用LIF检测NO3自由基与1-丁烯、反式丁烯、2-甲基-2-丁烯和2,3-二甲基-2-丁烯气相反应动力学

Berichte der Bunsengesellschaft für physikalische Chemie Pub Date : 2014-03-18 DOI:10.1002/bbpc.199800017

T. Berndt, I. Kind, H.-J. Karbach

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引用次数: 10

摘要

用NO3 LIF测定了NO3自由基与1-丁烯、反式丁烯、2-甲基-2-丁烯和2,3-二甲基-2-丁烯在298±2 K和3 mbar He压力下气相反应的速率常数。通过N2O5在400 K左右热分解生成NO3自由基，即N2O5+M→NO3+NO2+M。应用拟一阶条件，得到1-丁烯和反式丁烯的反应速率常数分别为(1.04±0.11)·10−14和(3.74±0.45)·10−13。2-甲基-2-丁烯和2,3-二甲基-2-丁烯在二级条件下的反应速率常数分别为(1.03±0.09)·10−11和(5.49±0.42)·10−11(单位:cm3分子−1 s1)。

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Kinetics of the Gas-Phase Reaction of NO3 Radicals with 1-Butene, trans-Butene, 2-Methyl-2-butene and 2,3-Dimethyl-2-butene Using LIF Detection

Rate constants for the gas-phase reaction of NO₃ radicals with 1-butene, trans-butene, 2-methyl-2-butene and 2,3-dimethyl-2-butene have been obtained in a flow system at 298±2 K and a pressure of 3 mbar He using NO₃ LIF measurements. NO₃ radicals were produced via thermal decomposition of N₂O₅ at ca. 400 K, i.e. N₂O₅+M → NO₃+NO₂+M.

Applying pseudo-first-order conditions, the rate constants for 1-butene and trans-butene were found to be (1.04±0.11)·10⁻¹⁴ and (3.74±0.45)·10⁻¹³, respectively. For 2-methyl-2-butene and 2,3-dimethyl-2-butene the rate constants were obtained under second-order conditions to be (1.03±0.09)·10⁻¹¹ and (5.49±0.42)·10⁻¹¹, respectively (unit: cm³ molecule⁻¹ s¹).

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Berichte der Bunsengesellschaft für physikalische Chemie

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