ELECTROCHEMISTRY

Introduction: 
Electrochemistry deals with the interconversion and relationship between chemical reactions and electrical
energy. 

All substances can be broadly divided into two types as far as conduction of electricity through them is
concerned. These are conductors and insulators. Substances which allow the passage of electricity through
them are called conductors, while those which do not allow electricity to pass through them are called
insulators.

Conductors may be classified into two types – electronic and electrolytic. 

Electronic conductors are those substances which conduct electricity without undergoing any dissociation.
Electricity is conducted through them by the flow of electrons. (e.g. metals, graphite, and certain minerals)

Electrolytic conductors or electrolytes are those substances which undergo dissociation when electricity is
passed through them. Electricity is conducted by the movement of ions. (e.g. acids, bases, salt solutions and
fused salts)

Electrolytes have been classified into two types, strong and weak electrolytes depending on their tendency to
ionize.

Strong electrolytes are substances, which are completely ionized, and conduct electricity to a large extent. E.g.
strong acids (e.g. HCl, H2SO4, HNO3), strong bases (e.g. NaOH, KOH) and salts in solution or molten state
(e.g. NaCl, KCl).

Weak electrolytes are substances which are not completely ionized in solution and hence do not conduct
electricity to a large extent. E.g. weak acids (e.g. CH3COOH) and bases (e.g. NH4OH),

Solutions of non-ionic substances such as urea, glucose, etc. do not conduct electricity and are called non-
electrolytes. 

Electrical resistance and electrical conductance:1
Resistance (R): The resistance of a conductor is given by Ohm’s law, according to which R = E/I, where ‘E’ is
the voltage applied to the ends of a conductor, and ‘I’ is the current flowing through it. 

The current is usually measured in amperes, whereas voltage is measured in volts. 

If 1 ampere current flows through a conductor when a voltage of 1 volt is applied to it, the resistance of the
conductor is equal 1 Ohm (Ω). 
All electrolytic conductors, like metallic conductors, obey Ohm’s law. 

Conductance (G): The reciprocal of the electrical resistance is called the conductance. 
G = 1/R
The conductance of a solution is a measure of the ability of the solution to allow the passage of an electric
current. 
The units of conductance are siemen (S) or ohm−1 (or mho). 

Specific conductance (κ): 

The specific conductance of a solution is defined as the conductance of a solution taken in a cell in which
the electrodes have unit area of cross-section, and are unit distance apart. 
It may also be defined as the conductance of unit cubic volume (1 m3) of the solution of the electrolyte. 

Mathematically, κ = × = G × 

Where, the factor (l/a) is called cell constant (l is the length and a is the area of cross section of the solution).
Unit of specific conductance: ohm−1m−1 = Sm−1

Equivalent and molar conductance: 

Equivalent conductance (Λeq) is defined as the conductance of that volume of solution which contains 1
equivalent of dissolved electrolyte placed between two parallel electrodes unit distance apart and large
enough to hold the whole of the electrolyte solution. 

It is the conductance of the solution containing 1 equivalent of the electrolyte at a given temperature. 

Λeq = , where, c is the concentration in eq m−3 
SI unit of Λeq is S m2 eq−1

Note: If the concentration is expressed in normality (eq dm−3) 

Λeq = ( 1 eq dm−3 = 1000 eq m−3)

According to IUPAC recommendations, the use of the term equivalent conductance is discontinued.

Molar conductance (Λm) is defined as the conductance of that volume of solution which contains 
1 mole of dissolved electrolyte placed between two parallel electrodes unit distance (1 m) apart and large
enough to hold the whole of the electrolyte solution. 
It is the conductance of the solution containing 1 mole of the electrolyte at a given temperature. 

The molar conductance of an electrolyte is v 


Where, c is the concentration in moles m−3 
SI unit of Λm is S m2 mol−1 

Note: If concentration is expressed in molarity (mol dm−3), 

Λm = ( 1 mol dm−3 = 1000 mol m−

Debye-Huckel theory
The increase of molar conductance with dilution in the case of weak electrolytes can be explained on the
basis of Arrhenius theory, which suggests that the conductance increases because the ionization of a weak
electrolyte increases with dilution. However, in the case of strong electrolytes, as they are almost completely
ionized even at moderate concentration, the increase in molar conductance with dilution must be due to some
additional factors.

