Part - I: Practice Test-1 (Iit-Jee (Main Pattern) ) : Electrochemistry

Electrochemistry
 Marked Questions may have for Revision Questions.

This Section is not meant for classroom discussion. It is being given to promote self-study
and self testing amongst the Resonance students.
PART - I : PRACTICE TEST-1 (IIT-JEE (MAIN Pattern))
Max. Marks: 100 Max. Time : 1 Hour
Important Instructions:
A. General %
1. The test paper is of 1 hour duration.
2. The Test Paper consists of 25 questions and each questions carries 4 Marks. Test Paper consists of
Two Sections.
B. Test Paper Format and its Marking Scheme:

1. Section-1 contains 20 multiple choice questions. Each question has four choices (1), (2), (3) and (4) out
of which ONE is correct. For each question in Section-1, you will be awarded 4 marks if you give the
corresponding to the correct answer and zero mark if no given answers. In all other cases, minus one
(–1) mark will be awarded.
2. Section-2 contains 5 questions. The answer to each of the question is a Numerical Value. For each
question in Section-2, you will be awarded 4 marks if you give the corresponding to the correct answer
and zero mark if no given answers. No negative marks will be answered for incorrect answer in this
section. In this section answer to each question is NUMERICAL VALUE with two digit integer and
decimal upto two digit. If the numerical value has more than two decimal places truncate/round-off
the value to TWO decimal placed.
SECTION-1
This section contains 20 multiple choice questions. Each questions has four choices (1), (2), (3) and (4)
out of which Only ONE option is correct.
1. The standard electrode potentials (reduction) of Pt/Fe3+, Fe2+ and Pt/Sn4+, Sn2+ are + 0.77 V and 0.15 V
respectively at 25° C. The standard EMF of the reaction Sn4+ + 2Fe2+  Sn2+ + 2Fe3+ is
(1) – 0.62 V (2) – 0.92 V (3) + 0.31 V (4) + 0.85 V
2. Which is/are correct among the following?
Given, the half cell emf’s E0Cu2 | Cu  0.337 , ECu
0
1
| Cu
 0.521
(1) Cu+1 disproportionates (2) Cu and Cu2+ comproportionates.
(3) E0Cu | Cu2
 ECu
0
1
| Cu
is positive (4) (1) and (3) Both
3. How many g of silver will be displaced from a solution of AgNO3 by 4 g of magnesium?

(1) 18 g (2) 4 g (3) 36 g (4) 16 g
4. The electrode potentials for Cu2+(aq) + e–  Cu+(aq) and Cu+(aq) + e–  Cu(s) are +0.15 V and + 0.50V
respectively. The value of EºCu2 /Cu will be :
(1) 0.500 V (2) 0.325 V (3) 0.650 V (4) 0.150 V
5. How much will the reduction potential of a hydrogen electrode change when its solution initially at
pH = 0 is neutralised to pH = 7 at 25ºC ?
(1) Increases by 0.059 V (2) Decreases by 0.059 V
(3) Increases by 0.41 V (4) Decreases by 0.41 V
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ADVECH - 57
Electrochemistry
6. Consider the following Galvanic cell as shown in
figure. By what will value the cell voltage change
when concentration of ions in anodic and
cathodic compartments are both increased by
factor of 10 at 298 K
(1) + 0.591 V
(2) – 0.0591 V
(3) – 0.1182 V
(4) 0 V
7. In a cell that utilise the reaction : Zn (s) + 2H+ (0.1M)  Zn2+ (aq) + H2 (g)
addition of 0.1 M H2SO4 to cathode compartment will :
(1) increase the cell emf and shift equilibrium to the left.
(2) lower the cell emf and shift equilibrium to the right.
(3) increase the cell emf and shift equilibrium to the right.
(4) lower the cell emf and shift equilibrium to the left.
8. The chemical reaction, 2AgCl(s) + H2 (g) 2HCl (aq) + 2Ag (s)
taking place in a galvanic cell (under standard condition) is represented by the notation.
(1) Pt(s) | H2 (g), 1 bar | 1 M KCl (aq) | AgCl(s) | Ag (s)
(2) Pt(s) | H2 (g), 1 bar | 1 M HCl (aq) | 1 M Ag+ (aq) | Ag (s)
(3) Pt(s) | H2 (g), 1 bar | 1 M HCl (aq) | AgCl (s) | Ag (s)
(4) Pt(s) | H2 (g), 1 bar | 1 M HCl (aq) | Ag (s) | AgCl (s)
9. For the cell, Pt | H2 (g)  H+ (aq) || Cu2+ (aq) | Cu (s) ; EºCu / Cu2 = – 0.34 V.
Then calculate approximate value of Keq ?
(1) 5 × 1012 (2) 2 × 1011 (3) 2 × 10–11 (4) 5 × 10–12
10. In the given figure, the electrolytic cell contains 1 L of an aqueous 1 M
Copper (II) sulphate solution. If 0.4 mole of electrons are passed through
cell, the concentration of copper ion after passage of the charge will be :
(1) 0.4 M
(2) 0.8 M
(3) 1.0 M
(4) 1.2 M
11. Cost of electricity for the production of 'X' litre H2 at NTP at cathode is Rs. X. Then cost of electricity for the
production 'X' litre O2 gas at NTP at anode will : (assume 1 mole of electrons as one unit of electricity)
(1) 2X (2) 4X (3) 16X (4) 32X
12. A current of 0.1 A was passed for 965 second through a solution of Cu+ solution and 0.03175 g of
copper was deposited on the cathode. Calculate the current efficiency for the copper deposition.
(Cu – 63.5)
(1) 79% (2) 39.5 % (3) 63.25% (4) 50%
13. A current of 9.95 amp following for 10 minutes, deposits 3 g of a metal. Equivalent weight of the metal is :
(1) 12.5 (2) 18.5 (3) 21.5 (4) 48.5
14. The specific conductance of a N/10 KCl at 25°C is 0.0112 ohm –1 cm–1. The resistance of cell containing
solution at the same temperature was found to be 55 ohms. The cell constant will be
(1) 6.16 cm–1 (2) 0.616 cm–1 (3) 0.0616 cm–1 (4) 616 cm–1
15. The equivalent conductance of a N/10 NaCl solution at 25ºC is 10–2 Sm2eq–1. Resistance of solution
contained in the cell is 50 . Cell constant is:
(1) 50 m–1 (2) 50 × 10–6 m–1 (3) 50 × 10–3 m–1 (4) 50 × 103 m–1
16. For an NaCl (aq.) solution, which of the following quantities go to zero as NaCl concentration goes to
zero? (Assume the solvent’s contribution to conductivity has been subtracted off).
(1) m (2)  (3)  m Na  (4)  m C   
ADVECH - 58
Electrochemistry

17. Find the value of eq for potashalum.
  
Given : m K  = 73.5 –1cm2 mol–1,  mAl 3  = 198  –1cm2 mol–1, mSO42  = 160  –1cm2 mol–1
(1) 145.6 –1cm2 eq–1 (2) 1165–1cm2 eq–1
–1 –1
(3) 532 cm eq 2
(4) 195.5–1cm2 eq–1
18. A graph of molar conductivity of three electrolytes (NaCl, HCl and NH4OH) is plotted against C
m
1
2
3
C
Which of the following options is correct ?
(1) (2) (3) (1) (2) (3)
(1) NaCl HCl NH4OH (2) NH4OH NaCl HCl
(3) HCl NaCl NH4OH (4) NH4OH HCl NaCl
19. 0.1 molar solution NaCl filled in different conductivity cell. Order of equivalent conductance of NaCl
solution is :
Cell – 1 Cell – 2 Cell – 3
A 5 cm2 6 cm2 10 cm2
l 2 cm 3 cm 4 cm2
Equivalents : a b c
conductance A = Area of cross section, l = distance between two electrode.
(1) Cell – 1 > Cell – 2 > Cell – 3 (2) Cell – 1 = Cell – 2 = Cell – 3
(3) Cell – 1 > Cell – 3 < Cell – 2 (4) None of these
20. Acetic acid is titrated with NaOH solution. Which of the following statement is correct for this titration?
(1) conductance increases upto equivalence point, then it decreases
(2) conductance increases upto equivalence point, then it increases
(3) first conductance increases slowly upto equivalence point and then increases rapidly
(4) first conductance increases slowly upto equivalence point and then drops rapidly .
SECTION-2
This section contains 5 questions. Each question, when worked out will result in Numerical Value.
21.
The E° in the given figure is X. Report the answer as 10X.

22. The standard reduction potential for Zn+2/Zn ; Ni+2/Ni ; and Fe+2/Fe are –0.76V, –0.23V, –0.44V
respectively. In how many of the following, the reaction X + Y+2  X+2 + Y will be non-spontaneous:
X Y
(I) Ni Fe
(II) Ni Zn
(III) Fe Zn
(VI) Zn Ni
23. A current is passed through 2 voltameters connected in series. The first voltameter contains XSO 4 (aq.)
and second has Y2SO4 (aq.). The relative atomic masses of X and Y are in the ratio of 2 : 1. The ratio of
the mass of X liberated to the mass of Y liberated is a : b. Find a + b
ADVECH - 59
Electrochemistry
24. The ratio of wt. deposited of metal x, y, z on passing electric charge in ratio of 1 : 2 : 3 respectively is
3 : 2 : 1 then the ratio of equivalent weights for the above metals respectively is a : b : c. Find a + b + c
25. A resistance of 50 is registered when two electrodes are suspended into a
beaker containing a dilute solution of a strong electrolyte such that exactly
half of the them are submerged into solution as shown in figure. If the
solution is diluted by adding pure water (negligible conductivity) so as to just
completely submerge the electrodes, the new resistance offered by the
solution would be :
Practice Test-1 (IIT-JEE (Main Pattern))

OBJECTIVE RESPONSE SHEET (ORS)
Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25
Ans.
PART - II : JEE (MAIN) / AIEEE OFFLINE PROBLEMS (PREVIOUS YEARS)

1. For the following cell with hydrogen electrodes at two different pressure p1and p2,
Pt | H2(g) | H+(aq) | H2 (g) | Pt
p1 1M p2
emf is given by : [AIEEE 2002, 3/225]
RT p RT p RT p RT p
(1) loge 1 (2) loge 1 (3) loge 2 (4) loge 2
F p2 2F p2 F p1 2F p1
2. Which of the following reactions is possible at anode : [AIEEE 2002, 3/225]

(1) 2 Cr3+ + 7H2O Cr2O72– + 14H+ (2) F2 2F–
1
(3) O2 + 2H+  H2O (4) displacement reaction
2
3. For a cell given below : [AIEEE 2002, 3/225]
Ag | Ag+ || Cu2+ | Cu
– +
Ag+ + e–  Ag Eº = x
Cu2+ + 2e–  Cu, Eº = y
The value of Eºcell is :
(1) x + 2y (2) 2x + y (3) y –x (4) y – 2x
4. For a cell reaction involving a two electron change, the standard emf of the cell is found to be 0.295 V
at 25°C. The equilibrium constant of the reaction at 25°C will be : [AIEEE 2003, 3/225]
(1) 1 × 10–10 (2) 29.5 × 10–2 (3) 10 (4) 1 × 1010
5. Standard electrode potentials of three metals A, B and C are +0.5 V, –3.0 V and –1.2 V respectively.
The reducing power of these metals is in the order : [AIEEE 2003, 3/225]
(1) B > C > A (2) A > B > C (3) C > B > A (4) A > C > B
ADVECH - 60
Electrochemistry
6. Consider the following Eº values :
0
EFe 3
/ Fe
2  = + 0.77 V ; E0Sn2 / Sn = – 0.14 V
Under standard conditions, the cell potential for the reaction given below is : [AIEEE 2004, 3/225]
Sn(s) + 2Fe3+(aq)  2Fe2+(aq) + Sn2+(aq)
(1) 1.68 V (2) 1.40 V (3) 0.91 V (4) 0.63 V
7. The limiting molar conductivities º for NaCl, KBr and KCl are 126, 152 and 150 S cm 2 mol–1
respectively. The value of º for NaBr is : [AIEEE 2004, 3/225]
(1) 128 S cm2 mol–1 (2) 176 S cm2 mol–1 (3) 278 S cm2 mol–1 (4) 302 S cm2 mol–1
8. In a cell that utilizes the reaction Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g),
addition of H2SO4 to cathode compartment will : [AIEEE 2004, 3/225]
(1) lower the E and shift equilibrium to the left.
(2) lower the E and shift the equilibrium to the right.
(3) increase the E and shift the equilibrium to the right.
(4) increase the E and shift the equilibrium to the left.
0
9. The EM 3
/ M2 
values for Cr, Mn, Fe and Co are – 0.41, + 1.57, + 0.77 and + 1.97 V respectively. For
which one of these metals, the change in oxidation state from +2 to +3 is easiest :[AIEEE 2004, 3/225]
(1) Cr (2) Mn (3) Fe (4) Co
10. Aluminium oxide may be electrolysed at 1000ºC to furnish aluminium metal (At.Mass of Al = 27 amu ;
1 Faraday = 96,500 Coulombs). The cathode reaction is Al 3+ + 3e–  Al0. To prepare 5.12 kg of
aluminium metal by this method, one would require : [AIEEE–2005, 3/225]
(1) 5.49 × 107 C of electricity (2) 1.83 × 107 C of electricity
(3) 5.49 × 104 C of electricity (4) 5.49 × 1010 C of electricity
11. The molar conductivities NaOAc

0
and HCl
0
at infinite dilution in water at 25°C are 91.0 and 426.2
Scm2/mol respectively. To calculate HOAc
0
, the additional value required is : [AIEEE–2006, 3/165]
(1)  H0 2O (2) KCl
0
(3) NaOH
0
(4) NaCl
0
12. Given data is at 25°C :

Ag + – Ag + e– ; E° = 0.152 V
Ag Ag+ + e– ; E° = – 0.800 V
0.474
What is the value of log Ksp for AgI : (Take = 8.065) [AIEEE–2006, 3/165]
0.059
(1) – 8.12 (2) + 8.612 (3) – 37.83 (4) – 16.13
13. Resistance of a conductivity cell filled with a solution of an electrolyte of concentration 0.1 M is 100 .
The conductivity of this solution is 1.29 Sm –1. Resistance of the same cell when filled with 0.02 M of the
same solution is 520 . The molar conductivity of 0.02 M solution of the electrolyte will be : (Take
129
= 0.248) [AIEEE–2006, 3/165]
520
(1) 124 × 10–4 Sm2mol–1 (2) 1240 × 10–4 Sm2mol–1
(3) 1.24 Sm2mol–1 (4) 12.4 × 10–4 Sm2mol–1
14. The equivalent conductances of two strong electrolytes at infinite dilution in H 2O (where ions move
freely through a solution) at 25°C are given below : [AIEEE–2007, 3/120]
 CH3COONa = 91.0 Scm /equiv and
0 2
HCl = 426.2 Scm /equiv
0 2
What additional information/quantity one needs to calculate º of an aqueous solution of acetic acid :
(1) The limiting equivalent conductance of H+ ( H ) (2) º of chloroacetic acid (ClCH2COOH)
(3) º of NaCl (4) º of CH3COOK
ADVECH - 61
Electrochemistry
15. The cell Zn | Zn2+(1M) || Cu2+(1M) | Cu : (E°cell = 1.10V) was allowed to completely discharge at 298 K.
  Zn2  
The relative concentration of Zn 2+
to Cu 2+    is : (Take 1.1 = 18.65) [AIEEE–2007, 3/120]
 Cu  
2  0.059
 
(1) 1037.3 (2) 9.65 × 104 (3) antilog (24.08) (4) 37.3
16. Given : E0 = – 0.72, E0 = – 0.42 V

Cr3 / Cr Fe2 / Fe
The potential for the cell Cr | Cr (0.1 M) || Fe2+(0.01 M) | Fe at 298 K is :
3+
2.303 R (298)
(Take = 0.06) [AIEEE–2008, 3/105]
F
(1) 0.339 V (2) – 0.339 V (3) – 0.26 V (4) 0.26 V
17. 0
Given : EFe3
/ Fe
= – 0.036 V, EFe
0
2
/ Fe
= – 0.439 V
3 2
The value of standard electrode potential for the change, Fe(aq) + e–  Fe(aq) will be :
(1) 0.385V (2) 0.770V (3) –0.270V (4) –0.072V
18. The Gibbs energy for the decomposition of Al 2O3 at 500ºC is as follows : [AIEEE–2010, 4/144]
2 4
Al2O3  Al + O2 ; rG = + 966 kJmol–1. The potential difference needed for electrolytic reduction
3 3
of Al2O3 at 500ºC is at least :
(1) 4.5 V (2) 3.0 V (3) 2.5 V (4) 5.0 V
19. The reduction potential of hydrogen half-cell will be negative, if : [AIEEE–2011(1), 4/120]
(1) p(H2) = 1 atm and [H+] = 2.0 M (2) p(H2) = 1 atm and [H+] = 1.0 M
(3) p(H2) = 2 atm and [H+] = 1.0 M (4) p(H2) = 2 atm and [H+] = 2.0 M
20. The standard reduction potentials for Zn2+/Zn, Ni2+/Ni and Fe2+/Fe are –0.76, – 0.23 and –0.44 V
respectively. The reaction X + Y2+  X2+ + Y will be spontaneous, when : [AIEEE 2012, 4/120]
(1) X = Ni, Y = Fe (2) X = Ni, Y = Zn (3) X= Fe, Y = Zn (4) X= Zn, Y = Ni
21. Given : E0Cr 3  / Cr = –0.74 V ; EMnO

