1-a)

Li( ) Li+() +e ( )(i)

( )
( )
Li e
( )
Li =
( )

Li
(e )= (Li )

Li+() +e () Li( ) (ii)

( )
( )
( )
Li e = Li

( )

Li
(e )= (Li )

The expression in terms of chemical potentials which represents the potential difference
between the electrons in the equations (i) and (ii), is:

()
Li
()
Li
(Li )
(Li )
(e ) (e )=
()
()
Li
Li (Li ) +
(e ) (e )= (Li )
( )

( )

e e =0

2 H +( ) +2 e( ) H (2 )(iii)

b)

( )
()
( )
H 2 e = H
2

'

Cd (k) Cd 2+() +2 e ( ) (iv)

()

( ' )
Cd 2 e
(k)
Cd =

()
H
1 ( )
)
(
e = H
2
2

( )
Cd
1 (k) 1
')
(

e = Cd
2
2

The expression in terms of chemical potentials which represents the potential difference
between the electrons in the equations (iii) and (iv), is:

()
H
()
Cd
1 (k) 1

2 Cd 2
1 ()

2 H
(e ) (e )=
2

'

()
()
Cd
1
+1
H (kCd)

2
2
)
( ) 1 ( )
(
e e = H
2
'

2-

PbSO4(s) + 2H2O(l) PbO2 (s) + 4H+(aq)+ SO4 2-(aq) + 2e- (i)

PbSO4(s) + 2 e- 2Pb(s) + SO42-(aq) (ii)

a) The equilibrium relationships in terms of electrochemical potentials for equations (i)

and (ii), can be written as presented below:

For (i), we have:

( )
( )
( )

()

( )

H 2 e =PbSO +2 H ( 2)

SO 4 4
( )
PbO +
4

2O

( )
( )
H iii
SO 4 2
1 ()
1 ( )
1
( )
()
e = PbSO + H PbO

2
2
2
4

2O

For (ii), we have:

()
SO 4 2
( )
( )
()
PbSO +2 e =Pb +
4

( )
1 ()
SO
( iv)
2 PbSO
1 ( ) 1
( )
e = Pb +
2
2

b) Subtracting the equation (iii) of the equation (iv), we have an expression for the
overall cell potential in terms of electrochemical potentials:

( )
( )
H
()
1 ( )
SO 4
2 PbSO
1 ( ) 1
+
2 Pb 2

SO 4 2
1 ( )
1 )
1

+ (H ) (PbO

2 PbSO
2
2
( )
( )
e e =
4

2O

()
()
()
1 ( )
SO 4
2 PbSO
1 ) 1
H (Pb

2
2
SO 4 2
1 ( )
1 ( )
1
( )
( )
( )
e e = PbSO
+ H PbO

2
2
2
4

2O

( )
( )
1 ()
SO4
2 PbSO
1 )
H (Pb

2
4

1 )
1 )
(e )(e )= (PbSO
+ (H ) (PbO
2
2
2
4

2O

c) The Nernst equation from the equilibrium relationships can be written as the
expression below:

( )
( )
()
1
SO4
2 PbSO
1 )
H (Pb

2
4

1 )
1 )
(e )(e )= (PbSO
+ (H ) (PbO
2
2
2
4

2O

F=z e F ( ( ) ( ) ) =(e )(e )

H +
H 2 RT ln a
1
SO 2
4 Pb 2
2

SO 4 RT ln a
1

F= PbSO + H PbO
2
4

2O

H +
SO 2
4 2 RT ln a
1
H PbRT ln a
2
SO 4 2
1
F=PbSO + H PbO
2
4

2O

SO 4
a

H +
F
lna

=F RT ln

SO 4
a

H +
a

RT

=
ln
F

d) The standard cell potential is:

PbO2 (s) + 4H+(aq) + SO4 2- (aq) + 2e- PbSO4(s) + 2H2O (l)
PbSO4(s) + 2 e- Pb(s) + SO42-(aq)

E = 1.685 V Anode
E = -0.356 V Cathode

PbSO4(s) + 2H2O(l) PbO2 (s) + 4H+(aq)+ SO4 2-(aq) + 2ePbSO4(s) + 2 e- 2Pb(s) + SO42-(aq)
__________________________________________________
2PbSO4(s) + 2H2O(l) PbO2 (s) + 2Pb(s) + 4H+ (aq)+ 2SO42-(aq)

E= -0.356 +(-1.685) = - 2.041 V

3Pb / PbO / KOH, H2O / PbO / PbO2 / Pb

PbO2 + H2O + 2e- = PbO +2OH-

(i)

