ELECTROCHEMISTRY
ELECTROCHEMISTRY
ELECTROCHEMISTRY
14.
15. In the electrolysis of aqueous sodium chloride solution which of the half cell reaction will occur at anode?
Reason : is negative.
27. Assertion : ECell should have a positive value for the cell to function.
Reason : Ecathode < Eanode
28. Assertion : Conductivity of all electrolytes decreases on dilution.
Reason : On dilution number of ions per unit volume decreases.
29. Assertion : Λm for weak electrolytes shows a sharp increase when the electrolytic solution is diluted.
Reason : For weak electrolytes degree of dissociation increases with dilution of solution.
30. Assertion : Mercury cell does not give steady potential.
Reason : In the cell reaction, ions are not involved in solution.
31. Assertion : Electrolysis of NaCl solution gives chlorine at anode instead of O2.
Reason : Formation of oxygen at anode requires overvoltage.
32. Assertion : For measuring resistance of an ionic solution an AC source is used.
Reason : Concentration of ionic solution will change if DC source is used.
33. Assertion : Current stops flowing when ECell = 0.
Reason : Equilibrium of the cell reaction is attained.
34. Assertion : EAg+/Ag increases with increase in concentration of Ag+ ions.
Reason : EAg+/Ag has a positive value.
35. Assertion : Copper sulphate can be stored in zinc vessel.
Reason : Zinc is less reactive than copper.
NERNST EQUATION AND GIBBS ENERGY
36. Two half cell reactions of an electrochemical cell are given below :
MnO–4(aq) + 8H+ (aq) + 5e– → Mn2+ (aq) + 4H2O (I), E° = + 1.51 V
Sn2+ (aq) → 4 Sn4+ (aq) + 2e–, E° = + 0.15 V
Construct the redox equation from the two half cell reactions and predict if this reaction favours formation of
reactants or product shown in the equation. (ANSWER = 1.36 V)
37. Given that the standard electrode potentials (E°) of metals are :
K+/K = -2.93 V, Ag+/Ag = 0.80 V, Cu2+/Cu = 0.34 V,
Mg2+/Mg = -2.37 V, Cr3+/Cr = -0.74 V, Fe2+/Fe = -0.44 V.
Arrange these metals in increasing order of their reducing power. More negative the value of standard
electrode potentials of metals is, more will be the reducing power.
38. Determine the values of equilibrium constant (Kc) and ΔG° for the following reaction :
Ni(s) + 2Ag+ (aq) → Ni2+ (aq) + 2Ag(s), E° = 1.05 V (1F = 96500 C mol-1) (ANSWER = -202650 J/mol and
K = 0.35 *107)
39. The standard electrode potential (E°) for Daniel cell is +1.1 V. Calculate the ΔG° for the reaction
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
(1 F = 96500 C mol-1). (ANSWER = -212.3 KJ/mol)
40. A copper-silver cell is set up. The copper ion concentration in it is 0.10 M. The concentration of silver ion is
not known. The cell potential is measured 0,422 V. Determine the concentration of silver ion in the cell.
Given : E°Ag+/Ag = + 0.80 V, E° Cu2+/Cu = + 0.34 V. (ANSWER = 13.93 M)
41. A voltaic cell is set up at 25°C with the following half cells :
Al/Al3+ (0.001 M) and Ni/Ni2+ (0.50 M)
Write an equation for the reaction that occurs when the cell generates an electric current and determine the
cell potential. E0Ni2+/Ni=−0.25V and E0Al3+/Al=−1.66V (Log 8 × 10-6 = -0.54) (ANSWER = 1.46 V)
42. The cell in which the following reaction occurs :
2Fe3+ (aq) + 2I– (aq) → 2Fe2+ (aq) + I2 (s) has E0cell = 0.236V at 298K. Calculate the standard Gibbs energy
and the equilibrium constant of the cell reaction.
(Antilog of 6.5 = 3.162 × 106; of 8.0 = 10 × 108; of 8.5 = 3.162 × 108) (ANSWER = 0.529 V)
43. Calculate the emf of the following cell at 25°C : Ag(s) | Ag+ (10-3 M) || Cu2+ (10-1 M) | Cu(s) Given E0cell =
+0.46 V and log 10n = n. (ANSWER = 0.31 V)
CONDUCTIVITY
44. Express the relation among cell constant, resistance of the solution in the cell and conductivity of the
solution. How is molar conductivity of a solution related to its conductivity?
