NAME OF UNIT – ELECTROCHEMISTRY

Electrochemistry: Redox reactions, EMF of a cell, standard electrode potential, Nernst equation
and its application to chemical cells, Relation between Gibbs energy change and EMF of a cell,
conductance in electrolytic solutions, specific and molar conductivity, variations of conductivity
with concentration, Kohlrausch's Law, electrolysis,Batteries,Corrosion
GIST OF LESSON
 Oxidation and Reduction: Oxidation is defined as a loss of electrons while reduction is
defined as a gain of electrons.
In a redox reaction, both oxidation and reduction reaction takes place simultaneously.
 Direct redox reaction: In a direct redox reaction, both oxidation and reduction reactions
take place in the same vessel. Chemical energy is converted to heat energy in a direct
redox reaction.
 Indirect redox reaction: In indirect redox reactions, oxidation and reduction take place
in different vessels.
In an indirect redox reaction, chemical energy is converted into electrical energy. The
device which converts chemical energy into electrical energy is known as an
electrochemical cell.
 In an electrochemical cell:
o The half-cell in which oxidation takes place is known as oxidation half-cell
o The half-cell in which reduction takes place is known as reduction half-cell.
o Oxidation takes place at anode which is negatively charged and reduction takes
place at cathode which is positively charged.
o Transfer of electrons takes place from anode to cathode while electric current
flows in the opposite direction.
o An electrode is made by dipping the metal plate into the electrolytic solution of its
soluble salt.
o A salt bridge is a U shaped tube containing an inert electrolyte in agar-agar and
gelatin.
 Salt bridge: A salt bridge maintains electrical neutrality and allows the flow of electric
current by completing the electrical circuit.
 Representation of an electrochemical cell:
o Anode is written on the left while the cathode is written on the right.
o Anode represents the oxidation half-cell and is written as: Metal/Metal ion
(Concentration)
o Cathode represents the reduction half-cell and is written as: Metal ion
(Concentration)/Metal
o Salt bridge is indicated by placing double vertical lines between the anode and the
cathode

o Electrode potential is the potential difference that develops between the

electrode and its electrolyte. The separation of charges at the equilibrium state
results in the potential difference between the metal and the solution of its ions. It
is the measure of tendency of an electrode in the half cell to lose or gain electrons.
o Standard electrode potential: When the concentration of all the species involved
in a half cell is unity, then the electrode potential is known as standard electrode
potential. It is denoted as E0.
 According to the present convention, standard reduction potentials are now called
standard electrode potential.
 Types of electrode potential: There are 2 types of electrode potentials namely,
o Oxidation potential
o Reduction potential
 Oxidation potential: It is the tendency of an electrode to lose electrons or get oxidized.
 Reduction potential: It is the tendency of an electrode to gain electrons or get reduced.
Oxidation potential is the reverse of reduction potential.
 The electrode having a higher reduction potential have higher tendency to gain electrons
and so it acts as a cathode whereas the electrode having a lower reduction potential acts
as an anode.
 The standard electrode potential of an electrode cannot be measured in isolation.
 According to convention, the Standard Hydrogen Electrode is taken as a reference
electrode and it is assigned a zero potential at all temperatures.
 Reference electrode: Standard calomel electrode can also be used as a reference electrode
 SHE: Standard hydrogen electrode consists of a platinum wire sealed in a glass tube and
carrying a platinum foil at one end. The electrode is placed in a beaker containing an
aqueous solution of an acid having 1 Molar concentration of hydrogen ions. Hydrogen
gas at 1 bar pressure is continuously bubbled through the solution at 298 K. The
oxidation or reduction takes place at the Platinum foil. The standard hydrogen electrode
can act as both anode and cathode.
 If the standard hydrogen electrode acts as an anode:

If the standard hydrogen electrode acts as a cathode:

 In the electrochemical series, various elements are arranged as per their standard
reduction potential values.
 A substance with higher reduction potential value means that it has a higher tendency to
get reduced. So, it acts as a good oxidising agent.
 A substance with lower reduction potential value means that it has a higher tendency to
get oxidised. So, it acts as a good reducing agent.
 The electrode with higher reduction potential acts as a cathode while the electrode with a
lower reduction potential acts as an anode.

