Lecture Presentation

Chapter 12

Solids and
Modern Materials

James F. Kirby
Quinnipiac University
Hamden, CT
© 2015 Pearson Education, Inc.
Classifying Solids Based on Bonds
• Metallic solids are held
together by a “sea” of
collectively shared electrons.
• Ionic solids are sets of
cations and anions mutually
attracted to one another.
• Covalent-network solids
are joined by an extensive
network of covalent bonds.
• Molecular solids are
discrete molecules held
together by weak forces. Modern
Materials

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 Two Other Types of Solids
 Polymers contain long chains of atoms connected by
covalent bonds; the chains can be connected to other
chains by weak forces. These molecules have
different properties than small molecules or metallic
or ionic compounds.
 Nanomaterials are crystalline compounds with the
crystals on the order of 1–100 nm; this gives them
very different properties than larger crystalline
materials.

Modern
Materials

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 One Organization of Solids
• Solids with a regular
repeating pattern of
atoms are crystalline.
• Amorphous solids are
characterized by a
distinct lack of order in
the arrangement of
atoms.
• Since crystalline solids
have a regular pattern,
they are of more interest
to most chemists. Modern
Materials

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 Unit Cell
• The basis of a repeating pattern is the
unit cell.
• The structure of a crystalline solid is
defined by
 the size and shape of the unit cell.
 the locations of atoms within the unit cell.

Modern
Materials

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 Lattice Points
• Positions that define the overall
structure of the crystalline compound
are called lattice points.
• Each lattice point has an identical
environment.
• Lattice vectors connect the points and
define the unit cell.
• The next slide shows how this works for
five different two-dimensional lattices.
Modern
Materials

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 2-D Lattices

Modern
Materials

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 3-D Crystal Lattices
• There are seven basic three-dimensional lattices:
cubic, tetragonal, orthorhombic, rhombohedral,
hexagonal, monoclinic, and triclinic.
• If have lattices points only on the corners it is called
primitive lattice. Placing additional lattice points in
specific locations result in the formation of centered
lattices

Modern
Materials

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 Primitive vs. Centered Lattices
• Primitive lattices
have atoms only in
the lattice points.
• Centered lattices
have atoms in
another regular
location, most
commonly the
body-center or the
face-center. Modern
Materials

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 Modern
Materials

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 Motifs
Sometimes, the atoms are not on the lattice points,
but the overall structure follows a particular unit
cell. The groups of atoms that define the overall
structure is called a motif.

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Materials

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© 2015 Pearson Education, Inc.
 Metals
• Metallic bonding: valance electrons are delocalized
• A regular array of cations in a “sea” of mobile
valence electrons.
• Lustrous surface
• High termal and electrical conductivity
• Malleable and ductile

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Materials

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 Metallic Structure
• The structures of many metals conform to one of the
cubic unit cells: simple cubic, body-centered cubic, or
face-centered cubic.
Examples: Po Fe, Cr, Na, W Al, Pb, Cu, Ag, Au

Modern
Materials

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 Cubic Structures
• Not every part of an atom on a lattice
point is completely within that unit cell.
One can determine how many atoms
are within each unit cell.
• Eight cubes meet at a corner, therefore
only 1/8 of that corner atom is within
any one unit cell meeting there.
• Two cubes meet at a face, therefore
only 1/2 of that face atom is within any
one unit cell meeting there.
• A body-centered atom is entirely
within the unit cell. Modern
Materials

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 Modern
Materials

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Section 10.4
Structure and Bonding in Metals

CONCEPT CHECK!
A metal crystallizes in a face-centered cubic structure.

Determine the relationship between the radius of the

metal atom and the length of an edge of the unit cell.

Length of edge = r  8

Copyright © Cengage Learning. All rights reserved 19

Section 10.3
An Introduction to Structures and Types of Solids

Three Cubic Unit Cells

and the Corresponding
Lattices

(4r)2 = 3d2
Copyright © Cengage Learning. All rights reserved 20
 Close Packing
• Nature does not like
empty space!
• The atoms in a crystal
pack as close together
as they can.
• The two common
types of packing seen
are
 cubic close-packing
(ccp)
 hexagonal close-
packing (hcp) Modern
Materials

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 Closest-Packed Structures
First Layer
• With spheres, it is more efficient to offset each
row in the gaps of the previous row than to line
up rows and columns

Tro: Chemistry: A Molecular Approach, 2/e 22 Copyright  2011 Pearson Education, Inc.
 Closest-Packed Structures
Second Layer
• The second layer atoms can sit directly over the
atoms in the first layer– called an AA pattern
• Or the second layer can sit over the holes
in the first layer – called an AB pattern

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 Closest-Packed Structures
Third Layer – with Offset 2nd Layer
• The third layer atoms can align directly over the
atoms in the first layer– called an ABA pattern
• Or the third layer can sit over the uncovered
holes in the first layer– called an ABC
pattern

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 • In both ccp and hcp,
each atom has 12
neighbours, 6 in the
same layer, 3 in the
above layer and 3 in
the below layer
• We say that each
sphere has a
coordination
number of 12.

