BCHCL138 Chemistry Lab IV

EXPERIMENT 11
TO STUDY THE KINETICS
OF SAPONIFICATION OF
AN ESTER BY TITRIMETRY

Structure
11.1 Introduction 11.4 Procedure
Expected Learning Outcomes 11.5 Observations
11.2 Principle 11.6 Calculations
11.3 Requirements 11.7 Results

11.1 INTRODUCTION
In the previous experiment you have learnt about and studied the kinetics of
acid-catalysed hydrolysis of methyl acetate using titrimetry to follow the
progress of the reaction. In this experiment you would study the kinetics of
base-catalysed hydrolysis of an ester. The base catalysed hydrolysis of an
ester is called saponification. It is an overall second order reaction being first
order with respect to both the reactants i.e., the ester and the base. You would
perform the reaction using equal concentrations of the ethyl acetate and
sodium hydroxide. Here again, the progress of the reaction will be followed
titrimetrically.

Expected Learning Outcomes

After studying about and performing this experiment, you should be able to

 define saponification reaction and state its importance;

 explain the principle of the study of kinetics of saponification reaction by

titrimetry;

 perform the saponification of ethyl acetate and follow its progress using
titrimetry; and

 process the obtained data to calculate the second order rate constant for the
170 saponification reaction.
Experiment 11 To Study The Kinetics of Saponification of an Ester by Titrimetry

11.2 PRINCIPLE
As mentioned earlier, the hydrolysis of ester is catalysed by acids and alkalis.
Soaps are prepared
The alkaline hydrolysis of ester is known as saponification. The equation for
by the alkaline
the saponification of ethyl acetate is given below:
hydrolysis of oils
CH3 COOC2 H5 (aq)  OH (aq)  CH3 COO (aq)  C2H5 OH(aq) …(11.1)
(which are ester of
fatty acids of higher
The reaction is found to be of first order with respect to both the reactants i.e., molecular weight).
ethyl acetate and hydroxide ions and the overall order of the reaction is two. Hence alkaline
The rate equation can be written as hydrolysis of esters
came to be known
 d[OH  ] as saponification.
 k [CH3 COOC 2H5 ][OH  ] …(11.2)
dt

If we perform the reaction with equal initial concentrations (c0) of the two
reactants, and assume that the concentration of each becomes (c0-x) after a
time t, then Eq. 11.2 can be written as,

 d[OH  ]
 k ( c 0  x) 2 ….(11.3) You have learnt
dt
about the integrated
On integrating Eq.11.3 in the suitable limits we get the following expression. rate equation for a
second order
1 1 reaction where the
  kt
( c 0  x) c 0 two reactants have
equal initial
The Eq. 11.4 can be rearranged to concentration in
Unit 13 of the
1 1 1 
k    …(11.5) course BCHCT-
t  (c 0  x) c 0  137.

Thus, according to Eq.11.5, in order to get the value of second order rate
constant for the reaction we need to know the value of (c0) and (c0-x) as a
function of time.

If we look at the Eq. 11.1 again, we observe that as in the case of acid
hydrolysis of methyl acetate (studied in the previous experiment) here also
acetic acid is formed as a product. However, here we have the reaction
mixture containing NaOH. The acetic acid formed would neutralise a part of
NaOH and the concentration of NaOH would keep on decreasing with the
progress of the reaction. (You would recall that in case of acid-hydrolysis of
methyl acetate, the acid content of the reaction mixture increased with time)

This reaction can be followed volumetrically by estimating the concentration of

OH−ions in the reaction mixture at different t values. The reaction mixture is
prepared by mixing equal volumes of a solution of sodium hydroxide (M/40)
and a solution of ethyl acetate (M/40) noting the time simultaneously. Then
equal volumes of reaction mixture are pipetted out at definite intervals and
added into a known excess of cold standardised hydrochloric acid (M/40). The
OH−ions in the reaction mixture get neutralised by the HCl and the left-over
excess acid is titrated with a standardised solution of sodium hydroxide
(M/40). 171
BCHCL138 Chemistry Lab IV
Pouring into excess standard hydrochloric acid solution neutralises the OH- in
the reaction mixture, thus quenching the reaction (you may recall that in the
previous reaction we used ice cold water to slow down the reaction). As the
reaction progresses, the concentration of OH− in the reaction mixture
decreases and the concentration of the unreacted hydrochloric acid in the
quenched reaction mixture increases. The data that we collect is the volume of
NaOH, Vt, required to react with the left-over hydrochloric acid in the quenched
reaction mixture at time t. Let us next see how we calculate k value from such
a set of data. In other words how to relate the titre value, Vt of NaOH solution
to (c0-x).

