Kinetics of Benzene Photochlorination

S. LEDAKOWICZ*
Institute of Chemical Engineering, t 6 d i Technical University, 90-924 t b d i , Poland

J. PERKOWSKI
Institute of Applied Radiation Chemistry, t 6 d i Technical University, 90-124 L 6 d i ,
Poland

Abstract
An empirical approach to the kinetic investigations of photo-initiated liquid-phase chlo-
rination of benzene is presented. Reaction order and the reaction constants for chlorine
consumption and for the production of hexachlorocyclohexane isomers were evaluated from
experimental data.

Introduction
Photochlorination of benzene essentially results in the formation of a
mixture of stereoisomers of hexachlorocyclohexane (HCH). One of them,
namely the y form, is an effective insecticide, known under the commercial
brands such as Lindan or Gamexane. The photochlorination of benzene
was first described by Faraday in 1825 [l]. The kinetic analysis of this
reaction was initiated by Slator [2] and by Luther and Goldberg [3]. Apart
from the industrial application of this reaction, the literature devoted to
the kinetics of benzene photochlorination is rather scarce [4-61. y-HCH
is produced in large quantities, and process data for its manufacture are
covered by patents [7,8].
At the present time a rigorous kinetic model of the process has not been
reported. However, Voss et al. [9] quite recently attempted to elaborate
on the kinetics of benzene photochlorination.

Reaction Kinetics and Mechanism

The chain and free-radical nature of benzene chlorination initiated
photochemically seems to be well established. Reaction initiation proceeds
* Author to whom correspondence should be addressed. Present address: Oldenburg
liniversity, Ammerlander Heerstr. 67-99, D-2900 Oldenburg, West Germany.

International Journal of Chemical Kinetics, Vol. 15, 119-128 (1983)

01983 John Wiley & Sons, Inc. CCC 0538-8066/83/020119-10$02.00
120 LEDAKOWICZ AND PERKOWSKI

according to eq. (l),representing the photodissociation of the chlorine

molecule:
hu
Clz -+ 2c1.

Chain propagation proceeds as follows:

(2) C6H6 + c1’ + C&jCk
(3) C6H6Ck -k clz ---* C6H6C12 -k ck

(7) C&&& + clz + C6H6C16 + c1‘

The chain termination could proceed according to the scheme
(8) c1-+ Ck - Clz
(9) C&$k (Or C&&$&, Or C6H6C15) + ck
C6H6C12 (Or CsH6C14, Or C6H6Cl6)
+

Certain suggestions concerning the scheme of free-radical mechanism

presented above as well as an alternative ionic mechanism are given by
Krasnousov and co-workers [10,11].
The mechanism of free-radical chain reactions is complex, and therefore
a detailed mathematical description of the reaction kinetics is rather
complicated. The most common mathematical approach is to express the
rate r of these reactions, initiated by radiation of intensity I , in the following
form:
(10) r = k[Aln[B]mI2
The above equation is usually an asymptotic solution of the true kinetics
[12],and the reaction orders n , m, and z are the elements of the set [0,1],
depending on which steps of the free-radical mechanism are controlling.
Experimental evaluation of the rate constants and orders of photo-
chemical reactions is quite complicated. Therefore the literature data
concerning the kinetics of benzene chlorination are incomplete and inco-
herent. Slater [2]stated that the reaction is second order with respect to
chlorine. Luther and Goldberg [3]have shown some oversimplifications
in Slator’s work and the weakness of the foundations on which his conclu-
sions are based. Lane and Noyes [4]have reported that the reaction order
for chlorine is 1. Krivonos [5]arrived at a similar conclusion. Furthermore
he noted the lack of influence of temperature on the reaction rate. He also
found that the reaction rate is proportional to the square root of the light
intensity. A quite different opinion is presented by Governale and Clarke
[6],who have demonstrated a linear dependence of the reaction rate on the
light intensity. It should be noted that none of the authors cited above
made actinometric measurements, basing their calculations only on the
 BENZENE PHOTOCHLORINATION 121

power of the lamps used. Furthermore, the kinetic measurements of

benzene photochlorination concerned only the rate of chlorine consump-
tion.
A somewhat broader approach to this problem was recently presented
by Voss et al. [9] who proposed the following reaction scheme:

where R-HCH are all HCH isomers except the y form. Voss et al. used 2
as a stoichiometric coefficient, but this is presumably an error. Their ki-
netic model for the photochlorination of benzene is based on the assumption
that the reaction is of the first order with respect to chlorine to the light
intensity.
The literature review presented above clearly shows that the kinetics of
the considered process is far from being fully understood. Hence the aim
of the present work is to propose a kinetic model of benzene photochlori-
nation and to identify the kinetic parameters of this model experimen-
tally.