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 Face centered cubic
unit cell

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 Simple Cubic

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 Cubic Unit Cells -
Body-Centered Cubic
• Nine particles, one at each
corner of a cube + one in center
• 1/8th of each corner particle lies
in the unit cell 4r
 two particles in each unit cell
3
8 corners x 1/8
+ 1 center
• Edge of unit cell = (4/Ö 3) times
the radius of the particle
• Coordination number of 8
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 Body-Centered Cubic

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 Cubic Unit Cells -
Face-Centered Cubic
• 14 particles, one at each corner
of a cube + one in center of
each face
• 1/8th of each corner particle +
1/2 of face particle lies in the
unit cell 2r 2
 4 particles in each unit cell
8 corners x 1/8
+ 6 faces x 1/2
• Edge of unit cell = 2 2 times
the radius of the particle
• Coordination number of 12
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 Face-Centered Cubic

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 Example 11.6: Calculate the density of Al if it
crystallizes in a fcc and has a radius of 143 pm
Given: face-centered
face-centeredcubic,
cubic,Vr==6.618
143 pm
1.43 xx10
10−8−23cm,
cmm3
,m
= 1.792
=1.792x x1010
−22
gg
−22

Find: density,
density,g/cm
g/cm3 3

Conceptual fcc mass r l V

Plan:
# atoms x mass of 1 atom l = 2r√2 V=l3
m, V d
Relationships: d = m/V
1 cm = 10 m, 1 pm = 10−12 m V = l 3, l = 2r√2, d = m/V
2

fcc = 4 atoms/uc, Al = 26.982 g/mol, 1 mol = 6.022 x 1023 atoms

Solution:

Check: the accepted density of Al at 20°C is 2.71 g/cm3, so the

answer makes sense
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 Practice – Estimate the density of Rb if it crystallizes
in a body-centered cubic unit cell and has an atomic
radius of 247.5 pm

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 Practice – Estimate the density of Rb if it
crystallizes in a bcc and has a radius of 247.5 pm
Given: body-centered
body-centered
body-centered cubic, V=rr=
cubic,
cubic, 1.868 x 10
=2.475
247.5xpm
10 cmcm,
−22 −8 3
, m=
m 2.839 x 10
= 2.839 10g−22 g
x −22
Find: density,
density,g/cm
density, g/cm
g/cm
333

Conceptual bcc mass r l V

Plan:
# atoms x mass of 1 atom l = 4r/√3 V=l3
m, V d
Relationships: d = m/V
1 cm = 10 m, 1 pm = 10−12 m V = l 3, l = 4r/√3, d = m/V
2

bcc = 2 atoms/uc, Rb = 85.47 g/mol, 1 mol = 6.022 x 10 23 atoms

Solution:

Check: the accepted density of Rb at 20°C is 1.53 g/cm3, so the answer

makes sense
Tro: Chemistry: A Molecular Approach, 2/e 36 Copyright  2011 Pearson Education, Inc.
 Sample Exercise 12.1 Calculating Packing Efficiency
It is not possible to pack spheres together without leaving some
void spaces between the spheres. Packing efficiency is the fraction
of space in a crystal that is actually occupied by atoms. Determine
the packing efficiency of a face-centered cubic metal.
Solution
Analyze We must determine the volume taken up by the atoms that reside in the unit cell
and divide this number by the volume of the unit cell.
Plan We can calculate the volume taken up by atoms by multiplying the number of atoms per
unit cell by the volume of a sphere, 4πr3/3. To determine the volume of the unit cell, we must
first identify the direction along which the atoms touch each other. We can then use geometry
to express the length of the cubic unit cell edge, a, in terms of the radius of the atoms. Once
we know the edge length, the cell volume is simply a3.
Solve
As shown in Figure 12.12, a face-centered cubic metal has four atoms per unit cell. Therefore,
the volume occupied by the atoms is

Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
 Sample Exercise 12.1 Calculating Packing Efficiency
Continued

For a face-centered cubic metal the atoms touch along the diagonal of a face of the unit cell:

Therefore, a diagonal across a face of the unit cell is equal to four times the atomic radius, r. Using simple
trigonometry, and the identity we can show that

Finally, we calculate the packing efficiency by dividing the volume occupied by atoms by the volume of the cubic
unit cell, a3:

Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
 Iridium has a face-centered cubic unit cell with an edge length of 383.3 pm. The
density of iridium is 22.61 g/cm3. Use these data to calculate a value for Avogadro's
Number.

Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
 Alloys
• Alloys are materials that contain more than one element
and have the characteristic properties of metals.
• It is an important means employed to change the
properties of certain metals.

