2.

ELECTROCHEMISTRY
Quick Revision Points
Electrochemistry: the study of production of electricity from energy released during
spontaneous chemical reactions and the use of electrical energy to bring about non-
spontaneous chemical reactions.
Differences Between
Galvanic cell or Voltaic cell or Electrolytic cell
electrochemical cell
A device in which electric current A device in which a nonspontaneous
(electrical energy) is generated from chemical reaction is carried with the help
spontaneous redox chemical reaction of electric current (electrical energy).
(chemical energy)
eg: Daniel cell, dry cell, lead storage eg : electrolysis of molten NaCl,
battery electrolysis of dilute aq.H2SO4 solution
using Pt electrode

.
Electrochemical cell e.g., Daniel cell
The overall cell reaction is:
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
The Daniel cell is represented as :

Zn(s)| Zn2+(aq)(C1) || Cu2+(aq) (C2)| Cu(s)

Left side Salt bridge Right side
Oxidation half reaction Reduction half reaction
Anode Cathode
Negative terminal Positive terminal

Salt Bridge and Its Functions: It consists of a glass

U-tube containing semi-solid paste of either KCl,
KNO3 or NH4Cl (inert electrolytes) in gelatine or agar-
agar jelly. It helps in flow of ions by completing the
circuit and maintains electrical neutrality.

Electrode potential and Cell potential (Ecell) Electromotive

standard electrode potential force(emf)
Electrode potential (Eelectrode) Difference between the Cell potential when no
A potential difference which electrode potential of the current is drawn
develops between the electrode cathode and anode. through the cell
(Metal rod) and the electrolyte (Measured in Volts
(solution containing metal ion). Ecell = Eright – Eleft
standard electrode potential Ecell = Ecathode – Eanode
( E°electrode) standard cell potential
When concentrations of all the E0cell = E0cathode – E0anode
species involved in a half-cell is
unity and temperature is at
298 K, then the electrode
potential is known as standard
electrode potential
Note: It is a common practice to express all the electrode potentials as reduction
potentials.
Reduction potential = - Oxidation potential.

Reversibility of Daniel Cell:

Measurement of electrode potential: SHE (Standard Hydrogen electrode) is used as a

reference electrode to measure the standard electrode potential of other electrodes by
assigning standard electrode potential of SHE is zero. It consists of Pt electrode coated
with Pt black, in acidic solution of 1M H+ ion concentration at 1 bar Pressure and 298 K
temperature.
Example: (i) When SHE is coupled with Zn, Pt(s) | H2(g, 1bar) || Zn2+(aq, 1M) | Zn(s)
EMF of the above cell = 0.76 V so E° Zn+2 / Zn =-0.76V
(ii) When SHE is couples with Cu, Pt(s) | H2(g, 1bar) || Cu2+(aq, 1M) | Cu(s)
EMF of the above cell = 0.34 V so E° Cu+2/ Cu = +0.32V

Nernst equation: It is an equation which gives the relationship between electrode

potential and the concentration of ions in electrolytic solution. For an electrode reaction
(reduction reaction),
Mn+ (aq) + ne– → M(s), Nernst equation can be written as:
𝑜 𝑅𝑇 [M]
𝐸M𝑛+ /M = 𝐸M 𝑛+ /M − ln
𝑛𝐹 [M 𝑛+ ]
2.303𝑅𝑇 1
𝐸M𝑛+ /M = 𝐸 𝑜 𝑛+ − log
M /M 𝑛𝐹 [M 𝑛+ ]
𝑜
where, 𝐸M𝑛+ /M = Electrode potential, 𝐸M 𝑛+ /M = Standard electrode potential R = 8.314JK /mol,

T = Temperature in kelvin, n = No. of electrons gained, F = Faraday constant (96500 C /mol)

Substituting the value of R and F we get

𝑜 0.0591 1
𝐸M𝑛+/M = 𝐸M 𝑛+ /M − log at 298 K
𝑛 [M 𝑛+ ]

Thus, the electrode potential increases with increase in concentration of ions.

