SOLID STATE

KEY CONCEPT
1. SOLIDS AS A STATE OF MATTER
Solids are characterised by the state of matter in which particles are closely packed and held together by
strong inter molecular attractive force.

1.1 Properties of solids

(a) In solid state the particles are not able to move randomly.
(b) They have definite shape and volume.
(c) Solids have high density. .
(d) Solids have high and sharp melting point which depends on the strength or value of binding energy.
(e) They are very low compressible.
(f) They show very slow diffusion.

Can you guess which type of kinetic energy will be more dominant is solids,
Rotational, translational or vibrational?

1.2 Types of Solids

Difference between crystalline and amorphous solids

S.N. Property Crystalline solids Amorphus solids
1 Shape They have definite and regular They do not have definite and regular
geometrical form. geometrical form.
2 Melting point They have definite melting point. They do not have definite melting point.
3 Heat of fusion They have a definite heat of fusion. They do not have definite heat of fusion
4 Compressibility They are rigid and These may be compressed to any
incompressible. appreciable extent.

5 Cutting with a They give clean cleavage i.e. they They give irregular cleavage i.e.
Sharp edged break into two pieces with plane they break into two pieces with
tool surfaces. irregular surface.

6 Isotropy and They are anisotropic. They are isotropic.

Anisotropy

7 Physical state True solids pseudo solids and are considered as

super cooled liquid .
Examples Quartz, Diamond Rubber, Plastic

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2. CLASSIFICATION OF CRYSTALS
According to attractive force which hold crystal together are generally of five types and thus crystal can
be classified into four types:

Type of Solid Intermolecular forces Properties Examples

Brittle, hard, high Melting point

Ionic Ion-Ion forces Insulator in solid but conductance NaCl, KCl, MgCl2
fused and aqueous solution

Dispersion
Molecular forces/Dipole-Dipole Soft, low melting point, Insulators H2O, Br2, CO2 , CH4
/H-bond
Covalent or
Covalent bonds Hard, Very high melting point C-Diamond, SiO 2
network
Variable hardness and melting
Metallic Metallic bonds point, malleable and ductile, Na, Zn, Cu, Fe
conducting

Classification of crystallie solids (on the basis of intermolecular forces in them)

Molecular Metallic Covalent Ionic

Molecules as Kernels and mobile Non–metal atoms linked Positive and negative
constituent electrons are constituent to adjacent atoms by covalent ions are constitution
particles particle, e.g., Fe, Cu, Ag bond are constituent particles. particles, e.g.,
They form giant molecule e.g., NaCl, MgO, ZnS, CaF2
diamond, SiC, SiO2, AIN, graphite

Polar molecular Non–polar H–bonded

solids molecular solids molecular solids
e.g., HCl, Solid SO2, e.g., He and Ar e.g., H2O (ice),
solid NH3 NH3, ROH

It is advisable that students should memories one or two examples of each

type of crystalline solids.

2.1 Type of Symmetry in Crystals

a. Law of symmetry : It states that all crystals of a substance possess the same element of symmetry.
Three important elements of symmetry are :
I. Plane of symmetry II. Axis of symmetry III. Center of symmetry

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 SOLID STATE

b. The total number of elements of a symmetry in a cubic crystal = 23

I. Plane of symmetry = 3 (rectangular plane of symmetry)

+ 6 (diagonal plane of symmetry) = 9

II. Axis of symmetry = 3 (four–fold or a tetrad axis of symmetry)

+ 4 (three–fold or a triad axis of symmetry)
+ 6 (two–fold or diad axis of symmetry) = 13

III. Center of symmetry or inversion of symmetry = 1

 Total number of elements of symmetry in a cubic crystals = 9 + 13 + 1 = 23

Axis of six–fold or a hexed axis of symmetry : This type of symmetry is

possible in hexagonal crystals and not in cubic crystals.

2.2 Parameters for the Study of Cyrstals

Crystal - Acrystal is a homogenous portion of a solid substance made by regular pattern of structural
units bonded by plane surface making definite angles with each other.

Space lattice: - The arrangement of constituents like atom, ions and molecules in different sites in three
dimensional space is called space lattice.

Unit cell : - The smallest repeating unit in space lattice which when repeats over and over again, results
in a crystal of the given substance called unit cell.

Face:- The plane surface of the crystal are called faces.

Edge:- An edge is formed by the intersection of two adjacent faces.

Interfacial angle :- The angle between two perpendicular intersecting faces is called interfacial angles.

