

 JEE Advanced Chemistry 10 Years Topicwise Questions with Solutions

®
PHYSICAL CHEMISTRY
ELECTROCHEMISTRY
1. Plotting 1/Λm against cΛm for aqueous solutions of a monobasic weak acid (HX) resulted in a straight line
with y-axis intercept of P and slope of S. The ratio P ⁄ S is [JEE(Advanced) 2023]
[Λm = molar conductivity

Λ °m = limiting molar conductivity

c = molar concentration
Ka = dissociation constant of HX]

(A) Ka Λ °m (B) Ka Λ °m / 2 (C) 2 Ka Λ °m (D) 1 / (Ka Λ °m )

0
2. The reduction potential (E , in V) of MnO 4– (aq)/Mn(s) is _______. [JEE(Advanced) 2022]

[Given : E 0MnO– = 1.68V ; E 0MnO s /Mn 2+ aq = 1.21V ; E 0Mn 2+ aq /Mn s = –1.03V ]

( 4 ( aq ) /MnO2 ( s ) ) ( 2( ) ( )) ( ( ) ( ))
3. Consider the strong electrolytes ZmXn, UmYp and VmXn. Limiting molar conductivity (Λ0) of UmYp and
2 –1
VmXn are 250 and 440 S cm mol , respectively. The value of (m + n + p) is _______.
Given:
n+ p+ n+ m– m–
Ion Z U V X Y
λ (S cm mol ) 50.0 25.0 100.0 80.0 100.0
0 2 –1

λ is the limiting molar conductivity of ions

0

The plot of molar conductivity (Λ) of ZmXn vs c

1/2
is given below. [JEE(Advanced) 2022]
Λ of ZmXn (S cm2 mol–1)

339

336

0.01 0.02 0.03 0.04

c (mol L–1)1/2
1/2

4. The correct option(s) about entropy (S) is(are) [JEE(Advanced) 2022]

[R = gas constant, F = Faraday constant, T = Temperature]
dE cell R
(A) For the reaction, M(s) + 2H (aq) → H2(g) + M (aq), if
+ 2+
= , then the entropy change of the
dT F
reaction is R (assume that entropy and internal energy changes are temperature independent).
(B) The cell reaction, Pt(s) | H2(g, 1bar) | H+(aq, 0.01M) || H+(aq, 0.1M) | H2(g, 1bar) | Pt(s), is an
entropy driven process.
(C) For racemization of an optically active compound, ∆S > 0.
(D) ∆S > 0, for [Ni(H2O)6]2+ + 3 en → [Ni(en)3]2+ + 6H2O (where en = ethylenediamine).

For More Material Join: @JEEAdvanced_2024

 JEE Advanced Chemistry 10 Years Topicwise Questions with Solutions ®
5. Some standard electrode potentials at 298 K are given below: [JEE(Advanced) 2021]
2+
Pb /Pb –0.13 V
2+
Ni /Ni –0.24 V
2+
Cd /Cd –0.40 V
2+
Fe /Fe –0.44 V
2+
To a solution containing 0.001 M of X2+ and 0.1 M of Y , the metal rods X and Y are inserted (at 298 K)
and connected by a conducting wire. This resulted in dissolution of X. The correct combination(s) of
X and Y, respectively, is (are)
(Given: Gas constant, R = 8.314 J K–1 mol–1,
Faraday constant, F = 96500 C mol–1)
(A) Cd and Ni (B) Cd and Fe (C) Ni and Pb (D) Ni and Fe
Question Stem for Question Nos. 6 and 7
Question Stem
2 2
At 298 K, the limiting molar conductivity of a weak monobasic acid is 4 × 10 S cm mol–1. At 298 K, for an
aqueous solution of the acid the degree of dissociation of α and the molar conductivity is
y × 102 S cm2 mol–1. At 298 K, upon 20 times dilution with water, the molar conductivity of the solution
becomes 3y×102 S cm2 mol–1.
6. The value of α is ______. [JEE(Advanced) 2021]
7. The value of y is ______. [JEE(Advanced) 2021]
8. Consider a 70% efficient hydrogen-oxygen fuel cell working under standard conditions at 1 bar and 298
K. Its cell reaction is [JEE(Advanced) 2020]
1
H2 (g) + O2(g) → H2O().
2
–3
The work derived from the cell on the consumption of 1.0 × 10 mol of H2(g) is used to compress
1.00 mol of a monoatomic ideal gas in a thermally insulted container. What is the change in the
temperature (in K) of the ideal gas ?
The standard reduction potentials for the two half-cells are given below.
O2(g) + 4 H+ (aq.) + 4e– → 2H2O () , Eº = 1.23 V,

2H (aq.) + 2e → H2(g), Eº = 0.00V.

