Revision Assignment

DAY – I : SOLVED OBJECTIVE EXAMPLES

Example 1:
An aqueous solution containing one mole per litre each of Cu(NO3)2, AgNO3, Hg2(NO3)2, Mg(NO3)2 is
being electrolysed by using inert electrodes. The value of standard potentials are

Eo  0.80V, E o  0.79V , E o  0.34V and E o  2.3V.

Ag | Ag Hg2  | Hg Cu2  | Cu Mg2  | Mg
2

With increasing voltage, the sequence of deposition of metals on the cathode will be
(a) Ag, Hg, Cu, Mg (b) Mg, Cu, Hg, Ag
(c) Ag, Hg, Cu (d) Cu, Hg, Ag
Solution:
The metal ions will be preferentially discharged on cathode in the order of their decreasing reduction
+
potentials. The order of deposition of metals will be Ag, Hg and Cu. Mg will not be deposited because H will
+
be preferentially discharged to release H2 and in an aqueous solution, H will never get completely consumed
during the time period of electrolysis.
 (c)

Example 2:
The standard EMF of the cell in which the reaction, MnO 4  5Fe 2   8H   Mn2   5Fe 3   4H 2 O
occurs is 0.59 V at 25°C. The equilibrium constant for the given reaction is approximately
(a) 50 (b) 10
50 5
(c) 10 (d) 10
Solution:
For the given cell reaction,
o
G° = nF E cell  RT ln K eq

5  96500  0.59 = 2.303  8.314  298 log Keq

49 50
Keq = 7.8  10  10
 (c)

Example 3:
2+ 2+ +
The standard reduction potentials of Cu | Cu and Cu | Cu are 0.34 and 0.16 V respectively. The
+
standard electrode potential of Cu | Cu half cell is
(a) 0.18 V (b) 0.82 V
(c) 0.52 V (d) 0.49 V
 Revision Assignment

Solution:
The reactions among various half cells are related as

+ 2e  Cu
2+
Cu ; G1  2F  0.34 =  0.68 F

+ e
+ 2+
Cu  Cu ; G 2  F  0.16 = 0.16 F

  
Cu + e  Cu
+
; G 3  G1  G 2  0.52 F   FE

 E° = 0.52
 (c)

Example 4:
The EMF of the cell, Ag | AgCl (saturated solution) || Cl (c1 M) | AgCl | Ag is given by

0.059 K SP 0.059 c1
(a) E cell   log (b) E cell   log
1 c1 1 K SP

0.059 K SP 0.059 c1
(c) E cell  log (d) E cell  log
1 c1 1 K SP
where KSP is the solubility product of AgCl.
Solution:
The given cell can be reduced to

+  K 
Ag | AgCl (satd. solution) || Ag  SP  | Ag
 [Cl  ] 
 
The reactions occurring at the two electrodes are

At anode: Ag  Ag A  e 

At cathode: Ag C  e   Ag
Net cell reaction: Ag C  Ag A

[ Ag A ] [ Ag C ]
 E cell  E ocell  0.059 log  0.059 log
[ Ag C ] [ Ag A ]

[Since, it is a concentration cell for which E ocell  0]

K SP K SP K SP
 E cell  0.059 log  0.059 log 
= 0.059 log
 c1
[Cl ] K SP [Cl ]

 (c)
 Revision Assignment

Example 5:
+
If the pressure of H2 gas is increased from 1 atm to 100 atm keeping H concentration constant at 1 M,
the change in reduction potential of hydrogen half cell at 25°C will be
(a) 0.059 V (b) 0.59 V
(c) 0.0295 V (d) 0.118 V
Solution:
The half cell reaction for hydrogen half cell acting as cathode is
2H + 2e  H2
+

0.059 PH
 E  Eo   log  22
H | H 2
2 H |H 2 [H ]

0.059 1
E  log  2
H | H 2 2 [H ]
+
Now, when the pressure of H2 gas is changed to 100 atm without changing [H ], the reduction potential
becomes
0.059 100
 E H | H   log  2
2 2 [H ]

0.059 100 [H  ] 2
 Change in reduction potential = E  E H | H = log  2  = 0.059 V
H | H 2 1
2 2 [H ]

 (a)

DAY – II : SOLVED SUBJECTIVE EXAMPLES

Example 1:
Calculate the EMF of the electrode concentration cell,
2+
ZnHg(c1 M) | Zn (aq) | Hg Zn(c2 M)
at 25°C, if the concentrations of the zinc amalgam are : c1 = 10 g per 100 g of mercury and
c2 = 1 g per 100 g of mercury.
Solution:
The cell reactions in the given electrode concentration cell are
+ 2e  Zn(c2)
2+
At cathode: Zn

