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6.3: Unit Cells

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    235788
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    Skills to Develop

    • Describe the arrangement of atoms and ions in crystalline structures

    Video \(\PageIndex{1}\): A preview of giant ionic solids and 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 Figure \(\PageIndex{1}\).

    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.

    Figure \(\PageIndex{1}\): 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 Figure \(\PageIndex{2}\). 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.

    Figure \(\PageIndex{2}\): .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 Figure \(\PageIndex{3}\), 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.

    <div data-mt-source="1"><img class="internal" alt="" style="width: 650px; height: 281px;" data-cke-saved-src="http://chemwiki.ucdavis.edu/@api/deki/files/61021/CNX_Chem_10_06_SimpleCub2.jpg" src="http://chemwiki.ucdavis.edu/@api/deki/files/61021/CNX_Chem_10_06_SimpleCub2.jpg"></div>

    Figure \(\PageIndex{3}\): An atom in a simple cubic lattice structure contacts six other atoms, so it has a coordination number of six.

    In a simple cubic lattice, the unit cell that repeats in all directions is a cube defined by the centers of eight atoms, as shown in Figure \(\PageIndex{4}\). Atoms at adjacent corners of this unit cell contact each other, so the edge length of this cell is equal to two atomic radii, or one atomic diameter. A cubic unit cell contains only the parts of these atoms that are within it. Since an atom at a corner of a simple cubic unit cell is contained by a total of eight unit cells, only one-eighth of that atom is within a specific unit cell. And since each simple cubic unit cell has one atom at each of its eight “corners,” there is \(8×\dfrac{1}{8}=1\) atom within one simple cubic unit cell.

    A diagram of two images is shown. In the first image, eight spheres are stacked together to form a cube and dots at the center of each sphere are connected to form a cube shape. The dots are labeled “Lattice points” while a label under the image reads “Simple cubic lattice cell.” The second image shows the portion of each sphere that lie inside the cube. The corners of the cube are shown with small circles labeled “Lattice points” and the phrase “8 corners” is written below the image.

    Figure \(\PageIndex{4}\): A simple cubic lattice unit cell contains one-eighth of an atom at each of its eight corners, so it contains one atom total.

    Most metal crystals are one of the four major types of unit cells. For now, we will focus on the three cubic unit cells: simple cubic (which we have already seen), body-centered cubic unit cell, and face-centered cubic unit cell—all of which are illustrated in Figure \(\PageIndex{5}\). (Note that there are actually seven different lattice systems, some of which have more than one type of lattice, for a total of 14 different types of unit cells. We leave the more complicated geometries for later in this module.)

    Three pairs of images are shown. The first three images are in a row and are labeled “Lattice point locations” while the second three images are in a row labeled “Cubic unit cells.” The first image in the top row shows a cube with black dots at each corner while the first image in the second row is composed of eight spheres that are stacked together to form a cube and dots at the center of each sphere are connected to form a cube shape. The name under this image reads “Simple cubic.” The second image in the top row shows a cube with black dots at each corner and a red dot in the center while the second image in the second row is composed of eight spheres that are stacked together to form a cube with one sphere in the center of the cube and dots at the center of each corner sphere connected to form a cube shape. The name under this image reads “Body-centered cubic.” The third image in the top row shows a cube with black dots at each corner and red dots in the center of each face while the third image in the second row is composed of eight spheres that are stacked together to form a cube with six more spheres located in the center of each face of the cube. Dots at the center of each corner sphere are connected to form a cube shape. The name under this image reads “Face-centered cubic.”

    Figure \(\PageIndex{5}\): Cubic unit cells of metals show (in the upper figures) the locations of lattice points and (in the lower figures) metal atoms located in the unit cell.

    Some metals crystallize in an arrangement that has a cubic unit cell with atoms at all of the corners and an atom in the center, as shown in Figure \(\PageIndex{6}\). This is called a body-centered cubic (BCC) solid. Atoms in the corners of a BCC unit cell do not contact each other but contact the atom in the center. A BCC unit cell contains two atoms: one-eighth of an atom at each of the eight corners (\(8×\dfrac{1}{8}=1\) atom from the corners) plus one atom from the center. Any atom in this structure touches four atoms in the layer above it and four atoms in the layer below it. Thus, an atom in a BCC structure has a coordination number of eight.