Modern
Materials

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 Types of Alloys

• Substitutional alloys: A second element takes the

place of a metal atom.
• Interstitial alloys: A second element fills a space in
the lattice of metal atoms.
• Heterogeneous alloys: components not dispersed
uniformly Modern
• Intermetallic compounds: Materials

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 Two Types of Alloys
(Homogenous)
 Substitutional Alloy – some
of the host metal atoms are
replaced by other metal
atoms of similar size and
chemical bonding
characteristics.
 Interstitial Alloy – some of
the holes in the closest
packed metal structure are
occupied by small atoms. Modern
Materials

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 24 karat = 100% gold
14 karat = (14/24) *100 = 58% gold

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 Heterogeneous Alloys
• Components are not dispersed uniformly
• Example: Pearlite has two phases

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 Intermetallic Compounds
• compounds, not mixtures
• distinct properties, definite composition
(since they are compounds)
• ordered, rather than randomly distributed

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Materials

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 Metallic Bonding

• 8-N rule = #of bonding

• Metals do not have enough valence electrons to form localized
electron pair bonds.
• So valence electrons are collectively shared.
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 Metallic Bonding – Electron
Sea Model
• One can think of a metal
as a group of cations
suspended in a sea of
electrons.
• The electrical and
thermal conductivity,
ductility, and malleability
of metals is explained by
this model.

Modern
Materials

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 Metallic Bonding – Electron
Sea Model
• It does not adequately
explain many properties
of metals
• Ex: According to electron
sea model, the strength
of bonding should
increase as the number
of valence electrons
increase-higher melting
point
Modern
Materials

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 The MO Theory has five basic
rules:
1. The number of molecular orbitals = the number of
atomic orbitals combined
2. Of the two MO's, one is a bonding orbital (lower
energy, strengthens the bond) and one is an
antibonding orbital (higher energy, weakens the
bond)
3. Electrons enter the lowest orbital available
4. The maximum # of electrons in an orbital is 2 (Pauli
Exclusion Principle)
5. Electrons spread out before pairing up (Hund's
Rule)
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Materials

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 A Molecular-Orbital Approach
As the number of atoms
in a chain increases, the
energy gap between the
bonding orbitals and
between the antibonding
orbitals disappears,
resulting in a continuous
band of energy. The
approach seen here
only takes into account
s-orbital population. Modern
Materials

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Section 10.4
Structure and Bonding in Metals

Molecular Orbital Energy

Levels Produced When
Various Numbers of Atomic
Orbitals Interact

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 Band Theory

• The structures of metals and covalent network

solids result in every atom’s orbitals being
shared by the entire structure
• For large numbers of atoms, this results in a
large number of molecular orbitals that have
approximately the same energy; we call this an
energy band

Tro: Chemistry: A Molecular Approach, 2/e 53 Copyright  2011 Pearson Education, Inc.
 Band Theory
• When two atomic orbitals combine they
produce both a bonding and an antibonding
molecular orbital
• When many atomic orbitals combine they
produce a band of bonding molecular orbitals
and a band of antibonding molecular orbitals
• The band of bonding molecular orbitals is
called the valence band
• The band of antibonding molecular orbitals is
called the conduction band

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 Molecular Orbitals of Polylithium

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 MO Approach with More Orbitals
• Most metals have d and p orbitals to consider.
• Their MO diagrams lead to more bands that
better explain conductivity and other properties of
metals. Ni = [Ar]4s23d8
Electrons near the top can
easily jump to empty
unoccupied orbitals
Overlap of energy bands is imp.

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Materials

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 MO Approach with More Orbitals
• MO model predicts that bonding first becomes stronger as
the number of valance electrons increase
• The bonds grow weaker as the electrons start populating
antibonding orbitals
• Strong bonds, high melting and boiling points, higher heat of
fusion, higher hardness etc.

Modern
Materials

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 Band Gap
• At absolute zero, all the electrons will occupy
the valence band
• As the temperature rises, some of the electrons
may acquire enough energy to jump to the
conduction band
• The difference in energy between the valence
band and conduction band is called the band
gap, Eg
 the larger the band gap, the fewer electrons there
are with enough energy to make the jump

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 Types of Band Gaps and
Conductivity

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 Band Gap and Conductivity
• The more electrons at any one time that a substance has in
the conduction band, the better conductor of electricity it is
• If the band gap is ~0, then the electrons will be almost as
likely to be in the conduction band as the valence band and
the material will be a conductor
 metals
 the conductivity of a metal decreases with temperature
• If the band gap is small, then a significant number of the
electrons will be in the conduction band at normal
temperatures and the material will be a semiconductor
 graphite
 the conductivity of a semiconductor increases with temperature
• If the band gap is large, then effectively no electrons will be
in the conduction band at normal temperatures and the
material will be an insulator
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 Semiconductors
• They have a gap
between the occupied
MOs (valence band)
and the unoccupied
ones (conduction
band).
• Electrons must enter
the conduction band for
electron transfer.
• Group IVA elements
have gaps between the Note: Band gaps over
bands of 0.08 to 3.05 3.5 eV lead to the material
being an insulator.
eV (7 to 300 kJ/mol).
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 What Forms a Semiconductor?
• Elemental Semiconductors : Among elements, only
Group IVA, all of which have 4 valence electrons, are
semiconductors.
• Compound Semiconductors:Inorganic semiconductors
(like GaAs) tend to have an average of 4 valence
electrons (3 for Ga, 5 for As).

