 6lelfl g"I4 eflaL+? cHlcooc'HsE bE-zI g"Is slAL+?
^lrJol
E148.3(b) -tri--4u11 tlql^l .lltsg"l lz|- te+ HI*g gea+. + ¤ E148.6(b) A+28-+C+D HISql Efl6J 2rI41 6f0.34dmrmol-r s-rol
eql^J qltsgg Etszl- r.22xr04 s rlololl 220mmol dm-r9E*rl trI. +¤¤-=4
=z\ tsszl zlzJ [A)=0.027moldm-3!+= [B]=0.l30mol dm-r
56.0mmol dm-3 o + A.t6l$,tr|. ol HI*E +E ^J+= +6Iq+. "l Elrtl 4gH (i) 20s +el (ii) 15min +ql= ce.l EzI
r-" g"ls
941,:41
EEJ "t4C E-do+ tr=6l.= UB

¤E EI]I
D14c.1t}Sol qtr TlzlE r HI* ^-Ezl "Jq E"+ql ,Js"6J f o1K..2 gE EE dEE d+g ¤E6Iq4. ol *H o + +g + 9t= HI
fl4Ls+i =Ag *9 ul4"lq= q¤ 4."14i
G^
r -tl
Etzrc.l(a) oJ=q. gralc_-E 4 rJol liloJ olde!ls+ H}gql rll+ gE E+ Elac.2(a) HI* A+B+C9 AHi*r+ qHI*E +E ^J+: 5.0x 106
¤eq^l Ssl ^lAol 27.6psolfloq, AHI*E 4s.145 rz.+ms-rol*. dm3 mol-r s-'(2i|)e}2.0x l04s'(lzi)oltr+. ol HIf,-E Be :.J+¤ +6Iq+.
+. q-HI-&q q6J +E tL+E +6Iq4. E14c.2(b) 6J o+ EZITI +Eeql eBEl= RI¤:el *lB drfzl 200o1fi.
814C.1(b) oJ+ B'6Je__e. 4'Jol lilt AHls"r+ qHl¤:E }lJ?.#71717+4 4. EsE ¤eql^] ol et} r+ae dxll4 oe zi| HI*"Jrll +E *#zl
24msel3emsH4. s-E .EE L B¤ " + ElEoITk Se+ 1.5x l08dm3 mol-r s-'olfr.tr|. BEa_E zl.Etr+El "J Ezlzl- a1l49= rzi
q+. ^ltg 4l&6I Hl*el +E ^J+= 9"lzl EIXIL+?
EEf .'l4D Arrhenius ll

¤E E^ll
Dl4D.1 *3 g.Eql^l Arrhenius ** ol+¤ ¤H6Iq4. D14D.2 k,=LnA-E^tRT 4 oJ¤¤. cE6tn ol qtr 4aql^J c
^lol "*zl ^.lel ^lol
B6l^=zl b6}q+.
EA 583
G^
r-'tl
Et4D.t(a) 6J ^Js+qL r+Aql^J El HI*e-l g'Ca+ qlLJzlTl 87kf mol-'olfl Arrhenius ul4"l el E A = 4.00 x tors s-rE- E^= 26tkl mol-, ol 4. (i) 20"C91 (ii)
4. gsz}3rc-+-+El Is'c-tr, Eqe q +E *izl9"t4
E6IA,L+? s0o"cql^l
^l=s+*E tlzJzl= +6Iq+.
E14D.r(b)gs+Hldqo}aEE 6Iel H}¤E gcE+ qlulzlzi ee.lkl mol-'
E14D.4(a) ol¤ Eeq E6ll HJ* +E d+= 3s'Cql^l 3.80x10-3dm3 mol-r
ol$.4.ol +E{}fzl.2s"Cql^19 {}trtrI r0o/o7l rl 4xlEgE=+4q
s-'ol-tr" 50"Cql^l 2.67xt0-2drn3 mol-rs'o14. ol HI+g Arrhenius ffiul
4. Et= +6Iq4.
ElaD.2(a) E =sokl mol-roJ zEzlE HI+g "J9zlE Exi eE Egol E14D.4(b) qtr EeE +6ll Hl* +E tI+=
2e"Cql^l 2.25xto-2dm3
0.r0ol q= gE= +6lq+. mol-r s-rol-tr 37'Cql^l 4.01x 10-2dm3 mol-r s-'o14. ol Hl89l Arrhenius
E14D.2(b) E"=80k1mol-roJ 2ezlE tI*"I s0oKql^l "JqB ult g"I"Jel s|4rlelE +6lq+.
+¤.E +E.01 HI¤¤ "Jea + 9l4lL+? ElaD.S(a) qE sl+ Hl89 4E7l gEE 24'C-e+El 4e"Ce k9rtq :
E14D.3(a) Clr+ H, 2717llll-* HI¤¤. +E uJsz} A=8.1x 10-10 m3 H]|e 51fi.tr1. gCatl.llHzlE +6Iq4.
^l."19
mol-' s-'ola, 9CEI9lHzlE E^=23k1mol-'oI4. sooKq^J ol HJ*g + Er4D.s(b) q¤ ElqL HI¤.E L-Ezl gEE 2s"C-tr+El 3s"C-e Sgcl'l z
E *+E 4l4I6Iq4. ts|]s E19.tr].. !l¤s} olluJzl$ +6Iq+.
Er4D.3(b) zlill-^J +6ll HI8 cnHr(s) -+2CrHn(s)q ql+
^l=s++E
EE "I4E HJ8 trI 7 IL E
¤E E^JI
Dr4E.r
^lA-¤B
714+ A+tr'4 714* qB4l trle+? olEol tol6.J Dr4E.4 HISel gCar} 9lHxlzl qBrI gE fig 714 + 9l=zlE ¤¤
a+= +4.g + 9l= ol+= ¤H6Iq4. 6Iq+.
D14E.2 tol6.J Hl* SAq^l= Hl* ).1+71qBrll HB + llEzlE ¤ Dr4E.s HI* zl+e+ gxlEE qB4l 4=+?
q1-o-
E6Ir qlE Eq+. Dr4E6 tI* "tlzlul=ql^l +E aA *A\zl7I+ Lfl Hi* +41+= +
Dt4E3 HI*el +EE4 zlH]]e+ gE+4 xltsll= +E6Iq4. ol E +: 6I '.lCg ¤6Iq+.
+E -r._E= 7l?g "J6ll lrote}.
G^
Jtr
E14E.1(a) rl¤-qlrlq#g 4zl 6ql^lE s+E 86il HI+ql 4all! zlltl E14E.2(b) 6J +6J HI¤-g qlT}q=g e%'-6}r+ E%}6JE gCaI qLlzlTI
¤ 4"14. zJzJ 27kl mol-'r] 35kf mot-rol utsIE .J"l4l "lq^-l gcsl
"ilHzlz} rskl mol-'oJ rtdol ^l-d-*l¤ol
gtrtE+. ol +!+ Hl¤-g gcs+ ql
Or-+Or+O k^ HzlE 9"IzI94lg+i^Hl¤:
Or+O+O, k:^
E14E.3(a) ul+l e,9 +6lt HI¤- rllzl.Qaol +gr+ ?Jr+a
O+Or-+Or+O, kb
^J4E+.
tn
,!41 B4lrI +E AA +41'Jg -Bola oloi^l o,ol EqqE HI¤.9 4s
Hlg o3ql +6ll^J 2ilolI. o,ql +6fl^j rir"Jg trq4.
a, # e*e A+B )P
El4E.l(b) +¤-o-qql^l 2-e+ eql*g cH2clcH2oHe+ +4lq- ol80l HI* A,E 44= lilola a9 zlldElS Aql +6ll^J 2iloltrl. E. A
A,ql +6ll^l
6Iq 4}q+qlB{! (cH,cH,)oE "JE= E}AE qlTiq=g q+4 ag + e+Bel Hl¤¤ Ae+ B E+ql *ollrl rilolq-. p9 ^8c +Eq qEl +E H
4lEe ol+qd4r "Jq4lr+. zlg (i) A,4 e
Îolel îd-BBg
7Ie6Ig (ii) Aql 46ll^J A+-tr-Ell
=
7tA6Iq +6Iq+.
^lBg trl^l g¤3rl5l= rtlzlul
(I ) CH2CICHTOH + OH- ¤l CH2CICHTO- + HrO E14E.3(b) Ae| BE ztg-e-tr.PEi 2+ +Col Hl+
(2) CH2CICHTO- -+ (CHrCHr)O+Cl- Els_r+ tqa ^J481+.
="1
+41 (1)ol -trElE ,rld-BB"l ol+q{+r 7ia6}E c^d e+sfu u-5H
+E7l u=kzrflcHzclcH,oHlloH-lzl E9 u-q4. ¤zl,rl ^}qqgflE
KE a4l +41
q ElloJ ¤B ^J+, r4I. /c,= E-7q +4ql 4,¤I4s t}+trI. ¤zlrl u= E$e+ +d"lr" H= "JC'J g9 4Col4. e9 B ÎolE
E14E.2(a) .J +!+ Hl*E q"J6J9 gdarl qlHzlzl. Hl¤+ 4 +=q +6H^l rzlola u7I Ae+ Btr 9Eolz}= Hlsg uql +
'il7}q=:g AoJ6.Fl a1.q rzlr|. rel-r. uz} H_tr q= HI¤e uql +6ll^J li}+. Hel tc 4s
z]4 zsUl mol-,4 38kl mol-'oJ utst= olq^J
AHI¤'
Îd-BB t}*ol "Jq+rBJ89 e} .il 4+ +E Hzlg (i) zl-cat:r" (ii) uql a+^}el
Cs+ "llulzlzl tOkl mol-'91 4r"rol Fl4Er+. "l +6J +tC Îd_¤Bg =ÎBg
e+ qlLlzli $ulz| 941.9+t 4+^14 +6Iq+.
s84 14 u3 +EE
E4 14F U3 DllT lLl=el ql

¤E E8I
D14F.r +41^l "t E4l +!+ Eil7lq=E g+ql +jr" +qlg D14F.3 aa-gqlz|$ HI*E +E= gEql ql4^J E^|6IH +rlt7l +EI
ae+q ^|"le-l ^l¤
+EE4 ul4"lel= +q+iJlE E- a"*g aag + 9i= %IHg 4ErJl, olAg Arrhenius 4(Eq l4D) o e ql^Jq= en+e| EB6l H.qt
"51q4. 4. ol a4= EzI faq^.i ¤B6Iq4
D14F.2 ri+ HI*ql *aJ Michaelis-Menten ,llrlq=E 54, old, re]-,l D14F.4 Lindemann-Hinshelwood
"ll7}q=ql
qgB t+zlE HI*E +E
q}4lq +4^l +E tr-+ql 4qI t, = k"kulAl/(ko + kllAl) llol olE saql^l (a) ri}4E
=6Iq4. Bzlol4 O) 2il +E B4ql rEle4l El=zlE +61q4
G^
Jtr
El4F.1(a) 2s"Cql^] qE .J ?1=9 F+-4u112}3 HI*el Michaelis +E ^J+: t.09kpaoJ rll t.zxt0-3s-'oltr,25paoJ all z.zxto-os-'o14. ol
^J+=
0.046mo1 dm-3o14. r?-l:r zl$ $-Etl0.105mo1 dm_3g ull9 "l HI* + qrlq=g gCsl +4lql qoJ +E ^J+E +6Iq4.
E_E Lummol dm-3 s-'o14. ol HI*el 4lEll +E= g"tz| EIAL+?
E14F.4(a) 6J +*ill7l- k.=1.39dm3 mol-rs-roltr, A7l +9lill tig.z}.
Et4F.r(b) 2s.Cql^-l qtr EI 7\49 F-+-+E|] I+ HISE Michaelis
^.I+= lo.0mmol dm-3t aaq^J +41^l 4Aq 44 +El¤r{. r=s.00h E"J +
0.032mo1dm-3oltrl. rell tl! \-tzl0.875mo1dm-39 "ll9 "l BJ¤- + 6J"l qlel
EE o.zosmmol dm-3 s-'o14. ol HI+g alq +E= 9"IzI Elds+? "JqHg +q+¤ +94 +tlE= 4lti6H4.
El4F.4(b) oJ +6Jill7} h=2.80x l0-2dm3 mol-' s'ola :azl tg4l Bgzl
Er4F.2(a) &/K"9 ul$- E-+$ .4ull a$ol+r 6'J+ tsE -trzl 14F.29 50.0mmoldm-3q_l aaql^l +41^l ,+aql q4 +*¤4. r=10.00h EoJ
rllolE.l= ol+6lq e4I B+ Eêl +']] E+9 4l4I6Iq+. +{}ol gq*g qE fi}E +gr+ +6JEE 4l&6}q4.
E14F.2(b) 2e8K.'llq t zlltet)el a.^_3,]] H+t Hlgql^l a4 tsE Er+F.5(a) s4i lii.ii tri+.',tl.',dll= +EJ:xliE 'J41-Eiljlr.l. zll.t.lzJl$ t.E_
zl leOx lO-emol dm-3"J 4l Kr,a=0.032moldm-3ol-y' u.*=4.25x l0-amol
zI3.6ts|]-tr. +7li;la- +9lzllE +EzI4.2HH ,JdqlqE +EE{ ,tl$.z3o1
s.i. r+r.z(a)ql^l eelq} o-Ê +o]l a&g al&6|.q4.
dm-3 s 'o1fr.tr}.
zI Bplul E6Ifl!.+?
E14F.3(a) Lindemann-Hinshelwood qlrlq+g ,*= 6J zlill $$el -gA E14F.s(b) S4 4Aql qq zfl,r.lillel fE_
^J^dq= +Eli.llE ^J4olltrz}.
41 143 1.30 kPaoJ ull z.soxt0-4s-'ol.a, t2paoJ rll z.toxltrss-'oltrl. z| ro.ouJf-tr A46Ir. +9lillg *Ezl s.otsH +7}EI+H +EEA \A ?J
ol ollzlr,1#9 gCsl t4lql +E ^J+E +6Iq4.
ElloJ olzl-Sul-r{ E6}AL+?
E14F.3(b) Lindemann-Hinshelwood ,ilrlq+g ,*b .J zlill ql$$ $a
EEf "t4G =Jsl+

¤E E^11
Dl,rc.lE¤E¤ *oI_H-r. 4g r+AE"l .Jq+E ¤i"Jq S+q= ^l,J ol9
"llulzl
old, ¤-"4 +ql^l "Jq+= atolgE r}"l9 dz} old 4c,
zlEE "JBs-e ++'Hq+ EE dz} tl4el +Î e^1, Ezl Eld ¤d., r4i1 .-4ill +ql^JE +E
EzI tlE' ¤+i, "JCxI olA HI*, FREr B4ql^l ol*El= B%t E4¤ rl
G^
Irr
El4G.1(a) +Ea s.HE 6J o}trl].&ql r.s-l AEDANS= *+A.J^l flqq 2.28mmol9 BrI ^8CElfl+. Aq Ej=g %tz}9 fE E"Iq 941
4 szlE gl1" +E 6lLlql= FrTC= a"#¤6J,<14 Ezl= Eil4. r.s_r L r-}?
ATDANS$ BoJ oJz| f Eol FrTCE i{}_e__tr l0olo #r6}*.q-. olulL El/rc.2(b) "JEIE HI* A-+B+Cql^l 500nm Hg ¤ trllE "Jz| +5Eg
tI= îolel 4 ?-l= B"Izl-= ElllL+?(4EI.J &q &3 s. l4c3g -H-oI4). l20mol einstein-toltrilleinstein=Imol photon).200mmo19 A= ol qql 4
814G.1(b) a+ sH9 q! oful5$oll r.s-r eroeNSE ro*¤6J^la Ezl Hqq r.77mmol9 B7l ^8dq$.tr}. Aql ¤:+g %tzl9 E"t4 941 ib
LL-}?
EBE+g B"J *zt t= Eol l.s-r AEDANSg r*e=? ls,/. Ai6lg.r+. qE E} gag B%I "Jz| fE¤ol 4r,o=0.35014. ol EaE B
gdg+t E14G.3(a)
+}cs+ zlE]e+ F-^ E.ts
Îolg 44= E"lzi "J +Bg +46l+ deq^l B* gi=ol 5.6nsg tlzJzl= zl\a_ rJ^l6l
oll9 *zi +-g 94. ol EAq ¤%l +E t}+E +6lq+.
E14G.2(a)
"J+qL HI8 n-+zs+Cgl^l 500nm Hg +
2I0mol einstein-'ol4(l einstein= I mol photon). 300mmol9 AE ol H9l e El4G.3(b) qE 6J Eeq B+r *xI f Eol 0r,o=0.16014. ol EeE B
=
EA s8s
%I +Eg +461.= dEqlî B%I %I=ol 1.5ns9 elzJzlE zlzla_ a46I E14G.4(b) ro=3.5ns91 +rl B* Eeg h=2.Sx lgedm3 mol-t stoJ d ;1-
S4. "l EeE E%I +E tr-+E +6Iq+. 4 ol99 zlzla- "l #zl E49 B"J îlzl= i$z'llz[
EL4.
^Bl^l7lqr.
E-qzixl *9tg'Iel aE 75o/oE zJ+,rlz1a1g rrlzllE t:EE gulE
ElztG.4(a) ro=6.0nsoJ *zl BoJ E43lco=3.0x lddm3 mol-r s-roJ d ++
ol¤¤ zlzla_ a+t^l7lelr. 6-J4. *zl E:49 BrJ drt^-ll7} E
d+q"l at4l,r+t
"l ^ll7lE gule ali
?j:glg ullel iiel 50o/oE a4^l7lqB *.EE
"lzlzl ^%lxllel
+qo} 6I4.L+?
EZll. 1O HJB 4-,E=

-5.6lxl ErTll
o tl -rL/\ll
rra.r %tg++ HI+q ql4^.1= z}]4^lE BB zll.d"l 4*slzl ?*sq, ^J trq.+ *3CE+4 "t ^}slql4 +e +ql= zlill +,H4I+ +alrl 5.q
cEr+ Hl¤¤el a+-^JEll Eo EE ¤B Ztr+ zrll tr}= + gl+. qls^l 9ltrH="6J4 ETll n4.l).dgBol ulzll +r+lzl= ¤dlg 4448 sn
A-+B HI¤:S ¤jlql 9"1lrl tlBslq r +E: r"olg : 9H}¤¤ zEx} EBql^l= 'J+= Y Fs +b4. + Bql Ag + il= Ag 7]i- "J+
^ll
E- HISs-E^l Hl$ 4Ez} k,[B],"]r+. Bel A+^]Ell E"EE $u[r]t ol {t s, Hq aq^-l dg^la + 9i= zJ¤zI r, :el;. Hq aH+ il_eqflA+
^.r+trllz} B¤
/J-Elle+ 4E olf+ +9ol+? +fl4+ E= Eqqfl4't 44¤ zllelzl RE ^ll d+"ltri. ol4+ 4Aq
g¤ ,llzlul¤i S-+r-+Roll 96IE trl-Sq Ag +E Hzl"l CBolloF
t14.2 Tlzll*ql^l "J+qI4
giel Hl¤-g dlccl.l/dt= "J4.
+E =-Etrs.Eg
k lcl2l'2l"'2el B4g trI=+ gA .Jqol EllB6l k¤- trI olel6-J +
s Hzlol +4+qH qtr qlT}q=ql 96ll^J "l HI¤.ol "Jq+aL+? #=-o, #=nI-or #=o,
qI+. qE
Îifl +,ll 4*ol4l
rrq.E .rJCEol +,11 +¤¤ 6l-= HI¤¤ z}^]l +rl|$+ t4l=
"lE 4ol4? Bol alzlzl{ fr
ol ol
,rl A-+P HI89 ?* 4s Hzlol u=k,[A)[Pl7] qq, ** 4E-zl-Pel +l "llzlr-|fr:9
elaxlE aaq-= ah al4l ql'J aag *.rel. ol ,llzlrl=.ql^l= dill
Eql Hlzllg + 9l= 1014. ol HI¤¤ agql qg Hi* AP-zl9ig + 9l oJ++zt "Jd6l+=, 4 S+I+R=NolelE dzjlE 6Ir fl=ql,
"lag
,l q+ql "J"l4zl ^l4I6Iq EJE p7I ^871q,
olaol olq^l x}4l 4oll
& zl4 ¤+l"ll E+ Î"J, "I t+ ol$ EE ^l7J 4E7l ol dgBE = d
HI*g "Jezlzll ¤4. (a) +E B4ol u=tq[AllPlT] q= A-+Pe] eg E Ei 3r{l Hl6ll^J ztr}s 4¤: z}cl{tr}= *ol 94.
I HISql q.J +E^lg zJ+6Iq q-g +418 trq$. ^la
rr+.s ,i}-*ull+*r+ Szl-+,HzI¤¤ SzlE¤ H++ql^]
^l^+ "Jq+=
Hl
tPl (r+b)e'' 8o14. (a) rf^g- "llriq+q ul4 nHzI ^8cEs 9L Bzl-+,ll4}+ HI¤-
el +E H4g +E6].q4.
IFI;= r+b"^
4zlr-l [P]og Pq a7l }:EolJ, a = ([A]o+ [P]o)k, r4.I. b =[P]0/[A]0 AH+B#rr.*o-

ol4. fle. +E B4 u=_dlAl/dr=k,[A]tplqlc [e]=[A]o_a relr
AH h ) ^JCE (+E-eA
lpl=[p]0 *rE L6tr F 6 z]Srll qL 6]L]e.l Es] +EE x9 6Jfs *
A- + +Al)
Eld+. ol e4e ge 4e +E E+H9 ol*a}4 4EElEilEg ras9 (b) trlg ,llzlul6"ll u14 uez| rJcEe q= &-+,ll4}+ Hl¤.E +E ts
+qz}e{ 4"rl x¤. -H.o}et). o) bq a}¤- tolal.4l +16}E^J [p]/[plog rql zl9-srap4..
4ullrJ E^l6Iq4. eL^8"1 ?3 44E- [p]/[p]o= r-et,,zl q= li] H]*
ql Eil'J a4 Hlj/d:e-E;rl [p]/[p]09 19 Erl E"Jql
"lil= z[x-ll +ull z[
*el a'q¤ Ebtq4. (c) *9 (a)e+ O)ql^] Eel.J xla]l +,|] rl{ql^l=
HA + H*
d-4 *r.
uJ* 4E.zl r_*=-(1/a)lnbql^l alqT} ¤g trq+. (d) + zlzll .4ufl q!$ HAH++B > BH*+AH (+E-ea +41)
A-+P9 +E Bzlol dlPl/dr=klAl'[P]s +4*tr}. r-oE# [A]nr+
=71El=
lploo +r "l +E Bzlg ¤q4. H}* 4gzt aElle
e
^lag +6l.
rrc.o 4* +q+4lel E a%iql 4EI =-¤t-^ll* ¤iI l<^/t> - (wzluz-e-
{4. (e) 4E s 6}+E A-+P HJ+ql^l= +E H4ol dlPl/d,=k lAllPl'z E¤p9 Et+e +4LIq4.r4r olaE ,<1zJ $fE.$ +6H+.
s +El*tr|. =zl :-o-E$$ [A]or] [p]oo + Eatr ol +E H4g H] rr+.2 Bil oJ%'- E e=*4 *t zll# E e=Je-l ulE (a) ts& p, o)
* +E.zl.4qs El= ^ltg +6}qe}. =qel.
olg zlzlr 4l4}6rq+. ^l¤ a
-*vla15
HLg
uoo -=. a{6l. -I -t
ol E4^ql^J= HI+el ,l*

444q1 +zlql Ezl¤ol qB zla aeJ4_o -+ +49 + ?l+. r4r s4* +& EI*4g
,ll 4E6l=zl$-zl..$Jal 3;.[a[ej_r. 6Jtr}. H]+ol "JqB q:. ols-" 6fcl 4cg
^8cEE *?J4 "l ^la4 HEl- _H_Q z].,rllal.
$x]. goJ=ql Hslzl- "Jq4l" 6ll?-l qlqzl cEq qlLl ,ll ¤E6l^= 1"14.
=
zlzl {El A'JE =
xll$ullslr., I ¤aJol #qzla E rse.r to-{ +oil^1q EJE; rsB.2 Eg-aE
Îolql ^l
e6Jol ¤Cqr 6J+
^H
olEl+ r+eE.q +EE-
=g4e-e.
4l&++= 43 zl=. lsc dol-c|E|l olE
6l qeJg "Jol+. rq+ +E E}g +?$+ Exll"llriel
"i&zt ole$ol.tl='dol-^J4 "lSB ¤B++. ol ol$oll.<J= Hl
zle zl.,<11*q]¤¤ 44"1 ,rizll Egzlot +d-6lzl ¤q r
Elg +E4E Ee 9Bzl 9tg Aol4. ol s,7l^ql^l= +
* Ezl-$ol $CatE$ BCaJ4l zle6kEl1, ol $rJffi
+ r+ "llHxl ,llal+E zlzlt- E6J + ql4. d"l /J.
$z| ,,.|o1"llrJ dzlold"l "Jq+jr" aoJol #qzljJ, ^l a =+lEg
4 "lEg oJs-"6[fl gq+4 c]4"lEl= 7l-^lr +E t1-+=
'J"l ¤Cq-,l6IH^J dflq= z$xlE AHI*el +E tL+= +48 + il9-q r?]6Lq ql+ +E= gqql4 *B o e +
{4 z}zl ,}Bql qq
4&6lt n;rz} 6Jq Tlal-^} H}go str_
4H + 914. ol "JBg +a4 +q^Jq HI¤ +E. u].4"lel
+q 'l]+"1 Big C-H-E gg += ilxl"J +rJ qtr"ol q. e+ ql ql*61 ¤4614.
Bg H]¤-==3 ¤=_t}+ql^l "Jq+q, ol aEE¤ ol+6IE ^l7l=
15C.1 Eyring tsC.2 EEtrt4 Ig; 15C.3 +EEq Eflfl+ al}
ol;l+ HI* +E= ql+6J + 9lg 4"14. ^.1;
lsA #01=
15D Erl#el
=+tr}
slE HI+ql +* 7l* dnoJ ++E olE* qHI¤ 9lHzl
ol e$oll.<J} Hl* +EE A+6}rll A"*4eE ¤¤g +
TttL
sH4 olE EEql^JE Ezl-59 +t¤ 0l+61-= 1"14. "l
9l='+¤. rag 4,o14. ol olE+ ++-J ,l4l-^J +
ol.a_',g
Eqql^l ¤Baldzl"J "l *Bg ol+6IE *f,-ol gq$ ql
E ^lol"ll^J "Jq+= HI¤¤ E6h= qlql"J ole"¤ f ?14. zl .Jq+= ql+61 z1416l EÎ6J + 9leq, EzI ¤9
E4e 6¤. olEg ole"o]q t Ezlzl += Ezlql "lzlE e ^lag
ol*6l.q olE¤ ¤+61+ g+.
4"Jg +.H rq6}ir" olq^J Crel r$$ E6Iq ol 5g. ql =A7l
15D.1 Ert ¤; rSo.Z EJEC *E; r5D.3 EIE!¤ oilLlrl EE; 1sD.4 d
lzlzl gs¤l AElql qBril +49Ezl= aAdlB= aol+. Brt llto._e+E1 ge e3[
rsa.r el8c EE; rsA.2 RRK -Eg
lsE Eglloil^1sl drt olE
1sB EJfi_rlH]| UB ol e$oll.<J=dol-^J4 "lEg "l+6}q +"4 +ql^l "Jq+
8.+ +ql^J "Jq+= HI¤+ F 6#e.'1-E + 9l+. + + HI Hl¤¤ EQ++ +"J Hl*4lE 3"+6}rll g 4"14. -J4 ol
=
I Ezlz} "J+= HlEql el4^J Hl* +Ez]-ffis]- '+t}- +qr ?Its rvrarcus olE+ dz} "lc9 g.cE+ vl.4"lrle+ 4
EzI tr-"ll +E+ 9lHzlzi +4qq ui4"lel
^tolE +al$ +6Ir" Sqd+ +=el 7=
zlu11 HI-a-6'4 E tI+
^JE "J+=
of HI*ol "Jq+='$Cs+-zlu]] Hlg5.'E F f:f_e. +i} a ol +alg +4.4= 4,o14.
ol+. *E HI*el Hl+ +E= eqill +q^JE +41 dd$ zi =71^1a-
1sE.1 Ert old +E H=l; r5E.2 flrt qH Eaq 9E; r5E.3 Erl 0l
E *s. 8#; tsE.4 ol=e.l de4 e=
EEf 15A #OIE
+5 +H4 o(tr4 1B), l?-l-r. Ae+ Bel "J"Jolf "Js,qr+

> ol EEJE ufl+= ol8
EIEIE Et +E EoF= Elqr utE *-d E?rl.
Exl-0il71-Ll=0fl
s6ql Hlql4o} B 4,o14. i,
AalT|9 Et E7 ElEol olE?ltll 0l olEe Xl=q"*ll^J gE6lq Nt*Ul
=E
7li{-8 HJSE rlîl-d oil7tLlEE EeEt + ?lxl slgrl'.
u * o\T I M), t, 9{oMs * o(T I M)tiz [A] [B]
> E4d TllE

rqq ololzlelE +E^lq
+Eol Hlso s_tr +E "llHzlzl-
0lEoll^l= 7lrJl8 2ErlE HJSoll^j= H-tB E^lill
== 4lA+ HI¤el "llHzl E', E+ 4ot *+. olag 4s dlfzl
trll olEJ -d EE ,J ol,sE alrll4 oilLl^l= z;t E ==-g
Erll
47J= "J=^lzot =E =u* Boltzmann olz| s-narollE Hl4loll"t 6J+ts 19 9"1*4. ol
E_1301 "JolLJqr a4Elrt.
zlf "Jzlt E B+ qqzl= *= +=E Egol+. trl+
=Jg.Et qlHl rl^l
=
> HI8 +EE +s=4 ?"1 448 + fl9 4o14.
^J
0lE40ll^1= 7li{lE E^l#=, E^F=E BE+qq *El
0lt6la. 0l4g 7F{l=61
1B)= HttE Lindemann-Hinshel- u * qTl Mltrzs-rtnr[A] [B]
^l(.EE
wood(E4 l4D rllT[Ll== ¤861.= E{l o]E:dtl. Fzl.4oe
Maxwell-Boltzmann9 Erl'++ EEÎE gE-g AolcHEE
ol 4 9- lse.ra^l+ A3- E+_ rlrlr]l$ r-|$r,+ Ag +4lE g
1B).
g+ 91tr1,.
k,* o(TlM)tt2e-E'tRr
ol ll,
"Jol-B f gg
q--q-l} zJ;o z$zl-E AHI*$ rj4raflez|. ^ldq^l +4= Arrhenius rsA.rb^le-l
9lil" fl^ gF qqzl r,ol HIAE gCp+
"llHzl e+
E g+=
A+B+P u=k,[A][B] (tsA.la)
ag "J + gl+ rEl+ +E "lE+ +qI Hlac9 e.'Je.(i
ol HI*el +E tl-+= Arrhenius trl4 trl-s-+ ¤ol 9s olzl +Hzj"J 4,o14, flql^J E E"JC$ Qld6J 4,"1 *
ql E=+trHEq l4D).
^lql =
g+.
qlqzl saol #q= +=ol4E +E^lE Hll6J
^Jql4
kr= Ae-E"tRr Arrhenius
^l
(15A.1b)
E Ef, zj*6llot qI*"] gq$ + ?l+. ol 'oJzll4 z4'g +
9zlrJ A='zl+ *zI4 oJzf(olJ. E ol qlLlzl'+. +^14 +71 +14^l= ol +E tr.+q+ "Jill oJzt pE Bq +
='¤}csl
Arrhenius zl3 zlxll-tlql^l Ezl¤"] +E=6}1
olo} d4. 4
"l r+Cql^J +
+qI qlqzlE g4l EIE HI*"1 "Jqu+= E'Jg zlzlr { k,* Po(TlM)tt2e-E'tRr (15A.2)
Ep + 9l+. +E EE s-'J4 "I*zlxle o1 E'JE zHC"l
99"t 6[zlu3 7l4l-tr- H]¤¤ b6l-= ¤Bd o -e.<J] -:.Ql-e. oF{ql^l zf,$lal ¤Bd-Azl"J ol !g +E ol$e-tr qtr"q
E 4q+6t+. 5!"J+ Eolq, C+4.J HI* +Eql gs+ ^ll 7171
= ^lr+
_s-ag +4L}lr 9l+.+,
it
ila
15A1 UE¤ gi{t 5z ==
HJE
x.)4
0llLJrl
==
t}*"l "Jq+= ql gs+ E4qL4 s_Ag ^84611 EH
krn
I
l5A.la4l o + +4U k q +6J "JHI4 gE 49 d4l qltr-6J F o(T t M)'tz e-E'tRr
+ ?l+ + HI* $E uE 6E tls"ll ul4ldi"F B 4"14, ul

4^J EzlE B+ 44 ,,n"**(Tt4rt2ql Hl4lts lolcH¤zl
(a)t lilloll^lE #4s.
,! Mg Ae+ BE E ¤t*g eE]+ 4"14). HI3 +E= E6J *ql^l q]1lql utg+ Bol RI-i +E tri{^l h3 Ezl¤e.l +
lsA # olE s8e
E HlEql el=qlq. "Ja Bqq ^lE *z} +ql^J "J¤qI ^l a4e+ +Elu "JzI |9 +E += 2+eE 44421 *zl 9l
A *"Jql "Jq+= (A,B) +=9 fE :z gEE +Ele+ ^lz} 6ll^l+(qlsrJ ,JE."le+ 4.tol* zJ*ols+ a.Eol4a eg
o + 4b 4."1 5E lE Zmol4. zlilltlqlî qI +zl7t oJ s 4"14).
7l- +E. qlE= sg rngl^l oltrl 4lt}+ u[ !lr[(rB.r2a4,
z=ot),"1e{). ol pffi ol+6}H z^Bql +6J 4¤. E¤. + il+.
2s"Ce+ 1.0 bar9 "Jq 4ql q= e4'E 4+, [Nr] =

"JE= LIEhL]l=
=E ^l 40mol m-3oJ ull o=0.43nm2, mN,=28.02ffiuA +98 #
Z=ou,6@ql^J iii4trlEl u,.r= *E tszl-Eel ¤+ ^J44 + "JE7I trl-q=r+ 2.ol ¤4.
Hol4, oE ¤:E tH4 "_=.^J, lB lsA.lql +4U Ble+ e
ol o=ndzol\ d_i@o+dr)o14. ¤=Jol +1(1'!-Sr"ro-" lr-')',(?gg5)
mooJ BzIe| d*ol "'^'"I
Z*,*, = (4.3x10-re n,') x [
nx28.02x(1.661x10-"kg) ]"'
)
msoJ $zl..r.].o19 +Eel a+qE Bf d-tril4 44"1 lB.llb
x(6.022xL0" mol-')2 x (40molm-')'
ll(r;..r= gkTlrylttrol4. ¤ zlrl p - m6msl(mo+,?,Jol+. trl+
= 8.4x103a m-'s-'
,<1 rzflel AEzITl
"J"Jol f
"Js s6oJ BBz[e+ +E=61+ +
Et: ou.ae\rB7l H+. ItI?+^l dill +E gE= ol {E.ollu} A ol A4"ll el6LH +5,JE= q+q =q, ,.,rr: gloll,rJE
EzIg "JuJ"l + "JE nAE *:+ ar+ tY+. + lps(ul7+)
^plql
8x 10163119 +=ol "Jqu+.
Zos= o*rMoNu (15A.3)
+ I9 +bE= [l], r?-lr

t]+E No4l 6]H I9
Avogadro
(b) ollLlrl
"J"J"l + 'JEE s=Neltlt} ¤+. "1. +41= ol+6lH + ê
+4 as ^lg e|l Etr|. # olEql E6IH HI+ql Tlqlq= ,qE HEI-+EE +E
EEql+ +E6J gluJzlE zlzla_ +=ol gqB g¤g EqL
Z^,="(H)" ru11e1n1 =E "JS
lxrrrrl
(15A.4a) 4+ rJtr+.+z}g 44+= # +H4 o4oil d"lBzl +l6}q
+E +H4g + +E +9 ^Jq d= S qlqzl(e)9 E}f
tr +ElLilr" ol d= gF qlqzlz} olp 6t+ # e. ololB ufl
4zl-E ol +E +84 o(e)zl0o + s.lal +=+.+q +¤61
A 4l,zl"J n(e"E HI+q SCEI glHzl E^71 Aq. :7ElE 5A+
olrjlol ?,.roJ Ae+ B
^Jril4 d= +q(¤+ +qol ^loleJ +
d
B
Eql ql6ltrlE rse.3^lql e-l6ll^l eqE Hcl ^-Ezl r+q=+ a
ol E+.
ol o
+ - -o(e)udMoMs (15A.5a)
fA lsA.l g0l7l.= E^1.(A)7|.EE E^l (B)el g-cr.7lalE E^t (A)

el Eq Erl (B)T?|e PtTtot -Lrtrt. 0l
=EE
+ ErlE 4r4 dog:y 6,
ol 49 trl-s_r+ zJol EE" sE zlzla- +4'J +E gl+.
=Col ^l#
# = )u,",\tAltBl
-o(e (1sA.sb)
*E Bs= 7:7181 IE ++ "Jqg zglt_ +4.J +E gl + g"Jole-l ^Jr-ll4 E4l Sql ql6J # ql''lz]rl g-!pu2,,1
oq, ol trll= rsA.aaal9 gr-"E= ll=n/V_p,lRTtr- rlE}Lil oltrt. tr+4^J tr-ql4 +q¤. u,"1-(?sttrr)r/2ol+. 9zlrJ reJ6I]
H E+.E¤i E4¤ +=ql^l= tr_i*oo1q, 15A.4a41 g Ag qlqzl eol t'&61 Hg B9l
^lEql^1g tla d=
of
^lole-l
ol r-l-e-$ ?ol 5|4.
-E EEqq ?19q, II+4^J %}+ +EAL 49 Boltzmann ollH
( r6kT\''' zl +s Bi/(e){l AA^J ¤# 6ll+"lo} *4. 4
nA - | jaI
Zoo=lol wilel'
lEm^
\ ""-A ) "Js. dlAl I e* I
(1sA.4b)
( \,,,rui141' =E
t=e
=ol #
4kT
\frm^ )
I =-xf=l
seo 1s u8=Jqt
¤zl,rJ fle)de$ d=
zlzl e4 e +de
^lolE <I*
"llLl
zl4 *
Eol+. ol ,.l¤. rsA.laal4 ul:zatE +E ^J+z| pol ffi$
99oF ql+.
rct
A
k,=N^l; o?)u,",f (e)de +E 8+ (1sA.7)
w-
"l 4+g+6IelE +E+H49 9lHzl 9=_ng "JoI"t{+
fg 1sA.2 Ael B + E^t7l trE=Eg nllE atrt|4 Etl ollLlxloll rH-d
EE4el E=E= 4ltbl"= rll olEEl= rta[olE]=.
@ ==EEEe.t
oilL1rl el=EJ4l =E
¤zlrJ ^J461= EgE #s- z}]H* AE+# 6J ollE Btl

9lHzlz| HI¤¤ "Jse + 914= 4014.
S.+- 49 9"1t4. EI+^l fl ^l.ll+ a=ao,^** ¤a_s=e,E
EAI 1 HI_&q ol+g= .ilHzle} +E ¤EI Bq+H +-q- j,+ eg ^lol +g+
+ += EzI Ae+ BzI ^Jq 44 u.de| ^Jql e+ ollulzl s=
*=qr 6IzI.+zl¤E +dol 1IEAE 4il-l d "Jql
iyu2,"1* ,^=r(#) ,r*e aEai". =(r-?)o
-qsH -J {el ¤=E=E ce. + 9lzl"J ol +ql= eH +E
4. 4E7l L1+ Tlgqzl ?lE aE 9lg + 9l+ 4+4e Ell s
+E *H4-oe Eh+q +4U
s ^J46Itrl4E ee+ szl AE+$$ 6]|ot HI+ol zlzJ _a4 glHzl_9¤ +E +H43 o,x*E ol+6Lq ^l
o(e)_naz^*gs
'i-, ^"'-- rrlrlr L ;- -zlalrrl ol-.1 zlrd*EOl
H"l= -t- O! O ',rt"i*i,'u':- = 'd'il6-E-= tdZl
i6t ctlr_lZl
r-r 'l f'lîl, nri2?:zH ise.iqiî Eo']r.r ¤¤ EE4 oei ?4.
^Ê
^JE"J$ zlzla_ Hl¤¤ ^J46J 4o14.
ol qlqzl CEe ¤{ 4411,
Ae+ Bel +dg E= Elqql ¤e+
^J'll +q dE u,"r,e_s7t
g+ o(e)= r-
tu
e,1
t o o(e)9 ollt-1x; e15 [e > (1sA.8)
cJAl2 CH+5 +E C+
o(e)91 4oJ olal-J rl3 E_q lsDqlî ¤Eg EzI A
:zH rsR.zql +4U utq ?ol 44 aY + EzI +dq 4=d =E
dE " + A¤+ Hel Dz
Îolel
HI¤¤ zlzlt_ +e6J Ar+e+
zl4"lq, d= + 6CE ol rgql
^l"lel 44r+. Ai4 Et+e+ rril +6J¤+(rH lsA.3).
+qd 7+E E ol+6rH q-q,=4 ae s4l= eg + 9l+.
+E +tszle-l qlqzl e-l= *Al7l olz-lH qcqE +E tr-
cos0= (d2 - o2\1/2/d
+= +B + 91trI.
/rel.A_B = t/..' cos0 = Ur"l

(#)" 0.8
o
X pm 1.95 eV
EI! 3 +Ee+.lltlzl ^lolE +41

u 0.6
q,
H
o
E B4l qlqzlb e =ipu?aol4. +Al z9 p45 ols-"alol ol x
0.4 1.0 101 pm2, 0.90 eV
+ "&3 ¤A^lzlfl ule-=4 ee +41= eg + 9l+. 0,2
urel,A-B= t/rel cos 0 cos2o= (d_ a2)/d,

0
¤ 0 5 10 15
ele
te-s = i truI", ,A_B = i lt(u,,,cos g)' =; pul,,cos2 0=¤ (++) ral 1sA.3 1sA.8^l= 7l^la- Ll'El',-.! HJ38 EE4el ollLl^loll ntE EEI-.
E=g H+Dr-+HD+D BJSoll EII-LI dC Tsukiyama et al., J.
tr,J4l4 =rEl'.(K.
"llHzl Eq t} Chem. Phys. M, 1934 (1986)).
azl rtzl\lql q4 AE+S9 Hd qqzl= A^ql+. ^JC
Eol "JEqzlE ql Eq glHzl s.z| pe6l-r+! 4* azl a
rllxl a**E 7l^14 olE+ El t+ aglrl= q}*ol gqg +
lsA # 0l= 5e1
y2
k, = oNo
8kT
e-r./R?' +E 8+ [== olE] (15A.9)
rsA.8^l o + gg +E +E4el {luJzl-9¤ +41= "l+61-H

"1,
rse.zzl9 4+g al4}g + fltrl.

E4! 1 i\daxvdt_Boltzmann +s^lg "l+q^J 44$/(e)de^l
ol gE 9=E7l 7l+ *zI4 "Jz}el E
^lql^J ^l+El+E
6J gE 9¤(xllE-*) a4-5 oJE6}E_E ol 4g Arrhenius 4l
Eq lBE lB.4^lql^J M/R r+lCql tttk3 Bq+E t44 EzI
g+. ,rl4rJ
+qql *t Ee4g Eg + 9l+ ., k,-/gElR'e+ eg
ql gsa} ali ¤+ =ol =+Carl
ollulzl E HI+
= zl+
"llHzl(d*d tr-ql^19)4 ?gq,
*zI4 .Jz}(teltBl= ++ +)= Tlill +ql^JE +E Hlsz}
f (u *t)du,", = +n(#)"
pul' Iz kr
Lt2",e- du,,,
g+E ag "J + 9l+
{g s-!Fu2,,t! +Zl= ol+6}q tF44 Btl 9l'J z1==_ zl ol k,g 4lt6l"= rI+ A++ rl$g Hl-Hl+^d +s$ zlzl
"l
zlr +EB + ?14. 2,.,= (2elp)tt2ole-e- du,,1-i(211t)tt2{1t2 de r e4+(qlE^l dcE +a "JE o +) E.= +zl tlzlE El
-det(2pe)'nol S4. olag Bq+H 919 Eelol r-]-o=$ p olrl s ++q Eg o&9 0l+61= Lol4. Ae+ BE ?=
g+. +E4g oeel or4l alH es +H4g 3rI4 = o+o
"l =TEd2
"l E+. ¤zlrl d_+(d^+ds)o14.=,

f (, *,)du,., = +n(
#)" (T)"' # -
o=*(o'l'+o'l')'
= r"(#),,,,,,,,_,, u,
de
zltrJEt q 1sA2
f(e)de
628Kql^J HI* Hr+CrHn+CrH6oll EllEl +E tr-+E q

tr,J/llz 4+ 4l4L
tr+{^l *4zl +6110}.J 4$ol trl+$ ?ol E4 E +I +I4I e=J pE 4l&++. tE+ 4l4}g 6IH
It-3.123x10-22 kgol +g+. u|4r1,
(2t/ tt)'/2
fr f etar=rn(#)";"rrl( T)" *r l2
-(.
Eu2e-'¤kldt: ( '1"'
J-o(e) _ f 8x(r.381x19-z: J6-r )x(628K) ) =2.65-..kms-'
[r/rr
-tt sr7.l)"'rl.-/rrr )l,t"t'1"-si*rdt
_(
.1
g lB.tql E6|H o (Hz) =0.27 nm2 -Lr-l-tr o (crHn) =

0.64nm2olE + ¤+ += +849 o (H2,C2H4) -0.44r:rlrt2
+HE 4Eg lsA.8^lel o(e)g ole"ol.{ q-q=r+ ?ol *B ol+. ol HI¤:el gd+ qlHzlE 180kJ mol-,ol4 trI4^J
+ el+.
2
k, = (4.4x10-re m )x $.022x1 023 mol-' )x(2.65 .. . x I 03 m s-' )
o(e) = (1-e./e) o; ¤ < EaB ttll o= 0
, mol-t
y(g.lus]K-r mol-r )x(628K )
Xe-(l.80xt0s
J-eo(e )e-ttkr d¤ -o l;'('-?)'-''*'de A
=7.05...x108 m'mol-'s-I xe-3.s" =7.5x10-7 m'mol-' s-'

X{EF) 4Ee.t
kr kr 1, 7.5x10-4dm3 mol-l s-' ol4.

r e- ¤t
de - t
ll^r-,,,, dr ] = (kT ), o
=
" { [ ^
e-'^t
tr+4^l
(c) gi{14 zsA

!* o@)u,",f
(e)de="(#)'''
"-"'r'
E lsA.lg += dE er+E+El +a} += +H4 ql"lEl=
Ell 3
+E t}+ql ++ 4+4 ol+6101 4l4I6J zl+ g-z}4 .Jzl9 {t9 errnenius E^ls+
E"=Ner.ols + e^lkT=E^lRTol+. ol=¤ Botfts +lql^l + El Ee <i4 ul:zal aol+. 01¤! + Hl+ql ql6llî= olEzl
6J 4+4 l5A.z3l o ++q trI+r+ Ag Arl-= gg + gltrI. e+ ¤Eil7I
^J'Jq A *zl"J 4"lzl HI¤¤ql 4"I^J= =
5e2 u8=E-ler'
E 1sA.1 Tlill+f USoll EllEI Arrhenius trtzlolE1x

+lol^l Ll'ZJ UBE
A/(dm3mol-tst) E"i(kJmol-t) P E^l
d¤ olE
2NOCI -+ 9.4 x loe 5.9 x l0t0 t02 0.16
I
H,\IE
oo=
2NO +2Cl
aot o./
2ClO -+ Cl2 + 02 6.3 x 107 2.5 x 10ro 0 z.s x to-3
-.lol /
H, + CrHn + CrFL 1.24 x L06 7.4 x l0rr 180 tzxrc4 a
'
K + Br, -+ KBr + Br 1.0 x 1012 2.1 x 10rr 0 4.8 r.g 1sA.4 EE4e'JoPl.= E^l'= Ef,al flZl'J 61.= E4 'Jolq,
HJSd .JE4e=E EJ- gq+Zl 61.= E4 'Joltrl.
* zle. ¤q trl "*9 alEol ++qq il4 =E^loll
il-olE+Elflr 9l+. "J+ a+ql= ¤eil7} 4ltlilB+ q ^l=

g"JolE"l d*gR4z} gq 44zly Hl_HI+c +=q
4 z}*f o}4ol+. "la3 ++qL 9lHzl9 6=0l Hl+q q] d= 44ql Hl6ll^J HI¤¤ "Jszlb 4= 44zl tt$6l z
tl Aal 7l+ol ¤ + Hsq +=61+ s+++Eel l}44 u]] 4. ol49 ol t}*ol at.s ollTlL|=ql E6H^J "J"l4zl rllEol
"JzIzI E+ ll4q"loh.Jg
6J4 Ag += g'"^16J.= 1"14. 4-n rll46J+. olElq} ¤.B{} Ea3 Kzl Br, Ezlql d=6i
+"J olq4 ol E +e] + HI¤¤ 69. olge_e. ql+q= a q E rFI9 A4zl +E6l zlll])zlH dzH4I¤-)zI rEP
E+E q zlf *zt4 oJzl¤ *Erll, olag EzLSol +E Q Br,-tr g"IzI+= HI¤- E¤ql^l +g 1"14. "le4l qH
= q uulE.zll
6l+ aH+E_ Hlg" 6l-= AilH _H.ol7ll alE 4"14. + +^J Ezlzl E+ olEol¤-e_s 4l
Îolql 4TJ2]|4 "J
4e+ olF ^tolel olBleI il¤_+e_o6t7l +l6ll^j gi{l ?lr} 4ol z}*6lrll ¤+. ol "Jqg zlgql Bfl ¤ql+ Hl+6J +
P= E"J6Ia olA4 +E +E4rlE +9 UA¤ EE4 o ll4. "l "J4"e + olgol d=6}rll qq HI+ol gq+^l
E sa=4. a d -potr- EaE4(lB rse.+). rqE +E ^J+ KBr+Brol sZl+ e+ 4g trllEql HI* +H401 ral tsq
z| rl-o-=4 ?ol ¤4. += dolq, +5 *H4g K+Br, ÎolE ++qI ?lAl4 a+
q rllql Ake_E +l6IH HI+ +E7l aAl$^Bzl!= 4+rl
k =poNo (#)" e'E^tRr (1sA.1o) B+.
ol !g + ql++ A+ ,JZ Eol+. gHI4 o e

rsR.zal o
ill oJzl+ rB+ qq zI*.+ *8
=zlE 4=+
"J
GZEU sitterrler +B
qlqzl H"tl^l rflzltr-*El Br, Ezl.E 43alzl dAl Hq
ztElEt q 15A3 Hg + 9l= 4?-l= 4l4lElq P,tAl 4Ig ,ll7Iq=q^JE P
<lg +6lq+. H}¤¤-=(+¤ol+:z ^J4L6J+)E HI^lEel
628Kqlî *8 4¤l xlf *zl4 tzl.
Hr+CrHn+CrHuql
aJ9 aoopmol4.
e_l ¤ql zlY r.z+xrddm3 mol-r s-,o14. ZI+d ql tsA.2ql
^J
Al&+ aq+ A=7.05...x19tt{,rr mol-r s-'o.l4. tr}4^J a.E{cl /.tEI *d
dxl- 4C r+Brr-+K++Br19l +4q
ol ++ql q+ Eill q-s_r+ ?ol 84. E= tlE {luJzlE got$trl. "l 4Cql 4fl "l "11
L+
"Jxl-b =
qzl= 4l Ttzl TlqE ol+qzlbEll, :z+ 6l-+= rflz}9
A:*p.,i-.n,l
p- 1.24xl069m3mol-ts-t .
- 7.O5...xl0lldm'mol-'s-'
A.rl.,,rrt"d =l.gxl0{ olgE+ qlqzl rol+.E qE Br29 dzl tls+g E.ol4. :
4r rjlrll 7lq= ole+ eol BCg + olg =+ Îol9 ^J
p9 <tol ollfl
z+r g^dEI qlqzlzl $z]1 trIEql Hl E4L+ "llHzl4. ol + olg R.J trllE ol ^J
"l ^lolE A4zl
¤¤ 4¤6J +E_tr 4lB^l7lqH +'HE alot d4. g+ Ezt+ qlqzl} -&t+negol4. "l ,t'll zlqel .Jol oj9-tr-
4 o + Ezl-Eol +*g++p9 <l"l 4L.I{+. +E] +9 <}e_E Hg trll(+ "l +ol 0"J ql), dzlzl +19
Hrll g+.
4El Rql^l 1$zlzl olda}H dE qlqzl Hslz} 4
"Jill qlzlE eets + 9t= HI+9 + ql= K+Br,--> =ol
KBr+Brol4, "l El+ql ql+ pE deil= 4.solr+. ol Hl+ql
94 *ol ¤+.
1sA # olE s93
E=r-E* #- {<
0.
G 5
Rol q¤ "J4l 7l R,-e+ A4l 9H ol 9lHzlE ool ¤4(-z -:.0.6
.Y
10
el-r R*-H+ zlg <k* zl4 ull= gsE ¤+). <F
to o.a
It
{r
-#F
o2) 0. 2
o=r-Eo Ht+q 4B R*-
ddI_EJ
0
0 10 20 30 40 50
+ + r1"l9 A4zl ol <i"l g trll, 4¤ol Ke+El Br,-E_ 8EH4 o1lL1^1, E/E.
Botz}{, EI+^l HI+ +843 6* =rR*2ol E+. + +B fal lsA.s 1sA.l1aloe +ol^l= +E ar+el ollLl^l el= BzlE 37Hel
(714) HI¤+=E elzlE9 *9 A=R(K)+R(Brz)4r B srJE TlxE LtElL.! rA.
oll ul-Hlg" C +5 +H4!- nd2ol4. oe+ del + #e--E
+q "Jill "Jzl¤ trl-.q=i,+ Bol 44'J + qg Aol+. ol qlqzl:-:z +zl-el E= e
ql +E+ qlqxlE 4rJ4s
,' 5 "J^lq ¤! EeElq, ol qlqzlz| $ziE tI 54 9lil(ql
- o - nd' _l
to_o*_7tR*2 -l+neod(I-E*)J
I
aql 6J a6J)ql gqSqe uI"J t}*ol "Jqg + 9tr+= a
^}^ll+ 4* rz=
olQ. z]-,r]l-J ¤Eg ol :tzllel fl,tlo1=E
¤zlrJ I-420k1mol-'(0.7alql 6l]BtJ4), E" =250k1 mol-'
_H_oI+.Ezl^= ¤-]="*szl]9 a+ {E4¤E ol+qrq il+r
(0.a2 al9l 6ilRql+), r4r d- olpmolH P=a.271 4+ zf{a}zluj ol olE9 +g AEC $Cs} flzl e.zl
olag deil(4.8)e+ EllillE g "*= 4,o14.
trll, ^jCE_e
a}4q= lBz}.5a Hl¤- +E tI+= q-q=r+ ?3 Kassel
^.!9-
xPl 87[ 15A"1 Nae] cl, .r.[o1c.] zr$ qlTtq= H]*ql E LIE}B + gltrl-= 4,o14.
trll+ p{}g +6Iq+. d=350pm, :l-ql E*=230klmol-t9
s-l
fl6}q+. ko(E; =
E*\
t-z) kb E > E- "J trll g+
1+^l_E HJB 4s (1sA.l1)
lrGsset +]l
z'2,&
9zlrJ kb= 949 Lindemann-Hinshelwood olEql^J ol+g

gCsl +eille-l B6ll +E t].+ol:r, E',= + e6-Jol #qzl7l
!-71 lsA.lg Eill .Jzl"ll ++ + TIzl +qu+. a4il +l5Hî 7l4oY 6l+ 4la6JE qlLJzl+.
E "J+ A+ql= "Jrll "Jz}el +zlE +eoJ =eg+ 9lsq, ,'l-4 tsA.ll^l_o + f9zlts +E ^J+fl qlqzl fl= Jg ¤4 s
,tl oJill "Jzl9 Tll$g {l-d ¤e$.r+r E + S+. E4l 5a <Iql qldl^J rH tse.sql +41|]8.4. "l ^lg trls=$ ?ol ;]]
g a+ +e4olzlql .ll++E HI¤j==g K+Brr-H-r{ ¤d ul 4g+ el+.
+d-6}q, r?]6lq p= r4zl drll +* + s+= 4o14.
+q{ 5g. qlqzloll.{E
=-E +E ^J+71q
sz}
ar"l-zlts ag ¤- f ?ltsrll, olag sz[ rfl $s
15A.2 RRK E.'J "llHzlzl- = +zlel EE 4lE"zl-= F6ll^J "JAl %r.
+ olf6F=ql aflb rlt"l El Aqxlzl ull
Lindemann-Hinshelwood {lzl-t169-ts fl#fl 44 zJZ zl ^le {r-
-
Eol+. 'lo
zll-^J l+zlE +*(Eq l4F)ql ql6]l^l= Rice-Ramsperser- Rr
Ezl rll+61 4zlfl go. oJE 6}0l l_tr d=6}q, ,lol
il
lGssel Etrg(RRK 5.'J)¤. 0l+6}0l oJal oJzI p= 41416ll
kb(E)71 qlqzle+ +zL L}] +l$zl +ql ++61]TI+
nlru
ol erjg
î +dts + 9ltrl le26Hql o. K. Riceel H. c. oltrll= o{Hzlz} 5=$6}zl ,ll$ql $ll zzlql +
Ramsperger, -a4-L 4el F^lql L.S. Kasselol t-ll+$ A99 4l$ol {lHzlTl "J!l %L^lql +HlE *olzll 9E
^J
+ql 9aH^l r]-E:qegq, r?-1610l olag
R.A. Marcus"jl
4o14.
'RRKM ep'olr-p qL+. ol eriel 7lt 5e¤- Ezlz} tI*
5e4 ls Ei8=Jer
=9-d7]lLJ=
I t. oEql^l= ¤:E HIE oJ4l "JzL r4r +
HI¤- +._Ezl D 3. g¤El ollLlrl= el* Ez]¤ol {-e. d=6J trI Hi¤¤ "Je
=E zlzl 9la[,r.1 7l4o! q+:alatE t]q4 qlHxl4.
6CCql ¤611^1 4i6.J E"E gE {lHzlE zlzlt_
o3-u3olzl.
+E.61"= +¤.q ulfllaf,Ql ^J46Jr+. a 4. gi{l 9.!r}= c*4"J +Eql gs+ El]o}g rB16ll+= 4¤
a 2. f; "JE= "JA-J ^lE ¤qql^l gA6J ^lrJ E.Jql gq "JzI4.
+= +rE=+E r gqg +i,le+ t'lzf, zf,lo e +5- <iol4. tr s. $¤El BÎE E6|| +E ^J+= RRK Etrgg "l+61-q +e
e}+ il4.
=sEj^l=
,^-l7l
oe, --1
I
+4 al Hg
iE E ,t3-olal
6= E.I
=+ Z N = 6 (8kT / 7rp )"'] Ni [A] [B] E^l¤, KMr(gz| ¤+E) l5A.4a
o9 .llHzl 9= o(e)= (l-e
^le)o
e2l^,olqEo=o 15A.8
+E ^J+ k. =PoNn (8 kT I np)tt2 g-

E^t Rr
KMT +E OIE 154.r0
r+zls. +E ^J+ ko(E;= (l-E*/E)'-'kb RRK ol$ (E>E-) 15A.l l
E4 158 EJtl_^lHt| U3
(a) UBel
> 0l E4E Hll+,ts ol8 =+
rll?Eel s|+ HJ- EE +0il^1 gqqq, el+= E^161 016ll +t'-+ +ill4 r+Ae ++6J "llrlq+$ ^J4I6I"] A+fl +E
6E1E olEE HJ8 !E 0l= +E= olEXl
^_E= +101 ^|H|l6lq
Etrl^le + fl=xl= 016l|6l= aol +E= trl-s4 rJol e9+ B! zqz+oll +6H^J tz|+r. 7IA++.
=s6ttl.
> 6_4fl TllLJ A+B+AB u=ka[A][B]
EE +oll^l golLl= trltrf ElSel +Ets HJEE=e-l E+tt +Ee.l
HJZLI SdEg trJEts Ezle] 0il11^lsl rlul|= E ¤E6t4l.zlr} ka(Ezl d= q4}g *q|+)= Ae+ Bel q.&
^lHH= =l.del
Ceql el6ll^J Ae¤+ ^J+EltI$ HI¤¤ "Jezlzl ?+g i]|
H l-r--r l.
EL-I.
e 34zl|+ HI¤¤ "Je4^l ^JCE PE g + 9l+ ol +

> -Jg-d qlHl rl^l
0l E4oll^1= 8+-8EH 14E)= 0lE6l.-L, Fick9
4*zl s.+ +Î-rzl. q!f,-ol+r 7Ie6|E(+o11zL ar¤= 6J
qtl =^|H(EE
tH.I(.tr.E 13C)g oJE6lXl Etl. Stokes-Einstein BZIÎ fE 91_o ee) olag r+q,=4 ?"1 448 + ?l+
(Erl t3C)E oJE6l-Zl Etl..
AB+A+B u=kllABl
AB-+P u=k,[AB]
ol ABel LoEEd+ ^J'H= 7la6}q q=q_4 ?3 ee9 ds

L" E HsI
8E +ql^J 'Jq+= HI¤+ TlAl +ql^J "Jq+= Hlg"r+ S +EE +4Ll]= ^l o E+El +e. + 9l+.
d6l 4q4.Ezl-=ol +t +ql^l ETldlol +E=61.= 4,ol oI
q+, qsl6|zlu3 gzl"J += gl= +iil +a +ql^J Eztel E+8E]l
+^l7l nl"Jej^l qlL1"h al-b 4,"14.

# = kalAl tBl -/c; [AB] -k"[AB] 0
ol 49 EH
15B.1 Ee4 +oll^lel u3
/c,r[A][B]
Ien1=
+qI +q^Je-l HI+ EzE9 dl+g Tlill +ql^l "Jq+= a k^+ki
4 dq d¤"] +qq *d *,}| 4"ll 5o}9l= HI+ E^l¤
E tr-+g Tlill +ql^JB+ Hlsz]. ql+61 *4. :44 tszI rq6lq ^J¤Eel ^Jc +E= r-}g=4 ?ol ¤4.
E"l zll zl-4= !!.= +E_E. trl]+61 y47l trIEql "J+ + HI k^ko
g Ezlzt ,r1e "Jutg zlillql^-l -Br+ s*Fql EqEq glrll # =ttoBl=k,[A][B] k,
k^+ki
(1s8.1)
¤4. "ls+ ?ol eL +^l7l *o]| E{¤el 471444 ql$ql +

Ezl +Hql "l$rll q= ¤^Jg HFLI E1plr aJ4. olB ol ++4"J a+= t4}e. + *+. "J"J ^J
-F
= ^ldql^l=
4l "J* 83 ilg ElHg uI= EI¤¤ "JezlTlql 6E* B,* xtol rqlE 34zl} Aszl *¤¤e != +Etr-+
=rt ql+61 Lg q= k;tABl <k^[AB]olq(tABl= tr-41^l7lH
"ilHzlE *xl *9ItrJ+E r Î"lql HI*ql Es+ +E+
ql
HzlE +4$ + 9l+. +.1 +ql^.1 tI*"] "JqB q= tr-H" o-J k; <k ), r?-l6lq +E +E *izl trl"gr+ Bol ¤c1.
{tol Su}]E EElAI"lzl trll$ql Hl* +z}e+ *,]| E{¤g +
zl4 d+ dill$ {lHzlE r.flafifzl ?+eE ?] qq, q-+^J Or=+ k,l +tl-^lHt| +-sf (15B.2a)
HI+E $Csl.llHzlzi zlzllollr.lE+ gd q +d-6i+

olBl6.J EJtt-rlu1 +:dql^J= HI* +EzI HI¤+E"I *oI] 4
-otr +4Iq= +Eql E6H^l AC¤+. 44*Eol eq}g rI
se6 1s uSEg-+
E 1s8.1 EE +0ll^lol 7[-E0tl E"-H UEEoll E|lE] Arrhenius trtz]

"J 6IE r +Eg E" 46lE urz| f,$alrli 4"14. "143 n
EIEl EzlE R.ql EB6J ollzlzlE S."lzl,.l ?*71 ullEol4. rall
/Bel ++l= tE/^lA"l otul+ Ee=&^ltol4=
+rll A/(dm3mol-ts-t) E"/(kJmol-t) ^tdg 4l
(cH3)1ccl g 7.1 x 1016 100
+ Ed6llot ++.
q+s 3.0 x 10'3 Lt2 cJAl 2 +"{g LoE tBlE ol+4^J 4Eql 4E r"E
1.4 x lOa 45 'il=*
=.e.-tr".E.E
ql+g 4.3 x
HEI¤ +4{=
CH.,CH,Br 10" 90 ^l
Al ++6171 +l6]|^J= +l ^lql^l ldlBl(r)/drol "JC6flol
uBTl
++ r?]6}q r>R*ol7l"J 6lE [B](r)=al blrol r{4o] ++.
$^de+ "llHzlz} tr]]*61 +e_EE 44*ol4 flzl¤9 x]| rqH dlBl(r)/dr=-btPol qJ. fdlB)(r)tdr=-brl E+. ^J+
= r qlFEol bE #3 r-+ """J trll tBl(dol qle} t:E [B]7] g+=
eEr HI¤_==g t}*o14. es+p HI*
g.&_zluH ae+
^[¤
"Jq+= ql qlqzlTl g,qts q= -g olSe}+. rq6}4 o=[B]71- EljE tr]4^l [B](r)= lBl+btrol
"l ^J'J6J $Ca+
=¤sl_
xfu|f uJlol "Jqtq. olull= k,tABl <kj[en]0lq(= k^<k;), g+. E r=R*oll,tJE. [B](r)=oolq, r?-l6tq b=-[B]R.zl- ¤
#s 4s- *izl ++4 ?ol S4. tr}.
=,
k^ko / R,,)
k,=
k;
--k^F gd+-^lul.l +El (1sB.2b) lBl(r)=tBl[r- , )
ol q+
tBl(d4 44 E= +41=:zH rsB.l.il +4.11fl
9zlrl kotk;-y1r"olq(Eq t4c), Kt: A+B+ABql q6J ¤ ^lql
+. tBxr)E 481.il +6J lil. EEI++ [B]R./lol+.trt+^J,
B tr-+q.ol laJoll,l}^J+{t"1 ffl .$r|]e$el qlqzlE
goi+461+ +E_q ,rl+ HI*"I {qq}+ "J+ ¤e ql"lEl
dlBlD/dr = IB)RYP
E-E lsB.lql +E5ll +gl+
ue=4Tlr2Drry 4nR*DoIB]
(o) *ttal HJB

EI! 3 HI-SE d4l4 +E
qr}-zlut] HI*E +E= HI+ +zl¤ol +r4l q&q. +E. HI¤- +E= +444H uuoil4 +a4+E A+z}q +E #6I
LEJ6I:Z AIÎ6J + 9ttr1.
+qot 6J+. Ael r4u3 *szl [A]olH +yl yel +.q +ql .
qfl= Ae4E fE lvolelvol+. q+^J HI;- +E(Ee=&
;l{ee 44dlz} trl-g-4 ?ol 94.
8E +ql^J EzI ee+ B7l- d=61-q tlszl 44zl R* ?Iql E HI*+E = urNo[A)V = 4uR*DBNA[A] [B]Y
olzl-E E q}*ol gq+q HI+ +E= EzI e4 B7I q
^JE
4}q= r+cql^J "J+b +Eql e_l6l]^l zlullsc|_L ^J46IZI. A$2f=ol d+ {zla}r. gl4a ^J46J += Ssq, rl4rl
Hl+ol gq+E A=ilE 89 :-oEzI e^'6}q BEZIE r-oE
zlgzlzl ^Jaq ol +E zlSzl trIEql A+e_tr BE q4l+
*ol ^Jzl4, ql*ol "Jq+= Eqlql= ol #*"1 "JC+ at
(tr-+)g f,zlp 4,o14. 0.8 +- --F
o
EAI 1 A ++lel +B Etrg E"r+61+ BBztel +E co
Iou
A= o}6l+ BBzlel (E-)+=Jg h4a 6tE, A EzI +Cq HI CO R*
zl=ol roltr EE4ol +nlol +Eg E"46Ib Be4g +E ui o.a

Io
(++l Ee%h)= trl-q=r+ ?ol ¤4.
^lt'J. 0.2
Ficke.lllllgfl 0
d[B](r) 0 2 46 8 10
us=47112 I ,,= 4tlr z uB
r-,, uJIl$, r/P"
dr
fa 1s8.1 E^l B7l E-4 +oll,(1 trl-= HJ8 Exl-_58o_e +tElq zal R*oll
gzl4 f E6l]ot 6J +s-6J de. +Hq tlzlEol R.Hrf =zl s'JiIE n]l EJ- goTl= e+oll rtl-d .l-E uerJ.
1sB EJ.AJ_rlull U3 5e7
+/J 4l+ DrE + +E +& 4l+el oJ D-Dr+DrE Hl^#q E ^J+= tr|.q=4 ?"1 5}4.
+qot el+. r4r HI¤: +E_E :-" 5,r^l{9-tr +E}4= aol
¤rl6l-E-e- +l "JHg ys ++q ,
o
8x(8.3145JK-rmol-')x(298K)
m' mol-' s -'
^19 =q.rqB, K,=-
3 x (3.26x10* *--ff
= 2'0 xl 07
kd
ol 4hlql^JE rJ=1L* m2 s-29 +!lE ole" 6|flQ. ol49 z.o

u= 4nR*DNo tAltBl
x t0r0dm3 mol-l s-t91 6llR6Jtrl. l.3x 10r0dm3 dEilb
u|4^l q-t}_zlul] HI¤-E +E trt¤-r+ g+ mol-l s-,oJrll, ol 4l4}ql^l Ell+61
^J+= g *. a4+.
^F8-6J =^l-= ^84618
ko = 4ruR*DNe ef&-^lu|.| HJB9 +E d+ (1sB.3)
158.2 EE-EE
zEtEt q 1s8.1
Î
"*e slqL Hl*ql^l HI¤¤E qtlol 4t6l +,qq} qgg +
R"el
=zl aE= 10-10m(100pm)ola E+ql^J +E+= +. qlE^J 4tr+ +eE &^zl ++qq Solz}* 4C"l*
ql ql+ D! zzl eE= t0-em2 $'ol+. trI4^J lsB.:^lql
tr14 trl+4 ee <tg Eg + 9t+. zlzllzl +o}] 4e f,$f1 + 9l+. +tI4'|]
4eE q-4IElE
+E 6I= Exl-=ol HI*6].= A+ qtrlql 4ltl¤- 6llot 6l-=zl
.JHI+g q&4(tr.q rrc)g 0l+6}0l asltr-zl-q 6J+
ka= 4n x(I0-torn) x (10-e6zs-r) x (6.022 x 1023mol-t)
=-
= 8 x lOsm3mol-ls-t
ol <ie- 10edm3 mol-l r'e]. ,JI:+.Ir|4^J eI*"] Er-+_zlul]

(a) #lEt
HI+ol qEJH +E tL+4 =_21 4E7l ol {Ez} 9"1"t HI+ +rl(E= ^Jill ^llE) +q 49 +q s_Ê .<j4tallez}.
++. I$zlzl q&r+ ql+ql el6H^J ol ¤9oe. dg- +
=qs=
of{ +gl} tol 448
"J +E= Eq l3cE t3c.e^lg
ole"
+ el+.
+^ll qql4 tlzlE RoeI RB6I_lL +fl^l 4+Y Stokes- atll _ D'[l] alll
Einstein +414(EB trC9 t3c.4b^1, Dt=kTl6n4Ry)S lsB.3 dt -" 6*"_,, dx
I.., q1t
^l
(1sB.s)
Bq=4. ol +41= 4,olo + Rn=Rs-]R,t4r

^lql =^t4oJ {zlrl uE 19 Ul= .JE}49.e +lile+
4+ EEE +Er.,
Fri4s rJ "lt9 ezlzl4E EqTLzl ?*e4, rq6}ol + el=++. 6J¤ s+q} HI*ql E6J g.r-"E9 da Hol¤
94 ?"1 +EI'g + 9l+. ^lzlql
*t7l +Î-liI ++ql E6H^J +'l$r+r d4ts a+ +gr+
,Ka=SRT qd-^tHtl BJ8 +E g+ (1s8.4)
Eol 44.g + 9l+
3n
("1 n3 zlzll Ell= +4i tL+714 #= -k'lt)

^l+E ^J++). HlzlE"l =
olzlzli 6Izl"J HI+C +E HlzlEol ,gd trl 4,<J ojujol!-
go+ "lzlH qlzlE="l * qe}^j lel dzll4.J }-E H01gg q-q=r+ ?"1 448 + 9l't.
ol 6;u3 olf,ollE.<-le_
"J4zll
4q= 4"14. olBl* +^l aaql^J. +E t}+rl H}gql + Eng Esoll rfl+oil u30ll
q6l+ +el Aillql'- 5.$ap +,]]e-l gEe+ dCql* el=
TlEEl= 7l?.!El= 7l?.!El=
49
EE}
6}rll q= 4o14.
I
aulrl) ^ a'Ul
z]trJEt o{l 1s8.2
dt
^ dx'
-
-,#-m Etr-E-d^l (1s8.6)
298Kqlî= d1ti9 d{Ez} 0.326cp(1p= l0-1kg m-' s')

r
olq, ol +rI +ql,q a q flxlz} zl]a*d-= HI+q + ol
^lg
Etr_ilB^lol+r qI+ HI* +E *#zl trI= Ul
=
zl-tsulE +EE +iR 4"14. rfl+ q& tr-+71 Z ql= f
s98 1s HJ8EeJtrl
7l o1 gq oJe-E gfl .qe+^J ol EoE eA= E6:6|]= 4 g LJq=+.

ol+. lq} gr+= +4.-ll= ql+ 6Jg u9 PqeI *E- zl&zl ^lql
EUI/dx9l ,rl4 Eeg ol ¤9 "Js-s ¤qEol4+ +sE +
qg + 9tr}.
[l]*(x,r)=ffi;
rqH r+s se+ ?a 4r]¤ Eg + 9l+.
(b)Etr_Efl^l$ 6fl
lll./(moldm') 4 q r"il,<l
ol Ee-+¤ zr| ¤ul+ "JA^leE.^.1 9tl4_"e r 6I
^lg t lmm 5mm lcm
+6Y7l7l 4a dzl 9*4 .ll+ ¤.s"l S.= a+(r
= 6}zl =E+ 6}l= 100 s 3.72 0 0
Hlg ?t= HI+ 8zl9lrJ4 ee)= ^J46}]_H_H "l 1000s r.96 0.45 0.00s
qBrll ¤qoF Bzl qs aE rJg 619 + flg aolq. 10000s 0.46 0.40 0.25
#='#-k,rrl (1s 8.7)
olilH Hlr4 a*EL ETlel a+qlE 611= +6171 e= E

*s"_"1 fig 6ll. [l](x,r)41 a]H
tril(+ k.=ooJ ql) ol
e +Balol *sq, sd6J Ee tB4q 5]]^16l]= +E. +
^le-l
tI*"I 9lg trll(/c.>0)E 6ll Ul.(x, 0= +-q-4 ?ol 84. 9l= a++ qq 5E6J 4 ? Sol4 HI* 8zl9 ¤41+ ^llE
.llE HI+ +E.Eql ++ tril++e-l al4l ¤+ql^J= +71 4l.t]
Il]
-(x,r) = (x,r)e-t,t HJB0I gcl-J nllel qC (158.8)
H o + 5ll. +6Ir. flsq, qaE]] l}* *zlel eolol ga1
[ J]
**"1 +t} *c^lel 6l]= Eq l3cql^J oltrl ¤H

$.¤- "llel 4+(+._4ql 4oJ 4Al z?Jql g6"t-9 rl¤¤ol H"J
qI HI 91trl.. . a7lql nJVeT}] Ezl9 601 Hol AoJ H +lql =+) ql+ z}^llq} 6l]=
"}]el ae dzllzl"J H}+4lql
alzll E-s*g
+q{+. ^JB6l flr| Er 9l+.
El4 9l= Alql ql6J 6||= trl-$- o +
^l
llDt
floe -*t
ll)G,t) - A(nDt)tt2 (1s8.9)
ol 49 fl9 e-tr+q :z
rse.s^lql Bq aHVl a7l -trH:o Dt = 0.05
+lE +.1 +e_E q41qq g4zlrJ HI¤¤ "Jea qlE rE
=
bE= +g + 9l+(rH rsB.2). Lri
-tlo
oI = 0.10
olrx
010
#rEt oll 158.3 l.J
EHlqol 5.0cm2oJ gE¤ *zl Htqlql r.og9 _sg_E

(3.emmol9 Ir)= BI r +l= d14}(D*4.ry 1s-r-zr-t) EoE+Ejel zltl, x
etr illfl4. s-s=rt qÎql ¤-4zlHd 4s trfzl fal 1s8.2 +tt uJBZI(q|AEH Ee4 T|$)oll^1 -d HJ$E01 A7loil= x=0oJ
k,=4.0x10-ss 'oJ +^| 1^l HI¤¤ gg{1+. ol {i# + 91= nllel 5E u+oJ. u30l gclLl^l ?J= nfl(al^4$ts EiE. u+"J01
lg 13c.ssl-,Jol'ctr|.
=oll
=s-d7t|EE
tr r. H]* Exlz} ++lE Soll Ezl¤E 4il44H q+ql +E tr 3. g$El-xlHll UBE +E= tI* Ezplol ?e6J "llHzlE +
tI* EzI ++lq e4 "lErll q= ¤tlg HFLI Erlzlr 45I= 4=91 96l^1 3l+¤+.
qFl. a 4. EE ilE^le HI¤+=E dillzJ?l LoE Eel-g¤ q& ql
a 2. qt!-rEt| UBE +E= +"] +ql^l tI8 Ezl-=ol ,tJtr trJ +, falr. HI+E 4E s"4 ¤+^laq.
;|3 g=oil 96fl^1 3l+g+.
1sB =Jt!_xlHH u3 599
=s-d^l=
,\lzl
oe, ,^l
--1 +^l al Ha
${l-zlu[ aof, kr=ka tl++Eu=kalAllBl l5B.2a
$dE]-zlufl +oJ k, = k^(Klf) AB+A+Bql 46ll^1, k"E ABE Eqlql Ell6llî 1sB.2b
q.t}-zlul] +E ^J+ ka = 4nR*DNe D=Dn*Ds 15B.3
ka= &RTl3n Stokes-Einstein +41= 7IC r58.4
Ee-+¤ ^l d1ltat = NllUdf -udliltdx - k,til q{lr+ Eflft li1 HI3 158.6
E4 lsc Col-c|Ell ol=
> o! EEfE u[+E olt

dol-8Efl olEoil^-E E_t8 Exl'flI dol-.8Elaln
61.= grl EEE Ed6l4, EJBE^187lDl?1rlE
+E 8¤ 0l grl dE4 Ea
Etr^lrJtrl'. HJ8#q 74e[ 0lE0l U8g trllE +5a 8+ K
5 HIO E
=,
Ee^lztrl. o r-iO=
^lol= {ru
Er
E' H {9
> E4C TllLJ oo=
UEEflIH6U g¤ElE¤ "J-=n 0la0l ,g,8=eEa|Eq.

> Elg'Et qHl rl^l u3 ats
0l EEoll^'l= F Tlxlel gzl= 0l¤:6|.=.t1L r 6lLl.= BE a+q fal lsc.l "JE U¤ioll EllEI tr1EJ!¤ ollLlxl re=J. U8Ezl8dE Al'019
:Br+ gE tso 17 l. HJ8g gdEl oilLlrlq.
EU]l tr4lolq(Eq rzF1, -E olLfts gE a+e]
^lolE
UteJ Gibbs ollLlxl, t!8tr1, =alz flle-enlgl eg gqet4
at+ Exlrl-(EE 6A). 4s. a+9 8E EEE L}EILI|E
^tolel
Arrhenius aiE
=I
?ioiot Et.i.
u= riE+. vjHj¤ qiLi^l=;Ei]_=. ilf o4 ol ?rl] ¤9
ol_f| flzl-E9 d+g gdal=ol4
HI+ Ezl¤ol
=i.lql^J
_r. eI4.+rlldg zlu +ql= flzI dt9 flzl¤ol zllull$q
q ^JcEql r++ 7l9l sB:"lal g+ trlHl¤ qlqzlE ¤+
dol-8E}| olE(gCEl+ olEol4r.s. ts4 P=r 9l+)ql^J
?-lql^J tl*ol ¤aq Ep=olirll, ol glHzlzl $cs] qlqzl
dol ^JEIE 71]'Jr+ ¤!41 gq49 z}lHg ol+alq +E
=
olE-(Eq lsA) o + e= a_H+ gd trl g'J6t4l +E E
"l+. rq+ ¤-= olEql^Je+ eol E= ol+zl ^ltrq+ a
^J+
E 414}ts + gl+. dol t4 0l#
oJill oJzl-ql 6H'J6l-= oJ .$
=Îzl"J
1ol4-z eopt 6Iq, +q q 7ill4 o + ¤E6I
"l zl-F4_o + 4eq, p= ¤ql 7I^J $zl6o"E9_e. B"l#zl flq q7l^J= F HI¤¤ +^1714*61 7l*Al d=6}q "Jr
?*ots 9ts old$ zlzla- 914. d"l tr-']] ol$g Hi+ tF+ 4xlr a+"J cJ "Jz4s4H ^JCEql ,l144l g+= aE
9 =zlE 4I+61+ + Seol #9."J21. HI+ Etr-ql^J "Jq s c46l]E ¤+. r?-l-I. oltrll ol+qzl= ea4 u}]g¤- Hl+
el dol 8E1|4r qL4.Ez}ql nl-+^l= dol tr4"ll Eglt+
+= ^lael E'Jg zlzlt_ E+6itreJ= 6l-+E ^lEtri.
7I HI¤¤e lEoitlzlE o}zlq} ol Hl]gg E"46IH gg4
o + IJCE$ q}.{l g+.
15C.1 Eyring Al
+ *+ + Ae+ B7I +# 6lq HI¤¤ oJezlts 4eql^J al EE dE g^l dol t4e} g.^Ja}Eg s6l eg *s-tr.
txzlE 6tzl"J 53 +E6i-= {ol ufr}a}4. ¤*dal+-e-
E EIHI¤ qlq^l}. rH lsc.lql -B"J %r-^lo-+ E6l+-aol "l
ElHl¤ qlLlzl +dE ¤+p-l +iJql^JE flzl¤9 d*illol
d¤4"14. "l :H3 tsg HI¤¤ ++U {olzl"J g-g HI*
4, dol 444 u|gg +E}dtrl-.
^JHol 5-^J4ge +Eit+ HI¤-ol "Jq4= s
qlE iilHl¤ ^JEH=
tr-ql^J es+ eE d6}4l qr" "J:4zla Eta4 fl4¤

g
^J-tr.
j/+6t4r+ r+lel4l q= 1"14. dol ^J4 olEql^l= Ae+ B Îolel HI¤¤ Bz.Joig- 6+11
mlEzll
^l-d BBg E6H^J ¤^dEsE/l "Jq*+:z ^J4+
+(rB lsc.2).
(a) #lEt
e}*g.e+El ^JCEol BCq= ql zld4eg +flq= g A+B--C* K+ -
PtrP" (1sc.1)
PoP,
47J A4e+ e6J4I F4 Ae flzl¤9 E+l= +q4= aol
lsc dol-8Ell olE 601
SE flC4"1 *rJo1-=¤ ,4lE?]= Egg g +E glirll,

a+q E|+^J= ol ${ffiol q+ L?-lrll Eld6}4+ E.=
=t¤aF=
mls4 3rld4q+E'Jilg+g + ++lE Eldg + 9l* aol
K tri. trl.4^J grJalgol dol t}qE E" 46lt +E.b H]* 4+E
5 H}O9
Jo=
o ql 6I+ "Jq+= TIEeI n54e+ ?Jqa- tr= trll{ olql Hl
{ru TOIAIEH
-El
E' H I=
ql++r _E-olot 6Iq, Irl?+^J q+!+ ?"1 448 + 9l+.
oc,=
k+ = tcy+ (15C.5)
uJ8 rlE
{zlrl rE Fu[ 4l+4r +-E=ql, E+E Ailzl flg uI=
leJ 1sC.2 HJB E+=J(HE HJSoll tH-eD. +B+e HJB
^lE=
+^l== trlEJl¤ ollLlrl= LlElL.!r.[. gdEl-=3 trlEJl¤ E+al
-r.al?
Eqotl
r #g'llill4 "E lE +l++.
6t|=J6lq, d0l 8Et|= Hl'E. 6t|=Jelc|-.
=i1
=Et|Eoll
z]=J:d 0{l 15c.1
q7l^J= ¤EE 9E"EE ptp"a +4,]lfl+.=4ql gE-
?+ 4Le BxF=q d¤4"J +zt 15 ulfi =.zl As-zl
a(czlol olE-a) eilol^lel Bd_e__tr olBal 6Le +Hel + ldcm-'olq(qlE^l C-H Aqlg Bq-1465cm-roltrI) trl
$$ +a6J + gtrll g$.b'll, "lEg + Ela_a Tlzlu 7z\ 4rJ rol3Hz azl AEE {t+ql 6il'}++. "J"J L+6}rll
6J + 9l= ¤+^dEl¤4 qel Hql^l +^16l-+. e'J¤ flzI d$ol ol_E_{ {F zI4 ** zzlE dEE+
+E sq pt3 pt=Rflll= oJ$all.<l +bE tflg +4qE += 7l7lr. TIE++I 7la6rH rf= 10rr-1012Hzzl g 4
gcEl¤E E.EE +94 ?"1 ¤B ti+(+-qHld)e+ +¤ ol+. olq+ +il= rl= 16tt-rgr2s-r-a- 9"lo}4, F4 4l+
rE -L 6hq ,r+4^l +Ag 4"14.
^la + 91trI.
lc*l= Yr*teltsl
p
(1sc.2)
*cE+g_q_ lEzlE +r.l HI+q 96il^J +E ^J+ tcz 7l7l

(c)B¤EfEE t-E
r ^JCE P-+. E6ll¤tr+.= Eq t2Fql^l ¤EoJ uI$ ?"1 ¤B tL+= *a rlolelE "l
+6ll^J 4l4}g + gl+. r7l6}q ol ¤g 12F.l0b^l(_tr= g E
c++P u=krlcr) HH .J+
{iE L+E+U K)¤. ol a+ql 4e 4+^l7lB +s-q-
(1sc.3)
trI4^J eg ^lg Eg + fl+.

NofS-
v = k,[A][B] k,-YkrKr (1sc.4)
_e
e-^&/RI (1sc.6)
"*- -e
1n1a
olTl^l
*e_E "Jg ol r+zlE +E tL+
6flot aJ /c+e+ B¤ tr-+ rc
- 4l^16l+ 4"14. AEo = Eo(c+) - Eo(A) - Eo(B) (1sc.7)
(b) g¤iElEE E4 *s. {zl,rl Noe}ri9 E+l= E+ mol-'o]{, tr}4^J rc= + qHl
grJalgol d"l Col E.$ +rE_6Iq ?+(gB ,r}fol o +'&¤6I+).
^J4E ¤14618 ^JCE"I ¤Cg+. EI¤: E ol Al&el 4+ $C+EE $u1l g;g- 4l&61.=
+41_e^J
gqql d=Elql
^l¤ol !lC+E "++ "J+ AoJol ¤Cq| ql adg *+q -H-zl. olu] z|{al u}e+ ?ol ${rffi- 5+g
4 aL"Izlq, E qts A6Jg ,J"lzl4+ #qd+. r?_l6}q r As$ g4L "Jqazl* 6|]E dol ^J{E |a ^J^jEE
Hl* ale.ll tr+4 gCEl¤el flzl-Eol tlE .g"Jel gE¤ 6t
HqzI+. ol 41t- *4E r]ffi tol+r alE "l dF "J
,ll gtrl ol trf,ol {ffi i. 7l7la_ gq+H $rJqg¤ g
E11+ tsHi er+E Eq l2Be_l l2B.ls^lql
^}q]E d=61.= {$fE s.6J f
ol? ilz[ {a$llz} d"l ^lq "I4 'l.gr+
= ol ¤ + 9l+.
7I E+. rBl+ HI* alg+ql q+ gq+= tl#ol sF
grJrl-Eg dol {}4s Er 7I= Ag
"tq+. qlE^l sld
602 15 u8EPl-+
(o) +s.8+
zlftllzl4l{}{ {qgg q-s-r+ *ol 6aJB + 9ltrI
K
5
o
1r,-\krK+
P
=K.+SSf-
NV'P
{ru
Er
E' T]E
=?I
ol +4lqlrl
"lzlel tl5+ t7I t}4lElq(a4), q+r+ ee
Eyrins 4"1 494.
HJB 4s *,-*ffffrcr Eyring

^l
(15C.10)
.f.al 1sc.3 dol 8Et| tr1EJ!¤ oilL1^l EEol HJ3 4}E.oll Etaf^l
=x1oll^1=
'-Ja g1l LHalgt=EI. 0l +E +oll^1 +-sr== zl9 .l.E4?]aEl T.!- -Lrtrl'.
¤zlrJ ++ glq¤- zlzla_ +Elu ¤B ti+ -ra= Ul =ptRr+
+4lE ol+6}q Eo E9 oJ+s +ElB + gl+. Ez}el r4r
1
e?]. alfl ol ¤¤ tr-+E E.-E_E_
+4U -r1& zlz.lr +4
{=;;**
E + ?l+.
ol {t4= Atr"4"J Ez} d#ql HI6H^J ¤d <t"l ar4. :z K(
ol+= ol tl$ol S{e]{¤ #"lzlZl 6l+ TlFolq^J El t}

fz}4t+al arzl rllEolck:_H rsc.:). Elul^J hitkT<lol q tAltBl c" RT ' RTc" -
t: e zl#o-^19 dz]|a}{ +H]] e-+= r+s'=l} 4"1 ¤ + 9l+.
rkT ol +4lE lsc.tg^lql Bq+E Eyring a]o1 ffi$ B3 E-e

7 - t-(t-hv+ lkT+...)- ,rr g+.
EI+^J $d4¤el BH]] 6J+E q-q-$ eol 94. *,-*ffrci Eyrins

^l ttl= E^ll (1sC.12)
^- kT-^ (1sc'8)
¤B tr"+ FE A, B, q c+E EH]] er+= zlzlt- 4l4lg + gl
'/Cr hV+'/ C,
o q, Ir|+^J Eyring^]e ol$tr9-e.E 2EzlE HI+E 2Z1 +

vzr+ ol TIE'J^lg zlle-l+ ol gcEl¤E 4= E= ¤+ HJ
4lEql 4eL EU]| 6J+E. +4U+ rflH ¤¤ fl+ rc= + r $ag HI¤¤$ !}CslEE +zI v+{"lEle+ F4 4lf r
94 4"1 84. .7l^la_ arue. + 9l= E¤.J rl"l ¤ dol+.
eI* Ezl¤9 EUll EL+= ts:*+4oE Ee qlqzl
=+l
ilg* K*-
N^7:'.-ÊolRr + E. s-q l2B EE '+s+ 4 ol$oll.<J ahI6J + gl
,6*=
hv* q:,qi
(1sc.e)
=g
+. rBl+ Eyring 49 "l*R trI= g.^dsl¤el $ufl oJfS-
4lt6]*= "Jol Ezll44ol4. C+= "JHI4_o e E.rtql4eE
¤zlri -Ic= 'J+E ¤¤ ^J+E^J, cel +lt Bal alq¤ ull
olU 4o14.
aÎ6J + S._o q(rfl+ trl+ ¤g Ho|BD, a aTle+ -s.oJ l
EJ.n +3= zlzJalzl ?*eE .J g+.
tl=JE! o{l 1sc.2 E@ +u'21fl=sJorg #

+z7l s.E g"Jol Ae+ B7I ¤-=-6I¤ zflz} Ezlzie da F zl]9 +471 S.E ^JE += + "J"J"l Ae+ szl-+=-61
gcqg¤ "JE+r ^J46IiEZL. zfl^l d*ill-e g +} ol z$zl Ezl-3 *g
+CEl¤¤ "JE= a+E ^J46t,r"
=
da}E¤ ael6l-= 1"14. ol +6JEg ITHE {¤. %r-^lg HI* A+B+P9 +E tI+E +4Lll= 4¤- +E6Iq+.
zl4"l6l-zl"J ol %F!g HI* als'ql ¤6ll^J "Jq+= g
r.4:g ,\l$ Hl¤¤Eg +^71 S,= gzl¤olE + ol5
Eolo + 7:,qlE 44421 g*=4. El+^l grdEl¤g s= 9 EU]] 6J+ql 4+ zlq= E41 6JE=+ol+.g-Cffig
E +H}] E++= EI{I+ Htl ¤t4 zlq"J *rll g+.
15C Eo|-8El| ol= 603
d*"1 ffi6=t1e*usoltr +C EHI_ezI IoJ 2gzt EzI e. 8kT

y2
k.=N^ *a-AEo/RT
"JE gCffiolQ. ol $rdrt$S + 41d- %F^lg zlzla_
6
"1,
?lzl"J A+d 4l rsc.zoll^-l ¤H6J utel ?ol ol %L4g HI
¤+lE +ql ,r+El "Jq+= ¤+-ql 4%L6l+ Aol+. trlz].
xP! B7[ 15C.1 **AB+c +Pzl d¤ ¤rJflg-g:aq1
,<i g.!ffiE E= E EHll ++= 3rld+ BTIE 7lq"J
.JqU+E HI¤¤4
^JCEg BUI EL+ql
q¤ "Jzl¤
^J
e + ol+qdq. +Hq= EHll q}+^lEg e.q 128 Eql azlle e **T-l?ffi#
bBEtvE'+rL EBtr t6nv E
+e+ 9l+.
Eol Htl Eull ++= r+q-l} ?Jtr+.
1t
_v; Al -
h ,ra
Y--re-
RT 15C.2 EE+4 a.E
4 (2nm,kT)'t' P
F4l gqqL4 'J^lE d"l ^J4 olEg {}d+=E +aE g

¤zldI=A, B, of C+o1\ mr+=mo+msol+. trI+lJ ol gl
+ 9l= 4*zl 9rl- "J 9zl ollEql +"J \++ql ++6}al g
c+Eq E= E- EUI eI+='l-gr+ *"1 84.
4. :44 ol %r-H o ++q +e 7]]H, HI¤¤4 ¤+CEI
AE =61
gqql4 "J+E LI+{
BT]
E ^lolel ¤¤ z|]H$ $Cs+ 4Ag
:_o zIkT _. V; r.z} 6J+ B+ trJ gHl4?l de "JBg E46i= Alzlzl 4
f i'=-n- " 7I
fl+.
ol j1g ¤EllE qd +E]] EI+(Eq 12B)$ olg
^lql^J=
o]-8.+. lsc.e^lql E6ll^J tr-+ trE q+r+ B"l EU11 el; (a)EdEl4elolEl
5g zlzlr. +49 + 9l+. qlg 11+5- 6I+E ¤B ^J+qr 6J et ,J^l
^J46lE(c*E
g 4la+71= 6IS.zl"J) olag'Ig4 ?ol EdEt cibbs 0ll
i&
LJII A+G_tr_'iElE + ?l+.
"+ - o QlkTth')v:t4,
r\ _N (vilrt)
v:t,t^)
\-/--
^-ÊolRr_
(*
.. - ^rf^r&\zrkT ^-oa,*,
[-4m)-F-' A*G = - RTInK+ gdtrl Gibbs ollLl^l [Ee]l (1sc.l3)
...-
,tA '18
"l ¤q EE A+x= s= gqq}4 +s7I q+"J a+)rolzlE|

tr++^J 1sc.l0^; o ++El r+e-=r+ ag A4E gg + 9l+. +a-6l]zlzl ?+E+ 617l f_16l].$ _E¤ ^JEll +EE ^J+*q. r
K- 4E tsc.tg^lql el6ll^J +E ^J+z| rl-e--q- 3ol ¤4.
KT RT
k, =K- o,="+F"-a*c/Rr
hp"^ tw)"*'"-û'^' (1sc.14)
Aoz',( 2IKT
=*T*^ t-7" rr'
e-AEo/RI qls ac= LH_TASoIE +, ¤+csl Gibbs glHzl= +s_4 e
ol B¤Et tlEE.trl A+se+ g8ct fl!=Jtrl a+HE ++q^l +4
¤El 4olzl roJ zflzl e4el +c .EHIE= Frrolq, g + et4.
4q 94 +alg Br +Fq
p=mamst(me+zs)o'14. o]
6Ji$ tr-4"1$ trl+4 Ag erll ¤4. A*G = A+H-TA+S gd+ flle_eqq fl!=Jtrl tgEl (1sC.1s)
= ^lg
k, = rN^
8kT
v2
Tcr2e-^htRr
lsc.ls^lg tsc.l4^lql Br E rcE SIE+El 6J +ql Eo'J^l
7lH trl-e-=$ Ae gg + 9l+.
"1, ^lg
¤-q E mf& HI* +H4 +sH ++oJ# d+r "lE k, = Beo"/*.-atH/RT ,=+F (1sc.16)
$ zlzl_n +* ^l(lsA.e^l)r+ ggo}al E"J6J trl+r+ eg
aryt+s+. ol rJ {zfl.r.l7lElE g^dg} slE.rle+ g.¤s} olluJzl ,r.}ol
^l¤-
E +AE "J"t"t ++ ol Eg zlzl ? a ol+ trIEql e *
604 ls HJ8=l-+
xl ?+tr}. arll olf+ E A+ue. + gleH #4l.Erll, "l

+¤- tr++^J
=
ae. r_oql^J"J 7l-L" 6l+. te- gsql^J= -E= +E a+ +
e ++l=ol d+qq, q4^J Rr azl CE(+F EH}l g?-lql
zlill-^J Hls" E 4*, E^= ZRT + L+H
E6]I^J)E 7lq= 6].rll gtrl-. Ezll ol+= zlz]]-^} r+Ag A+ ,qE6IE,

ataE a+ue| RT I,J+el zlTI 9l+= 4"14. "1=. +zI4"J
(a) A+H= E^- 2RT
_s"J# Etqo} alE 4o14.
(2EzlE Tlill-^J HI+) a+s$ Ea lfglol trZl (15C.17)
@ gg=l g!=trlet B¤Et oilL1rt (b) AtH = Eu- RT
zJll ^tolet (+.]+ql^l g z¤.zls_ Hl+)
gcEl qlq^l
ÎolE +41= + ^lql 9=*
g^dEl flBqe+
+. 6I+='¤¤ ^J<" rc9 9s E=¤. +4.11= +r.J c_ tr|+^J +E tr-+s=g ++4 ?"1 ¤4.
^lo
9 0s.z^14 eg dhrqS/dT= L+HtRTzolq, += 6I+= g.
=q +E 8+ [dol-.sEH olE,
Carl qlqzls^l Eq l4Del r+o.ral4 eg ge-l dlnk,/dr = k. = e'Beot'ttRe-EltRT 7li1l-8 HJSI (15C.18a)
E"/nrzo14. + ^l Îolql= Eni"g ^lql el6ll^J k,=(rckTthc")ft

ol
r4r
E +417t dB6J+. lnk,E +l6}q rql +El^J
ElE6l-
H rJ.g=r+ ee !g gg^le-l
+ 9t+. k. = eBeo't'Re-Ei
R?' +E 8+ ldol-dE|i olE.
Eq +oil^1sl 2E^lE uJSl (1sc.18b)
dln(_l,dlnl{j
-?7--Ta -U7- ¤ zl rJ - (kTth)(nzp")ol+(1sc.l6^l ql
3 e-l6]lî). rqa
Arrheruus txl^= -'i+4 ?ol S4.
olq^J dlnkJdT= E^tRT2g ol+6}q q+r+ ag +4E Eg
g^l-al E^f
+ el4. A = e'Beo't'o ^l+ Tln|,s
[28^f-E. u3]
(15C.19a)
E" = RT+Rr'
off: r4r
g^fal ?.1^f (1sc.1eb)
ol A+B+C+ E-el HI+ol zJill_rlql^J "Jq'+E A = eBeo"'* ^l+
t8E +oll&E 2E^lE uJSl
^ldq^J=
ar+ "+ill-^J"11^J "Jq+= ag +trp- pez[ 9l+. .]ill-^] gCa+ tlE +irl=
qlîE HI*el a+ql= *lB tF+= tE= zlzla- +qqlq, + HI+ +ol d=6}q 6J 6¤ "JE= E
slq ql+ 4oloe *"14. rBl+ tlEsirlzl- Ae+ Bz| o1
+l E4l 6J¤- cl olt 4l&g gsz]. sol +3 + z.lH ++6trll EBIBg *I qtlq= 4 olalE qele ql=
^lel ^*Htr
9l+.tr}+^1,
Arrhenius "JzI e9 <i"l tiql 6g- ol$_q E ql^Jq= 4}r
+.4_tr- HI*E 4*, E"= RT + L+H + lrll ¤4. fl=-+vlz} ol+ril ql^Je.ls *"lzl. Ag +5
Tlill-t} Hlg" 9 a+q= -K:7I rc(f E "Jqg z$lt- ++u) olEE gill "Jz}"ll zlqlq= ao +^-1, ol q+s] fl_Etr.rl A
el rJ^\ ?+sq 6J +4lE El rEj"ll+qo} ++. lsc.ll^lql a A*S,,.n.= q*+ *".l +E=EE Eîl qlzl pe+ +4lE+(E
EsIH ol E ^plql= l(_(p"tRTe")&E +4171CB+tr}. trl I tsel.
+^J,
p=6^'s,,.*/* p ?.lxt tEol-gEfl olEl (15c.20)
1lT A'H/RT2
dlnr(1 d. RTc"* dlnKt I

Et+^J .F +ol d+q= Eill4 adol !-$a14;q. A*s,,.n
9 <i"l trl r4l ¤-_e_E qll IrlzI^J pel <tE q L"I4ltrI.
a+H
-af =dr'n p" ar =T+
^7
ol
49 dln-Kt/drtr- +4U +19 ^lq Bq+H q-q=4 Ag zttrJEl q 1sc.3
AWt s+. o|,rll =.& s+ +"+ +qlî EEgrt}BtolSS
A-+H++pE EI¤¤ "J_qA+. 30.C -2.05xa
E" = Rr+Rt'
offj = nr*nr'I I _-l-_
A+H
= RT+RT+A+H 16r:6[rrr mol-r s-tol4.
=il"ll,rl
30"Cql^-]E ¤}dgl- flE erlE +6]
T' RT=
1sc Eol-8El| olE 60s
4E rsc.rgu^]g q+4 z.¤. E.e rA^l ^J+=- +Qr]]= ++ + ^lg A'J^lAq.

