Anda di halaman 1dari 23

SOLID STATE

By MUKESH SHARMA ,DPS JODHPUR


Introduction :
Solids are characterised by incompressibility, rigidity and mechanical strength. This indicates that the molecules,
atoms or ions that make up a solid are closely packed, they are held together by strong cohesive forces and
cannot move at random. Thus, in solids we have well ordered molecular arrangements.
Moreover solids are also characterised by a definite geometrical arrangement. Substances which satisfy all the
characteristics of a solid except the definite geometrical arrangement are called amorphous substances (e.g.
glass, rubber etc.).The definite geometrical arrangement of atoms, molecules or ions in a solid extends over the
entire structure of the solid. This is termed as long range order.
Classification of Solids
is classified according to the regularity with which atoms or ions are arranged
Crystalline Solids atoms are organized in a well ordered and regular geometrical pattern
Amorphous Solids atoms are organized in a disordered and irregular geometrical pattern
.. Although amorphous solids possess rigidity, incompressibility, refractive index etc., but do not have
Difference B/W Crystalline and Amorphous Solids:
Cause of anisotropy in crystals For instance, atoms along the edge of given
structure are more separated than along the face
diagonal. This causes anisotropy
Types of crystalline solids
Space Lattice and Unit Cell: A crystal can be considered to be generated
from the repetition of some basic unit of pattern such as atoms, molecules or ions. In other words, a well
ordered and regular arrangement of constituents in the three dimensional space is called crystal lattice. A space
lattice can be subdivided into a number of small cells known as unit cells. It can be defined as the smallest
block from which entire crystal can be built up by its translational repetition in three dimensions.
Unit cell: is the smallest unit of a space lattice which repeats itself to form the lattice.
In other words space-lattice is formed by face to face packing of unit cells
Characterizations of an unit cell
1. Axial property:
1 angle b/w two adjacent faces (sides)
Length of sides (edges)
2. Position of lattice point (constituent particle)
Types of Lattices
Seven Crystal Systems: The seven crystal systems are given below.
Crystal System Bravais Lattices
Parameters of Unit Cell
Example
Intercepts Interfacial angle
1. Cubic Primitive, Face Centered, Body
Centered = 3
a = b = c o = | = = 90
o
Pb,Hg,Ag,Au
Diamond, NaCl, ZnS
2. Orthorhombic Primitive, Face Centered, Body
Centered, End Centered = 4
a = b = c o = | = = 90
o
KNO
2
, K
2
SO
4
3. Tetragonal Primitive, Body Centered =2 a = b = c o = | = = 90
o
TiO
2
,SnO
2
4. Monoclinic Primitive, End Centered = 2 a = b = c o = = 90
o
,
| = 90
o
CaSO
4
,2H
2
O
5. Triclinic Primitive = 1 a = b = c o = | = = 90
0
K
2
Cr
2
O
7
,
CaSO
4
5H
2
O
6. Hexagonal Primitive = 1 a = b = c o = | = 90
0
,
= 120
o
Mg, SiO
2
, Zn, Cd
7. Rhombohedral Primitive = 1 a = b = c o = = 90
o
,|= 90
o
As, Sb, Bi, CaCO
3
Total = 14
Seven Crystal Systems and Fourteen Bravais Lattice
Simple
TETRAGONAL
Body Centred
c
a
a
Simple
End Centred
MONOCLINIC
c
a
b
b
a
a
a
Simple Face Centred Body Centred
CUBIC
Simple End Centred
ORTHORHOMBIC
c
a
b
Body Centred Face Centred
Types of cubic unit cells [cubic bravaise lattice]
1 Primitive Unit Cells: In a primitive unit cell, the same type of particles are present at all the corners
of the unit cell.
However, it has been observed that the particles may be present not only at the corners but
also at some other special positions within the unit cells. Such unit cells are called nonprimitive unit
cells. There are three types of nonprimitive unit cells as follows:
2 Face Centred: When atoms are present in all 8-corners and six face centres in a cubic unit cell then
this arrangement is known as FCC.
3 Body Centred: When atoms are present at 8 corners as well as in the body centre in a cubic unit cell
then this arrangement is known as BCC.
Calculation of number of effective atoms [Z] in a Unit Cell
.primitive BCC FCC
In a crystal atoms located at the corner and face center of a unit cell are shared by other cells and only a portion
of such an atom actually lies within a given unit cell.
i) A point that lies at the corner of a unit cell is shared among eight unit cells and therefore, only one
eighth of each such point lies within the given unit cell.
ii) A point along an edge is shared by four unit cells and only onefourth of it lies within any one cell.
iii) A facecentred point is shared by two unit cells and only one half of it is present in a given unit cell.
iv) A bodycentred point lies entirely within the unit cell and contributes one complete point to the cell.
Close Packing in Crystals
RHOMBOHEDRAL
a
a a
a
a
c
b
a
b g
TRICLINIC
a
120o
c
a
HEXAGONAL
In order to understand the packing of the constituent particles in a crystal, it is assumed that these particles are
hard spheres of identical size. The packing of the crystals is done such that they occupy the maximum available
space and hence the crystal has maximum density.
