664 Chapter15 Chemic.

rlEquilibrium
l

15.53 Hon' do the follou'ing changes affect the value of tire ( a ) U s ed a t ai n A p p e n d i xC t o c a l c u l a t leH ' t t x {
eclr.riliL.rirLnr
constant for a gas-phaseexothermic reac- actiorr.(b) lvill the cquilibriumconstantior thqel
tion: (a) removal of a reactant or prodtrct, (b) decrease increaseot decreaseu ith increasrngtemprerairr
in the vo|-rme, (c) decre.rsein thc tern;rer.rtr-rre,
(d) acldi- p l a i n . ( c ) . \ t e r ' r t s t a t t te m ; . s 1 - . 1 1 \. \' r(,r' L r i rJl c h a $
tior-rof a catalt'st? volume of tirc'containeraifect the fraction ot prc{
15.54 For a certain gas-phasereaction,the fractior.rof prr6{.,.1, the.eqr,rilibriummixturc? :'l
in ;rn equilibrium mixture is increase.clbv increasing 15.56 Metl-rtrirol(CH:OH) c;rn be rnaclebr the.rcacntd
the temperatr-rreand increaslrrgthe volume oi the reac- n'ith H.
tion vessel. (a) \\hat can \roLl conclutle about the
reaction irom the influence of ternpsr.llLlre orr the equi-
C O ( . , i ;- 2 H : ( . c ): CFI:OH(.1r
librium? (b) What can vou conclr-rclefrom the irrilr-rence (a) Use thermochemicaldata rn Appentlir C tc
oi increasingthe voltrmc? lH' for this reaction.(b) In orcle.rto maxinrrze
I5.55 Consider tl.refollou'ing equilibrium betn'een oxrclcsof Iibriunr vieki of nrcthanoi.n'oulcl r'rr-rusc a hr
nltrogerl l. (. ' ' n. .tl n' (, ' .r. ,. ). .h. .t r r ' (. 'c ) l r r r r r d r ' r t t ' t r r , t t i n t r z t .t h t
3 \Og) : NOl(5)- \ro[c) vieltl of rnethanol,u oukl r'or.rtrse.r high trr loi..

