CHEMISTRY OF

ENGINEERING MATERIALS
BASIC CONCEPTS OF
CRYSTAL STRUCTURES
OVERVIEW
• Crystal structures
• Unit cells
• Density computations
• X-ray diffraction by crystals
• Types of crystals
• Amorphous solids

General Chemistry
CATEGORIES OF SOLIDS
Crystalline solids - has rigid and long-range order and its atoms,
molecules, or ions occupy specific positions.

In a crystalline solid, the arrangement of particles is such that the

net attractive intermolecular forces are at their maximum.

Amorphous solids - observes absence of a well-defined

arrangement and long-range molecular order.

General Chemistry
CATEGORIES OF SOLIDS

General Chemistry
CRYSTAL STRUCTURES
Atoms or ions (described as crystalline structures) are thought of
as being solid spheres having well-defined diameters known as the
atomic hard-sphere model, in which spheres representing nearest-
neighbor atoms touch one another.
In this specific case all the atoms are identical. 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”.

General Chemistry
UNIT CELLS
UNIT CELLS
A unit cell is the basic structural (repeating) unit of a crystalline
solid.

For each sphere, it denotes an atom, ion, or molecule and it is

called a lattice point. 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.
General Chemistry
7 TYPES OF UNIT CELLS

General Chemistry
7 TYPES OF UNIT CELLS

General Chemistry
FACE-CENTERED CUBIC CRYSTAL STRUCTURE
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 .

General Chemistry
FACE-CENTERED CUBIC CRYSTAL STRUCTURE
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

General Chemistry
FACE-CENTERED CUBIC CRYSTAL STRUCTURE

General Chemistry
FACE-CENTERED CUBIC CRYSTAL STRUCTURE
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. The number of atoms per unit cell, N, can be computed.

General Chemistry
FACE-CENTERED CUBIC CRYSTAL STRUCTURE

General Chemistry
CHARACTERISTICS OF A CRYSTAL STRUCTURE
(a) the coordination number (for metals) wherein each atom has
the same number of nearest-neighbor or touching atoms
(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.

General Chemistry
CHARACTERISTICS OF A CRYSTAL STRUCTURE
For FCCs, the coordination
number is 12 as can be seen
in the given figure. Front face
atoms has four nearest
neighboring atoms around it,
four face atoms that are link
from behind, and four other
equivalent face atoms
positioned in the next unit cell
to the front which is not shown.
General Chemistry
ATOMIC PACKING FACTOR

General Chemistry
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. 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

General Chemistry
BODY-CENTERED CUBIC CRYSTAL STRUCTURE
The BCC crystal structure has 8 coordination number. The
atomic packing factor for BCC 0.68 which is lower than for FCC,
since BCC has lesser coordination number.

General Chemistry
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.

General Chemistry
EDGE LENGTH AND ATOMIC RADIUS RELATIONSHIPS

General Chemistry
HEXAGONAL CLOSE-PACKED CRYSTAL STRUCTURE
The final common metallic crystal structure is the hexagonal
close-packed (HCP). The top and bottom faces of the unit cell
consist 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.

General Chemistry
HEXAGONAL CLOSE-PACKED CRYSTAL STRUCTURE

General Chemistry
HEXAGONAL CLOSE-PACKED CRYSTAL STRUCTURE

2 6

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DENSITY COMPUTATIONS
DENSITY COMPUTATIONS

General Chemistry
DENSITY COMPUTATIONS

General Chemistry
DENSITY COMPUTATIONS

Au Au

Solution 1: Shift Solve

Solution 2: Math properties

General Chemistry
DENSITY COMPUTATIONS
3:

General Chemistry
DENSITY COMPUTATIONS

General Chemistry
OVERVIEW
• X-ray diffraction by crystals
• Types of crystals
• Amorphous solids

General Chemistry
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.

Figure 6 shows the interference phenomenon associated with waves. Since X-

rays are one form of electromagnetic radiation, therefore, we would expect that
waves exhibit such behavior under relevant conditions.
General Chemistry
X-RAY DIFFRACTION BY CRYSTALS
Figure 7 shows a typical X-ray diffraction setup. A beam of X rays is
directed at a mounted crystal. Atoms in the crystal absorb some of
the incoming radiation and then re-emit it; the process is called the
scattering of X rays.

General Chemistry
X-RAY DIFFRACTION BY CRYSTALS
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.

