Conductometric Titrations

Submitted to:
Dr Nasir Uddin Khan
Subject:
Physical chemistry lab

Submitted by:

FARAZ ANJUM (ROLL NO 09)

M.SC (previous)

Date: 21 September 2010

Department of chemistry
University of Karachi

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History
The word "titration" comes from the Latin word “titulus”, meaning inscription or title.
The French word titre, also from this origin, means rank.
TITRATION
The process, operation, or method of determining the concentration of a substance
in solution by adding to it a standard reagent of known concentration in carefully
measured amounts until a reaction of definite and known proportion is completed,
as shown by a color change or by electrical measurement, and then calculating the
unknown concentration. OR
Titration, by definition, is the determination of rank or concentration of a solution with
respect to water with a pH of 7 (which is the pH of pure H2O under standard conditions).

The origins of volumetric analysis are in late-18th-century French chemistry.

Types of titrations
Titrations can be classified by the type of reaction. Different types of
titration reaction include:
• Acid-base titrations are based on the
neutralization reaction between the analyte and an
acidic or basic titrant. These most commonly use a pH
indicator, a pH meter, or a conductance meter to
determine the endpoint.
• Redox titrations are based on an oxidation-reduction reaction between
the analyte and titrant. These most commonly use a potentiometer or a
redox indicator to determine the endpoint.
• Complexometric titrations are based on the formation of a complex
between the analyte and the titrant. The chelating agent EDTA is very
commonly used to titrate metal ions in solution.

Measuring the Endpoint of A Titration

There are many method to measure the end point of a titration such as by

• Volumetric titration
• Conductometric titration
• Potentiometer
• PH meter etc

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CONDUCTOMETRIC TITRATION:

Titration in which the end point is determined by measuring the resistance

of the solution to an electric current that is passed through it.

The conductance method can be employed to follow the course of a titration,

provided that there is a significant difference in conductance between the original
solution and the reagent of the product of reaction.

Conductance:
The conductance is the property of the conductor (metallic as well as electrolytic) which
facilitates the flow of electricity through it. It is equal to the reciprocal of resistance i.e.,

Conductance = 1/Resistance = 1/R

It is expressed on the unit called reciprocal ohm (ohm-1 or mho) or siemens
G = 1/R
It is a measure of the ability of a solution to conduct electricity. The conductance
of a solution is the sum of the conductances of all of the ions that are in the
solution.
G = Σ Gi

The conductance of a particular ion in solution depends upon the concentration of

the ion, the charge on the ion, and the size of the ion. As the concentration or the
charge of the ion increases, the conductance of the solution increases. In general
as the size of the solvated ion decreases, its mobility through the solution
increases and consequently the conductance of the solution increases. In water
the ion which has the greatest conductance is H+. Of the common, negative ions,
OH– has the greatest conductance. Molecular species (uncharged substances) do not contribute
to the conductance ofa solution.
Electrolyte solutions obey Ohm's law just as metallic conductors do. The current I passing
through a given body of solution is proportional to the applied potential difference V. The
resistance R of the body of solution in ohms (Ω ) is given by:
R = V/I

where the potential difference is expressed in volts and the current

in amperes. The conductance, defined as the reciprocal of the
resistance, of a homogeneous body of uniform cross section is
proportional to the cross-sectional area A and inversely
proportional to the length l, as shown in the Figure on the right:
G = 1/R = κ A/l (3)

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where κ is the conductivity with units Ω -1m-1:

κ = l/AR = C/R (4)

(By international agreement, the reciprocal ohm, Ω -1, is now called a siemens, 1 S = 1 Ω -1). One
can think of the conductivity as the conductance of a cube of material, 1 m on each edge. Since
it is difficult to build a cell with well defined geometrical parameters A and l, any cell should be
calibrated with a solution of exactly known specific conductance. From Eq.(5) we can determine
the cell constant C :

C = l/A (5)

The conductivity of a solution depends on the ions that are present in it. During many titrations,
the conductivity changes significantly

FACTORS AFFECTING ELECTROLYTIC CONDUCTANCE

In general, conductance of an electrolyte depends upon the following factors,

(1) Nature of electrolyte : The conductance of an electrolyte depends upon the number of ions present
in the solution. Therefore, the greater the number of ions in the solution the greater is the conductance.
The number of ions produced by an electrolyte depends upon its nature. The strong electrolytes
dissociate almost completely into ions in solutions and, therefore, their solutions have high conductance.
On the other hand, weak electrolytes, dissociate to only small extents and give lesser number of ions.
Therefore, the solutions of weak electrolytes have low conductance.

