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09 Giao Trinh CSLT Hoa Hoc Dao Hung Cuong PDF
09 Giao Trinh CSLT Hoa Hoc Dao Hung Cuong PDF
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Mc lc
Trang
Chng 1. M u
. ..............................................................................................1
1.1. Ho hc v nhim v ca ho hc . ............................................................2
1.2. Mt s khi nim c bn trong ho hc . ...................................................2
1.3. Mt s n v o trong ho hc. .................................................................2
Chng 2. Cu to nguyn t . .....................................................................................6
2.1. Nguyn t . ................................................................................................6
2.2. M hnh nguyn t c ht nhn. .................................................................6
2.3. M hnh nguyn t ca Bohr . ....................................................................9
2.4. Thuyt c hc lng t v cu to nguyn t . ..........................................9
Chng 3. S bin thin tun hon cu to nguyn t.
Bng h thng tun hon Meneleep . .....................................................18
3.1. S bin thin . ...........................................................................................18
3.2. Bng h thng tun hon cc nguyn t ho hc Meneleep . .................22
Chng 4. Lin kt ho hc . .....................................................................................28
4.1. Mt s khi nim c bn ca lin kt ho hc . .......................................28
4.2. Lin kt ion . ............................................................................................30
4.3. Lin kt cng ho tr . ..............................................................................32
4.4. Cu to phn t . ......................................................................................42
Chng 5. Nhit ng ho hc . .................................................................................57
5.1. Mt s khi nim c bn v nhit ng hc . ...........................................47
5.2. Pht biu nguyn l I nhit ng hc . ....................................................50
5.3. Nhit ng tch, ng p . ........................................................................51
5.4. nh lut Hess v cch xc nh nhit phn ng theo h qu
ca nh lut Hess . .................................................................................53
5.5. S ph thuc ca hiu ng nhit vo nhit . ........................................55
5.6. Nguyn l II nhit ng hc. Entropi . .....................................................57
5.7. Nguyn l III nhit ng hc. Entropi tuyt i . ....................................61
5.8. Th ng nhit - ng p . ........................................................................62
Chng 6.
ng ho hc . .............................................................................................65
6.1. Vn tc phn ng ho hc . ......................................................................65
6.2. Cc yu t nh hng n vn tc phn ng ............................................66
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Chng 1
M U
1.1.
HO HC V NHIM V CA HO HC:
Ho hc l mt trong nhng mn khoa hc c bn nghin cu cc quy lut v hnh
1.2.1. Vt cht:
Vt cht l mt khi nim tng qut, chung (ting Latinh: mater rerum ngi m
ca mi vt). Vt cht tn ti di hai hnh thc: cht v trng.
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MT S N V O TRONG HO HC:
Cng nh cc ngnh khoa hc khc, ho hc s dng tt c cc n v o ca H
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1,66.10-27kg 32 = 53,12.10-27kg.
* Khi lng phn t tng i ca hp cht:
Khi lng phn t tng i ca hp cht l khi lng trung bnh tnh theo
.v.C phn t ca hp cht. T gi tr ny s tnh ra c khi lng phn t kilogam
(theo n v SI). V d, khi lng phn t tng i ca CaCO3 bng 100 c ngha l
mt phn t CaCO3 c khi lng 100 .v.C, tng ng vi:
1,66.10-27kg 100 = 1,66.10-25kg.
1.3.2. Mol:
Mol l lng vt cht cha 6,022.1023 ht vi m (phn t, nguyn t, ion, electron,
photon...).
* Mol nguyn t:
Mol nguyn t l gi tr tnh ra gam ca khi lng nguyn t tng i ca
nguyn t (n chnh bng s .v.C nguyn t tnh ra gam). V d, t khi lng tng i
ca nguyn t Na bng 23 suy ra khi lng mt mol nguyn t Na l 23 gam.
* Mol phn t:
Mol phn t l tng khi lng ca 6.1023 phn t ca hp cht tnh ra gam (n
chnh bng s .v.C ca phn t tnh ra gam). V d, t khi lng tng i ca phn t
ng glucoz C12H22O11 l 342 suy ra khi lng mt mol phn t glucoz l 342 gam.
1.3.3. ng lng:
- ng lng ca mt nguyn t l s lng nguyn t c th kt hp hoc thay th
mt mol nguyn t hyro trong phn ng ho hc.
V d, trong cc hp cht HCl, H2O, PH3, CH4 ng lng ca cc nguyn t Cl, O, P,
C ln lt l 1, 1/2, 1/3, 1/4 mol nguyn t ca nguyn t .
- Khi lng ng lng () hay cn gi l ng lng khi ca mt nguyn t l
khi lng tnh ra gam ca mt ng lng ca nguyn t .
- Cch tnh ng lng khi:
+ ng lng khi ca mt nguyn t bng khi lng nguyn t (AZ) ca
nguyn t chia cho ho tr (n) ca n:
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Z =
Z
n
(1-1)
B =
(1-2)
+ ng lng khi ca mt axit bng khi lng phn t ca axit (MA) chia cho
s nguyn t H (n) ca n:
A =
A
n
(1-3)
Trong trng hp axit c nhiu nguyn t hyro tham gia phn ng th n c tnh
bng s nguyn t H tham gia vo phn ng ho hc . V d, A ca H3PO4
(M = 98) trong 3 phn ng sau:
H3PO4 + NaOH
= NaH2PO4 + H2O
H3PO4 + 2NaOH
= Na2HPO4 + 2H2O
H3PO4 + 3NaOH
= Na3PO4
+ 3H2O
O
n
(1-4)
+ ng lng khi ca mt mui bng khi lng phn t ca mui (MM) chia
cho (n) tch ca s nguyn t kim loi nhn vi ho tr ca n:
M =
(1-5)
1.3.4. S xi ho
S xi ho (ch s xi ho, bc xi ho) l gi tr in tch nguyn t ca mt
nguyn t c c nu gi s rng tt c cc lin kt vi nguyn t u l lin kt ion.
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Chng 2
CU TO NGUYN T
2.1. NGUYN T
C s l thuyt c bn nht v cu to vt cht - l kh nng phn chia vt l
cc cht thnh nhng phn nh m mi phn vn gi nguyn tnh cht ho hc ca n.
Cc phn nh c gi l phn t. Nu tip tc phn chia phn t th nhn c nhng
phn nh hn - l nhng nguyn t. Mt lot cc pht hin vo cui th k th XIX v
u th k th XX cho thy rng nguyn t c cu to rt phc tp.
Khi cho dng in i qua cht kh v cht lng ngi ta nhn thy trong c phn t
ln nguyn t u c mt thnh phn chung - l in t. Bng phng php dng catt
xc nh c in t c khi lng 9,1095. 10-28gam v c in tch -1,6.10-19
Culong.
Bng phng php cho dng in i qua dung dch in li cng m ra cc nh
lut in phn v pht hin ra s tn ti cc nguyn t mang in tch dng v mang
in tch m (cc cation v anion).
Kt qu cc thc nghim trn y cho thy rng nguyn t c cu to rt
phc tp t mt thnh phn l in t mang in tch m v mt phn khc mang in
tch dng. Vy vn t ra l quan h sp xp nh th no gia in vi phn mang
in tch dng ca nguyn t? tr li cu hi ny, trn c s ca cc th nghim cc
nh khoa hc ngh cc m hnh cu to nguyn t.
2.2. M HNH NGUYN T C HT NHN:
2.2.1. M hnh Thomson
Thomson nhn thy rng khi dng mt chm tia X bn ph qua l kim loi mng
th chm tia X b tn x khng ln lm khi hng i ban u. T th nghim ny
Thomson ngh m hnh : Nguyn t l mt hnh cu in tch dng c gn vi
nhng ht electron in tch m. Cc phn t tch in dng cng nh cc electron phn
tn u trong mt khi cu trn cc lp v ng tm khc nhau.
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10
ph ca n cng phi c cc vch lin tc cch u nhau. Thc t cho thy rng, ph ca
cc nguyn t khng phi l nhng vch lin tc cch u nhau (hnh 2.2).
Xanh
650
600
550
500
450
H
700
Tm
400
350 nm
hc
(2-1)
- bc sng
- tn s bc x
h - hng s Planck (6,63.10-34 J.s)
c - vn tc nh sng (300.000 km/s).
* M hnh cu to nguyn t ca Bohr
Vn dng thuyt lng t ca Planck, Bohr ngh mt m hnh cu to
nguyn t trong cc in t:
- Chuyn ng trn nhng qu o xc nh v khi quay trn cc qu o nng lng
c bo ton (trng thi dng).
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11
1
(eV) trong : n = 1,2,3...
n2
(2-2)
(2-3)
nh sng mang tnh cht sng: th hin qua cc hin tng nhiu x, giao thoa vi vn
tc truyn sng: c = lg
Mi quan h tnh cht sng ht (quan h nh nguyn) c biu th bng biu thc
Enstein-Planck sau:
l =
h
mc
(2-4)
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12
h
mv
(2-5)
m khi lng ca ht
v - vn tc chuyn ng ca vt cht
Tnh cht sng - ht ny c tt c cc ht vi m: electron, proton...
