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Effects of Oxygen: Experimental and VTST/DFT Studies on Cumene

Autoxidation with Air under Atmospheric Pressure
Yufeng Wu,* Jingnan Zhao, Qingwei Meng,* Mingshu Bi, Cunfei Ma, and Zongyi Yu
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ABSTRACT: The mechanism of how oxygen affects cumene

autoxidation related to temperature is still bewildering. Kinetic
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analysis of cumene autoxidation with air at a pressure of 1.0 atm was

investigated by experiments and variational transition state theory/
DFT. Oxygen was the limiting factor for cumene autoxidation above
100 °C, although it had negligible impacts on cumene autoxidation
at 70−100 °C. The kinetic analysis by VTST coupled with DFT
calculations proved that {k6,reverse[ROO•]}/{k7,forward[RH]0 [ROO•]}
> 103 (70−120 °C), suggesting that ROO• tended to decompose
back to R• and O2 rapidly, whereas it was much slower for ROO•
abstracting a hydrogen atom from RH to form ROOH. When the
concentration of oxygen was higher than the critical value
([O2]critical), it could not significantly affect the equilibrium
concentration of ROO•, which in turn could not affect the autoxidation rate significantly. Besides, the critical oxygen concentration
([O2]critical) was exponentially related to 1/T, which was consistent with Hattori’s experimental results.

1. INTRODUCTION Scheme 1. Kinetic Scheme of Cumene Autoxidation

Oxidations with molecular oxygen are awfully fascinating that
often address the priorities of green and sustainable
chemistry.1,2 At present, molecular oxygen has been success-
fully used in oxidations of alkenes, alcohols, thioethers, and
amines.1,3 One prominent industrial example is cumene
autoxidation to prepare cumene hydroperoxide (ROOH),
which was then converted into phenol with a production of
more than 11.4 × 106 t/a in 2013.4 The peroxidation processes
had also swept the industry5 because coproduct processes
(PO/SM and PO/TBA) and the Sumitomo process6 had been
widely used in the industrial production of propylene oxide,
which was the synthetic material for polyurethane foams and
polyester resins.7
Cumene autoxidation is a typical heterogeneous gas−liquid
reaction and attracts considerable attention.8−12 The mecha-
nisms and kinetic study of cumene autoxidation have received
extensive attention.2,8,13−15 An intricate series of elementary
reactions, in Scheme 1, were involved in cumene autoxidation.
Generally, it was deemed that reaction 7, which was not related
to oxygen, was slower and thus the decisive step to the chain
reaction.4 Nevertheless, oxygen was undoubtedly one of the
major factors and has attracted a lot of attention.16,17 Hattori et
al.16 found that the oxidation rate constant was not affected by Received: July 10, 2022
oxygen when the partial pressure of oxygen in the gas phase Accepted: September 6, 2022
was higher than a certain value. Ulitin et al.17 found that the Published: September 19, 2022
oxygen mass transfer rate did not affect the accumulation rate
of ROOH under reaction conditions of 1.013 × 105 Pa and
110 °C. Instead, when the concentration of oxygen dissolved in
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cumene was higher than a value that was linear with the reaction system through a pump and a gas flowmeter (set as
concentration of the initiator (ROOH), there was a weak 2.0 mL/min) and was successively dried with condensation at
dependence of ROOH’s accumulation rate on oxygen. Thus, −30 °C and soda lime.
the boundary concentration of oxygen related to temperature, 2.3. Kinetic Model of Cumene Autoxidation. Based on
to distinguish whether the oxygen affects cumene autoxidation, the mechanisms of alkanes’ autoxidation,17 a kinetic scheme of
is of great valuable, but no relevant reports have been found. cumene autoxidation proceeds by a chain mechanism including
Here, kinetic analysis of cumene autoxidation with air as chain initiation, chain propagation, and chain termination
oxidant was carried out through experiments and variational (Scheme 1). According to Figure S4, high selectivities (>90%)
transition state theory (VTST) coupled with density functional were obtained at conversions less than 8%. Thus, side reactions
theory (DFT) calculations. Both the forward and reverse were ignored here. The generation rate of ROOH was mainly
reactions were analyzed by VTST coupled with DFT determined by reaction 7 and thus eq 1 was used to describe
calculations, providing good insights into how oxygen affects the generation rate of ROOH.
cumene autoxidation. Besides, the critical oxygen concen-
tration [O2]critical related to temperature was present in this rROOH = rRH = k 7[ROO•][RH] (1)
work, providing theoretical and technical supports for cumene where [ROO•] and [RH] are the concentration of ROO• and
autoxidation. cumene, mol/L, respectively and k7 is the reaction constant for
2. EXPERIMENTAL AND CALCULATIONS reaction 7.
2.4. Computational Details. All geometry optimizations
2.1. Materials. Unless otherwise stated, all commercial of the reactants, transition states, intermediates, and products
reagents and solvents were used without further purification. were carried out with the Gaussian 16 program. The
Cumene (>99% purity, 0.47 mol % of ROOH was determined B3LYP19,20 hybrid exchange−correlation functional with 6-
by 1H NMR) was produced by Institute of Guangfu Fine 311 + g(d,p) basis set was applied for geometrical
Chemicals. K2CO3 was produced by Xilong Chemical Co., Ltd. optimizations and subsequent frequency calculations. The
1
H NMR (400 MHz) spectra were recorded on a Bruker optimizations were carried out at 378.15 K using cumene as
Avance II 400 spectrometer. the solvent. No imaginary frequencies were found in the
2.2. Cumene Autoxidation. Figure 1 illustrates the setup vibrational spectra of all reactants, intermediates, and products.
utilized in the experimental work. The reactor was a 50 mL Only one imaginary frequency corresponding to the reaction
coordinates was found for the transition states. The intrinsic
reaction coordinate calculations were carried out to further
verify the relationship between the reactants, transition states,
and products. The rate constant for the barrierless R• + O2
reaction were treated as Silva’s literature,21 using VTST
coupled with DFT calculations. The two-parameters Arrhenius
formula to calculate the rate constants related to temperature
for elementary reactions were obtained from KISTHELP
software.22

