Cu|Cu2+||Ag+|Ag

Zn +Cu+2 Zn 2 Cu

m
Zn Zn 2 2e
Cu 2 2e Cu

co

n.
Zn Zn 2 2e

io
Cu 2 2e Cu

IUPAC

at


uc


ed

Cu|Cu2+||Ag+|Ag

Cu |Cu2+ ||Ag+ |Ag
hi

Cu|Cu2+||Ag+|Ag
ks

Cu Cu 2 2e
2 Ag 2e 2 Ag

a

Cu 2 Ag Cu 2 2 Ag
.s

1M HCl250CH2
w

32
 M n ne M



RT
E E0 ln M n
nF

M n ne M

m
RT
E M n / M E 0M n / M ln M n
nF

co
E H / H 2

n.
E0 H / H 2
E H / H 2

io

at
E0 H / H 2
EMF
uc
Ni |Ni2+ ||Ag+ |Ag

ed

Ni|Ni2+||Ag+|Ag
hi
ks

2
RT Mg
E E ln
2F Ag 2
a

.s

w
w
w

Mg|Mg2+||Ag+|Ag
Mg Mg 2 2e
2 Ag 2e 2 Ag

Mg 2 Ag Mg 2 2 Ag

33
 KC E0
KCE0
2.303 RT
E0 log K C
nF
n=
F== 96500 C mol-1
T=
emf(E0) (G)
emf(E0)(G)

m
G0 nE 0 E (
G 0

co
n
F

n.
S.I
(k)

io

at
SI ohm 1m 1 or Sm 1 S
uc

lA
ed

l

A
hi

0 l
G R k
ks

A

a

m k
.s

m
w

m k
w

k
m ;c
w

c
c m
c m

34
 m

0m AB 0A 0B

0m

m
0A

co
0B

n.

io
Ect
m Q; m c t m ect ; m
96,500

at
e
t
uc
c
E
ed

hi

m1 E1

ks

m2 E2
Q# ^ Hi yOz # NaCl
a

NaCl
.s

2 NaCl 2 Na 2Cl
w

2Cl Cl2 2e
2 Na 2e 2 Na
w

K2SO4

K2SO4

K 2 SO4 2 K SO42
4e
4 H 2O 2 H 2 4OH

35
 4 e
2 H 2O O2 4 H
H 2O
H 2O
2H 2O O 4H 4e
2
H 2O

H 2O

H 2O e H 2 OH

m
2

co

n.

io
Pb SO 2 PbSO
2e

at
4 4
PbO2 SO 2
4 4H 2e PbSO4 2H 2O

uc
Pb PbO2 2H SO 2PbSO4 2H O
2 4 2

ed

CdO 2 Ni OH 3
CdO 2Ni OH 2 H 2O
hi

ks

.s

H 2 , O2
O2 2 H 2O 4e 4OH
w

2 H 2 4OH 4 H 2O 4e
w

2 H 2 O2 2H 2O
w

Fe2O3
Ag 2 S

36

2 Fe 2 Fe 2 4e E 0Fe2 / Fe 0.44V

O2 4 H 4e 2 H 2O EH / O / H 2O
1.23V
2

2 Fe O2 4 H 2 Feaq2 2 H 2O E 1.67 V

co

n.
ZnSO4 Zn
CuSO4 Cu

io

at
Zn / ZnSO4
Zn Zn 2 2e
uc
Cu / CuSO4
Cu 2 2e Cu
ed

Zn Cu 2 Zn 2 Cu
hi

ks

Zn | Zn 2 || Cu 2 | Cu
a
.s
w
w
w

37


Pt / H 2 / H

1
H 2 H 1m e
2

1 barH2
emf 298K

m
co
n.
io
at
uc
ed
hi

M n ne M Mn+
ks

RT
E E0 ln M n
nF
.s

M n ne M

w

RT
E M n / M E 0M n / M ln M n
w

nF
E M n / M

R 8.314 J / K mole
F 96487 c / mole
T
M n M n

38
 RT
E E0 ln C , C
nF

Ni 2 / Ni
0 RF 2
E E nF ln Ni

Pt , Cl2 / Cl
RT
E E0 ln C
nF

m
RT
E E0 ln Cl
F

co

n.

