Unit - 3 in the following cell :Zn(s)|Zn2+(aq)||Ag+ (aq)|Ag (s)

21. Rusting of iron becomes quicker in saline water?

ELECTROCHEMISTRY 22. Two metals A and B have reduction potential values of –
0.25V and 0.80V respectively. Which of these will
VSA QUESTIONS (1 - MARK QUESTIONS) liberate hydrogen gas from dilute H2SO4?
1. What is a galvanic cell? 23. Express the relation between conductivity and molar
2. Write the unit of Faraday constant. conductivity.
3. Give the cell representation for Daniell Cell. 24. Name the cell which was used in Apollo space
4. Mention the purpose of salt-bridge placed between programme.
two half-cells of a galvanic cell? 25. How many faradays are required to oxidize 1
5. Give the condition for Daniell Cell in which there is no mole of H2O to O2.
flow of electrons or current. SA (I) TYPE QUESTIONS (2 - MARK QUESTIONS)
6. How is electrode potential different from cell potential? 1. List two points of difference between metallic
7. Can you store zinc sulphate solution in a copper conductance and electrolytic conductance.
container? Give suitable reason. (EZn2+/Zn = – 2. List two points of difference between
electrochemical cell and electrolytic cell.
01.76V, E Cu2+/Cu = 0.34v) 3. List two factors which affect the conductivity of ionic
8. How does electrochemical series help us in predicting solutions.
whether a redox reaction is feasible or not? 4. A conventional method of representing a Daniel cell is
Write Nernst equation for the electrode reaction. Mn++ :
ne–  M(s) at 298 K and 1 bar pressure. Zn(s)|Zn2+ (1M)||Cu2+(1M)|Cu(s).
(i) Draw a diagram of the cell and mark anode
9. List the two factors that influence the value of cell
and cathode as current is drawn from the
potential of a galvanic cell.
cell.
10. How is equilibrium constant of a reaction related to
(ii) Write the reactions taking place at the cathode
standard cell potential?
and the anode during the operation of Daniel
11. Write the relation between Ecell and equilibrium constant cell.
(K) of cell reaction. *5. Suggest a method to determine the °m value of
12. Define cell constant. Write the SI unit of cell constant.
water.
13. How does specific conductance or conductivity of electrolytic
6. Write the cell reaction which occur in the lead
solution vary with temperature?
storage battery (a) when the battery is in use (b)
14. What is the SI unit of (i) Conductance; (ii) Conductivity?
when the battery is on charging.
15. Represent a concentration cell with a suitable example
7. Why absolute value of electrode potential cannot be
16. State one difference between a primary battery and
determined?
secondary battery.
8. Account for the fact that when chlorine is passed
17. Galvanized iron does not corrode even if the coating of
through a fluoride solution, no reaction takes
zinc is broken. Explain why?
place. Given E F 2F– = 2.87
(Given : E0 Fe 2+= – 0.44V; E0 Zn 2+= – 0.76V
2 2

