SUBJECT: CHEMISTRY ELECTROCHEMISTRY

NAME .. ENROLL NO . BATCH

SECTION-I (ONLY ONE CORRECT)

1. The molar conductivity of acetic acid at infinite dilution is 390 S cm2 mol–1. At the same temperature 0.001 M
solution of acetic acid it is 60 S cm2 mol–1. What is the degree of dissociation of 0.05 N acetic acid? [Assume
1 – α ≈ 1 for 0.05 N acid.]
(A) 0.24 (B) 0.52
(C) 0.024 (D) 0.052

2. Which of the following statements is not correct?

(A) Conductance measurement of electrolytic cell is done by balancing wheat stone’s bridge
(B) Equivalent conductance increases with increase in dilution
(C) Electrolysis of Na2 SO4 decreases pH of solution
(D) Electrolysis of CuSO4 solution decreases pH of solution

3. The EMF of the cell: Ag Ag+ (IM) I− (IM) Agl Ag is E. The solubility product of Agl can be expressed as
nF  δE 
(A) K sp = logE (B) lnK sp = nF  − E
2.303RT  δT 
nF nFE
(C) ln K sp = (D) logK sp =
E 2.303RT
4. The ionic conductance of Ca2 + and Po34− ions at infinite dilution are a and b ohm −1 cm2mol−1 respectively.
The equivalent conductance of calcium phosphate at infinite dilution will be
(A) 3b + 2a (B) 3a + 2b
(C) 2a + 2b (D) 3a + 3b

5. Conductivity of a saturated solution of AgCl in conductivity water at 25°C is 1.4×10–6S cm–1. Ionic
conductances of Ag+ and Cl− ions at 25°C, are 63 and 77.S cm2 mol−1 . Moles of KCl to be added to 5L of
1.0 × 10 −3 M AgNO3 for initiating precipitation of AgCl must exceed.
(A) 1.0 × 10 −8 (B) 5.0 × 10 −8
−7
(C) 1.0 × 10 (D) 5.0 × 10 −7

2+
6. Use the standard reduction potentials given below to calculate K f for  Zn (NH3 )4  at 25°C
e21.81 = 2.96 × 109 

Zn2 + ( aq ) + 4NH3 ( aq) Zn (NH3 ) 4

2+
Kf = ?
Zn (NH3 )4 + 2e Zn ( s ) + 4NH3 ( aq)
2+ −
E° = −1.04V
Zn 2+
( aq) + 2e −
Zn ( s ) E° = 0.76 V
(A) 6 × 10 18
(B) 3 × 10 +9
(C) 2 × 106 (D) 3 × 10 −9

7. Standard electrode potential data are useful for understanding the suitability of an oxidant in a redox
titration. Some half-cell reaction and their standard potentials are given below:
MnO−4 ( aq) + 8H+ ( aq ) + 5e − 
→ Mn2 + ( aq ) + 4H2 O ( l ) ; E° = 1.51V
Cr2 O72 − ( aq ) + 14H+ + 6e − 
→ 2Cr 2 + ( aq ) + 7H2O ( l ) E° = 1.38V
Fe3 + ( aq ) + e − 
→ Fe2 + ( aq ) E° = 0.77 V
2CO2 ( g) + 2e − 
→ C2 O24− ( aq ) ; E° = −0.49 V
Cl2 ( g ) + 2e − → 2Cl− ( aq ) ; E° = 1.40V
I2 ( g ) + 2e − 
→ 2I− ( aq ) ; E° = 0.53V
NO3 − ( aq ) + 2H+ + 2e − → NO2 ( aq ) + H2O ( l ) ; E° = 1. 52V
Consider the following statements regarding the quantitative estimation of Ferrous Oxalate
 (i) MnO −4 can be used with HNO3
(ii) Cr2O72 − can be used with HNO3
(iii) MnO −4 can be used with HCl
(iv) Cr2O72 − can be used with HCl
(v) MnO −4 can be used with H2SO4
(vi) Cr2O72 − can be used with HI
Correct statement(s) in the above is/are
(A) (i), (ii), (v) (B) (iv) and (v)
(C) (i), (ii), (iv), (v) (D) (ii), (iii), (vi)

8. Consider the following galvanic cell, at 25°C

PtH2 ( g) HA (100ml,0.1M ) H2SO4 ( 0.05M) PtH2 ( g)
(1.0 atm) (K a =10−3 ) (1.0 atm)
On addition 50 ml of 0.1 M NaOH into the anode compartment, the EMF of cell
(A) decreases 5 times (B) increases 5 times
(C) decreases 2 times (D) increases 2 times

9. Electrolysis of dil. H2SO4 generates H2S2O8 (per disulphuric acid). What current is needed to produces
H2S2O8 at the rate of 1 mole per hour assuming 75% charge efficiency.
(A) 71.48 amp. (B) 17.48 amp
(C) 35.74 amp (D) 53.74 amp.
10. Which of the following is not correct?
(A) The conductance of one cm3 of a material is called specific conductance
(B) Variation of equivalent conductance ( Λ eq ) with dilution for a strong electrolyte is represented as

Λ eq

Dilution

(C) The limiting equivalent conductances of weak electrolytes can not determined by extrapolation of the plot
of Λ against concentration (where Λ represents equivalent conductance)
(D) Specific conductance increase while molar conductance decreases on progressive dilution
11. º
Which of the following statement is incorrect is ECu Cu+2
= −0.34V and ESn
º
Sn+2
= 0.136 V, EHº + H = 0.0V
2

(A) Cu+2 ions can be reduced by H2 ( g ) (B) Sn can be oxidized by Cu+2

(C) Sn+2 ion can be reduced by H2 (D) Cu can’t be oxidized by H+
12. If a current of 10 mA be passed through silver coulometer for one minute to produce 0.638 mg silver, the
current efficiency would be
(A) 80% (B) 60%
(C) 95% (D) 100%
13. Fully charged lead Storage Battery contains 1.5L of 5.00 M H2SO 4 . If 2.5 amp of current is down for 965
minutes, then final left concentration of H2SO4
(A) 3.5 M (B) 2.00 M
(C) 4.25 M (D) 4.00 M

14. (
The resistance of 0.04 M acetic acid K a = 1.8 × 10 −5 ) solution, at 25ºC is?
[cell constant = 0.206 cm–1]
(A) 311.18Ω (B) 622.36 Ω
(C) 933.54 Ω (D) 211.5 Ω
15. In the following process of disporportionation
2ClO3− ClO2− + ClO4− E°ClO− ClO− = 0.36, E°ClO− ClO− = 0.33 V
4 3 3 2

Initial concentration of chlorate ion was 0.1 M. The equilibrium concentration of per chlorate ion will be
(A) 0.19 M (B) 0.1 M
 (C) 0.024 M (D) 0.019 M
16. Find the emf of the cell
( )
Hg, Hg2Cl ( s ) ; KCl ( saturated solution ) H+ 10 −3 M , Q, QH2 , Pt
Given Ecalomel = 0.25at 25º C
E(H)+ ,Q, QH = 0.7V
º
( 2 )
(A) 0.38 (B) 0.27
(C) 0.32 (D) 1.7
17. Solution of Potassium formate is processed for the electrolysis. Total number of gases evolved,
Gases evolved at cathode and gases evolved at anode will be respectively:
(A) 3, 2, 1 (B) 2, 2, 1
(C) 2, 1, 1 (D) 2, 1, 2
18. Consider the four different cells
Ag Ag+ ( Ag2CrO4 ,saturatedsol.) Ag+ ( 0.1M) Ag, Ecell = xV and K sp,Ag2 CrO4 = 'p'
Ag Ag+ ( AgClsaturatedsol.) Ag+ ( 0.1M) Ag, Ecell = xV and K sp,AgCl = ' q'
Ag Ag+ ( Ag3PO 4 saturatedsol.) Ag+ ( 0.1M) Ag, Ecell x V and K sp,Ag2 SO4 = 'r '
Pt H+ (1M) ( Ag2SO4 saturatedsol.) Ag+ Ag Ecell = x V and K sp, Ag2SO4 = ' s'
The correct option for solubility product for all the four cases is (by considering all cells are in equilibrium
stage)
(A) s > q > p > r (B) s < p < q < r
(C) r > s > q > r (D) r > q > p >s

