(Physical Chemistry) ELECTROCHEMISTRY

SECTION–I : Only One options correct Type

(3 Marks each, –1 for wrong answer)
Each question has four choices (A), (B), (C) and (D) out of which ONLY ONE is correct.
_____________________________________________________________________________________________________________________
1. Consider the following reactions:
IO3− + 6H+ + 6e– ⎯→ I– + 3H2O ; E° = +0.907 V

IO3− + 3H2O + 6e– ⎯→ I– + 6OH– ; E° = +0.260 V

Predict where does IO3− acts as a better oxidant?

(A) In acidic medium

(B) In basic medium
(C) In pure water
(D) Equally effective in both acidic and basic mediums
2. Which of the following statement is correct :
If ECu2+ /Cu = 0.34V

ESn 2+
/Sn
= −0.136V

EH+ /H = −0.136V
2

(A) Cu can be oxidised by H+ ion. (B) Sn2+ ion can be reduced by H2

(C) Sn can be oxidised by Cu2+ (D) Cu can be oxidised by Sn2+
3. A solution containing 4 M Cr2O72– & 2 M Cr3+ shows a pH of 2.0. Calculate reduction potential of

half cell reaction, [ 

2.303RT 
 = 0.06]
 F 
0
ECr 2−
2 O /Cr
3+ = 1.33V
7

(A) 0.5 V (B) 0.7 V (C) 1.05 V (D) 1.50 V

(E) 2 V
4. Select the correct option if it is know that
Ksp (AgCl) > Ksp (AgBr) > Ksp (AgI)
(A) EoI− /AgI/Ag  EoBr− /AgBr/Ag  ECl
o
−
/AgCl/Ag
(B) EoI− /AgI/Ag  EoBr− /AgBr/Ag  ECl
o
−
/AgCl/Ag

(C) EAg/AgI/I¯  EAg/AgBr/Br ¯  EAg/AgCl/Cl¯ (D) None of these

o o o

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(Physical Chemistry) ELECTROCHEMISTRY

Electrolytic
5.
Electrolytic Cell-2

Cell-1 Electrolytic
Cell-3

Content Resistance Volume of gas produced

(at same T & P)
Cell-1 CuSO4 (aq) 10  at anode is V1
Cell-2 NaCl (aq) 2 at anode is V2
Cell-3 ZnSO4 (aq) 6 at cathode is V3
The ratio V1 : V2 : V3 is
(A) 2 : 3 : 1 (B) 3 : 2 : 1 (C) 3 : 1 : 2 (D) 2 : 1 :
6. Select the incorrect option, when a lead storage battery is discharged -
(A) SO2 is evolved (B) Lead sulphate is produced at both electrodes
(C) Sulphuric acid is consumed (D) Water is formed
7. The molar conductivity of 0.04 M solution of MgCl2 is 200 Scm2 mol–1 at 298 K. A cell with
electrodes that are 4 cm2 in surface area & 8 cm apart is filled with MgCl2 solution.
How much current will flow when the potential difference between the two electrodes is 10 V?
(A) 0.32 A (B) 4 × 10–2 A (C) 4 × 10–4 A (D) None of these
8. Given that (in S cm2 eq–1) at T = 298 K :
 eq for Ba(OH2), BaCl2 & NH4Cl are 228.8, 120.3 & 129.8 respectively. Specific conductance for

0.2 N NH4OH solution is 4.766 × 10–4 S cm–1, then value of pH of the given solution of NH4OH
will be nearly
(A) 9.2 (B) 11.3 (C) 12.1 (D) 7.9
9. 20 mL of KOH solution was titrated with 0.20 mol L–1 H2SO4 solution in a conductivity cell. The
data obtained were plotted to give the graph shown below –
The concentration of the KOH solution was-
(A) 0.25 M (B) 0.30 M
(C) 0.50 M (D) 0.125 M

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(Physical Chemistry) ELECTROCHEMISTRY
SECTION–II: One or More than one options correct Type
(4 Marks each, –2 for wrong answer with partial marking)
This section contains multiple choice questions. Each question has four choices (A), (B),
(C) and (D) out of which ONE OR MORE THAN ONE option(s) may be correct.
1. An aqueous solution containing 1 M NiSO4 & 1M S2O82– is electrolysed using palladium
electrode, at 25°C
Ni+2 + 2e¯ ⎯→ Ni E° = – 0.25 V
2H+ + 2e¯ ⎯→ H2 E° = 0.00 V
O2 + 4H++ 4e¯ ⎯→ 2H2O E° = 1.23 V
Pd+2 + 2e¯ ⎯→ Pd E° = 0.92 V
S2O82– + 2e¯ ⎯→ 2SO42– E° = 2 V
pH of solution is 7.
Select the correct statement on the basis of above given information.
(Ignore over voltage & neglect variation of EoPd+2 /Pd with concentration)

(A) Reaction at anode is Pd ⎯→ Pd+2 + 2e¯

(B) Reaction at anode is 2H2O ⎯→ O2 + 4H++ 4e¯
(C) Reaction at cathode is Ni+2 + 2e¯ ⎯→ Ni
(D) Reaction at cathode is 2H+ + 2e¯ ⎯→ H2
2. Select the correct statement under standard condition based on following data :
EX /X−  EY /Y−  EZ /Z−
2 2 2

(A) Y2 can oxidise Z– (B) Y2 can oxidise X–

(C) X2 is the best oxidising agent (D) Z2 is the best reducing agent
3. Select correct statements for the cell
Ag | AgCl | HCl || AgNO3 | Ag ; (S)reaction = – ve
(A) ECell  0

(B) G° < 0

(C) Ecell decrease by increasing temperature
(D) Ecell decrease by diluting anodic solution
4. A current of 0.965 ampere is passed through the acetic acid solution for 100 minutes. Assuming
no change in volume and temperature of solution and all the gases obtained (if any) at any
electrode is collected separately at STP, the correct information (s) is /are - [Given : log2 = 0.3,
log3 = 0.48]
(A) 2.64 gm CO2 gas is produced at anode (B) 681 ml H2 gas is produced at cathode
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(Physical Chemistry) ELECTROCHEMISTRY
(C) C2H6 gas is also produced at anode (D) pH of final solution is 13.08
5. Which of the following statement is/are correct-
(A) Molar conductance (m ) is independent of length (l) and area of cell (A)
(B) Molar conductance may be equal to conductance of electrolyte in cell
(C) Molar conductance is always equal to conductance of electrolyte in cell
(D) Conductance of a given cell decreases as concentration of given solute decrease.
6. Which of the following are correct-
(A) Number of moles of electron transferred per mole of H2SO4 in lead storage battery is 1
(B) Value of limiting molar conductivity for HCl is greater than compared to KCl
(C) On diluting a given electrolytic solution, molar conductance increases and conductivity
decreases
(D) Mercury cell delivers a constant potential throughout its life