2.3 Crystal system

Bravais showed that there are only seven types of crystal system.
These are -
(a) Cubic (b) Tetragonal
(c) Orthorhombic (d) Rhombohedral
(e) Hexagonal (f) Monoclinic
(g) Triclinic

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Unit Cell Parameters

Crystal Systems Bravais Lattice Example
Intercepts Crystal Angles
Primitive, Face Centered,
1 Cubic a=b=c  NaCl, Zinc blend, Cu
Body Centered
Primitive, Face Centered, Rhombic sulphur, KNO3 ,
2 Orthorhombic abc 
Body Centered, End Centered BaSO4
White tin, SnO2 , TiO2,
3 Tetragonal Primitive, Body Centered a=bc 
CaSO4
Monoclinic sulphur,
4 Monoclinic Primitive, End Centered abc 
Na2SO4.10H2O
Caccite (CaCO3), HgS
5 Rhombohedral or Trigonal Primitive a=b=c 
(Cinnabar)
K2Cr2O7 , CuSO4.5H2O,
6 Triclinic Primitive abc 
H3BO3
7 Hexagonal Primitive a = b  c  Graphite, ZnO, CdS

Students should memories all the cell parameters for each type of crystal
systems. Remembering examples for each type is not required except for
very common substances like NaCl, Graphite etc.

2.4 Diagramatic representation of Seven Crystal System

Rhombohedral
abc
   90°

Although there are only 7 crystal systems or shapes, there are 14 different crystal
lattices, called Bravais Lattices. (3 different cubic types, 2 different tetragonal
types, 4 different orthorhombic types, 2 different monoclinic types, 1 rhombohedral,
1 hexagonal, 1 triclinic).

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PRIMITIVE AND CENTERED UNIT CELLS

Primitive Centered unit cells

Constituent particles are Constituent particles are
present only on the corners present on corner as
of a unit cell well as on other positions

Body–centered unit cell (bc) Face–centered unit cell (fc) End–centered unit cell(ec)
One constituent One constituent One constituent
particle at its body particle at the center particle at the center
center along with of each face along with of any two opposite faces
at its corners at its corners along with at its corners

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2.5 Types of Unit Cells

There are four types of unit cells.
(a) Simple or primitive. Particles are only at the corners of the unit cell.

(b) Face-centered cubic unit cell. In addition to corners, particles are present at the centre of each face of the
unit cell.

(c) End-face-centered unit [Link] is present at each corner plus particles are present on the end faces
of the unit cell.

(d) Body-centered cubic unit cell. In addition to the particles at the corners, there is one particle in the body-
centre of the unit cell.

3. ANALYSIS OF CUBIC CRYSTAL SYSTEM

3.1 Parameters involved in analysis of crystal systems

(a) Coordination Number

If atoms are represented by spheres, the number of spheres which are touching a particular
sphere is called coordination number of that sphere.

In ionic crystals, the coordination number may be defined as the number of

the oppositely charged ions surrounding a particular ion

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(b) The number of particles per Unit Cell

(i) An atom at the corner is shared by 8 unit cells. Therefore, its contribution is = 1/8.
(ii) An atom at the face is shared by 2 unit cells. Therefore. its contribution is = 1/2.
(iii) An atom present in the body is unshared. Therefore. its contribution is 1.
(iv) An atom present on the edge is shared by four unit cells. Therefore, its contribution
is = 1/4
The number of atoms per unit cell are in the same ratio as the stoichiometry of
the compound or the ratio of the number of particles A and B present per unit
cell gives the formula of the compound formed between A and B

(c) Packing fraction and Void fraction

The volume of a cubic unit cell is not completelyoccupied byatoms. The ratio of volume occupied
by the effective atoms to the volume of the unit cell is called packing fraction (PF). The fraction
of volume of a unit cell, that is empty is called void fraction (VF). Thus,

Volume occupied by the effective atoms in a unit cell

Packing fraction =
Volume of the unit cell (a 3 )

and void fraction = (1– Packing fraction)

3.2 Calculation of number of particle

(a) a primitive or simple cubic unit cell, the total number of particles is 1/8 × 8 = 1.

(b) a face-centred cubic unit cell, the total number of particles is 1/8 × 8 + 1/2 × 6 = 4.

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 SOLID STATE

(c) a body-centred cubic unit cell, the total number of particles is 18  8  1  2 .

3.3 Calculation of Packing Fractions

(i) Consider a simple cubic unit cell. Suppose the edge length of the cell is a and the radius of the sphere is
r. As the spheres are touching each other, a = 2r.

Number of spheres per unit cell = 1/8 × 8 = 1.0

4 3
Volume of the sphere = r
3
Volume of the cube = a3 = (2r)3 = 8r3
3
3 r
4
Packing fraction =  0.524 or 52.4 percent occupied.
3
8r
(ii) In a face-centred cubic structure.
Spheres on the face are in contact (touching) whereas the one at corners are not touching each other.

