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Chem 5

Chapter 13

Liquids, Solids, and Intermolecular Forces

Part 3

December 6, 2002

SOLIDS
Solids are either amorphous or crystalline.

AMORPHOUS SOLIDS:
- Considerable disorder in structure
Example: rubber, glass

CRYSTALLINE SOLIDS:
- Classified as Metallic, Ionic, Molecular, dependent
on the type of interaction (bond) that holds their atoms,
ions or molecules in place.
- Highly regular structure in the form of a lattice: a
three dimensional array of points representing the
centers of the components (such as atoms, ions or
molecules ) in the repeating pattern of the crystal

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LATTICE

We can pick out the smallest repeating unit – a unit cell.


A unit cell, when stacked together repeatedly without
any gaps, can reproduce the entire 3D crystal.

SCATTERING OF X-RAYS BY CRYSTALS

In the 19th century crystals were identified only by


their shape. People did not know atomic positions
within the crystal.

In 1895 Roentgen discovered X-rays.

Max von Laue suggested that a crystal might act


as a diffraction grating for X- rays …

because an X-ray wavelength is comparable to the


spacing between atoms in the lattice, on the order of
the Bohr radius.

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In 1912 Knipping observed X-ray diffraction patterns

X-Ray
Diffraction Pattern

The Braggs formulated a diffraction law.

BRAGG DIFFRACTION LAW


When electromagnetic radiation passes through
a crystal…

it interacts with the electrons and is scattered


in all directions. The waves constructively interfere
in certain directions and destructively interfere in
certain directions.

Constructive Interference Destructive Interference

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BRAGG DIFFRACTION LAW
nλ = 2d sinθ n is the order of diffraction
n = 1,2,3, …

Constructive
Demo, green and red lasers Interference

θ
λ light wavelength

In contrast, (n+1/2)λ=2d sinθ is the condition for destructive interference

DEMO: Diffraction of a laser beam by a transmissive grating

1.8 µm
comparable to
laser wavelength

The laser wavelength is 0.53µm, ~5000 times longer than X-ray wavelength.

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Demo

Diffraction of a laser
beam by the 2D
patterns

THE CUBIC UNIT CELLS


Simple Cubic (sc) Unit Cell
- Eight equivalent points at the
corners of a cube

Body-Centered Cubic (bcc) Unit Cell


- Eight equivalent points at the
corners of a cube and one at the
center

Face-Centered Cubic (fcc) Unit Cell


- Eight equivalent points at the
corners of a cube and six on the
center of the cube faces

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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.

Metals (e.g. Cu, Au, Na) usually have closest packed


lattices.

Closest Packing of Spheres into Lattices

First Layer

Now put on the second layer…

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For the second layer, spheres can fit into two
types of “dimples” formed by three spheres in
the first layer.

Note the inverted triangles

The second layer is formed by choosing one of the


two sets of dimples

Once one is put on, the others are forced


into half of the dimples of the same type.

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Fill the Second Layer

Note that the second layer only occupies half


the dimples in the first layer.

Fill the Second Layer


Occupied
Dimple

Unoccupied
Dimple

Note that the second layer only occupies half


the dimples in the first layer.

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The third layer is formed by choosing one of the
two sets of dimples.

NOTE:
the
inverted
triangle
1 2 2

1 1 2

FIRST CHOOSE OPTION 1...

Fill the Third Layer OPTION ONE!

1 1

SPHERE DIRECTLY ABOVE SPHERE IN THE FIRST LAYER

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THIRD LAYER OPTION ONE!
LAYERS ONE AND THREE ARE ON TOP OF EACH OTHER

THIS ABA ARRANGEMENT OF LAYERS IS


CALLED HEXAGONAL CLOSEST PACKING (HCP)

IT IS CALLED HEXAGONAL CLOSEST PACKING (HCP)


BECAUSE THE ABA ARRANGEMENT GIVES
A HEXAGONAL UNIT CELL.

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Again, the third layer has choices of two sets of
dimples.

NOTE: the
inverted
triangle

1 2 2

1 1 2

NOW CHOOSE OPTION 2...

THIRD LAYER OPTION 2!

2 2

THIS SPHERE DOES NOT LIE DIRECTLY


OVER THE SPHERES OF THE FIRST LAYER.

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FILL THE THIRD LAYER OPTION 2
GREEN SPHERES DO NOT LIE DIRECTLY OVER
THE BLACK SPHERES OF THE FIRST LAYER.