General Chemistry
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.

General Chemistry
IONIC CRYSTALS
There are two important characteristics of ionic crystals and they
are as follows:
(1) They are composed of charged species and
(2) anions and cations are generally quite different in size.
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.

General Chemistry
IONIC CRYSTALS
For example, the crystal which has a face-centered cubic lattice
(see Figure 8) 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, then, we calculate the length
of the edge to 2 (95+181) pm or 552 pm.

In Figure 8, the edge length shown was determined by X-ray

diffraction which has a value of 564pm.

General Chemistry
IONIC CRYSTALS
The difference between these two values tells us that the radius
of an ion actually varies slightly from one compound to another.

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IONIC CRYSTALS
Figure 9 shows the portions of the Na+ and Cl- ions within a unit
cell.

General Chemistry
IONIC CRYSTALS

General Chemistry
IONIC CRYSTALS
Most ionic crystals have high melting points which 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.

General Chemistry
COVALENT CRYSTALS
Covalent crystals exists when atoms are held together in an
extensive three-dimensional network by covalent bonds. Examples
are the two allotropes of carbon: diamond and graphite. Each
carbon atom of diamond is where it is bonded to four other atoms
(Figure 11).

General Chemistry
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.

General Chemistry
MOLECULAR CRYSTALS
The lattice points in a molecular crystal are occupied by
molecules which has 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.

General Chemistry
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
100oC.

General Chemistry
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.

General Chemistry
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.

General Chemistry
METALLIC CRYSTALS

General Chemistry
AMORPHOUS SOLIDS
AMORPHOUS SOLIDS
Amorphous solids lack a regular three-dimensional arrangement
of atoms.
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.

General Chemistry
AMORPHOUS SOLIDS

General Chemistry
AMORPHOUS SOLIDS

General Chemistry
AMORPHOUS SOLIDS
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;
and red glass which contains small particles of gold and copper.
Most of the ions mentioned are derived from the transition metals.

General Chemistry
CHEMISTRY OF
ENGINEERING MATERIALS
METALS
METAL

Metal is an element, compound or alloy that is a good

conductor of both electricity and heat.

Metal crystal structure and specific metal properties

are determined by holding together the atoms of a metal.

General Chemistry
METAL
With the exception of hydrogen, all elements that form positive ions
by losing electrons during chemical reactions are called metals.

They are characterized by bright luster, hardness, ability to resonate

sound, and are excellent conductors of heat and electricity.

Metals are solids under normal conditions except for Mercury.

General Chemistry
PHYSICAL PROPERTIES OF METAL
• State: Metals are solids at room temperature with the exception of
Hg, which is liquid at room temperature (Ga is liquid on hot days).
• Luster: Metals have the quality of reflecting light from their surface
and can be polished e.g., Au, Ag and Cu.
• Malleability: Metals have the ability to withstand hammering and
can be made into thin sheets known as foils. E.g., a sugar cube
sized chunk of gold can be pounded into a thin sheet that will
cover a football field.

General Chemistry
PHYSICAL PROPERTIES OF METAL
• Ductility: Metals can be drawn into wires. For example, 100 g
of silver can be drawn into a thin wire about 200 meters long.
• Hardness: All metals are hard except sodium and potassium,
which are soft and can be cut with a knife.
• Valency: Metals typically have 1 to 3 electrons in the outermost
shell of their atoms.

General Chemistry
PHYSICAL PROPERTIES OF METAL
• Conduction: Metals are good conductors because they have
free electrons. Silver and copper are the two best conductors of
heat and electricity. Lead is the poorest conductor of heat.
Bismuth, mercury, and iron are also poor conductors.
• Density: Metals have high density and are very heavy. Iridium
and osmium have the highest densities whereas lithium has the
lowest density.
• Melting and Boiling Points: Metals have high melting and
boiling points. Tungsten has the highest melting and boiling
points whereas mercury has the lowest. Sodium and potassium
also have low melting points.
General Chemistry
CHEMICAL PROPERTIES OF METAL
✔ Electropositive Character: Metals tend to have low ionization
energies, and typically lose electrons (i.e. are oxidized) when
they undergo chemical reactions. They normally do not accept
electrons.
For example:
• Alkali metals are always 1+ (lose the electron in s subshell)
• Alkaline earth metals are always 2+ (lose both electrons in s subshell)
• Transition metal ions do not follow an obvious pattern, 2+ is common (lose
both electrons in s subshell), and 1+ and 3+ are also observed