(Electrochemical series: some important electrodes taken )

 The potential difference between the 2 electrodes of a galvanic cell is called cell potential
and is measured in Volts.
 The cell potential is the difference between the reduction potential of cathode and anode.
E0 cell = E0 cathode – E0anode
 Cell potential is called the electromotive force of the cell (EMF) when no current is
drawn through the cell.
 Nernst studied the variation of electrode potential of an electrode with temperature and
concentration of electrolyte.
 Nernst formulated a relationship between standard electrode potential E 0 and electrode
potential E.

 Electrode potential increases with increase in the concentration of the electrolyte and
decrease in temperature.
 Nernst equation when applied to a cell, it helps in calculating the cell potential.

 At equilibrium, cell potential E0cell becomes zero.

 Relationship between equilibrium constant Kc and standard cell potential E0cell:

 Work done by an electrochemical cell is equal to the decrease in Gibbs energy

 The substances which allow the passage of electricity through them are known as
conductors.
 Every conducting material offers some obstruction to the flow of electricity which is
called resistance. It is denoted by R and is measured in ohm.
 The resistance of any object is directly proportional to its length l and inversely
proportional to its area of cross section A.

Where ρ is called specific resistance or resistivity.

 The SI unit of specific resistivity is ohm metre.
 The inverse of resistance is known as conductance, G
 Unit of conductance is ohm-1 or mho. It is also expressed in Siemens denoted by S.
 The inverse of resistivity is known as conductivity. It is represented by the symbol .
 The SI unit of conductivity is Sm-1. But it is also expressed in Scm-1.
 Conductivity = Conductance × Cell constant
 For measuring the resistance of an ionic solution, there are 2 problems:
o Firstly, passing direct current changes the composition of the solution
o Secondly, a solution cannot be connected to the bridge like a metallic wire or a
solid conductor.
 Conductivity cell: The problem of measuring the resistance of an ionic solution can be
resolved by using a source of alternating current and the second problem is resolved by
using a specially designed vessel called conductivity cell.
 A conductivity cell consists of two Pt electrodes coated with Pt black. They have area of
cross section A and are separated by a distance ‘l’. Resistance of such a column of
solution is given by the equation:

Where is called cell constant and is denoted by the symbol

 Molar conductivity of a solution: It is defined as the conducting power of all the ions
produced by dissolving 1 mole of an electrolyte in solution.
 Molar conductivity
Where = Conductivity and M is the molarity Unit of Molar conductivity is Scm2 mol-1

 Kohlrausch’s Law of independent migration of ions: According to this law, molar

conductivity of an electrolyte, at infinite dilution, can be expressed as the sum of
individual contributions from its individual ions.
 If the limiting molar conductivity of the cations is denoted by and that of the anions
by , then the limiting molar conductivity of electrolyte is:
Molar conductivity,
Where v+ and v- are the number of cations and anions per formula of electrolyte
 Degree of dissociation: It is ratio of molar conductivity at a specific concentration ‘c’ to
the molar conductivity at infinite dilution. It is denoted by.

 Dissociation constant: WhereKa is acid dissociation constant, ‘c’ is

concentration of electrolyte, α is degree of ionization.
 Faraday constant: It is equal to charge on 1 mol of electrons. It is equal to 96487 C /mol
or approximately equal to 96500 C mol-1.
 Faraday’s first law of electrolysis: The amount of substance deposited during
electrolysis is directly proportional to quantity of electricity passed.

 Faraday’s second law of electrolysis: If same charge is passed through different

electrolytes, the mass of substance deposited will be proportional to their equivalent
weights.

 Products of electrolysis: The products of electrolysis depend upon

 The nature of electrolyte being electrolyzed and the nature of electrodes. If electrode is
inert like platinum or gold, they do not take part in chemical reaction i.e. they neither lose
nor gain electrons. If the electrodes are reactive then they will take part in chemical
reaction and products will be different as compared to inert electrodes.
 The electrode potentials of oxidizing and reducing species. Some of the electrochemical
processes although feasible but slow in their rates at lower voltage, these require extra
voltage, i.e. over voltage at which these processes will take place. The products of
electrolysis also differ in molten state and aqueous solution of electrolyte.
 The charge on one mole of electrons is approximately equal to 96500 coulombs. This
quantity of electricity is called Faraday constant (F).