There are two common ways in which spheres of each size can be packed as shown below:
Arrnagement (I) Arrnagement (II)
In arrangement (I), the spheres are packed in such a
way that their centres are at the centres of an
equilateral triangle. Each sphere is surrounded by six
other similar spheres. This arrangement is called
hexagonal close packing.
This arrangement can be extended in three dimensions by adjusting spheres on the top of hollows or voids of
the two dimensional layers.
In the base layer shown in fig. (a), the spheres are marked as A and the two types of voids B/W the spheres are
marked as a and b. The efficient way of placing the spheres in second layer is to place them in the a voids
of the first layer, the b voids remaining unoccupied.
There are two types of voids in the second layer i.e. c and d. The a and b voids in the first layer are
triangular while only c voids of the second layer are triangular. The d voids are combination of two
triangular voids (one each of first and second layer) with the vertex of one triangle upwards and the vertex of
other triangle downwards.
The void surrounded by four spheres and placed at an angle of 109 28' is known as tetrahedral voids.
Now, there are two ways to build up the third layer:
i) When the third layer is placed over the second layer so as to cover the tetrahedral or c voids, a
threedimensional closest packing is obtained where the spheres in every third layer are vertically
aligned to the first layer. This arrangement is called ABAB., pattern or hexagonal (HCP) close
packing (calling first layer as A and second layer B).
ii) When the third layer is placed over the second layer such that the spheres cover the octahedral or d
voids, a layer C different from A and B is formed. This pattern is called ABCABCpattern or cubic
close packing (CCP).
A A A A
A
A A A A A
A A A A
a
b b b b
b b b
a a
a a a a
Fig. (a)
A A A A
A
A A A A A
a
d
c
a
a a a a
d d
a
c
Fig. (b)
In both HCP and CCP methods of packing, a sphere is in contact with six other spheres in its own layer. It
touches three spheres in the layer above and three spheres in the layer below. Thus a sphere is in direct contact
with 12 other spheres. In other words, the coordination number of that sphere is 12. Coordination number is the
number of closest neighbours of any constituent particle.
The HCP and CCP arrangements can be also be shown as below.
Hexagonal closest packing of spheres: (a) normal and
(b) exploded view
a
b b
(a)
(b)
Fig. (X): Cubic closest packing of spheres: (a) generation of unit from closestpacked layers,
and (b) rotation to show cubic symmetry
(a)
(b)
BY MUKESH SHARMA ,DPS JODHPUR
FEATURES OF HEXAGONAL CLOSE PACKING
this is an A-B-, A- B type packing in which every 3
rd
layer is similar to 1
st
layer in pattern of
packing
it is resulted from packing of 3
rd
layer point in tetrahedral void of 2
nd
layer
no of atom [point] in one unit cell is 6
co . no . of a lattice point[atom] is 12
6 from same plane and 3 from above and 3 from below the plane
packing efficiency is 74%
CUBIC CLOSE PACKING
this is an A-B-C, A- B C type packing in which every 4
th
layer is similar to 1
st
layer in pattern
of packing
it is resulted from packing of 3
rd
layer point in octahredral void of 2
nd
layer
no of atom [point] in one unit cell is 4
co . no . of a lattice point[atom] is 12
4 from same plane and 4 from above and 4 from below the plane
packing efficiency is 74%
Calculation of Spaces occupied i.e. Packing Fraction
a) In a simple cubic
Edge length = a
Radius of sphere = r
As the spheres are touching each other, a = 2r
No. of spheres per unit cell =
1
8
8
=1
Volume of the sphere =
3
4/ 3 r t , Volume of the cube = a
3
=
3 3
(2r) 8r =
fraction occupied (or packing fraction) =
3
3
4
r
3
8r
t
= 0.524 % occupied = 52.4%
b) In face centred cubic
PR = 4r
In right angled triangle PQR
PR = = = 4r
4
a r
2
=
Volume of the unit cell = a =
3
3
4 32
r r
2 2
| }
=
]
\
No. of spheres in the unit cell =
1 1
8 6
8 2
+ = 4
Volume of 4 spheres =
3 3
4 16
4 r r
3 3
t = t
Fraction occupied (or packing fraction) =
3
3
16
r
3
32r
2
t
= 0.74 or % occupied = 74%
c) In body centred cubic: The atom at the body centre centre
touches the spheres at the corners,
Body diagonal, PS = 4r
Face diagonal PR =
2 2
PR QR + = 2a
and Body diagonal PS =
2 2
PR RS + =
2 2
2a a 3a + =
Now, 3a 4r = a =
4
r
3
, Volume of unit cell = a
3
=
3
64
r
3 3
No. of spheres per unit cell =
1
8 1 1
8
+
= 2
Volume of two spheres =
3 3
4 8
2 r
3 3
t = t
Fraction occupied (or packing fraction) =
3
3
8
r
3
64
r
3 3
t
= 0.68 or % occupied = 68%
a
r
2r
r
a
a
B
C
a
2 2
PQ QR +
2 2
a a 2a + =
2a
4r
a
a
a
P
Q
S
R
Hexagonal Close Packing: Each corner atom would be
common to 6 other unit cells, therefore their contribution to one unit
cell would be 1/6. Total number of atom in 1 hcp unit cell =
12
6
(from 12 corners) +
2
2
(from 2 face centred +
3
1
(from body centre)
ABCD is the base of hexagonal unit cell
AD=AB=a. The sphere in the next layer has its centre F vertically above E it touches the three spheres whose
centres are A,B and D.
Hence FE =
h
2
=
2
2
2r
(2r)
3
| }

