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1. For an aqueous solution at 25°C, the Debye-Huckel limiting law is given by: [NET JUNE 2011]
(a) log   0.509 | Z Z |  (b) log   0.509 | Z Z | 

(c) log    0.509 | Z Z |  (d) log    0.509 | Z Z | 2

2. Given [NET JUNE 2011]
Ag + e → Ag, E0 = 0.50 V
+

Cu2+ + 2e → Cu, E0 = 0.34 V

A 100 ml solution is 1080 mg with respect to Ag+ and 635 mg with respect to Cu2+. If 0.1 mg Ag+ left in
the solution is considered to be the complete deposition of Ag +, the cathode potential, so that no copper
is deposited during the process, is: [NET JUNE 2011]
(a) 0.16 V (b) 0.84 V (c) 0.31 V (d) –0.16 V
3. Debye-Huckle screening length (k–1) is a measure of size of diffuse ion cloud around an ion, provided

 
1
2e2 NA
 30 nm molKg 1 at 298 K, which of the following values of k–1 is true for a 0.03 molal
0 k BT
solution for Na2SO4 in water (r  100) : [NET JUNE 2011]

10 9 10 2 9
(a) nm (b) nm (c) nm (d) nm
9 10 9 10 2
[O] 2
4. If the ratio of composition of oxidized and reduced species in electrochemical cell, is given as e ,
[R]
the correct potential difference will be: [NET JUNE 2011]
2RT 2RT RT RT
(a) E  E 0  (b) E  E 0  (c) E  E 0  (d) E  E 0 
nF nF nF nF
5. Which one of the following conductometric titrations will show a linear increase of the conductance
with volume of the titrant added up to the break point and an almost constant conductance afterwards.
[NET DEC 2011]
(a) A strong acid with a strong base
(b) A strong acid with a weak base
(c) A weak acid with the a strong base
(d) A weak acid with a weak base
6. For a potentiometric titration, in the curve of emf(E) vs volume (V) of the titrant added, the equivalence
point is indicated by: [NET DEC 2011]
2 2 2 2
(a) |dE/dV| = 0,|d E/dV | = 0 (b) |dE/dV| = 0,|d E/dV | > 0
2 2
(c) |dE/dV| > 0,|d E/dV | = 0 (d) |dE/dV| > 0,|d2E/dV2| > 0
7. The standard electrode potentials (E°) of Fe3+/Fe2+ and Fe2+ / Fe electrodes are + 0.77V and –0.44 V
respectively at 300 K. The E° of Fe+3/Fe electrode at the same temperature is: [NET DEC 2011]
(a) 1.21 V (b) 0.33 V (c) –0.11 V (d) –0.04 V
8. The overall reaction for the passage of 1.0 faraday of charge in the following cell
Ag(s)–AgCl(s)| KCl(a1)|KCl(a2)| AgCl(s) – Ag(s) is give by (t denotes the transport numbers)

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[NET DEC 2011]

(a) t+KCl(a1) → t+KCl(a2) (b) t+KCl(a2) → t+KCl(a1)
(c) t–KCl(a1) → t–KCl(a2) (d) t–KCl(a2) → t–KCl(a1)
9. The molar conductivities at infinite dilution  0m for Na2SO4, K2SO4, KCl, HCl and HCOONa at 300 K
are 260, 308, 150, 426 and 105 S cm–1 mol–2 respectively. Hence  0m for formic acid in the same unit
and at the same temperature is: [NET DEC 2011]
(a) 381 (b) 405 (c) 429 (d) 531
10. The spectrophotometric response for the titration of a mixture of Fe and Cu2+ ions against EDTA is
3+

given below: [NET JUNE 2012]

The correct statement is:

(a) VolumeabFe3 andvolumecd Cu 2+ 
   
(b) VolumeabCu 2 andvolumecd Fe3+ 
   
(c) VolumeabFe3 andvolumeabexesssD
 
(d) VolumeabCu 2 andvolumecdexesssD
 
11. The correct value of E°, of a half cell in the following graph of E vs log m (molality) is:
[NET JUNE 2012]

(a) CC’/AC’ (b) AB’ (c) BB’ (d) CC’

12. The correct Nernst equation for the concentration cell. [NET JUNE 2012]
Pt | H2(p) | HCl(a)1| AgCl(s)| Ag | AgCl(s) | HCl(a )1 H2(p) | Pt
Without liquid junction would be:
2RT (a  )1 RT (a  ) 2
(a) E ln (b) E ln
F (a  ) 2 F (a  )1
2RT (a  ) 2 RT (a  ) 2
(c) E ln (d) E ln
F (a  )1 2F (a  )1
13. Main assumption (s) involved in the derivation of Debye-Huckel equation is (are) the validity of
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[NET JUNE 2012]

(a) Only poission equation
(b) Poission equation and Boltzmann distribution
(c) Poission equation, Boltzmann distribution and |Ze| >>kBt
(d) Poission equation Boltzmann distribution and |Ze|<<kBT
14. For the deposition of Pb by electroplating, the best suited compound among the following is:
[NET DEC 2012]
(a) PbCl2 (b) PbSO4 (c) Pb(Et)4 (d) Pb(BF4)2
15. The Daniel cell is: [NET DEC 2012]
(a) PtI(s)| Zn(s) | Zn2+ (aq) || Cu2+(aq) | Cu(s) | PtII(s)
(b) PtI(s)| Zn(s) | Zn2+ (aq) || Ag+(aq) | Ag(s) | Pt II(s)
(c) Pt1(s)| Fe(s) | Fe2+ (aq) || Cu2+(aq) | Cu(s) | Pt II(s)
(d) Pt1(s)| H2(s) | H2SO4 (aq) || Cu2+(aq) | Cu(s) | PtII(s)
16. Kohlrausch’s law is applicable to a dilute solution of: [NET DEC 2012]
(a) Potassium chloride in hexane (b) Acetic acid in water
(c) Hydrochoric acid in water (d) Benzoic acid in benzene
17. On subjecting 9.5 ml solution of Pb of XM to polarographic measurements, Id was found to be 1 μA.
2+

When 0.5 mL of 0.04 M Pb2+ wad added before the measurement, the Id was found to be 1.25 μA:
[NET DEC 2012]
(a) 0.0035 (b) 0.0400 (c) 0.0067 (d) 0.0080
18. A solution of 2.0 of brass was analyzed for Cu electrogravimetrically using Pt-gauze as electrode. The
weight of Pt-gauze changed from 14.5 g to 16.0 g. The percentage weight of Cu in brass is:
[NET DEC 2012]
(a) 50 (b) 55 (c) 60 (d) 75
19. The equilibrium constant for an electrochemical reaction, [NET DEC 2012]
2Fe3+ + Sn2+ ⇌ 2Fe2+ + Sn4+
Is [E°(Fe3+/Fe2+) = 0.75 V, E°(Sn4+/Sn2+) = 0.15 V, (2.303 RT/F) = 0.06 V
(a) 1010 (b) 1020 (c) 1030 (d) 1040
20. The potential in Debye-Huckle theory is proportion to: [NET DEC 2012]
(a) 1/kr (b) exp[kr ] (c) exp[kr ] / r (d) kr
21. If the concentration (c) is increased to 4 times its original value (c), the change in molar conductivity for
strong electrolytes is (where b is Kohlrausch constant) [NET JUNE 2013]
(a) 0 (b) b c (c) 2b c (d) 4b c
22. In complex metric titration
S(substrate) + T(titrant) → P(product)
The end point is estimated spectrophotometrically. If S and P have ε = 0, the titration curve would look
like: [NET JUNE 2013]

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23. Identify, from the following, the correct ionic strengths for (A) 0.01 molal solution of NaCl and (B) a
0.01 molal solution of Na2SO4. [NET JUNE 2013]
–1 –1
(a) (A) 0.010 mol kg (B) 0.010 mol kg
(b) (A) 0.010 mol kg–1 (B) 0.030 mol kg–1
(c) (A) 0.010 mol kg–1 (B) 0.025mol kg–1
(d) (A) 0.010 mol kg–1 (B) 0.015 mol kg–1
24. Which is correct Nernst equation for redox reaction O + no ⇌ 𝑅? [NET JUNE 2013]
RT O  O   e RTnF ( E  E )
0

(a) E  E 0  In (b)
nF  R   R
(c)
O   e RTnF ( E  E )
0

(d)
O   e RTnF ( E  E )
0

 R  R
25. Electrolysis of aqueous solutions of 1.0 M NaOH results in: [NET DEC 2013]
(a) Na at the cathode and O2 at anode.
(b) H2 at the cathode and O2 at the anode.
(c) Na and H2 at the cathode, and O2 at the anode.
(d) O2 at the cathode and H2 at the anode.
26. The cell voltage of Daniel cell [Zn| ZnSO4(aq) || CuSO4(aq) | Cu] is 1.07 V. If reduced potential of
Cu2+|Cu is 0.34 V, the reduction potential of Zn2+| Zn is: [NET DEC 2013]
(a) 1.141 V (b) –1.41 V (c) 0.73 V (d) –0.73 V
27. Consider the cell: [NET DEC 2013]
Zn | Zn2+ (a = 0.01) || Fe3+ (a = 0.001), Fe2+ (a = 0.01) | Pt
𝑜
𝐸𝑐𝑒𝑙𝑙 = 1.71 V at 25°C for the above cell. The equilibrium constant for the reaction: Zn + 2Fe 3+ ⇌ Zn2+ +
2+
2Fe at 25°C would be close to [NET DEC 2013]
27 54 81
(a) 10 (b) 10 (c) 10 (d) 1040
28. The limiting molar conductivities of NaCl, NaI and RbI are 12.7, 10.8 and 9.1 mS m2 mol–1,
respectively. The limiting molar conductivity of RbCl would be: [NET DEC 2013]
2 –1 2 –1
(a) 32.6 mS m mol (b) 7.2 mS m mol
(c) 14.4 mS m2 mol–1 (d) 11.0 mS m2 mol–1
29. In the graph below, the correct option, according to Kohlrausch law, is: [NET JUNE 2014]

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(a) A is a weak electrolyte and B is a strong electrolyte

