Some substances form crystalline solids consisting of particles in a very organized structure; others form amorphous (noncrystalline) solids with an internal structure that is not ordered. The main types of crystalline solids are ionic solids, metallic solids, covalent network solids, and molecular solids. The properties of the different kinds of crystalline solids are due to the types of particles of which they consist, the arrangements of the particles, and the strengths of the attractions between them. Because their particles experience identical attractions, crystalline solids have distinct melting temperatures; the particles in amorphous solids experience a range of interactions, so they soften gradually and melt over a range of temperatures. Some crystalline solids have defects in the definite repeating pattern of their particles. These defects (which include vacancies, atoms or ions not in the regular positions, and impurities) change physical properties such as electrical conductivity, which is exploited in the silicon crystals used to manufacture computer chips. 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. The type of structure and dimensions of the unit cell can be determined by X-ray diffraction measurements.
39.1 The Solid State of Matter
When most liquids are cooled, they eventually freeze and form crystalline solids, solids in which the atoms, ions, or molecules are arranged in a definite repeating pattern. It is also possible for a liquid to freeze before its molecules become arranged in an orderly pattern. The resulting materials are called amorphous solids or noncrystalline solids (or, sometimes, glasses). The particles of such solids lack an ordered internal structure and are randomly arranged (Figure 39.1).
The entities of a solid phase may be arranged in a regular, repeating pattern (crystalline solids) or randomly (amorphous).
Metals and ionic compounds typically form ordered, crystalline solids. Substances that consist of large molecules, or a mixture of molecules whose movements are more restricted, often form amorphous solids. For examples, candle waxes are amorphous solids composed of large hydrocarbon molecules. Some substances, such as silicon dioxide (shown in Figure 39.2), can form either crystalline or amorphous solids, depending on the conditions under which it is produced. Also, amorphous solids may undergo a transition to the crystalline state under appropriate conditions.
(a) Silicon dioxide, SiO2, is abundant in nature as one of several crystalline forms of the mineral quartz. (b) Rapid cooling of molten SiO2 yields an amorphous solid known as “fused silica”.
Crystalline solids are generally classified according to the nature of the forces that hold its particles together. These forces are primarily responsible for the physical properties exhibited by the bulk solids. The following sections provide descriptions of the major types of crystalline solids: ionic, metallic, covalent network, and molecular.
39.1.1 Ionic Solids
Ionic solids, such as sodium chloride and nickel oxide, are composed of positive and negative ions that are held together by electrostatic attractions, which can be quite strong (Figure 39.3). Many ionic crystals also have high melting points. This is due to the very strong attractions between the ions—in ionic compounds, the attractions between full charges are (much) larger than those between the partial charges in polar molecular compounds. This will be looked at in more detail in a later discussion of lattice energies. Although they are hard, they also tend to be brittle, and they shatter rather than bend. Ionic solids do not conduct electricity; however, they do conduct when molten or dissolved because their ions are free to move. Many simple compounds formed by the reaction of a metallic element with a nonmetallic element are ionic.
Sodium chloride is an ionic solid.
39.1.2 Metallic Solids
Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms Figure 39.4. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties. All exhibit high thermal and electrical conductivity, metallic luster, and malleability. Many are very hard and quite strong. Because of their malleability (the ability to deform under pressure or hammering), they do not shatter and, therefore, make useful construction materials. The melting points of the metals vary widely. Mercury is a liquid at room temperature, and the alkali metals melt below 200 °C. Several post-transition metals also have low melting points, whereas the transition metals melt at temperatures above 1000 °C. These differences reflect differences in strengths of metallic bonding among the metals.
Copper is a metallic solid.
39.1.3 Covalent Network Solid
Covalent network solids include crystals of diamond, silicon, some other nonmetals, and some covalent compounds such as silicon dioxide (sand) and silicon carbide (carborundum, the abrasive on sandpaper). Many minerals have networks of covalent bonds. The atoms in these solids are held together by a network of covalent bonds, as shown in Figure 39.5. To break or to melt a covalent network solid, covalent bonds must be broken. Because covalent bonds are relatively strong, covalent network solids are typically characterized by hardness, strength, and high melting points. For example, diamond is one of the hardest substances known and melts above 3500 °C.
