CRYSTALLINE OF SOLIDS
Chemistry for Engineers and Engineering Technologist
LEARNING COMPETENCIES:
▪ Define crystalline solids;
▪ Enumerate the characteristics of crystalline
solids;
▪ Give the types of crystalline solids and their
examples;
▪ Describe the arrangement of atoms in the
common cubic crystal lattices;
▪ Calculate the packing efficiency for each
lattice; and
▪ Solve problems involving crystalline solids.
The Chemistry of Solids
▪ Solid posses the most
structural diversity
▪ Consist of molecules,
atoms, or ions that are
statically positioned.
▪ Structural interactions
between subunits
dictates the properties of
solid materials.
https://commons.wikimedia.org/wiki/File:Insulincrystals.jpg
Classification of Solids
Solids can be classified
based on the
arrangement of their
particles
▪ Crystalline solids
▪ Amorphous solids
https://byjus.com/chemistry/classification-of-solids-based-on-crystal-structure/
Fig. 1 Two-dimensional representation of quartz in its crystalline.
Crystalline Solids
▪ Possess long range,
regularly repeating units.
▪ Produced when the
atoms, ions, or molecules
have an opportunity to
organize themselves into
regular arrangement
(lattice).
▪ In nature, slow formation
under extreme
temperature and
pressure.
Crystal Lattice
▪ A unit cell
o the unit cell is the basic
and smallest repeating
structural unit of a crystal
lattice.
▪ Lattice point
o each sphere represent
an atom, ion or molecule.
Amorphous Solids
▪ Possess no long-range
structural order throughout
the solid.
▪ Considerable short-range
order over distances of 1-
10 nm or so,
▪ Lack of long-range
translational order
(periodicity) separates this
class of materials from
their crystalline
counterparts.
Comparisons
Crystalline Solids Amorphous Solids
▪ Formation is more ▪ Favored in kinetically-bound
thermodynamically- processes (e.g. CVD- carbon
favorable vapor deposition, sol-gel,
▪ Discrete melting solid precipitation)
temperature and heat of ▪ Undergo solid-liquid phase
fusion transition over a range of
temperature
*glass transition temperature
o temperature below which
molecules have very little
mobility
Types of Crystals
Ionic Crystals
▪ Lattice points occupied
by cations and anions
▪ Held together by
electrostatic attraction
▪ Hard, brittle, high
melting point
▪ Poor conductor of heat
and electricity
Types of Crystals
Covalent Crystals
▪ Lattice points
occupied by atoms
▪ Held together by
covalent bonds
▪ Hard, high melting
point
▪ Poor conductor of
heat and electricity
Types of Crystals
Molecular Crystals
▪ Lattice points
occupied by
molecules
▪ Held together by
intermolecular forces
▪ Soft, low melting point
▪ Poor conductor of
heat and electricity
Types of Crystals
Metallic Crystals
▪ Lattice points
occupied by metal
atoms
▪ Held together by
metallic bonds
▪ Soft to hard, low to
high melting point
▪ Good conductor of
heat and electricity
Crystalline Structures
Packing Spheres
Atomic Packing Factor (APF)
▪ It can be defined as the ratio between the volume
of the basic atoms of the unit cell (which represent
the volume of all atoms in one unit cell) to the
volume of the unit cell itself.
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙𝑠
𝐴𝑃𝐹 =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Or
4 3
𝑁𝑎𝑡𝑜𝑚𝑠 𝑉𝑎𝑡𝑜𝑚 𝑎𝑡𝑜𝑚 𝑥 𝜋𝑟
𝐴𝑃𝐹 = = 3
𝑉𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑎3
Packing Efficiency (PE)
▪ Represents the percentage of space that is
occupied in a given arrangement
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚 𝑖𝑛 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙𝑠
𝑃𝐸 = x 100%
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Four Basic Crystal Structures
A. Simple-cubic Cell (SCC)
▪ AAAAAAAA structure
▪ Simple Cubic has one lattice
point so its primitive cell
▪ Coordination number of
simple cubic is 6
▪ APF is 0.52, PE is 52%
▪ This structure is the least
efficient only one element is
under this structure
(polonium)
Solve for APF & PE for SCC
𝑎 = 2𝑟
𝑎𝑡𝑜𝑚𝑠 𝑥4Τ3 𝜋𝑟 3 1 (4ൗ
3 𝜋𝑟3 )
𝐴𝑃𝐹 = =
𝑎3 (2 𝑟)3
1 4Τ3 𝜋𝑟 3
= = 0.5236
8 𝑟3
APF= 0.5236~ 𝟎. 𝟓𝟐
𝐏𝐄 = 0.52 𝑥 100 = 𝟓𝟐%
B. Body-Centered Cubic Cell
(BCC)
▪ ABABABABAB structure
▪ BCC has two lattice points so BCC
is a non-primitive cell
▪ BCC has 8 coordination number.
▪ Each atom is in contact with its
neighbors only along the body
diagonal directions.