(b) A is a strong electrolyte and B is a weak electrolyte
(c) C is a strong electrolyte and D is a weak electrolyte
(d) C is weak electrolyte and D is a strong electrolyte
30. Solutions of three electrolytes have the same ionic strength and different dielectric constants, as 4, 25 and 81.
The corresponding relative magnitude of Debye-Huckel screening, lengths of the three solutions are:
[NET JUNE 2014]
(a) 4, 25 and 81 (b) 2, 5 and 9 (c) 1/2, 1/5 and 1/9 (d) 1, 1 and 1
31. Given; [NET JUNE 2014]
– –
A. Fe(OH)2 (s) + 2e → Fe(s) + 2OH (aq); E° = –0.877 V
B. Al3+ (aq) + 3e– → Al(s); E° = –1.66 V
C. AgBr(aq) + e– → Ag(s) + Br– (aq); E° = 1.07 V
The overall reaction for the cells in the direction of spontaneous change would be
(a) Cell with A and B : Fe reduced Cell with A and C : Fe reduced
(b) Cell with A and B : Fe reduced Cell with A and C : Fe oxidized
(c) Cell with A and B : Fe oxidized Cell with A and C : Fe oxidized
(d) Cell with A and B : Fe oxidized Cell with A and C : Fe reduced
32. 4+ 2+
For the cell reaction, Sn(s) + Sn (aq) ⇌ 2Sn (aq), separate electrode reactions could be written with
the respective standard electrode potential data at 25°C as [NET DEC 2014]
Sn 4 (aq)2e
Sn 2 (aq), E 0.15V
2
Sn (aq)2e
Sn(s), E 0.14V
When RT/F is given as 25.7 mV, logarithm of the equilibrium constant (ln K) is:
(a) 22.6 (b) 226 (c) 2.26 (d) 2.26 × 10–1
33. Fuel cells provide clean electrical energy to a variety of applications including automobiles and
stationary power sources. Normally hydrogen combines with oxygen to give electrical energy and water.
If we use butane instead of hydrogen at 1.0 bar and 298 K, the following reaction occurs:
[NET DEC 2014]
13
C4 H10 (g) O 2 (g) 4CO 2 (g)5H 2O(l)

If the change in the Gibbs free energy of this reaction is 2746.46 kJ mol–1, involving 26 electrons, its
open circuit voltage is:
(a) 1.55 V (b) 1.09 V (c) 3.15 V (d) 2.06 V
34. Dominant contribution to the escaping tendency of a charged particle with uniform concentration
in a phase, depends on [NET JUNE 2015]

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(a) Chemical potential of that phase

(b) electric potential of the phase
(c) thermal energy of that phase
(d) gravitational potential of that phase
35. The intrinsic viscosity depends on the molar mass as [] = KMa [NET DEC 2015]
The empirical constants K and a are dependent on
(a) solvent only (b) polymer only
(c) polymer solvent pair (d) polymer-polymer interaction
36. Differential pulse polarography (DPP) is more sensitive than D.C. Polarography (DCP). Consider
following reasons for it [NET DEC 2015]
(A) non-faradic current is lessin DPP in comparision to DCP
(B) non-faradic current is more in DPP in comparision to DCP
(C) Polarogram of DPP is of different shape than that of DCP
Correct reason (s) is / are
(a) A and C (b) B and C (c) B only (d) A only
37. The temperature –dependence of an electrochemical cell potential is
𝐺 𝐻 𝑆 𝑆
(a) 𝑛𝐹𝑇 (b) 𝑛𝐹 (c) 𝑛𝐹 (d) 𝑛𝐹𝑇
38. Conductometric titration of a strong acid with a strong alkali (MOH) shows linear fall of
conductance up to neutralization point because of [NET DEC 2015]
(a) formation of water
(b) increase in alkali concentration
(c) Faster moving H+ being replaced by slower moving M+.
(d) neutralization of acid.
39. In Kohlrausch law, m = 0𝑚 – √𝑐 , 0𝑚 and  [NET DEC 2015]
(a) depend only on stoichiometry
(b) depend only on specific identify of the electrolyte
(c) are independent of specific identify of the electrolyte
(d) are mainly dependent on specific identity of the electrolyte and stoichiometry, respectively
40. The concentration of a MgSO4 solution having the same ionic strength as that of a 0.1 M Na2 SO4
solution is [NET DEC 2015]
(a) 0.05 M (b) 0.067 M (c) 0.075 M (d) 0.133 M
41. Given that E0(Cl2/Cl–) = 1.35 V and Ksp (AgCl) = 10–10 at 25oC, E0 corresponding to the electrode
reaction [NET DEC 2015]
1 2.303 𝑅𝑇
Cl2(g) + Ag+ (soln.) + e  AgCl(s) is
– [ = 0.06𝑉]
2 𝐹
(a) 0.75 V (b) 1.05 V (c) 1.65 V (d) 1.95 V
42. The standard EMF of the cell Pt, H2(g) | HCl(Soln. ) | AgCl(s), Ag(s) [NET DEC 2015]
(a) increases with T (b) decreases with T
(c) remains unchanged with T (d) decreases with [HCl]
43. In a potentiometric titration, the end point is characterised by [NET JUNE 2016]
𝑑𝐸 𝑑2 𝐸 𝑑𝐸 𝑑2 𝐸 𝑑𝐸 𝑑2 𝐸 𝑑𝐸 𝑑2 𝐸
(a) = 0, 2 = 0 (b)
𝑑𝑉 𝑑𝑉 𝑑𝑉
 0, 𝑑𝑉 2 = 0 (c) 𝑑𝑉 = 0, 𝑑𝑉 2  0 (d) 𝑑𝑉  0, 𝑑𝑉 2 0
44. On titrating conductometrically a NaOH solution with a mixture of HCl and CH 3CO2H solutions,
plot of the volume of mixed acid added (b) in y-axis against the conductance (a) in x-axis is
expected to look like [NET JUNE 2016]

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45. The standard electrode potential E0 at a fixed temperature and in a given medium is dependent on
[NET JUNE 2016]
(a) Only the electrode composition
(b) The electrode composition and the extent of the reaction
(c) The extent of the electrode reaction only
(d) The electrode reaction and the electrode composition
46. Two aqueous 1:1 electrolyte systems A and B are at different temperature T A and TB and CA and CB
concentrations, respectively. Their Debye lengths will be equal if [NET JUNE 2016]
(a) TA = 2TB and CA = 2CB (b) TA = 2TB and CA = CB/2
(c) TA = √2TB and CA = 2CB (d) TA = 2TB and CA = √2𝐶 B
47. Aqueous solutions of NaCl, CaCl2 and LaCl3 show the following plots of logarithms of mean ionic
activity coefficient (ln ) vs molar concentration(c) [NET JUNE 2016]

(ln )

√𝒄
The correct option is then
NaCl CaCl2 LaCl3
(a) C B A
(b) A B C
(c) A C B
(d) C A B
48. The correct statement for d.c. polarography is [NET DEC 2016]
(a) E1/2 is concentration dependent
(b) Dropping mercury electrode is a macro electrode
(c) Limiting current is equal to diffusion current
(d) A large excess of supporting electrolyte eliminates migration current.
49. The ionc mobilities of N𝐻4+ and HC𝑂3− are 6  10–4 V–1 s–1 and 5  10–4 V–1 s–1, respectively. The
transport numbers of N𝐻4+ and HC𝑂3− are, respectively [NET DEC 2016]
(a) 0.545 and 0.455 (b) 0.455 and 0.545
(c) 0.090 and 0.910 (d) 0.910 and 0.090
50. The ionic strength of a solution containing 0.008 M AlCl3 and 0.005 M KCl is [NET DEC 2016]
(a) 0.134 M (b) 0.053 M (c) 0.106 M (d) 0.086 M
51. If the specific conductances of a sparingly soluble (1 : 1) salt (MW = 200 g mol –1) in its saturated
aqueous solution at 25oC and that of water are 1.5  10–3 ohm–1 and 1.5  10–5 ohm–1 dm–1,
respectively, and the ionic conductances for its cation and anion at infinite dilution are 0.485 and
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1.0 ohm–1 dm2 mol–1, respectively, the solubility, (in g L–1) of the salt in water at 25oC is
[NET DEC 2016]
(a) 1  10–6 (b) 1  10–3 (c) 2  10–1 (d) 2  10–4
52. Given, (i) Zn + 4NH3  Zn(NH3)2+ 4 + 2𝑒, E = 1.03 V
0 [NET DEC 2016]
(ii) Zn  Zn + 2e,
2+ E = 0.763V
0

The formation constant of the complex Zn (NH3)2+ 4 is approximately

2.303 𝑅𝑇
( 𝐹 = 0.0591)
(a) 1  105 (b) 1  107 (c) 1  109 (d) 1  1012
53. The electrochemical cell potential (E), after the reactants and products reach equilibrium , is (E0 is
the standard cell potential and n is the number of electrons involved) [NET JUNE 2017]
(a) E = E + nF/RT
0 (b) E =E – RT/nF
0 (c) E = E 0 (d) E = 0
54. The specific conductance of a solution is 0.176 –1 cm–1. If the cell constant is 0.255 cm–1, the
conductance ( –1) of that solution is [NET JUNE 2017]
(a) 1.449 (b) 0.690 (c) 0.045 (d) 0.431
55. The equivalent conductance at infinite dilution of strong electrolyte (0) can be obtained from the
plot of [NET DEC 2017]
1
(a)  vs. C (b)  vs √𝐶 (c)  vs. C2 (d)  vs. 𝐶
56. If the specific conductance of an electrolyte solution is 0.2 –1 cm–1 and cell constant is 0.25 cm–1,
the conductance of the solution is [NET DEC 2017]
(a) 1.25  –1 (b) 1.0  –1 (c) 0.8  –1 (d) 2.0  –1

57. The predicted electromotive force (emf) of the electrochemical cell [NET DEC 2017]
Fe(s)/Fe (aq) (0.01M) || Cd (aq) (0.01M)/ Cd(s) is
2+ 2+
0 0
(𝐸(𝐹𝑒 2+ /𝐹𝑒) = −0.447 𝑉 𝑎𝑛𝑑 𝐸(𝐶𝑑2+ /𝐶𝑑) = −0.403 𝑉)

