CHEMISTRY SOLID STATE

Matter

Solid Liquid Gas

Amorphous Crystalline

Molecular Metallic Ionic Covalent solid or

Solid solid solids Networked solids

Solid Liquid Gas

(1) Have definite volume Have definite volume Have indefinite volume
(2) Their shape is fixed Their shape is indefinite volume Their shape is indefinite
(3) They have strongest Their force of attraction is They have very weak force of
intermolecular attraction. intermediate between solids attraction . Hence molecules are
Hence their shape as well and gases . So shape is very - very loosely connected
as volume is fixed variable but volume is fixed. with each other and hence have
neither shape nor volume fixed.
The outstanding macroscopic properties of gases are compressibility and fluidity.
In contrast, the most noticeable macroscopic features of crystalline solids are rigidity, incompressibility and
characteristic geometry. We shall find that the explanation of these macroscopic properties in terms of the
atomic theory involves the idea of lattice: a permanent ordered arrangement of atoms held together by forces
of considerable magnitude.

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CHEMISTRY SOLID STATE

Thus the extremes of molecular behaviour occur in gases and solids. In the former we have molecular chaos
and vanishing intermolecular forces, and in the latter we have an ordered arrangement in which the interatomic
forces are large.

Types of Solids
a) Crystalline solids: In a single crystal the regularity of arrangement of the pattern extends throughout the solid and all
points are completely equivalent.
b) Amorphous solids: An amorphous solid differs from a crystalline substance in being without any shape of its own
and has a completely random particle arrangements, i.e. no regular arrangement. Example: Glass, Plastic

Crystalline solid Amorphous solid

1. The constituent particles are 1. The constituent particles are not

arranged in a regular fashion arranged in any regular fashion. There
containing short range as well as may be at the most some short range
long range order. order only.

2. They have sharp melting point 2. They melt over a range of temperature.

3. They are anisotropic i.e., properties 3. They are isotropic i.e., properties like
like electrical conductivity, thermal electrical conductivity, thermal
expansion, etc have different expansion, etc have same value in
values in different direction. different directions

4. They under go a clean cleavage. 4. They undergo an irregular cut

Temperature 
Temperature

a
b

Time  Times 
Crystalline substances Amorphous substances
Cooling Curve. (cooling curve)
(figure 1a) (figure 1b)

Classification of crystalline
Molecular solids : Those solids which consists of small molecules are called molecular solids.
(1) Non - polar molecular solids :
(electronegativity sequence (F > O > N  Cl > Br > S > C  H)
The solids which have zero dipole moment are called non-polar molecular solids.
The molecules are held together by weak Vander waal’s forces . Hence they are either gas or liquids
at room temperature.
They are poor conductor of electricity due to their non-polar nature.

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CHEMISTRY SOLID STATE

(2) Polar molecular solids :

Those solids which have non-zero dipole moments are called polar molecular solids.
Polar molecular solids have dipole - dipole interaction, which is slightly stronger than vander waal’s
force and hence they have larger melting and boiling points than the non - polar molecular solids .
Example : Solid CO2 , Solid NH3
They are generally liquids or gases at room temperature.
(3) Hydrogen bonded molecular solids :
Those molecular solids which are bonded with each other by hydrogen
bonds are called hydrogen bonded molecular solids .
Example : Ice
They are non-conductor of electricity
Generally they are liquid at room temperature or soft solids .
 IONIC SOLIDS : All those solids whose constituent particles are ions are called ionic solids,
Example : NaCl, CsBr, AgBr, CsCl
 METALLIC SOLIDS :
 All those solids which are bonded by metallic bonds are called metallic solids.
 Inner core electrons are immobile
 Metallic solids show a great electrical conductivity due to availability of large number of free electrons whose
movements constitute electric current.
 Metallic solids are malleable and ductile.
 Metallic solids have lustre.
 Metallic solids have good thermal conductivity.

 COVALENT SOLIDS OR NETWORKED SOLIDS :

Whenever electric field is applied, electrons move between the layers.
Graphite is a good conductor of electricity due to availability of free electrons.
Networked solids are hard and brittle.
Carbon - carbon bond has got partial double bond character in graphite.
Two layers in graphite are attached with each other by weak vander waal force.
Graphite can be used as a lubricant at high temperatures .

What is a crystal:
A crystalline solid consist of a large number of small units, called crystals, each of which possesses a definite
geometric shape bounded by plane faces. The crystals of a given substance produced under a definite set of
conditions are always of the same shape.
Unit Cells
In this topic we would be studying certain properties of a solid which depend only on the constituents of the solid and
the pattern of arrangement of these constituents. To study these properties, it would be convenient to take up as small
amount of the solid as possible because this would ensure that we deal with only the minimum number of atoms or
ions. This smallest amount of the solid whose properties resemble the properties of the entire solid irrespective of the
amount taken is called a unit cell. It is the smallest repeating unit of the solid. Any amount of the solid can be
constructed by simply putting as many unit cells as required.
Bravais Lattices
Bravais (1848) showed from geometrical considerations that there are only seven shapes in which unit cells can

