CLS JEEAD-18-19 XII Che Target-5 SET-2 Chapter-3 PDF

Chapter 3
Electrochemistry
Solutions
SECTION - A
Objective Type Questions (One option is correct)
[Conductance]
1. The correct order of equivalent conductance at infinite dilution of LiCl, NaCl, KCl is
(1) KCl > NaCl > LiCl (2) LiCl > NaCl > KCl (3) LiCl > KCl > NaCl (4) LiCl ~
 NaCl < KCl
Sol. Answer (1)
The ions formed are Li+, Na+ and K+, the hydration is maximum in case of Li+ because of which its mobility
is least and has least conductance.
Hence, the following order.
KCl > NaCl > LiCl
2. The specific conductance of a saturated solution of AgCl is K–1 cm–1. The limiting ionic conductances of Ag+
and Cl– are x and y, respectively. The solubility product of AgCl is
2 2
1000 K ⎛ 1000 K ⎞ 1000  143.5  K ⎛ 10 3  143.5  K ⎞
(1) (2) ⎜⎜ ⎟⎟ (3) (4) ⎜⎜ ⎟
⎟
xy ⎝ xy ⎠ xy ⎝ xy ⎠
Sol. Answer (2)

AgCl
Ag+ + Cl–
Specific conductance = K–1cm–1
K  1000

C
o o
 AgCl =  Ag  Cl = (x + y)
K  1000
 (x + y) =
C
1000K
 C = (x  y)
2
⎡ 1000K ⎤
 Solubility product = C2 = ⎢ ⎥
⎣ (x  y) ⎦
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142 Electrochemistry Solutions of Assignment (Set-2)
3. The equivalent conductances of CH3COONa, HCl and NaCl at infinite dilution are 91, 426 and 126 S cm2 eq–1
respectively at 25°C. The equivalent conductance of 1 M CH3COOH solution is 19.55 S cm2 eq–1. The pH of
solution is
(1) 5.3 (2) 4.3 (3) 2.3 (4) 1.3
Sol. Answer (4)

=  CH3 COO–  Na
o o
 CH3 COONa
= H   Cl–
o o o
HCl

NaCl 
= Na   Cl–
o
  

 CH = CH3COONa  HCl– – NaCl
3 COOH

 91 + 426 + (–126) = 391 =  CH3COOH
 C  19.55
C 19.55
=  = = 0.05
 391
[H+] = C = 1 × 0.05 M
pH = – log [H+] = – log (5 × 10–2)
 2–log 5 = 2 – 0.7 =1.3
4. The limiting equivalent conductance of NaCl, KCl and KBr are 126.5, 150.0 and 152.0 S cm2 eq–1 respectively.
The limiting equivalent ionic conductance of Br– is 76 S cm2 eq–1. The limiting equivalent ionic conductance
of Na+ is
(1) 25.5 (2) 52.5 (3) 75.5 (4) 57.5
Sol. Answer (2)
o o

NaCl = Na + Cl– = 126.5 ...(i)
o o

KCl = K  + Cl– = 150 …(ii)
o o

KBr = K  + Br – = 152 …(iii)
Adding (i) & (iii) subtract (ii)
o o o o o o o o
+ Cl– + K  + Br – – K  – Cl– = Na + Br –
Na
o
= (126.5 + 152 – 150) = (76) +  Na
o = 52.5
Na
 Equivalent ionic conductance for Na+ is 52.5.
5. The molar conductances at infinite dilution of BaCl 2, NaCl and NaOH are respectively 280×10 –4 ,
126.5 × 10–4, 248 × 10–4 S m2 mol–1. The molar conductance at infinite dilution for Ba(OH)2 is
(1) 523 × 10–4 S m2 mol–1 (2) 52.3 × 10–4 S m2 mol–1
(3) 5.23 × 10–4 S m2 mol–1 (4) 65 × 10–4 S m2 mol–1
Solutions of Assignment (Set-2) Electrochemistry 143
Sol. Answer (1)
  
BaCl2
= Ba2  2Cl– ...(i)
 

NaCl = Na  Cl– ...(ii)
 

NaOH = Na  HO– ...(iii)
for Ba(OH)2
(i) + 2(iii) –2(ii)
 (Ba(OH)2 ) = (280 × 10–4) + 2(248 × 10–4) – 2(126.5 × 10–4)
= 523×10–4 Sm2 mol–1.
6. At 25°C, the equivalent conductances at infinite dilution of HCl, CH3COONa and NaCl are 426.1, 91.0 and
126.45 cm2 –1eq–1 respectively.  for CH3COOH (in cm2 –1eq–1) is
(1) 391.6 (2) 390.6 (3) 380.6 (4) 309.6
Sol. Answer (2)
According to given condition:
o o

HCl = H + Cl– ...(i)
 o
=  CH3COO– Na

 CH3 COONa
...(ii)
o o

NaCl = Na + Cl– ...(iii)
Doing the operation
Equation (i) + (ii) – (iii)
o o
=  CH3COO – + H
  
HCl +  CH3COONa – NaCl

 (426.1 + 91.0 – 126.45) =  CH3COOH

  CH3 COOH
= 390.6 cm2 –1/eq
7. AgNO3(aq.) was added to an aqueous KCl solution gradually and the conductivity of the solution was measured.
The plot of conductance () versus the volume of AgNO3 is [IIT-JEE 2011]
   
volume volume volume volume

(P) (Q) (R) (S)
(1) (P) (2) (Q) (3) (R) (4) (S)
Sol. Answer (4)
Ag+ and K+ have nearly same ionic mobility
AgNO3 + KCl  AgCl(s) + KNO3
conc. of KCl
8. Which of following type of plot would you expect from the titration of AgNO3 against KCl solution?
Conductance
Conductance
Conductance
Conductance
(1) (2) (3) (4)
Vol. of KCl Vol. of KCl Vol. of KCl Vol. of KCl
Sol. Answer (3)

Fact.
[Electrolysis]
9. During electrolysis of aqueous solution of a salt under inert electrodes, pH in the space near one of the
electrode is increased. Which of the following salt solution was electrolysed?
(1) KCl (2) CuCl2 (3) Cu(NO3)2 (4) CuSO4
Sol. Answer (1)
In KCl solution the reaction at the electrodes are
2H+ + 2e–  H2
2Cl–  Cl2 + 2e–
 [H+] decreases in the solution because of which [OH] increases hence increasing the pH.
10. On passing 3 faradays of electricity through three electrolytic cells connected in series containing Ag+, Ca+2
and Al+3 ion respectively, the molar ratio in which three metal ions are liberated at the electrode is
(1) 1 : 2 : 3 (2) 3 : 2 : 1 (3) 6 : 3 : 2 (4) 3 : 4 : 2
Sol. Answer (3)
i × t is same for all the electrolytic solutions
⎛W⎞ it it
⎜M⎟ = = (Ag+ + e–  Ag)
⎝ ⎠ Ag nF F
⎛W⎞ it
⎜M⎟ = (Ca2+ + 2e–  Ca)
⎝ ⎠Ca 2F
⎛W⎞ it
and ⎜ M ⎟ = (Al3+ + 3e  Al)
⎝ ⎠ Al 3F
1 1
 Molar ratio is 1 : : or 6:3:2
2 3
11. A current of 2.0 A when passed for 5 hrs through a molten salt, deposits 22.2 g of metal (of atomic weight
177). The oxidation state of metal in metal salt is
(1) +1 (2) +2 (3) +3 (4) +4
Sol. Answer (3)
i = 2A, t = 5 hrs = 5 × 60 × 60 s
wM = 22.2 g; A = 177
Applying the equation
Eit Ait
w= w=
F nF
A i t 177  2  5  60  60
 n= = = 2.97
wF 22.2  96500
 n=3
M3+ + 3e–  M
 Oxidation state is +3.
12. In the electrolysis of aqueous solution of NaOH, 2.8 litre of oxygen at NTP was liberated at the anode. How
much hydrogen was liberated at cathode?
(1) 5.6 litre (2) 56 ml (3) 560 ml (4) 0.056 litre
Sol. Answer (1)
NaOH is electrolysed.
NaOH  Na+ + HO–
H2O  H+ + HO–
At cathode: 2H+ + 2e–H2
At anode: 4HO– 2H2O + O2 + 4e–
⎛w⎞ it ⎛ w ⎞ it
⎜M⎟ =
2F ⎜⎝ M ⎟⎠O2
; =
⎝ ⎠H2 4F
it it
 nH2 : nO2 = : 2:1  Volume ratio VH2 : VO2 = 2 : 1
2F 4F
VH2 2
=  VH2 = 2.8 × 2 = 5.6 L
2.8 1
13. Passage of one ampere current through 0.1 M Ni(NO3)2 solution using Ni electrodes bring in the concentration
of solution to _________ in 60 seconds.
(1) 0.1 M (2) 0.05 M (3) 0.2 M (4) 0.025 M
Sol. Answer (1)
The reaction taking place at the electrodes are
Anode : Ni  Ni2+ + 2e
Cathode : Ni2+ + 2e–  Ni
Hence [Ni2+] does not change.
 Concentration of Ni2+ is 0.1M.
14. When electricity is passed through a solution of AlCl3 13.5 g of Al is deposited. The number of faradays must
be
(1) 1.0 (2) 1.5 (3) 0.5 (4) 2
Sol. Answer (2)
The reaction at cathode is
Al3+ + 3e–  Al (n = 3)
Eit w
w= ⇒ F
F E
13.5 13.5
 i×t= ×F= F = 1.5 F
⎛ 27 ⎞ 9
⎜ 3 ⎟
⎝ ⎠
15. 0.5 faraday of electricity was passed to deposit all the copper present in 500 ml of CuSO4 solution. What was
the molarity of this solution?
(1) 1 M (2) 0.5 M (3) 0.25 M (4) 2.5 M
Sol. Answer (2)
i × t = 0.5 F
E  it ⎛w⎞ it 0.5F
w=  ⎜ ⎟ = = = 0.25 moles
F ⎝M⎠ 2F 2F
V × molarity = No. of moles
 500 × x × 10–3 = 0.25
0.25  103
 x= = 0.5
500
Molarity = 0.5 M
16. 25 g of a metal is deposited on cathode during the electrolysis of metal nitrate solution by a current of 5 A
passing for 4 hours. If atomic weight of the metal is 100. The valency of metal in metal nitrate is
(1) 1 (2) 2 (3) 3 (4) 4
Sol. Answer (3)
wM = 25 g, i = 5 A, t = 5 hrs = 4 × 60 × 60 second
A = 100 (metal nitrate was electrolysed)
Applying the equation,
E  it
w=
F
100 5  4  60  60
 25 = 
n 96500
100  5  4  60  60
 n= =3
(96500  25)
Hence, valency = 3
17. A well stirred (1 L) solution of 0.1 M CuSO4 is electrolysed at 25°C using copper electrodes with a current of
25 mA for 6 hours. If current efficiency is 50%. At the end of the duration what would be the concentration of
copper ions in the solution?
(1) 0.0856 M (2) 0.092 M (3) 0.0986 M (4) 0.1 M
Sol. Answer (3)
18. 50 ml of a buffer of 1 M NH 3 and 1 M NH4+ are placed in two volatic cells separately. A current of
3.0 amp is passed through both cells for 10 min. If electrolysis of water takes place as
2H2O + O2 + 4e–  4OH– (R.H.S.)
2H2O  4H+ + O2 + 4e– (L.H.S.)
then pH of the
(1) L.H.S. will increase (2) R.H.S. will increase
(3) R.H.S. will decrease (4) Both side will increase
Sol. Answer (2)
Because of the reactions of electrolysis, [H+] concentration will decrease as a result of which pH will increase.
19. 1 M aqueous solution of NaCl undergo electrolysis if 50 mA current is passed for 12 hours. Assume current
efficiency is 25%. The total volume of gas produced at standard state is
(1) 137 ml (2) 68.5 ml (3) 125.44 ml (4) 62.72 ml
Sol. Answer (3)
NaCl aq. solution undergoes electrolysis
NaCl  Na+ + Cl–
H2O  H+ + HO–
Reactions :
At cathode : 2H+ + 2e  H2(g)
At anode : 2Cl–  Cl2 + 2e
⎛w⎞ it it it
⎜M⎟ = + =
⎝ ⎠T 2F 2F F
3 25 12  60  60
 50  10  = nT
100 96500
 nT = 0.005595
 V = 0.005595 × 22400
  125.44 ml.
20. Vanadium electrode is oxidised electrically. If the mass of electrode decreases by 100 mg during the passage
of 570 coulomb, the oxidation state of vanadium in the product is (At. wt. of V = 51)
(1) 6 (2) 5 (3) 4 (4) 3
Sol. Answer (4)
i × t = 570 C
w = 100 mg = 100 × 10–3 g
E  it
w=
F
100  103 570

 =
51 96500  n
570  51
 n= =3
100  10 –3  96500
21. Which is correct increasing order of deposition?

