The differentiation of the five-component mutual system Li, Na, K, Ca // F, WO4 has been carried out using the software package on the basis of the graph theory and revealed internal secants. For the first time, the four-component system LiF-NaF-K2WO4-CaF2, a stable secant complex of the given five-component system, has been studied and the coordinates of the invariant point have been determined using the differential thermal analysis (DTA), the visual poly- thermal analysis (VPA), the X-ray phase analysis (XPA), and the projection-thermographic method (PTGM). The mu- tual salt pair matrix was used to find stable and metastable complexes, left and right part schemes of the four- component system reaction equations.
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