The observed deviations in the behavior of strong electrolytes are ascribed to inter-ionic attractions. Although
Arrhenius theory assumed the existence of ions, it does not take into account the electrostatic attractions
between the ions in solution. 

According to Debye-Huckel theory

● Although the electrolyte is completely ionized, its dissociation is incomplete. 
● Dominant forces acting between the ions in a solution of a strong electrolyte are coulombic in nature, which is primarily responsible for departure from Ostwald’s law. 
● According to Debye Huckel, the increase in molar conductance with dilution in the case of strong electrolytes is due to increase in the mobilities of the ions.
● Inter-ionic effect plays a great role in understanding the behavior of the solutions of strong electrolytes.
● The magnitude of the inter-ionic attraction and increase in the conductance with dilution is best understood by considering the asymmetry effect and electrophoretic effect suggested by Debye and Huckel. 

● Debye - Huckel - Onsager equation (DHO equation): 

● It was shown by Debye and Huckel that due to asymmetric ionic atmosphere and electrophoretic effect, the mobility of an ion in solution of a strong electrolyte is affected, resulting in a decrease in the conductivity of the solution. Both th
retarding effects are dependent on the square root of the concentration. Their mathematical treatment was subsequently modified by Onsager, who included the natural Brownian movement of the ions as well. 
● The equation is now known as the Debye Huckel Onsager equation. 
● For a uni-univalent electrolyte, it is written as 
● Λc = Λ0 − (A + B Λ0)
● Where, A and B are constants for a particular solvent at a particular temperature. 

●
A and B Λ0 are the measure of decrease in conductance due to electrophoretic effect and asymmetric effect respectively. 1
● Substituting for A and B, the equation can be written as: 
● Λc = Λ0 − 1
●
● Where, Λc = equivalent conductance at concentration c
● Λ0 = equivalent conductance at infinite dilution
● D = dielectric constant of the medium, η = viscosity of the medium
● T = temperature in K and 
● c = concentration of the solution in moles dm−3 

Applications of conductivity measurements: Determination of degree of dissociation and dissociation

constant of a weak electrolyte. 
The degree of dissociation of a weak electrolyte at infinite dilution can be obtained by dividing the molar
conductance of the electrolyte at a given concentration by the molar conductance of the same electrolyte at
infinite dilution. 

Degree of dissociation, α = 
α= 

From Kohlrausch’s law, Λ0 = + 

Where, and are the ionic conducatnces at infinite dilution of the cation and anion respectively.

Hence α=


Λm can be determined experimentally and the values of are available from literature, hence degree of
dissociation can be calculated. 

Dissociation constant can be calculated using the formula 

K= 

c is the molar concentration i.e., concentration in mol dm−3 

The degree of dissociation of electrolytes like NH4OH, CH3COOH, oxalic acid, etc. can be calculated in this
manner.
Conductometric titrations 
The titrations, in which the end point or equivalence point is determined by means of conductance
measurements, are called conductometric titrations. 

Principle:
They are based on the principle that the conductance of an electrolyte solution depends upon the number of
ions, their charges and mobilities. 
As a reaction proceeds during a titration, the number of ions or concentrations of ions vary. Also, the ions of
one kind are replaced by ions of another kind, differing in the mobilities. Hence, the conductance of the
solution changes with every addition of the titrant. At the equivalence point, a sharp change in conductance is
observed. Thus, if the conductance of the solution is recorded during the course of a titration, and the
conductance plotted against the volume of titrant added, the end point can be conveniently obtained by
extrapolation of straight lines obtained and finding out the point of intersection. 
Titrations are usually carried out by taking a solution to be titrated in a beaker and in which a conductivity cell
is dipped, and connected to a conductometer. The titrant is added from a burette, the solution stirred, and the
conductance measured after each addition. Conductance is plotted against the volume of the titrant and the
end point is obtained from the intersection of two straight lines. 
Conductometric titration of a strong acid versus a strong base:
Consider the titration of a strong acid (e.g. HCl) against a strong base (e.g. NaOH).1
A known volume of a strong acid solution (e.g. HCl) is taken in a beaker and a strong base (e.g. NaOH) is
added from a burette, when the following reaction occurs. 
Na+OH− + H+Cl− Na+Cl− + H2O

The net result is H+ and OH− ions are removed as weakly ionizing water molecules. In the course of the
titration, the highly mobile H+ ions are replaced by less mobile Na+ ions.
The conductance of the solution before the commencement of the titration is high and decreases
continuously as the alkali is added. This decrease in conductance continues up to the neutralization point. 
Beyond this point, the conductance begins to increase in proportion to the excess of NaOH added, due to the
presence of highly conducting OH- ions. 
A plot of conductance of the solution versus volume of alkali added gives two straight lines. The point of
intersection of the two lines gives the neutralization point. The volume corresponding to the point of
intersection give the volume of alkali required for complete neutralization, or is the end point of the titration. 