For electrochemical cell , Nernst equation can be given as:

∘ 0.0591 [Product]
at 298 K, 𝐸cell = 𝐸cell − log
𝑛 [ Reactant]
For example, (i) Nernst equation for Daniel cell (Zn – Cu cell) can be written as:

o 0.059 [Zn2+ ]
𝐸(cell) = 𝐸(cell) − log
2 [Cu2+ ]
(ii) Nernst equation for Ni – Ag cell
Ni(s)|Ni2+ (aq) ∥ Ag + (aq)|Ag(s)
The cell reaction is Ni(s) + 2Ag + (aq) → Ni2+ (aq) + 2Ag(s)
The Nernst equation can be written as
o 0.059 [Ni2+ ]
𝐸(cell) = 𝐸(cell) − log
2 [Ag + ]2
Equilibrium Constant from Nernst Equation:
[Zn2+ ]
At equilibrium, Ecell = 0, then [Cu2+ ]
= 𝐾𝑐
∘ 0.0591 ∘ 𝑛
In general, 𝐸cell = log 𝐾𝑐 or, log 𝐾𝑐 = 0.0591 𝐸cell
𝑛

Electrochemical cell and Gibbs Free Energy:

The work done by a reversible galvanic cell is equal to decrease in its free energy.
Mathematically, Δr 𝐺 = −𝑛𝐹𝐸cell
If concentration of all the reacting species is unity, then,
∘ ∘
𝐸cell = 𝐸cell and we get, Δ𝑟 𝐺 𝑜 = −𝑛𝐹𝐸cell
From Δ𝑟 𝐺 𝑜 , we can calculate the equilibrium constant of a reaction,

Δ𝑟 𝐺 𝑜 = −𝑅𝑇ln 𝐾𝑐 or Δ𝑟 𝐺 𝑜 = −2.303𝑅𝑇log 𝐾𝑐

Maximum work = Δ𝑟 𝐺 𝑜

Electrochemical Series: The arrangement of various standard half-cells/electrodes in

the order of their decreasing standard reduction potential values is known as
electrochemical series.

Metallic and Electrolytic Conductance

S. Metallic Conductance Electrolytic Conductance
No.

Movement of electrons is responsible for Movement of ions is

(i)
conduction. responsible for conduction.

Matter moves in the form of

(ii) Does not involve transfer of matter.
ions.
Increases with increase in
Decreases with increase in temperature
temperature due to decrease in
(iii) as kernels start vibrating which produce
interionic attraction or increase
hindrance in the flow of electrons.
in movement of ions
Electrolytic or ionic
Metallic conductance depends upon - conductance depends upon -
Nature and structure of the metal, Nature of electrolyte or
iii)
Number of valence electrons per atom interionic attractions, Solvation
and Temperature of ions, Nature of solvent and
its viscosity, and Temperature
Conductance of Electrolytic solutions:
Resistance (R) - Obstruction to the flow of current, R = ρ l/A, Its SI unit is ohm.

Resistivity (ρ) - electrical resistance of a conductor of unit cross-sectional area and unit
length.
ρ = R A /l, Its SI unit is ohm metre.

Property Formula Units Effect of dilution

Increases as larger
1 𝐴 𝜅𝐴 number of ions are
Ohm−1 (Ω−1 )/
Conductance (𝐺) = = produced or due to
𝑅 𝜌𝑙 𝑙 Siemens (S)
increase in movement of
ions
Specific
Decreases as number of
conductance (𝜅, 1 𝑙
or 𝐺 𝐴 Sm −1
ions per unit volume of
kappa) or 𝜌
solution decreases.
conductivity

Increases with dilution

Molar conductivity 𝜅 × 𝑉 or
S cm2 mol–1 due to large increase in
(Λ 𝑚 ) 1000
𝜅× 𝑉.
𝑀

Conductivity( 𝜅)=conductance(G) X cell constant (G*)

Coductivity is defined as conductance of unit volume of electrolytic solution.

Molar conductivity is defined as conductance of sufficient volume of the electrolytic

solution that contains one mole of the electrolyte.

Cell Constant is defined as the ratio of the distance between the two electrodes to their
area of cross section. Its SI unit is m-1

Limiting molar conductivity: When concentration approaches zero i.e., at infinite

dilution, the molar conductivity is known as limiting molar conductivity (Λ° m).