2.4.3. Nguyn l bt nh ca Heisenberg:
V c tnh sng - ht nn v nguyn tc khng th xc nh ng thi chnh xc c
ta ln vn tc chuyn ng ca ht. Do khng th v hon ton chnh xc qu o
chuyn ng ca ht. iu ny c th hin qua nguyn l bt nh ca Heisenberg:
X . VX
h
m
(2-6)
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13
8 2 m
(E - U) = 0
h2
2
=
x 2
2
trong :
2
+
y 2
(2-7)
2
+
z 2
m - khi lng ca in t
h - hng s Planck
Nghim ca phng trnh sng Schrodinger l cc hm s 1, 2, 3, .... n tng
ng vi cc mc nng lng E1, E2, E3, .... En. Nh vy, t nghim ca phng trnh sng
Schrodinger s tnh c lng t nng lng ca cc ht vi m .
A0 l nghim ca phng trnh Schrodinger.
A0 = 1. 2n
A0 = (n,l,m)
2.4.5. Orbital nguyn t (AO). Cc s lng t:
Orbital nguyn t c th vit di dng cc s nguyn c gi l cc s lng t:
n s lng t chnh
l s lng t orbital (s lng t ph).
m s lng t t.
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14
2 m e 4
n2h2
(2-8)
S lng t chnh n :
1 2
Lp:
K L M N . ...
h
2
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(2-9)
15
z
y
x
s
z
z
y
z
y
y
x
pz
py
px
d x 2-y 2
d z2
z
z
y
y
x
dyz
dxz
d xy
0 1 2 3 4 5 ....
Phn lp:
s p d f g h ...
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16
S lng t ph l
phn lp
1s
0, 1
2s, 2p
0, 1, 2
3s, 3p, 3d
0, 1, 2, 3
mh
2
(2-10)
S lng t t m
S lng t
-1, 0, 1
-2, -1, 0, 1, 2
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17
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18
7s
7p
7d
7f
6s
6p
6d
6f
5s
5p
5d
5f
4s
4p
4d
4f
3s
3p
3d
2s
2p
1s
Hnh 2.4. Quy tc sp xp nng lng Klexcopxki
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19
Cu hnh in t:
Cu hnh lng t:
Nguyn t Cl (Z = 17):
Cu hnh in t: 1s22s22p63s23p5
Cu hnh lng t:
3s2 3p5
2s2 2p6
1s2
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3d
20
Chng 3
2
He 1s
1S2
Y
X
n = 1
s
He 1s
2
n = 1
s
1s1
Y
X
3.1.2. Chu k 2.
chu k ny ang xy ra s phn b in t ca lp L (n = 2). Do vy, chu k ny
c 8 nguyn t (t Li n Ne) vi cc phn lp 2s v 2p. Di y l cng thc in t v
hnh dng orbital ca mt s nguyn t:
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21
z
1 s22 s22 p 1
5B
2s2
n = 2
n = 1
s
2p1
z
1 s22 s22 p 3
7N
2s2
n = 2
n = 1
x
2px
2py1
2 p z1
z
1 s22 s22 p 4
8O
2s2
n = 2
n = 1
x
2 p x1
2py1
2 p z2
3.1.3. Chu k 3:
chu k 3 ang xy ra s phn b in t ca lp M (n = 3) gm 8 nguyn t (t
Na n Ar) vi 3 phn lp 3s, 3p v 3d:
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22
1s22s22p1
11Na
[1s22s 22p6]3s1
3s
15P
[1s22s22p6]3s23p3
3s
18Ar
[1s22s22p6]3s23p6
3s
3p
3p
3p
3d
3d
3d
K 1s22s22p63s23p64s1
20
Ca 1s22s22p63s23p64s2
Sc 1s22s22p63s23p6 3d14s2
..........................................
26
Fe 1s22s22p63s23p6 3d64s2
...........................................
30
Zn 1s22s22p63s23p6 3d104s2
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23
21
- Dy 4d:
39
- Dy 5d:
57
59
90
3.1.5. Chu k 5.
Chu k 5 gm c 32 nguyn t. S phn b in t cc lp v phn lp ca chu
k ny xy ra tng t nh chu k 4: hai nguyn t u (37Rb - Rubidi, 38Sr - Stroni) in
t phn b trn 5s; su nguyn t cui (49In - Indi 54Xe - Xenon) trn 5p. Gia cc
nguyn t s v p ny cc nguyn t chuyn tip dy 4d:
39
3.1.6. Chu k 6.
Chu k ny gm c 32 nguyn t. S phn b in t cc lp v phn lp ca
chu k ny bt u t phn lp 6s ca hai nguyn t ( 55Cs - Cezi, 56Ca - Canxi), tip theo
10 nguyn t dy 5d (57La - Lantan 80Hg - Thu ngn), 14 nguyn t nhm Lantanoit
4f: (59Ce - Ceri 71Lu -Lutexi) v cui cng l su nguyn t ca phn lp 6p (81Tl Tali 86Rn - Radon).
3.1.7. Chu k 7.
Chu k 7 c bt u bng hai nguyn t s (88Fr - Franxi, 89Ra - Radi), tip theo
nguyn t d (89Ac - Actini), 14 nguyn t f nhm Actinoit (90Th - Thori
103
106
105
Db - Dubni,
Lr -
Sg -
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24
29
Cu 1s22s22p63s23p63d104s1
24
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25
25
Ne
20
F
Ar
N
15
C
Cl
Be
10
Mg
Si
Ca Ti
Sc
5
Na
Li
Zn
Al
11 13 15
Co Cu
V Mn
Fe Ni
Cr
17 19
As Br
Kr
Ge Se
Ga
Rb
21 23 25 27 29 31 33 35 37
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26
30
20
10
I1
F1
-10
1
H
2
3
He Li
4
5
Be B
6
C
7
N
8
O
9
F
10 11 12 13
Ne Na Mg Al
14
Si
15
P
16
S
17
Cl
18
Ar
19
K
20
Ca
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27
3.2.2.3. m in
m in l kh nng ht in t v pha mnh ca mt nguyn t ny so vi
nguyn t khc trong mt phn t. Theo Mallikel, m in c c th c xc nh theo
cng thc sau:
1
2
H
Li
1,0
Be
1,5
C
2,0
2,5
3,0
Na Mg Al Si P
S
0,9 1,2 1,5 1,8 2,1 2,5
Cl
3,0
K Ca Sc Ti Ge As
0,81,0 1,31,6 1,7 2,0
F
3,5
4,0
Se Br
2,4 2,8
Rb Sr Y Zr Sn Sb Te I
0,81,0 1,31,6 1,8 2,1
2,6
1,7
Cs Ba
0,7 0,9
1,0
2,0
3,0
4,0
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28
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Li
F O
Be
Ca
10
Ne
P
S
Cl
15
Al
20
25
30
Kr
40
50
Xe
60
Ra
7S
70
80
90
Ac Pa
7S
ThU PuAm
Np
Cm
Cf Md
Fr
W
Ti
Re OsPt Pb
IrAu
HgBi Po
Al
Rn
Hf
Ta
Lu
Ba
Ce
Nd
LaSm Eu
Dy
Gd Er Yb
Cs
Te I
Sb
Sr
Y
Te Nb
In
Zr Mn
Ru
Te
Rh Ag
4P
Cd
Sn
5S
Rb
As
SeBr
Sc
3S Ti Cr
Ga
V Mn Fe
K
Al
Cu
Mg
Co
Zn
Si
Ni
Ge
Na
100
29
(I1+I2+I3+I4)
eV
150
130
110
90
70
0
r, A
1,5
1,0
0,5
10 30 50 1
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30
Chng 4
LIN KT HO HC
4.1.
lin kt cng ho tr (cng ho tr khng phn cc Dc=0; cng ho tr phn cc 0< Dc<2).
4.1.1. Cc thng s c bn ca phn t:
Cu to phn t ca hp cht c th c xc nh qua vic nghin cu tnh cht
ho hc, vt l ca n. Ngoi ra, bng phng php phn tch vt l ngi ta xc nh cc
thng s c bn ca phn t: di lin kt, gc ho tr v cu hnh hnh hc phn t.
- di lin kt l khong cch gia hai tm ht nhn ca hai nguyn t lin kt ho hc
vi nhau. V d : di lin kt gia nguyn t hyr v xi trong phn t H2O l
0,92AO.
- Gc ho tr l gc to bi ng thng tng tng i qua tm cc nguyn t lin kt
ho hc vi nhau. V d, gc lin kt ho tr ca phn t nc H2O l 04,5o.
