Kinetics of CN(X 2Σ+) radical reactions with HCN, BrCN and CH3CN

S. Zabarnick*, Ming-Chang Lin

*Corresponding author for this work

Research output: Contribution to journalArticle

35 Scopus citations

Abstract

Absolute rate constants were obtained for CN (X 2Σ+) radical reactions with HCN, BrCN and CH3CN. The CN radical relative concentration was followed by laser-induced fluorescence (LIF) with a cw ring dye laser on the A 2Π-X 2Σ+ (4, 0) band at 621.5 nm. CN radicals were generated by laser photolysis of ICN at 266 nm. The following Arrhenius parameters were obtained over the temperature range 296-578 K: CN+HCN, k=10-11.41±0.15 exp[-(670±100)/T] cm3 s-1; CN+BrCN, k=10-10.7±0.4 × exp[-(1340±330)/T] cm3 s-1; CN+CH3CN, k=10-10.19±0.10 exp[-(1190±70)/T] cm3 s-1. The rates meas and that of Szekely et al. for CN+HCN could be well fitted by the form, k=10-16.20T1.57 exp (-50/T) cm3 s-1 over the range 300-3000 K, allowing extrapolation to the combustion temperature regime. The measured rates and those of Kayes and Levitt and Clark et al. for the CN+BrCN reaction could be fitted by the form, k=10-14.18T1.16 exp(-940/T) cm3 s-1 the temperature range 300-3000 K. In addition, the non-linearity of these data over a wide range of temperature could be satisfactorily accounted for by transition-state theory calculations for both of these reactions.

Original languageEnglish
Pages (from-to)185-191
Number of pages7
JournalChemical Physics
Volume134
Issue number1
DOIs
StatePublished - 15 Jun 1989

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