A
B
C

CALL THE THIRD LAYER C THIS TIME!


THE ABC ARRANGEMENT OF LAYERS.

FOURTH LAYER THE SAME AS FIRST.

B
C
A

WE CALL THE ABCA ARRANGEMENT


CUBIC CLOSEST-PACKED (CCP) …

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BECAUSE CCP GIVES A CUBIC UNIT CELL

THIS ABCA ARRANGEMENT RESULTS IN A


FACE- CENTRED CUBIC UNIT CELL.

COMPARISON OF THE TWO WAYS OF CLOSEST PACKING

HCP CCP
NOTICE the flip...

COORDINATION NUMBER (CN)


- the number of nearest neighbors that a lattice point has
in a crystalline solid. CN = 12 for both HCP &CCP

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COORDINATION NUMBER FOR SIMPLE CUBIC UNIT

How do we count
nearest neighbors?

How many nearest neighbors?


CN = 6

COORDINATION NUMBER
for the three types of cubic unit cells

Simple cubic (sc) CN = 6

Body centered cubic(bcc) CN = 8

Face centered cubic


(ccp same as hcp) CN = 12

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EFFICIENCY OF PACKING

FRACTION OF THE VOLUME OCCUPIED BY THE


SPHERES IN A UNIT CELL

 volume occupied by the spheres in the unit cell 


f = 
 
v
volume of the unit cell
V
= spheres

V unitcell

Vspheres= number of spheres x volume single sphere


Vunit cell = a3 cubic unit cell of edge length a

COUNTING ATOMS IN A UNIT CELL!

ATOMS CAN BE WHOLLY IN A UNIT CELL OR

COUNTS 1 FOR
ATOM IN CELL

ATOMS ARE SHARED BETWEEN ADJACENT UNIT


CELLS IN THE LATTICE

COUNTS FOR
CELL FACE 1/2 ATOM ON A
FACE.

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Atoms are shared between adjacent unit
cells in the lattice

COUNTS FOR
CELL EDGE 1/4 ATOM ON A
FACE.

COUNTS AS
CELL CORNER 1/8 FOR ATOM
ON A
CORNER.

FACE-CENTERED CUBIC UNIT CELL


What is the number of spheres in the cell?
A sphere on 8 corners and 6 faces.

spheres are shared


between adjacent unit cells

Each corner atom contributes? 1/8

Each face atom contributes? 1/2

Total spheres = 8 (1/8) + 6 (1/2) = 1 + 3 = 4

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WHAT FRACTION OF SPACE IS OCCUPIED IN
A FACE CENTERED CUBIC UNIT CELL?
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V 4( π r )3

f = spheres
= 3
v
V unitcell
a3
a

We need to express a in terms of r


Spheres touch each other on the
surface of the cell. a
FACE DIAGONAL = r + 2r + r = 4r
r
a2 + a2 = (4r)2; 2a2 = 16r 2
2r
a2 = 8r 2 a = r 8
4 * 4 πr3
fv = 3 = 0.740
(r 8 )3 r

CUBIC UNIT CELLS


SIMPLE CUBIC BODY CENTERED CUBIC FACE CENTERED CUBIC

Edge length in terms of r


4r
2r
3
r 8
# of spheres in the unit cell
1 2 4
Fraction of volume occupied by spheres
52.4% 68.0% 74.0%

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Calculating the density of a unit cell

mass
Density =
volume

Mass is the mass of the number of atoms in the unit cell.

Mass of one atom = atomic mass / NA

NA Avogadro’s number!

Calculation for Cu.

Cu crystallizes as a fcc

r = 128pm = 1.28x10-10m = 1.28x10-8cm

Volume of unit cell is given by:

V = (r 8 ) = ( 8 × 1.28 × 10 cm) = 4.75 × 10 cm


cell
3 −8 3 − 23 3

−1
63.54gmol
The mass of a Cu atom is m = = 1.055 × 10 g − 22

6.022 × 10 mol
23 −1

The density of the unit cell is

4 × (1.055 × 10 −22 g )
Density = −23 3
= 8.89 gcm −3
4.75 × 10 cm
4 atoms per unit cell! The measured density is 8.92gcm-3.

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Summary
Closest Packing
Cubic
Cubic Closest
Unit Packed
Cells (ccp)

Simple cubic Body-centered Face-centered


(sc) cubic (bcc) cubic (fcc)

Hexagonal
Closest
Packed
(hcp)

Hexagonal
unit cell

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