- Nng lng lin kt l c tnh quan trng ca lin kt ho hc, xc nh bn ca lin
kt. V gi tr, nng lng lin kt c tnh bng nng lng gii phng khi ph v mt
lin kt.
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31
Nng lng lin kt ca phn t c hai nguyn t chnh bng nng lng phn ly
ca phn t thnh nguyn t. Nng lng lin kt ca lin kt A-B trong phn t ABn
l gi tr trung bnh EA-B:
AB
AB
(4
-1)
E (kJ/mol)
800
400
-400
0,74 1
(Ao)
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32
4.2.
LIN KT ION
Cl (Z = 17)
1s22s22p63s1
1s22s22p63s23p5
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33
Anion Cl-
1s22s22p6
1s22s22p63s23p6
LIN KT CNG HO TR
Nh ni trn, khng th gii chnh xc phng trnh Shrodinger cho h thng
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34
Tnh bo ho
C 2s2 2p2
B 2s2 2p1
2
N 2s2 2p3
B* 2s2 2p1
2
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35
p -p
p -p
p -p
d -d
s-s
d -d
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36
1800
s p -o rb ita l
12
(s + p )-o rb ita l
(s + p + p )-o rb ita l
s p 2 -o rb ita l
109028'
(s + p + p + p )-o r b ita l
s p 3 - o rb ita l
Hnh dng orbital sp trn hnh 4.4 cho thy mt in t phn b v mt pha ln
hn pha bn kia. Kt qu l s xen ph ca pha c mt in t ln s to ra lin kt
bn hn so vi s xen ph ca s v p ring bit.
4.3.1.4. Cc loi lai ho
* Lai ho sp3
lm r vic t hp ca cc phn lp electron theo m hnh lai ho sp3, ngi ta
xt s to thnh phn t CH4. Nguyn t cacbon trng thi c bn c ho tr 2 vi cu
hnh electron 1s22s22p2. to thnh phn t CH4, nguyn t cacbon phi chuyn sang
trng thi kch thch C* c ho tr 4 vi cu hnh electron 1s22s12p3. Trong trng hp ny
phn t CH4 c to thnh bi ba in t 2p3, mt in t 2s1 ca nguyn t cacbon vi
bn in t 1s1 ca 4 nguyn t hyro:
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37
Nh vy, trong phn t CH4 s c 2 loi lin kt: 3 lin kt loi s-p v 1 lin kt
loi s-s. Thc t cho thy rng trong phn CH4 ch c duy nht mt loi lin kt ( 4 lin
kt hon ton ging nhau).
3
1
+
px
+
pz
py
3
1
1
2
1 0 9 0 ,5
iu ny c gii thch bng thuyt lai ho: to thnh phn t CH4, mt orbital
s t hp vi ba orbital to thnh 4 orbital lai ho sp3 c hnh dng v nng lng hon
ton nh nhau. Cc orbital sp3 ny khng ging orbital s v p ban u, c kh nng xen
ph cao hn to thnh lin kt bn hn.
Cc orbital lai ho u c in tch cng du v do vy chng s y ln nhau n
mt khong cch xa nht. i vi lai ho sp3, s phn b xa nht ca bn orbital ny
chng c phn b di nhng gc 109,28O, gc t tm ca t din u (hnh 4.5).
S lai ho sp3 tng t xy ra nguyn t N ca phn t NH3, nguyn t O ca
phn t H2O (hnh 4.6).
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38
H
CH
H 3N
O
H
H
H
1 0 4 ,5 0
1 0 7 ,3 0
109 28'
H 2O
Cl
B
12
0
12
Cl
b. Cu hnh hnh hc
Gc lin kt trong phn t BCl3 l 1200, lai ho sp2 l loi lai ho tam gic u.
* Lai ho sp
Lai ho sp l lai ho ca mt orbital s v mt orbital p to thnh hai orbital sp nm
trn mt ng thng vi gc lai ho 1800 (hnh 4.8).
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39
+
p
1800
sp
s ,p
Be
Cl
Cl
2
Phn t BeCl2
4.3.2. Phng php orbital phn t
4.3.2.1. Lun im c bn ca phng php Mo
Phng php MO xemphn t nh l mt tp hp ca cc ht nhn v electron
trong mi electron chuyn ng trong in trng ca tt c cc ht nhn v in t
khc. Tt c cc electron phn t (tng t nh trong nguyn t) c phn b vo cc
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40
orbital phn t theo cc trng thi nng lng xc nh. Mi orbital c vit bi cc s
lng t c trng cho tnh cht ca in t trng thi nng lng . Nh vy, v c
bn phng php MO l s vn dng m rng ca phng php AO, ch khc l orbital
phn t c nhiu trung tm ht nhn.
V orbital phn t c nhiu tm nn hnh dng ca n rt phc tp. n gin
ho, trong phng php gn ng ngi ta xem orbital phn t nh l mt t hp tuyn
tnh ca cc orbital nguyn t. iu ny c ngha l orbital phn t c to thnh bi kt
qu php cng + v php tr - cc orbital nguyn t. V d, nu orbital ca 2 nguyn
t A, B c k hiu l A , B th orbital phn t AB c to thnh t Av B s l:
+ = c1A + c2B
(4-2a)
- = c1A - c2B
(4-2b)
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41
MO
+
Xen ph?
AO
AO
s ls
+
+
AO
s ls
Hnh 4.9. S to thnh lin kt v
Tr
s *2Px
c
ng
2Px
2Px
s 2Px
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42
AO
MO
2P z 2P z
rt
c
ng
Z
X
_ s ls
1SB
1SA
-E
Nng l
ng E
s ls
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43
MO
Nng l
ng E
AO
AO AO
p*x p*y 2P
pz py
2P
2P
s *s
2S
2S
ss
2S
MO
s *x
sx
AO
2P
s *s
2S
ss
1
(n - n*)
2
(4-3)
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44
= lq
trong
(4-4)
l - di phn cc
q - in tch
(4-5)
a - phn cc ho
E cng in trng
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45
- +
-
+
+
C ch to thnh
lin kt ny ph thuc vo loi orbital tham gia cho nhn. V d, trong s to thnh phn
t NH4+, phn t NH3 s dng cp in t khng phn chia ca mnh cho vo orbital
trng ca H+
H
H N:
H
H+
H N H
Trong phc cht BF3.NH3, phn t NH3 s dng cp in t khng phn chia ca
mnh cho vo orbital trng ca BF3:
H
H-N:
H
F
+
B- F
H F
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H - NB - F
H
46
...H-F...H-F...H-F...
(4-5)
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47
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48
Chng 5
NHIT NG HO HC
Nhit ng hc nghin cu quy lut iu khin s trao i nng lng bao gm 2
quan im:
1. Quan im c in: ch thit lp h thc nng lng vi p sut (P), th tch (V), nhit
(T) m khng ch n cu to ca nguyn t, phn t v c ch chuyn ho.
2. Quan im nhit ng hc thng k: Xc nh nng lng da vo tnh cht ca cc
nguyn t v phn t.
Nhit ng hc p dng vo ho hc c gi l nhit ng hc ho hc. Ni dung
ch yu ca nhit ng ho hc da trn ba nguyn l c bn ca nhit ng hc. Trn c
s vn dng ba nguyn l c bn ny, nhit ng ho hc cho php :- Tnh c nng
lng trao i ca phn ng ho hc- Tin on c chiu ca ca phn ng ho hcGii hn t din bin ca mt phn ng ho hc.
5.1. MT S KHI NIM C BN V NHIT NG HC
5.1.1. H v mi trng
H l mt vt, mt nhm vt c tch ring ra c thc hoc bng s tng tng
nghin cu; phn cn li l mi trng.
H nhit ng hc c phn chia thnh nhiu loi khc nhau:
* H ng th: c tnh cht ng nht tt c mi im ca h. V d, kh nn
trong bnh, ru cha trong chai... (mt pha)
* H d th (h c hai pha tr ln): c tnh cht khng ng nht trong cc
phn khc nhau ca h c phn chia vi nhau bng b mt vt l. V d, nc v
nc 0 OC...
* H vt l: h m trong xy ra cc qu trnh thay i vt l nhng khng c s
thay i v bn cht ho hc. V d, s bin i cc trng thi vt cht nhit nng
chy, nhit si.
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49
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50
*Thng s cng :
Thng s cng khng c tnh cht cng tnh, khng ph thuc vo yu t dung . V
d, nhit ca nc (cng ) khng ph thuc vo th tch v khi lng ca n.
* Cn bng nhit ng:
Mt h trng thi cn bng nhit ng khi gi tr ca cc thng s trng mi
im u nh nhau v khng bin i theo thi gian.