+ 2e
2+
At anode: Zn(c1)  Zn
Net cell reaction: Zn(c1)  Zn(c2)
0.059 c 
E cell  log 1 (since E cell = 0)
2 c2

 10 
Ecell = 0.0295 log   = 0.0295 V
 1
Example 2:
By how much is the oxidising power of the MnO 4 | Mn2  couple decreases if the H concentration is
+

decreased from 1 M to 104 M at 25°C. Assume that the concentration of other species do not change.
 Revision Assignment

Solution:
In acidic medium, MnO 4 acts as oxidizing agent and reduces to Mn
2+
as per the reaction

MnO 4  8H   5e   Mn 2  4H 2 O

0.059 [Mn 2  ]
E  Eo  log
MnO 
4 | Mn
2
MnO 
4 | Mn
2
5 [MnO 4 ] [H  ] 8

0.059 [Mn 2  ]
 Eo  log
MnO 
4 | Mn
2
5 [MnO 4 ] (1) 8

0.059 [Mn 2 ]
E  Eo  log
M nO  2
MnO  [MnO 4 ] [10  4 ] 8
2
4 | Mn 4 | Mn 5

  0.059  [MnO 4 ] (1) 8 [Mn 2  ] 

  E M nO  | Mn 2   E M nO  | Mn 2     log    0.3776 V
 4 4  5  [Mn 2  ] [MnO 4 ] (10  4 ) 8 

Thus, the oxidizing power of MnO 4 | Mn 2 couple decreases by 0.3776 V from its standard value.

Example 3:
EMF of the following cell is 0.67 V at 298 K.
+
Pt | H2 (1 atm) | H (pH = X) || KCl (1 N) | Hg2Cl2(s) | Hg

Calculate pH of the anode compartment. Given: E o  = 0.28 V.

Cl | Hg2Cl2| Hg

Solution:
The reactions occurring in the electrochemical cell are
H2  2H + 2e
+
At anode:

At cathode: Hg2Cl2 + 2e  2Hg + 2Cl

Net cell reaction: H2 + Hg2Cl2  2H + 2Hg + 2Cl
+

0.059 [Cl  ] 2 [H  ] 2
 E cell  E o   Eo   log
Cl | Hg2Cl2 | Hg H | H2 2 PH2

(Hg and Hg2Cl2 do not appear as they are pure liquid and pure solid respectively)

0.059 [H  ] 2  (1) 2
0.67 = 0.28  log  0.28  0.059 log [H  ]
2 1
0.67 = 0.28 + 0.059 pH
 pH = 6.61

Example 4:
2+ 2+ 3+ +
Find the equilibrium constant for the reaction, In + Cu  In + Cu , at 298 K.
  
Given: E Cu2  /Cu = 0.15 V ; E In3  /In = 0.42 V & E In2  /In = 0.40 V.
Solution:
In + 2e  In
+3 +1
……(1)
In + e  In
+2 +1
……(2)
In  In + e
+2 +3
……(3)
(3) = (2)  (1)
FE° = 2F(0.42) + F(0.40) ; E° = 0.84 + 0.4 = 0.44 V
 Revision Assignment

+2 +2 +3 +
In + Cu  In + Cu ; E° = 0.15 + 0.44 = 0.59 V
0.59 10
n F E° = RT ln K ; = log K ; K = 10 .
0.059

Example 5:
For a saturated solution of AgCl at 25°C, specific conductance is 3.41  106 ohm1 cm1 and that of
water used for preparing the solution was 1.6  106 ohm1 cm1. What is the solubility product of

AgCl? Given: Λ eqv (AgCl) = 138.3 ohm1 cm1 equiv1.

Solution:
Specific conductance of AgCl = Specific conductance of solution  specific conductance of H2O.
= (3.41  1.6)  106 = 1.81  106 ohm1 cm1.
For saturated solution of sparingly soluble salt,

eq = eq

and concentration of AgCl = solubility of AgCl.

1000  specific conduc tan ce of AgCl
 eq = (since molarity = normality for AgCl)
So lub ility of AgCl

1000  1.81  10 6
 138.3 =
s

1000  1.81  10 6
s= = 1.31  105 mol/lit
138 .3
The solubility equilibrium of AgCl is shown as
Ag (aq) + Cl(aq)
+
AgCl(s)
 KSP = [Ag ] [Cl] = s  s = s
+ 2

= (1.31  105) = 1.72  1010 M

2 2

DAY – III

1. A dilute solution of sodium sulphate in water is electrolysed using inert electrodes. The products at
the cathode and anode are respectively
(a) H2, O2 (b) O2, H2
(c) O2, Na (d) O2, SO2

2. In an electrolytic cell, which of the following statement is not true?

(a) Cathode is negative terminal.
(b) Cathode is positive terminal.
(c) Reduction occurs at cathode.
(d) Electrons enter into cathode from the external cell.

