2.

Conductometry

Introduction
This is a method of analysis based on measuring electrolytic
conductance
Conductance: is the ability of the medium to carry the electric
current.
Electric current passes through metallic conductors, e.g. wires of
iron or copper in the form of electron flow. But conduction of
electricity through an electrolyte solution involves migration of
positively charged species towards the cathode and negatively
charged ones through the anode, i.e. current is carried by all
ions present in solution.
The conductance of the solution is a reciprocal of its resistance
and has the units of ohm-1 (seimen). That is,
G

From Ohms law

1
R

E is the potential difference, i is the current intensity.

R

E
i

The conductance of the solution depends on:

1. Temperature:
It is increased by increase of temperature. An increase of
temperature by 1oC is accompanied by 2 % increase in
conductance for this response the measurements must be
carried out at constant temperature using thermostatically
controlled water bath or the conductometer used has special
device which continuously calibrates for the temperature
increase during measurements.
2. Nature of ions
The velocity by which ions move towards the electrodes
carrying the electric current varies according to their nature, i.e.
size, molecular weight, number of charges the ion carries and
other factors.
3. The concentration of ions:
The electrical conductance of a solution is a summation of
contribution from all ions present. It depends on the number of
ion/unit volume of solution and their nature i.e. each ion presents
itself independently. As the number of ions increases the
conductance of the solution increases.

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Instrumental analysis

4. The size of the electrodes

Conductance is directly proportional to the cross sectional area
A and inversely proportional to the length L of a uniform
conductor.
GK

A
L

The conductance of electrolyte solution can be calculated

from :
L
A
K is the specific conductance or conductivity, it is the
K G

conductance of a cube of liquid on centimeter on a side.

If A and L are measured by centimeter, or of cubic meter if A
and L are taken by meter. The dimensions of K is 1/ohm.cm or
ohm-1cm-1 or seimen/cm.-1m-1)
L/A is known by the cell constant, K, is a constant value for
specific solution it changes if we change the concentration of
the solution it decreases by dilution as fewer ion will be present
per cubic centimeter.
Equivalent conductance
It is defined as the conductance of one gram equivalent of
solute contained between electrodes spaced one centimeter
apart.

For a substance
38

1000 K
C
Instrumental analysis

Where C is the concentration in gram equivalent per liter.

Equivalent ionic conductance:
At infinite dilution, interactions become nil; the overall
conductance of the solution consists of the sum of the individual
equivalent ionic conductance
o = +o + -o
Table. Equivalent Conductivity at Infinite Dilution at 250C
Cation
H+
Li+
Na+
K+
Rb+
Cs+

350
38.7
50.1
73.5
76.4
76.8

Anion
OHClBrNO3CH3COOClO4 SO42-

198
76.3
78.4
71.4
40.9
68
80

Where +o and -o are equivalent ionic conductance of the

cation and anion of the salt at infinite dilution. Individual ionic
conductance can be determined from other electrolytic
measurements.
Instrumentments used in conductometric determination
To carry out conductometric measurement it is necessary to
measure the resistance of the solution and the conductance is
i/r.

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Instrumental analysis

The instrument consists of two parts:

1. A mean to measure the resistance and then converts
it to conductivity unit this called conductivity bridge.
2. Conductance cell; in which the solution to be
measured is filled.
1. Conductivity bridge (Kohlrausch Bridge)
It is formed of:
a- Whetstone Bridge.
b- An oscillator.
The whetstone bridge shown in
the next figure used here to
measurement of resistance. The
power source S provides an ac
current at a potential of 6 to 10
V.
The unknown resistance Rx is
placed in the upper-left arm of the bridge.
A null detector ND (ac galvanometer) is employed to indicate
an absence of current between D and C.
To measure Rx the position of C is adjusted to a minimum as
indicated by the null detector (the position of C will change
rapidly and automatically till the balance point, where no
current is detected). At balance

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Instrumental analysis

Rs
R
x
R CB R AC

RX

R s R AC
R CB

1 BC
.
AB 100
R AC

1
x

R 1 100 - x

R x Rs

AC
BC

BC X

2. Cells used in conductometric measurements:

The cell is formed of two parallel sheets of platinum. Fixed in
position by being sealed into the sides of the measuring cell. The
distance between the two electrodes must be constant during
the

determination.

For a given cell with fixed electrodes the ratio of L/A . cm is a

constant known as cell constant. It is determined for each cell
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Instrumental analysis

using solutions of known conductivity. The cell must be dipped in

thermostatically controlled water bath or the instrumental has a
temperature calibration device.