Additional Exercises pressure in the t-lask at e'qtrilibritrrl? (b) \\l

r ' . r l t r co f K , , ?
15.57 Both thc fonr'.rrcireac-tiottantl the reverserc.rctitrntn thc
15.b3 .\r rlrr)\\n ilr I,rl.ll li.l, tht' t'rlrrilil.ritrrrr
krllon'ing ecluilibritrm are belicvcrl to be cler-trt'ntarr --' 2NHqi..''
thc rcactior \:(C) - 3H:lC) =
stcps:
'I 3-i r 1[) '.rt 3tJ0'C.I'r.rrcNH; is piacr'ciin.: :
CO(q)+Cl]qq) ::COCI(r'l -Cll.q)
.rn11allon ccl to rctrch crltrilibrir,rm at ti-ri:
At 25'C the ratc constants for tire fortvarcl .ltcl rt'r'erstt T h e r e a r c 1 . t ) 5 g \ F I 1 i n t h e e ' q r . r i l i b r i u mn r i r
: \ , \ 1 l s I a n d 9 . 3 l 1 0 r l rt \ l l s l , art' thr' Ilr,lssr':,'[ \.. ,rlrtlH' irr tlrt'r'.1trilil'rrue
s r t ,1 . - l r 1 r . )
r e a c t i o r ra
respectivclr-.(a) \\'hat is ihe valr-refor thc eqLrilibritrm (b) \\'hat n'.rs the initial m.r-sscrf ar-rrmorriap
constant at 15'C? (b) Are re.lct.lntsor ptodttcts mtrre vcssr:l?(c) \\Ihat is the toial pressLrrc in thc r
plentiiul at etluilibriunr? 15.64 For the t-tltrilibrir.rm
15.58 A mirtttre of CHa arrri I l1() is ;-;155..1 over a rrickel c.rta-
2lBr(.c) ;- I1(3) - llrr({)
lvst.rt l()00 K. Thc t'mergint gas is ccrllcctec'l in.r 5 (ll)-L
ilask at.rc1 is iotrntl to ctlrrtailtE.62g of C.O, b0 g tri I{', 2 K , . - E . 5 t < l L l I a t l 5 ( ) ' C .I f 0 . 0 2 5a t m o f I B r
t hga t c t l t r r -
1 3 . 0 g o f C I l . 1 , a n c i 1 E . - lg o f I I . ( ) . , \ s s t r r . r . r i n a 2.(l-Lc()11t.lint:r, n'hat is the pr;11i;lPrcssIrr.
libritrr-nhas bet'n reachccl,c.ticttl.lteK, .lntl K'. tor tl-rert'- sti'tnccattcr ecltrilibriLrnr is reachccll
i'tctton. I -.br I or tll\'('(lLllllnrltllll
1 5 . 5 9 \ \ h e n 2 . 0 ( ln r o l o f S O l C l l i s p l a c t ' t l i n . r 2 . 0 t 1l - f l a s k a t
PH:BCl:(s): PH3({) -' IlCl:r;
303 K,56'ri, oi thc SO:Cll clccomPost'sto S()1 arrclCl'
SOlCl3(t) :- SC):(t) ' Cl:(ll) Kr, : l).052 at 60''C. (a) Calctrlate K, (b)
PHrBClr is .rrlded to .r ciosed 0.500-Lve::c:
Calculate K. for this rcaction .rt this terlpcr.rtrtrc rvith 0.0121in.rolof BC
vessel is tht-r.rci.r..rrgctl
1 5 . 6 0 A m i x t t t r e o i H 1 , S , . r u t l H l S i s i r e l t l i n . r 1 ( l - l -I ' e s s c l' t i !\ihat is the t'tluililrrittnrcottct'ntr.ltionof l)Fi-.
90'C r-rntilthc follon'rng t'qr-riiitrriLrrl is .rcl.rit'r'eci:
[15.66] Solicl NII+HS rs introtluct'cl into .ru t'r''r.u
I I l ( 5 ) ' 5 1 q 1- : : F1'S(1) 2-l'C. The follou'ing rcarctiont.lkcs prl.rcc:
the rlirtttrt' contaitts 0.'16g of H15 antl
At ecltrilibrir-rrn
0.40 g H1. (a) \'Vritethe t'quilibritrnl-colrst.rntc\Prcsslon
ior this reaction. (b) Wh,rt is thc virlue trf K, ior the reac- (for
the totai pressr.rre'
At eriuilibrir,rrn
tion at this temperatr-rre?(c) \Vhl carr n'c ignore tire' takentogctl.rer)is (1.61-l
aim. \\rhatis K,
amoLrnttlf S n'her-rdoing tire c.rlcttl.rtionin part (b)? rium at1-l'C?
15.61 A sample of rritrosvl bromide (NOBr) clecomposesac- lls.67l A 0.E31-gsampleof SO:is placecl irra I tltLL-:
corcling to the etluatioll ht.rterl io 11tlllK. The SO: decomPosesto \L
2NOBr(q). - 2NOti) + BrrG)
2 SOIQ) ;- 2 SOl[g) - t
An equilibrir.tmmixture irr a 5.(lll-Lvesst'l.li 100'C con-
t a i n s 3 . 2 2 g o f N O B r , 3 . 0 8 g o f N O , a n c l 1 . . 1 9g o f B r l ' At ccl.rilibriumthe total pressurein
(a) Calcr.rlateK.. (b) \\rhat is thc tot.rl PrcssLtrcexertecl 1.300atm. Finclthe lalues c-riK,.and K.
bv the mixtr"rreof gases? a t 1 1 0 0K .
15.62 Consider the hr.pothetical reaction A(qt ;- I Big) A 15.68\itric oxide (NO) reactsreadilv u'ith
\vith0.55atnrof pureA, aftern'hichit is
flaskis charged iollou's:
allon'edto reachequillbriumat 0'C At eqr-Lilibrmmthe
partiaipressureof A is 0.36atm (a)\\'hatrs the total 2 NO(S) - CI]1q)5
 Exercises 663

