11c PDF

Chapter 11
Electrochemistry
Solutions
SECTION - A
Objective Type Questions
(Metallic/Electrolytic Conductors, Conductivity, Kohlrausch’s Law)
1. Which of the following is not a strong electrolytes?

(1) NaCl (2) KNO3 (3) NH4OH (4) FeSO4
Sol. Answer (3)
NaCl, KNO3, FeSO4  SASB salts
NH4OH  Weak base
2. The molar conductivity of strong electrolyte

(1) Increases on dilution slightly (2) Does not change on dilution
(3) Decreases on dilution (4) Depends on density of electrolyte itself
Sol. Answer (1)
Molar conductivity of strong electrolyte increases on dilution slightly due to decrease in interionic attraction.
3. The conduction of electricity through the electrolyte solution is due to

(1) Movement of molecules of electrolyte (2) Movement of ions of electolyte
(3) Movement of separate atoms (4) Movement of particles of the solvent
Sol. Answer (2)
Electrolytes get diasociated into ions on passing electricity so, ions start to move and produces conductance.
4. Which of the following is not correct?

(1) Molar conductance of a solution increases with dilution
(2) Equivalent conductance increases with dilution
(3) Specific conductance increases with dilution
(4) At infinite dilution each ion (cation or anion) plays a definite role towards electrical conductance
Sol. Answer (3)
Specific conductance
not increases with dilution because on dilution number of ions decreases per unit volume so, specific
conductance decreases.
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76 Electrochemistry Solutions of Assignment
5. Equivalent conductance of a weak electrolyte increases on dilution because of

(1) Increase in number of ions per unit volume
(2) Increase in molecular attraction
(3) Increase in degree of association
(4) Increase in degree of ionisation of the substance
Sol. Answer (4)
Equivalent conductance ( eq ) of a weak electrolyte increases on dilution because increase in degree of
ionization of substance = ions increases = movement of ions increases = eq increases.
6. As the dilution of an electrolyte increases

(1) Specific conductance decreases (2) Molar conductance decreases
(3) Resistance decreases (4) No change takes place in conductance
Sol. Answer (1)
dilution increases  specific conductance (  ) decreases because [number of ions per unit decreases volume]
7. The variation of equivalent conductance of strong electrolyte with concentration is correctly shown in which
figure?
(1)  (2)  (3)  (4) 
c c c c
Sol. Answer (2)
 b c
According to onsage equation m  m
i.e., on increasing concentration dissociation of

electrolyte decreases m or  eq decreases.
c
8. A 0.1M solution of monobasic acid at specific resistance of r ohms-cm, its molar conductivity is
(1) 10/r (2) 10r (3) 104/r (4) 104r
Sol. Answer (3)
Concentration = 0.1 M
  1000
m 
M
 ( = r)
1 1
 
 r
1 1000
   104/r
r 0.1
9. The specific conductivity of 0.5N solution is 0.01287 ohm–1 cm–1. What would be its equivalent conductance?
(1) 257.4 (2) 2.574
(3) 25.74 (4) 0.2574 ohm–1 cm2 (g. eq)–1
Solutions of Assignment Electrochemistry 77
Sol. Answer (3)
  1000 0.01287  1000

 eq    25.74
N 0.5
10. The specific conductance of saturated solution of CaF2 is 3.86 × 10–5 mho cm–1 and that of water used for
solution is 0.15 × 10–5. The specific conductance of CaF2 alone is
(1) 3.71 × 10–5 (2) 4.01 × 10–5 (3) 3.7 × 10–4 (4) 3.86 × 10–4
Sol. Answer (1)
(  ) of CaF2 solution = 3.86 ×10–5
(  ) of H2O = 0.15 × 10–5
⎡CaF2  H2 O  solution ⎤

⎢ ⎥
5
⎢⎣ x 0.15  10 3.86  105 ⎥⎦
x + 0.15 × 10–5 = 3.86 × 10–5
x = 3.86 × 10–5 – 0.15 × 10–5
 3.71 × 10–5
11. What will be the molar conductance ‘’,if resistivity is ‘x’ for 0.1 N H2SO4 solution?
x  1000 0.5
(1)  (2)   2  1000 (3)  x  1000
(4) 
0.1 x  0.1 0.5 1000 x
Sol. Answer (2)
  1000 H2SO4
m 
M
 N = m × n-factor
1 1000 0.1
=  M
 M 2
1000  2
=
x  0.1
12. The conductivities at infinite dilution of NH4Cl, NaOH and NaCl are 130, 218, 120 ohm–1cm2 eq–1. If equivalent
N
conductance of solution of NH4OH is 10, then degree of dissociation of NH4OH at this dilution is
100
(1) 0.005
(2) 0.043
(3) 0.01
(4) 0.02
Sol. Answer (2)
NH4Cl + NaOH  NaCl + NH4OH
   

  130 218 120 x
C
m 10
130 + 218 = 120 + x  
  0.043
m 228

x = 228 of NH4OH
N
13. The resistance of a KCl aqueous solution is 245. If the electrodes in the cell are 4 cm apart and area
10
having 7 cm2 each, the molar conductance of the solution will be
(1) 233 (2) 2.33 (3) 23.32 (4) 0.233
Sol. Answer (3)
  1000
  1000 N 1 1⎛ l ⎞ 1 4
m   
M n-factor  


R ⎜⎝ a ⎟⎠

245 7
1 4 1000
m    1
245 7 11 (n-factor for KCl = 1)
10
= 23.32
14. For strong electrolytes the values of molar conductivities at infinite dilution are given below :

Electrolyte m (Sm2 mol1 )
BaCl2 280 × 10–4
NaCl 126.5 × 10–4
NaOH 248 × 10–4
The molar conductance at infinite dilution for Ba(OH)2 is
(1) 523 × 10–4 Sm2 mol–1 (2) 52.3 × 10–4 Sm2 mol–1
(3) 5.23 × 10–4 Sm2 mol–1 (4) 6.23 × 10–4 Sm2 mol–1
Sol. Answer (1)
BaCl2 + 2 NaOH  Ba(OH)2 + 2 NaCl
–4 –4 –4
280 × 10 248 × 10 x 126.5 × 10
280 × 10–4 + 2 × 248 × 10–4 = x + 2 × 126.5 × 10–4
x = 776 × 10–4 – 253 × 10–4

= 523 × 10–4 of Ba(OH)2
15. The ionic mobility of alkali metal ions in aqueous solution is maximum for
(1) Na+ (2) K+ (3) Rb+ (4) Li+
Sol. Answer (3)
Li+(H2O)n, Na+(H2O)n, K+(H2O)n, Rb+(H2O)n
r+ increases  charge density decreases so, attraction with H2O decreases [r+ = cationic radius]
 movement of ion in H2O increases
i.e., Rb+
16. Which of the following solution will have highest specific conductance?
(1) 0.01 M CH3COOH (2) 0.01 M NH4OH (3) 0.01M NaCl (4) 0.01M K2SO4
Sol. Answer (4)
If concentration is same then conductance  number of ions, K2SO4 have total (3) ions which is maximum
among four so, it has highest conductance
K2SO4  2 K+ + SO4–2
17. The equivalent conductivity of 1M H 2 SO 4 solution would be if specific conductance is 26 × 10 –2 S cm –1 .
(1) 1.3 × 102 S cm2 sq–1 (2) 1.6 × 102 S cm–1
(3) 13 S cm2 mol–1 (4) 1.3 × 103 S cm2 mol–1
Sol. Answer (1)
  1000 26  102  1000 26  102  1000

 eq   
N M  n-factor 1 2
H2SO4  2 H+ + SO42
(n = 2)
 1.3 × 102 Scm2mol–1
18. The specific conductivity of N/10 KCl solution at 20°C is 0.0212 ohm–1 cm–1 and the resistance of the cell containing
this solution at 20°C is 55 ohm. The cell constant is
(1) 4.616 cm–1 (2) 1.166 cm–1 (3) 2.173 cm–1 (4) 3.324 cm–1
Sol. Answer (2)
1
  Cell constant, Cell constant =  × R = 0.0212 × 55 = 1.166 cm–1
R
19. Which of the following is a strong electrocyte?

(1) Ca(NO3)2 (2) HCN (3) H2SO3 (4) NH4OH
Sol. Answer (1)
HCN  Weak acid ⎫
⎪
⎪
NH4OH  Weak base ⎬  Weak electrolyte
⎪
H2SO3  Weak acid ⎪
⎭
Ca(NO3)2 – Strong base strong acid salt  Strong electrolyte
20. Equivalent conductance of NaCl, HCl and CH3COONa at infinite dilution are 126.45, 425.16 and 91ohm–1 cm2
respectively. The equivalent conductance of CH3COOH at infinite dilution would be
(1) 101.38 ohm–1 cm2 (2) 253.62 ohm–1 cm2
(3) 389.71 ohm–1 cm2 (4) 678.90 ohm–1 cm2
Sol. Answer (3)
eq  eq  eq CH3COONa + HCl  CH3COOH + NaCl
() ( )
91 + 425.16 = x + 126.45
x = 389.71 ohm–1cm2
(Electrolysis, Quantitative aspects of Electrolysis and Faraday's laws)

21. The amount of electricity that can deposit 108 g of silver from silver nitrate solution is
(1) 1 ampere (2) 1 coulomb (3) 1 faraday (4) 2 ampere
Sol. Answer (3)
Ag NO3  1e   Ag

108 g of Ag is 1 mole of Ag
Reduction
Ag+ required 1 mole of electron  1 faraday to reduce
22. The number of Faradays required to deposit 1 g equivalent of aluminium (At.wt. 27) from a solution of AlCl3
(1) 1 (2) 2 (3) 3 (4) 4
Sol. Answer (1)
The number of faradays required to deposit 1 g equation of Al is 1 faraday.
Al + 3 e  Al
+3 –
For 3 mole of electron  1 mole of Al +3
or 1 mole of Al  3 F
+3
Gram equivalent = mole × n-factor
Gram equivalent = 1 × 3 = 1 1 1
mole of Al  3 × = 1 F
+3
3 3 3
23. Electrochemical equivalent of Cu in the reaction Cu2+ + 2e– Cu is

63.5 63.5 63.5  2 96500
(1) (2) (3) (4)
96.5 96500  2 96500 63.5  2
Sol. Answer (2)
E
W  it
96500
M Cu2+
E 63.5
 Z  n  factor 
96500 96500 2  96500 (n-factor = 2)
24. Three faraday of electricity is passed through three electrolytic cells connected in series containing Ag+, Ca2+
and Al3+ ions respectively. The molar ratio in which the three metal ions are liberated at the electrodes is
(1) 1 : 2 : 3 (2) 3 : 2 : 1 (3) 6 : 3 : 2 (4) 3 : 4 : 2
Sol. Answer (3)
Ag+ + e–  Ag For 1 mole of Ag+, Ca2+,

Ca + 2e  Ca
2+ – Al+3 1 mole of e–, 2 mole of
electrons and 3 mole of electrons
Al3+ + 3e–  Al required respectively
1×3
i.e, for 3-faraday 2 × 3 mole electrons