3. RESULTS AND DISCUSSION

3.1. Saturated Solubility of Oxygen. According to
Hattori’s report,16 the concentration of oxygen dissolved in
cumene did not affect the reaction rate of cumene autoxidation
at a temperature below 120 °C when the concentration of
dissolved oxygen was greater than 7 × 10−4 mol/L. This
Figure 1. Cumene autoxidation experimental scheme. concentration corresponds to an equilibrium partial pressure of
0.1 bar in the gas phase.4 To verify whether oxygen affected
cumene autoxidation, the oxygen solubility in cumene was
reaction tube (outer diameter of 23 mm). K2CO3 (0.5 mmol,
calculated based on the gas−liquid equilibrium theory and
69.1 mg), cumene (3 mL), and a magnetic stirring bar (1 cm)
Hayduk’s semiempirical method23−25 at first. The detailed
were successively added to the reaction tube, which was then
calculation process is present in the Supporting Information.
put onto a metal plate above a magnetic stirring apparatus
When the reaction was performed with air as the oxidant under
(IKA Plate, RCT digital). Then, the reflux unit and dry air
a pressure of 1.013 × 105 Pa, the oxygen partial pressure,
preparation unit were connected as shown in Figure 1. K2CO3
poxygen, was calculated and the results are listed in Table S1,
was used to neutralize the organic acid generated in situ,
suggesting that the oxygen partial pressure decreased with the
preventing the decomposition of ROOH promoted by organic
increasing temperature. The mole fraction of oxygen (XT) in
acid.18 The effects of K2CO3 on cumene autoxidation are
cumene under an oxygen partial pressure of 1.0 bar at different
further discussed in the Supporting Information. To ensure
temperatures was about 10.9 × 10−4 and had a negligible
that the ratio of O2 and N2 over the surface of reaction liquor is
temperature coefficient (Table S1). This result was consistent
stable, drying air (2 mL/min) was fed into the gas phase
with Low’s literature.26 When air was used as the oxidant, the
continuously. The reaction proceeded at a specific temperature
(70, 80, 90, 100, 110, and 120 °C). The samples were sampled molar concentration of oxygen ([O2]ST ) at 70−120 °C was
on time and diluted immediately with DMSO-d6. Conversion calculated and is depicted in Figure 2. There was a clear
and selectivity were determined by 1H NMR. Dry air was downward trend (decreased from 12.84 × 10−4 to 7.40 × 10−4
prepared by the following steps: the air flowed into the mol/L) for [O2]ST when the temperature increased from 70 to
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Figure 2. Molar concentration of oxygen ([O2]ST ) dissolved in cumene

in an air atmosphere.

