EXERCISE # 1

is in a cell in which the electrodes are 5 cm apart and to

Q.1 In a conductivity cell the two platinum which a potential of 2 volts is applied. -
electrodes, each of area 10 sq. cm are fixed 1.5 cm (A) 3.62 × 10–3 cm2 volt–1 sec–1, 1.45 × 10–3 cm sec–1
apart. The cell contained 0.05 N solution of a salt. If the
(B) 5.2 × 10–4 cm2 volt–1 sec–1, 2.08 × 10–4 cm sec–1
two electrodes are just half dipped into the solution
(C) 3.2 × 10–4 cm2 volt–1 sec–1 , 1.05 × 10–3 cm sec–1
which has a resistance of 50Ω, find equivalent
conductance of the salt solution – (D) None of these
(A) 120 S cm2 eq–1 (B) 160 S cm2 eq–1 Sol.[A] Velocity = = 1.43 × 10–3cm/sec.
(C) 120 S m2 eq–1 (D) 125 S cm2 eq–1
Sol.[A] 50 = × × ⇒ 120 S cm2 eq–1 Mobility = 1.43 × 10–3 × = 3.6 × 10–3

Q.2 The resistance of a N/10 KCl solution is 245

Ω. Calculate the equivalent conductance of the solution Q.6 The equivalent conductance of an infinitely
if the electrodes in the cell are 4 cm apart and each dilute solution of NH4Cl is 150 and the ionic
having an area of 7.0 sq. cm - conductance of OH– and Cl– ions are 198 and 76
(A) 23.32 S cm2 eq–1 (B) 23.23 S m2 eq–1 respectively . If the equivalent conductance of a 0.01 N
(C) 2.332 S cm2 eq–1 (D) None of these solution of NH4OH is 9.6, What will be its degree of
Sol.[A] 245 = × × ⇒ Λeq = 23.32 dissociation ?
(A) 0.0353 (B) 0.0103
Q.3 The resistance of a solution 'A' is 50 Ω and that (C) 0.96 (D) 0.414
of solution 'B' is 100 Ω, both solutions being taken in Sol.[A] = 150 – 76 + 198 = 272
the same conductivity cell. If equal volumes of solution
A & B are mixed, what will be the resistance of the α= = 0.0353
mixture using the same cell. (Assume that there is no
increase in the degree of dissociation of A & B on Q.7 The specific conductivity of a saturated
mixing) - solution of AgCl is 3.40 × 10–6 ohm–1 cm–1 at 25ºC. If
(A) 60 Ω (B) 6.67 Ω = 62.3 ohm–1 cm2 mol–1 & λCl– = 67.7 ohm–1 cm2
(C) 66.67 Ω (D) 50 Ω
Sol.[C] conc. of both solution are halved mol–1 , the solubility of AgCl at 25ºC is -
∴ R1 = 100 Ω & R2 = 200 Ω (A) 2.6 × 10–5 mol L–1
∴ = + ⇒ R = 66.67 (B) 3.731 × 10–3 mol L–1
(C) 3.731 × 10–5 moL–1
(D) 2.6 × 10–3 gL–1
Q.4 Calculate molar conductivity at infinite Sol.[A] λsec = 62.3 + 67.7 = 130 ohm–1 cm2 mol–1
dilution of CH3COOH if molar conductivity at infinite S= mol/cm3 = 2.6 × 10–5 mol/lt
dilution of CH3COONa, HCl and NaCl are 91.6, 425.0
and 128.1 S cm2 mol–1 -
(A) 390.5 S cm2 mol–1 (B) 388.5 S cm2 mol–1 Q.8 Molar conductance of 0.1 M acetic acid is 7
(C) 490.5 S cm2 mol–1 (D) None of these ohm cm2 mol–1 . If the molar conductance of acetic
–1

acid at infinite dilution is 380.8 ohm–1 cm2 mol–1, the

Sol.[B] = – value of dissociation constant will be -
(A) 226 × 10–5 mol dm–3
= 91.6 + 425 – 128.1 = 388.5 (B) 1.66 × 10–3 mol dm–1
(C) 1.66 × 10–2 mol dm–3
Q.5 For H+ the value of λ∞ = 349.8 S cm2 eq–1 . (D) 3.442 × 10–5 mol dm–3
Calculate the mobilities of H+ ion and it's velocity if it Sol.[D] α = = 0.018
Ka = Cα2 ⇒ Ka = 0.1 × (0.018)2 = 3.38 × 10–5 Q.13 Which of the following statements about the
spontaneous reaction occuring in a galvanic cell is
Q.9 If is x1, is x2 then always true ?
(A) E0cell > 0, ΔGº < 0, and Q < K
will be :
(B) E0cell > 0, ΔGº > 0, and Q < K
(A) 3x2 – 2x1 (B) x2 – x1
(C) E0cell > 0, ΔGº > 0, and Q > K
(C) x2 + x1 (D) 2x1 + 3x2
(D) Ecell > 0, ΔG < 0, and Q > K
Sol.[A]
Sol.[A] Fact
—→ x1
—→ x1 × 2 …(i)
—→ x2 × 3 …(ii) Q.14 The standard reduction potentials at 298 K for
the following half-reactions are given against each.
⎯→?
Zn2+ (aq) + 2e= Zn (s) ; – 0.762
From equation (i) and (ii) Cr3+ (aq) + 3e= Cr (s) ; – 0.74 V
= –2x1 + 3x2 2H+ + 2e= H2 (g) ; ± 0.0 V
= 3x2 – 2x1 Fe3+ (aq) + e= Fe2+ (aq); + 0.77 V
Which is the strongest oxidising agent ?
Q.10 The EMF of the cell Ni | Ni2+ || Cu2+ | Cu(s) is (A) Zn (s) (B) Cr (s)
0.59 volt. The standard reduction (C) H2 (g) (D) Fe3+ (aq)
electrode potential of copper electrode is 0.34 volt. The Sol.[D] higher E°raduction means good oxidizing agent
standard reduction electrode
potential of nickel electrode will be Q.15 The standard oxidation potentials of Zn and
(A) 0.25 volt (B) – 0.25 volt Ag is water at 25ºC are,
(C) – 0.50 volt (D) – 0.025 volt Zn(s)⎯ → Zn2+ + 2e
Sol.[B] –x = 0.59 [Eº = 0.76 V]
x = 0.3.4 – 0.59 = –0.25 Ag(s)⎯ → Ag+ + e
Eº = – 0.80 V
Q.11 ΔGº of the cell reaction Which reaction actually takes place :
AgCl (s) + H2 (g) (A) Zn(s) + 2Ag+ (aq) ⎯ → Zn2+ + 2Ag(s)
(B) Zn2+ + 2Ag+ (s) ⎯ ⎯ → 2Ag+ (aq) + Zn(s)
= Ag (s) + H+ + Cl– is – 21.52 kJ. (C) Zn(s) + 2Ag(s) ⎯ ⎯ → Zn2+ (aq) + Ag+ (s)
ΔGº of 2AgCl (s) + H2 (g) (D) Zn2+ (aq) + Ag+ (aq) ⎯ ⎯ → Zn(s) + Ag(s)
= 2Ag (s) + 2H+ + 2Cl– is
(A) – 21.52 kJ (B) – 10.76 kJ Sol.[A] Zn(s) + 2Ag + → 2Ag + Zn2+
(C) – 43.04 kJ (D) 43.04 kJ E° = 0.76 + 0.8 = 1.56 V
Sol.[C] =
Q.16 Given that Eº values of Ag+/Ag, K+/K,
∴ ΔG = –n F E0 = –RT n KC
Mg+2/Mg and Cr+3/Cr are 0.80V, – 2.93V, – 2.37V, and
∴ ΔG2 = 2 × (–21.52) = –43.04 KJ – 0.74 V, respectively. Which of the following orders
regarding the reducing power of metal is correct ?
Q.12 The standard EMF of a Daniell cell is 1.10
(A) Ag > Cr > Mg > K
volt. The maximum electrical work obtained from the
(B) Ag < Cr < Mg < K
Daniell cell is
(C) Ag > Cr > K > Mg
(A) 212.3 kJ (B) 175.4
(D) Cr > Ag > Mg > K
kJ
Sol. [B]
(C) 106.15 kJ (D) 53.07 kJ
Greater the standard reduction potential, greater
Sol.[A] 1.1 × 96500 × 2 = 212.30 kJ
tendency to reducing power of metal. K has greater
value(–2.93) so K > Mg > Cr > Ag
Q.17 1/2 H2(g) + AgCl(s) = H+(aq) + Cl–(aq) + – RT = log
Ag(s) occurs in the galvanic cell :
(A) Ag/AgCl(s) | KCl(sol) | | AgNO3 (s) | Ag
(B) Pt/H2(g) | HCl (sol) | | AgNO3 (s) | Ag
(C) Pt/H2(g) | HCl (sol) | | Cl– |AgCl(s) | Ag
(D) Pt/H2(g) | KCl (sol) | | AgCl(s) | Ag P 2 > P1
Sol.[C] Fact
Q.22 If the solution of the CuSO4 in which copper
Q.18 Which of the following is not a function of salt rod is immersed is diluted to 10 times, the oxidation
bridge - electrode potential
(A) To maintain electrical neutrality of the solution (A) increase by 0.030 volt
(B) To complete the circuit so that current can flow (B) decrease by 0.030 volt
(C) To prevent voltage drop & to minimize liquid- (C) increase by 0.059 volt
liquid junction potential (D) decrease by 0.0059 volt
(D) To increase liquid-liquid junction potential Sol. [A]
Sol.[D] Fact Ecell = – log

Q.19 The hydrogen electrode is dipped in a = 0.34 – log

solution of pH 3 at 25ºC. The reduction potential of the
electrode would be (the value of is 0.059 = 0.34 – 0.03 log [10–1]
= 0.34 + 0.03 log10 10
V): = 0.34 + 0.03
(A) 0.177 V (B) – 0.177 V So increase by 0.03 Volt
(C) 0.087 V (D) 0.059 V Q.23 At pH = 2,
Sol.[B] Ered = + log EQuinhydrone will be(EºQuinhydrone = 1.30 V)-
+ 2H+ + 2e–

=0+ log [10–3]

= 0.059 × –3 × 1
= – 0.177 V
(A) 1.36 V (B) 1.30 V
Q.20 The half cell reduction potential of a (C) 1.42 V (D) 1.20 V
hydrogen electrode at pH = 10 will be Sol. [C]
(A) 0.59 V (B) – 0.59 V E = Eº – log [H+]
(C) 0.059 V (D) – 0.059
Sol. [B] = 1.30 – log (10–2)2
Ered = + log [Mn+]
= 1.30 – log 10–4
=0+ log [10–10]
= 1.30 + 4 × × 1 = 1.42
= + 0.0591 × –10 = – 0.59 V

Q.21 Pt | Cl2 (P1) | HCl (0.1 M) | Pt | Cl2 (P2) ; cell

reaction will be spontaneous if : Q.24 Which graph correctly correlates Ecell as a
(A) P1 = P2 (B) P1 > P2 function of concentrations for the cell
(for different values of M and M´) :
(C) P2 > P1 (D) P1 = P2 = 1 atm
Zn(s) + Cu2+ (M)⎯ → Zn2+ (M´) + Cu(s)
Sol. [C]
ΔG = –2.303 RT log K Eºcell = 1.10 V
for spontaneous ΔG = –ve
X-axis : log10 , Y – axis : Ecell

(A)

as we decrease log10 value decrease. Ecell value

(B)
and vice – versa.