Proposal of Kinetic Model

Theoretically 18 stereoisomers of hexachlorocyclohexane could be
formed, but only five forms of HCH ( a ,P, y,6, and E ) occur as the products
of benzene photochlorination. Each isomer of HCH is formed as a result
of the addition of three molecules of chlorine to a molecule of benzene.
Taking this into account, the authors suggest the following scheme for the
overall reaction of benzene photochlorination which comprises five parallel
reactions:

C6H6 + 3 C1, -
hv
(Y-HCH
P-HCH
7-HCH
hv
6-HCH
C6H6 + 3 CI, €-HCH

The process of benzene photochlorination is carried out in the absence of

any solvent. Thus because of a large excess of benzene with respect to
chlorine, the reaction of chlorine consumption may be treated as pseudo-
nth order:

where CA denotes chlorine concentration, g mol/dm3; I is light intensity,

quanta/(min-dm3);and n and m are reaction orders. Furthermore it is
122 LEDAKOWICZ A N D PERKOWSKI

assumed that the orders of reactions (12)-( 16) of HCH isomer formation
are the same and equal to the reaction order for chlorine. Therefore the
set of equations for the formation rates of HCH isomers takes the following
form:

where the subscript i varies from a to E (i = a, /3, y,6 , ~ ) .

This simplified kinetic model does not reflect the real mechanism of
benzene photochlorination. It should be emphasized, however, that the
model is a compromise between the exactness and the simplicity of de-
scription. It is evident that increasing the complexity of the model involves
an increase in the number of kinetic parameters which are necessary for
the mathematical description of the process, and consequently have to be
identified experimentally.

Experimental
The reactions were carried out in a homogeneous liquid system for the
three following reasons: chlorine liquifies easily, high chlorine solubility
in benzene, and the lack of reaction in the absence of light. Batch chlo-
rinations were run in glass ampuls of 10-cm3volume. The reaction mixture
was prepared by dissolving an appropriate amount of liquified chlorine in
benzene. The process of mixing these components was carried out in a
specially designed glass vessel. The vessel was connected to a 10-cm3
burette to which the ampuls were adjoined in order to fill them. The am-
puls, before filling, were carefully deaerated by means of a vacuum and
purged with helium. In order to avoid the initiation of chlorination, both
the mixing vessel and the burette were carefully darkened. The filling
ampuls were frozen in liquid nitrogen, the helium was then removed, and
the ampuls were sealed off from the vacuum line. The weight analyses
showed the uniformity of filling the ampuls with the reaction mixture to
be within 3%.
The ampuls containing the frozen reaction mixture were mounted on
a rotating disk which was placed in a constant-temperature bath filled with
water. The solution was unfrozen and reached the proper temperature
within 5 min, the operation being carried out in the dark. The glow-tube
lamp, characterized by an emission range of 300400 nm, was then switched
on. The lamp was located outside the constant-temperature bath. The
rotation of the disk with ampuls provided uniform illumination of all
samples and uniform mixing of the reaction liquid. After a given time three
ampuls were removed from the constant/temperature bath and immedi-
ately frozen in liquid nitrogen. Sampling time was small compared to re-
action time. These samples were replaced by ampuls containing benzene
 BENZENE PHOTOCHLORINATION 123