(1) Na+ < Mg+2 < Zn+2 < Ag+ (2) Ag+ < Zn+2 < Mg+2 < Na+
(3) Mg+2 < Na+ < Zn+2 < Ag+ (4) Mg+2 < Zn+2 < Na+ < Ag+
Sol. Answer (1)
Increasing order of deposition is related to the order of reduction and oxidation potential (in accordance with
preferential discharge theory)
 Na+ < Mg2+ < Zn2+ < Ag+
22. Which is the correct order of deposition of anion?

(1) SO4–2 > OH– > Cl– > Br– > I– (2) SO4–2 < OH– < CI– < Br– < I–
(3) SO4–2 > Cl– > Br– > I– > OH– (4) Br– > Cl– > I– > SO4–2 > OH–
Sol. Answer (2)
It is in the order of discharge potential
 In anion order of deposition is
SO2– – – –
4 < HO < Cl < Br < I
–
23. Rate of corrosion is maximum when

(1) An electrolyte is present in water (2) Metal has low S.R.P.
(3) Metal has high standard oxidation potential (4) All of these
Sol. Answer (4)
When metal has high standard oxidation potential, it has more tendency to undergo oxidation. In presence
of electrolyte, rate of Corrosion is maximum.
24. Which of the following cannot be extracted by electrolysis from aqueous solution of their salts?
(1) Zn (2) Ag (3) Cu (4) Pt
Sol. Answer (1)
As EoZn2 / Zn is less than Eo 

H /H
2
25. Zn amalgam is prepared by electrolysis of aqueous ZnCl2 using 9 gram Hg cathode. How much current is to
be passed through ZnCl2 solution for 1000 seconds to prepare a Zn amalgam with 20% by weight? (Atomic
mass, Zn = 65.4 g)
(1) 5.6 A (2) 7.2 A (3) 8.85 A (4) 11.2 A
Sol. Answer (3)
x
Let, x gram of Zn deposited on 9 gram of Hg. % of Zn in amalgam   100  25
9x
 x = 3 gram
32
Equivalent of Zn 
65.4
6 96500
Current    8.85 A
65.4 1000
26. Electrolysis of dilute aqueous NaCl solution was carried out by passing 10 milliampere current. The time
required to liberate 0.01 mol of H2 gas at the cathode is (1 faraday = 96500 C mol–1) [IIT-JEE 2008]
(1) 9.65 × 104 s (2) 19.3 × 104 s (3) 28.95 × 104 s (4) 38.6 × 104 s
Sol. Answer (2)
W it

E F
W 10  103  t
 0.01 2 
E 96500
t = 19.3 × 104 s
[E.M.F. (E° and Keq)]
27. By how much will the potential of half cell Cu+2/Cu change, if the solution is diluted to 100 times at 298 K?
(1) Increases by 59 mV (2) Decreases by 59 mV
(3) Increases by 29.5 mV (4) Decreases by 29.5 mV
Sol. Answer (2)
For Cu2+ + 2e–  Cu(s)
0.0591 1
E = Eº – log
Cu2  /Cu
2 [Cu2 ]
When Cu2+ solution is diluted to 100 times [Cu2+] decreases to 1/100
0.0591 100
E' = Eº – log
Cu2  /Cu [Cu2 ]
2
0.0591
E = Eº – [[log 100 – log [Cu2+]]
2
0.0591 0.0591 1
 E = Eº – ×2– log
2 2 [Cu2 ]
0.0591 1
 E = Eº – log – 0.0591
2 [Cu2 ]
 E = E – 0.0591, Hence, Potential decreases by 59 mV.
28. The Ecell of the reaction

MnO 4  Fe 2  H  Mn2  Fe 3  H2O is 0.59 V at 25°C. The equilibrium constant for the reaction is
(1) 50 (2) 10 (3) 1050 (4) 105
Sol. Answer (3)
Eocell = 0.59 V
MnO4– + Fe2+ + H+  Mn2+ + Fe3+ + H2O

0.0591
E = Eocell – log Qc
5
At equilibrium, E = 0; Qc = Kc
0.0591
 Eocell = log Kc
5
5  0.59
 = log Kc
0.59
50 = log Kc
 Kc = 1050.
29. Some Indian scientists tried to use a metal x for electroplating iron pillar in Mehrauli but they ended up with
Ecell of the reaction to be negative. They concluded that
(1) Reaction is spontaneous (2) Reaction is non-spontaneous
(3) Reaction is reversible (4) Reaction is non-reversible
Sol. Answer (2)
For electroplating Iron a metal ‘x’ is used.
Ecell is negative, it means that no reaction takes place and the reaction is non-spontaneous.
30. The equilibrium constant for the reaction Sr (s) + Mg+2 (aq) Sr+2 (aq) + Mg (s) is 2.69 × 1012 at 25°C.
The E° for a cell made up of Sr/Sr+2 and Mg+2/Mg half cells is
(1) 0.3667 V (2) 0.7346 V (3) 0.1836 V (4) 3.667 V
Sol. Answer (1)
The reaction is
Sr(s) + Mg2+(aq)  Mg(s) + Sr2+(aq)
Kc = 2.69 × 1012
At equilibrium, E = 0; Q = Kc
0.0591
 0 = Eº – log Kc
2
0.0591 0.0591
 Eº = log Kc = log (2.69 × 1012) = 0.3667 V
2 2
31. In which of the following pair, first specie is a better oxidising agent than second specie under standard
conditions?
(1) Br2 & Au3+ (2) H2 & Ag+
(3) Cr3+ & Cd2+ (4) O2 in acidic medium & O2 in basic medium
Sol. Answer (4)
32. M+ is not stable and undergoes disproportionation to form M and M2+. Calculate E for M+ disproportionation
E 2  0.153 V, E   0.53 V
M /M M /M
(1) +0.683 V (2) –0.367 V (3) 0.754 V (4) +0.3415 V

Sol. Answer (3)
Given
EoCu2 /Cu = +0.153 V and EoCu /Cu = 0.53 V
The reaction
2Cu+  Cu + Cu2+
o o
 EoCell = ECu /Cu2 + ECu /Cu
o
we required ECu /Cu2
Cu2+ + 2e  Cu; 0.153

Cu  Cu+ + e–; – 0.53
 Cu2+ + e–  Cu+
 –1 × F × Eº = [–2 × F × (0.153)] + [F × 0.53]
 –FEº = –2F (0.153) + 0.53 F
 Eº = –0.53 + (2 × 0.153)
 EoCu2 /Cu = – 0.224
or EoCu /Cu2 = 0.224
 Eº = 0.224 + 0.53 = 0.754 V
33. E(Na  /Na)  2.71 V, E(Mg 2 /Mg)  2.37 V
E(Fe  2 /Fe)  0.44 V, E(Cr  3 /Cr)  0.41 V
Based on this data, which is the poorest reducing agent?

(1) Na+ (2) Mg+2 (3) Fe+2 (4) Cr+3
Sol. Answer (4)
Cr3+ is the poorest reducing agent because of least value of oxidation potential.
34. The standard reduction potential of Cu+2/Cu and Cu+2/Cu+ are 0.337 V and 0.153 V respectively. The standard
reduction potential of Cu+/Cu half cell is
(1) 0.521 V (2) 0.490 V (3) 0.321 V (4) 0.290 V
Sol. Answer (1)
Given (i) ... Cu2+ + 2e–  Cu(s); E1o = 0.337 V
(ii)... Cu2+ + e–  Cu+ Eo2 = 0.153 V
Reversing equation (ii); we get

Cu+  Cu2+ + e– ...(iii)
Adding equation (i) and (iii)
We get, Cu+ + e–  Cu
o
Go  G1o  Go2 = (–1 × F × Eº) = –2  F  E1   +  –1 F  E 
o
2
 – FEº = [– 2× F × (0.337)] + [–F × –0.153]

– FEº = – 2 × 0.337 × F + (0.153) F
 Eº = (2×0.337) – (0.153) = 0.521 V
35. What is G° for the following reaction?

Cu+2(aq) + 2Ag(s)  Cu(s) + 2Ag+
ECu 2 /Cu  0.34 V, E Ag /Ag  0.8 V
(1) –44.5 kJ (2) 44.5 kJ (3) –89 kJ (4) 89 kJ

Sol. Answer (4)
The reaction given is
Cu2+ (aq) + 2Ag(s)  Cu(s) + 2Ag+
EoCell = E Ag/ Ag  ECu2 /Cu

o o
 EoCell = (– 0.8) + (0.34) = – 0.46
Gº = – n F × Eº = – 2 × F × (–0.46)
= – 2 × –0.46 × 96500 = 88780 J
or Gº = + 89 kJ.
o
36. For the reduction half reaction EQuinhydrone  1.30 V
O–H O
+ –
+ 2H + 2e
O–H O
At pH = 3 at 298 K, electrode reduction potential is (Consider quinone and hydroquinone have identical
concentration)
(1) 1.48 V (2) 1.42 V (3) 1.36 V (4) 1.3 V
Sol. Answer (1)
For the reaction, on applying Nernst equation
0.0591
Ecell = EoCell – log [H+]2
2
0.0591
Ecell = 1.30 – log (10–3)2
2
0.0591
=– × (–6) log 10 + 1.30 = 0.0591 × 3 + 1.30 = 1.477  1.48
2
37. Emf of the cell

Zn | Zn+2(aq) || Cu+2(aq) | Cu is independent of
(1) Quantity of Cu+2 and Zn+2 in solution (2) Concentration of Cu+2
(3) Concentration of Zn+2 (4) Temperature
Sol. Answer (1)
For the given cell
⎡ Zn2 ⎤
⎣ ⎦
0.0591
E = Eº – log
2 ⎡Cu2 ⎤
⎣ ⎦
When Zn2+ & Cu2+ quantity is changed the emf does not change because EMF depends upon concentration
and not the quantity.
38. Which metal oxide is thermally unstable?

