UNIT II ELECTROCHEMISTRY

15
 PRIMARY AND SECONDARY
BATTERIES
ELECTRODE POTENTIAL
PRODUCTS OF
BATTERIES ELECTROLYSIS
GALVANIC CELL

ELECTROLYTIC CELL AND

\
ELECTROCHEMICAL CELL
ELECTROCHEMISTRY ELECTROLYSIS

DANIELL CELL
NERNST EQUATION CONDUCTANCE VARIATION OF
OF CONDUCTIVITY AND
ELECTROLYTIC MOLAR CONDUCTIVITY
ELECTRO- SOLUTION WITH CONCENTRATION
FUNCTIONING EQUILIBRIUM
OF DANIELL CONSTANT
CHEMICAL
CELL FROM
NERNST CELL AND MEASUREMENT
EQUATION GIBB’S ENERGY OF THE
CONDUCTIVITY
OF IONIC
SOLUTIONS

Electrochemistry is 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
transformations.
A galvanic cell is an electrochemical cell that converts the chemical energy of a spontaneous redox reaction
into electrical energy. In this device the Gibbs energy of the spontaneous redox reaction is converted into
electrical work which may be used for running a motor or other electrical gadget like heater, fan, geyser,
etc.

16
Daniell cell is the one such cell in which the following redox reaction occurs.

Daniell cell having electrodes of zinc and copper dipping in the solutions of their respective salts.

The reduction half reaction occurs on the copper electrode while the oxidation half reaction occurs on the
zinc electrode. These two portions of the cell are also called half-cells or redox couples. The copper
electrode may be called the reduction half-cell reaction and the zinc electrode, the oxidation half-cell
reaction.

Electrode potential/Standard electrode potential:

A potential difference develops between the electrode and the electrolyte which is called electrode
potential. When the concentrations of all the species involved in a half-cell is unity then the electrode
potential is known as standard electrode potential. According to IUPAC convention, standard reduction
potentials are now called standard electrode potentials. In a
galvanic cell, the half-cell in which oxidation takes place is called anode and it has a negative potential with
respect to the solution. The other half-cell in which reduction takes place is called cathode and it has a
positive potential with respect to the solution. Thus, there exists a potential difference between the two
electrodes and as soon as the switch is in the on position the electrons flow from negative electrode to
positive electrode. The direction of current flow is opposite to that of electron flow.
The potential difference between the two electrodes of a galvanic cell is called the cell potential and is
measured in volts. The cell potential is the difference between the electrode potentials (reduction potentials)
of the cathode and anode. It is called the cell electromotive force (e.m.f.) of the cell when no current is
drawn through the cell.

17
EMF of a cell: The e.m.f. of the cell is positive and is given by the potential of the half-cell on the right-
hand side minus the potential of the half-cell on the left-hand side i.e.,
Ecell = Eright – Eleft
This is illustrated by the following example: Half-cell reactions:
Cathode (reduction): 2Ag+ (aq) + 2e– --->2Ag(s)
Anode (oxidation): Cu(s) --->Cu2+ (aq) + 2e–
Overall reaction: Cu(s) + 2Ag+ (aq) ----> Cu2+ (aq) + 2 Ag(s)
Silver electrode acts as a cathode and copper electrode acts as an anode. The cell can be represented as:
Cu(s)|Cu2+(aq)||Ag+(aq)|Ag(s)
Ecell = Eright – Eleft = E Ag+ /Ag – ECu2+/Cu
In view of this convention, the half reaction for the Daniell cell in Figure can be written as:
Left electrode: Zn(s) → Zn2+ (aq, 1 M) + 2 e–
Right electrode: Cu2+ (aq, 1 M) + 2 e– → Cu(s)
The overall reaction of the cell is the sum of above two reactions and we obtain the equation:
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
e.m.f. of the cell = E0cell = E0R - E0L = 0.34V – (– 0.76) V = 1.10 V

Nernst equation and its application to chemical cells:

For the electrode reaction:
Mn+ (aq) + ne– ---> M(s)
The electrode potential at any concentration measured with respect to standard hydrogen electrode can be
represented by:

but concentration of solid M is taken as unity and we have

R is gas constant (8.314 JK–1 mol–1), F is Faraday constant (96487 C mol–1), T is temperature in kelvin and
[Mn+] is the concentration of the species, Mn+.
In Daniell cell, the electrode potential for any given concentration of Cu2+ and Zn2+ ions,

Ecell = E0cell – (RT/2F) ln {[Zn2+] / [Cu2+]}

E (cell) depends on the concentration of both Cu2+ and Zn2+ ions. It increases with increase in the
concentration of Cu2+ ions and decrease in the concentration of Zn2+ ions.

