EXPT.

9 ARGENTOMETRIC DETERMINATION
OF CHLORIDE IONS BY MOHR’S and
FAJAN’S METHODS
Structure
9.1 Introduction
Objectives
9.2 Principle
9.3 Requirements
9.4 Solutions Provided
9.5 Procedure
9.6 Observations and Calculations
9.7 Result

9.1 INTRODUCTION
In the previous two experiments you have learnt about and performed redox titrations
involving I2 / I− redox couple. These involved the iodimetric determination of ascorbic
acid in a tablet of Vitamin C and the iodometric determination of available chlorine in
a sample of bleaching powder. In the current and the next experiment you will learn
about and perform precipitation titrations. As the name suggests these titrations are
based on the formation of precipitates between the titrant and the analyte. You would
recall from section 12.2 of Unit 12 of the MCH-001 course that a large variety of
titrants can form a precipitate with the analytes but very few titrant–analyte
combinations qualify to be used in an analytical determination involving precipitate
formation. The limitation of the number of precipitating agents is because of the slow
rate of formation of most precipitates. The most common examples of precipitation
titrations are the ones involving silver ions. These involve either the determination of
silver ions using halide ions as a titrant or the ones involving determination of halide
ions using silver nitrate as the titrant. The later are called argentometric titrations. In
this experiment you would learn about and perform the determination of chloride ions
in an aqueous solution using an argentometric titration. You would perform the same
determination using two different methods, namely, Mohr’s method and Fajan’s
method. Each of these employ a different method for the determination of the end
point.

In the next experiment you would learn about and perform the determination of zinc
ions in a solution by precipitating with potassium ferrocyanide.

Objectives
After studying and performing this experiment, you should be able to:
• define precipitation titrations,
• state and explain the principle of precipitation titrations with reference to the
determination of silver ions in an aqueous solution,
• explain different basis of end point determination in the argentometric titrations,
• prepare a standard solution of sodium chloride and use it for the standradisation
of silver nitrate,
• titrate the given solution of chloride ions with silver nitrate by using Mohr’s and
Fajan’s methods, and

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 • calculate the amount of chloride ions in the given aqueous solution by using
Mohr’s and Fajan’s methods

9.2 PRINCIPLE
As mentioned in the introduction, titrations based on the formation of a precipitate
between the titrant and the analyte are termed as precipitation titrations. The basic
requirements for a precipitation reaction to become a basis for analytical determination
are that the reaction must be sufficiently rapid and complete, and give a product of low
solubility and of reproducible composition. Further, a method must be available to
locate the end point for the titration. The argentometric determination of chloride ions
is based on the following precipitation reaction.
Ag + + Cl − → AgCl(s) ↓ Ksp = 1.82 x 10‾10

The curve for the titration of 100 cm3 of 0.0100 M KCl with 0.100 M AgNO3 is shown
in Fig.9.1.
10

6
pAg

0
0 2 4 6 8 10 12 14 16 18 20 22

Volume of 0.001
V olume M AgNO
of 0.1000 3 titrant,
M A gNO cm
3 titrant,m3 L

Fig.9.1: Calculated titration curve for the titration of 100.0 cm3 of 0.0100 M KCl with
0.1000 M AgNO3
You may note here that the titration curve is quite similar to the one for the titration
between a strong base and a strong acid. According to this curve there is a sharp
increase in the concentration of silver ions immediately after the equivalence point.
This is indicated by a sharp decrease in the value of pAg+ ( -ln(Ag+)). Such a sharp
increase in the concentration of silver ions can be detected in different ways and
accordingly there are three different methods of detecting the end point of the titration.
These, in turn form the basis for three different methods of performing argentometric
titrations. However, in this experiment you would be using two of these methods,
namely, Mohr’s method and Fajan’s method. Let us briefly learn about these methods.
( It will be worthwhile if you could revisit sections 12.5 to 12.8 of Unit 12 of MCH 001
course)

Mohr’s method
In the Mohr’s method the determination of the end point is based on the formation of a
second precipitate which is coloured. The requirement here is that the second
precipitate should have solubility slightly greater than the precipitate between the
analyte and the titrant. The indicator used is sodium chromate and the second
precipitate formed is brick–red coloured silver chromate, Ag2CrO4.

