Classification of Materials

 In general, materials can be subdivided into two

categories according to their atomic arrangement.
1. Crystalline materials
2. Noncrystalline materials
 In crystalline materials there is a three-dimensional
periodic pattern of the atoms, whereas no such long
range periodicity is present in noncrystalline
materials, which possess only short-range atomic
order.
 1. Crystalline Materials

 A CRYSTAL is a regular polyhedral form, bounded by

smooth faces, which is assumed by a chemical compound,
due to the action of its interatomic forces, when passing
from the state of a liquid or gas to that of a solid.

 Very slow cooling of a liquid allows atoms to arrange

themselves into an ordered pattern, which may extend of a
long range (millions of atoms). This kind of solid is called
crystalline (Crystallography)
 Crystalline Structure

 Atoms are bonded to each other by either primary or

secondary forces. In the solid state, they combine in a
manner that ensures minimal internal energy. The
result is that they form a regularly spaced
configuration known as a space lattice or crystal.
 A space lattice can be defined as any arrangement of
atom in space in which every atom is situated similarly
to every other atom. Space lattices may be the result
of primary or secondary bonds
 Crystal Forms

• During the process of crystallization, crystals assume various

geometric shapes dependent on the ordering of their atomic
structure and the physical and chemical conditions under
which they grow.
• These forms may be subdivided, using geometry, into six
systems.
6 large groups of crystal
CRYSTALLOGRAPHIC systems:
AXES
• (1) CUBIC
• (2) TETRAGONAL
• (3) ORTHORHOMBIC
• (4) HEXAGONAL
• (5) MONOCLINIC
• (6) TRICLINIC
(1) CUBIC (ISOMETRIC)
The three crystallographic axes
a1, a2, a3 (or a, b, c) are all
equal in length and
intersect at right angles (90
degrees) to each other.

(2) TETRAGONAL

Three axes, all at right angles,

two of which are equal in
length (a and b) and one (c)
which is different in length
(shorter or longer).

Note: If c was equal in length to a

or b, then we would be in the
cubic system!
(3) ORTHORHOMBIC
Three axes, all at right angles, and
all three of different lengths.
Note: If any axis was of equal length to
any other, then we would be in the
tetragonal system!

(4) HEXAGONAL
Four axes! Three of the axes fall in the
same plane and intersect at the axial
cross at 120 degrees between the
positive ends. These 3 axes, labeled a1, a2,
and a3, are the same length. The fourth
axis, termed c, may be longer or shorter
than the a axes set. The c axis also passes
through the intersection of the a axes set at
right angle to the plane formed by the a set.
(5) MONOCLINIC
Three axes, all unequal in length, two
of which (a and c) intersect at an
oblique angle (not 90 degrees), the
third axis (b) is perpendicular to the
other two axes.
Note: If a and c crossed at 90 degrees,
then we would be in the orthorhombic
system!
(6) TRICLINIC
The three axes are all unequal in length
and intersect at three different angles
(any angle but not 90 degrees).
Note: If any two axes crossed at 90 degrees,
then we would be describing a monoclinic
crystal!
 3-D Translations and Lattices

 Different ways to combine 3 non-parallel, non-

coplanar axes

3-D Lattice Types +c

Name axes angles
Triclinic abc   90o
+a
Monoclinic abc  = 90 90
o o 
Orthorhombic abc  = 90
o

Tetragonal a1 = a2  c  = 90
o  
Hexagonal
Hexagonal (4 axes) a 1 = a2 = a3  c  = 90o 120o +b
Rhombohedral a 1 = a2 = a3  90o Axial convention:
Isometric a 1 = a2 = a3  = 90 o
“right-hand rule”
 3-D translations

 Unit cell is a representation of the crystal

such that it can be repeated (by moving it)
to make that pattern
 If a crystal has symmetry, the unit cell must
have at least that much symmetry
Unit cells have at least as much symmetry as the
crystal (internal order > external order)

 Here is why there are

no 5-fold rotation axes!
If the unit cell cannot
be repeated that way
to make a lattice, then
a crystal cannot have
that symmetry…
 Unit cells – counting atoms
 Z represents the number of atoms the unit cell is
comprised of
•Atom inside cell
counts 1 each
•Atom at face
counts ½ each
Z=1 •Atom at edge
counts ¼ each
•Atom at corner
counts 1/8 each
 ELEMENTS OF SYMMETRY