    Three images are shown. The first image shows a cube with black dots at each corner and a red dot in the center while the second image is composed of eight spheres that are stacked together to form a cube with one sphere in the center of the cube and dots at the center of each corner sphere connected to form a cube shape.  The name under this image reads “Body-centered cubic structure.” The third image is the same as the second, but only shows the portions of the spheres that lie inside the cube shape.

    Figure \(\PageIndex{6}\): In a body-centered cubic structure, atoms in a specific layer do not touch each other. Each atom touches four atoms in the layer above it and four atoms in the layer below it.

    Atoms in BCC arrangements are much more efficiently packed than in a simple cubic structure, occupying about 68% of the total volume. Isomorphous metals with a BCC structure include K, Ba, Cr, Mo, W, and Fe at room temperature. (Elements or compounds that crystallize with the same structure are said to be isomorphous.)

    Many other metals, such as aluminum, copper, and lead, crystallize in an arrangement that has a cubic unit cell with atoms at all of the corners and at the centers of each face, as illustrated in Figure \(\PageIndex{7}\). This arrangement is called a face-centered cubic (FCC) solid. A FCC unit cell contains four atoms: one-eighth of an atom at each of the eight corners (\(8×\dfrac{1}{8}=1\) atom from the corners) and one-half of an atom on each of the six faces (\(6×\dfrac{1}{2}=3\) atoms from the faces). The atoms at the corners touch the atoms in the centers of the adjacent faces along the face diagonals of the cube. Because the atoms are on identical lattice points, they have identical environments.

    Three images are shown. The first image shows a cube with black dots at each corner and red dots in the center of each face of the cube while the second image is composed of eight spheres that are stacked together to form a cube with six more spheres, one located on each face of the structure. Dots at the center of each corner sphere are connected to form a cube shape. The name under this image reads “Face-centered cubic structure.” The third image is the same as the second, but only shows the portions of the spheres that lie inside the cube shape.

    Figure \(\PageIndex{7}\):A face-centered cubic solid has atoms at the corners and, as the name implies, at the centers of the faces of its unit cells.

    Atoms in an FCC arrangement are packed as closely together as possible, with atoms occupying 74% of the volume. This structure is also called cubic closest packing (CCP). In CCP, there are three repeating layers of hexagonally arranged atoms. Each atom contacts six atoms in its own layer, three in the layer above, and three in the layer below. In this arrangement, each atom touches 12 near neighbors, and therefore has a coordination number of 12. The fact that FCC and CCP arrangements are equivalent may not be immediately obvious, but why they are actually the same structure is illustrated in Figure \(\PageIndex{8}\). Table \(\PageIndex{1}\) summarizes the important characteristics of the three major unit cell types.

    Figure 4,1,8.jpeg

    Figure \(\PageIndex{8}\): A CCP arrangement consists of three repeating layers (ABCABC…) of hexagonally arranged atoms. Atoms in a CCP structure have a coordination number of 12 because they contact six atoms in their layer, plus three atoms in the layer above and three atoms in the layer below. By rotating our perspective, we can see that a CCP structure has a unit cell with a face containing an atom from layer A at one corner, atoms from layer B across a diagonal (at two corners and in the middle of the face), and an atom from layer C at the remaining corner. This is the same as a face-centered cubic arrangement.

    Cubic Cell Name Atoms per Unit Cell Structure Coordination Number

    simple cubic (sc)

    1

    clipboard_e3037bec26ec5c61944149e5c7c4c4b32.png

    6

    face-centered cubic

    4

    clipboard_e37338ff377e986dc541da72d86fd4421.png

    12

    body-centered cubic

    2

    clipboard_e836b3bc133ea3a27fbdeb1fe0637a80a.png

    8

    Table \(\PageIndex{1}\): A summary of the important characteristics of the three main types of unit cells.