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(Physical Chemistry) ELECTROCHEMISTRY
SECTION–III : Paragraph Type
(3 Marks each, –1 for wrong answer)
This section contains paragraphs describing theory, experiment, data etc. Each question
of a paragraph has only one correct answer among the four choices (A), (B), (C) and (D).
Paragraph for Question 1 to 3
H2O2 can be produced by the Ammonium hydrogen sulphate.
Reactions occurring in electrolytic cell.
NH4HSO4 ⎯→ NH4+ + H+ + SO42–
2SO42– ⎯→ S2O82– + 2e– (Anode)
2H+ + 2e– ⎯→ H2 (Cathode)
Hydrolysis of Ammonium persulphate
100%yield
(NH4)2S2O8 + 2H2O → 2NH4HSO4 + H2O2
1. What is the current efficiency when 100 Amp current is passed for 965 sec. in order to produce
17 gm of H2O2.
(A) 20 % (B) 40 % (C) 80 % (D) 100 %
2. What volume of hydrogen gas at 1 atm & 273 K will be produced at cathode in above question.
(A) 22.4 L (B) 11.2 L (C) 5.6 L (D) 2.8 L
3. How many moles of electrons are to be passed in order to produce enough H2O2 which when
reacted with excess of KI then liberated iodine required 100 ml of centimolar Hypo solution.
(A) 10–1 (B) 10–2 (C) 10–3 (D) 5 × 10–4
Paragraph for Q. No. 4 to 6
A fuel cell is the device to convert the energy of a fuel into electrical energy without the use of
heat engine, where the fuel is burnt directly. Such conversions are possible because the overall
reaction are highly exothermic. Electrical energy can be obtained indefinitely from a fuel cell as
along as the outside supply of fuel is maintained. In hydrogen – oxygen fuel cell, the following
reaction take place :
Anode reaction: 2H2 (g) + 4OH–(aq) ⎯→ 4H2O(l) + 4e–
Cathode reaction: O2(g) + 2H2O(l) + 4e– ⎯→ 4OH–(aq)
Overall reaction: 2H2(g) + O2(g) ⎯→ 2H2O(l)
Hf [H2O(l)] = – 290 kJ mol–1 and Gf [H2O(l)] = – 240 kJ mol–1 at 25°C.
4. What is the standard EMF of the cell?
(A) 0.615 V (B) 1.24 V (C) 2.46 V (D) 0.74 V

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(Physical Chemistry) ELECTROCHEMISTRY
5. How many litres of H2 gas at 1 atm and 273K will combined with excess O2 in the fuel cell in
order to produce 24kJ of useful work under standard conditions-
(A) 2.24 L (B) 4.94 L (C) 1.23 L (D) 2.46 L
6. The theoretical efficiency of the fuel cell is given by
(A) 67.53 % (B) 100 % (C) 82.75 % (D) 97.88 %

APNI KAKSHA 6
(Physical Chemistry) ELECTROCHEMISTRY
SECTION-IV : (Numerical Value Type Questions)
(3 Marks each, 0 for wrong answer)
The answer to each question is a NUMERICAL VALUE. If the numerical value has more
than two decimal places, truncate/roundoff the value to TWO decimal places.

1. Resistance of an aqueous solution containing 2 mole NH4Cl and is filled in between two
electrodes which are 20 cm apart was found to be 100 ohm. Calculate the m (Scm2mol–1) for
NH4Cl(aq.)
2. A solution contains A+ and B+ in such a concentration that both deposits simultaneously. If
current of 9.65 amp was passed through 100 ml solution for 55 seconds, then find the final
concentration of A+ ions if initial concentration of B+ is 0.1M.
Given : A+ + e– ⎯→ A E° = –0.5 volt
B+ + e– ⎯→ B E° = –0.56 volt
2.303RT
= 0.06
F
[Fill your answer by multiplying it with 103.]
3. Calculate log10 Keq for the reaction
3Br2(aq) + 6 OH–(aq) ⎯→ 5Br –(aq) + BrO3− (aq) + 3H2O

 2.303RT 
Given : EBr /Br− = 1 volt ; EBrO− /Br− = 0.5 volt  = 0.06 
2 3
 F 

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(Physical Chemistry) ELECTROCHEMISTRY
EXECISE (JEE-ADVANCED)
1. The reduction potential (E 0, in V) of MnO− 4 (aq)/Mn(s) is
0 0 0
[Given: E(M −
4 O4 (aq)/MnO2 (s))
= 1.68 V; E(MnO2(s)/Mn2+ (aq)) = 1.21 V; E(Mn2+ (aq)/Mn(s)) = −1.03 V ]

[JEE Adv.2022]
2. Consider the strong electrolytes Zm Xn , Um Yp and Vm Xn . Limiting molar conductivity (Λ0 ) of
Um Yp and Vm Xn are 250 and 440 S cm2 mol−1 , respectively. The value of (m + n + p) is
Given:

Ion Z n+ U p+ V n+ X m− Y m−

λ0 ( S cm2 mol−1 ) 50.0 25.0 100.0 80.0 100.0

λ0 is the limiting molar conductivity of ions

The plot of molar conductivity ( Λ ) of Zm Xn vs c1/2 is given below. [JEE Adv.2022]

3. Consider a 70% efficient hydrogen-oxygen fuel cell working under standard conditions at 1 bar
and 298 K. Its cell reaction is [JEE Adv.2020]

H2 ( g) + 1/2O2 ( g) → H2 O(I)

The work derived from the cell on the consumption of 1.0 × 10−3 mol of H2 ( g) is used to
compress 1.00 mol of a monoatomic ideal gas in a thermally insulated 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) + 4H + (aq) + 4e− → 2H2 O(l), E 0 = 1.23 V

2H + (aq) + 2e− → H2 (g), E 0 = 0.00 V

Use F = 96500Cmol−1 , R = 8.314 J mol−1 K −1 .

Passage 4 and 5

APNI KAKSHA 8
(Physical Chemistry) ELECTROCHEMISTRY
At 298 K, the limiting molar conductivity of a weak monobasic acid is 4 × 102 S cm2 mol−1. At
298 K, for an aqueous solution of the acid, the degree of dissociation is a 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− [JEE Adv.2020]

4. The value of α is _______ .

5. The value of y is _________.

6. For the electrochemical cell,

Mg(s)|Mg2+ (aq, 1 M) || Cu2+ (aq, 1 M)|Cu(s)

the standard emf of the cell is 2.70 V at 300 K. When the concentration of Mg2+ 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,
R
ln(10) = 2.30) [JEE Adv. 2018]
7. Consider an electrochemical cell: A(s) | An+ (aq, 2 M) || B2n+ (aq, 1 M)| B(s). The value of ΔHθ for
the cell reaction is twice that of ΔGθ at 300 K. If the emf of the cell is zero, the ΔSθ (in J
K–1 mol–1) of the cell 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.)R [JEE Adv. 2018]
8. The conductance of a 0.0015 M aqueous solution of a weak monobasic acid was determined by
using a conductivity cell consisting of plantinized Pt electrodes. The diatcane between the
elecrodes is 120 cm with an area of cross section of 1cm2 . The conductance of this solution was
found to be 5 × 10–7 S. The pH of the solution is 4. The value of limiting molar conductivity

