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By the end of this section, you will be able to:
  • Describe the arrangement of atoms and ions in crystalline structures
  • Compute ionic radii using unit cell dimensions
  • Explain the use of X-ray diffraction measurements in determining crystalline structures

Over 90% of naturally occurring and man-made solids are crystalline. Most solids form with a regular arrangement of their particles because the overall attractive interactions between particles are maximized, and the total intermolecular energy is minimized, when the particles pack in the most efficient manner. The regular arrangement at an atomic level is often reflected at a macroscopic level. In this module, we will explore some of the details about the structures of metallic and ionic crystalline solids, and learn how these structures are determined experimentally.

The structures of metals

We will begin our discussion of crystalline solids by considering elemental metals, which are relatively simple because each contains only one type of atom. A pure metal is a crystalline solid with metal atoms packed closely together in a repeating pattern. Some of the properties of metals in general, such as their malleability and ductility, are largely due to having identical atoms arranged in a regular pattern. The different properties of one metal compared to another partially depend on the sizes of their atoms and the specifics of their spatial arrangements. We will explore the similarities and differences of four of the most common metal crystal geometries in the sections that follow.

Unit cells of metals

The structure of a crystalline solid, whether a metal or not, is best described by considering its simplest repeating unit, which is referred to as its unit cell    . The unit cell consists of lattice points that represent the locations of atoms or ions. The entire structure then consists of this unit cell repeating in three dimensions, as illustrated in [link] .

A diagram of two images is shown. In the first image, a cube with a sphere at each corner is shown. The cube is labeled “Unit cell” and the spheres at the corners are labeled “Lattice points.” The second image shows the same cube, but this time it is one cube amongst eight that make up a larger cube. The original cube is shaded a color while the other cubes are not.
A unit cell shows the locations of lattice points repeating in all directions.

Let us begin our investigation of crystal lattice structure and unit cells with the most straightforward structure and the most basic unit cell. To visualize this, imagine taking a large number of identical spheres, such as tennis balls, and arranging them uniformly in a container. The simplest way to do this would be to make layers in which the spheres in one layer are directly above those in the layer below, as illustrated in [link] . This arrangement is called simple cubic structure    , and the unit cell is called the simple cubic unit cell    or primitive cubic unit cell.

A diagram of three images is shown. In the first image, a cube with a sphere at each corner is shown. The spheres at the corners are circled. The second image shows the same cube, but this time the spheres at the corners are larger and shaded in. In the third image, the cube is one cube amongst eight that make up a larger cube. The original cube is shaded a color while the other cubes are not.
When metal atoms are arranged with spheres in one layer directly above or below spheres in another layer, the lattice structure is called simple cubic. Note that the spheres are in contact.

In a simple cubic structure, the spheres are not packed as closely as they could be, and they only “fill” about 52% of the volume of the container. This is a relatively inefficient arrangement, and only one metal (polonium, Po) crystallizes in a simple cubic structure. As shown in [link] , a solid with this type of arrangement consists of planes (or layers) in which each atom contacts only the four nearest neighbors in its layer; one atom directly above it in the layer above; and one atom directly below it in the layer below. The number of other particles that each particle in a crystalline solid contacts is known as its coordination number    . For a polonium atom in a simple cubic array, the coordination number is, therefore, six.

Questions & Answers

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Source:  OpenStax, Chemistry. OpenStax CNX. May 20, 2015 Download for free at http://legacy.cnx.org/content/col11760/1.9
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