The OH-initiated oxidation of atmospheric peroxyacetic acid: Experimental and model studies

Reaction between CH<sub>3</sub>C(O)OOH (peracetic acid) and OH in the gas-phase: A combined experimental and theoretical study of the kinetics and mechanism

“…CC BY 4.0 License. k4 and k5 (298-353 K) The values we obtain for k4 are clearly much lower (by a factor > 200) than the one previous relative-rate determination of (Wu et al, 2017) who report a room temperature rate coefficient of ~ 1 × 10 -11 cm 3 molecule -1 s -1 . Below, we examine potential sources of systematic bias in our experiments and analysis.…”

“…This upper-limit is a factor ~300 lower than the single, previous experimental determination (Wu et al, 2017) who used a relative-rate technique, which, in principle, offers the advantage that absolute concentrations of CH3C(O)OOH need not be known as long as CH3C(O)OOH and the reference reactant are removed solely via reaction with OH and neither are reformed. However, the relative-rate method does not lend itself readily to the study of this reaction, especially when the 254 nm photolysis of H2O2 is used as OH source, which results both in the photolysis of CH3C(O)OOH and in formation of HO2, which via reactions with CH3C(O)O2 can result in reformation of CH3C(O)OOH.…”

“…The theoretical predictions of k4, k4a and k4b are plotted along with the experimental data from this work and that of Wu et al (2017) in Fig. 9.…”

“…(Orlando and Tyndall, 2003) whereby abstraction of the peroxidic H-atom (R4a), is expected to dominate. A single study of the rate coefficient has been published to date (Wu et al, 2017), in which the authors, deriving a rate coefficient of ≈ 1 × 10 -11 cm 3 molecule -1 s -1 in a relative-rate study, confirm the dominance of the OH-sink. There are no experimental studies of the branching ratio for the reaction between OH and CH3C(O)OOH, though a theoretical study indicates that k4a and k4b are comparable (Rypkema and Francisco, 2013).…”

Reaction between CH<sub>3</sub>C(O)OOH (peracetic acid) and OH in the gas phase: a combined experimental and theoretical study of the kinetics and mechanism

“…−1 s −1 , which is based on reactions of OH with other organic trace gases containing the -OOH group (Orlando and Tyndall, 2003) whereby abstraction of the peroxidic H atom (Reaction R4a), is expected to dominate. A single study of the rate coefficient has been published to date (Wu et al, 2017), in which the authors, deriving a rate coefficient of ≈ 1 × 10 −11 cm 3 molec. −1 s −1 in a relative rate study, confirm the dominance of the OH sink.…”