 A battery consists of two or more galvanic cells connected in series. There are two kinds
of batteries:
(a) Primary batteries: In primary batteries, when the reactants have been converted into
products, no more electricity is produced. The cell reaction cannot be reversed and the
battery becomes dead.
Cell reactions:

Mercury cell
 Cell reactions

(b) Secondary batteries: In secondary batteries (or cells), the cell reaction can be
reversed by passing electricity through the battery (charging). It means that the battery
can be used again and again through a large number of discharging and chargingcycles.
 The most common example of secondary battery is the lead storage battery.

Reactions of Lead Storage Battery:

 Electrical cells that are discharged to convert the energy from the combustion of fuels
(hydrogen, carbon monoxide, methane, etc.) directly into the electrical energy are called
fuel cells.

 The corrosion of metals is an electrochemical process. It occurs in presence of water

and oxygen.
 Corrosion of Iron (Rusting)
Rusting of iron which is the most commonly seen example happens when iron comes in
contact with air or water. The reaction could be seen as a typical electrochemical cell
reaction. Consider the diagram given below.
 Protection from corrosion
1. BARRIER COATINGS

Paint acts as a coating to protect the metal surface from the electrochemical charge that
comes from corrosive compounds.

2. HOT-DIP GALVANIZATION

The iron in the steel reacts with the zinc to create a tightly bonded alloy coating which serves as
protection.

3. CATHODIC PROTECTION

To prevent corrosion, the active sites on the metal surface are converted to passive sites by
providing electrons from another source, typically with galvanic anodes attached on or near the
surface. Metals used for anodes include aluminum, magnesium, or zinc.

Pipeline using cathodic protection.

QUESTIONS-ANSWERS

(A.)MULTIPLE CHOICE QUESTIONS: In the following questions,Q.1 to Q.15 four options

are given to each question, only one option is correct.

Q.1) On which of the following magnitude of conductivity does not depends?

(a) Nature of material
(b) Temperature
(c) Pressure
(d) Mass of the material

Q.2)Which of the following statements about galvanic cell is incorrect

(a) anode is positive
(b) oxidation occurs at the electrode with lower reduction
potential
(c) cathode is positive
(d) reduction occurs at cathode

Q.3) What flows in the internal circuit of a galvanic cell?

(a) Ions
(b) Electrons
(c) Electricity
(d) Atoms

Q.4) Faraday’s laws of electrolysis will fail when

(a) temperature is increased
(b) inert electrodes are used
(c) a mixture of electrolytes is used
(d) None of these cases

Q.5) Which of the following statement is not correct about an inert electrode in a cell ?
(a) It does not participate in the cell reaction.
(b) It provides surface either for oxidation or for reduction reaction.
(c) It provides surface for conduction of electrons.
(d) It provides surface for redox reaction.

Q.6) For the galvanic cell

Zn | Zn2+ (0.1M) || Cu2+ (1.0M)|Cu the cell potential increase if:
(a) [Zn2+] is increased
(b) [Cu2+] is increased
(c) [Cu2+] is decreased
(d) surface area of anode is increased

Q.7) At 25°C, the molar conductance at infinite dilution for the strong electrolytes NaOH, NaCl
and BaCl2 are 248 × 10–4,126 × 10–4 and 280 × 10–4 Sm2mol–1 respectively.Λ0m Ba(OH)2 in
S m2 mol–1 is
(a) 52.4 × 10–4
(b) 524 × 10–4
(c) 402 × 10–4
(d) 262 × 10–4

Q.8) Given that the standard reduction potentials for M+/M and N+/N electrodes at 298 K are
0.52 V and 0.25 V respectively. Which of the following is correct in respect of the following
electrochemical cell ?
M/M+| | N+/N
(a) The overall cell reaction is a spontaneous reaction.
(b) The standard EMF of the cell is – 0.27 V.
(c) The standard EMF of the cell is 0.77 V.
(d) The standard EMF of the cell is – 0.77 V.