]
\
The height of unit cell (h) =
2
4r
3
The area of the base is equal to the area of six equilateral triangles, =
2
3
6 (2r)
4
. The volume of the unit cell =
2
3 2
6 (2r) 4r
4 3
.
Therefore,
PF =
3
2
4
6
r
3
3 2
6 (2r) 4r
4 3

~

0.74; VF ~ 0.26 BY MUKESH SHARMA ,DPS JODHPUR
Type of Lattice point Contribution to one unit cell
Corner of cube 1/8
Edge centre of cube 1/4
Facecenter of cube 1/2
Body Center of cube 1
Type of Lattice point Contribution to one unit cell
Corner of Hexagonal unit cell 1/6
Facecenter of 1/2
Body Center of cube 3
Edge centre of hexagonal [only voids] 1/3
C
B
a
A
r
D
G
E
a
A
F
h/2
3 / a
E
a 2r =
c
Type of
UNIT
CELL
Lattice
point
Effective no. Atoms
[Z]
Coordinatio
n number
Relation
b/w a and
r
Packing
effeicency
Atoms in
contact
Primitive 8 [1/8X8]=1 6 2r =a 52 On
corner
Body
centred
9 [1/8X8]+[1X1]=2 8
4r=
68 On body
digonal
Face
centred
14 [1/8X8]+[1/4 X12]=4 12
4r=
74 On face
digonal
Hexagonal
primitive
17 [1/6X12]+[1/2X2]+3=6 12 Shortest
a=2r
74 In
hexagonal
plane
Different distances
Distance B/W nearest neighbour in primitive unit cell [two corner atom ]
2r =a
Distance B/W 2
nd
nearst neighbour in primitive unit cell [two face diagonal atom ]
Distance B/W 3
rd
nearst neighbour in primitive unit cell [twocube diagonal atom ]
Distance B/W nearest neighbour in FCC [corner to face cetre atom]
2r=
Distance B/W nearest neighbour in BCC [corner to body cetre atom] =
DistanceB/W 1
st
and4
th
layer of FCC [corner to corner on body diogonal]
DistanceB/W1
st
and2
th
layerofFCCanytwosuccessivelayer
Distance B/W atom and tetrahedral void in FCC
Distance B/W octahedral void and tetrahedral void in FCC
Distance B/W atom and octahedral void in FCC
BY MUKESH SHARMA ,DPS JODHPUR
Illustration 1: A solid has a cubic structure in which X atoms are located at the corners of the cube, Y atoms
are at the cube centres and O atoms are at the edge centres. What is the formula of the
compound?
Solution: Atoms of X are present at all the eight corners of the cube. Therefore, each atom of X at the
corner makes 1/8 contribution towards the unit cell.
Number of atoms of X per unit cell =
1
8 1
8
=
Y atom is present at the body centre, thus contribution of Y towards unit cell
= 1 1 = 1
O atom is present at each of the edge centre (number of edges of cube = 12)
And each O atom present at edge centre will make 1/4 contribution towards the unit cell.
The number of O atoms per unit cell =
1
12
4
= 3
The formula of the compound is, therefore XYO
3
Illustration 2: Potassium crystallizes in a body centred cubic lattice. What is the approximate number of unit
cells in 4.0g of potassium? Atomic mass of potassium = 39.
Solution: There will be eight atoms at corners of the cube and one atom at the body centre.
Number of atoms per unit cell =
1
8
8
+ 1 1 = 2
Number of atoms in 4.0g of potassium =
23
4
6.023 10
39

Number of unit cells in 4.0g of potassium =
23
4 6.023 10
39 2

= 3.09 10
22
IQ 1:
In a solid, oxide ions are arranged in ccp. One sixth of the tetrahedral voids are occupied by the cations A
while one third of the octahedral voids are occupied by the cation B. What is the formula of the compound?
Voids and Radius Ratio Rules
Octahedral void tetrahedral void
Radius Ratio Rules: The structure of many ionic solids can be accounted by considering the relative sizes
of the cation and anion, and their relative numbers. By simple calculations, we can work out as how many ions
of a given size can be in contact with a smaller ion. Thus, we can predict the coordination number from the
relative size of the ions.
Calculation of some limiting radius ratio values
a) Coordination Number 3: The adjacent figure shows the
smaller positive ion of radius r
+
in contact with three larger
anion of radius r

