163Ch11 SolidStatRevsu13

Chapter
11
The Chemistry of
Solids
SOLIDS
Solids are either amorphous or crys
AMORPHOUS SOLIDS:
Considerable disorder in structu
Example: rubber,
glass
CRYSTALLINE SOLIDS:
Highly regular structure in the for
of a repeating lattice of atoms or
Crystalline solids are classified

as:
atomic, metallic, ionic, or
covalent network, depending on
the type of force holding the
2
LATTICE EXAMPLE
We
can pick out the smallest repeating unit..
3
UNIT CELL
We can pick out the smallest repeating unit..
We call this the UNIT CELL..

4
UNIT CELL
We call this the UNIT CELL..
The
unit cell drawn here is a simple cubic cell
5
Examples of Unit Cells
UNIT CELL
What is a unit cell?
The smallest unit that, when stacked
together repeatedly without any
gaps can reproduce the entire
crystal.
The three unit cells we deal with
SIMPLE CUBIC
Eight equivalent
points at the
corners of a cube
We can imagine an equivalent point at the ce

spheres
BODY CENTRED CUBIC

Eight equivalent
points at the
corners of a cube
and one at the
centre
Another possibility...
9
FACE CENTRED CUBIC

Eight equivalent
points at the corners
of a cube and six on
the centre of the
cube faces
Summary..
10
THE CUBIC UNIT

CELLS
Simple Cubic Unit
Cell
KNOW
THESE!
Body-Centred
Cubic Unit Cell !!!
How do we
investigate
Face-Centred
solids?
Cubic Unit Cell
11
Unit Cells in the Cubic

Crystal System
Prentice-Hall 2002
General Chemistry: Chapter 13
Slide 12 of 35
METAL
e.g. copper, S
gold, steel, sodium, b
Good conductors of heat and

electricity
Shiny, ductile and malleable
Melting
low (Hg at -39C)
or high (W at 3370C)
points:
Can be
soft (Na) or hard (W)
METALS ARE CRYSTALLINE SOLIDS
13
Electron Sea Model of

Metals
Copyright Houghton
Mifflin Company. All
1014
Summary of Crystal
Structures
METALS
VIEWED AS CLOSELY PACKED SPHERES

HOW CAN WE PACK SPHERES?????
16
PACKING OF SPHERICAL
VEGETABLES
17
Packing Spheres into

Lattices
The most efficient way to pack

hard spheres
is
CLOSEST
PACKING
Spheres are packed in layers in

which each sphere is surrounded
by six others.
For example.
18

Lattices:
First Layer
Lets put in a few more spheres

19

Lattices
First Layer
20

Lattices
Next Layer The
next spheres fit into
a dimple formed by three spheres in

the first layer.
21

Next Layer The
Lattices:
a dimple formed by three spheres in

the first There
layer. are two sets of dimples...
22

Lattices:
Next Layer The
NOTE:
Triangle
the
not
inverte
inverted
d
The two types of dimples formed
by
triangle
three spheres in the first layer.
The second layer..
23

Lattices:
is formed by choosing one of the sets of dimples
Now put on second layer...

24

Second Layer Lattices:
Once one is put on the others are

forced into half of the dimples of the
25 same type.

Second Layer Lattices

26 same type.

Lattices:
Second Layer

27 same type.
And so on.

Lattices Inverted triangle
Second Layer
dimples are not filled.
Note that the second layer only occupies

half the dimples in the first layer.
28

Lattices
Second Layer
Occupied
dimple
Unoccupied
DIMPLE
Note that the second layer only occupies half the dimples in the
first layer.
THE THIRD LAYER...
29
PACKING SPHERES INTO

SECOND LAYER
LATTICES
HAVE TO CHOOSE A DIMPLE

30

LATTICES
THIRD LAYER,
Choose a dimple
(1) A DIMPLE DIRECTLY ABOVE SPHERE IN THE FIRST LAYER

31
THIS OR..

LATTICES
THIRD LAYER
NOTE:
the
inverte
d
triangle
(2) A DIMPLE DIRECTLY ABOVE A DIMPLE

CHOOSE OPTION 1..
IN 32THE FIRST LAYER..

THIRD
LAYER (option 1)
LATTICES
OPTION ONE!
SPHERE DIRECTLY ABOVE SPHERE IN THE

FIRST
ADD LAYER
SOME MORE..
33

THIRD LAYER
LATTICES OPTION ONE!
ADD SOME MORE..

34

THIRD LAYER
OPTION
ONE!
LATTICES
THE ABA ARRANGEMENT OF LAYERS.
LAYERS ONE AND THREE ARE THE

35

THE ABA ARRANGEMENT
OF LAYE
LATTICES
A
CALLEDHEXAGONAL CLOSEST PACKIN HCP

36

THE ABA ARRANGEMENT
LATTICES OF LAYERS
A HEXAGONAL UNIT CELL.
HEXAGONAL CLOSEST PACKING

37
HEXAGONAL UNIT CEL

ABA ARRANGEMENT HAS A
HEXAGONAL UNIT CELL.
HCP
38
SUMMARY...
SUMMARY
HEXAGONAL CLOSED PACKED STRU
EXPANDED VIEW
NOW OPTION TWO..
39

THIRD LAYER
LATTICES
OPTION 2!
THIS DIMPLE DOES NOT

LIE DIRECTLY OVER THE SPHERES OF THE FIRST LAYER.
MORE
40

THIRD LAYER
LATTICES
GREEN SPHERES
DO NOT LIE DIRECTLY
OVER THE SPHERES OF THE FIRST LAYER.
OPTION 2
THE THIRD LAYER IS DIFFERENT FROM

THE
FIRST.
41

NOT THE SAME
AS OPTION ONE!
LATTICES
THIRD LAYER
OPTION 2
A
WE CALL THE THIRD LAYER C THIS TIME!

