Duan Yanhao, He Jiuning, Chen Lei, Li Jianhua, Li Jia, Wang Xingzhi, Shi Shunping, Zhang Changhua, Li Ping, Chen Deliang
College of Mathematics and Physics, Chengdu University of Technology, Chengdu, Sichuan 610059, China.
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, China.
J Phys Chem A. 2024 Oct 17;128(41):8996-9014. doi: 10.1021/acs.jpca.4c03493. Epub 2024 Oct 3.
-Pentanol is acknowledged as a prospective alternative and a supplement to traditional fossil fuels. H-abstraction reaction assumes a pivotal role in initiating the chain reaction during -pentanol combustion. To investigate the oxidation characteristics of -pentanol, the composite quantum chemical methods CBS-QB3 and G4 are employed to obtain thermochemical and kinetic parameters in the H-abstraction reaction of -pentanol. The calculated isobaric heat capacity provides accurate predictions of the experimental results. Branching ratios underscore that H-abstraction at the C site serves as the primary channel between -pentanol and Ḣ/ĊH/ȮH. For the reaction between -pentanol and ȮH, the C site emerges as the most favorable channel due to the significant variational effect. The overall rate coefficient for H-abstraction from -pentanol by ȮH radicals is expressed as = 3565.11 × exp (1465.44/) (cm mol s), and the data obtained at the CBS-QB3 level demonstrate good agreement with experimental observations. Furthermore, the original model is modified based on current results, and the improved model demonstrates superior predictive capabilities for jet-stirred reactor (JSR) data and ignition delay times. Reaction path and sensitivity analyses are employed to identify fuel consumption pathways and critical reactions in the combustion of -pentanol.
正戊醇被认为是传统化石燃料的一种潜在替代品和补充物。氢提取反应在正戊醇燃烧过程中引发链式反应起着关键作用。为了研究正戊醇的氧化特性，采用复合量子化学方法CBS - QB3和G4来获取正戊醇氢提取反应中的热化学和动力学参数。计算得到的等压热容对实验结果提供了准确的预测。分支比强调在C位点的氢提取是正戊醇与Ḣ/ĊH/ȮH之间的主要通道。对于正戊醇与ȮH的反应，由于显著的变分效应，C位点成为最有利的通道。ȮH自由基从正戊醇中提取氢的总速率系数表示为 = 3565.11 × exp (1465.44/) (cm³mol⁻¹s⁻¹)，在CBS - QB3水平获得的数据与实验观测结果显示出良好的一致性。此外，基于当前结果对原始模型进行了修正，改进后的模型对喷射搅拌反应器（JSR）数据和点火延迟时间具有卓越的预测能力。采用反应路径和敏感性分析来确定正戊醇燃烧中的燃料消耗途径和关键反应。
