ELECTRO CHEMISTRY

1. Which of the following cells is used in hearing aids?

(A) Dry cell (B) Mercury cell (C) Nickel-cadmium cell (D) Fuel cell
2. During electrolysis of aqueous CuCl2
(A) H2 (g) is liberated at cathode (B) Cu is formed at cathode
(C) O2 (g) is liberated at anode (D) Cl2 (g) is liberated at cathode
- - -
At cathode: Cu2+ + 2e Cu, At anode: 2Cl Cl2 + 2e
3. During the electrolysis of aqueous NaCl, the cathodic reaction is:
-
(A) Oxidation of Cl ion (B) Reduction of Na+ ion
(C) Oxidation of H2O (D) Reduction of H2O
The products are NaOH, H2 and Cl2
- -
Na+ + e Na, ER0 = − 2.71V, H2O + e ½ H2 + OH−, ER0 = − 0.83V
Reduction potential of Na+ is less than Hydrogen, So at Cathode Reduction of H2O
Or Reduction of H+ takes place.
- -
At cathode: H+ + e ½ H2, Or H2O + e ½ H2 + OH−
- -
At anode: Cl ½ Cl2 + e
# During the electrolysis of Fused NaCl, the cathodic reaction is:
- -
At cathode: Na+ + e- Na At anode: Cl ½ Cl2 + e
4. The conductivity of 0·2 M solution of KCl is 2·48 x10-2 S cm-1. Calculate its
molar conductivity and degree of dissociation (α) Given: λ0 ( K+) = 73·5 S cm2
mol-1 λ0 (Cl-) = 76·5 S cm2 mol-1

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5. & 9 Calculate emf of the following cell at 25ºC:
Zn (s)/ Zn2+ (0·01M) || Cd2+ (0·1 M) /Cd (s) Given: E0Zn2+/Zn =0.76V,
E0Cd2+/Cd = 0.40V [log 10 = 1]

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6. State Faraday’s second law of electrolysis?
when the same amount of electricity passes through different electrolytes, the masses
of ions deposited at the electrodes are directly proportional to their chemical
equivalents.
EαW
Let W1 and W2 be the masses of deposited substances on the electrodes and their
chemical equivalents are E1 and E2 respectively then according to Faraday’s second
law
𝑊1 𝐸1
=
𝑊2 𝐸2

7. How will the pH of aqueous NaCl solution be affected when it is electrolyzed?

The pH of an aqueous NaCl solution, or brine solution, increases after
electrolysis because sodium hydroxide (NaOH) is formed as a product. NaOH is a
strong base, and bases generally have a higher pH value.
The reactions that occur during the electrolysis of brine solution are:
• Cathode: H2O(l) + e− → ½ H2(g) + OH−(aq)
• Anode: Cl−(aq) → ½ Cl2(g) + e−
• Overall reaction: NaCl(aq) + H2O(l) → NaOH(aq) + ½ H2(g) + ½ Cl2(g)
The final solution contains Na+ and OH−, which combine to form NaOH.
8. (i) Write any two advantages of the fuel cells over primary and secondary
batteries?
The galvanic cells in which the energy of combustion of fuels is directly converted
into electrical energy are called fuel cells. the reactants in fuel such as hydrogen,
methane or methanol etc.
Unlike conventional cells (primary and secondary batteries), the fuel cells do not
have to be discharged when the chemicals are consumed.
Advantages of fuel cells: (i) Fuel cells do not cause pollution (ii) Fuel cells have
infinite life time. (iii) Fuel cells have an efficiency of 60-70%.

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(ii) How many Faradays are required for the oxidation of 1 mole of H2O to O2?

For 1 mole of water oxidation

• H2O → 2H+ + 2e− + ½ O2
• 1 mole H2O → 2e− (2moles of electrons) 2e− → 2F
So, for the oxidation of 1 mole of H2O to ½ O2 2 Faradays required or
2 x 96500C = 1.93 x 105 Coulombs required.

