SCI 401

GENERAL CHEMISTRY

Engr. Ronna P. Dipasupil

Instructor
 Chemistry of Engineering
Materials: Basic Concepts
of Crystal Structures
● CRYSTAL STRUCTURES
● UNIT CELLS
● DENSITY COMPUTATIONS
● X-RAY DIFFRACTION BY CRYSTALS
● TYPES OF CRYSTALS
● AMORPHOUS SOLIDS
 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.
https://www.youtube.com/watch?v=RyIARZ8jG1c
 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”.
 Chemistry of Engineering
Materials: Basic Concepts
of Crystal Structures
● CRYSTAL STRUCTURES
● UNIT CELLS
● DENSITY COMPUTATIONS
● X-RAY DIFFRACTION BY CRYSTALS
● TYPES OF CRYSTALS
● AMORPHOUS SOLIDS
 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. https://www.youtube.com/watch?v=qAeaHYSX0h
SEVEN TYPES OF UNIT CELLS
SEVEN TYPES OF UNIT CELLS
The 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 .
The 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
The Face-Centered Cubic Crystal Structure
The 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 using the following formula:
Important 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.
 Important 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.
Atomic Packing Factor
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. 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
The Body-Centered Cubic Crystal Structure
From Equation 2, the number of atoms per BCC is 2. 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.
 The 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.
Edge Length and Atomic Radius Relationships
The 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.
The Hexagonal Close-Packed Crystal Structure
To compute the number of atoms per unit cell for HCP crystal
structure, the formula is shown below:

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. Using
Equation 5, the value of N for HCP can be found.
 Chemistry of Engineering
Materials: Basic Concepts
of Crystal Structures
● CRYSTAL STRUCTURES
● UNIT CELLS
● DENSITY COMPUTATIONS
● X-RAY DIFFRACTION BY CRYSTALS
● TYPES OF CRYSTALS
● AMORPHOUS SOLIDS
 Density Computations
A theoretical density (ρ) can be computed with a knowledge of the
crystal structure of a metallic solid through the relationship

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 1023 atoms/mol)
Density Computations
Density Computations
Density Computations
 Chemistry of Engineering
Materials: Basic Concepts
of Crystal Structures
● CRYSTAL STRUCTURES
● UNIT CELLS
● DENSITY COMPUTATIONS
● X-RAY DIFFRACTION BY CRYSTALS
● TYPES OF CRYSTALS
● AMORPHOUS SOLIDS
 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.
 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
 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.
 Chemistry of Engineering
Materials: Basic Concepts
of Crystal Structures
● CRYSTAL STRUCTURES
● UNIT CELLS
● DENSITY COMPUTATIONS
● X-RAY DIFFRACTION BY CRYSTALS
● TYPES OF CRYSTALS
● AMORPHOUS SOLIDS
 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
There are two important characteristics of ionic crystals
and they are as follows:
(1) They are composed of charged species
(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.
 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 the we calculate the length of the edge to 2
(95+181) pm or 552pm.

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

ray diffraction which has a value of 564pm.
 Ionic Crystals
The difference between these two values tells us that
the radius of an ion actually varies slightly from one
compound to another.
 Ionic Crystals
Figure 9 shows the portions of the Na+ and Cl- ions
within a unit cell.
Ionic Crystals
 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.
 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).
 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.
 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 100oC.
 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.
Metallic Crystals
 Chemistry of Engineering
Materials: Basic Concepts
of Crystal Structures
● CRYSTAL STRUCTURES
● UNIT CELLS
● DENSITY COMPUTATIONS
● X-RAY DIFFRACTION BY CRYSTALS
● TYPES OF CRYSTALS
● 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.
Amorphous Solids
Amorphous Solids
 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.