19. Three faradays of electricity are passed through Al 2O3 , aqueous solution of CuSO4 and molten NaCl taken
different electrolytic cells. The amount of Al, Cu and Na deposited at the cathodes will be in the ratio of
(A) 1 mole : 2 mole : 3 mole (B) 3 mole : 2 mole : 1 mole
(C) 1 mole : 1.5 mole : 3 mole (D) 1.5 mole : 2 mole : 3 mole
20. Which of the following shall be weaker reducing agents than Ag+ ( aq )
− +
(A)  Ag ( CN)2  (B)  Ag (NH3 )2 
(C) Ag+ gaseous (D) Cu+ ( aq.)
21. A metal rod is dipped in a solution of its ion. Its electrode potential is independent of
(A) temperature (B) conc. of solution
(C) area of metal exposed (D) nature of metal
22. Which of the following is/are correct statement?
(A) Presence of electrolyte always enhance the rate of corrosion
(B) Lead storage cell is a galvanic cell without salt bridge, when it is discharged
(C) Specific conductance increases on dilution of the electrolytic solution.
(D) Molten NaCl conducts electricity due to the presence of free electrons
23. Calculate Ecell for Cr Cr 3 + ( aq ) Cr 3 + ( aq ) Cr
0.04M (1M)
(A) 0.083 V (B) 0.027 V
(C) 0.33 V (D) 0.17 V
24 Consider the following statements:
When a direct current is passed through an aqueous concentrated solution of NaCl.
1. pH of the solution decreases.
2. Metallic sodium will be deposited at the cathode.
3. Chlorine gas will be liberated at the anode
4. pH of the solution increases.
Which of the statements given above are correct?
(A) 1 and 2 (B) 2 and 3
(C) 3 and 4 (D) 1 and 3
25. Which of the following reactions is not involved in the rusting of iron?
(A) Fe ( s ) 
→ Fe2 + ( aq ) + 2e −
(B) O2 ( g ) + 4H+ ( aq ) + 4e − 
→ 2H2O ( l )
(C) 2Fe ( s ) + O2 ( g ) + 4H+ ( aq ) 
→ 2Fe2+ ( aq) + 2H2 O ( l )
→ Fe ( s )
(D) Fe2 + + 2e − 
26. Which of the following statements is incorrect regarding the galvanic cell?
(A) A reaction is spontaneous from left to right if Ecell > 0.
 (B) A reaction occurs from right to left if Ecell < 0.
(C) If the system is at equilibrium, no net reaction occurs.
(D) Ecell is temperature independent.
27. The products obtained at cathode and anode made up of platinum by the electrolysis of aqueous solution of
cupric nitrate is
(A) Hydrogen and Nitric oxide (B) Hydrogen and Oxygen
(C) Copper, Oxygen (D) Copper and Nitric oxide

28 In which of the following cells, use of KCl as salt bridge would not change the EMF of the cell
(A) Ag( s) 0.1MAgNO3 0.2M AgNO3 Ag( s)
(B) Cu( s) 0.1MCuCl2 0.1M AgNO3 AG( s)

(C) Pt,Cl2(1atm) HCl ( 0.5M) HCl ( 0.05M) Cl2(1atm) ,Pt

(D) Ag( s) 0.2MAgNO3 HCl ( 0.2M) Cl2(1atm) ,Pt

29. The emf of the cell
Ag AgCl ( s ) KCl ( aq) Hg2 Cl2 ( s ) Hg
Is 0.055 V at 298 K and the temperature coefficient is 3.38 ×10–4 V K–1 what is the enthalpy and entropy
changes at 298 K
(A) ∆ H = 8.825 kJ/mole, ∆S = 65.23 JK −1 mol−1
(B) ∆ H = 9.825 kJ/mole, ∆S = 55.23 J K −1 mol−1
(C) ∆ H = 88.25 kJ/mole, ∆S = 652.23 J K −1 mol−1
(D) ∆ H = 98.25 kJ/mole, ∆S = 552.3 J K −1 mol−1
30. Given:
A 3 + + 3e − → A ( s ) Eº = 0.06v
→ B ( s ) Eº = −0.70v
B+ + e − 
C2 ( g ) + 2e − → 2C− Eº = 1.04v
The incorrect statements among the following is
(A) C2 ( g ) will oxidize both A and B
(B) A 3 + will oxidize B
→ 3C2 + 2A ( s ) will be spontaneous
(C) The reaction 6C− + 2A 3 + 
(1.0M) (1.0M) 1atm

(D) The oxidizing power is in the order C2 > A 3 + > B +

31. Which of the following is correct?
(A) During electrolysis of aq. NaCl using Pt as anode and Hg cathode; chlorine is liberated at anode
(B) Oxidation of pure water becomes easier if H+ ions are added to it.
(C) During electrolysis of molten NaCl current flows from cathode towards anode in external circuit.
(D) Reduction potential of H2O ( l ) is more if OH−  is more
32. At 25ºC, the molar conductance of
KNO3 varies with concentration as
follows: (Graph is not upto scale).
What is the value of Λ m∞ ?
(A) 158 S cm2 mol
(B) .013 S cm2 mol
(C) 126.4 S cm2 mol
(D) 0.016 Scm2 mol

33. During the electrolysis, the amount of product liberated a electrode is plotted against charge in faraday. The
correct graph is
 (A) (B)

(C) (D)

34. Which of the following statements is correct about the electrolysis of molten ICl3
(A) I2 is liberated at cathode and Cl2 is librated at anode
(B) I2 is liberated at anode and Cl2 is liberated at cathode
(C) Cl2 is librated at both the electrodes and I2 is liberated only at cathode
(D) Both I2 and Cl2 are liberated at both the electrodes
35. For the following sequential reaction Eº values in volts at 298 K are given:
MnO−4  0.564
→ MnO−42 
2.20
→ MnO2 0.95
→ Mn+3 
1.51
→ Mn+2
Calculate Eº for MnO−4 
→ Mn+2
(A) –1.81 volt (B) –1.18 volt
(C) 1.51 volt (D) 1.18 volt
36 The conductivity of 0.01 M HA is 3.8 × 10 −5 Ω cm−1 and the conductivity of solution formed by mixing 100 cm3
∞
of 0.01 M HA and 1cm3 of 1MNaOH is 80.0 × 10 −5 Ω −1cm −1 calculate λmA .
∞ −1
if λmNa + = 50Ω cm2mol−1
(A) 76.2 × 10 −5 Ω −1cm2 mol−1
(B) 76.2 × 10 −5 Ω −1cm2mol−1
(C) 30.0 × 10 −5 Ω −1cm2mol−1
(D) 30.0 Ω −1cm2mol−1

37. For the half reaction

at pH = 3, the electrode potential at 25ºC will be

(A) 1.20 V (B) 1.42 V
(C) 1.30 V (D) 1.48 V
38. Find the emf of the cell
( )
Hg, Hg2Cl2(s); KCl (saturated solution) H+ 10 −3 M ,Q,QH2 ,Pt
Given Ecalomel = 0.25 at 25º C
EºH+ ,Q,QH = 0.7V
( 2 )
39. Specific conductance of saturated solution of AgCl is 2.68× 10–4Sm –1 and that of water is 0.86 × 10 −4 Sm –1 at
298 K. Calculate the solubility product in mol/dm 3 unit if λmº for HNO3 ,AgNO3 and HCl are
421× 10 −1 Sm2mol−1,133 × 10 −4 Sm2mol−1,426 × 10 −4 Sm2mol−1 respectively.
(A) 1.74 × 10 −10 (B) 1.32 × 10 −5
(C) 1.32 × 10 −2 (D) 1.74 × 10 −4

40. For a reaction A + 2B3 → 2B+2 + A +2 , the value of cell potential Eº of given redox reaction is
A +2 + x 
→ A Eº ⇒ + x V
B+3 + e → B+2 Eº = + y V
 x+y
(A) x − 2y (B)
2
(C) x − y (D) y − x

41. Excess of solid AgCl is added to a 0.1 M solution of Br − ions, Eº for half cell
AgBr + e −  → Ag + Br − Eº = 0.095V
AgCl + e − 
→ Ag + Cl− Eº = 0.222V
−
The value of Br ion concentration at equilibrium is [Given – antilong (2.152) = 142 ].
(A) Br −  = 0.0317V (B) Br −  = 0.013 V
(C) Br −  = 0.99 V (D) Br −  = 0.099 V
42. The steps associated with H2 gas evolution at a smooth Pt– electrode are
(i) H+ + e − H ( atom )
fast

