UNIT 3 : ELECTROCHEMISTRY

Electrochemistry deals with relationship between electrical energy and chemical energy
and their inter-conversion.
Electrochemical cell is a device in which chemical energy is converted into electrical
energy

Electron flow

Anode Cathode

The electrode at which oxidation occurs is called anode and at which reduction occurs is
called cathode.

Salt bridge
It is inverted U like tube containing saturated solution of some electrolyte like KCl,KNO3,
NH4NO3 with agar-agar jelly or gelatine and connects the anode and cathodce in an
electrochemical cell.

Functions of salt bridge:-

 It allows the flow of current by completing the inner circuit.
 It maintains electrical neutrality in both the half cells.

Cell representation:
A cell with the following chemical reaction:

may be represented as

Electrode potential: - The potential difference set up between the metal and the solution
of its ions is known as electrode potential
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Standard electrode potential is the electrode potential of a metal in contact with it’s
ions when the concentration of ions is 1 molar at 1 bar pressure and 298K.It may be
standard reduction potential or standard oxidation potential.
EMF of the cell: - It is defined as the potential difference between the two terminals of
the cell when either no or very little current is drawn from it.

What is Electrode Potential?

When a metal is placed in a solution of its ions, the metal acquires either a positive or
negative charge with respect to the solution. On account of this, a definite potential
difference is developed between the metal and the solution. This potential difference is
called electrode potential.
For example, when a plate of zinc is placed in a solution having
Zn2+ ions, it becomes negatively charged with respect to solution and thus a potential
difference is set up between zinc plate and the solution. This potential difference is termed
the electrode potential of zinc. Similarly, when copper is placed in a solution having
Cu2+ ions, it becomes positively charged with respect to solution. A potential difference is
set up between the copper plate and the solution. The potential difference thus developed
is termed as electrode potential of copper. The potential difference is established due to
the formation of electrical double layer at the electrodes
Following two changes occur when a metal rod is dipped in its salt solution,
(a) Oxidation: Metal ions pass from the electrode into solution leaving an excess of
electrons and thus a negative charge on the electrode.

M → Mn + ne-
The metal ions go into the solution and the electrons remain on the metal making it
negatively charged. The tendency of the metal to change into ions is known as electrolytic
solution pressure.
(b) Reduction: Metal ions in solution gain electrons from the electrode leaving a positive
charge on the electrode. Metal ions start depositing on the metal surface leading to a
positive charge on the metal.
Mn+ + ne- → M
In the beginning, both these changes occur with different speeds but soon an equilibrium
is established.
M Mn+ + ne-
In practice, one effect is greater than the other,
If first effect is greater than the second, the metal acquires a negative charge with respect
to solution and
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If the second is greater than the first, it acquires positive charge with respect to solution,
thus in both the cases a potential difference is set up.
The magnitude of the electrode potential of a metal is a measure of its relative tendency
to lose or gain electrons, i.e., it is a measure of the relative tendency to undergo oxidation
(loss of electrons) or reduction (gain of electrons).

Depending on the nature of the metal electrode to lose or gain electrons, the
electrode potential may be of two types:
 Oxidation potential: When electrode is negatively charged with respect to solution,
i.e., it acts as anode. Oxidation occurs.
M → Mn+ + ne-
 Reduction potential: When electrode is positively charged with respect to solution,
i.e., it acts as cathode. Reduction occurs.
Mn+ + ne- → M
 It is not possible to measure the absolute value of the single electrode potential
directly. Only the difference in potential between two electrodes can be measured
experimentally. It is, therefore, necessary to couple the electrode with another
electrode whose potential is known. This electrode is termed as reference electrode.
The EMF of the resulting cell is measured experimentally.
 The EMF of the cell is equal to the sum of potentials on the two electrodes.
 Emf of the cell = EAnode + ECathode = Oxidation potential of anode + Reduction potential
of cathode
 Knowing the value of reference electrode, the value of other electrode can be
determined.

Standard Electrode Potential

In order to compare the electrode potentials of various electrodes, it is necessary to
specify the concentration of the ions present in solution in which the electrode is dipped
and the temperature of the half-cell.

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The potential difference developed between metal electrode and the solution of its ions
of unit molarity (1M) at 25°C (298 K) is called standard electrode potential.
According to the IUPAC convention, the reduction potential alone be called as the
electrode potential (EO), i.e., the given value of electrode potential be regarded as
reduction potential unless it is specifically mentioned that it is oxidation potential.
Standard reduction potential of an electrode means that reduction reaction is taking place
at the electrode. If the reaction is reversed and written as oxidation reaction, the numerical
value of electrode potential will remain same but the sign of standard potential will have
to be reversed. Thus

Standard reduction potential = - (Standard oxidation potential)

or
Standard oxidation potential = - (Standard reduction potential)

Reference Electrode
( Standard Hydrogen Electrode, SHE)

 Hydrogen electrode is the primary standard electrode.

