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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Time-resolved spectroscopic study of the reaction Cl plus n-C5H12 - HCl+C5H11 in solution
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Time-resolved spectroscopic study of the reaction Cl plus n-C5H12 - HCl+C5H11 in solution

机译：溶液中Cl + n-C5H12-> HCl + C5H11反应的时间分辨光谱研究

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We study the hydrogen abstraction reaction from pentane by chlorine radicals using four different experimental approaches. We use two different solvents (CH2Cl2 and CCl4) and two different chlorine atom sources (photodissociation of dissolved Cl-2 and two-photon photolysis of the solvent) to investigate their effects on the recombination and reactivity of the chlorine radical. All four experimental schemes involve direct probing of the transient chlorine population via a charge transfer transition with a solvent molecule. In one of the four approaches, photolysis of Cl-2 in dichloromethane, we also monitor the nascent reaction products (HCl) by transient vibrational spectroscopy. Probing both the reactants and the products provides a comprehensive view of this bimolecular reaction in solution. Between one-third and two-thirds of the chlorine radicals that initially escape the solvent cage undergo diffusive geminate recombination with their partner radical (either another chlorine atom or the solvent radical). The rest react with pentane with the bimolecular rate constants k(bi) = (9.5 +/- 0.7) x 10(9) M-1 s(-1) in CH2Cl2 and k(bi) = (7.4 +/- 2) x 10(9) M-1 s(-1) in CCl4. The recombination yield Phi(rec) depends on both the chlorine atom precursor and the solvent and is larger in the more viscous carbon tetrachloride solutions. The bimolecular reaction rate k(bi) depends only on the solvent and is consistent with a nearly diffusion-limited reaction.
机译：我们使用四种不同的实验方法研究了氯自由基从戊烷中提取氢的反应。我们使用两种不同的溶剂（CH2Cl2和CCl4）和两种不同的氯原子源（溶解的Cl-2的光解离和溶剂的双光子光解）来研究它们对氯自由基的重组和反应性的影响。所有这四个实验方案都涉及通过溶剂分子的电荷转移跃迁直接探测瞬态氯的数量。在四种方法之一中，Cl-2在二氯甲烷中的光解，我们还通过瞬态振动光谱法监测新生的反应产物（HCl）。探测反应物和产物都提供了溶液中这种双分子反应的全面视图。最初从溶剂笼中逸出的氯自由基中，有三分之一到三分之二会与它们的伙伴自由基（另一个氯原子或溶剂自由基）发生扩散性的晶格重组。其余部分与戊烷反应，双分子速率常数k（bi）=（9.5 +/- 0.7）x 10（9）M-1 s（-1）在CH2Cl2中，k（bi）=（7.4 +/- 2）在CCl4中x 10（9）M-1 s（-1）。重组收率Phi（rec）取决于氯原子前体和溶剂，并且在粘性更大的四氯化碳溶液中更大。双分子反应速率k（bi）仅取决于溶剂，并且与几乎受扩散限制的反应一致。

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