)(

Fundamentals of Electrochemistry

http://uqu.edu.sa/oahazazi

oahazazi@hotmail.com

)(34

Electrochemistry

:
/ .

st

01 Chapter
Oxidation and Reduction

)(35

Electrochemistry

:
/ .

)Oxidation and Reduction (Redox reactions

)(oxidation

)(reduction

)(oxidizing agent

)(reducing agent

)(anode

)(cathode

.
)
(.
)
(.
:
)( ) .(...

.
) Pt (Au
:
( ( Cl- , I- ) :
( )(H2O

.

.

)(36

Electrochemistry

:
/ .

) )

) (anode ) )(cathode

) (.
:

)(37

Electrochemistry

:
/ .

)(-
)( )(.

) : (- ) (

" ) (salt bridge

) (U
) (KCl ) (K2SO4
) (KNO3


.

)(38

Electrochemistry

:
/ .

)
(.
) (oxidation
)) (reduction (
.

) (
)
(.

.




.


) (... ) (-
) (
.

Electrochemistry

(39)

:
./

Fig. 1.2 : Electrolysis of molten sodium chloride. Chloride ions are oxidized to
Cl2 gas at the anode, and Na+ ions are reduced to sodium metal at the cathode

( -)
.

Fig. 1.3 : A diagram showing the electrode reactions during the electrolysis of
water

)(40

Electrochemistry

:
/ .

.
.

.


.
) (
) (
.



.

:
:

)

.(..

)(41

Electrochemistry

:
/ .

: :
)
(
"".
:
.

) (Zn
) (ZnSO4
(Zn(NO3)2.

.

)(42

Electrochemistry

:
/ .

) (U




.
) (-
)( )(.

Fig. (1-1) : A galvanic cell consisting of a Zn/Zn2+ (1 M) half-cell and a

standard hydrogen electrode. Electrons flow from the zinc anode to the
S.H.E. (cathode). The measured standard cell potential at 25 C is 0.76 V.

)(43

Electrochemistry

:
/ .

:


.


.



.
:

)( )(
:
)Zn(s) Zn 2+ (aq) H + (aq) H 2 (g) Pt (s

)(44

Electrochemistry

:
/ .

) (
)(.

.

)(45

Electrochemistry

:
/ .

)(-

:

)Zn(s) Zn 2+ (aq) H + (aq) H 2 (g) Pt (s

Fig. (1-2) : The Zn(s) Zn 2+ (aq, 1 M) H + (aq, 1M); H 2 (1 atm) Pt in which the
)following net reaction occurs. Zn(s) + 2H + (aq
Zn 2+ (aq) + H 2 (g) . In this
cell the standard hydrogen electrode functions as the cathode.

)(46

Electrochemistry

:
/ .

)Zn(s) Zn 2+ (aq) H + (aq) H 2 (g) Pt (s

) (
) (
) ( )
(

Zn
Zn 2+ + 2e


) (
:
2H + + 2e
H2
:

H + + e
1/2 H 2
.

)(47

Electrochemistry

:
/ .

:
oxidation
Zn
Zn 2+ + 2e
reduction
2H + + 2e
H2

Zn + 2H +
Zn 2+ + H 2

.
)(-
:
)2Ag + (aq) + Pb(s
) 2Ag(s) + Pb 2+ (aq

:
) (Pb ) ( .
oxidation
)Pb(s
Pb 2+ (aq) + 2e

)(48

Electrochemistry

:
/ .

) (Ag+ ) (

reduction
Ag + (aq) + e
) Ag(s

)
(.




:
oxidation
Pb 2+ (aq) + 2e
)Pb(s
reduction
) Ag(s
2 x Ag + (aq) + e

)2Ag + (aq) + Pb(s

) 2Ag(s) + Pb 2+ (aq

) (
.

)(49

Electrochemistry

:
/ .

)(-
:

)3Ni(s) + 2Cr 3+ (aq

) 3Ni 2+ (aq) + 2Cr(s

)(50

Electrochemistry

:
/ .

)(-
:
)2I- (aq) + 2Fe3+ (aq
) I 2 (s) + 2Fe 2+ (aq

) (I- ) ( .
)) (Fe3+( ) (
.

)(51

Electrochemistry

:
/ .

)(-
:
)Zn(s) + Cu 2+ (aq
) Zn 2+ (aq) + Cu(s

:
:

Zn 2+ (aq) + 2e
)Zn(s
) Cu(s
Cu 2+ (aq) + 2e

-----------------------------------------------------------------------------------

= Zn
= Cu2+

)Cu 2+ (aq) + Zn(s

) Zn 2+ (aq) + Cu(s

)(52

Electrochemistry

:
/ .

) ( )(Oxidation Number

.


)( )
( .
:

S8

O2

Cl2

H2

Cu

Ag

Na

.
:

Cl-

Na+

Ca2+

Al3+

S2-

O2-

-1

+1

+2

+3

-2

-2

)(53

Electrochemistry

:
/ .

.
:

NO3-

NH +4

PO3-4

SO 2-4

-1

+1

-3

-2

)
( .
:

H2SO4

NaBrO3

NO2

H 2O

:
)) (1 A (
).(+ 1
(Rb, K, Na, Li) :

)(54

Electrochemistry

:
/ .

:
) (2 A
).(+ 2
(Mg, Ca, Sr, Ba) :

:
) (
).(- 1
(F, Cl, Br, I) :


:

)(55

Electrochemistry

:
/ .

)(

Cl2O

2X + (-2) = 0
2X - 2 = 0
2X = 2
X = +1
1 + X + 3(-2) = 0

HClO3

1+X-6=0
X=-1+6
X=+5

) (+1
) (NaH
) (CaH2 ) (-1 :

NaH

X+1=0
X =-1

CaH2

2 + 2X = 0
2X = -2
X=-1

)(56

Electrochemistry

:
/ .

) (- 2 :
( ) (H2O2
) (Na2O2 ) (K2O2
) (CaO2
) (-1 :

H2O2

2(+1) + 2X = 0

2 + 2X = 0
2X = - 2 X = - 1
2(+1) + 2X = 0

2 + 2X = 0
2X = - 2
X=-1
2(+1) + 2X = 0

Na2O2
K2O2

2 + 2X = 0
2X = - 2 X = - 1

CaO2

2 + 2X = 0

2X = - 2
X=-1

)(57

Electrochemistry

:
/ .

( ) (OF2
) (+ 2
:

X + 2(-1) = 0

OF2

X-2=0
X= +2

( ) (KO2

1

2

KO2

1 + 2X = 0
2X = -1
1
2

X=-

)(58

Electrochemistry

:
/ .

)(-

K 2 Cr2 O 7 , NH +4 , S2 O32- , IO3- , H 2S, OF2 , NaH 2 PO 4 , Al2 O3 ,

+
33Na
O
,
)Fe(OH
,V
O
),Cr(OH
,
PO
,
)Pb(OH
2
2 5
6
4
3
2 2

2(+1) + 2X + 7(-2) = 0
+2 + 2X - 14

K 2 Cr O7
2

2X = - 2 + 14
12
2
X =6
=X

+ 6 = Cr
+
4

X + 4(+1) = + 1

NH

X+4=1
X=1-4
X=-3

(- 3) = N

)(59

Electrochemistry

:
/ .

2X + 3 (-2) = - 2
2X + (- 6) = - 2
23

2X - 6 = - 2
2X= 6 - 2

S2 O

2X = 4
X=+2

+ 2 = S
X + 3 (-2) = - 1
3

X + (- 6) = -1

IO

X=6-1
X =+5

= + 5
................................................................................................................
................................................................................................................

H2S

.................................................... = S
..............................................................................................................
................................................................................................................

OF2

................................................................................................................

.............................................. = O

)(60

Electrochemistry

:
/ .

..............................................................................................................
................................................................................................................

NaH 2 PO4

................................................................................................................
................................................................................................................
................................................................................................................

................................... = P
................................................................................................................
................................................................................................................

Al2O3

................................................................................................................
................................................................................................................

................................... = Al
................................................................................................................
................................................................................................................

Na 2O2

................................................................................................................
................................................................................................................

................................... = Na

)(61

Electrochemistry

:
/ .

................................................................................................................

Fe(OH)+2

................................................................................................................
................................................................................................................
................................................................................................................

................................................. = Fe
................................................................................................................

V2O5

................................................................................................................
................................................................................................................
................................................................................................................

................................................. = V
................................................................................................................

Cr(OH)3-6

................................................................................................................
................................................................................................................
................................................................................................................
................................................................................................................

....................................................= Cr

)(62

Electrochemistry

:
/ .

................................................................................................................
................................................................................................................

PO3-4

................................................................................................................
................................................................................................................
................................................................................................................

..................................................= P
Pb(OH)3

................................................................................................................
................................................................................................................
................................................................................................................
................................................................................................................
................................................................................................................
................................................................................................................
................................................................................................................

................................................. = Pb

)(63

Electrochemistry

:
/ .

Oxidation Reduction Reactions


.

)(-
:
1) NaCl
Na + + Cl 2) 2NaCl
2Na + Cl2
3) Fe3O 4 + H 2
3FeO + H 2 O
4) Na 2 O + 2HCl
2NaCl + H 2 O
5) CH 4 + 2O2
CO 2 + 2H 2 O

:
NaCl
Na + + Cl- (
-1

+1

-1

+1

Na Cl
Na + Cl+

)(64

Electrochemistry

:
/ .

) Na + + Cl-
( NaCl .

2Na + Cl2 (
: 2NaCl
0

)2(+1) 2(-1

2 Na Cl
2 Na + Cl 2
0

-2

+2

2 Na Cl
2 Na + Cl2

) (+1 ) (0
) (-1 ) (0
.
) 2Na + Cl2
( 2NaCl .

3FeO + H 2O (
: Fe3O4 + H 2
2(+1) -2

)3(+2) 3(-2

)+8 4(-2

+6 - 6

+8

Fe3 O 4 + H 2
3 Fe O + H 2 O
+2 -2

-8

Fe3 O 4 + H 2
3Fe O + H 2 O

)(65

Electrochemistry

:
/ .

2NaCl + H 2O (
: Na 2O + 2HCl
2(+1) -2

)2(+1) 2(-1

)2(+1) 2(-1

2(+1) -2

Na 2 O + 2 H Cl
2 Na Cl + H 2 O
+ 2 -2

+2 -2

+2 -2

-2

+2

Na 2 O + 2 H Cl
2 Na Cl + H 2 O

.
CO2 + 2H 2O (
: CH 4 + 2O2
)2x2(+1) 2(-2

)+4 2(-2

+4 -4

+4 - 4

)2(0

)- 4 4(+1

-4 +4

C H 4 + 2 O 2
C O2 + 2 H 2 O
C H 4 + 2 O 2
C O2 + 2 H 2 O

)(66

Electrochemistry

:
/ .

.

)(.

)(.

.

)(-
:
)Al(s) + 2H + (aq
) Al3+ (aq) + H 2 (g

Al3+ (aq) + 3e
)2 Al(s
) H 2 (g
3 2H + (aq) + 2e
--------------------------------------------------- 2Al(s) + 6H +
) 2Al3+ (aq) + 3H 2 (g

)(67

Electrochemistry

:
/ .

:
( ) (
)Ion Electron (Half Reaction Method

( .

.

: ) (

).(

:
) (

)(68

Electrochemistry

:
/ .

:
(
) (H+
.

:
) (H2O
) (OH-
.

.


) (.


) (.


.

)(69

Electrochemistry

:
/ .

)(-
:
ClO- + CrO -2
CrO 2-4 + Cl-

( :
-1

+ Cl-1

+ Cl-

-8
24

)+3 2(-2
2

)+6 4(-2
24

+1 -2
-

Cl O + Cr O
Cr O

+6

-4
2

+1 -2
-

+3

Cl O + Cr O
Cr O

.
( :

+6

-1

+3

Cr O -2
Cr O 2-4
+1

Cl O
Cl-

)(70

Electrochemistry

:
/ .

(

:

Cr O -2
Cr O 2-4

Cl O-
Cl-

Cr O -2 + 2H 2 O
Cr O 2-4

Cl O-
Cl - + H 2 O

( :
) (H+
:

Cr O -2 + 2H 2 O
Cr O 2-4

Cl O-
Cl- + H 2O

Cr O -2 + 2H 2 O
Cr O 2-4 + 4H +

Cl O - + 2H +
Cl - + H 2 O

( :
.

.

)(71

Electrochemistry

:
/ .

Cr O -2 + 2H 2 O
Cr O 2-4 + 4H +

Cl O - + 2H +
Cl- + H 2 O

CrO -2 + 2H 2 O
CrO 2-4 + 4H + + 3e
14
4244
3
14442444
3

ClO
+
2H + + 2e
Cl- + H 2 O
144
42444
3
14243
-1

-1

-1

-1

( :
CrO 42- + 4H + + 3e
2 CrO-2 + 2H 2 O
Cl- + H 2 O
3 ClO- + 2H + + 2e

:
2CrO-2 + 4H 2 O
2CrO2-4 + 8H + + 6e
3ClO- + 6H + + 6e
3Cl- + 3H 2O

(
:
2CrO 42- + 8H + + 6e
2CrO -2 + 4H 2 O
3Cl- + 3H 2O
3ClO - + 6H + + 6e
----------------------------------------------------------------------------------------------- 2CrO -2 + 4H 2 O + 3ClO- + 6H + + 6e
2CrO 2-4 + 8H + + 3Cl- + 3H 2 O + 6e

( :
2CrO-2 + 3ClO- + H 2 O
2CrO 2-4 + 3Cl- + 2H +

)(72

Electrochemistry

:
/ .

)(-
:
Cr2 O72- + S
SO 2 + Cr2 O3

( :
)2 (+3) 3 (-2

)+ 4 2(-2

)2 (6) 7 (-2
22
7

+6

+4 - 4

-14
22
7

Cr O + S
S O 2 + Cr2 O3
-6

12

Cr O + S
S O 2 + Cr2 O3

( :
reduction
Cr2 O 72-
Cr2 O 3
oxidation
S
SO 2

(

:

)(73

Electrochemistry

:
/ .

reduction
S
SO 2

oxidation
Cr2 O 72-
Cr2 O 3

S + 2H 2 O
SO 2

Cr2 O 72-
Cr2 O 3 + 4H 2 O

( :


:

S + 2H 2 O
SO 2

Cr2 O 72-
Cr2 O 3 + 4H 2 O

S + 2H 2 O + 4OH -
SO 2 + 4H 2 O

Cr2 O 72- + 8H 2 O
Cr2 O 3 + 4H 2 O + 8OH -

( :
.

.

S + 2H 2 O + 4OH -
SO 2 + 4H 2 O

Cr2 O72- + 8H 2 O
Cr2 O3 + 4H 2O + 8OH -

S + 2H 2 O + 4OH -
SO 2 + 4H 2 O + 4e

Cr2 O72- + 8H 2 O + 6e
Cr2 O3 + 4H 2 O + 8OH -

)(74

Electrochemistry

:
/ .

( :
2 Cr2 O 72- + 8H 2 O + 6e
Cr2 O 3 + 4H 2 O + 8OH -
3 S + 2H 2 O + 4OH -
SO 2 + 4H 2 O + 4e

:
2Cr2 O 72- + 16H 2 O + 12e
2Cr2 O3 + 8H 2 O + 16OH 3S + 6H 2 O + 12OH -
3SO 2 + 12H 2 O + 12e

( :
2Cr2 O 3 + 8H 2 O + 16OH 2Cr2 O 72- + 16H 2 O + 12e
3SO 2 + 12H 2 O + 12e
3S + 6H 2 O + 12OH -
------------------------------------------------------------------------------------------------------- 2Cr2 O 72- + 3S+22H 2 O + 12OH - +12e
2Cr2 O 3 +3SO 2 + 20H 2 O +16OH - +12e

( :
2Cr2 O 72- + 3S +2H 2O
2Cr2 O3 +3SO 2 + 4OH -

)(75

Electrochemistry

:
/ .

)(-
(
) ( :
NO 3- + Ca
N 2 + Ca 2+

5Ca + 2NO3- + 12H +

5Ca 2+ + N 2 + 6H 2 O :

)(-

) ( :
Cl 2 + S2 O 32-
SO 2-4 + Cl-

4Cl 2 + S2 O 32- +10 OH -

8Cl - + 2SO 42- + 5H 2 O :

)(76

Electrochemistry

:
/ .

)(-
:

IO 3-
I2

2IO 3- +12H + +10e

I 2 + 6H 2 O :

)(-
:

CrO 2-4
CrO -2

CrO 2-4 + 4H 2 O + 3e
CrO -2 + 2H 2 O + 4OH - :

)(-
:

Pb ( OH )3
PbO 2
-

Pb ( OH )3 + OH -
PbO2 + 2H 2O + 2e :
-

)(77

Electrochemistry

:
/ .

)(-
)
( :
1) Cl2 + S2 O32-
Cl- + SO 42- +
2) MnO -4 + N 2 H 4
MnO 2 + N 2
3) Br2
BrO3- + Br 4) Mn(OH) 2
Mn 2 O3

1) 4Cl2 + S2 O32- + 10 OH -
8 Cl- + 2SO 42- + 5H 2 O
2) 4MnO -4 + 3N 2 H 4
4MnO 2 + 3N 2 + 4H 2O + 4OH 3) 6Br2 + 12OH -
2BrO3- + 10 Br - + 6H 2 O
4) 2Mn(OH) 2 + 2OH -
Mn 2 O3 + 3H 2 O + 2e

)(-

) ( :
1) IO 3- + SO 32-
I 2 + SO 2-4
2) Zn + NO 3-
Zn 2+ + NH 4+
3) P4
H 2 PO -4
4)H 3 AsO 4
As 2 O 3

)(78

Electrochemistry

:
/ .

1) 2IO3- + 2H + + 5SO32-
I 2 + H 2 O + 5SO 42 2) 4 Zn + NO3- +10H +
4 Zn 2+ + NH +4 + 3H 2 O
3) P4 + 16H 2 O
4H 2 PO -4 + 24H + + 20 e
4) 2H 3 AsO 4 + 4H + + 4e
As 2 O3 + 5H 2 O

)(79

Electrochemistry

:
/ .

:
( ) (
.
( .
.
(
.
(
.
(
.
(
.

( :
(
) (H+ .

)(80

Electrochemistry

:
/ .

(
) (H2O
) (OH-
.
( .

)(-
:

Fe2+ + NO3-
Fe3+ + NO

(
) (Fe, N.
( :
+2 - 2

+3
3+

+5 +6
3

+2
2+

Fe + N O
Fe + N O

) (+2 ) (+3

) (+5 ) (+2 .

)(81

Electrochemistry

:
/ .

( ) (Fe2+
) (Fe3+ )(NO3-
) (NO
.

(
) (Fe2+, Fe3+ ) (3
) (NO3-, NO ):(1
3Fe2+ + N O3-
3Fe3+ + N O

(

.
3Fe2+ + N O3-
3Fe3+ + N O
3Fe2+ + N O3-
3Fe3+ + N O + 2H 2 O

)(82

Electrochemistry

:
/ .

(
) (H+
:
3Fe 2+ + N O3-
3Fe3+ + N O + 2H 2 O
3Fe 2+ + N O3- + 4H +
3Fe3+ + N O + 2H 2 O

)(-
:

Fe3O 4 + MnO -4
Fe 2 O 3 + MnO 2

( ))) (Fe, Mn
( :
Fe3O4 + MnO
Fe 2 O3 + MnO2
4

2Fe3O4 + MnO-4
3Fe 2O3 + MnO2

( :
)2 (-2

)+18 3 3 (-2

+4

)+ 7 4 (-2

+ Mn O -4
3 Fe 2 O 3 + Mn O 2
-8

+4

+18 - 18

-8
4

+7

)+16 2 4 (-2

2 Fe 3 O 4
+16 16

2 Fe 3 O 4 + Mn O
3 Fe 2 O 3 + Mn O 2

)(83

Electrochemistry

:
/ .

( ) (Fe3O4

) (Fe2O3 ) ( 2e

) ( MnO 4 ) (MnO2
-

) . ( 3e

( )(Fe3O4, Fe2O3

) (3 ) ( MnO , MnO
2

) (2 :
6 Fe3 O 4 + 2Mn O-4
9 Fe 2 O3 + 2Mn O 2

(
:
6 Fe3 O 4 + 2Mn O -4
9 Fe 2 O3 + 2Mn O 2
6 Fe3 O 4 + 2Mn O -4
9 Fe 2 O3 + 2Mn O 2 + H 2 O

)(84

Electrochemistry

:
/ .