.
In this figure, AB = BC = AC = 2r

BE = r

BD = r
+
+ r

ZABC = 60 ZBDC = 120 or ZBDE = 60


ZDBC = 30
A
B C
E
D
BD =
BE
cos30
r
+
+ r

=
r r
cos30 0.866

=

= 1.155r

r+ = 1.155r

r+ = 0.155r

r
r
+

= 0.155
b) Coordination Number 4: (tetrahedron)
Angle ABC is the tetrahedral angle
Z ABC = 109 28 Z ABD =
1
2
(109 28') = 54 44'
sin (ZABD) = 0.8164 =
AD r
AB r r

+
=
+

r r 1
r 0.8164
+

+
= = 1.225
r
r
+

= 0.225
A
B
C
D
c) Coordination Number 6: (Octahedron): A cross
section through an octahedral site is shown in the adjacent
figure and the smaller positive ion touches six larger negative
ions. (Only four negative ions are shown in the figure but there
is one sphere above and the below the plane of paper).
In this figure
AB = r
+
+ r

and BD = r

ZABC = 45 cos(ZABD) = 0.7071 =


BD r
AB r r

+
=
+
Solving, we get
r
r
+

= 0.414
A
B
C
D
Limiting radius ratio
r
r
+

| }
]
\
Coordination
number
Shape Examples
< 0.155 2 Linear BeF
2
0.155 0.225 3 Trigonal planar B
2
O
3
0.225 0.414 4 Tetrahedral ZnS, SiO
4
4
0.414 0.732 4 Square planar PtCl
4
2
0.414 0.732 6 Octahedral NaCl
0.732 0.999 8 Body centred cubic CsCl
Illustration 3: Iron crystallises in a body centred cubic structure. Calculate the radius of Fe atom if edge
length of unit cell is 286 pm.
Solution: Edge length, a = 286 pm
For BCC, radius of atom, r =
3
a
4
=
3
286
4
=
1.732 286
4

= 123.8 pm
IQ2:
Define coordination number, what is the coordination number of each sphere in
a) Cubic closepacked structures
b) Bodycentred closepacked structures
c) c) Hexagonal closepacked structures
Calculation of density of a cubic crystal from its edge: If we know the type of crystal
structure possessed by the cubic crystal, so that the number of particles per unit cell are known and the edge
length for it is known by XRay studies, the density of the crystal can be determined.
Case I: For cubic crystals of elements:
Let the edge of the unit cell = a pm
No. of atoms present per unit cell = Z
Atomic mass of the element = M
Volume of the unit cell = (a pm)
3
= a
3
pm
3
= a
3
10
30
cm
3
Density of the unit cell,
=
Mass of the unit cell
Volume of the unit cell
a
=
, ) , )
3 30
No. of atoms in its unit cell Mass of each atom
a 10

=
3 A
3 30
M
Z
N
g/ cm
a 10

(N
A
Avogadros number) =
3 30
A
Z M
N a 10


g/cm
3
Case II: For cubic crystals of ionic compounds: Here, Z is the number of formula units present in one
unit cell and M is the formula mass. The formula will remain the same viz.
Illustration 4: A facecentred cubic element (atomic mass 60) has a cell edge of 400 pm. What is its density?
Solution: For the facecentred cubic, Z = 4
=
3
3 30
0
Z M
g/ cm
a N 10


=
3 23 30
4 60
(400) (6.02 10 ) 10


= 6.23 g/cm
3
IQ3:
The unit cell in a crystal of diamond belongs to a cubic crystal system but doesnt correspond to the Bravais
lattice. The volume of unit cell of diamond is 0.0454 nm
3
and the density of diamond is 3.52 g/cc. Find the
number of carbon atoms in a unit cell of diamond?
Classification of Ionic Structures
Simple ionic compounds are of the type AB or AB
2
where A and B represent the positively and negatively
charged ions respectively. (In any solid of the type A
x
B
y
, the ratio of coordination number of A to B would be
y :x.
Structures of Type AB: Ionic compounds of the type AB means compounds having the positively and
negatively charged ions in the ratio 1:1. These compounds can have following three type of structures.
1. Rock salt (NaCl) type
2. Cesium chloride (CsCl) type
3. Zinc blende (ZnS) type
3
30
A
Z M
g./ cm
N 10

