Electrochemistry

EXERCISE-I

Galvanic cell, its Representation & salt bridge

Q.1 A cell from the following which converts electrical energy into chemical energy
(1) Dry cell (2) Electrochemical cell
(3) Electrolytic cell (4) None of these
Ans. (3)
Sol. In the electrolytic cell electrical energy change into chemical energy.

Q.2 Consider the Galvanic cell Zn  | ZnSO 4 || CuSO 4 | Cu  the reaction at cathode is

(1) Zn 2   2 e   Zn (2) Cu 2   2 e   Cu
(3) Cu 2   Zn  Cu  Zn 2  (4) Zn 2   Cu  Zn  Cu 2 
Ans. (2)
Cu 2   2e¯  Cu
Sol. 
Reduction

Q.3 The cell reaction Cu  2 Ag   Cu 2  Ag is best represented by

(1) Cu (s ) | Cu 2(aq ) || Ag  (aq ) | Ag (s)

(2) Pt | Cu 2 || Ag (aq ) | Ag (s )

(3) Cu 2 | Cu || Pt | Ag
(4) None of the above representations
Ans. (1)

Q.4 Saturated solution of KNO 3 is used to make ‘salt-bridge’ because

(1) Velocity of K  is greater than that of NO 3

(2) Velocity of NO 3 is greater than that of K 

(3) Velocities of both K  and NO 3 are nearly the same

(4) KNO 3 is highly soluble in water
Ans. (3)
Sol. Velocities of both K  and NO 3 are nearly the same in KNO 3 so it is used to make salt-bridge.

Q.5 In the reaction

Cu (s)  2 Ag  (aq )  Cu 2  (aq )  2 Ag (s)
The reduction half-cell reaction is
(1) Cu  2 e   Cu 2  (2) Cu  2 e   Cu 2 
(3) Ag   e   Ag (4) Ag  e   Ag 
Ans. (3)

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Q.6 Which of the following statements about galvanic cell is incorrect

(1) Anode is positive
(2) Oxidation occurs at the electrode with lower reduction potential
(3) Cathode is positive
(4) Reduction occurs at cathode
Ans. (1)
Sol. Anode has negative polarity.

Q.7 Which of the following is not used to construct salt bridge

(1) CH 3 COOK (2) KCl
(3) NH 4 NO 3 (4) KNO 3
Ans. (1)

Q.8 The standard reduction potential for Fe 2  / Fe and Sn 2 / Sn electrodes are 0 . 44 and 0 . 14 volt respectively.. For the
given cell reaction Fe 2   Sn  Fe  Sn 2  , the standard EMF is
(1) + 0.30 V (2) – 0.58 V
· (3) + 0.58 V (4) – 0.30 V
Ans. (4)
Sol. For the cell reaction, Fe acts as cathode and Sn as anode. Hence,
o
E cell  E cathode
o
 E anode
o
= – 0.44 – (– 0.14)= – 0.30V
The negative EMF suggests that the reaction goes spontaneously in reversed direction.

Q.9 Electrode potential of Zn 2  / Zn is 0 . 76 V and that of Cu 2  / Cu is 0 . 34 V . The EMF of the cell constructed between
these two electrodes is
(1) 1.10 V (2) 0.42 V
· (3) – 1.1V (4) – 0.42 V
Ans. (1)
Sol. o
E cell  E cathode
o
 E anode
o
 0. 34  ( 0 .76 )  1 .10 V .

Q.10 EMF of a cell whose half cells are given below is

Mg 2   2 e   Mg (s); E  2 . 37 V

Cu 2   2 e   Cu (s); E  0 . 33 V
(1) – 2.03 V (2) 1.36 V
· (3) 2.7 V (4) 2.03 V
Ans. (3)
Sol. o
E cell  E cathode
o
 E anode ; o
E cell  0 . 34  ( 2 . 37 )
o
E cell  2 . 71 V .

Q.11 Standard electrode potential of Ag  / Ag and Cu  / Cu is 0. 80 V and 0. 34 V respectively. these electrodes are joint
together by salt bridge if
o
(1) Copper electrode is work like cathode, then E cell is 0 . 45 V
o
(2) Silver electrode is work like anode then E cell is 0 . 34 V
o
(3) Copper electrode is work like anode then E cell is 0. 46 V
o
(4) Silver electrode is work like cathode then E cell is 0 . 34 V
o
(5) Silver electrode is work like anode then E cell will be 1 . 14 V

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Electrochemistry

Ans. (3)
Sol. Cell reaction is
Cu (s)  2 Ag   Cu 2   2 Ag
Two half cell reaction is
Cu  Cu 2   2e  Oxidation (anode)

Ag   e   Ag Reduction (cathode)
ECell  Eox  ERe d  0 .80  0 .34  0 .46 V

Q.12 The emf of a galvanic cell, with electrode potentials of silver = +0.80V and that of copper = + 0.34 V, is
(1) – 1.1 V (2) + 1.1 V
(3) + 0.46 V (4) + 0.76 V
Ans. (3)
Sol. E o  E oAg 2  / Ag  E Cu
o
/ Cu 2   0 .34  0 . 80  0 . 46 V .

Electrochemical series & its Applications

Q.13 If a strip of Cu metal is placed in a solution of ferrous sulphate
(1) Copper will precipitate out
(2) Iron will precipitate out
(3) Copper will dissolve
(4) No reaction will take place
Ans. (4)
Sol. Cu  FeSO 4  No reaction Because Cu has E o  0 . 34 volt and Fe has E o   0 . 44 volt.

Q.14 The standard reduction potentials at 298 K for the following half reactions are given against each

Zn 2  (aq.)  2 e 
  Zn(s) ; – 0.762
Cr 3  (aq )  3 e 
 Cr (s) ; – 0.740

2 H  (aq)  2e 
 H 2 (g) ; 0.00

Fe 3  (aq)  e  2
 Fe (aq) ; 0.770
Which is the strongest reducing agent
(1) Zn(s) (2) Cr (s)
(3) H 2 (g) (4) Fe 2  (aq)
Ans. (1)
Sol. More negative is the reduction potential, higher will be the reducing property, i.e. the power to give up electrons.

Q.15 Which of the following metal does not react with the solution of copper sulphate
(1) Mg (2) Fe (3) Zn (4) Ag
Ans. (4)

Q.16 A solution containing one mole per litre of each Cu ( NO 3 )2 , AgNO 3 , Hg 2 ( NO 3 )2 and Mg ( NO 3 )2 , is being electrolysed
by using inert electrodes. The values of standard electrode potentials in volts (reduction potentials) are
Ag / Ag   0 . 80 , 2 Hg / Hg 22   0 . 79 , Cu / Cu 2   0 . 34 , Mg / Mg 2   2 . 37 with increasing voltage, the sequence of
deposition of metals on the cathode will be
(1) Ag , Hg , Cu , Mg (2) Mg , Cu , Hg , Ag
(3) Ag , Hg , Cu (4) Cu , Hg , Ag
Ans. (3)

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Sol. A cation having highest reduction potential will be reduced first and so on. However, Mg 2  in aqueous solution will not

 
 0 
be reduced  E Mg 2 / Mg  E H 2O / 1 H 2  OH   . Instead water would be reduced in preference.
 2 

Q.17 The standard oxidation potential of zinc and silver in water at 298 K are

Zn (s)  Zn 2   2 e  ; E  0 . 76 V
Ag(s)  Ag+ + e–; E = –0.80 V
Which of the following reactions actually take place
(1) Zn(s)  2 Ag  (aq )  Zn   (aq)  2 Ag (s) (2) Zn   (aq)  2 Ag (s)  2 Ag  (aq )  Zn(s)

(3) Zn(s)  Ag (s)  Zn   (aq)  Ag  (aq ) (4) Zn   (aq)  Ag  (aq)  Zn(s)  Ag (s)
Ans. (1)
Reduction
o o
Zn (s )  2 Ag (aq)  Zn 2(aq)  2 Ag ( s)
Sol.
Oxidation

In this reaction zinc act as a anode and Ag act as a cathode.

Q.18 Which one of the following metals cannot evolve H 2 from acids or H 2 O or from its compounds
(1) Hg (2) Al (3) Pb (4) Fe
Ans. (1)
Sol. (1) Hg has greater reduction potential than that of H  and hence cannot displace hydrogen from acid.

Q.19 A standard hydrogen electrode has zero electrode potential because

(1) Hydrogen is easiest to oxidise
(2) The electrode potential is assumed to be zero
(3) Hydrogen atom has only one electron
(4) Hydrogen is the lightest element
Ans. (2)

Concept of DG
Q.20 The standard cell potential of Zn| Zn 2  (aq ) || Cu 2  (aq) | Cu cell is 1.10 V. The maximum work obtained by this cell will be
(1) 106.15 kJ (2) – 212.30 kJ· (3) – 318.45 kJ (4) – 424.60 kJ
Ans. (2)

Q.21 For a cell reaction involving a two-electron change, the standard emf of the cell is found to be 0.295 V at 25 o C . The
equilibrium constant of the reaction at 25 o C will be
(1) 1  10 10 (2) 29 .5  10 2 (3) 10 (4) 1  10 10
Ans. (4)
Sol. G  nFE o
G  2 .303 RT log K ; nFE o  2 . 303 RT log K

nFE o 2  96500  0 . 295

log K  
2 . 303 RT 2 . 303  8 . 314  298

log K  9 .97  K  1  10 10 .

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Electrochemistry

Q.22 The e.m.f. of the cell Zn | Zn 2  (0 .01 M )|| Fe 2  (0 .001 M )| Fe at 298 K is 0.2905 then the value of equilibrium for the cell
reaction is
0 . 32 0 . 32 0 . 26 0 . 32
(1) (2) (3) (4)
e 0.0295 10 0.0295 10 0.0295 10 0.0591
Ans. (2)
Sol. For this cell, reaction is: Zn  Fe 2  Zn 2  Fe

0 . 0591 c 0 . 0591 c
E  E0  log 1 ; E 0  E  log 1
n c2 n c2

0 . 0591 10 2
 0 . 2905  log  3  0 .32 V .
2 10

0 . 0591 0 . 32  2 0 . 32
E0  log K c ; log K c  
2 0 . 0591 0 . 0295

0 . 32
 Kc  .
10 0295

Nernst equation & its Applications (including concentration cells)

Q.23 The relationship between standard reduction potential of cell and equilibrium constant is shown by
n 0 . 059
(1) Ecell  (2) Ecell 
0 0
log K c log K c
0 . 059 n

log K c
(4) Ecell 
0
0
(3) Ecell  0 . 059 n log K c
n
Ans. (2)
2.303 RT 0.0591
Sol.
o
Ecell  log K  log K c at 298 K .
nF n

Q.24 The correct representation of Nernst’s equation is

0 . 0591
(1) E M n / M  E M n  / M 
o
log (M n  )
n

0 . 0591
(2) E M n / M  E M n / M 
o
log (M n  )
n

n
(3) E M n / M  E M n  / M 
o
log (M n  )
0 . 0591
(4) None of the above
Ans. (1)
RT 1 RT
(1) E  E  nF ln [M n  ] ; E  E  ln[M n  ]
o o
Sol.
nF

2 . 303 RT
E  Eo  log[ M n  ]
nF
Substituting the value of R, T (298K) and F we get
0 . 0591
E  Eo  log( M n  ) .
n

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 Electrochemistry

Q.25 Which of the following is correct expression for electrode potential of a cell
RT [product] RT [product]
(1) E  E  nF ln [reactant] (2) E  E  F ln [reactant]
o o

RT [reactant] RT [product]
(3) E  E  nF ln [product] (4) E   F ln [reactant]
o

Ans. (1)

Electrolysis
Q.26 Electrolysis involve oxidation and reduction respectively at
(1) Anode and cathode
(2) Cathode and anode
(3) At both the electrodes
(4) None of the above
Ans. (1)
Sol. In electrolysis process oxidation occurs at anode and reduction occurs at cathode.