of NO is
is K, :21x 103 If the iniiial concentratior-r
It not'indicateihedirec-
andCi2at 100"Cat equilibrium? 0.200,\{, u'hat are the equilibrium
concentrationsof NO'
mustproceed
tionthatthereaction !11+i*t^":q.Ttl*lt"l]
' = 1r ' LU '\r' N1, and 02?
( a )[ C O C I l l = 2 O r J l0- lLUl
x 10-.,t'i'-or =I
" \ l ' tco'121 15.44 For the equilibriutn
rCl"t= 6.62 i9 " ]9-^
i1'
'A4;
i."i = l i^= lo
',n4, tcl:l= 225x 1o BrzQ) - Clrk) :2BrCl(q)
0.0100^{,tcol= [Cl:]-.1a8x 10-" '\1'
iito.l.i mol of Br2 and 0 30 mol Clz are
K, ior the equilibrium at'100K, K. = 7'0 lf 0'30
s ;.:;;tt; in Tabie 15 2' at -100K' rvhat n'iil be
rntroclucecit'-ttoa 1'0-L container
of Br' ' Cll ' anc-lBrCI?
N:[q) - 3Hr[C) -- 2NH:[t) thc eqr-rililrriumconcentrations
r i l i it :z: r' x,' = 0 "116for the eqr'ri[brium
For each of the mixtures listecl
is -1.51x 10-i at'{50'C 2 NO[q) + Br2[g)
mixturc is at equilibrittm at 2 NOBr(q) '-
n"r". i,-tai.ott rvhether the
irrtlicate clirectiotr
.150'C.If it is not at t'quiliLrrir-rnr' ,tl.rc Iftlrc.pressr'rrestlfNol3r(g)andNo(q)areequal,n'lratis
'lrd reactants) Lrr$'hrch the nrir- Brlqq)?
(tor,varclproduct or to\^ the etltulibrium pressureof l for the cquilibrir-rnr
equilibrium- . : x 1il
t.tr" n',urt shift to achieve 15.46 At 21i'C, K 1.2
N F I j , 3 5 a t m N 2 ' J c ) 5a t n r f l : :
iul ,,)S a t r n
N t - t 1 H S ( s )' - Nll:(q) ' Ilr5[l)
atm H1' no N::
i t l : i n , t r rN H l , 5 9 5
i.i Zn o,n-tNtl3, 42 atnr
I-11'202 atnr N1' c()llcentr'1tionsof NI-1I arrcl
Calcr-riatetirc eqr'LilibriLlnl
3q At 100'C, K,
= 0 07E for the reactitln N H r H S i s p l a c e ' di l r a c l o s e t l
H " S i t . r s a r n p l go t - s o l i d
- until e''1trililrriuuris re'trchecl'
SO:[q) - Cl:tc) vessel arlcl dccc'rmposes
SO1C13i.q;'
i ..-1"'Corrsitlcrthe reat:tttltr
the'threeg'rses'ti-re'co11ccu-
ln an cquilibrium mixturt'of C.rS()11s).-
- SOll (rrrl)
C'11 1n'71
SO1 are tl l()fi 14 ancl 0 052 '\1' re-
ir.*ir.r,-r,of SO1C12and r
Cll in tht: is K' : 2 { ' l0 for
,p".ii..fu What is the pr'rrti'rlPressure of r\t 25'C tht't-quilibrir'tnrcottst;rtrt
CaSOa(s)is nri>redr'tith rv'rier
. ' , r u i l i h r i u nnr t i x t t t r e l this reaction (a) If t'xct'ss
reactiou has K" : 0 3'15: solutiorr-ofCaSClt' lr'hat
t nn )il ,oJ K the tolltrrriug at 25"C to Produce a satttratctl
*ltt'nttntiont of C-'tl- arntl SOll ?
.rre ther
2 SO"{rl) - O:[q) ;- 2 SC)3(q; "q'ifit""''i-t volunre of 3'0 L' rvhat
(b) lf the resulttng solutiotr hir-s-a
CilSC)a('s)neec-leclto achieve
urixtttre thc partial Lrressurcs
oi SOI is the mtuttnttn-"'o.l" of
In an eqtlilibriltm
.1 elr"
'rnd ll'755 atni' rt-sPe'ctir equiiibrrum?
ancl O1 are 0 65 atm in the = r 10'rforthereraction
pressure of SOr 1 5 . 4 8A i S ( l ' C , K . 1 . 8 7
Wn.a i, thc' cquilibriun.r prartial
*ixir'trt'? l,llrBCIr(s) :- PHr[C) * BCIrG)
constnrlt tol the rt'actttlt-t
^ ^ (a) Ai 1285'C the e'luililrriunl
'11.{l r'A()20(l-Lvessel ttf PLlr and
- Ir'il ''rl0 (a) C.rlculatt'thc equilibrir'tm collcelrtratiot-rs
ili,tci ="=zllr(q)i-sK, I'Fl:BCl: rs placetl in 'r closc.d
t-uixture of tht: g;rses h'rs tlClr it a solicl t"'tpf" of
ctlntaitring '-rn equilibritrm tqr'rilibriul'u is reirched'
is thc nrassof I3rqq)in the lt's- vesscl aucl tft.ttt't''ito"t trntrl
O.jit g Si2qqli" it \\hat 0 il){l I ' u'hartis the mtut-
r e a c t i o r t t l l ( 3) - l:ic) i 2Frlll]' (b) lf thc flask has 'i t t'lt'nt" oi
sel? (b)For the tir''rt mr'lst be ac'lc1et-l to the
()0-i-flask corrtair-ring' erltti-
'rn rlrLrrn flrass ot PH;BCl:(s)
^, = iS : at 700 K in a 2
gases'therc 'rre |J056 g H1 fl;rsk 1o'rcirieveetlr-rilibrir-ul?
Iibrium mirtr"rreof the three - Br2(g) # 2 lBr(g)' K' = ?8.0
mass of Hl irr tirc ilask? !i r.i lror the reactton l1(g)
nn.f t.36 g I1 lVhai is ihe .1 SOUmol lBr in a 1'00-L flask
is
cllstant ior l](q ) : f
at 50'C St'ppt"" in'-ttO
15.42 (a) At E00 K thc equilibrir-rm
\' in a
i!{')
10'0-l-' at 150'C lVhat are the
is K. : 3 1 x 10 If'X un equilibrium. tuirture ailou'ec1to '"ntit t'quilibrium
r ot of IBr' I2' and Brll
I'esseicontaurs7.67 10 g of I(C),-T*'n1'u1v grams t'tltlilibrlr'rmcouct-ntrations
(bj For 2 SO2[g) t O2(g) :
lr are in the mrxturc.? 15.50 At 25'C thc reactlon
'es::l th:
itir**i *, I I o x tot at 700K I. a 2'00-L C.rCrOr(s) i-' Car-(a'l; * CrO12 (n4)
1 57 g of SO: arnd0 125 g ot
equilibrium mlxture contirins
K, = t"
O. Hort' mall\' granls of SOl 'rre in the'r'esse'l? iras ..rncquilibriu.r coustarrt i " 19 :,-)]"\1t :t:
ior tht'reclctiorl of Ca- antl LrL)l- llr cl
15..13At 2000'C the equilibrium corrstant the t-quilibrium concentratrons
saturatetlsolutiou oi CaCrOl?
2 No[q)- N:(s)* o:[c)