9. Calculate emf of the following cell:

Zn (s) | Zn2+ (0.1 M) || Sn2+ (0·001 M) Sn (s)
(E0Zn2+/Zn = -0.76V) (E0Cd2+ /Cd = - 0.14V)
The cell reaction Zn(s) + Sn+2(aq) → Zn+2(aq) + Sn(s)
E0cell = EC −EA ⇒ (-0.14V) - (-0.76V) = -0.14V + 0.76V = 0.62V
Given concentrations: (Zn2+) = 0.1M and (Sn2+) = 0.001M

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10. State Kohlrausch law of independent migration of ions.
Kohlrausch's law of independent migration of ions states that the limiting molar
conductivity of an electrolyte can be represented as the sum of the conductivity of
the anions and cations. The conductivity of a solution decrease with dilution because
less ions are present for conduction in unit volume.
(i) Write an expression for the molar conductivity of acetic acid at infinite
dilution
According to Kohlrausch's law, the molar conductivity of acetic acid at infinite
dilution (λ0(CH₃COOH)) can be expressed as:
λ0 (CH3COOH) = λ0 (CH3COO−) + λ0(H+)

Where:
λ0(CH₃COOH) is the molar conductivity of acetic acid at infinite dilution.
λ0(CH₃COO−) is the molar conductivity of the acetate ion at infinite dilution.
λ0(H⁺) is the molar conductivity of the hydrogen ion at infinite dilution.

Thus, the final expression for the molar conductivity of acetic acid at infinite
dilution is:
λ0(CH3COOH) = λ0(CH3COO−) + λ0 (H+)
The molar conductivity of acetic acid at infinite dilution is the sum of the molar
conductivities of its ions, the acetate ion and the hydrogen ion.

(ii) Calculate the maximum work and log Kc for the given reaction at 298 K:
Ni (s) + 2Ag+ (aq) → Ni2+ (aq) + 2Ag (s)
Given: E0( Ni2+ / Ni ) = − 0·25 V, E0(Ag+ / Ag ) = + 0·80 V
The maximum work = ∆rG0

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1 F = 96500 C mol -1

11. (i) State Faradays law of electrolysis

Faraday’s first Law of electrolysis
Faraday’s First Law of electrolysis states that “The mass of a substance deposited at
any electrode is directly proportional to the amount of charge passed.”
Mathematically it can be expressed as follows.
W ∝ Q ----(1) [Or m ∝ Q]
• m or W = mass of a substance (in grams) deposited or liberated at an electrode.
• Q = amount of charge (in coulombs) or electricity passed through it
On removing the proportionality in equation (1)
m=ZQ
Where Z is the proportionality constant. Its unit is grams per coulomb (g/C). It is
also called the electrochemical equivalent.
Faraday’s second law of electrolysis
Faraday’s second law of electrolysis states that when the same amount of electricity
passes through different electrolytes, the masses of ions deposited at the electrodes
are directly proportional to their chemical equivalents.
EαW
Let W1 and W2 be the masses of deposited substances on the electrodes and their
chemical equivalents are E1 and E2 respectively then according to Faraday’s second
law
𝑾𝟏 𝑬𝟏
=
𝑾𝟐 𝑬𝟐
How much charge in terms of Faraday, is required for the reduction of 1 mol Cu2+
to Cu.?
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Cu2+ (aq) + 2e− → Cu(s)
For 1mole Cu2+ reduction 2moles of electrons are required.
2 moles of electrons = 2F (∵ 1𝑚𝑜𝑙𝑒 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 = 1𝐹)
Two faradays of charge are required to reduce one mole of Cu2+ to Cu. This is
because two moles of electrons are involved in the reaction.
(ii) Calculate emf of the following cell at 298 K for
Mg (s) | Mg2+ (0.1 M) || Cu2+ (0.01M) | Cu(s), [E0cell = + 2.71 V],
1 F = 96500 C mol-1, log 10 = 1]

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Q) Define electrochemical cell. What happens if external potential applied
becomes greater than E cell of electrochemical cell?