Q.27 When the sample of copper with zinc impurity is to be purified by electrolysis, the appropriate electrodes are
Cathode Anode
(1) Pure zinc Pure copper
(2) Impure sample Pure copper
(3) Impure zinc Impure sample
(4) Pure copper Impure sample
Ans. (4)
Sol. Impure metal made anode while pure metal made cathode.

Q.28 On electrolysing a solution of dilute H 2 SO 4 between platinum electrodes, the gas evolved at the anode is
(1) SO 2 (2) SO 3 (3) O 2 (4) H 2
Ans. (3)
Sol. (3) In between dilute H 2 SO 4 and platinum electrode O 2 gas evolve at anode.

Q.29 During the electrolysis of fused NaCl , which reaction occurs at anode
(1) Chloride ions are oxidized (2) Chloride ions are reduced
(3) Sodium ions are oxidised (4) Sodium ions are reduced
Ans. (1)
Sol. In fused NaCl chloride ions are oxidized at anode and it is called oxidation.

Q.30 A certain current liberated 0.504 gm of hydrogen in 2 hours. How many grams of copper can be liberated by the same
current flowing for the same time in a copper sulphate solution
(1) 12.7 gm (2) 15.9 gm (3) 31.8 gm (4) 63.5 gm
Ans. (2)
Weight of Cu Eq. weight of Cu
Sol. (2) Weight of H  Eq. weight. of H
2

Weight of Cu 63 . 6 / 2

0 . 50 1
Weight of Cu  15 .9 gm.

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Electrochemistry

Q.31 What weight of copper will be deposited by passing 2 Faradays of electricity through a cupric salt
(Atomic weight of Cu = 63.5)
(1) 2.0 gm (2) 3.175 gm (3) 63.5 gm (4) 127.0 gm
Ans. (3)
Sol. Cu 2   2e   Cu
2 Faradays will deposit  1 g atom of Cu  63 .5 g .

Q.32 The desired amount of charge for obtaining one mole of Al from Al 3 
96500 96500
(1) 3  96500 C (2) 96500 C (3) C (4) C
3 2
Ans. (1)
Sol. Al  Al 3   3 e  .
The charged obtained is 3  96500 C .

Q.33 One Faraday of electricity when passed through a solution of copper sulphate deposits
(1) 1 mole of Cu (2) 1 gm atom of Cu
(3) 1 molecule of Cu (4) 1 gm equivalent of Cu
Ans. (4)
Sol. One Faraday  1 gm of equivalent of Cu .

Q.34 When electricity is passed through the solution of AlCl 3 , 13 .5 gm of Al are deposited. The number of Faraday must be
(1) 0.50 (2) 1.00 (3) 1.50 (4) 2.00
Ans. (3)
13 . 5
Sol. Eq. of Al = 27 /3  1 .5 .

Thus 1.5 Faraday is needed.

Q.35 When electric current is passed through a cell having an electrolyte, the positive ions move towards the cathode and the
negative ions towards the anode. If the cathode is pulled out of the solution
(1) The positive and negative ions will move towards the anode
(2) The positive ions will start moving towards the anode, the negative ions will stop moving
(3) The negative ions will continue to move towards the anode and the positive ions will stop moving
(4) The positive and negative ions will start moving randomly
Ans. (4)
Sol. In the absence of electric field the ions in the solution move randomly due to thermal energy.

Q.36 In electrolysis of dilute H 2 SO 4 using platinum electrodes

(1) H 2 is evolved at cathode (2) NH 3 is produced at anode
(3) Cl 2 is obtained at cathode (4) O 2 is produced
Ans. (1)
Sol. (1) When platinum electrodes are dipped in dilute solution H 2 SO 4 than H 2 is evolved at cathode.

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Faraday’s law & its Applictions

Q.37 On passing one faraday of electricity through the electrolytic cells containing Ag  , Ni 2 and Cr 3 ions solution, the
deposited Ag ( At . wt .  108 ), Ni ( At . wt .  59 ) and Cr ( At . wt .  52 ) is
Ag Ni Cr
(1) 108 gm 29.5 gm 17.3 gm
(2) 108 gm 59.0 gm 52.0 gm
(3) 108.0 gm 108.0 gm 108.0 gm
(4) 108 gm 117.5 gm 166.0 gm
Ans. (1)
Sol. (1) Wt. of Ag deposited  Eq. wt of Ag  108 gm
Wt. of Ni deposited  Eq. wt . of Ni  29 .5 gm

Wt. of Cr deposited  Eq. wt . of Cr  17 .3 gm .

Commercial Cells & Corrosion

Q.38 Which of the following reactions occurs at the cathode of a common dry cell
(1) Mn  Mn 2   2 e  (2) 2 MnO 2  Zn 2   2 e   ZnMn 2 O 4

(3) 2 ZnO 2  Mn 2   2 e   MnZn 2 O 4 (4) Zn  Zn 2   2 e 

Ans. (2)
Sol. (2) In common dry cell.
Anode : Zn  Zn   2e 
Cathode: 2 MnO 2  Zn    2 e   ZnMn 2 O 4 .

Q.39 When lead storage battery is charged

(1) PbO 2 is dissolved
(2) H 2 SO 4 is regenerated
(3) PbSO 4 is deposited on lead electrode
(4) Lead is deposited on lead electrode
Ans. (3)

Zn(s ) | Zn 2  (aq ) | | Cu 2  (aq ) | Cu ( s)

Q.40 (anode) (cathode)
is

(1) Weston cell (2) Daniel cell

(3) Calomel cell (4) Faraday cell
(5) Standard cell
Ans. (2)
Sol. The cell in which Cu and Zn roads are dipped in its solutions called Daniel cell.

Q.41 Which of the following reactions occurs at the cathode during the charging of a lead storage battery
(1) Pb 2   2 e   Pb
(2) Pb 2   SO 42   PbSO 4
(3) Pb  Pb 2   2 e 
(4) PbSO 4  2 H 2 O  2 PbO 2  4 SO 42   2e 
Ans. (4)
Sol. PbSO 4  2 H 2 O  2 PbO 2  4 SO 4   2 e  .

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Electrochemistry

Q.42 When a lead storage battery is discharged

(1) SO 2 is evolved
(2) Lead sulphate is consumed
(3) Lead is formed
(4) Sulphuric acid is consumed
Ans. (4)

Sol. 
Pb  PbO 2  2 H 2 SO 4  
 2 PbSO 4  2 H 2 O .
Disch arg e
Re ch arg e

Sulphuric acid is consumed on discharging.

Q.43 Which of the following statements is true for fuel cells

(1) They are more efficient
(2) They are free from pollution
(3) They run till reactants are active
(4) All of these
Ans. (4)
Sol. (4) Fuel cells are more efficient, free from pollution and they run till reactants are active.

Q.44 Corrosion is basically a

(1) Altered reaction in presence of H 2 O
(2) Electrochemical phenomenon
(3) Interaction
(4) Union between light metal and heavy metal
Ans. (2)

Q.45 Rusting of iron is catalysed by which of the following

(1) Fe (2) O 2 (3) Zn (4) H 
Ans. (4)
Sol. Rusting of iron is catalysed by [H  ] .

Q.46 Which of the following is a highly corrosive salt

(1) FeCl 2 (2) PbCl 2 (3) Hg 2 Cl 2 (4) HgCl 2
Ans. (4)
Sol. HgCl 2 has corrosive action. It is highly poisonous. It sublimes on heating. It is, therefore, known as corrosive sublimate.

Q.47 Corrosion of iron is essentially an electrochemical phenomenon where the cell reactions are

(1) Fe is oxidised to Fe 2  and dissolved oxygen in water is reduced to OH

(2) Fe is oxidised to Fe 3  and H 2 O is reduced to O 22 

(3) Fe is oxidised to Fe 2  and H 2 O is reduced to O 2

(4) Fe is oxidised to Fe 2  and H 2 O is reduced to O 2
Ans. (1)
Sol. Fe  Fe 2   2e (anode reaction)
O 2  2 H 2 O  4 e  4 OH  (cathode reaction)
The overall reaction is
2 Fe  O 2  2 H 2 O  2 Fe(OH ) 2

Fe(OH ) 2 may be dehydrated to iron oxide FeO , or further oxidised to Fe(OH ) 3 and then dehydrated to iron rust,

Fe 2 O 3 .

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Electrical Conductance
Q.48 In infinite dilutions, the equivalent conductances of Ba 2  and Cl  are 127 and 76 ohm 1cm 1 eqvt 1 . The equivalent
conductivity of BaCl 2 at indefinite dilution is
(1) 101.5 (2) 139.5· (3) 203.5 (4) 279.5
Ans. (2)
1  2
Sol.   BaCl 2   Ba    Cl 
2

127
  76  139 . 5 ohm 1 cm 1 eq 1 .
2

Q.49 Specific conductance of 0.1 m nitric acid is 6 .3  10 2 ohm 1cm 1 . The molar conductance of solution is
(1) 630 ohm 1cm 2 mole 1 (2) 315 ohm 1cm 2 mole 1
(3) 100 ohm 1 cm 2 mole 1 (4) 6300 ohm 1 cm 2 mole 1
(5) 63.0 ohm 1cm 2 mole 1
Ans. (4)

Q.50 If X is the specific resistance of the solution and M is the molarity of the solution, the molar conductivity of the solution
is given by
1000 X 1000 1000 M MX
(1) (2) (3) (4)
M MX X 1000
Ans. (2)
1000
Sol. Molar conductivity = .
MX

Q.51 Conductivity (unit Siemen’s) is directly proportional to area of the vessel and the concentration of the solution in it and
is inversely proportional to the length of the vessel then the unit of the constant of proportionality is
(1) Sm mol 1 (2) Sm 2 mol 1 (3) S 2 m 2 mol (4) S 2 m 2 mol 2
Ans. (2)
K [ A] A C l Sm
Sol. C ,K   Sm 2 mol 1 .
l [ A] A mol m  3 m 2

Q.52 The unit of equivalent conductivity is

(1) ohm cm (2) ohm 1 cm 2 (gm equivalent ) 1

(3) ohm cm 2 (gm equivalent ) (4) S cm 2

Ans. (2)

Q.53 It has been observed that gaseous hydrogen chloride is a very poor conductor of electricity but a solution of hydrogen
chloride gas in water is a good conductor of electricity. This is due to the fact that
(1) Water is good conductor of electricity
(2) Hydrogen chloride gas in water solution ionizes
(3) A gas is non-conductor but a liquid conducts electricity
(4) Gas does not obey Ohm’s law whereas solution does
Ans. (2)

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Q.54 Electrolytic conduction differs from metallic conduction in that in the case of electrolytic conduction
(1) The resistance increases with increasing temperature
(2) The resistance decreases with increasing temperature
(3) The flow of current does not generate heat
(4) The resistance is independent of the length of the conductor
Ans. (2)
Sol. Electrolytic conduction resistance decreases with increasing temperature.