A covalent crystal contains a three-dimensional network of covalent bonds, as illustrated by the structures of diamond, silicon dioxide, silicon carbide, and graphite. Graphite is an exceptional example, composed of planar sheets of covalent crystals that are held together in layers by noncovalent forces. Unlike typical covalent solids, graphite is very soft and electrically conductive.
39.1.4 Molecular Solid
Molecular solids, such as ice, sucrose (table sugar), and iodine, as shown in Figure 39.6, are composed of neutral molecules. The strengths of the attractive forces between the units present in different crystals vary widely, as indicated by the melting points of the crystals. Small symmetrical molecules (nonpolar molecules), such as H2, N2, O2, and F2, have weak attractive forces and form molecular solids with very low melting points (below −200 °C). Substances consisting of larger, nonpolar molecules have larger attractive forces and melt at higher temperatures. Molecular solids composed of molecules with permanent dipole moments (polar molecules) melt at still higher temperatures. Examples include ice (melting point, 0 °C) and table sugar (melting point, 185 °C).
Carbon dioxide (CO2) consists of small, nonpolar molecules and forms a molecular solid with a melting point of −78 °C. Iodine (I2) consists of larger, nonpolar molecules and forms a molecular solid that melts at 114 °C.
39.1.5 Properties of Solids
A crystalline solid, like those listed in Table 39.1, has a precise melting temperature because each atom or molecule of the same type is held in place with the same forces or energy. Thus, the attractions between the units that make up the crystal all have the same strength and all require the same amount of energy to be broken. The gradual softening of an amorphous material differs dramatically from the distinct melting of a crystalline solid. This results from the structural nonequivalence of the molecules in the amorphous solid. Some forces are weaker than others, and when an amorphous material is heated, the weakest intermolecular attractions break first. As the temperature is increased further, the stronger attractions are broken. Thus amorphous materials soften over a range of temperatures.
Types of Crystalline Solids and Their Properties
|Type of Solid||Type of Particles||Type of Attractions||Properties||Examples|
|ionic||ions||ionic bonds||hard, brittle, conducts electricity as a liquid but not as a solid, high to very high melting points||NaCl, Al2O3|
|metallic||atoms of electropositive elements||metallic bonds||shiny, malleable, ductile, conducts heat and electricity well, variable hardness and melting temperature||Cu, Fe, Ti, Pb, U|
|covalent network||atoms of electronegative elements||covalent bonds||very hard, not conductive, very high melting points||C (diamond), SiO2, SiC|
|molecular||molecules (or atoms)||IMFs||variable hardness, variable brittleness, not conductive, low melting points||H2O, CO2, I2, C12H22O11|
39.1.6 HOW SCIENCES INTERCONNECT
Graphene: Material of the Future
Carbon is an essential element in our world. The unique properties of carbon atoms allow the existence of carbon-based life forms such as ourselves. Carbon forms a huge variety of substances that we use on a daily basis, including those shown in Figure 39.7. You may be familiar with diamond and graphite, the two most common allotropes of carbon. (Allotropes are different structural forms of the same element.) Diamond is one of the hardest-known substances, whereas graphite is soft enough to be used as pencil lead. These very different properties stem from the different arrangements of the carbon atoms in the different allotropes.
Diamond is extremely hard because of the strong bonding between carbon atoms in all directions. Graphite (in pencil lead) rubs off onto paper due to the weak attractions between the carbon layers. An image of a graphite surface shows the distance between the centers of adjacent carbon atoms. (credit left photo: modification of work by Steve Jurvetson; credit middle photo: modification of work by United States Geological Survey)
You may be less familiar with a recently discovered form of carbon: graphene. Graphene was first isolated in 2004 by using tape to peel off thinner and thinner layers from graphite. It is essentially a single sheet (one atom thick) of graphite. Graphene, illustrated in Figure 39.8, is not only strong and lightweight, but it is also an excellent conductor of electricity and heat. These properties may prove very useful in a wide range of applications, such as vastly improved computer chips and circuits, better batteries and solar cells, and stronger and lighter structural materials. The 2010 Nobel Prize in Physics was awarded to Andre Geim and Konstantin Novoselov for their pioneering work with graphene.
Graphene sheets can be formed into buckyballs, nanotubes, and stacked layers.