Q.9) On passing current through two cells, connected in series containing solution of AgNO3
and CuSO4, 0.18 g of Ag is deposited. The amount of the Cu deposited is:
(a) 0.529 g
(b) 10.623 g
(c) 0.0529 g
(d) 1.2708 g

Q.10) The standard emf of a cell, involving one electron change is found to be 0.591 V at 25°C.
The equilibrium constant of the reaction is (F = 96500 C mol–1)
(a) 1.0 × 101
(b) 1.0 × 105
(c) 1.0 × 1010
(d) 1.0 ×1030

Q.11) Which of the following is the use of electrolysis?

(a) Electrorefining
(b) Electroplating
(c) Both (a) & (b)
(d) None of these
Q.12) The ion of least limiting molar conductivity among the following is
(a) SO42-
(b) H+
(c) Ca2+
(d) CH COO-

Q.13) What is the standard cell potential E° for an electrochemical cell in which the following
reaction takes place spontaneously ?
Cl 2(g)+ 2Br- Br2 (g)+ 2Cl-, ∆G =50.6 kJ
(a) 1.2 V
(b) 0.53 V
(c) 0.26 V
(d) –0.53 V

Q.14) Specific conductance of 0.1 M HNO3 is 6.3×10–2 ohm–1 cm–1.The molar conductance of the
solution is
(a) 100 ohm–1 cm2
(b) 515 ohm–1 cm2
(c) 630 ohm–1 cm2
(d) 6300 ohm–1 cm2

Q.15) Electrolysis of fused NaCl will give

(a) Na
(b) NaOH
(c) NaClO
(d) None of these

B.)ASSERTION-REASON TYPE QUESTIONS: In the following questions Q.16 to Q.30,

each of these questions contain two statements, Assertion and Reason. Each of these questions
also has four alternative choices, only one of which is the correct answer. You have to select one
of the codes (a), (b), (c) and (d) given below.
(a) Assertion is correct, reason is correct; reason is a correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a correct explanation for assertion
(c) Assertion is correct, reason is incorrect
(d) Assertion is incorrect, reason is correct.

Q.16) Assertion : Ecell should have a positive value for the cell to function.
Reason : Ecathode < Eanode

Q.17) Assertion : On increasing dilution, the specific conductance keep on increasing.

 Reason : On increasing dilution, degree of ionisation of weak electrolyte increases and
molality of ions also increases.

Q.18) Assertion: In an electrochemical cell anode and cathode are respectively negative and
positive electrodes.
Reason: At anode oxidation takes place and at cathode reduction takes place.

Q.19) Assertion: Ni/Ni2+(1.0M)||Au3+(1.0M)|Au , for this cell emf is 1.75 V

if Eo Au3+|Au = 1.50, EoNi/Ni2+ = – 0.25 .
Reason: Emf of the cell = Eo cathode – Eoanode.

Q.20) Assertion:Salts like KCl, KNO3 i.e., inert electrolytes are used in salt bridge.
Reason: An inert electrolyte can easily be filled in the U-tube.

Q.21) Assertion: Emf and potential difference are the same for cells.
Reason: Both give the difference in electrode potential under any condition.

Q.22) Assertion: Current stops flowing when Ecell = 0.

Reason: Equilibrium of the cell reaction is attained.

Q.23) Assertion : Cu is less reactive than hydrogen.

Reason : Standard reduction potential of Cu is negative.

Q.24) Assertion: Conductivity decreases with dilution.

Reason: The number of ions per unit volume decreases on dilution.

Q.25) Assertion: It is possible to make a cell with a pair of same type of half cells.
Reason: Change in concentration varies the electrode potential.

Q.26) Assertion: When aqueous sodium chloride solution is electrolysed, Oxygen gas is
produced at the anode.
Reason: It is due to the overpotential for oxidation of water to oxygen.

Q.27) Assertion: Reduction of 1 mole of Cu2+ ions require 2 faraday of charge.

Reason: 1 Faraday is equal to the charge of 1 mole of electrons.

Q.28) Assertion: More negative the electrode potential greater is the power to act as oxidising
agent.
Reason: As the electrode potential becomes more negative there is greater tendency to
undergo oxidation.
Q.29) Assertion: Molar conductivity of an electrolyte increases with decrease in concentration.
Reason: The mobility of ions decrease with increase in concentration.

