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 - 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

CRYSTALLINE SOLIDS:

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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
Demo, green and red lasers
n is the order of diffraction n = 1,2,3, …
Constructive Interference

λ light wavelength

θ

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 1 1 2 2 2

FIRST CHOOSE OPTION 1...

Fill the Third Layer

OPTION ONE!

1 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

A

B A

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 1 1 2 2 2

NOW CHOOSE OPTION 2...

THIRD LAYER

OPTION 2!

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.

A 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
NOTICE the flip...

CCP

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 =  volume of the unit cell   V = V
v spheres 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 CELL FACE COUNTS FOR 1/2 ATOM ON A FACE.

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Atoms are shared between adjacent unit cells in the lattice
COUNTS FOR 1/4 ATOM ON A FACE. COUNTS AS 1/8 FOR ATOM ON A CORNER.

CELL EDGE

CELL 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? Each face atom contributes? 1/8 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?
V f = V
v

spheres

unitcell

4 4( π r ) = 3 a
3 3

a

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

a r 2r r

CUBIC UNIT CELLS
SIMPLE CUBIC BODY CENTERED CUBIC FACE CENTERED CUBIC

Edge length in terms of r

2r
# of spheres in the unit cell

4r 3

r 8
4

2 1 Fraction of volume occupied by spheres

52.4%

68.0%

74.0%

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Calculating the density of a unit cell
Density = mass 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
3 −8 3 − 23 cell
−1 23 −1

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63.54gmol The mass of a Cu atom is m = = 1.055 × 10 g 6.022 × 10 mol
− 22

The density of the unit cell is

4 × (1.055 × 10 −22 g ) Density = = 8.89 gcm −3 −23 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 Closest Packed (ccp)

Cubic Unit Cells Simple cubic (sc) Body-centered Face-centered cubic (bcc) cubic (fcc)

Hexagonal Closest Packed (hcp) Hexagonal unit cell

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