Cystalline modifications and structural phase transitions of NaOH and NaOD

Structural work on the three modifications of sodium hydroxide is reviewed. The monoclinic and cubic modifications were determined with neutron and X-ray diffraction, respectively. The phase-transition temperatures were determined by specific-heat measurements. The cubic to monoclinic transition is a first-order transition with a freezing of the rotational motion of the OH (and OD) groups. The monoclinic axes a, b and c* tend to be oriented parallel to the original cubic directions [{ 1}{ 1}2], [1{ 1}0] and [ 111], respectively. The orthorhombic to monoclinic transition is a nearly continuous displacive phase transition with a soft acoustic shear mode. The order parameter is the homogeneous shear of the crystal in the a direction. Its temperature dependence is described within Landau theory.