Q.30) Assertion: The electrode potential of standard hydrogen electrode is zero.

Reason: There is no potential difference at the electrode – solution interface in this
case.

(C) CASE BASED/SITUATION BASED QUESTIONS

PASSAGE 1
Read the passage given below and answer the following questions:
The reversible work done by a galvanic cell is equal to decrease in its Gibbs energy and
therefore, if the emf of the cell is E and nF is the amount of charge passed and ∆rG is the Gibbs
energy of the reaction, then ∆r G = – nFEcell .
It may be remembered that E(cell) is an intensive parameter but ∆rG is an extensive
thermodynamic property and the value depends on n.
Thus, if we write the reaction
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
∆r G = – 2FE(cell)
but when we write the reaction
2 Zn(s) +2 Cu2+(aq) → 2Zn2+(aq) + 2Cu(s)
∆rG = – 4FE(cell)
If the concentration of all the reacting species is unity, then
E(cell) = E0cell and we have
∆rG 0 = – nF E0cell
Thus, from the measurement of E0cell , we can obtain an important thermodynamic quantity,
∆rG 0, standard Gibbs energy of the reaction. From the latter we can calculate equilibrium
constant by the equation: ∆rG 0 = –RT ln K.

Q.1) The standard e.m.f. of a galvanic cell involving cell reaction with n = 2 is found to be 0.295
V at 25°C. The equilibrium constant of the reaction would be
(Given F = 96500 C mol–1; R = 8.314JK–1mol–1)
(a) 2.0 X1011
(b) 4.0 X1012
(c) 1.0 X102
(d) 1.0 X1010

Q.2) The standard emf of a cell, involving one electron change is found to be 0.591 V at 25°C.
The equilibrium constant of the reaction is (F = 96500 C mol–1)
(a) 1.0 × 101
(b) 1.0 × 105
(c) 1.0 × 1010
(d) 1.0 ×1030
Q.3) The maximum work that can be obtained from a galvanic cell is ………..
(a) + nFE
(b) – nFE
(c) 2F
(d) 96500

Q.4) For a relation ∆rG 0 = – nF E0cell

E(cell) = E0cell ,in which of the following condition?
(a) Concentration of any one of the reacting species should be unity
(b) Concentration of all the product species should be unity.
(c) Concentration of all the reacting species should be unity.
(d) Concentration of all reacting and product species should be unity.

Q.5) Which of the following statement is correct?

(a) ECell and ΔrG of cell reaction both are extensive properties.
(b) ECell and ΔrG of cell reaction both are intensive properties.
(c) ECell is an intensive property while ΔrG of cell reaction is an extensive property.
(d) ECell is an extensive property while ΔrG of cell reaction is an intensive property.

PASSAGE 2
Read the passage given below and answer the following questions:
In an electrolytic cell external source of voltage is used to bring about a chemical reaction. The
electrochemical processes are of great importance in the laboratory and the chemical industry.
One of the simplest electrolytic cell consists of two copper strips dipping in an aqueous solution
of copper sulphate. If a DC voltage is applied to the two electrodes, copper is dissolved
(oxidised) at anode and deposited (reduced) at cathode. Many metals like Na, Mg, Al, etc. are
produced on large scale by electrochemical reduction of their respective cations where no
suitable chemical reducing agents are available for this purpose.
Michael Faraday was the first scientist who described the quantitative aspects of electrolysis.,
Faraday published his results during 1833-34 in the form of the following well known Faraday’s
two laws of electrolysis:
First Law: The amount of chemical reaction which occurs at any electrode during electrolysis by
a current is proportional to the quantity of electricity passed through the electrolyte (solution or
melt).
Second Law: The amounts of different substances liberated by the same quantity of electricity
passing through the electrolytic solution are proportional to their chemical equivalent weights .

Q.1)Assertion: Sodium ions are discharged in preference to hydrogen ions at a mercury

cathode.
Reason: The nature of the cathode can affect the order of discharge of ions.
Q.2) Assertion: In electrolysis, the quantity of electricity needed for depositing 1 mole of silver
is different from that required for 1 mole of copper.

Reason: The molecular weights of silver and copper are different

Q.3) Assertion: A small amount of acid or alkali is added before electrolysis of water.