(a) –0.850 V (b) +0.044 V (c) +0.0850 V (d) –0.044 V

58. The standard cell potential of cell, Pt|H2(g)| HBr(aq)|AgBr(s)|Ag(s), was measured over a range of
temperature, and the data was fitted as E0(Volt) = 0.01–1  10–4 (T–298) – 2  10–6 (T–298)2 the
standard reaction entropy [NET JUNE 2018]
(JK–1 mol–1) and enthalpy (KJ mol–1) at 298 K are
(a) –9.65 and –3.85 (b) –3.84 and –9.65
(c) –18.3 and –7.68 (d) –7.68 and –18.3
59. A solution of Fe is titrated potentiometrically using Ce3+ solution at 25oC. the emf (in V) of the
3+

redox system thus formed when, (i) 50% of Fe3+ and (ii) 80% of Fe3+ are titrated, would
respectively be [NET JUNE 2018]
0
Given 𝐸𝐹𝑒 3+/𝐹𝑒 2+ = 0.77V, log10 2 = 0.301)
(a) 0.734 and 0.77 (b) 0.77 and 0.385
(c) 0.77 and 0.734 (d) 0.385 and 0.367
60. The correct statement among the following is [NET JUNE 2018]
(a) Salt bridge is required for the mixing of the solutions in the two half cells.
(b) Salt bridge allows current to flow between the half cells without mixing the solutions
(c) Salt bridge enhances the rate of the reaction
(d) Salt bridge consists of a non–electrolyte in a gel.
61. The standard free energy of the reaction [NET JUNE 2018]
AgBr(s)  Ag (aq) + Br (aq)
+ –

is closest to
(E0(AgBr/Ag, Br–) = 0.07 V, E0(Ag/Ag+) = 0.80 V; F = 96500 C mol–1)
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(a) 7 kJ mol–1 (b) 70 J mol–1 (c) 70 kJ mol–1 (d) 7 J mol–1

62. Conductivities of water and a saturated solution of a sparingly soluble salt AB2 are 7 and 21 S m–
1, respectively. Given, 02+ = 12.72 mS m2 mol–1 and 0 − = 7.64 mS m2 mol–1, the solubility of AB ,
𝐴 𝐵 2
in mol m–3, is [NET JUNE 2018]
(a) 5.0  10–4 (b) 5.0  10–3 (c) 5.0  10–5 (d) 5.0  10–6
63. The equilibrium constant of the following reaction : [NET JUNE 2018]
Sn(s) + Sn4+ (aq) ⇌ 2 Sn2+ (aq)
at 300K is close to
0 0 −1
𝐺𝑖𝑣𝑒𝑛 ∶ 𝐸𝑆𝑛 4+ /𝑆𝑛 2+ = +0.15𝑉 𝑎𝑛𝑑 𝐸𝑆𝑛 2+ /𝑆𝑛 = −0.15𝑉, 𝑅 = 8.314 𝐽𝐾 𝑚𝑜𝑙 −1 ;
( )
𝐹 = 96485 𝐶𝑚𝑜𝑙 −1
(a) 106.08 (b) 108.08 (c) 1010.08 (d) 1012.08
64. The cell potential (in V) of a Ag/AgCl/KCl electrode connected to the standard hydrogen electrode at 298 K is
0
closed to (Given 𝐸(𝐴𝑔𝐶𝑙/𝐴𝑔𝐶𝑙 − ) = 0.222 V and assume that the activity of KCl is 0.01) [NET DEC 2019]
(a) 0.197 (b) 0.297 (c) 0.340 (d) 0.440
65. The electrolyte solution that has the smallest Debye-length at 298 K is [NET DEC 2019]
(a) 0.01 M NaCl (b) 0.01 M Na2SO4 (c) 0.01 CuCl2 (d) 0.01 M LaCl3
66. In common Glass electrode, alkaline error caused at pH > 10 is least for [NET DEC 2019]
(a) 0.01 M NaCl (b) 1.0 M NaCl (c) 1.0 LiCl (d) 1.0 KCl
67. Match the items in column I with those of column II [NET DEC 2019]
Column X Column Y
A Conductometric titration I Voltage
B Amperometric titration II Resistance
C pH metric titration III I
D Differential pulse polarography
IV Id
Correct match is
(a) A–II; B–IV; C–I; D–III (b) A–III; B–I; C–II; D–IV
(c) A–III; B–II; C–IV; D–I (d) A–I; B–III; C–IV; D–II
68. For the electrochemical cell Ag|AgCl|MCl(0.01M)|MCl(0.02M)|AgCl|Ag, the junction potential is highest when
M+ is [NET DEC 2019]
(a) H+ (b) Li+ (c) Na+ (d) K+
69. The Eo(M+/M) of the cell. SHE||MX|M can be obtained from the plot of (Ecell is the cell potential
and m is the molality of ideal dilute . [NET NOV 2020]
1
(a) Ecell against (T log m) (b) Ecell against (𝑇 log 𝑚)
√𝑚
(c) Ecell against (T√𝑚) (d) Ecell against ( 𝑇 )
70. Molar conductivities of an electrolyte are 100 and 50 mS cm 2 mol–1 when concentrations are 4
and 9 mM. respectively. The limiting molar conductivity of this electrolyte in mS cm2 mol–1 is
closest to [NET NOV 2020]
(a) 150 (b) 200 (c) 250 (d) 300
71. The amount of Ba(NO3)2 (molecular weight 261.32 amu) required to be added to 500 g of a 0.11 mol
kg–1 solution of KNO3 in order to raise its ionic strength to 1.00 is approximately : [NET FEB 2022]
(a) 38.8 g (b) 19.4 g (c) 76.2 g (d) 126.5 g
72. For a weak electrolyte such as acetic acid, the relation among conductance (), equilibrium constant (K)
and concentration (C) can be expressed as : (0 is the conductance at infinite dilution)[NET FEB 2022]
1 1 𝐶 1 1 𝐶 1 1 𝐶 1 𝐶
(a) = − (b) = + (c) = + (d) =
 0 𝐾 0  0 𝐾 02 0  𝐾 02  𝐾 02

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73. 0
For the cell Cd | CdCl2 || AgCl |Ag ; 𝐸𝑐𝑒𝑙𝑙 0
= 0.675 V and d𝐸𝑐𝑒𝑙𝑙 |dT = – 6.5  10–4 V K–1 at 27oC.
The H(kJ mol–1) value for the reaction Cd + 2AgCl  2Ag + CdCl2 is closest to :[NET FEB 2022]
(a) –168 (b) –123 (c) –95 (d) –234
74. What is the cell potential (in V) at 298K and 1 bar for the following cell?
Zn(s)|ZnBr2(aq,0.20mol/kg)||AgBr(s)|Ag(s)|Cu
+2 /𝑍𝑛 = −0.762𝑉, 𝐸𝐴𝑔𝐵𝑟/𝐴𝑔 = +0.730𝑉, and assuming  of ZnBr2 solution = 0.462)
0 0
(given 𝐸𝑍𝑛
[NET SEP 2022]
(a) 0.298 (b) 2.198 (c) 0.531 (d) 1.566
75. The limiting molar conductivities, at 25oC, of few ionic compounds are given in the table below. The
limiting molar conductivity of AgI, in units of milli-siemens (meter)2mol-1 , at 25oC is:
[NET SEP 2022]
Ionic Compounds Molar Conductivity
(milli-siemens (meter)2mol–1)
Nal 12.69
NaNO3 12.16
AgNO3 13.34
(a) 13.87 (b) 12.73 (c) 11.63 (d) 10.78
0 0
76. Given that at 298.15 K, 𝐸𝐹𝑒 +3 /𝐹𝑒 = −0.04𝑉; 𝐸𝐹𝑒 +3 /𝐹𝑒 = −0.44𝑉. At this temperature, the value of
0
𝐸𝐹𝑒 +3 /𝐹𝑒 +2 is [NET SEP 2022]
(a)1.24V (b)1.00V (c) 0.40V (d) 0.76V
77. Consider the following statements, [NET DEC 2023]

I. Micelles form above the critical micelle concentration

II. Micelles form above the Krafft temperature

The Correct option is

(a) Only I is true (b) Only II is true

(c) Both I and II are true (d) Both I and II are false

78. For 0.001 M aqueous solutions of AlCl 3, CaCl2, and KCl at 25oC, the correct order of Debye length is
[NET DEC 2023]
(a) AlCl3 < CaCl2 < KCl (b) KCl < CaCl2 < AlCl3
(c) CaCl2 < KCl < AlCl3 (d) AlCl3 < KCl < CaCl2
1
79. If E0 for OCl– (aq)|Cl–(aq) and Cl–(aq)| 2 Cl2(g) half-cells, respectively, are 0.94 V and – 1.36 V, then
1
E0 (in V) for the OCl– (aq) 2 Cl2(g) half cell is [NET DEC 2023]
(a) – 0.42 (b) – 2.20 (c) 0.52 (d) 1.04
80. The temperature dependent standard electrode potential of [NET DEC 2023]
Ag(s)|AgBr(s)|Br–(aq) fits the expression
𝑇 𝑇 2
E0(V) = 0.0713–4.99  10–4 (𝐾 − 298) − 3.45 × 10−6 (𝐾 − 298) .
At 398 K, the entropy change, S0, ( in J K–1 mol–1) is

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(a) – 48.2 (b) –114.7 (c) 48.2 (d) 114.7

81. The resistances of 0.1 M KCl and 0.05 M NaCl in a conductivity cell are 90  and 200 , respectively.
If the specific conductivity of 0.1 M KCl is 11.2 × 10–3 S cm–1, then the molar conductance (in S cm2
mol–1) of 0.05 M NaCl is closest to [NET JUNE 2024]
5 2 3 4
(a) 10 (b) 10 (c) 10 (d) 10
82. The mean activity coefficient () of 0.1 m aqueous solution of CdCl2 at 298 K and 1 bar is 0.228. under
this condition, the potential of the cell,
Cd(s)|CdCl2(aq., 0.1 m)| AgCl(s)| Ag(s), is
[Eo (AgCl/Ag, Cl–) = 0.22 V; Eo (Cd2+/Cd) = – 0.40 V] [NET JUNE 2024]
(a) 0.75 V (b) 0.62 V (c) 0.89 V (d) 0.49 V
83. The ionic strength (in mol kg–1) of an aqueous solution of 0.03 mol kg–1 K3 [Fe(CN)6] is closest to
[NET DEC 2024]
(a) 0.27 (b) 0.18 (c) 0.12 (d) 0.15
84. For the given cell, [NET DEC 2024]
2+ +
Zn(s) | Zn (aq.,0.5 M)||Ag (aq., 0.1 M)|Ag(s),
the emf (in V) of the cell at 25 °C is closest to
0 0
[At 25°C, 𝐸𝑍𝑛 2+ /𝑍𝑛 = –0.76 V and 𝐸𝐴𝑔 + /𝐴𝑔 = +0.80 V.]

