Polymorphism of CBrCl3

The polymorphism of bromotrichloromethane (CBrCl3) has been investigated by X-ray powder diffraction and high-pressure density experiments. Phase transitions as a function of temperature and pressure between the different phases have been characterized at normal pressure as well as at high pressures (up to 300 MPa). From the p−v−T diagram (and the derived p−T diagram) the volume variations at the transition points have been calculated and compared with those obtained by means of X-ray powder diffraction characterization. Special attention is given to the lattice symmetry of the orientational disordered phase II, characterized as rhombohedral (a = 14.639(8) Å, α = 89.44(1)° at 240.2 K). The existence of a glass transition from the monoclinic low-temperature stable ordered phase (III) to its nonergodic state (associated with the freezing of exchange positions between Cl and Br atoms) is analyzed in terms of the asymmetry of the intermolecular interactions, and a new “fingerprint” for the glass transition is proposed on the basis of the aspherism index. Lattice parameters as a function of temperature were determined in order to build up the thermal expansion tensor.