Variation Molar Conductivity with Concentration:

For a strong electrolyte it is shown by Debye–Huckel Onsager equation:
Λm = Λ°m – AC1/2, Here, Λ°m = Molar conductivity at infinite dilution (Limiting molar
conductivity)
Λm = Molar conductivity at given concentration, A = Constant which depends upon nature
of solvent and temperature, C = Concentration.

For weak electrolytes: molar conductivity

increases steeply on dilution or decrease in
concentration due to increase in the number
of ions or increase in degree of dissociation.

For a strong electrolyte: molar conductivity

increases slowly on dilution or decrease in
concentration due to increase in the movement of ions. There is only a small increase in
conductance with dilution. (This is because a strong electrolyte is completely dissociated
in solution, so the number of ions remain constant and on dilution, interionic attractions
decrease as ions move far apart.)

Kohlrausch’s Law: It states that the limiting molar conductivity of an electrolyte can be
represented as the sum of the individual contributions of the anion and cation of the
electrolyte.
In general, if an electrolyte on dissociation gives 𝑣+ cations and 𝑣− anions then its limiting
molar conductivity is given by Λ0𝑚 = 𝑣+ 𝜆0+ + 𝑣− 𝜆0−
Here, 𝜆∘+ and 𝜆∘− are the limiting molar conductivities of cations and anions, respectively.

Applications of Kohlrausch’s law:

(a) Calculation of molar conductivities of weak electrolyte at infinite dilution: For example,
molar conductivity of acetic acid (weak acid) at infinite dilution can be obtained from the
knowledge of molar conductivities at infinite dilution of strong electrolytes like
HCl, CH3 COONa and NaCl as illustrated below:
Λ∘m(CH3COOH) = 𝜆∘CH3COO− + 𝜆∘H∗
= [𝜆oCH3COO− + 𝜆oNa+ ] + [𝜆oH+ + 𝜆oCl− ] − [𝜆oNa+ + 𝜆oCl− ]
i.e., Λo𝑚(CH3COOH) = Λ𝑜m(CH3COONa) + Λom(HCl) − Λom(NaCl)
(b) Determination of degree of dissociation of weak electrolytes:
Λ𝑐
Degree of dissociation (𝛼) = Λ𝑚
𝑜
𝑚
(c) Determination of dissociation constant (𝐾) of weak electrolytes:
𝑐𝛼 2
𝐾 =
1−𝛼

Electrolytic cell and electrolysis: Electrolysis is the process of decomposition of an

electrolyte by passing electricity through its aqueous solution or molten state.
Criteria for product formation: At cathode, when there is competition between many
cations or many reduction reactions, then the reduction reaction with higher E0 value is
preferred. Similarly at anode, the oxidation reaction with lower E0 value is preferred.

Products of Electrolysis:
Products Reactions involved
Electrolyte
At At
At cathode At anode
cathode anode

Molten Na Cl2 Na+

(𝑙) + 𝑒
−
1
NaCl metal gas Cl−
(𝑙) → Cl2(𝑔) + 𝑒
−
→ Na(𝑙) 2

H2 O(𝑙) + 𝑒 −
Aqueous Cl2 1 1
H2 gas → H2(𝑔) Cl−
(𝑎𝑞) → Cl2(𝑔) + 𝑒
−
NaCl gas 2 2
−
+ OH(𝑎𝑞)
+
H(𝑎𝑔) + 𝑒− 2H2 O(𝑙)
O2 +
Dil. H2 SO4 H2 gas 1 → O2(𝑔) + 4H(𝑎𝑞)
gas → H2(𝑔)
2 + 4𝑒 −
 +
H(𝑎𝑞) + 𝑒−
Conc. 2SO2−
4(𝑎𝑞)
H2 gas S2 O2−
8 1
H2 SO4 → H2(𝑔) → S2 O2−
8 (𝑎𝑞) + 2𝑒
−
2
AgNO3(aq)-
Ag+(aq) + e-
Ag Ag Ag+ Ag(s) → Ag+(aq) + e-
→ Ag(s)
electrode

AgNO3(aq)-
O2 Ag+(aq) + e- 2H2O(l) → O2(g) +
Pt Ag
gas → Ag(s) 4H+(aq) + 4e-
electrode

CuCl2(aq)- Cu O2 Cu+2(aq) + 2H2O(l) → O2(g) +

Pt gas 2e- → Cu(s) 4H+(aq) + 4e-
electrode

Overvoltage/Over potential: Oxidation of H2O is relatively slow process and thus needs
extra potential. This extra potential needed to oxidise H2O is called overvoltage/over
potential. Due to overvoltage, the oxidation of chloride ion occurs at anode in preference
to H2O.