( ) of this weak monobasic acid in aqueous solution is Z ×102 S cm–1mol–1. The value of Z is
0
m

[JEE Adv. 2017]

9. For the following cell,
Zn(s) ZnSO4 (aq) CuSO4 (aq) Cu (s)

when the concentration of Zn2+ is 10 times the concentration of Cu2+ , then expression for G
(in J mol–1) is [F is faraday constant ; R is gas constant; T is temperature; Eº (cell ) = 1.1V]
[JEE Adv. 2017]
(A) 2.303RT – 2.2 F (B) – 2.2 F
(C) 1.1F (D) 2.303RT + 1.1 F
10. For the following electrochemical cell at 298K, [JEE-Adv. 2016]
Pt(s) | H2(g, 1bar) | H+ (aq, 1M) || M4+(a), M2+(a) | Pt(s)

APNI KAKSHA 9
(Physical Chemistry) ELECTROCHEMISTRY
 M2+ ( aq.)
Ecell = 0.092 V when = 10x
 M ( aq )
4+

RT
Given : E0M4+ /M2+ = 0.151 V ; 2.303 = 0.059 V
F
The value of x is -
(A) –2 (B) –1 (C) 1 (D) 2
11. All the energy released from the reaction X → Y, rGº = –193 kJ mol–1 is used for the oxidizing
M+ and M+ → M3+ + 2e¯, Eº = –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-Adv. 2015]
12. 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 0X–  0Y–, the difference in their
pKa values , pKa(HX) – pKa(HY), is (consider degree of ionization of both acids to be <<1).
[JEE-Adv. 2015]
13. In a galvanic cell , the salt bridge – [JEE-Adv. 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
14. An aqueous solution of X is added slowly to an aqueous solution of Y as shown in List-I. The
variation in conductivity of these reactions is given in List-II. Match List-I with List-II and select
the correct answer using the code given below the lists : [JEE-Adv. 2013]
List-I List-II
(P) (C2H5)3N + CH3COOH (1) Conductivity decreases and then increases
X Y
(Q) KI(0.1M) + AgNO3(0.01M) (2) Conductivity decreases and then does not change
X Y much
(R) CH3COOH + KOH (3) Conductivity increases and then does not change
X Y much
(S) NaOH + HI (4) Conductivity does not change much and then
X Y increases
Codes :
P Q R S P Q R S
(A) 3 4 2 1 (B) 4 3 2 1
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(Physical Chemistry) ELECTROCHEMISTRY
(C) 2 3 4 1 (D) 1 4 3 2

15. The standard reduction potential data at 25ºC is given below [JEE-Adv. 2013]
Eº (Fe3+, Fe2+) = +0.77 V ;
Eº (Fe2+, Fe) = –0.44 V ;
Eº (Cu2+, Cu) = +0.34 V ;
Eº (Cu+, Cu) = +0.52 V ;
Eº (O2(g) + 4H+ + 4e– → 2H2O] = +1.23 V ;
Eº [(O2(g) + 2H2O + 4e– → 4OH–)] = +0.40 V ;
Eº (Cr3 +, Cr) = –0.74 V ;
Eº (Cr2+, Cr) = –0.91 V ;
Match Eº of the redox pair in List-I with the values given in List-II and select the correct answer
using the code given below the lists :
List-I List-II
(P) Eº(Fe3+, Fe) (1) – 0.18 V
(Q) Eº(4H2O 4H+ + 4OH+) (2) – 0.4 V
(R) Eº(Cu2+ + Cu → 2Cu+) (3) – 0.04 V
(S) Eº(Cr3+, Cr2+) (4) – 0.83 V
Codes :
P Q R S P Q R S
(A) 4 1 2 3 (B) 2 3 4 1
(C) 1 2 3 4 (D) 3 4 1 2
Paragraph for Question 16 and 17
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 0.059V. [JEE 2012]
16. The value of G (kJ mol–1) for the given cell is (take If = 96500 C mol–1)
(A) –5.7 (B) 5.7 (C) 11.4 (D) –11.4.
17. 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)
(A) 1 × 10–15 (B) 4 × 10–15 (C) 1 × 10–12 (D) 1 × 10–12
18. AgNO3 (a) 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
APNI KAKSHA 11
(Physical Chemistry) ELECTROCHEMISTRY
[JEE 2011]

Volume Volume Volume Volume

(P) (Q) (R) (S)

(A) (P) (B) (Q) (C) (R) (D) (S)

19. Consider the following cell reaction : [JEE 2011]
2Fe(s)+O2(g)+4H+(aq) → 2Fe2+(a)+ 2H2O() E° = 1.67 V

At[Fe2+] = 10–3 M, P(O2) = 0.1 atm and pH = 3, the cell potential at 25°C is –
(A) 1.47 V (B) 1.77 V (C) 1.87 V (D) 1.57 V
Paragraph for Questions 15 to 16
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 : [JEE 2010]
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.
20. For the above cell :–
(A) Ecell < 0 ; G > 0 (B) Ecell > 0 ; G < 0 (C) Ecell < 0 ; G0 > 0 (D) Ecell > 0 ; G0 < 0
21. 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 :–
(A) 35 mV (B) 70 mV (C) 140 mV (D) 700 mV
22. For the reaction of NO3¯ ion in an aqueous solution, E° is +0.96 V. Values of E° for some metal
ions are given below
V2+ (aq) + 2e¯ → V E° = – 1.19 V
Fe3+ (aq) + 3e¯ → Fe E° = – 0.04 V
Au3+ (aq) + 3e¯ → Au E° = + 1.40 V
Hg2+ (aq) + 2e¯ → Hg E° = + 0.86 V [JEE 2009]
The pair(s) of metal that is(are) oxidised by NO3¯ in aqueous solution is(are)
(A) V and Hg (B) Hg and Fe (C) Fe and Au (D) Fe and V