1. Rock Salt (NaCl) type Structure: Cl

is
forming a FCC unit cell in which Na+ is in the octahedral
voids. The coordination number of Na+ is 6 and that of
Cl

would also be 6. Moreover, there are 4 Na+ ions and


4 Cl

ions per unit cell. The formula is Na


4
Cl
4
i.e. NaCl.
Other examples for this type of structure are all halides of
alkali metals except CsCl and all oxides of alkaline earth
metals except BeO.
Na
+
Cl
-
2. Zinc Blende Structure (ZnS): Sulphite ions are
face centred and zinc is present in alternate tetrahedral
voids. Formula is Zn
4
S
4
, i.e. ZnS. Coordination number
of Zn is 4 and that of sulphide is 4. Other substance that
exists in this kind of a structure is BeO.
3. Cesium Chloride (CsCl) type structure:
CsCl has bodycentred cubic (bcc) arrangement. Each
Cs
+
ion is surrounded by 8 Cl

ions and each Cl

ion is
surrounded by 8 Cs
+
ions i.e. this structure has 8:8
coordination. A unit cell of CsCl consists of only one
unit of CsCl i.e. One Cs
+
ion and one Cl

ion. Few
examples of compounds having CsCl structure are CsBr,
CsI, CsCN, TlCl, TlBr, TlI and TlCN.
Cs
+
ion surrounded b
by 8 Cl
-
ions
Structure of Ionic Compounds of the Type AB2: These are the ionic compounds having
cations and anions in the ratio 1:2. Most of these compounds have calciumfluorite (CaF
2
) type structure. These
compounds have cubic close packing (CCP) arrangement in which Ca
2+
ions are present at the corners and the
centre of each face of the cube.
Each Ca
2+
ion is surrounded by 8F

ions i.e. it has a


coordination number of 8 whereas each F

ion is surrounded
by 4 Ca
2+
ions i.e. has a coordination number of 4. Thus this
structure has 8:4 coordination. Few examples of such
compounds having CaF
2
structure are BaF
2
, BaCl
2
, SrF
2
,
SrCl
2
, CdF
2
, PbF
2
and ThO
2
.
+ 2
Ca

F
In Na
2
O each oxide ion is coordinated to 8 Na
+
ions and each Na
+
ion to 4 oxide ions. Hence it has 4:8
coordination. This is called antifluorite structure. Others examples being Cl
2
O, K
2
O, Li
2
O, K
2
S, Na
2
S etc.
Ionic Radii: The internuclear distance B/Wthe ions at the adjacent corners of a unit cell can be taken as the
sum of the radius of the cation and the radius of the anion.
But its not simple to assign different values to constituting ions because its not possible to calculate the radius
of one ion without knowing the radius of other one.
It has been observed that radius of a cation is smaller than that of the corresponding atom. The reason is that
with the removal of one (or more) electrons from the valence shell of the atom, the effective nuclear charge
increases because now, it is acting on a smaller number of electrons, making the electron cloud pulled more
inward towards the nucleus than before.
On the other hand, the radius of an anion is larger than that of the corresponding atom, reason being, with
addition of one (or more) electrons to the valence shell, effective nuclear charge decreases because the same
+ 2
Zn
2
S
ions Zn
four by lly tetrahedra
surrounded ion S
2
2
+

nuclear charge is now acting on a larger number of electrons. Consequently, the force of attraction on the
electron cloud decreases and hence the ionic radius increases.
Ionic radius increases in a group with increase in atomic number as:
Li
+
< Na
+
< K
+
< Rb
+
< Cs
+
Similarly, in the halogens, the ionic radius increase as:
F

< Cl

< Br

< I

The reason for this increase is the increase in the principal quantum number though the number of electrons in
the valence shell remains the same. In the same period, the radius of isoelectronic ions (having same number of
electrons) decreases with the increase in charge of the ions. e.g. Na
+
<Mg
2+
< Al
3+
.
Illustration 5: If the close packed cations in an AB type solid have a radius of 75 pm, what would be the
maximum and minimum sizes of the anions filling the voids?
Solution: For closed packed AB type solid
r
r
+

= 0.414 0.732
Minimum value of r

=
r 75
0.732 0.732
+
= pm = 102.5 pm
Maximum value of r

=
r 75
0.414 0.414
+
= pm = 181.2 pm
IQ 4:
i) The radius of Na
+
ion is 95 pm and that of Cl

ion is 181 pm. Predict whether the coordination number


of Na
+
ion is 6 or 4.
ii) How many unit cells are there in a 1.0g cube shaped ideal crystal of NaCl?
iii) The ionic radii of K
+
and F