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On the addition of a solution of silver nitrate to the titrand (containing chloride ions-
the analyte and chromate ions-the indicator) two precipitates are formed. These are
AgCl and Ag2CrO4 respectively. The reactions can be given as under
Ag + + Cl − → AgCl(s) ↓ (white)

Ag + + CrO 24− → AgCrO 4 (s)

↓ (brick red)
The silver chromate having greater solubility stays in solution whereas silver chloride
precipitates out. At the end point the excess of silver ions forms the precipitate of
silver chromate that imparts distinct colour to the solution thereby marking the end
point.

The titration is carried out at a pH between7 to 10. This is so because in acidic Chromate ion is the conjugate
solution the chromate ion gets converted into chromic acid and the concentration of base of chromic acid
chromate ion becomes quite low. It is not sufficient to precipitate the silver ions as
silver chromate. On the other hand, at the pH greater than 10 a brown precipitate of
hydrated silver oxide is obtained. The pH is maintained in the suitable range by adding
sodium bicarbonate to the analyte solution

The Mohr’s method suffers with a drawback as it has an inherent titration error. The
end point is not observed immediately after the equivalence point but after a little over
titration, i.e., after adding a little extra silver nitrate. (Please refer Section 12. 8.1of
Unit 12 of MCH - 001 course.) This necessitates the determination of an indicator
blank. This is determined by suspending solid, white, chloride–free calcium carbonate
in distilled water and making the volume as that of the titrated solution at the
equivalence point. This would have the concentration of CrO42– equal to that at the
equivalence–point. The Ag+ reagent is added to this suspension until the end point
colour is observed. The volume of Ag+ reagent required to match the end point colour
is subtracted from the end point volumes measured in the titrations of chloride.

Fajan’s method
While the Mohr’s method is based on the formation of a coloured precipitate at the
end point, the Fajan’s method is based on the principle of adsorption indicator. In this
method the chloride ions are determined by titrating directly with silver ions (from Adsorption indicators are
silver nitrate) using fluorescein as the indicator. Fluorescein is a weak acid, which dyes that adsorb, or desorb
partially dissociates in water to form fluoresceinate anion. from, the surface of a
precipitate near the
HO OH HO O O equivalence point in a
precipitation titration. These
impart distinct colour to the
C C precipitate.
O O +H+
C C

O O

Fluorescein Fluoresceinate anion(Yellow green)

– +
In the titration of Cl ions with Ag in the presence of fluorescein, the precipitate
formed (AgCl) adsorbs negatively charged chloride ions and acquire a negative
charge. This negatively charged precipitate repells the fluoresceinate anions. The
fluoresceinate ions remain in solution prior to the equivalence point. At the
equivalence point, the colloidal AgCl can no longer adsorb the negatively charged
chloride ions because their concentration is drastically lowered. On the other hand the
precipitate now adsorbs the positively charged silver ions that are in excess and make
the precipitate acquire a positive charge. This positively charged precipitate now
adsorbs the negatively charged fluoresceinate ions as the counter ions on the AgCl

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 colloids. This imparts a distinct red colour to the precipitate particles which marks the
end point. In other words, at the end point the colour changes from yellow–green to
red or pink.

However, the adsorption indicators suffer with a disadvantage that the adsorbed layer
of dyestuff sensitizes the precipitates of silver halides to the action of light. Therefore,
these titrations should be carried out in dark with a minimum exposure to sunlight.

9.3 REQUIREMENTS
Apparatus Chemicals
Volumetric flask (100 cm3) –1 Silver nitrate
Burette (50 cm3) –1 Sodium chloride
Pipette (10 cm3) –1 Potassium chromate
Weighing bottle –1 Fluorescein
Burette stand with clamp –1
Conical flasks (100 cm3) –2
Funnel –1
Beakers (250 cm3) –2

9.4 SOLUTIONS PROVIDED

1. 5% potassium chromate indicator solution: It is prepared by dissolving about
1.0 g of potassium chromate in about 20 cm3 of distilled water taken in a 100
cm3 beaker
2. Fluorescein indicator: It is prepared by dissolving 0.2 g fluorescein in 100
cm3 of 70 per cent ethanol water mixture
3. 0.1 M Silver nitrate: It is prepared by accurately weighing about 8.5 g of dried
analytical grade silver nitrate and dissolving it in about 100 cm3 of distilled
water taken in a 500 cm3 volumetric flask. The volume is then made upto the
mark with distilled water.