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(Physical Chemistry) ELECTROCHEMISTRY
23. Electrolysis of dilute aqueous NaCl solution was carried out by passing 10 milli ampere current.
The time required to liberate 0.01 mol of H2 gas at the cathode is (1 Faraday = 96500 C mol–1)
[JEE 2008]
(A) 9.65 × 104 sec (B) 19.3 × 104 sec (C) 28.95 × 104 sec (D) 38.6 × 104 sec
Paragraph for Question Nos. 24 & 25 (2 questions)
Redox reactions play a pivoted role in chemistry and biology. The values of standard redox
potential (E°) of two half-cell reactions decide which way the reaction is expected to proceed. A
simple example is a Daniel cell in which zinc goes into solution and copper gets deposited.
Given below are a set of half-cell reactions (acidic medium) along with their E° (V with respect
to normal hydrogen electrode) values. Using this data obtain the correct explanations to
I2 + 2e– → 2I– E° = 0.54
Cl2 + 2e– → 2Cl– E° = 1.36
Mn3+ + e– → Mn2+ E° = 1.50
Fe3+ + e– → Fe2+ E° = 0.77
O2 + 4H+ + 4e– → 2H2O E° = 1.23 [JEE 2007]
24. Among the following, identify the correct statement.
(A) Chloride ion is oxidised by O2 (B) Fe2+ is oxidised by iodine
(C) Iodine ion is oxidised by chlorine (D) Mn2+ is oxidised by chlorine
25. While Fe3+ is stable, Mn3+ is not stable in acid solution because
(A) O2 oxidises Mn2+ to Mn3+
(B) O2 oxidises both Mn2+ to Mn3+ and Fe2+ to Fe3+
(C) Fe3+ oxidises H2O to O2
(D) Mn3+ oxidises H2O to O2
Paragraph for Question Nos. 26 to 28(3 questions)
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 coulombs)
[JEE 2007]
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(Physical Chemistry) ELECTROCHEMISTRY
26. The total number of moles of chlorine gas evolved is
(A) 0.5 (B) 1.0 (C) 2.0 (D) 3.0
27. If the cathode is a Hg electrode, the maximum weight (g) of amalgam formed from this solution
is
(A) 200 (B) 225 (C) 400 (D) 446
28. The total charge (coulombs) required for complete electrolysis is
(A) 24125 (B) 48250 (C) 96500 (D) 193000
Question No. 29 to 31(3 questions)
Tollen’s reagent is used for the detection of aldehyde when a solution of AgNO3 is added to
glucose with NH4OH then gluconic acid is formed
Ag+ + e– ⎯→ Ag ; E0red = 0.8 V
C6H12O6 + H2O ⎯→ C6H12O7 (Gluconic acid) + 2H+ + 2e– ; E0red = – 0.05 V
Ag(NH3)2+ e– ⎯→ Ag(s) + 2NH3 ; E0 = – 0.337 V
RT F
[Use 2.303 × = 0.0592 and = 38.92 at 298 K] [JEE 2006]
F RT
29. 2Ag+ + C6H12O6 + H2O ⎯→ 2Ag(s) + C6H12O7 + 2H+
Find ln K of this reaction
(A) 66.13 (B) 58.38 (C) 28.30 (D) 46.29
30. When ammonia is added to the solution, pH is raised to 11. Which half-cell reaction is affected
by pH and by how much?
(A) Eoxd will increase by a factor of 0.65 from E0oxd
(B) Eoxd will decrease by a factor of 0.65 from E0oxd
(C) Ered will increase by a factor of 0.65 from E0red
(D) Ered will decrease by a factor of 0.65 from E0red
31. Ammonia is always is added in this reaction. Which of the following must be incorrect?
(A) NH3 combines with Ag+ to form a complex.
(B) Ag(NH3)+2 is a weaker oxidising reagent than Ag+.
(C) In absence of NH3 silver salt of gluconic acid is formed.
(D) NH3 has affected the standard reduction potential of glucose/gluconic acid electrode.
32. We have taken a saturated solution of AgBr.Ksp of AgBr is 12 × 10–14. If 10–7 mole of AgNO3 are
added to 1 litre of this solution find conductivity (specific conductance) of this solution in
terms of 10–7 S m–1 mol–1.
[JEE 2006]

APNI KAKSHA 14
(Physical Chemistry) ELECTROCHEMISTRY
Given : 0 = 6 × 10–3 S m2 mol–1 ; 0 = 8 × 10–3 S m2 mol–1 ; 0 = 7 × 10–3 S m2 mol–1
( )
Ag+ ( )
Br− ( NO3− )
33. The half cell reactions for rusting of iron are: [JEE 2005]
1
2H+ + O2 + 2e– ⎯⎯→ H2O ; E0 = + 1.23 V, Fe2+ + 2e– ⎯⎯→ Fe ; E0 = –0.44 V
2
G0 (in kJ) for the reaction is :
(A) –76 (B) –322 (C) –122 (D) –176
34. (a) Calculate G0f of the following reaction

Ag+ (aq) + Cl– (aq) ⎯→ AgCl(s)

Given : G0f (AgCl) = –109 kJ/mole, G0f (Cl–) = –129 kJ/mole, G0f (Ag+) = 77 kJ/mole

Represent the above reaction in form of a cell

Calculate E0 of the cell. Find log10KSP of AgCl
(B) (b) 6.539 × 10–2 g of metallic Zn (amu = 65.39) was added to 100 ml of saturated solution of
 Zn 2+ 
AgCl. Calculate  2
log10 , given that
Ag + 

Ag+ + e– ⎯→ Ag E0 = 0.80 V ; Zn2+ + 2e– ⎯→ Zn E0 = –0.76V

Also find how many moles of Ag will be formed ? [JEE 2005]
35. Zn | Zn2+ (a = 0.1M) || Fe2+ (a = 0.01M)|Fe. The emf of the above cell is 0.2905 V. Equilibrium
constant for the cell reaction is [JEE 2004]
(A) 100.32/0.0591 (B) 100.32/0.0295 (C) 100.26/0.0295 (D) e0.32/0.295
36. Find the equilibrium constant at 298 K for the reaction,
Cu2+(aq) + In2+(aq) Cu+(aq) + In3+(aq)
Given that E0Cu2+ |Cu+ = 0.15V, E0In3+ |In+ = –0.42V, E0In2+ |In+ = –0.40 V [JEE 2004]

37. In the electrolytic cell, flow of electrons is from:

(A) Cathode to anode in solution
(B) Cathode to anode through external supply
(C) Cathode to anode through internal supply
(D) Anode to cathode through internal supply.
38. Two students use same stock solution of ZnSO4 and a solution of CuSO4. The e.m.f of one cell is
0.03 V higher than the other. The conc. of CuSO4 in the cell with higher e.m.f value is 0.5 M. Find
 2.303 RT 
out the conc. of CuSO4 in the other cell  = 0.06  . [JEE 2003]
 F 

APNI KAKSHA 15
(Physical Chemistry) ELECTROCHEMISTRY
39. Standard electrode potential data are useful for understanding the suitablilty of an oxidant in a
redox titration. Some half cell reactions and their standard potentials are given below:
MnO–4 (aq) + 8H+(aq) + 5e– ⎯→ Mn2+ (aq) + 4H2O (l); E° = 1.51 V [JEE 2002]
Cr2O72− (aq) + 14 H+ (aq) + 6e– ⎯→ 2Cr3+ (aq) +7H2O (); E° = 1.38 V

Fe3+ (aq) + e– ⎯→ Fe2+ (aq); E° = 0.77 V

Cl2 (g) + 2e– ⎯→ 2Cl– (aq); E° = 1.40 V
Identify the only incorrect statement regarding quantitative estimation of aqueous Fe(NO3)2
(A) MnO−4 can be used in aqueous HCl (B) Cr2O72− can be used in aqueous HCl