3×3
for 1 mole electrons = 1 faraday  1 mole of Ag+

1
for 1 mole electrons = 1 faraday  mole of Ca2+
2
1
for 1 mole electrons = 1 faraday  mole of Al3+
3
1 1
So for 3 faraday  1 × 3,  3,  3
2 3
3
3: : 1 or 6 : 3 : 2
2
25. The mass of Cl2 produced when 1A current is passed through NaCl solution for 30 minute is
(1) 0.33 g (2) 0.66 g (3) 0.33 mol (4) 0.66 mol
Sol. Answer (2)
71
E
W  it  2  1 30  60  0.66 g
96500 96500
26. A current of 9.65 A flowing for 10 minutes, deposits 3.0 g of a metal. The equivalent weight of the metal is
(1) 10 (2) 30 (3) 50 (4) 96.5
Sol. Answer (3)
E 3  96500  100
W  it, E
96500 9.65  10  60
E = 50 g
27. If 9 g of H2O is electrolyzed completely with 50% current efficiency

(1) 1 F of electricity will be needed
(2) 3 F of electricity is needed
(3) 5.6 L of O2 at STP will be formed
(4) 11.2 L of O2 at STP will be formed
Sol. Answer (3)
electrolysis of H2O
anode 2 H+ + 2 e–  H2 [cathode]
4 OH–  O + 2 H O + 2e–
2 2
22.4
for 36 g H2O volume of O2   11.2 litre
2
11.2
So, 9 g H2O volume of O2   9  2.8L
36
50% current efficiency 2 mole of O2  5.6 litre
28. If the density of copper is 8.94 g/cm 3 , the number of Faradays required to plate an area
(10cm × 10cm) of thickness of 10–2 cm using CuSO4 solution as electrolyte is
(1) 0.1 F (2) 0.28 F (3) 0.4 F (4) 0.5 F
Sol. Answer (2)
m
d m = d × v = 8.94 × 10 × 10 × 10–2 = 8.94 g
v
E
W Q
96500
63.5
2 Q
8.94 g =
96500
8.94  2
Q  96500 faraday
63.5
= 0.2 F
29. An electrolytic cell is composed of Cu and Zn. A current of 9.65 A is drawn from a cell for 1 hour. Then the
loss in mass at anode and gain in mass at cathode, respectively could be
(1) 11.77 g, 11.43 g (2) 11.77 g, 10 g (3) 22.86 g, 23.54 g (4) 23.54 g, 22.86 g
Sol. Answer (1)
For Cu (at cathode)
63.5
molar mass 63.5
E E 
W  it  2  9.65  1 60  60  11.43 g n  factor 2  (Cu2 )
96500 96500
30. Volume of gases evolved when dil. H2SO4 is electrolysed using 2F at STP
(1) 22.4 L (2) 11.2 L (3) 33.6 L (4) 44.8 L
Sol. Answer (3)
dil.H2SO4 electrolysis
2H+ + 2e–  H2 4 OH–  O2 + 2H2O + 4 e–
(cathode) (anode)
22.4
Equivalent volume of O2 =  5.6 L
4
22.4
Equivalent volume of H2  = 11.2 L
n  factor
Total volume = 11.2 + 5.6 = 16.8 L

This total volume is for 1-faraday
so, for 2 F  16.8 × 2 = 33.6 L
31. 2.5 faraday of electricity is passes through a solution of CuSO4. The number of gram eqivalents of copper deposited
on the cathode will be
(1) 1 (2) 2 (3) 2.5 (4) 1.25
Sol. Answer (3)
E
W  it Q = it = 2.5 F, 1 F = 96500
96500
W 1 2.5  F
Gram equivalent    it  = 2.5 g
E 96500 96500
32. If equal quantities of electricity are passed through three voltameter containing FeSO4, Fe2(SO4)3 and Fe(NO3)3,
then which of the following is not true?
(1) Amount of iron deposited in FeSO4 and Fe2(SO4)3 is equal
2
(2) Amount of iron deposited in Fe(NO3)3 is of the amount of iron deposited in FeSO4
3
(3) Amount of iron deposited in Fe2(SO4)3 and Fe(NO3)3 are equal

(4) Same gas will evolve in all three cases at anode
Sol. Answer (1)
According to second law of faraday
2
w1 E1  Fe (FeSO4 )
(i) 
w 2 E2  Fe3 (F2 (SO4 )3 )
56
2 3
 ⇒
56 2
3
3
w1 E1  Fe [Fe(NO3 )3 ]
(ii) 
w 2 E2  [FeSO 4 ]
56
3 2
 ⇒
56 3
2
56
w1 E1 1 (Fe 3 )
  3 ⇒
(iii) w 2 E2 56 1 (Fe 3 )
3
(iv) Same (O2) gas will evolve at anode due to oxidation of OH–
33. Which of the following statement is incorrect?
(1) Electrons enter through cathode in an electrolytic cell
(2) Electrons leave through anode in an electrolytic cell
(3) Cations in the electrolytic cell move towards cathode and anions towards anode
(4) Cations are reduced at anode and anions are oxidised at cathode in an electrolytic cell
Sol. Answer (4)
Electrons move from anode to cathode in galvanic cell and from cathode to anode in electrolytic cell [in inner
circuit] and outer from anode to cathode
Cation are reduced at cathode and anions are oxidised at anode.
34. When dil. HNO3 is electrolysed

(1) H2(g) is formed at anode
(2) O2 gas is formed at anode
(3) NO2 is formed at anode
(4) N2 is formed at anode
Sol. Answer (2)
HNO3 + H2O
dil.HNO3 i.e., 
+ – + –
H NO3 H OH
anode cathode
– + –
NO3  X (No product) 2 H + 2 e  H2
–
4 (OH )  O2 + 2 H2O + 4 e–
oxidation potential EOX(OH )  EOX(NO3 )

i.e., O2 is formed at anode and H2 is formed to cathode.
35. During electrolysis of aqueous solution of a salt pH in the space near one of the electrodes is increased.
Which of the following salt solution was electrolysed?
(1) KCl (2) CuCl2 (3) Cu(NO3)2 (4) CuSO4
Sol. Answer (1)
pH increased due to more basic nature of product of electrolysis.
1. aq.KCl  KOH (product of electrolysis)
2. CuCl2 Now KOH is more basic than
Cu(OH)2 Cu(OH)2 so, it increases pH much
3. Cu(NO3)2
more than Cu(OH)2
4. CuSO4
36. Which of the following cannot envolve H2 from dil acid?
(1) Pt (2) Zn (3) Mg (4) Pb
Sol. Answer (1)
Pt is less reactive than H2 so, it can evolve H2 from dill acid. S.R.P of Pt is more than H2
(Electrochemical Cell, Commercial Cells or Batteries, Corrosion of Metals)
37. The electrochemical cell stops working after sometime because
(1) The reaction reverse its direction
(2) One of the electrodes completely vanishes
(3) Electrode potential of both the electrodes equalise
(4) Electrode potential of both the electrodes becomes zero
Sol. Answer (3)
After some time in electrochemical cell Ecathode = Eanode.
[Zn2 ]
This is known as equilibrium. So cell stops working because concentration = constant (In Daniell cell)
[Cu2 ]
38. The equilibrium constant for a feasible cell reaction is
(1) < 1 (2) 0 (3) 1 (4) > 1
Sol. Answer (4)
For feasible cell reaction  G = –ve and acceleration to G° = –2.303 RT log KC
If (KC > 1)  (positive) then G° = (negative)
39. In the galvanic cell, true statement
(1) Current flows from anode to cathode (2) Anode is +ve terminal
(3) If Ecell < 0, it is a spontaneous reaction (4) Cathode is +ve terminal
Sol. Answer (4)
In galvanic cell
Current flows from

cathode to anode
Anode is negative terminal
G = –nF Ecell
If Ecell > 0, G = negative(spontaneous)
Cathode is positive terminal
40. The maximum current can be drawn from which of the following cells?
2 2 2 2
(1) Zn( s ) Zn ( 0.2M) Cu (0.2M) Cu( s ) (2) Zn( s ) Zn ( 0.002M) Cu ( 0.2M) Cu( s )
(3) Zn(s) Zn 2  ( 0.2M) Cu2  ( 0.002M) Cu(s) (4) All of these
Sol. Answer (2)
0.059 [Cu2 ]
E  E  log [n = 2]
n [Zn2 ]
0.059 (0.2)
E  E  log
2 (0.002)
If (Cu+2)  = E 
41. The standard reduction potential of Pb and Zn electrodes are –0.126 and –0.763 volts respectively. The e.m.f.
of the cell
Zn | Zn2+ (0.1 M) || Pb2+ (1 M) | Pb is
(1) 0.637 V (2) < 0.637 V (3) > 0.637 V (4) 0.889
Sol. Answer (3)
0.059 [Zn2 ]
E  E  log E  Ec  Ea = –0.126 – (–0.763)
n [Pb2 ]
 –0.126 + 0.763 = 0.637
0.059 0.1
 0.637  log
2 1
0.059
= 0.637  log(101 )
2
0.059 0.059
= 0.637  ( 1)log10  0.637   1  0.637  0.0295
2 2
= 0.6665
i.e., Answer (3) [> 0.637]
42. For given half cell; Al3+ + 3e– Al ; on increasing [Al3+], the electrode potential
(1) Increases
(2) Decreases
(3) No change
(4) First increases then decreases
Sol. Answer (1)
0.059 [Al3  ]
E  E  log
3 [Al]
so, if [Al3+]   E
43. Deduced from the following E° values of half cells, what combination of two half cells would result in a cell
with the largest potential?
(i) A3–  A2– + e–; E° = 1. 5 V (ii) B2+ + e–  B+ ; E° = 2.1 V
(iii) C2+ + e–  C+; E° = +0.5 V (iv) D D2+ + 2e–; E° = –1.5 V
(1) (i) and (iii) (2) (i) and (ii) (3) (ii) and (iv) (4) (iii) and (iv)
Sol. Answer (2)
E° = E°cathode – E°anode
(i) A–3  A–2 + e– E° = 1.5 V
for reduction A–2 + e–  A–3 E° = –1.5 V
(ii) B+2 + e–  B+ E° = 2.1 V
E° of (B) > E° of (A) so, (B) is at cathode and (A) is at anode
E° = 2.1 – (–1.5)  3.6 maximum
44. Calculate EMF of the cell
A | A 3 (0.1m) || B 2 (0.01 m) | B
Given E° A | A+3 = 0.75 V

E° B | B+2 = 0.45 V
(1) 0.30 V (2) 1.21 V (3) 0.26 V (4) 0.80 V
Sol. Answer (3)
2 A + 3B+2  2 A+3 + 3 B E  Ec  Ea  0.45  ( 0.75)  0.3

(n = 6)
0.059 [B2 ]3
E  E  log 3 2
6 [A ]
0.059 (0.01)3 0.059

 0.3  log = 0.3  log(106  2 )
6 (0.1)2 6
0.059 0.059
 0.3  log(10 4 )  0.3   ( 4)log10
6 6
 0.3 + 0.009 × (–4) × 1
 0.3 – 0.039 = 0.261 V
1  1  1 1
45. If G for the reaction is A+ + B–  A2+ + B2– is x, the G for the reaction is A  B  A 2  B 2 is
2 2 2 2
x
(1) (2) 2x (3) x2 (4) x
2
Sol. Answer (1)
G is an extensive property i.e., depends on number of moles (amount)
Reaction is divided by (2) so G also divided by (2)
A+ + B–  A+2 + B–2 G = x
1  1  1 1 ⎛ x⎞
A  B  A 2  B2 ⎜ G  ⎟
2 2 2 2 ⎝ 2 ⎠
46. Consider the following equations for a cell
A+B C + D ; E° = x volt , Keq = K1
2A + 2B 2C + 2D ; E° = y volt , Keq = K2
Then
(1) x = y, K1 = K2 (2) x = 2y, K12 = K2 (3) x = y, K12 = K2 (4) x2 = y, K12 = K2
Sol. Answer (3)
A B CD E  x
2A  2B 2C  2D E  y
E° remain same if reaction is multiplied by or divided by any coefficient because E° is intensive property
[independent of amount]
so E° (x = y)
(C)[D] (C)2 [D]2