General Chemistry
CHEMICAL PROPERTIES OF METAL

General Chemistry
OCCURRENCE OF METALS
OCCURRENCE OF METAL

General Chemistry
OCCURRENCE OF METAL

Clay (mineral of Aluminum) Bauxite (principal ore of Aluminum)

General Chemistry
OCCURRENCE OF METAL

Manganese nodule

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PRINCIPAL TYPES OF MINERALS

General Chemistry
METALLURGY
METALLURGY

General Chemistry
PRINCIPAL STEPS

General Chemistry
Froth flotation

Froth flotation is a process that selectively separates

materials based upon whether they are water
repelling (hydrophobic) or have an affinity for water
(hydrophilic).
Amalgamation
The amalgamation is the
process of extraction which is
used for the extraction of
metals such as gold and silver
or it may be a mixture of both
of them. In an amalgamation
process, the metals are
extracted from their ores by
addition of small quantities of
mercury to the amalgamation
drum or on an amalgamation
table.
PRODUCTION OF METAL

General Chemistry
BLAST FURNACE

General Chemistry
PRODUCTION OF METAL

General Chemistry
General Chemistry
PRINCIPAL STEPS

General Chemistry
BAND THEORY OF
ELECTRICAL
CONDUCTIVITY
BAND THEORY OF ELECTRICAL CONDUCTIVITY
• In solid-state physics, the band structure of a solid describes
those ranges of energy, called energy bands, that an electron
within the solid may have (“allowed bands”) and ranges of
energy called band gaps (“forbidden bands”), which it may not
have.
• Band theory models the behavior of electrons in solids by
postulating the existence of energy bands.

General Chemistry
BAND THEORY OF ELECTRICAL CONDUCTIVITY
Band theory - a model use to study metallic bonding
- states that delocalized electrons move freely through “bands”
formed by overlapping molecular orbitals.

This theory can also be applied to certain elements that are

semiconductors.

General Chemistry
BAND THEORY OF ELECTRICAL CONDUCTIVITY

General Chemistry
BAND THEORY OF ELECTRICAL CONDUCTIVITY

General Chemistry
General Chemistry
SEMICONDUCTORS

General Chemistry
SEMICONDUCTORS
Semiconductors are materials that have properties in between
those of normal conductors and insulators; they are often produced
by doping.

General Chemistry
SEMICONDUCTORS
Semiconductors are materials that have properties of both
normal conductors and insulators. Semiconductors fall into
two broad categories:

Intrinsic semiconductors - composed of only one kind of

material; silicon and germanium are two examples. These
are also called undoped semiconductors or i-type
semiconductors.

General Chemistry
SEMICONDUCTORS
Extrinsic Semiconductors - are intrinsic semiconductors with
other substances added to alter their properties — that is to say,
they have been doped with another element.

There are two types of extrinsic semiconductors that result from

doping:
1. n-type for negative, from group V, such as phosphorus
2. p-type for positive, from group III, such as boron

General Chemistry
SEMICONDUCTORS
N-Type Semiconductors are types of extrinsic semiconductor in
which the dopant atoms are capable of providing extra conduction
electrons to the host material (e.g., phosphorus in silicon). This
creates an excess of negative (n-type) electron charge carriers.

P-Type Semiconductors are types of extrinsic semiconductor in

which the atoms have one fewer electron (e.g., boron).

General Chemistry
General Chemistry
THE ALKALI AND
ALKALINE EARTH METALS
ALKALI METALS
• Chemical elements found in Group 1 of the periodic table.
They appear silvery and can be cut with a plastic knife.
• The alkali metals include: lithium, sodium, potassium,
rubidium, cesium, and francium.
• Hydrogen is not technically an alkali metal since it rarely
exhibits similar behavior.
• The word "alkali" received its name from the Arabic word "al
qali," meaning "from ashes", which since these elements
react with water to form hydroxide ions, creating alkaline
solutions (pH>7).

