Kinetics of the reactions of hydroxyl radicals with aldehydes studied under atmospheric conditions

Kinetics of the gas‐phase reactions of OH radicals with a series of α,β‐unsaturated carbonyls at 299 ± 2 K

“…These rate constants k 1 are also given in Table I [7] using a flash photolysis-resonance fluorescent technique, while those for acrolein and crotonaldehyde are also in excellent agreement with the relative rate constant data of Kerr and Sheppard [6]. However, the present value for acrolein is somewhat lower than that obtained by Maldotti et al [4], and that for methylvinylketone is somewhat higher than the datum of Cox et al [3], although the discrepancies are only just outside of the combined quoted error limits.…”

“…Hence the kinetics and mechanisms of the reactions of these a,&unsaturated carbonyls with the atmospherically important species 0 3 and OH radicals must be experimentally determined in order to understand the chemistry involved in these NO,-dialkene-air photooxidations. While kinetic data are available for the reactions of OH radicals with acrolein [4,6], crotonaldehyde (61, methacrolein [7], and methylvinylketone [3,7], there are only single rate constant determinations for crotonaldehyde and methacrolein, and the data for acrolein [4,6] differ by -50%.…”

Rate constants for the gas-phase reactions of a series of C3?C6 aldehydes with OH and NO3 radicals

“…As discussed previously [8,28], the rate constants obtained by Audley et al [14] show significant discrepancies with those of Kerr and Sheppard [13] and Semmes et al [15] for several of the aldehydes studied (2-methyl-1-propanal, pentanal, [19] a Indicated errors are two least-squares standard deviations. b Placed on an absolute basis using a rate constant for the reaction of the NO 3 radical with methacrolein of k 2 ϭ 3.3 ϫ 10 Ϫ15 cm 3 molecule Ϫ1 s Ϫ1 at 296 K [20].…”

Kinetic study of gas-phase reactions of pinonaldehyde and structurally related compounds

“…Typical plots for pinonaldehyde NO 3 and for pinonaldehyde O 3 are shown by Figures 3 and 4, respectively. These plots are corrected for wall loss, but in Figure 4 it can be seen that the slope does The rate constant for the OH reaction with 3-methyl-butanal has previously been measured as [14] (see Table III) with the use of GC-FID as their analytical technique. As can be seen the value reported here of obtained using isoprene with [13] as the reference compound is significantly larger.…”

“…This study shows that the chemical lifetime of pinonaldehyde in the atmosphere is essentially determined [17] (Estimated) Klamt [18 -20] (Estimated) Kerr and Sheppard [14] n.d. Table II and from the estimates of the OH radical reaction rates in Table III, that the reactivity of pinonaldehyde with the NO 3 radical and with O 3 is mainly linked to the aldehyde group, because the reactions rates of structurally similar compounds without the aldehyde group are significantly slower as shown by Table II. For the reactions of pinonaldehyde with OH radicals other sites like the two tertiary H-atoms could be of importance, see Table III under Klamt [18 -20], who does not calculate a significant difference between the rates of the reaction of pinonaldehyde with OH and that of the structurally similar compound with OH.…”