Thermochemistry of the gaseous fluorides of samarium, europium, and thulium

Abstract

The gaseous mono-, di-, and trifluorides of the lanthanide metals samarium, europium, and thulium were characterized thermochemically from high temperature equilibrium studies carried out by mass spectrometry. Reaction enthalpies and entropies were derived using second-law analysis throughout, and the results were used to evaluate the enthalpies of formation and bond dissociation energies (BDE) of the gaseous fluorides, and to obtain approximate values for the electronic entropies of the MF and MF2 species. The dissociation energies of the monofluorides D°0(SmF)=134 kcal/mole, D°0(EuF)=129 kcal/mole, and D°0(TmF)=121 kcal/mole, all ±2 kcal/mole, are in good agreement with values predicted by the Rittner electrostatic model, whereas values in the polyatomic fluorides show considerable variation and do not seem to follow any clear trends. Although the BDE values in some instances differ from previous estimates, their sums yield trifluoride heats of atomization that are in close accord with values derived from the vaporization thermodynamics of the solid trifluorides.