Sheet structure, dioctahedral

Fig. 2.12 Structural components and variations in the micas. (A) Plan view of the continuous aluminosilicate sheet (T), [Si,Al205] , a portion of the mica structure. (B) Stereographic representation of an idealized mica. The structure is composed of continuous layers containing two tetrahedral aluminosilicate sheets (T) that enclose octahedrally coordinated cations, or Mg (O). This layer or sandwich," the T-O-T or 2 1 aggregate, is held together by or Na ions. (C) The two possible positions (I and II) of octahedral cations in the micas. Sets of three locations for each are superimposed on the tetrahedral hexagonal aluminosilicate sheet. (D) The three possible directions of intralayer shift when octahedral set I (upper) or II (lower) are occupied. The dashed lines and circles represent ions below the plane of the paper. (E) Distorted hexagonal rings of apical oxygens in the tetrahedral sheet of dioctahedral micas compared with the undistorted positions of the apical oxygens in the tetrahedral sheet of trioctahedral micas.

Most of the celadonite samples lie in the area where some mixed-layering is to be expected. Although celadonite is commonly considered to be non-mixed, the literature suggests that little effort has been made to establish this. Of the 15 analyses examined by Wise and Eugster (1964) six reported adsorbed water and in the others it was not determined. In any event, the sheet structure of the celadonite is distinctly different from that of the other 2 1 dioctahedral clays (Radoslovich,1963a). It has a very thick octahedral sheet all three octahedral positions are of equal size (in the other 2 1 dioctahedral clay the two filled positions are smaller than the vacant position) and the interlayer separation is larger than in other contracted 2 1 dioctahedral micas (Radoslovich,1963a). 

In the dioctahedral 2 1 sheet-structure silicate with the occupied sites more than 85% occupied by Al, the structure seems to be able to compensate for the internal strain and can grow to a considerable size. The Al octahedral occupancy values of muscovite (>1.7) and the 2 1 dioctahedral clays (1.3—1.7) indicate that there is little overlap. It is likely that the decreased amount of tetrahedral twist induced by increasing the size of the octahedral cations and octahedral charge (decreasing Al) determines that a clay-size rather than a larger mineral will form. The R3+ occupancy value can be less than 1.3 when the larger Fe3+ is substituted for Al. When Al occupancy values are less than 1.3 (65%), in the absence of appreciable iron, the internal strain is such that growth is in only one direction. The width of the layer is restricted to five octahedral sites. Sufficient layer strain accumulates within this five-site interval such that the silica tetrahedral sheet is forced to invert to accommodate the strain. 

Many of the layer silicate clays common in soils are based on the mica structure (shown in Figure 2.9b) in which two tetrahedral sheets sandwich a single sheet of octahedrally coordinated cations. Consequently, they are termed 2 1 layer sihcates. Conceptually, it is useful to start with the neutral framework of the talc and pyro-phyllite structures, representing the trioctahedral (Mg in the octahedral sheet) and dioctahedral (AF in the octahedral sheet) members of the 2 1 group. These have the ideal formulae given below ... 

The 2-3 subscript for the B site in the formula expresses the fact that there are two families of mica structures, the dioctahedral and trioctahedral micas, based on the composition and occupancy of the intralayer octahedral sites. The trioctahedral micas have three divalent ions—for example, Mg or a brucitelike [Mg(OH)2] intralayer, and the dioctahedral group—two tri-valent ions—for example, Al or a gibbsitelike [AlfOHfa] intralayer, between the tetrahedral sheets. In the dioctahedral micas, therefore, one-third of the octahedral sites are vacant or unoccupied (Fig. 2.12C). 

The converse is true of the Mg ion. It is more abundant in the octahedral sheets of the low-temperature 2 1 dioctahedral minerals, attaining an average value of 3.55% in the montmorillonites and even higher values in glauconite and celadonite. Mg in the octahedral position increases the size of the octahedral sheet and decreases structural strain. 

In general, when either Al or Fe3+ is the dominant (greater than 1.0) cation in the octahedral sheet of a 2 1 dioctahedral clay, the maximum Mg content the sheet can accommodate is 0.50-0.60 (0.5 if Fe3+ is dominant and 0.6 if Al is dominant). When the Mg content is larger than 0.6, as for most celadonites, seldom is any other cation present in amounts greater than 1.0. This suggests structural control of composition. 

Table XXXVIII). Brindley (1955) has suggested that stevensite is a mixed-layer talc-saponite however, Faust et al. (1959) considered it to be a defect structure with a random distribution of vacant sites in the octahedral sheets. A small proportion of domains with few or no vacancies would then be present having characteristics of talc. The layer charge in stevensite is due to an incompletely filled octahedral sheet (Faust and Murata, 1953). This deficiency is minor (0.05—0.10) and the resulting cation exchange capacity is only about one-third that of the dioctahedral montmorillonites (100 mequiv./lOO g.).

The maximum amount of Al3+ tetrahedral substitution that 2 1 clays minerals formed at low temperatures can accommodate appears to be 0.80—0.90 per four tetrahedra. While this appears to place an upper limit on the amount of R3+ octahedral substitution, it is not clear why the limit should be such a low value. The dioctahedral smectites can accommodate more substitution (R2 + for R3+) in the octahedral sheet than can the dioctahedral micas. The reverse situation exists for trioctahedral equivalents. In the latter clays octahedral R3+ increases as tetrahedral Al increases. Thus, as one sheet increases its negative charge, the other tends to increase its positive charge. This is likely to introduce additional constraints on the structure. In the dioctahedral clays substitution in either sheet affords them a negative charge and substitution in one sheet is not predicted by substitution in the other sheet thus, one might expect more flexibility. 