Reason: Pure water is weak electrolyte.

Q.4) Assertion: When acidified zinc sulphate solution is electrolysed between zinc electrodes, it
is zinc that is deposited at the cathode and hydrogen evolution does not take place.

Reason: The electrode potential of zinc is more negative than hydrogen as the overvoltage
for the hydrogen as the evolution on zinc is quite large.

Q.5) Assertion: The conductance measurement of an electrolytic solution is made by using two
conductivity cells having different cell constants gives different values of conductance.
Reason: The conductance of the solution obtained will be different but the conductivity of
solution would be the same.

ANSWERS.
(A)MULTIPLE CHOICE QUESTIONS
1.d 2.a 3.a 4.d 5.d 6.b
7.b 8.b 9.c 10.c 11.c 12.d
13.c 14.c 15.a

(B)ASSERTION REASON TYPE QUESTIONS

16.c 17.d 18.a 19.a 20.c 21.d
22.a 23.b 24.b 25.a 26.a 27.a
28.d 29.a 30.c
(C)PASSAGE 1
1.d 2.c 3.b 4.c 5.c
(C)PASSAGE 2
1.a 2.b 3.a 4.a 5.b

(D) VERYSHORT ANSWER QUESTIONS

Q.1)What are the units of molar conductivity?
A.1) Ohm-1cm2mol-1 or S cm2mol-1

Q.2)What is the direction of flow of conventional current in a galvanic cell?

 A.2)From cathode to anode.

Q.3)Can we store copper sulphate in iron vessel?

A.3)No, because iron is more reactive than copper.

Q.4)Out of HCl and NaCl, which will have greater value of Λ0m.
A.4)HCl because ionic mobility of H+ ions is greater than Na+ ions.

Q.5)The Daniel cell becomes dead after some time. Why?

A.5)Because oxidation potential of zinc decreases and that of copper increases.

Q.6)In the electrolysis of aqueous NaCl, Na is preferentially discharged at Hg electrode. Why?

A.6)Because Hydrogen has higher over voltage at Hg electrode.

Q.7)Can absolute value of electrode potential of an electrode be measured?

A.7)No, because oxidation and reduction can not take place alone.Moreover, it has to be
determined with respect to reference electrode.

Q.8)Under what condition is Ecell = 0 ?

A.8)Under equilibrium.

Q.9)In an aqueous solution how does specific conductivity of electrolytes change with addition
of water?
A.9)Conductivity decreases because number of ions per unit volume decreases.

Q.10)Why is alternating current used for measuring resistance of an electrolytic solution?

A.10)To prevent electrolysis of electrolytic solution.

E) SHORT ANSWER TYPE QUESTIONS

1. Q.1) Aqueous copper sulphate solution and aqueous silver nitrate solution are electrolysed by 1
ampere current for 10 minutes in separate electrolytic cells. Will the mass of copper and silver
deposited on the cathode be same or different? Explain your answer.
A.1) The mass of copper and silver deposited at the cathode will be different. The amount of
different substances deposited by the same quantity of electricity passing through the electrolytic
solution are directly proportional to their chemical equivalents.

Q.2) Consider a cell given below Cu|Cu2+|| Cl-|Cl2,Pt. Write the reactions that occur at anode
and cathode.
A.2) Anode : Cu → Cu2+ + 2e–
 Cathode : Cl2 + 2e– → 2Cl–
Cu is anode as it is getting oxidised. Cl2 is cathode as it is getting reduced.

Q.3) Why on dilution the Λm of CH3COOH increases drastically, while that of CH3COONa
increases gradually?
A.3) In the case of CH3COOH, which is a weak electrolyte, the number of ions increase on
dilution due to an increase in degree of dissociation.

CH3COOH + H2O ⇌ CH3COO--(aq.) + H3O+

In the case of strong electrolyte such as CH3COONa, the number of ions remains the same but
the interionic attraction decreases.

Q.4) Two half cell reactions of an electrochemical cell are given below :
MnO–4(aq) + 8H+ (aq) + 5e– → Mn2+ (aq) + 4H2O (I), E° = + 1.51 V
Sn2+ (aq) → 4 Sn4+ (aq) + 2e–, E° = + 0.15 V
Construct the redox equation from the two half cell reactions and predict if this reaction favours
formation of reactants or product shown in the equation.