Faraday’s first law of electrolysis: The amount of chemical reaction which occurs at any
electrode during electrolysis is proportional to the quantity of electricity passed through
the electrolyte. m=ZQ,
m = Z × I × t, where Z = Electrochemical equivalent =M/nF where n= no of electrons or
valency, F=96487, M= molar mass of the metal

Faraday’s second law of electrolysis: Amount of various substances liberated by the

same quantity of electricity passed through the electrolytic solution is proportional to their
chemical equivalent weights. W1/E1 = W2/E2

Battery: Combination of galvanic cells in series and used as a source of electrical energy.
(i)Primary batteries are non-chargeable batteries such as Leclanche cell and Dry cell.
(ii) Secondary batteries are chargeable cells involving reversible reaction. Example, Lead
storage battery and Nickel-cadmium cells.

Dry cell (Leclanche cell): The anode consists of a zinc container and the cathode is a
graphite electrode surrounded by powdered MnO2 and C. The space is filled with paste of
NH4Cl and ZnCl2.
At anode: Zn(s) → Zn2+(aq) + 2e– At cathode: MnO2 (s) + NH4+(aq)+ 2e– →
MnO(OH) + NH3
The net reaction: Zn + NH4+(aq) + MnO2 → Zn2+ + MnO(OH) +NH3

Mercury cell: consists of zinc–mercury amalgam as anode and a paste of HgO and
carbon as the cathode. The electrolyte is a paste of KOH and ZnO. The electrode
reactions are:
Anode: Zn(Hg) + 2OH-→ ZnO(s) + H2O + 2e – Cathode: HgO(s) + H2O + 2e- →
Hg (l) + 2OH–
The cell potential is approximately 1.35 V and remains constant as the ionic
concentration of the solution is not changed during its life

Lead storage battery: Anode - Spongy lead Cathode - Lead packed with Lead dioxide
Electrolyte -Aqueous solution of H2 SO4 (38%)
Discharge reaction of cell:
At anode : Pb(s) +SO42–(aq) → PbSO4 (s) +2e–
At cathode: PbO2 filled in lead grid gets reduced to Pb2+ ions which combines with SO4 2–
ions to form PbSO4 (s). The reaction is PbO2 (s) + 4H+(aq) + SO42–(aq) + 2e– → PbSO4 (s) +
2H2O(l)
Complete cell reaction: Pb(s) + PbO2 (s) + 2H2 SO4 (aq) → 2PbSO4 (s) + 2H2O(l)
Recharge reaction of cell (charging): It changes the direction of electrode reaction.
PbSO4 accumulated at cathode gets reduced to Pb.
Overall Reaction: PbSO4 (s) + 2H2O(l) → Pb(s) + PbO2 (s) + 2H2SO4 (aq)

Nickel–cadmium cell which has longer life than the lead storage cell but is costly. Here,
the overall reaction during discharging: Cd(s) + 2Ni(OH)3 (s)→ CdO(s) + 2Ni(OH)2 (s) +
H2O(l)

Fuel cells: Electrical cells that are designated to convert the energy from the combustion
of fuels such as hydrogen, carbon monoxide or methane directly into electrical energy are
called fuel cells. the cell reactions are:
Anode: 2H2 (g) + 4OH– (aq) → 4H2 O (l) + 4e-, Cathode: O2 (g) + 2H2 O(l) + 4e– → 4OH–
(aq)
Net reaction: 2H2 (g) + O2 (g) →2H2O (l)
Advantages: high efficiency, free from pollution (eco-friendly),continuous source of
energy

