An ab initio kinetics study on 2-methyl-2-butanol oxidation induced by ˙OH radicals

Abstract

High-level ab initio calculations were performed to investigate the kinetics of the important initial steps of 2-methyl-2-butanol (2M2B) oxidation. Hydrogen-atom abstraction reactions by hydroxyl (ȮH) radical, water elimination reactions of...

Theoretical investigation on isomerization and decomposition reactions of pentanol radicals-part I: branched pentanol isomers

“…13 and 14 shows the comparison of the calculated rate constants in this paper and the data in the literature for the same reaction pathways. It is clear that the rate constants of 2-methyl-2-butanol radicals in this work are in good agreement with those reported by Guo et al 23 while the rate constants from this work are slightly faster than those reported by Guo et al in the low-temperature range. The calculation method used in this paper is similar to that employed by Guo et al 23 The reason for such a small discrepancy may be due to the different parameter settings in MESS input files, such as WellCutoff, GlobalCutoff, etc.…”

“…It is clear that the rate constants of 2-methyl-2-butanol radicals in this work are in good agreement with those reported by Guo et al 23 while the rate constants from this work are slightly faster than those reported by Guo et al in the low-temperature range. The calculation method used in this paper is similar to that employed by Guo et al 23 The reason for such a small discrepancy may be due to the different parameter settings in MESS input files, such as WellCutoff, GlobalCutoff, etc. Rate constant comparison between this work and the work conducted by Tang et al , 13 as shown in Fig.…”

“…Literature data for different species are mainly from the Active Thermochemical Tables (ATcT), 53 the Third Millennium Ideal Gas and Condensed Phase Thermochemical Database for Combustion (abbreviated as Burcat database in this paper), 54 and several other literature ref. 23, 44, 55–69 Heat capacities at different temperatures are shown in Table 5. It can be seen that most of the calculated formation enthalpies are in excellent agreement with the literature data (within 0.7 kcal mol −1 ), except for some species including trans -CH 3 CHCHOH, trans -CH 3 CHC(CH 3 )OH and (CH 3 ) 2 CCHOH at 298 K. The differences between this study and the findings of Turecek et al 62 for (CH 3 ) 2 CCHOH and trans -CH 3 CHC(CH 3 )OH are up to 5.5 kcal mol −1 and 4.4 kcal mol −1 , respectively.…”

“…The result reveals that entropies of the variational transition states significantly influenced the competition between various decomposition channels. Guo et al 23 employed the QCISD(T)/CBS//M06-2X/6-311++G(d,p) level of theory to calculate the potential energy surfaces of all the reaction pathways for 2-methyl-2-butanol, including the H-atom abstraction by hydroxyl radicals, subsequent isomerization and decomposition reactions, and dehydration reactions of 2-methyl-2-butanol molecules. The rate constants of the H-atom abstraction reaction were obtained through variational transition state theory, and the effect of hydrogen bonds on kinetics was also investigated.…”

High-Temperature Dissociation of Neopentanol: Shock Tube/Photoionization Mass Spectrometry Studies

“…The pyrolysis and oxidation of many alcohols including the isomers of butanol and some pentanol isomers have been studied due to their potential as “next generation” biofuels. − The high-temperature dissociation kinetics and mechanism of the most highly branched pentanol isomer, 2,2-dimethyl­propan-1-ol (neopentanol), do not appear to have been studied. However, the recombination reaction of tert -butyl and hydroxymethyl radicals yielding neopentanol was studied theoretically by Zhao et al and the rate coefficient was estimated by Tsang .…”