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Kinetic measurements of methyl and ethyl nitrate reactions with OH radicals
Author(s) -
Kakesu Masako,
Bandow Hiroshi,
Takenaka Norimichi,
Maeda Yasuaki,
Washida Nobuaki
Publication year - 1997
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(1997)29:12<933::aid-kin5>3.0.co;2-n
Subject(s) - chemistry , radical , nitrate , photodissociation , ozone , photochemistry , reaction rate constant , reaction rate , analytical chemistry (journal) , organic chemistry , kinetics , catalysis , physics , quantum mechanics
Reaction rate coefficients of methyl and ethyl nitrates with OH radicals were determined by the relative rate method in 1 atmosphere of oxygen. Reactions were initiated by the photochemical formation of OH radicals utilizing the reaction: H 2 O+O( 1 D)→2OH. O( 1 D) was obtained through a stationary photolysis of excess ozone in an experimental system under black light irradiation. Measurements were carried out for various combinations with different reference materials. Rate coefficients obtained were (0.30±0.032 (2σ)×10 −13 cm 3 molecule −1 s −1 (Temp.: 304–310 K) for methyl nitrate and (2.0±0.70)×10 −13 cm 3 molecule −1 s −1 (298–310 K) for ethyl nitrate. For methyl nitrate, this data indicates the preference of a smaller rate coefficient between the two values reported in the literature [1,2], which have shown large discrepancies of more than one order of magnitude. For ethyl nitrate, only one measurement has been reported [2]. However, the present result suggests that the reported value was overestimated by a factor of more than two. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet: 29: 933–941, 1997.