39.1.7 Crystal Defects
In a crystalline solid, the atoms, ions, or molecules are arranged in a definite repeating pattern, but occasional defects may occur in the pattern. Several types of defects are known, as illustrated in Figure 39.9. Vacancies are defects that occur when positions that should contain atoms or ions are vacant. Less commonly, some atoms or ions in a crystal may occupy positions, called interstitial sites, located between the regular positions for atoms. Other distortions are found in impure crystals, as, for example, when the cations, anions, or molecules of the impurity are too large to fit into the regular positions without distorting the structure. Trace amounts of impurities are sometimes added to a crystal (a process known as doping) in order to create defects in the structure that yield desirable changes in its properties. For example, silicon crystals are doped with varying amounts of different elements to yield suitable electrical properties for their use in the manufacture of semiconductors and computer chips.
Types of crystal defects include vacancies, interstitial atoms, and substitutions impurities.
39.2 Lattice Structures in Crystalline Solids
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.
39.2.1 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.
39.2.2 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 39.10.
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 39.11. This arrangement is called simple cubic structure, and the unit cell is called the simple cubic unit cell or primitive cubic unit cell.
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 39.12, 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.
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 39.13. 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 atom within one simple cubic unit cell.
A simple cubic lattice unit cell contains one-eighth of an atom at each of its eight corners, so it contains one atom total.
Calculation of Atomic Radius and Density for Metals, Part 126.96.36.199
The edge length of the unit cell of alpha polonium is 336 pm.
(a) Determine the radius of a polonium atom.
(b) Determine the density of alpha polonium.
Alpha polonium crystallizes in a simple cubic unit cell:
(a) Two adjacent Po atoms contact each other, so the edge length of this cell is equal to two Po atomic radii: l = 2r. Therefore, the radius of Po is
(b) Density is given by The density of polonium can be found by determining the density of its unit cell (the mass contained within a unit cell divided by the volume of the unit cell). Since a Po unit cell contains one-eighth of a Po atom at each of its eight corners, a unit cell contains one Po atom.
The mass of a Po unit cell can be found by:
The volume of a Po unit cell can be found by:
(Note that the edge length was converted from pm to cm to get the usual volume units for density.)
Therefore, the density of
Check Your Learning
The edge length of the unit cell for nickel is 0.3524 nm. The density of Ni is 8.90 g/cm3
. Does nickel crystallize in a simple cubic structure? Explain.
No. If Ni was simple cubic, its density would be given by:
Then the density of Ni would be
Since the actual density of Ni is not close to this, Ni does not form a simple cubic structure.
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 39.14. (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.)
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 39.15. 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 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.
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 39.16. 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 atom from the corners) and one-half of an atom on each of the six faces 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.
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 39.17.
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.
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 39.18. 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.
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…).
Calculation of Atomic Radius and Density for Metals, Part 188.8.131.52
Calcium crystallizes in a face-centered cubic structure. The edge length of its unit cell is 558.8 pm.
(a) What is the atomic radius of Ca in this structure?
(b) Calculate the density of Ca.
(a) In an FCC structure, Ca atoms contact each other across the diagonal of the face, so the length of the diagonal is equal to four Ca atomic radii (d = 4r). Two adjacent edges and the diagonal of the face form a right triangle, with the length of each side equal to 558.8 pm and the length of the hypotenuse equal to four Ca atomic radii:
Solving this gives
(b) Density is given by The density of calcium can be found by determining the density of its unit cell: for example, the mass contained within a unit cell divided by the volume of the unit cell. A face-centered Ca unit cell has one-eighth of an atom at each of the eight corners atom) and one-half of an atom on each of the six faces atoms), for a total of four atoms in the unit cell.
The mass of the unit cell can be found by:
The volume of a Ca unit cell can be found by:
(Note that the edge length was converted from pm to cm to get the usual volume units for density.)
Then, the density of
Check Your Learning
Silver crystallizes in an FCC structure. The edge length of its unit cell is 409 pm.
(a) What is the atomic radius of Ag in this structure?
(b) Calculate the density of Ag.
(a) 144 pm; (b) 10.5 g/cm3
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 3919. The axes are defined as being the lengths between points in the space lattice. Consequently, unit cell axes join points with identical environments.
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 39.20.
There are seven different lattice systems and 14 different unit cells.
39.2.5 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. Figure 39.21 illustrates both of these types of holes.
Cations may occupy two types of holes between anions: octahedral holes or tetrahedral 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 Figure 39.22. 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.
A cation’s size and the shape of the hole occupied by the compound are directly related.
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 Li2O, Na2O, Li2S, and Na2S. 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.
Occupancy of Tetrahedral Holes
Zinc sulfide is an important industrial source of zinc and is also used as a white pigment in paint. Zinc sulfide crystallizes with zinc ions occupying one-half of the tetrahedral holes in a closest-packed array of sulfide ions. What is the formula of zinc sulfide?
Because there are two tetrahedral holes per anion (sulfide ion) and one-half of these holes are occupied by zinc ions, there must be
or 1, zinc ion per sulfide ion. Thus, the formula is ZnS.
Check Your Learning
Lithium selenide can be described as a closest-packed array of selenide ions with lithium ions in all of the tetrahedral holes. What it the formula of lithium selenide?
The ratio of octahedral holes to anions in either an HCP or CCP structure is 1:1. Thus, compounds with cations in octahedral holes in a closest-packed array of anions can have a maximum cation:anion ratio of 1:1. In NiO, MnS, NaCl, and KH, for example, all of the octahedral holes are filled. Ratios of less than 1:1 are observed when some of the octahedral holes remain empty.
Stoichiometry of Ionic Compounds
Sapphire is aluminum oxide. Aluminum oxide crystallizes with aluminum ions in two-thirds of the octahedral holes in a closest-packed array of oxide ions. What is the formula of aluminum oxide?
Because there is one octahedral hole per anion (oxide ion) and only two-thirds of these holes are occupied, the ratio of aluminum to oxygen must be
:1, which would give
The simplest whole number ratio is 2:3, so the formula is Al2
Check Your Learning
The white pigment titanium oxide crystallizes with titanium ions in one-half of the octahedral holes in a closest-packed array of oxide ions. What is the formula of titanium oxide?
In a simple cubic array of anions, there is one cubic hole that can be occupied by a cation for each anion in the array. In CsCl, and in other compounds with the same structure, all of the cubic holes are occupied. Half of the cubic holes are occupied in SrH2, UO2, SrCl2, and CaF2.
Different types of ionic compounds often crystallize in the same structure when the relative sizes of their ions and their stoichiometries (the two principal features that determine structure) are similar.
39.2.8 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, (illustrated in Figure 39.23) 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.
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 39.24. 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.
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 39.25. 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.
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 39.26, 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 39.26 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.
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.
39.2.9 Calculation of Ionic Radii
If we know the edge length of a unit cell of an ionic compound and the position of the ions in the cell, we can calculate ionic radii for the ions in the compound if we make assumptions about individual ionic shapes and contacts.
Calculation of Ionic Radii
The edge length of the unit cell of LiCl (NaCl-like structure, FCC) is 0.514 nm or 5.14 Å. Assuming that the lithium ion is small enough so that the chloride ions are in contact, as in Figure 39.24
, calculate the ionic radius for the chloride ion.
Note: The length unit angstrom, Å, is often used to represent atomic-scale dimensions and is equivalent to 10−10 m.
On the face of a LiCl unit cell, chloride ions contact each other across the diagonal of the face:
Drawing a right triangle on the face of the unit cell, we see that the length of the diagonal is equal to four chloride radii (one radius from each corner chloride and one diameter—which equals two radii—from the chloride ion in the center of the face), so d = 4r. From the Pythagorean theorem, we have:
Solving this gives:
Check Your Learning
The edge length of the unit cell of KCl (NaCl-like structure, FCC) is 6.28 Å. Assuming anion-cation contact along the cell edge, calculate the radius of the potassium ion. The radius of the chloride ion is 1.82 Å.
The radius of the potassium ion is 1.33 Å.
It is important to realize that values for ionic radii calculated from the edge lengths of unit cells depend on numerous assumptions, such as a perfect spherical shape for ions, which are approximations at best. Hence, such calculated values are themselves approximate and comparisons cannot be pushed too far. Nevertheless, this method has proved useful for calculating ionic radii from experimental measurements such as X-ray crystallographic determinations.