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 Trends in Semiconductor
• Moving down a group, the band gap decreases.
C > Si > Ge > Sn
• The band gap increases as the difference in group
numbers of elements increases.
ZnSe > GaAs

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Sample Exercise 12.3 Qualitative Comparison of Semiconductor Band Gaps
Will GaP have a larger or smaller band gap than ZnS? Will it have a larger or
smaller band gap than GaN?
Solution
Analyze The size of the band gap depends on the vertical and horizontal positions of the elements in the periodic
table. The band gap will increase when either of the following conditions is met: (1) The elements are located
higher up in the periodic table, where enhanced orbital overlap leads to a larger splitting between bonding and
antibonding orbital energies, or (2) the horizontal separation between the elements increases, which leads to an
increase in the electronegativity difference and bond polarity.
Plan We must look at the periodic table and compare the relative positions of the elements in each case.
Solve Gallium is in the fourth period and group 3A. Phosphorus is in the third period and group 5A. Zinc and
sulfur are in the same periods as gallium and phosphorus, respectively. However, zinc, in group 2B, is one
element to the left of gallium; sulfur in group 6A is one element to the right of phosphorus. Thus, we would
expect the electronegativity difference to be larger for ZnS, which should result in ZnS having a larger band gap
than GaP. For both GaP and GaN the more electropositive element is gallium. So we need only compare the
positions of the more electronegative elements, P and N. Nitrogen is located above phosphorus in group 5A.
Therefore, based on increased orbital overlap, we would expect GaN to have a larger band gap than GaP.
Check External references show that the band gap of GaP is 2.26 eV, ZnS is 3.6 eV, and GaN is 3.4 eV.

Copyright  2011 Pearson Education, Inc.

Sample Exercise 12.3 Qualitative Comparison of Semiconductor
Band Gaps
Continued

Practice Exercise 1

Which of these statements is false?

(a) As you go down column 4A in the periodic table, the elemental solids become
more electrically conducting. (b) As you go down column 4A in the periodic table,
the band gaps of the elemental solids decrease. (c) The valence electron count for a
compound semiconductor averages out to four per atom. (d) Band gap energies of
semiconductors range from ~0.1 to 3.5 eV. (e) In general, the more polar the
bonds are in compound semiconductors, the smaller the band gap.

Practice Exercise 2
Will ZnSe have a larger or smaller band gap than ZnS?

The calculated band gaps are 3.97, and 3.10 eV for ZnS, and ZnSe, respectively.

Copyright  2011 Pearson Education, Inc.

• changing the conductivity Doping
of semiconductors by
adding an element with
more or fewer electrons
• n-type semiconductors
have more electrons, so
the negative charge
travels in the
conductance band.
• p-type semiconductors
have fewer electrons, so
the “hole” travels in the
valence band.
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Silicon Crystal Doped
with
(a) Arsenic and
(b) Boron

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 Energy Level Diagrams for
(a) an n-type Semiconductor (b) a p-type Semiconductor

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LED - DIODES

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 Sample Exercise 12.4 Identifying Types of Semiconductors
Which of the following elements, if doped into silicon, would yield
an n-type semiconductor: Ga, As, or C?
Solution
Analyze An n-type semiconductor means that the dopant atoms must have more valence electrons than the host
material. Silicon is the host material in this case.
Plan We must look at the periodic table and determine the number of valence electrons associated with Si, Ga, As,
and C. The elements with more valence electrons than silicon are the ones that will produce an n-type material upon
doping.
Solve Si is in column 4A, and so has four valence electrons. Ga is in column 3A, and so has three valence electrons.
As is in column 5A, and so has five valence electrons; C is in column 4A, and so has four valence electrons.
Therefore, As, if doped into silicon, would yield an n-type semiconductor.

Copyright  2011 Pearson Education, Inc.