Planes of Symmetry

Any two dimensional surface that, when passed through the center of the
crystal, divides it into two symmetrical parts that are MIRROR IMAGES
is a PLANE OF SYMMETRY
A cube has 9 planes of symmetry, 3 of one set and 6 of another.
In the left figure the planes of symmetry are parallel to the faces of the cube
form, in the right figure the planes of symmetry join the opposite cube edges.
 Axes of Symmetry
Any line through the center of the crystal around which the crystal may be
rotated so that after a definite angular revolution the crystal form
appears the same as before is termed an axis of symmetry. Depending
on the amount or degrees of rotation necessary, four types of axes of
symmetry are possible when you are considering crystallography:

When rotation repeats form every 60 degrees, then we have sixfold or

HEXAGONAL SYMMETRY.

When rotation repeats form every 90 degrees, then we have fourfold or

TETRAGONAL SYMMETRY.

When rotation repeats form every 120 degrees, then we have threefold
or TRIGONAL SYMMETRY.

When rotation repeats form every 180 degrees, then we have twofold or
BINARY SYMMETRY.
 Center of Symmetry

Most crystals have a center of

symmetry, even though they may not
possess either planes of symmetry or
axes of symmetry. Triclinic crystals
usually only have a center of
symmetry. If you can pass an
imaginary line from the surface of a
crystal face through the center of the
crystal (the axial cross) and it
intersects a similar point on a face
equidistance from the center, then the
crystal has a center of symmetry.
http://xrayweb.chem.ou.edu/notes/symmetry.html#crystal
https://symotter.org/tutorial/intro
 2. Noncrystalline Materials

 Structures other than crystalline forms can occur in the

solid state. For example, waxes may solidify as
amorphous materials so that the molecules are
distributed at random..
 The structural arrangements of the noncrystalline solids
don’t represent such low internal energies as do
crystalline arrangements of the same atoms and
molecules.
 Noncrystalline solids do not have a definite melting
temperature, but rather they gradually soften as the
temperature is raised .
 Polymorphism

 Existence of substance into more than one crystalline

forms is known as "POLYMORPHISM".
 Under different conditions of temperature and
pressure, a substance can form more than one type
of crystals. This phenomenon is called Polymorphism
and different crystalline forms are known as
‘POLYMORPHICS’
 Polymorphs are different crystalline forms of the
same pure substance in which molecules have
different arrangements and/or different molecular
conformation.
 Continue…

 Polymorphic solids have different unit cells.

Examples:
1) Mercuric iodide (HgI2) forms two types of crystals.
 a. Orthorhombic
 b. Trigonal
2) Calcium carbonate (CaCO3) exists in two types of
crystalline forms.
 a. Orthorhombic (Aragonite)
 b. Trigonal
Polymorphous substances have similar chemical properties
but different physical properties.
 Physical Properties Differ Among
Various Polymorphs
 Molar volume and density
 Refractive index
 Melting and sublimation temperatures
 Enthalpy (i.e., heat content)
 Solubility
 Vibration transitions (i.e., infrared absorption spectra
and Raman spectra)
 Dissolution rate
 Stability
 Hardness
 Allotropy

 Existence of an element into more than one physical

forms is known as "Allotropy"
Under different conditions of temperature and
pressure an element can exist in more than one
physical forms. This phenomenon is known as
Allotropy and different forms are known as
"Allotropes"
Example:
Coal, lamp black, coke, Diamond, graphite etc. are
all allotropic forms of carbon.
 Isomorphism
 Existence of different substances in one crystalline form is
known as "Isomorphism"
Or
 Different substances may exist in identical crystalline forms.
This phenomenon is called as Isomorphism and these
substances are known as ‘Isomorphous’.
 Examples:
 1) Na2SO4 & Ag2SO4 both exist in Hexagonal crystalline
form.
 2) KBF4 & BaSO4 both exist in Orthorhombic
 3) ZnSO4 & NiSO4 both exist in Orthorhombic
 4) CaCO3 & NaNO3 both exist in Trigonal
Properties of Isomorphic Substances
 Isomorphic substances have same atomic ratio
 Empirical formula of isomorphic substances is same

For example
 CaCO3 NaNO3

1:1:3 1:1:3
 NaF MgO

1:1 1:1
 They have different chemical & physical properties.

 When their solutions are mixed, they form mixed type of

crystals.