We know that, lnX = 2.303logX, R is gas constant (8.314 JK–1 mol–1),

F is Faraday constant (96487 C mol–1), T is temperature in kelvin, 298K. Then
18
For a general electrochemical reaction of the type:

Equilibrium Constant from Nernst Equation:

If the circuit in Daniell cell is closed then we note that the reaction
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) takes place and as time passes, the concentration of Zn2+ keeps on
increasing while the concentration of Cu2+ keeps on decreasing.
At the same time voltage of the cell as read on the voltmeter keeps on decreasing. After some time, we shall
note that there is no change in the concentration of Cu2+ and Zn2+ ions and at the same time, voltmeter gives
zero reading. This indicates that equilibrium has been attained. In this situation the Nernst equation may be
written as:
Ecell = 0 = E0cell – (RT/2F) ln{[Zn2+] / [Cu2+]}
E0cell = (RT/2F) ln{[Zn2+] / [Cu2+]}

But at equilibrium,
[Zn2+] / [Cu2+] = Kc
E0cell = (RT/2F) lnKc
E0cell = (0.059/2) logKc

at T = 298K the above equation can be written as

E0cell = (0.059/2) log Kc
(E0cell = 1.10 V)
log Kc = [(1.10V x 2)]/0.059 = 37.288
Kc = 2 × 1037 at 298K.
In general,
E0cell = (2.303RT/nF) ln Kc

This gives a relationship between equilibrium constant of the reaction and standard potential of the cell in
which that reaction takes place.

Electrochemical Cell and Gibbs Energy of the Reaction:

Electrical work done in one second is equal to electrical potential multiplied by total charge passed. If we
want to obtain maximum work from a galvanic cell then charge has to be passed reversibly. 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 ∆rG = – nFEcell
Ecell is an intensive parameter but ∆rG is an extensive thermodynamic property and the value depends on n.
Thus, if we write the reaction
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Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
∆rG = – 2 F Ecell
If the concentration of all the reacting species is unity, then Ecell = E0cell
∆rG0 = – n F E0cell
We can calculate equilibrium constant by the equation:
∆rG0 = –RT ln K.

Conductance of Electrolytic Solutions:

The electrical resistance is represented by the symbol ‘R’ and it is measured in ohm (Ω). The electrical
resistance of any object is directly proportional to its length, l, and inversely proportional to its area of cross
section, A. That is,
R ∝ l /A or R = ρ (l/A)
The constant of proportionality, ρ (rho), is called resistivity (specific resistance). Its SI units are ohm metre
(Ω m) or ohm centimetre (Ω cm).
The resistivity for a substance is its resistance when it is one metre long and its area of cross section is one
m2. It can be seen that:
1 Ω m = 100 Ω cm or 1 Ω cm = 0.01 Ω m
The inverse of resistance, R, are called conductance, G, and we have the relation:
G =1/R = A/ρ l = κ (A/l) [κ = 1/ ρ]
The SI unit of conductance is Siemens, represented by the symbol ‘S’ and is equal to ohm–1 (also known as
mho) or Ω–1.
The inverse of resistivity, called conductivity (specific conductance) is represented by the symbol, κ
(Greek, kappa). The SI units of conductivity are S m–1. Conductivity of a material in S m–1 is its
conductance when it is 1 m long and its area of cross section is 1 m2. It may be noted that 1 S cm–1 = 100 S
m–1.
Electrical conductance through metals is called metallic or electronic conductance and is due to the
movement of electrons. The electronic conductance depends on:
(i) The nature and structure of the metal
(ii) The number of valence electrons per atom
(iii) Temperature (it decreases with increase of temperature).
When electrolytes are dissolved in water its conductivity increases. The conductance of electricity by ions
present in the solutions is called electrolytic or ionic conductance. The conductivity of electrolytic (ionic)
solutions depends on:
(i) The nature of the electrolyte added
(ii) Size of the ions produced and their solvation
(iii) The nature of the solvent and its viscosity
(iv) Concentration of the electrolyte
(v) Temperature (it increases with the increase of temperature)
Conductivity of Ionic Solutions: In the conductivity cell the solution confined between the electrodes is a
column of length l and area of cross section A. The resistance of such a column of solution is given by the
equation:
R = ρ l/A = l/ κ A
The quantity l/A is called cell constant denoted by the symbol, G*. It depends on the distance between the
electrodes and their area of cross-section.
The cell constant, G*, is then given by the equation:
G* = l/A = R κ
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Κ = cell constant/R = G*/R

