The Chemistry Of Engineering

Materials
SCI 401: General Chemistry - Unit 3

Engr. Tiffany Jade Medrano

Basic Concepts of Crystal
Structures
Unit 3. The Chemistry of Engineering Materials

Engr. Tiffany Jade Medrano

Topic Outline

● Unit Cells
● Density Computations
● Types of Crystals
● Amorphous Solids
Crystal Structures
Categories of Solids

● Crystalline Solid
● Amorphous Solid
Crystalline Solid

● Has rigid and long-range order and its atoms, molecules, or ions occupy
specific positions.
● The arrangement of particles is such that the net attractive intermolecular
forces are at their maximum.
● The molecular forces responsible for the stability of a crystal can be ionic
forces, covalent bonds, van der Waals forces, hydrogen bonds, or a
combination of these forces.
Amorphous Solid

● There is an absence of a well-defined arrangement and long-range

molecular order
Atomic Hard-Sphere Model

Atoms or ions (described as crystalline structures) are thought of as being solid

spheres having well-defined diameters.

This is known as the atomic hard-sphere model in which spheres representing

nearest-neighbor atoms touch one another.

Sometimes the word lattice is used in the context of crystal structures; in this
sense lattice means a three- dimensional array of points coinciding with atom
positions or sphere centers.
Unit Cells
Unit Cells

A unit cell is the basic structural (repeating) unit of a crystalline solid.

Figure 1. (a) unit cell and (b) an extension of unit cell in three dimensions. The black
spheres denote either atoms or molecules

For each sphere, it denotes an atom, ion, or molecule and it is called a lattice
point.
Unit Cells

In many crystals, the lattice point does not actually contain such a particle.
Rather, there may be several atoms, ions, or molecules identically arranged
about each lattice point.
To be simple, we can assume that each lattice point is occupied by an atom
where cases are mostly metals.
Unit Cells
The Seven Types of Unit Cells
Angle α is defined by edges b and c

Angle β by edges a and c

Angle γ by edges a and b

The Face-Centered Cubic Crystal

A unit cell of cubic geometry is considered to be the crystal structure found for
many metals.

The face-centered cubic (FCC) is a crystal structure with atoms located at each of
the corners and the center of all the cube faces.

Some familiar metals having this crystal structure are copper, aluminum, silver,
and gold.
Figure a shows a hard-sphere model for the FCC unit cell,

Figure b, the atom centers are represented by small circles to provide a

better perspective on atom positions.

The aggregate of atoms in Figure c represents a section of crystal

consisting of many FCC unit cells.
FCC

These spheres or ion cores touch one another across a face diagonal;
the cube edge length, a and the atomic radius, R are related through:
Number of atoms per unit cell

In determining the number of atoms associated with each unit cell, that depends on
an atom’s location, shared with adjacent unit cells may be considered.

That is, some fraction of the atom is assigned to a specific cell.

For example, for cubic unit cells, an atom completely within the interior “belongs” to
that unit cell, one at a cell face is shared with one other cell, and an atom residing at
a corner is shared among eight.
Number of atoms per unit cell

The number of atoms per unit cell can be calculated using the
following formula:

Where Ni = the number of interior atoms; Nf = number of face

atoms and Nc = number of corner atoms
Number of atoms per unit cell

For the FCC crystal structure, there are eight corner atoms, six face atoms
and no interior atoms. Therefore:

A total of four whole atoms may be assigned to a given unit cell.

Two Important Characteristics of Crystal Structure

(a)the coordination number (for metals) wherein each atom has the
same number of nearest-neighbor or touching atoms; and

(b) atomic packing factor (APF) which is the sum of the sphere volumes
of all atoms within a unit cell (assuming the atomic hard-sphere model)
divided by the unit cell volume.
Two Important Characteristics of Crystal Structure

From the definition of APF, the formula is:

The Body-Centered Cubic Crystal Structure

A body-centered cubic (BCC) is another common metallic crystal structure

that also has a cubic unit cell with atoms located at all eight corners and a
single atom at the center of the cube.
The Body-Centered Cubic Crystal Structure

Body-centered cubic crystal structure

(a) a hard-sphere unit cell representation, (b) a reduced-sphere unit cell,

and (c) an aggregate of many atoms
BCC

Corner atoms and center touch one another along with the diagonal of the
cube, and unit cell length a and atomic radius R are related by the way
of:
Number of Atoms per BCC

The BCC crystal structure has 8 coordination number. The atomic packing
factor for BCC is 0.68 which is lower than for FCC, since BCC has lesser
coordination number.
Simple Cubic Crystal Structure

The possibility of a unit cell that consists of atoms placed only at the corners of
a cube do exist and it is called the simple cubic (SC) crystal structure.

Polonium, a metalloid or a semi-metal is the only simple-cubic element that has

a relatively low atomic packing factor.
Simple Cubic Crystal Structure

Simple cubic crystal structure

(a) hard-sphere unit cell, and (b) a reduced-sphere unit cell.

The Hexagonal Close-Packed Crystal Structure

In the hexagonal close-pack crystal structure (HCP), the top and bottom faces
of the unit cell is consist of six atoms that form regular hexagons and surround
a single atom in the center.