39.2.11 X-Ray Crystallography
The size of the unit cell and the arrangement of atoms in a crystal may be determined from measurements of the diffraction of X-rays by the crystal, termed X-ray crystallography. Diffraction is the change in the direction of travel experienced by an electromagnetic wave when it encounters a physical barrier whose dimensions are comparable to those of the wavelength of the light. X-rays are electromagnetic radiation with wavelengths about as long as the distance between neighboring atoms in crystals (on the order of a few Å).
When a beam of monochromatic X-rays strikes a crystal, its rays are scattered in all directions by the atoms within the crystal. When scattered waves traveling in the same direction encounter one another, they undergo interference, a process by which the waves combine to yield either an increase or a decrease in amplitude (intensity) depending upon the extent to which the combining waves’ maxima are separated (see Figure 39.27).
Light waves occupying the same space experience interference, combining to yield waves of greater (a) or lesser (b) intensity, depending upon the separation of their maxima and minima.
When X-rays of a certain wavelength, λ, are scattered by atoms in adjacent crystal planes separated by a distance, d, they may undergo constructive interference when the difference between the distances traveled by the two waves prior to their combination is an integer factor, n, of the wavelength. This condition is satisfied when the angle of the diffracted beam, θ, is related to the wavelength and interatomic distance by the equation:
This relation is known as the Bragg equation in honor of W. H. Bragg, the English physicist who first explained this phenomenon. Figure 39.28 illustrates two examples of diffracted waves from the same two crystal planes. The figure on the left depicts waves diffracted at the Bragg angle, resulting in constructive interference, while that on the right shows diffraction and a different angle that does not satisfy the Bragg condition, resulting in destructive interference.
The diffraction of X-rays scattered by the atoms within a crystal permits the determination of the distance between the atoms. The top image depicts constructive interference between two scattered waves and a resultant diffracted wave of high intensity. The bottom image depicts destructive interference and a low intensity diffracted wave.
Visit this site for more details on the Bragg equation and a simulator that allows you to explore the effect of each variable on the intensity of the diffracted wave.
An X-ray diffractometer, such as the one illustrated in Figure 39.29, may be used to measure the angles at which X-rays are diffracted when interacting with a crystal as described earlier. From such measurements, the Bragg equation may be used to compute distances between atoms as demonstrated in the following example exercise.
(a) In a diffractometer, a beam of X-rays strikes a crystalline material, producing (b) an X-ray diffraction pattern that can be analyzed to determine the crystal structure.
Using the Bragg Equation
In a diffractometer, X-rays with a wavelength of 0.1315 nm were used to produce a diffraction pattern for copper. The first order diffraction (n
= 1) occurred at an angle θ
= 25.25°. Determine the spacing between the diffracting planes in copper.
The distance between the planes is found by solving the Bragg equation, nλ
, for d
Check Your Learning
A crystal with spacing between planes equal to 0.394 nm diffracts X-rays with a wavelength of 0.147 nm. What is the angle for the first order diffraction?
39.2.13 PORTRAIT OF A CHEMIST
X-ray Crystallographer Rosalind Franklin
The discovery of the structure of DNA in 1953 by Francis Crick and James Watson is one of the great achievements in the history of science. They were awarded the 1962 Nobel Prize in Physiology or Medicine, along with Maurice Wilkins, who provided experimental proof of DNA’s structure. British chemist Rosalind Franklin made invaluable contributions to this monumental achievement through her work in measuring X-ray diffraction images of DNA. Early in her career, Franklin’s research on the structure of coals proved helpful to the British war effort. After shifting her focus to biological systems in the early 1950s, Franklin and doctoral student Raymond Gosling discovered that DNA consists of two forms: a long, thin fiber formed when wet (type “B”) and a short, wide fiber formed when dried (type “A”). Her X-ray diffraction images of DNA (Figure 39.30) provided the crucial information that allowed Watson and Crick to confirm that DNA forms a double helix, and to determine details of its size and structure. Franklin also conducted pioneering research on viruses and the RNA that contains their genetic information, uncovering new information that radically changed the body of knowledge in the field. After developing ovarian cancer, Franklin continued to work until her death in 1958 at age 37. Among many posthumous recognitions of her work, the Chicago Medical School of Finch University of Health Sciences changed its name to the Rosalind Franklin University of Medicine and Science in 2004, and adopted an image of her famous X-ray diffraction image of DNA as its official university logo.
This illustration shows an X-ray diffraction image similar to the one Franklin found in her research. (credit: National Institutes of Health)