Phase transition of potassium sulfate,K2SO4 (III); thermodynamical and phenomenological study

The orthorhombic-hexagonal phase transition of K₂SO₄ has been investigated by measurements of the temperature dependencies of the specific heat, expansion, and X-ray intensity of superstructure reflections, correlated with the structural point of view. The values of the net enthalpy and entropy changes are ΔH=4.28 KJ/mol and ΔS=4.98 J/mol·K at the phase transition temperature (587°C), respectively. The thermal expansion along the c axis shows strong anisotropic character above about 300°C and exhibits a very large discontinuous increase at 587°C, whereas those along the a and b axes increase linearly and exhibit small discontinuous decreases at 587°C. The X-ray intensity of superstructure reflections in the low-temperature form gradually decrease with increasing temperature, and come to extinction at 587°C, exhibiting a discontinuity. The observed entropy change and pressure dependence of the phase transition temperature were explained successfully by the use of results of the structural analysis and measured physical properties. The temperature dependencies of the spontaneous strain, X-ray intensity of superstructure reflection, and birefringence were consistently described by introducing a transition parameter on the basis of an instability at the M point in the Brillouin zone of the hexagonal phase.     

Geneses of Two Types of Mafic Rocks to Carry Placer‐Magnetite Ores in the Sanin Granitic Belt,SW Japan

Two types of mafic rocks from the central Sanin district, and their mafic minerals, were studied chemically and microscopically. They are classified into pyroxene‐containing gabbroid and hornblende–biotite quartz diorite. The gabbroid had higher color index but lower magnetite content; while the quartz diorite had lower color index, but higher magnetite content. The magnetite contents are also related to the amounts of hydrous mafic silicates. The gabbroic magma having pyroxene–amphibole assemblage, originated in the upper mantle, was considered essentially anhydrous, but became partly hydrous on the way to the site of solidification in the continental crust, and crystallized some magnetites with hypersthene and amphibole. The quartz dioritic magma was formed by partial melting of possibly subducting ocean‐floor basalts, once exposed to the sea‐floor then altered; thus the magmas became hydrous and oxidized originally, and precipitated abundant magnetite and hydrous mafic silicates from the early crystallization stage onward. Their weathered parts provided the most placer magnetite ores in the history.