The rate coefficients for the reactions of O3 with six unsaturated carbonyls have been measured with the relative-rate method in the presence of a sufficient radical scavenger. The experiments were conducted using a 6-m3 reaction chamber combined with a long-path FTIR system. The rate coefficients (measured in 10−18 cm3 molecule−1 s−1) were 1.58 ± 0.23 for crotonaldehyde, 1.59 ± 0.22 for trans-2-pentenal, 1.82 ± 0.26 for 3-methyl-2-butenal, 5.34 ± 0.73 for trans-2-methyl-2-butenal, 29.5 ± 4.1 for 3-pentene-2-one and 8.3 ± 1.1 for mesityl oxide. Conventional transition-state theory (CTST) calculations based on ab initio molecular orbital and density functional methods were performed to evaluate the rate constants for nine unsaturated carbonyls including six compounds examined in the present experiment as well as acrolein, methacrolein, and methyl vinyl ketone. A log–log plot of the rate coefficients measured in the present and previous works vs. the calculated results of the rate constants, showed a linear relationship.
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