Electrochemistry

Electrochemistry is a branch of chemistry which deals with inter conversion of

chemical energy into electrical energy vice versa.

Electrochemical cell
A electrochemical is device which converts chemical energy into electrical energy.

Electrolytic cell
A electrochemical is device which converts electrical energy into chemical energy.

Single electrode potential - Electrode potential is the potential developed by the

metal with respect to the solution, when the metal is in equilibrium with its own
ions in solution.

Standard electrode potential - Standard Electrode Potential is the potential

developed by a metal with respect to the solution when the metal is in
equilibrium with its own ions in one molar solution at 298K.
If the electrode contains a gas, its pressure shall be one atmosphere (101.3 Kpa).

Denial cell

Voltmeter

(-) (+)
Salt bridge
Zn Anode Cu cathode

ZnSO4 CuSO4

At Anode: Zn Zn2+ +2e- (Oxidation)

2+ -
At Cathode: Cu + 2e Cu (Reduction)

2+ 2+
Overall reaction: Zn + Cu Zn + Cu

Representation of Daniel Cell Zn (s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s)

(C1M) (C2M
EMF of cell can be calculated by using formula,

E° = E° / − E° /
Construction and working of SHE or standard hydrogen electrode
Construction of the electrode:
A rectangular platinum plate coated with platinum black is welded to a platinum
wire and the wire is fused in to a glass tube with the help of mercury.
This tube in sealed into a jacket having a side tube at the top. It acts as the
hydrogen inlet.
Two holes provided at the bottom of the outer jacket, which acts as hydrogen
outlet.
The outer jacket is immersed in a glass vessel containing 1M HCl.

Copper wire
H2 , 1 bar

1 M HCl
Pt plate

Working:
Hydrogen gas is passed from the top inlet. The pressure inside the jacket
increases. Due to this Acid level pushed down and platinum plate exposed to
hydrogen gas. Platinum adsorbs hydrogen. As a result pressure falls and acid
level increases. Now the adsorbed film of hydrogen comes in contract with
hydrogen ions of the solution and equilibrium is established and potential is
developed. The potential developed is taken as zero.
Cell reaction: H+ (aq) + e- ½ H2 (g)
Representation of Hydrogen Electrode: Pt (s)|H2 (g, 1 bar) |H+ (aq,1M)

Measurement of Standard electrode potential of zinc electrode measured by

using standard Hydrogen electrode

E° = E° − E°

E° = 0.0 V − E ° ∵ E ° = 0.0 V

0.76 V = − E °

∴ E° = − 0.76 V
Measurement of Standard electrode potential of Copper electrode measured
by using standard Hydrogen electrode

E° = E° − E°

0.34 V = E ° − 0.0 V ∵ E ° = 0.0 V

∴ E° = 0.34 V

Nernst equation

RT [M]
E( / ) E( / ) − ln
nF [M ]

Where
E = electrode potential
E0 = standard electrode potential.
n = valency of the metal ion
F = one faraday = 96,500C
T = temperature in Kelvin
R = gas constant = 8.314JK-1 mole-1

Concentration of solid M is taken as unity,

RT 1
E( / ) E( / ) − ln
nF [M ]

Converting natural logarithm inn to the base 10,

2.303 RT 1
E( / ) E( / ) − log
nF [M ]

On substituting the values of R, F and T= 298K,

0.059 1
E( / ) E( / ) − log
n [M ]

Nernst equation for EMF of the cell

For anode,
2.303 RT 1
E( / ) = E( / ) − log
2F [Zn ]

For Cathode,
2.303 RT 1
E( / ) = E( / ) − log
2F [Cu ]

Cell potential is given by,

 = E( / ) − E( / )

2.303 RT 1 2.303 RT 1
= E( / ) − log − E( / ) + log
2F [Cu ] 2F [Zn ]

2.303 RT 1 2.303 RT 1
= E( / ) − E( / ) − log + log
2F [Cu ] 2F [Zn ]

2.303 RT [Zn ]
=E − log
2F [Cu ]

At 298K,
0.059 [Zn ]
E =E − log
2 [Cu ]

