Add time:08/22/2019         Source:sciencedirect.com

The vaporization and sublimation reactions for the thulium-fluorine system have been investigated by mass-loss, X-ray powder diffraction and elemental analysis techniques. Thulium trifluoride was reduced only partially by elemental thulium; a reduced stoichiometric fluoride could not be isolated. Partially reduced TmF3 decomposes upon heating to a metal-rich vapor and a trifluoride-enriched residue. By a target collection Knudsen effusion method, equilibrium vapor pressures were determined for the reaction TmF3(s,l)=TmF3(g). From the slope-intercept data, the following thermodynamic changes with associated standard deviations were derived: ΔH°1579 = (86.24 ± 0.48) kcal mol−1 and gDS°1579 = (34.95 ± 0.32) cal mol−1K−1. Use of estimated and reported thermodynamic functions gives ΔH°298 = (108.2 ± 1.5) kcalmol−1and gDS°298 = (55.4 ± 1.3) cal mol−1K−1. Use of the third-law procedure yielded ΔH°298 = (107.5 ± 2.3) kcalmol−1. The derived thermodynamic values are compared with those of other lanthanide fluoride systems.

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