42

THIRD LAYER LATTICES
WE CALL THE THIRD LAYER C THIS TIME!
OPTION 2
A
THE ABC ARRANGEMENT OF LAYERS.

43
NOW THE FOURTH LAYER.

FOURTH LAYER
LATTICES
T SPHERE IN SO THAT
A
FOURTH LAYER THE SAME AS FIRST.

44

PHH p 509
LATTICES
FOURTH LAYER
THE SAME AS FIRST.
A
C
A
THE ABCA ARRANGEMENT..
THIS IS CALLED.
45

THE ABCA ARRANGEMENT..
LATTICES
A
C
A
CUBIC CLOSED PACKED.

46
WHY???
UNIT CELL OF CCP
CUBIC UNIT CELLL
THIS ABCA ARRANGEMENT HAS A
FACE- CENTRED CUBIC UNIT CELL (FCC)

A COMPARISON..
47
COMPARISON
HCP
NOTICE the flip...
CCP
NEAREST NEIGHBORS..
48
COORDINATION NUMBER
The number of nearest
neighbors that a lattice point
has in a crystalline solid
Lets look at hcp and ccp...
49
COORDINATION NUMBER
HCP
50
COORDINATION NUMBER
HCP
COORDINATION NUMBER =12

51
COORDINATION NUMBER
HCP
CCP

52
COORDINATION
NUMBER
HCP
CCP

53
COORDINATION
NUMBER
SPHERES IN BOTH HCP AND CCP

STRUCTURES
EACH HAVE A COORDINATION NUMB
QUESTION..
54
REVIEW QUESTION
Which is the closest packed arrange

1
Stacking a second
Top Row
closepacked layer of
Bottom Row
spheres directly
atop a
close-packed
below
2
Stacking alayer
second
closepacked layer of spheres in
the
depressions
formed by spheres in
the
close-packed layer below.
ANSWER..
55
Top Row
Bottom Row
REVIEW QUESTION
Which is the closest packed arrangem

1
Stacking a second
closepacked layer of
spheres directly
atop a
close-packed
below
2
Stacking alayer
second
closepacked layer of spheres in
the
depressions
formed by spheres in
the
close-packed
NEAREST NEIGHBOURSlayer
IN OTHERbelow.
UNIT CELLS..
56
Alloys
An alloy is a blend of a host metal and one or
more other elements which are added to
change the properties of the host metal.
Ores are naturally occurring compounds or
mixtures of compounds from which elements
can be extracted.
Bronze, first used about 5500 years ago, is an
example of a substitutional alloy, where tin
atoms replace some of the copper atoms in
the cubic array.
Substitutional Alloy
Examples
Where a lattice atom is replaced by an
atom of similar size
Brass, one third of copper atoms are
replaced by zinc atoms
Sterling silver (93% Silver and 7%Cu)
Pewter (85% Sn, 7% Cu, 6% Bi, and 2%
Sb)
Plumbers solder (67% Pb and 33% Sn)
Bronze
Alloys
Interstitial Alloy
When lattice holes (interstices) are filled with

smaller atoms
Steel best know interstitial alloy, contains
carbon atoms in the holes of an iron crystal
Carbon atoms change properties
Carbon a very good covalent bonding
atom changes the non-directional
bonding of the iron, to have some
direction
Results in increased strength, harder, and
less ductile
The larger the percent of carbon the
harder and stronger the steel
Other metals can be used in addition to
carbon, thus forming alloy steels
Carbon Steel
Unlike bronze the carbon atoms fit into the holes
formed by the stacking of the iron atoms. Alloys
formed by using the holes are called interstital
alloys.
Two Types
of Alloys
Substitutiona
l
Interstitia
l
1062
About Holes in Cubic

Arrays
Atomic Size Ratios and the Location of
Atoms in Unit Cells
Packing
Type of Hole
Radius Ratio
pm
hcp or ccp
Tetrahedral
0.22 - 0.41
hcp or ccp
Octahedral
0.41 - 0.73
Simple Cubic
Cubic
0.73 - 1.00
COORDINATION NUMBE
SIMPLE CUBIC
How do we count nearest neighbors?

Draw a few more unit cells...
64
COORDINATION NUMBE
SIMPLE CUBIC
Highlight the nearest neighbors.

65
COORDINATION NUMBE
How many nearest neighb

SIMPLE CUBIC
coordination number of 6
66
What about body centered cubic
COORDINATION NUMBER
In the three types of
cubic unit cells:
Simple cubic
CN = 6
Body Centered cubic
CN = ?
Lets look at this.

67
Body-centered cubic
packing (bcc)
COORDINATION NUMBER?????
In bcc lattices, each sphere has a

coordination number of 8
What about face centered cubic?