9.5 PROCEDURE
The determination of chloride ions in a solution using argentometric titration consists
of the following steps:
a) Preparation of standard solution of sodium chloride
b) Standradisation of silver nitrate solution
c) Determination of chloride ions in the given solution by titrating against
standaradised solution of silver nitrate.
Follow the instructions given below in sequential manner to perform the determination
of Chloride ions by Mohr’s and Fajan’s methods

a) Preparation of standard solution of sodium chloride

• Accurately weigh about 0.6g of sodium chloride in a clean dry weighing
bottle, and transfer the same to a clean volumetric flask of 100 cm3
capacity through a glass funnel.
• Add about 20 cm3 of distilled water and swirl the contents of the flask
until all the sodium chloride is dissolved
• Make the volume upto the mark by adding more distilled water

b) Standradisation of silver nitrate solution

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 • Pipette out 10 cm3 of the standard sodium chloride into a 100 cm3 conical
flask and add 10 drops of fluorescein indicator to it.
• Titrate the solution with silver nitrate solution taken in a burette. Perform
the titration in diffused light and ensure that the flask is constantly rotated.
With the progress of the titration, you would observe that the silver
chloride coagulates appreciably.
• Continue the titration and when the local development of pink colour on
adding silver nitrate solution becomes more and more pronounced slow
down the rate of addition of silver nitrate.
• The end point is indicated by sudden development of red or pink colour
on the precipitate. This does not disappear on swirling the titration flask.
• Repeat the standardization procedure at least three times and record your
observations in Observation Table 9.1.
• Use the data so obtained to determine the molar concentration of the silver
nitrate solution.

c) Determination of chloride ions in the given solution by titrating against the

standradised solution of silver nitrate
As mentioned above, you are going to determine the amount of chloride ion in
the given solution by using two different methods of end point determination.
Therefore the step c) is given in two parts; one for each method.

i) Mohr’s method
• Wash the burette with distilled water and rinse with standardised
solution of silver nitrate and then fill the burette with the same.
• Carefully pipette out 10 cm3 of given solution of chloride ions and
transfer into a 100 cm3 conical flask. Add 1 cm3 of the potassium
chromate indicator solution (it is advisable to use a 1 cm3 pipette for
the purpose).
• Titrate the solution with silver nitrate solution and ensure that the
flask is constantly swirled.
• With the progress of the titration, you would observe that the red
colour formed by the addition of each drop of Silver nitrate begins
to disappear more slowly; slow down the rate of addition of silver
nitrate.
The end point is indicated by sudden development of a faint but
distinct change in colour to reddish-brown. This does not disappear
on swirling the titration flask.
• Repeat the procedure for at least three times and record your
observation in Observation Table 9.2(a).

Determination of indicator blank

• In a clean and dry conical flask take distilled water equal to the
volume of titrand + volume of the titrant and add 1 cm3 of the
potassium chromate indicator solution with the help of a 1 cm3
pipette,
• Titrate the solution with silver nitrate solution while constantly
stirring the flask and determine the end point as above. ( As the
volume of silver nitrate used for the indicator blank is going to be

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 very small you are advised to add silver nitrate dropwise right from
the beginning of the titration).
• Note the volume of silver nitrate used for indicator blank and record
it after the Observation Table 9.2 (b)

ii) Fajan’s method

• Pipette out 10 cm3 of the given chloride ion into a 100 cm3 conical
flask and add 10 drops of fluorescein indicator to it.
• Titrate the solution with silver nitrate solution taken in a burette.
Perform the titration in diffused light and ensure that the flask is
constantly swirled.
• With the progress of the titration, you would observe that the silver
chloride coagulates appreciably.
• Continue the titration and when the local development of pink
colour on adding silver nitrate solution becomes more and more
pronounced, slow down the rate of addition of silver nitrate.
• The end point is indicated by sudden development of red or pink
colour on the precipitate. This does not disappear on swirling the
titration flask.
• Repeat the procedure at least three times and record your
observation in Observation Table 9.3.
• Use the data so obtained to determine the molar concentration of the
silver nitrate solution.

