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® 1
6. A 5.0 m mol dm–3 aqueous solution of KCl has
ELECTROCHEMISTRY
a conductance of 0.55 mS when measured in a
1. The electrode potential of M2+ / M of 3d-series
cell constant 1.3 cm–1. The molar conductivity
elements shows positive value of :
of this solution is _______ mSm2 mol–1.
(1) Zn (2) Fe (3) Co (4) Cu
(Round off to the Nearest Integer)
2. The magnitude of the change in oxidising
7. A KCl solution of conductivity 0.14 S m–1
power of the MnO4 / Mn2 couple is x × 10–4 V,
shows a resistance of 4.19  in a conductivity
if the H+ concentration is decreased from 1 M to
cell. If the same cell is filled with an HCl
10–4 M at 25°C. (Assume concentration of
solution, the resistance drops to 1.03 . The
MnO4 and Mn 2 to be same on change in H+
conductivity of the HCl solution is
concentration). The value of x is _______.
____× 10–2 S m–1. (Round off to the Nearest
(Rounded off to the nearest integer)
Integer).
 2.303 RT 
Given :  0.059 8. For the reaction
F 

3. Copper reduces NO3– into NO and NO2 2Fe3+(aq) + 2I–(aq)  2Fe2+(aq) + I2(s)
the magnitude of the standard molar free energy
depending upon the concentration of HNO3 in
change, rG°m = – ______ kJ (Round off to the
solution. (Assuming fixed [Cu2+] and
PNO = PNO ), the HNO3 concentration at which Nearest Integer).
2

the thermodynamic tendency for reduction of  EoFe2 /Fe(s)  0.440 V; E oFe3 /Fe(s)  0.036 V 
 
NO3– into NO and NO2 by copper is same is  EoI /2I  0.539 V; F  96500 C 
 2 
10x M. The value of 2x is _______. 9. The molar conductivities at infinite dilution of
(Rounded-off to the nearest integer) barium chloride, sulphuric acid and
o
[Given, E oCu 2 /Cu = 0.34 V, ENO– /NO = 0.96 V, hydrochloric acid are 280, 860 and 426 Scm2
3
mol–1 respectively. The molar conductivity at
o
E NO3– /NO2
= 0.79 V and at 298 K, infinite dilution of barium sulphate is _____

RT ___S cm2 mol–1(Round off to the Nearest

(2.303) = 0.059]
F Integer).

4. Consider the following reaction 10. Potassium chlorate is prepared by electrolysis of

MnO4 + 8H+ + 5e–  Mn2+ + 4H2O, Eº = 1.51 V. KCl in basic solution as shown by following
equation.
The quantity of electricity required in Faraday
6OH– + Cl– ClO3– + 3H2O + 6e–
to reduce five moles of MnO4 is____.
A current of xA has to be passed for 10h to
5 Emf of the following cell at 298 K in V is
produce 10.0g of potassium chlorate. the value
x × 10–2. ZnZn2+ (0.1 M)Ag+ (0.01 M) Ag
of x is _______. (Nearest integer)
The value of x is ______. (Rounded off to the
(Molar mass of KClO3 = 122.6 g mol–1,
nearest integer)
2.303RT
F = 96500 C)
[Given : E0Zn 2
/Zn
 0.76V; E 0Ag /Ag  0.80V;  0.059]
F

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11. Assume a cell with the following reaction 15. Given below are two statements :

Cu(s) + 2Ag+(1 × 10–3 M)Cu2+(0.250 M) + 2Ag(s) Statement I : The limiting molar conductivity

Ecell  2.97V of KCl (strong electrolyte) is higher compared

to that of CH3COOH (weak electrolyte).
Ecell for the above reaction is ___________V.
Statement II : Molar conductivity decreases
(Nearest integer)
with decrease in concentration of electrolyte.
[Given : log 2.5 = 0.3979, T = 298 K]
In the light of the above statements, choose the
12. Consider the cell at 25°C
most appropriate answer from the options
Zn | Zn2+(aq), (1 M) || Fe3+(aq), Fe2+(aq) | Pt(s)
given below :
3+
The fraction of total iron present as Fe ion at
(1) Statement I is true but Statement II is false.
the cell potential of 1.500 V is x × 10–2. The
(2) Statement I is false but Statement II is true.
value of x is ________ .
(3) Both Statement I and Statement II are true.
(Nearest integer)
(4) Both Statement I and Statement II are false.
(Given : E 0Fe  0.77V, E 0Zn 2 /Zn  0.76V )
3
/Fe 2 16. For the galvanic cell,