Electrochemical cell is a device used for production of electricity from energy

released during spontaneous chemical reaction. If external potential applied becomes
greater than Eo cell of electrochemical cell, then the reaction gets reversed.
Q) Define fuel cell and write its two advantages.
The galvanic cells in which the energy of combustion of fuels is directly converted
into electrical energy are called fuel cells. the reactants in fuel such as hydrogen,
methane or methanol etc.
Unlike conventional cells, the fuel cells do not have to be discharged when the
chemicals are consumed.
Advantages of fuel cell:
(i) It does not cause pollution
(ii) It has infinite life time.
(iii) It has an efficiency of 60-70%.
Q) Which cell is used as a power source in Apollo space program?
Fuel-cell
Q) which cell is used in automobiles and inverters?
Lead storage cell, is most important secondary cell used in automobiles & inverters
Q) which cell is used in hearing aids and watches?
Mercury cell or Button cell, it consists of zinc-mercury amalgam as anode and a
paste of HgO and carbon as the cathode.
Q) which cell does not have long life?
Dry cell does not have long life
Q) what type of battery is mercury cell why is it more advantageous than dry
cell?
The mercury cell, also called “mercury battery, mercury oxide battery”, is a primary
cell, which is a non-rechargeable, non-reusable electrochemical battery. The
Mercury cell has more advantages than the dry cell because dry cells have the
shortest life span because of the transformation of zinc into zinc chloride.
Kohlrausch's law:
The molar conductance of an electrolyte at infinite dilution is equal to the sum of the
conductance of the anions and cations
Q) State the Kohlrausch law of independent migration of ions. Why does the
conductivity of a solution decrease with dilution?
Kohlrausch's law of independent migration of ions states that the limiting molar
conductivity of an electrolyte can be represented as the sum of the conductivity of
the anions and cations. The conductivity of a solution decrease with dilution because
less ions are present for conduction.
Q) What is Kohlrausch's law? Explain any two applications of Kohlrausch's
law.
The molar conductance of an electrolyte at infinite dilution is equal to the sum of the
conductance of the anions and cations.

λ0m = xλ0+ve+ yλ0−ve

λ+ve and λ−ve are ionic conductance of cation and anion x and y = no. of ions.

(i) Calculation of molar conductance at infinite dilution for weak electrolytes

λ0m(CH3COOH) = λ0CH3COO- + λ0H+

(ii) Determination of degree of dissociation of weak electrolyte. If at any concentration C, the

value of molar conductance is λ m then
c

α = λ m/λ m
c 0

α = degree of dissociation
(iii) Dissociation constant for weak electrolyte.
(iv) Determination of solubility of sparingly soluble salt.
(v) Determination of ionic product of water.
Q) Define limiting molar conductivity. Why conductivity of an electrolyte
solution decreases with the decrease in concentration?

Limiting Molar conductivity is the conductivity of the solution at infinite dilution, i.e., all
the ions have dissociated or the ions are farther apart.
Conductivity of electrolyte decreases with decrease in concentration as number of ions
per unit cm of surface area decreases upon dilution.

Q) Define molar conductivity?

Molar Conductivity is defined as the conductivity of the solution of an electrolyte
divided by the Molar concentration of the electrolyte (or)
The conductive properties of a solution that contains one mole of an electrolyte.
The expression which is given below is used to represent molar conductivity
mathematically.

λm = k/c
Where K is specific conductivity and C is concentration in moles per liter.
Q) Define Secondary batteries:
Batteries which can be recharged by passing electric current through them and hence
can be used over again e.g., lead storage battery.
Faraday’s First Law of Electrolysis
Faraday’s First Law of Electrolysis states that “The mass of a substance
deposited at any electrode is directly proportional to the amount of charge passed.”
Mathematically it can be expressed as follows.
m ∝ Q ----(1)
• m = mass of a substance (in grams) deposited or liberated at an electrode.
• Q = amount of charge (in coulombs) or electricity passed through it
On removing the proportionality in equation (1)

m=ZQ
Where Z is the proportionality constant. Its unit is grams per coulomb (g/C). It is
also called the electrochemical equivalent.
Z is the mass of a substance deposited at electrodes during electrolysis bypassing 1
coulomb of charge
Faraday’s Second Law of Electrolysis: “the mass of a substance deposited at any
electrode on passing a certain amount of charge is directly proportional to its
chemical equivalent weight.”
Or “when the same quantity of electricity is passed through several electrolytes, the
mass of the substances deposited are proportional to their respective chemical
equivalent or equivalent weight”.
Mathematically it can be represented as follows: w ∝ E
Where w = mass of the substance, E = equivalent weight of the substance
It can also be expressed as: w1/w2=E1/E2
The equivalent weight or chemical equivalent of a substance can be defined as the
ratio of its atomic weight and valency.
Equivalent weight=Atomic weight/Valency
Q) Calculate the charge required in terms of Faraday for the following
reductions of 1 mole of ions:
Cu2+ to Cu.
Cu2+ + 2e– → Cu
Quantity of charge required for reduction of 1 mol of Cu2+ = 2F

Quantity of charge required for reduction of 1 mol of Cr2O7 2- = 6F

Q) How much charge is required for the following reductions?

Q) E°cell for the given redox reaction is 2.71 V

Mg(s) Cu2+ (0.01M) → Mg2+ (0.001M) Cu(s) Calculate Ecell for the reaction.
Write the direction of flow of current when an external opposite potential
applied is (a) less than 2.71 V and (b) greater than 2.71 V.