SEMINAR ON

CONDUCTOMETRIC TITRATION
&
HIGH FREQUENCY ANALYSIS
Presented by
1 7 May 2013
CONTENTS
1. CONDUCTOMETRY
Introduction
Laws and definitions
Conductometric measurements
Factor Affecting Conductivity
Application of Conductometry
2. CONDUCTOMETRIC TITRATION
Introduction
Types of Conductometric Titration
Advantage of Conductometric Titration
DisAdvantage of Conductometric Titration
Recent Development
Cont.

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3. HIGH FREQUENCY ANALYSIS (TITRATION)
Introduction
Instrumentation
High Frequency Titrimeters
Application of High Frequency method
Advantage of High Frequency method
Disadvantage of High Frequency method
References











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CONDUCTOMETRY
Introduction
Conductometric analysis is based on the
measurement of the electrical conductivity of the
solution. The electrical conductivity is entirely due to
the movement of ions.

The conductometry is used in direct and indirect
methods of physico-chemical analysis. It is widely
used in complexometric titrations, chemical kinetics,
precipitation titrations and plant laboratories.






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Ohms law
Ohms Law is obeyed by metallic as well as by
electrolytic conductors. According to this law, the
strength of current (I) flowing through a conductor is
directly proportional to the potential difference (E)
applied across the conductor and inversely proportional to
the resistance (R) of the conductor.
Mathematically, the law can be represented as
The current is measure in amperes, potential difference in
volts and electrical resistance in ohms.
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E
I
R
=

Conductance

In the case of electrolytes, the term conductance (C) is
generally used. It implies the ease with which the
current flows through a conductor.
Thus, the conductance is the reciprocal of resistance.
Mathematically,


It is expressed in units of reciprocal ohms or mhos.
Equivalent Conductance
It is conductance offered by a solution containing
equivalent weight of solute in it.

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1
C
R
=
Specific Conductance
Specific conductance can be defined as the
conductivity offered by a solution of length 1 cm
and area of 1sq.cm cross section. It is expressed
in mhos/cm. The specific conductance of an
conductor is the reciprocal of specific resistance
and is denoted by k . Mathematically,


Specific conductance= conductance X cell constant
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1 1
1 l
k ohm cm
R a

=

CONDUCTOMETRIC MEASUREMENTS

1.Electrodes
Two parallel platinized Pt. foil electrodes or Pt. black
with electrodeposited a porous Pt. film which increases
the surface area of the electrodes and further reduces
faradaic polarization.
2.Primary standard solutions
Primary standard KCl solution ,at 25, 7.419g of KCl
in 1000g of solution has a specific conductivity of
0.01286
-1
/cm.


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3.Conductivity Cell :
Avoid the change of temperature during determination.
4.Wheat stone bridge:
















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FACTORS AFFECTING CONDUCTIVITY
Size of ions
Temperature
Number of ions
Charge of ions



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APPLICATIONS OF CONDUCTOMETRY
It can be used for the determination of,
Solubility of sparingly soluble salts
Ionic product of water
Basicity of organic acids
Salinity of sea water (oceanographic work)
Chemical equilibrium in ionic reactions
Degree of dissociation of weak electrolyte
Degree of Hydrolysis


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CONDUCTOMETRIC TITRATION
Introduction
Conductometric Titration (measurements) provide a
convinent means for locating end point in Titration,
Sufficient measurements are needed to define the
Titration curve. After being corrected for volume change,
the conductance data are plotted as a function of titrant
volume. The two linear portions are then extraplotted, the
point of intersection taken as equivalent point (or) end
point.
cont.


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The conduct metric end point is completely
non-specific although it is potentially
Adaptable to all type of volumetric reaction.

Definition
It is defined as that the determination of
the end point of a titration with the help
of conductivity measurement is termed as
Conductometric Titration.













Apparatus for conductometric titarions
Measuring Circuit: In order to prevent concentration change
due to reactions at electrodes the conductivity of solution
generally measured with alternating currents at frequecies
from 60 to 1000cps. Most of the circuits used are of the
Wheatstone bridge type.
Commerical Apparatus: The commercially available equipment
is accurate enough for routine conductometric titarions. The
important advvantage of this instrument is that it is convinent
and can be set up and used without the knowledge of
electronic or electricity.
Other methods: Many workers have shown that conductance
can also be measured by using D.C. provided that the cell has
two unpolarisable electrodes, such as electrode.



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Ag AgCl

Types of conductometric titrations

Acid-Base Titration

Replacement Titration

Precipitation Titration

Redox -Titration

Complexometric Titration

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ACID-BASE TITRATION
(a) Titration of strong acid with strong base e.g. HCl with NaOH
(b) Titration of strong acid with weak base e.g. HCl with NH
4
OH



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2
4 4 2
H Cl Na OH Na Cl H O
H Cl NH OH NH Cl H O
+ + +
+ + +
( ( + +

( ( + +


(c) Titration of weak acid with strong base e.g. CH
3
COOH with NaOH
(d) Titration of weak acid with weak base e.g. CH
3
COOH with NH
4
OH

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3 3 2
3 4 3 4 2
CH COO H Na OH CH COO Na H O
CH COO H NH OH CH COO NH H O
+ + +
+ + +
( ( + +

( ( + +



REPLACEMENT TITRATION
Titration of strong acid with Sodium salt of weak Acid
e.g. HCl with CH
3
COONa


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When a strong acid reacts with sodium salt of weak
acid (Sodium acetate) the weaker acid will replace
first.