3. The density of Cu is 8.94 g cm3. The quantity of electricity needed to plate an area
10 cm  10 cm to a thickness of 102 cm using CuSO4 solution would be
(a) 13586 C (b) 27155 C
(c) 40758 C (d) 20348 C

4. During electrolysis of an aqueous solution of sodium sulphate, 2.4 L of oxygen at STP was liberated
at anode. The volume of hydrogen at STP, liberated at cathode would be
 Revision Assignment

(a) 1.2 L (b) 2.4 L

(c) 2.6 L (d) 4.8 L

5. During electrolysis of an aqueous solution of CuSO4 using copper electrodes, if 2.5 g of Cu is

deposited at cathode, then at anode
(a) 890 ml of Cl2 at STP is liberated (b) 445 ml of O2 at STP is liberated
(c) 2.5 g of copper is deposited (d) a decrease of 2.5 g of mass takes place

6. A current of 9.65 A is passed for 3 h between nickel cathode and Pt anode in 0.5 L of a 2 M solution
of Ni(NO3)2. The molarity of solution after electrolysis would be
(a) 0.46 M (b) 0.625 M
(c) 0.92 M (d) 1.25 M

7. Which of the following statement is correct?

If E oCu2 | Cu = 0.337 V and E oSn2 | Sn =  0.136 V.
(a) Cu2+ ions can be reduced by H2(g) (b) Cu can be oxidized by H+
(c) Sn2+ ions can be reduced by H2 (d) Cu can reduce Sn2+

8. The reduction potential of hydrogen halfcell will be negative if

(a) p(H2) = 1 atm and [H+] = 1 M (b) p(H2) = 1 atm and [H+] = 2 M
+
(c) p(H2) = 2 atm and [H ] = 1 M (d) p(H2) = 2 atm and [H+] = 2 M

  
9. If E Fe 3
|Fe
and E Fe2 |Fe are 0.036 V and 0.44 V respectively, then the value of E Fe 3
| Fe 2 
would be?
(a)  0.77 V (b) + 0.77 V
(c)  0.916 V (d) + 0.916 V

10. Consider the cell potentials,

 
E 2 =  2.37 V and E =  0.036 V.
Mg |Mg Fe3  |Fe

The best reducing agent among them would be

(a) Mg2+ (b) Fe3+
(c) Mg (d) Fe

ANSWERS – III

1. (a) 2. (b) 3. (b) 4. (d) 5. (d)

6. (c) 7. (a) 8. (c) 9. (b) 10. (c)

DAY – IV

1. The standard reduction potential values of three metallic cations, X, Y and Z are 0.52, 3.03 and
1.18 V respectively. The order of reducing power of the corresponding metals is
(a) Y > Z > X (b) X > Y > Z
(c) Z > Y > X (d) Z > X > Y

2. The standard reduction potentials of Cr3+ | Cr2+ and Cr3+ | Cr are 0.41 V and 0.74 V respectively.
The standard electrode potentials of Cr2+ | Cr halfcell is
 Revision Assignment

(a) +1.81 V (b) 1.81 V

(c) + 0.905 V (d)  0.905 V

3. In lead storage battery, during discharging process (Refer NCERT)

(a) PbO2 gets oxidised (b) H2SO4 is produced
(c) density of H2SO4 solution decreases (d) density of H2SO4 solution increases

4. Salts of A (atomic weight = 7), B (atomic weight = 27) and C (atomic weight = 48) were electrolysed
under identical conditions using the same quantity of electricity. It was found that when 2.1 g of A
was deposited, the weights of B and C deposited were 2.7 and 7.2 g. The valencies (n-factor) of A,
B and C respectively are
(a) 3, 1 and 2 (b) 1, 3 and 2
(c) 3, 1 and 3 (d) 2, 3 and 2

5. The standard potential for the reaction,

½ O2 + 2H+ + 2e  H2O
would be (Given: Kw of water at 25°C is 1014 and E OH | O2 ,H2O =  0.40 V)
(a)  1.23 V (b) 1.23 V
(c)  0.828 V (d) 0.828 V

6. 1 coulomb of electricity produces m kg of a substance ‘X’. Electrochemical equivalent of

