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1. SOLIDS
A substance is said to be a solid if it satisfies the following conditions:
(i) It must have a definite shape and volume.
(ii) It must possess rigidity and diffusion should be almost nil.
Some important characterstics of solids are: Definite shape and volume, Rigidity, High density, Nil Compressibility, Nil Diffusion
2. TYPES OF SOLID
There are two types of Solids
2.1 Crystalline solids are the substances whose constituent units are arranged in an orderly fashio, which repeates itself over very
long distances as compared to interatomic distances Crystalline solids have sharp melting points and are anisotropic i.e., their physical
properties such as refractive index and conductivity have different values in different directions. Sodium chloride, diamond and sugar
are some important examples of crystalline solids.
2.1.1 Types of Crystalline Solids.
Ionic Ions Coulombic NaCl, KCl, Hard but High High Conductor (in
CaO, MgO brittle (≃1000 K) (≃2000 K) molten state
and in
aqueous
solution)
2.2 Amorphous solids are the substances whose constituent units do not possess an orderly arrangement over a long range. An
amorphous solid on being cut with a sharp edged tool gives two pieces with irregular surfaces. Glass, plastics and fused silica are
some important examples of amorphous solids.
3. CRYSTALLOGRAPHY
Crystallorgraphy is the branch of secience, which deals with the properties, geometry and structure of crystalline substances.
3.1 Crystal Lattice or Space Lattice. The arrangement of points showing how molecules, atoms or ions are arranged at different sites
in three-dimensional space is known as space lattice or crystal latteice. The positions occupied by molecules, atoms or ions in the
crystal lattice are called lattice points or lattice sites
3.2 Structure determination of crystals by X-ray diffraction
Crystallography is the branch of science which deals with the geometry. Properties and structure of crystals and crystalline substances.
A monochromic X-ray beam is directed towards the surface of a slowly rotated crystal so as to vary the angle of incidence (). At
various angles, strong beams of deflected X-rays strike the photographic plate. The photographic plate after developing shows a
2
central spot due to primary beam and a set of symmetrically disposed spots due to deflected X-rays. Different kinds of crystals
produce different arrangements of spots.
This relation is called Bragg’s equation. Two successive planes d can be calculated from this equation. With X-rays of definite
wavelength, reflactions at various angles will be observed for a given set of planes separated by a distance d. These reflections
correspond to n=1, 2, 3 and so on and are spoken of as first order, second order, third order and so on. With each successive order,
the angle () increases and the intensity of the reflected beam weakens.
n λ=2 d sin θ
4. DESIGNATION OF PLANES IN CRYSTALS-MILLER INDICES
Planes in crystals are described by a set of integers (h, k and 𝖨) known as miller indices. Miller indices of a plane are the reciprocals of
the fractional intercepts of that plane on the various crystallographic axes. For caculation Miller indices, a reference plane, known as
parametral plane, is selected having intercepts a, b and c along x, y and z axes respectively
Thus, the Miller indices are:
a
h=
∫ ercept of the plane along x−axis
b
k=
∫ ercept of the plane along y −axis
c
I=
∫ ercept of the plane along z−axis
Consider the shaded plane ABD in fig, the
intercepts of the shaded plane along x, y
and z-axes are a/2, b and c/2, respectively.
Thus
a b c
h= =2; k= =1 ; I = =2
a/2 b c /2
The plane is, therefore, designed as (212) plane.
Some of the important planes of cubic crystals are shown below
3
The particles are very closely packed in some definite geometric pattern with very small voids. Inter-particles forces are very strong.
Partcle motion is restricted to vibratory motion only.
6. SPACE LATTICE
The geometrical form consisting only of a regular array of points in space is called a lattice or space lattice or it can be defined as an
array of points showing how molecules, atoms or ions are arranged in different sites, in three-dimensional space.
If the original appearance is repeated twice (after an angle of 1800), three (after an angle of 1200) , four times (after an angle of 900)
and six times (after angle of 600) in one rotation. These axes of symmetry are also called two-fold, three- fold, four-fold and six –
fold, respectively.
7.4 Elements of symmetry: The total number of planes, axes and centre of symmetry possessed by a crystal are termed as elements of
symmetry. A cubic crystal possesses a total of 23 elements of symmetry.
Planes of symmetry = (3+6) = 9 [fig. shown up (a) and (b)]
Axes of symmetry = (3+4+6) = 13 [fig. shown up (c), (d) and (e)]
Centre of symmetry = 1 [fig. shown up (f)]
Total number of symmetry elements = 23
8. CO-ORDINATION NUMBER
Representing atoms by spheres, the number of spheres, which are touching a particular sphere is called its co-ordination number. In
ionic crystals, the co-ordination number may be defined as the number of oppositely charged ions surrounding a particular ion.
