3.

ELECTROCHEMISTRY
It is a branch of chemistry that deals with the relationship between chemical energy
and electrical energy and their inter conversions.
Electrochemical cells
An electrochemical cell is a device in which chemical energy of a redox reaction is
converted into electrical energy. 
The simplest electrochemical cell is Daniel cell or Galvanic cell in which a zinc rod is
placed in a solution of Zn2+ ions (say ZnSO4) in the left container and a bar of copper
metal is immersed in a solution of Cu2+ ions (say CuSO4) in the right container. The
two metals which act as electrodes are connected by a metallic wire through a
voltmeter. The two solutions are joined by an inverted U-tube containing semi-solid
paste of either KCl, KNO3 or NH4Cl or in gelatin or agar-agar jelly. This arrangement of
u-tube is called salt bridge. A diagram of this cell has been shown in figure.

There is a deflection in the voltameter which indicates the flow of current through
the external circuit. The conventional current flows through the outer circuit from
copper metal to zinc metal, which implies flow of electrons from zinc to copper bar.

The overall cell reaction :

can be split into two half cells.

(a) At zinc electrode the metal undergoes oxidation and releases two electrons.

Since oxidation is taking place, the electrode behaves as anode.

1
These electrons travel through wire and reach the copper metal.

Since reduction is taking place, the electrode behaves as cathode.

As a result of the two half cell reactions, zinc metal dissolves in anode solution to
form Zn2+ ions, while the Cu2+ ions are discharged at the cathode by accepting two
electrons and are deposited at cathode. The electrical neutrality is maintained in two
half cells using a salt bridge. The anions of the inert electrolyte in the salt bridge
migrate to the anodic chamber and cations to the cathodic chamber. As a result, as
the reaction progresses, copper bar gains weight whereas zinc rod loses weight. As a
consequence the cell continues to function till either zinc metal or copper ions in
solution are consumed fully.
Functions of Salt Bridge 
A salt bridge carries out two important functions :

(a) it allows only flow of ions through it. Thus, the circuit is completed.

(b) it also maintains the electrical neutrality..

Cell Diagram or representation of an electrochemical cell

Anode half cell is written on the left hand side while cathode half cell on right hand
side

The Daniel cell is represented as follows :

Reversibility of Daniel Cell

1. When external voltage is less than 1.10 V, electrons flow from Zn to Cu but current
flows from Cu to Zn i.e., in opposite direction. Zinc dissolves at anode and copper
deposits at cathode [see Fig (a)]

2. When external voltage applied is less than 1.10 V and is increased slowly, it is
observed that the reaction continues to take place till the external voltage attains the
value 1.10 V. When this is so, reaction stops altogether and no current flows [see Fig.
(b)].

3. When the value of external voltage exceeds the voltage of Daniel cell (1.10 V), the
reaction takes place in opposite direction, i.e., the cell functions like an electrolytic
cell. [See Fig. (c)].

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Functioning of Daniel cell when
external voltage   
opposing the cell potential is
applied

Electrode Potential
It may be defined as the
tendency of an element, when it
is placed in contact with its
own ions to either lose or
gain of electrons and in turn becomes positively or negatively charged.

The electrode potential will be named as oxidation or reduction potential depending

upon whether oxidation or reduction has taken place.

Standard Hydrogen Electrode (SHE) : Measurement of Electrode Potential

The potential of individual half-cell cannot be measured. We can measure only the
difference between the two half-cell potentials that gives the emf of the cell. For this
purpose a half-cell called standard hydrogen electrode (SHE) is used.
It consists of a platinum electrode coated with platinum black.
The electrode is dipped in an acidic solution of one molar concentration and pure
hydrogen gas at 1 bar pressure and 298K is bubbled through it.
It is represented as Pt(s)/H2(g)/H+ (aq).

By convention, the electrode potential of SHE is taken as zero.

