Electrochemistry
Electrochemistry
Electrochemistry
Class: 12 2019-2020
Worksheet Number: 12/Chem/03/AK
The alkaline medium inhibits the rusting of iron. This is because it prevents the availability of H + ions. This in
turn reduces rate of oxidation of Fe to Fe+2. Thus the rusting of iron is inhibited.
The molar conductivity of a solution at infinite dilution is called limiting molar conductivity (λ om)
Zinc is more reactive than copper. Therefore, zinc can displace copper from its salt solution. If copper sulphate
solution is stored in a zinc pot, then zinc will displace copper from the copper sulphate solution.
When standard reduction potentials have a negative value it indicates the substance can undergo oxidation
more easily and hence will be a strong reducing agent.
sodium, potassium,aluminium,calcium
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Answer Key
Each question carries 2 marks : 2019-2020
7. Define fuel cell and write its two advantages
Galvanic cells that are designed to convert the energy of combustion of fuels like hydrogen, methane,
methanol, etc. directly into electrical energy are called fuel cells.
Advantages: High efficiency (70%), non polluting, run continuously as long reactants are supplied, by product
is water.
8. A galvanic cell has electrical potential of 1.1V. If an opposing potential of 1.1V is applied to this cell, what will
happen to the cell reaction and current flowing through the cell?
No chemical reaction.
Zn/Zn2+!!Ag+/Ag
(i)Zinc as it is anode.
10. Express the relation among the cell constant, the resistance of the solution in the cell and the conductivity of
the solution. How is the conductivity of a solution related to its molar conductivity?
a) Resistance ohm R
c) Conductance Siemen or Ω- G
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12. When acidulated water (dil.H2SO4 solution) is electrolysed, will the pH of the solution be affected? Justify your
answer
13. What are the factors on which conductivity of an ionic solution depends? How does it differ from electronic
conductance?
The law states that limiting molar conductivity of an electrolyte can be represented as the sum of the individual
contributions of the anion and cation of the electrolyte at infinite dilution.
15. Can Cell E ,V or ΔrG V for cell reaction ever be equal to zero? 30. Under what condition is E Cell = 0 or Δr G =
0?
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Answer Key
16. The following chemical reaction is occurring in2019-2020
an electrochemical cell:
=0.81-(-2.36)=3.17V
(i) Electrons move from Zn to Ag. (ii) Ag is the cathode. (iii) Cell will stop functioning. (iv) When E Cell = 0. (v)
Concentration of Zn2+ ions will increase and concentration of Ag+ ions will decrease (vi) When Ecell = 0
equilibrium is reached and concentration of Zn2+ ions and Ag+ ions will not change
18. Corrosion is essentially an electrochemical phenomenon. With the help of a diagram explain the reactions
occurring during the corrosion of iron kept in open atmosphere.
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Answer Key
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At a particular spot of an object made of iron, oxidation take place and that spot behave as anode.
Electrons released by iron at anodic spot move through the metal and go to another spot of metal which
behaves as cathode. Reduction of oxygen in the presence H + ions takes place. The H+ ions are formed by
dissolution of gases like carbon dioxide in water.
19. Define the term molar conductivity and indicate how molar conductivity of a substance changes with change in
concentration of a weak electrolyte and strong a strong electrolyte in its solution.
Molar Conductivity :-
Molar Conductivity of a solution is defined as the conductance of the solution which contains one mole
of the electrolyte such that the entire solution is place between the two electrodes kept one centimeter apart. It
is denoted by Λm.
Molar Conductivity, Λm = κ
Where, κ = conductivity and C = concentration in moles per litre. Its unit is S cm 2 moI -1
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Weak electrolyte: - When the concentration of weak electrolyte becomes very low, its degree of ionization
rises sharply. There is sharp increase in the number of ions in the solution. Hence the molar conductivity of
weak electrolyte rises steeply at low concentration.
