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PACKING FRACTIONS
Solid State Both of the above patterns of packing (i.e. hcp & ccp) though different in form are equally efficient. They occupy the maximum possible space which is about 74% of the available volume. Hence they are called closest packing.
Classification of Solids Space Lattice or Crystal lattice Bravais Lattices

In addition to the above two types of arrangements a third type of arrangement found in metals is body centred cubic (bcc) in which space occupied is about 68%.

Simple Cubic Lattice Close Packing in Crystals Packing Fraction

CALCULATION OF THE SPACE OCCUPIED

Interstitial Voids Locating tetrahedral and Octahedral

In simple cubic unit cell

Voids Sizes of tetrahedral and Octahedral Voids

Let a be the edge length of the unit cell and r be the radius of sphere. As sphere are touching each other Therefore a = 2r No. of spheres per unit cell = 1/8 8 = 1 Volume of the sphere = 4/3 r
3

Calculation Involving Unit Cell dimensions Structure Determination by X rays Structure of Ionic compounds Effect of temperature and Pressure on the Crystal structure Ionic Compound of the Type AB2

Volume of the cube = a3= (2r)3 = 8r3

Imperfections in Solids and defects in Crystals Consequences of Schottky defects

Fraction of the space occupied = 1/3r3 / 8r3 = 0.524

Non Stoichiometric Defects Properties of Solids

% occupied = 52.4 %

Answers to the Questions Part I Miscellaneous Exercises Part I

In face centred unit cell Let r be the radius of sphere and a be the edge length of the cube As there are 4 sphere in fcc unit cell Volume of four spheres = 4 (4/3 r3)

Answers to Miscellaneous Exercises Part I Solved Problems Part I Solved Problems Part II Objective Questions Part I Assignment Problems

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Questions Level I

In fcc, the corner spheres are in touch with the face centred sphere. Therefore, face diagonal AD is equal to four times the radius of sphere AD = 4r

Questions Level II Objective Questions Level I Objective Questions Level II Answers to Assignment Problems

But from the right angled triangle ACD IIT JEE Resources AD = AC + DC = a + a = 2a
2 2 2 2

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2a = 4r or a = 4/2 r

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volume of cube = (4/2 r)3 = 64 / 22 r3

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percentage of space occupied by sphere

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3 3

= volume of sphere / volume of cube 100 = 16/3 r / 64 /22 r 100 = 74%

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In body centred cubic unit cell

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Let r be the radius of sphere and a be the edge length of the cube

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As the sphere at the centre touches the sphere at the corner. Therefore body diagonal

AD = 4r

Face diagonal AC = AB + BC = a + a = 2a

In right angled triangle ACD =

AD = AC2 + CD2 = 2a2 + a2 = 3a

3a = 4r

a = 4r / 3

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Volume of the unit cell = a3 = (4r / 3)3 = 64r3 / 33

No. of spheres in bcc = 2

volume of 2 spheres = 2 4/3r

percentage of space occupied by spheres

= volume of sphere / volume of cube 100 = 8/3 r3 100 / 64r3 / 33 = 8/3 22/7 33/64 = 68%

Illustration 10. Show by simple calculation that the percentage of space occupied by spheres in hexagonal cubic packing (hcp) is 74%

Solution:

Let the edge of hexagonal base =a

And the height of hexagon = h

And radius of sphere = r

The centre sphere of the first layer lies exactly over the void of 2

nd

layer B.

The centre sphere and the spheres of 2

nd

layer B are in touch

So, In PQR (an equilateral triangle)

PR = 2r, Draw QS tangent at points

In QRS

QRS = 30,

SR = r

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Cos30 = SR/QR

QR = r / 3/2 = 2r / 3

PQ = PR2 QR2 = 4r2 4r2 / 3

h1 = 8r2 / 3 = 2 2/3 r

h = 2h = 4 2/3 r

Now, volume of hexagon = area of base x height

= 6 3 / 4 a h => 6 3/4 (2r) 4 2/3 r

[ Area of hexagonal can be divided into six equilateral triangle with side 2r)

No. of sphere in hcp = 12 1/6 + 1/2 2 + 3

= 2+1+3 = 6

Volume of spheres = 6 4/3r

Percentage of space occupied by sphere = 6 4/3 r / 6 3/4 4r 42/3 r 100 = 74%

Illustration 11. An element crystallizes into a structure which may be described by a cubic type of unit cell having one atom in each corner of the cube and two atoms on one of its face -24 3 diagonals. If the volume of this unit cell is 24 x 10 cm and density of the element is 3 7.20gm/cm , calculate no. of atoms present in 200gm of the element.

Solution:

Number of atoms contributed in one unit cell

= one atom from the eight corners + one atom from the two face diagonals

= 1+1 = 2 atoms

Mass of one unit vell = volume its density

= 24 1024 cm3 7.2 gm cm3

= 172.8 10

24

gm

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172.8 1024 gm is the mass of one unit cell i.e., 2 atoms

200 gm is the mass = 2 200 / 172.8 10

24

atoms = 2.3148 10

24

atoms

Illustration 12. Calculate the void fraction for the structure formed by A and B atoms such that A form hexagonal closed packed structure and B occupies 2/3 of octahedral voids. Assuming that B atoms exactly fitting into octahedral voids in the HCP formed by A

Solution:

Total volume of A atom = 6 4 / 3 rA3

Total volume of B atoms = 4 4/3 rA3 4 4/3 (0.414rA)3

Since rB/rA as B is in octahedral void of A

Volume of HCP = 242rA

Packing fraction = 6 4/3 rA3 + 4 4/3 (0.414rA)3 / 242rA3 = 0.7756

Void fraction = 1-0.7756 = 0.2244

Illustration 13. Lithium iodide crystal has a face-centred cubic unit cell. If the edge length of the unit cell is 620 pm, determine the ionic radius of I ion.

Solution: As LiI has fcc arrangement, I ions will occupy the corners and face-centres. These ions will touch each other along the face diagonal.

Face diagonal AB = 4r

= a + a = 2a

r1 = 2a / 4 = 1.414 620 pm / 4 = 219.17 pm

Illustration 14. When heated above 916C, iron changes its crystal structure from bcc to ccp structure without any change in the radius of atom. The ratio of density of the crystal before heating and after heating is:

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(A) 1.089

(B) 0.918

(C) 0.725

(D) 1.231

Solution: (B) dbcc / dccp = packing efficiency of bcc / packing efficiency of ccp = 67.92/74.02 = 0.918

Illustration 15. Select the correct statements:-

(A) For CsCl unit cell (edge-length = a), rc + ra = 3/2 a

For NaCl unit cell (edge-length =), rc + ra = l/2

The void space in a b.c.c. unit cell is 0.68

The void space % in a face-centered unit cell is 26%

Solution:

(A), (B), (C), (D). In bcc structure are r+ + r = 3/2 a

Hence, for CsCl, rC + ra = 3/2 a

(A) is correct

Since, NaCl crystalise in fcc structure

2rC + 2ra = edge length of the unit cell

Hence, rC + ra = l/2

(B) is correct

Since packing fraction of a bcc unit cell is 0.68

void space = 10.68 = 0.32

(C) is incorrect

In fcc unit cell PF = 74%

VF = 10074 = 26%

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(D) is correct

Exercise 4.

(a) What is the empty fraction in case of S.C., B.C.C and F.C.C?

(b)

Which is most packed structure S.C., B.C.C or F.C.C?

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