Conductometry

CONDUCTOMETRY
 Electrolytes are the substances that form ions in solution which conduct an electric
current. E.g., Sodium chloride, Copper sulphate and Potassium nitrate
 Non-electrolytes, on the other hand, are neutral molecules in solution. Their water-
solutions do not conduct an electric current. E.g., Sugar, alcohol and glycerol
Electrolysis
The phenomenon of breakdown of an electrolyte by passing electric current through its
solution is termed Electrolysis.
 The process of electrolysis is carried in an apparatus called the Electrolytic cell. The
cell contains water-solution of an electrolyte in which two electrodes are dipped.
These rods are connected to the two terminals of a battery (source of electricity).
 The electrode connected to the positive terminal of the battery attracts the negative
ions (anions) and is called anode.
 The other electrode connected to the negative end of the battery attracts the positive
ions (cations) and is called cathode.
Fig. The mechanism of electrolysis/Conductivity cell
Mechanism of Electrolysis
 The cations migrate to the cathode and form a neutral atom by accepting electrons
from it.
 The anions migrate to the anode and yield a neutral particle by transfer of electrons to
it.
Example: Let us consider the electrolysis of hydrochloric acid as an example.
In solution, HCl is ionised,
HCl → H+ + Cl−
At cathode:
H+ + e– → H ......(Reduction, gain of electrons)
At anode:
Cl– → Cl + e− ......(Oxidation, loss of electrons)
The net effect of the process is the decomposition of HCl into hydrogen and chlorine gases.
The overall reaction is:
2HCl → H2 + Cl2 ......(Decomposition)
Conductometric Titrations
 Titrations in which conductance measurements are made in determining the end-point

of acid-alkali reactions, some displacement reactions or precipitation reactions are
called conductometric titrations.
 In these titrations, the conductance of a solution at a constant temperature
depends upon the number of ions present in it and their mobility.
 For this purpose, the titrant is added from a burette into a measured volume of the
solution to be titrated which is taken in a conductance cell. The conductance readings
corresponding to the various additions are plotted against the volume of the titrant.
 In this way two linear curves are obtained, the point of intersection of which is the
end-point.
(1) Titration of a Strong acid against a Strong base
 Consider the reaction in which hydrochloric acid solution is titrated against a solution
of sodium hydroxide. Take 20 ml of the acid solution in the conductance cell placed
in a thermostat and determine its conductance. Now add 1 ml sodium hydroxide
solution from the burette at a time. After each addition, determine the conductance of
the solution after through mixing and plot the conductance of the solution against the
volume of the alkali added.
 It will be observed that the points lie on two lines which are almost straight. The point
of intersection of the interpolated lines will be the end point and the volume of alkali
corresponding to this point is the volume of alkali required to neutralise 20 ml of the
acid.
 The reason for this is that before the addition of alkali, the conductance of the solution
is due to presence of H+ and Cl– ions. Since hydrogen ions possess the greatest
mobility of any ion, the greater part of the conductance is due to it. As alkali solution
is added, the hydrogen ions are removed by combination with the hydroxyl ions.
H+ + Cl– + Na+ + OH– → Na+ + Cl– + H2O
 As a result of this, the conductance of the solution decreases and continues to fall with
every subsequent addition of alkali till the end-point is reached. After the equivalence
point, further addition of sodium hydroxide solution results in an increase of
conductance since the hydroxyl ions are no longer removed in the chemical reaction
in the form of ionised water. The point of minimum conductance, therefore,
coincides with the end-point of the titration.
(2) Titration of a Weak acid against a Strong alkali
When a weak acid like acetic acid is titrated against a strong alkali like sodium hydroxide,
the initial conductance of the solution is low because of the poor dissociation of the weak
acid. On adding alkali, highly ionised sodium acetate is formed. The acetate ions at first
tend to suppress the ionisation of acetic acid still further due to Common Ion Effect but
after a while the conductance begins to increase because the conducting power of highly
ionised salt exceeds that of the weak acid.
CH3COOH + Na+ + OH– → CH3COO– + Na+ + H2O
Immediately after the end point, further addition of sodium hydroxide introduces the fast
moving hydroxyl ions. Thus, the conductance value shows a sharp increase. The point of
intersection of the two curves, gives the end-point.
H+ + Cl– + NH4OH → NH4+ + Cl– + H2O
After the end-point has been reached, the addition of ammonium hydroxide will not cause
any appreciable change in conductance value as it is a weak electrolyte and its
conductance is very small compared with that of the acid or its salt.
(3) Titration of a Strong acid against a Weak base
 The curve obtained for the titration of a strong acid against a weak base is shown
in Fig. 25.11.
 In this case, the conductance of the solution will first decrease due to the fixing up
of the fast moving H+ ions and their replacement by slow moving NH4+ ions.
(4) Titration of a Weak acid against a Weak base
 The conductometric method is particularly suitable as such titrations do not give a

sharp end-point with indicators.
 Consider the titration of acetic acid with ammonium hydroxide. The initial
conductance of the solution in this case is also low due to the poor dissociation of
the weak acid. But it starts increasing as the salt CH3COONH4 is formed.
 After the equivalence point, the conductivity remains almost constant because the
free base NH4OH is a weak electrolyte. The end-point is quite sharp.
Applications of conductometric titrations
 To determine end point in case of acid-base and precipitation titrations.

 Purity of water can be checked by conductometric titrations.
 Salt content of water can be checked by this method.
 Used for tracing microorganisms in food.
 It is also used to check alkalinity of water.
 To study water pollution of rivers and lakes

Conductometry

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CONDUCTOMETRY

Fig. The mechanism of electrolysis/Conductivity cell

 Titrations in which conductance measurements are made in determining the end-point

(1) Titration of a Strong acid against a Strong base

H+ + Cl– + Na+ + OH– → Na+ + Cl– + H2O

CH3COOH + Na+ + OH– → CH3COO– + Na+ + H2O

H+ + Cl– + NH4OH → NH4+ + Cl– + H2O

(3) Titration of a Strong acid against a Weak base

(4) Titration of a Weak acid against a Weak base

 The conductometric method is particularly suitable as such titrations do not give a

Applications of conductometric titrations

 To determine end point in case of acid-base and precipitation titrations.

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