CHAPTER 3

ELECTROCHEMISTRY
ELECTROCHEMICAL CELL, BATTERIES AND CORROSION
1. Define electrochemical cell (or galvanic cell). What happens if external
potential applied becomes greater than E0cell of electrochemical cell?

2. Two half cell reactions of an electrochemical cell are given below:

MnO4-(aq) + 8H+(aq) + 5e- Mn2+(aq) + 4H2O(l), E0 = + 1.51 V
Sn2+(aq) Sn4+(aq) + 2e-, E0 = + 0.15
Construct the redox reaction from the standard potential of the cell and
predict the reaction is reactant favoured or product favoured.

3. Define electrode potential and standard electrode potential.

4. Write differences between electrochemical cell and electrolytic cell.

5. Given that the standard electrode potentials (E0) of metals are:
K+/K = -2.93 V , Ag+/Ag = 0.80 V, Cu2+/Cu = 0.34V
Mg2+/Mg = -2.37 V, Cr3+/Cr = -0.74 V , Fe2+/Fe = -0.44V
Arrange these metals in the increasing of their reducing power.

6. The standard reduction potential values of three metallic cations X,Y Z are
0.52 , -3.03 , -1.18 respectively. What will be the order of reducing power of
the corresponding metals?

7. On the basis of standard electrode potential values stated for acid solutions,
predict whether Ti4+ species may be used to oxidise Fe2+ to Fe3+.
Ti4+ + e- Ti 3+, E0 = + 0.01 V
Fe3+. + e- Fe2+ , E0 = + 0.77 V
8. What is the necessity to use a salt bridge in a galvanic cell?

9. Consider a cell given below:

Cu/ Cu2+ // Cl-/Cl2,Pt
Write the reactions at anode and cathode.

10. (i) Represent the galvanic cell in which the reaction

Zn(s) + 2 Ag+ →Zn2+(aq) + Ag (s) takesplace:
(ii) which electrode is negatively charged?
(iii) what are the carriers of the current in the cell?
(iii) Write reactions taking place at each electrode.

11. Can you store copper sulphate solution in a zinc pot?

12. Why does a galvanic cell become dead after some time?
13. Using the standard electrode potential given below, predict if the
reaction between the following is feasible:
i) Fe3+ and I- ii) Ag+ and Cu iii) Fe3+ and Br-
iv) Br2 and Fe2+ v) Ag and Fe3+
( given E0I2/I- = 0.541 V, E0Cu2+/Cu = 0.34 V, E0Br2/Br- = 1.090 V, E0Ag+/Ag = 0.80 V,
E0Fe3+/ Fe2+ = 0.77 V )

14. What is primary cell? Give an example.

15. What are secondary cells ? Give one difference between secondary cells
and fuel cells.
16. Name the electrolyte used in dry cell. Write its cathode and anode
reactions.

17. Why does a dry cell become dead after a long time even it has not been
used?

18. What is the role of ZnCl2 in a dry cell?

19. Mention the reactions occuring at anode and cathode, during working of
a mercury cell.

20. Why does the voltage of mercury cell remain constant during its
operation?
21. Write the overall reaction that occurs during use(discharging) of nickel-
cadmium cell. Is it a primary or secondary cell. Mention its one merit and
one demerit over the lead storage cell.

22. What type of battery is lead storage battery (lead acid accumulator)?
Write the anode and cathode reactions and the overall cell reaction occuring
in the operation of lead storage battery.

23. What are fuel cells? How do they resemble and differ from galvanic cells?

24. State advantages of H2 – O2 fuel cell over ordinary cell

 25. Suggest two materials other than hydrogen that can be used as fuel cels.

26. For the given cells : Lead storage cell, Mercury cell, Fuel cell and Dry
cell
Answer the following:
(i) Which cell is used in hearing aids?
(ii) Which cell was used in Appolo space programme?
(iii) Which cell used in automobiles and inverters?
(iv) Which cell does not have long life?
(v) Which cell used in transistors?

ELECTROLYTIC CONDUCTANCE
27. Express the relation among the cell constant, the resistance of the solution
in the cell and the conductivity of the solution. How is the conductivity of a
solution related to its molar conductivity?

