Kristy L. Erickson

Thermal decomposition of natural iowaite

The thermal decomposition of natural iowaite of formula Mg6Fe2(Cl,(CO3)0.5)(OH)16·4H2O was studied by using a combination of thermogravimetry and evolved gas mass spectrometry. Thermal decomposition occurs over a number of mass loss steps at 60°C attributed to dehydration, 266 and 308°C assigned to dehydroxylation of ferric ions, at 551°C attributed to decarbonation and dehydroxylation, and 644, 703 and 761°C attributed to further dehydroxylation. The mass spectrum of carbon dioxide exhibits a maximum at 523°C. The use of TG coupled to MS shows the complexity of the thermal decomposition of iowaite.

Use of Infrared Spectroscopy for the Determination of Electronegativity of Rare Earth Elements

Infrared spectroscopy has been used to study a series of synthetic agardite minerals. Four OH stretching bands are observed at around 3568, 3482, 3362, and 3296 cm−1. The first band is assigned to zeolitic, non-hydrogen-bonded water. The band at 3296 cm−1 is assigned to strongly hydrogen-bonded water with an H bond distance of 2.72 A. The water in agardites is better described as structured water and not as zeolitic water. Two bands at around 999 and 975 cm−1 are assigned to OH deformation modes. Two sets of AsO symmetric stretching vibrations were found and assigned to the vibrational modes of AsO4 and HAsO4 units. Linear relationships between positions of infrared bands associated with bonding to the OH units and the electronegativity of the rare earth elements were derived, with correlation coefficients >0.92. These linear functions were then used to calculate the electronegativity of Eu, for which a value of 1.1808 on the Pauling scale was found.

Studies of natural and synthetic agardites

Agardite of formula [(Al, Nd, REE)Cu(AsO) (OH)·3HO] has been discovered at Cobar, New South Wales, Australia. A series of synthetic agardites were analysed by X-ray diffraction and a correlation exists between the effective ionic radius of the REE in the M site and the unit cell size for each respective agardite mineral. No value for the effective ionic radius of 9-coordinate Bi has been reported but a value of approximately 115.5 pm is estimated from this correlation. The results of the TGA analyses show that the synthetic agardites are all fully hydrated, i.e., n = 3. Near infrared spectroscopy and mid- infrared spectroscopy has been used to characterise a group of synthetic agardites of formula ACu (AsO)(OH)· 3HO where A is a rare earth element. The hydroxyl stretching region is characterised by four bands observed at around 3568, 3489, 3382 and 3290 cm. The first two bands are attributed to the stretching mode of hydroxyl units and the last two bands to water stretching vibrations. The position of these bands indicates strongly hydrogen bonded water. The water in agardites is zeolitic type water. Near-IR spectroscopy shows a series of bands at 7242, 7007, 6809, 6770 and 6579 cm attributed to the first overtones of the hydroxyl fundamentals. The NIR spectrum of agardite (Sm) is different and may be affected by electronic bands. Combination bands are observed at around 4404, 4343, 4340, 4294 and 4263 cm. Bands attributed to water combination modes are found at around 5200, 5173, 5082 and 4837 cm. Agardites are a group of minerals known for their REE content and have been rarely studied. NIR spectroscopy is an excellent technique for the characterisation and ready identification of these minerals.