0

/ Mn2 
= 1.51 V
4
E0Cr O2 / Cr3 = 1.33 V ; E0Cl / Cl = 1.36 V

2 7
Based on the data given above, strongest oxidising agent will be : [JEE(Main) 2013, 4/120]
(1) Cl (2) Cr3+ (3) Mn2+ (4) MnO4–
22. Resistance of 0.2 M solution of an electrolyte is 50 . The specific conductance of the solution is 1.4 S
m–1. The resistance of 0.5 M solution of the same electrolyte is 280 . The molar conductivity of 0.5 M
solution of the electrolyte in S m 2 mol–1 is : [JEE(Main) 2014, 4/120]
(1) 5  10–4
(2) 5  10 –3
(3) 5  103
(4) 5  102
23. The equivalent conductance of NaCl at concentration C and at infinite dilution are C and ,
respectively. The correct relationship between C and  is given as : (where the constant B is positive)
[JEE(Main) 2014, 4/120]
(1) C =  + (B)C (2) C =  – (B)C (3) C =  – (B) C (4) C =  + (B) C
24. The metal that cannot be obtained by electrolysis of an aqueous solution of its salts is :
[JEE(Main) 2014, 4/120]
(1) Ag (2) Ca (3) Cu (4) Cr
ADVECH - 62
Electrochemistry
25. Given below are the half-cell reactions : [JEE(Main) 2014, 4/120]
Mn2+ + 2e– Mn ; Eº = –1.18 V
2(Mn3+ + e–  Mn2+) ; Eº = +1.51 V
The Eº for 3Mn2+  Mn + 2Mn3+ will be :
(1) –2.69 V ; the reaction will not occur (2) –2.69 V ; the reaction will occur
(3) –0.33 V ; the reaction will not occur (4) –0.33 V ; the reaction will occur
26. Two Faraday of electricity is passed through a solution of CuSO4. The mass of copper deposited at the
cathode is : (at. mass of Cu = 63.5 amu) [JEE(Main) 2015, 4/120]
(1) 0 g (2) 63.5 g (3) 2 g (4) 127 g
27. Galvanization is applying a coating of : [JEE(Main) 2016, 4/120]
(1) Cr (2) Cu (3) Zn (4) Pb
28. Given
º º
ECl / Cl–
= 1.36 V, ECr 3
/ Cr
= –0.74 V
2
º º
ECr O2  / Cr 3 
= 1.33 V, EMnO–
/ Mn2 
= 1.51 V
2 7 4
Among the following, the strongest reducing agent is : [JEE(Main) 2017, 4/120]
(1) Mn2+ (2) Cr3+ (3) Cl– (4) Cr
29. How long (approximate) should water be electrolysed by passing through 100 amperes current so that
the oxygen released can completely burn 27.66 g of diborane? [JEE(Main)-2018, 4/120]
(Atomic weight of B = 10.8u)
(1) 3.2 hours (2) 1.6 hours (3) 6.4 hours (4) 0.8 hours
PART - III : NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) STAGE-I

1. The increase in the equivalent conductance of a salt solution on dilution is due to increase in the
[NSEC-2000]
(A) attraction between the ions (B) degree of ionization of the salt
(C) molecular attraction (D) association of the salt
2. When 96500 coulombs of electricity are passed through a nickel sulphate solution, the amount of nickel
deposited will be [NSEC-2000]
(A) 1.0 mol (B) 0.5 mol (C) 0.1 mol (D) 2.0 mol [NSEC-2000]
3. When a piece of copper wire is immersed in a silver nitrate solution, the colour of the solution turns blue
due to [NSEC-2000]
(A) oxidation of silver (B) reduction of copper
(C) oxidation of copper (D) formation of soluble complex
4. The reduction potentials of Zn, Cu, Fe and Ag are in the order : [NSEC-2001]
(A) Zn,Cu,Fe,Ag (B) Cu,Ag,Fe,Zn (C) Ag,Cu,Fe,Zn (D) Fe,Zn,Cu, Ag
5. The standard reduction potentials of Cu2+/Cu and Cu+/Cu are 0.339 V and 0.518 V respectively. The
standard electrode potential of Cu2+/Cu+ half cell is : [NSEC-2001]
(A) 0.16 V (B) 0.827 V (C) 0.184 V (D) 0.490 V
6. How many coulombs are required for oxidation of 1 mole of H2O to O2 ? [NSEC-2001]
(A) 3.86 × 105C (B) 9.65 × 104C (C) 1.93 × 105C (D) 4.825 × 104C
7. The metal which can not be obtained by electrolysis of its aqueous salt solution is : [NSEC-2001]
(A) Au (B) Al (C) Ag (D) Cu
8. The units of conductivity are : [NSEC-2001]
(A) Siemen–1.cm–1. (B) Siemen.cm (C) Siemen.cm–1 (D) Semen.cm–2.mol–1
ADVECH - 63
Electrochemistry
9. The calomel electrode used a reference elecrode contains : [NSEC-2001]
(A) PbO2-PbSO4 mixture (B) HgCl2
(C) Hg2Cl2 (D) ZnCl2
10. KCl is used in a salt bridge because : [NSEC-2001]

(A) it forms a good jelly with agar-agar
(B) it is strong electrolyte
(C) it is a good conductor of elelctric current
(D) the transference number of K+ and Cl– ions are almost equal
11. During the electrolysis of fused NaCl, the reaction occurring at the anode is : [NSEC-2001]
(A) reduction of Na+ ions (B) oxidation of Cl– ions
+
(C) oxidation of Na ions (D) reduction of Cl– ions
12. On electrolysis, one mole of chromium ions will be deposited by : [NSEC-2001]
(A) three moles of electrons (B) two moles of electrons
(C) one mole of electrons (D) six moles of electrons
13. The quantity of electricity which deposits 1.08 g of silver from AgNO 3 solution is : [NSEC-2002]
(A) 96500 coulombs (B) 9650 coulombs (C) 965 coulombs (D) 96.5 coulombs.
14. In the conductometric titration of CH3 COOH vs NaOH, the titration curve obtained will be of the type
[NSEC-2002]
(A) (B) (C) (D)
15. The standared reduction potentials at 298 K for the half reactions are: [NSEC-2002]
(a) Zn2+ (aq) + 2e–  Zn(s) ; –0.762 V (b) Cr3+ (aq) + 3e–  Cr (s) ; – 0.740 V
(c) 2H (aq) + 2e  H2(g) ; 0.000 V
+ –
(d) Fe3+ (aq) + e–  Fe2+ (aq) ; 0.770 V
Which is the strongest reducing agent?
(A) Zn (s) (B) Cr (s) (C) H2 (g) (D) Fe2+(aq).
16. The molar conductivities of H+, Li+ and Na+ ions in aqueous solutions at infinite dilution are in the order :
[NSEC-2003]
(A) H+ > Li+ > Na+ (B) H+ < Li+ < Na+ (C) H+> Na+ > Li+ (D) Na+ > H+ > Li+.
17. Fe2+ + 2e  Fe .....(i)

Fe + e  Fe
3+ 2+
.....(ii)
The standard potentials (in volt) corresponding to the reactions (i) and (ii) are E1 and E2 respectively.
The value (in volt) of the standard potential corresponding to the reaction Fe3+ + 3e  Fe is
[NSEC-2003]
(A) (E1+E2) (B) (2E1+E2)/3 (C) (E1 +2E2)/2 (D) (E1+E2)/3.
18. The standard reduction potentials of Cu2+, Zn2+, Sn2+ and Ag+ are 0.34, –0.76, –0.14 and 0.80 V
respectively. The storage that is possible without any reaction is for [NSEC-2003]
(A) CuSO4 solution in a zinc vessel (B) AgNO3 solution in a zinc vessel
(C) AgNO3 solution in a tin vessel (D) CuSO4 solution in a silver vessel.
19. A certain current passed through CuSO4 solution for 100 seconds deposits 0.3175 g of copper. The
current passed (in A) is [NSEC-2004]
(A) 4.83 (B) 9.65 (C) 0.963 (D) 0.483
20. The salt that can be used in the salt bridge of an electrochemical cell is [NSEC-2004]
(A) FeCI3 (B) AgCI (C) CH3COONa (D) KNO3.
ADVECH - 64
Electrochemistry
21. The conductometric titration curve (of conductance vs mL of NaOH) obtained when acetic acid is
titrated against NaOH is [NSEC-2005]
(A) (B) (C) (D)
22. In an alkaline energy cell the overall cell reaction is as follows :

Zn(s) + 2MnO2(s) + 2H2O  Zn(OH)2(s) + 2MnO(OH).
Which of the following reactions is taking place at the cathode? [NSEC-2005]
(A) 2MnO2(s) + 2H2O + 2e  Zn(OH)2(s) + 2MnO(OH)(s)
(B) 2MnO2(s) + 2H2O + 2e  2MnO(OH)(s) + 2OH–(aq)
(C) Zn(s) + 2OH- (aq)  Zn(OH)2(s) + 2e
(D) Zn(OH)2(s) + 2e  Zn(s) + 2OH–(aq).
23. What is the charge on an ion of tin if 7.42 g of metallic tin is deposited by passage of 24125 coulombs
through a solution containing the ion ? [NSEC-2005]
(A) +1 (B) +3 (C) +2 (D) +4.
24. The cell potential (E) and free energy change (G) accompanying an electrochemical reaction, are
related by [NSEC-2005]
[NSEC-2005]
(A) G = nFE (B) G = nFE (C) G = nFlogE (D) G = nF logE. .
25. The mass of the copper, in grams, deposited during the passage of 2.5 ampere current through a Cu(II)
sulphate solution for 1 hour is [NSEC-2006]
(A) 5.96 (B) 29.8 (C) 2.98 (D) 59.6
26. The standard reduction potentials of Fe2+/Fe and Cu2+/Cu electrodes are –0.44 and 0.34 volts,
respectively. The following reaction would occur [NSEC-2006]
(A) copper will reduce Fe2+ ions (B) iron will reduce Cu2+ ions
(C) iron will oxidise copper metal (D) Cu2+ ions will reduce Fe2+.
27. Rusting of iron is due to the formation of [NSEC-2006]
(A) hydrated ferrous oxide (B) hydrated ferric oxide
(C) only ferric oxide (D) a mixture of ferric oxide and Fe(OH)3.
28. If the equilibrium constant of the disproportionation reaction
Hg22+ = Hg0 + Hg2+
at 298 K is 0.0795, the standard e.m.f. of the reaction is [NSEC-2006]
(A) –0.065 V (B) –0.212 V (C) 0.125 V (D) 0.110 V
29. The voltage for the cell: Fe /Fe2+(0.001M) // Cu2+(0.10M) /Cu2+ (0.10 M) / Cu2+ (0.10 M) / Cu is 0.807 V
at 25°C. What is the value of E° ? [NSEC-2007]
(A) 0.629 V (B) 0.689 V (C) 0.748 V (D) 0.866 V
30. A current of 2.0 A is used to plate Ni(s) from 500mL of a 1.0 M Ni 2+ aqueous solution. What is the [Ni 2+]
after 3.0 hours ? [NSEC-2007]
(A) 0.39 M (B) 0.46 M (C) 0.78 M (D) 0.89 M
31. Nickel metal is added to a solution containing1.0 M Pb2+(aq) and 1.0 M Cd2+(aq). Use the standard
reduction potential to determine which of the following reaction (s) will occur. [NSEC-2008]
Reaction 1 : Ni(s) + Pb2+(aq)  Pb(s) + Ni2+(aq)
Reaction 2 : Ni(s) + Cd2+(aq) Cd(s) + Ni2+(aq)
Reactions :
Pb2+(aq) + 2e = Pb(s) E° = –0.13 V
Ni2+(aq) + 2e = Ni(s) E° = –0.23 V
Cd2+(aq) + 2e = Cd(s) E° = –0.40 V
(A) 1 only (B) 2 only (C) both 1 and 2 (D) neither 1 nor 2
ADVECH - 65
Electrochemistry
32. An electrochemical cell constructed for the reaction, Cu2+ (aq) + M(s)  Cu(s) + M2+(aq) has an E° = 0.75 V.
The standard reduction potential for Cu2+(aq) is 0.34 V. What is the standard reduction potential for
M2+(aq) ? [NSEC-2008]
(A) 1.09 V (B) 0.410 V (C) – 0410 V (D) – 1.09 V
33. An electric current is passed through a silver voltameter connected to a water voltameter. 0.324 g of
silver was deposited on the cathode of the silver voltameter. The volume of oxygen evolved at NTP is :
[NSEC-2009]
(A) 5.6 cm3 (B) 16.8 cm3 (C) 11.2 cm3 (D) 22.4 cm3
34. The amount of copper (At. wt. 63.54) deposited by passing 0.2 faraday of electricity through copper
sulphate is [NSEC-2009]
(A) 3.175 g (B) 6.350 g (C) 31.75 g (D) 63.35 g
35. When aqueous solution of sodum chloride is electrolysed using platinum electrode the cathode reaction
is, [NSEC-2009]
1
(A) Na+ + e– Na (B) H2O + e–  H2 + OH–
2
(C) Na + OH Na + OH + e
+ – + – –
(D) Na + H2O + e  Na + H+ + OH–
+ –
36. The standard electrode potential values for four metals K, L, M and N are respectively, –3.05, –1.66, –
0.40 and +0.80V. The best reducing agent is – [NSEC-2009]
(A) L (B) K (C) N (D) M
37. 10Cl– (aq) + 2MnO4– (aq) + 16H+ (aq) 5Cl2 (g) + 2Mn2+ (aq) + 8H2O (l) [NSEC-2009]
The value of Eº for the above reaction at 25ºC is 0.15V. Hence, the value of K for this reaction is:
(A) 2.4 × 1025 (B) 4.9 × 1012 (C) 1.2 × 105 (D) 3.4 × 102
38. Adding powdered Pb and Fe to a solution containing 1 M each of Pb2+ and Fe2+ ions would result in the
0
formation of – ( EPb 2
/ Pb
 0.126V and EFe
0
2
/ Fe
 0.44V ) [NSEC-2010]
(A) more of Pb and Fe2+ ions (B) more of Fe and Pb2+ ions
(C) more of Pb and Fe (D) more of Pb2+ and Fe2+ ions
39. The cell Al(s)|Al3+(aq) (0.001 M) | | Cu2+(aq) (0.10 M) | Cu(s) has a standard cell potential Eº = 2.00 V at
25°C. The cell potential at the given concentration will be : [NSEC-2010]
(A) 2.07 V (B) 2.03 V (C) 1.97 V (D) 1.94 V
40. The mass of copper deposited when a current of 10A is passed through a solution of copper(II) nitrate
for 30.6s is [NSEC-2010]
(A) 0.101 g (B) 0.201 g (C) 0.403 g (D) 6.04 g
41. In the conductometric titration of silver nitrate against KCI, the graph obtained is [NSEC-2011]
Conductance
Conductance
Conductance
Conductance
(A) (B) (C) (D)
volume of KCl volume of KCl volume of KCl volume of KCl

42. Th emf of the cell (Zn | ZnSO4(0.1M) || CdSO4 (0.01M) | Cd) is [NSEC-2011]
( EoZn2 / Zn = – 0.76 V, EoCd2 / Cd = 0.40 V at 298 K)
(A) +0.33 V (B) +0.36 V (C) +1.13 V (D) –0.36 V
43. The conductivity of a metal decreases with increase in temperature because : [NSEC-2012]
(A) the kinetic energy of the electrons increases (B) the movement of electrons becomes haphazard
(C) the ions start vibrating (D) the metal becomes hot and starts emiting radiation
ADVECH - 66
Electrochemistry
44. The amount of electricity required to deposit 1.0 mole of aluminium from a solution of AlCl3 will be :
[NSEC-2012]
(A) 1 faraday (B) 3 faradays (C) 0.33 faraday (D) 1.33 faraday
45. Which is the strongest oxidising agent among the species given below? [NSEC-2013]
(i) In3+ Eº = – 1.34V (ii) Au3+ Eº = 1.40V
(iii) Hg2+ Eº = 0.867V (iv) Cr3+ Eº = – 0.786V
3+ 3+ 2+
(A) Cr (B) Au (C) Hg (D) In3+
46. Which of the following aqueous solution has the lowest electrical conductance ? [NSEC-2013]
(A) 0.01M CaCl2 (B) 0.01M KNO2 (C) 0.01M CH3COOH (D) 0.01M CH3COCH3
47. The value of the constant in Nernst equation
cons tant
E = Eº – ln Q at 25ºC is : [NSEC-2013]
n
(A) 0.592 (B) 0.0592 (C) 0.296 (D) 0.0296
48. When zinc rod is directly placed in copper sulphate solution [NSEC-2013]
(A) the blue colour of the solution starts intensifying
(B) the solution remains electrically neutral
(C) the temperature of the solution falls
(D) the weight of zinc rod starts increasing
49. For the following cell at 25ºC the E.M.F. is : [If Eº = 0.347 V ] [NSEC-2014]
M2  /M
M(S) | M2+ (1M) || M2+ (0.01M) | M(S)
(A) 0.089V (B) 0.598V (C) 0.251V (D) 0.764V
50. For a strong electrolyte, the change in the molar conductance with concentration is represented by :
[NSEC-2014]
(I) (II) (III) (IV)