Q.55 Conductivity of a strong electrolyte

(1) Increases on dilution
(2) Does not change considerably on dilution
(3) Decreases on dilution
(4) Depends on density
Ans. (2)
Sol. Strong electrolyte ionize completely at all dilutions and the number of ions does not increase on dilution. A small increase
in  m volume with dilution is due to the weakening of electrostatic attraction between the ions on dilution.

Q.56 Which one is not a conductor of electricity

(1) NaCl (aqueous) (2) NaCl (solid)
(3) NaCl (molten) (4) Ag metal
Ans. (2)
Sol. In solid state NaCl does not dissociate into ions so it does not conduct electricity..

Q.57 The unit of molar conductivity is

(1)  1cm 2mol 1 (2)  cm 2mol 1 (3)  1cm 2mol 1 (4)  cm 2mol
Ans. (3)

1
Sol. Molar condcutivity   M

So its unit will be  1 cm 2 mol 1 .

Q.58 The highest electrical conductivity of the following aqueous solutions is of

(1) 0.1 M acetic acid (2) 0.1 M chloroacetic acid
(3) 0.1 M fluoroacetic acid (4) 0.1 M difluoroacetic acid
Ans. (4)

76
 Electrochemistry

Q.59 ClCH 2 COONa  224 ohm 1 cm 2 gmeq 1 ,

 NaCl  38 .2 ohm 1 cm 2 gmeq 1 ,

 HCl  203 ohm 1 cm 2 gmeq 1 ,

What is the value of ClCH 2 COOH

(1) 288 .5 ohm 1 cm 2 gmeq 1 (2) 289 .5 ohm 1 cm 2 gmeq 1

(3) 388 .5 ohm 1 cm 2 gmeq 1 (4) 59 .5 ohm 1 cm 2 gmeq 1

Ans. (3)
Cl CH 2 COONa  HCl  ClCH 2 COOH  NaCl
Sol. ClCH 2COONa   HCl   
NaCl
ClCH 2 COOH

224  203   ClCH 2COOH  38 . 2

 ClCH 2 COOH  427  38 .2  388 .8 ohm 1 cm 2 gmeq 1 .

77
Electrochemistry

EXERCISE-II

Galvanic cell, its Representation & salt bridge

Q.1 In a galvanic cell
(1*) Chemical reaction produces electrical energy (2) electrical energy produces chemical reaction
(3) reduction occurs at anode (4) oxidation occurs at cathode
Ans. (1)
Sol. In galvanic cell/electro chemical cell electrical energy is produced due to some chemical reaction.

Q.2 Which of the following statements is wrong about galvanic cells ?

(I) Cathode is the positive electrode
(II) Cathode is the negative electrode
(III) Electrons flow from cathode to anode in the external circuit
(IV) Reduction occures at cathode
(1*) II & III (2) I & IV (3) both (4) None of these
Ans. (1)
Sol. Reduction and electronation take place at cathode elctrode, so it become positive electrode.

Q.3 Which of the following is/are function(s) of salt - bridge ?

(1) It completes the electrical circuit with electrons flowing from one electrode to the other through external wires and a
flow of ions between the two compartments through salt - bridge
(2) it minimises the liquid - liquid junction potential
(3*) both correct
(4) none of these
Ans. (3)
Sol. Salt bridge complete the electrical circuit and minimises the liquid - liquid junction potential.

Q.4 Salt bridge contains :

(1) calomel (2) corrosive sublimate (3) H2O (4*) agar-agar paste
Ans. (4)
Sol. Agar-Agar is a gelatin, it used in salt bridge along with KCl electrolyte.

Q.5 KCl can be used in salt bridge as electrolyte in which of the following cells?
(1) Zn | ZnCl2 || AgNO3 | Ag (2) Pb | Pb(NO3)2 || Cu(NO3)2 | Cu
(3*) Cu | CuSO4 || AuCl3 | Au (4) Fe | FeSO4 || Pb(NO3)2 | Pb
Ans. (3)
Sol. KCl can make precipitate with AgNO3, Pb(NO3)2 so can't be used along these electrolyte.

Q.6 1/2 H2(g) + AgCl(s) = H+ (aq) + Cl– (aq) + Ag (s) occurs in the galvanic cell :
(1) Ag/AgCl(s) | KCl (sol) | | AgNO3 (sol) | Ag (2) Pt/H2(g) | HCl (sol) | | AgNO3 (sol) | Ag
(3*) Pt/H2(g) | HCl (sol) | | Cl– | AgCl (sol) | Ag (4) Pt/H2(g) | KCl (sol) | | AgCl (sol) | Ag
Ans. (3)
Sol. In format of anode || cathode.

Q.7 The emf of the cell, Ni | Ni2+ (1.0 M) || Ag+ (1.0M) |Ag [E° for Ni2+ / Ni = – 0.25 volt, E° for Ag+/Ag = 0.80 volt] is given by-
(1) –0.25 + 0.80 = 0.55 volt (2) –0.25 – (+0.80) = –1.05 volt
(3*) 0 + 0.80 – (–0.25) = + 1.05 volt (4) –0.80 – (–0.25) = – 0.55 volt
Ans. (3)
Sol. Ecell = E°Ni / Ni2+ + EAg / Ag
= 0.25 + 0.80 = 1.05 Volt.

78
 Electrochemistry

Electrochemical series & its Applications

Q.8 Consider the cell potentials E º º
= – 2.37 V and EFe = – 0.04 V. The best reducing agent would be
Mg2  | Mg 3
| Fe
(1) Mg2+ (2) Fe3+ (3*) Mg (4) Fe
Ans. (3)
Sol. Lowest S.R.P., highest reducing power.

Q.9 If a spoon of copper metal is placed in a solution of ferrous sulphate -

(1) Cu will precipitate out (2) iron will precipitate
(3) Cu and Fe will precipitate (4*) no reaction will take place
Ans. (4)

Sol. E0 = 0.34 E0 = –0.44 volt

Cu2  / Cu Fe2  / Fe
So Cu can't displace Fe2+ .

Q.10 The position of some metals in the electrochemical series in decreasing electropositive character is given as
Mg > Al > Zn > Cu > Ag. What will happen if a copper spoon is used to stir a solution of aluminium nitrate ?
(1) The spoon will get coated with aluminium (2) An alloy of aluminium and copper is formed
(3) The solution becomes blue (4*) There is no reaction
Ans. (4)
Sol. Cu can't displace Al3+ ion from aluminium nitrate.

   
Q.11 Given E Ag  / Ag = 0.80V, E Mg2 / Mg = –2.37V,, E Cu2 / Cu = 0.34V, E Hg2 / Hg = 0.79 V.
Which of the following statements is/are correct
(I) AgNO3 can be stored in copper vessel
(II) Mg(NO3)2 can be stored in copper vessel
(III) CuCl2 can be stored in silver vessel
(IV) HgCl2 can be stored in copper vessel
(1*) II & III (2) I & IV (3) both (4) None of these
Ans. (1)
Sol. Lower S.R.P. containing ion can displace higher S.R.P. containing ion.

Q.12 For Zn2+ / Zn, E° = –0.76 V, for Ag+/Ag E° = 0.799 V. The correct statement is -
(1) the reaction Zn+2 getting reduced Ag getting oxidized is spontaneous
(2) Zn+2 undergoes reduction and Ag is oxidized
(3*) Zn undergoes oxidation Ag+ gets reduced
(4) No suitable answer
Ans. (3)
Sol. Lower S.R.P. containing ion can displace higher S.R.P. containing ion.

Q.13 Electrode potential data are given below.

Fe3+ (aq) + e–  Fe2+ (aq); E0 = + 0.77
Al (aq) + 3e  Al (s);
3+ – 
E0 = – 1.66 V
Br2 (aq) + 2e–  2Br– (aq) ; E0 = + 1.08 V
Based one the data given above, reducing power of Fe , Al and Br – will increase in the order :
2+

(1*) Br – < Fe2+ < Al (2) Fe2+ < Al < Br – (3) Al < Br – < Fe2+ (4) Al < Fe2+ < Br –
Ans. (1)
Sol. Lowest S.R.P., highest reducing power.

79
Electrochemistry

Q.14 Fe is reacted with 1.0 M HCl. Eº for Fe / Fe2+ = + 0.34 V. The correct observation(s) regarding this reaction is/are :
(I) Fe will be oxidised to Fe2+
(II) Fe2+ will be reduced to Fe
(III) since e.m.f. > 0, the reaction shall occur
(IV) since e.m.f. > 0, the reaction shall not occur.
(1*) I & III (2) II & III (3) both (4) None of these
Ans. (1)
Eº  Eº
Sol. Fe2  / Fe H / H2 ; So, Fe oxidised into Fe2+

Fe + 2H+  Fe2+ + H2 ECell = +ve.

Q.15 A standard hydrogen electrons has zero electrode potential because

(1) hydrogen is easier to oxidise. (2) this electrode potential is assumed to be zero.
(3) hydrogen atom has only one electron. (4) hydrogen is the lightest element.
Ans. (2)

Concept of DG

Q.16 E0 for F2 + 2e–  2F– is 2.8 V,,

1
E0 for F + e–  F– is
2 2
(1*) 2.8 V (2) 1.4 V (3) – 2.8 V (4) – 1.4 V
Ans. (1)
Sol. E0 is intensive property and it do not depend on mass of F2 taking part.

Q.17 Given standard electrode potentials :

Fe3+ + 3e¯  Fe ; E° = –0.036 volt
Fe2+ + 2e¯  Fe; E° = –0.440 volt
The standard electrode potential E° for Fe3+ + e¯  Fe2+
(1) –0.476 volt (2) –0.404 volt (3) 0.440 volt (4*) 0.772 volt
Ans. (4)
Sol. Fe3+ + 3e–  Fe , – 0.036 volt

Fe  Fe2+ + 2e– , 0.44 volt

Fe3+ + e–  Fe2+ + 3 × 0.036f –2 × 0.44 × f = – 1 × E° × f
E° = 0.772 Volt

Q.18 Cu+ + e–  Cu, E° = x1 volt ;

Cu2+ + 2e–  Cu, E° = x2 volt, then for

Cu2+ + e–  Cu+, E° (volt) will be -

(1) x1 – 2x2 (2) x1 + 2x2 (3) x1 – x2 (4*) 2x2 – x1
Ans. (4)

Sol. Cu+ + e–  Cu , E° = x1 Volt

Cu2+ + 2e–  Cu , x2 Volt

Cu  Cu+ + e– – x1Volt

Cu2+ + e–  Cu+

– 2 × x2 × f + 1 × x1 × f = –1 × Eº × f
Eº = 2x2–x1

80
 Electrochemistry

Q.19 Any redox reaction would occur spontaneously, if :

(1*) the free energy change ( G) is negative (2) the Gº is positive
(3) the cell e.m.f. (Eº) is negative (4*) the cell e.m.f. is positive .
Ans. (4)
Sol. G0 = – nFE0cell
If E0cell = +ve then G° = –ve and reaction is spontaneous.

