Solids

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Lecture Notes

Chemistry 112

Structure of Solids

Types of Solids
There are many ways to classify solids, The first classification involves grouping according to the regularity of the atoms/molecules within the solid. 1. Crystalline Solids contain atoms or molecules bonded together in a regular pattern. A good example of these is quartz crystals SiO2 where each Si is bonded to four oxygens which in turn are bonded to two silicons in a continuous covalent network extending in three dimensions. You can find these crystals in your quartz watch. The crystal vibrates at a frequency when electric charge is placed across certain directions. Your watch uses the vibrations to keep time. 2. Amorphous solids (or glasses) are made up of atoms or molecules with no regular arrangement. Quartz that has been melted into liquid and cooled (moderately) rapidly will form glass. Quartz glass is used for applications like windows on lasers, and fine optics like Zeiss lenses. In either of these, there can be several methods of bonding the atoms together. Solids can be classified in several ways. One way is to identify the type of bonding that holds the solid together. 1. Molecular solids consist of molecules that are held together by week intermolecular forces. A prime example of this is sugar. Molecules of sugar are held together by intermolecular forces far weaker than the covalent bonds that keep the atoms within each molecule. This type of solid may not have a high melting point none are higher than 400C. some actually decay before melting, as in Sugar which caramelizes and/or burns before melting. 2. Covalent (network) solids are made of atoms that are covalently bonded together to form one continuous network of covalently bonded atoms. One could almost think of this type of solids as macroscopic molecules (big enough to see). Diamonds are a prime example of such solids. This type of solid tends to have a high melting point and are normally quite hard. For example, diamond melts at 3600C. 3. Ionic (network) solids contain ions of opposite charge which hold together with electrostatic (Columbic) interactions. A good example of

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this is sodium chloride (table salt). In this crystal shown on the right, the atoms of Na+ alternate with atoms of Cl- such that each positive ion has neighbouring negative ions and vice versa. Ionic solids tend to have a melting point that ranges from quite low to moderately, depending on the strength of the ionic bond. 4. Finally, metallic (network) solids are made up of metal atoms, whose loosely held outer electrons are somewhat free their positive cores and form a continuous dissociated sea of negative charge binding the positive cores together. This type of material can have a low melting point and also tend to be soft. Metals can be reshaped by striking (malleable) or drawn through small openings (ductile) the way copper is formed into wires. Copper is shown in the model on the right. In Network solids there are no distinct molecules or clusters within the structure. The array of atoms extends continuously throughout the whole solid. Network solids can form a. one dimensional networks (plastic sulfur), These tend to form very soft plastic or even waxy/tar-like solids. b. two dimensional networks (graphite). These have planes of atoms that can easily slide over each. For example, graphite is used as lubricant. c. three dimensional networks (diamond). These tend to be very strong and hard.

Lattices
For the rest of this section, we will restrict our discussion to crystalline solids. These have atoms or groups of atoms arranged in a regular array or lattice in three dimensions. We should look at the term lattice and define it closely. A lattice is a mathematical abstraction that describes the way the atoms or groups of atoms are repeated in space. We must not mistake the diagrams that follow for arrangements of atoms. The following details only the mathematical points that make up the lattice. Let's first look at simple lattices in two dimensions. We will then extend the discussion into three dimensions. A unit cell is any subset of the lattice that contains enough information that the whole lattice can be rebuilt by starting with just the unit cell and translating or rotating according to the symmetry of the lattice. The simplest unit cell is one that contains the least number of points and needs only translations along the cell edges to repeat the pattern. Unit cells contain the "stuff" we want to repeat. The famous Dutch artist Escher regularly created paintings that were made up of repeating units.

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units. Can you find the unit cell here? The simplest of the 2d lattices is the square lattice. We can choose a unit cell (the repeating unit) in any such that it has equal length sides (a) and an angle of 90. we can locate the cell wherever we please. One choice puts one point of our lattice at each corner of the cell. We could have alternatively, placed the unit cell such that one point was at the centre. Less conveniently, we could have placed the cell with one point anywhere within its boundaries. In all cases, there is 1 point for each unit cell (the first choice saw only 1/4 of each vertex actually inside the boundaries of the unit cell.