(A) I (B) II (C) III (D) IV
51. The specific conductance of 0.01M solution of the weak monobasic acid is 0.20 × 10–3 Scm–1. The
dissociation constant of the acid is [Given: ºHA = 400 Scm2mol–1] [NSEC-2014]
(A) 5 × 10–2 (B) 2.5 × 10–5 (C) 5 × 10–4 (D) 2.5 × 10–11
52. The reaction given below is the cell reaction in a galvanic cell.
Cd(s) + Sn2+(aq)  Cd2+(aq) + Sn(s)
Where, [Cd2+] = 0.1 M and [Sn2+] = 0.025 M
1
Given: E Cd 2 / Cd  0.403V , E Sn2 / Sn  0.136V , F  96485Cmol
0 0
At 25ºC, the free energy change for this reaction is : [NSEC-2014]

(A) — 48.05 KJ (B) — 54.96 KJ (C) — 100.58 KJ (D) — 107.46 KJ
53. A current of 5.0 A flows for 4.0 h through an electrolytic cell containing a molten salt of metal M. This
results in deposition of 0.25 mol of the metal M at the cathode. The oxidation state of M in the molten
salt is (1 Faraday = 96485 C mol–1) [NSEC-2015]
(A) +1 (B) +2 (C) +3 (D) +4
54. The limiting molar conductivities of KCl, KNO3, and AgNO3 are 149.9, 145.0 and 133.4 S cm2 mol–1,
respectively, at 25ºC. The limiting molar conductivity of AgCl at the same temperature in S cm 2 mol-1 is
[NSEC-2015]
(A) 128.5 (B) 138.3 (C) 161.5 (D) 283.3
ADVECH - 67
Electrochemistry
55. The emf of a cell corresponding to the following reaction is 0.199 V at 298 K. [NSEC-2015]
Zn (S) + 2 H+ (aq)  Zn2+ (0.1 M) + H2 (g) ( Eº Zn/Zn2  = 0.76V)
The approximate pH of the solution n at the electrode where hydrogen is being produced is (p H2 = 1
atm).
(A) 3 (B) 9 (C) 10 (D) 11
56. The standard electrode potentials, Eº of Fe3+/Fe2+and Fe2+/Fe at 300 K are +0.77 V and –0.44 V,
respectively. The Eº of Fe3+/Fe at the same temperature is [NSEC-2015]
(A) 1.21 V (B) 0.33 V (C) –0.036 V (D) 0.036 V
57. Three Faradays of electricity are passed through aqueous solutions of AgNO3, NiSO4 and CrCl3 kept in
three vessels using inert electrodes. The ratio (in moles) in which the metals Ag, Ni and Cr are
deposited is : [NSEC-2016]
(A) 1 : 2 : 3 (B) 3 : 2 : 1 (C) 6 : 3 : 2 (D) 2 : 3 : 6
58. The standard potentials (E°) of MnO4– /Mn2+ and MnO2/Mn2+ half cells in acidic medium are 1.51 V and
1.23 V respectively at 298 K. The standard potential of MnO4– /MnO2 half-cell in acidic medium at the
same temperature is : [NSEC-2016]
(A) 5.09 V (B) 1.70 V (C) 0.28 V (D) 3.34 V
59. Given the E0 values for the half reactions :
Sn4+ + 2e–  Sn2+, 0.15 V
2Hg2+ + 2e–  Hg22+, 0.92 V
PbO2 + 4H+ + 2e–  Pb2+ + 2H2O, 1.45 V
Which of the following statements is true? [NSEC-2016]
(A) Sn2+ is a stronger oxidizing agent than Pb4+ (B) Sn2+ is a stronger reducing agent than Hg22+
(C) Hg2+ is a stronger oxidizing agent than Pb4+ (D) Pb2+ is a stronger reducing agent than Sn2+
60. The conductivity of 0.10 M KCl solution at 298 K is 1.29 × 10–2 S cm–1. The resistance of this solution is
found to be 28.44 . Using the same cell, the resistance of 0.10 M NH4Cl solution is found to be 28.50
. The molar conductivity of NH4Cl solution in S cm 2 mol–1 is : [NSEC-2016]
(A) 0.130 (B) 13 (C) 130 (D) 1300
61. Which of the following statements is not correct regarding the galvanic cells ? [NSEC-2016]
(A) Oxidation occurs at the anode.
(B) Ions carry current inside the cell.
(C) Electrons flow in the external circuit from cathode to anode.
(D) When the cell potential is positive, the cell reaction is spontaneous.
62. When a medal is electroplated with silver (Ag) [NSEC-2017]
(A) The medal is the anode (B) Ag metal is the cathode
(C) The solution contains Ag+ ions (D) The reaction at the anode is Ag+ + e– Ag
Use the table given below to answer questions 63 and 64
Reaction E0/V
Ag Ag+ + e– –0.80
Cr3+ + 3e– 3Cr –0.74
Zn2++ 2e– Zn –0.76
2(s) + 2e– 2 – 0.54
Co2+ + 2e– Co –0.28
Ni2+ + 2e–Ni –0.26
63. The best reducing agent among the following is [NSEC-2017]
(A) Ag+ (B) Zn2+ (C) Cr3+ (D) –
64. Eº of the given cell is : [NSEC-2017]
Ni | (Ni+2, 1.0 M) || (Co+2, 1.0 M) | Co
(A) +0.02V (B) –0.02V (C) –0.54V (D) +0.54V
ADVECH - 68
Electrochemistry
65. The reduction of O2 to H2O in acidic solution has a standard reduction potential of 1.23 V. If the pH of
the acid solution is increased by one unit, half cell potential will [NSEC-2017]
O2(g) + 4H+(aq) + 4e–  2H2O(l)
(A) decrease by 59 mV (B) increase by 59 mV
(C) decrease by 236 mV (D) increase by 236 mV
66. From the given standard electrode potentials [NSEC-2018]
Sn4+(aq) + 2e–  Sn2+ (aq) Eº = 0.15V
Br2(I) + 2e–  2Br–(aq) Eº = 1.07V
The approximate free energy change of the process 2Br– (aq) + Sn4+ (aq)  Br2(l) + Sn2+(aq) is
(A) 117.6 kJ (B) 355 kJ (C) –177.6 kJ (D) –355 kJ
67. Concentration of K+ ions inside a biological cell was found to be 25 times higher than that outside. The
magnitude of the potential difference between the two sides of the cell is close to (2.303 RT/F-can be
taken as 59 mV; difference in concentrations of other ions can be taken as negligible) [NSEC-2018]
(A) 4.2 mV (B) 195 mV (C) 82 mV (D) –82 mV
68. The standard redox potential for the reaction 2H2O  O2 + 4H+ + 4e– is –1.23V. If the same reaction is
carried out at 25ºC and at pH = 7, the potential will be [NSEC-2018]
(A) –0.82 V (B) –3.28V (C) 0.82V (D) –1.18V
69. The standard electrode potential (E°) of the Daniel cell is 1.1 V and the overall cell reaction can be
represented as Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s). Under which of the following conditions will the
cell potential be higher than 1.1 V ? [NSEC-2018]
(A) 1.0 M Zn2+, 1.0 M Cu2+ (B) 1.2 M Zn2+, 1.2 M Cu2+
(C) 0.1 M Zn2+, 1.0 M Cu2+ (D) 1.0 M Zn2+, 0.01 M Cu2+
70. An electrochemical cell was constructed with Fe2+/Fe and Cd2+/Cd at 25ºC with initial concentrations of
[Fe2+] = 0.800 M and [Cd2+] = 0.250 M. The EMF of the cell when [Cd2+] becomes 0.100 M is
Half cell Eº(V)
Fe2+(aq)/Fe(s) – 0.44
Cd2+(aq)/Cd(s) – 0.40
[NSEC-2019]
(A) 0.013 V (B) 0.011 V (C) 0. 051 V (D) 0.022 V
71. Molten NaCl is electrolysed for 35 minutes with a currect of 3.50 A at 40ºC and 1 bar pressure. Volume
of chlorine gas evolved in this electrolysis is [NSEC-2019]
(A) 0.016 L (B) 0.98 L (C) 9.8 L (D) 1.96 L
72. If the standard electrode potentials of Fe3+/Fe and Fe2+/Fe are –0.04 V and –0.44 V respectively then
that of Fe3+/Fe2+ is [NSEC-2019]
(A) 0.76 V (B) –0.76 V (C) 0.40 V (D) –0.40 V
PART - IV : HIGH LEVEL PROBLEMS (HLP)

THEORY
Solubility product and EMF (Metal-Metal Insoluble Salt Electrode) :
  A half cell containing metal M and its sparingly soluble salt MA in a saturated solution.
i.e M(s) | MA (satd) or a metal, its sparingly soluble salt in contact with a solution of a soluble
salt NaA of the same anion, i.e. M(s) | MA(s) | NaA is set up.
The solubility product of a sparingly doubles salt is a kind of equilibrium constant.
MX (s) M+(aq) + X– (aq) Ksp = [M+] [X–]
At Anode At Cathode
M (s) M+ (aq) + e– e– + MX(s) M(s) + X– (aq)
ADVECH - 69
Electrochemistry
Overall reaction : MX (s) M+ (aq) + X– (aq)
+
Cell representation : M | M (saturated sol.) || NaA | MX(s) | M (s)
Eºcell = E°red – E°ox
From thermodynamics G° = – nFE°
G° = –2.303 RT log Ksp
combining both equations – 2.303 RT log Ksp = – nFE°
2.303 RT
or E° = log Ksp
nF
0.0591
E° = log Ksp at 25°C
n
Example Calculate Ksp if (PbSO4) Ecell at 298 K of this electrode is 0.236 V

Pb(s) |PbSO4(s)|Na2SO4(aq)||Pb(NO3)|Pb(s)
0.01 M 0.1 M
0.059  0.01
Ecell = E0cell – log  
2  0.1 
0.059
0.236 = E0cell +
2
E0cell = 0.236 – 0.03 = 0.206
Solution I Let it be conc. cell
Anode Pb(s)  Pb(a) 2
+2e–
2
Cathode Pb(s) + 2e–  Pb(s)
2 2
Pb(c) Pb(a)
0.059  (Pb2 )a 
Ecell = E0cell – log  2 
2  (Pb )c 
0.059  (Pb2 )a 
0.236 = log  2 
2  (Pb )c 
(Pb2+)a = 10–9M
Ksp = (Pb2+)a (SO24 )a = 10–11
Solution II Let if it is not a conc cell
Anode : Pb(s) + SO24 (aq)  PbSO4(s) + 2e–
Cathode : Pb2+(aq) + 2e–  Pb(s)
Pb2+(c) + SO24 (a)  PbSO4(s)
 0 0.059 
0
E0cell = EPb 2
/ Pb
– E0SO2 | PbSO 0
= EPb2 – EPb 2
|Pb 
 log K sp 
4 4 |Pb |Pb
 2 
0.059
E0cell = – log Ksp
2
0.059 0.059  1   K SP  K 
0.236 = log Ksp – log  2 2  = log   = log  SP3 
log10–8
2 2  (Pb )c (SO 4 )a   0.1  0.01  10 
Ksp = 10–11
Calomel Electrode :
A calomel electrode consists of a platinum electrode dipping into mercury in contact with calomel
(dimercury (I) chloride, Hg2Cl2) and potassium chloride solution.
Usually the solution is saturated with potassium chloride.
ADVECH - 70
Electrochemistry
The cell has E0 = 0.28 V (with respect of SHE) at 25°C
Standard (normal) calomel electrode when [Cl – ] = 1M = 1N
At Anode At Cathode
2Hg()  Hg22 (aq) + 2e– Hg22 + 2e–  2Hg()
Hg22 (aq) + 2Cl–  Hg2Cl2(s) Hg2Cl2  Hg22 (aq) + 2Cl–(aq)
2Hg() + 2Cl–(aq)  Hg2Cl2(s) + 2e– Hg2Cl2(s) + 2e–  2Hg() + 2Cl-

Cell representation Cell representation
–
Pt(s) |Hg() | Hg2Cl2(s) | Cl (aq)|| cathode (Anode) || Cl–(aq) | Hg2Cl2|Hg() | Pt(s)
0
EHg | Hg Cl / Cl
= SOP E0Cl |Hg Cl = SRP
2 2 2 2 |Hg( )
RT
ECl / Hg Cl / Hg
= E0  – n[Cl–]
2 2 Cl / Hg 2Cl 2 / Hg F
RT 1
EMn  / M(Hg)Pt = E0 n  – n[ n ]
M / M(Hg)Pt F M
Thermodynamics of Cell Potential :
We know that :
  G0 = –nF E0cell
G = – nFEcell
G = H – TS
From thermodynamics H = E + PV enthalpy function.
Substituting G = E + PV – TS
By partial differentiation
dG = dE + PdV + VdP – TdS – SdT ...... (i)
st
according to 1 law of thermodynamics
E=q+W dW = –PdV
dE = dq – PdV
dq = dE + PdV ...... (ii)
nd
according to 2 law
dq
ds = = dq = Tds ...... (iii)
T
From (i), (ii) and (iii)
dG = VdP – SdT
at constant pressure, which is actually the condition for all normal cell reaction.
dG = –SdT
dG
S=
dT
d( G)
S = –
dT
ADVECH - 71
Electrochemistry
G = – nFEcell
dEcell
S = +nF
dT
dEcell
= temperature cofficient of cell reaction.
dT
G = H – TS
dEcell
H = – nF Ecell + nFT
dT
Kirchoff's equation
d
Cp = (H)
dT
nFdEcell d2Ecell nFdEcell
Cp = Cp (of products) – Cp (of reactants) = + nFT 2
+
dT dT dT
d2Ecell
Cp = nFT
dT 2
SUBJECTIVE QUESTIONS
2
1. Determine range of E° values for this reaction Xaq. + 2e–  X(s) for given conditions:
(a) If the metal X dissolve in HNO3 but not in HCl it can displace Ag+ ion but not Cu2+ ion.
(b) If the metal X in HCl acid producing H2(g) but does not displace either Zn2+ or Fe2+.
Given : EoAg /Ag  0.8V , o
EFe 2
/Fe
 0.44V ,
EoCu2  /Cu  0.34V , o
ENO
/NO
 0.96V , EoZn2  /Zn  0.76V
3
2. The standard reduction potential of TiO2+ and Ti3+ are given by

TiO2+ + 2H+ + e  Ti3+ + H2O Eº = 0.10 V
Ti3+ + 3e  Ti Eº = 1.21 V
Find the standard reduction potential of TiO2+ to Ti.
3. The standard oxidation potential for the halfcell
NO2– (g) + H2O  NO3(aq) + 2H+ (aq) +2e is 0.78 V.
Calculate the reduciton potential in 9 molar H+ assuming all other species at unit concentration. What
will be the reduction potential in neutral medium ?
4. Calculate the electrode potential at 250C of Cr3+, Cr2O72 electrode at pOH = 11 in a solution of 0.01 M
both in Cr3+ and Cr2O72.
Cr2O72 + 14H+ + 6e  2Cr3+ + 7H2O E0 = 1.33 V.
5. An electrochemical cell is constructed with an open switch as shown below:
V
Sn Salt Bridge x
0.5 M Sn2+ 0.1 M Xn+

ADVECH - 72
Electrochemistry
When the switch is closed, mass of tin-electrode increase. If Eº (Sn2+ / Sn) = – 0.14 V and for
Eº (Xn+ / X) = – 0.78 V and initial emf of the cell is 0.65 V, determine n and indicate the direction of
electron flow in the external circuit.
6. Equinormal Solutions of two weak acids, HA (pKa = 3) and HB (pKa = 5) are each placed in contact with
standard hydrogen electrode at 25°C (T = 298 K). When a cell is constructed by interconnecting them
through a salt bridge find the e.m.f. of the cell.
7. In two vessels each containing 500ml water, 0.5m mol of aniline (K b = 10–9) and 25 m mol of HCl are
added separately. Two hydrogen electrodes are constructed using these solutions. Calculate the emf of
cell made by connecting them appropriately.
8. Write cell reaction from given cell diagrams
(A) Cu | Cu2 || Cl– | Hg2Cl2 | Hg | Pt
(B) Ag (s) | AglO3 (s)|Ag+, HlO3 || Zn2+ | Zn (s)
(C) Mn (s) | Mn (OH)2 (s) Mn2+, OH– || Cu2+|Cu (s)
9. For the galvanic cell : Ag | AgCl (s)|KCl (0.2M) || KBr (0.001M) |AgBr (s) |Ag,
2.303RT
Calculate the EMF generated? (Take = 0.06)
F
[Ksp(AgCl)= 10–10 ; Ksp(AgBr)=10–13]
10. Given, E° = –0.27 V for the Cl– | PbCl2 |Pb couple and – 0.12 V for the Pb2+ | Pb couple, determine Ksp
2.303RT
for PbCl2 at 25°C ? (Take = 0.06)
F
11. The pKsp of Agl is 16. if the E° value for Ag+ | Ag is 0.8 V. Find the E° for the half cell reaction Agl(s) +
2.303RT
e–  Ag + l– ? (Take = 0.06 )
F
12. The EMF of the standard weston cadmium cell Cd (12.5%) in Hg | 3CdSO 4, 8H2O (solid) | saturated
solution of CdSO4 || Hg2SO4(s) | Hg is 1.0180 volts at 25° C and the temperature coefficient of the cell,
 E 
 T  = – 4.0 × 10 V/degree. Calculate G, H and S for the reaction in the cell when n = 2.
–5
1
13. H for the reaction Ag(s) + Hg2 Cl2 (s)  AgCl(s) + Hg() is +1280 cal at 25°C. This reaction can
2
be conducted in a cell for which the emf = 0.0455 volt at this temperature. Calculate the temperature
coefficient of the emf.
14. The standard electromotive force of the cell :
Fe | Fe2+ (aq) | | Cd2+ | Cd is 0.0372 V
The temperature coefficient of e.m.f. is –0.125 V K–1. Calculate the quantities Gº, Hº and Sº at 25ºC.
15. The voltage of a certain cell has standred potential at 25ºC and 20ºC are 0.3525 V and 0.3533 V
respectively. If the number of electrons involved in the overall reactions are two, calculate Gº, Sº and
Hº at 25ºC.
16. A metal is known to form fluoride MF2. When 10A of electricity is passed through a molten salt for 330
sec., 1.95g of metal is deposited. Find the atomic weight of M. What will be the quantity electricity
required to deposit the same mass of Cu from CuSO4 ?
17. Find the volume of gases evolved by passing 0.965 A current for 1 hr through an aqueous solution of
CH3COONa at 250ºC and 1 atm.
18. One of the methods of preparation of per disulphuric acid, H2S2O8, involve electrolytic oxidation of H2SO4 at
anode (2H2SO4  H2S2O8 + 2H+ + 2e–) with oxygen and hydrogen as by-products. In such an electrolysis,
9.722 L of H2 and 2.35L of O2 were generated at STP. What is the weight of H2S2O8 formed ?
ADVECH - 73
Electrochemistry
19. The standard reduction potential values, Eº (Bi 3+ / Bi) and Eº (Cu2+ /Cu) are 0.226V and 0.344V
respectively. A mixture of salts of bismuth and copper at unit concentration each is electrolysed at
25°C. To what value can [Cu2+] be brought down before bismuth starts to deposit, in electrolysis.
20. Calculate the dissociation constant (kdissociation) of water at 25°C from the following data :
 