Therefore, AC = 4r
Also AC = AB 2  BC 2 (since ABC is right angled triangle)

AC = a2  a2
4
AC = 2a  4r or a  r
2

3
 4  32 3
Volume of unit cell = a3 =  r = r
 2  2

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1 1
Number of spheres in unit cell =  8  6   4
8 2

Volume of 4 spheres = 4  4 3 r 3  16 3 r 3

16r 3 / 3
Therefore, fraction occupied =  0.74 or 74% occupied.
32r 3 / 2
(iii) In a body-centred cubic structure.
AD is the body diagonal and since the sphere at centre touches the one at corners, AD = 4r. Also

AD = AC 2  CD 2

Since AC = AB 2  BC 2  a 2  a 2  2a

AD = 2a 2  a 2  3a  4r

3
4r  4r  64r 3
Or a = 3
or the volume of the cubic cell = a =   
3  3 3 3

 1 
Number of spheres per unit cell =  8   1  1  2
 8 

4 3
Volume of 2 spheres = 2  r  8 3 r
3
3

8 r 3 / 64r 3
Packing fraction = 3 = 0.68 or 68% occupied.
3 3

3.4 Length of Unit Cell and Density of a Cubic Crystal

The density of the crystal can be calculated if the edge size of the cubic crystal and the type of structure
possessed by it is known.
If the length of the unit cell is a
volume of the unit cell = a3
Number of atoms in the
Mass of unit cell cell  Mass of each atom
And, density of the unit cell = =
Volume of unit cell Volume of unit cell

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Z M
Density () =
a3  Na
Z = Effective number of atoms in unit cell
Na=Avogadro’s number
M =Atomic mass

Illustration
1. Sodium has a bcc structure with nearest neighbour distance 365.9 pm. Calculate its density. (Atomic
mass of Na = 23)
Sol. For the bcc structure, nearest neighbour distance (2r) is related to edge length (a) as
3
2r = a
2
2 2
a= × 2r = × 365.9 = 422.5 pm
3 1.732
M = 23
zM 2  23
For bcc structure, z = 2 d = a 3  N  422.5  10 10  6.023  10 23 = 1.51 g/cm3
0

2. A compound formed by elements X and Y crystalises in the cubic structure, where Y atoms are at the
corners of the cube and X atoms are at the alternate faces. What is the formula of the compound?
Sol. Y atoms are at the corners of the cubic unit cell and contribution of each is = 1/8. So, the total number
of Yatoms per unit cell = 8 × 1/8 = 1. X atoms are on alternate faces and contribution of each = 1/2. So,
the number of X atoms per unit cell is 2 × 1/2 = 1. Hence, the formula is XY.

3. Calculate the number of atoms in a cubic unit cell having one atom on each corner and two atoms on
each body diagonal.
Sol. Atoms at the corner contribute 1/8 and so the total number of corner atoms per unit cell is equal to one.
Now, there would be four body diagonals in a cube and each diagonal has 2 atoms not shared by any
other unit cell. So, there are total 8 atoms within the body of the unit cell and the total number of atoms
per unit cell would be nine.

4. PACKING OF CONSTITUENT PARTICLES IN CRYSTALS

The structure of crystalline solids is determined by the packing of their constituents. During formation,
the constituent particles get closely packed together. The available space is most economically used and
a state of maximum possible densityis reached. The various modes of packing are considered byassuming
the particles to be spherical. The arrangement should be such that the spheres should occupy maximum
available space.

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4.1 The packing of spheres takes place as follows:

(i) When the spheres are placed in a horizontal row touching each other in such a way that the rows have a
horizontal as well as vertical alignment, the spheres are found to form a square. This is called square
close packing (Figure 1(a))

(ii) When the spheres are packed in such a way that the spheres in every second row are placed in the
depressions between the spheres of the first row and in the third row the spheres are vertically aligned
with spheres in the first row, a hexagonal close packing is obtained, since the packing of this type gives
a hexagonal pattern. (Figure 1 (b)).
A comparison of the two ways of packing of spheres shows that in arrangement (i) the spheres are less
closely packed than in arrangement (ii). It has been calculated that in arrangement (i) only78.54% of the
available space is occupied by the spheres. In the second arrangement, 90.7% of the space is occupied.
Thus, arrangement (ii) is more economical and, therefore, it represents a close packing of spheres. It can
be seen that in arrangement (i) each sphere is in contact with four other spheres.

On the other hand, in arrangement (ii), each sphere is in contact with six other similar spheres.
Thus, arrangement (ii) represents an efficient closest packing of spheres in a layer. We can now build
other layers over the first layer to extend the packing in three dimensions. Let us mark the spheres in the
first layer asA. It is clear from the following figure II(a) and figure II(b) that there are two types of voids
(hollows) in the first layer. These are marked as a and b.

