Addis Ababa University

College of Health Science

School of Pharmacy
Department of Pharmaceutical Chemistry and
Pharmacognosy

Pharmaceutical Analysis I Group Assignment

Section 2 Group 2

Title: Conductometry

March 14, 2023

 Pharmaceutical Analysis I
Group Assignment

Conductometry
By
1. Meron Kidane UGR/6943/13
2. Mohammed Shafi UGR/1427/13
3. Nathnael Demissie UGR/ 6617/13
4. Nebiyat Birhan UGR/2865/13
5. Niweds Yeshaw UGR/3741/13
6. Paulos Yibarkie UGR/0109/13
7. Rahmet Aragie UGR/6117/13
8. Redet Ababaw UGR/9929/13

Submitted to Mr. Wondosen

March 2023
 Acknowledgment

First of all we would like to give our gratitude for the Almighty God who helped us in
accomplishing this assignment. We would also like to give our deepest gratitude to the numerous
chemical analysts whose work was essential in accomplishing our task successfully. At last we
want thank our teacher Mr. Wondosen for pushing us beyond our comfort and giving us this
interesting topic to work on.

Thanks

i
Contents
Acknowledgment ........................................................................................................................................... i
1. Introduction ......................................................................................................................................... 1
2. Principle of conductometric titration ................................................................................................ 1
2.1. Definition of Terms and relations in conductometry ............................................................... 2
3. Instrumentation and conductivity measurement ............................................................................. 3
3.1. Instrumentation........................................................................................................................... 3
3.2. Measurement ............................................................................................................................... 4
4. Types of conductometric titration ..................................................................................................... 5
4.1. Strong acid with strong base ...................................................................................................... 5
4.2. Strong acid with weak base ........................................................................................................ 5
4.3. Weak acid with strong base........................................................................................................ 6
4.4. Weak acid with weak base.......................................................................................................... 6
4.5. Mixture of a Strong Acid and a Weak Acid vs. a Strong Base or a Weak Base: .................. 7
4.6. Displacement titration ................................................................................................................ 7
4.7. Precipitation Titration ................................................................................................................ 8
5. The general process of conductometric titration.............................................................................. 8
6. Factors affecting conductance of solution ......................................................................................... 9
6.1. Concentration of ions .................................................................................................................. 9
6.2. Nature of electrolyte.................................................................................................................... 9
6.3. Temperature ................................................................................................................................ 9
7. Application of conductometry............................................................................................................ 9
7.1. Determination of solubility of sparingly soluble material: ...................................................... 9
7.2. Kinetic research: ......................................................................................................................... 10
7.3. Determination of concentration:.............................................................................................. 10
8. Advantage and limitations of Conductometry ............................................................................... 10
References ................................................................................................................................................... 11
 Table of Figures
Figure 1: Types of Conductivity cells ............................................................................................................. 3
Figure 2: A wheat stone bridge circuit .......................................................................................................... 4
Figure 3: Strong acid with strong base conductometric titration ................................................................. 5
Figure 4: Strong acid with weak base conductometric titration................................................................... 6
Figure 5: Weak acid with strong base conductometric titration .................................................................. 6
Figure 6: Weak acid with weak base Conductometric titration ................................................................... 7
Figure 7: Mixture of a Strong Acid and a Weak Acid vs. a Strong Base or a Weak Base conductometric
titration ......................................................................................................................................................... 7
Figure 8: Displacement titration conductometric titration .......................................................................... 7
Figure 9: Precipitation Titration conductometric titration ........................................................................... 8
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 CONDUCTOMETRY

Conductometry
1. Introduction
Voltammetric titration and conductometric titration are the two categories into which electrometric
titration can be split. These two classes of titration are governed by fundamentally distinct
hypotheses. As the change in the potential of a suitable electrode is a linear function of the change
in the logarithm of the ion concentration or the ratio of the concentration of oxidant to reductant,
the theory of potentiometric titration is identical to that of ordinary titration.
A large increase in the potential difference at the equivalence point indicates a sharp change in the
color of a suitable indicator. Titration to a definite potential is similar to ordinary titration, in which
a reagent is added until the indicator reaches a specific color. As a result, in a potentiometric
titration, the electrode is more or less compared to a specific indicator for the ion or redox system
to be titrated.
In a conductometric titration, all ions present contribute to the solution's electrical conductivity. If
an electrolyte is added to a solution of another electrolyte without causing a significant change in
volume, the conductivity increases as long as the electrolytes do not react.
In a conductometric titration, the conductance is measured after adding successive amounts of
reagent in a conductometric titration. The obtained points are plotted to produce a graph consisting
of two straight lines intersecting at the equivalence point. As a result, the equivalence point is
found graphically. Measurements near the equivalence point have no special significance in
comparison to any other type of titration method.

