The polymorphism of Ba(OH)(2) described in the literature, has been in
vestigated by crystallographic, infrared spectroscopic, and calorimetr
ic techniques. From the X-ray powder diffraction pattern it has been f
ound that the beta phase has a monoclinic structure (space groups P2(1
) or P2(1)/m) with a = 6.7835(6), b = 7.9268(6), c = 9.4246(10) Angstr
om and beta = 95.823(9)degrees. A phase transformation to alpha-Ba(OH)
(2) occurs at 526 +/- 1 K, which upon cooling in a dry atmosphere rema
ins unchanged. However, a reversible phase transition alpha --> beta i
s observed in the presence of traces of water vapour, acting as a cata
lyst. The thermodynamic properties of alpha-Ba(OH)(2), including fusio
n, have been measured. In addition, the fusion properties of Sr(OH)(2)
are discussed.