Layer lattices

Solid cadmium(II) iodide Cdlj has a layer lattice —a structure intermediate between one containing Cd " and P ions and one containing Cdl2 molecules—and this on vaporisation gives linear, covalent I—Cd—I molecules. In solution, iodo-complexes exist, for example... 

The common structural element in the crystal lattice of fluoroaluminates is the hexafluoroaluminate octahedron, AIF. The differing stmctural features of the fluoroaluminates confer distinct physical properties to the species as compared to aluminum trifluoride. For example, in A1F. all corners are shared and the crystal becomes a giant molecule of very high melting point (13). In KAIF, all four equatorial atoms of each octahedron are shared and a layer lattice results. When the ratio of fluorine to aluminum is 6, as in cryoHte, Na AlF, the AIFp ions are separate and bound in position by the balancing metal ions. Fluorine atoms may be shared between octahedrons. When opposite corners of each octahedron are shared with a corner of each neighboring octahedron, an infinite chain is formed as, for example, in TI AIF [33897-68-6]. More complex relations exist in chioUte, wherein one-third of the hexafluoroaluminate octahedra share four corners each and two-thirds share only two corners (14). 

Hydrotalcite. Synthetic hydrotalcite minerals are gaining commercial acceptance for thein abiHty to costabiHze PVC ia the presence of other primary stabilizers (see Table 2). The performance of the mixed metal stabilizers are particularly boosted when an equal part level, about 2—3 phr, of hydrotalcite is added to the PVC formulation. These minerals function by trapping HCl within the layered lattice arrangement of atoms. The formula. 

Iron(II) bromide [7789-46-0] FeBr2, can be prepared by reaction of iron and bromine ia a flow system at 200°C and purified by sublimation ia oitrogea or uader vacuum. Other preparative routes iaclude the reactioa of Fe202 with HBr ia a flow system at 200—350°C, reactioa of iroa with HBr ia methanol, and dehydration of hydrated forms. FeBr2 crystallizes ia a layered lattice of the Cdfy type and has a magnetic moment of... 

Various other soft materials without the layer—lattice stmcture are used as soHd lubricants (58), eg, basic white lead or lead carbonate [598-63-0] used in thread compounds, lime [1305-78-8] as a carrier in wire drawing, talc [14807-96-6] and bentonite [1302-78-9] as fillers for grease for cable pulling, and zinc oxide [1314-13-2] in high load capacity greases. Graphite fluoride is effective as a thin-film lubricant up to 400°C and is especially useful with a suitable binder such as polyimide varnish (59). Boric acid has been shown to have promise as a self-replenishing soHd composite (60). 

Fig. 1. Diagrammatic representation of the succession of layers in some layer lattice siHcates (12) where 0 is oxygen , hydroxyl , siHcon o. Si—Al aluminum C, Al—Mg O, potassium , Na—Ca. Sample layers are designated as O, octahedral T, tetrahedral and B/G, bmcite- or gibbsitelike. The...

The crystal structure of many compounds is dominated by the effect of H bonds, and numerous examples will emerge in ensuing chapters. Ice (p. 624) is perhaps the classic example, but the layer lattice structure of B(OH)3 (p. 203) and the striking difference between the a- and 6-forms of oxalic and other dicarboxylic acids is notable (Fig. 3.9). The more subtle distortions that lead to ferroelectric phenomena in KH2PO4 and other crystals have already been noted (p. 57). Hydrogen bonds between fluorine atoms result in the formation of infinite zigzag chains in crystalline hydrogen fluoride... 

The structure of AICI3 is similarly revealing. The crystalline solid has a layer lattice with 6-coordinate Al but at the mp 192.4° the stmcture changes to a 4-coordinate molecular dimer Al2Clg as a result there is a dramatic increase in volume (by 85%) and an even more dramatic drop in electrical conductivity almost to zero. The mp therefore represents a substantial change in the nature of the bonding. The covalently bonded... 

