CHEM 112: General Chemistry 2

Module 4

BASIC CONCEPTS OF
CRYSTAL STRUCTURE

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4 CRYSTALLINE SOLIDS
OUTLINE

• Properties of Amorphous and Crystalline Solids

• Structures in Crystalline Solids

• Bonding in Solids

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LEARNING OUTCOMES

• Define and categorize amorphous and crystalline solids

• Identify basic crystal structure of metals
• Determine the number of atoms per unit cell given the type of
unit cell
• Calculate for the density of an element provided the type of unit
cell
• Predict whether the type of crystal formed by a substance is
ionic, covalent, molecular or metallic
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TYPES OF SOLIDS
Crystalline Solids Amorphous Solids
Crystalline solids have the following Solids that do not have a definite
fundamental properties. geometrical shape
1.  Have characteristic geometrical shape
1.  Particles are randomly arranged in
2.  Have highly ordered three-dimensional three dimension
arrangements of particles
3.  Bounded by PLANES or FACES 2.  Don’t have sharp melting points
4.  Planes of crystals intersect at particular 3.  Formed due to sudden cooling of
angles. liquid
5.  Have sharp melting and boiling points 4.  Melt over a wide range of temperature
Ex. CuSO4, NiSO4, diamond, graphite,
NaCl, sugar Ex. Coal, coke, glass, plastic, rubber, etc
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Adapted from Fig. 3.23(a),

Callister & Rethwisch 8e.
MATERIALS AND PACKING
Crystalline Materials
- atoms pack in periodic, 3D arrays
-  typical of metals, many ceramics, some polymers
Crystalline SiO2
Noncrystalline (Amorphous) Materials

Adapted from Fig. 3.23(b),

Callister & Rethwisch 8e.
-  atoms have no periodic packing
-  occurs for complex structures, rapid cooling

Noncrystalline SiO2 SLIDE

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METALLIC CRYSTAL STRUCTURE
Stacking in 2-dimensions

vs.

Close Packed Square Array

Arrangement
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METALLIC CRYSTAL STRUCTURES
• tend to be densely packed
• reasons for dense packing:
- typically, only one element is present so all atomic radii are the
same
- metallic bonding is not directional
- nearest neighbor distances tend to be small in order to lower
bond energy
• have the simplest crystal structures
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 4 CRYSTALLINE SOLIDS
CRYSTAL LATICE AND UNIT CELL
The atoms in a crystal are in a
regular repeating pattern called the
crystalline lattice.

Lattice Contribution:
Corner: 1/8 of a point
Face: ½ of a whole point
Body: 1 whole point

Portion of a 3-D crystal lattice

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 4 CRYSTALLINE SOLIDS
BASIC CUBIC UNIT CELLS

From left to right,

• simple cubic unit cell
• body-centered cubic unit cell (BCC)
• face-centered cubic unit cell (FCC)

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CHARACTERISTICS OF A CRYSTAL STRUCTURE

1.  Coordination Number – the number of atoms touching

a particular atom, or the number of nearest neighbors

2.  Atomic Packing Factor (APF) – the fraction of space

occupied by atoms assuming that atoms are hard spheres

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SIMPLE CUBIC UNIT CELL (SC)
-  rare due to low packing density (only Po has this structure)
- close-packed directions are cube edges

Coordination Number = 6
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ATOMIC PACKING FACTOR (APF) of SC
APF =​𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙∗/𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 *under the assumption that atoms
𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙  are hard spheres

volume
atoms atom
4
unit cell 1 π (0.5a) 3
a 3
APF =
R=0.5a a3 volume
Callister & Rethwisch 8e.

unit cell
Adapted from Fig. 3.24,

close-packed directions
contains 8 x 1/8 =
APF (for SC) = 0.52
1 atom/unit cell
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BODY-CENTERED CUBIC STRUCTURE (BCC)
-  atoms touch each other along cube diagonals
-  contains 1 center atoms in contact with 8 corner atoms
-  ex. Cr, W, tantalum, molybdenum

1 center + 8 corners (1/8) = 2 atoms per unit cell

Coordination Number = 8
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ATOMIC PACKING FACTOR (APF) of BCC

atoms volume
4 3
unit cell 2 π ( 3a/4 )
3 atom
APF =
3 volume
By using Pythagorean a
unit cell
R theorem, it can be
a determined that R = ​√ 3  APF (for BCC) = 0.68
𝑎/4 

[Sqrt(2a)] + a^2 = 16R^2

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FACE-CENTERED CUBIC STRUCTURE (FCC)
-  atoms touch each other along face diagonals
-  contains 6 face atoms and 8 corner atoms
-  ex. Al, Cu, Au, Pb, Ni, Pt, Ag

6 face(1/2) + 8 corners (1/8) = 4 atoms/unit cell

Coordination Number = 12
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ATOMIC PACKING FACTOR (APF) of FCC

Close-packed directions:
length = 4R = 2 a

2a atoms volume
4 3
unit cell 4 π ( 2a/4 )
3 atom
APF =
3 volume
a
a unit cell
APF (for FCC) = 0.74

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EDGE LENGTH AND ATOMIC RADIUS

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EDGE LENGTH AND ATOMIC RADIUS

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 4 CRYSTALLINE SOLIDS
PACKING IDENTICAL SPHERES

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 4 CRYSTALLINE SOLIDS
FCC Stacking Sequence – ABCABC
2-D projection
B B
C
A
A sites B B B
C C
B sites B B
C sites
A
B
C

FCC unit cell

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 4 CRYSTALLINE SOLIDS
Hexagonal Close-packed Structure (HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a Adapted from Fig. 3.3(a),
Callister & Rethwisch 8e.