Strong Electrolyte: - The molar conductivity of strong electrolyte decreases slightly with the increase in
concentration. This decrease is due to the increase in interionic attraction as a result of greater number of ions
per unit volume. With dilution the ions are far apart and interionic attractions become weaker and conductance
increases.
Section B
Conductivity of solution is the conductance of ions present in a unit volume of solution. On dilution the
number of ions per unit volume decreases. Hence the conductivity decreases.
What is the quantity of electricity in coulombs needed to reduce 1 mol ofCr 2O72- ?
From a given reaction, 1 mole of Cr2O7-2 ions require 6 mole of e-s to form Cr+3
22. Explain with an example how weak and strong electrolytes can be distinguished.
If the aqueous solution of electrolyte conducts electricity to a large extent, it is a strong electrolyte and if it
conducts to a small extent it is a weak electrolyte.
23. Arrange the following metals in the order in which they displace each other from the solution of their salts.
The following is the order in which the given metals displace each other from the solution of their salts.
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Answer Key
Each question carries 2 marks : 2019-2020
24. Using the standard electrode potentials given in Table 3.1,(NCERT) predict if the reaction between the
following is feasible:
Since for the overall reaction is positive, the reaction between Fe 3+(aq) and I−(aq) is feasible.
Since for the overall reaction is positive, the reaction between Ag + (aq) and Cu(s) is feasible.
25. In the button cells widely used in watches and other devices the following reaction takes place:
=0.80-(-0.76) =1.56V
We know that,
= −2 × 96500 × 1.56
= −301080 J/mol
= −301.080 kJ/mol
26. The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 Scm−1. Calculate its molar conductivity.
Given,
κ = 0.0248 S cm−1
c = 0.20 M
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Answer Key
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Molar conductivity,
= 124 Scm2mol−1
27. The resistance of a conductivity cell containing 0.001M KCl solution at 298 K is 1500 Ω. What is the cell
constant if conductivity of 0.001M KCl solution at 298 K is 0.146 × 10 −3 S cm−1.
Resistance, R = 1500 Ω
Cell constant = κ × R
28. Write the cell reaction which occurs in lead storage battery (i) when the battery is in use and (ii) when the
battery is charging.
During discharge
At Cathode :- PbO2 (S) + SO4-2 (aq) + 4H+ + 2e- PbSO4 +2H2O (Reduction)
During recharge
At anode :- PbSO4 + 2H2O PbO2 (S) + SO4-2 (aq) + 4H+ + 2e- (Oxidation)
On passing electricity Na+(aq) & H+(aq) move toward the cathode. While CI- (aq) & OH- (aq) ions toward the
anode.
At Cathode
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Both Na+(aq) & H+(aq) are present near the cathode. Since the discharge potential of H + ions is lower than
Na+ ions. Therefore H+ ions.
H+ + e- H.
H. + H. H2(g)
Thus H2 gas is evolved at the cathode while Na+ ions remain in the solution.
At Anode :-
Both CI- & OH- ions are present near the anode. Since the discharge potential of CI - ions is lower than that
OH- ions. Therefore CI- ions are discharge in presence of OH- ions.
=1F
(i)On the basis of E0 values, O2 gas should be liberated at anode but it is Cl2 gas which is liberated in the
electrolysis of aqueous NaCl.
(i)Due to overpotential / Overvoltage of O2 required for O2 which makes the process difficult to occur.
(ii)Conductivity depends on number on ions per volume. The number of ions per unit volume decreases.
Therefore conductivity decreases.
