5 (2011) 1179-1182
Received: August 01, 2011 / Accepted: September 06, 2011 / Published: December 10, 2011.
Abstract: In the present study the investigation of the glycerol hydrochlorination process has been presented. It is shown that water
concentration strongly affects the reaction rates. It deals with the phenomenon of hydration. The kinetic parameters of the reactions
have been determined.
definite answer in the literature. The understanding of non-catalytic reaction. But it was found that kinetic
the water role can help us to realize the mechanism of constant decreases with the increase of water
the process and the ways to control the reaction rates. concentration, namely, with the increase of molar ratio
between water and hydrogen chloride. Obtained data
2. Equipment, Analyses and Operating
are presented in Fig. 1.
Conditions
The obtained results may be explained by the
The experiments were carried out in continuous phenomenon of hydration [14-15].
mode in glass reactor, equipped with stirrer, electric There are polar organic compounds in the reaction
heater and reflux condenser. The concentration of mixture such as glycerol and chlorohydrins. They may
water in the feed mixture with glycerol had variations orientationaly interact and form hydrogen bonds both
from 1.6% to 40% by weight. Acetic acid was used as with each other and with molecules of water. But there
catalyst. Organic products were analyzed by the gas are chlorine anions in the same mixture. They bring
chromatograph. Determination of hydrochloric acid negative charge and have small radius. Molecules of
and acetic acid was carried out with the help of water may hydrate both glycerol (chlorohydrins) and
conductivity measurement device. chlorine anions. But it is clear that chlorine anions are
hydrated most strongly. Redistribution of negative
3. Results and Discussion
charge takes place in such hydrated chlorine anions.
It is commonly known that hydrochlorination of The more molecules of water are in such complexes,
alcohols is a reversible process described by the less the density of surface charge is.
bimolecular nucleophilic substitution (SN2) Anions, hydrated with one, two, three and more
mechanism. It was found that hydrochlorination of molecules of water, are different reagents and each of
glycerol is irreversible process [13]. them has its own kinetic constant.
Therefore, the hydrochlorination of glycerol is to be So, the experimental curves represent the
described by the second order equation: dependence of kinetic constant on the degree of
r k CGl HCl (1) chlorine anion hydration and they are described by the
We used this equation in our investigation of following kinetic equation:
Hydrochlorination of Glycerol-The Role of the Water on the Process 1181
4,5
4,0
3,5
3,0
117
k 105, l/(mols)
2,5
2,0
110
1,5
110
1,0
90
0,5
80
0,0
0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6 2,8 3,0
2/HCl
Fig. 1 Dependence of kinetic constant on the molar ratio between water and hydrogen chloride for the reaction of -MCH
formation at temperatures 80-117 C.
HCl ( a bT ) HCl ( a bT )
r k 0 e ( E / RT ) ( ) Gl HCl (2) r k0 e( E / RT ) ( ) Gl HCl AcA (3)
H 2O H 2O
where a and b are empiric coefficients. Catalytic rates were calculated as difference between
There is the factor of molar ratio between hydrogen observed rates and non-catalytic rates. It was found that
chloride and water in the empiric power. It non-catalytic rates are less than 3% of the observed
characterizes the effect of hydration. This factor rates. That is why the investigation of ,-DCH and
depends on the temperature and reduces with its ,-DCH formation was carried out only in the
increase. So the influence of the hydration on the presence of catalyst. The formation of ,-DCH and
reaction rates decreases at higher temperatures. And it ,-DCH is described by the following kinetic
is logical because of increase of system entropy and equation:
loosening of intermolecular bonds. HCl ( a b T )
r k0 e ( E / RT ) ( ) - MCH HCl AcA (4)
The values of pre-exponential factor, activation H 2O
energy and empirical coefficients for the reactions The values of pre-exponential factor, activation
of -MCH and -MCH formation are presented in energy and empirical coefficients for the catalytic
Table 1. reactions of -MCH, -MCH, ,-DCH and ,-DCH
Investigation of glycerol hydrochlorination in the formation are presented in Table 2.
presence of catalyst results in the similar kinetic
Table 2 The values of pre-exponential factor, activation
equation for the -MCH and -MCH formation:
energy and empirical coefficients for the catalytic reactions
Table 1 The values of pre-exponential factor, activation of -MCH, -MCH, ,-DCH and ,-DCH formation.
energy and empirical coefficients for the reactions of Reaction number corresponds to the one in the Scheme 2.
-MCH and -MCH formation. Reaction number Reaction No k0, l2/(mol2s2) , J/mol b
corresponds to the one in the Scheme 2. 1 1.24 1011 86000 25.63 0.056
Reaction No k0, l/(mols) , J/mol b 2 1.38 1010 91500 13.36 0.026
1 2.1 109 102000 10.5 0.023 3 2.51 104 47000 35.74 0.084
2 2.2 1012 132000 14.7 0.034 4 1.62 108 92000 16.85 0.038
1182 Hydrochlorination of Glycerol-The Role of the Water on the Process
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