68
COORDINATION NUMBER
In the three types of cubic unit
cells:
Simple cubic
CN = 6
Body Centered cubic

CN = 8
Face Centered cubic
CN = ?
Comes from ccp
Just like hcp CN = 12
PACKING EFFICIENCY?
69
EFFICIENCY OF PACKIN
THE FRACTION OF THE VOLUME THAT
IS ACTUALLY OCCUPIED BY
SPHERES..
volume occupied by the spheres in the unit cell
fv
volume of the unit cell
WHAT DOES THIS MEAN???
70
PACKING EFFICIENCY
FRACTION(F) OF THE VOLUME OCCUPIED BY THE
SPHERES IN THE UNIT CELL.
volume occupied by the spheres in the unit cell

fv
fv
Vspheres
V
unitcell
Vspheres= number of spheres x volume sin
Vunit cell = a3 cubic unit cell of edge lengt

Lets get NUMBER OF SPHERES
71
PACKING EFFICIENCY
COUNTING ATOMS IN A UNIT CELL!
ATOMS CAN BE WHOLLY IN A UNIT CELL OR
COUNTING ATOMS IN A UNIT CELL!
ATOMS CAN BE WHOLLY IN A UNIT
CELL OR ATOMS SHARED
BETWEEN ADJACENT UNIT CELLS
COUNTS 1 FOR ATOM IN CELL
IN THE LATTICE
COUNTS FOR 1/4 ATOM ON A FACE.
COUNTS FOR 1/2 ATOM ON A FA

COUNTS AS 1/8 FOR ATOM ON A CORNER.
72
FACE-CENTRED CUBIC
UNIT
CELL
What is the number of spheres in the fcc
unit cell?
Note: 1/8 of a sphere on 8 corners and of a
Sphere on 6 faces of the cube
8 (1/8)
Total spheres
= + 6 (1/2)
=1+3=4
QUESTION..
73
QUESTION
THE NUMBER OF SPHERES IN A BODY
CENTRED CUBIC CELL IS?
ANSWER.
74
QUESTION
THE NUMBER OF SPHERES IN A BODY
CENTRED CUBIC CELL IS?
ANSWER.
Atoms = 8(1/8) + 1 = 2
VOLUME OCCUPIED IN FCC.
75
CUBIC UNIT CELLS
WHAT FRACTION OF SPACE IS OCCUPIED INFA

CENTRED CUBIC CELL?
NUMBER OF SPHERES IS 4
NOW WE NEED THE VOLUME OF
A SPHERE, USING r FOR RADIUS
Vtotal
76
4 3
4=
( r )
3
THERE ARE 4 SPHERES IN THE

UNIT CELL
FACE-CENTRED CUBIC UNIT CELL
4 3
Vspheres
4( r )
3
radius of the sphere is
r.
Now we need the volume of the unit cell.
Why????
?
fv
V
spheres
V
unitcell
GET DIMENSIONS OF CUBE IN TERMS OF r..

77
GETTING THE CUBE DIMENSIONS IN TE

Let side of cube be a
a
NOW DRAW A FACE OF THE CUBE

REMEMBER THE SPHERES TOUCH!!
78
DRAWING CUBE FACE
REMEMBER THE SPHERES TOUCH

Draw a square..
Now we need to get a in ter
79
CONSTRUCT A
TRIANGLE ON THE
FACE
Why????
So we can use Pythagora
80
GET a in terms of r
r
2r
r
81
GET a in terms of r
FACE DIAGONAL = r + 2r + r=
PYTHAGORAS!
a2 + a2 =
(4r)2
2r2
82
2a2 = 16r
ar 8
a2 = 8r 2
Side of cube be in terms o
ar 8
Now we can calculate the

Vcell a 3
Vcell r 8
2r
83
NOW PUT IT ALL TOGETHER
FACE-CENTRED CUBIC UNIT CELL
fv
fv
Vspheres
V
unitcell
4
4 * 3 r 3
r 83
fv 0.740
84
fv
4
4* 3
83
We conclude..
FACE-CENTRED CUBIC UNI
fv
Vspheres
V
unitcell
fv 0.740
In a cubic closest packed crystal
74% of the volume of a is taken up by sphe

and 26% is taken up by empty
space.
QUESTION
85
Body Centered Cubic
2r
r
e
d
e
d2 = e2 + e2
d2 = 2e2
(4r)2 = e2 +
d2
16r2 = e2 +
2e2
r2 =
3e2/16
e =
4r/3
CUBIC UNIT CELLS

THE EDGE LENGTH IN TERMS OF r
SIMPLE
CUBIC
2r
NUMBER OF SPHERES
1
87
BODY CENTRED CUBIC
4r
3
2
FACE CENTRED CUBIC
r 8
4
VOLUME OCCUPIED
CUBIC UNIT CELLS

VOLUME OCCUPIED
SIMPLE
CUBIC
BODY CENTRED CUBIC
FACE CENTRED CUBIC
52.4%
74.0%
68.0%
2r
NUMBER OF SPHERES
1
88
4r
3
2
r 8
QUESTION...
4
QUESTION
The fraction of space occupied in a
hexagonal closest packed arrangement of
spheres is the same as that in..
1
simple cubic unit cell
face centered cubic unit cell
body centered cubic unit cell
none of these
ANSWER..
89
QUESTION
The fraction of space occupied in a
hexagonal closest packed arrangement of
spheres is the same as that in..
1
simple cubic unit cell
2
3
face centered cubic unit cell

body centered cubic unit cell
none of these
Summary...
90
SUMMARY
sc: 52.4%
bcc: 68.0%
fcc: 74.0%
hcp: 74.0%
of
of
of
of
space
space
space
space
occupied
occupied
occupied
occupied
by
by
by
by
spheres
spheres
spheres
spheres
Make sure you can do the fcc, bcc and sc

lattice calculations!
What other property of a substance
depends on packing efficiency????????
91
DENSITY
We can calculate the density in a uni

mass
Density
volume
Mass is the mass of the number of

atoms in the unit cell.
Mass of one atom =atomic mass/6.022
N0 = 6.022 x 1023 atoms per mo

Avogadros Number!
92
Volume of a copper unit

Cu crystalizes as a fcc
r= 128pm = 1.28x10-10m = 1.28x10-8cm
Volume of unit cell is given by:
Vcell r 8
Vcell
Vcell
93
3
8
8 1.28 10 cm )
4.75 10
23
cm
COPPER DENSITY
CALCULATION
mole Cu
63.54 g Cu
4 atoms unit cell

