EXPERIMENT 8

A SIMPLE TITRATION
Structure

8.1 Introduction
Objectives
8.2 Titration
Types of Indicators
Types of Titrations
Standard Solution
8.3 Titrimetric Experiment: Determination of the
strength of given Sodium Hydroxide Solution
Principle
Requirements
Procedure
Observations
Calculations
Result
8.4 Summary

8.1 INTRODUCTION
Titrimetric analysis or volumetric analysis is an important chemical method of
analysis for determination of the concentration of various solutions. Titrimetric
analysis is based on quantitative performance of suitable chemical reactions.
Therefore it is a quantitative method of analysis. Titrimetric analysis is
performed by accurately measuring the volume of a standard solution which is
required to completely react with a known volume of an unknown solution.
Therefore, it is also known as volumetric analysis. Laboratory technicians are
required to perform a number of titrations in the laboratory. In this experiment,
you will perform a titration of oxalic acid with sodium hydroxide.

Objectives
After performing this experiment, you should be able to:
prepare a standard solution,
I perform a titration of oxalic acid with sodium hydroxide,
determine the concentration of sodium hydroxide solution,
perform any other titration provided proper instructions are given,
determine end-point in a titration, and
classify various types of titrations.

8.2 TITRATION
In titrimetric analysis, one determines the volume of a standard solution which
is required to react quantitatively with a known volume of the other solution,
the concentration of which is to be determined. For this purpose, an aliquot of
the solution to be estimated is pipetted out and is transferred into a conical
flask. The standard solution is added dropwise from a burette to the solution in
the conical flask.
Basic Experiments The conical flask is continuously shaken to enable the two solutions to mix
in Chemistry thorougldy. Standard solution (Unit 7 of Block 2) is added till the two
solutions react quantitatively. This process is called tiration. The solution in the
conical flask is called the titrand and the one in the burette is called the
titrant. The total volume of titrant used in the reaction is called the titre.

We have said above that in a titration, the titrant is added till it reacts
quantitatively with the titrand. Such a stage, at which the quantities of titrant
and titrand are in their stoichiometric proportions (in terms of equivalents or
moles), is called the equivalence point. A question arises now, as to how do we
know that the equivalence point has been reached? At what stage shall we stop
adding the solution from the burette? Essentially we need some substance
which can indicate this stage by a change in a physical property like colour. A
substance which is used to indicate the equivalence point of a titration through
a colour change is called an indicator. Equivalence point so obtained is called
end point. It is not necessary that the end point is coincident with the
equivalence point, because of the delay in getting the indicator to show the
change, and other factors. Ideally end point and equivalence point should be as
close as possible. The indicator, to be used in a given titration, would depend
on the nature of the chemical reaction involved between the two reacting
solutions. The basic requirement for an indicator is that it should have
distinctly different colours before and after the end point because we need to
know the end point visually. If no visual indicator is available, the detection of
equivalence point can often be achieved by following the course of the tihation
by measuring the potential difference between an indicator electrode md a
reference electrode or the change in the conductivity of the solution.

8.2.1 Types of Indicators

The indicators can be of three types depending upon their usage:
i) Internal indicators: These have to be addeq! into the reaction solutian.
Examples are: phenolphthalein, methyl oranpe, diphenylamine, etc.

ii) External indicators: These are not added into the solution. The
indicator is kept out on a plate. A drop of the solution being titrated is
taken out with the help of a rod and put on the indicator. A change in
colour indicates the end point. Potassium ferricyanide is one such
example.
iii) Self-indicators: Sometimes either the titrand or the titrant changes its
colour at the end point and acts as a self-indicator. The example is
potassium permanganate used in permmgmatometry.

8.2.2 Types of Titrations

Depending upon the nature of the chemical reaction involved in a titration, the
latter can be classified into the following types:

i) Acid-base titrations or Neutralisation titrations: The reaction in

which an acid reacts with a base to give salt and water is called a
neutralisation reaction and the titration involving such a reaction is
called an acid-base titration or a neutralisation titration. An example is
the reaction between NaOH and HCI :
NaOH + HC1 ---b NaCl + H20
 The indicators used in these titrations depend upon the pH at the end Experiment 8
point, the familiar examples are phenolphthalein and methyl orange. t

ii) Oxidation-Reduction or Redox titrations: Titrations involving

oxidation-reduction reactions, i.e., those in which one component gets
oxidised while the other gets reduced are known as redox titrations. An
example is the titration between oxalic acid and potassium
permanganate in acidic medium, in permanganatometry. In this case,
potassium permanganate gets reduced to ~ n while ~ oxalic
+ acid gets
oxidised to CO2 and water. In this titration, potassium permanganate
acts as a self-indicator. The following equation represents the reaction:

Titrations involving potassium dichromate (Chromatometry) and iodine

(iodometry) are also examples of redox titrations.

iii) Precipitation titrations: In certain reactions, when the two

components react, a precipitate is formed. The end point is indicated by
the completion of precipitation. Such reactions are termed as
precipitation reactions and the tirations as the precipitation titrations; an
example is the titration between potassium chloride and silver nitrate as
per the following equation:
..

