Dr.

Puspendra Kumar

Conductometry

By
Dr. Puspendra Kumar
M. Pharm., Ph.D.

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 Dr. Puspendra Kumar

PRINCIPLE:
 The principle of conductometric titration is based on the fact that during the titration, one of
the ions is replaced by the other and invariably these two ions differ in the ionic conductivity
with the result that conductivity of the solution varies during the course of titration.
 The equivalence point may be located graphically by plotting the change in conductance as a
function of the volume of titrant added.
 The electrical conductance of a solution is a measure of its currents carrying capacity and
therefore determined by the total ionic strength.
 It is a non-specific property and for this reason direct conductance measurement are of little
use unless the solution contains only the electrolyte to be determined or the concentrations of
other ionic species in the solution are known.
 Conductometric titrations, in which the species in the solution are converted to non-ionic for
by neutralization, precipitation, etc. are of more value.
 Unit of Conductance is Ohm-1,Mho, Siemen.
EFFECT OF DILUTION
 The conductance produced by an ion is proportional to its concentration (at constant
temperature), but the conductance of a particular solution will in general not vary linearly
with added reagent, because of the dilution effect of water being added along with reagent
added.
 Hydrolysis of reactants or products, or partially solubility of a precipitated product, will also
cause departures from linearity.
CONDUCTANCE MEASUREMENT
 The conductance G is the reciprocal of the electrical resistance (1/R) and has the unit Siemens
(S) = Ω–1. The electrical conductivity is obtained by multiplying it with the cell constant.
Conductivity titrations only require the conductance G.
 The instrument used to measure conductance is called conductance bridge or conductometer.
 Classical circuit employed for measurement is wheatstone bridge.
 Conductance:(G) ease with which current flows per unit area of conductor per unit potential
applied & is reciprocal to resistance(R)
G=1 R

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 Dr. Puspendra Kumar

 Specific conductance (k): conductance of the body of uniform length(l) &uniform area cross
section(A)
K =CxL/A OR
K =1/R x L/A
 Molar conductance: (λ) Conductance of a solution containing 1 mole of the solute in 1000
ml of the solution which placed between two parallel electrodes which are 1 cm apart
λ = 1000 C.
 Equivalent conductance: (λeq): specific conductance of the solution containing 1gm
equivalent of solute in 1000 ml of solution.
λeq =1000k Ceq
TYPES OF CONDUCTOMETRIC TITRATIONS
1. Acid –base or neutral titrations
Strong acid-strong base: Eg: HCl vs NaOH
Strong acid-weak base: Eg: HCl vs NH4OH
Weak acid-strong base: Eg: CH3COOH vs NaOH
Weak acid -weak base: Eg: CH3COOH vs NH4OH
2. Replacement or displacement titrations
3. Redox titrations
4. Precipitation titrations
5. Complexometric titrations
6. Non-aqueous titrations

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 Dr. Puspendra Kumar

 Strong acid strong base:

Fall in conductance due to replacement of high conductivity Hydrogen ions by poor
conductivity sodium ions
Rise in conductance due to increase in hydroxyl ions

 Strong acid- weak base:

Fall in conductance due to replacement of hydrogen by ammonium ions.
Conductance remains constant due to supression of NH40H by NH4Cl.

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 Dr. Puspendra Kumar

 Weak acid –Strong base:

Initial decrease in conductance followed by increase due to NaOH
Steep rise due to excess of NaOH

 Weak acid- weak base:

Increase in conductance due to excess of CH3COOH
Constant conductance due to supression of NH4OH by CH3COOH

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 Dr. Puspendra Kumar

MERITS
1. Does not require indicators since change in conductance is measured by conductometer
2. Suitable for coloured solutions
3. Since end point is determined by graphical means accurate results are obtained with minimum
error
4. Used for analysis of turbid suspensions, weak acids, weak bases, mix of weak & strong acids
DEMERITS
1. Increased level of salts in solution masks the conductivity changes , in such cases it does not
give accurate results
2. Application of conductometric titrations to redox systems is limited because, high
concentrations of hydronium ions in the solution tends to mask the changes in conductance.
INSTRUMENTATION
The instrument used for measurement of conductance are know as conductometers
It consists of:
1. Current source: Alternating current source.
 Mechanical high frequency AC generator.
 When electrical potential is applied across electrodes two process occurs.
 Ions accumulate near the electrodes.
 Transfer of charge through the interface.
2. Conductivity cells: Wide mouthed cells, Cell for reactions producing precipitates,Dip type
cells.
 Made of pyrex or quartz and are fitted with two platinum electrodes.
 Should be placed in vessel containing water to maintain constant temperature
3. Electrodes
 Platinum sheets, each of 1 cm2 are fixed at distance of 1 cm
 The surface is coated with platinum black to avoid polarization effects and increase
effective surface area.
 Platinization of electrodes is done by coating solution of 3% chlorplatinic acid and lead
acetate on it to get uniform coating
 Electrodes usage depends on conductivity and concentration
 If conc is low then electrodes should be largely and closely packed.

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 Dr. Puspendra Kumar

APPLICATIONS
 Check water pollution in rivers and lakes
 Alkalinity of fresh water
 Salinity of sea water (oceanography)
 Deuterium ion concentration in water- deuterium mixture
 Food microbiology- for tracing micro organisms
 Tracing antibiotics
 Estimate ash content in sugar juices
 Purity of distilled and de - ionized water can determined
 Solubility of sparingly soluble salts like AgCl,BaSO 4 can be detected
 Determination of atmospheric SO2.
 Estimation of vanillin in vanilla flavor.

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