A.4) The reactions can be represented at anode and at cathode in the following ways :
At anode (oxidation) :
Sn2+ → = Sn4+ (aq) + 2e– ] × 5 E° = + 0.15 V
At cathode (reduction) :
MnO–4(aq) + 8H+ (aq) + 5e– → Mn2+ (aq) + 4H2O (I)] × 2 E° = + 1.51 V
The Net Reaction = 2MnO–4(aq) + 16H+ + 5Sn2+ → 2Mn2+ + 5Sn4+ + 8H2O
Now E°cell = E°cathode – E°anode

∴ Positive value of E°cell favours formation of product.

= 1.51 – 0.15 = + 1.36 V

Q.5) Given that the standard electrode potentials (E°) of metals are :
K+/K = -2.93 V, Ag+/Ag = 0.80 V, Cu2+/Cu = 0.34 V,
Mg2+/Mg = -2.37 V, Cr3+/Cr = -0.74 V, Fe2+/Fe = -0.44 V.
Arrange these metals in increasing order of their reducing power.

A.5) Ag+/Ag < Cu2+/Cu < Fe2+/Fe < Cr3+/Cr < Mg2+/ Mg < K+/K
More negative the value of standard electrode potentials of metals is, more will be the reducing
power.

Q.6) Determine the values of ΔG° for the following reaction :

Ni(s) + 2Ag+ (aq) → Ni2+ (aq) + 2Ag(s), E° = 1.05 V
(1F = 96500 C mol-1)

A.6) According to the formula

ΔG° = -nFE° = – 2 × 96500 ×1.05
or ΔG° = -202650 J mol-1 = -202.65 KJ mol-1
 Now ΔG° ⇒ -202650 J Mol-1
Q.7)The molar conductivity of a 1.5 M solution of an electrolyte is found to be 138.9 S cm2mol-1.
Calculate the conductivity of this solution.

A.7) C = 1.5 M, Λm = 138.9 S cm2 mol-1

∴K = Λm×C/1000=138.9×1.5/1000 = 0.20835 S cm-1

Λm = K×1000/c

Q.8) Following reactions occur at cathode during the electrolysis of aqueous silver chloride
solution :
Ag+(aq) + e– → Ag(s) E° = +0.80 V
H+(aq) + e– → 12H2(g) E° = 0.00 V
On the basis of their standard reduction electrode potential (E°) values, which reaction is
feasible at the cathode and why?

A.8) At the cathode Ag+ (aq) + e– → Ag(s)

reaction is feasible, because Ag+ ion has higher reduction potential i.e. higher E° value.

Q.9) Calculate the time to deposit 1.27 g of copper at cathode when a current of 2A was passed
through the solution of CuSO4.
(Molar mass of Cu = 63.5 g mol-1,1 F = 96500 C mol-1)

A.9) CuSO4 → Cu+ + SO42-

Cu2+ + 2e– → Cu
63.5 gram of copper is deposited = 2 × 96500 C
1.27 gram of Cu is deposited = 2×96500× 1.27/63.5
= I × t (Q = I × t)
t = 2×96500×1.27/63.5×2 = 1930 seconds

Q.10) (a) Define conductivity for the solution of an electrolyte

(b) How much electricity in terms of Faradays is required to produce 20 g of calcium from
molten CaCl2?

A.10)(a)Conductivity of a solution is defined as the conductance of a solution of 1 cm length and

having 1 sq. cm as the area of cross-section. It is represented by K.Its unit is S cm-1

(b) Ca22+ + 2e– → Ca

∴ 20 g of Ca will require electricity = 1F

Thus, 1 mole of Ca i.e. 40 g of Ca requires electricity = 2F

(F) LONG ANSWER TYPE QUESTIONS

Q.1) (i) State Kohlrausch law.

 (ii) Calculate the emf of the following cell at 298 K, Al(s)/Al3+ (0.15M)//Cu2+(0.025M)
/Cu(s)
(Given Eo(Al3+/Al) = –1.66 V, Eo(Cu2+/Cu) = 0.34V, log 0.15 = –0.8239, log 0.025 = –
1.6020)

A.1) (i) Kohlraush law. According to this law the limiting molar conductivity of an electrolyte
can be represented as the sum of the individual contributions of the anion and cation of an
electrolyte.