(2) Concentration of the solution : The molar conductance of electrolytic solution varies with the
concentration of the electrolyte. In general, the molar conductance of an electrolyte increases with
decrease in concentration or increase in dilution.

The molar conductance of strong electrolyte (HCl, KCl, KNO3) as well as weak electrolytes
( CH3COOH.NH4OH) increase with decrease in concentration or increase in dilution. The variation is
however different for strong and weak electrolytes.

The variation of molar conductance with concentration can be explained on the basis of conducting ability
of ions for weak and strong electrolytes.

For weak electrolytes the variation of Λ with dilution can be explained on the bases of number of ions in
solution. The number of ions furnished by an electrolyte in solution depends upon the degree of
dissociation with dilution. With the increase in dilution, the degree of dissociation increases and as a
result molar conductance increases. The limiting value of molar conductance (Λ 0) corresponds to degree
of dissociation equal to 1 i.e., the whole of the electrolyte dissociates.

Thus, the degree of dissociation can be calculated at any concentration as,

α = Λc/Λ0
where α is the degree of dissociation,

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Λc is the molar conductance at concentration C and

Λ0 is the molar conductance at infinite dilution.

For strong electrolytes, there is no increase in the

number of ions with dilution because strong
electrolytes are completely ionised in solution at all
concentrations (By definition). However, in
concentrated solutions of strong electrolytes there
are strong forces of attraction between the ions of
opposite charges called inter-ionic forces. Due to
these inter-ionic forces the conducting ability of the
ions is less in concentrated solutions. With dilution,
the ions become far apart from one another and
inter-ionic forces decrease. As a result, molar
conductivity increases with dilution. When the
concentration of the solution becomes very-very low,
the inter-ionic attractions become negligible and the
molar conductance approaches the limiting value
called molar conductance at infinite dilution. This
value is characteristic of each electrolyte.

1. (3) Temperature :
The conductivity of an electrolyte depends upon the
temperature. With increase in temperature, the
conductivity of an electrolyte increases. By
increasing the temperature, the mobility of the ions in the solution will increase. So
temperature has a direct effect on conductance of solution. E.g. by increasing the
temperature the conductance will increase.

2. Size of the ions

The conductivity of the solution is inversely proportional to the size of the
ions .if the size of the ions is increasing then the conductivity of the solution
will decrease because the mobility of the ions will decrease by increasing
the size of the ions.
e.g. The mobility of the hydrogen ions will be greater than the sodium ions
so the conductance of the solution containing sodium ions will be less than
the solution containing hydrogen ions. same principal is used here in this
experiment ,initially solution contain the hydrogen ions when this solution is
titrated against the base solution ,the base reacts with the acid and the
number of the hydrogen ions go on decreasing. Finally a stage reaches
when there is no hydrogen ion in the solution so the conductivity decreased
and remains constant. If further base is added then the number of negative
ions increases and the conductivity go on increasing. The point at which the
conductivity becomes constant is the equivalence point. The volume of base

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 used at equivalence point is used to calculate the morality of acid and then
the strength of acid. Consider a solution of a strong acid, hydrochloric acid,
HCl for instance, to which a solution of a strong base, sodium hydroxide
NaOH, is added. The reaction occurs. For each amount of NaOH added
equivalent amount of hydrogen ions is removed. Effectively, the faster
moving H+ cation is replaced by the slower moving Na+ ion, and the
conductivity of the titrated solution as well as the measured conductance of
the cell fall. This continues until the equivalence point is reached, at which
we have a solution of sodium chloride, NaCl. If more base is added an
increase in conductivity or conductance is observed, since more ions are
being added and the neutralization reaction no longer removes an
appreciable number any of them. Consequently, in the titration of a strong
acid with a strong base, the conductance has a minimum at the equivalence
point. This minimum can be used instead of an indicator dye to determine
the endpoint of the titration. Conductometric titration curve that is a plot of
the measured conductance or conductivity values against the number of
milliliters of NaOH solution

Migration of ions

Electricity is carried out through the solution of an electrolyte by migration of ions. Therefore,

(1) Ions move toward oppositely charged electrodes at different speeds.