‘X’ is
(a) m (b) m × 103
3
(c) m × 10 (d) all wrong

7. Electrochemical equivalent of a substance is .0006735. Its equivalent weight is

(a) 65 (b) 67.35
(c) 130 (d) cannot be calculated
o o o o
8. Given that E Ag | Ag = 0.8 volts, E 2 = 0.79 volts, E Cu | Cu2  = 0.34 volts, E Mg | Mg2  = 0.237
Hg Hg
| 2

volts. What is the order of deposition of these metals from their aqueous salts solution?
(a) Ag, Cu, Mg (b) Ag, Hg, Cu
(c) Mg, Ag, Hg, Cu (d) Cu, Hg, Ag

9. The charge of an electron is 1.6 × 1019 coulomb. How many electrons per second pass through a
cross section of a Cu wire carrying 1016 amp current?
(a) 300 (b) 1800
(c) 1200 (d) 625

10. A current of 2 amp passing for 5 hours through a molten tin salt deposits 22.2 g of tin.
The oxidation state of the tin in the salt is (atomic weight of Sn = 119).
(a) +4 (b) +3
(c) +2 (d) +1

ANSWER – IV

1. (a) 2. (d) 3. (c) 4. (b) 5. (d)

6. (a) 7. (a) 8. (b) 9. (d) 10. (c)

 Revision Assignment

DAY – V

[ Zn 2 ]
1. Which of the following graph (Ecell Vs log ) correctly correlates Ecell as a function of
[Cu 2 ]
concentrations of ions for the given reaction?

Zn(s) + Cu2+ (M)  Zn2+( M ) + Cu(s); E cell = 1.10 V

1.10 V 1.10 V
(a) (b)

 1.0 0 +1.0  1.0 0 +1.0

1.10 V
1.10 V
(c) (d)

 1.0 0 +1.0  1.0 0 +1.0


2. E Quinhydron e = 1.30 V. At pH = 2, EQuinhydrone will be [Assume that the concentration of hydroquinone
and quinone is (1M)]
OH O

+ 2H+ + 2e

OH O
hydroquinone quinone
(a) 1.36 V (b) 1.30 V
(c) 1.48 V (d) 1.20 V

3. Zn | Zn2+ (c1 M) || Zn2+ (c2 M) | Zn

For this cell, G would be negative, if
(a) c1 = c2 (b) c1 > c2
(c) c2 > c1 (d) None of these

4. The oxidation potential of a hydrogen electrode at pH = 10 and PH2 = 1 atm, would be

(a) 0.51 V (b) 0.00 V
(c) + 0.59 V (d) 0.059 V

5. At 25°C, standard EMF of the cell having reactions involving two electron change is found to be
0.295 V. The equilibrium constant of the reaction would be
(a) 29.5  102 (b) 10
(c) 1010 (d) 29.5  1010

6. The emf of the given cell, Zn | Zn2+ (0.1 M) || Fe2+ (0.01 M) | Fe is 0.2905 V at 298 K.
Keq of this cell will be
(a) 100.26/0.0295 (b) 100.32/0.059
0.32/0.0295
(c) 10 (d) e0.32/0.0295
 Revision Assignment

7. The emf of the half cell Cl(c1) | AgCl(Ksp) | Ag is

0.059 1
(a) E Cl | AgCl | Ag  E  Cl | AgCl | Ag  log
1 c1
0.059 K sp
(b) E Cl | AgC l | Ag E Ag |Ag  log
1 c1

(c) E Cl | AgCl | Ag  E Cl | AgCl |Ag  0.059 log c 1
 0.059 c
(d) ECl | AgCl | Ag  E Ag | Ag  log 1
1 K sp

o
8. E Cu2  | Cu = 0.34 V, what will be the reduction potential at pH = 14 for he same couple.
Given Ksp Cu(OH)2 = 1019.
(a) 0.11 V (b) +0.11 V
(c) +0.22 V (d) 0.22 V

9. Pt(P1), H2 | H+ || H+ | H2. Pt(P2) which one is true if cell is feasible

(a) P1 > P2 (b) P1 < P2
(c) P1 = P2 (d) none of these

10. The standard electrode potentials of the two half cells are given below:
Ni2+ + 2e  Ni ; E° = 0.25 volt
Zn2+ + 2e  Zn ; E° = 0.77 volt
The voltage of feasible cell formed by combining the two half cells would be
(a) 1.02 volt (b) +1.36 volt
(c) +1.02 volt (d) +0.52 volt

ANSWERS – V

1. (b) 2. (c) 3. (c) 4. (c) 5. (c)

6. (a) 7. (d) 8. (d) 9. (a) 10. (b)