Cu
unit cell 4.75X10-23
atoms
mole 6.022 X 1023

3
cm
Cu
= 8.89
g/cm3
Laboratory measured density:
8.92 g/cm3
DETERMINATION OF ATOMIC
RADIUS
At room temperature iron crystallizes with a
bcc unit cell.
X-ray diffraction shows that the length of an
edge is 287 pm.
What is the radius of the Fe atom?
EDGE LENGTH (e)e 4r
3e
r
4
3 287 pm
r
124 pm
4
95
AVOGADROS NUMBER
Sample Problem: Calculate Avogadros

number of iron if its unit cell length is 287 pm
and it has a density of 7.86 g/cm3.
55.85 g
Mole
Fe
Fe(s) is bcc Two atoms / unit cell
96
AVOGADROS NUMBER
Sample Problem: Calculate Avogadros
number of iron if its unit cell length is 287
pm and it has a density of 7.86 g/cm 3.
55.85 gcm3
Mole 7.86 g
Fe
97
AVOGADROS NUMBER
The density of Fe(s) is 7.86 g/cm3.
length of an edge is 287 pm.
V= e3 = (287pm)3 = 2.36x10-23cm3
pm3
55.85 gcm
Mole 7.86 g(10 -12)3 cm3
Fe
3
98
AVOGADROS NUMBER
The density of Fe(s) is 7.86 g/cm3.
length of an edge is 287 pm.
V= e3 = (287pm)3 = 2.36x10-23cm3
pm3
unit cell
55.85 gcm
Mole 7.86 g(10 -12)3 cm3(287 pm)3
Fe
3
99
AVOGADROS NUMBER
pm3
unit cell 2 atoms

55.85 gcm
Mole 7.86 g(10 -12)3 cm3(287 pm)3 unit cell
Fe
3
100
AVOGADROS NUMBER
pm3
unit cell 2 atoms

55.85 gcm
Mole 7.86 g(10 -12)3 cm3(287 pm)3 unit cell
Fe
3
= 6.022 X 10-23 atoms/mole
101
IONIC SOLIDS
Binary Ionic Solids: Two
types
of ions
Examples:
NaCl MgOCaCO MgSO
3
Hard, brittle solids
High melting point

Electrical
insulators
except when molten or dissolved in water.
These are lattices of ions.
102
IONIC SOLIDS
= Na+
= Cl
We notice that this is a cubic array of ions.

Why do ionic solids hold together?????
103
Sodium Chloride
Prentice-Hall 2002
General Chemistry: Chapter 13
Slide 104 of 35
IONIC SOLIDS
The stability of the ionic compound
results from the electrostatic
attractions
Li+
F
Li+
F
between
the ions:
The LiF crystal
consists
of a lattice of ions.
Li+
The attractions are

+
+
Li
F
Li
stronger than the
repulsions, so the
F
Li+
F
crystal is stable.
The stability is due to the LATTICE
ENERGY
How can we describe ionic lattices?
105
Li+
F
Li+
NaCl structure
ClNa+
Lets take this apart...
106
NaCl structure
ClNa+
Lets look at the black dot lattice.

107
NaCl structure
What unit cell do the black dots form?
The black dots form a fcc lattice!

Now look at the red dots
108
NaCl structure
What unit cell is this????
Cubic certainly But which one?????

Lets have another look.
109
NaCl structure
What unit cell is this????
Bring in a another array..
The red dots form a fcc array!

Now put these back together..
110
NaCl structure
FCC OF BLACK DOTS
Bring in red dots
NOTICE THE RED DOTS FIT NICELY IN
BETWEEN BLACK DOTS
THE RED DOTS SIT IN THE HOLES OF THE

BLACK DOT FCC ARRAY
111
NaCl structure
This is the NaCl structure.
ClNa+
Two interpenetrating fcc arrays, one of Na + ions

and one of Cl- ions.
The Na+ sit in the holes of the black (Cl-) lattic

SO HOW WE DESCRIBE IONIC SOLIDS???
112
IONIC SOLIDS
consist of two interpenetrating lattices
of
the
two
ions (cations and anions) in the solid.
We describe an ionic solid as a lattice of
the larger ions with the smaller ions
occupying holes in the lattice.
NOTE:
The anion is usually larger than the
cation.
HOLES????
113
HOLES IN A LATTICE.
Holes???
What holes?????
Lets look at a fcc lattice!
114
HOLES IN A FCC LATTIC
The black dots form a FCC lattice!

See the holes????
115
HOLES IN A FCC LATTICE
The black dots form a fcc lattice!

See the holes????
HOW MANY HOLES??????
116
HOLES IN A FCC LATTICE

The holes:
How many??
THIRTEEN:
ONE IN THE CENTRE
12 on the edges.
What shape is the hole ?
117
CENTRAL HOLE
OCTAHEDRAL HOLES:
There is one octahedral hole in the
centre of the unit cell.
If each one is occupied by an a

118
THE OCTAHEDRAL HOLE

1 atom
1/4 atom
If each one is occupied by an atom?

How many atoms per unit cell?
Number of atoms = 1 + 12 x (1/4) = 4
There are 4 complete octahedral holes per f

119
THE 13 OCTAHEDRAL HO
1 atom
1/4 atom
There are 4 complete octahedral holes per f

Notice that the number of octahedral holes is
the same as the number of atoms forming the
unit
cell!! + 6x(1/2) = 4) remember????
( 8x(1/8)
120
The octahedral hole is..
THE OCTAHEDRAL HOLE
Between two layers..

Other holes..
121
OTHER HOLES
There are other holes!

