STATES OF AGGREGATION

AND CRYSTAL STRUCTURES

 Any

material may be in either of the following state.

Gas state Liquid state Solid state Type of bond Energy of bond Stability of bond Sizes of atoms Temperature Pressure

The state of a material is governed by:

GAS STATE

Each individual molecule of a gas has an order. However, the overall structure has no order. Intermolecular bonding in gases is built by Van der Waals bonding which is a weak bond. Atoms are in continuous motion at high speeds which prevents them of having a fixed shape. The random movement of atoms will lead the gas to fill any container into which it is introduced.

LIQUID STATE

Liquids have more orderly structure than gases. However, this order is short ranged. The bond b/w particles is weak & limited. So, liquids can take the shape of the container easily.

The thermal expansion of liquids is less than that of gases.

1.

Liquids derived from Crystalline solids: These consist of small group of atoms still arranged in a crystalline structure. However, bonds are not strong enough for them to form a rigid mass. Liquids derived from amorphous solids: These are composed of large molecules which are flexible & mobile. The major difference b/w two liquid types is their melting point. First one has a definite melting point because all the bonds in the X-talline structure have the same strength & break down at the same temperature.

2.

SOLID STATE
Solid materials are classified according to the regularity with which atoms or ions are arranged with respect to one another. Crystalline Solids Amorphous Solids
In crystalline materials atoms are situated

in a repeating or periodic array over large atomic distances. (long range order) do not exist

In amorphous materials long range order

Upon solidification of a liquid the atoms will position themselves in a repetitive 3-D pattern in which each atom is bonded to its nearest atoms. Therefore, speed of solidification has a great effect on the type of solid.
Solidification occurs gradually Crystalline

Solidification occurs suddenly Amorphous

 The type of bond also affects the type of solid Ionic and Metallic Bonds Crystalline Covalent Bonds Amorphous
While passing from liquid state to solid state

there is no definite dividing line. (Gels are in between)

Gels are formed by very fine particles of solid

trapping liquid molecules within themselves. According to the type, strength and number of bonds, gels may be more liquid or more solid.

CRYSTALLINE SOLIDS
In a crystalline solid, particles which may be

(atoms, molecules or ions) are surrounded by like neighbors according to a definite geometrical repetitive pattern.

When describing crystalline structures, atoms or

ions are thought of as being solid spheres having well-defined diameters.

An example of the hard sphere model is the atomic arrangement of some common elemental metals shown in the figure.
In this example:
All atoms are identical. Sometimes the term lattice is used in the context of crystal structures.

Space-Lattice: 3-D arrays of points in space coinciding with atom positions.

Unit cell: is the smallest unit of a space lattice which repeats itself to form the lattice. In other words space-lattice is formed by face to face packing of unit cells.

Unit Cell Configurations

1. Simple Unit Cell: Lattice points are at every corner of the cell.

2. Base Centered Unit Cell: Extra lattice points in the center of two parallel faces.

3. Body Centered Unit Cell: An extra lattice points in the interior. 4. Face Centered Unit Cell: Extra lattice points at the center of each face.

CRYSTAL SYSTEMS
Based on unit cell configurations and atomic arrangements

Face Centered Cubic (FCC) Structure

Two representations of a unit cell

Atomic Packing Factor

Atomic packing factor shows us how dense the unit cell is:

Volume of atoms in a unit cell APF Total unit cell volume

APF = 1 ......... Unit cell is filled with atoms
APF = 0 ......... Unit cell is empty

Atomic Packing Factor of FCC

Remember!!! Atoms are hard spheres and they touch one another along cube diagonal for an FCC structure.
H E G

a 2 a 2 (4r ) 2 a 2r 2
Volume of unit cell, Vc

r
2r
D

r
A a B

C a

Vc a3 (2r 2 )3 16r 3 2

Number of atoms per unit cell:

Face atoms 6 x 1/2 = 3

Corner atoms 8x1/8 = 1

Total number of atoms in the unit cell = 4

Atomic Packing Factor of FCC

H E G

r
2r
D

Volume of atoms in a unit cell APF Total unit cell volume (4) * (4 / 3 r 3 ) APF 16r 3 2 APF 0.74

r
A a B

C a

Body Centered Cubic (BCC) Structure

r
E

F 2r
D

How many atoms are there in BCC structure?

