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Master Equation Modeling of the Unimolecular Decompositions of α‐Hydroxyethyl (CH 3 CHOH) and Ethoxy (CH 3 CH 2 O) Radicals
Author(s) -
Dames Enoch E.
Publication year - 2014
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20844
Subject(s) - chemistry , alkoxy group , decomposition , acetaldehyde , radical , context (archaeology) , thermodynamics , substituent , computational chemistry , medicinal chemistry , organic chemistry , alkyl , ethanol , paleontology , physics , biology
The unimolecular decomposition of two radical isomers of C 2 H 5 O (CH 3 CH 2 O/ethoxy, CH 3 CHOH/α‐hydroxyethyl) are investigated by means of Rice–Ramsperger–Kassel–Marcus/master equation simulations in helium and nitrogen bath gases on an accurate one‐dimensional potential energy surface. For ethoxy, simulations are carried out between temperatures of 406 and 1200 K and pressures of 0.001 and 100 atm. For CH 3 CHOH, simulations are carried out between temperatures of 800 and 1500 K and pressures of 0.001 and 100 atm. Results are compared with available experimental data, with good agreement. The dominant product of α‐hydroxyethyl decomposition is CH 3 CHO + H, with C 2 H 3 OH + H and CH 3 + CH 2 O, being minor channels. Rate coefficients are strongly dependent on temperature and pressure and are recommended with attendant uncertainty factor estimates. The relative roles of vinyl alcohol and acetaldehyde in the context of combustion chemistry are also discussed.