( )(H2O

) (OH- :
6 Fe3 O 4 + 2Mn O-4
9 Fe 2 O3 + 2Mn O 2 + H 2 O
6 Fe3 O 4 + 2Mn O -4 + 2H 2 O
9 Fe 2 O3 + 2Mn O 2 + H 2 O + 2OH -

( :
6 Fe3 O 4 + 2Mn O-4 + 2H 2 O
9 Fe 2 O3 + 2Mn O 2 + H 2 O + 2OH 6 Fe3 O 4 + 2Mn O -4 + H 2O
9 Fe 2 O3 + 2Mn O 2 + 2OH -

Electrochemistry

(85)

:
./

(-)
:
1) S + HNO3
SO 2 + NO
2) SO32- + MnO -4
SO 2-4 + MnO 2
3) Zn + NO3-
Zn 2+ + NH +4
4) MnO-4 + C 2 O 2-4
Mn 2+ + CO 2

1) 3S + 4HNO3
3SO 2 + 4NO + 2H 2 O
2) 3SO32- + 2MnO-4 + 2H +
3SO 42- + 2MnO 2 + H 2 O
3) 4Zn + NO3- + 10H +
4Zn 2+ + NH 4+ +3H 2 O
4) 2MnO-4 + 5C2 O2-4 +16H +
2Mn 2+ + 10CO 2 + 8H 2 O

(-)
:
1) ClO - + CrO -2
+ Cl- + CrO 2-4
2) Cl 2 + S2 O32-
Cl- + SO 2-4
3) MnO -4 + N 2 H 4
MnO 2 + N 2
4) Cl 2 + S2 O32-
Cl- + SO 2-4

1) 3ClO - + 2CrO -2 +2OH -

2CrO 2-4 + 3Cl- + H 2O
2) 4Cl2 + S2 O32- + 10 OH -
8Cl- + 2SO 42- + 5H 2O
3) 4MnO-4 + 3N 2 H 4
4MnO 2 + 3N 2 + 4H 2 O + 4OH 4) 4Cl2 + S2 O32- + 10 OH -
2SO 42- + 8Cl- + 5H 2 O

)(86

Electrochemistry

:
/ .

Na + + e
Na

Na
Na + + e

K + + e
K

K
K+ + e

Li + + e
Li

Li
Li + + e

Ag + + e
Ag

Ag
Ag + + e

F2 + 2e
2F-

2F-
F2 + 2e

Cl2 + 2e
2Cl-

2Cl-
Cl2 + 2e

Br2 + 2e
2Br -

2Br - B
r2 + 2e

I 2 + 2e
2I -

2I-
I 2 + 2e

2H + + 2e
H2

H 2
2H + + 2e

Zn 2+ + 2e
Zn

Zn
Zn 2+ + 2e

10

Cu 2+ + 2e
Cu

Cu
Cu 2+ + 2e

11

Fe 2+ + 2e
Fe

Fe
Fe 2+ + 2e

12

Fe3+ + e
Fe 2+

Fe2+
Fe3+ + e

13

Ni 2+ + 2e
Ni

Ni
Ni 2+ + 2e

14

Ca 2+ + 2e
Ca

Ca
Ca 2+ + 2e

15

Cd 2+ + 2e
Cd

Cd
Cd 2+ + 2e

16

Rh 2+ + 2e
Rh

Rh
Rh 2+ + 2e

17

Mn 2+ + 2e
Mn

Mn
Mn 2+ + 2e

18

Mg 2+ + 2e
Mg

Mg
Mg 2+ + 2e

19

Pb 2+ + 2e
Pb

Pb
Pb 2+ + 2e

20

Ba 2+ + 2e
Ba

Ba
Ba 2+ + 2e

21

Hg 2+ + 2e
Hg

Hg
Hg 2+ + 2e

22

Hg 2+ + e
Hg +

Hg +
Hg 2+ + e

23

/ /

)(87

Electrochemistry

:
/ .
/ /

Co
Co

24
25

+ 2e
Co

Co3+ + e
Co 2+

Co 2+
Co3+ + e

Se + 2e
Se 2-

Se 2-
Se + 2e

26

Al3+ + 3e
Al

Al
Al3+ + 3e

27

Cr 3+ + 3e
Cr

Cr
Cr 3+ + 3e

28

Au 3+ + 3e
Au

Au
Au 3+ + 3e

29

Au 3+ + 2e
Au +

Au +
Au 3+ + 2e

30

Au 3+ + e
Au 2+

Au 2+
Au 3+ + e

31

Au + + e
Au

Au
Au + + e

32

Mn 3+ + e
Mn 2+

Mn 2+
Mn 3+ + e

33

Sn 4+ + 2e
Sn 2+

Sn 2+
Sn 4+ + 2e

33

2+

+ 2e

Co

2+

AgBr + e
Ag + Br -

Ag + Br -
AgBr + e

AgCl + e
Ag + Cl-

Ag + Cl-
AgCl + e

)(

Hg 2 Cl2 + 2e
2Hg + 2Cl-

)(

2Hg + 2Cl-
Hg 2 Cl2 + 2e

Hg 2SO 4 + 2e
2Hg + SO 42-

2Hg + SO2-4
Hg 2SO4 + 2e

2H 2 O
O 2 + 4H + + 4e

35

36

37

38

39

O 2 + 4H + + 4e
2H 2 O
2H 2 O + 2e
H 2 + 2OH -

2SO
S2 O + 2e
28

24

40

)(88

Electrochemistry

:
/ .

O 2 + 2H 2 O + 4e
4OH -

2SO2-4
S2 O82- + 2e

4OH -
O 2 + 2H 2 O + 4e

41

42
43

:
MnO + 8H + + 5e
Mn 2+ + 4H 2 O
24

44

Sb 2O3 + 3H 2O + 6e
2Sb + 6OH -

45

2MnO 2 + H 2 O + 2e
Mn 2 O3 + 2OH -

46

Ag 2 O + H 2 O + 2e
2Ag + 2OH -

47

HgO + H 2 O + 2e
Hg + 2OH -

:
PbO2 + 4H + + 2e
Pb 2+ + 2H 2O

48

)(89

Electrochemistry

:
/ .

nd

02 Chapter
Galvanic Cells

)(90

Electrochemistry

:
/ .

Galvanic Cells

:

) (.

) (.





) ) ((-) (-

.

.

Electrochemistry

(91)

:
./

Fig. (2-1) : Summery of the terminology used in voltaic cells. Oxidation

occurs at the anode, and reduction occurs at the cathode. Electrons move
from the negative electrode (anode) to the positive electrode (cathode)
through the external wire. The electrical circuit is completed in the solution
by the movement of ions-anions move from the salt bridge compartment to
the anode compartment, and cations move from the salt bridge compartment
to the cathode compartment. The compartments can be separated either by a
salt bridge or a porous barrier.

Fig. (2-2) : A grapefruit battery. A voltaic cell can be made by inserting

zinc and copper electrodes into a grapefruit. A potential of 0.95 V is
obtained. (The water and citric acid of the fruit allow for an ion conduction
between electrodes). This cell is more complicated than the one in above
figure.

)(92

Electrochemistry

:
/ .

:
(
) (.
)
(
) ).((-

(

) (.
)
( )
).(-

Fig. (2-3) : Leclanche' dry cell and a cutaway view.

)(93

Electrochemistry

:
/ .

Fig. (2-4) : Lithium battery for use in a cell phone.

:


.
) (

" " ) ).((-

Electrochemistry

(94)

:
./

Fig. (2- 5) : A lead storage battery and a cutaway view of

one cell. Each electrode consists of several grids with a large
surface area so that the battery can deliver the high currents
required to start an automobile engine. The electrolyte is
aqueous sulfuric acid.

)(95

Electrochemistry

:
/ .

) ) (Galvani(

.

.

.


.

.

.


.

)(96

Electrochemistry

:
/ .

.

) (Volta


.


) (
.

)(97

Electrochemistry

:
/ .

:
) ) ((-

)
(
.


) (
.

.

) : (- .

Electrochemistry

(98)

:
./

((-) )

Fig. (2-7) :
a) A bent nail corrodes at points of strain and "active" metal atoms.
b) Two nails were placed in an agar gel that contained phenolphthalein
and potassium ferricyanide, K3[Fe(CN)6]. As the nails corroded they
produced Fe2+ ions at each end and at the bend. Fe2+ ions react with
[Fe(CN)6]3- ions to form Fe3[Fe(CN)6]2, an intensely blue-colored
compound. The rest of each nail is the cathode, at which water is reduced
to H2 and OH- ions. The OH- ions turn phenolphthalein pink.

.

.

.

)(99

Electrochemistry

:
/ .

) (NaOH

) (NaOCl .


.

.
) ) ((-

. .

) : (- ) (.

)(100

Electrochemistry

:
/ .

.

.

)(101

Electrochemistry

:
/ .

" ) (I
) (E )(R
E
R

=I

) (I ) (A )(E
) (V ) (R ) . (

) (
.

)(102

Electrochemistry

:
/ .

.


.

:

.

)(103

Electrochemistry

:
/ .

)(Oxidation
" :

".

2+
oxidation
3+
Fe
Fe
+3e
{
1
424
+2

+3 -1 = + 2

Zn
1
Zn42+24
+ 2e
{
3
oxidation

+2 - 2 = 0

)(Reduction


.

2+

reduction

3+

Fe
+3e
{
Fe
1
424
+2

reduction

+3 -1 = + 2
2+

{
Zn424
+ 2e
Zn
1
3
0

+2 - 2 = 0

)(104

Electrochemistry

:
/ .

) (Zn
) (CuSO4 ) )((-) (-
:
) (.
)( :
oxidation
2+
)Zn (s

Zn
(aq) + 2e
dissolution

.
)( :
reduction
Cu 2+ (aq) + 2e
) Cu(s
deposition

:
) (


.
.

.

Electrochemistry

(105)

:
./

Fig. (2-9) :
a) A strip of zinc metal is immersed in an aqueous copper sulfate
solution. The redox reaction takes place at the metal-solution
interface and directly transfers two electrons from Zn atoms to
Cu2+ ions.
b) As time passes, a dark colored deposit of copper metal appears
on the zinc, and the blue color due to Cu2+(aq) fades from the
solution.

Electrochemistry

(106)

:
./

Fig. (2-10) : An oxidation-reduction. A strip of zinc is placed

in a solution of copper (II) sulfate (left). The zinc reacts with the
copper (II) ions to produce copper metal (the brown-colored
deposit on the zinc strip) and zinc ions in solution.
Zn(s) + Cu 2+ (aq)
Zn 2+ (aq) + Cu(s)

As copper metal accumulates on the zinc strip, the blue color due
to the aqueous copper ions gradually fades (middle and right) as
Cu2+ ions are reduced to metallic copper. The zinc ions I aqueous
solution are colorless.

)(107

Electrochemistry

:
/ .

)
( :
)Zn(s) + CuSO 4 (aq
) ZnSO4 (aq) + Cu(s

:
)Cu(s
123

)deposition (reduction

)Zn 2+ (aq
14243

)Zn(s) + Cu 2+ (aq

)dissolution, corrosion (oxidation

:
)

:
)) (Zn(s ) (Cu2+(aq
.

:
)Cu(s
123

)deposition (reduction

)Zn(s) + Cu 2+ (aq
Zn 2+ (aq) +
14243
)corrosion (oxidation

) (cell
.

Electrochemistry

(108)

:
./

.((-) )

Fig. (2-11) :
a) A galvanic cell that uses the oxidation of zinc metal to Zn2+ ions and the
reduction of Cu2+ ions to copper metal. Note that the negative particles (electrons
in the wire and anions in solution) travel around the circuit in the same direction.
The resulting electric current can be used to light a lightbulb.
b) An operating Daniell cell. The salt bridge in part (a) is replaced by a porous
glass disk that allows ions to flow between the anode and cathode compartments
but prevents bulk mixing, which would bring Cu2+ ions into direct contact with
zinc and short-circuit the cell. The lightbulb in part (a) is replaced with a digital
voltmeter.

)(109

Electrochemistry

:
/ .

Galvanic Cells


)
(.
)
(
.
)(electromotive force) (e.m.f

.
) (anode

) (cathode

.

)(110

Electrochemistry

:
/ .

.

) (

) (



) (.

)(111

Electrochemistry

:
/ .

) (Daniel cell :
) (Zn )
.(ZnSO4
) (Cu )
.(CuSO4

)) (V (
.
)( ) )-
((-) ( )
( .
)(
) (two beakers )(half cell
).(cell electrode

).(half cell reaction

) ).((-) (-

)(112

Electrochemistry

:
/ .

) (KNO3
) (KCl )(
.

( .
.
(

)

(.
( )(
.

:
(
( .
.

Electrochemistry

(113)

:
./

Fig. (2-12) : The Daniel cell consists of copper and zinc

electrodes dipping into solutions of copper(II) sulfate and zinc
sulfate, respectively. The two solutions make contact through the
porous pot, which allows ions to pass through to complete the
electrical circuit.

: (-)

Electrochemistry

(114)

:
./

: (-)

Fig. (2-15) : A galvanic cell. The salt bridge (an inverted U tube) containing a KCl
solution provides an electrically conducting medium between two solutions. The openings
of the U tube are loosely plugged with cotton balls to prevent the KCl solution from
flowing into the containers while allowing the anions and cations to move across.
Electrons flow externally from the Zn electrode (anode) to the Cu electrode (cathode).

Electrochemistry

(115)

:
./

Fig. (2-16) : A simple electrochemical cell. The cell consists of a zinc electrode in a
solution containing Zn2+ ions (left), a copper electrode in a solution containing Cu2+
ions (right), and a salt bridge that allows ions to flow into and out of the two
solutions. When the two metal electrodes are connected by a conducting circuit,
electrons flow from the zinc electrode, where zinc is oxidized, to the copper
electrode, where copper ions from the solution are reduced

(116)

Electrochemistry
:
./

Fig. (2-18) : The zinc-copper voltaic cell utilizes the reaction :

Zn(s) + Cu 2+ (aq)
Zn 2+ (aq) + Cu(s) . The standard potential of this cell is 1.10 volts

Electrochemistry

(117)

:
./

Fig. (2-19) : Electrons produced by oxidation leave a galvanic cell at the anode (-), travel through
the external circuit, and reenter the cell at the cathode (+), where they cause reduction. The circuit
is completed inside the cell by migration of ions through the salt bridge. A salt bridge is
unnecessary when the two electrodes share a common electrolyte. The narrow red line outlines the
electrical circuit formed by the movement of electrons (through the external wire) and ions
(through the cell and salt bridge).

Electrochemistry

(118)

:
./

Fig. (2-19) : Practical setup of the galvanic cell described in

above figure. Note the U tube (salt bridge) connecting the two
beakers. When the concentrations of ZnSO4 and CuSO4 are 1
molar (1 M) at 25 C, the cell voltage is 1.10 V.

Fig. (2-20) : The cell potential is measured with an electronic

voltmeter, a device that draws negligible current so that the
composition of the cell does not change during the measurement.
The display shows a positive value when the (+) terminal of the
meter is connected to the cathode of the galvanic cell.

)(119

Electrochemistry

:
/ .

) : (- .

)(120

Electrochemistry

:
/ .

)(Connecting Electrodes


.


) .(electromotive force ) . .(
) (e. m. f
.

.




.

.

)(121

Electrochemistry

:
/ .

.
:
(

( .

:
:

)(-
(

.

)(122

Electrochemistry

:
/ .

) : (-

) (- .



.
.

) (-

)(123

Electrochemistry

:
/ .

) (Cd
) ( .
)(Cd2+
.

.


. ) (- .

) : (-

)(124

Electrochemistry

:
/ .

.
.

) (


) (potential liquid junction

).(0.15 V
) (

.

)(125

Electrochemistry

:
/ .

Flow of Current in Galvanic Cells
( ) .(-
) +
( :
(
) (Zn )(
)
( :
)Zn(S
Zn 2 + (aq) + 2e

).(Zn2+

) (anode
.

) . ( E Zn = - 0.763 V, E Cu = + 0.337 V

.
) (Zn
) (

)(126

Electrochemistry

:
/ .

) ( )
(cathode .
(

) (
:

) Cu(s

2+

Cu (aq) + 2 e

) (Cu2+ .
.
.

).(cathode

(127)

Electrochemistry

:
./

Zn 2+ (aq) + Cu(s) .
Fig. (2-25 A) : The zinc/copper voltaic cell utilizes the reaction : Zn(S) + Cu 2+ (aq)
The potential of this cell is 1.10 volts.

(128)

Electrochemistry

:
./

Zn 2+ (aq) + Cu(s) .
Fig. (2-25 B) : The zinc/copper voltaic cell utilizes the re action : Zn(S) + Cu 2+ (aq)
The potential of this cell is 1.10 volts.

)(129

Electrochemistry

:
/ .

( :

(aq) + 2e

2+

( Zn (s) Zn

(aq) + 2e
) Cu (s

2+

( Cu

) (Zn2+ )
(
) (.


.
.

)(130

Electrochemistry

:
/ .

(
)) (cations (Zn2+

) (Cu2+ .
)) (anions( ) ( SO 2-4
) (Zn2+
.
) ( .
(

) (KCl :
) (Cl- ) (
) (K+ ) ( .

)(131

Electrochemistry

:
/ .

:

:
)Zn (s
Zn 2 + (aq) + 2e

) Cu (s
Cu 2+ (aq) + 2e
---------------------------------------------------------------

) Zn 2 + (aq) + Cu (s
)Zn (s) + Cu 2+ (aq

:



.



:

)(132

Electrochemistry

:
/ .

)(

)(anode

)(

)(cathode

)(133

Electrochemistry

:
/ .

(
( ) Pt (
. ) (Pt
) (Zn Pt
) (Pt
.
( ) (ZnSO4
) (
( :
(
:
)(K2SO4
).(NaNO3
(
:
)(AgNO3
). (CuSO4

)(134

Electrochemistry

:
/ .

( :
)(Zn

( :
oxidation
)Zn (s
Zn 2 + (aq) + 2e

reduction
Cu 2+ (aq) + 2e
) Cu (s

) (Zn
.
(
.
.
(
:
( ) (Zn .

( ) (Cu2+ .

)(135

Electrochemistry

:
/ .

) (cathode :
) (kata- .
) (-hodos
) (kata-hodos ) (cathode
) (.
) (anode :
) (ana-
) (-hodos .
) (ana-hodos ) (anode
) (.
) ( ) (

.
.
) (electrode :

) (electricity
) (-hodos

)(136

Electrochemistry

:
/ .

)( .
)
( ) (electrode
) : () (.

) .(-
) (half cell .

) : (-

)(137

Electrochemistry

:
/ .

) (
Cell Representation

.
.

(
(
(
(
(

)|(
) (Pt|Fe2+,Fe3+
) (ZnSO4
)(CuSO4
) (,
)(Pt|Fe2+, Fe3+
) (salt bridge
) ( )||(
).(KCl
) (s, g, L
).(aq , 1 M

.

.

)(138

Electrochemistry

:
/ .

)Zn(s) ZnSO 4 (aq, 1M) CuSO 4 (aq, 1 M) Cu(s

:

)Zn(s) Zn 2+ (aq, 1M) Cu 2+ (aq, 1 M) Cu(s

:
) C u 2 + (a q , 1 M ) C u (s

{ 1 4 4 442 4 4 4 43
c o p p e r e le c tro d e - c a th o d e

re d u c tio n
C u 2 + (a q ) + 2 e

) C u (s

sa lt
b rid g e

) Z n (s ) Z n 2 + (a q , 1 M

1444
42 4 4 4 4
3
z in c e le c tro d e - a n o d e

o x id a tio n
Z n 2 + (a q ) + 2 e
) Z n (s

) (ZnSO4, CuSO4
) (1 M .
)
(



) ( E H = 0 .

)(139

Electrochemistry

:
/ .

) ) (- :
( ) (HCl
.
( ) (1 atm
.

) : (-

(140)

Electrochemistry

:
./

(-)
:
Cd Cd 2+ (aq , 0.01M) HCl(aq, 1M) H 2 (g , 1 atm) Pt

( Cd)

Cd(s) Cd 2+ (aq , 0.01M)

HCl(aq, 1M) H 2 (g , 1atm) Pt

14444244443 { 1444442444443

hydrogen electrode (cathode)- reduction

cadimium electrode(anode)- oxidation salt
bridge

reduction H (g)
oxidation Cd 2+ (aq) + 2e
2H + (aq) + 2e
Cd(s)
2

1444444444444424444444444444
3
Cd(s) + 2H + (aq)

overall reaction Cd 2+ (aq)

+ H 2 (g)

:
Cd (s)
Cd 2+ (aq) + 2e

oxidation reaction

2H + (aq) + 2e
H 2 (g)

reduction reaction

Cd(s) + 2H + (aq)
Cd 2+ (aq) + H 2 (g)

overall reaction

)(141

Electrochemistry

:
/ .

( ) ( :
Cd Cd 2+ (aq , 0.01M) HCl(aq, 1M) H 2 (g , 1 atm) Pt

( )) (HCl (aq ))(H2(g

))(Pt(s
(
( "",
H2(g, atm), Pt :

)(142

Electrochemistry

:
/ .

)(Electrode Representation

.

) (
) (reduced form ) (
) (oxidized form



.

:
Cu + Cu

:
Cu 2+ Cu

)(143

Electrochemistry

:
/ .

:
Cu 2+ , Cu + Pt

.



:
Cd 2+ Cd , Hg

.





:
H + H 2 , Pt

)(144

Electrochemistry

:
/ .

.

.

).(electrode diagram

)(Cell Representation

.
.

. :
( /
/ :
) (
2+
) ( Cu Cu

. ) (

)(145

Electrochemistry

:
/ .

2+
Zn Zn

. ) (M

:
Zn Zn 2+ M Cu 2+ Cu

) (0.15 mol/L ) (0.24 mol/L
:
Zn Zn 2+ ( 0.24 mol/L ) M Cu 2+ ( 0.15 mol/L ) Cu

(
:

. ) (
:
Zn Zn 2+ ( 0.24 mol/L ) Cu 2+ ( 0.15 mol/L ) Cu

)(146

Electrochemistry

:
/ .

(
+
) ( H H 2 , Pt
) : ( Cl Cl2 , Pt

:
Pt, H 2 ( 0.5 atm ) HCl ( 0.5mol/L ) Cl2 (1atm), Pt

)(HCl


.