• Coordination No. = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 SLIDE
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 4 CRYSTALLINE SOLIDS
Hexagonal Closed-packed Structure
- close-packed assemblage of hexagons in between 3 atoms at the
top and at the bottom

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AFP of HCP

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 Density Calculation

•  The density of a solid is that of the unit cell, obtained by dividing the
mass of the atoms (n atoms x Matom) and dividing by Vc the volume of
the cell (a3 in the case of a cube). If the mass of the atom is given in
amu (A), then we have to divide it by the Avogadro number to get
Matom.

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Theoretical Density, ρ

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g/cm^3 = (no of atoms)(g/mol)/(cm^3*6.02x10^23atoms/mole)
= 1 atom* 209g/mol/(((200*1x10^-12)*100 cm*2)^3)atom/
cm^3/atom*6.02 x10^23 atoms/mol
= 5.42 g/cm^3
Accepted value = 9.4 g/cm^3

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4 Densities of Material Classes
In general Metals/
Graphite/
Composites/
ρmetals > ρceramics > ρpolymers Alloys
Ceramics/
Semicond
Polymers
fibers
30
Why? Platinum
B ased on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia

ρ (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
Diamond
• less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2
Polymers have... Magnesium G raphite
Silicone
Carbon fibers
CFRE*
A ramid fibers
PVC
• low packing density PET
PC
AFRE *
1
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• intermediate values 0.3

Data from Table B.1, Callister & Rethwisch, 8e.
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Determination of the Density of the
CRYSTALLINE SOLIDS
Ex: Chromium, Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
SAMPLE PROBLEM 1

R a = 4R/ 3 = 0.2887 nm
Adapted from
Fig. 3.2(a), Callister & a
Crystalline Solid

Rethwisch 8e.
atoms
g
unit cell 2 52.00 ρtheoretical = 7.18 g/cm3
mol
ρ= ρactual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol SLIDE
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 = (0.2887/1*10^9)*100
= _0.2887x10^-7______ cm
Density = 2* 52.00_______________
[(0.2887x10^-7)^3]* 6.02x10^23
7.18

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SAMPLE PROBLEM 2 Determining Atomic Radius from Crystal Structure

PROBLEM: Copper had the most essential industrial

applications of the three coinage metals [Group
1B(11)]. Its crystal structure adopts cubic closest
packing, and the edge length of the unit cell is
361.5 pm. What is the atomic radius of copper?

PLAN: Copper crystallizes in cubic closest packing. This

structure has a face-centered cubic (FCC) unit cell,
and we are given the cell edge length. We refer to
figure on the right, with edge length A = 361.5 pm,
and solve for r.

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SAMPLE PROBLEM 2 Determining Atomic Radius from Crystal Structure

SOLUTION:
Using the Pythagorean Theorem to find the diagonal of the cell’s face, C,
C = √ A2 + B2
The unit cell is a cube, so A = B.

C = √ 2A2 = √ 2(361.5 pm)2 = 511.2 pm

C = 4r

r = 511.2 pm/4 = 127.8 pm

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4 CRYSTALLINE SOLIDS
Bonding in Solids
There are four types of solid based on bonds:
1.  Molecular (formed from molecules) - usually soft with low
melting points and poor conductivity.
2.  Covalent - very hard with very high melting points and poor
conductivity.
3.  Ionic (formed form ions) - hard, brittle, high melting points and
poor conductivity.
4.  Metallic (formed from metal atoms) - soft or hard, high melting
points, good conductivity, malleable and ductile. A solid with only
one type of atom is also called ‘atomic’
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 Examples of Types of
Crystalline Solids 4

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CRYSTALLINE SOLIDS

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Molecular Solids
• orderly collection of molecules held
together by van der waals force
• gases solidify only at low
temperatures
• easy to deform and compress
• poor conductors Dry Ice
• ex. most organics, and inert gases (O2, (Solid Carbon Dioxide)
N2, H2)
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Covalent Solids
• 3D collection of atoms bound by shared
valence electrons
• difficult to deform because bonds are
directional
• high melting point (difficult to deform)
• no free electrons à poor electrical
atomic structure of
conductor diamond (carbon)
• most solids absorb photons à opaque
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Ionic Solids
• individual atoms act like closed-shell, spherical structures
leading to non directional binding
• commonly salts that are held together by the strong force of
attraction between ions of opposite charge
• tight packed arrangement à poor thermal conductors
• no free electrons à poor electrical conductors
• strong forces à hard, and high melting points
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 4 CRYSTALLINE SOLIDS
Metallic Solids
• constructed of atoms which have very weakly bounded
outer electrons
• large number of vacancies in orbitals (not enough energy
available to form covalent bonds)
• Electrons aren't tightly bound to individual atoms, and are
free to migrate through the metal. As a result, metals are
good conductors of electricity and heat.

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Problem Set
CRYSTALLINE SOLIDS

1.  Lead, Pb, is used in solders and as radiation shield. It adopts

the face centered cubic unit structure with each of the atom
having a diameter of 0.35 nanometer. Find the theoretical
density of lead if the molecular weight of this metal is 207.2
g/mol.
2.  Tantalum is a rare, hard, blue-gray, lustrous transition metal
that is highly corrosion-resistant. It has a density of 16.4
grams per cubic centimeter and a molecular weight of
180.948 g/mol. What is the atomic radius of Ta if it adopts
the body centered cubic unit structure. SLIDE
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 2 ELECTROCHEMICAL ENERGY
References
[1] Chang, R. (2010). Chemistry: 10th Edition. New York, NY:
Mc-Graw Hill
[2] Brady, Jespersen, & Hislop (2012). Chemistry: Sixth
Edition. Asia: John Wiley and Sons
[3] Callister, W. (2007). Materials Science and Engineering:
Seventh Edition. USA: John Wiley and Sons

--------- END OF MODULE 3 ---------

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