Effect of pyridine and tribenzylamine on the hydrolysis kinetics of benzoyl chloride in water-dioxane system

Article abstract of DOI:10.14233/ajchem.2017.20556

The aim of this paper was to study the effect of tribenzylamine and pyridine on the kinetics of the hydrolysis reaction of benzoyl chloride in water-dioxane solution. The benzoyl chloride and water initial concentrations were 0.005 and 1 mol/L, respectively. While, the initial concentrations of pyridine and tribenzylamine varied in the range of 0.005-0.02 mol/L and 0.007-0.014 mol/L, respectively. It was found that the addition of tribenzylamine to benzoyl chloride hydrolysis reaction has no catalytic effect and hence the rate constant can be calculated using a first-order rate equation. In the presence of pyridine, reaction obeyed second-order rate. The relationship between the reaction rate constant and pyridine initial concentration was found to be linear with a rate constant of 0.752 × 10^–3 min^–1.

Full text of DOI:10.14233/ajchem.2017.20556

Asian Journal of Chemistry; Vol. 29, No. 9 (2017), 1888-1890
ASIAN JOURNAL OF CHEMISTRY
https://doi.org/10.14233/ajchem.2017.20556
Effect of Pyridine and Tribenzylamine on the Hydrolysis Kinetics of
Benzoyl Chloride in Water-Dioxane System
1,*
2
1
1
MOHAMMAD A. BATIHA , ELENA A. CHIZHOVA , MARWAN M. BATIHA , LEEMA A. AL-MAKHADMEH ,
1
3
1
SALEH RAWADIEH , MUAWIA ALQASAIMEH and ABDULLAH MARASHLI
1Faculty of Engineering, Al-Hussein Bin Talal University, 71111 Ma'an, Jordan
2Ivanovo State University of Chemistry and Technology, 153000, Ivanovo, Russia
3Faculty of Science, Al-Hussein Bin Talal University, 71111 Ma'an, Jordan
*Corresponding author: E-mail: mbatiha@ahu.edu.jo
Received: 31 January 2017;
Accepted: 12 April 2017;
Published online: 15 July 2017;
AJC-18459
The aim of this paper was to study the effect of tribenzylamine and pyridine on the kinetics of the hydrolysis reaction of benzoyl chloride
in water-dioxane solution. The benzoyl chloride and water initial concentrations were 0.005 and 1 mol/L, respectively. While, the initial
concentrations of pyridine and tribenzylamine varied in the range of 0.005-0.02 mol/L and 0.007-0.014 mol/L, respectively. It was found
that the addition of tribenzylamine to benzoyl chloride hydrolysis reaction has no catalytic effect and hence the rate constant can be
calculated using a first-order rate equation. In the presence of pyridine, reaction obeyed second-order rate. The relationship between the
reaction rate constant and pyridine initial concentration was found to be linear with a rate constant of 0.752 × 10–3 min–1.
Keywords: Benzoyl chloride, Hydrolysis kinetics, Tertiary amines, Tribenzylamine, Water-dioxane solutions.
and Harris [6] and fluoro alcohols or 1,1,1,3,3,3-hexafluoro-
INTRODUCTION
2-propanol by Kevill and D’souza [7].
Since the first article published in 1927 by Berger and
Olivier for acyl chlorides hydrolysis study, many studies were
published including benzoyl chloride hydrolysis as acyl chloride.
Diefallah et al. [1] studied the hydrolysis reaction of benzoyl
chloride in series ratios mixtures of iso-propyl alcohol with
water. They found a strong relationship between the observed
rate constant and the solvent composition.
A study of the reaction of glycine and benzoyl chloride
in an alkaline aqueous solution/dichloromethane two-phase
medium under inverse phase transfer catalysis was conducted
by Wang et al. [2]. The reaction was described by a pseudo-
first-order rate law. When the concentration of benzoyl chloride
was increased, the reaction rate decreases.
The hydrolysis kinetic studies of acyl chlorides involving
benzoyl chloride are necessary owing to the highly reactive
acyl chloride, as unique monomers, in approaches of synthe-
sizing polymers [8]. In previous study, the effect of pyridine,
2-methyl pyridine, 3-methyl pyridine, 2,6-dimethyl pyridine,
quinoline and tribenzylamine on the hydrolysis kinetics of
benzoyl chloride in water-dioxane solutions was studied [9].
The strongest catalytic effect on the hydrolysis reaction of
benzoyl chloride was for pyridine and 3-methyl pyridine, while
the weakest effect was for quinoline. In this paper, the effect
of pyridine and tribenzylamine on the hydrolysis kinetics of
benzoyl chloride in water-dioxane solutions was investigated.
EXPERIMENTAL
A kinetic study of reactions of aniline and benzoyl chloride
using ammonia as acid absorbent in a micro structured
chemical system was conducted by Wang et al. [3]. They found
that the reaction time is reduced by 99 % when ammonia was
used compared to condition without ammonia. Many kinetic
studies were also published for the hydrolysis of substituted
benzoyl chlorides. For examples, the hydrolysis of substituted
benzoyl chlorides in the presence of: α-, β- and γ-cyclodextrin
were studied by Bascuas et al. [4], hexafluoroisopropanol-
water by Bascuas et al. [5], acetic and formic acids by Bentley
The kinetic reaction:
C6H5COCl + H2O → C6H5COOH + HCl
(I)
was carried out in water-dioxane solution at 25 0.01 °C.
Pyridine and tribenzylamine were used as a tertiary amine in
reaction (I). Benzoyl chloride, pyridine and tribenzylamine
were purified according to methods described in Ivanova et al.
[10], while dioxane was purified according to Vorobuv and
Shebanova [11]. Double distilled water was used in this study.