9.6 OBSERVATIONS AND CALCULATIONS

a) Preparation of standard solution of sodium chloride
Mass of weighing bottle + sodium chloride = m1 g = ..............g
Mass of weighing bottle (after transferring sodium chloride) = m2 g = ............. g
Amount of sodium chloride transferred = (m1 – m2) g = m g = ............. g
Molar mass (Mm) of sodium chloride = 58.44 g mol−1
Volume of sodium chloride prepared = 100 cm3
Molarity of standard sodium chloride solution =
m × 1000 10m
M NaCl = = = .........M
100 × 58.44 58.44

b) Standardisation of silver nitrate solution

Volume of standard NaCl solution taken in conical flask, VNaCl = …cm3
Solution in the burette: Silver nitrate
Indicator used: Fluorescein

Observation Table 9.1: Standardisation of silver nitrate

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S.No. Volume of sodium Burette reading Titre value (in cm3)
chloride (in cm3)
Initial Final (Final-initial reading)
1
2
3
Concordant reading

The concentration of the given silver nitrate solution can be determined as follows.

The reactions involved:

AgNO3 + Na Cl → AgCl(s) ↓ + NaNO3
Molarity equation: M AgNO3VAgNO3 = M Sodium chloride VSodium chloride

M Sodium chloride VSodium chloride

M AgNO3 =
VAgNO3
Substituting the values, the molarity of silver nitrate =
The molarity of given silver nitrate is = ……….M

c) Determination of chloride ions in the given solution by titrating against the

standradised solution of silver nitrate

i) Mohr’s method
Volume of chloride ion solution taken in conical flask, = 10 cm3
Solution in the burette: Silver nitrate
Indicator used: Potassium chromate

Observation Table 9.2 (a): Determination of the amount of chloride ions in the
given solution by Mohr’s method

S.No. Volume of chloride Burette reading Titre value (in cm3)

ion solution (in cm3)
Initial Final (Final-initial reading)
1
2
3
Concordant reading

The volume of silver nitrate used for complete precipitation of chloride ions in the
given solution = A cm3 =….cm3

Determination of indicator blank

Volume of water taken in conical flask, = …. cm3
Solution in the burette: Silver nitrate
Indicator used: Potassium chromate

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 Observation Table 9.2 (b): Determination of indicator blank

S.No. Volume of water (in Burette reading Titre value (in cm3)
cm3) Initial Final (Final-initial reading)
1
2
3
Concordant reading

The volume of silver nitrate used in the indicator blank titration = B cm3 =….cm3

The net volume of silver nitrate used for complete precipitation of chloride ions in
the given solution = (A−B) cm3 = C cm3 = ….cm3

The molarity of the chloride ions in the given solution can be determined as
follows.

The reaction involved:

AgNO3 + Na Cl → AgCl(s) ↓ + NaNO3

Molarity equation: M AgNO3VAgNO3 = M Sodium chloride VSodium chloride

M V
AgNO3 AgNO3
M =
Sodium chloride V
Sodium chloride

Substituting the values, the molarity of chloride ions ( as NaCl) =

The molarity of given chloride ions is = ……….M

Substituting the values, of the molarity and the volume of silver nitrate used, the
molarity of chloride ions is found to be: = ......M

ii) Fajan’s method

Volume of chloride ion solution taken in conical flask, = 10 cm3
Solution in the burette: Silver nitrate
Indicator used: Fluorecsein

Observation Table 9.3: Determination of the amount of chloride ions in the given
solution by Fajan’s method

S.No. Volume of chloride Burette reading Titre value (in cm3)

ion solution (in cm3) Initial Final (Final-initial reading)
1
2
3
Concordant reading

The volume of silver nitrate used for complete precipitation of chloride ions in the
given solution = …. cm3

The molarity of the chloride ions (assuming obtained from NaCl) in the given
solution can be determined as follows.

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 The reaction involved:
AgNO3 + Na Cl → AgCl(s) ↓ + NaNO3

Molarity equation: M AgNO3VAgNO3 = M Sodium chloride VSodium chloride

M V
AgNO3 AgNO3
M =
Sodium chloride V
Sodium chloride

Substituting the values, the molarity of chloride ions ( as NaCl) =

The molarity of given chloride ions is = ……….M

Substituting the values, of the molarity and the volume of silver nitrate used, the
molarity of chloride ions in the given solution is found to be: = ......M

9.7 RESULTS
The molarity of chloride ions in the given solution as determined by Mohr’s method
= ….. M
The molarity of chloride ions in the given solution as determined by Fajan’s method
= ….. M

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