1

n mn v bo v kim loi. NXB i hc quc gia H Ni 2006.

T kho: n mn v bo v kim loi, Th in cc, Sc in ng ca bin in, in cc,
Lp in kp, Sc in ng.

Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc
ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc
v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc

Chng 3 Th in cc v sc in ng ca pin in .................................................. 2
3.1 in cc v nguyn nhn sinh ra th in cc........................................................ 2
3.2 Lp in kp trn b mt in cc.......................................................................... 2
3.3 S ph thuc ca gi tr th in cc vo nng cht phn ng .......................... 4
3.4 Phn loi in cc .................................................................................................. 6
3.4.1 in cc loi 1 ................................................................................................... 6
3.4.2 in cc loi 2 ................................................................................................... 7
3.4.3 in cc kh ..................................................................................................... 10
3.4.4 in cc oxi ho kh (Redox).......................................................................... 12
3.4.5 in cc oxit kim loi ...................................................................................... 12
3.5 S dng gi tr th in cc tiu chun xt chiu hng phn ng....................... 14
3.6 Pin in (Pin Ganvani hoc mch in ha)......................................................... 16
3.6.1 Pin in v cc phn ng xy ra trong pin........................................................ 16
3.6.2 Sc in ng ca pin in............................................................................... 17
3.6.3 Phn loi pin in............................................................................................. 18
3.7 Phng php o sc in ng v ng dng........................................................ 20
Chng 3. Th in cc v sc in ng ca
pin in
Trnh Xun Sn
2

Chng 3
Th in cc v sc in ng ca pin in
3.1 in cc v nguyn nhn sinh ra th in cc
in cc l mt h in ha gm cht dn in loi 1 tip xc vi cht dn in loi 2.
V d: Kim loi Cu tip xc vi dung dch mui sunfat ng Cu
2+
SO
4
/Cu hoc Cu
2+
/Cu
hoc Zn
2+
/Zn; Fe
3+
,Fe
2+
/Pt vv (mt gii hn gia hai pha rn v lng c k hiu bng
gch cho / hoc l gch thng).
V mt ha hc tm phn ra in cc tr v khng tr. Mt in cc c gi l in cc
tr nu dy dn loi 1 khng tham gia phn ng v ch c chc nng l trao i electron, v d
in cc Pt trong cc h in phn dung dch NaOH, dung dch H
2
SO
4
Ngc li, mt in
cc gi l khng tr nu cht dn in loi 1 c tham gia phn ng oxi ho kh trn mt gii
hn pha v sau mt thi gian lm vic khng cn nguyn vn nh lc ban u
V d: Anot Ni trong cc qu trnh m in. in cc Ni b ha tan theo phn ng:
Ni 2e Ni
2+
Sau thi gian phn ng khi lng anot niken b gim i v b chuyn thnh ion Ni
2+

i vo dung dch.
Trn b mt gii hn ca hai pha cht dn in loi 1 v 2 lun tn ti lp in kp v n
l nguyn nhn sinh ra th in cc
3.2 Lp in kp trn b mt in cc
Khi nhng mt kim loi Me vo trong dung dch mui cha ion Me
n+
ca n (v d nhng
kim loi bc vo dung dch AgNO
3
long, kim loi ng trong dung dch CuSO
4
) trn b
mt gii hn xy ra hin tng chuyn ion kim loi t kim loi vo dung dch.
Ta xt trng hp kim loi bc trong dung dch AgNO
3
long (hnh 3.1).



3
Hnh 3.1
S hnh thnh lp in kp trn mt gii hn pha
ca in cc Ag trong dung dch AgNO
3
long
a) S di chuyn ca ion Ag
+
(t kim loi) vo trong dung dch;
b) Lp in kp trn b mt gii hn pha; c)S phn b th theo chiu dy lp in kp
Trn hnh 3.1a m t s dch chuyn ion Ag
+
trn b mt kim loi (
KL
Ag
+
) i vo dung
dch AgNO
3
, thot u ion
KL
Ag
+
i vo dung dch vi tc ln v li electron trong kim
loi. V b mt kim loi Ag d in tch m nn ion
KL
Ag
+
th 2 i vo dung dch kh khn
hn, tip theo sau cc ion th 3, th 4 i vo trong dung dch cng kh khn hn na.
Ngc li, theo thi gian nng ion Ag
+
gn st b mt kim loi tng dn ln v lm d
dng cho cho s dch chuyn ion Ag
+
t dung dch i vo b mt kim loi. Sau mt thi gian
nht nh trn b mt gii hn pha t trng thi cn bng ca hai qu trnh ion
KL
Ag
+
i vo
dung dch v ion Ag
+
t dung dch i vo trong kim loi. Khi h t trng thi cn bng, trn
b mt gii hn hnh thnh lp in kp, vi hai bn tch in ngc du v chiu dy lp kp
c bn knh nguyn t () (xem hnh 3.1c). Do c lp in kp sinh ra th in cc E, s
phn b th in cc ca lp in kp trn mt gii hn pha theo chiu dy ca lp d l tuyn
tnh (hnh 3.1c).
Lp in kp gi tt l lp kp trn hnh 3.1b cn gi l lp kp c - lp kp Helmholtz
- lp kp ny ch yu l do lc tng tc tnh in v c p dng cho cc dung dch tng
i m c
Khi dung dch tng i long v tnh n s chuyn ng nhit cc ion gn b mt in
cc, th s phn b th ca lp kp theo chiu dy lp kp gm 2 phn: phn tuyn tnh v
phn khng tuyn tnh.