Specific conductance of H2O = 5.8 × 10–8 mho cm–1, H = 350.0 and  OH¯ = 198.0 mho cm2 mol-1
21. (a) Calculate Gº of the following reaction :

Ag+(aq) + Cl–(aq) AgCl(s)
Given : Gº(AgCl) = – 109 kJ/mole, Gº(Cl–) = – 129 kJ/mole, Gº(Ag+) = 77 kJ/mole.
Represent the above reaction in form of a cell.
Calculate Eº of the cell. Find log10Ksp of AgCl at 25ºC.
(b) 6.539 × 10–2 g of metallic Zn (atomic mass = 65.39 amu) was added to 100 mL of saturated solution
of AgCl.
[Zn2 ]
Calculate log10 at equilibrium at 25ºC, given that :
[Ag ]2
Ag+ + e–  Ag Eº = 0.80 V
Zn2+ + 2e–  Zn Eº = – 0.76 V
114 1.56
Also find how many moles of Ag will be formed. (Take = 0.59, = 26.44) [JEE 2005, 6/60]
193 0.059
ONLY ONE OPTION CORRECT TYPE

1
22. The standard potential of the reaction H2O + e–  H2 + OH– at 298 K by using Kw (H2O) = 10–14, is :
2
(A) – 0.828 V (B) 0.828 V (C) 0 V (D) – 0.5 V
23. Given : Hg22+ + 2 e 2 Hg , Eº = 0.789 V & Hg2+ + 2 e  Hg , Eº = 0.854 V,

calculate the equilibrium constant for Hg22+  Hg + Hg2+ .
(A) 3.13 × 103 (B) 3.13 × 104 (C) 6.26 × 103 (D) 6.26 × 104
24. MnO4– + 8H+ + 5e–  Mn2+ + 4H2O,
If H+ concentration is decreased from 1 M to 10–4 M at 25ºC, where as concentration of Mn2+ and MnO4–
remain 1 M.
(A) the potential decreases by 0.38 V with decrease in oxidising power
(B) the potential increases by 0.38 V with increase in oxidising power
(C) the potential decreases by 0.25 V with decrease in oxidising power
(D) the potential decreases by 0.38 V without affecting oxidising power
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O,
25. At equimolar concentrations of Fe2+ and Fe3+, what must [Ag+] be so that the voltage of the galvanic cell
made from the (Ag+ | Ag) and (Fe3+ | Fe2+) electrodes equals zero?
Fe2+ + Ag+ Fe3+ + Ag
Eº Ag |Ag = 0.7991 ; EºFe3  | Fe2  = 0.771
(A) 0.34 (B) 0.44 (C) 0.47 (D) 0.61
26. The cell Pt (H2) (1 atm) | H+(pH = ?) || I– (a = 1) | AgI(s), Ag(s) | Pt has emf, E298K = 0. The standard
electrode potential for the reaction AgI + e¯  Ag + I is – 0.151 volt. Calculate the pH value.
(A) 3.37 (B) 5.26 (C) 2.56 (D) 4.62
27. Using the information in the preceding problem, calculate the solubility product of AgI in water at 25°C
º
[ E(Ag
, Ag)
= + 0.799 volt]
(A) 1.97 × 10–17 (B) 8.43 × 10–17 (C) 1.79 × 10–17 (D) 9.17 × 10–17
ADVECH - 74
Electrochemistry
28. The solubility product of silver iodide is 8.3 × 10–17 and the standard reduction potential of Ag, Ag+
electrode is + 0.8 volts at 25° C. The standard reduction potential of Ag,Agl/l¯ electrode from these data
is
(A) – 0.30 V (B) + 0.15 V (C) + 0.10 V (D) – 0.15 V
29. The efficiency of an hypothetical cell is about 84% which involves the following reaction :
A (s) + B2+ (aq)  A2+ (aq) + B (s) : H = – 285 kJ
Then, the standard electrode potential of the cell will be
(A) 1.20 (B) 2.40 V (C) 1.10 V (D) 1.24 V
dE
30. The temperature coefficient, of the emf i.e. = – 0.00065 volt. deg–1 for the cell Cd | CdCl2 (1M) ||
dT
AgCl (s) | Ag at 25°C. Calculate the entropy changes S298K for the cell reaction, Cd + 2AgCl  Cd2+ +
2Cl + 2Ag
(A) – 105.5 JK–1 (B) – 150.2 JK–1 (C) – 75.7 JK–1 (D) – 125.5 JK–1
31. The standard emf of the cell, Cd(s) CdCl2(aq) (0.1 M) AgCl(s) Ag(s) in which the cell reaction is,
Cd(s) + 2AgCl(s)  2Ag(s) + Cd+2 (aq) + 2Cl–(aq) is 0.6915 V at 0°C and 0.6753 V at 25°C. The Hº
of the reaction at 25°C is :
(A) – 176 kJ (B) – 234.7 kJ (C) + 123.5 kJ (D) – 167.26 kJ
ZnSO4 CuSO4
32. The potential of the Daniell cell, Zn Cu was reported by Buckbee, Surdzial and
(1 M) (1 M)
Metz as E° = 1.1028 – 0.641 × 10–3 T + 0.72 × 10–5 T 2, where T is the temperature in degree celsius.
Calculate S° for the cell reaction at 25°C :
(A) – 45.32 EU (B) – 34.52 EU (C) – 25.43 EU (D) – 54.23 EU
33. Using the data in the preceding problem, calculate the equilibrium constant of the reaction at 25°C.
[Zn2 ]
Zn + Cu2+ Zn2+ + Cu, K =
[Cu2 ]
(A) 8.314 × 1024 (B) 4.831 × 1031 (C) 8.314 × 1036 (D) 4.831 × 1044
 d( G)   dE 
34. G = H – TS and G = H + T   then  cell  is :
 dT p  dT 
S nE
(A) (B) (C) – nFEcell (D) + nEFcell
nF S
35. One g equivalent of Na metal is formed from electrolysis of fused NaCl. No. of mole of Al from the fused
Na3AlF6 with the same current passed is :
(A) 1 (B) 3 (C) 1/3 (D) 2
36. The specific conductivity of a saturated solution of AgCl is 3.40  10 6 ohm 1 cm 1 at 25 ºC. If
 Ag = 62.3 ohm 1 cm2 mol 1 &  Cl = 67.7 ohm 1 cm2 mol 1, the solubility of AgCl at 25 ºC is :
(A) 2.6  10 5 M (B) 4.5  10 3 M (C) 3.6  10 5 M (D) 3.6  10 3 M
37. List-1 List-II
(P) Conductivity does not change much then increases (1) NH3 is added in C6H5COOH
(Q) Conductivity increases then does not change much (2) CH3COOH is added in NaOH
(R) Conductivity decreases then does not change much (3) KOH is added in HCl
(S) Conductivity decreases then increases (4) Conc. KCl is added in dilute AgNO3
(T) Conductivity tends to zero at the end point (5) MgSO4 is added in Ba(OH)2
(P) (Q) (R) (S) (T) (P) (Q) (R) (S) (T)
(A) 4 2 1 5 3 (B) 1 2 3 4 5
(C) 5 4 3 2 1 (D) 4 1 2 3 5
ADVECH - 75
Electrochemistry
38. The standard reduction potentials E° of the following systems are
System E°(volts)
(i) MnO4¯ + 8H + 5e  Mn + 4H2O
+ – 2+ 1.51
(ii) Sn + 2e  Sn
4+ – 2+ 0.15
(iii) Cr2 O7 + 14H + 6e  2Cr + 7H2O
2– + – 3+ 1.33
(iv) Ce + e  Ce
4+ – 3+ 1.61
The oxidising power of the various species decreases in the order
(A) Ce4+ > Cr2 O72– > Sn4+ > MnO4– (B) Ce4+ > MnO4– > Cr2 O72– > Sn4+
–
2– 4+ 4+
(C) Cr2O7 > Sn > Ce > MnO4 (D) MnO4– > Ce4+ > Sn4+ > Cr2 O72–
39. Consider the reaction : (T = 298 K)
Cl2(g) + 2Br¯(aq)  2Cl¯ (aq) + Br2 (aq.)
The emf of the cell, when [Cl¯] = [Br2] = [Br¯] = 0.01M and Cl2 gas is at 1 atm pressure, will be :
(E° for the above reaction is = 0.29 volt)
(A) 0.54 volt (B) 0.35 volt (C) 0.24 volt (D) –0.29 volt
40. 2Ce4+ + Co 2Ce3+ + Co2+, Eºcell = 1.89 V, EºCo2 / Co = – 0.277 V hence, EºCe4  / Ce3  is :
(A) 0.805 V (B) 1.62 V (C) – 0.805 V (D) – 1.61 V
41. MnO4– + 8H+ + 5e–  Mn2+ + 4H2O ; Eº = 1.51 V ; G10 = – 5 × 1.51 × F

MnO2 + 4H+ + 2e–  Mn2+ + 2H2O ; Eº = 1.23 V ; G02 = – 2 × 1.23 × F
EºMnO | MnO is
4 2
(A) 1.70 V (B) 0.91 V (C) 1.37 V (D) 0.548 V

42. G is the available energy (energy produced) during the electrochemical reaction in galvanic cell which
can be converted into useful work. In the light of second law of thermodynamics in the cell the change
in electrode potential with temperature will be equal to
S nF –2.303 RT
(A) (B) (C) – 2.303 RT log KC (D)
nF S nF
43. The reduction potential of hydrogen electrode when placed in a buffer solution is found to be – 0.413V.
The pH of the buffer is -
(A) 10 (B) 4 (C) 7 (D) 12
44. A gas Cl2 at 1 atm is bubbled through a solution containing a mixture of 1 M Br–1 and 1 M F–1 at 25ºC. If
the reduction potential is F > Cl > Br, then :
(A) Cl will oxidise Br and not F (B) Cl will oxidise F and not Br.
(C) Cl will oxidise both Br and F (D) Cl will reduce both Br and F
45. The oxidation potentials of Zn, Cu, Ag, H2 and Ni are 0.76, –0.34, –0.80, 0.00, 0.25 volt, respectively.
Which of the following reactions will provide maximum voltage ?
(A) Zn + Cu2+  Cu + Zn2+ (B) Zn + 2Ag+  2Ag + Zn2+
(C) H2 + Cu  2H + Cu
2+ +
(D) H2 + Ni2+ 2H+ + Ni
46. The reduction potential of a half-cell consisting of a Pt electrode immersed in 1.5 M Fe2+ and 0.015 M
0

Fe3+ solution at 25°C is EFe3
Fe2 
 0.770 V .
(A) 0.652 V (B) 0.88 V (C) 0.710 V (D) 0.850 V
[Zn2 ]
47. Zn + Cu2+ (aq) Cu + Zn2+ (aq) Reaction quotient is Q = . Eºcell = 1.10 V. Ecell will be 1.1591
[Cu2 ]
V when :
A
Ecell
O log Q
(A) [Cu2+]/[Zn2+] = 0.01 (B) [Zn2+]/[Cu2+] = 0.01 (C) [Zn2+]/[Cu2+] = 0.1 (D) [Zn2+]/[Cu2+] = 1
ADVECH - 76
Electrochemistry
48. Pure water is saturated with pure solid AgCl, a silver rod is placed in the solution and the potential is
measured against normal calomel electrode at 25°C. This experiment is then repeated with a saturated
solution of AgI. If the difference in potential in the two cases is 0.177 V, what is the ratio of solubilty
product (Ksp) of AgCl and AgI at the temperature of the experiment ? (In both cases normal calomel
electrode is cathod)
(A) 103 (B) 106 (C) 10–3 (D) 10–6
49. Conductance measurements can be used to detect the end point of acid-base titrations. Which of the
following plots correctly represent the end point of the titration of strong acid and a strong base ?
Conductance
Conductance
Conductance
Conductance
end point
(A) (B) (C) (D)
end point end point
end point
Volume of base added Volume of base added Volume of base added Volume of base added
50. Which one of the following will increase the voltage of the cell ? (T = 298 K)
Sn + 2Ag+  Sn2+ + 2Ag
(A) increase in the size of silver rod (B) increase in the concentration of Sn+2 ions
(C) increase in the concentration of Ag+ ions (D) none of the above
51. In a H2 – O2 fuel cell, 6.72 L of hydrogen at NTP reacts in 15 minutes, the average current produced in
amperes is
(A) 64.3 amp (B) 643.3 amp (C) 6.43 amp (D) 0.643 amp
52. The standard reduction potential of a silver chloride electrode is 0.2 V and that of a silver electrode is
0.79 V. The maximum amount of AgCl that can dissolve in 106 L of a 0.1 M AgNO3 solution is
(A) 0.5 mmol (B) 1.0 mmol (C) 2.0 mmol (D) 2.5 mmol
53. A cell Cu | Cu++ || Ag+ | Ag initially contains 2M Ag+ and 2M Cu2+ ions in 1 L electrolyte. The change in
cell potential after the passage of 10 amp current for 4825 sec during usage of cell is:
2.303RT
(Take = 0.06)
F
(A) – 0.009 V (B) – 1.00738 V (C) – 0.0038 V (D) –1.2 V
 Eº  –3 –1
54. At 27ºC   = –1.45 × 10 V K and Eº = 1.36 V
 T  P
For the cell Pt | H2 (g)  HCl (aq) | Cl2 | Pt. Calculate entropy and enthalpy change in this standard state.
(A) –962.48 JK–1, –346.435 KJ (B) –279.85 JK–1, –346.453 KJ
–1
(C) –1326.23 JK , –346.435 KJ (D) –280.24 KJK–1, –346.435 KJ.
55. If Ksp values of AgCl, AgBr & AgI at 298 K are 10–10, 10–13 & 10–17 respectively,
Compare Eo – , Eo – & Eo– :
Cl / AgCl/ Ag Br / AgBr / Ag I / AgBr / Ag
o o
(A) ECl–
/ AgCl/ Ag will have the least value and its value will be less than EAg / Ag
o o
(B) EI– / AgBr / Ag will have the least value and its value will be more than EAg / Ag
o o
(C) ECl– / AgCl/ Ag will have the least value and its value will be more than EAg / Ag
o o
(D) EI– / AgBr / Ag will have the least value and its value will be less than EAg / Ag
NUMERICAL VALUE QUESTIONS

56. Consider the cell Ag|AgBr(s)| Br– || Cl– | AgCl(s)| Ag at 25°C. The solubility product constants of AgBr &
AgCl are respectively 5 × 10–13 & 1 × 10–10 . For what ratio of the concentrations of Br– & Cl¯ ions would
the e.m.f. of the cell be zero ? Report as 1000  your answer.
ADVECH - 77
Electrochemistry
57. A silver coulom meter is in series with a cell electrolyzing water. In a time of 1 minute at a constant
current, 1.08 g silver got deposited on the cathode of the coulometer. What total volume (in mL) of the
gases would have produced in other cell if in this cell the anodic and cathodic efficiencies were 90%
and 80% respectively. Assume STP conditions and the gases collected are dry. (Ag – 108) (Molar
volume of any ideal gas at STP = 22.4 L). Report as (your answer ÷ 10)
58. During electrolysis of CH3COONa(aq), the mole ratio of gases formed at anode and cathode is :
59. Calculate the emf of the cell in mV

Ag (s), AgO3 (s)  Ag (xM), HO3 (1 M) Zn2 (1 M) Zn(s)
1
If Ksp = 3 ×10–8 for AgO3 and Ka = for HO3 and E0cell for 2Ag + Zn+2 
 2Ag+ + Zn is – 1.56 V.
6
2.303 RT
(log 3 = 0.48) (Take = 0.06) (Write magnitude of first two digits of your answer)
F
60. A saturated solution of MX is prepared KSP of MX is a × 10–b. If 10–7 mol of MNO3 are added in 1  of
this solution conductivity of this solution is 55×10–7 S m–1 :
 = 6 × 10–3 S m2 mol –1 ;   = 8 × 10–3 ; 
º
m
º º
x NO3– = 7 × 10
–3
Find the value of (a + b) ? Given that 10 < a < 100
61. Zn2 (aq)  4OH (aq) 

 Zn(OH)24 (aq)
Value of equilibrium constant (Kf) for above reaction is 10x then find x:
Given : Zn2 (aq)  2e  Zn(s); Eo  0.76V
Zn(OH)24 (aq)  2e  Zn(s)  4OH (aq); E  1.36V

o
RT
2.303  0.06
F
62. A cell reaction, Zn + 2Fe3+ 2Fe2+ + Zn2+, works at 25ºC with the cell emf 1.2 volt and at 45ºC
with the cell emf 1.718 volt. Assuming Sº to be constant in this temperature range, calculate Sº in
kJ/K. (Give your answer in the nearest integer).
ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

63. Which of the following statements is wrong about galvanic cells ?
(A) Cathode is the positive electrode
(B) Cathode is the negative electrode
(C) Electrons flow from cathode to anode in the external circuit
(D) Reduction occures at cathode
64. When a cleaned strip of zinc metal is placed in a solution of CuSO 4, a spontaneous reaction occurs.
Which of the following observation(s) is/are made ?
(A) the mass of zinc metal decreases gradually
(B) the copper metal starts depositing on either zinc plate or settles down to the vessel
(C) the solution remains electrically neutral
(D) the temperature of the solution decreases as it is an endothermic reaction.
65. Mark out the correct statement(s)
(A) Copper metal cannot reduce iron (II) ions in acidic solutions.
(B) Sodium can be obtained by the electrolysis of aqueous solution of NaCl using Pt electrodes.
(C) The current carrying ions in an electrolytic cell are not necessarily discharged at the electrodes.
(D) Cations having more negative oxidation potential than –0.828 V are reduced in preference to water.
ADVECH - 78
Electrochemistry
66. When a lead storage battery is recharged
(A) PbSO4 is formed (B) Pb is formed (C) SO2 is consumed (D) H2SO4 is formed
67. Which of the following statements is / are correct ?

