8-FeOOH dehydroxylation

Synthetic 5-FeOOH has a surface area which ranges from 20-300 m g depending on the thickness of the crystals. In a series of seven synthetic feroxyhytes the surface area increased from 140 to 240 m g (EGME method) as the crystallinity decreased (Garlson and Schwertmann, 1980). 5-EeOOH displays interpartide porosity, i.e. slitshaped micro- or mesopores between the plate like crystals (Jimenez-Mateos et al., 1988 Ishikawa et al., 1992). Both TEM observations and t-plot analysis showed that 0.8 nm micropores formed upon dehydroxylation at 150 °G in vacuo. The surface area rose steeply as the temperature exceeded 100 °G and reached a value close to 150 m g at 200 °C at which temperature, the sample was completely converted to hematite. 

The surface area of synthetic hematite depends upon whether the oxide was produced by calcination or grown in solution. The temperature of (dry) heating influences the surface area. Hematites produced at 800-900 °C have areas < 5 m g due to sintering of the particles. Hematites obtained by dehydroxylation of the various polymorphs of FeOOH or ferrihydrite at temperatures lower than 500-600 °C are mesoporous and have much higher surface areas - up to 200 m g". Commercial hematites are usually produced by calcination and hence have a low surface area. 

The end product of the dehydroxylation of pure phases is, in all cases, hematite, but with lepidocrocite, maghemite occurs as an intermediate phase. The amount of water in stoichiometric FeOOH is 10.4 g kg , but adsorbed water may increase the overall amount released. Thermal dehydroxylation of the different forms of FeOOH (followed by DTA or TG) takes place at widely varying temperatures (140-500 °C) depending on the nature of the compound, its crystallinity, the extent of isomorphous substitution and any chemical impurities (see Fig. 7.18). Sometimes the conversion temperature is taken from thermal analysis data (e. g. DTA), but because of the dynamic nature of the thermoanalysis methods, the temperature of the endothermic peak is usually higher than the equilibrium temperature of conversion. 

A common feature of the dehydroxylation of all iron oxide hydroxides is the initial development of microporosity due to the expulsion of water. This is followed, at higher temperatures, by the coalescence of these micropores to mesopores (see Chap. 5). Pore formation is accompanied by a rise in sample surface area. At temperatures higher than ca. 600 °C, the product sinters and the surface area drops considerably. During dehydroxylation, hydroxo-bonds are replaced by oxo-bonds and face sharing between octahedra (absent in the FeOOH structures see Chap. 2) develops and leads to a denser structure. As only one half of the interstices are filled with cations, some movement of Fe atoms during the transformation is required to achieve the two thirds occupancy found in hematite. 

Hematite derived from dehydroxylation of FeOOH at temperatures below 600 °C shows marked, non-uniform (differential) broadening of the XRD lines. Some authors have attributed this effect to the anisotropic shape of the coherently diffracting domains of hematite (Duvigneaud Derie, 1980), and others to the development... 

Thermal dehydroxylation of FeOOH has been studied both in vacuum and under various atmospheres. Kinetic studies of these transformations must be carried out under vacuum (Giovanoli Briitsch, 1974) and at a constant temperature. The temperature at which a phase transformation occurs, however, is determined by increasing the temperature of the sample in a controlled manner, i.e. by using a thermobalance (DTA or TGA method, see Ghap. 7). Mechanical and mechanochemical dehydroxylation of FeOOH at room temperature can also be achieved by grinding. 

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