Q.25 The reduction potential of hydrogen electrode

is – 118 mV. The concentration of H+ in the solution
is
(C) (A) 0.01 M (B) 2 M
(C) 10–4 M (D) 1 M
Sol.[A]
ECell = log[H+]

– 0.118 = log[H+]
(D)
= – log[H+] ⇒ pH = 0.01 M

Q.26 The temperature coefficient, of the emf i.e.

Sol.[B] = – 0.00065 volt. deg–1 for the cell Cd | CdCl2(1M)
Zn(s) + Cu+2(M) ⎯ → Zn+2 (M) + Cu(s)
Ecell = – log10 | AgCl(s) | Ag at 25ºC. Calculate the entropy changes
ΔS298K for the cell reaction,
–
Cd + 2AgCl → Cd + 2Cl + 2Ag -
++

graph will be straight line i.e. (A) – 105.5 JK–1 (B) – 150.2 JK–1
y = mx + C (C) – 75.7 JK–1 (D) – 125.5 JK–1
y = ECell Sol.[D] ΔS = 2 × 96500 × (–0.00065) = –125.5 J/K
x = log10
Q.27 The standard emf of the cell, Cd (s) | CdCl2(aq)
| | AgCl(s) | Ag(s) in which the cell reaction is,
Cd(s)+2AgCl(s) → 2Ag(s) + Cd+2(aq)+2Cl–(aq) is
0.6915 V at 0ºC and 0.6753 V at 25º C. The ΔH of the
reaction at 25ºC is -
(A) – 176 kJ (B) – 234.7 kJ
(C) + 123.5 kJ (D) – 167.26 kJ
Sol.[D] ΔH = –nFE + nFT E=

W= × 2.5 × 625 = 0.514 g

= – 2 × 96500 × 0.6753 + 2 × 96500 × 298
= –167.6 KJ
Q.31 In acidic medium , MnO4– is converted to Mn+2
when acts as an oxidizing agent. The quantity of
electricity required to reduce 0.05 mol of MnO4– would
Q.28 The potential of the Daniell cell, be
Zn Cu was reported by Buckbee, (A) 0.01F (B) 0.05F
(C) 0.25 F (D) 0.15 F
Surdzial, and Metz as Eº = 1.1028 – 0.641 × 10–3 T + Sol.[C]
MnO4– + 8H+ + 5e– → Mn+2 + 4H2O
0.72 × 10–5 T2, where T is the celcius temperature.
1 mol 5 mole
Calculate ΔSº for the cell reaction at 25º C -
1 mole MnO4 required = 5 mole e–
–
(A) – 45.32 (B) – 34.52 so 0.05 MnO4– required = 5 × 0.05
(C) – 25.43 (D) – 54.23 = 0.25
–
Sol.[D] = –0.647 × 10 + 2 × 0.72 × 10–5 T
–3 1 mole e required = 1 F
So 0.25 required = 0.25 × F
= 0.25 F
ΔS = 2 × 96500 × [–0.647 × 10–3]
+ 2 × 0.72 × 10–5 × 250] Q.32 The current of 9.65 A is passed for 3hrs
= –55.39 between nickel electrods in 0.5L of a 2 × 10–3 M
solution of Ni(NO3)2, the molarity of solution after
electrolysis would be
Q.29 In electrolysis of an aqueous solution of (A) 0.46 M (B) 0.625 M
sodium sulphate, 2.4L of oxygen at STP was liberated (C) 2× 10–3 M (D) 1.25 M
at anode. The volume of hydrogen at STP liberated at Sol.[C]
cathode would be Ni+2 + 2e– → Ni
(A) 1.2L (B) 2.4L 1 mole 2 × 96500C
(C) 2.6L (D) 4.8L Quantity of electric charge passed
Sol.[D] = 3.7 × 6 × 60 × 60 coulomb
at cathode at anode = 79920 Coulomb
Na+ + e– ⎯ → NaH2 ⎯ → 2H+ + 2e– No. of moles of Ni(NO3)2 decomposed or nickel
So 1 mole has 2.4 deposited
So 2 mole has = 2.4 × 2 = × 79920 = 0.4140
= 4.8
Q.30 A current of strength 2.5amp was passed No. of moles of Ni(NO3)2 present before electrolysis
through CuSO4 solution for 6 minute 265 seconds. The = 0.5 × 2 = 1.0
amount of copper deposited is No. of moles of Ni(NO3)2 present after electrolysis
(At wt. of Cu = 63.5); 1 faraday = 96500 coulombs = (1.0 – 0.4140) = 0.586
(A) 0.3175 g (B) 1.028 g Since. 0.586 moles are present in 0.5 litre.
(C) 0.514 g (D) 6.35 g molarity of the solution = 2 × 0.586
Sol.[C] = 1.72 M
W = ZIt when nickel electrodes are used, anodic nickel will
= ×I×t dissolve and get deposited at the cathode. The molarity
of the solution will thus remain unaffected.
= t = 6 minute + 265 sec
= 360 + 265 = 625 sec Q.33 When electricity is passed through a solution
I = 2.5 Amp of AlCl3, 13.5 g of Al is discharged. The amount of
charge passed is ( Al = 27)
(A) 1.5 F (B) 0.5 F Loss weight of Zn = ×I×t
(C) 1.0F (D) 2.0F
Sol.[A] = ×
Al+3 + 3e– ⎯ → Al
27 g
= 11.77 g
1 mole 3 mole
1/2 3/2 = 1.5 F gain of weight of Cu = ×I×t

Q.34 A current of 0.75A is passed through an acidic = × 9.65 × 60 × 60

solution of CuSO4 for 10 minutes. The volume of
oxygen liberated at anode (at STP) will be
= 11.43 g
(A) 0.261 dm3
(11.43g, 11.77)
(B) 0.261 cm3
(C) 0.261 x 102 mL 2X– + Y2 → 2Y– + X2
(D) 0.261 m3 X– greater tendency to accept electrons i.e. it's oxidising
Sol.[C] 2O2– ⎯ → O2 + 4e agent, W– not reduce to Y so reaction no possible but
mole of e = Z– reduce to X2 i.e. it's oxidising agent. So Conclusion
will be that Z– greater oxidisng agent
> > >
mole of O2 = = 0.0261 

Q.35 In an electrolysis of a metallic chloride Q.37 A solution of copper (II) sulphate can be stored
MClx 3.283 g of the metal (atomic mass 197g/mol) was in iron vessel.
deposited on the cathode by the passage of 4825C of Sol. Due to higher standard reduction potential of
electronic charge. The number of chloride ions in Fe. So copper sulphate can not be stored in iron vessel.
molecule is -
(A) 0.5 (B) 1.0 Q.38 Copper metal cannot reduce iron (II) ions in
(C) 2.0 (D) 3.0 acidic solutions.
Sol. [D] Sol. Yes, Fe his high standard reduction potential.
W = ZQ
W= ×Q Q.39 The amount of the product formed by the
passage of 1 coulomb of electricity through electrolyte
Q = 4825 C is called electrochemical
W = 3.283 g , Molecular mass of metal = 197 equivalent of the substance.
E= = = 65.66 Sol. w∝ Q
w = ZQ
E = equivalent weight of metal w = ZIt
E= = = 3.0 Z = Electro chemical equivalent of the substance.

