Stishovites

Crystalline Silica. Sihca exists in a variety of polymorphic crystalline forms (23,41—43), in amorphous modifications, and as a Hquid. The Hterature on crystalline modifications is to some degree controversial. According to the conventional view of the polymorphism of siHca, there are three main forms at atmospheric pressure quart2, stable below about 870°C tridymite, stable from about 870—1470°C and cristobaHte, stable from about 1470°C to the melting point at about 1723°C. In all of these forms, the stmctures are based on SiO tetrahedra linked in such a way that every oxygen atom is shared between two siHcon atoms. The stmctures, however, are quite different in detail. In addition, there are other forms of siHca that are not stable at atmospheric pressure, including that of stishovite, in which the coordination number of siHcon is six rather than four. 

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. 

Stishovite. Stishovite was first prepared (68) ia the laboratory ia 1961 at 1200—1400°C and pressures >16 GPa (158,000 atm). It was subsequentiy discovered, along with natural coesite, ia the Ari2ona meteor crater. It has been suggested that these minerals are geological iadicators of meteorite impact stmctures. Stishovite (p = 4.35 g/cm ) is the densest known phase of silica. The stmcture, space group P42/nmn is similar to that of... 

High-pressure stishovite phase data (Wackerle, 1962 Marsh, 1980 Jones et al., 1972 and Trunin et al., 1971). 

Figure 4.12. Shock velocity versus particle velocity for fused quartz. Three regimes are indicated low pressure, fused quartz regime, the mixed phase regime, and the high-pressure phase, stishovite regime.

Figure 4.15. Shock pressure versus specific volume for calcia and fused quartz indicating three regimes fused quartz, low-pressure regime is fused quartz, mixed phase regime, and high-pressure regime representing stishovite. In the case of calcia, the low-pressure phase is the B1 structure, mixed phase is indicated, and the high-pressure phase regime is in the B2 structure.

Figure 4.19. Shock pressure versus density Hugoniot states for initially porous quartz. Density of starting material is indicated on various curves. Porous properties of stishovite are represented by curves with 1.75, 2.13, and 2.65 Mg/m, initial density, whereas coesitelike properties are represented by 0.2-0.8 Mg/m curves (after Simakov and Trunin (1990)).

Figure 4.20. Gruneisen parameter versus pressure for different regimes are indicated. Pluses indicate properties of stishovite phase, half-filled circles and closed circles indicate properties of high-density molten material, whereas open triangles and open circles and upper branch indicate behavior of coesitelike phase (Simakov and Trunin, 1990).

In 1963, McQueen, Fritz, and Marsh (J. Geophys. Res. 68, p. 2319) suggested that the high-pressure shock-wave data for fused quartz (Table 1) and the data for crystal quartz pg = 2.65 g/cm, Co = 1.74 km/s and s = 1.70, both described the shock-induced high-pressure phase of SiOj, stishovite pg = 4.35 g/cm ), above 50 GPa. Assume Ej-j, = 1.5 kJ/g show that these shock data are consistent with a constant value of y = 0.9 in the 50-100 GPa range. 

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. 

Stishovite is a high-pressure modification of Si02 having the rutile structure. Should it have longer or shorter Si-O bond lengths than quartz ... 

Figure 2.15 Pressure-volume data for diamond, SiC>2-stishovite, MgSiC>3 and 8102-quartz based on third order Birch-Murnaghan equation of state descriptions. The isothermal bulk modulus at 1 bar and 298 K are given in the figure.

Demiralp E, Cagin T, Goddard WA(1999) Morse stretch potential charge equilibrium force field for ceramics Application to the quartz-stishovite phase transition and to silica glass. Phys Rev l tt 82 1708-1711 Dewar MJS (1977) Ground states of molecules. The MNDO method. Approximations and parameters. J Am Chem Soc 99 4899-4907... 

Only with silica was the nature of the surface groups studied as extensively as with carbon. Silica, like carbon, has several polymorphs. Apart from the amorphous state, it is known to exist in numerous crystalline modifications. The most important forms are quartz, tridymite, and cristobalite. Each of these can occur in a low-temperature form and in a high-temperature form of somewhat higher symmetry. Tridymite is only stable if small amounts of alkali ions are present in the lattice 159). Ar. Weiss and Al. Weiss 160) discovered an unstable fibrous modification with the SiSj structure. Recently, a few high-pressure modifications have been synthesized keatite 161), coesite 162), and stishovite 16S). The high-pressure forms have been found in nature in impact craters of meteorites, e.g., in the Arizona crater or in the Ries near Nbrdlingen (Bavaria). 

Stishovite is very interesting because it has the rutile structure with octahedral coordination of silicon. In all other forms of silica, each silicon atom is surrounded tetrahedrally by four oxygen atoms. 

The surface chemistry of coesite and stishovite was studied by Stiiber (296). The packing density of hydroxyl groups was estimated from the water vapor adsorption. More adsorption sites per unit surface area were found with silica of higher density. Stishovite is especially interesting since it is not attacked by hydrofluoric acid. Coesite is dissolved slowly. The resistance of stishovite is ascribed to the fact that silicon already has a coordination number of six. Dissolution of silica to HaSiFg by hydrogen fluoride is a nucleophilic attack. It is not possible when the coordination sphere of silicon is filled completely. In contrast, stishovite dissolves with an appreciable rate in water buffered to pH 8.2. The surface chemistry of. stishovite should be similar to that of its analog, rutile. 

Silica has 22 polymorphs, although only some of them are of geochemical interest—namely, the crystalline polymorphs quartz, tridymite, cristobahte, coesite, and stishovite (in their structural modifications of low and high T, usually designated, respectively, as a and jS forms) and the amorphous phases chalcedony and opal (hydrated amorphous silica). The crystalline polymorphs of silica are tectosilicates (dimensionality = 3). Table 5.68 reports their structural properties, after the synthesis of Smyth and Bish (1988). Note that the number of formula units per unit cell varies conspicuously from phase to phase. Also noteworthy is the high density of the stishovite polymorph. 

Polymorph Quartz Coesite Stishovite Cristobalite Tridymite... 

Table 5.70 Thermodynamic data for silica polymorphs. Stishovite and tridymite from Saxena et al. (1993) remaining polymorphs from Helgeson et al. (1978). ...

---