Unit 6.
Solid State
[Link] the following questions:
[Link] unit cell
A basic repeating structural unit of a crystalline solid is called a unit cell.
2. Give any three characteristics of ionic crystals.
1. Ionic solids have high melting points.
2. These solids do not conduct electricity, because the ions are fixed in their lattice positions.
3. They do conduct electricity in molten state (or) when dissolved in water because the ions are free to
move in the molten state or solution.
[Link] crystalline solids and amorphous solids.
Crystalline solids Amorphous solids
Long range orderly arrangement of constituents Short range, random arrangement of constituents
Definite shape Irregular shape
Generally crystalline solids are anisotropic in nature They are isotropic like liquids
They are true solids They are considered as pseudo solids (or) super
cooled liquids
Definite Heat of fusion Heat of fusion is not definite
They have sharp melting points. Gradually soften over a range of temperature and
so can be moulded.
Examples: NaCl, diamond etc., Examples: Rubber, plastics, glass etc
4. Classify the following solids.
P4, Brass Diamond NaCI iodine
1. P4 – Molecular solid
2. Brass – Metallic solid
3. Diamond –
4. NaCl – Ionic solid
5. Iodine – Molecular solid
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[Link] briefly seven types of unit cell.
1. Cubic – NaCl
2. Tetragonal – TiO2
3. Orthorhombic – BaSO4
4. Hexagonal – ZnO
5. Monoclinic – PbCrO4
6. Triclinic – H3BO3
7. Rhombohedral – Cinnabar Cubic
They differ in the arrangements of their crystallographic axes and angles. Corresponding to the above seven,
Bravis defined 14 possible crystal system as shown in the figure.
[Link] between hexagonal close packing and cubic close packing.
Hexagonal close-packing Cubic close packing:
ABA arrangement ABC arrangement
The spheres of the third layer are exactly aligned The spheres of the third layer are not aligned with
with those of the first layer those of the first layer or second layer.
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In HCP, tetrahedral voids of the second layer may be In CCP third layer may be placed above the second
covered by the spheres of the third layer layer in a manner such that its sphere cover the
octahedral voids.
The unit cell of hexagonal close packing has 6 The unit cell of cubic close packing has 4 spheres
spheres
The HCP is based on hexagonal unit cells with sides The CCP is based on the face centered cubic unit cell.
of equal length.
This type is found in metals like Mg,Zn This type is found in metals like Cu,Ag.
[Link] tetrahedral and octahedral voids.
Tetrahedral Void Octahedral Void
A sphere of second layer is above the void of the first When the spheres of the second layer partially
layer covers the voids of the first layer
The number of Tetrahedral void is given by ‘2n’ The number of octahedral void is given by ‘n’
3 Spheres in the lower layer and one in the upper 3 Spheres in the lower layer and 3 in the upper layer.
layer. Total 6 spheres.
When the 4 spheres are joined the center gives a When the 6 spheres are joined the center gives a
Tetrahedron octahedran
Coordination number is 4 Coordination number is 6
[Link] are point defects?
1. If the deviation occurs due to missing atoms, displaced atoms or extra atoms the imperfection is named as a
point defect.
2. Such defects arise due to imperfect packing during the original crystallisation or they may arise from
thermal vibrations of atoms at elevated temperatures
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[Link] Schottky defect.
1. The schottky defect arises due to the missing of an equal number of cations and anions from the crystal
lattice.
2. This effect does not change the stoichiometry of the crystal
[Link] solids in which the cation and anion are of almost similar size show Schottky defect.
4. Presence of large number of schottky defects in a crystal, lowers its density
5. Presence of Schottky defect in the crystal provides a simple way by which atoms or ions can move within the
crystal lattice.
Example: NaCl
10. Write short note on metal excess and metal deficiency defect with an example. Metal excess defect.
1. Metal excess defect arises due to the presence of more number of metal ions as compared to anions.
Ex: NaCl, KCl
2. The electrical neutrality of the crystal can be maintained by the presence of anionic vacancies equal to the
excess metal ions (or) by the presence of extra cation and electron present in interstitial position.
3. For example, when NaCl crystals are heated in the presence of sodium vapour, Na+ ions are formed and are
deposited on the surface of the crystal.
4. Chloride ions (Cl–) diffuse to the surface from the lattice point and combines with Na+ ion.
5. The electron lost by the sodium vapour diffuse into the crystal lattice and occupies the vacancy created by
the Cl– ions.
6. Such anionic vacancies which are occupied by unpaired electrons are called F centers.
7. Hence, the formula of NaCl which contains excess Na+ ions can be written as Na1+xCl.
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Metal deficiency defect
1. Metal deficiency defect arises due to the presence of less number of cations than the anions.
2. This defect is observed in a crystal in which, the cations have variable oxidation states.
3. For example, in FeO crystal, some of the Fe2+ ions are missing from the crystal lattice.
4. To maintain electrical neutrality, twice the number of other Fe2+ ions in the crystal is oxidized to Fe3+ ions.
5. In such cases, the overall number of Fe2+ and Fe3+ ions is less than the O2- ions
6. It was experimentally found that the general formula of ferrous oxide is FexO, where x ranges from 0.93 to
0.98.
