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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;
CRYSTALLINE OF SOLIDS ▪ Calculate the packing efficiency for each
lattice; and
Chemistry for Engineers and Engineering Technologist
▪ Solve problems involving crystalline solids.

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The Chemistry of Solids Classification of Solids

Solids can be classified
▪ Solid posses the most based on the
structural diversity arrangement of their
particles
▪ Consist of molecules, ▪ Crystalline solids
atoms, or ions that are ▪ Amorphous solids
statically positioned.
▪ Structural interactions
between subunits
dictates the properties of
solid materials.
https://commons.wikimedia.org/wiki/File:Insulincrystals.jpg https://byjus.com/chemistry/classification-of-solids-based-on-crystal-structure/

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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.
Fig. 1 Two-dimensional representation of quartz in its crystalline.

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Crystal Lattice Amorphous Solids

▪ Possess no long-range
▪ A unit cell
structural order throughout
o the unit cell is the basic the solid.
and smallest repeating
▪ Considerable short-range
structural unit of a crystal
order over distances of 1-
lattice.
10 nm or so,
▪ Lattice point
▪ Lack of long-range
o each sphere represent translational order
an atom, ion or molecule. (periodicity) separates this
class of materials from
their crystalline
counterparts.

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Comparisons Types of Crystals

Crystalline Solids Amorphous Solids
▪ Formation is more ▪ Favored in kinetically-bound
Ionic Crystals
thermodynamically- processes (e.g. CVD- carbon ▪ Lattice points occupied
favorable vapor deposition, sol-gel, by cations and anions
▪ Discrete melting solid precipitation)
▪ Held together by
temperature and heat of ▪ Undergo solid-liquid phase
electrostatic attraction
fusion transition over a range of
temperature ▪ Hard, brittle, high
*glass transition temperature melting point
o temperature below which ▪ Poor conductor of heat
molecules have very little and electricity
mobility

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Types of Crystals Types of Crystals

Covalent Crystals Molecular Crystals
▪ Lattice points ▪ Lattice points
occupied by atoms occupied by
▪ Held together by molecules
covalent bonds ▪ Held together by
▪ Hard, high melting intermolecular forces
point ▪ Soft, low melting point
▪ Poor conductor of ▪ Poor conductor of
heat and electricity heat and electricity

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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

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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
𝑁𝑎𝑡𝑜𝑚𝑠 𝑉𝑎𝑡𝑜𝑚 𝑎𝑡𝑜𝑚 𝑥 𝜋𝑟 3
𝐴𝑃𝐹 = = 3
𝑉𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑎3

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Packing Efficiency (PE)

Four Basic Crystal Structures
▪ Represents the percentage of space that is A. Simple-cubic Cell (SCC)
occupied in a given arrangement ▪ AAAAAAAA structure
▪ Simple Cubic has one lattice
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚 𝑖𝑛 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙𝑠 point so its primitive cell
𝑃𝐸 = x 100%
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 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)

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Solve for APF & PE for SCC B. Body-Centered Cubic Cell

𝑎 = 2𝑟 (BCC)
▪ ABABABABAB structure
𝑎𝑡𝑜𝑚𝑠 𝑥4Τ3 𝜋𝑟 3 1 (4ൗ
𝐴𝑃𝐹 = = 3 𝜋𝑟3 ) ▪ BCC has two lattice points so BCC
𝑎3 (2 𝑟)3
is a non-primitive cell
1 4Τ3 𝜋𝑟 3 ▪ BCC has 8 coordination number.
= = 0.5236
8 𝑟3 ▪ Each atom is in contact with its
neighbors only along the body
APF= 0.5236~ 𝟎. 𝟓𝟐
𝐏𝐄 = 0.52 𝑥 100 = 𝟓𝟐% 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%

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Solve for APF & PE for BCC C. Face-Centered Cubic Cell

𝑑 = 4𝑟 (FCC) or Cubic Close Packing
𝑏 2 = 𝑎2 + 𝑎2
(CCP)
𝑐2 = 𝑎2 + 𝑏 2
𝑐 = √3𝑎2 ▪ Atoms are arranged at the
a = 3 r = 4r corners and center of each
4𝑟 cube face of the cell.
a=
√3
𝑎𝑡𝑜𝑚𝑠 𝑥4Τ3 𝜋𝑟 3 2 (4ൗ
3 𝜋𝑟3 )
▪ ABCABCABC structure
𝐴𝑃𝐹 = = 4𝑟 3
𝑎3 (
√3
) ▪ Cu, Al, Ag, Au have this
2 4 1Τ3 𝜋𝑟 3 2𝜋 ( 3) crystal structure
= (4)(4)(4) = 16
3√3
𝑟3 ▪ It has 4 atoms
APF= 0.6802~ 𝟎. 𝟔𝟖 ▪ APF is 0.74, PE = 74%
𝐏𝐄 = 0.68 𝑥 100 = 𝟔𝟖% ▪ Coordination number is 12

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FCC Stacking Sequence

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Solve for APF & PE for FCC

𝑏 = 4𝑟
𝑏 2 = 𝑎2 + 𝑎2
16𝑟 2 = 2𝑎 2
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%

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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%

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Solve for APF & PE for HPC Summary

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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
𝑎2𝑐
2
(6)(4Τ3 𝜋𝑟 3 )
=3 3 2
(2𝑟 2 ) (4𝑟)
2 3

(6)(4Τ3 𝜋𝑟 3 ) 𝜋
= =
(
3 3
)(
2
)(16𝑟 3 ) √18
2 3

APF= 0.74048~ 𝟎. 𝟕𝟒 𝐏𝐄 = 0.74 𝑥 100 = 𝟕𝟒%

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X-ray Diffraction by Crystals Practice Exercises:

▪ Refers to the scattering of X rays by the unit of a 1. Polonium is the only metal that forms a single cubic
crystalline solid. crystal structure. Use the fact that density of polonium
▪ The scattering, or diffraction, patterns produced are used is 9.23 g/cm3 to calculate its atomic radius.
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

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2. Manganese forms a body centered cubic unit cell

and has an edge length of 285 pm. Calculate the
density of the manganese.

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3. Gold crystallizes in a face centered crystal structure

and has a density of 19.3 g/cm 3. Calculate the radius
of gold in picometers.

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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

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