The interaction of ozone with chlorobenzene

Article abstract of DOI:10.1134/S0036024407060088

The reaction of ozone with chlorobenzene was studied over the temperature range 77-305 K. Ozone was found to oxidize chlorobenzene starting with 77 K to produce a complex mixture of ozonides and peroxides of various compositions. The products of the reaction between chlorobenzene and ozone formed over the temperature range 77-305 K were analyzed by IR Fourier transform spectroscopy. Nauka/Interperiodica 2007.

Full text of DOI:10.1134/S0036024407060088

ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2007, Vol. 81, No. 6, pp. 878–882. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © T.A. Vysokikh, T.V. Yagodovskaya, S.V. Savilov, V.V. Lunin, 2007, published in Zhurnal Fizicheskoi Khimii, 2007, Vol. 81, No. 6, pp. 1010–1014.
CHEMICAL KINETICS
AND CATALYSIS
The Interaction of Ozone with Chlorobenzene
T. A. Vysokikh, T. V. Yagodovskaya, S. V. Savilov, and V. V. Lunin
Faculty of Chemistry, Moscow State University, Leninskie gory, Moscow, 119992 Russia
e-mail: sintestan@mail.ru
Received April 24, 2006
Abstract—The reaction of ozone with chlorobenzene was studied over the temperature range 77–305 K. Ozone
was found to oxidize chlorobenzene starting with 77 K to produce a complex mixture of ozonides and peroxides
of various compositions. The products of the reaction between chlorobenzene and ozone formed over the tem-
perature range 77–305 K were analyzed by IR Fourier transform spectroscopy.
DOI: 10.1134/S0036024407060088
INTRODUCTION
reported. This work is concerned with the possibility of
the oxidation of chlorobenzene with ozone at tempera-
tures close to the stratosphere temperature.
Among the great number of problems that trouble
the modern society, the protection of the environment is
one of the most pressing. The diversity of harmful
organic impurities in the biosphere is related to dis-
charges of industrial wastes and utilization of domestic
garbage by thermal treatment. This results in the release
of chlorinated benzene derivatives formed in the ther-
mal decomposition of polyethylene in the presence of a
source of chlorine (e.g., sodium chloride) [1]. One of
the methods for solving ecological problems such as
the purification of waste water, air, drinking water,
industrial wastes, and the products of garbage combus-
tion is the use of ozone as an effective ecologically
friendly oxidizer. For instance, chlorobenzene can long
exist in the upper atmosphere, and this is one of the
agents that destroy ozone in the stratosphere.
The oxidation of aromatic compounds with ozone has
been studied poorly. As is suggested in many works [4–
10], the mechanism of the reaction between ozone and
aromatic compounds is similar to the mechanism of
ozone–olefin interactions. The properties of the ozonides
produced, such as their impact or friction sensitivity, are
somewhat different. According to [11], the charge-trans-
fer complex formed initially under the action of ozone on
a multiple bond can transform along three parallel direc-
tions, with the formation of moloozonide, σ-complex,
and ion-radical pair at equilibrium with the complex. The
σ-complex can transform into epoxy and oxy deriva-
tives, and the ion-radical pair containing mobile hydro-
gen easily gives the R• and •éç radicals.
The ozonation of substituted benzenes was studied
in [11–13]. The authors showed that the attack of ozone
was electrophilic in character, that is, was directed at
the atom with the lowest localization energy [11].
According to [11], the reactivity of aromatic com-
pounds increases as the number of electron donor sub-
stituents in the ring grows. The presence of electron
acceptor substituents in the aromatic ring decreases the
rate of the reaction somewhat.
According to [2, 3], a decrease in the concentration
of ozone in the ozone layer is related to the presence of
active chlorine, whose source is HCl. A laboratory
study of the interaction of ozone with HCl under the
conditions close to stratospheric was performed. A
model of atmospheric clouds (ice–HCl–ozone, T =
77 K) [2, 3] was used to show that HCl interacted with
ozone over the temperature range 77–273 K to produce
chlorine oxides of various compositions. No similar
According to [14], the ozonation of chlorobenzene
data on chlorinated aromatic compounds were in chloroform at 228 K follows the scheme
Cl
Cl
C
H
C
C
H
Cl
O3
O3
O
O
O
O
COOH
+ 3O3
+ 2
+ Cl–
O3
H2O
C
C
H
O
H
EXPERIMENTAL
pure chlorobenzene with an ozone–oxygen mixture in a
bubbling reactor over the temperature range 273–305 K
and by the low-temperature ozonation of chloroben-
The reaction of ozone with chlorobenzene was per-
formed following two procedures, by the oxidation of
878

