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Published on: 01/10/2019
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1.
A metallic element exists as a cubic lattice. Each edge of the unit cell is 2.88\(\mathring { A } \). The density of the metal is 7.20 g cm-3. How many unit cells there will be in 100g of the metal?
2.
How do the spacings of the three planes (100), (101) and (111) of simple cubic lattice vary?
3.
Experiment shows that Nickel oxide has the formula Ni0.96.O1.00. What fraction of Nickel exists as of Ni2+ and Ni3+ ions?
4.
Explain Schottky defect.
5.
Calculate the percentage efficiency of packing in case of body centered cubic crystal.
6.
Explain AAAA and ABABA and ABCABC type of three dimensional packing with the help of neat diagram.
7.
Write short note on metal excess and metal deficiency defect with an example.
8.
What is the two dimensional coordination number of a molecule in square close packed layer?
9.
Why ionic crystals are hard and brittle?
10.
Calculate the number of atoms in a fcc unit cell.
1.
Volume of unit cell = (2.88\(\mathring { A } \))3 = 23.9 x 10-24cm3
Volume of 100 g of the metal \(=\frac { m }{ A } =\frac { 100g }{ 7.2{ gcm }^{ -3 } } \) = 13.9 cm3
Number of unit cells in this volume \(=\frac { 13.9{ cm }^{ 3 } }{ 23.9\times { 10 }^{ -24 }{ cm }^{ 3 } } \) = 5.82 x 1023
2.
Simple Cubic Lattice
100,101,111
\({ d }_{ hkl }=\frac { a }{ \sqrt { { h }^{ 2 }+{ k }^{ 2 }+{ l }^{ 2 } } } \)
\({ d }_{ 100 }=\frac { 1 }{ \sqrt { { 1 }^{ 2 }+0^{ 2 }+0^{ 2 } } } =1\)
\({ d }_{ 101 }=\frac { 1 }{ \sqrt { { 1 }^{ 2 }+0^{ 2 }+0^{ 2 } } } =\frac { 1 }{ \sqrt { 2 } } \)
\({ d }_{ 111 }=\frac { 1 }{ \sqrt { { 1 }^{ 2 }+1^{ 2 }+1^{ 2 } } } =\frac { 1 }{ \sqrt { 3 } } \)
\(\\ { d }_{ 100 }:{ d }_{ 101 }:{ d }_{ 111 }=1:\frac { 1 }{ \sqrt { 2 } } :\frac { 1 }{ \sqrt { 3 } } (or)\)
=1:0.707:0.577
3.
Formula is Nio.96 O1.00
So the ration of Ni = O = 96.00
So if there are 100 atom of oxygen, as atoms of Ni
Let the number of atoms of Ni+2 = x
The number of atoms of Ni+2 = 96 - x
Charge on Ni = charge on O
So that oxygen has charge = 2
3 (96 - x) + 2x = 2(100)
288 - 3x + 2x = 200
-x = -88
x = 88
Percentage of Ni + 2 = (atom of Ni+2 / total number of atoms of Ni 100.)
= 100.(94/98) x 100 = 96%
Percentage of Ni+3 = 100 - Ni+2
= 100 - 96 = 4%
4.
(i) Schottky defect arises due to the missing of equal number of cations and anions from the crystal lattice. This effect does not change the stoichiometry of the crystal.
(ii) Ionic solids in which the cation and anion are of almost of similar size show schottky defect.
Example: NaCl.
(iii) Presence of large number of schottky defects in a crystal, lowers its density.
(iv) Presence of Schottky defect in the crystal provides a simple way by which atoms or ions can move within the crystal lattice.
5.
In bcc unit cell, ΔABC
AC2 = AB2 + BC2
\(AC=\sqrt { { AB }^{ 2 }+{ BC }^{ 2 } } \)
\(\\ AC=\sqrt { { a }^{ 2 }+{ a }^{ 2 } } =\sqrt { { 2a }^{ 2 } } =\sqrt { 2 } a\)
In ΔACG
AG2 = AC2 + CG2
\(AG=\sqrt { { AC }^{ 2 }+{ CG }^{ 2 } } \)
\(AG=\sqrt { { \left( \sqrt { 2a } \right) }^{ 2 }+{ a }^{ 2 } } \)
\(AG=\sqrt { { 2a }^{ 2 }+{ a }^{ 2 } } =\sqrt { { 3a }^{ 2 } } \)
\(AG=\sqrt { 3a } \)
\(\sqrt { 3 } a=4r\)
\(r=\frac { \sqrt { 3 } }{ 4 } a\)
∴ Volume of the sphere with radius 'r' \(=\frac { 4 }{ 3 } { \pi r }^{ 3 }\)
\(=\frac{4}{3}\pi { \left( \frac { \sqrt { 3 } }{ 4 } a \right) }^{ 3 }\)\(=\frac { \sqrt { 3 } }{ 16 } \pi { a }^{ 3 }\)
Number of spheres belong to a unit cell in BCC arrangement is equal to two and hence the total volume of all spheres.
