CHEMISTRY

Fifth Edition

Gilbert ● Kirss ● Foster ● Bretz ● Davies

Chapter 12
Solids: Crystals, Alloys, and Polymers
Chemistry, 5th Edition Copyright © 2017, W. W. Norton & Company
Particulate Review

What type of bond is found in potassium

iodide?
A. Ionic bond
B. Nonpolar covalent bond
C. Polar covalent bond
D. Metallic bond
Chemistry: An Atoms-Focused Approach, 2nd Edition Copyright © 2017, W. W. Norton & Company 2
Particulate Review (cont. 1)

What type of bond is found in platinum?

A. Ionic bond
B. Nonpolar covalent bond
C. Polar covalent bond
D. Metallic bond
Chemistry: An Atoms-Focused Approach, 2nd Edition Copyright © 2017, W. W. Norton & Company 3
Particulate Preview

Which allotrope of carbon has a repeating

pattern that is planar?
A. Allotrope A
B. Allotrope B
C. Allotropes A and B
Chemistry: An Atoms-Focused Approach, 2nd Edition Copyright © 2017, W. W. Norton & Company 4
Particulate Preview (cont. 1)

Which allotrope consists of carbon atoms

covalently bonded to one another?
A. Allotrope A
B. Allotrope B
C. Allotropes A and B
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Particulate Preview (cont. 2)

Which allotrope consists of both covalent

bonds and weak interactions between layers?
A. Allotrope A
B. Allotrope B
C. Allotropes A and B
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Chapter Outline
12.1 The Solid State
12.2 Structures of Metals
12.3 Alloys and Medicine
12.4 Ionic Solids and Salt Crystals
12.5 Allotropes
12.6 Polymers

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The Solid State
• Crystalline solid – a solid made of an
ordered array of atoms, ions, or molecules
• Amorphous solids – a solid that lacks long-
range order for the atoms, ions, or molecules
in its structure
• Metallic solids – A solid formed by metallic
bonds among atoms of metallic elements
• Molecular solids – a solid formed by
intermolecular attractive forces among
neutral, covalently bonded molecules
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The Solid State (cont. 1)
• Atomic solids – a solid formed by weak
attraction between noble gas atoms
• Covalent network solids – a solid
formed by covalent bonds among
nonmetal atoms in an extended array
• Ionic solids – a solid formed by ionic
bonds among monatomic and/or
polyatomic ions

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Types of Solids

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Structures
• Crystal lattice – ordered three-dimensional array
of particles in a crystalline solid
• Crystal structure – a particular arrangement in
three-dimensional space that specifies the
positions of the particles relative to one another in
a crystalline solid
• Unit cell – basic repeating unit of the
arrangement of particles in a crystalline solid
• Hexagonal closest-packed (hcp) – a crystal
structure in which the layers of atoms or ions have
an ababab… stacking pattern
• Cubic closest-packed (ccp) – a crystal structure
in which the layers of atoms or ions have an
abcabcabc… stacking pattern
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Unit Cells
• Hexagonal unit cell: an array of closest-
packed particles that includes parts of four
particles on the top and four on the bottom
faces of a hexagonal prism and one particle
in a middle layer

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Cubic Unit Cells
• Face-centered cubic (fcc) – closest
packing unit cell in which atoms are
located on the
eight corners
and six faces
of a cube

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Cubic Unit Cells (cont. 1)
• Simple cubic (sc) – square-packing
arrangement; particles located at eight
corners of cubic unit cell

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Cubic Unit Cells (cont. 2)
• Body-centered cubic (bcc) – square
packing arrangement in which particles
are located at eight corners and in center
of cubic unit cell

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Crystal Structures of Metals

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Summary of Unit Cells

hcp and ccp: most efficient!

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Unit Cell Dimensions
• Simple cubic (sc):
– Atoms touch along
cell edge.

• Face-centered
cubic (fcc):
– Atoms touch along
face diagonal.

• Body-centered
cubic (bcc):
– Atoms touch along
body diagonal.