Molar conductivity: It is defined as the conducting power of all the ions produced by dissolving one mole
of an electrolyte in solution. It is denoted by the symbol Λm (Λ = lambda). It is related to the conductivity of
the solution by the equation:
Molar conductivity = Λm = κ/c
In the above equation, if κ is expressed in S m–1 and the concentration, c in mol m–3 then the units of Λm is
in S m2 mol–1.

Λm (S cm2 mol-1) = [κ (S cm-1) x 1000 (cm3/L)] / Molarity (mol/L)

Variation of Conductivity and Molar Conductivity with Concentration:

Both conductivity and molar conductivity change with the concentration of the electrolyte. Conductivity
always decreases with decrease in concentration both, for weak and strong electrolytes. This can be
explained by the fact that the number of ions per unit volume that carry the current in a solution decrease on
dilution. The conductivity of a solution at any given concentration is the conductance of one unit volume of
solution kept between two platinum electrodes with unit area of cross section and at a distance of unit
length.
This is clear from the equation: G = κ A/l (both A and l is unity in their units in m or cm)
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. Therefore,
Λm = κ A/l
Since l = 1 and A = V (volume containing 1 mole of electrolyte)
Λm = κ V

Molar conductivity increases with decrease in concentration. This is because the total volume, V, of solution
containing one mole of electrolyte also increases. At a given concentration, Λm can be defined as the
conductance of the electrolytic solution kept between the electrodes of a conductivity cell at unit distance
but having area of cross section large enough to accommodate sufficient volume of solution that contains
one mole of the electrolyte. When concentration approaches zero, the molar conductivity is known as
limiting molar conductivity and is represented by the symbol Λm0. The variation in Λm with concentration
is different for strong and weak electrolytes.

Molar conductivity Λm versus c½ for

acetic acid (weak electrolyte)
and potassium chloride (strong electrolyte)
in aqueous solutions.

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Strong Electrolytes
For strong electrolytes, Λm increases slowly with dilution and can be represented by the equation:
Λm = Λm0 – A c ½
If we plot Λm against c1/2, we obtain a straight line with intercept equal Λm0 and slope equal to ‘A’.
The value of the constant ‘A’ for a given solvent and temperature depends on the type of electrolyte i.e., the
charges on the cation and anion produced on the dissociation of the electrolyte in the solution. Thus, NaCl,
CaCl2, MgSO4 are known as 1-1, 2-1 and 2-2 electrolytes respectively. All electrolytes of a particular type
have the same value for ‘A’.

Kohlrausch’s law of independent migration of ions. The law states that limiting molar conductivity of an
electrolyte can be represented as the sum of the individual contributions of the anion and cation of the
electrolyte.
If λ°Na+ and λ°Cl – are limiting molar conductivity of the sodium and chloride ions respectively, then the
limiting molar conductivity for sodium chloride is given by the equation:
Λm0 = λ°Na+ + λ°Cl – ᶛ
In general, if an electrolyte on dissociation gives ᶛ+ cations and ᶛ– anions then its limiting molar conductivity
is given by: Λm0 = ᶛ+λ°+ + ᶛ– λ° –
λ°+ + λ° – are the limiting molar conductivities of the cation and anion respectively.

Weak Electrolytes
Weak electrolytes like acetic acid have lower degree of dissociation at higher concentrations, for such
electrolytes, the change in Λm with dilution is due to increase in the degree of dissociation. At any
concentration c, if is the degree of dissociation, then
= Λm / Λm0

ELECTROLYSIS: It is a process of decomposition of an electrolyte by the passage of electricity through

its aqueous solution or molten (fused) state of electric current.