are 133 and 136 pm, respectively. Calculate length of the unit cell of KF,
KF has rocksalt structure.
Imperfection in Solids
An ionic crystal which has the same unit cell containing the same lattice points throughout the crystal is known
as ideal crystal but crystals tend to have a perfectly ordered arrangement at only absolute zero. This
arrangement corresponds to state of lowest energy. And as the temperature increases, the crystals start deviating
from the perfectly ordered arrangement. This defect may appear at a point, along a line or over a surface.
A point defect could arise due to the absence of a particle (vacancy), presence of some foreign particle at a
lattice site, presence of a foreign particle at the interstitial site or displacement of a particle to the interstitial site.
Two main defects in crystals which are discussed as follows are Schottky and Frenkel defects
Schottky Defect: This defect is caused when some of the lattice points are unoccupied and those points
are called vacancies or holes fig. (a). The number of missing positive and negative ions is the same so that the
crystal remains neutral in all. Schottky defects are more common in ionic compounds with high coordination
number, and where the sizes of positive and negative ions are almost equal for example, NaCl, KCl, CsCl and
KBr.
The number of defects increases with increase in temperature. The number of defects increases to one in 106
sites at 775 K and one in 104 sites at 1075K. The presence of large number of Schottky defects in crystal results
in significant decrease in its density.
Frenkel Defect: This defect is caused when some of the ions leave their lattice sites to occupy an
interstitial site fig. (b). Frenkel defects are more common in ionic compounds with low coordination number
and where there is large difference in size B/W positive and negative ions for example, ZnS, AgCl, AgBr and
AgI.
In pure alkali metal halides, these defects
are not very common because the ions
cannot get into interstitial positions due to
their large sizes.
Fig. (a): Schottky Defect
B
-
A
+
A
+
B
-
B
-
B
-
B
-
B
-
B
-
A
+
A
+
A
+
A
+
A
+
A
+
A
+
B
-
A
+
Fig. (b): Frenkel Defect
B
-
B
-
B
-
B
-
B
-
B
-
A
+
A
+
A
+
A
+
B
-
A
+
B
-
A
+
A
+
Metal Excess Defect: This may occur in two different ways
F-Centres: A negative ion may be absent from its lattice site leaving a hole which is occupied by an electron,
thereby maintaining the electrical balance. This type of defect is formed by crystals which would be expected to
form Schottky defects. When compounds such as NaCl, KCl, are heated with excess of their constituent metal
vapours, or treated with high energy radiation, they become deficient in the negative ions and their formulae
may be represented by AX
1o
, where o is a small fraction. The crystal lattice has vacant anion sites which are
occupied by electrons. Anion sites occupied by electrons in this way are called F centres (F is an abbreviation
Farbe, the German word for colour).
Interstitial ions and electrons: Metal excess defects also occur when an extra positive ion occupies an
interstitial position in the lattice and electrical neutrality is maintained by the inclusion of an interstitial electron.
Their composition may be represented by general formula A
1+o
X. This kind of metal excess defect is much
more common than the first and is formed in crystals which would be expected to form Frenkel defects.
Examples include ZnO, CdO, Fe
2
O
3
.
Crystals with either type of metal excess defect contain free electrons, and if these migrate they conduct an
electric current. These free electrons may be excited to higher energy levels, giving absorption spectra and in
consequence their compounds are often coloured e.g. non-stoichiometric NaCl is yellow, non-stoichiometric
KCl is lilac.
F Centre
e

