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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Experimental Thermochemistry of the SiCl and SiBr Radicals; Enthalpies of Formation of Species in the Si-Cl and Si-Br Systems
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Experimental Thermochemistry of the SiCl and SiBr Radicals; Enthalpies of Formation of Species in the Si-Cl and Si-Br Systems

机译：SiCl和SiBr自由基的实验热化学; Si-Cl和Si-Br系统中物种形成的焓

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摘要

Gaseous reaction equilibria involving the radical species SiCl and SiBr were studied by mass spectrometric monitoring of the molecular beam issuing from a heated effusion cell source, and the results were used to derive the enthalpies of formation △_fH_(298)~°(SiCl.g) = 36.8 kcal mol~(-1) and △_fH_(298)~°(SiBr.g) = 48.7 kcal mol~(-1), along with the dissociation energies D_0~°(SiCl) = 98.9 kcal mol~(-1) and D_0~°(SiBr) = 84.7 kcal mol~(-1), all ± 2 kcal mol~(-1). Thermochemical data were also obtained for the species SiCl_2 and SiBr_2, confirming earlier data in the literature. Nonobservance of the species SiCl_3 and SiBr_3 was used to set lower limits of - 84 and - 40 kcal mol~(-1) to the enthalpies of formation of the gaseous trichloride and tribromide, respectively. The results are compared with experimental and theoretical values in the literature, clarifying previous discrepancies regarding the species SiCl_3 and SiBr_3. From a full evaluation of the literature and this work, a recommended set of enthalpies of formation of the gaseous silicon mono-, di-, tri-, and tetrahalide species is given.
机译：通过质谱监测从加热的渗出池源发出的分子束，研究了涉及自由基物种SiCl和SiBr的气态反应平衡，并将其结果用于推导形成焓△_fH_（298）〜°（SiCl.g ）= 36.8 kcal mol〜（-1）和△_fH_（298）〜°（SiBr.g）= 48.7 kcal mol〜（-1）以及解离能D_0〜°（SiCl）= 98.9 kcal mol〜（ -1）和D_0〜°（SiBr）= 84.7 kcal mol〜（-1），均为±2 kcal mol〜（-1）。还获得了SiCl_2和SiBr_2物种的热化学数据，证实了文献中的早期数据。不观察到SiCl_3和SiBr_3物种分别为气态三氯化物和三溴化物的形成焓设定下限-84和-40 kcal mol〜（-1）。将结果与文献中的实验值和理论值进行比较，以澄清先前关于SiCl_3和SiBr_3物种的差异。通过对文献和这项工作的全面评估，给出了一组推荐的形成气态硅单，二，三和四卤化物的焓。

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