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CHEMISTRY SOLID STATE

exist. These are: (i) Cubic (ii) Orthorhombic (iii) Rhombohedral (iv) Hexagonal (v) Tetragonal (vi) Monoclinic
and (vii) Triclinic. Moreover he also showed that there are basically four types of unit cells depending on the manner
in which they are arranged in a given shape. These are : Primitive, Body Centered, Face Centered and End Centered.
He also went on to postulate that out of the possible twenty eight unit cells (i.e. seven shapes  four types in each
shape = 28 possible unit cells), only fourteen actually would exist. These he postulated based only on symmetry
considerations. These fourteen unit cells that actually exist are called Bravais Lattices.
Primitive Cubic Unit Cell
In a primitive cubic unit cell the same type of atoms are present at all the corners of the unit cell and are not present
anywhere else. It can be seen that each atom at the corner of the unit cell is shared by eight unit cells (four on one layer,
as shown, and four on top of these). Therefore, the volume occupied by a sphere in a unit cell is just one-eighth of its
total volume. Since there are eight such spheres, the total volume occupied by the spheres is one full volume of a
sphere. Therefore, a primitive cubic unit cell has effectively one atom. A primitive cubic unit cell is created in the
manner as shown in the figure. Four atoms are present in such a way that the adjacent atoms touch each other.
Therefore, if the length of the unit cell is ‘a’, then it is equal to 2r, where r is the radius of the sphere. Four more spheres
are placed on top of these such that they eclipse these spheres. The packing efficiency of a unit cell can be understood
by calculating the packing fraction. It is defined as ratio of the volume occupied by the spheres in a unit cell to the
4 3
r
volume of the unit cell and void fraction is given as 1 – Packing fraction. Therefore, PF = 3 3 0.52 . (This implies
(2r )
that 52 % of the volume of a unit cell is occupied by spheres). VF  0.48

r r

Figure 3(b)

Fig. 3 (a). Primitive Cubic unit cell

a

Body Centered Cubic Unit Cell

A Body Centred unit cell is a unit cell in which the same atoms are present at all the corners and also at the center of
the unit cell and are not present anywhere [Link] unit cell is created by placing four atoms which are not touching
each other. Then we place an atom on top of these four. Again, four spheres eclipsing the first layer are placed on top
of this. The effective number of atoms in a Body Centered Cubic Unit Cell is 2 (One from all the corners and one at
the center of the unit cell). Moreover, since in BCC the body centered atom touches the top four and the bottom four
4
2 r 3
3  0.68
atoms, the length of the body diagonal ( 3 a ) is equal to 4r. The packing fraction in this case is = 4r 3
( )
3
VF  0.32

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CHEMISTRY SOLID STATE

r
a
2r

a r
C
a
Fig. 4 (a) Body Centered Cubic unit cell

figure 4(b)

Face Centered Cubic Unit Cell

In a fcc unit cell, the same atoms are present at all the corners of the cube and are also present at the centre of each
square face and are not present anywhere else. The effective number of atoms in fcc is 4 (one from all the corners, 3
from all the face centers since each face centered atom is shared by two cubes). Since, here each face centered atom
touches the four corner atoms, the face diagonal of the cube ( 2 a ) is equal to 4r..
a
a
4 4r
4 r 3
packing fraction 3 0.74
 4r 3 VF  0.26
( )
2

Figure 5(b)

Hexagonal Primitive Unit Cell

Each corner atom would be common to 6 other unit cells, therefore their contribution to one unit cell would be 1/6.
Therefore, the total number of atoms present per unit cell effectively is 6.

F
D
C
a h/2
a
E G
A B
r
A a/ 3 E

Figure 6(b) ABCD is the base of hexagonal unit cell AD=AB=a. The sphere in the next layer has its centre F vertically
above E and it touches the three spheres whose centres are A,B and D.

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CHEMISTRY SOLID STATE

A
A

B 
B

A Figure 6(a)

HEXAGONAL CLOSE PACKING (HCP)

2
2 3 a 2r h  2r 
 AE   a  Hence FE = = (2r )   
2
 The height of unit
3 2 3 3 2  3

2
cell (h) = 4r
3

3
The area of the base is equal to the area of six equilateral triangles, = 6× (2r ) 2 . The volume of the unit cell =
4

3 2
6× (2r )2 ×4r .
4 3
Therefore

4
6 πr 3
3
PF = 3 2 = 0.74 VF  0.26
6 (2r )2 4r
4 3

Density of crystal lattice

The density of crystal lattice is same as the density of the unit cell which is calculated as
mass of unit cell number of effective atoms  mass number
 = volume of unit cell = volume of unit cell  Avogadro number

nM
 = N V
A

Seven crystal systems : The seven crystal systems are given below.

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CHEMISTRY SOLID STATE

Crystal System Bravais Lattices Parameters of Unit Cell

Intercepts Crystal angle Example
Primitive, Face Centered, Pb,Hg,Ag,Au
1. Cubic a=b=c  =  =  = 90o
Body Centered = 3 Diamond, NaCl, ZnS
Primitive, Face Centered,
2. Orthorhombic Body Centered, End abc  =  =  = 90o KNO2, K2SO4
Centered = 4
o
3. Tetragonal Primitive, Body Centered =2 a=bc  =  =  = 90 TiO2,SnO2
o
 =  = 90 ,
4. Monoclinic Primitive, End Centered = 2 abc CaSO4,2H2O
  90o
K2Cr2O7,
5. Triclinic Primitive = 1 abc       900
CaSO45H2O
0
 =  = 90 ,  =
6. Hexagonal Primitive = 1 a=bc o Mg, SiO2, Zn, Cd
120
 =  = 90o,  
7. Rhombohedral Primitive = 1 a=b=c As, Sb, Bi, CaCO3
90 o
Total = 14

