The molecules GeCu, GeCo, GeFe, and GeCr have been shown to exist in the vapor phase over liquid solutions of germanium and transition metal at temperatures above 1600°K. Using information derived from a combination of effusion and mass spectrometric techniques the equilibrium constants and energetics of the gaseous reactions GeX+Ge=Gea+X, where X=Co, Fe, and Cr and 2GeCu=Ge2+Cu2, have been determined. The dissociation energies of the molecules GeCu, GeCo, GeFe, and GeCr as obtained by the third-law method are 47.8±5, 56±6, 49.4±7, and 39.6±7 kcal/mole, respectively.