Kinetic study of the gas-phase reaction of O3 with three unsaturated alcohols

Rate constants for the reactions of ozonewith 1-octen-3-ol, 1-nonen-3-ol and 1-nonen-4-ol have been determined at 298 +/- 1 K and atmospheric pressure for the first time. The experiments were performed in a 100-L FEP Teflon film bag using absolute rate method; the rate constants were (1.91 +/- 0.19) x 10(-17), (1.89 +/- 0.20) x 10(-17), and (0.83 +/- 0.08) x 10(-17) cm(3)/(molecule.sec) for 1-octen-3-ol, 1-nonen-3-ol, and 1-nonen-4-ol, respectively. The rate constants have been compared with those of unsaturated alcohols structural homologs, and used to estimate the reaction reactivity. The electronegativity of carbon-carbon double bond was calculated by atomic charges analysis. The calculated results show that the electronic effect of the lone pair electrons of hydroxyl oxygen is the main cause of the difference in rate coefficient. According to the obtained rate constants, the atmospheric lifetimes of studied unsaturated alcohols were also estimated, which indicates that the reaction with ozone is an important loss pathway in the atmosphere, especially in polluted areas. (C) 2018 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.