For Ni-Ag Cell:

Ni (s)|Ni2+ (aq) || Ag+ (aq)|Ag(s)

The cell reaction is

+
Ni(s) + 2 Ag (aq) Ni2+ (aq) + 2 Ag (s)

Nernst equation is,

2.303 RT [Ni ]
E =E − log
2F [Ag ]

For general reaction

aA+bB cC+dD

Nernst equation is,

2.303 RT [C] [D]

E =E − log
nF [A] [B]

Equilibrium Constant from Nernst equation

For Daniel Cell,
 Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s)

Nernst equation is written as,

2.303 RT [Zn ]
E =E − log
2F [Cu ]

At equilibrium,

[Zn ]
E = 0 and = K
[Cu ]

2.303 RT
E = log K
2F

At 298 K,

0.059
E = log K
2

For Daniel cell, E = 1.1 V

1.1 2
log K = = 37.288
0.059

∴ K = 2 x 10 at 298K.

In General,

2.303 RT
E = log K
nF

Gibb’s free energy of cell reaction

Electrical work done is given by,

W = −n F E

Where n = number if electrons transferred.

F = 96,500 coulombs
ECell = EMF of the cell

This work done is at the cost of Gibb’s free energy,

Gibb’s free energy of cell reaction (∆r G) is given by,

∴ ∆ G = −n F E
 .
∴ ∆ G = −2.303 RT log K ∵ E = log K

Conductance of Electrolytic Solutions

Distinguish between Metallic conductors and Electrolytic conductors

Metallic conductors Electrolytic conductors

Conductivity due to free electrons Conductivity due to ions
Conductivity takes place in molten
Conductivity takes in solid state state or aqueous solution.
There is no mass transfer. There is mass transfer.
No chemical change There is chemical change.
Conductance decrease with Conductance decrease with
temperature temperature
Ex: HCl, NaOH, NaCl etc. Ex. sugar, urea benzene etc.

Factors affecting electrolytic conduction

1. Concentration of electrolyte
2. Temperature,
3. Nature of electrolyte
4. Nature of solvent and its viscosity.

Electrolyte
Substance which conduct an electricity in molten state or aqueous solution is
called electrolyte.
Ex : NaCl, KCl

Strong Electrolytes
Substances which undergo complete dissociate into ions, when dissolved in water
are called strong electrolytes.
Examples:
Strong acids: HCl, HNO3, H2SO4, etc.,
Strong bases: NaOH, KOH
Salts: KNO3, CH3COONa, NH4Cl.

Weak Electrolytes
Substances which undergo incomplete dissociate into ions, when dissolved in
water are called weak electrolytes.
Examples:
Weak acids: CH3COOH
Weak bases: NH4OH

Resistance
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.

l
R= ρ
a

Where ρ is called specific resistance or resistivity.

The SI unit of specific resistivity is ohm metre.

The reciprocal of resistance is known as conductance, G R=

The reciprocal of resistivity is known as conductivity.

It is represented by the symbol k .

K= =G

The SI unit of conductivity is Sm-1 or Scm-1

1 Scm-1 = 100 Sm-1 or 1 Sm-1 = 10-2 Scm-1

Conductivity = Conductance × Cell constant

Measurement of Conductivity of electrolyte solution

For measuring the resistance of an ionic solution, there are 2 problems:
a) Firstly, passing direct current changes the composition of the electrolytic
solution.
b) Secondly, a solution cannot be connected to the Wheatstone bridge like a
metallic wire or a solid conductor.

The above problems can be resolved by,

1. Alternate current (A) can be used.
2. Conductivity cell can be used to connect to the Wheatstone bridge.

Conductivity Cell
Conductivity cell consists of two platinum electrodes coated with platinum black .
These electrodes have area of cross section equal to ‘A’ and are separated by
distance ‘l’.

