Kinetic Relationships of Liquid-Phase Oxidation of Styrene with Hydrogen Peroxide in the Presence of Polyoxotungstate Modified with Cerium Cations

Article abstract of DOI:10.1134/S1070427220050146

Liquid-phase oxidation of styrene with hydrogen peroxide in the presence of a catalytic system based on (NH₄)₁₀W₁₂O₄₁ + Ce(NO₃)₃ + H₃PO₄, supported on a microstructured carbon material and treated with an aqueous Н₂О₂ solution, was evaluated. The major reaction products are phenyloxirane and benzaldehyde, with phenylacetaldehyde, 1-phenylethane-1,2-diol, and benzoic acid also present. The kinetic relationships of the process were investigated, and a kinetic model according to which phenyloxirane is the primary reaction product was suggested. Aldehydes were accumulated by parallel routes, namely oxidation of phenyloxirane and of its hydrolysis product, 1-phenylethane-1,2-diol. With an increase in the styrene, Н₂О₂ molar ratio, oxidation of 1-phenylethane-1,2-diol became the major pathway of the aldehyde formation.

Full text of DOI:10.1134/S1070427220050146

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2020, Vol. 93, No. 5, pp. 729–740. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Prikladnoi Khimii, 2020, Vol. 93, No. 5, pp. 722–734.
CATALYSIS
Kinetic Relationships of Liquid-Phase Oxidation of Styrene
with Hydrogen Peroxide in the Presence of Polyoxotungstate
Modified with Cerium Cations
H. M. Alimardanova,*, F. M. Veliyevaa, N. I. Garibova, and E. S. Musayevaa
a Mammadaliyev Institute of Petrochemical Processes of National Academy of Sciences of Azerbaijan,
Baku, AZ1025 Azerbaijan
*e-mail: hafiz_alimardanov@yahoo.com
Received June 11, 2019; revised November 20, 2019; accepted December 14, 2019
Abstract—Liquid-phase oxidation of styrene with hydrogen peroxide in the presence of a catalytic system based
on (NH4)10W12O41 + Ce(NO3)3 + H3PO4, supported on a microstructured carbon material and treated with an
aqueous Н2О2 solution, was studied. The major reaction products are phenyloxirane and benzaldehyde, with
phenylacetaldehyde, 1-phenylethane-1,2-diol, and benzoic acid also present. The kinetic relationships of the
process were studied, and a kinetic model according to which phenyloxirane is the primary reaction product was
suggested.Aldehydes are accumulated by parallel routes: oxidation of phenyloxirane and of its hydrolysis product,
1-phenylethane-1,2-diol. With an increase in the styrene: Н2О2 molar ratio, oxidation of 1-phenylethane-1,2-diol
becomes the major pathway of the aldehyde formation.
Keywords: oxidation, styrene, hydrogen peroxide, phenyloxirane, benzaldehyde, cerium polyoxotungstate, kinetic
model
DOI: 10.1134/S1070427220050146
Oxidative functionalization of unsaturated hydro-
carbons with hydrogen peroxide is one of priority di-
rections of organic and petrochemic al synthesis [1, 2].
The oxidation products (epoxides, alcohols, ketones,
aldehydes, ethers, esters) are used for producing phar-
maceuticals, perfumes, biologically active compounds,
epoxy resins, and plasticizers.
are active intermediates in introduction of oxygen-
containing fragments into the starting molecules.
Only a few studies deal with the kinetic relationships
of the oxidation of styrene and its derivatives; molecular
oxygen or NaIO4 is used in these studies as an oxidant
[10, 13]. It should be noted, however, that the mechanism
of the oxidation of this substrate with hydrogen peroxide
differs essentially from the mechanism of its oxidation
with molecular oxygen.
Epoxidation of olefins on the commercial scale is
performed either with molecular oxygen in the presence
of a catalyst containing silver oxide nanoparticles [3]
or with organic hydroperoxides with the participation
of various molybdenum and tungsten compounds [4, 5].
Epoxidation of styrene (St) and its derivatives in the
presence of various homogeneous and heterogeneous
catalytic systems is performed using such oxidants as
hydrogen peroxide [6–8], NaClO [9], and NaIO4 [10].
Tungsten or molybdenum polyoxo complexes show
high activity and selectivity in oxidation of unsaturated
hydrocarbons [11, 12]. The peroxotungstates or
peroxomolybdates formed from these complexes
This study was aimed at determining the kinetic
relationshipsoftheliquid-phaseoxidationofstyrenewith
hydrogen peroxide in the presence of polyoxotungstate
modified with cerium cations and at developing a kinetic
model of the multiple-route process.