5.1.4. Bin i thun nghch v bt thun nghch :
* Bin i thun nghch:
Mt h ang trng thi cn bng (P,V,T) chuyn qua cn bng mi (P,V,T1) bng
s thay i T T1 qua nhiu bc Ti khc nhau:
(P,V,T) (P,V,T1) (P,V,T1) (P,V,T1) ... (P,V,T1)
c gi l s bin i thun nghch (do c s thay i v cng nh nn trong tng bc
h c th tr li trng thi ban u).
* Bin i bt thun nghch:
Bin i bt thun nghch l bin i ch xy ra nhanh, qua mt bc ln. N hon
ton ngc li vi bin i thun nghch l h khng th tr li trng thi ban u.
Vy: Bin i thun nghch l qu trnh cn bng;
Bin i bt thun nghch l qu trnh t din bin.
5.1.5. Hm trng thi :
Mt hm nhit ng c gi l hm trng thi nu s thay i gi tr ca n ch
ph thuc vo cc gi tr thng s trng u v cui m khng ph thuc vo cch thc
bin i ca qu trnh.
V d, nu F (P,V,T,...) l hm trng thi th khi:
F1 (P1,V1, T1,...) F2 (P2,V2,T2,...), ta c:
F = F 2 - F1
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51
V1
(5.1a)
(5-1b)
NHIT NG TCH, NG P :
* Nhit ng tch:
Nhit ng tch l nhit lng thu vo hay thot ra ca h trong qua trnh bin i
ng tch (V = const).
T (5.1a ):
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52
QV = DU
(5-2)
(5-3)
QP = QV + P V
(5-4a)
Nu thay: PV = nRT, ta c:
QP = QV + nRT
(5-4b)
trong : n = (mol tham gia phn ng) - (s mol kh to thnh sau phn ng)
i vi mt phn ng dng tng qut:
aA + bB = eE + qQ
Ta c:
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53
DH1
CO2(k)
DH3
DH2
CO (k) + O2 (k)
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54
Hthun
Hthun + Hnghch = 0
F1
F2
Hnghch
* Nhit sinh:
Nhit sinh (nhit to thnh) ca mt hp cht l nhit lng thot ra hay thu vo
khi to thnh mt mol cht t cc n cht bn vng ban u iu kin xc nh,
c k hiu: DHs
Nhit sinh xc nh trng thi chun gi l nhit sinh chun, c k hiu: DH0298,s.
Nhit sinh chun ca cc n cht bng khng: DH0298,s(n cht) = 0.
n v: J/mol; cal/mol.
* H qu 2:
Hiu ng nhit ca mt phn ng bng tng nhit sinh ca cc cht to thnh tr i
tng nhit sinh ca cc cht tham gia.
i vi phn ng tng qut:
Ta c:
aA + bB = eE + qQ
* Nhit chy:
Nhit chy ca mt cht l nhit lng thot ra khi t chy hon ton mt mol
cht thnh cc xit cao nht iu kin xc nh, c k hiu: DHc.
Nhit chy xc nh trng thi chun gi l nhit chy chun, c k hiu:
H0298,c.
n v: J/mol, cal/mol.
* H qu 3:
Hiu ng nhit ca mt phn ng bng tng nhit chy ca cc cht tham gia tr i
tng nhit chy ca cc cht to thnh.
V d, hiu ng nhit DH ca phn ng:
C2H4 + H2 = C2H6
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55
= 2CO2(k) + 2H2O(h)
DH1,c
H2(k) + 1/2O2(k)
= H2O(h)
DH2,c
DH3,C
1/2Cl2 (k)
H1
DH4
H2
Cl (k)
Na (k)
NaCl (r)
DHNaCl
H5
H3
Cl- (k)
+
Na+ (k)
Suy ra:
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56
5.5.
H
T
(5-5)
QP = DH = CPdT
(5-6)
(5-7)
QV = DU = CVdT
(5-8)
CV =
Suy ra:
= [e
T ,S
(E ) + q T , S (Q )] [a T , S ( A ) + b T , S (B )]
Suy ra :
(Q )
(B )
(E )
( A )
+q
a
+
b
= e
P
P
= [eC P (E ) + qC
P
(Q )] [aC P ( A ) + bC P (B )] =
d =
dT
P
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1
C P
57
Trong :
CP
(5-9)
an = an (cui) - an (u)
Suy ra:
2 = 1 + a n n d
(5-10)
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58
Ar
Ar
a. trng thi 1
b. trng thi 2
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59
ny xc sut nhit ng ca h mi to thnh (W) khng phi bng tng m l bng tch
xc sut ban u ca cc h. V d, nu 2 h c xc sut nhit ng tng ng l W1 v
W2 th ta c:
W = W 1 . W2
V vy cn phi tm mt hm s xc sut sao cho khi ly cc gi tr xc sut nhn
vi nhau th s thu c gi tr ca hm bng tng cc gi tr cc hm tng ng vi xc
sut cng li vi nhau. S ph thuc ch c th biu din bng hm logarit. Hm s
logarit ny c gi l Entropi, k hiu l S:
S = klnW
(5-11)
S = S 2 S1 = K ln W2 K ln W1 = K ln WW12
Nh ni trn, y l mt h t din bin t trng thi 1 c xc sut W1 nh
hn sang trng thi 2 c xc sut W2 ln hn: W2 > W1 nn suy ra S > 0.
Vy trong h nhit ng c lp, ch c nhng qu trnh (k c phn ng ho hc
ni ring) xy ra vi s tng entropi mi t din bin.
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60
Q
T
(5-12)
ta c:
Qtn =
Suy ra:
S =
RT
dV
V
= RT
ln
V2
V1
Q tn
V
V
RT
=
ln 2 = R ln 2
T
T
V1
V1
(5-13)
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61
S =
(5-14)
Q
T
dT
T
(5-15)
S = C P
T2
T1
dT
T
= C P ln 2
T
T1
(5-16)
S = CV
T2
dT
T
= CV ln 2
T
T1
T1
(5-17)
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62
S0 = klnW = kln1 = 0
(5-18)
TH NG NHIT - NG P :
http://hhud.tvu.edu.vn
(5-19)
63
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64
Chng 6
NG HO HC
ng ho hc l mn khoa hc nghin cu v quy lut xy ra (din bin) ca cc
qu trnh ho hc trong c vn tc phn ng ho hc v cc yu t nh hng n vn
tc . Vic nghin cu ny nhm mc ch iu khin phn ng xy ra vi vn tc cao
t c hiu sut phn ng ln nht.
6.1.
VN TC PHN NG HO HC
Vn tc phn ng thng c o bng bin thin nng ca mt trong cc cht
tham gia hoc to thnh trong mt n v thi gian. Vn tc phn ng c biu th bng
n v mol/l.s.
Vn tc phn ng cng c th biu din bng s thay i ca mt trong cc tnh
cht khc ca h nh mu sc, dn in, p sut...
Nu ti thi im t1 v t2 nng ca mt trong cc hp cht ca h phn ng c
gi tr tng ng l C1 v C2 , ta c vn tc v ca phn ng l:
v =
C 2 C1
C
=
t 2 t1
t
(6-1)
Trong cng thc trn, du (+) c s dng khi tnh theo cht to thnh sau phn
ng; du (-) khi tnh theo cht tham gia phn ng.
Trong cc phn ng ho hc, nng ca cc cht lun lun thay i nn thng ngi
ta hay s dng cng thc tnh vn tc tc thi:
v =
dC
dt
(6-2)
(6-3)
65
6.2.
CC YU T NH HNG N VN TC PHN NG
v = kC
m
A
C Bn
(6-5)
trong : k hng s vn tc
CA v CB - nng tng ng vi cc hp cht A v B.
6.2.2. nh hng ca nhit n vn tc phn ng
S tng nhit trong a s cc trng hp u lm tng vn tc phn ng. T kt
qu nghin cu mt s lng ln phn ng, Vant Hoff rt ra quy tc kinh nghim sau:
Nu nhit phn ng tng thm 10 0C th vn tc ca a s phn ng s tng 2
4 ln.
Quy tc kinh nghim Vant Hoff c biu din bng cng thc sau:
v2 =
T 2 T1
10
v1
(6-6)
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66
k = C e
Ea
RT
(6-7)
trong : k hng s vn tc
C hng s trc lu tha
Ea nng lng hot ho
6.2.3. Thuyt va chm hot ng :
Thc nghim cho thy vn tc phn ng khng phi ph thuc vo tn s va chm
(s va chm trong mt n v thi gian) gia cc phn t ca cc cht tham gia phn ng
m ch ph thuc vo tn s va chm gia cc phn t hot ng cao. l nhng phn
t c to thnh do s tng nng lng nhit ng ca phn t, s tng ni nng, s
phn ly thnh cc gc t do hoc cc ion. Nng lng cn thit cung cp cho cc phn t
c trong mt mol (s Avogadro) chuyn tt c chng thnh cc phn t hot ng c
gi l nng lng hot ho ca phn ng, c k hiu Ea. Ni cch khc n l nng lng
cn tiu tn chuyn phn t ca cc cht tham gia phn ng thnh phc cht hot ng
(hnh 6.1).