8.1 Calculation of Number of Particles per unit cell. The number of atoms in a unit cell can be calculate keeping in view the
following points:
1
i) An atom at the corner is shared by eight unit cells. Hence, contribution of each atom present at the corner =
8
1
ii) An atom on the face is shared between two unit cells. Hence, contribution of each atom on the face =
2
iii) At atom present within the body of the unit cell is shared by no other unit cell Hence, contribution of each atom within the
body = 1
1
iv) An atom present on the edge is share by four unit cells. Hence, contribution of each atom on the edge =
4
v) No. of atom present in the face-centred unit cell
1 1
¿ × 8 (¿ corners )+ × 6 ( ¿ face centres )=4
8 2
vi) No. o atoms present in the body-centre unit cell
1
¿ × 8 (¿ corners )+ 1 ( body centre )=2
8
9. PACKING OF CONSTITUENT PARTICLES IN CRYSTALS
The packing of spheres of equal size takes place of follows:-
9.1 When the spheres are placed in a horizontal row, touching each other, an ege o the crystal is formed.
9.2 Two dimesnsional packing. The rows can be combined in two different ways:
i) The particles when placed in the adjacent
rows show a horizontal as well as vertical
alignment and form square figure. This type
of packing is called square close packing.
ii) The particles in every next row are placed
in the depressions between the particles of
the first row. This type o packing gives a
haxagonal pattern and is called hexagonal
5
close packing.
The second mode of packing (i.e., hexagonal close packing) is more efficient as more space is occupied by the spheres in this
arrangement.
In square close pacing, a central sphere is in contact with four other spheres whereas in hexagonal close packing, a central sphere is in
contact with six other spheres.
10. VOIDS
10.1 Octahedral Voids
The position in a close-packed unit cell where a foregin atom is in contact with six host atoms in the form o an octahedral is called
an Octahedral Void.
i) In FCC unit cell:
A. Octahedral void is existed at the centre of
each edge and hence there are 12 such
types of octahedral void.
B. One octahdral void is located at the centre of unit cell.
C. Contribution of each octahedral void existed
6
iii) Location of tetrahedral voids: Tetrahedral voids are presented on the body diagonals, and one body
diagonal contains two tetrahedral voids, since there are four body diagonal. Hence, there are eight tetrahedral void, each presented ¼
of the body diagonal from each corners of the cube.
iv) Radius (r) of the tetrahedral void = 0.225 R
11. TYPES OF UNIT CELLS
11.1 Simple or primitive cubic unit cell
A cubic unit cell is said to be primitive if
i) All the eight corners of the cube are occupied by the same atoms.
ii) There is no such atoms present any where in the cube except corners.
1
iii) Contribution of each atom or sphere for one unit cell is of the volume of each sphere.
8
iv) Therefore, number of effective atoms in a unit cell,
1
Z = no. of corner atoms × contribution of each atoms ¿ 8 × =1
8
v) The four spheres in bottom layer are in contact with adjacent spheres. If the centres of these four spheres are joined , we get a bottom
face of the cube and similarly we can get top layer and these top layer is in contact with bottom leyer.
vi) That is each face made by four corner atoms are in correct with each other.
7
vii) Relation between edge length (a) of cube and radius of a sphere (r)
a = 2r ∴ r=a /2.
4
Hence, volume of unit cell = a 3=(2 r )3=23 r 3=8 r 3 and volume occupied by these spheres in a unit cell = Z+ πr 3
3
viii) Packing fraction (PF): it is defined as the ratio of the volume occupied by the spheres in a unit cell to the volume of the unit cell.
Volume occupied by the same spheres∈a unit cell
PF=
Volume of unit cell
4 3
Z × πr
3
¿
a3
4
1× πr 3
3
¿ , z=no . of effective atoms∨spheres∈aunit cell
8 r3
π
¿
6
¿ 0.5236=52.36 %
ix) Percentage of vacant space = (100 – 52.36)% = 47.64%
11.2 Body-centred cubic unit cell (bcc unit cell)
A body centred cubic unit cell is said to be an ideal body centred cubic unit cell if
i) All the eight corners of the cube are occupied by the same atoms.
ii) One similar atom is also present exactly at the centre of the cubic lattice.
iii) Contribution of each atom present at eight corners for a unit cell is 1/8 of the volume of a sphere and contribution of one body
centred atom is 1×volume of a sphere.
iv) Therefore, number of effective atoms in a unit cell.
1
= no. of corner atoms × +no . of body centred atom× 1
8
1
¿ 8 × +1× 1
8
¿ 1+1
¿2
v) The four spheres in bottom layer are not in contact with adjacent spheres as well as the four spheres in top layer, but all the corners
atoms are in contact with body centred atom.
4 r= √¿ ¿
Or 4 r= √ 3 a ∴ Body diagonal of cube ¿ 4 r=√ 3 a
3
∴ r =√ a
4
3
4r
3
vi) Therefore, volume of unit cell ¿ a =
( )
√3
And volume occupied by the spheres in the unit cell
= Z × volume of a sphere
4
¿ 2 × πr 3 [Z=2 for bcc ]
3
4 3
2× πr
3
¿
4r
( )
√3
= 0.6802
= 68.02%
viii) Percentage of vacant space = ( 100−68.02 ) %=31.98 %
ix) If the atoms present at the corners and at the body centred position are of different types then the unit cell is called pseudo bcc or bcc
like.