"l¤-*trI.
A u#,
a+S =Rln , {zlri U -YY =L.592x10" dm'mol-' s-'
=o*t.*,
eB np
,.Iztrl, rqE ++4 ag 49 eg + 9l+.
o,= T,U)/ce.
2.05x10'3dm3mol-'s-r
A+S=or,
.. "' =Rln 0.0473. ac'
K_ aeas _K , [c*]r" KT
Tc*
ex 1.592x10t4 dm3 mol-'s-'
{e-l{B-l I TB
- 25.4 f K-t mol-'
=
r?-lr,
E =/qtAltBl k,-lL
dtPl
(15C.21a)
glCs+el Gibbs ollHzl, flBi{, rflr tjs+ul(:z4l !} Krt"
"t g+=*)e ¤e HI* +E 5al 8o]] +ql^l "J

^d+ +.,tl
q+= *zlr+4 qI+ +E= H n6t= ql ts4 "l*94 gl4.
olEg 561 lnK(=, -L,ctRD= lnk (o149- -t+ctRTql Hlell
r 6IH +E tI+= r-fq-l; Aol +4H + ?l+.
q}+)ql q6H^l E^l6I: Atrd ^J+
ol$all.<J BB
=AHg k, _k?
-Kr logk, = logk? -logK, (1sc.21b)
e+ HI+ 4r.<io19 +41. ¤+6|= EllqlE ?l+¤+. ql+E
el a+ql= tr-+ +Ar7|d¤trll, olae HI*ol gqqi4
"l
o + rl $ola114;5. r +E *izl +7I¤I+= ag *qI+
E.ETI *g rI= tr1"94 eg gel Debye-Htickel*¤l H4(E
9 sn .61 sE.27al, log1 - -Alz*z-llttz)-e' rAl^-l !}EE alf$
(rH 1sc.4). ol dB dr-+C qEql ol E4Bg CE rl.8 0ll
+a4el ol$.rllzl r= 7l7la_ +E}8 + gl+. rqq q7l^J g
Llrl EJ7{I(LFER: linear free energy relation)4-trE +e-trl. olgSql
s6J a¤. zflzfl
'll+ alolzl ¤+ =+rE"Eql +6J ^l
ol otqq, rr-16}¤ log y--Azlr,o^lg ol$-allo| 6J6J+. =
(b) olE= HJB
^l-olel
+.1 +ql^l "Jq+= HI+g *ol]z} g{sl¤ql^l +s_* q
(15C.22a)
log In --flzf,Itrz log Iu --flzfiIrn
tsg 617l ql$ql Fal gqqr4 olES 4*^lzlzlzl Eil+61 2e8KE ++aI +ql^'l= A=o.S1eolJl" zoe| zs=. zlzJ Ae+ B
+d-61-+. d"l-t4 olEg gEqL4 u}^leE +ei.llfl +E E d6l++.$Cail+--e- l4lel Aolgl} lTflel Bolgol Hls"6L
+q^lE HI¤¤ +617171++6l]zlq, ul-olt4 4lqlE zl+ q ^g^dg BrJr]E.olE+ g^dsl¤g da14g zo+zuzl $Q
gE+4 "JBql^l= +E H44 gE+4 B¤
^lrJ + 9l+. (zE oJolgql q6ll^J= "Jola golgql 46ll^J= *"141. r|
+^J,
logf ,, =-fl(zo+ zr)zUrz (15C.22b)

l*G(a)
a
AIG b
ol +alE 1sc.21b^lq Hq+H q+r+ ee arl-= eg +
()
---: ArG(b) 91trI.
K
5 lA,Gl
6
a log k, - log 4-A{zR+ z3- (zo+ zu)zlltt2
¤
(9
l,G(
a,G(b)
- log ki+2flzozullz (1sc.23)
E6IH +.-q +ql^J "Jq+= olg= Î"lE HI+

1sc.23^lql
ol8 rllzl9l tr14 E6l+tll, ol
^t¤g +
"J3 rlE ql^J= +E
^J+zI
fal 1sC.4 +aJq= "JzJel HJSoll,tl= aEPE b-e EJoll qal gdat EE4 EErt4r ei4tf-H 1sc.5). ol 4g r+s=r+ ?ol al]4
AAdlI +E df+7f E=
Gibbs 0tlL1^l7l UJB Gibbs ollLl^lel aTVl e7l g + 91tri.
6lq, 0l *Jl E= UB Gibbs ollujxlTl tr1 '-*0|'Tltrl. CB 0llL1^l
aJ4lel= Eq==+=
l+Gel a,Ge rHi1l4?.1 dE ag¤o-e+E1 +aHE
^t3
^[ole.l
a0lcl.
606 i 5 u8=l-+
0.6
I 0.0050 0.0100 0.01s0 0.0200 0.02s0 0.0300
0.4
lt2 0.071 0.100 0.t22 0.141 0.158 0.t73
+ los(k//f,) -0.14 -0.20 -0.2s -0.29 -0.32 -0.35
{
e_0.2
+ 7t + ol rllolelg E^l6J Lol :zB tsc.6ol+. 44 zl*Eq *
-r<
6o0 +
0
0
+ CE zl&zl} -2.04q, El+^] z6ze=-)o14. ol ¤4
¤E6IEiH gdEl¤¤ BC6k ql +q6l+ + +ol
-0.2 -bq v+ L.
=
z=*2oJ [coBr(NHr)r]'*9] z---r"J oH- olgEol 4"1"t
-0.4
0
I
0.1 0.2
++.relfl d6l¤el gol -2zl B + 9l+.
ItD
-14 lsc.s2e8KE +tEoll^1 "JolLI= HJ8oll rH-d +EE4 EaqE

# q7l^J= ulz.l /g$a}zl ?*9lzl"J +E t}+ ,l]A
6^16[= ¤:d. 018 BEH= 7-+ u1e1q1fleq, )l37l= L|EILH= C=3 E tr-..|l +dgE ¤6JE BL_+.
Debye-H uckel 9 l-d E =.lrl t sC.zr 4 o-ePE'l Ll= 7i0 trl.. I
"J"J HI+
olgEol Ae +sE d6l¤ 7LA qb -0.1
("fl4r.il "JolgEzlel, E= solgEzlr] HI+g { \o
ull) xll:9 olgg zlo1l.<1 ol$ ,<llzl= +7I^l7lE J
8+.2
+E 1l+71+716Jtr+.
*.9 T16l-= 714. + ol$e_e$q +g +"J d6I {r n2 \
E $Csl¤ol g BCe + 9leelts ¤¤q= ^l| 6
-tr-g ols + g}^d3rl¤ol trJ ?Ia6lrll qE+ +q4 tr rU
0 0.1 0 .2
9 "18 EflzlE tq +qo} 6l-= 4.o14.

11t2
orn
fal 1sc.6 zl'45-,' USel ^-E Ar+oll 0l-l= 018lll7lErl. 0l 7lE

ole+ HlrllE Hltril d6}el olgEe tg olg
^ll7l zlE ol8atG +E Szloll^1 BdEl= Edal=9 d6l BEt|oll g-d
=8
E +aq +ql^J q L44l Hls"ql+. oltrll= g-^d3r} trH= E= + ?Itr|. E^loll olEE qlolEl= H7l1sC:410l+.
Eol B^dElfl.<J {a}z} tr-4lg c* olg Eflzlq
E ?IAgI ttszl$ol :"J* ,J+.q7l ullEol4.
rPl 87[ 1rc.2 +te] {alg-*E ol3ol +E "l¤ ol
gr+ ¤lCEl¤g "J=+. 2e8Kel ++"-qql^J r-H. qlolq
E 0l+6}{ ol ctE "lgel d6.l.+E +61q4.
GfuE7 ^-EEe Eaq=
oE:d Ejlo lE'l 6114
I 0.0050 0.0100 0.0150 0.0200 0.0250 0.0300
ffi [coBr(NHr)r]2*E gzl.$ zzlql^lel z[ffiap {l$ kllc 0.u7 0.791 0.7s0 0.717 0.690 0.66
+E tr-+= oirll r-llolQs+ ?ol +aqE ol$ ,<llzlql q=
qI+. +I;-44 *Zlql^J BCq= g^d+BE d6}ql + t-:E
6H^J qts AEg Eg + !lL+? ol ¤Eol HI$ Ell?Lq+
ql +6ll^J ++u}|¤¤ "J-o|]+L+?
I 15C.3 +E=4
kllc
0.0050 0.0100
0.718 0.631
0.0150
0.s62
0.0200
0.515
0.0250
0.475
0.0300
0.M7
=+lflÊ4
r¤ FaJ HI+'llriq=g TIA6lqE ^JCEol "JEolzlE
rqE r.lEI lsc.23^lq qz} bs(k/k )E /'/2oll qql^l E 4Aql^J "Jq+= flzl¤9 Hsi r+Cg E+6171 +16}l^l r.oJ
zlgzlzl 2AzezsoJ zld"l +e+"F *tr|. 2e8KE + g *g de# f!{a1lo1 {}+.+EE4
^l6LE ^ll"J6l-ril =?lfla
+"+ql^J ,A=0.509o1= + zl&zl:- t.\2zozrol4. "l z1&zl
E+El grJqg¤ "JE= olg=E d6l¤ i=.-E + 9l+. + HI* L--Ezl ei6|= ¤rJ"lc}.
31ffi +A6IH +E- ol
ec +zlql^J "Jq+= a.J-B+ Îag flal 4Eg + 9l
+d trl+r+ Ae EE EI=+. +. r?-16l-9 ti} +E=51 E4= +E eC +41qI
=ol =+1fl4
lsc dol-8E]| 0l= 607
trl(c-D) = 0rcH/Fco)t/2a,(c-H)olq, pE ¤*9= +-tr {=J"l

+.uI+^J,
o -
II
oI
ttJ
K (c-D)- E, (c-H) N Aho(c-H){1-(
5
6
E" = +
# )"' }
{ru gdsl oilLl^loil Dl^lE Sfapl a4- 0sc.24)
UJJ
--l
E'
++4E1.'ll E6J]^J Arrhenius zl+ *zl-4 "Jzl-7I H6I^l ?*E
tr|H + +ql ql+ +EE ulzf clê=;| e-ol ¤4.
HJB lls
:IaJ 1sC.7 C_H ,l:dol $= nllg u13 =_+"J Ea[. 0l r=Joll,\l= k, ( C-D) c-DFE" (c-H )yRr
((c-s; --"--
E. ( E" ( C-oFE" ( c-H )}/NAkr
--s^-r
{
c-Het c-D =+4e1.

zsal T.!Eo-e LE[|,|flrl. EEIE c-D7l C-HEtrf
=Er= =
't3 0E oilL1^l= 171 nflEoil "JolLl= U8Esl otr oilq^l EatsolEl.
0lal-d ,3r:te c-DtrEol c-HtrEe.cl gd+ 0ilL1^l7f cl ]trl'. {zlrJ R=Nekol4. ol ^lE E (c-D)-E"(C-H)E rsc.z+al9l
Bq+H +94 *3 44s EAt ¤+.
^J
Eqfl= ¤.Jol ¤+q=zlE +e++.
flzll E+lfl^z} k,(c-D)
(=,t#{,_(H),,}
2il ^-,E=4 E4= 59lflazl EEL¤ eElol #q ile_H) =e-(,4zlrl
4^l ^JCEol
=+lflI
qzl ?+EqlE HI+ +E7| LejzlE s44. ol +E 8+oll El^l= E.rl (1sc.2s)
=+4tr1
+ E4= t flzlz} +49 E+lfltE ;(l++qH 0a 4lE ql
vlzlzl HeLe-ElJ $¤nl 9lHzlz} H6I7l trIEql .Jq+= flco)FcHolg+ (>0014, 44rl tol Eg
k.(C-D)/k.(C-H)<
++6Iq4. :-B rsc.Ttr- rlqlflH ai.tH +E tF+= ++
4o14. olxll ol lz} +EE4 ¤'+lgd Eq¤- =+ q z|,rllal
aE+q E6H^J A^6J+.
AEEzI.
c-H ABol #qzl= + Hl*g /8416llg^l-. ol AEIE ¤
$ol 4s-44 +AlolE(Eq 14E) HI+ 4+sE c-H aq}9 z]trJEt q 1sc.4
41*ql ql'J6iq qd¤ glHzl s+gol :aH lsc.z$ po1
E+. 6+a ^l+l¤- qtg qlE HsI= e'JE 0d qll,lzl 4e-ld r-trlEfl deql el6lfl c-u ¤g}9 zle 41+ Tl
*^r+(++r $lxlzf q +azl=ullEoltrl). rq+ dill4"J F %L^lE tl*+:. "j 3ooocm-,o14. ol 1lf,fg o=2nci
HI* =e.gg *olzlzl ?*=ql, :a vl*Z $Cafl¤ql^J$ + E +4lE ols-"ol.{ 4_1lt+ ot_2nva Hl-#trl..
fl tlfol tr|]*61 *e E tr"+E 7lz]4 r44q "l + A+ @ = 2Tc x (2.999 x 10ro cm s-r) x (3000 cm-r)
el 9C+EE HI+ s}se+ +flq= 0d qlqzl= 4el H6I = 5.65... X 1014 s-r
zl ?*zl ull$ol4. olelo.J raJql oJ46ll^l ++AEl el*ol $
,ti¤ +tr A+=el Hl= ++4 ?ol ¤4.
Csl qlLJzl"ll ulil= Er+E tr+4$- + 9l+.
ltcn _( *r*,
*r+uo ) \_.(
@it+EiEE+tflÊrh lr.r-lmnm" )^\ mrm" )
( tz.otxt.ooza \ / rz.or+z.orao \
tszl-$ c-H agl ¤+g ^J46]] E-z|. olBlEI H]+ql^l= --l [ rz.or+r.oo78 /^[ rz.orx zlt+o )
=
c-H tr.u+"] d+q= +Fol Hi+ alg'ql 4+^l gqB+r = 0.539...
qlqzl=
^J4I6l+ 4ol ¤4at4. 4+^l 3.r.|{_e-tr ¤}^"i3'}
t+ d+E 0d "llHzl inoE Hsl.ll elaN,<1u3.Jqt4l zI relr 1sc.2s4lg
-lvl 0l+610l +g
-l arug ++
c6Jtrl. rqH :aH rsc.zql q+^J tris=r+ ?ol ¤ + 9l+. (t.os?_x_tg_'nl!)I(s.os...xto'ns-'
,_ r;
)
x(l_0.s39...,/2)
E" (c-D)-E" (C-H) N^{}ar(C-H) -}ftar(C-o)}
' 2x11.38rxro-23; r-';x1zla
=
=1.92 ...
= ; N oh{ctt(C-H) - a;(C-D)}
r"-]ir"
¤zlrJ r,;E S*q. dE9 tlt++. Eq ltcql gl6IE
608 ls U8E+l-el
f.lg-Pl =.'-,ez
-' __0.146
k (c-H)
{-
a+ deql^J: +s aa$ol E"J+ + c-H AoJol fio
ulo
trtE -Et+
H
c-D a*E+ E 7H]|+ uulsl fe_E #qa+= 4r+214 o.l
g+. :r-elLt ¤zl,tJ 714* t$6'l C6Iq, K

5
^l-&* -E"JE o
dxllE k (c-oylr(C-H)E deA= lsc.2s^l o + gg At {ru
u;l
4 trIs4. E-
=z.ll
u3 lts
a+q E|+^l= +4= ++iE ilqt6t$ k,(c-D)/ fg 1sc.8 gd^|.= HJ8Erl adE¤,Jal-=ts Bda[ oilL1^l gq= EJ'J
-ddle.e Frl.g + fleq, ral6lq 8EE ?F ts017f '*0lrlr g8^l,old
k.(c-H)E Aol lsc.25lo + ql^Jsl= AB+ gd *eq, gdxlE trt-oE-Br+E
UBE Asty + ?ltl. 0l Ezl= 8q
Etr+ sd+ Egg alr u1lzlzl4."lBlq} Hlc^J4"J +E =71-g
La1^1 LIEtLHflrt.
=x10tl^1
g¤^1.E1'J EAre HJ3.=E01 gE g+Oil '=blXl El=
utP 8Eoll,(1oJ 6e6El.
Ezl E+lga s!+= +a flz}7} "Jzlqq}4 Elts a_a= ¤l
6ll^J +}cp+ tlqg trllEol+(rH rsc.s). tlqg F
+r+6171
r+61-= qts ¤tr-+Eg g"Jol9 d=Jol ?zI¤++ ea6l zI oldol +0161-= HI*E a+ql= *3 Ssql^J= g^dsl
q(Eq 7D), :r.?-16}¤ 6+e= +i!-+ tlgg E"+61+ a glHxl tlE¤- H= +zl.+zl 9"t "J qq "JzlE+4 EIE
E7I *_e-q rql tr}+ HI¤: +s-zl L4+. +^ gz}+ "J^J Fr+ H]+ol zlull{ 4Col g + 9l+
=s-d7]lLJ=
tr l. d"l s4 olEql^J= EgaEol HI¤¤r| ¤Bg olEqr D 4. +EE4 E Az}= Hl-gC E9 zlqlg ull
"11"1
olgE
Î
olE +E t}+ql Elil= arlol+.
^J4.Jtr|.
a 2. grJaqgol
^JCBS
trJE= +E= "l{"l dol gEll= Fr+ tr s. +E=4 E+1fl4 E4= +¤¤E + gzl¤ +4+ flzlg
6l+ +Eql E='*4. ;<l+tl{g trll +4+= s}q} H}Afl *s *#z} A16l+ s
D 3. +E ^J+= gcslr+ag cibbs ollLlrl, fl!=.Eq, :4a s! 4trI.
=Jtr!= El4"lelE +49 + fltr}.
^{,1^-l
=s-d4=
.^lzl ,\l z.)f, al
oe. --1 I --'t Ha
gC+E ¤CE ¤¤ t}+ f ,
= (N. y,; I ,l;,ii )s-rr"rrnr c+9 e {E *rl"l Frl¤ ¤¤S z}C, 15C.9
Eytt"g k,=r(kTlh)1trtr.)k' dol_tlEl] olE lsc.l0

^l k,=r<(kT thf )KI l5c.l2
g¤El Gibbs 9lHzl a*G = -RTlnK' zl ol
o-1 l5C.l3
g¤EI Q]gtle+ SIE eE a'G = atH-ra's cel 15c.15
ut4"lrlsI k, = e"Bet't'ê-f.l/Rr n = 2 zllllli HI*, =I 89 +q^J l5c.r8
15c.19
A "J,+ A = e'Be'*''R
P OJZ} P = gr
)r"''x rsc.20
+EE4 g ET} log k, = log k. + 2nzo4rltt2 Debye-Hiickel *6J H zl zlC rsc.23
ril +EE4 E+lg^' Erl k,(C-D)/k.(C-H)= e-: +E aa +4lql^J c-H/D eqig gqd Lsc.25
(=(ha(C-H)l2kT)x
{l-(1,r, I 1t,.,.,)''' I
E4 15D Erl-=Eq
=+-+
zlill EzI ¤ +ql^l Ezl-=E ¤t zl-ft Bezt Hl--B
> ol EEIE uil+ 0l+ =
el zlEE+ gd q SLrll 99 tszl¤ g:e +=ol "J
el+rlEe +qt EJBE .8^1Fd al¤oll SCE 7l^|a 9leq, l Îolql
qB 4o14. olBl6J +=ol "Jq+E EzI ¤E 1168 HJ6.JeE
AAq E+ SEg Et ErPl qE Erl-e] ?¤fl= ES
6l'Xl E= HJBf "JHel 5,tl-6|==E6lG
a0lq. ¤+%L"l oldqq +fl q-44 5=ol +q+al ¤4.:_4H
=qtr|$
EzI ¤.E Ezl-=ol Hl+* 44 "e. BolzlZl qq, Eq E"r+
> E{C 7il8 all $olpffi E4¤ol E +E6}rll ¤4. "lel,* aaql
Tlillsoll^jE Erlill ^J.g
EJ8 +Ets tr1El¤ oilLl^l EEtloil^1 015
EgqI qE¤ Erl E=ol+r ++. g,qql q+^J= +E d
61ts +ll4= 4,\l'61.= "JEoe E?g + ?,Itrl
E tlilE ol+6}q gd+ +Eq flzl4 Ezl¤ dtrp +E
> r=e.il qHl rl^l 9l+(rB lsD.t).
0l Er-.,r3 +E 8+9 zt|ul(Erl t4A)= ulEle.E 6|q, g+ tseJ ol BlqL ++el +zI tql^J= +E ul4ol Maxwel-
Boltzmann ++ + qltlq= <i$trl gd q 44. ol qltl e-l
:Et+e.l
rl8oll^'l= EHt| 7t|E(tr,iif 128)E 0|Eett|.. trlH!¤ oilH^l
trEE tsE= 8d40l7l= z{N9 rtill-gg¤ I
0IE{EE eE)olr}.
o=|.xlDJ:.
=fle e.63 Es= EzI t 4 EzlE"l *e Bd s-EE ?*71 ql
Eol4r 6114g + glq(rH rso.z). "l BTI ¤5 gr= rr
zJuTlzlu 4qa + fl+
"lBlql E= a+ 49 Exl¤9
¤+ +qg ol $z|-a ¤ EF ^J4E zl4l +ql^Jel ¤+E
trIE ¤lt q Eulsq, ol ql$ql ol+l6J EE .=¤ AE+ E
HI+ Ezl-= rlol9 +E EqEg HI*E +E= zlufl6Ji e
?lg TI1L ^ll"J+ +=ql^l a^t$ + 9l+. ol ¤+= * zlzl
E"l4r il+
a¤+ E= sEg-E+El +ijl q+4 EE ¤99'^zl
*B-"e. ol+qxllrll, r qi "JBg EzI tg ol$ap {ol qeq zlzllE sot4H ol a¤+ E= s+
I +e 6I+= olE4 4lÎ ar+= 0l+61+ 4,o14. "l'E eqL]]r
g q ¤4ql *E+ Ert ¤s "JE + ?14. g+i E
oJel lL=e-tr_{, *4421 Tlill
^zl"l=
9E"}71^l *
15D.1 EI} E =$f ^J4e
6}rll dle_er l BTI &E! gszl.
$olzl3 49 "-lol.64r:zH
qq}4 EE ¤
Ert g¤: rl*+g F46ll 4ziE ¤qslg 7l-L++ +
+71
lsD.3). E¤ a=olr{
=$$ tsz} ¤g +ill
"14 aag "*+q +g(qlB^J =
z| c$ol{, ol Ezl-¤¤-
e¤l sld4 Tlt- "J^l) fl+ 4tr-+z}e+ +=^lzla o1u11 u1 "J=3
++= ^JCEE ^JEH= aÎ++. +E ^J+= tr"le} 471 * ?J=71
EllE HI¤¤Eol 4+ r+eE - -

^JEIE SCEe H6l]7I= _Er= .Il=.
ql aa B+g ilal {ollr e _E
"lBl¤i ++e_l ¤Ez} ?ig"t t}

Lio o
CE 8xl
+d +=ol "Jqg +EI+= 4C d-s. +EE + 9l+.
oll
EE
g=fl
(a) d:d UH
fal lsD.t E^l.g Sxlel 7lE ut|il. fl^l-Ll-E^lE TlgE HJ=Bee+Ej
Ezl-a ¤E.il ol+q= 7l+4"J tlil Hllgg:2fl rso.rgl L[e[^j g+Eol ?iE alt flHJe._e E _as. cE gil(EE 180il,\1 ¤B-d
+44fl+. ,J=ge + *el flzl4 ExlzHf,q_d-.rJeb zI 4r:l ,J?)= Ei7f6HLtZfl.. ol=P E4 7lill(rl-= E^l Al0l E40l E fs.
gg 4q Tlill ^JEll_E uJ=+) 4s+ ul--Bg E"46lq 1I ?ltt)oll el6H^l taJqq g8-d 4Eoll *= 2A=7le 7l+Etl.
rxF¤ t-doll^l= + HJ=flo + +81 4?+ 801-Lf Set|e=ol7l-^j dEE Erl g=
+ dE5 +e-E EqzI+. +Î %I=fl +ql il= +rlE "J Llg7il -d trl-= 0l=01 +4lee -Lrf. ral-r. 4E_+ |lalq=
4* *zl^lA +gql Hl-lf$g E6]] +s_r| 6lH B=q =E=dPil =tr-d
E^l{HJ8ol "Jol,-J ttH= SdEg +tr 91tr[)= ?J=7|tr a=E]tr|".
610 1s uSEe-+
Hfr
Maxwell-Boltzmann
+O
t},.lE 'Bzl b'4 "*E= H"l9 gg("Ji-ll4r-do_E
+qzlE)
ir:E
+e_a +^l7l4i*qq EgzlE +E_ d/= zlzl:t-,+4utrI

+E-
L-=
+=
(re 1sD.4). ol +E= trlE tlgJ EE4 o= 7l7la- +E},llE

ql, olag dre+ "J^l-q¤ r, e4 EzI9 tszl-f "JE e(
^1171
r4I ^lE +E d-e. dx r}"l9 Hlql +41. ++
ulr z)ol
tr|+$ Ae Hlql
'll= ^lE ^J++.
E^t+?.1 dI = ol9'l'dx EIE AlzJ EE4 tEgl (1sD.l)
.r.g 1sD.2 E=+ !.- t4 LfEEt= EE +alE 0l=r| EE
^l'EiI= ol og <t(H"lE qfld)g + += +4¤ ÎolE z7) atr_
el +zl 4?-l"J tr}alElEl b(rH lsD.s)e+ zt^]lq} Ezla
qg eEol+ qlg +qq gs+ qHf¤q E=oJ+. =4
TlalE +E^l7jî I,J=i7l
E qI+. +4 E|+"lqE q6Jg + r}{l+el +49 zlzla_ drll ol
a¤+ H+ +E Ezl¤g *e Hd +F gE. 7Ie + 6ll6J + ?lr+(rH lsD.6). trJoj b=0olE gol.7lb +71 4q.
"J "Iq+ *g
qdr+ dE gsE *=+. 4zlrJ E:"]t 3rl
d"l4 Tl+ gE= d4ls +¤q= tr4 zll4li +s= +4 71 0=n41 glg qlql"J e¤¤+. +4 ii}4"lelz}'I+61 4
,rl f-i-ol dg + flg rllHb>Ro+Rr) &*ol "J"i+zl ?*9.
+rll 6l+ ss^lE gE= "JqI+. rq+ Eld ¤.
Boltzmann
t %r-^lg Hd tr-48+ Lflal ¤B{l sB:"}q, df,- r}^lg 4 e=09 4le-l+ E= 4Eql^19 &+ +H4o1 ool4. 0 <
q ++ L4rll ¤Bql E-E6IE-8. Eld ^JElle+ TlE ^JelE b < Ro+Ru"J a+qlE EflE HIB HJ6J6 +9lE ggql^l
THill+= EzI +e 9F 9sql 6}lR6l+ <tg ++U+. r4 tEf ^1i7iri +{kJtri.
zlz)llzl qHl
6lq qd %F^lg e+ roKE zI4,+ r?-la {8 "J^lE A+ "IH ¤xll Bzlq &+ +9= ^ll,J+ EzlA
ql= E 100KE z|H+ql 6HR6l-= E3 8s= +4U+ ¤"ll E=6}q, Ezlzl +¤ol otH ull= Hl¤-"JcqlE 9+6J
E4 Tlillb +i4 ^lE"J +E 9la E += EzI ¤"J + +.+"J otq+ ol t*e + +$f;q ^Jqt d= +EqlE E
=
E 91trI. a= tiil= ql"Jil "Jq4l, 'EEElrJ',(zlaJ9 gE- ql+61 uut= Ezl-= EE flqzlzl $-r. ,J+ tr-E
=++. =
q=_g ol+6}.q oJrI
"llulzl$ frzlalf A+AD, EE +zl-=
4+ ¤qg E46l] +e + 9lsq, 4szl LB Ell= 'J* 4
^Jql 9lq+E A^l sq9f;.4z| rrll +lq4
qrJ + 9l
*d ol$p]^la q-¤. {z} f,tzlE a=fl-= olg a=71 Eol .tr.
++¤ ^JztE qq 914. a+ql q4^J= t+q= +z}el El +(rH $D.7). trI4î &+ +H4"1 t4 d= +Eql qB
da} {t ^JEHE pxr"s+4 BB " e. e¤6J +E ?l+. ,ll el=6I=7J-= ol+al$ tszlz} ^JE4I+E H+lql ^ll7le+
+6J A-H.E eg + 9l+.
(b) ¤-d Ert
da
tszI ¤ d¤E 1iI4 dE A5t= "JrI EzI ¤ +el E!¤ol
5A6J 4E_E tI+El= +-$ol+. ol Ege "JHl4e_+ e=
e
UI'E+B
lg 1sD.4 d"al= geTl= giil4 doe; 501.
7lill E=
.J
I
or= 47lDl
b
gtsal 8^l
fal 1sD.3 0lE6tq E^|" gE +E1 g+ E^1"= AqLHcl EBEI
^7l+l=a=+ Erl¤= :19 1sD.s EEtElEi b= g"Jol=el *t I 3e= +4
trE= Eq=-e.eu "J=rt. 7lalE+,
=4 ^plsl
lsD Erl EE=fl EaJ-+ 611
)JE,JA
RA
b>r?o+_fr*
o
b=0
(a) (b)
b< Ro+ R, fB 1sD.8 'J3 HJgee 7l= + zSEtl Bfit9:*40e Ad= geil+.
0l raJE e+q|= {.1:d u:doe grl I]E¤ goiltrl.
. ts a-471+4+= 43 olEl* +%Iq + qlol+).

(c)
Eal Ho-e rq6H+qot g olz| a$u,<llzll szJ.$ 4l$
fg 1sD.6 + ?J^11+71=E--J tr]lel 1'll 7l^l PE. (a) b=0014, +oJ ol *+
"Jolol
olu ql^J +4+= 4o14. "lag +zlTlle+
99iltr1'. (b) b>Ro+Rrolft, Eg taJ= gsiltrl. (c) 0<b<Ro+RrOlfr, ^taJ=
+Ag "*+4 "llzlr-lfi"]l elafl^l rJzlb 4ee.(i +rPH tt
gE:Lf 4E_e taJElolral s$= 0lEtrl.(E4 Ert= q=J6l +71+l^l dtr aJol+r eFt. ¤tr-E gqlg ¤B6J 4ol :zH tsD.e+.6
40+ E^lol^l ?j=trlz g4-dtr|.). "l
E El4"lel7l er$ql q+ &*4ol +Ell7l-q= dol +4
4=rll, oltrll. aEE ^l-olE tdql 96]l^J c] &* Hol 4
cl 4ol R dg +E aqzl rdEelol oI'14
-r.BJ6IoF
4+r1 ¤+. ole+ eol dgtdb=lol !r &*ol ^llrll +4+=
"Jzlqq,IE zlHl]. g=4= rldol4. r?]6l.q +4-¤q 4E=+rl7H tJaJ4 aol4r t+.
tsa_q__++q Aezltlxlq E^l7l f6|= E= r
=
Îolql^J Ezl a}"ll +48 + 9l= E 6l+E ¤tr-3 t 6"1 += +ql
dzJ +llE-=. rfl ffi oJujol=E r+*:cg qL cE reJ6]- el6ll^J Eqq= 4,o14. a¤+ EzI d.E 4rE +F gETI
-7 ol$,tfololl,tJ "Jq+= Zld ar+= ^J46ll"F aFL 4o14. =
q+61 *zl rll$"ll van der Waals ErlTl-
^Ja + 9l= aol
+ "JzlEqI4 Er+71-zlat 6_s*ql, a4= 5A6J +
7lz.]1 q qla'H A4 ezlvanderWaals Eol4 +A Aqlql 9allrl es
E u].4"lEl= *= oJEJolTI Eztt qHl¤E qlq gEs+ e+ ee 4¤-g
"J= + fl= aolq. ¤4-qr4_oe ol4t EzL
B=6Iq Hlg +C +-e-E flfl42} r*rl ol Hlts +Cql E Eol ++ a lEl$.=rll, ArHCl, (HCl)2, AICO2, 'l (HrO)2 tol
.Jq ¤q +eE Hlgq"l 4zld Ag de HJ-6J=e-tr
olelq} Bzl¤ol+. olqq} !¤-E=E $xlql4 CAg aÎ6tH
"H^l
4l+6H^J BolzlE 4"14(:-H 1sD.8). rqq "JB Ezl^b 3 Exlt trlHl¤ql Sql z|,qlal etrE gg + 9itrI.
+4 r}+r,lEl= 714^l flzl ?*zl qlEql a+ 4lq "J.&g
rqE frzlel4. ol + +¤E asE f6l-= gtrJolE-E irl-Er
6J+= Adg 6}rll Elq dB oJ6J9 ,rllzlzl H6J+. ol :r4 15D.2 HJE# #
E glll T!=ol4r +q. "lag 'la$ Eill +$lql Ble + EzI ¤, Eil Ert g(rB rsn.r)¤- ol-e" olB HI+C +
*"1 44+= *E4 '+* _tr4'e+ qeg ¤tlol+. (qqql =61
$ql^J "Jq+= r+A=q '|]qI F+e z}^ll* zl^lg eg +
E6H^l ulflzl9 :zHzITl ++ flq ^Ja
rll :z +flql 9t+. + Ezi Eq += {^dEg e=6F= e=rl= olBl d-
^!i]]
L_aJ EII
bel ')JL
uul= E^l-
o +q tJaJ4, 9,
-)
fal 1sD.7 IEJ EE= trl.aFlEi EU olLlal dEll tr= +EollE el= ral 1sD.e +^l7H tEJ= Ll.EtLH= 'Jeq 7Jtr. b7l aÊoll E[+ L|.EfLf=
BE= U"J=E r
:dtrl-. gclLl= qal ,JE= /.l0lsl
T.l-Lf LfElLHIL, ++lsl Bqe fl7lal
elol-Lr ilrtl lEJr_+o1 +^l7H LEJ4 40lrl. 0l talr_toll^1
=g
?lal qEJ¤ gqoll 6H'J:Lrtrl,.
=C= ,Jd= czJ lllTl= -J^l6lzl ul+Gl=trl.
612 1s EtSEeJtrt
ol6J 4Etr_ + glzl Elq glq^J ^J^dEE 4E +

"lF^lvJ 7
6
E= +$$ + 9t+ "JÎq= EzI ¤ 49 Ez]¤9 "llHzl 5
4
g6I= E}le- aAB + flqq(ela4 sld^l dE tlile+
=
a¤+ r=-g rAi^j ¤+ 9lHzlE a¤6Er, ellolzl$ ol
3
H4l
s"6I{ {f t}el= dq4ee a{6}j4 e. dzl1tg ol+6fl 2
rJ t"le} H||6&g ol+rll g + 9ltri), olfl+ HfE"l +=ql

qE ¤6Jg Eliljr, E+ q
^Jcqq +sE- "J"J"l9 ceql v
tr g6&9 ulzllzlg ¤+ts + 9l+ 0
.f.g 1sD.10 o+CS-+Co+s HJSel

8dE?] COzf t-fl$E 4elC El'+
(a) UBC #9 =Jrl "JBA TIE SEllE COT| HFJB Es= olF;' 9lrl7l EB SEHe galqE^1
+E nl=
_H,\l.c= LH=71 nflEoil LlEl'Jtr[. TIE 8EtlE grtl4 7Hi.il+E LfEt
6J HlHg 4e-ld trltrt,Jts
^JCEel 9lulzl EE= a^t6|= LHr, E^{E +^l trl¤xi= +8El= Eol= LfEtL.!E[.
EoltrI. ol ,,JHql^lE E=E tlti ttEl]el Exlzl EtqI^JEilE q

E"l-zJ 41 qLaE 4e.ld aÎ+tri. ol
ÊEH¤.
HdEE ^ll7lE aÎ6tE ^JCEq qBi TIE tr4E9^trJE
= zl]zl]
t1-'H4 d= +q¤- Boltzmann Bs^lql r|4 zl^6: ¤#+ a
+ 44.11fl+. ol s-qE rse.z^l k,=No [io(e)u,,,f (e)de
+# ac6J + gl+(rB rsp.ro). E 6J 7l^lE HlHg eilol
_o
r.l-+g EBg ol+6r= 4o14. ol HJHqI^J= EllolzlE ol¤- e r-ls-r+ tol 448 + 9l+.
^J^dEE 5C6J dE fld =+l=
6L"l E=E7ll qI q-g.ql ol
k. = (oiu..,)\ (15D.2)
+3 ^JE]]E+E +s= ¤=Jg EqEl6Iol !+ tl+-sld tr"
49 z1lz1;g zlzl:t_ 6ll46]]U+. E+ 4t Ez}zl ar+4 o ¤zlrl 44 ggE Boltzmann *ld¤ +4\U4.+xi g u*
E B'J¤- 4+zl *ts trll= Raman E+IH(Eq rrelg o13- %r-Hql^J=HI¤¤E a7l {lEll n o +PEl ^JCEE al+ ^JEll
6i"t Hl+E c4g Eqq+ + 9l+. n'eE-el Hl*C d"lgl ql6J$E}|-$E]| EE4 on4 AEfl-A
el| *s.8+ k,,el 4l'Jg ol+6}q ol +E tF+E a+ EJ A
E+ ¤* EzlE ¤+6i= ql= qtsxl 013tr](Mpr:
multiphoton ionization) *89 ol-$alzlE oJ4. ol MPI HJH
g6}rll +48 + ?l+.
ql^l= ql EzITl-94 *{-3 g+6.Iq, g+q} *zl-59 drll
knn'=(o,,r'ur",)No dEll-dE|.| +E d+ (1sD.3)
9lHzlzl-Ezl.9 "lgs+ qlLlzl_H_+ ull= ol $zlz| olgsl
= rflH +E d-+ k¤ s= fl+ ^J{e+ Boltzmann-2ffi aj9
¤4. uplel ql +.q¤I H¤e EB +EfrI ol8ilH(REMpr:
resonant multiphoton ionization)9-191, ol HJBq,tJi alu| Ei E +4U EZ z7l ^J4(HI¤¤-==* t4 Ss. rql^lE r+
r ol^JE EzlE dxl ^}4E EoZl ql q-sql +=
rJzl--E-
+ +Eql 4-E zHzll+E 7171tr llo p +)ql aa +E ^J+
*zl-E +7ls ol.$all.<J "l E= ^J4E+E] olg¤- ^Jzlzll oJ 59 ajeE +Elu d"=x tL4 +E t}+tr+.+
4. ol REMrTE ,*4+ Eilolzl tl545 5C+ Ez1q dzi-
tr-Ell ¤-+ qql E"a^la + ?lzl ullEql ¤e6l+ r}*ol fl k,-}k,,,(T) f ,,(T) (1sD.4)
6l+ HI¤¤ol+ d¤+g Elgqs g+6J + 9l+= ,n
=+^J
4o14. {zld f,Q)+ gE Tql^J9 soltzmanr, "Jz}tr}.4+ o}H+l6J
olgEE 4E Bs= HJB $dE gSEg "l+6lq eC d= +E* =zl "i 4+ t}4Eql 'l]+ tr-El]-t}4 +H4g
g+ 914. ol EJHqI^J= 4zl** ol+4q ^J^JE olgg aaE+ + 9t4+ 414}ts + glsH Hl*ql qlql +E tr"+=
"J%I ^=il +e-a 7l+^14 olgEol ^'=flq +44= d 4l&.J + 91. 4014.
# d6}-eoJ a-^l(CCD: charge-coupled device)E zlxll $
ts|^laq. zrElEt oil 1sD.1
6J aE+ dt-ztz} re+ E"J+ +.n ¤*4 e ^J+E 4=
(b) $E11-gE1 U3=a;_E += rl+z}e+ +=++a 6IzI. +g "JEE ++lE+El
Eq lsAql^J 6E=E4 ¤+^14 CE +H4E T}IHS E"J E4l tlFxlE E"J+ qqxlzl _s.Eqr
^J
=9lErrJ =E
ai HI 9leq, 2il-HI+ +E ^J+ /c.g Hl*C += SH44 461-E +-zl9 tlEol E#: ^JEI_tr-ql +E t}+zl Ez u
150 Exl#el=Htrt 613
trlEJl¤ ollL1^l
el u' t4Eq r-|]614 k,,t= k?6,,,21qq, ,(D - -vhukr1r1,
tszI 41tl +H]] e'+ Eq 12B)"J trlle_l gs. rql.<-lE d
=
ill4 +E *izl r+q-r} e."1 ¤4.
tf 7-t
k,
q ,L"*t" (l u,
Br. Fo,
15D.3 trlE!¤ ollLlrl t'E lal t

H+Hr-+Hr+H
sD.l 1 Hel H2sl +a fl^Pl E"J 4.lc8oll ++EJ it|e. golLl=
îl trlEJl¤ ollLlIlEE.
HJSOI EII-LI
Ez|gE dE er+= Eelotr ^J=|] tI=|] +f1 t$4g 4l

t6l-= rll peal 7l* +9-e} zHHg 6I+= EI+q +o16l+ lsD.12).
E= gzl¤E tr"'il4 flzlE Et+E +4u trlHl¤ qlHzl,4 RorE SzlalH.! Ru.E Es}^la ,lt ol s.Hgl
Zt-e-e
HI+E trlEJ!¤ oilL1rl EEol+. qfl¤ ql',121 _EH3 de ql
=
+E|+* ElHl¤ qll,lzl H+= +49 n, +xI9 46J ?Jo)71
olE]E+q ++zlE 611, "Jzlqql4 Zl& er+E+El +61 HR trI ^JzlE ElHl¤ olluJzl Hs+e+ e+. qlE,\-l Ror=oooll
zlr a34(Eq eE). olE-ztuJ$g ole"olej$ ¤fl zlalel4 ol g.Hg z|-e.H H,9 ¤6J Elfl¤qqzl +dol +g+
^J
HlJgg zfzla_ Ale-l qlt lzl= ill4l4_e-e 4l4}6lloh 6J+. Eq E Ru.zf q+61 *ql^J z|-=E +49 H^H, +zl-q qHl
1al rJZ SEql 4l4i ,JHg ols" 6I¤ ExI4
¤Bt =
eEql^l ¤ qlLJzl *dol qeq.
EzL qaJillql^l .\e zpty?la+ trqa+ 6l+ z$4f ,<|ol
E ^JE++91 zlqlEl= dz} t**4lE r46li +qot ++. zlEJEt q 1sD.2
olqq} dzl. ttS*AlE Aq6}al dqB= 4l4}g 6lElE
'll 2ezlE HI* s*or+oH+ot. ¤i H}+ql^l +3-* q
+61 a rlZ}"l g,q6tq, r46}q ¤41 f69 olE al&ql^J 6Jg +trI. ol +¤+ Ho, 4Hl¤ EHr+ +F d=C RHo^
E u*Hr+Hr+H{ H+H2o+oH+Hrql^Je} Ag Hlr4 el Roô,oll El]+ + 4q- zlzlt- +48 + gl4.R*,o^7I
+++ "J"J"]E ^l-olel tI*"JS +l+6lr :14. "lag qill q*61 Q= Ho, ElHl¤ qlqzl9 &ô,ql q. Hs+zI
¤e4 ol$rlr ?lEril, ol "JBql^J= = Ezle-l 46J 7Jol7t He- trllel iilHl¤ qlqzl
6l-71 9-16}]^l HI
'JBol +4¤ 2*r
i{Hl¤ qlqzl EHg +C6l-=trll 4l4I A$e+ ¤E u}4"lel Hsle+ ,JEI.u|$zlzlE Rro^7I ql+61 trlb ElHf¤ ql
E Et4l ole"*4. =
qlE 5q^J ElHl¤ qlqzl
qzl +E"l +4¤ oH+qe9 EzI trlQl¤ "llHzl *d
ÎolE +E¤.
H?lzl.e+ H2ts:zl ol gtrl.
EHE 5Ag ¤H611 tr41+.zt^llq} 414I A!+ql el6lH Hi+
I "Jezl= trJl gs+ 9lHzlE nogxlz| Hr-H. +ql q4
d=6Hob zl* qq, rq6lq z-l¤=ql= "lBl6J +"Jd
+41
^J
^JE +Eql ^J4I++. rBlH Ho-Hu
ql6H^l"J rl."l9 44
Rorel Hr-Fr. r}ol9 44 nr.E F u}4"lEl+g zlzlr Q
7J A?-l# +49 + 91tri.
+501 ^l+g 41E Rorz} *t401-r, RBC= HrE BB a Br.
R ?"lE *=+. rTlr c*4"J HI*^d +Eol "Jqt +ql

b Rr.z1 ++qiolr R*E H,el *J¤ ¤aJ aolE TtzlTll g
4. olE 3g^t 4lel dnl {lHzli r.q ^}'H4 4"]q E
EzI +llse'f ol$9tr olag 4ltllt f :i4. ol$ Bo,
=61q,
,ll +6J 4lE dill 9lHzlE Rou$ RBCqI q6ll^l E;.lai$ ol
f.al 1sD.12 rB lsD.l1el ollLl^l EEoll q,|36IE 5^ld raJ. R"E Hz
tt"Jdt}el HI*ql ql+ qfl¤ .|uJzl Etsg Eril g+(rH ExlE BE e-E' aol(E"Jdtll "Jdl-E I1BE A^P|. +e!61 Eal ?l= ttllg
1sD.l1). ol s.Bg "JHl4eE Eild l3 o + +E}u+(rB ,J)= LI-EIL.IE1..
61t, 15 U8Eel-qt
trlEJl¤ oilLlrl I
I
R6L
c*
Bo, Rr.
0
Ro, feJ 1sD.14 Eol 8Etl= Af utl^l=o| ¤a4?l u3¤ fl4= Elal-
^1lEsl
717l 916H,\1 57fo-t|0F 6l= 8Et|(q7l,\l= E+¤^4oe +EF.! gl'88= xlLl=
f.al 1sD.l3 :1eJ 1sD.12E trlEJl¤ ollLlrl EE= Erl6l.= qa1 u3 3E
d0ltrl-).
ee A= RBcTl g¤6f1l 8^lElE^1 HATI tr=El= 3e= LEILI|Z ee B=
=zl+rl RBCT[ =q+= Ae=
HATl E=Elts LlEfL,!trl. ].al-L AE C=
trlEJl¤ zl=E Hl._f= qal7lts ee+.
146lol EI¤¤ oJezlTl +l6fl^l= qltlfi qlLJzltr-+ gd
q dill qlqz.li_ zlzlo} 6J+. olel+ A$e ¤84" +
+E=$Cql,tJ flzl-5E ¤z,ll AE= olEE dAl qlq z.l,
=
++ g¤E| qlqzlE olE4 o e 4l,lI.J ?Ield qlqzlE+
3E 9lulzle+ trlQl¤ qlLlzlel oJql E=++. rBl+ rz}4 = r+.
E6l tr-'J6l
o 4 AlTl ol+g + 9l= AEE tr]fl¤ qqzl"ll 6llR
fl^
6l+ a.tr.Elg rEldlttrI. qls^J HoTl HBHcql d=6J trllE 15D.4 g:dzt 4ltte.E+Et E= 'Jal
trlEl¤ otlulzl Eslq}g _H-ts aol+. "Jg Ho.7l d=6F= a
Tlql HB-H. e6J z)olzl "JA6Irll +zlq$ H, ElaJillE El "JzlEqI4 E]'J ¤tlol +61 +i gz}4 dzt old HI¤-4
¤l¤ qq \zl tfl 1sD.13E d eE s^l+ As= 44 *zl ,J? 4+ HI+Cql g6&9 AzlY olzlu3 +d qzl^J=
ts 4o14. r46}"j HoE EzI oJeE "Jolts"lE 4lE trlHl
=
ojulol$ol trlHl¤ -trEt]-q^l +4q= -LLd4 +ll4g ^J4
¤ qlqxlz} u1l$ +olA+z} H.zI E4 trq4 4ztE^J # qi+. r?-16}0l Hl¤¤e+El
^JCE +e_E C+4s-e Hq
46}al eaa}al ¤+.+¤ HoTl "izl H4 Eq4 ?lE rllE TlqH E{¤ol +Eel eE qlq \$ zlzla_ 9lq^l .JtlA
HB-Hca6J aolzl *zlt;lAl El= 4= ql+ aE(B)= ^J4 Tlzl $t\23 + gltri. trl4^l t}.ll4 d= +E(EZL ¤q +E)
E +E qlcl. ol$ + HI+ AeE$ Ezl-$ol iJ+ql ++61 e+ rlEE E*: AEE- He+^l7lE^J HI+ol .J94EzlE ¤
$F {lHzl$ zlz\zluf, at$ Ezl#o-J ag olrlzloJ ,tll iila E tlE tr-4el ^JcEol +s=zlE $eeal {Q
= zl .sE9==
flzls +3 qlqzl ¤9 o + zlzlt_ zl} 4Eol4. -5lo"h9 ¤E4eE
=Îg +
gl+(rH rsp.rs). ql
7l**Z "llHzl9 AE= C-tr s^lg {+e.<1, q
EIHI¤ _tr^J EzI ¤g 7|zlr. g + 9l= + 7I^l fl+= el* tE"l
7l^1. HoTl d=+ql trl.4 RscTL.q+r HueI9 Etlol ¤ glHzlE zlzl:il_ +E6lE+ 6l-= a4
'-ll=JE Ed eE =
cqzl ^146J+. oltrll= Hu-Hc aoJol d=6l] e-= gz} ull dE qq zl$ zlzla- +=6IE+ 6l+ ar+el qL +ol HI+
Eql olsElq, qlqzlzl-oJzJ _E"J 999 c* s^l7} ¤ ?J8 I "Jezlzloll rl s44ol,t= aÎ6l+ 4,"14.f, zlf,q-q
Ellz) ftzlalz1a! ++ A+ 4A trlHl¤ "llHxl9 HI+ aE EE TlF tr-4E HrHi Ezl¤ zlzla_ ^146k ci AEe+ r
a.P cE trl4 ==7(lzlz g4zt4 "Jtldg 4a += EaI ?-ln di] qlLJzl= *zl"J Bd eF {lHzlTl z cI aEe}
=
7lE tr|{ 44zlE aoJtrll, ol 44"+ AEql^J HcTl-trq^l E qL +ol q s44 o + HI*g "Jea + ilE. 4"JzlE
4zlr- ^l] He-uu prlol B¤ ?ole ¤q=q-. ol {ez} u} B= aol+.
e H}* 3+s+.
olxllE ++ +Eql +qI d"l r}4 olE(Eq rsc)g 4+ (a) 84 'J=dul'Eel
qlLlzle+ Hl++ dill qlqzlE zI4 ull
^la + 91trI. "J+d :.H rso.16g Hgzlzlurszl¤ t"lel zJEE t46ir r
E trlQj¤ {luJzl sfltlE +ll4g ol$all.<J 444zl{, dol ol]"l-4 H, ¤6J3 44 ?ole Ssl¤ uI9 qfl¤ qlq
tr|4 "Jq+71 916l]^l 46110} 6t=
4 Al
^JEH= tl¤-ol 4 +ll4¤-
rao
& ar+= Eol+= 4,o14. qHr¤ tlqe *ql^J zlz$flrJ u|

"J4l ^JEll +ae+ eg aol+(re 1sD.l4). slHl¤ qluJzl E e+ ?ol E"Jdtr-ql 4+^J f,t49 oll zll"J 4ltr1. (r+t+ +=
Etr-el .I5+E +J4=e zld ?l+4t421 &*zlzl ?+sq,
4IEtr+qE +4E Hl¤¤ "Jsa + gleq diil HI* +E
rso Exl#el=al-+ 61s
F-
Br.
I
) H
H
(a) (b)
.f.EJ 1sD.16 H7l dlol-d .4 4E= 7l^la- Hroll d=Ef nll LIE1LI=
Hl5'Jd trJEJltr oilLJ^l EEt E"J 4.lCgg 7EI |_*3 qE!¤ gEE
LIE|.1.!E|.. 4 g^l =rl0l
Hll:efoll EH6ll,\l HJ8 rtE.oll n[= tr1EJ!¤ ollLlrl=
LlElL.!tr|'. =iNe
c3
(c) (d)
g g + fleq, E6J q}*ol lps oJullql ¤Wi= oJ
^t¤E
.r.B lsD.ls dA4oJ EJ'J(-)II Hl.5E4?] U'J. (a) ci-= Zl+E HI'JE + 91tri.
rlel-7l.= ee (b) cI= A7f Tl= afEHE BC Erloil tr=atl.r1 Il5 arEtlE AB
E^Pl Bdcla Ll7lts 3-e; (c) C3= A7f Hl-tl5 8Et| BC E^loll
EEJoI^1
C7f
EE-61= 'JE?.lr]l ETI EE oilH^l7l'E=+:d 'J? (d) c4E A7l t]E gEHg
(b)flal¤ "J ugc tr1EJl¤ oilL1r! EE
BC E^toil tr=ap e-e?.!r11, ollLl^l+ TIE +lg0l HJ- oJezlzlql +4a EI+ql q{^J= .|Hzlz} {+ "J^l_e-e. dil4zl 9S.L+
3+= LfEfL,lEl.
E= rqlE Htl gF %ral-"e. Bot?l=+ql +6H^l o}l+ "J
ed-+ qlE^l F ur +zl^= ++cal "ilHzl9 + tsl]+ q= ql
ql 7lq++= ag Bd6]lot +tri.) *ts rB 1sD.17g clg HzlE zlzla_ 6'5^l4E ol ollHzlzl d+ Hd gE "llHzl
zlz| 111$-xlqld=g trl "Jq+b slfl¤-qqzl HEIE *4 E 9lg trll= HI¤¤ "Jezlzl ?*=+. F+HCI+ct+HF Hl*
u 4ol+. +A fl4¤ E4Al+ HI4 lo.9 ?l+ oJe_E *4 g a+q= aill qlq zlzl z;q4s Hclol a4l1 H ]==E. TIF
6J trI ElHl¤
^JEol 44zl ¤4. "l A4= +=
olEE "Jill ^JEHqlil¤- oIzI Hlq 41:t ^J4q1 flg trllE+ +{ Hl]+ m}
"JzL4l^}4 +^16I+= ag +rL_,6I¤4. e. +=ol ol HI¤- sril HI¤¤ "Jea+.

d ?l+ "J"ll Eqz}= aol olul= + ¤;E="I4 HI¤¤ "Jezl qfl¤-qlqzl EHg aÎ6l] EE olq* eaEE
=gg
zl= *ql+. "J + 9l+. rg lsD.rsg HI* alstr"ll 9zlzJzl "Jzldol
+Eol B+rColq^J HI+ +=ol +Ea6J oll, rle EqEq g'Eg +4U 4"14. r4r:aH rsD.re=
'+e}+= ?l+¤
qd6}4l qE d= ".L6J"l sd6l -?9"lal4l qq *Aldol *rll +++= U'Jd EEg +ElB 4o14. + "J6J
^J ^J^dE
"JBC"J EEg r HIE]]
g + LCe] HJdJqs +e}*+.+ qdg d+ ql= "* lpsz| o+ H}6}eg= HlgCol+.
arlq, trr{^l olEtrI 5}g ^lA olqlql +s.ol p-+H !}^ds}
E"l "li] oJ Eldg 6}zl *6Fr E ^J^dEg HJt6Je_E
=CqI q1+E
Flq+A+. qls^J Ke+ I,elE 5-5ql^J= ^JCEol d
HJe_s Flq+aq.d%pr+.+%pg e* +c 4l-s4lql^J +
,a
'o-b
7
E H}¤{i=el e=* +dql a}s ?ldol ?lr Ez|pol gdql

9lg ,ll +=ol .JqlJ+r Egtg ollel ,J6Jg "J*4l. olull
CI
oo- a71
o-
^-lax1
el C^dE EE= g|?-lql^l dol t4zl-+4+= +g EllTl-
q={Eq lsA)4 +'Js+ ole+ qla4_oe. K7I cH3re+ +
EB Ell= olE +ol trll+61 zlztsl d=6lloF H]+ol gqw}.
ol ollT}q+ql el6IH K7I qEBql +E=61+ 44 ?l" olull Hl,\.lExl o-
"lOo- =.71
^JC¤ rlz} F*c-s Flq +A+. ^JCE9 Ba"J6J 4E

ol
lH 1sD.17 Ctol 61q1 tr=g nlle-l trlEJ¤ oilL1rl 88. 0l e+ql= H3xl.=
EE= +A6IH HI¤¤ "JezlE ull $eoJ d= 44e+ uHaJ EaJul.= flg ?Jo-E Clfl^Pl tr=6t|01U30l "JqH + ?ltrl-.
616 ls HJ8EPJ-+
9 szl$t'l of,$fillzl &4zlAl g+. olqoJ {E g-5g. H}

+41= "J*4t*21 d|l "Jq gel^J ^JCE 4l+e_p EA=
4. "l a+ql= ^J^dE Ezlzl E=Ezl ?+g dE ^Jelql glrll
g+. trI4î Hlg^J trlHl¤ EHg *= HI¤+ tl5 9lHzlE
C 4"J_oE_ 7l4o! s_r+4 oe "Jqg + gl+. olqt qlE^J=
H+Cl, + HCI+CI Hl+g E + 9l+.
+
z].!Et oll 15D.3

lal 1sD.18 oJal5 rqEJ!¤ ollLl^l EE. ¤=i4 "J'J(c-)01 gGl+alE F3
gI] A= qlLl^l7l =Js6lq, tlE AfE}lel 8¤E0l 8Ztl. H+cl,-+HCl+cl HI-&g Hlgd trl¤l¤ sHg *=+.
=E H+Clr(u)+HCl(u')+Cl HI*ol E"J'J dTll qlLlzl== zlzl
;. cl* ull (u,u') r+cql trl+ "Jq+= a+E ^J46l] Ezh
(a) (0,0), (b) (2,0), (c) (0,2), rElI. (d) (2,2).
+d?lq^d EE¤. ,Barol]szl-(rH lsD.l8). g4+El E- "l +q^J HI8
E llE ^JEHql 9i= +zte+ "Jrt flzl-7} trlt= HI+41 +E=g +l$"l E-E_r. Sd+E=g tlfol E=Ezl ?*= (b)E
=L5E
71 4e c. *ril ¤4. oltrfl= HI¤¤ gqql^J zJol sl6lr+14 t}$"l "Jqg ffio1 ,IeF t+.
7l q$ql "J*$t4zl drll 94zlzl *ti+ r*l+ eg "Jq
9lulzlTl 4+ HTI qqzlE 9lg tr1]. H}+4lzt c,-. tr+{
dal qltld¤- Hq ^J^dE ¤9 " e EqzI+. El-+^J "Jq^d (c) 2tr19-84 tlEt olE
r{Hl¤ oll,J zl sE{ tr|{ "Jq+= EI¤¤ t.lld Hrl +E ;laqelg "l+6IE tl*
9"Jol59 4E, d-.-|14 HH6J, t:i
,J^le-l
"llHzl= 7l4ov s44_"_e. q}*ol "Jqt+ s"J oi ql+ qqzl Eel zzl zzlg olezli flzl.
"l$alq HI¤¤
.-14 ol trlql¤ qlqzl s$g -H-H ol +ll4ol "J+ qlfldg E9 HI* +llE. Al4I4q HI+ql^J "Jq+= r+C# qq
Hq^lH ^8CE 4l+el 7l+s qg q4 g4a ffi ol$z] +ql^J reJE + 9l+. ral+ ad4 +ll4 4l^lql^J= flzl-,
4 E_o e ez[{,<1 4l+ "Jee qez}+. Hh+q ,5otH
=B]
dzl "l q ¤.E +Fol "Jzl-EEg zlHl]= g=+= Îdg
^JdEol =E {f ^JE{E zlzla_ ^JAt+. _r.BJ6Izl ?+r gl+. r46l.q ?ll4E ,H'J trH4lql i-l¤. tL4E
q-gql= HIEC sHg .Baral].BzH-zB lsD.te). ?ll4 cql HI¤¤4 "Izlq'- t}EllE ^Jc+g '+4.+l= q-F++= ol+
qlLJzlTl +e B4l ,J^lol+. ¤-E +=ol d=6.J 6I= "JBg oJ$-allo| alt 4,o14.
^l= +5
ql u++ trlQl¤ 9lHzlzl-g+t+. ol=e 4l+e-l *e¤ E .J +q{ ¤-Eql^l "Jz}E+4 e H}* TJ44 +E t}+
"
g
"++ &4zl4z| HI¤¤ ¤9_"_e. HI^Lqq EolA+.
r4 E Ed6tAl al^l6leJH HI+41 +E 4 flzls+ +471d+B
6Iq qlqzl= Hl+3 oJezlTlql ++6Izl"J a¤¤. szl * + gl= dz}, dEo, "t qd tlEll# EF relallo; alzl ull
6}rll ¤+ EI¤ +{4 c.ql^l= H}¤¤e-l qqzl "JPz} tl* Eql q+61 zl+6l.+. ¤ltr-4eE= "Jzlqq}4ee 6l+q
BE|]E 9leq, ol+lal {+ trll$ql Hl+alr| !l+E ol+zJ+ tlEHq fl= "J+9 Exl# 6t+E i]|ts(AE)E AE+
= :z4E
4. + +qd s-Eql^J Hl¤¤# +44= "t3 i]].-J
E4 zlê"t ^8¤E# +4,]1= "te iH'JEol glAl 9Erll,
olq* iH'J= 6l+qzl"J +E a¤- 6l+
ÎolE "JP dolE
gzl t*E+. g"J otq+ d"lEol E+ slq} HI¤¤ "JezlE
4,9 "Ir-l+. qlE^J H|+oH+Hr+oH. 4Cg Hrel oH Î
C* olg "lluJzl dol"ll,q :zzlzluJ Hr*+oH+Hro+H r+ag
slE HI¤¤ ++U+(.s^l= dol t4E +4utr1). rflql
ol ++6J +flz} AIE A+ql^J a^tE yl-rEio 6J+e+ +E
^J+
ql +.J "JzLqqL4 4l4}g q+61 $1t-ajq1, a_ vlgs_ El +
fal lsD.le BJtlJd trlE!¤ ollLlrl sg. dg4 oJH(c,,)o| oJolLl'z1E il8 "ltl 9sql^lE "te Hl+C illts# Eql^J ^J^dE H,o+H
+E1 LIE 8Et|7l Ee6|"q SdEol tsE ET] EE ollLl^l= 7f^l1l Etrl-.
zI +g f ?lzl ull$ol4. r?]6lq +s-r+ *3 -,re¤ dutl
==
BJ30l q! el +e_e ?]aldolE r HJq]+. ug¤01 qlqzl Eql^Jel +4 u3 4E Fto= aE6J+.
Etr|..
15D Erl#elEa+t 617
F1r1=)4,tr) +E HJB qE (lsD.s) dF

i,i k.(T) - J-n-trr-ukr +E d+ (1sD.6)
hq*(T)
¤zlrJ P,j(E)= HI* EE ,e+ jÎolE d"l"tl 4
^J^dE EE {zl,rl gE. rql^Jel H}¤+=9 EU]] Et+ "JE(EH]]
QR(D=
aJ s+E¤. +44q, 6JCg SCEe olqzlE E= 7l+* d 6J+E- pqe Llb)oltrl. rso.ozl3 de4"J oJ"J +E
^J+
olql ** stol4. rflH +E tl+rl trl-*$ ?ol #{{+= s+ FfO= zld ¤¤rl4=+= E"-lE4 9"lE
"lE4oJ "J
49 u-"J + 1l+. 4=4.
7HE=
=g:et
tr l. E^l gg rl+ +71 +¤- B0r+6ll +s= Ezl¤E *lq3rlg rl-8,J EBE, trEf^l 018+H(Mpr), BB trEfx[ oltstH
zlE ExI qEol4. (REMPI), r?]r UB 8d= gtlE1 Eol 9itt.
- 2. ExI ¤ql^J ¤41 Ezl¤q 4I+ +9= glz}9q}4 ar+e+ tr s. EIEJ!¤ ollllrl E'Ee HI*ql +q6t= EE gzl-=9
^J.il4
^ll"J6J
EzlzJ qHl¤ql E=ql+. +lilg e+_e +Elu ElHl¤ qlHxl rHol4
D 3. E9 ffiol van der Waals 6Jol+ +i e6J9_E A9+ sz|
en ! 6. eal¤ EEql^J= qltlfl(sladlol t]* alE tlql "J4 +
54Eq^l "lF9tl 4.9 van der vilaals Erlelr +q. E}+4.
Z 4. HI-&C # artal-b'JHq-= 4sld Ele gtsH, eilol a 7. HJ.'lJd EEql^l= "J*dol HI* alE tr-ql *al +ElU4.
=s-d^l=
,{lzl
oe. AI
-1 +^l al Ha
EzI4}tl9 4s dI = olNdx o= ulB tI+ EH4 15D.1
Hi* +E tI+ k = (ou6)\ 15D.2
^JEll_tr-Ex +E ^J+ )\
ftn,' = (o,,'u,", 15D.3
dill4 +5. ^J+ k,=\k,,,,{T)f,(T) 15D.4

tt'
+4 Hl* +E F1r;= )rrtr)

j
i,
15D.5
Hlg
L-:O -4.E
-+
,(I-A.
O I t.1ry=J-F1 E1e-E'kr d,Ethq^(T) q-trts EUll *f "JE 15D.6
E4 lsE EgTlloll^1 ol E^l old
ol D+A- +qlEe a+4^J olgEol +o+ +e__a q&qq

> 0l Etr|E ull+.= ol3
qr^ ?lxl lolLl sE= E"_4trE +a+ ?l+.
=,_t_{tr-+H+fl E^l 0lE
lole_l
ute ?¤ ¤Et4 qg= ettrt dxt oltE E-d
"t8oil^-l =eEl
ilgEt Hl-,8=trfE +0H 4toil^,lE 6eEt q-g=:drl. D+A- -\ o* + A- (15E.2c)
> -._{c TllLJ olzll Eq r4Eql^J ¤Hql %lBg ol+6}q Aill HI*
+7H-"J7H ErlolE 4s. g;5 C^l +7Het
+Eoilîe-l "J|1 D+A+D*+A-ql Eil+ +E tI+E o + ¤ + 9l+.
g 71a:1, E= HJB Gibbs ollL1rl :Lelr flxlEel ^l0l
Ht|goll ^l
EE6l.= rll Es-d oilqxloil el=Eltrl. =¤-z|
Ee4 +oll^l "JolLl.= E^|' olEol ^-E
> Ele.:d qHl xl^l otl.^
0l Eqql^j= Eol dlEll olE(Eq lsc)g olE1ttrl-. s.-et EjE
fl8E z]|uJ(EB 7D), ¤+8E]| =JHEE 14E), :tel.I. Franck- +d dill H}¤{tsp.t^l)e r ^JcEol tsE-lg
oJ$$olEg
Condon gal(EE 11F)E o|Eeltrl. ol dill HI*E +E= 15E.2c41 o + +4U +4le-1 +Ee+ E
EorLf= a= ++rYluT.
-^!:!.-r ! A +l
-t Î:l_I
q7l^J= d"l t4 olE4 "JzlEE TllH¤- ol+6}q +.J41 u = ka[D*A-]
9 Ezl¤ ^l-olql 4zlzl oldq= ql+61 zI++ $ag ¤+ olq^l+* t4l# tr|E+.
B 1o14. ¤zlrl Bd^l7l= olEg ole" ol.fl olBlqI a" F9
dz} "ld +E. ql+6J + flsq t 44zl Hlr4 eq6l E4l 1 + ++48"il Eil+ A+tlEil r'Î^l 4+
+. +?J4l DAe+ D+A-z| +EI+q olEql+ A+-^Jq
27lle)
148)= 4+^lZltrl. +d,
=
^HEq
15E.1 drt old -+= EEI
# = k",1oel - k;[D.A-] - /cdlD.A- I = o
+E +q 4 A4l t o-e+q Bzl] 6 Atr- T3.47I oldE4r

rl+4 tol 448 + 9l+. tr++^l
^J46IzI. dill4 HI¤+
kl+ko
D+A-+D*+A- u=k,[D][A] (1sE.1) [oe1= ku,
lD.A-l
+d r-tl7}q=E a t4l= D4 ez| +'-4 +ql^l q4lqq ^J DAqIE c+-tr-4 4+^lZlr}.:4H

s "JLt^l +-JE DAE "JE= 4"14. =^l¤
D+A5oo (15E.2a) # =k lDltAl- kjtDAl- k,[DA]+ k;[D.A-]= 0
k"
ol +6]¤qlî e= olEg HI? E g

q-gql= ol
^lE
a^4 6J¤. r *E ^lel tDAl_tr_ zlQ|.r.14 tr+
De+ 4n-l d"JE gr+
^l-olE
q4 gl+r ^J4tL+. olq^J ol +6.JE "Jql^J {z} ol{ol ee 49 e=q.
.Jq+^J D+A-zl + (k'"+ ko\k!+ k,)[D.A-
^Ja+a ^J4++. k. tDI [A] - ] + kj [D.A- ]
k"[D][A]- [D.A-] [ {*;,+t oXkj+k, )- ,.,

kd
DA dk: D*A- (1sE.2b)

=
l-----E' ""
lsE tg4loll,\'lel crl old 61e
(ki, +ko X't]k )-kJ,k k,[DA] > k'JDAl"J trll= k,=k^zl qq,
= k"[D][A]- [D.A-, ,
'- o ^3CEE ^J
^d +E= +"-q +ql^l +6JE
DA= "JEol4E e
q+^l g+ og +Eql g6I^J zlEH¤+.
q-4I #
aJ¤ h,lpAl </c'JDAI'J ,1= k,-(k^lk)k,,-Kk",7l
tr
[D.A)=1Lu,*1ryy*1r,1-1r'",1r^tD]tAl qq, K= q&c "JBE BB tr"+I. ol r+ag k, ffi,
ql E6H^l zlul]g4. - DAqdJEql^Jg dz}
\^\.': ,,
"ld
-=,,,,
k!,k!+kok!+kok,, tDltA] E +lCarl-"llulzl9l E6ll^J zluHS4.
cJ4l2 +Et+q q+^l

dill HI*E +E= u=kalD+A-lolq, ,'|+^l ++4 ?ol 4 15E.2 drlel El,-J ESel E:g
4.J + 9l+. 6l]4¤- q gd^lzlzl $la1l.<l dol-/J.4 olEql^J gg
9E
h, *e-^'GrnrE
oleo oJ4. a+GE gcs| qlqzl+. trl-4^l
Gibbs
'=koU-Ltlt^t<'Jt<^k-tDltAl Ezll= Hlql tr-+e+ a+c= +6lloh d-= aol+. :z=la[{ {z}
old $Aql +6Hî R.A. Marcus, N.S. Hush, VG. Levich, l4-7
ol 43 u=k,lD)tAle+ t"J+ Eolq, k,ol +*4 ?ol ¤4. R.R. Dogonadze$ol 5B4e=E gd^la ++4 gg + +,q
k^k"rkd k^krrkd olE¤.

t- _
- T'^k',t+li(+lr-ll..t -EW+EJ+ER '.ll+E "l+q}+.
'\,
dzlt ElHl¤ tleg FI+d-= qE ¤tr-ql elafl,t1 o16
q=ql, ol tlqE tolb f$fzl o e DAe+ p+4-el ol-e
E4! 3 +l C4
^lE EI qlqzlql Edlî acg+. dz}9 EIE Fr+= /r.,"il
$!el +Eel ezle+ +E= kak,E +ts trl-g Ct']= 6}|+
^lE
E trl+r+ ?ol 84. ++ ^l +E *i
zzlql ¤'&9
Hlql
=+.
+.JE DAe+ "lag Eqrîr 9l= +rl] Ezl* 4zlzl
,-
*'- k^ oldlzl dql +a z]]Hl|gg ol$rl. olfi xlluflg$ +fl
k:(k:,+ko)/(,ko+l
¤ qlqzl6l.-r. s= H]+ Gibbs qqzlql 96ll^l L+G7l
a+ q-s=r+ ee e4= eg + 9t+ eas+.

Franck-Condonflq(Eq llF)oll E6IH dz} dol= qel
ll
k,- k^'
k:
[,t- [", ,- (k',,+ko)
t- [d + uqql +a7l q= +,r+ H6l-71 dql ql+61 4j+6}4l "J
--_-l-
qlJ+ ol g?]= DAE 4zlzl D+A--tr "1¤:6I= rle, DAq
trl+^J +aql e-l=61-= 9lulxl .gH*o ++El D*A-E qlqzlE +4
,ll= qlqzl sse e 4zlzl olEo 6l-b 4cqlE 4+g+. +
+ElE(qI+ +.JE DAe+ ^JC +Et D*A-)E slHl¤ "llHzl
+=+-#(,.f) d^l old HJ8 +E 8+ (1sE.3)
(H ciuus qlqzl) sHg arj} {5ql r+¤} sEcg ola" o}
q HI+ als qE. zlxlt- I+EI'J + 9l+(rH rsr.r;. ol Hl*
slEE 716I+4 7a flrt= +El.'}l= 4ee.q EzH, az\l,
ol .ll+r+ +._4ol{ +E= Ae6I
+ql^19 dzl r4r e" rll9 +ill4 ¤.E- "J4g LlEI.ll= 4o14.
^le-l
s"Jg Fe6l7l +14^J D+A-el +g Atr Aezy o1 Franck-Condon gqq E6IH Alzl 4zl oldql +Hl9q
=
g_q-E 6Hqq= 4,ol4l zi{allEz}. 4 ka)k',.,, Ir}4^l
HI¤¤ -EHo e+El ^JCE EHo + Hqe 4l 4E3 "lzl
kdlD+A-l >k'.tlD+A-lol4l z|{ollEz}. :24ts ++4 eg ufl$ {ffi "JsA,r}olz} fltr}.,r}4,<l oA9 ullgol ¤4 ,q
e+= Eg + el+. Fql E6H^J re lsE.tel qr,+ + s$Col :zrla[!: aisql
sg trI 4zlzl olde + 91trI.
+=*(,.f) /c.,ql +6J
^l
+E Hlzll *+* E4 o + EE pn +qlE'll
+ql^J HI* alszl q+41Sg trl 4zlzl old6}q HI¤¤ pa
7I
^JCE D+A--E
q= HI8 +EE AE= +4U+. ol r+A
620 1s uSEaJ-+
DA
K
5
K 6
5 {ru
o
a El i=! o-
o.J
-o+l ^lrH E'
-o
s DA D-A- E^l 0lE
(9 '-...i (a) (b) d
AGE
f
Exl.E9l o-H tHgl
D-A-
q'
E?t, q K
5
6
f.g 1sE.l E^l olEoll gqalE DAe[ sr.4-g Gibbs ollLl^l EEe {il
cEoil r.8-d EEdo+ LlEtg + 9Joq, H+l qts z{19 zlal*4 êl
+a -EJ
E-
^lE d
EEI-= LlElLJtrt. go P:
c)
fg 1sE.2 (a) q8e E^lEl= "-4

uHgoll^1= DAE+E1 oltE dxtTl
g ol6ll6tzl 91afl,<J3 De+ A + 44 dql^Jg +q{ HoMoE tr+61'r fleq D.A-9 LUMots E^l'= E= + gt= EIE-tr Etrl.
^LolE (b) -"-4=01 s+-e ur;q= HtlEe qal DAg HoMoe[ D.A-9
q al*e-l xllull$ol DAe+ D+A-el dz} 1l4 qlqzl Ggl9l "l ^tlutlEEoll
LUMOTlollLl^l Eoll,\1 Hl="-tl^14 I^l'71 El'J +4= -stcl. (c) 4lE q6e srl
ilE ar+E rJ4al]solot 6J+(re rc8.2). iJgql= DAq q= D.A-el BE -"j UllE SEl1e SetEr]-. 0l .8EH01l l= DAg LUMOT|
HOMOT} D*A-el LUMO-H+ *+(r+
EE.2a).45o1 :zB D*A-E HOMOEtrI tsl| Etrl'. (R.A. Marcus and N. Sutin, Biochim.Biophys.
1sE.2bel q+-e*r1El= ++tr 4uHgBql ,r|+ DAE HoMo Acto 811,265 (1985).)
elD+A-E LUMOe-l qlHzlzI uliollzl4 dzl old"l 7ls"6L

,ll gtrI. relr Hln4 *+ 4=l dql^l= f¤ dzl old oll {zlrl ^tolE 44, E dzl- tl4 ¤Et
d= AE "J EE
De+
7}q=lg:.H rsr.zbql^le+ ?"1 ¤d¤ qlqzl alqg Ell-J BE fltE A4ql q6J 9= CE. +4Ll]= 44"1E, :-4
Fr+ ,J^l e oldq= a"]4. 4zlzl DAE HoMotr_+q
o -r. H:t= d=ooJ "ll9 dzt ^JEH e6J Bg gÊ <lol+. Bel
D+A-el LUMOE oldg +gql. 4l7I sslqq :H r5E.2c <i* f4]-++q Bzl]E old6l+ 4zlzl -Eorl+6l]ot 6l+ r]la
E d,s -*.^lq= Hl]9-e- ¤4. olB4l qE rBqlrJpt ?ol ql 9+6J+. 11t +ql^l= 28nm-r.B.35nm-'ola, qI¤ +
p*A-9
"llHzlz} DA_H-+ *41 qq, trI{^J nz| ffig i1](A- zl]e+ Ezl] ,r.l-olzl. EzlE ¤A*g 4l= p=enm-'oI4.
e)E relr. D7l ts+g il](D+_tr_)-tr B= aol gE+4eE

"JA6l+. 15E.3 Er[ old -'+s.8+
dx} old$ "Jezl= Eltr ¤te tr-$ zogl^l ¤Et ar+
Hli6}zl*, qzlrJE DAel dz} ul-=i"or-:- VrooJ h,*e-^*G/*rel Hlell tL++. l5E.44l o + +El.u H",(4rql Elql
=.gE$rl
4zlzl D*A-E dz} ¤+ls rl.J 545- o|{ ffior-r vrooJ 6Jtrl-. z|,<.llal 4l4I a4ql E6IE(q7lî= 4ltlg
^J+-J+)
tlqlE ¤+= 4,o.|4. VoooJ rgr*o_oJ f k,ql +"-J Ed+ 4g r+q-r+ ?"1 94.
=+ls+q
+ls dzITI oldsl= +E= trl-94 ae 4+9 xll#"ll ulql
qI+. (1sE.s)
H,t =tvooivr-o d'

¤zld AE^3 I1|H}|E ollLlxlE^l DAzl D*A-el zlal-qr4 7a
¤zlrl h= dÎ lt-rfl u1-s-orr-:-E a6J(1}g4so)g +4t}]= B¤g olFzl +l61]^J "Jq+"F 6t= Ezl xllullzloll gs6J ql
hamilton ¤t}zl+. H",E g-6l 'dxl tF4 a6J BB flt'e|-tr Hzl4. olE Ezl-zHuflzlolli DA oJql^Jel De+ Ag tItrH4"J
+-q_+. trlql¤ tleg +4{+ Elts +4 +Eg "JqI4 "e_ zl]Hl]6}4 DAE E4Atr gl= +rl] EzI9 tl44o1 z|lullalzf
*qE +ql zl+gl+4 0 + e-l=+q(Eq 7D), rr-l6tol + zl E6Jg+. lsE.s^19 ol*alrlH t++ dzl-old 4AE
84 *ol 444oF aJ 4o14. _E'Jg olf-aH.<J g.csl Gibbs glHzlgl +6J +6Hot +
^lg
+.
Hrr(d)2 = ftozs-N (1sE.4)
1sE Eg4loll^'lel Exl op 621
EJAIZ q*E ol*4,rJ ++ ^l +E a+Goll

Gibbs glHzlE qI¤¤ EEdq +^d q_0& zl?eE 14
R
6trr.E q+91 *t e+E] trL.q=4 eg ar+. gg + gltrI.
P
k.e' ^ls
K
5
6
a LrG
aatl¤1 (M* +A,Ge )'
-o G -- k,qt' = r" =
s(, ^+ I )' 4k,ql,'
AGE
I
k"(q-goP)z+A,G" AE*
ol +++ eol AÊ+g+.

