The rate constant for the [formula omitted] reaction

Abstract

The rate constant for the reaction CO + H 2O 2 → HOCO + OH (R1) at 713 K is determined based on the batch reactor experiments of Baldwin et al. [R.R. Baldwin, R.W. Walker, S.J. Webster, Combust. Flame 15 (1970) 167] on decomposition of H 2 O 2 sensitized by CO. The value, k 1 ( 713 K ) = 8.1 × 10 2 cm 3 mol - 1 s - 1 , is consistent with spin-unrestricted density functional theory. Extrapolation to a wider temperature range through ab initio calculations yields the rate constant k 1 = 3.6 × 10 4 T 2.5 exp ( - 14 425 [ K ] / T ) cm 3 mol - 1 s - 1 . The reaction is probably of minor importance in combustion. The present analysis reconciles the batch reactor data of Baldwin et al. with recent high-level theoretical work on the CO + HO 2 reaction.