Аннотация:The emf technique with liquid electrolyte solves a fundamental problem for complete thermodynamic analysis of equilibrium phase diagrams. It gives not only the experimental set of the thermodynamic values: relative chemical potential and Gibbs energy, partial and integral enthalpies and entropies of formation of phases, enthalpy of phase transitions, enthalpy at infinite dilution, and capacity but also it permits to study the lines of liquidus and solidus, miscibility gap and invariant points, order-disorder transformation at large temperature and concentration intervals.
We show the universality and self-sufficiency of the method for the systems which were studied. Emf remains one of the most important methods in metallurgical thermodynamics. The main experimental steps which are involved: alloy synthesis, salt mixture dehydration, pure molten salt and salt ingot preparations, and cell assembly.
We applied this technique successfully to the following systems:
binaries : Tl-S, Tl-Se, Tl-Te; Cd-Te; Pb-Pd; In-P; In-Sn; In-Sb; Sn-Sb; Bi-Se; Mn-Te; Rare Earth Metals (REM) with In, Sb, Pb, Te;
ternaries : Cd-Hg-Te; In-Sn-Sb; Pb-Sn-Sb; Pb-Sn-Zn; In-Bi-Ag; In-Ni-Sb; Pb-Cu-Zn; Pb-In-Zn.
We cite as examples the two classic systems: Pb-Pd [1] et HgTe-CdTe [2].
[1] Vassiliev V. Voronin G.F. Borzone G. Mathon M., Gambino M. Bros J.P. Thermodynamics of the Pb-Pd system. J.Alloys Comp. 269, 123 -132 (1998).
[2] Vassiliev V.P., Pentine I.V., Voronine G.F. Conditions of the thermodynamic stability of solid solution CdTe-HgTe // J. Phys.IV France 113, 97-100 (2004).