120 °C. Therefore, the influence of oxygen on cumene

autoxidation under experimental conditions could be neglected
because [O2]ST was greater than 7 × 10−4 mol/L at 70−120 °C.
3.2. Kinetic Study of Cumene Autoxidation without
Considering the Oxygen Solubility. Based on the above
analysis, the influence of oxygen on cumene autoxidation
under experimental conditions could be neglected. Therefore,
reaction 7 was the rate-controlling step for cumene
autoxidation. According to the assumption of pseudo-steady-
state,13 k7[ROO•][RH] = k6[R•][O2] could be obtained when
ignoring the side reactions. g(T) was assumed as the total
concentration of radicals and [ROO•] + [R•] ≈ g(T). Then, eq
2 was derived to calculate the concentration of ROO•. The
values of [ROO•]/g(T) at different temperatures were first
calculated using parameters from Somma’s report15 (log k70 =
7.6, log k60 = 8.4, ΔEa6 = 0, and ΔEa7 = 53.16 kJ/mol) and the
results are listed in Table S2. The value of [ROO•]/g(T)
decreased from 0.9997 to 0.9946 when the temperature
increased from 70 to 120 °C, suggesting that the concentration
of ROO• was close to the total concentration of radicals
independent of temperature. Thus, the effect of temperature
on the reaction rate will be much more pronounced than
[ROO•] at 70−120 °C.
Figure 3. Linear regression analysis of ln K1 with 1/T, with error bars
g (T )
[ROO•] = of 2%. (a) temperature range of 70−120 °C; (b) temperature range of
k70 [RH] Ea6 Ea7
1+ k60 [O2]
exp ( RT ) (2)
70−100 and 100−120 °C, respectively; and (c) pure oxygen and air
were used as the oxidant at 120 and 70−100 °C, respectively.
To simplify the kinetic study of cumene autoxidation, a
hypothesis that the concentration of ROO• was not sensitive Koshel’s report8 and they deemed that the activity of PINO•
to temperature at 70−120 °C and K1 (= k7[ROO•]) was may be different in the two temperature ranges. From this
introduced. Eq 1 was rewritten as eq 3 to study the reaction perspective, the activation energy of reaction 7 were 62.54 and
kinetics between ROO• and RH, indicating that ln(1−x) and t 13.38 kJ/mol in the temperature ranges of 70−100 and 100−
have a linear relationship. x is the conversion of cumene. The 120 °C, respectively. However, in our opinion, the change of
regression lines and equations of ln(1−x) with t at 70−120 °C oxygen concentration in the reaction liquor may lead to this
are shown in Figure S3 and listed in Table S3. The values of K1 situation as well. Figure S4c,d also indicated that the cumene
at different temperatures were equal to the corresponding autoxidation rate at 120 °C significantly increased using high
slopes of the regression lines as shown in Figure S3. lnK1 and purity oxygen instead of air, indicating oxygen was the limiting
1/T should have a linear relationship according to Arrhenius factor at 120 °C. Notably, R2 = 0.99372 as shown in Figure 3c
eq 4. Unexpectedly, as shown in Figure 3a, R2 = 0.89927 was was obtained for the linear regression analysis of lnK1 with 1/T
obtained for the linear regression of lnK1 and 1/T in the when the value of K1 at 120 °C using high purity oxygen as the
temperature range of 70−120 °C, suggesting a poor reliability. oxidant was used. Therefore, the concentration of oxygen was
Figure 3b also showed that lnK1 and 1/T were linear with a the limiting factor for cumene autoxidation above 100 °C,
good degree of reliability in the temperature ranges of 70−100 although it had negligible effects on cumene autoxidation at
and 100−120 °C with R2 = 0.98218 and R2 = 0.92307, 70−100 °C. Based on Figure 3c, the activation energy of
respectively. The slope value in the temperature range of 70− reaction 7 was 61.92 kJ/mol.
100 °C was obviously greater than that in the temperature
range of 100−120 °C. Same situation was discovered in ln(1 x) = K1t (3)

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Figure 4. Energy and Gibbs free energy profile (at 378.15 K) for cumene autoxidation, calculated at B3LYP/6-311 + G(d,p) level of theory.

