Thermodynamic properties halides

A critical assessment of the chemical thermodynamic properties of the actinides and their compounds is presently being prepared by an international team of scientists under the auspices of the International Atomic Energy Agency (Vienna). As a result of this effort, four publications (1, 2, 3, 5) have already become available and a further ten 6-T4), including the halides (8) and aqueous complexes with Tnorganic ligands (12),... 

Wicks, C. E. and Block, F. E. "Thermodynamic Properties of 65 Elements - Their Oxides, Halides, Carbides, and Nitrides", Bureau of Mines, Bulletin 605, 1963. 

Pankratz LB (1984) Thermodynamic properties of halides. US Dept, of Interior Bureau of Mines, Washington DC Lin JS, Catlow CRA (1993) J Mater Chem 3 1217 Guo XC, Hoffman A, Yates JT (1989) J Chem Phys 90 5787... 

George, J. W., Halides and Oxyhalides of the Elements of Groups Vb and Vlb George, Philip and McClure, Donald S., The Effect of Inner Orbital Splitting on the Thermodynamic Properties of Transition Metal Compounds, and 2 33... 

The ionic radii of the commonest oxidation states are presented in Table 2. There is evidence of an actinide contraction of ionic radii as the 5/ orbitals are filled and this echoes the well established lanthanide contraction of ionic radii as the 4/orbitals are filled. Actinides and lanthanides in the same oxidation state have similar ionic radii and these similarities in radii are obviously paralleled by similarities in chemical behaviour in those cases where the ionic radius is relevant, such as the thermodynamic properties observed for halide hydrolysis. 

In the early part of this century, many types of solid electrolyte had already been reported. High conductivity was found in a number of metal halides. One of the first applications of solid electrolytes was to measure the thermodynamic properties of solid compounds at high temperatures. Katayama (1908) and Kiukkola and Wagner (1957) made extensive measurements of free enthalpy changes of chemical reactions at higher temperatures. Similar potentiometric measurements of solid electrolyte cells are still made in the context of electrochemical sensors which are one of the most important technical applications for solid electrolytes. 

Recent work has shown 103) that for alkali halides the Debye characteristic temperature is not very sensitive to volume changes produced by thermal expansion. This probably indicates that, in general, volume changes of an adsorbent will not markedly affect its bulk thermodynamic properties. 

The physical properties of the thallium halides have been tabulated.1 Crystalline T1F has a distorted rock-salt lattice, with two independent thallium sites.333-335 The thermodynamic properties of the solid have been reassessed.336 At high temperature, the vapor phase contains TLF and T12F2 molecules,337 and matrix isolation studies have demonstrated the presence of both T1F and T12F2 in the solid the dimers have linear symmetry.338... 

The pentahalides of niobium and tantalum are predominantly covalent. Their volatility decreases from the fluorides to the iodides. Nb and Ta belong to the few elements which form stable pentaiodides. Selected physical and thermodynamic properties for the halides are listed in Table 2. All are sensitive to moist air, water or hydroxylic solvents. 

Block, Thermodynamic Properties of 65 Elements Their Oxides, Halides, Carbides and Nitrides , US BuMines Bull 608 (1963)... 

Thermodynamic. Thermodynamic properties of Pu metal, gaseous species, and the aqueous ions at 298 K are given in Table 8. Thermodynamic properties of elemental Pu (44), of alloys (68), and of the gaseous ions Pu+, PuO+, PuO+2, and PuO 2 (67) have been reviewed, as have those of aqueous ions (64), oxides (69), halides (70), hydrides (71), and most other compounds (65). 

This work was undertaken as a part of a study of divalent lanthanide halides in an effort to obtain more accurate thermal data on EuC12 and to determine if the close similarity of the high-temperature thermodynamic properties of divalent europium and alkaline earth compounds emphasized earlier (13-16) could be extended. 

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