Metal halides energetics, 605

Rowley, A. T. et al., Inorg. Chem. Acta, 1993, 211(1), 77 Preparation of metal oxides by fusing metal halides with lithium oxide in a sealed tube leads to explosions if halide hydrates are employed, particularly lanthanide trihalide hydrates. The preparation succeeds with anhydrous halides. This will be purely a question of vapour pressure above an exothermic reaction the question is whether the vapour is water, or metal halide, and the reaction oxide formation, or hydration of lithium oxide. Like other alkali metal oxides, hydration is extremely energetic. 

Scheme 4 Energetics of the BIE for self-ionisation of a metal halide...

All the metals react with the halogens (equation 10.4) and H2 when heated (equation 10.5). The energetics of metal hydride formation are essentially like those of metal halide formation, being expressed in terms of a Bom-Haber cycle (see Section 5.14). 

Mass spectrometry has been used to study the energetics of solvation and has shown that the enthalpies of attachment of successive water molecules to either alkali metal or halide ions become less exothermic as the number of water molecules increases (Kebarle, 1977). The Gibbs free energies of attachment for water molecules have also been found to be negative. 

He did not think of it then, and when he did, he showed that apparently the formation of a metal-carbon bond was unlikely on thermochemical grounds [68] in other words, he was taken in by his own propaganda but in a Note added in Proof in that same work he indicated that electrochemical factors (solvation and Coulombic energies) could make this initiation exo-energetic. However, at that time, 1960-1970, such a suggestion would have been no more plausible than when it was made by others. It was only the painstaking and detailed exploration of the nature of the solutions of A1X3 in alkyl halides [104, 112] that provided the basis of fact which was required to make the theory plausible. 

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