 It consists of a small platinum strip coated with platinum black as to adsorb hydrogen
gas.

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 A platinum wire is welded to the platinum strip and sealed in a glass tube as to make
contact with the outer circuit through mercury.
 The platinum strip and glass tube is surrounded by an outer glass tube which has an
inlet for hydrogen gas at the top and a number of holes at the base for the escape of
excess of hydrogen gas.
 The platinum strip is placed in an acid solution which has H+ ion concentration 1 M.
 Pure hydrogen gas is circulated at one atmospheric pressure.
 A part of the gas is adsorbed and the rest escapes through holes. This gives an
equilibrium between the adsorbed hydrogen and hydrogen ions in the solution.
 H2 2H+ + 2e-
The temperature of the cell is maintained at 25 0C. By international agreement the
standard hydrogen electrode is arbitrarily assigned a potential of exactly ± 0.000 . .. volt.
The hydrogen electrode thus obtained forms one of two half-cells of a voltaic cell. When
this half-cell is connected with any other half-cell, a voltaic cell is constituted. The
hydrogen electrode can act as cathode or anode with respect to other electrode.
SHE half reaction Electrode potential

H2 → 2H+ + 2e- 0.0 V (Anode)

2H+ + 2e- → H2 0.0 V (Cathode)

Measurement of Electrode Potential

The measurement of electrode potential of a given electrode is made by constituting a
voltaic cell, i.e., by connecting it with a standard hydrogen electrode (SHE) through a salt
bridge.
1 M solution is used in hydrogen half-cell and the temperature is maintained at 25oC.

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The EMF of the cell is measured either by a calibrated potentiometer or by a high
resistance voltmeter, i.e., a valve voltmeter. The reading of the voltmeter gives the
electrode potential of the electrode in question with respect to the hydrogen electrode.
The standard electrode potential of a metal may be determined as it is the potential
difference in volt developed in a cell consisting of two electrodes: the pure metal is contact
with a molar solution of one of its ions and the standard hydrogen electrode.

Determination of Standard Electrode Potential of Zn/Zn2+ Electrode

 A zinc rod is dipped in 1 M zinc sulphate solution. This half-cell is combined with a
standard hydrogen electrode through a salt bridge.
 Both the electrodes are connected with a voltmeter.
 The deflection of the voltmeter indicates that current is flowing from hydrogen electrode
to metal electrode or the electrons are moving from zinc rod to hydrogen electrode.
 The zinc electrode acts as an anode and the hydrogen electrode as cathode and the
cell can be represented as

Cell Representation Oxidation half reaction Reduction ha

Zn|Zn2+ (aq)/Anode(-) || 2H(aq)| H2 (g)/Cathode (+) Zn → Zn2+ + 2e- 2H+ + 2e- → H

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 The EMF of the cell is 0.76 volt
 ECell = EoAnode + EoCathode
0.76 = EoAnode + 0 or EoAnode = +0.76 V
 As the reaction on the anode is oxidation, i.e.,
Zn → Zn2+ + 2e,
 EoAnode is the standard oxidation potential of zinc. This potential is given the positive
sign.

 Eoox (Zn/Zn2+) = +0.76 volt

 So standard reduction potential of Zn, i.e., Eo (Zn/Zn2+)
= Eoox = -(+0.76)
= -0.76 volt
 The EMF of such a cell gives the positive value of standard oxidation potential of metal
M. The standard reduction potential (Eo) is obtained by reversing the sign of
standard oxidation potential.

Determination of Standard Electrode Potential of Cu2+/Cu, Electrode:

A copper rod is dipped in 1 M solution of CuSO4. It is combined with hydrogen electrode
through a salt bridge. Both the electrodes joined through a voltmeter. The deflection of
the voltmeter indicates that current is flowing from copper electrode towards hydrogen
electrode, i.e., the electrons ate moving from hydrogen to copper electrode. The hydrogen

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electrode acts as an anode and the copper electrode as a cathode. The cell can be
represented as

Cell Representation Oxidation half reaction Reduction half reac

H2 (g)|2H+ (aq) ||Cu2+ (aq) |Cu H2 → 2H+ + 2e- Cu2+ 2e- → Cu

 The EMF of the cell is 0.34 volt.