Q.2) The given figure, represents variation of (Λm) vs c for an electrolyte. Here (Λm) is the

molar conductivity and c is the concentrationof the electrolyte.

(a) Define molar conductivity.

(b) Identify the nature of electrolyte on the basis of the above plot. Justify your answer.
(c) Determine the value of Λ0m for the electrolyte.
(d) Show how to calculate the value of A for the electrolyte using the above graph.

A2.)
(a) Molar conductivity of a solution at a given concentration is the conductance of the
volume V of solution containing one mole of electrolyte kept between two electrodes
with area of cross section A and distance of unit length.
(b) Strong electrolyte, For strong electrolytes, Λm increases slowly with dilution
(c) Λm = Λm° – Ac 1⁄2
Λm° = 150 S cm2 mol–1
(d) A = – slope
= –(149 – 147.8/0.010 – 0.022)
= 100 S cm2 mol–1/(mol/L–1)1⁄2

Q.3)
(a)State the relationship amongst cell constant of a cell, resistance of the solution in the cell and
conductivity of the solution. How is molar conductivity of a solution related to conductivity of its
solution?
(b) A voltaic cell is set up at 25oC with the following half cell;
Al/Al3+ (0.001 M) and Ni/Ni2+ (0.50 M)
Calculate the cell voltage. [EoNi2+/ Ni = –0.25V, E°Al3+/Al = –1.66V]

A.3)
(a)We know that, reciprocal of resistance in the conductance of the cell,
G = 1/R
Conductivity of the cell is given as
K = G × Cell constant
Substituting the value of conductance in the above equation
K = 1/R× Cell constant

Molar conductivity is the product of conductivity and volume of the solution containing
one mole of electrolyte.
Λm = K × V
Therefore, upon dilution, the conductivity of the electrolyte decreases but the volume of
the solution containing one mole of electrolyte increases. This increase in the volume is
more pronounced than the decrease in the conductivity, thus molar conductivity increases.
Therefore, we can conclude that the molar conductivity increases as the conductivity
decreases with increase in volume of the solution.

(b)
Q.4)
(a) The standard electrode potential for Daniell cell is 1.1 V. Calculate the standard Gibbs energy
for the cell reaction. (F = 96,500 C mol-1)
(b) Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S cm–1. Calculate its molar
conductivity. If limiting molar conductivity for acetic acid is 390.5 S cm2 mol–1.

Ans.4)(a) Given : E° = 1.1V, F = 96,500 C mol-5, n = 2

Zn + Cu2 ⇌ Cu + Zn2+
Using ΔG° = -nFE° = -2 × 96500 × 1.1
= 212,300 CV mol-1

(b)

Q.5)

(a) When a bright silver object is placed in the solution of gold chloride, it acquires a golden
tinge but nothing happens when it is placed in a solution of copper chloride. Explain this
behaviourof silver.

[Given: E°Cu2+/Cu = + 0.34 V, E°Ag+/Ag = + 0.80 V, E°Au3+/Au = + 1.40 V]

(b) Calculate the standard cell potential of the galvanic cell in which the following reactions
takes place:
Fe2+ (aq) + Ag+ (aq) Fe3+ (aq) + Ag (s)
Calculate the ∆rG° and equilibrium constant of the reaction also.
(E°Ag+/Ag = 0.80 V; E°Fe3+/Fe2+ = 0.77 V)
Ans.5) (a) The standard electrode potential, E° for silver is 0.80 V and that of gold is 1.5 V,
hence silver can displace gold from its solution. The replaced gold is deposited on silver object
due to
which golden tinge is obtained. On the other hand E° for Cu is 0.34 V which is lower than that
of silver, thus silver cannot replace copper from its solution.

(b) E°cell = E°Cathode – E°Anode

= 0.80 V – (0.77 V)
= 0.03 V
∆rG° = –nF E°Cell

∴ ∆rG° = –2895 J mol–1

= –1 × 96500 C mol–1 × 0.03 V

log KC = E°Cell/0.0591

∴ KC = antilog 0.508
log KC = 0.508

∴ KC = 3.221