Quantitative Aspects of Electrolysis

Faraday’s Laws of Electrolysis:
(i) Faraday first law of electrolysis: 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).
w ∝ Q or w = ZQ, Where Z is called electrochemical equivalent. If a current of I amperes is passed for t seconds,
then Q = It so that, w = ZIt

(ii) Faraday first law of electrolysis: The amounts of different substances liberated by the same quantity of
electricity passing through the electrolytic solution are proportional to their chemical equivalent weights
(Atomic Mass of Metal ÷ Number of electrons required to reduce the cation).
For example, when same current is passed through two electrolytic solutions, containing copper sulphate
and silver nitrate connected in series, the weight of copper and silver deposited are:

(Weight of Cu deposited) / (Weight of Cu deposited) = (Eq. wt. of Cu) / (Eq. wt. of Ag)

22
The amount of electricity (or charge) required for oxidation or reduction depends on the stoichiometry of
the electrode reaction. For example, in the reaction:
Ag+ (aq) + e– → Ag(s)
One mole of the electron is required for the reduction of one mole of silver ions.
The charge on one electron is equal to 1.6021× 10–19 C.
Therefore, the charge on one mole of electrons is equal to:
NA × 1.6021 × 10–19 C = 6.02 × 1023 mol–1 × 1.6021 × 10–19 C = 96487 C mol–1
This quantity of electricity is called Faraday and is represented by the symbol F.
For approximate calculations we use 1F ≃ 96500 C mol–1.

Mg2+ + 2e– → Mg
Al3+ + 3e– → Al
For the above electrode reactions, one mole of Mg2+ and Al3+ require 2 mol of electrons (2F) and 3 mol of
electrons (3F) respectively.

Products of Electrolysis:
The products of electrolysis depend on the different oxidising and reducing species present in the
electrolytic cell and their standard electrode potentials. Moreover, some of the electrochemical processes
although feasible, are so slow kinetically that at lower voltages these do not seem to occur. For the
occurrence of such reactions some extra potential (called over potential) is required.
(i)Electrolysis of molten sodium chloride: During the electrolysis of molten NaCl, the products of
electrolysis are sodium metal and Cl2 gas. The reactions may be expressed as:
At cathode: 2Na+ + 2e– → 2Na (reduction)
At anode: 2Cl– →Cl2 + 2e– (oxidation)
The overall reaction: 2NaCl ---> 2Na + Cl2

(ii) Electrolysis of aqueous sodium chloride: During the electrolysis of aqueous sodium chloride solution,
the products are NaOH, Cl2 and H2.
At the cathode: Na+ (aq) + e– →Na (s) E0cell = – 2.71 V
H+ (aq) + e– →½ H2 (g) E0cell = 0.00 V
The reaction with higher value of E0 is preferred and therefore, the reaction at the cathode during
electrolysis is:
H+ (aq) + e– →½ H2 (g)
But H+ (aq) is produced by the dissociation of H2O, i.e., H2O (l) →H+ (aq) + OH– (aq)
Therefore, the net reaction at the cathode: H2O (l) + e– →½H2 (g) + OH– (aq)
At the anode: Cl– (aq) →½ Cl2 (g) + e– E0cell = +1.36 V
2H2O (l ) → O2 (g) + 4H+(aq) + 4e– E0cell = +1.23 V
The reaction at anode with lower value of E0 is preferred and therefore, water should get oxidised in
preference to Cl– (aq). However, on account of over potential of oxygen, the reaction Cl– (aq) →½ Cl2 (g) is
preferred. Thus, the net reactions may be summarized as:
NaCl (aq) H2O Na+ (aq) + Cl– (aq)
At cathode: H2O (l ) + e– →½ H2(g) + OH– (aq)
At anode: Cl– (aq) →½Cl2 (g) + e–
Net reaction: NaCl (aq) + H2O (l) →Na+(aq) + OH–(aq) + ½H2(g) + ½Cl2(g)
NaCl (aq) + H2O (l) →NaOH (aq) + ½H2 (g) + ½Cl2(g)

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Dry Cell:
A dry cell consists of a metal container in which a low
moisture electrolyte paste covers the graphite rod or a
metal electrode. Generally, the metal container will be
zinc whose base acts as a negative electrode (anode) and
a carbon road acts as a positive electrode (cathode).
It is surrounded by manganese dioxide and low moisture
electrolyte like ammonium chloride paste, which will
produce a maximum of 1.5V of voltage, and they are
not reversible.