11.3 Face centred cubic unit cell (fcc unit cell)
A face centred cubic unit cell is said to be an ideal face centred cubic unit cell if:
i) All the eight corners of the cube are occupied by the same atoms.
ii) And all the six face of the cube are also occupied by same atoms as well as that atoms which are present at each corner of cube.
iii) Contribution of each atom present at eight corners for a unit cell is 1/8 of the volume of a sphere and contribution of each face
centred atom is half of volume of a sphere.
iv) Therfore, number of effective atoms in a unit cell
1 1
= no. of corner atoms × +no . of face centred atoms ×
8 2
1 1
¿ 8 × +6 ×
8 2
¿ 1+3
¿4
v) Each corners atoms are not in contact with each other but the face centred atoms are contact with the four spheres present at the four
corners of a face.
vi) Also it is noted that all the six face centred atoms are in contact with each other.
4 r= √a 2+ a2=√ 2 a
∴ face diagonal of the cube
¿ 4 r=√ 2 a
2
∴ r =√ a
4
1
∴ r= a ,∨a=2 √ 2 r
2 √2
3
vii) Therfore, volume of unit cell ¿ a3 =(2 √ 2r ) and volume occupied by the spheres in the unit cell
¿ Z × volume of a sphere
4
¿ 4 × πr 3
3
Volume occupied by the spheres ∈theunit cell
viii) Packing fracation ( PF ) =
Volume of unit cell
4 3
4×πr
3
¿
¿¿
¿ 0.7406
¿ 74.06 %
ix) Percentage of vacant space = (100 – 74.06)% = 25.94%
9
x) If the atoms present at the corners and at the face centred positions are of different types, then the unit cell is called pseudo fcc or fcc
like.
11.4 Hexagonal primitive unit cell (hcp)
A hexagonal primitive unit cell is said to be an ideal hexagonal primitive unit cell if
i) All the six corner of hexagonal contained same type of atoms i.e., bottom and top hexagonal, both have same atom at their corners.
ii) Each of hexagonal face contains same type of atom as that of corners atom.
iii) Upper and lowear hexagonal planes are same type and it is said to be A layer.
iv) Another layer is B layer, it is completely inside the unit cell. There are three atoms, present at this layer which is completely inside
the unit cell and area in contact to each other.
v) Contribution of each atom present at the twelve corners (six corner at bottom + six corner at top) of hexagonal primitive units cell is
1/6 of the volume of a atom and for each atom present at two hexagonal face is 1/2 of the volume of a atom and contribution of each
atom present inside the hexagonal primitive unit cell is 1.
vi) Therefore, number of effective atoms in a unit cell
= no. of corner atoms ×1 /6+ ¿ no. of face centred atom ×1 /2+¿ no. of atoms inside the hexagonal primitive unit cell ×1
1 1
¿ 12× +2 × + 3× 1
6 2
¿ 2+1+3
¿6
vii) The face centred atom is in contact with six spheres present at the corners of hexagon and two corner sphere are also in contact with
each other.
viii) If let us consider a is the length of hexagonal unit cell and r be the radius of sphere then a = 2r
Volume occupied by spheres∈the unit cell
ix) Packing fraction ( PF ) =
Volume of unit cell
4 3 4
6× πr 6 × πr 3
3 3
¿ =
base area ×height
( 6 × √43 a )× ( 4 r √ 23 )
2
4 3
6× πr
3
¿ =0.74=74 %
√3 2
6 × (2 r )2 × 4 r
4 √ 3
Percentage of vacant space = (100–74) = 26%
12. RADIUS RATIO RULES
For the stability of an ionic compound, each cation should be surrounded by maximum numbr of anions and vice versa (for maximum
electrostatic forces of attraction). The number of oppositely cahrged ions surrunding each ion is called it co-ordination number.
Radius Ratio=Radius of the cation ¿ ¿
Evidently, greater is the radius ratio, the larger is the size of the cation and hence greater is its co-ordination number. The relationships
between the radius ratio and the co-ordination number and the structural arrangement are called radius ratio rules, and are given in
table
iii) For exact fitting of Zn2+¿¿ ions is the tetrahedral voids, in the close packing of S2−¿¿ ions, the ratio ¿ should be 0.225, however this
ratio is slightly large (0.40).
There are four Zn2+ ions and four S2– ions per unit cell
Thus , the number of ZnS units per unit cell is equal to 4.
Some more examples of ionic solids having zinc blende structure are CuCl, CuBr, Cul, Agl.