DAY – VI

1. Define conductivity and molar conductivity for the solution of an electrolyte.

2. Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is 100 . If the resistance of the
same cell when filled with 0.02 mol L–1 KCl solution is 520 , calculate the conductivity and molar
conductivity of 0.02 mol L–1 KCl solution. The conductivity of 0.1 mol L–1 KCl solution is 1.29 S/m.
3. The electrical resistance of a column of 0.05 mol L–1 NaOH solution of diameter 1 cm and length 50
cm is 5.55 × 103 ohm. Calculate its resistivity, conductivity and molar conductivity.
 Revision Assignment

4. The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm–1. Calculate its molar conductivity.
5. The resistance of a conductivity cell containing 0.001M KCl solution at 298 K is 1500 What is the
cell constant if conductivity of 0.001M KCl solution at 298 K is 0.146 × 10–3 S cm–1.

6.  m for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm2 mol–1 respectively. Calculate Å for HAc.

7. The conductivity of 0.001028 mol L–1 acetic acid is 4.95 × 10–5 S cm–1. Calculate its dissociation

constant if  m for acetic acid is 390.5 S cm2 mol–1.

8. Why does the conductivity of a solution decrease with dilution?

9. 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  0 = 349.6 S cm2 mol–1 and  0 = 54.6 S
M,(H ) M, (HCOO )

cm2 mol–1

10. Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S cm–1. Calculate its molar conductivity and if

M for acetic acid is 390.5 S cm2 mol–1, what is its dissociation constant?

SOLUTION – VI

1. Try yourself
mol S mol
2. Given, c1  0.1 , R1  100,k1 1.29 ands c 2  0.02 , R1  520 , k 2  ?
L m L
l
We know that, k  c 
A
l l k c
k1  c1  ....(1) and k 2  c2  ....(2)  from (1) and (2)  2  2
A A k1 c l

c2 0.02
 k 2  k1   (1.29 Sm1 )   0.258 S m1
cl 0.1

So,
S ml 1 m3
(0.258 )  (1000  6 )
k  1000 m L 10 ml
Molar conductivity = M    129  104 S m 2 mol –1
c mol
0.02
L
3. Given, R = 5.55  103 ohm, diameter = 1 cm, l = 50 cm, c = 0.05 mol L-1
Cross sectional Area (A) = 3.14  (0.5 cm)2 = 0.785 cm2 = 0.78510-4 m2
R =   l /A   = RA/l = 5.55103 ohm  0.785  10-4 m2 / 0.5 m = 0.87135 ohm-m
Conductivity (k) = 1/ = 1.147 S m-1
 Revision Assignment

S 1000 ml 1m3
(1.147 ) (  6 )
m L 10 ml
Molar Conductivity ( M ) = k  1000/c = 1
 2.294  10 2 S m2 mol 1
0.05 mol L

S ml 1 cm3
(0.0248 )  (1000  )
k  1000 cm L 1 ml
4. Molar conductivity = M    124 S cm2 mol –1
c mol
0.2
L
l
5. Cell Constant = = R  k = 1500 ohm  0.146 10-3 S cm-1 = 0.219 cm–1
A

6. 0M(HAc)  0HCl  0NaAc  0NaCl = 425.9 + 91.0 – 126.4 = 390.5 S cm2 mol–1
7.
ml 1cm3
( 4.95 105 Scm1 ) 1000 ( )
k  1000 L 1ml
m   1
 48.15 Scm2 mol1
C 0.001028 mol L
Given,  m  390.5 Scm mol 1
0 2

m 48.15
Therefore,   0
  0.123
m 390.5

c 2
Therefore, K a   c 2  0.001028  (0.1232 ) 1.56 105 mol L–1
(1   )
8. Conductivity of an electrolyte depends on number of ions per unit volume, which decreases with the
dilution of electrolyte. That’s why conductivity of a solution decrease with dilution.
9.
Given, c  0.025 mol L1 ,  M  46.1 S cm2 mol1
 0M (HCOOH)   0 (H )   0 (HCOO )  349.6  54.6  404.2 S cm2 mol 1
M M

M 46.1
Therefore, deg ree of dissociation ( )    0.114
 0M 404.2
c 2
Therefore, K a   c 2  0.025  (0.1142 )  3.25 10 4 mol L–1
(1   )

10.Given, conductivity (k) = 7.896 × 10–5 S cm–1 , c = 0.00241 M

k  1000 7.896  105 1000
Molar conductivity = M    32.76 S cm2 mol –1
c 0.00241
M 32.76
Therefore, deg ree of dissociation ( )    0.084
 0M 390.5

c2
Therefore, dissociation cons tan t (K a )   c2  0.00241  (0.0842 ) 1.7 10 5 mol L–1
(1   )