Q.20 Which of the following statements about the spontaneous reaction occurring in a galvanic cell is always true?
(1) Eºcell > 0, Gº < 0, and Q < K (2) Eºcell > 0, Gº < 0, and Q > K
(3) Eºcell > 0, Gº > 0, and Q > K (4*) Ecell > 0, G < 0, and Q < K
Ans. (4)
Sol. For spontaneous reaction in every condition
Ecell > 0, G < 0 and Q (reaction quotient) < K (equilibrium constant).
Q.21 Zn | Zn2+ (C1)|| Zn2+ (C2)|Zn. for this cell G is negative if -
(1) C1 = C2 (2) C1 > C2 (3*) C2 > C1 (4) None
Ans. (3)
Sol. Zn Zn2C1  + 2e–

Zn2C2  + 2e– Zn

Zn2C2  Zn2C1 

0.0591 C1
E=0– log C
2 2

E  +ve When C1 < C2

Q.22 Given : Hg22+ + 2 e 2 Hg , E0 = 0.789 V & Hg2+ + 2 e  Hg , E0 = 0.854 V,

calculate the equilibrium constant for Hg22+  Hg + Hg2+ .
(1) 3.13 × 103 (2) 3.13 × 104 (3*) 6.26 × 103 (4) 6.26 × 104
Ans. (3)
Sol. Hg22  + 2e–  2Hg , 0.789 Volt
Hg  Hg2+ + 2e– , –0.854 Volt
Hg22+  Hg + Hg2+ , –0.065 Volt
G = – 2× (– 0.065) × 96500 = –8.314 × 298 ln Keq. ; Keq.= 6.3 × 10–3

Q.23 One mole of electron passes through each of the solution of AgNO3, CuSO4 and AlCl3 when Ag, Cu and Al are deposited
at cathode. The molar ratio of Ag, Cu and Al deposited are
(1) 1 : 1 : 1 (2) 6 : 3 : 2 (3) 6 : 3 : 1 (4) 1 : 3 : 6
Ans. (2)
Sol. Molar ratio
All have the same equivalent
equiv.
& mole =
nf.

1 1 1
 ratio : ; :
1 2 3
 6:3:2

81
Electrochemistry

Q.24 Salts ofA(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 of A, B and C respectively are
(1) 3, 1 and 2 (2) 1, 3 and 2 (3) 3, 1 and 3 (4) 2, 3 and 2
Ans. (2)
2 .1 2 .7 7 .2
Sol. x= ×y= ×z
7 27 48
y z
 ratio x = =
3 2
If x = 1  y = 3, z = 2

Q.25 The efficiency of an hypothetical cell is about 84% which involves the following reaction :
A (s) + B2+ (aq)  A2+ (aq) + B (s) : H = – 285 kJ
Then, the standard electrode potential of the cell will be (Assume as S = 0)
(1) 1.20 (2) 2.40 V (3) 1.10 V (4*) 1.24 V
Ans. (4)
2 2
Sol. A(s) + Baq.  A aq. + B(s) , H° = – 285 KJ

Assuming s to negligible , G° = H° = –285×103×0.84 = –2×E°×96500

E° = 1.24 Volt
Q.26 Using the data in the preceding problem, calculate the equilibrium constant of the reaction at 25°C.

[ Zn2 ]
Zn + Cu++ Zn++ + Cu, K =
[Cu2 ]
(1) 8.314 × 1024 (2) 4.831 × 1031 (3*) 8.314 × 1036 (4) 4.831 × 1044
Ans. (3)
Sol. E 298 = 1.1028 – 0.641 × 10–3 × 25 + 0.72 × 10–5 × (25)2 = 1.091275 Volt
= –8.314 × 298 ln K= – 2 × 1.091275 × 96500
K = 1036.91 = 8.128 × 1036.
Q.27 The standard reduction potentials of Cu2+/Cu and Cu2+/Cu+ are 0.337 and 0.153 V respectively. The standard electrode
potential of Cu+/Cu half cell is :
(1) 0.184 V (2) 0.827 V (3) 0.521 V (4) 0.490 V
Ans. (3)
Sol. 2e– + Cu2+  Cu : 0.337
Cu2+ + e–  Cu+ : 0.153
Cu+  Cu2+ + e– ; – 0.153
________________________
e– + Cu+  Cu

E 2  0.337  1  0.153
 =
Cu / Cu
1
= 0.674 – 0.153
= 0.521 V

Nernst equation & its Applications (including concentration cells)

Q.28 The electrode potential becomes equal to standard electrode potential when reactants and products concentration ratio is
-
(1*) equal to 1 (2) greater than 1 (3) less than 1 (4) none of the above
Ans. (1)
0.0591 [Product ]
Sol. E = E0 – log
n [Reactant ]
[Product ]
if = 1 then E = E0.
[Reactant ]
82
 Electrochemistry

Q.29 The standard emf for the cell reaction Zn + Cu2+  Zn2+ + Cu is 1.10 volt at 25°C. The emf for the cell reaction when
0.1 M Cu2+ and 0.1 M Zn2+ solutions are used at 25°C is
(1*) 1.10 volt (2) 0.110 volt (3) –1.10 volt (4) –0.110 volt
Ans. (1)
0.0591 0 .1
Sol. E = 1.1 – log  E = 1.10 Volt
2 0 .1


Pt H2 H H H2 Pt
Q.30 (p1) (1M) (1M) (p2 ) (where p1 and p2 are pressures) cell reaction will be spontaneous if :

(1) p1 = p2 (2*) p1 > p2 (3) p2 > p1 (4) p1 = 1 atm

Ans. (2)
Sol. H2( p ) 2H+ + 2e–
1

2H+ + 2e– H2( p )

2

X2 ( p )
X 2( p )
1 2

0.0591 p2
E=0– log p
2 1

P2 < P1 for E  +ve

Q.31 Pt | (H2) | pH = 1 || pH = 2 | (H2)Pt

1 atm 1 atm
The cell reaction for the given cell is :
(1) spontaneous (2*) non - spontaneous (3) equilibrium (4) none of these
Ans. (2)

Sol. H2  2H(10– 2 M) + 2e–

2H+(10–3 M) + 2e–  H2

2H(10– 3 M)  2H(10– 2 M)

2
 10 –1 
0.0591  
E=0– log  – 2 
2  10 
E  – ve (Non spontaneaous).

Q.32 The cell Pt (H2) (1 atm) | H (pH = ?) || I - (a = 1) | AgI(s), Ag has emf, E298K = 0. The standard electrode potential for the
reaction AgI + e¯  Ag + I is – 0.151 volt. Calculate the pH value.
(1) 3.37 (2) 5.26 (3*) 2.56 (4) 4.62
Ans. (3)
0.0591
Sol. 0 = (– 0.151 – 0) – log [H+].
1
0.0591 × log[H+] = – 0.151
0.151
pH = = 2.56
0.0591

83
Electrochemistry

Q.33 Using the information in the preceding problem, calculate the solubility product of AgI in water at 25°C [ E º =+
( Ag , Ag)
0.799 volt]
(1) 1.97 × 10–17 (2*) 8.43 × 10–17 (3) 1.79 × 10–17 (4) 9.17 × 10–17
Ans. (2)

E0 0 0.0591 1
Sol. Ag| Ag I |I –
= E Ag |Ag – log K
1 SP

0.0591 1
– 0.151 = 0.799 – log K
1 sp

0.0591 log Ksp = – 0.151 –0.799

log Ksp= – 16.074
Ksp = 8.43 × 10–17

Q.34 The solubility product of silver iodide is 8.3 × 10–17 and the standard reduction potential of Ag+, Ag electrode is + 0.8 volts
at 25° C. The standard reduction potential of Ag,Agl/l¯ electrode from these data is
(1) – 0.30 V (2) + 0.15 V (3) + 0.10 V (4*) – 0.15 V
Ans. (4)
0.0591 1
Sol. E Ag / AgI / I– = 0.8 – log K
1 sp

= 0.8 + 0.0591 × log 8.3 × 10–17

= – 0.15 Volt
or

E º Ag / Ag /  –  E º RT
1
Ag / Ag   . ln k
F sp

8.31 298  2.303

= – 0.8 – log ksp
96500
= – 0.8 – 0.0591. log 8.3 × 10–17
= – 0.8 + 0.095 = 0.15 V.


2 H (Pt ) H3 O  (aq) Ag 0
Q.35 Consider the cell 1 atm Ag. The measured EMF of the cell is 1.0 V. What is the value of x ? E Ag ,Ag
pH  5.03 x M
= + 0.8 V. [T = 25°C]
(1*) 2 × 10–2 M (2) 2 × 10–3 M (3) 1.5 × 10–3 M (4) 1.5 × 10–2 M
Ans. (1)
Sol. H2(Pt) (1 atm) | H3 O  | | Ag+(xM) | Ag

0.06 [H ]
1.0 = (0 + 0.8) – log
1 x

0 .2 [H ]
– = log
0.06 x

10
= pH + log x
3
log x = – 1.7

84
 Electrochemistry

– 5 .5
10
= 1.62 × 10–4
x
x = 2 × 10–2 M

1
Q.36 The standard potential of the reaction H2O + e–  H + OH– at 298 K by using Kw (H2O) = 10–14, is :
2 2
(1*) – 0.828 V (2) 0.828 V (3) 0 V (4) – 0.5 V
Ans. (1)
1
Sol. H+ + e– H , E° = 0 ,G° = 0
2 2
H2O H+ + OH– , G° = – 8.314 × 298 ln 10–14
1
H2O + e–  H + OH– , –1 × E° × 96500 = –8.314 × 298 ln10–14
2 2
E° = – 0.828 Volt.

M
Q.37 The EMF of a concentration cell consisting of two zinc electrodes, one dipping into sol. of zinc sulphate & the other
4

M
into sol. of the same salt at 25C is
16
(1) 0.0125 V (2) 0.0250 V (3*) 0.0178 V (4) 0.0356 V
Ans. (3)
0.0591 16 0.0591
Sol. E=0– log =– ×2 log 2 = – 0.0591 × 0.301 = – 0.0178 Volt.
2 4 2
If connected in reverse direction,E = 0.0178 volt.

Q.38 MnO4– + 8H+ + 5e–  Mn2+ + 4H2O,

If H+ concentration is decreased from 1 M to 10–4 M at 25ºC, where as concentration of Mn2+ and MnO4– remain 1 M.
(1*) the potential decreases by 0.38 V with decrease in oxidising power
(2) the potential increases by 0.38 V with increase in oxidising power
(3) the potential decreases by 0.25 V with decrease in oxidising power
(4) the potential decreases by 0.38 V without affecting oxidising power
Ans. (1)
Sol. MnO –4 + 8H+ + 5e–  Mn2+ + 4H2O

0.0591 [Mn 2  ]
E1 = E° – log
5 [MnO 4– ]  18

0.0591 [Mn2 ] 0.0591

E2 = E° – log 8 =– × 32 = –0.37824
5 5
[MnO 4– ]  10 – 4 
 
E1–E2 = 0.38 Volt.