13. The conductivity of a weak acid HA of
concentration 0.001 mol L–1 is 2.0 × 10–5 S cm–l.
If om (HA)  190 S cm 2 mol 1 , the ionization
Zn(s)+Cu2+(0.02 M)Zn2+ (0.04 M)+ Cu(s),
Ecell =_______ × 10–2 V. (Nearest integer)
[Use : E 0 Cu /Cu = –0.34 V, E 0 Zn / Zn =+0.76 V,
2 2

constant (Ka) of HA is equal to _________ ×

2.303 RT
= 0.059 V]
10–6. F

(Round off to the Nearest Integer) 17. The resistance of a conductivity cell with cell

14. For the cell constant 1.14 cm–1, containing 0.001 M KCl at

298 K is 1500 . The molar conductivity of

Cu(s) | Cu2+(aq) (0.1M) || Ag+ (aq) (0.01M) |
0.001 M KCl solution at 298 K in S cm2
Ag(s)
mol–1 is_______. (Integer answer)
the cell potential E1 = 0.3095 V
18. Consider the following cell reaction :
For the cell
Cd(s)+Hg2SO4(s)+ 9 H 2 O( l ) 9
CdSO4 . H2O( s )  2Hg( l )
Cu(s) | Cu2+ (aq) (0.01 M) || Ag+(aq) (0.001 M) | 5 5

Ag(s) The value of E 0cell is 4.315 V at 25°C. If

the cell potential = ______ × 10–2 V. (Round off
H° = –825.2 kJ mol–1, the standard entropy
the Nearest Integer).
change S° in J K–1 is ______. (Nearest integer)
[ Use : 2.303 RT  0.059 ] [Given : Faraday constant = 96487 C mol–1]
F

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19. Match List-I with List-II
List-I List-II
(Parameter) (Unit)
(a) Cell constant (i) S cm2 mol–1
(b) Molar conductivity (ii) Dimensionless
(c) Conductivity (iii) m–1
(d) Degree of dissociation (iv) –1 m–1
of electrolyte
Choose the most appropriate answer from the
options given below :
(1) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii)
(2) (a)-(iii), (b)-(i), (c)-(ii), (d)-(iv)
(3) (a)-(i), (b)-(iv), (c)-(iii), (d)-(ii)
(4) (a)-(ii), (b)-(i), (c)-(iii), (d)-(iv)
20. If the conductivity of mercury at 0°C is
1.07 × 106 S m–1 and the resistance of a cell
containing mercury is 0.243 , then the cell
constant of the cell is x × 104 m–1. The value of
x is _______.(Nearest integer)

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SOLUTION for same thermodynamic tendency

1. Official Ans. by NTA (4) ENO /NO  ENO /NO

3 3 2

Sol. Only copper shows positive value for electrode

2+
potential of M /M of 3d-series elements. 0.059 P
or, E oNO /NO  log NO 4
3
3 yy
E / V(Cu2 /Cu) : 0.34

