Short Research Communication

Kinetics of the Esterification Reaction Between

Ethanol and Acetic Acid
F.S. Atalay
Department of Chemical Engineering, Ege Univets& Bomova-lzmir, TURKEY

The esterification reaction between ethyl alcohol and acetic acid, catalysed by sulficric
acid, has been investigated over a wide range of temperatures and catalyst
concentrations. A batch reactor was used to obtain operating data which may be applied
to a process of simultaneous distillation with chemical reaction. The experiments were
carried out at constant initial ethanol and acetic acid concentrations and the results were
evaluated by a differential analysis method. The orders of the forward and reverse
reactions were found to be 1 and 2, respectively. Reaction-rate constants have been
related to the reaction temperaturefor each catalyst concentration, and the frequncy
factors and the activation energies have been determined. Models representing the
effects of temperatureand catalyst concentrationon the reaction rate constants have also
been developed.

Experimental Details
The kinetic experiments were performed in a heated two-litre flask. The reaction
temperature was controlled by a contact thermometer and the reaction mixture was
agitated using a magnetic bar. A condenser was used to prevent the escape of any
vapor from the reactor and 1 ml liquid samples were taken fiom the reactor. When
the reactants reached the reaction temperature, then prepared catalyst (using pure
sulfuric acid and distilled water) was added.
Samples were taken from the reactor for analysis at 15 minute intervals during
the two hour experiment. All the samples were analysed using gas chromatography
with a flame ionisation detector, and the conversion of acetic acid for each run was
calculated.
(Tabulated results from the experiments are available from the author upon request.)

Results and Discussion

A relation between the conversion of acetic acid and the reaction time was obtained
by using the second-order polynomial regression technique. The first derivatives of
these relations were evaluated as the reaction rates. The order of each reaction and
the reaction rate constants were obtained as follows.
The rate of the esterifhtion reaction can be determined thus:

k,
CH3 COOH + C2H5 O G C H 3 C02 C2H5 + H20 (1)
k2

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FS.Alalay

(2) dt ASA EtA

-HZ0
If C A ~C, E ~and
, C H are~ the initial concentrations of acetic acid, ethyl alcohol
and water, respectively, and x is the conversion at time t, then the reaction rate
equation can be expressed as:

In all the experimental runs, 6.93 mom of acetic acid and 8.26 mom of ethyl
alcohol were used as initial concentrations, and the initial water concentration for
each run was calculated with respect to the prepared catalyst concentration.
In order to obtain the orders of reaction (mp,p,q) and the reaction rate constants
Q1, k$, a computer program written in Quick BASIC 4.0 was used. The H o o k and
Jeeves optimization technique [ll was applied. The results showed that the calculated
reaction rates are best described by the model with values of m = n = 0.5 and p = q
=1, for the overall temperatures and catalyst concentrations studied. Therefore, the
reaction-rate constants were calculated using these values, and the results obtained
are given in Table 1. The Arrhenius' law was used to model the effect of temperature
on the reaction rate constants at constant catalyst concentration. The results in Table
2 show variations in the activation energies and frequency factors due to changes in
the catalyst concentration.

Table I . Calculated reaction rate constants (kl and k2) at various

temperatures and catalyst concentrations (wt.95 H2SO4).
~~ ~ ~ ~~

Temperature ("C) wt.% H@O4 kl x lo3 k 2 x 103

48 0.382 1.9275 0.3755

59 0.382 5.8065 0.9541
67 0.382 6.0473 0.9096
75 0.382 11.3362 1.3982
51 1.91 8.7320 0.9976
59 1.91 11.5300 1.21 30
67 1-91 12.3300 1.4325
75 1.91 22.6300 1.5580
48 2.66 11.5032 1.3843
59 2.66 12.9115 1.4786
67 2.66 15.1091 1.a76
75 2.66 16.9204 1.7560
48 3.79 14.5620 1.7381
59 3.79 14.6780 1.7184
67 3.79 17.5870 2.0440
75 3.79 21.5421 2.2400

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 Kinetics of the Erterijiuawn Reaction Between Ethanol and Acetic Acid

Table 2. The frequencyfactors (A) and the activation energies (E)for forward and
reverse reactions at constant catalyst concentration (wt.95 HzS04).

Forward reaction Reverse reaction

Wh H2S04 El A1 E2 A;!
0.382 57035 4130876 41963 2878
1.91 31728 1099.41 17258 0.6152
2.66 13553 1.8132 9420 0.0458
3.79 13494 2.145 9314 0.0545

Different model equations were derived which represented the effect of reaction
temperature and catalyst concentration on the rate constants. The forward and
reverse reaction rate constants of the esterification reaction between ethanol and
acetic acid (catalysed by sulfuric acid) were determined. The values are given by the
expressions:
k l = 4.86 x + 0.496 exp(-310/r) + 0.205 (20.85
k2 = 3.715 x + 0.01572 exp(-220/T) + 0.09785 C1*38
Conclusions
Earlier studies [2-51 of the esterjfication reaction between ethyl alcohol and acetic
acid considered it to be second order for both the forward and reverse reactions.
Previously, empirical equations relating the rate constants with temperature and
catalyst concentration have not been available. In this study, the forward and reverse
orders of reaction were found to be 1 and 2, respectively. The relationships
representing the effect of temperature and catalyst concentration on the reaction-rate
have also been developed.

Nomenclature
Frequency factor for the forward reaction(l/min)
Frequency factor for the reverse reaction (m3/kmol min)
Sulphuric acid concentration (wt%)
Initial acetic acid concentration (km01/m3)
Acetic acid concentration(km0Vm3)
Initial ethyl alcohol concentration (kmoVm3)
Ethyl alcohol concentration (km01/m3)
Ethylacetate concentration (kmoUm3)
~nitialwater concentration ( I U ~ O V ~ ~ )
water concenmtion (km01d)
Activation energy for forward reaction (kJ/kmol)
Activation energy for reverse reaction (kJ/kmol)
Forward reaction rate constant (l/min)
Reverse reaction rate constant ( m 3 h o l min)
Order of forward reaction for ethyl alcohol (-)

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FS.Atalay

n Order of forward reaction for acetic acid (-)

p Order of reverse reaction for ethylacetate (-)
q Order of reverse reaction for water (-)
rA Rate of reaction -0vm3 min)
T Reaction temperature ("C)
t Time (min)
x Conversion of acetic acid (-)

References
1. Kuester, LJ. and Mize, J.H.1973. OptimizationTechniques With Fortran.pp. 309-319.
McGraw-Hill, New York.
2. Kirk-Oher. 1980. In.Mark H.F.(ed), Encyclopedia of Chemical Technology. Vo1.9. pp.
291-309. Wiley. New York.
3. Amikar, H.J.,Rao. T.S.,and Bodhe, A.A. 1970. A gas chromatographic study of the
kinetics of uncatalysed estenfication of acetic acid by ethanol. J . Chrumutogrqhy, 47.
265-268.
4. Venkataraman, S., Chan. W.K., and Boston, J.F.1990. Reactive distilation using ASPEN
PLUS.Chem. Eng. Prog., 86(8), 45-54.
5. Mochida, I., Anju, Y.. Kato, A., and Seyama, T. 1971. Esterification of ethanol with
acetic acid. J . Catalysis, 21,263-269.

Received: 21 November 1992; Accepted after revision: 27 August 1993.

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