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首页> 外文期刊>Physical chemistry chemical physics: PCCP >Observation of unique pressure effects in the combination reaction of benzyl radicals in the gas to liquid transition region
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Observation of unique pressure effects in the combination reaction of benzyl radicals in the gas to liquid transition region

机译：观察到气体中苄基自由基到液体过渡区的结合反应中独特的压力效应

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The combination reaction of two benzyl radicals has been studied in a wide range of pressures (0.01-1000 bar) and temperatures (250-400 K) in various bath gases (Ar, N-2 and CO2). The measured second-order combination rate constants of benzyl radicals were independent of the pressure and the bath gas below 1 bar, as expected for a limiting "high pressure'' rate constant of a termolecular combination process. However, the reaction becomes steadily faster when the pressure in Ar is further raised until it finally starts to decrease when densities corresponding to diffusion controlled kinetics are reached. Such a unique pressure dependence was more strongly accentuated in CO2 and at lower temperatures. Our results seem to provide first clear indications for a contribution of the radical-solvent interaction in the combination reaction kinetics of such large radicals as benzyl in the gas to liquid transition range. [References: 23]
机译：在各种浴气（Ar，N-2和CO2）中，在很宽的压力（0.01-1000 bar）和温度（250-400 K）范围内，研究了两个苄基的联合反应。如对分子结合过程的极限“高压”速率常数所期望的那样，测得的苄基的二级结合速率常数与压力和低于1 bar的浴气无关，但是，当反应速率稳定时，反应稳定地加快。 Ar的压力进一步升高，直到达到与扩散控制动力学相对应的密度时最终开始下降，这种独特的压力依赖性在CO2和较低温度下更加明显，我们的结果似乎提供了第一个明确的证据自由基与溶剂的相互作用在气态至液态转变范围内诸如苄基这样的大自由基的联合反应动力学中[参考文献：23]

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