2. Official Ans. by NTA (3776) 0.059 PNO2

 EoNO /NO  log
Sol. Eqn is-
3 2
1 y  y2

MnO4  H  5e  Mn 2  4H2O 0.059 P 0.059 PNO

or, 0.96  log NO5
 0.79  log 3 2
Nernst equation: 3 y 1 y

0.059  Mn 2   1  8
0.059 PNO 0.059 P
Ecell  E0Cell  log or, 0.17 =  log 3 2 
5  MnO4   H  1 y 3
log NO
y5

(I) Given  H   1M
0.0591 PNO 0.0591 P
0.17 =  log 3 2 + log NO
0.059  Mn 2  1 y 3 y5
E1  E 0  log
5  MnO 4 
3
0.0591 PNO 0.0591 P
(II) Now :  H   104 M 0.17 =  log 9 2  log NO
3 y 3 y5
0.059  Mn 2  1
E2  E  0
log 
 MnO 4  10 4 8 0.0591  
 3
5 PNO PNO
0.17 =  log 5  log 9 2 
3  y y 
0.059 Mn 2 0.059
 E0  log  log10 32
5  MnO4  5
0.0591  PNO y 9 
0.059 0.17 =  log 5  3 
therefore : E1  E 2   32 3  y PNO2 
5
–4
= 0.3776 V = 3776 × 10 Assume PNO  PNO2 = 1 bar
x = 3776
0.17  3
3. Official Ans. by NTA (4)  log y 4  8.644
0.059
Sol. If the partial pressure of NO and NO2 gas is
8.644
taken as 1 bar, then Answer is 4, else the log y =
4
question is bonus.
NO3– + 4H+ + 3e–  NO + 2H2O log y = 2.161

E oNO   0.96V y = 102.16

3 / NO

NO3– + 2H+ + e–  NO2 + H2O  2x = 2 × 2.161 = 4.322

EoNO /NO 0.79 Answer (4)
3 2

Let [HNO3] = y  [H+] = y and [NO3–] = y 4. Official Ans. by NTA (25)

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5 Official Ans by NTA (147) 7. Official Ans. by NTA (57)
–
Sol. Zn(s)  Zn 2
( aq.)
+ 2e 1
Sol.  = ·G *
R
2Ag+(aq.) + 2e–  2Ag(s)
For same conductivity cell, G* is constant and
_________________________________________
hence .R. = constant.
Zn ( s ) + 2Ag (aq.)  Zn (2aq.)

2Ag(s)
 0.14 × 4.19 =  × 1.03
_______________________________________
0.14  4.19
E0cell  E0Ag /Ag  E0Zn2 /Zn or,  of HCl solution =
1.03
= 0.80 – (–0.76) –1
= 0.5695 Sm
= 1.56 V –2 –1 –2 –1
= 56.95 × 10 Sm  57 × 10 Sm
0.059 [Zn2 ]
Ecell = 1.56 log 8. Official Ans. by NTA (46)
2 [Ag  ]2
Official Ans. by ALLEN (45)
0.059 0.1
= 1.56  log 0
E1 E2
0

2 (0.01)2 Fe3+ Fe2+ Fe

0.059
0
Sol. E3
= 1.56  3
2 E10  2E02  3E30
= 1.56 – 0.0885
E10  3E30  2E02
= 1.4715
= 147.15 × 10–2 = 3 (–0.036) – 2(–0.44)
6. Official Ans. by NTA (14) = + 0.772 V
n m.mol E0cell  E0Fe3 /Fe2  E0I /I = 0.233
Sol. Given conc of KCl = 2

L
 r G 0 = – 2 × 96.5 × 0.233 = –45 kJ
: Conductance (G) = 0.55 mS
9. Official Ans. by NTA (288)
 
: Cell constant    1.3 cm 1 Sol. From Kohlrausch's law
A
 
To Calculate : Molar conductivity (m) of sol. m (BaSO4 ) = m 
(Ba2 ) +  m (SO24 )
  
1 k m (BaSO4 ) = m (BaCl 2 ) + m (H2SO4 )
 Since  m   ......(1)
1000 m 
–2 m (HCl)
–3 mol
 Molarity = 5 × 10 = 280 + 860 – 2 (426)
L
= 288 Scm2mol–1
 Conductivity = G     0.55 mS  1.3 m 1
A 1 10. Official Ans. by NTA (1)
100 Sol. Given balanced equation is
–1
= 55 × 1.3 mSm
 ClO3  3H 2 O  6e 
60H  Cl 
n 1 55  1.3 mSm 2
eq (1)  m  
10
1000  5  mol  10g KClO3  mol KCO3 in obtained
  122.6
 1000 
mSm 2  from the above reaction, it is concluded that by
  m  14.3
mol 6F charge 1 mol KClO3 is obtained.