gas;(f) SO1(q;is removed

is increasedbr.adcling a noble
Le chStelie/s PrinciPle fror-nthe svstem'
ior n'hich -\H < 0: JH' = 2816kJ'
I i.5l Considerthe tollorvrngequilibriun.r' 15.52 For the foiior't'rngreactiorr'
2 SO2G)- OzG) -- 2 SO:({) C . H 1 1 O " 1 s -) 6 O : ( t )
5CO2$) + 6H:O(l) --
change-sattectarl eqlrr- vieid oi C6H11O6 affectec-l
br'
Hor'r.rvill eachof the follor'r'ing llon' is the eqtrilibriLrm
(a)O:,(S)rs addedto
it'irt". -","re oi the threegaies? (c)the (a) urcreasinglttr^ ' (b) incieasing temperature',(tl Tl]:.:
mixture is heated; (e) retrtotu.tg
,f-r.^rr'r,.., (b) the reaction ins, CO-, (d) Jecreasirrg
thc tt'tal Ftt:"1:t
voiumeoi the reactron vesselis doubled;(d) 'r catalvsits (f '.rcatalvst'
oi the slstem part trf ihe C-H ' rO^ ' ) a'1dutg
;;;;i" the mirture; theiotal Pressure
(e)

, r , * l , uI E !i ?3 lii =iii'