Illustration 1: Lithium borohydride crystallizes in an orthorhombic system with 4 molecules

per unit cell. The unit cell dimensions are a = 6.8Å,
b = 4.4Å and C = 7.2Å. If the molar mass is 21.76g. Calculate density of crystal.
Solution: Since
n  mol. wt
Density,  = Volume  Av. No.
Here n = 4, Av. No = 6.023  1023, &
Volume = V = a  b  c
= 6.8  10–8  4.4  10–8  7.2  10–8 cm3 = 2.154  10–22 cm3
4  21.76
 density,  = = 0.6708 gm/cm3
2.154  10  22  6.023  10 23
Close Packing of Spheres
Atoms are space filling entities and structures can be described as resulting from the packing of spheres. The most
efficient, called Closest Packing, can be achieved in two ways, one of which is called Hexagonal Close Packing
(Hexagonal Primitive) and the other, Cubic Close Packing (ccp or fcc). Hexagonal close packing can be built up as
follows:
Place a sphere on a flat surface. Surround it with six equal spheres as close as possible in the same plane.
Looking down on the plane, the projection is as shown in Fig. 7 (a). Let us call this layer as the A layer. Now
form over the first layer a second layer of equally bunched spheres, Fig 7 (b), so as to nestle into the voids. It
will be clearly seen that once a sphere is placed over a void, it blocks the void which are adjacent to that void.
Let us call this layer as the B layer. Now, it can be clearly seen that there are two types of voids created by the
B layer of spheres. If a sphere is placed on the x - type of voids, it would resemble the A layer of spheres in the

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CHEMISTRY SOLID STATE

sense that it eclipses the spheres of the A layer. This arrangement (i.e., ABAB……) is called the hexagonal
close packing (hcp) or hexagonal primitive. On the other hand, if the spheres were to be placed on the y
- type of voids, it would neither eclipse the A layer nor the B layer of spheres. This would clearly be a unique
layer. Let us call this layer as the C layer (as seen in figure 7(c). This arrangement (i.e, ABCABC...) is called
the Cubic Close Packing (fcc).

Fig. 7 (a)' A' layer of spheres. ‘x’ type void ‘y’ type voide
Fig. 7(b)' A' and 'B' layer of spheres.

Exercise 1: It can be seen now that both fcc and Hexagonal Primitive Structure have the same packing
fraction. Moreover this is also the highest packing fraction of all the possible unit cells with one type of
atom with empty voids. Can you explain this?
Octahedral and Tetrahedral Voids
The close packing system involves two kinds of voids - tetrahedral voids and octahedral voids. The former has
four spheres adjacent to it while the latter has six spheres adjacent to it. These voids are only found in either fcc
or Hexagonal Primitive unit cells. Let us first consider a fcc unit cell (as shown in the figure 8(a).). Not all the
atoms of the unit cell are shown (for convenience). Let us assume that there is an atom (different from the one
that forms the fcc) at the center of an edge.
Let it be big enough to touch one of the corner atoms of the fcc. In that case, it can be easily understood that
it would also touch six other atoms (as shown) at the same distance. Such voids in an fcc unit cell in which if we
place an atom it would be in contact with six spheres at equal distance (in the form of an octahedron) are called
octahedral voids (as seen in fig. 8(a).
On calculation, it can be found out that a fcc unit cell has four octahedral voids effectively. The number of effective
octahedral voids in a unit cell is equal to the effective number of atoms in that unit cell.
Let us again consider a fcc unit cell. If we assume that one of its corners is an origin, we can locate a point having
coordinates (¼,¼,¼). If we place an atom (different from the ones that form the fcc) at this point and if it is big enough
to touch the corner atom, then it would also touch three other atoms (as shown in the fig. 8(b) which are at the face
centers of all those faces which meet at that corner. Moreover, it would touch all these atoms at the corners of a
regular tetrahedron. Such voids are called tetrahedral voids (as seen in fig. 8(b).
Since there are eight corners, there are eight tetrahedral voids in a fcc unit cell. We can see the tetrahedral voids
in another way. Let us assume that eight cubes of the same size make a bigger cube as shown in the fig. 8(c).
Then the centers of these eight small cubes would behave as tetrahedral voids for the bigger cube (if it were
face centered). The number of tetrahedral voids is double the number of octahedral voids. Therefore,
the number of tetrahedral voids in hcp is 12.
Radius Ratio Rules
The structure of many ionic solids can be accounted for by considering the relative sizes of the positive and negative
ions, and their relative numbers. Simple geometric calculations allow us to workout, as to how many ions of a given
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CHEMISTRY SOLID STATE

size can be in contact with a smaller ion. Thus, we can predict the coordination number from the relative sizes of the
ions.
Co-ordination Number 3
The adjacent fig. 9(a) shows the smaller positive ion of radius r+ is in contact with three larger negative ions of radii r-
. It can be seen that AB = BC = AC = 2r-, BD = r- + r+. Further, the angle ABC is 60o, and the angle DBE is 30o. By
trigonometry Cos 30o = (BE / BD). BD = (BE / Cos 30o), r+ + r- = r- / Cos 30o = (r- / 0.866) = r-  1.155, r+ = (1.155
r-) - r- = 0.155 r-, Hence (r+ / r-) = 0.155.
Co-ordination Number 4 (Tetrahedron)
Angle ABC is the tetrahedral angle of 109o 28' and hence the angle ABD is half of this, that is 54o44'. In the triangle
r r  r  1
ABD, Sin ABD = 0.8164 = AD / AB =   . Taking reciprocals,   1.225 , rearranging, we get,