Can you spot them??????
Where are the other holes in the FCC unit ce

Look at one of the small cubes
122
SMALL CUBE
Take a point at the centre of this cube

There are eight of these.
123
SMALL CUBE
8 CUBES

Another one of these.
124
SMALL CUBE
8 CUBES

An so on .
125
SMALL CUBE
8 CUBES
This is a TETRAHEDRAL HOLE.

126
TETRAHEDRAL HOLES
Notice that
there are
twice as
many
tetrahedral
holes as
atoms
There is one tetrahedral hole in each of
forming the
the eight smaller cubes in thelattice!
unit cell.
That
wouldthe
be 8
All the holes are completely within
holes.
cell, so there are 8 tetrahedral
holes per
fcc unit cell
This hole.
127
TETRAHEDRAL HOLES
Formed by three spheres in one

layer and
one sphere in another layer sitting in the
dimple they form.
There is one more hole.
128
TRIGONAL HOLES
The smallest h
Formed by three spheres in one layer.

Formed from the space between three
ions in a plane.
Which hole????
129
HOLE OCCUPANTS?
Which holes are used by the cation??

Which of the holes is used depends upon
the size of the cation and..
The size of the hole in the anion lattice..
Why??????
130
HOLE OCCUPANTS?
Which hole will a cation occupy??????
They occupy the holes that result in
maximum attraction and minimum
repulsion.
To do this...
131
Which hole will a cation occupy?????

M+ or M2+ cations always occupy the
holes
with the largest coordination number
without rattling
around!
TIGHT
FIT
Consequently the radius of the cation
must be
greater than the size of the hole!
This causes the X anions to be pushed
apart,
which reduces the X X repulsion.
So we will investigate the size of these hole

132
Which hole will a cation occupy?????
Investigate the size of these hole
The size of the hole depends upon

size of the ion (usually anion) that
forms the lattice into which the
cations are to go...
OCTAHEDRAL HOLE IN FCC.
LOOK AT HOLE.
133
OCTAHEDRAL HOLES IN FCC

Look at plane
Draw a square.
Put in spheres.
These are the anions
Fit a small sphere in
134

Look at plane
Draw a square.
Put in spheres.
These are the anions
Fit a small sphere in
This will be the cation

Draw diagonal
135
Put in distances..

Look at plane
Radius of ion =
R
Radius
of hole = r
2r
136

Look at plane
Radius of ion = R
Radius of hole = r
= (2R + 2r)2
(2R)2+(2R)2
8R2 = (2R + 2r)2
2r
R
R
2 2R 2 R 2r
( 2 2 2) R 2r
2 1 R r
0.414R = r
137

Look at plane
Radius of ion = R
Radius of hole = r
R
2r
R
0.414R = r
The size of cation
that just fits has a
radius that is
0.414 x radius of anion(
roctahedral hole = 0.414 R
What about the tetrahedral ho

138
Using similar calculations, we can find

the radius of other types of holes as
well:
fcc
rtetrahedral = 0.225 R
roctahedral = 0.414
R
r = radius of ion fitting into hole (usually
cation)
Rthe
is the
radius of the ion forming the lattice (usually
DO IT!!!!!!!
RADIUS RATIO:
The ratio between the radius of a hole in a

cubic lattice
and the radius of the ions forming the hole
What about other cubic cell syst

139
SIMPLE CUBIC
If the M+ cations (e.g. Cs+) are
sufficiently
large, fit into octahedral
they
can no longer
holes
of abest
fcc lattice.
The next
closest packed X array
adopted by the anions is a simple cubic
structure, giving cubic holes which are
large enough to hold the cations.
YOU can show that...
rcubic = 0.732 Ranion
DO IT!!!!!!!
140
The cubic hole
The coordination number in the cubic

8 hole
rcubic = 0.732 Ra
In contrast for a fcc lattice...

The coordination
number in the fcc
tetrahedral
hole is ?
4
!
141
The coordination
number in the fcc
octahedral
6! hole is ?
SUMMARY:
Face centred cubic:
Trigonal hole
Too small to be occupied
Tetrahedral hole
CN = 4
rcation = 0.225Ranion
8 of these
Octahedral hole
CN = 6
rcation = 0.414Ranion
4 of these
Simple cubic:
Cubic hole CN = 8rcation = 0.732Ranion
For a given anion
rtrigonal < rtetrahedral < roctahedral < rcubic
142
1 of these
SUMMARY
Face centred cubic:
Trigonal hole
Too small to be occupied
Tetrahedral hole CN = 4 rcation = 0.225Ranion 8 of these

Octahedral hole CN = 6 rcation = 0.414Ranion 4 of these
Simple cubic
CN = 8 rcation = 0.732Ranion 1 of these
For a given anion
rtrigonal < rtetrahedral < roctahedral < rcubic

Which hole will a cation occupy??????
143
INTO WHICH HOLE WILL THE ION

GO??
TETRAHEDRAL
The hole filled is tetrahedral if:

rtetrahedral < rcation < roctahedral
0.225Ranion < rcation < 0.414Ranion
144

GO??
OCTAHEDRAL
The hole filled is octahedral if:
roctahedral < rcation < rcubic
0.414Ranion < rcation < 0.732Ranion
145

GO??
CUBIC
The hole filled is cubic if:
rcubic < rcation

0.732Ranion < rcation
Lets look at these ideas in action.
146
NaCl
Na+ has a radius of 98p

Cl- has a radius of 181p
Consider a fcc array of Cl- then:
Radius of the tetrahedral hole is 0.225 x 181
Radius of the octahedral hole is 0.414 x 181=

Consider a sc array of Cl- then:
Radius of the cubic hole is 0.732 x 181=132p
So the best fit is the octahedral hole in the fc

