Mineral polymorphism

Mineral polymorphs of this type are the usual sort of geochemical examples used to define metastable equilibria, and the usual definition centers on the fact that the metastable phase has a higher energy content than the stable phase. By focusing on the constraint that prevents the metastable phase from changing to the stable phase, we have not changed the concept of metastability but have simply broadened its applicability, as shown in the other examples. The perfect analogy between the partitioned gas example and the polymorph example should demonstrate the utility of the extra constraint definition we have used. 

In addition to the three principal polymorphs of siUca, three high pressure phases have been prepared keatite [17679-64-0] coesite, and stishovite. The pressure—temperature diagram in Figure 5 shows the approximate stabiUty relationships of coesite, quart2, tridymite, and cristobaUte. A number of other phases, eg, siUca O, siUca X, sihcaUte, and a cubic form derived from the mineral melanophlogite, have been identified (9), along with a stmcturaHy unique fibrous form, siUca W. 

Australia, is the doyen of materials scientists who study the elastic and plastic properties of minerals under hydrostatic pressure and also phase stability under large shear stresses (Paterson 1973). J.-P. Poirier, in Paris, a professor of geophysics, was trained as a metallurgist one of his special skills is the use of analogue materials to help understand the behaviour of inaccessible high-pressure polymorphs, e.g., CaTi03 perovskite to stand in for (Mg, FelSiOi in the earth s mantle (Poirier 1988, Besson el al. 1996). 

In the vapour phase As is known to exist as tetrahedral Asa molecules with (As-As 243.5 pm) and when the element is sublimed, a yellow, cubic modification is obtained which probably also contains Asa units though the structure has not yet been determined because the crystals decompose in the X-ray beam. The mineral arsenolamprite is another polymorph, e-As it is possibly isostructural with metallic orthorhombic P. 

HgS is polymorphic. The red a-form is the mineral cinnabar, or vermilion, which has a distorted rock-salt structure and can be prepared from the elements. )3-HgS is the rare, black, mineral metacinnabar which has the zinc-blende structure and is converted by heat to the stable a-form. In the laboratory the most familiar form is the highly insoluble black precipitate obtained by the action of HzS on aqueous solutions of Hg. HgS is an unreactive substance, being attacked only by cone HBr, HI or aqua regia. HgSe and... 

Pressure-induced phase transitions in the titanium dioxide system provide an understanding of crystal structure and mineral stability in planets interior and thus are of major geophysical interest. Moderate pressures transform either of the three stable polymorphs into the a-Pb02 (columbite)-type structure, while further pressure increase creates the monoclinic baddeleyite-type structure. Recent high-pressure studies indicate that columbite can be formed only within a limited range of pressures/temperatures, although it is a metastable phase that can be preserved unchanged for years after pressure release Combined Raman spectroscopy and X-ray diffraction studies 6-8,10 ave established that rutile transforms to columbite structure at 10 GPa, while anatase and brookite transform to columbite at approximately 4-5 GPa. 

Mercuric sulfide (HgS) is dimorphic. The more common form, cinnabar (red a-form), has a distorted RS, trigonal structure which is unique among the monosulfides, for the crystal is built of helical chains in which Hg has two nearest neighbors at 2.36 A, two more at 3.10 A, and two at 3.30 A. Bulk a-HgS is a large-gap semiconductor (2.1 eV), transparent in the red and near IR bands. The rare, black mineral metacinnabarite is the 3-HgS polymorph with a ZB structure, in which Hg forms tetrahedral bonds. Upon heating, 3-HgS is converted to the stable a-form. The ZB structure of HgS is stabilized under a few percent admixture of transition metals, which replace Hg ions in the lattice. 

In the previous paragraph, it has been stated that minerals have the same structure but different compositions (phenomenon of isomorphism of minerals) while some minerals have the same composition but different structures (phenomenon of polymorphism of minerals). Mineral composition and structure are both important in studying and classifying minerals. The major class of minerals - based on composition and structure - include elements, sulfides, halides, carbonates, sulfates, oxides, phosphates, and silicates. The silicate class is especially important, because silicon makes up 95% of the minerals, by volume, in the Earth s crust. Mineral classes are divided into families on the basis of the chemicals in each mineral. Families, in turn, are made of groups of minerals that have a similar structure. Groups are further divided into species. 

