Abstraction and addition reactions of four γ-lactones with H-atoms and methyl radicals

IF 1.5 4区化学 Q4 CHEMISTRY, PHYSICAL International Journal of Chemical Kinetics Pub Date : 2023-03-26 DOI:10.1002/kin.21638

Judith Würmel, John M. Simmie

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Abstract

The five-membered cyclic esters, or γ-lactones, are promising candidates as biofuel additives and green solvent components. A comprehensive study of thermochemical and kinetic properties of γ-butyrolactone (GBL), γ-valerolactone (GVL), γ-caprolactone (GCL), and γ-heptalactone (GHL) has been conducted. The entropy, , specific heat, , enthalpy function, , and the enthalphy of formation at 298.15 K, , as well as the adiabatic ionization potential and single bond dissociation energies are reported. Bimolecular rate constants for the abstraction of H-atom by H^• and CH $_{3}^{•}$ are presented on a per abstractable hydrogen basis; abstraction at the tertiary carbon site is consistently favored, while abstraction by CH $_{3}^{•}$ lags behind H^•. Addition reactions of H^• and CH $_{3}^{•}$ have high barriers and favor addition to the C-center.

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四种γ -内酯与H -原子和甲基自由基的萃取和加成反应

五元环酯或γ-内酯是生物燃料添加剂和绿色溶剂成分的有前途的候选者。对γ-丁内酯(GBL)、γ-戊内酯(GVL)、γ-己内酯(GCL)和γ-庚内酯(GHL)的热化学性质和动力学性质进行了综合研究。给出了其熵、比热、焓函数和298.15 K时的生成焓，以及绝热电离势和单键离解能。给出了H•和CH 3•$_3^\bullet$抽象H原子的双分子速率常数;叔碳位的萃取一直是有利的，而ch3•$_3^\bullet$的萃取则落后于H•。H•和ch3•$_3的加成反应具有较高的势垒，有利于加成到c中心。

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来源期刊

International Journal of Chemical Kinetics 化学-物理化学

CiteScore

3.30

自引率

6.70%

发文量

审稿时长

3 months

期刊介绍： As the leading archival journal devoted exclusively to chemical kinetics, the International Journal of Chemical Kinetics publishes original research in gas phase, condensed phase, and polymer reaction kinetics, as well as biochemical and surface kinetics. The Journal seeks to be the primary archive for careful experimental measurements of reaction kinetics, in both simple and complex systems. The Journal also presents new developments in applied theoretical kinetics and publishes large kinetic models, and the algorithms and estimates used in these models. These include methods for handling the large reaction networks important in biochemistry, catalysis, and free radical chemistry. In addition, the Journal explores such topics as the quantitative relationships between molecular structure and chemical reactivity, organic/inorganic chemistry and reaction mechanisms, and the reactive chemistry at interfaces.

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