K1  , K2 
(A)[B] (A)2 [B]2
So, K 2  K12
47. The EMF of a chemical cell is positive when free energy change of reaction
(1) > 0 (2) < 0
(3) = 0 (4) No relationship of free energy change and e.m.f.
Sol. Answer (2)
G = –nFECell
If ECell = positive then G = negative [less than zero]
48. Hydrazene can be used in fuel cell N2H4(aq)  O2(g)  N2(g)  2H2O( ) . If G° for this reaction is –600 kJ,
what will be the E° for the cell?
(1) 1.25 V (2) 1.50 V (3) 1.57 V (4) 1.75 V
Sol. Answer (3)
Change on two nitrogen atom
change = 4
–4
Change on one nitrogen atom –2
N2H4 + O°2  N2° + 2 H2O–2 so (n = 4)

change = 4
G° = –nFE° = –4 × 96500 × E°
–600 × 103 = –4 × 96500 × E°
600  103
E   1.55 V
4  96500
49. Saturated solution of KNO3 is used to make salt bridge because
(1) Velocity of K+ is greater than that of NO3 (2) Velocity of NO3 is greater than that of K+
(3) Velocity of K+ and NO3 are nearly same (4) KNO3 is highly soluble in water
Sol. Answer (3)
Velocity of K+ and NO3 are nearly same so that neutralisation of opposite ions take place at same rate or
at same time by which current flows with same rate.
50. Find out the E°cell from the given data

(a) Zn | Zn+2 || Cu+2 | Cu ; E°cell = 1.10 V (b) Cu | Cu+2 || Ag+ | Ag ; E°cell = 0.46 V
(c) Zn | Zn+2 || Ag+ | Ag ; E°cell = ?
(Given E  2  0.34V )
Cu /Cu
(1) – 0.04 V (2) + 0.04 V (3) + 0.30 V (4) 1.56 V

Sol. Answer (4)
Zn  Cu2  Zn2  Cu E° = 1.10 V, G1 = –nFE  –2 F(1.10)  –2.20 F
Cu + 2 Ag+  2 Ag + Cu+2 E° = 0.46 V, G2 = –2F(0.46)  –0.92 F
Addition
Zn + 2 Ag+  Zn+2 + 2 Ag  G3 = G1  G2
–2 F E3  –2.20 F – 0.92 F
3.12 F
E3 ⇒  1.56 V
2 F
51. An electrochemical cell has two half cell reactions as,
A 2   2e   A ; E  0.34V
X  X2   2e  ; E  2.37V
The cell voltage will be
(1) 2.71 V (2) 2.03 V (3) –2.71 V (4) –2.03 V
Sol. Answer (1)
E  Ec  Ea
 0.34 – (–2.37) = 0.34 + 2.37
 2.71 V
52. If Eº Fe  2 |Fe is x1, E ºFe  3 |Fe is x2; then Eº  3  2 will be

Fe |Fe
(1) 3x2 – 2x1

(2) x2 – x1
(3) x2 + x1
(4) 2x1 + 3x2
Sol. Answer (1)
(i) Fe 2  2e   Fe E° = x0, G1 = –2Fx1
(ii) Fe3  3 e  Fe E° = x2, G2 = –3Fx2

Fe+3 + e–  Fe+2
This reaction is obtained by subtraction of (ii) – (i)
Fe + 3e  Fe
+3 –
– Fe+2 + 2e–  Fe G3  G2  G1

Fe + e  Fe
+3 – +2
1 FE3 ⇒  3Fx 2  ( 2F)x1

E3 ⇒ 3x 2  2x1
53. Purpose of hydrogen-oxygen fuel cell is to
(1) Generate heat (2) Create potential difference
(3) Produce high purity water (4) Remove adsorbed oxygen from electrode surface
Sol. Answer (2)
In hydrogen - oxygen fuel cell H2 is at cathode and oxygen is at anode by which H2 is produced by reduction
of H+ and O2 is oxidised so, that e– flows from anode to cathode i.e., current flows from higher reduction
potential to lower reduction potential [create potential difference]
54. In which of the following cell the energy of combustion of the reaction is directly converted into electricity?
(1) Lechlanche cell (2) Concentration cell (3) Fuel cell (4) Lead storage battery
Sol. Answer (3)
In fuel cell combustion of gases produces electricity.
55. Corrosion is basically

(1) Altered reaction in presence of H2O
(2) Electrochemical phenomenon
(3) Union between two light metals and a heavy metal
(4) Self oxidation and reduction
Sol. Answer (2)
In corrosion air oxidized metal and self reduces i.e., Redox reaction  electrochemical phenomenon
56. The main factors which affect corroision are

(1) Position of metal in electrochemical series (2) Presence of CO2 in water
(3) Presence of impurities in metals (4) All of these
Sol. Answer (4)
(1) Higher reactive metal can oxidized easily by air.
(2) Presence of CO2 in H2O  H2O + CO2  H2CO3
+ –2
2 H + CO3
increases acidic nature
or gain e– from metal
to reduce at cathode
(3) Some impurities are can easily oxidised so all of these effect corrosion.
57. During the recharging of lead acid storage cell the reaction at anode is
2 2 4 2 4 2
(1) Pb  Pb (2) Pb  Pb (3) Pb  Pb (4) Pb  Pb
Sol. Answer (2)
During recharging
anode Pb2SO4  H2O  Pb4 O2  H  e  SO42
58. In lead storage battery, the anode reaction is

2   
(1) Pb  2e  Pb (2) Pb  H2 SO 4  PbSO 4  2H  2e
(3) PbO  H2SO4  PbSO4  H2O (4) 2PbO  Pb  2Pb  PbO2
Sol. Answer (2)

At anode
Pb + H2SO4  PbSO4 + 2H+ + 2e–
At Cathode
PbO2 + 4H+ + 2e–  Pb+2 + 2H2O
Pb+2 + SO4–2  PbSO4
59. Which of the following is cathodic reaction?

2 3 
(1) Fe  Fe (2) 4OH  2H2O  O2
 2 2
(3) 2H2 O  2OH  H2 (4) 2SO 4  S2 O8
Sol. Answer (3)

Cathodic reaction is the reduction reaction
1. Fe+2  Fe+3 + e– (Oxidation)

2. OH  H2O + O2 + e (Oxidation)
– – Anodic reaction
4. 2 SO4–2  S2O8–2 + 2 e– (Oxidation)

3. 2 H2O  20 H– + H2  (Reduction)  Cathode
60. E° values of Mg2+|Mg, Zn2+|Zn and Fe2+|Fe are –2.37 V, –0.76 V and –0.44 V respectively. Which of the following
is correct ?
(1) Mg2+ oxidises Fe (2) Zn oxidises Fe2+ (3) Zn reduces Mg2+ (4) Zn reduces Fe2+
Sol. Answer (4)
S.R.P.  Fe > Zn > Mg
So oxidising power is also  Fe > Zn > Mg
Fe and Zn reduces Mg+2, Zn reduces Mg+2
61. The standard reduction potential value of three metallic cations X, Y and Z are 0.52, –3.303 and
–1.18 V respectively. The order of reducing power of the corresponding metals is
(1) Y > Z > X (2) X > Y > Z (3) Z > Y > X (4) Z > X > Y
Sol. Answer (1)
S.R.P X Y Z
0.52 –3.303 –1.18 V
⎡ 1 ⎤
Y<Z<X ⎢Oxidising power  Re ducing power ⎥
⎣ ⎦
Oxidising power Y < Z < X
Reducing power  Y > Z > X
62. A solution is 1 molar in each of NaCl, CdCl2, ZnCl2 and PbCl2. To this Sn metal is added, which of the following
is true?
Given E°(Pb2+/Pb = –0.126V)
E   0.136V, E   0.40V
Sn2  /Sn Cd2  /Cd
E   0.763V, E   2.71V
Zn2  /Zn Na /Na
(1) Sn can reduce Na+ to Na (2) Sn can reduce Zn2+ to Zn

(3) Sn can reduce Cd2+ to Cd (4) Sn can reduce Pb2+ to Pb
Sol. Answer (4)
S.R.P or (oxdising power) Pb > Sn > Cd > Zn > Na
Higher value of S.R.P  more is oxidising power and less is reducing power
So, (Sn) can oxidise Cd, Zn and Na but not Pb
i.e., Sn can reduce Pb2+ to Pb
63. Electrode potential data are given below

3
Fe(aq)  e   Fe(aq)
2
; E° = +0.77 V
3
Al(aq)  3e   Al(s) ; E° = – 1.66 V
Br2(aq)  2e   2Br(aq)


; E° = + 1.66 V
Based on the above data which statement(s) is incorrect?

(1) Fe2+ is stronger reducing agent than Br– (2) Fe2+ is stronger oxidising agent than Al
(3) Al is stronger reducing agent than Fe2+ (4) Br – is stronger reducing agent than Al
Sol. Answer (4)
S.R.P or (Oxidising power) Br2 > Fe > Al
Reducing power Br2 < Fe < Al Al is strongest reducing agent than Br–
So, 4th option in incorrect.
64. Fluorine is the best oxidising agent because it has

(1) Highest electron affinity (2) Highest E°red
(3) Highest E°oxi (4) Lowest electron affinity
Sol. Answer (2)

F2 is the best oxidising agent because it has highest Ereduction which is due to low bond dissociation energy
–
and high hydration energy of F
65. Ag2O  H2O  2e  2Ag  2OH