H2 ( adsorbed )
slow
(ii) 2H

(iii) H2 ( adsorbed ) H2 ( g )
fast

Which of the following step(s) is/are responsible for over voltage in hydrogen electrode?
(A) i only (B) iii only
(C) ii only (D) both (i) and (ii)

43. What is the solubility product of a sparingly soluble BaSO4 solution present in conductivity cell. Given that
the equivalent conductance of BaCl2 , H2 SO4 and HCl are 250 S cm2 eq–1, 400 S cm 2 eq–1 and 150 S cm2
eq–1. The specific conductance of BaSO4 solution 1.6 × 10 −3 S cm−1 . Kf of water is 1.86 k/molal.
(A) 5.29 × 10 −6 (B) 2.56 × 10 −8
(C) 2.12 × 10 −5 (D) 1.03 × 10 −6

44. A fuel cell develops an electrical potential from the combustion of butane at 1 bar and 298 K.
13
C4H10 ( g ) + O2 ( g ) → 4CO2 ( g ) + 5H2O ( l ) ∆Gº = 2746KJ / mole
2
º
The cell Ecell of the fuel cell is
(A) 4.74 V (B) 0.547 V
(C) 4.37 V (D) 1.09 V
45. In the following process of disporportionation
2ClO3− ClO2− + ClO−4 º
EClO −
ClO−
= 0.36 , EClO
º
−
ClO−
= 0.33 V
4 3 3 2

Initial concentration of chlorate ion was 0.1 M. The equilibrium concentration of per chlorate ion will be
(A) 0.19 M (B) 0.1 M
(C) 0.024 M (D) 0.019 M
46. A quantity of electricity required to reduce 123 g of nitrobenzene to aniline for the current efficiency 50% is
(A) 1158000 C (B) 579000 C
(C) 231600 C (D) 289500 C
47. A cell is represented as Zn Zn ( 0.1M − 1litre ) Cu+2 Cu. The cell is discharged till its emf reaches 1.10V,
+2

( 0.9M −litre )
then it is charged (reversing discharge process) by passing 0.6 F.
2.303RT
(Given: EºZn Zn+2 = 0.76V, ECu
º
+2
Cu
= 0.34, = 0.06, log2 = 0.30 )
F
Select the incorrect option:
(A) Concentration of Cu+2 becomes 0.5 M, when emf reach 1.10 V
(B) Concentration Zn+2 becomes 1 M when emf reach 1.10 V
(C) emf of the cell just after charging is 1.118 V
(D) after charging concentration of Cu+2 becomes 0.8 M

SECTION-II (ONE OR MORE THAN ONE)

1. For the reaction
Zn ( s ) + Cu+2 (M) → Zn+2 (M' ) + Cu ( s )
E°cell = 1.1V
  Zn+2 
A graph is plotted between Ecell on y-axis and log10 on x-axis. For different values of M and M’ which
Cu+2 
of the following graph is incorrect?

(A) (B)

(C) (D)

2. Consider the following cell

If volume of solution in each compartment is 1 L and E° 2+ = −0.76 V

Zn Zn

°
ECu Cu2+
= −0.34V

Then choose the correct statement regarding the above cell after passage of 0.1 F charge
(A) Moles of Cu2 + reduced in compartment (III) is 0.025
(B) Concentration of NO3− in second compartment 0.95 M
(C) In second compartment Cu2+ ,K + and NO3− ions present
(D) Concentration of SO24− in compartment (III) is 0.975 M
3. Which of the following formulae is/are valid for potash alum? ( λ ∞eq is equivalent conductance at infinite
dilution)
1 ∞ 3 ∞
∞
(A) λ eq ( alum ) =
4
( )
λ eq K + + λ eq
4
( ) (
Al3 + + λ eq.
∞
SO42− )
(B) λm∞ ( alum ) = 8λ eq
∞
( alum )
1 ∞ 1 1
(C) λm∞ ( alum ) =
4
( ) ( )
λ aq K + + λm∞ Al3 + + λm∞ SO24+
3 4
( )
1 3 1
∞
(D) λ eq ( ) ( )
( alum ) = λm∞ K + + λm∞ Al3 + + λm∞ SO42+
2 2 4
( )

SECTION –III (ASSERTION & REASONING)

1. STATEMENT-1: 0.05 F charge is passed in 100 ml 0.1 M NaCl solution. pH of the solution is 13 (assuming
no volume change in solution) at 25°C.
and

STATEMENT-2: Given amount of NaCl is completely electrolysed by 0.05 F charge

(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
2. STATEMENT-1: In electro-chemical cell, we cannot use KCl in the salt bridge if anodic or cathodic
compartment contains Ag+ or Pb 2 + ion.
and
STATEMENT-2: Salt bridge is employed to maintain the electrical neutral and to minimize the liquid – liquid
junction potential.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1
(B) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
3. STATEMENT-1: Electrochemical cell corresponds to reaction H+ + OH H2O is a concentration cell.
and
STATEMENT-2: In above reaction at both the electrodes H2 gas electrodes can be used with same pressure
of H2 gas and same pH of solutions at both the electrodes
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1
(B) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True

SECTION-IV (PARAGRAPH)

A student performed two experiments:

Experiment I: An electrochemical cell is constructed by immersing a piece of copper wire in 25 ml of 0.2 M CuSO4
solution and a zinc strip in 25 ml of 0.2 M ZnSO4 solution and its cell potential is found to be E1 volts at 25°C.
Experiment II: In this experiment a 25 ml of 3.0 M NH3 (aq.) are added to the CuSO4 solution of experiment I and
the corresponding cell potential is found to be 0.68 V at 25°C.
 ° ° 2.303RT 
 ECu2+ Cu = 0.34 V andE Zn Zn2+ = 0.76 V & = 0.06V 
 F 
Now, Answer the following questions:
1 The value of E1 is
(A) 1.10 V (B) 0.42 V
(C) 2.20 V (D) Zero volts
2+
2 K f ( formationcons tan t ) of Cu (NH3 ) 4  is
(A) 2.5 × 10 +13 (B) 1.366 × 1011
(C) 3.415 × 1012 (D) 6.830 × 1013

PARAGRAPH-II
EMF of a cell depends on temperature and concentration. Temperature dependence and concentration dependence
of EMF is given by a mathematical equation, knows as nearest equation which is given as
2.303RT
Ecell = E°cell − log Ω.
nF
Where Ecell and E°cell are cell potential and standard cell potential at a temperature (T), n = n-factor of the
cell reaction, F is Faraday’s constant, and Q is the reation, quotient of the cell reaction.
A ( s ) A n+ ( aq) B3 + ( aq ) B ( s )
Where both A and B are metals. The variation of Ecell will log Q is as shown below:
In the graph, θ = tan−1 ( 0.01) and OP = 0.72V
[All the measurements are made at a constant temperature of P
2.303RT
of 298 K and assume = 0.06 and EB° B2+ = +0.04 V ]
F
Ecell
Now, answer the following questions ( volts )
θ
O logQ
3. Value of ‘n’ in the above cell reaction is
(A) 1 (B) 2 (C) 3 (D) 4
4. E°A + is
(A) –0.78 V (B) –0.58 V (C) + 0.78 V (D) + 0.58 V
n+ 3+
5. If  A  = 0.10M and B  = 0.10M, then find EMF of the cell at 25°C is
(A) 0.72 V (B) 0.73 V (C) 0.74 V (D) 0.75 V

PARAGRAPH-III

The emf of the given cell is –0.46 V

( )
Pt (H2 ) H2PO4− ( 0.4M) , HPO4−− 6.4 × 10 −3 M M2 + ( 0.81M) M ( s )
1atm 1444444424444444 3
1L solution

If EºM +2
M = −0.76 V ( log3 = 0.477, log2 = 0.3010 )  and temperature is 25ºC.