4

Hnh 3.2
a) Lp kp c tnh n chuyn ng nhit;
b) S phn b th E(V) theo chiu dy lp kp
Trong trng hp ny Stern chia lp kp thnh 2 phn:
+ Phn Helmholtz - Cn gi l lp kp c (c k hiu l (*) trn hnh 3.2b).
+ Phn khuch tn - Phn Goui- Chapman (c k hiu (**) trn hnh 3.2b).
Nghin cu v cu trc lp kp l mt vn rt hp dn cc nh in ha, v n c
ngha khoa hc rt ln, song c nhng hn ch nht nh v lp kp rt phc tp. Vn ny
c trnh by y hn trong cc gio trnh chuyn .
3.3 S ph thuc ca gi tr th in cc vo nng cht phn ng,
phng trnh Nernst
Trn b mt gii hn pha cht dn in loi 1 v loi 2 ca in cc xy ra phn ng oxi
ha kh dng:

i
Ox
i
+ Ze
i
Red
i
(3.1)
Khi
i
= 1 ta c:
Ox
i
+ Ze Red
i
(3.2)
V d trn in cc Cu
2+
/Cu xy ra phn ng :
Cu
2+
+ 2e Cu (3.3)
Gia bin thin ha th ca phn ng (3.3) v th in cc E quan h vi nhau theo
phng trnh:
= A
Max
= Z.F.E (3.4)
trong : Z l s electron trao i;
F l hng s Faraday (96493 C);
A
Max
l cng cc i hu ch.
p dng phng trnh (3.4) cho phn ng (3.3) ta c:
5
=
C

SP
(3.5)
trong :
C
: Tng ha th ca cc cht u tham gia phn ng;

SP
: Tng ha th ca cc cht sn phm c to ra.
Ta c: =
2
Cu
+
+ 2
e

Cu

=
2
o
Cu
+
+ RTln
2
Cu
a
+
+
e

Cu

=
2
o
Cu
+
+ 2
e

Cu
+ RTln
2
Cu
a
+
= ZFE
Vy th in cc E bng:
E =
2
2
o
e Cu
Cu
Cu
2 RT
lg a
ZF ZF
+
+
+
+
E = E
o
+
2
Cu
RT
lg a
ZF
+
(3.6)
trong : E
o
=
2
o
e Cu
Cu
2
ZF
+
+
gi l th in cc tiu chun ( 25
o
C).
Vy: E = E
o
khi hot
2
Cu
a
+
= 1.
Phng trnh (3.6) gi l phng trnh Nernst. Cn ch rng bng con ng l thuyt
v thc nghim khng xc nh trc tip c gi tr tuyt i ca th in cc tiu chun E
o
.
Phng trnh Nernst vit cho phn ng tng qut (3.1) nh sau:
E = E
o
+
i
oxi
i
Redi
RT a
ln
ZF a

(3.7)
hoc 25
o
C ta c:
E = E
o
+
i
oxi
i
Redi
0,059 a
lg
Z a

(3.8)
trong k hiu l tch s cc hot .
V d vit phng trnh Nernst cho cc in cc sau:
Zn
2+
/Zn vi phn ng in cc Zn
2+
+ 2e Zn 25
o
C:

2
Zn
Zn
E
+
=
2
o
Zn
Zn
E
+
+
2
Zn
Zn
a 0,059
lg
2 a
+

Fe
3+
, Fe
2+
/Pt vi phn ng in cc Fe
3+
+ 1e Fe
2+
25
o
C:

3
2
Fe
Fe
E
+
+
=
3
2
o
Fe
Fe
E
+
+
+
3
2
Fe
Fe
a 0, 059
lg
1 a
+
+

O
2
(Pt)/H
2
O vi phn ng in cc O
2
+ 4e + 4H
+
2H
2
O 25
o
C:
6

2
2
O
H O
E =
2
2
o
O
H O
E +
2
2
4
O
H
2
H O
p .a
0,059
lg
4 a
+

Thng thng hot kim loi tham gia phn ng c quy c bng n v (tr trng
hp kim loi trong hn hng thy ngn), hoc hot ca nc bng n v.
i vi cht kh thay cho vic biu din nng ngi ta dng khi nim p sut v d
2
O
P ,
2
H
P ...
T cc phng trnh (3.6), (3.7), (3.8) cho thy rng, mun xc nh gi tr th in cc E
cn phi bit chnh xc nng cc cht tham gia phn ng v gi tr th in cc tiu chun
E
o
.
Gi tr th in cc tiu chun E
o
ca mt in cc bt k c xc nh da vo th in
cc tiu chun hiro c gi tr chp nhn bng 0,00 V. V d th in cc tiu chun ca in
cc km: Zn
2+
/ Zn c gi tr bng 0,76 V NHE, c ngha l n c so vi th ca hiro
(v in cc hiro s c cp n trong phn sau) hoc vi in cc ng Cu
2+
/Cu c gi
tr th tiu chun bng 0,34 V NHE; qua nhng v d ta c th nh ngha gi tr th in
cc tiu chun E
o
nh sau: "Gi tr th in cc tiu chun E
o
ca mt in cc bt k cn xc
nh l sc in ng E ca pin in gm in cc tiu chun hiro (
H
a
+
= 1 v
2
H
P = 1
atm) v in cc tiu chun ca in cc cn xc nh". Du ca gi tr th in cc tiu
chun chp nhn l du dng so vi in cc tiu chun hiro nu trong pin in, in cc
tiu chun cn xc nh l cc dng (catot) so vi in cc tiu chun hiro v ngc li.
Trn c s o gi tr th in cc tiu chun ca cc in cc ngi ta xp cc gi tr th in
cc tiu chun thnh bng (xem bng 3.1) gi l bng gi tr th in cc tiu chun.
Nng cc cht phn ng ca in cc thng c biu din qua i lng hot a
ca cc ion tham gia phn ng, trong trng hp dung dch long th hot a ca cht phn
ng c thay bng nng C (mol/l).
V d i vi in cc Fe
2+
/Fe vi phn ng in cc l:
Fe
2+
+ 2e Fe
25
o
C vi C
Fe
+ 2

= 10
6
mol/l th ta c gi tr th in cc ca cp Fe
2+
/Fe l:

2
Fe
Fe
E
+
=
2
o
Fe
Fe
E
+
+
2
Fe
Fe
C 0, 059
lg
2 C
+

hoc
2
Fe
Fe
E
+
= 0,441 +
6
0, 059
lg10
2

= 0,618 V
3.4 Phn loi in cc
Trong in ha c nhiu cch phn loi in cc v c th chia thnh mt s loi chnh
nh sau:

3.4.1 in cc loi 1
7
in cc loi 1 l in cc lm vic thun nghch vi cation. a s cc in cc gm kim
loi nhng vo dung dch mui ca n u thuc in cc loi 1 v c th vit dng tng
qut sau:
Me
n+
/Me vi phn ng in cc:
Me
n+
+ ne Me (3.9)
Phng trnh Nernst c dng:

n
Me
Me
E
+
=
n
o
Me
Me
E
+
+
n
Me
Me
a 0,059
lg
Z a
+
25
o
C (3.10)
V d 1: Zn
2+
/Zn hoc (ZnSO
4
/Zn) vi phn ng in cc:
Zn
2+
+ 2e Zn
25
o
C ta c:
2
Zn
Zn
E
+
=
2
o
Zn
Zn
E
+
+
2
Zn
Zn
a 0,059
lg
2 a
+


2
Zn
Zn
E
+
= 0,76 +
2
Zn
0, 059
lg a
2
+
V d 2: Cu
2+
/Cu hoc (CuSO
4
/Cu) vi phn ng in cc:
Cu
2+
+ 2e Cu
25
o
C ta c:
2
Cu
Cu
E
+
=
2
o
Cu
Cu
E
+
+
2
Cu
Cu
a 0,059
lg
2 a
+


2
Cu
Cu
E
+
= 0,34 +
2
Cu
0,059
lg a
2
+

V d 3: Fe
2+
/Fe hoc (FeSO
4
/Fe) vi phn ng in cc:
Fe
2+
+ 2e Fe
25
o
C ta c:
2
Fe
Fe
E
+
=
2
o
Fe
Fe
E
+
+
2
Fe
Fe
a 0, 059
lg
2 a
+


2
Fe
Fe
E
+
= 0,441 +
2
Fe
0,059
lg a
2
+

Cc in cc kim loi trong hn hng tip xc vi dung dch mui ca n cng thuc vo
in cc loi 1.
3.4.2 in cc loi 2
in cc loi 2 l in cc lm vic thun nghch vi anion. Thng thng in cc loi
ny gm kim loi nhng vo dung dch mui t tan ca n.
V d: in cc bc Cl

/ AgCl / Ag c phn ng in cc l:
Ag
+
+ e Ag hoc AgCl + e Ag + Cl

Ta thy rng nng Ag
+
rt nh v mui AgCl rt t tan v bng:
8

Ag
C =
AgCl
Cl
T
C


trong T
Ag
l tch s tan ca mui AgCl, phng trnh Nernst i vi in cc bc
25
o
C l:

AgCl
Ag
E =
o
AgCl
Ag
E +
Ag
0, 059
lgC
1
+


AgCl
Ag
E =
o
AgCl
Ag
E +
AgCl
0, 059
lg T
1
0,059
Cl
lgC

(3.11)
trong :
o
AgCl
Ag
E =
o
Ag
Ag
E
+
+
AgCl
0,059
lg T
1

hoc
AgCl
Ag
E = 0,2224 V NHE khi
Cl
C

= 1M
Vy
AgCl
Ag
E = 0,2224 0,059
Cl
lgC


Gi tr th in cc bc ph thuc vo nng ion Cl

(bng 3.1).
Bng 3.1 Gi tr th in cc bc ph thuc vo nng ion Cl

25
o
C
in cc Gi tr th (V) v NHE
1,00N KCl, AgCl/Ag 0,2384
0,10N KCl, AgCl/Ag 0,2900
0,10N HCl, AgCl/Ag 0,2890
Trng hp tng qut i vi in cc loi 2 l: X

, Me
x
X
y
/Me, trong X

l halogen,
phng trnh Nernst 25
o
C l:

x y
Me X
Me
E =
x y
o
Me X
Me
E
y
X
0,059
lg a
y

(3.12)
V d 2: in cc calomen, in cc ny c s Cl

, Hg
2
Cl
2
/Hg.
Phn ng in cc: Hg
2
Cl
2
+ 2e 2Hg + 2Cl

p dng cng thc 3.12, gi tr th in cc calomen c xc nh theo phng trnh:

2 2
Hg Cl
Hg
E =
2 2
o
Hg Cl
Hg
E
Cl
0,059lgC

(3.13)
hoc
2 2
Hg Cl
Hg
E = 0,2768
Cl
0, 059lgC


Gi tr th in cc calomen thay i theo hot ion Cl

v ph thuc nhit .
Bng 3.2. S ph thuc ca gi tr th in cc calomen
vo nng ion Cl

v nhit
9
Nng dung dch KCl Gi tr th in cc trong khong 0
o
100
o
C
0,1N 2 2
Hg Cl
Hg
E = 0,336 7.10
5
(t 25
o
C)
1,0N 2 2
Hg Cl
Hg
E = 0,2801 2.10
4
(t 25
o
C)
Bo ha 2 2
Hg Cl
Hg
E = 0,2412 7.10
5
(t 25
o
C)
in cc calomen (xem hnh 3.4) cho gi tr th rt n nh, do c dng ph bin,
song v s dng thy ngn nn ngy nay c xu hng thay th in cc calomen bng in
cc bc.