(C) MnO−4 can be used in aqueous H2SO4 (D) Cr2O72− can be used in aqueous H2SO4

40. The reaction, [JEE 2001]

3ClO–(aq) ⎯→ ClO–3 (aq) + 2Cl–(aq)
is an example of
(A) Oxidation reaction (B) Reduction reaction
(C) Disproportionation reaction (D) Decomposition reaction
41. The correct order of equivalent conductance at infinite dilution of LiCl, NaCl and KCl is
(A) LiCl > NaCl > KCl (B) KCl > NaCl > LiCl [JEE 2001]
(C) NaCl > KCl > LiCl (D) LiCl > KCl > NaCl
42. Saturated solution of KNO3 is used to make salt bridge because
(A) velocity of K+ is greater than that of NO–3
(B) velocity of NO–3 is greater than that of K+
(C) velocities of both K+ and NO–3 are nearly the same
(D) KNO3 is highly soluble in water [JEE 2001]
43. The standard potential of the following cell is 0.23 V at 15° C & 0.21 V at 35° C
Pt | H2(g) | HCl (aq) | AgCl(s) | Ag(s)
(i) Write the cell reaction.
(ii) Calculate H0 ,S0 for the cell reaction by assuming that these quantities remain unchanged
in the range 15°C to 35°C.
(iii) Calculate the solubility of AgCl in water at 25°C. Given standard reduction potential of
the Ag+/Ag couple is 0.80 V at 25°C. [JEE 2001]
44. For the electrochemical cell, M | M+ || X– | X, E° (M+/M) = 0.44 V and E° (X/X–) = 0.33V. From this
data , one can deduce that [JEE 2000]
(A) M + X ⎯→ M+ + X– is the spontaneous reaction
(B) M+ + X– ⎯→ M + X is the spontaneous reaction
APNI KAKSHA 16
(Physical Chemistry) ELECTROCHEMISTRY
(C) Ecell = 0.77 V
(D) Ecell = –0.77 V
45. Copper sulphate solution (250 mL) was electrolysed using a platinum anode and a copper
cathode. A constant current of 2 mA was passed for 16 mintue. It was found that after
electrolysis, the absorbance (concentration) of the solution was reduced to 50% of its original
value. Calculate the concentration of copper sulphate in the solution to begin with.
[JEE 2000]
46. The following electrochemical cell has been set up
Pt(I) | Fe3+, Fe2+(a =1) || Ce4+ , Ce3+ (a = 1) | Pt(II)
E0Fe3+ /Fe2+ = 0.77 V and E0Ce4+ /Ce3+ = 1.61 V

If an ammetter is connected between the two platinum electrodes. predict the direction
of flow of current. Will the current increase or decrease with time? [JEE 2000]
47. A gas X at 1 atm is bubbled through a solution containing a mixture of 1 M Y and 1 M Z at 25°C.
If the reduction potential of Z > Y > X, then [JEE 1999]
(A) Y will oxidise X and not Z (B) Y will oxidise Z and X
(C) Y will oxidise both X and Z (D) Y will reduce both X and Z.
48. Calculate the equilibrium constant for the reaction, 2Fe3+ + 3I– 2Fe2+ + I3–. The standard
reduction potentials in acidic conditions are 0.77 and 0.54 V respectively for Fe3+ / Fe2+ and
I3– / I– couples. [JEE 1998]
49. Find the solubility product of a saturated solution of Ag2CrO4 in water at 298 K if the emf of the
cell Ag|Ag+ (satd.Ag2 CrO4 soln.) || Ag +(0.1 M) | Ag is 0.164 V at 298K. [JEE 1998]

APNI KAKSHA 17
(Physical Chemistry) ELECTROCHEMISTRY
ANSWER KEY
SECTION - 1
1. (A) 2. (C) 3. (C) 4. (B) 5. (A) 6. (A) 7. (B)
8. (B) 9. (C)
SECTION – 2
1. (B,C) 2. (A,C) 3. (A,B,C,D) 4. (A,B,C,D) 5. (A,B,D)
6. (A,B,C,D)
SECTION – 3
1. (D) 2. (B) 3. (C) 4. (B) 5. (A) 6. (C)
SECTION – 4
1. (B) 2. (5) 3. (50)
EXERCISE (JEE-ADVANCED)
1. (0.77) 2. (7) 3. (13.32) 4. (0.215) 5. (0.86)
6. (10) 7. (–11.62) 8. (6) 9. (A) 10. (D)
11. (4) 12. (3) 13. (A,B) 14. (A) 15. (D)
16. (D) 17. (B) 18. (D) 19. (D) 20. (B)
21. (C) 22. (A,B,D) 23. (B) 24. (C) 25. (D)
26. (B) 27. (D) 28. (D) 29. (A) 30. (A)
31. (D) 32. (55 S m–1) 33. (B)
34. (a) E0 = 0.59 V, log10KSP = –10 (b) 52.8, 10–6 moles

35. (B) 36. (KC = 1010) 37. (C) 38. (0.05) 39. (A)

40. (C) 41. (B) 42. (C)

43. (H0 = – 49987 Jmol–1, S0 =– 96.5 J mol–1 K–1, s =1.47 ×10–5 M)
44. (B) 45. (7.95 × 10–5M)
46. (decrease with time) 47. (A)
48. (KC = 6.26 × 107) 49. (Ksp = 2.287 × 10–12)

APNI KAKSHA 18
(Physical Chemistry) ELECTROCHEMISTRY
SOLUTION
SECTION-1
3. Cr2O72– + 14 H+ + 6 e– ⎯→ 2 Cr3+ + 7 H2O
0.059
4. EoI¯/ AgI/Ag = EoAg
+
/Ag
+ log Ksp
1
5. Cell-1 Cell-2 Cell-3
Product O2 Cl2 H2
n-Factor 4 2 2
Equivalent from the 1 3/4 1/4
given resistance
Mol 1/4 3/8 1/8
Volume ratio 2 3 1
m.M 200  0.04
7. k= = = 8 × 10–3 Scm–1
1000 1000

k = G    8 × 10–3 = G  
l 8
A  4
G = 4 × 10–3
I
V = IR =
G
I = V × G = 10 × 4 × 10–3 A  0.04 A
8. (I) Λ∘ eq Ba(OH)2 = λ∘ Ba2+ + λ∘ eq, OH −
(II) λ∘ eqBaCI2 = λ∘ eqBa2+ + λ∘ eq, CI−
(III) λ∘ eq NH4 CI = λ∘ eqNH4+ + λ∘ eq, Cl−
(IV) λ∘ eq, NH4 OH = λ∘ eq, NH4+ + λ∘ eq, OH − IV = I + III − II
⇒ λ∘ eq, NH4 OH = (228.8 + 129.8) − 120.3
= 238.3 cm2 eq−1
4.766×10−14 ×1000
λ eq, NH4 OH = = 2.383
0.2

λ eq , NH4 OH
α= = 10−2
λ0 eq N NH4 OH
NH4 OH ⇌ NH4+ + OH −
c(1 − α) Cα Cα
[CH − ] = 0.2 × 10−2 = 2 × 10−3
POH = 3 − log 2
⇒ PH = 14 − (3 − log 2) = 11.3