(A) The conductance of one cm3 (or 1 unit3) of a solution is called conductivity.
(B) Specific conductance increases while molar conductivity decreases on progressive dilution.
(C) The limiting equivalent conductivity of weak electrolyte cannot be determine exactly by
extraplotation of the plot of eq against c.
(D) The conductance of metals is due to the movement of free electrons.
68. Peroxodisulphate salts (Na2S2O8) are strong oxidizing agents used as bleaching agents for fats, oil etc.
Given
O2(g) + 4H(aq) + 4e–  2H2O() Eº = 1.23 V
S2O8–2 + 2e–  2SO 4–2 (aq) Eº = 2.01 V
Which of the following statements is (are) correct ?
(A) Oxygen gas can oxidize sulphate ion to per-oxo disulphate ion (S2O8–2) in acidic solution.
(B) O2(g) is reduced to water
(C) Water is oxidised to O2
(D) S2O8–2 ions are reduced to SO4–2 ions.
69. 0.1 molar solution of NaBr solution is electrolysed by passing 965 column charge. After electrolysis
which statement is correct for resulting solution.
(A) Specific conductance increases (B) molar conductance increases
(C) No change in molar conductance. (D) Specific resistance increases.
70. A beaker contains a small amount of iron Fe(s). Which of the following aqueous solution, when added
to the beaker, would dissolve the iron i.e. convert Fe(s) to Fe2+ (aq) ?
Half cells Eº at 25ºC
Zn + 2e  Zn
2+ – –0.76
Fe + 2e  Fe
2+ – –0.41
Al + 3e  Al
3+ – –1.66
O2 + 2H + 2e  H2O2
+ – 0.70
2–
Cr2 O7 + 6e + H  2Cr
– + 3+ 1.23
O2 + 4H+ + 4e–  2H2O 1.30
(A) Cr2O72– (acidic solution) (B) H2O2 (acidic solution)
(C) Al3+ (D) Zn2+
COMPREHENSION
Comprehension # 1
Given EoZn2 |Zn = – 0.76 V Kf [Cu(NH3)4]+2 = 4 × 1011

EoCu2 |Cu = 0.34 V
Answer the following.
ADVECH - 79
Electrochemistry
2.303  R
71. The emf of cell at 200 k is [Given : = 2  10-4 and assume that Eº values are independent
F
on temperature.]
(A) 1.7 V (B) 1.08 V (C) 1.09 V (D) 1.10 V
72. When 1 mole NH3 added to cathode compartment than emf of cell is (at 298K)
(A) 0.81 V (B) 1.91 V (C) 1.1 V (D) 0.72 V
73. At what conc of Cu+2 emf of the cell will be zero (at 298K) and conc. of Zn+2 is remain same
(A) 1.19 × 10–37 (B) 1. 19 × 10–20 (C) 3.78 × 10–4 (D) 0.0068
Comprehension # 2
Strong Acid Versus Strong Base
The principle of conductometric titrations is based on the fact that during the titration, one of the ions is
replaced by the other and invariably these two ions differ in the ionic conductivity with the result that the
conductivity of the solution varies during the course of the titration. Take, for example, the titration
between a strong acid, say HCl, and a strong base, say NaOH. Before NaOH is added, the
conductance of HCl solution has a high value due to the presence of highly mobile hydrogen ions. As
NaOH is added, H+ ions are replaced by relatively slower moving Na+ ions. Consequently, the
conductance of the solution decreases and this continues right upto the equivalence point where the
solution contains only NaCl. Beyond the equivalence point, if more of NaOH is added, then the solution
contains an excess of the fast moving OH– ions with the result that its conductance is increased and it
continues to increase as more and more of NaOH is added.
If we plot the conductance value versus the amount of NaOH added, we get a curve of the type shown
in Fig.
The descending portion AB represents the conductances before the euivalence point (solution contains
a mixture of acid HCl and the salt NaCl) and the ascending portion CD represents the conductances
after the equivalence point (solution contains the salt NaCl and the excess of NaOH). The point E which
represents the minium conductance is due to the solution containing only NaCl with no free acid or
alkali and thus represents the equivalence point. This point can, however, be obtained by the
extrapolation of the lines AB and DC, and therefore, one is not very particular in locating this point
experimentally as it is in the case of ordinary acid-base titrations involving the acid-base indicators.
Weak Acid versus Strong Base

Let us take the specific example of acetic acid being titrated against NaOH. Before the addition of alkali,
the solution shows poor conductance due to feeble ionization of acetic acid. Initially the addition of alkali
casuse not only the replacement of H+ by Na+ but also suppresses the dissociation of acetic acid due to
the common ion Ac– and thus the conductance of the solution decreases in the beginning. But very
soon the conductance starts increasing as addition of NaOH neutralizes the undissociated HAc to
Na+Ac– thus causing the replacement of non-conducting HAc with strong-conducting electrolyte Na+ Ac–
. The increase in conductance continunes right up to the equivalence point. Beyond this point
conductance increases more rapidly with the addition of NaOH due to the highly conducting OH– ions.
The graph near the equivalence point is curved due to the hydrolysis of the salt NaAc. The actual
equivalence point can, as usual, be obtained by the extrapolation method.
In all these graphs it has been assumed that the volume change due addition of solution from burrette is
negligible, hence volume change of the solution in beaker the conductance of which is measured is almost
constant throughout the measurement.
ADVECH - 80
Electrochemistry
74. The nature of curve obtained for the titration between weak acid versus strong base as described in
the above passage will be :
Conductance
Conductance
Conductance
(A) (B) (C) (D)
volume of NaOH volume of NaOH volume of NaOH
75. The most appropriate titration curve obtained when a mixture of a strong acid (say HCl) and a weak
acid (say CH3COOH) is titrated with a strong base(say NaOH) will be
Conductance
Conductance
(A) (B)
V1 + V2 V1 V2
volume of NaOH volume of NaOH
Conductance
Conductance
(C) (D)
V1 V2 V1 V2
volume of NaOH volume of NaOH
PART - V : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))

Max. Time : 1 Hr. Max. Marks : 66
Important Instructions
A. General %
1. The test is of 1 hour duration.
2. The Test Booklet consists of 22 questions. The maximum marks are 66.
B. Question Paper Format
3. Each part consists of five sections.
4. Section 1 contains 7 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
of which ONE is correct.
5. Section 2 contains 5 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
of which ONE OR MORE THAN ONE are correct.
6. Section 3 contains 6 questions. The answer to each of the questions is a numerical value, ranging from 0
to 9 (both inclusive).
7. Section 4 contains 1 paragraphs each describing theory, experiment and data etc. 3 questions relate to
paragraph. Each question pertaining to a partcular passage should have only one correct answer among
the four given choices (A), (B), (C) and (D).
8. Section 5 contains 1 multiple choice questions. Question has two lists (list-1 : P, Q, R and S; List-2 : 1, 2,
3 and 4). The options for the correct match are provided as (A), (B), (C) and (D) out of which ONLY ONE
is correct.
C. Marking Scheme
9. For each question in Section 1, 4 and 5 you will be awarded 3 marks if you darken the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus one
(–1) mark will be awarded.
ADVECH - 81
Electrochemistry
10. For each question in Section 2, you will be awarded 3 marks. If you darken all the bubble(s)
corresponding to the correct answer(s) and zero mark. If no bubbles are darkened. No negative marks will
be answered for incorrect answer in this section.
11. For each question in Section 3, you will be awarded 3 marks if you darken only the bubble corresponding
to the correct answer and zero mark if no bubble is darkened. No negative marks will be awarded for
incorrect answer in this section.
SECTION-1 : (Only One option correct Type)

This section contains 10 multiple choice questions. Each questions has four choices (A), (B),
(C) and (D) out of which Only ONE option is correct.
1. An initial solution of x M, 1L Fe+2 was reduced to Fe(s) on passage of 1 A current for 965 seconds. If
after electrolysis 0.1M, 10 ml acidified KMnO4 solution was required to oxidize remaining Fe+2 solution
then the value of ‘x’ is -
(A) 10–2 (B) 10–3 (C) 5 × 10–3 (D) 5 × 10–2
2. A solution of 100 mL, 0.2 M CH3COOH is mixed with 100 mL, 0.2 M NaOH solution. The molar
conductance for 0.1 M CH3COOH at infinite dilution is 200 S cm 2 mol–1 and at any concentration is 2.0
S cm2 mol–1. Then calculate pH of the solution?
(A) 7 (B) 8 (C) 5 (D) 9
3. The specific conductance of saturated solution of silver bromide is K (–1 cm–1). The limiting ionic
conduction of Ag+ and Br– ions are a & b respectively. The solubility of AgBr in g lit –1 is:
(Molar mass of AgBr = 188g mol–1)
1000 K K  1000  188 a  b 1000
(A) K × (B) × 188 (C) (D) ×
ab ab ab K 188

4. The conductance ratio = 0.936 given this for a certain solution of KCl and  = 122 –1cm2 eq–1 and
º
º 0.98
= . Calculate the limiting values of Ionic conductance of K and Cl– ions in –1cm2 eq–1.
º 1.98
(A) 64.51, 65.83 (B) 74.60, 26.40 (C) 30.31, 69.69 (D) 70.12, 29.88
5. Osmotic pressure of 0.1 M weak acid HA is 3 atm. If molar conductance of 0.1 M HA is 30–1cm2mol–1.
than molar conductance at infinite dilution is :
(A) 150 –1cm2 mole–1 (B) 300 –1cm2 mole–1
(C) 100  cm mole
–1 2 –1
(D) 200 –1cm2 mole–1
6. The molar conductivity of 0.05 M solution of MgCl2 in a cell with electrodes of 1.5 cm2 surface area and
0.5cm apart and 0.15 amphere current flow when a potential difference of 5 volt is applied between two
electrodes –
(A) 200–1 cm2 mol–1 (B) 195.6 –1 cm2 mol–1
–1 2
(C) 149.8 cm mol –1
(D) 169.5 –1 cm2 mol–1
7. 5 litre solution of 0.4 M CuSO4(aq) is electrolyzed using Pt electrode. A current of 482.5 ampere is
passed for 4 minutes. The concentration of CuSO4 left in solution is (Assume volume of solution to be
remained unchanged):
(A) 0.16 M (B) 0.28 M (C) 0.34 M (D) 0.40 M
8. For a concentration cell :
Pt | Ag (s) | Ag+ (aq., C1) || Ag+ (aq., C2) | Ag (s) | Pt
C2
EMF of the cell is X volt then calculate the ratio of ?
C1
 x   x   4x 
(A) anti log  0.059  (B) anti log   (C) anti log  0.059  (D) None of these
   2  0.059   
ADVECH - 82
Electrochemistry
9. A saturated solution of Fe(OH)3 is present in a solution of pH = 12, what is the reduction potential of
0 2.303  RT
Fe3+/Fe in solution ( EFe3  /Fe = –0.036V, Ksp of Fe(OH)3 = 10–26), [ = 0.06]
F
(A) –0.436V (B) 0.39V (C) + 0.36V (D) – 1.2 V
10. Under which of the following condition direction of flow of current will be opposite i.e. from Zn electrode
2.303  RT
to Cu electrode at 298 K : [Given : = 0.06] ; Eºcell for Zn|Zn2+||Cu2+|Cu = 1.1 V
F
(A) [Zn2+ ] > e84.4 [Cu2+] (B) [Zn2+] < e84.4 [Cu2+]
(C) [Zn2+ ] = e84.4 [Cu2+] (D) [Cu2+] = e84.4 [Zn2+]
Section-2 : (One or More than one options correct Type)

This section contains 6 multipole choice questions. Each questions has four choices (A), (B),
(C) and (D) out of which ONE or MORE THAN ONE are correct.
11. Two test tubes  &  contain solutions of sodium salts of halide in water. When Br 2 was added to both
the solutions then following observations were noted.
Test Tube Observation
 Violet vapous emerged
 No reaction occurred
If halides in the tubes I & II are X– and Y– (and their molecular forms being X2 & Y2 respectively) then
the true options would be :
(A) SRP of Br2 is more than the SRP of X2 (B) SRP of Br2 is more than the SRP of Y2
(C) Y2 can oxidize X– into X2 (D) Y2 can oxidize Br– into Br2.
12. In the concentration cell

HA HA
Pt H2 (g) H2(g) Pt
NaA NaA
Value of cell potential will depend on –
(A) Value of pKa of HA (B) Temperature
(C) Concentration of HA in two electrodes (D) Concentration of NaA in two electrodes
13. 20 millimolar solution of aq. CuSO4 (500 ml) is electrolysed with sufficient amount and a total of 0.04
faraday of electricity is supplied. Then :
(A) Total volume of gases evolved at STP = 224 ml
(B) Total volume of gases evolved at STP = 448 ml
(C) Total volume of gases evolved at STP = 672 ml
(D) Resulting solution after electrolysis becomes acidic
14. Emf of cell Ag|Ag+ (saturated solution of Ag2CrO4) || Ag+(0.1 M) | Ag is 0.164 volt at 298 K. Then
(A) Ksp of Ag2CrO4 in water is nearly 2.3 × 10–12
(B) Given cell is a concentration cell
(C) Ksp of Ag2CrO4 can’t be determined by given data.
(D) Concentration of Ag+ ion in anode compartment when EMF is 0.164 volt is nearly 1.66 × 10–4 M
15. EºMg2  / Mg  2.4V , EºSn4  / Sn2  0.1 V , EºMnO –

, H / Mn2 
 1.5 V , Eº  / –
 0.5 V
4 2
Here,
(A) MnO4– is the strongest Oxidizing Agent and Mg is the strongest Reducing Agent.
(B) Sn4+ + 2–  Sn2+ + 2 is a nonspontaneous reaction.
(C) Mg2+ + Sn2+  Mg + Sn4+ is a spontaneous reaction.
(D) Here, Weakest oxidizing agent is Sn4+ and weakest reducing agent is Mn2+
ADVECH - 83
Electrochemistry
16. The following diagram shows an electrochemical cell in which the respective half cells contain aqueous
1.0 M solutions of the salts XCl 2 and YCl3. Given that:
3X(s) + 2Y3+(aq)  3X2+(aq) + 2Y(s) Ecell > 0
Which of the following statements is correct?

