Lecturer Notes –Electrochemistry

Lecturer Session No: 07 – Topic: Conductometric titrations (acid-base – HCI vs, NaOH)
titration).

Conductometric titration of strong acid against a strong base:

The course of neutralization of a strong acid by a strong base can be determined by

condutometric method (without the use of indicator). The principle of conductometric titration
is that the conductance of a reaction follows a specific trend before the completion of the
reaction and it follows a different trend after the completion of the reaction. From the change
in trends, the end point of the reaction can be determined graphically. The model graph for
this titration is shown in fig. Conductance (mho)
Conductance (mho)

Vol. of titrant (ml) Vol. of titrant (ml)

Neutralisation titration Precipitation titration

In the case of neutralization of strong acid (say HCl) by a strong base (say NaOH), the
conductance of HCl (taken in a beaker) is determined at regular additions of NaOH, from the
burette.
H+Cl- + Na+OH- → Na+Cl- + H2O

The conductance of the reaction mixture (HCl) decreases till the end point because lighter
protons (H+) are replaced by heavier Na+ ions, whose mobility is lower than that of protons.
The conductance of the reaction mixture increases after the end point because heavier chloride
ions (Cl- whose atomic mass is 35.5) are replaced by lighter hydroxyl (OH-) ions (with mass
17), whose mobility is higher than that of chloride ions. A plot of the conductance of the
reaction mixture against the volume of the titrant gives two straight lines of opposite slopes.
The point of intersection of the straight lines is the end point.
Conductometric titration of weak acid against a strong base:

The course of neutralization of a weak acid by a strong base can be determined by

condutometric method (without the use of indicator). The principle of conductometric titration
is that the conductance of a reaction follows a specific trend before the completion of the
reaction and it follows a different trend after the completion of the reaction. From the change
in trends, the end point of the reaction can be determined graphically. In the case of
neutralization of weak acid (say CH3COOH) by a strong base (say NaOH), the conductance of
CH3COOH (taken in a beaker) is determined at regular additions of NaOH, from a burette.
CH3COOH + Na+OH- → CH3COO-Na+ + H2O
(weak) (feebly ionized)

The conductance of the reaction mixture (CH3COOH) is initially low because of the poor
dissociation of the weak electrolyte. On the addition of strong alkali, the strong electrolyte,
sodium acetate is formed. It tends to suppress the ionoization of acetic acid, due to common
ion effect. Further there is increase in conductance of the reaction mixture, because of the larger
proportion of the strong electrolyte, CH3COONa. Immediately after the end point, the
conductance increases sharply because of the fast moving hydroxyl ions compared to the
acetate ions. A plot of the conductance of the reaction mixture against the volume of the titrant
gives two straight lines of positive, but varying slopes. The point of intersection of the straight
lines is the end point.

Conductometric titration of strong acid against a weak base:

The course of neutralization of a strong acid by a weak base can be determined by

condutometric method (without the use of indicator). The principle of conductometric titration
is that the conductance of a reaction follows a specific trend before the completion of the
reaction and it follows a different trend after the completion of the reaction. From the change
in trends, the end point of the reaction can be determined graphically. In the case of
neutralization of strong acid (say HCl) by a weak base (say NH4OH), the conductance of HCl
(taken in a beaker) is determined at regular additions of NH4OH, from a burette.
H+Cl- + NH4OH → NH4+Cl- + H2O
(weak)
The conductance of the reaction mixture (HCl) decreases sharply, with the addition of the weak
base, ammonium hydroxide, because of the formation of the salt ammonim chloride, which is
a weaker electrolyte than HCl. Immediately after the end point, the conductance decreases
further but slowly because ammonium hydroxide is a still weaker electrolyte than ammonium
chloride.A plot of the conductance of the reaction mixture against the volume of the titrant
gives two straight lines of negative, but varying slopes. The point of intersection of the straight
lines is the end point.

Conductometric titration of weak acid against a weak base:

The course of neutralization of a weak acid by a weak base can be determined by condutometric
method (without the use of indicator). The principle of conductometric titration is that the
conductance of a reaction follows a specific trend before the completion of the reaction and it
follows a different trend after the completion of the reaction. From the change in trends, the
end point of the reaction can be determined graphically. In the case of neutralization of weak
acid (say CH3COOH) by a weak base (say NH4OH), the conductance of CH3COOH (taken in
a beaker) is determined at regular additions of NH4OH, from a burette.
CH3COOH + NH4OH → CH3COONH4 + H2O
(weak)

The conductance of the reaction mixture (CH3COOH) increases gradually with the addition of
the weak base, ammonium hydroxide, because of the formation of the salt ammonium acetate.
Immediately after the end point, the conductance remains almost constant, because the titrant,
ammonium hydroxide is a weake electrolyte. A plot of the conductance of the reaction mixture
against the volume of the titrant gives first a sloping line and a line parallel to one of the co-
ordinate axes. The point of intersection of the straight lines is the end point. This method is
quite suitable when there is no proper indicator available, particularly this case.