Corrosion: The process of slow conversion of metals into their undesirable compounds
(usually oxide) by reaction with moisture and other gases present in the atmosphere.
Rusting of iron:
Oxidation: Fe(s) → Fe+2 (aq) + 2e-, Reduction: O2(g) + 4H+(aq) + 4e-→ 2H2O(l)
Atmospheric oxidation: 2Fe+2(s) + ½ O2 (g) + 2H2O(l) → Fe2O3 + 4H+(aq)
Fe2O3 + xH2O → Fe2O3.xH2O(rust)
Prevention of Corrosion:
(i)Barrier protection: By covering the surface with paint or a thin film of grease or by
some chemicals (eg-bisphenol).
(ii) Sacrificial protection: Sn, Zn (by galvanization), sacrificial anode- Mg, Zn (iii)
Alloying

MULTIPLE CHOICE QUESTIONS (1 MARKS)

Q1. Which metal is used as electrode which do not participate in the reaction but
provides surface for conduction of electrons? (a) Cu (b) Pt (c) Zn (d) Fe
Q2. An electrochemical cell can behave like an electrolytic cell when
(a) Ecell = 0 (b) Ecell > Eext (c) Eext > Ecell
(d) Ecell = Eext
Q3. 4. Which cell will measure standard electrode potential of copper electrode?
(a) Pt(s)| H2 (g, 0.1 bar)| H+ (aq., 1 M) | | Cu2+ (aq., 1M)| Cu(s)
(b) Pt(s)| H2 (g, 1 bar) | H+ (aq., 1 M) | | Cu2+ (aq., 2M)| Cu(s)
(c) Pt(s)| H2 (g, 1 bar) | H+ (aq., 1 M) | | Cu2+ (aq., 1M)| Cu(s)
(d) Pt(s)| H2 (g, 1 bar) | H+ (aq., 0.1 M)| | Cu2+ (aq., 1M)| Cu(s)
Q4. The positive value of the standard electrode potential of Cu2+/Cu indicates that
(a) this redox couple is a stronger reducing agent than the H+ /H2 couple.
(b) this redox couple is a stronger oxidising agent than H+ /H2.
(c) Cu can displace H2 from acid.
(d) Cu can displace H2 from acid
Q5. On increasing temperature,
(a) ionic conductance increases and electronic conductance decreases.
(b) ionic conductance decreases and electronic conductance increases.
(c) both ionic and electronic conductance increase.
(d) both ionic and electronic conductance decrease.
Q6. The electrolyte used in the mercury cell is
(a) paste of NH4Cl and ZnCl2 (b) paste of HgO and carbon
(c) paste of KOH and ZnO (d) paste of PbO and H2SO4
Q7. A device that converts energy of combustion of fuels like hydrogen and methane
directly into electrical energy is known as:
(a) dynamo (b) Ni-Cd cell (c) fuel cell (d)
electrolytic cell
Q8. Which one of the following is always true about the spontaneous cell reaction in a
galvanic cell?
(a) E° cell > 0, ΔG° < 0, Q >KC (b) E° cell < 0, ΔG° < 0, Q <KC
(c) E° cell > 0, ΔG° > 0, Q >KC (d) E° cell > 0, ΔG° < 0, Q <KC
Q9. Charge carried by 1 mole of electrons is
(a) 6.023 × 1023 coulomb (b) 9.65 × 104 coulomb
(c) 1.6 × 10–19 coulomb (d) 6.28 × 1019 coulomb
Q10. To calculate the standard emf of the cell, which of the following options is correct if
E° is reduction potential values?
(a) emf = E°cathode – E°anode (b) emf = E°anode – E°cathode
(c) emf = E°anode + E°cathode (d) None of these

ASSERTION REASON TYPE QUESTIONS(1MARKS)

Given below are two statements labelled as Assertion (A) and Reason (R)
Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
Q1. Assertion (A) : Ecell should have a positive value for the cell to function.
Reason(R) : Ecathode < Eanode
Q2. Assertion (A) : Copper sulphate cannot be stored in zinc vessel.
Reason (R) : Zinc is less reactive than copper.
Q3. Assertion (A) : Current stops flowing when Ecell = 0.
Reason (R) : Equilibrium of the cell reaction is attained.
Q4. Assertion (A) : Conductivity of all electrolytes decreases on dilution.
Reason (R) : On dilution number of ions per unit volume decreases.
Q5. Assertion (A) : Conductivity decreases for weak electrolyte and increases for strong
electrolyte with decrease in concentration.
Reason (R) : On dilution, the number of ions per unit volume that carry the
current decreases.
VERY SHORT ANSWER TYPE QUESTIONS (2 MARKS)
Q1. In the plot of molar conductivity (Λm) vs square root of concentration (C1/2), following
curves are obtained for two electrolytes A and B.