Ea7 Table 1. Kinetic Parameters for the Reactions 6 and 7 at

ln K1 = ln K10 343.15−398.15 K
RT (4)
elementary reactions A E (kJ/mol)
3.3. Kinetic Study by VTST/DFT Calculations. Kozuch
and Martin27 have reported that there are no rate-determining k6,forward
9.62 × 106 −8.91
R• + O2 ROO•
steps, only rate-determining states. Inspired by Kozuch’s
report, we believe that there may be new breakthroughs in k6,reverse
ROO• R• + O2 3.87 × 1014 69.44
the in-depth study of kinetics from the perspective of transition
state theory and reversible reactions. Here, the energy and k 7,forward 7.50 × 108 61.58
ROO• + RH ROOH + R•
Gibbs free energy profile (at 378.15 K) for cumene
k 7,reverse 1.38 × 109 47.53
autoxidation, calculated at B3LYP/6-311 + G(d,p) level of ROOH + R• ROO• + RH
theory, is depicted in Figure 4. Potential energy surface scan
results (Figure S5) showed that the reaction of O2 with R• to
form ROO• is barrierless. It was consistent with the previous
reports28−30 that the reaction of alkyl radicals with oxygen was reaction of reaction 7. Thus, the reverse reaction of reaction 6
barrierless. Rate constants for R• + O2 at each point along the should not be ignored in the kinetic study of cumene
potential energy surface were calculated and are depicted in autoxidation. Denisov and Afanas’ev31 have also reported
Figure S6. The location of the variational transition state that some peroxyl radicals, such as cyclohexadienyl peroxyl
(vTS1) is at a R−OO bond length of 2.43 Å. As a result, radicals, have a weak C−OO bond and decompose back to R•
activation free energy barriers of 88.75 and 95.00 kJ/mol were and O2. It was consistent with our results. Nevertheless, the
required for the reaction of O2 with R• to form ROO• and its addition reaction of O2 to R• was regarded as a one-way
reversible reaction, respectively. Only one imaginary frequency reaction process in the previous kinetic studies of cumene
(91.82i) was found for vTS1. The process that ROO• autoxidation.8,13,16
abstracted a hydrogen atom from RH required to overcome The reaction rates for those elementary reactions consuming
an activation free energy barrier of 120.58 kJ/mol and only one ROO•, such as reactions 12, 15, and 16, were of course much
imaginary frequency (1766.35i) was found for TS1. The Gibbs slower than reaction 7. Therefore, eq 5 was used to describe
free energy change for the entire reaction was −14.35 kJ/mol, that the generation rate of ROO• was equal to its consumption
suggesting a feasible process. rate in view of the quasi-steady-state assumption. Because
Two-parameters Arrhenius formulas were used to calculate k6,reverse/(k7,forward[RH]0) > 103 and k6,forward[O2]/k7,reverse > 106,
the minimum rate constants related to temperature for the eq 6 was used to calculate the ratio of R• and ROO•. It was
main elementary reactions and its reversible reactions, using clear that the ratio of R• and ROO• was mainly determined by
VTST coupled with the B3LYP/6-311 + G(d,p) level of theory temperature and the oxygen concentration. Both increasing the
in the temperature range of 343.15−398.15 K. The concentration of O2 and decreasing temperature could lead to
corresponding parameters are listed in Table 1. The fitted a decrease of the ratio of R• and ROO•. When the
activation energy (61.58 kJ/mol) for reaction 7 was close to concentration of oxygen was higher than the critical value
our experimental value (61.92 kJ/mol). Interestingly, it was ([O2]critical), it could not significantly affect the equilibrium
also found that {k6,reverse[ROO•]}/{(k7,forward[RH]0) [ROO•]} concentration of ROO•, which in turn could not affect the
> 103 (70−120 °C), suggesting that the rate for the reverse autoxidation rate significantly. Eq 7 was derived to calculate K1
reaction of reaction 6 was much faster than that for the forward (= k7,forward[ROO•]). Interestingly, as shown in Figure 5, the
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to M/N. We assumed that there was a weak dependence of

cumene autoxidation on oxygen when K was 0.85 times Kmax
(i.e., m = 0.1765). Thus, the critical oxygen partial pressures
related to temperature were calculated (PO2,critical: 110 °C,
d

0.157 atm; 120 °C, 0.241 atm; and 130 °C, 0.327 atm).
Interestingly, lnPO2,critical and 1/T were linear with a good
d

degree of reliability (R2 = 0.9968) in the temperature range of

110−130 °C (Figure 6). Therefore, PO2,critical = 4.25 ×
d

Figure 5. Plot of lnK1 over 1/T, set error bars of 2% for the
experimental results.