Pb + 2OH- = PbO + H2O + 2e-

(ii)

Fu = zeF(-) = e-e (iii)

The equilibrium relationships in terms of electrochemical potentials for equations (i)

and (ii), can be written as presented below:
For (i):

1
1

OH H O PbO
2
2
1
e = PbO +
2
2

For (ii):
1
1
OH PbO H
2
2
1
e = Pb+
2

Replacing the equations (i) and equation (ii) in equation (iii):

PbO

Pb O2

PbO +2 H O
2

Pb +2 H O

FE=e e =

2
2

Pb PbO PbO Pb O
FE= =

2
2

Then,
0

0
0
0
Pb O
1 PbPbO PbO Pb O
1 Pb
E=

=
0PbO +
F
2
2
F 2
2
0

) (

If we calculate E treating each electrode reaction as a reduction:

O H
a
( 2 ]
1
1
1
( a Pb O ) ( a H O ) ( a PbO) (A)
RT
E =E 0
ln
F
2

O H
a
( 2 ]
1
1
1
( a PbO ) ( a H O ) ( aPb ) (B)
RT
E =E0
ln
F
2

Subtracting the equations (A) and (B):

0
0Pb O RT
( a Pb O ) ( a Pb )
1 Pb
0
E=
PbO +
+
ln
2
F 2
2
F
( a PbO )

All of these activities are equal to one (these species are neutral), so:
0

0
Pb O
1 Pb
E=
0PbO +
F 2
2

The standard cell potential:

PbO2 + H2O + 2e- PbO +2OH-

Ered = +0.28 V (Cathode)

PbO + H2O + 2e- Pb + 2OH-

Ered = -0.576 V (Anode)

PbO2 + Pb 2PbO
E= Ecathode - Eanode
E = 0.28 (-0.576) = 0.856 V

4-a)

AgI + e- Ag(s)+ I- (aq)

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

Ered = -0.152 V
Ered = +0.799 V

Ag(s) + I- AgI + eAg+(aq) + e- Ag(s)

______________________
Ag+(aq) + I-(aq) AgI

Anode
Cathode

 E= Ecathode - Eanode
E= 0.799 -( 0.152) = 0.951 V
Since E>0,

G= -NFE < 0, Spontaneous reaction

Galvanic Cell

Ag(s)/ I- (aq) / AgI // Ag+(aq)/ Ag (s)

Salt bridge

b) PbO2 (s) + 4H+(aq) + SO4 2- (aq) + 2e- PbSO4(s) + 2H2O (l)

Anode
PbSO4(s) + 2 e- Pb(s) + SO42-(aq)

E = 1.685 V

E = -0.356 V

PbSO4(s) + 2H2O(l) PbO2 (s) + 4H+(aq)+ SO4 2-(aq) + 2ePbSO4(s) + 2 e- 2Pb(s) + SO42-(aq)
__________________________________________________
2PbSO4(s) + 2H2O(l) PbO2 (s) + 2Pb(s) + 4H+ (aq)+ 2SO42-(aq)

E= -0.359 +(-1.69) = - 2.041 V

Since E<0, G= -NFE > 0, Non- Spontaneous
Electrolytic Cell

Pb / PbSO4 / H2SO4, H2O / PbSO4 / PbO2 / Pb

Cathode

c) 2H+(aq) + 2 e- H2(g)
O2 (g) + 4H+ + 4e- 2H2O

E = 0.000 V

Anode

E =1.23 V

Cathode

2H2(g) 4 H+(aq) + 4 eO2 (g) + 4H+(aq) + 4e- 2H2O (l)

____________________________
2H2(g) + O2 (g) 2H2O (l)

E= 0.123 (0.000) = 0.123 V

Since E>0,

G= -NFE < 0, Spontaneous reaction

Galvanic Cell

Pt/ H2(g) / HCl (l),H2O (l) / O2 (g) / Pt

The HCl is used to increase the electric conductive of the solution. The electrodes of Pt
are used because they are inert to the solution, and also they are considered as catalyst.

5- a) Ag(s)+ I- (aq) AgI + eAg+(aq) + e- Ag(s)

Negative electrode
Positive electrode

b) PbO2 (s) + 4H+ + SO4 2- + 2e- PbSO4(s) + 2H2O

PbSO4(s) + 2 e- Pb(s) + SO42-(aq)

c) 2H2(g) 4 H+(aq) + 4 eO2 (g) + 4H+ + 4e- 2H2O

Negative electrode
Positive electrode

Positive electrode
Negative electrode