EXPERIMENTAL
The liquid-phase oxidation of styrene was performed
using a catalytic system (CS) prepared by mixing and
boiling for 2 h aqueous solutions of (NH4)10W12O41 and
729

730
ALIMARDANOV et al.
(a)
(b)
nm
Y, nm
X, nm
Z, nm
Fig. 1. (a) 3D image and (b) surface histogram of the synthesized carbon material, taken with an atomic force microscope.
Ce(NO3)3 (Sigma–Aldrich, 99.9%), 85% H3PO4, and a
microstructured carbon material. The resulting mixture
was evaporated, and the solid residue was dried at 100–
120°С and heat-treated at 180–200°С [14]. A carbon
material prepared by stirring aluminum metal turning
with excess CCl4 at 75–76°С [15],
with ethyl acetate, and the ester extracts were combined
with the organic layer. After distilling the solvent off, the
oxidation products were analyzed.
The styrene oxidation products were identified using
gas–liquid chromatography, mass spectrometry, and IR
spectroscopy.
Efficient separation of styrene oxidation products
was reached on a Tsvet-100 m chromatograph under
the following conditions: thermal conductivity detector,
carrier gas helium, 1 m × 2 mm column, stationary phase
Apiezon L (15 wt % on Chromaton N-AW-HMDS). The
IR spectra of the oxidation products and catalyst were
recorded with an Alpha Fourier IR spectrometer in the
range 400–4000 cm–1 or with a Vertex spectrometer
(Bruker) in the range 100–700 cm–1. The absorption
bands were assigned in accordance with the reference
data. Elemental analysis was performed with a TruSpes
Micro analyzer (LECO Corporation, the United States).
2Al + 3CCl4 → 2AlCl3 + C2Cl6 + C,
2Al + C2Cl6 → 2AlCl3 + 2C,
was used as a support. The reaction was performed for
3–4 h until the aluminum was completely consumed.
The resulting carbon material was separated by
filtration, washed with CCl4, dried in a nitrogen stream
at 80–120°С, and heat-treated at 200–250°С until the
НCl evolution and AlCl3 sublimation ceased (Fig. 1).
Prior to use in styrene oxidation, the catalytic system
was kept in a 35% Н2О2 solution at the ratio CS : Н2О2 =
1 : 200 (Fig. 2). According to [11, 12], such catalytic
system consists of various peroxo complexes of the
general formula [РkWmOn(O2)p]x.
Images of cerium polyoxotungstate and cerium
polyoxoperoxotungstate samples were taken with an
Oxford Instruments Nano Analysis (OINA) 5-3400N
scanning electron microscope (SEM).
The styrene oxidation was performed in
a
temperature-controlled 50-mL glass reactor equipped
with a thermometer, a magnetic stirrer, a reflux
condenser, dropping funnels, and a unit for sampling
at 60–80°С. The reactor was charged simultaneously
with styrene (0.1–0.15 mol), hydrogen peroxide (35%
aqueous solution, 0.1–0.3 mol), catalyst, and toluene
(10 mL).Asolution of H3BO3 in n-butanol or α-naphthol
(0.5% relative to the reaction mixture) was added to the
reaction mixture to prevent oxidative oligomerization
of styrene. After the reaction completion, the organic
layer was separated, the aqueous layer was extracted
The surface relief of the microstructured carbon
material was examined with an NC-AMF scanning
atomic force microscope.
Analysis by gas chromatography–mass spectrometry
(GC–MS) was performed with a GC 7890A-MSD5975C
device (Agilent Technologies) under the following
conditions: HP5-MS column, programmed heating in
the range 40–280°С, carrier gas helium.
In the IR spectra of the catalyst samples, the
absorption bands at 406, 486, 566, 587, 603, 620, and
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KINETIC RELATIONSHIPS OF LIQUID-PHASE OXIDATION
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6.40 μm
36.7 μm
4.01 μm
12 μm
20.0 μm
2.00 μm
56.4 μm
100 μm
100 μm
(a)
(b)
Fig. 2. Electron microscopic images of the surface of Ce peroxotungstate samples treated with (a) phosphoric acid and (b) hydrogen
peroxide.