Q.39 At equimolar concentrations of Fe2+ and Fe3+, what must [Ag+] be so that the voltage of the galvanic cell made from the
(Ag+ | Ag) and (Fe3+ | Fe2+) electrodes equals zero ?
Fe2+ + Ag+ Fe3+ + Ag
Eº Ag |Ag = 0.7991 ; Eº Fe 3  | Fe 2  = 0.771
(1*) 0.34 (2) 0.44 (3) 0.47 (4) 0.61
Ans. (1)

85
Electrochemistry

0.0591 1
Sol. 0 = (–0.771 + 0.7991) – log  0 = 0.0281 +0.0591 log X
1 x
0.0281
log X = –  X = 0.335 M
0.0591

Q.40 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 25ºC with be
(1) 0.059 V (2) 0.59 V (3) 0.0295 V (4) 0.118 V
Ans. (1)
0.0591
Sol. Ecell = Eº – log Qeq.
n
2H+ + 2e–  H2 Eº = 0

PH
2 0.0591
Qeq. =  2 , Ecell log 100 = –0.0591
(H ) 2
Ecell = 0.0591

Q.41 The equilibrium constant for the reaction

Sr(s) +Mg+2 (aq) Sr+2(aq) + Mg(s) is 2.69 × 1012 at 25ºC
The Eº for a cell made up of the Sr/Sr+2 and Mg+2/Mg half cells
(1) 0.3667 V (2) 0.7346 V (3) 0.1836 V (4) 0.1349 V
Ans. (1)

0.0591 Sr 2 
Sol. Eo cell = log
2 Mg2 

0.0591
= log (2.69 × 10 +12) = 0.3667
2
0
Q.42 A silver wire dipped in 0.1 M HCl solution saturated with AgCl develops oxidation potential of –0.25 V. If EAg / Ag = –

0.799 V , the Ksp of AgCl in pure water will be :

(1) 2.95 × 10–11 (2) 5.1 × 10–11 (3) 3.95 × 10–11 (4) 1.95 × 10–11
Ans. (2)
Sol. Ag  Ag+ + e–

Eo = –0.799 Ecell = –0.25

Ecell = –0.25 Eocell = –0.799
0.0591
 Ecell = Eocell – log (Ag+)
1
–0.25 + 0.799 = –0.0591 log (Ag+)
0.799  0.25
log (Ag+) =
0.0591
(Ag+) = 5.13 × 10–10
Ksp = (Ag+) (Cl–) = 5.13 × 10–10 × 0.1
= 5.13 × 10–11

86
 Electrochemistry

Q.43 Consider the folowing Galvanic cell.

Voltmeter

H2(g) Cl2(g)

+ –
K NO3

HCl HCl
Pt(s)

Anode Cathode

By what value the cell valtage change when concentration of ions in anodic and cathodic compartments both increased
by factor of 10 at 298 K.
(1) + 0.0591 (2) – 0.0591 (3) – 0.1182 (4) 0
Ans. (2)
Sol. Anode
H2  2H+ + 2e–
Cathode
2e– + Cl2  2Cl–
H2 + Cl2  2H+ + 2Cl–
[(H+)2 (Cl–)2] = Keq.
0.0591
Ecell = Eº – log (H+)2 (Cl–)2
2
= Eº – 0.0591 log [H+] [Cl–]

Q.44 For the cell

Pt|H2(0.4 atm)| H+(pH = 1)||H+(pH=2)|H2(0.1 atm)|Pt
The measured potential at 25º C is
(1) – 0.1 V (2) – 0.5 (3) – 0.041 (4) None
Ans. (3)
Sol. H2  2H+ + 2e–
0.4 atm 10–1
2H + 2e  H2
+ –

10–2 0.1 atm

______________________
H2 + 2H+  H2 + 2H+
0.4 0.01 0.1 0.1 Eº = 0

0.0591  (0.1) (0.1) 

2

Ecell = – log  2  = –0.041

2  (0.01) (0.4) 

Electrolysis
Q.45 The passage of current through a solution of certain electrolye results in the evolution of H2 at cathode and Cl2 at
anode. The electrolytic solution is -
(1) Water (2) H2SO4 (3) aq. NaCl (4) aq. CuCl2
Ans. (3)
– +
Sol. In this Cl will oxidise to give Cl2 ,Na reduction potential has lower potential than water reduction polenlid so water will reduce to give
H2.
(3) NaCl

87
Electrochemistry

Q.46 In an electrolytic cell current flows from -

(1) Cathode to anode in outer circuit (2) Anode to cathode outside the cell
(3) Cathode to anode inside the cell (4) Anode to cathode inside the cell
Ans. (1)
Sol. As electron flows from anode to a cthode and so current flows from cathode to anode in outer drcuit

Q.47 When an aqueous solution of H2SO4 is electrolysed, the ion discharged at anode is-
(1) H¯ (2) OH¯ (3) SO42– (4) O2–
Ans. (2)
2–
Sol. Water oxidation at anode can be represented and SO4 can't be discharged
so
+ –
2H2O  4H + O2 + 4e
–
so ion which will be discharged at anode will be OH .

Q.48 A solution of Na2SO4 in water is electrolysed using Pt electrodes.The products at the cathode and anode are respectively
-
(1) H2, SO2 (2) O2, NaOH (3) H2, O2 (4) O2, SO2
Ans. (3)
Sol. At cathode
– –
4H2O + 4e  4H2 + 4OH
At anode
+ –
2H2O  4H + O2 + 4e
Thus at cathode we will get H2 whereas at anode we will get O2.

Q.49 In electrolysis of a fused salt, the weight deposited on an electrode will not depend on-
(1) Temperature (2) Current intensity
(3) Electrochemical equivalent of ions (4) Time for electrolysis
Ans. (1)
Sol. In electrolysis of a fused salt, the weight deposited on electrode will not depend or temperature.

Q.50 The electrolysis of a solution resulted in the formation of H2 at the cathode and Cl2 at the anode. The liquid is-
(1) Pure water (2) H2SO4 solution
(3) NaCl solution in water (4) CuCl2 solution in water
Ans. (3)
– +
Sol. In this Cl will oxidise to give Cl2 Na water reduction potential has higher potential than that of water reduction potential,
so water will reduce to give H2.

Q.51 Which loses charge at cathode -

(1) Ions (2) Cations (3) Anions (4) Both anions and cations
Ans. (2)
Sol. Cation loses charge at cathode as it gave electron.

Q.52 In the electrolysis of CuSO4, the reaction: Cu2+ + 2e¯  Cu, takes place at :
(1) Anode (2) Cathode (3) In solution (4) None
Ans. (2)
Sol. As reduction will take place at cathode
2+
so reaction Cu + 2e  Cu
Will take place at cathode

Q.53 If mercury is used as cathode in the electrolysis of aqueous NaCl solution, the ions discharged at cathode are-
(1) H+ (2) Na+ (3) OH¯ (4) Cl¯
Ans. (2)

88
 Electrochemistry

Sol. If mercury is used as cathode in the electrolysis of aqueos NaCl solution then the metal is discharged at mercury to from
amalgam.

Q.54 The density of Cu is 8.94 g cm–3. The quantity of electricity needed to plate an area 10 cm × 10cm to a thickness of 10–2 cm
using CuSO4 solution would be
(1) 13586 C (2) 27172 C (3) 40758 C (4) 20348 C
Ans. (2)
Sol. Volume : 10 × 10 × 10–2 = 1 cm3
mass of Cu = 8.94 g
8.94
mole of Cu =
63.5

8.94
EQuivalent of Cu = ×2
63.5

8.94
Charge = × 2 × 96500 C = 27172 C
63.5

Q.55 During electrolysis of an aqueous solution of sodium sulphate if 2.4 L of oxygen at STP was liberated at anode. The
volume of hydrogen at STP, liberated at cathode would be :
(1) 1.2 L (2) 2.4 L (3) 2.6 L (4) 4.8 L
Ans. (4)
Sol. Equivalent of H2 = Equivalent of O2
2.4
= ×4
22.4

2.4 1
 mole of H2 = ×4×
22.4 2

2.4  2
Volume of H2 = × 22.4
22.4
= 4.8 L

Q.56 During electrolysis of an aqueous solution of CuSO4 using copper electrodes, if 2.5 g of Cu is deposited at cathode, then
at anode.
(1) 890 ml of Cl2 at STP is liberated (2) 445 ml of O2 at STP is liberated
(3) 2.5 g of copper is deposited (4) a decrease of 2.5 g of mass takes place
Ans. (4)
Sol. At both electrodes oxidation of Cu & reduction of Cu takes place
Anode Cu  Cu2+
Cathode Cu2+  Cu
So If 2.5 g deposited at cathode 2.5 of Cu mass decreased from anode

Q.57 A solution of sodium sulphate in water is electrolysed using inert electrodes. The products at the cathode and anode are
respectively.
(1) H2, O2 (2) O2, H2 (3) O2, Na (4) None
Ans. (1)
Sol. Cathode
2H2O + 2e–  H2 + 20H–
Anode
2H2O  4H+ + O2 + 4e–

89
Electrochemistry

Q.58 When an aqueous solution of lithium chloride is electrolysed using graphite electrodes
(1) Cl2 is liberated at the anode.
(2) Li is deposited at the cathode.
(3) as the current flows, pH of the solution around the cathode remains constant.
(4) as the current flows, pH of the solution around the cathode decreases.
Ans. (1)
Ans\Sol.LiCl (According to S.R.P.)
Cathode
2H2O + 2e–  H2 + 2OH–
Anode 2Cl–  Cl2 + 2e–
2Cl–  Cl2 + 2e–
At cathode (OH–)  pH  and pH 

Q.59 In an electrolytic cell of Ag/AgNO3/Ag, when current is passed, the concentration of AgNO3
(1) Increases (2) Decreases (3*) Remains same (4) None of these
Ans. (3)

Sol. At anode A  Ag+ + e–

At cathode Ag+ + e–  Ag

+
So conc. of Ag will remain same .

Q.60 On electrolysis, in which of the following , O2 would be liberated at the anode ?

(1) dilute H2SO4 with Pt electrodes (2) aqueous AgNO3 solution with Pt electrodes
(3) aqueous NaOH with a Fe cathode & Pt anode (4*) All correct
Ans. (4)

Sol. (1) Anode 2H2O  O2 + 4H+ + 4e–

(2) Anode 2H2O  O2 + 4H+ + 4e–

(3) Anode Cu  Cu2+ + 2e–

(4) Anode 2H2O  O2 + 4H+ + 4e–

Q.61 One gm metal M+2 was discharged by the passage of 1.81×1022 electrons. What is the atomic weight of metal?
(1) 33.35 (2) 133.4 (3) 66.7 (4) 55
Ans. (3)
22
1.81  10 1
Sol. 23 = At. mass × 2
6.02  10
rxn. Mn2+  Mn
nf = 2

2  6.022  1023
At mass = = 66.7
1.81  1022

Q.62 How many faradays are required to reduce one mol of MnO4¯ to Mn2+ -
(1) 1(2) 2 (3) 3 (4*) 5
Ans. (4)

Sol. 8H+ + 5e– + MnO4–  Mn+2 + 4H2O

(1 mole)
5 mole e– = 5 Faraday.

90
 Electrochemistry

Q.63 Three faradays of electricity was passed through an aqueous solution of iron (II) bromide. The mass of iron metal (at. mass
56) deposited at the cathode is -
(1) 56 g (2*) 84 g (3) 112 g (4) 168 g
Ans. (2)
1
Sol. Mole of Fe deposited = × 3 = 1.5 mole
2
WFe = 1.5 × 56 = 84 gm.