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Shared Atoms in Unit Cells

• Atoms on corners:
– Shared by eight cells; 1/8 in each cell
– (1/8 per corner) × 8 corners = 1 atom
• Atoms on faces:
– Shared by two cells; ½ in each cell
– (½ per face) × 6 faces = 3 atoms
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Shared Atoms in Unit Cells (cont. 1)

• Atoms in body:
– Completely located in unit cell
– 1 atom
• Atoms on edges:
– Shared by four cells; ¼ in each cell
– (¼ per edge) × 12 edges = 3 atoms
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Number of Atoms in a Unit Cell
• Simple cubic cell:
– Eight atoms on corners;
1/8 × 8 = 1 atom/cell
• Body-centered cubic (bcc):
– Eight on corners + one in
center
– (1/8 × 8) + 1 = 2 atoms per
unit cell
• Face-centered cubic (fcc):
– Eight on corners + six on
faces
– (1/8 × 8) + (½ × 6) = 4 atoms
per unit cell
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Characteristics of Unit Cells

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Practice: Atomic Radius
• Tantalum crystallizes with a bcc unit cell.
Its unit cell has an edge length of 330.3
pm. Calculate the radius in picometers of
the tantalum atoms.
• Collect and Organize:
– We are given the unit cell (bcc) and edge
length ℓ = 330.3 pm of tantalum. We need to
calculate the radius, r.

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Practice: Atomic Radius (cont. 1)
• Tantalum crystallizes with a bcc unit cell.
Its unit cell has an edge length of 330.3
pm. Calculate the radius in picometers of
the tantalum atoms.
• Analyze:
– The tantalum atoms do not touch along the
unit cell edges or along any face diagonal,
but they do touch along the body diagonals.
The relationship between r and ℓ is given by:

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Practice: Atomic Radius (cont. 2)
• Tantalum crystallizes with a bcc unit cell.
Its unit cell has an edge length of 330.3
pm. Calculate the radius in picometers of
the tantalum atoms.
• Solve:
– Substituting the edge length into the formula
for r:
330.3 pm 3
r= = 143.0 pm
4

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Practice: Atomic Radius (cont. 3)
• Tantalum crystallizes with a bcc unit cell.
Its unit cell has an edge length of 330.3
pm. Calculate the radius in picometers of
the tantalum atoms.
• Think About It:
– The value of r, 143 pm, is indeed less than
half the value of the edge length
(ℓ/2 = 165 pm), so the result of this calculation
is reasonable.

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Alloys
• Alloy – a blend of a host metal and one or
more other elements, which may or may
not be metals, that are added to change
the properties of the host metal
• Homogenous alloys – a solid solution in
which atoms of host and added elements
are randomly and uniformly distributed
• Heterogeneous alloys – a matrix of host
metal atoms with “islands” of atoms of
added elements interspersed

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 Substitutional Alloy: Bronze

• Substitutional alloy – atoms of nonhost metal

replace host atoms in the crystal lattice
• Bronze (substitutional, homogeneous):
– Host = Cu; added element = Sn (up to 30%)

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Interstitial Alloys
• Interstitial alloy – atoms of added element
occupy the spaces between atoms of the
host
– Octahedral: larger; cluster of six host atoms
– Tetrahedral: smaller; cluster of four host atoms

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Interstitial Alloy: Carbon Steel
• Fe at high temperatures
forms fcc lattice
(austentite). Carbon
atoms occupy
octahedral spaces
between Fe atoms in
lattice structure.

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Salt Crystals: Ionic Solids
• Ionic solids:
– Monoatomic or
polyatomic ions held
together by ionic bonds
(most are crystalline, e.g.,
NaCl)
– Cubic closest packing
(fcc) of Cl– ions with Na+
ions in octahedral holes
(rock salt structure)

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Other Ionic Crystals: Sphalerite
• Sphalerite (ZnS):
– fcc unit cell of S2– with
Zn2+ in four of the eight
tetrahedral holes

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Practice: Lattice Structures
• Sphalerite (ZnS) has S2– ions in an fcc
structure with Zn2+ ions occupying four of
the eight tetrahedral holes in the unit cell.
Verify that the unit cell is neutral.
• Collect and Organize:
– We know the lattice structure and the formula
unit for ZnS.

