Abstract
Rate constants for the gas-phase reactions of OH radicals, NO3 radicals and O-3 with the C-7-carbonyl compounds 4-methylenehex-5-enal CH2=CHC(=CH2)CH2CH2CHO, (3Z)- and (3E)-4-methylhexa-3,5-dienal CH2=CHC(CH3)=CHCH2CHO and 4-methylcyclohex-3-en-1-one, which are products of the atmospheric degradations of myrcene, Z- and E-ocimene and terpinolene, respectively, have been measured at 296+/-2 K and atmospheric pressure of air using relative rate methods. The rate constants obtained (in cm(3) molecule(-1) s(-1) units) were: for 4-methylenehex-5-enal, (1.55+/-0.15)x10(-10), (4.75+/-0.35)x10(-13) and (1.46+/-0.12)x10(-17) for the OH radical, NO3 radical and O-3 reactions, respectively; for (3Z)-4-methylhexa-3,5-dienal: (1.61+/-0.35)x10(-10), (2.17+/-0.30)x10(-12), and (4.13+/-0.81)x10(-17) for the OH radical, NO3 radical and O-3 reactions, respectively; for (3E)-4-methylhexa-3,5-dienal: (2.52+/-0.65)x10(-10), (1.75+/-0.27)x10(-12), and (5.36+/-0.28)x10(-17) for the OH radical, NO3 radical and O-3 reactions, respectively; and for 4-methylcyclohex-3-en-1-one: (1.10+/-0.19)x10(-10), (1.81+/-0.35)x10(-12), and (6.98+/-0.40)x10(-17) for the OH radical, NO3 radical and O-3 reactions, respectively. These carbonyl compounds are all reactive in the troposphere, with daytime reaction with the OH radical and nighttime reaction with the NO3 radical being predicted to dominate as loss processes and with estimated lifetimes of about an hour or less.
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