▪ Many metals (Fe, Li, Na etc)
including the alkalis and several
transition elements choose the
BCC structure
▪ APF is 0.68, PE is 68%
Solve for APF & PE for BCC
𝑑 = 4𝑟
𝑏 2 = 𝑎2 + 𝑎2
𝑐 2 = 𝑎2 + 𝑏 2
𝑐 = √3𝑎2
a = 3 r = 4r
4𝑟
a=
√3
𝑎𝑡𝑜𝑚𝑠 𝑥4Τ3 𝜋𝑟 3 2 (4ൗ
3 𝜋𝑟3 )
𝐴𝑃𝐹 = = 4𝑟 3
𝑎3 ( )
√3
2 4 1Τ3 𝜋𝑟 3 2𝜋 ( 3)
= (4)(4)(4) 3 = 16
𝑟
3√3
APF= 0.6802~ 𝟎. 𝟔𝟖
𝐏𝐄 = 0.68 𝑥 100 = 𝟔𝟖%
C. Face-Centered Cubic Cell
(FCC) or Cubic Close Packing
(CCP)
▪ Atoms are arranged at the
corners and center of each
cube face of the cell.
▪ ABCABCABC structure
▪ Cu, Al, Ag, Au have this
crystal structure
▪ It has 4 atoms
▪ APF is 0.74, PE = 74%
▪ Coordination number is 12
FCC Stacking Sequence
Solve for APF & PE for FCC
𝑏 = 4𝑟
𝑏 2 = 𝑎2 + 𝑎2
16𝑟 2 = 2𝑎2
a= 8r
𝑎𝑡𝑜𝑚𝑠 𝑥4Τ3 𝜋𝑟 3 4 (4ൗ
3 𝜋𝑟3 )
𝐴𝑃𝐹 = =
𝑎3 ( 8 𝑟)3
(4)(4)(1Τ3 𝜋𝑟 3 )
=
16 2 𝑟 3
APF= 0.74048~ 𝟎. 𝟕𝟒
𝐏𝐄 = 0.74 𝑥 100 = 𝟕𝟒%
D. Hexagonal Close Packing (HCP)
▪ Has a form of ABABABAB
▪ The coordination number is 12
▪ Unit cell contains 6 atoms/unit cell
6 𝑎𝑡𝑜𝑚𝑠
3 +(1/2*2) + (1/6 *12) =
𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
▪ Metals do not crystalize into the
simple hexagonal crystal structure
because the PF is too low
▪ The atoms can attain a lower
energy and a more stable condition
by forming the HCP structure
▪ APF is 0.74, PE is 74%
Solve for APF & PE for HPC
8 2
If a = 2r, H(HCP) = √ a and c (ccc) = 4 𝑟,
3 3
3√3
Volume of HPC unit cell = 𝑎2 c = 24√2 𝑟 3
2
𝑎𝑡𝑜𝑚𝑠 𝑥4Τ3 𝜋𝑟 3 6 (4ൗ
3 𝜋𝑟3 )
𝐴𝑃𝐹 = =
𝑎3 3 3 2
𝑎 𝑐
2
(6)(4Τ3 𝜋𝑟 3 )
=3 3 2
(2𝑟 2) (4𝑟)
2 3
(6)(4Τ3 𝜋𝑟 3 ) 𝜋
= 3 3 2
=
( 2 )( 3 )(16𝑟 3 ) √18
APF= 0.74048~ 𝟎. 𝟕𝟒 𝐏𝐄 = 0.74 𝑥 100 = 𝟕𝟒%
Summary
X-ray Diffraction by Crystals
▪ Refers to the scattering of X rays by the unit of a
crystalline solid.
▪ The scattering, or diffraction, patterns produced are used
to deduce the arrangement of particles in a the solid
lattice
▪ Bragg equation for calculating the distance between
planes of atoms in a crystal lattice.
2d sin ∅ = nλ
Where:
λ = wavelength of x-ray ; n = integer, order of reflection
d = distance ; sin ∅ = angle between x-rays
Practice Exercises:
1. Polonium is the only metal that forms a single cubic
crystal structure. Use the fact that density of polonium
is 9.23 g/cm3 to calculate its atomic radius.
2. Manganese forms a body centered cubic unit cell
and has an edge length of 285 pm. Calculate the
density of the manganese.
3. Gold crystallizes in a face centered crystal structure
and has a density of 19.3 g/cm3. Calculate the radius
of gold in picometers.
4. X rays of wavelength 0.154 nm strike an aluminum
crystal; the rays are reflected at an angle of 19.3°.
Assuming that n= 1, calculate the spacing between the
planes of aluminum atoms (in ppm) that is responsible
for this angle of reflection. The conversion factor is
obtained from 1 nm = 1000 pm.
Given:
λ = 0.154 nm , ∅ = 19.3°
Find: d
Formula: 2d sin ∅ = nλ
d = nλ / 2 sin ∅
1000 𝑝𝑚
d = (1) (0.154 nm) ( ) / 2 sin19.3°
1 𝑛𝑚
d = 233 pm