    Because closer packing maximizes the overall attractions between atoms and minimizes the total intermolecular energy, the atoms in most metals pack in this manner. We find two types of closest packing in simple metallic crystalline structures: CCP, which we have already encountered, and hexagonal closest packing (HCP) shown in Figure \(\PageIndex{9}\). Both consist of repeating layers of hexagonally arranged atoms. In both types, a second layer (B) is placed on the first layer (A) so that each atom in the second layer is in contact with three atoms in the first layer. The third layer is positioned in one of two ways. In HCP, atoms in the third layer are directly above atoms in the first layer (i.e., the third layer is also type A), and the stacking consists of alternating type A and type B close-packed layers (i.e., ABABAB⋯). In CCP, atoms in the third layer are not above atoms in either of the first two layers (i.e., the third layer is type C), and the stacking consists of alternating type A, type B, and type C close-packed layers (i.e., ABCABCABC⋯). About two–thirds of all metals crystallize in closest-packed arrays with coordination numbers of 12. Metals that crystallize in an HCP structure include Cd, Co, Li, Mg, Na, and Zn, and metals that crystallize in a CCP structure include Ag, Al, Ca, Cu, Ni, Pb, and Pt.

    Two images are shown. The first image, labeled “Hexagonal closest packed,” shows seven green spheres arranged in a circular sheet lying atop another sheet that is the same except the spheres are purple. The second sheet is offset just a bit so that the spheres of the top sheet lie in the grooves of the second sheet. Two more alternating green and purple layers of spheres lie below the first pair. The second image shows seven blue spheres, labeled “Layer C,” arranged in a circular sheet laying atop another sheet, labeled “Layer B” that is the same except the spheres are green. The second sheet is offset just a bit so that the spheres of the top sheet lie in the grooves of the second sheet. Two more alternating purple and then blue layers of spheres lie below the first pair. The purple layer is labeled “Layer A” and the phrase written below this image reads “Cubic closest packed.”

    Figure \(\PageIndex{9}\): In both types of closest packing, atoms are packed as compactly as possible. Hexagonal closest packing consists of two alternating layers (ABABAB…). Cubic closest packing consists of three alternating layers (ABCABCABC…).

    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 Figure \(\PageIndex{10}\). The axes are defined as being the lengths between points in the space lattice. Consequently, unit cell axes join points with identical environments.

    A cube is shown where each corner has a black dot drawn on it. A circle in the bottom of the cube is composed of three double-ended arrows. The left top of this circle is labeled “alpha,” the top right is labeled “beta” and the bottom is labeled “gamma.” The bottom left corner of the cube is labeled “a” while the bottom of the back face is labeled “b” and the top, back, left corner is labeled “c.”

    Figure \(\PageIndex{10}\): A unit cell is defined by the lengths of its three axes (a, b, and c) and the angles (α, β, and γ) between the axes.

    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 Figure \(\PageIndex{11}\).

    A table is composed of two columns and eight rows. The header row reads “System / Axes / Angles” and “Unit Cells .” The first column reads “Cubic, a equals b equals c, alpha equals beta equals gamma equals 90 degrees,” “Tetragonal, a equals b does not equal c, alpha equals beta equals gamma equals 90 degrees,” “Orthorhombic, a does not equal b does not equal c, alpha equals beta equals gamma equals 90 degrees,” “Monoclinic, a does not equal b does not equal c, alpha equals gamma equals 90 degrees, beta does not equal 90 degrees,” “Triclinic, a does not equal b does not equal c, alpha does not equal beta does not equal gamma does not equal 90 degrees,” “Hexagonal, a equals b does not equal c, alpha equals beta equals 90 degrees, gamma equals 120 degrees,” “Rhombohedral, a equals b equals c, alpha equals beta equals gamma does not equal 90 degrees.” The second column is composed of diagrams. The first set of diagrams in the first cell show a cube with spheres at each corner labeled “Simple,” a cube with spheres in each corner and on each face labeled “Face-centered” and a cube with spheres in each corner and one in the center labeled “Body-centered.” The second set of diagrams in the second cell show a vertical rectangle with spheres at each corner labeled “Simple” and a vertical rectangle with spheres in each corner and one in the center labeled “Body-centered.” The third set of diagrams in the third cell show a vertical rectangle with spheres at each corner labeled “Simple,” a vertical rectangle with spheres in each corner and one in the center labeled “Body-centered,” a vertical rectangle with spheres in each corner and one on the top and bottom faces labeled “Base-centered,” and a vertical rectangle with spheres in each corner and one on each face labeled “Face-centered.” The fourth set of diagrams in the fourth cell show a vertical rectangle with spheres at each corner that is slanted to one side labeled “Simple” and a vertical rectangle with spheres in each corner that is slanted to one side and has two spheres in the center is labeled “Body-centered.” The fifth diagrams in the fifth cell show a cube that is slanted with spheres at each corner while the sixth diagram in the sixth cell shows a pair of hexagonal rings that are connected together to form a six-sided shape with spheres at each corner. The seventh diagram in the seventh cell shows a rectangle that is slanted with spheres at each corner.