).(cell diagram

)(147

Electrochemistry

:
/ .

Measurements of Electromotive Force for A Galvanic Cell

)
(.
) (

) (
) (I
.


.


) (electromotive force e.m.f
.

:

)(148

Electrochemistry

:
/ .

E
R

=I

:
: E .
: R .
:
R = Re + Ri

:
(Rexternal) : Re

) +

(.
: (Rinternal) : Ri .
) (I :
E
) (Re + Ri

=I

) (e.m.f
.

)(149

Electrochemistry

:
/ .

( )(Voltametric Method
) (
.
.

(

.
(

.

.

)(150

Electrochemistry

:
/ .

( )(Potentiometric Method
.

) (Poggendorff compensation principle
) (
)) (e.m.f (
)) (potentiometer cell
).((-

) : (-

)(151

Electrochemistry

:
/ .

(
) (G
) (Es ).(AB
(
) (Eu )' (AB
.
( ) (Eu ) (S
) (ab . :
E s AB
'E u AB
Es
AB
=
Eu
'AB

(Estandard) : Es )(.
(Eunknown) : Eu.

Es
AB
=

'AB
Eu

) (Eu

:
Es
AB
=
Eu
'AB
' AB
= Eu
Es
AB

)(152

Electrochemistry

:
/ .

) (
)(Measurement of E. M. F

) (galvanometer ) (
.

) . .(
) .(voltmeter

.
(
(

.
(
)..(
.

)(153

Electrochemistry

:
/ .

) . .(
) (voltmeters
) (high impedience .
(
) (
) (potentiometer )(balance
.

) ( ) . .(

) .(poggendroff compensation principle
)
(
) . .( .

).(Weston cell

)(154

Electrochemistry

:
/ .

( .

) : (-

) (H
.

).(CdSO4.8/3H2O

) (12% ) (14%
.

.
.

.

)(155

Electrochemistry

:
/ .

Cd
Cd 2+ + 2e

Hg 2SO 4 + 2e
2Hg + SO 2-4

24

Hg 2SO 4 + Cd
2Hg + Cd + SO
2+

:
Hg 2SO4 + Cd + 83 H 2O
2Hg + CdSO4 . 83 H 2O

Cd
Cd 2+ + 2e

24

Hg 2SO 4 + Cd
2Hg + Cd 2+ + SO 2-4

Hg 2SO 4 + 2e
2Hg + SO

)(156

Electrochemistry

:
/ .

)(reproducible

.
.

:
E = 1.01830 - 4.06 10-5 (t - 20) - 9.5 10-7 (t - 20) 2

) (25 C ).(1.01807 V

)(157

Electrochemistry

:
/ .

) (-
.

) : (-

) (- )(W

) (ab ).(ab

)(158

Electrochemistry

:
/ .

) . .( ) (Ew
).(ab
) (X ) (ab
) (a ) (c
) (S ) .(ab
) . .( ) (Ex
).(ac
) (Ex ) (S
) (ab
) (balance
:
E W ab
E X ac

:
EW
ab
=
EX
ac
ac
EX = EW
ab

) (EW ) (ab ) (ac

) (EX .

)(159

Electrochemistry

:
/ .

:
) (EW ).(EX

) (ab
) (c
.

)(160

Electrochemistry

:
/ .

" "
rd

03 Chapter
(Determination of EMF
)Electromotive Force

)(161

Electrochemistry

:
/ .

" "
(Electromotive Force) EMF

E cell = E cathode - E anode

:
: E cell
: E cathode

: E anode .

.
)

anode

( E

) ( E cell = E cathode - E anode

:

)(162

Electrochemistry

:
/ .

( = + .

E cell = E cathode + E anode

( = - .

E cell = E cathode - E anode

:

E cell = E cathode - E anode

.
:
( ) (cathode

cathode

(E

) ( E R )(R

).(right
( ) (anode
) ( E anode ) ( E L )(L
).(left
:

E cell = E cathode - E anode

)(163

Electrochemistry

:
/ .

E cell = E R - E L
) (-

)
( .

(

:

E cathode > E anode

:
) (
) (E = + )
(.
) (
).(E = -
.

)(164

Electrochemistry

:
/ .

Reduction Potential or Oxidation Potential
.


:
"
".
:
"
".

"
.

.

)(165

Electrochemistry

:
/ .

) .(0.337 V
( .
).(0.337 V

(
. ) (+ 0.337 V
) (- 0.337 V
.

)(166

Electrochemistry

:
/ .

.



) (.

:

Cu 2+ + 2e
Cu
:

H 2
2H + + 2e

) (reduction electrode
).(oxidation electrode


:

Cu
Cu 2+ + 2e

)(167

Electrochemistry

:
/ .

2H + + 2e
H2

.



.

) (0.337 V
) (0.337 V .
:
( ) (+ 0.337 V

) (- 0.337 V .

:
" ) (+ 0.337 V )(- 0.337 V
.

)(168

Electrochemistry

:
/ .

)(+ 0.337 V

).(- 0.337 V

.
"

"
) (.

)(169

Electrochemistry

:
/ .

)(Cell Potential


) (Ecell


) (
.
) .(Daniel cell

) (1.0998 V ).(1.1 V

)(170

Electrochemistry

:
/ .

) (+ 0.337 V
) (- 0.337 V
) (- 0.7628 V
).(+ 0.7628 V
/
/
:

Cu 2+ + 2e
Cu
:

Zn
Zn 2+ + 2e
.

)(171

Electrochemistry

:
/ .

:
E red = + 0.337 V

Cu
Cu 2+ + 2e

)(1

E oxi = + 0.7628 V

Zn 2+ + 2e
Zn

)(2

____________________________________________
E cell = + 1.0998 V

Cu 2+ + Zn
Cu + Zn

)E cell = E (1) + E (2


.
:

)(172

Electrochemistry

:
/ .

( :
E oxi = - 0.337 V

Cu
(1) Cu 2+ + 2e

E oxi = + 0.7628 V

Zn 2+ + 2e
(2) Zn

____________________________________________
E cell = + 1.0998 V

Cu 2+ + Zn
Cu + Zn

)E cell = E (2) - E (1
( :
E red = + 0.337 V

(1) Cu 2+ + 2e
Cu

E red = - 0.7628 V

(2) Zn
Zn 2+ + 2e

____________________________________________
E cell = + 1.0998 V

Cu 2+ + Zn
Cu + Zn

)E cell = E (1) - E (2
) (
. .

)(173

Electrochemistry

:
/ .

)(Sign Convention
)
(
.



.

.



.

) ( )
( .

)(174

Electrochemistry

:
/ .

.


.

) (

) (
.

) (Eright ) (ER

) (Eleft ) .(EL
)( )(
) (R :
) (right reduction
.

:
)E cell = E (R) - E (L

)(175

Electrochemistry

:
/ .

)(-
:
)(E Zn = - 0.7628 V, E Cd = - 0.4029 V

(
(
.

( ) . (E cell

:
)E Cd (- 0.4029 V) > E Zn ( - 0.7628 V

144
42444
3
anode - oxidation

144
42444
3
cathode - reduction

)( :

oxidation reaction

reduction reaction

)Zn(s
Zn 2+ (aq) + 2 e

Cd 2+ (aq) + 2e
) Cd(s

)Zn(s) + Cd 2+ (aq
) Zn 2+ (aq) + Cd(s

)(176

Electrochemistry

:
/ .

) ( E cell :

E cell = E cath o d e E an o d e

E an o d e
123

Zn

E cell = E cath o d e42 4

3
1
C
d

) E cell = (- 0 .4 0 2 9 ) - (- 0 .7 6 2 8
E cell = 0 .3 5 9 9 V

) ( E cell = 0.3599 V .

:
( ( )(1 M
(
)(25 C = 298 K
(
).(1 atm

) ( E cell

:
RT
EcelllnQ
1424
3 zF

Ecathode - Eanode

= Ecell

)(177

Electrochemistry

:
/ .

:
R
T
z
F
Q

)(8.314 J/mol. K

) = .( +

) (.
).(96500 C

)( E

)(178

Electrochemistry

:
/ .

Single Electrode Potentials




.

) (Nernest
.

Origin of Potential Electrode



.
) (equilibrium pressure
.

)(179

Electrochemistry

:
/ .

.
.

) (active metals
) (Na, K, Zn, Fe

) (positive ions

.

) (electrical double layer ) (-
)(-
) (M .
:

M
M z+ + ze

)(180

Electrochemistry

:
/ .

)(-

) (less active metals
) Au Ag ...Cu (

)(181

Electrochemistry

:
/ .

).(-

)(-

) (chemical potential :

) (electrical double layer

)(182

Electrochemistry

:
/ .

).(electrode potential

.


)
(
:



:
)Zn(s
Zn 2+ (aq) + 2e

.

) ).((-

)(183

Electrochemistry

:
/ .

Cu 2+ + 2e
) Cu (s


.
) ).((-

)(184

Electrochemistry

:
/ .

(
( :





) .(-

)(-

)(185

Electrochemistry

:
/ .

) ( :

) (Zn ) (ZnSO4
.
.

) ).((-

Fig. (3-4) : Anions move toward the anode to neutralize the positive charge of the
cations produced in solution when zinc metal is oxidized.

)(186

Electrochemistry

:
/ .

)

(

) .(metal/solution interface
) (electrode
) .(electrode potential
.
( ""
(
.
(

)
) (reference electrode (

.


. )(hydrogen electrode

)(187

Electrochemistry

:
/ .

)(Development of Electrode Potential


) (



.

.


.

)(188

Electrochemistry

:
/ .

:


)
( .

.


).(ionization process

)(189

Electrochemistry

:
/ .

.

).(ion-discharge process

.

).(charge separation



) (electrostatic attraction

)(190

Electrochemistry

:
/ .

) .(electrical double layer ).(-

) : (-

.



.

.

)(191

Electrochemistry

:
/ .

:
:
Cu
Cu 2+ + 2e

:
Cu + 2e
Cu
2+

Cu 2+ + 2e
Cu

:
( ( :
Cu
Cu 2+ + 2e

)
(.

)(192

Electrochemistry

:
/ .

( ( :
Cu 2+ + 2e
Cu

.



) (charge separation


) (reversible electrode potential

.

) (
.

)(193

Electrochemistry

:
/ .

)(Measurement of Electrode Potential

.

.

) (-

.


.

)
(.

)(194

Electrochemistry

:
/ .

) : (-

.
.


.


.

)(195

Electrochemistry

:
/ .

Standard Electrodes

:
(
) ) ((-) (-

) (
) (H+
) (HCl .
(
)(standard electrode

)(1 atm
) (25 C
)( .

.

)(196

Electrochemistry

:
/ .

(



) (e.m.f
)(e.m.f

).(relative electrode potential

)H 2 (g
2H + (aq) + 2e

2H + (aq) + 2e
) H 2 (g

Electrochemistry

(197)

:
./

: (-)

Fig. (3-8) : A hydrogen electrode operating under standard-state

conditions. Hydrogen gas at 1 atm is bubbled through a 1 M HCl solution.
The platinum electrode is part of the hydrogen electrode.

Electrochemistry

(198)

:
./

Fig. (3-9) : The standard hydrogen electrode.

Fig. (3-10) : The standard hydrogen electrode. Hydrogen gas at 1 atm

pressure bubbles over an inert platinum electrode that is immersed in a
solution containing exactly 1 M H+ ions at 25 C. The potential for
this electrode is defined as exactly 0 V.

)(199

Electrochemistry

:
/ .

)( )(secondary reference electrodes

.
( :

:

(
:
(
)
(.
( .
(
.

)(200

Electrochemistry

:
/ .

).(Secondary Electrodes

( )(

) (
.
(
:
( ).(calomel electrode
( / ) (glass electrode

).(pH meter
( pH.

)(201

Electrochemistry

:
/ .

)(Other Reference Electrode

:
( .
( )
) (.
( .
( .
(

:
(
(
(
(

)(202

Electrochemistry

:
/ .

:
)(Calomel Reference Electrode

) (
)) (Hg2Cl2 (

)
( ) .(-

)(-

:
Hg Hg 2 Cl2 KCl

)(203

Electrochemistry

:
/ .

.

) KCl

(Cl-

.
.
) (- ) ((-
) (Hg
) (Hg2Cl2
) KCl ( .
.
(

) (KCl
:
)(KCl saturated, (1 mol/L), (0.1 mol/L

)(204

Electrochemistry

:
/ .

. ) (-
).(25 C
)(-
KCl
saturated
1N
0.1 N

0.2415 V
0.2800 V
0.3338 V

) : (-

)(205

Electrochemistry

:
/ .

) : (-
.

(

:
)2Hg(L) + 2Cl- (aq
Hg 2 Cl 2 (s) + 2e

:
Hg 2 Cl 2 (s) + 2e
) 2Hg(L) + 2Cl- (aq

)(206

Electrochemistry

:
/ .

(

:
)Pt H 2 (g, 1 atm) HCl(aq , a = 1) KCl(aq , a = 1) Hg 2 Cl 2 (s)Hg(L

)H 2 (g
2H + (aq) + 2e
Hg 2 Cl2 (s) + 2e
) 2Hg(L) + 2Cl- (aq
)H 2 (g) + Hg 2 Cl 2 (s
) 2H + (aq) + 2Hg(L) + 2Cl- (aq

)(207

Electrochemistry

:
/ .

: /
)(Silver/Silver Chloride Electrode
( /

/
)
.(- .

) : (- /

)(208

Electrochemistry

:
/ .

( /
/

)(e.m.f

.
( /

/
) .(-
KCl
saturated
1N

)(-
/
0.200 V
0.222 V

( /

/
:
)(oxidation

)Ag(s) + Cl- (aq

AgCl + e

/
:
)(reduction

AgCl + e
) Ag(s) + Cl- (aq

)(209

Electrochemistry

:
/ .

( /

:
)Pt H 2 (g, 1 atm) HCl(aq , a = 1) KCl(aq , a = 1) AgCl(s) Ag (s

)H 2 (g
2H + (aq) + 2e
2 AgCl + e
) Ag(s) + Cl- (aq

H 2 (g) + 2AgCl
2H + (aq) + 2Ag(s) + 2Cl-

)(210

Electrochemistry

:
/ .

)(Glass Electrode
) (pH meter
.
] [H+
) ( .

)
) ((-) - (-
.

.
:
| | | |

H2SiO4
:
+ Gl
{
solid

+
+

H
H
Gl-

{
{

solution

solid

.
.

)(211

Electrochemistry

:
/ .

.
.
) (pH
) (pH
) ( 0.01 ).(pH

) : (- .

Electrochemistry

(212)

:
./

Fig. (3-16) : A glass electrode that is used in conjunction with a reference electrode in
a pH meter.

Fig. (3-17) : A glass elect ode consists of a silver wire coated with silver chloride that dips
into a reference solution of dilute hydrochloric acid. The hydrochloric is separated from
the test solution of unknown pH by a thin glass membrane. When a glass electrode is
immersed in the test solution, its electrical potential depends linearly on the difference in
the pH of the solutions on the two sides of the membrane.

)(213

Electrochemistry

:
/ .

)(-
:
Cd Cd 2+ (a = 1) KCl (1 N) Hg 2Cl 2 (s) Hg

) (0.683 V ) (25 C
).(0.28 V

E cell = E Cathode - E anode

{ 123
Cd

Hg 2 Cl2

E anode = E Cathode E cell

{ 123
Hg 2 Cl2

Cd

E anode = 0.28 0.638

{
Cd

E anode = - 0.358 V
{
Cd

)(-

)(214

Electrochemistry

:
/ .

) (e.m.f
.
:
)Zn(s) ZnSO 4 (a = 1) KCl (1 N) Hg 2 Cl 2 (s) Hg (L
)Hg (L) Hg 2 Cl 2 (s) KCl (1 N) CuSO 4 (aq) Cu(s

:

)(1.083 V
)(0.018 V

).(0.281 V
:
( .
(

) (

) (

)Zn(s) ZnSO 4 (a = 1) KCl (1 N) Hg 2 Cl2 (s) Hg (L

)Hg (L) Hg 2 Cl2 (s) KCl (1 N) CuSO 4 (aq) Cu(s

E cell = E Cathode - E anode

{ 123

E cell = E Cathode - E anode

{ 123

E anode = E Cathode E cell

{ 123

E Cathode = E cell + E anode

{
123

E anode = 0.281 1.083

{

E
= 0.018 + 0.281
123

E
= - 0.802 V
{

E
= 0.299 V
123

Zn

Hg 2 Cl2

Hg 2 Cl2

Zn

Zn

anode
Zn

Hg 2 Cl2

Hg 2 Cl2

Cu

Cu

Cathode
Cu

Cathode
Cu

)(215

Electrochemistry

:
/ .

)(-
:
) P t(s) H 2 (g , 1 atm ) H C l(aq, 1 M ) K C l(aq) H g 2 C l 2 (s) H g(L

(
( .

) (
) (.
)KCl(aq) Hg Cl (S) Hg(L

)Pt(s) H (g, 1 atm) HCl(aq , 1M

2
2
1444442444443

2
1444444
424444444
3

reduction
Hg 2Cl2 (s) + 2e
)2Hg (L) + 2Cl- (aq

oxidation
)H2 (g
2H+ (aq) + 2e

calomel electrode - cathode

hydrogen electrode - anode

144444444444444424444444444444443
overall reaction
) 2H+ (aq) + 2Hg(L) + 2Cl- (aq
)H 2 (g) + Hg2 Cl2 (s

)(-

) (1 N :
)P t(s

) H g (L

)H g 2 C l 2 (s

) K C l(aq , 1 N

) C d 2 + (aq , 1 M

)C d (s

)(216

Electrochemistry

:
/ .

( .
( E Cd

) ( E cal = 0.2676 V
) (298 K ) . ( E cell = 0.6830 V

(
)Cd(s) Cd 2+ (aq, 1M

)KCl(aq, 1N) Hg Cl (s) Hg(L) Pt (s

2
144444444
2244444444
3

1444
424444
3

calomel electrode - cathode

cadmium electrode - anode

oxidation
Cd 2+ (aq) + 2e
)Cd(s

reduction
Hg 2 Cl2 (s) + 2e
)2Hg (L) + 2Cl- (aq

144444444444444
42444444444444444
3
overall reaction
)Cd(s) + Hg 2 Cl2 (s
) Cd 2+ (aq) + 2Hg(L) + 2Cl- (aq

( :

C al

= E

c e ll

Cd

C al

= E

Cd

= 0 . 2 6 7 6 0 .6 8 3 0

Cd

Cd

c e ll

- E

= - 0 .4 1 5 4 V

)(217

Electrochemistry

:
/ .

)(-
:
)Pt(s) H g(L) H g 2 C l 2 (s) K C l(aq, 1N ) C u 2+ (aq, 1N ) C u(s

(
(
) ( E cell = + 0.0570V
) = + 0.2676 V

Cal

(E

)Cu 2+ (aq, 1N) Cu(s

14442444
3

copper electrode(cathode) - reduction

)Pt(s) Hg(L) Hg 2 Cl2 (s) KCl(aq, 1N

1444444
424444444
3
calomel electrode (anode) - oxidation

oxidation
Hg 2 Cl2 (S) + 2e
)2Hg (L) + 2Cl- (aq

reduction
) Cu(S
Cu 2+ (aq) + 2e

14444444444444244444444444443
overall reaction

)Cu 2+ (aq) + 2Hg(L) + 2Cl- (aq

) Cu(s) + Hg 2 Cl2 (s

( :
E cell = E C u - E C al
E C u = E cell + E C al
) E C u = ( 0 .0570 ) + ( 0.2676
E C u = 0 .3 2 4 6 V

Electrochemistry

(218)

:
./

(-)
a) Write the chemical equation for the cell reaction
resulting from the following half-reactions :
Hg 2+
2Hg(L)
2 (aq) + 2e
2Hg(L) + 2Cl- (aq)
Hg 2 Cl2 (s) + 2e

b) Write the cell diagram and draw a schematic picture

of the cell and its contents, label the anode and cathode,
and indicate the direction of electron flow. Assume that
the cell contains a salt bridge filled with a KCl gel.

Answer :
a)
Hg 2+
2Hg(L)
2 (aq) + 2e
2Hg(L) + 2Cl- (aq)
Hg 2Cl 2 (s) + 2e
------------------------------------------------------Hg 2+
Hg 2 Cl2 (s)
2 (aq) + 2Cl (aq)

b)
Hg(L) Hg 2 Cl2 (s) HCl(aq) Hg 2 (NO3 ) 2 (aq) Hg(L)

)(219

Electrochemistry

:
/ .

)(-

)(220

Electrochemistry

:
/ .

Electrochemical Series
) ( E

) .(-

.
)(reduction potential
)(oxidation potential

.


.


.

)(221

Electrochemistry

:
/ .

(

(
) (cathode
) (anode :

> anode

cathode

(E

.
)
) (1 atm

). ((1 M

)(222

Electrochemistry

:
/ .

).(-

).(+

:
.
) (25 C
.
) (a = 1

) . ( E
)
(mol/L .

] [.

)(223

Electrochemistry

:
/ .

)( )
(.