6. The pH of left compartment initially is

(A) 6.398 (B) 3.45
(C) 12.96 (D) 4.5687
7. pK a for reaction H2PO−4 HPO−42 + H+ is
(A) 6.84 (B) 7.94
(C) 5.2 (D) 9.2
M
8. If 1968ml NaOH is added in left compartment initially what will be the new emf of the cell
10
(A) –0.486 V (B) –0.358 V (C) + 0.25 V (D) –0.45 V

PARAGRAPH-IV
An electrochemical cell can be constructed as follows
M ( s ) M+2 ( aq ) x +3 ( aq ) x ( s )
( 0.01M) ( 0.1M)
The emf of the above cell at 298 K is observed to be 0.04 V and a graph can be plotted between E and T as:

It is given that the slope of the curve = 0.001

9. Calculate ∆S for the above cell reaction.
(A) 579 JK −1 (B) 289.5 JK −1
(C) 191JK −1 (D) 96.5 JK −1
10. The change in enthalpy for the above cell reaction can be calculated as
(A) 74.69 kJ (B) 49.19 kJ
(C) 24.87 kJ (D) 96.5 JK–1
11. The standard emf of the above cell is observed to be
(A) 0.078 V (B) 0.0006 V
(C) 0.038 V (D) 0.032 V

PARAGRAPH-V
For an electrode reaction written as
Mn + + ne − → M
RT 1
Ered = E ºred − ln n + (Nernst equation )
nF M 
0.0591 1
= E ºred − log n + at 298 K.
n M 
For the cell reaction, aA + bB xX + yY
 [ X] [ Y ]
x y
° RT
Ecell = E cell − log
[ A ] [B]
a b
nF

0.0591 [ X ] [ Y ]
x y

= E cell
º
− log at 298 K.
[ A ] [B]
a b
n
For pure solids, liquids or gases at 1 atm, molar concentration = 1.
Standard free energy change, ∆Gº = −nFE º cell where n is the number of electrons transferred in the redox reaction of
the cell, E º cell is the standard emf of the cell. F stands for 1 faraday i.e 96500 C mol–1. Standard free energy change,
∆Gº = −2.303RT log K C , where K C is the equilibrium constant at T K. K C can be calculated from E º cell by using the
0.591
relation E º cell = × logK C .
n
12. E º for the cell, Zn Zn2 + ( aq ) Cu2 + ( aq ) Cu
Is 1.10 V at 25ºC. The equilibrium constant for the cell reaction Zn + Cu2+ ( aq) Cu + Zn2 + (aq)
is of the order of
(A) 10 −37 (B) 1037
(C) 10 −17 (D) 1017

13. The EMF of the cell Zn Zn2 + ( 0.01M) Fe2 + ( 0.001M) Fe, at 298 K is 0.2905 V. The value of the equilibrium
constant for cell reaction is
0.32 0.32
(A) e 0.0295 (B) 10 0.0295
0.26 0.32
(C) 10 0.0295 (D) 10 0.0591
14. On the basis of information available from the reaction
4 2
Al + O2 → Al2 O3 , ∆g = −827 kJ mol−1
3 3
(
the minimum emf required to carry out an electrolysis of Al2O3 is F = 96500 C mol−1 )
(A) 2.14 V (B) 4.28 V
(C) 6.42 V (D) 8.56 V

PARAGRAPH-VI
A current of 20 ampere is used to plate Zn from ZnSO4 bath. Both H2 and Zn are formed at cathode the current
efficiency of Zn formation is 70%. [Atomic mass of Zn = 65.37]
15. The volume of H2 formed per hour at STP is
(A) 6.62 lit (B) 2.51 lit
(C) 4.18 lit (D) 5.02 lit
16. The volume of O2 formed per hour at STP is
(A) 6.62 lit. (B) 2.51 lit.
(C) 4.18 lit. (D) 5.02 lit.
PARAGRAPH-VII
When a certain conductance cell was filled with 0.02 M KCl solution (conductivity 0.002768 Scm –1), it has a
resistance of 82.4Ω at 298 K. When filled with 0.005 M K2SO4, it had a resistance of 324Ω.

17. Calculate conductivity of 0.005 N K 2SO4 solution

(A) 3.088 × 10 −3 S cm−1 (B) 7.04 × 10 −4 S cm−1
(C) 0.22 × 10 −4 S cm −1 (D) 7.04 × 10 4 S cm −1
18. Calculate conductance of 0.02 M KCl solution
(A) 0.002 S (B) 0.012 S
(C) 0.228 S (D) 0.003 S
19. Molecular conductivity of 0.005 N K2SO4 solution
(A) 140.80 S cm2 mol–1 (B) 140.81 S mol–1
(C) 281.6 S mol –1 (D) 281.6 S cm2 mol–1
PARAGRAPH-VIII
A galvanic cell employs a following spontaneous chemical reaction at 298 K to produce an electric current
Cr2 O7 −2 + 14H+ + 6Fe +2 
→ 2Cr +3 + 6Fe +3 + 7H2 O
( )
Given: Eº Cr2O7−2 , H+ , Cr +3 Pt = 1.33 V

(
Eº Fe ,Fe+3 +2
)
Pt = 0.77 V
Then answer the following questions

20. The emf of the cell can be increased above the standard emf by
(A) increasing Fe +3  (B) increasing Cr +3 
(C) decreasing pH (D) decreasing Cr2 O7 −2 
21. Upon discharge of a cell by 1 ampere for 80 min, the mass of anode decease
(A) 6.6 g (B) 10.8 g
(C) 0 (D) 5.4 g
1
22. If Fe +3  reduced to M keeping all other concentrations at unity. Then Ecell will be changed by
2
(A) 0.0356V (B) 0.0178V
(C) +0.0178 V (D) 0.0591V

PARAGRAPH-VIII
According to Kohlrausch law at infinite dilution each ion makes a definite contribution towards molar conductance of
electrolyte irrespective of the nature of the other ion with which it is associated and λmº = λ +º + λ −º
Although at infinite dilution, all electrolytes dissociates completely but their conductances differ from each other
because of the difference in their mobilities, defined as the distance travelled by an ion per sec under a potential
gradient of 1 V/m

23. The degree of dissociation of pure water at 55ºC is 2.8 × 10–8. Then the specific conductance of water in
moh m –1) at this temperature will be
Given: λHº + = 349.83 mho cm2 mol−1
λ OH
º
− = 198.5mho cm
2
mol−1
(A) 7.4 × 10 −8 (B) 3.2 × 10 −4 (C) 7.2 × 10 −6 (D) 8.5 × 10 −5

24. A dilute solution of NaCl is palced between two Pt electrodes which are 8.5 cm apart. A potential difference
of 7.5 volt is applied across the electrodes, what will be the distance travel led by Na + in 1 hr.
−1
Given λNaº
+ = 70 Scm mol
2

(A) 2.3 cm (B) 4.8 cm (C) 3.5 cm (D) 7.8 cm

25. When a conductivity cell was filled with 8×10–5M, HA its resistance was 105 Ω where as when it was filled
with 3 × 10 −3 M NaCl its resistance was 254Ω, . Then the % dissociation of HA will be:
Given specific conductance of 3×10–3 M NaCl = 0.25 Sm −1
λ ºA − = 70Scm2mol−1
λHº + = 350 Scm2mol−1
(A) 23 (B) 19
(C) 28 (D) 38

SECTION-V (MATRIX MATCH)

1. Match Column I with Column II
Column-I Column-II
 (A) Lead Storage Battery (p) Electrochemical cell

(B) Nickel-cadmium Battery (q) Primary cell

(C) Dry cell (r) Secondary cell

(D) Mercury cell (s) Rechargeable

2. Match the compound mentioned in column A with their products on Electrolysis mentioned in column B
Column-I Column-II

(A) CH3 COONa ( aq.) (p) Na

(B) conc. H2SO4 (q) H2

(C) NaNO3 solution (r) Marshal’s acid

(D) Fused NaCl (s) O2

(t) CO2
3. Match Column I with Column II
Column-I Column-II

(A) Eº = 0 (p) Cell is discharged

(B) E=0 (q) Q=K

(C) ∆G = 0 (r) 96500 coutomb

(D) 1 Faraday (s) 1 mole electrons

(t) Concentration cell
4. Match Column I with Column II
Column-I Column-II

(A) LiH (molten) (p) On electrolysis gives H2 gas at cathode

(B) HCOONa (aqueous) (q) On electrolysis gives H2 gas at anode

(C) E 4H4 (molten) (r) On electrolysis gives CO2 gas at anode

(D) Palladium hydride (molten (s) Does not exist

(t) Non-stoichiometric

5. Match the following

Column-I Column-II

(A) Lead Storage Battery (p) Electrochemical cell

(B) Nickel-cadmium Battery (q) Primary cell

 (C) Dry cell (r) Secondary cell

(D) Mercury cell (s) Rechargeable

SECTION-VI (INTEGER)
1. I2 ( s ) I− (1.0m ) half cell isconnectedtoH(+aq) H2 (1atm ) ,Pt half cell and its cell potential is found to be

0.7714 V. If standard reduction potential of I2( s ) I− is0.535 V the pHof H(+aq) H2 half cell will be

2. If during the electrolysis of molten Al2O3 , the volume of O2 ( g ) obtained at anode is 134.4 lite at STP, then,
the moles of Al metal deposited at cathode in the same time, will be...........