(1) Al2O3 (2) Na2O (3) BaO (4) Ag2O
Sol. Answer (4)
Ag2O decomposes as

1
Ag2O   2Ag + 2 O2.
39. H2(1 atm) | 2.26 M HCOOH || 0.222 M CH3COOH| (1 atm) H2

Ka(HCOOH) = 1.77 × 10–4,
Ka(CH3COOH) = 1.8 × 10–5
Emf of the cell is (Neglect the liquid-liquid junction potential)
(1) 0.0591 V (2) –0.0591 V (3) 0.02955 V (4) –0.02955 V
Sol. Answer (2)

HCOO– + H+
HCOOH
C1(1 – ) C1 C1
[H+]L = C1 = (Ka)1  C1

CH3COO– + H+
CH3 COOH
C2(1 – )C2 C2
 [H+]R = (Ka)2  C2
0.0591 [H ]L
E = Eº – log
1 [H ]R
0.0591 K1  C1
E=0– log
1 K 2  C2
0.0591 1.77  10 4  2.26

or E = – log
2 1.8  10 5  0.222
0.0591
E=– log 100 = – 0.0591
2
40. Given that

NiO2 + 4H+ + 2e–  Ni2+ + 2H2O, E° = 1.678 V
NiO2 + 2H2O + 2e–  Ni(OH)2 + 2OH–, E° = –0.49 V
For the following reaction
Ni(OH)2 + 2H+ Ni2+ + 2H2O
Gibb’s free energy change (in kJ mol–1) is
(1) 418.424 (2) –229.284 (3) –418.424 (4) 229.284
Sol. Answer (3)
NiO2  4H   2e –  Ni 2  2H2O
 , E1o  1.678 V
Ni(OH)2  2OH –  2e –  NiO2  2H2O  2e – , Eo2   0.49 V

Ni(OH)2  2H   Ni 2  2H2O
 , Eo  x V
Go = G1o  Go2  – nF(E1o  Eo2 )
= –2 × 96500 × (1.678 + 0.49) J mol–1

= –418.424 kJ mol–1
41. Emf of cell given, Ag(s), AgCl(s)||KCl(aq)|Hg2Cl2(s)|Hg(s) is 0.05 V at 300 K and temperature coefficient of the
cell is 3.34 × 10–4 VK–1. Calculate the change in enthalpy of the cell.
(1) 965 (2) 9650 (3) 96500 (4) 96.5
Sol. Answer (2)
2Ag  2Ag+ + 2e– : (anode)
Hg22+ + 2e–  2Hg : (cathode)
∵ n=2
⎛ Ecell ⎞
H = –nFEcell  nFT ⎜ ⎟
⎝ T ⎠P
= 2 × 96500(300 × 3.34 × 10–4 – 0.05)
= 9650 J mol–1
42. Given : Ag+ + e–  Ag; E°red = 0.799 V
Dissociation constant for [Ag(NH3)2]+ into Ag+ and NH3 is 6 × 10–14. Then for the following half-cell reaction:
[Ag(NH3)2]+ + e–  Ag + 2NH3, calculate E° at 298 K.
(1) 0.019 V (2) 0.03 V (3) 0.014 V (4) 0.19 V
Sol. Answer (1)
Ag  Ag  e – ;
 EoOP  – 0.799 V
Ag(NH3 )2  e – 
 Ag  NH3 ; o
ERP ?
Ag(NH3 )2 Ag  2NH3
o 0.0591 [Ag(NH3 )2 ]

Ecell  Ecell  log10  0 at equilibrium
1 [Ag ] [NH3 ]2
 Eocell  0.0591  log10 K C  0.0591  log10 (6  10–14 )

= –0.780 V
 EoOP( Ag/ Ag )  ERP(

o
Ag(NH 
3 )2 / Ag)
 EoAg(NH   – 0.780  0.799

3 )2 / Ag
= +0.019 V
43. Consider the following cell reaction:


2Fe(s)  O2(g)  4H(aq) 2  2H O(l)
 2Fe(aq) 2 ; E° = 1.67 V
At [Fe2+] = 10–3 M, P(O2) = 0.1 atm and pH = 3, the cell potential at 25°C is [IIT-JEE 2011]
(1) 1.47 V (2) 1.77 V (3) 1.87 V (4) 1.57 V
Sol. Answer (4)
0.0591 [Fe2 ]2
Ecell  1.67  log
4 pO2  [H ]4
0.0581 (103 )2
 1.67  log
4 0.1 (103 )4
0.0591 106
 1.67  log
4 1013
0.0591
 1.67  log107
4
0.0591
 1.67   7  1.57
4
44. For the following electrochemical cell at 298 K,
Pt(s)|H2(g, 1 bar)|H+(aq, 1 M)||M4+(aq), M2+(aq)|Pt(s)
[M2 (aq)]
Ecell  0.092 V When 4
 10 x
[M (aq)]
 RT
Given : E 4   0.151 V; 2.303  0.059 V
M /M2  F
The value of x is [JEE(Advanced)2016]
(1) –2 (2) –1 (3) 1 (4) 2
Sol. Answer (4)
H2 (g)  2H  2e –
M4   2e –  M2 
H2 (g)  M4   2H  M2
H 2  M2  (1)2  M2  M2  , º

Ecell  Eº 4 – Eº  = 0.151 – 0 = 0.151 V
Qx    /M2 
M4  M 4 M4  M H /H2
0.059
E  0.151– log10 x
2
0.059
0.092  0.151– log10 x
2
On solving, we get x = 2
45. For the following cell,
Zn(s) | ZnSO4(aq) || CuSO4(aq) | Cu(s)
when the concentration of Zn2+ is 10 times the concentration of Cu2+, the expression for G (in J mol–1) is
[F is Faraday constant; R is gas constant; T is temperature; E°(cell) = 1.1 V] [JEE(Advanced)2017]
(1) 2.303RT – 2.2F (2) 1.1F
(3) –2.2F (4) 2.303RT + 1.1F
Sol. Answer (1)
Zn | ZnSO4 || CuSO4 | Cu
(aq) (aq)
G =G° + RT In Q
G = G° + 2.303 RT log Q

⎛ [Zn2 ] 10 ⎞
⎜⎜ Q   ⎟
⎝ [Cu2 ] 1 ⎟⎠
G°= – nF E°Cell
= – 2F  1.1
= – 2.2 F
10
G = – 2.2 F + 2.303 RT log
1
G  2.303 RT – 2.2 F
SECTION - B
Objective Type Questions (More than one options are correct)
1. Which of following is/are correct?

(1) The metallic conduction is due to the movement of electrons in the metal
(2) The electrolytic conduction is due to the movement of ions in the solution
(3) The metallic conduction increases with increase in temperature whereas electrolytic conduction decreases
with increase in temperature
(4) None of these
Sol. Answer (1, 2)
The metallic conduction is due to the presence of electrons in the metal and electrolytic conduction is due
to the movement of ions in the solution.
2. Molar conductance of 2 M H2A acid is 10 S cm2 mol–1. Molar conductance of H2A at infinite dilution is
400 S cm2 mol–1. Which statement is/are correct?
(1) Degree of dissociation is 2.5% and pH of solution is 1.0
(2) Degree of dissociation is 4 and pH of solution is 1.4
(3) Dissociation constant of H2A is 6.24 × 10–5
(4) Dissociation constant of H2A as per H2 A 2H  A 2 is 2.56 × 10–4
Sol. Answer (1, 4)
m 10 1
 0
   2.5%
m 400 40
At equation, H A
2 2H  A 2
C(1   ) 2C C
(2C )2  C
K eq 
C(1   )
Putting C = 2 M,  = 0.025
Keq = 2.56 × 10–4
[H+] = 2C = 0.1 = 10–1
pH = – log 10–1 = 1
3. Which compounds have maximum conductivity?

(1) 0.2 M [Cr(NH3)3Cl3] (2) 0.15 M [Cr(NH3)4Cl2]Cl
(3) 0.1 M [Cr(NH3)5Cl]Cl2 (4) 0.07 M [Cr(NH3)6]Cl3
Sol. Answer (2, 3)
[Cr(NH3)4Cl2]Cl  [Cr(NH3)4Cl2]2+ +Cl–
 0.15 × 2 = 0.30
and for
[Cr(NH3)5Cl]Cl2  [Cr(NH3)5Cl]2+ + 2Cl–
 0.1 × 3 = 0.30
4. For electrolyte AxBy which is/are not correct relation between molar conductivity (M) and equivalent conductivity
(eq)
(1) M = xy eq (2) eq = xy M (3) xM = y eq (4) yM = x eq
Sol. Answer (2, 3, 4)
For the electrolyte Ax By
n-factor = xy
M = (xy) eq
Only 1st option is correct & others are incorrect option.
5. The cell constant of a conductivity cell is defined as ( = cell constant, l = length between the electrode,
A = area, R = resistance, G = conductance, K = conductivity,  = specific resistance)
l  G
(1)   (2)  (3)  = (G)–1 (4)  
A R K
Sol. Answer (1, 3)
l 1 1 l
R=   
A  RA
l
K = C
A
RA l
 ;  and   (G)1
l A
6. Which of following plots will not be obtained for a conductometric titration of HCl and NaOH?
Conductance
Conductance
Conductance
Conductance
(1) (2) (3) (4)
Vol. of NaOH Vol. of NaOH Vol. of NaOH Vol. of NaOH

In the conductometric titration of HCl and NaOH conductance first decreases, reaches a minimum value and
then increases.
7. 1.0 L of 0.1 M aqueous solution of KCl is electrolysed. A current of 96.50 mA is passed through the solution
for 10 hours. Which is/are correct? (Assume volume of solution remains constant during electrolysis)
(1) After electrolysis molarity of K+ is 0.064 and molarity of Cl– is 0.064
(2) After electrolysis molarity of K+ is 0.1 and molarity of Cl– is 0.064
(3) At S.T.P. 202 ml of Cl2 produced when current efficiency is 50%
(4) At S.T.P. 606 ml of total gases produced when current efficiency is 50%
Sol. Answer (2, 3)
i = 96.50 A, t = 10 × 60 × 60 s
Solution is 1.0 L and 0.1 M
Moles present = 1 × 0.1 = 0.1 moles
Reactions :
2H+ + 2e  H2 : 2Cl–  Cl2 + 2e–
w it w 96.50  10  60  60  10 –3
= = = = 0.018
M nF M 2  96500
For Cl– = 0.036; Molarity = 0.1 – 0.036 = 0.064

0.018  22.4
VCl2 = = 0.202 L or 202 ml.
2
K+ will not discharge.
8. 1000 ml 2 M CuSO4 is electrolysed by a current of 9.65 amp for 2 hours. Which is/are correct?
(1) After electrolysis remaining concentration of Cu+2 is 1.64 M using Cu electrode
(2) After electrolysis remaining concentration of Cu+2 is 1.64 M using Pt-electrode
(3) When remaining concentration of Cu+2 is 1.822 then volume of solution is reduced by 10% using Pt-
electrode
(4) 17.15 g copper deposit when current efficiency is 75% using copper electrode
No. of moles of CuSO4
= 1000 × 2 = 2000 millimoles = 2 moles
i = 9.65 A; t = 2 hrs = 2 × 60 × 60 s
E  it
Cu deposited is w =
F
63.5 9.65  2  60  60
 w= × = 22.86
 96500
W
n= = 0.36
M
 2 – 0.36 = 1.64
Hence, molarity = 1.64 M using Pt electrode
63.5 75 (9.65)  2  60  60
w= × = 17.15 g
2 100 96500
9. Which statement is correct about electrolysis of CuSO4?

(1) At cathode Cu will deposit and at anode O2 will be produced using Pt-electrode
(2) At cathode Cu will not deposit but Cu dissolve at anode using Cu-electrode
(3) At cathode Cu will deposit and at anode O2 will be produced using Cu-electrode
(4) At cathode Cu will deposit and at anode Cu will dissolve using Cu-electrode
Sol. Answer (1, 4)
Using Pt electrodes
CuSO4  Cu2+ + SO2–

4
H2O  H+ + HO–
At cathode : Cu2+ + 2e–  Cu
Anode : 4HO–  2H2O + O2 + 4e–
Products are Cu and O2
Using Cu electrodes
Anode : Cu  Cu2+ + 2 e–
Cathode : Cu2+ + 2 e–  Cu
10. Aqueous solution of which electrolyte produces H2 gas at cathode, when electrolysed among inert electrodes?
(1) NaCl (2) MgCl2 (3) CuCl2 (4) AgCl
Sol. Answer (1, 2)
H+ has lower discharge potential as compared to Na+ and Mg2+
Hence, in case of NaCl and MgCl2 reaction is 2H+ + 2e–  H2.
11. For the electrolysis of CuSO4 solution which is/are correct?