Q.40 In galvanic cell, the cathode is a – ve

SO3 Chloride ions.
terminal of the cell.
Sol. In galvanic cell cathode → +ve terminal
Q.36 A current of 9.65 A is drawn from a daniell cell
for exactly 1hr. If molar masses of Cu and Zn are 63.5 Anode → –ve terminal
g/mol and 65.4 g/mol respectively, the loss in mass at
anode and gain in mass at cathode, respectively, are Q.41 In SHE the pressure of H2 gas should be 10 atm
(A) 11.43 g, 11.77g(B) 11.77g, 11.43g and pH of solution should be zero.
(C) 22.86g, 23.4 g(D) 23.54, 22.86g Sol. In SHE
Sol.[B]
Ecell = log Q.43 During electrolysis of aqueous solution of
CuSO4 using Pt electrodes the product at anode is
..........
Pressure can be low at 1 atm but pH of solution should
Sol. O2
not be zero otherwise Ecell = 0 will be it's False.
Q.44 The quantity of electricity required for
complete reduction of 0.5 mole of MnO4– to Mn2+ is
......... C.
Sol. 0.5 × 5 × 96500 C
Q.42 Lead is able to displace silver from AgNO3
solution because its standard oxidation
potential is ........ than that of silver.
Sol. Higher
 EXERCISE # 2
potential is measured against normal calomel electrode
at 25ºC. This experiment is then repeated with a
saturated solution of AgI. If the difference in potential
Q.1 The following facts are available
in the two cases is 0.177V. What is the ratio of
2X– + Y2⎯ → 2Y– + X2 solubilities of AgCl and AgI at the temperature of the
2W– +Y2⎯ → No reaction experiment ?
2Z– + X2⎯ → 2X– + Z2 (A) 103 (B) 106 (C) 102 (D) 104
Which of the following statements is correct? Sol.[A] =
(A)
= 988 ≈ 103

(B) Q.5 MnO4– + 8H+ + 5e– → Mn2+ + 4H2O

If H concentration is decreased from 1 M to 10–4 M at
+
(C)
25ºC,
(A) the potential decreases by 0.38 V with decreases in
oxidising power
(D) (B) the potential increases by 0.38 V with increase in
oxidising power
Sol.[B] 2X– + Y2 → 2Y– + X2 ⇒ >
(C) the potential decreases by 0.25 V with decreases in
2Z– + X2 → 2X– + Z2 ⇒ > oxidising power
(D) the potential decreases by 0.38 V without affecting
2W– + Y2 → no reaction ⇒ > oxidising power
Sol.[A] ΔE = [10–4]8 = –0.378V
Q.2 The cell Pt(H2) (1 atm) | H+ (pH = ?), I– (a = 1)
| AgI(s), Ag has emf, E298K = 0. The standard electrode
potential of the reaction Q.6 ΔG = ΔH – TΔS and ΔG = ΔH + T
AgI + e– → Ag + I– is – 0.151 Volt. Calculate the pH
value - then is -
(A) 3.37 (B) 5.26 (C) 2.56 (D) 4.62
Sol.[C] 0.151 = pH (A) (B)

pH = 2.56 (C) – nFEcell (D) + nEFcell

Sol.[A] Fact

Q.3 Using the information in the preceding

Q.7 Three moles of electrons are passed through
problem, calculate the solubility products of AgI in three solution in succession containing AgNO3, CuSO4
water at 25ºC [ = + 0.799 Volt] - and AuCl3, respectively. The molar ratio of amounts of
cations reduced at cathode will be -
(A) 1.97 × 10–17 (B) 7.91 × 10–17 (A) 1 : 2 : 3 (B) 2 : 1 : 3
–17
(C) 1.79 × 10 (D) 9.17 × 10–17 (C) 3 : 2 : 1 (D) 6 : 3 : 2
Sol.[B] AgI + e → Ag + I– E° = –0.151 Sol.[D] For same charge Ag : Cu : Au
Ag ⎯ → Ag + e E° = –0.799
+ = 1 : . = 6: 3: 2

AgI ⎯ → Ag+ + I– Q.8 In H2 – O2 fuel cell the reaction occuring at

E° = –0.95 + 96500 × 0.95 = – RT × 2.303 log K cathode is -
K = 8.4 × 10–17 (A) 2H2O + O2 + 4e– → 4OH–
Q.4 Pure water is saturated with pure solid AgCl, a
(B) 2H2 + O2 → 2H2O()
silver electrode is placed in the solution and the
(C) H+ + OH– → H2O
(D) H+ + e– → H2 ηcurrent = × 100

Sol.[A] Fact = 95.1%

Q.12 During the preparation of H2S2O8 (per

Q.9 The standard reduction potentials Eº of the disulphuric acid) O2 gas also releases at anode as
following systems are
byproduct, When 9.72 L of H2 releases at cathode and
System Eº(Volts)
2.35 L O2 at anode, the weight H2S2O8 produced in
(i) MnO4– + 8H+ + 5e → Mn2+ + 4H2O 1.51
gram is -
(ii) Sn + 2e → Sn
4+ 2+
0.15
(A) 87.12 (B) 43.56
(iii) Cr2O7 + 14H + 6e → 2Cr + 7H2O 1.33
2– + 3+
(C) 83.42 (D) 51.74
(iv) Ce4+ + e → Ce3+ 1.61
The oxidising power of the various species decreases in Sol.[B] ⎯ → H2S2O8 + 2e
the order – 2O2– ⎯ → O2 + 4e
(A) Ce4+ > Cr2O72– > Sn4+ > MnO4– = 0.105 0.42 mole
(B) Ce4+ > MnO4– > Cr2O72– > Sn4+
(C) Cr2O72– > Sn4+ > Ce4+ > MnO4–
2H+ + 2e ⎯ → H2
(D) MnO4– > Ce4+ > Sn4+ > Cr2O72–
0.87 mole mole
Sol.[B] As per data

Q.10 A hydrogen electrode placed in a buffer
solution of CH3COONa and CH3COOH in the ratios of
x : y and y : x has electrode potential values E1 volts
and E2 volts, respectively at 25º C. The pKa values of
acetic acid is (E1 and E2 are oxidation potentials) -
(A) (B)
(C) – (D)
Sol.[A] –n FE1 = 2.303 RT log Ka + 2.303 RT log
–n F E2 = –2.303 RT log Ka + 2.303 RT log
– log Ka =
pKa = = (A)
mole of e for H2S2O8 = 0.87 – 0.42 = 0.45 mole
∴ mole of H2S2O8 = 0.225 mole ≡ 43.65 gm
Q.13 Saturated solution of KNO3 is used to make
'salt bridge' because -
(A) Velocity of K+ is greater than that of NO3–
(B) Velocity of NO3– is greater than that of K+
(C) Velocities of both K+ and NO3– are nearly
the same
(D) KNO3 is highly soluble in water
Sol.[C] Velocity almost same, so conductivity in
cathodic and anodic compartments is not effected.
Q.14 Conductance measurements can be used to
detect the end point of acid-base titrations. Which of
the following plots correctly represent the end point of
the titration of strong acid and strong base ?
(B)

Q.11 Electrolysis of a solution MnSO4 in aqueous

sulphuric acid is a method for the preparation of MnO2.
Passing a current of 27 A for 24 hours gives 1 kg of
MnO2. The current efficiency is -
(A) 100% (B) 95.185%
(C) 80% (D) 82.951%
Sol.[B] Mn → Mn4+ + 2e
2+

mole of MnO2 produced = = 11.49 mole

Q used = 11.49 × 2 × 96500 C

(C) (D) ⇒ moles is same
Cu2+ Ag+ Hg2+ Mg
moles 1 1 1 1
v.f 2 1 2 2
greater value R.P. ⇒ greater is its tendency to get
reduced.
Sol.[A] Fact On increasing voltage hot metal gets easily deposited
Q.15 The density of Cu is 8.94 g cm–3. The quantity having higher R.P
of electricity needed to plate an area Ag > Hg > Cu
10cm × 10 cm to a thickness of 10–2 cm using CuSO4 Mg → cannot deposited because its R.P. is –ve
solution would be ∴ It will oxidize easily and H2O will reduce
(A) 13586 C (B) 27172 C
Q.18 If the pressure of H2 gas is increased from
(C) 40758 C (D) 20348 C
1 atm to 100 atm keeping H+ concentration constant at
Sol.[B] (a × b × c) × ρ =
1 M, the change in reduction potential of hydrogen half
(10 × 10 × 10–2) × (8.94) = × cell at 25°C will be
(A) 0.059 V (B) 0.59 V
(It) = 27172 C (C) 0.0295 V (D) 0.118 V
Sol.[A] Ecell = – log(pressure) P
Q.16 During electrolysis of an aqueous solution of
sodium sulphate, 2.4 L of oxygen at STP was liberated
H2⎯ → 2H+ + 2e–
at anode. The volume of hydrogen at STP, liberated at
(P)
cathode would be
Ecell = + logP {as conc [H+] = 1}
(A) 1.2 L (B) 2.4 L
(C) 2.6 L (D) 4.8 L
Sol.[D] Na2SO4(eq) ⎯ → electrolysis I Ecell = log1 = 0
reduction of H2O oxidation of H2O
no. of equiv at anode = cathode II Ecell = log102 = 0.0591
=
E = 0.0591
=

4.8L = V Q.19 Consider the following Galvanic cell

Q.17 An aqueous solution containing one mole per

litre each of Cu(NO3)2 , AgNO3, Hg2(NO3)2, Mg(NO3)2
is being electrolysed by using inert electrodes. The
value of standard potentials are
,

and

With increasing voltage, the sequence of deposition of

By what value the cell voltage change when
metals on the cathode will be concentration of ions in anodic and cathodic
(A) Ag, Hg, Cu, Mg (B) Mg, Cu, Hg, Ag compartments both increased by factor of 10 at 298 K
(C) Ag, Hg, Cu (D) Cu, Hg, Ag (A) +0.0591 (B) –0.0591
(C) –0.1182 (D) 0
Sol.[C] conc is same = 1 m
Sol.[C] H2 ⎯ → 2H+ + 2e– (C) (D)
Cl2 + 2e– ⎯ → 2Cl–
H2 + Cl2 ⎯ → 2H+ + 2Cl– Sol.[C] λm = =
Let initial conc . [H+] = [Cl–] = 1
I. Ecell = – log 1 ⇒ Ecell =
 ρ = x ∴ λm =
+ –
Now, cone. [H ] = [Cl ] = 10
II. Ecell = – × 4 log 10
m=y
Ecell = – 0.1182
ΔE = ( )II – (Ecell)I = – 0.0591

