There is great current interest in understanding interactions between H2O and its components and various Earth materials. Here, questions such as the bulk water content of the mantle, and what phases can incorporate OH- and in what concentrations come immediately to mind. In this regard, the hydrogarnet substitution (i.e., O4H4↔SiO4) has received special attention, because it is a verified mechanism for allowing the incorporation of OH- in garnet and possibly in other silicates as well. At relatively low temperatures there is complete solid solution between Ca3Al2Si3O12 and Ca3Al2O12H12. The latter, pure OH-containing end-member is termed katoite/hydrogrossular. Its crystal structure has been investigated by various workers using X-ray and neutron diffraction, including at high pressures. Little is known about its vibrational properties and its thermodynamic behavior is not fully understood. Thus, we studied the low temperature IR spectra and measured the heat capacity of katoite in order to investigate its vibrational, crystal-chemical and thermophysical properties. Katoite was synthesized hydrothermally in Au capsules at 250 °C and 3 kb water pressure. X-ray powder measurements show that about 98-99% katoite was obtained. Powder IR spectra were recorded between 298 K and 10 K. The spectra are considerably different in the high wavenumber region, where O-H stretching modes occur. At room temperature the IR-active O-H band located around 3662 cm-1 is broad and it narrows and shifts to higher wavenumbers and also develops structure below about 80 K. Concomitantly, additional weak intensity O-H bands located around 3600 cm-1 begin to appear and they become sharper and increase in intensity with further decreases in temperature. The spectra indicate that the vibrational behavior of individual OH groups and their collective interactions measurably affect the lattice dynamic (i.e. thermodynamic) behavior. The low temperature heat capacity behavior was investigated with a relaxation calorimeter between 5 and 300 K on a mg-sized sample. The heat capacity data are well behaved at T < 300 K and show a monotonic decrease in magnitude with decreasing temperature. A standard third-law entropy value of S° = 421.7 ± 1.6 J/mol.K was calculated. Using this new calorimetric-based S° value and published standard enthalpy of formation data for katoite, a calorimetric-based Gibbs free energy of formation at 298 K can be obtained as ∆G°f = -5021.2 kJ/mol. The Cp data show no evidence for any phase transition as possibly expected by the change in OH-mode behavior with decreasing temperature. It is worth noting that the katoite, in terms of lattice dynamic or thermodynamic behavior, should be thought of having OH groups and not O4H4 clusters or polyhedral units as is often written in the literature. The single crystallographic OH group in katoite shows very weak, if any, hydrogen bonding and the H atoms have large amplitudes of vibration. Very weak H bonding or the lack of it affects the nature of low energy OH-related vibrations and this leads to katoite's large S° value.
AGU Fall Meeting Abstracts
- Pub Date:
- December 2011
- 1011 GEOCHEMISTRY / Thermodynamics;
- 1030 GEOCHEMISTRY / Geochemical cycles;
- 3934 MINERAL PHYSICS / Optical;
- and Raman spectroscopy