Therefore, solution placed between these electrodes is a column of length l and

area of cross section A.
 Connecting
Wires

Platinized Pt Platinized Pt
electrode electrode

Measurement of conductivity involves following steps

Step 1. Determination of Resistance of solution using Wheatstone bridge

R2 R1

P Detector

R4 R3

AC Source

R R R R
= ∴ =
R R R

Step 2. Measurement of conductivity of the solution

∗
K= =G K= Where G* is called Cell constant

Step 3. Determination of Cell constant

Conductivity = Conductance × Cell constant

∗
∗
K= = RK

Molar conductivity :
It is conductivity to all the ions produced by dissolving 1 mole of an electrolyte in
solution.

The SI unit of conductivity is S m2 mol-1 or S cm2 mol-1

1 S m2 mol-1 = 104 S cm2 mol-1 or 1 S cm2 mol-1 = 10-4 S m2 mol-1

K(S m )
Λ (S m mole ) =
1000(L/m ) x C (mol L )

K(S cm ) 1000(cm / )
Λ (S cm mole ) =
x C (mol L )

Variation of Conductivity and Molar conductivity wit Concentration

Variation of Conductivity
Conductivity decreases with decrease in concentration for both strong and weak
electrolytes. Because number of ions per unit volume decreases.

For Strong electrolytes: Conductivity sharply decreases because number of ions

per unit volume decreases.

For Weak electrolyte: Conductivity gradually decreases. Because decreases in

number of ions per unit volume is compensated by increase in degree of
dissociation.

Variation of Molar Conductivity

Molar Conductivity increases with decrease in concentration for both strong and
weak electrolytes.

For Strong electrolytes:

For Weak electrolyte:

Weak electrolyte
0
Λm

Strong electrolyte
2
Λm ( S cm )

√C
Limiting Molar conductivity: Molar conductivity of a electrolytic solution at
infinite dilution is called limiting molar conductivity.

Kohlrausch’s Law of independent migration of ions:

The limiting molar conductivity of an electrolyte can be represented as the sum of
the limiting molar conductivities of individual cation and anion.

= Υ Λ +Υ Λ

Determination of limiting molar conductivity of acetic acid using limiting

molar concavities of strong electrolytes NaCl, HCl, And CH3COOH

Λ° = Λ° + Λ° − Λ°

Λ° = Λ° + Λ° + Λ° + Λ° − Λ° − Λ°

Application of Kohlrausch’s Law

1. Degree of dissociation of weak electrolyte;

∧
α=
Λ

2. Dissociation constant of weak electrolyte:

∝
=
1−∝

∧
Λ cΛ
= ∧ =
1− Λ (Λ −∧ )
Λ

Faraday's first law of electrolysis

The amount of substance deposited or liberated at any of the electrodes is directly
proportional to the quantity of electricity passed through the electrolyte solution.
w  Q
where Q = I x t where I is current in amperes and t is the time in seconds.

Electrochemical equivalent
Electrochemical equivalent is defined as the amount of substance deposited when
ampere current flows for one second.
Units: Grams per Coulomb.

Faraday’s 2nd law of electrolysis

When the same amount of electricity is passed through different electrolytes, the
masses of the substances discharge at the electrodes are directly proportional to
their equivalent masses.
Quantity of electricity required to liberate one mole of ions = n x F

Where n is the valency of the ion.

Products of electrolysis

Products of electrolysis depend on

1. The nature of material being electrolysed and the type of electrodes being used.
2. If the electrode is inert (e.g., platinum or gold), it does not participate in the
chemical reaction and acts only as source or sink for electrons.
On the other
3. If the electrode is reactive, it participates in the electrode reaction.