3. How many of the following compounds can conduct electricity in aqueous solutions
CoCl3 ,6NH3 ,CoCl3 .5NH3 ,CoCl3 .4NH3 ,CoCl3 .3NH3 ,Ni ( CO )4 ,CoCl2 .6H2 O,Co (NO2 )3 3NH3
4. The electrolysis of a metal salt was carried out by passing a current of 4 amp for 45 minutes. It resulted in
the deposition of 2.977 g metal. It atomic mass of the metal is 106.4g mol–1. Calculate the charge on metal
cation.

5. Molar conductance of saturated BaSO4 solution is 400 ohm−1 cm2 mol−1 and its specific conductance is
4 × 10−5 ohm−1 cm−1 . Hence solubility product value of BaSO4 can be concluded as x × 10 −8 M2 . Identify x.

6. When the voltage of the following galvanic cell:

Cu Cu ( S2 O3 )2 ( 0.001 M) , S2 O32 − ( 2M) Cu+ ( 0.05M) Cu
3−

Was measured, a value of 0.862 volt was obtained. The overall formation constant for the complex
Cu ( S2O3 )2 Cu ( S2 O3 )2 ; is
3− 3−
complex which is formed according to the reaction Cu+ + 2S2O32−
x × 1012 , find x.

7. The value of Λ m0 for HCl, NaCl, CH3 COONa are 421.5, 126 & 91 Scm2 mol respectively. The resistance of
conductivity cell with cell constant 2.01 cm –1 is 520Ω, when filled with 0.1 M CH3 COOH. Find pH of solution
in the conductivity cell.
8. How many moles of electrons flow when 160 g of pure Fe2 O3 is reacted with excess of Al powder (reaction
initiated by burning Mg ribbon)
9. Electrolysis of mononuclear complex of metal M (Molar mass = 184) using 1.1 A for 40 min produces 0.838
gm of M. What is the oxidation state of metal ‘M’ in the complex?
10. What current (in amp) is to be passed for 0.20 sec. For deposition of a certain weight of metal. Which is
equal to its electrochemical equivalent

11. If during the electrolysis of molten Al2O3 , the volume of O2 ( g ) obtained at anode is 134.4 lite at STP, then,
the moles of Al metal deposited at cathode in the same time, will be...........
12. The conductivity of a saturated solution of Co Fe ( CN)6  is 2 × 10–6 Ω −1cm −1 & that of H2O used is

4 × 10 −7 Ω −1cm −1 & ionic molar conductivities of Fe ( CN6 )

4−
& Co2 + are 444 & 86Ω −1cm2 mol–1 respectively. If
x
Ksp of Co2 Fe ( CN)6  is 70.3 × 10 − x , find the value of . (all data is at 25°C)
3
13. Find the no. of cells that can be constructed showing the same redox change Cr + 2Cr 3 + 3Cr 2+ ; and
same value of ∆Gº but different Eº and n values. (given that Eº Cr 3 + Cr 2+ = −0.40, Eº Cr 2 + / Cr = −0.91V
and Eº Cr 3 + Cr = −0.74 V)

14. The conductivity of 0.001 M Na2 SO4 solution is 2.6 × 10–4 Scm–1 and increases to 7.0 × 10 −4 Scm −1 , when
the solubility is saturated with CaSO4 . The molar conductivities of Na + and Ca2 + are 50 and 120 Scm2
mol−1 respectively. By neglecting conductivity of used water, the solubility product of CaSO4 is calculated
as x × 10 −6 M 2 . Find the value of x.
15. A current of 80 µA is passed through AgNO3 solution for 61 minutes using Pt electrodes. 75% of the cathode
is occupied by a single atom thick silver layer. If one silver atom occupies 5.5 × 10 −16 cm2 surface area then
the total surface area of the cathode is a × 102 cm2 where a will be:

16. The sum of Eº (to the nearest integer) for the following reactions at 298 K is
Ag (NH3 )2 + e −
+
Ag + 2NH3
Ag ( CN)2 + e −
−
Ag + 2CN
Given: E ºAg+ Ag
= 0.8V

K 0d for Ag (NH3 )2 = 10 −8
+

K 0d for Ag ( CN)2 = 10 −19.072

−

17. The half cell potentials of a half – cell,

A x + , A ( ) Pt
x +n

Were found to be as follows

% of reduced form :24.4 48.8
Potential ( V ) :0.101 0.115
Determine the value of n

ANSWER

SINGLE CORRECT
1. C 11. C 21. C 31. A 41. D
2 C 12. C 22. B 32. C 42. C
3 D 13. D 23. B 33. A 43. B
4 B 14. B 24. C 34. D 44. D
5. D 15. D 25. D 35 45. D
6. B 16. B 26. D 36 D 46. A
7. B 17. D 27. C 37. D 47. B
8. D 18. A 28. B 38. B
9. A 19. C 29. A 39. A
10. D 20. 30. C 40. D

ONE OR MORE THAN ONE

1. A,C,D
2. A,B,D
3. AB
ASSERTION & REASON
1. C
2. B
3. C
PARAGRAPH
1 A 6. D 11. B 16. C 21.
2 D 7. A 12. B 17. B 22.
3. B 8. B 13. B 18. B 23. D
4. A 9. A 14. A 19. D 24. A
5. B 10. D 15. B 20. 25. B

MATRIX MATCH
1.
2. A→q,t B→q, r; C→q, s; D→p
3. A→t; B→p,q; C→s; D→p
4. A→q; B→p,q,r; C→q; D→s,t
5. A→ p, r, s; B→ p, r, s; C→p, q; D→p, q
INTEGER
1. 4 6. 2 11. 8 16. 0
2. 8 7. 2 12. 6 17. 2
3. 4 8. 13. 3
4. 4 9. 6 14. 4
5. 1 10. 5 15. 3

SOLUTION

SINGLE CORRECT
1. C
Λv
For 0.001 M CH3 COOH α =
Λ∞
60
α= = 0.1538 0.154
390
Cα 2
Ka
1− α
( 0.001)( 0.0154 )
2

Ka = = 2.80 × 10 −5
(1 − 0.154 )
For 0.05 N acid K a = Cα 2
Ka 2.80 × 10 −5
∴α = =
C 0.05
= 0.0236 0.024
2 C
Balanced WSB with AC supply and galvanometer replaced by headphone is used for
conductance measurement.
 On dilution equivalent conductance increases to maximum/optimum value for both strong as well
as weak electrolyte.
1
Na2 SO2  → 2Na + + SO24− ; at cathode :H+ + e 
→ H2
2
(Electrolysisof Na2SO4 ) ; at anode : 4OH− → 2H2 O + O2 + 4eΘ
→ Cu+2 + SO−4
CuSO4  at cathode : Cu+2 + 2e → Cu
−
at anode :4CH  → 2H2O + O2 + 4e
3 D
 Ag+  Anode
× 2.303log  + 
RT
E =0−
nF  Ag  Cathode
1 nFE
= log =−
K sp 2.303.RT
4 B
Ca3 (PO4 )2 
→ 3Ca2 + + 2PO34−
∞ ∞ ∞
Λ Ca 3 ( PO4 )
= 3λ Ca 2+ + 2λ
Po3−
2 4

= 3a + 2b
Λ ∞YA = Λ ∞XZ − Λ ∞XA − Λ ∞YZ = 110 + 108 − 160 = 58
5. D
Λ m( AgCl) = Λm° ( AgCl)

= Λ °Ag+ + Λ Cl
°
−

= 63 + 77 = 140 S cm2mol−1
Concentration of saturated solution = solubility (mol/L)
1000K 1000 × 1.4 × 10 −6
Hence solubility ( AgCl ) = = = 1.0 × 10 −5 mol L−1
Λ m° 140