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To determine the electrode potential of an electrode, it is connected in series with
the standard hydrogen electrode and the emf of the resulting cell is determined by
the equation, Ecell = ER – EL
Since the electrode potential of SHE is zero, the value of Ecell is equal to the
electrode potential of the given electrode.
The hydrogen electrode can act both ways, i.e., as an anode or as a cathode.

If the standard electrode potential of an electrode is greater than zero (i.e. +ve), then
its reduced form is more stable compared to hydrogen gas.
Similarly, if the standard electrode potential is negative then hydrogen gas is more
stable than the reduced form of the species.
Standard Oxidation Potential (Eoox)
It is the potential difference when a given electrode in contact with its own ions of
1M concentration undergoes oxidation when coupled with SHE.

Here SHE acts as cathode (reduction electrode) and the metal electrode as anode
(oxidation electrode).

Example :

Standard Reduction Electrode Potential (Eored)

It is the potential difference developed in a cell in volts, when a given metal electrode
in contact with its ions (c = 1M) undergoes reduction when it is coupled with SHE.

Here SHE acts as anode (oxidation electrode) and the metal electrode as cathode
(reduction electrode)

Example :

Standard Electrode Potential (Eo)

When the concentrations of all the species involved in a half-cell is unity then the
electrode potential is known as standard electrode potential.

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According to IUPAC convention, standard reduction potential is taken as the standard
electrode potential.

Both oxidation and reduction potentials are equal in magnitude but opposite in sign.

E.M.F. of the Cell

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.
The cell electromotive force (emf) of the cell is the potential difference between the
two electrodes, when no current is flow through the cell.
Ecell= Ecathode − Eanode

Since anode is put on left and cathode on right, it follows therefore, E cell  = ER − EL

For a Daniel cell, therefore

E0(cell) = E0(Cu2+/Cu) - E0(Zn2+/Zn) = 0.34-(-0.76) = 1.10V

Nernst Equation

Nernst showed that it is not necessary that the concentration of all the species
involved in the electrode reaction is unity. So, Nernst equation gives the relationship
between the electrode potential and ionic concentration of the electrolytic solution.

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Where, Eo= Standard electrode reduction potential
E = Electrode reduction potential

R = Molar gas constant (8.314 JK−1 mol−1)

T = Absolute temperature

F = Faraday constant (96487 ≈ 96500 c mol−1 )

n = Number of electrons involved in electrode reaction and

[Mn+]  = concentration of Metal ion, Mn+

[M] = Unity (1), since concentration of pure solid and liquid is taken as unity.

Since the concentration of any solid is taken as unity, the above equation becomes:
E(Mn+/M) = E0(Mn+/M) -- RT ln 1
nF [M n+]
Or, E(Mn+/M) = E0(Mn+/M) -- 2.303RT log 1
nF [M n+]
or, Eel. = E0el. – 0.059 log 1
n [M n+]
In Daniel cell, the electrode reactions are:
Cu2+ + 2 e- Cu(s) (cathode)
2+
Zn(s) Zn + 2 e- (anode)
The electrode potentials are given as
For Cathode:
E(Cu2+/Cu) = E0(Cu2+/Cu) – 0.059 log 1
2 [Cu 2+]
For anode:
E(Zn2+/Zn) = E0(Zn2+/Zn) -- 0.059 log 1
2 [Zn 2+]
The cell potential, Ecell = E(Cu2+/Cu) - E(Zn2+/Zn)

= E0(Cu2+/Cu) – 0.059 log 1 -- E0(Zn2+/Zn) -- 0.059 log 1

2 [Cu2+] 2 [Zn 2+]

= [E0(Cu2+/Cu) – E0(Zn2+/Zn) ] – 0.059 log [ Zn2+]

2 [Cu 2+]

= E0cell -- 0.059 log [ Zn2+]

2 [Cu2+]

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For a general electrochemical reaction of the type:
a A + bB ⎯-⎯→ cC + dD
Nernst equation can be written as:

