CONDUCTOMETRY

BY

DR.RAMESH KUMARI DASGUPTA BENGAL SCHOOL OF TEHCNOLOGY

Conductometry is an electrochemical method of analysis used for the
determination or measurement of the electrical conductance of an
electrolyte solution by means of a conductometer.
Principle
Conductimetry is based on the principle of determination of changes in
conductivity. Changes in conductance due to the replacement of ions in
the each other. Ion conductivity is different for different ions.
Conductance
Flow of electricity through the electrolyte solution due to the migration
of ions by applying potential difference between two electrodes.
Cathode(-ve charged) will attract cations(+ve charged)
Anode(+ve charged) will attract anions(-ve charged).
Electric conductivity of an electrolyte solution depends on :
Type of ions (cations, anions, singly or doubly charged
Concentration of ions
Temperature
Mobility of ions
The main principle involved in this method is that the movement of the
ions creates the electrical conductivity. The movement of the ions is
mainly depended on the concentration of the ions.
The electric conductance in accordance with ohms law which states that
the strength of current (i) passing through conductor is directly
proportional to potential difference & inversely to resistance.
i =V/R
Conductance is denoted by G and it is reciprocal of resistance(R).
G = 1⁄ R. Its unit is mhos or Siemens.
Specific conductance
Resistance of a substance is directly proportional to the length(l) and
inversely proportional to the cross sectional area(a) of conductor
through which the conductivity take place.
R ∞ l/a R=ρX l/a ρ- specific resistance
If length is 1meter and area is 1 meter square then
R=1/1/Xρ m/sqm Xρ
R=ρ

Specific resistance(ρ) is resistance offered by a conductor of unit length

and having unit cross section. And units are ohm/cm.
Specific conductance is a conductivity offered by a conductor of unit
length and having unit cross section. And units are mhos
Specific conductance is reciprocal of specific resistance is denoted by
kappa K=1/ρ putting the value of ρ
k=1/a/l X R
K=l/a X1/R
K=l/a X G
Unit for specific conductance
K=l/a X G
m/m2 X siemens =Siemens/meter
Equivalent conductance: (^eq)- is conductivity of a solution containing 1
gram equiv1lent of solute between electrodes 1 meter apart and 1m sq.
meter surface area and volume is 1m3
G=K= ^eq
^eq= KX1/conc
if 1 equivalent solution is taken then K= ^eq unit are siemen m sq./
gram equivalent.
Molar conductivity (µv)- conductance of 1 molar solution is molar
conductance.
µv=1/cm if molarity is 1 then
µv=k1/1, µv=k
Units= Siemen m2/ mole
Factors effecting conductance
The conductance of the solution depends on:
Temperature: It is increased by increase of temperature.
Nature of ions: size, molecular weight, number of charges the ion carries
and other factors
The concentration of ions: As the number of ions increases the
conductance of the solution increases.
The size of the electrodes
Instrument
conductivity

-
burette

Digital -. ; Titrant
display 2.123 - -
- .;- - - - ; ;-
..... -
Power -- - -- - - - -
switch - - - - - -- - - - --- - -
calibrator - - - - --- ----- ------- --
Anode cathode
- - -- -- ---- -- - - - - - - -
-------- -. - .- .. .. . Megnatic stirrer

conductivity meter

NH4OH is taken in burette and CH3COOH is taken in beaker . Slowly drop

by drop NH4OH is added and conductance is noted.
Current source
1. Alternative current source is used
2. High frequency alternative generator is employed.
3. Electric potential is applied, ions will be transferred ultimately
conductance takes place
4.DC current is not employed in conductance measurement because
electrodes becomes polarised leading to high cell resistance.
Conductivity meter
1. Digital display
2. Calibrator
3. Power supply
Conductivity cell
It is made up of Pyrex or quads fitted with two electrodes
1.Cathode(-ve charged) will attract cations(+ve charged)
2.Anode(+ve charged) will attract anions(-ve charged).
Electrodes
1.Electrodes are made up of platinum. Electrodes are coated with
Platinum black.( to avoided polarization, to increase surface area)
Platinisation of electrodes is done by coating solution of 3%
chlorplatinic acid and lead acetate on it to get uniform coating.
2. Area of surface of these electrode in 1cm square
3. Distance between these electrodes in 1cm.
4. Electrodes usage depends on conductivity and concentration.
5. If conc is low then electrodes should be largely and closely packed.
The instrument used to measure conductance is called conductance
bridge or conductometer.
1.Classical circuit employed for measurement is wheatstone bridge.
2. Various types are:
• Kohlrausch conductance bridge
• Direct reading conductance bridge
• Phillips conductance bridge
• Mullard’s conductance bridge
• Pye’s conductance bridge Measurement
 R1 R2