(A) The electrode made from metal X has positive polarity.
(B) Electrode Y is the anode
(C) The flow of electrons is from Y to X
(D) The reaction at electrode X is an oxidation
Section-3 : (Numerical Value Questions)

This section contains 6 questions. Each question, when worked out will result in a numerical
value from 0 to 9 (both inclusive)
17. By how many of the following actions, can the Ecell be increased (S = + ve) for the cell reaction
A | A+ (aq) || Cl– | Cl2(g) | Pt
(a) By dilution of anodic solution.
(b) By dilution of cathodic soltuion.
(c) By decreasing temperature.
(d) By increasing pressure of Cl2 in cathodic compartment.
(e) By increasing the mass of anode (A(s))
(f) By increasing temperature
18. At infinite dilution the molar conductance for CH3COONa is 150 S cm 2 mol–1, for HCl is 200 S cm 2 mol–1
and for NaCl is 125 S cm2 mol–1. Then calculate pH of 0.001 M CH3COOH ?
(Given : Molar conductance of CH3COOH at 0.001 M concentration is 2.25 S cm 2 mol–1).
19. The conductivity of an aqueous solution of a weak monoprotic acid is 0.000032 ohm –1cm–1 at a
concentration, 0.2 M. If at this concentration the degree of dissociation is 0.02, calculate the value of 0
(ohm–1 cm2 /eqt).
20. Pt, H2(g) | 2 M CH3COONH4(aq) || 2 M NaCl(aq) | H2(g), Pt

20 atm 0.2 atm
Given pKa(CH3COOH) = 4.74 pKb = (NH4OH) = 4.74
2.303 RT
If E is emf of the cell in volt, calculate 1000 E. [Take : = 0.059]
F
21. EMF of the following cell is 0.634 volt at 298 K Pt | H2 (1 atm) | H+ (aq) || Hg22+(aq.,1N) | Hg(). The pH
of anode compartment is :
0 2.303 RT
Given EHg 2
|Hg
= 0.28 V and = 0.059
2 F
ADVECH - 84
Electrochemistry
SECTION-4 : Comprehension Type (Only One options correct)
This section contains 2 paragraphs, each describing theory, experiments, data etc. 6 questions
relate to the paragraph. Each question has only one correct answer among the four given
options (A), (B), (C) and (D)
Paragraph For Questions 22 to 24

Consider the cell :
Pt | H2 | NaOH (aq), NaCl (aq) | AgCl (s) | Ag
(0.01 M) (0.012 M)
at TºC
Ecell = 1.05 V and EoAgCl / Ag = 0.22 V
RT
Using this knowledge ; and taking = 0.06 (log 1.2 = 0.08)
F
Answer the following questions.
22. Which of the following is overall cell reaction for the given reaction ?
1
(A) H2(g) + AgCl(s)  H+(aq) + Cl¯ (aq) + Ag
2
(B) H2(g) + 2OH¯ (aq) + 2AgCl(s)  2H2O + 2Ag(s) + 2Cl¯ (aq)
(C) H2 + 2Ag+  2H+ + Ag
(D) H2 + 2OH¯ + 2Ag+  2Ag + 2H2O
23. Find the value of pKw of water at TºC.

(A) 14.91 (B) 12.91 (C) 13.91 (D) 14.15
24. What can be said about the temperature TºC ?

(A) It is greater than 25ºC (B) It is smaller than 25ºC
(C) It is equal to 25ºC (D) Nothing can be said from given information
Paragraph For Questions 25 to 27
The specific conductance of 0.001 M Na2SO4 solution is 2.6 × 10–2 –1m–1 and it increases to
7×10–2 –1m–1 when the solution becomes also saturated with CaSO4. The limiting molar conductance
of Na+ & Ca2+ are 0.005 –1 m2 mol–1 and 0.006 –1 m2 mol–1.
25. Limiting molar conductivity of SO2–

4 is -
(A) 0.006 –1m2 mol–1 (B) 0.016 –1m2 mol–1 (C) 0.012 –1m2 mol–1 (D) 0.01 –1m2 mol–1
26. Concentration of SO2– 2+

4 & Ca in the given solutions is -
(A) [SO2– 2+ 2– 2+
4 ] = 0.002 mol/lt, [Ca ] = 0.002 mol/lt (B) [SO4 ] = 0.001 mol/lt, [Ca ] = 0.002 mol/lt
2–
(C) [SO2– 2+
4 ] = 0.003 mol/lt, [Ca ] = 0.002 mol/lt (D) [SO4 ] = 0.001 mol/lt, [Ca2+] = 0.001 mol/lt
27. Solubility product of CaSO4 is -

(A) 6 × 10–6 (B) 4 × 10–6 (C) 2 × 10–6 (D) 10–6
ADVECH - 85
Electrochemistry
SECTION-5 : Matching List Type (Only One options correct)
This section contains 1 questions, each having two matching lists. Choices for the correct
combination of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of
which one is correct
28.
List-I List-II
(P) Molar conductivity (1) Conductivity
Molarity
(Q) Conductivity (2) Conductivity
Limiting molar conductivity
(R) Degree of dissociation (3) Molar conductivity
Limiting molar conductivity
(S) Solubility of sparingly soluble salt (4) Decreases with dilution
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) 1 4 3 2
Practice Test-2 (IIT-JEE (ADVANCED Pattern))

OBJECTIVE RESPONSE SHEET (ORS)
Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25 26 27 28
Ans.
ADVECH - 86
Electrochemistry
PART - I
1. (1) 2. (4) 3. (3) 4. (2) 5. (4)
6. (3) 7. (3) 8. (3) 9. (2) 10. (3)
11. (1) 12. (4) 13. (4) 14. (2) 15. (1)
16. (2) 17. (1) 18. (3) 19. (2) 20. (3)
21. 6 22. 3 (I, II, III) 23. 2 24. 13 25. 50
PART - II
1. (2) 2. (1) 3. (3) 4. (4) 5. (1)
6. (3) 7. (1) 8. (3) 9. (1) 10. (1)
11. (4) 12. (4) 13. (1) 14. (3) 15. (1)
16. (4) 17. (2) 18. (3) 19. (3) 20. (4)
21. (4) 22. (1) 23. (3) 24. (2) 25. (1)
26. (2) 27. (3) 28. (4) 29. (1)
PART - III
1. (B) 2. (B) 3. (C) 4. (C) 5. (A)
6. (C) 7. (B) 8. (C) 9. (C) 10. (D)
11. (B) 12. (A) 13. (C) 14. (B) 15. (A)
16. (C) 17. (B) 18. (D) 19. (B) 20. (D)
21. (A) 22. (B) 23. (D) 24. (A) 25. (C)
26. (B) 27. (D) 28. (A) 29. (C) 30. (C)
31. (A) 32. (C) 33. (B) 34. (B) 35. (B)
36. (B) 37. (A) 38. (A) 39. (B) 40. (A)
41. (B) 42. (C) 43. (B) 44. (B) 45. (B)
46. (D) 47. (D) 48. (B) 49. () 50. (B)
51. (B) 52. (A) 53. (C) 54. (B) 55. (C)
56. (C) 57. (C) 58. (B) 59. (B) 60. (C)
61. (C) 62. (C) 63. (D) 64. (B) 65. (A)
66. (A) 67. (C) 68. (A) 69. (C) 70. (B)
71. (B) 72. (A)
ADVECH - 87
Electrochemistry
PART - IV
1. (a) 0.34 < E° < 0.8 ; (b) –0.44 < E° < 0 2. –0.8825 volt
3. 0.836 volt, 1.1937 volt 4. 0.936V

5. n = 3, Since mass of Sn increasing, Sn - electrode is working as cathode and X - metal electrode anode
and electrons are flowing from X-electrode to Sn-electrode in the external circuit.
6. E = 0.059 V 7. E = 0.395 V 9. –0.042 V 10. KSP = 10–5 11. –0.16V
12. G = – 196.5 kJ ; H = 198.8 kJ ; S = – 7.72 J deg–1 13. 3.389 × 10–4 volt deg–1
14. Sº = – 24.125 kJ K–1 ; Gº = – 7179.6 J ; Hº = – 7196.43 kJ
15. Sº = – 30.88 JK–1 Hº = – 77.23 kJ Gº = – 68.03 kJ
16. A = 114, Q = 5926.8C. 17. V = 1.763 L 18. 43.456 g
19. [Cu2+] = 10–4 M. 20. 2 × 10–16 mole / litre.
21. (a) Eº = 0.59 V, log10Ksp = – 10 ; (b) 52.88, 10–6 mole.

22. (A) 23. (C) 24. (A) 25. (A) 26. (C)
27. (B) 28. (D) 29. (D) 30. (D) 31. (D)
32. (D) 33. (C) 34. (A) 35. (C) 36. (A)
37. (D) 38. (B) 39. (B) 40. (B) 41. (A)
42. (A) 43. (C) 44. (A) 45. (B) 46. (A)
47. (B) 48. (B) 49. (A) 50. (C) 51. (A)
52. (B) 53. (A) 54. (B) 55. (D) 56. 5
57. 14 58. 3 59. 11 60. 26 61. 20
62. 5 63. (BC) 64. (ABC) 65. (ACD) 66. (BD)
67. (ACD) 68. (CD) 69. (AB) 70. (AB) 71. (B)
72. (A) 73. (A) 74. (A) 75. (C)
PART - V
1. (A) 2. (D) 3. (C) 4. (A) 5. (A)
6. (A) 7. (B) 8. (A) 9. (A) 10. (A)
11. (ACD) 12. (BCD) 13. (BD) 14. (AD) 15. (AB)
16. (D) 17. 4 (a, b, d, f) 18. 5 19. 8 20. 59
21. 6 22. (B) 23. (C) 24. (A) 25. (B)
26. (C) 27. (A) 28. (D)
ADVECH - 88
Electrochemistry
PART - I
1. Ecell  E0Sn4  / Sn2  + EFe

0
2
/ Fe3 
 0.15 — 0.77 = – 0.62 V
2. 2Cu  Cu + Cu
+1 +2
2Cu+1 + 2e 2Cu
Cu – 2e Cu+2
––––––––––––––––––––––
2Cu+1 Cu+2 + Cu
––––––––––––––––––––––
2  0.521  2( 0.337)
 E° = = 0.184
2
W1 W2 4 WAg
3. = ;  ; W Ag = 36
E1 E2 12 108
4. Cu2+ + 1e–  Cu+ E10 = 0.15 v G10 = - n E10 F 1
Cu+ + 1e–  Cu E02 = 0.50 v G02 = – n E02 F 2
Cu2+ + 2e–  Cu Gº = Gº + Gº

1 2
(–1) n Eº F = (–1) n 1 E10 F+ (–1) n2 E02 F

n1E10  n2E02 0.15  1 0.50  1
Eº = = = 0.325V
n 2
1 .0591 1
5. H+ + e–  H2. E=0– log10  = + 0.0591 log10[H+].
2 1 [H ]
E1 = 0 {pH = 0}.
E2 = + 0.0591log10[10–7] = – .0591 × 7 {at pH = 7} = – 0.41 V.
0.0591 0.0591
6. Ecell = Eºcell – log10[H+] [Cl–] and E’cell = Eºcell – log10 100[H+] [Cl–].
1 1
E'cell – Ecell = – 2 × 0.0591 = – 0.1182.
8. Cell notation is anode || cathode.
0.06
9. 0.34 = log Keq
2
log Keq = 11.3 or Keq = 2 × 1011
10. Number of moles of Cu2+ produced from anode = number of moles of Cu2+ deposited at cathode.
11. For same charge passed mole of H2 produced = 2 × moles of O2 produced.
W it 3 9.95  10  60
13.      E = 48.5
E 96500 E 96500
1  1  
   0.0112 = 
55  a 
14. K= = 0.616
R  a a
1  –3  1 
  G *   10   G *   10 –3
15. eq =  R   10–2 =  50   G* = 50 m–1
N 1/10
16.  
m (NaCl),  m Na , m(Cl–) keep on increasing as concentration decreases but  keeps on
decreasing with dilution.
ADVECH - 89
Electrochemistry
 3 2
17. (i) K2SO4. Al2(SO4) . 24 H2O  2 K aq + 2 Al aq + 4 SO aq .
  
m (Potash alum ) = 2 mK   + 2  mAl 3  + 4 mSO2 
4
= 2 × 73.5 + 2 × 189 + 4 × 160

= 1165 r–.cm2.mol—1
V.F. for Potash alum = 8 . (total Positive charge)
eq Potash alum  eq Potash alum  1165
= = = 145.6 — cm2 eq—1
8 8
mPotash alume 
1165
eq Potash alume  = 145.6 = 8 : 1
m
(ii)  = V.F. of Compound, V.F. of Potash alume = 8.
eq
18. HCl  H  Cl– NaCl  Na  Cl–

SA  SASB
H+ have highest mobility in comparison with Na, both compound 100% dissociate.
because Molar mass of H+ is less than Na ion and NH4OH is weak basic.
19. Equivalent conductance in different cell is equal :

 eq K  1000
= K and N are constant
N
20. CH3COOH + NaOH  Na+ + CH3COO– + H2O Conductance Ist increases slowly since no. of ions
increases. After end point it increases sharply due to OH– ions.
21. ClO3– + 2H2O + 4e ClO– + 4OH– ; G1°

1
ClO– + H2O + e  Cl2 + 2OH– ; G2°
2
1
Cl2 + e  Cl– ; G3°
2
–––––––––––––––––––––––––––––––––––––––––––––––––
ClO3– + 3H2O + 3e  Cl– + 6OH– ; G°
–––––––––––––––––––––––––––––––––––––––––––––––––
 G° = G1° + G2° + G3°
– 6FE° = – 4F × 0.54 – 1F × 0.45 – 1F × 1.07
3.68
 E° = + = + 0.61 V
6
22. Zn + Ni+2  Zn+2 + Ni
o o
Eº = ENi2 / Ni – EZn2 / Zn
= –0.23 – (–0.76) = + 0.53 V
Positive value shows that the process is spontaneous.
Rest of all (I) (II) (III) combination have negative Eº value.
(I) Eº = –0.44 – (–0.23) = –0.21 V
(II) Eº = –0.76 – (–0.23) = –0.53 V
(III) Eº = –0.76 – (–0.44) = –0.32 V
ADVECH - 90
Electrochemistry
AX
mX
Q mX
23. = 2  =1  AX = 2AY
mY AY mY
Q
1
24. Let wt of metal deposited for x, y, z is 3a, 2a, a respectively & let moles of e– passing for x, y, z be 1, 2
and 3 respectively then the wt of x, y, z deposited is Ex, 2Ey, 3Ez (where Ex, Ey, Ez are equivalent wt. of
x, y, z)
 Ex = 3a
a
2Ey = 2a  Ey = a & 3Ez = a  Ez =
3
 Ex : Ey : Ez
= 3a : a :
= 9:3:1
1
25. R=
k A
Dilution upto twice of initial volume just complete submerge of electrodes, k becomes half and A
becomes double. Hence R remains 50 .
PART - II
1. The Eo of cell will be zero.
2. Here Cr3+ is oxidised to C2O72
3. At LHS (oxidation) 2 × (Ag  Ag+ + e– ) Eºox = –x
At RHS (reduction) Cu + 2e Cu
2+ –
Eºred = + y
2Ag + Cu2+  Cu + 2Ag+, Eºred = (y – x)
0.059
4. 0 = 0.295 – logK ; log K = 10 ; K = 1010.
2
5. A B C
Eored +0.5 V –3.0 V –1.2 V
The reducing power follows the following order: B > C > A.
6. Eºcell = 0.77 + 0.14 = 0.91 volt.
0
7.  NaBr = 126 + 152 – 150 = 128 S cm2 mol–1.
8. Zn + 2H+(aq) 
 Zn2+ (aq) + H2 (g)
0.0591 [Zn2 ] pH2
E = Eº – log
2 [H ]2
Adding H2SO4 means increasing H+ and therefore Ecell will increase and reaction will shift to forward
direction.
9. Cr 2 | Cr 3  0.41V Mn2 | Mn3  1.57V
Fe2 | Fe3  0.77V Co2 | Co3  1.97V
As Cr will have maximum oxidation potential value, therefore its oxidation will be easiest.
10. Al3+ + 3e– 
 Al.
5.12  103
=189.62 mol.
27
Charge = 189.62 × 3 × 96500 = 5.489 × 107 coulomb.
ADVECH - 91
Electrochemistry
11. CH3COONa + HCI  CH3COOH + NaCI From the reaction,
 0CH3COONa + oHCI =  0CH3 COOH + oNaCI or  0CH3COOH =  0CH3COONa + oHCI – oNaCI
Thus to calculate the value of one should know the value of oNaCI along with and oHCI.
0.059
12. 0.152 = – 0.8 – log KSP ; log KSP = – 16.11.
1
13. C = 0.1 M, R = 100 
1
K = 1.29 Sm-1 = × .
100 A
C = 0.02 M, R = 520 .
1
 129
1 520
K= × 129  ÅM = = 124 × 10–4 Sm2mol-1.
520 1000  0.02
14. According to Kohlrausch's law the molar conductivity at infinite diluation (o) for weak electrolyte
CH3COOH is
oCH3COOH = oCH3COONa + oHCI – o NaCI
So for calculating the value of oCH3COOH , value of oNaCI should also be known.
0.0591 [Zn2 ] [Zn2 ] [Zn2 ]
15. 0 = + 1.1 – log ; log = 37.3. ; = 1037.3 Ans.
2 [Cu2 ] [Cu2 ] [Cu2 ]
0.059 [Cr 3 ]2 0.056 (0.1)2
16. Ecell = E0cell – log = 0.3 – log = 0.3 – 0.04 = 0.26 V
6 [Fe2 ]3 6 (0.01)3
17. Fe3+ + 3e–  Fe G1 = –3 × F × EFe
0
3
/ Fe
Fe2+  Fe G2 = –2 × F × EFe

0
2
/ Fe
Fe3+ + e–  Fe2+ G = G1 – G2

G = 3 × 0.036F – 2 × 0.439 × F = – 1 × E0 (Fe3+/Fe+2) × F
E0 (Fe3+/Fe+2) = 2 × 0.439 – 3 × 0.036 = 0.878 – 0.108 = 0.770 V
2 4
18. Al2 O3  Al + O2
3 3
rG = +966 kJ mol–1 = 966 × 103 J mol–1
G = – nFEcell
966 × 103 = – 4 × 96500 × Ecell
Ecell = 2.5 V
19. 2H+ (aq) + 2e–  H2 (g)
0.0591 PH2 0.0591 2 0.0591
Ered = Eºred – log  2
; Ered = 0 – log 2
; Ered = – log2
n (H ) 2 (1) 2
 Ered is forund to be negative for (3) option.
20. X + Y  X2+ + Y
2+
For reaction to be spontaneous Eº must be positive.