Vol. 29, No. 9 (2017)
Effect of Pyridine and Tribenzylamine on the Hydrolysis Kinetics of Benzoyl Chloride 1889
The first distillation was carried out by adding KMnO4 (Tb =
99.8 °C at P = 756 mm Hg).
TABLE-2
RATE CONSTANTS k1 AND k2 FOR THE HYDROLYSIS
REACTION OF BENZOYL CHLORIDE IN PRESENCE
OF PYRIDINE AND TRIBENZYLAMINE
In all experiments, only freshly prepared dioxane and
water were used. Methods of kinetic experiments and analysis
of the reaction mixture were the same as reported by Ivanova
et al. [10]. In all the experiments, the initial concentration of
benzoyl chloride was taken to be 0.005 mol/L and the initial
concentration of water was 1 mol/L. The initial concentrations
of pyridine and tribenzylamine were varied in the range of
0.005-0.02 mol/L and 0.007-0.014 mol/L, respectively.
k2 × 103
(min–1)
Initial concentration (mol/L)
k1 (L/mol
min)
k2/C0,p
Pyridine
0.0050
0.0075
0.0100
0.0150
0.0200
Tribenzylamine
0.007
1.28
1.27
1.25
1.19
1.24
1.25
6.45
8.11
12.44
16.28
22.96
13.25
1.29
1.08
1.24
1.09
1.15
1.17
0.014
0.014
0.014
0.014
Average
RESULTS AND DISCUSSION
kobs = k1′ + k2′C0,p
(3)
The observed reaction rate constant (k1) for reaction (I)
carried out in the presence of pyridine was calculated using the
equation:
where k1' is the rate constant for non-catalytic reduction stage
of the process of hydrolysis of benzoyl chloride; and k2' is the
rate constant for the catalyzed stage by pyridine.
The dependence of k1 on the initial concentration of
pyridine is shown in Fig. 1. The relationship is linear and k1 is
0.752 × 10–3 min–1, as it was defined in previous work [12].
C0,p (C0,b − x)
1
k1 =
ln
τ(C0,b − C0,p ) C0,b (C0,p − x)
(1)
where C0,b and C0,p are the initial concentration of benzoyl
chloride and pyridine, respectively; x is the change in benzoyl
chloride concentration at time t from the start of the reaction.
It was found that the hydrolysis of benzoyl chloride in an
aqueous solution in the presence of pyridine obeys second-
order rate reaction. It was established experimentally that when
calculating according to eqn. 1, the rate constants values retain
their constancy to the degree of conversion equal to 60-70 %.
Table-1 lists the arithmetic means of the observed rate constant
(k1) for a concentration of benzoyl chloride of 0.005 mol/L
and different initial concentrations of pyridine in the reaction
mixture.
2.5
2.0
1.5
y = 1.0913x + 0.0942
1.0
R2 = 0.9994
0.5
TABLE-1
0
OBSERVED REACTION RATE CONSTANTS FOR THE
HYDROLYSIS REACTION OF BENZOYL CHLORIDE IN
DIOXANE CONTAINING 1 mol/l mol OF WATER AT 25 °C
0
0.5
1.0
C × 102 mol/L
Fig. 1. Dependence of k1 on the initial concentration of pyridine
1.5
2.0
2.5
Initial concentration (mol/L)
k1 (L/mol min)
