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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Kinetics of the Reactions of Allyl and Propargyl Radicals with CH_3
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Kinetics of the Reactions of Allyl and Propargyl Radicals with CH_3

机译：烯丙基和丙炔基自由基与CH_3反应的动力学

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The allyl-methyl and propargyl-methyl cross-radical reactions were studied by laser PhOtOIYSis/Photoionization 'mass spectroscopy. Overall rate constants were obtained in direct real-time experiments in the temperature region 301-800 K and bath gas (helium) density (3-36) x 1016 atom cm-3. The observed overall C3Hs + " CH_3 (I) and C_3H_3 + CH_3 (2) rate constants demonstrate negative temperature dependencies. Master equation modeling of coUisio~al effects indicates that the C_3Hs + CH3 reaction is near its high-pressure limit under all I experimental conditions used. Minor corrections for the falloff effects (on average, 18% at the highest temperature) applied to the experimental values result in the high-pressure-limit temperature dependence of the rate constant of reaction I: k1 = 1.55 x 10-9 T -oS_4exp(117 K/1) cm3 molecule-1 S-I. The temperature dependence of k1~ combined with the thermochemistry of reaction 1 results in the rate constants of the reverse ,reaction of thermal decomposition of I-C4H8 k-1~(T) = I.I x 1016exp(-39Ioo K/1) S-I. On the other hand ;j the C_3H_3 + CH_3 reaction is not near the high-pressure limit and faUoff in reaction 2 cannot be neglected at 0'; temperatures above 500 K. Falloff corrections applied to reaction 2, on average, reach a factor of 2 at 800 K ;,1 and introduce substantial uncertainties in the extrapolated high-pressure-limit rate constant values. The evaluated~'~ high-pressure-Iimit rate constants of reaction 2 can be represented with the expression k2 = 6.80 x 10-11 ~;;i exp(130K/1) cm3 molecule-1 S-I. C4H8 and C4H6 were identified as primary products of the reactions I and 2,respectively.
机译：烯丙基-甲基和炔丙基-甲基的自由基反应通过激光PhOtOYSis /光电离质谱法研究。在直接实时实验中，在301-800 K的温度区域和浴气体（氦气）密度（3-36）x 1016原子cm-3下获得了总速率常数。观测到的总体C3Hs + CH_3（I）和C_3H_3 + CH_3（2）速率常数显示出负温度依赖性。主效应方程模型建模表明，在所有I实验下，C_3Hs + CH3反应均接近其高压极限。对实验值应用的衰减影响（在最高温度下平均为18％）的较小校正导致反应速率I的高压极限温度依赖性：k1 = 1.55 x 10-9 T -oS_4exp（117 K / 1）cm3分子-1 SI。k1〜的温度依赖性与反应1的热化学结合产生I-C4H8 k-1〜（热分解反应的速率常数） T）= II x 1016exp（-39Ioo K / 1）SI。另一方面; j C_3H_3 + CH_3反应不接近高压极限，并且反应2中的faUoff在0'时不能忽略;温度超过500 K 。应用于反应2的衰减校正平均达到一个因子在800 K;，1处的2表示，并在推断的高压极限率常数值中引入了很大的不确定性。反应2的评估的高压模拟速率常数可以用表达式k 2 ＝ 6.80×10-11表示; i exp（130K / 1）cm 3分子-1 S-1。 C4H8和C4H6分别被确定为反应I和2的主要产物。

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