The 98pm is bigger than 75pm but less than
OR USING RATIOS.
147
NaCl
Na+ has a radius of 98p

Cl- has a radius of 181p
rcation rNa 98 pm
0.54
ranion rCl 181 pm
rcation
0.225
tet
ranion
tet
rcation
0.414
oct
ranion
oct
rcation
0.732
cubic
ranion
cubic
0.54 lies between 0.414 and

0.732
so the sodium cations will occupy octahedra
in a fcc (ccp) lattice
Is the stoichiometry ok???
148
NaCl
1:1 stoichiometry is
required
How many complete octahedral holes in
face centred cubic
array
of
Cl
?????
4
How many Cl- needed to form the fcc

4 array???
Therefore 4 Cl- and 4 Na+
So stoichiometry is ok!!
Lets do another example..
149
Example: Predict the structure of Li2S

Li+ is 68 pmS2- is 190pm
STEP ONE:
Examine the cation-anion radius ratios
to find which type of holes the smaller
ions fill
rcation rLi
68 pm
Calculate ratio..
0.36
ranion
rS 2
190 pm
COMPARE with ratios.
rcation
0.225
tet
ranion
tet
rcation
0.414
oct
ranion
oct
Which is the best hole????

TETRAHEDRAL!!!!
150
Example: Predict the structure of Li2S

Li+ is 68 pm S2- is 190pmCalculate ratio..
rcation rLi
68 pm
0.36
ranion rS 2 190 pm
This requires
tetrahedral
holes.
Which
lattice has
tetrahedral holes???
face- centred cubic
array
Thus the S2- will form a fcc lattice ...
Lets look at the structure...
151
FCC unit cell with

tetrahedral holes
ANION
CATION
How many are occupied?
Four anions
in the unit
cell.
There are 8
tetrahedral
holes.
STEP TWO: Determine what fraction of

those holes must be filled to give the So???
152
correct
chemical formula
FCC unit cell with

tetrahedral holes
S2-
Li+
How many are occupied?
Four
anions in
the are
unit8
There
cell.
tetrahedral
holes.
Next Step.
Li2S needs two Li+ for each S2-
Therefore all the tetrahedral holes are occupi

153
FCC unit cell with tetrahedral

holes filled
= S2
= Li+
all the
tetrahedral
holes have to
be occupied.
STEP THREE: Describe the solid as an array
of the larger ions with the smaller ions
occupying the appropriate holes.
154
Which is..
FCC unit cell with tetrahedral

holes filled
= S2
= Li+
all the
tetrahedral
holes have to
be occupied.
Li2S is a face centered lattice of S2- with all
of the tetrahedral holes filled by Li+ ions.
155
Now do CsCl.
+
Cs
is
167
pmCl
is 181pm
Calculate rati
CsCl
rcation rCs 167 pm
0.92
ranion rCl 181 pm
rcation
0.732
cubic
ranion
cubic
Compare...
0.92 is greater than 0.732

the cesium cations will occupy cubic
holes of a simple cubic lattice.
STOICHIOMETRY?????
156
There are the same number of cubic holes

and lattice points in the cubic lattice.
Hence stoichiometry OK!
CsCl is composed of a simple cubic lattice

of chloride anions with cesium cations in
all157the cubic holes.
Cesium Chloride
ZnS:
Calculate
rati
Zn2+ is 64 pm S2- is 190
pm
rcation rZn2
64 pm
0.35
ranion rS 2 190 pm
rcation
COMPARE tet 0.225
ranion
tet
This requires
tetrahedral
holes.
rcation
0.414
oct
ranion
oct
The sulfide ions will form a facecentered cubic array because.

that is the only type to possess tetrahedral
What about stoichiometry??????
159
ZnS:
Calculate
rati
Zn2+ is 64 pm S2- is 190
pm
rcation rZn2
64 pm
0.35
ranion rS 2 190 pm
rcation
COMPARE tet 0.225
ranion
tet
This requires
tetrahedral
holes.
rcation
0.414
oct
ranion
oct
The sulfide ions will form a facecentered cubic array because.

that is the only type to possess tetrahedral
What about stoichiometry??????
160
We need an equal number of zinc and sulfide ions.

There are the twice as many tetrahedral
holes(8) as S2-(4) that form the fcc lattice.
Therefore, half the tetrahedral holes will be filled

161
We need an equal number of zinc and sulfide ions.

Half the tetrahedral holes will be filled.
ZnS is composed of a fcc lattice of sulfide anions

with zinc cations in half the tetrahedral holes.
162
There are two forms of ZnS
One is the zinc blende that we have talked ab
This is an
example of
polymorphism.
The other is wurtzite based on hcp lattice.

163
QUESTION
A crystal has Mg2+ ions at the corners of a cubic unit cell, F- ions at
the midpoints of all the edges and K+ ions at the body centre. The
empirical formula is
1
KMgF3
K3MgF2
KMg2F2
K2Mg2F
K2Mg2F3
164
ANSWER
A crystal has Mg2+ ions at the corners of a cubic

unit cell, F- ions at the midpoints of all the edges
and K+ ions at the body centre. The empirical
formula
is
1
KMgF
3
K3MgF2
KMg2F2
K2Mg2F
K2Mg2F3
165
QUESTION
A COMPOUND CONTAINS THE ELEMENTS Na,O and Cl. IT CRYSTALLISES IN
A CUBIC LATTICE. THE O ATOMS ARE AT THE CORNERS, THE Cl ATOMS
ARE AT THE CENTER AND THE Na ARE AT THE CENTRES OF THE FACES OF
THE UNIT CELL. THE FORMULA OF THE COMPOUND IS...
1
Na2ClO
Na3ClO
NaCl3O
NaClO3
NaClO
166
QUESTION
A COMPOUNDCONTAINS THE ELEMENTS Na,O and Cl. IT CRYSTALLISES IN
A CUBIC LATTICE. THEO ATOMS ARE AT THE CORNERS, THE Cl ATOMS
ARE AT THE CENTER AND THE Na ARE AT THE CENTRES OF THE FACES OF
THE UNIT CELL. THE FORMULA OF THE COMPOUND IS...
1
Na2ClO
Na3ClO
NaCl3O
NaClO3
NaClO
167
This is the flourite structure:

MX2anions occupy the tetrahedral holes(8)
the
= Ca2+
in a fcc
array of
the
cations(4).
= F-
Does this fit radius ratios???????

