Kinetics of the R + NO2 Reactions (R = i-C3H7, n-C3H7, s-C4H9, and t-C4H9

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• 作者：Matti P. Rissanen ; Suula L. Arppe ; Arkke J. Eskola ; Matti M. Tammi ; Raimo S. Timonen
• 刊名：Journal of Physical Chemistry A
• 出版年：2010
• 出版时间：April 15, 2010
• 年：2010
• 卷：114
• 期：14
• 页码：4811-4817
• 全文大小：159K
• 年卷期：v.114,no.14(April 15, 2010)
• ISSN：1520-5215

文摘

The bimolecular rate coefficients of four alkyl radical reactions with NO<sub>2sub> have been measured in direct time-resolved experiments. Reactions were studied under pseudo-first-order conditions in a temperature-controlled tubular flow reactor coupled to a laser photolysis/photoionization mass spectrometer (LP-PIMS). The measured reaction rate coefficients are independent of helium bath gas pressure within the experimental ranges covered and exhibit negative temperature dependence. For i-C<sub>3sub>H<sub>7sub> + NO<sub>2sub> and t-C<sub>4sub>H<sub>9sub> + NO<sub>2sub> reactions, the dependence of ordinate (logarithm of reaction rate coefficients) on abscissa (1/T or log(T)) was nonlinear. The obtained results (in cm<sup>3sup>s<sup>−1sup>) can be expressed by the following equations: k(n-C<sub>3sub>H<sub>7sub> + NO<sub>2sub>) = ((4.34 ± 0.08) × 10<sup>−11sup>) (T/300 K)<sup>−0.14±0.08sup> (203−473 K, 1−7 Torr), k(i-C<sub>3sub>H<sub>7sub> + NO<sub>2sub>) = ((3.66 ± 2.54) × 10<sup>−12sup>) exp(656 ± 201 K/T)(T/300 K)<sup>1.26±0.68sup> (220−489 K, 1−11 Torr), k(s-C<sub>4sub>H<sub>9sub> + NO<sub>2sub>) = ((4.99 ± 0.16) × 10<sup>−11sup>)(T/300 K)<sup>−1.74±0.12sup> (241−485 K, 2 − 12 Torr) and k(t-C<sub>4sub>H<sub>9sub> + NO<sub>2sub>) = ((8.64 ± 4.61) × 10<sup>−12sup>) exp(413 ± 154 K/T)(T/300 K)<sup>0.51±0.55sup> (201−480 K, 2−11 Torr), where the uncertainties shown refer only to the 1 standard deviations obtained from the fitting procedure. The estimated overall uncertainty in the determined bimolecular rate coefficients is about ±20%.