r r r 0.8164
r
0.225 .
r
Co-ordination Number 6 (Octahedron) or 4 ( Square Planar)
A cross section through an octahedral site is shown in the adjacent figure and the smaller positive ion (of radius r+)
touches six larger negative ions (of radius r-). (Note that only four negative ions are shown in this section and one is
above and one below the plane of the paper). It is obvious that AB = r+ + r- and BD = r-. The angle ABC is 45o in
r
the triangle ABD. cos ABD = 0.7071 = (BD / AB) = r . Rearranging, we get, r+/r–= 0.414
r  r

r Co – ordination
Limiting radius ratio x Shape Example
r number
x < 0.155 2 Linear BeF2
0.155  x  0.225 3 Planar Triangle AlCl3
0.225  x  0.414 4 Tetrahedron ZnS
0.414  x  0.732 4 Square planar PtCl42-
0.414  x  0.732 6 Octahedron NaCl
0.732  x  0.999 8 Body centered cubic CsCl
Exercise 2: The radius of a calcium ion is 94 pm and of an oxide ion is 146 pm. Predict the
crystal structure of calcium oxide.
Classification of Ionic Structures
In the following structures, a black circle would denote a cation and a white circle would denote an [Link] any solid
of the type AxBy, the ratio of the coordination number of A to that of B would be y : x.
Rock Salt Structure
Cl- is forming a fcc unit cell in which Na+ is in the octahedral voids. The coordination number of Na+ is 6 and therefore
that of Cl- would also be 6. Moreover, there are 4 Na+ ions and 4 Cl- ions per unit cell. The formula is Na4Cl4
i.e,NaCl. The other substances having this kind of a structure are halides of all alkali metals except cesium halides and
oxides of all alkaline earth metals except beryllium oxide.

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CHEMISTRY SOLID STATE

–
Cl
+
Na

Figure 10 Unit cell structure of NaCl

Zinc Blende Structure
Sulphide ions are face centered and Zinc is present in alternate tetrahedral voids. Formula is Zn4S4, i.e, ZnS. Coordination
number of Zn is 4 and that of sulphide is also 4. Other substance that exists in this kind of a structure is BeO.
Fluorite Structures
Calcium ions are face centered and fluoride ions are present in all the tetrahedral voids. There are four calcium ions
and eight fluoride ions per unit cell. Therefore the formula is Ca4F8, (i.e, CaF2). The coordination number of fluoride
ions is four (tetrahedral voids) and thus the coordination number of calcium ions is eight. Other substances which exist
in this kind of structure are UO2, and ThO2.
Anti-Fluorite Structure
Oxide ions are face centered and lithium ions are present in all the tetrahedral voids. There are four oxide ions and
eight lithium ions per unit cell. As it can be seen, this unit cell is just the reverse of Fluorite structure, in the sense that,
the positions of cations and anions is interchanged. Other substances which exist in this kind of a structure are Na2O,
K2O and Rb2O.
Cesium Halide Structure
Chloride ions are primitive cubic while the cesium ion occupies the center of the unit cell. There is one chloride ion and
one cesium ion per unit cell. Therefore the formula is CsCl. The coordination number of cesium is eight and that of
chloride ions is also eight. Other substances which exist in this kind of a structure are all halides of cesium.

Corundum Structure
The general formula of compounds crystallizing in corundum structure is A2O3. The closest packing is that of
anions (oxide) in hexagonal primitive lattice and two-third of the octahedral voids are filled with trivalent
cations. Examples are : Fe2O3, Al2O3 and Cr2O3.
Pervoskite Structure
The general formula is ABO3. One of the cation is bivalent and the other is tetravalent. Example: CaTiO3, BaTiO3.
The bivalent ions are present in primitive cubic lattice with oxide ions on the centers of all the six square faces. The
tetravalent cation is in the center of the unit cell occupying octahedral void.
Spinel and Inverse Spinel Structure
Spinel is a mineral (MgAl2O4). Generally they can be represented as M2+M23+O4, where M2+ is present in one-
eighth of tetrahedral voids in a FCC lattice of oxide ions and M3+ ions are present in half of the octahedral
voids. M2+ is usually Mg, Fe, Co, Ni, Zn and Mn; M3+ is generally Al, Fe, Mn, Cr and Rh. Examples are
ZnAl2O4, Fe3O4, FeCr2O4 etc. Many substances of the type M 4  M 22  O 4 also have this structure. In an inverse
spinel the ccp is of oxide ions, M2+ is in one-eight of the tetrahedral voids while M3+ would be in one-eight of
the terahedral voids and one-fourth of the octahedral voids.

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CHEMISTRY SOLID STATE

Exercise 3: The unit cell of silver iodide (AgI) has 4 iodine atoms in it. How many silver atoms must be
there in the unit cell.
Exercise 4: The co-ordination number of the barium ions, Ba 2+, in barium chloride (BaF2) is 8. What
must be the co-ordination number of the fluoride ions, F .