In the above chemical reaction
(1) Water is oxidised (2) Silver is oxidised (3) Silver is reduced (4) Hydrogen is reduced
Sol. Answer (3)
Ag21O  H2 O  2 e  2 Ag0  2OH

i.e., Ag+ is reduced to Ag
SECTION - B
Objective Type Questions
(Metallic/Electrolytic Conductors, Conductivity, Kohlrausch’s Law)
1. The resistance of 0.0025 M solution of K2SO4 is 326 ohm. The specific conductance of the solution, if cell
constant is 4.
(1) 4.997 × 10–4 (2) 5.997 × 10–7 (3) 6.997 × 10–4 (4) 1.20 × 10–2
Sol. Answer (4)
1 1⎛ l ⎞ 1
    4  1.20  102
 R ⎜⎝ a ⎟⎠ 326
2. The conductivity of four electrolytes P, Q, R, S in ohm–1 cm–1 are as follows P(5 × 10–5), Q(1× 10–10), R(7 × 10–8);
S(9.2 ×10–3). The one which offers highest resistance to the passage of electric current is
(1) P (2) S (3) R (4) Q
Sol. Answer (4)
1
Conductivity (  ),    Cell constant
R
⎡ 1⎤
⎢  R ⎥  Resistance
⎣ ⎦
(Q) has minimum conductivity so, maximum resistance
(Electrolysis, Quantitative aspects of Electrolysis and Faraday's laws)
3. The coulombic charge on one mole electron is
(1) 1.6 × 10–19 C (2) 96500 C (3) 6.02 × 10–23 C (4) 1.6 × 10–23 C
Sol. Answer (2)
Charge on i.e., = –1.6 × 10–19C
On 1 mole e–  |1.6 × 10–19 × NA|
96500 C  known as 1 faraday
4. Zn rod is placed in 100 mL of 1M CuSO4 solution so that molarity of Cu2+ changes to 0.7 M. The molarity of
SO42– at this stage will be
(1) 0.8 M (2) 1 M (3) 0.7 M (4) 1.8 M
Sol. Answer (2)
–2
CuSO 4  Cu + SO 4
+2
1m 1m 1m
after reaction SO42 becomes spectator ion so, their concentration will not change.
5. The time taken by the galvanic cell which operates almost ideally under reversible conditions at a current of
10–16A to deliver 1 mole of electron is
(1) 19.30 × 1020 s (2) 4.825 × 1020 s (3) 9.65 × 1020 s (4) 3.4 × 1011 s
Sol. Answer (3)
Q = it, charge on 1 mole of electrons = 1 Faraday = 96500 C
96500 = 10–16 × t
96500
t  96500  1016  9.65 × 1020 sec
1016
6. A direct current deposits 54 g of silver (atomic mass = 108) during the electrolysis. The same quantity of
electricity would deposit aluminium (atomic mass = 27) from aluminium chloride in molten state equal to
(1) 4.5 g (2) 5.4 g (3) 54 g (4) 27 g
Sol. Answer (1)
108
w1 E1 54 M 108 27

w 2 E2   1 E1   for Ag , E2  for Al3 
w2 27 n-factor 1 3
3
54  9
 w2   4.5 g
108
7. During the electrolysis of water 4 mol of electrons were transferred from anode to cathode. The total volume
of gases produced at STP will be approximately
(1) 67.2 L (2) 22.4 L (3) 44.8 L (4) 89.4 L
Sol. Answer (1)
H2 (cathode)  11.2 L
By electrolysis of H2O 16.8 L (Total) for 1 faraday
O2 (anode)  5.6 L
So, for 4 mole of electrons = 4 faraday
 4 × 16.8 L = 67.2 L
8. The quantity of electricity required to reduce 12.3 g of nitro benzene to aniline assuming 50% current
effeciency is
(1) 115800 C (2) 57900 C (3) 231600 C (4) 28950 C
Sol. Answer (1)
(change = 6)
+3 –3
NO2 NH2
C6H5NO2 = 12 × 6 + 5 + 14 + 32 = 123
W = 12.3 g
Given wt.
Current efficiency = Deposited wt. (Theoritical)  100
50 12.3

100 w
12.3  100
w  24.6
50
E
w Q
96500
Mol.wt. of nitrobenzene
24.6  Q
96500  6(n-factor of nitrobenzen)
123 1
24.6   Q
96500 6
24.6  96500  6
Q  115,800 C
123
9. A 100 watt, 110 volt lamp is connected in series with an electrolytic cell containing CdSO4 solution, the weight
of Cd deposited by the current for 10 hrs is (At. wt. of zCd = 112.4)
(1) 19.06 g (2) 38.12 g (3) 1.906 g (4) 3.812 g
Sol. Answer (1)
P = I.V
P 100
I 
V 110
E
w  it
96500
+2
n-factor of Cd
112.4
2  100  10  60  60  19.06 g

96500 110
10. The two platinum electrodes fitted in a conductance cell are 1.5 cm apart while the cross sectional area of each
electrode is 0.75 cm2. What is the cell constant?
(1) 1.25 cm (2) 0.5 cm (3) 2.0 cm–1 (4) 0.2 cm–1
Sol. Answer (3)
l 1.5
Cell constant    2 cm1
a 0.75
11. A current of 2.0 A is passed for 5 hours through a molten metal salt deposits 22.2 g of metal
(At. mass: 177). The oxidation state of the metal in metal salt is
(1) +1 (2) +2 (3) +3 (4) +4
Sol. Answer (3)
E
w  it
96500
Atomic mass
w  n  factor  it
96500
n-factor (oxidation-state)
Atomic mass  i  t 177  2  5  60  60

   2.97 3
96500  w 96500  22.2
12. A current of 0.965 ampere is passed through 500 ml of 0.2 M solution of ZnSO4 for 10 minutes. The molarity of Zn2+
after deposition of zinc is
(1) 0.1 M (2) 0.5 M (3) 0.8 M (4) 0.194 M
Sol. Answer (4)
w1
M
M  V(L)
w1  1000
0.2 
65  500
w1  6.5 g
Deposited mass after passing electricity,
65
w 2  2  0.965  10  60 = 0.195 g
96500
left mass of (Zn+2)  w1 – w2 = 6.5 – 0.195 = 6.305
So, M  6.305  1000  0.194 M

65  500
13. Electrolysis of H2SO4 (conc.) gives the following at anode

(1) H2 (2) O2 (3) H2S2O3 (4) H2S2O8
Sol. Answer (4)
Electrolysis of concentration H2SO4  H+ + HSO4–
At Cathode At Anode
2HSO4  H2S2O8  2 e
2H+ + 2e–  H2 
Marshall acid
(Electrochemical Cell, Commercial Cells or Batteries, Corrosion of Metals)
14. In SHE, the pH of the acid solution should be

(1) 7 (2) 14 (3) 0 (4) 4
Sol. Answer (3)
In SHE  concentration of solution is 1 MHCl  H + Cl–
1m
pH = –log(H+) = –log(1) = 0
15. E.M.F. of Ni(s)|Ni2+ (aq) || Cu2+ (aq)|Cu(s) cell can be increased by

(1) Adding NH3 in the right half-cell
(2) Increasing the conc. of Ni2+ ions
(3) Adding dimethyl glyoxime into the left half-cell
(4) Changing the electrolyte present in salt bridge
Sol. Answer (3)
Ni  Cu2  Cu  Ni2
0.059 [Ni][Cu2 ]
E  E  log
2 [Cu][Ni2 ]
(1) Cu+2 + 4 NH3  [Cu(NH3)4]+2
i.e., Concentration of Cu+2 decreases which decreases (E)
(2) (Ni+2) increases  E decreases
(3) CH3 – C – N – OH
+ Ni+2  [Ni(dmg)2]
CH3 – C – N – OH
complex
(dimethyl glyoxime)
or dmg
i.e., concentration of Ni+2 decreases  Ecell increases
16. For given cell; Zn |Zn+2 (C1) || Zn+2 (C2)| Zn; G is negative if
(1) C1 = C2 (2) C1 > C2 (3) C2 > C1 (4) Can't be predicted
Sol. Answer (3)
+2 +2
Zn | Zn || Zn | Zn
 This is concentration cell
(C1) (C2)
0.059 (Zn2 ) cathode

E  E  log [ECell ] cathode and anode are same
2 (Zn2 )anode
0.059 C
ECell  0  log 2   ve
If C2 > C1  Ecell = positive then G  ( )nFECell negative
2 C1
17. The emf of the cell, Zn|Zn2+|Ag+|Ag is independent of

(1) The volume of Zn2+ and Ag+ solution
(2) The molarity of Zn2+ ions in solution
(3) The molarity of Ag+ions in solution
(4) Temperature
Sol. Answer (1)
0.059 [Ag ]
E  E  log
2 [Zn2 ]
Volume of both Ag+ and Zn+2 remain same so, it does not effect Ecell.
18. Standard cell voltage for the cell Pb/Pb2+||Sn2+/Sn is –0.01V. If the cell is to exhibit Ecell = 0, the value of
log [Sn2+] /[Pb2+] should be
(1) 0.33 (2) 0.5 (3) 1.5 (4) –0.5
Sol. Answer (1)
0.059 [Sn2 ]
E  E  log
2 [Pb2 ]
0.059 (Sn2 )
0  0.01  log
2 (Pb2 )
0.059 (Sn2 )
0.01  log
2 (Pb2 )
(Sn2 ) 0.01 2
log   0.33
(Pb2 ) 0.059
19. The voltage of a cell whose half cell reactions are given below is
Mg2  2e   Mg(s); E  –2.37 V
Cu2  2e   Cu(s); E  0.34 V

(1) –2.03 V (2) 1.36 V (3) 2.71 V (4) 2.03 V
Sol. Answer (3)
E  ECathode  EAnode The higher value of S.R.P shows cathodic reaction and lower value shows anodic reaction
= 0.34 – (–2.37) = 2.71 V
20. The hydrogen electrode is dipped in a solution of pH = 3 at 25°C. The reduction potential of the electrode would be
(1) 0.177 V (2) 0.087 V (3) –0.177 V (4) 0.059 V
Sol. Answer (3)
pH = 3, pH = –log10(H+) (H+) = 10–3, 2 H+ + 2 e–  H2
3 = –log10(H+) E°S.H.E = 0, PH2 = 1, log10 = 1
0.059 (H )2
E  E  log
2 PH2
0.059 (103 )2
 0 log
2 1
0.059
 ( 6)  log10  (–)0.059 × 3 = –0.177 V
2
2 2
21. Zn | Zn(ag) || Cu(ag) | Cu E° for the cell is 1.10 V at 25°C. The equilibrium constant for the cell reaction is of the
order of
(1) 10–37 (2) 1037 (3) 10–17 (4) 1017
Sol. Answer (2)
0.059
E  logK C
2
0.059
1.10  log10 K C
2
1.10  2
log10 K C 
0.059
log10 K C  37.2 37
KC = 1037
22. What will be the emf of the given cell?


Pt | H2(P1) | H(aq) | H2(P2) | Pt
RT P1 RT P RT P2 RT P
(1) ln (2) ln 1 (3) ln (4) ln 2
F P2 2F P2 F P1 2F P1
Sol. Answer (2)
0.059 (PH ) Cathode ⎡Cathode 2H  2e   H2

E  E  log 2 ⎢
2 (PH2 ) Anode ⎢⎣ Anode H2  2H  2 e
0.059 p
 0 log 2 ES.H.E.  0
2 p1
0.059 p
or E log 1
2 p2
2.303RT p RT p1
or E log 1  ln
2F p2 2 F p2
23. Which of the following can oxidise fluoride ions?

(1) O3 (2) Cl2 (3) Br2 (4) No chemical substance
Sol. Answer (4)
F– can never oxidised by other oxidising agent because F2 itself is strong oxidising agent due to maximum
standard reduction potential.
24. If the standard reduction potential E° for four divalent elements X, Y, Z, W are –1.46 V, –0.36V, 0.15 V and
–1.24 V respectively then
(1) X will replace Z2+ from aqueous solution
(2) Y will replace Z2+ from aqueous solution
(3) W will replace Z2+ from aqueous solution
(4) All statements are correct.
Sol. Answer (4)
Z  Y  W X
S.R.P or oxidising power  [S.R.P = Reactivity]
Reactivity
⎡ X  will replace, (Z, Y,W) ⎤

so, ⎢ Y  will replace  Z ⎥ all are correct
⎢ ⎥
⎢⎣ W  will replace  Z and Y ⎥⎦
more reactive metal replace less reactive metal.