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Answer Key
Each question carries 3marks : 2019-2020
32. How much charge is required for the following reductions:
(i)
Required charge = 3 F
= 3 × 96487 C
= 289461 C
(ii)
Required charge = 2 F
= 2 × 96487 C
= 192974 C
(iii)
i.e.,
Required charge = 5 F
= 5 × 96487 C
= 482435 C
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Answer Key
= 2 × 96487 C 2019-2020
= 192974 C
= 96487 C
Formulate the galvanic cell for their combination. What will be the standard cell potential for it? Calculate ∆ rG0
for the reaction
At Cathode :-
Cu+ + e- Cu
At Anode
Cu+ Cu+2 + e-
∆G= -nFEo
35. At 291K, molar conductivies at infinite dilution of NH 4Cl, NaOH and NaCl are 129.8, 217.4, 108.9 ohm-1 cm2
mol-1 respectively. If molar conductivity of 1M of NH 4OH is 9.33 ohm-1 cm2 mol-1.what is the degree of
dissociation of NH4OH solution? Ans. 3.9%
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Answer Key
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By Kohlrausch’s law :-
Eq I + eq II -- eq III
Λom NH4+ + Λom CI- + Λom Na+ + Λom OH- - Λom Na+ - Λom Cl-
36. The conductivity of sodium chloride at 298 K has been determined at different concentrations and the results
are given below:
Calculate for all concentrations and draw a plot between and c½. Find the value of .
Answer :
Given,
Given,
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Given,
Given,
Given,
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0.031 0.141 0.223 0.316
0.1
6 4 6 2
118. 106.7
123.7 115.8 111.1
5 4
Since the line interrupts at 124.0 S cm2 mol−1, = 124.0 S cm2 mol−1.
37.
Conductivity of 0.00241 M acetic acid is 7.896 × 10−5 S cm−1. Calculate its molar conductivity and if for
acetic acid is 390.5 S cm2 mol−1, what is its dissociation constant?
Now,
= 0.084
Dissociation constant,
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Answer Key
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38. A solution of Ni(NO3)2 is electrolyzed between platinum electrodes using a current of 5 amperes for 20
minutes. What mass of Ni is deposited at the cathode?
Given,
Current = 5A
Time = 20 × 60 = 1200 s
= 5 × 1200
= 6000 C
= 1.825 g
39. Three electrolytic cells A,B,C containing solutions of ZnSO 4, AgNO3 and CuSO4, respectively are connected in
series. A steady current of 1.5 amperes was passed through them until 1.45 g of silver deposited at the cathode
of cell B. How long did the current flow? What mass of copper and zinc were deposited?
= 1295.43 C
Given,
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Answer Key
Current = 1.5 A 2019-2020
Time
= 863.6 s
= 864 s
= 14.40 min
Again,
= 0.426 g of Cu
= 0.439 g of Zn
40. Zinc rod is dipped in 0.1M solution of ZnSO4. The salt is 95% dissociated at this dilution at 298K. Calculate
the electrode potential. Ans. -0.79 V
100
n Zn
E = Eo + 0.0591 log[0.095]
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Answer Key
2 2019-2020
= -0.76 - 0.030
= - 0.79V
41. Calculate the cell emf at 25o C for the following cell:
Calculate the maximum work that can be accomplished by the operation of this cell.
Eo Cell = ER - EL
n [Mg] [Sn2+]
2 10-1
= 2.206 + 0.059
ΔGo = - nF E cell
42. One half-cell in a voltaic cell is constructed from a silver wire dipped in silver nitrate solution of known
concentration. Its other half –cell consists of a zinc electrode dipped in 1.0 M solution of Zn(NO 3)2. A voltage
of 1.48 V is measured for this cell. Use this information to calculate the concentration of silver nitrate solution
used .
