Combined Ab lnitio, Kinetic Modeling, and Shock Tube Study of the Thermal Decomposition of Ethyl Formate
Publication in refereed journal

替代計量分析
.

其它資訊
摘要The potential energy surfaces (PESs) and reaction rate constants of the unimolecular decomposition of ethyl formate (EF) were investigated using high-precision theoretical methods at the CCSD(T)/CBS(T-Q)//M06-2X/6-311++G(d,p) level of theory. The calculated PESs of EF dissociation and molecular decomposition reactions indicate that the intramolecular H-shift to produce formic acid and ethylene is the dominant decomposition pathway. A detailed chemical kinetic mechanism for EF pyrolysis was constructed by incorporating the important reactions of EF and its radicals into an existing mechanism previously developed for small methyl esters. The updated mechanism was first used to reproduce CO, CO2, and H2O concentration time histories during EF pyrolysis in the shock tube reported by Ren et al. [Ren , W. , Mitchell Spearrin , R. , Davidson , D. F. , and Hanson , R. K. J. Phys. Chem. A 2014 , 118 , 1785 - 1798]. The rate of production and sensitivity analyses show that the competing dehydration and decarboxylation channels of the intermediate formic acid control the final product yields of EF pyrolysis. The EF mechanism was further validated against the shock tube data of OH, CO, CO2, and H2O time histories measured during EF oxidation (equivalence ratio Phi = 1.0) at 1331-1615 K and 1.52-1.74 atm. This revised EF mechanism captured all of the species' time histories over the entire temperature range. Such modeling capability was due to the more accurate rate constants of EF reactions determined by high-precision theoretical calculations and a high-fidelity C-0-C-2 basis mechanism.
著者Ning H, Wu J, Ma L, Ren W, Davidson DF, Hanson RK
期刊名稱Journal of Physical Chemistry A
出版年份2017
月份9
日期7
卷號121
期次35
出版社American Chemical Society
頁次6568 - 6579
國際標準期刊號1089-5639
電子國際標準期刊號1520-5215
語言美式英語
關鍵詞Chemical kinetics, shock tube, thermal decomposition, ethyl formate

上次更新時間 2021-08-05 於 00:21