Journal of Physical Chemistry A, Vol.112, No.40, 9978-9982, 2008
Thermochemistry of the gaseous vanadium chlorides VCl, VCl2, VCl3, and VCl4
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.