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Cranswick, Lachlan M. D.
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article
Synthesis and thermal decomposition of tetragonal RbClO4 and volume of fluid O2 from 2 to 9 GPa
Abstract
<p>Orthorhombic (O) RbClO<sub>4</sub> transforms to a new tetragonal (T) form at pressures above 20 kbar. Thermal decomposition proceeds through the reversible equilibrium reaction T RbClO<sub>4</sub> = B2 RbCl + 2O<sub>2</sub> at modestly increasing temperatures centered ∼550°C over the pressure range investigated from 20 to 90 kbar. Cell volumes for T RbClO<sub>4</sub> and B2 RbCl were determined by high-pressure, high-temperature, in situ X-ray diffraction on station 16.4 of the Daresbury Synchrotron Radiation Source, from which the partial molar volume of O<sub>2</sub> along the decomposition curve was determined. This volume (∼10 cm<sup>3</sup>/mol) is in close agreement with volumes determined from studies of the thermal decomposition of KClO<sub>3</sub> and KClO<sub>4</sub> but is difficult to reconcile with fluid O<sub>2</sub> volumes determined using shock wave techniques. If these new O<sub>2</sub> partial molar volumes are relevant to molten iron solutions, then storage of substantial amounts of O<sub>2</sub> in the core becomes feasible.</p>