13.4 Structure of Calcium Fluoride or Fluorite structure
i) In CaF 2 , Cs2+ ¿¿ ions possess face centered cubic lattice. Fluoride ions occupy all the
tetrahedral voids in the lattice of Cs2+ ¿¿ ions.
ii) Each Cs2+ ¿¿ is in constant with eight
fluoride ions and each fluoride ion is in
contact with four calcium ions. Thus co–
ordination no. of Ca 2+¿ ¿ ions is 8 and that
of fluoride ions is 4. So calcium fluoride
has 8:4 co-ordination.
iii) In calcium fluoride each unit cell has
four calcium ions and eight fluoride
ions as shown below
InFe3 O 4 , Fe 3+¿¿ ions are present in the ratio 2 : 1 and may be considered as FeO. Fe2 O3. In Fe3 O 4, oxide ions arranged in ccp.
Fe2+ ¿¿ ions occupy octahedral voids while Fe3 +¿¿ ions are equally MgFe 2 O 4 also has similar structure of magnetile, in which
Mg 2+¿¿ ions are present in place of Fe2+ ¿¿ ion in Fe3 O4.
13.7 Normal Spinel Structure
1
In spinel, a mineral MgAl 2 O 4 , oxide are arranged in ccp with Mg 2+¿¿ ions occupied th of tetrahedral voids and Al3 +¿¿ occupied
8
1
of octahedral voids. Many ferites (such as ZnFe2 O 4 ¿ also possess spinel structure. These are very important magnetic materials
2
and are used in telephones and memory loops, in computers.
Magnetic also possess spinel structure. Hence divalent ions ¿ ¿ are in octahedral voids while the trivalent ions are in a set of
tetrahedral voids.
13.8 Structure of Calcium Carbide
The structure of CaC 2 is similar to that of sodium chloride in which sodium ions are replaced by calcium ions while chloride ions by
carbide ions. The carbon atoms in carbide are associated in pairs, which are aligned in parallels.
Unlike sodium chloride, the cubic symmetry is distorted in calcium carbide.
The structure of FeS2 similar to that of CaC 2, the S2units in FeS2, do not align parallel.
13.9 Structure of Titanium Dioxide (or TiO2 , Rutile Structure ¿
In rutile structure each Ti 4 +¿¿ ion is surrounded by six O2−¿ ¿ ions arranged in a distorted octahedron and each O2−¿¿ ion is
surrounded by three Ti 4 +¿¿ ions arranged in a planar triangular manner. Thus, the co-ordination numbers of Ti4+ and O2– and 6 and 3,
respectively.
The structure of titanium dioxide cannot be considered to be cubic as one of the axes is shorter than the other by 30 percent.
The brief study on some ionic cubic solids is reported in table.
13.10 Characterstic of Some Cubic Ionic Solids.
13.11 Effect of Temperature and pressure on Crystal Structure – Conversion of NaCl into CsCl Structure and Vice – versa. On
applying high pressure, NaCl structure having 6 :6 co-ordination changes to CsCl structure having 8:8 co-ordination. Similarly, CsCl
having 8 : 8 co-ordination on heating to 760 K changes to NaCl structure having 6 : 6 co-ordination. Thus increase of pressure
increases the co-ordination number whereas increase of temperature decreases the co-ordination number.
13
13.12 Examples of Some Substance having close packed structures. Examoles of some substances which crystallized in the close
packed structures are given below:-
i) Noble gases : All noble gases crystallize in ccp structure except helium, which has hcp structure.
ii) Metals Be, Cd, Co, Mg and Zn have hcp structure while Al, Ag, Au, Cu, Ni and Pt have ccp
iii) Molecular substance. Molecular substances having nearly spherical molecules have close packed arrangement. For example, solid
H2 has hcp structure while solid CH4, HCl and H2S have ccp structure
iv) Ionic substance. Most of the ionic compounds have close packed arrangement in which one type of ions (usually larger ones) form
the close packed arrangment and the other type of ions (smaller ones) occupy the voids. A few examples are given below.
ii) ZnS S2– ions (ccp) Zn2+ ions in alternate tetrahedral voids
13.13 Structure of the oxides of Iron. Iron forms three important oxides, which are FeO, Fe2 O 3 and Fe3 O 4. These compounds have
no-stoichiometric composition and are easily oxidized or reduced into each other. These aspects are explained on the basis of their
crystal structure as follows:
i) Structure of FeO. If the oxide ions ¿ ¿ form a cubic close packing with all the (100%) octahedral voids occupied by Fe2+ ¿¿ ions, we
will get perfect rock salt (NaCl) lattice. The formula of the oxide then would be FeO. However actually the oxide is found to be non-
stoichiometric with the composition of Fe0.95 O (called wustite). This structure can be explained by assuming that a small number of
Fe2+ ¿¿ ions in these octahedral voids are replaced by Fe3+ ions (of course every three Fe2+ ions would be replaced by two Fe3+ ions to
maintain electric neutrality). Consequently we get Fe deficient crystal.