6
2
3
5
1
4


2
8
1
4
7
5
3
6

Hnh 3.3
Cu to in cc bc
1. Dung dch HCl; 2. Mui AgCl;
3. Dy bc kim loi; 4. Dy dn in;
5. L b sung dung dch; 6. L xp
Hnh 3.4
S in cc calomen
1. L xp; 2. L xp; 3. Hg
2
Cl
2
;
4. Thy ngn; 5. Dy platin;
6. Dy dn in; 7. Dung dch KCl;
8. L np dung dch KCl
V d 3: in cc thy ngn sunfat, Hg
2
SO
4
/Hg.
Phn ng in cc l: Hg
2
SO
4
+ 2e 2Hg + SO
4
2
Phng trnh Nernst tnh gi tr th in cc:
2 4
Hg SO
Hg
E = 0,6156
2
4
SO
0,059
lgC
2

(3.14)


10
3.4.3 in cc kh
Thng thng cc in cc kh gm kim loi tr, v d platin c din tch rt rng hp
th kh, kh tip xc vi dung dch cht in li c cha ion ca nguyn t dng kh. Vic
nghin cu cc in cc kh hiro v oxi rt c ngha i vi vic gii thch n mn in
ha ca kim loi trong cc mi trng cht in li, chng ta s ln lt xt cc in cc kh
hiro v oxi.


H
2
H
2
1
3
2

Hnh 3.5
S in cc kh hiro
1. Platin; 2. Dung dch H
x
+

3. Cu ni
V d 1: in cc hiro (xem hnh 3.5).
S in cc hiro: H
x
+
/H
2
(Pt)
Phn ng xy ra trn in cc:
2H
+
+ 2e H
2

C th xem in cc hiro l in cc lm vic thun nghch vi cation.
Phng trnh Nernst tnh gi tr th in cc 25
o
C:



2
2H
H
E
+
=
2
o
2H
H
E
+
+
2
2
H
H
a 0,059
lg
2 P
+
(3.15)
Nu p sut ca kh hiro bng n v
2
H
P = 1 atm v
H
a
+
= 1 th ta c:
11

2
2H
H
E
+
=
2
o
2H
H
E
+
= 0,0000 V
v gi l th in cc tiu chun ca hiro.
Ngi ta dng in cc tiu chun hiro xc nh th in cc tiu chun ca cc in
cc khc. V vy ta c bng gi tr th in cc tiu chun ca cc in cc theo thang hiro
(k hiu l NHE hoc SHE), khi
2
H
P = 1 atm phng trnh 3.15 c dng:

2
2H
H
E
+
= 0,059pH (3.16)
hoc t rH = lg
2
H
P ta c:

2
2H
H
E
+
= 0,059 + 0,0295rH (3.17)
in cc ny cng knh, d b ng c lm sai lch gi tr th in cc. Ngy nay ngi
ta c th thay n bng in cc calomen, do c thang th calomen (SCE) hoc thay bng
in cc bc v ta cng c thang chun theo in cc bc.
V d 2: in cc kh oxi
Cu to in cc oxi: OH

/ O
2
(Pt)
Khc vi in cc hiro, in cc oxi l in cc khng thun nghch v oxi c th phn
ng vi kim loi b hp ph.
Phn ng in cc trong mi trng kim:
O
2
+ 4e + 2H
2
O 4OH

(3.18)

2
o
O
OH
E

= 0,401 V (NHE)
Trong mi trng axit:
O
2
+ 4e + 4H
+
2H
2
O (3.19)

2
2
o
O
H O
E = 1,229 V (NHE)
V mt ng hc cc phn ng trn u c xem l thun nghch, do th cn bng
ca chng ng vi cc gi tr sau:
i vi phn ng (3.18):

2
o
O
OH
E

= 0,401 + 0,059 lg
2
1/ 4
O
OH
P
a

(3.20)
i vi phn ng (3.19):

2
2
o
O
H O
E = 1,229 + 0,059
( )
1/ 4
2
O
H
lg a .P
+
(3.21)
12
Hai phng trnh (3.20) v (3.21) l tng ng nhau nu thay th hot OH

2
H
a =
W
H
K
a
+
=
14
H
10
a
+

; nu t
2
O
lg P = rO th cc phng trnh (3.20) v (3.21) c dng:

2
2
O
H O
E = 1,229 0,059pH 0,0148rO (3.22)
3.4.4 in cc oxi ho kh (Redox)
in cc oxi ho kh l mt h in ho gm mt dy dn kim loi tr (v d Pt) tip xc
vi dung dch cha cht oxi ho kh.
V d 1: in cc oxi ho kh thun tu, trong dung dch ch c mt h oxi ho kh Fe
3+
,
Fe
2+
/Pt vi phn ng in cc:
Fe
3+
+ e Fe
2+

Phng trnh Nernst tnh th in cc:

3
2
Fe
Fe
E
+
+
=
3
2
o
Fe
Fe
E
+
+
+
3
2
Fe
Fe
a 0, 059
lg
1 a
+
+

hoc
3
2
Fe
Fe
E
+
+
= 0,771 +
3
2
Fe
Fe
a 0,059
lg
1 a
+
+
(3.23)
Trong trng hp tng qut:
Ox + Ze Red
v
Ox
Red
E =
o
Ox
Red
E +
Ox
Red
0, 059 a
lg
Z a
(3.24)
V d 2: in cc oxi ho kh hn hp. i vi trng hp ny, trong dung dch ngoi
cc cht oxi ha v kh cn c cc cht ng vai tr l mi trng phn ng, v d H
+
hoc
OH

.
V d: in cc MnO
4

, Mn
2+
, H
+
/Pt
Phn ng in cc:
MnO
4

+ 5e + 8H
+
Mn
2+
+ 4H
2
O (3.25)
Phng trnh Nernst tnh th in cc 25
o
C :

