Equilibria involving gaseous species CuLi, AgLi and AuLi have been investigated using a Knudsen effusion technique combined with mass spectrometric analysis of the vapour composition. The following dissociation energies were derived by the third law procedure from the measured ion intensities, free energy functions and auxiliary data :Di (CuLi) = 189.3 & 8.8 kJ mol-1 DG(AgLi) = 173.6k6.3 kJ mol-' Di(AuLi) = 280.8 2 6.5 kJ mol-I. 'The measured dissociation energies are considerably lower than those calculated from the Pauling model of the polar bond.There has been considerable interest recently in gaseous intermetallic compounds.1.2 The high stability of many of these compounds has been explained in terms of the Pauling model of the polar bond. No intermetallic gaseous compound of lithium has been observed so far, although one can expect relatively stable molecules between lithium and the elements of the IB group due to the large electronegativity difference between them.
The reaction Li(g)+BO(g)=LiBO(g) has been studied by Knudsen effusion mass spectrometry. Heats of reaction ΔrH00 =(−332.5±5.0), (−317.4±5.0), and (−251.2±5.0) kJ mol−1 were determined for the linear structures Li–O–B and O–B–Li and for the bent structure (LiBO), respectively. These results are compared with values obtained theoretically.
Knudsen effusion mass spectrometric determination of the dissociation energy of diniobium, Nb2(g), and the heat of sublimation of solid niobiumIn the course of a systematic investigation of gaseous lithides, the species in the saturated vapor above condensed phases in the system Sb-Li have been studied. As new molecules, SbLi, Sb,Li, SbLi" Sb,Li" and Sb 3 Li were identified. Enthalpy data derived from the analysis of several gas eqUilibria led to the following atomization energies: Do·(SbLi) = (169.0± 10.0) kJ mol~'; Do·(Sb,Li) = (472.2±6.8) kJ mol~'; Do·(SbLi,) = 378.5± 10.2) kJ mol~'; Do·(Sb,Li,) = (688.8± 12.4) kJ mol~'; Do·(Sb 3 Li) = (698.2±30.0) kJ mol ~ I. These experimental atomization energies are appreciably higher than those of the corresponding compounds of lithium with bismuth. The experimental dissociation energy of SbLi is lower than predicted by Pauling'S rule as was also found for BiLi. . 5218
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