ii) Structure of Fe2O3. If all the Fe2+ ions are replaced by Fe3+ ions, then as every three Fe2+ ions can be replaced by two Fe3+ ions, then
as every three Fe2+ions can be replaced by two Fe3+ ions to maintain electrical neutrality, the ratio between Fe and O will now be 2:3
and not 1:1 i.e. we get the oxide Fe2O3.
iii) Structure of Fe3O4 (magnetite). This oxide is obtained by replacing exactly two thirds of Fe2+ ions (in the structure of FeO) by Fe3+
ions. The remaining Fe2+ ions as well as 50% of the Fe3+ ions occupy the octahedral voids whereas the remaining 50% of the Fe3+ ions
occupy the tetrahedral voids.
iv) Ferrites. In the structure of Fe3O4, if Fe2+ ions are replaced by divalent cations such as Mg2+, Zn2+ etc. the compounds obtained are
called ferrites. Thus ferrites are the compounds having the general molecular formula A Fe2O4 where A is a divalent cation such as
Mg2+ orZn2+ i,e. these of Fe3O4 by divalent cation such as Mg2+or Zn2+ i.e. these are obtained by replacing Fe2+ ions in the stucture of
Fe3O4 by divalent cations. These belong to the general category of compounds having the formula AB2O4 where A is a divalent cation
and B is a trivalent cation e.g., B3+, Fe3+ or Al3+. In these compounds, divalent cation occupy tetrahedral voids whereas trivalent cations
occupy octahedral voids. This type of arrangment is called spinel structure. Most of the ferrites having spinel structure are used in
telephone as well as in memory loops of computers.
14. CALCULATION OF DENSITY OF A CUBIC CRYSTAL FROM ITS EDGE.
Knowing the edge of a cubic crystal from X – ray studies and knowing the type of crystal structure possessed by it so that the number
of particles per unit cell are known, the density of the crystal can be calculated.
14.1 For cubic crystals elements.
Suppose the edge of the unit cell = a pm
Number of atoms present per unit cell = Z
Atomic mass of the element = M
∴ Volume of the unit cell ¿ ¿
Mass of the unit cell
Density of the unit cell ¿
Volume of theunit cell
Mass of the unit cell = Number of atoms in the unit cell × Mass of each atom ¿ Z × m
Atomic mass M
Where m= =
'
Avogadro s number N 0
14
Z × M / No
∴ Density of the unit cell =
a 3 ×10−30
i.e.
Z ×M
ρ= 3 −30
g /cm3
a × N 0 ×10
14.2 For cubic crystal of ionic compounds. The formula is the same except the now Z is the number of formula units present in one
unit cell and M is formula mass.
Z×M
Note. In terms of SI units, M is kg mol–1, a is in meters, than ρ 3
kg m−3
a × No
15. SOME IMPORTANT RELATIONSHIPS
d=a 3 a a 3 a
r =√ a
d=
√2
a
¿ 0.866 a
d=
√2
=0.707 a r=
2 4
¿ 0.433 a
r=
2 √2
¿ 0.3535 a
Let radius of the atom in the packing = r, edge length of the cube = a, volume of the cube V =a3
4 vz 3
Volume of the atom (spherically) v= π r 3 z , thn packing density ¿ = 3
3 Z a
1. Simple cubic a 4 a 3
π
r
2 π
3 2 () 6
=0.52
A few examples of ionic compound exhibiting Schottky defect are NaCl, KCl, KBr and CsCl.
Effect on density. As the number of ions decreases as a result on this defect, the mass decreases whereas the volume remains the
same. Hence the density of the solid decreases.
17.1.2 Frenkel defect. If an ion is missing from
Its lattice site (causing a vacancy or
a hole there) and it occupies the interstitial
site, electrical neutrality as well as the
stoichiometry of the compound are
maintained. This type of defect is called
Frenkel defect. Since cations are usually
smaller, it is more common to find the
cations occupying interstitial sites.
The above two defects are called intrinsic defects or thermodynamic defects.
The Frenkel defect in which one cation is called missing from the lattice site and is occupying the interstitial site is shown in fig.
Types of compounds exhibiting Frenkel defects. This type of defect is present in those compounds, which have
i) low co-ordination number and
ii) larger difference in the size of cations and anions
A few examples of ionic compounds showing this defect are AgCl, AgBr, Agl, ZnS etc.
Effect on density. Since no ions are missing from the crystal as a whole, therefore density of the solid remains unchanged.
17.1.3 Some other consequences of Schottky and Frenkel defects
Solids having these defects conduct electricity to small extent. This is because if an ion moves from its lattice site to occupy a ‘hole’ it
creates a new ‘hole’. In which way a hole moves across the crystal, which as a result moves a charge in the opposite direction.
Due to presence of holes, the stability (or the lattice energy) of the crystal decreases. In Frenkel defect, similar charges come closer.
This results in the increase of dielectric constant of the crystals.