168
CaF2:
Calculate ratio
Ca2+ is 99 pm F- is 136 pm
rcation rCa 2
99 pm
0.727
ranion rF 136 pm
FOR TETRAHEDRAL HOLES
rcation
0.225
tet
ranion
tet
OOPS!!!!
The radius ratio is too BIG!!!!
This shows Radius Ratios do not always work

properly
But CaF2 can be thought of as a simple cubic of Fwith Ca2+ at alternate cubic holes!!!!!!!
169
CaF2:
SIMPLE CUBIC
Ca2+
Ca2+
Ca2+ in alternating cubic sites.

Alternative description
What is Antiflourite????
170
This is the flourite structure: MX2

the anions occupy the tetrahedral holes(8)
= Ca2+
= F-
in a fcc
array of
the
cations(4).
The antifluorite structure M2X (eg
Kthe
2O) cations occupy the tetrahedral holes
and the anions form the fcc array.
171
Ionic Compound Density

MgO fcc of O2- Mg2+ in octahedral holes
Calculating the density of an ionic
compound
A face.
Edge= roxide ion+ 2rMg ion+ roxide

Now calculate volume
4 Mgs and 4 O2172
REMEMBER.

compound
R = 86 pm
A face.
r = 126 pm
Edge = 424 pm
V = (424)3 =
7.62X107 pm3

4 Mgs and 4 O2173
REMEMBER.

compound
R = 86 pm
A face.
r = 126 pm
Edge = 424 pm
V = (424)3 =
7.62X107 pm3

4 Mgs and 4 O2174
REMEMBER.
DENSITY OF IONIC
CRYSTALS
For example calculate the density of MgO a fcc crystal with
762 pm for the length of its unit cell.
40.61g MgO
mole
DENSITY OF IONIC
CRYSTALS
40.61g MgO mole

mole
6.022 X 1023 FU
DENSITY OF IONIC
CRYSTALS
40.61g MgO mole

4 FU
mole
6.022 X 1023 FU unit cell
DENSITY OF IONIC
CRYSTALS
40.61g MgO mole

Unit Cell
4 FU
mole
6.022 X 1023 FU unit cell 7.62X107 pm3
DENSITY OF IONIC
CRYSTALS
40.61g MgO mole

Unit Cell
pm3
4 FU
mole
6.022 X 1023 FU unit cell 7.62X107 pm3 10-36m3
DENSITY OF IONIC
CRYSTALS
40.61g MgO mole

Unit Cell
pm3 10-6m
4 FU
mole
6.022 X 1023 FU unit cell 7.62X107 pm3 10-36m3 cm3
DENSITY OF IONIC
CRYSTALS
40.61g MgO mole

Unit Cell
pm3 10-6m
4 FU
mole
6.022 X 1023 FU unit cell 7.62X107 pm3 10-36m3 cm3
= 3.54 g/cm3
Diamond and Graphite

Covalently Networked Crystalline Solids
Copyright Houghton
10182
Diamond and Graphite

The p Orbitals (a) Perpendicular to the
Plane of the Carbon Ring System in
Graphite can Combine to Form (b) an
Extensive pi Bonding Network
10183
SCATTERING OF X-RAYS BY
CRYSTALS
In 19th century crystals were
identified by their shape..
Crystallographers did not know atomic
positions within the crystal.
In 1895 Roentgen discovered X-rays...
And Max von Laue suggested that...
crystal might act as a diffraction
grating for the X- rays.
184
X-Ray Diffraction
SCATTERING OF X-RAYS BY
CRYSTALS
In 1912 Knipping
observed..
X-RAY DIFFRACTION
PATTERN
Von Laue gets Noble
Prize.
How can we
understand this???
186
X-ray Diffraction
X-ray diffraction (ERD) is a technique for
determining the arrangement of atoms or
ions in a crystal by analyzing the pattern
that results when X-rays are scattered
after bombarding the crystal.
The Bragg equation relates the angle of
diffraction (2) of X-rays to the spacing (d)
between the layers of ions or atoms in a
crystal: n2dsin.
Cell Structure by X-ray

Diffraction
BRAGG DIFFRACTION
LAW
W.H. Bragg and W.L.Bragg noticed that
This is reminiscent of reflection..