io

at
emfEnF, r G
uc
r G = -nFE
E r G n
ed

Zn Cu 2 Zn 2 Cu
r G = -2FE
hi

2Zn 2Cu 2 Zn 2 2Cu r G = -4FE

ks

E r G r G K C

a

r G RT ln K c
.s

i
w

ii
iii
w

iv
v




iDC

ii
39
 AC

m
co
n.

io
l
R
k A

at
l ; A ; k
l
uc
G *
A

G Al R k
ed
*

hi

ks

R1 R4
R2 R3
a

k G * R
.s

unit length

40
 m
co
n.
io
kA
G
l

at
A
V
uc
kA
m k
l
ed

l 1, A V
m kV
hi

V
ks

0m
a

m
.s

KCl
w

KCl
K+

m Q; m c t
Ect
m ect ; m
96,500

41
 e= t=
c= E=

m
co
n.
io
at
KCl
uc

2 KCl 2 K 2Cl
ed

2Cl Cl2 2e
2 K 2e 2 K
hi

ks

(Z) Q# KCl CuSO4 K2SO4

KCl
a

2 KCl 2 K 2Cl
.s

2Cl Cl2 2e
w

2 K 2e 2 K
w

CuSO4O2

w

2 CuSO4 2Cu 2 2SO42

2Cu 2 4e 2Cu
2 H 2O 4e O2 4 H

K 2 SO4

K 2 SO4 2 K SO42

4 e
4 H 2O 2 H 2 4OH
42

4e
2 H 2O O2 4 H






Pb SO42 PbSO4 2e
PbO2 SO42 4 H 2e PbSO4 2 H 2O

m
Pb PbO2 2H 2 SO4 2PbSO4 2H 2O
H2,O2

co

n.

io

H2,O2

at
NaOHH2,O2

uc


O2 2 H 2O
4 e
4OH
ed

2 H 2 2OH 2 H 2O
2 e

hi

2 H 2 O2 2 H 2O

ks

.s

2 Fe g 2 Fe 2 4e E 0Fe2 / Fe 0.44V

w

O2 4 H 4e 2 H 2O EH / O 1.23V
w

2 / H 2O

2 Fe O2 4 H 2 Fe 2 2 H 2O E 1.67V
w

43


m
ZnSO4 Zn
CuSO4 Cu

co

Zn / ZnSO4

n.
Zn Zn 2 2e
Cu / CuSO4

io
Cu 2 2e Cu

at

Zn Cu 2 Zn 2 Cu
uc

Zn | Zn 2 || Cu 2 | Cu
ed

hi

ks

Cu | Cu 2 || Ag 2 | Ag

a

.s

Pb SO42 PbSO4 2e
w

PbO2 SO42 4 H 2e PbSO4 2 H 2O

w

Pb PbO2 2H 2 SO4 2PbSO4 2H 2O

44
 m
co
n.

io

k

at


uc
SI ohm 1m 1 or Sm 1 S

ed

hi

iDC

ks

ii
AC
a

.s
w
w
w

45
 l
R
k A
l ; A ; k
l
G *
A

G Al R k
*

m

R1 R4
R2

co
R3

k G * R

n.
io
at
uc
ed
hi
a ks
.s

0m AB 0A 0B
w

0m
0A

0B

46




(extrapolation)

HCl , NaCl , CH 3 COONa

CH 3COONa 0 CH 3COO Na 1

m

Hcl 0H Cl
o
II

co

CH 3COONa Hcl NaCl Na H Cl Na Cl

n.