Now, if a second layer is placed with spheres vertically aligned with those in the first layer, its voids will
come above the voids in the first layer and this would again be an inefficient way of filling the space.
Obviously, for the second layer, the spheres are to be placed in either of the voids.

All the voids are equivalent, but the spheres of the second layer may be placed either on the voids
marked ‘a’ or on the other set of voids marked ‘b’. It may be noted that it is not possible to place
spheres on both types of voids.

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Let us place the spheres on hollows marked ‘a’ to make the second layer which may be labelled as ‘B’
layer. Obviously, the holes marked ‘b’remain unoccupied while building the second layer. The second
layer is indicated in the following figure.

Now, there are two types of voids in the second layer. These are marked as ‘c’and ‘d’. The voids ‘c’(of
the second layer) are ordinary voids which lie above the spheres of the first layer whereas voids ‘d’ lie on
the voids of the first layer and hence are combination of two voids, one of the first layer and second of
the second layer.

The ‘a’ and ‘b’ voids of the first layer are both triangular whereas only ‘c’ voids of the second layer are
triangular. The ‘d’voids of the second layer which are a 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.

A simple triangular void in a crystal is surrounded by four spheres and is called a tetrahedral void or a
hole. Adouble triangular void like ‘d’is surrounded by six spheres and is called an octahedral void.

Now, there are two ways of building a third layer.

(i) When a third layer is placed over the second in such a way that the spheres cover the tetrahedral or ‘c’
voids, a three dimensional closest packing is obtained, where the spheres in every third layer or alternate
layers are verticallyaligned. The arrangement is calledABAB pattern or hexagonal close packing (hcp).
Mo, Mg, Zn, Cd, Be, etc. have an hcp structure.

(ii) If the third layer is placed over the second layer in such a way that the spheres cover the octahedral or
‘d’ voids, a different layer ‘C’ is formed. In this case, every fourth layer will be vertically aligned. This
arrangement is called ABCABC..... pattern or cubic close packing (ccp) Fe, Ni, Cu, Ag, Au, Pt etc.
have a ccp structure.

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These two arrangements are depicted in figures III and IV. Both hcp and ccp arrangements of packing
are equally efficient. In these patterns, the maximum possible space (74% of the available volume) is
occupied. Only 26% of the space remains empty. That is why these are referred to as close packings.
In both hcp and ccp, a sphere is in contact with 6 others in its own layer and three spheres in the layer
above and three spheres in the layer below. The coordination number is 12 in both the patterns.

Figure III. Actual view of (I) hexagonal close packing (II) Cubic close packing

Figure IV. Simplified view of (I) Hexagonal close packing (AB AB....pattern)
(II) Cubic close packing (ABC ABC.... pattern)

In addition to these two types of close packings, a third type of arrangement is found in metals. It is
body- centerd cubic packing (bcc). This is found in metals like Li, Na, K, Rb, and Cs. In this packing,
the spheres are opened up and not touching. ‘B’is placed on ‘A’. The building of third layer is exactly
like the first. The coordination number is 8 and 68% of volume is occupied.

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It is seen that even in closely packed spheres and most efficient arrangements, certain hollows are left
vacant. These holes or voids are called interstitial sites. Two important interstitial sites are (a) tetrahedral
voids and (b) octahedral voids.
The voids are not tetrahedral or octahedral but the arrangement around it is such that if the spheres are
arranged in the voids, the geometric figure generated is like that.
1. In the closest packed system for each sphere, there are two tetrahedral voids and only one octahedral
void. The two tetrahedral voids are present above and below each atom and octahedral void is midway
between two closely packed layers.
2. In ionic crystals, it is not possible for both cations and anions to have a close packed structure due to
their different sizes. However, it is common for the bigger ion (usually anions) alone to approach a close-
packed structure and smaller ions to fit into voids in the structure. The radii of interstitial sites that is, the
voids in these close-packed structures are related to the sizes of the spheres present in them. If ‘R’ is the
radius of the spheres in the close-packed structures, then
Radius (r) of tetrahedral void = 0.225 R
Radius (r) of octahedral void = 0.414 R.
Therefore, the limiting size of cations which can fill voids without disturbing the closest packing is for
rc rc rc
octahedral void = ra  0.414 , tetrahedral void = ra  0.225 , and for cubic voids ra  0.732

where rc = radius of cation and ra = radius of anion.

3. In a close-packed arrangement hcp or ccp, the number of octahedral voids are equal to the number of
atoms present in the close-packed arrangement and the number of tetrahedral voids are equal to 2x
(number of octahedral voids) and consequently are equal to 2x (number of atoms).