28. Define specific conductance or conductivity.

29. Why does conductivity of a solution decreases with dilution?

30. Define molar conductivity of a solution and explain how molar
conductivity changes with change in concentration of solution for a weak and
strong electrolyte.

31. What is meant by limiting molar conductivity?

32. Why on dilution the Ʌm of CH3COOH increases drastically while that of

CH3COONa increases gradually?

33. State Kohlrausch law of independent migration of ions.

34. Write an expression for the molar conductivity of acetic acid at infinite
dilution according to Kohlrausch law.

35. Suggest a way to determine the Ʌ0m value of a) water and b)acetic acid.
ELECTROLYSIS AND ELECTROLYTIC CELLS
36. Define electrolyic cell. What is the change in free energy for electrolytic
cell?

37. State faraday’s first and second laws.

38. Predict the products of electrolysis in each of the following:

a) An aqueous solution of AgNO3 with silver electrodes.
b) An aqueous solution of AgNO3 with platinum electrodes.
c) A dilute solution of H2SO4 with platinum electrodes.
d) An aqueo-us solution of CuCl2 with platinum electrodes.

39. Why does an aqueous solution of NaCl on electrolysis give H2 gas at

cathode and not sodium metal?
 40. Define overvoltage.

41. During electrolysis of aqueous NaCl, why Cl is oxidised at anode instead

of water? Or
During electrolysis of NaCl solution, at anode : Cl2 and not O2. Account.

NUMERICALS
PROBLEMS RELATED TO ELECTROCHEMICAL CELL

1. Calculate the potential of hydrogen electrode in contact with a solution whose

pH is 10.

2. Zinc rod is dipped in 0.1M solution of ZnSO4. The salt is 95% dissociated at
this dilution at 298 K. Calculate the electrode potential.
Given : E0Zn2+/Zn = -0.76 V.
 3. Write the cell formulation and calculate the standard cell potential of the
galvanic cell in which the following reaction takes place:
Fe2+ (aq) + Ag+ (aq) Fe3+ (aq) + Ag (s) [Eo Ag+/Ag = 0.80V , Eo Fe3+/ Fe2+ =
+0.77V]

4. Calculate the emf of the following cell at 298 K:

Fe (s) / Fe2+(0.1 M)// Ag+ (0.1 M) /Ag(s)
Given E0 Fe2+/ Fe = -0.44 V , E0 Ag+/Ag = 0.80 V, R = 8.31 JK-1 mol-1, 1F = 96500 C
mol-1

5. Calculate potential of the cell

Cd (s) / Cd2+(0.10 M)// H+ (0.20 M) / Pt, H2 (0.5 atm)
Given E0 Cd2+/Cd = -0.40 V
 6. Calculate the cell potential, E at 25oC for the cell if the initial concentration of
Ni(NO3)2 is 0.100 molar and the initial concentration of AgNO3 is 1.00 molar.
[ Eo Ni2+/Ni = -0.25V ; Eo Ag+/Ag = 0.80V; log 10-1= -1]

7. Consider the cell composed of two half cells:

Cu (s) / Cu2+ (aq) and Ag (s) / Ag+ (aq) Calculate:
(i)the standard cell potential and
(ii) the cell potential at 298 K when Cu2+ is 2M and Ag+ is 0.05 M. ( Eo Cu2+/Cu =
0.34V ; Eo Ag+/Ag = 0.80V)
 8. The Eo values at 298 K corresponding to the following reduction electrode
processes are :
(i) Cu+/ Cu = +0.52 V ; (ii) Cu2+/ Cu+ = + 0.16 V
Formulate the galvanic cell for their combination. What will be the cell potential?
Calculate the ΔrGo for the cell reaction.

9. In the button cell widely used in watches the following reactions occurs:
Zn(s) + Ag2O(s) + H2O (l) Zn2+(aq) + 2Ag (s) + 2OH-(aq)
Determine E0 for the cell Zn2+(aq) and ΔrGo for the reaction.
(Given : Zn2+(aq) + 2 e- Zn(s) ; E0 = -0.76 V
Ag2O(s) + H2O (l) + 2 e- 2Ag (s) + 2OH-(aq) ; E0 = +0.80 V)

10. The cell in which the following reaction occurs:

2 Fe3+ (aq) + 2 I- (aq) → 2 Fe2+ (aq) + I2 (s) has E0cell = 0.236 V at 298 K.
Calculate standard gibbs energy and equilibrium constant of the cell reaction.
11. Calculate E0cell for the following reaction at 298 K:
2Cr (s) + 3Fe2+ (0.01M) 2Cr3+ (0.01 M) + 3 Fe (s)
Given : Ecell = 0.261 V .