+ –

–1 –1 –1
Use F = 96500 C mol , R = 8.314 J mol K
9. For the electrochemical cell, [JEE(Advanced) 2018]
2+ 2+
Mg(s)|Mg (aq, 1M)||Cu (aq, 1M) | Cu(s)
2+
the standard emf of the cell is 2.70 V at 300 K. When the concentration of Mg is changed to x M, the
cell potential changes to 2.67 V at 300 K. The value of x is______.
F
(given, = 11500 KV–1, where F is the Faraday constant and R is the gas constant, ln(10) = 2.30)
R
10. Consider an electrochemical cell: A(s) | A
n+
(aq, 2M) || B2n+ (aq, 1M) | B(s). The value of ∆Hθ for the cell
θ θ
reaction is twice that of ∆G at 300 K. If the emf of the cell is zero, the ∆S (in JK mol ) of the cell
–1 –1

reaction per mole of B formed at 300 K is______.

(Given : ln (2) = 0.7, R (universal gas constant) = 8.3 J K–1 mol–1. H, S and G are enthalpy, entropy and
Gibbs energy, respectively.) [JEE(Advanced) 2018]
2

For More Material Join: @JEEAdvanced_2024

 
 JEE Advanced Chemistry 10 Years Topicwise Questions with Solutions
®
11. 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
2
with an area of cross section of 1 cm . The conductance of this solution was found to be
5 × 10 S. The pH of the solution is 4. The value of limiting molar conductivity ( Λ 0m ) of this weak
–7

monobasic acid in aqueous solution is Z × 102S cm–1mol–1. The value of Z is. [JEE(Advanced) 2017]
12. For the following cell : [JEE(Advanced) 2017]
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 , Eº(cell) = 1.1V]
(A) 2.303 RT + 1.1F (B) 2.303 RT – 2.2F
(C) 1.1 F (D) –2.2 F
13. For the following electrochemical cell at 298K, [JEE(Advanced) 2016]
+ 4+ 2+
Pt(s) | H2(g, 1bar) | H (aq, 1M) || M (aq.), M (aq.) | Pt(s)

[M 2+ (aq.)]
Ecell = 0.092 V when = 10 x
[M 4+ (aq.)]

RT
Given : E 0M 4+ /M2+ = 0.151V ; 2.303 = 0.059
F
The value of x is -
(A) –2 (B) –1 (C) 1 (D) 2
All the energy released from the reaction X → Y, ∆rGº = –193 kJ mol
–1
14. is used for the oxidizing M+ and
M → M + 2e¯, Eº = –0.25 V.
+ 3+

+
Under standard conditions, the number of moles of M oxidized when one mole of X is converted to Y is
–1
[F = 96500 C mol ] [JEE(Advanced) 2015]
15. 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 (0.1 M). If λ
0
X– ≈ λ0Y–, the difference in their pKa values,
pKa(HX) – pKa(HY), is (consider degree of ionization of both acids to be <<1).
[JEE(Advanced) 2015]
16. In a galvanic cell , the salt bridge - [JEE(Advanced) 2014]
(A) Does not participate chemically in the cell reaction
(B) Stops the diffusion of ions from one electrode to another
(C) Is necessary for the occurence of the cell reaction
(D) Ensures mixing of the two electrolytic solutions

For More Material Join: @JEEAdvanced_2024

 JEE Advanced Chemistry 10 Years Topicwise Questions with Solutions ®
SOLUTIONS
1. Ans. (A)
Λm
Sol. For weak acid, α =
Λ0

Cα 2
Ka = ⇒ Ka (1 – α) = Cα2
1− α
2
 Λ  Λ 
⇒ Ka  1 − m  = C  m 
 Λ0   Λ0 

Λ m K a CΛ 2m
⇒ Ka − =
Λ0 (Λ 0 )2

Divide by ' Λ m '

K CΛ m K a
⇒=a
+
Λm (Λ 0 )2 Λ 0
1 CΛ m 1
=
⇒ +
Λ m K a (Λ 0 ) 2
Λ0

1
Plot vs C Λ m has
Λm
1
Slope = =S
K a (Λ 0 )2
1
y-intercept = =P
Λ0
1
P Λ0
Then, = = Ka Λ0
S 1
K a (Λ 0 )2
2. Ans. (0.74 - 0.80)
+7 +4

