Rate coefficients for reactions of NO3 with a few olefins and oxygenated olefins

The rate coefficients for the reactions of NO3 with 2-methyl-3-bulene-2-ol (methyl butenol, MBO, k(1)), 1-butene (k(2)), trans-2-butene (k(3)), methacrolein (MACR, k(4)), and methyl vinyl ketone (MVK, k(5)) were measured directly using a flow tube coupled to a diode laser absorption system where NO3 was measured. The measured values of the rate coefficients are k(1) = 4.6 x 10(-14) exp(-400/T) cm(3) molecule(-1) s(-1), k(2) = 5.2 x 10(-13) exp(-1070/T) cm(3) molecule(-1) s(-1), k(3)(298 K) = (4.06 +/- 0.36) x 10(-13) cm(3) molecule(-1) s(-1), k(4)(298 K) less than or equal to 8 x 10(-15) cm(3) molecule(-1) s(-1), and k(5)(298 K) less than or equal to 1.2 x 10(-16) cm(3) molecule(-1) s(-1). The observed reactivity trends are correlated in terms of the presence of electron-withdrawing substituents, which reduces the reactivity of alkenes toward NO3 addition to the double bond. The contribution of NO3 reactions to determining the tropospheric lifetimes of these compounds are also calculated.