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CRYSTALLOGRAPHY

INDROTUCTION

I.

NaCl Structure [Ionic compound Na + , Cl ions] :

1.

No. of Atom Per Unit Cells :

THEROY

There are 8 Na + ions at the corner and each corner atom shared by 8 unit cells.
Hence contribution of corner atoms is (i.e.

1
8

8= 1)

And 6 face centered atoms & each shared by two unit cells. Hence contribution of
face centered atom is (i.e. 6

1
6

= 3)

No. of atoms per unit cell = 1 + 3 = 4


Calculation for Cl :
There are 12Cl atoms at the edges, each shared by 4-unit cells. Hence
contribution of edge centered atoms = 1

2.

Total No. of Cl atom = 3 + 1 = 4

4 Na + 4 Cl = 8

Co-ordination Number (CN) :


In NaCl, given anion is surrounded by 6cations or vice-versa. Hence,

Co-ordination Number = 6
Some common material like MgO, FeO, LiF exhibits this structure.

CRYSTALLOGRAPHY

3.

INDROTUCTION

THEROY

Atomic Radius (r) :


From Fig.
a = 2r+ + 2r
2r+ = Radius of Na+
2r = Radius of Cl
We cant take radius r because radius of Na+ & Cl are different .

4.

Atomic Packing Factor :

Atomic packing Factor =

(n

34 r3+ ) + (n 34 r3 )
a3

Where n = 4

Description of NaCl Structure :

a)

The space lattice of NaCl structure is FCC, with basis consist of Na+ and Cl , One
located at lattice point (0, 0, 0) and other at one half of the body

diagonal of the

cube.
b)

The structure may also be viewed as an interpenetration of two FCC

sub-

lattices, one composed entirely of Na+ ions having their origin at


c)

(0, 0, 0) and one composed of Cl ions having their origin at , say, (2a , 0, 0)

CRYSTALLOGRAPHY

INDROTUCTION

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d)

There are 4-molecules at NaCl.

e)

In the formation of NaCl crystal, Na-atom loses its outermost e and

acquires

a excessive +ve charges while Cl-atom accepts one e from Na and, acquire ve
charge .
f)

There are electrostatic force of attraction between the opposite charges and
strong repulsive forces between the electronic shells of two ions

when they

come closer.
g)

When attractive and repulsive forces balance, equilibrium, reached,

resulting

in stable structure.

Importance of stable structure.


II.

Diamond Structure [FCC] :


Carbon atom bonded to four other carbon atom to covalent bonding.

1.

No. of Atoms Per Unit Cell :


In diamond structure, there are eight corner atoms, each corner atoms shared

by 8-unit cells. Hence the contribution of face cnetred atom is 1.

(i.e.

1
8

8= 1)

CRYSTALLOGRAPHY

INDROTUCTION

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And there are 4 inside atom which is not shared by any other unit cell
Hence n = 1 + 3 + 4 = 8

No.of atoms
Unit cell

2.

=8

Co-ordination Number (CN) :


For any corner atom of diamond, three nearest neighbours are face

atom and one nearest neighbor is inside atom belonging to that

entered

corner atom.

Hence,
Co-ordination Number = 4
For any corner atom of diamond, three nearest neighbours are face
atom and one nearest neighbours is inside atom belonging to

entered

that corner atom.

Hence, Co-ordination Number = 4


3.

Atomic Radius (r) :


In Bcc, body centered atom touches to the corner atoms and corner

not touch to each other.


From Fig.
AB 2 = AD2 + BD2
= a2 + (a2 + a2 )

atoms do

CRYSTALLOGRAPHY

= 3a2

INDROTUCTION

AB 2 = 3a
Hence length of body diagonal is 3a .
And

1
4

, Body diagonal = 2r

3a = 2r
4

r =

3a

Atomic Radius =

4.

Atomic Packing Factor :

n 34 r3

Atomic packing Factor =

a3

For Diamond ,

n = 8, r =

3a

n 34

8
3

(4

APF =

APF = 0.34

a3

a)

THEROY

CRYSTALLOGRAPHY

4.

INDROTUCTION

Void Space :
Void Space

= (1 APF)
= (1 0.34)
= 0.66

5.

Void Space = 0.66

Packing Efficiency :

Packing efficiency = APF 100%


= 0.34 100%
= 34 %

Packing efficiency = 34 %

THEROY

CRYSTALLOGRAPHY

INDROTUCTION

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III.

Zinc Sulphide [ZnS] :

a)

The structure of Zinc sulphide identical to the Diamond Cubic

b)

This is an ionic compound.

c)

The Bravais lattice of ZnS is a face centered cubic [FCC]

d)

It consist of two interpenetrating FCC Sub-lattice which are occupied by two


different elements and are displaced from each other by one

structure.

quarter of

body diagonal.
e)

There are four ZnS molecules For unit Cell.

1.