11. Calculate the number of atoms in a fee unit cell.
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12. Explain AAAA and ABABA and ABCABC type of three-dimensional packing with the help of a neat
diagram.
1. AAAA type of three-dimensional packing
(i) This is Simple cubic arrangement*
(ii) This type of three-dimensional packing arrangements can be obtained by repeating the AAAA type two
dimensional arrangements in three dimensions
(iii) spheres in one layer sitting directly on the top of those in the previous layer so that all layers are identical.
(iv) All spheres of different layers of crystal are perfectly aligned horizontally and also vertically so that any unit
cell of such arrangement has a simple cubic structure
(v) In simple cubic packing, each sphere is in contact with 6 neighbouring spheres – Four in its own layer, one
above and one below and hence the coordination number of the sphere in simple cubic arrangement is 6.
2. ABABA type of three-dimensional packing:
(i)This is body centered cubic arrangement*
(ii) The spheres in the first layer (A type) are slightly separated and the second layer is formed by arranging the
spheres in the depressions between the spheres in layer A
(iii) The third layer is a repeat of the first.
(iv) This pattern ABABAB is repeated throughout the crystal.
(v)In this arrangement, each sphere has a coordination number of 8, four neighbors in the layer above and four
in the layer below.
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3. ABCABC type of three-dimensional packing
(i)This is face centered cubic arrangement
(ii)First layer Is formed by arranging the spheres as in the case of two dimentional ABAB arrangement
(iii)This is layer a, Second layer is formed by placing the spheres in the depression of the first layer.
This is layer B
(iv)There are two voids x and y
v)If void y in the first(a) are partially covered by the spheres of layer(b), it is an octahedral void
vi)Third layer(c ) may be placed over the second layer (b) in such a way that all the spheres of the third layer fit
in octahedral voids
This third layer (c ) is different from the other two layers (a) and (b), This is called Cubic closed packed structure
Coordination number of each sphere is 12
13. Why ionic crystals are hard and brittle?
i) Ionic crystals are hard because they are bound together by strong electrostatic attractive forces
ii)To maximize the attractive force, cations are surrounded by as many anions as possible
iii)To electrostatic repulsion can be enough to split or disorient completely the lattice infrastructure. Thus
imparts the brittle character.
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14. Calculate the percentage efficiency of packing in the case of a body-centered cubic crystal. Packing
efficiency.
In body-centered cubic arrangement the spheres are touching along the leading diagonal of the cube as shown
in the In ∆ABC,
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15. What is the two dimensional coordination number of a molecule in square close packed layer?
Square close packing – When the spheres of the second row are placed exactly above those of the first row.
This way the spheres are aligned horizontally as well as vertically. The arrangement is AAA type. Coordination
number is 4.
16. What is meant by the term “coordination number”? What is the coordination number of atoms in a bcc
structure?
1. Coordination number – The number of nearest neighbours that surrounding a particle in a crystal is
called the coordination number of that particle.
2. Coordination number of atoms in a bcc structure is 8
17. An element has bcc structure with a cell edge of 288 pm. the density of the element is 7.2 gcm-3. How
many atoms are present ¡n 208g of the element.
An elemeñt has bec structure with a cell edge of 288 pm. The density of the element is 7.2 gcm-3. For the Bec
structure, n = 2
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18. Aluminium crystallizes in a cubic close packed structure. Its metallic radius is 125pm. Calculate the edge
length of unit cell.
19. If NaCI is doped with 102 mol percentage of strontium chloride, what is the concentration of cation
vacancy?
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20. KF crystallizes in fcc structure like sodium chloride, calculate the distance between K+ and F– in KF.
(given : density of KF is 2.48 g cm-3)
21. An atom crystallizes ¡n fcc crystal lattice and has a density of 10 gcm3 with unit cell edge length of
100pm. calculate the number of atoms present in 1 g of crystal.
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22. Atoms X and Y form bcc crystalline structure. Atom X is present at the corners of the cube and Y is at the
centre of the cube. What is the formula of the compound?
23. Sodium metal crystallizes in bcc structure with the edge length of the unit cell 4.3 x 10-8 cm. Calculate
the radius of sodium atom.
24. Write a note on Frenkel defect.
i) Frenkel defect arises due to the dislocation of ions from its crystal lattice
ii) The ion which is missing from the lattice point occupies an interstitial position
iii) This defect is shown by ionic solids in which cation and anion differ in size.
iv) Unlike Schottky defect, this defect does not affect the density of the crystal
v) For example AgBr, in this case, small Ag+ ion leaves its normal site and occupies an interstitial
position
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