.
:

) ( E Zn = - 0.763 V

) (Pt/ Fe2+, Fe3+ ) .(0.771 V

)
( ) (Fe3+

)
( :
)(oxidation

Zn 2+ (aq) + 2e
)Zn(s

)(reduction

) Fe 2+ (aq
2 Fe3+ (aq) + e

__________________________________________
)Zn(s) + 2Fe3+ (aq
) Zn 2+ (aq) + 2Fe 2+ (aq

)(224

Electrochemistry

:
/ .

.

.


.
.
:
E = +
3.045
V
14
243

oxidation
)Li(s
Li + (aq) + e

E = -13.045
V
424
3

oxidation
Li + (aq) + e
) Li(s

) (IUPAC
) (1953
.
)series

(electrochemical

.
.

) E Ag = 00.799 V

( E Cu = 0.337 V,

)(225

Electrochemistry

:
/ .

)(
) (
) (.

:
oxidation

Cu 2+ (aq) + 2e
)Cu(s

) Ag(s
2 Ag + (aq) + e
reduction
________________________________________
)Cu(s) + 2Ag + (aq
) Cu 2+ (aq) + 2Ag(s

) (Cu
) (Ag+


.

)(226

Electrochemistry

:
/ .

.
( :
.

........................................................................................

........................................................................................

........................................................................................

........................................................................................

........................................................................................

........................................................................................

: :
).(a = 1, T = 25 C

(227)

Electrochemistry

:
./

(-)
25 C
Standard Potentials at 25 C
Electrochemical Series ()
N2/N3

N3-/N2
N2/N3Li+/Li
K+/K
Rb+/Rb
Cs+/Cs
Ra2+/Ra
Ba2+/Ba
Sr2+/Sr
Ca2+/Ca
Na+/Na
Ac3+/Ac
La3+/La
Ce3+/Ce
Pr3+/Pr
Nd3+/Nd
Pm3+/Pm
Sm3+/Sm
Eu3+/Eu
Gd3+/Gd
Tb3+/Tb
Y3+/Y

Species

Reduction half-reaction
3
N 2 + H + + e
HN 3 (g)
2
3
2

N 2 + e
N3-

3
N 2 + H + + e
HN 3 (aq)
2

Li + + e
Li
K + + e
K
Rb + + e
Rb
Cs + + e
Cs
Ra 2+ + 2e
Ra
Ba 2+ + 2e
Ba
Sr 2+ + 2e
Sr
Ca 2+ + 2e
Ca
Na + + e
Na
Ac3+ + 3e
Ac
La 3+ + 3e
La
Ce3+ + 3e
Ce
Pr 3+ + 3e
Pr
Nd 3+ + 3e
Nd
Pm3+ + 3e
Pm
Sm3+ + 3e
Sm
Eu 3+ + 3e
Eu
Gd 3+ + 3e
Gd
Tb3+ + 3e
Tb
Y 3+ + 3e
Y

E, V
- 3.40

- 3.20
- 3.09
- 3.045
- 2.925
- 2.925
- 2.923
- 2.916
- 2.906
- 2.888
- 2.866
- 2.714
- 2.6
- 2.522
- 2.483
- 2.462
- 2.431
- 2.423
- 2.414
- 2.407
- 2.397
- 2.391
- 2.372

(228)

Electrochemistry

:
./
2+

Species

Mg /Mg
Dy3+/Dy
Am3+/Am
Ho3+/Ho
Er3+/Er
Tm3+/Tm
Yb3+/Yb
Lu3+/Lu
H2/HH+/H
Sc3+/Sc
AlF6-3/Al
Pu3+/Pu
Th+4/Th
Np3+/Np
Be2+/Be
U3+/U
HfO2, H+/Hf
Hf4+/Hf
Al3+/Al
Ti2+/Ti
Zr4+/Zr
SiF62-/Si, FYb3+/Yb2+
TiF62-/Ti, FV2+/V
Mn2+/Mn
Sm3+/Sm2+

Reduction half-reaction
Mg + 2e
Mg
2+

Dy3+ + 3e
Dy
Am3+ + 3e
Am
Ho3+ + 3e
Ho
Er 3+ + 3e
Er
Tm3+ + 3e
Tm
Yb3+ + 3e
Yb
Lu 3+ + 3e
Lu
1
2

H 2 + e
H-

H + + e
H(g)
Sc3+ + 3e
Sc
AlF63- + 3e
Al + 6FPu 3+ + 3e
Pu
Th 4+ + 4e
Th
Np3+ + 3e
Np
Be 2+ + 2e
Be
U 3+ + 3e
U
HfO2 + 4H + + 4e
Hf + 2H 2 O
Hf 4+ + 4e
Hf
Al3+ + 3e
Al
Ti 2+ + 2e
Ti
Zr 4+ + 4e
Zr
SiF62- + 4e
Si + 6FYb3+ + e
Yb 2+
TiF62- + 4e
Ti + 6FV 2+ + 2e
V
Mn 2+ + 2e
Mn
Sm3+ + e
Sm 2+

E, V
- 2.363
- 2.353
- 2.320
- 2.319
- 2.296
- 2.278
- 2.267
- 2.255
- 2.25
- 2.1065
- 2.077
- 2.069
- 2.031
- 1.899
- 1.856
- 1.847
- 1.789
- 1.7
1.70
- 1.662
- 1.628
- 1.529
- 1.24
- 1.21
- 1.191
- 1.186
- 1.180
- 1.15

(229)

Electrochemistry

:
./
3+

Species

Nb /Nb
WO42-/W
PaO2+/Pa, H2O
Po/H2Po
Se/Se2TiO2+/Ti
H3BO3/B
H3BO3/B
SiO2/Si
Ta2O3/Ta
OH-/H2
Zn2+/Zn
Zn2+/Zn(Hg)
TI/Tl
Cr3+/Cr
Te/H2Te (aq)
Te/H2Te (g)
SbO2-/Sb
Tl, Br/Tl, BrNb2O3/Nb
U+4/U+3
As/AsH3
TlCl/Tl, ClGa3+/Ga
Sb/SbH3
H3PO2/P
H3PO3/H3PO2
S/S2-

Reduction half-reaction

PaO 2+ + 4H + + 5e
Pa + 2H 2 O

E, V
- 1.099
- 1.05
- 1.0

Po + 2H + + 2e
H 2 Po

> - 1.00

Nb + 3e
Nb
3+

WO 2-4 + 4H 2 O + 6e
W + 8 OH -

Se + 2e
Se 2TiO 2+ + 2H + + 4e
Ti + H 2 O
H 3BO3 (aq) + 3H + + 4e
B + 3H 2 O
H 3 BO3 (s) + 3H + + 3e
B + 3H 2 O
SiO 2 (quartz) + 4H + + 4e
Si + 2H 2 O
Ta 2 O3 + 10H + + 10e
2Ta + 5H 2 O
2H 2O + 2e
H 2 + 2OH Zn 2+ + 2e
Zn
Zn 2+ + Hg + 2e
Zn(Hg)
TlI + e
Tl + ICr 3+ + 3e
Cr
Te + 2H + + 2e
H 2Te(aq)
Te + 2H + + 2e
H 2 Te(g)
SbO-2 + 2H 2O + 3e
Sb + 4OH TlBr + e
Tl + Br Nb 2 O3 + 10H + + 10e
2Nb + 5H 2 O
U +4 + e
U 3+
As + 3H + + 3e
AsH 3 (g)
TlCl + e
Tl + ClGa 3+ + 3e
Ga
Sb + 3H + + 3e
SbH 3
H 3 PO 2 + H + + e
P(white) + 2H 2 O
H 3 PO3 (aq) + 2H + + 2e
H 3 PO 2 (aq) + H 2 O
S + 2e
S 2-

- 0.92
- 0.882
- 0.8698
- 0.869
- 0.857
- 0.812
- 0.809
- 0.7628
0.7627
- 0.752
- 0.744
- 0.739
- 0.718
- 0.67
- 0.658
- 0.644
- 0.607
- 0.607
- 0.5568
- 0.529
- 0.510
- 0.508
- 0.499
- 0.447

(230)

Electrochemistry

:
./
2+

Species

Fe /Fe
Eu3+/Eu2+
Cr3+, Cr2+/Pt
Cd2+/Cd
Se/H2Se
Ti3+, Ti2+/Pt
PbI2/Pb
Pb, PbSO4/SO42Cd2+/Cd(Hg)
PbSO4/Pb(Hg)
Tl+/Tl
Co2+/Co
Ni2+/Ni
Mo3+/Mo
Sn2+/Sn
Pb2+/Pb
Ag, AgBr/BrTi4+, Ti3+/Pt
D+/D2, Pt
H+/H2, Pt
Ge2+/Ge
Sn4+, Sn2+/Pt
Cu2+, Cu+/Pt
Ag, AgCl/ClHg, Hg2Cl2/ClCu2+/Cu
Fe(CN)64-, Fe(CN)63-/Pt
OH-/O2, Pt

Reduction half-reaction
Fe + 2e
Fe
2+

Eu 3+ + e
Eu 2+
Cr 3+ + e
Cr 2+
Cd 2+ + 2e
Cd
Se + 2H + + 2e
H 2Se(aq)
Ti3+ + e
Ti 2+
PbI 2 + 2e
Pb + 2IPbSO 4 + 2e
Pb + SO 2-4
Cd 2+ + Hg + 2e
Cd(Hg)
PbSO 4 + Hg + 2e
Pb(Hg)
Tl+ + e
Tl
Co 2+ + 2e
Co
Ni 2+ + 2e
Ni
Mo3+ + 3e
Mo
Sn 2+ + 2e
Sn
Pb 2+ + 2e
Pb
AgBr + e
Ag + Br
Ti3+
Ti 4+ + e

D + + e
1/2D 2
H + + e
12 H 2
Ge 2+ + 2e
Ge
Sn 4+ + 2e
Sn 2+
Cu 2+ + e
Cu +
AgCl + e
Ag + ClHg 2 Cl2 + 2e
2Hg + 2ClCu 2+ + 2e
Cu
Fe(CN)64- + e
Fe(CN)3-6
O 2 + H 2 O + 2e
2OH -

E, V
- 0.4402
- 0.429
- 0.408
- 0.4029
- 0.399
- 0.369
- 0.365
- 0.3588
- 0.3516
- 0.3505
- 0.3363
- 0.277
- 0.250
- 0.20
- 0.136
- 0.126
- 0.0713
- 0.04

- 0.0034
0.000
+ 0.01
+ 0.15
+ 0.153
+ 0.2224
+ 0.2678
+ 0.337
+ 0.36
+ 0.401

(231)

Electrochemistry

:
./
+

Species

Cu /Cu
I-/I2, Pt
Te4+/Te
MnO4-, MnO42-/Pt
Rh2+/Rh
O/OFe3+, Fe2+/Pt
Hg22+/Hg
Ag+/Ag
Hg2+/Hg
Hg2+, Hg+/Pt
N5+/N2+
Pd2+/Pd
Br-/Br2, Pt
Pt2+/Pt
O/O2Mn2+, H+/MnO2, Pt
Tl3+, Tl/Pt
MnO2/Mn2+
Cr3+, Cr2O72-, H+/Pt
Cl-/Cl2, Pt
Au3+, Au+/Pt
Pb2+, H+/PbO2, Pt
ClO3-/Cl2
Au3+/Au
Mn3+, Mn2+/Pt
Mn3+, Mn2+/Pt
Ce4+, Ce3+/Pt

Reduction half-reaction

Cr2 O 72- +14H + + 6e

2Cr 3+ + 7H 2 O

E, V
+ 0.521
+ 0.5355
+ 0.56
+ 0.564
+ 0.60
+ 0.68
+ 0.771
+ 0.788
+ 0.7991
+ 0.854
+ 0.91
+ 0.96
+ 0.987
+ 1.0652
+ 1.2
+ 1.229
+ 1.23
+ 1.25
1.28
+ 1.33

Cl2 + 2e
2Cl-

+ 1.3595

Cu + e
Cu
+

I 2 + 2e
2ITe 4+ + 4 e
Te
MnO-4 + e
MnO 2-4
Rh 2+ + 2e
Rh
O 2 + 2H + + 2e
H 2O2
Fe3+ + e
Fe 2+
Hg 2+
2Hg
2 +2e
Ag + + e
Ag
Hg 2+ + 2e
Hg
Hg 2+ + e
Hg +
NO3- + 4H + + 3e
NO + 2H 2 O
Pb 2+ + 2e
Pd
Br2 + 2e
2Br Pt 2+ + 2e
Pt
O 2 + 4H + + 4e
2H 2 O
MnO 2 + 4H + + 2e
Mn 2+ + 2H 2 O
Tl3+ + 2e
Tl+
MnO 2 + 4H + + 2e
Mn 2+ + 2H 2 O

Au 3+ + 2e
Au +
PbO 2 + 4H + 2e
Pb + 2H 2 O
+

2+

2ClO3- +12H + + 10e

Cl2 + 6H 2 O
Au 3+ + 3e
Au
MnO 2-4 + 8H + + 5e
Mn 2+ + 4H 2 O
Mn 3+ + e
Mn 2+
Ce 4+ + e
Ce3+

+ 1.402
+ 1.455
+ 1.47
+ 1.498
+ 1.51
+ 1.51
+ 1.61

(232)

Electrochemistry

:
./
+

Species

Cl /Cl
SO42-, H+/PbSO4, PbO2 ,Pb
Au+/Au
O-1/O-2/Pt
Co3+, Co2+/Pt
S2O82-/SO42O/O2H-/H2, Pt
Hg2Cl2/Hg, ClF -/F2, P t

Reduction half-reaction
2HOCl + 2H + 2e
Cl2 + H 2 O
+

PbO 2 + SO 2-4 + 4H + + 2e
PbSO 4 + 2H 2 O
Au + + e
Au
H 2O 2 + 2H + + 2e
2H 2O
Co3+ + e
Co 2+
S2 O82- + 2e
2SO 2-4
O3 + 2H + + 2e
O2 + H 2O
H 2 (g) + 2e
2H - (aq)
Hg 2 Cl2 (s) + 2e
2Hg(L) + 2Cl- (aq)
F2 (g) + 2e
2F- (aq)

E, V
+ 1.63
+ 1.682
+ 1.691
+ 1.776
+ 1.808
+ 2.00
+ 2.07
+ 2.2
+ 2.27
+ 2.87

)(233

Electrochemistry

:
/ .

(
) (
) (-
) ( ) (Li

) . ( E Li = - 3.045

(
(

) ( .
) ( ) (F2

) . ( E F = + 2.87
2

( ) (


.

)(234

Electrochemistry

:
/ .

(
:

E cathode > E anode

:

= 1.3595 V, E Pb2+ /Pb = - 0.1260 V

Cl2 /2Cl-

(E

:
) E C l 2 (1 .3 5 9 5 V
1 442 4 43

c a th o d e

re d u c tio n
C l 2 (g ) + 2 e

) 2 C l - (a q

<

) E P b (- 0 .1 2 6 0 V
1 4 42 4 43

anode

o x id a tio n
) s

P b 2 + (a q ) + 2 e

44444444
42 4 4 4 4 4 4 4 4 4
3
o v e ra ll re a c tio n
) P b (s ) + C l 2 (g

) P b 2 + (a q ) + 2 C l - (a q

E c e ll = E C l 2 - E P b
E c e ll = 1 .3 5 9 5 - ( - 0 .1 2 6 0 ) = 1 .4 8 5 5 V

(
) (
) ( )
(

) (- .

(235)

Electrochemistry

:
./

Fig. (3-19) : The significance of standard potentials. Only couples

with negative standard potentials (and hence lying below hydrogen) can
reduce hydrogen ions to hydrogen gas. The reducing power increases as
the standard potential becomes more negative.

( E Cu

2+

/ Cu

= + 0.337 V

)
: ( H+
Cu(s) + 2HCl
(no reaction)

Cu(s) + 2H + (aq)
(no reaction)

)(236

Electrochemistry

:
/ .

( ) (
) (
) ( )
(

.

) (Zn

) ( E Zn = - 0.7624 V )
(H+
:
)Zn(s) + 2HCl(aq
) ZnCl 2 (aq) + H 2 (g

)Zn(s) + 2H + (aq
) Zn 2+ (aq) + H 2 (g

( :
E = - 0.7624 V

E = - 0.7624 V

Zn 2+ (aq) + 2e
) Zn(s

2 Zn 2+ (aq) + 2e
) Zn(s

( :
E = - 0.7624 V

E = + 0.7624 V

reduction
Zn 2+ (aq) + 2e
) Zn(s

oxidation
)Zn(s
Zn 2+ (aq) + 2e

)(237

Electrochemistry

:
/ .

(
.

.
( :
(
( )(25 C
( )(1 atm

)(238

Electrochemistry

:
/ .

:
( .
( .
( .

:

RT
lnQ
14243 zF

E cell

= E cell

Ecathode - Eanode

:
: Ecell .

: E cell .

: R )(R = 8.314 J/mol K

: T )(K = C + 273
: z )

(.

)(239

Electrochemistry

:
/ .

: F )(1 F = 96500
: Q

.
: ln )
.(ln = 2.303 log10

) (.

)(240

Electrochemistry

:
/ .

( ) (Ecell = +
) (spontaneous

:
E cell = + 0.442 V

)2Ag + (aq) + Cu(s

) 2Ag(s) + Cu 2+ (aq

( ) (Ecell = -
) (non spontaneous

.

:
E cell = - 0.442 V

)2Ag(s) + Cu 2+ (aq
) 2Ag + (aq) + Cu(s

:
E cell = + 0.442 V

)2Ag + (aq) + Cu(s

) 2Ag(s) + Cu 2+ (aq

)(241

Electrochemistry

:
/ .

)(-
:
)Cu(s

)Cu 2+ (aq, a = 1

)Cd(s) Cd 2+ (aq, a = 1

) (298 K
:
) = - 0.4029 V, E Cu = + 0.337 V

Cd

(E

.
:
) C u 2 + (a q , a = 1 ) C u (s
1444
42 4 4 4 4
3
c o p p e r e le c tro d e - c a th o d e

re d u c tio n

) C u (s
C u 2 + (a q ) + 2 e

) C d (s ) C d 2 + (a q , a = 1
1444
42 4 4 4 4
3
c a d m iu m e le c tro d e - a n o d e

o x id a tio n

C d 2 + (a q ) + 2 e
) C d (s

1 4 4 4 4 4 4 4 442 4 4 4 4 4 4 4 4 43
e ra l re a c tio n
o v

) C d 2 + (a q ) + C u (s
) C d (s ) + C u 2 + (a q

:
- E C d

Cu

= E

cell

)E cell = (0.337 ) ( 0.4029

E cell = 0.7399 V

)(242

Electrochemistry

:
/ .

)(-
:

= 1 .3 5 9 5 V , E M n O 2 - = 1 .5 2 0 0 V
4

2 /2 C l

= 0 .5 3 6 0 V , E C l

I 2 /2 I -

(E

(
) ( :
) 2Cl- (aq,1M) + I 2 (s
)1. Cl 2 (g, 1 atm) + 2I - (aq, 1M
5
)Cl2 (g,1atm
2

)2. MnO -4 (aq,1M) + 8H + (aq,1M) + 5Cl- (aq,1M

Mn 2+ (aq) + 4H 2 O(L) +

( .

): (
) C l2 (g , 1 a tm ) + 2 I - (a q , 1 M
) 2 C l - ( a q ,1 M ) + I 2 ( s
x id a tio n
) 2 I - ( a q
o

I 2 (s) + 2 e

e d u c tio n
C l 2 ( g ) + 2 e
r

) 2 C l- (a q

E c e ll = E c a t h o d e - E a n o d e
E c e ll = E C l 2 - E I 2
E c e ll = 1 .3 5 9 5 - 0 .5 3 6 0
E c e ll = 0 .8 2 3 5 V

)(243

Electrochemistry

:
/ .

): (
5
)Cl (g,1atm
2 2

)MnO -4 (aq,1M) + 8H + (aq,1M) + 5Cl- (aq,1M

Mn 2+ (aq) + 4H 2 O(L) +
5
oxidation
)5Cl- (aq,1M

Cl 2 (g,1atm) + 5e

2
+
reduction
MnO 4 (aq,1M) + 8H (aq,1M) + 5e

) Mn 2+ (aq) + 4H 2 O(L

E cell = E cathode - E anode
E cell = E MnO- - E Cl2
4

E cell = 1.5200 - 1.3595

E cell = 0.1605 V

.

.

.

.

)(244

Electrochemistry

:
/ .

)(-
:
)Fe(s) + Ni 2+ (aq
) Fe 2+ (aq) + Ni(s

:
( .
( .
( :
) = - 0.44 V, E Ni = - 0.250 V

Fe

(E

( )( ) : (-

)(-

)(245

Electrochemistry

:
/ .

( :
( )( :
)Fe(s
Fe 2+ (aq) + 2 e

( )( :
Ni 2+ (aq) + 2e
) Ni(s

( :
)Fe(s) + Ni 2+ (aq
) Fe2+ (aq) + Ni(s

( :
Ecell = ENi - EFe
Ecell = - 0.25 - (- 0.44) = + 0.19 V

( )(+ 0.19 V
)(-
)(
) (II
) ( E Cu = + 0.34 V
.
.

)(246

Electrochemistry

:
/ .

)) ((-) (-
.

) : (- )( .

Fig. (3-22) : The standard copper-SHE cell :

)Pt H + (aq, 1 M); H 2 ( 1 atm) Cu 2+ (aq, 1 M) Cu(s

In this cell, the standard hydrogen electrode functions as the anode. The net
)reaction is H 2 (g) + Cu 2+ (aq
) 2H + (aq) + Cu(s

Electrochemistry

(247)

:
./

Fig. (3-23) : A cell consisting of a copper electrode and a

hydrogen electrode. This cell is operating under standard-state
conditions. SHE acts as anode.