Thus, the products of electrolysis may be different for reactive and inert
electrodes.The products of electrolysis depend on the different oxidising
and reducing species present in the electrolytic cell and their standard
electrode potentials

Electrolysis of aqueous sodium chloride

NaCl(S) Na+ (aq) + Cl- (aq)

+ -
H O (l) H (aq) + OH (aq)
2

At Cathode

Na+ (aq) + e- Na (s) E / = −2.71

+
H (aq) + ½ H2 (g) E / = 0.00

At Cathode, Reaction with high Eo is preferred

+ -
H (aq) + e ½ H2 (g) E / = 0.00

-
H O (l) + e ½ H2 (g) + OH- (aq) E = 0.00
2 /

At Anode

Cl - (aq) ½ Cl2 (g) + e- E / = 1.36

+ -
2H2O (l) O (g) + 4 H (aq)+ 4 e E / = 1.23
2

At Anode, Reaction with lower Eo is preferred. Due to over potential of oxygen,

chlorine is liberated.
 Cl - (aq) ½ Cl2 (g) + e- E / = 1.36

Net Reaction;
NaCl(aq) Na+ (aq) + Cl- (aq)

- -
At Anode: H2O (l) + e ½ H2 (g) + OH (aq)

- -
At Cathode: Cl (aq) ½ Cl2 (g) + e

-
Net Reaction: NaCl(aq + H2O (l) Na+ (aq) +½ H2 (g) + OH (aq)

Primary Cell
Dry Cell:
A dry cell is also known as Lechlanche cell.
Anode: Zinc Container.
Cathode: Graphite rod surrounded by carbon powder and paste of manganese
dioxide.
Electrolyte: paste of ammonium chloride and zinc chloride.
Reaction at anode: Zn Zn 2+ + 2 e-
Reaction at cathode: MnO2 + H2O + e- MnO(OH) + OH-

Zn 2+ + MnO(OH) + OH-
Overall cell reaction: Zn +MnO2 + H2O
Potential: 1.5 V.

Mercury cell
Anode: Cylindrical shaped Zinc amalgam.
Cathode: Mercuric oxide with 5- 10% graphite.
Electrolyte: 40% potassium hydroxide saturated with zinc oxide.
Reaction at anode: Zn (Hg) + 2 OH- ZnO ( s ) + H2O + 2 e-
Reaction at cathode: HgO + H2O + 2e- Hg (l) + 2 OH-

Overall cell reaction: Zn (Hg) + HgO (s) ZnO ( s ) + Hg (l)

Potential: 1.35 V.

Lead storage battery.

Anode : Grid filled with spongy lead
Cathode: Grid filled with lead dioxide.
Electrolyte: 38% Sulphuric acid.
 Reaction at anode: Pb (s ) + SO4-2 (aq) PbSO4 (s) + 2 e-

Reaction at cathode:
+ -2 -
PbO2 (s) + 4H (aq) + SO4 (aq) + 2e 2 PbSO4 (s) + 2 H2O ( l )
Net cell reaction:
Pb (s) + PbO2 (s) + 2H2SO4 (aq) 2 PbSO4 ( s ) + 2 H2O ( l )

H2-O2 fuel cell

H 2O

Anode Cathode

H2 O2

H2-O2 fuel cell consists of

Anode: Porous graphite electrodes (catalyst platinum or palladium )
Cathode: Porous graphite electrode ( catalyst platinum or silver)
Electrolyte: Aqueous solution of KOH.

Working: Hydrogen is continuously supplied at anode and oxygen is

continuously supplied at cathode.

Reaction at anode: 2 H2 (g) + 4 OH- (aq) 4 H2O(l) + 4 e-

Reaction at cathode: O2 (g) + 2 H2O(l) + 4e- 4 OH- (aq)

Overall cell reaction: 2 H2 (g) + O2 (g) 4 H2O(l)

The net reaction is the combustion of hydrogen. The cell continuously as long as
the reactants are supplied. Fuel does not store energy.

Corrosion
The destruction of surface of a metal by the constituents of environment is called
corrosion.
E.g.: Rusting of ion, formation green coating on copper or bronze articles,
tarnishing of silver.

Mechanism of Corrosion – Electrochemical theory of Corrosion

Anode: Atoms iron
Cathode: other impurity atoms
Electrolyte: Moisture containing dissolved CO2, O2 acts as electrolyte.