E (kJ/mol)
. ......................... phc cht hot ng
Ea
....... sn phm
DH > 0 (phn ng thu nhit)
. ...........................................
cht u
DH < 0 (phn ng to nhit)
........ .sn phm
Tin trnh phn ng
Hnh 6.1. Gin nng lng ca phn ng ho hc
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67
CH2=CH2 + H2O
CuO
CH 3-CHO + H2
CH3-CH2-OH
Tc dng ca xc tc dng lm gim nng lng hot ho xy ra nh sau. Ga s
hai hp cht A v B c kh nng phn ng vi nhau qua bc to thnh phc hot ng A
... B, cho sn phm AB (DG < 0):
A + B A ... B AB
Nhng do nng lng hot ho ca phn ng ny rt ln nn thc t vn tc phn
ng gn nh bng khng. lm tng vn tc phn ng ngi ta cho thm cht xc tc
K. Cht ny d dng phn ng vi A to ra phc hot ng A ... K (phn ng xy ra d
dng tc l phn ng c nng lng hot ho thp):
A + K A ... K AK
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68
A...B
B...AK
A+B
2
A+B+K
H
AK
AB
H
AB+K
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69
Chng 7
CN BNG HO HC V CN BNG PHA
7.1. CN BNG HO HC :
a s cc phn ng u xy ra theo 2 chiu v khi vn tc phn ng thun bng
vn tc phn ng nghch, phn ng t trng thi cn bng. Ti y c phn ng thun ln
phn ng nghch vn tip tc xy ra nn cn bng loi ny c gi l cn bng ng. V
d, cn bng trong cc phn ng to thnh HI t H2 v I2 (hnh 7.1):
H2 + I 2
2 HI
% [HI]
100
80
60
40
20
20 40 60 80 100
t (ph)
eE + qQ
v1 = k 1 [ ] [B ]
a
v 2 = k 2 [E ] [Q ]
e
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70
k1 [] [B] = k 2 [E ] [Q ]
a
Suy ra:
T l
k1
[E ] [Q ]
=
k2
[ A ]a [B ]b
e
k1
l mt hng s c gi l hng s cn bng, k hiu l KC
k2
C
e
q
[
E ] [Q ]
=
[A ]a [B ]b
(7-1)
K P = K C (RT )
vi
( 7-2)
Ee Qq
Aa Bb
K P = K N P n
e
vi
NE NQ
N
a
A
Ni =
ni
n A + n B + n E + nQ
P
= Kn
n
i
KP
vi
NB
(7-4)
n E nQ
nA nB
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71
eE + qQ
ang trng thi cn bng 1 (G1 = 0). Nu ta thay i ch mt trong cc thng s trng
thi (P, C hoc T...) th cn bng s b ph v (G 0): phn ng s xy ra theo mt
chiu (gi s chiu thun):
aA + bB eE + qQ
cho n khi thit lp c mt cn bng mi 2 (G2 = 0) tng ng vi iu kin mi.
Vy s chuyn t mt trng thi cn bng ny sang mt trng thi cn bng khc
di tc ng ca cc yu t iu kin phn ng c gi l s chuyn dch cn bng.
7.3.2. nh hng ca cc yu t iu kin phn ng n chuyn dch cn bng
Ba yu t c nh hng ln nht n s chuyn dch cn bng l nng , nhit
v p sut.
7.3.2.1. nh hng ca nng
T biu thc tnh hng s cn bng theo nng :
[E ]e [Q ]q
[A ]a [B ]b
Ta thy vi KC = const, nu tng [A] hoc [B] th cn bng s chuyn dch theo chiu t
tri qua phi lm tng [E] v [Q] (lm gim [A] hoc [B]). Nu gim [A] hoc [B] th
cn bng s chuyn dch theo chiu t phi qua tri lm gim [E] v [Q] (lm tng [A]
hoc [B]).
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72
d ln K
=
dT
RT
(7-5)
KP = KN Pn
d ln K N
n
=
dP
P
(7-6)
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73
K=R-q
http://hhud.tvu.edu.vn
74
(7-7)
t 0C
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76
Chng 8
DUNG DCH
8.1.
8.1.1. H phn tn
Mt h gm hai (hay nhiu tiu phn ) trong mt tiu phn dng cc ht b tn
nh c phn b vo trong tiu phn kia th h c gi l h phn tn
Cht phn b c gi l pha phn tn, cn cht trong c pha phn tn phn b
gi l mi trng phn tn. Mi trng phn tn c th l cht kh, cht lng hoc cht
rn.
V d : H phn tn bi, khng kh (pha phn tn - cc ht bi, mi trng phn
tn- khng kh)
Tnh cht ca mt h phn tn , c bit tnh bn ca n ph thuc vo kch thc
ca pha phn tn. Pha phn tn c kch thc ht cng ln th h phn tn cng t bn
v ngc li h c pha phn tn c kch thc ht cng nh th cng bn. Da vo kch
thc ht ca pha phn tn ngi ta phn chia thnh cc h phn tn sau:
* H th:
Trong h ny ny ht pha phn tn c kch thc ht t 10-7 n 10-4 m. H ny
gm c huyn ph v nh tng, h ny khng bn.
- Huyn ph l h c to thnh bi pha phn tn th (cht rn) v mi trng phn tn
(cht lng ) . V d: Nc c
- Nh tng l h c to thnh t hai cht lng trong cht ny c phn b vo
trong cht kia . V d: Sa ng vt.
* H keo:
L h phn tn c cc ht pha phn tn c kch thc t 10-7 n 10 -9m. Nhng ht
ny khng b lng xung theo thi gian, i qua c giy lc v khng quan st c
bng knh hin vi thng thng...
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* H phn tn phn t :
L h phn tn c cc ht pha phn tn c kch thc bc phn t . y cht ho
tan c phn chia thnh cc phn t ring bit V d : cc dung dch tht ca ng,
ru, axeton...
* H phn tn ion:
Trong h ny cc ht pha phn tn tn ti di dng nhng ion ring bit . Trng
hp ny c c trng cho dung dch ca cc cht in li nh NaCl, KNO3, KCl... Kch
thc ca ht phn tn v ca mi trng phn tn l bng nhau.
8.1.2. nh ngha dung dch
Trong ho hc hai h phn tn c ngha nht l phn t v ion c gi l dung
dch:
Dung dch l mt h ng th c thnh phn bin i trong mt phm vi tng i
rng gm khng t hn hai cht trng thi phn t hay dng ion
* Dung mi:
Mt h ng th c ngha l cc tiu phn ca h c phn tn vo nhau di
dng phn t , nguyn t v ion..Tiu phn c trng thi khng thay i khi to thnh
dung dich c gi l dung mi. Trong trng hp dung dch c to thnh bng
phng php trn cht kh vi cht kh , cht lng vi cht lng , cht rn vi cht rn th
dung mi l tiu phn no c khi lng tri hn , cht cn li l cht tan. Cn c vo
trng thi tn ti, dung dch c chia thnh dung dch kh, dung dch lng, dung dch rn
* Dung dch kh:
iu kin p sut thng dung dch kh c xem nh l mt hn hp kh . V
d khng kh l mt hn hp gm cc cht kh ho tan vo nhau (Nit 78%, Oxi 21%, kh
tr 1%, ioxit cacbon, hi nc...)
* Dung dch rn:
Dung dch rn c to thnh khi lm lnh mt hp kim lng ca cc kim loi ( c
cng mt loi mng li tinh th v c kch thc nguyn t xp x nhau...) ho tan trong
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78
Ci =
mi
100 (%)
m
(8-1)
ni
1000 (molan)
m
(8-2)
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79
V d: dung dch KOH 1N c ngha l trong lt dung dch c 1 ng lng gam KOH.
Trong phng php nh phn ngi ta thng s dng rng ri biu thc v nh
lut ng lng sau y:
Nu cho VA ml dung dch A nng NA tc dng va vi VB ml dung dch B
vi nng NB th ta c:
NA.VA= NB.VB
(8-3)
Ni =
ni
n
= i
n1 + n2 + n3 + L ni
(8-4)
Ni = 1
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80
Cl-
Na+
Cl-
Na +
Na
Na +
Cl
Na
Cl
+
-
Cl-
Na+
Cl-
Na +
Cl-
Na+
Cl-
Na +
Cl-
G = Hht - TS < 0
(8-5)
Hht = Hs + HCT
(8-6)
Trong
S = Spt + SS
(8-7)
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81
(8-8)
Trong :
m- Khi lng kh ho tan trong mt th tch xc nh ca cht lng
k- H s t l ph thuc vo bn cht ca cht kh v dung mi
* ho tan cht lng vo cht lng:
ho tan ca cht lng vo cht lng c th l v hn (ho tan ca ru etylic
vo nc), nhng thng th c gii hn (ho tan ete vo nc).
