3 Electrochemistry: Solutions

Chapter 3
Electrochemistry
Solutions
SECTION - A
School/Board Exam. Type Questions
Very Short Answer Type Questions :
1. Express mathematically the relation among resistance, specific conductivity and cell constant.
1 l
Sol. K  
R a
Where K = specific conductivity, R = Resistance, (l/a) = cell constant

2. What is the effect of dilution on (i) conductivity and (ii) molar conductivity?
Sol. Conductivity of an electrolyte decreases with dilution whereas molar conductivity increases.
3. Why does molar conductivity of strong electrolytes increase marginally with dilution even though they are
completely ionised?
Sol. Molar conductivity of strong electrolytes is less in the high concentration region as the mobility of ions is slow
due to inter ionic attractions. As the concentration decreases, the conductance marginally increases as the
mobility of ions increases due to weaker inter ionic attractions.
4. What happens to the reduction potential of Pt | H2 (P atm) | H+ (1 M) at 298 K when P increases from 1 atm
to 10 atm?
0.059 (pH2 )
Sol. EH /H   log .
2 2 [H ]2
As pH2 increases from 1 atm to 10 atm keeping [H+] = 1 M at 25°C, the reduction potential of hydrogen
electrode decreases from 0 to –0.0295 V.
5. What is the effect of increase in concentration of Zn2+ ions on the electrode potential of zinc electrode
(EZn2 /Zn ) ?
o RT 1
Sol. EZn2  /Zn  EZn2  /Zn  2F ln .
[Zn2 ]
As the concentration of Zn2+ ions increases the reduction potential of Zn/Zn2+ half cell increases.
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20 Electrochemistry Solutions of Assignment (Set-1)
6. Predict whether F2 and Na will react with each other or not? Also give suitable explanation.
Given Eo 
o
 2.87 V; ENa   2.71 V .
F 2 /F /Na
Sol. 2Na + F2  2NaF
Eocell  EFo –
o
 ENa   2.87  ( 2.71)  5.58 V
2 /F /Na
Since, Eocell is positive, sodium will react with fluorine.
7. How do we measure the conductance of an electrolytic conductor?
Sol. The conductance of an electrolytic conductor is measured by immersing the conductivity cell into the electrolyte
and connecting it to one of the arms of Wheatstone bridge.
8. Write electrode reactions taking place in Ni – Cd cell. Is it primary or secondary cell?
Sol. Anode : Cd  2OH  Cd(OH)2  2e 

Cathode : NiO2  2H2O  2e   Ni(OH)2  2OH
Cd  NiO2  2H2O  Cd(OH)2  Ni(OH)2
It is a secondary cell.
9. How does standard reduction potential of Ag | AgX | X– vary with the solubility product of AgX at 25°C?
Sol.

Ag  X
AgX  G1o  RT lnK sp
Ag  e  Ag Go2  FEoAg / Ag
 Ag  X Go3  FEo 
AgX  e   RT lnK sp
Ag / Ag
 FEoX |AgX|Ag  FEoAg |Ag  RTlnK sp
RT
EoX |AgX|Ag  EoAg |Ag  lnK sp
F
As Ksp increases, the standard reduction potential of Ag|AgX|X– half cell increases.
10. What are the products obtained at cathode and anode during electrolysis of an aqueous solution CdCl2 using
mercury cathode and platinum anode?
Sol. CdCl2  Cd2+ + 2Cl–

 
H  OH
H2O
Cathode : Cd2+ + 2e  Cd; Cd + Hg  Amalgam
Anode : 2Cl–  Cl2 + 2e
Solutions of Assignment (Set-1) Electrochemistry 21
Short Answer Type Questions :
11. Define specific conductivity of a solution. The specific conductivity of 0.15 M. NaOH solution is 0.48 S cm–1.
Calculate its equivalent conductance.
Sol. Specific conductivity of a solution is the conductance of 1 cubic centimeter of the solution. If ‘K’ is the specific
conductivity, ‘C’ the conductance, ‘l’ the distance between electrodes and ‘a’ is the area of cross-section of
l
the electrodes then K  C  S cm1 .
a
Equivalent conductance (eq) of an electrolyte is given by
K  1000 0.48  1000

eq    3.2  103 S cm2 eq1
Normality 0.15
12. Calculate pH of electrolyte in the half cell Pt | H2 (1 atm) | H+, if its reduction potential at 25°C is –0.30 V.
Sol. Pt | H2 (1 atm) | H+
0.059 pH
EH /H   log  2 2
2 2 [H ]
–0.30 = –0.059 (pH)

 pH = 5.08
13. The standard emf of the following cell reaction is 0.89 V
3Sn4+ + 2Cr  3Sn2+ + 2Cr3+
Calculate standard free energy change for the reaction.
Sol. 3Sn4+ + 2Cr  3Sn2+ + 2Cr3+ Eocell  0.89 V
G  nFEocell = –6 × 96500 × 0.89 = 515.31 kJ

