Phase formation was studied in the Fe–Ge and Cr–Ge thin-film systems by means of Rutherford backscattering spectrometry and x-ray diffraction. In the Fe–Ge system, FeGe was the first phase to form while in the Cr–Ge system, Cr11Ge8 was found to form first. The results are compared with the predictions of the effective heat of formation model. Heats of formation were calculated using the Miedema model. The effect of the transformation enthalpy term ΔHtr, used to convert a semiconducting element into a hypothetical metallic one in the Miedema model, is also discussed.