Titrations involving AgN03 are also called argentometric titrations.

iv) Coslplexometric titrations: A complexation reaction involves the

replacement of one or more of the coordinated solvent molecules,
which are coordianted to a central metal ion, M, by some other groups.
The groups getting attached to the central ion are known as ligands, L.

M(H20), + nL =+ML, + nHzO

The titration involving such type of a reaction is called a

complexometric titration. For example, determination of hardness of
water using ethylenediaminete&aacetic acid (EDTA) as the complexing
agent. The indicator used in thR case is eriochrome black T.

8.2.3 Standard Solution

A standard solution is defined as the one whose concentration (strength) is
known accurately, i.e., we know exactly how much of the solute is dissolved in
a known volume of the solution. A standard solution may be prepared by
dissolving an accurately weighed, pure stable solid (solute) in an appropriate
solvent. Preparation of a standard solution is generally the first step in any
quantitative experiment, so it is important to know how to prepare a sta~dard
solution.

Primary and Secondary Standards

In titrimetry, certain chemicals are used frequently in defined concentrations as
reference solutions. Such substances are classified as primary standards or
secondary standards. A primary standard is a compound of sufficient purity
Basic Experiments from which a standard solution can be prepared by weighing a quantity of it
in Chemistry '
directly, followed by dilution to give a definite volume of the solution. The
following specifications have to be satisfied for a substance to qualify as a
primary standard:
1. It must be easily available and easy to preserve.

2. It should not be hygroscopic nor should it be otherwise affected by air.

3. It should be readily soluble in the given solvent.

4. The reaction with a standard solution should be stoichiometric.

5. The titration error should be negligible.

Few available primary standards for acid-base, redox and comlexometric

titrations are given in Table 8.1.
Table 8.1: Some primary standards.

S.No. Compound Formula unit Relative Type of titration

molar
mass, M ,
1. Potassium hydrogen CsHs04K 204.23 Acid-base
phthalate (KHP)

2. Anhydrous sodium Na2COj 106.00 Acid-base

carbonate
I I I I

3. Sodium Salt of EDTA 372.30

Na2HZCIOH1208N2.2HZ0 Complexometric

4. Copper(I1) sulphate CuS04.5H20 249.54 Iodometric

I I I 1

5. Potassium dichromate K2Cr207 294.19 Redox

I I I I
6. Arsenic(II1) oxide As20; 197.85 Redox

7. Potassium iodate
I

I
KIO3
I

I
214.00
I

I
Redox
I
1
I

8. Sodium oxalate NazCz04 134.00 Redox

9. "' Fendus-ammonium FeS04.(NH4)2S04.6H20 392.16 Redox

sulphate
I
Oxalic acid
I
r--

, - I I
10. (COOH)7.2H20 63 .OO Redox/acid-base

Solutions prepared from the primary standards are called primary standard
solutions.

Substances which do not satisfy all the above conditions, are known as
secondary standards. In such cases a direct preparation of a standard solution is
not possible. Examples are alkali hydroxides and various inorganic acids.
These substances cannot be obtained in pure form. Therefore, concentration of
these can be determined by titrating them against primary standard solutions.
This process is called standardisation and the solution so standardised is called
a secondary standard solution:
 Experiment 8
Preparation of a Standard Solution
To prepare a standard solution of volume, v cm3, of known molarity, M mol
dm", the mass of the solute required, m g, of molar mass M, can be calculated
as follows:
M.M,.V
Mass of the solute (m)= g
1000

The solute is then weighed on an analytical balance, transferred into a standard

flask and dissolved first in a small quantity of the solvent, the solution is then
made up to the mark and shaken thoroughly to get a homogeneous solution.

In preparing a standard solution whose concentration is, say, around 0.1 M, the
amount of the substance weighed need not be exactly equal to that
corresponding to 0.1 M. It can be slightly less or more, but the weighing must
be accurate. From the weight of the solute actually taken, molarity of the
solution can be calculated using Eq. 8.1.

8.3 TITRIMETRIC EXPERIMENT: DETERMINATION

OF THE STRENGTH OF GIVEN SODIUM
HYDROXIDE SOLUTION
Having learnt about titration in general, types of titrations and indicators, you
would now like to learn how you would do an experiment, make observations,
record data and calculate the result. It is also important to examine the result
critically, compare it with known or expected value, look for the sources of
error so that improvement can be made. We will illustrate all this in the
following example. Of course, you will have to perform various experiments
according to the procedure given in each case. We consider here a simple
titration involving a weak acid and a strong base, viz. oxalic acid and NaOH,
using phenolphthalein as the indicator.