 EoCell = EoAnode + EoCathode
0.34 = 0 + EoCathode
 Since the reaction on the cathode is reduction, i.e.,
Cu2+ + 2e- → Cu, EoCathode is the standard reduction potential of copper. This is
given the +ve sign.
 E°, i.e., standard reduction potential of Cu2+/Cu = 0.34 volt
So E°x (standard oxidation potential of copper) = -0.34 volt
 The EMF of such a cell gives positive value of reduction potential of metal electrode.
The standard oxidation potential of this electrode is obtained by reversing the sign of
standard reduction potential.
 The EMFof such a cell gives the positive value of standard oxidation potential of metal
M. The standard reduction potential (E°) is obtained by reversing the sign of standard
oxidation potential.

 It is thus concluded that at the metal electrode which acts as anode with respect to
hydrogen electrode (cathode), the reduction potential is given the minus sign and at
the metal electrode which acts as cathode with respect to hydrogen electrode (anode),
the reduction potential is given the positive sign.
Some Other Reference Electrodes
Since a standard hydrogen electrode is difficult to prepare and maintain, it is usually
replaced by other reference electrodes, which are known as secondary reference
electrodes. These are convenient to handle and are prepared easily. Two important
secondary reference electrodes are described here.

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
Calomel Electrode
It consists of mercury at the bottom over which a paste of mercury-mercurous chloride is
placed. A solution of potassium chloride is then placed over the paste. A platinum wire
sealed in a glass tube helps in making the electrical contact. The electrode is connected
with the help of the side tube on the left through a salt bridge with the other electrode to
make a complete cell.
The potential of the calomel electrode depends upon the concentration of the
potassium chloride solution. If potassium chloride solution is saturated, the electrode
is known as saturated calomel electrode (SCE) and if the potassium chloride solution is
1 N, the electrode is known as normal calomel electrode (NCE) while for 0.1 N potassium
chloride solution, the electrode is referred to as decinormal calomel electrode (DNCE).
The electrode reaction when the electrode acts as cathode is:
1/2 Hg2Cl2 + e- Hg + Cl-

Nernst equation:
This equation is used to measure the electrode potential of any half cell at any
concentration with respect to SHE.

The concentration of a solid is unity, so the equation becomes

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Relationship between equilibrium constant and standard electrode potential

Relationship between standard Gibbs free energy and standard electrode

potential
Relationship between standard Gibbs free energy and equilibrium constant

CONDUCTIVITY AND MOLAR CONDUCTIVITY

The conductance is the property of the conductor (metallic as well as electrolytic) which
facilitates the flow of electricity through it. It is equal to the reciprocal of resistance i.e.,

Units of conductance : :
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Specific Conductance or Conductivity
The resistance of any conductor varies directly as its length (l) and inversely as its cross-
sectional area (A), i.e.,

Mathematically

Where ρ is called the specific resistance.

l/A is known as cell constant.
If l = 1 cm and A = 1 cm2, then
R=ρ
The specific resistance is, thus defined as the resistance of one centimeter cube of a
conductor.
The reciprocal of specific resistance is termed the specific conductance or it is the
conductance of one centimeter cube of a conductor.
It is denoted by the symbo (kappa)l .
Thus,

Where kappa → the specific conductance

Specific conductance is also called conductivity.
Further,

or Specific conductance = Conductance × cell constant

In the case of electrolytic solutions, the specific conductance is defined as the
conductance of a solution of definite dilution enclosed in a cell having two electrodes of
unit area separated by one centimeter apart.
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Unit of specific conductance:

Equivalent Conductance
One of the factors on which the conductance of an electrolytic solution depends is the
concentration of the solution.
In order to obtain comparable results for different electrolytes, it is necessary to take
equivalent conductance's.
Equivalent conductance is defined as the conductance of all the ions produced by one
gram equivalent of an electrolyte in a given solution.
It is denoted by A.

According to definitions,
Conductance = Specific conductance (K) = Equivalent conductance (Λ)
If the solution is diluted to say (9 cm3) (9 mL), the conductance of the solution will be the
same but specific conductance becomes 1/9th as it contains nine cubes.
The conductance is also equal to the equivalent because the solution still has 1 g
equivalent of the electrolyte.
Equivalent conductance ( ) = 9 × k
In general,
Λ=kx v
where V is the volume in mL containing 1 g equivalent of the electrolyte.