EºZn / Zn+2 + EºNi2+ / Ni = 0.76 + (– 0.23) = + 0.53 (positive)
21. Higher the SRP, better is oxidising agent
Hence MnO4- is strongest oxidising agent
22. x = 1.4 S/m.
R = 50 
M = 0.2
ADVECH - 92
Electrochemistry
1
K= ×  = 1.4 × 50 m–1.
R A A
Now, new soltuion has M = 0.5, R = 280 
1
1 1 1 K 1
K= × =  1.4  50   M =  4   5  104
R A 280 4 1000  M 1000 0.5 2000
23. c     B C (Debye Huckel onsagn equation)
24. Reason: Higher the position of element in the electrochemical series, more difficult is the reduction of
its cations.
If Ca2+ (aq) is electrolysed, water is reduced in preference to it. Hence it cannot be reduced
electrolytically from an aqueous solutions.
E0 1.51V E0 1.18V
25. Mn2 
1
 Mn2+  2
 Mn
 for Mn2+ disproportionation, E0 = – 1.51 V –1.18 V
= – 2.69 V < 0
Reaction is non-spontaneous.
26. Cu2+ + 2e–   Cu

2F 1 mole
= 63.5 g.
27. Galvanization is applying a coating of Zn.
28. For strongest reducing agent EOP should be maximum.
EOP Cr / Cr 3 = 0.74 V
Whereas,
EOP Mn2 /MnO  = –1.51 V  EOP Cr3  / Cr O2 = –1.33 V  EOP Cl– / Cl = –1.36 V
4 2 7 2
29. B2H6 + 3O2 B2O3 + 3H2O

1 mol 3 mol
3 mol O2 is required for Burning 1 mol B2H6
H2O  1
  H2  O2
Electroly sis (V.F. of O2 = 4)
2
Equivalent of O2
 mol of O2 = 3
V.F.of O2
 (100A)  t sec.  1 = 3  t = 3  96500  4 hr. = 3.22hrs.
  4 100  3600
 96500 
PART - IV
1. (a) Metal should below hydrogen and Cu2+ but should above Ag+ in series.
(b) Metal should above hydrogen but should below from Zn2+ and Fe2+ both.
2. TiO2+ + 2H+ + e–  Ti3+ + H2O , 0.1 V G1º = – 2 × F × 0.1

Ti3+ + 3e–  Ti – 1.21 V G2º = – 3 × (– 1.21) × F
TiO2+ + 2H+ + 4e–  Ti + H2O
– 4 × Eº × F = – 1 × 0.1 × F + – 3 × (– 1.21) × F
0.1– 3.63
Eº = = – 0.8825 volt.
4
ADVECH - 93
Electrochemistry
0.0591 0.0591
3. Eoxidation = – 0.78 – log 92 = – 0.78 – × 2 × log 9 = –0.836 volt
2 2
Ereduction = –Eoxidation = 0.836 volt
In neutral medium,
0.0591
EOxidation = – 0.78 – log (10–7)2 = –1.1937 volt
2
4. Cr2O72– + 14H+ + 6e–  2 Cr3+ + 7 H2O, 1.33 volt
0.0591 (0.01)2 0.0591
E = 1.33 – log 3 14
= 1.33 – log 10–2 × 1042
6 (0.01)  (10. ) 6
0.0591 0.0591
= 1.33 – × log 1040 = 1.33 – × 40 = 0.936 volt
6 6
 0.0591   0.0591 1 
5. 0.65 = Eoxid + Ered = 0.78 – log (0.1) + 0  0.14 – log 
 n   2 0.5 
0.0591 0.0591  1 0.301
0.01 = – × (– 1) – × 0.301= 0.0591  –
2 
n=3
n 2 n
Electrons flow from X electrode to Zn electrode.
6. Pt / H2O / H+ (HA) // H+ (HB) / H2 / Pt

H2  2H+ + 2e–
2H+ +2e–  H2
2H+(HB)  2H+HA Eº = 0
0.0591 [H ]2 [H ]2
E=0– log  HA2
But Ka =
2 [H ]HB C
0.0591 10 3  C
=– log = – 0.0591
2 10 –5  C
the cell is constructed in reversed direction.
Ecell = 0.0591 volt.
7. Pt / H2 / H+ (C6H5NH2(C) // H+(HCI) / H2 / Pt
H2  2H+(10–8M) + 2e– , C6H5NH2 + H2O  C6H5NH3+ + OH–
(OH– )2
2H+ + 2e–  H2 Kb =
5 10 4
0.5
2H+(5×10–2)  2H+(10–8)
0.0591 (108 )2 0.0591 0.0591
E=0– log 
=– log 10–14 × 4 = . [log4 – 14] = 0.396 volt
2 (5  10 )2 2 2 2
8. (A) Hg2Cl2(s) + Cu(s) Cu2+(aq) + 2Cl– (aq) + 2Hg(l)
(B) 2Ag(s) + 2IO3– + Zn2+ 2AgIO3(g) + Zn(s)
(C) Mn(s) + 2OH– + Cu2+ Mn(OH)2(s) + Cu(s)
.06 10 –10 / 0.2

9. E=0– log = –0.042 V
1 10 –13 /10 –3
.06 1 1
10. E0cell = log  – 0.12 + 0.27 = .03 log  KSP = 10–5
2 K SP K SP
11. E0Cell = 0.06(–log KSP)  0.8 – EI0– / AgI / Ag = 0.96  EI0– / AgI/ Ag = 0.16V
ADVECH - 94
Electrochemistry
12. Cd (12.5%) in Hg / 3Cd SO4, 8H2O (solid) / satd sol of CdSO4 || Hg2SO4(s) | Hg, E = 1.018 volt
 dE  –5
 dT  = – 4 × 10 volt deg–1.
P
G = – nEF = – 2 1.018 × 96500 = – 196.474 kJ

 dE 
S = nF.  = 2 × 96500 × (– 4 × 10–5) = – 7.72 JK–1.
 dT  P
G =H – TS
298  (–7.72)
H = – 196.474 + = – 196.474 – 2.3 = 198.774 kJ
1000
1
13. Ag(s) + Hg2CI2(s)  AgCI(s) + Hg(l), H = 1280 cal.
2
E = 0.0455 volt
dE
H = – nEF + nF.T.
dT
dE dE
1280 × 4.18 = – 1 × 0.0455 × 96500 + 1 × 96500 × 298 × .  = 3.387 × 10–4 volt deg–1.
dT dT
dE
14. = – 0.125 VK–1. Eº = 0.0372 volt
dT
Gº = – nEF = – 2 × 0.0372 × 96500 = – 7.1796 kJ.
 dE 
Sº = nF ×  = 2 × 96500 × (– 0.125) = – 24.125 kJ K-1.
 dT  P
Hº = Gº + T Sº = – 7.1796 – 298 × 24.125 = – 7196.43 kJ
15. E025ºC = 0.3525 volt E020ºC = 0.3533 volt n=2
dE  E0 – E020ºC  0.3525  0.3533

=  25ºC  = = – 1.6 × 10–4 volt deg–1.
dT  T2 – T1  25  20
Gº25 = Hº25 – 298 × Sº25 = –2 × 0.3525 × 96500 = – 68.03 kJ
Sº = 2 × 96500 × (– 1.6 × 10 ) = – 30.88 Jk.
–4
30.88
Hº = Gº + TSº = – 68.03 – 298 × = – 77.23 kJ
1000
16. v.f. of metal = 2.
w = Zit.
E M  it 
1.95 = it = M = 114 g.
96500 v.f.  96500
63.5  (it) 63.5  (it)
vc Cu ds fy,, w =  1.95 =  it = 5926.77 C.
2  96500 2  96500
 C2H6  2CO2 + H2
Electrolysis
17. 2CH3COONa 
at anode Cathode
0.965  60  60
Electric supplied = = 3.6 × 10–3 F
96500
3.6  10 3 0.0821  298
VH2 = × = 0.44 lit ; Vtotal = VC2H4 + VCO2 + VH2 = 4 × 0.44 = 1.76 lit.
2 1
ADVECH - 95
Electrochemistry
18. Reaction at anode 2H2SO4 H2S2O8 + 2H+ + 2e–
H2S2O8, O2 are the product at anode.
2H2O O2 + 4H+ + 4e–
Reaction at cathode 2H2O + 2e– H2 + 2OH–
Eq. of H2 = Eq. of O2 + Eq. of H2S2O8
9.722 2.35
×2= ×4+x×2  x = 0.244 mole  WH2S2O8 = 43.49 g.
22.4 22.4
3+
19. Eº Bi /Bi = 0.226 volt Eº Cu2+ / Cu = 0.344 volt
0.0591 1
0.226 = 0.344 log 2
 – log [Cu2+] = 4 [Cu2+] = 10–4 M.
2 [Cu ]
20. K = 5.8 × 10–8 Scm–1,  oH = 350 Scm2  oOH = 198 Scm2
1000  5.8  10 8  H2O (1000  5.8  10 8)

H2O = ; = = = 0.1907 × 10–8 = 1.907 × 10–9
55.5  o
H2O 55.5  (350  198)
Ka = C2 = 55.55 × (1.907)2 × 10–18 = 2.02 × 10–16.
21. (a) Gºr = – 109 + 129 – 77 = – 57 kJ/mol

Cell representation : Ag | AgCl | | Cl –| Ag+ | Ag.
– 1× 96500 × Eº = – 57 × 103.
Eº = 0.59 volt.
0.059 1
0 = 0.59 – log .
1 K SP
log KSP = – 10.
(b) Zn  Zn2+ + 2e–, 0.76 volt.
2Ag + 2e  2Ag, 0.80 volt.
+ –
__________________________________
Zn + 2Ag+  Zn2+ + 2Ag, Eºcell = 1.56 volt.
__________________________________
6.539  102
nZn = = 10–3 mol, [Ag+] = K sp = 10–5 M.
65.39
0.059
0 = 1.56 – log K nAg+ = 10–5 × 0.1 = 10–6 M.
2
nAg = 10–6 mol.  log K = 52.8.
1
22. H+ + e–  H2 , E° = 0 ,G° = 0
2
H2O H+ + OH– , G° = – 8.314 × 298 ln 10–14
1
H2O + e–  H2 + OH– , –1 × E° × 96500 = –8.314 × 298 ln10–14
2
E° = – 0.828 Volt.
23. Hg22 + 2e–  2Hg , 0.789 Volt
Hg  Hg2+ + 2e– , –0.854 Volt
Hg22+  Hg + Hg2+ , –0.065 Volt
G = – 2× (– 0.065) × 96500 = –8.314 × 298 ln Keq. ; Keq.= 6.3 × 10–3
ADVECH - 96
Electrochemistry
24. MnO4– + 8H+ + 5e–  Mn2+ + 4H2O
0.0591 [Mn2 ]
E1 = E° – log
5 [MnO4– ]  18
0.0591 [Mn2 ] 0.0591
E2 = E° – log =– × 32 = –0.37824 E1–E2 = 0.38 Volt.
 
8
5 [MnO4– ]  10 –4 5
0.0591 1
25. 0 = (–0.771 + 0.7991) – log  0 = 0.0281 +0.0591 log x
1 x
0.0281
log x =–  x = 0.335 M
0.0591
0.0591
26. 0 = (– 0.151 – 0) – log [H+].
1
0.151
0.0591 × log[H+] = – 0.151 ; pH = = 2.56
0.0591
0.0591 1
27. E0 = E0Ag |Ag – log
Ag | Ag I |I – 1 K SP
0.0591 1
– 0.151 = 0.799 – log
1 K sp
0.0591 log Ksp = –0.151 –0.799

log Ksp= – 16.074
Ksp = 8.43 × 10–17
0.0591 1
28. EI– / AgI / Ag = 0.8 – log
1 K sp
= 0.8 + 0.0591 × log 8.3 × 10–17 = – 0.15 Volt
or
1 8.31  298  2.303
Eº Ag / Ag /  –  Eº RT . ln = – 0.8 – log ksp
Ag / Ag  k sp 96500
F
= – 0.8 – 0.0591. log 8.3 × 10–17 = – 0.8 + 0.095 = 0.15 V.

2 2
29. A(s) + Baq.  A aq. + B(s) , H° = – 285 KJ
Assuming s to negligible , G° = H° = –285×103×0.84 = –2×E°×96500
E° = 1.24 Volt
d
30. = –0.00065 Vol deg–1
dt
dE
S298 = n.F. = 2×96500× (–0.00065) = – 125.5 J/K.
dT
dE (0.6753 – 0.6915)
31. = = –6.48×10–4 V deg–1
dT (25 – 0)
dE
H298 = – neF + nFT = – 2 × 0.6753 × 96500 + 2 × 96500 × 298 × (–6.48×10–4)
dT
= 2 × 96500 (– 0.6753 – 0.1931) = – 167.6 KJ.
ADVECH - 97
Electrochemistry
32. E° = 1.1028 – 0.641 × 10–3 T + 0.72 × 10–5 T2
 dEº  –3 –5
 dT  2S = –0.641 × 10 + 2 × 0.72 × 10 T = (–0.641 + 0.36) × 10–3 = –0.281 × 10–3
dEº
S° = nF = 2 × 96500 × (–281 × 10–3) = – 54.23 EU
dT
33. E298 = 1.1028 – 0.641 × 10–3 × 25 + 0.72 × 10–5 × (25)2 = 1.091275 Volt
= –8.314 × 298 ln K= – 2 × 1.091275 × 96500
K = 1036.91 = 8.128 × 1036.
 d   dE 
34. S = –  ( G) = + nF 
 dT p  dT  p
 dE  S
 dT  = nF
p
35. Na+ + e–  Na(s)

1mole 1 Faraday
Al3+ + 3e– Al(s)
1 Faraday
1
No. of mole of Al = mole.
3
36.  Ag = 62.3 Scm2 mol–1 ,  Cl = 67.7 Scm2 mole–1

KAgcl = 3.4 × 10–6 Scm–1
1000  3.4  10 –6
 AgCl = (62.3 + 67.5) =
S
3.4  10 –3
S= = 2.6 × 10–5 M
(62.3  67.5)
38. Higher the std. reduction potential, higher is the oxidising power.
0.059 0.01  (0.01)2

39. Ecell = 0.29 – log or Ecell = 0.35 volt
2 (0.01)2  1
40. Eºcell = 1.89 ; EºCe4+/Ce3+ + EºCo/Co2+ = E + 0.277  E = 1.62 V
5  1.5 – 2  1.23
41. EºMnO / MnO = = 1.7 volt
4 2 3
nFd Ecell d Ecell  S

42. S = or =
d t d t n F
1 0.414
43. – 0.413 = 0 – 0 .059 log 
or = – log H+ = pH or pH = 7
[H ] 0.059
44. Z > Y > X (Non metals like F2 > Cl2 > Br2)
So, Y will oxidise X– but not Z–
Z will oxidise both X– and Y–
X can't oxidise Y– or Z– .
45. Eºcell = 0.8 – (– 0.76) = 1.56 V

ADVECH - 98
Electrochemistry
0.059 1.5
46. Ecell = 0.77 – log = 0.652 V
1 0.015
0.059 [Zn2 ] [Zn2 ]

47. 1.1591 = 1.1 – log or = 10–2 = 0.01
2 [Cu2 ] [Cu2 ]
48. Ag Ag+ + e–
E1 = Eoxid + Ecalomel
0.0591
= E' – log Ksp1 + Ecalomel
1
0.0591 K sp1
E2 = E' – log Ksp2 + Ecalomel  E2 – E1 = 0.177 = 0.0591 log
1 K sp2
K sp1
= 106.
K sp2
49. H+ + CI– + NaOH  Na+ + CI– + H2O to conductance Ist decreases since no. of ions decreases after
end point it inceases.
0.059 [Sn2 ]
50. Ecell = Eºcell – log Ag+ increase, Ecell increase.
2 [Ag ]2
i  15  60 6.72
51. = ×2  i = 64.3 amp.
96500 22.4
52. AgCl + e–  Ag + Cl– E° = 0.2 V
Ag  Ag+ + e– E° = – 0.79 V
––––––––––––––––––––––––––––––––––––––––
e
AgCl 
 Ag+ + Cl– E° = – 0.59 V
0.059 0.059
E° = log K  – 0.59 = log KSP  KSP = 10–10
n 1
Now solubility of AgCl in 0.1 M AgNO3
S (S + 0.1) = 10–10  S = 10–9 mol/L
Hence 1 mole dissolves in 109 L solution
hence in 106 L amount that dissolves in 1 m mol.
53. Q = 10 × 4825 = 48250 C
48250
no. of faraday = = 0.5
96500
1 1
Ag + Cu++  Ag+ + Cu
2 2
2.00 2.00
2–0.25 2 + 0.50
0.0591 [Ag ]
Ecell = EºCell – log
1 [Cu ]1/ 2
0.0591 2.00
E1 = EºCell – log
1 (2.00)1/ 2
0.0591 2.50
E2 = EºCell – log
1 (1.75)1/ 2
ADVECH - 99
Electrochemistry
0.0591  2.50  0.0591
E = E2 – E1 = log 2  log = [log 1.41 – log 1.88]
1  1.75  1
0.0591 0.0591
= [0.1492 – 0.2742] = – × 0.125 = – 0.00738 V.
1 1
 Eº 
 = Sº = –2 × 96500 × 1.45 × 10 = –279.85 JK
–3 –1
54. nF 
 T 
Gº = –nFEº = –2 × 1.36 × 96500 = –262.48 KJ.
Hº = Gº + TSº
= –262.48 × 103 – 300 × 279.85
= –262480 – 83955 = –346.435 KJ
55. EoX– / AgX / Ag = EoAg / Ag + 0.059 log10 Ksp (AgX)