Q.20 For the fuel cell reaction Q.23 In an electrolytic cell 1 L of 0.1 M aqueous
2H2(g) + O2(g) ⎯ → 2H2O(l); solution of MnO42– is converted to MnO4– at the
cathode. What is correct about the
ΔfH°298 (H2O, l) = –285.5 kJ/mol
statement ?
What is ΔS°298 for given fuel cell reaction ?
(A) The above process occurs at the anode
Given : O2(g) + 4H + (aq) + 4e– ⎯ → 2H2O(l) (B) Oxidation number of Mn changes from
(A) –0.322 J/K (B) –0.635 kJ/K + 6 to + 7
(C) 3.51 kJ/K (D) –0.322 kJ/K (C) Oxidation number of Mn changes from
Sol.[D] Given E° = – 0.5 V, ΔH = – 285.5 kJ/K + 7 to + 6
T = 298 K (D) The entire process requires the passage of 9650 C
ΔG = ΔH – TΔS of electricity.
ΔS = Sol. [A,B,D]
This process occurs at the anode
(H2O + H2 ⎯ → H2O + 2H+ + 2e–)
4e– + 4H+ + O2 ⎯ → 2H2O Mn+6 ⎯ → M+7 + e–
2H2 + O2 ⎯ → 2H2O (n = 4) This entire process require the passage of 1 Faraday
= – 285.5 kJ/mol–1
electricity
ΔG0 = – 4 × 96500 × 0.5
ΔS° =
Q.24 Choose the correct statement(s) -
(A) At the anode, the species having minimum
Q.21 Equivalent conductance of 0.1 M HA (weak reduction potential is formed from the oxidation of
acid) solution is 10 Scm2 equivalent–1 and that at corresponding oxidizable species
infinite dilution is 200 Scm2 equivalent–1 Hence pH of (B) In highly alkaline medium, the anodic process
HA solution is during the electrolytic process is
(A) 1.3 (B) 1.7 4OH– → O2 + 2H2O + 4e–
(C) 2.3 (D) 3.7 (C) The standard potential of Cl– | AgCl | Ag half–cell
Sol.[C] [H+] = C α is related to that of Ag+ | Ag through the expression
= 0.1 = + n Ksp (AgCl)

(D) Compounds of active metals (Zn, Na, Mg) are

= 2.5 × 10–4 reducible by H2 whereas those of noble metals (Cu, Ag,
 pH = – log[H+] Au) are not reducible.
Sol.[A,B] Fact
Q.22 If x is specific resistance of the electrolyte Q.25 On electrolysis of 10–6 M HCl solution
solution and y is the molarity of the solution, then (A) O2 gas is produced at the anode
is given by (B) Cl2 is produced at the anode
(A) (B) (C) O2 gas is produced at the cathode
(D) H2 is produced at the cathode.
Sol. [A,D] (B) aqueous AgNO3 Solution with Pt electrodes
On electrolysis of 10–6 HCl solution (C) dilute H2SO4 with Cu electrodes
at cathode at anode
(D) fused NaOH with a Fe cathode & a Ni anode
2H+ + 2e– → H2 2Cl– + 2e– →Cl2
Sol.[A,B,D]
Q.26 The measured reduction potential for the 2OH– → H2O + O2 + 2e
reaction Mg2+ + 2e– ⎯ → Mg(s) depends upon
(A) Concentration of Mg2+ in solution
(B) area of Mg plate Q.31 Mark out the correct statement(s) regarding
(C) temperature
electrolytic molar conductivity -
(D) % purity of magnesium plate
Sol. [A,C] (A) It increases as temperature increases
ECell = + log [Mg2+] (B) It experiences resistance due to vibration of ion at
the mean position
depend on (C) Increase in concentration decreases the electrolytic
(i) Concentration of Mg+2
molar conductivity of both the strong as well as the
(ii) temperature
(iii) Nature of electrode weak electrolyte
(D) Greater the polarity of solvent, greater is the
Q.27 When galvanic cell started, with passage of
time - electrolytic molar conduction
(A) spontaneity of the reaction decreases; Ecell Sol.[A,C,D]
decreases Fact
(B) reaction quotient Q decreases; Ecell increases
(C) reaction quotient Q increases; Ecell decreases Q.32 If same quantity of electricity is passed
(D) at equilibrium Q = Kc ; Ecell = 0 through three electrolytic cells containing FeSO4,
Sol.[A,C,D] fact Fe2(SO4)3 and Fe(NO3)3, then -
(A) the amount of iron deposited in FeSO4 and
Fe2(SO4)3 are equal
Q.28 During discharge of lead storage battery,
(B) the amount of iron deposited in FeSO4 is
which of the following is/are true ? 1.5 times of the amount of iron deposited in Fe(NO3)3
(A) lead sulphate is formed (C) the amount of iron deposited in Fe2(SO4)3 and
(B) lead is formed Fe(NO3)3 are equal
(C) H2SO4 is consumed (D) the same amount of gas is evolved in all three cases
(D) H2SO4 is formed at the anode
Sol.[B,C,D]
Sol.[A,C] As per cell reaction
Fe2+ + 2e → Fe I Anode
Q.29 The passage of electricity through certain
+ 3e → Fe II 2OH– → H2O O2 + 2e
electrolyte results in the liberation of H2 gas at the
cathode. The electrolyte could be
+ 3e → Fe III
(A) KCl(aq) (B) CuCl2(aq)
(C) MgCl2 (aq) (D) AgNO3
Sol. [A,C]
K and Mg+2 have greater standard electrode Electrode
+
The following questions consists of two statements
Reduction Eº (Volt) So these are reducing agent. So
each, printed as Assertion and Reason. While
evolved H2 gas answering these questions you are to choose any one
of the following four responses.
Q.30 On electrolysis, in which of the following, O2 (A) If both Assertion and Reason are true and the
Reason is correct explanation of the Assertion.
would be liberated at the anode ?
(A) dilute H2SO4 with Pt electrodes
(B) If both Assertion and Reason are true but (A) Zn | Zn2+(C)| (P) Electroche
Reason is not correct explanation of the Assertion. |Zn2+(2C)| Zn mical cell
(C) If Assertion is true but the Reason is false. (B) Cu |Cu2+(0.01M) (Q) Electrolytic
(D) If Assertion is false but Reason is true. || Ag+(0.1M)| Ag cell
(C) Cu |Cu2+(0.1M) (R) Spontaneou
Q.33 Assertion : Salt-bridge is used generally in the || Cu2+(0.01 M)| Cu s cell
electrochemical cells. (D) Conversion of (S) Concentrati
Reason : The ions of the electrolyte used in the salt- electrical energy on cell
bridge should have nearly same transport numbers
into chemical nergy
Sol.[B] Salt bridge keeps the solutions in two half cells
electrically neutral. it also prevent transference or
diffusion of the solutions from one half-cell to the
other. So correct (B) option. Sol.[A] [A] Zn → E° > 0 nernst equation

Zn2+ (2C)→ Zn (i), (iii), (iv)

Q.34 Assertion : Absolute value of Eºred of an [B] Cu → Cu2+
electrode can not be determined. (0.01 M)(i), (iii)
Reason. Neither oxidation nor reduction can take place Ag + → Ag
alone. [0.1 M]
Sol.[A] Yes, because oxidation and reduction take [C] Cu → Cu2+
place simultaneously. (0.1 M) (i), (iv)
Cu → Cu
2+
Q.35 Assertion : The cell constant of a cell depends
(0.01 M)
upon the nature of the material of the electrodes.
[D] (ii)
Reason : The observed conductance of a solution
depends upon the nature of the material of the Q.39
electrodes. Column-I Column-II
Sol.[D] does not depend on material (A) +2
Zn/Zn (c1) (P) =0
|| Mg2+(c1)/Mg

Q.36 Assertion : Gold chloride (AuCl3) solution

(B) Zn/Zn+2(c1) (Q) ≠0
|| Ag+(c1)/Ag
cannot be stored in a vessel made of copper, iron, nickel
(C) Ag/Ag+ || (R) = +ve
chromium, zinc or tin. Ag+/Ag at
Reason : Gold is very precious metal. equilibrium
Sol.[B] Reduction potential of Au is higher than Cu (D) Fe/Fe+3 || Ag+/Ag (S) = –ve

Q.37 Assertion : Molar conductivity of a weak Sol. Factual

electrolyte at infinite dilution cannot be determined (A) no spontaneous (ii,) (iv)
experimentally. (B) Spontanceous (ii), (iii)
Reason : Kohlrausch law help to find the molar (C) ΔG = 0 (i)
conductivity of a weak electrolyte at infinite dilution. (D) spontaneous (ii), (iii)
Sol.[B] Activity of ions becomes was & close towards
conc. of [H+] & [OH–]
Q.40
Column-I Column-II
(Quantities) (Factors on
which
Q.38 Dependency
Column-I Column-II exist)
 (A) Molar (P) Temperature [A] (i), (ii), (iii)
conductance [B] (i), (ii) (iii)
(B) Electrode (Q) Concentration of [C] (i), (iii)
potential species involved
[D] (i), (ii), (iii)
(C) Standard (R) Nature of
electrode substance
potential involved
(D) emf of a cell (S) Stoichiometric
in operation coefficient of
the reaction

Sol. Factual

EXERCISE # 3
Al + → Sn2+ + Al3+ E° = 1.81 V

E° > 0 feasible
Q. 1 Determine the feasibility of the reaction :
2Al(s) + 3Sn4+ (aq) 2Al3+ + 3Sn2+ (aq)
Given that Q. 2 The overall formation constant for the reaction
= + 1.66 V of 6 mol of CN– with Cobalt(II) is 1 x 1019. Calculate
the formation constant for the reaction of 6 mol of CN–
= – 0.15 V with Cobalt(III).Given that,
Sol. Al → Al3+ + 1.66 V Co(CN)6–3 + e ⎯ → Co(CN)6–4
Sn → Sn2+ + 0.15V
4+ EºRp = 0.83 V
Co+3 + e⎯ → Co+2
 EºRp = 1.82 V Eº = = 1.84
Sol. When Eº is positive the cell reaction will be
spontaneous and serves as a source of electrical energy Eº = + 1.84
In this reaction Eº is positive
Q.6 Calculate the equilibrium constant for the
= 1.66 + 0.15
reaction ;
= 1.81 Volt Fe + CuSO4 FeSO4 + Cu at 25ºC.
Given = 0.44V
Q.3 The standard free energy change for the
reaction: = –0.337V
H2 (g) + 2AgCl(s) ⎯ → 2Ag(s) + 2H+(aq) + 2Cl–(aq)
Sol. Fe → Fe2+ + 2e–
is –10.26 kcal mol-1 at 25ºC. A cell using above
reaction is operated at 25ºC under = 1 atm, [H+] Cu+2 + 2e– → Cu = 0.44 + 0.337

and [Cl–] = 0.1. Calculate e.m.f.of cell. = 0.777

Sol. ΔG° = –nFE° = log K
E° = = 0.222
= log K
E = 0.222 – log
log K = 26.06
= 0.34 V K = 1.71 × 1026