In case, if the concentration of the solution is c gram equivalent per litre, then the volume
containing 1 g equivalent of the electrolyte will be 1000/e.
So equivalent conductance
= k × 1000/c
= k × 1000/N
where N = normality
Unit of equivalent conductance:

Molar ConductanceThe molar conductance is defined as the conductance of all the ions
produced by ionization of 1 g mole of an electrolyte when present in V mL of solution. It
is denoted by .
Molar conductance Λ = k ×V

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where V is the volume in mL containing 1 g mole of the electrolyte. If c is the concentration
of the solution in g mole per litre, then
Λ = k × 1000/c
Units of molar conductance:
Equivalent conductance = (Molar conductance)/n
where
n = (Molecular mass)/(Equivalent mass)

Measurement of Conductance
It is now known to us that when the solution of an electrolyte is taken between two parallel
electrodes of cross-sectional area 'a' and 'l' cm apart, then the specific conductance, k,
should be:

Thus, knowing the values of R, l and A, the specific conductance can be measured.
 The resistance of the solution between two parallel electrodes is determined by
using Wheatstone bridge method.
 The diagram of the apparatus is shown in AB is a uniform wire and X is a sliding contact
which moves over it.
 C is the conductivity cell containing the solution of the electrolyte and S represents the
source of alternating current.
 R is the resistance box and T is a headphone to detect the flow of current.
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 A suitable resistance is taken out from the resistance box and the sliding contact X is
moves on the wire to search a point of minimum sound in the headphone. At this point,
the bridge is balanced.
 (Resistance of solution)/(Resistance from resistance box) =(Resistance
XB)/(Resistance XA) =(Length XB)/(Length XA)
 Resistance of solution can be used because it produce two complications.

Cell Constant
Since the electrodes are not exactly 1 unit apart and may not possess a surface area of
1 square unit, the measured resistance does not give the specific conductance of the
solution. Actual measurements of l and a being inconvenient, an indirect method is
employed to determine the value of which is a constant quantity for a particular cell and
is known as cell constant.
We know that
(Specific conductance)/Conductance=l/A= cell constant

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The resistance of cell, i.e., conductance is measured when filled with a standard solution
(say N/10 KCl solution) at a given temperature.
The standard values of specific conductance of KCl solutions of various concentrations
at different temperature are known.

Thus, the cell constant is calculated by using the above equation. The sane cell constant
applies to a measurement with any other solution.
The determination of specific conductance of an electrolytic solution, thus, consists of two
steps:
 Determination of cell constant by using a standard KCl solution of known concentration
in the conductivity cell.
 Determination of resistance of he given solution using the same cell. The reciprocal of
this gives the value of conductance.
Multiplication of conductance and cell constant gives the value of specific conductance of
the solution.
In order to determine equivalent conductance or molar conductance, the concentration of
the experimental solution should be known.
In conductance measurements, the solutions are always prepared in conductivity water
which has no conductance due to dissolved impurities.
VARIATION OF CONDUCTIVITY AND MOLAR CONDUCTIVITY WITH DILUTION
Conducctivity decreases with dilution whereas molar conductivity increases with dilution

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When concentration approaches zero then molar conductivity is called limiting molar
conductivity

Kohlrauschlaw of independent migration of ions: It 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.
o o 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:

Applications of Kohlrausch law: This law is used to measure the limiting molar
conductivity degree of dissociation and dissociation constant of weak electrolytes.

Electrolytic cell In this cell electric energy is used to carry non spontaneous chemical
reaction. An electrochemical cell works as electrolytic cell if external voltage supplied is
more than the emf of the cell.
Faraday’s Laws of Electrolysis
(i) First Law: The amount of chemical reaction occurs at any electrode during electrolysis
proportional to the quantity of electricity passed through the electrolyte (solution or melt).
M = Zit (M=Mass of substance obtained at electrode, i = current in Ampere, t= time in
seconds)
(ii) Second Law: 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).

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Batteries: Any battery (actually it may have one or more than one cell connected in
series) or cell that we use as a source of electrical energy is basically a galvanic cell.
There are mainly two types of batteries.

Primary batteries In the primary batteries, the reaction occurs only once and after use
over a period of time battery becomes dead and cannot be reused
Dry cell or Leclanche cell:

Mercury or Button cell:

T
The cell potential is 1.35 V and remains constant during its life as the overall reaction
does not involve any ion in solution whose concentration can change during its lifetime.

Secondary Batteries: A secondary cell after use can be recharged by passing current
through it in the opposite direction so that it can be used again.
Lead Storage Cell:
The cell reactions when the battery is in use are

overall cell reaction consisting of cathode and anode reactions is:

On charging the battery the reaction is reversed

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Nickel Cadmium cell:

Fuel Cell : fuel cell are galvanic cell that convert energy of combustion of fuel directly
in to electrical energy. Fuel used are hydrogen, methane , methanol. Its efficiency is
about 70% .

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 Corrosion: the phenomenon of degradation of upper layer of metal in presence of
oxygen, moisture and atmospheric gases etc.
e.g rusting of Iron

Prevention of Corrosion-
1. Barrier protection through coating of paints or electroplating.
2. By the use of antirust solutions (bis phenol).
3. By cathodic protection in which a metal is protected from corrosion by connecting it to
another metal that is more easily oxidized.

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