^lg
0 d Qo'
n (4.G" +M* )'
rt (r=---ZAE;-
E9, g A Gibbs ollLl^l (1sE.6)
=|dol
f.al tsE.3 E^l 0lC rl¤0ll EH-d g¤nl-Gibbs ollLl^l= 4ltl6l.= tll
olE6l.= -e.'J 41.
ol E6lE A.G"=-AE*p 4l A+G=0o14, zJlH]]g .tlHzl

^lql
E.= HI+ Gibbs ollHzloll elall,tJ t}419+. ol a{oJ ,<Jfl
uJ-d
=
6IH HI+ol gCar} tlqql el6H^J Lelzlzl ?+.+.
^loll ^l
1sE.6^le- EZIE +417]. gl+. elE^J ol 43 fzl]e+ tsz]
dz} old r+CE $Csl Gibbs 9lHzlql +.J !g +E6t ofql {x}astg 4= 4eg ¤H6I=+ qFEi aq}e
+ 7l* Z}++ "JH¤- Egg ol.g-" 6lf. a?_lql, ol er$oll.r.J Î"lE
DA(Rtr -E'^lEl='HI+ +ElE',)e+ D+A-(P-E E^lq= "B
dzlgC +=ol ¤iB6l E;l BqA.\l(d>lnm) EIE Fr+7lr
= 44E zlfolfE g trll= +r-}*+. eI* ¤6J ++g 4rI4
d +6JEJ)ql 'l]e} + qlqzl EHg +^de_l +lil7} tolaJ
sEd¤ +d E_o}_q_e. +4L}]r ol59 HI* 3+s qql El]6l] {ql^J "Jq+= +EAE ÎolE dz} "lA HI¤¤ Eo-JqI Et
g +e-l dz} old HI*q 4e" ¤+. Voel V/D7l a_41
E^l+q(re 1sE.3). ralr ++s+ +4eE HI¤¤ e
^J Aa ql= d *g4+ol += ++el zle"4 Eiril "Jq+q,
ECq +idq 9l,.lE q=0eE +r ol +idg z)freg El'-J F4 +E= r-.1 olt ++* ,l?-lel zlfer-fz} 9zl 9*
Gibbs 9lHzlE +Aql+. r-BiE,
tj e6J4lE ql-tr.^l= sE}-+l4t7l 24 d #+ ffiol u3
=+.
E= "JHI4] L,M"*-B-MI*L,E +g-g E + ?ltsrll, ol 4LE
G,,,*(4) = k,Q' $ c-,r(q) = k,(q- q|o)' + A.G"
ql^J= ol dzlgc ++ olgEol r* q6J 4tg BE
{zlrJ qr= ^JCE sEdE +idql^l 4 qr"k,k.= EE ql +11 e.JElqfl4. olsl+ 4lql^J Y d<l.0nmol g+.
Îol
dE +Eg +E}rll= ^J+, r?]r A,G.b dzl. "ld 4e
DA-+D*A-el s.= HI+ 9lHzl4. Gibbs
15E./, ol=el gE4 a=
R9 alszl q=ooE+El pel ¤B A qfie H3r+R q9
Gibbs 9lHzl Hirl¤ AE*=G-,*(qil=k q3,9f, ++.d+. gC
k,el dql q6J e-l= +4lE 4=" el 7l* +gq} deg +"J +
sI cibbs 9lHzl A+G=G-,*(q*) -k,q+'Y algzl q=09E*q zl]q E.zl]E ¤4 EzI ¤Aillql eoJ^l7l= HIB so eE o15
q+s HEle- ullE RE Gibbs qlqzl HsI+ "lq^J q+ +41 7-lfl= HElrlTlE^J +e6F= aol+(qlE^J (r)ql^J
ql i+84. ^l-olE
?z]]"J HlEllH zl4 *zilql A). olqel aa 6Iql^J= lsE.s^l
E4l 1 gcq¤g 9lil q"J 9.1
.-r'c,nr6;ol ge *izl qq, "l zI¤ 4+E Ail +
^lE
B¤irl¤-a- ol F s$dol j/il6}= dql^l da+. ., .$ rsE.+zl$ ol*alfl ++4 eC !g eg + 91trI.
k"qr' = k"(qr - ql)' + A.Ge ln k., =-Bd+ ^J+ (1sE.7)
AE*
ul4rJ hk.,= dql Ell6l]^J EÎ6IE zl&zl7l -B"J zldol *
= k,Qr' - 2k,ql qr + k,ql' + A.Ge e+"h -J+.
ol !g A?-]6IH q+91 St +gr+ Ae ^lg Eg + 9t+
q
* _ AEo+A.Ge
2k"ql,
A
1
622 15 HJ8Etrl-qf
8* + LERI4RT 10
o o
9
/\I./\
d-r-
.Y 6
{c o,
o 8
o
7
/
AER
0.5 1.5 2 2.5

o -a G"/ev
o -a,Ge
I
ral lsE.s 7rt1 (1)E +cl^la zJ'J-zt ql 1sE.l0ll^1 ¤EEt ulel' 'zJol
fg 15E.4 15E.8 lo e ql8q= hk"tE -A,G"oll nl= EEdE el=E gaJE a[-crEFll cH:zf logk",9 -a,Geoll ttl= Eel. J.R. Miller et al., J. Am.
Chem.Soc. 1 06, 3047 (1984)E+Ei gfllolHcl.
#zfl-tszfl offi ,tlolE A?-le+ ,rI{^J 4HHE gluJ ^l7l "J

a6lril +zlq= 4lz zlzlr k",el .tr= Hl+ Gibbs "llHzl
ql rll+ E=E= aÎ6}fl+.olq.AJ k".o..-atcrRrr-- lnk",=
2e6KE 2-qle-qlEet6l_= ++* +ql^l (t)e-l +a= 4=
-AtG/RT+tl-+e+ gg-!_-tr. l5E.6al e+El trl+4 ,JZ 44
o
"JHE 3tlqr+q z$lt- +EE4 +Ag 6}9tr1. fzfl(El
E eg + el+. gE olE "Jdel +.J
Hl$llB 7l)e+ tsz]] e
ÎolE 4r-l=
_ _ (A,_G_"jAi?* )' Eql^J Ez}-gAalzl ES6}g-E "JA6l+. Bz]]==$ 4zi
Lk +
,
o** ^J+ r+6J s= d+lE zlzl4, q+^J dzl old 4Cql q+
sf Gibbs gflel 4::Hl$"l-tr| +s+. :zH
glLJzl= ol
__ (a.G")' _ A,G'r44"F
+'d -r lsE.sE d¤ tsc.azl$ ol$$ A4olq ol EE{E +'il
=-
4RTAE* - ztr 4fr
-
-L,Ge =AER= 1.4 eV= l.4x ldkJ mol-'9|^l +EIUQ.
^l7l
tr14^J,
,n(,= uffi(+r)'-*(*F).** (1sE.8)
ol ql el6IH ln k*(Ei- log k., = ln k.,/ln l0)E A,G "(E

EEd4 ?¤. e."3=o1=
(a) (b) (c)
^l
-A.G)ql ql6H^J E^l*g ull 6I6J
o o o
4elot 6J+(rB 1sE.4). g:6J ol
^J+= E6iH 4s
^lql R1
-A.G"=AEp7l 9 "llzlzlE L,G"zl eLAEtql trl.+ 67}6ir.,

ol +4lE HeE tl*"] trJ
"J-^J&^dol Eql
q"+(- L,G"7l R2
El gol Eql q+) +E *izt A^6F= Ufl gq_e_e Hl+ o o o
EqTpt +4 ol Hld ¤9ol .JHE 5E* sl.JEql^J

AlTl (d) (e) (f) Rr =H, Rz=H
(s) R1 =H, Rz=Cl
444Ecll, ol4e} irl6J$ql^1. dz} fzlg+ *4lzl Tlz.lE (h) Rl =Cl ,R2=Cl
adg a7l= += EzI ?J4-4+7}le+ ++eqls-e- EAS
+(rH lsE.s).
15E Eglloll,\1el t^l olt 623
=sEtT]lE!=
tr l. dzl. oldg 4 alszl ¤4 o + s5'qq +4e+ Ezl]z} E a 2. $z| uflglol oezl o*R-9 ¤B zlale}4 u}l¤g ol+E+
"Jil uI]¤9 *= Aql *g trI "JqB + 9l+. Ed-= rll $-g-il.llHzl= I]|H]IE ollLlrl+-a 6J+.
=9.-d^l=
,rlxl
ci e, --1 +^l al Ha
Î
dz} old +E tr-+ I lk,=l lftâ1ki lk^k")(l+k*/ko) C*-t4 zt¤ 1sE.3
E]ts F4 +E H,r(A'- lloLs$d 714 15E.4
+E ^J+ kn= $ t h)(n3 / RTAE* )"', H,,(d)', e-

o*
"' ^' dol t4 olE 15E.s
!}CE+ Gibbs olluJzl 6+5=1A,Ge+AE*;'/4AE* sEd¤ ElHf¤ {Hzl zl4 158.6

624 t s U8EPl-qt
-E. 71 ,\.15 tjoo E a{6}

HF9.
-l -l
E4 15A OIE
=E
¤B E^ll
DrsA.t HI* +Îel +d-6J +zzl +E ^J+ il{ nlzl} -trq¤ ¤E6I DlsA.3 ol 6'¤ olE"l .$xll zlzlloll trl]6ll^J= qB4 H6lio}6la'-+?
q+.
D1sA.4 zlg "il7iq#9 zle 5e¤- ¤B6Iq4.
DrsA.2 zlrll9 ¤:E olE"l zl4l EzI +E"Eq qe4l E+61+zlE E6I
q4.
G-^.
Jti
E15A.1(a)zlrll_t HlaE +E olEg olsa}q 0sorglrlel a*g oJ EzI9 oJ +eoJ Aq}g

#Erll gg.q} qlqal= 200kJ mol-'olr}. RRK
H,+I,-+HI+HIql qlal 2iI +EtI+¤ 4lt6}q4. +5 *Eg 0.36nm2, EBg "l*6}q /cb(EykbE 414i4q4.
+|ti e=*g 332xr0-27kg,:a41 gCpI "tlHzlb tTlkf mol-rolrl. (oJill ElsA.4(b) qB 6J +Eql^J 500kImol-'g qqzlE gg + ?lbr'll, s=rz
(1'l
r-:"1
7l= r=
e rE -k-.^L=L\
-6 - l"l .,, o.1
$zl9 6J Eao,I eoJg if,*iull g.e.* ollul zli 300 kl mol-'olQ. RRK
ElsA.l(b) zlzll-t HI*g +E "lEg "l¤.6}q +so r"llrl9 aH}* sgg ol+6}q h(E)/kb$ 4lt6lq4.
Dr+Brr+DBr+DBroll ElloJ 2iI +E
^J+E 4l{}6}q4. +E tHg Er5A.5(a) 30"Ce+ rz0kPagl^l d=380pmoJ oJE-qolql^Jg +E H_lE ze+
0.30nm2, +tI AF*g 3.930mu, rfl-r' gCs+ 9lulzlE 200 kl mol-'o14.
6E gETI ¤-42}ts ol 7l
(oJill oJzl-= ls +olu}.) "JE zoo= 4l4i5}q4. "JA-+sl 6Iql^J 10K
$ol q vo frzlelfli-t-yz.
ElsA.2(a) HI*q 4¤I Hl*C += ElE49 zlf SzI
A+B-+P Tlill^J ElsA.s(b) 30"Ce| tzokpa"llrl d=360pmoJ "J4I3r++4ql^lE +E oJs z
4 "JxI9 +ifltrlq e.2xtu22m2ol +*+. r7l:l ArJ Ca e+ +E gE ZAAE 4l&6}q+. "JA +q 6}ql^l &E7l rOK g+7|B ol
s+El *sl=Czle+q
ee+ n9 +¤ +H4g zl4 0.gs* o.osnm20l4. ol HI*q ql <lE"l $-u,f"zya1.AL+?
t "Jill "JxI pE +6Iq4. Et5A.6(a) ¤!E olEg ol+6leJB HleC tr-g ¤+ qLJzlz} al46J E,
ElsA.2(b) A+B-+P Tlill^d-HI*ql Eil.J H}SC +E EE49 zlf *zI oJ EzI +=E E¤-g goloh 6.J+. (l) 3s0Ke+ (2) e00Kqlî (i) E,=2s
4 "JzI9 +Cils+q +9ltrlL-l s.zx1s-zz-zol +*f+ r4r &Hl Ce
"llE += +gg E"l*l
kl mol-r, (ii) E"= 100 kl mol-'oJ
E+q +6'J Ae| BE ¤E ElE4g 44 o.asr} o.+onm20l4. ol +*ql ql
EtsA.6(b) eE "lEg "l+6lelE Bl4d ^JE ¤+ qlLlzlT} ali6J E
o.J
"Jijl "JzI pE +6Iq4. +zl-+59 E+g got"F qI+. (l) 300KeI (2) s00Kql^.1 (i) E"=ls
"J
Et5A.3(a) szH9 ?lzle E HldB +ztel tBzlE +6ll= nm olE"tl trl kf mol-r, (ii) E"= t50kl mol-'oJ ,I9 +E Egg E"I{i
4 rA4 gz|. ko(E)/k5=3.0x rorolE ElEq ato1 $r:izl- 94,!+? ¤+' rse.o(a)ql^] gETI rorc 94ziB r ¤¤Eol q y" 4 ?
ErsA.3(b) +zl|9 flxfe B de Ez}el rExlE edE RRK olEql qq
E15A.7(a)
zia}4lL4?
aa6il BzI. h(E)/h=0.02solE RtEg 6[o] $u[zf E-laL+?
ErsA.7(b) ¤+ lsA.6(b)ollrJ gs.z} ror ¤-4zlE r +g=ol Hv" 4 ¤
ElsA.a(a) qtr qI +=q^l 250kImol-'9 9luJzlE ?g + 9|5rll, s=10 zl-al4lL4?
Eq 1sB qftl-xlHH HJB

¤E E^ll
DrsB.l Hl-+q tr+ql^l ^J+ ag qgg ¤B6Iq+. D1sB.2 qt-zlu]] HI*+ BCs+-zluH HI¤:
ÎolE
ilolE "J:"l.o14. E 4
g¤sl{lHxlE +!+?
E+ 625
o{ -^-
L-'u
ElsB.l(a) n=0.8ecpoJE4"llrl + gzlT} zI]AEt B trilel 4t-xlu|l tI 4 zzl },.EE 44 o.rssmol dmj4 o.lesmol dm-3o + flflg qq a
* 4s ^J+E a71= ezorollrl alt6}q?+. Hl¤+=g azl t.E= 7l HI* +E dlpl/dr= rsB3^lg
"l+6l.q 4lt6}q4. 1s8.4^lg +E6l=
1.5mmol dm-3 oe. 7IA+E ol |.Ez| HIe_e += ql E"I"J6J rlzJ"l ?
"l+q} =^lel EI'JCgEB6[q4
ql
fl]LL+? ol Hl.$g 7}d6}qe}.
E15B.3(a) 2s"cE ++E +ql^l zI9 E4-Eg dB4?l +t 4l+=
Hl4l +ql^l + ?zl7i zHa6J g'IE 94}-zluH
^H}+olQr
ElsB.l(b) n=0.60tcP"J
6x10-em2 s'o14. "J4l HI+ 4?-l= O.Snm$-tr alE qt}-zluH eI*91 4
Hl* +E tl+g a7l3 320Kql^l 4lt}6}q4. HI¤+=9
=zl bE-E qI zz}4s tl-fzi 9"I4 94lg4i
2.0mmol dm-30-E- 7Ia6IH ol :-oE7} Hle--tr. += EJI g"I"J6J rltol E
ErsB.3(b) 2s'c9 ++"1 +ql^.1 eI* Ezl-Eg dB4"J +4I 41+E
41lu*i "l HIS$ 4+*ol+r 7l461.01a1.
5.2x l0-em2 r'o14. "J4l HI* 4?-l= 0.40nm{-J. a}E 94}-zlull H}*ql
Er5B.2(a) zlEol 7+7+ 6sspme| razopmt +C slql+ Ae+ BzI40"Cql^l 46J 2iI4s tfzl 9"I4 qA!+?
ACE 2.e3x l0-3 kg--' s'"J *r}] +ql^l *4}-xlufl HI* e+s-+ PE oJ
-g-Aq. Ael Bq a7l }"F-E 44 o.ttomol dm-34 0.350mo1 dm-3-o -+ +l E158.4(a) 2e8Kql^l (a) E, O) Slts +q 5q il= +E 9.tl-zlull eI*
+E ^J+9 a71= 4lt}6}q+. olEel dCE= 7+7+ r.C[xtO{ kg m-r s-t
iRg trIE =71 Hl-a- +E dlPl/dfE lsB.3^lg ol¤:6lq 4l&610l?+. olq^J
rss.+.19 ol*6}q ol 4ltig l$ol 6H4. rsr.+al$ +E6]=!- rll ol+
* Z.Zxl0-a kg m-' s-rol4.
ElsB.4(b) 2e8Kq^J (a) Hl¤Hltl, O)tlql +& +ql Eq 9l= +el +&
6J 4%r"Cg 5B6lq+ altsH Hl$ +E ^J+e] a7\= 4lt6rq4. olEel ACE= zlz] t.36cp4
=Î9l
EtsB.2(b) zJzl 41rpme| s+spmgl +^d sl++ A4 sz} 20"Cql^l
^lg.ol 27cPo14.
A¤E t.35cpt +rl] +ql^J qt}-zluH Hl* e+s-+pE oJsrJtrl. Ael B
E4 lsc troI-d|EH olE

gxll
==
Dlsc.l+EE4 g trr+el E"]+4 tgg ¤B6Iq4. ,]]eel *'il + Drsc.3 A+BC H}*ql^] C¤ :flz} qql4el 9rJr|5o1 BCg+. q¤
d$ol "lil= E+E a7l+ +Eol+? "J^lg +^loJ f ll4l=+t
Dlsc2 +EE4 E$lSn aalg ol+6IH EI$ {l7}qf;:g q$4l F+ Dlsc.4 Eyring 49 "JE= r+Ag ¤B6Iq+.
Bf :lg+i
G-\
l -tl
El5C.1(a) HI8 UrOr(aq)+I-(aq)+H*(aq)-+HrO(l)+HIO(aq)9 4g *f .(err4K)/r dm3 mol-r s-'E #"ltlr+. 30"cql^l "l Hl+ql
qe A*GE 4lta}
ol HI*ol gqLI= ++eIE ol$ ,rllzloll ql"J6IZl E+'J+. gETl ¤4.r=1ol4r }otq.
=
25.col_L olg ,rllzlzl. 0.0525oJ trllgl +E ^J+= lq=r2.2dm6 mol-2 min-r El5C.4(b) 25"C +E *#zl k.=(4.98x10r3)e-(4e72K)/rdm3 mol-r
olQ. Debye_Hrjcketg +6J Heg 0l+6ll^l olg z.llzlzl- 0"J trllE +E t =i]ql^l ol HI¤:ql 46J AtG=
s-,s +q4lq. 2s"cql^l 4ltl4q4. *=1olr-p. $
+= +4q+. oI+.
Ersc.l(b) gETI2s"coltr ol$,rllzlzl. 0.0241oJ qE HI*E +E
'lie.l ^J Er5C.5(a) F2e+ IFs Tlill^J sl6J HI¤+ 4 HI¤¤ql $oll.tl 1zl-o1
f7l k,=l.ssdm6 mol-2 min-rol4. ol HI¤¤ + B"J A6I "Jolg9 +Eol Îolel
4. "l t}Sel gdEi 9lHzlE s8.6kl mol-roltr, +E ^J+= 6s"cql^l
+E-AA +4loltrI. Debye-Hockelel +'* B49 0l+6ll^l ol$.$lzlz| 0 7.84x l0-3kPa-' s'o14. 6s'Cql^19 ¤}Ca+ dE +irlE 4ltl6}q+.
g uilE +E tl+itg +6Iq+.
Ersc.s(b) t zlzlltt rl|aq+ e}¤:ol 4 Hl¤¤q +qlî lil-ol+. ol HI¤.el
E15C.2(a) C-HeoJql^l ,Hq ,Hel ^J'll4 il++Eql
"lzl= 1zI+EE
zl E9lg^ En+e.l zzl AEZ +C6iq4. 3EE +q+H 017l7l G-71 olr|. 65.cgl^19 g-cs+ glE +q= 4l4I6Iq+.
4AL+? k(c-H)=+soN m-r-o ? ;6l-r;. E15c.6(a) 300Kql^l F zl|9 Azzl S.= g"JolTI {-E=6J'Iel g}Ca+ Sl
Etsc.2(b) C-oe6Jql^.1 '6oe_1. '8oE t'-q4 il*+ +Eql
"lil= lzl +E e +ulE +6Iq+. M=65gmol-'afll o=0.35nm2o8 Fot+. flg -tr
Ezl E+l+l^ Er+el azl ay= +C6Iqe+. gEE kq+H ol7l7l + 7l lsc.lg +r6}q4.
zlol4lL*? k{C-O;= l7s0N m-r9-E Fl-e}. Elsc.6(b) 4s0Kql^l F zl]9 +371s,= "J"Jol7I +ra=oJ ultE ++^dp+ fl
Elsc.3(a) o]..t]ltr-,il S+ 8sq +ql^l r&EÎs.eg *olg A-= tr + ul E +6|q +. M=92 gmol-' 1el-tr- o = 0.45nm2gg }:oI+.
A-+H+-+pel ag ,il7}q=:E HI¤¤ "Jsil+. 30"C *Aql^l ol +E_
rJg de4ee +qd+. E15c.7(a) *e .Jqql^l "Jq+= e=E Tlill* +6ll Hl+ql rll6J zl+
lq=(2.05xl0r3)e-(868rK)/rdln3 mol-r s-,al
^J+E
3O"cql^lel g^d3r+ fl'Jirle+ gcsl {e_eu1g- 4l^}6}qe}.
*zI4 qlzlE 4.6x l0r2dm3 mol-r s-rol-tr r gdsl qlLlzl= 10.0kImol-l
ol4. zqaKql^J (i) ++Csl flEeq, (ii) gCal 9lBEl, "l (iii) gCa+
815C.3(b) HI* e-+H+-+PE +E ^J+= k,=(6.92x lQt2)s-(se2sK)/r
cibbs ollLl zl$ +6[q+. *= 1o]a]-tr. }o]4.
dm3 mol-, s,4 ,Jg dE4" + +qd+. 2s"Cql^lE gCEl SlBrlel *} Elsc.7(b) *e sqql^l "Jq+= s=9 Tlill^J 86il HISql 4eI xlf
Cs+ SIE-Eul= 4lt}6}q4.
*zI4 "Jzl^L 2.3x l0t3dm3 mol-r s-tola r
glCa+
"llulzlE 30.0k1 mol-'
El5c.a(a) s# rsc.r(a)9 tiSol q+t¤ +rllE 30 7o -E$6f!- q+Î olu|.2e8Kql^l (i) ++csl tlEErl, (ii) g.csl slBrl, q (iii) gc+
Gibbs qlHzlE +6l.q4. lole]-tr FI4.
"=
626 r s HJ8=l-el
EE lsD E^l #el

=al-+
¤B Eîl
DtsD.r EI¤:g "J+d "lluJxlqgCEl qlqzl

^l-olel
+4lEb6}q4. DlsD3 ez} gol Ezlt qfl¤g 3 16l+ Ell qB4l ol*q=zl ¤B6I
.Jqc r*= q4
DrsD2 ElHl¤
"lluJzl -sE¤- HI¤.¤- ^84611 Etrt. HI-& qlq
zl! Zzl +E7I Hl¤¤ 844 o + dq^l7l= 9l ¤"}4 a44"Jzl E DrsD.4 4elC atlq g%IH, ellol4 +g EC"JB, ffizl. olgElH, *E +
6lq+. HlgC qd¤ 9lHzl -sE9 A+E zlz\a- ol4oJ Eel= l$ol *zI olSElB, :41
Hi* ^8¤E ¤tl$ Eol s++ Eqqig fl+61-= Ell
6Iq4. qBrtl ¤H6Iq4.

"l¤-9=zl
ol-^
I -t=
tlf,_ ffio1 "llulzl"ll ++6lH rsD.6^lel gzle gl

+4 zl4zlelg ^JCE-= qBrll EEslolo[ o1
î"lql dE"r| Btl 9lHzlE"l
Et5D.1(a) "J"J
^Jq= 4r.545
gEql qB4 E=6}AL.+? 4ls+t
ElsD.t(b) "Jg +zi ll$ffiol ^JH kol yE+ ** "lluJzl"J A+ql= 2tD.r(b) 6J +la}e} zflz} tszI t}s4*ol HlgC ElHl¤ qlqzl
^l-olel
14 zF_ trJ g$ trll* igt}4E rso.0rlE e^l-tr. ql*El= +E ^J+= -s.tsg zlz\a- ¤B¤4. drE"r+ H{ 9lulzlEol t}*E¤ ^}"lql qg4l
gEql qB4l E+6ld!+?
qfl¤ qlqzl zl4zl44 ^8C+= dE"4 Bd qlqzl$ol q$4l EEslqoF 6I
ÎolE ts4*ol "Jq^d
ElsD.2(a) qI gzle+ zflz} BzI ^lolql
s.Eg zlzla- dBg+. {Er+ Htl 9ltJzlE"l H}*+= qg4l xis+i
^}"lql
BsE.l {ol uJ¤¤ ¤+4 o e zl4zl{-4? 7l* C*49--e HI¤¤
EE 1sE Egzloil^lel tr^l olE

gxll
==
DlsE.l dz} old r+cql^l Etts ¤^Jol qB qg¤- 6}!+? DlsE3 ffi 4q^lE dz} old +EE qBril ¤'J1g +
olzl-pol +"J
¤g6l-¤eh dz} azllg+ Bzll rlol9 zl4, ol ,+cel _tr6 Gibbs oilH
D1sE2 dEg gqql^l uJ*"I Bq q oj-+srdo1 g++ 9l dz} old =xl
zl, :a-l_il.4IeI-+Hl4"4 ?H E|lael qlqzl.
4s r}fzl A46l+zl ¤B6Iq+. ^lltsl]g
G-^-
Jrr
ElsE.l(a) t a}9 dx} fzJl4 BzH9l 4dlrl d=r:tn-"J 4l k",=2.02x E15E.3(a) 2e8Kq^l 6J tlg dx} #zHe+ Ez||9l 4ollrl H",(4=0.04cm-r,
l05s-'ol.a, r=t.23nmoJ 4l k,=+.Stxl04s-'o14. ol + ¤Eql^l A,6f.r+ A,d=-0.185ey _l_4r. k",=37.ss-tol+. ++ ig-tr9llqE ol$al.{ xlull
M*9 7t5ol eql z|{ap pel <kg +6}q+. g qqzl {tg +6}o14.
E1sE.l(b) ¤+ rsE.l(a)E +r6}q d=l.5enmoJ trll k",E #g +6lq+. EtsE.3(b) 2e8Kql^] qItlE dz]. #z}]c+ BzH9l 1116ll^l ka=2.02x105s-,ol
J1A.G'=_0.oosevol4. dz} Bzllgl4 zl{}zlE ,}flqq .s.f H}8 cibus
El582(a) f=9nm-'oJ 4lq^J d7l t.lnmtr.*E Z.Onne, +7ltJ n\ H",(A' old +E
3 9uI4 H6lA!+? "llHxlzI td=-0.975eV-tr- E6l-l. dz]. ^J+z| k",=3.33xtoost
E H6}fi.tr1. ?zl]c+ pzll .r.1o1E ,14= + ¤eq^l aL+a z[{a}r.
ElsE.2(b) f=30nm-'oJ 4q^l dzl t.onmilPel z.onm-+. f;z|$ rll
H",(d)e+ AE*9 AEg +6Iq+.
H*(Are 9"I4 H6IAL+?
EA 627
IE714 ts HJB E++

.4.5lll o r.ll
o tl ll/'ll
-]
rrs.r *-*ts dxl old HI¤:E +E= zluflalf s"JE¤ Marcus olEql Inx! =x lnx-xE$ Stirling +Î4g ol+6}q s- t ( n- n*oJ 4l p =
q4 b4q4. E +LB qlLlzl "ld9 +EE zluflali s"JE¤ Forster ol l(n-n*)lnl'-,ol Eg Bq4. flE: 4f 6J +E n-n*+s-19 r-n*E $
gEq t+c)"ll ul+ b6}q4. g olaol Ell+ tzl.J ql= rE}le ol*6lq+.
11s.2 RRK E'J(B jr'aHE E^lolE d|^ll* r.lgrzE -E-ol4).ll 9alH p Irs.g HI*+E^lql +s=.EHl] ¤-+E9 zzl AE= +6ll BzI. dB4
"Jzl7I trl-s=r+ aol +q{q. .J Ezl-59 y,I/N^, f,, 1",f9 azl CEE "5"I¤4. +471Sb F Ezt
7I ¤¤6J oll9 zlf *zI4 qlz|b gg ol-g_9._a qldr-El= fig
+s-l) =zl {s.
D_
l-
nt (n-n*
(n-nfi+;n 7l +*+ q"J6tq+. 4l+6ll^l HIdB 3Ez} E4¤ql ec+ nz| e+n-+n
el HJ+g "Jee qel "Jill "Jxl-= 4lt6lqq.
-+vla 16
\17 IEB
'zlzl *H' z1#2 EzI 49 44 d4¤el t}Ell= 16C NrilRol =Jl 7lH
gq+= d"lE Elzl6}='ll ol*¤+.^fl .q zlzl ^l
"lglrJ *8,
(NMR) +%r"Be q d"lE +A6Iq, ZI++ f'zl plel altl Nun +ur-Bql^l= dzl-71 +^L g1= ole"ol.I, {zl
^S
5e=e$ei ^}ill r$zt{l ol-azl 4zl4 +";=qI E4-E9 * +s= tls=E4EL+. ol ,JBg E+ ej/t ¤E zl
^J
ae+ Sqqlg ¤+atE rll ts4 ol$Elr 9l= zl$ol4. 'd +E gdql rll+ Ul$ zl-}.^Jg gq+r 9l+. ol e$oll.<l
z[ 1tz[z],! tB' (EpR) E"JB* 4 zizl +l.84 zlH ulit NMRqI^JE sclql +6H^l ¤H6Lr ol HIB-o + 'q
oErl E dzl-$ *= EE+E9 dz| l¤ dolE Er-461-= = ^s
overhauser a.4E oleo 6J EzL faE BÎ6J-= %lflql +611
ql ol+g+. .<]r {SaP^1. ++.
16C.1 rlTlit trlEJ; 16C.2 eJil; 16C.3 ÊJ EB; r6C.4.-4
ÊJ =B
Overhauser Erl
16A gHJ flAI
ol e$oll.<l Y ,l7l*ol ¤{]B

tsxI ?Iql Eqfl= q==4
oll 16D dxt 8irl7l
=B
d4-59 tF4=- Îol9 qlqzle+ +%l.q}4 {ol$ zlull
^¤
6l+ g?-l$ ¤Hg 4"lc}. r4a olelal dol# Bzl6J f
x}^llq} EpR r-El= Bg ¤- dzle+ g dzle+ tls4r-e" 6l= q
E9 Ezt¤tAg q}¤6Jtr1. +49 Eail dxl E
fl= A+* ¤e +^lql +6H^J ¤EaJ 4o14. ÊEH
E7I qB4 +&9ts zlE ql+g + 9l+.
^S
16A.1 6_4 rtTl 8B; 16A.2 Erl 8lt7l8
=B 16D.1 gil; 16D.2 *Ellll 75'
168 N1MR,r.rlEHgl g r[-E

=g 0l xl-Eel EE=?
ol Eqql^l= *d zlzl^d eE C¤ol r dz| E9lzl$ i
+lql fl= 4E zlzlC qql el"|]^J qts g.Jg tsbzlE E
*83
zl-zl frzlElqi4 ^8Els,I EolotlrJ e+*E-g " ^r
=al
ap :. +z 44¤. 6k rll ol+El= E¤rrlg ,Jq6J E+
zll4^l 4zlzl tHBql +6H^J {$a}az} aJ4. ol4ei zll
= ftol4. 4 zlzl +Ee e-lEql^J +E*lzlrll ¤+!r 9lq.
H=¤ olo_" 6|s EzI +a7l-+.lol+ r.illql^lE NMR /-.E 'zlzl *E g^J(MRr)g rill qtlE 49 "JczI EE g^J¤-
EH E"&9 q$rll zlufl6ft.zl= ¤HB + 9l+.
168.1 Etetrl 015; 168.2 7[al= 8+el fl?]; rOe.s 0l^ll 7.I; 168.4
+44q(guJF zl), B¤. rl+61-= rlq+ ftol E.lr1 9l+. g
:2il llE; 168.s zi{l SEll NMR
a3=zzglrl= z}]-E4+4 dzl ttzlTlc +Eol g
^Je+Eql^l
"ILI +&9zlE ¤B6I +gltri +, ^Jill lE44 +]. +a
g-a4 tlE+¤¤ 6F= ql Ela"l q$ril "l$9tszl 4
^g
+zl4 +=e+ r ++lel Ee+ql "Ja+ EPR ¤.%r-89 "l*
ql +6H^J ¤H6I*+
EEl 15A gHJ flEI
4gF=*e] a7l+ {r((r+ r)),/rfr ol 4.

> 0l EirJE Hll+= olf;.
Eq E#4 drl'dlxPld AE #e fl¤El gqoil^j
xPl AE
ql B^lg +k+)
^JE 4 eE* d#
mfiolq, {r
ilo
ffit=l,I-1, ..., -Iolr+. Rr

Erl.=
^lE6tl.
+I= e86h= trll 'Jal ol8Ez ?ltrt olag rPl
il
0Fll6lqE xtTl¤Iol Eqr+ E^lE9 AtrJ 8E}| ollHxloll olE g:e}= 4gF=+, trI+^J zlzl E{i=.el ufla}s- m,4 *,9 olrlj
+-rlE 0l6ll6t|0i E!trl. E a6l4l+.
> o_4C TllLJ ol Ezil

^deql
e_l6LH qq 4L+E-*, tr++^l a- 471 EHIE
rplg oJoil^jE
E4al d^fsl4E gEt|Eol gol-d 0il11^l= 7l^lq,
+ +ql ql6H^J ^Jq4 " E 2I+r4 tlolal H]]il}-9 444ot
CE+el C^l7l +^1.= \tE^l7lfl 0l= /.lolotlAl -:1E =
4-BfEl
EolTl gqH + ?lrl.
*4. ,H 491=]olq, I zlzl E-HIE= + H}l6J +q qL 6L
+
'l-= ++E 4"14(mF*i, -i).mF++ ^JEll= "JHl4e a
> Els.Et qHl rl^l
q r4l mF-i ^JE.lt= B-e. *,<1ql4. ,nN 43 /= lolq, rr}
gfilq+4 TllLl(EE 8B), BolEmann EE(E Lxll Er{ xF.l 4^j ^-ll Hl]6J +E q- 6Lq¤ +48 4"]14@,=*1, 0, -l).
tr?} EE 12A), .Lalr gHE "JHJ4 de(E4 11A)E +xl
Ê!E s tz6e| '60g I=0o14,44rl zlzl EH!trz| 0ol+.
6l-n ?lolot elq.
(a) x[zlet +oill-lel -4s! oilLlrl

zlzl* o 49ld zlzl E_{]E t9 9lulzlE olEe] Âq #
dzle+ "*.g 4Eg'^fl'oi+r 6l-= tA4"J 4+F=J Ce
$ z]-zlr. ?14. ol lflo e "J"l"Joi zlzl E_HI=7]. ^871q,
_o + fol{+(Eq 8Cq Elqzlel tl^l zzE Eot4).
r?-l6}q ol5"l 4I¤. +rllz}44 u-ol 4E" 6J4. ol$ zlzl E E=-|t.ts (16A.1)
HIEE {lHzl} el+ql^J 4+61+ ztzl$49 Hll'Jql el=

++. Cq44l s¤6tH (B+'471 .?g'o14, Ell+?+(T)E *+lE
qrt dzl-^g qlqzl r}"l9 d"lE +e6F= E%I +4utr1. 1T= 1k8 A-'ol+. 7l-+r-+b ul-Sr tgl(c)E. zl-
'-,
=+lE
Bql^JE rl5fzl-EgeI df{¤ ^lolE d p.J(^JE4I+)
# ol+q=Ell 1r=104Gol+. "Jzlqol4e + ol qlqzlql ql
so 6lE hamilton
fl,tlzl-b q^q=+ ,JL+.
I "JezlE +H ¤tlg ol+ql+. ^ld^J _EE E,}Bg dz}
7le.4 $zi,r.1o1g +H Aql9 "J¤=olzl"J tsrll zlzl *B9l
qlqzl zlzl*4 "*E+ a¤61+ 1o14, z. 9
tt -- tr.ts (16A.2)
^l= =+lE¤- 49 xlzl EEIE ¤tlzlt 4gF* ¤&zl-ql Hlell++.

4C"l olqq.
^fl
tr-y*i (t6A.3a)
15A.1 EI rPI EB
¤zlrJ Elell tI+ r*3 4 zlzlgd ulgerJ, 4g a"Fql E
-44E 2$t+ 1. qE "Je6J r+ Cdol4,' 4zl9l trI4^J r (}g dB4 " + ¤AE+(E 16L.2). z+ HJ6Je--tr
=6Iq
r <lol Cfol4+(09 EgI6J) HI-C+ol+(.E t6A.l). q
sol 44Ll]= 4+E=Je +E ++el 4¤+%l(Eq 7F)4 ^ E 16A.1 -4el dEal."+-^trJ gr^|.+,,
+g+ cas q4u+.+ "JCzl9 f +Cz}el + I

d).
-1 I
dx
--1 I 0
6l-
=l
6,A
=l Cf (t, 2,3,...)
4l)-
--1 I
6l-
HI-A+ (+, +,1,...)
=l
6,4 p,14.
r --1 HI-C+ (+,+,r,...)
^J4e} t"lal e9 ^J4=
EE e Hlql HlqI =l
I
dlEL ^Jqle+ tr-ol+

* zl4 =
+ 9l+. ¤zl,<l} Hlq tlE|| "Jg rE6JtrI. ^{ . Eol uI*
^Jqlql
glg q
164 gHJ flal 531
tllzlzl zlzltol er$¤ ullE r6e.zal9

aooJ nu*itton fl{!z}
zf ul-e--4 *ol ¤4. 9.-,= -l
H --lt"tso=-T*Eoi, (16A.3b) ^l-718

a= qt ^t718
fl= nfl
yh@,
^fl 4+F*q 4+ ¤&4 i,4 t-+zlb m,h ol

z+ C+ql
trl-. tr+4^J 16A3b^19 hamilton ¤tlz}9 a+il, +
:"1+q= qq qlHzlE trl^g_r+ rJ"l = ^l7l*
"ll^l 84.
a' m,= +l
E^,=-y*hBom, xtTlg +o1,'.le.l -4 ^r3el
ollLlll (16A.4a)
lal l6A.t gE HIB= rf= 4E!-+ -"_l(rH+ Aol +
'3C
^l7ltrlE
0ll 91= ttflg -"-4 ,\El 011L1^l 0l
^l7lB
ollLl^l iPl dxl7l8e.l
ol 49 gelztga q+r+ eg -4 E[:11{lErrN4 -"4
se!x}s' Brl-E qlq^lg| *qE q
=91. =+l=
gclutrl.. ^lolsl
=:8ol
A 7l4a- ++Ur+.
ll"= z*,
en
-"-I ofrLjlE t6gl (16A.4b) +Î+q t]t+= Bohr9 tl*+ 4zl LE_hv9l 9aH^J rJ¤.
4 ee +B 4ag "J+^l4ot e}4(re 16A.1).
(qzl mpY "JCzl9 a"+oltrt.)
^l
ly-y*trBo, a v- T*Eo
2n
NN/Roil^lel
=iB â
(16A.6)
g,-X "j goJxl.tEEl (16A.4c)

ol+AlE EB aZ"l4.l. 6Iq, vb 49 NMR 1154ala,tL
+. 16,{.6^13 qg 7lzlr. +E* 4,"lzl"J -'-glol 0ol
rBlH l6A.4a^l"l +¤.4 ?ol ¤4. ^S-+
olu trI= E= "lql ql6l]^JE_ 4+g+.
E,,,=-g,lnBnffi, IlTlg +oll,r.jsl -q lge-l ollLlll (16A.4d)
a+ql q{^l3 zlzlC qg 4Le u-|Ql z1.! c e -H-= *zI
EqI4 "Jtr-4 r.A4 "Jtlg ullaN_H_| aE +q44. "l "-|
q
"IrqlEE Ag IrN=5.051 x10-271].roltr, 4 g"Jxl+ "J
4 xI49 el+ql^l zlzl** 4r-+^la ql zlzl* HJ6J ++lE
HI4 "s. -64 ÎolE Atg *=r].(-s 16A.2).sp+ rN9 (}
+6
zlgq4 sld6l+ l{Ft g# ,*+(rB rcA.z). ol ,rllz} $
Eol oJolH zlzl E_{lE7]. r-g 4¤-F=J EEle+ E"J %r-6}9
FE +E vr9 Larmor l1!il 13zil. *+.
ol+r 9l+= -tr^l+. rqr olEol +olH zlzl EHIE9| ,- =
sol *4 "J6Jol4= s.^l+. vt.= T*Eo TIE+ ttrell (16A.7)
"i9 Larmor
zlzl* +ql^l= F^J49E +lE6I= 'He+ '3C q=g
2n ^llxf
IN>0o14 *,>0"J tl49 qlqzlTl mt<O"J ^JqlE+ *+ vr9 r6R.6^lE *H 4l#e+ e+. Hl-+
^llz} TI5+
Larmor
r=*oJ liiJ-+ -"4e-l a+, at49 qlqzlzl B^J4E+ *-qq, .Jq+rll 61.=
ol= qlqzl ,J4z r+s_4 g+. "l "5"I8 at4e} ptr-'X ^l-olE *B dolE
Îolel +^l-rlel 4l¤+= Larmor ^lli} a5+c+ trl+^J q
=-"J6|+.
g+E 6l-111 6}=
zlzlE-{lE= +Qqt= tE
qr-r.|] z}4ol
LE=E-r,r-E+uz= try*it&o-(-iy"nBo)=yytt&, (16A.5)
aC al+ $xlzl*) zlzl CEel 4l$ffi ol q xlzl EHI
tr++^J ol + d"lE "Jezlts Ell gsql sel al5;e-1- E"J6irll ¤ ullztzl H+^l7l= aol+r
^J4 Îol9 13.zlzl| ^84
jE 16A.2* _"j
dtr
^trJ
Eil
-1 zl¤ 34uU"z" r goJzt, Sr zlzlEld uJ$, y*/(10? rr sr) NMR d# (lToll^-l), vtMHz
^¤,I
rH 99.98 5.586 26.7s 42.576
2
2H 0.02 I 0.857 4.Il 6.s36

r3c 1.1 I I
) 1.405 6.73 10.708
llB 80.4 3 r.792 8.58 13.663
2
l4N 99.& I 0.404 r.93 3.078
. zlE ¤oll rl e*3 <IEol ++qq 9lq

632 16
^Pl=E
z
I
EEE
^l.q
I EJIlTl
fg 16A.2 rE50e q qle 4rg "JEl,l
=d=-dq-.
el+ 18 +oll^1 0l
= ^t7l¤
E.fllE= trlElst eo
^l4rl'Jol
I
:.JEal'H
rl'718 g-d
^t7 ^1.4E
:dtrl'. ^t7l +cEIlt
++loll^1 8E¤ IapIOHE
_rt E_
+cEtrl
^11^l' +t!71 trl+^l'
g + el+. fg 16A.3 E:d=?l ruun E8zllel Hfl^l. ?l= =J^l7l

gfoll==tr|'. ^lE= ^l7lB =Coil
z]tr.tEt ol! 16A1 EH-d 7lq

12.0TE zlzltr.oll.<J oj.rJz(l=+)E NMR d#L 16A.6^l
=¤l ^1l7loil
4zlzl +ÎE ¤+ +E= *e .ilHzl tr-E]lE zflzllf(^fl-]
-o + +$ + flsq, gs.* yN9 7}9 .E 16A.10ll^l *g
49 A+ N")ql Hlql6}q zH %r-=E +E= +e qlqzl ^J
+ el+.
49 zHill+(Np)ql Hlql6J+. zlzl *Eol +44= d¤4?l
Yru rft *e {t+ql^J= zl-g-4 H}¤ol ql+61 y47l ulEql ola
v-
(2.6752x10s '1-t r-')x (12.0T) g +^l6J + 9l+ trI{^J g:=J ¤tr +E= Tflill+ Hlql
= 5.1lx108 s-r = 511MHz ^Hl
2n
+++
ol +^Lde +C t-4lqi +îroi g+ +E*N"-^h
î+E]= {t.E+ %qej
+ E4l 1 7t4l+ iltr. +4U ¤+ ^ll7l
g4t,t1lzl, + qlqzlz| ¤+q= +E= gxl +E(*zI7I g.
+q= +E)ql+ 4 ,JzI9 "tlHzlE E$ A+ Atr+.ol l}z}
(o) lttrrn #JIl E qlqzl= "JÎ +^ldE df,fq Hlqlqlq(E=ftvE Edl
*Hol "JqB u|b "l tl$fz} zlollzl5 zrTlelql Hlill
NMRFJ4I(rH r0n3)9 +s. +^d si= LJ= d ^J).
^lEE- f,4(v=I*Edzn! E" ol|rJ). tr}+^1,
zl-4"14. ad +%r-4lE ror ol^Jel zlzl*2 "J= + gt=
g;g ,r1lzl* ¤4. 4s x "J.zl9 "llHzl (16A.8a)
a-dE z}4g ols"¤I4. olelal z1.49 Al^lA +"J "JC¤
zlzl*& "J. + 919q, dqg Âzl g:-lLE ol zlzlz}¤- # ". (N"-Np) x hy*{BJ2n
zlts + 9l+. zl-49 0l$ap 9lE NunS E+ d cJ4l2 7n4+el El
^lsqE
zlzl ^dlEHg +d +ir}+(sooMHz gqg ole"aJr| *d soltzmann Es4(E _u.x11e4 d4l zl^l ¤+ E.q t2A)g
(*E ZI++ ql= BoI+). Ei+^J q =il) olf,-oll.<J Tflill+ El= +ql+.
dolE E
^fl$gqe_l
IIzll 6p. BzlB + gl= +ddir} +irl+
îolel
E]+tlzle+
f4lzlE ole" ¤14. "l d"lE-=EZl 6Ir Erzl6l= z}^ll¤I "J AE e-'='l -x+
B3 eq r6cql^J ¤Eg 4"14. enfrJr--r =l- TnhB,

e^l-e- .JHl4g.E +Etr-q-tr. ElEq fr4 *zl"ll ff= KT
.+q^l zt4
^lE=
"J+ql dqB=+.riil ^lFtr zlH¤- ol 6B-y*hBo<kT"J ulli zlfo}9 dzH(e9 see] 3tl*z}9 ^J
=E6J
+6I"i e I6J + 9l+. adEill z[! z[xl]] "lill gE gE rl rz= _Hol-4)z} zl+.6tq, q A+ql= "JHI4 ".e
gE. ^flE
^lE= B= tzle dql
(4K) Tlvlole $zl6}zl"J ol aaol
"J+B+
+444 ¤4qq el+. EAI 3 ,t{l+ itE zllz{lf ulSi z}zlI +4U
NMR d"l9
^ll7l= ¤4
.Jzl-ql E=6Iq, + 1S tl{el ^1
Tl]ill+ il-e+ dill q lgE + Ar4E ul (N"-Np)/Ng r*6I
,]|zil+ql el=q}+.
z|ill+ Hl. +44= ol.o" ol$ ol HIE trl-S4 A
=ql, ^lg
"l ++H + 9l+.
16A gHJ flzl 533
1- y*htso/kT B dolE- ++6I= 4"1 dx| gr\lT lc EBH(EpR: electron

N, -Np _ N"(1 -Np /N*) _ I - Np /No
paramagnetic resonance, $-$ dz} tEB ESR: electron
- - ^9
olfl+ a" #9 Er*Hg.
No +Nu N.,(1 +Nu /No ) I + Np /N" spin resonance)o1q-. NMR4 +Fq=
N ,ffo,u, qq ECg zlzla 914.
_I- (1
-T*hBolkT) _y*hcBolkT
-TTO-TidJ@- z (a) xlz I8 +oil^lg Ertel oilLJrl
=1
$zl! zlzl EHIE= r 4g 4e+"3=q ulqlt4. dx1
q+^J I ^{ z}zl -E-H]E- g&{.e} dzl-9 zl-zlet49 t}E4}+
hamilton fltlxlÊ 7+7+ t+e-81+ ?JY+.
No-Np =w 7H^ll + [Ê: -4] (16A.8b)

^l
fu=y"3, l?-]tr g--y"$.3 (16A.9a)
"l 49 16A.8a^lql Br ruqI ^J+E +^16].E

rllzl"ll ++ !g Eg + ^¤4
91tr|
=+ 9zlrJ 3= 4I¤+=J S4}zlolr. y,* 484 Ag dzlE
^S
rlTlEld HlEoltrt.
s* ^,tlzl*%4 =B ^1171
(16A.8c)
y" __ 8,'
2ffi" d^lsl HIE (t6A.9b)
^fTlald
{zlr"l o
erJ dz}9 SuI"l+. (¤zll #"J9 ol
g+ zlzl*4 rllzlE +q+E
cSql HIell6IE_E_ 8"_2.002 31e...
^ll7l=
zlE tl-Ezl EolAl+. E +g xlTltlg ole"o|fl IEEB9
^]
s{lg zlzlsld Hlgel AEql EsL^lA+) Dirac9 r}'lld "J
zl olE¤ Schrodingerzl$ Einstein9 $f tl"tr|]C olEr+ g+
_5r"Jol zlt6l]ri^J(Eq 1680ll^l ol dg ¤EB 4,"14)
EHg B+ dal 614g fz| ?14. ¤-e_E E=J r]lzlb y*r9l ûl qE+ 7l]d6J aoJEll, ol olEql ElsH 8"=20]|4, 0.002 3re
7l q.qZI Ae dzlTl aE ++lE EslrAlr 9l= 1l+E
E HlEll6Iq q= E= aaEol ES6I+H zLTlEld Hlg
= 4zlzl eEo 4 tlg4r-¤¤ 6F= ql Ir|= aol+. y"9 ¤-9 zls
9 qzHqlE^l 'H)zl zlzlqd Hlgol *g qzHqlE^J ',C)
E+qdg+E"Jsa+. E(dzI d6lel zlcoll ,l"J¤+) zlzl E{lEq o}o}ol 4e
F*J EIEIe+ HI'lt"Jg Eq=q.
a7l $ooJ zlzl$ol zHJt6}e__tr_ zle" ¤ ullE hamitton ¤{lzl
zEtEt 0ll 16A2
,Hql qql^JE
z].ffi4?ol 84.
),*=2.675x108rr s-rol4. tr+4^l 20"Cql^J
r 000 000zflel "JCzl-zI 10re-l zlzl|* +ql ilg trI= trl-S g (16A.10)
--y"Eo3,
r+ ee 44zl Lle+
¤tlz}3,= 4¤+*9 z+ CEql qlEL ¤tzlol4. ola
N h Eo ^S
el r+il. m,_ !*o1+. tr+4^l zlzl* +.ll^l= dz}
N,-NU =
I000000x( 2.675x1 0* T-,s-,)x (1.055x 10-'n J s)x(tOt)
9 .lluJzlT| trl¤.r+ *ol ¤4. ^fl
2 x (1.38 I x t g-zr J1-' )x(293K)
\----------- \----Y-
T
k
E^,=-T"h Eom +oil^]el (t 6A.1 1a)
=35 ^plg ollLl^l
E^l ^rJg
ole4 d xlzlt +ql^lE +E 4+ 3s7Hg 7ll4l uq"J zll ol qlqxl=g "Jqlzl-"-e Bohr EELI|E pr$ zlzla +QL}|
+ zlol +r-ql ql +4++. olElql zl9 zHztl+ il ql$ql Erll, ol pe}. r}s=4 *E+.
5E+ d+zt"J zlBE"l Ed6lfl+.
etr
l1'= 2nt" Bohr ofrt-llP (16A.11b)
16,L2 Ef] gtaPl¤ EEI Bohr EtrtllEg <le e.274xft-241r-'"lE+. ol "JE Ae s

6l .E HlEel 7lE olzl-e fl;-6PlE 6JEI. Bohr ntr'-ll
^l7l
47]1r- +ql^] dzlE qlLlzl L+= * Eg q ElrLllE-tr+ "+ 2000ts11+ rq, r++^l ,J4 471 E
=9E Îolql^l "Jq
63t+ 16 rPl=E
Urmr= +l +E "JEqLil= zlz)*Z ole" qfe(uls +lE ZI++ {E e_

ol-zt). d¤4oJ ¤.,J4lel ul]zlEE rg 16A.sql +Elr]l
ppR
8.4. ol ¤+I4l= +d 11t+__r.A ulolr_e.ul "JS("JHI4

^l-718
a= qt ^l-718
eE qt o F Gunn 4lE" z}4a 6J+ aill dzl zlzl), .tlEzl. E-g +
9"FaBo
"]+"1+ 4¤+g B= +F, ulol= +uI ?421, rel-r. 7IH

zlz)*Z "JE= dzt4Ee ol+q4 9l+. EpR_tr +ep+
^l
tr= g dzl¤ zlzl:t- qlgol 6lq, q4^l 44*"14 d ++
P, mr= -l +Eole}.t qI+.¤+ +dg Bxlalt 7l¤tr-el ol+ qlEql
fal 16A.4 +oll^lE drf aAtetl E?lHct g+ +d9:. 1zI E.e-+-tr. +4U+(rH roe.o).
^P18 ^rJ =fl.pAEt|g =+l7l
H lBol 30171 nllEoltrl). g^l- +^lc ,r]lzli uf$
'Jtrl= aE +E6Eal(E^|.E ltrldxl-7 NMRqI^Js+
E T.!E+7l ol ollLlrl ,J4oll 6}|=.!6|"= Tl#e[ "Jq= q 8B0l golutrl.
"t&zlzlE EpR ^trlEHdEE
tlEil=. THill+ ilql E=6J4. dzl9 ?*
^JE}le+
=E ^t"lE
q= Btl4el qlLl zlzl a*Allr+ *sq, qql 46ll^Je+ Hli
BIE= 4 ztzl E-HIEH+ r zJruJT q r+. 16A.eb^lg
+ EEql q+ r+q=4 eg A4= eg + 9l+.
ol86LE t6A.t1aal9 T,hq olol -g.eDl2m"7l94, olag +
16A.11b^lE sohr ullt{lEel CE= ol+6}q -&rrs4l
^l Np-Nr=W THiJl+ il td^ll (16A.13)
+ + 9l+. ,r|+^J
¤zlrl Ng Aill +4
E^.--g"1.LrBom,
^l7lg
+oll,*.1e.l d^l Elej ollLl^l (16A.11c)
^gg
rflrl m,--tila) m,=-i\F) qlq
^l
7i4
ol r-l-e=$ *ol =+ivl =+l ^'rojel
¤4. Efol= eq 4nl7l
Bfl
L,E = E *r,r- E -r,r = i g
"lts&o
- (- * g "t uBo) = g
"lru&o
(1 6A.1 6a)
ÎEE
=.=
oo
{zlrJ Brl*2 ol 7J4e q+4 eg d54 9t8

=91+. "llul^l
7lo
EO
v9 ajzlzl+$ t$g "JsAu}. 7Jal7l

\
\-
hv= g"ltuBo EPRE 8B (16A.16b)
^Z d^|4
tHx
Ljr
ola{
tl --
'll++E ^l+q. E%IAH E o.:3rel zlzllt$

EpR o1 6|il
+El+.r?-l6iq EPR+E {5-45 trl+4 rJtr+. lg 16A.s dE4?l EpREB4lel B|1iIE cB4oe o|EEl= xl7l8P
0.3ToJt1l, 0l AB= "J.e.7l= 0f0|=.eu|:9GHz(3cm)7f EEf.
^lTleUN
9o lla /lo
(2.0023) x(9.274xt0"n T-';x (0.33T)

v- 6.626x10-34
J
|s
A
h =8,
=9.2x10e s-t=9.2GHz
7la7
ol {¤f=
u}ol=e y} ¤qql +fl+ 3.2cm y}tlql ql ,lol
-4 7l=71
=J6lq, dE+E XIrl,+r 6JtrI
^t718,
=!+ol
EO-
EEI'+, dNda
(o) rpn Bll rg 16A.6 flA-AB )Au:l7l= 1^l'E:Et+7f t!6+
q++E rl+ ppn E lalEg ulolr+ul. gqE EpR TIE Ll8trl. # E?4= E:Br'+7l.001
^l.Q-:gtttl=EB^ll7lE
El= E4 eEE +E-6fqal'.
16A gHJ flal 635
zt=J:d q 16A4 rq6}q d zll 6E E 241g4 Tl]ill+ iP| +El.+4. :-4

20"C(2e3K)ql^l 10007HE dzl. t.0T9 zlzllioll :.. 4 dz}"ll 4* ol Tflill+ zl+ q A+(++* ql
^flol
trI= r+q=$ *9 zllrllf zITl LtqtQ. 16A.2)-E-+ ql+61
^flel
olag *9 zlzlat +ql^lE dz}
=g =.4.
el tIEIE ÎolE qlHzl iITL q q6ll^]_E-tr}
N9e 11s ao ^fl
r7l ullEol+. ^¤ql
1000x2.0023 x(9.274x10'n; T-';x (1.0 r)
N No
2x(1.381 x 1g-z: 16-' )x(293K)
T
=2.3
a
=e-etTHEE
tr l. -e4
Bhl*r= "JE A+zlq HIA+4.1= ooJ +E 9l+. 4. NnanqlrJE g+ ^ll7l7t 4I+ zlzl*4 ^ll7l(,4)q 44 ?zl
ÊJ = 6lq, qq zlzl fl{ul¤9 xll$il Hlql'Jtr}.
a 2. zlzl* +ql^l= 4ol ^Jolt m, *4l rl"Jq= 2/+lzilel ql
Hzl 6fl9 *=rt. n s. zlzl* +ql^lE 4zlzl u* F tlqt=ql Ells" 61"= F ql
D 3. rlTl E}B(NMR)$ ^l7ltl 4"ll ¤zflali Qol {tS g+
-4 LJ^l *=+. ^fl
=+lE
6IE ?+qsr| d¤+ ¤qE 4zlzl +^l-= +e6l-b Aol I drl CfxP[ EB(EPR)$ zITlzJ 491 ¤xflal-b g dz.Izi
6.
+ +H g+61+ nlol= eo| 4zlzl +^l-= +e6F= 1"14.
=s-d^l=
.^lzl
oe, +^l al Ha
^l
zlzl* +ql^1E q qqzl E^,=-y*ttBom, l6A.4a
^{9 16A.4d
=-grllxBomt
q,rtrqlE 1t*=ehl2mo lN =5.051x16-zz;1-' l6A.4b
¤l.B ea(^¤_+ q) hv=y*hBo 16A.6
Larmor Tf5f vr=y"@ol2n T64.7

zlzlEld ul¤(dzl) y"=-g"el2m" g"= 2.m.23lg 16A.9b
zlzl* +ql^JE dz} .llHzl E^"=-y,h(Bom, 16A.1la
^S9 l64..11c
= g.llrBoffi,
9o61u[:u]lg 4tr=ehl2m, lls=9274x10 'o]T ' 16A.nb
+B aa(dzD hv=g,pr(Bo 16A.l2b
EEI 168 NN/R ^,rlcaJq
=8
EzI {*ql d+E +g^l7l= i.qq "ls ?l6J +C tr||tl
> ol EEIE Hl|+= ol* zlzl4 qql 4L+61+ +zl4 zlzl*4 q
NMR ÊEE$ E46[r E 4{EaJotl EgE E+-d 8H= ^ll7l= ++lel ^ll+
glolLfl7l g;|],qts ESol E^t +6el olEXl ,8EEI= 4 dz} 7a{l E=6iq, 44^l r}ole} E}+4 zlql +61-=
rl= gopF ert ÊEHE 49 rlolal TIfl+ ^J+E *rll g+. ol trll$.ll 49 Larmor
4l51(tr|+^l *H {$f) vr$ 7*6ot2n*flQ Q-e_g pol
> Eqd 7ilts H++.
xPld e{g AB Tl#= Ixf 5917|et ?!= xlTld "jE
o{e}.g. u}r-rl =x.10fl
Oci= ELEI.
(168.3)
> EJe.Et qHl rl^l
gHJ4 flal(e4
tl5fE t9 flr9 4"14s r
16A)= +rl6E1?,tolot:drl.
^rTlgBE 49 Larmor ++aq q4
94r14.
eq tE {lt+q 7l= e=ilql q6J il¤ st-44 0l=
ol4a qf{. iHei i3cJrl E}3 EiiE4rjiBd*(Si(CHr)0, E
4 xlzl EHIE= +44 zlzl*, + r+ ql^} e +lzlql^Jel E rus4r ? E4)"1+. oJ qE tB 11#e+ E
zlzl*4 ^Js4t¤¤ ++. ol +zl4 zlzl*Z ++ qltl eg il-= q+ t}e_l =4ql
Hlql6H^J zlzlts'll,
= Îolel ^ll7lql "lag
Eflr+a 9l= +99 dzl-E9 ¤6Jl} +zI +E 4E zlzld Larmor +l5fz} e-l+ 4L+ zlzlarql ulellalzl ull+ol4.
qEE trllEql e]+ql.<J zlap zlzlz.4 trl-= + gt+ 3rI+4 olt+ trIg4 ?3 0 4E. olgall,<J +4U+.
=^ll
r7-l6}q ol qE NMR 4l# dzll4 " e EzI +aq EI
A6L+. r-I";16u
5= 6 4E ttrEl (168.4a)
158.1 Elet{ ol= olTl^Jv'9 .*E +E t1#+.#J4lE 4E tl# y,p..,3

"JHI4 " + aÎ qt} 4Eol ++rll= Larmor {H=E +
9.f, z|zl^J$ Ez| ql+ollrJ dzl# qd^lzlb s43 4 a ¤E ztg 4617) qlEql vog v.*.,4 Ell+61 ulfa[{ :.r-]
4U4. "l dzl Eldg d+e+ Hl+6Iq q4^J zlzl^Jg ^J atq ol al9 E-s vog V,p".,-tr_ HF+qE itolTt s.gq, l
zl4l aJ4. tt|?+^J qql 4ts"6l+ dill zl-7ltl(=rl4 xl7l8 ?-l6iol 6 4EE q^q=4 ?ol 44t4.
=
6r*)9 el+ql^l 4+6t= zlzl* 6oe| dzl¤9 fld"ll zl.J
99 +zl-4 o + +++= zlzl* 0oe+9 aJ"l ¤ 4,"14. v-vo
6= xloo (16B.4b)
Yro.o
@to,= Eo+ 6{8 (168.1)

+o,t.4 olffi ol+al ++.llfl el+ +el ^llTlql ++6i+E
"1 +zl4 zltl]$$ e-l+ zf+ zlzl^J9l Hlql6}q,
"l4g +f etdol 9l+(+Ee+ Ezlzl E+ e]+ zlzltlql ulellalzl ull$
ol+).rq+ +E TIt+ zlill= +¤61
4 o _e q-s=r+ aol +4u+. 'l*+ e.ol 9P t}
9,rllzlql el=++.
6(8= -o(Bo )lttz a+ ttreil (168.2)
¤zld +-qflCE 49 Tlalt ga4a **

Hlql^J+ oE v=vo+
[**),
(168.s)
4(oE "JHI49E oJ=olzluJ +"J +E gltrt) el$ zlzl$ol

168 NMR .rul-=aJolEB 637
z}trJ-d 0{l 168.1 4zl! d* zla*- E=q 7lr-l* tL++. 7I"-l+ *i ozl4
olaf 714¤-"1 4"le++) 6.6zl6.J4. EleL4 ol5
4L.$6I= NMR E:"J4lql^J TMSE +
s00.r30 ogMHzoll^J =(+
oi qg zril H.441+r "J6J + 9l+. "J+ dB4.J slqi
Bol soo.r275lMHzql^J +4t+. r4E soo.rzs2lMHz =
el +E 4i#E EltrI4 olf,$ q+r+ ?Jq. 4 olffi:19 16B.rql +448.4. ol rH ¤Eql +Elt HI
q+
?ol e=q +E4 olE H9l= g^ql 6p4 =.2il +e+.
(s00. 1 28 2s MHz )- (599._?7 50 MHz ) olq+ +"JqI olE4 olE H+l= Ez[ "Jql^J qE dz] E
" 5{
6= -'^"
v,0.., ",
oo -
500.13000I
*, oo
E +aol 4"Jolzl ull$ol4. fliel flxI B-s7l +71uJ++
= 1.5 q ++lql 471 +71 "*"|zlq q+^l 7t7-l+ Hglz} 441+.
gg *IAIE {tg 41, 6,=t.zse} 6z=5.75oJ + *Eel A +44 o-E NMR 671- e-E5---e--E+q g+-q-e +
ÊEHS
g4 zli q-q_q eol 16Bs^lg ol+6l]^J +B + gltrI. T16}rll -5a^l6]]=+.
v z-v,= (f ),6,
-d,,=
[*r#q*)
(s.7s-|.2s)
=2250H2 E]il1HNMRÊ4E{gst 6tt4

tH rcg.z= 1-ql+^l-2-E+Sg, CH3OCH2COCH3E 'H
NMR qrl +4t 3rlq}4 "l5¤ ¤E6tot+.
ÊEHol+.
rqFJ dzl¤ flzlz} 9l+H :. affi I
trE dE 8^.! 6E AE +ql Eq"lE rouo14= "Jzl-uilE ^lEl =olql=
B"ll"t ++. olel+ flzl-b e6Jg "Jczl¤ z7il H.zlq,
ql Bg Ef,ql^l olag ++4 0l# ppme + 444zls
g"-l Bqd "JCzlql4l= 9BJ 445 Elrl+. Be+ c *B
6|zluj :zE ¤-s-zl S.trI. '6= t0ppmol4I + ag EH ola
el qL {ol Hflzt 2e+ 3ql Eil+61+zlE gl4"t al-b'll,
¤- 6= l0 o e allfalr. r6s5^lglE ol {tg "l+6}E E+.
+ !lr-B +el 6t'-l¤ ol+g + 9l+. ol+ + %IBe 4=j=
E e++zl olE qlolElzl. ffi$ E¤g E= aol+. E 6t
r0s.r^19 r6B.aa^loll Bq+H 6el o ^Lolel trI-s4 eg +
+E ,&B* del '4El +B ++fl E9 H"l
4= eg + ^trlEfl
9ttr1.
E. 4"14. ¤+"]e_l Holts=++"]E +44= qel
=
a=ffi'ro' +ql Hlql6J+. ol 4ts9 tH
+ EoJ +dq r-ErlEer o
rcs.zql^le+
+ +4+q, 4lt
?ol 6d¤ 4l
EolTL 4E
ldl<< I
{}ql Blql++.
-9'-{
I-O"
ylgu (o"-o)xlOu 6el o szl (168.6) g.zl 2e+ 3s-l +a flzl.= d4¤ d.oEt= oJol tl
^lolel
=ol
&a gz;s+ ad:6}r glb cflzlql aqlqq 9lq-. +¤
s.zl lE Hflzlt oflxlE+q E"-l trqrq fl+. tr++^-l
Rcr. tul%-cn Ezl 2e+ l9 ufl4* _trzl lel HflzlE4 H.4 .artrz1-3
.: i. : affipf,"z
. 4o14, r46rq 2e+ 39 Hfl{+ rg HflzlE+ slql
:
,
:
66_66^ om___CI_
":rArC-CH^
"- -"3 ,
=
-CO-CH"j''
-u=urt- ltIEI
!. :ffiArOH -r-Lr'. i +lzl lE sflzl-ql tsHaq= 4"l"l"t 6J+. E ol
ql E6lH ¤+"-l Bel zlEg ++"-l c9 4+84ÊEH:
!
EEa.-H
-co OH ffi_cHo
::!
^' " :
21086 20 =.4(3
a
5
4
2e ar+), trl-+^J ¤+?] B= +lil ag uflzlql EIEL as
B.C-H
l
,
E HHAqqoF 6Ia ++4 c= +lil zg uflztql HHe^l
RrC-
a + el+.
:
-C=C-
, -C=C<
C-X in ArX
R_CHO
R-C=N xlTl B7l 168.1 ot^,llE"JqlqEq NMR
R-COO H
ÊEHql=
+4'J+. qL ^$ilE
RrC=O
i R=C=R 6-2.204 6=e.8091
R"ct ÊEedE"l
(b)
300 200 5 100 0 Hdg cHo "JCzl"ll Hl]Be. f :ls+i
0g'6=9:E
lg 168.1 (a) lH EB4 (b) '3C BB9 EB4?l a[+4 olE H+l
638 rP I
=E
o 4 Ae Lamb 49 ol+61]^J 4ltg + 9l+'.

B A
o
Hsc' C H3
e'Ho
C 3 H2 6d=
l2nm,
(rlr) Lamb (168.9)
2 ^l
q7l^l p,e rl* F4E rg dz}-q 44, t4r. (...)E zl
qlil+.
__T__-__r_
4.0 3.5 3.0 6 2.5 2.0
.f.al 168.2 1-qlEAl-Z-ueEAE 'H-NMR ,rEl-=.H. 4lE

E-?.alE 4E dA= LElL|1q(E+al gE
Eg!+dg
'JoD, 4lEE Eolb 4.Eotl
fflftfl Lamb^let ot8
Hle{l:ettrl. zffi Hflzlql^lE "Jczl."ll 4tI zI4* d¤ 4l&qq4.
a.q-g IEI Lamb 49 ol8a}¤ oaE 4l^l6ielE fi ts
+llEoJ+ql .]]ql Ur! zlrlzl= al4}6llot *+.
168.2 Ttalt 8+o! fl?.! EJÎ"J6J dBg S 8A.1ql, 4r j¤3 E 7F.lql ++qq
el+.
TIpl+ ^J+E al+6iElE EzlE Hlqr-^Jqle+ E. tlqtql^J
9 dz} "Js Eeql +qI z|^ll+ zl^14 r iff: "llHzl E"1l =ol
f4 rs +llEql+ql '11+ ¤+EI r+-" sL+E trl+4
a+(Eq qqxlel tl^l 2lg -H-oIq).
SqL AEzI ¤sate-E z}++ Ezl-E A+qlE r zjl{lol u1l
7Fq
+ qB+. r+zl"J sI+4 ol*"ll 4El ^}oltl zl$pol zla-l ttt

( I )
U2
+ tr"+q "lzl= "J44 a6J.g olallali 1_o e + E¤-ol Y 1 e-rloo

(. lla;
)
=
Etr}.
ol ais.4lql^J= +E a ^7| dr=sineidr *tn
ola,g olallali f3"6J + rl$g TIEI+ *#zl trlg=r+ g d0a4o1q,
g zlolE ol+qd+r 7l-C6l+ 4o14. .! t/r9 714il= tr1g.l1 e+.
^ll
2r 4E E.1
o- o(local) + o(neighbour) + o(solvent) (168.7)

(rtr>--lryor=* J'"apJ"ri no d,o [,* re-)rta'' 4,
¤zlrl o(loc)b Ezll9 qg EEL6I-= gzl-9 {zl-$ol zlol
6l+ 7lq+. o(neighbour)i Ez}el 4"lzl ffi$ ol 1 rr l
=lta;,x4nx.=-
1 au
+= =IlE
+= zlf1sl flz|Eol 7lq6i= 7lqq.
?1tr71 r4r
o(solvent)t.$rH Ezl¤ol zJ{afi EE[| 7lfiol4. trl-+^J
)
u^
e- ,U _ (1.602x 10-'e C)2 x(4nxt0-' Is' C-' m-' )
(a) +rl4 7lq " a- l2nnt"an t2nx(9.t09 x t0-3' kg)x(s.292x I 0-" m)
,Iel* ^J+ql 4t tzl4 zlol= ++4 eol U^171tr 7lq (1.602x10-te)?x(4nxl0-7),.C'ls'C-'m-'
=unr1o.rory^---qm
ooel Sxlzld 7lq oo9 aJee. H= aol ¤p-l6l-+.
=I.775xIO-5
o(local)=oo*oo
)ltl3 d:+oil (16B.8)
rH-d 7lq
=^15 ol 4l4lq^l= r J_ l kg *, rzg o1a-" a|flr|.
4,* elztzld zlol= q+ zlzl*4 q686}q _nEl
o(loc)oll rPl 87[ 168.2 q d6P] zql +^¤ flzl-oll 4+q=
q^J eg 714=tr+.HlEq o(loc)9l 4* tzlzlB zlq= el
oaql 4t "JHI4g +E6lq+.
P ztzlat$ -BrJ6Lq rq qtr qg H4+= -E.q-E- ++U oo'
wlt71 1
otl
raT --
e
o :6
q. r?-16l-9 oo>04 op<ool ¤El.
tlzlzld 7lq= 9P zlzl*ol 9zl9 HlqltlEl] dz} Ee
ql^J d6l= qd^lzlzl qlEql +4ttri. d6IE Eld ¤+"l g6J ?d9 zltl +4 tr-Elt flxt9 49 dz| E=21 7q
"Jq+E el++r+ Hlqlq. zlzlzlol xjzll rEl6I"1 qg
714+L+. oo! q e-l=61-q, +g t ol .,?E 4eg xlzl¤9 Molecularquantummechanics(2Oll)E +:il.6l.q
=zl= =aE dxt "Jsql 4.
168 NMR 639
ÊaJq =d
El+rtsl 8^l 29 8=rlt! x}7la|
a
0o
W
,-'l
o
Rr
4zlzl* olEql el6}ts zg zlzl_ffi2| p-e+q r ".I# E
rlol
rlol
2
qd xE zlzl** q++ *L+.
'lol
CH"CH \
a= Fo,(rr-3(P:r)r)
[U
ol
) '"- 4n t\n r,
xll 3
N
)
9zlrl Fog 4.* zlzl FrlE(zl$ $fer.'l r <lg
rlllil
-o
Br CI F
4nxt0-7 T2 rt *r)o14. z+ %}6}el zlzl* ¤Ee q+4
I
I
2 2.5 3 3.5 4
geulE zlzl zEE, t Rol S4.
fa 168.3 a[+4 Tleltel E7l E-8Eoil nt= EEI'. 0ll=J $Sxtoll r|1e]
0l- gezlE d7l=¤E e)Pl a[-+4 olE¤ e7l^l,J ?tola|.= qEtrt
g^lEltrt. -LajLl El-qr4 0lEol zttrlEE :d&J= e66h= oll=Jil! gdrtoll ",=#(u,-ryY)
rllsl{,\J= 0l e-BFol q|,84 HJLHE LfEfUrf. 0l= gd^loll EH6H I= trl-= 7lq
(C-Hel'c-x e-sf=E HlEU¤)7l ¤zlrl z=rcosg=4El EEI rA zZ d$oltrt trF}^l ztTl
^1714 ^lut|40ltl. ,yd-ja-1471 2+4 ¤4618 El^g-r+ ¤ol ¤4.
ql= HlzlTlc 71¤zI zI4¤- t}+ql 4+ *"J+ zl¤ P'r z
'Ha"J
4 EzIg A+q flatz} T3.zlzl d6IZl "J:_44fl= q += B,= lto (; 3(prcos0)(rcos0) Hlo,
= 4rrr' (r-3cos2o)
'
E qC dzl¤E +B 'llag ol+r ?19 4."14. u+{^J q
4nr3
CP dzl} zlr-l-S E+ql s{ *zlzl4 z1q. 6J Sol4.

qlzlzl4 zlq= +c 4t} 4ol +6t= flz}9 xz1 "Jrgl
HlEll]*+. q+^l dzl *ds7l= gÎ7I ilq^J 6]]'J (z)ol4l ++. 4 lli,,au..a -18so14. HlzlTl¤ flzltg 9P
=i]ql zlzl*4 qlql Hlaje_E #B zl-zl _EHI_EE 44421 q$ql
flz19 dzt EsTl ¤qEE ol zI48 a.4zl +^++. qld
flz}9 dzl *dszl *zl.*ql q+ 7|?-l+ol A^¤4= a ol zlfizl +E <lg +4t+.
g nlqr-4 ol¤- 07I6zI*49 E"l ¤4(rg 168.3). #B xlzl e.HjEi "Jdzlql ++4= zlzl*& ^Jzlzll eI
Hlq^JEilql^J d+qzl ?+gtH ?llEEI+= ola" 6|{ 4zlzl 4. cl*zlE tl^-l zg"llrJ ¤BqI uts+ t"l l$ts zlzl EHIE
Ezl- dzllq ea ¤E" 6J + glrll 6IE fl+ zlzl$o1 +zl4 tr+El n"J* trqd z-l4.tl 7+Ii0= ol+I or- arolli{loll
tzlzld ooil zlqg + fl+. e]+ zlzl$ol *4 ti4 flzL +4U) Qê=$ t3 llzl4 zlzl*"1 4L+6J 4"14.
+ dB Ezlt9ld4 Hc=cH)E a+ql= +zl-+ql q+ 4
+g uI= ol z1{z} ool g+. oltrll= dzl¤ol z}ffiAl dfl r
g + 9lr Ez| + "J.JsB 4s"6lt el+tlol d4¤¤ 4 pi
+llEEL+E *4+zl *6Jtr|. ¤rll + 9lb TIqe g I

= =¤
z(q zlzlololl.<J fl*z} $xlzl d+= {ElE + 9l=)e+ * 1
I E=E ^J4= *= +zHq+ tLq Eql^J tlrJal dFzI f, Elor ln

#ir,..lr..d
(1-3cosr 0) +^14 (168.10a)
ts¤ + glEJq A+ql= tlziTl^J zl4zl +qB + 9lg r 3
^|-71A|
=
4."14.d41E f^ ol99 flz}9 +zl4 zlq= +s*471 ol=tzl4 zlzl^J$ $+ 4L+ zlzl*4 ¤q6rq, 4 0= e-l+
4 zl$z| zlull{olu1. 4* zlzl*e-l ,J6Jl} "l F zlrol4. + He+ x ,tlol9 zl4
=
E ^ll4l#ql +Hlqld-= zlTl1tol "J^dzl4l +zl4os 716|]
(b) ?1tr717lq zl= aol+. zlzlffiol ExI Hlla}ql rue- a+ql=(+
.Jdzl 7lq= qldq= flz}*ql +Bq= d+ ulEql =i-'*
^Ja t"J a+) 1-3cos20g + d4ql aa^l ¤+IRg q1 ool ¤
+. qlE^l H-xe+ Ag EÎql^l "Jd flzItr xz} Hgl "lil= q. rfl+ zlzlffiol olf 4Eql el
Ezlzt zlzl* H|]6J4
tr]t= +zl4 zlzl*4 ¤+ilz| ool 9zl ?*9=
s.4=- rj{a}lgz}. xoll E-gg d4s=* e]+ tl-ql el6ll^J d + 9t+
=g
+= +44q er+4 o + q+ tlq Hlull6l+ +g-z}7l -EHl qls^J "Jd7l71 4 qlag 4=+a ^J46}] ezHr¤! A.JE
-EE +4441 ¤+. ol Hlr{ ^}+= ol "Jd7l xE z}zlffi A+ql^le+ *ol). r?-16}0l q+ 4I+ zlzlltol ol qla+4
640 16 rPl=E
+
rlr )
*Lt
r\
) + EI E+ j
\
^l-718
! I J
lg 168.4 tr g=^l.nliEoil g7l= r=Jg 1/R3

q4 aa6F= ^t7l ^l'716l. ^11 ^49ilel
oil Ll-EfLHq, 4?14 E= 4 zelql^-le.l 89 z= f.al 168.6 el+ Soll E6H^1 Eldlaelotl +'JE g E+el 7|eJ ArE|. Xa
^l7lg ^1171=
Eal. ralql =JzJ gd^f= xTlrlrl"J ilEJTloil Ecl^1 14 fle flolLl-S
dEg 4E 9== LlEfL.!trl.
g¤rl'= 7lalT.lrl.
¤q"J qi= ^l-7lE+gol /,oll. zl4"J QlEzr4_1.6}zl. ola c1 Hl-+Hldel zlzlal$$ 444-cll, z ol.?E e]+ tL
g E= gz1. ullalql +6[^J ¤t6|]+H 4?-] Rql gil,t] q9 =
ol EzI Hql ls"g q rfl= ul4 dzl-z} dq6}
+z161711
?14& ^J+q +$4 Ag EE ,l"l=
"lil= 44zl g+. "l E dEE *E:"Izl ullEol4. rq6lq ol Eql fl= "J^d
zl.= H.4zlzluJ(:.8 r0e.0) ol E9 +l+ "Jql +olrll El=
"JC zHzl¤tzl el "J+E^J )E rI4 4l+.
o ( neighbo w) * ( xt- r r(=#9 )
?tE7t 7tq (16B.lob) (c) En[| zlG
trfla++ qql
ulq +,H= eql 4+6I= +zl4 zlzl*ql q 4 zVl "J^l oe ¤
{zlri o(EllEz})= ^Lol9
4sol ql6J
6Jg- +=tr11, olq+ g.JeglE *rlls+ +a
+(2). 16B.10b^lql E6IE "Jdzl 7lq= + zITlq¤E ^J'11 ÎolE ^JE++
(qlAq +i eo-Jol ^82144 rewis &-E7l 4Eol ^JzlEl.ll
4 =zl* ¤)HJ6Jql q4 "Jol g +E gln gol g +E gltrl. zl"Jq= aE 9l+.+r]] +zI9 HIEHIC zlzlffiE, 561
s4.2" <O <125.3"018 r -3cos2@71 ojgE qr r+zl gtg
oJ6J+ $oH Exl-"J
'll E+ +zl4
zlzl*2 "JE + 9I4.
trll= *ol gq(rH t6B.4e+ t6B.s).
6l +e EzIq ¤:rll EzI LlalzluJ r++ ^JE++ =
Î"lql
I "Js.zl= "Jill sr+zl 9lg trI= 8¤ Ezl- "J9 "Jdzlz}
¤-oll Ezlql qql^J qH tr"'H4 +lil. a6l.L+ql ul4 zI4
X
¤ +E glr s Hl4E H4A +E 9l+. Hldl4 ag HJ-J+
x,
+,]1= ¤-d EzI oJ9 "JCzl¤ 714+4* H.zlb +zl4 d
+E ^J7lAl g + 9l+. tfl rct.zql +4u ullaloll,<J| ${
2
qlo}5s +E+ _s.r+E ++Url Hidl l-4 BzlE "JCzl-3 714+41g+.

"J6J+ "Jdzl
.B
o 0
o
o
o
.-
(o
I
L !
b-.
-2
ol" n
rg 168.7 g:d+ E0H(q7l^1= slcl)= EE Exl' gtE oJdxl.= 7l-21
@
+zLt Hz1 45 +^14 E+= UEtrl. q7h1et ee E0l]el-Etrel 8EH4
LH 168.s -d* t -:cos2@9 @oll tttE E+. Bt|:efoll^]= EE E^l'E gd^l7l 7E1dtrl.
168 NrUR,\E4EaJg 641
=A
168.3 ElAil 75 Err,rrrr,. =hJm r,mr. 4E-4trJ

=-st
ollLl^l (168.11)
:7H 168.8g 'H NMR ol tsz}"ll (a) sg

=s+q+E ÊEHol+.
,llBfl(cH,) "Jczle+ qlB(cH,) "Jczl9 + Ê4EaJel
^Jol+ +
a"
=
9 "Jdztz} ol$ol 414:z+,* slql4 old$ + NMRqI^J= e+q}4 "lE"l z4l += qE=g ^JE E?-l gq
=qileq, d gv+Bl + Ae| x)e. E^l6l-=ql, olae. slE
El-U+.S"J otq++E q4 z]]9 ¤Er==E e =zHdB4g
^4Eedol
trl^ll ?E+r- 6J+. rqa ?Jq
4 "lE ^l7l lql Hl6ll^J d#ql ql+6Jtr|= 49 +El.+l
4zltsrll, ola¤. = oltol Hli* q$g
tl +4E di$ ÊEHel El6"11ol4r 6JtrI
zl g]afl,t'1r1. l?-]tr, +qI4 \e zlt\
ol ul,rll +a=.J qel +H {547I +e qe.1 4S s "JrlBl Ae+ B)-tr E^l6J+.
^Jq =zl.(qldql
slE4 rlolalq
+d "lfol e6J 9lHxlE
ql g6&3 += e:d qlEql +4*+. ac4s-E "J + Ll4g + 9i.
=.zll ^g-^S
as+ xE Ee'61+ Ax
6l-H * qql^JE^gal
168.11^l-0
+zl4 zlzl$ol +-a /-.gE tlql4 H1]6Jql ^s-+q
4l= ^J46l]tr-zl-. 4 e= mF t*4 + 4S ^JE.llE *Erll, ol
q+B oI ¤et"l +4*+ ol :-glol qL qL ^JEl](ql
ES aoe| Bo-e sr1++. 4 xs s6J m*= t+E + +
d4 a).ll â49lg ,ll +zl4 zlzl$ol +714+H, '-flol trlE ^g
el= *=4(axel F*). 44^J Ax4l= a,6%y, do\*, Fod*, oi
tr4("1 A+ Oql ilg q= +zl4 xlz\$ol ei*+. tr++
uHalol a4 0zl 5{zl qlEql aI4 B^B*E ql t4z| 9lg + :14. olE ^Jele-l "llHzl= I
^l E4l 49 ^4Eedol
^¤
a4 aqlg +^l6tH q-q=4 ?ol ¤4.
z[ o[rJr Eol +4+= aolq.
LvJa} eEt L¤+ hamilton ¤&zlE (hlth2) i,.io}c
^Jc E -- -T h (l - o o)E om o - y tt (l - o *)(B om *
e ++4=rll, olzl.rJ l,ug 6l N(=t E= 2)el q 4+E ^ ^^, " " (168'12a)
^fl
l1
=-nv Am^-nvxmx
=*ql 4+ S&2I4. "l eo-J 6}0l B_o e -E^l¤+=
ag a,J tls++ qlLJzlTI + q ê4 E]]olql E q7l^J voe| v1E 4rJ t* X9 Larmor d#4(l6B34). r
^J'-il4
^gE
4o14. ^JE++E rllzlE aezl g ron.og g+ql +4u 4414 d"l "l 4ss+q +e a
=*tri= ^l-¤g "J6lt+= +. +¤ -^fl e'Jg aBJ 6ll+ts( g
a+ /el zte-e +qd+. (h1ril i,.r,.J 49 n,3 + ,+ o
I
^fl q-q=+
1 68. 1 I
^l
o
l$afl ,tj )
=-Er
¤.E=J r.+iJs+q +s= frrg ^J4l^lzl4, r?-16l-"1 qlq qlqzl +q7l eol ¤+.
zlzl ryol Elr,
/= Tlt+(*fl1Hz)zl ¤4. "l aB-tF+= oJ
E - hv om - hv * m * + hl m om * (168.12b)
r --
ol+ *ol ¤ + fleq, zlzl*,rllzl"ll ++61+. ^ ^^ ^
+ A6J(tr-szls" ) 49 rarmor {$f5ol ,<l_tr r4l tr}=

ullts olEE 3t
+E7l aAl +sq, olEel zlzl E_HI
^llz}
s9 x44l+ C+=g 4a v+7I "J *sq, z+ dB"Jol FoF* th
1/zhvo+ 1/zhv^
gE 4r{l ++6i{l z;g u}a}e_tr. ABqq #
^llzt ^44
(hlthr) ir,.irF +Elt+. ir,9 l#il rn,_ftolq, tr+e}^J eoJ
K
5
6
6JE r+il= r-lP-r=$ ?ol ¤4.
1/zhvo- 1/zhv^ Fo0,
.AEl-,\El
,\El-,\El 77Al
7{51 ol.9 rrll =H
=H
H
=
*il
0oF*
?l= nll
1/zhv*
CHgCHzCI -|/zhvo+
cnF,
0o0,
CHgCHzCI
1/zhv,
0o0,
-1/zhvo-
:tal t6B.e AXZIE oilq^l rl.=e] Lll ge

=fl. Lll =fl= Ê-AE =--J=,3+71-
7l^l ?J= F gsl
Êsl -9 =+|ts a|¤E= îtJ-Ê =-cr
oilL1^l ol^l==+l=0lrl-.
BBF= LlEl'.! aolq. n9 aE 8Et|7l
3.5 3.0 2.5 5 2.0 1.5 =?loll
aEPE'l Be B= 618 x= E6l^l =¤^4
g= 3?= LIE|.L.! aolE-|-. -dE
=+lel,
fH 168.8 rH(g¤rD NMR H= =J^1.= q-ec= 81q aEIE= X-.jsl 0loll ttl36l.= dol= LlEl.,! 7,ioltl. q7N= E e,o|-Eq
Ll9ll dt= =eeollEJel ^trlEH.
gd^l'= LtqLHq, 0l g¤xlE el-d ,Jalde q+
^4
l.folol ttflEoll Z-d aqE r[l6t|^1 LIEILÎÎU dllsl arJ-afl
tr1"=c=01 LIEtuEl. ^rJa|. =-cF
4tE q-d aoll Hl6H^1 Etl 4rtr1..
=E'oll
^l7l8oll
642 rP I
=g
I FoP*
EO 60
11 Fo0, flo flo
0oF' x
tt
0o0x
J J
fg 168.10 ral 168.90ll Ll'El-,-J ollLl^l=+lel E0l= trlE u^]o+ Ll'El'J
raJ. q7 l^1E a45 rEl6t|^1 LtEtLHfltrl. vA vx
Ê!-.Ê
fg 168.11 AX ÊEaJ .loil LlEtLl= nJ_48! ga^f8 E4. 449
A+4.qE +E+= qlqzl rHg:H 16B.eel e-= EB tlE+= J U= EqE F 26Eoe
TIE+(qtt E+lE)oll 6CE +r, += 6l'Ll= X9
'2JalT.!trI.
-d 2=de A9 Larmor
=+l Larmor tlE+oll
+ql ++.11fl4. aûxqB^B* ^J'}l=g E + *h/"J+ g+7I Fn 9l+. =CE
L ao\"q Foax ^J4=g E + +hl "JA LHqA+./>0"J A
+ AqI 6JE Er+.= aol*q Foax tI=llEE qlHzlE *Al 6I AX,oll lE
X=B
r, +. + *4E gluJzlE +q+ril g+./<0"J trll= r HI
4zI ¤4.
dolzl gqB ql s4 4 ez1 r H]]uJaa- Hh+H dq +4 AX0ll^-lsl
q E6il^J mo4 mx*9 qL 6I+71 !l"J+ E6ir E + H X
^JEil7l aaqr Ael t}=il"J

6tzl ?+=4. oltrll= xE
^¤
ol Foaxe-aoa*e} FoF"e a/x9 + Aol"J "Jqg + 9l
4. "l .ll¤¤:ae t6B.eql +4LllHir, Et tolaJ:=E _zB
168.r6qlE +EI.ll*.4. olE dol9l +Hlq= qlqzl= trl-¤-
I
vx
4e+. fg 168.12 AX2ÊJ 4lE X=:E q^l 2=doJr1l, I 0l8E + X-4

0l trfJ -.lrl rJol =.J=6t71 ttllEoltrl. -Laiq Cll4?.! lll7l= --d
nxluJ 4l
LE= hvrr+hl (168.13a)
I e+oll HldH^l 2Bl|7|- Etrf. =+
tr+4^ln9 dolql 7l"Jq= 49 Larmor liff

q +cg E ?J4 14 2+.JolÊEH$ g+. Ael tr4z} aeq
^s
:z xE
^¤ ^J{"Jol H6l+ dolgl Ell6ll^JE- Hl+qI ¤Bg
6]]¤ + il4t:H 168.11). ol ulle"E:.fl r6n.rs1 r0n.ro"ll 4
+4fle4, ol dol 9lHxlE +¤.4 rJol 94.
LE -hvx!+hl (16B.13b)
rrl4^J x+EE 2J4"1 uf$zizlE /"J + do + ol+9zlE

Ell, ol a+q= X9 Larmor d#ql +Cg E z65ol +r-}
v^
u+. dill4e-e- Ax4lel ,-ElEHg 24lE z6d_q e ol+q
r1+. fg 168.13 AX2ZIE nrE! 3E0l t :z: 19 35Co+ El= fl?]. Ael
ol¤¤ +4r]l: E 6l-+E xqol ABg -Lf X-"jalE el6fl,\j Ee galÊ, E
+ CA 44 Xe4rl. 0l
z]¤- xe+ E"Jel slqlzj q ^1l2el
e-Joll E6t|,\i 4 xu-4Eol Eg-Lf ,JalEE aotltl nt|Eoll
=:B'oll
EzI "Jql M,4fl 4l) +lql^J ¤HaJ ex =e,Jalctrl.