2. Principle of conductometric titration

If an ion of one electrolyte interacts with an ion of the other electrolyte to produce a slightly
dissociative/slightly soluble product, or if there is any change due to oxidation and reduction, the
solution's conductivity can be altered in three ways. The reaction between the analyte and the
reagent may be expressed by the equation:
B+ + A- + C + + D - BD + A- + C +
Where A and B are electrolytes to be determined and C and D are reagents.
Case 1: The conductance may decrease
When the reagent CD is added to the BA solution, the conductance decreases. This is most
common in titrations of strong acids with strong bases or in reverse titration. The hydrogen and
hydroxyl ions are distinguished from the other ions by their much greater mobility.
Case 2. The conductance may remain the same
AB and Ac are the same. The addition of CD has no effect on the conductance until the equivalence
point is reached. Most precipitation reactions encounter this case. When silver nitrate is titrated
with barium chloride, the barium ion replaces the silver ion, and because both ions have roughly

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 CONDUCTOMETRY

the same mobility, the conductivity does not change during the reaction. When sodium chloride is
used as a reagent instead of barium chloride, the conductivity decreases slightly. When potassium
chloride is used as a reagent, the conductivity increases slightly.
Case 3: The conductance may increase
If a slightly dissociated substance is titrated and the reaction product is a strong electrolyte, the
conductivity increases from the start of the titration. In general, this occurs when a weak acid is
neutralized by a strong base or a weak base is neutralized by a strong acid. In any case, once the
equivalence point is reached, the conductivity increases, at least if the reagent is a strong
electrolyte.

2.1. Definition of Terms and relations in conductometry

Ohm’s Law: states 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.
I = E/R
Conductance(C): is the ease with which the current flows through the conductor, thus the
conductance is reciprocal to resistance.
C= 1/R
Specific resistance (ρ): is the resistance offered by a substance of 1cm length and [Link] surface
area.
R = ρ l/a
Where, ρ is the specific resistance or resistivity; l is the length; a is the cross-sectional area of the
homogenous material. Unit of measurement is ohm cm.
Specific conductivity (kv): is the conductivity offered by a substance of 1cm length and [Link]
surface area, Unit of measurement is mhos cmˉ1
Cell constant: since the electrode in the cell are not exactly one cm apart and their sq. cm is not
exactly one centimeter, cell constant need to be determined for the system. The cell constant is
calculated as:
1\observed conductivity specific conductivity
Cell constant= 1\specific conductivity = observed conductivity

Then, the specific conductivity will be:

Specific conductivity= 𝑐𝑒𝑙𝑙 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 × 𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑣𝑖𝑡𝑦
Equivalent conductivity (λv): is the conductivity of a solution containing equivalent weight of
the solute between electrodes 1cm apart and 1sq cm surface area. Unit of measurement is mhos
cmˉ1
𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑎𝑛𝑐𝑒(𝜆) = 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑎𝑛𝑐𝑒(𝑘) × 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
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 CONDUCTOMETRY

Molecular conductance: the conductance of a solution containing 1gm mole of electrolyte when
placed between two sufficiently large electrodes placed 1cm apart. It is denoted by µv and is
measured in mhos
𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑎𝑛𝑐𝑒 = 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑎𝑛𝑐𝑒 × 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

3. Instrumentation and conductivity measurement

3.1. Instrumentation
The resistance of a solution cannot be measured by directly measuring the current passing through
it when two electrodes are inserted to it and a potential difference is applied across the electrodes.
This is the case because the electrodes will be polarized upon the application of potential difference
and increase the resistance of the solution. These will falsify the result measured.
To avoid this problem special instruments should be used. Therefore to conduct conductometirc
titration three types of instrumentation should be present and connected. These instruments
include:
1. Current source
2. Conductivity cell
3. Electrodes
1. Current source
In different conductometry titration experiments, different scientists have used different current
sources. The most common current sources used are:
 Mechanical high frequency AC generator by Washburn.
 Vreeland oscillator by Taylor and Acre.
 Vacuum tube oscillator by Hall and Adams.
2. Conductivity cells
Conductivity cells of various types are available. They are commonly made of Pyrex or quartz and
are fitted with two platinum electrodes. While choosing among these cells different factors like
shape, size, and electrode placement are considered for precision measurement.

