Rate constants for the reaction of hydroxyl radicals with acetaldehyde from 244–528 K

Abstract

The rate constant for the reaction of hydroxyl radical with acetaldehyde OH+CH3CHO → products has been measured from 244–528 K with the discharge flow-resonance fluorescence technique. The temperature dependence, expressed in Arrhenius form, is k1(T)=(5.52±0.80)×10−12 exp(610±103/RT) cm3 molecule−1 s−1, where R is in cal mol−1 and the errors are at the two standard deviation level. This result is compared to earlier flash photolysis-resonance fluorescence work. Mechanistic considerations are additionally discussed, and it is concluded that acetyl radicals are the most probable products of the reaction. Lastly, theoretical calculations are presented which delineate theoretical issues to be addressed in ab initio potential energy calculations.