Tridymite structural properties

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. 

Normal ice is analogous to tridymite water has the quartz structure with a greater density. The occurrence of the density maximum at 4°, a unique property of water, must be attributed to the gradual transition of the tridymite structure into the quartz-like structure, while at higher temperature the normal thermal expansion again gets the upper hand. 

The fact that silsesquioxane molecules like 2-7 contain covalently bonded reactive functionalities make them promising monomers for polymerization reactions or for grafting these monomers to polymer chains. In recent years this has been the basis for the development of novel hybrid materials, which offer a variety of useful properties. This area of applied silsesquioxane chemistry has been largely developed by Lichtenhan et al With respect to catalysis research, the chemistry of metallasilsesquioxanes also receives considerable current interest. As mentioned above, incompletely condensed silsesquioxanes of the type R7Si70g(0H)3 (2-7, Scheme 4) share astonishing structural similarities with p-tridymite and p-cristobalite and are thus quite realistic models for the silanol sites on silica surfaces. Metal... 

As water is a unique liquid, so is amorphous silica a unique solid. They are much alike, both consisting mainly of oxygen atoms with the smaller hydrogen or silicon atoms in the interstices. As pointed out by Weyl and Marboe (2), Some properties of water and silica are so similar that the transition between hydrated silicic acids and the aqueous matrix is a gradual one. Washburn (3) noted that water and amorphous silica both have a temperature of minimum. volume. Ephraim (4) observed another similarity between silica and water in that water is much less dense than e, pected from close packing of the constituent atoms and from X-ray diffraction studies. Bernal and Fowler (5a) concluded that water molecules are arranged in a rather open structure like quartz, and undcrcooled water has a still ifiore open structure, like tridymite. Another model has been proposed by Weres and Rice (5b). 

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