Imperfections in a Crystal
The discovery of imperfections in an other wise ideally perfect crystal is one of the most fascinating aspects of
solid state science. An ideally perfect crystal is one which has the same unit cell and contains the same lattice
points throughout the crystal. The term imperfection or defect is generally used to describe any deviation
of the ideally perfect crystal from the periodic arrangement of its constituents.
Point Defect
If the deviation occurs because of missing atoms, displaced atoms or extra atoms, the imperfection is named as
a point defect. Such defects can be the result of imperfect packing during the original crystallisation or they
may arise from thermal vibrations of atoms at elevated temperatures because with increase in thermal energy
there is increased probability of individual atoms jumping out of their positions of lowest energy. The most
common point defects are the Schottky defect and the Frenkel defect. Comparatively less common point
defects are the metal excess defect and the metal deficiency defects. All these defects have been discussed
below in some details.
Schottky Defects: The defects arise if some of the lattice points in a crystal are unoccupied. The points
which are unoccupied are called lattice vacancies. The existence of two vacancies, one due to a missing Na+
ion and the other due to a missing Cl– ion in a crystal of NaCl, is shown in figure 16. The crystal, as a whole
remains neutral because the number of missing positive and negative ions is the same.

–
+
Na missing Cl missing
Figure 16

Schottky defects appear generally in ionic crystals in which the positive and the negative ions do not differ
much in size. Sodium chloride and cesium chloride furnish good examples of ionic crystals in which Schottky
defects occurs.
Frenkel Defects:
These defects arise when an ion occupies an interstitial position between the lattice points. This is shown
in figure for the crystal of AgBr.

Ag + Br– Ag + Br– Ag+ Br– Ag+ Br– Ag +

Br – Ag + Br – Ag+ Br– Ag+ Br– Ag + Br–
+

Ag + Br– Ag
Br– Ag+ Br– Ag+ Br– Ag +
Br – Ag + Br – Ag+ Br– Ag+ Br– Ag + Br–
Figure 17: Frenkel Defects in a Crystal

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CHEMISTRY SOLID STATE

As can be seen, one of the Ag+ ions occupies a position in the interstitial space rather than its own appropriate
site in the lattice. A vacancy is thus created in the lattice as shown. It may be noted again that the crystal remains
neutral since the number of positive ions is the same as the number of negative ions. The presence of Ag+ ions
in the interstitial space of AgBr crystal is responsible for the formation of a photographic image on exposure of
AgBr crystals (i.e., photographic plate) to light.
ZnS is another crystal in which Frenkel defects appear. Zn2+ ions are entrapped in the interstitial space leaving
vacancies in the lattice.
Frenkel defects appear in crystals in which the negative ions are much larger than the positive ions. Like
Schottky defects, the Frenkel defects are also responsible for the conduction of electricity in crystals and also
for the phenomenon of diffusion in solids.
Metal Excess Defects. The Colour Centres. It has been observed that if a crystal of NaCl is heated in
sodium vapour, it acquires a yellow colour. This yellow colour is due to the formation of a non-stoichiometric
compound of sodium chloride in which there is a slight excess of sodium ions. What happens in this case is that
some sodium metal gets doped into sodium chloride crystal which, due to the crystal energy, gets ionised into
Na+ and e–. This electron occupies a site that would otherwise be filled by a chloride ion, as illustrated in figure.

+
Na Cl
–

–
e

F Centre
F-centre in a Sodium chloride crystal
Figure 18
There is evidently an excess of metal ions although the crystal as a whole is neutral. A little reflection would
show that there are six Na+ sites adjacent to the vacant site occupied by the electron. The extra electron in thus
shared between all the six Na+ ions which implies that this electron is not localised at the vacant Cl– site. On the
other hand, this electron is similar to the delocalised  electrons present in molecules containing conjugate
double bonds. Light is absorbed when this delocalised electron makes an easy transition from its ground state
to an excited state. As a result, the non – stoichiometric form of sodium chloride appears coloured. Because
of this, the sites occupied by the extra electrons are known as colour centres. These are also called F-
centres. This name comes from the German word Farbe meaning colour. The non-schiometric sodium chloride
may be represented by the formula Na(1+)Cl where  is the excess sodium metal doped in the crystal because
of its exposure to sodium vapour.
Another common example of metal excess defects is the formation of a magenta coloured non-stoichiometric
compound of potassium chloride by exposing the crystals of KCl to K metal vapour. The coloured compound
contains an excess of K+ ions, the vacant Cl– sites being filled by electrons obtained by the ionization of the
excess K metal doped in to the crystal.
Metal Deficiency Defects. In certains cases, one of the positive ions is missing from its lattice site and the
extra negative charge is balanced by some nearby metal ion acquiring two charges instead of one. There is
evidently, a deficiency of the metal ions although the crystal as a whole is neutral. This type of defect is generally
found amongst the compounds of transition metals which can exhibit variable valency. Crystals of FeO, FeS
and NiO show this type of defects. The existence of metal deficiency defects in the crystal of FeO is illustrated.

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CHEMISTRY SOLID STATE

Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe 2+ O 2– Fe2+ O2–

O2– Fe 2+ O2– Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+
Fe2+ O2– Fe2+ O2– Fe2+ O2– O 2– Fe2+ O2–
O2– Fe 2+ O2– Fe2+ O2– Fe+3 O2– Fe+3 O2– Fe2+
Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe 2+ O 2– Fe2+ O2–
Figure 19

