CHEMISTRY FOR ENGINEERS

Module 7: Basic Concepts of Crystal Structure

MODULE 7

BASIC CONCEPTS OF
CRYSTAL STRUCTURE

ENGR. JENNIFER B. IGAT

Prepared by

Biological Sciences Department

College of Science and Computer Studies
De La Salle University-Dasmariñas
Dasmariñas City, Cavite

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 CHEMISTRY FOR ENGINEERS
Module 7: Basic Concepts of Crystal Structure

CRYSTAL UNIT CELL, LATTICE, AND SYSTEMS

Crystallography, which began only in the latter part of 18th century, is the experimental science of the
arrangement of atoms in solids. It originates from the Greek words crystallon, which means “cold drop /
frozen drop” referring to all solids with some degree of transparency, and grapho, which means “write”.
A crystal is any solid material whose structure is highly ordered and symmetrical over macroscopic
distances. It is made of an array of atoms, ions, or molecules packed together in a regular pattern, and
whose surface regularity reflects its internal symmetry. In crystallography, a crystal structure is described
by giving the lattice and motif of the crystal. The lattice gives the periodicity of the crystal structure by
telling how atoms or molecules are repeated in space, while Motif tells us what atom, ion or molecule is
being repeated. On the other hand, Crystals system tells us about certain characteristic point symmetry
elements that this crystal structure will possess.

A. Unit Cell

A unit cell is the smallest portion of a crystal lattice that is repeated through space without rotation and
without gaps or overlaps. A crystal can be thought of as the same unit cell repeated over and over in
three dimensions. For filling space without holes, a unit cell must be either a parallelogram (in 2D) or a
parallelepiped (in 3D).

Unit cell Crystal

lattice

Lattice
point

When a unit cell is repeatedly translated to fill all space, the vertices of all the unit cells in the filled
space constitute a lattice. A lattice is an infinite array of regularly-spaced points. The absolute positions
of the points of a lattice, and hence the unit cell, are arbitrary with respect to a pattern.

Not all lattice points need coincide with unit cell vertices. Primitive unit cells use every lattice point as a
unit cell vertex. Non-primitive unit cells, however, contain extra lattice points not at the corners.

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Module 7: Basic Concepts of Crystal Structure

B. Lattice and Unit Cell Parameters

A lattice may be specified by two non-coincident vectors in 2D, and by

three non-coplanar vectors in 3D. The vectors lie along the edges of
the unit cell, and are labeled a, b, and (in 3D) c. The magnitude of the
vectors is given by the dimensions of the unit cell in the real crystal
under study.

The parameters of the unit cell are the following:

1) Lengths along the three edges -- a, b, and c

2) Angles α, β, and γ between the pairs of edges:
- angle α between edges b and c
- angle β between edges a and c
- angle γ between edges a and b

C. Lattice System

In crystallography, the Bravais lattice concept of an infinite array of discrete points is expanded using the
concept of a unit cell which includes the space in between the discrete lattice points as well as any atoms in
that space. There are two main types of unit cells: primitive unit cells and non-primitive unit cells. In three-
dimensional space, there are 14 Bravais lattices. These are obtained by combining one of the seven lattice
systems with one of the centering types. The centering types identify the locations of the lattice points in the
unit cell.

Three Types of Crystal Systems

Simple Cubic Body-Centered Face-Centered

In a simple cubic In a body-centered cubic In a face-centered cubic

(primitive cubic) unit cell, unit cell, the atoms or unit cell, there are atoms
atoms or ions are ions are at the corners or ions at the corners and
arranged at the corners and in the center of an in the center of each face
of an imaginary cube. imaginary cube. There of an imaginary cube.
There is one atom in a are two atoms in a body- There are four atoms in a
simple cubic unit cell. centered cubic unit cell. face-centered cubic unit
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Module 7: Basic Concepts of Crystal Structure

Lattices can be classified into "systems", each system being characterized by the shape of its
associated unit cell. In three dimensions, the lattices are categorized into seven crystal lattice
"systems". Within several of these, lattices supporting non-primitive unit cells can be defined. The
classification scheme yields a total of 14 possible lattices (called Bravais lattices).

Seven Crystal Systems

System (shape) System Lattices Lattice Parameters Primitive UC Sample

Triclinic (parallelepiped) primitive a ≠ b ≠ c, α ≠ β ≠ γ ≠ 90o

Primitive a ≠ b ≠ c, α = γ = 90o
Monoclinic
end-centered on B-
(paralleogramic prism)
face β ≠ 120o

Primitive
End-centered on C-
Orthorhombic (rectangular
face a ≠ b ≠ c, α = β = γ = 90o
prism)
Body-centered
Face-centered

Primitive
Tetragonal (Square prism) Body-centered a = b ≠ c, α = β = γ = 90o

Primitive
Body-centered
Isometric (Cubic) Face-centered a = b = c, α = β = γ = 90o

Trigonal/Rhombohedral Primitive or
(equilateral, equiangular rhombohedral a = b = c, α = β = γ ≠ 90o
parallelepiped) primitive

a = b ≠ c, α = β = 90o,
Hexagonal Primitive
(120o rhombic prism)
γ = 120o

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 CHEMISTRY FOR ENGINEERS
Module 7: Basic Concepts of Crystal Structure

14 – Bravais Lattices

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Module 7: Basic Concepts of Crystal Structure

D. Coordination Number (CN)

Coordination Number (CN) is the number of nearest neighbors that each atom has.

The coordination number is 6, 8, and 12 for simple cubic,

body-centered cubic, and face-centered cubic unit cells,
respectively, as shown in the figures below.

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Module 7: Basic Concepts of Crystal Structure

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 CHEMISTRY FOR ENGINEERS
Module 7: Basic Concepts of Crystal Structure

E. Atomic Packing Factor (APF)

The Atomic Packing Factor (APF) is used to express the percent of an object is made of atoms
against its empty space. This indicates how atoms are packed tightly and can be viewed as
volume density. Calculating the atomic packing factor for a crystal can be done by dividing the
volume of the atoms inside by the total volume.

Infographics on the APF determination for (a) Simple Cubic (b) Body-Centered Cubic and (c)
Face-Centered Cubic unit cells are shown below. (Reference: [Link]
packing-factor/)

(a) Simple Cubic Unit Cell

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Module 7: Basic Concepts of Crystal Structure

(b) Body-Centered Cubic Unit Cell

(c) Face-Centered Cubic Unit Cell

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Module 7: Basic Concepts of Crystal Structure

F. Theoretical density

The theoretical density of the crystal structure of a metallic solid can be determined
using the equation as shown in the sample computation below.

Sample computation:

Compute for the theoretical density of copper:

Given:
(1) Structure: FCC
(2) Atomic weight (M): 63.55 g/mol
(3) Radius (r) = 0.128 nm
Required: Theoretical density (ρ)
Solution:

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