Conductometric Titration

Mixture of Acids Vs. Base

IISC, Bangalore

Dr. Moumita Koley

Titration Methods
Titration methods
Indicator method- not suitable i) for colored solution
ii) weak acid vs. weak base
iii) error

pH Electrode based on measurement of pH

Conductometry: method based on measurement of
electrolyte conductivity.

Introduction
Conductance: is the ability of the medium to
carry the electric current. (solution: ions, in
metal: electron)
Conduction of current :migration of positively
charged species towards the cathode and
negatively charged ones through the anode while electrons are transferred to & from the
ions at the electrode surface to complete
current path., i.e. current is carried by all ions
present in solution.

Example-Strong and Weak Electrolyte

In solution strong electrolyte, HCl
H+ + ClIn the electrolytic cell: H+ ions will move toward the
cathode and Cl- ions will move toward the anode.
At cathode: H+ + e H (Reduction) .
H + H H2
At Anode: Cl- Cl + e (Oxidation)
C l + Cl Cl2
The overall reaction is: 2 HCl H2 + Cl2 (Decomposition)

Measurement of Conductance
Conductivity: measured by
applying an alternating
electrical current (I) to two
electrodes immersed in a
solution and measuring
the resulting voltage (V)the cations migrate to the
negative electrode, the
anions to the positive
electrode and the solution
acts as an electrical
conductor.

Conductance
Conductance= reciprocal of resistance,

1
G=
R

ohm-1(seimen)

The conductivity meter in fact measures the resistance, and displays

the reading converted into conductivity

From Ohm law,

V
R=
I
V is the voltage (volts),
I is the current intensity (amperes).
R = resistance (ohm)

Expressions of Conductance
Conductance of solutions can be expressed in
different terms

Specific conductivity or Specific conductance

Equivalent conductance
Molar conductance

Specific Conductivity ()
Specific conductance or specific conductivity:
The reciprocal of specific resistance and is defined as the
conductance of one cubic centimeter (cc, mL) of a solution of an
electrolyte.

= G x cell constant
= 1/R x L / A = L/RA = l/
G = 1/ R and k = 1/

= the specific conductivity, its unit is Ohm-1cm-1 (Siemens cm-1 )

G= conductance (observed) . Cell constant= L/A;
L = the distance between the two electrode (cm)
A = the area of the electrode (cm2)
R = resistance. = specific resistance

Equivalent Conductance ()
Definition: The conductance of an electrolyte
obtained by dissolving one gram equivalent
(eq. wt.) of it in V cc of water.
=kxV
= specific conductance
V= volume of the solution in cc (mL)
containing one gram equivalent of the
electrolyte

Molar Conductance ()
Definition: The conductance of all ions
produced by dissolving one mole (one gram
molecular weight) of an electrolyte in a
certain volume, V cc of water.
=kxV
k = specific conductance
V = volume of the solution in cc (mL) containing
one mole of the electrolyte.

Effect of Dilution on Conductance

specific conductance decreases with dilution where as equivalence
/molar conductance increases-Why?.

-conductance of one cc of the electrolyte solution-dilution

decreases concentration of ions per cc specific
conductance decreases.
-increase as - products of specific conductance and the
volume of the solution containing one gram-equivalent or
one mole of the electrolyte, respectively.
- With dilution the first factor (k) decreases, while the
volume increases.
- The increase in (V) is much more than the decrease in
the first factor (k).

The conductance of the solution depends on:

1. Temperature:
It is increased by increase of temperature. 1oC increase 2%
2. Nature of ions
Velocity of ions: Size, number of charges (di-positive 2 times of mono
positive) the ion carries and other factors-related to velocity.
3. The concentration of ions:
As the number of ions increases the conductance of the solution
increases.
4. The size of the electrodes

L
k =G
A

L/A is cell constant

k is the specific conductance or conductivity
ohm-1cm-1 or seimen/cm.

The conductance of the solution depends on:

5.The magnitude of the applied electric field:
increasing applied potential between the two electrodes
increase in conductance.
6.Viscosity of the solvent:
by increasing viscosity decreasing the rate of migration,
decreasing the conductance
7. Dielectric constant of the solvent [DEC]:
Increase in DCE of media will increase conductance

Application of conductivity
Direct or absolute measurements
1. checking purity of distilled water or other chemicals.
2. determination of physical constants such as
ionization constant.

Conductometric titrations
1. Very dilute solutions.
2. Turbid and highly colored solutions.
3. Reaction which is not complete and where there is no suitable indicator,
e.g. reaction between weak acid and weak base.

Conductometric Titration
Any reaction in which the reactants differ
markedly in conductance from the products
can be, in particular, the basis of a
conductometric titration.
In such titration, the conductance of the
solution is measured after the addition of
each increment of titrant solution, and
resulting values are plotted versus volume of
the titrant.

Conductometric Titration
1. Titration of strong acid with strong base:
The reaction is represented by the following equations
e.g. H+ + Cl- + Na+ + OH- H2O + Na+ + Cl-

Weak vs. Strong

2. Very weak acid with strong base or a very
weak base with stronger acids

Mixture of Acids
Determination of mixture of hydrochloric acid
(strong acid) and acetic acid (weak acid) with
sodium hydroxide (strong base)

Advantages Vs. Disadvantages

Advantages-Easy to perform, same electrodes
for different types of titrations, easy to
maintain faster response, work in dilute,
colored and turbid solutions.
Disadvantages-not suitable for conc. Solution
(contribution of non-participant ions). Not for
complexometric or redox titrations.