Kinetic study of the dehydroxylation of chrysotile asbestos with temperature by in situ XRPD

 The kinetics of the dehydroxylation of chrysotile was followed in situ at high temperature using real-time conventional and synchrotron powder diffraction (XRPD). This is the first time kinetics parameters have been calculated for the dehydroxylation of chrysotile. The value of the order of the reaction mechanism calculated using the Avrami model indicates that the rate-limiting step of the reaction is a one-dimensional diffusion with an instantaneous nucleation or a deceleratory rate of nucleation of the reaction product. Hence, the rate-limiting step is the one-dimensional diffusion of the water molecules formed in the interlayer region by direct condensation of two hydrogen atoms and an oxygen atom. The calculated apparent activation energy of the reaction in the temperature range 620–750 °C is 184 kJ mol⁻¹. The diffusion path is along the axis of the fibrils forming the fibers. The amorphous or short-range ordered dehydroxylate of chrysotile is extremely unstable because forsterite readily nucleates in the Mg-rich regions. Moreover, it is less stable than the dehydroxylate of kaolinite, the so-called metakaolinite, which forms mullite at about 950 °C. This difference is interpreted in terms of the different nature of the two ions Mg²⁺ and Al³⁺ and their function as glass modifier and glass-forming ion, respectively. Received: 10 April 2002 / Accepted: 7 January 2003 Acknowledgements This work is part of a COFIN project (04 Scienze della Terra, NR 17, 2000) supported by MURST. Dr Dapiaggi is kindly acknowledged for help during the data collection at the Dipartimento di Scienze della Terra, University of Milan.     

In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite,FeOH(SO<Subscript>4</Subscript>)·5H<Subscript>2</Subscript>O

The thermal dehydration process of fibroferrite, FeOH(SO₄)·5H₂O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO₄)·4H₂O, appearing at about 80 °C due to release of one interstitial H₂O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.     

Kinetic study of the kaolinite-mullite reaction sequence. Part II: Mullite formation

The present work is a follow-up of the investigation on the decomposition reaction of kaolinite as a function of the defectivity of the starting material and the temperature of reaction. In the present work we study the high temperature reaction of mullite synthesis from kaolinite, from the starting point of the results obtained in the first part.Time resolved energy-dispersive powder diffraction patterns have been measured using synchrotron radiation in isothermal conditions. The apparent activation energy for mullite nucleation and growth is found to be related to the defective structure of the starting kaolinite, which thus must have an influence on the chemical homogeneity of the amorphous intermediate phase.     

Kinetic study of the kaolinite-mullite reaction sequence. Part I: Kaolinite dehydroxylation

The decomposition reaction of kaolinite has been investigated as a function of the defectivity of the starting material and the temperature of reaction. Time resolved energy-dispersive powder diffraction patterns have been measured using synchrotron radiation, both under a constant heating rate (heating rates from 10 to 100° C/min) and in isothermal conditions (in the temperature range 500 to 700° C). The apparent activation energy of the dehydroxylation process is different for kaolinites exhibiting a different degree of stacking fault density. The results of the analysis of the kinetic data indicate that the starting reaction mechanism is controlled by diffusion in the kaolinite particle. The diffusion process is dependent on the defective nature of both kaolinite and metakaolinite. At high temperatures, and at higher heating rates, the reaction mechanism changes and the resistance in the boundary layer outside the crystallites becomes the rate-limiting factor, and nucleation begins within the reacting particle. During the final stage of the dehydroxylation process the reaction is limited by heat or mass transfer, and this might be interpreted by the limited diffusion between the unreacted kaolinite domains and the metakaolinite matrix.     

Trace elements and the panspermia hypotheses

The modal concentrations of elements in four representative classes of organisms, namely bacteria, fungi, plants, and land animals, are compared with the concentrations of the elements in sea water. A strong correlation is found between these concentrations, and this correlation reduces to an expected linear concentration law when only “trace” elements are considered. Deviations from strict linearity are shown to arise from the chemical natures of the elements Apart from suggesting an oceanic genesis for terrestrial life, the data are strongly against a nonterrestrial origin of life as proposed by the panspermia hypotheses.     

