Conductance: flow
of electricity through a electrolyte solution due to migration of ions by
applying potential difference between two electrode.
-
Cathode (-ve
charged) will attract cations (+ve charged)
-
Anode (+ve
charged) will attract anions (-ve charged)
It is denoted by G. and is reciprocal of
resistance R.
So, G= 1/R
Units of conductance is siemens (S).
Specific Conductance:
Resistance is directly proportional to the length (l)
and inversely proportional to the cross-section area (a) of the conductor.
R ∝ l/a
R= ฯl/a where, ฯ= specific resistance
R= ฯ= Specific resistance (having 1 m length and 1 m2
area)
·
Specific
conductance (k): reciprocal of specific resistance
(k)= 1/ ฯ,
k= l/a *1/R,
K=l/a * G
Unit of specific conductance is siemens.m-1
Equivalent conductance:
·
Conductance one
gram equivalent solutions. If l=1 m, volume= 1m3 and 1 gm equivalent
solution is taken then,
·
G=k
·
It is denoted by
the symbol “ฮ”. And its unit is siemens.m2/gram equivalent.
Molar conductivity:
·
Molar conductivity can also be defined as the conducting
power of all the ions that are formed by dissolving a mole of electrolyte in a
solution.
ฮm =
K / C
·
Where K is the specific conductivity and c is
the concentration in mole per litre.
·
The unit of molar
conductivity is Siemens⋅m2⋅mol-1.
Principal:
Conductometry
is based in the principal of determination of changes in conductivity. Change
in conductance is due to replacement of ions with each other.
Ionic conductivity is different for different ions.
Instrumentation:
Current Source:
-
Alternative
current source is used.
-
High frequency
alternating current generator is employed.
-
Electrical
potential is applied, ions will be transferred and ultimately conductance takes
place.
Conductivity meter:
-
Digital display
-
Calibrator
-
Power switch
Conductivity Cell:
-
It is made up of pyrex or quartz
-
Fitted with 2 electrodes
: cathode
: anode
Electrodes:
-
Electrodes are
made up of platinum
-
Area of electrode
surface = 1 cm2
-
Distance between
two electrode is 1 cm
-
Electrodes are
plated with platinum black: to avoid polarization
: to increase the surface
area
-
Coating is done
through 3% chloroplatinic acid and lead acetate
Conductometric titration
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 can be located graphically by plotting the changes of
conductance as a function of the volume of the added titrant.
The most important advantages of this method are that
it can be used for determination of:
– turbid and highly coloured solutions,
– very dilute solutions,
– 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 M hydrochloric acid the titrant sodium hydroxide should
be at least 0.1 M. By this way dilution that takes place during titration is
minimum and this is necessary because conductivity decreases with dilution.
2. Avoid the presence of ions which will not take part
in the reaction, such as the presence of buffer or concentrated acids. These
ions will increase the initial conductivity and its change during the titration
will be comparatively small and can not 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.
Some typical conductometric titration curves are:
1. Strong Acid with a Strong Base, e.g. HCl with NaOH
Before NaOH is added, the conductance is high due to
the presence of highly mobile hydrogen ions. When the base is added, the
conductance decreases due to the replacement of hydrogen ions by the added
cation as H+ ions react with OH- ions to form
undissociated water.
This decrease in the conductance continues till the
equivalence point. At the equivalence point, the solution contains only NaCl.
After the equivalence point, the conductance increases due to the high conductivity
of OH-ions.
Fig: Conductometric titration of strong acid (HCl) vs.
strong base (NaOH).
2. Strong Acid with a Weak Base, e.g. 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 ionised in the presence of ammonium chloride (Fig. 2).
Conductometric titration of strong acid (HCl) vs. weak
base (NH4OH).
3. Weak Acid with a Strong Base: e.g. CH3COOH with
NaOH
Initially a slight decrease in the conductance is
caused by binding a small amount of hydrogen ions, originating from
dissociation of acetic acid, into water molecules. Next, the gradual
conductance increase is connected with the substitution of the weakly
dissociated acetic acid by the well dissociated sodium acetate. After the
equivalence point has been reached, the conductance increases significantly due
to the increasing concentration of OH ions (Fig. 3).
Conductometric titration of weak acid (CH3COOH) vs.
strong base (NaOH).
4. Weak Acid with a Weak Base: e.g. CH3COOH with
dilute ammonia
Initially a slight decrease in the conductance is
caused by binding a small amount of hydrogen ions originating from dissociation
of acetic acid and next an increase is observed because of well dissociated
salt - ammonium acetate formation. After the equivalence point the conductance
increases but much less (Fig. 4).
Conductometric titration of weak acid (CH3COOH) vs.
weak base (NH4OH).
Application of Conductance measurement
- They are used to determine the purity of water by checking the
pollution levels of various water bodies.
- Conductometric titration is also used to examine the alkalinity of
freshwater bodies and the salinity of seawater.
- Conductometry is also used in the food industry by
microbiologists in order to trace microorganisms.
- The application of conductometric titration is also found in the pharmaceutical
industry. It is used to check the basicity of organic acids and to detect
antibiotics.
- It is used to determine the purity of distilled water or its
freshness by examining the chemical equilibrium in ionic reactions.
Advantages
of conductometric titration
Some
of the main advantages of such titration are given:
1.
It is quite difficult to select
suitable indicators for the titration of colored solutions. In such cases,
conductometric titration can be carried out.
2.
Titration of very diluted solution and
weak acids versus weak bases can not be carried out in volumetric titration but
titration of such acid bases can be carried out quite easily with the help of
conductometric titration.
3.
In a volumetric titration, special
attention is needed near the endpoint to detect the color change but in this
titration, no such special care is required near the endpoint.