(i) Packing fraction = \(=\frac{Total \quad volume \quad occupied \quad by \quad spheres \quad in \quad a \quad unit \quad cell}{volume \quad of \quad the \quad unit \quad cell}\times100\)
\(\therefore\)Volume of all spheres \(=2\times \left( \frac { \sqrt { 3 } \pi { a }^{ 3 } }{ 16 } \right) =\frac { \sqrt { 3 } \pi { a }^{ 3 } }{ 8 } \)
Packing fraction \(=\frac { \left( \frac { \sqrt { 3 } \pi { a }^{ 3 } }{ 8 } \right) }{ ({ a }^{ 3 }) } \times 100\)
\(=\frac { \sqrt { 3 } \pi }{ 8 } \times 100\)
\(\\ =\sqrt { 3 } \pi \times 12.5\)
= 1.732 x 3.14 x 12.5
= 68%
6.
AAAA type of three dimensional packing:
1. This is simple cubic arrangement.
2. Three dimensional packing arrangement can be obtained by repeating the AAAA type two dimensional arrangements in three dimensions.
3. Spheres in one layer sitting directly on the top of in the previous layer so that all layers are identical.
4. All spheres of different layers of crystal are perfectly aligned horizontally and also vertically.
5. In simple cubic packing, each sphere is in contact with 6 neighbouring spheres
6. Four in its own layer, one above and one below and hence the coordination number of the sphere in simple cubic arrangement is 6.
ABABA type of three dimensional packing:
(i) This is body centered cubic arrangement.
(ii) The spheres in the first layer 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) Each sphere has a coordination number of 8, four neighbors in the layer above and four in the layer below.
ABCABC type of three dimensional packing:
(i) This is face centered cubic arrangement.
(ii) In this arrangement (FCC) second layer spheres are arranged at the dips of first layer. Third layer spheres are arranged in a manner such that it cover the octahedral void.
(iii) Then no longer third layer is similar to first or second layer.
(iv) Third layer gives different arrangement. Fourth layer spheres are similar to first layer.
(v) If the first, second and third layer are represented as A, B, C then this type of packing gives the arrangement of layers as ABCABC.. and the sequence is repeated.
7.
Metal excess defect:
(i) It arises due to the presence of more number of metal ions as compared to anions.
(ii) Examples: NaCl, KCl
(iii) The electrical neutrality of the crystal can be maintained by the presence of anionic vacancies equal to the presence of extra cation.
(iii) For example, when NaCI crystals are heated in the presence of sodium vapour, Na+ ions are formed and are deposited on the surface of the crystal.
(iv) Chloride ions (Cl-) diffuse to the surface from the lattice point and combines with Na+ ion.
(v) The electron lost by the sodium vapour diffuse into the vacancy created by the Cl- ions.
(vi) Such anionic vacancies which are occupied by unpaired electrons are called F centers. Hence, the formula of NaCl can be written as Na1+xCl.
Metal deficiency defect:
(i) Metal deficiency defect arises due to the presence of less number of cations than the anions. This defect is observed in a crystal in which, the cations have variable oxidation states.
(ii) For example, In FeO crystal, some of the Fe2+ ions are missing from the crystal lattice. To maintain the electrical neutrality, twice the number of other Fe2+ ions in the crystal is oxidized to Fe3+ ions. In such cases, overall number of Fe2+ and Fe3+ ions is less than the O2- ions.
8.
Linear arrangement of spheres in one direction is repeated in two dimension (i.e.) more number of rows can be generated identical to the one dimensional arrangement such that all spheres of different rows align vertically as well as horizontal.
If we denote the first row as A type arrangement, then the above mentioned packing is called AAA type, because all rows are identical as the first one. In this arrangement each sphere is in contact with four of its neighbours.
9.
The structural units of an ionic crystal are cations and anions. They are bound together by strong electrostatic attractive forces. To maximize the attractive force, cations are surrounded by as many anions as possible and vice versa. Hence they are hard and brittle.
10.
Number of atoms in a fcc unit cell = \(\frac{N_{c}}{8}+\frac{N_{f}}{2}=\frac{8}{8}+\frac{6}{2}=1+3=4\)
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