Spatially resolved methane band photometry of Saturn: I. Absolute reflectivity and center-to-limb variations in the 6190-, 7250-, and 8900-Å bands

We present spatially resolved measurements of Saturn's absolute reflectivity in methane bands at 6190, 7250, and 8900 Å and in nearby continuum regions. Images were obtained through narrow-band interference filters with a 500 × 500-pixel charge-coupled device. Band/continuum ratios were measured to high accuracy by referencing to the ring brightness in each image. Several data processing techniques enhanced the quality of the observations. These are the use of the ring symmetry to find center position and orientation, accurate subtraction of ring light, and constrained image deconvolution. Uncertainty in the continuum absolute reflectivity is ±10%. Uncertainties in band/continuum ratios are from one to several percent. The Equatorial Zone was much brighter than any other latitude in the strong 8900 band image. Northern mid-latitudes were brighter than southern mid-latitudes. The latter observation indicates fewer high-altitude aerosols in the south, a possible result of atmospheric dynamics or seasonal sublimation of NH₃ crystals. The data are tabulated and presented in a form suitable for quantitative scattering model analyses.     

High temperature dehydroxylation of muscovite-2M1: a kinetic study by in situ XRPD

Muscovite-2M₁ shows a major phase transition at about 800°C, which is generally attributed in the literature to the structural dehydroxylation process, although a number of structural models have been proposed for the dehydroxylated phase, and different transformation mechanisms have also been put forward. The observed first order transformation involves an increase in the cell volume, and it is not clear to date how the cell expansion is related to the loss of hydroxyl groups. The phase change has been re-investigated here by in situ high temperature powder diffraction, both in non-isothermal and isothermal modes, to combine for the first time the structural and the kinetic interpretation of the transformation. The results unequivocally confirm that the reaction taking place in the temperature range 700–1000°C is truly a dehydroxylation process, involving the nucleation and growth of the high temperature dehydroxylated phase, having Al in 5-fold coordination. Structural simulations of the basal peaks of the powder diffraction patterns indicate that the model originally proposed by Udagawa et al. (1974) for the dehydroxylated phase correctly describes the high temperature phase. The kinetic analysis of the isothermal data using an Avrami-type model yields values for the reaction order compatible with a reaction mechanism limited by a monodimensional diffusion step. Apparent activation energy of the process in vacuum is about 251 kJ/mol. Experiments carried out at temperatures much higher than the onset temperature of the reaction show that the dehydroxylation reaction overlaps with the reaction of formation of mullite, the final product in the reaction pathway. Received: 24 April 1998 / Revised, accepted: 12 October 1998     

The thermal stability of sideronatrite and its decomposition products in the system Na2O–Fe2O3–SO2–H2O

The thermal stability of sideronatrite, ideally Na₂Fe³⁺(SO₄)₂(OH)·3(H₂O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na₃Fe(SO₄)₃ compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe³⁺(SO₄)₂(OH)] _∞ ^2? chains and the formation of an intermediate transient amorphous phase precursor of Na₃Fe(SO₄)₃. (d) for T > 500 °C, the Na₃Fe(SO₄)₃ compound is replaced by the Na-sulfate thenardite, Na₂SO₄, plus Fe-oxides, according to the Na₃Fe³⁺(SO₄)₃ → 3/2 Na₂(SO₄) + 1/2 Fe₂O₃ + SO_x reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.     

Book reviews

AUSTRALIA AND ITS URBAN “CENTRES (Urbanization of the Earth No. 6) by B. Hofmeister. 19 × 28 cm, xii and 254 pages. Gebruder Borntraeger: Berlin 1988 (ISBN 3 443 37008 X) DM130 (hard).

CONTEMPORARY AUSTRALIA: Explorations in Economy, Society and Geography by D. J. Walmsley and A. D. Sorenson. 19 × 25 cm, xxiv and 328 pages. Longman Cheshire: Melbourne 1988 (ISBN 0 58271150 9) $A29.95 (soft).

WATERING THE GARDEN STATE: Water, Land and Community in Victoria 1834–1988 by J. M. Powell. 16 × 24 cm, xv and 319 pages. Allen & Unwin: Sydney 1989 (ISBN 0 04 3600 74 3) SA39.95 (hard); (ISBN 0 04 364024 9) SA24.95 (soft).

THE BUREAUCRATS DOMAIN. Space and the Public Interest in Victoria 1836–1884 by R. Wright. 15 × 23 cm, xv and 350 pages. Oxford University Press: Melbourne 1989 (ISBN 0 19 554866 3) $A39.95 (hard).

SOUTHERN APPROACHES: Geography in New Zealand edited by P. G. Holland and W. B. Johnston. 17 × 25 cm, 361 pages. New Zealand Geographical Society: Christchurch 1987 (ISBN 0 9597 863 0 9) $A56.50 (soft).