14. Explain Kohlrausch's law of independent migration of ions. Mention one application of Kohlrausch's law.
Sol. Kohlrausch’s law states that at infinite dilution when dissociation is complete molar conductivity of an electrolyte
is equal to sum of contributions due to cation as well as anion. For example, molar conductivity of Na2SO4
at infinite dilution is given by
 
m (Na2SO4 )  2m (Na )  m

(SO24 )

It helps to calculate m of weak electrolytes. Example
 
m (CH3COOH)  m (H )  m

(CH3COO )
 
m (NaCl)  m (Na )  m

(Cl )
 
m (HCl)  m (H )   Cl

(Cl )
 
m (CH3COONa)  m (Na )  m

(CH3COO )
   
 m (CH3COOH)  m (CH3 COONa)  m (HCl)  m (NaCl)
15. Consider the given E° values in volts for 1 M solution
Fe2+ | Fe = –0.4 V; Fe3+ | Fe2+ = +0.80 V
Mn2+ | Mn = –1.2 V; Mn3+ | Mn2+ = +1.5 V
Comment on the relative stabilities of +2 and +3 oxidation states of iron and manganese.
o o o o
Sol. Since EMn3  /Mn2   EFe3  /Fe2  and EMn2  /Mn  EFe2  /Fe , Fe3+ is more stable than Fe2+ whereas Mn2+ is more
stable than Mn3+. This is supported by their electronic configuration also. Both Fe3+ and Mn2+ have stable
configuration i.e., 3d5.
16. The same quantity of electrical charge deposited 0.583 g of Ag when passed through AgNO3 and AuCl3
solutions. Calculate the weight of gold deposited. [Atomic mass : Ag = 108, Au = 197]
Sol. Equivalents of gold = Equivalents of silver [∵ Q is same]
WAu 0.583

(197/3) 108
 WAu = 0.354 g
17. Calculate the volume of Cl2 at STP produced during electrolysis of MgCl2 which produces 5.4 g Mg (Atomic
mass of Mg = 24).
5.4
Sol. Equivalents of Cl2 = Equivalents of Mg 
12
Volume of one equivalent of Cl2 at STP = 11.2 litre
5.4  11.2
 Volume of Cl2 at STP   5.04 litre
12
18. In a fuel cell H2 and O2 react to produce electricity. In the process H2 gas is oxidised at anode and O2 gas
is reduced at cathode. If 67.2 litre of H2 at STP reacts in 20 min, what is the average current produced?
Sol. In a fuel cell

Anode : [H2  2OH  2H2O  2e]  2
Cathode : O2  2H2O  4e  4OH
2H2  O2  2H2O
Volume of 1 equivalent of H2 at STP = 11.2 litre
67.2
 Number of equivalents of H2  6
11.2
 Charge (Q) = 6 F = 6 × 96500 C
Charge (C) 6  96500

Current (amp)    482.5 A
Time (s) 20  60
19. Ecell of Pt | H2 (1 atm) | H+ (pH = 6) | | H+ (pH = x) | H2 (1 atm) | Pt at 25°C is 0.118 V. What is the value of x?
Sol. Pt | H2 (1 atm) | H+ (pH = 6) | | H+ (pH = x) | H2 (1 atm) | Pt
1
Anode : H2  H  e
2
1
Cathode : H  e  H2
2
(H )cathode  (H )anode
[H ]anode
Ecell  0.059 log
[H ]cathode
0.118 = 0.059 [(pH)anode – (pH)cathode]

(pH)cathode = 4
20. The E° of a cell in which the following reaction occurs is 0.59 V at 25°C
MnO4– + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ + 4H2O
What is equilibrium constant (KC) of the given reaction?
Sol. Eocell  0.59 V at 25°C
RT 0.059
Eocell  ln K  log K at 25°C
nF n
MnO4– + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ + 4H2O
Here, n = 5
0.059
 0.59  log K
5
 K = 1050
21. How much copper is deposited on the cathode of an electrolytic cell if a current of 5 ampere is passed through
a solutions of CuSO4 for 45 minutes? [Atomic mass of Cu = 63.5]
Sol. i = 5 amp, t = 45 × 60 s
13500
Q = it = 5 × 45 × 60 C = 13500 C  F
96500
Mass of copper deposited = Q(F) × Eq. wt. of Cu
135 63.5
   4.44 g
965 2
22. How many grams of Ag could be plated on a shield by electrolysis of a solution containing Ag+ ions for a period
of 4 hours at a current strength of 8.5 ampere?
Sol. i = 8.5 A, t = 4 × 3600 s
1224
Q = it = 8.5 × 4 × 3600 C = 122400 C  F
965
1224
Mass of silver deposited   108  137 g
965
23. What is corrosion? Describe the role of zinc in cathodic protection of iron. Can we use tin in place of zinc
for this purpose ? Give reasons.
Sol. Corrosion is a process in which metals are oxidised on exposure to moist air. The rusting of iron, tarnishing
of silver, development of green layer on the surface of copper are examples of corrosion. Metal looses electrons
to other electronegative elements like oxygen or sulphur to form metal oxide or sulphide on its surface. Corrosion
is essentially an electrochemical phenomenon. For example, corrosion of iron is the electrochemical oxidation
of iron to Fe2+ and reduction of O2 in presence of H+ formed due to dissolution of CO2 and other acidic oxides
present in air into water
o
Anode :  Fe2 (aq)  2e
Fe(s)  (EFe 2
/Fe
 0.44 V )
Cathode : O2 (g)  4H (aq)  4e 
 2H2O(l) (EHo  /O  1.23 V )
2 /H2 O
2Fe(s)  O2 (g)  4H (aq) 

