RATE CONSTANTS FOR THE GAS-PHASE REACTIONS OF O3 WITH A SERIES OF ALKENES AT 296-K+/-2-K
RATE CONSTANTS FOR THE GAS-PHASE REACTIONS OF O3 WITH A SERIES OF ALKENES AT 296-K+/-2-K
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DOI：
10.1002/kin.550240905
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发表时间：
1992-09-01
影响因子：
1.5
通讯作者：
ATKINSON, R
中科院分区：
文献类型：
--
作者：
GREENE, CR;ATKINSON, R
在空气常压（约740 torr）和296 +/- 2k条件下，用相对速率法研究了O3与一系列烯烃的气相反应动力学，并且有足够的正辛烷来清除这些反应中产生的OH自由基。相对于k（O3 +丙烯）= 1.00，得到的速率常数为：1-丁烯0.975 +/- 0.030；2-甲基丙烯，1.14 +/- 0.04；2-甲基-1,3-丁二烯（异戊二烯），1.21 +/- 0.02；1,4-环己二烯4.75 +/- 0.23；环己烯，7.38 +/- 0.48；顺-2-丁烯，12.8 +/- 0.8；反式2-丁烯，21.5 +/- 1.5；2-甲基-2-丁烯，42.1 +/- 2.8；环戊烯64.9 +/- 4.3；2,3-二甲基-2-丁烯123 +/- 11。这些相对速率常数是用O3与丙烯反应的速率常数1.01 x 10(-17) cm3分子-1 s-1在296 K下得到的绝对速率常数。由此得到的速率常数可得到O3与这些烯烃反应的一组自洽的室温数据。
The kinetics of the gas-phase reactions of O3 with a series of alkenes have been investigated at atmospheric pressure (ca. 740 torr) of air and 296 +/- 2 K, using a relative rate method in the presence of sufficient n-octane to scavenge any OH radicals generated in these reactions. Relative to k(O3 + propene) = 1.00, the rate constants obtained were: 1-butene, 0.975 +/- 0.030; 2-methylpropene, 1.14 +/- 0.04; 2-methyl-1,3-butadiene (isoprene), 1.21 +/- 0.02; 1,4-cyclohexadiene, 4.75 +/- 0.23; cyclohexene, 7.38 +/- 0.48; cis-2-butene, 12.8 +/- 0.8; trans-2-butene, 21.5 +/- 1.5; 2-methyl-2-butene, 42.1 +/- 2.8; cyclopentene, 64.9 +/- 4.3; and 2,3-dimethyl-2-butene, 123 +/- 11. These relative rate constants have been placed on an absolute basis using a rate constant for the reaction of O3 with propene of 1.01 x 10(-17) cm3 molecule-1 s-1 at 296 K derived from an analysis of the available literature data. The resulting rate constants then lead to a self-consistent set of room temperature data for the reactions of O3 with these alkenes.