Thermochemistry of rare-earth trifluorides II. Estimation of standard enthalpies of formationa

Add time:09/26/2019    Source:sciencedirect.com

Using the most recent crystallographic data, the Born-Landé equation was employed to calculate lattice energies of the rare-eath trifluorides. The excellent agreement (<0.5 per cent) observed between these calculated values and the values derived from Born-Haber-cycle calculations based on experimental enthalpies suggest that these trifluorides are essentially ionic in character. Based on the experimentally measured enthalpies of formation of the rare-earth trifluorides(1) and the Born-Landé calculational routine, all the unmeasured enthalpies of formation, (ΔHof(MX3, c, 298.15 K), can be estimated. The magnitude of the monotonic change of ΔHof(MX3) for the rare-earth trihalides series (14 4f electrons) is comparable to the energy change between Sc and Ti in which only one 3d electron is added. This energy change is consistent with the chemical evidence that the electrons in the f-orbitals of rare earths contribute negligibly to the bonding.

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