(a) 0.05 (b) 0.04 (c) 1.56 (d) 1.51

ANSWER KEY
1. C 2. C 3. A 4. A 5. D 6. C 7. D 8. A 9. B 10. C
11. C 12. C 13. D 14. D 15. A 16. C 17. C 18. D 19. B 20. C
21. B 22. C 23. B 24. B 25. B 26. D 27. B 28. D 29. C 30. B
31. B 32. A 33. B 34. B 35. C 36. A 37. C 38. C 39. D 40. C
41. D 42. B 43. B 44. D 45. D 46. A 47. B 48. D 49. A 50. B
51. C 52. C 53. D 54. B 55. B 56. C 57. B 58. A 59. C 60. B
61. C 62. A 63. C 64. C 65. 66. 67. A 68. A 69. A 70. B
71. A 72. B 73. A 74. D 75. A 76. D 77. C 78. A 79. C 80. B
81. B 82. A 83. B 84. D
SOLUTION
1.
Ans. (c)
Sol. For an aqueous solution at 25oC, the Debye – Huckel limiting law is
log  = –A|Z+ Z–| √
log  = –0.509|Z+ Z–| √ [∵ A = 0.509]
2.
Ans. (c)
Sol. For, Cu+2 + 2e Cu, E0 = 0.34 V
1
0.059 1 0.059 635 10−3
Ecell = 0
𝐸𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔 [𝐶𝑢+2] = 0.34 − 𝑙𝑜𝑔 𝑔
2 2 63.5
𝑚𝑜𝑙
 0.1 𝐿𝑖𝑡
0.054
= 0.34 – 𝑙𝑜𝑔 10 = 0.31 𝑣𝑜𝑙𝑡
2
So, when Ecell = 0.31 volt will reach, then deposition of Cu will start.

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For Ag+ + e  Ag, E0 = 0.50 V

on completion of this reaction,
0.059 1 0.1  10−3
Ecell = 𝐸𝑐𝑒𝑙𝑙
0
− 𝑙𝑜𝑔 [𝐴𝑔+] [Given : [Ag+] = 𝑀]
1 108  0.1
1
0.059 0.1 ×10−3
Ecell = 0.50 – 𝑙𝑜𝑔 108 ×0.1 = 0.203 𝑣𝑜𝑙𝑡
1
So, we will have to fix cathode potential above 0.31 volt so that no Cu is deposited at the cathode
We can not reduce the potential upto 0.203 V. So, that all Ag + has been deposited
3.
Ans. (a)
𝑒 2 𝑁𝐴
Sol. We have  = √ (∑𝑖 𝐶𝑖 𝑍𝑖2 )
0 𝑟 𝑘𝐵 𝑇

√∑𝑖 𝐶𝑖 𝑍𝑖2 −1
1 2𝑒 2 𝑁𝐴
= √∑𝑖 𝐶𝑖 𝑍𝑖2 × × √ = 30 (nm √𝑚𝑜𝑙𝑘𝑔−1 )
√2 𝑟 0 𝑘𝐵 𝑇 √2 𝑟

√2×0.03×12 +0.03 ×22 (√𝑚𝑜𝑙𝑘𝑔−1 ) −1

= × 30 × 𝑛𝑚−1 × (√𝑚𝑜𝑙𝑘𝑔−1 )
√2 ×100
√0.18 9
= × 30𝑛𝑚−1   = 10 nm–1
10 √2
10
Therefore, Debye–Huckel screening length (–1) = nm
9
4.
Ans. (a)
Sol. For oxidation reduction half-cell
Oxidized state (O) + ne– ⇌ Reduced state (R)
From modified nernst equation (in terms of formal potential E 0)
𝑅𝑇 [𝑅]
 E = E0 – 𝑛𝐹 𝑙𝑛 [𝑂]
𝑅𝑇 1
or, E–E0 = – 𝑛𝐹 𝑙𝑛 𝑒 2
𝑅𝑇
or, E – E0 = – 𝑛𝐹 ln (e–2)
𝑅𝑇
or, E–E0 = – (–2) 𝑛𝐹 𝑙𝑛 𝑒 [∵ 𝑙𝑛 𝑒 = 1]
2𝑅𝑇
or, E – E0’ = + 𝑛𝐹
5.
Ans. (d)
Sol. CH3COOH + NH3OH  CH3COO– (aq.) + N𝐻4+ (aq) + H2O
weak acid weak base ionised salt

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When weak base is added to weak acid then salt is formed which is more dissociated w.r.t.
weak acid, so conductance increases upto end point but after the end point only concentration
of weak base increases which remains in almost undissociated form so does not lead toincrease
in conductance.
6.
Ans. (c)
Sol. In potentiometric titration the rate of change in slope of E vs V graph has maximum at the
equivalence point
𝑑 𝑑𝐸 𝑑2 𝐸
 ( )=0  𝑑𝑉 2 =0
𝑑𝑣 𝑑𝑉
𝑑𝐸 𝑑𝐸
And as 𝑑𝑉 can be positive or negative, But |𝑑𝑉 | will always be greater than zero.
7.
Ans. (d)
Sol. Fe+3 + e Fe+2, 𝐸10 = 0.77 V, G1 = –nF𝐸10 = –F  0.77 ....(i)
Fe+2 + 2e  Fe, 𝐸20 = –0.44 V, G2 = – nF𝐸20 = –2F (–0.44) ....(ii)
Adding above half cell reactions
Fe+3 + 3e–  Fe
G3 = G1 + G2  –3F𝐸30 = −0.77𝐹 + 0.88 F = 0.11 F
0.11
𝐸30 = – 3 𝑉 = −0.036𝑉 ≃ −0.04𝑉
8.
Ans. (a)
Sol. Let one faraday of electricity is withdrawn from the cell
(i) Electrode reaction at anode Ag(s) + Cl– (a1)  AgCl(s) + e–
(ii) Electrode reaction at cathode AgCl(s) + e–  Ag(s) + Cl– (a2)
(iii) Migration of K ions
+ t+ K+ (a1)  t+K+(a2)
(iv) Migration of Cl– ions t– Cl–(a2)  t–Cl– (a1)
The net effect is obtained by adding the above four changes, which gives
Cl–(a1) + t+K+(a1) + t–Cl–(a2)  Cl–(a2) + t+K+(a2)+t–Cl–(a1)
Or, t+K+(a1) + Cl–(a1)–t–Cl–(a1)  t+K+(a2)+Cl–(a2)– t– Cl–(a2)
t+K+(a1)+ t+ Cl–(a1)  t+K+(a2)+t+ Cl– (a2)
9.
Ans. (b)
Sol. 0(𝐻𝐶𝑂𝑂𝐻) = 0(𝐻𝐶𝑂𝑂− ) + 𝑜(𝐻 +)
1 1
= 𝑜(𝐻𝐶𝑂𝑂𝑁𝑎) + 𝑜(𝐻𝐶𝑙) − { 𝑜(𝑁𝑎2 𝑆𝑂4 ) + 𝑜(𝐾𝐶𝑙) − 𝑜(𝐾2𝑆𝑂4 ) }
2 2

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1 1
= 105 + 426 – {2 (260) + 150 − 2 (308)} = 405 𝑆 𝑐𝑚2 mol–1.
10.
Ans. (c)
11.
Ans. (c)
Sol. If we take a half-cell
1
H+ + e–1 = 2 H2
𝑅𝑇 1
E = E0 – 𝑙𝑛 𝑀
𝐹 𝐻+
𝑅𝑇
E = E0 + ln MH+
𝐹
Then E vs log m graph gives intercept E0 intercept in the given figure is BB’

12.
Ans. (c)
Sol. Ecell = EL + ER = (𝐸𝐶𝑙 −|𝐴𝑔𝐶𝑙|𝐴𝑔 − 𝐸𝐻 +|𝐻2 |𝑃𝑡 ) + (𝐸𝐻 + |𝐻2 |𝑃𝑡 − 𝐸𝐶𝑙 −|𝐴𝑔𝐶𝑙\𝐴𝑔 )
𝐿 𝑅
Nernst equation for each potential.
1
𝑅𝑇 𝑅𝑇 (𝑃|𝑃 𝑜 )1/2 𝑅𝑇 (𝑃|𝑃 0)2 0
Ecell = 0
[𝐸𝐶𝑙 − |𝐴𝑔𝐶𝑙|𝐴𝑔 − 𝑙𝑛 (𝑎𝐶𝑙 − )1 + 𝑙𝑛 ] + [− 𝑙𝑛 (𝑎 ]− 𝐸 𝐶𝑙 − |𝐴𝑔𝐶𝑙|𝐴𝑔
+
𝐹 𝐹 (𝑎𝐻+ ) 𝐹 𝐻+ ) 2
𝑅𝑇
𝑙𝑛 (𝑎𝐶𝑙 − )2 ]
𝐹
𝑅𝑇 (𝑎 + ) (𝑎𝐶𝑙− )2 𝑅𝑇 (𝑎 ± )2
Ecell = 𝑙𝑛 (𝑎𝐻 2
=2 𝑙𝑛 (𝑎
𝐹 𝐻+ ) (𝑎𝐶𝑙− )1 𝐹 ± )1
1
13.
Ans. (d)
Sol. Debye–Huckel equation, –log  = A|Z+ Z–| √𝐼
Since, total number of ‘+’ ion per unit volume = n+
total number of ‘–‘ ion per unit volume = n–
 n+ = n 𝑒 −𝑖 /𝑘𝑇 and n– = n 𝑒 −𝑖 /𝑘𝑇 [∵ i = e]
𝑐ℎ𝑎𝑟𝑔𝑒
Since charger density () = 𝑣𝑜𝑙𝑢𝑚𝑒
𝑧 2𝑛 2𝑒 2 
 = (n+ –n–) e = (n 𝑒 −𝑧𝑒/𝑘𝑇 − 𝑛𝑒 −𝑧𝑒/𝑘𝑇 ) = – 𝑘𝑇
Then we expand them and put e << kT condition. Then we apply poission equation to
4
calculate the potential. The equation is 2 = – 
𝑟
14.
Ans. (d)