Illustration
4. The packing fraction in fcc and hcp structure is same. Moreover, this is the highest packing fraction of all
the possible unit cells with same atoms . Can you explain this ?
Sol. The arrangement of atoms in hcp is ofABABAB ... type and in case of fcc is ofABCABCABC... type.
Both in hcp and fcc, the layers are formed of same atoms in similar arrangement but the only difference
is the placement of layers on top of each other. Hence, both have same packing fraction.

In both the arrangement, the number of atom of same size present around the atom is maximum, i.e., 6
So, the packing fraction is highest.

5. In 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 cations (B). What is the formula of the
compound. ?
Sol. O2–  fcc = 4
1 4 1 4
A 8 = B ×4=
6 3 3 3
 Unit cell formula is A4/3 B4/3 O4
or A4B4O12
 Chemical formula is ABO3 Ans.

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5. RADIUS RATIO RULES

Following conditions must be satisfied simultaneouslyduring the stacking of ions of different sizes in an
ionic crystal:
(a) An anion and a cation are assumed to be hard spheres always touching each other.
(b) Anions generally will not touch but may be close enough to be in contact with one another in a limiting
situation.
(c) A cation should surround itself with as many anions as possible. Each ion tends to surround itself with
as many ions of opposite sign as possible to reduce the potential energy. This tendency promotes the
formation of close-packed structures.

5.1 Radius ratio

5.1.1 Radius ratio for co-ordination number 3

r
(TriangularArrangement) : = 0.155
r

5.1.2 Radius ratio for coordination number 4

(Tetrahedral arrangement):

r
= 0.225
r

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5.1.3 Radius ratio for coordination number 6:

r
(Octahedral Arrangement) = 0.414
r

5.1.4 Radius ratio for coordination number 8 :

(Body centered cubic crystal)

r
= 0.732
r

Ligancy as a function of radius ratio in 1 : 1 or AB–type structure

[Link]. Ligancy or Range of Configuration Structure Examples

coordination radius ratio type
number

r*
0.0 < < 0.155
R

r
0.155  < 0.225
R

r
0.225  < 0.414
R

r
0.414  < 0.732
R

r
0.732  < 1.0
R

r
= 1.0
R

*r = radius of cation ; R = radius of anion

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The radius ratio rule is not the sole criteria for deciding crystal structure and
it is possible that some crystal structures are not in accordance with the ra
dius ratio rule.

Illustration
6. A solid A+ B– has a sodium-chloride-type close-packed structure. If the anion has a radius of 250 pm,
what should be the radius of the cation? Can a cation C+ having a radius of 180 pm be slipped into the
tetrahedral site of the crystal A+ B–?

Sol. As A+ B– has a sodium-chloride-type packing, A+ ions will be present in octahedral voids. The ideal
radius of the cation will be equal to the radius of the octahedral void as then the cation will touch the
anions and the arrangement will be close packed.

Radius of octahedral void = rA  0.414  rB 

Therefore, rA  0.414  250 pm  103.4 pm

The radius of tetrahedral site is = 0.225  rB   0.225  250 pm

= 56.25 pm
Obviously, cation C+ of 180 pm dimension cannot be slipped into the tetrahedral site.

On applying a high pressure, sodium chloride structure (6 : 6 coordination)

changes to cesium chloride structure (8 : 8 coordination). Similarly, cesium
chloride structure on heating to 760 K changes to sodium chloride structure.
Obviously, an increase in pressure enhances the coordination number whereas
an increase in temperature causes a reverse effect.

6. Structure of Some Ionic Crystals

6.1 Sodium Chloride (NaCl) Type AB. (Rock Salt)

Cl¯
+
Na

Rock salt structure

r r = 0.524 suggests octahedral voids.

Na + Cl –

(a) It has face-centred cubic (fcc) arrangements (also called cubic close packing ccp). Cl– are large and
present at the corners and face centres whereas Na+ (in octahedral holes) are present at the body centre
and edge centre.

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(b) Since the number of octahedral holes is equal to the number of anions, the formula is NaCl. In this
packing, each Na+ is surrounded by six Cl– and each Cl– is surrounded by 6 Na+. (In this packing, there
are six octahedral holes.) Therefore, the coordination number of Na+ and Cl– is six, that is, this structure
has 6 : 6 coordination.
(c) In the unit cell, Cl– are at the corners and at the face centres; therefore, the number of Cl– per unit cell is
1 1
8  6  4 .
8 2
Similarly, Na+ are at the body centre and edge centre.

1
Total number of Na+ per unit cell = 1  12   4.
4
Thus, there are four NaCl units per unit cell.
Other crystals which have a similar structure are AgCl, AgBr, oxides and sulphides of alkaline earth
metals (except BeS) and halides of K, Rb and NH4Cl, NH4Br and NH4I.

6.2 Zinc Blende (ZnS)-Type Structure

2–
S
+2
Zn

Zinc blende structure

r r = 0.40, that is, a tetrahedral arrangement.