4
2
MnO ,H
Mn
E
+
+
=
4
2
o
MnO ,H
Mn
E
+
+
+
4
2
2
8
MnO H
4
H O
Mn
a .a
0,059
lg
5
a .a
+
+

hoc
4
2
MnO ,H
Mn
E
+
+
= 1,507 0,0945pH +
4
2
2
MnO
4
H O
Mn
a
0,0118lg
a .a

+

3.4.5 in cc oxit kim loi
in cc oxit kim loi c cng thc Me
x
O
y
/Me, OH

.
13
Phn ng in cc:
Me
x
O
y
+ yH
2
O +2ye xMe + 2yOH

(3.26)
Loi in cc ny thng xy ra trong qu trnh to mng th ng kim loi.
V d 1: in cc oxit antimon c cng thc: Sb
2
O
3
/Sb, OH

trn b mt c ph lp
Sb
2
O
3
hoc lp Sb(OH)
3
.
Phn ng in cc:
Sb
2
O
3
+ 6e + 3H
2
O 2Sb + 6OH

Phng trnh Nernst tnh th in cc ca in cc ny 25
o
C l:

2 3
Sb O
Sb,OH
E

=
2 3
o
Sb O
Sb,OH
E

OH
0,059lg a

(3.27)
i vi mi trng axit in cc ny c cu to: Sb
2
O
3
, H
+
/Sb hoc Sb(OH)
3
, H
+
/Sb vi
phn ng in cc:
Sb
2
O
3
+ 6e + 6H
+
2Sb + 3H
2
O
Phng trnh Nernst tnh th in cc ca in cc ny 25
o
C:

2 3
Sb O .H
Sb
E
+
=
2 3
o
Sb O .H
Sb
E
+

2 3
2
6
Sb O
H
2 3
Sb H O
a .a
0, 059
lg
6 a .a
+

Nu chp nhn
2 3
Sb O
a = 1,
Sb
a = 1 v
2
H O
a = 1 th ta c:

2 3
Sb O .H
Sb
E
+
=
2 3
o
Sb O .H
Sb
E
+
0,059pH (3.28)
V d 2: in cc oxit thu ngn, cu to ca in cc: HgO/Hg, OH

.
Phn ng in cc:
HgO + 2e + H
2
O Hg + 2OH

hoc HgO + 2e + 2H
+
Hg + H
2
O
Phng trnh gi tr th in cc 25
o
C:

HgO
Hg,OH
E

=
o
HgO
Hg,OH
E

+
HgO
2
Hg
OH
a 0,059
lg
2
a .a


Nu
HgO
a = 1, a
Hg
= 1 th ta c:

HgO
Hg,OH
E

=
o
HgO
Hg,OH
E

0,059
OH
lg a

(3.29)
C th dng in cc ny lm in cc so snh nu mi trng c pH > 7, cn trong mi
trng axit th oxit thu ngn b ho tan.



14
3.5 S dng gi tr th in cc tiu chun xt chiu hng phn ng
Bng gi tr th in cc tiu chun c gii thiu trong phn ph lc bao gm cc gi
tr th in cc tiu chun khc nhau v chng c xp theo chiu tng gi tr th in cc,
s dch chuyn t gi tr m nht n gi tr dng nht (t 3,02 V 3,06 V).
Cp oxi ho kh c th tiu chun cng m th cht kh ca cp cng d dng nhng
in t v kh nng nhn in t ca cht oxi ho cng km.
Hy xt chiu hng ca phn ng oxi ho kh xy ra khi trn 2 cp oxi ho kh vo
nhau. V d xt hai cp oxi ho kh Ce4+/Ce3+ v Fe3+/Fe2+ ng vi cc gi tr th tiu
chun 1,61 V v 0,77 V. Phn ng ring ca cc cp l:
Ce
4+
+ e Ce
3+

T th cn bng ca n 25
o
C bng:

4
3
Ce
Ce
E
+
+
= 1,61 +
4
3
Ce
Ce
a
0,059lg
a
+
+
(3.30)
v Fe
3+
+ e Fe
2+

Vi th cn bng 25
o
C bng:

3
2
Fe
Fe
E
+
+
= 0,77 +
3
2
Fe
Fe
a
0,059lg
a
+
+
(3.31)
Sau khi trn hai h oxi ho kh trn vo nhau v phn ng t trng thi cn bng nu
cc phng trnh (3.30) v (3.31) bng nhau:
1,61 +
4
3
Ce
Ce
a
0,059lg
a
+
+
= 0,77 +
3
2
Fe
Fe
a
0, 059lg
a
+
+

v Ce
4+
+ Fe
2+
Ce
3+
+ Fe
3+
vi K
cb
=
3 3
4 2
Ce Fe
Ce Fe
a .a
a .a
+ +
+ +
= 10
14

K
cb
rt ln, ngha l phn ng xy ra vi nng cht to thnh
3
Ce
C
+
v
3
Fe
C
+
rt ln.
Vy phn ng xy ra theo hng oxi ho ion Fe
2+
thnh Fe
3+
v kh ion Ce
4+
thnh ion Ce
3+
.
Ta cng c th ly v d khc xt chiu hng phn ng xy ra khi cho kim loi hot
ng phn ng vi dung dch mui y kim loi km hot ng ra khi mui. V d nhng
kim loi st vo dung dch CuSO
4
. Cc phn ng xy ra 25
o
C:
Fe
2+
+ 2e Fe

2
Fe
Fe
E
+
= 0,4402 +
2
Fe
0,059
lg a
2
+
(3.32)
Cu
2+
+ 2e Cu

2
Cu
Cu
E
+
= 0,3370 +
2
Cu
0,059
lg a
2
+
(3.33)
15
Ti trng thi cn bng:
Fe + Cu
2+
Fe
2+
+ Cu
v cc phng trnh (3.32) v (3.33) bng nhau ta c:
0,4402 +
2
Fe
0,059
lg a
2
+
= 0,3370 +
2
Cu
0,059
lg a
2
+

vi K
cb
=
2
2
Fe
Cu
a
a
+
+
= 10
26

Hng s cn bng rt ln, vy phn ng xy ra theo chiu kim loi st chuyn thnh ion
Fe
2+
v ion Cu
2+
chuyn thnh ng kim loi mt cc hon ton, ngha l nu hot ca ion
Fe
2+
= 1 th hot ca ion Cu
2+
= 10
26
, khi trong dung dch nng ion Cu
2+
rt nh.
Tt c nhng nguyn t dng kh trong dy th oxi ha kh c in th m hn th
in cc tiu chun hiro u khng bn nhit ng hc khi tip xc vi nc.
V d 1 : Kim loi Na trong cp oxi ha kh Na
+
/Na c
o
Na
Na
E
+