Reaction at anode: 2 Fe 2Fe2+ +4 e- (oxidation)

Reaction at cathode: O2 (g) + 4 H+ + 4 e- 2 H2O (Reduction)

Overall cell reaction:

+
2 Fe (s) + O2 (g) + 4 H (aq) 2 Fe2+ (aq)+ 2 H2O (l)

Composition of rust: Fe2O3 .x H2O

Prevention of corrosion
Barrier Protection
1. Surface coating with a thin film of oil and grease painting.
2. electroplating with a thin layer of non-corrosive metal like chromium.

Sacrificial protection
Iron is coated with more reactive metals like tin (tinning) or zinc (galvanizing).
Being more reactive they take part in the electrochemical process and gets
sacrificed.
Cathodic protection.
The metal to be protected is made as cathode by connecting it to a more
electropositive metal like Mg.
 Electrochemistry

Questions carrying one Marks each:

1. Write the mathematical expression for limiting molar conductivity of
sodium chloride [NaCl]. ( March 2017 )
Ans. Λ ( ) = Λ + Λ

2. How many coulombs of electricity are required to oxidise one Al to Al+3

? ( July 2015 )
Ans. 3 x 96500 Coulombs

3. Which gas is liberated at cathode during the electrolysis of aqueous

solution of NaCl? ( March 2016 )
Ans. Hydrogen

4. Write the overall reactions taking place in Daniel Cell. ( March 2016 )
Ans. Overall reaction

2+ 2+
Overall reaction: Zn + Cu Zn + Cu

5. Write the equation for anodic reaction during rusting of iron. ( March
2016)
Ans.

Reaction at anode: 2 Fe 2Fe2+ +4 e- (oxidation)

6. Write Nernst equation for Daniel cell.

Ans.
2.303 R T [Zn ]
E = E − log
nf [Cu ]

7. What happens to molar conductivity when one mole of KCl is dissolved

in one liter is diluted to five times? ( March 2015 )
Ans. Increases.

8. Write the S. I. unit of molar conductivity. ( July 2014 )

Ans. Sm2 mol-1.

9. What is a secondary cell? ( March 2014 )

Ans. The cell that can be recharged.

10. What are fuel cells? (March 2015)

Ans. A fuel cell is a device that converts the chemical energy from a fuel into
electricity through a chemical reaction of positively charged hydrogen ions
with oxygen or another oxidizing agent.

11. Give one use of primary batteries.

Ans. It is used in remote controls.
12. State Faraday’s 1st law of electrolysis.
Ans. The amount of substances deposited or liberated at any of the electrodes
is directly proportional to the quantity of electricity passed through the
electrolyte solution.

13. Write the equation for the reaction occurring at the anode in the lead
acid battery when it is in use.
Ans.
Reaction at anode: Pb (s ) + SO4-2 (aq) PbSO4 (s) + 2 e-
14. State faraday’s 2nd law of electrolysis. ( July 2014 )
Ans. When the same amount of electricity is passed through different
electrolytes, the masses of the substances discharge at the electrodes are
directly proportional to their equivalent masses.

15. Two metals A & B have reduction potential values -0.76 V and +0.34 V
respectively. Which of these will liberate hydrogen gas from dilute
H2SO4?
Ans. Metal A

16. Define limiting molar conductivity?

Ans. The molar conductivity of a solution when concentration approaches
zero is called limiting molar conductivity.

17. What is the quantity of electricity needed to liberate one equivalent of a

substance?
Ans. one Faraday or 96500 Coulombs.

Questions carrying two Marks Questions:

1. Write the cathodic and anodic cell reactions of Hydrogen-Oxygen fuel
cell. ( March 2017 )
Ans.

Reaction at anode: 2 H2 (g) + 4 OH- (aq) 4 H2O(l) + 4 e-

Reaction at cathode: O2 (g) + 2 H2O(l) + 4e- 4 OH- (aq)

2. Mention any two factors on which conductivity of an electrolytic

solution depends. ( March 2017 )
Ans.
1. Dilution,
2. Temperature,
3. Nature of electrolyte
4. Nature of solvent.