No. of Atom Per Unit Cells :


Calculation for Zn :

Contribution of corner atoms is (i.e.


atoms is (i.e. 6

1
6

1
8

8 = 1 ) and contribution of face centered

= 3)

Hence Total no. of Zn- atoms = 1 + 3 = 4


Calculations for S :

There are 4-inside atoms present on the

Total No. of Cl atom = 3 + 1 = 4

4 Zn + 4 S = 8

1
4

th of body diagonal of Unit

Cell.

CRYSTALLOGRAPHY

2.

INDROTUCTION

Co-ordination Number (CN) :


In ZnS, given cation is surrounded by 4 anions or vice-versa. Hence,

3.

Co-ordination Number = 4

Atomic Radius (r) :

Hence, S-present at

4.

1
4

th of body diagonal

1
rZn + rs = 3 a
4
Atomic Radius (r) = + =

Atomic Packing Factor :

Atomic packing Factor =

(nzn

34 r3zn ) + (ns 34 r3s )


a3

THEROY

CRYSTALLOGRAPHY

INDROTUCTION

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IV.

Hexagonal Closed Packed (HCP) Structure :

a)

Consider a layers of similar atoms with each atoms surrounded by 6

atoms in

one plane. (layer A) .


b)

Another similar layer B can be placed on top of layer A such that the
layer B occupy the alternate valleys formed by the atoms of

c)

atoms of

layer A.

If a new layer is placed on top of the B-layer such that each atom of it is exactly
above the atoms of layer A, then this new layer will be exactly identical to the layer
A & this type of stacking is repeated successively .

d)

The following layered arrangement is obtained.


---------- ABABAB ---------------

e)

This type of stacking is called HCP stacking & the structure is known as
Hexagonal close packed structure.
[Note : In FCC the third layer is not identical to A

--------------- ABCABCABC -------------- ]

Hexagonal Close Packed Structure [HCP] :


Hexagonal close packed (HCP) structure is one of the most metallic structure
about 25 metals exhibit this structure.

CRYSTALLOGRAPHY

1.

INDROTUCTION

THEROY

No. of Atoms Per Unit Cell :


In HCP, each corner atoms of hexagonal face is shared by six unit cells. Hence the
distribution of corner atoms is

1
6

. There are six corner atoms on each face. (i.e

upper and lower face)

Therefore contribution of corner atoms to the unit cell = 2 (6

1
)=2
6

There are two hexagonal face centered atoms and which is shared by two unit
cells. Hence contribution of face centered atom to the unit cell

= 2 (2

1
)=1
2

And three atoms are forming a triangle in the middle layer are there in the body
to cell and they are not shared by adjacent cells. Hence,

No.of atoms
Unit cell

2.

=2+1+3=6

Co-ordination Number (CN) :


For any face centered atom, there are 6-nearest neighbours in same hexagonal
plane, 3-nearest neighbours are above the plane & 3-neearest neighbours are
below the plane.
Hence,
Co-ordination Number = 12

CRYSTALLOGRAPHY

3.

INDROTUCTION

THEROY

Atomic Radius (r) :


The atoms are in contact along the edges of hexagonal.
a = 2r

5.

r =

a
2

Atomic Radius =

a
2

Atomic Packing Factor :

Atomic packing Factor =

n 34 r3
Volume of unit cell

---(1)

Volume of unit Cell :


Volume of Hexagon = Area of bade hight of cell

---(2)

Area of Base = 6 Area of ABC

Area of ABC =

1
2

base height

Draw r AD to BC .

Sin 60 =

AD

=
AB

AD
a

---(3)

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Height of ,
AD = a sin 60

AD =

3a

--- (4)

Substitute eqn (3)

Area of ABC =

1
2

3a

3a2

Consider height of unit cell = h


O is centroid (orthocenter) of ABC

AO =

&

AM = 2r = a

From AOM,

AD

AM 2 = AO2 + OM 2

2
2
h 2
= ( AD) + ( )
3
2
2

2 3 a
h 2
= (
) + (2)
3 2

h2
4

2a2
3

--- (5)

CRYSTALLOGRAPHY

INDROTUCTION

a
3

--- (6)

From eqn (5) and (6)

Hence, Volume of Unit Cell =

3a2

+ ( a)
3

= 32 a3

4.

= 32 a3

Volume of Hexagonal U.C

Volume of Hexagonal U.C = 3

Atomic Packing Factor :

n 34 r3

Atomic packing Factor =

When, n = 6, r =

APF =

n 34

a
2
3

(4

a)

32 a3

6 34 (2a )
32 a3

APF = 0.74

Volume of unit cell

, Volm = 32 a3

APF =

THEROY

CRYSTALLOGRAPHY

5.

INDROTUCTION

Void Space :
Void Space

= (1 APF)
= (1 0.74)
= 0.26

6.

Void Space = 0.26

Packing Efficiency :

Packing efficiency = APF 100%


= 0.74 100%
= 74 %

Packing efficiency = 74 %

THEROY