Sodium chloride type structure

Sometimes the atomic arrangement of a crystal is such as not to permit the formulation of a covalent structure. This is the case for the sodium chloride arrangement, as the alkali halides do not contain enough electrons to form bonds between each atom and its six equivalent nearest neighbors. This criterion must be applied with caution, however, for in some cases electron pairs may jump around in the crystal, giving more bonds than there are electron pairs, each bond being of an intermediate type. It must also be mentioned that determinations of the atomic arrangement are sometimes not sufficiently accurate to provide evidence on this point an atom reported equidistant from six others may be somewhat closer to three, say, than to the other three. 

In deriving theoretical values for inter-ionic distances in ionic crystals the sum of the univalent crystal radii for the two ions should be taken, and corrected by means of Equation 13, with z given a value dependent on the ratio of the Coulomb energy of the crystal to that of a univalent sodium chloride type crystal. Thus, for fluorite the sum of the univalent crystal radii of calcium ion and fluoride ion would be used, corrected by Equation 13 with z placed equal to y/2, for the Coulomb energy of the fluorite crystal (per ion) is just twice that of the univalent sodium chloride structure. This procedure leads to the result 1.34 A. (the experimental distance is 1.36 A.). However, usually it is permissible to use the sodium chloride crystal radius for each ion, that is, to put z = 2 for the calcium... 

In Table XVIII are given values of the radius ratio for the salts of beryllium, magnesium and calcium (those of barium and strontium, with the sodium chloride structure, also obviously satisfy the radius ratio criterion). It is seen that all of the sodium chloride type crystals containing eight-shell cations have radius ratios greater than the limit 0.33, and the beryl-... 

The radius ratios for sphalerite and wurzite type crystals with eighteen-shell cations do not conform to our criterion, so that some other influence must be operative. Without doubt this is deformation. Here again it is seen that the tetrahedral structure is particularly favorable to deformation, for the observed Zn++—O distance (1.93 A.) is 0.21 A. shorter than the theoretical one, while in cadmium oxide, with the sodium chloride structure, the difference is only 0.01 A. 

Based on the ionic radii, nine of the alkali halides should not have the sodium chloride structure. However, only three, CsCl, CsBr, and Csl, do not have the sodium chloride structure. This means that the hard sphere approach to ionic arrangement is inadequate. It should be mentioned that it does predict the correct arrangement of ions in the majority of cases. It is a guide, not an infallible rule. One of the factors that is not included is related to the fact that the electron clouds of ions have some ability to be deformed. This electronic polarizability leads to additional forces of the types that were discussed in the previous chapter. Distorting the electron cloud of an anion leads to part of its electron density being drawn toward the cations surrounding it. In essence, there is some sharing of electron density as a result. Thus the bond has become partially covalent. 

Although the structure of CsCl is quite different from that of NaCl, even CsCl can be transformed into the sodium chloride structure when heated to temperatures above 445 °C. Some of the other alkali halides that do not have the sodium chloride structure under ambient conditions are converted to that structure when subjected to high pressure. Many solid materials exhibit this type of polymorphism, which depends on the external conditions. Conversion of a material from one structure to another is known as a phase transition. 

By means of the radius ratio, we have already described the type of local environment around the ions in several types of simple crystals. For example, in the sodium chloride structure (not restricted to NaCl itself), there are six anions surrounding each cation. The sodium chloride crystal structure is shown in Figure 7.4. 

As was discussed in Chapter 7, there are numerous solids that can exist in more than one form. It is frequently the case that high pressure is sufficient inducement for the structure to change. An example of this type of behavior is seen in KC1, which has the sodium chloride (rock salt) structure at ambient pressure, but is converted to the cesium chloride structure at high pressure. Other examples illustrating the effect of pressure will be seen throughout this book (see especially Chapter 20). It should be kept... 

Despite the fact that not all details of the photographic process are completely understood, the overall mechanism for the production of the latent image is well known. Silver chloride, AgBr, crystallizes with the sodium chloride structure. While Schottky defects are the major structural point defect type present in most crystals with this structure, it is found that the silver halides, including AgBr, favor Frenkel defects (Fig. 2.5). 

The sodium chloride structure is adopted by a large number of compounds, from the ionic alkali halides NaCl and KC1, to covalent sulfides such as PbS, or metallic oxides such as titanium oxide, TiO. Slip and dislocation structures in these materials will vary according to the type chemical bonding that prevails. Thus, slip on 100 may be preferred when ionic character is suppressed, as it is in the more metallic materials. 

The nature of a surface will depend upon which atoms are exposed. For example, the surface of a crystal with the sodium chloride structure might consist of a mixture of atoms, as on 100 (Fig. 3.34a), or of just one atom type, as on 111 (Fig. 3.34b and 3.34c). However, it must be remembered that no surface is clean and uncontaminated unless it is prepared under very carefully controlled conditions. Absorbed gases, especially water vapor, are invariably present on a surface in air, which leads to changes in chemical and physical properties. 

The same analysis can be applied to more complex situations. Suppose that cation vacancy diffusion is the predominant migration mechanism, in a sodium chloride structure crystal, of formula MX, which contains Schottky defects as the major type of intrinsic defects. The relevant defect concentration [ii] is [Eq. (2.11)]... 

Few oxide superconductors were known prior to 1985 and we shall now return to these so that we can discuss these materials in reference to their crystal structure classes. There are only three broad structural categories in which most of the oxide superconductors occur. The important structural types include sodium chloride (rocksalt, or Bl-type), perovskite (E2X), and spinel (Hlx). 

Oxides generally have complex crystal structures. The oxides of composition MO (M = metal) show a wide range of structural types. For example FeO, VO, NiO and MnO oxides have the ionic sodium chloride structure (figure 1.4(a)). Other structural types relevant to catalysis are described here. 

FIGURE 5.5 Sodium chloride type structure, depicting (a) coordination octahedron of central cation and (h) coordination octahedra of central cation and adjacent vacancy. 

Fig. 1.10 The sodium chloride (a) and nickel arsenide (b) structure types. From Wells (1986).

The structures of the hydrides, oxides and nitrides in this group are rather peculiar, for they can always be described as lattices, as found in pure metals, with the negative ions inserted in the octahedral holes of these structures. In the case of TiN, TiO and, in general, all compounds AB, all octahedral holes are occupied, and the structure is that of the sodium chloride type. There are nitrides of other types, too, e.g. A2N, A3N, etc., in which cases only a part of the octahedral holes are occupied. 

In some crystals such rotation occurs at room temperature. One of the simplest examples is potassium cyanide, KON the structure is of the sodium chloride type (Fig. 127), and this can only mean that the CN ion is rotating it does not necessarily mean that all orientations are equally probable, but it does mean that frequent changes of orientation occur, such that the effective symmetry of the ion is the highest possible in the cubic system neither carbon nor nitrogen atoms occupy specific positions in the structure but are in effect spread over a number of positions. 

A simpler example is the iron sulphide pyrrhotite, the composition of which is roughly FeS but which always contains rather too little iron. The X-ray pattern indicates the sodium chloride type of structure, and it appears that while the negative ion positions are fully occupied by sulphur, there is a deficiency of iron atoms in the positive ion sites. (Laves, 1930 Hagg and Sucksdorff, 1933.)... 

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