Figure 1: Types of Conductivity cells

Generally there are 3 types of conductivity cells used in conductometric titration.

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 CONDUCTOMETRY

1. Wide mouthed cells (Type A): This type of cell have wide bottom fitted with ebonite
covers that have provisions for platinum electrodes and burettes. This type of cell is
majorly used for low conductance measurement.
2. Cells for precipitating type of reaction (Type B): In this type the electrodes are
firmly fixed in the Perspex lid which is provided with opening for the stirrer and the tip
of the burette. The stirrer may be replaced by magnetic stirrer. This type of cell is more
suitable for precipitate giving reactions since the face of electrode plates are vertical
and parallel.
3. Dip type (Type C): In a wide bore corning glass tube is fixed copper wires, the tip of
which have two platinum plates of 1 sq. cm in size fixed at 1 cm apart. The terminals
of copper wire are taken out for connections. The position of wire is fixed in glass tube
by rosin. The two inside faces of platinum electrode of cell are plated with platinum
black. This reduces polarization effect and allows absorption of ion on its surface.
3. Electrodes
To avoid polarization while applying potential difference, the electrodes that can be used in
conductometric titration are hydrogen calomel, and platinum electrode. The use of electrodes
depends on the conductance of the solution. If the solution have low conductance then more packed
electrodes should be used and Vis versa.
Platinum electrode is the most common type of electrode used in this setting. To prepare platinum
electrode the electrode should be coated with platinum black by using 3% chloroplatinic acid and
lead acetate on it to get a uniform coating.
4. Conductivity water:
Conductivity of solution of any electrolyte is very sensitive to presence of impurities. It is
therefore necessary that water used in a measurements of conductance should be of high degree of
purity. For the purpose of conductometry, ordinary distilled water is not suitable due to dissolved
CO2 and traces of laboratory gases.
Thus absolutely pure water, known as conductance water is used. It can be prepared by distilling
ordinary distilled water containing an acidified solution of KMnO 4, through an alkaline
solution of KMnO4, and condensing the vapors by a tin condenser in a flask of glass provided with
a soda lime guard tube.

3.2. Measurement
Conductivity meter

Figure 2: A wheat stone bridge circuit

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 CONDUCTOMETRY

The conductance measures are made by using a conductivity ground. The conductivity measures
are made by using a wheat gravestone ground circuit. In this cell placed in one arm of the wheat
gravestone ground circuit ab and resistance R constitutes the arm ac the arms bd and dc are in the
form of calibrated slide line resistor. The balance point of d is a sliding contact which shows no
signal to sensor D. This sensor is either a galvanometer, earphone, oscilloscope, magic- eye or
now-a-days calibrated digital display.
A source of interspersing current (V) with a frequency of 50- 60 Hz or a mains operated oscillator
giving a current with frequency up to 3000 Hz is used in the circuit by connecting b and c.
Conductivity measures have a range switch (chooser range) to elect applicable standard resistances
(or standard conductance), a calibrate switch (calibrate) with which the instrument is calibrated to
an asked value of conductance. A number of conductivity measures are commercially available.
To measure the conductance of electrolyte result, conductivity cell is dipped into it and outstations
connected to test outstations of Conductivity Bridge. The chooser switch is set to the applicable
conductance range and reading is recorded from the galvanometer read out cadence.