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Sol. PbCl2 and PbSO4 are ionic compounds and insoluble in cold water. Therefore, cannot be used for
deposition of Pb and Pb(Et4) is toxic.
15.
Ans. (a)
Sol. Daniel cell consists of two half cells. The half cell on the left contains a zinc metal electrode dipped
in ZnSO4 solution. The half cell on the right consist of copper metal electrode in a solution of
CuSO4. The half cell joined by a salt bridge.
Oxidation half reaction, Zn(s)  Zn +2 (aq) + 2e–
Reduction half cell, Cu2+ (aq) + 2e–  Cu(s)
Net Zn(s) + Cu+2 (aq)  Zn+2 + Cu(s)
16.
Ans. (c)
Sol. Due to Kohlrausch’ law at infinite dilution, when dissociation is complete, each ion makes a
definite contribution towards molar conductance of the electrolyte irrespective of the nature of
the other ion with which it is associated and that the molar conductance at infinite dilution for any
electrolyte is given by the sum of the contribution of the two ions. Only hydrochloric acid in water
completely dissociation and contribution with equal ion.
17.
Ans. (c)
18.
Ans. (d)
Sol. The weight of Pt-gauze as electrode increases by 16–14.5 = 1.5 g because 1.5 g of Cu is deposited
on Pt–gauze. Therefore, weight of Cu in 2.0 gram brass is 1.5g.
1.5
Therefore, percentage weight of Cu in brass = 2.0 × 100 = 75
19.
Ans. (b)
Sol. 2Fe+3 + Sn+2 ⇌2 Fe+2 + Sn+4
Fe+3 + e–  Fe+2  2 ....(1)
Sn  Sn + 2e
+2 +4 – ....(2)
2Fe + 2e + Sn  2Fe + Sn+4 + 2e
+3 – +2 +2

Since, we know that at room temperature, equilibrium constant

𝑛𝐸0 𝑛𝐸0
log Keq = 0.0591 = 0.06
E0 = 𝐸𝑟𝑖𝑔ℎ𝑡
0 0
− 𝐸𝑙𝑒𝑓𝑡 ⇒ 𝐸 0 = 0.75 − 0.15 ⇒ 𝐸 0 = 0.60
2×0.60
log Keq = 0.06
log Keq = 20  Keq = 1020
20.
Ans. (c)
−2𝑛 𝑒 2 
Sol. From Debye–Huckel limiting law, charge density () = 𝑘𝐵 𝑇
4 4 −2𝑛𝑒 2 
According to Poission equation of electrostatics [  = −  ] = −  [
2
]
𝑟 𝑟 𝑘𝐵 𝑇
8𝑛𝑒 2  1 𝜕 𝜕
2 = (2 = 𝑟 2 𝜕𝑟 𝑟 2 𝜕𝑟 )
𝑟 𝑘𝐵 𝑇
8𝑛 𝑒 2 
The equation may be written as 2 = k2 (𝑤ℎ𝑒𝑟𝑒, 𝑘 2 = )
𝑘𝐵
𝑧𝑒 𝑧𝑒 𝑒 −𝑘𝑟
The solution of this equation is equal to  = 𝑒 −𝑘𝑟 = , the term is total potential in
𝑟 𝑟 𝑟 𝑟
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Debye–Huckel it means electrical potential.

𝑒 −𝑘𝑟 𝑧𝑒 𝑧𝑒 𝑧𝑒 𝑘 𝑧𝑒 𝑧𝑒
Expand term  =  𝑟 [1 − 𝑘𝑟] =  𝑟 − = − 1
𝑟 𝑟 𝑟 𝑟 𝑟 𝑟 𝑟 (𝑘)
(I) (II)
Potential due to the Potential on the ion
given ion itself
21. due to its ionic

Ans. (b) atmosphere

Sol. m = 0𝑚
− 𝑏 √𝑐 ....(1)
If the concentration four times increased.
m’ = 0𝑚 − 𝑏 √4𝑐  m’ = 0𝑚 − 2𝑏√𝑐 .....(2)
From equation (1) and (2), we get
m – m’ = 0𝑚 − 𝑏√𝑐 − 0𝑚 + 2𝑏 √𝑐
m – m’ = b√𝑐
22.
Ans. (c)
Sol. If S and P have  = 0, then titrant shows parallely and after end point goes increasingly with
respect to substate.
23.
Ans. (b)
Sol. NaCl ⇌ Na+ + Cl–
0.01 0.01 0.01
1 1 1 1
I = 2 ∑ 𝑚𝑖 𝑧𝑖2 == 2[m1𝑧12 + 𝑚2 𝑧22 ] = 2 [0.01(+1)2 + 0.01(−1)2 = 2 [0.01 + 0.01] = 0.01
Na2SO4 ⇌ 2Na+ + S𝑂4−2
0.01 20.01 0.01
1 1 1
I = 2[2  0.01(+1)2 + 0.01(–2)2] = 2 (0.02+0.04) = 2 (0.06) = 0.03
24.
Ans. (b)
Sol. O + ne ⇌ R
𝑅𝑇 [𝑅]
Nernst equation, E = E0 – 𝑛𝐹 𝑙𝑛 [𝑂]
−𝑅𝑇 [𝑅]
E – E0 = 𝑙𝑛 [𝑂]
𝑛𝐹
[𝑅] 𝑛𝐹 [𝑂] 𝑛𝐹
ln [𝑂] = − 𝑅𝑇 [𝐸 − 𝐸 ]  –ln [𝑅] = − 𝑅𝑇 [𝐸 − 𝐸 0 ]
0

𝑛𝐹 0]
[𝑂] 𝑛𝐹 [𝑂]
ln[𝑅] = 𝑅𝑇 (𝐸 − 𝐸 0 )  [𝑅] = 𝑒 𝑅𝑇[𝐸−𝐸
25.
Ans. (b)
Sol. Anode : 4OH–  2H2O + O2 + 4e–
Cathode : 2H+ + 2e–  H2 
26.
Ans. (d)
Sol. Zn  Zn+2 + 2e– (oxidation)
Cu+2 + 2e–  Cu (reduction)
E0 = 1.07V, E0 = 0.34, E = Eright – Eleft

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1.07 = 𝐸𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 − 𝐸𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛

𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙
𝑟𝑖𝑔ℎ𝑡 𝑙𝑒𝑓𝑡
1.07 = 0.34–𝐸𝑍𝑛+2|𝑍𝑛  1.07 – 0.34 = –𝐸𝑍𝑛+2|𝑍𝑛  0.73 V = –𝐸𝑍𝑛+2 |𝑍𝑛
 𝐸𝑍𝑛+2|𝑍𝑛 = – 0.73
27.
Ans. (b)
Sol. Zn + 2Fe+3 ⇌ Zn+2 + 2Fe+2
Nernst equation,
2
0.0591 [𝑍𝑛 +2 ][𝐹𝑒 +2]
Ecell = E0 – 𝑙𝑜𝑔 [𝐹𝑒 +3]2
2
0.0591 [0.01][0.001]2
 Ecell = E0 – 𝑙𝑜𝑔 [0.01]2
2
0.0591
 1.71 = E0 – 𝑙𝑜𝑔 10–4
2
0.0591
 1.71= E0 – 2
 (−4)𝑙𝑜𝑔 10
0.0591
 1.71 = E0 + 2
4 1 .71 = E0 + 0.1182
 E0 = 1.5918
G = –RT ln Keq  –nFE0 = –2.303  8.314  298  log Keq
 –nFE0 = 2.303  8.314  298  log Keq
 –2  96500  1.5918 = – 2.303  8.314  298  log Keq
307217.4
log Keq = 5705.8 = 53.84 ⇒Keq  1054
28.
Ans. (d)
Sol. ∞
𝑁𝑎𝐶𝑙 = 𝑁𝑎 + + 𝐶𝑙 −
∞ ∞
...(i)
∞
𝑁𝑎𝑙 = 𝑁𝑎 + + 𝑙−
∞ ∞
...(ii)
∞
𝑅𝑏𝐼 = 𝑅𝑏+ + 𝑙−
∞ ∞
...(iii)
Add (i) and (iii) substract (ii)
∞
𝑁𝑎 + + 𝐶𝑙 − + 𝑅𝑏 + + 𝑙− − 𝑁𝑎 + − 𝑙− = 12.7 + 9.1 − 10.8
∞ ∞ ∞ ∞ ∞

∞
𝐶𝑙 − + 𝑅𝑏+ = 21.8 − 10.8
∞

𝑅𝑏𝐶𝑙 =11.0 mSm2mol

∞

29.
Ans. (c)
Sol. According to Kohlrausch law molar conductance of strong electrolyte decreases linearly with
square root of concentration while that of weak electrolyte decreases exponentially. Hence, (c) is a
strong electrolyte while D is a weak electrolyte.
30.
Ans. (b)
Sol. Debye–Huckel screening lengths
𝑒 2 𝑁𝐴
=√ (∑ 𝑐𝑖 𝑧𝑖2 )
0 𝑟 𝑘𝐵 𝑇
1   𝑘 𝑇
= √𝑒 20𝑁 1𝑐𝐵 𝑧 2
 𝐴 𝑖 𝑖
1
∝ √ 0

1 1 1
  ∝ √4 2    √25 5    √81 9

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31.
Ans. (b)
Sol. (I) Cell A and B
Fe(OH)2 (s) + 2e–  Fe(s) + 2OH– E0 = –0.877 V
Al3+ + 3e–  Al E0 = 1.66 V
E = 𝐸𝑟𝑖𝑔ℎ𝑡 − 𝐸𝑙𝑒𝑓𝑡
0 0 0