17.1.4 Differnece between Shottky and Frenkel defects. The main points of difference are listed below
i) It is due to equal number of cations and anions missing from the i) It is due to the missing of ions (usually cations) from the lattice
lattice sites. sites and thse occupy the interstitial sites.
ii) This result in the decrease in the density of the crystal. ii) It has no effct on the density of the crystal.
iii) This type of defect is found in highly ionic compounds with iii) This type of defect is found in crystals where the difference in
high co-ordination number and having cations and anions of the size of cations and anions is very large e.g. AgCl, AgBr,
similar sizes e.g., NaCl, CsCl etc. ZnS etc.
16
17.2 Non – Stoichiometric Defects. If, as a result of the imperfections in the crystal, the ratio of the caions to the anion becoms different
from that indicatd by the idea chemical formula, the defects are called non – stoichiometric defects.
These defects result in either excess of the metal atoms or excess of the non-metal atoms (or deficiency of the metal atoms). These can
occur as follows
17.2.1 Metal excess. This may occur in either of th following two ways:-
i) By anion vacancies. A negative ion may be missing form its lattice site, leaving a hole which is occupies by an electron, thereby
maintaining the electrical balance. The electrons thus trapped in the anion vacancies are called F – centres F – centres because they
are responsibl for imparting colour to the crystals (F– Farbe which is a German word for ‘colour’).
For example, which NaCl is heated in an atmosphere of Na vapour, the excess of Na atoms deposit on the surface of NaCl crystal. Cl –
ions then diffuse to the surface where they combine with the Na atoms, which become ionized by losing electrons.
This defect is similar to Schottky defect and is found in crystals having Schottky defects.
ii) By the presenc of extra cations
in the interstitial sites. Metal excess
may also be caused by an extra cation
occupying the interstitial site. Electrical
neutrality is maintained by an electron
present in another intrstitial sit. This
defct is similar to Frenkel defect and
is found in crystals having Frenkel defects.
For example, when ZnO is heated, it loses oxygen and turns yellow due to
following reaction.
1 −¿ ¿
2+ ¿+ O2 +2 e ¿
ZnO → Zn 2
The excess of Zn2+¿¿ ions thus formed get trapped into the vacant interstitial sites and the electrons in the neighbouring interstitial
sites.
Crystals with either type of metal excess defects contain some free electrons. Hence such materials acts as semi-conductors.
17.2.2 Metal Deficiency. This defect occurs when the metal shows variable valency i.e. for transition metals. The defect usually occurs
due to the missing of a cation from its lattice site and the presence of the cation having higher charge (e.g., +2 instead of +1) in th
adjacent lattice site. Examols include FeO, FeS and NiO.
17.3 Impurity Defects. These defects arise when foreign atoms are present at the lattic site (in place of host atoms) or at the vacatn
interstitial sites. In the formers cas, we get substitutional solid solutions while in the latter case, we get interstitial solid solutions. The
formation of the former depends upon the electronic structure of the impurity while that of the latter on the size of the impurity.
17.3.1 Introducing impurity defect in covalent
solids. For example group 13 elements such P
and As enter Ge or Si of group 14
substitutionally. The group 15 elements have
one excess valence electron (compared to Si or
Ge) after formed by group 14 elements. The
Excess electrons give rise to electrical
conduction.
17
A group 13 element, which has only three valence electrons forms an electron –
Deficient bond or a hole. Such hols can move across the crystal giving rise to electrical conductivity. Thus impurity – doped * Si and
Ge and semi – conductors whose conductiveiy increases with increasing temperature. This is unlike metals whose conductivity
decreases with increase of temperature.
Group 14 elements doped with group 15 elements are called n – type semi – conductore, the symbol ‘n’ indicating that negative
charge flows in them. Group 14 elements doped with group 13 elements are called p – type semiconductors, the symbol ‘p’ indicating
the movement of positive hole through the lattice.
17.3.2 Introducing impurity defect in ionic solids. In case of ionic solids, the impuritis are introudced by adding impurity of ions. If
the impurity ions are in a different valence state from that of the host ions, vacancies are created. For example, if molten NaCl,
containing a little SrCl2 as impurity is allowed in cool, in the crystal of NaCl formed, atsome lattice sites Na + ions are substituted by
Sr2+ ion. For every Sr2+ ion. For every Sr2+ ion thus introduced, two Na+ ions are removed to maintain electrical neutrality. One of thse
lattice sites is occupied by Sr2+ ion and the other remains vacant. These vacancies result in th highr electrical conductiveiy of the solid.