(1) Cathode reaction : 2H+ + 2e  H2 using Pt electrode
(2) Cathode reaction : Cu+2 + 2e–  Cu using Cu electrode
(3) Anode reaction : Cu  Cu+2 + 2e– using Cu electrode
(4) Anode reaction : Cu  Cu+2 + 2e– using Pt electrode
Sol. Answer (2, 3)
CuSO4(aq) forms the ions
Cu2+, H+, HO– and SO2–

4
Using Pt electrode
At cathode; Cu2+ + 2e  Cu
Using Cu electrodes
At anode : Cu  Cu2+ + 2e–
12. Which solution(s) become(s) more acidic after the electrolysis using inert electrodes?
(1) NaCl solution (2) CuSO4 solution (3) AgNO3 solution (4) Na2SO4 solution
Sol. Answer (2, 3)
In the electrolysis of CuSO4 solution and AgNO3 solution, H2SO4 and HNO3 are formed respectively.
13. Zn | Zn+2 (1M) || Ni+2 (1 M) | Ni, antilog (0.7411) = 5.5

E Zn 2 /Zn  0.75 V, ENi 2 /Ni  0.24 V
Which statement is/are correct for above cell?
(1) Emf of cell is 0.51 V and cell reaction is spontaneous
(2) Emf of cell is –0.51 V and cell reaction is non-spontaneous
(3) Emf of cell is zero when concentration of Ni+2 is 5.5 × 10–18 M
(4) Cell reaction is non-spontaneous when concentration of Ni+2 is less than 5.5 × 10–18 M
The given cell is
Zn|Zn2+(1M)||Ni2+(1M)|Ni
Eº = (0.75) + (–0.24) = 0.51V
and cell reaction is spontaneous.
0.0591 [Zn2 ]
E = Eº – log
2 [Ni2 ]
 E = 0; [Ni2+] = 5.5 × 10–18 M
The cell reaction is
Non-spontaneous when concentration of M2+ is less than 5.5 × 10–18 M.
14. Which is/are correct statements about salt bridge?

(1) Velocity of ions of salt bridge are almost equal
(2) Salt bridge completes the electric circuit
(3) Ions of salt bridge discharge at electrode
(4) Ions of salt bridge do not discharge at electrode
Salt Bridge contains electrolyte which do not participate in the electrochemical change, completes the cell
circuit and it is also necessary that velocity of ions of salt bridge are almost equal.
15. Ksp for AgBr = 8 × 10–13

Ag, AgNO3 (1.0 M) || KBr (1.0 M), AgBr, Ag
For above cell which is/are correct?
(1) Ecell = 0.715 V (2) Ecell = –0.715 V
(3) G = –1 × 96500 × 0.715 (4) G = 1 × 96500 × 0.715
Sol. Answer (2, 4)
For the 1st Half cell
Anode : Ag  Ag+ + e–
Cathode : Ag+ + e–  Ag
0.0591 [Ag ]L
E=  log
1 [Ag ]R
1
E = –0.0591 log
[Ag ]
Ksp (AgBr) = [Ag+] [Br–]
8  1013
[Ag+]R = = 8 × 10–13 M
1
1 1013
E = –0.0591 log 13 = –0.0591 log
8  10 8
 0.0591 log 8 × 10–13.
0.0591 (0.6 – 13) = – 0.715 V
and  G = –nFE = +1 × 96500 × 0.715
16. Which statement is/are correct?

(1) In voltaic cell electrons flow from anode to cathode
(2) In voltaic cell, anode is negative electrode and cathode is positive electrode
(3) Oxidation take place at anode and reduction take place at cathode in electrochemical cell
(4) In electrolytic cell oxidation take place at cathode and reduction take place at anode
At cathode always reduction takes place and at anode always oxidation takes place.
Hence (4) will not the correct statement.
17. E Zn 2 /Zn  0.76 V, ENi 2 /Ni  0.24 V
EFe  3 /Fe  0.04 V, ECd 2 /Cd  0.40 V
Which is/are correct statements?

(1) Zn+2 + Cd  Cd+2 + Zn, spontaneous (2) Ni+2 + Cd  Ni + Cd+2, spontaneous
(3) Fe+3 + Ni  Ni+2 + Fe, spontaneous (4) Cd+2 + Zn  Zn+2 + Cd, spontaneous
For (1)
Zn2+ + Cd  Cd2+ + Zn
Eº = ECd/Cd2  EZn2 /Zn = (0.40) + (–0.76) = –0.36 < 0
o o
Non-spontaneous
For Ni2+ + Cd  Cd2+ + Ni
Eº = ECd/Cd2  ENi2 /Ni = (0.40) + (– 0.24) > 0 is spontaneous
o o
for Fe3+ + Ni  Ni2+ + Fe

o o
Eº = ENi/Ni2  EFe3  /Fe = (0.24) + (–0.04) > 0 i.e. spontaneous
and for reaction
Cd2+ + Zn  Zn2+ + Cd
Eo = EZn/Zn2  ECd2 /Cd = (0.76) + (– 0.40) > 0 is spontaneous.

o o
18. In which of the following cells, reaction quotient is equal to one?

(1) Pb|PbC2O4, CaC2O4, CaCl2(0.1 M)||CuSO4(0.1 M) | Cu
(2) Zn|ZnSO4(0.1 M)||CuSO4(0.1 M)|Cu
(3) Zn|ZnSO4(0.1 M)||Hg2Cl2, KCl(0.1 M)|Hg, Pt
(4) Cu|CuSO4(0.1 M)||SnCl2(0.1 M)|SnCl4(0.1M), Pt
Sol. Answer (1, 2)
In (3),  = 10
In (4),  = 0.1
19. Which of the following cells give the cell potential to their standard values?
(1) Zn|Zn2+(0.01 M)||H3O+(0.1 M)|H2(1 atm), Pt (2) Cu|Cu2+(0.25 M)||Ag+(0.5 M)|Ag
(3) Cd|Cd2+(0.01 M)||pH = 1|H2(1 atm), Pt (4) Zn|Zn2+(0.1 M)||pH = 1|H2(1 atm), Pt
o
For Ecell  Ecell , K C  1.
20. Daniell cell : Zn|Zn 2(aq) || Cu 2(aq)|Cu operates as electrolysis cell for 60 min and a current of
( 50 ml 1M) ( 50 ml 1M)
0.965 A is passed. Which is/are correct?

(E  Cu 2 /Cu  0.34 V, E  Zn 2 /Zn   0.76 V)
(1) After electrolysis Zn+2 concentration is 1.36 M (2) After electrolysis Cu+2 concentration is 0.64 M
(3) After electrolysis Zn+2 concentration is 0.82 M (4) After electrolysis Cu+2 concentration is 1.18 M
Sol. Answer (1, 2)

31.75
WCu (deposited) = × 0.965 × 60 × 60 = 1.143 g
96500
Total weight of copper = 50 × 10–3 × 1 × 63.5 = 3.175 g
Left weight of copper = 3.175 – 1.143 = 2.032 g
2.032 1000
Molarity of Cu2+ solution =  = 0.64 M
63.5 50
Molarity of Zn2+ solution = 1 + 0.36 = 1.36 M
21. Saturated solution of KNO3 is used to make ‘salt-bridge’. Then incorrect option(s) is/are
(1) Velocity of K+ is zero (2) Velocity of NO3– is zero
(3) Velocity of both K+ and NO3– are nearly the same (4) KNO3 is highly soluble in water
Sol. Answer (1, 2)
Fact.
22. For the reduction of NO3– ion in an aqueous solution, Eo is +0.96 V. Values of Eo for some metal ions are
given below [IIT-JEE 2009]
V2+ (aq) + 2e–  V Eo = – 1.19 V
Fe3+ (aq) + 3e–  Fe Eo = –0.04 V
Au3+ (aq) + 3e–  Au Eo = +1.40 V
Hg2+ (aq) + 2e–  Hg Eo = +0.86 V
The pair(s) of metals that is(are) oxidized by NO3– in aqueous solution is(are)
(1) V and Hg (2) Hg and Fe (3) Fe and Au (4) Fe and V

Oxidation of V
Eo = 0.96 – (–1.19) = 2.15 V
For Fe,
Eo = 0.96 – (–0.04) = 1.0 V
For Au,
Eo = 0.96 – 1.4 = – 0.044 V (not feasible)
For Hg
Eo = 0.96 – 0.86 = 0.1 V
23. Which is/are correct?

(1) If temperature coefficient is greater than zero, cell reaction is endothermic
(2) If temperature coefficient is less than zero, cell reaction is endothermic
(3) If temperature coefficient is less than zero, cell reaction is exothermic
(4) If Ecell is negative then G is negative and cell reaction is spontaneous
Sol. Answer (1, 3)
It is known fact that H and temperature coefficient are related as,
⎛ E ⎞
H > 0 for ⎜ ⎟ >0
⎝ T ⎠
⎛ E ⎞
and H < 0 for ⎜ ⎟ <0
⎝ T ⎠
24. The standard emf of the cell
Fe | Fe+2(aq) || Cd+2 | Cd is 0.0372 V and temperature coefficient of emf is –0.125 VK–1. Which is/are correct
about the cell (at room temperature)?
(1) G° = 7.18 kJ, H° = –7196.43 kJ (2) G° = –7.18 kJ, H° = 7196.43 kJ
(3) G° = –7.18 kJ, H° = –7196.43 kJ (4) S° = –24.125 kJ K–1, reaction is spontaneous
Sol. Answer (3, 4)
The emf of cell

Fe|Fe2+||Cd2+|Cd, Eº = 0.0372
 Gº = –nFEº = – 2 × 96500 × 0.0372
 Gº = – 7179.6 J = – 7.18 kJ
⎛ Ecell ⎞
(S) = nF ⎜ T ⎟
⎝ ⎠P
 (Sº) = 2 × F × (–0.125)
 – 7180 = – ΔHo + 298 {2 × 96500 × 0.125}
 ΔHo = – 7196.43 kJ
25. When a lead-storage battery is discharged, then incorrect option(s) is/are
(1) H2SO4 is consumed (2) Pb is formed
(3) SO2 is evolved (4) PbSO4 is consumed
Pb is consumed and PbSO4 is formed. SO2 is not evolved.
26. Which is/are correct about corrosion?

(1) Due to corrosion FeO.xH2O formed
(2) Due to corrosion Fe2O3.xH2O formed
(3) Presence of air and moisture increases the rate of corrosion
(4) Magnesium is used as sacrificial anode

In corrosion
Fe  Fe2+ + 2e is formed and the formation of oxide i.e., Fe2O3.xH2O takes place and presence of air and
moisture is must.
Mg can be used as sacrificial anode.
27. In a galvanic cell, the salt bridge [JEE(Advanced)2014]
(1) Does not participate chemically in the cell reaction
(2) Stops the diffusion of ions from one electrode to another
(3) Is necessary for the occurrence of the cell reaction
(4) Ensures mixing of the two electrolytic solutions
Sol. Answer (1, 2)
In a galvanic cell, the salt bridge does not participate in the cell reaction, stops diffusion of ions from one
electrode to another and is not necessary for the occurrence of the cell reaction.
SECTION - C
Linked Comprehension Type Questions
Comprehension-I
An electrochemical cell is constructed by immersing a piece of copper wire in 50 ml of 0.1 M CuSO4 solution
and zinc strip in 50 ml of 0.1 M ZnSO4 solution
[E Cu 2 /Cu  0.34 V, E Zn 2 /Zn  0.76 V]
1. The emf of cell is

(1) 1.07 V (2) 1.1 V (3) 1.3 V (4) 1.13 V
Sol. Answer (2)
EoCu2 /Cu = 0.34 V and EoZn2 / Zn = – 0.76 V
0.0591 [Zn2 ]
ECell = Eº – log
2 [Cu2 ]
[Zn2+] = [Cu2+] = 1M
o o
 E = Eº = EZn/Zn2  ECu2 /Cu
 E = (0.76) + (0.34)
 E = Eº = 1.1 V
2. The emf of cell increases when small amount of concentrated NH3 is added to
(1) ZnSO4 solution (2) CuSO4 solution (3) Both (1) & (2) (4) Can't say
Sol. Answer (1)
When NH3 is added to ZnSO4 solution, NH3 reacts with Zn2+ in the following manner :

Zn2+ + 4 NH3
[Zn(NH3)4]
2+
i.e., [Zn2+] decreases.