APNI KAKSHA 19
(Physical Chemistry) ELECTROCHEMISTRY
SECTION – 2
1. At cathode
Ni+2 + 2e¯ ⎯→ Ni E° = – 0.25 V
1
H+ + e¯ ⎯→ H2 E° = 0.00 V
2
H2O ⎯→ H2 + OH¯ kw = 10–14
-------------------------------------------------
1
e¯ + H2O ⎯→ H2 + OH¯ E° = –0.827
2
--------------------------------------------------
By Nernst equation at pH = 7 EH2O/H2 = −0.42

At anode
Pd ⎯→ Pd+2 + 2e¯ E° = – 0.92
2H2O ⎯→ O2 + 4H+ + 4e¯ EoH2O/O2 = –1.23

at pH = 7  E H2O/O2 = – 0.82

4. At cathode : 2H2 O(l) + 2e− ⟶ H2 ( g) + 2OH − (aq.)

At anode : CH3 COO− (aq. ) ⟶ CH3 COO + e−
CH3 COOH ∙ ⟶ CH3 ∗ + CO(g)
2CH3 ⋅⟶ CH3 − CH3 ( g)
0.965×100×60 W
(A) = 44 × 1 ⇒ W = 2.64gm
96500
0.965×100×60 V
(B) = 22.71 × 2 ⇒ V = 0.681 L
96500
0.965×1000×60
(D) = nOH produced × 1
96500

∴ nOH produced = 0.06

0.06
∴ [OH − ]final = × 1000 = 0.12M
500
∴ pH = 14 + log (0.12) = 13.08
SECTION – 3
4. G° = –nF ECell

or 2 × (– 240 × 103) = – 4 × 96500 × ECell

 ECell = 1.24 V

5. Mole of H2 needed for 240 kJ of useful work = 1

 Mole of H2 needed for 24 kJ of useful work = 0.1

APNI KAKSHA 20
(Physical Chemistry) ELECTROCHEMISTRY
nRT 0.1 0.0821 273
 VH2 = = = 2.24 l
P 1
G −240
6. Theoretical Efficiency of cell 100% = 100% = 82.75%
H −290
SECTION – 4
G.l2 K.V.
 m = =
n n
1 400
 = 2 Scm2mol–1
100 2
0.06 1 0.06 1
 −0.5 − log [ A+ ]
= −0.56 − log [ B+ ]
1 1

0.06 [B+ ]
0.06 = log +
1 [A ]
[B+ ]
= 10
[A+ ]
[ A+ ]initial = 0.01
9.65×55
Total equivalent of charge = = 5.5meq
96500
0.5
Final [A+ ] = = 0.005
100
∘ ∘ ∘
 Ecell = EBr2 /Br
− − EBrO− /Br
3 2

= 1 − 0.4 = 0.6 volt

6 × 0.5 = 5 × E1 + 1 × 1
2
E1 = = 0.4 volt
5
∘ 0.06
Ecell = log K eq
n
0.06
0.6 = log K eq
5

log K eq = 50

APNI KAKSHA 21
(Physical Chemistry) ELECTROCHEMISTRY
EXERCISE (JEE-ADVANCED)
1. (1)

MnO− + ∘
4 (aq) + 4H + 3e → MnO2 (s) + 2H2 O; E = 1.68 V

ΔG1o = −3F(1.68) = −5.04 F

(2)

MnO2 (s) + 4H + + 2e → Mn2+ + 2H2 O; E ∘ = 1.21 V

ΔG2o = −2F(1.21) = −2.42F

(3)

Mn2+ (aq) + 2e → Mn(s); E ∘ = −1.03 V

ΔG3o = −2F(−1.03) = +2.06F

Adding (1), (2) and (3),

MnO− +
4 (aq) + 8H + 7e ⟶ Mn(s) + 4H2 O

ΔG = ΔG1o + ΔG2o + ΔG3o

= (−5.04 − 2.42 + 2.06)F

−7FE ∘ = −5.4 F

E ∘ = 0.77 V

2. λm = λom − A√C
For electrolyte Zm Xn and from given curve

λm (Zm Xn ) = λom (Zm X n ) − A√C

336 − 339 3
−A = =−
0.04 − 0.01 0.03

⇒ A = 100

∴ For λm = 336 S cm2 mol−1

⇒ 336 = λom (Zm Xn ) − 100 × 0.04

λom = 336 + 4 = 340Scm2 mol−1

Zm Xn → mZ n+ + nXX −

APNI KAKSHA 22
(Physical Chemistry) ELECTROCHEMISTRY
∴ 50 m + 80n = 340

⇒ 5 m + 8n = 34 … (i)

Um Yp → mUOp + pYP m−

∴ 25m + 100p = λom (Um Yp ) = 250

⇒ m + 4p = 10 … (ii)

∴ 100 m + 80n = 440

⇒ 5 m + 4n = 22 … (iii)

From equation (i) and (iii)

n=3

m=2

From equation (ii)

p=2

∴ m+n+p =2+3+2= 7
0
3. Ecell = 1.23 volt
0
ΔG0 = −nFEcell {−2 × 96500 × 1.23}J

Since, Work derived from this fuel cell = 70/100 × (−ΔG∘ cell ) × 1.0 × 10−3 = x J
Since insulated vessel, hence q = 0
From equation, for monoatomic gas,

w = ΔU ⇒ x = nCV,m ΔT

3R
{CV,m = }
2

Or

70/100 × 2 × 96500 × 1.23 × 10−3 = 1 × 3/2 × 8.314 × ΔT

ΔT = 13.32

4 & 5. Solution for Questions 4 and 5 .

Molar conductivity of HX at infinite dilution

Λ∞
m

= 4 × 102 S cm2 mol−1

APNI KAKSHA 23
(Physical Chemistry) ELECTROCHEMISTRY
Molar conductivity of HX at conc. c1 = y × 102 S cm2 mol−1
c
Λ m1 y × 102 y
α1 = = =
Λ∞m 4 × 102 4

On 20 times dilution of the solution of HX

c
Λ m2 3y × 102 3y c1
α2 = = = [c2 = ]
Λ∞m 4 × 102 4 20

α1 1
= ⇒ α2 = 3α1
α2 3

HX ⇌ H + + X −

c1 (1 − α1 ) c1 α1 c1 α1

c1 α12 c2 α22 c1 (3α1 )2

Ka = = =
1 − α1 1 − α2 20(1 − 3α1 )

1 9
=
1 − α1 20(1 − 3α1 )