18. PROPERTIES OF SOLIDS
The three main properties of solids which depend upon their structure and composition are briefly described below:-
18.1 Electrical Properties. Based on their conductivity, solids can be divided into three categories:
i) Conductors. The solids through which electricity can flow to a large extent are called conductors. They are further classified as
metallic conductors and electrolytic conductors. In the metallic conductors, the flow of electricity is due to flow of electrons
(electronic conductors) without any chemical change occuring in the metal. In case of electrolytic conductors like NaCl, KCl etc., the
flow of electricity takes place to a good extent only when they are taken in the molten state or in aqueous solution. The flow of
electricity is due to flow of ions. However, in the solid state they conduct electricity only to a small extent which is the due to the
presenc of defects (holes, electrons etc).
ii) Insulators. The solids which almost do not allow the electricity to pass through them are called inculators e.g. S, P, lastic, wood,
rubber, etc.
iii) Semi – conductors. The solids whose conductivity lies between those of metallic conductors and inculators are called semi-
conductors. The electrical conducativiey of semi – conductors and insulators is due to the presence of impurities and defects. Their
conductivity increases with increase in temperature as the defects (such as holes) increase with increase of temperature.
Similar variation is observed among the sulphides of transition elements.
18.2 Magnetic Properties. Based on the behaviour in the external magnetic field, the substances are divided into different categories as
explained below:-
i) Diamagnetic substances. Substances, which are weakly repelled by the external magnetic field are called diamagnetic substances e.g.
TiO2, NaCl, benzene etc. the property thus exhibited is called diamagnetism. This property is shown only by those substances which
contain fully – filled orbitals i.e. no unpaired electrons is present. the magnetic moment possessed by an electron with spin in one
direction is cancelled by that with spin in the opposite direction.
ii) Paramagnetic substances, Substances, which are attracted by the external magnetic field are called paramagnetic substances. The
property thus exhibited is called parmagnetism. This property is shown by those substances whose atoms, ions or molecules contain
unparied electrons e.g. O2, Cu2+ , Fe3+ etc. These substances, however, lose their magnesium in the absence of the magnetic field .
iii) Ferromagnetic substances. Substances which show permanent magnetism even in the absence of the magnetic field are called
ferromagnetic substances, e.g., Fe; Ni, CO, CrO2 show ferromagnetism. Such substances remain permanently magnetized, once they
have been magnetized. This type of magnetism areises due to spontaneous alignment of magnetic moments due to unpaired electrons
in the same direction, as shown in fig. this is a case of large amount of paramagnetism.
iv) Anti-ferromagnetism substances. Substances which are expected to possess paramagnetism or ferromagnetism on the basis of
unpaired electrons but actually they possess zero net magnetic moment are called anti-ferromagnetism is due to the presence of equal
number of magnetic moments in the opposite directions as shown in fig.
v) Ferrimagnetic substances.
Substances which are expected to
possess large magnetism on the basis
of the unpaired electrons but actually
have small net magnetic moment are
called ferrimagnetic substance e.g.,
Fe3 O4 , ferrites of the formula M 2+¿ Fe O
2 4 ¿
18
18.3 Dielectric Properties. Insulators do not conduct electricity because to the electrons present in them are held tightly to the
individual atoms or ions and are not free move. However, when electric field is applied, polarization takes place because nuclei are
attracte to one side and the electron cloud to the other side. These newly formed dipoles may align themselves in an ordered manner
so that such crystals have a net dipole moment. Such polar crystals show the following interesting electrical properties:
dispersion forces these forces are attractive is nature and the interaction energy due to this is propotional to
( r1 ) .
6 Thus, these forces
1
are important at short distance
( )
r6
Thus, these forces are important at short distances (≃ 500 pm ¿ this force also depends on the
polarisabiity of molecule.
19.3 Dipole-Dipole Forces: These type of forces occur between molecules having permanent electric dipole. In HCl bond between H
and Cl is formed by sharing of electrons, but shared electron pair is near to chlorine because of its higher electronegativeiy
compaired to H-atom. Thus bond formed is said to be polar and a partial charge is developed on both atoms. There is interaction of
the dipole with HCl molecule, and interaction energy is also proportional to 1/r6 where r is the distance between the polar molecules.
19.4 Dipole-induced Dipole Forces : Attractive forces are operative not only between the two molecules with permanent dipoles but
also between a molecule having a dipole moment and a molecule without any dipole moment like CH4. As the size of the atom
increases the influence of the electric dipole on it also increases. The electron could of the molecule is deformed in the electric field
of the permanent dipole. This causes a shift in the centre of gravity of the negative charge relative to the nuclear charge and leads to
the information of an induced dipole moment. The interaction energy is also proportional to 1/r 6 and also depends upon (1) dipole
moment of the permanent dipole and (2) the polarizability of the second molecule. molecules of larger size have higher
polarizability. Interaction between tow dipolar molecules also includes additive dipole-dipole induced interactions.
20. SUPERCONDUCTIVITY
When any material loses its resistance for electric current, then it is called superconductor. Kammerlingh Onnes (1913) observed
this phenomenon at 4 K in mercury. The materials offering no resistance to the flow of current at very low temperature (2-5 K) are
called superconducting materials and phenomenon is called superconductivity.
Examples are :
i) Nb3Ge alloy (before 1986)
ii) La1.25Ba0.15CuO4(1986)
20
Distance nm,
I −¿¿ Cl–
Suggest why there is such a small difference in internuclear distance between LiI and NaI compound to that between LiCl and
NaCl.