+ed C017|' g^lElol1fif,lel HPaf + d3ll Bl6H^l2Ht|E Eltrf.
=xfl{trlfl(qlE^l
ql^le+ rJol ex,6E x*¤"1 Aql E6ll^l 26do+ e+d
^1l717l
+(:ae 168.12). r44q AE *Eg + xql E"ll^J zJ4ol I

g1 z5r3_" + z3t)-zl:t_ ol 2+d=ol zll29 xql el6|]^J +^l zl r:2: loJ 37HE d"l 44++(+CE tI5+zI +,J^l"tl
,JZ 7J4es e+d4(rH 168.13). ol A+A qlEql +4+zl ull$"l4).
^ll7l ^J
168 NN/R,\E4EeJq 6t+3
=g
rPl B7l 148.3 'sNHlg "},¤zl¤g'H rEeH4'uN

qH
ÊEHql^l "lrll +aE +44419+i e^_ls=
4"14.
^g-+ Fr9E t:tr:g:r:t ?Eat-rcV Nsr ELaf 'tr,,,&Z t:t SBatrrs? Hr .E
(b) Eil 8+"! 37!

vA r\/7l]E AdJe_tr ¤e¤ + qE )-vJ+ e6J tr-+- .JHI49
fg 168.14 AX3 A=Eol 1 :3:3:19 46Co+ El= fl?.I. raJ E N/E +E}q]r. +Hq= qq a"+= 6}ezlE -E^l6l]
=sl 4 C-
168.13oll -H.?l AX2 X-'lol 2=o-E '2Jatts-=tl. llTl rel6}q '3cgzlql 4d flAg "JdzI9 A6J tF+= ,/.nB =+.
Es= Eg ollLl^|g =9 ^ll3sl
col alt= BJB^14 olE + qAg Bol F A6Je__e. olqflg ol(,,C_C_H"il^le+
=rl.
Aol)= rl.n1 +4U+. ,/.n9 de4"J <ig 120 rllzl 250H2
olq, %H= 10+El 20Hz tle+ nl+ r-EEH o + B-
Îolol+.
37Ig #+ xq(Ax3a¤ 4l)g AE +Eg
^l\7171
I :3: zlg + flg eEolxl"J dBol q glotzlfl gHI4 o + +^l
3 : roltr zJ4ol /oJ az11E do + zJ4xlAl ++(rB 168.14). 6J + 9l+.
rq+ aoll zl"Jq= x+Bg 7J4ol PJ z6.nol g+. r4 16B.t2b^lq olq^l !.flo-J uls+ Bol /*"9 +s= A6J ^J
6Iq gHI4 o + NT]]el f,f,{ qg "Jd6}} 4gol+ E4+_q=E 5A +olzl=zl E= yfolzlizl
qlq zl
oJd6l-= E+* ^g-+
7lE *¤¤- N+rzflel d_oE e+ =q7l qlqzl
E Ae-Jq.DoolH HI¤¤
zlal 6Iq ol dEE ^g=E
.r1lzl $:E* pascalel {tz,}B(3)ql q=+. qlqzl ++l7l *"1+14.=fl7!*"Izlr,
^SE
/<0olH ¤q dE a4ql el
ol AL4¤g "t+g ¤9: +lgE + "Jd +E 6Jg zlzl:il_ olB ,/cnE ^¤q
g6l "Joltr, ,/rnE g.al $oll,
Lt4u+. %nE g6l "Jol+. ¤zl^l + zlzl azlt;ll^l E +
g ae /9 {}ol eqlE rlol9 4ql II|+ H+
11 +:. aol+(rB 16B.ls). qlE^l %n a6J tL
+E. q+4 ?"1 olH4I 0(4)ql Ea_61+ql ol 4
15101051
!$ Xarplr",t tolep +q.
3 ,LH = A+ Bcos@ + Ccos2Q tGrptus 4 (168.14)
ol ¤84 {rfEe.l.1 HCCH Eql-ql q6]|

A, B, H C=
^lql^J
4Y z]r] *7Ha -tHz, r4r *5Hz #g *=tr]-. tr+
Eftf, *q=Ergtrt^l+EtrB =zlel
rH r0s.sql E"J "Jdzt NMR
+4+= =EEql*9 ÊEHql
El^ll +a= ¤H6Iqq. 14
r.e{p| ?+?+E f,f,E} "J¤z} +el(qla4 lZ19 q1 12 NUUN

^l¤}
E "Jdzi)7|+s oJCzI +flE di$g q$rll e?+r-6= --
N
10
zl= ^844]] Eolo| ++. f,=o t "JCzL +fl "Jqlî. e <t-

8
/ /'-
io
4d"l ql ^JA+. rBlr ?+ ?J+4 EoJg pascal9 AL4¤ 'l0lJ
ffru 6
g 7l=6]|^J AC6IE ¤tri. -Hl
<l 4
HNCH
_+______-
\
I
cH, o#JzlE *"J t¤g / -/

-HJ
cHrzle-l "Jczlt
=ol +48 I : 3 : 3 : 19 +=!d9 + A?+r-6=trI. uttlzl-
îl
<l 2
0
"J.=:4 0nl2n
cH27lE + "Jczlt cH' oJ={z}el +"J *Eg / "J 7], Q
^\tr_
E4 E?]¤ | :2 :IE 3+.S e e eelts=q. lal 168.1s HCCHT|eI HNCHTlollA]el trJ-Êl eEf 8+9 4E 9=g
Karplus alo+ +El
=i+.
6t+t+ rP I gE
+^l "Jflgl +fl +6JEql^J9 %n +AzlE ol$a|{ rE Ynfi !o

I ¤Ell. a4g + 9t+ '/.,9 zlg E6J ++ql +4u EI (2.82 I x lo-zo ;1-' )x(4nx 1o-' T' I-' m' )
(l -3 cos2 O)rnl
g+
a-"1 cgzlE scqlE q=++ ''nu'= 4nr(3.orloa,o-t'
x(-l)
p3
sp sp2 sp3
tl =1.0x10-a --
T=0.l0mT
rnlHz 250 160 165
zFJ:d o{l 168.2

+"1 +ql fl= EzlE e.J3 trJ= 0llTlLl=g
¤r]tsqEql^lel H-N-C-H a6Jg aÎ6lE "l slqlE ^g-^fl
zlzla- ¤Hg + 9i+. ol ollzlrlfql el6IH tlE4L¤+ Ei
el ¤ql= BL6l= ql Egol ¤4. oltsldJ Tlql^J 4 rhr 4 qI aq+i$ E6]]^J diil¤+. {zlrJ
^J4g + 9l= 7l*
?J
'Jql qql^l= A=*5.lHa B--r. tlrz r4.I' C=t3.Ztfz ++ ql= xe+ y7I dzBJ Aq+e-E ¤eg e"J qlE
ol+. +d¤ +'Jillql^l= qzl no"ql zlt4*4, olfl trll= ,/*rol4. ad- qlTlq=ql^J= dal dzle+ q lsq ^¤-+
g+. +^J BEilql^l= pzf tao'"ll zlnl*A, "l ^JEll
'/HH= 4Hz7l 4 uHa}{l qq qlLJzlz} flap ^l-d¤. ole"aJr}. ol Az}-q
olfl trll= 3lrnt=to Hzzl g+. tr|4^J '/"r9 Atg de4e a.Jg zlzlr.Jol{,4+z}c ,u.gz}*ol4+ E=
_tr +c6lB + +4 +E qL aol Tl+-ql 4"JzlE ¤4 =t4e+
Fermi d+ ^JE4i+9 qL 6I++. Fermi E+ tlEr,tEg +
s+ fl+. $4 ¤ol reg ol$-rN.<J ¤Hg + 9l+. +d eE zlzl E_
Hlqz} ^JzlE ag Hlzl$ol ol q4 Bl+6J ultal r?-l q]
qiî d+zi dElo=i7i qiEoi+r
^J4B.i+(r+ i6ts.i6). dlg
e+q tr4 trqd *ql^l= r.4E+q ^Ja zlzlatg d
ol
Ê_^trJ =Eq fl?l zlzl-ffizlql E6}|^J ^JA zlzl*4 *Al E + 9ltrt rel+
(c)
EzI rll+ql^Jel zlz)4 ^JE L¤¤ rg6tH ^¤-^¤ aEI a4 Tlvl-olql^l= ol zlzl$ol d ,rd".r-zlql E6J ztTltlr+ 4
4 zzl+ +s= a+61 d46J f $.zl$ _:. g"Jg qE =+. ol Hl-,'d+ztC tI$ dz}9 zlzl E-{lE ^}olE zlzl *
=
{r 5ga3 + ?l+. qE ^g 4}¤+a}el z+ d$ol "Jz|+ s4L+"1 e+ ^Jszl$"l4. d+ ^Js4l¤-(A-{.{zl. z|{ol
mra ?4A ql= ol @e_trgq R EJ+ Bq{f dql 4*9zl ?*=)e 4zlzl qql 'il+t;l 7l4Al d=ts *ll "Jq
_e c1g-4 ** z4 ,.lzl* cE 6nu.ol ++'J+
=^}4e +q :z46r{ dz}z} s fllro;-;5- z}z1a3 q"J "JqB + 9l
4(lcr7l ECcI Hlgql E=61-= ag ol rllgolcl).
E^",-#(r-3cos2 o)m, (168.1s) dz} 4fl4 q HI-¤qol?+oH+A sz}9 "J¤zis+
^¤olqlLJzl
dz}"ll 'ilei A+ae) Eql^J +?-16l-+r ^l4ra1z1. "j
7+ e+ (l)ql^J eEE 1o14. ol !g .J+E r0B.tOa^lol4. "J xqol a4H
ol e6Jtlg B1j.zlt} ol 4 zlltslq il. a
rq+ +.-4ql^J. +^l7l uu|trzll ^]]+E Hzl oll$oll G",.E
E= 0<lql Aa^l ¤+"]] +qoF qlq. olnl $oll,<l +*H HL
eI ?ol l-3cos2g9 ¤+3 0olq, q+^J lSE zlA
^l-"lel
4o3 rgfzlc ^Jg
L¤¤ zlzlri +._4 + Ezl.el
ql ÊEH
+EI+= El^ll +a= ¤Hg + S.+.
#J:d q 168.3
Ezl-=ol 3rld6}^l ?+= aill ^J4ql^l= qE 4d

^l-olql
:19 168.16 Fermi E4 AfEAr"Eol ?aH. E *oll^l= + E+(?de q^4 +
q alE6l'= -4 E6t= LfEtL.!tf)011 7l?.lEl= gf=^pll sldt|,\l 8Z
,l"Jqq R=0.30nm$ g=0oJ 9lilql tzlE zlzl*9 z+ ,jal ?JLI.:1a1+ I^l7l 0l +e LtElL.! ZZ ^l7l80l ^r
)tDlovtl^l E=6|'11 EIE 0l
^d$g
q=q.=+ Bol 84. E^loll 4'861.= tr g=^l EEa|'z + g.tl. qE^1 E^l7f 0l +
EoE Afrt1
^1.718=
q7 ql 4-861.= = 4E EAe 00 | El^l E=tr|..
=ol7tE ^t7ldp.l
168 NMRIEEaJ9I=8 645
Fermi Pauli Fermi *g qq \S zlzlzll BtrI ol trllT}Ll+ql E6IE Yel

^$o1
rA xel BB"J q qlLJzlz| {oi4l+. *ol 94.
X O,
lv ? ^fl$
Fermi d+ trs4l+ ,J^lql E+ q
='lrr7l
dz}
^sr+ ^gr+
el
^JE++s "JCzl ^Bg A+ql= Ell+61 f.qalzlq} 4
E a"+E qql ql6ll^J= r+zl ?+g +E 9l+. olqal q=
x$ gY g rSqÎc qlrlq=ql el6l]î dzl.9 ztzl EHltre+ tls4}
¤¤ g + 9lr ol.el ?llE ¤-F6}l.E tr-E L¤¤ ts + ?l
leJ 168.17 Ê-{EJ e:ct('Jc*)sl trJ= trllTtLl=. + ut|gg EZ$ 0llLl^l
eq, vl "Jol g^l E= +ol ¤zlE E^l6J ttr6J *B"l $.
il= LIEfL.!tr|. 0l e9q|ts tr! 4E=01 UE-"JS xll Dl g0l qq, qlLl^l7f
tr}. 4^f,-rzlc qr+ +H "orcx| E+e+E tls4
'frI ^Js4}+_e_s
¤¤ ¤Eg + ileqH E^l-=ol xllf E Hq+E r B+ol
0ol qzl ?+=+. oltrll= tszl$ol r-:cos209 z-ll==9tr El
ol qlqzl Eql^l +E-l6}q(:ae l6B.t7).ol eE}q E4 dzl-
4, ol{el ¤tg 0ol qzl ?*=tr}.
E a^SS zl\"Y 4q(Eq s9 pauli tl"-lql 96ll^J) +E
e-JE H ¤ +ql "lE4 qlgo} 6Jtri(dzl_E=g d-g. qlgg (d)
4+^lzlzl gla1l.<J ^JE g?-l gleEl= a.J1g zlzlzl ullEql). -:d-4
rqH yE dzl-l¤4 HI¤q"J Eol u|$zlals-+ 6J +flel 4Eol EztE rlla allql el6ll^J g+qr E q
Yqg B^gg ^Sg*= aol a^Sg ?*Y 4H+ *e ollHzlE eg ElqL4 ol5¤ ++B ull} ol$$ trl.6l4oe fii6t+
7lz.l4l g+.Hl.+ol ,f"lzt$ q-^flol HI¤B"J ull$ol paJ _a "J6JtrL. +q}4eE ¤E" * qEg "JHlzle p+q}4 7l=ql
dzts+9 zlzl4 e'JE e4E "J6ll^J ¤B"J H]]SB+ *g ^JE

E+6J 4Eol4. El44 " E ¤+6J +"J olq+ E6J +
"llHzlE zlzl4l g+ +,/.nE "J"l
g+. zI "JE 4E zlzlC qEr+ E"J+ ^Js4L¤¤ 6I
qEe xPl{o+ EE6}+a gq}+. ^g-^fl
H-c-Hql^Jel %r"ll qld)]^Je+ *o1 ,t*r! <tg ¤¤6}zl
=
+l"l^J= 5tC cgÎ(zI4lE q *zl tlE ,2cg +E
9l+)E E6ll^J
^¤gqlrtq+g ols-" aflo[ fl
Hl]gol dgral=
^S
4. ol a+ql-(rH r0s.re) a^¤9 7Id xqol r ¤aJ 4 E|+zl f,f,$ zlzl4 t¤. ^l-ol9 il+ cH2F2eI Hrc=cF'
9 dzl# ¤+^14\ azJzl$ c4 zlnp glril 6ll E * 7l^1a_ ¤B6J + gl+("Fg qol+). ol= 7+7+
=+. ^fl-+
9 flz19lrl= + $zlzy Bqf, *b uH9ol r-J #4 9 Ez}"ild 4E("JCzllg'ilag olFzl qlEql Ei+
lH
^gg
6tF +(tr-9 ss9 Hund9 +zl) "Jd AoJe) a{zlzl c4 zL 4o #."614.rq+ cH2F2el "Jdzl¤e zlzllgE
v]pla s= Hll¤ol B4 +46llrl+. Irl4^J ol a6.J +E Bd E F"6J +Hql cHr=cFrel "JCzl¤9 rezl ?++.+
zL= yq zlzlololl.<l Bdgzl +l+q rq6}q Yqg a"J 4l cHr=cFrel * "Jdzl-= 6J +qTI Fqr+ cis ^-$4.J ^Js
4L¤¤ ol-= +¤ E4l H "JCzl-b trans *e +trI.
ole+ qla4e + cH2F2ql^J= +
Hund
"Jczlz} eF ?9tl p
qr+ E"J+ AqlsE ¤aqq ileq EI+^l ol$,r.l.ololl
Pauli
tot
lct Pauli
o}+fl il-olE H+.
Fermi ,.'l
..I't Fermi g"J6}4l "5"Izlts cH3cH2c14 Ag Ez}qlrl .ql cH3 oJ
YA
bY dzl¤9 *ol9 2H4g *zl ollEql ?:r+ cH, oJ,tJxIe+ tr-
I
I oloJ paj$-
"lE + ?lo
o+ zlzl\-oe #6}zl ?*4. z
44 dxllql 9lq^JE cH, 7lE mi. +tr+ 3tlA^14 ol4
.leJ 168.18 2Jr, .,tg_,.,rJ edoll EH-d E+ ollT lLl=. 80|-d flIl. fllE-tsr+ + il$$ ¤=sl^14 ol oJCzl-=-o| zlzl4 o + d'
=:e-erqe
+sl ExlEol oJ:d îiJg nfl LJe oilLi^l= ?*=trt= ollTLlaaEH q.6Eoll Eo}rll "JE + 9l+ 3rlE4e t+6|zl"J zlzl{_o_+ 55
S-el Hund9 ?41)It Hl+-Lf ollT[Lffoll q+,\rJ +4 LHEoI el ,l-er'e-e 6tzl ?+g +E=g r]]+61 +A'-+ l{Eeg +EI{q(qlE^J
+El cl-= eEre.e EgEtrl..0l 3?= J<oop,\1, E4 E=01 E=d"J tr|l
HrC=CFr$ "JCztel "FE 4trlEfl.g zJzl t2t\l9 d " +
0ll L1^ 17 I H0ll= e+oll 6l|=J-Jtr1.
^
646 16 rtTl=E
qqfl+), q7l^J= rJ
*4t+. olt _r.El6}zl /,or",= 1, Mt=-1
+
plqr4 olfiol ul
" + t=" ¤I zlzl4 eE ¤I +sEl =49
BB
/\EI-/\Irl -,\El-/\irl
-u
77tl -u
+ ^JE a'J tls4¤¤ 6l-zl"J ol a.Jg E"Jql 71el
=u =ti
ÊEe
ot+a ¤6JE +zl ?+-+E aolq. ol7l+ 44zl +4+= S.= nll glE n]l
olf+ A, 1fl \\fl zlzla_ ¤BR + 91tr1". t d t4l-tr- qlLl op+pa

crp - pct
/ro,",= 1' M,=0
zl -r.36floh ++.
=+l$$ /ro,",= 0' M,=0
/,oru,=1'M,=+1
3tr rl OG hJ
=+l
27]rl4 4g-+ 49 zltl A,41. ^J4I6II +d 1¤-4S Aq+ fal 168.19 Ê_^rJ flE nllE A24lE ollLl^l g+oll LIEI.
=?l=
AElg r
ol S.g UIE qlqzl =-crol gE.49
^J46ll HÎ.
LHfltrl. ollLl^l L[E[Utf. Eill
^trJ-ltrJ =-ct= r.a16H+E
=fl=
+6|71 +16ll^l glulzl$ 4l4l6J ull= sd{}
^S-^S Elql6} E!
^rJol /tot"r=1?.! 1lA|Et|(3=-$= -E+ E=d
=Pl7l-
ArJoll dl|=J6|"q ollLl^l Eg:d
^l(/,./,ql a7le=_ LfElL.lrt(J7l g:oltrl-). 0lel Eil54oE /,o,.r=0?.! Sell(E"J-d)=
ol4g Larmor {Ffz} 596lr. E.
qL+. 01lL1Il7l' '*0|-Ctr|. Eal^q C9.e E',t.lE -=lE t0lEP A/,o,u,=00|-tr,
= ^l)g ^l-8-6]]0}
,i=
qI Larmor tltlfzl rJolts oIqI LM,=+t ?l Soltrl. 0l= Eol= f! B.= titlel +'J?
=Î^l(Irrlrr)? =zll "l+E = ^rJ- =-Erol
+ 9l= A"lzl rllE"l4. aB Tl#oil^l "Jolutrl..
E4l 1 tF4EE +qI4 ¤t}"1 Sg q.el olEel

qlHzl ^g-^{
ql T]lel qlqzl ?fl71=z]]6J+ ol=g dill
/,=Ir=jols + ^¤-^S AC+ qlqxlz| ffi$ *ol ¤4.
4+E%i
I,o,(¤ri dzi,li 4+ se+ +î.-i-+)r+ ojz'ri ^S
ivirs iixiL
p-rht[r tr -r-r\-fl
2,., lLlret \.tor , ^,, 2 )
J z+ CEg zlzlt- +Eg + fl+ 4,/,o,=toJ :2fle1 ^3-4 q6|]^JE tola rrl-{^l E=++hlol qq,
868 rtot= HIB
eI I,",=goJ E 6i+E
^JE{s +B$ + 9l+. ^Sql
16B.1eE sE +ql +4.11fl+.
}'gEol ¤B"J oll,
{o, = I' Mf tl ao.
M,=0 (|2uz){s$ + pcr}
M'=-1 PF 4l&g 6llHE ltota= loJ ^'ll ^JEll= E+ qlq \zl rtz$\l
lflEol zI9 "lE 41, {";0' Mt=0 (Uzrz){sB - Fcx}
HJ-6J'9_tr A¤- "J"J+4 ?zl*4./,ota=OoJ +"J.J¤- HIEI] ,J
6}e__tr 3H1] trJ+ AA6J+. *B d"l{l^l= flEel tr44 u}]
olE trlilE zlzl*4 s.r+E- :zH r6s.reel ffiql
ull tr-EHq 6Jol H6J + S.gq, EI+^J /,*aol tolel tlEilE ÎolE dol
+448.4.M,=0 oJ + ^J']]e-l "llHzlts zlzl*9 g63.3 g ?+=+. LM,= r 1E dq +!E "J+qqot 6tq,
zl *=ql, olag olEol ESEL HlgE a^¤4 B^g-e--tr- = "Jqt+zl
4L+F%i4 *x}g ++l _H_¤ggo} d+. :r_H 16B.1e
ol+qzl_,4 ol + F"J6J Larmor {f,f$ zlzlzl ull ^flol
ql E.J uts+ R"l -d+q= E+olq, olEE qlHzl
Eol+.
^flol =+lE
7J4ol E"J6I7I ql$ql .sg+ Affi ÊtrHql .+4d
cJAl2 q+ +. El+^l a'J ^Js4I¤+ A2EzlE ¤
^¤-^{ ^}Ezt+el oJS ^fl-^fl
fzl ?+=+. ^trlEHq
E=(hllh2)It.Iz4 +E 144 a':3 d4l 4 Afl 1,o,=/r+12=
olf-oll.<l +EB + 9l+.
(e) e-dEJ eI
I.,", = (I, + Ir).(I, * Ir) = Irz + I] + 2Ir-\ ^llll
a6Jol 9tg tril +++= NMR trl^6d
ol r+g-r+ Ae Ar+= Eg +
^g-^s
g + A+ ÊEHq
slE4 olf; zlz| rE
^lg C?-l6tH
914.
^flE ^l-ol9
a6J ^J+tr+ gd q
^l-ols'l ^S-
ql Hlr4 a+6l.ril 6H4g +
IfIr= +U.2",- Ir'- 4I ^s
gl4. q}4l= g6l ffit Eilol4l=
"f"IE e44 o + qq
"l
zllE: 6.J¤¤ olEel += lE-EH9 ti[.,rnflegol+r 6J+
']¤-q "Jzlqtrl4 <te_E Hh+q=+.
s+trizJ olE-E zlz| a6J tls++4 EHI+e- ull
Ir.Ir= +{I,",(I,", + 1) - I,(I, + l) - I2U2+ l)}hz -'l-
Ê--\g
ffiEzI B+ +flql gg +$qlq 6H4i;17)71 q
=lC
168 NMR 4E4EaJol -=rt 647
H
C
(d) voAd << J

L N
L
lcl v'L5 = 2J
fg 168.21 0| + 0llE7 lE S30l d0l6|'q rElN 61tr14 SA0l
E^loll^1=
-s0l6l-tr|'. c-N +gel elcoe + 7l7l Hl+lE -d rll=7171
(b)v'Ad = 20J
+ ge =-ctEE:dtr|.
g+ ^lE =tr
^pE
4.=lz] qlLlzl9 B4= aH rcB.ztq +{qlB.4.ol BEHqI

(a) v'Ad >> J
.rA 168.20 (a) AXZlel'(d) Zsl A2el eg 4lel NMR 44EaJ=3'E+' F "llB zlE ¤i]="6}zl ?+s4,6I+= zteE_B Tlql ql6ll
aEEaJo ltrl'(EE-d A24l0lE A6= 00lrl). a[+4 olE^lal Ê-aE ^J
rJ cisolL E alu}-'- transol4. tr+q^l ol + 7l= qlAol ,!tr
1
^l'
8Eg d|Etl4 'J(bel'c)g tttlts Etl.EElEl {l
=:Bfol =rJ =-ct ÊEaJol +sq q4^J +qt4 olEol t"la}4.
LfEtutrl. AX ?J+ F d0l ,'.le 71,l?.^la_,
:Lalr = Ê4EaJq
Az^trjlEaJ9 3C EECo e E6ilA+. ^1l7l7l =716lr,
C_N AEL ++lE 180" fl{.rlzlts +"J+ B4z} 4_tz1"j
cHrzlTl + t}olal ¤+a r.++84. "l F ¤E]]
Îolql^J ^Lol
vYtr+#tr+. olel6J lllll 4l4r "5"I4 lEE E EE ^-Ezl Lg trll= 4I CH3t+aql rlt* + dol E+6l.
^fl41. =EIEJ
H9 zrl ,Ê]=gol4r q]+. olBl6J dEq ,ll +ElB+. ral+ ol EE 4szl ml-= Q= F EleL4 "lE
eF* ÊEHql=olEE zl-
zl-4e*rl el B+ql 6llR6l-= t"J dol :-slsflgl +$trtr}.+7J 4E
+l717l a6JE A+ql +Q't"t ts
el EE +Eql^J: dEol Holzlzl ll4rafQ A+3 He +
+4+q,,rllzlE_ r|_=_L, EeI a+ql 44^JE +714"J
r-lql
dE=E +E|ts+. d a6J dEs] 11t+ "Jd-"e Bql$q-. ol Ho-Jg rp-r+ 7JC 44ol ;ta-g trll
e+ ElE4 olEo4 A.J
^qEH
^¤iEee-rlol9
S4l7l "+* Aq+ "Jqu+.
^J+=E zt
g trile+= gq *+6lzl ?++.
2t2
-r.B 168.20g + e6Jg 4t Nun + ?-_
Trov
+ N1MR C=sl E-J al (168.16)
slqtzl ol='^gEq
Ttel Er-+st ++uÊEH9
1o14. zH
^¤E ÎolE
16B.20a(AX +E)ql^J= ol ilz[ qI* eo-Je] A+84
¤zlrJ ?= il +AE f$"l{, 6vb F {+Ae-l Larmor tl#
=4, ilol+.
d=el 4lzlzl s+ +Ag F z613ol ++ttr1.. slel4 ol5
TJiE'-ql q+
^l7l "J+ dEq ^llTlzl ftzlolt- Hle dEq
dlzlzl r"J+ +êlq. r4r ol olgzlz| 0?l +*(A, Ê zEtEt 0{l 168.s
EH)ql^l= Hl? cEol s.qzl-r. "J+ dEol +e¤q. N,N-q gq E tr.ôlEl, (CH3)2N-NO(5)ql.<J ttOzlE
"ll
5. qol "Jg ^Jol6J gAql +6l4Ll(qlaq B6e{'H) e N-N a-J ++lE qdg 6p ol qlEq + cru7lE 471
e- fle+E ^Jolq} ¤.ol?lôlH(qE^J 'He+ ,H) ol=el 4 {+aol t}g H+}94. ooouHz Er}4lql^l= + cH,zl
Larmor tjffzl rz]l 4-=s + L4 AlTl.Jtl-.+6141 A-J6I
E +HoJ looHz "J# Eq4 +4U4. "l ¤E]]Eq ¤+
r qe}^J Ax4lE ¤E6J + gt+ E]"J + 4ol F"J g^q +Ee 16B.16^lql E6ll^J q*q-r+ ?ol ¤4.
4EolH 4SZl. E=.-4 z\fj{!E ¤EB i :ll" ol$ol drol
{} fla=9 4olB ol=-4 ¤B6l]0} *4
2v2
T= =1.2ms
Êll.g nx(390s-')
-
16B..t, EEJ EE!
zlzl4 4ol tol6J +a uu[tr.zll EqIC + 9lg *]l=

L
^l-ol=
NMR E"J"l E++. qle^l MN-q4lBqlEol-
ÊEHE
ulr HCoN(CH3)2e+ Bzl-= liltaNgz|. ol EzLql^l= C
eg
o-c-N7l= ¤Hg ol+4, c-N A6J ++lE 4dol zllaJg s ,U,U-qql=LlE-tr40ltrJ
6t+8 Il-71
=E
olBloJ +Hg ut_870s-'el lz} +E ^J+ql 4'J++. trI

qr-E6}a)e+eg y*e clq|+Ee Ee4"J r^ll tlEllE 9lg
ullz| ¤7 41lol{, xd El¤H oE
+^l tl-s Hi+ +E7l ol zig a4a1E + *Ed"l H* "lag ACts + H+.
olel+ A+ql= rill ol$-al],rJ
g+. ^JEll NMR$ ^l.EE +ae+
E4 CAg Ae6iloF *4.
rillg d+g xll zlz) # zlolE ol+qzlErll, aail= q
zlzl t+zl tszl+ol+. ^s-^fl
^lE +z}e+
oJdzl-= n++ts
+ 9l= +ql +qlrJ "JdzI9 ^flE ÎolE 4d4oJ
ul,gl faTl- s,qzl3 aE +lql^Je+ Hl*6}rll ¤BB + gl Aq+g 5.e_l6J ¤¤6J ulpt ?ol 4 ztzl EHIE= q ++l
trll
11. qled q+gE el +l^lql ,rI4 : "Jolol tolel +zl4 zlzl*& "J=trt. el
oHzlel +Ee +"Jde
ÊEHql^J
E +4\i+(rH rcr..22). ol Ezl-9 6lE+d "JdzFb E E * zlzl*E "J6Jql ¤e+ CE"J$ IEI6J ulE(dzlle ol
zlE "JCzte+ l+t¤4(+o]] *"ilE 5E6l +E= 6l-zl ?*= dg"Jol +sq} -Er+=- ++U+) +qzlE ^&al zgql^J
4l+ rd4 alg ol+al.{ "l +zl4 zlzl*4 3_7]|= trl+r+
^
eL E +ll7l B+Ee^J Eqfl|l u}fl"l4). $|zlfol r$
9E "l*l+ trt+4 a*ol "Jq+E RoH Ezl9 a^S *C Bol 44'-J + 91trI.
z(noH"E g,tlo-J4)zl RoHre. Efl4z1 olq^J E RoH*tr
lE"IzlE fl4. ol4g E Ezlzl "Jelg ,'-g uflaj$ zlz\t_ E,*=ry#(r-3cos2o) (168.17a)
ilq^J S9ol oldq= oJCzlz|. +4tCE .<g u11ffi zfzl

I ?lzl ullEol4. 8"lql^le+= E.4 l4l +ql^l= tszI *Fol se u + ol zi
TltlE B+ilzI ool 9zl 9*84. :4alq eI +d ..lltr-qql
"l o+ql4 t+| 4C94szl eq+ tr"+ /E #B+ uul-s$,
Ut >/olE + lslEH"l Hqlqq +"Jcg ++.Irll g 6lt dill 1zl4 zlzl*2 "*9 Q.e+Elel zl{z} a;-
zls"
=
+ a6J ^J+e_l (ls=g d¤4eE i H, c=_o1o + ol slql 4tt d"l"i, îE +el q4 iioioj e"ii zl+6'r= xizl*el
4 l¤|"1 L7lal "Jq4rlelr xu1_=Hol 34^lzl ?+= a H+lE Hqd+ d¤4oj tt-lz[ z[zl*3 lrnrE .uzlolq,
ol4. $r]] +E ++g tsxlal z1146}0l oHzle-l j/+ +E= olag,HE a+ lokHz aEq 34d"14 c+ql 5ll'&6J+.
+Bfl *al 6IE ?J+Aol +4l3 + 9l+ zlu 0zl04 g*.* He. + 9lg trll= l-3cos2g9
Îolql^JtrJ
¤E-ol -(cos20-,,+cos0-,,,)7} E+= ag B"J + 9l+. "l a
r+E- 16B.12a44 eq+6l]+E ¤+ +zl4 ,.lzl*ol +¤.4 a
168.5 r.i{l-8E]l NMR
"l ¤+.
*.-! +E .(lEzi NMR trl^tl +4.444ts rll
^trlEHql El4 Elqr-4
H}6iol, lill =ry#(cos' g-"* +cos g-u* ) (168.17b)
^lEE ÊEH$ Hrll "lf,-$ tsE Bror,^t
g + Hrll 6Jtri. :Hzl"J olBl+ Bag ++6lEJr ol]A=

ag rE"Jd ¤lE6J ol+7} ?lzl qEol+. r el ol+= d
zlEtEt q 168.6
E rfltr"plaJEol +.-q +ql^l E.Je6Izl+ B*^d"J + 9l+
=
aol+. g"J otq4 +Elill(6JdB 1"14 zl94ql ag 0,,,o-30oo'll R= 160pmoJ rllE oJCzlql E6il^J
^JzlE *
zlfi zlzl$ol trl-s=$ eol 94.
hthlto mt cos2 or., + cos 0r.,
CHsCHzOH
CHgCHzOH
GIo.,o.,=
(3.546... x10-32T-',)* 6.GB
4nx(1.60xI0-'o m)'
CHsCHzOH \--n-
c
=5.57x10{ T=0.557mT
4.0 3.0 6 2.0 1.0

d+ql q6J Ezil Tlol= e+E4 olEol +44= HIEHJ^d
f.g 168.22 lH(gd^l) gxl= tr|.=dB
oilEJ=e_l
ÊjE=. +^4
NMR
"Jql Xz1 c.Eg +g^l7l= e-l+
"l+. sl-+4
ol.E,¤. BxI
LIEILH= 717:9 g¤xl.= LfEF.lEl. OH s¤xlel.Eo|1 +sl EErf /.l0lE
nEl4l* rl|EolloH g¤rtelE TloJEl='Jzl'EB L|'EtLf^l ?j=tr|. zlzl*4 bq q$q ++tr}. oJtl4_"e. ol }-qg e-l+ tL
=:stoll
168 NN/R 6t*9
ÊlEaJg =d
ql ql6J tszt9 tl.ilZ] ufla}"ll tr++ trIs+ +.+ql^Jb EzITI ^/
uu|$ fr_+ z]l+= Heq, ol4rl Ei+4 ol5-el ¤+zl7t t+

Elkitrl. rq+r.ill +ql^l czl ^JEHql 9l= EzI9 a+ql=
HIF%FCE ¤+il7| 0ol qzl ?+eq, Exl¤* -z uflaJ"ll rl
4 ,<J.olal d#ql^J +Eg "Jezlrll ¤+. slql4 olFE Bl

E"Bde e_l+ tI4 Ezt ++ uI4 r_3cos20
Îolel 4s.gl
EOJ + H6Jtrl.
O
clall zlol= d7l 4+ +4 trs4¤"l4. I > +"J 49 dzl E+

^l-718
4+ +^l EHIEE ^Jzlzll 6I= d6t +EE A=+(qlE^J "J
a6I7I 4E ++l+ + +ql d+qq9i+). 4zl q* +zl-=
421* zl&zle+ tlE4l+g 6t=ql, olBlqI 4¤+ d6}7l q fg 168.23 e#?: alcEoil^.i=
^lE=ol
E+
^l-7lAioll
Et|6]|^1 s4.74"(=
arccos 1/31/2)E 4s-+ ffilell xtE,\lTlE
0l+41 dlE,\i IlC,\lZEl. 8--Il
++lq +¤-oE EEqzl ?*zl ollEq "Jqt4. "l tlE4L+ -8+^t SEltEzl El+4 olEsl Hl=Bdol 00+ EEaIE+.
E l-3cos209l tr}4 EqI+.
+6J6lE r.ill ^lEe-l d+¤ ¤q ¤ + 9t= *BEol ql
4. r t ulBol g=4 rldH(MAS: magic-angle spinning)ol ,q+4ql^Jg <l"J 0o + ¤#s+¤+. ol MASSI^J= r zld
Ell, ol13 t-3cos2gol ,r$'-z|-.[l^--z] t]E++, Hlf,*C E] tldfzl d+Er+ 4ol^J= ?] qq, El+^l "lag
qzl olE, :ar-]tr 421 q* +zl ^trlEfl + 6ll+qot qI4=
^Js4r"+ql E=++. Îd f 4e"il== Atr 1"1 "lelg Ezll+. ¤
9 "l+alE 4o14. ^lE fld tlil.
,q+49 r-3cos20=09 EI+^lzlY zJ {E zlill-+Er ol+6ll^J s0kHz CE-
^lE.
tr +^J sq.zq"4l6ll'JoJ+ ol HlBql^l= e-l+ t1-ql vlrl e{l Eld^lrJ + fleq "l *H o + gg ¤+71-ol+
^lE= 'l]
5I^J ,q_+49 olFAl 6IH^J mlE +EE zldrlA+(rH qa+
168.23). rflH :r= 6lazlC tr-Ezle"rI +¤ BIE*tol ol
7t|E=
=sEl
ll. eq flEt{ ol5g tB 154e+ zl=o e a= E= 3lB I9. ^¤-.9 A6Jg E= rllTlLlE4 Fermi E+ tFg.=tEE ol
at+ ^l"lE
iloltrI. *5ll^l ¤H6J + 914.
fJ2. TlalE 8+= +^14 zl¤, qldzl zl¤, f?-lr +ol] zl¤E Dl0. + q ^plg Eiqzl olszlz| + q ^l"lE a6J,!-+E_4 r
'Jt 4o14. H EEI e:d 4fl414I 6Iq, ol olf,ilzr A6J ^J+q Hl"ll
tr3. +xl4 7lq= qlzlzlc zl¤e+ tzlzl¤ zl¤49 6}oltrI. ,tJ z]'98 rj! 41e}a aJQ.
=-sF;-g
e4. ?lE7l 7|q= "Jdq= flxttq +gg d+ trilEq ^84+. trll. ffi{oe EsoEJ eg Eg'J 3r}q4 olf,f +E}U+. rtTl
trs. EBl| 7lq= +er+ +"]| Î"lE 5Aa tlszi+ trIEql ^J 40e qq ql6il^ls u|4!zl-zl"J gqq, tr|= qEql
-ooJ
?Jr+. 4+ e6J ^J+E¤+'+ eE. 44ql ql6il^.1 e4.
D6. o[.ll ?;Eb *Eol a.Jql 961i^'l 4]E4 dE=E atz. BEll+ F+trI4 4Aql 9dl^"1 4ol El44 $A ^l"lql^l UBI
^¤-^gtrlfCg
aqd lolrt ol5 zJ4dg +E-E J-++¤l rllE Nund=ol B'Jgtrl.
"JE4.
=
g=4
L) /, E-Û E:dg 4E E:d 8+ /= zlzl:il- 444irll, F D 13. rlEE(MAS)g r,i'll
^lE=
e.l+ zI+ zlzl6toll rflall
q Hfiolql E=.JtrI. t1 s+.t+"# ol+rll 6IE^l ztd^lA oe^l aill .tltroll +EI
Êel ^Jrlt4qg
D8. a6J t1-+= F E4^lzl= ¤.J9 fzl fi.zl$o1l tr|+ 4b Nun c+¤ +t^lvlY zl¤olrl'
e^++.
6s0 16 xPl=E
=s-d^l=
.rlzl
de. -1I +4 4Ha
El+4 ol59 64E f ={(v-v.)/vo}xlo6 ct
ol
z-l --1
16B.4a
Elut4 olE" 4 z|?-l* t+ ^lole-l
f =(6o-o)x106 168.6
+4t
714& tr-+"il'il+ +zlzi 7lq o(local) = o6* o, r68.8
Lamb
^l
o o=(e2 1to I l2nm,)(l I r) flxl-591 48 168.9
zlEl* tl+ql 4'J qldzl zl¤ o(neighbour) * 06r- )(,.X(l - 3cos'? @) / R3 l 168.10b
Karplus ll 3/Hn=A+Bcos@+Ccos?S A, B, dE4 tL+
'i C= 168.14
+ NMRCEoI H6Jq= 4a T=2't2 lfi6v rE f,iT I+AE +B 168.16

EE 16C NN/Roll^lol '=^ 7lE
zlzl1 q z)olzl {r(r+r)}'/2 Egloll z+ d*ol *,*

> ol EEIE Hll+ts ol* ^Sg
+lzl. 9E EqE ++g + 91trI. EqCC gplql el6ll^l 4
Er|{4 xl-7lAgHslflq4 E9l= 0|6H6E1E E40il ?S+trt+
gF=*E ,+ ¤¤.4/+ CEe E^lg f Hzl"J ol ulrlzl-z
tr4
EAE olg4l 0lE6U M4_=aJE E=^l= gotot:drl.

+ ++lE ?lg^JE qL *"Jrlql +lil++= aEle q¤6I
> qqd 7llLJ 4.r:+oJ lgE 4* *,=-+.J rI z)olzl +J3"J 4r.l7l ?+
gaJg ? N Trh gÊ 0|e-6lol e4 4E!= Eeil otq Ezplg It arccos{}/(+,-'5)}= s4.7"E 49 olT;, flgq(rB toC.t), s.
NMR AE4EHS Lt94 alI:. Ee+ Al?.!= 6] 7n,:-l.J trilE z-44 olt ?JE+.
=8e}tr'l.
= '+z
> gsil qlHl zlzl$ol S¤- trl]=
^lE +ql
oE
^fl4 04
^fl"]
*+
^l^.1
EiBol gHJ4 gal(c.q ron "f 168)cl ?_JEE*el EEI e E99lsq, olE ulelzl ?lE ^Jq +4'"e6}rll *"J4. :z
^l7l
s.J(Etrl 7F)E +^16l.r,9loloF:Lltl. 0l EEg ¤861.= al¤011,\1 44q ^leel ¤E q zlzl E_{ltroJ xPlE}Mol 0ol g+(r
Larmor TIE+(EEI 16A)E T.!E-6|E lllil EEel TtlE= 0lEolXl H t0c.za; . a-7)zl EooJ zlzl** z+ HJ6J e-E 4L+^l7lE +
Erl.
Hslz} +4U+.
F tr-Ellel ollHxlzl H6'[q, a1fl9 *e qlq 4+
altl Nrun #Hql^Jts.Larmor 4l5++ r ^flrelI-B^gg +g
o E, qlqzl $9_+ olE"t4(7*>0
d.r cl
=z]el
+d_41t+E +^H.g^')= *Bzl "e zr+^14 e 4¤g "J A+).
EErll +trt ol g^ 4l+se E=E ^fls=g ¤B ^JqE q Eq E'JqlrJE ol + EelS Larmor {Ef(Eq t6A,
E"tzlHrJ +^l-i4¤ q+=tr}. ol ^lt-g= {sE zl$a}r. s]dol{I ,H(+,
vy=fy(Bsl2n)9
^'11Î ^J46JtrI. l0Tql^l:
'Fourier H¤I(+ ¤¤61-=)9 6ll+H Ezil ¤4. ol 'oJCzl-')9 Larmor 4lFfz} 427MHzolq, e-l+ zlzlltel
^4Eeg ,t'1.|
q6J
"JBg Fourier EE ruun(FT-NMR)ol4r ++. ,ll4^l zlzl frzlx]g]
"Iz} Larmor tlf,fz} +7li;la_ îli}
sldol E
++Br+ Br- NMR "JBe 4 ?ol ¤:0.uyo1 TIE6I= Tl+ +Tl+.
+= e=61+ 4,olzl"J *Hol .<le Q-e.4. .zli4al, HlBql . 94 *lB ^JEllql^JE + ^J49 z|zllltl HoI4, a
g^d Btlzl$ $Czlql g{ql q+, gC-?lE {54
^J= ^s
#zl94$el +B+ EA "*"t{+(Eq 16A).
+Î^l7lE^l +q+ ¤-c¤- Eq]I" "lq^J +Bol "Jq+ ^gel
=
+d "JzlE +g trll4r +ql^l +s= tlE= Fourier H+|g {a. z}zJE}3 ulrl ar"e 444E']], Eq9 =zl= 7H^ll+
^14^J
+9 +|.B Affi
"J"tU+. ilql Hlell6}r z4* 6J*trHrH r0c.zu). ol ¤tr ztzlo] ul
zllq^l "JH.il Hl6ll^J Fr_NMRg zlEzl zzl 6zl-el4= qE azl6}= 4"1 trl ,lBel +d rlz,ll"l+.
oldg zlz];:il_ 9l+. rq{ ,JBE dzll4 ?tA!- "Jdel
"l
qBl g^= trHle_e 4+^14 4 a¤g + gl+=
4"14. ol HlHg 0l+6l$ 5A+ ^flg zlaofb
=Ag
g eg f gll rl ulz[.{ Ez}9 += Ceg AC6F= ÊEe
'1l"ll
E ole"B + gl+.
'I
16C.1 rPlEl ElEl lls
g^ HJ^lg olaflalzl +lql^J

"*g f,_}6J 4 o + g ^l lal r6c.1 mr =*?l .Jg 4E!-+ --jq 4EE-Joll rH-et EE1 E.J. flg 8g
^g-+
EE ^J46|| HzI. Eq TFql^J ¤E+ 4gE=*E 4*g+ "I4l ulElg 9lil=
=+E0ltrl'.
652 15 rPl=E
M M
M
v
ct,
\
p ----------------
v=va
(a) (81 (b) (81
(a) (b)
fg 16c.3 (a) "J4 NMR ¤-doll.t'l! 9'5-1154 Ei.l.CE tE^lZ dA

leJ 16c.2 .^rJ-+ e4Eol +l 91ts ,\lBe] xtTl+ EEI= l= Ê E+E ulEl= zioePEl aEqq LlTlAl -drl. 0l xyE8ql
xlTl sfllE= -drl (a) 9P flE trll= z=(9P89 BEI ^l7ltrl
Larmor tlE+= Tlxla- trlE6l.= qZ =^tcg
8.7l4l:dtr|. (b) Larmor tlE
=r+trt. ^l'71801 ^1718
++loll +lttr-d 4Ee HI|BFE oÊrlBÊlgl +7|. eeq rfTlel EEI= 45 z[xlr elEa|.E E 9loll gelEl^] HE q0l tr^lE Aîg Eg 'zloltrl'.
ool'EEt. (b) E+ lt8'g ullts a4rJ9 +7|'pÊlE tt/trt e+rJ tr1 -r.al-r. ulEl= q T?lE elEalq, reldlq qEl
^17l8oI ^lEE ^[7lsl
7l z=oE+Ej 0lE6lr. xy dEE^171et ^17lel-
"lJo tt!tr|'. o | trllEoll z* B:*9 ¤E xfz E[ Mo I LlElt-Jtrt ralLt ]yE Aloll^1= 7l'^l1l EE[.
qE6l^rJfll ++E6l4l ullgElol Etrt.
^l7l:el7l001
"l+al 6LEJH gÊ 67=Qty*8, E"J zl+^l4ot t4. zl+

tlz] 6x*=nt2(T*8,)4 90" E4(90.ts 0=n lz t+q"J)E 4L+
(a) +d+trt+ rPldE Elt zlz)* ulelzl z+etr+q xr-tse_tr. sld¤4t:zB
zlzlp] ^l7lE
Eq= +d-4lE+ +Îd Go& 4¤-^l7lH BB +lil l6C.5a).
s+El qdqq Eq4 'IzI+. +Îd (Bo*x7B9ld Larmor
d5${ooql 44 +s+ rH l6c.3a)-tral{afg zlzl* a,
9 ^Jzlzl EltrI. "l r+Ag oloflalzl glollrJ ,la z+ ++l= LEIET 0ll 16C.1
41f,$g irlA6l-= fld
r.armor g+H+l rj4ta|4. o1 +d_41# ¤^9 zl+ ^lzlg q4 \lz)ql E+++. "J
=ql
34d 5ql^J BE 6,zl.7lt}"l 4z16|r. fl= Ail4 y44 4 o=| e0"
E^zI lops EoJ Bs-a1r4g "Jdzl-9l Ell6J,4el ^'ll
t6c.3b).
"lrHrB 717l tr|e--r+ Bol ¤4.
dfld E tril= 9* zlzlatol u]--tr "JzI+ +ol q
=ql^.|
q
^gg "l +ql rll6ll^J a4 Fzl B+. rfl+ sld Eql^l ,8, = =5.9x10n T
_H_E q+ 4& 421*ol alelzlr 4zl d.4 Et ,J
^l7l*e] /r't Ar
^||sg "JÎp+ +ol ¤+. 4¤+* tlEll==g "l +ql
6}0l Eil
6ll^JE 27H4 Ai"Jg ++qlq,

"lag a'1] B'eE 444zl 4, o.sg mTol+
_tr.6J+. ol5g ++.H= EEI= o1 ,rllE-$ +fl gg
^Jql^l
Larmor 4lEf t't=TNE,t2nZ zlzla- sld++. ol 11f,f5-
'rBo Larmor dE t'4 +E6t7l +l
^]litE +4rll=
6o ??19
M
dl^J 'Gr Larmor tlE f'+a +=+.
4!+61 ^J46I7l glaflrJ, a
^lE +ql ^{5"J =4laJr}-r.
d4ollHz}. Eld Eql^l EE ol. ulelzl Eld d+ p'
=E
?lE-el tr-+q E"JtrHrB r0c.+;. olEg @, fgltr-
^llil¤¤r v
¤. 6Iq, El+^l ryH 4o + olE"El4. EE p
^¤E =46I
4, "153 d+ p' gge] "J +ql Eolq, ,<llzf$:=" E- ++. g
4 ¤¤"1 ol+qzlH B o aflE+ 4s4, :_4aI¤
^gol
fal 16c.4 trlE -EE 4E= LIEI-L[|= ElEl7l Bro4 tre-lEl=
=oll
¤ 7l7la_ c, B6J ??le. sld6l-rll ¤+. qq, =oll,\1
El-d d|Et|7l- 0l +9 flE¤ rtal -Lrtrl. Go=oll^lE E"J-d
^llil¤EE
+d-+Et+ +Î g1= a,r t17J E."J 4L+^l7lH zlzl* EE(8^4)ts ¤r114e.-e= a'a+ P' EE Soll^l 8.Pe "Ja19alil a'4 P'
ulelzl zJs E=Lrx(y*E,l2n)x2n "E{+q"J *9lE) qA
.8E|l=E aolEl.(=e += gg doil^1E ol=E
=de
EEI= ry-EON eldalAl Eq'. Eefle.l
^$. ^q
B^'JE
^llxl'EEo_e_e
L}EIL[|= ulels
6J+. 4rE= B^q EE4ol+r e}+. trI+^J EE4 0E ^Pl+
0lel =dEZltrl'. =oll^1
"l P^l6t1l
16C NMRoll^lel-J4 7lH 6s3
90. ajr @o
,.Ji
D=
=ol
!-
,7N'
,tol
-4
M
vt ,\l7J, r
E1
(a) (b)
fal 16c.s 131 g.!_fnl.+4tr-d E?J"J 4+E^l7lE

ulEl= xy-Edc-e gc_lTl l -g=ÊI=
+ 91=t11, ola=^|a
90" rJ4atL:Lttrl. (b)
^l7ltrl
ElE17l gE BEEky-E)oil ell EIE Larmor T.!E#E 7l.Ê ,%8 ++l=
^PE[ rg 16C.6 =fJ dE+E 'J= 4E LIEIL[|= E+-d BE-x121
Lt|alel E.?,t= tttl). xPlqf u]E1= zt= agg +714 ad. =E ^la7l
flE6l.1l Eq(ad ^tR
?goiltrh TIE c+= +g/.lTlq r cETl =J^lErl-.
=oll^1
o+ EE/\j rlLtTfq,
e0" B^ zl+ql= zlzl* ulelzl x7_Hgl ?14. 4d -r. FrD= olel+ TlqEq 6}e__e. ol+q{+.FrDql
+q LHBJe+^l czl
=e
_H-E zlzl* ulelzl x7_Eglrl col aI4s"J trI= A+61 r 1]t+= AeB f glzl"J ^slEetl
=gl^J
Larmor {ffi zlz\a- qd6}= ag E + 9lg 4ol4(:z a.zf $a3qflg ql= 4E Ezl-e" aI4. "lelql a+ql=
^l+
H r0c.su). NMR #J4lql= 49 a"Jol .rl-E ++lql Goql tlql^l iz}]t ule+ t"l Fourier E¤}(4ulz}9 dFal mlg "1
+zl6t4l aagleq, azl4 o + ^llitsldg 6l+ zl-7lsl El +6ll^J {s$ $lalop 6Jtr1.
4zl Azl4_o _+ a"Jg il+6}r. r qld 60ql^J Larmor1l$ Fourier H++ql^J= dE-A{ '^lzl Hq' EI+ s(f)z} "Jq¤
+E dE6I= 4Ig A+E +g^lzltrl. ol tl* d+= +d- +. rfla +$4 ac 4E 4ltle-s tsolzlb'rlt+-¤q'
rl# frlzle a=++ EL+ /(?)el
^trlEBol =qgq.
rltol zl+H zlzlfli zle u;aj= CEol H= ¤¤ ^JqE
qFlt+. ol+rll 9H a"Jql +EqflH rlE 4l-:rz\ oo 1(v) =
J-
S1r 1.or (2nvt)dt (16C.2)
zliE}++ u}4rl ol
^la tr-+ rr4
E e^l¤u}. ol +4=
¤zlrl /(v)E tlt+ v9 rllzlol+. SA+ d5+-gq EL+
tlsel dill4"J E"Je:aH r0c.6ql Ll-+u 4lE-e4 ¤^l ol 4+g Tl# ¤Eql aa^l 4B + iE=E
9 .f,S.-xt7l xl$ #4.1(FID: free-induction decay)zl Elq, q-e- ^4EBe
ol+qd+.
4 ee Eol gtrt. 6Jg
^lt-Hq 4lc.z1- 16c.1^lql^Js+ Ag +"J AE-rJ4
s(r)= Sn cos(2rcv yt)e-ttr' P-E-^f7l rJ^l (16c.1) -tr6J6tH Fourier H+Iol rl-¤.4 eol ¤trHfl^fo1= e] +ElzI
^l+ /*^l
e] 30ql qlql +714H).
zlfillzli
154 +^l-= 7}A6ifl+. rfl+
coql^J eq6J Larmor
+E+Et H.q+E a $uzl e0' BÊ zl+ ^ltel q+ql

4l#E 4l+6]-b +d-
{xll{c-_e.E Larmor TIE /(v)=ffi (16C.3)
HI6I^J 4¤-
'l= E"JqI a.4g +48 + gl+ ¤2il4 " + "l ^lel rqs} +Cg E +ol sorr9 4a E+?-l
v=yr_91
Larmor {ffe+ e+ZI tlolal eq ¤+4.E
ÊlEHol ^ "J
olE u['LorentzB +dol gq.r7]r H]-¤+4 kol{lrl
4Ee +c +=q l1ffql g6fl^l e0. g-r-71-tlB
9 d+g rtnTrolq(rB rcc.7). "J"J rn +dol +lE-A^l
6l s+= ag qe^la+(d +d-TIH =Eq,
+rlttol Grg e0" Ei+EE q+e-E ol+qAg ullt Fourier {qlol "JflE qq
sld^la *# ^llE +HI¤+). rlE+E B*4Ee ol+qa +4U+.
^slEHg
¤# +4_" _+ 4zlE *4 "tr. FrD aEg A6lq rcc.24
(b) g dE+HE
^lzl-Eq ¤- Nun e+qs +il 4E:6].fl+. :.8 roc.sg il-ellE +t
^trlEaJ
NMReI 4 zlzl4 zlzlq' BlElq Tlqlq= aol 6l]zl= 37HE tolal FIDeI d#-Hq 6J+E
^lZI-Hqr+
+a ^J4BÊEHdg
+ 9l+. "l EElTi +H x7-He + qd!$ fl]R tsol=trI.
{ffi zlz.la_ ol Eql^l ^lli} qCg 6J+ trI
ÊEHdE
+^l 4 zlzl* ulEl= e^l-T]E .Jg e= 4lEql 7lq. 6t
65t+ rP I 8E
ElEtr[el 8*l s0 fo.rrPr EE
Fourier Hflg qq+ irl¤E aelu|(sine tri cosine)E +A 6l+ A¤+ 7lol.,+4U 4"l4.LA e^l= zl-dt+ zl
o e 44U+. +Bol ¤*+ s(0"J trli= 4IE"*+ cos(2nvt) q7I +{lolq mI= e!= }f {s-f/ zlolT| +^ll6Jg
9 zl¤ r(v)zl q*q-r+ *3'cosine Hs oe. +qd+. ++al-¤4
¤e a+ol E'-+ (v) zlxll-== +4r-l]4 ¤ ufl= 6|1'Jr61+
I(v) =
J-S1r)cos1
2nvt)dt (1) 4ls= trl-$r+ eg q-Fourier HaJ9 ol+ql^J +^l EI. +
el+
+iE]-+ql qdfl^JE +^l-¤l H{}ol 7l-b6}q, g^l-olEql^J
ol +qz}el tl^lq 4aJ +zl erl. elr6lq+ "JB ta ? (3)
S(r) =
!,- tlvlcos(2nvr)dv
zl uel|I Hslo}fl xl-4154 *zl zl* Z 71qE EI+. r
illr. uul=zll H6l-= {s= r-{E+ Tlqql 9EI 4ol4.tl Fourier H+g *a ++qlE 4+^la + ql4. "lEE Hli
"J EH 4loz1 s(r)=5..-tr'ge-l +++ zl+¤ ztal aJfolfl 6[r]1 6l]4B f ?lzl"J 7ioi6l+ r]E +t]g zlzlt_ t46l-
{ff v9 ulzl q--q-4 zJZ zlq$ qlq. aol q 4q}61+.r?]619 E}+z| 4?-lql oI4rJ oI+ L
=
E-lrll H6IH Fourier H+3 +s tr--u}* z\ol= *=+. EI"J
1(v) = srl.-.-" cos(2nyr)d t =
affrO. (2)
e'-fz} 44ql q4^l uule_zll H6IE(A{ qlE dzt ,JEe+
?-ol) * rlt} E*"1+.
ofr-ll lzllzl 13 uul= e4e+ Lfl ,J41, :a?-]tr ¤zl9l 4*
3
Fourier E --)
2.5
\
0.8
\ Fou rier EE
\ 2
\ -E
0.6 \vltSo
s(r)
r= 3s
1.5
\=r S
0.4
I
1
0.2 \' \ r= 1S
0.5
-\_
\-_
0
0 1 2 3 4 5 6 0.5 1.5 2 2.5 3
t/s 2nvlsa
arilil 1
16C.2 eJEt
Ê
0.8
eJE].= zlzlo]zl ¤B #ge 9Eotz]ts 44o14. ol ^ldql
a,t',,r= 1lrT,
a 0.6 xelrC$(zl-e
.<J CEol S,+)q15 ffia|{ zf$ a5o1
oJ-J
Ju
nl
I
E aftlol Ezllz} ¤4. z]|zl] qf,$ zlzlt- "$tztfl,
E ^SE
0.4
B¤sEq d=g + t4 a4B^l-ole-l dolzl gq+^J
+
^¤94 ¤Bol ol+qzl= aol+a E
tr"Eilel Tl]ill+
0.2
-I ^lolql
+ gl+ Eql ol ¤¤ol "l+qzlElH zl]z}l 49 zlzl E-HIE
0
0 7l a=q + ?l+i tr-ql "JelE zJLtr_ E+qqot ¤l+.
+iil+ xf, v- v, ol"l ¤Eei ul-$ ?ol e0" g^z} 4+6J +ql= ztzls| ul
fg 16C.7 LorentzB gBC. EJ-Eololl,'.19 C+3/.lrJ-Eq CE9 AÊ Qzl g+. ol ullaj$ ¤ed
xy-Be-tr- "Jzl--+el +aql^J E
lrJ Af+ rroll E=zltl.
=81= 41 a^{4 04¤ol t'J+E rBzl f}eS z}zl
=416110}zl
16C NMRoll,\1ol =J^7lH 655
M r(t)".e-'tr' 7le BI-BF

sJot
^lzJ
tlell (16C.5)
"l L= M,ry(4ql Hlell6l-= $E-zlzl zl+ e^lE +4'}l= a

{01
?
r
^la 4 E"J+ aol+.
(a)
dE*, v
(a) Sel rl!7lLl=

zlzlsl9 z-c+"l ¤¤ ae_e Eola+= 4,¤: ae+ B^g tr-
4Eol Bottzmann B.:LE ol+E+ r= ^l-ol9 dolzl "J9
,tol
?
)'lzJ, t
"lBlqL dolE F <+ a{olfl +E

Lt"t ++= 49 9"1{4.
(b) T.!E#, v 1l5+ zlzlololJ,! sE6l= +zl4 zl-zlargl E6H^l "JqtJ
4. ol +zl4 zlzl*Z +"J* geq Eql^J "J"l4zl"J zI^J
tr¤4-e-E= zlzlC 4ol4 ¤ dxl9l E6]]^J "Jqt
=ilE
,tol 4. olE zlzl** +ill ^lE +ql^JE Ezl¤9 *6xllul9l 9
? t
"J"J Ezl¤9 +r-=:^llHlTi +E d¤+ql
^17J,
6ll^l sEo ++. Hl6]]
q+ L44q q+ mlsH pe+ a rlol9 dolE 4-=-g +

(c) ^J
T.!5*,
s.g atr + q+ L4zl+ q+ g4^l T1"l aqTl4. Ezlz}
v
f.al 16c.8 fttr-xl7l A4( lil-Eq)el Fourier EBg-e Eg 6[=J

*E 4]t+.il^J +ezllHl= 6J oll"J ef, zfzllrol 4+
^l+
4ElEg(TlE+EE). (a) Hl-'JEt AEB, (b) -d Ax4lsl ABB, (c) -d AzX:419
HzlE a44 o + +E6Iq rr]6}q ^¤
T,"l 6t"IT1+.
AgIXEB.
Ezl¤9 *;tzllul +E- gEql q+^J rflr e" "l19 d
CE- at^ql q4^l 6zlal.4, r46}q .sir+
^lA E=E7l
a-
p]9 z*6J CEol 84. :44 B^zI E+r 94 H r6c.ggl E"J 1al rJ¤ 4._o + qltlg+. ge+ ^lzlg c%r
=z[6}111
B¤ol ol+qzlfl Boltzmann EE= 44401 al 4e + ++elH Ez| ¤+- EEJ¤. ^ll+r q4}4(Eg rrc)4
q ^flgol
flol 0^fl8+ "*"Izll(yN)o"J oll), xlzlsl.9 z*6J CE Ae 49 slA ¤+ql 4+^14"t aJ4.
ol sol 9zl t*Eul. z}Tls+el z*6J CEol ¤¤e zlzl* EHI=zl gE
"le+ eol zfe u3-a3= Sfl+ zflzll
Î"lql
e 9Eotrl-= rlCg AllE HJ=d
frEl4L qIrJ ol ${$,tll ^S9
El4+elql ,r|+ r tr-ql4 H]]gg Szl gq++. +
"ll+ql
.=. r*-d gE[ ,\lz_tol+r +s=
^lz} tr-+
r,$ zlzlt- z]] tIE}lE Î"lE dolE EEL6J "luloJ 4C"l4s "l+lq}
s+4_"_tr +flo}Al E+. ^lle Sslql^J= ttJ6J ++l ^s
+4eslql zl{E 6J+.= Îs HJ-6} olg¤ "Jezl= r+ee
qlqzl oldol ^gr+
(4^l') +Hlqss ^la tr-+ r,g 9¤ 4ol4 zle u3'a3 S3r+qlE zlq= qI+. e, alulel zl{
^plql
g-4z} Ss+ f"ll^J zlzlE]9 z*6J
^ qql el6ll^J 4lzlqi +zl4 zlzl*4 EsltrI. ol zlzlzJ-$
^lzlolr-|rE +=+. ^lt =
cB"l M,(t)olE rl-¤-4 ag q4 ¤B <I M," + qE sFol Lg ql= 4 Ezl¤ol I +zl4 ++aql ol+sq, ^-ll
ola+. ^lq
M,(t) - Mon s-ttr'

^lle
UJBF
Eal-
^lrJ
[tr"|] (16C.4)
e0. EJ^
^tdg a* I
zl+ql zlzls} ulelzl-x7-Egl 9l+=
n$ol +H+ %rrls _+ HHgElq^J zlzlsl9 ¤E CEol xy- t
Eql +El-t+= ag E"l+{.r*l+ 94 ¤Bol ol-folzl nJ
? rt=
E I gg tlql +4r-C+ 4E= "l+q zlzlsl9 ,lo{
^SEol
zI-sE CEol Sq{+ olelq} z|e groj= zlzlo]zl0e_+ q
oll
T2
¤¤ ^JelEel sq¤ 7lE HJd sJal+r ++ "JHl4e e Lla ,QE go o-

XE
oo+ E Llq
= xu X{/\l E
^1/\l do+
ol ${i 7!,E HJ-d gtrt lZl rr(rE EE}

^¤-1{ ^le)+ E5 *E ->
r +q= ^lz} tL+E- zlzlt- zl+EL+4_o + "Jq*+. ^lz} lal 16c.e E^PI EE +oll^1 E6rilHl= 6t= +Eoll qal + Sal
fql^J 7|_tr_ HJ-6J=z|7lsl7l M.y(t)olH q¤r+ Ag ,rI+ s ^1zJ01
^lql E6lE Egf. +8=e 8su1 EdE= LlElLJtfr + 9,1tr|-. 3E *s.zf
ElzI "JolE4. EalrlE + S+ ,Jol-T.!tr|= a= +E-6tqal. =
^lrJol
656 15 rPl=E
zI Eld +E= 619 q=6IEE 1$ ul]aJ=ol gE +

^llTlql Tz - Pa u;sgBF So| t8e-ll (16C.6)
+l"tl mlerll +4A4Zl H]]6JB+. HF+q "$"IH gfl EzI S
fiLvr,.,
^lA
Fg #¤, r,ql "H'*6J+. +471 "J"J t zlzl *4 o +Prl ¤zlrl 6rt/2t- HI-+olql^lel C$ol4(LorentzB *dS zI
+= +Ae-q mle.zll ole"6fS +zl4 zlzl*9 E+ EqzI e) d^ll4 +E $f"J6I/l HqA
o Lorentz¤
¤+4 o + 0ol g+. 4 zllzl lflEol azll {t"lt 4s_e .rll ^dlEfldol
3 otB 4olq, trI+^l ol S+7I zl+-++4o14 ^lA tr-+
iI qa¤. 6}zl g:e_q sqE"J +q^l zie u3'o3=$Elz[ m] Iie ++E + 9l+= 714+ aolq. ¤E4sE
s4l "Jq4zl *84. ol UBI= gElg 7J r,ql 6l]B*+(re =^l-4?l
+CEl= d+g $f"J¤4 zle u;aj= SEle] i- 71{s "lF
r6c.q"ll -H-"J Hl.e+ B"l). 4tI A4ql E6lE ol ¤+iol tsxte q¤ zl9
"l+l 4"14. Fzl* ¤.6l Eg d= =7t4r ++.
H zlE ^lA tr-+E *=+.
Br6J $slzt El+qL
%1-6}J+
^ll51 z| zlull{"JxlE ¤+ trl]^} +z}4le+ 4-4E aql e-l+6J4.
#rtEt oll 16c.2

(b) r,El r2g +8
HI-AC +rflql +ol9l= 4Lg Ez}fl ,Hql 4fl L9 <l"l {ls',J6J S+ ^lt 7,e UE A= g$g ol.$-a]1.<J +Cg
i=tl ¤ Atr + ?J + fl+. 6il'J6l+ d+ + gl+ ol %r-Bql^J= +d a +alE ,<l.E-914 180. gl:.
ÊEHdE
GI-¤+r-l +olql^J +A+)g Unrrolq. rz=3.0s9 Qli. E 4L+^lzJ4. ol 180. g^= zlzl* 8,2 e0" g^ql ql+
ol d+ol q-q_r+ *"1 ¤4.
aE + a4l 4L+^14 zlzlq. EEIE ^llzt ef;- %16&9
H||E
180. E7)l aI{ ol ulelz} -z*6"t¤- .}6}zl al-b 4"1+(rB
L,v il2- 0 I Hz
TETI - rux(3.0 s) - r6c.10a). g4= + zfl;1;g- qd^lzlt- B:-$ol al
=+lE
+ltrtrl. rl "*"1-zlrll
6t= s,r+E +ElU+.
¤zl9l Egl 5ol9l= +Eel} ee +z}} ?,
Hl6ll^J
z.lzlri-zl7Ie
= 180. ¤1 4+ql= ^d$g {zl $e:.
HJ-6.J
7I gd q sg-q 30msE ulcd."l "Lq+.relI 6ll'J.6} oi+fl
E Bzl a"Jql 4lo-tr LI44zl ?*=+.rq+B4g
d+g nHzol+. g + alqlo + 9EotztE s+ 4e¤- H:al Elq, rq6H
=
zlzls{ ulelzl 0o + q oel¤H4z} tI4 HJ6J9_e. Gll6l7l
zllztlzli 4L+61+ zlzl$ol +"J6iq ^l4L6Iq B¤
ZteE slEolz}tr}. olaol "Jgulzl dql ^lt
^lE= E6l"l E 7J4 ill zl$ + e0. B4E 4L+^lZl4.
.J6J #g 7144 Larmor {$fzt
^lE
L}l+el
^Je4+ql E "l $Lzl tsot9lE
zlzlv} EEIE zCEg xy$se qd^lzll o14"1 rn da
6H^J"J"Jqt+i1 ^J46Ifl+. rq+ ¤xll glolrl= {49
E ++rllfll g+. :zBlE EE %r-Bql q+ Fourier H+|g 6l-
"JE= 'l+^Jq qEl+ qEql sdsl +"JqI zfzl$.$ u35 q a#_Hq
+ Heq rle ?I9 +l^l"ll ul4 zl-zl^J"l +e+. ol3l6J E eril g+.
^4EH¤-
+"J^dql el6}l^l *Bdol ffig¤ d+=7!$ 44d4. ol
olBlel
"JB9E ¤E I4EHE rllzlE rTEe-tr qd¤
zlzlsi ulEle.l rTlql el=++. ol dlEl a71Y r,
E+"JC d+-67IE ¤E= 16c.s^14 Ag +41= ol+6}q ^l7l ^J+
$ zlzla- ^l+-.J+4 o e H6Iq + g4 7J4
ff 7lE-'J:d gEt Ll?J TT== zlzla_ +4u+. ^tolE ^l7J
ol aqAq q+ zl+.J+4 o + ?zl6}q q4,tl lul-E_B
E zlE tA *zl4l ,rI+ zl+.J+4 o + 6zlaJ4. tr+4^J
,<1f
trolql &k* zlzla- "Jds_l ee q+91 {zl9l

190. rj.,,. ÊEH9
*E zlfaJf +dg *e.E r,g +g + 9l+
M
r,(ri* trz}l9)E +C6l-eJE Et"J¤ d+-+z| affi
90'rj,t 4l4aH"F ++. q7l^J ol+q= EBg NMRoI E"J¤ +ql
lrJ
ol+q 4 zl* +s+ Bdol4l 'J + 9l= otl"t?-lE
7171
U
-,
.I 7171
L-,
?
! 0l+61+ L"14. ^S
E trllolal= g-J Hl+q= zlzl ullo|44. ¤zl
(a) (b) "ll"Ialql
.f.g 16C.10 (a) eld H= xt7ltrl trlElollr|' 180. =J4= 7t-d
groll,\l ^l "JqLt= +iI4
r+Ai$:.H roc.rlql +$LllB.+. +itl
=
er|el'0lcl^1 7l-d e0. "J4 Er.l. dE+Eq 44EgE Tl+01 "J4
(b) ! zlzlEli ¤4 ^J"laJ zlzlfl-==_tr ol+qd 4ol4l E +
7J?:011qal E6l=t11, ,\lil zjzlol eEalq gg =eJal-21 gleq, ols zlzlo| ^dEg ,<]E Hl*+ qel
gclutrl-.^l7J
^1019 ^1|.e ^lli} d¤+z|
15C NruRoll^lel =J4 7lE 657
z
"J¤6IAI tso|:l:. +zlzl zlzle.oil ++61+= aol+. ¤+
90. aj,^.
M ilB+ +g +zl4 zlzl*e] 4¤¤ ts= gq +el
-*--] fl$e ol+q+l uut=
^lE ^
+ ^lz} ?J4& F6]]^l +
'_---> ^fl-+¤¤
4 ?Jol HHIE +E= frxla}q, zl9 rrlt E"Jql gg Ag
\x/// <___r/
I
L-al
ffi 7.1z} E?}q q+=+. ol qlEql zlzl*4 Br"Jc"l
180":p,t r
I T
+ r?J4 ¤i"J "JAaI4l frzlqe ,'l+^J ,ll"l-4e_l a7l7l ol
,i_\ .,rEt
1.
"--- >
I
<_rEr_r
I
zlzl*4 H'JCql ++6}rll q= 4o14.
+-
\ '>!E I
olz,ll 7|tr
"J-J ss+ a+=
.${allEx}. ol $E}b Ez} c
ffil-=
I
J
Eq 4zl 4Eql^J H{-= zlzl* qlgql ^JzlE 4o14, trl4
--\îIJxl ,! zflz|ls_l 'uuls' lflol
^Hd++ +ltl-ql^JE'Bule'+E= +
I ^l.l-d+E
^17lal
T
zl*+r *Elg + S.+. olq+ A+ql= + ?Iel
*H-'-l
----->
^S-++
tl+ 12= 7l^1a &zH¤rl.trl4^J ol $4.s
I
^flEol ^la
.f.g 16C.11 TIE+E elCaE trll^'l -H?t= ttHE trJ oll0lal ItE
4E 4d4qzl ?*eq qloi?-lel aTlY ^lZI ^J+ rz= Tl,.l
Larmor
90"_r_180"-rg til4 tEl. 90" E4= x+ ++.le 4rE6tIl.J 180. iiJ r e|^lgtrI. "llol-?-l F9 tls rilzlE gflq r {tgl 4
y4 ffle l+E-Llrtts a= +E6l-qal. 'uut=' L4/Le!' Ell= qI= = ^g
6H^J +e6}l., ol rJl"lel$ ol$alq q. Ae++.
tlE+ql EH-d arEH4 +elolr[.
16C.3 Ê =il-=aJ
qEE lfl-#e + o1f"ltl 4olrl. d$fzl u]zl3
^]lz}
ae E+ zlzl* 6ool $f"J6Iq ^lEE 4I ++q 4l+fl= BA-t:9 z|¤4 Bl= t.t o/o
+Iqqq, q{^l slE+-
*
={
zlzl*4 4lzlzl;razl ?*zl ullEql +ElU+.^lE +ql .lBl ++. 6J EzI 4"ll
^trJ =ol{ril. '3c 4"1 E "lt[ Eq ilg
ElqI4 olfol trolo-J flE"l qlqlE ol+l* uldol + 9l= +Eg rI+61 *sq q{^l r3c-r3c 4S-^S ^&s
=qilg L+g "J+4es i1el6[ ¤ B,qzt $.4.
"JqB + 9l+. "le+ 4a4 "e
"l +ilzl ,+¤ql tr}{ +d ,,.le.oll4 e0" gÊ 4g^la
,H E+lgi9 ¤x]] ulE rooyo4l zlt4*4, :4a|{
4. :z4l olq^l qd Eq g4+^J ii14 o e "Jq+= 4 uJ Eol4l 6J+.t EzI +E +i fl2}43 d+ =+^
'Hol'lrl,
ei$ _H-rll q=Ell, ol Eql^J BE Glol x49l $alJ,<J {zl oli-,tlole.l 4o.;-sffi +eg + 9l+r TIAa.J + gl+
z1z1o1 Eq= 1789 /+ qd6l= ail qqi-^fl +E=g NMR E+r-Hql^J +3qq +zI +ql
^JEHql fl-::. ^Jql^J =
H Bg 4o14. ,\g ft$ ^dEEg tt"l+ Larmor 4lE+E zl]6l= ++-^g +Er+ aqlg ol+a gl+. gH}4ee
g ?*71 qlEql B^zI 716111 4+ql= +i]lg.e {lzflslzl .<l '3C-NMR IEEHg B6flol EzI +E ¤4 q=+ 'u
4I++. rH ro.rr3 F dB4 r-{ +99 z}zlp} ulEli$ S eqlg oiFzl q$ql 4+61 +d-6I+. rfl+ g¤rt
^
=
+4rH= a,olH,.utsIe,rqa,Lfl,_tr^l- sld Eq 41t+ Er_=aJ ,JHg olo_" ol.fl olBl+ +alEL lElEHg +4 oe
(Larmor d5f)E 7l=* 4"14. Eld Eg Larmor 4l:+ol s+s|^lvJ + 914. "l ',J$ql^l= +d-41E+ +Îdg ,H
U + 'UBI.E' Eqg+ 'Lfl' EE]= O] EqI^J -HH H}q]E B"J Larmor {t+ql 4+^l7lE^l '3C FrDE: +Aq}+. ole+ ?ol
4o14.
,H qg zl+^lzlH "lE9 :-¤ rJ4zI #+614l HaIq, :24
*d zl-e groS $Eli $.zl"J tlg E+g6}r+r 6LzI &7H ofol r11-r3c AEl¤- ¤+4_o + 0ol q4l Eq=+. r4E 4
,tlz] 7zl zlu ++ql sld Eel /HJ6Je-E rso. 94E zI¤- qg g{-aj q-f=d
'3c '{dq +"J Cg +Q.]]rll ¤+. ^tr]
^la+. rqE ol g^= zlzlE* EEIE a_ + ++lE qd^l EHol ++ifl¤ $}EI otq+ E= 4lzlzl +"J dql d+$trI.
/ yzg4l +6H^J 4gtlol qril ++. +sg d4 zJol
E"JtI HJ6Jotr 4l+6ll^l +E6Iq
^s
HJ-6Je--e
9E"l-t4. 16C.1 e4 Orerhauser EEI
/=.
r?-lr $lzJ +ql= _E-= +¤¤ol y4 tlql xl] cB6}rll g
+.+ Hall tlz}] tlzf, 7zl E+H a7\716zla}9 al s+= gezl* +zl4 zlz)*4 E^J4 +^l7lc e
^lsE =+]3gl*z}9
{AI"J 'r-S "llolel'ql EE:"Iz)l Etri. + tlE Hg^dql el ÎolE 8=rt-8=rl SE4tEol+(Eq
r6BE ^J.^l
6ll^J +4*rl{lzflz}'zlld+'q= aol+. 2e). o1
^Js4I+ql^lE a4 ^SE zlzl {qziz} r-fl$} z}
,JHE +go-J ,llolflE zzlzl * t tlzJ rlolgl Tltlol E4ll 4sg) zlzl rS+z]-e+tls4+g 6J+. tgzl
"l "l
=Cg
6s8 rPl=E
-AN FoF*
,tllzlE qF"lzll 6i"l 1g d"lz| "Jg{zl ?*Al 6]|oF +
+ A
4. "l zlz\** +E6l e*E?I a^l-6ll+H x^¤ dolT} -rr
1 3tlqq + qlqzl zll{lizl E"J6Lrll E+.r;l6}q r
=flE
K
5 0 0o0* 0os* 0 H r0c.r:agl^lel ,Jo) uoaxe0efx dol9 a+ + dol9
o zllAlizl +ANol Elir, += x4¤ dol* -+ANol S4. "14
6J 7lli]l+ H3zPt gq+= E"Jql A^s d"l z.I"l9 THill+
0e0x zJ-= B6-19 tsxl g*g{(aoa*<+ Fxax "i aof*ep,np*) aN
AN
fg 16C.12 AX 4lel oilLi^l=glel.0l

al"l Halzl g+=+ tr}4^l A^g d"l9 rJlzlE ¤a}g tszl
8r|14 7lli{l+. ?l+el oll-rL
=?l=E =91 r5'E"1
LllE= EEUcl tse 7tlill+E LlElLHn, "JE g^4 LllE= EEtcl
.
=^4 u11i1145 LfElL,lrl.

H3 =91
+3 7lA= rJE Tt|il|+e+E1el ol=J= LlElLJrt. olzll $oi a4g rj4ralJEz|. ol $Etb Ae+ xlSE
r}"l9 ^fl
^4
{-qz}-xt-lzl. ^}s4+ql E6H^J "Jqg f ql4. "l
tl-g4l+{l {qI hamilton S&zl-b + qE ¤{lzlql Hl
+ ^ll7l= l/R3ql Hlellq-q(Rg + 1B ÎolE 44), Ei'J Bll6iq, r +ql + ^g
Frl4-o + fldq^l aoc*E FoF*
gEE ztzlqd Hl¤.E #ql Elql++. ol a4E trszl+ ^ ^Sg
E_ "J=qe + il= 6}0l ol 2+ +ldzl 4c3
"l =qfl+ "l
g E6J $-g xlzl9d Hlgel qql E|]6]|^J + EF zfl;1;5 :zH r6c.r3bql .E-oJ u}q Bol olEE
=-44C"14 zlzl:n- =+lE
,q6I+.*3 'H= fl= AB4"J frzl EzI+ ^Je+qI ¤B A"J AMlt -ANs tr qEolzlzll 6J+. ol+al 9E e^
EzI9lrjE ,'dl+zl_rd+x} I+ql 7l.Jg= +^14 7l7l g dols ¤eEl= ^JEHE Tllill+ zl-= 3,ANol qq B
^JE ^lolE
*ol fE +slE + 9l+. B tlEl] <tE+ 4Ti+. gelh:olz|fl X^s c"ls+ r5t-:z-zJ.-6t-l
=?l"J 'i:r6Lrl7lr- aaLol
-ij zlolgl
0_16!.= _Lt..i,
z_l -if.R a.,...u1 r.llzl.B.9_*zlzll
E4 Overhauser Ez(NOE: nuciear overhauser effect) ,.1 iL 'e.-fj--i ,-r ii--i_i ..ii.. ie E I I ,l
'its.li =
q }gE ffi{-ffi2[ r]cz]*ql zl"Jq= S ahb 1"14.
^J= ^lolel
q¤ ol-ao qL+. ol s4E ^Ja {+z|_Xt^lz| SEI¤ "Jezl}- .95r+z}_,r6qz}tszl¤:-ql ql.J hamitton ¤&zl-s 1g#
+ +E + zlzl** aÎ6IH Exll q1q1 ulrjeE FlAq+E rr]4q AIE a*B*e+El Foa*e
^¤ ^Sql ^¤eE+El
E *E ^1\7l'71H6I= ¤^Jg ole" rJr|. {fz}-ffiz} ^}s4} zl4zlY ¤tl4-=E aqlg s6JqL+. ol 4Ag "lE ^J
¤+ + NoETt +Ag+= ae +olq= + q ^g
ql5e] 2fl2145-:zB r0c.r3c"ll^J4 ?"1 ¤¤
^JEIE 714?J
=-44ColF
ol zlll<l 9l+= 49 9"la}4 Ezl- +4. zlzla_ ol E4 4. ol+r1 qH *ql^Je+ eol A^g dole ¤aq= ^JEilE
E 6l]4ts + ?l+. THill+ zlz| $a39. *zl"J olHql= olSol ++ANE
Îolel
ol sffi olallolzl +l6fl^l :zH res.r2ql +ElU Hte+ eg AA6Iq Alg dol} ffiz|-ffi2[ $a48"] S.g trll5t
54 ex 4le-l iil
=+l5ql
4t zHxllf EE=.${allEz}. $ 4:. \lztzl E611rl+.
4 ¤¤ ^J4ql^l* ato,x tl4lizl TI1L "*r p,fi" q7l^J EE6J
ae + ^JHlq= Er+7I +48+= 4,"14.
=+le]
919 zHillizl tl* 4+. +"lzl + qlLJzlzl- = 6I+= AlS d"lE tq^J aoa** 0.#*
=flEe ^JE ^l-ol9 dol= frg
49 ulid].q +a aEE THill+E *=+. ol ¤B 44 o + rlzlE S+e+ E a}+-=- ao\"* Foax ,rllzl$ a}
ÎolE Xo1
ol5 ql ++lel zi4l+zl ¤+ilE+q qBal olBqEzl arlzlE dol4. qH s4z| zlull!"JzlE ol. + gEl a
= EH Ee_l ^JEH4 froil 4+ aC¤4. roc.244 SsI
"J +E6I+ :r.al6}q p.nux ¤+7lE+ "*3 z]| ^ltql^J
4l+= 714q, FoF"
=fl=
¤+xlB+ zl3 z]]z]l+E 7l^l
q, +E + =9=
¤+ile+ E"J6J 41111;5- *=4r ^J46I (ol a+ql= E 2vr)E tl¤-g ullE ,rllzl= +rJ^lzly \oF"
=+l=
zl.. :alalq ¤+ilE+qE olBg oooxoll 46l]^J aN, BJx * anax SEI -o.gol ++. uftzlzlE 4+zI ^Jol "JCB oll
ql q6I^J -aN, relr q= + Eil6H^J= 0ol+r 6l-zl. tr-=l]e+ 4+ tlel r}"l9 tlt+ itzl S,g trle+ es-)
=+lql
ol zflx-llf il-= rB 16c.l2ql +e}.]1fl4. dol ,rllzlE +qq ={ilg
ao\x - lnax Ssl trgol t+. 4Ig Ezl-= 2vrollrl
^ldtl-
+ qlqzl T|ill+ zl¤ Hlg6I4, ull dol d$el A uule.4l Fld6l= gf,-$ +q. q+^J FoF** drdx Qezy z1
= ol ,H{l+ =+lel
I ^H*g a-+e a)E 4yoltr Hl dol9
+ rll uNzlof o.f ,<J A^fl aolE
^1l7l7l
+71614184. "l 6zl¤'"J
zlzl 4* E"J6|]"F B 4o14. 9 NoE =?ol4-,1 ++.{lS E4+ L4rll Fld6lzl trll
= ol
NoE ¤eql^J= +d-Tl# zlzl** a^t61q + x^.S golf 2v1oll^lE gfol ei++. A+qli a,np* * Ftax
dol(aoa*euefrx "i Boa*<+ Frfi"l= "Jq+al 6l+tr11, Aiel Aazl zlull{olo-l^J Ar-.9 d"l9 tllzlzl e'is+. ol Ai
16C NruR0ll,\lel -J4 7lE 659
_1/AN -1/zLN
-AN 2lr\- Fo0,
Fo13*
sal ^71
oo
000, EI
txl x\
1
1,/zAN
\.-( uoF, Fos*
K
5 ooF* 0oc"
A/
.-0oP, 'lOl
oll 0o0,
-l/zLN
sal
o 71,\
;)
E4
-71
oo
/\
'r'
VzL,N
+1/zA,N
(a) (b) 0odx (c) 0o0*

0eGx
AN
I t6c.13 (a) xEol7t .g-i+q$E 41= + dtllE 7llill+Eol Zotllq, raJq .ErE Hlet ee 7[i1l+E LtElttl(ral 16c.120ll.t1el E"J--J 7|.a). b) E-Jl-
S?xt SalE ooel F0 doE golLFll Aq r= E.llel 7lli1l+E EIe4l EllEEt 0l erE AEoE E=El= 7llill+ it= 57[^lZ]Et (c) g+xt-
^plq
E=-^t EE
-ct!f=
qfel Ba 8Ell=9 THill+E r=E EE AeE El= P Pll E-+cL 0 l4g Ado le EBEE Tllill+ ilE +Êct
+rJol+r. ql+.
NoE ?l?]tLg_EE NoEq ,tllzlE ol-a"alol ¤eJ4 o + +
4qE
='gE
NOE z"7i+- oE q-s=4 ae. ir|+ulq 4E 7l^la_ g+ ?lxl"J olag += a"+q sEl EJ+E-E rel6l] +q
"JHI4
H 7*+. of 6J+.
NoE +rJ +4ulq n9 alg Aelxel ztTl3rld Hlg-=qlE
,=\* tr|af lEl E=*+. 49 zlzlEld Hl¤-e ,l]ill+e+ SEI +E
NOE o 06c.7) =+l5E
el "J+ql g.Jg +71 trli$ol+. ol+q
=3 alE A+ al{
*zi Aol g+.
^g
q7l^J rie sE+El71 44 q Aql TlqlEl= 4lEel rllzlol{, <k"1tr]^-q=r,+
/A= x^g9 Nor, dsz} +e6l +4ts Atr + +^ltql e Tx

a(-H-E-e-E r,9 f Hll AE) x^¤g +E6l sEl^lA +el
n (16C.8)
2y
.rllzlolQ. 5.q 4lolH^J s+ ft]ol ffiz|-ffi2|
^JE4r-+ql ,+7+ xE zlzlElc ul&o14.
zl"Jq= y{Al ¤zlrl TeeIIxE 4 Ae+
"J A+ql= q7l fld6l= a+el -l(gE +
a4 uElE_ril Fld6l= a+9 ++(*E +?h Îolel *& ?*
{xll{s.e} +E Ss} flEol a}t ¤4]a}{ :r-la}ol zFJEt q 16C.3
=+.
ol ql4l zt"l 44+= a++ 4el S+
16c.8^lr+ E. 16A.2-EPel ,,C-'H dlq ql+ alq NOE +
NMR #JBql^J ^5l+zl-,'6:qÎ Qie+"Jol "Jqg + 9l+= zJ El4"lEE +6IH r+q=4 ?."1 ¤4
Îdg
s4 ol ¤4E ssl.jl el
ols-"al-!.aol NoEol+.=
6]]^J"J + Erl4 " e fldqe + fl+= ^l-dg ol+ Tt
alt 4014.^flol
r46iol 4 xz1 sglqr 4 ne*q9 dol r'll n-_-
2.675x108 T-'s-' I (Ju
L')/
zl Hs*zl-t+++al{ + q r}a4r$-ol "- 2x76.73x10? T-' s-' )-
Îolql 6t-lx}-{t-lz} :_
ql"lot 6J+. ol {toz}¤¤ l/R3ql ulflJap(Rg + r-¤
^}ol
4 A"-l) "llol "JgzlE $el!. "l ttszl*9 zll#"ll ulfll
6IE_tr NOE= 1/R6oll Hlell++. EI+^J + rlolgl ^JB
il eEq 4^=zI-.15E-zI $s+zl. gleelB olE ^fl 44zl +rlg "l+6}q '3c NMR ltrlEeE eE- 2fl.$alzl
ol
^l-oJg
zl$:t(tH eq a+ 0.5nm oltr- trqrq :lzl ?*4), rq6lq E 6J+. zlEotzl dql ,H qg e,<].af{ ol$
NoE= zlttsl{t 4ol ll4E A^d4 -E^lE ol¤¤ + 9l+.
= ÊEH9 qE
g EEIÎ/zlzla_ NoE
'3c +,ri^lvJE+.
^4Eeg
660 15
^PIEE
=sEtTHE=
trr. 3tr-rPl r|'3 AAI(FrD)= z[e u3-43' z]zlE]9 ,rllz]E+el + el+.
+s= ^lt-EE 41E+. tr 6. 7lE H.!Ef gEt ,t.lzj 4= ,llolt-lE ol$all.<.] +A'Jq.
rJ2. rID +d9 Fourier H++^l7lE Nun lul=flol +9tr1. a 7. ^fl
g5xl %'-Hql^l= "JCzlE
'3c-NMR
^trlEHE
erl,rl4 r3c-rH =B-=aJ
tr3. {Le ga galr¤-4zt s4)= x}zls}9 z+ ^dEol ¤¤ 4.|44_o_a TloJEl=
A'*"11 A+eg fl.}]
Ales ElEolTI= 4C"14.
=tr}.
rJ4. 7lE tJd sEfi^g-^{ s4)= z}zlE}9 x A ft dB"l tr s. e4 overhauser Eali'J +B r.]lzlE- 4= Ael Effi o1g
¤¤ <t oe + 9EolzlE 4C"14. s4b +
ql,r-l zll.rj,r.la4. ol ,$a ffi21-i6-qz| $
^gol
trs. ltl-E HJd gEt lrJ r,g UC EIE ,Jgg ol$-oll.<l +CB ffi ol o z3 oll"J 99t4.
=s-d^l=
,A-lz1
o=, -1
l
+4 4Ba
$=.-2121 zI+ A4l S(r)= S,, cos(2 nv,t)e'''' T2Y 7le,rJ6} $e+ t6c.l
^lz}
NMR d9 t}-t"l * Lv,,.=11n7. irl¤ zlC
Lorentz
%L.J sc+ M-(t)-M,,*e "'i r,g gsi 16c.4

^llE ^¤-4zI ^lrJ
zlE HJ[6J
$El- M,,(f)*e "'l r6C.5
NoE ¤!* u}4olE 4=(i,-1.)/1^ AE r6c.7

EE 16D d^l ci^17 ltr=B
=
++ T]Ffe+ *Hg "Jezlal ++. r4H ++
> 0l E4E H[+= ol8 ÊEH
4=E +lil= zlzl*9 rllzlE zlzlt_ 'IQE + 9l'I.
".-]3 EEr-=al.8LEl¤t4 4loll= dxl.= ,*ts EErElol ?trl.
goJ olLlat =
F-lEt HJSoll qa|. ,l= E ExPl =al
trl?l=
trJEo1^l7lE Elt|.. Exl 8rl7l8 SB(EPR)3 0l- =r.txjlEol
E+61.= ZrtrJ:d 0ll 16D.1
=g-d
#-qfq 'JHoltl. e.2330GHz(ulolrE+ gqfl xqql +6t= +ÎC)ql^l
> E4d 4L5-6l-= BrJ4l= ol+6}q ,ilp EpR
T}ILJ "+qpe] ÊEH
EPR 44EaJ= 0lE6l'E Extq "JE Esoll Ezt 8E=
g 4eH r +Col 32e.40rnrql +lil6l+ dEol +e1.U
^l^llet
O{o
E= -T--\ Olr[
,(Ll
= +. ,rI+^J ol +qt9 g7i3 trl+r+ ?ol 84.
> "Jg-d qHl rlAl ht'

Ext T[|LJ(EE 8B)q gBoil *Et gHJ4 gal(EE (6.62608xt 0i4 J s)x (9.2330x t0e s-' )
^rJE ^Pl 6 = 2'0027
t6A)= +xl6lr.9lolot e+q. 0l -Er4g ¤861.= zt8oil^-|ts fl^l 0.2740x1g-z+ 11-r)x(0.32940T)t
gtoll^1E Fermi E4
^rJ-+lE eg(Etrl 8c)rl Exl ?Jollî9
$E4IE(EE 168)= 0lEopll Erl-.
l-ta
-_/%
dzl tz}zlC *B(EPR: electron paramagnetic resonance)* d s(}g 9* zlzl^&ol Ezl-84 "Jql Bo|4 drll dzt -qE
zI electron spin resonance)olep.E 6lq, g d ¤. "Jezl4, :41 ol dFzL E"I+ dl zlzlt¤- +g-^l7lL
*E(gSn:
^S
zl-=i E6J6l+ 41E. ¤+61"= ol+g+. rille+ o_qill
Ell 'I= +qLH= Aolq q+^J ol g#3 13.zl:l4ql ++ qL
^lE7I
¤+ ql^Jolq, zlzll ^J ^lE= Ezl-59 zI.+ Eld trllEql + eEE cB. +4U'i. olfl Eql.! Ernglrlg s#3 NMR
ql^Jel ,l-?_l¤' t}+e+ e3 qee 6Jqr E- + ?14.g.84
aL6I+.
zt$ g{t$ Ez} q}ql4 4zlzl e-l+ z}7ltr-E_+ 4}e zlzl*
E ¤6Jg geq, HlEql &.tr+ Ag ql= +g xlzl*q
16D.1 er ¤6&9 B=+.
=
dz} ^JEHq q4^J= ol F lalzl + +
=E
Eq r6AE ¤Eql E6lE zl-f, dz|Tl m,--!=fle+ ffi,=*i 4B + el+.
dolE "Jsa qlel +E {f,f= tr}94 ArI s(}g + ,q.J qEql &all+ il¤ +E].,J+. aail eql o +
=fl Îolqlrj dzlE=* i=== tr-E|] +llEEL+E 0l+6}0l tszl- 34 dHlg 5
6H^J +++6lrll qq(rH reo.r), dzl¤E olfl+ ++e_s +
hv - g"ltrBo 8E [^l+ E^l] (16D.1)
^Z ,.lTl*ol rdzlAl qq 9P zlzl^Jg Hs+^l7l= Aol+.
qzl^l ^14
fl+ zlzl$o) +zI p-4 *ql qlqxl
^]lzl= 44*ol4 4LEE
s"=2.0023o1+. ol +gEl= d+el A
={]6l-H
4#zl +Eqr ol d+ql 7l"Jq= +zl4 zfzl$ol
^87171 4 AEql qlulfllB 4,ol4.Ealls olE =91
d+"tl zl.J9ol dz}
qlgql g zlzl** 9P zlzlt4 a# qe
dzlql 4s" 6lt ++61*= zlz]1*4 r'llzlE r-g-?llE A6J ^J+ 6(Eq
4. "l il-=- r46l]fzl 9laH^l s.E gE uJ^fr. +!B aag + Êql Blql++. r?-16l-0l
8c)ql sa}r+&<tr+e] ctÊql Hlql,*
*4 tol +4,J+. ^l+
+r aEg + 9ltrt B3 a+ql olEl6J HlEll+4lr\ +ag
hv-g1tu(Bo EPR 8g 4A (16D.2)
q- Be f.zl 44e$e_l 4* ar= =;r ((gaql ql6H^J)=
4lsq r?]6lq s#"1 2.0027qt zV4*4 s.<leE*q =.zll
q7l^J 8=+qaE gziol4. H.94zl ?*=+. +rl +qAEC "JHI4e e +4e fl4-E
EPR r-slEBg gHI4e + ulol=eu| +^l-dE Tlffi E ol+q4^J +g e6J,!-+= +E+r]]q, L.eel2.r
rc^lzlt_ zlz\t9 rllzl= HsI^lAzl44 4zlzl ol ulol rlol9 s7lg {=tr|.^fl_+llE
*zlzlC d ++ zl¤E s{l==3 s.Z}l+ o
662 16 rrTl=E
*=+. ^lE +ql Eq fl= +q*9 HI* z,=+*9 zlzl4,

r?-16}0l ol Hlg 9* zlzlatol ffi z4* "J+^la rll +
Eg 6l.ril E+.
hv= gtt*(ao+;a), E= a;ff-+o (16D.4a)
4"lzl *(m,=-iJ)g q=q aAg "J+^la ql *Eg 6IZI

g+.
fal 16D.1 el+0ll,\1 7|.6t|^lE sl6H^j E^F=P r EE 8Et| flE
^t7l8oll
trt+E olE6l.= ilE E+= goiltrl(E c).
^4
hv=gttu(ao-+o), E= a,-ft++o (16D.4b)
*y) enyzlql ol=-E ^JR6l il¤ +4Lll= 4*zl g61 9l tr|4^J +"J d 44lq soll 96ll^J acq= tL
olag =
d TllEg}+r="l 4zlge+q tr.E4}+_os 4Lg ÊEHql=
q +cg E ?J4 ag F dol E4q
bull, Hlql 6}l'JF6t=
^llTlel
e44g +44q(E4 ttrl zt"tzlzl 4Eol4. rllzlE zlzla_ +4+rll E4t:_B t6D.2).
Ê7l
gtt* HlF,'Jcol4, :z ErlcE eE= 9P zlzltlql r.l] +qA 491 tz11E '4N Q11= l)ol Eq *sB, ol qg ^.ll 4
el 4qzJ9 ullo} 4E.{l E=++. ElSo}Cg e]$ z}zlltol fl u]]o}$ +4,3 + glr" ^lE +E d{l +qrJ9 *4ol "l
EzILH d+= +g.o]+ CE tr++^l +zl4 zlzl*E CE= E ?+ H}]6Jag +48 4olo + EpR r-.sleH3 :zgq ffi6J
Ezls+ zlzl*4 tI.{4 Hll6}ql E=++ +._4ql^l= E4¤ dg +4u+. gHlzi o e. qe rilzl7l +
^fl_l ÊEH9
"l tsEI- +.; + **z,lluJE alE_e.gzl_"I **il"Jol +Elt+. "JaJzr+rz]]9 ="l,r1l do+ eq+=tr1
,rI4rJ s<lol HIFHJ¤$ +Et{= ae ri.ll +ql ts=BJgi= 6J +q* +ql ¤4 zll9 zlzl$ 4ol E{ 1
+qAE 4 ? Sol4. 9lg trI= 4zlzl E+ ltr]=Hg aul^ll + .t ,t ,

+tr eel+¤. + gltrl olEol t=" ¤I oJcz} 1 3 3 1
16D.2 Eol{l 75 g ul=(qlg^J cH3cH, 44e +E F cH, 1 4 6 4 1
"JCzt) .aulrll dEel 9*zI "Jzlql+. 4

1
EpR r-trJ=H9 zlat +,qq}$eg z}|z]]9 r qa +q Nzflel f,f,al "JCzizI ilg ql=
ÊEHdEol0 e =q
olEol pascal9 ^flEfl
^dBe-s e+4^l aEI^j! +8. ++4= 4,o14. "JEI4 ol N+l7flel e
=ul;t]l4lo e4zlq dL4¤9
¤.:,lqlql^J '=ulr]l 7 +'+= +q= czle+ q E +qzl.|.<-llzl +EE +F+utrI(l).rH r0o.:"ll +4u HI
^LolE ^Js4I
¤-(49 d d6}e+el tlri4l¤¤ zllelqDql +4q=
ÊEH
E +a- 714?Jr+. EpRql^l =ulrll +471 +++= g"Jg aEl^ll ,Jal'd B.= n}l ---> c[N
17t| gf.g^loil g-d _+

dz} r94 4q* +q 9l= +^14 zlzl*& "JE= qe.l zl p*
zl ffizl EBIE ttgzi*"l "J94zl ullEol4.