4. Types of conductometric titration

4.1. Strong acid with strong base
When titrating hydrochloric acid with sodium hydroxide, the first decrease in conductance is
brought on by the substitution of sodium ions with slow ionic mobility (50) for high ionic mobility
hydrogen ions (350). Once an excessive amount of hydroxyl ions (199) are introduced, the
endpoint conductance increases. The following graph is obtained

Figure 3: Strong acid with strong base conductometric titration

4.2. Strong acid with weak base

The graph in figure is produced by titrating a strong acid, such as hydrochloric or sulfuric acid,
with a diluted ammonia solution. The gradual decrease in conductance is caused by the elimination
of highly mobile hydrogen ions during neutralization. Since the formation of ammonium chloride
or ammonium sulphate during the neutralization process prevents the ionization of ammonia, the
graph almost turns horizontal after the end.

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 CONDUCTOMETRY

Figure 4: Strong acid with weak base conductometric titration

4.3. Weak acid with strong base

The form of the graph in the titration of weak acids, such as acetic acid or boric acid, with strong
bases, such as NaOH, depends on the concentration as well as dissociation constant of said acid.
As a result, the ionization of a little volume of acetic acid is what causes the first conductance in
the neutralization of acetic acid. Conductance is increased by the gradual salt production, which
in turn suppresses acetic acid ionization. These two antagonistic effects cause conductance to dip,
then increase. A pause takes place just after neutralization, revealing an increase in conductance
caused by hydroxyl ions.

Figure 5: Weak acid with strong base conductometric titration

4.4. Weak acid with weak base

Titration of weak acids, such as acetic acid or phenol, with weak bases, such as aqueous ammonia
solution, produces the graph shown in the figure, as an example.
Because of the weak acid's salt formation, conductance increases. Because the salt created prevents
ammonia from ionizing, a surplus of aqueous ammonia solution will have no impact on
conductivity after the equivalence point.

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 CONDUCTOMETRY

Figure 6: Weak acid with weak base Conductometric titration

4.5. Mixture of a Strong Acid and a Weak Acid vs. a Strong Base or a 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.
However, when the titrant is a weak base, it remains almost constant after the end point.

Figure 7: Mixture of a Strong Acid and a Weak Acid vs. a Strong Base or a Weak Base conductometric titration

4.6. Displacement titration

Conductometers can be used for the titration of weak acid salts like sodium acetate with strong
acids as HCl and weak base salts such as ammonium chloride with strong bases like sodium
hydroxide. A graph such as the following is produced

Figure 8: Displacement titration conductometric titration

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 CONDUCTOMETRY

The initial increase in conductivity in the sodium acetate with HCl titration is caused by somewhat
greater ionic mobility of chloride ions than acetate ion. Solution has enough CH3COONa to
prevent the ionization of released CH3COOH until replacement is fully achieved.
The acetic acid is significantly ionized around equivalent point to increase conductivity. High
conductance is caused by an oversupply of hydrochloric acid beyond the equivalence point.
Similar to this, the initial decrease in conductance in the titration of ammonium chloride with
sodium hydroxide is caused by the sodium ion replacing the ammonium ion (high mobility) (low
mobility). The sodium hydroxide hydroxyl ion is what causes the conductance to sharply increase
after the equivalence point.

4.7. Precipitation Titration

This type of titration is only done when the reaction product is sparingly soluble, forms stable
complex and the precipitate don’t have strong adsorbent property.
For example, the titration of silver nitrate with KCl and/or sodium sulfate with barium chloride
yields the following graph.

Figure 9: Precipitation Titration conductometric titration

5. The general process of conductometric titration

For the conductometric titration of an acid with a base, the general process is as follows
Step 1: 10 ml of the acid must be adulterated with roughly 100 ml of distilled water (so that the
changes in the conductance brought on by the addition of the base come small).
Step 2: A burette must now be filled with the base and the original volume must be noted.
Step 3: In this step, a conductivity cell must be fitted into the diluted acid result in a way that both
the electrodes are fully immersed.
Step 4: Now, the conductivity cell can be connected to a digital conductometer in order to gain an
original reading.
Step 5: The base must now be added drop wise into the acid result. The volume of base added
must be noted along with the corresponding change in the conductance.

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 CONDUCTOMETRY

Step 6: A sharp increase in the conductance of the result implies that the endpoint has been
reached. Still, a many further readings must be taken after the endpoint of the titration.
Step 7: These observed values must now be colluded graphically. The parity point can be attained
from the point of crossroad between the two lines.
The strength of the acid can now be calculated via the formula S2 = (V1S1)/ 10; where S2 is the
strength of the acid, V1 is the volume of base added (as per the parity point on the conductometric
titration graph), and S1 is the strength of the base (formerly known).