 2Fe2 (aq)  2H2O(l) (Eocell  1.67 V)
The Fe2+ ions are oxidised by atmospheric oxygen to form hydrated ferric oxide which is called rust
1
2Fe2 (aq)  2H2O(l)  O (g)  Fe2O3 (s)  4H (aq)
2 2
Corrosion of iron can be prevented by covering its surface by Zn which itself undergoes oxidation in preference
to Fe and thus saves the iron. Tin can also be used in place of Zn.
24. Zinc rod is dipped in 0.1 M solution of ZnSO4. The salt is 90% ionised at this concentration at 25°C. Calculate
the electrode potential.
Given Eo 2   0.76 V
Zn / Zn
Sol. Zn | ZnSO4 (0.1 M) at 25°C
2
ZnSO 4

Zn
 SO24
Conc. 0.1(1  0.9) M 0.09 M 0.09 M
Zn2+ + 2e  Zn
0.059 1
EZn2  /Zn  EoZn2  /Zn  log
2 [Zn2 ]
0.059 1
 0.76  log
2 0.09
= –0.79 V
25. Calculate the emf of the following cell at 25°C
Fe | Fe2+ (0.1 M) | | Ag+ (0.1 M) | Ag
Given : Eo 2   0.44 V and EoAg / Ag  0.80 V

Fe /Fe
Sol. Fe | Fe2+ (0.1 M) | | Ag+ (0.1 M) | Ag at 25°C

o
EFe 2
/Fe
 0.44 V and EoAg / Ag  0.80 V
Anode : Fe  Fe2  2e

Cathode : 2Ag  2e  2Ag
Fe  2Ag  Fe2  2Ag
o 0.059 [Fe2 ]
Ecell  Ecell  log
2 [Ag ]2
0.059 0.1
 [0.80  ( 0.44)]  log
2 (0.1)2
= 1.2105 V
26. Calculate the quantity of charge in coulombs required to reduce 16.2 g of p-benzoquinone if current efficiency
is 75%.
O OH
+
Sol. + 2H + 2e
O OH
16.2
Moles of p-benzoquinone   0.15
108
Charge (Q) = 0.15 × 2 = 0.30 F
Qtheoretical
Current efficiency   100
Qexperimental
0.30  100
Qexperimental  = 0.40 F = 38600 C
75
Long Answer Type Questions :
27. 0.05 N solution of a weak acid has a conductivity 4.65 × 10–4 S cm–1. The degree of dissociation of acid at
this dilution is 0.055. Calculate the equivalent conductivity of weak acid at infinite dilution.
Sol. Degree of dissociation,  = 0.055
Conductivity, K = 4.65 × 10–4 S cm–1
K  1000 4.65  104  1000

 eq    9.3 S cm2 eq1
Normality 0.05
 ceq 9.3
 o
;  eq   169.09 S cm2 eq1
 oeq 0.055
28. The equivalent conductivity of 0.15 N CaCl2 solution is 89.6 S cm2 eq–1 at 298 K. A conductivity cell with a
cell constant 0.28 cm–1 is filled with 0.16 N CaCl2 solution. How much current flows when the potential
difference between the electrodes is 5 V?
Conductivity  1000
Sol. Equivalent conductivity 
Normality
89.6  0.15
or Conductivity  = 13.44 × 10–3 S cm–1
1000
Conductivity = Conductance × Cell constant
13.44  103
or Conductance   0.048 S
0.28
1
Resistance  ohm
0.048
Potential difference
Current  = 5 × 0.048 = 0.24 amp
Resistance
29. At 25°C the molar conductivities of H+ and CH3COO– ions at infinite dilution are 345 and 40 S cm2 mol–1
respectively. The conductivity of 0.003 N solution of acetic acid is 1.62 × 10–4 S cm–1 at the same temperature.
What is the degree of dissociation of acetic acid?
o
Sol. m o
(CH3 COOH)  m (H )  m
o
(CH3 COO ) = 345 + 40 = 385 S cm2 mol–1
K  1000 1.62  10 4  1000