= –0.87 – (–1.66) = + 0.79 V

G = –nFE (E = +ve)
G = –ve (spontaneous)
Fe reduced
(II) A and C
Fe(OH)2(s) + 2e–  Fe(s) + 2OH–(aq) E0 = –0.877
AgBr + e–  Ag(s) + Br–(aq) E0 = 0.071
E0 = 𝐸𝑟𝑖𝑔ℎ𝑡 − 𝐸𝑙𝑒𝑓𝑡
0 0

= 0.071–(–0.877) = 0.948
G = –nFE0 (E0 = +ve) (Reaction spontaneous)
G = –ve
in this cell Fe carried negative reduction potential goes to left hand side of the half cell and in this
half cell oxidation occur.
Fe oxidised
Note : In electrochemical series (Al+3, Al) stay below to (Fe+2, Fe) and (AgBr)(s), Br– : Ag) stay
above . So, (Al+3, Al) reduced and (AgBr, Br–. Ag) oxidised by (Fe+2, Fe).
32.
Ans. (a)
𝑅𝑇
Sol. Ecell = 𝐸𝑐𝑒𝑙𝑙
0
− 𝑛𝐹 𝑙𝑛 𝑄 ....(1)
At equilibrium Q = K (equilibrium constant) and Ecell = 0
𝑅𝑇
So, 0
𝐸𝑐𝑒𝑙𝑙 = 𝑛𝐹 𝑙𝑛 𝐾 ....(2)
Sn4+ + 2e–  Sn2+ E0 = +0.15 (Reduction potential of cathode)
Sn2+ + 2e–  Sn E0 = –0.14 V (Reduction potential of anode)
0 𝑟𝑒𝑑 𝑟𝑒𝑑
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 = 0.15 − (−0.14) = 0.29 𝑉
Putting value of 𝐸𝑐𝑒𝑙𝑙
0
in equation (2)
0 𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝑛𝐹 𝑙𝑛 𝐾
𝑅𝑇
0.29V = 𝑙𝑛 𝐾
𝑛𝐹
𝑅𝑇
n = 2, = 25.7 × 10−3 𝑉
𝐹
25.7 ×10−3
0.29 = 𝑙𝑛 𝐾
2
0.29 ×2
= 𝑙𝑛 𝐾
25.7×10−3
ln k = 22.6
33.
Ans. (b)
Sol. G = –nFE (G = –ve for spontaneous)
G = 2746.06  10 joule/mole
3

2746.06  103 = –26  96500  E

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2746.06 ×1000 2746060

E= 26×96500
 𝐸 = 2509000 ; E = 1.09 volt

34.
Ans. (b)
Sol. 𝑧 𝑖 ′ = 𝑧𝑖′′ + ziF

Electrochemical Chemical Electrical

part potential potential part
For a electron, e’ = e’’ – F zi = –1
If  is negative e’ > e’’
* Escaping tendency of charge species more
If the negative electrical potential is applied then the electrochemical potential is larger than the
chemical potential. So, it means that the tendency of oxidation reaction is increased If the positive
potential is applied then it means the reduction of electron is increased.
35.
Ans. (c)
36.
Ans. (a)
Sol. The residual current in case of DCP is non-faradic current which should be minimum to get the
accurate result. This problem of non-faradic current is overcome by use of DPP in which non-
faradic current is less than DCP. That is why DPP is more sensitive than DCP.
Though the polarograph is different in both cases but it has nothing to do with sensitivity.
37.
Ans. (c)
Sol. G = –nFEcell
Gibb’s – Helmholtz equation,
(𝐺)
G = H + T ( 𝑇 ) ...(1)
𝑃
G = –nFE
Therefore, we get
(𝐺) 𝐹
( 𝑇 ) = −𝑛𝐹 (𝑇 ) ....(2)
𝑃 𝑃
From equation (1) and (2), we get
𝐸
–nFE = H–nFT (𝑇 ) ...(3)
𝑃
Rearranging we have,
𝐸
H = –nF [𝐸 − 𝑇 ( 𝑇 ) ]
𝑃
But, G = H – TS
𝐻−𝐺
S = 𝑇
From equation (3) and equation(4), we get
𝐸
–TS = –nFT ( 𝑇 )
𝑃
𝐸 𝐸 𝑆
S = nF ( 𝑇 )  (𝑇 ) = 𝑛𝐹
𝑃 𝑃
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𝑆
Temperature dependence = 𝑛𝐹
38.
Ans. (c)
Sol. When a strong alkali e.g. sodium hydroxide is added to a solution of a strong acid, e.g.
hydrochloric acid, the reaction.
(H+ + Cl–) + (M+ + OH–)  M+ + Cl–+ H2O
 During the reaction highly conducting H+ are replaced by M+ which has much lower
conductance, so addition of alkali to acid solution is accompanied by a decrease of
conductance.

 When neutralization is complete then the further addition of alkali results in an increase of
conductance, since the sodium ion and hydroxyl ion are no longer used up in the chemical
reaction.

 At the neutral point the conductance of the system will have a minimum value.
39.
Ans. (d)
Sol. K  Kohlrausch’s constant is specified for uni-univalent electrolyte (stoichiometry) and strong
electrolyte (specific identify)
40.
Ans. (c)
Sol. 0.1M Na2SO4 ⇌ 2Na+ + S𝑂4−2
20.1 0.1
1 1 1
I = 2[m1𝑧1 + 𝑚2 𝑧22 ] = 2 [0.2 + 0.4] = 2 × 0.6 = 0.3
2

MgSO4 ⇌ Mg+2 + S𝑂4−2

let conc. m m m
Ionic strength = 0.3
1
I = 2 [m1𝑧12 +m2𝑧22 ]
1
0.3 = 2 [m  4 + m  4]
8𝑚
0.3 = ⇒ 8𝑚 = 0.6
2
0.6
m= = 0.075𝑀
8
41.
Ans. (d)
Sol. Reaction–1 :
1
Cl2 + e–  Cl– E0 = 1.35 V
2
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Reaction –2 :
0.06
AgCl ⇌ Ag+ + Cl– E0 = 𝑙𝑜𝑔 ksp
𝑛
0.06
E0 = 1 𝑙𝑜𝑔10−10 = −0.6
Reaction–3: On reversing reaction–2
Ag+ + Cl– ⇌ AgCl E0 = 0.6
On adding reaction(1) and reaction (3), we get
1
Cl2 + Ag+ + e–  AgCl(s)
2
𝑛1 𝐸1 +𝑛2 𝐸2 (1)(1.35)+(1)(0.6)
E3 = = = 1.95 𝑉
𝑛3 1

42.
Ans. (b)
1
Sol. H2  H+(aq) + e–
2
AgCl + e–  Ag + Cl–
1
H2(g) + AgCl(s)  Ag(s) + H+(aq) + Cl–(aq)
2
𝐸
S = nF (𝑇 )
𝑃
As entropy of reaction decreases because gaseous is being consumed. So, S < 0
𝑆
(𝑇 )< 0 0
𝐸𝑐𝑒𝑙𝑙 decreases with increase in temperature.
43.
Ans. (b)
Sol.

At end point,
𝑑𝐸 𝑑2 𝐸
It shows, 𝑑𝑉  0 & 𝑑𝑉 2 = 0
44.
Ans. (d)
Sol. NaOH + (HCl + CH3COOH)
First NaOH will react with HCl will use NaOH is completely titrated during this process
conductance will decrease due to less of OH– ions.

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Second after that, as NaOH is completely consume. So, simple addition of mixture of HCl and
CH3COOH will only increase the conductance.

45.
Ans. (d)
Sol. The standard electrode potential E0 at a fixed temperature and in a given medium is dependent on
the electrode reaction and the electrode composition.
46.
Ans. (a)
Sol. Debye–Huckel screening length
𝑒 2 𝑁𝐴
 = √ (∑ 𝑐𝑖 𝑧02 )
0 𝑟 𝑘𝐵 𝑇
1   𝑘 𝑇
 = √𝑒 2𝑁0 𝑟∑𝐵𝑐 𝑧 2
𝑘𝐴 𝐴 𝑖 1

1 𝑇𝐴
= √𝐶 ...(i)
𝑘𝐴 𝐴

1 𝑇
= √𝐶𝐵 ...(ii)
𝑘𝐵 𝐵
1 1
= 𝑘 only if TA = 2TB ; CA = 2CB put this value in equation (i)
𝑘𝐴 𝐵
1 2𝑇 𝑇
= √2𝐶𝐵 = √𝐶𝐵
𝑘𝐴 𝐵 𝐵

1 𝑇
= √𝐶𝐵 from equation (ii)
𝑘𝐵 𝐵

Equation (i) = equation (ii)

47.
Ans. (b)
Sol. log  = –2.303A | Z– Z+| √𝐼
For same concentration of electrolyte |Z–Z+| √𝐼 will be smallest for NaCl and largest for LaCl3. As
negative sign is there so slope of NaCl will be least negative and slope of LaCl3 will be most
negative.
48.
Ans. (d)
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Sol. In d.c polarography supporting electrolyte is taken in excess, so that all migration current is
carried by suporting electrolyte. Thus electroactive species remain free from migration current.
1. E1/2 does not depend on concentration of electroactive species.
2. DME is a micro electrode.
3. Limiting current is sum of diffusion current and residual current
ij = i d + i r
49.
Ans. (a)
𝑢+
Sol. t+ = 𝑢
+ +𝑢−
u+ = 6  10–4 u– = 5  10–4
6  10−4 6
t+ = 6 10−4+ 5  10−4 = 11 = 0.545
t– = 1–t+ = 1– 0.545 = 0.455
50.
Ans. (b)
Sol. AlCl3  Al+3 + 3Cl–1
0.008 0 0
0 0.008 0.024
KCl  K+ + Cl–
0.005 0 0
0 0.005 0.005
1 1
I = 2(C1𝑍1 + 𝐶2 𝑍2 + 𝐶3 𝑍32 + 𝐶4 𝑍42 ) = 2 (0.008(3)2 + 0.024(1)2 + 0.005(1)2 +
2 2