. .. .- ,. .,
- -.
. ,.- . -- .. -- .-
.

L M N

Conductometer circuit
Hence, conductivity of unknown solution:
1 ⁄ R2 =NL ⁄ ML × R1
The measured conductivity (1/R1) is not always equal to the specific
conductivity of solution , because the physical configuration of platinum
electrode i.e, length and area of electrodes varies from one another.
Hence conductivity of solution is obtained by calculating a factor called
“cell constant”.
Cell constant: Defined as ratio of distance between the two electrodes(l)
to the area of electrodes(a) Therefore, θ =l ⁄ A
Conductometric titrations
Conductometric Titrations Principle
1. The determination of end point of a titration by means of
conductivity measurements is known as conductometric titration.
2.During the course of titration, the conductivity of the solution
changes, since there is change in the number and the mobility of ions.
3.At the end point of the titration, there is a sharp change in the
conductivity of a solution shown by the intersection of the lines in the
graph of conductivity Vs volume of titrant added.
Before going to the Conductivity curve we should know the molar
conductivity of various ions.(Siemen cm2/ mpl) H+ -349.6
OH- -199.1
Cl- -76.35
NH4+ -73.5
NO3- -71.46
-61.9
Ag+
50.1
Na+
COO- 40.9
Types of conductometric titrations
1.Acid –base or neutral titrations
1.Strong Acid with a Strong Base HCl+NaOH NaCl+H2O
Vessel+ burrette

When the base is added in HCl solution, the conductance falls due to the
replacement of hydrogen ions by the added cation as H+ ions react with
OH − ions to form undissociated water. After the equivalence point, the
conductance increases due to the large conductivity of OH- ions

conductance
Equivqlent point

Volumr of NaOH
2.Strong Acid with a Weak Base
HCl with dilute ammonia • Initially the conductance is high and then it
decreases due to the replacement of H+. • But after the endpoint has
been reached the graph becomes almost horizontal, since the excess
aqueous ammonia is not appreciably ionized in the presence of
ammonium chloride HCl+NH4OH NH4Cl +H2O
NH4Cl NH4+ +Cl-
NH4OH NH4+ +OH-

conductance

Equivqlent point

Volume solution of dilute of NH4OH

3 Weak Acid with a Strong Base
Acetic acid with NaOH • Initially the conductance is low due to the
ionization of acetic acid, followed by increase due to NaOH • Beyond the
equivalence point, steep rise due to excess of NaOH.

CH3COOH+NaOH CH3COONa+H2O

conductance

Equivelent point

Volume NAOH
4. Weak Acid with a Weak Base
Acetic acid with dilute ammonia • The nature of curve before the
equivalence point is similar to the curve obtained by titrating weak acid
against strong base. • After the equivalence point, conductance virtually
remains same as the weak base which is being added is feebly ionized
and, therefore, is not much conducting due to conmen ion effect
CH3COOH+NH4OH CH3COONH4+H2O
CH3COONH4 CH3COO- +NH4+
NH4OH NH4+ +OH_

conductance

Eqivqlet point
Applications :
1. Check water pollution in rivers and lakes
2. Alkalinity of fresh water
3. Salinity of sea water (oceanography)
4. Deuterium ion concentration in water- deuterium mixture
5. Food microbiology- for tracing micro organisms
6. Tracing antibiotics
7. Estimate ash content in sugar juices
8. Purity of distilled and de - ionised water can determined
9. Solubility of sparingly soluble salts like AgCl,BaSo4 can be detected
10.Determination of atmospheric o2,etimation of vanillin in vanilla
flavour.