3. State Faraday's first law of electrolysis. Write its mathematical form

using usual notations. ( March 2016 )
 Ans. The amount of substance deposited or liberated at any of the electrodes
is directly proportional to the quantity of electricity passed through the
electrolyte solution.
w  Q
where Q = I x t where I is current in amperes and t is the time in seconds.

4. Calculate Λ0m MgCl2. the limiting molar conductivities or Mg+2 and Cl-1
ions are 106.0 Scm2 mol-1 and 76.3 S cm2 mol-1 respectively. ( March
2016 )
Ans.
Λ° = Λ° + 2 Λ°

Λ° = 106.0 + 2 x 76.3

Λ° = 258.6 S cm mol

5. What is secondary cell? Write the equation for the cathodic reaction of
lead storage batter. ( June 2016 )
Ans. A cell that can be recharged again is called secondary cell.
Reaction at cathode:
+ -2 -
PbO2 (s) + 4H (aq) + SO4 (aq) + 2e 2 PbSO4 (s) + 2 H2O ( l )

6. Write the equations of anodic & cathodic reactions occur during rusting
of iron. ( June 2016 )
OR
Write the reaction taken place at anode & cathode during corrosion of
iron.
Ans.
Reaction at anode: 2 Fe 2Fe2+ +4 e- (oxidation)

Reaction at cathode: O2 (g) + 4 H+ + 4 e- 2 H2O (Reduction)

7. State :
i) Kohlrausch’s law
ii) Faraday first law of electrolysis ( June 2015 )
Ans.
i) Kohlrausch’s law- The limiting molar conductivity of an electrolyte can be
represented as the sum of the individual contribution of individual anion and
Cation of an electrolyte.

ii) Faraday first law of electrolysis- The amount of substances deposited or

liberated at any of the electrodes is directly proportional to the quantity of
electricity passed through the electrolyte solution.

8. Calculate emf of the cell in which the following reaction takes place.
Ni (s) +2 ( ) ( . ) → ( )( . ) + 2 Ag(s) Given ; E = 1.05 V. ( June
2015 )
 Ans.
0.059 [Ni ]
E E − log
n [Ag ]

0.059 [0.160]
E 1.05 − log
2 [0.002]

E 0.91 V

9. State Faraday's first law of electrolysis. For the electrode reaction

Zn2+ + 2 e- Zn(S), What quantity of electricity in coulombs is
required to deposit one mole of Zinc? ( March 2015 )
Ans. Faraday first law of electrolysis- The amount of substances deposited
or liberated at any of the electrodes is directly proportional to the quantity of
electricity passed through the electrolyte solution.

2 x 96500 coulombs or 2 Faradays

10. What is Corrosion? Name one method to prevent it. ( July 2014 )
Ans. The destruction of surface of a metal by the constituents of environment
is called corrosion.
Method of prevention – Painting.

11. What is molar conductivity? How is it related to the conductivity of a

solution whose concentration is ‘C’ mol m-3‘? ( March 2014 )
Ans. Molar conductivity is defined as the conductivity due to all the ions
produced by one mole of electrolyte at a given concentration.

Λ =

12. Write the differences between metallic conductors and electrolytic

conductors.
Ans.
Metallic Conductors Electrolytic conductors
Conductivity is due to electrons Conductivity is due to ions
There is no mass transfer There is mass of transfer
There is no chemical change There is Chemical change
Conductivity is decreases with Conductivity is increases with the
the increase in temperature increase in temperature

13. Name the gases liberated at anode & cathode respectively when an
aqueous solution of sodium chloride is electrolyzed.
Ans. At anode : Chlorine At Cathode: Hydrogen

14. Calculate the mass of aluminium deposited at cathode when 193C of

current is passed through molten electrolyte containing dissolved
alumina. Given molar mass of Al = 27g mol-1, IF = 96500 C mol-1.
Ans.
96,500 coulombs deposits 9 gram of Aluminium
 193 coulombs deposits = 0.018 grams

15. How is standard electrode potential of zinc electrode measured by using

standard Hydrogen electrode?
Ans.