In the equation
0.0591 [Zn2 ]
E = Eo – log
2 [Cu2 ]
[Zn2 ]
If [Zn2+] decreases then log decreases hence, EMF of cell increases.
[Cu2 ]
3. In a separate experiment, 50 ml of 1.5 M NH3 is added to CuSO4 solution. Emf of the cell is
[Kf ([Cu(NH3)4]+2) = 5.88 × 1013]
(1) 0.933 V (2) 1.327 V (3) 1.467 V (4) 0.696 V
Sol. Answer (4)
Due to the complex formation, [Cu2+] decreases & it can be calculated by the reaction,
Cu2   4HN3

[Cu(NH3)4]2+
50  0.1 50  1.5
50  0.1
[Cu (NH3 )4 ]2 100
[Cu2+] = = = 9.3 × 10–15 M
[NH3 ]4  k f (0.55)4  5.88  1013
0.0591 ⎛ 0.1 ⎞
Ecell = 1.1 – log ⎜⎜ –15 ⎟⎟ = 0.715 V
2 ⎝ 9.3  10 ⎠
Thus, the e.m.f. of cell decreases.
Comprehension-II
Molar conductivity of ions are given as product of charge on ions to their ionic mobilities and Faraday constant
  n F (here  is the ionic mobility of An+). For electrolytes say A B , molar conductivity is given by
An  An  x y
m(A xBy )  x n F  ym F.

An  Am 
ions ionic mobility
K+ 7.616 × 10–4
Ca+2 12.33 × 10–4
Br– 8.09 × 10–4
SO4–2 16.58 × 10–4
1. The equivalent conductance of CaSO4 at infinite dilution is

(1) 279 (2) 28.51 × 10–4 (3) 31.82 × 10–4 (4) 306
Sol. Answer (1)
Equivalent conductance of CaSO4 is the sum of ionic conductance of Ca2+ & SO2–
4 .
 
=  Ca2    SO2–

 CaSO 4 4
 2
Ca 
= UCa2   F

SO2–
4

= USO2–
4
F
U
Ca2  & USO24 are ionic mobilities

 CaSO 4
= F {12.33 + 16.58} × 10–4

 CaSO 4
= 96500 × 10–4 × 28.91 = 278.98  279
 Equivalent conductance of CaSO4 is 279
2. If degree of dissociation of CaSO4 solution is 10% then equivalent conductance of CaSO4 is

(1) 27.9 (2) 2.851 × 10–4 (3) 3.182 × 10–4 (4) 30.6
Sol. Answer (1)
We know that
C
=

C
 (0.1) =
(279)
C = 279 × (0.1) = 27.9
 Equivalent conductance = 27.9
Comprehension-III
Given below are a set of half-cell reactions (in acidic medium) alongwith their E° (in volt) values.
I2  2e 
 2I E  0.54
Cl2  2e 
 2CI E  1.36
Mn3  e 
 Mn2 E  1.50
3  2
Fe  e 
 Fe E  0.77
O2  4H  4e 
 2H2 O E  1.23
1. Among the following, identify the correct statement

(1) Cl– is oxidised by O2 (2) Fe+2 is oxidised by iodine
(3) I– is oxidised by chlorine (4) Mn+2 is oxidised by chlorine
Sol. Answer (3)
2. While Fe+3 is stable, Mn+3 is not stable in acid solution because
(1) O2 oxidises Mn+2 to Mn+3
(2) O2 oxidises both Mn+2 to Mn+3 and Fe+2 to Fe+3
(3) Fe+3 oxidises H2O to O2
(4) Mn+3 oxidises H2O to O2
Sol. Answer (4)
3. The strongest reducing agent in aqueous solution is

(1) I– (2) Cl– (3) Mn+2 (4) Fe+2
Sol. Answer (1)
Comprehension-IV
Chemical reactions involve interaction of atoms and molecules. A large number of atoms/molecules
(approximately 6.023 × 1023) are present in a few grams of any chemical compound varying with their atomic/
molecular masses. To handle such large numbers conveniently, the mole concept was introduced. This concept
has implications in diverse areas such as analytical chemistry, biochemistry, electrochemistry and
radiochemistry. The following example illustrates a typical case, involving chemical/electrochemical reaction,
which requires a clear understanding of the mole concept.
A 4.0 molar aqueous solution of NaCl is prepared and 500 mL of this solution is electrolysed. This leads to
the evolution of chlorine gas at one of the electrodes (atomic mass: Na = 23, Hg = 200,
1 faraday = 96500 coulomb). [IIT-JEE 2007]
1. The total number of moles of chlorine gas evolved is

(1) 0.5 (2) 1.0 (3) 2.0 (4) 3.0
Sol. Answer (2)
4  500
nNaCl = 2
1000
 nCl2  1.
2. If the cathode is a Hg electrode, then the maximum weight (g) of amalgam formed from this solution is
(1) 200 (2) 225 (3) 400 (4) 446
Sol. Answer (4)
nNa deposited = 2
 nNa–Hg formed = 2
 Mass = 2 × 223 = 446.
3. The total charge (coulomb) required for complete electrolysis is

(1) 24125 (2) 48250 (3) 96500 (4) 193000
Sol. Answer (4)
Total charge required = 2F = 2 × 96500 = 193000 C.
Comprehension-V
The concentration of potassium ions inside a biological cell is at least twenty times higher than the outside. The
resulting potential difference across the cell is important in several processes such as transmission of nerve
impulses and maintaining the ion balance. A simple model for such a concentration cell involving a metal M is
M(s) | M+(aq; 0.05 molar) || M+ (aq; 1 molar) | M(s)
For the above electrolytic cell the magnitude of the cell potential |Ecell| = 70 mV. [IIT-JEE 2010]
1. For the above cell

(1) Ecell < 0; G > 0 (2) Ecell > 0; G < 0
(3) Ecell < 0; Gº > 0 (4) Ecell > 0; Gº < 0
Sol. Answer (2)
Cell reaction
M 
 M
(1 M) (0.05 M)
Apply Nernst equation
0.059 0.05
E  Eº – log
1 1
0.059
E–
1

log 5  10 –2 
0.059
E– ⎡ –2   log5 ⎤⎦
1 ⎣
2. If the 0.05 molar solution of M+ is replaced by a 0.0025 molar M+ solution, then the magnitude of the cell
potential would be
(1) 35 mV (2) 70 mV (3) 140 mV (4) 700 mV
Sol. Answer (3)
E1 log0.05

E2 log0.0025
E1 log5  10 –2

E2 log25  10 –4
E1 70(given)
70 –1.3 1
 
E2 –2.6 2
Comprehension-VI
The electrochemical cell shown below is a concentration cell.

M | M2+ (saturated solution of a sparingly soluble salt, MX2) || M2+ (0.001 mol dm–3) | M
The emf of the cell depends on the difference in concentrations of M2+ ions at the two electrodes. The emf of
the cell at 298 K is 0.059 V. [IIT-JEE 2012]
1. The solubility product (Ksp; mol3 dm–9) of MX2 at 298 K based on the information available for the given
concentration cell is (take 2.303 × R × 298/F = 0.059 V)
(1) 1 × 10–15 (2) 4 × 10–15 (3) 1 × 10–12 (4) 4 × 10–12
Sol. Answer (2)
0.059 0.001
0.059   log 2 
2 (M )
0.001
log 2
[M2  ]
0.001
 100 K sp = 4  (10 5 )3 = 4  10 15
[M2  ]
[M2  ]  10 5
2. The value of G (kJ mol–1) for the given cell is (take 1 F = 96500 C mol–1)
(1) –5.7 (2) 5.7 (3) 11.4 (4) –11.4
Sol. Answer (4)
G = –nFE
= –2 × 96500 × 0.059
= –11387 joule mol–1
 –11.4 kJ mol–1
SECTION - D
Assertion-Reason Type Questions
1. STATEMENT-1 : The molar conductivity of strong electrolyte decreases with increase in concentration.
and
STATEMENT-2 : At high concentration, migration of ion is slow.
Sol. Answer (1)
Molar conductance is given by the following expression
K  1000
 = (K × V) =
c
Here ‘c’ is the concentration

More is the concentration lesser is the molar conductance
Hence, both statements are correct and statement-2 is the correct explanation of statement-1.
2. STATEMENT-1 : Electrolysis of molten PbBr2 using platinum electrodes produces Br2 at anode.
and
STATEMENT-2 : Br2 is obtained in gaseous state at room temperature.
Sol. Answer (3)

PbBr2  Pb2+ + 2Br–
At cathode :
Pb2+ + 2e–  Pb
At anode :
2Br–  Br2 + 2e–
Br2 obtained in liquid state at room temperature.
 Statement-1 is correct and statement-2 is false.
3. STATEMENT-1 : For the concentration cell, Zn(s) Zn  2 (aq) Zn  2 (aq) Zn for spontaneous cell reaction C1 < C2.
C1 C2
and
RT C
STATEMENT-2 : For concentration cell, E cell  loge 2 for spontaneous reaction Ecell = +ve  C2 > C1.
nF C1
Sol. Answer (1)
The given cell is
Zn|Zn2+(C1) ||Zn2+ (C2)|Zn
Zn(s)  Zn2+ + 2e–
0.0591
E o
= E Zn/ Zn2 – log (C1)
Zn/Zn2 
2
0.0591 ⎛ 1 ⎞
E = EZn2 /Zn – log ⎜ C ⎟
Zn2  /Zn
2 ⎝ 2⎠
0.0591 ⎛ C1 ⎞
 E = (E Zn/ Zn2  E Zn2 / Zn ) –
o o
log ⎜ C ⎟
2 ⎝ 2⎠
 EMF of cell
– 0.0591 ⎛C ⎞
E= log ⎜ 1 ⎟
2 ⎝ C2 ⎠
⎛ C1 ⎞
log ⎜ C ⎟ < 0 for spontaneity
⎝ 2⎠
⎛ C1 ⎞
log ⎜ C ⎟ < log 1
⎝ 2⎠
 C1 < C2.
 Statement-1 and statements-2 is correct and it is also the correct explanation.
4. STATEMENT-1 : A saturated solution of KCl is used to make salt bridge in concentration cells.
and
STATEMENT-2 : Mobility of K+ and Cl– are nearly same.
Sol. Answer (1)
Mobilities of ions involved in salt bridge is same which is used in concentration cells.
5. STATEMENT-1 : The molar conductance of weak electrolyte at infinite dilution is equal to sum of molar
conductances of cations and anions.
and
STATEMENT-2 : Kohlrausch’s law is applicable for strong electrolytes.
Sol. Answer (2)
 
AB =  A   B–
Kohlraush law is applicable for weak electrolyte and not for strong electrolyte.
6. STATEMENT-1 : When a copper wire is placed in a solution of AgNO3, the solution acquires blue colour.
and
o
STATEMENT-2 : ERP of Cu+2/Cu is lesser than E o .
Ag / Ag
Sol. Answer (1)
Cu + AgNO3  Cu2+ + Ag
Eo for reaction is positive because Eo  Eo

Cu2  /Cu Ag / Ag
7. STATEMENT-1 : G° = –nFE°.

and
STATEMENT-2 : E° should be positive for a spontaneous reaction.
Sol. Answer (2)
Go = – nFEo
But Go does not decide the spontaneity only G decides the spontaneity of reaction.
 Both statements are correct but statement-2 is not the correct explanation.
8. STATEMENT-1 : One coulomb of electric charge deposits the weight that is equal to electrochemical equivalent
of substance.
and
STATEMENT-2 : One faraday deposits one mole of substance.
Sol. Answer (3)
One faraday deposits one equivalent of substance.
9. STATEMENT-1 : If an aqueous solution of NaCl is electrolysed, the product obtained at the cathode is H2 gas
and not Na.
and
STATEMENT-2 : Gases are liberated faster than metals.
Sol. Answer (3)

Na+ + Cl–
NaCl

H2O +
H + OH
–
Among cations, hydrogen has higher standard electrode potential and among anions chlorine has low standard
electrode potential. Thus, at cathode preferentially H2 gas is evolved, and at anode Cl2 gas is evolved.
10. STATEMENT-1 : H2 + O2 fuel cell gives a constant voltage throughout its life.
and
STATEMENT-2 : In this fuel cell, H2 reacts with OH– ions, yet the overall concentration of OH– ions does not
change.
Sol. Answer (1)
In H2 + O2 fuel cell,
Anode : 2H2(g) + 4OH–(aq)  4H2O() + 4e–
Cathode : O2(g) + 2H2O() + 4e–  4OH–(aq)
OH– consumed is reformed, so [OH–] does not change.
Hence, fuel-cell gives constant voltage throughout its life.
SECTION - E
Matrix-Match Type Questions
1. Match the following

Column-I Column-II
Complex (with coordination number Maximum molar conductivity (S cm2 mol–1)

of Co3+ as equal to six)
(A) CoCl3.6NH3 (p) 97
(B) CoCl3.5NH3 (q) 0
(C) CoCl3.4NH3 (r) 404
(D) CoCl3.3NH3 (s) 229
Sol. Answer A(r), B(s), C(p), D(q)
[Co(NH 3 ) 6 ] Cl 3 will give maximum number of ions(4) because of which conductivity is maximum
i.e. 404.
In [Co(NH3)3Cl3] no ions are given
Hence molar conductivity is zero.