Conductometric titration of a weak acid versus a strong base:

Consider the titration of a weak acid (e.g. CH3COOH) versus a strong base (e.g. NaOH). The weak acid is
dissociated only slightly, and has a low conductance. On addition of the base NaOH, a highly conducting salt
CH3COONa is formed. 1

CH3COOH + Na+OH− CH3COO− Na+ + H2O

The conductance of the solution therefore increases gradually till the end point. After the equivalence point,
the conductance increases sharply due to the presence of excess of highly conducting OH- ions. 
Note: Initially there is a slight decrease in the conductance due to common ion effect.

Conductometric titration of a mixture of strong and weak acid versus a strong base:
Consider a mixture of a strong acid (e.g. HCl) and a weak acid (e.g. CH3COOH) being titrated against a solution
of a strong base (e.g. NaOH). 1
As NaOH is added to the mixture of the acid solution, the strong acid, due to high ionization, is neutralized first.
The conductance of the solution starts decreasing due to replacement of H+ ion by Na+. This continues till
HCl is fully neutralized. 
At this stage, the conductance will start increasing moderately due to reaction of acetic acid with NaOH to
form CH3COONa, which is a strong electrolyte and hence highly ionized. 
After complete neutralization of CH3COOH, the conductance will show a sharp increase due to the addition of
excess of highly conducting OH- ions. Hence, two equivalence points are obtained, as shown in the figure.
Variation of conductance with dilution:
Specific conductance, κ: For strong as well as weak electrolytes κ decreases with dilution. This is because
number of ions per unit volume decreases on dilution and hence the conductance.
In the case of strong electrolytes number of ions decreases proportionally and hence κ decreases rapidly.
However in the case of weak electrolytes the decrease in the number of ions per unit volume is slightly offset
by increase in the degree of dissociation resulting in the formation of extra ions. Hence κ decreases more
gradually when compared to strong electrolytes.

Molar conductance, Λm:1

The molar conductance of an electrolyte increases with dilution and finally attains a maximum value at infinite
dilution. 
In the case of strong electrolytes there is only a slight increase in the molar conductance with dilution. In this
case, the molecules are ionized completely even in concentrated solutions and the ions per mol remain the
same on dilution. The slight observed increase in Λm for strong electrolytes is attributed to weakening of inter-
ionic forces of attraction and also reduced viscosity resulting in greater freedom for ions to move.

Strong electrolytes give a linear relationship when molar conductance is plotted against square root of
concentration. 
To explain the linear relationship between Λ0 and , Kohlrausch proposed the equation 
Λ = Λ0 − K 
Where, K is a constant. Λ0 or is called the molar conductance at infinite dilution and is defined as the molar
conductance of the electrolyte solution in which ionization is complete and ions move independent of each
other’s influence. 
The straight line can be extrapolated to meet the Y axis at Λ0. 

In the case of weak electrolytes, the molar conductance increases rapidly with dilution because the ionization
of the weak electrolyte increases with dilution and the number of ions per mole increases. Hence, a plot of Λ
versus is not linear and there is no extrapolated limiting value, and hence Λ0 cannot be obtained from the
graph. The curve can be approximated to a rectangular hyperbola. 
Λ0 for a weak electrolyte can be obtained from Kohlrausch’s law.

Kohlrausch’s law:
At infinite dilution, when dissociation is complete, each ion makes a definite contribution towards the
equivalent/molar conductance of the electrolyte irrespective of the nature of the other ion with which it is
associated and that the value of the equivalent conductance at infinite dilution for any electrolyte is given by
the sum of the contributions of the two ions. 

Λ0 = + 
Where, and are the ionic conducatnces at infinite dilution of the cation and anion respectively. 
Note: 
1. This law is valid at any dilution but is applied only at infinite dilution. 
2. This ionic conductance at infinite dilution of any ion is a constant at a given temperature whatever might be the nature of the other ion associated with it.