Eggleston and Bailey (1967) published a study on dioctahedral chlorite and gave five examples of chlorites having a pyrophyllite-like layer and a brucite-like sheet (designated di/trioctahedral by the authors with the trioctahedral sheet including all species of chlorite with 5 to 6 octahedral cations per formula unit and dioctahedral 4 to 5 octahedral cations per formula unit). Identification of di/trioctahedral chlorites is indirectly accomplished. Eggleston and Bailey stated that identification depends on the intermediate value of c (060), on chemical analysis of impure material, and on the ideal compositions of the recrystallization products of static heating . The composition of one such chlorite for which they refined the structure is ... 

Vermiculite and vermiculite layers interstratified with mica and chlorite layers are quite common in soils where weathering is not overly aggressive. (A few references are Walker, 1949 Brown, 1953 Van der Marel, 1954 Hathaway, 1955 Droste, 1956 Rich, 1958 Weaver, 1958 Gjems, 1963 Millot and Camez, 1963 Barshad and Kishk, 1969.) Most of these clays are formed by the removal of K from the biotite, muscovite and illite and the brucite sheet from chlorite. This is accompanied by the oxidation of much of the iron in the 2 1 layer. Walker (1949) has described a trioctahedral soil vermiculite from Scotland formed from biotite however, most of the described samples are dioctahedral. Biotite and chlorite with a relatively high iron content weather more easily than the related iron-poor dioctahedral 2 1 clays and under similar weathering conditions are more apt to alter to a 1 1 clay or possibly assume a dioctahedral structure. 

The maximum amount of Fe2+ the octahedral sheets of the 2 1 dioctahedral clays generally contain is 12% (Fig.26). This is equivalent to approximately 0.25—0.30 octahedral positions. Due to the relatively large size of the Fe2 + ion, the structure can apparently adjust to only about half as much Fe2+ as Mg. 

IHite/Smectite. Another common intergrowth of sheet silicates is the mixed-layering of illite and smectite. As discussed above, illite and smectite are clay minerals whose basic structures resemble the mica muscovite. Their compositions may differ significantly from muscovite, but they generally have a lower occupancy of the interlayer sites than mica. Numerous other compositional differences are possible for smectite however, this discussion will be restricted to a dioctahedral illite and a dioctahedral smectite containing potassium and vacancies in the interlayer sites as given above. 

Montmorillonite has some important characteristics that justify its use as a model substance for the study of the interfacial processes of rocks and soils. It is a dioctahedral three-layer clay (2 1 clays, TOT) an A10(0H) octahedral sheet is between two tetrahedral Si04 layers (Chapter 1, Table 1.2). The distance between the layers is not fixed (—O—O-bonds) the layers can be expanded. Because of the layered structure, it has two surface types external and internal surfaces. The external surface is the surface of the particles (edge surface), and its size depends on particle size distribution. Its area can be measured by the BET method, usually by the adsorption of nitrogen gas at the temperature of liquid nitrogen (Chapter 1, Section 1.1.3). The internal surface is the surface between the layers (interlayer surface), and its size can be determined by introducing substances into the interlayer space (e.g., water) (Chapter 1, Section 1.1.3). The internal surface area is independent of particle size distribution. 

The EXAFS results reported for the untreated samples (see Section 8.3.4) led to the conclusion that Zn may form highly ordered inner-sphere sorption complexes with gibbsite surfaces or substitute into an octahedral Al-hydroxide layer of some sort. The use of sequential extraction enabled more concrete conclusions to be made. For the nonextracted soil samples (bulk and coarse), second-shell Al coordination numbers did not exceed four, in fine with the dioctahedral structure of gibbsite sheets (only two out of three metal positions are occupied). Elsewhere, a gradual increase was observed in Al coordination up to six with each extraction step, indicating that Zn is part of a fully occupied, trioctahedral Al-Zn2+ layer and not part of gibbsite or another dioctahedral Al compound.67 While dioctahedral Al-hydroxide layers are... 

Figure 5.3. Side view (along the a-axis) of ideal structures of two common configurations of layer-lattice aluminosilieates. A. 1 1 layer lattice, consisting of alternative octahedral and tetrahedral sheets. B. 2 1 layer lattice, consisting of two tetrahedral sheets sandwiching the octahedral sheet. Where the octahedral cations are trivalent, only two out of three octahedral sites are occupied and the mineral is dioctahedral. Where the octahedral cations are divalent, all octahedral sites are occupied and the mineral is trioctahedral.

Smectites, which are based on either the trioctahedral 2 1 (talc) or dioctahedral 2 1 (pyrophyllite) structure, differ from these neutral structures by the presence of isomorphous substitution in the octahedral or tetrahedral sheet. For example, the dioctahedral smectite, montmorillonite, has the general formula... 

Exploration of the pillar-clay sheet reactivity and connectivity also indicate the important role of the specific clay type. 27 1 and 29si-MASNMR experiments have shown distinctive differences between pillaring mechanisms in trioctahedral hectorite and dioctahedral montmorillonite. Whereas Plee et al. (22) concluded that chemical crosslinking may occur between the pillar and tetrahedral layer in a beidellite montmorillonite, Pinnavaia et al. (23) showed that it did not occur in a hectorite. These are the first observations of a complex process that may depend upon several structural and chemical factors, such as substitution of Al in the tetrahedral layer, or the need for vacancies in the octahedral layer to allow rotation of structural units or migration of reactant species to facilitate crosslinking. Ongoing research should further elucidate refinements on these mechanisms, and direct the technology towards more optimized catalysts - presumably those which form chemical bonds between the pillar and clay layer. 

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