Ecell = E0cell -- 0.059 log [C]c[D]d

n [A]a[B]b

Ecell = E0cell -- 0.059 log [products]

n [reactants]

Equilibrium Constant from Nernst Equation

For a Daniel cell, the emf of the cell at 298K is given by:

Ecell = E0cell -- 0.059 log [ Zn2+]

2 [Cu 2+]

When the cell reaction attains equilibrium, Ecell = 0

So, 0 = E0cell -- 0.059 log [Zn2+]
2 [Cu2+]
Or, E0cell = 0.059 log [Zn2+]
2 [Cu2+]
But at equilibrium, [Zn2+] = Kc
[Cu2+]

So the above equation becomes, E0cell = 0.059 log Kc

2
0
In General, E cell = 0.059 log Kc at 298 K
n

Electrochemical Cell and Gibbs Energy of the Reaction

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
ΔG is the Gibbs energy of the reaction, then ΔG = – nFEcell
If the concentration of all the reacting species is unity, ΔG0 = –nFE0 cell
Thus, from the measurement of E0cell, we can calculate the standard Gibbs energy of
the reaction.
Electrochemical Series
When the elements are arranged in order of decreasing reduction potential (or
increasing negative reduction potential),the series formed is known as
electrochemical series.

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Application of electrochemical series.
(i) For calculation of the EMF of an electrochemical cell, EMF = E cathod − Eanode

(ii) To prodict the feasibility of cell reaction.

(for a redox reaction to be spontaneous the EMF of the cell must be positive.)

(iii) To compare the reactivity of metals.

(iv) To calculate standard free energy of the reaction ΔG0 = −nFE0

A negative E0 means that the redox couple is a stronger reducing agent than the
H+/H2 couple.
A positive E0 means that the redox couple is a weaker reducing agent than the
H+/H2 couple.

Conductance of Electrolytic Solutions

Resistance (R) : It is the property of a substance by which it obstructs the flow of
current through it. Its SI unit is ohm (Ω)

Here,   is fixed for a conductor, called cell constant and ρ(Rho), the constant of
proportionality is called the Resistivity or specific resistance.

Hence, Resistance = Resistivity x cell constant.

If, in a uniform conductor, l = 1m, A = 1m2 then R = ρ

Resistivity of a uniform conductor is equal to its resistance when its length is 1 m
and its cross-sectional area is 1 m2.
The SI unit of resistivity is ohm m (Ωm).

Conductance (G): It is the reciprocal of the electrical resistance.

G = 1/R
G= 1 x A

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 ρ l
Or, G = ƙ x A/ Ɩ
It is expressed as ohm−1 or mho and its unit is siemen, S (  Ω−1).
Conductivity (ƙ) or specific conductance is the reciprocal of resistivity or specific
resistance (ρ).

It is defined as the conductance of a conductor having unit length and unit area of
cross-section.

Its unit is ohm-1 m-1 or mho m-1 or Sm-1

1 S cm-1 = 100 S m-1
1 S m-1 = 10-2 S cm-1

Measurement of the conductivity of ionic solutions

We know that, conductivity G = ƙ x A/ Ɩ
So conductivity, ƙ = G x Ɩ/A
The quantity Ɩ/A is called cell constant (G*). It depends on the distance between the
electrodes and their area of cross-section.Its unit is m-1.
i.e. conductivity = conductance x cell constant
So in order to determine the conductivity of an electrolytic solution, first determine
the resistance by using a Wheatstone bridge. It consists of two resistances R 3 and R4,
a variable resistance R1 and the conductivity cell having the unknown resistance R2. It
is connected to an a.c source and a suitable detector. Direct current cannot be used
since it causes the decomposition of the solution.

The bridge is balanced, when no current passes through the detector.

Under this condition,
R1 = R 3
R2 R4
Therefore, the unknown resistance, R2 = R1R4

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 R3
By knowing the resistance, we get the value of conductance and conductivity.
Conductivity cell
It consists of two platinum electrodes coated with platinum black. The electrodes are
separated by a distance Ɩ and their area of cross-section is A.
The cell constant of a conductivity cell is usually determined by measuring the
resistance of the cell containing a solution whose conductivity is already known (e.g.
KCl solution).

