Kinetics and Mechanistic Studies of the Atmospheric Oxidation of Alkynes

Abstract

Kinetics studies of the OH-initiated oxidation of 2-butyne, propyne, and acetylene were conducted at 100 Torr and 298 K using turbulent flow chemical ionization mass spectrometry. The major oxidation products were identified, and with the aid of supporting electronic structure thermodynamics calculations, a general OH-initiated oxidation mechanism for the alkynes is proposed. The major product branching ratio and the product-forming rate constants for the 2-butyne-OH adduct + O(2) reaction were experimentally determined as well. The atmospheric implications of the chemical oxidation mechanism and kinetics results are discussed.