Q.4 The e.m.f. of cell Zn | ZnSO4 || CuSO4| Cu at

25ºC is 0.03 V and the temperature coefficient of e.m.f. Q.7 Calculate the maximum work that can be
is –1.4 × 10–4 V per degree. Calculate heat of reaction obtained from the cell.
for the change taking place inside the cell. Zn |Zn2+ (1M) || Ag+ (1M)| Ag
Sol. According to Gibb's Helmholtz equation, Given that
heat of reaction ΔH, given as = 0.76 V
ΔH = nf and = – 0.80 V

Sol. Wmax. = nFEº

T = 273 + 25 = 298 K, n = 2, F = 96500 C, E = 0.03 CV = 2 × 96500 × 1.56 Eº = 0.76 + 0.80
= – 1.4 × 10–4 V/K = 301.80 kJ = 1.50
= log k
ΔH = 2 × 96500 [298 × (–1.4 × 10–4)] – 0.03
= – 13842 Joule = – 13.842 kJ/mole = log k
Q.5 EMF diagram for iron is given as:
Eº (volts) FeO42– Fe3+ log k = 26.06
(Fe = + 6) (Fe = + 3) k = 1.71 × 1026
Fe2+ Fe0 Q.8 The voltage of the cell :
(Fe = + 2) (Fe = + 0) Pb|PbSO4| Na2SO4.10H2O (salt)|Hg2SO4| Hg
Determine the value of . is + 0.9647 at 25°C. The temperature coefficient is 1.74
× 10–4 V. K–1.
Sol.
(i) What is the cell reaction?
(ii) Calculate the values of ΔG, ΔS and ΔH.
Sol. (i) Pb + Hg2SO4 ⎯ → PbSO4 + 2Hg
ΔG3 = ΔG1 + ΔG2 ΔH (Heat of reaction)
–n×F× = – 3× F × 2.20 – 1 × F × 0.77 ΔH = – nF
–4× = – 6.60 – 0.77
= 2 × 96500 [298(1.7×10–4) – 0.9467] Determine the molar conductivity of oxalate ion. Given
= – 42.1 k cal/mol at 25ºC, conductivity of water is 6.2 x 10–6 ohm–1 cm–1
ΔG = – nFE and molar conductivity of Ag+ at infinite dilution is
= – 2 × 96500 × 0.9467 62 ohm–1cm2mol–1 and Ksp of Ag2C2O4 is 1.1 x 10–11
= – 44.49 k cal/mole ?
Sol. S= = 1.4 × 10–4 M
ΔG = ΔH – TΔS
TΔS = ΔH – ΔG
ΔS = = 1.4 × 10–7 mol/cm3
2 × 62 + =
=

= 103.1 ohm–1 cm2 mol–1

= – 42.1 + 44.49
=
Q.12 A galvanic cell is consisted of metallic zinc
plate immersed in 0.1 M Zn(NO3)2 solution and a lead
= 8.02 Ca K–1 mol–1 plate immersed in 0.02M Pb(NO3)2 solution. Calculate
emf of the cell. Given :
Q.9 For the cell process : = – 0.76V and = – 0.13V
Sn(s) + Pb+2 (aq) ⎯ → Pb(s) + Sn+2 (aq) Calculate ratio
of Pb+2 to Sn+2 ion concentration for spontaneity . Sol. = – 0.76 V
Given
Zn2+ + 2e– → Zn = – 0.76 V
= – 0.136 V
Zn → Zn2+ + 2e– = + 0.76 V (oxidation)
= – 0.126 V Pb2+ + 2e– → Pb = – 0.13 V (Reduction)
= +
Sol. Pb2+ + Sn → Sn2+ + Pb
E° = – 0.126 + 0 0.136 = 0.01 V = 0.76 + (– 0.13)
– 2.303 × 8.31 × 298 log K = 0.63 V .
= –2 × 96500 × 0.01
K = 2.18 Q.13 Construct the galvanic cell by coupling the
∴ = = 0.458 following pairs of electrodes Justify your answer:
(i) Cu(s)/Cu2+ (aq), Ag+ (aq)/Ag(s)
(ii) Zn(s)/Zn+2 (aq), Cu2+ (aq)/Cu(s)
Q.10 Determine the solubility and solubility product (iii) Mg(s)/Mg2+ (aq), Ni(s)/Ni2+ (aq)
of Co2[Fe(CN)6)] in water at 25ºC from the following = 0.34 V
data : Conductivity of saturated solution of
= 0.80 V
Co2[Fe(CN)6] = 2.06 × 10–6 ohm–1 cm–1 and that of
water = 4.1 × 10–7 ohm–1 cm–1. The ionic molar = – 0.76 V
conductivities of Co2+ and [Fe(CN)6]4– are 86 and 444
ohm–1 cm2 mol–1 respectively. and = – 0.25 V
Sol. Conductivity of ion Co2+ & [Fe(CN)6]4– Sol. (i) Cu/Cu+2 , Ag+/Ag
= 2.06 × 10–6 – 4.1 × 10–7ohm–1Cm–1 = 0.34 V
= 1.65 × 10–6ohm–1Cm–1
∴ S= = – 0.34 V

= +
= 2.67 × 10–9 mol/cm3 = 2.67 × 10–6 mol/lt
= – 0.34 + 80
∴ Ksp = 4s3 = 7.69 × 10–17
= 0.46
(ii) Zn/zn+2 , Cu+2/Cu
Q.11 The conductivity of a saturated aqueous
= +0.75 + 0.34
solution of Ag2C2O4 is 3.8 x 10–5 ohm–1 cm–1 at 25ºC.
 = 1.1 V = 1.10 g
(iii) Mg/Mg+2 , Ni/Ni2+
= +

= 1.81 + 0.25
Q.17 A current of 4 amperes was passed for 2 hours
= 212 V
through a solution of copper sulphate when 5.0 g of
copper was deposited. Calculate the current efficiency
Q.14 Calculate the potential of the standard
(Cu = 63.5).
Iron-Cadmium cell after the reaction has proceeded to
Sol. W= ×i×t
80% completion. Initially 1 M of each taken and Eº for
cell = 0.04 V.
Sol. Ecell = – log Ical = =

= – log22 = = 2.11

= – × 2 × 0.3010 Current efficiency = × 100

= 0.04 – 0.03 = × 100

= 0.01 V

Q.15 The e.m.f. of the cell, H2(g) |Buffer| |Normal = 52.76 %

calomel electrode is 0.6885 volt at 25ºC when
barometric pressure is 760 mm Hg. What is pH of the Q.18 10 g fairly concentrated solution of CuSO4 is
buffer solution. Eºcalomel = 0.28 volt electrolysed using 0.01 Faraday of electricity.
Sol. Ecell = – log Calculate:
(a) the weight of resulting solution.
(b) the number of equivalents of acid or alkali in
0.6883 = 0.28 – log[H+] solution. (At weight of Cu = 63.5)
Sol. Electrode process during electrolysis of
aqueous
[ = 1 atm = 760 mm of
CuSO4 may be given as
Hg] Cu+2 + 2e– → Cu (cathode)
= – log[H+] 2OH– → H2O + 1/2O2 + 2e–
Mass of copper deposited at cathode by 0.01 faraday
6.91 = – log[H+] [ – log [H+] = pH charge
pH = 6.91 = 0.01 × 31.75 = 0.3175 g
[Here 31.75 is the equivalent mass of Cu+2 ]
Q.16 A 200 W, 110 V incandescent lamp is mass of oxygen evolved by 0.01 faraday charge
connected in series with an electrolytic cell of = 0.01 × 8 = 0.08 g
negligible resistance containing a solution of ZnCl2. Total weight loss from solution
What weight of Zn will be deposited from the solution
= 0.3175 + 0.08 = 0.3975 g
on passing current for 30 minutes? (At.wt. of Zn = 65.4)
Sol. Power = Volt × Current mass of resulting = 10 – 0.3975 = 9.60 g
200 = 110 × i 1 Faraday Produced = 1 equi of Acid
i = 20/11 [E = ] So 0.01 Faraday produced = 1 equi. of Acid
Q.19 The density of copper is 8.94 g ml–1. Find out
W= ×i×t the number of coulomb needed for the electro-
deposition on a plate of an area of 10 × 10 cm2 to a
thickness of 10–2 cm using CuSO4 solution as
= × × 30 × 60 electrolyte. Atomic weight of Cu = 63.6.
 During the same time, 31.75 g of Cu was deposited in
Sol. Mass of the deposited substance the copper voltameter in series with the electrolytic
= volume × density cell. Calculate the percentage yield of NaOH obtained.
Sol. Equivalent mass of Cu = = 31.8
(a × b × c) × d =  It = Q
Equivalent mass of Na = = 23
=Q
Mass of Cu deposited = 3.175
=Q According to faraday's second law of electrolysis