Molar conductivity (Λm): It is the conductivity of 1 mole of an electrolytic solution

kept between two electrodes with unit area of cross section and at a distance of unit
length. It is related to conductivity of the solution by the equation,
λm= ƙ/C (where C is the concentration of the solution)

Mathematically,

Where, V = Volume of solutions (in cm3)  containing one mole of electrolyte

Cm = molar concentration (mol L−1) or molarity.
Units of molar conductivity = ohm−1cm−2mol−1 or S cm2 mol-1.

Factors affecting molar conductivity :

(A) Nature of electrolyte i.e. strong or weak.
(B) Temperature
(C) Concentration of electrolytes in solution.

Variation of conductivity and Molar conductivity with concentration

Both conductivity and molar conductivity change with the concentration of the
electrolyte.

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 For both strong and weak electrolytes, conductivity always decreases with
dilution :This is because conductivity is the conductance of unit volume of electrolytic
solution. As dilution increases, the number of ions per unit volume decreases and
hence the conductivity decreases.
For both strong and weak electrolytes, the molar conductivity increase with
dilution (or decrease with increase in concentration), but due to different reasons:
For strong electrolytes, as dilution increases, the force of attraction between the ions
decreases and hence the ionic mobility increases. So molar conductivity increases .
When dilution reaches maximum or concentration approaches zero, the molar
conductivity becomes maximum and it is called the limiting molar conductivity (λ 0m).
For strong electrolyte like KCl, HCl etc. the variation is given by the following
equation.

Λm = Λmo − Ac1/2

A = a constant which depends on the types of electrolyte for a given solvent and
temperature.
All electrolytes of a particular type have the same value for 'A'.
Λmo = molar conductivity of infinite dilution or when concentration of the solution
approaches to zero, known as limiting molar conductivity.
c = Concentration of solution in mol L−1

For weak electrolytes, as dilution increases, the degree of dissociation increases. So

the number of ions and hence the molar conductivity increases.

The variation of λm for strong and weak electrolytes is shown in the following graphs:

For strong electrolytes, the value of λ0m can be determined by the extrapolation of
the graph.

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 But for weak electrolytes, it is not possible since the graph is not a straight line. So
their λ0m values are calculated by applying Kohlrausch’s law of independent
migration of ions.
Kohlrausch’s law of independent migration of ions
The law states that the limiting molar conductivity of an electrolyte can be
represented as the sum of the individual contributions of the anion and the cation of
the electrolyte.
Thus if an electrolyte on dissociation gives n(+) cations and n(-) anions, its limiting
molar conductivity is given
λ0m = n(+)λ0(+) + n(-)λ0(-)
For NaCl, λ0m(NaCl) = λ0(Na+) + λ0(Cl-)
For CaCl2, λ0m(CaCl2) = λ0(Ca2+) + 2 x λ0(Cl-)

Application of Kohrauch’s law :

(i) For determination of  Λmo of weak electrolytes, for example,

(ii) For determining degree of dissociation (α) of an electrolyte at a given dilution,

(iii) For calculation of dissociation constant   of a weak electrolyte at

concentration c of solution,

Electrolytic Cells and Electrolysis

In an electrolytic cell, the electrical energy is converted to chemical energy. The
dissociation of an electrolyte by the passage of electricity is called electrolysis.
1) Faraday’s first law

It states that the amount of substance deposited or liberated at the electrodes (m) is
directly proportional to the quantity of electricity (Q) flowing through the electrolyte.
Mathematically, w α Q
Or, w = zQ
Where z is a constant called electrochemical equivalent.
Electrochemical equivalent (Z) is the amount of substance deposited when a current
of one ampere is passed for one second through the solution.

