DETERMINATION OF CONDUCTIVITY OF

GIVEN ELECTROLYTES AT INFINITE

DILUTION AT DIFFERENT TEMPERATURES
& THEIR CORELATION WITH THE
VISCOSITIES OF MEDIA
THEORY:
CONDUCTANCE
Conductivity is the ability of a solution, a metal or a gas in brief all
materials - to pass an electric current. In solutions the
current is carried
by cations and anions whereas in metals it is carried by
electrons.
Or
The reciprocal of the resistance is
called conductance. It is denoted by C.
C=1/R
Resistance refers to the opposition
to the flow of current. For a conductor of uniform cross
section(a)
and length (l); Resistance R,

R I: R l/a: R=l/a
Where is called resistivity or
specific resistance.
TYPES OF CONDUCTIVITY:
Specific Conductivity (conductance)
Specific conductivity of K of a solution is the
conductance of a solution whose length is one cm & area
of cross section is 1 cm2
R = l/a
= ohm.cm2/cm = ohm.cm
The specific conductivity K is the reciprocal of specific
resistance
K =1/
Units: ohm-1 cm-1 or Siemen/cm
Equivalent conductance
equivalent conductance is the conductance of all the
ions produced from one gram equivalent of the
electrolyte dissolved in Vcm3 of the solution, when the
distance b/w the electrode is 1 cm & area of electrode is
so large that whole of the solution is contained b/w them
Mathematically

=KV
= K . 1000/C

 = K. 1000/normality
Units: ohm-1.cm2(g eq)-1 or S.cm2(g eq)-1
Molar conductance
it is the conductivity of a solution produced by the
conductance of all ions produced by one mole of the
electrolyte dissolved in V cm3 of solution when the
distance b/w the electrodes is 1cm & area of the
electrode is so large that whole of the solution is
contained b/w them
m=K.V
m=K.1000/C=K .1000/molarity
Units: ohm-1cm2mol-1
ELECTROLYTES
Electrolytes are substances containing ions, i.e. solutions
of ionic salts or of compounds that ionise in solution. The
ions formed in solution are responsible for carrying the
electric current. Electrolytes include acids, bases and
salts and can be either strong or weak. Most conductive
solutions measured are aqueous solutions, as water has
the capability of stabilising the ions formed by a process
called solvation.

Strong electrolytes
Strong electrolytes are substances that are fully ionised in
solution. As a result, the concentration of ions in solution
is proportional to the concentration of the electrolyte

added. They include ionic solids and strong acids, for

example HCl.
Solutions of strong electrolytes conduct electricity
because the positive and negative ions can migrate
largely independently under the influence of an electric
field.

Weak electrolytes
Weak electrolytes are substances that are not fully
ionised in solution. For example, acetic acid partially
dissociates into acetate ions and hydrogen ions, so that
an acetic acid solution contains both molecules and ions.
A solution of a weak electrolyte can conduct electricity,
but usually not as well as a strong electrolyte because
there are fewer ions to carry the charge from one
electrode to the other.
How is conductivity measured?
Conductivity may be measured by applying an alternating
electrical current (I) to two electrodes immersed in a
solution and measuring the resulting voltage (V). During
this process, the cations migrate to the negative
electrode, the anions to the positive electrode and the
solution acts as an electrical conductor.
CALIBRATION OF CONDUCTIVITY METER
Calibration is important because the result is the correct
value of the cell constant in working conditions. The cell
constant is a factor that is used to convert the measured
conductance to conductivity.

Conductivity* (Scm-1) = cell constant (cm-1) x

conductance (S)
It is determined by the geometry of the cell, but in
practical terms can only be measured using a standard of
known conductivity, for example KCl 0.01 M solution. The
cell constant changes with time. Some modifications can
occur due to contamination or due to physical-chemical
modification in case of platinised cells. It is therefore
recommended to calibrate the cell at least once a week.
However, if platinised cell is used, it is advisable to
perform a daily conductivity measurement in a standard.
If the result obtained is in accordance with the theoretical
value, continue measurements. If not, cell needs to be
cleaned (if non-platinised) or replatinised (if platinised).
For high-precision measurements, it is necessary to
determine the cell constant by performing a calibration
measurement on a standard thermostated at the desired
temperature.

FACTORS DETERMINING THE CONDUCTANCE OF

AN ELECTROLYTE
How well a solution conducts electricity depends on a
number of factors:
Concentration.

Conductivity increases with increase in concentration of

analyte.
Nature of electrolyte.
The conductivity changes with the electrolyte nature.
Temperature
Conductivity measurements are temperature dependent,
if the temperature increases, conductivity increases. For
example the conductivity measured in a 0.01 N KCl
solution at 20C is 1.273 mS/cm whereas, at 25C, it is
1.409 mS/cm.
Dilution factor
Specific conductance decreases with dilution. The reason
is that, the number of current carrying particles i.e ions
cm-3nof solution becomes less at low concentration due to
dilution. No doubt the degree of dissociation increases
with dilution but the number of ions per cm3 is decreased
to such an extent that even a complete dissociation does
not produce as many ions per cm3 as are present before
dilution.
The equivalent conductance increases with dilution &
finally attains a maximum value at infinite dilution. The
reason is that equivalent conductance is the product of
specific conductance & volume of the solution containing
one gram equivalent of an electrolyte.
= K.V

The decreasing value of specific conductance due to

dilution is more than compensated by increasing value of
V & so the value of increases with dilution.

VARIATION OF CONDUCTANCE WITH

CONCENTRATION OF STRONG & WEAK
ELECTROLYTES
Equivalent conductance of an electrolyte increases on
dilution.

Two types of graphs i.e for strong & weak electrolytes is

shown above;
1. In the graph of strong electrolytes like HCl & KCl, the
equivalent conductance approaches a certain limiting
value at which the solution is so dilute that the
concentration approaches zero. This is the value of
equivalent conductance at infinite dilution. It is

denoted by we get its value by the extraplotation

of graph.
2. In cae of weak electrolytes like CH3COOH, there is no
limiting value even when the concentration
approaches to zero. So equivalent conductance of a
weak electrolyte at zero concentration can not be
obtained by extraplotation of curve.the conductance
of solution depends upon the degree of ionization of
the weak electrolyte. With the increasing degree of
ionization with dilution, the value of equivalent
conductance increases.
When the limitng value of equivalence conductance is
reached then the degree of dissociation is unity. At this
stage there is complete dissociation of electrolyte. This is
true for strong electrolytes.
In the case of weak electrolytes the degree of dissociation
is not completed even at great dilution. It bears the
following formula
= /
= equivalent conductance at given concentration
= equivalent conductance at zero concentration
(infinite dilution)
The vlue of can be found out by Kohlrausch law of
independent migration of ions.
The molar conductivity of strong electrolytes in high
dilutions decreases linearly according to Kohlrausch
equation:

m = m a C
In this case, the limiting conductivity may be determined
directly from the molar conductivity measurement.
Designation by the graphical method involves the
preparation of a graph. of m = f( C ) dependence and
extrapolation to concentration of zero.
In the case of weak electrolytes the molar conductivity
changes in more complex way with dilution and hence
conductivity boundary cannot be determined directly
from the measurements. In this case the limiting
conductivity can be calculated from the Kohlraucsh law of
independent migration of ions
m =+ + + - -