775 cm–1 characterize the –О–Се–О fragment. The
bands at 980, 925, 880, and 871 cm–1 belong to stretching
vibrations of WO4+ and W=O fragments. The bands at
1015, 1030, and 1065 cm–1 in the Fourier IR spectrum of
the polyoxophosphotungstate complex characterize the
PO43– stretching vibrations. The reaction of these catalyst
samples with a 35% aqueous Н2О2 solution yields a
mixture of at least two peroxo complexes of golden
yellow color. The absorption bands at 890, 680, 589, and
561 cm–1 belong to stretching vibrations of the peroxide
When using the peroxopolytungstate catalytic system,
the styrene conversion and oxidate composition vary
in a wide range depending on the reaction temperature
and stirring rate. Because variation of the stirring rate in
the range 700–900 rpm (Fig. 3) does not influence the
styrene conversion, the kinetic studies were performed
at 700 rpm. Under these conditions, there is no external
diffusion hindrance.
The degree of styrene oxidation and the composition
of reaction products significantly differ depending
on the polyoxotungstate modification (Table 1). For
example, when using unmodified polyoxotungstate
under the conditions chosen as standard (80°С,
5 h, styrene : Н2О2 molar ratio 1 : 1.2), the styrene
bond
. The IR spectra of the heterogenized samples
contain all the above-indicated absorption bands. As
shown by SEM (Fig. 2) and X-ray diffraction analysis,
the crystalline structure of the sample undergoes
amorphization on treatment with Н2О2.
Conversion, %
The elemental composition of the catalyst is
as follows: C 24.58, Ce 3.55, P 1.57, W 56.0, and
О 18.3 wt %, which corresponds to C 53.0, Ce 0.77,
P 1.56, W 9.4, and О 35.3 at. %.
h
h
h
h
RESULTS AND DISCUSSION
h
h
Recentpublisheddataconcerningthestyreneoxidation
with hydrogen peroxide are quite contradictory, which
is caused by the use of different catalytic systems [6–8,
16–18]. Taking this fact into account, we first performed
experiments without catalyst. A mixture of 0.05 mol of
styrene, 6 g of 35% Н2О2, and 30 mL of toluene was
stirred at 80°С for 3 h. The styrene conversion was 4.0%;
i.e., without a catalyst styrene is not noticeably oxidized.
ν, rpm
Fig. 3. Styrene conversion as a function of the rate of stirring
the reaction mixture at 70°С (St : H2O2 molar ratio 1, solvent
toluene).
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ALIMARDANOV et al.
Table 1. Results of catalytic oxidation of styrene with hydrogen peroxide in the presence of various forms of polyoxotungstate
(Т = 80°С, τ = 5 h, styrene : Н2О2 = 1 : 1.2)
Oxidate composition, wt %
Styrene
Catalyst
conversion,
%
phenyl-
benz-
phenyl-
phenylethane-
diol
benzoic oligomeric
styrene
oxirane aldehyde acetaldehyde
acid
products
(NH4)10W12O41·nН2О (I)
29.5
32.6
67.3
4.4
17.7
14.5
2.6
6.2
3.0
4.0
9.4
8.2
–
–
(NH4)10W12O41 + H3PO4
(II)
1.7
1.0
(NH4)10W12O41
Ce(NO3)3 + H3PO4 (III)
+
42.7
45.0
54.0
4.5
1.9
3.2
14.4
18.4
27.3
8.8
8.7
9.8
6.0
6.9
7.8
9.3
10.4
4.7
4.1
2.0
3.7
2.9
1.7
3.5
Catalyst III + carbon
material (IV)
Catalyst IV + H2O2 (V)
conversion is 29.5%, and the major reaction products
are phenyloxirane and 1-phenylethane-1,2-diol. With
unsupported cerium polyoxotungstate, the styrene
conversion reaches 42.7%, and the amount of aldehydes
in the oxidate increases (Table 1). The use of the
catalyst supported on the carbon material increases the
styrene conversion to 45.0% with higher selectivity of
phenyloxirane and benzaldehyde formation. However,
the highest conversion of styrene is reached in the
presence of the catalytic system preliminarily treated
with hydrogen peroxide (Table 1).
the following formula for evaluating the effect of the
internal diffusion:
where r is the reaction rate (mol gkg L–1 min–1); dp, cata-
lyst particle size (cm); сs, substrate concentration (M);
and De, diffusion coefficient of the starting compound in
the solvent (cm2 min–1). According to published data, at
Φ < 1/[n] the effect of diffusion on the reaction order n
can be neglected.
