Oxidation of pentan-2-ol – Part I: Theoretical investigation on the decomposition and isomerization reactions of pentan-2-ol radicals

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

“…The asymmetric Eckart model 34 was applied to quantify the tunnelling effects. In the master equation modeling, the collisional frequency was modeled by using the Lennard–Jones (L-J) potential, 35 with the parameters σ = 3.6 Å, ε = 68 cm −1 for N 2 and σ = 6.27 Å, ε = 341.3 cm −1 employed for another C 5 H 11 O system 21 adopted here for the 2M2B and 2M2B radicals by analogy. The exponential-down model 36 was employed to describe collisional energy relaxation, with the average downward energy transferred per collision estimated as 〈Δ E down 〉 = 200 × ( T /300) 0.75 cm −1 .…”

“…The exponential-down model 36 was employed to describe collisional energy relaxation, with the average downward energy transferred per collision estimated as 〈Δ E down 〉 = 200 × ( T /300) 0.75 cm −1 . 21 The calculated phenomenological rate coefficients for title reactions were fitted by modified Arrhenius expression and are provided in the ESI †…”

“…Xing et al 20 implemented multi-path variational transition state theory (MP-VTST) to calculate the rate coefficients of H-atom abstraction of 3-methyl-1-butanol by OH radicals. Bai et al 21 investigated the kinetics of the decomposition and isomerization reactions of 2-pentanol-2-yl radicals at the ROCCSD(T)/CBS// B2PLYPD3/6-311++G(d,p) level of theory, and calculated the thermochemical properties of the important species involved in the reaction process. Bai et al 22 studied the energetics of the H-atom abstraction reactions of 1-pentanol, 2-pentanol, and 3-pentanol by hydroxyl radicals at the CCSD(T)/CBS//M06-2X/ 6-311+G(d,p) level and calculated the rate coefficients by using the multi-structural variational transition state theory (MS-VTST) together with small curvature tunnelling (SCT) correction.…”

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

“…43 For N 2 , σ = 3.6 Å and ε = 68 cm −1 were used, while the parameters for Ċ 5 H 11 O radicals were σ = 6.269 Å and ε = 341.3 cm 1 . 44 A single-parameter exponential down model with 〈Δ E 〉 down = 200 × ( T /300) 0.75 cm −1 45 was used to represent the collisional energy transfer function. The calculated rate constants were fitted using the modified Arrhenius expression k = AT n exp(− E a / RT ).…”

Oxidation of C5 esters: Influence of the position of the ester function

“…With the growing interest on higher alcohols, [8][9][10][11][12][13] esters with higher energy content can be produced and burned in engines for ground transportation, especially diesel engines. 14,15 Therefore, this paper focuses on the influence of the position of the ester function along the carbon chain, as depicted in Table 1, and highlights the importance of the nature of the products formed by the different molecular reactions in terms of global reactivity or product TA B L E 1 Chemical structure of C 5 esters, heat of formation (kcal mol -1 ), and entropy (cal mol -1 K - distribution.…”