E° = E° − E°

E° = 0.0 V − E ° ∵ E ° = 0.0 V

0.76 V = − E °

∴ E° = − 0.76 V

16. Write the reactions occur at a anode and cathode in Lechlanche cell.
Ans.
Reaction at anode: Zn Zn 2+ + 2 e-
Reaction at cathode: MnO2 + H2O + e- MnO(OH) + OH-
17. Write the diagram of Denial cell and half-cell reactions.
Ans.

Voltmeter

(-) (+
Salt bridge )
Zn Anode Cu cathode

ZnSO4 CuSO4

At Anode: Zn Zn2+ +2e- (Oxidation)

2+ -
At Cathode: Cu + 2e Cu (Reduction)

18. What is the effect of dilution on conductivity & molar conductivity of a

solution?
Ans.
Conductivity decreases with the increase in dilution.
Molar conductivity increased with increase in dilution.
19. How is molar conductivity related to the conductivity of solution? Which
one of these has higher molar conductivity : 0.1M KCl or 0.01 M KCl?
Ans.
K
Λ =
1000 x C

0.01 M KCl solution has higher molar conductivity.

20. Write the symbolic representation of standard hydrogen electrode & give
its standard potential value.
Ans. Representation of Hydrogen Electrode: Pt (s) | H2 (g, 1 bar) | H+ (aq,1M)

Questions carrying three Marks Questions:

1. The electrode potential for the Daniel cell given below is 1.1 V.
Zn(s) / Zn2+(aq) II Cu2+(aq) / Cu(s)
Write overall cell reaction and calculate the standard Gibb's energy for
the reaction. [F = 96487 c/mol]. ( March 2017 )
Ans.

At Anode: Zn Zn2+ +2e- (Oxidation)

2+ -
At Cathode: Cu + 2e Cu (Reduction)

2+ 2+
Overall reaction: Zn + Cu Zn + Cu

∆G = −n F E

∆G = −2 x 96487 x 1.1 = 212271.4 J = 212.27 KJ

2. Resistance of a conductivity cell filled with 0.02 M KCl is 520 Ω.

Calculate conductivity and molar conductivity of that solution.
(Cell constant = 1.29 cm-1 ) (March 2016)
Ans.
G∗ 1.29
Κ= = = 0.00248 Scm
R 520

K x 1000 0.00248 1000

Λ = = = 124 Scm
C 0.02

3. Draw a neat labelled diagram of Standard Hydrogen Electrode ( SHE ) and

write its symbolic representation. ( June 2015, March 2016 ) OR
Draw a neat labelled diagram of Standard Hydrogen Electrode ( SHE ) and
write its half cell reaction and E0 value. ( March 2014 )OR
Describe the construction and working of standard Hydrogen Electrode. (
July 2014 )
Ans.
 H2 1 atm

Copper wire

1M HCl Platinum plate

Cell reaction: H+ (aq) + e- ½ H2 (g)

Representation of Hydrogen Electrode: Pt (s) | H2 (g, 1 bar) | H+ (aq,1M)

4. Find the value of ∆G0 at 25°C for the following electrochemical cell,
Cu/Cu2+ (1M) || Ag+ (1M)/Ag [ = +0.34 V & = 0.8 V]. F = 96487 C
(June 2016)
Ans.

E° = E° / − E° /

E° = 0.88 V − 0.34 V

∴ E° = 0.54 V

∆G = −n F E

∆G = −2 x 96487 x 0.54 = 104205.96 J = 104.20 K J

5. Calculate the EMF of the cell for the reaction at

Mg(s) +2 ( ) → ( ) +2 Ag(s) ; / = -2.37 V. / = 0.80 V.
[ Mg 2+ ] = 0.001 M: [ Ag+ ] = 0.0001 M and log 105 = 5 ( March 2015 )

Ans.
E° = E° / − E° /

E° = 0.80 V − ( −2.37 ) V

∴ E° = 3.17 V
2.303 RT [Mg ]
E E − log
nF [Ag ]
 2.303 x8.314 x 298 [0.001]
E 3.17 − log
2 x 96,500 [0.0001]

