標題: Anharmonic Effect of N-Propyl Peroxy Dissociation
作者: Song, Liguo
Pan, Xinxiang
Li, Qian
Ding, Yang
Yao, Li
Lin, Sheng-Hsien
應用化學系
Department of Applied Chemistry
關鍵字: Rate constant;RRKM theory;Anharmonic effect
公開日期: 十二月-2016
摘要: The anharmonic and harmonic dissociation rate constants of alkylperoxy (RO2) in different pathways, as well as those for the reactions of the n-propyl peroxy radical, were calculated using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. When the temperature/total energy increased, the rate constants of the different pathways varied independently, causing changes in the dominating/leading products. Anharmonic rate constants were larger than harmonic rate constants, and their difference increased with increasing temperature/energy. Therefore, the anharmonic effect cannot be neglected. The rate-determining steps of CH3CH2CH2OO dissociation are discussed. Then the anharmonic effect was found clearly for CH3CH2CH2OO dissociation, especially for the hydroperoxyalkyl radical (QOOH) dissociation. At low temperature, the rate constants were similar to those found from experiment, which indicated the RRKM theory was suitable for calculating the dissociation rates of RO2 species.
URI: http://dx.doi.org/10.1002/jccs.201600091
http://hdl.handle.net/11536/133271
ISSN: 0009-4536
DOI: 10.1002/jccs.201600091
期刊: JOURNAL OF THE CHINESE CHEMICAL SOCIETY
Volume: 63
Issue: 12
起始頁: 1038
結束頁: 1050
顯示於類別:期刊論文