c
m    54 S cm2 mol1
Molarity 0.003
c
m 54
 o
  0.14 or 14%
m 385
30. A cell consists of two hydrogen electrodes dipped into the same 0.1 M HCl. One electrode is supplied with
pure H2 at 1 atm pressure, the other with a mixture of H2 and Ar also at 1 atm pressure. What is the mole
fraction of H2 in this mixture when emf of the cell is 10 mV at 298 K?
Sol. Pt | H2 (1 atm) | HCl (0.1 M) | H2 (P atm) | Pt Ecell = 10 mV at 298 K
Anode : H2  2H  2e

Cathode : 2H  2e  H2
(H2 )anode  (H2 )cathode
0.059 (pH2 )cathode

Ecell   log
2 (pH2 )anode
0.059 P
10 2   log
2 1
 P = 0.458 atm
In cathode half cell H2 and Ar are present at 1 atm pressure
Partial pressure of H2
 Mole fraction of H2   0.458
Total pressure
31. If Kw of water at 25°C is 10–14, calculate the standard reduction potential of the following reaction at 25°C
2H2O + 2e  H2 + 2OH–
1
Given H  e –  H2 Eo  0V
2
Sol.

H  OH
H2O  G1  RT ln K w
1
H  e 
 H2 G2  0
2
1
H2O  e 
 H2  OH G3  RT ln K w
2
 H2  2OH
2H2O  2e  G  2RT ln K w
–2FE° = –2RT ln Kw
RT
E ln K w = 0.059 log 10–14 = –0.826 V
F
32. Find the solubility product of a saturated solution of silver chromate in water at 298 K if emf of the cell Ag | Ag2CrO4
(saturated solution) | | Ag+ (0.1 M) | Ag is 0.164 V at 298 K.
Sol. Ag | Ag2CrO4 (satd. sol.) | | Ag+ (0.1 M) | Ag Ecell = 0.164 V at 298 K
If x mol L–1 is the solubility of Ag2CrO4
Ag | Ag+ (2x M) | | Ag+ (0.1 M) | Ag
[Ag ]anode
Ecell  0.059 log
[Ag ]cathode
2x
0.164  0.059 log
0.1
 x = 8.3 × 10–5 M

 2
2Ag (aq)  CrO4
Ag2CrO4 (s)
2x x
Ksp = (2x)2x = 4x3 = 4(8.3 × 10–5)3 = 2.29 × 10–12
33. An electrode is prepared by dipping a silver strip into a solution saturated with AgSCN and containing 0.1 M SCN–.
The emf of the voltaic cell constructed by connecting this as the cathode to the standard hydrogen half-cell as the
anode is 0.45 V at 25°C. What is Ksp of AgSCN? [Given EoAg / Ag  0.80 V ]
Sol. Pt | H2 (1 atm) | H+ (1 M) | | SCN– (0.1 M) | AgSCN | Ag Ecell = 0.45 V at 25°C
Ecell  ESCN | AgSCN| Ag  0
 ESCN | AgSCN| Ag  0.45
o 1
ESCN | AgSCN| Ag  ESCN  0.059 log
| AgSCN| Ag
[SCN ]
EoSCN | AgSCN| Ag  0.45  0.059 log 0.1  0.391 V
RT
EoSCN | AgSCN| Ag  EoAg / Ag  ln K sp
F
0.391 = 0.80 + 0.059 log Ksp
 Ksp = 1.17 × 10–7
34. An excess of liquid mercury was added to 10–3 M acidified solution of Fe3+ ions. It was found that only 5%
Fe 3+ ions remained as Fe 3+ ions at equilibrium at 25°C. Calculate Eo at 25°C for

Hg/Hg2  2
o
2Hg  2Fe3   Hg22  2Fe2 ( EFe2  /Fe3   0.7 )
Sol. 2Hg  2Fe3  

 Hg22  2Fe2
0.95  103
103 (1  0.95) 0.95  103
2
[Hg22 ][Fe2 ]2 (0.95  103 )3

KC  3 2
  0.171
[Fe ] 2  (0.05  103 )2
RT
Eocell  ln K C
nF
o o 0.059
EFe 3
/Fe2 
 EHg2
/Hg
 log 0.171
2 2
EHg2  /Hg  0.77  ( 0.0226)  0.793 V
 EHg/Hg2   0.793
2
35. A solution containing 4.5 mM of Cr2O72 and 15 mM of Cr3+ shows a pH of 2.0. Calculate the potential of
half cell reaction. The standard potential of the reaction Cr2O72  Cr 3  is 1.33 V.
Sol. Cr2O72– + 14H+ + 6e  2Cr3+ + 7H2O EoCr O2  /Cr 3   1.33 V