In kinetic studies of styrene oxidation in the presence
of heterogeneous catalysts, the internal diffusion
hindrance is revealed by varying the catalyst particle
size. According to the SEM data, the particle size of the
catalyst used is 1–3 μm, which does not allow revealing
the effect of the internal diffusion hindrance on the
reaction rate. Sarbak and Lewandowski [19] suggest
With an increase in the initial concentrations of sty-
rene, hydrogen peroxide (Table 2), and catalyst (Fig. 4)
at constant concentrations of the other components,
accumulation of oxidation products linearly increases.
The styrene oxidation rate (rSt) was determined using
the formula
where rSt is the styrene transformation rate (mol L–1 h–1);
c10, initial styrene concentration (M); c1τ, styrene
concentration after the experiment (M); Kс1, styrene
conversion (rel. units); and τ, experiment time (h).
Without catalyst, the reaction rate is low. With
an increase in the catalyst concentration from 0 to
11.0 g L–1, the reaction order with respect to the catalyst
approaches unity (Fig. 4). In the interval 11.0–12.5 g L–1,
this parameter varies from zero to unity, and above
12.5 g L–1 it is equal to zero. The catalysts supported
on the carbon material preserve their activity for a long
time (Fig. 5).
ccat, g L–1
Fig. 4. Influence of the catalyst concentration on the styrene
oxidation rate.
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KINETIC RELATIONSHIPS OF LIQUID-PHASE OXIDATION
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ALIMARDANOV et al.
Run no.
Fig. 5. Variation of the activity of catalyst V in the course of repeated runs (time of each run 5 h). (1) Styrene conversion and (2) selectivity
with respect to the sum of oxidation products.
In the examined range of the initial concentrations
of styrene and hydrogen peroxide, the rate of their
consumption is a linear function of the concentration of
the starting components. Hence, the formal reaction rate
is determined by the formula
styrene and hydrogen peroxide concentrations (M); and
CAT, catalyst amount (g L–1).
Based on the experimental data (Table 2), we suggest
two schemes of the oxidative transformation of styrene
and accumulation of reaction products (Schemes 1, 2).
Oxidation of unsaturated hydrocarbons with
hydrogen peroxide occurs along multiple routes via
formation of the corresponding epoxide. Hence, it can
be assumed that the reaction occurs in successive steps
involving further transformations of the peroxides
WSt = k[c1][c2 × CAT],
where WSt is the formal rate of styrene transformation
(mol L–1 h–1); k, rate constant (L mol–1 h–1); c1 and c2,
Scheme 1.
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KINETIC RELATIONSHIPS OF LIQUID-PHASE OXIDATION
735
Scheme 2.
formed. To check this version, we plotted the styrene
conversion curves (Fig. 6) in the S–K coordinates (S is the
selectivity with respect to epoxide, and K is the styrene
conversion). Phenyloxirane at K → 0 is not the only
product of styrene oxidation (found by extrapolation of
the curves at different temperatures) (Fig. 6).
IV, V, and VII. Both the first (reactions III, VII) and
the second (reaction III) schemes include the styrene
oxidation to aldehydes in one step.
According to published data [20, 21], vanadium-
substitutedheteropolymolybdicacidexhibitshighactivity
in benzene hydroxylation to phenol [21, 22], and the
heteropoly compound (NH4)8[La(PMo9V2O39)]·6H2O is
highly active in phenol oxidation to hydroquinone [22].
It is assumed that these systems operate in hydrocarbon
oxidation similarly to Fenton’s reagent (Fe2+ + H2O2)
[23, 24]. Taking these facts into account, we assumed
Phenylacetaldehyde, benzaldehyde, and phenyle-
thane-1,2-diol are formed along with the epoxide. The
results of the studies show that the reaction occurs via
parallel-consecutive transformations of styrene and
oxidation products. This pattern is probably caused by
the formation of tungsten peroxo complexes of dif-
ferent structures, exhibiting different activity in this
reaction. The assumption that such styrene oxidation
products as benzaldehyde, phenylacetaldehyde, and
phenylethane-1,2-diol are formed exclusively via trans-
formation of the epoxy intermediate is groundless. Such
products can also be formed directly by the oxidation of
styrene itself.
The first step in both schemes of the process is
directly the styrene epoxidation. However, whereas in
the first scheme reactions II, V, and VI illustrate the
transformation of the oxirane formed into benzaldehyde,
phenylacetaldehyde, and phenylethane-1,2-diol, in the
second scheme the above aldehydes are formed from
phenylethane-1,2-diol and phenyloxirane by reactions
Conversion, %
Fig. 6. Reaction selectivity with respect to phenyloxirane as
a function of the styrene conversion at (1) 50, (2) 70, (3) 75,
and (4) 80°С.