Zn 2+ S2–

(a) The crystal has a cubic close packing (ccp) in which S2– form a face-centred cubic structure and thus are
present at the corners and at the centre of each face, whereas Zn2+ occupy the tetrahedral holes.

(b) For every atom or ion closely packed, there are two tetrahedral holes and only half are occupied by
Zn2+ to have the formula ZnS (1 : 1 stoichiometry). Only alternate holes are occupied by Zn2+.

(c) Each Zn2+ in a tetrahedral hole is surrounded by 4 sulphide ions and each sulphide ion is surrounded by
four Zn2+. Thus, the coordination number of both ions is 4 or it has 4 : 4 coordination.
(d) In a unit cell
Out of 8 tetrahedral voids, Zn2+ occupy four.
Therefore, the number of Zn2+ per unit cell = 4.

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Sulphide ions occupy the corners and face centres.

1 1
So, the number of sulphide ions is 8   6   4 .
8 2
So, there are four ZnS units per unit cell.

(e) BeS, AgI, and halides of copper have a similar structure.

6.3 Cesium Chloride (CsCl)-Type Structure

Cs+
Cl–

(a) It has a body-centred cubic (bcc) arrangement plus a hole (cubic).

(b) Cl– form a simple cubic arrangement and occupy corners of a cube and Cs+ is present in the body in
interstitial hole.
(c) Each Cs+ is surrounded by 8 Cl– and each Cl– is surrounded by 8 Cs+. The coordination number is 8 :
8.
(d) In a unit cell,

1
the total number of Cl– is 8   1
8
and the total number of Cs+ = 1
Therefore, there is one unit of Cs Cl per unit cell.
(e) CsBr, CsI, TlCl, Tl Br, Tl I, and TlCN have a similar structure.

6.4 Calcium Fluoride (CaF2) (Fluorite)

Ca+2
–
F

(a) This is also a ccp or fcc structure. Each Ca2+ is present at corners plus centre of each face. F– occupy
tetrahedral sites.

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 SOLID STATE

(b) Since there are two tetrahedral holes for each Ca2+, there would be two F– per calcium ion. The
stoichiometry is 1 : 2.
(c) Each Ca2+ is surrounded by 8 F– and each F– (in tetrahedral hole) has 4 Ca2+ around it. Therefore, the
coordination number of Ca2+ is 8 and that of F– is 4, or the coordination number of the crystal is 8 : 4.
(d) The unit cell has

1 1
Ca2+ = 8   6   4
8 2
F– = 8 within the body
Therefore, there are 4 CaF2 units per unit cell.
(e) PbF2, BaCl2, BaF2, SrF2, SrCl2, Cd F2, and ThO2 have this type of structure.

6.5 Antifluorite Structure (Reverse of Fluorite)

Na+
O2–

Examples are Li2O, Na2O, etc.

In this, the oxide ions form a cubic arrangement and Na+ or Li+ is in tetrahedral hole. The oxide ions are
surrounded by8 Li+ or Na+ whereas each Li+ or Na+ is surrounded byfour oxide ions. So, the coordination
number of Li or Na is 4 and that of oxide is 8 or it has 4 : 8 coordination.

Metals like Al, Ag, Au, Cu, Ni and Pt have a ccp structure and Be, Cd, Mg, Co and Zn have a
hcp structure.
Illustration
7. The radius of a calcium ion is 94 pm and of an oxide ion is 146 pm. Predict the crystal structure of
calcium oxide.
r 94
Sol. The ratio   0.644
r ¯ 146
The prediction is an octahedral arrangement of the oxide ions around the calcium ion. Because the ions
have equal but opposite charges, there must also been an octahedral arrangement of calcium ions
around oxide ions. Thus, we would expect a rock salt (NaCl) structure.

Noble gases (except He, which has a hcp structure) have a ccp structure.

6.6 Structure of FeO, Fe2O3, and Fe3O4

(a) FeO. This oxide is non-stoichiometric and has a composition FexO (Generally ‘x’ varying from 0.92 to
0.97). The oxide ions form a cubic close packing. The octahedral voids are occupied by Fe2+ but a

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small number of Fe2+ are replaced by Fe3+ ions. Three Fe2+ will be replaced by two Fe3+ to maintain
electrical neutrality but then what we obtain is an iron-deficient crystal.

(b) Fe2O3. If all Fe2+ are replaced by Fe3+, the ratio between Fe:O will be 2 : 3 (since 3 Fe2+ are replaced
by 2Fe3+) and not 1 : 1. As such, we obtain Fe2O3.