 Practice Exercise 1

Which of these doped semiconductors would yield a p-type

material? (These choices are written as host atom: dopant
atom.)
(a) Ge:P (c) Si:Ge (b) Si:Al (d) Ge:S (e) Si:N

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 Ionic Solids
• In ionic solids, the lattice
comprises alternately charged
ions.
• Ionic solids have very high
melting and boiling points and
are quintessential crystals.
• Do not conduct electricity
because the valence electrons
are confined to anions, are not
delocalized
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Materials

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 Lattice Energy

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Materials

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• Most favorable
structures have cation– Ionic Solids
anion distances as
close as possible, but
the anion–anion and
cation–cation distances
are maximized.
• Three common
structures for 1:1 salts:
 CsCl structure
 NaCl (rock salt)
structure
 zinc blende (ZnS)
Modern
structure Materials

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 Rock Salt Structures
• Based on face centered cubic lattice
• Coordination number = 6
• Cl─ ions (181 pm) in a face-centered
cubic arrangement
 ⅛ of each corner Cl─ inside the unit cell
 ½ of each face Cl─ inside the unit cell
• Na+ (97 pm) in holes between Cl─
 1 in center of unit cell
 ¼ of each edge Na+ inside the unit cell
• Na:Cl = (¼ x 12) + 1: (⅛ x 8) + (½ x
6) = 4:4 = 1:1,
• Therefore the formula is NaCl

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 Zinc Blende Structures
• Based on face centered cubic lattice
• Coordination number = 4
• S2─ ions (184 pm) in a face-centered
cubic arrangement
 ⅛ of each corner S2─ inside the unit cell
 ½ of each face S2─ inside the unit cell
• Each Zn2+ (74 pm) in holes between
S2─
 1 whole particle in ½ the holes
• Zn:S = (4 x 1) : (⅛ x 8) + (½ x 6) =
4:4 = 1:1,
• Therefore the formula is ZnS

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 Effect of Ion Size on Structure
• Size and stoichiometry are two main determinants of the
structure
• The size of the cation compared to the anion (radius ratio) is
the major factor in which structure is seen for ionic
compounds.
• When anion and cation are similar in size, large coordination
number is favored

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Materials

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 Fluorite Structures
• Coordination number = 4
• Ca2+ ions (99 pm) in a face-centered
cubic arrangement
 ⅛ of each corner Ca2+ inside the unit cell
 ½ of each face Ca2+ inside the unit cell
• Each F─ (133 pm) in holes between
Ca2+
 1 whole particle in all the holes
• Ca:F = (⅛ x 8) + (½ x 6): (8 x 1) =
4:8 = 1:2,
• Therefore the formula is CaF2
 fluorite structure common for 1:2 ratio
• Usually get the antifluorite structure
when the cation:anion ratio is 2:1
 the anions occupy the lattice sites and
the cations occupy the tetrahedral holes

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 Empirical Formula
• As the cation/anion ratio goes down there are fewer
cations to surround each anion

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Materials

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 Sample Exercise 12.2 Calculating the Density of an Ionic Solid
Rubidium iodide crystallizes with the same structure as sodium chloride. (a)
How many iodide ions are there per unit cell? (b) How many rubidium ions are
there per unit cell? (c) Use the ionic radii and molar masses of Rb+ (1.66 Å ,
85.47 g/mol) and I– (2.06 Å, 126.90 g/mol) to estimate the density of rubidium
iodide in g/cm3.
Solution
Analyze and Plan
(a) We need to count the number of anions in the unit cell of the sodium chloride structure, remembering that ions
on the corners, edges, and faces of the unit cell are only partially inside the unit cell.
(b) We can apply the same approach to determine the number of cations in the unit cell. We can double-check our
answer by writing the empirical formula to make sure the charges of the cations and anions are balanced.
(c) Because density is an intensive property, the density of the unit cell is the same as the density of a bulk crystal.
To calculate the density we must divide the mass of the atoms per unit cell by the volume of the unit cell. To
determine the volume of the unit cell we need to estimate the length of the unit cell edge by first identifying the
direction along which the ions touch and then using ionic radii to estimate the length. Once we have the length
of the unit cell edge we can cube it to determine its volume.

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Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
 Sample Exercise 12.2 Calculating the Density of an Ionic Solid
Continued

Solve
(a) The crystal structure of rubidium iodide looks just like NaCl with
Rb+ ions replacing Na+ and I– ions replacing Cl–. From the views of
the NaCl structure in Figures 12.25 and 12.26 we see that there is
an anion at each corner of the unit cell and at the center of each
face. From Table 12.1 we see that the ions sitting on the corners are
equally shared by eight unit cells (1/8 ion per unit cell), while those
ions sitting on the faces are equally shared by two unit cells (1/2
ion per unit cell). A cube has eight corners and six faces, so the
total number of I– ions is 8 (1/8) + 6 (1/2) =
4 per unit cell.

Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
 Sample Exercise 12.2 Calculating the Density of an Ionic Solid
Continued

(b) Using the same approach for the rubidium cations we see that there is a rubidium ion on each edge and one at the
center of the unit cell. Using Table 12.1 again we see that the ions sitting on the edges are equally shared by four
unit cells (1/4 ion per unit cell), whereas the cation at the center of the unit cell is not shared. A cube has 12 edges,
so the total number of rubidium ions is 12 (1/4) + 1 = 4. This answer makes sense because the number of Rb + ions
must be the same as the number of I – ions to maintain charge balance.
(c) In ionic compounds cations and anions touch each other. In RbI the cations and anions touch along the edge of the
unit cell as shown in the following figure.