6. Factors affecting conductance of solution

6.1. Concentration of ions
The ions that are present in electrolytes are the only factors contributing to their conductivity. As
there are more charge carriers if the ion concentration is higher, the conductivity of electrolytes
will be high. This is because the conductivity of electrolytes increases with an increase in ion
concentration.
As the concentration of the solution drops, molar conductivity rises. The conductance of the entire
volume of a solution containing one mole of solute is known as its molar conductivity. Because
the volume grows with dilution rather than the number of molecules, the force of attraction
between the ions weakens, allowing them to flow more freely and increasing conductance.

6.2. Nature of electrolyte

The composition of electrolytes has a considerable impact on electrolytic conduction. The
concentration of ions in the solution and, consequently, the conductivity of electrolytes are
determined by the degree of dissociation of the electrolytes. Weak electrolytes are substances like
CH3COOH that have a low degree of separation because they have fewer ions in the solution and
therefore have a lower conductivity. Strong electrolytes like KNO3 have a high degree of ion
concentration in their solutions due to their high degree of ion dissociation, making them good
electrolytic conductors.

6.3. Temperature
The amount to which an electrolyte dissolves in a solution is influenced by temperature. Higher
temperatures have been found to improve the solubility of electrolytes and, in turn, the
concentration of ions, increasing the rate of electrolytic conduction.

7. Application of conductometry
7.1. Determination of solubility of sparingly soluble material:
A saturated solution of a sparingly soluble salt's specific conductance (k) is determined. The
equivalent conductance of a sparingly soluble salt in saturated solution is thought to be nearly
equal to the limiting conductance value. This can be calculated by adding the limiting
conductance of the constituent ions. Solubility can be determined by measuring specific
conductance and limiting the conductance of constituent ions of sparingly soluble material.

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 CONDUCTOMETRY

7.2. Kinetic research:

Kinetic studies of reactions rely on measuring conductivity before, during, and after a chemical
reaction. The course of any reaction in which ions are produced, consumed, or exchanged can be
tracked.
For example, in the alkaline hydrolysis of ethyl acetate.

7.3. Determination of concentration:

The determination is based on determining the conductivity of a solution at various concentrations.
A series of solutions with known electrolyte concentrations are prepared, their conductivities are
determined, and the calibration curve of solution conductivity versus electrolyte concentration is
plotted.
The calibration curve is then used to determine the conductivity of the unknown solution and the
concentration. Direct conductometric analysis is particularly useful for routine analysis of
solutions containing a single electrolyte, particularly if the solutions are colored or turbid.
Industrial conductometers are widely used in chemical plants for automatic control of solution
concentration.

8. Advantage and limitations of Conductometry

This is a list of some benefits of conductometric titration.
 When titrating extremely diluted solutions and weak acids, this method is quite helpful.
 As compared to a few other titration techniques, this method's end-point is extremely
precise and crisp.
 This kind of titration is appropriate for colored or turbid solutions, when the endpoint of
the titration using conventional indicators cannot be readily seen by the naked eye.
 Acid-base titrations, redox titrations, precipitation titrations, and complicated titrations
are only a few of the many uses for conductometric titration.
These are the two main drawbacks of this kind of titration:
 This method can only be used for a small number of redox titrations. This is due to the
unusually large concentration of hydronium ions in the solution, which obscures the
solution's conductivity.
 When the electrolyte concentrations are high, conductometric titration's precision is poor,
which leads to an unsatisfactory titration procedure.

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 CONDUCTOMETRY

References

Chatwal, G. a. (2003). Instrumental Methods of Chemical Analysis. Mumbai: Himalaya Publishing

House.
Khopkar, S. (2004). Basic concepts of Analytical Chemisty. New Delhi: New Age International Limited.
Kolthoff, I. M. (1930). Conductometric Titrations. Industrial & Engineering Chemistry Analytical
Edition, 225 - 230.
Pungor, E. (1965). Oscillometry and Conductometry: International Series of Monographs in the Science
of the Solid State. Elsevier Science \& Technology. Retrieved from
[Link]
University, G. T. (2018, october). Conductometry lecture note 1-4. Gujarat, India.

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