Fig. (3-24 : The standard Cu/SHE cell

Electrochemistry

(248)

:
./

Fig. (3-25) : A galvanic cell consisting of a Cu2+(1 M)/Cu half-cell and a standard
hydrogen electrode (S.H.E). The S.H.E. is a piece of platinum foil that is in contact
with bubbles of H2(g) at 1 atm pressure and with H+(aq) at 1 M concentration.
Electrons flow from the S.H.E. (anode) to the copper cathode. The measured
standard cell potential at 25 C is 0.34 V.

Fig. (3-26) : An electrochemical cell using the Cu2+/Cu half-cell and the standard
hydrogen electrode. A voltage of + 0.34 V is produced. In this cell, Cu2+ ions are
reduced to form Cu metal, and H2 is oxidized at the standard hydrogen electrode.
The reaction at the standard hydrogen electrode (anode)
is :
+
H 2 (g) + 2H 2O(L)
2H 3O (aq) + 2e .

Cathodic half-cell reaction is : Cu 2+ (aq) + 2e

Cu(s) .

)(249

Electrochemistry

:
/ .

:
) ( :
)H 2 (g
2H + (aq) + 2e

) ( :
Cu 2+ (aq) + 2e
) Cu(s

:
)H 2 (g) + Cu 2+ (aq
) 2H + (aq) + Cu(s

:
E cell = E Cu - E H
E cell = 0.34 - (0.000) = 0.34 V

)(-
)(
) (II

) ( E Cu = - 0.7642 V

. .

Electrochemistry

(250)

:
./

(( -) (-))
.

Fig. (3-27) : The Zn(s) Zn 2+ (aq, 1 M) H + (aq, 1M); H 2 (1 atm) Pt in which

the following net reaction occurs. Zn(s) + 2H + (aq)

Zn 2+ (aq) + H 2 (g) .
In this cell the standard hydrogen electrode functions as the cathode.

Fig. (3-28) : The Zn/Zn2+ (1.0 M) //H+(1.0 M), H2 (1 atm)/Pt cell in which
Zn 2+ (aq) + H 2 (g)
the reaction Zn(s) + 2H + (aq)

Electrochemistry

(251)

:
./

Fig. (3-29) : A galvanic cell consisting of a Zn/Zn2+ (1 M) half-cell and a

standard hydrogen electrode. Electrons flow from the zinc anode to the
S.H.E. (cathode). The measured standard cell potential at 25 C is 0.76 V.

Fig. (3-30) : An electrochemical cell using a Zn2+/Zn(s) half-cell and a

standard hydrogen electrode. In this cell, the zinc electrode is the anode and
the standard hydrogen electrode is the cathode. The cell voltage is + 0.76 V.
Zinc is the reducing agent and is oxidizing to Zn2+; H3O+ is the oxidizing
agent and is reduced to H2. In the standard hydrogen electrode, reaction
occurs only where the three phases-gas, solution, and solid electrode- are in
contact. The platinum electrode does not undergo any chemical change, and
in the cell pictured here the cathodic half-cell reaction is :
2H 3O + (aq) + 2e
H 2 (g) + 2H 2 O(L) .

The anodic half-cell reaction is : Zn(s)

Zn 2+ (aq) + 2e .

(252)

Electrochemistry

:
./

(-)
Design a galvanic cell that uses the redox reaction :

Fe(s) + 2Fe 3+ (aq)

3Fe 2+ (aq)
Identify the anode and cathode half-reactions, and
sketch the experimental setup. Label the anode and
cathode, indicate the direction of electron and ion flow,
and identify the sign of each electrode.

Anode (oxidation)

Fe(s)
Fe 2+ (aq) + 2e

Fe 2+ (aq)
2 Fe3+ (aq) + e
-------------------------------------------------------------------------------Cathode (reduction)

Overall cell reaction

Fe(s) + 2Fe3+ (aq)

3Fe 2+ (aq)

Fig. (3-31)

(253)

Electrochemistry

:
./

(-)
A simple voltaic cell is assembled with Ni(s) and
Ni(NO3)2(aq)

in

one

compartment

and

Cd(s)

and

Cd(NO3)2(aq) in the other compartment. An external wire

connects the two electrodes, and a salt bridge containing
NaNO3 connects the two solutions. The overall reaction is :

Ni 2+ (aq) + Cd(s)
Ni(s) + Cd 2+ (aq)
a) What is the reaction at the anode/
b) What is the reaction at the cathode?
c) What are the directions of electron flow in the external
wire and of ion flow in the salt bridge? Complete the cell
diagram by indicating the anode, the cathode, and the
directions of electron flow and ion flow.

Fig. (3-32)

Electrochemistry

(254)

:
./

Cd 2+ (aq) + 2e
a) Anode : Cd(s)
Ni(s)
b) Cathode : Ni 2+ (aq) + 2e

(oxidation)
(reduction)

c) The completed voltaic cell is shown below (Fig. (3-33)

Fig. (3-33)

(255)

Electrochemistry

:
./

(-)
The cell illustrated in the following drawing (Fig. (3-34))
generates a potential of (E = 0.51 V) under standard
conditions at 25 C.

Fig. (3-34)

The net cell reaction is :

Zn(s) + Ni 2+ (aq, 1 M)
Zn 2+ (aq , 1 M) + Ni(s)

The half-cell potential for Zn(s)/Zn2+(aq, 1 M) is (- 0.76 V).

a) Determine which electrode is the anode and which is the
cathode.

(256)

Electrochemistry

:
./

b) Show the direction of electron flow outside the cell,

and complete the cell diagram.
c) Calculate the standard potential for the half-cell
Ni 2+ (aq) + 2e
Ni(s)

a) Zinc is the anode; nickel is the cathode.

b) The cell diagram is shown in the drawing below
(Fig. (3-35)).
c) 0.25 V

Fig. (3-35)

(257)

Electrochemistry

:
./

(-)
Consider the following galvanic cell (Fig (3-36)) :
a) Complete the drawing by adding any components
essential for a functioning cell.
b) Label the anode and cathode, and indicate the
direction of ion flow.
c) Write a balanced equation for the cell reaction.
d) Write the shorthand notation for the cell.

Fig. (3-36)

)(258

Electrochemistry

:
/ .

)(-
) (Ag ) (Cu
:

= + 0.799 V, E Cu
= + 0.337 V
2+
/Cu

Ag + /Ag

(E

:
)Cu(s) Cu 2+ (aq, 1 M) Ag + (aq, 1M) Ag (s

:
)Cu(s) + 2Ag + (aq
) Cu 2+ (aq) + 2Ag(s

)).(-

)(259

Electrochemistry

:
/ .

)Fig. (3-37

)Fig. (3-38) : The standard Cu(s) Cu 2+ (aq, 1 M) Ag + (aq, 1M) Ag (s

)(260

Electrochemistry

:
/ .

)(-
(
:
)H 2 (g
2H + (aq) + 2e
Co3+ (aq) + e
) Co 2+ (aq
( )(cell diagram

) (schematic picture
) (label
).(direction of electron flow

( :
)H 2 (g
2H + (aq) + 2e
2 Co3+ (aq) + e
) Co 2+ (aq
----------------------------------------------------------- )H 2 (g) + 2Co3+ (aq
) 2H + (aq) + 2Co 2+ (aq

( :
)Pt(s) H 2 (g) H + (aq) Co3+ (aq), Co 2+ (aq) Pt(s

)).((-

)(261

Electrochemistry

:
/ .

Fig. (3-39) : The narrow red outlines the electrical circuit formed
by the movement of electrons (through the external wire) and
ions (through the cell and salt bridge).

)(-
:
)Fe(s) + Cd 2+ (aq
) Fe2+ (aq) + Cd(s

:
( .
(
) = - 0.44 V, E Cd = - 0.40 V

Fe

(E

)(262

Electrochemistry

:
/ .

( ) (-
.

)(-

:
)Fe(s
Fe 2+ (aq) + 2e

Cd 2+ (aq) + 2e
) Cd(s
:
)Fe(s) + Cd 2+ (aq
) Fe 2+ (aq) + Cd(s

( :
E cell = E Cd - E Fe
E cell = - 0.40 - (- 0.44) = 0.04 V

)(263

Electrochemistry

:
/ .

)(-
) (Mg
) (Mg(NO3)2
.Pb(NO3)2
:
)(E Mg = - 2.37 V, E Pb = - 0.130 V

( .
( .
( .

)(-

)(264

Electrochemistry

:
/ .

(
)( :
)Mg(s
Mg 2+ (aq) + 2e

)( :
Pb 2+ (aq) + 2e
) Pb(s

:
)Mg(s) + Pb 2+ (aq
) Mg 2+ (aq) + Pb(s

( :
E cell = E Pb - E Mg
E cell = - 0.13 - ( - 2.37) = 2.24 V

)(-
( :
)2Al(s) + 3Cu 2+ (aq
) 2Al3+ (aq) + 3Cu(s

( .
( :
) . ( E Al = - 1.66 V, E Cu = 0.34 V

)(265

Electrochemistry

:
/ .

)(-

( :
)2Al(S) + 3Cu 2+ (aq
) 2Al3+ (aq) + 3Cu(S
oxidation
reduction
6444447444448
6444447444448
2Al3+ (aq) + 6e , 3Cu 2+ (aq) + 6e
) 3Cu(s
)2Al(s
1444444444444424444444444444
3
)2Al3+ (aq) + 3Cu(s

overall reaction

)2Al(s) + 3Cu 2+ (aq

( :
E cell = E Cu - E Al
E cell = 0.34 - ( - 1.66) = 2 V

)(266

Electrochemistry

:
/ .

)(-
:

E Mg = - 2.36V, E Ca = - 2.86 V, E Al = - 1.66V, E Sn

= - 0.14 V, E H = 0.000,

E Ag = 0.8 V, E Ni = - 0.250 V, E Br = 1.0652 V, E Cl

= 1.3595V

.
)1................Mg(s) + Ca 2+ (aq
) Mg 2+ (aq) + Ca(s
)2................2Al3+ (aq) + 3Sn(s
) 3Sn 2+ (aq) + 2Al(s
)3................H 2 (g) + 2Ag + (aq
) 2H + (aq) + 2Ag(s
)4.................Ni(s) + Br2 (s
) Ni 2+ (aq) + 2Br - (aq
)5..................Cl 2 (g) + 2Br - (aq
) Br2 (L) + 2Cl- (aq

:
oxidation - anode
reduction - cathode
64444
744448
6444
4744448
2+
2+
)Mg(s
Mg (aq) + 2e , Ca (aq) + 2e
) Ca(s

E cell = E Ca - E Mg

{ {
anode

cathode

E cell = - 2.86 - (-2.36) = - 0.5 V

)(267

Electrochemistry

:
/ .

:
)Mg 2+ (aq) + Ca(s
) Mg(s) + Ca 2+ (aq
:
)2Al3+ (aq) + 3Sn(s
) 3Sn 2+ (aq) + 2Al(s
oxidation- anode
reduction - cathode
64444
4744444
8
64444
4744444
8
2+
3+
)3Sn(s
3Sn (aq) + 6e , 2Al (aq) + 6e
) 2Al(s

E cell = E Al - ESn
{ {

anode

cathode

cell

E = - 1.66 - (- 0.14) = - 1.52 V

:
)3Sn 2+ (aq) + 2Al(S
) 2Al3+ (aq) + 3Sn(S

:
) 2H + (aq) + 2Ag(s
)H 2 (g) + 2Ag + (aq
oxidation - anode
reduction - cathode
64444
744448
64444
4744444
8
+
+
2H (aq) + 2e , 2Ag (aq) + 2e
) 2Ag(s
)H 2 (g

E cell = E Ag - E H2
{ {
anode

cathode

cell

E = 0.8 - (- 0.000) = 0.8 V

(268)

Electrochemistry

:
./

:
Ni 2+ (aq) + 2Br - (aq)
Ni(s) + Br2 (s)
oxidation - anode
reduction - cathode
64444
744448
64444744448
Ni 2+ (aq) + 2e , Br2 (s) + 2e
2Br - (aq)
Ni(s)

E cell = E Br2 - E Ni
{ {
cathode

anode

E cell = 1.07 - (- 0.25) = 1.32 V

.
:
Cl2 (g) + 2Br - (aq)
Br2 (L) + 2Cl- (aq)
oxidation - anode
reduction - cathode
64444744448
64444
4744444
8
2Br (aq)
Br2 (L) + 2e , Cl2 (g) + 2e
2Cl (aq)

E cell = E Cl2 - E Br2

{ {
cathode

anode

cell

E = 1.36 - 1.07 = 0.29 V

)(269

Electrochemistry

:
/ .

)(-
:
)Fe(s) + Ni 2+ (aq
) Fe2+ (aq) + Ni(s

. ( E cell = 0.19V, E Fe = - 0.44 V ) :

:
E cell = E N i - E Fe

E N i = E cell
+ E Fe

)E N i = 0.19 + (- 0.44
E N i = - 0.25 V

)(-
= - 0.44 V, E Cu = + 0.34 V ) :

Fe

(E

:
( ).(II
( ).(II

)(270

Electrochemistry

:
/ .

( )(II

) ) ((- ) ( E Fe < E Cu

.

)(-

( )(II
) ) ((- ) ( E Cu > E Fe
.

)(-

)(271

Electrochemistry

:
/ .

)(-
:

= 0.80 V, ESn
) = - 0.14 V

Ag

(E

:
)Sn 2+ (aq, 1 M) + 2Ag(s
) Sn(s) + 2Ag + (aq, 1M

.
:
)Sn 2+ (aq, 1 M) + 2Ag(s
) Sn(S) + 2Ag + (aq, 1M

)(
)(.

E cell = E cathode - E anode

{ 123
Ag

Sn

E cell = - 0.14 - (0.8) = - 0.94 V

) (.

)(272

Electrochemistry

:
/ .

:
)Sn(S) + 2Ag + (aq, 1M
) Sn 2+ (aq, 1 M) + 2Ag(S

:
E cell = E cathode - E anode
{ 123
Sn

Ag

E cell = 0.8 - (- 0.14) = + 0.94 V

)(-
:

= 0.80 V, E Sn
) = - 0.140 V

Ag

(E

:
)Sn 2+ (aq, 1M) + 2Ag(s
) Sn(s) + 2Ag + (aq,1M

( .
( .
.

(
oxidation
reduction
)2Ag(s
2Ag + (aq) + 2e
Sn 2+ (aq) + 2e
) Sn(s
anode
cathode
144444444444444244444444444444
3
overaal reaction
2+
+
)Sn (aq, 1M) + 2Ag(s) Sn(s) + 2Ag (aq,1M

)(273

Electrochemistry

:
/ .

(
) (anode ) (cathode :
E anode
{

E cathode
123

)Ag (EAg = 0.80 V

= E cell

Sn (ESn
)= - 0.140 V

)E cell = (- 0.140 V) - (0.80 V

E cell = - 0.94 V

:
)Sn 2+ (aq, 1M) + 2Ag(s
) Sn(s) + 2Ag + (aq,1M

:
)Sn(s) + 2Ag + (aq,1M
) Sn 2+ (aq, 1M) + 2Ag(s

)(
)( . :

E anode
{

Sn (ESn
)= - 0.140 V

E cathode
123

= E cell

)Ag (E Ag = 0.80 V

)E cell = (0.80 V) - (- 0.140 V

E cell = + 0.94 V

(274)

Electrochemistry

:
./

(-)
Consider the following galvanic cell (Fig. (3 - 45))
a) What is the quantitative change in the cell voltage on
increasing

the

ion

concentrations

in

the

anode

compartment by a factor of 10?

b) What is the quantitative change in the cell voltage on
increasing the ion concentrations in the cathode
compartment by a factor of 10?

Fig. (3-45)

Electrochemistry

(275)

:
./

(-)
Consider the following galvanic cell (Fig (3 - 46)) :
a) What is the quantitative change in the cell voltage on
decreasing the ion concentrations in the anode
compartment by a factor of 100?
b) What is the quantitative change in the cell voltage on
decreasing the ion concentrations in the cathode
compartment by a factor of 100?

Fig. (3-46)

)(276

Electrochemistry

:
/ .

)(-
:
) = - 0.7628 V, E Cd = - 0.4029 V

Zn

(E

(
(
( .

( :



E c a th o d e > E a n o d e
{
123
Zn

Cd

( :
oxidation

Zn 2+ + 2e
Zn

reduction

) Cd(S
Cd 2+ (aq) + 2e

overall reaction

) Zn 2+ (aq) + Cd(s
)Zn(s) + Cd 2+ (aq

(277)

Electrochemistry

:
./

: (

E cell = E cathode - E anode

123 {
Cd

Zn

E cell = - 0.4029 - (- 0.7628)

E cell = + 0.3599 V
(-)
:
Cd(S) Cd 2+ (aq, 1 M) KCl(1.0 N) Hg 2 Cl 2 (S) Hg(L) Pt(s)

Ecell = 0.6830 V, EHg2Cl2 = 0.2676 V :

C d (S ) C d 2 + (a q , 1 M )
1 4 4 42 4 4 43
a n o d e (C d )

E c e ll = E c a th o d e - E a n o d e
123 {
c a lo m e l

Cd

0 .6 8 3 0 = 0 .2 6 7 6 - E a n o d e
{
Cd

E a n o d e = 0 .2 6 7 6 0 .6 8 3 0
{
Cd

Cd

= - 0 .4 1 5 4 V

K C l(1 .0 N ) H g 2 C l 2 (S ) H g (L ) P t(s )
1 4 4 4 4 442 4 4 4 4 4 43
c a th o d e (c a lo m e l)

)(278

Electrochemistry

:
/ .

)(-
:
)Ni(s) + 2AgCl(s
) Ni 2+ (aq) + 2Ag(s) + 2Cl - (aq

)Ni(s) Ni 2+ (aq) Ag + (aq) Ag(s

)(-
:
)Ni(s) Ni 2+ (aq , 1 M) Fe3+ (aq , 1M), Fe2+ (aq , 1M) Pt(s

:
)Ni(s
Ni 2+ (aq) + 2e

:
Fe 2+ (aq) + 2e
) Fe(s

:
)Ni(s) + Fe 2+ (aq
) Ni 2+ (aq) + Fe(s

)(279

Electrochemistry

:
/ .

)(-
:
)Cd(s) Cd 2+ (aq , a = 1) Cu 2+ (aq , a = 1) Cu(s

(
(

) = - 0.4029 V, E Cu = + 0.337 V

Cd

(E

(
)Cd(s)/Cd 2+ (aq , a = 1) // Cu 2+ (aq , a = 1)/Cu(s
144424443 144424443
anode

oxidation
Cd2+ (aq) + 2e
)Cd(s

cathode

reduction
Cu 2+ (aq) + 2e
) Cu(s

144444444
42444444444
3
overall reaction
)Cd(s) + Cu 2+ (aq
) Cd2+ (aq) + Cu(s

( :
E cell = E cathode - E anode
{ 123
Cd

Cu

)E cell = 0.337 - (- 0.4029

E cell = 0.7399V

)(280

Electrochemistry

:
/ .

)(-
:
)Ni 2+ (aq) + Fe(s
) Ni(s) + Fe 2+ (aq

( )( )(.
( .
( .
( )(1 M
(E Fe = - 0.44 V, E Ni = - 0.25 V) :

(
)( :
) (:
Ni 2+ (aq) + 2e
) Ni(s

.
)( : ) (
)(.
)Fe(s
Fe 2+ (aq) + 2e

)(281

Electrochemistry

:
/ .

.
( ( :
) (- :

)(-

( :
:
2+
RT Fe
E cell = Eln
ZF Ni 2+

cell

RT
) E cell = ( E cathode - E anode)ln (1
123 { ZF
Fe
Ni

E cell = ( - 0.25 - ( - 0.44) ) - 0

E cell = 0.19 V

)(282

Electrochemistry

:
/ .

) (ln Q
) (ln 1 = 0
) . (E cell = E cell
)(-
:
)Cl- (aq) Cl2 (g

)Cu(s) Cu 2+ (aq

= + 0.337 V, E Cl2 = 1.3595 V

Cu

(E

( .
( .

)Cl- (aq) Cl2 (g

144
42444
3

chlorine electrode - cathode

reduction
Cl2 (g) + 2e
) 2Cl- (aq

)Cu(s) Cu 2+ (aq
144424443

{
salt
bridge

+ 2e

copper electrode - anode

oxidation
)Cu(s
) Cu 2+ (aq

144444444444424444444444443
)overall reaction Cu 2+ (aq) + 2Cl- (aq
)Cu(s) + Cl2 (g

E Cell = E cathode
- E anode
{ 123
Cu

Cl2

E Cell = 1.3595 - 0.337

E Cell = 1.0225 V

)(283

Electrochemistry

:
/ .

)(-
:

)Cl2 (g) Cl- (aq) Cu 2+ (aq) Cu(s

:

= + 0.337 V, E Cl2 = 1.3595 V

Cu

(E

( .
( .

