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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Gas phase kinetics and equilibrium of allyl radical reactions with NO and NO_2
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Gas phase kinetics and equilibrium of allyl radical reactions with NO and NO_2

机译：NO和NO_2的烯丙基自由基反应的气相动力学和平衡

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Allyl radical reactions with NO and NO_2 were studied in direct, time-resolved experiments in a temperature controlled tubular flow reactor connected to a laser photolysis/photoionization mass spectrometer (LP-PIMS). In the C_3H_5 + NO reaction 1, a dependence on the bath gas density was observed in the determined rate coefficients and pressure falloff parametrizations were performed. The obtained rate coefficients vary between 0.30-14.2 × 10~(-12) cm~3 s~(-1) (T = 188-363 K, p = 0.39-23.78 Torr He) and possess a negative temperature dependence. The rate coefficients of the C_3H_5 + NO_2 reaction 2 did not show a dependence on the bath gas density in the range used (p = 0.47-3.38 Torr, T = 201-363 K), and they can be expressed as a function of temperature with k(C_3H_5 + NO_2) = (3.97 ± 0.84) × 10~(-11) × (T/300 K)~(-1.55±0.05) cm~3 s~(-1). In the C_3H_5 + NO reaction, above 410 K the observed C3H5 radical signal did not decay to the signal background, indicating equilibrium between C_3H_5 + NO and C_3H_5NO. This allowed the C_3H_5 + NO a? C_3H_5NO equilibrium to be studied and the equilibrium constants of the reaction between 414 and 500 K to be determined. With the standard second- and third-law analysis, the enthalpy and entropy of the C_3H_5 + NO a? C_3H_5NO reaction were obtained. Combined with the calculated standard entropy of reaction (ΔS_(298) = 137.2 J mol~(-1)K~(-1)), the third-law analysis resulted in ΔH ~(298) = 102.4 ± 3.2 kJ mol~(-1) for the C_3H_5-NO bond dissociation enthalpy.
机译：在与激光光解/光电离质谱仪（LP-PIMS）连接的温控管式流动反应器中，在直接的时间分辨实验中研究了NO和NO_2的烯丙基自由基反应。在C_3H_5 + NO反应1中，在所确定的速率系数中观察到浴气体密度的依赖性，并且进行了压力下降参数化。获得的速率系数在0.30-14.2×10〜（-12）cm〜3 s〜（-1）之间变化（T = 188-363 K，p = 0.39-23.78 Torr He），并且具有负温度依赖性。 C_3H_5 + NO_2反应2的速率系数在所使用的范围内（p = 0.47-3.38 Torr，T = 201-363 K）不显示与浴液密度的相关性，它们可以表示为温度的函数其中k（C_3H_5 + NO_2）=（3.97±0.84）×10〜（-11）×（T / 300 K）〜（-1.55±0.05）cm〜3 s〜（-1）。在C_3H_5 + NO反应中，在410 K以上，观察到的C3H5自由基信号没有衰减到信号背景，表明C_3H_5 + NO和C_3H_5NO之间达到平衡。这允许C_3H_5 + NO吗？研究C_3H_5NO平衡，并确定414和500 K之间反应的平衡常数。通过标准的第二定律和第三定律分析，C_3H_5 + NO a的焓和熵？获得C_3H_5NO反应。结合计算的标准反应熵（ΔS_（298）= 137.2 J mol〜（-1）K〜（-1）），三次定律分析得出ΔH〜（298）= 102.4±3.2 kJ mol〜（ -1）对于C_3H_5-NO键解离焓。

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