Basic Concepts of Crystal Structures

SOLIDS

Can be categorized into two types based on crystallinity:

Crystalline

❖ Possesses rigid and long range-order Unit Cell

❖ Its atoms, molecules, or ions occupy specific The unit cell is the smallest unit of volume that permits
positions identical cells to be stacked together to fill all space.

By repeating the pattern of the unit cell over and over in

all directions, the entire crystal lattice can be
constructed.

Lattice: 3D array of points coinciding with atom positions

Example: (center of spheres)

❖ Table salt

❖ Quartz

Amorphous

❖ Lacks a well-defined arrangement and long

range molecular order

Example:

❖ Rubber

❖ Polymer

Crystals

A CRYSTAL is any solid material in which the component

atoms are arranged in a definite pattern and whose Number of atoms per unit cell, N
surface regularity reflects its internal symmetry. The
basic building block of the crystal structure. It defines the
entire crystal structure with the atom positions within.

The crystal structure is the manner in which atoms, ions,

or molecules are spatially arranged.
Ni = the number of interior atoms
Example:
Nf = number of face atoms
Galena, Quartz, Pyrite
Nc = number of corner atoms
Crystallinity

- repeating or periodic array over large atomic distances.

3-D pattern in which each atom is bonded to its nearest
neighbors

Coordination Number

- each atom has the same number of nearest-neighbor or

touching atoms

Atomic Packing Factor (APF)

Practice Problem No.1
- the sum of the spheres volumes of all atoms within a
unit cell (assuming the atomic hard-sphere model) Calculate the volume of an FCC unit cell in terms of the
divided by the unit cell volume atomic radius R.
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
𝐴𝑃𝐹 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
1. Simple Cubic Structure

2. Face Centered Cubic Structured

Practice Problem No. 2 4) Hexagonal Closed Packed Structure

Show that the packing factor for the FCC crystal

structure is 0.74

Theoretrical Density

3. Body Centered Cubic Structured

Problem

Copper (A=63.5 g/mol) has an atomic radius of 0.128 nm,

an FCC crystal structure, and an atomic weigh of 63.5
g/mol. Compute its theoretical density, and compare the
answer with its measured density.

Problem 2

Gold (Au) crystallizes in a cubic close-packed structure

(the face-centered cubic unit cell) and has a density of
19.3 g/cm3. Calculate the atomic radius of gold in
picometers.
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.

Max von Laue (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

An electron-density contour
map tells the relative
electron densities at various
locations in a molecule.
 2) Covalent Crystals

Exists when atoms are held together in an extensive

three dimensional network altogether by covalent
bonds.

An arrangement for obtaining the X-ray diffraction

pattern of a crystal. The shield prevents the strong
Diamond
undiffracted X rays from damaging the photographic
plate. X-ray diffraction pattern of crystalline lysozyme, a Each carbon of diamond is sp3 hybridized where it is
protein. The white "L" is a shadow of the sample holder bonded to 4 other atoms
and shield (Chang & Goldsby, 2017).
The unusual hardness and very high melting point (3550
Type of Crystals ℃) of diamond are attributed by the strong covalent
bonds that exist in three dimensions
1. Ionic Crystals
- They are composed of charged species. Anions Graphite
and cations are generally quite different in size.
For graphite, each atoms are arranged in six-membered
- Most ionic crystals have high melting points
rings
which is an indication of the strong cohesive
forces holding the ions together. The atoms are sp2- hybridized and each atom is
- A measure of the stability of ionic crystals is the covalently bonded to 3 other atoms
lattice energy; the higher the lattice energy, the
more stable the compound. Graphite is considered as a good conductor of electricity
- Since the ions are fixed in position, therefore in direction along the planes of carbon atoms, since
these solids do not conduct electricity. The ions electrons are free to move around
are free to move when in the molten state The hardness of graphite is caused by the covalent
(melted) or dissolved in water, thereby the bonds that exist in layers which is held together by
resulting liquid is conducting electricity. weak van der Waals forces

The layers of graphite can slide on one another, that’s

why it is slippery to touch and is an effective lubricant

3) Molecular Structures

The lattice points in a molecular crystal are occupied by

molecules which has a van der Waals forces and/or
hydrogen bonding.

The molecules in a molecular crystals (except for ice) are

packed together as closely as their size and shape allow.

Note that the intermolecular hydrogen bonding is mainly

responsible for maintaining the three-dimensional lattice
of ice.
Since van der Waals and hydrogen bonding are generally AMORPHOUS SOLIDS
quite weak as compared with ionic and covalent bonds,
Amorphous solids lack a regular three-dimensional
molecular crystals are more easily broken apart than
arrangement of atoms.
ionic and covalent crystals.
Glass commonly refers to an optically transparent fusion
Indeed, most molecular crystals melt below 200°C.
product of inorganic materials that has cooled to a rigid
state without crystallizing.

Solids are most stable in crystalline form. However, if a

solid is formed rapidly (for example, when a liquid is
cooled quickly), its atoms or molecules do not have time
to align themselves and may become locked in positions
other than those of a regular crystal.

The resulting solid is said to be amorphous.

4) 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.

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.