2 7
[Cr2O72–] = 4.5 × 10–3 M; [Cr3+] = 15 × 10–3 M; [H+] = 10–2 M
0.059 [Cr 3  ]2
ECr O2  /Cr 3   EoCr O2  /Cr 3   log
2 7 2 7 6 (Cr2O7 )[H ]14
0.059 (15  103 )2

 1.33  log
6 (4.5  103 )(102 )14
= 1.07 V
36. During the discharge of a lead storage battery, the density of H2SO4 falls from 1.294 g/cc to 1.139 g/cc. H2SO4
of density 1.294 g/cc is 39% by weight and that of density 1.139 g/cc is 20% by weight. The battery holds
3.5 litre of acid. Calculate the number of ampere-hours for which the battery must have been used.
Sol. In a lead storage battery, the following reaction takes place
Pb + PbO2 + 2H2SO4  2PbSO4 + 2H2O
Total charge drawn from the battery = Moles of H2SO4 consumed
3500  1.294  39
Initial moles of H2SO4   18.023
98  100
3500  1.139  20
Final moles of H2SO4   8.136
98  100
Moles of H2SO4 consumed = 18.023 – 8.136 = 9.887
Charge drawn = 9.887 F = 9.887 × 96500 C
1 amp. – hour = 3600 C
9.887  96500
 Number of amp. hour   265.03
3600
37. A lead storage cell is discharged which causes H2SO4 electrolyte to change from a concentration of 34.6%
by weight (density 1.261 g/cc at 25°C) to one of 27% by weight. The original volume of electrolyte is 1 litre.
Calculate the total charge used at the anode.
Sol. Pb + PbO2 + 2H2SO4  2PbSO4 + 2H2O
Charge drawn from the cell = Moles of H2SO4 consumed
= Moles of H2O formed
1000  1.261  34.6

Initial mass of H2SO4   436.3 g
100
Percentage of H2SO4 in the final solution = 27%
Let xF charge is drawn from the cell
Final mass of H2SO4 = (436.3 – 98x) g
Final mass of solution = 1261 – 98x + 18x
= (1261 – 80x) g
436.3  98x 27
 
1261  80x 100
 x = 1.255 F
38. An acidic solution of Cu2+ salt containing 0.4 g of Cu2+ is electrolysed untill all the copper is deposited. The
electrolysis is continued for 7 more minutes with the volume of solution kept at 100 ml and the current at 1.2 amp.
Calculate volume of gases evolved at NTP during the entire electrolysis. (Atomic mass of Cu = 63.5)
Sol. Let the Cu2+ salt the CuSO4 and the acidic medium be dil H2SO4. In the first part of electrolysis when copper
is deposited at the cathode
Cathode : Cu2+ + 2e  Cu
Anode : 4OH–  2H2O + O2 + 4e–
0.4  2
Equivalents of O2 = Equivalents of Cu 
63.5
0.8  5600
Volume of O2 at NTP   70.55 ml
63.5
In the second part of electrolysis

Cathode : 2H+ + 2e  H2
Anode : 4OH–  2H2O + O2 + 4e

1.2  7  60
Q  5.2  103 F
96500
Equivalents of H2 = Equivalents of O2 = 5.2 × 10–3
Volume of H2 at NTP = 5.2 × 10–3 × 11200 = 58.24 ml
Volume of O2 at NTP = 5.2 × 10–3 × 5600 = 29.12 ml

Total volume of O2 at NTP = 70.55 × 29.12 = 99.67 ml
39. A current of 15 amp per hour is employed to Ni plate in a NiSO4 solution. Both Ni and H2 are formed at the
cathode and volume of hydrogen produced is 2.5 litre at STP.
(i) How many gm of Ni is plated on the metal sheet per hour?
(ii) What is the thickness of coating if the cathode consists of 4 × 4 cm square metal sheet which is coated
on both faces. The density of Ni is 8.9 g/cc and atomic mass of Ni = 58.7?
15  3600
Sol. Q  F  0.56 F
96500
Equivalents of Ni + Equivalents of H2 = 0.56
2.5
Equivalents of H2   0.2232
11.2
 Equivalents of Ni = 0.56 – 0.2232 = 0.3368
58.7
Mass of Ni deposited per hour  0.3368   9.88 g
2
9.88
Volume of Ni deposited per hour  cc
8.9
9.88
Thickness of coating   0.035 cm
8.9  2  16
40. The Eo 2  and EoAg / Ag are 0.337 V and 0.799 V respectively. Construct a galvanic cell using these
Cu /Cu
electrodes so that Eocell is +ve. For what silver ion concentration will the emf of the cell at 25°C be zero if
[Cu2+] = 0.01 M?
Sol. Cu | Cu2+ (1 M) | | Ag+ (1 M) | Ag
Eocell  EoAg / Ag  ECu

o
2
/Cu
= 0.799 – 0.337 = 0.462 V
o 0.059 [Cu2 ]
Ecell  Ecell  log
2 [Ag ]2
If [Cu2+] = 0.01 M and Ecell = 0
0.059 0.01
Eocell  log
2 [Ag ]2
0.462  2 0.01
 log
0.059 [Ag ]2
 [Ag+] = 1.477 × 10–9 M
SECTION - B
Model Test Paper
Very Short Answer Type Questions :
1. Why is equilibrium constant K related to E°cell and not Ecell?
Sol. Equilibrium constant K is related to E°Cell because ECell is zero at equilibrium
2. Write nernst equation for the reduction potential of Zn/Zn2+ half cell.
RT [Zn2 ]
Sol. EZn|Zn2  EZn| Zn2 – log
2F 1
3. Give an example of a fuel cell.

Sol. Pt |H2(P1atm)| KOH (M)|O2(P2atm)| Pt. This is hydrogen-oxygen fuel cell.
4. How does cathodic protection of iron operate?
Sol. The more reactive metal gets oxidized electrochemically in preference to iron.
5. Express the relationship between degree of dissociation of an electrolyte and its molar conductivities.
c
m 
Sol.   
c
, where m is molar conductivity at concentration c and m is molar conductivity at infinite dilution.
m

6. Depict the galvanic cell in which the following reaction takes place?
Fe2   Ce 4   Fe3  + Ce3 

Indicate the current carriers inside and outside the cell and give the reactions at each electrode.
Sol. The galvanic cell will be represented as Pt Fe2 ,Fe3  Ce4  ,Ce3  Pt
The current is carried by mobility of ions inside the cell and electrons outside the cell. The electrode reactions are
Anode : Fe2   Fe3   e
Cathode : Ce 4   e  Ce3 
Fe2  Ce 4   Fe3   Ce3 
7. How many grams of silver could be plated out on a shield by electrolysis of a solution containing Ag+ ions
for a period of 2.5 h at a current strength of 5 ampere? [Atomic mass: Ag = 108]
Sol. Charge passed (Q) = i × t = 5 × 2.5 × 3600 C
5  2.5  3600
=  0.4663 F
96500
Equivalents of silver doposited = Charge in faraday

= 0.4663
Mass of silver deposited = 0.4663 × 108 = 50.36 gm
8. What is meant by specific conductivity of an electrolyte? The specific conductivity of 0.25 N. KCl solution is
3.2 × 10–2 S cm–1. Calculate its equivalent conductivity.
Sol. Specific conductivity of an electrolyte is the conductance of 1 cm3 of the electrolyte i.e. conductance of that
part of electrolyte placed between two electrodes of 1 cm2 area of cross-section and kept at a distance of
1 cm apart.
Equivalent conductivity  eg  1000  K

Normality
1000  3.2  10 –2
=
0.25
= 128 S cm2 eq–1
9. How much time would it take in minutes to deposit 1.64 g of copper on an object by passing a current of
1.8 amp through an aqueous solution of CuSO4? [Atomic mass: Cu = 63.5]
1.64
Sol. Moles of copper deposited =
63.5
Cu2+ + 2e  Cu
Charge passed (Q) in faradays = 2 × No. of moles of Cu deposited
2  1.64
=
63.5
i × t = Q × 96500
2  1.64  96500
t= second and
1.8  63.5
2  1.64  96500
= = 46.15 minute
1.8  63.5  60
10. Calculate Ecell and G for the following cell at 25°C
Zn Zn2 (1M) Cd2 (1M) Cd
Given that E  –0.76 V and E°  –0.403 V

Zn2  /Zn Cd2  /Cd
Sol. The cell reactions are
Anode: Zn  Zn2  2e
Cathode: Cd2  2e  Cd
Zn  Cd2  Zn2  Cd
Ecell  Ecell  E – E
Cd2 /Cd Zn2 /Zn
= –0.403 – (–0.76) = 0.357 V

G = G° = –nFE°Cell
= –2 × 96500 + 0.357 J
= 68.9 kJ mol–1.
11. The electrical resistance of a column of 0.04 M NaOH solution of diameter 1 cm and length 50 cm is
5.82 × 103 ohm. Calculate its resistivity, conductivity and molar conductivity.
Sol. Area of cross section (a) = r2 = 3.14 × (0.5)2 = 0.785 cm2
Length of conductor = 50 cm
R  a 5.82  103  0.785

Resistivity () =   91.374 ohm cm
l 50
1 1 –2 –1
Conductivity (K) =   91.374  1.094  10 S cm
K  1000 1.094  10 –2
Molar conductivity  m  = 
Molarity 0.04
= 0.2735 S cm2 mol–1
12. Define corrosion. Why does CO2 increase rate of corrosion? Give the chemical changes involved in corrosion
of iron.
Sol. Corrosion is a process in which a metal reacts with substances present in atmosphere. It requires presence
of air, moisture, and H+ ions. carbon doxidide increases the concentration of H+ ions which increases the rate
of corrosion.
The chemical changes involved in corrosion of iron are
1. Fe  Fe2   2e
1
2. 2H  O2  2e  H2O
2
1
3. 2Fe2   Fe2O3 .xH2 O  4H
O2  (x  2)H2O 
2
13. Calculate the equilibrium constant of the following electrochemical cell reaction at 25°C
Ni(s) + Cu2+  Ni2+ + Cu(s)
Given that E  –0.25 V; E  0.34 V

Ni2  /Ni Cu2  /Cu
Sol. Ecell  ECu2  |Cu – ENi2  |Ni  0.34 – (–0.25)  0.59 V
RT 0.059
Eocell  lnK  log K
nF 2
0.59  2
 log K =  20
0.059
K = 1020
14. The standard emf of the following cell is 0.826 V at 25°C
Pt |H2 (1 atm)| OH–(1 M)| |H+(1 M)| H2 (1 atm)| Pt
(i) Write half cell reactions and the overall cell reaction
(ii) Calculate equilibrium constant KC for the cell reaction
(iii) Calculate G° for the cell reaction.
Sol. (i) The half cell and overall cell reactions are
1
Anode : H2  OH–  H2O  e
2
1
Cathode : H  e  H2
2
H  OH–  H2O
(ii) Eocell = 0.059 log KC at 25°C
0.826
 log KC =  14
0.059
 KC = 1014
(iii) G° = – nFE° = – 1 × 96500 × 0.826 = 79709 J
15. Calculate emf of the following galvanic cell at 298 K
Fe|Fe2+ (0.05 M)|| Ag+(0.1 M)| Ag
Given that E 2   –0.44V; E   0.80 V; log 5  0.7

Fe /Fe Ag / Ag
Sol. The given cell reactions are
Anode : Fe  Fe2   2e
Cathode : 2Ag  2e  2Ag
2Ag  Fe  Fe2  2Ag

Ecell  E
Ag |Ag
– E
Fe2  |Fe  
0.059
2
log
[Fe2 ]
[Ag ]2
0.059 0.05
= 0.80 – (–0.44) – log
2 (0.1)2
0.059
= 1.24 –  0.7 =1.219 V
2
16. What current strength in amperes is required to deposit 2.81 g of cadmium from a solution of CdCl2 on mercury
cathode in 2 hour? [Atomic mass of Cd = 112.4 g mol–1]
Sol. Cd2   2e  Cd
Charge passed in faradays = 2 × No. of moles of Cd deposited
2.81
=2×
112.4
2  2.81  96500
Q C
112.4
2  2.18  96500
i amp [∵ Q = it & t = 3600 sec]
112.4  3600
= 1.34 amp
17. Conductivity of 0.01 M CH3COOH solution is found to be 1.648 × 10–4 S cm–1. Calculate its molar conductivity.

If m for CH3COOH is 390 S cm2 mol–1, what is its dissociation constant?
Sol. Conductivity (K) = 1.648 ×10–4 S cm–1
1000  K 1000  1.648  10 –4

c
m    16.48 S cm2mol1
molarity 0.01
c
m 16.48
Degree of dissociation = 
  0.0422
m 390
Dissociation constant, Ka is given by
C 2 (0.01)(0.0422)2
Ka  
1–  1– 0.0422
(0.01)(0.0422)2 = 1.78 × 10–5

18. An aqueous solution of NaCl on electrolysis gives H2, Cl2 and NaOH. A direct current of 25 ampere with a
current efficiency of 62% is passed through 20 litres of NaCl solution . How long would it take to produce
1 kg of Cl2 gas ?
1000
Sol. Moles of Cl2 gas evolved =
71
2000
Q, charge in faradays = 2 × moles of Cl2 =
71
2000  96500
Q C
71
i = 25 × 0.62 = 15.5 amp
2000  96500
t  48.71 hours
71  25  0.62  3600
Long Answer Type Questions :

19. Calculate the cell emf at 25°C for the following cell
Zn | Zn2+ (0.15 M) | | Pb2+(0.015 M) | Pb; Eo  –0.76 V; Eo  –0.13 V

Zn2  /Zn Pb2  /Pb
Calculate the maximum work done by the cell

Sol. The overall cell reaction is
Anode: Zn  Zn2   2e
Cathode: Pb2  2e Pb
Zn  Pb2  Zn2  Pb
Using Nernst equation, emf of the cell is given by
0.059 [Zn2 ]
Ecell  Eocell – log
2 [Pb2 ]
0.059 0.15
  –0.13 – (–0.76) – log
2 0.015
0.059
 0.63 –  0.6005 V
2
Maximum work done by the cell = G = – n FEcell

G = –2 × 96500 × 0.6005 = –115896.3 kJ
= –115.896 kJ mol–1
20. Write a note on lead storage battery.
Sol. Lead storage battery is a secondary cell i.e. it is rechargable.
Anode Pb
Cathode PbO2 packed with Pb
Electrolyte = 38% H2SO4
Reaction of discharging
PbO2 + Pb + 2H2SO4  2PbSO4 + 2H2O
Reaction of charging
2PbSO4 + 2H2O  PbO2 + Pb + 2H2SO4


3 Electrochemistry: Solutions

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3 Electrochemistry: Solutions

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Chapter 3

Where K = specific conductivity, R = Resistance, (l/a) = cell constant

Sol. 2Na + F2  2NaF

Since, Eocell is positive, sodium will react with fluorine.

7. How do we measure the conductance of an electrolytic conductor?

8. Write electrode reactions taking place in Ni – Cd cell. Is it primary or secondary cell?

Sol. Anode : Cd  2OH  Cd(OH)2  2e 

 FEoX |AgX|Ag  FEoAg |Ag  RTlnK sp

Sol. CdCl2  Cd2+ + 2Cl–

Cathode : Cd2+ + 2e  Cd; Cd + Hg  Amalgam

Anode : 2Cl–  Cl2 + 2e

K  1000 0.48  1000

–0.30 = –0.059 (pH)

G  nFEocell = –6 × 96500 × 0.89 = 515.31 kJ

Volume of 1 equivalent of H2 at STP = 11.2 litre

Charge (C) 6  96500

0.118 = 0.059 [(pH)anode – (pH)cathode]

Sol. Eocell  0.59 V at 25°C

2Fe(s)  O2 (g)  4H (aq) 

Sol. Zn | ZnSO4 (0.1 M) at 25°C

Given : Eo 2   0.44 V and EoAg / Ag  0.80 V

Sol. Fe | Fe2+ (0.1 M) | | Ag+ (0.1 M) | Ag at 25°C

Anode : Fe  Fe2  2e

Charge (Q) = 0.15 × 2 = 0.30 F

Long Answer Type Questions :

Sol. Degree of dissociation,  = 0.055

Conductivity, K = 4.65 × 10–4 S cm–1

K  1000 4.65  104  1000

Conductivity = Conductance × Cell constant

K  1000 1.62  10 4  1000

Anode : H2  2H  2e

0.059 (pH2 )cathode

Sol. Ag | Ag2CrO4 (satd. sol.) | | Ag+ (0.1 M) | Ag Ecell = 0.164 V at 298 K

If x mol L–1 is the solubility of Ag2CrO4

Ag | Ag+ (2x M) | | Ag+ (0.1 M) | Ag

Ksp = (2x)2x = 4x3 = 4(8.3 × 10–5)3 = 2.29 × 10–12

anode is 0.45 V at 25°C. What is Ksp of AgSCN? [Given EoAg / Ag  0.80 V ]

Sol. Pt | H2 (1 atm) | H+ (1 M) | | SCN– (0.1 M) | AgSCN | Ag Ecell = 0.45 V at 25°C

Ecell  ESCN | AgSCN| Ag  0

 ESCN | AgSCN| Ag  0.45

EoSCN | AgSCN| Ag  0.45  0.059 log 0.1  0.391 V

0.391 = 0.80 + 0.059 log Ksp

 Ksp = 1.17 × 10–7

Fe 3+ ions remained as Fe 3+ ions at equilibrium at 25°C. Calculate Eo at 25°C for

Sol. 2Hg  2Fe3  

[Hg22 ][Fe2 ]2 (0.95  103 )3

EHg2  /Hg  0.77  ( 0.0226)  0.793 V

Sol. Cr2O72– + 14H+ + 6e  2Cr3+ + 7H2O EoCr O2  /Cr 3   1.33 V

[Cr2O72–] = 4.5 × 10–3 M; [Cr3+] = 15 × 10–3 M; [H+] = 10–2 M

0.059 (15  103 )2

Sol. Pb + PbO2 + 2H2SO4  2PbSO4 + 2H2O

Charge drawn from the cell = Moles of H2SO4 consumed

= Moles of H2O formed

1000  1.261  34.6

Percentage of H2SO4 in the final solution = 27%

Let xF charge is drawn from the cell

Final mass of H2SO4 = (436.3 – 98x) g

Final mass of solution = 1261 – 98x + 18x

Anode : 4OH–  2H2O + O2 + 4e–

In the second part of electrolysis

Anode : 4OH–  2H2O + O2 + 4e

Volume of O2 at NTP = 5.2 × 10–3 × 5600 = 29.12 ml

Eocell  EoAg / Ag  ECu