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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 C_2H_5O_2 + NO_x Reactions: Temperature Dependence of the Overall Rate Constant and the C_2H_5ONO_2 Branching Channel of C_2H_5O_2 + NO
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Kinetics of the C_2H_5O_2 + NO_x Reactions: Temperature Dependence of the Overall Rate Constant and the C_2H_5ONO_2 Branching Channel of C_2H_5O_2 + NO

机译：C_2H_5O_2 + NO_x反应的动力学：总速率常数和C_2H_5O_2 + NO的C_2H_5ONO_2分支通道的温度依赖性

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The temperature dependence of the overall rate constant for the C_2H_5O_2 + NO reaction and the rate constant for the minor branching channel resulting in the production of C_2H_5ONO_2 have been measured using the turbulent flow technique with high-pressure chemical ionization mass spectrometry for the detection of reactants and products. The temperature dependence of the overall rate constant for the C_2H_5O_2 + NO reaction was investigated between 299 and 213 K at 100 Torr pressure, and the data was fit to the following Arrhenius expression (with 2 standard deviation error limits indicated): 3.8_(-1.3)~(+2.1) * 10~(-12)exp[(290 ± 110)/T] cm~3 molecule~(-1) s~(-1). The temperature dependence of the overall rate constant agrees well with the current recommendation for atmospheric modeling. The minor reaction channel C_2H_5O_2 + NO → C_2H_5ONO_2 was directly observed for the first time, and the temperature dependence of the rate constant for this channel was investigated between 298 and 213 K at 100 Torr pressure. The following Arrhenius expression was determined for the minor channel: 1.6_(-1.2)~(+4.0) * 10~(-15)exp[(1160 ± 310)/T] cm~3 molecule~(-1) s~(-1). The Arrhenius expressions for the overall rate and the C_2H_5ONO_2 producing channel indicate a branching ratio of about 0.006 at 298 K and 0.02 at 213 K at 100 Torr pressure. The temperature dependence of the overall rate constant for the C_2H_5O_2 + NO_2 reaction was also investigated between 299 and 213 K at 100 Torr pressure, and the data was fit to the following Arrhenius expression: 4.7_(-1.4)~(+2.0) * 10~(-13)exp[(620 ± 89)/T] cm~3 molecule~(-1) s~(-1).
机译：使用湍流技术和高压化学电离质谱法测量了C_2H_5O_2 + NO反应的总速率常数与导致生成C_2H_5ONO_2的次要分支通道的速率常数对温度的依赖性，以检测反应物和产品。在100 Torr压力下，在299和213 K之间研究了C_2H_5O_2 + NO反应的总速率常数的温度依赖性，该数据符合以下Arrhenius表达式（指出了2个标准偏差误差极限）：3.8 _（- 1.3）〜（+2.1）* 10〜（-12）exp [（290±110）/ T] cm〜3分子〜（-1）s〜（-1）。总速率常数对温度的依赖性与当前对大气建模的建议非常吻合。第一次直接观察到次要反应通道C_2H_5O_2 + NO→C_2H_5ONO_2，并在100 Torr压力下研究了该通道的速率常数在298 K和213 K之间的温度依赖性。确定了次要通道的以下Arrhenius表达：1.6 _（-1.2）〜（+4.0）* 10〜（-15）exp [（1160±310）/ T] cm〜3分子〜（-1）s〜 （-1）。总速率和C_2H_5ONO_2产生通道的Arrhenius表达式表示在100 Torr压力下，在298 K时的支化比约为0.006，在213 K时的支化比约为0.02。还研究了在100 Torr压力下299至213 K之间C_2H_5O_2 + NO_2反应的总速率常数与温度的关系，该数据符合以下Arrhenius表达式：4.7 _（-1.4）〜（+2.0）* 10〜（-13）exp [（620±89）/ T] cm〜3分子〜（-1）s〜（-1）。

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