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82
Mt khc khi nhit tng th ho tan ca cht lng vo trong cht lng c th
tng (ho tan nc vo ete) hoc c th gim (ete vo nc).
2.4
160
2.2
140
2.0
120
1.8
100
1.6
80
60
40
20
0
O3
180
KN
hoatan, g/100g nc
1.4
l
4C
NHaCl
N
1.2
1.0
O4
CuS lO3 Cl2
KC Hg
0.8
20 40 60 80 100
0.6
20
40
60
80
100
120
Nhi
t
, C
a
Nhi
t
, C
b
ho tan ca hu ht cht rn vo cht lng tng ln khi nhit tng (Hnh 8.2
a ). Tuy nhin trong mt s trng hp khi nhit tng ho tan ca cht rn gim
(Hnh 8.2 b)
Khi nhit gim th ho tan ca cht rn gim. Gi s nhit t1 ho tan
ca cht rn l s1 v nhit t2 l s2 . Vy khi nhit gim t t2 n t1 th c mt
lng cht rn a = s2 - s1 kt tinh li . Tuy nhin trong mt s trng hp nu ta lm
ngui tht cn thn dung dch bo ho ca mt s cht th khi n nhit gim n t1 ta
khng thu c mt lng cht rn a kt tinh li. Dung dch nh vy gi l dung dch qu
bo ho - dung dch c nng ln ho tan nhit .
Dung qu bo ho khng bn do ch cn khuy nh hoc cho vo dung dch ny
mt mt vi tinh th mm kt tinh th lng cht rn a s kt tinh li v dung dch s tr
thnh bo ho.
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83
8.2.
(8-9)
(8-10)
N1 = 1 - N2
Thay N1 vo (8-10), ta c:
P1 = P10 .(1- N2)
10 1
= 2
10
hay
= 2
10
(8-11)
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84
n2
n
m
= 2 =
2 =
0
n1 + n2 n1 n1 M
1
Trong :
(8-12)
t2
O
O'
t1
O''
t,0C
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85
T = k . e
(8-13)
T S = k S . e
(8-14)
trong :
Td = k d
m . 1000
MD
(8-15)
TS = k S
m . 1000
MD
(8-16)
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86
1
2
(8-17)
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87
Nu n2 l s mol cht tan c trong th tch V ca dung dch , m l s gam cht tan
c trong th tch v M l khi lng phn t cht tan ta c :
Pt =
nRT mRT
=
V
MV
(8-18)
8.3.1. Thuyt in ly
8.3.1.1. Tnh cht bt thng ca dung dch in li
Tt c cc hp cht c chia thnh 2 loi: cht in li v cht khng in li.
Cht in li (axt, baz, mui) l nhng hp cht m trng thi dung dch lng
hoc nng chy c kh nng dn in. Cht khng in li (ru, ete, hydrocacbon...) l
nhng cht khng dn in. Trong phn tip theo ch nghin cu dung dch nc ca axt,
baz v mui.
Nghin cu tnh cht ca dung dch in li ngi ta nhn thy rng cc gi tr:
gim p sut hi bo ho Dp', gim nhit ng c Dt', tng nhit si Dt's v
p sut thm thu Pt' thu c bng thc nghim u ln hn Dp, Dt, Dts, P tng ng
tnh theo l thuyt ca dung dch cht khng in li.
8.3.1.2. Thuyt in li ca Arrhennius
Tnh cht bt thng trn y ca dung dch cht in li c Arrhenius gii thch
bng thuyt in li. Theo ng khi ho tan trong nc cc phn t cht in li phn li thnh
cc phn t mang in tch dng (ion dng) v cc phn t mang in tch m (ion
m). Hin tng cc phn t phn li thnh cc ion gi l s in li hay s ion ho. Di
tc dng ca dng in, cc ion dng chuyn n catot v cc ion m chuyn n anot dung dch dn in.
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88
t' = ik.C
t's = iks.C
P' = ic2RT
Suy ra:
i=
p t
t s
(8-19)
Nh vy, i vi dung dch cht in li ta c i >1, dung dch cht khng in li i=1.
ngha vt l ca h s Van't Hoff.
I=
(8-20)
S phn t ho tan
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89
2. S in li ca hp cht phn cc
V d: S ho tan ca HCl vo H2O (hnh 8.5 ) y di tc dng ca H2O phn
t HCl tr thnh phn cc hn v dn dn chuyn thnh ion.
b
Cation
Anion
x
x
hoc = .100%
n
n
(8-21)
Trong :
x - s mol phn t cht tan phn li;
n - s mol phn t cht tan c trong dung dch.
T (8-20) ta nhn thy 0 1 hoc 0 100%.
Nh vy i vi cht khng in li = 0. i vi cc cht in li thng chia
thnh 3 loi:
-
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90
s cn bng K.
V d, hng s cn bng ca axt axtic:
CH3COOH '
[H ] [CH COO ]
+
K=
CH3COO- + H+
_
[CH 3 COOH ]
K=
2
.C
1-
(8-22)
Phng trnh (8-22) l biu thc ton hc n gin nht ca nh lut pha long
Ostwald. Theo (8-22) ta thy nu a tng th K tng, do mun K = const th C phi
gim. Tc phi lm long dung dch. i vi cht in li yu a c gi tr nh 1-a tnh gn
ng bng 1 suy ra (8-22) c dng:
K = 2.C
(8-23)
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91
a=
Trong :
N N + nN
N
i 1
n 1
(8-24)
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92
C6U5NH- + NH +4
C6H5NH3+ + HO-
baz
HCl
axt
H2O
NH +4
HO-
Cl-
axt
+
NH3
NH +4
baz
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93
H3O+
H2O
axt 1
baz 2
axt 2
Clbaz 1
HCl Cl- v H3O+ H2O l cc cp axt - baz lin hp. so snh mnh,
yu ca cc cp axt - baz ngi ta thng ly cp H3O+ H2O lm chun gi l thang
axt - baz i vi nc.
8.4.3. Tch s ion ca nc - ch s hyr ( pH)
Cp H3O+ - H2O ca nc t ion ho
hay
H2O +
H2O
H3O+
baz 1
axt 2
axt 1
H3O+ +
2H2O
+ HObaz 2
HO-
H 2O
H O+ + HO
3
Suy ra:
5,5.10 6 1 , m 1
= 10 4 mol.m 3 = 10-7 M
4
1
2
1
(350 + 198)10 .m .mol
[H3O+] = [HO-] =
http://hhud.tvu.edu.vn
(8-25)
K H 2 O = 10-7
94
Suy ra:
(8-26)
[H3O+] [HO-] =
pH + pOH = p = 14
(8-27)
HA + H2O
[ H 3 O + ][ A ]
[ HA]
(8-28)
(8-29)
B + H2O
[BH + ][HO ]
[B ]
(8-30)
(8-31)
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95
HA + H2O
Ka =
HA + HO-
Kb =
Ka.Kb = . = [H3O+][HO-] =
Tch:
Suy ra:
pKa + pKb = 14
(8-32)
pH = -lg[H3O+] = -lgCa
(8-33)
* Axt yu:
Phn ng phn li axt yu:
H3O+ + A-
HA + H2O
Phn ng phn li nc:
2H2O
H3O+ + HO-
[H 3O + ][A ]
[HA ]
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96
Phn ng phn li y ch yu l:
H3O+ + A-
HA + H2O
Do
[H3O+] = [A-]
[HA] = Ca - [H3O+]
Do :
[H 3O + ]
Ka =
C a [H 3 O + ]
Suy ra:
[H3O+] =
K a K a2 + 4K a C a
2
(8-34)
Suy ra:
[H3O+] =
KaCa
(8-35)
2H2O
B + H3O+
BH+ + H2O
[H3O+] =
Suy ra:
pH = -lg[H3O+] = 14 + lgCb
http://hhud.tvu.edu.vn
(8-36)
97
* Baz yu:
Phn ng phn li ca dung dch baz yu
2H2O
Cng (1) v (2) ta c:
H3O+ + HO-
B + H3O+
BH+ + H2O
B + H2O
BH+ + HO-
(1)
(2)
[BH + ][HO ]
[B ]
V t
Kb =
[HO ]2
[C b [HO ]
Suy ra:
[HO-] =
K b K 2b + 4K b C b
2
(8-37)
[HO ]2
Cb
K bC b
(8-38)
(8-39)
H3O+ + HO-
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98
CH3COONa =
Na+
H3O+ + HO-
'
2H2O
+ CH3COO-
CH3COO- + H3O+
'
CH3COOH + H2O
NH4Cl
=
'
2H2O
NH 4+ + HO- '
+ ClHO- + H3O+
NH4OH
CH3COONH4 + H2O
K
CH3COOH
1,76.10-5
NH4OH
1,79.10-5
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99
8.5.