12. The emf of the following cell is found to be 0.20 V at 298 K.

Cd (s) / Cd2+(?)// Ni2+ (2.0 M) /Ni(s)
What is the molar concentration of Cd2+ ions in the solution?
Given E0 Cd2+/Cd = -0.40 V and E0 Ni2+/Ni = -0.25 V
PROBLEMS RELATED TO ELECTROLYTIC CONDUCTANCE

13. The resistance of a conductivity cell containing 0.001 M KCl solution at 298 K
is 1500 ohm. What is the cell constant if the conductivity of 0.001 M KCl
solution at 298 K is 0.146 x 10-3 Scm-1?

14. The electrical resistance of a coloumn of 0.05 M NaOH solution of diameter 1

cm and length 50 cm is 5.55 x 103 ohm. Calculate its resistivity, conductivity
and molar conductivity.

15. At 298 K, the electrolytic conductivity of 0.2 M KCl solution is 2.50 x 10 -2 S

cm-1. Calculate its molar conductivity.
16. 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 the solution?

17. Conductivity of 0.00241 M acetic acid solution is 7.896 x 10 -5 S m -1. Calculate

its molar conductivity. If Ʌom for acetic acid be 390.5 S cm2 mol-1 , what would
be its dissociation constant?

18. The molar conductivity of 0.025 mol L-1 methanoic acid is 46.1 S cm2 mol-1.
Calculate its degree of dissociation and dissociation constant. Given λo (H+) =
349.6 S cm2 mol-1 and λo (HCOO-) = 54.6 S cm2 mol-1 .
 19. Calculate the degree of dissociation of acetic acid at 298K , given that :
Ʌm (CH3COOH) = 11.7 S cm2 mol-1
Ʌom (CH3COO-) = 40.9 S cm2 mol-1
Ʌom (H+) = 349.1 S cm2 mol-1

PROBLEMS RELATED TO QUANTITATIVE ASPECTS OF ELECTROLYSIS

20. A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5

amperes. What is the mass of copper deposited at the cathode? ( molar mass of
Cu = 63.5 g mol-1)

21. A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a

current of of 5 amperes for 20 minutes. What mass of nickel deposited at the
cathode? ( molar mass of Ni = 58.7 g mol-1)
22. Calculate the strength of the current required to deposit 1.2 g of magnesium
from molten magnesium chloride in one hour.( At. Mass of Mg = 24)

23. Two electrolytic cells containing silver nitrate solution and copper sulphate
solution are connected in series. A steady current of 2.5 ampere was passed
through them till 1.078 g of Ag were deposited. How long did the current flow?
What weight of Cu will be deposited? .( At. Mass of Cu = 63.5 and Ag = 108)

24. Three electrolytic cells A, B and C containing solutions of zinc sulphate, silver
nitrate and copper sulphate respectively are connected in series. A steady
current of 1.5 ampere was passed through them until 1.45 g of silver ere
deposited at the cathode of cell B. How long did the current flow? What mass
of Copper and Zinc were depositedin the concerned cells? ( At mass of Ag =
108, Zn = 65.4 , Cu = 63.5 )
25. Silver is electrodeposited on a metallic vessel of surface area 800 cm2 by
passing a current 0.2 ampere for 3 hours. Calculate the thickness of silver
deposited. Given the density of silver as 10.47 g/cc ( Atomic mass of Ag =
107.92 amu)

26. How much charge is required for the following reduction?

a) 1 mol of Al3+ to Al
b) 1 mol of Cu2+ to Cu
c) 1 mol of MnO4- to Mn2+

27. How much electricity in terms of Faraday is required to produce

(a) 20.0 g of Ca from molten CaCl2
(b) 40.0 g of Al from molten Al2O3?

28. If a current of 0.5 ampere flows through a metallic wire for 2 hours, how
many electrons flow through the wire?