^l-"lql
hv
(a) -.4
^trJsl EEI 0
4q* + qflzl{l Eq fl= t"J ,uqoJ EpR

B
( hv
Elz.l= g.r+= r]4ra|lHz|. "JdzI l$.$ zlzl** ^¤lEflql

"JEq, r
q Hl]6Jql q+ q+ zlzl*& z4l 6J +E 9lr E 4L
^flE
zl 6J +E gitrl. trl4^J dzll =tzl4 ztzl*e q-q_4 a.ol ¤
p,
c[N
+ el+.
fal 16D.2 E^1el .^rJ-+ oI anl^1| dE|r'Eoll e.l6tl^1 E
LJloe ^tolsl ar4BxP -qE E^l 8Et|= ^1=oll=
Gror=Eo+amt mt=XI (16D.3) o|fitrJ ollLl^l 'Jaldtrl. LlElL.!E[.
=+lTl 17l| Et|coll
0l trll=ollaqEaJqls 27Hg .N(^11717|- e9J0l LfEfurl. 0l
EE= rJ.Jet "fEtl raJ= 7l^la- LlEl''J + ?Itrt. rtl4d=g E+ ^1171
¤zlrl ai- Eolrll e-d $#(aul,til ?JQfl tl+)qr 6J+. nflE dlEt|=g oilqrl EE|= LfElLilq, 0l ,8Ell=E 7J71ol ^1.718=
ol'oE_eut
r0o.:rloll E6l-E ai zlzl*4 E"J+ ++l(qlaql ql+q). =7},^l,J0llLl^l(oJ8-.J
Bxl'sl '2Je.e rE,\lilq'Jo[e q 8E0l "JolUtrl.
15D crl ErlT H EB 663
1.61 mT
0.35 mT
---------)
xl.7lEi^ll7l
I1:2:1 1:2:1 1:2:1

II
rg 16D.3 +# s4ill +el UIEI alqe 301801 7J71 o4 4El^11 'JelE
L|EILll= EpR .Ê]l=B. EEaJE elqeE gileE_ fg 16D.4 17t|E '4N6-4(/=1)r|. 27tlsl EEEI gd^l= 7l^la 9]= alqe
= =Ce =EErl.. 9 no|,t1;+I6H4.
{f 4qe*o189 1 : 6 : 15 : 20: 15 : 6 : lel .<ll

^trlEHg
7l Blsg z*Y t4l9 do + qqglsq, :Z46}01 67l]el E
fal "JCzITt Eq gl= +qt9 a"1,r1l +ae+ "Jxl++. "J
HI4 "-= +qe +ql "Jzh7l-/?J Nzflel Eg"+ 4Eol
Eqflg rllE oI4 ^g
_E-zlql,t1e1 Ag H¤g pascal9 AL4¤ql
EEEil a*lEH9 Enl^ll TE ql+

BrR
q¤ 4qa 4ql a"lrll e6J *izl1.61mroJ '4Nfl(l= r)
6L+e+
="l,rJl eq+ tr-+zl
o.zsrnToJ 24lq #+ "JCzI 1367631
(I-!)zl il+. EPR qH EE +4+4lL feJ 16D.s rzt|9 EEel14Ne4E 7l^la- 9l= alq=E AoEl 74. a6.
+?
=q ÊEHol
r.aig Al'El 4 ++el 4ol4 f,="* eEE #4zI ¤ol

q^J +44E a"1,r1l +a= q_e-e. dg
^J4++. + + (O) trrtcConnell Al
,J+Arll 6Lr" olq^l e+{ dE¤--=4 q(E= qE
"l EpR :-trf =H9 +a= ^lE +q +qeg ^lE6l+
a"1,r1l
el +n])eE zJ+zlrll 6}ir" olfl al o + 4l+6ll zl
^lE +ql Eqil= +qe# ^lE
'+a+. zlE4 eg q6Jg 6Iq,
+ql= aEl^ll e+Ag ^ll"J z4l +44= e+El ^146t 6l-= Ell ol+¤+. g"J olq4 a"l^ll +aE e4d aE=.
4ol sBol+. rq+ +^l7I B|+lqE a4b +4\ + zlzlc q +=E g dz} Ese+ +4lqss, rpn êl=Hg
=e E e q=rll
+^J= q6ilE tl+S+. g 4zlzl d+6|= EzI +llE6J+ zlE. r?-l= rllr o1e" g
l.6lrrilolI ,t'llzl$ol +eg:zH9 a
'4Ng 7J4ol + el+.
=01
trl^lld$$ +4Ur}. ol dEg ,+?+ ann H "JCzlql el qlE^l CuH;9
=olrJl 3ald3 o.3TsrnTol+. lTHel "JdzI
6il^l A4ol 035 mToJ 2*Coe ,J4zlt_ ol 2+dEg 7l ¤ dz} lfl "JEE 6EE 19 *= qL cgzl(ol {4fol
E E^l 7J4olo3srnToJ 26Co + e+{+(rH r0o.+;. -ZEl ++lql +"J61-rll tr14 9l_o Ir +) zlTlolql 9lotrE 6J
z6dol ,Ji-l7lH +"Jql Elaq= col r8zlq, Ir|4^J "J "JCzI"il E6ll^J +"J "Jd c gzlql d4 "s ++qq fl=
CzL p4d o + zJ4olg.3srnToJ | :2 : lE 3+dol Llg dz} n$q +4+= =tr]^]l A4dg 6x0.375mr=2.25mT
+. trI4^l dill Hql= | :2 : r"J t?d rzll 7I qqot ¤L+. "J"J +E 6J +qeol aul^ll ?J+4
"JoJ+
^trltr ^jl7l7l
7L#*=s+4++. tf ,E +4U+H AtrJ "J.E(g dzlzl-"Jd c flzl"ll flg
\l7l$;l qE) pE ul'q-4 ?3 Alo e 4ltB + 9l+.
16D.1 34lE 556J t+1qoilol
.q fl= 4qa tr,lcConnell
9 spn^trlEHg "itr Eol qdr+r a= Qp N/cConneil (16D.5)

^.1
'soer Er.E
{zlrJ Q=2.2SrnTolA p:. Bt flzl-9 'JE, J/:t_ a
^¤
664 15 rPl=E
ol Ba gzlq eq+¤ +a gzl9 ¤-J ttfolrf. E 16D.1 flrl=sl EEI^ll a+ a/mr*

= ="1,111 =-Et
EilA
-1 0 s" %Ic atl HIE%IC AB
z!tE! q
rH s0.8 (1s)
16D.2
rH 7.8 (1s)
+sg{l 4qe 9"18 ltrlFH9 a"l
c,oH;(2)sl EPR rlN 5s.2 (2s) a.8 Qp)
qzlq
^ll +a= F" "JCzl¤e ¤ + +qE trI
zJzJ qL I'F 1720 (2s) 108.a (2p)
Eql +El-*tr}r 6}14e. + gl+. L, 4, s,4 e +lilel "J .zlE ¤ql r-l "*¤. *E"l ++qq 9lq
p = 0.221 I d zlES a - 0.4e0 mT ol
p = 0.Og z' a_ 2,3, 6, ,,i 7 +lilE ag
7
3 6
a=o.l83mT9 e+Ag +
4 tlp4}¤+ + ?l+. qlE^J ei flz}g zp dzl*
^J'Jr61
z El_U+. trIq^J McConnell =
l4NqsE+Et +s= :.+rrnE zlzl*4 tlE4¤¤ ql+.
"*
419 ols-" olE "JE=ol zqzl r\.$$ ?"1 ¤4. r4a +d gz}9 r. dzl-b 6C "JCzle|9 Fermi d+ ^J
Ê
s4l+ql el6ll^J qt sorrn9 zlzl*4 ^Js4L¤¤ 6}rll g+.
:_ q l*3 a}59 -s r0o.r9l ++6il +9t+ +qeql^J +4+
,=##=0.218, 4 r=r =0.0813
E d+ tr-E4}+q =.zl cEE g 4zlzl a+q-= EzI +J
E++el s¤49 zlzl:n- 6]]46J + 9leq, ffi{-ffiz} ^J
=-
s+$s pC49 zlzlt_ 6|]46J + 9l+. trI+^l aulrll 7a
E46lH ¤. 13.zlzl itzldl.ril. 9i= EzI ?llE6-J+el +ae+
= gî +liE6j:+.qi +-i il+f, zi,llg gg
reljl Ei
(c) Eolîl ctaEt8el =6i
+ el+
=fl
p+{se}i9 dzl-b eql E}lt6l Tlvl4lvl-zl d3a}zl= *6}
q tr+4^l ol {z}z} tr-E4}¤¤ 6l+ z}714-g { zfzl ffi z]tr'tEl o{l 16D.3
zls+q +e a4 eg aol4r g + gl4. olBl{} ^}84} _s. 16D.1oll E6IE zs dzlel AA ?lz} 4 rlol9 a"lrll tl
¤¤ $=rl-$+^t SErl$ol+a 6J+. zlzl{ 4ol ol4e} s4l¤--q- ss.2rnTol+. NOr9 EpR :-.9.1eH3 s.zrrnE E
g dzt9l 4L+^l7l= +zl4 zlzl*? 168.1s^14 ge 4¤- %rc ="l,ql {raz}¤¤ +4d+. ¤. dz}zt a+6F= +
zlzla- ++E + 9l+((t -3cos2?)tt'ql BlEll6l-= E¤^d). ol zI +llE++9 rC 4? s.zts5.2=0.10o14.
qt ++q ^JE4L+g HlFrlCql 4ol 44*ol
zlf5.ril fldg + glg uI= ¤t4e e 0ol =Aolq,
g+. trI4^J tI
+z|_,'L:qz| rfa4¤-ql 7l"Jq= aEl^ll +a= aill +ql E
qqq flE 44*=="Jol +48 + 9l+. cuHi ¤.o194 4e oloJ+ 4qe ¤.olg.E 3ul,$l fe
a"lrll a4dg 4E e. 6t+q 7lq= -reJallo| *4. d flqlg +le] + d-s4lso e_E ¤EEzl ?+=+ olE llEE *
' illoljl El-+^J 44*Eol zllTg- H¤- + 9,lo o + r
zI= q ++lql +B-oE +Eqq fleq, r46toi -l.ill =ul,tll
^l-E-
+ql^JE 4t-{z}-{fz]. t}s }+ol B+4 o + 0ol B+. r
Bzl"J s dzlt 4t44| d=g f glo o_e olullg ^Jg L+
Hund
g + 3-,rd..r-rzl¤.rlol9 tls.4}so etr A#B f S.rI. olpt Pauli Fermi
t ,\
pol {-ffizt ?+. s dz}e} 4 rl"ol9
^}s4}+ol 4+qzl
i\
cl t
t1-s1'-¤+ e.9 rosgl^l ¤EqI'Fermi d+ tls4d'g 4+
rl4"F 6J+. ol d+ ^JE L¤+ F%r^J"lq(+ 44*9 uHaJ
LJe ollLl^l 7 E3 oilL1rl
ql ++6Iq), :146Iq +ill +ql^l uu|g gEE zllffi t'l (a) (b)
9l= Ezl¤E A+qlE ut4\i4(sC4e1 ,JE= z)zluf,
6l-E)
^g fg 16D.6 r dI|. 4ollll SE4tEoll tH-Lf trl=a] qlTtLl=.
afEl'zJollllel
(a)9 U|.|EP (b)q ullEHtl ollLlrlTf 'Jeq, rzlolq E^letg¤^1.^l"ololl
p dzl¤9 ffiz|-ffi2| rla484 s dz|9 Fermi d4 !E40J 'JEtol "Jclutrl.
=
160 drl8rt715 665
=B
+z7l ffiz| ffizi tls++ql Tl"Jqzl ?+=+. +"J olq g rI "J.l*zl d4t:_B 16D.6). trI4^l HI'll *= d
4 "JCztE g 4zlzl ilzl6l+ n +llself9 "14 Hql +l7l zl+ A+9 += + ¤lql gl= cflz} zlttsl4l ^gg
glzll E 4"1
6Iq El4^J
=tr]^ll azzl
Fermi d+ tr-s
'-+q
,l.Jg + 4. cgzlql flE g TJ,zlzl dzlel ¤BolH
ol olaE 9lHzl
E H+. olBlo-J a+9 aslrll +=. NMRqI^l g-^fl A 7I tr+ *_e_4(Hunde-l +zlql qeE oJ flztglrl= dzl-=
6Jg.
"Jq+rtl ltfl a4 Eli6J E= ofl7tL!=g zlzll ¤E ol dolaflo} qlq), E++^J $- Czl-b Ad4eE oJdz}9
ol
aI"I +4. 4 *Czls+ dzl-= rl-ol9l zlzl4 *s4¤* 199 Bzlolzll ¤4. "l E¤ql tr++^J al+I6J a"lrll tr-s4l
"l
d{¤ +fl 6L+z| "JCzL tsAg =]-E:ol ql+61 }- ¤+ de*of, 2.25rrns+ ¤ "+5trI.
=i]ql^J
=e.-d71lE=
tr l. rpn*E z49- +qAg s,Jg zlzl:t- +4UtrI. a 4. +qa +ql 10J luz]lel ¤*+ 4"1 501?le
a 2. g{tg 9B x}zlatol 442J9 +zl4 d+E *E-"lt b4 H zrur+

^fl "JzI+7t
tzJl$dSol +4lJ + 91trt.
=ul.ql
4 "l d$ll zl.J!"l dz}"ll zls"6l-b zlzltrgl E+tl+. tr s. ="lrll +6= 8=rt-8=rl f-g:tt Fermi tr+ tlE=l8,
D 3. EpR ,,.,tr1eH9
Eoht!iE= dzlq zltl 4 rqr E=+ rllTlL|Eql E6ll^J da+.
^ggcESe ^t"lel
zlzl rlazi+ql E6H^l zHzI]9 *Hd5ol zJ+zl tr 6. flz}9 ^rJ "JE= :. ilzlz| g d4¤ z|{ $$$ zJrl-.
ts ¤t"14.
=s-d^lE
ca AI
'1 +^l rl {-c,
EPR +H AA hv= g4tu$o aul,tll d"Eft+ol Sg ril r6D.2
hv= gltr(Qotja) dzte+ "JCxl
^l-"lel
aEl^'ll tls4}+ 16D.4
McConnell ]] a=@ Q= 2.25rril 16D.5
666 xP I
=B
E71 ,\.16 \17 IEB
.=4 t6A gU flal

gxlt
==
Dl6A.1 Larmor tlt+*+9ol+? ol49 Egg+9.o1+?
zITl +-Bql^l 0l*61+ ol+= ¤B6Iq4.
D16A2 Ntun E*H o e :z¤zl.el +a= 44617lr+16ll^l= ol$ zl$'oJ Dr6A.3 4 "llHzle| dzt "llHzl"ll "lzlE ztzl*9 n4g ¤B6Iqa}.
4llE zlz]1*4 df+ql^l zlf6|= E+1-41= olelal z4&
^l-.*o.Jtrl.
ol=el il-= ¤B6Iq4.
o{-^
L-l tl
Er6A.l(a) ts.+r9 zlzl* +ql fl= "c49 q

Îolel tl*+
E16A.s(b) ,H q("Jczl)ql qi6J NMR {¤+z} s00 MHzzl9E z}zlat9l
zll(MHze)g 4l&6}q 4. zlzl sl d g.3- 6.73^fl
x tg-7=+lE
H T' s-' ol 4.
I
rJ9 rpn +B d5f} 9"IzI!d:+i
Er6A.r(b) r+.+r9 zlzl* +ql fl= '0N49 q +fl= Î"lel dE
^g t0-7T-' s-'o14.
+ ?J4(MruE.)g 4lt}6l-q4. xlzl4d Hlgg l.e3x
E16A.6(a) 4 * 4$Idel +"Jql 4 zlzlsld ol9 y*el +flb
g"Jzl g,b
Ell+qe+ dle:+ qB4 +qzl4lL+?
E16A.2(a) +qd zlzllrql,rl trl-g 4lE 6: qe 4ol rl qlLJzl +91 ,J E16A.6(b) 4 gglz} g,i F-4{lCq +"JEll 4 z}zlsld ul& y*9 +9-l=
49 LI44fl,L+? (i) tsN, (ii) 3'n = sI zlt +9lF- qBrll #qzl4l.g*i
E16A.2(b) +qT! zlzllroll.r.j trl^g 4lE 6 9: 4."1 rl qqzl +9 ,J E16A.7(a) 'H q("JCzDE a+ r
= 6ll'J6}E zt 4¤+%LE aTle+ 6l¤-Elb z+
49 +44419+i 'Hql (i) rll+ 4lH 600MHz9 Ntun"ll cEe qB4l qg+i ol Rg hE tsll+E ^g +4qlq4. ol 4¤¤zJ9 zl+'
,l+ +q ,,N, (ii) 0.300T zlzl* +E dzt qL Hll6&3 z+4 ol? E 4E= zlzla- rlElqq4.
E16A.3(a) 25'Coll.r.l (i) 0.30T, (ii) l.sT, "l (iii) ror9 zlzl* +ql 9l E16A.7(b) ',N 49 4* t- ^g 4¤+*9 d+9= z4 CEe
"J^dztE tq4 zHrllf 211w"_w,)/N= 4l4I6Iq+.
=q qBril qe+? ol Bg a9 ul]f e +El4q4.=zle+ ol 4¤+'alE zl+.6J B}l6J
=
Er6A.3(b) zs"collrl (i) 0.s0T, (ii) 2.sT, "l (iii) rs.sr9 zlz]r* +ql Eq 9l * ,14 ol? = 4E= zlzla- +$.Xq+.
{4l#z}1iv"_wrll9 4l4i6iqq. Er6A.8(a) r:.s 19 zlzl* +q^lE rH q("JCzD9 Nun dffi
= '3CqE ^J4zl 4l,t}
,H
E16A.4(a) (i) q,1ii; ,3C49
^J'HZJ
z|l4lf iI (N"-Nd71y$ 5ufle f;z| 6Iq+. Bg MHz_e. LlEI4q4.
rlzl4E 9P zlzlr}el H ufle 6ll+qot 6IdL+? Er6A.8(b) rz.r 19 zlzl* +q^lE ',F qel Nun {5f¤ 4l,ti6}q+.
^llzl$
Et6A.4(b) ,n 49
^J'il4 4lill+ iI (N"-NB)Iw9 d¤"ll,rJel 7,[e] sulle B9 t',tHz-e L}$.flq4.
gEE H Hlls 6il+qot 6t4lL+? gEE Esl^l7l
=!7I^l7lelts ^lEE Er6A.e(a) $Sg q^{ o}2149 }oll q g"Jzl-= o.qzag4. o.s0019 zt
aol aE= .Eol= ¤84 grEo1fl=+?
= ,lf,l +ql 9lg,IE q d-Eilel qlqzl(6e)= 4lt}6tol+.
E16A.5(a) "J+ ppn ¤+r4l* 3 -ro ulol= 4i4(QEl')= ^l-S6J+. zI El6A.e(b) '4Nel q^{3 ^So}2145 toll 4 goJzl* o.+o+4. 10.s0Tq z}
^l+ trll
7l*E xllzlzl9"1"J ,l* +ql flg "I9 q ^JEIE qlqzl(6s)E 4lt}6}q4.
*B ad"l "J+q4.L+?
^fl
EE 168 NtMR^trlEHel
=8
¤E E^JI
Dt6B.'t Fermi
ql q$rll
d4 ,!lEAIe" r+ ¤+sI 4lzlH69 NUn9 4{-49 A6J Dr6B.3 714& ^J+q 4aJ 4zl4 zl¤, "Jdzl zl{, :,r-ln *o|] zl{9
zl{apxl$ ¤86}q4. +l"Jg z|.tllal E6lq4.
D168.2 tl#= -Za^l7lr zlzl*& +^}6Iq ¤
z71E Nun ts*41= D168.4 t++ d*ol olE "JCzl¤ Îolq
"JCzI
4zj_"e +ElLtE zlTl+g 491+. +g ziTllHl^l +LBg "Jezl
*B A6Jg. LlElr-llzl ga xil:9 ?*g)ql el6ll^J= ^g_^g
=xll6l=444E
"l
¤+?-lE¤'+e +' r?-lr *g tlql^1g ¤+?-l#'*3 ^J'ol4a +E ¤E6Iq4. ^¤(}f,6}zl
=
¤E6IH4. .+g tp+.LI_a- A,ol+= *oizl sl+4 ol¤.!} ,Ielgq + D16B.s zlzl{_oE E+oJ 4E=4 E}qr4 " + 5'j="+ q5 il-= ¤
oll,q 5-3 ffi zlzlr 9lL+?
Batr, 7+7+ 2711'4 ql= Eq+. ^}olel
Ee 667
G-^-
Jtr
'Hql qdl^l 400.130oooMHzoll^l z+56I= +r*4ql^1,

E168.1(a) qlqL4 5ls"+ ^g-+ qql 46J a6Je-e ql^Jsl= trl+E= "J:"l¤4.
olF"l 6=e.804 6=2.20J + 'H-NMR a4EH ¤+4
^tolE tl5f 'J
24lE F"qI
E16B.7(b) eql 4E! e*e-e ql^Jq= q+EE ql
4? Hrze.9"].zI 911.9+l +4q4. ^¤-r
(b)'3cql 4 oll ri 100. 130 000 MHzoll r.l
6l* ts*41 ql slE4
zlE"
168.l3r} 168.l4ql _Bt an+ Hl*oJ "JBg olf-r|{ zzll9
El 68.1
^-1, El68.8(a) rae
olEol 6=50.011 6=25.5oJ F ,3C ++el ^lol9 tlt+ ?J4? Bol Es" alzl 9+g aqlg olg trll qtlq= q-6:E_E 'J6Iqq.
Hz-". $ulz| !AL+? ÊEH
^fl-+
E168.8(b) "JCzlzI 27Hg ¤-E 6}z1 9+g qn+ e6Jg olE ql ql^J
Er6B.2(a) 'Hql Ell6J|Î 400.130 00oMHzoll,tl 4E6l+ ts+I4lql^J, 550H2 qg ffis.E E-olq+. ^¤-r
dFÎql ql*61+ ,H /.slrEe ¤+4 ?J4? 64tr + g"tz}941
r-*? Îolel E16B.e(a) lB 168.13r+ l6B.14ql -H-"J Ar+ Hli*'JHg ols-" 6].$ 2zllel
682(b),3cql 46}l^1 200.130 000 MHzql^l zl*6l+ ts+I4lqlî, 2s C0orlz

¤¤6J ?.J9 olE tr]l q^JEl= tr|6!E= "J6lq4.
El
/-qlEEl ¤+4
^g-;4ol
E16B.e(b) 37HE -E+i6} 1g-; 4ol ¤i*9 olE trll ql^JEl= trl+E= "J
{Fi}q 4s"6lt '3c ^}olel
?J4z 64tre 9"}z} I
6H+.
4l,g+t
E168.10(a) 1-=E_e.-4-H e q Hltlel rH qEg +E4 o ++ E= zl7l4
o|,tllr=$rllolE(ql*9el CH3 oJCalE slqlzj olt-e 6=2.20
E16B.3(a)
ol{, CHo "JCz}9 +6+4 olt+ 6= e.80o14. el+ z}+ xl.7|+ol (i)
o e 5+d. #4Ee r
56al.{4. ol+E ¤¤6}q4.
r.sI (ir) rsroJ ull ol Ezl9 ol F ¤Eql^lE +zl4 zlzl** qL AE
E16B.1o(b) 1,2,3-E 4=e.-aHldlE eE¤: s++4 o e+
'H E| zlzl!-o
E ¤-E"* F4Ee ¤+a}q4. r ol+E ¤E6Iq+
E il-= ++LIAL+?
E168.3(b) qqlBqlElls9 cH, "JCzI9 El+4 ol¤.g 6=1.16o1{, CH, Er6B.11(a) PFs9 'eF q59 Elqr4 ".g E= zITlzi9 e F="6J +4e +
"JCxl-g slq}4 ol¤¤ 6= 336014. E+ 4+ zlzlerol (i) l.eT (ii) 16.sT +6Iq4. r
ol+E ¤H6Iq4.
"J rll ol BzlE ol F gqqlrl9 i.zl4 zlTl+3 qL cEE il¤ LlEl ul4"lg)9 'eF q# E]44 o + E= zlTl4se E
E168.11(b) SF;(44
441=4i E"*+ele ts+al.{4. ja ol+= ¤H6}q4.
El6B.4(a) 6e=1.00, &=2.00, reJI/ax=lOHzoJ AX 4l7I (i) 250Mtlz; Er68.12(a)olCzlzl 6=2.74 6=4.89 + 9lil ,tlololl,tl EEg ++.
(ii) 800MHzql^J 4IE6l-= ¤+4lql 44.J 1o + ^g qlt'-ElE 'H-NMR
^' ss0MHz9l^l zlE"6IE +"J4ql^l tlEH++ lE7l 9"19 4l F tlEzl
slEH Eo#3.rllil6lq4. +*l 4E= Hze +4l]loh 6lq, rMSe.+El E.J C_q-e H6IAL+?
E +Bg zlio e 6IqaI. El68.12(b) "JCzlzl- 6=4.2e1- 6=5.59 F 9lil ,tlololl,tJ EEg 6JtrI.
E168.4(b) 6e= 1.50, &=4.50, rqI /ex=5HzoJ M, 5fl 4lzl 500MHzgl 3s0MHzoll! 4tE6l^= Ert4lql^l tlsB++ +szl g"I"J oll + +lE._zI
Ll4B 4, o + qltlEl= 'H-NMR +oJ C_q_s H6IA!+?
^l 4IE6l+ ¤-rJ.4lql
E_oJg
+B aE= Hzs +41+lo} 6lq, rMs-tr+Elel ^8lEH
*89 zl3
^rllil4q4.
_oe 6|q4.
El68.13(a) TMS-tr.+Elel 'H+Eol 500.130 000q1^l "Jqt3+.
¤-+4E sl+4 "1fl6 4tr +)g gulolfl_LrJ?
s00.l32s00Mru.ll^19
E168.5(a) '0BF1z| +$L|]= 'eF NMR
I'B NMR adlEBE g: E168.13(b) TMS-tr+El9 ,rC +Bol r2s.r3O 000q1^l "Jq$4.
g ÊEH1+ r2s.t4sTsoMHzgldg ¤+?]E +Ezl olfl6 atr e)g g"tolxl-*i
^?ilzl6lq?+.
E16B.s(b) "BFlz]. +Er]l= NMR l8lEHr+ '0B NMR
g ,H
g
'eF
ÊEHel E16B.14(a) s00.130 oOoMHzoll^l +Bg +e6iE+ "J= H}4lq^]
^4lil6}q4. rMS_H_trI 75oHz El * d¤+ql^l *Bol .Jq*q. ol B+4el s}+zl
El6B.6(a) "pp;E .rlez[ +44= 3'P NMR g.g .4lil+q olfl6 zltr +)g ¤o}"l4L-4i
+. ^s]EBe] E168.14(b) 12s.130 oooMHzgl^l ''C +Bg +g6lE+ EIE Er*alq^l
E168.6(b) '4NHI9+ 'sNHig tH
NMR.EEBq rMS-Htrl t875Hz El *g tl¤+q^l *Eol "Jq*q ol +??]E ++
=¤ ^4lil6}q4. zl o15(6 zltr e).g gulolflLu|?
E168.7(a) lB 168.13r+ 16B.l4ql tr.J ar+ Hl*6.J %r-Bg ol$a|{ +zflel
EE 16C NIMReI =J4 7lE

gxll
==
Dr6c.1 6+isl¤ +s++^ +4 +ql^l 4Ig E^kHld!+ Ae)E Dr6c.3 +"J C+ 6tl* H"J +7} ^lolE il¤ ¤B6Iq4.
^g-
4z| $3rlrltg SszI tolA++ f;zlalirjl Hl6Iq EzH6:6Ji-lle+ qg ,*= alql e0. gê} 180. gÊ z}
= Dr6c.4 44 zlzl*ql^l
ee)= rJ^{-= ol+E ¤E6Iq+. ^{-+
*^lag al9 a4E- z|*llal 56Iq4.
Dl6c.2 fl Overhauser -849 g"Jg ¤B6l-J, ei Ezl +E 'Jd "JCzl gd q
D16C.s '3C qE gEl ,rlzJol rH qE ssl
golLH= r-ll ol a$z} qBrll ol¤-q= zl ¤B6Lq4.
zJ ol*E ¤E6Iq4.
^laE+ dBzloe
=
668
^t7l8B
G^
JE
El6c.1(a) 9l*{Ho}^]lE't})q '3C NMR 6=2loll 6Cg +a E16C.3(a) e0"+ 180' gÊ zl+ tt9 ,9lzl c,ql E++tr}. 180" ¤
^dlEHg
gqeg +44= 4+dg +EIUE+. F"J+ 12.5ps E"J zl+^lTlelH
^ltg
q¤ 9"I4 ^llrll 4+qo| a].fl=ufi E rJ
r3oHzq
gt^slEHg "JdxI ^$
e6J EHg ol$ql^l q +e e+AE g qql^l e0. g4= slllg+i
+A6IH B9Co-e HaJtrl.
^ll7l9 ^l+ ^lrJol 9"lz|
4+Cg 6= t78oll +dg +r 91r+. ol +i{E ¤Bg ole" 6}E +"J
A6J E16c.3(b) eo"Ll 180' gêl zl+ t[e] c,ql E=¤]+. e0" ¤
^lrJg ^ll7l
do + H6Jtrl. ol-=. dil .ll+E ol+= ¤B6Iq4. 1E 5ps E"J zl+^lTlelE 6,¤- 9"i4 ^llrll Eil+qo} o}4l!*? E?J+
eql+&el t3C NMR 6=7eoll +dg E trl+ r-il219 6rql^-l 180. ¤4b zl+ qaLLF
E16c.t(b)
=+a ^4EHg ^ltol E"IzI
dg +{Utl. E.J-J "JCzl eq} EHg olf.611^J +A6lE qo1 t.sHz"J trilE +E zle gaJ' $EI rlzJ
ÊEegE+q. gt q a4aE q= ffi,tjol +B Cq
E16C.4(a) Lorentz
r60Hz9 Ae}d 26Coe
6= tTeoll +Cg +r 9l+. ol ffi{E e6J=,e EBg ol*6}E ol6d o + 9 tsutz} qfl!+?
H.J4 ol5 d,¤ 4+el ol+= ¤B6lq+.
E16c.4(b) Lorentz tB CE 4o1 tzuz"J trIE +tr 7le BF6J e}3r+
^lA
3 g"IzI g4lg+i
E16c.2(a) NoE-a rtpT| oj'$xlql AqlE ag +A1I q Eg- + fl= aql Er6c.5(a) faE- zlzl 4+ A49 tl+ol r.0 s rlololl t! zzl A^lel Hi
)g ql+6l.q 4.
e-_tr
o A}'6194. zle *6J SEI ^l7J r,9 6[9 BuloldL+?
E16c.2(b) NoEs trpzl. oj,fzlq AB¤ ag
=:rJ(4A +p$'I gg + 9l= slql g"I4 zlLlo} +
E16C.s(b) zle gtaJ' ss|
Glt(qilog)g ql+6}q?+. ^la t7| 50msol4B ^lrJ"l
E471zF+ A4 d+ol il¤. alel Hle-tr. A4614'-+?
EE 16D E^l d|^l.7 l8 AE

*= gxll
D16D.1 *21 442J9 ppn g Azlql d+g +z| Dt6D.2 Fermi d4 tlg4+r+ ¤+3tl 4lzlU69 EPRE tlqzt+
q q+4 7lq6l+rl= ¤B6Iq+. =trl^ll
4E6ln r rBg ++4= êlEHg
Eil qB4 ol+El=zl ¤86H4. ',llErf,:+E
G -^-
L-l t=
El6D.1(a) aul,t]l ?!l {}fzt 4?+ 2.}rnTq 2.6rnToJ 2rH.e.l H6Ixl ?+g E16D.4(a) t"J zlTlc 49 zit +qeE EPR ldlegg,rllzlz]. rJ* q
oJCzl-= EEI6I-= 44rJol 332.srnrql +Cg E .slEHg +41ilfltr}. z}l9 d-o e a4d+. ol eg 9"141
qB zlzlat"il^l atrl^ll +4 cEol +4+q E olEE tr-..il4 4lrl= g El6D.4(b) 27HE -E+i6'J +EoJ^gg 3"F9 49 zltl 4qeg EPR rdl-eg
ulz| !AL+? ol ,tlfzlz]- r:2:3:2: loJ sTllel do + ,J4Tlr}. ol qE ¤n}*i
^fl9
=sl,\'ll ¤E} tfzt 4zJ
El6D.t(b) z.n mT,2.s7mT fel.z 2.8erriToJ 37ll
Er6D.5(a) e.2z3rcHzoll^J 4E6l-= E{}alE 6IE gz} ^J4 +i9
E ?*3 "JCzl-= sg}6l^= 4qzJol 332.8rnrq +dg E EPR l4E8 6dol 32e.r6rnrql +4t+. ol flz}9 g(l3 9u}*t
^Fs"
EHg +4.11fl4. {¤ zlzl1t9l,t] aul{l +a d$ol +4+q E ^trI
=+:6lzl olE
^]-S6IE Szl t4 6fa
Er6D.s(b) e.2482GHz4l^l +t6l+ #j4lE
I tlrfl4 g"izt 94t4i
^]l7l= 9 ppn 6Col 330.02mrq1 ++S+. ol gzlels<13 E"i4t
El6D.2(a) (i) .C,Hre+ (ii) .C2Hrol+4.11= EpR r-EEH9 a"1,r1; d=:g ^BlEe
E16D.6(a) 2rIel 5¤6J "JCzl-= I:EL6}= +qeE EPR /-slEHol t
9H EE= '+4Lll1t!+?
,rllzl
: 2: 19 E.*.= ,*Y 34lE CS ::o.znrt 332.sntt, r4.7 334.8mT
El6D.2(b) (i) .C'H2C'Hrel (ii) .C2HrCzHrol +Eltll= EPR ]dleH9 a"l ^'llzl ?+
d=g qtr +sE LI4q]dL+?
ql^J +4Ur+. *Czlql QloJ iul,rll e{lt'-+= 9"14i ol f-$zllz|
^ll ^ll7l e.3leGHz9l^J +Eqlq. ol 4qeg g<19 7a144.
Et6D.3(a) Hld 4qe ¤.olgg sIlg 2.002so1trI-. (i) e.313GHz, (ii) El6D.6(b) 3419 5,.="¤I "JCzFE -troJfl+ 4qaq EpR r.EEfloJ t:3
4F61.= ts+'4lq^l= zlzlat : 3: 19 ,r'llzl Es.E z*Y +\14 d9 r:r.+nt[ 333.6mT, 335.8mI r4r
^llTlql^l +Hol "Jq
33.80GH291î
"lE
+aL+? 33s.grnrql^l +4U+ 4 "JCzl{l ql6J atrl^ll at+ tr'+= 9"|4i ol
Er6D.3(b) +sg{l 4qA ¤.ol89 s<lZ z.wz4ol+. (i) e.s0tGHz, (b) B*4lzi e.332GHz4l^J zlE" 6J4. "l 4qeq g{ig *a}{4.
3a.77GHz{l^l 4IF6|= ¤+Alq^l= "lH zlzlet ^llTlql^J +Bol "Jq
4ds+i
Ee 66e
-*21.t. 1u xl7 I aE
o 6lxl
-5. u --'r E^l
rro.r -=.9 gEqlrl ¤E6J 4l&'JBg ol+6lq -E-?l HIe| ziol olulL.l} 48I vu,-E 1"14. el+zl I+fol EBI-E +tr+ "JqB ql=
olFol4"t aJ
qEde qq ^JsI+4 dz} old t}¤:.ll +q6l^=Ell, ol4t Hl* qs E.J6J r49 "JCzl NMR z..trleHol +"J ¤+qs ol+q^lq, r +¤
^J= 4E =Jq+C4lql^l
gol o,E 4}3r+5le Hlar} "Jîsl tls| 4aql^l {$ ,y y=fiv,+fp,v'E foltl4. ¤zlrJ ,= UI/([I]+ [EI])e] fi,=lEr|
o,7I Etr +|flqE HI¤¤¤ 5 + 9l+. oleloJ dz} "ld uJ+"l gq+ (ul+[Er])= ?+?+ +4 ^J4 rc+ a'* t]EH 19 E&o14. ol rllolrl$ all{
4Aql^l ElE4l ol o}trl]EÎel
44zJol ¤cslq, e^l¤ql "JE 6l+ Ell= {++ il. 6v=v-v,4 Av=vr,-v,$ "l*oJ* 4ol ¤4414. I
=
zl-*zlEI¤4. {]+^l +qee qet 4qeE 4¤{}
(a) sgl -uoJ ^g gB el it¤- EE 1r1oo1 E9 z-lg *.E_ [E]o_H-+ g{ ull= IrloE (6v)-,oll 4
o + ol*9r gl+. ExI eB ¤41 +o
=9Jqe+ *^J"l CAql 44I ,JB qI s^121 4dg +Elrllq, a_ 7l&7]|+ [E]Avolr. = y+ *E ¤¤g -K,7i
(HI_¤,¤H"I4 s+ +_olEH)g ole" 6l.{ oflz}e} s 49 E= cgz}ql ¤g Eq4.
al1}6lq4. 0) s9 EpR ÊlEe Eo$g q+4Eolel. rl*4 gg "Jflel Ezl#
^lel ^g "JE= rro.+ ^84"ilszl- HIdl, qBHIdl, E4g+
o
e-strtlB{ldl, H!3qEB, "i qEe{ldlql^l +d Efl^} cflz}ql q5il^l
sl4 +lilq H, CH3, CF3, CN, 4 NOrzl zJzJ xl\\zlg 59zI 914.(a) 4
z|7I CA6J 4l&uJHg ol+6}q olE "JflE +Tlexlql^J ol$ ilQlzl
s trJlg^l alrl= ql ru6ll^l EIE +lilql il= c+lzt tE ¤g. d6l-= 4lt6]-q+. o) dtr
ar+ql e]6r{ E|+ C?lztel '3c slqt4 ol5g rllBqldl, Hltl, Eq¤-+s
t16.2 F +elE "JCzl-Eol 44 6=a.04 6=5.2E T}zlq +9C Exl9 eqlBHl4L flaqEg, q E + Hldl +-e-E 6rlqlq. '3c s+ql4 olEo 4 c
olCAillslql 9aHrl dlg H+84. eouuz ¤+l4l= ¤ trl]= r-ulegol
280Kql^l *"J Co+ H6l+ql 300MHz= ¤ tril= 300Kql^J ol Hsizi
flxI r}9 ¤a ,s6I 4l&il Îolql d¤ 1'-++4171-cBd-4194? (c) ql
,,.jol {{l,t}s-e 4^tq} 4 Ezl-E9 +4 cgz}el
'3c s}+4
ol¤+ o}4
Lt+++. + gEql^J9 trs H¤IE HI¤- +E tr-+e+ gcsl qlqal=
"l e+ e4.
+6Iq+.
zlitzl CH, H CF, CN NO,
t16.3 NMR E"*Bg ol+6IH o^ lxllzll re+ eg 4Ig EzIe+ A^ Eel
6 128.4 1285 1289 r29.r 129.4
eg +Ee ^J+= aCg +
EI6J trf8.r+ ee di"-l B¤
ÎolE +6Jillql
91tr}. ol "J¤E E},i¤qlî ul4 cflzlgl ,3c slq}4 olEo4 cgzl t}E da d
EI--E I K,= [E]tIl/tEIl
6Ie+ dB tl++4lrl ^dB6le+? (d)
"J"J (c)9lrl t**4lz\ ¤B+trIts
+ ol
^J++alE gflql4 g"Jql +6||^l ¤E6Iq _H-oI{.
e++4 jl+ol e;-|rll gqLI= ++ql^J= I+9 "J^dz1. lqyp -r.ur=flol
27HE +8, + 5I+= +el ^Jq Iql EilqI v,olr trlE 6I+= A'* t}Eil Iql
E,lA 17
EII/ISE Al.E
Ezlz} tl[+¤-q Ez}el 4zl4 te oIEq +4$tr1. ffi 17C o4i{l

trol ¤c9r" r+z}q +ae+ zlbol 4+qg $z| {aJill
zl $z)a- 6l-= Ag ol trszl¤¤ zlzl:il- ¤EB + flr+. ol Eqql^l= qillql^lE +zI tr-sAr-+q st zla olEg
rB4+ Eo+Ad-e_E ¤ag dESe "l+q4l+. olEe ¤H6Ij4 olq^J .lill g.HE ^dag ¤¤ 4ol+. 'sE alql
E4ql flg-q, +rl + Elol4 E ?IqlE ?14. "lE + g+E '-E lls zls"l 'sE "+ ¤cl r4r ¤+ E"r| ag +_s+ a
A¤4olq, +'J+(d*a Eo), gqflqE(+EA gA 5), q¤¤ gqq}4-g-E ¤B!+ 4o14.

:1qn E.qh=Elsq=(DNA Eo) Eol qTlql +++.E oJ 17C.1 Ei{ +oil^'lel ErtrJ SEttE; 17c.2 Ei{l-=71 zllE; r7c.3.EE
E; 17C.4 3+
++ Elc(+"JEr+ E-?-lÊ{l E" )o14. z}e- Ez}e+ Ez}
=
Eg zlil qql.l+= 4{ql 96fl^-l EL4l Efl$q r$zlil
H BE" 6lt sl{li]$ u3$zlE {r+.
17D zErl
l$xl¤9 -Eolg EzI tr-sz}+ql el6ll^l AC$Q. ol Eq
17A E^lel d7l4 ¤tr ql^J= +"J"J BEl]= r.El6}zlEl +B4el '5-4t-{ a"J',r+ +
B4"J BEI]gI 7"Jql 3Ag E aol+. {zl,rJE rEz}g ¤
E4¤9 +s+ 4zl4 Ce-e.='{zl ;!*ztEHIES}'¤+
=l]e+
qqtzl "t gzl ce +4lE r+B lolr}.
.E-'. E + 914. "lq+ CeEg E+71flz}9 4"1 Ezl "J ^L"lE
17D.1 EE E EaJ: 17D.2 80lE! +=el +r; 17D.3 +1t3 i.g;
9 dzl# qu {+ + zluflalizl. H}g{+ a o +^1, + 17D.4 Eqr'4 ¤E; t7D.s E11 ¤g
aq1 ¤9.| dzl_$ +4qrtl 6la+ E= d4¤ol g* dzl

tll} qL CEE HI¤¤ 6iE+ 6Jtr1.
g=^} EEIE;
17A.1 {171 17A.2 El*E; 17A.3 tr= 17E rlfll E-Et
flzL zI* Ezl, "l r$zl¤g A+ql El+^J= zlzll o1a3 a1

178 Ert=.t l'o;o; SEAIE Cg t6]]^J q6Jill= ql=q. "l Eqql^J='E-E_o1=' 'o,
=
¤l r4r ^Jill"+ql +6]]^J r.a6}4r 6l+ql, olE- {aJzll}
ol Sa{ol,<J= goJ ?4 Ezl-$ 'vanderWaals tt-E$ qL eEel d¤zl"J Ezl ^Je4 dElill zlillE r+,* ^de
^}olel
+,4.f + a.J!+ ee- +s+ Ezlz} {.Ez}+ql *t zla $ zlxlr. ol+q4}+. {zl^J='i+d ts4r.$'ol$=,tI +
olEq +4^J ¤E6Ir-zI s+. E*e .441e+ aillEg ol Eq
ql^J Hi+6}rzl 61.= Hq -&d .tr-E4+_e_e +dqq fl+.
s6J EzI ^Js++E ¤Ee- a"Jrll, "l *sz]"¤* +,]]el el
tr erl HEI trIEq "Jqt+.
{}"J "Irl4 "le1a3 $Ezt¤* l$zl9 +aql^lE +3-6J 17E.1 17E.2 0lgrl 3i{l E
qgg*+. =-trol-:
178.1 +E fl6lE gEqti; fiB..2 +^ trEl; rZa.S fli{l gErlt
^tolE
g rl.-E 0l rrEq EE=? q +e EzI4 +Ee4 ?3 e+"1 tri +E¤"1+ e4]4
=
eg s4 +zlE i& zi4ql eqI6F= trll S6ll^J r
=AqI
EzI tr-E L¤+ ^JaL6l"+ ^JE-EtrIql.<l iet qFlg 6Ir +61fl+ olelql eq} ¤^Jel p++4 ¤4e eHE deol 9
fl+. A¤ ag4ê r CE$ +a E qq Eqlî ql{ rB ^llE]= 4,"14.
zle+ +etr}. +Ear+ q4}"l +4.I= tolt +=E +aql
+6ll^l= gaJ=zrollrl re6}s.4. g* z+qrlE +dg Hl-+
EEI 17A Erl-el fi7 14 ¤E
E ,L]-+zt -E-flEql ++ d+4 g+zloJ Peter oebye9 olE

> 0l EEI= EH+= 0l+ ql^J Hl*E 4 o e^J, olE + *+l r+q-4 eg +
Exl uE= Exl .8E4|E= E^lsl c7l4 ^l-olql=
¤ECplLf tr_lEFill=
Al?l 4B++.
= qal^'l
8tr011 "Jtrlgt3 aolq. Exlel Exl +azt ol*Jxl 01il
.sE= LlEfLHll 61"!-rl= gopt Eltrl.
lD = 3.33564 x 10-'o Cm (17 A.2)
> "-!d 7}lH

gxl-=el tr4= Exl Exl-=E xlHt|6lq 0l-
?Je.l gEoil + d6I tt +r4 -e7l roopm"J# trq4 9i= H4 tr-HlE
=8-d E r.0 x 10-2eC molq, 4.8Dql 6H'J+tr1. 41"3 +z}el .93+zI
4^l7l7lE 6fr. !E el+ C7l¤Joll tt|SoPllE:dtl.
E.HIE= tr}lillE l Dol+.
> =Js-d qlHl xl4 Ert= ¤+ d7l 'td+zl. EHIE= zltl Ez].4. olelt
Coulomb9 H4(EE 2AE El¤lrlE 8^]6), Exle-l 7l6ltrt4 +4,
=d
g7 $=rt EEIE= E{¤ oli flzl¤"] dzl *Cs9
f.alr. +llEE+ 0lE, HoMoel LUMo ollLjrl =
ilol+=7} E= el.6l-7ll -tr¤6}zl{
=rl =61 ^l0lE EzI LH+ql^Jq d6I
il4(EE eE)7.1EaJfl olEE +xl6lr. flqot
:dtrl-. g+ xlttoil
Boltzmann tsE E4= olEg AolryEq 12A). "JEq +zl4 HsI trl$ql +r}ki{(Eq eE). ulE-r3 Ezl^b
^1ts 421* +ql^l r dz} Ese+ qE +lil7t 9:-4zlzl ullE"ll
+g 8=rl EE!E. EAI ¤q. r4q ol +ts,8+zt E-Hl
E= "J^14"J aoe4 4zl*ol îl4qH +
^1411+.+d
EzI9 4z)4 Cee ql"* EiilE Be ^J¤EE fl"Jol 94. +ztE dzl*"] zle"¤ rllE zlEel ffiz[ EHjFzl-g^14
o e H6LtrI
Ezl Q].el da} EeTl 4+ $f$g ol+H E^l¤ Îolql
+UUl.
6t-lr.9P zlzlatql e+6}zlE *trt. E= ol+4 zflz} Ezl-= +^"ig +4.llq, dB4"J p9 (}
tsat+ol 9"lr-tzlE g Hclol 1.08D, r4.]1 Hrzl0.42Dolr+(-E 17A.1). EzI qla
I4flz} Ez}q +C q+E A46l-= +,q+ eqlolQ. ,r.19
17A.1 T!zl$=rl -EElE ,..3-
Ezl .Iae Ez;= +^dq-= flz]_Eol E"J flaql +61_=
zlg q+E+ q +soJ + 9t'i. Fe q?lz} E4.g a+ ql
d7l 8|--r[E 442] nq]# Eqd + A6i +ee+ -ae Elq
Auzl *r- flzl-Eol -frf,alzl ?*g +lzl= zlzla3 ql= +C
il4. "l Rol ++zle+El e) /?-lql H]6]]^J ql+61 49 uI=
ol dzl ,xr-=-2ffi E i7l ,g=rlelr +¤+. olBl+ d6I HH 'J fz| ?14.
gg d7l 8=^l EE!E4I 6l+ ElEl p_tr srlaliql(t), ol

ElEl= gd6}E+q "Jd6l¤ 6}6lq r]-q=4 z!! azl$ z)
:--.
I- rL
E 17A.1 8=rl -e.E!=(p)e|. nJ=E. Ftrl(s')*

ll=QR I7l 8=^l _EElE9 17l [trg] (17A.1)
o//(10-mm3)
LtlD
-a +A ccl.r 0 10.5
H2 0 0.819
HrO 1.85 1.48
1 l)l g|=^l-
HCI 1.08 2.63
HI 0.42 5.45
{-lz} EHIEE sr tr+l= EE "lq(c m)olzlE} "JH}4e +
Hl-sr ++lql r-llulo11D)71ol+qr gl4. ++l 849 EzI "l " zlE ¤ql rl "*9 alE"l ++Elq 9l+
671, ETPJtE¤
e].Jtt ofl 17A1 lJ1 /u res
Hld¤ Ezl-s-¤ or(2)3 s" 4 E p

zfolzluJ +d ogz}Tl olEel o u^
flzls+ +sr(6d flxl^b + g 4 8=^[ E"ElEsl H¤

zle] paJalI "J¤E flzlÊ aI 2 9'E, O.
+e+ A.J6tr gl4). r?-lr 4L
¤,*"1 "JE* aJ*zl EHIEE
.qe 49 ol+q tr"{qzl ?*zl
5#h5 !.". = Uti + tri +2 Lt,lrcos@)"'
EHI-=zI eg q=(q=P +Hidql^le+ ?ol) ol

(17A.3a)
3 .lctrlE^' co2 + ''5qzl

qlEql +dol+. ol+q aflzl. d
4ol ffi$ ztol z]$6H4j+.
¤ EzI co29 a+ql=,r11 $lzlz[ sF dto]g 4.$ {a}
Tl,.la_ glzlE| oc AqlE r!-=-xl. EHIEE Co AEIE
0= zcos2to
=
ffiz[ EHIEe+ %]6]"1 cH]qlq^J ^JE t]4lqzl ollE9l
l+cos
11,", = {2 tti 0 + cos @ ) }'/' =2ltrcos]@ (17A.3b)

ol Ezl-b ul*C"lrHr).
zlEEt q 17A2
4flz} EzlE 4+zI EHIE: *rl4 o + Ezl "Jq qBl Hltlg e = E(1,2-)e+'ll+(1,3-) 2zl+Alb ?+?+ @ortho= 60o
* trI+^J r7A.3b^lql el6lt^l olE9 dzl

7l=el Tlqe+ olSE uJlaJ,e-tr E6]lg + gl+(rB 174.1). @^,to= 120"014.
qiEî i,+-rjf,-+ +'tldlei A+qi= + 55Ef o-cl jlHIEzl 6l-=-z]. gHIE l7l Bl-'L-- q+r+ gol g+.
,<Je ul-f 6F"l* .]]ag ol+i1 glzl ullEql Hl+^dol4(ol&
e}Bn9 a+s+ +e+). r4+ r,z-4¤iE_e.Hfdg 2714? F,",.o,tho _cosi@o,,ou _ cosi(60') _ + _ -.uz _1 .7
llr"r,,,,r,o
- cos j@.",,, - cos j(120") - L't
+ eHldl 4+zI EBIE= 60.9 ers_e Hl]S6l] +g a4 e
? zzlel ,t6qzl. ltHIE= ,*+E+. ol 'HlE] 'Ld' "JB¤- "l*
6IH q4 zVl tszl¤9 ffizf EHIEE Hln4 Cq6}|l +
ts + 9l+. + {qz} EHIE tt,$ t4,7l 0E ol+r ffizl. EHIE. 4l&61-= q e+6J rJHe sE flzl-59
^Je 4E
?lg trll(4) +Erll= F...E ql4l4 o + trl-+4 z}ol aig 44 +E d6le-l +lzle| azl$ 0l+61-= 4,"14. ++ d6I9 =.
E + ?14(Eq 8cel ElqlzlE t}^l zzE Hol-4). 7l= g.e +zi +a J-FE?Jq ulzlzl9 +ql Eqfl+.
=q4 flzI
qls^J rd+zl EHIEE xCEg 4l&6lElE tt9 *
qI
+ d6}e+ 4 flzl-E9 Ezl ?IE dql qfl tl44 alsfi
"JoI"F 6lq, ols$ ol+6}q q-g_$ ag H.Cg 6iE g+.
I
r. =)Q,r, (17A.4a)
11
ojzl^J e,b flzI I ^JE ++ d6h xyE flzI 19 x=lg, :24
-)
(a) ;roo. = 1.57D
(b) !ob. = 0, =0
r Hdg EzI +E E.= flzl¤ql aa 4o14. yc¤4 z4
T
I1"ur"
Es- ulaaj !$ ol.$6|]^J 4l4}6Jtr}.1J,z]'4 o + 6d"J Ezt
E a+, 6+Ee-l Eae .J9e +lB + glzl"J 44zl zI*6I
tV,I ,ll +s-E+ q6l+ 4ol ¤4._E= Elq.q 5+q= +4lzl
\ "Jp9 a-71Y tr}s=$ ,Jol p,,F, 9 L..el ^'ll CEg zlzlt-\
^-/
(c) 2.7D (d)
+E + el+.
lTroo, = 2.25D, !."u,"= 1,t.0. = 1.48D, l)"ur"= 1.6D
fal 17A.1 El=+eElu 0ldtri1l((b)+El (d)z|'^l)E 8=^l'EEIE= tt-(tt',+ yt'r+ pl),' (17A.4b)
EtrEHldl(a)g 8|--'Il-EE!E(/lou,= 1.57D) BlEl .lc-d ?i4
-=,r.l.rp_e
#ct((c)el (d)e.l
-
^l+^4).
174 EI[e.l d7l4 ¤tr 675
O t=xt
GZ@ Err g=r-rl
altt sfllel
(s)ql +e].U a4 Ae ++ 1a(e9 ul]f)s+ ulaulelE e O tt=xt 8= +^l-
+4U CE gzl¤q 4lEE- ol+6}q ol olulc Tlel d e O Oa6 +xt
zl ffizl EHIE$ a7\e+ H]]6&3 +6}o14
e9
(182,+20) 4= 86 +^l-
+0.18H
(132.0,0)
+0.45
(o,o,o)
ee =Î
-0.36 fi A.2 tr71 rl-= +xloll r|,|3ol.ts d6l' Ht|E. gelel A--J-d E6l EEotl
(-s2,107,0)
=eJ
-0.38 7l?]Elts 83 trl-= +^lEsl TloJEl= 8=E 7l^la_ Ll-El-g +
5
?1trt.
=doil =d=
a.4:g Al¤l r7A.aa^19 ol+4q 4+zI EHlEq ,+ c

E=¤ 4l&6}r" olq^l l7A.4b^lg ol+6}q olE
^ll ^J +zLql tr|{^J= d d6l¤ol Hl] 6+
EEe+rl ,5h:z-z| EHIEE a71= 4l4I++. +E d6l+ gg q +g q.= 714 +
7lE d6I e--t.60e x t0-'eC9 Ell+"Jg i9"1l"F *4. ol il+(re uA.2).
=rt=
+al4 o E "J="'I 6-
6+ 6-,
olulc 7l= +c +zlE + E"+olq, q+^J 4IE gd-g zl4. n* *3 mE =-,rl -E-H]E- 5+
"JEE dCE + S.+. ¤zlrJE ?ldg +^ gz|e+ "Jil zlxlQ *g z.l-+el EHIEY ?*
q4 fl61-9+. zl ?+= A d6l¤9 u]]¤"14. 9l
-e.^J E=It= A d6}olq, ++
7 ollEJ' cH4
p,ql +* !g q-q=!+ ?"1 ¤4.
=ol z| EflE= dill d6}*g "Jd+.
11, = (4.36e)x ( I 32 pm )+ (0.45e) x (0 pm)+ (0. 1 8e) x (l 82 pm) ,Bqz[(n = 2)] olul ¤Et H]e+ aol + d6tel u]]¤"14 E
+(-0.38e)x(-62.0pm)
+zI EHIsE *zl &}=+(= dg. d6}z| ool4). 4=
=8.8epm
(n = 3)|; d.g d6|+ ''L:qÎ EEIE= 4zl ?*= A d6l¤9
=rt
= 8.8x(1.602x10-te C)x(10-t'? m)= 1.4x10-'o Cm
u1]$ol4({laq Co2 +z}, 3). r4ir.8E *rKn = 4)E + d
r?.ld-q tt,-+o.42DzI H4.rryq +* !g ffi$ pol olz| so1q, d-ja__rz} EHIE+ 4+ +^l EHIEE *zl t*E d
s+. d6l¤E u]]9"l4({la4 cH4 +zl.,7).
It,,= (-0.36e) x (0pm) + (0.45e) x (0pm) + (0.18e) x (-87pm)
+ (-0.38e)x (107pm) 17A.2 E!*=
=-56epm
= -9.02x10-'o Cm
q d6I7I +H d4# d4eE zluflalzl * 6J+= ag
dz|$ol 9}- dzl^Jql e¤¤ + 914= 49 9"laJ4. :z
r"]4q Fv=-2.7DzI ¤+.olulE 7l= ¤H *ao1=* 44q 9* dzl^J$ Ezl-= "J:z4zlrll $gEI olq+ ¤+
pts 0ol+. trl+^l {zl ffiz} jLH]E# "Jd6}rll Hll6}^l?J + '44. 4lzlzl r
.J el+ dzlz}.ll Hlrllall^l +tsq= 8g g=rl EEIE p*=
tt=l(O.42D)'z+(-2.t D)'I''' =2.7 D
t =zl p*71r+q=4 aol +qTl+.
*, y,A z CEEoI o.+2, -2.7, o) o tglzl qE+ 2.7 *+)
el ,JolE *= EEl=. r?]B ,'5r-+z} EHlEel Hl]6J1g g F* _ AE, uJ*s tgel1 (17A.5a)
g + ?14. ol +Al= (s)ql E7ll Hlql rllzlrl El"Je.

^J+ aE EzI9 E=E+:z ¤L+. ^J9
trll
+44fl+. -O.38oto.tta.ot .= ¤+Ezl =-=11+g {l{z[ E{]E7l 4d+. +g xl]
lo
E.7l 17x1 (o)el r]lolqg +0.02 A,o,o,o, zl-b dzlzJ4 ¤B6I^l ?*g + 9lo t:.e Sd+ Al&ql^J=
^l7l
ol+6}q E$oJrllalg9 dzl tt +orv/c\+o.re olag EEI "Jss +44q, olull= LvJ+ aE 3 x r BE a
t-sa,+r,olH
H(ga,+r,o)
+^| -E-BIE. 4lt}6lq+. 6 e 444"h +4.

a s'z IZEFY:Az'¤,tE 9* dzl^Jol 4B6l ,Jts ullHqlaq d+E qlolzJ) +
g ,6qz} EflEE a7l7l zlzl* rllzloll d¤ " e. ulzllalzl
676 ErtZidE ¤
?+9-q 4g=4 rJol 444"t ei4. 1 7}4el EE

trJ1l
# qlqzl- ¤+4eE AE(HoMO-LUMO ?J4=o L+E+
F* = dE+ +gE' + "' jEE+E [89] (17A.sb)

.ll})e+ ?Jqa 7}e6ljr" E 7l* +g+ {ol aol-=-z} EHls
¤zl,rJ FE ol +zlE (rzDEsJ?s.4L tl4. dzlE d6l"*ql+ +^t9 tlxlE Rg #El a4
=
E e+r -H-H ol
=Î4e
lJ¤¤ 0161g + 9lg ?."14.
S+Eq +9= C2 m2 l-,,. (EE-"lEl),/=ol+. rfl+ Ba ol
^lql
ol E+E +9= E¤6I71 qlEql "JHlzi o tr r+q=4 ag EJ rllE ol 4ol ffi$ ?ol ¤4.
i=t-E
+tr1 a'93 Hh+q^l ¤!4.
^l-s" d= 2e'R'
LE
a
a' - trJ*-=, +tr; [dg] (17A.6)
"l ^lql E6iE uy Ezlz} 44"il tr14 fizlola_, E g E

4neo
¤zlrJ eo$ d* +dg(E9 ze9 El$zI9 dl:|0;o1u1.4neo 5++(+, LEzl +g++) dzll ?zld+ trI+^J E+E=
E ++l= c2l-t m-IolF ? o/g +iilel ++l= AE4tol ullE HoMo-LUMo 7J4ol zJ4g;$ *zlaJ4.
ql ol E?"1
^Ja+). ¤+E +q= dzll EzI +rle+ a7l7l
cJ4lz flzI el4# zlzla- +4u # qqxl
ulfalr|( t6-30 -3, 10-3nm3,? Argl zlfl.f"l 4).
"Jg *"J "Jd6}ql +61+ dzl¤ zl4 ne.gq +a;!Qle zl-
4tlY trll gs+ qlHzlE *rI4 o + qlqzle+ a.+r
=*:
-BE AE = et4f/woRol4a + + il4. ol +41. a"ll *6J ^l
tr++î ql Bq=+.
HrO9 ¤+E +El= 1.48 x 10=30m3o14. l7A.sae+
17A.6E F zl-"-+Prl p. =4ntod(il} +9-:z E e;+ tL
g =2e2 R2" nn!'^ =zx4n¤nR3
1.0x tgsV m-'oll E6ll^J +gg Ez}fl ffi{ EBIEeJ e'
rzl(g+ rd+z} e_dqgl rJal{)z} q-q-r,+ ?ol ¤4. ol aE ¤+E *4 +reo o + ++r olz| 2E +^l6IH d = R3
Lt = 4n x (8.854 x 10-12l'Cz m-') x (1.48 x 10-30m3) "l Lls=Ell,

olag Ezl +ule+ eg zlfl,+! z_214.
x (1.0 x losvm-l)
1V = 'l JC-r +lql^J ?ol ¤+E +q. szl4 Ezlel
-H_ql ule+
1.65 x 10-3sC m= 4.9 x 10-6D = 4.9tlD HoMo_LUMo 7144 tl+g+. LUMoTI HoMoe+ qlqzl
Eql^J Tlvl+$ {z} $Ez} drll "J:4e + qls :z4a}¤
¤+E7l + ?14. ruuozl HoMoBtrl t¤ r,il= e]+ +
=
Ezl-E ¤+E +jil +cil# s l7A.lql ++6]l +9t+ *zlzl*"1 dz} +EE rTtl j/+tlzlzl *6tq r?-l6lq ts
¤+E +ul= flz}4 Bz}q {z} uflzls} +4lg+ aEzl *4. HotVto-LUMo zJ4ol ar* E4¤8 dB4e
E
=-q, +"J"J dzl# zlzl-r. 9lu}.
..ll++E Exl-E=$ ¤+E7I HltHJCoJtrJl, olag E+EE
@ E=Eq=xt'i^
a7l7l Ezt9 dzl^J.]I r]]ql ^J'il4 tsll6}ql el¤*+= ag
z+ B-6}e_tr.9 EzI ¤+E= "Jzlqq}4e _+ trl-s-r=4 Ag
o + +q4l+.1
^l 9"lel4. Hldlel ¤+E +rl= dzlttol r?-lql +z16}z]1 4
s"¤ 41ts 0.0067nmrol_z -r_elfl_g_+ zle"¤ 4lE O.Orz3nm3
ol E+. olq6J HIFHJ^d ¤+E= 9d naman
^trleHol *l
*=r>#+ c"Jzlg q+E rre*+(Eg rrs).
¤zlri z+ oJ'Jg dol dzl d+z} gHIE+^J, dz].

Fôn? 16A.3 E!=
7I Htql^J{E+Q olE" 6I¤ s== tr-Ell= "JE trll "Jq+E d
6l-E olt. aE= +Elrll= 4o14. 'tce glHzl Ejr)el E= ffiz} e41= uJEE E=+r +eq ps s^l
^lEE {zl
^J4Eq 4al 1o14. ol-brll,
"lag r+q=4 Rol tsx}el ¤+ {zl Xt-iz} eq1_=
fu)ql+ Ezl^+ "Js yv= N/yE #el 4olc}.
t ol al9 +E= xlzl¤9 physical chemistry: Quanta, matter and change
p= ri- t-^ron fi7A.7\
(2014)= -u-"t4. Ut)N r-l--1 t c:'---11
rzn Erlel d7t4 ¤tr 677
+.di{l= E*ol zl^L" 6J uldsd olld"l4. E4l 3 4Ee-l 4l+

16= ltE,lkTE -.,69E ol
^lol
ffi$ ?ol t'J6ll BoJtrI.
(a) trJ*el Tl=+ ol=
pfi""'dcosgsinodo
f+c +dill= 9P dzl^Jol $..g ull :z Ezl-Eol geFql 0t )
_
E6H^J ++CEI HlloJ1g +l6IE_+ Q) = ool 4"1 ¤*ol ool Ji**'singdg

E+. q+6J
9F ^Jol 4+e ql= BzI ]Lr+z}el dzl^Jql 4 olq^J ./= cosg-E +r" d/=-rin ede= ols"*4. f_elr 4
eI uflo.J{l q-+ qlLlzlz| Salq, *g gluJzl u]]o.J9 +471 B 6J4l= f = -r(0 = roll^l)eI f = r(0 = sql^-l)_tr Hl^3r+. rBl
q "*"t44. "l al}E *l+ {t-]z} EHIE ool gzl ?*eq, dr--l r
Bottzmann tsE= olso 6Iq (p)= +6J + gl+
^19+ X.IET F T
e+e e-e
I . _I I _I
rl9 *s. 17X2 trta g+rl EfllE0ll EH-d Al PI'-,yr-'dv x )

x-
01.)= -/.1
ex -e -x
+H +4|sql^J ++i +*.E ezJ\ H"1("JC tlzl5.llrl) Uy x
E sin0d0dQol+. {zl ffiz} -E-$le 7l ol +EH 4zJe- o} 4E E.3
ali $2145 ol Hole| Boltzmann oJzl. e-E(qtkre+! fiql Hl et +e-' 1

-p e-e
el++. dzl*ol z+ql ¤qtr ql= qlqzlzl "J94 oql ru t -r
^
6l-r} trl+,(1 ffizl.7]r q+ 421* ++lE "J919 ,J+14 oql
0e+ 0 + d0 4E ¤q"il H}l6}g q¤ dp= trIg4 e
ol !g +*4 2lol ¤ i gl4(, : yr,tkT).
^J ÎolE
ol +49 + 9l+. orro_r I
'
0,r,)= 1tL(x) . 1
, {zlr.J L(x)= !_, - -x
e^-e.'
, e-E(o)'kr sin0dg EE E7l 8+^l EE!= (17A'8a)
oP=
J;"*r*rri,.,odo
*f :d+4r 6Jq(rB uA.3).'H+EE
qzlrJ rol4. 9P dzlar sl z1%I6JolH 4+zL
0<0< r(x)= Lansevin
EHI=q E* zl "J6Jol 94 :_ B+il7I r+s=4 u.ol ¤ 4 a+ql=xz| Ql$al 4l+.qlE^J u=rDol.l. T=300K9 ull
dTltl ^117171 100kV cm-' oltol qqot xz| o.org Hz.ll
"14. =
9}-rlJ, ql++el dflql^l= "lB+ q+.oJ
dzlzJ$ olf-
=ld
6J4. x < roJ ullt: Langevin EL+E zlf a;45
ot,) - I u,dt {zflap .a'l
ql oJ"Jg ¤"-lH L(x) - a,xrl E+. El+^l ¤+ EzI ,J+zL
EZI 1 .nl^=-z[el 4zl* +q^]e_l .llHzl sHlE= q+4 ?ol ¤4.
9lHzl E(0)= ol
46:r-+zlE ffizfzl &tl*,6e1- o15i lts.
eql +-q-4 *ol 9¤qI4. p'8.
(/t, ) =
5tr 8+^l--EflEE Eil^l tqFil E7l8l (17A.8b)
E(0) = -1tE cos0
tr,J4lz 4+xt E{Eel z+ cBg ¤+q +*

^-l
el+ 4+ dzlz}9l ¤q6J rd+z} EHIE CEE B+il= + 0.8
7 7
*4 ?ol g+. 0. 6
x
!z -J
cos0e-u(')'tr sin0d0 0.4
J
Ut,)=lffiGar =u
!""-t,rlu, singd0 o.2
E(0)=-lEcos0 0
0 0.5 1.5 2 2,5 3
x
cososinodo
=ll Ji'o""'ut .f,g 1 7A.3 EE E7l 8+^l E fllE= lltlal'= Ell 0lEEl= Langevin -d#
singd0 (^t+^$. xt I 4Z ttfl= qEl E7 lLt 7lE(8^4)=
l"ert*,t,r, 0 l8-dtr|.
678
=xtzdE¤
zJ21* tllzlzl ql*61 +.9 agE *zI.J9l ulr* EzL 4'+^t ol AE¤ dE EE=+ dz} t4 #ql
4+B E"J otq4,
sHlg9 uflalol 4zl* ++ls E -,qE6lq, ¤+ 4+zI EHI tl*ifzt +7lBql II|4 ¤+Ezl- ¤olq a}i6l+ ol+= ¤
EE B+e- alrllil Q) =pE d=,_e}4. E6l-= qlqlE ol+g+.
gf- dzlarE H.J trll= g+ H{. E_Hitr
HJ6Jol ,<1.<Jal
7t alg nI4^J x}l_u]lolpl gl+. rq4 4zl* E E+

^lz}4 ¤.?z|
(b)
ol +g ddt'= zlzla_ TlE"6J trll= g+ 4+{-EHlezI
,lle +ql^l r"Jt trqd + d6l-Q,4 Q
trlzl qrlql "*+q^J d+6}zll zll-ullajlzl *alq,r}+î Îolel ^JE4+ =
^l + E]¤i¤ 9lHzlE rl+4 ?ol ?9t14.
Eel ¤+ql o}+fl TlqE 4zl *qlq. "l4g +?-1= g+
4+zI EHle qlEql ^JzlE ul|:d trJi"l +e a5+ql^J ^l 919'
,' = 4ner (rzA.e)
4A+r "J*trI. #zlzl +ill +ql,rJ r44"J9 sld6]-= ql

eI rpszl a4FE * r0"Hz(ulol=+r+ g9) ol/J.9 tlE {zlrl e3 ul]AE SdEolq, "JH}4 o e. tiEll +d99 ol*
6H^J e = r,ro o
P +4U+(E9 zaE ElqzlE ^}al 01. 6J E
+q^J tF l] +d¤-g +c6trll qH ¤+ql El]+ oleJf, ul]6-j
ael ^J4 +dge +42]19 dzl +=*g r EAol Eqflg
¤+E zl4zl Î4tl+. trlle+ Hlq gi¤- rI ul:z $z$alq?+?+ ce| co), ¤E e. _ ctco
rlffi t"J trl E 6l+e] ¤+ C+e E:a1g E
ol+. tlql +a¤.g +"_q +q olg= r}"l9 tr-E++,rllzloll
Êq=
ol ¤+g gp dzl^Jgl el6l]^J qE +lil7} oJrElzlTl
=ol+.
qlEql
ql+61 g+9 "lrl+. qlE^J E3 zs"cql^J ^Jr]] +dg
^JzlE 4olci.Ezls=g 9P dzletgl
e_l6l]^l ELfl4 4l =
ol zsol{, tr}+^l olgz} coulomb
tlg 6Lq, rflotq +zlE .trol-:z-.,2| EHIETI H6IAI ¤4. EzI ^}s4}+ 9lH zlE 4l+ +
qlîel 7ttr+ 4E + zt4+ +^^lvJr+.
zf aiolzlS Ell e?-j= q+
^ltg Ezl-= TIE^l7l= T]¤+el ;-,t3olzt* T,tr + g+q7l 4ls Ezie g Eeg
e+ 4el Asq, relo}ol +Îdel {$fzt 4e-1d gq qq_E = ^Jql
*zlalAt qH "J:14d ¤*"1 44421 gfll g+.

+dgg +4u+.'HeE E=¤ ol+61-E Ezl¤9 t}'ll +
dg4 4zl4 ca Î"lE e=J4 +4lE eg + 9leq, ol
"Jr+ld S+e t4l4-" + ¤ol"l "Jq+= 4 trl+4 ?3
*al= dzltlE 4l#z} Êg+.tlt %r-^lE tlE+tr 4o1 u|_E oeoye *1"14.
^tr =CtI
Ll 4¤ u1l"t4 "Jqt+. z|^lo.Id gqql^l= +3 4l#ql
Debye (17A.10)
.9s zI4S dzl-"J"I ii+flal H6l= +el "J6Jq +8p- + ¤,+2- M ^l
fleq, rrl6l.q "lql= d4_"e. dzt E.trql zl.Jq= ¤+ ¤zlrJ pE rle9 e* "JE, MZ tszl-9 E a*, :.el_L p*
"Jol Bzll ¤4. "l4t Ezt ¤+EE CBg flrl
trJ=E+r. g trl-94 ?"1 C99= E="1+.
qI+ ol ¤+E. aÎ6lelB z+ HJ-6.Je-s t15+ aZ 7l7l =
-Z a*6l+ 4zl* +ql^l= ExI9 s+E7l- trl-.q-4 ee "J p'
*=*( a+ 3kT
=
rJ+ tgsll (17A.11)
ztqq}4 o + +q{l+= ^}dg ols"¤}4.,
^l
¤zlrl a3 ¤*EolrJ. 1t2t3kr} ]j.7]r*ol ¤zll6J trll g4e
0ro l"l: .ttn
a(a)=1> E Bte+¤ 4"+zI EHIE trIEql rJzlE oSolQ(17e.sb^l).
alo- @'
n*0
g+ ,td+z[ eq1= 4 zl¤zl s.9 rllb o] rl"l 4¤-4 ?"1
9zl{ tt@,0=B(o) - E6o)g p$ dsfo.|4. ¤zl^l Q¤,4 a 94, o14,9 Clausius-Mossotti llol4l *E4
e + aEg "J6J+ 9l+.
t, -1 pN oa
¤,+2- 3Me, Ctausius-tr/ossotti4.l (17A.12)
0olE ol zlol
ar _+ a4 ¤+Eql +qI ^l o + H6J+.
HlEql oz| cll$al qlHBz].9 qts E+: {f,fs4
= Ezlzl- Hl+^dol4+ sE dzltlE +ul+z} !]*61 +oI^J
E gd El 4^l EE +g d,og +^lR + glg atrE)
Ezlzl ol dzlz}el ,J6J H+= +lul4ztH,<] ufia]slzl *6t
¤+E7l-trIs=4 ?ol ¤4. q ¤+ {zl ffiz} Efl-E7l. ¤+ql TlqE 6}zl *e- oll "l
Clausius-Mossotri 49 J-s" ql+.
a (ro) = - #L:,.,01 r,,., n
-+0, a))q"J tr]]
@ g=rlEElEtE=Eg
Z ol al9 +E= zlz|59 physicd chemistry: Quanta, matter and change
,Js=(8)el
=E
gEql^J +CaI{
(2014)=i -e"IzI. ^J'H +d$g "JflE "l-4
1?A ErlqlcTl4 8E 67e
e+Ae qlolElg Eflq. AEs E

z[$ .[t-=_z[ E{Ee+ ¤+E +q=
118
+6Iq+. o !
o
2114
E {
E
o
8 #-9.= F
o--
el"c p/(g cmi) er 110
0 0.99 12.5
20 0.99 tt.4 106
2 3 4
N 0.99 10.8 (103 Kyr
60 0.99 10.0
aal fiA.4 ils_=el trJ=Ee| g=xt -EEIEE ?6171 ?l6tl,\1 E7l
80 0.99 9.s0 1 7A.2oll^l 0 lE-d P./(cm3 mol-l )9 (1 03 K)/Toll EH-d E,l. l'Jr[.
100 0.99 8.90
r20 0.97 8.10
140 0.96 7.@

160 0.9s 7.tr
olag E^l6J 4"1 :zB r7A.4tr+. +zl+ ^Je_l ¤¤g p,"/
200 0.91 6.2r (cm3 mol-t) = 83.5oll 9lf q4.rJ Noa/3eo = 83.5cm3 mol-l
= 8.35 x 10-sm3 mol-,o]4. trl+,(],

r.E{E
^lE} ^}ql +dge E ¤+(r7A.r0^l)ql E=6}q, ¤o
E ol E ¤+e gE ¤+E rala g+ a7l 4'qz| E_ 4Jtr{
_ 3 x (s.854 x l0-" 1-r C2m-t )

x 8.35 x 10-s m'mol-'
HIEE a71\7A.r1^l)ql E=q}4 r7A.r1^lg r-l-e=$ pol 6.02xI023 mol-r
Ht¤ + 9l+. NÂ
EE 7lz7l -_J
,:ffi* N.u2^
'm 3Eo
A'
geok
v-
I
T
=3.68x10-3e C2 m2 J-'
17A.64-]99+El a' = 3.31x 10-2em3 = 3.31 x 19-23.-3

olE +al= tol ol*el4.
q^-q=4
"l+. E- 71&7lE ro.ssolq, q{^J N4tteeok= 1.055 x
. oJH9 Ssollrl e,9 +C+ ++ 4 .$Eql^JE
10acm3 mol-r K= 1.055 x
e_E+El
10-2m3 mol-rKo.la flg-l
trl¤4 ee ar+= eg +
%FHql
(e.- 1)/(e.+2)= 4l&6J.I, olq^J Uttp= q¤. ^J

+g p,"ql ++ ^l
=rr6J
el+.
17A. l0^l_q__E+el p,"g +*4.
. P,"¤ l/Tq qlql^l E^l++. ¤o k
v2
9 x (8.854x10-'2 J-'C'm-r) x (1.381 x tO-'r JK-')
relH zl&zlzl N4tteeokzl 5i,t_ uT= 0ql^lE ¤¤ol ll= 6.022x l023mol-'
Noa/3rr?l zld"l +g+. NA
Eol erg=q A+q= M - 152.23g mol-rol4. olE rll 7lz7l

olElE ols-" 6[S trls-r+ gg s= E]= + 9t+. x (t.ossxto-'m3mol-'K t''
=4.39x 10-'oC m= 1.32D

el"C (IdK)/7 er @,- l)l(e,+2) P^/(cm3mol-t)
0 3.66 t2.5 0.793 r22 Debye 43 zl-* qdg aFb Ezl-3 +F+ql= lolo + ol
20 3.41 11.4 0.776 119 qlolEl= r7s"c7l 99"F += ,Js= 7l a41+ql^] sld
lr8 ol Ezl-b qlill4 s e +¤"14.
40 3.19 10.8 0.766
++b ag Bq=+.
60 3.00 10.0 0.750 115
80 2.83 9.s0 0.739 tL4 TlTl $,71 17A.2 E-eeq141el tlql +dge 20'cql
100 2.68 8.90 0.725 lll r.l s.ztol-rl, 2s"Cql^J s.62r+. "JE= gA6lqr z|{ap.
120 2.54 8.10 0.703 110
(1.11g.--'), ol EAE ¤+E +i{e+ nl':z-z| EEIE= +
r40 2.42 7.60 0.688 109
160 2.3r 7.rl 0.67t 108 6Iq+.
200 2.tl 6.21 0.635 106
cI z'I '.ru: oz-0l x 7'I .E
580 ExlztE¤
,HeE E¤8,?e d*ql^Jq Hq +E'e+,IA +ql^lel H¤g fi¤Eol {l"lt gEg E"4B ull :z dq %r-6}9 Hl-
4E c'49 ul"l4. 4 n,- ctCo\4. 4zlzl +^l+e-l Ceql E+. q+^l dB4.J zlrlr"rd9 dE+ gE(E 10's q
s¤l Maxwelt E6IE d¤+9 {(zf.,.lr3ol4 z} zl 1016H2)9l,rj .rleel Eeg-g +C6lr olag ctausius-
^lql =a+
e-ld)ql ql+ EeEg +-q'=r+ B"l :z tl$+ql^JE tlr]] + Mossotti^_lq Bq +E ol gqql^JE E ¤+E p*4 trI+^J
dgql +4lg+. EzL ¤+s. aE +B + 9l+
nrr- gtl2 EtrE$ ,5l8fl SdA g4l (17A.13)

^PlE
=s-d7]lLJ=
trl d7! 8=rl= + d6I +Qe+ -Q r4r ulel nE. s^lq= I +44= 4014.
AEE
ol= zl4-e ol+qa+. 16. E*s(:.4r E= +tr])= flzlE4 EzI=E HoMo-
Îole-l
22. d7l 8=rl gfl!= 11= {+zlE gA6IE*el "Jdate o} LUMo ?J4al +fl¤4.
al-b ulelol4, : aTlYp = QRoJQ. rJ7. ,Hee-l E=e {zl ffiz|- EBIE "JE+.
tr3. Erl= g+ a7l {.+zl¤ *= Bz}trt. I8. H]le EJ=g g+ ,'s+zi _ELHlEql 7l.JEI= ¤+oltrI.
=.5
o4. Ezl¤g ailE $zl 116' +zl-= 714 + 9i4. nE tr9. ts=a1g E=e e.l+ +ql 9+ e +lilE "Jr4d9l zl"J
=rl=
n6 azl E.HjEE +4,11= d d6tE ufl¤oI4, 4 *3 e 9E E?o14.
HIE= 4444 ?*=tr}. I10. drl trJ+E= az} EEE "J:z4dql 7l"Jq= E+Eol+.
Ds. E!=E= dzlttol EzlE ,d+^t jrHlEE +B^l7l= bq
=s-d^l=
.^-lzl
oa Î
--1 +î al Ba
{zl ffix} EHIEE r7l lt=QR
ol
zlo-1 t7A.r
+,18+zI E{lezt +4.]l= 771 1t,", = Uti + fi +z 1t., 1t. cos @)"' 17A.3a
+8,%qz} EHI_EE
=.7I 11* = dE C¤ t^h oE ¤*E 17A.5a
!* = ar'+ I7tr D<ltJ B= aE+E l7A.5b

=^h
¤+E +sl d,'= d, l 4tt¤o
z-l
6--1
ol 17/..6
¤+ P -- (tt)tr zl ol
o-1 T7/^.7
Debye al (e,-l)/(e, +2)= pP,,lM 174.10
E¤+ {, = (N^/3e,, )(a+ l11l3kT) 174.11
Clausius-Mossotti 4] (e, - l)/(e. + 2) = pNoal3Meo L7A.r2

Etri iTB E^l= lolsl 8a4tE
++. olE d6l+ d+ +ql tsH6}qq ileq ul4^J e=to

of
> ol EEIE HH+= ol+ o++¤.+gl+r^J4+tr1
qal EEHeI E^tJ dE4tEoll E6H^1 ¤ESOlLl'= E^t al:sr-i1l7l
E_ffflctrt. r
p1
> 6_{fl 7}lLJ +O, -o,1 a2

eHd +lErt# aElg go.7lrltrJ HJ"Jd 8E4rEe EESI
E{s=ol dEF{E q= a=
"Jol=tr}.
> -JgEl qlHl xl^l EAI 1 + Ad¤49 +E4+q zl"Jq= q{¤.llHzl al

8d7ler9 gHJ4 LllEE +xl6lr. ?,l,olot Ettrl. coutomb F"J d6l¤ r}"l9 HlE.r+ tolal d6l-= ^l-olE "Jqql ,l.J
=61
ls\t$15E 2A9 aF$lg| a^l6), La|rErl-E 8--^lE'E!Eel EE ulfl¤ qlLlzlE -Jg +$4 e+.
IIEEe+ ee E7l= 8trzl 7E.t 1o|E tr4lE E 0l6ll6tr
=^l'E
:drHEE
?lolo} 17A). x = ll2r
Q,Q,r I r )
"=+(-ffi.*s) Zrsl(.- l-x * t+x )
eJAl2 r4.axJS 4 ,r,3^=_x|tr_ f*

van der Waals 8E4tEg gel ee +zl¤ qle ^J
a a4"J ullb I ( rolr= + 19 6JE¤ trI.94 ?"1 dzl]*4
^l-olel
s++"lq(9lulzl= *+=) + ts{¤
Îolel 44el
l/1691
el=EI+. ol g"Jei zl+g a+ H+l= H-"i^l E= Hl-aoJ 1,1-,
l+x I- x
*s4!"ll-zl EELÎa + 914. "153 {4 zl-zl ¤E]]E ++
+q E+7I i E d6l¤ Îolg ^J_q4}+ql zl{aJ4. ol EE ilg + 6}7lzltrJ a6lE +lel q^q=4 #l EuI.
^l"l
4Cel q= ^Js4t¤+ Eq 2Ael ol4zl9 8^l 6ql ,=
=Eol rlHl¤ qlqzl y_q,etfintrol4. ffi{- (r+x+. ..) + (1-x+...)} =W = - W*os
¤B6JCoulomb
^l
#, = Qr/olr= E ol +s=J+ ?"1 ¤4.
^le-
178.1 +E d6l'= SAEfE xi l-TL-xlE xl=L /\l'=xl.Q.
^lolel r r ltrQ, E O_'.t Lvt
t19 e+l
O__O
(178.1)
4fiEor'
4+^l d6l¤ rlol9 zJ4 tol ol ffizl$ +e6I= 44 roll
H|6]]^J gd 49 trll}{/ < r) ol r,3t4zl$ E $=-xpE 6J+.
p= Q= "lelB r4r ¤ ++rHH

(a) Eat-8='-,xtS-e=fE wl =+-trlElE,
AE +qA+.
=o_e_tr"
(t)ql^Je+ Ag HH6Jql^l= ol 6fol $ol
+= A6I fl= + d6l-e-l coulomb ElHl¤ qlqzl=
q, ¤g "Jqg +4U+. d d6}zi ,,8+zI +ql q6l] 4 1s
=4ql ElHl¤ qluJzlE zlzlt_ @3 olFl flg rl= ol
cos@E +6ll+qot 6t4, oll
d A6Ie+ 6t-ixl.$ +ts + 9leq, ^lql+
dol tl*ol "t,-l$$ eo 44lq eg B"lf"lot ¤14.
F 4-r--rz}
^|olE ^JE4L+qlE +AL 4+^la + 9ltrl
^Js4+ 9lHzlE + d fla|,<1o1E tla+8(l/rql Hlql)
H+ q HEIE-Al(t/lql Hlql) d d6ie+ rya^l7l +.J61 g?-l
@ tr E6lel tr g+rl',\fo;o; dE4'E
Eqeg rls-l <tql 00 + +7tt}trl. ol43 +"J d6le] +a
ffizf EH]E a7l7l d ,r[qz}e+ d d6l- e,zl-(l)
1lr = e,/oJ ql^l E. *ll, 714 rol
"l+
,d+z}e_l ++ dalz1a34
ql^le+ pol uflolq*¤. oI9 r}"19 ^JE4¤¤ r+6l] ,i^l tl4lqzl ==zlEr9l
ull$ol4(rfl
"15 178.1).
682
=rliltE¤
,5r-^JE L+q 6Jol E+. + EHI¤ qlqzlqlq ¤-q 7lq=
6l+ Hlq d6l¤
^l-olel
+ "Jq oJ$, "J9 zlq= 6F= f,-f;
6}e_l 6Jol g+.
d6l-=
ÎolE + Hlg
E}l 1 5 ffi{ tlE d6l¤9 tl[zl+{ zl{q= iEl¤l
¤ qlqzl
olE ql Tlqel *g q-q=4 ?ol 448 + 9l+.
a\-at
tlr
,r- L (Q,Qr,Q,Qr,Q,Q, Q,Qr)
fg 178.1 E7l At=^l-E 801 Tlalql rqzl A46h= Ejl= F 7l^l 7lq7l '-4"sr[-Vn- r - r --r:l)
?Itr|. 71zl7l qal
E6le-l tr1EJ]¤o1 A^6ln(q7l^J= elol6tl^l=
=LlEtLJtrl)=71'Ao|l
E F E6l7l -d.Jolal^1al ElTl ti]|Eoll 0l F.Eatoll E6tlAI x=l/r
^1PlE qEJl¤8 Tjzl Eat"J Ar8-g nllErf trl uulell00e tr=-drl.
sA+E Q,Q,
4neor (*-,.*)
tr,JAlz rdq4¤9 d d6IE fl+
ri*olg4 E EzHp = 1.85D)71 t.onmtrJ? ¤q4 fl+a

*ql^le+ ztol t< ¤ d4lE at¤ xoll +qI + 6Jg d7}l6IE
trls=+ ?"1 ¤4.
6lz}. ol olg9 d d6}e+ E +z}e_l a3"qzlft.(l)ql^Je+ e
I u}l99 ol+I ll4. :_48 olE rlol9 tr"g4}+ qlq l/(l + x) 1/(1 - xl
zlE rze.r^lql el6ll^J tri=q,=4 ?ol s4. v-- 4ntnr

Q,Q, (l-x+x2
+...-2+1+ x+x2 +...)
Q,, Haro
{zlrl a^qE 6Js=3 6J*.9 oll o"l qq, 2t'"J tsrll E+. r
,,, _
--
(1.602x10-'' C) x (1.85x3.336x10{0 C m)
E]8,
4
\------------.v
,,, x=llr
=-8.9x10-"J rr zx'QrQ, 2I,Q,Q,

'
v
=--
4n¤or 4fi¤or3
ol 9luJzlE -s.+t<l mol-'91 611*++.
trl+^l 1rr = Qr/ rfla Fz= Qzlolo + (2)ql +4U Hflgql^l

E ^JE4L+ iil$j¤ 9lHzlE q^.q'=r+ *"1 ¤4.
(b)8=rt-gt=rl 8E4tE
!,!z - F g*xl /.lolel gs^_rE
*E Eel. qt}6l-q (2)ql^le+ gg Hllgg ol= 7 9l= + v-- 2Tc¤or3 [(2)e.l HtlE]
(178.2)
ffi4f rlol9 tls4}+qlE 4*^la + gl+.

l-t
r
p2
ol rlazl* *E a+E+ ¤d rJ EEI-EZl(l/t'
qluJzlE HIE
ql q4) 0o + d=++ olull=; $az}* +Al7l g
1
*4, -o1 +O, -C.2 ^JE

r-l trq4 ilg
"I +^dzlfl tr.J+.
2 178.24? (2)e+ ZF$ u1]gql ql6H^J"J 4+¤+. + +C +
zlzt (s)4 ?9 uHgql tr}+ Ele rtrJ* Eq4 ?19 ullE ol
F Ezl¤ rl-ol9 /JE L+ ElHl¤ "ilHzlz| rl-e-=4 ?ol ¤4.
@ = E &--xr=
^r.orer
ala+a oilLjrr
l( tt'' r)!r' P )\
Tl+ +ql^J (2)ql^Je+ ,J"l Ael r"JE trqal 9t= +,1d-+zl. V_
4fi¤or3
lt,. lt z -
I tr-E++ slHf¤ 9luJulE *ql^Je+ qAe "JBg ols-"6f F tr B+^1^lolE Ata^+E (178.3a)
q Arug + fl=ql, ¤zlrJE + ^Jg4'-+ qlqzlzl47HE ,J [(3)st utlg]
Ext= tlElt8 583
^lolel
u2
e
p +4, o2 p1
r
r 5
o
111
+O., I F,F, cos0

lJ1
4
v - 4twrrr
Utrl.trcoso-3p,p, cosO) -- 2'fitnr3
3
(ol ol izzl] fl.tlo1_=E ,t^fl+ 4*s9 _H_olel.) o}4e+ ?J? 44 trl$ql cos09 ¤+^l= 0ol ¤trI
^lel =il=
+ rd+zl7l @)e+ ?ol ufl$!flg tr|]= ul'J¤ "llHzlz} ttr
7E
6l-7ll r-l-e-r=4 B"l ¤4. Hol e^
EE!=6tE0ll^1E 2n 0
P tfr ?fr
cosO sin0 d9d@
,,v:-.11,l't2f (O) J. Jn 1," oOl_,.dx =o
- 4'rT,¤.or'
t fOl=l-3cosr@ cos0=x; dcos0=-sin0d0
tr 8=^l 8e+E (178.3b)

= ^lolel
[(4)e-] HIlEI trI+^J B+ tr-EAI+ ollLlzlE 0ol ¤+. ol Ar+= 5 {-lzf
E tr-ql4 +lil7} qBzl qE ++6l.41 4+9trI.
+ zI+ Eld ,'d+zle-l ¤+ tlElt+ qlulzlE 0olzl,,J +
4¤g 7l4l-tlql^JE sd6l zlf.E'rll sld6l.zl ?+sq, ol ^J
17B3b^lg ol+6IH; olulE 7l
ÎolE
a3qzffi tlE4L+ c L+ glHzlE olEel ^J'H4 Hllolql E=++. *3 "tlHzl
iilql¤ qlqzl= 41&g + 9l+. ol + zlzl t.lnrn EH B uflalol a+g *,9lal4 EI+^l 3c Ezl¤
Î"lel ¤+ ^Js
qri 9lr@= 180"(4r{.rJ cos@=-1oli4 1-3cos2@ --2) 4L+ qlLJzl= 0ol qzl ?+=+.+ *C Ezl-E tr-s4l
^|"lE
4l z146}r" Fr= Fz= 2.7D, 9.0 x 10-30C mE ?lalH ¤- qlqzl al4}g q]+61 +d;6rzllrJ 4+4 " + gqzl= a
q-s=4 eg ar+= eg + fl+. = 4='H+61 A+61-Zl eg + 9l+.
!#z t-3cos2@ @ qc Ext= gaEf8 ott
L'lrl= LIEhL|l= =¤ ^totet

^l
(s)ql EoJ HHgql rlloJ ++6J ^Js4+ Eg¤- ^l-sB + 9l
fo
Exll l|t-]zl+ zherfi 4l qdo}zluJ E-$ Hll6}-9 F"J6L
13
--/
_ (9.0xt0ro)'?x (-z) =ql,
9'-' zll 44421= ?+=trI.
4nx(8.854x10-'' ) x (3.0x10-e)3 J-rC2 m-' m'
=-5.4x 10-'3 |
trJz{l 1 gg $E48.llHzl{l +* ^l
"JA+ 44 r"llrl sld6l+ + +c EzlE ¤+ tls4}+ ql
ol {lul zlb -:: J mol-roll fl$,*+. HzlE trl-s-$ ?"1 f9{4.
(y)= - tTE¤or-
r<cosg)
=!,1,
l7B3b^lg aill +ql^J Be6l4l ae¤ Hl]olg ol+r 9l
+c Eztgl Ezl-Eol zlf+'41 sld6l+ +illql
4+g+ ¤zlrJi E_! ullalol t+otril gqts f s.o o_+ (coso)E
= zI+ qC E4-59 E"J ++ z$a[,<1-o1E 4"-1e+ H] +41 "J^l-= ga]6p. :lol"t +4.
^J= +
ril +E d6l¤ 44zl Hliflq ol + f E d6l¤
^lolel ^l-
.J4l2 +C+ E[6]"1 +E
+E}9
rd+{¤
"lel "Jq4 Hltsol t4i9t:+ + Î"lE ^JgAI+ .5trz-z| 271 +H +4IEq $ol a + sin odod@(:aH 178.2)ql
r|:qzffi-ol
ol $fall.<J 0ol E+. qlE^J + 15)ollr.J4 rJol u|] ql_s_ E+Eg trl-q=4 ?JE+.
olql 6J rd-+z|7l Eldg ++H tl-E++ i{H!¤ qq
^l+
xlz| 494 *ol ¤4. vy--
r. e-l'(ov&r sinO dOd@
v@)= - 211¤t)r'
^W- ,oro
sin? dldQ
J; J-e-\,(aytr
684 ErPJdE¤
z ztti tti
<n=-3 t= r1n** lGesom SEAIE 078'4)
tdu
ad q^g',$
178.4^19 +gq} ?ol ,qqf6J + ?l+
=Ag
I Y
¤t ta+¤"
I
ol +9 +Eolo+
x'' ^lol "Jqd
ol+.
¤+ tr-Ezf+ 9lHzlzt r9 0zll#9 q+ql Hlql6}
azJ fi8.2 EE LJol 94= LIEILH= EE. u + o14,3 lran der Waals tlg4}+ol+.
{r
gEql EHlell 6J+= ag s-ErI tole a+ g -
'lo
Rr
¤5.ol {+z}E ta ulq= -Er+E .JE6].rll E+ il
'lol
{zlr-l e-v(o)tkrt Boltzmann "JzJ.4. cos09 zl-6 ¤+zl= + ag 9"loJ4. 0lil
=
94 e+. 9-6xllEol +4+= ae g-lzll#9 tr-s4}
+ ElHl¤"] q^l 4?-1E g-:xll*"ll Blql4=
. Boltzmann .JE qlq \E zlrt9zl oll$"l4.
(cos0) = J, I, .-"'')'e' cosgsin o d,ed|
JcosOdp = r,, )/er
sin g d gd@
l.'" J".- zl=JEt oll 178.3
E4l 3 4+ 4lÎ E EzHpr = 1.85 D)Apq r.o nm
D)71 olul = 7l(U, _ 2.7
. t^-,-,t^..1 tl rl = z-lHr!-r,l-farnl
i'o',_r-;ii/;.,ii ;t1'riiî
_LXUrl Zl uaL
u-lt1lt2t LtLtttto, =_ -rr-? il-Te
- 6=ii -r._r-r aElqiî slds'J + ?i4. zs"c(2esK)qiî ojE9 ¤a
H ?lzl- znzl49H, , = cos0E +=+). tlszl+ 9lHzli olulle+ *"1 ¤4.
-d cos 0
!t u^
2fif," e-"""il?m =zn! ,e-"'dx =-4{r"-e-")

t,, _ 2 x (1.85x3.336x10-30 Cm)' x(2.7x3.336x10-30 Cm)'
--
r4I Ezl* 4+61-E'l¤-4 ?ol 94. (4neo)2k
\-----a- \_J
u""g
znl,i" cos0 si n0 d.0 = 2nJ'
,xe-"'
d,x = -4.0x10-23 |
ol tr-s4l+ qlqzl={Avogadro r}+E #6}q) -z4l mot-l

='4 k -e-,,) -T r",+ e-" )
ql 4'J6l+ql, ol <le +qL a6Jol #qzlrl+ qlE
^Ja
trI4^1, Hl6H^J Ell*61 4L+
"llHxl"ll
1 A -d
(cosg)--1_+]-:-=L@)
u e-e
d6ls=r+ tls4}+ql ++ qq E lTB.lql
ol+*H _,qE6l + t+. ol
nl-z_zl-==el
^l#
ole"6l.fl q +g +=
{zlrJ L@)i Eq l7Aql^J Langevin -d#4.tr}+^1,
^lE¤
17A
=rKEq
9lrl dzl tr]¤! +zl¤¤ ¤E6}g+)el tls4r"+ glHzl"ll *
(v)= - l'!r4a1 + 49 Eg + ?14. ¤zl^J 6J zlzl $,flaflot R +ae q-+
zTE¤,or'
+zl-E 7tr71tola++ tr-s t+ rJ uulEzll trqd

"ilHxlzl
Eq rTAqlrJe+ z)ol a < lolE r(r) = a3ol4. oI4rJ,
+= a"l+.czl lJF4 n*azl+ czl t4
m*a_71^lolel
(Y) =
altllz tti tti tlE4l+ qHr¤ gluJzlE trl+4 rJol A4ql trlu} H++.
6ntrr3 Lzn'elkTro
Erll l$zlzl +ql= q+BQ]=(ge6J 44ql^l)

1.4I A v*;^ 8^l ,8E|l r[6
,sEarg =^l=
ollLl^l
(178.s)
^[ole_l
E4 dxll4"J 4ltql^JE qlzl iol E 3l+4ss
=q7}q ol^lH 4 Elql ul4 cJ mls4l
alafl+ "lf+ *ql^Je+ +tr+.
tr]++ *SKeesom t!6=l8q +eI 49 grll g+.
+ L++ +zlql zlq6l+ zflzll {a}9 izl *o}df E dat
585
=xlE ^lolelS-e.rt8
r. 178.1 gErt8. tr{EJ!¤ 0llLlrl z[,r.[o1e1 tr-s ]+ El¤l¤ "llHzlzt l/t'ql Hlql6]71 qEql
qHI¤ xlAzl +s= 4014.
*Ezl+ "IIHZI
r: o
9luJzll
--1
+4
==
-dTr E ,l?-l el+ (kImol-')
olsolg Llr 250 olgE zltrJEt oll 178.4

^l-"lql^J"J
+^ aE+ 20 x-H...Y
q7l^l
tlE I l0-rc m)"J +zHqlaql HCI)z| ¤+E +q
= l.0D(3.3 x
4"so,=9 X, Y
=N,O,EEf d - ro x lO-rm3oJ +zHqlaq fl41" g l7A.r)g+el o.:nm
olgffiz| llr2
r$:z_z|_ffix[
l5
t4 *C ¤q4 flg *IE 97 1ta4* 9lHxlE trl*4 e+.
ll13 2 Czl
Ezl¤ r}"l
ll16 0.3 Eld +c Ezl-= rr
v _ (3.3x10-roCm)'x(loxlo-3omr)
--
^tol
London(E^J) ll16 2 E= ="+E EZT
e+ olgE =-1.4x 10-2'J
^lol
ol Ztg Avogadro t6tE -0.83kI mol-'oll 6l]BoJ+.
^J+=
$el Hflgol 4?-lql q+ q EuItr.Al +^J ,S+_e_E -BolTll q
zl ullEol4. Ezlzl. qq tolal El+ +zl¤ol +eg
t t
6l- +E= 714 +E 9leq, olEl6J a+e-l tr-s4}+ qlq zl= (d) a,J g=rl-8,J 8=rl.8E=tE
lTB.srl o + 4l&q} z,l {tEE Et4 a+= ag ++61-0.l+ Hl+C E^l-=-(Ar$ Ag E6J ee flzFB sprall,<1;$ $7
,J+zI EHIE= zlzl:t_ ?lzl *zl"J tlE "Jqg +4u+. +
(c)8?xl-*"J 8=rl SEEiE A+ ol-E=ol *g s_Eql^J ¤+g+=71 E Hldol ^Jgql
*C Ezlb "Jd6I= ¤* z]{- +zlql+ r6-q{S +g^lA ^J
Eill+= ÎdEe olBlq} Hl+c +4-= Îolql t'-E4L+
ol ¤xll+4= +4ol+.
+ 9l+(rB rzn.:;. ol +gE ,6qz]g z1g. tsz1e-l ¤+ adl
+zle+ ^Js4¤¤ 6Iq F Ezlzl gq'Ja+. ol ¤t Hl+^d E{¤ ^l-"lel ^Js4L¤+ dz|9 +rJ4 llil sF
^Je
^JzlE ft dol
ql+ql ,'!:r-+zlql 94^l
^Jq++ "llHzl= Ezlt t)Azl r"J
"ll
tr1.*4 *"1 ¤4. ^Ja+. "146J ^J
ola|lalzl +16l^l zl+ + tszt qI9 dzl-Eol
E4i+E
=gg
- - ttlai E^lsl E= 7l-5 E^l tlE6l."l +a rd-:a__lzlr/I. += dzl. ts]lg¤. +4u+r 6IzL.
v --+ 4'fieo =¤
^l.olE
trlEl¤ oilLl^l (178.6)
ol ,!8+zl.= += tszl-= ¤+^lvJ + 9l= d7lllg "JEq,
ol Ez}"il4 +A 6t-izl tt,E +B^lA+.rBlH ol F {f
¤zlrJaj! Ezl 2E ¤+E *vloll, p,9 ExI lE g+ ;^J zli ^JE 3"lBzl4 :z4al-¤ ol + tszl-E ,lHl¤ 9lHzlz}
+zl-E{lE+. ol +e] c+ t7B.4al"l4 "}4 +s= 4E
^l *olal4. aal H +zlE d+zi$ a71e+ HJ6Jol 4l+4es
+E Ce+ +s+. ole+ gol +"J6J C. Tlz'la_ Ctr6* +El-U
H6l-71= 6Izl"J Ezll H EzlE dz} Egzi olag fltrl=+
1,9 olE +Î^dg rla6|Tl f-l6llî+.
^le_l
8=rl-*g 8=rl 8E4tE 9lHzlE gEq roqlql, ol
. + 4qzli ^J+q= rJ6J1g +l6JtrHre rze.+). ol t}+c
ql$ql + +t 4+zI
Îolel "JB
s4i ¤+4 o + 0ol El
a* geEol ¤+ 4eq g.&g a4 ?*zl ullE"l4. S"J zl *r f;.g g=^l-A,J 8=rl SEatEg +E|'11rll g+. ol
olqq ol tr1fl¤ qlqzlr 4-qzl.-{-lz} ^Jc++ql^Je+ g
e1.j $E t¤¤ E,tl SEqE, E=
ol 1/160ll E+++. ol 44 9=s= .<llzl(tri+^l +B "l ¤^J¤. zl¤-e-s ¤E
^J9
,r6!+Îel zzl)zl r/r3gl E=6l-r. E. g+ ffizla{ +g H
F (a) (b)
(a) (b)
feJ 178.4 (a) Et ga48oll,\l= -d E^l.sl f,J g|=^l7l.rl,E E^lollEt
.f.g 178.3 (a) *d E^t(B^4 El¤)= Hl=¤ E^toiltrt g=rl.= +g^lz 8=^|.= +g/.l7li4 a,Jt] = 8=^pl8EAIEE 6p{ 0jlL1^171.'_*o|-Tltrl-.
+ fleq(A^q trEI), (b) +rl'= fl^1lLl gsl ?tel Ht|:dE tt|.=tr|.. qal^1 8E (b) + +rJ ts=^l= +il#z-pll HH:Brol EJa[^FlU 8*El7l ttl|Eoll 'JE
,8E4tE0l ooe E|xl E=rl-. ^1e
^t8e
Et= 6lE ool El^l ?i=tl'.
686 ErPJ tE¤
t rritzlondon9 olE¤ ntrJ mnaon dE$Eoleps gg z}4g +41. g"J6l-zl :.$ ;;. s.9-+ N, o, u) rzy zy
= E+4?l
trI. eL flr5"1u1.
+A rd-ja-z} EHIE pl: q d6IzI 49
dz}"ll 4aJ Fxll +^ aqlg Hel ++ "Jd6Ie+ BE Y E *d6I ^t"lE d
Eg g= +t}
aE.ql E+6Fr-E ^JE
L+E
^ll7lb arl E E +E ?lg e. A, H, 4 sz} 4zl 4--E flxI +llE
=ol+r
z|el ¤+Eql q=++. ol trszl¤¤ E+ Ezll EzI9 ¤* EI+E+EI 3zflel Hl+xlo+ tszI +llEElfzl ¤^"iq=
=E{}
EqlE 9¤altrll, "149 S+E= 4= Ezlql el6ll^J ,'d+ ¤!E po3olrJr. ts +E ?l4t_zfl r7B.s). de4 644 ol
zlz[ $u[+ flal +gg f gl}zl¤ ++4= 4olzl ul]E"l E4 bel= ol + +dg E+ +E6l-q Sd6l 6[Aqzl ?*
+. ¤+ tlE4L¤¤ ¤xllE 4l&6lBJH tlB6l +d:6lzlEJ 4 :z 9l+.
B* r+Ag *'l,rl fll4lalE q+4 *3 ronoon 4g B EzI +llg.++ -g.gql^J A-HA6-Je Ael TllEBJf vro
=Î
g+el+ e+ +i9 ts ?llEg}f vnE ol+qzl-z 89 TllE6Jf vn
aB d+q$.+a E+. olfl ExI 2471 ^)
dzl-B'-e--e.
v=-2 c=1raia',ll'-*r =
London
^l
(178.7) d=6IH ol$ ^ll +{EEL+EPrI :21e1 +zl +llE6J+
_tr.
v = ctve.t czvu+ crryuTl ¤c¤rE B= aol4. "16 qI E

¤zlrl r,4 12= + Ezl¤9 ol¤.E] 9lulzl4. ol rla4¤- 9l z[ 1]ra;45 eq], E 6l-+= 4E Hleq], rqr +"lzl 6]
qzlE 9rl EzLrJ 449 oxll#ql qHlql6}q, vanderwaals += Hla6-J(Eq eE)o1q-. olE îl +llE6}+ql +zI9 dzltE
^Js4l+ql
ql+ }lall H zl4zl ¤+. "JHi4e+ +tl {l:r+ 3 e_H 4a3e_epElolr E Eg BE rB {zffie-E+q)
¤+ +i a.Jg ^llel6l.E E= Ezla tls4}¤¤ zlu}ld4. 7l EqTlzll lErll, Ee Aql fllra65- 4"lzl Eg Hle6J
+llE++E A+++. ElAq+ +llE6J+zI HlqglTll qoe A
q 44etr qiLiziTi-'xoie + ?i= zi"i4tz-19 ujpajt ,'.llr
Z]tr.Et 178.5
E'-+E eq6J +lilql el=al+).
F CHnEzlzl0SnmtrE trq4 9ig trI= d =2.6 x l0-rm3, dzlle ol +r a,*g * zot<l mol-r eEE 4=+
I =TO}kJ mol-'g ols-" olE q-q=4 ,J+ 44rI +g+.
^ll7lE
EE a+ql= el EzI * zz\l9 +i e6J"l ,,821
(._qill tr-=l]
m')' (7.00x10'lmol-')' 4. :- s= +E qrBrlTl & 2c.lql E6lB 44kI mol-'ol+).