E 3.17 − 0.14

E 3.03 V

6. Calculate the equilibrium constant of the reaction at 298 K.

Mg(s) +2 ( ) → ( ) +2 Ag(s) ; = +3.16 V.
Ans.
0.059
E = log K
n

0.059
3.16 = log K
2

3.16 2
log K = = 107.11
0.059

K = antilog (107.11) = 1.31 10

7. Calculate EMF of the cell represents below.

Zn/Zn+2 (C = 0.1 M) ⃦ Cu+2 (C = 1M) | Cu at 250 C Given: = 0.34 V and
= - 0.76 V.
Ans.
E° = E° / − E° /

E° = 0.34 V − ( −0.76 ) V

∴ E° = 1.1 V
2.303 RT [Zn ]
E E − log
nF [Cu ]

2.303 x8.314 x 298 [0.1]

E 1.1 − log
2 x 96,500 [ 1]

E 1.1 + 0.0292

E 1.129 V

8. Calculate standard free energy change for the reaction:

Zn(s) + 2 Ag(aq) Zn+2 (aq) +2Ag(s). = 1.56 V Given IF = 96500 C mol-1.
Ans.
∆G = −n F E

∆G = −2 x 96500 x 1.56 = 301080 J = 301.08 KJ

 9. The resistance of solution of a salt occupying a volume between two
platinum electrodes 1.8 cm apart & 5.4 cm2 in area was found to be 32
ohms. Calculate the conductivity of the solution.
Ans.
1 l 1 1.8
Κ= = x = 0.01042 Scm
R a 32 5.4

10. For the standard cell Cu(s) | ( ) || 0 2+

( ) | Ag(s) [ E Cu /Cu = + 0.34 V
and E0Ag+/Ag = + 0.80 V].
(i) Identify the cathode and the anode as the current is drawn from the
cell.
(ii) Write the reaction taking place at the electrodes.
(iii) Calculate the standard cell potential.
Ans.
i. Anode: Zinc cathode: Copper
ii.

At Anode: Zn Zn2+ + 2e- (Oxidation)

2+ -
At Cathode: Cu + 2e Cu(Reduction)

2+
Overall reaction: Zn + Cu Zn2+ + Cu
iii.
E° = E° / − E° /

E° = 0.34 V − ( −0.76 ) V

∴ E° = 1.1 V

11. The molar conductance of sodium chloride, hydrochloride and sodium

acetate at infinite dilution are 126.45, 426.16 and 91.0 ohm-1 cm2 mol-1
at 25°C respectively. Calculate the molar conductance at infinite
dilution.
Ans.
Λ° = Λ° + Λ° − Λ°

Λ° = 91 + 426.16 − 126.45

Λ° = 390.71 S cm mol

12. Write the Nernst equation and calculate the emf of the following cell at
298 K.
Mg(s) | Mg2+ (0.001 M) || Cu2+ (0.0001 M) | Cu(s).
Given /
= -2.36 V and /
= +0.34 V.

Ans.
 E° = E° / − E° /

E° = 0.34 V − ( −2.36 ) V

∴ E° = 2.7 V
2.303 RT [Mg ]
E E − log
nF [Ag ]

2.303 x8.314 x 298 [0.001]

E 2.7 − log
2 x 96,500 [0.0001]

E 2.7 − 0.0295

E 2.67 V

13. Write neat diagram of H2-O2 fuel cell. Mention the reactions taking place
at anode & cathode when it is functioning.
H 2O

Anode Cathode

H2 O2

H2-O2 fuel cell consists of

Anode: Porous graphite electrodes containing catalyst platinum or
palladium.
Cathode: Porous graphite electrode containing catalyst platinum or silver.
Electrolyte: Aqueous solution of KOH.

Reaction at anode: 2 H2 (g) + 4 OH- (aq) 4 H2O(l) + 4 e-

Reaction at cathode: O2 (g) + 2 H2O(l) + 4e- 4 OH- (aq)

Overall cell reaction: 2 H2 (g) + O2 (g) 4 H2O(l)