In203 has the C-type M2O3 structure (p. 1238) and InO(OH) (prepared hydrothermal ly from In(OH)3 at 250-400°C and 100-1500 atm) has a deformed rutile structure (p. 961) rather than the layer lattice structure of AIO(OH) and GaO(OH). Crystalline In(OH)3 is best prepared by addition of NH3 to aqueous InCl3 at 100° and ageing the precipitate for a few hours at this temperature it has the simple Re03-type structure distorted somewhat by multiple H bonds. 

Structure of nickel arsenide showing (a) 3 unit cells, (b) a single unit cell NiaAsa and its relation to (c) the unit cell of the layer lattice compound Cdia (see text). 

The predominantly ionic alkali metal sulfides M2S (Li, Na, K, Rb, Cs) adopt the antifluorite structure (p. 118) in which each S atom is surrounded by a cube of 8 M and each M by a tetrahedron of S. The alkaline earth sulfides MS (Mg, Ca, Sr, Ba) adopt the NaCl-type 6 6 structure (p. 242) as do many other monosulfides of rather less basic metals (M = Pb, Mn, La, Ce, Pr, Nd, Sm, Eu, Tb, Ho, Th, U, Pu). However, many metals in the later transition element groups show substantial trends to increasing covalency leading either to lower coordination numbers or to layer-lattice structures. Thus MS (Be, Zn, Cd, Hg) adopt the 4 4 zinc blende structure (p. 1210) and ZnS, CdS and MnS also crystallize in the 4 4 wurtzite modification (p. 1210). In both of these structures both M and S are tetrahedrally coordinated, whereas PtS, which also has 4 4... 

The molecular and bulk properties of the halogens, as distinct from their atomic and nuclear properties, were summarized in Table 17.4 and have to some extent already been briefly discussed. The high volatility and relatively low enthalpy of vaporization reflect the diatomic molecular structure of these elements. In the solid state the molecules align to give a layer lattice p2 has two modifications (a low-temperature, a-form and a higher-temperature, yS-form) neither of which resembles the orthorhombic layer lattice of the isostructural CI2, Br2 and I2. The layer lattice is illustrated below for I2 the I-I distance of 271.5 pm is appreciably longer than in gaseous I2 (266.6 pm) and the closest interatomic approach between the molecules is 350 pm within the layer and 427 pm between layers (cf the van der Waals radius of 215 pm). These values are... 

A detailed discussion of individual halides is given under the chemistry of each particular element. This section deals with more general aspects of the halides as a class of compound and will consider, in turn, general preparative routes, structure and bonding. For reasons outlined on p. 805, fluorides tend to differ from the other halides either in their method of synthesis, their structure or their bond-type. For example, the fluoride ion is the smallest and least polarizable of all anions and fluorides frequently adopt 3D ionic structures typical of oxides. By contrast, chlorides, bromides and iodides are larger and more polarizable and frequently adopt mutually similar layer-lattices or chain structures (cf. sulfides). Numerous examples of this dichotomy can be found in other chapters and in several general references.Because of this it is convenient to discuss fluorides as a group first, and then the other halides. 

All three metals form a wide variety of binary chalcogenides which frequently differ both in stoichiometry and in structure from the oxides. Many have complex structures which are not easily described, and detailed discussion is therefore inappropriate. The various sulfide phases are listed in Table 22.4 phases approximating to the stoichiometry MS have the NiAs-type structure (p. 556) whereas MS2 have layer lattices related to M0S2 (p. 1018), Cdl2, or CdCl2 (p. 1212). Sometimes complex layer-sequences occur in which the 6-coordinate metal atom is alternatively octahedral and trigonal prismatic. Most of the phases exhibit... 

There are few systematic guidelines which can be used to predict the properties of AB2 metal hydride electrodes. Alloy formulation is primarily an empirical process where the composition is designed to provide a bulk hydride-forming phase (or phases) which form, in situ, a corrosion— resistance surface of semipassivating oxide (hydroxide) layers. Lattice expansion is usually reduced relative to the ABS hydrides because of a lower VH. Pressure-composition isotherms of complex AB2 electrode materials indicate nonideal behaviour. 

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