The kinetic study of excited singlet oxygen atom O(1D) reactions with acetylene

Abstract

Understanding the multi-channel dynamics of O(1D) reactions with unsaturated hydrocarbon molecules in low temperature reaction kinetics is critically important in stratospheric chemistry, plasma chemistry, plasma assisted fuel reforming, materials synthesis, and plasma assisted combustion. A photolysis flow reactor coupled with highly selective mid-infrared Faraday Rotation Spectroscopy (FRS) and direct ultraviolet-infrared (UV-IR) absorption spectroscopy (DAS) techniques was developed for the first time to study the multi-channel dynamics of excited singlet oxygen atom O(1D) reactions with C2H2 and the kinetics of subsequent reactions. Time-resolved species concentrations of OH, HO2 and H2O were obtained and used to develop a validated kinetic model of O(1D) reactions with C2H2. The branching ratios of O(1D) reaction with C2H2 and subsequent HO2 kinetics were also quantified. It is found that, contrary to O(1D) reactions with saturated alkanes, OH formation via direct H abstraction by O(1D) is negligible. The results revealed that two chain-branching and propagation reactions via direct O(1D) insertion are the major pathways for radical production. The present study clearly demonstrated the advantage of radical detection and kinetic studies using FRS in the effective suppression of absorption interference from non-paramagnetic hydrocarbons.