25. The following facts are available
2A– + B2 
 2B– + A2
2C– + B2 
 No reaction
2D– + A2 
 2A– + D2
Which of the following statement is correct?
(1) Eo   Eo   Eo   Eo 
C /C2 B /B2 A /A 2 D /D2
(2) Eo   Eo   Eo   Eo 
C /C2 B /B2 A /A 2 D /D2
(3) Eo   Eo   Eo   Eo 
C /C2 B /B2 A /A 2 D /D2
(4) Can’t predict

Sol. Answer (2)
According to given reactions
 B2 can oxidise A–, and cannot oxidise C–
 A2 can oxidise D–
C2 > B2 > A2 > D2
So, reduction potential 
(C) can reduced (A) reduced
but not oxidised by D
–
by B 2
So, oxidation potential  C2 < B2 < A2 < D2
SECTION - C
Previous Years Questions
1. Consider the change in oxidation state of Bromine corresponding to different emf values as shown in the diagram
below :
– 1.82 V – 1.5 V
BrO4 BrO3 HBrO
–
Br 1.0652 V Br2 1.595 V
Then the species undergoing disproportionation is [NEET-2018]
(1) BrO3 (2) BrO4 (3) HBrO (4) Br2

Sol. Answer (3)
1 0
o
HBrO  Br2 , EHBrO/Br2
 1.595 V
1 5
 BrO3 , Eo
HBrO   1.5 V
BrO3 /HBrO
Eocell for the disproportionation of HBrO,
Eocell  EHBrO/Br
o
 Eo
2 BrO3 /HBrO
= 1.595 – 1.5
= 0.095 V = + ve
Hence, option (3) is correct answer.
2. In the electrochemical cell, Zn|ZnSO4(0.01M)||CuSO4(1.0 M)|Cu, the emf of this Daniel cell is E1. When the
concentration of ZnSO4 is changed to 1.0 M and that of CuSO4 changed to 0.01 M, the emf changes to E2.
RT
From the following, which one is the relationship between E1 and E2? (Given, = 0.059) [NEET-2017]
F
(1) E1 = E2 (2) E1 < E2 (3) E1 > E2 (4) E2 = 0 ≠ E1

Sol. Answer (3)
Zn|ZnSO4(0.01 M)||CuSO4(1.0 M)|Cu
o 2.303RT (0.01)
 E1  Ecell –  log
2F 1
When concentrations are changed
o 2.303RT 1
 E2  Ecell –  log
2F 0.01
i.e., E1 > E2
3. If the Eºcell for a given reaction has a negative value, which of the following gives the correct relationships for
the values of G° and Keq? [NEET (Phase-2) 2016]
(1) G° > 0; Keq < 1 (2) G° > 0; Keq > 1 (3) G° < 0; Keq > 1 (4) G° < 0; Keq < 1
Sol. Answer (1)

o
∵ Ecell  – ve
 G° = +ve & Keq = –ve i.e., G° > 0 & Keq < 1
4. The molar conductivity of a 0.5 mol/dm3 solution of AgNO3 with electrolytic conductivity of 5.76 × 10–3 S cm–1
at 298 K [NEET-Phase-2-2016]
(1) 2.88 S cm2/mol (2) 11.52 S cm2/mol (3) 0.086 S cm2/mol (4) 28.8 S cm2/mol
Sol. Answer (2)
  1000 5.76  103  1000

m   = 11.52 S cm2/mol
M 0.5
5. During the electrolysis of molten sodium chloride, the time required to produce 0.10 mol of chlorine gas using
a current of 3 amperes is [NEET-Phase-2-2016]
(1) 55 minutes (2) 110 minutes (3) 220 minutes (4) 330 minutes
Sol. Answer (2)
For 1 mole Cl2, 2 F electricity is required
 For 0.1 mole Cl2, 0.2 F electricity will be required
 Q=I×t
Q 0.2  96500
or, t    110 min.
I 3  60
6. The number of electrons delivered at the cathode during electrolysis by a current of 1 ampere in
60 seconds is (charge on electron = 1.60 × 10–19 C) [NEET-Phase-2-2016]
(1) 6 × 1023 (2) 6 × 1020 (3) 3.75 × 1020 (4) 7.48 × 1023
Sol. Answer (3)
Q=It
= 1 A  60 s = 60 C
60
 No. of electrons = = 3.75  1020
1.602  1019
7. Zinc can be coated on iron to produce galvanized iron but the reverse is not possible. It is because
[NEET-Phase-2-2016]
(1) Zinc is lighter than iron
(2) Zinc has lower melting point than iron
(3) Zinc has lower negative electrode potential than iron
(4) Zinc has higher negative electrode potential than iron
Sol. Answer (4)
EZn2(  ) /Zn  0.76 V


EFe 2(  )
/Fe
 0.44 V
8. The pressure of H2 required to make the potential of H2 – electrode zero in pure water at 298 K is
[NEET-2016]
(1) 10–4 atm (2) 10–14 atm (3) 10–12 atm (4) 10–10 atm
Sol. Answer (2)
2H+ + 2e–  H2(g)
0.0591 PH 0.0591 PH2

E  Eº –  log 2 2 = 0 –  log
2 [H ] 2 (10 –7 )2
10 –14
 For potential of H2 electrode to be zero, PH should be 10–14 i.e., log 0
2 10 –14
9. Aqueous solution of which of the following compounds is the best conductor of electric current?
[Re-AIPMT-2015]
(1) Ammonia, NH3 (2) Fructose, C6H12O6 (3) Acetic acid, C2H4O2 (4) Hydrochloric acid, HCl
Sol. Answer (4)
In aqueous medium, HCl easily ionises to H and Cl(–), thus the HCl solution would be the best conductor of
all the given options.
10. A device that converts energy of combustion of fuels like hydrogen and methane, directly into electrical energy
is known as [AIPMT-2015]
(1) Ni-Cd cell (2) Fuel cell (3) Electrolytic cell (4) Dynamo
Sol. Answer (2)
Fact
11. When 0.1 mol MnO24 is oxidised the quantity of electricity required to completely oxidise MnO24 to MnO4 is
[AIPMT-2014]
(1) 96500 C (2) 2 × 96500 C (3) 9650 C (4) 96.50 C
Sol. Answer (3)
q
 n-factor  0.1
96500
q = 1 × 0.1,  q = 9650 C
12. The weight of silver (At. Wt. = 108) displaced by a quantity of electricity which displaces 5600 mL of O2 at STP will
be [AIPMT-2014]
(1) 5.4 g (2) 10.8 g (3) 54.0 g (4) 108.0 g
Sol. Answer (4)
Wt( Ag ) VO2
1 4
108 22.4
Wt(Ag) 6500
 4
108 22400
108  4
Wt(Ag) 
4
Wt(Ag)  108 g
13. A button cell used in watches functions as following

Zn(s)  Ag2O(s)  H2O(l )
2Ag(s) + Zn2+ (aq) + 2OH– (aq)
If half cell potentials are
Zn2+ (aq) + 2e–  Zn(s) ; E° = –0.76 V
Ag2O(s) + H2O(l) + 2e–  2Ag(s) + 2OH– (aq), E° = 0.34 V
The cell potential will be [NEET-2013]
(1) 0.42 V (2) 0.84 V (3) 1.34 V (4) 1.10 V
Sol. Answer (4)
E  ECathode  EAnode  0.34 – (–0.76) = 1.10 V
14. At 25°C molar conductance of 0.1 molar aqueous solution of ammonium hydroxide is 9.54 ohm–1 cm2 mol–1 and at
infinite dilution its molar conductance is 238 ohm–1 cm2 mol–1. The degree of ionisation of ammonium hydroxide at
the same concentration and temperature is [NEET-2013]
(1) 20.800% (2) 4.008% (3) 40.800% (4) 2.080%
Sol. Answer (2)

C
m  9.54  1 cm2 mol1 ⎤ C
m 9.54

⎥   
  0.04008  0.04008  4.008%
m  238  1 cm2 mol1 ⎥⎦ m 238
15. A hydrogen gas electrode is made by dipping platinum wire in a solution of HCl of pH = 10 and by passing
hydrogen gas around the platinum wire at one atm pressure. The oxidation potential of electrode would be?
[NEET-2013]
(1) 0.59 V (2) 0.118 V (3) 1.18 V (4) 0.059 V
Sol. Answer (1)
∵ pH = 10  ⎡⎣H ⎤⎦  10 10 M
For, 2H  2e  H2
0.059 PH
Ereduction  E  log  2 ,  ES.H.E  0
2 (H ) 2
0.059 1 0.059
= 0  2
log 10 2 = log1020
(10 ) 2
0.059
Ereduction   20  log10 = –0.059 × 10 = –0.59 V so, Eoxidation = +0.59 V
2
16. Limiting molar conductivity of NH4OH ⎛⎜ i .e.  m (NH4 OH) ⎞⎟ is equal to


[AIPMT (Prelims)-2012]
⎝ ⎠
o o o
(1) m (NH4OH)  m (NH4Cl) – m (HCl) (2) mo (NH4Cl)  mo (NaOH) – mo (NaCl)
(3) mo (NH4Cl)  mo (NaCl) – mo (NaOH) (4) mo (NaOH)  mo (NaCl) – mo (NH4Cl)
Sol. Answer (2)
m(NH4OH)    

m NH
4  
m OH(  ) 
        m  
=  
m NH
4

m Cl(  )  
m Na  
m OH(  )  
m Na  
m Cl(  ) 
i.e., m(NH4Cl)  m(NaOH)  m(NaCl)  m(NH4OH)
17. Standard reduction potentials of the half reactions are given below
F2(g) + 2e–  2F–(aq); E = +2.85 V
Cl2(g) + 2e–  2Cl–(aq) ; E = +1.36 V
Br2(l) + 2e–  2Br–(aq) ; E = +1.06 V
2(s) + 2e– 2–(aq) ; E = +0.53 V
The strongest oxidising and reducing agents respectively are [AIPMT (Mains)-2012]
(1) F2 and – (2) Br2 and Cl– (3) Cl2 and Br– (4) Cl2 and 2
Sol. Answer (1)
S.R.P/oxidising power  F2 (Strongest oxidising) > Cl2 > Br2 > I2
Reducing power  F2 < Cl2 < Br2 < I2 (Strongest reducing
o
18. Molar conductivities m   at infinite dilution of NaCl, HCl and CH3COONa are 126.4, 425.9 and 91.0 S cm2
o
mol–1 respectively, m for CH3COOH will be [AIPMT (Mains)-2012]
(1) 425.5 S cm2 mol–1 (2) 180.5 S cm2 mol–1 (3) 290.8 S cm2 mol–1 (4) 390.5 S cm2 mol–1
Sol. Answer (4)
CH3COONa + HCl  CH3COOH + NaCl
° 91 + 425.9 = x + 126.4
m
m  x  (91  425.9)  126.4  390.5 Scm2 mol1

(CH3COOH)
19. The Gibb's energy for the decomposition of Al2O3 at 500C is as follows
2 4
Al O Al+O2 ; rG = +960 kJ mol–1
3 2 3 3
The potential difference needed for the electrolytic reduction of aluminium oxide (Al2O3) at 500C is at least
[AIPMT (Mains)-2012]
(1) 4.5 V (2) 3.0 V (3) 2.5 V (4) 5.0 V
Sol. Answer (3)
G 960  1000
Ecell =   V  2.487 V  2.5 V
nF 4  96500
20. The electrode potentials for Cu2  e  Cu and Cu  e  Cu are +0.15 V and +0.50 V respectively.
(aq) (aq) (aq) (s)
The value of Eo will be [AIPMT (Prelims)-2011]