But quantity of electricity is the product of current in ampere (I) and time in second
(t).

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i.e. Q = It
Therefore, w = zIt (1)
1 Faraday is the charge of 1 mole of electron and its value is 96500 C/mol.
(6.023 × 1023 × 1.6 × 10-19 ≈ 96500 Coulombs)
For the deposition of 1 mole of Na (23g), the amount of charge required = 1 F
(Since Na+ + e- → Na)
For Ca, Q = 2F (since Ca2+ + 2e- → Ca)
nF deposits an amount of equal to 1mole.
nx96500C deposits an amount of equal to 1mole (atomic mass in gram)
1C deposits an amount of equal to M / n x 96500
Z = M/nF
Eqn (1) becomes w = MIt
nF

Faraday’s Second Law of Electrolysis

When same quantity of electricity is passed through different electrolytes, the
amount of different substances deposited or liberated at the electrodes is directly
proportional to their chemical equivalence.

Products of electrolysis
The products of electrolysis depend on
1.The nature of the electrolyte : molten or aqueous
2. The type of electrodes used: If the electrode is inert (e.g. Pt, gold etc.), it does not
participate in the electrode reaction. While if the electrode is reactive, it also
participate in the electrode reaction.
Moreover, the products of electrolysis depend on the different oxidizing and
reducing species present in the electrolytic cell and their standard electrode
potentials.
Some of the electrochemical processes are feasible, but kinetically so slow that at
lower voltages these do not seem to take place and extra potential (called
overpotential) has to be applied, which makes such processes more difficult to occur.

Predict the products of electrolysis in each of the following :

1. Molten NaCl :

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The products of electrolysis of molten NaCl are sodium metal (Na) and Cl2 gas, as
follow

2) Aqueous NaCl solution :
During the electrolysis of aqueous NaCl solution, the products are NaOH, Cl2 and H2. 
In this case we also have H+ and OH- ions besides ions along with the solvent
molecules, H2O
At the Cathode there is competition between the following reduction reactions:

The reaction with higher Eocellvalue is preferred, so the reaction at cathode is,

Therefore, the net reaction at cathode is the sum of the two reactions and we have

At the anode following oxidation reactions are possible,

The reaction at anode with lower value of Eo is preferred and therefore water should
get oxidised in preference to Cl-(aq). However, due to overpotential of oxygen, the
reaction 

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Thus, the net reactions may be summarised as :

3) An aqueous solution of AgNO3 with silver electrodes.

At the cathode: deposition of silver

Ag (aq)+e−
+
→Ag(s) ; E0 = 0.80 V

At the anode:, the silver electrode dissolves in the solution to form Ag +.

Ag Ag+ + 1e-

4) An aqueous solution of AgNO3with platinum electrodes.

At the cathode: deposition of silver

Ag+(aq)+e− → Ag(s) ; E0 = 0.80 V

At the anode: liberate O2

2H2O(l)→O2(g)+4H +
(aq)+4e−

5) A dilute solution of H2SO4with platinum electrodes.

At the cathode: H2 gas.

H +
(aq) + e− → 1/2 H2(g)

At the anode: O2 gas

2H2O(l) → O2(g)+4H (aq)+4e− ;

+
E0 = +1.23 V —–(i)

6) Con. H2SO4with platinum electrodes

At the cathode: H2 gas.

H +
(aq) + e− → 1/2 H2(g)

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At the anode, S2O8−2

2SO2 −4
(aq) → S2O8 (aq)+2e− ;
−2
E0 = +1.96 V —–(ii)

7) An aqueous solution of CuCl2 with platinum electrodes.

At the cathode: deposition of copper

Cu2+(aq ) + 2e− → Cu(s) ; E0 = 0.34 V.

At the anode: Cl2 gas.