Application of conductivity

1. Direct or absolute measurements:

This is used in industry for checking purity of distilled water or
other chemicals. Also for determination of physical constants
such as ionisation constant.
In this method a series of standard solutions of extra pure grade
of the substance to be determined is prepared, the conductivity
is determined and a calibration curve is plotted representing
conductivity against concentration.
A solution of the substance to be tested is prepared and
checked from conductivity calibration curve.
2. Conductometric titrations
A conductometric titration involves measurement of the
conductivity after successive addition of the reagent. The end
point is obtained from a plot of conductivity against ml of titrant.
Here it is the change of conductivity of the solution during the
course of reaction which is important.
The most important advantages of this method are that it can
be used for determination of:
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Instrumental analysis

a- Turbid and highly coloured solutions.

b- Very dilute solutions.
c- Reaction which is not complete and where there is no
suitable indicator, e.g. reaction between weak acid
and weak base.
Precaution to be considered in conductometric titrations:
1. Upon carrying on titration the titrant used should be at
least 10 times concentrated as the solution to be determined,
e.g. on determination of 0.01 N hydrochloric acid the titrant
sodium hydroxide should be at least 0.01 N. By this way dilution
that takes place during titration is minimum and this is
necessary because conductivity decrease with dilution.
However a correction factor must be used to compensate for
this dilution.
Correction factor

Vi Vt
Vi

Where; Vi = initial volume of the solution

Vt = titrant volume added.
2. Avoid the presence of externous ions which will not enter
the reaction such as the presence of buffer ort concentrated
acids. These ions will increase the initial conductivity and the
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Instrumental analysis

change in it during the titration will be comparatively small

and cannot be accurately observed.
3. The method is suitable for detection of end point in
neutralization, complexation and precipitation reactions but
not redox reaction, as there is no electron transfer at the
electrode surface.
Neutralization titrations:
a-

Titration of strong acid with strong base:

The reaction is represented by the following equations

H+ + X- + M+ + OH- H2O + X- + M+
e.g. H+ + Cl- + Na+ + OH- H2O + Na+ + Cl-

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Instrumental analysis

Initial conductivity is high as it is that of HCl H+ + Cl- (mobility,

for H+ = 350 and for Cl- = 76) upon addition of NaOH (H+ + OH
H2O) water, which is weakly ionized is formed, hydrogen ion is
removed from the medium and sodium ions added, i.e.
hydrogen ions are replaced with sodium ions which has 43
mobility so decrease in conductivity occurs this will continue till
the end point. Beyond the end point there is excess sodium and
hydroxide ions with 43 and 198 mobility. So, there is a continuous
increase in conductivity and the curve will have a V shape the
end point is the minimum of the curve.
In ideal condition the two arms are straight and end point is the
point of intersection. The slope of the curve depends on the ratio
of mobility of sodium to hydrogen ions and on the initial
concentration of the sample the higher the concentration the
sharper the curve.
In many cases the curve minimum is blunt and the end point is
obtained by extrapolation of the curve, this curvature increases
with dilution and a usage of correction factor. The more
concentrated the solution the sharper will be the change.

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Instrumental analysis

b) Very weak acid with strong base or a very weak base with
stronger acids
Very weak acids such as phenols, boric acid or those which their
salts are coloured also weak bases as alkaloids, amines,
xanthenes dyes can be determined by this method. The initial
conductance is low as solute is weakly ionizable and minute
amount of ions present to conduct electric current. An example
of this type of titration, determination of boric acid (Ka= 6x10-10)
with sodium hydroxide. This reaction is so incomplete that a
potentiometric or visual indicator end point is unsatisfactory.
Before titration the conductivity is low due to small amount of
hydro-gen and borate ions obtained from ionization of boric
acid, upon titration with sodium hydroxide water is formed which
is less ionizable than boric acid but sodium ion will be added and
slight decrease in conductivity occurs, but since a salt (sodium
borate) is formed a buffer is rapidly established that imparts to
the solution relatively small and nearly constant hydrogen ion
concentration. The added hydroxides ions are consumed by this
buffer and thus do not contribute to the conductivity.
A gradual increase in conductivity occurs due to the increase in
sodium and borate ions.

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Instrumental analysis

At and beyond the equivalent point addition of base causes

rapid increase of conductivity due to added sodium and
hydroxide ions. In case of moderately weak acid such as acetic
acid (Ka = 1.8 x 10-5) the solution initially has a moderate
concentration of hydrogen ions. Addition of base results in
establishment of buffer system. The decrease conductivity due
to decrease of hydrogen ion concentration is balanced by its
increase due to formation of sodium acetate (completely
ionizable) and nearly a horizontal line is obtained. Beyond the
equivalence point there is a sudden increase in conductivity due
to addition of hydroxide and sodium ion from sodium hydroxide.

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Instrumental analysis

c) Determination of mixture of hydrochloric acid (strong acid)

and acetic acid (weak acid) with sodium hydroxide (strong
base)
The following figure represents the titration curve obtained
upon determination of a mixture of hydrochloric acid and acetic
acid with sodium hydroxide:
The initial conductivity is high it is due to hydrochloric acid which
by common ion effect suppress the ionization of acetic acid. So
a rapid decrease in conductivity occurs upon titration due to
replacement of hydrogen ions with 350 mobility by sodium ion
with 43 mobility till all hydrogen ions from hydrochloric acid are
neutralized. Acetic acid will thus ionize and react with sodium
hydroxide and change in conductivity occurs as described in
the previous paragraph.

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Instrumental analysis