10.6 Lattice structures in crystalline solids  (Page 5/29)

In general, a unit cell is defined by the lengths of three axes ( a , b , and c ) and the angles ( α , β , and γ ) between them, as illustrated in [link] . The axes are defined as being the lengths between points in the space lattice. Consequently, unit cell axes join points with identical environments.

There are seven different lattice systems, some of which have more than one type of lattice, for a total of fourteen different unit cells, which have the shapes shown in [link] .

The structures of ionic crystals

Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.

Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite charge and (2) when the cations and anions are in contact with each other. Structures are determined by two principal factors: the relative sizes of the ions and the ratio of the numbers of positive and negative ions in the compound.

In simple ionic structures, we usually find the anions, which are normally larger than the cations, arranged in a closest-packed array. (As seen previously, additional electrons attracted to the same nucleus make anions larger and fewer electrons attracted to the same nucleus make cations smaller when compared to the atoms from which they are formed.) The smaller cations commonly occupy one of two types of holes (or interstices) remaining between the anions. The smaller of the holes is found between three anions in one plane and one anion in an adjacent plane. The four anions surrounding this hole are arranged at the corners of a tetrahedron, so the hole is called a tetrahedral hole    . The larger type of hole is found at the center of six anions (three in one layer and three in an adjacent layer) located at the corners of an octahedron; this is called an octahedral hole    . [link] illustrates both of these types of holes.

Depending on the relative sizes of the cations and anions, the cations of an ionic compound may occupy tetrahedral or octahedral holes, as illustrated in [link] . Relatively small cations occupy tetrahedral holes, and larger cations occupy octahedral holes. If the cations are too large to fit into the octahedral holes, the anions may adopt a more open structure, such as a simple cubic array. The larger cations can then occupy the larger cubic holes made possible by the more open spacing.

There are two tetrahedral holes for each anion in either an HCP or CCP array of anions. A compound that crystallizes in a closest-packed array of anions with cations in the tetrahedral holes can have a maximum cation:anion ratio of 2:1; all of the tetrahedral holes are filled at this ratio. Examples include Li ₂ O, Na ₂ O, Li ₂ S, and Na ₂ S. Compounds with a ratio of less than 2:1 may also crystallize in a closest-packed array of anions with cations in the tetrahedral holes, if the ionic sizes fit. In these compounds, however, some of the tetrahedral holes remain vacant.