Conductometri

c Titrations
Nothing in life ie
feared;it is only to
be understood
-Marie Curie

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 PRINCIPLE
The principle of conductometric titration is based on
the fact that during the titration, one of the ions is
replaced by the other and 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 may be located graphically by
plotting the change in conductance as a function of
the volume of titrant added.
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Types of
Conductometric
Titrations
 Acid-Base
Redox
Titration
Titration

Precipitation Complexometric
Titration Titration

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 ACID-BASE
TITRATION
In this method, the conductance of the
hydrogen ions and hydroxyl ions are
compared with the conductivity of the
sample solution.
TYPES OF ACID-
BASE TITRATION
⦿ Strong Acid with a Strong Base
⦿ Weak Acid with a Strong Base
⦿ Strong Acid with a Weak Base
⦿ Weak Acid with a Weak Base
⦿ Mixture of a Strong Acid and a
Weak
Acid vs. a Strong Base or a Weak Base

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 STRONG ACID WITH
STRONG BASE
⦿ Example:- 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.

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⦿ 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

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[H+Cl- ]+ [Na+OH-] →[Na+Cl-] + H2O
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 WEAK ACID WITH STRONG
BASE
⦿ Initially the conductance is low due to the poor ionization of
acetic acid.
⦿ Theoretically on addition of base, highly ionized sodium
acetate is formed and hence conductance begins to increase.
⦿ When acid is completely neutralized further addition of
base introduces hydroxyl ions which has high ionic
mobility

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⦿ Thus conductance of solution begins to increase more
sharply and when two lines intersect we get endpoint.
⦿ But practically this does not happen because initially, the
addition of a very small amount of NaOH(aq) to
CH3COOH (aq) will decrease the concentration of
highly mobile H+ (aq) in solution because the production
of acetate ions, CH3COO- (aq), will repress the
dissociation of acetic acid
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⦿ But soon, the conductance increases on adding
NaOH as NaOH neutralizes the un-dissociated
CH3COOH to CH3COONa which is the strong
electrolyte.
⦿ This increase in conductance continues raise up to
the equivalence point. The graph near the
equivalence point is curved due the hydrolysis of
salt CH3COONa. Beyond the equivalence point,
conductance increases more rapidly with the
addition of NaOH due to the highly
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-
 CH3COOH+ [Na+OH-] → CH3COONa +
H2O

Therotical graph Experimental graph

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 STRONG ACID WITH WEAK
BASE
⦿ Example:- HCl with NH4OH
⦿ 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 sulphate

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[H+Cl- ]+ NH4OH→ NH4Cl + H2O

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 WEAK ACID WITH WEAK BA

⦿ 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

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CH3COOH + NH4OH→NH4CH3COO +
H2O

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MIXTURE OF STRONG ACID AND
WEAK ACID WITH STRONG
BASE/WEAK BASE
⦿ In this curve there are two break points. The first break point
corresponds to the neutralization of strong acid. When the
strong acid has been completely neutralized only then the
weak acid starts neutralizing.
⦿ The second break point corresponds to the neutralization of
weak acid and after that the conductance increases due to the
excess of OH- ions in case of a strong base as the titrant.
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⦿ However, when the titrant is a weak base, it remains
almost constant after the end point

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 REDOX TITRATION
In this method, the decrease in the hydrogen ions concentration
shows the decrease in the conductivity at the end point.
Example: The titration of the ferrous ions with the dichromate
ions.
6Fe2++ Cr2O7 2- + 14H+→6Fe3+ + 2Cr+3 + 7H2O
The hydrogen ions show sharp decrease in the conductivity. After
the equivalence point, the addition of the excess of the titrant
shows the stability in the conductivity.
Redox titration curve

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 PRECIPITATION
TIRATION
When compared to the acid–base titrations, precipitate titrations are not that
much accurate because of the more number of the interferences. These
are also known as the replacement titrations. The precipitate formation is
taken as the end point when the conductivity is measured.
Example: Potassium chloride is titrated with the precipitating agent such as
the silver nitrate solution.
KCl + AgNO3 →AgCl + [K+NO3 -]
 Initially the addition of the silver nitrate to the
potassium chloride shows the stability in the
conductivity and the excess of the silver nitrate
addition increases the conductivity because of
the formation of the single precipitate.

Precipitation
titration curve

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 COMPLEXOMETRI
C TITRATION
This was first proposed by Werner. In this method, the two end points are
observed. First is the formation of the metal ion and the second one is the
formation of the complex.
Example: The titration of the potassium chloride with the mercuric chlorate.
Hg(ClO4)2 + 4KCl Image HgCl4 2-+ 2K+ + 2KClO4
HgCl4 2-+ 2K+ →K2HgCl4
Initial end point is shown by the formation of the HgCl4 2- and the other end
point is shown by the formation of the K2HgCl4
Complexometric titration curve

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 FACTORS
Temperature: The conductivity of the electrolyte increases with
the temperature increase. This is because of the ions mobility by
increasing the temperature.
Concentration of the sample solution: The concentration of the
solution is inversely proportional to the conductivity of the sample
solution. The conductance is decreased with the increase in the
concentration. Hence diluted solutions are used for the
measurements.
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  Number ions present in the sample solution: This is mainly
based on the dissociation of the compounds into ions. That is
mainly of the number of ions present in the solution. The
number of ions present in the solution is directly proportional
to the conductance. Strong electrolytes completely dissociate
into ions and have high conductance.
 Charge of the ions: Negative charge of the ions increases the
conductivity where as the positively charged ions decreases
the conductivity.
 Size of the ions: The conductivity is inversely proportional to
the size of the ions. That is the increase in the size of the
ions increases the conductivity. 28
 APPLICATION OF
CODUCTOMETRIC

TITRATION
The determination of water purity,salinity of seawater, alkalinity of freshwater can
be done using conductometry.
 It can be used to determine the chemical equilibrium in ionic reactions
 Conductometry titration can be used in the quantitative analysis of compounds.
 Used to detect microorganisms in food industries.
 Conductometry titration used to determine the basicity of organic acids.
 The deuterium ion concentration in the water can be determined by the
conductometry.

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 ADVANTAGES OF
CONDUCTOMETRIC
TITRATION
⦿ This process is very useful in the titrations of very dilute
solutions and weak acids.
⦿ The end-point of this titration is very sharp and accurate when
compared to a few other titration processes.
⦿ Applicable for solutions that are coloured or turbid, and for
which the endpoint of the titration with normal indicators
cannot be observed easily by the human eye.
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 DISADVANTAGES OF
CONDUCTOMETRIC TITRAT
⦿ The accuracy of conductometric titration is low when the
concentrations of the electrolyte are high, making the
titration process unsatisfactory.
⦿ Only a few specific redox titrations can be done with the
help of this process. This is because the conductivity of
the solution is masked by relatively high hydronium ion
concentration.
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THANKS!
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