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A hexagonal lattice contains points arranged such that a unit cell can be drawn with angles of 60 and all sides of length a. A complete hexagon is drawn for visual effect.

Another type of lattice is a rectangular lattice. The unit cell in this lattice would have angles of 90 like the square lattice but would have different length sides a and b.

The Rhombic lattice has a unit cell with equal length sides but an angle that is neither 60 nor 90 .

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Finally, the least symmetric of all two dimensional lattices is the fully rhombic (parallelogram) lattice. Here, the angles are neither 90, nor 60 degrees and the sides of the unit cell are not all the same length.

In two dimensions, there are only these 5 lattices. In three dimensions, the lattices are called space lattices or Bravais lattices. There are 14 Bravais lattices. For our purposes, we will look only at two basic types of three dimensional lattices, cubic lattices and hexagonal lattices. Cubic lattices There are several cubic lattices. We will focus on three of them here. These include the simple cubic lattice, the body-centred cubic lattice and the face-centred cubic lattice. The simple cubic lattice has only one 1 lattice point within each unit cell. Notice that there seem to be eight spheres (points) associated with this unit cell (the box). It is important to recall that only the part of the point that is inside the box is truly in the unit cell. Since only 1/8 of each corner point is actually inside the unit cell, there is really only 8 1/8 = 1 point for each unit cell. Each lattice point has 6 nearest neighbours (four are shown here). We define this as the coordination number.

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A body centred cubic (bcc) unit cell has two points associated with it. The 81/8=1 corner points and the one point in the centre of the cell. Monatomic bcc lattices obviously have a coordination number of 8

The face centred cubic (fcc) lattice, has 4 points associated with its unit cell. The 81/8=1 corner points and 61/2=3 face-centred points. These points are only half inside the box and so we only get to claim half of the point for the unit cell. An alternate name for the face centred cubic lattice is the cubic closest packing (ccp). This is one of two closest-packing arrays where the points have packed in the most efficient (least volume) way possible. The 3d model on the left shows the lattice points. the diagrams on the left show two different views of monatomic structures that use fcc packing. The far left one shows stacking layers abc and allows us to count the nearest neighbours to a particular atom (red). We see that the coordination number for this type of crystal is 12. The other diagram shows the fraction of each atom that is actually inside the unit cell.

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The other major class of three dimensional crystal lattice is one that gives a hexagonal unit cell. Like the hexagonal 2d array, the hexagonal 3d array has some angles of 60 with 90 directions perpendicular to that. The unit cell of the hexagonal closest packing (hcp) array has two sides of length a, separated by angles of 60 and one side of length b at an angle of 90 to the two others. This is the other closest packing array where the points are packed in their most efficient (least volume) way possible. You can see that this unit cell has one point fully inside and 8 apex points 4 have 8.33% inside and 4 have 16.66% inside the unit cell which between them add up to one point inside.

hcp lattice with unit cell highlighted.

hcp lattice with closest neighbouring points highlighted.

Metals
In metals, the valence electrons tend to be quite loosely held. These outer electrons are easily lost or shared with little effort. Lets consider a solid piece (crystal) of metal (for example, Sodium) where the outer orbital (s) of the neighbouring metal atoms all overlap each other.