Cu2  /Cu
(1) 0.150 V (2) 0.500 V (3) 0.325 V (4) 0.650 V

Sol. Answer (3)
Cu+2 + e–  Cu+ ; E° = 0.15 V, G1  nFE  1 F  (0.15)
Cu+ + e–  Cu ; E° = 0.50 V, G2  1 F  (0.50)
On adding
Cu+2 + 2e–  Cu
G3  G1  G2
2FE3  F(0.15)  F(0.50)
2FE3  0.65F
0.65
E3   0.325 V
2
21. Standard electrode potential for Sn4 / Sn2 couple is +0.15 V and that for the Cr 3+ /Cr couple is
–0.74 V. These two couples in their standard state are connected to make a cell. The cell potential will be
(1) + 1.83 V (2) + 1.19 V (3) + 0.89 V (4) + 0.18 V
Sol. Answer (3)
E  Ec  Ea higher value of S.R.P  Cathodic reaction
= 0.15 – (–0.74) = 0.89 V
22. If the Eocell for a given reaction has a negative value, then which of the following gives the correct relationships
for the values of G° and Keq? [AIPMT (Prelims)-2011]
(1) G  0; K eq  1 (2) G  0; K eq  1 (3) G  0; K eq  1 (4) G  0; K eq  1
Sol. Answer (1)

G° = –nF ECell = –nF ECell 
i.e., G° > 0  positive
G° = –2.303 RT log10KC
If G° = positive then KC must be negative, so KC < 1.
23. An increase in equivalent conductance of a strong electrolyte with dilution is mainly due to
(1) Increase in ionic mobility of ions
(2) 100% ionisation of electrolyte at normal dilution
(3) Increase in both i.e. number of ions and ionic mobility of ions
(4) Increase in number of ions
Sol. Answer (1)
On increasing dilution mobility of ions of strong electrolyte increases.
24. For the reduction of silver ions with copper metal, the standard cell potential was found to be +0.46V at 25C.
The value of standard Gibbs energy, G will be (F = 96500 C mol–1) [AIPMT (Prelims)-2010]
(1) –89.0 kJ (2) –89.0 J (3) –44.5 kJ (4) –98.0 kJ
Sol. Answer (1)
2 Ag  Cu  2 Ag  Cu2
G  nFECell
2  96500  0.46
 kJ
1000
= –88.78 kJ –89 kJ
25. Which of the following expressions correctly represents the equivalent conductance at infinite dilution of
o
Al2(SO4)3. Given that  oAl3 and SO24 are the equivalent conductances at infinite dilution of the respective ions?
[AIPMT (Mains)-2010]
o o o o o o 1 o 1
(1) 2 Al3  3 SO24 (2)  Al3  SO24 (3) (  Al3   SO24 )  6 (4)  3   oSO2
3 Al 2 4
Sol. Answer (2)
Equivalent conductance eq⎣⎡Al2 (SO4 )3 ⎦⎤  Al3(  )  SO2

4
26. Consider the following relations for emf of an electrochemical cell
(a) emf of cell = (Oxidation potential of anode) – (Reduction potential of cathode)
(b) emf of cell = (Oxidation potential of anode) + (Reduction potential of cathode)
(c) emf of cell = (Reductional potential of anode) + (Reduction potential of cathode)
(d) emf of cell = (Oxidation potential of anode) – (Oxidation potential of cathode)
Which of the above relations are correct? [AIPMT (Mains)-2010]
(1) (c) and (a) (2) (a) and (b) (3) (c) and (d) (4) (b) and (d)
Sol. Answer (4)
E C ell  E C athode  E A node
(R eduction ) (R eduction)
or ECell  EOxidation  EReduction


(Anode) (Cathode)
or ECell  EOxidation  EOxidation

(Anode) (Cathode)
27. Given
(i) Cu2+ + 2e–  Cu, Eo = 0.337 V
(ii) Cu2+ + e–  Cu+, Eo = 0.153 V
Electrode potential, Eo for the reaction,
Cu+ + e–  Cu, will be [AIPMT (Prelims)-2009]
(1) 0.90 V (2) 0.30 V (3) 0.38 V (4) 0.52 V
Sol. Answer (4)
Cu2+ + 2 e–  Cu ; E° = 0.337 V …(i)
Cu2+ + e–  Cu+ ; E° = 0.153 V …(ii)
(i) – (ii),
Cu2+ + 2 e–  Cu  G1  2 F(0.337)
Cu2+ + e–  Cu+  G2   F[0.153]

– –
Cu+ + e–  Cu  G3  G1  G2
 1 F  ECell  2F(0.337)  ( F  0.153)
 FECell  2F  0.337  0.153F
 FECell  0.52F
 ECell  0.52 V
28. Al2O3 is reduced by electrolysis at low potentials and high currents. If 4.0 × 104 amperes of current is passed
through molten Al2O3 for 6 hours, what mass of aluminium is produced? (Assume 100% current efficiency, At.
mass of Al = 27 g mol–1) [AIPMT (Prelims)-2009]
(1) 8.1 × 104 g (2) 2.4 × 105 g (3) 1.3 × 104 g (4) 9.0 × 103 g
Sol. Answer (1)
27
E Al 3  4  104  6  60  60 = 8.05 × 104 g
w I t =
96500 96500
M
29. The equivalent conductance of solution of a weak monobasic acid is 8.0 mho cm2 and at infinite dilution
32
is 400 mho cm2. The dissociation constant of this acid is [AIPMT (Prelims)-2009]
(1) 1.25 × 10–6 (2) 6.25 × 10–4 (3) 1.25 × 10–4 (4) 1.25 × 10–5
Sol. Answer (4)
C 2
K for weak electrolyte 1   1; (( )  1)
1 
K  C 2
C
m 8
  

m 400
2
1 ⎛ 8 ⎞
Now K   1.25  105
32 ⎜⎝ 400 ⎟⎠
30. Kohlrausch's law states that at [AIPMT (Prelims)-2008]
(1) Infinite dilution, each ion makes definite contribution to equivalent conductance of an electrolyte, whatever
be the nature of the other ion of the electrolyte
(2) Finite dilution, each ion makes definite contribution to equivalent conductance of an electrolyte, whatever
be the naure of the other ion of the electrolyte
(3) Infinite dilution each ion makes definite contribution to equivalent conductance of an electrolyte depending
on the nature of the other ion of the electrolyte
(4) Infinite dilution, each ion makes definite contribution to conductance of an electrolyte whatever be the nature
of the other ion of the electrolyte
Sol. Answer (1)

Kohlrauschs law.
31. Standard free energies of formation (in kJ/mol) at 298 K are –237.2, –394.4 and –8.2 for H2O (l), CO2 (g) and
pentane (g) respectively. The value of Ecell for the pentane-oxygen fuel cell is [AIPMT (Prelims)-2008]
(1) 0.0968 V (2) 1.968 V (3) 2.0968 V (4) 1.0968 V
Sol. Answer (4)
C 5H 12 + 8O 2 5CO 2 + H 2O
[change in oxidation state(n) = 32]
Greaction = Gproducts – Greactants
Greaction = ⎡⎣5  G(CO2 )  6  G(H2O) ⎤⎦  ⎡⎣G(C5H12 ) ⎤⎦
= [(5 × –394.4) + 6 × (–237.2)] – [–8.2]
= (–1972 – 1423.2) + 8.2
 –nFE°Cell = –3387 kJ
3387  103
ECell   1.09 V
32  96500
32. On the basis of the following E° values, the strongest oxidizing agent is
[Fe(CN)6]4–  [Fe(CN)6]3– + e–1; E° = – 0.35 V
Fe2+  Fe3+ + e–1; E° = – 0.77 V [AIPMT (Prelims)-2008]
(1) [Fe(CN)6]3– (2) [Fe(CN)6]4–
(3) Fe2+ (4) Fe3+
Sol. Answer (4)
E°oxidation E°oxidation
[Fe(CN)6]
–4
(Fe )
+2
Oxidation potential  = Reducing nature , so oxidising nature 
–0.35 V –0.77 V
i.e., E°Reduction E°Reduction  Strongest oxidising agent

+3
[Fe(CN)6]–3 (Fe )
33. The equilibrium constant of the reaction

Cu(s) + 2Ag+ (aq)  Cu2+(aq) + 2Ag(s) ; E= 0.46V
at 298 K is [AIPMT (Prelims)-2007]
(1) 4.0 × 1015 (2) 2.4 × 1010 (3) 2.0 × 1010 (4) 4.0 × 1010
Sol. Answer (1)
Cu + 2 Ag+  Cu+2 + 2 Ag E° = 0.46 V
G = –nFECell = –2.303 RTlogKc
–2 × FECell = –2.303 × 8.314 × 298 logKc
–2 × 96500 × (0.46) = –2.303 × 8.314 × 298logKc
log10Kc = 15.55
Kc = (1015.55) antilog = 4 × 1015
34. The efficiency of a fuel cell is given by [AIPMT (Prelims)-2007]

S H G G
(1)  G (2)  G (3)  S (4)  H
Sol. Answer (4)

G
Efficiency of fuel cell =
H
35. If E° = –0.441 V and E° = 0.771 V, the standard EMF of the reaction Fe + 2Fe3+  3Fe2+
Fe2+ / Fe Fe3+ /Fe2+
will be [AIPMT (Prelims)-2006]
(1) 0.330 V (2) 1.653 V (3) 1.212 V (4) 0.111 V
Sol. Answer (3)
Fe2+ + 2 e–  Fe
Fe3+ + e–  Fe+2
Fe+ 2Fe3+  3 Fe2+
Cell representation Fe | Fe2+ || Fe3+ | Fe2+
ECell  E  E
Fe3  |Fe2  Fe2  |Fe
= 0.771 – (–0.441) = 1.212 V
36. A hypothetical electrochemical cell is shown belowA|A+(xM)||B+(yM)|B, the emf measured is +0.20 V. The cell
reaction is [AIPMT (Prelims)-2006]
(1) A+ + B  A + B+ (2) A+ + e–  A ; B+ + e–  B
(3) The cell reaction cannot be predicted (4) A + B+  A+ + B
Sol. Answer (4)
E  Ec  Ea
G = –nFECell
ECell = positive  so G = negative  i.e., given reaction is feasible reaction
i.e, A + A+ + e– (Oxidation)
B+ + e–  B (Reduction)
net reaction A + B+  A+ + B
37. 4.5g of aluminium (at. mass 27 amu) is deposited at cathode from Al3+ solution by a certain quantity of electric
charge. The volume of hydrogen produced at STP from H+ ions in solution by the same quantity of electric
charge will be [AIPMT (Prelims)-2005]
(1) 22.4 L (2) 44.8 L (3) 5.6 L (4) 11.2 L
Sol. Answer (3)
Al+3 + 3 e–  Al [4.5 g] = w1 2H+ + 2e–  H2 (Volume = ?)
(G.E)Al  (G.E)H2
w 22.4
 
