Automated Reaction Mechanism Generation Including Nitrogen as a Heteroatom

Automated Reaction Mechanism Generation Including Nitrogen as a Heteroatom
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包括氮作为杂原子的自动反应机制生成

DOI：
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发表时间：
2018
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通讯作者：
W. Green
W. Green
中科院分区：
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文献类型：
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作者：
A. G. Dana;B. Buesser;S. Merchant;W. Green

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开源的基于速率的反应机制生成器（RMG）软件及其热化学和动力学数据库进行了扩展，包括氮作为杂原子。具体的变化RMG和挖掘的热化学和反应动力学数据进行了讨论。这个新版本的RMG已通过生成一个详细的热解和氧化模型乙胺（EA，CH 3CH 2NH 2）在~1400 K和~2巴进行了测试，并比较它最近的激波管研究。最近的实验数据的反应网络的验证表明，生成的模型成功地再现了观察到的物种以及点火延迟测量。在热解过程中，EA最初通过C-C键断裂分解，并且CH 2NH 2产物随后通过α-断裂在该系统中产生第一个H自由基。随着H浓度的增加，主要的EA消耗反应变成H自由基在H2O位点的H提取，导致链式反应，因为其产物产生更多的H自由基。在氧化过程中，主要的N2产生途径是由NO和N2 O介导的。观察到的是相对敏感的C-C和C-N EA键断裂反应，以及EA的热力学值; EA的热力学数据计算在CBS-QB 3水平2，并在此报告。本工作证明了RMG的能力，以构建适当的含氮物种的动力学模型，并讨论了EA的热解和氧化机制。
The open source rate-based Reaction Mechanism Generator (RMG) software and its thermochemical and kinetics databases were extended to include nitrogen as a heteroatom. Specific changes to RMG and the mining of thermochemistry and reaction kinetics data are discussed. This new version of RMG has been tested by generating a detailed pyrolysis and oxidation model for ethylamine (EA, CH3CH2NH2) at ~1400 K and ~2 bar, and comparing it to recent shock tube studies. Validation of the reaction network with recent experimental data showed that the generated model successfully reproduced the observed species as well as ignition delay measurements. During pyrolysis, EA initially decomposes via a C–C bond scission, and the CH2NH2 product subsequently produces the first H radicals in this system via -scission. As the concentration of H increases, the major EA consuming reaction becomes H abstraction at the site by H radicals, leading to a chain reaction since its product generates more H radicals. During oxidation the dominant N2 producing route is mediated by NO and N2O. The observables were found to be relatively sensitive to the C–C and C–N EA bond scission reactions as well as to the thermodynamic values of EA; thermodynamic data for EA were computed at the CBS-QB3 level 2 and reported herein. This work demonstrates the ability of RMG to construct adequate kinetic models for nitrogenous species, and discusses the pyrolysis and oxidation mechanisms of EA.