Na
+
Cl

F-centre in a Sodium chloride crystal


A
+
Metal excess defects caused by interstitial cations.
A
+
B

A
+
B

A
+
B

A
+
B

A
+
B

A
+
B

A
+
B

A
+
B

A
+
A
+
B

A
+
B

A
+
B

A
+
B

Metal Deficiency Defect: This defect is caused by


the missing cation from its lattice site. The extra negative
charge may be balanced if the adjacent metal ion has higher
positive charge. This can be possible by compounds of
transition metals (variable valency). Crystals of FeO, FeS
and NiO show this defect.
Properties of Solids
Electrical Properties: Solids can be broadly classified into three types, on the basis of electrical
conductivity.
a) Metals (conductors)
b) Insulators
c) Semiconductors
Electrical conductivity of metals is very high and is of the order of 10
6
10
8
ohm
1
cm
1
whereas for insulators,
it is of the order of 10
12
ohm
1
cm
1
. Semiconductors have intermediate conductivity in the range of 10
2
10
9
ohm
1
cm
1
. Electrical conductivity of solids may arise through the motion of electrons and holes (positive) or
through the motion of ions. The conduction through electrons is called ntype conduction and through
(positive) holes is called ptype conduction. Pure ionic solids where conduction can take place only through
movement of ions are insulators. The presence of defects in the crystal structure increases their conductivity.
The conductivity of semiconductors and insulators is mainly due to the presence of interstitial electrons and
positive holes in the solids due to imperfections. The conductivity of semiconductors and insulators increases
with increase in temperature while that of metals decrease.
Band Theory Consider a molecule with two atomic orbitals.
The result must be that two molecular orbitals will be formed
from these atomic orbitals: one bonding and one anti-bonding,
separated by a certain energy
- If this is expanded to a molecule with three atoms,
assuming 1 atomic orbital for each, then the result must
be that 3 molecular orbitals will be formed.
- Now , let's take it to 10 atoms. As the
number of molecular orbitals increases, the
energy difference between the lowest bonding
and the highest anti-bondig increases, while
the space between each
individual orbital decreases
Consider a metal with
an infinite number of atoms. This will form an
A
+
A
+
B
-
B
-
A
+
A
+
A
+
A
+
A
2+
B
-
B
-
B
-
B
-
B
-
A
+
A
+
B
-
B
-
B
-
Metal deficiency due to cation vacancy
infinite number of molecular orbitals so close together they blur into one another
forming a band.
Conductivity according to MOT is related to ease of
availability of conduction [empty band ] band for
movement of electrons from valance band
1.valance band : highest occupied band and 2.
Conduction band : lowest un occupied band
Energy gap of semiconducter
According to MOT the
substance in which band
gap is intermediate of
Conductors and insulator
and small as well, which make promotion of electron from
valance band to conduction band possible
1. n-type Semiconductor 2 . p-type Semiconductor
n-type Semiconductor Doping with an element of extra
valence electrons into a element. There is NO
extra room for these electrons in the valence band;
consequently, they are promoted into the conduction
band, where they have access to many vacant orbitals
within the energy band they occupy and serve as
electrical carrierse.g.Silicon (4v es-)doped with
phosphorous(5 ves-)
In general 14 th group element with 15
th
group element
p-type Semiconductor : Doping with an
element of less electrons in order to create electron
vacancies or positive holes in the system. Because the
valence band is incompletely filled, under the influence
of an applied field, electrons can move from occupied
molecular orbitals to the few that are vacant, thereby
allowing current to flow.
e.g.
Silicon (4 ves-)doped with aluminium (3 ves-)
In general 14th group element with 13
th
group element
Magnetic Properties
n= no of unpaired e-.
PARAMGNETISM
The materials which are weakly attracted by magnetic
field are called paramagnetic materials. These materials
have permanent magnetic dipoles due to presence of
atoms, ions or molecules with unpaired electron. e.g. O
2
,
Cu
2+
, Fe
2+
etc. But these materials lose their magnetism in the absence of
magnetic field.
Ferromagnetic Materials: The materials which show permanent magnetism even in the absence of
magnetic field are called ferromagnetic materials. These materials are strongly attracted by the magnetic field.
e.g. Fe, Co, Ni and CrO
2
. Ferromagnetism arises due to
spontaneous alignment of magnetic moments of ions or
atoms in the same direction.
Alignment of magnetic moments in opposite directions in a
compensatory manner and resulting in zero magnetic
moment gives rise to antiferromagnetism
ferromagnetism
||||||| ;
Anti ferromagnetism
|+|+|+| ;
Ferrimagnetism
|++|++|
for example, MnO, Mn
2
O
3
and MnO
2
.to unequal number of
parallel and antiparallel magnetic dipoles give rise to
ferrimagnetism e.g. Fe
3
O
4
.
Ferromangetic and ferrimagnetic substances change into paramagnetic substances at higher temperature due to
randomisation of spins. Fe
3
O
4
, is ferrimagnetic at room temperature and becomes paramagnetic at 850 K.
Property Definitions Example
Diamagnetic Repelled by ex. MF.
because absence of unpaired electron
NaCl
Paramagnetic Weakly attracted and shows magnetism
Only in presence of ex. MF
O
2
,Cu
2+
Ferromagnetic Strongly attracted and shows magnetism
even in absence of ex.MF
Fe,Co,Ni
Ferrimagnetic Observed magnetic moment is lesser than
calculated because unequal alignment
Fe
3
O
4
Antiferromagn
etic
Observed magnetic moment is zero
because of exactly equal no opposite
alignment
MnO
Dielectric Properties: The electrons in insulators are closely bound to the individual atoms or ions and
thus they do not generally migrate under the applied electric field. However, due to shift in charges, dipoles are
created which results in polarisation. The alignment of these dipoles in different ways i.e. compensatory way
(zero dipole) or noncompensatory way (net dipole) impart certain characteristic properties to solids.
If the dipoles align in such a way that there is net dipole moment in the crystals, these crystals are said to exhibit
piezoelectricity or piezoelectric effect i.e. when such crystals are subjected to pressure or mechanical stress,
electricity is produced. Conversely, if an electric field is applied to such a crystal, the crystal gets deformed due
to generation of mechanical strain. This is called inverse piezoelectric effect.
Some crystals which on heating, acquire electric charges on opposite faces, are said to exhibit pyroelectric
effect.
The solids, in which dipoles are spontaneously aligned in a particular direction, even in the absence of electric
field are called ferroelectric substances and the phenomenon is known as ferroelectricity. If the alternate dipoles
are in opposite direction, then the net dipole moment will be zero and the crystal is called anti ferroelectric
.
Ferroelectric solids Barium titanate (BaTiO
3
), sodium potassium tartrate (Rochelle salt) and potassium
hydrogen phosphate (KH
2
PO
4
). Antiferroelectric Lead Zirconate (PbZrO
3
).
LEVEL I (CBSE LEVEL) Review Your Concept
1. An element crystallizes in a structure having a FCC unit cell of an edge 200 pm. Calculate its density if
200g of this element contains 24 10
23
atoms.
2. Copper crystal has a face centred cubic structure. Atomic radius of copper atom is 128 pm. What is the
density of copper metal? Atomic mass of copper is 63.5.
3. An element occurs in BCC structure with a cell edge of 288 pm. The density of metal is
7.2 g cm
3
. How many atoms does 208g of the element contain?
4. The density of crystalline sodium chloride is 2.165 g cm
3
. What is the edge length of the unit cell. What
would be the dimensions of cube containing one mole of NaCl?
5. The density of potassium bromide crystal is 2.75 g cm
3
and the length of an edge of a unit cell is 654
pm. The unit cell of KBr is one of three types of cubic unit cells. How many formula units of KBr are
there in a unit cell? Does the unit cell have a NaCl or CsCl structure?
6. When heated above 916C, iron changes its crystal structure from bodycentred cubic to cubic closed
packed structure. Assuming that the metallic radius of the atom does not change, calculate the ratio of
density of the BCC crystal to that of the CCP crystal.
7. The unit cell length of NaCl is observed to be 0.5627 nm by Xray diffraction studies; the measured
density of NaCl is 2.164 g cm
3
, Correlate the difference of observed and calculated density and
calculate % of missing Na
+
and Cl