[Co(NH3)5Cl]Cl2 & [Co(NH3)4Cl2] Cl forms 3 & 2 ions.

Column-I Column-II
(Amount of charge used for diposition/liberation)

(A) 1 mol Al+3 (p) F
(B) 2.3 gm of Na+ (q) 3F

(C) 3.6 gm of Mg+2 (r) 0.1 F
(D) 11.2 L H2 at S.T.P. (s) 0.3 F
Sol. Answer A(q), B(r), C(s), D(p)
(A) 1 mole Al3+
w it wF
=  it =
E F E
⎛ wF ⎞ wF
it = 3 ⎜ ⎟ = = 3F
⎝ M ⎠ E
(B) 2.3 g Na+
w 2.3
it = F= F = 0.1 F
E 23
(C) 3.6 g of Mg2+
3.6
it = F = 0.3 F
12
11.2 1
(D)
22.4
=
2
nH 
2
w it w
=  it = F
E F E
⎛w⎞
= 2⎜ ⎟ F
⎝M⎠
1
= 2 F=F
2

Column-I Column-II
c
m
(A) , specific conductance (p) 
m

(B)  m , molar conductance (q) m
(C) , degree of dissociation (r) Decreases with dilution
(D) Kohlrausch law (s) Decreases with increase in concentration of strong
electrolytes
Sol. Answer A(r), B(s), C(p), D(q)
(A) Specific conductance decreases with dilution
(B) Molar conductance decreases with increase in concentration of electrolyte
m
(C)   and decreases with dilution
m
l
(D) Resistance  and decreases with dilution
A

Column-I Column-II
(A) Calomel electrode (p) Electrolyte concentration cell
(B) Zn-Cd(C1) |CdCl2| Zn-Cd(C2) (q) Metal-insoluble anion half cell
(C) Quinhydrone electrode (r) Electrode concentration cell
(D) Pt|H2(1 atm)|H+(C1)||H+(C2)|H2(1 atm)|Pt (s) Redox half cell
Sol. Answer A(q), B(r), C(s), D(p)

Column-I Column-II
(Electrolysis) (Observation)
(A) Aqueous solution of NaCl using inert (p) Metal loss at anode
electrodes
(B) Very dilute aqueous solution of NaCl (q) Chlorine gas evolved at anode
using mercury cathode
(C) CuSO4 using copper electrodes (r) Oxygen gas evolved at anode
(D) 50% H2SO4 solution (s) A compound with peroxide bond is formed
Sol. Answer A(q), B(r), C(p), D(s)
6. The standard reduction potential data at 25°C is given below.
E°(Fe3+, Fe2+) = + 0.77 V;
E°(Fe2+, Fe) = – 0.44 V
E°(Cu2+, Cu) = + 0.34 V;
E°(Cu+, Cu) = + 0.52 V
E°[O2(g) + 4H+ + 4e–  2H2O] = + 1.23 V;
E°[O2(g) + 2 H2O + 4e–  4OH–] = + 0.40 V
E°(Cr3+, Cr) = – 0.74 V;
E°(Cr2+, Cr) = – 0.91 V
Match Eº of the redox pair in Column-I with the values given in Column-II and select the correct answer using
the code given below the Columns : [JEE(Advanced)-2013]
Column-I Column-II
(A) Eº(Fe3+, Fe) (p) –0.18 V

4H+ + 4OH–)
(B) Eº(4H2O (q) –0.4 V
(C) Eº(Cu2+ + Cu  2Cu+) (r) –0.04 V
(D) Eº(Cr3+, Cr2+) (s) –0.83 V
Codes :
A B C D
(1) s p q r
(2) q r s p
(3) p q r s
(4) r s p q
Sol. Answer (4)
+3 +2
(A) Fe + e Fe ºG1 = – 1F × 0.77
+2
Fe + 2e Fe ºG2 = + 2F × 0.77
+3
Fe + 3e Fe ºG3 = – 3F × EºFe+3/Fe
ºG3 = ºG1 + ºG2
– 3F × EºFe+3 /Fe = – 0.77 F + 0.88 F
– 3EºFe+3 /Fe = 0.11 (V)
0.11 (V)
EºFe+3 /Fe = – = – 0.036 (V)
3
+
(B) 2H2O O2 + 4H + 4e Eº = – 1.23 V
–
4e + O2 + 2H2O OH Eº = + 0.40 V
+ –
4 H2O 4H + 4OH Eº = – 0.83 V
(C) Cu2+ + 2e Cu Eº = + 0.34 V

2+
2Cu Cu + 2eu Eº = – 0.52 V
2+ +
Cu + Cu 2Cu Eº = – 0.18 V
+3
(D) Cr + 3e Cr ºG1 = + 3 × F × 0.74
+2
Cr Cr + 2e ºG2 = + 2 × F ×0.91
+3 +2
Cr + e Cr
EºCr+3 /Cr+2 = – 0.4 V
7. An aqueous solution of X is added slowly to an aqueous solution of Y as shown in Column-I. The variation in
conductivity of these reactions is given in Column-II. Match Column-I with Column-II and select the correct
answer using the code given below the Columns : [JEE(Advanced)-2013]
Column-I Column-II
(A) (C2H5)3N + CH3COOH (p) Conductivity decreases and then increases
X Y
(B) KI (0.1M) + AgNO3 (0.01M) (q) Conductivity decreases and then does not
X Y change much
(C) CH3COOH + KOH (r) Conductivity increases and then does not
X Y change much
(D) NaOH + HI (s) Conductivity does not change much and
X Y then increases
Codes :
A B C D
(1) r s q p
(2) s r q p
(3) q r s p
(4) p s r q
Sol. Answer (1)
Conductivity
(A)
(C2H5)3N
Firstly it decreases due to nutrilization of CH3COOH and replacement of H+ by but thereafter buffer
formation takes place and [H+] becomes constant and increases hence conductivity increases but after
equivalence point (C2H5)3N is not ionized due to much higher concentration of in solution.
Conductivity
(B)
VKI
AgNO3  KI  AgI(S)  KNO3
Initially only Ag+ is replaced by K+ hence conductivity remain the same thereafter equivalence point [K+]
increases hence conducitity increases.
Conductivity
(C)
VCH3COOH
Initially conducitity decreases due to replacement of OH– by CH3COO– and then almost constant due
to buffer formation
Conductivity
(D)
VNaOH
Decreases due to removal of H+ by Na+ then increases due to OH–.
SECTION - F
Integer Answer Type Questions
1. The half cell potentials of a half cell | A  x n  , A x  | Pt were found to be as follows:
% of reduced form 24.4 48.8

Half cell potential (V) 0.101 0.115
Determine the value of 'n'.
Sol. Answer (2)
 x n 
A  ne –  A x 
0.059 ⎛ 75.6 ⎞
0.101  ERP
o
 log ⎜ ⎟
n ⎝ 24.4 ⎠
0.059 ⎛ 51.2 ⎞
0.115  ERP
o
 log ⎜ ⎟ ⇒n2
n ⎝ 48.8 ⎠
o o
2. The standard reduction potential of EBi3  /Bi and ECu2 /Cu are 0.226 V and 0.344 V respectively. A mixture of
salts of Bi and Cu at unit concentration each is electrolysed at 25°C. At what value of  log Cu2  does Bismuth
starts to deposit during electrolysis.
Sol. Answer (4)
The passage of current would initially deposit Cu2+ till ECu2 /Cu becomes 0.266 V because then only Bi3+ will
be deposited.
0.059
Thus, ECu2 /Cu  Ecu
o
2  log Cu2  
/Cu
2
0.059
0.266  0.344  log  Cu2   ⇒  log Cu2    4
2
3. A cell is containing two H electrodes. The negative electrode is in contact with a solution of pH = 6. EMF of
the cell is 0.118 V at 25°C. Calculate pH at positive electrode.
Sol. Answer (4)
H  cathode
Ecell  0.059log
H  anode
= 0.059 [pH anode – pH cathode]

0.118 = 0.059 [6 – pH]
pH = 4
4. How many faradays of electricity is required to deposit 2 mol copper from CuSO4 solution?
Sol. Answer (4)
Equivalent weight of copper = 63.5/2
Hence, 2 mol require 4 F electricity.
5. A current of 3 ampere has to be passed through a solution of AgNO3 solution to coat a metal surface of
80 cm2 with 0.005 mm thick layer for a duration of approximately (y)3 seconds. What is the value of y?
(Density of Ag is 10.5 g/cm3)
Sol. Answer (5)
Volume of surface = 80 × 0.0005
= 0.04 cm2
WAg = 0.04 × 10.5 = 0.42 gram
Eit

96500
108  3  t
 0.42  ⇒ t  125.09 s  y 3
96500
 y5
6. The cost at 5 paise per kWh of operating an electric motor for 8 hours, which takes 15 ampere at 110 V, is
11y paise. Calculate y.
Sol. Answer (6)
Total energy consumed for 8 hours = iVt
= 15 × 110 × 8 × 10–3 kWh = 13.2 kWh
Total cost = 5 × 13.2 = 66 paise
11y = 66
 y=6
7. All the energy released from the reaction X  Y, rG° = –193 kJ mol–1
is used for oxidizing M+ as M+  M3+ + 2e–, E0 = –0.25 V
Under standard conditions, the number of moles of M+ oxidized when one mole of X is converted to Y is
[F = 96500 C mol–1] [JEE(Advanced)-2015]

Sol. Answer (4)
X  Y; rG° = – 193 kJ mol–1
M+  M3+ + 2e– E° = – 0.25 V
Hence G° for oxidation will be
G° = – nFE°
= –2× 96500 × (–0.25)
= 48250 J = 48.25 kJ
48.25 kJ energy oxidises one mole M+
193
 193 kJ energy oxidizes mole M  4 mole M
48.25
8. The molar conductivity of a solution of a weak acid HX (0.01 M) is 10 times smaller than the molar conductivity
of a solution of a weak acid HY (0.10 M). If  X   Y the difference in their pKa values, pKa(HX) – pKa(HY),
0 0,
is (consider degree of ionization of both acids to be <<1) [JEE(Advanced)-2015]

