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Updated: Aug 26, 2025

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Published on: August 17, 2019
Effects of Oxygen: Experimental and VTST/DFT Studies on Cumene Autoxidation with Air under Atmospheric Pressure
Yufeng Wu1, Jingnan Zhao1, Qingwei Meng1
1School of Chemical Engineering, Dalian University of Technology, Dalian, Liaoning 116024, China.
Abstract:
The mechanism of how oxygen affects cumene autoxidation related to temperature is still bewildering. Kinetic 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 {k 6,reverse[ROO•]}/{k 7,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.
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