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Thermodynamic assessment of the phase stability of the solid solutions of superionic alloys of the Ag3SBr1-xClx(I) system in the concentration range 0 ≤ x ≤ 0.4 and temperature range 370–395 K was performed. Partial functions of silver in the alloys of solid solution were used as the thermodynamic parameters. The values of partial thermodynamic functions were obtained with the use of the electromotive force method. Potential-forming processes were performed in electrochemical cells. Linear dependence of the electromotive force of cells on temperature was used to calculate the partial thermodynamic functions of silver in the alloys. The serpentine-like shape of the thermodynamic functions in the concentration range 0–4 is an evidence of the metastable state of solid solution. The equilibrium phase state of the alloys is predicted to feature the formation of the intermediate phase Ag3SBr0.76Cl0.24, and the solubility gap of the solid solution ranges of Ag3SBr0.76Cl0.24and Ag3SBr.
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