CH 3COO H CH 3COOH

io
m
m

at
0

ka 2 .C
uc
S
ed

BaSO4 , PbSO4 , AgCl

k 1000
S
hi

k
ks

.s

Zn Zn
Zn C MnO2
NH 4Cl ZnCl2
EMF 1.5V

MnO2 NH 4 e MnO OH NH 3
Zn 2MnO2 2 H 2O Zn 2OH 2 MnO OH

47


m
co

n.
lead storagebattery

io

at
Pb SO42 PbSO4 2e
uc
PbO2 SO42 4 H PbSO4 H 2O

ed

Pb PbO2 2 H 2 SO4 2 PbSO4 2 H 2O

hi

PbSO4 Pb, PbO2

ks

2 PbSO4 2 H 2O Pb PbO2 2 H 2 SO4

a
.s
w
w
w

48


K / K 2.93V Ag / Ag 0.80V Cu / Cu 0.34V
Mg / Mg 2.37V Cr 3 / Cr 0.74V Fe2 / Fe 0.44V

E0 K / K 2.93V Mg 2 / Mg 2.37V
Ag / Ag 0.80V Cr 3 / Cr 0.74V

m
Cu 2 / Cu 0.34V Fe 2 / Fe 0.44V

co

n.
Ag Cu Fe Cr Mg K
250 C emf

io
Cr | Cr 3 0.1M || Fe2 0.01M | Fe, ECr

3
/ Cr

0.74V EFe 2
/ Fe
0.44V

at

Cr | Cr0.13 M || Fe0.01
2
M
| Fe
uc
Cr 3 / Cr E 0 0.74V
E 0 of Fe 2 / Fe E 0 0.44V
ed

0.059 0.059
ECr 3 / Cr E 0 log10 Cr 3 0.74 log 0.1 0.76V
3 3
hi

0.059
EFe2 / Fe 0.44 log 0.01 0.44 0.059 0.499V
ks

2
emf ERHS ELHS 0.499 0.76 0.261V
a

Zn 2 0.001M Zn Zn 2
.s

EZn 2
/ Zn
0.76V
w

R 8.314 JK 1mol 1; f 96500C mol 1

w

Zn | Zn 2 0.001M , EZn
0
2
/ Zn
0.76V
w

2.303RT
E E0 log M n
nF
0.059
R 8.314 J / K mole; F 96500 c / mole, E E 0 log C
n
0.059 0.059
0.76 log 0.001 0.76 3
2 2
0.76 0.0295 3

49
 0.76 0.0885 0.8485V
G 0
Zn Ag 2O H 2O Zn 2 2 Ag 2OH

E Ag
/ Ag
0.80V ; EZn 2
/ Zn
0.76V

Ag / Ag E 0 0.80V
Zn 2 / Zn E 0 0.76V
Zn / Zn 2 || Ag / Ag
emf ERHS ELHS 0.80 0.76 1.56V

m
G nEF 0 2 96500 1.56 301.08kJ / mole

co
emf
Al / Al 3 0.001M , Ni / Ni 2 0.50M ENi 2 / Ni 0.25V

n.
E Al 3 / Al 1.66V log 8 106 5.0969

io
Al 3 / Al E 0 1.66V
Ni 2 / Ni E 0 0.25V

at
3 2
Al | Al 0.001M || Ni 0.50 M | Ni
uc

0.059
E Al 3 | Al E Al0 3 / Al log Al 3
ed
n
0.059
1.66 log 0.001 1.66 0.059 1.719V
3
hi

0.059 0.059
0
E Ni 2 / Ni ENi log Ni 2 0.25 log 0.5
ks

2
/ Ni
n 2
0.25 0.0295 0.3010 0.25 0.0088795 0.25888V
a

emf ERHS ELHS 0.25888 1.719 1.46012V

.s

K C
w

Ni 2 Ag Ni 2 2 Ag ; E 1.05V

w

Ni 2 Ag Ni 2 2 Ag E 1.05V
w

0 0.059
E E log K C
n
E 0
0.059 0.059 2.1
E log K C ,1.05 log K c , log K c K C 3.42 1035
n 2 0.059
0.1M K 2 Cr2 O7 0.2 M Cr 3 1.0 104 MH
Cr2 O72 14 H 6e 2Cr 3 7 H 2O

50
 Cr O
2
2
7 / Cr 3 E 0 1.33V

0.059
0 0 0.059 Cr 3 H 2 O
EE log Q, E E log 14
n 6 Cr2 O72 H

1.33
0.059
log
0.2 1.33
0.059
log
0.04
14
6 0.1 1104 6 0.1 1 1056

1.33 0.00983 55.6021 0.783V

m
298K K C

co
Zn Cu 2 Zn 2 Cu; EZn

2
/ Zn

0.76V ; ECu 2
/ Cu
0.34V ;
G 212.300kJ .mol 1

n.