The distance the unit cell edge is equal to r(I–) + 2r(Rb+) + r(I–) = 2r(I–) + 2r(Rb+). Plugging in the ionic radii we get
2(2.06 Å) + 2(1.66 Å) = 7.44 Å. The volume of a cubic unit cell is just the edge length cubed. Converting from Å to
cm and cubing we get
Volume = (7.44 × 10–8 cm)3 = 4.12 × 10–22 cm3.

Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
 Sample Exercise 12.2 Calculating the Density of an Ionic Solid
Continued

From parts (a) and (b) we know that there are four rubidium and four iodide ions per unit cell. Using this result and
the molar masses we can calculate the mass per unit cell

The density is the mass per unit cell divided by the volume of a unit cell

Check The densities of most solids fall between the density of lithium (0.5 g/cm 3) and that of iridium (22.6 g/cm 3),
so this value is reasonable.

Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
 Cesium Chloride Structures
• Based on the primitive cubic cell
• Anions sit at lattice points at the
corner
• A cation sits at the center of the
cubic cell
• Coordination number = 8
• ⅛ of each Cl─ (184 pm) inside the
unit cell
• Whole Cs+ (167 pm) inside the unit
cell
• Cs:Cl = 1:1 (8 x ⅛), therefore the
formula is CsCl

Tro: Chemistry: A Molecular Approach, 2/e 86 Copyright  2011 Pearson Education, Inc.
 Molecular Solids
• The lattice sites are occupied by molecules
 CO2, H2O, C12H22O11
• The molecules are held together by
intermolecular attractive forces
 dispersion forces, dipole–dipole attractions, and
H-bonds
• Because the attractive forces are weak, they
tend to have low melting points
 generally < 300 °C

Tro: Chemistry: A Molecular Approach, 2/e 88 Copyright  2011 Pearson Education, Inc.
 Molecular Solids
• Consist of atoms or
molecules held
together by weaker
forces (dispersion,
dipole–dipole, or
hydrogen bonds).
• Shape (ability to
stack) matters for
some physical
properties, like
boiling point.
Modern
Materials

© 2015 Pearson Education, Inc.

 Covalent-Network Solids
• Atoms are covalently
bonded over large
network distances with
regular patterns of
atoms.
• Tend to have higher
melting and boiling
points.
• Diamond is an
example.
• SiO2, SiC, BN Modern
Materials

© 2015 Pearson Education, Inc.

 Network Covalent Solids
• Because of the directionality of the covalent
bonds, these do not tend to form closest-packed
arrangements in the crystal
• Because of the strength of the covalent bonds,
these have very high melting points
 generally > 1000 °C
• Dimensionality of the network affects other
physical properties

Tro: Chemistry: A Molecular Approach, 2/e 91 Copyright  2011 Pearson Education, Inc.
 The Diamond Structure:
a 3-Dimensional Network
• The carbon atoms in a diamond each have four
covalent bonds to surrounding atoms
 sp3
 tetrahedral geometry
• This effectively makes each crystal one giant
molecule held together by covalent bonds
 you can follow a path of covalent bonds from any
atom to every other atom

Tro: Chemistry: A Molecular Approach, 2/e 92 Copyright  2011 Pearson Education, Inc.
 Properties of Diamond
• Very high melting point, ~3550 °C
 need to overcome some covalent bonds
• Very rigid
 due to the directionality of the covalent
bonds
• Very hard
 due to the strong covalent bonds holding
the atoms in position
 used as abrasives
• Electrical insulator
• Chemically very nonreactive

Tro: Chemistry: A Molecular Approach, 2/e 93 Copyright  2011 Pearson Education, Inc.
Section 10.5
Carbon and Silicon: Network Atomic Solids
Partial Representation of the Molecular Orbital Energies in
a) Diamond b) a Typical Metal

Copyright © Cengage Learning. All rights reserved 94

 The Graphite Structure:
a 2-Dimensional Network
• In graphite, the carbon atoms in a sheet are
covalently bonded together
 forming six-member flat rings fused together
 similar to benzene
 bond length = 142 pm
 sp2
 each C has three sigma and one pi bond
 trigonal-planar geometry
 each sheet a giant molecule
• The sheets are then stacked and held together by
dispersion forces
 sheets are 341 pm apart

Tro: Chemistry: A Molecular Approach, 2/e 95 Copyright  2011 Pearson Education, Inc.
 Properties of Graphite
• Hexagonal crystals
• High melting point, ~3652 °C
 need to overcome some covalent bonding
• Slippery feel
 because there are only dispersion forces
holding the sheets together, they can slide
past each other
 glide planes
 lubricants
• Electrical conductor
 parallel to sheets
• Chemically very nonreactive

Tro: Chemistry: A Molecular Approach, 2/e 96 Copyright  2011 Pearson Education, Inc.
Section 10.5
Carbon and Silicon: Network Atomic Solids

The Structures of Diamond and Graphite

Copyright © Cengage Learning. All rights reserved 97

 Polymers
• Polymers are molecules of high molecular weight
made by joining smaller molecules, called
monomers.