Examample:9 Suggest the probable structure of the unit cells of the following:
Species r+ r–
Example: 10 The redius of calcium ion is 94 pm and of an oxide ion is 146 pm. Predict the crystal structure of calcium oxide.
Example:11 The diffraction of barium with X– radiation of wavelength 2.29 Å gives a first –order reflection at 30 0. What is the
distance between the diffracted planes?
Example:12 The length of the unit cell edge of a ‘bcc’ lattice metal is 352 pm. Calculate radius of the atom of the metal.
Example:13 The composition of a sample of wustite is Fe0.93O. What percentage of the iron is present in the form of Fe(III)?
Example:14 If NaCl is doped with 10–3 mol% of SrCl2, calculate the concentration of cation vacancies.
Example:15 Ice crystallises in a hexagonal lattice. At the low temperature at which the structure was determined, the lattice
constants were a = 4.53 Å and b = 7.4 Å. How many H2O molecules are contained in a unit cell? d(ice) = 0.92 g/cm3.
Example:16 Calcium crystallises in a face-centred cubic unit cell with a = 0.556 nm. Calculate the density, if
i) It contained 0.1% Frankel defects,
ii) It contained 0.1% Schottky defects.
Example:17 Zeolite is not a silicate of:
a) Al b) Hg
c) Na d) Na and Al containing X number of H2O moles.
Example:18 Potassium has a bcc structure with nearest neighbour distance 4.52 Å. Its atomic weight is 39. Its density will be:
a) 454 kg m–3 b) 804 kg m–3
–3
c) 852 kg m d) 908 kg m–3
Example 19 In a crystal, th atoms arelocated at the position of
a) maximum P.E. b) minimum P.E.
c) zero P.E. d) infinite P.E.
Example :20 In the crystalline state of an ionic comound MX of a metal M. having cations and anions of radius r M and rX
respectivel, the co-ordination number of M will be 4 if the value of rX/rM and rX respectively, the co-ordination number of M will
be 4 if the value of rX/rM is between:
a) 1 and 1.4 b) 1.4 and 2.4
c) 2.4 and 4.6 d) 4.6 and 5.6
Example:21 The second order Bragg diffracation of X–ray with λ=1.0 Å from a set of parallel planes in metal occurs at an angle
600. The distance between the scattering planes in the crystal is
a) 0.57 Å b) 1.00 Å
c) 1.15 Å d) 2.00 Å
Example:22 The number of unit cells in 119 g of KBr is nearly:
a) 6 ×10 20 b) 3 ×1022
c) 1.5 ×1023 d) 0.5 ×1024
Example:23 In aluminium oxide, the oxide ions (O2–) are arranged in hexagonal close paxked (hcp) arrangement and the
aluminium ions occupy 2/3 of octahedral voids. The formula of the oxide is
22
a) AlO b) Al2O3
c) Al3O2 d) AlO2
Example:24 A metallic element crytallilses in simple cubic lattic. Edge length of the unit cell is 3 Å. The density of the element is
8g/cm3. Number of unit cells in 108 g of the metal is:
a) 2 ×1024 b) 5 ×1023
c) 2.7 ×10 22 d) 1.35 ×1020
Example :25 A binary solid (A+B–) has a zinc blend structure with B–ions forming the lattice and A+ ions occupying 25%
tetrahedral sites. The formula of the solid is:
a) A B b) AB2
c) A2B d) AB4
Example:26 Titanium crystallises in a face centred cubic lattice. It combines with carbon or hydrogen to form carbide or hydride
in which carbon occupies octahedral voids whil hydrogen occupis tetrahedral voids. The formula of carbide and hydride of
titanium are:
a) TiC2, TiH b) TiC2, TiH2
c) TiC, TiH2 d) Ti3C, TiH2
Example :27 Sodium crystallizes in bcc lattice with edge length = 4.26 Å. The radius of the sodium atom is:
a) 8.16 Å b) 6.81 Å
c) 2.94 Å d) 1.86 Å
Multiple choice questions (with more than one correct choice)
Example:28 In Na2O structure
a) Na+ ions occupy all the tetrahedral holes
b) O2– ions constitute ccp.
c) O2– ions constitute ccp and Na+ ions occupy 50% of tetrahedral and 100% octahedral holes
d) Na+ ions constitute ccp and O2– ions occupy half of octahedral holes
Example:29 For the structure of zinc blende, the correct statement is/are
a) S2– ions form hcp
b) S2– ions form ccp
c) S2– ions occupy octahedral sites and Zn2+ ions tetrahedral sites
d) Both Zn2+ and S2– ions occupy tetrahedral sites.
Example:31 In a AB unit crystal of NaCl types assuming Na+ forming FCC
a) the nearest neighbour of A+ is 6 B– ion
b) the nearest neighbour of B– is 6 A+ ion
c) the second neighbour of A+ is 12 A+