Phase barograms–phase diagrams of vapor pressure: Eutectoid phase formation in binary systems

Phase barograms are specific representations of conventional (x, T) phase diagrams considering the vapor pressure as additional thermodynamic parameter. Thus, the determination of the vapor pressure is complementary to conventional DTA or DSC measurements. A stringent relationship between the phase diagram and the corresponding phase barogram is derived by thermodynamic considerations of phase relations for complex heterogeneous equilibria. For that purpose, a derivative of the three-dimensional Clausius–Clapeyron equation is utilized. As a result, a validation of DTA/DSC measurements becomes feasible by the transformation of characteristic effects of vapor pressure measurements into thermal effects in conventional phase diagrams.The system CsBr/SeO2 is presented as a case study of systems with a eutectoid phase formation. CsSeO2Br is formed from the binaries at ϑf = 180(5) °C; the compound decomposes peritectically at ϑp = 470(10) °C.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Thermodynamic considerations of complex heterogeneous equilibria. ► Derivative of the three-dimensional Clausius–Clapeyron equation. ► Relationship between phase diagram and related phase barogram. ► Transformation of thermal effects of vapor pressure measurements. ► Eutectoid phase formation CsSeO2Br in the system CsBr/SeO2.