(2) During electrolysis, ions are discharged or liberated in equivalent amounts at the two electrodes, no
matter what their relative speed is.

(3) Concentration of the electrolyte changes around the electrode due to difference in the speed of the
ions.

(4) Loss of concentration around any electrode is proportional to the speed of the ion that moves away
from the electrode, so

Loss around anode/Loss around cathode = Speed of cation/Speed of anion

The relation is valid only when the discharged ions do not react with atoms of the electrodes. But when
the ions combine with the material of the electrode, the concentration around the electrode shows an
increase.

.
Experiment:
Conductometric Titration of Hydrochloric Acid and Acetic Acid with Sodium
Hydroxide

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 During the titration of hydrochloric acid with sodium hydroxide, the reaction that
takes place in the titration vessel is

H+ + Cl- + Na+ OH- H2O + Cl- + Na+

Before the end point, H+ is removed from the

solution by reaction with OH–, and
Na+ is added to the solution. Since the relative
conductance of H+ is about seven
times that of Na+, the conductance of the
solution decreases prior to the end point.
After the end point, no H+ is available to react,
and the conductance of the solution
increases as a result of the addition of Na+ and
OH–. Consequently the titration
curve has a V-shape as shown in the figure. The
end point of the titration
corresponds to the intersection of the
extrapolated linear portions of the titration
curve.Diagrams of the conductometric titration
curves. A, the titration of HCl withNaOH
theconductance of the solution after the end
point increases more rapidly than it didbefore the
end point. The end point corresponds to the intersection of the
extrapolated linear portions of the curve.
Conductance is usually measured with an alternating current between two
identical, platinized platinum electrodes. Use of an alternating current prevents
the buildup of reaction products around either electrode and consequently
prevents polarization of the solution. The electrodes must be rigidly held at a fixed
distance apart during the titrations in order to prevent changes in conductance
that result from an altered solution volume between the electrodes.
Principle:
Basic principle is the changes in conductivity of a solution when no. of ions that
are the responsible for the conduction of electricity is changing

2.Temperature:

By increasing the temperature, the mobility of the ions in the solution will increase.
So temperature has a direct effect on conductance of solution. E.g. by increasing
the temperature the conductance will increase and vice versa.

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Procedure:
1. 100 Ml of acid was taken in beaker.
2. Solution was kept at room temperature for at least 10 minutes.
3. Then Dip the electrode of conductometer in solution.
4. Measure the initial conductance of solution.
5. First reading of conductometer was noted.
6. Then this solution was titrated against the Base solution of known strength
using burette.
7. Observe the change in conductance of acid solution after every 5 ml addition
of base.
8. Plot these values to find the equivalence point.
9. Volume of base used till the equivalence point is the volume which is
required to fully neutralize the acid.

Calculations:

Acid Base
M1 V1 = M2 V2

M=molarity

v=volume used

M1=M2V2V1

Volume of Base used (mL) Conductance

0 28.2

5 28

10 27.7

15 27.2

20 26.6

25 21.8

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 30 20.6

35 19.4

40 18.6

45 17.6

55 16.6

65 13.6

75 12

85 10.6

95 9

105 7.8

110 7.2

115 6.6

120 6

130 5

135 5.1

140 5.3

150 5.9

160 6.3

170 6.8

185 7.4

M1=M2V2V1

M1=0.1×130100 M

M1=0.13 M

Strength of acid = molarity x

molecular wt

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 =0.13 X 36.5=
4.745 g/mL

GRAPHICAL REPRESENTATION:

APPLICATIONS OF CONDUCTOMETRIC TITRATIONS

Acid-base titrations redox titrations are known to us in which commonly

indicators are used to locate the end point e.g., methyl orange,
phenolphlthalene for acid base titrations. However electricalconductance
measurement can be used as a tool to locate the end point.
1. This method can be used with much diluted solutions
2. This method can be used with colored or turbid solutions in which end
point can not
Be seen by eye
3. This method can be used in which there is no suitable indicator
4. has many applications, i.e. it can be used for acid base, redox,
precipitation, or complex titrations
5. Determination of sulphur dioxide in air pollution studies
6.Determination of soap in oil
7.Determination of accelerators in rubber
8.Determination of total soap in latex
9.Specific conductance of water

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