Sol.
M nO 4– → M nO2 
(3) (2)
→ Mn +2 
(2)
→ Mn
7
For the required reaction ∆G° = ∆G°1 + ∆G°2 + ∆G°3
⇒ 7 × E = 1.68 × 3 + 1.21 × 2 + (–1.03) × 2
5.4
=
E = 0.7714
7
Ans. = 0.77

For More Material Join: @JEEAdvanced_2024

 
 JEE Advanced Chemistry 10 Years Topicwise Questions with Solutions
®
3. Ans. (7)
Sol. ( )
Λ° U m Yp = m × λ °
Up
+ + p × λ ° Ym −= 250

25m + 100p = 250

m + 4p = 10 ....(1)
Λ° ( Vm X n=
) m × λ Vn + + n × λ °X m=
− 440
100m + 80n = 440
5m + 4n = 22 ....(2)
340

339

336

0.01 0.04

From the extrapolation of curve

Λ° ( Z m X n ) = 340

m × λ °Z n + + nλ °X m − = 340
50m + 80n = 340
5m + 8n = 34 ....(3)
(3) — (2) ⇒ 4n = 12 ⇒ n = 3
Putting in (2) we get m = 2
Putting in (1) we get p = 2
m+n+p=2+3+2=7
4. Ans. (B, C, D)
Sol. ∆G = ∆H – T∆S
 d∆G 
∆G = ∆H + T  
 dT p
 dEcell 
–nF   =–∆S
 dT 
dEcell ∆S R
= = ( given )
dT nF F
⇒ ∆S = nR
For the reaction, M(g) + 2H⊕(aq) → H2(g) + M2⊕(aq)
n=2
⇒ ∆S = 2R
Hence, option (A) is incorrect

For More Material Join: @JEEAdvanced_2024

 JEE Advanced Chemistry 10 Years Topicwise Questions with Solutions ®
For the reaction, Pt(s) |H2(g), 1 bar| H⊕aq(0.01M)|| H⊕(aq, 0.1M) | H2(g, 1 bar)| Pt(s)
0.0591 0.01
Ecell = E°cell − log =
0.0591V
1 0.1
Ecell is positive ⇒ ∆G < 0 and ∆S > 0 (∆H = 0 for concentration cells)
Hence, option (B) is correct
Racemization of an optically active compound is a spontaneous process.
Here, ∆H = 0 (similar type of bonds are present in enantiomers)
⇒ ∆S > 0
Hence, option (C) is correct.
2+ 2+
Ni ( H2O )6  + 3 en → Ni ( en )3  + 6H2O is a spontaneous process
more stable complex is formed
⇒ ∆S > 0
Hence, option (D) is correct.
5. Ans. (A, B, C)
Sol. x(s) → x
+2
(0.001 M) + 2e¯ (anode)
y +2
(0.1 M) + 2e¯ → y (s) (cathode)
______________________________
0.06 x +2
Ecell = E°cell − log +2
2 y
Ecell = E°cell + 0.06
(A) Cd and Ni E°cell = + 0.4 – 0.24 ; Ecell = 0.22
(B) Cd and Fe E°cell = – 0.04 ; Ecell = 0.02
(C) Ni and Pb E°cell = 0.11 ; Ecell = 0.17
(D) Ni and Fe E°cell = – 0.2 ; Ecell = –0.14
since in (A) (B) (C) Ecell is positive hence answer is (A) (B) (C).
6. Ans. (0.21 or 0.22)
Λ 2m C
( )
Sol. Ka =
Λ °m Λ °m − Λ m

C
(y ×10 2 )2 × C (3y ×10 2 )2 ×
Ka = = 20
4 ×10 (4 ×10 − y ×10 ) 4 ×10 (4 ×10 − 3y ×10 2 )
2 2 2 2 2

1 9 44
⇒ = ⇒y=
(4 − y) 20 (4 − 3y) 51
44
×10
α = 51 2
4 ×10
α = 0.2156 (α = 0.22 or 0.21)
y = 0.86

For More Material Join: @JEEAdvanced_2024

 
 JEE Advanced Chemistry 10 Years Topicwise Questions with Solutions
®
7. Ans. (0.86)
8. Ans. (13.00 - 13.60)
Sol. E 0cell = 1.23 – 0.00 = 1.23 V
∆G 0cell = –nF E 0cell = –2 × 96500 × 1.23 J
∴ Work derived from this fuel cell

× ( −∆G cell )
70 −3
= 0
× 10= xJ
100
Since insulated vessel, hence q = 0
From equation, for monoatomic gas,
 3R 
w = ∆U ⇒ x=nCV,m ∆T CV ,m = 
 2 
70 3
or, × ( 2 × 96500 × 1.23 ) × 10 −3 = 1 × × 8.314 × ∆T
100 2
∴ ∆T = 13.32
9. Ans. (10)
Sol. Mg(s) + Cu (aq) → Mg (aq) + Cu(s)
2+ 2+