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Answer Key
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Eo (Zn2+ / Zn) < Eo (Ag+ / Ag) and so reduction takes place at silver electrodes
- 0.76 + 0.80 v
= -0.80 V – (-0.76 V)
= 1.56 V
n [Zn] [Ag+]2
2 [Ag+]2
= 4.429 x 10-2 M
43. (a) How many moles of mercury will be produced by electrolyzing 1.0 M Hg(NO 3)2 solution with a current of
2.00 A for 3 hours? [molar mass of Hg = 200.6g mol-1] Ans. 0.1119
mol
Hg2+ + 2e- Hg
Q = I x t = 2 x3x60 x 60 = 21600 C
2x96500
44. A voltaic cell is set up at 25oC with the following half cells Al3+ (0.001M) and Ni2+ (0.50 M). Write an equation
for the reaction that occurs when the cell generates an electric current and determine the cell potential. Given :
Eo Ni2+/Ni = -0.20 V , Eo Al3+/Al = -1.66V
Al Al3+ + 3e- x 2
Ni2+ + 2e- Ni x 3
2Al + 3 Ni 2+ 2 Al +3 Ni
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Answer Key
Eo Cell = -0.2 + 1.66 = 1.46K 2019-2020
n [Ni2+]3
6 (.5)3
= 1.46 + 0.049
= 1.509 V
n [Cu2+]
2 [0.1]
= 0.46 +0.059
= 0.519V
46. Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.For hydrogen
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Answer Key
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electrode, , it is given that pH = 10
∴[H+] = 10−10 M
= −0.591 V
Section C
48. Solutions of two electrolytes ‘A’ and ‘B’ are diluted. The m Λ of ‘B’ increases 1.5 times while that of A
increases 25 times. Which of the two is a strong electrolyte? Justify your answer.
Electrolyte ‘B’ is strong as on dilution the number of ions remains the same, only interionic attraction decreases
therefore increase in ∧m is small.
49. Cu does not dissolve in HCl but dissolves in nitric acid. Explain why?
Nitric acid is a good oxidizing agent whereas HCl is reducing in nature.Cu dissolves in nitric acid to form
copper nitrate.
50. In each of the following pairs, which will allow greater conduction of electricity and why?
(a) Silver wire at 20 0 C, Same silver wire at 50 0C (b) NaCl solution at 20 0C, Same NaCl solution at 50 0C
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(b) NH4OH solution at 20 0C, Same NH4OH solution at 50 0C (d) 01.M acetic acid solution, 1M acetic acid
solution
(a) Silver wire at 20 0C because with increase in temperature, metallic conduction decreases due to vibration of
kernels.
b) NaCl solution at 50 0C because in case of a strong electrolyte with increase in temperature, the ionic
mobilities increase
c)NH4OH at 50 0C because in case of a weak electrolyte, dissociation increases with increase in temperature
(d) 0.1 M acetic acid because with dilution, dissociation/ ionization increases
Solution B will have greater molar conductivity becauseΛm=ҡ x V. With dilution, ҡ decreases but V increases
much more so that product increases.
52. A 0.1 M aqueous of Na2SO4 is diluted by adding water. What will happen to the values of its conductance (G),
conductivity (ҡ), molar conductivity (Λm) and equivalent conductivity (Λeq) ?
Ҡ decreases whereas G, Λm, Λeq increase with dilution.(Give the formulas respectively.)
53. Out of HCl and NaCl, which do you expect will have greater value for Λ 0m and why?
HCl because H+ ions are smaller than Na+ ions and hence H+ ions have greater ionic mobility than Na+ ions
54. How will the pH of brine (aq. NaCl solution) be affected when it is electrolyzed ?
When aqueous NaCl solution is electrolyzed, H2 is liberated at cathode, Cl2 at anode and NaOH is formed in
the solution. Hence pH of the solution will rise.
55. Solutions of two electrolytes’A’ and ‘B’ are diluted. The Λm of ‘B’ increase 1.5 times while that of ‘A’
increases 25 times. Which of the two is a strong electrolyte? Justify your answer.
“B” is a strong electrolyte because on dilution of a strong electrolyte, number of ions remains the same. Only
interionic attraction decreases and therefore increase in Λm is small.
56. What advantage do the fuel cells have over primary and secondary batteries?
Primary batteries contain limited amount of reactants. These cells become dead when the reactants are
consumed. Secondary batteries can be recharged but take a long time for recharging. Fuel cells can be run
continuously so long as the reactants are supplied and the products are removed continuously.
