Abstract

Ions formed by electron bombardment of the vapor in thermodynamic equilibrium with BaO solid have been studied mass spectrometrically. The BaO solid was heated in a Knudsen cell and a sample of the effusing vapor entered the ion source of a mass spectrometer. At cell temperatures between 1500°K and 1800°K, ion currents of Ba+, BaO+, Ba2O+, Ba2O2+, and Ba2O3+ were observed. The variations of ion intensities with temperature were measured and appearance potential curves were obtained. Possible mechanisms of ion formation were considered, and evidence for the existence of gaseous molecular species of BaO, Ba2O, Ba2O2, and Ba2O3 was obtained. The major molecular species, effusing from the Knudsen cell, was BaO. A thermodynamic treatment of ion currents yields the following heats of reaction BaO(s)=BaO(g); ΔH0∘=104±4 kcal/moleBaO(g)=Ba(g)+O(g); ΔH0∘=130±5 kcal/moleBa2O2(g)=2BaO(g); ΔH1700∘=89±11 kcalBa2O(g)=Ba(g)+BaO(g); ΔH1700∘=93±17 kcal.

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