Answer the following:

(i)Predict the nature of electrolytes A and B.
(ii)What happens on extrapolation of Λm to concentration approaching zero for electrolytes
A and B?

Q2. Calculate Δ𝑟 𝐺 ∘ and log 𝐾𝑐 for the following reaction at 298 K :

2Cr (𝑠) + 3Fe2+ (𝑎𝑞) ⟶ 2Cr 3+ (𝑎𝑞) + 3Fe(𝑠)
0
Given: 𝐸cell = 0.30 V

Q3. Three iron sheets have been coated separately with three metals 𝐴, 𝐵 and 𝐶 whose
standard electrode potentials are given below. Identify in which rusting will takes place
faster when coating is damaged.
Metal 𝐴 𝐵 𝐶 Iron
𝐸0 −0.46 V −0.66 V −0.20 V −0.44 V

Q4. Can you store copper sulphate solutions in a zinc pot?

Q5. Suggest a way to determine the Λ0𝑚 value of water.

Q6. Why on dilution the ⋀m of CH3COOH increases drastically while that of CH3COONa
increases gradually?

Q7. (a) What is the role of ZnCl2 in a dry cell

(b) Unlike dry cell, the mercury cell has a constant cell potential throughout its
useful life. why?

Q8. (a) Value of standard electrode potential for the oxidation of Cl– ions is more positive
than that of water, even then in the electrolysis of aqueous sodium chloride, why is Cl–
oxidised at anode instead of water?
(b) How will the pH of brine (aq. NaCl solution) be affected when it is electrolysed?

Q9. (a) Which type of a metal can be used in cathodic protection of iron against rusting?
(b) Write the name of the electrolyte used in fuel cell

Q10. Depict the galvanic cell in which the reaction Zn(s) + 2Ag+ (aq) → Zn2+ (aq) + 2Ag(s)
takes place. Further show: (i) Which of the electrode is negatively charged?
(ii) The carriers of the current in the cell.

SHORT ANSWER TYPE QUESTIONS (3 MARKS)

Q1. (a) Calculate the cell emf and Δ𝐺 ∘ for the cell reaction at 25∘ C for the cell :
Zn(𝑠) |Zn2+ (0.0004M) ∥ Cd2+ (0.2M)|Cd(𝑠) 𝐸 ∘ values at 25∘ C: Zn2+ /Zn = −0.763 V
Cd2+ /Cd = −0.403 V; 𝐹 = 96500Cmol−1 ; 𝑅 = 8.314 J K −1 mol−1 .
(b) If 𝐸 ∘ for copper electrode is 0.34 V, how will you calculate its emf value when the
solution in contact with it is 0.1M in copperions? How does emf for copper electrode
change when concentration of Cu2+ ions in the solution is decreased?
Q2. The molar conductivity of sodium acetate, sodium chloride and hydrochloric acid
are 83,127 and 426 mho cm2 mol−1 at 250∘ C respectively. Calculate the molar conductivity
of acetic acid solution.

