Anharmonic effect of the unimolecular dissociation of CH₃COOH

Abstract

Anharmonic and harmonic rate constants of the reactions have been calculated with the Rice-Ramsperger-Kassel-Marcus theory, and the anharmonic results are higher than the harmonic ones. The anharmonic effect and isotopic effect on the decomposition reactions have also been examined. The anharmonic effect in all the four reactions is obvious, especially at the high temperatures or energies. Relatively, the anharmonic effect on the reaction trans-acetic acid → TS2 radical is the least obvious among the four reactions. In the microcanonical system, the difference of the rate constants between the deuterated results and the non-deuterated results is not negligible; in other words, the isotopic effect is obvious in all the four reactions. Among these reactions, three of the deuterated results (d, d3 and d4) have a big difference.

Infrared Chemiluminescence Study of the Reaction of Hydroxyl Radical with Formamide and the Secondary Unimolecular Reaction of Chemically Activated Carbamic Acid

“…For convenience, energy parameters for H 2 O and CO 2 products from NH 2 COOH and CH 3 COOH are collected in Table 4. The energies of the transition states for CH 3 COOH decomposition were taken from the most recent theoretical study 52 using CCSD(T)/6-311G(d,p) methods.…”

Diol isomer revealed as a source of methyl ketene from propionic acid unimolecular decomposition

“…Blake and Jackson 23 expanded on the earlier work and published rate constants for the two main reactions of acetic acid via static and flow experiments. Since Bamford and Dewar, 22 numerous experimental 24–26 and theoretical works 27–34 have studied the competing reactions for acetic acid decomposition. More recently, Leplat and Vandooren 35 studied low‐pressure premixed flat flames of acetic acid/O 2 /Ar and developed an acetic acid submechanism to model their results.…”