in order to keep the geometry of the system unchanged and to eliminate

the possibility of nonuniform illumination. The light intensity within the
reaction liquid was determined by uranyl-oxalate actinometry [ 131. The
number of quanta absorbed in the sample was calculated on the basis of
the emission spectrum of the light source, the quantum yield of oxalic acid
decomposition in the presence of uranyl sulfate, and the absorption spectra
of benzene saturated with chlorine, of water, and of glass. The light in-
tensity was calculated as a sum of the quanta of various wavelengths ab-
sorbed per unit time in a unit volume of reaction mixture. The scatter of
the results for several ampoules did not exceed 5%.
The chlorine content in the sample was determined by an iodometric
method, while the concentrations of HCH isomers were obtained by gas
chromatography. The parameters of the gas chromatographic analysis
were as follows: glass column 2 m long, 4 mm inner diameter; column filling
3%OV-17, deposited over chromosorb G of granulation 60-80 mesh; column
temperature 463 K; temperature of the flame-ionization detector 493 K;
rate of argon flow 30 cm3/min. Quantitative analysis required the appli-
cation of an internal standard triphenylamine. The calibration and the
determination of the correction factors were made by the use of standard
HCH isomers provided by the Polish National Bureau of Standards.
Nine batch photochlorinations were run, changing the initial chlorine

1.01

-
0.9
--- ---.
0.8 -

0.7-

*%2%
0.6

0.5-
~

s- 04 -

0.3-

0.2 -

0.1-
_/*-
Y

"-30 0 20 LO 60 80 106
t , min
Figure 1. Concentration of chlorine versus time for light intensity I = 1.67 X lo2' quanta/
(min-dm3). 1-Chlorine in benzene solution determined by an iodometric method; 2-
chlorine bounded chemically in HCH isomers determined by gas chromatography.
124 LEDAKOWICZ AND PERKOWSKI

I
0.12

0 M LO . 60 BI) 100
t ,min
Figure 2. Concentration of separate HCH isomers versus time for light intensity I = 1.67
X 1OZ1quanta/min.dm3 and initial chlorine concentration CAO= 0.824 g mol/drn3.

concentration in the range of 4-12 wt-% and the light intensity in the range
of (1.39-1.9) X 1021quanta/(min-dm3). The range of the initial conditions
followed from the reaction rate, the equilibrium solubility of chlorine in
benzene and the exactness of the analytical methods used to determine the
reactant concentrations. All experiments were carried out a t a constant

Cb
mole/di

0
Ct
-e/4m3

0
zci
aole/dm3
0.m
I
0.006 0.001 0.064
0.009 0.002 0.106
0.012 0.004 0.149

r
0.015 0.007
w
0
0.0161

0
0.006

0
0.203

0.022
+
0.049 0.031 0.029 0.007 0.001 0.117
, 0.014 0,042 0.031 0.610 0.013 0.184
' 0.0% 0.060 O.OS8 0.014 0.012 0.240
0.307 0.061 0.053 0.M 0.019 0.267

0.003 0 0 0
L I

0 0.003 t
0.- 0.018 0.096 0.001 0 0,072
0.088 0.046 0.W2 0.015 0.004 0.192
0.131 0.078 0.072 0.025 0.012 0.318
0.150 0.099 0.091 0.039 0.008 0.SG
 BENZENE PHOTOCHLORINATION 125

temperature of 298 K. It has been proved experimentally that in the

temperature range of 283-323 K, the temperature coefficient of the reaction
is approximately equal to 1, the activation energy for the reaction E N
0.
Concentration versus time histories for the reactants and products in
a typical chlorination run are shown in Figures 1 and 2. Some results of
benzene photochlorination are also presented in Table I. It can be noticed
in Figures 1 and 2 that a so-called “dark reaction” proceeded to a small
extent, which slightly changed the initial conditions.

Identification of Kinetic Parameters

In order to determine the kinetic parameters of the proposed model for
benzene photochlorination a simple optimization method was utilized. The
objective function J (performance index), defined as the sum of the squares
of the deviations of experimental concentrations from the calculated ones,
was minimized. Too small a range of variations of the light intensity
[(1.39-1.9) X loz1quanta/(min-dm3)] did not allow us to determine accu-
rately the reaction order with respect to the light intensity. Hence we used
the rate constant k a = k A I m instead of using discretely the intrinsic rate
constant k A and the reaction order m. In this case the integrated form of
eq. (17) is
(&)n-l - (&)n-l = ( n - l)k’,t

By taking logarithms and subtracting both sides of eq. (19) we obtained

the objective function J:

The inner summation concerns the chlorine concentration and the outer
one the time.
It should be noted that eq. (19) is true for every value of n but 1. For this
reason the assumption of a reaction order of unity with respect to chlorine
was checked carefully. The rate constant obtained by fitting the experi-
mental data was found to be dependent on chlorine concentration. The
objective function J = f ( n ,log k a ) is nonlinear only with respect to n , as
follows from Eq. (20). Therefore it was decided to fix the variable n. Then
J becomes the linear function of one variable, J = f(1og kk),, and the
minimizing values can be obtained from the following condition:
dJ
d(1og k a ) =
For a given value of n and for value of k k obtained from eq. (21) one could
126 LEDAKOWICZ AND PERKOWSKI

calculate the value of the performance index J , applying the experimental

data to the expression (20). Repetition of this procedure for several values
of the reaction order n E [0, 1)gave at last a discrete dependence J = f ( n ) ,
reaching a minimum at n = 0.4. The corresponding values of the rate
constants are presented in Table 11.
To determine the rate constants for the production of HCH isomers one
applies the assumption that the orders of reactions (12)-(16) are the same
and equal to the reaction orders for chlorine and light intensity. Dividing
eq. (18)for the rate of product formation by eq. (17) for the rate of chlorine
consumption and integrating the quotient yields the relation between rate
coefficients:
(22) (Ci - C ; O ) / ( ~ -
AOCAI = ki/kA
where i = a , 0,y, 6, or t.
It follows from eq. (22) that the dependence of the concentration of any
HCH isomers on chlorine concentration Ci = ~ ( C Ais) a linear function,
independent of the reaction order. The least-squares method was used
to find the values of the rate constants ki for the production of HCH iso-
mers. The performance indices in this case have the following forms:

The necessary conditions for the minimum of the functions Ji are

where i = a , 0,y, 6, or E .
The “most probable” values of the rate constants for the production of
HCH isomers obtained in this way are listed in Table 11. An additional
test for the validity of the obtained results can be provided by stoichiometry

TABLE11. Rate constants of benzene photochlorination.

 BENZENE PHOTOCHLORINATION 127

analysis, which leads to the following correlation:

(29) 3(kk + kb + kk + k6 + k : ) = k a
The accuracy of the identified rate coefficients is presented in Table I1 as
a relative percent deviation between the two sides of eq. (29), and in any
case does not exceed 3%.

Summary and Conclusions

A simplified kinetic model of benzene photochlorination has been pro-
posed, based on a literature survey and experimental studies. The main
assumptions of the model are that the process proceeds in five parallel re-
actions and that the orders of the reactions of HCH isomer formation are
the same and equal to the reaction orders for chlorine and the light inten-
sity. In order to identify the kinetic parameters of power-law kinetic re-
lationships for the formation of HCH isomers and for chlorine consumption,
several batch photochlorinations were run. The reaction proceeds at 298
K, because according to earlier investigations the temperature effect in the
range of 283-323 K is insignificant. The initial conditions for light intensity
and chlorine concentration were changed in the range of (1.39-1.9) X 1021
quanta/(min.dm3) and 4-12 wt-%, respectively.
Numerical identification of kinetic parameters obtained by applying
optimization methods gave a reaction order for chlorine of 0.4and the rate
constants (Table 11). The rate constants of HCH isomer formation cor-
respond well with the rate constants of chlorine consumption, deviating
by less than 3%. It should be emphasized, however, that the purpose of
the present work was to find a simplified mathematical description of
benzene photochlorination, regardless of the true mechanism of the reac-
tion. This description should be valid in certain industrially important
ranges of the variables. Therefore, ascribing any strict physical meaning
to the kinetic parameters of the model would be unjustified. The future
kinetic investigation of benzene photochlorination should be aimed a t
comparing the homogeneous chlorination results with the heterogeneous
ones.

List of Symbols
CA chlorine concentration, g mol/dm3
Ci concentration of one of HCH isomers, g mol/dm3
h Planck’s constant
Z light intensity, quanta/(min.dm3)
J objective function, performance index
k~ rate constant of chlorine consumption, (g m ~ l / d m ~ ) ~ . ~ / m i n
128 LEDAKOWICZ AND PERKOWSKI

hi rate constant of formation of HCH isomer, (g rn0l/dm~)~.6/min

n reaction order for chlorine
m reaction order for light intensity
r reaction rate
t time

Subscripts
0 initial value
i ith isomer of HCH

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Received June 2,1981

Accepted September 23,1982