Sol. Answer (3)
1  HX 2  HY
(m )HX (m )HY

1  o
2  o
m m
K a1  C112 K a2  C2 22
2 2
(m )HX (m )HY
 0.01 o 2
 0.1 o 2
( m ) ( m )
2
K a1 2
0.01(m )HX ⎛ ( ) ⎞ 2
  2
 0.1⎜ m HX ⎟  0.1⎛⎜ 1 ⎞⎟ = 10–3
K a2 0.1(m )HY ⎝ (m )HY ⎠ ⎝ 10 ⎠
K a1
pK a (HX)  pK a (HY)   log   log10 3 = 3
K a2
9. The conductance of a 0.0015 M aqueous solution of a weak monobasic acid was determined by using a
conductivity cell consisting of platinized Pt electrodes. The distance between the electrodes is 120 cm with
an area of cross section of 1 cm2. The conductance of this solution was found to be 5  10–7S. The pH of
 o
the solution is 4. The value of limiting molar conductivity m of this weak monobasic acid in aqueous solution
is Z × 102 S cm–1 mol–1. The value of Z is [JEE(Advanced)-2017]
Sol. Answer (6)
⎛ l ⎞
  C⎜ ⎟
⎝A⎠
120
 5  107 
1
= 6 × 10–5 S cm–1
  1000
M 
M
6  10 5  1000

15  10 4
 M = 40 S cm2 mol–1.
[H+] = C = 10–4
10 4 1
 
15  10 4 15
M
  º
M

 M = 40 × 15
= 600 = 6 × 102 S cm–1 mol–1
SECTION - G
Multiple True-False Type Questions
1. STATEMENT-1 : Corrosion of iron is essentially an electrochemical phenomenon.
STATEMENT-2 : Corrosion reaction at anode : 2Fe  s  2Fe3   6e
STATEMENT-3 : Corrosion reaction at cathode : O 2  g  4H  aq  4e   2H2 O l

(1) T T T (2) TFT (3) TFF (4) FFT
Sol. Answer (2)
Facts about corrosion
Statement 2 : 2Fe  s   2Fe2   4e
2. STATEMENT-1 : Using Kohlrausch's law of independent migration of ions, it is possible to calculate 0 for
any electrolyte from the ° of individual ions.
STATEMENT-2 : Limiting molar conductivity of an electrolyte can be represented as the sum of the individual
contributions of the anion and cation of the electrolyte.
STATEMENT-3 : When concentration approaches zero, molar conductivity reaches the lowest limit.
(1) T T F (2) TTT (3) FTT (4) FFT
Sol. Answer (1)
Fact.
3. STATEMENT-1 : Electrolysis of acidulated water using inert electrodes results in evolution of gases at cathode
and anode both.
STATEMENT-2 : Al3+ discharges more readily than Zn2+ at cathode.
STATEMENT-3 : In an electrolytic cell, cations move towards anode.
(1) F T T (2) TTT (3) FTF (4) TFF
Sol. Answer (4)
In electrolysis of acidulated water, H2 and O2 is evolved in 2 : 1 volume ratio, at cathode and anode
respectively.
EoAl 3 /Al  EoZn2 / Zn  Zn2+ discharges more readily at cathode.
In an electrolytic cell, cations move towards cathode, i.e., negative electrode.
SECTION - H
Aakash Challengers Questions
1. The standard potential of the following cell is 0.23 V at 15°C and 0.21 V at 35°C.
Pt|H2(g)|HCl (aq)||AgCl(s)|Ag(s)
(i) Write the cell reaction.
(ii) Calculate H° and S° for the cell reaction by assuming that these quantities remain unchanged in the
range 15°C to 35°C.
[Given SRP of Ag+(aq)|Ag(s) is 0.80 V at 25°C]
1
Sol. (i) H2 (g)  AgCl(s) H (aq)  Ag(s)  Cl– (aq)
2
⎛ E ⎞
(ii) S  nF ⎜ ⎟ , n  1, F  96500 coulombs
⎝ T ⎠P
E = 0.21 – 0.23 = – 0.02 V, T = 35 – 15 = 20°C
⎛ –0.02 ⎞ –1 –1
S  1  96500  ⎜ ⎟  – 96.5 JK mol
⎝ 20 ⎠
o
G15  –1  0.23  96500  – 22195 J mol–1
o
H15  G – TS
= –22195 – 288 × (–96.5)

= –49987 J mol–1
⇒ S  – 96.5 J k –1 mol–1 , H  – 49987 J mol–1
2. Calculate Gro of the following reaction
Ag+(aq) + Cl–(aq)  AgCl(s)
Given: Gro (AgCl)  –109 kJ mol–1; Gro (Cl– )  –129 kJ mol–1; Gro (Ag )  77 kJ mol–1
(i) Represent the above reaction in form of a cell.

(ii) Calculate E° of the cell.
(iii) Find log10Ksp of AgCl.
Sol. (i) Ag(s) | Ag+ | | AgCl | | Cl– | Cl2, Pt
o o o o
(ii) Gr  GAgCl – GAg – GCl– (Ag+(aq) + Cl–(aq)  AgCl(s))
= –109 – (–129) – 77
= –57 kJ mol–1
–57000
G  – nFE ⇒ Eocell 
–1  96500
⇒ Eocell  0.59 V
(iii) G° = –2.303 RT logK
–57000
⇒ logK   10
–2.303  6.314  298
K = 1010
1
K sp   10 –10 ⇒ log10 K sp  –10
K
3. The following electrochemical cell has been set-up:

Pt1|Fe3+|Fe2+(1M)||Ce4+ | Ce3+ (1M)|Pt2
o o
EFe 3
/Fe2
 0.77 V and ECe 4
/Ce3
 1.61 V.
If an ammeter is connected between the two platinum electrodes, predict the direction of flow of current. Will
the current increase or decrease with time?
Sol. SRP of Fe > SRP of Ce
 Fe acts as anode and Ce acts as cathode
Eocell  Eocathode – Eanode

o
 1.61 – 0.77  0.84 V
Hence, flow of current is from cathode to anode (right to left)

Current will decrease with time.
4. An excess of liquid mercury is added to an acidified solution of 1.0 × 10–3 M Fe3+. It is found that 5% of Fe3+
o
remains at equilibrium at 25°C. Calculate EHg2
/Hg
assuming that the only reaction that occurs is
2Hg + 2Fe3+  Hg22+ + 2Fe2+ [Given Eo 3 2  0.77 V ] .

Fe /Fe
Sol. 2Fe3   2Hg  2Fe2  Hg22

At t  0 1  10 –3 M 0 0
0.95  10 –3
at t(eq) 0.05  10 –3 M 0.95  10 –3 M M
2
2
0.0591 ⎡Fe2 ⎤ [Hg22 ]
Ecell  Eocell – log10 ⎣ ⎦
n [Fe3  ]2
o 0.0591 (0.95  10 –3 )2  (0.475  10 –3 )

At eqb., 0  0.77 – EHg2 – log10
/ Hg 2 (0.05  10 –3 )2
o
⇒ EHg2
/Hg
 0.792 V
5. Chromium metal can be plated out from an acidic solution containing CrO3 according to the following equation.
CrO3(aq) + 6H+(aq) + 6e–  Cr(s) + 3H2O.
(i) How many grams of chromium will be plated out by 24000 coulombs?
(ii) How long will it take to plate out 1.5 g of chromium by using 12.5 ampere current?
Sol. 52 gram of Cr is deposited by passing 6 × 96500 coulomb
52  24000
(i) Amount of Cr deposited = = 2.155 g
6  96500
(ii) M = Zit
52
⇒ 1.5   12.5  t
6  96500
 t = 1336.15 s
6. The specific conductivity of a saturated solution of AgCl is 2.30 × 10–6 ohm–1 cm–1 at 25°C. Calculate the
solubility of AgCl at 25°C if    61.9 ohm–1 cm2 mol–1 and  –  76.3 ohm –1 cm2 mol–1.
Ag Cl
1000
Sol. Dilution = Solubility
oAgCl   Ag   Cl –  61.9  76.3  138.2 ohm–1 cm2 mol–1
o
Sp. Conductivity × dilution =  AgCl
1000
2.30  10 –6   138.2
s
Solubility (gram per litre) = 2.382 × 10–3 g lt–1

7. Neglecting the liquid-liquid junction potential, calculate the emf of the following cell at 25°C.
Pt | H2(1 atm) | 0.5 M HCOOH | | 1 M CH3COOH | (1 atm)H2 | Pt
(Ka for HCOOH and CH3COOH are 1.77 × 10–4 and 1.8 × 10–5 respectively)
Sol. [H ]HCOOH  K a  C  1.77  10–4  0.5  0.9407  10–2 M
[H ]CH3COOH  1.8  10 –5  1  4.2426  10 –3 M
[H ]RHS 4.2426  10 –3

Ecell  0.0591 log10  0.0591 log10
[H ]LHS 0.9407  10 –2
 Ecell = –0.0204 V
8. For the cell reaction, Mg | Mg2+(aq) | | Ag+(aq) | Ag.
Calculate the equilibrium constant at 25°C and maximum work that can be obtained by operating the cell.
o
[ Given EMg2
/Mg
 – 2.37 V, EoAg / Ag   0.80 V ]
Sol. Eocell  0.80  2.37  3.17 V
nEocell 2  3.17
log K c    107.2758
0.0591 0.0591
Kc = 1.89 × 10107
Maximum work = – G  nFEocell = 2 × 96500 × 3.17 = 611.81 kJ
9. Under standard conditions
(i) Will Cu reduces Ag+ to Ag? (Eo   0.799 V, Eo 2  – 0.337 V)

Ag /Ag Cu / Cu
o o
(ii) Will Fe3+ be reduced to Fe2+ by Sn2+? (EFe3 /Fe2  0.771 V, ESn2 / Sn4  – 0.13 V)
(iii) Would you use a silver spoon to stir a solution of Cu(NO3)2?
Sol. (i) Yes, Eocell of Cu | Cu2+ | | Ag+ | Ag is positive
(ii) Yes, Eocell of Pt, Sn4+ | Sn2+ | | Fe3+ | Fe2+, Pt is positive
(iii) Yes, the reaction between silver and Cu2+ does not occur
10. A weak monobasic acid is 5% dissociated in 0.01 mol/lt solution. The limiting molar conductivity at infinite
dilution is 4 × 10–2 ohm–1 cm2 mol–1. Calculate conductivity of 0.05 molar solution of acid.
Sol. Ka = C2 = 0.01 × (0.05)2 = 2.5 × 10–5
Ka 2.5  105
For C = 0.05 M,   
C 0.05
  = 0.0223
M
  o
⇒ M  0.0223  4  10 2
M
11. 500 ml CuSO4 solution was electrolysed using a current of 2 amp (efficiency = 75%) for 60 min. Calculate
the pH of solution at the end of electrolysis at 298 K. (Assume initial pH = 7)
Sol. When CuSO4 solution is electrolysed then H2SO4 is formed.
1 75
Equivalents of H2SO4 = 2 × 60 × 60 = 0.0559
96500 100
0.0559
NH2SO4 = = 1.12 × 10–1
500
1000
Now, [H+] = 1.12 × 10–1

pH = – log [H+] = – log 1.12 × 10–1
pH = 1 – 0.05 = 0.95
12. A constant current flowed for 30 min through a solution of KI oxidising the iodide ion to iodine. At the end of
experiment, the iodine was titrated with 10 ml 0.075 M Na2S2O3 solution. Calculate the strength of current.
Sol. t = 30 min = 30 × 60 = 1800 s
KI  K++I–
H2O  H++HO–
(Cathode) 2H+ + 2e H2
(Anode) 2I–  I2 + 2e–
eq. (I2) = eq. (Na2S2O3) = 10–3 × 10 × 0.075 = 0.75 × 10–3
w it wF (0.75  10 –3 ) (96500)
 =  i= =
E F Et 30  60
i = 0.04 A
13. A direct current of 3.0 amp (efficiency 75%) was passed through 400 ml 0.2 M Fe2(SO4)3 solution for a period
of 60 min. The resulting solution in cathode chamber was analysed by titrating against acidic KMnO4 solution
20 ml of KMnO4 required to reach the end point. Determine the molarity of KMnO4 solution.
1 75
Sol. Equivalents of Fe2+ formed = 3 × 60 × 60 = 0.0839
96500 100
Equivalents of Fe2+ = Equivalents of KMnO4
0.0839 = NKMnO4 × 20 × 10–3
0.0839
NKMnO4 = × 103
20
NKMnO4 = 4.195
In acidic medium, n-factor for KMnO4 is 5.
4.195
MKMnO4 = = 0.84 M
5
14. H2O2 can be produced by successive reactions