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Practice: Lattice Structures (cont. 1)

• Sphalerite (ZnS) has S2– ions in an fcc

structure with Zn2+ ions occupying four of
the eight tetrahedral holes in the unit cell.
Verify that the unit cell is neutral.
• Analyze:
– From the lattice unit cell information we can
calculate the number of each ion in the unit
cell.

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Practice: Lattice Structures (cont. 2)

• Sphalerite (ZnS) has S2– ions in an fcc

structure with Zn2+ ions occupying four of
the eight tetrahedral holes in the unit cell.
Verify that the unit cell is neutral.
• Solve:
– S2–: For the fcc lattice, there are four ions per
unit cell = total –8 charge from sulfide ions.
– Zn2+: Four tetrahedral holes completely
contained within the unit cell = four Zn2+ ions
= total +8 charge from Zn ions.
Chemistry, 5th Edition Copyright © 2017, W. W. Norton & Company 35
Practice: Lattice Structures (cont. 3)

• Sphalerite (ZnS) has S2– ions in an fcc

structure with Zn2+ ions occupying four of
the eight tetrahedral holes in the unit cell.
Verify that the unit cell is neutral.
• Think About It:
– The total number of positive and negative
charges in the lattice unit cell sums to zero,
which would be expected for an ionic formula
unit.

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Other Ionic Crystals: Fluorite
• Fluorite (CaF2):
– Ca2+ ions form an
expanded fcc array to
accommodate the larger
F– ions, which occupy all
eight tetrahedral holes.

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Allotropes of Carbon
• Allotropes – different
molecular structures of
an element
• Allotropes of carbon
– Diamond:
• Network covalent solid
• All carbon atoms sp3
hybridized; tetrahedral
configuration
• Hard; nonconductive; high
m.p.

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Allotropes of Carbon (cont. 1)
• Graphite:
– Two-dimensional
covalent network of sp2
hybridized carbon atoms
in sheets of fused six-
membered rings
– Sheets held together by
dispersion forces
– Soft; good lubricant;
conductive

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Allotropes of Carbon (cont. 2)
• Carbon nanotubes:
– Graphite sheet structure
rolled into tubes
– sp2 hybridized carbon
atoms
– Semiconductor behavior
– Extreme strength!

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Allotropes of Carbon (cont. 3)
• Fullerene:
– Three-dimensional
network of sp2
hybridized carbon
atoms in fused five- and
six-membered rings to
form molecular clusters
of 60, 70, or more
carbon atoms

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Polymers
• Polymer (macromolecule) – a very large
molecule with high molar mass formed by
bonding together a large number of small
molecules of low molecular mass
• Monomer – small molecule that bonds
with others like it to form polymers
• Oligomer – molecule that contains a few
monomers; the middle ground between
small molecules and polymers

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Polymers of Alkenes
• Homopolymer – a polymer composed of
only one kind of monomer unit
– Example: polyethylene (PE)
n CH2 = CH2 → –[–CH2–CH2–]n–
• Addition polymer – macromolecule
prepared by adding monomers to a growing
polymer chain
• Addition reaction – a reaction in which two
reactants couple together to form one
product without the loss of any atoms or
molecules
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Polymers of Alkenes (cont. 1)

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 Other Polymers: Teflon

• Teflon
(polytetrafluoroethylene)

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Polymers Containing Aromatic Rings

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Polymers of Alcohols and Ethers

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Polymers
• Copolymer – macromolecule formed
from the chemical combination of two
different monomers (e.g., poly(ethylene-
co-vinyl alcohol)

• Heteropolymer – polymer made of three

or more different monomer units
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Esters and Amides
• Condensation reaction – two molecules
combining to form a larger molecule and a
small molecule (typically water)

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Synthesis of Polyesters

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Synthesis of Polyamides

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Kevlar

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Visual Problems
1. Which
representation
depicts an ionic
compound?

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Visual Problems (cont. 1)
2. Which
representation
depicts an
interstitial alloy?

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Visual Problems (cont. 2)
3. Which
representation
depicts the
formation of a
substitutional
alloy?

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Visual Problems (cont. 3)
4. Which polymers
are formed by an
additional
polymerization
process?

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Visual Problems (cont. 4)
5. Which polymers
are formed by a
condensation
polymerization
process?

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