Between the top and bottom planes, there is another plane that provides three
additional atoms to the unit cell. The atoms in this midplane have as nearest
neighbors atoms in both of the adjacent two planes.
The Hexagonal Close-Packed Crystal Structure

(a) a reduced-sphere unit cell (a and c represent the short and long edge lengths,
respectively), and (b) an aggregate of many atoms
Number of Atoms per unit cell of HCP

One-sixth of each corner atom is designated to a unit cell instead of 8 as with the cubic
structure. This is because, HCP has 6 corner atoms in each of the top and bottom faces for a
total of 12 corner atoms, 2 face center atoms (one from each of the top and bottom faces),
and 3 midplane interior atoms.
Number of Atoms per unit cell of HCP

There are 6 atoms assigned to each unit cell

Density Computations
Density Computations

A theoretical density can be computed with a knowledge of the crystal

structure of a metallic solid through the relationship:
Density Computations

where:
n = number of atoms associated with each unit cell
A = atomic weight
VC = volume of the unit cell
NA = Avogadro’s number (6.022 x 10^23 atoms/mol)
Density Computations
X-Ray Diffraction by Crystals

X-ray diffraction refers to the scattering of X-rays by the units of a crystalline solid.

The patterns produced by scattering, or diffraction are used to deduce the particle
arrangement in the solid lattice.
X-Ray Diffraction by Crystals

X-rays are one form of electromagnetic radiation, therefore,

we would expect that waves exhibit such behavior under
relevant conditions.
In 1912, Max von Laue, a German physicist recommended
that since the wavelength of X-rays is comparable in
magnitude to the distances between lattice points in a
crystal, then the lattice should be able to diffract X-rays.
Interference in the waves associated with X-rays produced an
X-ray diffraction pattern.
X-Ray Diffraction by Crystals

Constructive interference (a) and destructive interference

(b) of two waves of the same wavelength and amplitude
X-Ray Diffraction by Crystals

A beam of X rays is directed

at a mounted crystal. Atoms
in the crystal absorb some of
the incoming radiation and
then reemit it; the process is
called the scattering of X
rays.
X-Ray Diffraction by Crystals
The X-ray diffraction technique gives the most accurate method for determining
bond lengths and bond angles in molecules in the solid state.

Chemists can construct an electron- density contour map from the diffraction
patterns because X-rays are scattered by electrons but it is with the use of a
complex mathematical procedure.

An electron-density contour map basically tells us the relative electron

densities at various locations in a molecule. The densities reach a maximum
near the center of each atom and in this manner we can determine the
positions of the nuclei and thus the molecular geometric parameters.
Types of Crystals
Types of Crystals

In determining the structures and properties of crystals, such as melting point,

density, and hardness it is important to consider the kinds of forces that hold the
particles together.

The classification of any crystal has four types: ionic, covalent, molecular, or
metallic.
Ionic Crystals

Two important characteristics of ionic crystals:

(1) They are composed of charged species and

(2) anions and cations are generally quite different in size.

Ionic Crystals

The radii of the ions must be known because it is helpful in understanding

the structure and stability of these compounds. It is hard to measure the
radius of an individual ion but sometimes it is possible to come up with an
estimation.
Ionic Crystals

The radii of the ions must be known because it is helpful in understanding the
structure and stability of these compounds. It is hard to measure the radius of
an individual ion but sometimes it is possible to come up with an estimation.
For example, if we know the radius of I- in KI is about 216 pm, we can
determine the radius of K+ ion in KI , and from that, the radius of Cl- in KCl,
and so on.
Ionic Crystals

For example, the NaCl crystal which has a face-centered cubic lattice
shows that the edge length of the unit cell of NaCl is twice the sum of
the ionic radii of Na+ and Cl-.

Getting the values of ionic radius given in some references the we

calculate the length of the edge to 2(95 + 181) pm, or 552pm. In The
edge length shown was determined by X-ray diffraction which has a
value of 564pm.

The difference between these two values tells us that the radius of an
ion actually varies slightly from one compound to another.
Crystal structures of (a) CsCl, (b) ZnS, and (c) CaF2.
● CsCl has the simple cubic lattice because Cs+ is considerably larger than
Na+.
● ZnS has the zincblende structure, which is based on the face-centered
cubic lattice. If the S2- ions occupy the lattice points, the Zn2+ ions are
located one-fourth of the distance along each body diagonal.
○ Other ionic compounds that have the zincblende structure include CuCl,
BeS, CdS and HgS.
● CaF2 has the fluorite structure. The Ca2+ ions occupy the
lattice points, and each F- ion is tetrahedrally surrounded by
four Ca2+ions.
○ The compounds SrF2, BaF2, BaCl2 and PbF2 also have the
fluorite structure.
Ionic Crystals

Most ionic crystals have high melting points which is an is an indication of the
strong cohesive forces holding the ions together.

A measure of the stability of ionic crystals is the lattice energy; the higher the
lattice energy, the more stable the compound.

