Multiple Crossed Isopolymorphism;Two-Component Systems CC14+CBr2Cl2 and CBrCl3+CBr2Cl2;Inference of a Metastable Rhombohedral Phase of CBr2Cl2

摘要

The phases diagrams of the two-component systems CC14+CBr2Cl2 and CBrCl3+CBr2Cl2 have been determined by means of X-ray powder diffraction and thermal analysis techniques from the low-temperature ordered phase to the liquid state.The isomorphism relationship between the stable orientationally disordered (OD) face-centered cubic (FCC) phases of CBrCl3 and CBr2Cl2 and the metastable OD FCC phase (monotropic behavior with respect to the OD rhombohedral stable phase) of CCU has been put into evidence throughout the continuous evolution of the lattice parameters and the existence of the two-phase equilibrium [FCC+L] for the whole range of composition in both two-component systems.This equilibrium interferes,for the CCU+CBr2Cl2 system,with a rhombohedral (R) plus liquid ([R+L]) equilibrium giving rise to a peritectic invariant.In addition,whatever the system,[R+FCC] equilibrium also interferes with the low-temperature equilibria between the low-temperature monoclinic (C2/c) phase and the OD R and FCC phases.In regards to the low-temperature monoclinic phases,isomorphism is evidenced,and by means of Rietveld profile refinement,any ordering of the molecules by varying the fractional occupancy of the halogen sites has been detected.The thermodynamic assessment,conducted by means of the concept of crossed isopolymorphism,coherently reproduces all the involved equilibria and provides a coherent set of data for the thermodynamic properties of nonexperimentally available phase transitions of pure compound CBr2Cl2 which enables us to obtain the topological properties of its pressure-temperature phase diagram and to infer the existence of a high-pressure R phase for such a compound.