Benzoyl chloride
0.005
Pyridine
0.0050
0.0075
0.0100
0.0050
0.0150
0.0200
The results confirm that reaction (I) obeys the first order
kinetic law. Experiments showed that the addition of tribenzyl-
amine has no catalytic effect on the studied reaction and rate
constant in this case can be calculated using a first-order
equation. If pyridine is used as a tertiary amine, then, as can
be seen from reaction (I), hydrogen chloride released during
reaction process is bound to pyridine hydrochloride and the
concentration of pyridine in the reaction mixture varies over
time.
In this paper, preliminary kinetic study showed that during
hydrolysis process of benzoyl chloride, the released benzoic
acid and pyridine hydrochloride acid have no effect on the
rate of the studied reaction.
1.28 0.09
1.27 0.09
1.25 0.09
1.28 0.06
1.19 0.03
1.24 0.06
1.25 0.07
0.005
0.005
0.005
0.005
0.005
Average
When tribenzylamine (C = 0.007 0.014 mol/L) was
added to the reaction mixture, the observed rate constant was
calculated using the following first-order reaction rate equation:
C0,b
Cb
1
k2 = ln
2
(2)
It is well known that the hydrolysis reaction of benzoyl
chloride in aqueous solution proceeds slowly [10,12] and in
the studied concentration range its rate can be neglected in
comparison with the rate of catalytic hydrolysis reaction in
the presence of pyridine.
Table-2 lists the values of k1 and k2 for the hydrolysis
reaction of benzoyl chloride in the presence of pyridine and
tribenzylamine. The initial concentrations of water and benzoyl
chloride were 1.000 and 0.005 mol/L, respectively.
From Table-2, it follows that the addition of tribenzyl-
amine did not affect the hydrolysis reaction of benzoyl chloride;
it only binds HCl released during the reaction. From the results
listed in Table-2, the rate constants for the hydrolysis reaction
without catalyst were calculated as:
Conclusion
The effect of tribenzylamine and pyridine on the hydrolysis
kinetics of benzoyl chloride in water-dioxane solutions was
investigated successfully. In the presence of pyridine, reaction

1890 Batiha et al.
Asian J. Chem.
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obeys second-order rate. The addition of tribenzylamine did
not affect the hydrolysis reaction of benzoyl chloride; it only
binds HCl released during the reaction.The dependence of k1
on the initial concentration of pyridine was 0.752 × 10–3 min–1.
Kinetic study showed that during hydrolysis process of benzoyl
chloride, the released benzoic acid and pyridine hydrochloride
acid have no effect on the rate of the studied reaction.
7. D.N. Kevill and M.J. D’Souza, J. Phys. Org. Chem., 15, 881 (2002);
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