Let us assume that 10 cm3 of the reaction mixture is added to 25 cm3of M/40
HCl for quenching.

Volume of reaction mixture = 10 cm3

Volume of M/40 HCl added to it = 25 cm3

We know that

25 cm3of M/40 HCl Ξ 25 cm3of M/40 NaOH

Let us say that the volume of M/40 NaOH required for neutralization of the
excess hydrochloric acid = Vt

This means that the volume of acid used for the neutralisation of unreacted
NaOH in 10 cm3of the reaction mixture = (25 - Vt)cm3 of M/40 NaOH

Thus, the concentration of unreacted NaOH in the reaction mixture

( 25  Vt ) M ( 25  Vt )
 ( c0  x )  .  M ...(11.6)
10 40 400

Since equal volumes of M/40 ester and M/40 alkali are mixed, the initial
concentration of NaOH would be

c0 = M/80 ...(11.7)

Using Eq. 11.5 to 11.7, we get

1 400
k (  80 ) …(11.8)
t ( 25  Vt )

Therefore, by substituting the values of Vt at different time intervals in Eq.

(11.8), the rate constant k can be calculated.

Alternatively, by rearranging, Eq. 11.8 we get

Thus, there are two
methods for 400
 80  kt …(11.9)
determining the rate ( 25  Vt )
constant of
saponification This is an equation of a straight line. According to Eq. 11.9 a plot between
reaction studied by 400
and t, would give a straight line whose slope would be equal to k.
titrimetry. ( 25  Vt )
thus, we can determine the value of rate constant graphically also.

172 Slope =k …(11.10)

Experiment 11 To Study The Kinetics of Saponification of an Ester by Titrimetry

11.3 REQUIREMENTS
Apparatus Chemicals

Burettes (50 cm3) 2 Methyl acetate

Beaker (250 cm3) 1 Hydrochloric acid

Conical flasks (250 cm3) 2 Phenolphthalein

Conical flasks (100 cm3) 4 Sodium hydroxide

Pipettes (10 cm3) 2 Oxalic acid

Stop watch 1 Distilled/ deionised

water

Water trough / thermostat 1

Solutions Provided
The following solutions would be provided by your counsellor.

1. M/40 CH3COOC2H5: prepared by pipetting 4.9 cm3 of ethyl acetate into a

If 4.9 cm3 of ester is
2dm3 flask containing some deionised water and then making up the
made upto 2 dm3 in
volume to the mark with deionised water. This solution should be prepared
a standard flask,
on the day it is to be used because a slow hydrolysis reaction takes place
- the molarity of the
even in the absence of OH ions. A more exact solution of ester can be ester can be
prepared by adopting the following procedure. This method also reduces calculated using the
error due to the volatalisation of the ester. density and molar
mass as follows
Take a clean dry weighing bottle and weigh it with some deionised water.
Pipette 4.9cm3 of the ester into the weighing bottle and weight it again. Molarity of ester =
Transfer the ester solution carefully into a 2 dm3 volumetric flask,
repeatedly wash the weighing bottle with deionised water and transfer the 4.9 cm3  0.9 gcm-3
 0.025 M
88 gmol1  2 dm3
washing also into the standard flask. Finally make up the solution to the
mark.
Volume of the ester  density of the ester
Molarity of ester =
Molar mass  Volume of solution of ester ( in dm3 )

2. 0.1 M NaOH (approximately): an approximately 0.1 M NaOH solution can

be prepared by dissolving 8 g (weighed approximately on a rough
balance) of sodium hydroxide pellets in 2 dm3 of deionised water. The
exact strength of this solution is found by titrating against a standard
solution of potassium hydrogen phthalate or standard solution of oxalic
acid. Let the molarity of this solution be p.

3. M/40 NaOH: prepared by diluting (200/40p cm3 =50/p cm3 ) of sodium

hydroxide solution of molarity p prepared above, in a 2 dm3 standard
flask. The volume of the solution is made up to the mark with deionised
water and shaken well. The resultant solution is M/40 NaOH. 173
 BCHCL138 Chemistry Lab IV
3
4. M/40 HCl: prepared by transferring about 4.5 cm of concentrated HCl
using a measuring cylinder to a 2 dm3 volumetric flask containing
approximately 1 dm3of deionised water. The addition of acid is made in a
large number of small lots and the solution is shaken after the addition of
each lot of hydrochloric acid. The volume is made up to the mark with
deionised water. The HCl solution prepared above is standardised with
M/40 NaOH solution prepared above using phenolphthalein indicator.