E°Cell = 2.70 ECell = 2.67 Mg2+ = x M

2+
Cu = 1 M
RT
ECell = E°Cell – ln x
nF
RT
2.67 = 2.70 – ln x
2F
R × 300
–0.03 = – × ln x
2F
0.03 × 2 F 0.03 × 2 × 11500
lnx = × =
300 R 300 × 1
lnx = 2.30 = ln(10)
x = 10
10. Ans. (–11.62)
+n +2n
Sol. A(s) | A (aq, 2M) || B (aq, 1M) | B(s)
∆H° = 2∆G°0 Ecell = 0
Cell Rx A → A + ne ] × 2
+n –

B + 2n e → B(s)
+2n –

2A(s) + B+2n ( aq ) → 2A + n ( aq ) + B ( s )
1M 2M

[ A + n ]2
∆G = ∆G° + RT ln
[ B+2n ]
[ A + n ]2 22
∆G° = – RT ln +2n = – RT. ln = –RT.ln 4
[B ] 1
∆G° = ∆H° – T∆S°
∆G° = 2∆G° – T∆S°
∆G ° RT ln 4
∆S° = = − = – 8.3 × 2 × 0.7 = –11.62 J/K.mol
T T
7

For More Material Join: @JEEAdvanced_2024

 JEE Advanced Chemistry 10 Years Topicwise Questions with Solutions ®
11. Ans. (6)

1000 l
κ× G ×   × 1000
Λ c = κ × 1000 = a
C
+ m
Sol. For weak acid [H ] = cα = c =c×
Λ ∞
m
∞
Λm Λm∞
Λ ∞m

 120 
5 × 10−7 ×   × 1000
10–4 =  1  ⇒Z=6
Z × 102

12. Ans. (B)

Sol. ∆G = ∆G + 2.303RT logQ

0

∆G = – nFE + 2.303RT logQ

0

Given : Eº = 1.1 V and n = 2

[Zn +2 ]
∆G = (– 2 × 1.1 × F) + 2.303RT log [
Cu +2 ]

∆G = –2.2 F + 2.303RT

13. Ans. (D)

Sol. At anode : H2(g) 2H+ (aq) + 2e–

4+ – 2+
At cathode : M (aq) + 2e M (aq)

Net cell reaction : H2(g) + M4+ (aq) 2H+ (aq) + M2+ (aq)

2
 H +   M 2 + 
Now, Ecell = (E º
M 4+ / M 2+
− E Hº + / H
2
) −
0.059
n
.log
PH .  M 4 + 
2

0.059 12 ×  M 2 + 
or, 0.092 = (0.151 – 0) – .log
2 1 ×  M 4 + 

 M 2 + 
∴ = 10 2 ⇒ x = 2
 M 4 + 

14. Ans. (4)

Sol. |∆G| = – nFE

193 × 103 = x × 2 × 96500 × 0.25

+
(where x is the number of moles of M oxidised)

x=4

For More Material Join: @JEEAdvanced_2024

 
 JEE Advanced Chemistry 10 Years Topicwise Questions with Solutions
®
15. Ans. (3)
x
Sol. Λ m (HX) = Λ m (HY) =
x
10

Λ m (HX) / Λ0m (HX) (x / 10) / Λ 0m (HX) α 1

= = 1 =
Λ m (HY) / Λ m (HY)
0
x / Λ m (HY)
0
α 2 10

HX 
 H+ + X– HY 
 H+ + Y–
0.01 – – 0.1 – –
0.01(1 – α1) 0.01 α1 0.01 α1 0.1(1 – α2) 0.1 α2 0.1 α2

=
K a1 0.01α12 K a=
2
0.1α 22

K a1 1 α12 1
= =. 2
K a 2 10 α 2 1000

log Ka1 – log Ka2 = – 3

pKa1 – pKa2 = 3
16. Ans. (A, B)
Sol. Note : We feel option (C) is incorrect because in some type of concentration cells, salt bridge is not
required. Which can be confirmed from NCERT (XII-Chemistry, Part-1) in Sub section 3.2 Galvanic Cell.
"The electrolytes of the two half-cells are connected internally through a salt bridge as shown in Fig. 3.1.
Sometimes, both the electrodes dip in the same electrolyte solution and in such cases we do not require a
salt bridge. "

For More Material Join: @JEEAdvanced_2024