Q = 27129.54 colombs =

Q.20 A zinc rod of 25 g was kept in 100 ml of one or mass of Na deposited = Mass of Cu
molar copper sulphate solution. After certain time the deposited ×
molarity of Cu2+ in solution dropped to 0.8 M.
Calculate
(a) molarity of sulphate ion. 31.75 × = 23g Na
(b) weight of zinc rod at that instant.
Sol. (a) Molarity of sulphate ion does not change Now 1 mol Na = 1 mol NaOH
because no. of moles of solution not change Meq = N ∴ 23g Na = 23 + 16 + 1 = 40g NaOH
1000 ml of 1 N NaOH solution contains = 40 g NaOH
×V ∴ 600 ml of 1 N NaOH solution contains
Meq. of Cu+2 before reaction = 100 × 1 × 2 = = 24g NaOH
= 200
+2
Meq. of Cu after reaction 100 × 0.8 × 2 ∴ % yield of NaOH obtained = ×100 = 60%
Meq. of Cu+2 lost = 200 – 160 = 40
Meq. of Zn lost = 40 Q.23 In two vessels each containing 500 ml water ,
× 1000 = 40 0.5 m mol of aniline (kb = 10–9) and 25 m mol of HCl
are added separately. Two hydrogen electrodes are
constructed using these solutions. Calculate the emf of
WZn = 1.308 g
cell made by connecting them appropriately.
Net weight of Zn rod = 25 – 1.308 g Sol. Pt| H2 | H⊕| H⊕ | H2 |Pt
= 23.692 g (C1) (C2)
H2 ⎯ → 2H⊕ + 2eΘ → a
Q.21 The emf of the cell Ag|AgI|KI(0.05M)|| C1
AgNO3(0.05M) | Ag is 0.788 V. Calculate the solubility 2H⊕ ⎯ → H2 → C
product of AgI. C2
Sol. 0.788 = E° – log 2H⊕ ⎯ → 2H⊕
C2 C1
Ecell = – 0.0591 log
E° = 0.788 + 0.153 = 0.942 Ag+ + I– AgI
–2.303 × 8.31 × 298 log K = –1 × 96500 × 0.942 In 1st vessel [C6H5NH2]2 = × 1000
Ksp = = 1.15 × 10–16
= 10–3 M
[OHΘ] =
= = 10–6
Q.22 After electrolysis of NaCl solution with inert [H+] = 10–8 = C1
electrodes for a certain period of time. 600 mL of the
solution was left. Which was found to be 1N in NaOH.
In 2nd vessel [H+] = × 1000 Pb + PbO2 + 4H+ +

= 5 × 10–2 = C2 Since 2 requires 2 electrons

for Ecell > 0
∴
C 1 < C2
Ecell = – 0.0591 log Now, before electrolysis
= = 5.15

= – 0.05591 (0.30 – 7)
Now, mole of H2SO4 = 5.15 × 3.5 = 18.025
Ecell = 0.3959 V
and after electrolysis
Q.24 From the standard potentials shown in the = = 2.325
following diagram, calculate the potentials and
Mole of H2SO4 = 2.325 × 3.5 = 8.1375
.
∴ mole (or equivalents) of H2SO4 used
= 18.025 – 8.1375 = 9.8875
 = ⇒ i.t = 9.8875 × 96500

= 954143.75 ampere sec = 265.04 ampere hr

Q.26 Same quantity of electricity is being used to
Sol. liberate iodine (at anode) and a metal x (at cathode).
The mass of x deposited is 0.617 g and the iodine is
completely reduced by 46.3 cc of 0.124 M sodium
thiosulphate. Find the equivalent mass of x
Sol. 2e + I2 ⎯ → 2I–
⎯→ + 2e
–5 = – 4 (0.54) – 0.45
eq. of metal = eq. of I2 = eq. of hypo
–5 = – 2.16 – 0.45 5 = ( = )
2.61
= , = 0.52 V ∴ =

Emetal = 10.7.47
–5 = – 1.07 = – 6
– 3.68 = – 6
Q.27 Estimate the cell potential of a Daniel cell
= 0.613 having
1 M Zn++ & originally having 1 M Cu++ after sufficient
Q.25 During the discharge of a lead storage battery NH3 has been added to the cathode compartment to
the sulphuric acid fell from 1.294 to 1.139 g ml–1. make NH3 concentration 2 M. Kf for [Cu(NH3)4]2+ = 1
H2SO4 of density 1.294 g mL–1 is 39% and that of × 1012 , E° for the reaction,
density 1.139 g mL–1 is 20% by weight. The battery Zn + Cu2+ ⎯ → Zn2+ + Cu is 1.1 V.
holds 3.5 L of acid and the volume practically remains Sol. Cu2+ + 4NH3 ⎯ → [Cu(NH3)4]2+ Kf = 1012
constant during the discharge. Calculate the number of 1m
ampere hours for which the battery must have been y –2 ≈1
used. The discharging reactions are = 1012
(anode)
y=

(cathode) y=
Sol. On adding charging and discharging reactions
taking plase in lead storage battery.
Ecell = 1.1 – log Ag(NH3)2+ + e– → Ag + 2NH3
Ag+ + e– → Ag, E° = 0.799 V
Ecell = 1.1 – (13.2) Sol. [Ag(NH3)2]⊕ ⎯ → Ag⊕ + 2NH3 (1)
[Ag(NH3)2]+ + eΘ ⎯ → Ag + 2NH3
Ecell = 0.71 V
AgΘ + e– ⎯ → Ag–2 E°2 = 0.799
(1) + (2) = (3)
Q.28 Consider the cell Ag | AgBr(s) | Br– ||Ag Cl–(s),
+ =
Ag |C|– at 25°C. The solubility product constants of
AgBr & AgCl are respectively 5 × 10–13 & – RT n RT – (1) F 0.799 = – F
1 × 10–10. For what ratio of the concentrations of Br– &
Cl– ions would the emf of the cell be zero ? = 0.799 + n Kd
Sol. Ag|AgBr(s)|BrΘ || Ag Cl(s)|Ag|ClΘ
Ksp(Ag Br) = 5 × 10–13 = 0.799 + 0.0591 log (6 × 10–8)
Ksp(Ag Cl) = 10–10 = 0.373 V
0=0– log

C2 = C1 = Passage - I (Q. 31 to 33)

The cell potential for the unbalanced chemical reaction
=1 :
Hg22+ + NO3– + H3O+ ⎯ → Hg2+ +HNO2 + H2O
is measured under standard state conditions in the
= electrochemical cell shown in the accompanying
diagram. the cell voltage is positive : EºCell = 0.02 V
=

= 5 × 10–3 =

Q.29 The pKsp of AgI is 16.07. If the E° value for

Ag+ | Ag is 0.7991 V. Find the E° for the half cell
reaction AgI(s) + e– ⎯ → Ag + I–
Sol. Pksp AgI = 16.07 Given
AgI(s) + eΘ ⎯ → Ag + IΘ (3) NO3– + 3H3O + 2e– ⎯ → HNO2 + 4H2O
Θ
Ag + e ⎯ → Ag(s)
⊕
(1) Eº = 0.94 V
Θ
AgCl ⎯ → Ag + I
⊕
(2) Q.31 Which of the following statements must be
Ag⊕ + AgCl ⎯ → Ag(s) + IΘ true of the solutions in order for the cell to operate with
the voltage indicated ?
–F – RTln Ksp = – F
(A) The solution in Dish A must be acidic
= + ln Ksp (B) The solution in Dish B must be acidic
(C) The solutions in both Dish A and Dish B must be
acidic
= 0.7991 + (0.0591)(–P Ksp) (D) No acid may be in either Dish A or Dish B
= 0.7991 + (0.0591)(– 16.07) Sol.[C]
According to reaction
= – 0.1511V
NO3– + 3H3O + 2e– → HNO2 + 4H2O
Q.30 Kd for complete dissociation of [Ag(NH3)2]+ HNO3 is an acid which reduced in HNO2 which is also
into Ag+ and 2NH3 is 6 × 10–8 . Calculate E° for the acid so dish A and B are must be acidic.
following half reactions ;
Q.32 At what pH will the cell potential be zero if the The standard potentials for two nonadjacent species can
activity of other components are equal to one ? also be calculated by using the concept that ΔGº as an
(A) (B) – additive property but potential is not an additive
property and ΔGº = – nFxº. If a given oxidation state is
(C) (D) × a stronger oxidising agent than in the next higher
oxidation state, disproportionation can occur. The
reverse of disproportionation is called
Sol.[D] comproportionation. The relative stabilities of the
Ecell = + log [H+] oxidation state can also be understood by drawing a
graph of ΔGº/F against oxidation state, known as Frost
Ecell = 0 diagram, choosing the stability of zero oxidation state
arbitrarily as zero. The most stable oxidation state of a
= 0.02
species lies lowest in the diagram. Disproportionation
0 = 0.02 + log [H+]] is spontaneous if the species lies above a straight line
joining its two product species.
= – log [H+] Q.34 What is the potential of couple at

pH = pH = 14 ?
(A) 1.78 V (B) – 0.94 V
(C) 0.89 V (D) – 0.89 V
Q.33 How many moles of electrons pass through the Sol.[C] ClO– → Cl–
circuit when 0.6 mole of Hg2+ and 0.30 mole of HNO2 E° – = 0.89 V
are produced in the cell that contains 0.5 mole of Hg22+
and 0.40 mole of NO3– at the begining of the reaction ?
(A) 0.6 mole (B) 0.8 mole
(C) 0.3 mole (D) 1 mole
Sol.[A]
Balanced chemical reaction
Hg2+2+NO3–+3H3O++2e–
→2Hg+2+HNO2+4H2O
intial mol 0.5 0.4 0
0
at t = time 0.6 0.3 Q.35 Which of the following statement is correct ?
1 mol Hg2+2 produced = 2 mol Hg+2 (A) Cl2 undergoes disproportionation into Cl– and
So 0.5 Hg2+2 produced = 2 × 0.5 × 0.6 –
ClO both at pH = 0 and pH = 14
= 0.6 mole
(B) Cl2 undergoes disproportionation into Cl–
= 0.6 mole e– required to produced balanced
and ClO– at pH = 14 but not at pH = 0
reaction.
(C) Cl2 undergoes disproportionation into Cl– and
Passage - II (Q. 34 to 36) –
ClO at pH = 0 but not at pH = 14
If an element can exist in several oxidation states, it is (D) None of these
convenient to display the reduction potentials
corresponding to the various half reactions in Sol.[B] From data
diagrammatic form, known as Latimer diagram. The
Latimer diagram for chlorine in acid solution is – Q.36 For a hypothetical element, the Frost diagram
ClO4– ClO3– HClO2 is shown in figure ? Which of the following oxidation
HClO Cl2 Cl– state is least stable ?

