TITRIMETRIC ANALYSIS

Topic 4
BACK TITRATION

1st March 2011

DrSabiha/CHM421/Dec 10-Apr11

Back titration
Back titration is a process in which the
excess of a standard solution used to
consume an analyte is determined by
titration with a second standard solution.
Example: Determination of acetylsalicylic
acid in aspirin.

1st March 2011

DrSabiha/CHM421/Dec 10-Apr11

Sometime direct titration of an analyte with a

Reagent is not FEASIBLE. This is due to the following
reason:
1. The reaction kinetics is slow or the rate of reaction
is slow.
2. No suitable indicator in the direct titration.
3. The colour change at the end point is slow or delay
or not sharp.
4. The end point is far from the equivalence point.
5. Standard solution lacks stability.

1st March 2011

DrSabiha/CHM421/Dec 10-Apr11

Example of back titration

The titration of insoluble organic acid with NaOH
is not practical because the reaction is slow.
CH3COO-C6H4-COOH + 2NaOH

CH3COONa + HO-C6H4-COONa

To overcome it, add NaOH in excess and allow the

reaction to reach completion and then titrate the
excess NaOH with a standard solution of HCl.
NaOH + HCl
NaCl + H2O
1st March 2011

DrSabiha/CHM421/Dec 10-Apr11

The system has gone from being ACID , past the

equivalence point to the BASIC side (excess base),
and then back to the equivalence point.
The final titration to the equivalence point is
called a BACK TITRATION.

1st March 2011

DrSabiha/CHM421/Dec 10-Apr11

Example1
150.0 mL of 0.2105 M nitric acid was added in
excess to 1.3415 g calcium carbonate. The excess
acid was back titrated with 0.1055 M sodium
hydroxide. It required 75.5 mL of the base to reach
the end point.
a) Name a suitable indicator used in above titration
b) Draw the titration curve for the above titration.
c) Calculate the percentage (w/w) of calcium
carbonate in the sample.

1st March 2011

DrSabiha/CHM421/Dec 10-Apr11

a) Suitable indicator:
phenolfthalein/methyl orange
b)

1st March 2011

DrSabiha/CHM421/Dec 10-Apr11

c) First write a balance equation for the above

reactions.
2HNO3 + CaCO3 Ca(NO3)2 + CO2 + H2O
HNO3 + NaOH NaNO3 + H2O
From Equations above:
2 mole HNO3 = 1 mole CaCO3 (initial)
1 mole HNO3 = 1 mole NaOH (back titration)

Initial amount of acid:

mole of acid = 0.2105 x 0.150
= 31.58 x 10 -3 mol
1st March 2011

DrSabiha/CHM421/Dec 10-Apr11

1 mole HNO3 = 1 mole NaOH (back titration)

So, remaining/excess acid during back titration:
mole of excess acid = 0.1055 x 0.0755
= 7.965 x 10-3 mol.
Then, mole of acid reacted with CaCO3
= ( 31.58 x 10 -3 7.965 x 10 -3 )
= 23.61 x 10 -3 mole HNO3

1st March 2011

DrSabiha/CHM421/Dec 10-Apr11

2 mole HNO3 = 1 mole CaCO3 (initial)

23.61 x 10 -3 mole = ?
mole of CaCO3 = x mole acid
= x 23.61x 10 -3
= 11.805 x 10-3 mol CaCO3

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Gram CaCO3 = mole x molar mass

= 11.805 x 10-3 x 100
= 1.1805 g.
% CaCO3 =

weight CaCO3
weight of sample

x 100

1.1805
X 100
1.3415

87.99 % (w/w)

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DrSabiha/CHM421/Dec 10-Apr11

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Example 2 (back titration)

The sulfur content of a steel is determined by
converting it to H2S gas. The H2S gas is then
adsorb using 10.0 mL of 0.0050 M I2, and back
titration is done to react the excess I2 with
0.0020 M Na2S2O3. If 2.60 mL Na2S2O3 is
required for the titration, how many milligrams
of sulfur are contained in the steel sample?

1st March 2011

DrSabiha/CHM421/Dec 10-Apr11

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H2S + I2 S + 2I- + 2H+ (slow rxn)

I2 + 2S2O32- 2I- + S4O621 mol I2 2 mol S2O32-

mmol I 2
1

mmol Na 2S2O3
2

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Solution:
Initial mol I2 = 0.005 x 0.010 = 0.05 x 10 -3 mol
or 0.05 mmol
mol Na2S2O3 = 0.002 x 0.0026 = 0.0052 x 10 -3 mol
or 0.0052 mmol
From back titration : I2 + 2S2O32- 2I- + S4O62Remaining mmol I2 = mmol Na2S2O3 = x 0.0052
= 0.0026 mmol

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mmol I2 reacting with H2S

= initial I2 - remaining I2

= 0.05 - 0.0026 = 0.0474 mmol

mmol I2 = mmol H2S = mmol S = 0.0474 x 32
= 1.5168 mg S

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