Q3. A strip of nickel metal is placed in a 1 molar solution of Ni(NO3 )2 and a strip of silver
metal is placed in a 1 molar solution of AgNO3 . An electrochemical cell is created when
the two solutions are connected by a salt bridge and the two strips are connected by
wires to a voltmeter.
(i) Write the balanced equation for the overall reaction occurring in the cell and calculate
the cell potential.
(ii) Calculate the cell potential, 𝐸, at 25∘ C for the cell if the initial concentration of
Ni(NO3 )2 is 0.100 molar and the initial concentration of AgNO3 is 1.00 molar.
0 0 −1
[𝐸 2+ = −0.25 V; 𝐸Ag+/Ag = 0.80 V, log 10 = −1]
Ni /Ni

Q4. The electrochemical cell given alongside converts the chemical energy released
during the redox reaction to electrical energy: Zn(𝑠) + Cu2+ (𝑎𝑞) ⟶ Zn2+ (𝑎𝑞) + Cu(𝑠)
It gives an electrical potential of 1.1 V when concentration Zn2+ and Cu2+ ions is unity.
State the direction of flow of current and also specify whether zinc and copper are
deposited or dissolved at their respective electrodes when:
(i) an external opposite potential of less than 1.1 V is applied.
(ii) an external potential of 1.1 V is applied.
(iii) an external potential of greater than 1.1 V is applied.

Q5. Explain redox potential. Reduction potentials of some ions are given below. Arrange
them in decreasing order of oxidizing power.
Ion ClO−
4 IO−
4 BrO−
4

Reduction potential E ⊖ /V E 0 = 1.19 V E 0 = 1.65 V E 0 = 1.74 V

LONG ANSWER TYPE QUESTIONS (5 MARKS)

Q1. (i) State two advantages of H2—O2 fuel cell over ordinary cell.
(ii) Silver is electrodeposited on a metallic vessel of total surface area 500 cm2 by
passing a current of 0.5 amp for two hours. Calculate the thickness of silver deposited.
[Given: Density of silver = 10.5 g cm–3, Atomic mass of silver = 108 amu, F = 96,500 C
mol–1]

Q2. (i) Define limiting molar conductivity and fuel cell.

(ii) Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is 100 ohm. If the
resistance of the same cell when filled with 0.02 mol L–1 KCl solution is 520 ohm,
calculate the conductivity and molar conductivity of 0.02 mol L–1 KCl solution. The
conductivity of 0.1 molL–1 KCl solution is 1.29 × 10–2 ohm–1 cm–1.
CASE BASED QUESTIONS
Read the passage carefully and answer the questions.
Redox reactions play an important role in chemistry. Whenever a redox reaction takes
place directly in a single beaker, chemical energy in the form of heat is produced. By
suitable means, it is possible to bring about the redox reactions indirectly so as to convert
the chemical energy into electrical energy. A device used to convert the chemical energy
produced in a redox reaction into electrical energy is called an electrochemical cell. If a
redox reaction is allowed to take place in such a way that oxidation half reaction takes
place in one beaker and the reduction half reaction in another beaker, the electrons given
out by the former will be taken by the latter and the current will ow. The two portions of
the cell are called half cells. The values of standard redox potential ( 𝐸 0 ) of two half cell
reactions decides in which way the reaction will proceed. A redox reaction is feasible when
the substance having higher reduction potential gets reduced and the one having lower
reduction potential gets oxidised. For example, In Daniel cell, zinc goes into solution and
copper gets deposited.
1.Formulate the galvanic cell for: Zn(𝑠) + 2Ag + (𝑎𝑞) ⟶ Zn2+ (𝑎𝑞) + 2Ag(𝑠)

2. Is it safe to stir AgNO3 solution with a copper spoon? Why or why not?
0 0
Given: 𝐸Ag+/Ag = 0.80 volt and 𝐸Cu2 +/Cu = 0.34 volt
3. Two half-cell reactions of an electrochemical cell are given below:
MnO− + − 2+ 0
4 (𝑎𝑞) + 8H (𝑎𝑞) + 5𝑒 ⟶ Mn (𝑎𝑞) + 4H2 O(𝑙), 𝐸 = +1.51 V
Sn2+ (𝑎𝑞) ⟶ Sn4+ (𝑎𝑞) + 2𝑒 − , 𝐸 0 = +0.15 V
Construct the redox reaction from the two half-cell reactions and predict if this reaction
favours formation of reactants or products shown in the equation.

OR

(i) State the factors affecting cell potential of: Mg (𝑠)|Mg 2+ (𝑎𝑞) ∥ Ag + (𝑎𝑞)|Ag(𝑠)
0
(ii) Can 𝐸cell or Δ𝑟 𝐺 0 for cell reaction ever be equal to zero?