Laboratoire Réactions et Génie des Procédés, CNRS, Nancy Université, ENSIC, 1, rue Grandville BP 20451 54001 Nancy Cedex, France.
J Phys Chem A. 2012 Jun 21;116(24):6142-58. doi: 10.1021/jp211434f. Epub 2012 Feb 8.
This paper revisits the primary reactions involved in the oxidation of n-butane from low to intermediate temperatures (550-800 K) including the negative temperature coefficient (NTC) zone. A model that was automatically generated is used as a starting point and a large number of thermochemical and kinetic data are then re-estimated. The kinetic data of the isomerization of alkylperoxy radicals giving (•)QOOH radicals and the subsequent decomposition to give cyclic ethers has been calculated at the CBS-QB3 level of theory. The newly obtained model allows a satisfactory prediction of experimental data recently obtained in a jet-stirred reactor and in rapid compression machines. A considerable improvement of the prediction of the selectivity of cyclic ethers is especially obtained compared to previous models. Linear and global sensitivity analyses have been performed to better understand which reactions are of influence in the NTC zone.
本文重新研究了正丁烷在低温至中温（550-800 K）下氧化过程中的主要反应，包括负温度系数（NTC）区。使用自动生成的模型作为起点，并重新估算了大量的热化学和动力学数据。烷基过氧自由基异构化生成（•）QOOH 自由基以及随后分解生成环状醚的动力学数据是在 CBS-QB3 理论水平上计算的。新获得的模型可以对最近在射流搅拌反应器和快速压缩机器中获得的实验数据进行令人满意的预测。与以前的模型相比，特别获得了对环状醚选择性的更好预测。进行了线性和全局敏感性分析，以更好地了解哪些反应在 NTC 区有影响。