20 − 60α1 = 9 − 9α1

⇒ α1 = 11/51 = 0.215

Y = 4α1 = 0.086

6. Mg (s) + Cu2+ (aq) ––→ Cu (s) + Mg2+ (aq)

RT  1
Initially : E = 2.7 = E° – n    E° = 2.7
2  F  1

When : [Mg2+] = x
300 x
E = 2.67 = 2.7 –  n 
2 11500 1
n x = 2.3  x = 10
7. 2A (s) + B2n+ (aq) ––→ 2A n+ (aq) + B(s)
Given H° = 2G°
G° = H° – S°
 G° = 2 G° – TS°
G° = TS°
G = G° + RT n Q = 0
APNI KAKSHA 24
(Physical Chemistry) ELECTROCHEMISTRY
 22 
G° = –8.3 × 300 × n   = 300 × S°
1
S° = – 8.3 × n 4 = –8.3 × 2 × 0.7 = –11.62 J/K
120
8.  =G× = 5 × 10–7 × = 6 × 10–5 Scm–1
A 1
10−4
[H+] = c = 10–4 M   =
0.0015
K 1000 6 10−5 1000
m = = = 40 Scm2mol–1
0.0015 0.0015
m 
=  m = m

m 
40
 m = = 6 × 102
10−4
0.0015
 Z=6
9. Zn (s) + Cu2+(aq) ––→ Zn2+ (aq) + Cu (s)
[Zn 2+ ]
Qc = = 10
[Cu 2+ ]
G° = –2 × F × 1.1
G = G° + RT n Q = –2.2 F + RT n 10= 2.303 RT – 2.2 F
10. H2(g) + M4+(aq) ––→ 2H+(aq) + M2+(aq)
[H+ ]2 [M2+ ] 1  [M2+ ]
Q= = = 10x
PH 2 [M4+ ] 1  [M4+ ]

0.059
E = 0.092 = 0.151 – log10x  x = 2
2
11. M+ ⎯→ M3+ + 2e–
G0 = –nFE0 For 1 mole of M+
G0 = –2 × 96500 × (–0.25) J
= + 48250 J/mole = 48.25 KJ/mole
Energy released by conversion of 1 mole of
X ⎯→ Y G = –193 KJ
193
Hence mole of M+ convert = =4
48.25
12.  −   −
X Y

APNI KAKSHA 25
(Physical Chemistry) ELECTROCHEMISTRY
  + +  −    + +   −
H X H Y

 
 HX  HY (1)
m
Also = , So m (HX) =  m 1 and m (HY) =  m 2
m 

(Where 1 and 2 are degrees of dissociation of HX and HY respectively.)

Now, Given that
m (HY) = 10 m (HX).

 m 2 = 10 ×  m 1

2 = 10 1 (2)
C2
Ka = , but  << 1, therefore Ka = C2 .
1– 
2
Ka (HX) 0.01α12 0.01  1  1
 = = ×  10  = 1000 .
Ka (HY) 0.1α22 0.1  

 log (Ka (HX)) – log (Ka (HY)) = –3.

 pKa (HX) – pKa (HY) = 3.
13. Salt bridge is introduced to keep the solutions of two electrodes separate, such that the ions in
electrode do not mix freely with each other. But it cannot stop the process of diffusion.
It does not participate in the chemical reaction. However, it is not necessary for occurence of cell
reaction, as we know that designs like lead accumulator, there was no salt bridge, but still
reactions takes place.
X Y
14. (P) (C2H5 )3 N + CH3COOH ⎯→ CH3COO– (aq) + (C2H5)3NH+ (aq)

As CH3COOH is a weak acid, its conductivity is already less. On

addition of weak base, acid-base reaction takes place and new ions
are created. So conductivity increases.
(Q) KI (0.1 M) + AgNO3 (0.01 M) ⎯→ AgI  (ppt) + KNO3 (aq).
As the only reaction taking place is precipitation of AgI and in
place of Ag+, K+ is coming in the solution, conductivity remain
nearly constant and then increases.
(R) CH3COOH + KOH ⎯→ CH3COOK (aq) + H2O
OH– (aq) is getting replaced by CH3COO–, which has poorer
conductivity. So conductivity dereases and then after the end point,
due to common ion effect, no further creation of ions take place. So,
conductivity remain nearly same.

APNI KAKSHA 26
(Physical Chemistry) ELECTROCHEMISTRY
(S) NaOH + HI ⎯→ NaI (aq) + H2O
As H+ is getting replaced by Na+ conductivity dereases and
after end point, due to OH–, it increases.
So answer of 39 is : (P) – (3) ; (Q) – (4) ; (R) – (2) ; (S) – (1). Answer is (D).
15. (P) EºFe3+, Fe

 1 × 0.77 + 2 × (– 0.44) = 3 × x
0.11
 x=– V ~ – 0.04 V.
3
(Q) 4H2O  4H+ + 4OH–

2H2O ⎯→ O2 + 4H+ + 4e– – 1.23 V

+ O2 + 2H2O + 4e– ⎯→ 4OH– + 0.4 V
_____________________________________
4H2O  4H+ + 4OH– – 0.83 V

(R) Eº(Cu2+ + Cu → 2Cu+)

x × 1 + 0.52 × 1 = 0.34 × 2
x = 0.16 V.
 Cu2+ + e– ⎯→ Cu+ 0.16 V
+ Cu ⎯→ Cu+ + e– – 0.52 V
______________________________________________________________
Cu2+ + Cu ⎯→ 2Cu+ – 0.36 V
However, in the given option, – 0.18 V is printed.
(S) Eº(Cr3+, Cr2+)

x × 1 + 2 × (– 0.91) = 3 × (– 0.74)
x – 1.82 = – 2.22
 x = – 0.4 V
Hence, most appropriate is (D).
(P) – (3) ; (Q) – (4) ; (R) – (1) ; (S) – 2.
16. G = – nFEcell = – 2 × 96500 × 0.059 × 10–3 kJ/mole

APNI KAKSHA 27
(Physical Chemistry) ELECTROCHEMISTRY
= – 11.4 kJ/mole.
17. M|M2+ (aq) || M2+ (aq) | M
0.001 M
Anode : M ⎯→ M2+ (aq) + 2e–
Cathode: M2+ (aq) + 2e– ⎯→ M
____________________________
M2+ (aq)c  M2+ (aq)a

0.059  M2+ (aq)a 

Ecell = 0 – log  −3 
2  10 
0.059  M2+ (aq)a 
0.059 = − log  −3 
2  10 
 M2+ (aq)a 
– 2 = log  −3 
 10 
10–2 × 10–3 = M2+ (aq)a = solubility = s
Ksp = 4s3 = 4 × (10–5)3 = 4 × 10–15

18.
0.059 [Fe2+ ]2
19. E = Eº – log + 4
4 [H ] PO2

0.06 (10−3 )2 0.03

= 1.67 – log −3 4
= 1.67 – log107
4 (10 )  0.1 2
0.03
= 1.67 – × 7 = 1.67 – 0.105 = 1.565 = 1.57 V.
2
20.
21. M (s) | M+ (aq, 0.05 M) || M+ (aq, 1 M) | M(s)
Anode : M (s) ⎯→ M+ (aq) + e–
Cathode : M+ (aq) + e– ⎯→ M (s)
_____________________
M+ (aq) |c  M+ (aq) |a

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(Physical Chemistry) ELECTROCHEMISTRY
0.0591 M+ (aq) |a
Ecell = E°cell – log
1 M+ (aq) |c
0.0591
=0– log
1
= + ve = 70 mV and hence G = – nFEcell = – ve.

