自动氧化
异丙苯
过氧化氢异丙苯
氧气
化学
光化学
大气压力
催化作用
有机化学
海洋学
地质学
作者
Yufeng Wu,Jianzhang Zhao,Qingwei Meng,Mingshu Bi,Cunfei Ma,Zongyi Yu
出处
期刊:ACS omega
[American Chemical Society]
日期:2022-09-19
卷期号:7 (38): 34547-34553
被引量:1
标识
DOI:10.1021/acsomega.2c04362
摘要
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 {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.
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