It is evident from the above discussion that all types of point defects result in the creation of vacancies or ‘holes’
in the lattice of the crystals. The presence of holes lowers the density as well as the lattice energy or the stability
of the crystals. The presence of too many holes may cause a partial collapse of the lattice.
MAGNETIC PROPERTIES :
The macroscopic magnetic properties of material are consequence of magnetic moments associated with the
individual electron. Each electron in an atom has magnetic moment due to two reasons. The first one is due to the
orbital motion around the nucleus, and the second is due to the spin of electron around its own axis. A moving
electron may be considered to be a small current loop, generating a small magnetic field, and having a magnetic
moment along its axis of rotation.
The other type of magnetic moment originates from electron spin which is directed along the spin axis. Each
electron in an atom may be thought of as being a small magnet having permanent orbital and spin magnetic
moments. The fundamental magnetic moment is Bohr Magneton, s equal to 9.27 × 10–24 Am2 . For each electron
in an atom, the spin magnetic moment is ± B (depending upon the two possiblities of the spin). The contribution of
the orbital magnetic moment is equal to i B, where i is the magnetic quantum number of the electron.
Based on the bahaviour in the external magnetic field, the substances are divided different catagories.
(i) Diamagnetic substances : Substances which are weakly repelled by the external magnetic field are called
diamagnetic substances, e.g. TiO2, NaCl, Benzene.
(ii) Paramagnetic substances : Substances which are attracted by the external magnetic field are called paramagnetic
substances, e.g., O2, Cu2+, Fe3+.
(iii) Ferromagnetic substances : Substances which show permanent magnetsim even in the absence of the magnetic
field are called ferromagnetic substances e.g., Fe, Ni, Co, CrO 2.
(iv) 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 substances, e.g., Fe 3O4.
(v) Anti-ferromagnetic substances : Substances which are expected to posses paramagnetic behaviour,
ferromagnetism on the basis of unpaired electron but actually they possess zero not magnetic moment are called
anti-ferromagnetic substances, e.g., MnO2
Note : Ferromagnetic, Anti-ferromagnetic and Ferrimagnetic solids change into paramagnetic at some temperature. It
may be further pointed out here that each ferromagnetic substance has a characteristic temperature above which
no ferromagnetism is observed. This is known as Curie Temperature.
DIELECTRIC PROPERTIES :
Insulators do not conduct electricity because the electrons present in them are hel tightly to the individual atoms or
ions and are not free to move. however, when electric field is applied, polarization takes place because nuclei are
attracted to one side and the electron cloud to the other side. Thus dipoles are formed. In addition to these dipoles,
there may also be permanent dipoles in the crystal. These dipoles may align themselves in an ordered manner so
that such crystals have a net dipole moment.
Such polar crystals show the following interersting propeties :
(i) Piezoelectricity or Pressure - electricity : When mechanical stress is applied on such crystals so as to deform
them, electricity is produced due to displacement of ions. The electricity thus produced is called piezoelectricity
and the crystals are called piezoelectric crystals. A few examples of piezoelectric crystals include Titanates of

PAGE - 13
CHEMISTRY SOLID STATE

Barium and Lead, Lead zirconate (PbZrO3), Ammonium dihydrogen phosphate (NH4H2PO4) and Quarts. These
crystals are used as pick-ups in record players where they prodduce electrical signals by application of pressure.
They are also used in microphones, ultrasonic generators and sonar detectors.
(ii) Ferroelectricity : In some of the piezoelectric crystals, the dipoles are permanently polarized even in the absence
of the electric field. However, on applying, electric field, the direction of polarization changes, this phenomenon is
called ferroelectricity due to analogy with ferromagnetism. Some examples of the ferroelectric solids are barium
titanate (BaTiO3), Sodium potassium tartarate (Rochelle salt) and Potassium dihydrogen phosphate (KH 2PO4)
Note : All ferroelectric solids are piezoelectric but the reverse is not true.
(iii) Anti-ferroelectricity : In some crystals, the dipoles align themselves in such a way that alternately, they point up
and down so that the crystal does not posses any net dipole moment. Such crystals are said to be anti-ferroelectric.
A typical example of such crystals is Lead zirconate (PbZrO3)
Superconductivity :
A substance is said to be superconducting when it offers no resistance to the flow of electricity.
Isomorphism :
The property shown by crystals of different chemical substances which exhibit the same crystalline form is known
as isomorphism.
Such substances have similar chemical formula, e.g., Na2HPO4. 12H2O and Na3ASO4. 12H2O
• Chemically substances having same type of formulae are not necessarily Isomorphous.

MAGNETIC PROPERTIES OF CRYSTALS

Properties Information Magnetic Example Application
Alignment
1. Diamagnetic Repelled weakly in magnetic field. Benzene NaCl, Insulators
Such solids have only paired TiO2, V2O5, etc.
electrons.
2. Paramagnetic Have unpaired electrons; weakly O2, VO, CuO, TiO Electronic
attracted in magnetic field. They devices
cannot be permanently
magnetised.
3. Ferromagnetic Also, have unpaired electrons. Fe, Ni, Co, CrO2 CrO2 is used
Strongly attracted in magnetic in audio, video
field. Such solids can be tapes.
permanently magnetised. On
heating to a temperature called
Curie Point, these solids change
to paramagnetic solid.
4. Antiferrro- In these solids change electrons Cr2O3, CoO, Used in the
magnetic align themselves in such a way Co3O4, Fe2O3 instruments of
that resultant magnetic moment MnO, MnO2 magnetic
is zero. susceptibility
measurement
5. Ferrimagnetic unpaired electrons align themselves Fe3O4, ferrites –
in such way that there is a net OR
magnetic moment.

and so on

PAGE - 14
CHEMISTRY SOLID STATE

ELECTRICAL PROPERTIES OF CRYSTALS

Properties Information Dipolar Example Application
Property
1. Piezoelectri- When a crystal of dielectrics is Development of Quartz and
city subjected to mechanical stress, charge in some Rochelle salt
then small magnitude current part of crystal
is produced. It is called direct
Piezoelectric effect.