THE INTERACTION OF OZONE WITH CHLOROBENZENE
879
Transmission
Transmission
(b)
(‡)
1
2
1
2
0.9
0.6
0.3
0
0.8
3
0.4
0
3
700
800
900
1600
1800
ν, Òm–1
ν, Òm–1
Fig. 1. IR spectra of the (1) ice–chlorobenzene system at 77 K, (2) ice–chlorobenzene–ozone system at 77 K, and (3) ice–chloroben-
–1
zene–ozone system at 273 K over the frequency ranges (a) 650–950 and (b) 1500–2300 cm .
zene with the use of a flow vacuum electric discharge metrically (Finnigan MAT 112S with a Varian 3300 gas
chromatograph).
unit. The latter reaction was studied in situ by IR spec-
troscopy over the temperature range 77–292 K. The
main part of the flow vacuum electric discharge unit
was a discharge tube for the preparation of pure ozone
from a glow discharge plasma in oxygen. The unit was
connected to a low-temperature optical cell with a
system of three golden mirrors, on which vapors of
RESULTS AND DISCUSSION
When gaseous ozone was introduced into the low-
temperature cell with a layer of water and chloroben-
zene deposited on the surface of mirrors at 77 K, the
the substances studied condensed. Prior to measure- instantaneous interaction of ozone with the system
ments, the unit was evacuated to 10–4 torr. Water and
chlorobenzene were sequentially deposited at 77 K
onto the mirrors of the low-temperature optical cell
from a vaporizer held at 292 K. The cell was
mounted in the light beam path of an IR Fourier
transform spectrometer. The reagents were intro-
was observed, which manifested itself by the appear-
ance of new characteristic bands in the IR spectrum
(Fig. 1).
The wave numbers of the products of chlorobenzene
interaction with ozone at 77 K are listed in Table 1. The
spectra of the reaction products were different from that
duced in a pulsed mode, by turning the capillary cock of the initial ice–chlorobenzene system (Fig. 1, spectra 1
and 2), they contained new absorption bands that might
be assigned to stretching vibrations of phenols and the
corresponding ozonides.
of the vaporizer. The ice–chlorobenzene system pre-
pared this way was brought in contact at a 6 × 10–3 torr
residual pressure (77 K) with ozone, whose initial
pressure was 1.0 torr. Reaction products were ana-
lyzed by recording their IR spectra over the wave
number range 600–2500 cm–1.
The absorption bands of ozone (656 and 678 cm–1)
and chlorobenzene (740 cm–1) disappeared as the tem-
perature of the sample increased to 273 K, and the
intensities of the characteristic lines at 1727, 1688, and
886 cm–1 decreased (Fig. 1, spectra 2 and 3). These
lines can be assigned to ozonides of aromatic com-
pounds. Simultaneously, new absorption bands at 854,
1752, and 1850 cm–1 corresponding to vibrations of
aromatic peroxide compounds (830–890 and 1755–
The ozonation of liquid chlorobenzene was studied
in the bubbling reactor. The unit contained ozonizer,
trap, ozonometer, reactor, and connecting pipes. An
ozone–oxygen mixture was introduced into the reactor
filled with chlorobenzene through an exhaust pipe with
a glass splitter for the gas mixture jet. The splitter 1785 cm–1 [18–20]) appeared. This was evidence that
the reaction between chlorobenzene and ozone contin-
ued.
welded at the end of the pipe had the shape of a hollow
ball. The reaction was performed at the initial ozone
concentration 90–92 g/ml; the volume flow rate of the
é3/é2 gas mixture was 0.2 l/min. The products were
analyzed IR spectroscopically (FSM 1201), by gas
chromatography (Agilent Technologies 6890N with a
Groups of absorption bands of the corresponding
ozonides and peroxo compounds (886 cm–1), ozone
(1267 and 1285 cm–1), and chlorobenzene (1446, 1477,
and 1700 cm–1) [18–20] disappeared sequentially as the
flame-ionization detector), and chromato-mass spectro- temperature of the sample increased to 292 K and the
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VYSOKIKH et al.
Table 1. IR absorption spectra of the ice–chlorobenzene-ozone system at 77 cm–1; wave numbers ν (cm–1) according to
(I) our and (II) literature data
I
II
Assignment
656, 678, 1105
1267, 1285
1688
612, 705, 1110 [2, 15]
1260, 1280 [16, 17]
1660–1620 [18]
882, 1720 [18]
3654 [19]
Ozone O–O bond stretching vibrations
Stretching vibrations of the C=C bond conjugated with the O atom
Ozonide O–O stretching vibrations
886, 1727
3595
Phenol absorption bands
2980, 3061
1700
3030–3060 [19, 20]
1625–1575 [19, 20]
1475–1525 [19, 20]
1465–1440 [19, 20]
680–720 [19]
Chlorobenzene C–H stretching vibrations
Chlorobenzene aromatic ring in-plane C=C stretching
vibrations
1477
1446
685, 704
908
Monosubstituted benzene out-of-plane C–H bending
vibrations
900 [19]
746
742 [20]
C–Cl stretching vibrations
Table 2. IR spectrum of the solid phase; wave numbers ν (cm–1) according to (I) our and (II) literature data
I
II
Assignment
H2O stretching vibrations
3650–3100
3069
3400, 3220 [21]
3030–3060 [19, 20]
1590–1575 [19, 20]
1475–1525 [19, 20]
1440–1465 [19, 20]
1175–1125 [19, 20]
1110–1070 [19, 20]
1070–1000 [19, 20]
1000 [18]
C–H stretching vibrations
1585
Aromatic ring C=C stretching vibrations
1477
1446
1154
Aromatic compound in-plane C–H bending vibrations
1081
1023
1004
Peroxo compound O–O vibrations
Ozonide O–O vibrations
904, 1770, 1792
740
882, 1772, 1792 [18]
742 [20]
C–Cl stretching vibrations
684, 702
720–680 [19]
Out-of-plane C–H bending vibrations
compounds specified were removed from the surface of chlorobenzene first caused turbidity and then the pre-
the low-temperature cell mirrors.
cipitation of a white powder.
When pure chlorobenzene was ozonized in the bub-
bling reactor, a virtually instantaneous change in liquid
phase coloration was observed. The intensity of the
color of chlorobenzene increased as the temperature of
the reactor grew, and the solution took on various tinges
of yellow. At 273 K, it was pale yellow with a tinge of
green, at 293 K, it was yellow, and, at 305 K, it was
bright yellow. According to [14], the observed colora-
tion could be caused by the formation of a colored
A study of the liquid phase by gas chromatography
showed that the major solution component was chlo-
robenzene (98 vol %). The composition of the complex
mixture of ozonation products (2 vol %) was analyzed
by chromato-mass spectrometry; it was found to con-
tain phenol and chlorophenols.
The solid phase formed in the reaction was insoluble
in either water or organic solvents (n-pentane, n-hex-
π-complex between chlorobenzene and ozone. Subse- ane, ethanol, benzene, and toluene). It exploded in the
quent bubbling of the ozone–oxygen mixture through dry state in air under the slightest mechanical actions.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 81 No. 6 2007

