Kinetics and mechanism of the reaction of hydroxyl radicals with acetonitrile under atmospheric conditions

The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH{sub 3}CN (1) and its isotopic variants, OH + CD{sub 3}CN (2), OD + CH{sub 3}CN (3), and OD + CD{sub 3}CN (4). Reactions 1 and 2 were studied as a...

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Bibliographic Details
Published in:Journal of physical chemistry (1952) 1991-02, Vol.95 (3), p.1232-1240
Main Authors: Hynes, Anthony J, Wine, P. H
Format: Article
Language:English
Subjects:
400500 - Photochemistry
540120 - Environment, Atmospheric- Chemicals Monitoring & Transport- (1990-)
ACETONITRILE
ARRHENIUS EQUATION
ATMOSPHERIC CHEMISTRY
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
ENVIRONMENTAL SCIENCES
EQUATIONS
Exact sciences and technology
EXPERIMENTAL DATA
FLUORESCENCE
Free radicals chemistry
HYDROXYL RADICALS
INFORMATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
KINETICS
LASERS
LUMINESCENCE
NITRILES
NUMERICAL DATA
Organic chemistry
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PRESSURE DEPENDENCE
RADICALS
REACTION KINETICS
Reactivity and mechanisms
TEMPERATURE DEPENDENCE
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Summary:The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH{sub 3}CN (1) and its isotopic variants, OH + CD{sub 3}CN (2), OD + CH{sub 3}CN (3), and OD + CD{sub 3}CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N{sub 2}, N{sub 2}/O{sub 2}, and He buffer gases. In the absence of O{sub 2} all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-firt-order rate constants which were proportional to substrate concentration. Data obtained in N{sub 2} over the range 50-700 Torr at 298 K are consistent with k{sub 1} showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures is k{sub 1}(T) = (1.1{sub {minus}0.3}{sup +0.5}) {times} 10{sup {minus}12} exp(({minus}1,130 {plus minus} 90)/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The kinetics of reaction 2 are found to be pressure dependent with k{sub 2} (298 K) increasing from (1.21 {plus minus} 0.12) {times} 10{sup {minus}14} to (2.16 {plus minus} 0.11) {times} 10{sup {minus}14} cm{sup 3} molecule{sup {minus}1}s{sup {minus}1} over the pressure range 50-700 Torr of N{sub 2} at 298 K. Data at pressures >600 Torr give k{sub 2}(T) = (9.4{sub {minus}5.0}{sup +13.4}) {times} 10{sup {minus}13} exp(({minus}1,180 {plus minus} 250)/T) cm{sup 3} molecule{sup {minus}1}s{sup {minus}1}.
ISSN:0022-3654
1541-5740
DOI:10.1021/j100156a037