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ALIMARDANOV et al.
Table 3. Observed rate of accumulation of key substances in styrene oxidation with hydrogen peroxide at various temperatures
ωi, mol L–1 h–1
ω7
ω8
–ω1
(styrene)
ω3
ω4
ω5
ω6
–ω2 (Н2О2)
(benzoic (oligomeric
acid)
(phenyloxirane) (benzaldehyde) (phenylacetaldehyde) (phenylethanediol)
products)
60°С
5.05
4.92
5.16
4.70
10.85
8.0
3.8
0.75
0.31
–
–
–
–
–
–
–
–
–
–
–
–
3.5
1.067
1.02
0.247
0.327
0.410
5.6
2.842
2.35
5.35
1.408
70°С
4.56
5.60
5.52
4.90
9.695
7.833
6.60
3.825
4.00
0.55
0.185
0.383
0.400
0.452
–
–
–
–
–
–
0.817
0.902
0.875
–
0.4
3.48
0.20
0.18
0.538
0.271
5.91
2.947
70°С
10.2
12.65
12.78
9.30
6.50
5.44
3.60
3.77
1.60
1.883
1.90
1.81
0.80
0.81
0.96
0.754
0.5
–
0.3
9.88
0.633
0.47
0.377
0.217
0.220
0.186
0.783
0.86
0.644
8.064
7.543
8.57
70°С
11.52
11.20
9.408
8.52
17.08
13.79
10.33
8.77
6.00
5.82
4.77
4.06
2.55
2.63
1.86
1.89
1.235
1.113
1.02
0.475
0.420
0.628
0.68
0.21
0.32
0.21
0.18
0.105
0.90
0.92
0.76
0.95
70°С
12.24
12.68
10.848
9.017
14.325
13.87
11.85
9.446
7.25
6.91
6.16
5.17
3.21
3.09
2.84
2.34
1.29
1.20
1.16
0.91
0.49
0.34
0.31
0.26
–
–
0.33
0.26
0.19
0.8
0.112
0.143
75°С
13.02
12.72
11.28
9.34
14.92
14.95
12.146
9.76
7.55
6.40
5.12
4.78
2.205
2.62
2.48
1.94
1.05
1.43
1.49
1.18
0.75
0.70
0.64
0.51
0.5
0.665
0.963
0.926
0.61
0.6
0.62
0.31
80°С
15.9
17.94
18.86
13.46
12.11
8.225
7.157
6.082
5.323
2.41
3.60
2.57
2.75
1.42
2.16
1.66
1.47
1.05
1.53
0.92
0.80
1.10
1.42
0.83
0.69
1.695
1.367
0.90
17.24
12.96
11.78
0.742
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KINETIC RELATIONSHIPS OF LIQUID-PHASE OXIDATION
737
Scheme 3.
that Се3+ cations participate in generation of Ȯ2Н
radicals in accordance with the Scheme 3.
ω1 = r1 – r3 – r8,
ω2 = r1 – 2r3 – r6 – r7,
ω3 = r1 – r2 – r5,
ω4 = r3 – r6 + r7,
ω5 = r4 + r5,
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
To refine the kinetic relationships, we performed
experiments with the binary mixtures styrene +
phenyloxirane, styrene + benzaldehyde, styrene +
phenylacetaldehyde, and styrene + benzoic acid in
various ratios. At the degree of the styrene oxidation no
higher than 40–45%, the above products do not inhibit
the styrene oxidation, except benzoic acid, which is
incorporated into the ligand surrounding of the catalyst,
cerium-containing polyoxotungstate, decreasing its
activity. However, benzoic acid is formed under harder
conditions; therefore, its effect on the mechanism of the
liquid-phase oxidation of styrene was not considered.
ω6 = r2 – r4 – r7,
ω7 = r6,
ω8 = r8,
where ω1 and ω2 are the experimentally determined
rates of consumption of styrene and available oxygen
in hydrogen peroxide, and ω3–ω8 are the rates of accu-
mulation of phenyloxirane, benzald-ehyde, phenylacet-
aldehyde, phenylethane-1,2-diol, benzoic acid, and oxi-
dative oligomerization product, respectively (Table 3).