5. Phenolphthalein indicator: Prepared by dissolving 1 g of phenolphthalein

in 100 cm3 of ethanol and adding 100 cm3 of water to it with constant
stirring. If there are any solid particles, the solution is filtered.

11.4 PROCEDURE
Follow the following instructions sequentially to study the kinetics of
saponification of ethyl acetate.
1. Bring all the required apparatus and solutions as given under sec. 11.3 to
your working table
2. Keep approximately 250 cm3of M/40 HCl taken in a conical flask or beaker
100 cm3of the reaction
in ice bath for cooling.
mixture contains 50cm3 of
M/40 NaOH solution and 3. Transfer 50 cm3of M/40 ester (from the common burette kept for the class)
50 cm3 of M/40 ester into a 250 cm3conical flask.
4. Rinse and fill a clean and dry burette with M/40 NaOH. Transfer 50 cm3of
M/40 NaOH from the burette into a 250 cm3beaker and fill the burette
again.
5. Keep the conical flask containing the ester solution and the beaker
containing NaOH in a water trough (or thermostat) and note the
temperature.
6. Start the reaction by pouring NaOH (in the beaker) into the ester solution
taken in the conical flask. You should start the reaction only after HCl
solution (that has been kept for cooling) has reached a temperature of
nearly 5oC.
7. Pipette 25 cm3 of ice cold HCl into a 100 cm3 conical flask and to this add
10 cm3 of the reaction mixture with another pipette. Note the time of mixing
when half the pipette has been emptied. Add a drop of phenolphthalein and
titrate the solution with M/40 NaOH.
8. Repeat step 7 at least 3-4 times with interval of 5 minutes initially and then
another 3-4 times at the intervals of 10-15 minutes. In all take about 8-9
readings.
9. Record the time of mixing of the reaction mixture with HCl and the
corresponding burette readings in Observation Table-I.

11.5 OBSERVATIONS
Room temperature =…. 0C
Record your observations on time of mixing of the reaction mixture with HCl and the
174 corresponding burette readings here
Experiment 11 To Study The Kinetics of Saponification of an Ester by Titrimetry
Observation Table -I
3
S.No. Time / min Burette reading Titre value / cm
Initial Final (Final-initial burette reading)
1 5
2 10
3 15
4 20
5 30
6 40
7 55
8 70
9 90

11.6 CALCULATIONS
You would recall from Section 11.2 above that we can determine the rate
constant for this reaction by two methods. These are, by integrated rate
equation method and the graphical method. We would follow both of these.
Let’s first take up integrated rate equation method. The progress of reaction is
followed in terms of the concentration of NaOH in the reaction mixture.
I. The initial concentration of NaOH (from Eq. 11.7) = c0= M/80
II. The concentration of unreacted NaOH in the reaction mixture
( 25  Vt ) M ( 25  Vt )
 ( c0  x )  .  M
10 40 400

Where, Vt is the titer value, the volume of M/40 NaOH solution used for the
neutralisation of excess HCl at time t
Copy the titre values from Observation Table-I to the column III of the following
table. Calculate and complete the data in column IV to VI in the same.

Time Titre C0/ M (C0-x) = 1 400

k (  80 ) /
S.No. / min value, 400 t ( 25  Vt )
M
Vt ( 25  Vt ) -1
M min
-1

1 5 1/80
2 10 1/80
3 15 1/80
4 20 1/80
5 30 1/80
6 40 1/80
7 55 1/80
8 70 1/80
9 90 1/80

Calculate the average value of the rate constant obtained in column VI

Average value of the rate constant = 175
BCHCL138 Chemistry Lab IV
III. Graphical method

400
Plot a graph between (on y-axis) and t (on x-axis) using the
( 25  Vt )
data from column V and column II respectively of the table given above.

400
( 25  Vt )

Time 
Calculate the slope of the line = slope=k

= ……….M-1s-1

11.7 RESULTS
The observed rate constant for the saponification of ester studied titrimetrically
are:

(i) by integrated rate equation method =…………………..M-1s-1

(ii) by graphical method =……………………….M-1s-1

176