Mass spectrometric studies at high temperatures. Part 35.—Stabilities of gaseous GeCl2and GeBr2

Abstract
Mass spectrometric studies of the equilibrium vapour species for the systems, Ge(s)+ GeCl4(g) and Ge(s)+ GeBr4(g), have been conducted using a gas-inlet Knudsen cell. The disproportionation reactions, Ge(s)+ GeCl4(g)= 2GeCl2(g)(I) and Ge(s)+ GeBr4(g)= 2GeBr2(g)(II) were the only equilibria involved; no polymeric species were observed. The heats of reactions (I) and (II) were ΔH°r, 298(I)= 40.6 ± 2.0 kcal mole–1 and ΔH°r, 298(II)= 40.4 ± 1.5 kcal mole–1. The heats of formation and atomization energies for gaseous GeCl2 and GeBr2 were estimated to be ΔH°f, 298[GeCl2(g)]=–42 ± 1 kcal mole–1, ΔH°f, 298[GeBr2(g)]=–13 ± 1 kcal mole–1, ΔH°atoms[GeCl2(g)]= 188 ± 5 kcal mole–1, and ΔH°atoms[GeBr2(g)]= 164 ± 5 kcal mole–1.

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