(c) Fe3O4. This is obtained byreplacing exactly two thirds of Fe2+ byFe3+ (in FeO structure). The remaining
Fe2+ ions and 50% of Fe3+ ions occupy the octahedral voids. The remaining Fe3+ ions occupy tetrahedral
voids.
If in the structure of Fe3O4, the Fe2+ ions are replaced by divalent cations such as Mg2+, Zn2+, etc., the
compounds obtained are called ferrites. In ferrites, divalent cations occupytetrahedral voids and trivalent
cations occupy octahedral voids. This structure is called spinel structure.
7. IMPERFECTIONS IN SOLID
Any deviation from the perfectly ordered arrangement constitutes a defect or imperfection. These defects
sometimes called thermodynamic defects because the number of these defects depends on the temperature.
Crystals may also possess additional defect due to the presence of impurities. Imperfection not only
modify the properties of solids but also give rise to new properties.
7.1 Electronic imperfection
Generally, electrons are present in fullyoccupied lowest energy states. But at high temperatures, some of
the electrons may occupy higher energy state depending upon the temperature.
For example, in the crystals of pure Si or Ge some electrons are released thermally from the covalent
bonds at temperature above 0 K. These electrons are free to move in the crystal and are responsible for
electrical conductivity. This type of conduction is known as intrinsic conduction.
The electron deficient bond formed by the release of an electron is called a hole. In the presence of
electric field the positive holes move in a direction opposite to that of the electrons and conduct electricity.
7.2 Atomic imperfection
The compounds in which the number of irregularity present in the arrangement of atoms or ions are
called- atomic imperfections. It is of two types -

8. STOICHIOMETRIC DEFECTS
Those compounds in which the number of positive and negative ions are exactly in the ratio indicated by
their chemical formula are called stoichiometric compounds. eg NaCl (1 : 1)
These solids show following types of defects:
8.1 Schottky defect : This type of defect is created when same number of positive ion and negative ion are
missing from their respective positions leaving behind a pair of holes. Schottky defect is more common
in ionic compounds with high co-ordination number and where the size of positive and negative ions are
almost equal. The presence of large number of schottky defects in crystal results in significant decrease

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in its density. Eg. NaCl, KCI, CsCl, KBr etc.

8.2 Interstitial Defect : This type of defect is caused due to the presence of ions in the normally vacant
interstitial sites in the crystal.
8.3 Frenkel Defect : This type of defect is created when an ion leaves its correct lattice site and occupies
an interstitial site. Frenkel defects are common in ionic compounds which have low co-ordination number
and in which there is large difference in size between positive and negative ions. Eg. ZnS,AgCI,AgBr,
Ag etc.

8.4 Non Stoichiometric Defect Frenkel Defect

There are many compound in which the ratio of positive and negative ions present in the compound
differs from that required byideal formula of the compound. Such compounds are called Nonstoichiometric
compounds. eg. VOx (Where x can vary between 0.6 to 1.3.)
In these compounds balance of positive and negative charges is maintained by having extra electrons or
extra positive charge.
So, these defects are of following types:
8.4.1 Metal excess defects due to anion vacancies
A compound may have excess metal ion if a negative ion is absent from its lattice site, leaving a hole
which is occupied by electron to maintain electrical neutrality.
The holes occupied by electrons are called F-centres and are responsible for the colour of the compound.
Eg.
 The excess sodium in NaCl makes the crystal appears yellow.
 Excess potassium in KCl makes it voilet.
 Excess lithium in LiCl makes it Pink.
Greater the number of F-centres greater is the intensity of colour. This type of defects are found in crystal
which are likely to possess schottky Defects.

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8.4.2 Metal excess defects due to interstitial cations

It may occur if an extra positive ion is present in an interstitial site. Electrically neutralityis maintained by
the presence of an electron in the interstitial site.
This type of defects are exhibited bythe crystals which are likelyto exhibit “Frenkel defects”. [Link]
colour of ZnS.

8.4.3 Metal deficiency due to cation vacancies

The non-stoichiometric compound may have metal deficiency due to the absence of a metal ion from its
lattice site. The charge is balanced by an adjacent ion having higher positive charge.
This type of defects are generally shown by compounds of transition metals.

Illustration
8. Analysis shows that nickel oxide has the formula Ni0.98O. What fractions of the nickel exist as Ni2+ and
Ni3+ ?
Sol. 98 Ni atoms are associated with 100 O atoms. Out of 98 Ni atoms, suppose Ni present as Ni2+ = x
Then Ni present as Ni3+ = 98 – x
Total charge on x Ni2+ and (98 – x) Ni3+ should be equal to total charge on
100 O2– ions.
Hence, 2 × x + 3 × (98 – x) = 100 × 2
or 2x + 294 – 3x = 200
 x = 94

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94
 Fraction of Ni present as Ni2+ =  10  96%
98
4
Fraction of Ni3+ present as Ni3+ =  100  4%
98

9. PROPERTIES OF SOLIDS
9.1 Electrical properties of solids :
On the basis of electrical conductivity, solids are classified into three types.
i. metals ii. semi-conductors iii. insulators
Electrical conductivity of metals is very high and is of the order of 106 – 108 ohm–1 cm–1.
Electrical conductivity of solids is due to the movement of electrons and positive holes or through the
motion of ions.