= 2,71 V, khi
cho vo nc s phn hy nc gii phng hiro:
Na + HOH = Na
+
+ OH

+
1
2
H
2

V d 2: Cho Ti
2+
trong cp oxi ha kh Ti
3+
/Ti
2+
vi
3
2
o
Ti
Ti
E
+
+
= 0,37 V, khi
cho vo nc s phn hy nc gii phng hiro:
Ti
2+
+ HOH = Ti
3+
+OH

+
1
2
H
2

Tt c nhng in cc c th in cc tiu chun m hn so vi th in cc oxi u
khng bn nhit ng hc khi chng tip xc vi oxi v nc, dn n chng s d dng kh
oxi, v d kim loi st tc dng vi oxi trong khng kh theo phn ng:
Fe +
1
2
O
2
+ H
2
O = Fe
2+
+ 2OH

(
2
o
Fe
Fe
E
+
= 0,44 V)
hoc Cu +
1
2
O
2
+ H
2
O = Cu
2+
+ 2OH

(
2
o
Cu
Cu
E
+
= 0,34 V)
Trong trng hp vi nhng cp oxi ha kh c th in cc tiu chun dng hn th
in cc tiu chun ca oxi (
2
2
o
O
H O
E = 1,229 V), trng thi cn bng chng khng bn v
mt nhit ng hc v lm phn hy nc gii phng oxi. V d trong dung dch cha ion
Ce
4+
(
4
3
o
Ce
Ce
E
+
+
= 1,61 V) d dng chuyn thnh ion Ce
3+
v gii phng hiro theo phn ng:
Ce
4+
+
1
2
H
2
O = Ce
3+
+ H
+
+
1
4
O
2

nh gi bn nhit ng hc ca cc in cc trong dung dch nc ngi ta dng
gin th - pH (xem phn tip theo) ca Poubaix.
16
Da vo cc gi tr th in cc tiu chun bit tnh gin tip th in cc tiu
chun ca mt cp oxi ha kh kh xc nh.
V d: Tnh
3
o
Fe
Fe
E
+
khi bit
2
o
Fe
Fe
E
+
= 0,44 V v
3
2
o
Fe
Fe
E
+
+
= 0,77 V. tnh c gi tr
th tiu chun ca cp Fe
3+
/Fe ta lp chu trnh sau:

Fe Fe
3+
G
o
3

3e
Fe
2+
2e 1e
G
o
1
G
o
2

Da vo chu trnh trn ta c:

o
3
G =
o
2
G +
o
1
G


v suy ra:

o
3
3FE

=
o
2
2FE +
o
1
FE

o
3
3E

=
o
2
2E +
o
1
E
Vy

o
3
E =
3
o
Fe
Fe
E
+
=
o o
2 1
2E E
3
+

hoc
3
o
Fe
Fe
E
+
=
2 3
2
o o
Fe Fe
Fe
Fe
2E E
3
+ +
+
+
= 0,036 V
3.6 Pin in (Pin Ganvani hoc mch in ha)
3.6.1 Pin in v cc phn ng xy ra trong pin
Mch in ha l mt h in ha gm t nht 2 in cc ghp li. Vic nghin cu v
pin in rt c ngha khoa hc trong vic gii thch n mn in ha.
Khi m t mt pin in c quy c nh sau:
Cc in cc c xp thnh mt hng, gia cc mt tip xc c quy c: mt gch
thng ng l gii hn gia pha rn v pha lng, hai gch thng l mt gii hn pha gia hai
cht lng tip xc (hoc l cu ni ca hai dung dch cht in li).
in cc t bn tri l cc m c gi l anot, in cc t bn phi l in cc
dng c gi l catot.
V d: Ghp hai in cc CuSO
4
/Cu v ZnSO
4
/Zn thnh pin in:
() Zn|ZnSO
4
Cu|CuSO
4
(+)
17

Hnh 3.6
S pin in Danien - Jacobi (pin ng km)
1. Dung dch ZnSO
4
; 1. Dung dch CuSO
4
; 2,2. Km v ng kim loi;
3. Cu ni 2 dung dch (cu aga); 4. Ampe k
Khi khp kn mch bng dy dn loi 1 (dy ng) pin s hot ng v c ch th qua
ng h ampe, trn hai in cc xy ra cc phn ng sau:
Trn anot (): Zn 2e Zn
2+
;
2
o
Zn
Zn
E
+
= 0,76 V
Trn catot (+): Cu
2+
+ 2e Cu ;
2
o
Cu
Cu
E
+
= + 0,34 V
Phn ng chung ta c: Zn + Cu
2+
Zn
2+
+ Cu (3.34)
3.6.2 Sc in ng ca pin in
Bin thin th ng nhit ng p ca phn ng (3.34) v cng in ca pin Danien -
Jacobi c quan h vi nhau theo phng trnh:
G = A
Max
= ZF (3.35)
trong : A
Max
l cng cc i hu ch; sc n ng ca pin in; F hng
s Faraday (96493 C); Z s electron trao i.
Theo quy c, sc in ng ca pin in c tnh theo cng thc sau:
= E
+
E