)Cu(s) Cu 2+ (aq

14442444
3
copper electrode - cathode

)reduction Cu(S
Cu 2+ (aq) + 2e

{
salt
bridge

)Cl- (aq) Cl 2 (g

1442443
Cl2 (g) + 2e

chlorine electrode - anode

oxidation
)2Cl- (aq

144444444444
42444444444444
3
)overall reaction Cu(s) + Cl (g
)Cu 2+ (aq) + 2Cl- (aq
2

E Cell = E Cathode - E Anode

{ {
Cl 2

Cu

E Cell = 0.337 - 1.3595

E Cell = - 1.0225 V

)(284

Electrochemistry

:
/ .

.

) (1.0225 V
:
-

overall reaction
)Cu (aq) + 2Cl (aq
) Cu(s) + Cl 2 (g
2+

) (1.0225V .
)(-
/
.
( .
( .
(

= 0.799 V, E Cu
= 0.337 V :
2+/
Cu

Ag + /Ag

(E

)(285

Electrochemistry

:
/ .

) (
.

Fig. (3-48) : The copper/silver voltaic cell utilizes the reaction :

)Cu(s) + 2Ag + (aq
) Cu 2+ (aq) + 2Ag(s

The potential of this cell is 0.46 volt.

)(286

Electrochemistry

:
/ .

)(-
) ( PH = 1
2

) (25 C ).(pH = 5

) H 2 (g
2H + + 2e
PH2
0.0591
log
2
2
] [H2

E H = E H -

0.0591
1
log
2
2
] [H2

EH = 0 -

0.0591
2
] log [ H 2
2
2 0.0591
EH = +
] log [ H 2
2
] E H = 0.0591log [ H 2
EH = +

)] E H = - 0.0591( - log [ H 2
E H = - 0.0591pH

) = - 0.0591pH

E H = - 0.0591pH
)E H = - 0.0591 (5
E H = - 0.2955 V

: ( EH

)(287

Electrochemistry

:
/ .

)(-
)
)5

((pH

) . ( E calomel = + 0.242 V

(
( ).(e.m.f
( .

( :
E H = - 0.0591pH
)E H = - 0.0591 (5
E H = - 0.2955 V

( :
E cell = E cathode - E anode
{ 123
H

Hg 2 Cl2

) E cell = 0.242 - ( - 0.2955

) E cell = 0.242 - ( - 0.2955
E cell = 0.5375 V

)(288

Electrochemistry

:
/ .

( :
2H (aq) + 2e
)H 2 (g
+

) 2Hg + 2Cl- (aq

Hg 2 Cl2 (s) + 2e
________________________________________
)H 2 (g) + Hg 2 Cl2 (s
) 2H + (aq) + 2Hg + 2Cl- (aq

)(-

) (e.m.f )

=1

(P

H2

) + 0.242 V

= ( E calomel )V

(0.480

) .(25 C .

E cell = E calomel - E Hydrogen

0.480 = 0.242 E Hydrogen
E Hydrogen = 0.242 0.480
E Hydrogen = - 0.238 V

:
E H = - 0.0591 pH
- 0.238 V = - 0.0591 pH
- 0.238
= pH
- 0.0591
pH = 4.030

)(289

Electrochemistry

:
/ .

)(-
) (e.m.f
) (0.01 M
) (0.425 V ) .(25 C
.

) = 0.7991 V, E Cu = 0.337 V

Ag

(E

Cu 2+ (aq) + 2e
Cu
Ag
2 Ag + (aq) + e
__________________________________
)Cu(s) + 2Ag + (aq
Cu 2+ (aq) + 2Ag

:
)Cu(s) + 2Ag + (aq
Cu 2+ (aq) + 2Ag
E cell = E Ag - E Cu

0.0591
1 0.0591

0.425 = E Aglog
- E Cu +
log Cu 2+
2
+

2
2

Ag

2
0.0591
0.0591

0.425 = E Ag +
log Ag + - E Cu
+
log Cu 2+
2
2

0.0591

0.425 = ( 0.7991 +0.0591 log ( 0.01) ) - 0.337 +

log Cu 2+
2

0.0591
0.425 = 0.6809 - 0.337 log Cu 2+
2
0.0591
log Cu 2+ = 0.6809 - 0.337 - 0.425
2
0.02955 log Cu 2+ = 0.0811
0.0811
= log Cu 2+

0.02955
log Cu 2+ = 2.7445
Cu 2+ = 1.80 10-3

)(290

Electrochemistry

:
/ .

)(-
) (Fe3+/Fe2+ ) (25 C
) (Fe3+/Fe2+ :
) , 1 10-1 , 100 , 1 101 , 1 102

-2

(1 10

. E Fe3+ /Fe2+ = 0.771 V

Fe 2+
Fe3+ + e
Fe 2+
- 0.0591 log
Fe3+

E = E Fe3+ /Fe2+

Fe3+
+ 0.0591 log
Fe 2+

Fe3+ /Fe 2+

Fe3+
+ 0.0591 log
Fe 2+

Fe3+ /Fe 2+

E=E

E=E

(291)

Electrochemistry

:
./
Fe3+
1.
= 1 10-2
Fe 2+
E=E

Fe3+ /Fe 2+

Fe3+
+ 0.0591 log
Fe 2+

E = 0.771 + 0.0591 log (1 10-2 )

E = 0.6528 V
Fe3+
= 1 10-1
2.
Fe 2+
Fe3+
E = E Fe3+ /Fe2+ + 0.0591 log 2+
Fe

E = 0.771 + 0.0591 log (1 10-1 )

E = 0.7119 V
Fe3+
3.
= 1 100
2+
Fe
Fe3+
E = E Fe3+ /Fe2+ + 0.0591 log 2+
Fe

E = 0.771 + 0.0591 log (1 100 )

E = 0.771 V
Fe3+
= 1 101
4.
2+
Fe
E=E

Fe3+ /Fe 2+

Fe3+
+ 0.0591 log
Fe 2+

E = 0.771 + 0.0591 log (1 101 )

E = 0.8301 V
Fe3+
5. 2+ = 1 102
Fe
E=E

Fe3+ /Fe 2+

Fe3+
+ 0.0591 log
Fe 2+

E = 0.771 + 0.0591 log (1 102 )

E = 0.8892 V

)(292

Electrochemistry

:
/ .

)(-
:
)Pt MnO -4 (aq, 1 10-2 M), Mn 2+ (aq , 2 10-3M), H + (aq,1 10-2 M

= 1.51 V

2+

. ( E MnO /Mn
4

:
MnO -4 (aq) + 8H + (aq) + 5e
) Mn 2+ (aq) + 4H 2 O(L
Mn 2+
0.0591

log
8
5
MnO -4 H +

E MnO- /Mn 2+ = E MnO- /Mn 2+

4

) 2 10-3
(
0.0591
E MnO- /Mn 2+ = 1.51log
8
4
5
) (1 10-2 ) .(1 10-2
) 2 10-3
(
0.0591
E MnO- /Mn 2+ = 1.51log
8
4
5
) (1 10-2 ) .(1 10-2
E MnO- /Mn 2+ = 1.329 V
4

)(-
:
5Fe2+ + MnO-4 + 8H +
5Fe3+ + Mn 2+ + 4H 2O

= 0.77 V, E MnO2+ /Mn 2+ =1.51 V

4

Fe2+ /Fe3+

(E

)(293

Electrochemistry

:
/ .

+ MnO-4 + 8H +
) 5Fe3+ + Mn 2+ + 4H 2 O

2+

:
5

Fe3+ Mn 2+
=K
5
8
Fe2+ MnO-4 H +

:
5Fe2+
5Fe3+ + 5e
MnO-4 + 8H + + 5e
Mn 2+ + 4H 2 O

:
5Fe3+ + 5e
5Fe 2+
5

Fe3+
0.0591

E Fe3+ /Fe2+ = E Fe3+ /Fe2+ +

log
5
5
Fe 2+
Fe3+
0.0591

E Fe3+ /Fe2+ = E Fe3+ /Fe2+

log
5
Fe 2+
Mn 2+ + 4H 2 O
MnO-4 + 8H + + 5e
Mn 2+
0.0591

log
8
5
MnO-4 . H +

MnO-4 /Mn 2+

E MnO- /Mn 2+ = E
4

( 5Fe

Electrochemistry

(294)

:
./

:
E MnO- /Mn 2+ = E Fe2+ /Fe3+
4

Fe3+
Mn 2+
0.0591
0.0591
E
log
= E MnO- /Mn 2+
log
+
8
4
5
5
Fe 2+
MnO -4 . H +
Fe3+
Mn 2+
0.0591
0.0591
0.77 +
log
log
= 1.51
8
5
5
Fe 2+
MnO -4 . H +
Fe3+ 0.0591
Mn 2+
0.0591
log
log
1.51 0.77 =
+
8
5
5
Fe 2+
MnO -4 . H +

Fe3+ /Fe 2+

Fe3+
Mn 2+
0.0591

0.74 =
log
+ log
8
2+
+

5
Fe
MnO 4 . H

Fe3+ . Mn 2+
0.0591

0.74 =
log
2+
+ 8
5
Fe . MnO 4 . H

0.0591
0.74 =
( log K )
5
0.74
log K =
0.0591/5
0.74 5
log K =
0.0591
log K = 62.606
K = 4.03 1062

)(295

Electrochemistry

:
/ .

)(-
) (
:
)a) H 2 (g) + I2 (g
) 2HI(aq
)b) Mn 2+ (aq) + In + (aq
) Mn 3+ (aq) + In(s
)c) Hg 2 Cl2 (s) + Cd(s
) 2Hg(L) + CdCl2 (aq

)(-
:
a) Pt, H 2 HCl AgCl,Ag
b) Pt Fe2+ ,Fe3+ Sn 4+ ,Sn 2+ Pt
c) Pt,Cl2 HCl CrO2-4 Ag 2 CrO 4 ,Ag

)(-
/

) (Ag/Ag+ )(Hg,Hg2Cl2/Cl-

) .(0.2360 V (+
) 0.2812 V .
0.5172 V :

)(296

Electrochemistry

:
/ .

)(-
:
a) Fe Fe 2+ H + H 2 , Pt
b) Zn ZnCl2 AgCl,Ag
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................

)(297

Electrochemistry

:
/ .

)(-
:
Hg 2 Cl2 + Cd
2Hg + CdCl2
Hg 2SO 4 + Pb
2Hg + PbSO 4
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................

)(298

Electrochemistry

:
.

" "
th

04 Chapter
The Relationship Between
Potential and Concentration
""Nernest Equation

)(299

Electrochemistry

:
.

" "
The Relationship Between Potential and Concentration

Dependence of Electrode Potential Concentration

:

"".

:
aA + bB
cC + dD

) (a, b, c, d
) (A, B ).(C, D
G

:
G = G + RT lnQ

a a
+ RT ln C a D b
aA aB
d

G = G

)(300

Electrochemistry

:
.

c
d

aC aD

a
b
G = G + RT ln

a
a

A
B

:
G = G + RT lnQ

:
: a

: G .

: Q .

).(Vant Hoff's Isotherm

lnQ = ln 1 = 0 . G = G

:
G = - RT lnK

: K .
:

G = - z E F

(301)

Electrochemistry

:
.

:
G = - z E F

G = - RT lnK G = - z E F
:

c
d

aC aD

G = G + RT ln

a
b

a
a
A B

a a
+ RT ln C a D b
aA aB
c

G = G

G = - RT ln K
G = - n E F

a a
- z E F = - RT ln K + RT ln C a D b
aA aB
c
d
aC aD

-zEF
- RT
RT
=
ln K +
ln
-zF
-nF
- z F a A a a B b
c
d
aC aD

RT
RT
E=
ln K RT ln
a
b
zF
zF
aA aB
c

RT
ln K = E
zF

RT

ln K

zF

(302)

Electrochemistry

:
.

RT

ln K = E

zF

c
d

RT
RT a C a D
ln K ln
E =

a
b

z
F
z
F
a
a

A
B

c
d

a
a

RT
C
D
ln
E = E
a
b

z
F
a A a B

c
d

RT a C a D

ln
E = E
a
b

z
F
a A a B

: G = - z E F
c
d

a
a

G = G + RT ln C a D b

a A a B

a a
G = G + RT ln C a D b
aA aB
c
d
aC aD

- z E F = - z E F + RT ln
a
b
aA aB
c
d
a
a

RT
E = E ln C a D b
zF
aA aB
c

:
RT a C a D
E=E ln
a
b
zF
aA aB
c

)(303

Electrochemistry

:
.

RT

ln Q
E = EzF

) (Nernest's Equation
( )
.
:
R = 8.314 J/K . mol = 8.314 V . C/K. mol

V
:
Volt

C : coulomb

: R .
: T ).(K = C + 273
: z
(
).
: F

) (96487 96500 C

.
: Q ( ) =

) (x, y

)(304

Electrochemistry

:
.

) (Vant Hoff's Isotherm :
G = G + RT lnQ

: Q ) (K .
.



.
) (Wele :
Wele = z E F

G = - z E F
:

)(305

Electrochemistry

:
.

G = G +RT lnQ
- z E F = - z E F + RT lnQ
-zEF
- z EF
RT
=
+
lnQ
-zF
-zF
-zF
RT
E = ElnQ
zF

:
RT
lnQ
zF
2.303 8.314 298
E = Elog Q
z 96500
0.05916
E = ElnQ
z
E = E -

9881.

)(306

Electrochemistry

:
.

()1-4

Cu(s) + 2Ag + (aq)

) Cu 2+ (aq) + 2Ag(s
.

a Cu 2+

=Q

a Ag+

.

.
()2-4

) Cl2 (g) + H2 (g
2Cl- (aq) + 2H+ (aq)

a a P . P
a a a a
H2

H2

Cl2

Cl

Cl2

Cl

=Q

)(307

Electrochemistry

:
.

) (M = mol/L
) (a

:
Zn(s)
Zn 2+ (aq) + 2e
Zn 2+
=Q
1
2+
Cu (aq) + 2e
) Cu(s
1
Cu 2+

( )(25 C
) (25 C = 298 K
lnQ = 2.303 logQ :
RT
lnQ
zF
8.314 J/K. mol 298.15 K (2.303) logQ
E = E)z (96500 C
0.0592 V
E = Elog Q
z
E = E -

)(308

Electrochemistry

:
.

(
)25 C :
RT
lnQ
zF

E = E -

0.0592
logQ :
z

E = E -

)(309

Electrochemistry

:
.

()3-4

RT
lnQ
ZF

E Electrode = E Electrode -

): (25 C
)Zn Zn 2+ (aq, a = 0.1

EZn = - 0.7628 V

Zn 2+ (aq, a = 1)
) Zn 2+ (aq

( ): ((T = 298 K, a = 0.1

RT
lnQ
zF
2.303 R T
1
= E Znlog
zF
a Zn 2+

E Electrode = E Electrode -

2.303 8.314 298

1
log

2 96500
0.1

E Zn

E Zn = - 0.7628 E Zn = - 0.79240 V

)(310

Electrochemistry

:
.

lnQ = 0
:
RT
lnQ = 0
zF

E = E

.

ln Q 0

)(311

Electrochemistry

:
.

:
RT
lnQ 0
zF

:
RT
ln Q
zF
RT
ln Q
zF

E Cell = E Cell
-

E Cell

= E Cell

E Cell = E Cathode - E Anode

) (E

) (E . z F ln Q

RT

( ) :
RT
lnQ
zF

E = E -

: z (
( ) .
) (z
) (z .

)(312

Electrochemistry

:
.

()4-4
): (25 C
Zn Zn 2+ (aq, a = 0.01) Cl- (aq, a = 0.1) Hg 2Cl2 ,Hg

= - 0.7628 V, EHg2Cl2 = 0.2678 V

Zn

:
Zn(s)
Zn 2+ (aq) + 2e
Hg 2 Cl2 (s) + 2e
) 2Hg(L) + 2Cl- (aq
___________________________________________
Zn(s) + Hg 2Cl2 (s)
) Zn 2+ (aq) + 2Hg(L) + 2Cl- (aq

E cell = E cathode
- E anode
Zn

Hg 2 Cl2

E cell = 0.2678 - - 0.7628

E cell = + 1.0306 V

)(313

Electrochemistry

:
.

:
Zn(s) + Hg 2Cl2 (s)
) Zn 2+ (aq) + 2Hg(L) + 2Cl- (aq

2.303 RT
log a . a
zF

RT a Hg . a Cl- . a Zn 2+

= E cellln
zF
a Hg Cl . a Zn
2

Zn 2+

E cell

Cl-

E cell = E cell

2
0.0591
log a Cl- . a Zn 2+
2
0.0591
2
= 1.0306log 0.1 . 0.01
2
= 1.1488 V

E cell = 1.0306E cell

E cell

) .(a = 1
) (a ) (m ) (M
:
a=F.m
a=F.M

) (F .

)(314

Electrochemistry

:
.

.
()5-4
z=2

Cu(s)
Cu 2+ (aq) + 2e

z=1

Ag + (aq) + e
) Ag(s

) (z
:
Cu(s)
Cu 2+ (aq) + 2e
2Ag + (aq) + 2e
) 2Ag(s
------------------------------------------------------------------z=2

Cu(s) + 2Ag + (aq)

) Cu 2+ (aq) + 2Ag(s

: ln = 2.303( 2.303 log

).

)(315

Electrochemistry

:
.

E Electrode

( )

).(1 atm

).(E

EElectrode ) (Ecell
)(Nernest Equation

)(316

Electrochemistry

:
.

()6-4
Zn(s)
Zn 2+ (aq) + 2e
) (a Zn 2+

) = (a Zn 2+
1
Cu 2+ (aq) + 2e
) Cu(s
1
) (a Cu 2+

=Q

=Q

) (a .

()7-4

): (Hydrogen Chlorine
)Pt, H2 (s) HCl (aq) Cl2 , Pt (s

)
.
) ) (a
).(P

)
)(oxidation

H 2 (g)
2H + (aq) + 2e

)(reduction

Cl2 (g) + 2e
) 2Cl- (aq

________________________________________
H 2 (g) + Cl2 (g)
) 2H + (aq) + 2Cl- (aq

)(317

Electrochemistry

:
.

z = 2 :

a H+ . a Cl-

0.0591
log
2
a H2 . a Cl2

E = E -

:
2

0.0591
E=Elog a . a
2
a + . a Cl0.0591
E = Elog H
2
PH2 . PCl2
2

()8-4

Cl

:
)Zn(s) ZnCl2 (aq) Cl2 , Pt (s

)
.
) ) (a
).(P

)(318

Electrochemistry

:
.

)(oxidation

Zn(s)
Zn 2+ (aq) + 2e

)(reduction

Cl2 (g) + 2e
) 2Cl- (aq

________________________________________
Zn(s) + Cl2 (g)
) Zn 2+ (aq) + 2Cl- (aq

): (z = 2

a a
0.0591
E=Elog
2
a 1 P 1
0.0591
E=Elog a a
2
2

a 2+ a Cl0.0591
E = Elog Zn
2
a Zn a Cl2

2+

Cl

Cl2

Zn

Zn

Cl

2+

Zn

()9-4

) (0.001M .

) (1 M ).(298 K

:
= + 0.337 V, EZn = - 0.7628 V

Cu

(319)

Electrochemistry

:
.

oxidation reaction
Zn(s)
Zn 2+ (aq) + 2e

Zn(s) + Cu2+ (aq)

reduction reaction
Cu 2+ (aq) + 2e

Cu(S)

overall reaction

Zn2+ (aq) + Cu(s)

ECell

E Cell =

ECell = ECathode
- EAnode

RT
ln Q
ZF

( 25 C)
overall reaction
Zn(s) + Cu 2+ (aq)
Zn 2+ (aq) + Cu(s)

E cell =

E Cell

E cell = Ecathode - Eanode

E cell

0.0591
log Q
Z

Zn 2+
0.0591
=
E
log
Z
=
2
Cu 2+

E cell = 0.337 - (- 0.7628) = 1.10

E cell = 1.10 -

Cell

0.0591 0.001
log

2
1

E cell 1.10 0.02955 log 0.001

E cell 1.10 0.02955 (-3)
E cell 1.10 0.08865
E cell 1.18865 V
E cell 1.19 V

:
: ( Ecell = 1.10 V)

Zn

2+

= 1 M, Cu 2+ = 1M

)(320

Electrochemistry

:
.

= 0.001 M, Cu 2+ =1M

= 1.19 V) :

cell

2+

Zn

(E

) (Cu2+ ) (Zn2+ .

()9-4

) (Zn2+, Cu2+ :
( )1-4 ) (Zn Cu
)(298 K
][Cu2+]//[Zn2+
1.16
1.13
1.13
1.10
1.10

[Zn2+], M
100
10
10
1
1

[Cu2+], M
0.1
1.0
0.1
1.0
0.10

()11-4
) (Cu2+, Zn2+
.

).(298 K

) (Ecell = 0 :

(321)

Electrochemistry

:
.

E Cell =

E cell

E cell = Ecathode - Eanode

E cell

0.0592
log Q
Z

2+

Zn
0.0592
=
E cell
log 2+
Z=2
Cu
E cell = 0.337 - (- 0.7628) = 1.10

Zn 2+
Zn 2+
0.0592
0.0592
0 = 1.10 log
1.10
log
2
2
Cu 2+
Cu 2+
Zn 2+
Zn 2+
1.10
1.10 0.0296 log

log

Cu 2+
Cu 2+ 0.0296
Zn 2+
log
37.162
Cu 2+

Zn 2+
1.45 1037
2+
Cu

)11-4(
:
Zn(s) Zn 2+ (aq, 0.1 M) Cu 2+ (aq, 0.2 M) Cu(s)

Zn

= - 0.76 V, ECu
= 0.34 V

:
Zn(s) + Cu 2+ (aq)
Zn 2+ (aq) + Cu(s)

: Q

)(322

Electrochemistry

:
.

