This article presents the results of tests carried out on rapid quenched Fe-based alloys. The alloys were made using an injection-casting method. The actual structure of the alloys was also studied using an indirect method, based on H. Kronmüller's theorem. Based on analysis of the primary magnetization curves, in accordance with the aforementioned theory, it was found that Mo causes a change in internal regions associated with changes in the direction of the magnetization vector. The evolution of the thermal properties with increasing volume of Mo has been confirmed by the DSC curves. Addition of Mo, at the expense of the Nb component, results in changes to the crystallization process (i.e. the crystallization onset temperature and number of stages). The study showed that the addition of Mo at the expense of Nb reduces glass forming ability. Based on the DSC analysis, free volumes were determined for the alloys tested. These values were compared with the analysis of primary magnetization curves. It was found that the DSC curves can be used to indirectly describe the structure of amorphous alloys similar to the theory of the approach to ferromagnetic saturation. This approach is new and can be used by many researchers in this field.