Modern
Materials

© 2015 Pearson Education, Inc.

 Polymers
• Natural Polymers:silk, leather, wool,
natural rubber
• Synthetic polymers: plastics
– Thermoplastics: can be reshaped ex:
polyethylene in plastic milk containers
– Thermosetting plastics: cannot be
reshaped ex:nylon and polyesters
– Elastomer: rubbery elastic behavior,
regains shape upon removal of the
disturbing force ex: rubber Modern
Materials

© 2015 Pearson Education, Inc.

 Polymers
• Polymers are molecules of high molecular weight
made by joining smaller molecules, called
monomers.
• There are two primary types of polymers:
 Addition polymers are formed when a bond
breaks, and the electrons in that bond make two
new bonds.
 Condensation polymers are formed when a small
molecule is removed between two large molecules.

Modern
Materials

© 2015 Pearson Education, Inc.

 Addition vs. Condensation
Polymerization

Modern
Materials

© 2015 Pearson Education, Inc.

 Some Common Polymers

Modern
Materials

© 2015 Pearson Education, Inc.

 Recycling plastics

Modern
Materials

© 2015 Pearson Education, Inc.

 Copolymers

Polymers formed from two different monomers

are called copolymers

Modern
Materials

© 2015 Pearson Education, Inc.

 Bulk Properties of Polymers
• The molecules are not straight
lines—the longer the chain, the
more twisting happens.
• Chains can have a variety of
lengths, and therefore a variety
of molecular weights.
• The material can be very
flexible (plastics).
• Mostly amorphous
• Short range order can lead
to crystallinity in the solid. Modern
Materials

© 2015 Pearson Education, Inc.

 Properties of Polymers
• Increased crystallinity results in denser,
harder, less soluble, more heat resistant
polymer

Modern
Materials

© 2015 Pearson Education, Inc.

 Changing the Polymer’s
Physical Properties
• Degree of crystallization depends on
the average molecule weigh, thus “n”

• LDPE= low density poly ethylene –used

in forming films and sheets MW in the
range of 104 amu, density< 0.94 g/cm3

• HDPE= highy density poly ethylene –

used in bottles, pipes, drums MW in theMaterials
Modern

range of 106 amu, density > 0.94 g/cm3

© 2015 Pearson Education, Inc.
 Changing the Polymer’s
Physical Properties
• Chemically bonding
chains of polymers to
each other (cross-linking)
can stiffen and strengthen
the substance.
• The greater the number of
crosslinks, the stiffer the
polymer

Modern
Materials

© 2015 Pearson Education, Inc.

 Vulcanization of Natural Rubber-
Charles Goodyear 1839
In vulcanization, chains are cross-linked by short chains
of sulfur atoms, making the rubber stronger, less
susceptible to oxidation and other chemical degradation

Modern
Materials

© 2015 Pearson Education, Inc.

 Plastic electronics –
conducting polymers

Modern
Materials

© 2015 Pearson Education, Inc.

 Nanomaterials
• Particles that have
three dimensions
on the 1–100 nm
size Nano = 10-9
• Their properties
are the study of
many labs around
the world.

Modern
Materials

© 2015 Pearson Education, Inc.

 Semiconductors on the Nanoscale
• Small molecules have discrete orbitals; macroscale
materials have bands. Where does it switch over?
• Theory tells us 1–10 nm (about 10–100 atoms).
• Quantum dots are semiconductors this size.
• As the particle gets smaller, the band gaps gets larger

Modern
Cd3P2 Materials

© 2015 Pearson Education, Inc.

 Metals on the Nanoscale
• Finely divided metals can have quite different
properties than larger samples of metals.
• Would you like “red gold” as in many old
stained glass windows?

Modern
Materials

© 2015 Pearson Education, Inc.

 Carbon on the Nanoscale

• Diamond (sp3)-
graphite(sp2)
• 1985 C60 –
buckmisterfullerene
or buckyball

Modern
Materials

© 2015 Pearson Education, Inc.

 Carbon on the Nanoscale
• Carbon nanotubes can
be made with metallic
or semiconducting
properties without
doping.
• They are very strong
materials.
• Graphene has been
discovered: single
layers with the
structure of graphite. Modern
Materials

© 2015 Pearson Education, Inc.