45. Question 13.
The molar conductivity of a 1.5 M solution of an electrolyte is found to be 138.9 S cm2 mol-1. Calculate the
conductivity of this solution. (ANSWER = 0.20835 S cm-1)
46. The conductivity of 0.20 M solution of KCl at 298 K is 0.025 S cm-1. Calculate its molar conductivity.
(ANSWER Λm = 125 S cm2 mol-1)
47. The conductivity of 0.001 M acetic acid is 4 × 10-5 S/cm. Calculate the dissociation constant of acetic acid, if
molar conductivity at infinite dilution for acetic acid is 390 S cm2/mol. (1.46 *10-6)
48. State Kohlrausch law of independent migration of ions. Why does the conductivity of a solution decrease
with dilution?
49. Define conductivity and molar conductivity for the solution of an electrolyte. Discuss their Variation with
change in temperature.
50. Calculate the degree of dissociation (a) of acetic acid if its molar conductivity (Λm) is 39.05 S cm2 mol-1.
Given: λ°(H+) = 349.6 S cm2 mol-1 and λ°(CH3COO–) = 40.9 S cm2 mol-1 (ANSWER = 0.1)
51. The electrical resistance of a column of 0.05 M NaOH solution of diameter 1 cm and length 50 cm is 5.55 ×
103 ohm. Calculate its resistivity, conductivity and molar conductivity. (ANSWER = 229.6 S cm2/mol)
52. When a certain conductance cell was filled with 0.1 M KCl, it has a resistance of 85 ohms at 25°C. When the
same cell was filled with an aqueous solution of 0.052 M unknown electrolyte, the resistance was 96 ohms.
Calculate the molar conductance of the electrolyte at this concentration.
[Specific conductance of 0.1 M KCl = 1.29 × 10-2 ohm-1 cm-1] (ANSWER = 219.23 S cm2/mol)
53. Conductivity of 2.5 × 10-4 M methanoic acid is 5.25 × 10-5 S cm-1. Calculate its molar conductivity and
degree of dissociation. Given : λ0(H+) = 349.5 Scm2 mol-1 and λ0(HCOO–) = 50.5 Scm2 mol-1. (ANSWER =
0.525)
ELECTROLYSIS
54. (a) Following reactions occur at cathode during the electrolysis of aqueous silver chloride solution :
Ag+(aq) + e– → Ag(s) E° = +0.80 V
H+(aq) + e– → 12H2(g) E° = 0.00 V
On the basis of their standard reduction electrode potential (E°) values, which reaction is feasible at the
cathode and why?
55. Calculate the time to deposit 1.27 g of copper at cathode when a current of 2A was passed through the
solution of CuSO4. (ANSWER = 1930 s) (Molar mass of Cu = 63.5 g mol-1,1 F = 96500 C mol-1)
56. Following reactions may occur at cathode during the electrolysis of aqueous CuCl2 solution using Pt
electrodes:
On the basis of their standard electrode potential values, which reaction is feasible at cathode and why?
57. How many coulombs are required to reduce 1 mole Cr2O72- to Cr3+?
58. How much electricity in terms of Faradays is required to produce 20 g of calcium from molten CaCl2?
59. A current was passed for 5 hours through two electrolytic cells connected in series. The first cell contains
AuCl3 and second cell CuSO4 solution. If 9.85 g of gold was deposited in the first cell, what amount of
copper gets deposited in the second cell? Also calculate magnitude of current in ampere.
Given: Atomic mass of Au = 197 amu and Cu = 63.5 amu. (AMOUNT = 4.76 g of Cu and I = 0.8 A)
60. (i) Calculate the mass of Ag deposited at cathode when a current of 2 amperes was passed through a solution
of AgNO3 for 15 minutes. [Given: Molar mass of Ag = 108 g mol-1 1F = 96,500 C mol-1)
(ii) Define fuel cell. (ANSWER = 2.0145 g)
61. (a) How many moles of mercury will be produced by electrolysing 1.0 M Hg(NO3)2 solution with a current
of 2.00 A for 3 hours? [Hg(NO3)2 = 200.6 g mol-1] (ANSWER = 0.1119 mole)
(b) A voltaic cell is set up at 25 °C with the following half-cells Al2+ (0.001 M) and Ni2+ (0.50 M). Write an
equation for the reaction that occurs when the cell generates an electric current and determine the cell
potential. (Given : E0Ni2+/Ni = – 0.25 V, E0Al3+/Al = – 1.66 V) (ANSWER = 1.46 V)
62. Predict the products of electrolysis in each of the following:
(i) An aqueous solution of AgNO3 with platinum electrodes.
(ii) An aqueous solution of H2SO4 with platinum electrodes.
(b) Estimate the minimum potential difference needed to reduce Al2O3 at 500°C. The Gibbs energy change
for the decomposition reaction 23 Al2O3 → 43 Al + O2 is 960 kJ
(F = 96500 C mol-1) (ANSWER = -2.487 V)