2. Anti In some solids, electric field Crystal suffers –

piezoelectricity developes mechanical effect. elastic deforma-
tion in an
electric field
3. Ferroelectricity Piezoelectric crystals having BaTiO3, KH2PO4 Electromagnetic
permanent dipoles are said to Rochelle salt appliances.
possess ferroelectricity
4. Anti Piezoelectric crystals with zero PbZrO3
ferroelectricitydipole are said to posses anti Lead zirconate
ferroelectrictity.
5. Pyroelectricity Some polar crystals produce electric – Crystals of Used in fire alarms,
impulse on heating. tartaric acid. thermostat.

Solved Objective Problems

Ex.1 Select write statement (s)
(A) 8 Cs+ ions occupy the second nearest neighbour locations of a Cs + ion
(B) Each sphere is surrounded by six voids in two dimensional hexagonal close packed layer
(C) If the radius of cations and amions are 0.3 Å and 0.4 Å then coordinate number of cation of the
crystal is 6.
(D) In AgCl, the silver ion is displaced from its lattice position to an interstitial position such a
defect is called a frenkel defect.

voids

Sol. (A) 6 Cs+ ion second nearest neighbour (B)

r
(C) r = 0.75 (BCC) 8 : coordination no. (D) True
–

Ex.2 Which of the following statement is/are incorrect in the rock-salt structure if an ionic compounds
?
(A) coordination number of cation is four where as that of anion is six.
(B) coordination number of cation is six where as that of anion is four.
(C) coordination number of each cation and anion is four.
(D) coordination number of each cation and anion is six.

PAGE - 15
CHEMISTRY SOLID STATE

Sol. Coordination no. of cation = 6

coordination no of anion = 6
Ex.3 Which of the following statements are correct :
(A) The coordination number of each type of ion in CsCl is 8.
(B) A metal that crystallises in BCC structure has a coordination number 12.
(C) A unit cell of an ionic crystal shares some of its ions with other unit cells
(D) The length of the unit cell in NaCl is 552 pm. [rNa  95 pm; rCl–  181 pm]
Sol. r+ + r– = a/2
(95 + 181)= a/2
 a = 276 × 2
a = 552 pm
Ex.4 A cub ic solid is made up of two elements A and B. Atoms B are at the corners of the cube and A at
the body centre. What is the formula of compound.
1
Sol. A = 1 (Body center) B=8× = 1 (for corner) formula = AB
8

Ex.5 A compound alloy of gold and copper crystallizes in a cubic lattice in which gold occupy that lattice
point at corners of the cube and copper atom occupy the centres of each of the cube faces. What is
the formula of this compound.
1 1
Sol. Au =  8  1, Cu = 6  3 Formula = AuCu
8 2

3
Ex.6 A cubic solid is made by atoms A forming close pack arrangement, B occupying one. Fourth of
tetrahedral void and C occupying half of the octahedral voids. What is the formula of compound.

1 1 8
Sol. A= 6  8 =4 B= no. of void (tetrahedral)
2 8 4
=2
C = Total no. of octahedral voids / 2 no. of octahedral voids ( effective)
= 1 + 12 × 1/4 = 4 Bodycenter edgecentre
C = 4/2 = 2 formula = A4B2C2

Ex.7 What is the percent by mass of titanium in rutile, a mineral that contain Titanium and oxygen, if
structure can be described as a closet packed array of oxide ions, with titanium in one half of the
octahedral holes. What is the oxidation number of titanium ?
1
8
1 1  12  1 / 4  4
2
Sol. O2– = + × 6 =4 Ti =
8 2 2 2
TiO2 formula Ti (At mass) = 47.88
47.88
% Ti =  100 = 59.94 % Ox. State = +4
79.88

PAGE - 16
CHEMISTRY SOLID STATE

Ex.8 Spinel is a important class of oxides consisting of two types of metal ions with the oxide ions
arranged in CCP pattern. The normal spinel has one-eight of the tetrahedral holes occupied by one
type of metal ion and one half of the octahedral hole occupied by another type of metal ion. Such a
spinel is formed by Zn2+, Al3+ and O2–, with Zn2+ in the tetrahedral holes. Give the formulae of
spinel.
Sol. Zn2+ = 8/8 = 1
Al3+ = 4/2 = 2
O2– = CCP (4)
ZnAl2O4
1
Zu2+ = × 8 octahedral voids
8

1
Al2+ = 4 octahedral voids
2
O2– = CCP arrangment (1+3) = 4

Ex.9 Iron occurs as bcc as well as fcc unit cell. If the effective radius of an atom of iron is 124 pm.
Compute the density of iron in both these structures.
Sol. In bcc z=2
2  56 a 3 4  124
 , r=  a= in pm
NA (a3 ) 4 3

2  56
= 3 = 7.92 × 106 g/cm3
 4  124 
   10–36  6.022  1023
 
 3 

4  56
In FCC , Z = 4,  3
= 8.6 g/cm3
 4  124  –36 23
   10  6.022  10
 2 

Ex.10 A closed packed structure of uniform spheres has the edge length of 534 pm. Calculate the radius of
sphere, if it exist in
(A) simple cubic lattice (B) BCC lattice (C) FCC lattice
Sol. (A) Simple cubic lattice
a 534
2r = a  r = = = 267 pm
2 2