1
o
Thus, salt having least value of Ksp will have least value of EX– / AgX / Ag and all values will be less than
EoAg / Ag (since 2nd term will always have a negative values).
56. If cell is taken to be conc cell, Eºcell = 0

Anode : Ag Ag+a + e–
Cathode : Ag+c + e–  Ag
–––––––––––––––––––
Agc+ Aga+
From Nernst eq,
0.059 [Ag ]a  0.059 [Ag ]a
Ecell = Eºcell – log 0=0 – log
1 [Ag ]c 1 [Ag ]c
K sp of AgBr K sp of AgCI 5  10 13 [Br  ] [Br  ] 1
 [Ag+]a = [Ag+]c  = or , = = = .
[Br  ] [CI ] 10 10 [CI ] [CI ] 200
57. Charge passed = 0.01 Faraday

 1 
At the anode  H2O  O2  2H  2e   with 90 % efficientcy 0.01 × 0.9 F have been used and will
 2 
1
produce × 0.01 × 0.9 mole of O2 i.e. 0.00225 mol O2 .
4
2e
At the cathode 2H2O   H2 + 2OH–
0.01  0.8
moles of H2 produced = mol = 0.004 mol
2
Total moles produced of gases = 0.004 + 0.00225 = 0.00625 mol
vol. at STP = 0.00625 × 22400 mL = 140 mL
C 2 1 2
59. Ka =  =
1  6 1 
1  (1)2  4  6  1 1  1  24 1
 = = =
12 12 3
1 1
 [O3–] = 1 × = M
3 3
ADVECH - 100
Electrochemistry
3  10 8
 [Ag+] = = 9 × 10–8 M
1
3

2e
Now 2Ag + Zn+2   2Ag+ + Zn
0.06 1
Gives: E = – 1.56 + log = – 1.1376 V
2 (9  10 8 )2
Ans. 11
60. MX M
+
+ X–
a + 10–7 a
–7
KSP = (a + 10 ) a
55  10 7 = (6 × 10–3 (a + 10–7) + 8 × 10–3 a + 7 × 10–3 × 10–7)
1000
55 × 10–10 = 6 × 10–3 a + 6 × 10–10 + 8 × 10–3 a + 7 × 10–10
42 × 10–10 = 14 × 10–3 a
a = 3 x 10–7
KSP = 12 × 10–14
61. Eocell  ERP(RHS)

o
 ERP(LHS)
o
= – 0.76 – (– 1.36) = 0.6

r G  RT ln K eq ;
o
nFEo 2  0.6 2  0.6

or log K eq  = = 20   20; K f  1020
RT  2.303 0.06 0.06
dE 1.718  1.2
62. Sº = nF = 2 × 96500 × = 5000 Joule/K.
dt 20
63. Reduction and electronation take place at cathode elctrode, so it become positive electrode.
64. (A, B, C) Reduction Potential of Ce is higher than that of Zn.
º º
65. (A) because ECu 2
/ Cu
> EFe 2
/ Fe
.
66. Recharging reaction: 2PbSO4 (s) + 2H2O. 

 Pb(s) + PbO2(s) + 2H2SO4 (aq)
67. On dilution specific conductance decreases while molar conductivity increases.
68. Create a cell with required cell reaction

O2 + SO 4–2  S2O8–2 + H2O Eocell = 1.23 – 2.01 < 0
 Nonspontaneous cell reaction
69. Electrolysis of NaBr Solution
At Anode 2Br–  Br2 + 2e–
–
2H2O  2e –
at cathode  H2 + 2OH
It is clear that Br– ion are replaced by OH–.
Hence molar conductance & specific conductance increases.
ADVECH - 101
Electrochemistry
70. (A) For Cr2O72– (acidic solution)
o
Eº = 1.23 which is greater than E(Fe2 /Fe) hence it can oxidize Fe
(B) H2O2  2H+ + O2 + 2e– Eº = –0.70 V
O2 + 4H+ + 4e–  2H2O Eº = 1.30 V
(–0.70  2)  (4  1.30)
H2O2 + 2H+  2H2O Eº = = 1.9
2
o
Here Eº is grater than E(Fe2 /Fe) hence H2O2 in acidic medium can oxides Fe.
2.303 RT (Zn2 ) 2.303  8.31  200 2

71. Ecell = Eºcell – log 2
= 0.76 + 0.34 – log = 1.08 volt.
nF (Cu ) 2  96500 0.2
72. Cu+2 + 4 NH3 [Cu (CH3)4]+2

0.2 1 0
x 1–0.8 0.2
0.2 1
kf = 4.0  1011 = =
x  (0.2) 4
x  (0.2)3
1011
x=  x = 3.125 × 10–10 [Cu+2] = 3.125 × 10–10
(0.2)3  4
0.0591 2
Ecell = 0.75 + 0.34 – log
2 3.125  10–10
0.0591
= 1.1 – (10 – 0.194) = 1.1 – 0.29 = 0.81 volt
2
0.0591 [2]
73. Ecell = 1.1 – log =0
2 [Cu 2 ]
[2] 1.1 2 2
log 2
= = 37.23  = 1.68 × 1037  [Cu+2] = 1.19 × 10–37
[Cu ] 0.0591 [Cu 2 ]
74. First conductance decreases due to nutralisation of free H+ ions of weak acid, then it increases due to
formation of salt and after equivalence point it increases more fastly due to increasing of OH– ions.
75. First conductance decreases due to nutralisation of strong acid H+ ion then after it increases due to
nutralisation of weak acid and after equivalence point it increases more fastly.
PART - V
1. Fe+2 + 2e–  Fe
(965)(1)
Number of milimoles of e– passed = × 1000 = 10
96500
 Milimoles of Fe+2 reduced = 5
 Milimoles of Fe+2 left = 1000 x – 5
 By equating mili equivalent = (1000x – 5) × 1 = (0.1)(10)(5)  x = 10–2
2. CH3COOH + NaOH CH3COONa + H2O
milli moles 100×0.2 100×0.2 – –
0 0 100×0.2
Then,
ADVECH - 102
Electrochemistry
100  0.2  10 3  2.0
[CH3COONa] = × 1000 = 0.1 D.O.D () for CH3COOH = m = = 10–2
200 m0
200
Then, Ka of CH3COOH = C2 = 0.1 × (10–2)2 = 10–5
 pKa = 5 for CH3COOH.
So, pH of CH3COONa salt is :
1 1 1 1
pH = 7 + pKa + logC. =7+ × 5 + log0.1 = 9.
2 2 2 2
 
3. m =  Ag +  Br –
=a+b
K K
m = K × 1000  S= × 1000  S (g/lit) = × 1000 × 188
S m ab
 122
4. = º = 0.936
º 
º = 130.34 –1cm2 eq–1
º 0.98 º 0.98
=  =
º 1.98 130.34 1.98
ºK = º = 64.51 –1cm2 eq–1
And
º– º º 0.98
º =1 –  º =1 –
 º  1.98
º– 1 130.34
130.34 = 1.98  º– = 1.98 = 65.83 –1cm2 eq–1
5.  = iCRT
1
3 = i × 0.1 × × 300
12
i = 1.2
i = 1 + (n–1)
1.2 = 1 + (2–1) = 0.2
30 
0.2 =   m = 150 –1cm2 mol–1
m
V 5 100
6. V = iR R= = = 
i 0.15 3
1 3 0.5
K=  = × = 10–2
R a 100 1.5
M = K  1000 = 10–2 × 1000 = 200–1 cm2 mol–1
M 0.05
7. Cu2+ + 2e–   Cu
482.5  4  60
2mol mol
96500
= 1.2 mol electrons
+2
2 mole electrons then Cu reacted = 1 mole
ADVECH - 103
Electrochemistry
1
When 1.2 mole electrons then Cu+2 reacted = × 1.2 = 0.6
2
so, remaining Cu+2 moles = 2 – 0.6 = 1.4 moles
1.4
Remaining [CuSO4] = = 0.28 M.
5
8. For concentration cell Eºcell = 0

Ag (s) 
 Ag+ (C1) + e–
Ag+ (C2) + e– 
 Ag (s)
____________________________
Ag+ (C2) 
 Ag+ (C1)
C 
Then, Ecell = X = 0 – 0.059 log  1 
 C2 
C  X
 log  2  =
 C1  0.059
C2  x 
 = anti log  0.059 
C1  
K sp 10–26
–
9. Fe(OH)3 +3
Fe + 3OH ; +3
[Fe ] = = = 10–20
[OH– ]3 (10–2 )3
0 0.06 1 0.06
EFe3 /Fe = EFe 3
/Fe – log 3 = –0.036 – × 20 = –0.036 – 0.4 = – 0.436
3 [Fe ] 3
10. For cell reaction to take place in opposite direction. Ecell must be negative.
Ecell < 0
0.06 [Zn2 ]
Eºcell – log < 0
2 [Cu2 ]
0.06 [Zn2 ]
1.1 – log < 0
2 [Cu2 ]
0.06 [Zn2 ]
log > 1.1
2 [Cu2 ]
[Zn2 ]
log > 36.67
[Cu2 ]
[Zn2 ]
n > 84.4
[Cu2 ]
[Zn2+] > [Cu2+]e84.4
11. X¯ is I¯
Y¯ is Cl¯
SRP Cl2 > Br2 > 2
K a [HA]anode
RT [H ]anode RT [NaA]anode
12. Ecell = – n  =– n
nF [H ]cathode nF K a [HA]cathode
[NaA]cathode
ADVECH - 104
Electrochemistry
13. Anode : 2H2O  O2 + 4OH¯ + 4e–
0.01 mol 0.04 F
Cathode : Cu2+
+ 2e –
 Cu(s)
–3
20×10 ×0.5 0.04 faraday
= 10–2 mol –0.02
= 0.01 mol = 0.02 F
2H2O + 2e–  H2(g) + 2OH¯
0.02F 0.01 mol
Total volume of gases evolved at STP = (0.01 + 0.01) × 22.4 = 448 ml
0.0591 0.1
14. 0.164 = 0 + log10 [Ag ]
1 anode
 [Ag+]anode = 1.66 × 10–4 M.

 1.66  10 –4 
+ 2
Ksp = [Ag ] × [CrO2–
4 ] = 1.66 × 10 –4
×  2

 
15. Hint: Reverse of (B) & (C) is spontaneous; weakest Oxidizing Agent here is Mg2+]
0.6 [A  ][Cl ]
17. (a, b, d, f) E = Eº – log
n PCl2
18. ºCH3COOH = ºCH3COONa + ºHCl – ºNaCl
= 150 +200 – 125 = 225 S cm 2 mol–1.

cCH3COOH = 2.25 S cm2 mol–1.
cCH3COOH 2.25
= = = 10–2
0CH3COOH 225
Then [H+] for CH3COOH = C = 0.001 × 10–2 = 10–5

 pH = – log[H+] = – log(10–5) = 5
19. K = 3.2 × 10–5 –1.cm–1

103 K
=
C
3.2  102
 = = 16 × 10–2
0.2

 =

 16  10 2
  = = =8
 0.02
ADVECH - 105
Electrochemistry
0.059
20. E = Eºcell – . log Q
2
(10–7 )2 0.2 1
Q= × –7 2
=
20 (10 ) 100
0.059 1 0.059
E=0– . log = × 2 = 0.059
2 100 2
 1000E = 1000 × 0.059 = 59
1
21. At cathode : Hg22+ + e– 
 Hg(l)
2
1
At anode : H2(g) 
 H+(aq) + e–
2
______________________________
1 1
Hg22+ + H2(g) 
 Hg(l) + H+(aq)
2 2
0.059
Ecell = E0cell – log [H+]
1
or 0.634 = (0.28 – 0) + 0.059 pH
0.634  0.28
or pH = =6
0.059
22. Overall reaction should be the one which is written in term of species present in the given electrode/cell.
Hence at anode H2 + 2OH¯  2H2O + 2e–
At cathode 2AgCl + 2e–  2Ag + Cl¯
23. We can assume the given cell to be:

Pt | H2 | H+ (aq), Cl¯ (aq) | AgCl (s) | Ag
o
With this assumption, Eocell = EAgCl / Ag– – ESHE
o
= 0.22 V
And cell reaction is :
1
H2(g) + AgCl(s)  H+(aq) + Ag(s) + Cl¯(aq)
2
0.06
 Ecell = Eocell – log (H+) (Cl–)
1
Kw
1.05 = 0.22 – 0.06 log (Cl¯)
(OH¯)
 (Cl– ) 
 – logK w – log 
0.83 = 0.06  (OH– ) 

83 0.012
= pKw – log
6 0.01
83
= pKw – log(1.2)
6
83
 pKw = + log(1.2) = 13.91
6
ADVECH - 106
Electrochemistry
24. pKw = 13.91
i.e. Kw > 10–14
Hence T is greater than 25ºC.
25. For the solution of Na2SO4

K 2.6  10–2
= =
C 1
2Na
o
 +
SO
o
2– = 0.026
4
SO
o
2– = 0.026 – 0.01 = 0.016 
–1
m2 mol–1
4
mol
26. For the Na2SO4 solution saturated with CaSO4 (Let x be the solubility of CaSO4)
m3
Ksolution = KNa + K SO2–
4 + K Ca2 
0.07 = (  Na  × [Na+]) + ( SO2–

o
o
4 × [ SO2–  2 2+o
4 ]) + ( Ca × [Ca ])
= (0.005 × 2) + 0.016(1 + x) + (0.006x)

0.07 = 0.01 + 0.016 + 0.016x + 0.006x
X = 2 mol/m3
 [Ca2+] = 0.002 mol/lt, [ SO2–
4 ] = 0.003 mol/lt
27. Solubility product of CaSO4 = [Ca2+][ SO2–

4
] = 0.002 × 0.003 = 6 × 10–6
ADVECH - 107

Part - I: Practice Test-1 (Iit-Jee (Main Pattern) ) : Electrochemistry

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Electrochemistry

 Marked Questions may have for Revision Questions.

B. Test Paper Format and its Marking Scheme:

3. How many g of silver will be displaced from a solution of AgNO3 by 4 g of magnesium?

The E° in the given figure is X. Report the answer as 10X.

Practice Test-1 (IIT-JEE (Main Pattern))

PART - II : JEE (MAIN) / AIEEE OFFLINE PROBLEMS (PREVIOUS YEARS)

2. Which of the following reactions is possible at anode : [AIEEE 2002, 3/225]

11. The molar conductivities NaOAc

12. Given data is at 25°C :

16. Given : E0 = – 0.72, E0 = – 0.42 V

21. Given : E0Cr 3  / Cr = –0.74 V ; EMnO

E0Cr O2 / Cr3 = 1.33 V ; E0Cl / Cl = 1.36 V

PART - III : NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) STAGE-I

10. KCl is used in a salt bridge because : [NSEC-2001]

(A) (B) (C) (D)

17. Fe2+ + 2e  Fe .....(i)

(A) (B) (C) (D)

22. In an alkaline energy cell the overall cell reaction is as follows :

(A) (B) (C) (D)

volume of KCl volume of KCl volume of KCl volume of KCl

(I) (II) (III) (IV)

At 25ºC, the free energy change for this reaction is : [NSEC-2014]

PART - IV : HIGH LEVEL PROBLEMS (HLP)

Example Calculate Ksp if (PbSO4) Ecell at 298 K of this electrode is 0.236 V

Hg22 (aq) + 2Cl–  Hg2Cl2(s) Hg2Cl2  Hg22 (aq) + 2Cl–(aq)

2Hg() + 2Cl–(aq)  Hg2Cl2(s) + 2e– Hg2Cl2(s) + 2e–  2Hg() + 2Cl-

2. The standard reduction potential of TiO2+ and Ti3+ are given by

0.5 M Sn2+ 0.1 M Xn+

21. (a) Calculate Gº of the following reaction :

ONLY ONE OPTION CORRECT TYPE

23. Given : Hg22+ + 2 e 2 Hg , Eº = 0.789 V & Hg2+ + 2 e  Hg , Eº = 0.854 V,

41. MnO4– + 8H+ + 5e–  Mn2+ + 4H2O ; Eº = 1.51 V ; G10 = – 5 × 1.51 × F

(A) 1.70 V (B) 0.91 V (C) 1.37 V (D) 0.548 V

NUMERICAL VALUE QUESTIONS

59. Calculate the emf of the cell in mV

Find the value of (a + b) ? Given that 10 < a < 100

61. Zn2 (aq)  4OH (aq) 

Zn(OH)24 (aq)  2e  Zn(s)  4OH (aq); E  1.36V

ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

67. Which of the following statements is / are correct ?

Given EoZn2 |Zn = – 0.76 V Kf [Cu(NH3)4]+2 = 4 × 1011

Weak Acid versus Strong Base

volume of NaOH volume of NaOH volume of NaOH

PART - V : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))

SECTION-1 : (Only One option correct Type)

Section-2 : (One or More than one options correct Type)

12. In the concentration cell

15. EºMg2  / Mg  2.4V , EºSn4  / Sn2  0.1 V , EºMnO –

Which of the following statements is correct?

Section-3 : (Numerical Value Questions)

20. Pt, H2(g) | 2 M CH3COONH4(aq) || 2 M NaCl(aq) | H2(g), Pt

Paragraph For Questions 22 to 24

23. Find the value of pKw of water at TºC.

24. What can be said about the temperature TºC ?

Paragraph For Questions 25 to 27

25. Limiting molar conductivity of SO2–

26. Concentration of SO2– 2+