Absolute rate constant for the reaction of O(3P) with thiophene from 238 to 448 K

Abstract

Interests in the gas‐phase oxidation of organic sulfur compounds have become increasingly evident due to the important roles that these compounds may play in combustion processes, atmospheric chemistry, and photochemical air pollution. The rate constants for the reaction of O(³P) with thiophene (C₄H₄S) have been determined for the first time under pseudo‐first‐order reaction conditions, using the discharge flow–resonance fluorescence technique. The measured rate constants over a temperature reange 262–448 K are well represented by the Arrhenius expression k = (3.34±0.34)×10⁻¹¹exp[−(1130±60)/RT] cm³ molecule⁻¹ s⁻¹. However, a discontinuity in the Arrhenius plot is noted around 262 K. The results are discussed in terms of different reaction pathways and compared with other compounds having similar molecular structures and various reactivities.