General Chemistry
ALKALI METALS

General Chemistry
COMMON PROPERTIES OF ALKALI METALS
• The most electropositive or the least electronegative elements
• Common oxidation state +1
• Found dissolved in seawater due to geologic erosion of
minerals
• All the discovered alkali metals occur in nature.
• These metals have a BCC structure with low packing efficiency.
• Low melting point.
• Lithium - lightest known metal and has great chemical reactivity.
Do not occur free in elemental form, are combined in halides,
sulfates, carbonates, and silicates
General Chemistry
ALKALINE EARTH METALS

General Chemistry
ALKALINE EARTH METALS
• Less electropositive and less reactive than Group IA
• Common oxidation state +2
• IIA Metals attain stable electron configuration of the
preceding noble gases
• Have much higher melting points than the alkali metals,
harder metals than the Group 1A elements, but are soft and
lightweight compared to many of the transition metals.
• The chemistry of radium is not well established due to its
radioactivity.

General Chemistry
ALKALINE EARTH METALS
Emerald is a variety of beryl, a
mineral that contains the alkaline
earth metal beryllium.

Beryllium only occurs naturally

in combination with other
elements in minerals.

General Chemistry
ALUMINUM
 ALUMINUM
• Most abundant metal and the 3rd most
plentiful element in the Earth’s crust.
• Elemental form doesn’t occur in nature
• Principal ore: Bauxite (Al2O3 • H2O)
• Other minerals containing aluminum are
orthoclase (KAlSi3O8), beryl (Be3Al2Si6O18),
cryolite (Na3AlF6), and corundum (Al2O3).
Charles Hall, pioneer of
• Considered a precious metal until Hall development of Aluminum
production
developed a method of Aluminum production

General Chemistry
PREPARATION OF ALUMINUM
Anhydrous aluminum oxide (Al2O3 or corundum) is reduced to
aluminum by the Hall process. The cathode is also made of carbon
and constitutes the lining inside the cell.

The key to the Hall process is the use of cryolite, or Na3AlF6

(melting point is 1000°C), as the solvent for aluminum oxide
(melting point is 2045°C).

The mixture is electrolyzed to produce aluminum and oxygen gas.

Oxygen gas reacts with the carbon anodes to form carbon
monoxide, which escapes as a gas.
General Chemistry
PREPARATION OF ALUMINUM
The liquid aluminum
metal (melting point
is 660.2°C) sinks to
the bottom of the
vessel, from which it
can be drained from
time to time during
the procedure.

General Chemistry
 RECYCLING OF ALUMINUM
• Aluminum is one of the most recycled and most recyclable materials
on the market today. Nearly 75% of all aluminum produced in the
U.S. is still in use today.

• Aluminum can be recycled directly back into itself over and over
again in a true closed loop.

• Recycling aluminum costs 95% less energy compared to producing

primary aluminum.

General Chemistry
RECYCLING OF ALUMINUM

General Chemistry
TRANSITION METALS
TRANSITION METALS
Transition Metal – any of various chemical elements that have
valence electrons—i.e., electrons that can participate in the formation
of chemical bonds—in two shells instead of only one.
̶ Transition elements are the elements that are found in Groups 3-
12 (old groups IIA-IIB) on the periodic table.

̶ Transition metals typically have incompletely filled d subshells or

readily give rise to ions with incompletely filled d subshells.

̶ Many transition element compounds are brightly colored due to

the inner-level d electron transitions.
General Chemistry
PROPERTIES OF TRANSITION METAL
Transition metals have similar properties, and some of these
properties are different from those of the metals in group 1.

Physical properties
̶ they are good conductors of heat and electricity

̶ they can be hammered or bent into shape easily

̶ they have high melting points (but mercury is a liquid at room

temperature)
̶ they are usually hard and tough

̶ they have high densities

General Chemistry
PROPERTIES OF TRANSITION METAL
Chemical properties
The transition metals have the following chemical properties in
common:

̶ they are less reactive than alkali metals such as sodium

̶ they form colored ions of different charges
̶ some are very unreactive (silver and gold)
̶ many are used as catalysts

General Chemistry
USES OF TRANSITION METALS
Transition metals have a wide range of uses. Their properties are very similar but
not identical. It is important to choose the right transition metal for the required
purpose.

GOLD

General Chemistry
USES OF TRANSITION METALS
SILVER

COPPER

General Chemistry
USES OF TRANSITION METALS
IRON
Iron is usually too soft to be used as the metal alone. It is usually mixed with
small amounts of other elements to make steels, which are harder and stronger
than iron, but easily shaped. However, iron and steel react slowly with water
and air to produce rust. They must be protected with, for example, a layer of
paint.

General Chemistry
USES OF TRANSITION METALS
CHROMIUM

General Chemistry