,r_ )x(2.6x10-'n ., ol a6J3 +llEs}+Eol aad "eal ¤cq= "J+q d+
'- (o3oxto-'mf ^@
= - 4.9klmol-r ^d tlE++e_-E^J, AHzl Be+ d+qH BCEI trqzlH o
ol ¤+. +i A6Jol fzflalE olaol *ql^J ¤E* EE van
qlB6l 4dzl"J ol alg qla6ll -B + il= a"l ,ll+E + der waals
^Jg+¤# oJE-ql+ qlE^J E4 g+ql^J= E
E flBq 8.2k1 mot-'ol4. rBl+ +B Slgi4= +zllz} C zl¤ ?]= van der waats 4+ A4B+ gd 6r+. ¤
ÎolE 4
¤o]4, EEI tv7le) oJol 714q4 g:e_E_E ol ul-il.= c e.Jg ol+zl ?*a gl= flzl-E Îolel ,l4E 7l=6l]
q.J ag *94. ^ltr-E
.rl van der Waals HJrlEg AE6F=ql E +zl-ql^l- ol <I
AH
oo
B
178.2 *+ rJ.a 1
zlfritlzl ¤B6J tl-tr4l¤-==g EE E{¤ol I ,]]!lel

q1 ffia[r]l +48 + ?l= _H-¤4ql lEolflr]. :24+ 5E
6J3Cg *= E4¤ Îolql"J +++= trszl*ol 9l+.+

=¤
K
5
6-
o
a al-E ol
fli=-Erol+a
^Js1}¤+ k¤ dzl ¤.cg 4= +
e4 B7l-BE lB dxl+}g E6l]^l A-H...B9+ a.3
=e
¤eq= eq+oltrI. +A eq+g ffizl os N, o, "i Fql"J,tI rg
@
178.s E^1.+lEAr+E 7l^la 6l|5zr A-H.'.B +A 'J6J -d¤. A, H,
g Bol 3rl+lE-Er+E+El illE-Br+7|-d¤E + gltrh(ol=el 8r|14
A¤+a ^J46Iq $[zlt} Bz| $o1-o- 6"lzl"J 6l-H(cl-olg ^11 =xf LJe
TlqE=^11 +9 aT le upplgtl). ollLl^lel illE-Bf+=Uol tr+qq
4 ee) +^ AEtg "JE + ?i+.+^ ABJqI +.lB + 9l qa|.î B
= !trEqa
H16|,|^'1 qlLlxlTl -*tf.
==J4?]AHef =All
Erl= A!¤atE 687
^tolel
ol +sq, uI4rJ ol$,rl-ololl ,Jq* "Jq t'-Ez].+ol ¤xllel 178.3 di{l SEEIE
+= ag 9"loJ4. ol *sz}-$ol f+ e6J ql$ol+r ^J4
t!+. qlE^J O-H...Oql^lE O-O 44- van derWaals Hlzl olxll f + a6Jg ¤^dE+ + gl= Ezl# 4ls_l6}r ^J4LqlH
E:e-e 4l{!6lts 280pmzl99"t 6lzl"J dzlleE 270pm !| zl. slAd+ Ezl¤ "Jq ^JE4L+ qlHzlE rJ
Îolel dill
q "J ¤+. +"J olq+ H...o 4al= 260pmzl qqo} 6[zl +z}-;d+z|, ffi4--+g,dq4.,:za.lr ++i tr-s+¤¤¤ q
q! tzopm ql"ll qxl ?*=+. + aq eq. + +471 q+ Hl+Cg oilE ¤+ tla4l+"J
e.Jg'Ha4"J +E glr Hlqla4"J +E gl4 trl]
+i ol +s"+4.+ill-tlql^J= ElHl¤ glHzl"tl 4t rll zl{E"l
a +^ a6Jqlî. sflxlz} +E + flzt9 +tql 9il6J+. EF EzlA 4"-lE 6all#ql HltslEil6iEtr_ trI-94 ?"1 448
olBl+ H}|il= 96}zl= ?*zl"J F-H...Fql^l +E+=ql q + ei+
7l^1. ol!; a-J z)olzl t20pmolQ. rfl+ E^J4fl ag
A-H A6Jol H...B AoJ-H-+ Alg Elqa tsIil+. A-H...8. v=-*r (17B.8)
d d6l¤9 u]lg_e f;-6}r(As+ sz| ++ -gd6l¤-4r. H

7l i E "Jd6l-= *=) Zl*61 cdzlq ^Je_E tr|r.i_H_E + ¤zlrj ++ql el¤fl+ tl++.
cu$ EzlE
gdo}z} ,Itl Et-l trq4 glll q= d¤ Aqlol *e qlq Eztz} .Jq tr-s4}¤¤ gal rzn.s^l_9.-tr. ulQLflzli alzl
zlel HtlEol ¤4. rqq ¤E4oJ +a g+ A4ql E6iE ol 4e E+%+cgl aJ4lzl- 9t+= ag g+ql +qoi 6Jtrl-
"J
olE=$ dB"J +E 9lr Hld¤"J +E ?l+.
a4l= zllnlzl xr-z_zl. t]-g4}+"Jg l4glEril, "14,3
=
ol ,}s4*"1 zl* gz]EC Eol4, Ezlzl B+ 44zl Z
z]trJEt q 178.6 qlql zlH]]4e+ 4t-s-"a19. 4"lzl ullEolfl+. rBl+ sE6I
,ll 6IEIE 4+ +z}e+ q rzle-l trl+ +Î tr-s4¤¤E rEJ
Ftr-4.J +^ Aqle EoILI ggql^l
6110} 6lq, Ezlz} 4zl4 {qz} EHIEE *zl ?*9 trll=
el ?"1 o_Hzle] oflÎ
^Lolql ¤c R
q q r++. EallE "l 49 +^l7l Hlr4 zlf¤;al slae. =
q= aol+. a 4zl4 jtEJS 0l+61
¤ ol tr-E++ trlHl¤ qlLJxlE ooH
o
r H
+ 9l+r z|{ap +Ed 4,"14. ritlq Ee ,l]A +ql^J
4LE((6)q^JE @) 9=s.= al4}6iq 6 +zl7| rc$ ullajgE +=q ?l o =.e Boltzmann Bt
=
r Ar+E:zB rzs.ooll rr.1a1g+. a H"l CB6I^] ?+eq, q{^J {t-=z} ffix} trsz}$o| rtrj
t} ,<1lzli oHogzl-=ol {d t ll Folb @ = g"ll^J 44 (17B3b^l aH)ql Hlql6}rll ¤+.
zI E+. ag "J + ileq, ol trllE E EHI¤ "llHzl} *#zl4E e. 6|+E zllEg 178.8^lol eL tlE .$z| ,r.1-o1
el tr.s4}+Elg
-lekl mol-'ol s+. ol tlg4}+ glHzl=- -12'eI +12' Î ^J4I6H^] Eg aol+= ^Ldol+. ^11 EzI
olql^J"J gol qq("Jqc tlg++), :ael6}q fl4¤ol (E= trJ E+g Ezl-) rlol9 tr-E4I+ qlqzlTl olBl+ ,,dlt}
49 dB ul¤ol ¤+= ag +=-6Iq+ tls4+ .JalE"J
iq4ot B ol-,?= s+. ¤xll
"lluJzl9
tr g-J ed flzl¤ .ilHzlE +¤-r+ ae
^fl Îolel + +&
Axilrod-Teller al o F +q4lq
300
C6 C6,
v-- 9" C'
Axilrod-Teller^.1 (178.9a)
!
o
f
6
e.s 4-;:^* o*..ar'
E
-)
.Y
St ¤ zlrl
j
K
5
o C' - a(3cos0o cosOu cos0. +1) (17B.eb)
qru 0
JrI4 o 4 Wq4 e+. r?]r 4E aEg

u.l
E' 44"lq aE
^ll
-10
-90 0 90 180
flzlE ¤ t}4¤(7)el 4+45olc|. ulzlql c6J(l^dl4t ^Ja4
7l
-, ol" .$9 ul-z}4]¤g +44=)e flzl¤ol d¤ ul]¤g 611 9l
fal 178.6 +A eae] SEA}E 0llLl^l7l(8E7l4 s.Joll "J4-d O-H g trll= gel Ztg(tr|+^J "JC+ uflgolct), r4r EH AI4l
el ozl 4Eoll qal E6l= Eg.
^tolel B o + q6J6I-r. ?lg trll= *E at(= E?Ia6J Hl]g)g +EI
688 Erl'Zl+E ¤
Utrt. .441 ole+E ?*.llE ol B 6

ffg trlEltr oilL1^|,
ar-ill tl.g. }+ 6}0l + t}g4+ lo, 1l 12
4
9lHzl9 eI ro oro A,szl B+=
rsc OJ
sl
Î¤ol Elee+.
A
fco
Sz
j
Eill
Ezl# 7l4Al "J9EolH q 7
K 2 1/6
4 dz}9 +gqol Ezlt "JH -50

6
{ru
9 bzlalal ¤+ ol ^Ja. Hlge EzlzJ 44zl + El . o EJI¤ gllLl^1,
=qEE ts 1tf
t;lAl 4x14, ol el= +41= Eq eEql^l ¤Hql A+ rJ
4
e 4+ +*qL +zl-+a 4l&g E6ll^J AltB + 9lq:ag 0 0.5 7ltl, rlr, 1 1.5
17B.7).
fg 17B.8 Lennard-Jones rlEJl¤ ollLlll
rfl+'11+EE a+q= ol qlg qlqzl= z].,tllal +61-=
qldql 7l+61 H z]]9 a¤ +{trlEl$ ol$all.{ r "JH}zl
(' rr2
5Ag +49 + 9l= ^lg "JEq^l ++. ol*l6J (t)'l
=ÎBE v=4ei
Y -ac ftl-ttll
\' )
Lennard-Jones
l:T?ld-l?l:?
utl¤ ollLl^l 078.12)
at4z} Zti{F. trJE!¤ 0llL1rl4i1 6}= a"Jql, ol "}Bql^J= 1(.',i J
"J"JolE ^l-olE 44zl d_E ¤qE *ll tr]fl¤ qlLlzlzl i4 ¤zlrl e4 rn$ u}4"lEl="Jql, e.$ ulHI¤ +Eel 4olgl oll
617ll
^Jô
6Jqr zteoJ+. + R6tr, rs+^ v - 0"J ultE +zlZI 4alcHs vB.2).
Lennard-fones tr.|fl¤g "*g !l1!ql^l ol+qol SzIEI t/r''
-, r (d oj ufl
V_ 3ll? trlE!¤ ollLlrl (178.10) g HIts trlQl¤g 4q}6}r1l +EI{zl *6Iq, s6lEl e-,tnal7J
0, /)d "J ql
e gq 4+q+7i Br tri ¤ *.=clE 49 Erli qfl+. fl
Bg ^d¤Eol "lz.lfl o}]+ ZI$EI i{fl¤ qlqzl ^l_oE g x[ffiau-z] H AElql^J zl+oJ+4_oE e^l'= ag +
¤Bg+. E 6f+E 'J4 aolE trP-r+ zJg trlie r1 El-{= rllE zlfelfz} 46J6Iq, q+^J Hlgel fl"Jol !ts
EJ!¤ oilL1rl+.
=ÎHg aag +$ql= qlqlE zllt;]fzl 4.Js 4o14. zl+6J+
Hlg6J4 174 q1{a}e_tr- ¤ qfl¤ qlLJzlE exe6 tr1E!¤ 0ll
rr C, C^
rr/ie rlEJ!¤ ollLl^l (178.11) Llrlol4r +=4. "l*lal qHl¤ qlqzl.g Eq lce+ 12D
rr
fim
ql^J ¤HqI uls+ e-ol TlillE Hl4"J
4l+E al4}6l-= trll ol
s"B f fleq,.E6J ola¤. ¤l6l]^j dxll zlillE
¤zlrl n> mol4. e4l 6Jg Hlgg 4441" E4l 6Jg "Jq "lEl ceg
g ++U4. uie ul$l¤ql^J n = r2s4. m - 6* A6J c}s= r+ g 4l4I6J + 9t+ ol lEg ¤+ +ill^JE +aE +EIL||= Ell
3 49 Lennard-Jones iilEJ!¤ ollLlxl+r. q}+(re 178.8). {ls ol*$tr}.
glx[ zz]el E]ar+ -EE oJg .Eqq6l+ flrlzJ-:d
^tolE
flE|](AFM: atomic force microscopy)91 T}|gg Ezl¤ Îolql
zle"6lt Eg zld +ae. + glril qfl+(E4 rge). a; rb
ElHl¤ qlqzlE 99 zl97lolq, q+^l zflzfl $2ffi;
^l-olE
l- ug trlEJl¤ oilLl^l
.=
--: 8 178.2 Lennard-Jones (12,6) tr'lEJ!¤ OllLJxl 4etElElx
K
5
6
?lal qEl¤ oilL1^l (etk)tK rlpm
{ru ill
LrlJ
Ar I I1.84 362.3
H-
0 BF, 104.29 357.1
CuHu 377.46 617.4
CI, 296.27 448.5
7ltl, r
N, 91.85 39r.9
178.7 E^lrJ trlEJl¤ ollLl^l +csl "JHJ4 szl(+ =Ja utr nlEJ!¤ o2 tt3.27 365.4
=zJ =el
ollLl^l= 0l= /.tolol 71al Eetoll rH6]|,'.1 LtE|.1.! raflE). E7.1alo{l,\]= Xe 2t3.96 426
afEAr'Eol ?lq40l^lu ErlEol tr+-g EETI EIE uJg 8E4tE0l
=116l . zLE ¤ql
zl=7[drf. c-l "*9 *E-ol ++qq ?lE+
Erl= tlE4|E 68e
^lolel
'H r= Lennard-fones tr]fl¤ qlqzlel A+ r+g-4 ?ol 94. u|4r1,
,=-{=+{,(+)*-(?)'} (17B.13)
,=(+)''' ro=r.244r0
"l 44oll^l +s"61+6'Jg+¤-4aol E4

E@[ Lennard-Jo.es trlE!¤ ollHxl= olE:d E
rlzl ?l+el 4ltt ,=+{,(*d"-(&)'}= *^,
Lennard-|ones i4Hl¤ qlLJzl 49 ol+6lq F N, EzI
Î
olel 4lrfl ¤s ?lqg +A6lq+. E. tzg.zql E6tH s-1.268x l0-2rlo'lr ro=3.9t9 x 10-10
mol4. ,r|4rJ,
r.el-g ,t.]¤I "Jqq a7l+ dFtdr= 09 "J+^lzlE rollrl
al4zt s+. Ir++^l 17B.13^lg rgl *dl^l "lE+'l-9,
IN=lJm-r
r ar+.0o + :---L rgl +6ll^J ++.=-e-E ol ,9 &9 2.396x (1.268x10-'' l)
178.13^lql Ba ql+61-= Fel <tg +ql+ - 3.919 x l0-'o m
= -7.752x10-" N
EOI dfldx=,ex't-rolEe Fq ,oll *fl eg4E trl-q-r+
*ol ¤4. + ¤E a-71+ qf spN"1tr+.
xlTl EJT| 178.1 Lennard-|ones trlHl¤g "l+6IE trlHl

# =
T{,(-+1ff)} =,n,,'
{* #} ¤ qqzl +d
uti
^Jql +^d"l 44+= ¤ 9"|z| qAL
Et+^l +s-4*ol ¤ ull dgar=0ol ¤+. oln,r7
= I :6
7 26rl _
rr
8 14
o, 4 7ru -26ruo=g
T}lLa{=
=gEt
-l l. E{l eA EzL= r}ol9 van der waals SErtEg aE 7J _l
l. flzt9 van der waats urlEg Hl-eEL rJ4 flzl¤g 4=
49 0*'ll HlHlelltJtr+. d aP-lql "J46ll^J eg aol+.
- 2. 6so.J +zlt tlE4l+rqg r}gr| ?J? /.-=014, daF r -1. +a A-H...BS+ eg gql^lE $a48olQ, {zl,r.l
C6l, C6t-g=r[, g=rl-8+rt, 8=rf-B"J 8=xl,
=gg
ee+ sE "JHI4 " .e. N, q E= rol4.
+A
=tl -l 5. LennardJones tr{E!¤ ollLlrE
(tonOon), "t H}Bg EE}6J dill Ez}zJ
=-d.
ulHl¤ 9lHxlE LIEI{= 6J Egoltrl.
6e0 ErlztEi¤
=e-d^l=
zA-l
,\-lzl
oe, -1
Î I --r 4Ha
+9 d ;tqz}e+ d-d6}
"]]A V = -l.trQ.l4neur2 d¤ uHts T7B.I
+ rA 4q^l¤ î"19 tr'g++ qlLJzl V = I,t,LtJ(@)l4neur3, ¤6J rd+zl¤ l78.3b

f(O)=1-3cosr@
+ Eld ;d+zl-= ^1"19 tt-Ez++ ollHzl v = -2lt)r[t)l 3(4rc,,))kTf t78.4
*C Ezlg+ ¤=. zJ$. $z[,t[o1g ^]E4]+ qlLJzl V = -Lt2,ail4rceuf t78.6
London 4] v = -lui a|(I,I,l(l, + Ir))tf 178.7
Lennard-fones rlHl¤ "llHzl V= 4e l?,tlr)rrt - (r,,,lr)61 L7B.t2
EEf 17C Ei{l
7l tsaB ffiol anrug{r)fdrol 9EE AEq= Et++. q

zlrJ nrg dillzl +zL+ "JE4(ar= N/I/). +g+ Eeql^J
".JP a5qt uJ=01
o-4i11 Lt|+ollll gGlUtl.
¤84oJ
^zJoll,\l
qef^l E^ll-8rl a le|-"] ZlE"l +I= 0l6|'|6E, ¤E-g +
E s(r) = lol4. olfl %l!eE A96IH %IÎ¤ Ee 6J+=
9lolo[ -drl. =) ol +4 49 Ez]-fg+ ole+ F"Jql +El +q Eqilg +"J
qI Ezl+e+e-l Hle+ ++l E +E il+. + SAE} 44ql^J
g(r)>lolH +"JaJ E¤ql^1tr+ q "*9 Ezl¤"] Eqgl1
s4illel gE=3 +aJ +q +oil^lel EÊq E^le,t +i]l
=71.-l g(')< lol$ E s+.
EEoll^1el E^l dE¤ HJg6l-= aol+. =qil"l"t
sd aeql^J= flxl¤ol zJ
4zlaql +lzl6lEE(4^l 4
> Es-d qHl rl^l elol4 ¤¤¤ol sg ult) ol srfz| ?zl4"J qlEl+ ¤+"]
ErlEol gE+E¤ 6lE g^l(E4 I zs)= gl. ?lolot 6tq, . +F+U4. ol+l+ +zl¤e ACe-l Evlzl ¤+qq, tr+4^l
Helmholtz ef cibbs ollLixl(EE 3D) ralr
olEel elelE +xl ACg 8Za! tr^18 *:q-r "J++. ¤Col ¤+qH tlrl
6[1 9lol0] -L[tl. 0l EEoll 'l= Boltzmann Eg'(CXl rl^.lr] .EE
?-l e^J7I +qzlr" ql gzts+q Er-l Eqd gEqlî= E
12A)e.l zt|LJs.4= oltg aolq.
zh= ga$ ffiol qq^J+ aril ¤4. rBl+ dxl EzI9
Ele qd6l E4el "Jd Ezlz[ Qlz]lB g4E 9zl
=4ql=
q "lEel ql¤. 4"14, E ,r.|l gzlzf Ell4l tsl?lq Eqzlq4
E{¤$ r zl$el + H]]AE trq4 ilg tr11= .!e ¤{'&
E. qlzllE r zlzlaJq. rq6hq 6C tszle$E ,,"J
zlzl"J oJEol d6J 8E7I EIH 4;l ;.J_tr HlB6JtrI ol "Jq Îr-lE
q$ql ffi $ol ¤dqq, Hlg trll$ql aqill(q rill)= "JC 4?-lql "Jd +zLzL +Ei+= +4 ¤9"1 gll" u Qlxll-tr r,oJ
+ +r]$i-7!=+. Ezll tl4ql^l= +zl¤fl e+ qlqzlzl I 4{q Eal H qld EzLrI +48 +4l S9ol qi$ 4o14.
olEl6J E4el tr^171-=46171 qlEql oJÎ¤ Ee 9.45 u
fl¤ qlqzle{ ulfa}{, ol trfl$ql ol;ll E{-==$ 561 *g
gEql^l .li-llE+El sd6l trq4 4zlzl t6|r" d^ll +a C Ezle*el r,9lrl +g ¤+4E, r,ollrl *3 B+4E :z
,I +E4ol ¤+. .-{ill$ BCrll 6l+ ol +dqe E+ "+41 4r:- q*lql^'l= E+ q a+.J ++q# ++4= 4l#
e+ += atErll, ol 4lBg ETllel ololzl-zll
E+.
^J ^l-olE alEg +4+ril
gEqL4 Ce4 844 g6;19 E4l tr-4 E+ql^J 4Ii g4¤q "JÎ¤ E*. gI+E =4
^Jeql =+. 6J Ar+E aA vc.r"tl 444S.4. ztrll+ E4 e$ql E6t
H 4qE a4l H +a ¤q "Jql^J= +c E EXITI

17C.1 Ei{l +oll,\1el Er}z} 8E4tE ^lH4l
+zl4e; += E BzlE=E Efl AI-q 914. roo"cql^JE dr)
rill= E E"&g -HH E^Lt ^JE4L¤{ol a+ql= +E +d AoJ)
EE6l-=
^lgdg e^l A¤qI Sd ACel +a+(E ujzlzl olel+ +zl4 +z7l +
I rae). r4r zlill= EE{-= ^lgdg Sd zlztl Ezl-59 "l oll9 zlaN,rl #=A ule
d4 "-=. +e^J+ EE+(Eq 1A). .lillb ol + ++E +a zlg+. Raman e]6tfl .-4ill ^JEll Eql^J= q++
^trlEflql
ol+. alillel +ae+ gqql4 CAg Ezlt tls4l+e] 9 Ezl¤ol 3 ullzl 47Hq +4 AElg ol+r fl4. :24-:r. 4
^dA
ql 9=6I{, :.
^}El]^lg d4l zl;llE zlzla_ trg.'J 44 ul 9d rE=.Hql 96IH +i e".Jel * govozl +Aql^l r
EllE +zlqq, #=dql^J * z\o/oe +i6Jtri.
*oJ *H-o-e EIE + 9l+
NTHE +zls g .lillqlrJ EzI 14 zgl El]qI "J^l-¤ Es
6J+E q_q_4 E3 al o + +qd+.
(a)
"JrlE Es:d+
.lill +q "J"JolE9 ¤+ tlEH4 +lil= HJ^[E EE -d+ I
g(r,.) = dr,dr, dr*
g(r)E zlzlt_ +48 + 91tr|. oJ alfS il Ezl-e+q Hlzl w; NZJ"-''''
. ..
,J^l U-g EE Er+

E ,"J *ql il. trli +41 dr9 t4(+4 ddl e}glrl tszI
(17C.1a)
6e2 EÎZJAE 48
2
o- o" ?o"? \
t
Or
OC
25 C
100'c
)\e
0"
r b-e I
{e
/ b-e (
<l-
40-o
+l
n|J v/ /\" ./ \sz )rer k
I ,'o/t ,l
16.0
U o" of { o
io
0
0 200 400
EJÎE, r/pm
600 800 1000
)\er b-e Ib'o/ I
aal fic.2 El g"Jol7l E7l9 TlqE E6H Ll7l.E HJEH + TlqE E6H^1
.fg 17C.1 '-4i11 dEt| t flxtoll tt|-Lr eGoll^lel B^lE EE -Er+. rq 71B8ol Eol7Pll El= +714 ?3Al 0lE6H^1 2ilfl
=E 4= E + ^11
Eill. ^1= ^lEa1lol.N-d
?=t1=4,J+e "JdEl= 91tr1.(A.H. Narten, M.D. Danford,
and H.A. Levy, Discuss. Faraday. Soc. 43, 97, (1967)).
+71^lvJ + tzl-59 4zll# r +flql+ +

gl+), olBlt
¤zlrJ d?,E +zI ,ql ql6J +q Q +, F = rlkT, v¤ iv-"J"Jol ol+r "+ill E¤g "JE+(rB rlc.2). tzl9 + AAIE9
E ElHl¤ 9lHzl, rflr zE rl-q=4 ?3'u}lzl tzl 4E'(E E6ll^J oJEJolTI mt44zlE r $e.
Hlql+ azlts¤- :a" afl.rJ
I tzo1"1u1. 3 "J"J"l7r .=-qg4.tzl-+ql Eqfl= +.J"J"19 trlBl¤

glHzlE ol ojulolzl-{tz} +E += E= g"Jole+ fi-c.4}+
g 6Ir E +714 o + Hr+q= 4E .u= tiî +9 Exi¤
Z=fiJ.-'" dt,dt,...dr, B11^l tgell (17c.1b)
=rJ ^lE 4E ^Jg I¤¤ ql+r u__z 4lt}9 6l]ot 6J+.
Monte Carto HJHqI^J= ^Jzt +E g"JolEg +d ++A
ol rzc.laAlg Ell*61 +d-6ll -Holzl"J :/El r|]^J F "JtrJ"lE
6irll Bs/lzl-L olq^l a+4 ol +zla 4?]E ol5.^lA+.
zile_l6J 4lE +qzl E= oJEJol=-ol
"Jg= 421* +ql^lel olq^l tz} 49 N7|| oJEJolel dill i{Ql¤ "llHzl He+Ay-
ol + 9"JolEil tl]+ Boltzmann Eg4ql zl+zl *= aol
g 4lt}6}r, ol ,$tr-$ +se-l ElHl¤ "llHzlz} a+tr+ *e
4.Ezl-$ tszl$ol S.g ul(+ vru=0)E Z=vNlI{.
^plql H ol EE. E l-=.J+ i4Hf¤ glHzlTI zlg E+ 4e "I
ol qir" q+^l HJÎ¤ EE EI+z| cl-e--a.1- ?ol 84.
AVrol "J9 7,|ol g trll= *g slHl¤ qqzl= *= trI
==
vN-2 +sE4 ¤¤g ol+H^l + 9i= 4qlzlE eE6tl
=
g-ot"t ++ r?]6}q Boltzmann =46Jzl+ oJzI 6wtkrTl04 I
g(r,,)=w_fr;r, Jdr.,dr,...dr, ^t
lv>> "lE {tg *izlE Hlnp}+.
"l zl+ oJz}z}
"l {lE+
=
trll
ol +sE B"l¤"J f ilr" 4¤. trl= z]fs-q 4^l

1
N(N-1) N(N-l) = ^14

=_=_
N,V, N,
-1 6}0l +sE +{+4.
^l]
olal+ dq $Cg 0l+6].8, 9lHzlz} E+ *g Eeeq
ts+r*"I H= +ill= +"J6]loh B 4"14, ol g(',r)9 zi4 oldf q+qa +g qlqzlel $++9
"lFS E7l+.6}zl
"JzlB 4"14. ?+zl"J glHzlz} tolai= qel+lzlrll ¤+. "l A4E e
=
+El ^lEBiloldql^J= ¤FBfl6J Hllgg 846[zl"J t-e ql
(o) g(r)el lltt Hzl u]Jgg 4el =o;il17lzl ?+=u+.?+?+E -"1+ElE H|]z.lotl
r7c.r4 +e-l 4Ee 4ltlol "1+ qal+q r?]6}q qq + ql6H^l A4zl roJ EzI tlE +E ol pffi al89i:r
^llg
il 4lt %FHg ol¤-alol ,JÎB EE ++. Z1416Il. gl HHgql ea ¤Eg +lEI+. ,9 {t9 H+^l7lE^J ol r+c
=
4. olelql al4lg 6i7l +16l]^l= Ezla qfl¤ .llHzlE g HI+6iE drlg +g + 9l+
Lennard-|ones tr-t} tlE4}+(-tr q 17B)r+ z!$ \9 F ¤^16ll ,JHq^l= +zlz| qHl¤4 olEol
Erl "lil= c
oF +tr}. el ¤6J =4trt
q-ql^J gf{+ E= "J,jol.el +llzlg 41{a}e-tr
olq+ +il 4lt}"il^J= .JHI4_o e * ro,zlq oJBolTt E 4 zzl H}]il ^JEll. +46J4. olelql 4l4lg "+illql ']]+ "J
q fl= tzl-$ +l6}a(e+qE ++ol 4A++ $,Jol f E flq ol{ g e$q sql^le} ee H}Bql
^l-{4 aeq,
^ts
17C e4ill 693
ol 49 HlxlEol rolr a^lzl droJ *7J@$ 49 EzI f

anMg\r)fdrqlq v,?)* +qL q--*ql r"ll +6ll^1 4+6lH 6J
2
l-o
EL
tr--]
d+
E
Ezls+ 4E g= +zl¤ dill
^Jc L+ qqzlz[ Qe
\ Î"lel
5 olzlql4 Ng +6lH -trE E4-=E Aill tlszl+ ollHzl,
-tr,
j
K
5 + 4+ glHzlz} ¤+= 49 u-q=4. "JzI ++ 4 tr-E4+
6
{il
* z+o-t 4l&61-zl ?*zl fla qlz14. uftzlzle ,^J-r^dL
^Jg
ill }+s_l 7lq= EgL6J #g +illel +4 %r-a^le ffi$ pol
E'
gtr|.
0
0 4
r!#
2 3
uJxl$, r/d
fg 17C.3 Hl"J+d 'J^ll+= 7$.la- -Lf g^rd EE --J+

l# =, - # !- u,g(r)r' d,r, u,(r) -
(17C.3a)
^lEallolcE
¤zlrJ uz?)z Hlelgiol+r *+(Hlrl"J rr-el^lg q7l^J +
4E olEol+). ol !g r+q=r+ gol 4H E4qL4 99E "l
61]g + ql9 1"14.
gF qlqzl=
"l4dr)g 4l&g + 9t+.Ezl¤9 ¤+ Btl nRT 2n
al4}6}l. +F Etsll ?l?-l(Eq zeel E]$z|el r}^l 7)= ol+ -'+ g(r)E ol8at|.!
P - + w' t* u,(r)s(r)r' dr gral
L|EILJ
(17C.3b)
6tq, +, (i*ri) =',kT= 4 alEql ql6ll^J 4l&6IH 4lE g

EE +A6J + 9l+(qzlq qY 4 als CE). ol lll¤¤ q-q=4 pol goJ$ + 9t+.
^lE
"Jq ^JE4L¤¤ 6l-zl ?+= ,J4l+tr. ¤ +ill(^l++.
oJEJol
5q +iil). 7l^la_ olBl6J +il 4ltlg aH_H_E EzI t4ol +HE aal] 6Jg $4-o-+rl zl-f+Zl -g
=+-+4
+g trlt= 1]rE" 6l+ "}î¤ EE E'-+7t +4k}+(rg uc.3). Eo 6l-b
Ez|9 +4ql elEl "Jq 7lq. +Elu+. {r
-
,to
rp-l6lq .lill +aql g."rg += + -s"Jg ,Jxll+=.J?-.14 Erql 6.Je- oL4ql^J ¤BaI4l.zlEI o tr- Lll4 Rr-
=84 ,lOl
oE +"1¤4E zlate}4 ExllzJH !_oJ+. ¤zlls ¤I +q4I "JB n, = (duldv) ,-+-^J(Eq 2D), $zlt oJq el nl
nlfl
gEql^J ,JAI+E ol+qd .+illel oJ^l¤ Es 6J+= +E 6J Sq zlq. +4U+.

q,qq} e_89 EillEtri rJ ¤2]* Tl+ ++g +4u+. q
Hl¤el oJ{ 5-g-ol ol zl$ +aE \l.jt;ll}zl= 6l-zlq}, ¤^ll Lil4 "Jgql q6J +4lE olollalelH + +4-= B"lzlzll
'-4ill= +4rll= qel*9 flHql= ElHl¤ 9lHzl9 'Jq4 6l+ Ell gsq| a;ol -dvrtdr(uz{l +6J +el)olq, q4^J
^l
Hlgel F cBol Hl+6IzI +sd-+= L"14. -(dv,tdr)g + Ezl-E r"J# qlq+= cll peal "Jol S4E
6J+. Eal 6Je q4^J ol "Jg A-tL 4 4 g
Îdg "J^l6]]ot
1"; e{i{19 EE-+4 ¤tr qql erl ¤+, . ral r+ dr rlol9 44ql^J + BzlTI ga
E +E"J angQ)td& 7l*^la ¤#ol+. t*61 E:"IE "l
"Jtdag+6tE olag ol$all.! 'lillel gqql4 Ce5g.
lltlg f ilzl"J "JszI +olzlfl 4l&ol E|]+61 +d:6HT1+. 4+ql+ +4+ gEq 4l+g *i6IE AlrI S+¤ ,llel 4+
"llHzl HsI fautaWrTl
qq ql+4 "Jq4 A4l gtrI.
Esz| ¤xll zlille+ tr ,(iTl-s.g etr+ *g "+zjlql ql6l]^J '.+4^J
ol :/zllel fl.r.l.o1=E
^J,rllt
q+9= _HE ol 6H4g 0l+6l.
al4}ol ++6itrI. "lelt a+q1= 4 Ezl-alE tr-Elt¤¤
=
t"J r^dltl ulql¤ Er+
%(dE +qTl+r 7}A6IE q+ qq { ¤zll zlillel Hlrl"J ^}EI^lg ++g + 9ta s6J van der
q+4 waals]il4"lel59 6ll!g + ?l+.
zlql ql6J zl4zl ?"1 iqrl+= 4]47l +1tr1-.
l7fib^lel *Eg 8+9, HI"J+C "lill zlf "J"ll zl-
2nN2 61zl= "Jq$= d:d ru+ =4o14. AeJ "JE7l p,+ol7l
U,n,"r".,,on (T )
V llr,t lrrr)r'd,r h, a4a- +H4ol AoJ .-4ill T]FE e=*g phAo|4. zl+
qH+ ollL1^l0ll tll-d g-8 S.eArEel 7lq 07C.2a) q=o} 7l+E-7I &..oJ +qtlq^l ol zlfol trl;<l= 6I6J 6Jg
ol +s_4 ?ol r.l H+6l|l +48 +E 9l+. phAs,,ol4(zt+ u|:"t zh4E= "JHI4 o e sE +4Lilzl"J ol
^lg Eqql^J= HJÎ¤ +E oJ+e+ +E6I7l +l6ll^J ol$zlJ Erl
uin,..".,ion (T) = + N
l; % k)Iar$g(r)lr' dr (17C.2b) 6ifl+). ol Eg 6'Jol 7l-6Jlzl= Hol AE +b aol a+*ol
694 E^tJda¤
tr+.., E 17C.1 eqiJEel 293 Koll,\lel EE ahel-
P= N^rrh E+g tulg'4¤ q^{l fi7c.4) /(mNm-')

HIdI 28.88
ol 'Jqol +4+= fl"Jg EzI ffql^J +¤.4 ?ol ¤E -r:r
l-O
4 72
g + gl+. "_4ill= HI"Jqdol4 tr++^l 6'J EZITI oltl6}qE ql+g 22.6
olaol ol+6J + 9l= tAol ql{o} ++. "J"J EAI +el 4 ll

E 72.75
olzl ho) *q qL
" t
d ++q + +z|7t ez} zlE"Ja +l .zlE ¤ql q y*g il5ol tTllElq "J4. rmN m-r= lml m-2o14
e 94zI4H :919 kol hE "-qill Tlfol +zl zlE"J# g
4zI"F +4. olufl p-9-al g3 ol +zt T]FE +Hzlg o4t- gal"l4l 6J+ "lael quce
6lE pg"..hazl Ylq. ol 6Jg pg^,,h4 "Jqq t}l*+trt. E qr ¤zlrl Hlql tI+ 1l=- EE
ollulzllHololq, -L Sr t+l} B%t"lEl R A, I m.ol4.
Ezl-z} * o + ExI zl$ "JE olfalfl ol ^]] $lil +lel ._!ill
zl5ol 91_+ 947lot {r+. r4r olullE p9^,,h4 "Jqql ql
rq+ g}e-E ¤Eal4l,zl"J Pl tig s-+ "lEi 'J= +rH, + N
m-r o+ 44d4(t I = 1N ,nolF ? 1) 6-z = 1N m-,o14). E
B6l+ a;o1 sealr|. Eztz} q]EJg= a+qlE oJ $zlz| ol
rTc.tql "J+ d¤4"J <t# +4.11fl+. "JA.J +qe+ e
zlf $c + *Azlxl zI?-lE 4+qot 6[sE olr]lollr $.<l
E 6Iql^J= sH ¤^dql gs,* gol Helrnholtz "llHzl Esl
"Jqql 6l]B6l+ E"l ¤s6i+. olfl HJ^l o + 6l]4
p8u,,h4
e+ eeq, q-+^l +-q=r+ rJol ¤ fzl ?14.
6IE Hl+ +qg ot4+o + 4t+6}zl"J C+*ol FBCoI
9E + ll9 4"14. ralr r.ill zlfol +Îc ¤
ol-,9¤ .J 4n - ydo (17C.6)
+"Jg *4421 g' ol$E "J + flg aol+. + Ezl¤ol

+= E4¤¤:.llilr zl\zlz\ *6Iq, r44q 9zl"ll aliB s.E4oj z',iroip(<io<0) Heimhoitz "jiH zizi z]:,rQi+(dA
6l+ ¤ol 1Lo-" alzl ?+= d"14. <0. ezl ei6}= 4eg z}ts4"lq, EI+^J EHg ztg4
o + ut44Eql
zt-a6l-31= a6&g ol43 ol¤e.l zl$ 59
ql,<J rz|ql ¤e4 ql6J gEqI4 ¤8"14.
16C.2 Ei{l-=71 AIE ^l-¤ql
"l!le+ f;zl .tlo1e4

4lHE CAe ol llflol zl+¤ol E7l17C.1 E.E 8q OlE
=-$ei
4 ol*9 Ezl=ql ++61-= col E= HJ-6Je.-a ?zl ?*48 aH vc.4+ ?JZ tlil$ ol+6ll^J z)olzl /"J e^h= "+
4o14. ills+El +ol h "J+ ¤.q gel 4^14¤ E4l "Jg "Jtr
fl4. zo"cql^J ,Jolzl s.ocmoJ A^F= 5ol 2.0 cmllzl
(a) EE 8aJ ql gsel gg 4lt}6l-q4 E9 EH Alqe
r =qgEl=
"lill= -EH4ol alrz| El. E"J-g +Q.llej-::. a15u1, o1 T=72.75m1 --rol4, +q ElHl¤ qlLJzli f,(ld.{e}.
43 zl^="el il E}e Ezl¤ol till +ql rlEdî "l* Ezl zalg IB s.Hol ^}]-tr. ¤CEl= !+eql^J I .*H tlq
E=-tr.
Eelalolell 617l trll$ol+. 4Lg .+ill olgol 7¤ o e ol flal-zl ?*=r}8 s$g ao"J* Ql ,= yAo"J*
q= ag oJull EE +ulg ulz]. zlJ.+ gzl ollE"l+. + =fl}
'}l
++q Eol ar*al-H ol/J.4 eo3=o1 zllzlirll, $ol
= "l4ql ol
E
+q4 ae 4I¤¤ BeH +4E alzllTl-¤Eg +49

=
+ el+. Eill .Jol
s.E g'4= Helmholtz qlqzl Ae+ Gibbs qlqzl G(-trq 3D) h
z 7l^la- 6l]4ts + 9l+. Eq 3Dql^J ¤E+ uls.]. pol laJ
+ aa 6iql^J= dAe+ dG= 4lql q6]lzl= grl ag-q, s
H Hol= E+^lzlE rll $eal "JE qTlql EEL¤q. alE
sE Hol oE "14%F do trJE HE+^l7l= ql gs* "Jg + \..
*4 *"1 dogl Hlell6J+
tr
=e vC.4
0l E.'JE 0lE6tE ,Jol7t l?.1 lE uj^l EE= tAl h trJ=
Eq Ezl "-4ill Eol edqxl 61.= Ell =JeEl gg 4lttg + ?ltrl'.
4* - ydo rE 8al tEEl (17C.s)
17c Ei{l 695
Hol x"J4=4nfporol4.
9 9ol 99-6l-+. g.ts4g +Prl zl^14¤ HolE ¤l
oo
7t6kql *+l "JHol ^Ja+E 49 -re1q1ot ++. .J4l2 sH +q"il zlglq= fl
Eol zlÎ4¤el H"lE thol4,trl4^J *zlt'J EH"+g tlzl$"l rE$rl r+ dre H6J trll -tr{ Holi ffi$ ?ol H
6J+.
HolE ztho!4. El-+^J ql "Jg 2ytho\q. zo.c"llrl 7Jal7l
S.ocmoJ A^l-= tol 2.ocmzlzl E9.g4= rll pgo-J $ do= 4n(r + dr)z -
- 4fir2 Snrdr
g q-q=r+ ?ol ¤4.
(22| ulg (dr)r$ +^16}r.). q"+^J -s$ol ol"J+ ql
w=2x(72.75-l--') x (5 x t0-2m) x(2x q+4 Aol +49 + ?t+. =qB
10-2m) = 0.15m1 46ll^l= "Jg
+4 2yth?2ytxh,+4 x 4441 8+ *4.zyt?zJ dw-ydo-Snyrdr
olz| /ol aÎql 4+61-= "*^J= Eolq, yE alqol+r
+_s-z +fl= "lEl B +rE{Nm-ty9tr_ +e}'|]= aE ol x4q= "Jolo+ HlzlE¤ dr"Jt *zlt-14 qlE *î=
El
rlg"lu(ul?+^J //g },-E +fl-e +4U Eol g+). cg q-q_r+ 4"1 ¤4.
rPl 87[ 12C.1 sE t]qol y"J .+ill +ql H]xlEol roJ F - Snyr
+¤ +f,$ I,JE} Ell gsql "Jg +$Lll= ^lg +E6I
trt{^l "J+g 6J"l-= dal Eg Mfpou,+ 8nyrolr{.
¤4. zo"cql^l E 491 elzlE r.ocm9 +# "JEE ql
gs+ "JS ol !s+ 4l&6lq+. E4t 3 ql6J i14 el'J flE +¤
Iur 1OO'O ',|"4tttr:55
H qlE "Jqg p ol4r 6IE sgql 4L+6i= E6J Cg
hfpôl g+. ¤B tr"=ilql^Jb e]'J er+ 4oJ fl"l +¤g
ol+qo} 6'tq, q-4^J trh8. +417I cB+trI.
(b) +EE 4nrzp rn -- 4fir2 p ou,
+ SITyr
EillTI r EH HolE lAr},llzlzl fla1l.<-l= +EEg "JE

"JHg 4nf e e ++H trl-q=4 ?3 Laprace Alg g4l ¤+.
7lE ql+. Se "+ +q +zl(E= *zle+ t'J{Dzl e-d 9l=
¤qg 7E+-r.6Iq, *zlzl il 9l=.+ill +E +He a= .2y Laplace 41 07C.7)
ol4r ++ EI+^J Eill +E '7lE'= g'J6i7ll "J6H^J +F Prn= Pou, r
ol4. tlal zlE= + sH("+E "J+ql 6I+ 4)g ztzlq, *
ff E 6l+el spg *E+. ol + 717)= +-fi "JBg Hl Laplace E6LH +E HlzlEol #*4zI B trll(+ sE
^lql
+6Izl"J TlEel a+ql= s.H4ol 2ullolzl ql+q 2+s ql ol ¤H"J trll, t4
rzc.s)E oJqzlz} ool ¤tr+. 4Lg +E+
4¤ Eq +qo} oJ+. tI¤ ?zl(*7lE se.6l^l)-tr- EEr+ +¤ HlzlEiol ql+61 4}e-rr-E -sE "J+E $q,(}7l rll+61
"J 4Ig +rlE
.lill= e4i{! uEol4r 6J+.
=4.
+F.ll+E $lqe Bt?E+ 4"F o}4. ol + "Jqil¤ +6I
49 +E6]l _H-olA+.
=
@ =E?-fq+st
ga: a.
ilr
.lill +9 +Fg:z sB4"l r-il+e-l "Je

6n
oI
EE 8al y9 ¤tl
a6J4 lF
=qEEj= g+
ol f,zJ-alEl= a6}ol+¤g ol= ql ¤B
^J=Iql flal
J
EEql ++6I= 1116} 6-J4 el6} 6Jol eg q ¤¤"1 "lF

=
qd+. Pou,
o utrrE, r
E4l 1 E+ "Jqql 7l.Jq= ql
r.al t7C.s a-eE L}|+el gr+01 sE9 HJSoll E=61ts s?fE 8olE}
HlzlEol r"J 7¤ *E .trEql 4I+6l"= q+ oJq p",,9 gE gaJE ?d+= 7l\la LlElL.U raJ. =E
696 EXI'JtE¤
#JEt q 17C.1
78
26.Cql^J tlzl;. 200nm?l +B E%r-gE E'H "J+ql^Jq 74 ---1-
sqiF= Laplace^1g ol+al^l r+s=4 B"l 7E + 9i+. E

z70
E
>.
7*.,", 20"coll,$
mi oo
io
fi
2x(72.75x10-3 Nm-' ) E-r
ra -6 rout 2.ooxlo-? m H62
r
--/ 58
0204060 80 100
= 7.28 x 10s N m-' =7281<Pa ?E, ol'c
azJ vc.7 E9 EE AaJq EEoil nl-= Eg[.
(c) .r-tlltr 4E .lalE Eq gBJ Bcq= "lill 7lE gE c+sol

'H+el
+aol tg
E^ll+(ol4z}*"1+ +Hqq +4)g Eiil +ql el+ $gl} Rolzl4l 6J+(rB 17c.6). rr]6|q ETlE-ol h
B:H er]*$ ^J+6IEJ= 4o&9 +ElU+. ol A
.-{illz} ol
"J+ g+7tqH a+oJol 17c.4^lql q4 ps^,,h71¤4. ¤zl
agg F-riltr lt8"l4r 6l-=ql, olag EillE E.H tlq ul]E al pE EE A=+ gEolr. &..E zl+ q6I 7Ia-Eol+. ulr+
ql "Jq+= ¤tol4. Eg +rl -sHql d+qqE a.Jg zl rJ EzlF "Jql^JE dill "Jqg p=(p-2ytr)+pg^,,h71 g+.
xll go4,:-4al-¤ fr4e ¤ .trîlSg E +ql RUH * trl+^l 2ytr=pg^,,h7194 olag e?-l6iB trl^.q=r+ ?ol 84.
d sg._42]l "_l"l E_^ll+ EEo + El4+Z_f4. ol *$ qoi
2T
al4 4zlH tr-s4+ qlEql glHzlzl a^q= 1"14. ol E h= (17C.8)
Pgu,,f
E"+ol E^ll+ Tlqg ,lq gqAql qr+ + .J+el .+ill E
H"l *H9 ol+rll qq, HIE +lql^J ¤B6J ul-$ ,Jol ol + ol ZI*6J 0l+619 Eillel sH tlqg
^JR"l Aqo}4l
^lg-
H qEql EH"+ ""t4oll SqaLTI Sa+. r46}q qlq^4 +Cg + 9l+.sts tlqg SEzI +ztg++ rJa6l-Eql(r
Ht.E +1, . s+ts +el sqol u|-tr_ r gE E+E +el 4 Uc.t), olag Exl¤"I gg+E +7ltr. sEr+ ts.ill Îol
^ E q mfe_41 ol*g f ?lzl ulEol4.
"J4-a+ +4l ¤+.
ol s$ol HI-+¤ol:il:1 *zl$ol rol41 7I{6IH ol $t
q ,(l-b Laplace^loll E61l^J 2ytrol g+. rqH sH HIE +l
z]trtEl ql fic.z
el gr-qg 4zl "J4 p*zJt_ -s.H HIE BE .Jqg p-Zytr
El! + Eillql 4+61-= 4zl $H3 E^ll+ 2s"Cql^JE<Hs eeT.tkgm-3)ol tlzlE 0.20mm9 E^'ll+
"l g+. _E^ll+
*t36cm "JE g+7I+E ol gEql^lE EE EH tlq
g r+q=r+ Aol g+.
p
p - 2ylr
y=ipg,rrh'
= *x(997 .lkg --' x (9.8 I m s' ; x 12.36x I 0-2 m) x ( 2.0x I 0-o m )
F'
)
p-2ylr+ p
kgms-2=N
h
=72mNm-
Eille+ _5r^ll+ 7lq Ea qq;ll Ezl¤

^plE "Jqol ^Jst
fa 17C.6 .EÎ+= Eill +oll --leE Ei1l7l 7lE= qal EafTE e-l +dqE+ e+g *ll=(+4+ +el +s-4 ?JZ 4+) E^ll
EEol ,gztrl-. ollLl.^71,\ BtE ^llf qTlg ga;e* 2y/r trJZ
=
zfil.
"Jsl "J+e
0l 7l?]E|ts gq^l7l-o-4i.ll TlEsl E+g@su,,h)011sl6H^1 S tlElE +.ltE .4al7L 7lq o ++El trqzleJ_z 6J+. ol ull$oll EH
=E011
o-4i11
Eill= E6U g+01 ,Jol.tltl. ol $$flzlr +g "Jq +ol ol-4s 4ela+. EI+^J "+ill
="J =0loll^lsl
17c Efll 697
+1
Yss
60
(J
Ytr
1 2
wualYb
fal 17c.8 tr+4 e,= 8JlAl6lE Cq EA.
.fA 17C.9 wua/ys1 HlTl'E:doll tq'al. d+,-+01 E6l'= Eg.
dap E"6I¤ *9 4"lgl^l eg

"Jflol +Et+48 "_4ill E d+4ol 90'sI 180" ÎolE(+ -t ( cosO. < 0 ^Lol
ol ql4zlrJ +EH e.il dzlE +e
"Jqg ^J4ll^14"t d4. E) .lillT} r4l s.Eg 4^lzl g*E+. ol aag
+ E^ll+ ztt;lzl gq'I"t qL+.
o < w t
"ll 6ll'&++.
'I++E A+ ,ilq^714e-l ¤+ 7\q ^lolq 4sE oo] âly1r<
olqr+. ol d+4ol 0.9 trll= 17c.8^lE +Hq+ cosQ
"J"J i3"l d+g qlE e. -140071 qq, q4^J wâtTte
+i-le+
=0.2301 Elq +gq +?-lql 'll+ d+"Jol rJ44_o-e *q
ql^J cE #¤ol "l+qzlzl flall.rl +E}u+(rB 17c.8). Ag +44=ql, ol4g +eE .I+ +dqol ,J6I7l trllE
rill-zf z-fl, _r.ill-oli-ll, q qill-zlill -EE tlqg 7]7J T,e,T,p =
ol+.
4 6e +448, ffi 6{o1 "J+¤ oll olE +zl CE +¤
"l "lF9tl4. 17C.3 EEI tr+
0. (17C.9a)
Trg= Yrt+ lrcos
_trE6q 6Cg a^l6l-= ql= +.l9 .gHg Sril eqqtq
q+^1, r a^dg E46i= A+flH^J_E_ ^fldg 7l+g g a + 6l+
BB"l ol+Elq *+.E _sH "+E E44 CAE ¤+qH
cosQ=5: (17C.eb) 4. rEzt F4lel EE"+g EE^!.=ol4r aI4, ol tBzl-a
g aill zlzl* glql #4--3 L9 Lansmuir-Blodgett tr+01
..1i1=rzlql d+^lzlL rll E,9e(zpr.g4"J) ge *91 H 4r.,814. ol Bd3 ol EH "+ql +ql ¤e 7l+3 Ed^la
oxill-rill 4lHol s+qEJ Irvin Langmuirgl Katherine Blodgettgl ol$g tr aol+.
"l 'JE dar "Je +ElB + 9l+.
E a;ll-zlill 4lflr+ Eill-7];ll 4lflol S"l4oF 6Iq q4^l
ol S+ql gs+ dg- gg q-q=4 *"1 ¤ + 9l+. sE "Jal
(a)
w^d= Trr+ Trr- (17C.10a) sE +Ezl+g ¤+6I= ql= EE-E rl$(Langmuir-

tA
Tr,
Blodgett +HL tzc.lo)ol +trol elil= "Jg
"l+g+.
tr++^l *-el
^lol
q*q_r+ e.ol ¤4. +Hl4 ol +HI qlE "_4i{ EEg u}4 "lE" B + 9l= E4 "+
E11E qq gleq, ol +4
"+E}|e. .E-HtIE BEzl*3 "J+
.
coso -wô -l E+4 (17C.10b)
^la +
gl+.
++6J +,]]e+ +Eel tlq f sE i(n: _ y)Z
T,,
EE g+ol+r 6hErll, ol s.H "Jqg tBzl-a9 z|"ri:olb
tr14^l +¤-r+ ee EH ¤tlg ol6l]6J + ?l+ *es EE +lq E+l+e 3E "+qlql HIEB a+dg +4
xl/ zlzla_ +A++ ol +zlE Eq += ++{1=
d+4ol 04 e0" rlolH(4 0<cosQ < 1
^l-olE) {r =4EllE
4-E=FqEqQfg tr+6101 onill-Iill 4lH u15"ll ^JzlE s
.-qillT} g.Eg 4^lq, .lillT} *.H +l.E ElTl+ -
'lo
ffi zllzlÎ4=tr}. dxll dflql^J= de6}el= sE gCzll

a vc.tob^lql el6ll^J=t<w^4ty"r<2"J
Rr
trfl= .+ill7l ,pl
il
rlrx
E A=J(E 0.01mg)$ flBC +.+ql +qztzll E EHql +
ol *.+. r4I E4 "+'H. olf^14 t$xl+$ oJ+rlzl
6e8 ExtZtE¤
o4ill + rE gdrll
o
H
- 1 .Êllote+t, c17H35cooH
o-{i1l o-4ill
o
g+E Eil"-+Itl tlo on
TTr E.-. HO
2 ola.Êllol=,Ll, crzHsscooH
fal 17c.10 EE oJqolLf T|EI EE Eg +861.= Ejl ol8El=
:l-^lel EE EE gdx1E +HJE E EEoll =dE
+sll7lr, 0lcl^1 Eal EEH=
EE Er|] 4_oE olE/.lTlE,\l 0l EE "f= gr+ lilcl. 3s. EEt|0ll= HEaJ
E=Elol 91ol^1 EEHLI qL -d +ofl eelts gralit=
=+dol
sLlEl:g + ?lxl Eol?Itrl. =+cg
H^l eE "+'ilql 4L+61+ sH "Jqg Eqq++. o

I
o- P-O
sH 'J"J&ol *9 trll= EE "J4"1 s.flel dnl Hol.ll il
o
*ulfllaJ4. ol Ceg 2i|fl $d zlille+ HliaJQl(p o |y),
3 oJu-= al-Pralld
olag EHql il= +zl¤ ql+61 7l^J ol=
^LolE A4zl
^tole_l
tsar*ol *s_alzl g:zl ullE"l4-IL + gl+. "ll^l6J
HolE 4l+6l^l ea^l7lH sE $4ol tfl tzc.rrglrlel aH vc.tlel Erll +4.$ ql& E4-p-=flldfl E"8 *d
?ol rl uu|tr_zll fizlxlzl ^lz+q}+. "lel6J Ceg .$zlfol ul o1 :-qlols{! Eg +d5ql Hl6tl^J H zl-ul.s+= ^}d
t4 tlt ll d6l]9l-= tEzl*g Bd6lzl rllE"l4l ^J4 ={d
ol+. olElal itol= "Jt =4-p-rqld -trfl"+ol ^qlotstl
e. + + ol $fif2ffi$ .4ap+ +^16|7ll ul-oJ+r.Jol sl
9l+. s.E EE+ gt q g "Jqg + 9l¤¤ -trol= ao eî ol
aol+. Eg +tE zl* zlq* ++g e],J6IH sdql E9 {lolal +zI +=e+ g +qlq. ¤4o14.
= +"J +EzFeql 6]l*6l-= HolE eg + 9l+. ol ¤lg +d=E ,jl4l EAg g+ol+r +s= al
"Jd
rB rzc.rrollrJ E + 9l= HIe+ eol oli =al
r s.H "J4ol4. ol +q Eq ol{lee S$xla$ $+^l7l
^qlol_=_^Hl)l}
ql ols^H2)e 3r+q4 -e-E= Ell+61 ulfalzl uJ(rJ H:o14a H t${+ol q+ alq4^J 4$zl-a E+e-E +qg+. rH
^ gl= qlETlE 9liluJol QE+) ++zl-+ql^J ol
^l-+ ¤"ll
t7c.l Eo9 *dE"l +$r]]= ute+ ?ol EE "+
E-ol ilzl6l+ H"lE ?41 +s+. E:. ol Eql HI6IE gl4} =
^qlolstl
e 5g +q "Jqg 444zl"J "JtI _=4_p_rql¤e *J{ *
4-p-a4ld(3)g gd q He Hol$ zlzlaliql, ol EI6+E e #g +$.llq olAol el+ stsql"Jg +4.Ir ?l+.
g ¤+61^l ?*I I o e qd 8"14.
(b)EE=el EE-qt
50
EE g¤gl= rl+^J tI4 c+^J tr-^l_"l.el a4lEr+ ae +
40 t rl-ol9 4lHql^l ¤+^dg +ElrI= Eaol+. sH ¤+cz.ilb
olel+ AlEql +4qq r s-E tlq4 .trE Sqg E3r+^la
h ,\ F.llol=
z30 ^f +. .EEql^-lel .trH g^d4lE Eo Ee| olaql 7l"Jq= -EH zJ
E
E
( l q HEI r]ol9 +41= ojo[Hz] +16]q + t] a* Fzl
20 ^ls d
mi
ol+ Êll0lEtt gl= 4l= ^J4oll}LzI. ?+r+E Eiil + LH+q^J= aCol
;n "l
"JA6Izl"J 4lH ¤qel a^dg $Czllfl E"E elEql g+e
El ro ?.!+J-Eal- >aall¤
H
0 \ --_-.---- + el+.
0 0.2 0.4 0.6 0.8 ol 4lE dill cibus qlHzlE + gilltlE zl4 G(a)ol crBl
EII'.J LjOl/nm2
r?]r EE Gibbs ollLlrlG(o)9 Tlq.tr. ol+qd+. +,
.fal 17c.1r sE g'alol EE gdl1l E^pt ilrl6lts 'Jololl trlal E6l.=
E.g. +Bd- Erl gelE LtEt'Jtrt.
17c Eill 69e
G = G(cx) + G(B) + G(o) EE Gibbs oflLJ^l t6sll (17C.11) EII 3 ^lq

ol
4= d^{l Gibbs ollHzl
ol ll +H4 ?+ C{EE uli H4t Q¤4 E"l d4l Gibbs
Hl*f,. %IBql q+ Ee Iel dill Ee"+ n,i a*4 F qlqzl HEle+ ,Jtr+.
"le+
+ +q Eqfl= EAUJ nt(a)* nt($6la- 4lH gEE Ee=J
n,(o)9 TlqE E + 9l+. - n, - n{a) + n,(F) + rz,(o)44 E dc(o ) = y do +o dy +\ ttdr,(o) +\n,(o)dltt
+ gl+. 4E tr-el Ee=6Lg EE rl.gg rrE zlzlt_ q-q=4 .,JAIA c= TEXEI+el-3ll"1lE o1g
*ol 44tr*.
Gibbs 9luJzlE tI{ 'J+oje + 919 dc(o)ql ++ +
^lg
EoJ6lloI tL+. r?-l4q ol + 4g ?JAl+eH q-.q_4 eg
r n,(o)
o
sE +geJ t8ell 67cj2)
+4149 eg + 9l+
{zlrJ oE EE H"14. sE tiqE EH 4"Jql ql6J +41,
ody +\n,(o)dp, = o
q+^l $^d4]el 4lH r-" Eql E}|EI +al$ oLflql^J +E6]] _H_
olaq. ol oE ++]L EE r+.Jel eE(4 = nt@)to)= ol¤-6IH

^l-g
EE tr-qel HEle+ 4lE ^Jq il= Eee_l sI+ EIHI¤ Es+
t AlE gg8l 5E q-q=4 ?3 cioos 5E+lol Llg+.
zJxl ^folol ^tolg +41= +E}.11=
oJtI4 E4{l dy =-\f dtrt,
"e. 7,p,,) el6ll^l trls=r+
ny9 (17C.13)
Gibbs "llHzlE Gibbs 5E^l
2.ol HaJq(sA.6^l).
dG = -SdT +vdp +\[tdn,

EZI 5 aC.ll trl= 4q iqql¤el H+
ol ffi$ B"l ¤4.

¤zlrJ prE E¤ IE slq! slHl¤"I'i. "J¤+ sqql^l=
vdp= 0ol-I- E "Ja+ gEql^J= sdT=oolq, :.r-la|{ 9 dy= -Ildg,
+E !* + 6}01 0ol B+.
= #3 +'+ +ql +46}= sI++ IE slqi qHl¤3 p, =
E4l 1 4lHg .llrixl H+= +4rI=
Gibbs pi + RTln (c/ c") o a +q
dq. ¤ zl ,ti c1E $Lo Eo ltr c"t: -7
^.1
4lHql q6H^l ol +414-9 4+^lTlelH 41Eg EqTl 916l] s= +Eol+. q4^J ga,* gEql^J= dp, = RTdln(c/c")ol
,<l all.foloh 6l-= +714 oJ ydo(tzc.s^l)g EoJ6IloF ++. +
S4. "l dp,E t7c.l3^lql Bq+E qg-r+ eC
4lBel Gibbs qlq^l H+= +EL'-}]= 4¤. trl-.q-4 ?ol 44 ^l"l +gtri.
4ot eI4.
dy =-RTr. dln(c/c')
dc(o) =ydo +\ttdn,(o) ol !g +94 ?ol C46J + 9l+.

¤Bql^J= 4I dEel EloI qHr¤ol EE tlql^J eolo} 6lq, dy
= _RTI-s
EE galg (17C.14)
olagr/re Ll44zl-tr. 6J+. Dln(c/ c" )
EE 5E EE
7'
=JAl2 ul^ H49 4E

EE+g EEg qe+
"Irlzlzltr EHql "+EHEq sA)
ol .rr ¤lCxllz} alEql +4qE sH r+"Jol ololr t7c.l4^lol
g "JA-J gE sH flq, f_?]tr a¤ql^j 4E6IH q-q=rl (4= Dln(c/c")).<0ol ¤+. + EB ¤*Czllz} +4qH sE zJ
ee a4= eg + et+. 4ol e.a*+. 7E r-o Eql q= HEI¤ +e4a 17c.14^lg
ol+6Lq _EH r+"Jg +e6ifl EE gCzll 6J +^l7l *.Eql
gl+. rI¤- Ezl9l^J ol +41=
G(o) =p +ZF,n,(o) ^j ^|z16l+ HolE +eB +
-H_ola+.
700 Exl.rJtE 5¤
4. elzlE t pm4 E"J9E fi!-, zs"cgld p/p.9 ul

@
7{X{
EE rt?trt sE g¤nlt ErtE EE Esi I nm?_l
y 7+7+ qI r.oor4 3ol+. .gz}9 A+ql= a_ +^l7l a7)y
=<j
6tzl"J E"J$E zl$ol eI roz11 AEElql ?I 9= Ezte I
zo.collri 1-olul1c$+tl +*.+E EH f,tqg L" E9 B
+-tr- +ca|{ d/dln(c/c")=-40pNm-'oJ a+= gfl+.
9 ?l-o Ire 4lHJ^Jol s.eq, 4l&E zATl Ed^B+. dz}
ol 9dzll9 sE r+"Jr+ +fl ¤%r-r,lEl B E445 41* E A+q= r ELalTl 9"t 9zl ?*zl"J ql+61 +s.+ e4
61q4. Ea4B+ 9l+.
qls^J +=E ¤cg
^J46ll Ezl. Hr ^tJ6J +71= r+|.
rHEt ,tl¤l 17c.14^lg olo-"olH dyl0ln(clc")el +A il E ZITI+ ¤9 " t"6J4. qL CE9 t"lzlzl 94zlH
e
s+qq EH r+"Jg zld +e + 9l+. -trH 4"Jq4 $sz} oll+ *oI4^J gEql4e e #zl7| q{ill EB+ E
Avogadro tL+= +6ll+H ¤%r"lrl B EzlfTI +g+. qq, q+^l +G,7l7I EuJge qq +=:"1 ¤¤q
?IC6Irll
17c.14^l-o +.+El trl-s-!+ eg 44= E¤. + 9l+. ol"t 6J 4,o14. olBl6J $4E z7l al4+ gg +E E +zI
=ol 7I trll. zlfl.4z| EqEq^l
"l^llql Erl¤-g "li= 4,"14
r,=-#(#a), r ^J46J + 9l+. rfl+
Erlgg ql+61 zlzl oll$
olelal
ql +e 6zl "J49 zt¤ 4"14, tr|4^l E*¤ol zl4z1i.4
I
= - (83145JK-r mol-r ).x(293K)
x (-4'0x10-s Nm-' ) B ="gqq qp-la "J 4o14. olEl+ +e. +g a6}ql E6|]
iJ+el ¤+qBJ= Cd"l 9zll9a +717r "Je6izll ¤z]]
^J
= 1.6 x 10-t molm-' 6J + fl= aol+. olel+ +rl *g rtEEt q*.+r el4.
"l
El{^J ¤%r"lrl B Ezt += Npsol+ 4ss} *zlb q4illql HI6I]^J= gqq}4es E"JC6IZI"J
eq;.llt"l tCslzl dql g¤^] o_s tts4"t {+ &,9 E*g
NoIl - (6.022x 1023mol{; x 1t.e x l0{molm-2) ql Hl6tH E"Ja6Izl ?*eq, tr|4^l ++6J zld4t
=9.6x 10lsm' 'llrlq
ol +g EuJgol
^Je + s= a"l+.
=ie-_ts
rPf Ef7] 17c.2 +lql^t Ee Ar+E ol+6l-q 1-olulL E*¤"1 +gqEl= a'Jol $xllslr. +Eol ¤cB + 9l
++& t Ezlz} i}^l6l+ HolE 4l&6rq4. ,il 6l+ ae + !+c
'IEol+r ^J4g+. +d a4E +E
.urupl x o.t :E 6l gg +E E +^l7l ^ls EBIEq^J zlfq-q EHlg
g ¤C6Ir "l ql$ql +e +g s4zl "lil +4421 =
?*E
+r ^J46I= Lol4. rel+ olBl+ rlEl4 Ed ECol
-4
^JrJ
7|.}.^dg'li$6l *eq, q{^J "lag Hlzl /871= +g
17C.t+
- ollzlr-l#ol+a E + S.+. E 6l+sl 4{qlî= et$ Hzl
olzfl ol Eq$ s-9 +s9 ,|]Hi$ 6Jrq^J zlzllzl "-4ills * "J"Jol4 += ="+g "le Ee "J"J"lg E¤¤ {zllB a}i
+q= ¤tlg {sapx} ++. Eq 4Bqlrl ¤HaJ H}e+ e 4o14. + olq+ "J"JolEe E +z|7l
=q+g
i ll. s
qq:{lel +rl Sq p+ a-
"44q1 +714 "JB arzl 7].6llzl
Eg zll+6JeEA] ffi "JezlE E6Jg aFb 4"14.
-4
"l
H +zRlr+. 4B.24ql E6IH p- p*e'^tpr^tol4, q7l^l p.= "+ill= #= d oldreE +E glr q=a olalE a[
,-J4¤ +E 9l+. "+Eg
+714 "J4"1 T}6llzlzl ?*9tg "ll9 "Jq"lq y_(Dg EillE "l= 4 a+qlE e Bc 6d"l Hg uI +
g +rlol+. .lill ,"Fgg :z *_E'H qEql Laplace 4ozc.z ++= ¤++4 "JCE qlEql gqq}4qE "Ja+ tol 4
96ll^1 2ytrRJZ4 +714 Sqg B=+(rg EHel HI 44zl *g + fl= aolq. qlE^j r+g ^JEHrl-+4+= a
^l)ql
+s.244 apgl ol <Ig Bq+ts "-44lrl *zlE ,9 *
g +F '-l]+E ¤=71 "Jqol yfo|.! 4r3 zlezl $zlq+E
^lE).
gs +4Iqflg oll9 :z Eillel +rl "Jqg ++.ll= q--q-l} c|.rl q Effizl ullEol4. Hl4 +E Eg Lzl $}r TIgp
olel+ B"JceI ,lJ."l iJzlq, sszl #=d olrlc_tr. ¤-
B3t<elvin 49 gg + 9l+.
oll
4z}trI. 7J4 Tlar| gotH:¤. AEE zz\tr z}4=ql, oltrll=
p - p*ezYv^(t)trRr lGlvin l (17C.15)
d6|rll Fl= ¤^Jol FIE=+. aqill= rlat #Edql^J "Jd6I
Al #416LrlH +4 E"+"14 *zl 4*?J+ e ¤^d ¤=Cg
s+Hql q6il^J= .lill Hl? +q "Jqol "J+q E.qtr+
q"+^l Bq +qo} ++
*eq, *el ^lql^l zl+el +gE Hl-+7lrrJ 6lH E
17c Eill 701
=e-d7]lLJ=
D l. 7-d4 4
qI tsÎE+q HlzlEol r"J *ql 9l= +41 dr"J i 44ztE) A6J"l+.
qlEqfl= 4= E4^fz| anMg\r)fdrol qE+ aEq= q trs. EE g;alg ++6J +,]|e+ +EE sH Alq zlr+.
E "JEddE g^tEl EE -d++r +trl". tr6. Eq galg -sgEol +zllp. + 9l= alql EE SHol4.
a 2. "JÎB E-* q43 Monte Carro -EBolq E& J7. EE gd{k t}= r}ol9 4lflql +4qq s.E +qr+ E
H9 ols" olq +il 4l4Ie-E +B + 9l+.
=4-+4 "J E "Jqg H3tl^la+'
I J. .lill=:_ -EE HolE a.liE+^l7l= Eolg +ElU+. D8. -4 E¤e E4-E"l E3l¤-g + 9l= eEg "J=q r?_16l-
"l ffi "Jq+41 + 9i+.

a 4. E ql$ 4tAg .lill7[ _E^]l+ +¤. .!-4o 6]q=(A+ql q?+^l 6J
=s-et^l=
,('lzI
oe --1
I z.^l
I --1 al {a
z]o -A- ol-gj
I ]J--1 P = Pf,^,,h
Hl"J+c +ill 17c.4
Laplace 4] Pu,= Puur+2Y lr 7= Ets tlq t7c7
zlzzl
ll
-
--1 coso = wôlyrr-l r7c.l0b
G=G(o)+G(p) +G(o) z-l ol t7c.rl

-EE ciuus "llHxl o--
EH 4""1 r- \(o)lo ol
z-l
o-1 17c.r2
Gibbs E"
S! ay =-\f d.1t, t7c.L3
sE g^dzt1 5r9l qE sE tlq Epl (dyldln(clc' ))r = -RTf. 17c.r4

Kelvin 4l p = p* t7c.t5
")t\'",rtvrnt
EEf 17D UEÎ
17D.1 tsE= EU
aExlts r
E EeJll -e.g= 5,'.16lr ¤861.= E^llel 1a)l=
Erll= r1l7l-Lrtt. rE^lE9 Eal4 LH^l=
tll E+ !i.lt +-Jill= .JA+ +"J E e=+g *=+. r*l+.J
e|*4 dE=^tleE
=¤61= 0l6H6falE -r.E^lel olal-et Tzsq 8E= GIEXI C +.Jill= rl¤ 2ol4 E e+=ol ^Jolq} Ezl-=ol g,EtE
¤E6}|0r6lE^l= ts Esu lfl= a0l+. +tr Ptlol+. ol4,t} +aL E& EeE E e=Jg +A "JB
ql q+ t"lal
++e_l ¤til7l-+g+.
+trJE EaJ III^Z +-q=r+ TJal 7+ E a"+ql+ ^lE +ql
-lExlq +6= 0l6H6fa1E r +5 trJd|4^l0l =
L|EILH= qa1 80I-d
=+9 ^l¤olLf
+=q HHE= Ia16H0f -srtl.
r
EqgI= Eeel $zl4g- 7l+^14^J qa11f ¤tol4.
> ggEl qlul xl^l tu=*>,r,r, +_gil

=
traJ tge| (17D.1a)
r.ErtE Egg ErlE Hl-eEt 8E4tE

(EE 178)g =el6lalE ^tole] gq4
ts9(E4
12E)el
0l6l|at|0t Lltrl-.
tlE-Enloll tr-"t EA I
Lt|+ ollLlxlE 7i|E(EE 2A)0ll el+"t10[ Eltrt. g+ llt]oll
¤zlrl dill E4f4.
N,= g- dt+ol M"J EzlE i N.,a9
! lL- D.-.!+--.---- tiEI={rH*t rrtl
ol ¤+g "JHI49E E e+g A"* *r-Hee +¤ts qi
EIi nlQX} 7171 7lO F"llclt}I{
-ia5E --rl.{ -Eu d/iia'{-
^lE Dultzllldllll E-=
=d=
traJ M-= Ezl¤9 E A"*ql+
^lE +
gH= olEg aottrHEE 2A). +e+.+xl-EJE
=
ql ilY ?+?+9 a+3 7l+^14^l 4l4I+ ¤+ol+.
=q =
aErl= Bg 4I3 Ezl-5"1 Cal zl*"ll^J ^J.JCS E6l]^J NI
1
=-ffitotul L*,M, +ZI-EE EaJ t8ell (17D.1b)
=
+, dEdql^l p]4zl.ql E6|^l+, E= &EiflE HI¤: tlil
"-
+ql^J a6Jg trl]+61 +zl¤olq. a¤4_o e ^J7l= aE ¤zlrl m,Y E d*ol lr,"J EzlE + d*ol:g rng ^1tr-9
zl¤ +ql= gr +ê+=g3 +'J+, +Ea Eê+ eg E4 dill ¤"*ol+. ol46J ="#q ¤tg +z]-el "J 4i+ :.qg
tsqq r4r ql+^l4trqt(DNA)r+ ee ol-4" alzlrJ E= 11+ ?lCqg *r fld{+ +"-q +qlîel
=4+=qlsEl
E 5-ol 9l+. ol Eqql^J= rBzl-=¤ a;ig 4
+s ql^d oJ"Jol EEE- +46I"1 +g + gl4.
ol+. 6J^d aezlql= 4e LlaJi{l=ol arll eq}qr E +H
e + et-Jqa o1,<i ^Ja +.JEol+ eg
i{l-E+?i+(re 17D.r).
=p-lÊlflfq =Et
GE@ +BEzt+4t-EJEat$
ol*alq g?-l-gn}HlH
olzll cllolelE
^lEel +-¤+ "t
+rll-¤+ E A+g +6Iq+
+7J I 2 3 4 5 6
M/(kgmol') 7.5 12.5 17.5 22.5 27.5 32.s
(a)
mlg 9.6 8.7 8.9 5.6 3.1 t.7
=grlt
r.E{:g AtB t7D.rall4 17D.lb^lg ol+6}E g+.
N= niNeolo + +-Bfl! g e=+g Ee"*(E +)g zlzlr:
(b)
+4.J + 9l+.
(c) $l&t+tf,0 fun =il";I n,N nM, =
*!^2n
*
fA 17D.1 5+.(a) =Jf-d dE 6:BFi1l, (b) cl'al
-l"a[L (c) E¤=gxll
^ll =Et =:BFi1l,
Et
=:cFillel =+.
170 .zErl zoe
9zlrl n,E E dtt"l M"J Ez}9 Eee&E f)oltr n.,a

g dill EzI9 E4=J"l4.r+ +7JE EE dE 8^l -rBzl.9 e"*g Bflor;ol+= +9lE +
^lEE e"6}g +
a_
4ql=ql. lDa= m,ol4(m"= 1.661 x l0-27kg). tDaS EzI
a9 ¤+ E e*sE ++q +H 4 +?J9 EA+g 4l ¤eJ 4solzl E e%hg +41fl= aE= olHg ++aI{
+ 9l+. + n,= m/M,zl-94. :aqr ,+ +?JE E e 4.+"1= qH rBztg d=J=oltE d*ol olq+) 100kDa
ÎB
* M,z ?J +7J "J9 Ez]¤E Ee"d= (r) o + 7l+^)a ¤
+r 'JEl + flgq t4 ?*"1 100 x 103 x rauol+), E* g
+ile+ 4* (M,) " + 7re^l{l ¤+il= 4lcd+. d=Jol t00ks mol-Iol4tr "Jg +E 9l+. r+l+ E ?*ol
Eol ,+ +?JE EA"d=g r-l-s-E4 e+. t00kDa4-a "J6lE qI ¤+(¤zllE olBzll Bol if r glzl=
6t+).
+7J I 2 3 4 5 6
M/(kgmol ') 7.5 t2.5 17.5 22.5 27.5 32.5
n,/mmol 1.3 0.70 0.51 0.25 0.11 0.052
dill Ee*3 re,o,a =2.92mmolol4, +-¤+ E g*g + 17D.2 80lEt t=ol 7=

*4 ?ol ¤trI.
Hllgol+ ++lillE *tt uI]¤
r+zl-9 '+4' ,l]Eg
^l¤E
L4, t (kgmol-' >- x x r2.5+ 0.s 1 x t7 .5
q +6ll^J *4zl ^J461+ HLql Ir+4 94 ^J"l* +=9 F
)1t .3 7 .5 + 0.7 0
+ 0.25x22.5 + 0.11 x27.5 + 0.052 x 32.5) = 13 * zl4 + 9t+. +d +qlzllE olF h zI3 BzI tzlE9 t
^J=
rBzl9 rx1+E4r 6J+. &zl= a
+ +Al-¤+ E e?*g +q =.alqlflql^lel
^lEE dill e6+ol
zz.69olo ol 6l.I E E4oEgolulcoll.<Je} a."1 t
^l+g "JEzls
{ rlloJQE+El trl-s-r} A"l 4d 4ltB + gl+. ol+
^l¤ Îolql +4 Aqlol
ol-folzli -${-a3 "}^} +aE
"JEzlE EL+. q+C ++illel a+ql= 4E
gE rlzlEol E
L4* l(lKgmol-' > fiO.T x7.5+ 8.7 x r2.5 +8.9 x I7.s oJ6Iq, ,rl4rl q+Cq
"l+!= B+lillE "lE"J "5"1-H *ts
+ 5.6 x 22.5 + 3.0x 27 .5 + 1.7 x 32.5\ - 16 6I+. qlE^J g4qlEHlE HI+ ++l= -cHxcH,-olq, ol
o E E^lg + gl+. q+^d E
^l+E +a= -(cHxcHr),- o
lz}
+q + ¤+zl7| trol6l+= ag +.:r-6I¤4. "l a+ql c +6Jill+ ^Jill rEzl+ gEI4 + t"l* $4fe ol$
Z ilIJ-luI"= 1.2014.
qd trllEql ri} +aq THHol +eltrlElzl g:+. ql
gqzlE ¤+ ^L+"171
r[7] 87[ 17D.1 ar] de s-E. e*e E^J +Eeg q4 t"lt oiulL&Eol(oJ 20 o
tuIr=Z,N,tuti t\ N,M,'o]4, olag Z-4& =- 4ej=olalr. +) EqE E-d -coNH-(r)ql el6]]^l ¤eg N
EI+. ol ¤E9 ,r.,le.oll ql6J z-¤+ E A+g +6Iq+. EalnJEIcol+. ^Jill aEzI
I
^l+ol 5}g CE
H
:6
,-1our8161
li}
#q^l= +aE +r-lE slEl4l aJ I! E{ltrl=-
Bst_
77El
=s
=H
tr}.
Ezl-^l¤9 ^Jol6} ++EE "JillzJ Hllgg Eell+l +=

[4*tL4^3 (E trU) E|ttS.(e.= 'tr1¤r-E tj z]f' pDr: poly-
Erjl, g+E r A.J+ +fle sld^lrl$ Bqlz| H
index) 4i1 +-q r ('D-stroke' +r
^l+E
dispersity 9l s.,<1 qp4. 6J+. r+z}e_l B4= +a +4uq. rBz}q zxt
=tr|)-tr- ^ll =+le
p=4o Etl-=. (17D.2)
e +4 +ql^J= EqqlEHl Ezl-9 271 +271 5-42$ aoJ
M,, t6El
ol+.+r]]7I flg trll= rll 1007H Ett;llu}4 "l?-]fl sooteE
ol zlfz[ l.l ol6ioJ 6JC +.Ji]l= S+4_o + ++ +^Jol flq4l *tr- aag qlg=ql, EEzlzl "l"J + +q +*ill
+r ++. ^lsq= +4q8fl ,r.l_EE ^J'&61 f}-*"Ja|.{, ol 7I qE r ElHl¤ qlLJzlTI 94 ++a ¤¤¤ olzB + 9l
zlizl "J :0"14 ¤+ E ¤=Jol ¤2il Eeg .Jc +qlill= 7l trll$g 4"14. 6J¤ BEAA zzl+a= +E +r A6Jql
rill ^Jqlql^J rtrq 3il-g g4?-l ¤^J.'l+l.llq Ir++^J aaq=
el6H^l rrtrE z44ql u]]gE^l +4r"4 7"J, Lld
gEe+ +=aE ++. ol +se] +e +4s+ Hla aag d E(re uD.Za), E= Bzfal Eo&g 6lr += Bz}9 6J 5A
C6l-= Ell ttI+^J g+A + ilq. ElqE ol+r ?lq.
704 Erlzl d6¤
ololol
E---.1-l
{,
7l=
-I
) ololol
E ---{ ---{
)l=
-!
()
(a) ( (b)
aeJ fiD.4 3xffl 94t5 eeq, -d r g-BF=
^l'+
?Jo =:Bt^l=3
P I trF,Jtrl.
=3rl =33
aeJ 17D.2 (a) SEal}ts 7 tr + LIC BEHE 2il +4= LlElg + "JEtro l^ lLf
?ltl. 0l LIC +4= flE:o.E ^=.lalE
LIEfLHfltt. (b) Ttlel LtCe EE=01 Sg
f
+ArE ?9tr EeqE,t.l 3^l +4= olF;' 9itt.
=
ololol
E-l-l
7lC.
-.!
0
0
I a
7
\^
0
t" 0
(
rEJ 17D.s 'J*?f= r.tr,\l7ll(qlaEtl lEi1l4e.9 g-BF +9le
-r- :rTJo I tf tru rt
Ll xo TlrlrI I LQr[ =-Et+
a[-rr :al'JE
^l/ lL i Li-Li.
=E =-i,
.f.g 17D.3 _r.?6J 3^l +6=,*= E 7He] Aft?lill=O| -sr'uil

=qz\l
4il. E-il-zl6}zl ?+sq, q+^Jtrolt ffi$ol t-g +zI
74= olErt. ^l-+el
¤qg ifzlal + 9l+r S4++ dzll"ll flq^l 4 A-Je
r *q e6.J "J6J ++1=- gE- 4E_E"J sld6}q(rB vD.s)
3i174= +z}el +ill4"J :zl-fl +aE EqI+. qlE^J r ¤zll rl¤3 E"J
^l+ ^Jel + ? Eol
zl-g4_slEcg +4
4 tzo.zbql E.J 7l*4"J *Eeg *g +4Ia a"J E"+e L}]q Eg tIÊ ztzl6}zl ?+eq ol E'Je 4E4Al +++
-e ¤Ag +d +a gqg zlzla- 9l4.ol +d +a gqe E 4014a E + il4. zlt4"J rzl¤9 xlfr e6J ^l¤'ql^J
tlE4l¤-g 6I"l il'J* 3zl- +2. olE+. E= +%iill tflEol 4dtiq flsq "l*E=!+E 4E=
rBzlE 4rl ?E= Ezl¤ol e{6-Ja}q "JEE +,Et + =
0.0144 rao"o1'}. 3il-flE 4+ A!+
^l¤ql^l= t*4lEol
a+. aA uD.3+ 7+?+=r+t} 3it +a=- *E +211E A++l 4dol4 Hql"J 4q}9zl S.+.
illTl-*dg E"&3 Eq=+. olel* 4il +a= ^JE+ql^J
Ell+61 +s6i+. qlE^J 4I^-+HI +Ee6llE=EHlg 444
=z IE 8E
(a)
A'J$lill=_tr ol+q4 9lsq, olE"l +lso_q_E OrE *ol¤ zl+ e6J ,r.l-olzl. gqzl glg +E
a7l+
ollr. E q+= "Jg qI+. ^l+el ^l¤ "J+
ql E=El+. lil-fl +4Le zlzltol qÊS 4ruts +
^l+g
el+.
17D.3 +Et8
=g il.fl +arE ?goil^-lel EfE .EE
+^ += qE ¤4q -IL+q} a.Jg trJE-zl *6l"
aEtol+
@ 1
#6J ++l.E ¤ Î+el TI1I rE=¤I ¤E}l= +af8 =. ¤zlrl +E6l= 4? ?Jolzl 1o1N7HE *+le I rzJ-fl zlf,-
=
g"14. ,it} A+'* ql= trq4 ilg += pE +61= aol
A++ +4I a6J
^l-aE "J+"1
ntrJ==
=elqlHHlol+.71*
C agel E'Jg'zl+ AEL ^l¤'qlql, ¤zlrlb qtr eEtol +(^l-=E + aol= Mol+).
+ E+ r sq aqlql ql6l]^J zlf+:zl "JEel 4E= olE Efil 1 F_nL4+¤ o}d]+ A{}9 +
+ glqr ^J4tI4t:24 tzo.+). E6J 4 *ed=41 ++l= +vl lil-fl zI+ e6J ^l-=E B4= ++g.J6I= e.JE f(Nn)
17D .VErl ZOS
e+ 3++g 5J:"1* aqlE +(Nr)E zlzlt_ +F+8 + gl+. 1
Î
¤ "J+ ÎolE ,14= (Nn _ NL)r"l ¤+. tr}+4 n _ (NR _ NL) 0.8
ol g+. + +fl f}. Lr= Nn * Nr"lq EI+^J N* = j(N+ n),
r4a NL= *(N- /,)ol ¤+.
S
=H
0 .6
N
EJAI2 +qI4l7I + B^l¤ 4rl= +49 qE
"J+ ^LolE
N
0
++a6i4l daqi +.JillE "J+9 A4zl m/ol E q¤ p=

nrni
'pll
+gr+ p."l u1.49 + 9l+. 0. 2
"J+ Îole-l 44zl rzloJ ¤qE + -2 0 2 4

'
H_
7k+ B4Ee-l + + n/M/2
fB 17D.6 1il-g +2\t8 aB9 SJ lel ?J4oil rH-d += Es. ig FJ

ol +.J4lq N**ill ++l ?+?+c g+g 6F"t4't eE+¤-
^l.o
/.l0lsl )1zl= n/01fi, /= 4.JaJi1l"l Z0ltrl.
5F"I4, tr|+^l 7l-tsq} di.ll B4g zNol 84. Nz11 gg1 iL
el olq|;.].ole-l
¤ + 9t= "JBel + w= +
44zl ntol
^l-+
+¤-6FoI= A6J NR|]zH4{zlE fl+g aj:op.) +e}lj "J
ol !g +^l 4H q-q-$ *ol ¤4.
He-l +e+ e+ q4,<J w5 al4I6IElE d4l Nrl] ++l +ql y2
2 at= tlE
^l
sp+g 6J:"1E N*ol 448 %r-Hq += +6IH E+. ol P
d e
-n2 t2N
Exl--
D --r-
L!
g zgl
(17D.3)
49 n4e1 'll^JE dtsE+el n*zfl9 '|]tr-E$. dq6l+

4+ rJ? Exllolq(Eq 12A) q-q=4 ?ol ¤4. ol glffi tfl tzo.eoll rr.1a19r.1
N!
'=mffa;:dt - {}(N+n)}!{}(N-r)}!
Ei+^J,
N= 1000 r?]r /= t5opmrJa a1z1-. lil-?l ++C i"JE
P
W
=1rrryN!
oJE ^l-olel A4zl n/= 3.00nm71 e +=g rzn.:ul$
- ol+6lq /, = (3.00 x 103pm)/(1s0pm) = 20.09 Brz al&B
+ eltr}.
E4l 3 "Jd¤ ^l+el a+
ol m(Nol E Atr_+ "Jd*g trll=lnp$ 4f61717l
q ^l¤ol
¤?]6I+. "ltrll= 4lffi$ Stirting t2A)ql q
o= (
,r.ftdd)''' ._-'o'o'"'xlooo) - 0'0207
=Î^l(Eq
+ +6J + ?l+. {zlrlt hx! = xtnx-F=-E 'll{ql +
=^} + ol z4ql^J Eag ffiol 4sBE rol+,
*4 ee E+ e"J+ gg 4= tsol 46J6I+. q
lnx!= ln(2n)tt'+ (x+l)lnx - x
rqE y*e- +4 4141¤.:a"o|l,rl r+q=r+ eg a+= gg + 17D3^lg 3zl-g E"

tql^l zl-+ Eldg 6k
^l¤ "J+9 4
91tr|. 4zlrl r+ dr S9 rlol9l 9lg +Eg al4}6|= Qls ol8¤
U2
+ 9l+. ol +Eg r+g_4 +ol f(r)drE +4U+.
2
lnP=ln ,rN - *(N+r+l)ln(l+v) -i(N-n+1)ln(l-v)
a
f(r)=4n U2
r 2
e
-a2
E}E EE
{zlrl 1) ol
TC
v= n/NolQ.
^l+ol $u4a}H(n<
u+
(17D.4)
^lq+ =^}4 ( l [3D +^16 ioJ]
-d
o-tr In(l + v) =ry +4lE ol+g + flgq, :7+lH

-#4 ltrz
qg-+ eg '=lrNF )
+g+.
=Î^l"l
2
v2 {zlrJE EE += *ql^lE rl¤ zJ"l7l N olr}e_tr 8 +
lnP = ln
,[N - ]Nv' $.+= ^ldg 5-rlalr. 914. rzp.4^lql E6IE r>Mol g +
706 ETPJtE¤
Ee r {Ig szt H+l ?}ql EqA AE +ql

0ol q}9zl"J
"J
g+. +g ,14 g9 6, "Jql^J= El¤ I,JE7I H6Izl ?J:= 60
4-r. u;r f@6& ahlEi+. ol 6114 ElBg uffil,<J r.lE \

^lg t
E
+E 4 Ezlzl aJ ¤4e+q qE ¤Elle #"JS.ol #qdq- m+o -..1
r ^J4$ +E gl+. rflE fQ)dr? "Je_lg +zlql ^l+ "J+ K

Hn
r4 r+ dr rl-ol9 <k& zl4 ffio1 gq. F

^tolel A4zl rFl zo
H0
nj
zrtrJEt oll 17D.2 0

0 1000 2000 3000 4000
ZI++ {l tzo.tql^J f#I{H w= 1000 r4r l= 150pm SaJillE +, N
"J ^l+g ^J46lzI.

qzldE N= 1000 relr /= 150pm =zJ
17D.7 3^l-fl +ard -7,g gE 7ialoil rH-d +BE-îlEil R,,,
^l0lE
olzl"J 3ilgolq o Zkol trl+r+ *"1 ¤4. 5 gglxll9 +oil q+ E:dtrl-.
( l \r/2
-- z'st" 'x10-'pm-'
'= [ ztrooo*1rsoffi ) Nol q={*e_s 4l+6Hî ol+rll ,}eq}+) z}lz}]g EqE
=
ol +zl"e6lzll u|alrlu + Ezil 6&44)g 0ol ¤+. r46lq
tr|{^l r= 3.o0nmql^Jq q¤ gEzl vo.q4ql E61l^J +
94 *"1 84.
N/26JtrJ b+=+. r46}q +4LC Tgql ql6l]^J= r qHId
ol $ulz| 9'J rls_4 zJ* *AlzI
^dfl+tri.
z'sa :1,?-'e'-'
/ (3.oonm) = 4TEx(
NI t2l
)' R rms Tlal [+lttr ?oJ] (17D.6)
=-u;3-rllE
xlo {pm' 1:1300*l0rpm)l
+zlA i
X(3'00X10'p-)' Xe-(2s8 ol 4ql el6IH +*ill +flE fzl ftzlt;]jl ,r++
=1.92x10-*p--,
"J "J¤ ^lolel *_¤t_zll# 4r-lz| ivuzoll El+^J +7I4q
r++^J :.oonm"llr-l 6r= t0.0pm9 63 ¤9
(rB 17D.7), EI+^J 3zl-fl Tgq +q= N3/2ql "lr* ?zl-t
^l¤ "J+ol + +. ^l+ol zL+ aqlol oiH ulb ge_l a4q+ qI glzl-= +
"Jql^l gag q¤¤{H}6}q1 5-$a}ll) q^94 ?"1 ¤4.
ql+q oF *4("t4e _H_ol-+).
/(3.00 nm)6r = (1.92 x 10-a pm-') x (10.0 pm) = 1.92 x l0-3
=."Jel dE! url=
a_71+ Rs= zlzl:t_ +El'3 +E 9l+.
olaf.
ol dq HlzlES dzll +z}e+ 4* mol zta_ E dzll EzI$
"J szo E9 19 ffio14.
5"J+ +C EHltr. *Hul4rl sld 5rdg +EI.I=) +
ol Hlqfl= *9 qlzl$ol+. rz|fl +zie i"Jg zlzlt_
\
E 4l& rlgg o|4ql^l _H_olfl,q.
+4Le i"Jel 7l6IqI4 a7l= ++4= "JBe ¤4

zlzl
7l- 91trI. E+ Uol R.= gzlE+A flzlnlzlel EEqIE tl+4^l ctrl tJrl=oll rJEt
^l
+coJ rEztE z3ololr|. ?+7+4 z)olzl /oJ Nz11E ++lillE
ge 34. ?olE 4=trI.
,+r+E 4*"1 raoJ ru2fle1 +"+ill ++ltr. ¤ rzl-fl ++A a
E r$zl+ trl+r+
olag mâ44 aAl +=+
"JE +d EHI-E
^lg ^ll+-r.
R =N/
c
3+ Zo | (17D.s) {zlrJ ffirca? +oJill Ezl-E dill e*9-E4 mn^t=Nraol4.
E4l 1 +¤ E{Eql ++ ^l
Zq R.,n,E i."Jel oJ E ÎolE ,i4E ¤t ^ll
=-EJE-88 ,+7+q ¤=Jol rn ru211s_1 ss" + t=Jlle E 12191 +4le
*- {tE 4lt?ol4. r46}q ^l+ "JEg ",lE ElElTl. Rola "J
a"Jel EHIE(+*4lEol al+E +"J6I4l
4 +"+ill= Eq <tg r,olH R=IL r,7l s)a_ q-q_4 ?J+ 4 ^l¤ +Cql +C
Hl+qrrE a4H +"+illql ql6J a4 a+)= rl-e=$ pol
4zl dB6J+.
++B + ei+
(R') = (R.R) = i,r.,,)

i, j=r
=im * j{-.,, )
t=l
1=\m,dl=*Zdi
i=l
1?D IEII 707
¤zlr-l d,= 6d9-E+q 4* m,Tlzlel 444. "l 4?-l=

ElEl d,el Aololq, +d-9-tr.+El rH ¤89 *d lg.ElJ
++ E"+Eol zffig;rll AElg ,tl$olr-1-a g- + 9l+. +
E"+E z)olzl aI asrr-ol-l N= 200oJ DNA= q-s=4 e
d,=L'pl,o14. g lt# +4BtHldnm= 1pmol4).
5..412 + E}=*4lel 6.H_e_E+qE ¤+ aE
17D.6^lg +eI 414]ql^le+ pol ffi u1]¤¤ ole" *4. 17D.5 4]g-.tr-+Elr R. = 200 x 45 nm = 9.0pm
(2}O)rtz x 45nm = 0.64pm

^]gE+q,R,-. -
17D.6
i12
r r7D.7b ls-e.+Eli R, = (#)"'x 45nm = 0.26pm
j,k=l j=r j+k
{zl.!E +4}A 7"Jel A+ql= a4 o}ol 0ol Elq, E}+^l

+4LC i"J Egg s" rl]$ Egg +^l+tr}. B* e" {]= 7
(dr,) = il2ol:t i-oJE ¤t +^J EHIE= r+¤.4 Aol gtrI(+ .Jg ++6i4l +zlrll 6|q +e-+,H d+g lrrf.17l{a
q{ ?l+r -H-o}ot ++).
a4ql^JE ?lae-l "}+ql +ed=ill7}
B 1o14, +"* +r]]E r Hlqlel -sr+E +4']]rll ts 4o14.
rrle}^l ol Egql E46J ll{!e +=* +{] +ql^lb +6Jillel
1+2+... N=+N(N+ t)=*N2
rTlql EI6J 6I6Jol 9l E+ s" ol] +ql^lb +6Jillel rTlql
(r) = zm\(di) = 2ml'\ i=N 'ml'=Nm,oral'
i=l i=l
?*Al H trIl%L azll ^lE +9 +Billql Ell6ll^l 7l+ * *=+.
E4l 3 Csl Hl4E
ggE ol +^d EHIEE 21o1.1Rg24 ?JL+a +gq' rflE (b) +HJEJ
& = Mrol E+. trI4^J, ^l¤
zF.+ aoJ r
E'Jql^J EaJ4ol gtr alol4 4 zl4
^l+ i
R, =N"'/ dal HJÎE
[1D +ar8 ?g]
(17D.7a) il+= zl-+EE $..HH ol suJlol gC q +"tA + il+. a
^l-AE A+q=
++61 "Jd A6Ji$ 6J +?-lE +q^J ol
+q=E H]]6&9 ^84s4 zHzll9 e.J=g Hl+ "Jd aqlql
3zl-g +4Le i"JE a+qlE Hl*¤l 4l&g 6iH trl-s-r,4 e qldl^J zJE 04 gg tr-ql 4*9zlql ¤4 zll9 AB-e-_E g
ol E+.
+t]} ++C+ E}|6&3 +48 + 9lg 4oJrI. ole| pol zfl
7HE A-J 4Cql +?-l= leloNizl +l6]l^J a zlzl:il_
N del BJ^l= ^l+g
Rs (17D.7b) ee zll# ,1"-le+ dE qlzl$ql Eil6J
6 )''" [3D +4tr 70J]
=-¤+- ^lEqlq-+S
r+ eg qlxl¤ E6H=+.
ol A+ql= qBdE +78 agol q a"J6t|l qq dfl l-cosg
[ )"'
Hlzl=."l EJ L"td+. '-[t+cos0/
"_ (17D.8)
dq *zlE-$ 4E zlolqr4 +aql qloil^JE 4lt+ + 9l

+. qlE^J HlzlE"l R"J +"J+ ai.ll +E a+ql= & = (i),,,R 4Hill eqlE a+q= coso = -j(+ g = 10e.5")"lq F - 2U271
ol4, 4olzl 7o17I= +"J6J "+'ilel a+qlE t}+ql +zl* E+. tr|4^l
+ +flel Eldql ql6l]^l Re= Lt(t2)12o1+. +4La a.J4 E +EE 4E^11
(2N)'t'l
"J.J qlzlE4 A+9 *= ,Jill+= dxll4 o + apalzl ufl R,n,. =
^-=({)"" ^t+9 =.71
8E
(17D.9)
Eql dq HlzlEol cl =-4.

+ LA a"J EztE Eg¤- 41 4aj EAg 6I+qE qd
z]=JEt q 17D.3
6l +d ol E'Jql^J= olzlE + tl
E'Jo| Er+6I+.
zlzl=Î4
¤."J +4= ilzlg + fl+=
ulzl 3zffl +4LA i"JilH +lr ulSqzlE +!+ill=
q{= ^ldg 146l]
q
+zl ?*r
^J gl4.
"l4t zlzll IEJ6]]+H i"Jol +¤ 1o14,
4toll Ez[. re]+ ol l$z[ .Ie] zrg E"+s 3 fl"lzlzl
d4l a|ql ql+ 6}+(+rl] Et4zl s¤- trll)
r++^J R._,el RsE
?+sq, r?-l6lq ol a-$zli ,Jolq fzl zlz; t4 NoJ + ol4r B= aol +4.
708 ErlrJda¤
(c) #4 Z!-r.fl ig TlTl EJT| 17D.2 39 :z]-fl a"J9 +q Ep+ +Sg 4l
^l+E +¤cg +44=,tI +,q* 4E=

rH eol 6o1tri. t}6}qq
ol aol= a.4 +=Jal-$r+{I Ao-J dtr-ql "JE= ore ,E
^F+ ^l-+
el Fg 4olE +4U+. ,Jiil "Jql"J trll= zl+ eol
^l+ol
z[ El ,Jole] A+. z]+ 2o3 ffiC a"J9 4*"11E zl4
z)olzl + +"d=ill ++lE ?ols+ zJ4. zl4 zJol=
^l+E a 17D.t, Eqt4 ¤E
zl^del eE.+4Ll]= 4o14.
zl$ zjolT\ *%Iill zJ"le4 a oJ=q! rlolE
¤+ zI+ e6} Eg$ oJs-" alB +.Jillel t*r]. #4 4+
^h=E ^l+
^ll# 44= +44
a"Jql^JE+ e 4"141 zl49}cll, ol
=tFJ6l
Bg+ 9l+.
ag a.JE +Ezl 444 ull$ql ToJol t+6l|l +azlzl
?*zl ull+olQ. zl..rllE} 4lÎ a4q el6IH R,,,,<Iol q-q_4 g (a) Ee;| E==tr;
ol g+.
+4e a"J$ +47l7\tr-S.= +q+4E ^l-= ¤4o14 "l.4
^l ¤4
qlE +iilzl- al4"J tlEllql 6l]B6J+.
"l ;1gg a#ol
R,n,,= N"'/F. ¤zlrJ .=(?-r)"' (17D.10)
+E A}"t Atlzl ^Jzll SIF +ulz} a"iql4. HIE}IE
=?]H
E4 "*"1 trlt] BEl]E+q +4r-e 7"Je q= r+cg zlg4
+4LA z"JE a+ql= \ _ tolq, q4^J *ql^le+ ?ol 4aol4tflgul 7lq7l zltlg +zl ?+= eD. "l sgg ol¤:
R,,n,=rytrz;ol Er|. 6rlolH, F>lolq, q+qlE a"Jol PE alr-l rzl.fl trllel E4l q+4 tl_= e
^l+ol 42141l. "J+¤
q{+. q Hqlql fle;l E=e4 Hpl.ll +E-l {g +Eg + el+.
rl.* Eell ucE.trl=

@ H4zFl =gq =-EJt-4tEizat ztt} LIEhLll= =Et ^l=sl
^l
N= r000oJ {l6Jill zl! z)olz} (e+ ?olle$el
^|+E *+lE g zl+ ¤eL rz]-?l ^l+g 7)fl xEJ
z)olzl loJ ru21e1
-S$ zlolel 2.5o7oztlzl H6IH ol faJll
^l+ "J+E =-¤ + 4l+^l7l4L+ "J+^1il+r ^J46IZI. ^l-+el ¤4 d=+
+-zll# zl4zl ell6lflu + E= rJd6}4_t-+?
ri]. 4l&61-48 nolt mann EE^l Ozn.t{, S = kln w)g ol+
r.alE Sqr zJolE R. = Mol4. L = /oJ trll= ^l¤ 6]lot 6lq, ol 4cql^l + B4E olE + gl= "JHsl
^td
ol +4IA agolr R*',*do_.oil = Nr/2/ol+. trl?+^l l7D.l0 + wE 7lg ae61]ot ¤l+. =a6J
49 +4'J + 9l+. trI4,rJ
R,-. = FR.-,,.*do-.o,E
Ell 1 wE 4l4I
=-B
+-7-ll# 4"-lel EoI Egg q-q-4 ?"1 ¤4.
tl^Jol gle4H s=-+g 6}:ol-=- 4uu*)z} $$$-a3
^tse_l
6t= +(N.)E+ t*ot"t qI+. r?-l6}q
R-.-&.'."ndo..o, R.-. NL + N* = 7y, :.r-l-:1
- -( '/o
-,^-[ )"' -1
Rr*r,rrn.ln..oil Rrnrr,.r,r,lo..ui, / -,') N* - N, =,l.Ne_tr_ 5L lE -1(A+ g+)r+ 1(d+ _qE4)
9 Atg ,*E+ ++. relE N* = j(t +,t)lw] N. = *(r -
4+ +41"il^j ol Hs+ E¤.g u4E&e +Elu+. ol qr dtlg ,lrl= x =,a.N/(EE f&)ol g+. olE +E^)N
Eol e H+ Egg q+r+ a Bg.il6l-= rlBE ++(+ALe i"Jql ++ *9 ¤Eql^Je+
^
6 = 0.ozsR. = 0.025Molo
ol ¤+. Bol) q=q-4 eol +48 + 9l+.
&,n, - &rr,ondom coil

( zxo.ozsNl U2
- -1
R*.,.ndo..oil [-------'
= (0.050N-1)"'-1 tr,JAI? s"ll ++
^l
wql ++ ol Boltzmann^l o e +-gr+ ag Ar+= gg
N= 10009 Bq+B HEI Egg 6.0001 qq, El+^J ^l!+
= + el+
s/ k : ln N! - tn{;1r+1)N}! - tn{;1r-1;r,r}r
170 .ZEII 709
0
= -0.050k
-\< -0.1 R =Nekol Ir +E Ql-E + irl H+= AS* - -0.050R, I -0.+z

=
D
-i,tol
J K-r mol-'ol ¤+.
_0.2
5r
E-
ru
ml,_0.3
6:r (b) EJ¤
=Ehll
-0.4
tlAlEl4+ .J+El= +gC +.JillE
e.l+ Cql el6]]^J dll
-0.8 -0.4 0 0.4 0.8
Et¤ ++. +^d +.Jill= qel +?-l aq}g zlxlt-
{!8, 1= xlNll=x/R"l =:sFi{l4r
glq^J
Êql^. 4l4d-H ol +?-l ¤etol E4 tlElle EIE
fg 17D.8 gE EJd 6:E'-r]lel C= Eeloll rlE fl!=+tr| EEl. ,1=+13
qL B:tsFo_eL[ 316l EOIU SEt|oll 6t|=J6[ff, glE +tr171 7l+l tse /. = 03
olzlela 4q 6'Jill= !g ^JqE !E"Iz||l 6J+. frzl .fr
+6Jill= +i-{li a-J ^Jel ffi zlaj^d ++q qlgql
+AtE ?oJoll 6H=JElrl..
^te +¤g ++U+ zI+ aEI trI=
^l¤ol+E 4ltlol +g
+C +6Jalz]e eE"6J+. .+}d E^dill,. r Lll+ qlLJzlzl
¤zlrl 4l^"E3 zzl ull$ql(= 4ltlE A+E ,lle-l6l-H) d+ql ++6J +q+!l"lq, ^l+E ttl4 "J+r+ +fl¤ 4+l
ln x! = (x + ])lnr - x + i.ln(zn) E9 Stirting *r}4g oleo 6iq qg +E6I= rll "16.¤4.
r+g=4 ee 49 Eg + gl+.
eJE EJ¤i.ile.l LIEIL|{=

S/ k = -ln(2r)'tz + (N+l)ln 2
=+laj= ^.1
- j In{N'N*' (l
t*r )*'
z)oltl /oJ E+l NT}lE ¤ rrlg +4Ia i"JE ¤ sgg 0l*
t-'1 Ft
+ ( ru + i )tn N +.1.)Nt (1 + 1 )ttr( I
E4l 3 SEE]4 Hel.ll ++

6Iq +C +qlillE 4lt}4 gF<4 4 *-vl "J#)oll +fl¤ +
^l r= +44= !g +E6l= aol +4ol+.
a"Jol 5ol4zl 9+r al'llE +4|e B4fr = 0)E +48 *ll +14
=
ol fl= +vlz} ++4 ?ol 94. 1 +flqg SEeiile+ ¤+^l7l= gqq
EAI
S/k = -ln(2n)"' + (N+1) InZ -|ln N +C!l. zI94 o + 4r-l &"J+ z|94-o e 4jtl^l? ull ol
+^dillql ql+qot 6L= "Jg Fdrol+ 'il+ qlqzl H+=
^l+3 ++^le qlel Ql= +ul {oJ+ ol
,.R.trJ+ dU = dw,", + dq.""oljL dQ,"u= Tdsol+. trl{,\l dU = Fdx + TdS
=.?-14+
44 +41 2E ^lr+E zte+ e+. olBal +e ar+= eEl6l.a "l+.Et{^J
Eo$ ttlql 46]]^J= trIg-4 ?"1 84.
N> 1ol4= ol+6IE q-q_4 ,J* 4+7I +g+.
Î¤g AU AS
= F+T
dx dx ),
65=-]kNln{(1+,,1)'-'(t-1)'-^}. ¤zlrJ tr= xl R,
-drtl ?!=e.q Eo|. tlD +ArE ?oJ] (17D.11) Sd +C +*illql^J} Sd Tlilloll^Je+ *"1 4B "llHzlzl-
qHfCq ++6Iq("Je6J gEotl^J), rrl4^J @Utdx)r= 0014.
ol gIffi ae uD.89l rr^1a1*.9q, tl^J"l al^"J ollzl al r+{^J $7leol rl-e-$ *"1 Ert.
4 tl-=e-ulq 't13.g+= ag trqfa ?l+.
AS
F=-T dx T
L]trJEt q 17D.4
E4lz ¤4 s=eEl HEIE+EI E +6Pl
N= 1000 rqa /= r50pmq^l &= l50nm4a 6lz]. + B4 Ql= +ul(rzp.r1^l)= v|4"14 L= 717]|a- +4U+. 1
4e t"J(lil-tl)g r.snmtrJ# tol¤4H(l= 1/l00oll 6ll
tt} xz x=,a.N/(EE x = i.R.)E +E|4= rll ol¤-* ui-4
B) d= eulz| rJ-o-=q- ?ol H*4. =
trlElol+. tr++^J xgl *6J EEt+=,tql ++ EoJ+e Bl^+a
dx= Md,l"g +=+. :zelH,
AS = -j kx (1000)r,"{(,.
# (,- #
)''"'oo' )'''^*' } tr__rf as) __rf a^s)
N/(.alJr- MI a2 Jr
710 Er}'JdE¤
4 HooK?= -Ei.i
N 2
]--
A< j
E 0 -1
Ei
nl-
Hi I
F !
dr
---1
-1 -0.5 0 0,5 Es' r

t!8,,1= xlNl
.f.al 17D.10 Etd 6El"r1lel eEq Et= Hl+trlel Eei.0l + 4ld
fg 1 7D.e l^|fl EtdSI +fle F. EEol 4r= ttH= F7l' USoll +.8= sl+J6lG oJLl= Eol +al Eol .gE IsolE[.
=cal
dB4oe Hlall6lq Hooke9 =-cF^ll9
gzs]E
"J+^|iltrl.
azl {E +tl <tg z}6]lzlE tt}ql ++6l.71 qEql s= (5000 x 0.l5nm) = 2.0 x l0-3o1 ¤+. 1<tolt'+ 293Koll^J
^s
s f,oIE S4}+ olzlJ 17D.11^lg ole"ol$ +s=r+ Ag A4 e-l e.il43 rzp.r2b^lql 96ll^J trl-s-r+ a.ol EEI4.
Eeg+?l+
Nm
(' j"-
r= 3*
lY, /. $m{{r*1)'.i
OlL
*,
(l-2)'-r} ,= ':lllo ,: l]I('.?'")
5000x(i.5xi0-'''m)'
xr.5x r0-em = 5.4x10-'[4 N
= # #UL+,tr.) ln( t+ L) + (r- h) ln( 1-,1)J - s4fNoJ gr+

--
ff tLn( l + /.) - ln( l-,1 )l
7-
-l ,
17D.5 E4 dE
F_
KT
ln
t+7
7 1
x [1D (17D.12a)
=flei ?gl
M +lttr
2l r-T "t ^J 6JC +EI4IE AACS SszI +B6l tol-zlE g¤+ql E
6H^J ulq¤ + 9i+.
"lBl¤I acc H+= ee^d r;llz| $
.:=-5 ffia ToJE H6l-= tsx}4 ¤-8:4 r\-e- aol4I
^J4I
Holz} +g trllHl(1, x<Mql qiR6}q, trl4^l x<&) g + 9l+ +.Jill ¤+E E.6J I++ EE r,qlî "Jq
r}l+.Jg -eE
ln(t + L) = L* ln(t L) = 4"a dzlle}4. :rBlH,
- 4=rll, ol ¤¤ e-E= EzlZ} tr-g4l+q ^ll7le+ |zl rtzf;3
r LkT=NP*
kT -Hllan
t= +oltlq. qlE^J r4l ^JEHql^J rl¤E"l "J:"tzll ^Js4I
'= r [1D
-ll-
+4'g ioJ]
(17D.12b)
¤¤ 6l+
=?-lqp{lg
7', = 41411o17, l+E
Îolql 'J+
+i e-Jol ol+qzla 9l= +"JE 669 T* = s3gKolr+. d
+ EolTl 4* Q= ^lEzI uooke9 B4q q.q(rg +4"J Hql^JE C+e+ * ¤+ gEE *=
r7D.e). + H9l9l HlEll6iq, c tI+ &E rl-q-4 ?"1 =4^qEol
=iilqol aol H|*zl6|+
g+.
E_= q+c +Elill= *al dol c-E(rs)4r 6l-=.a+ g
.kT Eql^J olE^dol +e. tlEllE+El *g /J.EIE9 d"l
^l+E
"Jea+. +C +'JillE gE. *+q+H qts ¤tlol "J
t-_ (17D.12c)
"r- Nr
= d"l SsE ol6ll6J + flg a
+?-l
"l4alEzl. ^J46H-E_E
ol+. Ctl¤rq1,ri=- ¤*E"l +Cg qdg "J o zll #¤
qlqzl$ zlzla 9l+.
^l+=ol E=4B + 9lg eEq
6J
N = 5000 rql +Elill ^l¤g ^J46il
/ = 0.15 nmoJ
trl *g gEql^J= E=A4= eE9 d*ol +4l6la- rsvl
Ezl.
^l-+ "J+g
t.5nm{lt *"1¤48 1= (1.5nm)/
zl $Ez| 4flzlfl ol SEol $d6l gqpq ,rlez} *4
rz0 tElrl ltt
^l-.&q= *c +.Ji-llE
gtrt. c^J gEql^l :z #4 fr4 dol gEql^J= +'Jill ^l+3 ol? Eqlr=E +f;iol
^Jql-tr-
=
dol $szJ. roorE+ +ld oJ-o + {4zloh qLr+. 6ilJi19 +oJillE Hl-+rl(A=+ 'JEel q+)= gEql q
==7}6IE_E
6ll^J E^l6I¤ rrE ecB +E gl4(rB vB.4).
f'4 dol gEe+ 8& 8s= E4l=JHge +Cg + 9l+.
TllLI=
=sEl
tr1. zExl= at* Exl-Eol Eq^l "J=qd ql+61
= olq4^l
EÎ+. tr8. 4rt 74= 4= r$z}e+ qq}6}q
=
ts{¤ Bt6l-= *!
42. -8 trrteJi{lQl 6l+ 4}g E9z} {ffiol
"l+.
"JEqd 4,o14, A+ql q?+^l= ol!- ,r.l.ololl ii} ?aJ"l
=EE{IE
19. rl* /.t= Eflql^l= +.Jill .Jg A-Jg qL aolLt
ol-folzlzls. aJ4. =:d
f *9 A*ql ql6ll^J zl-fi-Ezll .JEE 49 olE + 914.
tr3. aE^l.= E¤zlol EoJ 4.E=E ¤ E+ E,ll"J +E glr" E. tr 10. +4 BEll= ,lel +El.Xzl ?+= rBzl-= +48
=gol4r
ealol uJZl Elti trl= !!,u"J +E 914. aJ4. +a=
"l Î.+
aq+
^l-+
Egg zlzla_ +4utrI.
e4. zEzI ^l-+E tr"lt +E=E +rJ ul]gg Eelle+r {}4. Dll. EJ,$-=:sFi{l= el+ 6Jql E6ll^J drll {lt}qa+ .J+g +
trs. rBzlE 1il +5= +qlill= ol= atg EzI &2159 ri ei+.
=
¤o14. arz. 6.JillE *44 A^l= EE -gEq^J +qgq.
tr6. 2il ?a= 4lzlSol ^l+ql LlQtll= +rJ E1goltrI. tr 13. 6JC +Elill= 8El dol EEql^J +e olEE ^JElls+q
47. 3il7E= lEzI9 +ill4 ril-?l +a+. L+e- olrEo EE lJ.EllE dolzl
"Jqtq.
=sEt^l=
.&-lzl
o=. ,\l
-1
ZA) al Ha
I --',t
oJ"Joli ¤+ E ¤%r M.=;i )ru, M I
I I total
zlo --1
ol l7D.la
+zl-¤+ g a%F Mn
I CE
ffitot^l L^,M, 17D.1b
-e-,r.I-c D=M*lMn ol
z-l
t- Ll+ o-- r7D.2
-d
Hs
el-= u* P = (2lT^Dtt2e-n2t2N lil-?l++¤ noJ 17D.3
flr) = 4n(alntt2)3 fen2z 3^|g +4Le ag t7D.4

a = (3l2NP)tt2
+zl{ i"J$ gqr zJol R.=M r7D.s

+ LA igE 44 R.-. = Nl/2/ 4uiqzl ?+g ^l¤ t7D.6
=_¤r-z]E
+zlC a"JE dEl tlzlE &=M/2/ +q}qzl ?*3 rx1+l,,.16 l7D.7a
& = (N/6)'/2/ 4ulqzl ?*g 3il-tl ^l+ t7D.7b

+ i"Jg *-Bt-rll# 44
LC R.,,,, = (Zlt|1rrz1 +E¤ 4Bill ^l¤ T7D.9
+ IC a"Jg tltlql IIIE ¤E1l 45 = -]kN ln{(1 + /,)'+,t(1 -,1.;t-i, 17D.rl

ril+l +4C a.JE ++lq P = (kTl2t) ln{(I + L)l(r - L)} l7D.l2a
f = kT/NP)x r<<R. 17D.rzb
Eq 17E rli{l trEt
ql+ olp ojulolE d"l?_o + H"J"J#

> 0l EEE ut|+= ol3 =ol+r
E =+
qa1 7l= H Elal| ttgel 7l*71
9l+.
4tg E^Ll E^l=9 El:BEll= o-qillT} .lill +ql +&g a(qle^l ++)e oilEfiolrtl
=
Eq. ol4-d Lt|E- 0l6lloPl +l6t|^'l= ol=el +Iet dE-
golol:drl. 6J+.
zlzllzl Ei]l +qlEt}g 4* zlEol+r E}+.
> "-Id 7llE
H3 Ex F-l :rE^ lEe-l r l^1 l-dcol I e.l6t|,\1 r llJJ4 o.tr
==eo s e1 E
Ee.o1=- g.+ t!E¤r+ 4E¤o e tsF6[7]s ++.
I
=61
Edqq ExPJ AtElttoll e.l6H^1 E=al?lrl. Eol +oHg trI= r!+C El A+,gol* +qE rf$a;|u|. aol
d ++ ¤ ?J+ Aol gl+. TlaqC ¤eol==
> rrJe.il qHl xl^l =sol=ql=
+^ e-Jg B^d6J + 9l= _oHzl *=4HzI 6Iq g
8EEIE{EE 178), Eillel B8(EE 16C),:raE olEE
HI4eE +"Iie+ s+q}4 os =¤
+Î* ^dAg z$lt_ fl+. AaI
=r[rJ
c|E4rE{EE sE)oil Il6fl^1 +^16}r ?lolot Elr}.
^lolel c ¤ol qlrill ^J'HE ol+r il= ag 4ol4l ql+.
qlqE¤g xllzllzle{ eg 7!*+ 54}eEE "J=qd+
(ES{6J qlq +-¤). dpd_"lu| 4l-gillql^l= ol4 zlzl *H
er9 Ezl+ l1+zl+ Coulomb, B&, +i e6J E= i+^d
r}s4e" 4 ?3 EzlrJ 0l+6}r gl+. EtI,I] +zl] 4ql^J Eag ?oI f L uJ
^JE4+ql E6l]^J +rl +tlql xli{l- =ol
E-sFi{E "J=+. a4ill edel BC"l4Ezl ztll ol^}el ¤4 HE 9lr(qls^J 4gE EEol_=), s dzl"ll+ d+E E
=
BqE ^J+E E *EAg 4iI +a= "lBl+ z|{ 4a;-E ql 4^|4^J d+g Ee.o1= zzle_ +lBlzlrll 614+ E4I"ll
+ql^l #4 a;g¤ zlzla_ olrE "Je4^J peolrz].,rj
=ol+. 7l4l 6J +E 9l+. sl+ adql E6H^l g-trJolzt
^J
=solE
?J + 9leq, E ol"l B^dg edq+ ¤Hzlle+ ee EAg
17E.1 EeO;=
flzirfl,rl ad¤- Et^lvJ +E gl+(qls^l a e =q-g ed
+ EeE +e g"Jol=0l +E Ee +ql +tElq +qql 3 s q =+e$r+ Ag EH^llE- ,lî Et^lvJ + 9l+). A
gE "Jeq.ll E6H^l Eqzlbrll ¤zlrJE ou-
E6l]^J z].4*zl ?+= ^Jg EEo15, E= E,ttSol+r ql4. "l9ol ¤H
olTl^J '41+. 4,',3 xlE"l E 500nm(z|^l%Idel rlrl aE) zlls 4L+6J+.
qEAe trE + CEg'J4l sEH rJzlEHl "11
4iq^J
oldtoJ 49 9"1,*+ rl]++el ¤EolE= +L-gulol(zl$
ol q]+ 100nm ol6l-el
g *Ap|^lzlzl fl6]]^J= qlgAolzll$ Bq +qot elQ. ql
"J"J"l)EE trE._4ol+. "JHI4gE
ol$flolE| ge+/l g}9 flzl{ Ez|zl-*d¤ 4olzl"J EdElzllg: Hl+(a ^l+E zl"J&g)+ += *= g¤x{L
r4E LJ+ 4t-oI^J B.Elel +rei ¤"la "E= _Aolzl ?+=+. e-= +{l^J +flql+ H6"+g ElSq+= ti.-4C ¤ol 4"J
+. E+ql zl"}ol Ecg qlEd"J ++q a+ql= "J*zlzl
1ry 56et x{E Eq 9l= BEa"J zl.,rllolo1 "llBdslzll_tr.4+6Ir. :14. :z
Bl+ 7|^jlqlg ++= sd6l ?}csl^lzlzl {a}q r46iq
+4lq= + tiE ++ql q-+ H{ol B4rl4. EHql rBol ¤cg+ ol rHe E&g xl*ol zlEHJge
=.EolE=
a_zllzl aqill +ql +&g a(qlE^J E+ql E4I¤ # +a^J stsql trl g+g 4o14. aeol ¤^Jq= Ag q'-e3l
flzl9 fletz.ll)"]+ rillzl t_tll +ql BtI¤ a(ql-+ E qlEdg +d E}l+61 #4l BtI^l4ot e}'l. :a$ule u3g
^l +4 4{1 ?ol +tlg +Hl +?]= = + 9l}ql,
r 6}rll
^lq +E
olEJ a.45- Eg + ilErll olElpl zl4E 6J
t}+ql E-* 4ol4l3 ++ ++¤'te'++4r.6J+.

^qg =ol+r .Jzl]4 ,'-uqloJ
e4;llzl. Tlill +ql E&E a(qlE^J qlqE+g "JEE 6J ol$g Tlillel E^l-= olf-all,<l olrll
f,)
olr-i Iillzl zlzll +ql B&g a(qltrrl ¤zl)3 0llolE E ++^l7l= aol+. ++q= "_4i]ql+ d6l-= zrg^l7lE
17E E-d 713
^li{l
44z1zl Hig zl+ ,4l#glBtl"l q a ¤4. ol %r-He qlE

I
dS "Jg= EllqlE ole" ¤4. q7l^l= 6l-dg "-qill^Jg +=
e4i]l +e_E E¤^14^l qlEdg "Jg= 4o14.
gEolE= Czllalt rjlE F4ol g6l ol+¤+. ol *Hg
ols"6IH
"JE trll olg Eeg zll4+ f
=-EolE= =qZI
9lq(+ql ¤EaI4lzl"J $dal zll4^l 7l zl ?*=+). +,ls+ "l
gg Er+^l7lzltrJ a7l7l EEoIE ojulol= 5:4^l7lzl
?+= "+(qls^l gEEe ="-l)g- d6o1oh
6J+. F4g "JHI I
4 o + r]l+61 L?]q ol qlEql E*3 zlzlL glt: lal 17E.1 4 E^tE ,\l'ololl= tlffoll ulall6l.= "Jqol "'JP
=eol=7} ^+E6[^1"J,
d6l¤ dzlatg 0l+6ll^1 7l^+^l7l= +4 BH"l ol+qr Erl=Ql *r3 Tlal(c-d Bq).E.q-= Eal EolT.! 71al(Ee gq)oil
=rtl6l-r]e
Eill8E4tE ollLl^l= Hg q+E 1/R0ll Hlall6H^1 trl Ad:dtr|.
:14. olq+ "JEg d7l F.4ol+a 5J+ ^1^161
ol$ee*l ¤.d619 449=_ "J=+. r44q "l zl%r ,Jg=

(b) 74q ?IEE g ag a6F= 7*a_ EElEzl ?+rll g+.
^JE ^JE
¤ils 9lg trllH+ gqql4eE B"JC6I+.
=EolEE =
=
gqql4_o + E oll, gAql gEe+ "Jq 6lql^l rleel E (c) dzl2-
H4ol doql* HB tr]l= 419 Helmholtz glH zlzl dA _ ydo s"E4 ?}aEq +g g"Jg "J"Jol -EEql gl
"J+ H6lq(Eq uc), trl4^J sH4ol a}ig oil aa<ool =sol=g
d6I+. "l d6I qlEql HI4 C6I9 ol9ol r E?-l
¤+ qzl\ yY -EH tlqol+. u}+{ Sigolce-l e-latr-el =
Elr =zlql
ol qlEql E¤|E olgql^Je+ u[]z[z]E ol$
4q ti?]
"JCE= +E"+4 s4ql 7l9]++a Ezl 9+¤- + Strl. + zlzl BdE+(Eq sF).
gqq!4etr= E"Ja6Izl"J $.E"+4e+ "J¤ ol d6l+ + ¤9 o + Lli-q^l
=EolE= ++. +d arll= ^846l]"t
6I+.
Ee.o1= "J"Jol s.Bql ++6lrll Eg olg=E +H.Jql
abql= rel+ gE" qL4 o P tr ¤Bol ?l g 1?ol E"J ol 6ql= E +z}7l-E6Jq7lE +trilEol zlzl ullpoj a+).
+.= Esol= "J"J"]E3 grtqql^lE ^l.E ,g.ol¤q rq ol ?E+ E{z}zle.l l}zl# EE HJrl=olQr 6l+ql, ol
al-¤ olE olE¤ 6J'"iq?-lE +-+El= tL44 .J
Îolql= 43 "J"Jo1e-1 olf,rE Ae6l+ +s qlxl4. :_41 Eill ,ll
ol zle" t4. ol *44 c3 trl-sr+ ?ol d4R + gl+ +
aq q+ ol d+ tlxlEoilrJg ^J44 d7l4 tr{EJ!¤(d+l)g
d ^JE +E- EEolc Qfulolq +d+ + gz} ,'eli ^l"lql= 414 d+l 6,E= llE $fl+l+r 6J+ E{ls ol alz$zlli
l/Rtql E=61+ "Jq qlqzlzl-4*drHEq 17B). olE E=
HlEil d6l9 ol+d olgEq E?lzlE.qBa+. ol 4+ d
tlt} tlg4}¤¤ q61l= dill ^Jg I+ qlqzl= l/R,ql Hlql t;l4e4 Ble ol9 E+lzl= E7l 2==ol4r 6J+
6l+ AqzI E+(A+4ril= "J"J"l9 jroJr+ E}gqlE E= Aaq^d EÎE E{r{l +6J "lE* s. Derjaguin4 I-.
++). {zlrJ Rg + "J"Jol9 +c ^}ole_l ,l?-l+. Landau{l elall^J rqr ol=r+ 584_o-e E. Verwey$ I.T.G.
=EolE
HfzI e o e.+ri 2_tr E6k- ae 5}g 44ql^J= A+q + EdqB.eq, "lag DLVO ol$olrE qI
overbeek9l E6ll^]
z]EJzl4"J tEAL¤¤ 6Izl"J g?-l Eq4 flg trl]= "*g +
4. "l olEql^J= olf $ujolEE 4zl z#"1 += dfl¤
zl¤ol CE Bl+qI 4?-lql^J 4 ?ol tls4l+ "llHzlql zlq
^lolE Hlgq 9"8"1 49 Ezl¤ ^Lolel
vanderWaals tl-g,
.6Iq(rH rzr.r), ¤4zl " + t"J Ezl--EzI {rs4+ql^l 4L+q ts"1"J3 tr-E oJqol +Bg ol$+r zlz$af,Q. $zl
ile #+614tlf{r{^l ?*zl ullEol4. =ol aoJ ojujol$ol 4= 47]r 2#E HlBql 7l"Jq= irlHl
"l al|?] "Jqql "+^J= qfl zlzl eols-ol gl+. qls ¤ qlqzl| rle=$ BP Ee +qdq"
$ulol EHql= Ec.q}o1 ilq^l 4lB¤-
"Jc
^J =solE
e+^l7lr. E +E oJ"JolTl Ea_ Eqszl *6}4l ++. ql
t
Aa
2Y2
4.prl.ion -I -b (17E.1)
E^J +¤-q +E E+=q g.H flzl-b Elq| HI+ql E6I^l "-'t"'
-Pt(OH)rHrE H49q 4+= H_a-6Il +r 9l+. E zlHJg ¤zlrJ A= ^J+, (E zll4 trlHl¤, Rg +d. ÎolE 44,
'
Hl+ql el6]|^l qlpdEi q=ql, oltrll= Bl+E A +q+i rz + "J"J"lg sE ÎolE 44("J"JolzI qlzlEol a"J 7B
= trllEs=R
4zI zl$ 4{ {lzl-7 :7 zle.+.(171(o}d ,tllzll9 a+ql= "J -2a4), rall. roE2#E +41+.*4&z+
,lE} 4+rl) El?-l= zlHJ9 sB_o + +e+ Er+ +^ a6-Jg +g 4= arg "J"JolE a+(ro)a)qlE ol ^lol ¤- "*=tr}.
71t+ ErtzJtE¤
,*E z6e"l $9 <a)ts trl+ o ol=HtZaTl "JqB + 9l+.

^lg 4d -+ AloF +r+,
4l(ro
olg, 561 s$ d6I9 ol9¤ 716}| +E ol$.rllzlzl *zl
Y..p,r.ion +
- i Ba' (' ln(1+e-'/"1 (17E.2) a}q :_4aI{ ol4e} olgE"l gzJzll9 4}¤¤ ++.
r
+EE +.g d6h+ "lgql el6l]^J
Rlql
^+
^J
=EolE.
6l trr+4 o + 3 %zlAl ¤+= aol HI-tr ¤E4sE ge =
Hlq d6l¤ Îol9 "Jqql 96J dE+ g6J4 g&Eql E6J Schulze-Hardy ffiE
t{Sol+. EHI 49 olgol +61
Eilill ar+ z+¤¤ rEJ+ q-q-4 ag 4¤. ol+ ^'*
E+4olq ol ql+ql olag eol s"r= +E6l+ EE e_E
Îolel a^J
6ll^J +B f ?lErll, ol Debye-Hu.1.1 ol$9_tr ol¤- E ol+qr fl4. tr-Ellg TIgEol 6}aql^J HI+E g
^le. =eolE
9izl9 +41= +1{H aolq(EQ srg+ ol nxll fl,t}o1ee1 +l q= A+Eol {g "J"J"IES Szlzll 6J+. olag
=qA
tl^llt 48 rl. 6l-+ql ?4eel +s g?lol+.
^JZl
++,tI+E ¤Eg "Jd6l¤ qel= a6'lol fleq +aI +l
( eRT \'/2
+
'D-[
-l
I
87lze=94 +t{l (17E.3) ++ ¤g *d6l-= trlElE AoJ"l il4. zI¤4 o + ^JzlE I
2PF2Ib" )
Ezl¤E Eq E+g trll d6l-= eAl qq, EEAoI+ zlEl
ol rE +q4g olg
z|¤t r+zlq ¤l +s6J 5^dg olEE dill d6Pl ,l]eel
r=*z,z,,b,tb. {zlrJ
-
^lql^J ^-ll7l(sF.z8ll, pH"il E=ELtrl= 4o14. qlsî
+|aql^J= "Jczlz} ¤
b" = rmolkg-r), p= r a*
'JEoltrI. E- F|. Faraday tf"l ^ld dE d6l7l "Jol g+.
Tlql EqBg-q, r?l6lq rEzlE
I" e3 +dgtr^J e =s,sool4. oJ¤ tlg "Jqql zlqllE I
¤zlC qlA +ql^l= "J^Jzl¤ Szl rlEql dtr {o}z} $o1
fl¤ qlqzl= trl++ *r+. g+.EldE pugl.rJ= rBzI9 da d6J.7t o"l ¤4.
L
%**on s
(17E.4)
GZEil EE4tret
=tEeE
¤zlrl c= E. += t1-+4. olE diil ElHl¤ qlLlzlel 4?-lql iE q{a E+"lld dzlt}el ¤6}_e__tr ol
"J+"J(BSA)oI
trl= E+= t4 vp..zql +Elqlflq. Eo6l* +qg ¤4 pu"ll^J +86l.{ o].4e} ?9 rll"lel
efl+. ol +EAE Eddg +6Iq+
oJ$ ,rllzlTl t¤ ullE
"lg +sl7l7l aeq, qHr¤ qq =
zlE tL'J6l H 4?-lql^J xil2el + dg +4u+ ol xll2 *
pH 4.20 4.s6 s.20 s.6s 6.30 7.00
idE .JC+ Erl trllE9l ..JzlE ¤.dg Ezol4jl el4. ol 44/(pms,) 0.50 0.18 -0.25 -0.65 -0.90 -r.2s
Be tr"qlql^J= ElBl¤ 9luJzl *Eol geq, q{^l ^ll4l j/
Hlg 6fl+E +^l E4Ig "JsA+. "J"J"IE Îolel 44214 ralE IB ol +qg pHgl q6ll^l EÎ6IH qr*Hg
+61 zl"l-4^J ol ojulolgol ElHl¤ qlqzl +dE zflr lr ol+6}q 44ol 0ol q= pH= +B + gl4. ol pHoilrl
dql $qz[-L vanderwaals oJo] zlHfl4ol ¤ rllE zllECS ol +Ee EzlE dg. a6}zf oo1 q= aol+.
zlu "J"JolEol ulzf${ o + Erarq^l oJ"J"lE Ha}E
ol rllolQ$ E^l+ 4.ol :zB 17E.3ol+. ol +qg
= =ol
pH = 4.8oll^l odg F46Iq, trl-z}^l pH = 4.801 Eo
ddolcl.
ro9 57[
fo>> 3 1
fo<< 3
0.5
4.8
j 'r,a0
K E
5
{ru
o
0
Y.o.u 6?6h
ffir
Er
E' R {r
olo -1
o17l
oo ))tl, s
-1.5
aE,J 17E2 F gflJol gE^tE tr1El¤ oilLi^lE g{J=g 45pH67
Zalq r+at E6lB{, EEI SJol =7|(U^l= ag! ?E SJol)et =C
^tolE
E7l ^tolE
25= lEl 17E.3 -aErtE 015 ++g pHoll 4atl,ti E,lFlG +qol 001 F.l=
Fzll reel9 ul0ls, EEztcI. 3]1et g40l golLl= gqql^1ts 0l trlEJ!¤
0l,i0l #tr01tr1. qTlE Htl
ollHrlTt Lt|4Bt=tr|.
pHE *eE E1lolEE t7E.1E aol+.
rzr x[i{l flfl 715
ItTf 87[ 17E.1 offi r]lolQ= += .J +Ee$ zlzlt-

Eg aol+.
pH 3.s 4.s s.0 5.5 6.0
+41{U*r-,; 0.10 -0.10 -0.20 -0.30 -0.40

Fdde_l pHE +6Iq+.
o't'E
fg 17E.s EJel#a EÊ Eol Ealg r]|= H2O ExlEol HFq Egq
+aE Bd:Lltrl. Eol olal-d?4= ,*11 EIE r El=+ulzl AA6[q, ElelA
EJa4^rt 54011 EttEl= ?lP ?le-anl Eoll^l EaEtct -r,a1Lt 0E +ale
4zl z#el +qE+g g"rE" qL4 "JaEE 441 al-b 4,ol 5l-Ll'6fLtE EJel#+zl- olg= E¤61'E +alE E8:*trJ E ErlTI
=ailt?.! EE0l'7[q ral6lq
+.+ E=_o1= oJEJolTI +E6Iol 2# El E9zl^J + Eill?4-e Eleerl$
=7l^lilEl.
E"l4zI qEJE ol + oJEJolTI qlq
=
\$ zlzla_ +rE=6Lq
s.tsE ol3+ol4 +r|]El Ezl-?$ z]]Efl4+ E= g+F zllaJQI rj4rallEz|. oltrll=
4 Ezlel A+C ^l¤ol E EzI
ql E6I^J -EEql +49 d6PI gEEJ Bqe f fl"i"F + E +ElE EqAt"J 4"14(:H rzr,.s). olElql e^J= EE ql
4. "]fl ¤^Jg +e gEql^J "Jqts + flsq, ¤9 zlEE = eqE .tfaP tL=1|ql^JE 4 olalE zlt,<lA+. +*ql=
'l S7l+ 4E olaol t ol*o14. ol i+c ^l+=ol +ad 4+ tIEl]E ^J4ollHzl-. "lqoJ +
idol 419 fll= +!lE *+ol izlE 6lzl"J +?-19 izl4
17E.2 EItral gfll+ o}Ti^l *e E +471{f+rl ol$ts + glzl EtrI. El+^J
A+^J rl¤Eol E-zlE E ts4¤g azlol eiqq r4
++.-4 +ql^J EH ¤}C EzI+ ol# Ee-o1= 6|q 4lE 8i= eulzl 'd¤4 + *zYolAl E+. +rll(E)el
0
ol =qEq^l
a7l4 "J"Jol"J EHe 9=rll, ul.$oll,$= r afrJ :14 ol 8l-=+sl 6zlE E+ql^l A?B TlEol zlg4s-+ E.l6J
.ol glr4l Eolr(i+^d tr-E4}+ql E6l]^l) Tr?H "14 zl gtrI= ag("JE4.J tl$q s47I S.=.J) 9"laJ4. E4
ql^l TlEol "l7lH zlB4 "_e. +Azl= ae EE6l
^+d
Ezlt ¤ qE"l4r g + glsq ol cg 4+d dEsf8ol
(a) a#C 8E4tE +r'*q
ol $-all(ulg ¤C4 ++6lrll) $eg gqql4"J Hql^J
¤lB-t-¤<cH3cH2cH2cH2cHroH)4 ?Je 7J
^l¤ "J7¤¤ lda]JeH ol r+eg oJaflali ql q E¤.ol ¤ 4"14. i+
^J46}]
_H_z|. $ffia
afr.JolI oHzlS tl?tso]4.
^F=g
rl?HE + Sqg 4= slq}++ g=8 Ezt4r- c Ezlz} Eql +6119 trll= +t}q= +eg +-s-o 6l-71 +16l]^l
^?Hr+
6J+. "J-C Eeg Eql a+ +eq, ol 4cg olalalzll I E Ez}el A4zl H6l]oh 6lq r?-l6l-q
slE + trl= oJE
+611
H "l¤"14 ^Jill +a7l qB4l ¤d9Ezl$ olaflo3 + gl+ alol E4(Aa*.s">0). ol 4ag E4l^l oE ¤:g r+aolzl"J
ol +6]1 4Ag a+ q +ill4 e_tr olollalzl 9l6H^J 7l.i4 (Aa,*,H")o) +6ll Gibbs qlLlzl(Ad*G")E ot4 HlolElql^J ts-
o e ol "J7gol ,Htr4"J BzI ^Jqls + 9i= ul-s+ ?ol AB4s+ +el <tg +4U+.
=7lql= E+ql^l =
q*dl ar*rfl Ao*s?
(klmol-') (klmol ') flK-tmol-t)
cH3cH2cH2cH2oH -lo +8 161
cH3cH2cH2cH2cH2oH -13 {A +70
ffi =
+6il qeJ= a6&4l^+ i"*_e-_+)ol
A EzlE E^Jql 9fl zlqe+ E Ezt9 +a Hsloil TltEl
E Ql= +rl Hs| utiEol4r s4g + gl+. "J* +a Ezl
+4+. ?l"Je +
,I +4qH E +zl- +z7l q H6lq "lgg ¤c6l4l {}+.

aeJ vE.q +E trl¤el EE Tl+d 7l= +4. LtElLtlr 4+d EJal.+^
ol deil5.g CH,- zlzl al\ *zlt'J oll"l-4 .s= cibbs glH
LlElLHfltrf.0l=7|=P ?E¤= 7l^lr. ?Itr[.
^la=e =)14
716 ExtZ! tE¤
zlzl -3kl mol-'trJ# H++= +zl4 g "*=+.

"JHI el "JC+ dol ¤Eql^J Eel4 C¤Eol t"E9l q+ g+}6l-
ol belr+ag 86il^l +il+ ^le + il+. 4L zluJ ul.rj$4 + H++. ElEe_l Er14o .ll++ TlEHlg
= "
e +zld Rel A?Hg
7l ^?Bg
r+q=4 4."1 C99= 4a,5 8+ 4zlzl +EHe + fl+6J Hlql 96lE ul¤ 4P
r+ g^1614.
n= Tlz.la_ A*4q+ +4U+. ql^J Be++i :l4=
^JB+ +E^Jg zlzlt- ileq,
ql* +
El+^ +ql^l Eq Ea zllEg q tsg aE+. ElgS:z I
, m
z=lo$
s(RX)
611 4+ qEql &B4eE+ dE+4 o + q+61 +,q-6I+
A+ t¤e1 (17E.s)
^+d qlE^J ge Ee$ol ul¤9 .ll+q +6il9 trl-g Eql
{zlrJ s(Rx)E E+6JE RxE E4;4 +'lle *E-r- ^+¤
E6ll^J eHlg + gl+ ol trI+ql "lE al=
^?B ^]q^lls^J, *zl
gql rI+ g +tilEel Eq q+ E +6ilEe+e-l Hlol-,E s(Hx) ilolr ?l+.
^l+ fl+ Eql
*^d, ++ d"J, "t
s+.JE rx9 +Egq g +6ilEe+ Eq q+ E +6il EE g.^d Ezlzl dBillTI gzl rlzlts trll sH gc Ezl
= '|]qI
EelE ul"l4. trI+^l 7g9 atol "JolH RXTI RHE+ q i+ cl zl-alfl BE +C"l "Jq+rl ol¤9 z}ll e6J
c"Jg ++Lll= 4"14. dit a4q el6tH q++E TlEel =zlls{=+"J
zzlzl fzlalE +44q, r?]6}q ul¤"I -4
rtlS x(oH, NH" F)9 ++ql E=6lzl ?g=+. rq+ de 4l
=tg
BCq+7la46l7ll t*"1 4zl4l g+. "J"J zJufl{_o + 5
Ar+ql 96lE n(13 cHrzlTl 71614 ull"I4 E"J+ zzltr- afl6l-= ul,tj Mrol NTH$ +"*Al Mo + ol+qd+E +gr+
#zlaJ4. ?3 zluflzl ¤¤g ^J4"llot
6J+.
-R -CH, -cH2cH3 -(cH2)2cH3 -(cH2)3cH3 -(cH2)4cH3 NM i= MN (17E.6a)
ft 0.5 1.0 1.5 2.0 2.5
*iziri= +%F4iq Eii+qi fr. +l{E.+ ziAolzl".I ol -8

=7i
er] $fl4aE El rl¤ 4olzl rt2fi;);
tr++^l Hl-rr-l
"_4¤. "l^J4"l4l zlzJap
g-t.E 4{ql E-tsE=
^l-*6l.
+ q $lJ o + g+r t:J6J + 914. olei6J ao-lg ^l+E fl4. "l¤e=z 7J7J lvzH tfzl-s=e. ol+qe+a_ 7l^d6l*.9 Ir
tsi gzl^+z} fzlebll ,tl{ ad*c"7t q g-e-E q=ql, + -e. g.E gCzll9 dal bE= [M],o,a = [M] + N[Mr]ol g+.
ts-r-94 SIE-I-99 qlolEl(*E ilg -H-o}+)ql 9alH : trI4^J(+d-6}zl 9*rll c"E
^J$otI),
fS a.4i fl-E eqql zl"J¤4.
(O) OI¤ E¤
^-m
tz- [Mr] (17E.6b)
tllgg g4 trlE critical micelle concentration) ol4-

=E(CMC:
g E"EelKraffi _.e'E ol^J"ll,rl"J Bc$rl. CMC= +qqE E ztEEt 0ll 17E1
ca, r +ql^JE.61 E- dEtrE +Eq41 E¤+4 17E.6b^lg +il al{}e_E Eq^l trlgel t.EE dill Ets
+EE ++E +48 + ?lg-q, r er+E "J+=
"-14
Ho15 tr 7 *olg + flcHrB 17F,.6). cMCql^J #H6Izl {*rdxll
?+i. Eflzi ^JeE $.zl ?*eq, olfl6J CeEg cMC ++l t4 rze.zql +4'llfl4.wl trll= ul¤e +
= =^116l+
xl-=el
^Jqzl
EoEzl +46}111 4zlE ag E f ?l}rll,
olaol cMC= +4'll= 4."14.
ctrtr
B{ x}a{
LJ O-
Kru
{0 Hlolg^d -g.E ¤Idzll Ezl^b 10007H ol^JE +z\7l q.J6l
Rr
il
o[ll { "l¤g "J.q, aJ¤ olgrJ sE g¤zllE "lel zlg.r.l-o1
Al.EO}
o-T- tl E ¤ 1J214 Hlg trllEql BE l00zflulu3g Ezl-tr. ¤ "l¤g
O
"J=r+. rBl+ "l¤g B4rlTlEl= Er,+L d6lB+= *14
++el *s_ zzlql q =.rll E=+trI. qls^J srlldE*&-4E
c)
ggîl tsE
E(sosl o
1 + tr E+-^ll B E?-l Ell E "JEE{crAB)e+ ?9 ol 3
fal 17E.6 E.ElHgttqEEE +a-Eol r g4l El¤ Jollll
c sH gCxilE 4B+ *Eql^l
LlElLtl= 8trEE dE4E Eet -egf.
-EE(CMC) = "+q E"J "lgg ElEzlEL
=al4
17E rli{lE:* 717
0.4
T
olll 0.3
nl-l
tll
rlo
R
Klt
ru
0.2
N=3
-z
Tru
E 0.1 /(= 30 (x 1Oo P E}IH )
lal 17E.8 +B alE+E .JE +4-
0
0 2 46 8 10
uSxll E^19 Eill+ 4. "l¤9 "l*l+ e^14"J u]]¤g trlE¤ EZ!88o1+r 6I
a4 fiE.7 K= 1?.1 e+, Elgsl tsE= Eill 4lE g¤^11 tsEq EEg
.ql, E5'o-441 ?c^Jol4l +=+.
g|'#e +EtL,! raJ Hl+^d +'il +ql^J= Etrl¤ol BClErll, {zlr-lb sH
$Cxll9 4Ig +^d "i4 ++ol "lB l-ll+= 6F"E" Pulz}
4zl} A+d :z?-l ++ol *zl +{| '.||=+-tl +e-E +e+ 9l
¤=J sH 9d4lE 4^ll4 " + 4Le +¤ "l¤g qlE4. "l¤ 4. olElql +¤ d.JillEg r tll¤ q+ql +=JE E9 zlF
Eg g6l +fL Etg ol+q z]]zl]9 ul$ !_olE ^dE EH {E-e-Eal #zl *r]] +E Eg zll4^lvJ + ?Itr+. E.E $d
,B-C tszl.el E*, Eo E, rElr gEql ul4 H*trt. trl¤el E 419 E"E7I t$ "ll= d'J:ll7l *At-l +lil e^J= +Q'llE
"Je q-n_=* ae- EE g¤gl trlaFlEl N,E ol+6ll^J s!+4 + Hllgg 6Lq "Joli]+ +4¤ E* +"J* ¤E]lel +4
o+ ql^Jg+gl+. . +4U+ =-
ol"l ¤EeI ule| ?"1
"l¤g A+C ^Js|L+ql Efl^-l ¤
,,=* EE gd^ll tr|afolEl (17E.7) Cg+. ol "l¤ ¤^d qfp4ts "l¤ LI+ql^JE ,,lE ^l+=
t89l
^lolel tis4ls"r+
+C "14 ++r+ ++l "l]e4E 1t44-$
¤zlrJ y= a+c rz4E +rl, A= rl?H "lr-l +89 H"l, 9 zl{e ol+qd+ q4^l El¤ Bc sBq= dzl EEq
r4a /g r/BI ++9 al4 ?o14. s, rzr,.r3 srl6Jill +ae+ zl ?+. "J^Jg +EI4q "JE <tg +El-HtrHsg) +E a}g
EE g^dzll ul4"lrl
^l-olE
E+ +41= Bq++ 4o14. +Eltfl+1$g) 6J+. "*3 ul-olgC "l¤g gg4e.e ¤d
++E +ql^J= tA ttp..+e+ Ae 7¤ "l¤ol e^dq=ql, Elq gdzil rE * nryl rOkl mol-'9 zt4f7l- ¤+. ol4*
EE gc4lq +^J "14 ++ol ul¤ sEql 9lq^J *,ll+ "l¤ol cMC "ltr-ql^J ¤Cg+= 43 "lEe] SC flE +rrl
+,]] +9 olg4 ¤al t1-s4l¤¤ tI+. "l¤ {+ql^J= 7I "Jolr+"F il+= 4¤- 9"lalq, +C A4ql el6LH "l Ql
+^d tlazl*ol EH ¤ICzllE A?ts r?-l q6Jg "JeE+^l
^ E +rl H+= ¤gql^J +1401K-r mot-r AI;7l g+.
a+. dE aa 6|ql^j. a|E+g ¤^dd+ql, ¤zlrl

=aEI
?]E+E 4+E 6;E6l-= eÎel 4P sflol el+= 6F"l-b (c) 268, E-4.9., :laE Erltr+
=
e.l+ +e_E Eqr+"J aol4(:zH 17E.8). ol r]E#e e.+ +
ql^J Hl+c E +zl¤ +HI6l-= trll ol+¤ + 9l+
CMC-H-+ *'J6l k3 E"Eql^l g+ "l¤g + +zl +4lel
H¤- +xI EolE trJ,s 2==¤ "J=+. q7l^J= 4 Ezl-Eol
++EE ol$,tllzlzl |zlal$ sH $Czll "14 5 E Î"l Eql +z16}4l F"lEHl, ++Eql^J= rl+^dzpl ayzg
9 t}tsol e^6}q gFB "l¤"1 BCB + 9l+. ol 9]5= "lg
g +^l E ^J'JqL a"J-+"J(+4 "Jdq) B{E +LolzlE qL ffi o51--r. Hl+C ,l]e +ql^l= .J+g 6J$+. +tr-
"laol
2#4.J+= dqsrllfl ESEJE E-Ê(4L$ f"lt])z}
E 17E.1 EE gSIl 4afnlEloll nl= olS fle11ol E:-l "JEqzlErll, {zlrlE +¤E i+^d 2# ?¤ol ,-ll+ +
+.-q {}r+ q+ ++aq zlg +?-l^l7lr 9i+.
N,
"l¤ s"J 2# +7a aÎ6l+ ql
^Jill ^lls"+r} +^l-6}q, ^Jal
4.33 +e s.gE zt+ "l+E+ :.fl{ ¤4lel ^lleqls E|]+61 +$
0.33-0.50
0.50-1.00
?]E"B EqI
uLr--u.
-1 4
+ +eE zlzla_ gl+. ^]lE"-19 zlt +a s_a= sr-+q
1.00 ¤H z6e E-7fl(1)4 eg "Jxld"Jrll, ol "J7la-7fl9 a +E++i
>1.00 qrJ6J
"l¤4 zl4 ¤4 ^l-+(EE
c,n 4zl c* H+lE)4 qBl +oJel +^J 7l(qla4
718 ExtT tE¤
-CH2CH2N(CH3)3+e+ Ag)= 7l^la-"l A+^d ^l+g

?14.
+q^l "j s"- +4lE 2# "J=+. zl¤ Ezlz| "l¤9 ¤
^d6tzl 9*l
olel¤| 2fffi "JE= 49 +q4a ^l¤'ol LJ
+ +q= ,*71 qBq +¤ql zVt# irlqlills +g + S
=
7l trll$ol{.
o
!tcHtr-=,_
crs -(cH2)7cH,
OWfrmfi
(a) (b)
o- o
JO>_\ fg 17E.e 2¤¤ êl EJel+^ BE80l SEoll Elal E6l.=
+(H3C)3N
\-/o-P-o
6 (CH1.,o-61''1.
^l¤ gEoil^1=
a=qr4
-=.$. (a) qr lEg ^t=E
trî=,*^l,J
^l=el
E-d E#
flr 25=01 e4r1l ,JE-oE 1 (b) Eszlxl LtlaUfE ,\]¤ol
1 E.^trlElg3al rHill4oe EoEz 2#,J =rHzl'trl. =8Ef
8Etl7f Etr|..
2#z tg "l+d +aE zlzlt_ ?l+. +sl+a ^l+5

"l +d7l ÎolE gEql^l #"Js"l HIEH+ E"tZl4 c. E.
"J "i'14 "Jzl¤ Ezl-=ol EE +lql^l Eot+qzlr
ajq. 41 +q trl4 /J.ol* Hl¤.E Eqfleq, zleel A+^d ^l+ol +
EElg g+^d +Z7l otqq, Eg rooull# q= d^dEE 7I +:61 +"lzl g+rll s}e-Eal B++ as gqE= ag "+r"
zlr 9l= d¤ol +ill$r ^J461+ 4ol ¤4. d¤4 o +
=
r?-l6}q +dg ^JB+ gE Hflq Aa ulzlzll
^lls"+E
^llEEt "Jql^l
.Jzla +zl-=rE E"Jql t4.
eI r pmE olE" qI+.
EE zl4 z# 6J gEq^J +e- ,r.lf ol:aoEq ^JElls
+El *g olEoE ^J4E dolE "JgzlEHl, ol $E| zlp
9 7a9l el=El+. "l d"lE zltlololzl +l6]l^J ¤-E= 4
El+ql nl+ ol¤al H6I4lEzlE
^J46}]HZI(rB
^lls"_lol
r7E.e). A*4"J gEql^J= eoJol qlC¤ qdg 6lr. E +
HO
2
¤6J
^l+ol e¤¤ 6J + flg eEE +E+ g+5 ql
B6J =allÊll=
HzlE 714 + qi4. :4+ ^tlE"+! z#"1 E+!lE CE=
otqr qd6l +3 +a e^J= zlzla_ ilq^J aqill eer+ q 17E.-.2
Z]ErtEt
^J4g + 9l+. ¤.51zt rJ gfolxlH E6J SEol E
El+6}r.ll
ollzl:z Eteq 6J 5a+ gEql^J ol $d;ol gqBrll ¤+. += gEq A.Jg q+flEJH E{¤ ^l"le-l tr-gz}+
7l= aÎ6llo} *+. zl rl¤9 sg
^,11
i+^d tls
cill"+g g tlEl]+r qlq. sEqt4 ¤.Eql^l
olEl6J tr-Elle_l ^l+E+
4I+sE q Eqglril E 4olo+ += gE= zle
^llal
^Jal"+=ol Eill AC ^JEHe =z]]q}+.
= g4l"+H¤- ol+6IE ..Jill'_lol a tr-qe+q .lill ac tL E +E++^ ^l+E ?ol9l ul4 Eole Aol+. Hlgql A
4-e 5s Ag +eE+ + 9t+ ¤E ar+= zleE +ae+ +
tlE i?B ^l¤ Hl]E¤. 9zllalt +a s_d= qL aol
+ +=dg *+q=q. ¤xlle c=c¤6Jg *E E.lrE+lI
+d ^l-"lE +4lE +4u+. ^Jill"+E "Jzl3 ^l-olql= EEil
ag qr--d9ltsrll, ol +E i
¤* zlzla 9l= zle.$ C-CA6J,JoI E*¤ EE|;1gg
^qlE(2)r+ ^qlEol zlzlt- ^qlE==g zlzlt- glE aB+ \ifiol *+.
9iu1. lql.g
f,tJolzl"J 4l+^J -oHzl= ^ll.jlel +
t
rti{l fl:d 719
=9.-d71lE=
Dl. + 4Ie ga "J"Jolzl 4.g Ee +ql ¤+g 4o14.
E,tt-41=
=trI.
rJ2. EEolg3 a.+illcr+ ae{i114 o .E ++*+. tr8. geg=Eol= "J"JolEq Tlqzl q*"1+.
tr3. EE g¤ril= + tr-ol+ EeE alBql +4q= Eaolq. tr9. 3r= E-solE oJ"Jol=9 Hl7Iq4 q6J"l+.
D4. t}B+g "J"JolE gq+4ee= E.JC6tzl"J tr10. SchuftzsHardv 7*loll 96IH i?B kg d6t
=sol=
eE" q4 o e= ?IC6I+. +9 Hlq d6l olgql =EolE=
E6H^l 7lt'- E!+4 o-e tzJ4
'J 5. dE urlEe- "J"J"l"ll ++614 +zig 13al +zl lll. g=,8 sl.6}Es a+del + ¤qg zlzl=. 914.
zl= E+61+ =Eol=
*9 tlxlE"l4. ^+^J4
a12. E+ql^l Hl+C +g 4+¤ tF-e=l89l E61l^l +ad+.
D6. 4lE 5c+l= A+ *zlBrJ9 ElHl¤g g?-l gqA q=J I 13. trl$g g}l E!¤ tsEe+Kraft 8E oltr-"ll^l BCq= geol
,l]Ael {I9 zl6-e + 6I^l +4U 4o14. = =7lE +zI sl6Ji]l+.
47. 4+ d6]- 444 9P B?lzlzl E*4 " e E7l 2==g "J I14. $8 E-4E= gad B* e";9 "l¤"14.
=s-d^l=
A-IZI
ai=
l.l
-1 +4 4Ha
4zl z?*E +rtl ro=@RT l2pF'Ibt)''' Debye-H0ckel o]E r7F,.3
*+ z=log{s(RX)/s(Hx)} z-l
'o ol
-1 t7F,.5
^+t
sE gczll ul4"lrl AE 17E.7
N,=V lAl
720 EII'J.AE¤
trEl 17A E^lel E7 14 ¤tr

¤E E^jl
17A.1 +zlE {zl {t^=-x} EHIEE ead+ Ell ol+6J + 9l= d+l %'-H 17A.2 +zlE ¤+,'d---lzi¤+E7[ qB4l ^SzlLzl ¤86]q4
5LHIE9+
g ¤B6Iq4.
17A.3 Eztel S+E7I+e dF+ql^l ell zlealgxl ¤B5Iq+.
G-\
l -tl
¤+E Pulz]. 2.6x lfrsm,(COre| ag)"J EzI9l l.opD =.zl

E17A.1(a) I +¤+3 4lt}5}q4. dEil= r.33ol+.
9 dzl ,8+zl stlE= +ts^l7l* rll g.g¤I dzlt9 ,rllzlE g"IzI I 5 d*ol 72.39mot-tolr" "JE7I 86skg m-3"J 6J Eillel *+
Er7A.s(b)
4e+? 4 d*+ql^lel {+E +El-= 2.2x tvnm,ol4. ol sqillel E¤+3 aru
E'r7A.1(b) ¤+E Pulz} 1.05 x l0-2em3(ccl4e+ eg"J +zlq 2.5pD a- 6Iq4.
zl9 4zl6l=--,z]- E.HIEE: #tsrlzl* ql gs.J dzl^J9 ,r-llzl= g"IzI rffiz| sqlE= l.sTDolI r ¤+E +ul=
El7A.6(a) Eeeq141e1
sldg*i r a*
1.23x l0-23cm3o14. 25"cql^l "JEE r.r73gcm-3eE +l6la ^J
El7A.2(a)5+a +Udl 3tl9 s ¤+EE rtql qe} H6Iq, 3sl.0Kql rI +d¤¤ +6Iq+.
4 zo.62cm3 mol-r, J.Bl-tr 423.2Kq1^l 62.47cm3 mol-'ol4. ol ExI9 ¤* u+eHltl9 ffiz| EHIE=. 5.t7x l0-30Cmoltr r ¤+E
E17A.6(b)
s_e| ffiz| EHIEE 4l4I6Iq+. +q= 3,rlzl o e 1.5 x lfr2emrol+. 2s'cql^J r e* "JE= 1491kg m-3
El7A.2(b) q¤ +,*E 3zl4 g {+E= r'ql 44 H4q,320.0Kql^l o e +l6E tl4 +d¤¤ +61q4.
75.74cm3 mol-r, -7?-l-1 421.7Kql^l 71.43cm3 mol-,o14. "l EzI9 S+E E17A.7(a) CIF3, 03, 9 srOr69l^J +Cg +E E{+ oltr 4ol*l
el-,'6l+z]- ESIEE 4l&6}q 4 El7A.7(b) SO} XeF.,, 4 SFn6ql^-l +^dg '*= E4+ oltr 4ol4i
Et7A.3(a) o'Cq]^J ClFl Eillg g ¤+E=
27.rrcm3 mol-'oli], r e* E
EE l.8egcm-3o14. olExllE tr-'11 +dsg alÎ6}q4.
El7A.8(a) az\zl l.sDoJ ,ta:q-zle| 0.8DoJ + {-+^} l09.s"E 49
ol+r 9lg trIg er+= ^-l_e.
817A.3(b) 0"Cql^l qts .-qillE g ¤+E= 32.t6cm3 mol-roli, -f
4l4}6iq+.
a=& "JE= t.e2g cm-rol4. ol "+illE ^J4 +a¤-g 4l&6J.q4.
El7A.8(b) a71712.sDoJ d+z}e+ o.soDoJ + ld+z} ,tle rz0'9 49
ol+I 9lg
M= 85.09 mol-'9 i{6}q4. "IE e+= 4l,t}6}q+.
E'r7A.e(a) x/Eql d6}7i r+q-r+ rJol uH99q 9l+ (0,0)ql 3e, (0.32nm,
El7A.4(a) CH2I2e-l EeEg 656nm Hql Ell6ll^l 1.732014, ee.i "JE= r 0)oll -e, r4r r+-q-E+El 20"E 49 ol+r +ldg-s+q 0.23nmoJ d
20"cql^J 3.329 cm-3o14. ir+6}ql^l ol BziE ¤+EE 4h}6l-q+.
"l ql -ze.ol B}]gg 4+zI E.HIE aTle+ "Jolg 4l4I6Iq4.
qE +6JEE EeEg 643nm Hql qfl^l t5z2olq, r ee}
Er7A.4(b) El7A.e(b) ,/Bq a6l7} +.q-r+ zJ"l u|lEqq 9ltrh (0,o)ql 4e, (162pm,0)
gE= 2o"Cql^l 2.eegcm-3o14. Elt'-ql^l ol EalE ¤+E= 4l4i6}
"l 4l -2e, relr x+-g_a+q 30"e.1 4¤. ol+r ge o ++El la3pmoJ d
94. aa= 6s.sg mol-'9 fl6}q+. ql -ze.ol ull¤9 {qzi EtlE a-7le+ %r-6}9 4l,|}6l.q4.
El7A.s(a)
"&q|4 dt+ql^J Hro9 ¤+E +sl= l.5x l0-2acm'o14. E
Eq 178 E^l=,t.lol"l 8E4rE

¤E E^ll
D17B.t Ezl-S "Jq tlEz}Sol r/t'ql qq A4q 9=tiJg D]78.3 +!+illql 44^J= 4ltrl= ¤eg +4.11= Lol :l4.Kevlar(3)E
Îolel "*g
olE4 0 + ¤E6Iq+. *ts=zlg zlle e 4g f + + zlo|_r.600Kql olg rllzlzl "Ja6I4. qtr
EztzJ trsel*ol ol falzllel BCr+ oJeEql TlqE 6IAL+?
D178.2 +i eq} BCg (a) Cdzl4 tlEz}+4 O)+zI +llEoJ+E ol
+6|q ¤E6Iq+. qL + Egol trl +g^l= q¤4
^lE6Ia,L+?
EA 721
Dr7B.4 ffi rlgol+

^l
+9 6J=E aill$ Ei6lr, olSol CB6].= a
1*+p'4 3 Kevlar
n
ag
tt ztt
D17B.s
"J6}qzh (a) y = -Qr1t,l4zuol, (b) V = -ezLtfos ll4rwof ,4 (c) y =
Jl - 3 cos20) I
S{z}, ffiz}, 43
4rc of .
--^1, rEla
I :41" "l5el dzl^J"ll 4¤I ,14 9=rz1 tl.ol,t} ol.?= ¤B6Iq4.
8=: +z}ql ql¤:6}= d6} EI]¤E-
G-\
L-i tl
E178.1(a) F C¤ +6 +^l7l E.J zldt}ql zlzl rtrJ* Eq4 gig rll

"l
olz|.
I+ qfl¤ a4ql fl= + Ar ga} ÎolE e4I t'-E I+ qlLJzl
Î"19 tlE "llHzlE 4lt6}q4.
E E178.4(b) l.0nm9
E17B.1(b) + d¤ +6 +471E46tZl 44 r".E trq4 ilg tril olE E 4lt6'Iq?-(London rl9 "l*alq+). gsql qlolEl= zle ¤ql^l *
olel 1tc.4l+ iqA¤ qlLlzlE 4l4l6}q+. ^l olz|.
El78.2(a) 298Kql^J ll = I DoJ 6J tiel +al7| O.5nmtrJE Eq4 E17B.5(a) Li+ ol$9-trPQ toopm flilql flE Hro EzlE %}6.19',Jql
'l8l^J rll gs¤I E qlqzl$
9lg trltE ¤+ ^JE4I+ qlqxlE 4l^l6}q+. ol ollulzl$ "l Ezl¤9 ¤ q-q._E Eei+: 4lt4q4. Eel J!+x| EHIE=
+ g Bde5 oilHzle+ ullal{4. 1.8sDol+.
El78.2(b) 273Kq^.] 11 = 2.5DoJ + n}E Tlall^J Ezlz}
t.0nmtrJ* Eq4 El7B.s(b) Mg2+ oJ$e-E$Q soopm 9lilql ?lE ucr EzI9 *6&3 Hlql
9lg tr19 ¤+ t}Ez|8 qlqalE 4l4i6lq+. ol 9lulzlE ol +zl¤9 B +-q a Eel+: cll $e¤I g qlqzl= 4l.t}6}q+. HCIE ffi4 E.HIE
+ E Brl¤+ qlulzlel ulna}q4. r.08Dol+.
=
El7B.3(a) E +z}e+ Hldl Ezlz} t.onm"Jfi trq4 9ig trI ol$ îolE ¤ E]7B.6(a) tl++q^l 3.0nm4 0=45"8 Eq4 il=+ olulc 7l ^lolel
g ffi4 gE-46qz} tlg4l+ qlLJzlE E B at mol-')-tr 4l&6}qq. -5 ,r8-f__1xI
t}E I+ ElHl¤ l7B3b^lg ol+6}q 4lÎ6Iq4. Fr= ttz=21D
8178.3(b) E Ezle+ CCl, $zlz| r.0nmEH Bq4 9lg q olE B ol4.
Îolel
+ t+z}_+B.^!r-+z} tlE I¤: glulxlE E B at mol_,)E 4lt}6.Iq+. El78.6(b) tr'EI +dgol 3.s?l ,lle +ql^l 3.onmel 0=45o8 Eq4 il=
oluf = 7lt$=2.7D)e+ E ez}(p = 1.85D) E 'jd+z} t'-gz}*
ElHl
Et7B.4(a) + He $21 Îolel +t tlg+¤. "llHzl
l.0nm9 ae-lql fl.b
¤ rze.eu^]g ol+6}q 4l4I6Iq+.
Îolel
E 4lt6lqeHlondon 49 "l*olqq). geEI E'llolEl= Îs eql^l *
EE 17C e4ill
¤E EI1I
D17c.1 -- 4e¤. ¤E6lq+. Dt7c.2 .-qill +ql^lE "JÎB Es EI+E 4lÎ6h= Monte Carlo %IH4
5q+4 "JEg ¤H6lq4.
G^
JtJ
E17c.1(a) EE d+49 lql 7l4L\4?"1 0.300mm
zll*6J +elHql^.1 9Eql^l EE ae} "JEE eeTlgcm-3eE +r EE EE tlqg 41416I
"J Zl*aJ +?-l s^ll+ ?]q^l 20"ce.l gol +.rcm k.olTtzl g+71+. ol q+.
gEq^l E9 "Js= ee8.2ksm-3e-E- -.ar EH ar"q¤ 4lt.1q+. E17C.3(b) BJzlEol 0.300mmoJ 4l*6J +4 .EL^ll+ "Jq^l 2s"ce-l $ol
E17c.1(b) Al*6J +?-lHq^l EE d+49 o9l zRi4. 4d"l 0.320mm 10.00cm +ol4zl g+7t+ ol gs:oll,r] Eel e* EJEE 0.es00B cm-ro
"J A*al +4 Eîl+
g}ql^l 30'cel gol e.tlcm $-olzlzl 942t4. ol -e +r EE sE *qg 4ltl6}q4. d+49 oolqI 7IA6Iq4.
gEql^] EE e* "JEE 0.e56g cm-3e-E +r. sE tlqg 4lt}6lq4.
El7c.4(a) 2o'Cql^J HlxlEol l0nmoJ +B E%Ig4 ¤zl Sqg 4l{}6}
E17c.2(al 2o'Cql^J HlzlB"l 200nmoJ +B E lg -EE "J+9 Sqil¤ e4. .}l%+ +E Eel ol gEql^l I ?zl "Jqg 2.3kpaolr e* "JE=
4l&6}q+. 0.9982gcm-3o14.
El7c.2(b) 20.Cql^l HlxlEol 220.0nmoJ +B qltsg %Ig sE "J+el $ Er7c.4(b) 3s'cqlî HlzlEol 20.0nmoJ +B E%|99 *z\ Sqg 41416}
q ZF= 4l&6}q?+. ol $roll.tl q+g EE +qg 22.3emN m-'o14. q4. rll%b +El EE ol $E.ollrl4 6z\ sqg 5.623kpaolr e3J gE=
994.0kg m-3o14.
Er7c.3(a) 4a+ +"]Hq4 EE d+49 }ql 7Y-*q.4c"l 0.500mm
"J 4l*ql +e] E^]l+ oJql^l 2s.cE ¤l-ol s.8ecm tol4zl g47l+. ol
722 Erl'ZjtE¤
EE 17D rEÎ
¤E
=81
D]7D.1 +zlc ?"Jol +¤4oJ azltg TIeo +r&l +4Lt= ar+= q Dl7D.3 6B419 +ts gEel *4 dol gE= qBrll 4s+?
ts 4ol4e g"Jolf-B+, +rll-B+, r"l.I. z-Bi il¤ ¤B6Iq?+.
D17D.4
^|ol9
D17D.2 r+* {$g ,{+r+ olE9 "JHICE +fl= ¤go}q+ (a) R. = olE 44E e-BE Eg + flE ¤Eg "J6lq+.
Nr, (b) R.-, = Nr/2/, (c) R*.=(2N)t/21, (d) R*=N"'lF, (e) &=Nt"l, (f)
Dr 7D.s r+zlE ti:I, z1l, 3zL'l 4ii +aEol q B4l
^JoloJr{ ¤Bqq 4.
R* =(N/6)'/21, (g) & =(N/3)'/21.
G^
Jti
E17D.1(a) 10002il9 t"Jille
E tzlg ¤:Elr]l zJf polz| (aEl E'r7D.6(b) ?+44 z)olzl l.125nmoJ t2004lE EE_9_E B 6tl4lzl 91trI.
zjol)-tr.*E ^l+E ol.${ g-e +96}tr}H ol
$$
zlo1e4 S.ovoe Hg trll
^l+ *-¤t_zll+|
"JE
^lolel
zl
^l+ol ^l¤ "Jtq *-¤t-zll# A4zl ¤"}zl-
4E Hy.4 +7H+) g.= A4'(-)44!.+? E. a"Jel +irl= H,/"+ H6I 941:*i
dr4i E17D.7(a) E ¤zlol 2s0ks mol-t?l tz}+l E?-lqlB{l ^l¤E S+ eol(^}
Er7D.1(b) 10007l|e1 *Eli]l-a 5:'Bill ^l¤el ^l+ 7Jol7l (eql
¤ tzlg
zJ"l)e+q &qr ?ol9 2.5o/oe H6'J trll +g +rI EH¤- uI9 aollc+ ^l¤ "J+ Î"lE a?-lE 4lt
elE q%+ +7H+) E'b a^'(-)6}aL+? ^l+ "J¤ ÎolE =-¤+-4lB Z 6iq4. =-B+-41+
E 7"J9 +El= H7"+ H6I
^l¤E ffi
Er7D.7(b) E ¤e.tol tT4kgmol-'oJ liffll $4ueg{l zlol
4.94i (^l+g Erll ull9 ?oll4
^l+ "J+ Îolel +-¤+-^{{i aflE
E17D.2(a) 150pm zJ"l9 +9lzll B 3il-?lE ++zl ,Jal +tl*ll
100041.e 4l,ti6}q4. =f,$
el dq *=lE;S +d;Ig.rlul 2.1nm94 ol +qlillel zl{ zfoli $_ul
7I qaL+?
rr /u.u(a) "J ,.]
î+ +î9tEl HixiEol z.3ruucle. ol /.1¤g C-C E
q+e.g ol+q{ 4o14. ol +z}A ToJe zl$t;laol ^l¤g ol+
Er7D2(b) 164pm ,Jol9 E9l^11 tsoozHe- E:z1gE +Ezl ,J4l 6qloll ^l+g
el dsl tlzl$S +A6l9qq 3.0nm94. ol +*illg zl$ poli $u[
r 9l= e6JE +E +6Iq+.
Et7D.8(b) + a EzIg Csl tlzlEol t8.enmol4."l ^13=3450pm
7l qa!+? ,JolE Aq+s_E ^l¤
"l+qd 1o14. ol +zla 7"Js 7Ia6Ia ol Î
E17D.3(a) E delol 65kg mol-'ol til-?l ¤49lHl ^l-+ "J*g 20"cql^J ¤9 olFr 9lb Ae}el +E +6Iq4.^l+g
l.0nm olE^la¤- qlel ++l4g 4l&61q"+.
E]7D.e(a) E E=Jol 65kg mot-'?1 5?-lqlfl
El7D.3(b) E d=*ol 85kg mol-'ol lil-g 5Eqlfl
^l+g 2s"Cql^-l 2.0nm B H ?, -:. o"ht ^l+3 lzl-?l ^l+ e6J ^l+
r0nmzl g +E¤. 4l&6}q4.
ol+^lflg qel e+lqg 4l&6}q4. ^|olE 44zl
E'r7D.e(b) E d*ol 85kg mol-rol E4qlfl lil-tl zF+ e* ^l+
Et7D.4(a) E 3*ol 65kg mol-'ol rzlg 54qH! rl¤ "J*g r.or'* Eol -a H , :z "Jt
^l+3414I4q4.
B ++9
Î"lel A4zl
lsnmz}
^14 ltg
4t9 E-Sle-ei4 HEI¤ alt}6}q4. Er7D.10(a) E d*ol 65kg mol-'oJ +qqHI 3il+l zl-+ 3B rl¤
E ¤*ol tzl-?l 5491H! rJ¤ "J+g E ^l+9
E]7D.4(b) 85kg mol-'oJ 2.0nm
e H i, I oJE ^lolg A4zl10.0nmel 10.1nm ^rolql flg +E¤-
a]&
9zlz.ll llg trIel E-qlE eEl H+= al^}6}q4. 6].q4.
M=62l9mol-'oJ +!+ille+ M=784mol-'oJ ftlillE rJg g
E17D.5(a) Er7D.r0(b) E: d=*ol 75kg mol-'ol E:4qfl 3il-?l e6J
tr. jl?, -z "JE
^l+3 qEg ^l¤
^Fft
a=*4 sE+^lag 49 "J"Jol-+ B+ E g%Lr+ +rll ¤+ E. e?d:g 4l Îol9 44zl la.0nme| l4.lnm
Î"lql fl-" 4l4I
tI6Iq4. 6iq4.
Er 7D.s(b) M = 62\*mol-'oJ +q+illel M = Zskgmol-toJ #6J{lE r,z E
^l¤q^l C+ +9lE Î"lei 4.* 4szl E n"Jg
gt}^la¤- rI9 ErTD.rr(a) 6J 6qli.ll l0e"B
e"d' Hle "J"Jol-+ B+ E e"*r+ +ril ¤+ E e+g E= ^ll
4t6}q+. 'JB a+ Carl HlzlEe Hyo+ +7H+) Ar(-)6l1LL+?
+q= Hy"+ E6tde+?
?+4E z)olzl0.e0nmoJ 7007HE -trE-g--E- ¤ tzlg fqlillzl Er7D.il(b) + +qlill z3iy z;utl120o-tr. 4l+¤
^l-Aql^l dEE Îolel
Er7D.6(a)
gl4. rl¤ol oltr4 o e +¤6I4H ol 44zl cg "l ¤lEl4lel oJ+ z 4= H,zo4 GzH+) E= aa
^l-= "J+el =-B+-4l# (-)6IAL+? g' i"JE ^lol =_Bt_ztlE.
Eolzl qAL+? +sl= H'2,4 H6Id!+?
Eiif 17E 1ldl E-El

¤E EIJI
Dl7E.r 4EE-grll¤ +4I+EE "J4l "l¤ +E= g3rl+EE 3zl=*ol D17E.2 ¤4l:qlEol rllsqH 44 2?+E {ol $Ez} qtr g6}9 E
-o.4zl444Exl ol+= ¤86H4
+TIElql IIl+ rJi+tr}. 9l old g + 9l4L+?
EA 723
ulql4ol {lEe+ agql^J d++ a q+

^leql^l C+qI
Dr7E.3
^lE ^.llE=
olf+ +9.o1+?
EB+ Ess+ ^l-=E elxl¤¤- cl "*ol qlC6l+ D17E.s 4+d tlg.4+g ¤B6la r qlE E"le|.
D17E.4 ¤ qlEa, f-eln a+ ilol= ¤B6Iq4. ?+?+el ql= E
ÎolE
G-^
Jtr
El7E.r(ar f&9+ql^l dzl*9 ¤6&9 Er 0156l+ EI +EAE ol* Er TE r (b) ++.-q +ql^l 4?1*9 ¤alg $l ol:a" a1g. f, EuId9 olF
fE u* Bqql^l ul(1tm s-r) = a + b(pH) + c(pH)2 +

3.0<pH<7.09 pH $E aE 3.0<pH<5.09 pH gqq^l ul(Vm s-r) = c + b(pH) + c(pH)'?zl
d(pH)'^lql q4 H+tr} ¤zld a=0.50, b=-0.10, c=-3.0x t0-3, f-E]r ql q4 H.JtrI. ¤zlrl a=0.80, b=-4.0x 10-3, relA c=-5.0x l0-2o14.
d=5.0 x rtraol4. ol +EeE Fddg +6Lq+. ol +Eeg Edag +61q4.
-vvlLtt E^l 8E4rE

-4.alxl o r.ll
O tl ----r L!/'ll
rr 7 r ez} tllE6J+ Al4l %IBg ol86IH EzlE9 6)-=-xl. EflE= ql^J o

g + 91tr1. (a) ExI sB "J=zl
ÊE+llqe+
q}^Jol ca6}fla+ a+71
CA+ 44} %lBg ol+6}q rrars_N_4lEo|,rlleolulc(7)e+ gg E'Jq
HN 4 N
flqE at}el {+z} EtlE= 4lt}6}q+. ol ffixfi ^}"lg /J.a++

9lulzlE Eq uBel +a4ql B"J HHgql.! r= 3.0nms +r 4E oql qi N
6ll^l E^l6Iq+. O) (a)s+q +qI,'A'-+zl4+zl d-Ezl+ qlLlzlE 4lEll Es
il= ^8i'll 4lql^lE ?lB4t +i A6J tlEz}+q qlLlzl TtoJ zokJ mol-'
r+ Hlr6}ol?+. 8 TIBO
o 117.3 tolEp
.:z-+E trIe-l gqqg S46Iq -E-zI. 7I++*3 =J4 r
4 zJol lofu(zlzlloll 4ttpot y6}I, +^16I+). dw=lflJolse 7lE 4g
N'cHs
H
du= TdS + tdlol4. G- rs - ,,-s +-r. dce+ dAql ++
= IJ
^-]g
+6J trl¤-
q +g
^ Maxruell +4.l^lg +E6Iq4.
7 trans-N-Dll=J0l- llEoltrl E
[#),=-(#), (#),=(#),
tl7.2 ol +z.llE Ezl dgl ol lxllel fl.ri.o1eE gaj z4E glolB"I4. s+
6JE- rrBo(8)E +EillEg ellE+HlB RNAE DNA-tr. H+t^l7l= +E]]
olq^l +g_n+ ,J3 -lgq tlEll ,JA^lg +E6lq+.
q.Jg 6].b E-dÎEAql
'il611^l
9xll ar89.J+. qq rrBo +Eill5
el gcql EItIQSARg E4 e4ql E6IE q-gr+ ?J?s4l7l
^dB'J+ (#),='-'(#),
logA = bo+ brS + brW
¤21.,..1s= EE Eql {oJ *oilre}+4lsl: ul4"lel"l:u, w= 8ql troJ ;z+ olEall=¤zl d{l ol lxllel fl.tlo1eg ¤tJzt$ !.loleopl.;.1
zl++ill x +E 47il ?lxt.el +rl +4l5lE ui4"144. (a) olel rllolQ$ +q= +E_E+llq(]ill4
o -g 'molecular mechanics' EE 'conformational
ol*61q bo, bt, bzE <t$$ ee6}q+. 6JE ol eSAR4g qI ++ H+ search' irEE9Jq)E ol+61-E Ramachandran E^lE g + 9i+. E +
log A$ + 5B E+ se+ g+^lA+. EllolElql "*+elH ++

w6}-r.
=+JqLI -'|-EellEÎ-E-E ol+6}q EI6 El+lHE a14}g Ê AE +q +El} il+Elqfl4.(a) *d R=H-E +r1, a4lg Q=+75",
"ll"I dcl. V=-65", E4lg Q=V=*180o, r4r jlzllg Q=*65", V/=+35'E *-
XH CI scH3 ocH3 CN CHO Br CH, CCH -:I. olE qflqEq a7l B4E:ael4. olq^l a+71d¤611 #
?llq= ol+6}q 4 ¤EIEq 716}+zl +4= 46J6I7tl ae6}q dill ^r'eq
logA 7.36 8.37 8.3 7.47 7.25 6.73 8.52 7.87 7.53
fl¤ qLlzlE alî6lr 4 A+ql rlltl 4+ 0q v 4EE +6lq+. 0)
s 3.53 4.24 4.09 3.45 2.96 2.89 4.39 4.03 3.80 R = CH: o r Fz, (a)oll^.le| E"J6J %IEql u|4 ,r1l a7l eqEq 4.J zl
w 1.00 1.80 r.70 1.35 1.60 1.60 1.95 1.60 1.60 t}g 6Iq+. R= Hel R= CHsoJ qtsqEg 4+ eqlE"l LI44: +^l
A4 ziolAg 6'J44e-_tr_ ¤B6ll -tsoI+.
(b) s= 4.84e1togA= 7.60oJ Eq Eil+ wE Ag 9"Izi 99ot 4AL+?
721, ErPJ tE¤
o n7.8 ol E^ll= E7l tql ol r{lel E^}olEE gr'} 239 g.loltsote}. E

H
zIrJ +*illE +a= ql+6tE ql +xI +llEEI+ 4l,ilol
N
,A N- DNAE 26 +C +a= +fl+ ule-l"lB ¤zlE rlol9 +a e6Jql 96]]
"l+ql91tri.
H
HH
^J
BCg+. DNAoil^l +a a6Jg BC6J + 9l= + grlSel EBe^J
I r84oilezt.
"llB"Icllu(10, R= cHr)rl *,u-qnJ(rr, R= cH:)g BlHg Exl (a)
Ee ¤41 +EE?llqe| eliJol4 a+71ca6J 4l4I 0l+6}0l oll
n 7.s ++A i'Jq +E HIÎE ab C9 tlzlE &e| o = y&9 *4lE zl.
xlq, 1'= o.asol4. zFft e¤, +E4l AB4g ,*= B-olqlu4 ,llB-El"Jg E= gz} ^Jel d6l-= 4l4I6Iq4. O) q}^Jol 4l
^l+q 4
(a)
^L=r+ tul +lt SzI d6}q oJ7+6ll^J qlp-olqlHr+'tlB-El"JE qH +lzl¤ol +4
6ti^l +c t+lE +E 7l7la_ +Elu c.F Hl4"J
4l+ Bq s6'J
^l+
+E6Iq4. N= 4000 olJ. I= l54pmoJ ull9 r= +6Iq+. g eelol M"J
^lg e6Jg ¤ce. lol4l ^J46IL+? (c) DNAollrl= A-H...BEEE cB
+4IA a"J E4qB{l ^l¤ql 4e} r= +6}r olq^J M=56Bmol-,oJ ¤¤"1 "l+q4op o.Jrl= Îdg g+q +l. +^ Aql_e.-E ¤Ag + il
rllg ol (t¤- 41416I{4. a=arlouoE ol86}q4. ¤zl.,,l uob *"J Ez} E= 7l!"t "lrJlu-4"J ,48-g rel4. ol +4lql^J= +zl¤¤ 46J6l4l
ql E6J uflxjl $ulolQ.
=
E9tErll EzI gB ¤41 +sE?llq= "l*6J + 9ltrt (d) g6} Bg *
n6tq ol^J"l (c)ql,rl Eg ad. dlE + qL a"l DNA EzlqrJ zls4
rrz.o rlEzl* slHl¤ 9lHzlzI c6ltrEs +qrqr doJ wzfl gx1 o+
"Jq+= 4"JzlE "JolEoI+. (e) .<lE{l$ +o}U %tg s6.J DNAqI
^lB"l
E B+ tr-A++ {luJxlE u=-2$Cot3vfroe +q{g trq+. vY 7l .,.1 ¤zla}$ ¤^d$trI-. olfi$ zlzla- (a)-(d) +^ll$ l$ol Eq$.
4l7I Eq fl= Srlel Pulol4, _s= qlq* -o.4E- +^lqRg qle-l <lol+.
+
ol e+tr-+Q n2alV = (EUldIr)rE ol+6}q vanderWaals ul4"lel a* Cu NHz
o
ÎolE
SAl= +6lq+. N cHe
HN\
t17.7 F. Luo et al. (J. Chem. Phys. 98, 3564 (1993))= g*E"J +A"l "J El
$.8 He, zl-Eoll +.J dQl A+= Hn6I9+. ol dql$. flt rllE tmr
N
I
oA*/
+i]E z.lgol gS-6I9=Ell, ol rlde. Hezoll 4q} hcD,zl qI t.st x 10-231, R A
hcDozl ef z x 10-'?61, -lel-I. pol zgTpmoJ ol$zl Ar+el +*g+. (a) He-
10 R = CH3, oll=-oltilU 11 R = CH3, oll=J-ElE!
He tEzl*q rItI Lennard-|ones u|4ulrl roele9 +6II. He-He tl-Ez}
+ql qltJ Lennard-fones ul¤l¤9 E^ldlq?+. (b) a= 5.79 x 10r0m-r o +
{:-J1. Morse $fl¤9 E^16}q4.
-#v14 1g
zi{l
ol s7l^ql^l= r.Al9 +ae+ E"-14 Caq +4^l r.a6t 18C r,t{l0hl9

eir d4. ¤'l] ,+ol zl¤9 zl-bz]l + q++9 EAE* r =-Bt
ill t'-q'}. a+r+ qql^J ol¤-qE 'J.H+l+ ++E 7td-,
-]1o a4lel ¤+j==¤. qq t'-g4}+ql E6I^l EEq a+6J ca
aE *qr+ *uHdql ol+q= Hls.4q ++ E^ll, a+4-9. g +4U4. ol EEql^l= ol*lal deg q$ril ¤Ba}:l ol
s ;-++ qiil4+r gt=
^,il49,
:_4r d+ ¤'I Eol +e1.rfl* CAg bEotzl fl+ Tlaql +6I^l ¤Eg a
ÎqE Elg
H¤4 {|E Eeql ^ôl= 17z$ql^] ÎE4
Azflfl a;l3 ol4.
q A¤ +qlill=g 4*zl r.ill {tQl$olr}. rsc.r 18c.2 ole eg zx{l; 18c.3 SBaB ri{e} Ert rfll
=4;
18A 7J47a 180 a.iilel e+4 ¤tr
ACE r++ +Ce r CBE"I +zlzlql H11gg olF n 9l rAlE qs+zl da +q= qq "Jtlel arCg E + 9ttr1.
q= aolq. oJ 5a$ol.<l= olel+ +4Cg olE tsllgE 4a "lelt CAE$ rill$ +ae+ +fl$ 9, zlzl ulQulQ$ ol
$ zlxlr. ¤H6In olq^l ol H11gg C%r4 " e +Elq= %'" +4^l +48 + 9ltrt
Bql +6il^l ¤E6tnz} *+.
18A.1 +71¤ e8 4rl; 18A.2 4rlEel
^lE!
18E r.i.ilel d714 ¤tr
188 Eltr 7lE rxll9 + ql+61 +e* Cee d+= E"4^14 + 9l= b
Hol4. ol Eqq,r]| lzllE :r. dzl F4sq "14 q¤rll
9¤ zlHS ol+o}ts 4Î qtr.a4l9 +aE zl.,!lal aCB ¤+6Ia E olEol ,+44E qel t}"lt CeEg 4zl aa
+ gl+. ol e{of.<l= xd 3I]¤H'E 7la gElE ¤Ho}a ol E trl olEg "l+6rq qBrll d.el3,} ^la + ilEzl.ll *"11
q^J ele +gE dz} EE- EEE zlzlt_ qBzl 444b4
^J
a*E 4,"14. 4l+6il^l E.+EgbEtr. dzlalH *
*g
ql +6ll^-1¤Bg 4"14. drle+ +¤zI sleg oJ$-a].{ 7z} E4lel Cd"l z4l E6l+ ol+= ¤H6Ijr" Ed ol s.q¤-
4 o e rxl +E zllzll $zle| gzlel ]z7lzl $e + ilq. ol+ql^] 4+l dztTl =oqql^l ts?-l ol+qr fl=. H}s.r1g
188.2 xC eEq; 188.2 Eltrrt Ir] 3{El q$ril I,JE= zlql +611^l re$ 4,o14.
=¤r[ HJSi1l; 18E.3 Ed.E.i{l
18E.1 Ei{l; 18E.2 ¤Ei{et
=+¤
18F zi{le! rP!4 ¤tr g rl-E 0l rl-Eel Es.=?
aillE zlzl4 ¤Ag 'zlzlffi'$ zlzlt- +49 f ?14. zI ^Jill a+zl- "JE eE flzl¤g +l,.l= ee6}='ll ol*sl
7t4 +4ol +BzlolQ olE Cdol z]]z]] dz} zlql¤ b xd sl¤Bel tsdse ^J++4 Ezl ^JE+ ETzI E4l
^S9l
+ gl+. "J"J +cEol trs4¤¤ g trI= rlzlc4 ae c 4_o e gd6}fl+ SoJ zsglrJts ,l-tl ++4"J xd ¤t zl
4ol 448 + 9l+. ¤9 eollzf 6Jtr}. ? oue ziqrg-_+f-El Eq4i r+6J +
18F.1 rtTlaFE; tgr.z g+ g 3g x[7] -EElE; 18F.3 *EEi{lol xlTl 9= eq oNe9 2+ +C sBg "JE= rjl ol+q= 4¤¤
x{ .A.txt
-i o=
solrz[ 6Jtr]. 4]L-"14 z_21 dEC flz] daJxll9 9*z]
¤4J tlg4_o + +C^l-71 4a gl=ql g6J 25ql^J ol=E
=
qlCq +tl ¤Hg B 4o14.
18G ri19 =J-qt4 ¤tr
rillE dz} +aE R^qd+ +g E+= ts.E.Hol4.¤.%lH
I "l8alH 14 Ee9 dzl ul +aE B^49 + flg +"J
^J-EZI+qI zl{q= ¤tr-g Fe
olBI+ Ee L+l+E
"ILI4
g + 9l+. qaql "J+ rill= cl +Îcg 4q+ts HldB
4 o e e*6lq d5f tsI+4 ag +e"t ¤^}g 44421
s.t4.
18G.1 E^lE: 18c.2
=+rl
U.Ei{l; 18c.3 HldE gEt4 fl8
E4 18A 4872s
oaaaoo o a
> ol E4= Hll+= ol* a oaaao a o
litlts qa1 6a-d ag Eopll^] -ri1l9 Dl^14 \
=8d =s6|H, o a o oao o a
?I= 0l6|16lE 0l=el qqf4, C714, Bql4, :rall
,\{xtEo A{EHa}.^. OlrL ^l7lE o o a aao a o
ci=== =da T ^/iLl. 77T171
o a a aaa a r' -/'l
E
> 6_4fl TllLJ o o o oaa a

+7ld egoil^.lE 3xl=e_l +44 Bt|g= E+l 7l^la_
LhEl-'J + ?lrl.
^jls= a a a aoa a /^*'
fal 18A.1 4 4^lE3 76 p+1q1e^1 E^l.Ll'!E=
Erl d.J=E 9lil=
> gg'Et qHl xl^l 8rJ 4xlts SE6l 4^l.E=el Ht|golq, ed +6= 4^loll Eqel'
LtElL.lEl.
tt|dE ¤8618 Ell g+ EolEol ol8Etl. H]ISE +4 9 EEtoltrt.

^lEE =9
oooa o a a o
\
aaaa O a a a
aeE ql+ +a= flzl, olg, $$ $zlfE +44 ul]¤o14.
ol +zlzl H]]gel 54, z}îl+ +"J "J^14 qEld ¤i3 I a o a a o o
alE +ae+ ¤aE

= o \ o o o a
ÎolE
+4lE +4.11= +_,qq}5C"14. \
o aa O a o
18A.1 +71¤ trE 4rt o o o a o
a o a a o a
+El4?l flzL EzL E= gz}4 EzI4 olg=E d
=gg lg 18A.2 E?l B=.JE(4]^l4B0l Bol0l B "Js= fltr|')E ,*=
E E"4 *Z'+z Q4'$ol +!4-oE HI+q"l ol${t] sgolq, 0l Eg=^1lE=
ETI 0lE^l7l7lU 6G,\l(U/.h alE, !E= HJdol ol.U)
4,o14. ol+l+ += _s_aEel +lil$ dE=E ++B +9(rB d^11 +6= trJ= + ?Itrt.
=d
18A.1)= 8Z_t 4rlzlr qI+. E|+^l *ZI 4zl-b a4 7ao1l
'Ifl +^J4"J EEqle+ eg aol+. 4* rJ fifl{ e E:"}z}

o
ts +t 4zlt aEE +++ rilfl uJl$B,rJ, aag 7lE +

aE eEql +q, 4 ds=g +43 %I4 "e. r ++lE dE
e EElr+"J+. + +a s
^7I
* 4zld9 +dg itzl6l.= o
a+E glzlq] :Bzl ?+g +E 9l+. 4 4zldE"l 5|]="t
+a s_i. 7*7]|trJ 6IH ea +4714s_zll g+. tag ill
*zlts 6Izl"J H4l qa¤- *zl t*E al-azlc r.illE 8^[
z!8ol4r ++. ¤zlrJ} ?zlC AA"J$ fl+g 4o14, "l feJ 8A.3 r=t ! +n Le E/. El {al ,J? .J+l ,r{sts ?lol 'J 4^ lE 0 | ?lE
1 l..
tt6l eCol+r zlaB 1ol.-I.

l
87HE +rlEEoI 44 0l*zl 89ElE =J?l^llsoll= ?J{4ss:"14^1tr"J0I

=¤El+l 7l*4 ¤4+EillE^1, olEel Brl H9l"Jg +61'11 Etrl.
îls=
zlzl:il_ Sd6J *zJ 4zl= +48 + 9l+(rH rse.z). ol t
+l
^llE=
qld6l+ 4zld59 4d"e. ¤a6lH
^Je + 9t 4.:z]-fl"]]^lE ui{z}zl 49214+qe g^l ++l ^llEel 8
^llE= fl l îlE4r
olEl+ t+l qL+(rB 18A.3). -l zll 4zldr==3 zJzJ sz[A'Jd 4zI4 ="f44 ++l
=ql, ^llE=
B rsn.z9 zzl-fl E9 ^ll*g dEe ql ?+rJ \l .Jd EI 4zld* zlzlal ¤+. A+q 4+^l= ^llE +Col+ qI
^llEe+
="+Elq. q+^J ol 4zl^= d¤4 o + 4zldg al4"J *E r5iE uli_H_ts E^Jq 4zld$ *= q HI-fl^| trJ91 ,t{!+
=
728 18 ri{l
s46l+ 4ol ¤4ts trIE 9l+. eL 4zL= +Elg + 9l= c3

=
++l ^llE= ^J'Jl61 qel TIzlE ^J4e. + gl+. rBl+ "JHl ca
4e + H9 4olzl zl* sl1. o1-=oJ ,tJtr. 49 +zl.J ag

eEFl.ol +fl ^llEE H=el polE a,b,o) cE 4448 ol
E Îolq 7J? a,B, Bl 7E +4d+(rH 18A.4).
gg1 ,rllEE r sld qa s+ql E6ll^l "JE zll9 e84lE ,zl
¤+++.
. gt* E+l aHzll tsl]gg "l-? 44]9 3+ sld+
îlE= =
$ zlz)a_ glq(re 18A.s). lal 18A.s gHJ
=EXloll
+6t= E?l
^lls=
4Eill H}|EE 3= aC+
. EAI E+l l{lE= rTlle] 2++g zlzlt- il+(rg 18A.6).
. Al l E+l AllE= qd rl4=o ,*zl ?+eq, "JHI49E
^ll
H4 4l zquzl tr+ ^lE +s+(rB rse.z;.
++l ^llE7I .=4+ ec4lql +6t71 +16ll^1 714"v 6l^= 7lE
Etle59 s. t8A.lql +=.611 +?t+.
:zl_?l 44 4^ly laf,gol4. olEol :.H rsR.sql +F+u c2
Bravais 4rl-=oltrl. olelql 4zl¤9 H]]g.$ g^l ++l

^llEel
Bl-g^l 991 ,rllEE zlzlt_ +4.11= 4"1 ¤4aI4. 4zI
"l
E9.**r,I Ag zl_o+ +48+
fl^! E+l szl 4ztdEol 91trI.
+lql"J
i{!d E+l r +CqlE 4x}d="l 9l+
^1lE(P)= lB 18A.6 E^|. e84loll +61.= trJ?l 6l'Llel 2= AE+(A'aloll
^1lE.(I)= Ll-El-1,!)E z [x l_L 9lrl. ^ls=
Ed E?l +lg"J olq+ 67}lel H9 +CqlE
^llE(F)=
4zldSol ?t+
E+l lllE(A, B, E= C)= Lll ?le+ r4r El-+B
=EC
* + HE +dql 4xldEg zlzlr 9l4.
t+ql +aE ^J46J trll= +a a +ql +61+ ,* fl2}4, E
zlE ¤:Cg 4zldol4 ++l e q6t= Lol ¤
^llE +xld_o
?]6}zl"J ole|l al*b 4ol gs aag olt-]4. Bravais {z}
E ++l ^llE qlql^J +g* +ag ?*+ 44a# H 4
z|flolap ++.
lB 18A.7 Ar ltrJ?l^11.E= eltr rtl8=='f^l B=rl.
b s, 18A.1 gE
=841.
\ d6 44?4 7le qla
ol ,c b
4 ,-p iIî cBo
tlE
+Î 6I+E C, +
ÎoJ
ztlg4 i4 cri
nLEg
I ET+ 6I+9 c, +
erJ aI+E c, +
+"J 6I+9 c6 +
olHl-
rJo 4714 +Hzll Hl]g c, +
reJ 18A.4 E+l lllEel Erl 4E s,tlE. >]E a? (b,c)E 8oil AEE +
q6Uel. . C,, +g ,r* p]d¤ LI4'flq, 360"/r Eld9 rlzlH 5F"J +4ll +ElU+
18A +4. 72e
=8
f
a
a
a
aa
l1
M
l'1.'1.!
18A.2 4rtElE
^lEI
Lry
a
9¤B " e +fl ^llE9 =zle+ r +ql

a
Ezl¤E H]]
=q?l=
gg +a6IElH AAH$ E"r+o].= EEel H]]6J4 7J4g "J
olril_p o tH l_tI otH}_trI
uo I tlct tlo
ol4ot ¤I+(Eq 18B). 3z}?l 4zlE+= z7lfl 4zlzl A*
b O1
aa' o
a ; o s|617] il*s + q7l^l= *d zz1-g 4z!-e zlzl:r_ 4zlH9
'aoa p oa
c
,}lH¤. 42fl6p. olq^l ol zl]'19 3zl-fl 4zlql+
^lB6l*=
a qt}^l7ld\tr+.4zlH==3 4zld# :a" $alzl gj:otE g+=
a
a
I-{Hl_p
ool
xi
OO
H l-tI
EÎ-P trJ,\l'-c ag +E6Iq4.
-J
a b
(a) Miller rl+
c o a
a O
o >i
.-=--J ,r--i r--a .=.1/ H9 4olzl a, boJ Bf.l ^llE-e. ¤ zzl-fl zlÎ4B 4zl¤ rJ
46ll-H-zI(rH rsn.ro). ol rHql +4U 4L *B==e. E-rJ4
l'J-P /.l"J-c /.lBf-l Al."J-F
a.aa.a o o-/-5- HEE ^llE= Eq=+. olE 4 ^llEel BHE¤ +4qlE +
.-7-;
120"
a
"JHe
gdql zf! zlnl$ ¤E(gAg Eo46tzl ?+=)g ol
a 120"
c G B c
o
+61-= 4q_irll, ol fl+dfl$ ol gol a44 E 6Ir EI+=
o
oo'
o
a¤nlzlq 4?-l= zlzlt_ +El.J + 9t+. qls^J ol= 4ElE
Af,\l
oHl
"ro
/\t7l._El
E- ll
3 (a) (ra, tb), (b) (ia, !b), (c) (-ra,1b), lel.I. (d) (."a, t&)
ol4, *E Hol +ql ¤44q +q}4ql^J "JB+= ag +
.f.g 18A.8 la'z19] Bravais 4^l'. E- 4xEl0lq, 0l Eoll flIPl r+ flclot
5|^ts a.= olLltrf. p= fl^l E?l 4^toll Et|6t|^1= R), tts illc .J+l $UtrI. :zfl+ "J"J llls+q ¤+ 4"-lE +{Lll= ql r HJ
^llE(34
F= Ec E?l l1l-s, rz|.Z c(.EE= ALI B)= + ol+Hs Eoll 4rl-tr01 6JE ++l 6IE olE Eg (1, l), (i +),
^llE,
9t= E9 LlElL.!trf. 34 4^l'= +Et ttr 9ltrl ^llE aolE-++ls ^ls"
(E ^llEE ^l-u4lLl-qB4loil (-1, 1), relI (*, t)E E+ ZI*6111 +48 +E ?l+. zl+
18A.1).
rH tse.roel {z}z} :zffie-l ^}o} Aafll 4zl-= +lql^J t.ll
q+ g:flolr}l 6IH +lE E==g sF c44 +6Jqlql^J
z!EE! q 18A1 IrJB 4".|4 n}+^] ol= HE ]Lzl= (1, 1, *), (i *, *), (-1,
rB rse.eql EoJ 2zl-fl 4zl-b 4zldE9 4^lr+4 4 l, *), r4tr. (-, l, *)71¤ 4"14.
zlfiEe] +gE^J, ?+ 4^l4B +dql 4zl4 t7ll7l 6I+ Ezl +ql ++'I ooz[ rJeE B¤g q61+.J u]Bg ol
q rF-l6}q g^l ++l ol-q+. ol *g E Ezlel E+E fl6l+ 4,"14. "lal+ ¤¤ zlrlE q+=
=qfl-g.q ^lls7l.
¤ HE +Cd- F46l-= 2+ qla+g zlzlt- ql4. ol
E + ++lel Elde 4Hill +lq 9l= 4zld59 tt-E. EsI
+cql gl= 4zldg HEI^lz)zl ?+=+. El+^J \ \ I I I
TI
I
^lTlzlEJ I
+lql fl= 4zldEg #6Izl"J 6dq il= 4zldg \ \ \ \ S
s:s St-
5016I+. \ \ \ \ \ \ S*\ S :\
c2
b
\
a
\ ss ssss s s S-
(a) (b)
,/ ./ ,/
,/ ./ ,/ ,/ ,/ ./ I
,/ ,/
c2
-/ ,/ ,/ III
./ ./ ,/
,/ ./
(c) (d)
.f.al 18A.9 ,.}'J-d ql 18A.10ll^l ol8el2^ffl 4^1. 0l Hl-fl^|
r=Tl 'J0lE LlElLHfltrl. 0l E+l 7loil ?l= 4xE!= 26 rHd+
^1lE= fg 18A.10 4l^l'48 gil 4rtoil LlEl-g + gl= +)J71EEsl
^jlE=.
++lelsldillslEq, ^llEE 0l44tE
4xEe g:BF= E^l?JEtrl.. BEE3 I[f^4o+ LtElLHfltl. 4 EEoll cHE] miller
=ce] ^llEel
(a) {110}, (b) {230}, (c) {T1O}, (d) tolO}0|tr[.
^l+(hkO=
730 18 ri{l
a
a
(hko
(110) (111)
a a/k
b a
a/h
(010) (111)
c fal 18A.12 E+l 4^ltrE Erl6l.= Eoil EH-d s4l.
^llsel ^l+el0lEel
fal 18A.11 3xfflo{l^1E dB4e E=rt r=9 Miller xl#. Etre
^lf
4xlEoe LE|Ll1flrt. xl+ 0e 6t|=.161.= +oll EB:d E- LtE|LHq, r]
^4
4 rlE= ?+^l gts E+l 4E^14 + ?ltrt.
^1lEoilE
$$ ^J46]]tr_zHrH rse.rz). 4zlHE ÎolE 448 @k0)
H_q E+El fldzizl9 +4 Aqe+ aq. ,+ Q4 ci4Et+4
Millerrl+4.a +q. qlE^l (i i *)"J E3 tvtitter zl#zl Eg ol req
4?+ 3?+4q H¤- zlzla_ q-g_4 eol +49
(2:01o1r4. + "Jrll qdzl"J ol E,tl %}83 qBl "*e- oldg + el+.
zlzla- 914. tutiu.r zlfE trl+4 ag zlzlL 9l4.
=49 doro _ hdoro du*
- (alk)
kdoro
. +q zli= G10)r+?ol f +lql4"+'Htr=Et+. sin@ = (alh)- a

cos@
a
. 7lg (hkt)z zl]zl]9 Eg +4.ilq, t ^]lEel ¤4+ H + rB + ol-4 4zJ tzJCql^J Miller zlf ftE glHol a49
Eg 7ls lhws +r}utr}. gde ++Q athoJ 44qlî -il.z}6l+ ag +4q1u + ol 3
rJ-s-rl tol {lE E + 914. 4LBel glEE ?ol: athzl ¤4."t&zlzltr- 9l :4Be-l BIH
9 ?ol}- alkzl g+. r?]a}¤ sin20 * cos2p= lol E + trl-Sr+
+:==!+ -il.Î6l+ A (a,b,w) (ia*b,*c) (--a,b,*c) (*a,b,q) ?ol ¤ + 9l+.
filg' Qfl,$ zllzl (1,1,"o; (j,i-) (-1,1,".; (-,1,-)
q+ f6}7l (1,1,0) (2,3,0) (-1,1,0) (0,1,0) U,,
zli+ sr,l (110) (230) (110) (010)
a )'.('f"')'='
¤Bts=E u10) {T1o} ll"l 4g.4.
"JHg d'n o 4 +h-z C4E 6IH
{230} {o1o} trl'g.
^]IE
" + {h/cl}oll,<-1 he-l {Iol 4}¤++ Hg a4"ll rl ¤

"JHlzl
ol I h'+k' - a
,, , Jfu- uhko-@+W
rl- ) _
B6IAI ¤uH:244 {h00}Hs=3 qle-lol+). ol +41= ke+ b-+ il-

:aflr t+ ,+ Îolql q4^lE u|{z}zlQ. h = 0"J 4lE olag 3il-flo + q+q-H E"J 4xlE ihlc4$.
ÎolE Z4
^lol,
a+gl ql6J ol Eg ¤¤ol #,t}4olq q+^J {0k4EE=3 a4
z| r-l-o-=4 Aol g+.
ql ¤86i4.
"I&zlzlL {hlt$s=3 bftql ¤fl6}r {h/c0}H
r==g c+ql
¤B6ttrl. ol Ll]¤-==g "JzlaH +H Egol ¤+ I + k'+l'
rH rse.llg Hl-zl-il.+¤- ?*+ 44= E6J+ "J* lzlg il-
h2
-7 E=
^t0t9
t"J'J 4^ll
a4 (18A.1a)
4zl.9lrJ9 HEE dq HJ4g +E}U 4o14. )-a

unu-
11.,11rt+12y
(b) ?1tr E=el z!4

Milter zli= .Jd HE
ol 4¤. "JHlEl^l7lH "JHI4 4z}"ll ql6J rle-=4 eg
^lolel 4"]- +4.11:
Ell trl]+61 ¤ Î%L
q6I+. 49 eg + 9l+.
1 h' k' l' E= ,rlo 19 7J?l
@ 4rlE=q 7J?1=L|'EILH=
^l d -a''b''c'
--]--r-
l^l"Jtrzl 4^l]
(18A.1b)
H9 ,Jolzl aL +f] ol+q{ +Eill 4zl9 {h/c0}H

^lls-tr-
18A 74 731
=8
EEEEU Mirerrl+Eol8 nI+^J

a = 0.82nm, b - O.94nr.rt,
ol c = 0.75nmoJ lI%I ACal ++] do*
(a) {r23}H=r+ o) i246}EE r}ol9 ,J4g 4l$ drh,nk,nl --
n
^llEql^l
6iqE}
zl+E¤- l8A.lb^lql Bq +H q^q-!+ zJ? Aalzl
.r'!.4EI Al¤l a Hrll E4l= +qd zleE¤ l8A.lb^loll =ol
+$tri.
Bq +H 94. o)ql q16l]^JE eg %IHg + + 9lzl"J
E4 ^-llEE HEq Ell6ll^J. aal a+_H-4 Miler zlizl 11222 , 3' ,^ =22.0...nm-'
* (0.75nm)'
dlu
I-
'
2tsll7l ¤4. rse.rbal"ll el6IH h,tsq./E <t=q n¤*dl (o.82nm)'? (o.94nm)'z
A4. {nh, nk, n04E r}"19 Z}4HE

^}"lE 44ol ffi tr14^l dw= 0.21nmo14. :_41 drnu? ol Aq HL +
4 Bol ¤+ 0.l1nmz| ¤+.
=l /d2na
rlTl-B7118A1 zJ? 4zl"llrJ (a) U33)BEI+ O) {3ee}E
h7 k2 n
2
Ee-l a4g al&6}q4.
*=ry*Y.ry=,'( a
12
__L__L_
AztbztC2 ruu¤90'0 'uru6I'0 .E
TI|LJ=
=g:d
D l. +71¤ ece *44 "e. HI+g= +a _s_iE.tr. ol+q4l tr s. 991 ,rllEi r qa qlaql q?+ "J# E+tI+. +
=811E
4. 9l ^lls=g "lEE 7lE qlaql qe} goJ, EAL E= gAl
a 2. 4r[= 7a e+1gz]4, tsz]4, E= flz], +z[, +g z{15-e. E+++.
"lg5q ,l)Eel gil= +EI,-}]= dEol "JE= +9+.
=!Zl
n 6. Bravais 4rt= 147Hq troloJ 3il-g *zJ 4xpolr+(rg
r 3. E9l ++lE Htl HI+ +fl= EEL6I-=
'h'-4
g 18A.8).
^1lE=.J
q+EiI"l+. a 7. Bravais4zl9 gg1 ,glEE fl,\l(p), i{ld(D, Ed(F), "t +E
a 4. fl,\l E9l 4z}d5ol flql"J gleq, dill4oe + C(A, B, E= c)E ts+6Jr+.
^{s= Hl-flll
4zld"J¤ *=+. E9l 6dol+ trt+ -H.= D 8. AAEg + ^llEE Miller rl+ (h/cD= zlzla- +E+q]q, 6J
^flE=
Eg +"JqlE 4zldg zlzlr 914. ^llEE AAEE9 lhktlF=
zlzlt- +ElUtrI.
=sEt^l=
,\{zl
de. --1I 7j al Ha
.J* 4xI9 EE ,J4 lld2hH= (hz+ l¤+ l2)la2 h, k, o) /3 Miller zlf 18A.la
ÎolE
rI* 4zI9 HE ,J4 lld21,p1= h2laz + l¤lF + 12lC 18A.1b
Î"lE
E4 18B Eltr 7lE
+gs+q +a= .JoI4E d4l r+eg A*6Izl ?tsq, x

> ol EEE uil+ts ol.B
d fl¤ rllolelESEl +aE eA6F= Ell gsel +qL4 ¤it
ri{H ¤trE ¤B6EiE ol=E xt^llEt +z!E 016116lr., q*l ga+ril +d.6lzlE} ¤E tlilql e+q7l aAl EEqq
TlgE ol8atol 01758 olgXl e86kxl= golot:dtrt = EzI+
+d.tl Jzllzlzlu 49 zl-F4e+ EllolEl 44zl
> q!! TllLJ
=
7k4aq. ol xd "JHg B^t EB ¤41H4 6}41 olso 6lE
sltr T|EE ol8olE +7ld e8ql,'.19 fl^F=q 3414 H}lg= 3¤ EgElqI +a= 844 0 e plg fz| ?14.
g+ ?Itr}.
xdg ul*"l l0-r0m CEq dzlvl"lq, ++q1q l-.il
> Els-et qHl rl^l Hxl dzlE +=^l7lE ^Ja+(rB lsB.l). 4zlzl ++ +
74= dB6ll. Miller rl¤ olEdtG 3EEE Ll'ElLll= e+ Hq Eqa q= +Ezl zlrflH^J XlHfl6J ultl g
=8 +116lr ?lol0r attrHEE 18A). .E.El dxpl q^lE EIE
HJES qE g+ xdol %r¤qEcll, ol ¤4 +Îdg EIE EJl.d
oe LIE[LI[= arilEE 7A9 El¤lxte] 8Al t3), Fourier HEtoll (Bremsstrahlung)olap +++. +"Jqg zll5 E=
Bremset:
sil 7lE cE(Erl l6cel EiFlrrel c|4 so)s +116[r. ?lol0] al+s=, r?]r Strahlungg H9 9"1d4. ol ¤+ xdql +e
Eic[. de Broslie gAh](EE 7A)rl G EH}| flal(Eq 2Ael
qq^J +g ^llTlel ql"J+ dSol H z|l +ElkltrHrH ran.z;.
El¤trlE g^l 7)E qF,rJ 0!t614! E 7.1olr-1.
"lEg ++ gzlel .ll+ ?¤ dzls+ +lq EqA dzlelel
t'-s4+ qEql +4+= 4"14.+ ol +5ql E6H^J Ll]+
4zlzl *A4t- el+ eeql ?l= $.$ qlqzl tF4E 4zlzl
ol H_l z}qs Bqa ull, :. qEE glHzlzl xd rlzl-tr-^l *
sld zlB9 ol*6IH ac olg, gzl, 9 EzI9
_r.illql^Jel 1ol4(zB rsn.:). 4zlzlK44(/,= lt).E EqzlE
z[^]l+ H]]gg 4+61 A"J4al AAg + 9l+. ol zl$e ¤
=q=
r xdg'K$,{pi'ol4r 6'}q, L44@ = 29_l)r]. M44@ - 3
zH r4l gd6}q q¤ qlolElq:_41 +e= zlzl:il_ 6146I HJ^l os s^l++. olE cl +*EI d
"J)EE dolE=E ag
ts ulg"l +Aql ++qq r tr e {*slzl qr1 9l+. #r,,Kp, Ee-E E^lqI+.Xd qe ¤eql ^J=.E-trEE
+Îd(EP rze;o1 d=:4 " + f*ol ol*qr 9i.rll, ol43
ol +ÎdE +e 4lzl ullEql sl¤ +9E zlEzl toizlTl
198.1 Xc
=8et rllEol4.
4*xI9 tr+l rr(E_q ze)ql.<l ¤E6J ule+ a."1 q+el 47lE Ela +a Alzlql^l= %lH+l+ +t}q xdg +a
olE"l Eg t+ 99"| ¤{]E trll= Adg ++ = Aql aq= q+ pl¤ +H= ^l4l o + 49+. olel6J %FBg
^J3 ^JE
aol+. + ¤+"-l+ E= g.ol alilqE *ql^Jb H+l * ol¤* +g EI+ql qql^J= ol +aeol q¤99 q6Jg
= =
+{Lllr" ++"-le+ gol $zlaJft.*ql^l= q+ H+l= +
=
+U+b 4"14.tr|tr ¤tle ulel AEql il= qlt}E trIEql xd
^jzl5 tdol{, ¤44_" + +4+= rllzl Hp] E"&g Eltr
+H+r +q. slpe qe qltl{ zzlTl +Î iii+4 Hl+oJ
q gqki+. LHTl/'
o- I
I
---t dxt g
=..4
E-
(a) xd E!tr ITA{
I-
sll=JE xd
xdq 4zl-HEg ,J4r+ ulfalzl qlEql xdol E ,<t
o
cg ¤l4,* trIE El¤ol g+. r=l6l.q xd sl¤g rill E fal 188.1 'J4E
=+
E401ltrt ExfAI= slcl +E xCol LtEtL-Jtr|. Bil=JEg
eel +== g+6-1+ rlq6J fE"l gq.rq+ +aEI El¤ Xdoll +E6tq(4 fl^l'7171^lr ?l= d^l+71atTl tt]|E) 8e..e 0BEtrl.
188 sltr 7lH 733
K0
U6tl4
E^l'C
^1lE
0|'alrL[olE
tr[8,2 20 30 40 50 60 70 80
a|oJ^Pj,zeto
fg 188.2 Ltlts= Xce E+4E 'JA rjlE Hl.EEt 0l HtEJoll
6dE qlel-d =+01
-E,\IC
Eolc=-E Elcl flq. EXIK= drPlKaEE HJ^lzlE EqE fg 188.4 CaCo39 F oldtrill "JEtl44 ol'ellLtolEq Xd E"J Atr
nll Ll-g= +^|'gE L[EIL,!tr[. +!1. + +!l= +al6[4] +eq ralalq ol^l +oil 0ldEill=
.\lt#6|
-i== -\ Olrl
-T-
^lE =q91=
aLl.
B drr xc ,'-l---.
\--l
ol8st
d^t+l
XN
K
5 *=
Hl^l
6 L
,J=7le
K
feJ 188.3 Xc= Ll-911 .-lE rl.8=. "J^l.El= Erl= trl{K'aEol)el fal 188.s 4eld+ altr7ll Ut|B +E(0, yu 0,9! o) dEg a+El7l- aE51q,
Erl.= g=/.lrJrl.. 0lcl^.i Ef= E^t(o1 r=Joil^l= L,Atr$71. 0l ?1(hkt) uJ^l-= iELa ELlEjslq a 7l=:dtrl.
=E6|q
HJrEle *JGl^lE^1 xc Brttr ,J=:Ltrl,. ^1171-
+gel oilLj^l=
r{flttzl qd^l*tr+.
44 +ql= '*3 tolal ^,]lEel HEol 9l
+48+ H]]6&g 6El 9l-g f ?lzl"J "J"J "6lH+1+
6l.7lql
oE H]^l-zl- "Jq+= zlEzl t*ol ll4. El+^J Sd+ qlol
e
+t}q qg itE a8g qB4l uflaj;.lzlrJafE a_ * * rlt} qE geqB *rl-zl "Jq+= 4Ee+ q],rf ,<llzl$ E+ 7l+
9 H"l El¤g "JeA + 9|$ 4"lzl ullEolfl+. e+^J
ole" o|{ u}t} gEg xdg =4q 6l]ot ++.
^JaEEE¤- ^}R6J H+l +^}^l
vJ+ glrll Elq ol Hl$ql 4qlSdol q¤o$r 9l+
+44 qe +9.'4ElA+ ElA4l'E tlzla- =ddril:zH
,JBql^J= 18B.s). "J+ dE+ A¤E q{]Cr+ 44ol El:dzlfl 4 E]¤
E+ H¤4"J E^q +^ld4 +"J
^ljlE ^l-8- +9 ¤+elE Cq+ +lile+ rllzlE +g6F= ql g,q* El¤
6l+ql, EBg AAfl "JPzI fllg +Elrll=
^l-*6IE "l^ll .+"J
ql 4ql6irll H]I6JS+. 3l4l¤ 419 uJl sld 4E= da6H=+. 3l4l +il= Hol HzlTle+ g
sla4l'ql^ly 4zzl7l-E
q+g EgI6I= ¤Etlql^l ^J+"1 tr-+qq
qe +g= 6l+4 il?-l6}zl gir. ,3ill ¤q
sl¤ rilzl
Î ^ltri ++l= EH^J g ¤.^14 e -+ il?-l6Lq qlolqE t+6}4l z-lr-l6J + gl4
dz} tl,.lE EqEl6Iq 7l+++. +"J sl¤Eg ol¤-6l.E
=- q¤
Ii-ll
^lErI +4q= +lile+,tllzl$(:.fl
ÊEH{E r (o) Braggel E=l
188.4) trllolq gBel a4 Hlr6.Je_e.Al eillE Br-
^lEe-l
-"iB + ql4.ol "JHg ols-"olp EJg tr-Eel a^Jg eC6I aTlql= dcol "J=qLH= El¤ +9= 6114617l +16l.01 4
-n r46iq tr-¤¤ rflg rE + 914. ol +EHe E.6J E zI Eg HIFE 4¤"141 E9teq,
"lBlql 4zI tsE"l
7J4
9l ^llEel aTle+ 'Iag ri}4 o e aa6k rlls "1¤.84. d= 7l^la_ B"J 4ol ¤gol4l s4L6IHtrHrH 188.6). ol
4E EE ,Bql xd AAE ¤++ Bragg *zlzl gd^lA E_Cg ol+6ig Aeql+ q¤ 4E_e xd Hgg "J^l^14
,JHql z)=Z +r 9l+(olr+lzl William4 oJf Lawrence). ol o| t!_zJ. tdol
"Jq4=zlE- dzl 4lt6J + gl+. _HrJ +^J
Eg +eer| +4 xd Hgg;l$op. ACg Hl^Pl-+g qlE-ql +4+= ^llTlel dE¤ u^lEla +s_+
=
734 18 r.i{l
zttrJEt q 188.1
e
:ilrJ"l 154pmol Cu(r<a) xdol + "J%r- 4zI9 {111}Hql
A C qEÎ4 zezl zz.+""J trll EI^l-= +4H4. l8B.lb^lql
^l
E6IH {1tr}fl5o] sleg "JszlElE ts 7J4ol drrr=).t
e (2sin0)z} 99oF ++.
B -
dr,, =
L t54um
Zaina = Zsirf t 2" = 396Pm
-r.al 188.6 Brass E=l= +dl.= EE4 ggollA1= 4 4rlEol g^l +^l
o-J¤ Hel z)o\zl a"J
C= HJ^l^|il+r 84-Lrtrt. U^l-= geTl= ?.!tr E=9 3-a rp AB + BC "Jtr 4zI9 {111}HE:E A4g
oJtll, 0laP qg [4 eoll sl=Ertrl. l|e zJd(= 'HJ [)01
"JclLl-a]E Eq l8Ael l8A.la^lq e-16il^J dnt= al3ttzol4. "|4^J
AB + BCTl trl'8e-l E+BH7l Elo10t Elt[.
a=3tt2dnr- 687pmoltr|
ul^J"l El"J* + ¤B 4Aol rlH 1sB.6ql^Je+ Ae + ?l

4 4zl Hql el6l]^l HlÎBr+:/ 6].zI. + Hgg 91 4zL H9 ++l ^llEql q4^l= :[+6IE^JE drll ^ltrq= d=e]
Ddg oll4zltl +E ql Hge ABtrJ+E 448 Q z|.<J u1 +9E. +EI4E 4"1 :14. qlE^l +gl îl89 zlfz| aoJ oJ
E "JEg rll4"I ++. u}4lzfzltr HI^|¤ qgg BC"J+E * 4zi.ilrl= HEel zJ4ol Eq lsAE 18A.1atl(d1,fr/ =at(hz+
aEi|= rH rss.0ql +4U ufe] pol AB
TlzlAl ¤ 4"14. k2+t2)U2)o + iolzlq, III4^J {h/<[So1 lit q¤¤- +4Lil=
e+ BC= E + dsin 0ol4 + qgE dill a.e il+ trl-e--4 a 4E=ffirl o++qd+.
aI r:lrl
"t tr.
dn*,=o/(h2+P+P1tt2
AB+BC=2dsin9 1
sing= - th2 + k' + l'1''' ^za
*
¤zlrJ 20= qg^l4ol+(H¤g ils B;6Jes+El 2evJA
4ols.+ e7l olq4 zezl9ol"F tltrI). 'll++E q"JÎ4ql a+q zl+ <t=¤ Bq +flg trl ol4 +4u HIel eol E
qq Aezlzl +tlE c+Hl]e+ ?xl ?*eq r46l.q ^J e+ ,t4 t r+ k2+tzol444zlE ?*=+.
^J= *q*g
4l ad"l "Jq*4. :-44 ol aE 471 cfuHs+ ? =
g trll(AB + BC
- il"oJ trll)= Hl^LEl: Hol E"J 9t9 zl-zl
lnkt
h2+k2+12
{100}
t
{1
2
lo}
J
{l1u {200}
4
{210}
5
q r;-l6}q BrJ zld¤- +4u+ + q"Jrl-4ol ++!i ae lhktl {2r 1} 12201 {3oo} 1221]t {310}
h2+k2+12 6 8 9 9
Braggo! EElg "J+^lA ql= HlÎzI +EI*+.
10
qlE^J h2+ k2+12 =7(A Is, . . .)ol mI4 9l+= ag +ra--,61q

n)"-2dsin0 Brags9 E^l (18B.1a)
+ e44e-a qAC.q +9ql^J {21r}4 {220} ql.<},t1-o1e1
n = 2,3, . . .oJ Hl^l-= 271, 3),1,. .. HIÎ+I aJ4. "153 2, 3, . ,J4+ r ?J EE+ g2tl(h2+ k2+t2 = 14ol
=zl Îol9 =.q,
6}|B6l+ fiezyzy ltg trIE HI^l= ++UtrI.
. . H]]el v++ql +)4 {400xft2+k2+/2 = 16014) ^}olE 7J4E u}4!z}zlE r
Aq4"J HlHql^lE rg d+ql EELÎz)a_Brasg B4g trl-g ,J HE+ r+. olBlq} ad:==g t+l ^llsql r+
=il ÎoleJ
4 ?ol +ElU+. ¤I 15o14, ol=e ++l ^llE. ql ol+gtrI.
^1tr61^=
)"= 2dsin 0 Braggg g^l ttl= -d^ll (188.1b) (c) SJ ?.!rl

rr-l-r. nzl HI^l¤ {nh nk nI} HEE*q +s= aol4r E xdol t+q= 4? 4zlzl'4zl flzI tI9 dzlE TIE^l7l
4. Hzl l8A.lql^J ¤E6J uls+ ?"1 {nh nk,?4 EE ^}olE 7l ullEol+. rEl6l.q +aa d4¤ B:ol Tl.zlr gl= gz}
,J4e dnx/nol4("171 4 dno& {hkl} EE ^l-olE t4"14). E zt48 flztB4 q ,J6J 4l*g "J_qA+. dz} fil 4*
g* HI^|= +4.]1= ?+ eE +6I7lIrJ 6I olBlq} q= +zl= +4lll= 401 flae-l sJ ?lxl/+.&*
^lql 96IE
Brass
H +tls "J A+ d= 4l4lg i glo oe ol =H xdg ^llrll &+^la+. ¤zlrJ 4l4I 4¤9 azl]
oJzl-zl
49 rzl4 o+
4zl # ÎolE zl=lE +6I= rll lr"JtrI. 6}zl= ?+Azl"J dz} "Js EEzI p(r).J +¤ Ella flxi9 4
18B altr 7lg 735
40
Br
zlfiql ea^l .J6ll+H flzI .J9l Eqil= ddl dzl^fz| ¤
+. ,q-+^J ae %1"6J=ollrlE/= N.olr+. qlEî Na+, K+, "l cr
30 el &+ oJzl^b zJzJ 10,18, q 180.14.
K
-ol 20
nll cr-
<t
10
(o) Exl gs
* ++l ^llE +ql EqflE E= g4¤E +lilel ¤+= E
0
0 0.2 0.4 0.6 0.8 1.2
+ rel+ {h/c[ qy.1g ¤a 4]+g T5' ?!r[e[r 6tq Fftre
lsin9ltl g^lfl+. ol +4 oJz|b flzl-E9 +l^le+ tI+ ql4-= zlzla_
fg 188.7 flxlLl 0l8el t}al ?.1^1.= flxl-HEel-4E0ll 9=:dtr1. tlB +4,J + gltrt.
g:d(e=0, qalN $in9)fi"=09 B:d)o+sl ttpl zxl.= r E Lroll
9l= d^tel +q eq. =q
flrF=el +lil .J ceJ ?lxE[?zl ?.!rt
/.l0lol EJ4l
E 2oql^JE 4I* qlÎ= trl-q=4 4"1 94. zl+ a +fl ^lls +q 4I+ "JzlzU"J g4¤ol qfTl (xp,yp,
z,c)41 9l+r 6LzI xF flrl j9 aB6J 4Is'= z)ol aA E¤-e
f (o)=4"[; p|)ffr'ar k- 4n sin0 (188.2)
L+4U 4o14. trlE ulalzlzlr|.
L ^ ?l^l
^laJ "J'J
ol/E zlg dq *6Jql^J(0 = 0, :78 188.71 al4zl- slq, ol E4l t
h= loJ (ft001 qp.y
HJ6Jql^J
/E flxL 'H+el dzl^f N.e+ e'1. :H rss.sql B"J HlÎ= "Jd6l+ AHEg+E]E + E+E +
4U 4"14. ol ffiel +ltr-il+ zn4.ol + 69 ,r.1.olel xE
g AElql BgzITI ?lg Ellb AHI^l9l Eilall^l 2nx{ +ltr-il¤
@ Tl=dBlBtaJ?l^l
z*Y u|lzl ul-$ 4o14. qoJolzl +l6ll^J x_ 0ol$ gl
lE+ + S,o tr + (snkr)tkr "149
Ed"1lo} 6J a +!li- sinkrol
*7171 S,gq, x = 0.5olH +ltITIzl no\a-, E x = lolE Bg
=
E #e k + 0ol Eql qal al4zi g+= 1o14. olag zlzl ,J9 flzI z}4ql el^l +l{-z}z} zTcTl g+= A* ++
sin 0 + 0, nI+^J 0 + goil 6llR.J+. trl+^J &* "Jzl+ TI¤
6Iq4.
,rJ6Jql^J alQzt g+.
cJAl2 h=2oJ(ft00)HI^t
dB %r-.Jql^lel qlxF= +6IEIH k+0"J +qlg +l
Î+ oltrll- + A:o s_tr+qE rl¤ zxzn{ fltz|7| Lt+
61]01 6Lq, EI+^J 18B.2^lql^J kr+0ol 99oF ++. tr++^J ^Lolql
sin x= x-+f+ . . .9 +q, +oJ tzl x= o.sql flg "l= I A:o g-tr+Elel 4* zn
"l+6lq c}s=4 ?ol ¤ + 9t+.
,TTI =IixLlPY=hm{r-*( kr)'+" '}=t

+lAtil' = 2xx $l$il=2x2xx
ol ++ql^l= lsB.2^lol cl-e_$ TJol TJA-o+¤+
-t
a
f (o)=rim+nJf p1r;'il'*' ,,d, B
+tr| s.4. A /
= +nJl o?)r'dr = ll o@+n 'a) glSif = 2r 9l8il'=2x2n
(a) (b)
¤zld +nfd"e HlzlEol roltr a^lzl dro) az:yel +vl+. leJ 188.8 + =o+E 3^|'e E tr|tr. (a) AEEEgEle.l (100)
=8eE+EjE
rl'31 2n9 9lAhlE LIEtLH^loJ (b)
ol +4 qlql Eqfl= dzl¤E ++= rgl^J9 dz} "JsE
HJ^tq e+q|E oJtr E=+Ej U^l.El=
(200) HJÎE e+oll= 9lti^l'71"4r-e Eq. AE-o-e+E1 EE Tlalxoll ?l= B
0l
ol +4E +iilq +"}]= +ntp(r)dr+ gsq, olag E= HI Eo-e+El9 U^lE 0l= ?lAF^tollctxE EEI "J=E ?lAFilTl LlEl''Jtr|.
736 18 ri{l
++el fl^Ji|= ,*Y -q7l Ll¤ aol+. rq6lq "JH}4"J E

g +lil r.ll ?19 trll= (200) t}l}"ll .llt +l^Flzl zxznxTl Na*
¤ 4o14. (1,0,1)
T, t1,1,1)
t
E4l 3"JHI+^]A a4 \ I \
"J*4-9=e (hoo1 Erpl ql4^JE hx2nxq +ltr-i}7} ++U
, I / , /
ct-
4. :^1gE A+ql= ol pffi Qna= zn(hx + lE + lz)e] z;o1 a

, , 7
gHlp+^la + 9l+. (o ),0) I 1
EJAI t}Elqs ulEE A4l d+ a
zl; eflztE+El tl+q= +E {1+ol Aazlql^l /oolH +l (1 ,0,0 (1,1,0)
4|il- o,,r"J BE+q &+q= ,+E d+g /se'o,*rolu1 4q^J
-f,al 188.9 E7l 18B.1ollA ?a EII= Zltl6l= /.lg--d flxF=E +l^1.
4fzlql^19 dill {+g Q^gr+ ?ol ¤cI.
Ell
E+¤^q # Na.0l4 + Cl-01c.[.

=4
Fû= f ^+ fr""'o
94, olag ZI+61 e^ = (-r),o e +48 + 9l+= ^l^d
94 flzl¤ol fxllap. ol= 7+7+E 4l+ tllzlzlr"la +ltr-
r oJo|;= 4"1 ¤4aI4.
7l7l Qna[):2n(lai+lEi+/zj)"J trll= (h/cf ql,<1E dill A+,
+ +z of,zlzl q-q=r+ ?ol 84. fll Na+olgql q+ SBEE' trl+4 ?"1 84.
4,,,, = I-f,.'''*" " +ôJr5 (188.3) 9lzl
t-:-'t
EzIl
t'n t r,
)
7
-
(n,
rfN
,,
I I
8
0 0 0 0
2 I
8
I 0 0 2nh
I
GZIry 3 I 0 0 Znk
8
TzE?trtEattt 4 I I I 0 zn(h + k)
rH res.g9 Nacl ++l
^llgq 4+ +e oJzl¤ 4l&61-
5
8
I 0 0 I Znl
q4 8
6 I
8
I 0 I 2n(h + t)
.a.alE r88.3^l +g qldg 4l4I6IoF oJ+. ol *c 7 I 0 I zn(k + t)

^l¤l
1
8
g +fl oJE EE flzl¤ql aa^J alallfolo} 6Iq, 8 I zn(h+k+t)

^llE I
8
1 1
At flzl¤E +lzl= ul4"lElel ESg zlz];a

*+l 9 I I I zn(lrh + *k)
^-lls ) 2 7 0
444ot 6Jtri. "J+ flz| alsu olul rHoll +e+ gttrI E t I I
zn(ih +
ol* ++l
10 0 it)
"J^llE +lql +lil+ fl4¤9 87}]el
2 2 2
^llE Îolql ll I I t
zn(ik +
="*94 E|+^J +4 oJzl-= 4hle- oI ol flzF=e +E + 2 0 2 2 it)
4l. r*Al ollo} ol-4 olEel &* "Jzl-= r,/s a4o} 6.J+. t2 I
2 I I
2 2
I
Zn(h+lk+IIl
Hql fl= fl4¤e + ^lls ^l"l"ll =" *9H tr|4^J +e] + 13
I
2
I
2 I 2
I
zn(ih+k+jI)
4l¤ zl4ot 6iq, Hql fl= flzlE=g +zJl .<1le ^l-olql * I I I
I 2n(jh+jk+I1
+qe qq^l *el +Al= 7l4ol ++.Na*olg9 &* ql
L4 ) 2 2
^l=f*,
r4r crE &* "Jzl¤,fE +Elqlr" t+61 g
+4eE t*ol Hl-dq fl;6}e-E "Jqt+= Î¤g + ol Eglrl xl*
Naflxl¤ql 46J gltl. "Jzl-ts eF
sz]]9
+rol4, olg zlzJE +rll= *olo+ +a "Jzlq ql+ d
"Jzl-= *r cl-E
,r.l6p. EE Na*zt +ag &+ ul&z}
zl4r ^J4l++. Eall= a3 zldt +¤. %FHg +4, +lil, 417l¤E1."1r1. 4"lzl 67l] gzl-E=g E+ +Al7t +olq,
r4r +ltlg Ll.4.11= gBs= "JE= 4o14. +l/J. "Jzl olEE +a "Jzlq 46J 7lq= r-l-q=r,+ 4.ol 84.
e4*3 h, k,9. /ol E+ A+4= Î¤¤. g+ql ;r. 4l4l Llri2r(hrz+*tz\ * rizn(t tz+ttz) * rizr(*tz+tt2) + ei2n(h+kt2+tt2)
qI+. r"]r
d"n= nol 4fg 4l +r"1;4 g+"J oll -r"l '+ei2rlhl2+kl2+l\r'l
. i2fi(ht2+k+lt2\
+e
188 altr 7lH 737
&h, eook, "l C,' 6J¤g dP +to1q, Ele[^-l EE ^'ll 6]9 1+1+rl--4V.+f-)
q-s_r+ Aol ZlÊ+g+. . h, k, "l /ol E+ g+H, = a$*-f-) Fr,ru
z\
. .I4zl ¤+olr Eol 4.fol4+ E= r HIEI]H,
Llei 2 n ( h t 2+ k t z I * ri 2 tr ( h I 2+l t 2 I
+ ei
2 tc ( k t 2+l t 2)
+
2 a (kt z* I t
"i Frru=o
* ,i2n(hl2+ll2) + ei2r(,r/2+k/2)l
hktol E+ g+"J ullE olEol E+ 4I+"J trllE+ dE

îl
.i,rn - (-l),9 ols" 6IE q-q-r+ ?ol rl Aip+E+ zlz| lt-olq, "J+ HIÎ= 44421 ?*=+.
+ [(-t )u.' + (-t )'*' + (-l )o*' + (- I )**' + (-1 )'*' + (- I )u*u ] +4 f* =f--9 trllE sE"* flzl-Sol "J%r--P ul|¤9 ol$
= (-l)u** + (-l)o*'+ (-1)**'
r ?lg qlql 4=J6l-4 ololi} hHE q+71g-+"J del ^ll
zlzl 44 0ol gq.
nF+^J Na*olg9 +a q]+ di]l Tlol= q-q=r+ a+
"Jzlql 188.1 ?B-l 4zl9 A+ qH qlrl¤ol 44
^l7l$.71
f-lt+ (-t)** + (-l)u*'+ (-1)*'] 4zl t*r+r
O =Hqt '[tn Fo{rE *7; lol + )t + q +\
qI¤ crolgql El]tI "J*s= q-q=4 ?"1 84.
+lzl +41 x v a Qnu
HIÎE 4lzl= jIlE Tl+e_l 4l+ql Hltsll6}q, E ol +E Tl
I I
4 )
I
0 0 nh
+E 4l+g +4 qlzl Fhk,ql Hlql++. uI4^J +4 oJ^l7l
2
I
4 0
I
2 0 nk f6+ freo*olfl ,<llzl looft r+g=4 ?ol ¤4.
I I
3 4 1 ) 0 zn(h + \k) Iro,o. FnTo,Foxr= (f o+ fr"-'Q"')(f o+ fret4* 1
I I
4 I 0 zn(*h + k)
fi + f ofr(r"'u * .-roru )
4 7
- fi+
I I
5 4 0 0 2 nl
ei'+e-i'=2cosx
I I
6 4 1 0 2 zn(h + !I)
I I f i,* f,i +2f ofncos@,,*,
7 4 0 I 2 zn(k it) +
#ql tr}+,\ fi,+fiql q6flzl4+ E=

6}3
I I
8 4 I 1 2 2n(h+k+it) {zlrJ cos Qro,A
9 I 2
I I
)
I
2 zn(lh+]/<+|I1 *:"Hzl{, E ol pnrp h, k, o) l4 x, y, o) z.ll 9¤814. r?-l
l0 I
4 2
I
0 I zn(lrh + t) 6Iq HIÎg rllzlzlhkt{l tr++^J H6}ril g+.Ae+ Bsl HIÎ=
l1 I
4 0
I
7 I zn(ik + t)
gltrzlzl n"J 4l tr-41 adg "Jezlq, :4atq Elg + gzl.
t2 I
4 1
I
a I 2n(h+ik+tl E t}+}.ol eg ql= dill HI^L ^llTlzl-0ol EtrI. qlE^J E
I I
l3 4 2 I I 2n(|h+k+I)
^Jzl+ (h + gtrl u++xl h + k + /9 fiol Ef"J HI
k+ t)nzl
Na*olgoll 46ll^J HH ar+ Hl++ %r"Bg ol$-a].{ o}zfl
^t= Ae+ BE+qE ffiol r"J+
gl/J-ol H+lqtr_+ Ae+ B
e+ ee crolgel +a ql6J 7lq= Eg + gl4 ,I E"Jg 41ts lggu1.
"Jztql
"J"J-pel 4zt sl¤g E= {hk\q\ ql6ll^J 7R:6}q, q+^J
+(-l)" +(-l)* +(-t)'
E%r--Pql q6J q¤ Fgle+El g+ ttq h+k+lel q}rlg
,f- [(-t )u.*' ]
r?-lflq r+q-+ *++^ qlzl¤ gg+ fl+ EF uEn.llH "J"J-r 4z}"ll qlql El¤ +97I qgt} ole+ ul-4}
zlzlf, "J"J-F 4zLq^J= h, k, oA I +4 $ol ¤4olr +ol
zl alulz| 4-i"14+ IE= Eol 4.+ola ululzl alulz| 5
*
F,,r, = f ll +(-1 )o** + (- 1 )o*' + (- I )*.' ]
+,f - [(-t)'.0*' +(-l )' +(-l)* +(-1)' ] ?l H1^l¤ol trd"l ¤+. EE +e}+b olelql i{l
114
ÊEH{
4zt B4E 4B6l+ Ql ole"* f gl4t:H
r?-l+q ++ .I¤¤¤ ++6t71 Hl*+. =dEg
18B.10).
. h, k, 'l /ol -lt+ 4+4., Fn*t-f *{t + I + I + l} +f -{t + {h/c[ q!,t19 .<llz]= lF*,|'"ll Hlql6]q, E]+^l ol$r]e-e.
6l]'&61+ rllzlE9 4l# +l+e-eri de4eE +a q_l
738 rill
o
o No 6
(, No
(ro
c)
g 7I li}+lol= + 'JCg zl+ hql aa^J"J op. rzrit"-oJiE
ee =
o o
-- o
;-OeeNcleFNNN
Fo=No- oo=rOFN
OFi-(YrNNF)
NO
(\ro
g9 g rEl6lt+H 94.
!
N N N N N(Y)(ON(Y) (Y' ststt(Y)$sf(Y,
o tH|_PI
tlo
! =ol
F_r,= Fholg +
'Jcg h = --PQ +*7lzl f6}zl
?*r. l+El lallzl fl6IE g+.
o tHI_lI
tlci
lt ! v p(x) = !ro.'"* = F, * itro.-'
=Fn
^* +iie'n'^')
I !
h=l
otril_tr
tlo r
= 4+ |g,o{e-,"* +e,n*)
h=l
fg gg :atfe
188.10 7f^lE"J eltr +9et 4E9 LEIL.! eo+e-*=2cosx
gg ^ll
AllsE ill4l4 =rl'E
'Jd; U"J-F(fcc; h, k, /ol fl-7 E+ol7lLl d+
^11
a
EHJ-l(bcc; h + k+ /= ?l aEol =+?l
gg-P. E"J l'tlE Fu+ z\F,,cos2nhx
0lajEl=x0,
=01
+Llel' HlEo-[ EE r E+l
=+ + =ril,
?lrl. qfld= d=E h=L
^1lE= ^.lE-g ^lEr

flile+E1 7:g + 9ltrl-.
ls7||E 4llE"J +qAeq, :7?-l6lq p(x)!. Aol
=^t4
pffi:r.B
E 4o14. ol +{Ll|9fiultr4l. "l 18B.t1ql
EI+= 37HE +H,6J +.Idg +4.I=ql, olEg ^ll gz}
zF= ACg + 914(144 oI4E _H_ol-El-). r?-l6lq :rE + E +laql 4'J61.= aEolr+.
a "Jzl Fnr& "J + fltr}H trl-g ol.a" o|{ +91 !g ^lls +
ol ,"1,\o if-il- -,\ o zlolrl
_zJz-l Elr=
_-1 -r_f,.1 arp\r,,e | t- ol
,4 -= /l--i-i.
=
:dd (188.4)
P ? ) - i},,*"-2ni(hx+kY+tz)
Fourier
hkt
3
9zlrJ v= tr91 4lEel +El+. r8B.4^lg dzt Esq +6J ui
Fourier gt¤"14L 5-gO. Fourier H+g slE AHlg E"l]^J
oil
K
qBi ¤els +4+q, q z}^ll6J
'}]¤¤ Eq l6cel Elqlz}9
kJ
tr4 roql _H_r| zf,r11al ¤E6l] +9I+. ol a+ql "l+El= HJ 0
H9 Ezl-L tfl ^llE tlel dz} I,JE Eq¤-sine4el cosine

00.5x1
+e_l +e_g-E +ELH= 4"14.
fal 188.1 1 H7l 18B.2oll^l 4lt:"t Exl' "JEsl -E,\l e;tHqeJ^q)et xl
7I
";7 I 1 8B.2el
=rH^l+ ^{).
fflftfl Ext "JE lltt
Fourier El¤otl elEt
qE AAel {/,oo}HEol x4 8.6}e-tr +t61 tsq9l+r +4 ElCg 6l+ 6}e-l fz| u$-$ffi E+ El AEq1 d
{46}z}. xd +4 4+ +z "Jzl¤"I trl=q=r+ *"1 44 6[ "JEe-l E^l Ar+7] r+g+. +.$ AE h(q]C +el +E]
*+. tl9 cosine 6J)91 6ll'061+ 6.J¤. dz} ,JEE Hq¤ tr-+
^ll"J6}al
+4u+. He E"Jg *e ltg hE+q +g+.
h 01 2 3 45 6 7 8 9
F,n 16 -10 2 -1 7 -10 8=32 3 xlTl -E^71 18B.2 f4 l==?llq= ols-" afl.rJ ^}ol* 7
h 10 11 t2 l3 1 415 a "Jzl¤(41+ HsIe+ .+a ua6 Eql+)g zlzl:ilol 4l
F,n 6-5 3 I 21 &g ^lE6ll _H_ol-e}. qlE^l +lql^le+ ,J2 rn=.rl-o" 6fft.r-ll,
ql6ll^lb +g= E_+ oJ_e-tr +=+.

relil 4E Blea+. ol ++l ^llsE x4 dgl
F_r,=Fh?l h > 6ql
Lt++= dz} EsE E^l6Iq4. (hv 5v)tt's8l ftr :6

z4g ol {lE9 188.4^lql Bq+qo} al*41, Exll
^tEl
188 Eltr 7lH 73e
(e) 74"! zlElEt q 188.2

=8
dz} "JsE 4l&61+ q1 ols-" 6]} rss.+^19 +a "Jxl+ "J :-H rsn.r2a9l B?l dz} "Js9l 6ll'J6l-= Patterson zlE=
HI4e + +A EL+ lF*le-_E _s.^l¤+.¤zl! lFro,lE tl* :.H rss.r2bs] z;r4. ¤zlql +4+= 4 *dE9 gdql
ol:L aE Fu*4 +lt"l4(ol '+ltP3 +r+E 2^1fl. rBe
']l+ tL44 +lzl= E4e-l +a +ql Eq il= 4 flzI ^J
e 44H oll ol¤-qE 7l]'Jolq, e.9 zc9 El4xl9 ^Jal r0 E 44e+ tlql4 Hflo.lg +{UtrI. patrerson zlE= +C-
9 s"I4).rq+ d+51= rmE. +a oJzI9 zll# lF*,|'ol 4dolq gdql ,J+ Hldg +4U+= ag +u-6}q+.
4, :_4a}"l d+ A4E+q= +l^Jq +6I^-l ot+aE g +
s,sq o+q 2n ^Lolel qH atg alofofizl E + s.rl. ol
q6J .}irlldol Hts +.1c| Efilolq, ia ar+= Eol+:. Aol
R
-uH rss.rrol4.ol rg¤.+a "JzlE +l^Jg He+^]71a4. R3
R4
+¤-rqg {.711 --9 4o14. qtr "JBS-e.E +a oJzlql+ R

R
flflg +ol6llot 6Lq, r$zl *$ ull= rsn.+^19 ol$al-¤ p R3

-R2
. +B + H+ +C-qla ++l ^,llEq A+ql. +4. oJ47l
-R3
d+q^J a|l f,izllzl flxl ?*zl"J r?-llE qd6l Fr*rol "JoJ -R4
zl 9"Jzl9 s{lTl h+=tr+.
gltt Extl} ¤4 zl-zl %FB " + qL AEvlz)Y qlA$ + (a) (b)
9l+. r zI^J +,q+ aq al4z} *+l ^llE +ql Hli4 4g leJ 188.12 (a)9 Exl "JEoll tll36l'= Patterson xlE= (b)oll LIE|LH
f9 flz}7} Eq 9l= +71 E¤4 +rle flzLzL E fltrt. 4 BJtr=el flEo.e+qe.l T"lalel,Ht|-Bte (a)oll,\i9 fl^l-Z 71a;19
qfl= *zl E¤ql ts4 lroll ?lE^+9 patterson :d¤Hol4. Htj-dzl )1zl= LIEfL,!r[. sE ?EolEe
=
HJtrol LlEltitrl. g+ de4?]
zalelolEE (b)oll rH-d 7lq= Rr Eie-e +Ell|1fltrl.
ol +a oJzl trfldql ,rllzlE+e] ol]rl]col s.
Fr,u
"JHql^J=
"l eqzlE lFno,l, <t9 "]86]]^1 188.4^lr+ Hliql q-s=4 a
e ^lg "JEq^J ++. +4+ fl4-b &* "JzI7l A^J(gzI HsE =zl ¤s-) &
+g xlEfl6lq 4+^J olEE +lil. d4l EF"IB + ?l+. r
P(r) =
# lq-,I' e-2ni(hx+kY+tz) Palterson gdts (188.5) 4r ol +ag flz}9 +gl ^llE +ql^lE flilE+El Fn*9
hkl
+s=- alt}6J + fleq, "lEql El]6l]^J 4l&+ +l^Je dill
¤zlrJ ,9 ale ++l ^llE "Jql gzl¤ ElEl ++l ^llEql El]+ +ltl4 E"Jg ffiol +tr}. ole]. #"1 4E
=q?i= ÎolE g.Jg EEIE +d +d-4a
,1"-l'|. + g4¤ ,1"-1e+ oJ.J1g +4u+. dz} "Js
^llsel +a "Jzlzl
rle--$ z;
ÎolE
6J# p(r)z} flxl-=9 +lilel q¤- trJE= r+4rll= HlHql 6J 3 E-a gtr}E 4* ++6l]ot ++.
f p(r)= fl4¤ rlol9 4"-1=. +EIq= q¤- r,JE_$ xlrol F= (t[r,..,,* (t)f.,rn,+ (+)f,,rn,*"' (188.6)
4: P(r)E ¤al Patterson ll5.4L qg4. "lel6J zlEql^J=
gd-o ++e ElEl rtr $.tlElE +lilql^JE *?4zt 44 , ¤zlrl -fi."r= +49 flzl9 &+ ?lzl."ljL firn,= ,Iqg g
++ Bqd flzI dl.ql 96ll^l +4+= lolr}.r46}q ?l zlE &+ "Jzlol4.,6rn,==g E+,f,*r_tr+ gt z+gq, Elg
zl tzl (x6, /6, zr) ?lzl9l 9lr flz| fz| (xe, /s, zu) 9lzl9l ?l ol Tfqe fl4-Eol +fl ditl= t6ll^] +Eqq flg
^llg.
g trll= Patterson zlEoll^J (\- xs,/e- ts, ZA.- zs) +lilql + Q5 "lE9 gl1lol 4+zJ +4teq-rll 94. EI+^l [ur,,zl-r"ll
*4zl +El+trI. ol5 al-89 *ol q= *qlE S*4zI 44 "lil= d s4=,6*rql E+ aql ulall,<l o]]* "le+6t{, :.
q=rll, olag As+El BEE ElEle+ ul.{z}zlE B-e.*rl e r-16lol +7j9 flz}9 +lilE+q 4l&* a4 +eg +
F=
EE EE]E glzl ullEol4. ol zlEql +4+= ¤f-4fl +ol gE *=41 Eqs ¤cI. ol +l^Jg HI^l-^ll7lE+El +a+
+ flz}9 gz} Hsq + ZAZBqI Hlull6Jr+. patterson zl.E lFle+ aq+48 ++l
^,llsE
Sdql dx}'Jsql +6J Fourier
= E6.J:z
flEql z_l flzl ^LolE 4r-le+ r zt^llql 7l"Jq= BCg B + 9leq, r?-l6lq +A+ flxl-s+ B4l zlHe g
=
,J+ HlAg qqd't. 4¤E q\vl^lE_ "JotB + 9l+.
7t+0 18 rill
+a 6H4Hql^J= 4trEg ftr_ .x;r ?14. ol ,JHg

4l4l
a.alfl lEl de Broglie +Al^lgolzl +1611^l= +^d
oJe"
flzl-Eol +9 ^llE +ql^J zl-ti4 " + 5.4r4alzll +lil*+ zl9 g$+g g"t"F 6Lq, q-ul^l olEE +E= "J.I"t
-:r H l(+Îdq +dql^l), +fl F4lBg ole" 6|{ fltEol
++. ol +E= +F EH]] ?lrl= zffiap E* rz1-g g
5e+ Zi$$ z|{ =ffi$ +6J+. . .J+ +a t{E=r} + 4l +F "IHzl EK_+krE+El 414}ts + gltrHE9 ze9
+a "Jzl¤E a;i1:zel-a ^ll#eJ -J)r+E ,rl-ol9 +41= + slclzl9 t4 zg -H-otzD. +tz}g e=j=g -szl "lgoll
=
+e+ 91tr1.
zluJa|fl "*g +Eol +trI)g zlzlAl6I= Er+E +4U4.
qlE^J trl-*!+ ae gg *E Savre +E trI|^lg + 9l Eol +F EH]] g"-lq el'lE 9s rqJ.<l ,HJ-6Je_E gE
rl. = 6l-= +^dzl-g ¤t Brl # glHzlb Ey-lkrcl. ol e
OI H-=t-
fDh + h,, k + l(, I +fY-{ tn-= m* t e"+ol+. trr+î p _ @kT)Vzol;4 de Broglie *41
(Fr,u9 +s) x (Fr,,r,r9 +s)e+ A¤- +Eol ++. 4 L=htp4l E4^l +CztE +tls trl+4 ?"1 ¤4.
Sayre gE SZIÎ (188.7)
^h
)_
/L-
qlE^l Frrr* FrrrTl E-F 7r g"J ,ll= F*n7l azlul6lE "J @kTY
ol g z|bd"l ++ tt|4^J 373Kql^J= rJ-q-r+ *ol E4.
44 +v= 4+4eE qe6}7l f-l6H^J= q¤ +HE+
El +EeI +a E¤ql E46]]^l 4¤ llzlE 4l&6ir ol4ol , _ 6.626x10-30ls
'" - l(L.67 5xL0-" kg ) x ( r .38 I x l 0-" r-' x 1 : 23 K ) ) "'
dxllE +eil A4e+ + "*rll EIE+ +a +fl ul4"lqE
J ;
(qlE^l gzl9 +lzl)¤. ill4l4_eE a¤6l+qoF ¤l+. ol r+ lJ=lk9m-s -

6.626x10-34
CS +ael E"J fE"l{r -J+. ol A'J +4 4Aql elsll
kgm's-'
(1.675 x 10-27 x 1.38 I x I 0-23 x37 3)'t 2 ( kg' *' s-2 )r/2
^J
E+l ^lls +ql Eqil= fl4¤E fl7]|71cq6}al aae
+"J olq4 ol4 ?ol TC +lzle+ ¤!* ,Jol rzlr AEP+ =2.26x10-'o m = 226pm
EE si|= +Ap fzt ?14. "l 4dg E" 619

flz|E"l tl xlTl$:1 188.3 +Cz}e] ul-^Jol 100pmz| qE ql gs
F6i= rl+g +a6J +E 91trI. +gE= 4l&6}q+.
)I oo5l .E
188.2 EItrEt C^t Eltr

=8rt
+^JzIe+ dzl* rEg qE^d q+ql sle ¤tlg ++B + +^dz} &+e xd &+r+ + 7l^l Hql^l rTil +s+. a4l
ll4. :24-r. ol=E ,I+s de Broglie +41^l(E1 7A, )" - htp) E +^dztg &+e 4 ¤ttol4. +c4+ flz}9 dz} 7
=
_o + 448 +:i4.flz}-sql^J
^J^Jqq
g+F+tr-+ A+ 4 +& Er+6Iq, 4zl-E9 Elzll +!-aI ?l5.'7olg qq'g
g +^dzl-= xdr+ Hl+6.J zlzl4, tr|4^l sle ¤eql Fql^J q=4 tr-E+¤-q 6J+ tr+4^J GBzlzl t+q= ^,il
ol+g + gltri qlE^J ?lzlEql^J +g 6c^l_= *4xil(+s 7\+ 4^l +oil ++614, azl& s ^Jel "Jd gzlql E{} +
4 asJe+ ggol +=^l4rJ * 4km s-, aEE +EE 44l ^dzt tI+
tllzlzl ¤zla}4l trolts + 9t+. +^dz} t}+g ol
alfl :29 .,4^Jol "j roopmTl ¤+. d^llql 9lq^J= +^dz} +6IH Ae slqlE +q .q flE Nr4 co ?9 grEE g
HAol tr-'& ¤EE rltlg *xl"J z]leu|h +AA4 ,J2 4 zl-= EER + flsq, pecogl^J9 d^J-+A^J dol ?3 I
¤ o + sl¤g ^14^J +4 H¤g da6J + ?l+. E ¤+g + 9l+. Ezlle +^.izl-= r zlolsli zlzl
^gql
EHIE= 4=+= 4o14. ol zlzl EHIE= dC 4zl- "J9
gz}+ ol¤14}1xl ?J:= dzlE 7l-41)ol "JE= zlzl*4 4
EEEU E=c^lEdeetrEtzttt
q}$ + fleq, r?-l6Lq sle +H= Hs+^lvJ + 91trt. ol trll
373 KE ++le+ g4 ¤¤g olE +c,(lE dB4"J +1}
g 4l&6lq?+. A+61z]l ol "J"JolEe t!¤ql^J tr.E"t! Eql 6^Jzl qag zlzl4 a^lE ?*Y 44= a.<[a[i r]l
Qr. zl-4aP4.
ols" B + 9l+. zlzl4 drl 4zl-*
"Jd flz|Eol E"J* g
aols,r]E rEE dzl-^flol {rolal Ello}g +E}8 + 9l=
4z}4t:ze 188.13).
188 iltr 7lE 741
7171q, q"+^J El¤ dBql zlq+6}+ t}gtE 44zl R,olL

?+ 0= ol+r
"J^l dzt ¤.(EE +cz} ¤)ql EI6H^J "Ja+
gl= flzl-rdlol {zf(EE: +cz})E &+^laqr ^J4}6]]EZ}.
ol $xlz| {4 z}]9 gxl¤s slqflg *ilE &+.tllzli ol
E= flzl-tE9 zlq. aJ* 4,ol g+. ol dill &+ ^ll7l
=
(0)='l+r+ ?3 werl 4 o + +qTl+.
fg 18B.13 HJrl.T
ld Etroll^1= zf
^1lEE
fl^l'atrJol tl= -Lr
^1lEE
fl^l' \o)-Zf f,-^*: s-ffsinlo Wierl
^l
(18B.8)
.^rJrl EjEBElzl tr^1= 0lFL 4rlEoll uHEElol ?leq, 0ln|l=
^le
58rl-71-+ I:,Jzl Eol,J.J+ gHJ 4rlel Solel rl7l4 ,sEA|'EE 9Jez1
atol-d Eltr +tr|= LfElL.lEl. -La1Lf Xc atre= .J"J bcc 4^l.e?J a^lE ¤zlrl ,t= dzl-gg ol=
=
dzl-g .r}lrol:t /= drl sJ
g0ltrl. ?.!rh flzl9 dz| &*H +4utl. dxl El¤ "JBe +
s -EE= g+ql ol+g+(Eq rse;.
40kvE illHl¤il¤ ¤!6l]^1 7l+¤ dzlE "* 0pm9 ,ltlg
=9-d7]lLJ=
Ir. U t= +CtL %Lalo e trrJ tdql zl.J99 L}EIL+= CI tr8. glg $rtk sl¤E ^JlTlrrJol
+ag + glr g^Jg +a6J
^llzlE Hgol4. f $,zl trll$ql L}$ttr}. ol Ar+s Fourier -JCg ol-$all,tl
o2. q-g/.Pt 20= H¤ol sl¤q= 7+EEI dx}'JsE zld ACg + S= 4"14.
I3. Bragg9 g=!e + +qd 4zlH ^llE7I +4rjl= Ela H¤ tr9. l*rtterson rlE= flzlzJ ulEl9 ^lEtrI.
el 4Ee+
4xlEE Îolg +41= L+E}ur}. tr10. ElflEql^lb EAl4 "JHg ol+6rq El¤g geAqr ^8
44. tleJ Erl= flzlz} +Îdg t}*^l7l= aE= +Eiutrl. 4q= 9l^Jg add-= *H"14.
Ds. +4 ?.!rH {hk4Br+ ++l ^lls +ql E&qq9l= flzl¤q trll. +3E 8trJ +¤ol+r 6l+ ag +c.J sl¤ F99 ,rllzl
e-1611^l qe!= +9 dill tl+ol+. e+'JCqI E"gE Al&* +9E rllzl= g *ril 6ll+71 +l6J
I6. dz} 'JEe+ Ele +9 ÎolE +al= +E]..ll=- {ol Fourier 7a ul4olEl5q +Ag.'Je+.
HiI"l4. atz. Wierl {$ dzl9 &+ ^ll7l$ .<le 49 flzI ltoi rlol9 zl
47. Fourier Edg tI+ "J^rs+q r+g dz} ,Js EE= BC 4e+ ¤+^lrJ+= alol4
6Jr+.
=s-d^l=
ce l.l
-1 +^l +l Ha
nragg9 Hzl ), =2dsn0 dy 4^l zjl,20=. q"J^r4 188.1b
tlt oJzI y= +"fttoe)sinkrl t kr)r, dr , k = (4n I l)sinl *B 44 flxI 18B.2
+= ?lzt Frr-Zf ,r"rr',', ho?)= 2r(hx ,+ ky

,+ lz,) a9 18B.3
Fourier BC P0) = 1 tI v ;)40," -2fti( hx +kv+b) Y= ++l 4lsel +El 18B.4

IH
Patterson Bd P(r) = 1U V lll 4-,1

2
1
18B.5
,rtl "-zxt{hx+kv*tz
Wierl \0) =Yj i(sinsR, /sR, ), s =

(+n I h)sinlO 188.8
^l i,j
EEf lgc Jli{loll^Jol
=-Et
> 0l EEIE Hfl+.= ol8

ili1l EtrE dtrr+ B+E +5E 0l6tl6[e1E flrh 0lg r.alr
Ex[= EEn fl= eBE ¤+= g0l0F:dc[.
IIII
> 6_4d T|ILJ III /.
Lll
lall.
Tlxl E^lel
=il EdErl.
Erl rrll7l =¤oll
el6tl^J
=+
0l8.Li1l, 88=At lli1l,
IIIJ
> rJ.e.il qHl rl^.! fg r8c.1 3il-g 4"J e|g ?I= oJE= 1&l fl 4"J gg
"EE =
E^lrJ+lE4rE{EE 178)r+ eg 749 "JU4 gtr(EE 18A)=
+116l'1 9lolot elq. E+ eEtE tseldPl +16|{,(1= Hrickel9 E^l
fllE-d+ olgEr4 eE)el flalE gi1 ?loloi elq. 0|8 eEr=
EE6l= tllE tlgrlE TtlLJ= olE"t|ot eEl. i
,JBql= zlzlzl ll4. :- + ,JHg dail +"1 +^l +4+
,ll +¤ ¤-EIFI ABA +99 +"1 +s4 al-E 4,ol4t:ze
r8c.3a). s atu}9 *Be .rl4l +g a4l +el F +lql ge+
o[ ABC +9E *ol 4sr]l 6l-= 4ol4(:zB rsc.rb). ol +
rill= E+, olga6-J trz.ll, -2" +aoJ(E+ EllJ.) trill, "i e ,*"J *rlol +4 HJ-6Jetr. HI+q7l qiEql + q^+¤ +471
z| -Zxll_e_ ¤+6J + 9l+ "lEg ?+?+ 4E guJ"lE ÎolE ^Ja + 9lE aol+.
eq+ ^d4ql q= *=+
=cg Eg 4.g-Sftcp: hexagonally close-packed): ABA Fg
,l HI+Elq ABABAB . . . 690l ++t+.
19c.1 gB 4.E-S(ccp: cubic close-packed): ABC F9zl- Hl4
=+ 9"1 escABC. . . +gol ++B+.
#+ql^JE t-g"* "JolgEE El]g diilql 44 Ezllqol ol
olgE¤ d+ ++6t4l aEL,r.Jzlfl.<jE flc4 dcg zl-zl olBl+ EaEE +4= rH rsc.+E EH 016l]g + ilg a
,ll 6J+. ++ gÊq eC BE+= ut44zl +16ll^l= #+
olrJ. ccp +e= Ed ++l ^llE. +sal 6lq "J"J-F(E=
flxl¤ d+= t+.6J rJ4l+E -8. jrBg olf-allo| *+ 'il fcc: face-centered cubic)r-f-LE + tAq] +^l
-*^l6J+. +Eol
E +"J +E glzltrJ hcpei- ccp ffiq +a.ol z[1t fgai
+EE ++ g^=g,rll zlzl ++tI eA BE|] +E q! qL
aag "JE=Ell, ol + Eg 'Jill+7| 44H ul]g tl4E + 4. olBl+ +aE *= ?lÊ¤ s l8c.rql f+all +9t+.
"J 40141 E+.
a"J-+g +aE a"J AE= "Je-lE * flzlE Eqr+a
(a)aES
lB rsc.r¤. ¤-]q"* +=ol -"1+ *rJg 4qtlEe ol$-all.<J Y Y
n
+fl a¤- LI4u+. a"J-+"J 3i}+l +a= olBl6J.aIrJ_+ I
g'+s$ Ezfl glol,<-1 *3 4"l4.rq+ ff$ E7l] +=

%r-Hg t zlxl Sol otrl{, :z46lq q.=E ].azy +EIB

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,

Peter Atkins I Julio de Paula I James Keeler

,J"Jg zozolE2g rB r4l

rsBN 979-11-5909-578-8 93430

. 0 I :49 EEq EJ r.l 1tile Oxford Pubrishing^lgtol EE zl e+ o + 1a1 ;r +sr.ql ?]aq q

il^t| LHE: t7H

qd4?l > .Jg-d qHl

+Eel zls. s.7I deflr+. srll E+ll6J olE s7r PE +q 2

¤4"J {}E¤- st"f"lz1l 6t7l +l6J d"14. ^IE

flli.ol ol,'lel 7l4al

EIEtrlE 8^l qqrlE8 l6 ?J!} 0{L1rl

GJilqI zltrJEt q?E:z

"lE gqsse4 ol !l s¤+ rsokhq zlrlTl roTnq EtQl el+

e g+ +4E ++.J fzl Exll5olq, fl+¤ 4# tls E ,t4^1

goll aTHE Eia +714 rle

IM PACT 1 . . .ON ENVIRONMENTAL SCIENCE A DEEPER LOOK 2 The fugacity

=zl =+. A=EE

dfil rl^l ollL1xl,3-E, "J Et+ 2A.3 tsA g 36

=g:d j 2D.1 SE olEr+ESC EIE 57

(a) EE E|EE 4l+ 178

S.Zl,t 7 gfrp 221 EE 7F EII EE 267

¤E EXL EA 316 ¤B Exlt, EA 359

E'7{4 9 Exl T= 319 844 10 Er[ E]|e 363

(b) +B qa 398 11F.2 tr|fl^fE^l 440

EE 12E Lt|+ ollLlxlel glEetrl 485 529

7HE= 573 1sD.4 dErl Zltio_++El Eg 614

Ez1,t 1U HJB 587 ¤B EA 624

TllLJ= ffi 17D.3 +4t8 ig 704

751 Eiil loFl

(d) E4r'4 =J4rE d-Ee++EE e8 780

E 1A.1 galel E+l 4 8 6D.1 2e8Koll.,\lE E= trlEJl¤ 2t0

E 1B.1 (E) 7E{ 8+ t4 8 6D.2 ETIE[-+4 2t3

E 1C.l Hlalg Al*, alkm3mot-]) 2l 8,7F.1 7E aal g4 273

t 1c.4 g+ 8Ell^l= 25 E 88.2 ++ flAEe_l flrl.url:e, r/pm 302

E 2A.1 qa{ 7}rl=+el g 37 E 88.3 013 HJxIE, r/pm 303

C,,^/(JK-1 mol-1) = a + bT + c/T2 47 E 8B.s drt TIE.IE E"/(Hmol-l) 3M

8 2C.4 +71 ElElEel E= gd t!gtrl(2e8K0t!^l) 52 E 9D.1 Pauling9 d7l#E 343

E 5F.2 179 E 13B.I 2e8 Koll^jel Ei{lE EdE 514

E 208.3 I.l-E!El .4.E r+ti!

E. 14G.1 Ekepf 45 574 E 18A.1 gE 728

Arrhenius EEFIEI 596 E 18F.1 2e8 Koil lE xPIilE 761

ilEtrlel 8*l r 2trt E+t 5 El¤txlel 8al to Euler9 L! 242

ElEtrle] 8Ll z qal Eillg gtr 6 ElEtrle.l AlAl

El=lrlel 8+l : .gEAE,T

ElEtrlel 8*.! + I{tl

ElElrle] 8+l s EIE 22 ElEtrte.l /\l^l

ElEtrlsl 8*l 0 grt oilLJrl 33 it=lrlel ,\l^l

aFtrlsl 84 z ¤EUll flAI 35 aFlrle.l .,\t^l

Erqrtgl 8+.1 s E6h d+, flaJ "J 0llLlrl 4l El¤lrlel ,\l^l

ElElrlel 8*l g II{E6T.A

ElElrlsl 8^l r o ST EIE tw ilEtrlol ,\t^l

ElEtrtel 8^l r z E+ E71l l5l E[Elxle.l lAl L,

a]trtrtel 8*l r: ErPl=^l 223 ElEtrle.l /\l/\l

ElElrlel 8^l r + -H./\^

1 The Debye-H rlckel theory

4 The energy of the bonding molecular orbital of Hj

6 Vibrational selection rules

7 The van derWaals equation of state

8 The electric dipole-dipole interaction

9 The virial and the viria! equation of state

10 Establishing the relation between bulk and molecular properties

11 The random walk

12 The RRK model

13 The BET isotherm

4. 9 #e ^lEE dA e"q1 ffio}{ trEI^I ^lEel E $B/aun: 0.936 0.252 0.012

^J +E gqg 6110} EE-14flE= =tr}.