Mercury cell: It 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 for the cell are given below:

The cell potential is approximately 1.35 V.

It is suitable for low current devices like hearing aids, watches, etc.

A secondary cell (lead storage battery) commonly used in automobiles and invertors. It consists of
a lead anode and a grid of lead packed with lead dioxide (PbO2) as cathode. A 38% solution of
Sulphuric acid is used as an electrolyte.
The cell reactions when the battery is in use are given below:

On charging the battery the reaction is reversed and PbSO4(s) on anode and cathode is converted
into Pb and PbO2, respectively.

Another important secondary cell is the nickel-cadmium cell which has longer life than the lead
storage cell but more expensive to manufacture.
The overall reaction during discharge is:
Cd (s) + 2Ni (OH)3 (s) CdO (s) + 2Ni (OH)2 (s) + H2O (l)

Fuel cells: To convert the energy of combustion of fuels like hydrogen, methane, methanol, etc.
directly into electrical energy are called fuel cells.

24
Fuel cells use the reaction of hydrogen with oxygen to form water. The cell was used for providing
electrical power in the Apollo space Programme. Fuel cells are pollution free.

Fuel cell using H2 and O2 produces electricity.

The electrode reactions are given below:

Corrosion:
In corrosion, a metal is oxidised by loss of electrons to oxygen and formation of oxides. Corrosion of
iron (commonly known as rusting) occurs in presence of water and air. The chemistry of corrosion is
an electrochemical phenomenon.

Corrosion of iron in atmosphere

We can write the reaction

Anode: 2 Fe (s) 2Fe2+ + 4 e – E0 (Fe2+/Fe) = – 0.44 V
–
Cathode: O2 (g) + 4 H (aq) + 4 e →2 H2O (l)
+
E0 (H+/O2/H2O) = 1.23 V
The overall reaction being:
2Fe(s) + O2 (g) + 4H+ (aq) →2Fe2+ (aq) + 2 H2O (l) E0cell =1.67 V
The ferrous ions are oxidised by atmospheric oxygen to ferric ions which come out as rust in the
form of hydrated ferric oxide (Fe2O3. x H2O) and with further production of hydrogen ions.
Prevention of corrosion can be done by covering the surface with paint or by some chemicals (e.g.
bisphenol).

25
ASSIGNMENT:
Q1. The charge required for the reduction of 1 mol of MnO4– to MnO2 is
(a) 1 F
(b) 3 F
(c) 5 F
(d) 6 F
Ans. (b) 3 F

Q2. If limiting molar conductivity of Ca2+ and Cl– are 119.0 and 76.3 S cm2 mol-1, then the value of limiting
molar conductivity of CaCl2 will be
(a) 195.3 S cm2 mol-1
(b) 271.6 S cm2 mol-1
(c) 43.3 S cm2 mol-1
(d) 314.3 S cm2 mol-1.
Ans. (b) 271.6 S cm2 mol-1

Q3. The emf of the cell:

Ni / Ni2+ (1.0 M) // Au3+ (1.0 M) / Au (E° = -0.25 V for Ni2+/Ni; E° = 1.5 V for Au3+/Au) is
(a) 1.25 V
(b) -1.25 V
(c) 1.75 V
(d) 2.0 V
Ans. (c) 1.75 V

Q4. In a dry cell, which of the following is the electrolyte?

(a) Potassium hydroxide
(b) Sulphuric acid
(c) Ammonium chloride
(d) Manganese dioxide
Ans. (c) Ammonium chloride

Q5. Which of the following statements about a lead storage cell (or a lead-acid battery) is false?
(a) It is a primary cell
(b) The cathode is made up of lead (IV) oxide
(c) The anode is made up of lead
(d) The electrolyte used is an aqueous solution of Sulphuric acid
Ans. (a) It is a primary cell
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Q6. Λm0 for NaCl, HCl and CH3COONa are 126.4, 425.9 and 91.0 S cm2 mol–1 respectively. Calculate Λm0
for CH3COOH.
Solution: Λm0 (HCl) + Λm0 (CH3COONa) - Λm0 (NaCl)
425.9 + 91.0 - 126.4 = 390.5 S cm2 mol–1