0.005(1)2)
1
I = 2(0.072 + 0.024 + 0.005 +0.005) = 0.053
51.
Ans. (c)
Sol. Ksalt = Ksolution –Kwater = (1.5  10–3 – 1.5  10–5) ohm–1 dm–1
Ksalt = 1.5  0.99  10–3
𝐾
Solubility (s) = 𝑠𝑎𝑙𝑡
𝑠𝑎𝑙𝑡
(1.5 0.99  10−3 )𝑜ℎ𝑚 −1𝑑𝑚 −1
s= (0.485+1)𝑜ℎ𝑚 −1𝑑𝑚 2 𝑚𝑜𝑙−1
1.485 𝑚𝑜𝑙 𝑚𝑜𝑙
s= 1.485
 10−3 𝑑𝑚3  s = 1  10–3 𝑑𝑚3
𝑔𝑚 𝑔𝑚
s = 1  10  200 𝑑𝑚3
–3  s = 2  10–1 𝐿
(∵ 1dm3 = 1L)
52.
Ans. (c)
Sol. (1) Zn + 4NH3  Zn(NH3)2+ 4 + 2e
– E0 = 1.03 V
(2) Zn  Zn + 2e
2+ – E0 = 0.763 V
on reversing 2nd reaction and adding it to reaction 1
Anode Zn + 4NH3  Zn (NH3)2+ 4 + 2e
–

Cathode Z𝑛2+ + 2𝑒 −  𝑍𝑛
Zn2+ + 4NH3  Zn(NH3)2+4
Equilibrium constant of above cell reaction is formation constant
0 0 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 0 𝑎𝑛𝑜𝑑𝑒
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑒𝑑 − 𝐸𝑟𝑒𝑑
but values in equation given are of oxidation potential
so 𝑜 𝑐𝑎𝑡ℎ𝑜𝑑𝑒
𝐸𝑟𝑒𝑑 = −0.763
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𝑜 𝑎𝑛𝑜𝑑𝑒
𝐸𝑟𝑒𝑑 = −1.03
𝑜
𝐸𝑐𝑒𝑙𝑙 = −0.763 + 1.03
𝑜
𝐸𝑐𝑒𝑙𝑙 = 0.267
0.0591
Now, 𝐸𝑐𝑒𝑙𝑙
𝑜
= 𝑛 𝑙𝑜𝑔 Keq
0.0591 0.267 ×2
0.267 = 𝑙𝑜𝑔 Keq  = 𝑙𝑜𝑔 Keq  9.03 = log Keq
2 0.0591
Keq = 109.03  Keq ≃ 109
53.
Ans. (d)
Sol. At equilibrium E is zero, because G is zero at equilibrium.
G = –nFE
if G = 0
So, E=0
54.
Ans. (b)
𝑙
Sol. k=G𝐴
0.176 176
0.176 = G  0.255  0.255 = 𝐺 255 = 𝐺
0.6901 –1 = G
55.
Ans. (b)
Sol. For strong electrolyte , 0 can be obtained from the plot of  vs √𝑐
56.
Ans. (c)
𝑙 𝐴 0.2
Sol. R =  𝐴  𝐺 = 𝑘  𝑙 ; 𝐺 = 0.25 = 0.8 –1
57.
Ans. (b)
0.0591 0.01
Sol. Ecell = (𝐸𝑟𝑖𝑔ℎ𝑡
0 0
− 𝐸𝑙𝑒𝑓𝑡 )− 𝑙𝑜𝑔 [0.01]
2
Ecell = –0.403 + 0.447 ; Ecell = 0.044V
58.
Ans. (a)
Sol. Pt|H2(g)|HBr(aq)|AgBr(s)|Ag(s)
E0 = 0.01–110–4 (T–298)–210–6(T–298)2
𝐸0
( ) = 1 × 10−4 − 2 × 2 × 10−6 (𝑇 − 298)
𝑇 𝑃
𝐸 0
( 𝑇 ) = −10−4 − 4 × 10−6 (𝑇 − 298)
𝑃
𝐸
S0 = nF( 𝑇 ) = 2 × 96500 {–10–4 –4  10–6 (298–298)}
𝑃
19.3
=–193000  10–4 = –19.3 JK–1 = = −9.65 JK–1 mol–1
2
𝐸
H0 = –nFE0 + nFT ( 𝑇 )
𝑃
= –96500  [0.01–10–4(298–298)–2  106 (298–298)2 + 298  (–9.65)]
=–965–2875.7 = –3840.7 Jmol–1 = –3.840 kJ mol–1
59.
Ans. (c)
Sol. Fe3+ + e–  Fe2+
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0 0.0591
𝐸𝐹𝑒 3+ |𝐹𝑒 2+ = 𝐸𝐹𝑒 3+ |𝐹𝑒 2+ − 𝑙𝑜𝑔 𝑄
𝑛
0 0 0.0591 |𝐹𝑒 2+ |
𝐸𝐹𝑒 3+ |𝐹𝑒 2+ = 𝐸𝐹𝑒 3+ |𝐹𝑒 2+ − 𝑙𝑜𝑔 |𝐹𝑒 3+|
1
(1) When 50% of Fe3+ is titrated
Fe3+ + e–  Fe2+
x 0
0.5x 0.5x
0 0.0591 0.5𝑥
𝐸𝐹𝑒 3+ |𝐹𝑒 2+ = 𝐸𝐹𝑒 3+|𝐹𝑒 2+ − 1 𝑙𝑜𝑔 0.5𝑥
0
𝐸𝐹𝑒 3+ |𝐹𝑒 2+ = 𝐸𝐹𝑒 3+ |𝐹𝑒 2+ = 0.77

(2) When 80% pf Fe3+ is titrated

Fe3+ + e–  Fe2+
x 0
0.2 x 0.8x
0 0.8𝑥
𝐸𝐹𝑒 3+ |𝐹𝑒 2+ = 𝐸𝐹𝑒 3+ |𝐹𝑒 2+ − 0.0591 𝑙𝑜𝑔
0.2𝑥
𝐸𝐹𝑒 3+ |𝐹𝑒 2+ = 0.77 − 0.0591 𝑙𝑜𝑔 4 = 0.77 − 0.0591 × 2 𝑙𝑜𝑔 2
= 0.77–0.0591  2  0.301 = 0.77–0.0357 = 0.734
60.
Ans. (b)
Sol. Correct statement : Salt bridge allows current to flow between the half cells with out mixing the
solution.
61.
Ans. (c)
Sol. The given cell, AgBr(s)  Ag+ (aq) + Br– (aq) can be written as
Cathode (Reduction)

Ag(s) + AgBr(s)  Ag+(aq) + Br–(aq) + Ag(s)

𝑜 0 0
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐵𝑟 − |𝐴𝑔𝐵𝑟|𝐴𝑔 − 𝐸 +
𝐴𝑔 |𝐴𝑔 = 0.07 − 0.80
Anode (Oxidation) 0
𝐸𝐶𝑒𝑙𝑙 = −0.73 𝑉
G = –nF 𝐸𝑐𝑒𝑙𝑙 = −1 × 96500 × −0.73 = 70445𝐽𝑚𝑜𝑙 −1 = 70.4 𝑘𝐽𝑚𝑜𝑙 −1 = 70kJ mo𝑙 −1
0 0 ( )
62.
Ans. (a)
Sol. ksaturated solution = 𝑘𝐻2 𝑂 + 𝑘𝐴𝐵2
𝑘𝐴𝐵2 = 21 − 7 = 14𝑆𝑚−1 = 14 × 10−6 𝑆𝑚−1
AB2 ⇌ A2+ + 2B–
𝐴𝐵
0
2
= 𝐴02+ + 20𝐵−
𝐴𝐵
0
2
= 12.72 + (2 7.64) = 28 𝑚𝑆𝑚2 𝑚𝑜𝑙 −1 = 2810−3 𝑆𝑚2 𝑚𝑜𝑙 −1
𝑘 𝑘𝐴𝐵 14  10−6
𝐴𝐵
0
2
𝐴𝐵
= 1000  𝑆2 ⇒ 𝑆𝐴𝐵2 = 1000  20 = 103 2810−3
𝐴𝐵2 𝐴𝐵2
𝑚𝑜𝑙
𝑆𝐴𝐵2 = 0.510−6 ⇒ 𝑆𝐴𝐵2 = 510−7 = 510−4 𝑚𝑜𝑙𝑚−3
𝐿
63.
Ans. (c)
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Sol. Sn + Sn4+ Sn2+ + Sn2+

Reduction (cathode)
Oxidation (Anode)

0 𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝑛𝐹 𝑙𝑛 𝑘𝑒𝑞
2.303×8.314×300
 0
𝐸𝑆𝑛 0
4+ |𝑆𝑛 2+ − 𝐸𝑆𝑛 2+ |𝑆𝑛 = 𝑙𝑜𝑔 𝑘eq
2×96485
 0.15–(0.15) = 0.02976 log keq
 log keq = 10.08  keq = 1010.08
64.
Ans. (c)
0.059
Sol. 𝑜
Ecell = 𝐸𝑐𝑒𝑙𝑙 − 𝑛 log ,
e– + Ag Cl  AgCl + Cl– n=1
0.059
Ecell = 0.222 – 1 log{𝐶𝑙 − }
= 0.222 – 0.059 log 10–2
= 0.222 + 0.118
= 0.34 V
65.
Ans.
1 1
Sol. k–1  I=  CiZi2
(𝐼)1/2 2
𝑍+ 𝑍−
LaCl3  & Z; I, k–1
+3 −1
max. charge so, lowest kc–1

66.
Ans.
𝑜 2.303 𝑅𝑇
Sol. E = 𝐸𝐶𝑒𝑙𝑙 + 𝐹
𝑃𝐻
cation size , alkaline error 
So, kcl.
67.
Ans.
Sol. Conductometric  Resistance
Amperometric  ld
PH-metric  Voltage
Diffn pulse polarography  1
68.
Ans. (a)
𝑅𝑇 𝑎
Sol. LJP = t+ 𝑛𝐹 ln 𝑎2
1
LJP  t+
1 1
LJP t+  mobility  charge  𝑆𝑖𝑧𝑒 × 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛
So, H+
69.
Ans. (a)
Sol. SHE||MX|M  Pt/H2(g)/H+//MX/M
1
Oxidation Anode H2(g)  H+(aq) + e–
2
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Reduction Cathode M+(aq) + e–  m(s)