Since the ions are fixed in position, therefore these solids do not conduct
electricity. The ions are free to move when in the molten state (melted) or
dissolved in water, thereby the resulting liquid is conducting electricity.
Covalent Crystals

Covalent crystals exists when atoms are held together in an extensive three-
dimensional network altogether by covalent bonds. Examples are the two
allotropes of carbon: diamond and graphite.
Covalent Crystals

Each carbon atom of diamond is sp3 hybridized where it is bonded to four other
atoms.

The term “sp3 hybridization” refers to the mixing character of one 2s-orbital
and three 2p-orbitals to create four hybrid orbitals with similar characteristics.
In order for an atom to be sp3 hybridized, it must have an s orbital and three p
orbitals.
Covalent Crystals

The unusual hardness and very high melting point (3550°C) of diamond are
attributed with the strong covalent bonds that exist in three dimensions.

For graphite, carbon atoms are arranged in six-membered rings.

The atoms are all sp2-hybridized and each atom is covalently bonded to three
other atoms. There is a remaining unhybridized 2p orbital that is used in pi
bonding.
Covalent Crystals

(a) The structure of diamond. Each carbon is tetrahedrally bonded to four

other carbon atoms. (b) The structure of graphite. The distance between
successive layers is 335 pm
Covalent Crystals

Graphite is considered as a good conductor of electricity in directions along the

planes of carbon atoms, this is because electrons are free to move around in this
extensively delocalized molecular orbital.

The hardness of graphite is caused by the covalent bonds that exist in its layers
which are held together by weak van der Waals forces. Furthermore, the layers of
graphite can slide one another, that’s why it is slippery to the touch and is
effective as lubricant. It is also used in pencils and ribbons made for computer
printers and typewriters.
Covalent Crystals

Another example of covalent crystal is quartz (SiO2). The silicon atoms in

quartz has a similar arrangement to that of carbon in diamond, but in quartz
there is a presence of oxygen atom between each pair of Si atoms. A polarity
exist in Si - O bond because Si and O have different electronegativities.

Still, SiO2 is similar to diamond in many aspects because of its hardness and
high melting point of 1610 °C.
Molecular Crystals

The lattice points in a molecular crystal are occupied by molecules which has a
van der Waals forces and/or hydrogen bonding.

Solid sulfur dioxide (SO2) is an example in which the predominant attractive

force is a dipole-dipole interaction. The intermolecular hydrogen bonding is
mainly responsible for maintaining the three-dimensional lattice of ice. I2, P4
and S8 are other examples of molecular crystals.
Molecular Crystals

The molecules in a molecular crystals (except for ice) are packed together as
closely as their size and shape allow.

Since van der Waals and hydrogen bonding are generally quite weak as
compared with ionic and covalent bonds, molecular crystals are more easily
broken apart than ionic and covalent crystals.

Additionally, most molecular crystals melt at temperature below 100 °C.

Metallic Crystals

Metallic crystals has the simplest structure because every lattice points in the
crystal are occupied by an atom of the same metal.

Metallic crystals are usually body-centered cubic, face-centered cubic or

hexagonal close-packed, therefore metallic elements are usually very dense.
Metallic Crystals

The bonding electrons in a metal are delocalized over the entire crystals which
is actually different from other types of crystals. The metal atoms in a crystal
can be imagined as an array of positive ions immersed in a sea of delocalized
valence electrons and these delocalized electron makes metals a good
conductor of heat and electricity. And also, metal’s strength is caused by the
great cohesive forces resulting from delocalization.
Amorphous Solids
Amorphous Solids

We all know that crystalline form of solids are most stable, but if it solidify
rapidly then its atoms or molecules do not have time to align themselves and
may become locked in positions other than those of regular crystals. This
resulting solid is said to be amorphous.

Amorphous solids lack a regular three-dimensional arrangement of atoms.

Amorphous Solids

Glass is an example of an amorphous solid. Glass commonly refers to an

optically transparent fusion product of inorganic materials that has cooled to a
rigid state without crystallizing.

By product of a fusion, we mean that the glass is formed by mixing molten

silicon dioxide (SiO2), with compounds such as sodium oxide (Na2O), boron
oxide (B2O3), and certain transition metal oxides for color and other properties.
Amorphous Solids

Silicon dioxide is the chief component of glass.

In some aspect glass acts more like a liquid than a solid.

Glass lacks a long-range periodic order as results shown in X-ray diffraction

studies.
Amorphous Solids

Two-dimensional representation of
(a) crystalline quartz and (b)
noncrystalline quartz glass.

The small spheres represent silicon.

In reality, the structure of quartz is
three- dimensional. Each Si atom is
tetrahedrally bonded to four O
atoms
Composition and Properties of Three Types of Glass
Amorphous Solids
There are about 800 different types of glass in common use today.

The color of the glass is because of the presence of metal ion (as oxides). For
example:
● Green glass contains iron(III) oxide, Fe2O3, or copper(II) oxide, CuO
● Yellow glass contains uranium(IV) oxide, UO2;
● Blue glass contains cobalt(II) and copper(II) oxides, CoO and CuO;
● Red glass which contains small particles of gold and copper.

Most of the ions mentioned are derived from the transition metals.