The conduction through electrons is called n-type conduction and through positive ions is called p-type
conduction.
Pure ionic solids, where conduction takes place only through motion of ions, are insulators.

The presence of defects in the crystal structure increases their conductivity.

The solids whose conductivity lies between those of metallic conductors and insulators are called semi-
conductors.
Semi - conductors have conductivity which lies in the range of 102 – 10–9 ohm–1 cm–1.
The solids which do not allow the passage of electric current through them are called insulators.
Eg: Wood, rubber, sulphur, phosphorus etc..

The conductivityof semi conductors and insulators is mainly due to the presence of interstitial electrons
and positive holes in the solids due to imperfections.
The conductivity of semi conductors and insulators increases with increase in temperature while that of
metals decreases.

9.2 Magnetic properties of solids :

The substances which are weakly repelled by magnetic field are called diamagnetic substances.
Eg : TiO2, NaCl, benzene etc..
Diamagnetism arises when all the electrons are paired.
The substances which are weakly attracted by magnetic field are called paramagnetic substances.
Atoms, ions or molecules with unpaired electrons exhibit paramagnetism.
Paramagnetic substances lose their magnetism in the absence of magnetic field.
Eg : TiO, VO2 ,CuO etc.
The substances which are strongly attracted by magnetic field are called ferromagnetic substances.
Ferromagnetic substances show permanent magnetism even in the absence of magnetic field.
Eg : Iron, cobalt, nickel, CrO2 etc.
Ferromagnetism arises due to spontaneous alignment of magnetic moments in the same direction.

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Anti ferromagnetism arises due to the alignment of magnetic moments in opposite direction in a compen-
satory manner and resulting in a zero magnetic moment.
Eg : MnO, MnO2, Mn2O3.
Ferrimagnetism arises due to alignment of magnetic moments in opposite directions resulting in a net
magnetic moment.
Eg : Fe3O4, M2+Fe2O4 ; (M = Mg, Cu, Zn etc.)
Ferromagnetic and ferrimagnetic substances change into paramagnetic substances at higher tempera-
tures due to randomisation of spins.

9.3 Dielectric Properties :

A dielectric is a substance in which an electric field gives rise to no net flow of electric charge. The
electrons in a dielectric are tightly held by individual atoms.

Due to shift in charges, dipoles are created which result into polarisation.

The dipoles may align in an ordered manner such that there is some resultant dipole moment in the
crystals.

The dipoles may align in such a way that the dipole moments cancel each other and resultant dipole
moment is zero.

There may be no dipoles in the crystal but only ions are present.
Depending upon the alignment of the dipoles, the properties of crystals are:
i. Piezoelectricity ii. Ferroelectricity [Link]-ferroelectricity iv. Pyroelectricity

i. Piezoelectricity :
The crystals in which the dipoles may align in an ordered way having some dipole are referred to as
piezoelectrics and such crystals exhibit piezoelectricity.
Piezoelectric crystals act as mechanical-electrical transducers.
When these crystals are subjected to a pressure or mechanical stress, electricity is produced. These
crystals are used as pickups in record players by the application of pressure.

ii. Ferroelectricity :
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 called ferroelectricity.
The direction of polarisation in these substances can be changed by applying electric field.
The examples are barium titanate (Ba TiO3), sodium potassium tartrate (Rochelle salt) and potassium
dihydrogen phosphate (KH2PO4).

iii. Anti-ferroelectricity :
If the alternate dipoles are in opposite direction, then the net dipole moment will be zero and the crystal
is called anti-ferroelectric and the phenomenon is antiferroelectricity.

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iv. Pyroelectricity :
Some of the polar crystals when heated produce small electric current. This phenomenon is called
pyroelectricity.

10. Super Conducting Materials

 Super conducting materials are those which offer no resistance to the passage of electricity. Electrical
resistance decreases with decrease in temperature and becomes almost zero near the absolute zero.
 In this state, the materials become diamagnetic and are repelled by the magnets.
 Most metals become super conducting at very low temperatures (2 - 5K).
 The highest temperature at which superconductivity was known is 23K in alloys of niobium
(e.g.Nb3 Ge).
 Some organic compounds also become super conducting at temperatures below 5 K.
 Some complex metal oxides passes super conductivity at higher temperatures.
Super conductors are used in electronics, building magnets, power transmission, levitation transportation,
(trains which move in air without rails).

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THE ATLAS

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