Q.64 A current of 9.65 ampere is passed through the aqueous solution NaCl using suitable electrodes for 1000 s. The amount
of NaOH formed during electrolysis is
(1) 2.0 g (2*) 4.0 g (3) 6.0 g (4) 8.0 g
Ans. (2)
Sol. 2H2O + 2e– H2 + 2OH–
9.65  1000
No. of Faraday passed = = 0.1 F
96500
nOH– formed = 0.1 mol
nNaOH = 0.1 mol  4 gm.

Faraday laws & its Applictions

Q.65 1 mole of Al is deposited by X coulomb of electricity passing through aluminium nitrate solution. The number of moles
of silver deposited by X coulomb of electricity from silver nitrate solution is-
(1) 3(2) 4 (3) 2 (4) 1
Ans. (1)
Sol. Since to deposit 1 mole of aluminium 3 columb of electricity is required, as the alency of silver is + 1 so 3 mole of silver will
be deposited by 3C of electricity

Q.66 A certain current liberates 0.504 g of H2 in 2 hours. How many grams of copper can be liberated by the same current
flowing for the same time in CuSO4 solution -
(1) 31.8 g (2) 16.0 g (3) 12.7 g (4) 63.5 g
Ans. (2)
Sol. gm eq. of H2 = gm eq. of Cu
0.504 w
2= 2
2 63.5

63.5  0.50 R
W= = 16.0 gm
2

Q.67 A currnet of 2.6 ampere is passed through CuSO4 solution for 6 minutes 20 seconds. The amount of Cu deposited is (At.
wt. of Cu = 63.5, Faraday = 96500 C)-
(1) 6.35 g (2) 0.635 g (3) 0.325 g (4) 3.175 g
Ans. (3)
it
Sol. No. of F = = gm eq of Cu
96500

gm eq. of Cu
moles of Cu =
2
2.6  380
moles of Cu =
96500  2
2.6  380
wt. of Cu = × 63.5
96500  2
= 0.325 gm

91
Electrochemistry

Q.68 Three Faradays of electricity are passed through molten Al2O3, aqueous solution of CuSO4 and molten NaCl taken in
three different electrolytic cells. The amount of Al, Cu and Na deposited at the cathodes will be in the ratio of-
(1) 1 mole : 2 mole : 3 mole (2) 1 mole : 1.5 mole : 3 mole
(3) 3 mole : 2 mole : 1 mole (4) 1 mole : 1.5 mole : 2 mole
Ans. (2)
Sol. gm equivalent of Al = gm eq. of Cu = gm eq. of Na
3=3=3
3/3/ = 3/2 = 1
1 : 1.5 : 3

Q.69 The quantity of electricity required to liberate 0.01g equivalent of an element at the electrode is-
(1) 9650C (2) 96500C (3) 965C (4) 96.5C
Ans. (3)
8
Sol. gm equivalent =
96500

8
0.01 = = 965 C
96500

Q.70 The unit of electrochemical equivalent is-

(1) gm ampere–1 (2) gm/coulomb (3) gm-ampere (4) coulomb/gram
Ans. (2)
Sol. Z = w/it
w in gm
it in columb.
so z = gm/columb

Q.71 One faraday of electricity will liberate one mole of metal from a solution of-
(1) AuCl3 (2) CuSO4 (3) BaCl2 (4) KCl
Ans. (4)
Sol. Since KCl has the n-factor of 1 so 1 faraday of electricity will liberate one mole of metal from a solution.

Q.72 The number of faraday required to generate 1 mole of Mg from MgCl2 is-
(1) 1(2) 2 (3) 3 (4) 4
Ans. (2)
Sol. Since magnesium has the n-factor 2 so the number of faraday rquired to genereate 1 mole of Mg will be 2 .

Q.73 If 0.224 L of H2 gas is formed at the cathode, the volume of O2 gas formed at the anode under identical conditions, is
(1) 0.224 L (2) 0.448 L (3*) 0.112 L (4) 1.12 L
Ans. (3)
Sol. equivalence of H2 = equivalence of O2
0.224 volume of O 2
2 = 4
22.4 22.4
0.112 litre = volume of O2.

Q.74 Three moles of electrons are passed through three solutions in succession containing AgNO3, CuSO4, and AuCl3,
respectively. The molar ratio of amounts of cations reduced at cathode will be
1 1 1
(1) 1 : 2 : 3 (2*) : : (3) 3 : 2 : 1 (4*) 6 : 3 : 2
1 2 3
Ans. (2)

92
 Electrochemistry

Sol. Ag Cu Au
equivalent 1 : 1 : 1
ratio
1 1 1
Mole ratio : :
1 2 3
6 : 3 : 2.

Q.75 One g equivalent of Na metal is formed from electrolysis of fused NaCl. No. of mole of Al from the fused Na3AlF6 with the
same current passed is :
(1) 1 (2) 3 (3*) 1/3 (4)2
Ans. (3)
Sol. Na+ + e–  Na(s)
1mole 1 Faraday
Al3+ + 3e–  Al(s)
1 Faraday
1
No. of mole of Al = mole.
3

Commercial Cells & Corrosion

Q.76 In H2  O2 fuel cell the reaction occuring at cathode is :
(1*) 2 H2O + O2 + 4 e  4 OH (2) 2 H2 + O2  2 H2 O (l)
1
(3) H+ + OH  H2O (4) H+ + e  H .
2 2
Ans. (1)
Sol. H2–O2 fuel cell

At anode : 2OH– + H2  2H2O + 2e–

At cathode : 2 H2O + O2 + 4e–  4OH–

Q.77 When a lead storage battery is discharged

(1*) PbSO4 is formed (2) Pb is formed (3) SO2 is consumed (4*) H2SO4 is consumed
Ans. (1)
Sol. Discharging reaction

Pb(s) + PbO2(s) + 2H2SO4 (aq)  2PbSO4 (s) + 2H2O.

Electrical Conductance
Q.78 The specific conductance of a solution is 0.3568 ohm–1. When placed in a cell the conductance is 0.0268 ohm–1 cm–1.
The cell constant is-
(1) 1.331 cm–1 (2) 13.31 cm–1 (3) 0.665 cm–1 (4) 6.65 cm–1
Ans. (2)
–1
Sol. K = 0.3568  cm
–1
condutance = 0.0268 
K = G ×1/A
0.3568 = 0.0268 ×1/9
–1
13.31 cm

Q.79 A conductance cell was filled with a 0.02 M KCl solution which has a specific conductance of 2.768 × 10–3 ohm–1
cm–1. If its resistance is 82.4 ohm at 25ºC, the cell constant is-
(1) 0.2182 cm–1 (2) 0.2281 cm–1 (3) 0.2821 cm–1 (4) 0.2381 cm–1

93
Electrochemistry

Ans. (2)
Sol. K = G. L/A
–3
10 × 2.768 = 1/R ×L/A
–3
L/A = 228.08 × 10
–1
= 0.2281 cm

Q.80 Which of the following solutions has the highest equivalent conductance ?
(1) 0.01M NaCl (2) 0.050 M NaCl (3) 0.005M NaCl (4) 0.02M NaCl
Ans. (3)
Sol. Higher the dilution higher will be the equivalent conductance

Q.81 The resistance of 0.01N solution of an electrolyte AB at 328K is 100 ohm. The specific conductance of solution is (cell
constant = 1cm –1)-
(1) 100ohm (2) 10-2 ohm–1 (3) 10-2 ohm–1 cm–1 (4) 102 ohm–cm
Ans. (3)
L
Sol. K=G
A

1 L
K= 
R A

1
 1 , K = 10  cm
–2 –1 –1

100

Q.82 For an electrolytic solution of 0.05 mol L–1, the conductivity has been found to be 0.0110 Scm–1.The molar conductivity
is-
(1) 0.055 S cm2 mol –1 (2) 550 S cm2 mol –1 (3) 0.22 S cm2 mol –1 (4) 220 S cm2 mol–1
Ans. (4)
K  1000
Sol. m =
M

0.0110  1000
m =
0.05
2 –1
= 220 S cm mol

Q.83 Two electrodes are fitted in conductance cell 1.5 cm apart while the area of cross section of each electrode is 0.75 cm2.
The cell constant is-
(1) 1.125 (2) 0.5 cm (3) 2.0 cm–1 (4) 0.2 cm–1
Ans. (3)
Sol. L/A is cell constant.
1.5 –1
= 2.0 cm
0.75

Q.84 The best conductor of electricity is in 1M solution of-

(1) CH3COOH (2) H2SO4 (3) H3PO4 (4) Boric acid
Ans. (2)
Sol. That electrolyte will be the best electrolyte which has maximum number of ions.

Q.85 Equivalent conductance of 0.1 M HA (weak acid) solution is 10 Scm2 equivalent–1 and that at infinite dilution is 200 Scm2
equivalent–1. Hence pH of HA solution is
(1) 1.3 (2) 1.7 (3) 2.3 (4) 3.7
Ans. (3)

94
 Electrochemistry

10 1
Sol. = =
200 20

1 1
[H+] = C = 0.1 × =
20 200

1
pH = – log = log 200 = 2.3
200

Q.86 If x is specific resistance of the electrolyte solution and y is the molarity of the solution, then ^ m is given by:
1000 x y 1000 xy
(1) (2) 1000 (3) (4)
y x xy 1000
Ans. (3)
1
Sol. K=
x

1000 1 1000 1000

^=k = × y = xy
M 

Q.87 The dissociation constant of n-butyric acid is 1.6×10–5 and the molar conductivity at infinite dilution is 380 × 10–4 Sm2mol–
1
. The specific conductance of the 0.01 M acid solution is
(1) 1.52 × 10–5 Sm–1 (2) 1.52 × 10–2 Sm–1 (3) 1.52 × 10–3 Sm–1 (4) None
Ans. (2)

Scm2 1000
Sol. 380 × 10–4 × 104 =k×
mole M

Molarity of ion

x2
1.6 × 10–5 =  16 × 10–8
0.01  x
16 ×10–8 = x2
x = 4 × 10–4

380  M 380  4  10 4
K= 
1000 1000
= 152 × 10–6 Scm–1
= 1.52 × 10–2 Sm–1

Q.88 The ionization constant of a weak electrolyte is 25 × 10–6 while the equivalent conductance of its 0.01 M solution is 19.6 S
cm2 eq–1. The equivalent conductance of the electrolyte at infinite dilution (in S cm2 eq–1 ) will be
(1) 250 (2) 196 (3*) 392 (4) 384
Ans. (3)
Sol. Ka = 25×10–6  eq = 19.6 Scm2 eq–1 , C = 0.01

 = 25  10 –6
Ka = 0.01 × 2 = 5 × 10–2
10 – 2

19.6 19.6

 = 5 × 10–2 =    eq = = 392 Scm2 eq-1.
eq 5  10 – 2

95
Electrochemistry

Q.89 Which has maxmium conductivity :

(1) [Cr(NH3)3 Cl3] (2) [Cr(NH3)4 Cl2]Cl (3) [Cr(NH3)5Cl]Cl2 (4*) [Cr(NH3)6]Cl3
Ans. (4)
Sol. Molar conductivity  no. of ions per mole of electrolyte.

