High-tridymite

Refinement of the framework coordinates was difficult because of the acentricity and pseudosymmetry. A stable least-squares solution was obtained for the framework atoms in which the T-0 distances indicate alternation of A1 and P atoms. However, the 0 atoms showed large displacements from the centroid, particularly 0(2) for which a difference-Fourier map indicated three spearate peaks (Figure 3). Because there is no optical or X-ray evidence for symmetry lower than hexagonal, it is assumed that there are microdomains with tilted tetrahedra, as proposed for high-cristobalite(6) and high-tridymite( 7). For convenience, the displacements of the oxygen atoms are approximated by ellipsoids. 

Quartz low Quartz high Tridymite S-1 Tridymite S-II Tridymite S-TII Tridymite S-IV Tridymite S-V Tridymite S-VI Tridymite Mrl Tridymite M-Il Tridymite M-IIl Cri.stobalite low Cristobalitc high... 

Figure 3.16 Structures of (a) HP-tridymite (high tridymite) and (b) P (high-)-cristobalite.

Except for siUca and natural abrasives containing free siUca, the abrasive materials used today are classified by NIOSH as nuisance dust materials and have relatively high permissable dust levels (55). The OSHA TWA allowable total dust level for aluminum oxide, siUcon carbide, boron carbide, ceria, and other nuisance dusts is 10 mg/m. SiUca, in contrast, is quite toxic as a respkable dust for cristobaUte [14464-46-1] and tridymite [15468-32-3] the allowable TWA level drops to 0.05 mg/m and the TWA for quartz [14808-60-7] is set at 0.1 mg/m. Any abrasive that contains free siUca in excess of 1% should be treated as a potential health hazard if it is in the form of respkable dust. Dust masks are requked for those exposed to such materials (see Industrial hygene). 

Results obtained at high temperatures indicate that the solubihties of the crystalline modifications of sihca are in the order tridymite > cristobahte > quartz, an order that parallels to some extent the chemical reactivity of these forms. Lower values for solubihty of crystalline as compared to amorphous sihca are consistent with the free-energy differences between them. 

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. 

The stmcture of tridymite is more open than that of quart2 and is similar to that of cristobaUte. The high temperature form, probably S-IV, has a hexagonal unit cell containing four Si02 units, where ttg = 503 pm and Cg = 822 pm > 200° C, space group Pb./mmc. The Si—O distance is 152 pm. 

The existence of tridymite as a distinct phase of pure crystalline siUca has been questioned (42,58—63). According to this view, the only tme crystalline phases of pure siUca at atmospheric pressure are quart2 and a highly ordered three-layer cristobaUte having a transition temperature variously estimated from 806 250°C to about 1050°C (50,60). Tridymites are considered to be defect stmctures in which two-layer sequences predominate. The stabihty of tridymite as found in natural samples and in fired siUca bricks has been attributed to the presence of foreign ions. This view is, however, disputed by those who cite evidence of the formation of tridymite from very pure siUcon and water and of the conversion of tridymite M, but not tridymite S, to cristobahte below 1470°C (47). It has been suggested that the phase relations of siUca are deterrnined by the purity of the system (42), and that tridymite is not a tme form of pure siUca but rather a soHd solution of minerali2er and siUca (63). However, the assumption of the existence of tridymite phases is well estabUshed in the technical Hterature pertinent to practical work. 

As a result of its unique chemical and physical properties, silica gel is probably the most important single substance involved in liquid chromatography today. Without silica gel, it is doubtful whether HPLC could have evolved at all. Silica gel is an amorphous, highly porous, partially hydrated form of silica which is a substance made from the two most abundant elements in the earth s crust, silicon and oxygen. Silica, from which silica gel is manufactured, occurs naturally, either in conjunction with metal oxides in the form of silicates, such as clay or shale, or as free silica in the form of quartz, cristobalite or tridymite crystals. Quartz is sometimes found clear and colorless, but more often in an opaque form, frequently colored... 

This is the process of the crystallization of one or more of the constituents of glass. Generally a glass is thermodynamically unstable with respect to these crystals, but at ordinary temperatures the crystallization rate is quite negligible. Crystallization may occur when the glass is worked at high temperature. The crystals which appear in a supercooled melt are not necessarily those of the stable solid phase at the temperatiure concerned for example, cristobalite can appear at temperatures for which tridymite is the stable crystalline... 

A number of factors contribute to the disparity between the predictions of kinetic theory and conditions observed in the field, as discussed in Section 16.2. In this case, we might infer the dissolution and precipitation of minerals such as opal CT (cristobalite and tridymite, Si02), smectite and other clay minerals, and zeolites help control silica concentration. The minerals may be of minor significance in the aquifer volumetrically, but their high rate constants and specific surface areas allow them to react rapidly. 

To develop effective catalysts for the C02 reforming of methane, other supports were also used for nickel catalysts, including perovskite (244), Y zeolite (245,246), 5A zeolite (247), high-silica ZSM-5 zeolite (248), and AIPO4 (tridymite) (249). 

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). 

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. 

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