Zn 2+
=Q
Cu 2+

0.1
0.2

=Q

E cell = E Cu
- E Zn
anode

cathode

E cell = 0.34 V - (- 0.76) = 1.1 V

: 25 C
RT
lnQ
ZF
8.314 J/K.mol 298 K ln 0.1
= 1.1

2 96500
0.2
= 1.109 V

E cell = E cell
-

E cell
E cell

()12-4
:
2Al(S) + 3I2 (S)
) 2Al3+ (aq) + 6I- (aq

Al3+ = 0.1 mol/L, I- = 0.01 mol/L :

)(323

Electrochemistry

:
.

. EAl = - 1.66 V, EI = 0.54 V :

2

-1
E cell = E I2 - E Al
anode

cathode

)E cell = 0.54 - (-1.66

E cell = 2.2V

-2
).(Z = 6
-3 : Q
2Al(s) + 3I 2 (s)
) 2Al3+ (aq) + 6I - (aq
6

Q = Al3+ I-
Q = 0.1 (0.01)6
2

:
RT
lnQ
ZF
8.314 J/K.mol 298 K ln 0.1 2 (0.01)6
= 2.2
6 96500
= 2.34 V

E cell = E cellE cell

E cell

)(324

Electrochemistry

:
.

()13-4

( )0.005 M
) (0.01 M

= 0.8 V, ECu
= 0.34 V :

Ag

) .
) .
)

) .

) :
oxidation
Cu(s)
Cu 2+ (aq) + 2e
reduction
2Ag + (aq) + 2e
) 2Ag(s
----------------------------------------------------overall reaction
Cu(s) + 2Ag + (aq)
) Cu 2+ (aq) + 2Ag(s

) :
E cell = E Ag - E Cu
anode

cathode

E cell = 0.8 - 0.34

E cell = 0.46 V

)(325

Electrochemistry

:
.

) :
overall reaction
Cu(s) + 2Ag + (aq)
) Cu 2+ (aq) + 2Ag(s

Cu 2+
=Q
2
Ag +
)(0.01
(0.005)2

=Q

) :
RT
lnQ
ZF
(8.314 J/mol. K) (298 K) 0.01
E cell = 0.46ln
2
2 96500
(0.005)
E cell = E cell -

E cell = 0.38 V

()14-4
:
)Cd(s) Cd 2+ (aq , 0.1 M) Cu 2+ (aq , 0.2 M) Cu(s

= 0.34 V, ECd
= - 0.43 V

Cu

) .
) :
Cd 2+ = 0.001 M, Cu 2+ =1 M

)(326

Electrochemistry

:
.

Cd 2+

Cu 2+

Ecell 0

Cd(s) + Cu 2+ (aq)
) Cd2+ (aq) + Cu(s

) :

E cell = E Cu
- E Cd
anode

cathode

)E cell = 0.34 - (- 0.43

E cell = 0.77 V

)
:
RT
lnQ
ZF
(8.314 J/K.mol) (298 K) 0.001
E cell = 0.77ln

2 96500
1
E cell = 0.859 V
E cell = E cell -

)(327

Electrochemistry

:
.

Cd 2+
Cu 2+

: Ecell 0

RT
lnQ
ZF
)(8.314 J/K.mol) (298 K
0 = 0.77lnQ
2 96500
0 = 0.77 - 0.013 lnQ
0.77
= lnQ
59.23
0.013
Cd 2+
59.23
25
=Q
=
e
=
5.29

10
Cu 2+
E cell = E cell -

()15-4
:
)Ag(s) Ag + (aq, 0.1 M) Pb2+ (aq, 2 M) Pb(s

) .
)
= 0.8 V, EPb = - 0.13V

Ag

) Ecell = 1.6 V Pb2+ .

(328)

Electrochemistry

:
.

: )
Ag(s) Ag + (aq , 0.1 M)
anode

oxidation
2Ag(s) 2Ag + (aq) + 2e

Pb 2+ (aq , 2 M) Pb(s)
cathode

reduction
Pb 2+ (aq) + 2e Pb(S)

2Ag(s) + Pb 2+ (aq)
2Ag + (aq) + Pb(s)
overall reaction

: )
Ag(s) Ag + (aq , 0.1 M)

Pb 2+ (aq , 2 M)/Pb(s)

anode

cathode

E cell = E cathode - E anode

Pb

Ag

E cell = - 0.13 - (+ 0.8)

E cell = - 0.93 V

)(329

Electrochemistry

:
.

) : Ecell = 1.6 V
overall reaction
2Ag(s) + Pb 2+ (aq)
) 2Ag + (aq) + Pb(s

RT
lnQ
ZF
8.314 J/K.mol 298 K lnQ
)1.6 = (- 0.932 96500 C
1.6 = - 0.93 - 0.0128 lnQ
0.0128lnQ = - 0.93 - 1.6
E cell = E cell -

- 0.93 - 1.6
0.0128
2.53
lnQ
0.0128
lnQ = - 197.66
= lnQ

Q = 1.44 10-86
2

Ag +
(0.1) 2

=Q
=
= 1.44 10-86
2+
2+

Pb

Pb

2+
83

Pb
= 6.94 10 M

()16-4
)
) (0.001 M ) (Zn2+
= 1 M
(R = 8.314 J/K. mol, T = 25 C, F = 96500 C :

)(330

Electrochemistry

:
.

= 0.337 V, EZn = - 0.7628 V

Zn 2+
Cu 2+

Cu

( .)25 C

:
2+
RT Zn
E cell = Eln
ZF Cu 2+

cell

0.0591 0.001

E cell = E cathode - E anode log

2
1

Zn
Cu

0.0591
0.001
E cell = (0.337 - (- 0.7628)
log

2
1
E cell = 1.0998 + 0.0888
E cell = 1.1886 V

) (0.09 V ) (1.1 V
( )
.

)(331

Electrochemistry

:
.

Zn 2+
Cu 2+

( :)25 C
) (Ecell = 0

Zn 2+
Cu 2+

:
2+
RT Zn
E cell = Eln
ZF Cu 2+

cell

Zn 2+
Zn 2+
0.0591
0.0591
0 1.1
log
1.1
log
2
2
Cu 2+
Cu 2+
Zn 2+
1.1
log

37.16
)Cu 2+ (0.0296
Zn 2+
= shift log 37.16 = 1.445 1037
2+
Cu

()17-4
) ): (25 C
)Sn(s) Sn 2+ (aq, a = 0.6) Pb2+ (aq, a = 0.3) Pb(s

:
= - 0.136V, EPb = - 0.126 V

Sn

)(R = 8.314 J/mol K, F = 96500 C

)(332

Electrochemistry

:
.

) .
)
.

:
Sn(s) + Pb2+ (aq, a = 0.3)
)Sn 2+ (aq, a = 0.6) + Pb(s

= 0.6, Pb2+ = 0.3

2+

Sn

:
Sn(s) + Pb 2+ (aq, a = 0.3)
) Sn 2+ (aq, a = 0.6) + Pb(s
Sn 2+
RT
log
nF
Pb 2+

Sn 2+
log
Pb 2+
Sn 2+
log
Pb 2+

2.303 8.314 V. C mol-1 K -1 298 K

2 96500 C
2.303 8.314 V. C mol-1 K -1 298 K
2 mol e 96500 C
0.0592 V
0.6
log
2
0.3

cell

E cell = E

cell

E cell = E

cell

E cell = E

E cell 0.126 (0.136)

0.0592
log 2
2
1.089 10-3 V

E cell 0.01
E cell

)(333

Electrochemistry

:
.

) :
(aq, a = 0.3)
Sn 2+ (aq, a = 0.6) + Pb(s)

2+

Sn(s) + Pb

G = - n E F
G = - 2 1.089 10-3 96500
G = - 210.177 J

) :
G = - n E F
G = - 2 0.01 96500
G = - 1930 J

G = - 210.177 J

= - 1930 J

. )(a = 0.6
).(a = 0.3
()18-4

:
) )([Zn2+] = 0.01 M, [Cu2+] = 0.001M
) )([Zn2+] = 0.001 M, [Cu2+] = 0.01M

) (25 C :

. ECu = 0.337 V, EZn = - 0.7630 V

(334)

Electrochemistry

:
.

: ( )
Zn(s)
Zn 2+ (aq) + 2e
Cu 2+ (aq) + 2e
Cu(s)
_________________________________
Zn(s) + Cu 2+ (aq)
Zn 2+ (aq) + Cu(s)

:
:
:
([Zn2+] = 0.001 M, [Cu2+] = 0.01M)
E cell = E

cell

Zn 2+
0.0591
log
2
Cu 2+

E cell = E cell
E Cu - EZn

Zn 2+
0.0591
log 2+
2
Cu

([Zn2+] = 0.01 M, [Cu2+] = 0.001M)

E cell = E

cell

E cell = E

Zn 2+
0.0591
log
2
Cu 2+

cell

E Cu - EZn

Zn 2+
0.0591
log
2
Cu 2+

E cell = 0.337 - (- 0.7630

0.0591
0.001
log

2
0.01

E cell = 0.337 - (- 0.7630

E cell = 0.337 - (- 0.7630

0.0591
0.001
log

2
0.01

0.0591
0.01
log

2
0.001

E cell = 0.337 - (- 0.7630

0.0591
0.01
log

2
0.001

E cell = 1.1

0.0591
0.001
log

2
0.01
= 1.130 V

E cell = 1.1
E cell

0.0591
0.001
log

2
0.01

E cell = 1.1

0.0591
0.01
log

2
0.001
= 1.07 V

E cell = 1.1
E cell

0.0591
0.01
log

2
0.001

(335)

Electrochemistry

:
.

:
Ecell = Ecathode - Eanode
Zn(s)
Zn 2+ (aq) + 2e
[Zn2+] = 0.001
Zn(s)
Zn 2+ (aq) + 2e
0.0591
log Zn 2+
2
0.0591
= - 0.7630 +
log 0.001
2
= - 0.8520

Cu 2+ (aq) + 2e
Cu(s)
2+
[Cu ] = 0.01
Cu 2+ (aq) + 2e
Cu(s)
0.0591
1
log
2
Cu 2+

E Zn = E Zn +

E Cu = E Zn -

E Zn

E Cu = 0.337 -

E Zn

0.0591
1
log
2
0.01

E Cu = 0.2780

E cell = E Cu - E Zn

E cell 0.2780 0.8520

E cell 1.130 V
Zn(s)
Zn 2+ (aq) + 2e

Cu 2+ (aq) + 2e
Cu(s)

[Zn2+] = 0.01

[Cu2+] = 0.001

Zn(s)
Zn 2+ (aq) + 2e
0.0591
log Zn 2+
2
0.0591
= - 0.7630 +
log 0.01
2
= - 0.822 V

Cu 2+ (aq) + 2e
Cu(s)
0.0591
1
log
2
Cu 2+

E Zn = E Zn +

E Cu = E Zn -

E Zn

E Cu = 0.337 -

E Zn

0.0591
1
log
2
0.001

E Cu = 0.248

E cell = E Cu - E Zn

E cell 0.248 0.822

E cell 1.07 V

)(336

Electrochemistry

:
.

()19-4

:
Pb2+ (aq) + Sn(s)
) Pb(s) + Sn 2+ (aq

) .

) :

) :

= Pb2+

2+

Sn

=1 10-2 mol/L, Pb2+ = 0.2 mol/L

2+

Sn

= 0.4 mol/L, Pb2+ = 0.005 mol/L

2+

Sn

.
....................................................................................................................................... ............................
....................................................................................................................................... ............................
....................................................................................................................................... ............................
....................................................................................................................................... ............................
....................................................................................................................................... ............................
....................................................................................................................................... ............................
....................................................................................................................................... ............................
....................................................................................................................................... ............................
....................................................................................................................................... ............................
....................................................................................................................................... ............................
....................................................................................................................................... ............................
....................................................................................................................................... ............................
....................................................................................................................................... ............................

)(337

Electrochemistry

:
/ .

cell

05th Chapter
Determination of Equilibrium Constant From
EMF Measurement

The Relationship Between

Equilibrium Constant
and E

cell

)(338

Electrochemistry

:
/ .

Equilibrium Constant From EMF Measurement

E
The Relationship Between Equilibrium Constant

and E cell

cell

.
:

Ecell = Ecathode - Eanode

)(339

Electrochemistry

:
/ .

( )

( )
= Ecathode - Eanode

Ecell

.
)(exhausted cell

:
RT
lnQ
zF

E cell = Ecell
-

G = G + RTlnQ

)(340

Electrochemistry

:
/ .

:
E=0
G = 0
Q=K

:
RT
lnK
zF
G o = - R T lnK
= E ocell

:
RT
o

lnK
= E cell
zF

o
G = - R T lnK

:
G = - z Ecell F

:
G = - R T ln K & G = - Z E cell F
- R T ln K= - Z E cell F
R T ln K= Z E cell F
Z E cell F
RT

E cell F/RT

= lnK
Z

K = e

)(341

Electrochemistry

:
/ .

E cell :

R T ln K = z E cell F
lnK

RT
zF

cell

= E

)(K
:
Z E cell F
RT

= lnK

lnK

RT
ZF

= E cell

RT

E
=
lnK

cell ZF

Electrochemistry

(342)

:
./

Fig. (5-1) : Relationships among Ecell , K and G

, K . Given any
Fig. (5-2) : The relationships linking G , E cell
one of the values, the other two can be calculated.

)(343

Electrochemistry

:
/ .

()1-5
): (25 C
Hg 2Cl2 (s) + Zn(s)
) 2Hg(L) + 2Cl- (aq) + Zn 2+ (aq

= - 0.7628 V, EHg2Cl2 = 0.2678 V

Zn

:
Zn(s)
Zn 2+ (aq) + 2e
Hg 2 Cl2 (s) + 2e
) 2Hg(L) + 2Cl- (aq
___________________________________________
Zn(s) + Hg 2Cl2 (s)
) Zn 2+ (aq) + 2Hg(L) + 2Cl- (aq

:

Z E cell F
RT

= lnK

Z
F

R
T

E cell

2 0.2678 - (-0.7628) 96500

8.314 298

80.28

k=e

G = - z E F
G = - 2 0.2678 - (- 0.7628) 96500

k=e

k = e

k = 7.331 1034

G = - 198905.8 J

)(344

Electrochemistry

:
/ .

G o = - R T lnK
- 198905.8 = - 8.314 298 lnK
- 198905.8
= lnK
- 8.314 298
- 198905.8

- 8.314 298

K=e

K = e80.28
K = 7.331 1034
()2-5
)(Ag+/Ag
)V

(0.7991

) (Ksp = 4.95 10-13

)(Ag, AgBr/Br-

:
Ksp = 4.95 10-13

) Ag + (aq) + Br - (aq
AgBr(s)

H2 O

)(345

Electrochemistry

:
/ .

:
E anode 0.7991 V

Ag(s)
Ag + (aq) + e

? E cathode

AgBr(s) + e
) Ag(s) + Br - (aq

________________________________________
AgBr(s)
) Ag + (aq) + Br - (aq

Ecell = Ecathode
- Eanode

( )
:
RT
ln K sp
zF
8.314 x 298
= E cell
ln 4.95 10-13
2 96500
E cell = - 0.7275 V
= E cell

E cell = E cathode
- E anode

- 0.7275 = E cathode 0.7991

E cathode - 0.7275 + 0.7991
E cathode 0.0716 V

)(346

Electrochemistry

:
/ .

()3-5
) (K :
)Zn(s) Zn 2+ (aq, 1 M) Cu 2+ (aq, 1 M) Cu(s

:
= - 0.7628 V, ECu = + 0.337 V

Zn

z E cell F
= lnK
RT
2 0.337 - (- 0.7628 ) 96500 C
= lnK
= 85.69
)(8.314 J/K.mol) (298 K
K= e85.69 =1.64 1037

()4-5
:
)Ni(s) Ni 2+ (aq, 1 M) Cu 2+ (aq, 1 M) Cu(s

= - 0.25 V, ECu
= 0.337 V

Ni

)(347

Electrochemistry

:
/ .

:
)
)
)

) :
)Cu 2+ (aq, 1 M)/Cu(s

)Ni(s) Ni 2+ (aq, 1 M

cathode

2+
Cu (aq) + 2e
) Cu(s

anode

Ni(s)
Ni 2+ (aq) + 2e

Ni(s) + Cu 2+ (aq)
) Ni 2+ (aq) + Cu(s

) :

E cell = E cathode - E anode

Ni

Cu

)E cell = 0.337 - ( - 0.25

E cell = 0.587 V

) :
G = - z E cell F
G = - 2 (0.587) 96500
G = - 113291 J
G = - 113.3 kJ

)(348

Electrochemistry

:
/ .

()5-5
:
)Ag + (aq, 1 M) Ag(s

)Zn(s) Zn 2+ (aq, 1 M

:
= - 0.764 V, EAg = 0.799 V

Zn

)
)

Zn 2+
Ag +

)(0 V

) :
Ecell = E cathode - E anode
Zn

Ag

E = 0.799 - (- 0.764) = 1.563 V

Zn 2+
Ag +

:
Zn(s) + 2Ag + (aq)
) Zn 2+ (aq) + 2Ag(s

(349)

Electrochemistry

:
./

:
2+
RT Zn
E cell = E ln
ZF Ag + 2

Zn 2+
0.0591
0 =1.563 log
2
2
Ag +

cell

Zn 2+
0.0591
1.563 =
log
2
2
Ag +
Zn 2+
1.563
log

2
0.02955
Ag +
Zn 2+
log
52.89
+ 2
Ag
Zn 2+
= 7.76 1052
2
Ag +

)6-5(
:
Cu(s) Cu 2+ (aq ,1M) Pb2+ (aq ,1M) Pb(s)

Cu

= 0.337 V, EPb = - 0.126 V

)(350

Electrochemistry

:
/ .

)
)

) :
)Pb 2+ (aq ,1M) Pb(s

)Cu(s) Cu 2+ (aq ,1M

cathode

anode

E cell = E cathode - E anode

Cu

Pb

E cell = - 0.126 - 0.337

E cell = - 0.463 V

) :

G = - z E cell
F

G = - 2 (- 0.463) 96500
G = + 89359 J
G = 89.4 kJ

:
Cu(s) + Pb2+ (aq)
) Cu 2+ (aq) + Pb(s

)(351

Electrochemistry

:
/ .

:
Pb(s) + Cu 2+ (aq)
) Pb2+ (aq) + Cu(s

:
)Pb(s) Pb2+ (aq,1M) Cu 2+ (aq,1M) Cu(s

G = - 89.4 kJ
) :
G = - RT lnK
G
= lnKRT
89.4 103 J
= lnK(8.314J/K.mol) 298
K = e 36.084 = 4.69 1015

)(352

Electrochemistry

:
/ .

()7-5

:
Zn(s) + Cd 2+ (aq)
) Zn 2+ (aq) + Cd(s

)
)

= - 0.76 V, ECd
= - 0.4 V :

Zn

) K
)

) :
oxidation
reduction

Zn(s)
Zn 2+ (aq) + 2e
Cd 2+ (aq) + 2e
) Cd(s

----------------------------------------------------------------------------Zn(s) + Cd 2+ (aq)
Zn 2+ (aq) + Cd (s) overall reaction

)(353

Electrochemistry

:
/ .

) :

E cell = E cathode
- E anode
Zn

Cd

)E cell = - 0.4 - (- 0.76

E cell = 0.36 V

) :
RT lnK = z E cell F
z E cell F
= ln K
RT
2 0.36 96500
=ln K
8.314 298
2 0.36 96500
8.314 298

K=e

K = 1.51 1012

) :

G = - z E cell
F

G = - 2 0.36 96500
G = - 69480 J
G = - 69.480 kJ

)(354

Electrochemistry

:
/ .

()8-5
:
Cl2 (g) + 2I- (aq)
) 2Cl- (aq) + I2 (s

=1.36 V, EI2 0.53 V

Cl2

)
)
) G

) :
Cl2 (g) + 2I- (aq)
) 2Cl- (aq) + I 2 (s
anode

cathode

E cell = E cathode - E anode

I

Cl

E cell = 1.36 - 0.53

E cell = 0.83 V

)(355

Electrochemistry

:
/ .

) :
Z E cell F = RT lnK
z E cell F
= lnK
RT
2 0.83 96500
=ln K
8.314 298
lnK = 64.66
K= e64.66
K =1.21 1028

) :

G = - z E cell
F
G = - 2 0.83 96500
G = - 160190 J
G = - 160.190 kJ

()9-5
:

)Pb(s) Pb2+ (aq) Ag + (aq) Ag(s

:
= - 0.13 V, EAg = 0.8 V

) E

cell

Pb

)(356

Electrochemistry

:
/ .

) G

) :
)Ag + (aq)/Ag(s

)Pb(s) Pb 2+ (aq

cathode

anode

E cell = E cathode - E anode

Pb

Ag

)E cell = 0.8 - (- 0.13

E cell = 0.93 V

) :
RT lnK = z E cell F
8.314 298 ln K = 2 0.93 96500
2 0.93 96500
= ln K
8.314 298
lnK = 72.45
K= e72.45 = 2.9 1031

) :

G = - z E cell
F

G = - 2 0.93 96500
G = - 179490 J
G = - 179.490 kJ

)(357

Electrochemistry

:
/ .