3 3
CH COO Na H Cl CH COO H Na Cl
+ + + +
( ( ( ( + +


PRECIPITATION TITRATION

The precipitation titration cant be carried out so effectively as
the acid-base titration. This is so because the acid-base
titrations are characterized by sharp breaks because both the
hydrogen and hydroxyl ions have very high equivalent
conductance's.
Consider the titration between silver nitrate and potassium chloride.


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3 3
K Cl Ag NO K NO Ag Cl
+ + + +
( ( ( ( + +

REDOX (OXIDATION-REDUCTION) TITRATION
In case of oxidation reduction titrations, there is a decrease
in hydrogen ion concentration.



The redox reactions give good result only when the initial
concentration of acid is low.






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2 2 3 3
2 7 2
6 14 6 2 7 Fe Cr O H Fe Cr H O
+ + +
+ + + +
COMPLEXOMETRIC TITRATION
Complexometric Titration have been use in the study of
formulae of complex compounds. Job titrated roseo - cobaltic
sulphate [Co(NH
3
)
5
H
2
O]
2
(SO
4
)
3
with Barium hydroxide and
obtained two breaks in the titration curve.


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ADVANTAGES OF CONDUCTOMETIC TITRATIONS
No need of Indicator.
Temperature is maintained constant throughout the
titration.
End point can be determined accurately and errors are
minimized as the end point is being determined
graphically.
They can be used in the case of coloured liquids
where ordinary indicators cannot work.
They can be used for the analysis of dilute solutions
and also for very weak acids.
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ADVANTAGES OF CONDUCTOMETIC TITRATIONS
It become less accurate and less satisfactory
with increasing total electrolyte concentration.
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RECENT DEVELOPMENTS
In refinery Industries.
In the Estimation of poly electrolytic solution.
In biotechnology.
In Micro biosensors for environmental monitoring.

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HIGH FREQUENCY ANALYSIS (TITRATION)
Introduction
High frequency titrimetry is closely related to
conductometric end point determinations. The titration
vessel is kept in the field of high frequency oscillator and
change in the conductivity of the solution produce
capacitance change which result in the unbalance of the
detector circuit. The chief advantage of high frequency
Titrimetry is that is eliminate the introduction of
Electrodes and other undesirable elements into the
solution being analyzed.


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INSTRUMENTATION

The instrument used for measuring the concentration
of a solution at high frequencies are quite different
from simple wheat stone bridge Instruments. The
technique of high frequency analysis was developed
by F.N. Jensen and A. L. Parrack in 1946.
The unique advantage of high frequency alternating
current is that the electrode can be placed outside the
vessel and out of direct contact with the solution.
The electrode can be made without the danger of
electrolysis or electrode polarization and without
altering or consuming any solution.

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CELLS
For the high frequency
titrations, two types of cells
are used . These are
(i) capacitative type
(ii) Induction type
In the capacitative cells the
variable parameters is
capacitance which depends
mainly on dielectric
constant of the solution and
the resistance of the solution
in the cells.
In case of Induction cell the
variable parameter is the
inductivity of cell which
almost independent of
native of solution and
resistance.

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OSCILLATOR CIRCUIT

The fundamental circuit of
an oscillator has capacitance
C, an inductance L and
Resistive component R.
When the adjustment of
circuit capacitance or
turning is done, a attained
which is called Resonance.
When the condenser is
discharged through the
inductance, current will
surge back and forth from
the inductor to the capacitor
at the frequency represented
by
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1
2
f
LC t
=
Hi gh Frequency Ti tri meters
The Instrument used for high frequency titrimetry range from
simple magic eye tube circuit of hall to complex commercial
oscillometer of sargent. The analysis of the electrical variables
involved has been given by Reilley Mccurdy in 1953.
The simple cell is put in parallel with the calibrated capacitor.
In order to return to the resonant frequency, it is necessary to
remove the exact amount of capacitance which was added by
the sample.
The offer convenient method is to measure the output
frequency of two identical oscillator circuits. One of the circuit
contain the sample cell as part of oscillator capacitance f and
the other circuit serve as reference unit fo. The output form the
two unit are then fed into mixer unit.
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Appl i cati on of Hi gh Frequency method

It is used in Acid-Base titration
In the Analysis of mixture of organic
compounds
In complexometric Titrations
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Advantage of Hi gh Frequency method

This method doesnt require any special type of
Conductivity cell.
As metal electrodes are not placed in contact with
the solution, the polarization of electrode and
chemical interaction of materials are eliminated.
There is no possibility of catalytic or surface
effects taking place on platinised electrodes
dipping into the solution.
These titrations can also be carried out in non-
aqueous media.

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Di sadvantage of Hi gh Frequency method

The complexity of the technique used and
difficulty of tuning.
The sensitivity of titrimeter is less than the
wheatstone bridge. The sensitivity can
however be increased by using well designed
intruments.
For quantitaive analysis the sensitivity of high
frequency method is not better than the low
frequency measurements.

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References
Skoog, Douglas A.,f.James Holler and Timothy Nieman.
Principle of instrumental analysis. 5
th
Edision. Newyork, 1998 .
Instrumental analysis 5
th
Edision Galen W.Ewing McGRAW-
HILL international edision.
Instrumental method of chemical analysis 5
th
Edision,
Gurudeep R. Chatwal, sham K. Anand Himalaya publishing
house. P.No.2.482-2.497
Daniel christain, Text Book of Analytical chemistry 2
nd
edition,
Wiley India P.No. 274.
Hovert H.Willard, Instrumental method of Analysis CBS
Publishers 1986 P. No. 732-750.
A textbook of Analytical Chemistry Instrumental Technique
Mahinder singh P.No.164-170




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