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Product formation from the reaction of the NO 3 radical with isoprene and rate constants for the reactions of methacrolein and methyl vinyl ketone with the NO 3 radical
Author(s) -
Kwok Eric S. C.,
Aschmann Sara M.,
Arey Janet,
Atkinson Roger
Publication year - 1996
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1996)28:12<925::aid-kin10>3.0.co;2-b
Subject(s) - methacrolein , chemistry , methyl vinyl ketone , isoprene , reaction rate constant , ketone , photochemistry , free radical reaction , radical , product (mathematics) , organic chemistry , catalysis , kinetics , copolymer , physics , quantum mechanics , methacrylic acid , polymer , geometry , mathematics
Using a relative rate method, rate constants for the gas‐phase reactions of the NO 3 radical with methacrolein and methyl vinyl ketone were determined to be (4.4 ± 1.7) × 10 −15 cm 3 molecule −1 s −1 and <6 × 10 −16 cm 3 molecule −1 s −1 , respectively, at 296 ± 2 K. The molar formation yields of methacrolein and methyl vinyl ketone from the gas‐phase reaction of the NO 3 radical with isoprene at 296 ± 2 K and atmospheric pressure of air were measured to be 0.035 ± 0.014 each. The tropospheric implications of these kinetic and product data are discussed, and it is concluded that the nighttime NO 3 radical reactions with methacrolein and methyl vinyl ketone are not important. However, during nighttime the formation of methacrolein and methyl vinyl ketone from the reaction of isoprene with the NO 3 radical may dominate over their formation from the O 3 reaction with isoprene. Atmospheric pressure ionization tandem mass spectrometry (API‐MS/MS) was used to investigate the products of the reactions of the NO 3 radical with isoprene and isoprene‐d 8 , and C 5 ‐nitrooxycarbonyl(s) (e.g., O 2 NOCH 2 C(CH 3 ) (DOUBLEBOND) CHCHO), C 5 ‐hydroxynitrate(s) (e.g., O 2 NOCH 2 C(CH 3 )(DOUBLEBOND) CHCH 2 OH), C 5 ‐nitrooxyhydroperoxide(s) (e.g., O 2 NOCH 2 C(CH 3 )(DOUBLEBOND) CHCH 2 OOH), and C 5 ‐hydroxycarbonyl(s) (e.g., HOCH 2 CH(DOUBLEBOND) C(CH 3 )CHO) and their deuterated analogs were observed from these reactions. © 1996 John Wiley & Sons, Inc.