THE CRYSTAL CHEMISTRY OF ZEOLITES

Abstract

This chapter discusses the crystal chemistry, emphasizing observed chemical variations, for those zeolites that completely fulfill the requirements of Smith (1963) for a zeolite. These requirements include: (a) a three-dimensional framework of tetrahedra occupied more than 50% by Si and Al; (b) an “open” structure with a framework density (i.e. number of tetrahedral atoms per 1000 A3) lower than 20 (Brunner and Meier 1989) and hence enclosing cavities connected by windows larger than regular six-membered rings; and (c) an extraframework content represented by cations and water molecules. Thus, this chapter will not deal with those phases which are commonly classified as feldspathoids (leucite, pollucite) and those that can be classified as beryllo-phosphates (pahasapaite, weinebeneite), beryllo-silicates (chiavennite, hsianghualite), or zinc-silicates (gaultite). The requirements of Smith (1963) account for the characteristic properties of zeolites (molecular sieve, reversible dehydration, cation exchange), and although for some zeolite species, cation exchange is incomplete or is not yet reported, the presence of large windows (requisite b) reasonably assures its feasibility. Using the above criteria, all minerals known to date which can be classified as zeolites are listed in Table 1⇓. View this table: Table 1. Schematic chemical formulae of natural zeolites. STC = Structure Type Code; Ra = Average Si/(Si+Al+Be); Rr = Range of Si/(Si+Al+Be); DEC = Dominant Extraframework Cations; SEC = Subordinate Extraframework Cations. Italic: Be-bearing species. Underlined: species with an “interrupted framework” In the general formula MxDy[Alx+2ySin-(x+2y)O2n]· m H2O, where M are monovalent and D are divalent cations, it is possible to distinguish two parts, which although very different, are mutually dependent and form a homogeneous complex endowed with exclusive chemico-physical properties. The portion in square brackets represents the tetrahedral framework and is characterized by an overall negative charge which increases as