Cl−
(aq) → ½ Cl2(g) + e−; E0 = 1.36 V

Batteries
A battery is basically a galvanic cell in which the chemical energy of a redox reaction
is converted to electrical energy. They are of mainly 2 types – primary batteries and
secondary batteries.
a) Primary cells:
These are cells which cannot be recharged or reused. Here the reaction occurs only
once and after use over a period of time, they become dead
E.g. Dry cell, mercury cell etc.
1. Dry Cell
It is a compact form of Leclanche cell. It consists of a as
Anode: Zinc container
Cathode: A carbon (graphite) rod surrounded by powdered manganese dioxide
(MnO2) and carbon.
Electrolyte: A moist paste of ammonium chloride (NH4Cl) and zinc chloride (ZnCl2).

The electrode reactions are:

Ammonia produced in this reaction forms a complex with Zn2+ and thus corrodes the
cell. The cell has a potential of nearly 1.5 V.

2. Mercury cell

Anode : Zinc – mercury amalgam .

Cathode : A paste of HgO and carbon.
Electrolyte : A paste of KOH and ZnO.

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The electrode reactions are:

The overall reaction is : Zn(Hg) + HgO(s) → ZnO(s) + Hg(l )

The cell has a constant potential of 1.35 V since the overall reaction does not involve
any ion in solution.
b) Secondary cells
A secondary cell can be recharged and reused again and again. Here the cell reaction
can be reversed by passing current through it in the opposite direction.
1.Lead storage cell, which is used in automobiles and invertors.

Anode:Lead
Cathode: A grid of lead packed with lead dioxide (PbO2) .
Electrolyte : 38% H2SO4 solution.

The cell reactions are:

i.e. The overall reaction is:

The overall cell reaction is: Pb(s)+PbO2(s)+2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)

On charging the battery, the reaction is reversed and PbSO 4(s) on anode and cathode
is converted into Pb and PbO2, respectively.

2. Nickel-cadmium cell which has longer life than the lead storage cell but costly.
Anode : Cadmium
Cathode : Metal grid containing NiO2
Electrolyte : KOH solution
Here, the overall reaction during discharge of the battery is:

Fuel cells
These are galvanic cells which convert the energy of combustion of fuels like
hydrogen, methane, methanol, etc. directly into electrical energy.
One example for fuel cell is Hydrogen – Oxygen fuel cell, which is used in the Apollo
space programme. Here hydrogen and oxygen are bubbled through porous carbon

17
electrodes into concentrated aqueous sodium hydroxide solution. To increase the
rate of electrode reactions, catalysts like finely divided platinum or palladium metal
are filled into the electrodes.
The electrode reactions are:

Advantages of Fuel cells

1. The cell works continuously as long as the reactants are supplied.
2. It has higher efficiency (upto 70%)as compared to other conventional cells.
3. It is eco-friendly (i.e. pollution free) since water is the only product formed.
4. Water obtained from H2 – O2 fuel cell can be used for drinking.
Corrosion
It is the process of formation of oxide or other compounds of a metal on its surface
by the action of air, water-vapour, CO2 etc.
Some common examples are: The rusting of iron, tarnishing of silver, formation of
green coating on copper and bronze etc.
Rusting of iron: It occurs in presence of water and air. It is a redox reaction. At a
particular spot of the metal, oxidation takes place and that spot behaves as anode.
Here Fe is oxidized to Fe2+. Electrons released at anodic spot move through the metal
and go to another spot on the metal and reduce oxygen in presence of H + . This spot
behaves as cathode. The ferrous ions (Fe2+) are further oxidised to ferric ions (Fe3+ )
and finally to hydrated ferric oxide (Fe2O3. xH2O), which is called rust.

Methods to prevent corrosion

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1. By coating the metal surface with paint, varnish etc.
2. By coating the metal surface with another electropositive metal like zinc,
magnesium etc. The coating of metal with zinc is called galvanisation and the
resulting iron is called galvanized iron.
3. By coating with anti-rust solution.
4. An electrochemical method is to provide a sacrificial electrode of another metal
(like Mg, Zn, etc.) which corrodes itself but saves the object (sacrificial protection).

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