 Sample Integrative Exercise Putting Concepts Together

Polymers that can conduct electricity are called conducting polymers. Some polymers can be made
semiconducting; others can be nearly metallic. Polyacetylene is an example of a polymer that is a semiconductor.
It can also be doped to increase its conductivity.
Polyacetylene is made from acetylene in a reaction that looks simple but is actually tricky to do:

(a) What is the hybridization of the carbon atoms, and the

geometry around those atoms, in acetylene and in
polyacetylene?
(b) Write a balanced equation to make polyacetylene
from acetylene.
(c) Acetylene is a gas at room temperature and pressure
(298 K, 1.00 atm). How many grams of polyacetylene
can you make from a 5.00-L vessel of acetylene gas at
room temperature and room pressure? Assume acetylene
behaves ideally, and that the polymerization reaction
occurs with 100% yield.
(d) Using the average bond enthalpies in Table 8.4, predict
whether the formation of polyacetylene from acetylene
is endothermic or exothermic.
(e) A sample of polyacetylene absorbs light from 300 nm
down to 650 nm. What is its band gap, in electron volts?

Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
 Sample Integrative Exercise Putting Concepts Together
Continued

Solution
Analyze For part (a) we need to recall what we have learned about sp, sp2, and sp3 hybridization and geometry.
(Section 9.5) For part (b), we need to write a balanced equation. For part (c), we need to use the ideal-gas
equation. (Sections10.4) For part (d), we need to recall the definitions of endothermic and exothermic and
how bond enthalpies can be used to predict overall reaction enthalpies. (Section 8.8) For part (e), we need
to relate the absorption of light to the differences in energy levels between filled and empty states in a material.
(Section 6.3)
Plan For part (a), we should draw out the chemical structures of the reactant and product. For part (b), we need to
make sure the equation is properly balanced. For part (c), we need to convert from liters of gas to moles of gas,
using the ideal-gas equation (PV = nRT); then we need to convert from moles of acetylene gas to moles of
polyacetylene using the answer from part (b); finally, we can convert to grams of polyacetylene. For part (d), we
need to recall that ∆Hrxn = Σ(bond enthalpies of bonds broken) – Σ(bond enthalpies of bonds formed).
(Section 8.8) For part (e), we need to realize that the lowest energy absorbed by a material will tell us its band gap
Eg (for a semiconductor or insulator) and combine E = hν and c = λν together (E = hc/λ) to solve for Eg.

Solve
(a) Carbon always forms four bonds. Thus, each C atom must have a single bond to H and a triple bond to the other
C atom in acetylene. As a result, each C atom has two electron domains and must be sp hybridized. This sp
hybridization also means that the H—C—C angles in acetylene are 180° and the molecule is linear.

Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
 Sample Integrative Exercise Putting Concepts Together
Continued

We can write out the partial structure of polyacetylene as follows:

Each carbon is identical but now has three bonding electron domains that surround it. Therefore, the
hybridization of each carbon atom is sp2, and each carbon has local trigonal planar geometry with 120° angles.
(b) We can write:

Note that all atoms originally present in acetylene end up in the polyacetylene product.
(c) We can use the idea-gas equation as follows:
PV = nRT
(1.00 atm)(5.00 L) = n(0.08206 L-atm/K-mol)(298 K)
n = 0.204 mol

Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
 Sample Integrative Exercise Putting Concepts Together
Continued
Acetylene has a molar mass of 26.0 g/mol; therefore, the mass of 0.204 mol is
(0.204 mol)(26.0 g/mol) = 5.32 g acetylene
Note that from the answer to part (b), all the atoms in acetylene go into polyacetylene. Due to conservation of
mass, then, the mass of polyacetylene produced must also be 5.32 g, if we assume 100% yield.
(d) Let’s consider the case for n = 1. We note that the reactant side of the equation in part (b) has one C‚C triple
bond and two C―H single bonds. The product side of the equation in part (b) has one C ═ C double bond, one
C―C single bond (to link to the adjacent monomer), and two C―H single bonds. Therefore, we are breaking
one C ≡ C triple bond and are forming one C ═ C double bond and one C―C single bond. Accordingly, the
enthalpy change for polyacetylene formation is
∆Hrxn = (C ≡ C triple bond enthalpy) – (C ═ C double bond enthalpy) – (C—C single bond enthalpy)
∆Hrxn = (839 kJ/mol) – (614 kJ/mol) – (348 kJ/mol)
= –123 kJ/mol
Because ∆H is a negative number, the reaction releases heat and is exothermic.
(e) The sample of polyacetylene absorbs many wavelengths of light, but the one we care about is the longest one,
which corresponds to the lowest energy.
E = hc/λ
E = (6.626 × 10–34 J s) (3.00 × 108 m s–1)/(650 × 10–9 m)
E = 3.06 × 10–19 J

Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
 Sample Integrative Exercise Putting Concepts Together
Continued
We recognize that this energy corresponds to the energy difference between the bottom of the conduction band
and the top of the valence band, and so is equivalent to the band gap Eg. Now we have to convert the number to
electron volts. Since 1.602 × 10 –19 J = 1 eV, we find that
Eg = 1.91 eV

Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus