An absolute- and relative-rate study of the gas-phase reaction of OH radicals and Cl atoms with n-alkyl nitrates

Ole J. Nielsen; Howard W. Sidebottom; Michael Donlon; Jack Treacy

doi:10.1016/0009-2614(91)87051-C

An absolute- and relative-rate study of the gas-phase reaction of OH radicals and Cl atoms with n-alkyl nitrates

Ole J. Nielsen^*, Howard W. Sidebottom, Michael Donlon, Jack Treacy

^*Corresponding author af dette arbejde

40 Citationer (Scopus)

Abstract

Rate constants for the reaction of OH radicals and Cl atoms with CH₃ONO₂, C₂H₅ONO₂, n-C₃H₇ONO₂, n-C₄H₉ONO₂, and n-C₅H₁₁ONO₂ have been determined at 298 ± 2 K and a total pressure of approximately 1 atm. The OH rate data were obtained using both the absolute-rate technique or pulse radiolysis combined with kinetic spectroscopy and a conventional photolytic relative-rate method. The Cl rate constants were measured using only the relative-rate method. Evidence is presented from the kinetic studies that reaction of OH radicals with alkyl nitrates may involve both addition and abstraction pathways. The data show that the -ONO₂ group substantially decreases the rate constant for H-atom abstraction by OH radicals from groups bonded to the -ONO₂ group and also decreases that for groups in the β position. Similar resuls were found for the reaction of Cl atoms with these compounds. The results are discussed in terms of reactivity trends.

Originalsprog	Engelsk
Tidsskrift	Chemical Physics Letters
Vol/bind	178
Udgave nummer	2-3
Sider (fra-til)	163-170
Antal sider	8
ISSN	0009-2614
DOI	https://doi.org/10.1016/0009-2614(91)87051-C
Status	Udgivet - 22 mar. 1991

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title = "An absolute- and relative-rate study of the gas-phase reaction of OH radicals and Cl atoms with n-alkyl nitrates",

abstract = "Rate constants for the reaction of OH radicals and Cl atoms with CH3ONO2, C2H5ONO2, n-C3H7ONO2, n-C4H9ONO2, and n-C5H11ONO2 have been determined at 298 ± 2 K and a total pressure of approximately 1 atm. The OH rate data were obtained using both the absolute-rate technique or pulse radiolysis combined with kinetic spectroscopy and a conventional photolytic relative-rate method. The Cl rate constants were measured using only the relative-rate method. Evidence is presented from the kinetic studies that reaction of OH radicals with alkyl nitrates may involve both addition and abstraction pathways. The data show that the -ONO2 group substantially decreases the rate constant for H-atom abstraction by OH radicals from groups bonded to the -ONO2 group and also decreases that for groups in the β position. Similar resuls were found for the reaction of Cl atoms with these compounds. The results are discussed in terms of reactivity trends.",

author = "Nielsen, {Ole J.} and Sidebottom, {Howard W.} and Michael Donlon and Jack Treacy",

year = "1991",

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doi = "10.1016/0009-2614(91)87051-C",

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T1 - An absolute- and relative-rate study of the gas-phase reaction of OH radicals and Cl atoms with n-alkyl nitrates

AU - Nielsen, Ole J.

AU - Sidebottom, Howard W.

AU - Donlon, Michael

AU - Treacy, Jack

PY - 1991/3/22

Y1 - 1991/3/22

N2 - Rate constants for the reaction of OH radicals and Cl atoms with CH3ONO2, C2H5ONO2, n-C3H7ONO2, n-C4H9ONO2, and n-C5H11ONO2 have been determined at 298 ± 2 K and a total pressure of approximately 1 atm. The OH rate data were obtained using both the absolute-rate technique or pulse radiolysis combined with kinetic spectroscopy and a conventional photolytic relative-rate method. The Cl rate constants were measured using only the relative-rate method. Evidence is presented from the kinetic studies that reaction of OH radicals with alkyl nitrates may involve both addition and abstraction pathways. The data show that the -ONO2 group substantially decreases the rate constant for H-atom abstraction by OH radicals from groups bonded to the -ONO2 group and also decreases that for groups in the β position. Similar resuls were found for the reaction of Cl atoms with these compounds. The results are discussed in terms of reactivity trends.

AB - Rate constants for the reaction of OH radicals and Cl atoms with CH3ONO2, C2H5ONO2, n-C3H7ONO2, n-C4H9ONO2, and n-C5H11ONO2 have been determined at 298 ± 2 K and a total pressure of approximately 1 atm. The OH rate data were obtained using both the absolute-rate technique or pulse radiolysis combined with kinetic spectroscopy and a conventional photolytic relative-rate method. The Cl rate constants were measured using only the relative-rate method. Evidence is presented from the kinetic studies that reaction of OH radicals with alkyl nitrates may involve both addition and abstraction pathways. The data show that the -ONO2 group substantially decreases the rate constant for H-atom abstraction by OH radicals from groups bonded to the -ONO2 group and also decreases that for groups in the β position. Similar resuls were found for the reaction of Cl atoms with these compounds. The results are discussed in terms of reactivity trends.

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U2 - 10.1016/0009-2614(91)87051-C

DO - 10.1016/0009-2614(91)87051-C

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AN - SCOPUS:0001501471

SN - 0009-2614

VL - 178

SP - 163

EP - 170

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 2-3

ER -

An absolute- and relative-rate study of the gas-phase reaction of OH radicals and Cl atoms with n-alkyl nitrates

Abstract

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