(
K sp ( AgCl ) = S2 = 1× 10 −5 )
2
= 1.0 × 10 −10 M2
Cl−1  required to initiate precipitation of AgCl
Ksp 1× 10 −10
= = −3
= 1.0 × 10 −7 M
+
 Ag  1.0 × 10
Moles of [Cl] = [Moles of KCl] required for 5 L of AgNO3 solution
= 5 × 1.0 × 10 −7 = 5.0 × 10 −7 moles
6. B
Zn2 + ( aq ) + 4NH3 ( aq) Zn (NH3 ) 4 ( aq ) E° = 0.28
2+

RT lnK f = nFE° = 2 × 0.28 × 96500

0.56 × 96500
ln K f = = 21.81
8.314 × 298
K f = 3 × 109
7. B
8. D
Anode half cell: H 2( g) ( g)  → 2Ha+ ( aq ) + 2e −
Cathode half cell: 2Hg+ ( aq) + 2e− → H2 ( g)
Net cell reaction H2 ( g) + 2Hg+ ( aq) → 2H+4 ( eq) + H2 ( g)
2 2
H+4  × PH2 C H+4 
Qo =   2 = 2
,n=2
Hc+  × PH2c Hc+ 
Since, it is concentration cell, so E°cell = 0
 2
−0.0591 Ha+ 
So, Ecell = log 2
2 Hc+ 

Hc+ 
log  
0.0591
or Ecell = ...(i)
1 Ha+ 
Before addition of NaOH: HA H+ + A −

∴Ha+  = k a × C = 10 −5 × 10 −1 = 10 −3 M
Hc+  = 10 −1M
0.0591 10 −1
So, E1 = log −3 = 2 × 0.0591volts
1 10
HA + NaOH NaA + H2O
5 0
After addition of NaOH Liq.moles 10
Liq.moles 5 0 3

So, it is a case of buffer.

So, ph = pK a = 5 or H3+  = 10 −5 M and Hc+  = 10 −1M
10 −1
So, E2 = 0.0591× log −5 = 4 × 0.0591volts
10
So,E2 = 2 × E1
Hence (D) is the correct answer.
9. A
2HSO−4 → 2e − + H2 S2O 8
1molality

2 mole/hr electrons need to be released = 2F

8
= F (assuming 75% charge efficiency)
5
8
= × 96500C = 1× 60 × 60
3
i = 71.48 amp.
10. D
11. C
12. C
Ag+ ( aq) + 1e− → Ag( g)
Number of faraday = No. of moles of Ag
10 × 10 −3 × 1× 60
Weight of Ag would be deposited = = 0.67mg
96500
0.638
Current efficiency = × 100% = 95%
0.67
13. D
PbO2 + 4H+ + SO −42 + 2e − → PbSO4 + 2H2O
By releasing 2F charge 2 moles of H2SO4 in consumed
2.5 × 965 × 60
Left moles of H2SO4 = 1.5 × 5 − = 6.
98500
6
Conc. of H2SO4 = = 4.0M
1.5
14. B
Ka R 1
Use, λm = λmº & λm = × 1000 & k = × cell cons tan t
C C R
15. D
ClO3− ( aq) + H2O ( l ) 
→ ClO4− + 2H+ + 2e −
2H+ + ClO3− ( aq) + 2e − 
→ ClO−2 ( aq ) + H2O ( l )
2ClO3− ( aq ) ClO2− ( aq) + ClO4− ( aq )
 E°cell = 0.33 − 0.36 = −0.03V
0.059
E = E° − logQ
n
At equilibrium, E = 0, n = 2, Q = K
0.059
O = −0.03 − logK
2
Log K = –1
K = 1/ 10
2ClO3− ( aq ) ClO2− ( aq) + ClO4− ( aq )
t0 0.1 0 0
t eq ( 0.1 − 2x ) x x
x×x 1
K= =
( 0.1 − 2x )
2
10
x = 0.019
16. B
17. D
18. A
0.059  Ag+ 
For first cell x = 0 − log anode

1  Ag+ 
cathode

Let a mole/L be the solubility of Ag2 CrO4

K sp = ( 2a ) a = 4a3
2

Then  Ag+  = 2a
 K sp 
= 2 
 4 
13
p
2× 
x =0−
0.059
log 4
1 0.1
Similarly for 2nd cell reaction
0.059 q1 2
x =0− log
1 0.1
rd
for 3 cell reaction
14
 r 
3
27 
log 
0.059
x =0−
1 0.1
for 4th cell reaction
0.059 1
x =0− log 13
1 s
2× 
4
At equilibrium Ecell = x = 0, sp
13 14
p  r 
2  3 
4 q1 2
=  
27 1
= = 13
=1
0.1 0.1 0.1 s
2 
4
p = 5 × 10 −4
q = 10 −2
10 −4
r=
3
s = 0.5
s>q>p>r
19. C
At cathode: Al+3 + 3e − → Al
Atomic mass
E Al =
3
At cathode: Cu+2 + 2e − → Cu
Atomic mass
ECu =
2
At cathode: Na + + e − → Na
atomic mass
ENa =
1
For the passage of 3F:
Mole atoms of Al deposited = 1
Mole atoms of Cu deposite = 1.5
Mole atoms of Na deposite = 1× 3 = 3
20.
21. C
22. B
(A) in presence of basic electrolyte, rate of corrosion decrease
(C) specific conductance decreases while equivalent conductance increase on dilution.
(D) In molten NaCl, electricity conduction occurs due to presence of free Na+ and Cl– ions
23. B
0.059 (1)
E= log = 0.0274 V
3 ( 0.04 )
24. C
NaOH is formed in the solution. Hence pH increases. Electrolysis of aqueous NaCl solution gives
H2 at the cathode and not Na. Cl2 gas is liberated at the anode.
25. D
26. D
27. C
Possible reaction at cathode Cu+ + + 2e → Cu; Eº = +0.34V [ ∆G = negative ]
NO3 − + 2H+ + e → NO2 + H2O;Eº = −040 [ ∆g = positive ]
So copper is deposited as cathode
At anode: 2H2 O  → 4H+ + O2 + O2 + 4e; so oxygen is evolved at anode.
28. B
Cl– constituting the KCl in the salt bridge migrates towards the half cell in which oxidation occurs
and hence this half-cell should not have any ion reversible w.r.t to electrode which may precipitate
by Cl– ion or the half – cell must no be reversible w.r.t Cl– ion.
29. A
  δE  
  = − ( 96500 ) 0.0558 − ( 298 ) 3.38 × 10 
−4
∆G = −nF E − T 
  δT P 
= 8824.732 J mol−1 = 8.825kJ mole
 δe 
∆S = nF  
 δT P
( )
= 2 × ( 96500 ) 3.38 × 10 −4 = 65.23 JK −1 mol−1

30. C
E0C2 > E0A 3+ and EB0 +
E0A3+ > EB0 +
6C− + 2A 3 + → 3C2 ( g ) + 2A ( s )
∴ Reaction not possible
31. A
(B) ⇒ 2H2O 4H+ + O2 ↑ +4e − ;
If PO = 1atm
2

Eox = E − 0.0591 log H+ 

0
ox

i.e if H+  ↑(increases) ⇒ Eox (H2O ) ↓ ( decreases )

 (D) ⇒ For 2H2O ( l ) + 2e− H2 ↑ +2OH− ;
On addition of OH– ions reduction potential decreases
32. C
Λ mc = Λ ∞ − b C for strong electrolyte (b is a constant)
125.2 = Λ m∞ − b 200 ...(1)
∞
124.2 = Λ − b 500
m ...(2)
∞
123.7 = Λ − b 1000
m ...(3)
∞
On solving ⇒ Λ = 126.37 S cm mol
m
2

33. A
According to the Faraday’s 1st law of electrolysis
ltE
W=
96500
W = ( nF ) E
nF = Number of faraday of charge
y = mx
When amount deposited is plotted against the number of faraday of charge then we get straight
line passing through origin and the slope of line (m = E) will give the equivalent mass of the
substance.
34. D
Molten ICl3 is existed as [ICl2 ] and [ICl4 ]
+ −

