Experimental Study of the Reaction of OH Radicals with Carbonyl Sulfide between 365 and 960 K: Kinetics and Products

Abstract

Reaction OH + OCS → products (1) has been studied in a discharge–flow reactor combined with modulated molecular beam mass spectrometry. The reaction rate constant has been determined under pseudo-first-order conditions through monitoring OH decays in a high excess of OCS: k1 = (2.35 ± 0.25) × 10−12 exp(−(2144 ± 56)/T) cm3 molecule−1 s−1 at T = 365–960 K (the uncertainties represent precision at the 2σ level, the total 2σ relative uncertainty including statistical and systematic errors on the rate constant being 20% at all temperatures). The rate constant of reaction (1) was found to be similar at a total helium pressure of 1, 2, and 8 torr at around 500 K. The SH radical was identified as the primary product of the reaction, and its yield was determined to be about 100% at T = 500 and 750 K. The kinetic and mechanistic data from the present study are compared to previous experimental and theoretical work.

Keywords

• OH radical
• carbonyl sulfide
• OCS
• SH
• kinetics
• rate constant