CHT CH TH MU
xc nh chnh xc pH ca dung dch in li ngi ta s dng phng php
'
mu axt
Ka =
H3O+ + Ct m
mu baz
[H 3 O + ][Ct m ]
[HCt m ]
Suy ra:
[H3O+] = Ka.
hay
pH = pKa + lg
[HCt m ]
[Ct m ]
(8-40)
(8-41)
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100
3,1
Metyl da cam
4,4
da
cam
hng
Qu
10
14
vng
tm
Phenolphtalein
khng mu
xanh
hng
AgCl
v
2
Ag+ + Cl-
Trong : v1 = K1.S
v2 = K2.S (aAg, aCl )
K1, K2 - hng s
S - din tch b mt cht rn
Ti thi im cn bng v1 = v2
K1S = K2S a Ag.aClSuy ra :
K1
= aAg + a Cl
K2
'
nAm+ + mBn-
ta c:
TA n B m = [Am+]n .[Bn-]m
(8-41)
Tch s ho tan T l hng s khng c ngha nng ca cc ion trong dung dch
bo ho cng l hng s. V d nu trong trng hp trn ta thm HCl vo dung dch th
nng ion Cl- s tng ln. Ti thi im ny ta c:
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101
http://hhud.tvu.edu.vn
102
Cl-
Cl-
Fe
O+
Cl-
Cl-
FeO+
O
Fe
Cl -
FeO +
ClCl-
FeO
ClFe
O+
FeO
FeO
O
Fe
+
ClClCl
Cl-
FeO+
Nh
n
FeO +
Cli xe
n
Cl-
[Fe(OH)3]m
Ha
t keo
Cl-
Cl-
ClCl Cl -
Cl-
{[Fe(OH)3]m.
lp b hp ph
nhn
xCllp khuych tn
ht keo
mixen
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103
http://hhud.tvu.edu.vn
104
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105
Chng 9
PHN NG OXI HO KH V IN HO
9.1.
PHN NG XI HO KH. CP XI HO - KH
Phn ng xi ho - kh l loi phn ng xy ra cng vi s thay i s xi ho ca
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106
Kt qu l electron cha trong kim loi d (kim loi tch in m), nc cha
cation kim loi (tch in dng) v do lm xut hin mt lc ht tnh in trn ranh
gii gia kim loi v cht lng (hnh 9.1). Ngi ta ni y xut hin mt lp in tch
kp v hiu in th trn b mt ny c gi l th in cc.
Zn
H2O
e
E02
2e
E01
Cu2+ O
O
Zn
Zn-2eZn
2+
2e
Cu
Cu2+ +2eCu
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107
Cu2+Cu(+)
Trong vch n biu th ranh gii phn cch gia in cc vi dung dch, vch
kp ranh gii gia cc dung dch, (-) v (+) l du ca cc in cc.
9.2.3. Th in cc tiu chun
Th in cc ca tng in cc ring bit gi l th in cc tuyt i. Th in
cc ny rt kh xc nh nn trn thc t ngi ta thng dng th in cc tng i.
Th in cc tng i c tnh bng cch so snh th in cc tuyt i ca mt
in cc cn xc nh vi mt in cc chun c th in cc qui c bng khng. Th
in cc chun c s dng so snh l th in cc hydro, c cu to trn hnh 9.3
(phn bn tri). l mt ci bnh c hnh dng c th cha dung dch H2SO4 vi nng
[H3O+] = 1 g-ion / lit. Mt thanh platin ph mui platin c nhng vo dung dch v
thi hydro i qua bnh. Trn ranh gii phn cch Pt, H2H3O+ xut hin mt hiu in th
xc nh c qui c bng khng ( iu kin 25OC, v 1atm).
Pt
H2
H+2 SO4
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108
Dng electron
Cu
Pt
H2
H2SO4
CuSO4
KCl
H2
(9-1)
/ H 2 ( tra 'i )
Cu2+ Cu (+)
Vi phn ng to dng l:
Cu2+ + H2 + 2H2O = Cu + 2H3O+
Thc nghim o c S l 0,337V c dng in i t tri qua phi nn:
oCu2 + / Cu = + 0,337 V
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109
Zn2+ Zn (-)
Vi phn ng to dng:
Zn + 2H3O+ = Zn2+ + H2 - + H2O
c dng in i t phi qua tri, suy ra:
oZn 2 + / Zn = -0,763V
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110
Phn ng in cc
(vn)
Li+ Li
Li+
+ e
Li
-3,045
K+
K+
+ e
-2,925
Rb+ Rb
Rb+
+ e
Rb
-2,925
Cs+ Cs
Cs+
+ e
Cs
-2,923
Ca2+ Ca
Ca2+
+ 2e D
Ca
-2,870
Na+ Na
Na+
+ e
Na
-2,714
Mg2+ Mg
Mg2+ + 2e
Mg
-2,370
Be2+ Be
Be2+
+ 2e
Be
-1,850
Al3+ Al
Al3+
+ 3e
Al
-1,660
Mn2+ Mn
Mn2+ + 2e
Mn
-1,180
Zn2+ Zn
Zn2+
+ 2e
Zn
-0,763
Cr3+ Cr
Cr3+
+ 3e
Cr
-0,740
Fe2+ Fe
Fe2+
+ 2e
Fe
-0,440
Cr3+,Cr2+ Pt
Cr3+
+ e
Cr2+
-0,410
PbSO4 Pb
PbSO4 + 2e
Pb + SO42-
-0,356
Co2+ Co
Co2+
+ 2e D
Co
-0,277
Ni2+ Ni
Ni2+
+ 2e
Ni
-0,250
Sn2+ Sn
Sn2+
+ 2e
Sn
-0,136
Pb2+ Pb
Pb2+
+ 2e
Pb
-0,126
H3O+ H2 ,Pt
2H3O+ + 2e
H2 + 2H2O
Cu2+,Cu+ Pt
Cu2+ + e
Cu+
+0,153
Cu2+ Cu
Cu2+ + 2e D
Cu
+0,337
OH- O2, Pt
+0,401
Cu+ Cu
Cu+
Cu+
+0,52
I- I2, Pt
I2
2e
2 I-
+0,536
Fe3+ ,Fe2+ Pt
Fe3+
+ e
Fe2+
+0,771
http://hhud.tvu.edu.vn
0(theo qui c)
111
Hg2+ Hg
Hg2+ + 2e
2Hg
+0,798
Ag+ Ag
Ag+ + e
Ag
+0,799
Hg2+ Hg
Hg2+ + 2e
Hg2+
+0,854
2Hg2+ + 2e
Hg22+
+0,91
Br- Br2,Pt
Br2
2Br-
+1,066
Mn2+ + 2H2O
+1,236
Cr2O72- ,Cr3+ Pt
2Cr3+ +7H2O
+1,33
Cl- Cl2,Pt
Cl2
Pb2+ PbO2,Pb
Pb2+ + 2H2O
+1,455
Au3+ Au
Au3+ + 3e
Au
+1,50
Mn2+ +2H2O
+1,51
Hg2+,Hg22+
Pt
MnO4-, H3O,Mn2+ Pt
+ 2e
+ 2e
D
D
2Cl-
+1,359
Ce4+,Ce3+ Pt
Ce4+
+ e
Ce3+
+1,61
Au+ Au
Au+
+ e
Au
+1,70
F- F2,Pt
F2
+ 2e
2F-
+2,87
oNa + / Na = -2,714V nn
4
4
Mn 2 + , Pt
= +1,507V
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112
oZn 2 + / Zn
V d:
= -0,763V v = + 0,799V
nn phn ng xy ra l:
Zn + 2Ag+ = Zn2+ + 2Ag
Qua nhn xt ny suy ra ch nhng kim loi no c th in cc tiu chun nh
hn khng mi y c hyro ra khi dung dch axt long.
