SADAF IQBAL

ROLL NO. 57
BS-Chemistry
7th Semester
Submitted to; MA’AM MADIHA
BATOOL
Subject;Practical of Inorganic
Chemistry

TOPIC;
CONDUCTOMETRIC
&
HIGH FREQUENCY
TITRATIONS
CONDUCTOMETRY
 INTRODUCTION

 PRINCIPLE

 IMPORTANT DEFINITIONS & RELATIONS

 INSTRUMENTATIONS

 MEASUREMENT OF CONDUCTIVITY

 CONDUCTOMETRIC TITRATIONS
 INTRODUCTION
 TYPES
1) ACID-BASE TITRATION
2) DISPLACEMENT TITRATION
3) REDOX TITRATION
4) PRECIPITATION TITRATION
5) COMPLEXOMETRIC TITRATION

 ADVANTAGES & DISADVANTAGES OF

CONDUCTOMETRIC TITRATIONS
 LIMITATIONS

 APPLICATIONS OF CONDUCTOMETRY
 CONCLUSION
 REFERENCES
CONDUCTOMETRY
INTRODUCTION
➤ It is an electrochemical method of analysis concerned with electrical
conductance through an electrolyte solution.

(or)

➤ It is defined has as determination or measurement of the electrical

conductance of an electrolyte solution by means of a conductometer.

❖ electric conductivity of an electrolyte solution depends on :

1. Type of ions (cations, anions, singly or doubly charged)

2. Concentration of ions

3. Temperature

4. Mobility of ions

PRINCIPLE

➤ Based on the conductance of electrical current through electrolyte solutions

similar to metallic conductors

The electric conductance in accordance with ohms law which states that the
strength of current(I)passing through conductor is directly proportional to
potential difference & inversely to resistance.

I=V/R

Important definitions & relations

➤ Conductance
➤ Specific conductance
➤ Molar conductance
➤ Equivalent conductance
➤ Resistance
➤ Specific resistance

Conductance(G):
Ease with which current flows per unit area of conductor per unit
potential applied & is reciprocal to resistance(R) .
G = I/R
Specific conductance (K):
Conductance of the body of uniform length(l) & uniform area
cross section(A).
K=l/Rxl/A

Molar conductance: (^)

Conductance of a solution containing 1 mole of the solute in 1000
cm of the solution which placed between two parallel electrodes which are 1
cm apart .
^ = 1000/C

Equivalent conductance (^eq):

Specific conductance of the solution containing 1gm equivalent of

solute in 1000cm³ of solution.
^eq =1000k/Ceq

Resistance (R):

Is a measure of the conductors opposition to the flow of electric

charge
R =I/G

Specific resistance (p):

Is resistance offered by a conductor of unit length and having unit

cross section
p=AR/l

The conductance of the solution depends on:

Temperature: It is increased by increase of temperature.
• Nature of ions: size, molecular weight, number of charges the ion carries
and other factors
• The concentration of ions: As the number of ions increases the
conductance of the solution increases.
• The size of the electrodes
G = kvA/L L/A is cell constant
kv = GL/A K is the specific conductance or conductivity
ohm-1cm-¹ or seimen/cm.

Instrumentation
The instrument used for measurement of conductance are known as
conductometer.
It consists of:

1. Current source
Alternating current source

2. Conductivity cells
 Wide mouthed cells
 Cell for reactions producing precipitates
 Dip type cells

3. Electrodes

CURRENT SOURCE

I. Mechanical high frequency AC generator by Washburn.

II. Vreeland oscillator by Taylor and Acree.
III. Vacuum tube oscillator by Hall & Adams.

When electrical potential is applied across electrodes two process

occurs.
 Ions accumulate near the electrodes.
 Transfer of charge through the interface.
Note: DC current is not employed in conductance measurement because
electrodes becomes polarised leading to high cell resistance.

Conductivity cells

 Made of pyrex or quartz and are fitted with two platinum electrodes.

 Should be placed in vessel containing water to maintain constant

temperature.

 Types:

1. Wide mouthed cell

2. Cell for reactions producing precipitation
3. Dip type cells

Wide mouthed cell:-

• Measurement of low conductance
• Wide mouthed fitted with an ebonite cover which has provisions for
platinum electrodes and burettes.

Cell for reactions producing ppts:-

 Mainly used for ppt reactions
 Also wide mouthed fitted with ebonite cover which has provisions for
burette,electrode ,stirrer.
 Stirrer may be mechanical or magnetic.

Electrodes

• Platinum sheets, each of 1 cm² are fixed at distance of 1 cm

• The surface is coated with platinum black to avoid polarization effects and
increase effective surface area.
• Platinisation of electrodes is done by coating solution of 3% chloroplatinic
acid and lead acetate on it to get uniform coating
• Electrodes usage depends on conductivity and concentration
• If concentration is low then electrodes should be largely and closely packed

Measurement
• The instrument used to measure conductance is called conductance bridge
or conductometer
• Classical circuit employed for measurement is wheatstone bridge
• All other work on this principle
• Various types are:
1. Kohlrausch conductance bridge
2. Direct reading conductance bridge
3. Phillips conductance bridge
4. Mullard conductance bridge
5. Pye's conductance bridge

Kohlrausch conductance bridge:-

• Consists of a meter bridge XY with fixed resistors r' & r" at both ends. One
arm of bridge consists of resistance box 'R' & other arm with conductivity cell
'C'. Detector D is head phone while inductance coil 'J' is AC source which is
operated by battery.

Direct reading conductance bridge:-

• In this head phone is replaced by magic eye which is electronic device.

The set up for Measurement :

consists of meter bridge LN attached to standard resistance R1 & unknown
resistance R2.
Cell is connected to standard resistance to one side , meter bridge LN
at other. The sliding contact with galvanometer (G) can be moved on the wire
of meter bridge by means of jockey (M) so that resistance of unknown is
balanced with that of standard.
When galvanometer shows null deflection, the resistance of unknown
is measured by following equation:

ML/NL =R2/R1

R2 =ML/NL x R1

Hence conductivity of unknown solution:

I/ R2= NL / M L x R1
The measured conductivity (I/R1) is not always equal to the specific
conductivity of solution, because the physical configuration of platinum
electrode i.e, length and area of electrodes varies from one another Hence
conductivity of solution is obtained by calculating a factor called "cell
constant".

Cell constant:
Defined as ratio of distance between the two electrodes(l) to the area of
electrodes(A) Therefore,
O=l/A

CONDUCTOMETRIC TITRATIONS:
INTRODUCTION:
• Is process of qualitative chemical analysis in which concentration of sample
is determined. Which is done by adding a reagent( titrant) of known
concentration in measured volumes to the sample (analyte).
TYPES OF CONDUCTOMETRIC TITRATIONS:
• Acid -base or neutral titrations
• Replacement or displacement titrations
• Redox titrations
• Precipitation titrations
• Complexometric titrations

ACID- BASE OR NEUTRAL TITRATIONS

>STRONG ACID-STRONG BASE
EG: HCL vs NaOH

>STRONG ACID-WEAK BASE

EG: HCL vs NH4OH

>WEAK ACID-STRONG BASE

EG: CH3COOH vs NaOH

>WEAK ACID -WEAK BASE

EG: CH3COOH vs NH4OH

Strong acid strong base:

• Fall in conductance due to replacement of high conductivity Hydrogen ions
by poor conductivity sodium ions
• Rise in conductance due to increase in hydroxyl ions
Strong acid- weak base:
• Fall in conductance due to replacement of hydrogen by ammonium ions
• Conductance remain constant due to supression of NH40H by NH4Cl

Weak acid -Strong base:

• Initial decrease in conductance followed by increase due to NaOH
• Steep rise due to excess of NaOH

Weak acid- weak base:

• Increase in conductance due to excess of CH3COOH
• Constant conductance due to suppression of NH4OH by CH3COOH

DISPLACEMENT TITRATION
While a salt of a weak acid is titrated along with a strong acid, a anion of the
weak acid is exchanged through that of the strong acid and weak acid itself is
liberated within the undissociated form. As same, further of a strong base to
the salt of a weak base, a cation of the weak base is replaced through that of
the stronger one and the weak base itself is produced in the undissociated
form. If for instance, M-HCl is added to 0.1 M solution of sodium acetate, the
curve displays in Figure is acquire, the acetate ion is replaced through the
chloride ion after the endpoint. An initial rise in conductivity is because of the
fact in which the conductivity of the chloride ion is slightly greater than which
of acetate ion. Until the replacement is nearly finished, the solution contains
sufficient sodium acetate to suppress the ionization of the liberated acetic acid,
so resulting a negligible increase in the conductivity of the solution. Therefore,
near the equal point, the acetic acid is satisfactorily ionized to affect the
conductivity and a rounded portion of the curve is obtained. Beyond the
equivalence point, while excess of HCl is present (ionization of acetic acid is
extremely much suppressed) thus, the conductivity arises rapidly. Care must
be taken that to titrate a 0.1 M-salt of a weak acid, a dissociation constant
should not be more than 5×10-4, for a 0.01 M -salt solution, Ka < 5 ×10^-
5 and for a 0.001 M-salt solution, Ka < 5 ×10^-6, i.e., the ionization constant
of the displace acid or base divided by the real concentration of the salt must
not exceed above 5 ×10^-3. Also involves the titration of 0.01 M- ammonium
chloride solution versus 0.1 M- sodium hydroxide solution. The reduction in
conductivity during the displacement is caused through the displacement of
ammonium ion of grater conductivity through sodium ion of smaller
conductivity.

Figure: Conductometric titration of a salt of weak acid (sodium acetate) vs.

strong acid (HCl); salt of a weak base (NH4Cl) vs. a strong base (NaOH)

REDOX TITRATION
 Redox titration is the type of titration which applies the oxidation-reduction
reaction. The analyte and the titrate react through this reduction or redox
technique. Similar to acid-base titration, the endpoint or the equivalent point
in the redox titration is known through the use of an indicator, also called a
potentiometer. Redox titration is one of the usual techniques used to
determine and identify the concentration of various unknown analytes in a
given solution.Instead of examining the concentration, it is proven to be more
convenient to examine the potential of the reaction in redox titration. Hence,
it is crucial to obtain the shape of the correlated titration curve.

PRECIPITATION TITRATION

Precipitation titration is a type of titration in which the titrant is made to react

with an analyte to form a precipitate. During this experimentation of titration,
an insoluble substance is formed after the analytical procedure is completed
and every drop of the analyte is used for the formation of the precipitate. In
case the titrant is in excess, it will automatically react with indicators like
potassium chromate, silver nitrate or fluorescein ions, and provide a signal to
terminate the titration procedure. Basically, the principle on which the
precipitation titration method works is that the amount of reagent added
should be equal to the amount of the precipitate formed.It is used in many
pharmaceutical industries and food industries to measure the level of the
content of salt in different food and drinks.The precipitation titration is not
conducted with just a single method. In fact, there are three types of distinct
methods that are used to carry out this titration, namely Volhard’s method,
Fagan’s method, and Mohr method.
eg Potassium chloride Vs Silver nitrate
KCI + AgNO3→ AgCl + KNO3
• When silver nitrate added, the first part of the curve shows no increase in
conductivity as there is only replacement of chloride ions with nitrate ions.
• After end point conductivity increases because of increase in the
concentration of silver as well as nitrate ions.
COMPLEXOMETRIC TITRATION

Commonly known as chelatometry, complexometric titration is used to specify

an endpoint of a titration through the formation of a colored complex by
volumetric analysis. The reason replacement titration is also termed
volumetric analysis is that it involves the measurements of volumes of titrants
that are reacted. The process involves the tracing of a mixture of metal ions in
the solution.The reaction is brought to equilibrium by adding drops of titrants
in the solution in succession. The most common titrant that is used is the
EDTA (ethylenediaminetetraacetic acid) titrant. Complexometric titration is
one of the most widely used types of titrations because it gives a very accurate
identification of the equivalent points. For the most part, this titration is used
to titrate phosphates, oxalates, and benzoates.The commonly used indicators
in this titration method are Calmagite and Eriochrome Black T (EBT). Using
these indicators there are two methods by which the endpoint can be
detected- the visual method and the instrumental method.

ADVANTAGE OF CONDUCTOMETRIC TITRATIONS:

1. Does not require indicators since change in conductance is measured by
conductometer.
2. Suitable for coloured solutions.
3. Since end point is determined by graphical means accurate results are
obtained with minimum error.
4. Used for analysis of turbid suspensions, weak acids, weak bases, mix of
weak & strong acids.

Disadvantages of conductometric titration:

1. Increased level of salts in solution masks the conductivity changes, in such
cases it does not give accurate results
2. Application of conductometric titrations to redox systems is limited because,
high concentrations of hydronium ions in the solution tends to mask the
changes in conductance

Limitations of Conductometric Titration

With various advantages, conductometric titration has few limitations as well
which are listed below By conductometric titration technique, only a few
specific redox titrations can be carried out. It shows less accurate results when
the total electrolytic concentration is high in solution. It makes it less
satisfactory.

Applications:

 Check water pollution in rivers and lakes.

 Alkalinity of fresh water.
 Salinity of sea water (oceanography).
 Deuterium ion concentration in water- deuterium mixture.
 Food microbiology- for tracing micro organisms.
 Tracing antibiotics.
 Estimate ash content in sugar juices.
 Purity of distilled and deionized water can determined.
 Solubility of sparingly soluble salts like AgCl, BaSo4 can be detected.
 Determination of atmospheric so2, estimation of vanillin in vanilla flavour.

Conclusion:
The electrical conductance of a solution is a measure of the solution's ability to
conduct electricity. The ability of a solution to conduct electric current
decreases as the resistance of the solution increases. Electricity is conducted
in a solution by ions of electrolytes. Conductance of electrolytes increases with
the increase of temperature and concentration of electrolytes. The
conductance of a solution is the sum of the conductance of all the ions in the
solution. The conductance of an ion in solution is related to the charge, size
and concentration of the ion. Conductometry can be used to locate the end
point of the titration. Conductometric titration is useful for acid-base,
precipitation, and complexation titrations.
REFERENCES
 Instrumental analysis by A. Skoog, F. James Holler and Stanly R. Crouch.
 Text book of pharmaceutical analysis, third edition by Dr.S.Ravi sankar.
 https://www.slideshare.net/ProfYogitaThakare/lect-8-conductometric-
titration
 https://www.vedantu.com/chemistry/conductometric-titration
 https://www.slideshare.net/KrishnaKumar1406/conductometry-titration
 https://testbook.com/chemistry/conductometric-titration
 https://www.slideshare.net/RabiaAziz6/conductometric-titration
 Termmate: https://www.termmate.com/rabia.aziz 2
 https://www.youtube.com/channel/UCKxWnNdskGHnZFS0h1QRTEA
 https://web.facebook.com/Chemist.Rabia.Aziz/
 https://chemistry-academy.blogspot.com/
 Experimental chemistry Titration part 1 Chemistry with
Modern Technology By Eman Shams
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Harris (Author), Charles A. Lucy (Author)
 Vogel's Quantitative Chemical Analysis 6th Edition by J.
Mendham (Author)
 Principles of Analytical Chemistry: A Textbook 2000th Edition, Kindle
Edition by Miguel Valcarcel (Author) Format: Kindle Edition
 Quantitative Analysis 6th ed. Edition by R A Day (Author), Arthur L
Underwood (Author), A L Underwood (Author)
 Dean's Analytical Chemistry Handbook 2nd Edition
by Pradyot Patnaik (Author)