1
Overall reaction – 2 H2(g) + M+(aq)  M(s) + H+(aq) [H+] = 1
2.303 1
Nernst equation Ecell = 𝐸𝑐𝑒𝑙𝑙
0
− 𝑅𝑇 log [𝑀+]
𝑛𝐹
1 𝑜
Ecell + kT log [𝑀+] = 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑀
0
+ /𝑀
𝑜
− 𝐸𝑆𝐻𝐸
2.303 𝑅𝑇 0
k= Ecell – kT log [M+] = 𝐸𝑀 + /𝑀
𝑛𝐹
0
+ /𝑀 can be obtained from the plot of E cell vs Tlog [M ]
𝐸𝑀 +

70.
Ans. (b)
Sol. m = 100  at [Conc] = 4 mm
mS cm2 mol–1
m = 50 mS cm2 mol–1 [Conc] = 9 mm.
𝑜𝑚 = ?
Using Debye Huckel Theory
m = 𝑜𝑚 - b √𝑐
100 = 𝑜𝑚 - b√4 100  + 50  2 = 𝑜𝑚
50 = 𝑜𝑚 - b √9 𝑜𝑚 = 200
– – + mS cm2 mol–1
50 = b (3–2)
71.
Ans. (a)
Sol. 𝐼𝑘𝑁𝑂3 + 𝐼𝐵𝑎 (𝑁𝑂3 )2 = 1
1
𝐼𝑘𝑁𝑂3 = 2 ([𝑘 + ] × 12 + [NO3]–  (1)2]
= 0.11
𝐼𝐵𝑎[𝑁𝑂3 ]2 = 1 − 0.11 = 0.89 Let c be conc of [Ba (NO3)2]
1
([Ba2+]  4 + [N𝑂3− ] × 1) = 0.89
2
1 0.89 ×2
(4C + 2C) = 0.89 C= = 0.2967
2 6
𝑊 1000 0.2967 ×261.32
× = 0.2967 W = = 38.76 g
261.32 500 2
72.
Ans. (b)
𝑐∝2
Sol. k = 1−∝ (𝑓𝑜𝑟 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑 )
CH3COOH ⇌ CH3COO– + H+
(1–) C C
𝑐 2/𝑜2
k= 
1− 𝑜

 2
k (1 − 𝑜 ) = 𝐶 𝑜2
𝑜  𝑐 2
− 𝑜 = 𝑘 𝑜2
𝑜
1 1 𝑐
= 𝑜 + 𝑘 𝑜2


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73.
Ans. (a)
𝑜
Sol. 𝐸𝑐𝑒𝑙𝑙 = 0.675 𝑉
𝑜
𝐸𝑐𝑒𝑙𝑙
( ) = −6.5  10–4 Vk–1
𝐸 𝑃
𝑜
𝑜 𝐸𝑐𝑒𝑙𝑙
T = –nF (𝐸𝑐𝑒𝑙𝑙 −𝑇( ) )
𝑇 𝑃
= – 2  96500 (0.675 – 300  (–6.5  10–4))
= – 167910 J mol–1 = –167.9 kJ mol–1
74.
Ans. (d)
Sol. We know,
0.059
E = Eo – 𝑛 log 𝑄
Zn(s)|ZnBr2(aq, 0.20mol/kg) || AgBr(s)|Ag(s)|Cu
Zn + AgBr  ZnBr2 + Ag
𝑜 𝑜
Eo = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
= 0.730 – (–0.762)
= 1.492
0.059 [𝑍𝑛𝐵𝑟2 ][𝐴𝑔]
E = Eo – 2 log [𝐴𝑔𝐵𝑟][𝑍𝑛]
0.059 (0.20)×(0.462)
= 1.492 –  log
2 1
0.059
= 1.492 – × (−1.0343)
2
= 1.492 + 0.0305
= 1.53V
75.
Ans. (a)
Sol. 𝐴𝑔
𝑜
= 𝑜𝑁𝑎𝐼 − 𝑜𝑁𝑎𝑁𝑂3 + 𝐴𝑔𝑁𝑂
𝑜
3
= 12.69 + (12.16) + 13.34
= 13.87 milli-siemens m2 mol–1
76.
Ans. (d)
Sol.

Fe3+ + 3e– Fe n1 = 3 𝐸1𝑜 = 0.04 𝑉

Fe2+ + 2e– Fe n2 = 2 𝐸20 = −0.44𝑉
Reversing it, we get
Fe  Fe2+ +2e– n2 = 2 𝐸2𝑜 = +0.44 𝑉
Fe3+ + e– Fe2+ n3 = 1 𝐸3𝑜 =?
n3𝐸30 =n1𝐸1𝑜 + 𝑛2 𝐸2𝑜
𝑛1 𝐸1𝑜 +𝑛2 𝐸2𝑜 3×(−0.04)+2×(0.44)
𝐸3𝑜 = 3
= 1
𝐸3𝑜 = −0.12 + 0.88
= 0.76 V
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77.
Ans. (c)
Sol. Both I & II are correct
78.
Ans. (a)
Sol. According to Debye Length
1
D 
√𝐼
I = ionic Strength
1
(I = 2  MiZi2)
IKCl = k+ + cl–
0.001
0.001
1
I = 2 [0.001 + 0.001] = 0.001
(Ikcl = 0.001)
= 𝐶𝑎2+ + 2Cl–Ical–
𝐼𝐶𝑎𝐶𝑙2 0.001 0.002
1
= 2 [0.001  (2)2 + 0.002]
1
= 2 [0.004 + 0.002]
𝐼𝐶𝑎𝐶𝑙2 = 0.003
3+ 3𝐶𝑙 −
𝐼𝐴𝑙𝐶𝑙3 = 𝐴𝑙 +
0.001 0.003
1
= 2 [0.001  (3)2 + 0.003)
1
= 2 [0.009 + 0.003)
1
= 2 (0.012)
= 0.006
Hence D kcl > D CaCl2 > D AlCl3
79.
Ans. (c)
Sol. OCl– + 2e– + 2H+  H2O + Cl– (Eo = 0.94)
(n1 = 2)

1
Cl–  2 Cl2 + e– (Eo = –136V)
(n2=1)
1
OCl– + e– + 2H+  2 Cl2 + H2O
(n3 =1)
We know
𝑛1 𝐸1 + 𝑛2 𝐸2 2 ×0.94𝑉+1 ×(−1.36𝑉)
E3 = =
𝑛3 1
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E3 = 0.56
80.
Ans. (b)
Sol. E(v) = 0.0713 – 4.99  10–4 (T–298) – 3.45  10–6 (T–298)2
E(v) = 0.0713–4.99  10–4 T + 4.99  10–4  298– 3.45  10–6 (T2 – 2T298 + 2982)
𝐸
( 𝑇 ) = –4.99  10–4 – 3.45  10–6  2T + 3.45  10–6  2  298
398𝑘
= – 4.99  10–4 – 3.45  10–6  2  398 + 3.45  10–6  2  298 (At 398 K temp)
= – 4.99  10–4 – 3.45  10–6  2 (398 –298)
= – 4.99  10–4 – 3.45  10–6  2  100
= – 4.99  10–4 – 6.90  10–4
𝐸
( 𝑇 ) = – 11.89  10–4 VK–1
398𝑘
For Entropy change
𝐸
S = nF 𝑇
S = 96500  – 11.89  10–4 VK–1 (∵ n = 1)
S = –114.7 JK–1 mol–1

81.
Ans. (b)
Sol. RKCl = 90 & and RNaCl = 200
Specific conductivity KKCl = 11.2  10–3 Scm–1.
1 𝑙
and, K = 𝑅 (𝐴)
𝑙
=kR
𝐴
𝑙
Cell constant , 𝐴 = 11.2  10–3  90 cm–1
𝑙
= 1.008 cm–1
𝐴
Cell constant is same in both the cells.
1
So, Specific conductance of NaCl, kNaCl = 200 × 1.008
= 5.04  10–3 Scm–1
𝑘×1000
Molar conductance = 𝑀
5.04×10−3×1000
= 0.05
= 100.8  102
82.
Ans. (a)
Sol. at anode : Cd(s)  Cd2+ + 2e–
[𝐴𝑔𝐶𝑙+𝑒 −  𝐴𝑔+𝐶𝑙 − ]×2
At cathode : 2𝐴𝑔𝐶𝑙+𝐶𝑑(𝑠) 𝐶𝑑2++ 2𝐴𝑔(𝑠)+ 2𝐶𝑙−
Nerust equation,
𝑜 0.0591
Ecell = 𝐸𝑐𝑒𝑙𝑙 − 2 log(𝑎𝐶𝑑2+ )(𝑎𝐶𝑙− )2
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 + 𝐸𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛
= 0.40 + 0.22
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= 0.62 V
0.0591
Ecell = 0.62 – 2 log(𝑚+ 𝛾+ ) (m– –)2
0.0591
= 0.62 – 𝑙𝑜𝑔 (m+ m–) (+ 2− )
2
0.0591
= 0.62 – log (0.1) (0.2) ()3
2
0.0591
= 0.62 – 𝑙𝑜𝑔 (0.02) (0.228)3
2
0.0591
= 0.62 – log (0.000237)
2
0.0591
= 0.62 – 2  (–3.625)
= 0.62 + 0.107
= 0.73 V
83.
Ans. (b)
Sol. Compound: K₃[Fe(CN)₆]
It dissociates in water as:
K3[Fe(CN)6] = 3K+ + [Fe(CN)6]3-
From 1 mole of K₃[Fe(CN)₆], we get:
3 moles of K⁺ (charge = +1)
1 mole of [Fe(CN)₆]³⁻ (charge = –3)
Given concentration: 0.03 mol/kg
So:
[K⁺] = 3* 0.03 = 0.09 mol/kg
[[Fe(CN)₆]³⁻] = 0.03 mol/kg
I = 1/2 ∑cizi2 = 1/2 [0.09(1)2 + (0.03)(-3)2] = 1/2[0.09+0.27] = 1/2 *0.36 = 0.18 mol/Kg
84.
Ans. (d)
Sol. This is a galvanic cell, so:
Anode (oxidation): Zn → Zn²⁺ + 2e⁻
Cathode (reduction): Ag⁺ + e⁻ → Ag
E0cell = 0.80- (-0.76) = 1.56V
Ecell = E0cell - (0.591/n)log([Zn2+]/[Ag+]2)
= 1.56-(0.591/2)log(0.5/(0.1)2) = 1.56- 0.2955log50 = 1.51V

***

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