18. Write the name of a chemical substance which is used to 2Cl– Cl 2Cl– = 1.36V
prevent corrosion.Show is the direction of flow of electrons 9. Copper does not dissolve in HCl (aq) but dissolves in
 HNO3 (aq) producing Cu2+ ions. Explain the 3. Give reasons for :
difference in behaviour. (a) For a weak electrolyte, its molar
[Given E0Cu2+ Cu– = 0.34V; E0Cl 2Cl– = 1.36V and conductivity of dilute solution increases as
NO 4H+ +3e– NO (g) + 2H O, ENO NO = 0.97V]3 3
2 the concentration of solution is decreased.
(b) Molar conductivity of a strong electrolyte like
10. Explain the following observations : KCl decreases almost linearly while increasing
(a) The product of electrolysis of molten NaCl concentration?
are sodium metal and chlorine gas. (c) It is not easy to determine °m of a weak
(b) The product of electrolysis of aqueous sodium electrolyte by extrapolation of c s m
chloride solution are NaOH, Cl2 and H2. curves?
11. What are fuel cells? Describe the principle and 4. (a) Write the mechanism of the corrosion of metals.
overall reaction involved in the working of (b) How is underground iron pipe is protected from
hydrogen–oxygen fuel cell or CH3OH – O2 fuel corrosion?
cell. 5. Formulate the galvanic cell in which the following
12. Explain the meaning of the terms
reaction takes place : Zn(s) + 2Ag+ (aq) 
(a) Ionic mobility. (b) Overvoltage.
*13. Account for the following observations : Zn2+ (aq) + 2Ag(s)
(a) In a dry cell, the build up of ammonia around State
the carbon cathode should disrupt the electric (a) Which one of its electrodes is negatively
current, but in practice this does not happen. charged?
(b) Ordinary dry cells are not rechargeable. (b) The reaction taking place at each of its
16. You are aquainted with the construction and electrode.
working of a lead storage battery. Give the (c) The direction of current within this *7. The standard
plausible reasons for these facts. reduction potentials are as given below :–
(a) There is only a single compartment unlike
other electrochemical cells which have two Half Cell E° Value
compartments Zn (OH)2/Zn – 1.245 V
(b) Addition of water is necessary from time to time Mg (OH)2/Mg – 2.690 V
for maintenance Fe (OH)2/Fe – 0.877 V
Fe (OH)3/Fe – 2.30 V
SA (II) TYPE QUESTIONS (3 - MARK QUESTIONS) Under standard conditions :
1. State the relationship amongst cell constant of a (a) Which is the strongest reducing agent?
cell, resistance of the solution in the cell and (b) Which reducing agent could reduce Zn(OH)2 to
conductivity of the solution. How is molar Zn?
conductivity of a solute related to conductivity of (c) Which reducing agent could reduce Fe(OH)2 to
its solution? Fe?
2. Describe the composition of anode and cathode in a
mercury cell. Write the electrode reactions for this LONG ANSWER TYPE QUESTIONS (5 MARKS)
cell. Why does it provide constant voltage 1. (a) Explain with example the terms weak and strong
throughout its life? electrolytes.
 (b) Calculate the emf of the cell 3. (i) Define molar conductivity. Draw the plots
Mg Mg 2 (0.001M Cu2 (0.001M
 ) Cu E Cu2  0.34V; E  showing the variation of molar conductivity for
strong and weak electrolyte with square root
Mg 2  2.375V Cu Mg
of concentation.
[Ans. : 2.651 V]
(ii) Resistance of a solution (A) is 50 ohm and that
2. (a) Explain Kohlrausch law of independent
of solution (B) is 100 ohm, both solutions being
migration of ions. Mention two applications of
taken in the same conductivity cell, if equal
this law.
volumes of solutions (A) and (B) are mixed,
(b) The conductivity of 0.001M CH3COOH is 4.95 ×
what will be the resistance of the mixture,
10–5 Scm–1. Calculate its dissociation using the same cell? Assume that there is no
constant. Given for acetic acid °m is 390.5 S increase in the degree of dissociation of (A)
and (B) on mixing. [Ans. : 66.66 ohm]
cm2 mol–1.[Ans. : = 0.126] [Hint. : k = Conductivity, y = Cell constant]
1

4. (a) State Faraday’s first and second laws of

electrolysis.
(b) Silver is deposited on a metallic vessel of
surface area 800 cm2 by passing current of
0.2 ampere for 3 hours. Calculate the
thickness of silver deposited.
(Density of silver = 10.47 g cm –3, Molar
atomic mass of silver = 107.924 g mol–1]
[Ans. :
2.9 × 10 –4 cm]
5. (a) Draw the diagram of standard hydrogen
electrode. Write the electrode reaction.
(b) Calculate the equilibrium constant
for the reaction : Fe2+ + Ce4+
 Ce3+ + Fe3+


Given E Ce4
 
 1.44V ; E
Ce3
Fe3 Fe2
 0.68V

[Ans. : 7.6 × 1012]

