Theoretical Investigations on the Mechanisms for the Reactions of Sevoflurane Radicals[(CF3)2C(·)OCH2F, (CF3)2CHOC(·)HF] with O2and the OH· Radicals Regeneration

doi:10.6023/A18080317

Acta Chim. Sinica ›› 2018, Vol. 76 ›› Issue (10): 793-801.DOI: 10.6023/A18080317 Previous Articles Next Articles

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两种七氟醚自由基[(CF₃)₂C(·)OCH₂F,(CF₃)₂CHOC(·)HF]与氧气反应及OH·再生机理的理论研究

武卫荣^a,b, 员晓敏^a, 侯华^a, 王宝山^a

a 武汉大学化学与分子科学学院武汉 430072;
b 济宁学院化学与化工系曲阜 273155

投稿日期:2018-08-04 发布日期:2018-09-28
通讯作者: 王宝山 E-mail:baoshan@whu.edu.cn
基金资助:
项目受国家重点研发计划（No.2017YFB0902500）和国家电网有限公司总部科技项目（环保型管道输电关键技术）资助.

Theoretical Investigations on the Mechanisms for the Reactions of Sevoflurane Radicals[(CF₃)₂C(·)OCH₂F, (CF₃)₂CHOC(·)HF] with O₂and the OH· Radicals Regeneration

Wu Weirong^a,b, Yuan Xiaomin^a, Hou Hua^a, Wang Baoshan^a

a College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China;
b Department of Chemistry and Chemical Engineering, Jining University, Qufu 273155, China

Received:2018-08-04 Published:2018-09-28
Contact: 10.6023/A18080317 E-mail:baoshan@whu.edu.cn
Supported by:
Project supported by the National Key Research and Development Program of China (No. 2017YFB0902500) and Science and Technology Project of State Grid Corporation of China:The key Technology of Environment-Friendly Gas-Insulated Transmission Line (GIL).

Sevoflurane is an excellent volatile anaesthetic which has been widely in clinical use. However, it was found that sevoflurane is a potent green-house gas with a significant global warming potential. Atmospheric degradation of sevoflurane is desired for its long-term application. The reaction of sevoflurane with hydroxyl radicals (OH·) produces two radical species, namely, (CF₃)₂C(·)OCH₂F and (CF₃)₂CHOC(·)HF, which have different reactivity. Under the low-NO atmospheric conditions, it was found that both radical fragments enable to initialize the regeneration of OH·radicals in the presence of molecular oxygen (O₂). Microscopic mechanisms for the reactions of the two radicals with O₂ have been investigated for the first time in this work. Geometries of various intermediates and transition states on the doublet potential energy surfaces were optimized at the M06-2X/6-311++G (d,p) level of theory. Moreover, the single-point calculations were carried out using the composite model CBS-Q to refine the reaction energetics to the chemical accuracy. It was revealed that the formation of peroxy intermediate (RO₂·) undergoes via the definitive barriers of 1.3 or 1.8 kcal·mol^-1, in contrast to the barrierless association between the alkyl radicals and O₂. Apparently, the association of the fluorinated alkyl radicals with O₂ takes place more slowly due to the substitute effect. Although the addition of O₂ to the fluorine-rich radical site is more preferable than that to the fluorine-poor site, the latter is more exothermic in view of the exothermicity of the intermediates RO₂·. The barriers for the subsequent H-migration of RO₂·to form the QOOH intermediates are 17.9 and 21.5 kcal·mol^-1, respectively. Both barriers lie well below the reactant asymptote, indicating the isomerization paths are energetically favorable. Decomposition of QOOH takes place via three competitive mechanisms, including the step-wise bond fission, the three-body concerted cleavage, and the four-center intramolecular S_N2 reaction, to produce OH·radicals predominantly. All the reaction pathways could be competitive for (CF₃)₂C(OC(·)HF)OOH because the energies of the corresponding barriers are close. In contrast, only the S_N2 displacement energetic route is dominant for (CF₃)₂C(·)OC(HF)(OOH). Neither step-wise nor three-body pathways is important because the barrier height is roughly 7 kcal·mol^-1 higher than that for the S_N2 pathway. The isomerization of QOOH to alkoxy intermediate is of little importance due to the significant barrier even though it is highly exothermic. Implication of the current theoretical findings in the OH·radicals recycling reaction in atmosphere has been illustrated.

Key words: sevoflurane, reaction mechanism, OH·, radicals regeneration, atmospheric degradation, quantum chemistry

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Wu Weirong, Yuan Xiaomin, Hou Hua, Wang Baoshan. Theoretical Investigations on the Mechanisms for the Reactions of Sevoflurane Radicals[(CF₃)₂C(·)OCH₂F, (CF₃)₂CHOC(·)HF] with O₂and the OH· Radicals Regeneration[J]. Acta Chim. Sinica, 2018, 76(10): 793-801.

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两种七氟醚自由基[(CF₃)₂C(·)OCH₂F,(CF₃)₂CHOC(·)HF]与氧气反应及OH·再生机理的理论研究

Theoretical Investigations on the Mechanisms for the Reactions of Sevoflurane Radicals[(CF₃)₂C(·)OCH₂F, (CF₃)₂CHOC(·)HF] with O₂and the OH· Radicals Regeneration

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两种七氟醚自由基[(CF3)2C(·)OCH2F,(CF3)2CHOC(·)HF]与氧气反应及OH·再生机理的理论研究