Q7. Calculate Ecell for the reaction given below, if E0cell = 3.17V
Mg (s) + 2Ag+ (0.0001M) →Mg2+ (0.130M) + 2Ag (s)
Solution:
Ecell = E0cell – (0.059/2) log {[Mg2+] / [Ag+]2 }

= 3.17 – 0.0295 log [(0.130)/ (0.0001)2]

= 3.17 V – 0.21V = 2.96 V

Q8. A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5 amperes. What is the mass of
copper deposited at the cathode?
Solution: t = 10 x 60 = 600 s
Q = I X t = 1.5 A × 600 s = 900 C
According to the reaction:
Cu2+ (aq) + 2e– = Cu(s)
We require 2F or 2 × 96500 C to deposit 1 mol or 63 g of Cu.
For 900 C, the mass of Cu deposited
= (63 g mol–1 × 900 C)/ (2 × 96500 C mol–1)
= 567 / 1930 g
= 0.2938 g.

Q9. The electrical resistance of a column of 0.05 mol L–1 NaOH solutions of diameter 1 cm and length 50
cm is 5.55 × 103 ohm. Calculate its resistivity, conductivity and molar conductivity.
Solution:
A = ᴨ r2 = 3.14 × 0.52 cm2 = 0.785 cm2 = 0.785 × 10–4 m2
l = 50 cm = 0.5 m
R = ρ l/ A
ρ (resistivity) = RA/l = [5.55 × 103 ohm x 0.785 cm2] / 50 cm = 87.135 ohm cm
Conductivity (κ) = 1/ ρ = [1 / 87.135] S cm-1 = 0.01148 S cm–1

Molar conductivity, Λm = [κ (S cm-1) x 1000 (cm3/L)] / Molarity (mol/L)

= [0.01148 ×1000]/ 0.05
= 229.6 S cm2 mol–1

Q10. Conductivity of 0.00241 M acetic acid is 7.896 x 10-5 S cm-1. Calculate its molar conductivity. If Λ0m
for acetic acid is 390.5 S cm2 mol-1. What is the dissociation constant?
Answer: Molar conductivity, Λm = 32.76 S cm2 mol-1
= 32.76/390.5 = 8.39 x 10-2
Dissociation constant = 1.86 x 10-5
Q11. Explain the following:
1. How much charge is required for 1 mol of MnO4- to Mn2+

27
 2. How much electricity is required in coulomb for the oxidation of 1 mol of H2O to O2
3. How much electricity in terms of Faraday is required to produce 40g of Al from molten Al2O3
Ans. 1. Reduction of 1 mol of MnO4- requires = 5 x 96500 C
2. Oxidation of 1 mol of H2O requires = 2 x 96500 C
3. Al3+ + 3e- → Al
1 mol of Al requires 3 mol of electrons or 3 F
27g of Al requires = 3F
40g of Al requires = (3 x 40) / 27 = 4.44F

Q12. The standard electrode potential for Daniell cell is 1.1V. Calculate the standard Gibbs energy for the
reaction: Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
Solution: ∆rG0 = – n F E0cell
The value of n in the above equation is 2, F = 96500 C mol–1 and E0cell = 1.1 V
Therefore, ∆rG0 = – 2 × 1.1V × 96500 C mol–1
= – 212300 J mol–1
= – 212.3 kJ mol–1

Q13. Calculate the equilibrium constant of the reaction:

Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)
E0cell = E0Ag+/Ag - E0Cu2+/Cu = 0.80 – 0.34 = 0.46 V
Ans. log Kc = (2 x 0.46)/0.059 = 15.59
Kc = 3.92 × 1015

Q14. The standard electrode potential for Daniell cell is 1.1V. Calculate the standard Gibbs energy for the
reaction: Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
Solution: ∆rG0 = – n F E0cell
The value of n in the above equation is 2, F = 96500 C mol–1 and E0cell = 1.1 V
Therefore, ∆rG0 = – 2 × 1.1V × 96500 C mol–1
∆rG0 = – 212300 J mol–1
∆rG0 = – 212.3 kJ mol–1

Q15. Write the cell reaction of a lead storage battery when it is discharged. How does the density of the
electrolyte change when the battery is discharged?
Ans. Pb + PbSO4 + 2H2SO4 → 2PbSO4 + 2H2O
Density of electrolyte decreases because water is formed and sulphuric acid is consumed as the product
during discharge of the battery.

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