The closest agreement between the calculated and
experimental data (Table 3) is reached when using the
following kinetic equations constructed taking into
account the independent reactions in Scheme 2:
The rate constants were calculated using the modified
fourth-order Runge–Kutta method with the Matlab-6.5
program. The experimental rate constants were
determined graphically using the method of initial rates
and refined by minimization of the rms deviations of
the calculated data for Eqs. (9)–(16) from the observed
values.
r1 = k1[с1][с2]
r2 = k2[с3]
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
r3 = k3[с1][с2]2
r4 = k4[с6]
Table 4. Calculated values of the preexponential factor k0i
and activation energy Ei for the rate constants of oxidative
transformation of styrene (reactions I–VIII, Scheme 2)
r5 = k5[с3]
r6 = k6[с2][с4]
r7 = k7[с2][с6]
r8 = k8[с1][с2]
Rate constant
k1, L mol–1 h–1
k2, h–1
k3, L mol–1 h–1
k4, h–1
Ei, J mol–1
74200
44724
55788
40802
25939
42751
16488
26988
k0i
1.02 × 109
1.16 × 108
1.41 × 108
1.96 × 107
3.32 × 106
6.76 × 106
3.32
where k1–k8 are the rate constants of reactions I–VIII;
r1–r8, rates of product accumulation in accordance with
the corresponding stoichiometric equations; and c1–c6,
compound concentrations (M) (Table 2).
The rates of transformation/accumulation of styrene
and oxidation products formed in reactions I–VIII were
calculated using the following equations:
k5, h–1
k6, L mol–1 h–1
k7, L mol–1 h–1
k8, L mol–1 h–1
2.25
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ALIMARDANOV et al.
Table 5. Step scheme of styrene oxidation with hydrogen peroxide in the presence of CePO4∙PW12O41∙nH2O/carbon material
No.
· ZOn
+ ZOn
a ZOn and ZOn+1 are oxo- and peroxotungstates containing Сen+ cations.
The calculated rate constants of reactions I–VIII
(Table 4) agree with the experimental data. The rms
deviation of the calculated rate constants from the
experimental values was 9.2–11.4% for the main
reactions I–IV and 14.6–18.0% for the side reactions
V–VIII. The other models of styrene oxidation lead to
considerably larger discrepancies.
number of stoichiometric pathways (Р) corresponding
to the step scheme is determined by the equation Р =
S – J = 8, where S is the number of steps and J is
the number of intermediates forming a complex with
the catalyst. Thus, the suggested scheme completely
describes the diversity of reactions occurring in the
system [25].
The results obtained allow the liquid-phase
oxidation of styrene to be described by a set of steps
given in Table 5. The step involving the interaction of
styrene with the catalytic complex formed is chosen as
the limiting step. The other steps are assumed to be fast
or equilibrium. According to Horiuti’s rule [25], the
The developed kinetic model of liquid-phase
oxidation of styrene with hydrogen peroxide in
the presence of polyoxotungstate can be used for
mathematical modeling and optimization of the process,
and also in studying kinetic relationships of other
multiple-route oxidative processes.
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https://doi.org/10.1016/j.apcata.2004.09.001
CONCLUSIONS
7. Duarte, T.A.G., Estrada, A.C., Simões, M.M.Q.,
Santos, I.C.M.S., Cavaleiro, A.M.V., Neves, G.P.M.S.,
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Thekineticrelationshipsandmechanismoftheliquid-
phase oxidation of styrene with hydrogen peroxide in
the presence of polyoxotungstate modified with cerium
cations were studied. The styrene oxidation follows a
complex scheme with the predominant formation of a
mixture of phenyloxirane and benzaldehyde. The rate
equations of the accumulation of reaction products were
constructed, the kinetic parameters were calculated,
and the model including the main reaction routes was
suggested. According to the suggested model, the
primary product of styrene oxidation is phenyloxirane,
which then undergoes hydrolysis, isomerization, and
oxidation following a consecutive-parallel scheme. The
ratio of the epoxide and aldehydes can be varied by
varying the temperature and substrate : oxidant molar
ratio.
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FUNDING
https://doi.org/10.1021/ja004000a
The study was performed within the framework of the
government assignment for the Mammadaliyev Institute of
Petrochemical Processes, National Academy of Sciences of
Azerbaijan.
12. Timofeeva, M.N., Pai, Z.P., Tolstikov, A.G., and
Kustova, G.N., Russ. Chem. Bull., 2003, vol. 52, no. 2,
pp. 480–486.
https://doi.org/10.1023/A:1023495824378
The study was financially supported by the National
Academy of Sciences of Azerbaijan.
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CONFLICT OF INTEREST
The authors declare that they have no conflict of interest.
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