Applications The general applications of XRD comprise routine phase identification, quantitative analysis, compositional studies of crystalline solid compounds, texture and residual stress analysis, high-and low-temperature studies, low-angle analysis, films, etc. Single-crystal X-ray diffraction has been used for detailed structural analysis of many pure polymer additives (antioxidants, flame retardants, plasticisers, fillers, pigments and dyes, etc.) and for conformational analysis. A variety of analytical techniques are used to identify and classify different crystal polymorphs, notably XRD, microscopy, DSC, FTIR and NIRS. A comprehensive review of the analytical techniques employed for the analysis of polymorphs has been compiled [324]. The Rietveld method has been used to model a mineral-filled PPS compound [325]. 

Different modifications of a compound are frequently designated by lower case Greek letters a, j3,..., e.g. a-sulfur, j3-sulfur, or by roman numerals, e.g. tin-I, tin-II etc. Polymorphic forms of minerals have in many cases been given trivial names, like a-quartz, P-quartz, tridymite, cristobalite, coesite, keatite, and stishovite for Si02 forms. 

Any two samples of a particular mineral, whatever their source or place of origin, have the same basic composition and characteristic crystal structure moreover, no two different minerals have identical chemical composition and crystal structure (see Textboxes 8 and 21). Quartz, for example, is a common and abundant mineral composed of silicon dioxide, a compound that occurs naturally not only as quartz but also in other crystal structures, known as polymorphs (polymorphs are minerals that have the same chemical composition but different crystal structure), some of which, listed in Table 23, have been used for a variety of purposes. The crystal structure, which is essential for the characterization of solid materials, is just one of a wide range of physical properties, that is, properties not involving chemical differences, which provide convenient criteria for characterizing and identifying solids. 

Lucotte G, Mercier G, Burckel A. The vitamin D receptor FokI start codon polymorphism and bone mineral density in osteoporotic postmenopausal French women. Clin Genet 1999 56[3] 221 224. 

As a second example, we choose quartz (or any silica polymorph) as a component for a system containing an aqueous fluid and quartz. Now the mole number for the quartz component includes not only the silica in the quartz mineral, the real quartz, but the silica in solution in species such as SiC>2(aq) and IGSiO. Again, the mole numbers of component quartz and real quartz are not the same. A common mistake in geochemical modeling is confusing the components used to describe the composition of a system with the species and phases that are actually present. 

From a plot of the saturation states of the silica polymorphs (Fig. 23.7), the fluid s equilibrium temperature with quartz is about 100 °C. Quartz, however, is commonly supersaturated in geothermal waters below about 150 °C and so can give erroneously high equilibrium temperatures when applied in geothermometry (Fournier, 1977). Chalcedony is in equilibrium with the fluid at about 76 °C, a temperature consistent with that suggested by the aluminosilicate minerals. 

They made several assumptions about which minerals could precipitate from the fluid. The alkaline lakes tend to be supersaturated with respect to each of the silica polymorphs (quartz, tridymite, and so on) except amorphous silica, so they suppressed each of the other silica minerals. They assumed that... 

By suppressing the other silica polymorphs, we prevent them from forming in the calculation. We will show, however, that except at large At these minerals tend to become supersaturated in the low-temperature end of the fracture. In reality, therefore, these minerals would be likely to form within the fracture under such conditions. 

Ostwald s step rule holds that a thermodynamically unstable mineral reacts over time to form a sequence of progressively more stable minerals (e.g., Morse and Casey, 1988 Steefel and Van Cappellen, 1990 Nordeng and Sibley, 1994). The step rule is observed to operate, especially at low temperature, in a number of min-eralogic systems, including the carbonates, silica polymorphs, iron and manganese oxides, iron sulfides, phosphates, clay minerals, and zeolites. 

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