So they formulated diffraction in
terms of reflection from planes of
electron density in the crystal..
189
BRAGGS LAW
BRAGG DIFFRACTION
LAW
A plane of lattice points.
Now imagine reflection of X-rays

191
Bragg Equation Derivation
sin = x/d
Wave length = 2x
x
x = d sin
= 2d sin
n = 2d sin
n due to multiple layers of particles
BRAGGS LAW
Only at certain angles of will the waves from different

planes be in phase, thus n = 2dsin
By adjusting the angle of the x-rays until constructive
interference is obtained, distance (d) between atoms is
obtained
BRAGG DIFFRACTION
LAW
The Braggs also demonstrated diffraction

And formulated a diffraction law...
When electromagnetic radiation passes
through matter.
It interacts with the electrons and
Is scattered in all directions
the waves interfere..
194
The Band Theory (MO

theory)
Review the Li MO diagram
Many vacant MOs
In fact only sigma is filled

This is for two atoms
Now how about four atoms more MOs
How about a mole of atoms, tons of MOs
For magnesium, which is HCC, look at the
bands
The lower band holds electrons, but the next
highest vacant MO is just a small energy jump
away
Electrons do not flow in the lower band since
they bump into each other
But a slight amount of energy promotes them
to the conduction band where they flow freely
Molecular
Orbital
Energy Levels
10196
Molecular
Orbital
Energy Levels
10197
Magnesium Band Model

Looking at the band diagram for Mg
The 1S, 2s, 2P electrons are in the
well(localized electrons)
The valance electrons occupy closely
spaced orbitals that are partially filled
Why then do nonmetals not conduct

There is a large energy difference between
conduction and non conduction band
There are more valence electrons
A Representation of the Energy

Levels (Bands) in a Magnesium
Crystal
Copyright Houghton
10199
Molecular Orbital Energies
Insulator (diamond) Conductor(m

etal)
10200
Semi Conductors
For metalloids the distance between the
conducting band and the nonconduction
band are lower, in between that for metals
and nonmentals, thus called
semiconductors.
For example silicon is a semiconductor,
with the same structure as diamond, since
it is in the same group.
Diamond has a large gap in its band model,
but silicon, being a semi conductor, has a
smaller gap, thus promoting conduction.
Semi Conductors
At higher temperatures more electrons are
promoted into the conduction band and
conductivity increases for semiconductors.
adding impurities, such as phosphorus or
gallium in metalloids (usually silicon)
changes the conduction characteristics of
the metalloid (silicon).
When a small fraction of silicon atoms are
replaced with phosphous atoms, each with
one more electron than silicon, then extra
electrons are available for conduction
(Called an n-type semi conductor)
Semi Conductors
N-type semi conductors, using a phosphorus impurity,
provide more electrons than the original semi
conductor, usually Silicon.
These electrons lie closer to the conduction band
and less energy is required for conduction
This is called an n-type due to extra negative charge
Conductivity can be enhanced by an element such as
boron that has one less valence electron than silicon
These are called P-semiconductors
Since we are missing an electron then there is a
hole, which an electron fills thus creating another
hole
Holes flow in a direction opposite to the flow of
electrons, since lower lying electrons are promoted
to fill the hole
Called p for positive charge, due to one less electron
Energy-Level Diagrams for (a) an NType Semiconductor and (b) a P-Type

Semiconductor
As is example
Copyright Houghton
B is an example
10204
Semi Conductors
Important application is to combine an n-type and a ptype together, called a p-n junction
When they are connected some of the electrons from the ntype flow into the open holes of the p-type, thus creating a
charge difference
Once the charge difference is achieved then electron flow
ceases, this is called contact potential, or junction
potential
If an external voltage is applied then electrons will only flow
in one way
From the n-type to the p-type
The holes flow in the opposite direction
P-n-junctions makes an excellent rectifier, a device that

produces a pulsating direct current from an alternating
current
The overall effect is to convert alternating current into
direct current
Old rectifiers were vacuum tubes, which were not very
reliable
Semi Conductors
Some electrons flow to create opposite charges
No current flows, called reverse bias
Current flows, called forward bias
The End

163Ch11 SolidStatRevsu13

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Chapter

Solids are either amorphous or crys

Crystalline solids are classified

We call this the UNIT CELL..

We call this the UNIT CELL..

Examples of Unit Cells

The three unit cells we deal with

We can imagine an equivalent point at the ce

BODY CENTRED CUBIC

FACE CENTRED CUBIC

THE CUBIC UNIT

Unit Cells in the Cubic

General Chemistry: Chapter 13

Good conductors of heat and

Electron Sea Model of

VIEWED AS CLOSELY PACKED SPHERES

Packing Spheres into

The most efficient way to pack

Spheres are packed in layers in

Packing Spheres into

Lets put in a few more spheres

Packing Spheres into

Packing Spheres into

a dimple formed by three spheres in

Packing Spheres into

a dimple formed by three spheres in

Packing Spheres into

Packing Spheres into

is formed by choosing one of the sets of dimples

Now put on second layer...

Packing Spheres into

Once one is put on the others are

Packing Spheres into

Once one is put on the others are

Packing Spheres into

Once one is put on the others are

Packing Spheres into

Note that the second layer only occupies

Packing Spheres into

PACKING SPHERES INTO

HAVE TO CHOOSE A DIMPLE

PACKING SPHERES INTO

(1) A DIMPLE DIRECTLY ABOVE SPHERE IN THE FIRST LAYER

PACKING SPHERES INTO

(2) A DIMPLE DIRECTLY ABOVE A DIMPLE

PACKING SPHERES INTO

SPHERE DIRECTLY ABOVE SPHERE IN THE

PACKING SPHERES INTO

ADD SOME MORE..

PACKING SPHERES INTO

LAYERS ONE AND THREE ARE THE

PACKING SPHERES INTO

CALLEDHEXAGONAL CLOSEST PACKIN HCP

PACKING SPHERES INTO

HEXAGONAL CLOSEST PACKING

HEXAGONAL UNIT CEL

HEXAGONAL CLOSED PACKED STRU

PACKING SPHERES INTO

THIS DIMPLE DOES NOT

PACKING SPHERES INTO

THE THIRD LAYER IS DIFFERENT FROM

PACKING SPHERES INTO

WE CALL THE THIRD LAYER C THIS TIME!