8.3.1 Principle
! Sodium hydroxide is not a primary standard. Therefore, it should be
standardised with a suitable primary standard such as oxalic acid. Sodium
hydroxide reacts with oxalic acid according to the following equation:.

From the above reaction, you can see that sodium hydroxide reacts with oxalic
acid in 2: 1 molar ratio. Hence
No. of molesof oxalicacid --
1
No. of molesof sodium hydroxide 2

where 1111 = molarity of oxalic acid

Vl = volume of oxalic acid taken
MZ= molarity of sodium hydroxide
Basic Experiments V2 = volume of sodium hydroxide taken
in Chemistry
A slight excess of sodium hydroxide at the end point imparts a distinct pink
colour to the solution, when phenolphthalein is used as an indicator.

8.3.2 Requirements
Apparatus Chemicals
Analytical balance 1 No. Oxalic acid
Beaker 400 c d capacity 1 No. Sodium hydroxide solution
Burette 50 cm3 capacity 1 No. (approximately MI10)
Burette stand 1 No. Phenolphthalein indicator
Conical flask 250 cm3 capacity 1 No.
Funnel small 1 No.
Pipette 20 cm3 capacity 1 No.
Volumetric flask 250 cm3 capacity 1 No.
Wash bottle 1 No.
Weighing bottle 1 No.

8.3.3 Procedure
1. Preparation of a standard solution of oxalic acid
As the concentration of the given sodium hydroxide solution is approximately
0.1 M, you will have to prepare a standard solution of oxalic acid of about 0.05
M concentration. As the molar mass of oxalic acid is 63, you will require
1.5750 g of oxalic acid for preparing 250 cm3 of 0.05 M solution. This can be
calculated as shown below.

m = MxM,xV
= 0.05 mol dm-3x 12.60 g mol-' x 0.25 dm3
= 1.5750 g

In Unit 2 of this course, you have studied the handling of different types of
analytical balances. Weigh out an empty weighing bottle on an analytical
balance and record its mass. Then weigh out the weighing bottle with about
1.60 g of pure oxalic acid accurate1 and record the mass in your note book.
Then transfer the solid to a 250 cmY clean volumetric flask through a glass
funnel. Weigh the weighing bottle again accurately and record its mass.
Dissolve the solid in 40-50 cm3 of distilled or deionised water. Make the
solution up to the mark wi!h distilled water. Stopper the flask and shake it well
to make the solution homogeneous.

2. Standardisation of sodium hydroxide solution

First collect the sodium hydroxide solution in a 250 cm3 bottle from your
counsellor. Take a clean burette. Rinse the burette with sodium hydroxide
solution and fill it up with this solution. Note the initial reading of the burette
and record it in the observation Table 8.2 under the initial readin column.
Q
Pipette out 2fl cm3 of standard oxalic acid solution into a 250 cm conical flakk.
Add one or two drops of phenolphthalein indicator. Titrate this solition by
slowly adding small amounts of sodium hydroxide solutioa from the burette
and continuously shaking the conical flask. Continue adding sodium hydroxide
solution until a permanent pink colour appears. This indicates the end point of
the titration. Note the burette reading and record it in the observation Table 8.2
 under the 'final reading' column. The difference of the two readings gives the Experiment 8
volume of NaOH used.

Repeat the titration to get at least two concordant readings to ensure a correct
and exact measurement. Record your readings in Table 8.1 and calculate the
t strength of sodium hydroxide solution. This solution now can be used to
determine the strength of other acid solutions.

8.3.4 Observations
Approximate mass of the weighing bottle =rnl = ..........g
Mass of weighing bottle + oxalic acid = m 2 = ..........g
I
Mass of weighing bottle after transferring oxalic acid = m3 = ..........g

I
Molar mass (Mr) of oxalic acid = 63.0 g mol-'
i
Volume of oialic acid solution prepared = 250 cm3 = 0.25 dm3

Table 8.2: Titration of oxalie acid with sodium hydroxide solution

r
S.No. Volume of oxalic Burette Reading Volume of NaOH in
acid cm3(Final-Initial)
vt Initial Final v2

1. 20 cm3
2. 20 cm3
3. 20 cm3

8.3.5 Calculations

Molarity of oxalic acid solution MI = -

m
Mr. V

-
- (m2 -m3)
"4
mol dm-
63

Volume of oxalic acid taken Vl = 20.0 cm3

Volume of sodium hydroxide used = V2 cm3
Molarity of sodium hydroxide solution = M2
Using Eq. 8.2,
Basic Experiments
inshemistry

8.3.6 Result

Molarity of sodium hydroxide solution = . .. . . .... . . . . . ... mol dm-3

8.4 -
SUMMARY - - - -

In this experiment, you have performed the following:

prepared a standard solution of oxalic acid,
performed an acidimetric titration of a standard solution of oxalic acid
against a sodium hydroxide solution,
determined the strength of the sodium hydroxide solution.