    Figure \(\PageIndex{11}\):There are seven different lattice systems and 14 different unit cells.

    Unit Cells of Ionic Compounds

    Many ionic compounds crystallize with cubic unit cells, and we will use these compounds to describe the general features of ionic structures. When an ionic compound is composed of cations and anions of similar size in a 1:1 ratio, it typically forms a simple cubic structure. Cesium chloride, CsCl, (Figure \(\PageIndex{12}\)) is an example of this, with Cs+ and Cl having radii of 174 pm and 181 pm, respectively. We can think of this as chloride ions forming a simple cubic unit cell, with a cesium ion in the center; or as cesium ions forming a unit cell with a chloride ion in the center; or as simple cubic unit cells formed by Cs+ ions overlapping unit cells formed by Cl ions. Cesium ions and chloride ions touch along the body diagonals of the unit cells. One cesium ion and one chloride ion are present per unit cell, giving the l:l stoichiometry required by the formula for cesium chloride. Note that there is no lattice point in the center of the cell, and CsCl is not a BCC structure because a cesium ion is not identical to a chloride ion.

    Three images are shown. The first image shows a cube with black dots at each corner and a red dot in the center. This cube is stacked with seven others that are not colored to form a larger cube. The second image is composed of eight spheres that are grouped together to form a cube with one smaller sphere in the center. The name under this image reads “Body-centered simple cubic structure.” The third image shows five horizontal layers of purple spheres with layers of smaller green spheres in between.

    Figure \(\PageIndex{12}\): Ionic compounds with similar-sized cations and anions, such as CsCl, usually form a simple cubic structure. They can be described by unit cells with either cations at the corners or anions at the corners.

    We have said that the location of lattice points is arbitrary. This is illustrated by an alternate description of the CsCl structure in which the lattice points are located in the centers of the cesium ions. In this description, the cesium ions are located on the lattice points at the corners of the cell, and the chloride ion is located at the center of the cell. The two unit cells are different, but they describe identical structures.

    When an ionic compound is composed of a 1:1 ratio of cations and anions that differ significantly in size, it typically crystallizes with an FCC unit cell, like that shown in Figure \(\PageIndex{13}\). Sodium chloride, NaCl, is an example of this, with Na+ and Cl having radii of 102 pm and 181 pm, respectively. We can think of this as chloride ions forming an FCC cell, with sodium ions located in the octahedral holes in the middle of the cell edges and in the center of the cell. The sodium and chloride ions touch each other along the cell edges. The unit cell contains four sodium ions and four chloride ions, giving the 1:1 stoichiometry required by the formula, NaCl.

    Three images are shown. The first image shows a cube with black dots at each corner and a red dot in the center. This cube is stacked with seven others that are not colored to form a larger cube. The second image is composed of eight spheres that are grouped together to form a cube with one much larger sphere in the center. The name under this image reads “Body-centered simple cubic structure.” The third image shows seven horizontal layers of alternating purple and green spheres that are slightly offset with one another and form a large cube.

    Figure \(\PageIndex{13}\): Ionic compounds with anions that are much larger than cations, such as NaCl, usually form an FCC structure. They can be described by FCC unit cells with cations in the octahedral holes.

    The cubic form of zinc sulfide, zinc blende, also crystallizes in an FCC unit cell, as illustrated in Figure \(\PageIndex{14}\). This structure contains sulfide ions on the lattice points of an FCC lattice. (The arrangement of sulfide ions is identical to the arrangement of chloride ions in sodium chloride.) The radius of a zinc ion is only about 40% of the radius of a sulfide ion, so these small Zn2+ ions are located in alternating tetrahedral holes, that is, in one half of the tetrahedral holes. There are four zinc ions and four sulfide ions in the unit cell, giving the empirical formula ZnS.