Q.90 Molar conductances of BaCl2, H2SO4 and HCl at infinite dilutions are x1, x2 and x3, respectively. Equivalent conductance of
BaSO4 at infinite dilution will be :
[ x1  x 2  x 3 ] [ x1  x 2  x 3 ] [ x1  x 2  2x 3 ]
(1) (2) (3) 2 (x1 + x2 – 2x3) (4*)
2 2 2
Ans. (4)
 eq.,BaSO 4
Sol. m,BaSO 4 = (x1 + x2 x – 2x3)   eq.,BaSO 4 =
n  factor

( x1  x 2 – 2x 3 )
 eq.,BaSO 4 =
2

Q.91 The conductivity of a saturated solution of Ag3PO4 is 9×10–6 Sm–1 and its equivalent conductivity is 1.50×10–4 Sm2
equivalent–1 . The Ksp of Ag3PO4 is ;
(1) 4.32 × 10–18 (2) 1.8 × 10–9 (3) 8.64 × 10–13 (4) None of these
Ans. (1)
1000
Sol. 1.5 × 10–4 ×104 = 9 × 10–8 ×
N
 N = 6 × 10–5
5
6  10
 M= = 2 × 10–5
3
n factor
Ksp = (3S)2 (S) = 27S4 = 27 × 16 × 10–20
= 432 × 10–20 = 4.32 × 10–18

Q.92 The conductivity of a saturated solution of BaSO4 is 3.06 × 10–6 ohm–1 cm–1 and its equivalent conductance is 1.53 ohm–
1
cm2 equiv–1. The Ksp for BaSO4 will be
(1) 4 × 10–12 (2) 2.5 × 10–13 (3) 25 × 10–9 (4*) 10–6
Ans. (4)

1000  3.06  10 –6
Sol. 1.53 = Normality
Normality = 2 × 10–3 M
2  10 –3
Molarity = = 10–3 M
2
Ksp = 10–6 M

Q.93 Molar conductance of 0.1 M acetic acid is 7 ohm 1 cm2 mol 1 . If the molar cond. of acetic acid at infinite dilution is 380.8
ohm 1 cm2 mol 1 , the value of dissociation constant will be :
(1) 226  10 5 mol dm 3 (2) 1.66  10 3 mol dm 1 (3) 1.66  10 2 mol dm 3 (4*) 3.442  10 5 mol dm 3
Ans. (4)
2
 7 
Sol. Ka = C2 = 0.1×   = 3.38 × 10–5
 380.8 

96
 Electrochemistry

Q.94 The conductivity of a solution of AgCl at 298 K is found to be 1.382 × 10–6 –1 cm–1. The ionic conductance of Ag+ and Cl–
at infinite dilution are 61.9 –1 cm2 mol–1 and 76.3 –1 cm2 mol–1 , respecitvley. The solubility of AgCl is
(1) 1.4 × 10–5 mol L–1 (2) 1 × 10–2 mol L–1 (3*) 1 × 10–5 mol L–1 (4) 1.9 × 10–5 mol L–1
Ans. (3)
Sol. K = 1.382 × 10–6 s cm–1
10001.38210 –6
AgCl = 61.9 + 76.3 = 138.2 = S

S = 10–5 M.

Q.95 Asaturated solution in AgA(Ksp = 3 × 10–14) and AgB(Ksp = 1 × 10–14) has conductivity of 375 × 10–10 Scm–1 and limiting molar
conductivity of Ag+ and A– are 60 Scm2 mol–1 and 80 Scm2 mol–1 respectively then what will be the limiting molar conductivity
of B–(in Scm2mol–1)
(1) 150 (2) 180 (3) 190 (4) 270
Ans. (3)
Sol. AgA Ag+ + A– ; 3 × 10–14
S1 + S2 S1
AgB + –
Ag + B ; 1 × 10 –14

S1 + S2 S2
–7
S1 + S2= 2 × 10 ; S1 = 1.5 × 10 –7

S2 = 0.5 × 10–7
375 × 10–10 = K Ag  K A   KB 

( Ag )(MAg ) (  )(M  ) (  )(M  )

A A B B
= + +
1000 1000 1000

= 60 (S1 + S2) + 80 S1 +  B –S2

After putting value of S1 & S2
 = 270
B

Q.96 The resistance of 0.5 M solution of an electrolyte in a cell was found to be 50 . If the electrodes in the cell are 2.2 cm apart
and have an area of 4.4 cm2 then the molar conductivity (in S m2 mol–1) of the solution is
(1) 0.2 (2) 0.02 (3) 0.002 (4) None of these
Ans. (3)
1  2.2 1
Sol. C= ; = =
50 a 4.4 2

C 1 1
K= = × = 10–2
a 50 2
1000
m = k ×
M
1000
= 10–2 × = 20S cm2 mol–1
0 .5
= 20 × 10–4 Sm2/mol
= 0.002 Sm2/mol–1

97
Electrochemistry

Kohlrausch law and its applications

Q.97 Which of the following curve represents the variation of M with C for AgNO3 ?

(1*) (2) (3) (4)

Ans. (1)
Sol. For strong electrolyte

CM = M – b C

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 Electrochemistry

EXERCISE-III

JEE-MAIN
PREVIOUS YEAR’S

Q.1 For the following cell with hydrogen electrodes at two different pressure p1and p2,
Pt | H2(g) | H+(aq) | H2 (g) | Pt
p1 1M p2
emf is given by : [AIEEE 2002]

RT p RT p RT p RT p
(1) log e 1 (2*) log e 1 (3) log e 2 (4) log e 2
F p2 2F p2 F p1 2F p1
Ans. (2)
Sol. The Eo of cell will be zero.

Q.2 Which of the following reactions is possible at anode : [AIEEE 2002]

(1*) 2 Cr3+ + 7H2O Cr2O72– + 14H+ (2) F2 2F–
1
(3) O + 2H+  H2O (4) displacement reaction
2 2
Ans. (1)
Sol. Here Cr3+ is oxidised to C 2O72

Q.3 For a cell given below : [AIEEE 2002]

Ag | Ag+ || Cu2+ | Cu
Ag+ + e–  Ag Eº = x
Cu2+ + 2e–  Cu, Eº = y
The value of Eºcell is :
(1) x + 2y (2) 2x + y (3*) y –x (4) y – 2x
Ans. (3)
Sol. At LHS (oxidation) 2 × (Ag  Ag+ + e– ) Eºox = –x
At RHS (reduction) Cu2+ + 2e–Cu Eºred = + y
2Ag + Cu2+  Cu + 2Ag+, Eºred = (y – x)

Q.4 Conductance (with unit Siemens S) is directly proportional to area of the electrode plates and the concentration of the
solution in the cell and is inversely proportional to the separation between the electrode plates. Then the unit of the
constant of proportionality is : [AIEEE 2002]
–1 2 –1 –2 2 2 2 –1
(1) Sm mol . (2*) Sm mol . (3) S m mol. (4) S m mol .
Ans. (2)
1 1 
Sol. K 
 RA

Q.5 For a cell reaction involving a two electron change, the standard emf of the cell is found to be 0.295 V at 25°C. The
equilibrium constant of the reaction at 25°C will be : [AIEEE 2003]
(1) 1 × 10–10 (2) 29.5 × 10–2 (3) 10 (4*) 1 × 1010
Ans. (4)
0.059
Sol. 0 = 0.295 – logK ; log K = 10 ; K = 1010.
2

Q.6 Standard electrode potentials of three metals A, B and C are + 0.5 V, – 3.0 V and – 1.2 V respectively. The reducing power
of these metals is in the order : [AIEEE 2003]
(1*) B > C > A (2) A> B > C (3) C > B > A (4) A> C > B

99
Electrochemistry

Ans. (1)
Sol. A B C
Eored +0.5V –3.0 V –1.2 V
The reducing power follows the following order : B > C > A.

Q.7 Consider the following E0 values :

E0 3  2 = + 0.77 V ; E0 2 = – 0.14 V
Fe / Fe Sn / Sn

Under standard conditions, the cell potential for the reaction given below is : [AIEEE 2004]
Sn(s) + 2Fe3+(aq)  2Fe2+(aq) + Sn2+(aq)
(1) 1.68 V (2) 1.40 V (3*) 0.91 V (4) 0.63 V
Ans. (3)
Sol. Eºcell = 0.77 + 0.14 = 0.91 volt.

Q.8 The limiting molar conductivities º for NaCl, KBr and KCl are 126, 152 and 150 S cm2 mol–1 respectively. The value of º
for NaBr is : [AIEEE 2004]
(1*) 128 S cm2 mol–1 (2) 176 S cm2 mol–1 (3) 278 S cm2 mol–1 (4) 302 S cm2 mol–1
Ans. (1)
0
Sol.  NaBr = 126 + 152 – 150 = 128 S cm2 mol–1.

Q.9 In a cell that utilizes the reaction Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g),
addition of H2SO4 to cathode compartment will : [AIEEE 2004]
(1) lower the E and shift equilibrium to the left. (2) lower the E and shift the equilibrium to the right.
(3*) increase the E and shift the equilibrium to the right. (4) increase the E and shift the equilibrium to the left.
Ans. (3)
Sol. Zn + 2H+(aq)  Zn2+ (aq) + H2 (g)
0.0591 [ Zn2  ] pH2
E = Eº – log
2 [H ]2
Adding H2SO4 means increasing H+ and therefore Ecell will increase and reaction will shift to forward direction.

0
Q.10 The EM3  / M2  values for Cr, Mn, Fe and Co are – 0.41, + 1.57, + 0.77 and + 1.97 V respectively. For which one of these
metals, the change in oxidation state from +2 to +3 is easiest : [AIEEE 2004]
(1*) Cr (2) Mn (3) Fe (4) Co
Ans. (1)
Sol. Cr 2 | Cr 3   0.41V Mn2 | Mn3   1.57V
Fe 2 | Fe3   0.77V Co2 | Co3   1.97 V
As Cr will have maximum oxidation potential value, therefore its oxidation will be easiest.

Q.11 The highest electrical conductivity among the following aqueous solutions is of : [AIEEE–2005]
(1) 0.1 M acetic acid (2) 0.1 M chloroacetic acid
(3) 0.1 M fluoroacetic acid (4*) 0.1 M difluoroacetic acid
Asn. (4)
Sol. Difluoroacetic acid will be strongest acid due to electron withdrawing effect of two fluoring atoms so as it will show
maximum electrical conductivity.

Q.12 Aluminium oxide may be electrolysed at 1000ºC to furnish aluminium metal (At.Mass of Al = 27 amu ;
1 Faraday = 96,500 Coulombs). The cathode reaction is Al3+ + 3e–  Al. To prepare 5.12 kg of aluminium metal by this
method, one would require : [AIEEE–2005]
(1*) 5.49 × 107 C of electricity (2) 1.83 × 107 C of electricity
(3) 5.49 × 104 C of electricity (4) 5.49 × 1010 C of electricity

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 Electrochemistry

Ans. (1)
Sol. Al3+ + 3e–  Al.

5.12  103
=189.62 mol.
27
Charge = 189.62 × 3 × 96500 = 5.489 × 107 coulomb.

Q.13 The molar conductivities 0NaOAc and 0HCl at infinite dilution in water at 25°C are 91.0 and 426.2 Scm2/mol respectively..

To calculate 0HOAc , the additional value required is : [AIEEE–2006]

0
(1) H2O (2) 0KCl (3) 0NaOH (4*) 0NaCl
Ans. (4)
Sol. CH3COONa + HCI  CH3COOH + NaCI From the reaction,

0CH COONa + oHCI = 0CH COOH + oNaCI

3 3

or

0CH 0
=  CH3COONa + oHCI – oNaCI
3COOH

0 0
Thus to calculate the value of  CH3COOH one should know the value of oNaCI along with  CH3COONa and oHCI.