2NH4HSO4  H2 + (NH4)2S2O8
60%
(NH4 )2 S 2O 8  2H2O   2NH4HSO 4  H2O 2
The first reaction is an electrolytic reaction and second is steam distillation. What amount of current
would have to be used in first reaction to produce enough (NH4)2S2O8 to yield 100 gm H2O2 per hour?
(Assume current efficiency is 75%)
Sol. Given
(NH4)2S2O8 + H2O 2NH4HSO4 + H2O2
228 g 34g
34 gm of H2O2 is produced by 228 g (NH4)2 S2O8
228
100 g of H2O2 will be produced by × 100 = 670 g
34
670  100
Since efficiency is 60% hence mass of (NH4)2 S2O8 required will be = = 1116.66 gm
60
Equivalent mass of (NH4)2 S2O8 may be calculated
2NH4 SO4–  (NH4)2S2O8+2e–
ENH  S O = M = 228 = 114

4 2 2 8
2 2
From I- law
Ei t
w=
F
75
i  3600  114
1116.66 = 100
96500
i = 350.09 A
15 During discharge of a lead storage battery the density of sulphuric acid fell from 1.3 to 1.15 gm/ml. Sulphuric
acid of density 1.3 gm/ml is 40% H2SO4 by wt and that of density 1.15 gm/ml is 20% by wt. The battery holds
4.0 L of the acid and volume remained practically constant during the discharge. Calculate the number of amp-
hours for which the battery must have been used.
Pb + SO4–2  PbSO4 + 2e– (discharging)
PbO2 + 4H+ + SO4–2 + 2e–  PbSO4 + 2H2O (discharging)
Sol. Adding the charging and discharging reactions.
We get
Pb + PbO2 + 4H+ + 2SO2–

4  2PbSO4 + 2H2O
NH2SO4 = MH2SO4 (since 2SO2–

4 requires 2-electrons)
i.e., Normality = Molarity

Before discharge
40  1.3  1000
MH2SO4 = = 5.3 M
98  100
Moles of H2SO4 = 5.3 × 4 = 21.22

After discharge
20  1.15  1000
MH2SO4(ii) = = 2.34 M
98  100
Moles of H2SO4 = (2.34) (4) = 9.38

Moles or equivalents of H2SO4 Used = 21.22 – 9.38 = 11.84
i × t = (11.84) × 96500 = 317 ampere H.
16. The resistance of a conductivity cell filled with 0.01 N KCl at 25°C was found to be 500 . The specific
conductance of 0.01 N KCl at 25°C is 1.41 × 10–3 –1 cm –1. The resistance of same cell filled with
0.3 N ZnSO4 at 25°C was found to be 69 . Calculate the cell constant, equivalent and molar conductivities
of ZnSO4 solution.
1 l
Sol. K = ×
R A
1 l
 (1.41 × 10–3) = ×
500 A
l
= 1.41 × 10–3 × 500 = 0.705
A
K  1000 1 l 1000
m = = × ×
M R A M
1 1000
= × 1.41 × 10–3 × 500 ×
69 0.3
= 34.1 –1 cm–1 eq–1.

 Molar conductivity = 68.2 –1cm–1mol–1.
17. The equivalent conductance of 0.1 N of H3PO4 at 18°C is 96.5 –1 cm2 eq–1. If °HCl = 378.3, °NaCl = 109,
Λ NaH2PO 4  70 Ω –1 cm 2 eq –1 respectively, calculate the degree of dissociation and dissociation constant for
the reaction :
H3PO4 H+ + H2PO4–
o o o o
Sol. H3PO4 = HCl  NaH2PO4 – NaCl = 378.3 + 70 – 109 = 339.3
H3PO4 96.5
= = = 0.2844
Ho 3PO4 339.3
C. 2 0.1  (.2844)2

K= = = 1.13 × 10–2
(1 –  ) (1 – .28844)
18. Ag(s) | AgCl (saturated salt), KCl (C = 0.025) || KNO3, AgNO3 (C = 0.2) | Ag
The emf of above cell is 0.43 V.
(a) Write down the cell reaction.

(b) Calculate the solubility product of AgCl.
(Antilog (4.2758) = 1.887 × 104)
Sol. The given cell

Ag(s) |AgCl (Saturated Salt), KCl (C = 0.025 M)||AgNO3(C=0.2)|Ag
E = 0.43V
(a) Reaction in L.H.C. and R.H.C.
Ag Ag+ + e– (Anode)
Ag+ + e– Ag (Cathode)
o 0.0591
(b) E = E Ag/ Ag – log [Ag+]L
Ag/ Ag 1
o 0.0591 1
E
Ag / Ag
= E Ag / Ag – log
1 [Ag ]R
EMF of cell = E E
Ag/ Ag Ag / Ag
o o 0.0591 [Ag ]L
 E = (E Ag/ Ag  E Ag / Ag ) – log
1 [Ag ]R
⇓
0
0.0591 [Ag ]L
 E= log
1 (0.2)
0.43 [Ag ] 0.43 0.2

– = log or = log
0.0591 (0.2) 0.0591 [Ag ]
0.2
 = 1.887 × 106 ; [Ag+] = 1.05 × 10–10 M.
[Ag ]
Therefore, [Ag+] = 1.05 × 10–10 M
K   Cl–
KCl  0.025 0.025
 Ksp (AgCl) = (0.025) (1.05 × 10–10)
 Ksp = 2.64 × 10–10
19. Pt | H2(1 bar), H+ || KCl (1.0 M saturated) | Hg2Cl2 | Hg was used to measure the pH of 0.05 M acetic acid
in 0.04 M CH3COONa. Calculate the cell potential.
K a(CH3 COOH)  1.8  10 5 , EHg Cl /Hg, Cl–

 0.28 V
2 2
[Acid] 0.05
Sol. [H+] = Ka × = 1.8 × 10–5 × = 2.25 × 10–5
[Salt] 0.04
o 0.059 [H ]
ECell = (EHg – – Eo  )– log
2Cl2 /Hg, Cl H /H2 1 1
0.059
ECell = 0.28 – log 2.25 × 10–5
1
ECell = 0.28 + 0.275 = 0.555 V
20.
V
Ag Salt bridge Zn
Zn(NO3)2
0.5 M AgNO3
(A) (B)
(a) If the cell emf is – 1.58 V, what is the concentration of Zn+2?
(b) If NH3 added to half cell A, how emf of cell will change?
E Ag /Ag  0.8 V, E Zn 2 /Zn  0.76 V Antilog (0.6768) = 1.4768
Sol. (a) [Zn+2] = 0.054 M; (b) emf increases
21. ECu2 /Cu  0.34 V, EZn/Zn2  0.76 V
A cell formed by the combination of Cu and Zn.
(a) When CuSO4 is added to Cu+2 compartment what is the effect on emf of cell?
(b) When NH3 is added to Cu+2 compartment what is the effect on emf of cell?
(c) When ZnSO4 is added to Zn+2 compartment what is the effect on emf of cell?
(d) When Zn+2 is diluted what is the effect on emf of cell?
o o
Sol. ECu2 /Cu = 0.34V; E Zn/ Zn2 = 0.76 V
 EMF of the cell is

o o
Eº = E Zn/ Zn2 + ECu2 /Cu
 (0.34) + (0.76) = 1.1V

(a) According to Nernst equation
0.0591 [Zn2 ]
E = Eº – log
2 [Cu2 ]
[Cu2+] increases
Hence log terms will decreases and therefore EMF increases.
(b) When NH3 is added it combines with Cu2+ and, hence, [Cu2+] decreases
4NH3 + Cu2+  [Cu (NH3)4]2+.
With decrease in [Cu2+], log tem increase hence EMF decreases.
(c) [Zn2+] will increase as result of which EMF decreases.
(d) Zn2+ dilution means concentration decreases and EMF increases.


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Chapter 3

Adding (i) & (iii) subtract (ii)

 Equivalent ionic conductance for Na+ is 52.5.

volume volume volume volume

Vol. of KCl Vol. of KCl Vol. of KCl Vol. of KCl

Sol. Answer (3)

100  103 570

21. Which is correct increasing order of deposition?

22. Which is the correct order of deposition of anion?

23. Rate of corrosion is maximum when

As EoZn2 / Zn is less than Eo 

28. The Ecell of the reaction

MnO4– + Fe2+ + H+  Mn2+ + Fe3+ + H2O

(1) +0.683 V (2) –0.367 V (3) 0.754 V (4) +0.3415 V

EoCu2 /Cu = +0.153 V and EoCu /Cu = 0.53 V

Cu2+ + 2e  Cu; 0.153

 EoCu2 /Cu = – 0.224

or EoCu /Cu2 = 0.224

 Eº = 0.224 + 0.53 = 0.754 V

33. E(Na  /Na)  2.71 V, E(Mg 2 /Mg)  2.37 V

E(Fe  2 /Fe)  0.44 V, E(Cr  3 /Cr)  0.41 V

Based on this data, which is the poorest reducing agent?

Given (i) ... Cu2+ + 2e–  Cu(s); E1o = 0.337 V

(ii)... Cu2+ + e–  Cu+ Eo2 = 0.153 V

Reversing equation (ii); we get

 – FEº = [– 2× F × (0.337)] + [–F × –0.153]

35. What is G° for the following reaction?

(1) –44.5 kJ (2) 44.5 kJ (3) –89 kJ (4) 89 kJ

EoCell = E Ag/ Ag  ECu2 /Cu

 EoCell = (– 0.8) + (0.34) = – 0.46

37. Emf of the cell

38. Which metal oxide is thermally unstable?

39. H2(1 atm) | 2.26 M HCOOH || 0.222 M CH3COOH| (1 atm) H2

[H+]L = C1 = (Ka)1  C1

C2(1 – )C2 C2

0.0591 1.77  10 4  2.26

40. Given that

Go = G1o  Go2  – nF(E1o  Eo2 )

= –2 × 96500 × (1.678 + 0.49) J mol–1

o 0.0591 [Ag(NH3 )2 ]

 Eocell  0.0591  log10 K C  0.0591  log10 (6  10–14 )

 EoOP( Ag/ Ag )  ERP(

 EoAg(NH   – 0.780  0.799

43. Consider the following cell reaction:

H2 (g)  M4   2H  M2

H 2  M2  (1)2  M2  M2  , º

G = G° + 2.303 RT log Q

1. Which of following is/are correct?

3. Which compounds have maximum conductivity?

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

Vol. of NaOH Vol. of NaOH Vol. of NaOH Vol. of NaOH

Sol. Answer (2, 3, 4)

For Cl– = 0.036; Molarity = 0.1 – 0.036 = 0.064

9. Which statement is correct about electrolysis of CuSO4?

CuSO4  Cu2+ + SO2–

11. For the electrolysis of CuSO4 solution which is/are correct?

Cu2+, H+, HO– and SO2–

13. Zn | Zn+2 (1M) || Ni+2 (1 M) | Ni, antilog (0.7411) = 5.5

14. Which is/are correct statements about salt bridge?

15. Ksp for AgBr = 8 × 10–13

Ksp (AgBr) = [Ag+] [Br–]

16. Which statement is/are correct?

17. E Zn 2 /Zn  0.76 V, ENi 2 /Ni  0.24 V