    Two images are shown. The first image shows a cube with black dots at each corner and a red dot in the center of each face of the cube. This cube is stacked with seven others that are not colored to form a larger cube. The second image is composed of eight spheres that form the corners of a cube with six other spheres located in the face of the cube. The spheres are connected to one another by lines. The name under this image reads “Z n S, face-centered unit cell.”

    Figure \(\PageIndex{14}\): ZnS, zinc sulfide (or zinc blende) forms an FCC unit cell with sulfide ions at the lattice points and much smaller zinc ions occupying half of the tetrahedral holes in the structure.

    A calcium fluoride unit cell, like that shown in Figure \(\PageIndex{15}\), is also an FCC unit cell, but in this case, the cations are located on the lattice points; equivalent calcium ions are located on the lattice points of an FCC lattice. All of the tetrahedral sites in the FCC array of calcium ions are occupied by fluoride ions. There are four calcium ions and eight fluoride ions in a unit cell, giving a calcium:fluorine ratio of 1:2, as required by the chemical formula, CaF2. Close examination of Figure \(\PageIndex{17}\) will reveal a simple cubic array of fluoride ions with calcium ions in one half of the cubic holes. The structure cannot be described in terms of a space lattice of points on the fluoride ions because the fluoride ions do not all have identical environments. The orientation of the four calcium ions about the fluoride ions differs.

    Two images are shown. The first image shows a cube with black dots at each corner and a red dot in the center of each face of the cube. This cube is stacked with seven others that are not colored to form a larger cube. The second image is composed of eight small green spheres that form the corners of a cube with six other small green spheres located in the faces of the cube. Eight larger green spheres are spaced inside the cube and all of the spheres are connect to one another by lines. The name under this image reads “C a F, subscript 2, face-centered unit cell.”

    Figure \(\PageIndex{15}\): Calcium fluoride, CaF2, forms an FCC unit cell with calcium ions (green) at the lattice points and fluoride ions (red) occupying all of the tetrahedral sites between them.

    Summary

    The structures of crystalline metals and simple ionic compounds can be described in terms of packing of spheres. Metal atoms can pack in hexagonal closest-packed structures, cubic closest-packed structures, body-centered structures, and simple cubic structures. The anions in simple ionic structures commonly adopt one of these structures, and the cations occupy the spaces remaining between the anions. Small cations usually occupy tetrahedral holes in a closest-packed array of anions. Larger cations usually occupy octahedral holes. Still larger cations can occupy cubic holes in a simple cubic array of anions. The structure of a solid can be described by indicating the size and shape of a unit cell and the contents of the cell.

    Glossary

    body-centered cubic (BCC) solid
    crystalline structure that has a cubic unit cell with lattice points at the corners and in the center of the cell
    body-centered cubic unit cell
    simplest repeating unit of a body-centered cubic crystal; it is a cube containing lattice points at each corner and in the center of the cube
    coordination number
    number of atoms closest to any given atom in a crystal or to the central metal atom in a complex
    cubic closest packing (CCP)
    crystalline structure in which planes of closely packed atoms or ions are stacked as a series of three alternating layers of different relative orientations (ABC)
    face-centered cubic (FCC) solid
    crystalline structure consisting of a cubic unit cell with lattice points on the corners and in the center of each face
    face-centered cubic unit cell
    simplest repeating unit of a face-centered cubic crystal; it is a cube containing lattice points at each corner and in the center of each face
    hexagonal closest packing (HCP)
    crystalline structure in which close packed layers of atoms or ions are stacked as a series of two alternating layers of different relative orientations (AB)
    hole
    (also, interstice) space between atoms within a crystal
    isomorphous
    possessing the same crystalline structure
    octahedral hole
    open space in a crystal at the center of six particles located at the corners of an octahedron
    simple cubic unit cell
    (also, primitive cubic unit cell) unit cell in the simple cubic structure
    simple cubic structure
    crystalline structure with a cubic unit cell with lattice points only at the corners
    space lattice
    all points within a crystal that have identical environments
    tetrahedral hole
    tetrahedral space formed by four atoms or ions in a crystal
    unit cell
    smallest portion of a space lattice that is repeated in three dimensions to form the entire lattice

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