Zn s Cuaq2 Znaq2 Cu s

io
Zn 2 Zn E 0 0.76V

at
Cu 2 / Cu E 0 0.34V
E 0 ERHS ELHS 0.34 0.76 1.1V
uc
G 0 RT ln K C 2.303RT log K C
ed

212300
212300 2.303 8.314 298 log K c , log K c 37.207
2.303 8.314 298
K C 1.6 1037
hi

298K emf
ks

Sn | Sn 2 0.05M || H 0.02 M | H 2 1atm .Pt.; ESn

0
2
/ Sn
0.144V
Sn 2 H Sn 2 H 2
a

.s

0.0591
0
Sn 2
w

EE log 2
2 H
w

EMF 0 0.144
0.0591
log
0.05
w

2
2 0.02
0.0591
0.144 2.097 0.144 0.0620 0.078V , EMF 0.078V
2
0.1M Cu 2 , Ag
Cu , Ag 0.422V
Ag / Ag E 0 0.80V
Cu 2 / Cu E 0 0.34V

51
 E 0 ERHS ELHS 0.80 0.34 0.46V
2
Cu | Cu 0.1M || Ag | Ag

0.059 Cu 2 0.059 0.1

E E0 log 2
,0.422 0.46 log 2
n
Ag 2 Ag

0.1 0.038 2 0.1

log 2
1.288, Ag 5.176 10 3
Ag 0.0295 19.32

Ag 51.76 104 7.16 102 M

m
emf

co
Ni s 2 Ag 0.002M Ni 2 0.160M 2 Ag S E 0 1.05V

n.
0.0591
0
Ni 2 0.0591 0.160
EE log 1.05V log

io
2 2
n Ag 2 0.002

at
0.0591 0.0591
1.05 log 4 104 1.05 4.6021 1.05 0.14 0.91V 0.91V
2 2
uc
Cu 2 2e Cu; E 0 0.34V
Ag e Ag ; E 0 0.80V
ed

250 C Ag emf Cu 2 0.1M
log 3.919 0.593
hi

Cu | Cu 2 || Ag | Ag
ks

emf ERHS ELHS 0.80 034 0.46V

a

0.059
0
Cu 2
E E 2 log 2 , emf 0
.s

Ag
w

0.059 0.1 0.1 0.46 2

E0 log 2
, log 2
15.5668
2 Ag Ag 0.059
w
w

0.1 2 0.1
2
3.688 1015 , Ag 15
0.0271 10 15

Ag 3.688 10

Ag 0.02711016 0.5207 108 ; Ag 0.5207 10 8 M

298K 0.20M KCl 0.0248 S cm 1

k 0.0248 S cm 1 0.0248ohm 1cm 1

52
 0.2 mol
c 0.20 mol L
1
3
2 104 mol / cm 3
1000 cm

1 1
k 0.0248ohm cm
m c 2.0 104 mol cm 3

124S mol 1cm 2
298K CH 3COOH

m

CH 3COOH
11.75 cm 2 mol 1
0
CH 40.95 cm 2 mol 1

co
COO 3

0
H
349.15cm 2 mol 1

n.


11.75 cm 2 mol 1

io
CH 3COOH

CH 40.95 cm 2 mol 1

at
COO 3

H
349.15cm 2 mol 1
uc

CH 3COOH
CH COO H 40.95 349.15 390.1
3
ed

11.75
0.03 3 102 , 3 10 2
390.1
hi
a ks
.s
w
w
w

53