E V
4.5 22.4 w 2
  
27 V E2
3
4.5 w 2
 
9 2
2
 w2 = 0.5 g
for 2g H2  22.4 L
22.4
 1g 
2
22.4
 0.5 g   0.5  5.6 L
2
38. A solution contains Fe2+, Fe3+ and I– ions. This solution was treated with iodine at 35°C. E° for Fe3+/Fe2+ is
+0.77 V and E° for I2/2I– = 0.536 V. The favourable redox reaction is
(1) I– will be oxidised to I2 (2) Fe2+ will be oxidised to Fe3+
(3) I2 will be reduced to I– (4) There will be no redox reaction
Sol. Answer (1)
S.R.P or oxidising power
Fe > I
(Fe) can oxidise (I) or Fe+3 reduced and I– will be oxidised.
39. Standard reduction potentials at 25°C of Li+ / Li, Ba2+ / Ba, Na+ / Na and Mg2+ / Mg are –3.05, –2.90, –2.71 and
–2.37 volt respectively. Which one of the following is the strongest oxidizing agent?
(1) Ba2+ (2) Mg2+ (3) Na+ (4) Li+
Sol. Answer (2)
S.R.P/oxidising power  Mg+2(Strongest oxidizing agent) > Na+ > Ba+2 > Li+
40. To protect iron against corrosion, the most durable metal plating on it, is
(1) Copper plating (2) Zinc plating (3) Nickel plating (4) Tin plating
Sol. Answer (2)
Most durable metal for iron is zinc [Fact].
41. An electrochemical cell is set up as :
Pt; H2 (1 atm) |HCl (0.1 M) || CH3COOH (0.1M) |
H2 (1 atm) ; Pt. The e.m.f. of this cell will not be zero, because
(1) Acids used in two compartments are different
(2) e.m.f. depends on molarities of acids used
(3) The temperature is constant
(4) pH of 0.1 M HCl & 0.1 M CH3COOH is not same
Sol. Answer (4)
HCl  H+ + Cl– CH3COOH CH3COO– + H+
Strong acid Weak acid
more pH less pH
pH different
so concentration of both are different
ECell  0
42. Electrode potential for the following half-cell reactions are

Zn  Zn2+ + 2e–; E° = + 0.76 V;
Fe  Fe2+ + 2e–; E° = + 0.44 V
The EMF for the cell reaction Fe2+ + Zn  Zn2+ + Fe will be
(1) – 0.32 V (2) + 1.20 V (3) – 1.20 V (4) + 0.32 V
Sol. Answer (4)
Zn  Zn+2 + 2e– Eoxidation  0.76 V  Ereduction

  0.76 V
Fe  Fe+2 + 2e– Eoxidation  0.44 V  Ereduction

  0.44 V
E  Ec  Ea at cathode at anode


= –0.44 – (–0.76) 2e
Fe2   Fe Zn  Zn2  2e
= +0.32 V
43. How many grams of cobalt metal will be deposited when a solution of cobalt(II) chloride is electrolyzed with a
current of 10 amperes for 109 minutes (1 Faraday = 96,500 C; Atomic mass of Co = 59 u)
(1) 0.66 (2) 4.0 (3) 20.0 (4) 40.0
Sol. Answer (3)

CO+2  Co
59
E
w  it  2  10  109  60  19.9 20 g
96500 96500
44. A 5 ampere current is passed through a solution of zinc sulphate for 40 minutes. The amount of zinc deposited at
the cathode is
(1) 0.4065 gm (2) 65.04 gm (3) 40.65 gm (4) 4.065 gm
Sol. Answer (4)
65
E
w  it  2  40  60  5  4.065 g
96500 96500
[Zn+2 + 2e–  Zn]
45. The molar conductances of NaCl, HCl and CH3COONa at infinite dilution are 126.45, 426.16 and 91 ohm–1 cm2
mol–1 respectively. The molar conductance of CH3COOH at infinite dilution is
(1) 698.28 ohm–1 cm2 mol–1 (2) 540.48 ohm–1 cm2 mol–1
(3) 201.28 ohm–1 cm2 mol–1 (4) 390.71 ohm–1 cm2 mol–1
Sol. Answer (4)
CH3COONa + HCl  CH3COOH + NaCl
°m = 91 + 426.16 = x + 126.45
x = 390.71
°m(CH3 COOH)
46. E° for the cell, Zn|Zn 2+ (aq)||Cu 2+ (aq)|Cu is 1.10 V at 25ºC, the equilibrium constant for the reaction
Zn + Cu2+ (aq) Cu + Zn2+ (aq) is the order of
(1) 10+18 (2) 10+37 (3) 10–28 (4) 10–37

Sol. Answer (2)
0.059
E  E  logK c
n
At equilibrium
0.059
E  log10 K c
2
0.059
1.10  log10 K c
2
Kc = 10+37
47. For the cell reaction, Cu2+ (C1 · aq) + Zn(s) = Zn2+ (C2 · aq) + Cu(s) of an electrochemical cell, the change in Free
Energy G at a given temperature is a function of
(1) ln (C2) (2) ln (C2/C1) (3) ln (C1) (4) ln (C1 + C2)
Sol. Answer (2)
Cu2  Zn  Zn2  Cu
C1 C2
(Zn2 )
 G  2.303RT log
(Cu2 )
C2 C
 G  2.303RT log or G  RT ln 2
C1 C1
48. The specific conductance of a 0.1 N KCl solution at 23°C is 0.012 ohm–1 cm–1. The resistance of cell containing
the solution at the same temperature was found to be 55 ohm. The cell constant will be
(1) 0.918 cm–1 (2) 0.66 cm–1 (3) 1.142 cm–1 (4) 1.12 cm–1
Sol. Answer (2)
1 ⎛l⎞
   Cell constant
R ⎜⎝ a ⎟⎠
1 ⎛l⎞
0.012  
55 ⎜⎝ a ⎟⎠
⎛l⎞ 1
⎜ a ⎟  0.012  55  0.66 cm
⎝ ⎠
49. For the disproportionation of copper 2Cu+  Cu2+ Cu, E° is (Given E° for Cu2+/Cu is 0.34 V and E° for Cu2+/Cu+ is
0.15 V)
(1) 0.49 V (2) –0.19 V (3) 0.38 V (4) –0.38 V
Sol. Answer (3)
2Cu+  Cu+2 + Cu E° = ?
1. Cu2  2 e   Cu E  0.34 V; G1  2F(0.34)
2. Cu2  e   Cu E  0.15 V; G2  F(0.15)
Reaction (2) is multiplied by (2)
So, 2 Cu2  2e  2 Cu (E° = 0.15 V) …(3)… G3  2F[0.15]
Now reaction [(1) – (3)] then we get required reaction.
Cu+2 + 2 e–  Cu  G°1

–2Cu + 2 e  2 Cu  G°3
+2 – +
–Cu+2  Cu – 2 Cu+

2 Cu  Cu + 2 Cu G°4
+ +2
or
So, G4  G1  G3
nFE4  2F(0.34)  ( 2F  0.15)
1 FE4  2F(0.34)  2F  0.15
E4  0.38 V
50. Cell reaction is spontaneous when
(1) G° is negative (2) G° is positive (3) E°Red is positive (4) E°Red is negative
Sol. Answer (1)
For spontaneous reaction G° = negative.
51. Equivalent conductances of Ba2+ and Cl– ions are 127 and 76 ohm–1 cm2 eq–1 respectively. Equivalent conductance
of BaCl2 at infinite dilution is (in the unit ohm–1 cm2 eq–1)
(1) 139.5 (2) 101.5 (3) 203 (4) 279
Sol. Answer (3)
 eq   eq
 
  eq  127  76  203
(Ba2 ) (Cl )
52. Standard electrode potentials are

Fe2+/Fe ; E° = –0.44 volts
Fe3+/Fe2+ ; E° = 0.77 volts
Fe2+, Fe3+ and Fe blocks are kept together, then
(1) Fe3+ increases (2) Fe3+ decreases
(3) Fe2+/Fe3+ remains unchanged (4) Fe2+ decreases

Sol. Answer (2)

2e
Fe2   Fe E° = –0.44
Fe 3  e   Fe 2 E° = 0.77
Fe+3 have more S.R.P than Fe+2 so, Fe+3 reduces more than Fe+2. i.e., Fe+3 is converted into Fe+2 which means
Fe+3 decreases  Fe+2 increases
53. PbO2  PbO G298 < 0

SnO2  SnO G298 > 0
Most probable oxidation state of Pb and Sn will be
(1) Pb4+, Sn4+ (2) Pb4+, Sn2+ (3) Pb2+, Sn2+ (4) Pb2+, Sn4+
Sol. Answer (4)
Pb+4O2  Pb+2O G < 0, negative
Spontaneous
i.e., Pb+4  Converted into Pb+2, so Pb+4 decreases, Pb+2 increases
Formation of Pb+2 increases  stability increases
Sn+4O2  Sn+2O G > 0, positive
Non-spontaneous
i.e., Sn+4 cannot easily converted into Sn+2 i.e., formation of Sn+2 decreases
 Stability of Sn+2 decreases
 Stability of Sn+4 increases
54. The most convenient method to protect the bottom of ship made of iron is
(1) Coating it with red lead oxide (2) White tin plating
(3) Connecting it with Mg block (4) Connecting it with Pb block
Sol. Answer (3)
55. In electrolysis of NaCl when Pt electrode is taken then H2 is liberated at cathode while with Hg cathode it forms
sodium amalgam
(1) Hg is more inert than Pt
(2) More voltage is required to reduce H+ at Hg than at Pt
(3) Na is dissolved in Hg while it does not dissolve in Pt
(4) Conc. of H+ ions is larger when Pt electrode is taken
Sol. Answer (2)
During electrolysis of NaCl using Pt electrode then H+ is higher discharge potential than Na+
So, H+ get reduced and form H2 at cathode but using Hg cathode H+ is lower discharge potential than Na+
so Na+ get reduced and form amalgam
i.e., H+ required more voltage at Hg
56. On the basis of the information available from the reaction of O2,
4 2
Al  O2  Al2O3 , G  827 kJmol1 ,
3 3
the minimum e.m.f. required to carry out electrolysis of Al2O3 is (F = 96500 C mol–1)
(1) 2.14 V (2) 4.28 V (3) 6.42 V (4) 8.56 V
Sol. Answer (1)
4 2 +3 G = –827 kJ/mole
Al  O2  Al2O3
3 3
2
Total change  6  4 one [Al  (+3)], so (2) Al  +6,
3
G = –nFECell = –4 × 96500 × ECell
–827 × 103 = –4 × 96500 × ECell
827  103
ECell   2.14 V
4  96500
57. The e.m.f. of a Daniel cell at 298 K is E1
Zn ZnSO4 CuSO4 Cu
(0.01M) (1.0M)
When the concentration of ZnSO4 is 1.0 M and that of CuSO4 is 0.01 M, the e.m.f. changed to E2. What is the
relationship between E1 and E2?
(1) E1 > E2 (2) E1 < E2 (3) E1 = E2 (4) E2 = 0  E1
Sol. Answer (1)
0.059 (Zn2 )
E1  E  log
2 (Cu2 )
0.059 0.01
E0  E  log …(1)
2 1.0
0.059 0.059
 E  log102  E  ( 2)
2 2
E1 = E° + 0.059
0.059 1
E2  E  log
2 0.01
0.059
E2  E  log102
2
0.059  2
 E 
2
 E° – 0.059
E1 = E° + 0.059 [E2 = E° – 0.059]
i.e., E1 > E2
58. The standard e.m.f. of a galvanic cell involving cell reaction with n = 2 is found to be 0.295 V at 25°C. The
equilibrium constant of the reaction would be (Given F = 96500 C mol–1, R = 8.314 J K–1 mol–1)
(1) 2.0 × 1011 (2) 4.0 × 1012 (3) 1.0 × 102 (4) 1.0 × 1010
Sol. Answer (4)
0.059
E  logK c
n
0.059
0.295  log10 K c
2
0.295  2
log10 K c 
0.059
log10Kc = 10
Kc = 1010
59. The mass of carbon anode consumed (giving only carbon dioxide) in the production of 270 kg of aluminium metal
from bauxite by the Hall process is (Atomic Mass: Al = 27)
(1) 270 kg (2) 540 kg (3) 90 kg (4) 180 kg
Sol. Answer (3)
change = 4
O +4
C + O 2  CO 2
(w1) = ?
(n-factor = 4)
⎛ w1 ⎞ ⎛ w2 ⎞ Al2O32H2O + Na2CO3  NaAlO2