9.2.3. Phng trnh Nernst
Mt trong nhng nh hng ln n gi tr th in cc l nng ca ion kim
loi lm in cc. S ph thuc c tnh bng cng thc Nernst
M n + / M = oM n+ / M +
RT
ln[M n + ]
nF
(9-2)
Trong :
0,059
lg[M n + ]
n
(9-3)
'
n'iA'i
i = io +
0,059 [ Ai ] hi [oxi ]
.
lg
n
[ A'i ] n 'i [kh]
(9-4)
GT = - nFE
(9-5)
nhit T = 298oK:
G o298 = -nFEo
http://hhud.tvu.edu.vn
(9-6)
113
(9-7)
el - th in cc cp oxi ho kh dng hn
eb - th in cc cp oxi ho kh m hn
n / Pt
Vi in cc kh HO-/O2, Pt
O2 + H2O + 2e = 2HO1/ 2
HO
Ta c:
/ O2 , Pt
o
HO / O2 , pt
PO 2
0,059
+
lg
2
[ HO ] 2
Zn 2 + / Zn
= -0,763V;
Cu2+ Cu(+)
oCu2 + / Cu = + 0,337V
Ta c cc phn ng in cc:
Cu2+ + 2e = Cu
Zn2+ + 2e = Zn
oZn 2 + / Zn = -0,763
(2)
eo = +0,337 V
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114
Zn - 2e = Zn2+
o = + 0,763V
E = 1,10V
V d 2: Xt chiu ca phn ng
2Cu2+ + 4I- = 2CuI + I2
oCu2 + / Cu + = + 0,17V ; o2 I / I 2 = + 0,54V
Bit:
v TCuI = 10-12
2 I / I2
> o
Cu 2 + / Cu +
th phn ng xy ra
theo chiu
I2 + 2CuI 2Cu2+ + 4ITrn thc t do c s to thnh CuI t tan lm nng Cu+ gim dn n th ca
cp
Cu 2 + / Cu +
thay i
Cu2 + / Cu + = oCu2 + / Cu + + 0,059lg
Thay [Cu+] =
[Cu 2 + ]
[Cu + ]
TCuI
ta c
[I ]
Cu2 + / Cu + = 0,17 + 0,059lg
[Cu 2 + ][I ]
TCuI
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115
lnK =
nFE o
nE o
hay lgK =
RT
0,059
(9-8)
9.3.1. in phn
Trong cc phn trn y chng ta ch ch kho st trng thi cn bng gia in
cc v dung dch khi khng c s lu thng dng in trong h in ho. Nu trong
trng hp cc phn ng trn in cc c gy ra bng mt ngun in bn ngoi (trong
h in ho c s lu thng dng in) th l s in phn.
Vy s in phn l qu trnh oxi ho v kh xy ra in cc khi cho dng in
mt chiu i qua cht in li nng chy hoc dung dch cht in li.
Cc phn ng xy ra trn in cc l th nng lng in nng; trong catot cht kh v n cho cation electron, anot - cht oxi ho v n nhn electron.
V d s in phn mui NaCl nng chy trn hnh 9.5
e- - + e-
Dong electron
ANOT
KATOT
e
Na+
e-
Cl-
K'
Nao
S
Clo
A'
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116
ng thi trn anot xy ra phn ng oxi ho cn Cl- bng nng lng ca ngun
in:
2Cl- - 2e = Cl2
hiu c r hn cc quy lut xy ra trn catot v anot, cn lm quen vi cc
khi nim s phn cc in cc, th phn hu v qu th.
9.3.2. S phn cc
Khi dng in i qua ranh gii phn chia in cc - dung dch th lm cho trng
thi in ca in cc thay i. Hin tng gi l s phn cc in cc. nu s thay
i th in cc dch chuyn v pha dng hn so vi th cn bng th gi l s phn cc
anot v ngc li - s phn cc catot.
S phn cc in cc c chia thnh cc loi nh: phn cc nng , phn cc ho hc,
phn cc in ho.
S phn cc nng sinh ra bi s bin i nng cn lp gn b mt in
cc khi c mt ca dng in i qua. Trong trng hp ny th ca in cc anot tng
(tr thnh dng hn) do nng ca ion kim loi ho tan tng ln, tri li th in cc
catot gim (tr thnh m hn) do nng ion trn b mt ca n gim.
S phn cc ho hc sinh ra do phn ng gia mi trng hoc cht in li vi vt
liu lm in cc khi c dng in i qua lm bin i tnh cht ca b mt in cc dn
n s thay i th.
S phn cc in ho c sinh ra do dng electron (n catot ni vi cc m v
ri anot ni vi cc dng ca ngun in) khng i qua c dung dch in li khi c
in p gia 2 cc cha t c mt gi tr cn thit lm xut hin mt hiu in th
ngc chiu vi chiu ca ngun in ngoi.
9.3.3. Th phn hu
Nh ni trn y, s in phn ch bt u xy ra mt in p hon ton xc
nh. in p ti thiu gia hai in cc s in phn bt u xy ra gi l th phn
hu (k hiu eph). Th phn hu c xc nh bng thc nghim. Trn bng 9.2 l th
phn hu ca mt s cht in phn.
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Cht in
eph(V)
Cht in phn
eph(V)
HNO3
1,69
NaNO3
2,15
AgNO3
0,70
H2SO4
1,67
Na2SO4
2,21
CuSO4
1,49
H3PO4
1,70
HCl
1,31
ZnSO4
2,35
NaOH
1,69
HBr
0,94
NiCl2
1,85
KOH
1,67
HI
0,52
NiSO4
2,09
phn
phn
eph(V)
9.3.4. Qu th
Hai qu trnh in ho (mt xy ra trong nguyn t ganvani v mt trong in
phn) u c chung mt bn cht. l phn ng oxi ho in cc. im khc nhau ca
hai qu trnh ny l chng xy ra theo hng khc nhau. Do vy cho s in phn bt
u xy ra, v mt l thuyt ch cn t mt in p c gi tr bng S ca nguyn t
ganvani tng ng nhng ngc chiu.
V d: S ca nguyn t ganvani:
(-) Ni| Ni+2
qt = ph - E
Trong v d trn:
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Ca+ + 2e = Ca
(+) Ant:
2Cl- = Cl2 + 2e
(1)
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Vy khi in phn dung dch nc, ch nhng kim loi no ng sau nhm v
khng k nhm mi thot ra trn in cc.
Nu dung dch cha cc ion kim loi khc nhau th phn ng kh s xy ra theo
hng gim dn th in cc tiu chun tng ng vi kim loi.
V d i vi hn hp Ag+, Cu2+, Fe2+ th Ag+ b kh trc ( oAg
tip n Cu2+ ( oCu
2+
/ Cu
2+
/ Fe
/ Ag
= +0,779V)
= - 0,440V)
* Trn in cc anot:
Cc phn ng xy ra trn anot ngoi s ph thuc vo s c mt ca H2O cn ph
thuc vo vt liu lm in cc: anot tan v khng tan.
1. Nu s dng anot tan nh Cu, Ag, Zn, Cd, Ni, Fe... th phn ng trn in cc l phn
ng ho tan anot: M - ne = Mn+ ch khng phi anion dung dch b oxi ho.
2. Nu s dng anot khng tan (anot tr) nh than, graphit, Pt th trn in cc c th
anion dung dch hoc ion HO- b xi ho:
- Nu anion dung dch l nhng ion khng cha oxi (Cl-, Bv-, I-, S2-, CN-...) th chng s
b oxi ho trn anot.
V d:
2Cl- - 2e = 2Cl
2Cl CL2
-
Nu anion dung dch l nhng ion c cha oxi (NO3-, SO42-, PO43-...) th chng s
khng b oxi ho trn anot m ch c HO- b oxi ho:
HO- - 2e = H+ + O
2O = O2 -
Nhng do nng HO- rt nh (10-7M) nn ngi ta coi nh phn t H2O b oxi ho:
2H2O - 4e = 4H+ + O2
Nu dung dch cha cc anion khc nhau th phn ng oxi ho trn anot s xy ra
theo th t: u tin l cc anion khng cha oxi, tip n HO- v cui cng l cc anion
cha oxi.
V d: S in phn dung dch CuCl2 vi in cc graphit nh sau:
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Catot: Cu2+ + 2e = Cu
Anot: 2Cl- - 2e = Cl2
Cu2+ + 2Cl- = Cu + Cl2
CuCl2 Cu + Cl2
Hay
Anot:
PIN V ACQUY
Nh kho st trn y phn nguyn t ganvani, in nng c th sn xut trc
Mt trong nhng hnh dng cu to ca pin c trnh by trn hnh 9.6 P. Cc phn
ng c bn xy ra khi c s phng in trong pin nh sau:
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- Ti cc m:
2Zn 2Zn2+ + 4e
2Zn2+ + 4NH4Cl [Zn(NH3)4]Cl2 + ZnCl2 + 4H+
-
Ti cc dng:
2MnO2 + 4H+ + 4e 2MnO(OH)2
Loi pin ny c S khong t 1 - 1,5V
1
2
1. Cc dng (ng)
2. Phn cch in
3. Li than ch
4
5
6
4. Cc m (nhm)
5. Bt nho(NH4Cl)
6. Bt (MnO2)
7. Lp v ngoi
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Nhin li
u
Sa n pham
phng
tch in
2PbSO4 + 2H2O
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2Ni(OH)2 + Fe(OH)2
phng
2NiOOH + Fe + 2H2O
Ngoi ra ngi ta cng s dng tng i rng ri cc loi acquy kim nh: niken cadimi, niken - km, bc km.
9.5.
N MN IN HO V CCH CHNG N MN IN HO
n mn kim loi v hp kim l qu trnh t ph hu cu trc kim loi v hp kim
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H3O+ + e
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Fe
H2
H+
Cu
H+
Fe2+
Fe(OH)3 = Fe
OH
+ H2O
Hp cht Fe
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ng
ng
Zn2+
Zn2+
Me+
H+
Kem
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