35
36 D
k 80 × 10 −5 Ω −1cm−1
λm∞ (NaA ) = = = 80 × 10 −3 Ω −1cm−1dm3 mol−1 = 80Ω −1cm2mol−1
c 0.01moldm−3
Now salt form will be a strong electrolyte and the solution is fairly diluted. The value of λm (NaA )
is almost λm∞ NaA = λmNa
∞ ∞
+ + λ mλ

37. D
Use Nernst Equation

E = Eº −
0.0591
log
[Pr oduct ]
n [ ac tan t ]
Re
38. B
E = EQ − Ecal
0.0591 1
= 0.7 − log − Ecal
( )
2
2 H+
39. A
(A) 1.74 × 10 −10
AgNO3 + HCl → AgCl + HNO3
(
λ 0º AgCl = 133 × 10 −4 + 426 × 10 −4 − 421× 10 −4 Sm2mol−1 )
(
= 138 × 10 −4
) Sm mol
2 −1

For AgClλm = λmº

( )
λm AgCl ( pure ) = 2.68 × 10 −4 0.86 × 10 −4 Sm−1 = 1.82 × 10−4 Sm−1
κ × 1000
λm = , here C = solubility
C
Ksp ( AgCl) = C2
40. D
41. D
 → Ag + Cl−
AgCl + e 
Ag + Br − → AgBr + e
Br → Cl−
0.1 0
( 0.1 − x ) x
E º
cell = ER = Et
⇒ 0.127
0.059  x 
Ecell = Eº − log  
x  0.1 − x 
 x 
0.127 = 0.059log  
 0.1 − x 
x = 0.099V
42. C
Over voltage depends on the slowest step of the mechanism
43. B
Equivalent conductance of BaSO4 = λBaCl2 + λH2 SO4 − λHCl
= 250 + 400 − 150 = 500S cm2 eg−1
1.6 × 10 −3 × 1000
∴ Normality of BaSO4 = = 3.2 × 10 −3
500
3.2 × 10 −3
Molarity of BaSO4 = = 1.6 × 10 −3
2
(
Solubility product = 1.6 × 10 −3 = 2.56 × 10 −6 )
44. D
∆Gº
º
Ecell =
nF
( −2746 ) × 1000
=
26 × 96500
= 1.09V
45. D
ClO3− ( aq.) + H2 O ( l ) 
→ ClO4− + 2H+ + 2e −
2H+ + ClO3− ( aq.) + 2e − → ClO2− ( aq ) + H2 O ( l )
2ClO3− ( aq ) ClO2− ( aq ) + ClO4− ( aq)
º
Ecell = 0.33 − 0.36 = −0.03V
0.059
E = Eº − logQ
n
At equilibrium, E = 0, n = 2, Q = K
0.059
O = 0.03 − logK
2
logK = −1
K = 1 10
2ClO3 − ( aq ) ClO2− ( aq.) + ClO−4 ( aq)
t0 0.1 0− 0
t eq ( 0.1 − 2x ) x x
x×x 1
K= =
( 0.1 − 2x )
2
10
x = 0.019
46. A
 NO2
NH2

+ [H] → +2H2 O

Nitrobenzene Aniline

Molecular mass
Equivalent mass of nitrobenzene =
6
123
= = 205
6

Mass
Number of equivalents of nitrobenzene =
Equivalent mass
123
=6 =
20.5
Amount of charge required = 6 × 965000 = 579000 C
Amount of charge when current efficiency is 50% = 2 × 579000C
= 1158000 C
47. B
+2
Zn + Cu → Zn+2
0.9M 0.1M − initial
0.5M 0.5 −after discharging
0.8M 0.2−after charging

0.06 0.2
E = 1.1 − log = 1.118V
2 0.8
ONE OR MORE THAN ONE
1. A,C,D
2. A,B,D
0.1
Moles of Zn2 + = = 0.05
2
+ve charge in 1st compartment
NO3− will migrates from second compartment to 1st compartment

( Zn ) in 1st compartment = 1 + 0.05

2+

2
= 1.025M

Compartment of NO3− in second compartment = 1–0.05 = 0.95M

0.05
In 3rd compartment moles of Cu2 + reduced = = 0.025
2
0.025
SO−4 − reducing in 3rd compartment 1 − = 0.975M
2
3. AB
Its n factor is 8
λm∞ ( alum ) = λ ∞eq ( alum ) × n factor
( ) ( ) ( )
2λm∞ K + = 2λm∞ Al3 + + 4λm∞ SO24− = λm∞ ( alum )
2λ ( K ) + 2 × 3λ ( Al ) + 4 × 2λ ( SO ) = 8λ ( alum )
∞
eq
+ ∞
eq.
3+ ∞
eq.
2
4
∞
eq.

1 3
λ (K ) + λ ( Al ) + λ ( SO ) = λ ( alum )
∞
eq
+ ∞
eq.
3+ ∞
eq.
2−
4
∞
eq.
4 4

ASSERTION & REASON

1. C
Only 0.01 F charge is used for electrolysis
Amount of OH– formed from 0.01 F charge
2e − + 2H2 O → 2OH− + H2 ↑
 2Cl− 
→ Cl2 + 2e −
0.01 mol of OH− is formed
0.01
OH−  = × 1000 = 0.1
100
pOH = 1
pH = 13
2. B
3. C
PARAGRAPH
1 A
The cell reaction,
Zn ( s ) + Cu2+ ( aq.) → Zn2 + ( aq.) + Cu ( s )
 Zn2+ 
log  2 + 
° 0.06
E = Ecell −
2 Cu 
0.06 0.2
= 0.34 − ( −0.76 )  − log = 1.10
2 0.2
Hence (A)
2 D
After adding NH3 , let, ‘x’ be the molarity of Cu+2 in cathode chamber.
0.06 0.1
E = 0.68 = 1.1 − log
2 x
On solving, x = 1 ×10–15M.
Such a low value of ‘x’ indicates that almost all Cu+2 ions have gone into complex.
2+
Cu2+ + 4NH3 Cu ( NH3 )4 
Initial con. 0.1M 1.5M 0
At equilibrium. 1× 10 −15 M 1.1M 0.1
0.1
Kf = = 6.830 × 1013
(1.1) × (1× 10−15 )
4

Hence (D).
3. B
4. A
5. B
6. D
0.0591 H+ 
0.46 = −0.76 − log using Nernst equation
2 0.81
Cell reaction 2H  → 2H + 2e − ( anode )
2

→ M ( cathode )
Mi+2 + 2e− 

log
(H ) + 2
 0.6   0.6 
= − = =−
1
 
.81  0.059   0.06  10
 
0.81 
log  = 10 = log1010
 H+  2 
  
(H )
+ 2
= 81× 10 −12
H+ = 9 × 10 −8
pH = 8 − 3log3
pH = 4.5687
7. A
H2PO2− HPO −4 + H
0.4M 6.4 × 10 −3 9 × 10 −4
 6.4 × 10 −3 × 9 × 10 −6
Ka =
0.4
pK a = 9 − [ 4log2 + 2log3 ] = 6.8419
8. B
−−
H2PO4− + OH− 
→ HPO + H2 O
400 196.0 6.4
200.2 0 203.2

Solution act as a buffer solution.

pH = pK a2 + log
[Salt ] = pK = 6.84
[ Acid] a2

2
0.0591 H+ 
Hence, new Ecell = −0.76 − log
2 0.81
0.0591
Ecell = 0.78 + 0.059pH + log0.81
2
Ecell = 0.358 V
9. A
10. D
11. B

Solution for Q. No. 09 to 11

M ( s ) M+2 ( aq ) x (+aq
3
) x (s)
( 0.01M) ( 0.1M)
 ∂F   ∂E 
∆S = nF   (where   is temperature coefficient)
 ∂T P  ∂T P
∆S = 6 × 96500 × 0.04
= −23160 joule
∆H = ∆H − T ∆S