⎜ ⎟ ⎜ ⎟ H2O
⎝ E0 ⎠c ⎝ E2 ⎠ Al
NaOH + Al(OH)3
⎛ w1 ⎞ E1 
`⎜ w ⎟  E reduction
⎝ 2⎠ 2 Al Al2O3
w2 = 270 kg
12 n-factor = 3 (Al+3)
w1 3
 4 
270 27 9
3
3
w1   270  90 kg
9
60. Consider the half-cell reduction reaction :

Mn2+ + 2e–  Mn, Eo = –1.18 V
Mn2+  Mn3+ + e–, Eo = –1.51 V
The Eo for the reaction 3 Mn2+  Mn0 + 2 Mn3+, and possibility of the forward reaction are, respectively
(1) –2.69 V and no (2) –4.18 V and yes (3) +0.33 V and yes (4) +2.69 V and no
Sol. Answer (1)
Mn2  2e  Mn G1  2F( 1.18) V
Mn2  Mn3  e ]  2 G2  2F( 1.51)

On addition
3 Mn2  2 Mn3  Mn G3  G1  G2
2FECell  2F( 1.18)  2F( 1.51)
2FECell  5.38F
5.38
ECell  ( )  2.69 V
2
SECTION - D
Assertion-Reason Type Questions
1. A : Molar conductivity of solution increases with dilution for weak electrolyte.

R : Degree of ionization increases with dilution.
Sol. Answer (1)
x  1000 ⎛ x  1000 ⎞
m   V⎜ ⎟
(M  n / V) ⎝ n ⎠
m  V.
and according to Ostwald's law
 V
2. A : H2 and O2 is obtained if dil. solution of Na2SO4 is electrolysed using Pt electrodes.

R : Platinum electrode is inert electrode.
Sol. Answer (2)
In case of dil solution, H2 at cathode and O2 at anode are obtained.
3. A : Anode is positive electrode and cathode is negative electrode in electrolytic cell.

R : Anode is negative electrode and cathode is positive electrode in electrochemical cell.
Sol. Answer (2)
In electrolytic cell : (+)ve end of battery is connected to anode while (–)ve end to cathode.
Electrochemical cell : Oxidation takes place at anode while reduction takes place at cathode.
4. A : Lithium is the strongest reducing agent in the periodic table.

R : Fluorine is the strongest oxidising agent in the periodic table.
Sol. Answer (2)
Li = highest oxidation potential.
F2 = highest reduction potential.
5. A : Electrode potential of hydrogen is pH dependent.

R : Electrode potential of hydrogen electrode is always zero.
Sol. Answer (3)
RT
o
Ecell  Ecell  log[H ]
nF
Eocell  0
[Ecell  0]
6. A : Sodium ions are discharged when aqueous solution of NaCl electrolysed using mercury electrode.
R : The nature of electrode can affect the order of discharge of ions.
Sol. Answer (2)
Na+ + e–  Na
Fact
e.g., In case Pt electrode, H2 is released while in case of Hg electrode, Na+ ion are discharged.
7. A : Copper rod turns colourless solution of zinc sulphate to blue.

R : Zinc reduces Cu2+ ions to Cu+.
Sol. Answer (4)
Zn replace Cu+2 ion from its solution and turn blue colour to colourless solution.
Cu+2 + Zn  Cu + Zn+2.
8. A : At equilibrium Ecell becomes zero.

R : At equilibrium reduction potential of both the electrodes becomes equal.
Sol. Answer (1)
Ecell = 0 = G
Ecell  Eooxi  Ered  0
⎡Eroe d(C)  Eroe d(A) ⎤

⎢ ⎥
⎢Eooxi(A)  Eooxi(C) ⎥
⎣ ⎦
9. A : Molten aluminium chloride when electrolysed using 0.1 F, deposits o.1 g equivalent of aluminium.
R : Mass of substance deposited  quantity of electricity.
Sol. Answer (2)
Al+3 + 3e–  Al
3 mole charge = 1 g equivalent electron = 1 F charge is required to deposit 1 mole of Al.
 0.1 F  0.1 mole Al is deposited.
 [W = ZQ] (Independent statement)
10. A : Lead storage battery does not require salt bridge.

R : The solid nature of each oxidising agent and reducing agent prevent direct cantact.
Sol. Answer (1)
Fact.
11. A : Electrolysis of molten calcium hydride produces hydrogen gas at the cathode.
R : Hydrogen in calcium hydride is present as H+ ion.
Sol. Answer (4)
CaH2
2H–  H2 + 2e– (anode)
12. A : Molar conductivity of 0.1 M NH4OH solution is less than that of 0.001 M NH4OH solution.
R : Dilution increases the degree of ionisation of NH4OH.
Sol. Answer (1)
K  1000
m 
M
1
 m  , m
M
n
 [ m  V] ⎡∵ M  ⎤
⎢ V ⎥⎦
⎣
13. A : Block of magnesium are often stapped to steel hulls of ocean going ships.
R : Magnesium causes cathodic protection of iron.
Sol. Answer (1)

Mg is more reactive than iron or oxidation potential of Mg > oxidation potential of Fe.
14. A : Salt bridge is used generally in the electrochemical cell.

R : The ions of the electrolyte used in the salt bridge should have the nearly same transport numbers.
Sol. Answer (2)
Salt bridge is used to maintain electrical neutrality of solution.
Velocity of ions is nearly same.
15. A : When CuSO4 is electrolysed using Cu electrodes then O2 gas is evolved at anode.
R : The discharge potential of OH– is more than SO42–.
Sol. Answer (4)
At anode,
Cu  Cu+2 + 2e–
16. A : One faraday electricity deposite 1 mole of Na & 2 mole of Cu in NaCl & CuSO4 solution respectively.
R : One faraday electricity always deposite 1 mole of any substance.
Sol. Answer (4)
One, faraday
= 1 mole of electron
1
 1 mole of electron  1 mole of Na deposit and mole of Cu deposit.
2
Cu+2 + 2e–  Cu, Na+ + e–  Na.


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Chapter 11

(Metallic/Electrolytic Conductors, Conductivity, Kohlrausch’s Law)

1. Which of the following is not a strong electrolytes?

2. The molar conductivity of strong electrolyte

3. The conduction of electricity through the electrolyte solution is due to

4. Which of the following is not correct?

5. Equivalent conductance of a weak electrolyte increases on dilution because of

6. As the dilution of an electrolyte increases

(1)  (2)  (3)  (4) 

i.e., on increasing concentration dissociation of

  1000 0.01287  1000

⎡CaF2  H2 O  solution ⎤

Sol. Answer (2)

  1000 26  102  1000 26  102  1000

19. Which of the following is a strong electrocyte?

(Electrolysis, Quantitative aspects of Electrolysis and Faraday's laws)

Ag NO3  1e   Ag

23. Electrochemical equivalent of Cu in the reaction Cu2+ + 2e– Cu is

Ag+ + e–  Ag For 1 mole of Ag+, Ca2+,

i.e, for 3-faraday 2 × 3 mole electrons

for 1 mole electrons = 1 faraday  1 mole of Ag+

27. If 9 g of H2O is electrolyzed completely with 50% current efficiency

Total volume = 11.2 + 5.6 = 16.8 L

(3) Amount of iron deposited in Fe2(SO4)3 and Fe(NO3)3 are equal

34. When dil. HNO3 is electrolysed

oxidation potential EOX(OH )  EOX(NO3 )

Current flows from

Anode is negative terminal

If Ecell > 0, G = negative(spontaneous)

Cathode is positive terminal

(3) Zn(s) Zn 2  ( 0.2M) Cu2  ( 0.002M) Cu(s) (4) All of these

Sol. Answer (2)

 –0.126 + 0.763 = 0.637

44. Calculate EMF of the cell

Given E° A | A+3 = 0.75 V

2 A + 3B+2  2 A+3 + 3 B E  Ec  Ea  0.45  ( 0.75)  0.3

0.059 (0.01)3 0.059

(C)[D] (C)2 [D]2

N2H4 + O°2  N2° + 2 H2O–2 so (n = 4)

49. Saturated solution of KNO3 is used to make salt bridge because

Sol. Answer (3)

50. Find out the E°cell from the given data

(1) – 0.04 V (2) + 0.04 V (3) + 0.30 V (4) 1.56 V

Zn  Cu2  Zn2  Cu E° = 1.10 V, G1 = –nFE  –2 F(1.10)  –2.20 F

Cu + 2 Ag+  2 Ag + Cu+2 E° = 0.46 V, G2 = –2F(0.46)  –0.92 F

Zn + 2 Ag+  Zn+2 + 2 Ag  G3 = G1  G2

–2 F E3  –2.20 F – 0.92 F

51. An electrochemical cell has two half cell reactions as,

52. If Eº Fe  2 |Fe is x1, E ºFe  3 |Fe is x2; then Eº  3  2 will be

(1) 3x2 – 2x1

(ii) Fe3  3 e  Fe E° = x2, G2 = –3Fx2

– Fe+2 + 2e–  Fe G3  G2  G1

1 FE3 ⇒  3Fx 2  ( 2F)x1

55. Corrosion is basically

56. The main factors which affect corroision are

anode Pb2SO4  H2O  Pb4 O2  H  e  SO42

58. In lead storage battery, the anode reaction is

Sol. Answer (2)

59. Which of the following is cathodic reaction?

Sol. Answer (3)

1. Fe+2  Fe+3 + e– (Oxidation)

4. 2 SO4–2  S2O8–2 + 2 e– (Oxidation)

(1) Sn can reduce Na+ to Na (2) Sn can reduce Zn2+ to Zn

63. Electrode potential data are given below

Br2(aq)  2e   2Br(aq)

Based on the above data which statement(s) is incorrect?

64. Fluorine is the best oxidising agent because it has

65. Ag2O  H2O  2e  2Ag  2OH

Ag21O  H2 O  2 e  2 Ag0  2OH

Atomic mass  i  t 177  2  5  60  60

left mass of (Zn+2)  w1 – w2 = 6.5 – 0.195 = 6.305

So, M  6.305  1000  0.194 M

13. Electrolysis of H2SO4 (conc.) gives the following at anode

(Electrochemical Cell, Commercial Cells or Batteries, Corrosion of Metals)

14. In SHE, the pH of the acid solution should be

15. E.M.F. of Ni(s)|Ni2+ (aq) || Cu2+ (aq)|Cu(s) cell can be increased by