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 By the passage of 6F charge = 1 mol KClO3 13. Official Ans. by NTA (12)
x  10  60  60
 By the passage of F charge 
96500 Sol.  m  1000 
M
1 x  10  60  60
 
6 96500 2  10 –5
= 1000  = 20 S cm2 mol–1
x  10  60  60 10 0.001
Now 
6  96500 122.6
 m 20  2 
 =  
x=
10  965

965
 1.311 1  m 190  19 
60  122.6 735.6
OR HA H  A–
E
W  It 0.001 (1–) 0.0010.001 
F
122.6 2
10 =  x  10  3600  2
96500  6 0.001   
  
2
 19 
X = 1.311  ka = 0.001  
1    2
1  
Ans.(1)  19 
11. Official Ans. by NTA (3)
0.059 [Cu 2 ] = 12.3 × 10–6
Sol. E  E  log
2 [Ag  ]2 14. Official Ans. by NTA (28)
0.059 0.25
 2.97  log  2  2.81V Sol. Cell reaction is :
2 (10 )
12. Official Ans. by NTA (24) Cu(s) + 2 Ag+ (aq)  Cu2+ (aq) + 2Ag (s)
Sol. Zn 
 Zn2+ + 2e–  Cu 2  
o 0.059
Now, Ecell = E – log ... (1)
2Fe3+ 
 2e– + 2e2+
Cell 2
2  Ag  
_____________________________________________

Zn + 2Fe3+ 
 Zn2+ + 2Fe2+ 0.059 0.01
 E1 = 0.3095= E oCell – . log 2 ... (2)

_____________________________________________
2  0.001
E0cell  0.77 – (0.76) From (1) and (2) , E2 = 0.28 V = 28 × 10–2 V
= 1.53 V
2
15. Official Ans. by NTA (4 )
0.06  Fe 2 
1.50 = 1.53 – log  3  Sol. Ion H+ K+ Cl– CH3COO–
2  Fe 
m Scm2 /mole 349.8 73.5 76.3 40.9
 Fe 2  0.03 1
log  3   
 Fe  0.06 2 So m CH3COOH  m (H )  m CH COO
3
[Fe 2 ]
= 101/2 = 10
3
[Fe ] = 349.8 + 40.9
[Fe3 ] 1 = 390.7 Scm2/mole
2

[Fe ] 10
m KCl  m (K )  m (Cl )
[Fe3 ] 1 1
2 3
 
[Fe ]  [Fe ] 1  10 4.16 = 73.5 + 76.3
= 0.2402
= 149.3 Scm2/mole
= 24 × 10–2
So statement-I is wrong or False.

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As the concentration decreases, the dilution 18. Official Ans. by NTA (25)
increases which increases the degree of Sol. G o  nFEo  Ho  TSo
Ho  nFEo
dissociation, thus increasing the no. of ions, 
T
which increases the molar conductance.

 825.2  10    2  96487  4.315
3

So statement-II is false. 298

825.2  10 3  832.682  10 3
420 
400 298
365
7.483  10 3
250   25.11 JK 1mol 1
298
200
140 KCl  Nearest integer answer is 25
CuSO4
CH3COOH
O 19. Official Ans. by NTA (1)
0 0.2 0.4
 
Sol. Cell constant =   Units  m–1
A
16. Official Ans. by NTA (109)
Molar conductivity (m) Units  Sm2 mole–1
Sol. Galvanic cell: Conductivity (K) Units = S m–1
2
Zn (s)  Cu (aq.)  Zn 2  Cu(s) Degree of dissociation () Dimensionless
0.04 M
0.02M
 (a) – (iii)
0.059 [2n 2 ]
Nernst equation = Fcell = Eocell  log (b) – (i)
2 [Cu 2 ]
(c) – (iv)
0.059 0.04 (d) – (ii)
 E cell  E ocell  E oZn 2 / Zn   log
2 0.02
20. Official Ans. by NTA (26)
0.059 2
 E cell  0.34   0.76   log Sol. k = 1.07 × 106 Sm–1, R = 0.243 
2
1 1
0.059        G=   –1
 E cell 1  1   0.3010 R 0.243
2
k = G × G*
–2
= 1.0911 = 109.11 × 10
k 1.07  10 6
G* = = 26 × 104 m–1
= 109 G 1
0.243
17. Official Ans. by NTA (760)

Sol. 1 1
K A 1.14 S cm 1
R 1500

1.14
1500
m 1000 S cm 2mol –1
0.001

= 760 S cm2 mol–1

 760