0.0591
= 70 mV + log 20 = 140 mV.
1
22. The species having less reduction potential with respect to NO3– (Eº = 0.96 V) will be oxidised by
NO3–. These species are V, Fe, Hg.
  t (sec)
23. Faraday law equivalents of H2 produced =
96500
10  10−3  t
0.01  2 = = 96500  2 = t
96500
t =19.3  104 sec
24. Cl2 + 2I– ⎯→ I2 + 2Cl– .
Eº = 1.36 + (– 0.54) = 0.82 V (+ ve). Spontaneous.
25. Mn3+ + e– ⎯→ Mn2+, 1.50 volt.
2H2O ⎯→ O2 + 4H+ + 4e–, 1.23 volt.
_____________________________________
4Mn3+ + 2H2O ⎯→ 4Mn2+ + O2 + 4H+, Ecell = 1.5 – 1.23 = 0.27 volt. (+ ve).
So Mn3+ will oxidise H2O.
26. Mol of NaCl = 4 × 0.5 = 2 mol.
1 1
No. of mole of Cl2 evolved = × mol of NaCl = × 2 = 1 mol.
2 2
27. Taking the 1 : 1 molar combination of Na–Hg amalgam.
weight = 2 × 23 + 2 × 200 = 446 g.
28. 2Na+ + 2e– ⎯→ 2Na.
No. of Faraday required = 2.
 total charge = 2 × 96500 = 193000 coulomb.
29. 2Ag+ + C6H12O6 + H2 ⎯→ 2Ag(s) + C6H12O7 + 2H+, Eº = 0.8 – 0.05 = 0.75 volt.
0.0592
0 = 0.75 – log K.
2
ln K = 2.303 × log K = 2.303 × 25.34 = 58.38.
30. [H+] = 10–11 M.

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(Physical Chemistry) ELECTROCHEMISTRY
0.0591
Eoxide = – 0.05 – log(10–11)2 = – 0.05 + 0.65
2
or, H = 0.65 volt.
31. Standards electrode potential does not depend upon on concentration.
32. AgBr (s)  Ag+ + Br–

(s + 10–7) × s = Ksp = 12 × 10–14 .

s = 3 × 10–7 M.
[Ag+] = 4 × 10–7 M ; [Br–] = 3 × 10–7 M ; [NO3–] = 10–7 M.
Ktotal = Ag+ + Br– + NO3–
Ktotal = 4 × 10–4 × 6 × 10–3 + 3 × 10–4 × 8 × 10–3 + 1 × 10–4 × 7 × 10–3.
Ktotal = 24 + 24 + 7.
Ktotal = 55 Scm–1.
33. Fe ⎯→ Fe2+ + 2e–, 0.44 V.
1
2H+ + O2 + 2e– ⎯→ H2O, 1.23 V.
2
____________________________________________
1
Fe + 2H+ + O2 ⎯→ Fe2+ + H2O, Eº = 0.44 + 1.23 = 1.67 volt.
2
Gº = – 2 × 1.67 × 96500 = – 322.3 kJ.
34. (a) Ag+(aq) + Cl–(aq) ––→ AgCl(s)
Gorxn = –109 – (–129) – 79

= –57 kJ/mole
G° = –nFE°
–57 × 100 = –1 × 96500 × E°
E° = 0.591 V
1
G° = –RT n = –57 × 100
Ksp
log Ksp = –10

(b) 2Ag+(aq) + Zn(s) ––→ Zn2+(aq) + 2Ag(s)

E° = 0.8 + 0.76 = 1.56 V
0.06
E° = log Kq = 1.56
2
Kq = 1052

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(Physical Chemistry) ELECTROCHEMISTRY
35. Zn + Fe2+ ––→ Fe + Zn2+
0.1
Q= = 10
0.01
0.0591
E = E° – logQ
2
0.0591
0.2905 = E° – log(10)
2
E° = 0.32
0.0591
E° = logK = 0.32
2
K = 100.32/0.0295
36. In+ ⎯→ In3+ + 2e–, E° = 0.42 V

In2+ + e ⎯→ In+, E° = – 0.4 V

______________________________
In2+ ⎯→ In3+ + e–
______________________________
Eº = 0.44 V
Eºcell = 0.15 + 0.44 = 0.59 V
0.059
0 = 0.59 – log K.
1
K = 1010
37.
0.06 [Zn 2+ ]
38. E + 0.03 = Eº – log .
2 0.5
0.06 [Zn 2+ ]
E = Eº – log . M = 0.05 M.
2 C
39. MnO4– ion can oxidise both Fe2+ to Fe3+ as well as Cl– to Cl2 . So Fe(NO3)2 cannot be estimated
quantitatively with MnO4– ion in HCl.
EºCell for the cell Pt, Cl2(g) (1 atm) | Cl– (aq) | | MnO4– (aq) | Mn2+ (aq). is euqal to (1.51 – 1.4)
= 0.11 V.
40. Disproportionate reaction
1
41. conductance 
Hydrated radius of ion
42.

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(Physical Chemistry) ELECTROCHEMISTRY
43. (i) H2(g) + 2AgCl(s) ––→ 2Ag(s) + 2H+ (aq) + 2Cl–(aq)
(ii) G° = H° – TS° = –nF°
At 15°C : H° – 288 × S° = –2 × 96500 × 0.23
At 35°C : H° – 308 × S° = –2 × 96500 × 0.21
On solving
H° = –49587 J/mole
S° = –96.5 J/mole-K
44. E°cell = 0.33 + 0.44 = 0.77 Volt
since E°cell is positive therefore reaction is spontaneous.
45. Let initially [Cu2+] = C M
C  250
 moles of Cu2+ in the solution = = 0.25 C moles
1000
After electrolysis
0.25  C
Moles of Cu2+ =
2
0.25  C
Eq. of Cu2+ = × 2 = faraday of electricity.
2
0.25 × C = 2 × 10–3 × 16 × 60/69500
2 10−3 16  60
C= = 7.95 × 10–5 M
0.25  96500
46. Cell reaction :
Fe2+ + Ce4+ ––→ Ce3+ + Fe3+
Q=1
E = E° = 1.61 – 0.77 = 0.84 V
 Direction of flow of current is cathode to anode which will decrease with time.
47. The specie having higher reduction potential oxidizes the specie having lower reduction
potential.
0.06
48. E° = 0.77 – 0.54 = 0.23 = logK
2
K = 6.26 × 107
49. Ag+(cathode) ––→ Ag+(anode)
0.1 M 2S
2S
Q=
0.1

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(Physical Chemistry) ELECTROCHEMISTRY
0.06  2S 
E = 0.164 = – log  
2  0.1 
S = 9.23 × 10–3
Ksp = 4S3 = 2.287 × 10–12

APNI KAKSHA 33