In basic solution it is :
ClO4– ClO3– ClO2–
ClO– Cl2 Cl–
 (A) – 1 (B) 0
(C) + 2 (D) + 3
Sol.[D] At n = + 3 is maximum
 EXERCISE # 4
From given data
= 1.51 – 140 = 0.11 V ]
Q.1 Saturated solution of KNO3 is used to make
'salt-bridge' because - [IIT - 2001] is positive hence ΔGº is negative. Thus, above cell
(A) velocity of K+ is greater than of NO3– reaction is feasible but MnO4– ion can oxidise Fe+2 to
Fe+3 and Cl– to Cl2 in aquous medium also, therefore,
(B) velocity of NO3– is greater than that of K+
for quantitative estimation of aqueous Fe(NO3)2, it is
(C) velocity of both K+ and NO3– are nearly the same
not suitable reagent. In electrolytic cell, flow of e– is
(D) KNO3 is highly soluble in water
Sol.[B] Q = 0.01 × 2 × 96500 C possible from cathode to anode through internal supply.
∴ t= = 1.93 × 105 sec. Q.4 In an electrolytic cell, flow of e– will
be - [IIT - 2003]
Q.2 The correct order of equivalent conductance (A) from cathode to anode in solution
at infinite dilution of LiCl, NaCl and (B) from cathode to internal source
KCl is - [IIT - 2001] (C) from cathode to external source
(A) LiCl > NaCl > KCl (D) from anode to cathode
(B) KCl > NaCl > LiCl Sol.[D] Factual
(C) NaCl > KCl > LiCl
(D) LiCl > KCl > NaCl Q.5 For Zn(s) |Zn2+ (0.1M )| |Fe2+ (0.01 M) Fe (s)
Sol.[A,B,D] For data E° > 0 Ecell= 0.2905 at 298 K.
Q.3 Standard electrode potential data are The equilibrium constant for the reaction
useful for understanding the suitability of an oxidant in Zn(s) + Fe2+ (aq) Zn2+ (aq) + Fe (s) at
a redox titration. Some half cell reactions and their 298 K is - [IIT - 2004]
standard potentials are given below- (A) e0.32/.0295 (B) 100.595/0.76
[IIT - 2002] (C) 100.0259/0.32 (D) 100.32/0.0295
MnO4– (aq.) + 8H+ (aq.) + 5e–
Sol.[D] For all Zn/Zn+2 (a = 0.1 M) || Fe+2 (a
⎯ ⎯ →Mn2+ (aq.) + 4H2O(l)
=0.01M)|Fe
Eº = 1.51 V
Cr2O72– (aq.) + 14H+ (aq.) + 6e– The cell reaction.
⎯ ⎯ →2Cr3+ + 7H2O(l) (i) Zn(s) → Zn+2(aq.) + 2e–
Eº = 1.38 V (ii) Fe+2(aq) + 2e– → Fe(s)
Fe3+ (aq.) + e– – ⎯ ⎯ → Fe2+ (aq.) Zn(s) + Fe+2(aq.) → Zn+2(aq.) + Fe(s)
Eº = 0.77 V Nernst equation
Cl2 (g) + 2e–⎯ ⎯ → 2 Cl– (aq.) Ecell = – log10
Eº = 1.40 V
Identify the only incorrect statement regarding the
quantitative estimation of aqueous Fe (NO3)2 0.2905 = – log10
(A) MnO4– can be used in aqueous HCl
(B) Cr2O72– can be used in aqueous HCl ∴ = 0.32 V
(C) MnO72– can be used in aqueous H2SO4
At equilibrium Ecell = 0
(D) Cr2O72– can be used in aqueous H2SO4
Sol.[A] The reaction between MnO4– and HCl may be 0= – log10 Kc
represented as follow.
2MnO4–(aq.) + 16H+ + 10 Cl → log10 Kc = 0.32
2Mn+2(aq) + 8H2O(l) + 5Cl2(g)
Thus, on the basis of this reaction following log10 Kc =
electrochemical cell will be represented Pt Cl(g) (1
atm/Cl–(aq.) || MnO4–(aq.) /Mn+2(aq.) ]
Kc = 100.32/0.0295 Pt |H2(g) | HCl (aq.) | AgCl (s) | Ag (s).
(i) Write the cell reaction
Q.6 2H+ + O2 + 2e → H2O (l) Eº = 1.23 V (ii) Calculate ΔHº and ΔSº for the cell reaction by
assuming that these quantities remain unchanged in the
Fe2+ + 2e⎯ → Fe(s) range 15º to 35ºC.
E0 = − 0.44V (iii) Calculate the solubility of AgCl in water at 25ºC.
What is the ΔGº of the net corrosion Given The standard reduction potential of the Ag+
reaction? [IIT- 2005] (aq)/Ag(s) couple is 0.80 V at 25ºC.
(A) – 322 kJ (B) – 152 kJ [IIT 2001]
(C) – 161 kJ (D) – 76 kJ Sol. (i) AgCl(s) + 1/2 H2 (g) → H+ (aq.) + Ag(s) +
Sol.[A] Reaction Cl–
(i) Fe(s) → Fe+2 + 2e–, Eº = + 0.44 V (ii) ΔS = – 96.5 JK–1 ΔH = – 49987 J mol–1
ΔG10 = – nEºF = – 2 × 0.44 × F (iii) 1.24 × 10–5 mol L–1
(ii) 2H+ + 2e– + 1/2O2 → H2O (l)
Q.10 Two students construct Daniel cell in the
Eº = + 1.23 F
laboratory using common stock solution of ZnSO4 .
ΔG2 = – 2 × (1.23) × F
0
The e. m.f. of one of the cells is 0.03 V higher than the
Net reaction other with Cu as positive electrode. If the concentration
Fe(s) + 2H+ + 1/2O2 → Fe+2 + H2O(l) of CuSO4 in the cell with the higher e.m.f is 0.5 M, find
ΔG30 = ΔG10 + ΔG20 its concentration in the other cell.
Given = 0.06 [IIT 2003]
= – 2 × (0.44) × F + (–2 × 1.23 × F)
= – 0.88 F – 2.46 F = – 3.34 F
Sol. 0.05 M
= – 3.34 × 965005
= – 322.31 kJ = 322 kJ Q.11 Find the equilibrium constant for the reaction
In2+ + Cu2+⎯ → In3+ + Cu+ at 298 K
Q.7 Electrolysis of dilute aqueous NaCl solution given :
was carried out by passing 10 mA current. The time = 0.15 V
required to liberate 0.01 mole of H2 gas at cathode is (1
faraday = 96500 coulomb mol–1) – = – 0.40 V,
[IIT- 2008] = – 0.42 V, [IIT 2004]
(A) 9.65 × 104 sec(B) 19.3 × 104 sec
(C) 28.95 × 104 sec(D) 38.6 × 104 Sol. Eºcell = logKC
sec
Sol.[B] Q = 0.01 × 2 × 96500 C Q.12 (a) (i) Represent the following reaction in the
∴ t= = 1.93 × 105 sec. form of a cell
Ag+ (aq) + Cl– (aq) ⎯ ⎯ → AgCl(s)
(ii) Calculate ΔG° of the above reaction from the
Q.8 For the reduction of ion in an aqueous following data :
solution, E is + 0.96V. Values of E0 for some metal
0 ΔG°f (AgCl) = –109 kJ/ mol
ions are given below - ΔG°f (Cl–) = –129 kJ/ mol
V2+(aq) + 2e– → V E0 = –1.19V ΔG°f (Ag+) = 77 kJ/ mol
Fe3+(aq) + 3e– → Fe E0 = –0.04V (iii) Calculate E° of the cell.
Au3+(aq) + 3e– → Au E0 = +1.40V (iv) Calculate log10 Ksp for AgCl
Hg2+(aq) + 2e– → Hg E0 = + 0.86V (b) 6.539 x 10–2 g of metallic Zn (65.39 amu.) was
The pair(s) of metals that is (are) oxidized by in added to 100 ml of saturated
solution of AgCl. Calculate
aqueous solution is (are) log10 , given
[IIT- 2009]
(A) V and Hg (B) Hg and Fe
(C) Fe and Au (D) Fe and V Ag+ + e–⎯ ⎯ → Ag
Sol.[A,B,D] For data E° > 0 E° = 0.80 V
Zn2+ + 2e–⎯ ⎯ → Zn
Q.9 The standard potential of the following cell is E° = – 0.76 V
0.23 V at 15ºC and 0.21 V at 35ºC.
Also find how many moles of Ag will be formed. C6H12O6 + H2O ⎯ → C6H12O7 + 2H+ + 2e–
[IIT 2005] ;
Sol. (a) (i) Cell Representation Ag/Ag+/AgCl/Cl–/Cl2 E = E° – n = E° – n[H+]2
Pt. (ii) ΔG° = –57 kJ (iii) Eº = 0.59 Volts
(iv) Ksp = 10–10
(b) log = 52.8 E – E° = – × n(–pH) = 0.0591 × 11