(3.36)
trong : E
+
th in cc dng; E

th in cc m.
T phng trnh 3.34, da vo bin thin ho th c quan h vi sc in ng ca pin
in rt ra c cng thc tnh sc in ng ph thuc vo nng cc cht phn ng xy
ra trong pin.
Vy:
=
o
+
2
2
Zn
Cu
Cu
Zn
a .a RT
lg
ZF a .a
+
+
(3.37)
18
Phn ng 25
o
C th ta c:
=
o
+
2
2
Zn
Cu
Cu
Zn
a .a 0,059
lg
Z a .a
+
+

Vi phn ng tng qut xy ra trong pin l:

2
Red
2
+
1
Ox
1

2
Ox
2
+

1
Red
1

Vy =
o
+
2 1
2 1
' '
1 2
2 1
Red Ox
Ox Red
a .a
RT
lg
ZF
a .a


(3.38)
Vi iu kin th in cc tiu chun
1
1
o
Ox
Red
E >
2
2
o
Ox
Red
E , khi hot cc cht phn
ng bng n v (
1
Ox
a ,
2
Ox
a ,
1
Red
a ,
2
Red
a = 1) th sc in ng ca pin bng sc in ng
tiu chun
o
. i vi pin Danien - Jacobi sc in ng tiu chun bng:

o
=
2
o
Cu
Cu
E
+

2
o
Zn
Zn
E
+
= 0,337 ( 0,76) = 1,097 V
Nu a
Cu
= a
Zn
= 1 ; phng trnh (3.37) c dng:
= 1,097 +
2
2
Cu
Zn
a 0,059
lg
2 a
+
+
(3.39)
Vy sc in ng ca pin in ph thuc vo hai gi tr l sc in ng tiu chun v
nng cc cht tham gia phn ng.
3.6.3 Phn loi pin in
Pin in c nhiu loi, song c th chia lm hai nhm chnh sau y:
1. Pin ho hc
Pin ho hc l mt h in ho gm hai in cc c tnh cht ho hc khc nhau ghp li,
n c phn chia thnh nhiu loi
a) Pin ho hc n gin
Pin ho hc n gin l h in ho gm hai in cc khc nhau nhng c chung cht
in li ghp li.
V d 1: Pin hiro v oxi, pin ny c s Pt, H
2
/H
2
O/Pt, O
2
.
Phn ng chung xy ra trong pin l:
H
2
+
1
2
O
2
+ H
2
O 2H
+
+ 2OH

(3.40)
Gi tr
sc
in ng 25
o
C l:
=
o
0,059lgK +
2 2
1/ 2
H O
0, 059
lg P .P
2

=
o
0,059lg10
14
+
2 2
1/ 2
H O
0,059
lg P .P
2

19
=
o
+
2 2
1/ 2
H O
0,0295lg P .P (3.41)
V d 2: Pin tiu chun Weston
S pin: () Hg(25% Cd) / CdSO
4
(dd) / HgSO
4
/ Hg (+)
Trong pin dung dch CdSO
4
c dng chung cho c hai in cc, cc m l in cc
loi 1, cc dng l in cc loi 2, phn ng xy ra trong pin l:
Cd + HgSO
4
Cd
2+
+2Hg + SO
4
2

Gi tr sc in ng:
=
o

2 2
4
Cd SO
RT
lg a .a
2F
+

=
o

4
CdSO
RT
lg a
F

(3.42)
Vi dung dch CdSO
4
bo ho, gi tr s ca pin bng 1,018 V, gi tr ny rt n nh v
ph thuc vo nhit :
= 1,018 4.10
5
(t 20
o
C) V
Cc cquy axit, cquy kim c xp vo loi pin ha hc n gin.
b) Pin ho hc phc tp
Pin ho hc phc tp l mt h in ho gm hai in cc loi 1 khc nhau ghp li. V
d Pin Danien - Jacobi.
S pin: () Zn / ZnSO
4
// CuSO
4
/ Cu (+)
Khp kn mch xy ra phn ng tng cng:
Cu
2+
+ Zn Cu + Zn
2+
(3.43)
Trong n mn in ho thng tn ti loi pin ny khi c hai kim loi tip xc vi nhau
c t trong mi trng cht in li (s nghin cu phn sau).
i vi pin Pin Danien - Jacobi sc in ng c tnh:
=
o
+
0, 0591
2
lg
2
2
C u
Z n
a
a
+
+

= 1,1 +
0, 0591
2
lg
2
2
C u
Z n
a
a
+
+

Khi pin nm trng thi cn bng th hng s cn bng K
cb
ca phn ng c tnh:
1,1 =
0,0591
2
lgK
cb
Suy ra: K
cb
= 10
37
ngha l khi
2
Zn
a
+
= 1 th
2
Cu
a
+

= 10
37
, khi nng ion Cu
2+
rt
nh v km hon ton b n mn, qu trnh ho tan km y xy ra mt cch t din bin.
2. Pin nng
20
Pin nng l mt h in ho gm cc in cc ghp li to ra pin in, song nng
cht dn in loi 2 hoc cht dn in loi 1 khc nhau.
Loi pin ny tn ti trong cc loi n mn in ho, v d s n mn in ho do s
chnh lch nng oxi (n mn khe, n mn l).
Sau y l mt s v d:
V d 1: Pin nng
() Ag / AgNO
3
// AgNO
3
/ Ag (+)
a
1
a
2

Gi thit a
1(
AgNO
3
)
< a
2(AgNO
3
)
.
Ti anot xy ra phn ng:
() Ag 1e Ag
+
(a
1)

(+) Ag
+
(a
2
)

+ 1e Ag
Ag
+
(a
2
) Ag
+
(a
1
)
Qu trnh pin hot ng gn lin vi s gim hot Ag
+
ti khu catot v tng hot
Ag
+
ti vng anot. Pin khng hot ng khi hot Ag
+
ti

hai vng catot v anot bng nhau.
Sc in ng: =
RT
F
lg
2
1
a
a
v 25
o
C.
= 0,0591lg
2
1
a
a