THE INTERACTION OF OZONE WITH CHLOROBENZENE
Transmission
881
0.8
0.4
0
500
1000
1500
2000
2500
3000
ν, Òm–1
–1
Fig. 2. IR spectrum of the solid phase at 292 K over the frequency range 500–3500 cm .
Wetting the precipitate with solvents decreased the
probability of explosion.
A comparison of the vibrational frequencies
observed with the literature data allowed us to approx-
imately assign them to stretching vibrations of the chlo-
robenzene ozonide molecule likely stabilized by the
presence of chlorine in the benzene ring. According to
[11, 14, 22], the following interaction mechanism can
be suggested:
To model the composition of the solid phase formed,
a sample deposited on a KBr pellet was analyzed IR
spectroscopically. The results are shown in Fig. 2 and
listed in Table 2.
Cl
Cl
Cl
O
+ O3
O3
(π-comple)
O
products
O
(moloozonide)
6. P. S. Baley, S. Bath, F. Dobinson, et al., J. Org. Chem. 29,
The major product at early stages is moloozonide.
697 (1964).
To summarize, a comparison of the experimental
and literature data showed that ozone reacted with chlo-
robenzene over a wide temperature range (77–305 K)
with the formation of a complex mixture of compounds
and moloozonide as an intermediate product.
7. M. G. Sturrock, B. J. Cravy, and V. A. Wing, Can. J.
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8. P. S. Baley and J. E. Batterbee, J. Org. Chem. 29, 1400
(1964).
9. P. S. Baley, J. E. Batterbee, andA. G. Lane, J.Am. Chem.
Soc. 90 (4), 1027 (1968).
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