= 0.065
Passage - I (Q. 13 to 15) So, Eoxidation increases over by 0.65 V.
Tollen's reagent is used for the detection of aldehyde
when a solution of AgNO3 is added to glucose with Q.15 Ammonia is always added in this reaction.
NH4OH then gluconic acid is formed Which of the following must be incorrect ?
Ag+ + e– ⎯ → Ag Eº = 0.8 V (A) NH3 easily forms complex with Ag+
C6H12O6 + H2O ⎯ → C6H12O7 + 2H+ + 2e–
(B) Ag (NH3)2+ is a strong oxidising reagent than Ag+.
= –0.05V
(C) In absence of NH3 silver salt of gluconic acid is
Ag (NH3)2+ + e– ⎯ → Ag (s) + 2NH3 formed
Eº = 0.337V (D) NH3 has affected the standard reduction potential
[IIT 2006] of glucose/gluconic acid electrode.
Q.13 For the following reaction Sol.[D] During Tollen's test, oxidation of silver ion
Glucose + H2O + 2 Ag+ requires an alkaline medium. Under these conditions it
Gluconic acid + 2 Ag Determine the forms insoluble silver oxide, hence to dissolve this
value of n Keq : oxide a complexing agent, ammonia is added, which
(A) 58.8 (B) 46.2 brings silver ion as diamminosilver (I) ion,
(C) 28.3 (D) 66.13 .
Sol.[A] In the given reaction
Ag ions reduces to AG and Glucose is oxidized to Passage - II (Q.16 to 18) [IIT - 2007]
gluconic acid as per the given reaction. Chemical reactions involve interaction of atoms and
Ag+ + e ⎯ → Ag; = + 0.800 V and molecules. A large number of atoms/molecules
C6H12O6 + H2O ⎯ → C6H12O7 + 2H+ + 2e–; (approximately 6.023 × 1023) are present in a few grams
Gluconic acid of any chemical compound varying with their
= – 0.05 V atomic/molecular masses. To handle such large
Hence, = 0.8 – 0.05 = 0.75V numbers conveniently, the mole concept was
introduced. This concept has implications in diverse
= – nFE = –2F × 0.75 = – RT n K
areas such as analytical chemistry, biochemistry,
⇒ n k = (0.75) = 2 × 38.92 × 0.75 electrochemistry and radiochemistry. The following
example illustrates a typical case, involving
= 58.38 chemical/electrochemical reaction, which requires a
clear understanding of the mole concept.
Q.14 With the increase in concentration of NH3 pH
increases to 11. Consider there is no change in A 4.0 molar aqueous solution of NaCl is
concentration of C6H12O6 & C6H12O7 on addition of prepared and 500mL of this solution is electrolysed.
NH3. This leads to the evolution of chlorine gas at one of the
Which of the following is correct ? electrodes (atomic mass : Na = 23, Hg = 200; 1 Farady
(A) Eox increases by 0.65V from Eºox
= 96500 coulombs).
(B) Eox decreases by 0.65V from Eºox
(C) Ered increases by 0.65V from Eºred Q.16 The total number of moles of chlorine gas
(D) Ered decreases by 0.65V from Eºred
evolved is -
Sol.[C] For the reaction
(A) 0.5 (B) 1.0
(C) 2.0 (D) 3.0 Q.19 The value of ΔG(kJ mol–1) for the given cell is
Sol.[B] Reaction at anode : 2Cl– ⎯ → Cl2 + 2e– (take 1F = 96500 C mol–1) : [IIT 2012]
moles of Cl– = 4 × 500 × 10–3 = 2
moles Cl2 = × 2 = 1 (A) – 5.7 (B) 5.7
(C) 11.4 (D) –11.4
Sol.[D] ΔG° = –
Q.17 If the cathode is a Hg electrode, the maximum
= – 2 × 96500 ×
weight (g) of amalgam formed from this solution is :
(A) 200 (B) 225 = – 11.387
(C) 400 (D) 446 – 11.4
Sol.[D] 500 ml of 4.0 molar NaCl has 2 mole of NaCl
By electrolysis we can get a maximum of 2 moles of Q.20 The solubility product (Ksp; mol3 dm–9) of
sodium which can combine with exactly 2 moles of
MX2 at 298 K based on the information available for
mercury to give amalgam.
the given concentration cell is (take 2.303 × R × 298/F
∴ The maximum weight of amalgam which can be
formed from this solution = 0.059 V) [IIT 2012]
= weight of 2 mole of sodium + weight of 2 mole of (A) 1 × 10–15 (B) 4 × 10–15
mercury (C) 1 × 10–12 (D) 4 × 10–12
= 2 × 23 + 2 × 200 = 446g Sol.[B] Ecell = 0 – log

Q.18 The total charge (coulombs) required for

M+2 = 1 × 10–5
complete electrolysis is :
(A) 24125 MX2 M+2 + 2X–

(B) 48250 S 2S
(C) 96500 Ksp = S(2S)2
(D) 193000 = 4S3
Sol.[D] Na+ + e– ⎯ → Na = 4 × (10–5)3
Total number of moles of Na+ discharged at cathode =
2 mole = 4 × 10–15
∴ The number of electron required for this purpose =
2 mole
∴ Total charge required
= 2 faraday = 2 × 96500 = 193000 coulombs

EXERCISE # 5
(A) – 1.347 V (B) – 0.793 V
(C) – 0.125 V (D) – 1.110V
Q.1 An excess of liquid Hg was added to 10–3 M
Sol.[B] E° = –0.77 – log = –0.8
acidified solution of Fe+3 ions. It was found that only
5% of the ions remained as Fe+3 at equilibrium at 25ºC.
What is Eº for 2Hg/Hg2+2 at 25ºC for- [IIT-
95] Q.2 The standard reduction potential for Cu+2/Cu
2Hg + 2Fe+3 Hg2+2 + 2Fe+2 is + 0.34V. What will be the reduction potential at pH
and = – 0.77 V
= 14 for the above couple, Ksp of Cu(OH)2 is 1.0 × 10– (B) 62.6 × 109
19
[IIT- 96] (C) 0.626 × 105
(A) – 3.2013 (B) – 0.2205 (D) 6.26 × 1010
(B) – 0.913 (B) – 1.23 Sol.[A] E° = 0.77 – 0.54 = 0.23 V
Sol.[B] [OH–] = 1 2 × 96500 × 0.23 = 2.303 × 8.31 × 298 log K
[Cu2+] = 10–19 M K = 6.07 × 107
E = 0.34 – log
Q.6 Calculate the quantity of electricity that
= –0.22 V would be required to reduce 12.3g of nitrobenzene to
aniline. If current efficient is 50%. If the potential drops
Q.3 What is the equilibrium constant for reaction across the cell is
Fe+2 + Ce+4 Fe+3 + Ce+3 3.0 volts – [IIT- 98]
Given (A) 369000 colulomb
EºCe+4/Ce+3= 1.44V (B)115800 coulomb
and = 0.68V (C) 32100 coulumb
(D)521900 coulumb
[IIT- 97]
Sol.[B] N ⎯ → N3– n = 6
(A) KC = 1.3 x 1010
Q=6× × =- 11520 C
(B) KC = 3.2 x1010
(C) KC = 7.6 x 1012
(D) KC = 7.6 x 105 Q.7 A gas X at 1 atm is bubbled through a solution
Sol.[C] E° = 1.44 – 0.68 = 0.76 V containing a mixture of 1 M Y– and 1 M Z– at 25º C. If
1 × 96500 × 0.76 = 2.303 × 8.31 × 298 log K the reduction potential of
K = 7.2 × 1012 Z > Y > X, then - [IIT - 99]
Q.4 Electrolysis of a solution of MnSO4 in aqueous (A) Y will oxidize X and not Z
sulphuric acid is a method for the preparation of MnO2 (B) Y will oxidize Z and not X
as per reaction (C) Y will oxidize both X and Z
Mn+2 (aq.) + 2H2O (D) Y will reduce both X and Z
MnO2 (s) + 2H+ (aq) + H2 (g) Sol.[D] On the basis of reduction potential (Z > Y > X)
Passing a current of 27A for 24 hours gives A spontaneous reaction will have the following
1 Kg of MnO2. What is the value of current efficiency characteristics :-
- [IIT- 97] Z reduced and X oxidised
(A) 50% (B) 94.8% Y reduced and X oxidised
(C) 95.9% (D) 78.3% Z reduced and Y oxidised ]
Sol.[B] η = × 100 = 95 % Hence, Y will oxidise X and not Z

Q.8 In the commercial electrochemical process

for aluminium extraction, the electrolyte used is-
Q.5 What will be the equilibrium constant for the [IIT - 99]
reaction 2Fe+3 + 3I– 2Fe+2 + I3–. The standard (A) Al(OH)3 in NaOH solution
(B) an aqueous solution of Al2 (SO4)3
reduction potential in acidic conditions are 0.77 and
(C) a molten mixture of Al2O3 and Na3AlF6
0.54V respectively for Fe+3/Fe+2 and I3– /I– couples
(D) a molten mixture of AlO(OH) and Al(OH)3
[IIT- 98]
(A) 6.26 × 107 Sol.[D] A molten mixture of AlO(OH) and Al(OH)3
Q.9 For the electrochemical cell, M | M+ || X– | X, ∴ i= =

Eº (M+/M) = 0.44 V and Eº (X/X–) = 0.33 V. = 0.804 ampere

From this data one can deduce that-
Q.11 How long a current of 3 ampere has to be
[IIT - 2000] passed through a solution of silver nitrate to coat a
–
(A) M + X → M + X is the spontaneous reaction
+
metal surface of 80 cm2 with a 0.005 mm thick layer ?
(B) M+ + X– → M + X is the spontaneous reaction Density of silver is 10.5
(C) Ecell = 0.77 V(D) Ecell = – 0.77 V g/cm3. [IIT-1985]
Sol.[A] For the electrochemical cell Sol. Volume of the surface (V) = area × thickness
M/M+//X–/X Given,
Eº (M+/M = 0.44 V) and Eº (X/X– = 0.334 V) area = 80 cm2, thickness = 0.005 mm
Thus, reaction, = 0.0005 cm
∴ V = 80 × 0.0005 = 0.04 cm3
(i) X– ⎯ → X + e– Eº = – 0.334 V
mass of Ag (w) = V × density
(ii) M+ + e– ⎯ → M Eº = 0.44 V
= 0.04 × 10.5 = 0.42 g
M++X– ⎯ → M+XEº = 0.106 V Ag+ + e– ⎯ → Ag
Eº cell is positive, hence this reaction is spontaneous. ∴ wAg =
Q.10 In an electrolysis experiment current was
passed for 5 hours through two cells connected in
0.42 =
series. The first cell contains a solution of gold and the
second contains copper sulphate solution. 9.85 g of
gold was deposited in the first cell. If the oxidation ∴ t= = = 125.09 s
number of gold is +3, find the amount of copper
deposited on the cathode of the second cell. Also Q.12 A 100 watt, 110 volt incandecent lamp is
calculate the magnitude of the current in ampere. connected in series with an electrolyte cell containing
(At.wt. of Au = 197 and At.wt of Cu = 63.5) cadmium sulphate solution. What weight of cadmium
[IIT-1983] will be deposited by the current flowing for 10 hours.
Sol. Equivalent of gold formed = Equivalent of Cu [IIT-1987]
formed Sol. Watt = Ampere × Volt
∴ = ∴ Ampere (i) = =

 Au3+ + 3e– ⎯ → Au Now, w=

and Cu2+ + 2e– ⎯ → Cu
∴ = ∴ wCd =

wCu = = = 4.763 g = = 19.06 g

Also w =

∴ 4.763 =