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Kinetics of the reactions of pinonaldehyde with OH radicals and with Cl atoms

✍ Scribed by Barbara Nozière; Markus Spittler; Lars Ruppert; Ian Barnes; Karl H. Becker; Manuel Pons; Klaus Wirtz

Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
193 KB
Volume
31
Category
Article
ISSN
0538-8066

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✦ Synopsis

The rate constant for the reaction of OH radicals with pinonaldehyde has been measured at 293 Ϯ 6 K using the relative rate method in the laboratory in Wuppertal (Germany) using photolytic sources for the production of OH radicals and in the EUPHORE smog chamber facility in Valencia (Spain) using the in situ ozonolysis of 2,3-dimethyl-2-butene as a dark source of OH radicals. In all the experiments pinonaldehyde and the reference compounds were monitored by FTIR spectroscopy, and in addition in the EUPHORE smog chamber the decay of pinonaldehyde was monitored by the HPLC/DNPH method and the reference compound by GC/FID. The results from all the different series of experiments were in good agreement and lead to an average value of k(pinonaldehyde ϩ OH) ϭ (4.0 Ϯ 1.0) ϫ 10 Ϫ11 cm 3 molecule Ϫ1 s Ϫ1 . This result lead to steady-state estimates of atmospheric pinonaldehyde concentrations in the ppbV range (1 ppbV Ϸ 2.5 ϫ 10 10 molecule cm Ϫ3 at 298 K and 1 atm) in regions with substantial ␣-pinene emission. It also implies that atmospheric sinks of pinonaldehyde by reaction with OH radicals could be half as important as its photolysis.

The rate constant of the reaction of pinonaldehyde with Cl atoms has been measured for the first time. Relative rate measurements lead to a value of k(pinonaldehyde ϩ Cl) ϭ (2.4 Ϯ 1.4) ϫ 10 Ϫ10 cm 3 molecule Ϫ1 s Ϫ1 . In contrast to previous studies which suggested enhanced kinetic reactivity for pinonaldehyde compared to other aldehydes, the results from both the OH-and Cl-initiated oxidation of pinonaldehyde in the present work are in line with predictions using structure-activity relationships.

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