Q.14 Given data is at 25°C :

Ag + – Ag + e– ; E° = 0.152 V
Ag Ag+ + e– ; E° = – 0.800 V
0.474
What is the value of log Ksp for AgI : (Take = 8.065) [AIEEE–2006]
0.059
(1) – 8.12 (2) + 8.612 (3) – 37.83 (4*) – 16.13
Ans. (4)
0.059
Sol. 0.152 = – 0.8 – log KSP
1
log KSP = – 16.11.

Q.15 Resistance of a conductivity cell filled with a solution of an electrolyte of concentration 0.1 M is 100 . The conductivity
of this solution is 1.29 Sm–1. Resistance of the same cell when filled with 0.02 M of the same solution is 520 . The molar
129
conductivity of 0.02 M solution of the electrolyte will be : (Take = 0.248) [AIEEE–2006]
520
(1*) 124 × 10–4 Sm2mol–1 (2) 1240 × 10–4 Sm2mol–1 (3) 1.24 Sm2mol–1 (4) 12.4 × 10–4 Sm2mol–1
Ans. (1)
Sol. C = 0.1 M, R = 100 
1 
K = 1.29 Sm-1 = × .
100 A
C = 0.02 M, R = 520 .
1
K = × 129
520

1
 129
520
Å M = 1000  0.02

= 124 × 10–4 Sm2mol-1.

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Electrochemistry

Q.16 The equivalent conductances of two strong electrolytes at infinite dilution in H2O (where ions move freely through a
solution) at 25°C are given below : [AIEEE–2007]

0CH = 91.0 Scm2/equiv and 0HCl = 426.2 Scm2/equiv

3COONa

What additional information/quantity one needs to calculate º of an aqueous solution of acetic acid :

(1) The limiting equivalent conductance of H+ (H  ) (2) º of chloroacetic acid (ClCH2COOH)
(3*) º of NaCl (4) º of CH3COOK
Ans. (3)
Sol. According to Kohlrausch's law the molar conductivity at infinite diluation (o) for weak electrolyte CH3COOH is
oCH COOH = oCH COONa + oHCI – o NaCI
3 3
So for calculating the value of oCH COOH , value of oNaCI should also be known.
3

Q.17 The cell Zn | Zn2+(1M) || Cu2+(1M) | Cu : (E°cell = 1.10V) was allowed to completely discharge at 298 K. The relative

 Zn2  
    1 .1
concentration of Zn2+ to Cu2+   is : (Take = 18.65) [AIEEE–2007]
2 
 Cu   0.059
   

(1*) 1037.3 (2) 9.65 × 104 (3) antilog (24.08) (4) 37.3
Ans. (1)

0.0591 [ Zn2  ] [ Zn2  ] [ Zn2  ]

Sol. 0 = + 1.1 – log ; log = 37.3. ; = 1037.3
2 [Cu2  ] [Cu2  ] [Cu2  ]

0 0
Q.18 Given : ECr 3  / Cr = – 0.72, EFe2 / Fe = – 0.42 V

2.303 R ( 298 )
The potential for the cell Cr | Cr3+(0.1 M) || Fe2+(0.01 M) | Fe at 298 K is : (Take = 0.06) [AIEEE–2008]
F
(1) 0.339 V (2) – 0.339 V (3) – 0.26 V (4*) 0.26 V
Ans. (4)

0.059 [Cr 3 ]2
Sol. Ecell = E0cell – log
6 [Fe  2 ]3

0.056 (0.1)2
= 0.3 – log = 0.3 – 0.04 = 0.26 V
6 (0.01)3

0 0
Q.19 Given : EFe3  / Fe = – 0.036 V, EFe2  / Fe = – 0.439 V

3 2
The value of standard electrode potential for the change, Fe(aq) + e–  Fe(aq) will be :
(1)0.385V (2*) 0.770V (3) –0.270V (4) –0.072V
Ans. (2)
0
Sol. Fe3+ + 3e–  Fe G1 = –3 × F × EFe3  / Fe

0
Fe2+  Fe G2 = –2 × F × EFe 2  / Fe

Fe3+ + e–  Fe2+ G = G1 – G2

G = 3 × 0.036F – 2 × 0.439 × F = – 1 × E0 (Fe3+/Fe+2) × F
E0 (Fe3+/Fe+2) = 2 × 0.439 – 3 × 0.036
= 0.878 – 0.108 = 0.770 V
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 Electrochemistry

Q.20 The Gibbs energy for the decomposition of Al2O3 at 500ºC is as follows : [AIEEE–2010]
2 4
Al2O3  Al + O2 ; rG = + 966 kJmol–1. The potential difference needed for electrolytic reduction of Al2O3 at 500ºC is
3 3
at least :
(1) 4.5 V (2) 3.0 V (3*) 2.5 V (4) 5.0 V
Ans. (3)
2 4
Sol. Al O  Al + O2
3 2 3 3
rG = +966 kJ mol–1 = 966 × 103 J mol–1
G = – nFEcell
966 × 103 = – 4 × 96500 × Ecell
Ecell = 2.5 V

Q.21 The reduction potential of hydrogen half-cell will be negative, if : [AIEEE–2011]

(1) p(H2) = 1 atm and [H+] = 2.0 M (2) p(H2) = 1 atm and [H+] = 1.0 M
+
(3*) p(H2) = 2 atm and [H ] = 1.0 M (4) p(H2) = 2 atm and [H+] = 2.0 M
Ans. (3)
Sol. 2H+ (aq) + 2e–  H2 (g)

0.0591 PH2 0.0591 2 0.0591

Ered = Eºred – log  2 ; Ered = 0 – log 2 ; Ered = – log2
n (H ) 2 (1) 2

 Ered is forund to be negative for (3) option.

Q.22 The standard reduction potentials for Zn2+/Zn, Ni2+/Ni and Fe2+/Fe are –0.76, – 0.23 and –0.44 V respectively. The reaction
X + Y2+  X2+ + Y will be spontaneous, when : [AIEEE 2012]
(1) X = Ni, Y = Fe (2) X = Ni, Y = Zn (3) X= Fe, Y = Zn (4*) X= Zn, Y = Ni
Ans. (4)
Sol. X + Y2+  X2+ + Y
For reaction to be spontaneous Eº must be positive.
EºZn / Zn+2 + EºNi2+ / Ni = 0.76 + (– 0.23) = + 0.53 (positive

0 0
Q.23 Given : E Cr 3 / Cr = –0.74 V ; EMnO  / Mn2  = 1.51 V
4

E0 0
= 1.33 V ; E Cl / Cl = 1.36 V
Cr2O72  / Cr 3 

Based on the data given above, strongest oxidising agent will be : [JEE(Main) 2013]
(1) Cl (2) Cr3+ (3) Mn2+ (4*) MnO4–
Ans. (4)
Sol. Higher the SRP, better is oxidising agent
Hence MnO4- is strongest oxidising agent

Q.24 Resistance of 0.2 M solution of an electrolyte is 50 . The specific conductance of the solution is 1.4 S m–1. The resistance
of 0.5 M solution of the same electrolyte is 280 . The molar conductivity of 0.5 M solution of the electrolyte in S m2 mol–
1 is : [JEE(Main) 2014]
(1*) 5  10 –4 (2) 5  10–3 (3) 5  10 3 (4) 5  10 2

Ans. (1)
Sol. x = 1.4 S/m.
R = 50 
M = 0.2
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Electrochemistry

1 
K= ×
R A


 = 1.4 × 50 m–1.
A
Now, new soltuion has M = 0.5, R = 280 

1  1 1
K= × = 1.4  50 
R A 280 4

1
K 1
 M =  4   5 10  4
1000  M 1000  0.5 2000

Q.25 The equivalent conductance of NaCl at concentration C and at infinite dilution are C and , respectively. The correct
relationship between C and  is given as : (where the constant B is positive) [JEE(Main) 2014]
(1) C =  + (2)C (2) C =  – (2)C (3*) C =  – (2) C (4) C =  + (2) C
Ans. (3)
Sol.  c     B C (Debye Huckel onsagn equation)

Q.26 The metal that cannot be obtained by electrolysis of an aqueous solution of its salts is : [JEE(Main) 2014]
(1) Ag (2*) Ca (3) Cu (4) Cr
Ans. (2)
Sol. Reason : Higher the position of element in the electrochemical series, more difficult is the reduction of its cations.
If Ca2+ (aq) is electrolysed, water is reduced in preference to it. Hence it cannot be reduced electrolytically from an
aqueous solutions.

Q.27 Given below are the half-cell reactions : [JEE(Main) 2014]

Mn2+ + 2e¯ Mn ; Eº = –1.18 V
2(Mn3+ + e¯  Mn2+) ; Eº = +1.51 V
The Eº for 3Mn2+  Mn + 2Mn3+ will be :
(1*) –2.69 V ; the reaction will not occur (2) –2.69 V ; the reaction will occur
(3) –0.33 V ; the reaction will not occur (4) –0.33 V ; the reaction will occur
Ans. (1)
E1 1.51V
0
E  1.18 V
0
Mn 2 
2+
Sol.   Mn 2   Mn
 for Mn2+ disproportionation, E0 = – 1.51 V –1.18 V = – 2.69 V < 0
Reaction is non-spontaneous.
E1 1.51V
0
E  1.18 V
0
Mn 2 
2+
  Mn 2   Mn

Q.28 Two Faraday of electricity is passed through a solution of CuSO4. The mass of copper deposited at the cathode is : (at.
mass of Cu = 63.5 amu) [JEE(Main) 2015]
(1) 0 g (2*) 63.5 g (3) 2 g (4) 127 g
Ans. (2)

Sol. Cu2+ + 2e–  Cu

2F 1 mole
= 63.5 g.

Q.29 Galvanization is applying a coating of : [JEE(Main) 2016]

(1) Cr (2) Cu (3*) Zn (4) Pb

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 Electrochemistry

Ans. (3)
Sol. Galvanization is applying a coating of Zn.

Q.30 Given [JEE Main - 2017]

ECl 

= 1.36 V, E Cr3 /Cr = – 0.74 V
2 /Cl

ECr 2 3

= 1.33V, E MnO4 /Mn 2 = 1.51 V
2 O7 /Cr

Among the following, the strongest reducing agent is:

(1) Cr (2) Mn2+ (3) Cr3+ (4) Cl–
Ans. (1)

Sol. EMnO /Mn 2 = 1.51 V ....(i)

4

ECl  = 1.36 V .....(ii)

2 /Cl

ECr 2 3 = 1.33V ......(iii)

2 O7 /Cr

E Cr3 /Cr = – 0.74 V ....(iv)

Since Cr3+ is having least reducing potential, so Cr is the best reducing agent.

Q.31 How long (approximate) should water be electrolysed by passing through 100 amperes current so that the oxygen released
can completely burn 27.66 g of diborane ? (Atomic weight of B = 10.8 u) [JEE Main-2018]
(1) 0.8 hours (2) 3.2 hours (3) 1.6 hours (4) 6.4 hours
Ans. (2)
Sol. B2H6 + 3O2  B2O3 + 3H2O
27.6
moles of O2 required = 3x moles of B2H6 = 3 × =3
27.6

I t
= moles of O2 × 4
96500

100  t
=3×4
96500

3  4  96500
t=  3.2 hours
100

105