ions.
8. CsCl has cubic structure of ions in which Cs
+
ion is present in the body centre of the cube. If density is
3.99g cm
3.
a) Calculate the length of the edge of a unit cell.
b) What is the distance between Cs
+
and Cl

ions?
c) What is the radius of Cs
+
ion if the radius of Cl

ion is 180 pm?


9. An element having atomic mass 52, occurs in body centred cubic (BCC) structure with a cell edge of
288 pm. The density of the element is 7.2 g cm
3
. Evaluate Avagadros number?
10. The element having atomic mass 60 has face centred cubic unit cells. The edge length of the unit cell is
400 pm. Find out density of the element.
LEVEL II Brush Up Your Concepts
1. In a crystalline solid, having formula AB
2
O
4
, oxide ions are arranged in cubic close packed lattice while
cations A are present in tetrahedral voids and cations B are present in octahedral voids.
i) What percentage of the tetrahedral voids is occupied by A?
ii) What percentage of the octahedral voids is occupied by B?
2. Calculate the value of Avogadro number from the following data:
Density of NaCl = 2.165 gm cm
3
, distance between Na
+
and Cl

ions in NaCl
crystal = 281 pm
3. In a cubic close packed structure of mixed oxides, the lattice in made up of oxide ions, oneeighth of
tetrahedral voids are occupied by divalent ions (X
2+
) while one half of octahedral voids are occupied by
trivalent ions (Y
3+
). What is the formula of the oxide?
4. Sodium crystallizes in b.c.c. lattice of side length 4.30 . How many atoms are present in a unit lattice?
What is density of the metal? Atomic weight of Na = 23.
5. Sodium metal crystallises in body centred cubic lattice with cell edge, 4.29. What is the radius of
sodium atom?
6. Potassium crystallises in a BCC lattice, (edge length, a = 5.20)
a) What is the distance between nearest neighbours?
b) How many neighbours does each K atom have?
c) What is the density of crystalline K?
7. KBr crystallises in the FCC unit cell (NaCl type)
a) How many K
+
ions and how many Br

ions are in each unit cell?


b) What is the edgelength if
K
r
+
= 1.33,
Br
r

= 1.95?
c) What minimum value of r
+
/r

is needed to prevent anionanion contact in this structure?


8. Lithium borohydride crystallizes in an orthorhombic system with 4 molecules per unit cell. The unit cell
dimensions are a = 6.8 , b = 4.4 and c = 7.2 . If the molar mass is 21.76. Calculate the density of
crystal.
9. Compute the limiting radius ratio r
+
/r

for (a) a square planar crystal structure in which B

ions are at the


corner of the square and A
+
ions are the centre, and (b) an equilateral triangular crystal structure with B

at the apex and A


+
at the centre.
10. A solid PQ has the NaCl structure. If the cation radius is 100 pm, calculate the maximum possible value
of the radius of the anion. Answer to Assignments (Subjective)
LEVEL I
1. 41.6 g cm
3
2. 8.9 g/cm
3
3. 24.16 10
23
atom 4. 3 cm
5. 4, fcc 6. 0.918
7. 0.016 g/cm
3
, 0.775% 8. a) 412 pm; b) 356.8 pm; c) 176.8 pm
9. 6.04 10
23
10. 6.2 g/cm
3
LEVEL II
1. 12.5%, 50% 2. 6.02 10
23
3. AB
2
O
4
4. 2, 0.96 g
3
cm
5. 1.86 6. 4.05, 8, 0.925 g/cm
3
7. 4, 6.56, 0.414 8. 0.6709 g cm
3
9. 0.414, 0.866 10. 241.5 pm
BY MUKESH SHARMA ,DPS JODHPUR