57. Why on dilution the Λm of CH3COOH increase drastically, while that of CH3COONaincreases gradually?
CH3COOH is a weak electrolyte. On dilution, degree of dissociation increases and hence the number of ions
increases and therefore Λm increases drastically. On the other hand, CH3COONa is a strong electrolyte. On
dilution, number of ions remain the same. Only interionicattractions decreaseand hence Λm increases gradually
58. Write the name of the cell which is generally used in hearing aids. Write the reactions taking place at the anode
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Answer Key
and the cathode of this cell 2019-2020
Mercury cell
59. Write the name of the cell which is generally used in inverters. Write the reactions taking place at the anode and
the cathode of this cell
60. Write the name of the cell which is generally used in transistors. Write the reactions taking place at the anode
and the cathode of this cell
Leclanche cell
61. The electrical resistance of a column of 0.05 mol L –1 NaOH solution of diameter 1 cm and length 50 cm is
5.55 × 103 ohm. Calculate its resistivity, conductivity and molar conductivity.
Resistance
62. Tarnished silver contains Ag2S. Can this tarnish be removed by placing tarnished silver ware in an aluminum
pan containing an insert electrolytic solution such as NaCl. The standard electrode potential for the half
reactions :
Ag2S(s) + 2e- 2Ag(s) + S2- is -0.71V and for Al3+ + 3e- Al(s) is -1.66V.
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Answer Key
Ag2S (s) + 2e- 2Ag(s)+S2-Eo = - 0.71V 2019-2020
Since Eo (Ag2+ / Ag) >Eo (Al3+ / Al), reduction will occur at the silver electrode.
63. Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is 100Ω . If the resistance of the same
cell when filled with 0.02 mol L–1 KCl solution is 520 Ω, calculate the conductivity and molar conductivity of
0.02 molL–1 KCl solution. The conductivity of 0.1 mol L–1 KCl solution is 1.29 S/m.
(i) At cathode:
The reaction with a higher value of takes place at the cathode. Therefore, deposition of silver will take
place at the cathode.
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At anode: 2019-2020
The Ag anode is attacked by ions. Therefore, the silver electrode at the anode dissolves in the solution to
form Ag+.
(ii) At cathode:
The reaction with a higher value of takes place at the cathode. Therefore, deposition of silver will take
place at the cathode.
At anode:
Since Pt electrodes are inert, the anode is not attacked by ions. Therefore, OH− or ions can be
−
oxidized at the anode. But OH ions having a lower discharge potential and get preference and decompose to
liberate O2.
(iii) At the cathode, the following reduction reaction occurs to produce H 2 gas.
For dilute sulphuric acid, reaction (i) is preferred to produce O 2 gas. But for concentrated sulphuric acid,
reaction (ii) occurs.
(iv) At cathode:
The reaction with a higher value of takes place at the cathode. Therefore, deposition of copper will take
place at the cathode.
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At anode: 2019-2020
The following oxidation reactions are possible at the anode.
At the anode, the reaction with a lower value of is preferred. But due to the over-potential of oxygen,
Cl− gets oxidized at the anode to produce Cl2 gas.
________________________________________________________
E°ox = -0.340 V
Log K = n E0 x F/ 2.303RT
= 3.98 x 1020
66. Calculate the quantity of electricity (Coulombs) necessary to deposit 100.00 g of copper from a CuSO 4 solution
Cu2+ + 2e¯ Cu
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Answer Key
Therefore, every mole of Cu plated out requires2019-2020
two moles of electrons.
67. Write the cell reaction and calculate the emf of the following cell at 298K:
2 AgCl (s) + H2 (g) (1 atm) → 2Ag (s) + 2H+ (0.1 M) + 2Cl– (0.1 M)
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69. (a) Write the reaction that occurs at anode on electrolysis of conc.H 2SO4using platinum electrodes.
Cell potential in mercury cell remains constant but not in dry cell.
71. 0
How can you determine limiting molar conductivity, ( ˄m ) for strong electrolyte and weak electrolyte?
0 ❑ 0
˄m for strong electrolyte is obtained as intercept from the plot of ˄m verses √c whereas ˄m for
weak electrolyte is obtained from Kohlrausch’s law
0
˄m=ν+ λ 0++ν – λ 0 –
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