38 Kinetics of a (Solid-Liquid) Esterication Reaction

Aim
To determine the reaction rate constants for the forward and backward reactions for esterication
of acetic acid with butanol at dierent temperatures.

Reaction
CH3 COOH + C4 H9 OH ←→ C4 H9 COOCH3 + H2 O
Acetic Acid + Butanol ←→ Butyl Acetate + Water

Theory
The synthesis of butyl acetate is done through esterication of acetic acid with n-butanol. The
ester has wide application as a versatile solvent in chemical industry. It is a reversible reaction that
takes place in the presence of acid catalyst. The catalyst used in the present experiment is a solid
heterogeneous catalyst. Hence, reaction takes place on the surface of the catalyst. If the reaction
is performed in a batch reactor, the conversion will increase and the reaction rate will drop with
respect to time. Eventually it will attain equilibrium.

Kinetic Model
Among all the models the simplest model is the pseudohomogeneous model given by the following
rate equation:
− rCH3 COOH = k1 CCH3 COOH CC4 H9 OH − k2 CC4 H9 COOCH3 CH2 O (38.1)
where K is the reaction equilibrium constant (i.e. k1 /k2 ) that can be independently calculated
using the following relation:
0(l)
K ∆HR 1 1
ln
K0
=
R
[ − ]
T0 T
(38.2)
0(l)
where, K 0 = exp[− ∆GRT ]
R
0

Data: ∆HR0(l) = - 3.887 kJ/mol, ∆GR

0(l)
= - 8.889 kJ/mol

Apparatus
The set-up consists of ve heating chambers whose temperature can be set independently thus,
enabling conducting ve runs at dierent temperatures simultaneously. The reaction is performed
in a 300 ml glass reactors equipped with stirrer and condenser and placed in respective heating
chambers for the attainment of the required temperature. The stirrer is driven by a motor with a
control over the speed of agitation. The speed can be measured using a non-contact type tachometer.
Digital temperature indicators are provided to measure the temperature of the reaction mixture in
all the reactors.

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Procedure
1. Set the temperatures of the heating chambers (atleast four) at the desired levels and start
heating.

2. Take measured quantities of acetic acid and n-butanol in the two reactors.

3. Place the reactors in the oil baths, start slow stirring and observe the reactor temperature.

4. Once the desired temperature of the reaction mixture is attained, add the measured quantity
of cation exchange resin (Amberlyst-15) in the reactor. Consider this time as the zero reaction
time. Increase the speed of agitation to 1200 rpm.

5. Remove samples from all the reactors. Keep removing the samples as per the time intervals
indicated in the tables.

6. Titrate weighed quantity of the sample against 0.5 M NaOH. Record the titration readings
and calculate conversions at every time interval.

Outline of the Process

Data
Mole ratio of reactants:
Amount of catalyst:

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Figure 38.1: Schematic diagram of the Esterication setup

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Observation and Results Table
Chamber 1 Temperature = ____ Chamber 2 Temperature = ____
Time Weight of Titer Val. Conversion Time Weight of Titer Val. Conversion
(min) sample (g) (ml) (Xobserved ) (min) sample (g) (ml) (Xobserved )
0 0
5 5
10 10
15 15
20 20
30 30
45 45
60 60
k1 k1
k2 k2
Chamber 3 Temperature = _____ Chamber 4 Temperature = _____
Time Weight of Titer Val. Conversion Time Weight of Titer Val. Conversion
(min) sample (g) (ml) (Xobserved ) (min) sample (g) (ml) (Xobserved )
0 0
5 5
10 10
15 15
20 20
30 30
45 45
60 60
k1 k1
k2 k2

k0 for forward reaction =

k0 for backward reaction =
E for forward reaction =
E for backward reaction =

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Calculations
1. Calculate the conversion at all times for each temperature and plot the kinetic data (X vs t)
for comparison, where X is conversion.

2. Calculate the reaction rate constant by Integration and Dierential method

Integral Analysis

1. The rate equation can be integrated to give k1 t = f1 (X)

2. Find f1 (X)

3. Plot f1 vs t to get k1 and k2

Dierential Analysis

1. The rate equation can be written as dX/dt = k1 × f2 (X)

2. Find f2 (X)

3. Calculate dX/dt at each time interval for X vs t plot.

4. Plot dX/dt vs f2 (X).

5. Calculate k1 and k2 from the above plot.

Integral Analysis

1. Plot ln k1 and ln k2 vs 1/T .

2. Evaluate Arrhenius parameters k0 and E for both backward and forward reactions from the
graph.

Conclusion and Comments

Questions
1. Suggest the algorithm to evaluate k1 by regression analysis.

2. If K is not known, how will you evaluate k1 and K from the kinetic data you have generated?

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