Abstraction and addition reactions of four γ‐lactones with H‐atoms and methyl radicals. Issue 6 (26th March 2023)

• Record Type: Journal Article
• Authors: Würmel, Judith; Simmie, John M.
• Is Part Of: International journal of chemical kinetics. Volume 55:Issue 6(2023)
• Page Start: 324
• Page End: 332
• Publication Date: 2023-03-26
• Subjects: addition reactions -- computational chemistry -- gamma‐lactones -- H‐abstraction -- reaction kinetics -- thermochemistry; Chemical kinetics -- Periodicals; 541.394
• DOI: 10.1002/kin.21638
• Languages: English
• ISSNs: 0538-8066

Abstract

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 $_3^\bullet$ are presented on a per abstractable hydrogen basis; abstraction at the tertiary carbon site is consistently favored, while abstraction by CH 3 $_3^\bullet$ lags behind H . Addition reactions of H and CH 3 $_3^\bullet$ have high barriers and favor addition to the C‐center.