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Rules of molten salt phase diagrams of binary system MeX-Me’X4 (Me is monovalent metal, Me’ quadrivalent metal, X halides) were investigated using chemincal bond parameter and pattern recognition-artificial neural networks method. Formability of intermediate compounds, chemical stiochiometry, melting type (congruent or incongruent) of intermediate compounds Me2Me’X6 and MeMe’X5 were summarized and predicted, the results were of good reliability.