Khi nng
2
1
a
a
= 10 th sc in ng E = 0,0591 (V).
V d 2: Pin nng oxi
Trong n mn in ho ho tan kim loi th oxi ng vai tr l cht nhn in t. Song s
c mt ca oxi ti cc vng khc nhau to ra cc in cc oxi c nng oxi khc nhau. Khi
khp kn to thnh pin nng oxi v lm tng tc n mn (xem chi tit trong phn n
mn kim loi trong iu kin c mt nng oxi khc nhau).
3.7 Phng php o sc in ng v ng dng
o sc in ng ca mt pin in cho php suy ra th in cc ca kim loi b n mn
trong mi trng cht in li. Trong mc nht nh, vic so snh th in cc n nh ca
kim loi trong mi trng n mn cho php suy on bn vng chng n mn ca vt liu.
V vy, vic o chnh xc gi tr th in cc c ngha nht nh.
o chnh xc sc in ng ca pin in ngi ta dng phng php b chnh. S
cu b chnh o sc in ng ca pin in c trnh by trn hnh 3.7 v trong :
iu kin o:
cquy
>
x
.


Nguyn tc o v tnh
x
: Di chuyn con chy K trn in tr AB sao cho khng c dng
i qua pin
x
v in k G ch s khng. Khi cu cn bng v ta c:
21

cquy
AB

x
AK
Vy:
acquy
E

=
AB
AK


Hnh 3.7
S cu b chnh o sc in ng pin in

cquy
: Sc in ng cquy; AB: Dy in tr u;
x
: Sc in ng pin o;

w
: Sc in ng pin chun; G: in k; K: Con chy tip xc;
K: Con chy tip xc; O: Tip xc ng ngt in
Rt ra:

x
=
cquy
.
AB
AK
(a)
V gi tr in ng
cquy
khng hon ton chnh xc nn phi chnh li gi tr
cquy
bng
pin chun Weston c gi tr
w
= 1,018 V. Gi tr ny khng thay i theo v tr song c thay
i theo nhit v kh nng phc hi ca pin ny rt nhanh.
Tng t trng hp xc nh, thay
x
bng
w
(xem hnh 3.7) v m tip xc O, ta li di
chuyn con chy K, tm v tr ng vi in k G ch s khng v d im K, ta c:

cquy
AB ;
w
= AK.
Ta c:
cquy
=
w
.
AB
AK
.
AB
AK'
(b)
Kt hp hai cng thc (a) v (b) ta c:

x
=
w
.
AB
AK'
.
AB
AK
= 1,018.
AK
AK'
(V)
Vy ta ch cn xc nh AK v AK l o c sc in ng E ca pin in. Ch : c
th thay dy in tr u AB bng cc hp in tr.
22
Ngy nay php o sc in ng ca pin in c ng dng rt rng ri trong vic ch
to cc thit b o: o pH, o th in cc, chun in th ca phng php in ho... Sau
y l mt s v d ng dng php o sc in ng ca pin in.
Nh bit, thng qua vic o nhit lng k xc nh c hiu ng nhit phn ng,
hoc nng lng G. Mt khc c th o sc in ng pin in tnh cc hm nhit ng.
Ta xt phn ng xy ra trong pin in Danien - Jacobi:
Cu
2+
+ Zn Cu + Zn
2+
(c)
tnh G phn ng ny bng cch o sc in ng ca pin Danien - Jacobi:
Ch to pin in theo hnh (3.6).
o sc in ng pin in 25
o
C thu c gi tr o .
Vy: G = 2F
o
= 2 96493.
o
(3.44)
tnh H ca phn ng (c) ta p dng:
G = H TS (3.45)
V:
p
G
T

= S hoc 2F
p
T

= S (3.46)
Vy: G = H T2F
p
T

(3.47)
hoc: 2F
o
= H T2F
p
T

v
o
=
H
2F

+ T
p
T

(3.48)
tnh H ca phn ng theo (3.48) trc ht phi xc nh h s nhit ca sc in
ng
p
T

bng cch o sc in ng ph thuc nhit v t cc s liu th nghim suy
ra
p
T

.
Phng trnh (3.48) cn c dng:

o
=
p
Q
2F




+ T
p
T

(3.49)
trong
p
Q gi l nhit phn ng. Phng trnh (3.49) cho bit quan h gia sc in
ng v nhit phn ng.
23
Nu
p
T

= 0 th ton b nhit phn ng chuyn thnh cng in v
p
T

< 0 th ch
c mt phn nhit phn ng chuyn thnh cng in, trong mt phn chuyn cho mi
trng. Vy khi pin lm vic th mi trng xung quanh nng ln.
Nu
p
T

> 0 th cng in thu c ln hn nhit phn ng chuyn thnh cng.
sinh cng in, pin lm vic thu nhit ca mi trng, v th khi pin lm vic mi trng s b
gim nhit .
Mt v d khc, o sc in ng pin in tnh pH
x
ca mi trng.
Mun o sc in ng tnh pH
x
ca mi trng ta phi chn hai in cc to ra pin:
+ 1 in cc so snh (in cc bc hoc Calomen)
+ 1 in cc ch th H
x
+

(in cc hiro hoc in cc thu tinh, in cc oxi ho kh
quinon v hiroquinon). y ta chn in cc hiro 2H
x
+
/ H
2
(Pt), vi
2
H
P

= 1 atm.
Ghp cc in cc to thnh pin in 25
o
C:
() (Pt) H
2
/ 2H
x
+
/ Cl

, AgCl / Ag
+
(+)
o sc in ng ca pin ny ta c
o
v theo quy c ta c:

o
= E
(+)
E
()

hoc
o
= 0,2222 V ( 0,0591pH
x
)
Vy: pH
x
=
o
0, 2222
0, 0591

(3.50)
(Trong th in cc bc chn bng 0,2222 V).