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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Thermochemistry of the gaseous vanadium chlorides VCl, VCl2, VCl3, and VCl4
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Thermochemistry of the gaseous vanadium chlorides VCl, VCl2, VCl3, and VCl4

机译：气态氯化钒VCl，VCl2，VCl3和VCl4的热化学

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摘要

Gaseous equilibria in the V-Ag-Cl system were studied at elevated temperatures by effusion-beam mass spectrometry, where the pertinent species were generated by reaction Of Cl-2(g) with V + Ag granules in the effusion cell source. Reaction enthalpies were derived from the equilibrium data, and the standard enthalpies of formation at 298 K of gaseous VCl, VCl2, and VCl3 were found to be +49.7, -34.8, and -85.6 kcal mol(-1), respectively. The corresponding bond dissociation energies at 298 K are D(V-Cl) = 102.9 kcal, D(ClV-Cl) = 113.5 kcal, D(Cl2V-Cl) = 79.8 kcal, and D(Cl3V-Cl) = 69.5 kcal. From these data, the dissociation energy D degrees 0(VCl) = 101.9 kcal mol(-1) or 4.42 eV is obtained. An alternate value, Delta H-f(298)degrees(VCl3,g) = -87.0 kcal mol(-1) was derived from third-law analysis of literature sublimation data for VCl3(s). In addition, literature thermochemical data on VCl4(g) were re-evaluated, leading to Delta H-f(298)degrees = -126.1 kcal mol(-1). The results are compared with various estimates in the literature.
机译：V-Ag-Cl系统中的气态平衡是通过喷射电子束质谱在高温下进行研究的，其中相关物种是通过Cl-2（g）与V + Ag颗粒在喷射细胞源中反应生成的。从平衡数据得出反应焓，发现在298 K时气态VCl，VCl2和VCl3的标准生成焓分别为+ 49.7，-34.8和-85.6 kcal mol（-1）。 298 K时相应的键解离能为D（V-Cl）= 102.9 kcal，D（ClV-Cl）= 113.5 kcal，D（Cl2V-Cl）= 79.8 kcal和D（Cl3V-Cl）= 69.5 kcal。从这些数据，获得离解能D度0（VCl）= 101.9 kcal mol（-1）或4.42 eV。替代值Delta H-f（298）degrees（VCl3，g）= -87.0 kcal mol（-1）是从对VCl3的文献升华数据的三次定律分析中得出的。此外，对VCl4（g）的文献热化学数据进行了重新评估，导致Delta H-f（298）度= -126.1 kcal mol（-1）。将结果与文献中的各种估计值进行比较。

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