curve of lnK1 over 1/T for the fitting results (when g(T) = 1.21
× 10−4 mol/L) was consistent with our experimental results.
k6 ,forward[R•][O2] + k 7 ,reverse[R•][ROOH]
= k 7 ,forward[ROO•][RH] + k6 ,reverse[ROO•] (5)
Figure 6. Linear regression analysis of lnPO2,critical and 1/T in the
d

•
[R ] k6 ,reverse 4.0 × 107 exp( 9423.4/T ) temperature range of 110−130 °C, set error bars of 3%.
=
[ROO•] k6 ,forward[O2] [O2]
(6) 105exp(−5668.73/T) or
k 7 ,forwardg (T ) [O2]critical 2.96 × 104 exp( 5668.73/T ). This result was
K1 = k 7 ,forward[ROO•] = consistent with our derivation that the critical oxygen partial
1 + [R•]/[ROO•] (7)
pressure was exponentially related to 1/T though some
3.4. Mathematical Model to Calculate the Critical differences existed between the experimental results and
Concentration of Oxygen. Both Hattori16 and Ulitin17 theoretical derivations. We deemed that the difference was
found that there was a weak dependence of ROOH’s mainly caused by the conditions of the experiments using a
accumulation rate on oxygen when the oxygen concentration bubble column reactor, where the oxygen partial pressure
or the partial pressure of oxygen was higher than some value. gradually decreases from bottom to top of the reaction system.
To our knowledge, there were no reports to solve the general Besides, the saturated vapor pressure of cumene was not
critical oxygen concentration related to temperature. Accord- considered in Hattori’s report, which may result in this
ing to eqs 6 and 7, the value of {k7,forward[ROO•]}, as well as difference as well.
the ROOH’s accumulation rate, will increase with increase of
[O2]. The closer the ratio of R• and ROO• is to 0, the closer 4. CONCLUSIONS
the reaction rate is to the maximum reaction rate. When the In conclusion, kinetic analysis of cumene autoxidation with dry
concentration of oxygen was higher than the critical value air as the oxidant under conditions of 70−120 °C and 1.0 atm
([O2]critical), it could not significantly affect the concentration was studied by experiments and VTST/DFT calculations.
of ROO• by increasing oxygen concentration, which in turn Oxygen was the limiting factor for the rate constant of cumene
could not affect the autoxidation rate significantly. We assumed autoxidation above 100 °C, although it had negligible impact
that when [R•]/[ROO•] ≤ m, there is a weak dependence of on cumene autoxidation at 70−100 °C. The reaction rate at
ROOH’s accumulation rate on oxygen. This is to say “m” can 120 °C was significantly increased by using high purity oxygen
be regarded as a threshold ({[R•]/[ROO•]}threshold = m) to instead of air. Reaction 6 was reversible in the view of VTST
judge whether the concentration of oxygen could affect the coupled with DFT calculations, thus determining the
autoxidation rate. Eq 8, to solve the critical oxygen equilibrium concentration of ROO•. It provides good insights
concentration ([O2]critical), could be derived from eq 6. m is into how oxygen affects cumene autoxidation. Finally, the
recommended to be in the range of 0.1−0.20. Similarly, the critical oxygen concentration ([O2]critical ) grew exponentially
critical oxygen partial pressure was also exponentially related to with 1/T. It was consistent with Hattori’s experimental results.
1/T, when the saturated vapor pressure of cumene was
ignored.
4.0 × 10 7
■
*
ASSOCIATED CONTENT
sı Supporting Information
[O2]critical = exp( 9423.4 /T ) The Supporting Information is available free of charge at
m (8)
https://pubs.acs.org/doi/10.1021/acsomega.2c04362.
16
Hattori reported that the rate constant K and the partial Saturated solubility of oxygen calculated by Hayduk’s
pressure of oxygen obey the function of K = MPO2/(1 + NPO2).
d d

semiempirical method and gas−liquid equilibrium

Thus, the maximum value of K (Kmax) would be infinitely close theory; effects of K2CO3 on cumene autoxidation;
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■ ACKNOWLEDGMENTS
This work was supported by the National Regional Innovation
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Technology Bureau (2019J1CY006), and Dalian University (22) Canneaux, S.; Bohr, F.; Henon, E. KiSThelP: A Program to
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