∴ ∆H = −23160 + ( 298 × 579 ) = 149.38kJ

3M ( s ) + 2X3 + ( aq ) → 3M+2 ( aq ) + 2X
3
M+2  ( 0.01) 10−6
3

Q= = = −2 = 10 −4
( 0.1) 10
2 2
 X3 + 
∆G = ∆Gº +2.303RT logQ.
−231160 − ∆Gº −2.303 × 4
∆Gº = −23160 + 2.303 × 8.314 × 298 × 4
−23160 + 22823.4
= –336.6 joule
−336.6
∆Gº = −nF Eº = = 0.00058V
−6 × 96500
12. B
13. B
14. A
15. B
16. C
Solution Q. NO. 15 & 16
1
Anode 2OH → H2 O + O2 + 2e −
2
Cathode Zn2 + + 2e − → Zn
2H+ + 2e − → H2
W it 20 × 60 × 60
At cathode = = = 0.7461gm
E 96500 96500
At anode WH = 0.74461× 30 × 2 = 0.2238gm
2
100 2
0.2238 × 22.4
WO2 = = 2.51 lit.
2
0.2238 × 22.4
VH2 = = 2.51lit
2
5.9688
VO2 = × 22.4 = 4.178lit
32
17. B
R = 324Ω
1 1
C= = = 3.086 × 10 −1 S
R 324
1
K = C × = 3.086 × 10 −3 × 0.0081 = 7.04 × 10 −4 S cm−1
a
18. B
R = 82.4Ω
1 1
C= = = 0.012136 S
R 824
19. D
1000 1000 × 2
ΛM = K × = 7.04 × 10 −4 × = 281.6 Scm2mol−1
M 0.005
[M = 2M, because K 2SO4 is valent ]
20.
21.
22.
23. D
λHº 2O = λHº + + λHO
º
−

K × 1000
λm = αλ m =
C
24. A

70 × 10 −4
º
uNa + = = 7.25 × 10 −8
96500
speed
º
uNa + =
potentialgradient
Speed = 7.25 × 10 −8 × 7.5 0.085
= 6.4 × 10 −6
Dist = 2.3 cm
25. B
Cell constant = K1R1 = K 2R 2
0.25 × 254
K HA = = 63.5 × 10 −5
105
K 63.5 × 10 −5
λm = =
C 8 × 10 −2
λ 7.93 × 10 −3
α = mº = = 0.19
λm 420 × 10 −4

MATRIX MATCH
1.
2. A→q,t B→q, r; C→q, s; D→p
3. A→t; B→p,q; C→s; D→p
4. A→q; B→p,q,r; C→q; D→s,t
LiH and E 4H2 are ionic hydride end in molten state H+ ions are present and are oxidised to give
H2
Molten PdH2 (interstial) does not exist, because before reaching its m.pt it decomposes.
5. A→ p, r, s; B→ p, r, s; C→p, q; D→p, q
INTEGER
1. 4
The galvanic cell so set up is
Pt, H2atm H+ ( aq )( pH = ? ) I− ( aq )(1.0M) I2 ( s )
H2 → 2H+ + 2e −
I2 + 2e − → 2H+ + 2I−
H2 + I2 → 2H+ + 2I−
Ecell = ER − EL
2 2
H+  I− 
log    
° 0.0591
or 0.7714 = E I2I− −
2 PH2
0.0591
0.7714 = 0.535 − × 2log H+ 
2
0.7714 = 0.535 + 0.0591 pH
0.7717 − 0.535 0.2364
pH = = =4
0.0591 0.0591
2. 8
3. 4
4 compounds CoCl3 .6NH3 ,CoCl3 .5NH3 ,CoCl3 .4NH3 CoCl3 .4NH3 ,CoCl3 .6H2 O will dissociate into
ion in aqueous solution, but CoCl3 .3NH3 ,Ni ( CO )4 and Co ( NO2 )3 .3NH3 are neutral complexes.
4. 4
Let the charge on metal cation be n+ . The reduction half reaction would then be
n+ −
M + ne  → M
1mole mmole 1mole =106.4g

The quantity of electricity required to deposit

106.4g metal = n mole of electron
= n × 96500 C
n × 96500 × 2.977
∴2.977 g metal will be deposited by =
106.4
= n × 2700C of electricity
The electricity actually passed = 4 × 45 × 60C
∴4 × 45 × 60C = n × 2700C
4 × 45 × 60
n= =4
2700
5. 1
Molar conductance = (specific conductance × 1000)/(solubility)
4 × 10 −3 × 1000
Solubility = = 10 −4
400
( )
2
K sp = 10 −4 = 10 −8
6. 2
Half reaction
Cu ( S3 O3 )2 + e −
1
Cu + 2S2O32 −
Cu+ + e − Cu
Cu ( S2 O3 )2
3−
Cu+ + 2S2O32−
Cu ( S2 O3 )3 − 
log 
0.0592 2 
E = Eº − 2
1 Cu+  S2 O32 − 
10 −3
⇒ 0.862 = Eº −0.0592log = Eº +0.136
( 0.05 )( 2 )
2

º
nEcal 0.726
E0cal = 0.726V; logK f = = = 12.3
0.0592 0.0592
 ⇒ K f = 2 × 1012
⇒x = 2
7. 2
8.
9. 6
W it
×n = ; n = n factor
m 96500
n = 6= oxidation state of metal at ‘M’ reduces to M°.
10. 5
Q = zit
1 = i × 0.20
1
i= =5
0.20
11. 8
12. 6
Λ m = 2 × 86 + 444 = 616
Co2 Fe ( CN)6  = 2 × 10 −6 − 4 × 10 −7
Conductivity of
= 16 × 10 −7
K
Λm =
solubility
16 × 10 −7
Solubility = = 2.597 × 10 −9 mol cm3
616
Solubility in mol/lt. = 2.597 × 10 −6
( )
3
K sp = 4S3 = 4 × 2.597 × 10 −6

≈ 4 × ( 2.6 ) × 10 −18
3

= 70.3 × 10 −18
x = 18
x
=6
3
13. 3
Cell I
Cr Cr 3 + Cr 3 + , Cr 2 + Pt
→ Cr 3 + + 3e − ; Eº = +0.74V
Cr 
3Cr 3 + + 3e 
→ 3Cr 2 + ; Eº = −0.40V
Cr + 2Cr 3 + → 3Cr 2 + (Here n = 3 )
Eº = 0.74 − 0.40 = 0.34V
∆Gº = −3 × 0.34V × F = −1.02F
Cell II
Cr Cr 2+ Cr 3 + Cr
3Cr → 3Cr 2 + + 6e; Eº = 0.91V
3+
3Cr + 6e → 2Cr; Eº = −0.74V
Cr + 2Cr 3 + → 3Cr 2 + ( Here n = 6 ) ; Eº = 0.17V
∆Gº = −0.17 × 6 × F
=–1.02F
Cell II
Cr Cr 2 + Cr 3 + , Cr 2 + Pt
Cr → Cr 2 + + 2e; Eº = 0.91V
3+ 2+
2Cr + 2e 
→ 2Cr ; Eº = −0.40V
Cr + 2Cr 3 + → 3Cr 2 + ( here n = 2 ) ; Eº = 0.51V
 ∆Gº = −2 × 0.51× F
= −1.02F
14. 4
Conductivity of Na2 SO4 = 2.6 × 10 −4
100 × 2.6 × 10 −4
Λ m (Na2SO4 ) =
0.001
= 260 S cm2 mol–1
( )
λm SO24− = Λ m (Na2 SO4 ) − 2λm Na + ( )
= 260 − 2 × 50
= 160 S cm2 mol−1
Conductivity of CaSO4 solution = 7 × 10 −4 − 2.6 × 10 −4
= 4.4 × 10 −4 S cm−1
Λ m ( CaSO4 ) = λm Ca2+ + λm SO24− ( ) ( )
= 120 + 160
= 260 S cm2 mol−1
1000 × k 1000 × 4.4 × 10 −4
Solubility C = =
Λm 280
= 1.57 × 10 −3 M
K sp of CaSO4 = Ca2 +  SO24− 

( )(
= 1.57 × 10 −3 1.57 × 10 −3 + 1× 10 −3 )
−8
= 4 × 10 M 2

15. 3
ItE
w=
96500
80 × 10 −6 × 60 × 61× 108
96500
= 3.28 × 10 −4 g
Total number of Ag atoms deposited
3.287 × 10 −4
= × 6.022 × 1023
108
= 1.833 × 1018 atoms
Surface occupied by deposited silver = no. of silver atom × area of single Ag atoms
= 300 cm2
= 3 × 102 cm2
16. 0
E0 = E0Ag+ Ag − 0.0591 log K 0d
E + = 0.8 − 0.0591 log 10 −8
NH3 Ag(NH3 )2 Ag

= 0.3272 V
ECN Ag CN − = 0.8 − 0.0591 log 10 −19.072
( )2 Ag

= − 0.3272 V
(I) + (II) = 0
17. 2