()11-5
:
)Zn(s) Zn 2+ (aq, 1 M) Pb2+ (aq, 1 M) Pb(s

:
= - 0.76 V, EPb = - 0.13 V

Zn

)
)
)

) :

)Pb 2+ (aq, 1 M) Pb(s

)Zn(s) Zn 2+ (aq, 1 M

cathode

anode

E cell = E cathode - E anode

Zn

Pb

E cell = - 0.13 - ( - 0.76) = 0.63 V

)(358

Electrochemistry

:
/ .

:K
RT lnK = z E cell F

8.314 298 ln K = 2 0.63 96500

2 0.63 96500
= ln K
8.314 298
lnK = 49.08
K = e49.08 = 2.07 1021

G = - z E cell
F

G = - 2 0.63 96500
G = - 121590 J
G = - 121.590 kJ

)(359

Electrochemistry

:
/ .

()11-5
Al(s) Al3+ (aq, 1M) Ag + (aq, 1M) Ag(s) :

:
= - 1.67 V, EAg = 0.8 V

Al

)
)
) G

)Ag + (aq , 1M) Ag(s

cathode

reduction
3Ag + (aq) + 3e
) 3Ag (s

)Al(s) Al3+ (aq , 1M

anode

oxidation
Al (s)
Al3+ (aq) + 3e

overall reaction
Al (s) + 3Ag + (aq)
) Al3+ (aq) + 3Ag (s

) :

E cell = E Ag - E Al
)E cell 0.8 (1.67
E cell = 2.47 V
) :

)(360

Electrochemistry

:
/ .

G = - z E cell
F

G = - 3 2.47 96500
G = - 715065 J
G = - 715.065 kJ

()12-5

:

) Sn 2+ (aq) + Pb(s
Sn(s) + Pb2+ (aq)

:
= - 0.136 V, EPb = - 0.126 V

Sn

: :

E cell = E cathode
- E anode
Sn

Pb

E cell = - 0.126 - - 0.136

E cell = 0.01 V

: :

)(361

Electrochemistry

:
/ .

G = - z E cell F
G = - 2 0.01 96500
G = - 1930 J

:
G = - R T lnK
- 1930 = - 8.314 298 ln K
- 1930
- 8.314 298

= ln K

- 1930

8.314

298

K=e

K = e0.779
K = 2.18

) Sn 2+ (aq) + Pb(s
(aq)

2+

Sn(s) + Pb

2.18

a Sn 2+
a Pb2+

=K

) (2.18
()13-5

)(362

Electrochemistry

:
/ .

Pt Fe2+ , Fe3+ Hg 2+ , Hg 2+
2 Pt

) (25 C :

= 0.771 V, E Hg2+ /Hg2+ = 0.910 V

2

Fe3+ /Fe2+

Pt Fe2+ , Fe3+ Hg 2+ , Hg 2+
2 Pt
:

Pt Fe 2+ , Fe3+ Hg 2+ , Hg 22+ Pt
oxidation
2 Fe 2+
Fe3+ + e
reduction
2Hg 2+ + 2e
Hg 2+
2

___________________________
2Fe 2+ 2Hg 2+
2Fe3+ Hg 22+
:

)(363

Electrochemistry

:
/ .

2Fe 2+ 2Hg 2+
2Fe3+ Hg 22+
E cell = E cathode - E anode
Fe3+ / Fe 2+

Hg 2+ / Hg 2+
2

E cell = 0.910 - 0.771

E cell = 0.139 V
:
2Hg2+
2Fe3+ Hg22+

2+

2Fe

G = - z E cell
F

G = - 1 0.139 96500
G = - 13413.5 J
: K
G = - R T lnK
- 13413.5 = - 8.314 298 ln K
- 13413.5
- 8.314 298

= ln K

- 13413.5

- 8.314 298

K=e

K = e5.414
K = 224.53

:

)(364

Electrochemistry

:
/ .

2Fe2+ 2Hg 2+
2Fe3+ Hg 22+

a
=K
= 224.54
a a
2

Hg 2+
2

a Fe3+

Hg 2+

2+

Fe

Fe2+
2+
Hg

)(224.54

()14-5

)(365

Electrochemistry

:
/ .

Ecell , G
)Zn(s) Zn 2+ (aq, 1 M) Cd 2+ (aq, 1M) Cd (s
Pb(s) Pb 2+ (aq, 1 M) Cl- (aq, 1M) Cl 2 (g, 1 atm), Pt
)Ni(s) Ni 2+ (aq, 1 M) Cu 2+ (aq, 1M) Cu(s

E Zn = - 0.7628 V, E Cd
= - 0.403 V

E Pb = - 0.126 V, E Cl2 = 1.358 V

E
=
0.23
V,
E
=
0.337
V
Ni
Cu

)(366

Electrochemistry

:
/ .

" "

th

06 Chapter
Changes of Enthalpy and Entropy

)(367

Electrochemistry

:
/ .

)(Enthalpy and Entropy Changes

G H

)(Gibbs-Helmholtz Equation :
G = H - TS
:
H = G + TS
S:
dE
S
=
zF

dT

:
dE

dT :

)(368

Electrochemistry

:
/ .

dE

dT

(
) .
dE

dT
.

dE

S = zF dT

H = G + TS :
H = G + TS
dE
S = zF

dT
dE
H = G + T zF

dT

)(E
G :
G = - z F E

(369)

Electrochemistry

:
./

G = - z F E
: H = G + T zF dE

dT

dE
H = G + T zF

dT

G = - z F E

dE

H = - z F E + T zF dT

dE
H = - z F E + zFT

dT

H = - z F E +

dE
zFT
dT

:
dE
H = G + zFT

dT
dE
H = - z F E + zFT

dT

dE
H = - z F E - T

dT

dE
H = z F - E + T

dT

dE

H = z F T
- E
dT

)(370

Electrochemistry

:
/ .

( ) H
)(E
dE

dT .

)(E )(F H
.
:

dE
H = G + zFT dT

dE
S = zF

dT

:
dE
dT

.

.

)(371

Electrochemistry

:
/ .

dE

dT
*

dE

0
dT

H = G + zFT

:
dE
H = G + zFT

dT
dE
when :
0
dT

H = G

G, H, S

dE
. dT

E
.
*
T P
E

. 0 :
T P

)(372

Electrochemistry

:
/ .

()1-6
:
Pt, H2 HCl (aq) AgCl, Ag

)(0.2224 V ) (25 C
dE

= - 6.45 10-4 V K -1

dT

:
Pt, H 2 HCl (aq) AgCl, Ag
H 2 (g)
2H + (aq) + 2e

2 AgCl + e
Ag(s) + Cl- (aq)

______________________________________
H 2 (g) + 2AgCl
) 2H + (aq) + 2Ag(s) + 2Cl- (aq

G , H , S :
G = - z F E = - 2 96500 0.2224 = - 42923.2 J
dE
-4
-1
S = z F
= 2 96500 - 6.45 10 = - 124.485 J K
dT
H G + TS - 42923.2 298 - 124.485 80019.73 J

)(373

Electrochemistry

:
/ .

()2-6
H, S :
) ZnCl2 (aq) + 2Ag(s
Zn(s) + 2AgCl(s)

)(Ecell = 1.015 V

dE

-4

- 4.02 10 V/K
dT

) (H :
dE

H = z F T
- E
dT

H = 2 96500 273 - 4.020 10-4 1.015

H = - 217075.978 J
H = - 217.076 kJ
H = - 51.9 kcal

) (S :
dE
S = zF
dT

S = 2 96500 - 4.020 10-4 V/K

S = - 77.59 J/K

)(374

Electrochemistry

:
/ .

()3-6

:
a) Pb, PbI 2 I - AgI, Ag
dE
= 1.27 10-4 VK -1
dT
b) Pb, PbCl 2 Cl- AgCl, Ag
E = 0.211 V,

dE
= 1.86 10 4 VK -1
dT

E = 0.4902 V,

) .
)
.

25 J k -1

- 105.3 kJ,

a) 33.3 kJ,

b) - 40.74 kJ, - 9461 kJ, 25 J k -1

..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................

)(375

Electrochemistry

:
/ .

..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................

)(376

Electrochemistry

:
/ .

()4-6
( )3-6
:
PbCl2 + 2AgI
PbI2 + 2AgCl
E
:
T p

E, G , S, H,

E = 0.2791 V, G = - 53.87 kJ, S= - 61 JK -1

H = - 72 kJ, E = 3.16 10- VK -1

..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................

)(377

Electrochemistry

:
/ .

()5-6
:
Pt, H 2 HCl 0.01 m AgCl,Ag
E = 0.2002 V
E
-5
-1
= - 8.665 10 VK
T

)
) .

E
-1
G
=
44.3
kJ,
=
8.4
JK
,
H
=
41.8
kJ

..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................

)(378

Electrochemistry

:
/ .

)(G

E
th

07 Chapter

The Relationship Between (G) and E

)(379

Electrochemistry

:
/ .

) (G E
and E (G) The Relationship Between
:
G = - z . E electrode . F

G = - z . E cell . F
:
: z ()
.
: F )(96500 C
: E

) (Eelectrode ) (Ecell

RT
lnQ
zF

E = E -

)(380

Electrochemistry

:
/ .

G = - z . E . F

) (P = 1 atm, a = 1, T = 25 C
G = - z . E . F :

G = - z . Eelectrode . F

G = - z . Ecell
. F

G = - z . Ecell . F :
:
)1 (

)
. G = - ve
)2
. G = + ve
)3
. G = 0 :

)(381

Electrochemistry

:
/ .

G = - z . Ecell . F :
)1 )(E = + ve

)2 ).(E = - ve
)3 ).(E = 0

)1 )1 .
) (E ) (G .
)2 )2
) (G .
)3 )3 ) (E = 0 ) (G
.

+
0

Ecell
+
0

)(382

Electrochemistry

:
/ .

()1-7
G :
Zn(s) + 2H+ (aq)
) Zn 2+ (aq) + H2 (g

= - 0.7628 V, EH2 = 0.000 V

Zn

:
E cell

.F

G = - Z .

)E cathode (H) - E anode (Zn

G = - 2 (0 - (- 0.7628) 96500
G = - 2 (0.7628) 96500
G = - 147220.4 J
G = - 147.220 kJ

()2-7
)(25 C
.
Pb(s) Pb2+ (aq , a = 1) Ag + (aq , a = 1) Ag

)(383

Electrochemistry

:
/ .

:
= - 0.126 V, EAg = 0.799 V

Pb

:
Pb(s) Pb 2+ (aq , a = 1) Ag + (aq , a = 1) Ag
oxidation
Pb(s)
Pb 2+ (aq) + 2e
reduction
2 Ag + (aq) + e
Ag(s)
___________________________________________________________

E cell = 0.799 - (- 0.126) = 0.925 V

Pb(s) + 2Ag + (aq)

) Pb 2+ (aq) + 2Ag(s

:
G = - z E F
G = - 2 0.925 96500
G = - 178525 J
G = - 178.525 kJ

Ecell = 0.925 V

G 178.525 kJ

)(384

Electrochemistry

:
/ .

.
:

) (z

. G = - z E F

(aq)
Pb2+ (aq) + 2Ag(s)

Pb(s) + 2Ag

) (1/2 :

E
E

= 0.925 V

cell

= 0.925 V

cell

Pb(s) + 2Ag + (aq)

Pb2+ (aq) + 2Ag(s)

1
2

Pb (s) + Ag + (aq)
) 12 Pb2+ (aq) + Ag (s

1
2

.
:
Pb(s) + Ag + (aq)
12 Pb2+ (aq) + Ag(s)

1
2

G = - z E F
0.925 96500

- 2

1
2

= G

G = - 89262.5 J
G = - 89.2625 kJ

) (z = 1/2 .

)(385

Electrochemistry

:
/ .

()3-7
:
Cu(s) + Cl2 (g)
) Cu 2+ (aq) + 2Cl- (aq

= 0.337 V, ECl2 = 1.36 V

o
Cu

).(25 C

Cu(s) Cu 2+ (aq) Cl- (aq , a = 1) Cl2 (g , 1 atm) , Pt

E cell = E cathode
- E anode
Cu

Cl2

E cell = 1.36 - 0.337

E cell = 1.023 V

:
G = - z E cell F
G = - 2 1.023 96500
G = - 197439 J
G = - 197.439 kJ

)(386

Electrochemistry

:
/ .

.
()4-7
)(25 C
:
2Fe2+ (aq) + I2 (s)
) 2Fe3+ (aq) + 2I- (aq

.
:

= 0.5355 V, EFe3+ /Fe2+ = + 0.771 V

:
(aq) + I2 (s)
2Fe3+ (aq) + 2I- (aq)

2+

2Fe

Pt Fe2+ , Fe3+ I- (aq) I2 (s), Pt

I2 /I-

)(387

Electrochemistry

:
/ .

2Fe3+ (aq) + 2I- (aq)
2Fe2+ (aq) + I2 (s)

E cell = E cathode
- E anode
Fe3+ / Fe2+

I2 / I-

E cell = 0.5355 - 0.771

E cell = - 0.2355 V
:

G = - z E cell
F

G = - 2 (- 0.2355) 96500
G = + 45451.5 J
G = + 45.45 kJ

.
:
(aq) + I2 (s)
2Fe3+ (aq) + 2I- (aq)

2+

2Fe

:
2Fe3+ (aq) + 2I- (aq)
) 2Fe2+ (aq) + I2 (s

)(388

Electrochemistry

:
/ .

:
2Fe3+ (aq) + 2I- (aq)
) 2Fe 2+ (aq) + I 2 (s
E cell = E cathode - E anode
I2 /2I-

Fe2+ /Fe3+

E cell = 0.771 - 0.5355

E cell = + 0.2355 V

G = - z E cell
F

G = - 2 ( 0.2355) 96500
G = - 45451.5 J
G = - 45.45 kJ

. :

Pt, I2 (s) I- (aq) Fe2+ , Fe3+ Pt

)(389

Electrochemistry

:
/ .

th

08 Chapter
Cell Potential and
Temperature

)(390

Electrochemistry

:
/ .

Cell Potential and Temperature
:
RT
lnQ
zF

E = E -

).(T

) (80 C E

) (25 C

)(391

Electrochemistry

:
/ .

)(25 C

G = - z E F
G
= EzF

E .
G

)(25 C
:
:
G = H - TS

H ) (S

) . (G

)(392

Electrochemistry

:
/ .

H :

H = Hf (products) - Hf reactants

) ) (S

) (S

) (S :

)S = S (products) - S (reactants

H ) (S

H f ) (S
) (25 C
H ) (S ) (25 C

)(393

Electrochemistry

:
/ .

. H ) (S

) (25 C
) (Kirchhoff's Equation :
H2 = H1 + Cp T2 - T1

H 2 ) (T2
H1

) (T1

:
Cp T2 - T1

Cp
:
)Cp = Cp (products) - Cp (reactants

) (Cp

) (100 %

) (Cp
.

)(394

Electrochemistry

:
/ .

S :
T2
T1

S2 = S1 + Cp ln

S2

) (T2

S1 :

T2
Cp ln
T1

) (Cp
.
H S

G ) (E .

)(395

Electrochemistry

:
/ .

()1-8
): (80 C
Ag,AgCl KCl KBr Br2 , Pt

) (0.8428 V
) (25 C :

) (S

J/K. mol
- 141.8
50.74
75.69
25.35
136.4

J/K. mol

kJ/mol
- 121.55
- 127.07
0
0
- 167.16

82.4
96.11
152.23
42.55
56.5

substance

:
Ag,AgCl KCl KBr Br2 , Pt
2 Ag + Cl-
AgCl + e
Br2 + 2e
2Br__________________________
2Ag + 2Cl- Br2
2AgCl + 2Br -

Br
AgCl
Br2
Ag
Cl-

(396)

Electrochemistry

:
./

( 25 C)

:
2Ag + 2Cl- Br2
2AgCl + 2Br H1 = H f (products) - H f reactants

H1 = 2H f (Br - ) 2H f (AgCl) 2H f (Ag) 2H f (Cl - ) H f (Br2 )

H1 = 2 (- 121.55) 2 ( 127.07) 2 0 167.16 2 0
H1 = - 162.92 kJ
S1 =

S (products) - S (reactants)

S1 = 2S (Br - ) + 2S (AgCl) - S (Br2 + 2S (Ag) + 2S (Cl - )

S1 = 2 (82.4 2 96.11 (152.23) + (2 42.55) + (2 56.5)
S1 = 6.69 JK -1
Cp = C p (products) - C p (reactants)

Cp = 2C (Br - ) + 2C (AgCl) - C (Br2 + 2C (Ag) + 2C (Cl - )

Cp = 2 (-141.8 2 50.74 (75.69) + (2 25.35) + (2 -136.4)
Cp = - 35.71 J/K

:( 25 C = 298 K)
G1 = - z E F
G1 = - 2 0.8428 96500
G1 = - 162660.4 J
G1 = - 162.660 kJ

)(397

Electrochemistry

:
/ .

H , S

) (80 C = 333 K :
H 2 = H1 + Cp T2 - T1
H 2 = - 162.92 103 35.611 (353 298
H 2 = - 164878.605 J
H 2 = - 164.879 kJ
T
S2 = S1 + Cp ln 2
T1
353

298

S2 = 6.69 + - 35.611 ln

S2 = 0.658 J/K

G 2 :

G 2 = H 2 - TS2

G 2 = - 164.879 103 - 353 0.658

G 2 = - 165111.274 J
G 2 = - 165.111 kJ

)(398

Electrochemistry

:
/ .

) (353 K :

G = - z E F
G
= EzF
3
165.111

10

= E2 96500
E = 0.8555 V

) (Cp

H 2
S2 ) (Cp

) (T1 )(T2

) (Cp

:
Cp = a + bT + cT2 + dT3

:
'c
T2

Cp = a' + b'T +

)' (a, b, c, d, a', b', c

.

)(399

Electrochemistry

:
/ .

th

09 Chapter
Measurement of pH

)(400

Electrochemistry

:
/ .

Measurement of pH

) (H+

H2/H+

) (H+

:
)(anode, oxidation
)(cathode, reduction

H 2 (g, 1atm)
2H + (aq, unknown M) + 2e
2H + (aq, 1M) + 2e
) H 2 (g, 1atm

-------------------------------------------------------------------------------------------2H + (aq, 1M)

) 2H + (aq, unknown M

) (E = 0

) (Ecell

Electrochemistry

(401)

:
./

: )(z = 2) (
2

E cell = E cell -

H +
unknown

0.0592
log
2
2
H +
standard

H +
= 1 M and E cell = 0,
standard
2
0.0592
E cell = log H +
unknown
2
since log x 2 = 2 log x,
E cell =

- 0.0592
2 log H +
unknown
2

E cell = 0.0592 log H +

unknown
Because - log H + = pH, the final expressionis:

E cell = - 0.0592 - log H +

unknown

E cell = 0.0592 pH
Therefore, by measuring E cell , pH unknown can be measured.

:
pH unknown =

E cell
0.0592

)(402

Electrochemistry

:
/ .

()1-9

)(pH

) (pH )(H+
)( (1.0 M

)(0.366 V

) (pH 25 C

)(reduction

2H + (1 M) + 2e
) H 2 (g,1atm

)(oxidation

H 2 (g,1atm)
2H + (unknown M) + 2e

-------------------------------------------------------------------------------E cell = 0.366 V

2H + (1 M)
) 2H + (unknown M

(403)

Electrochemistry

:
./

: (25 C)
2

E cell = -

0.0592
log
2

H +
unknown
H +

2
0.0592
lg H +
unknown
2
0.0592
0.366 = 2log H +
unknown
2

0.366 = -

0.366 = - 0.0592 log H +

unknown

0.366 = 0.0592 - log H +

0.366 = 0.0592 pH unknown
0.366V
0.0592V
pH unknown = 6.18
pH unknown =

unknown

)(404

Electrochemistry

:
/ .

()2-9
) (pH
) (3.66

( (Ecell

( (H+ ) (pH = 3.66 :

pH = 3.66
- log H + =3.66
log H + = - 3.66
) H + = anti log (- 3.66
H + = 2.188 10-4

:
2

H +
0.0592
solution
= E celllog
2
2
H +

standard

2
0.0592
lg H +
solution
2
0.0592
= 2log H +
solution
2

= E cellE cell

E cell = - 0.0592 log 2.188 10-4

E cell = 0.217 V

)(405

Electrochemistry

:
/ .

:
E cell = 0.0592 pH
E cell = 0.0592 3.66
E cell = 0.0592 3.66
E cell = 0.217 V

)(406

Electrochemistry

:
/ .

The pH Meter

) (pH

) (pH

) (pH ((pH
) (pH ( )1-9 (: )2-9

( (Ag/AgCl

) (HCl
) (very thin glass membrane

) (Pt

) (KCl

Hg 2Cl2 (s) + 2e
2Hg(L) + 2Cl- (aq) E = + 0.27 V

) (converted electronically ) (pH

Electrochemistry

(407)

:
./

Fig. (9-1) : The electrodes and reactions of the pH meter. The glass electrode is
(Ag/AgCl) half-cell in a standard HCl solution that is enclosed by a glass membrane.
It is sensitive to the external H+ in the solution relative to the H+ in the internal
standard HCl solution. The saturated calomel electrode is the reference electrode.

Fig. (9-2) : A pH meter uses the voltage of a cell to measure the H+ concentration in a
solution. Each change of one pH unit causes a voltage change of 0.0592 volts.