Journal of Chemical Thermodynamics, Vol.28, No.9, 1019-1028, 1996
Thermochemistry of Tetrachalcogen-bis-Hexafluoroarsenate Salts M(4)(Asf(6))(2) (M=se or Te) Containing Lattice-Stabilized Cyclic M(4)(2+) Cations
The massic energies of combustion of the tetrachalcogen-bis-hexafluoroarsenates of selenium and tellurium in fluorine : Se-4(AsF6)(2)(cr) + 11F(2)(g) = 4SeF(6)(g) + 2AsF(5)(g) Te-4(AsF6)(2)(cr) + 11F(2)(g) = 4TeF(6)(g) + 2AsF(5)(g) have been determined by combustion calorimetry, and from them the standard molar enthalpies of formation have been derived at T = 298.15K : Delta(f)H(m)(o){Se-4(AsF6)(2)} = -(3092.5 +/- 5.0)kJ . mol(-1); Delta(f)H(m)(o){Te-4(AsF6)(2)} = -(3353.6 +/- 10.6)kJ . mol(-1), where the uncertainties correspond to twice the standard deviation of the mean. The enthalpy of the reaction : M(4)(AsF6)(2)(cr) = 2M(2)AsF(6)(cr) is estimated to be positive for M = Te, which indicates that Te-4(2+) is lattice stabilized in the solid state. For the reaction with M = Se, the uncertainty is very much larger than the enthalpy of reaction, so the thermochemical information allows no firm conclusion to be drawn about the stability of Se-4(2+).
Keywords:CRYSTAL-STRUCTURES;THERMODYNAMIC PROPERTIES;TEMPERATURE 298.15-K;POLYATOMIC CATIONS;SULFUR;(S7I)4S4(ASF6)6;SELENIUM;OLEUM