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We see here that the loosely held electrons can freely roam from atom to atom with no hindrance. In effect, the sodium cores (+1 charge) are floating in a sea of electrons (negative charges). This allows for several properties characteristic of metals. 1. malleable: if you strike the metal, the atoms can slide over each other without breaking any actual bonds. Gold can be hammered into gold-leaf (10 atoms thick) without fracturing the metal. 2. ductile: metals can be drawn through a small opening as in copper is pulled through a hole in a steel plate to form wire. 3. lustrous: Because of the large number of overlapping orbitals, the energy levels are very closely spaced such that photons of a large range of frequencies are absorbed and instantly re-emitted (alias, reflected). 4. electrically conductive: since the electrons are quite mobile, metals easily conduct electricity. Because of the non-directional bonding that occurs in metals, atoms of metal crystals tend to pack in a very efficient manor. The two most efficient packing methods are ones that follow the hcp and ccp lattices, which have identical packing efficiencies (about 74% of the crystal volume is actually atoms). A third common packing method of metals is bcc, which is not as efficient as hcp or bcc. Most metals tend to have monatomic crystal structures. They have only one atom associated with each crystal lattice point. This makes it easy to compare atomic positions with crystal lattice positions. We can choose to exactly overlap the atomic positions with the lattice points. This (very common) choice leads to confusion by some who think that the atom is the lattice point. This is merely a coincidental choice made in monatomic crystals for the sake of simplicity. Iron tends to pack in a monatomic bcc crystal structure. This means that there is only one atom associated with each lattice point in the crystal lattice. For convenience, we tend to put the atoms exactly on the lattice points but this is not necessary as long as all lattice points share exactly the same spacial arrangement with one and only one atom per point. Iron's atoms have 8 nearest neighbours and thus have a coordination number of 8.

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Copper tends to pack in a monatomic ccp arrangement, where each atom is associated with its own lattice point in the ccp lattice. Recall that this is the face centred cubic lattice array. Each atom has a coordination number of 12, i.e., there are 12 nearest neighbours for each atom of copper. Zinc atoms tends to arrange themselves in a monatomic hcp crystal structure where one and only one atom of Zn is associate with each lattice point in the hcp crystal lattice. Each Zn atom has 12 nearest neighbours, i.e., the coordination number is 12.

Ionic Solids
Ionic solids do not form monatomic crystal structures but many still form closest packing arrangements since the ionic bonds are non-directional. To envision the crystal structure of many ionic crystals, we need to look at many factors, including the relative size of the positive and negative ions and the relative number of them. Lets look at the packing arrangement of the atoms in a close-packing structure. We see that there are two types of spaces between the atoms. 1. Tetrahedral spaces exist where four atoms come together (atom from layer b on top of triangular hole from layer a).

2. Octahedral spaces occur where six atoms come together (three atoms from layer b surround a hole from layer a)

Since the octahedral holes are larger than the tetrahedral ones, they can accommodate larger cations, relative to the size of the anions. Take Sodium chloride. The chloride ions (green in the model to the left) are significantly larger than the sodium ions (blue) and we can consider the sodium chloride to be a closest packing fcc array

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of chloride ions with sodium ions filling the octahedral holes between them. Since there are two "atoms" associated with each lattice point, NaCl has a diatomic fcc crystal structure. The calcium fluorite (CaF2) structure has Calcium cations in the tetrahedral spaces between fluoride ions. Note that there are different ratios of holes to atoms for tetrahedral (1 hole : 2 atoms) versus octahedral (1:1) holes.

Cell calculations
Once we understand the structure of crystals, we can do many different types of calculations using this information. For the sake of simplicity, we will restrict ourselves to calculations involving monatomic (metallic) cubic crystal structures. Let's first look at the geometry of a cube.

The cube has all sides of length a. Each face has a face diagonal of length b and the body diagonal has a length c. Using Standard trigonometric relationships, we can easily derive the following relationships. b2 = 2 a2 or and c2 = 3 a2 or c = (3 a2)1/2. b = (2 a2)1/2

Thus, if we are dealing with a Body centred cubic structure, the body diagonal is the only cell direction that is a simple multiple of atom radii.

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Here, we see that c is equal to four atomic radii. c = 4 r

or

r = c/4

By the same logic, in a face centred cubic structure, the face diagonal would be equal to 4 times the atomic radius. b=4r or r = b/4

Example: The length of a unit cell of iron (monatomic bcc) is measured to be 286 pm using x-ray diffraction. What is the size (radius) of the iron atom? Since Fe is monatomic bcc, we have

Example: Vanadium has a unit cell structure like iron. x-ray diffraction shows the unit cell dimension to be 305 pm. What is the density of Vanadium?

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