 (b) Will the cell generate emf when concentration
NUMERICAL PROBLEMS becomes equal?
*1. The emf of the following cells are: [Ans. : (a)
Ag Ag+ (1M Zn Zn2+ (1M 0.295V, (b) No.]
Cu (1M) Cu, E = 0.46V Cu2+
2+
3. Calculate the equilibrium constant for
(1M) Cu, E = 1.1V Calculate emf the reaction at 25°C. Cu(s) + 2Ag+
of the cell : (aq)  Cu2+ (aq) + 2Ag (s)
An (s) Zn2+ (1M Ag2+ (1M) Ag (s) The standard cell potential for the reaction at 25°C is
0.46V.
[Given R = 8.314 JK–1 mol–1] [Ans. :
2. For concentration cell
4.0 × 1015]
Cu (s) Cu2+ (0.01M Cu2+ (0.1M) Cu (s) 4. Calculate G° for the reaction.
Cu2+ (aq) + Fe(s)  Fe2+ (aq) + Cu(s)
(a) Calculate the cell potential.
E    0.34 V; E
Cu2+
Cu
   0.44 V
Fe2
Fe
 [Ans. : –150, 540 kJ]
6. Write the Nernst equation and calculate the emf Cu(s) | Cu2+ (0.130M) || Ag+ (10–2 M) | Ag(s)
of the following cell at 298K.
Given 
E Cu2+
Cu
  0.34 V; E
Ag 
Ag
  0.80 V [Ans. : 0.37V]
Calculate the electrode potential
7. A zinc rod is dipped in 0.1M solution of ZnSO4. The
salt is 95% dissociated at this dilution at 298K.
 
E


Zn2+
Zn
 
 – 0.76 V .  [Ans. : –0.7902V]

8. For the electrode Pt, H2 (1 atm) | H+ (aq) (xM), the reduction electrode
potential at 25°C is – 0.34V. Write the electrode
reaction and calculate the value of x. and the pH
of solution.
[Ans. : x = 1.807 × 10–
6, pH = 5.743]
9. For what concentration of Ag+ (aq) will the emf of
the given cell be zero at 25°C if concentration of
Cu2+ (aq) is 0.1M?
 
Given E Ag+
Ag
 0.80 V; E
Cu2
Cu
   0.34 V .
EØ Br2 / Br – / Pt = 1.09V.
Cell : Cu (s) | Cu2+ (aq) || Ag+ (aq) | Ag(s) [Ans. : 5.3 × [An
10–9] s. :
10. Zinc granules are added in excess to 500 mL of 1.0 –
M nickel nitrate solution at 25°C until the 1.29
equilibrium is reached. If the standard reduction 7V]
15. In the button cells widely used in watches and other
potential of Zn2+ | Zn and Ni2+ | Ni are –0.75 V
derices, the following reaction takes place :
and – 0.24 V respectively, find out the
2+ Zn(s) + Ag2O (s) + H2O (l)  Zn2+ (ag) + 2Ag(s) +
concentration of Ni in solution at equilibrium.
[Ans. : 5.88 2OH–(aq)
× 10–18M] Determine rGØ and EØ for the reaction.
11. The molar conductivity of 0.1M CH 3COOH solution is
Given EØ = – 0.76V; EØ = 0.8V
Zn2+/Zn Ag+/Ag
4.6 S cm2 mol–1. Calculate the conductivity and [Ans.: –301.08 kJ / mol.,
resistivity of the solution. cell
E
[Ans. : .00046 S cm–1, 2174  cm]
12. The molar conductivities of NH+ ion and Cl– ion are = 1.56V]
4
73.5 S cm2 mol–1 and
76.255 cm2 mol–1 respectively. The specific
conductivity of 0.1 M NH4Cl is
1.288 × 10–2 S cm–1. Calculate the dissociation
constant of NH4Cl.
[Ans. :
7.396 ×
10–2]
13. Molar conductivity at infinite dilution for NH 4Cl,
NaOH and NaCl solution at 298K are respectively
129.8, 218.4 and 108.9 Scm2 mol–1 and m for
10–2 M solution of NH4OH is 9.33 S cm2 mol–1.
Calculate the degree of dissociation of NH 4OH.
[Ans. : 0.039]
14. Write the Nernst equation and emf of the following cell at
298 K; Pt(s)/
Br2(l)| Br–(0.010M) || H+(0.030M) | H2(g) (0.9 bar) | Pt(s).