APF of BCC?

r
A

2
B

How many atom are in the bcc unit cell?

APF Volume of atoms in a unit cell Total unit cell volume
APF 0.68

2.4.R 3 / 3 2.4. .R 3 / 3 APF 4R a3 ( )3 3

1 atom in core + 8 x 1/8(atoms on corner) =2 atoms atoms

Unit cell

ADF =

( 3a/4 ) 3

body atom

a3

Body of unit cell

Birim hcre

DENSITY COMPUTATION
Since the entire crystal can be generated by the repetition of the unit cell, the density of a crytalline material can be calculated based on the density of the unit cell.
: Density of the unit cell M : Mass of an atom Vc : Volume of the cell

nM Vc

n : Number of atoms in the unit cell

Mass of an atom is given in the periodic table in atomic mass units (amu) or gr/mol. To convert (amu) to (gr) use avagadros number.

DENSITY COMPUTATION
Avagadros number, NA= 6.023x1023 atoms/mol Therefore,
: Density of the unit cell

nA Vc N A

n : Number of atoms in the unit cell A : Atomic mass Vc : Volume of the cell

NA : Avagadros number

EXAMPLE

Crystal structure = FCC: 4 atom/unit cell Atomic mass = 63.55 g/mol (1 amu = 1 g/mol) Atomic diameter = 0.128 nm (1 nm = 10 cm) V c = a3 ; for FCC, a = 4R/ 2 ; Vc = 4.75 x 10 -23 cm 3

nA Vc N A

Therocical result Cu = 8.89 g/cm 3

Real result

Cu = 8.89 g/cm 3

Characterictics of some lements at oC

Element Aluminum Argon Barium Beryllium Boron Bromine Cadmium Calcium Carbon Cesium Chlorine Chromium Cobalt Copper Flourine Gallium Germanium Gold Helium Hydrogen
Symbol Atomic mass

Density. 3

Atomic diameter Cyristal str

Al Ar Ba Be B Br Cd Ca C Cs Cl Cr Co Cu F Ga Ge Au He H

26.98 39.95 137.33 9.012 10.81 79.90 112.41 40.08 12.011 132.91 35.45 52.00 58.93 63.55 19.00 69.72 72.59 196.97 4.003 1.008

(g/cm ) 2.71 -----3.5 1.85 2.34 -----8.65 1.55 2.25 1.87 -----7.19 8.9 8.94 -----5.90 5.32 19.32 -----------

(nm) fcc 0.143 ----------bcc 0.217 HSP 0.114 Rhomb ---------------HSP 0.149 fcc 0.197 Hex 0.071 bcc 0.265 ----------bcc 0.125 HSP 0.125 fcc 0.128 ----------Ortho. 0.122 Dia. cubic 0.122 fcc 0.144 ---------------------

POLYCRYSTALLINE MATERIALS

Most crystalline solids are composed of many small crystals or grains termed as polycrystalline. During the solidification of a polycrystalline solids, the crystallization may start at various nuclei with random crystallographic orientations. Upon solidification, grains of irregular shapes may form. The structure will have grain boundaries that could be seen under a microscope.

Stage 1

Stage 2

Stage 3

Stage 4

POLYMORPHIC TRANSFORMATION

Materials having the same chemical composition can have more than one crystal structure. These are called allotropic or polymorphic materials.
Allotropy for pure elements. Polymorphism for compounds.

These transformations result in changes in the properties of materials and form the basis for the heat treatment fo steels and alloys.

POLYMORPHISM

Carbon may exist in two forms:

Graphite ( 2D layers)

Diamond (3D structure)

POLYMORPHISM
Iron (Fe) may also exist in several forms:
BCC at room temperature iron FCC at 910C iron BCC at above 1400C iron Above 1539C liquid

Upon heating an iron from room temperature to above 910C, its crystal structure changes from BCC to FCC accompanied by a contraction (reduction in volume).