534 3
(B) 4r = a 3  r = = 231.23 pm
4

534 2
(C) 4r = a 2 r= = 188.79 pm
4

PAGE - 17
CHEMISTRY SOLID STATE

Ex.11 Calculate the density of diamond from the fact that it has face centered cubic structure with two
atoms per lattice point and unit cell edge length of 3.569 Å.
Sol. In simple FCC Z = 4
but here from questins two atoms per lattice point

 8  12 
8  M / NA  6.022  1023 
 z=8   =   g / m3 = 3.5 × 106 g/m3 = 3.5 g/cm3
a3 (3.569  10 )10 3

Ex.12 An element crystallizes into a structure which may be described by a cubic type of unit cell having
one atom on each corner of the cube and two atoms on one of its body diagonals. If the volume of
this unit cell is 24 × 10–24 cm3 and density of element is 7.2 g cm–3, calculate the number of atoms
present in 200 g of element.
Sol. z = 3
M
3
7.2 = N A  M = 34.68
24  10–24

200
no. of atoms in 200 gram = × 6.022 × 1023 = 3.47 × 1024 atoms
34.68
Ex.13 Silver has an atomic radius of 144 pm and the density of silver is 10.6 g cm –3. To which type of cubic
crystal, silver belongs?
z  108 / NA 3
Sol. 10.6 × 106 g/m3 = 3  a  1.692  10–29
a z
4 3
PF =
z
3
r
=

4 / 3  144  10 12 
3
 100  74 %  F.C.C.
 100
a3 1.69  10–29

Ex.14 AgCl has the same structure as that of NaCl. The edge length of unit cell of AgCl is found to be 555
pm and the density of AgCl is 5.561 g cm–3. Find the percentage of sites that are unoccupied.
 143.5 
 4  6.022  1023 
Sol.     5.575 g / cm3
(555  1012 )3

If 100% sites occupied  =5.575 but density is 5.561

5.561
% sites occupied =  100
5.575
% sites unoccupied = 100 – (99.75) %
= 0.25%
Ex.15 Xenon crystallises in the face-centred cubic lattice and the edge of the unit cell is 620 pm. What is
the nearest neighbour distance and what is the radius of xenon atom ?

PAGE - 18
CHEMISTRY SOLID STATE

Sol. nearest neighbour distance = 2r (in FCC)

 a 2 = 4r

a 620
 2r = =
2 1.414
2r  438 .47
r = 219.23
Ex.16 The two ions A+ and B– have radii 88 and 200 pm respectively. In the closed packed crystal of
compound AB, predict the co-ordination number of A +.
r
Sol.  0.44
r–

It could be square plamer or octahedral void

but for closed packed crystal  it is octahedral void = coordination no. = 6
Ex.17 CsCl has the bcc arrangement and its unit cell edge length is 400 pm. Calculate the interionic
distance in CsCl.
Sol. interionic distane
a 3
r+ + r– = = 200 3 = 346.4
2
Ex.18 Gold crystallizes in a face centered cubic lattice. If the length of the edge of the unit cell is 407 pm,
calculate the density of gold as well as its atomic radius assuming it to be spherical. Atomic mass of
gold = 197 amu.
Sol. FCC : Z = 4

 197 
4  23

6.022  10 
  g / m3 = 19.41 × 106 g/m3 = 19.41 g/cm3
(407  10 12 )3

a 2 a 2
& 2r =  r  143.9 pm
2 4
Ex.19 The density of KBr is 2.75 g cm –3. The length of the edge of the unit cell is 654 pm. Show that KBr
has face centered cubic structure.
(N = 6.023 × 1023 mol–1, At. mass : K = 39, Br = 80)
M
z
Sol. NA

a3

a3 119 / 6.023  1023


z 2.75
= 7.18 × 10–23 z = (654 × 10–10)3 / (7.18 × 10–23)  4  FCC

PAGE - 19
CHEMISTRY SOLID STATE

Ex.20 An element crystallizes in a structure having FCC unit cell of an edge 200 pm. Calculate the
density, if 200 g of this element contains 24 × 1023 atoms.
Sol. 24 × 1023 atom contain by 200g
6 × 1023 atom contains by
200
g = 50 g
4
M  50 g/mole

50
4 4  50 4  50 2000
 6  1023 = = =  = 41.67 g/cm3
(200  10 10 )3 6  10  8  10–24
23
48  10 1
48

Ex.21 The effective radius of the iron atom is 1.42 Å. If has FCC structure. Calculate its density
(Fe = 56 amu)

56
4 4r
Sol.  = NA a= = 4.016 Å
2a  4r  2
a3

4  56
 23 = 0.574 × 107 g/m3
6.022  10  (4.016)3  10  30

= 5.74 × 106 g/m3  = 5.74 g/cm3

Ex.22 A crystal of lead (II) sulphide has NaCl structure. In this crystal the shortest distance between Pb +2
ion and S2– ion is 297 pm. What is the length of the edge of the unit cell in lead sulphide ? Also calculate
the unit cell volume.
Sol. NaCl type FCC
a
r+ + r– = = 297  a = 297 × 2 = 594 pm
2
= 594 × 10–10 cm = 5.94 × 10–8 cm a3 = volume % = 2.096 × 10–22 cm3

Ex.23 If the length of the body diagonal for CsCl which crystallises into a cubic structure with Cl – ions at
the corners and Cs+ ions at the centre of the unit cells is 7 Å and the radius of the Cs + ion is 1.69 Å,
what is the radii of Cl– ion ?
Sol. a 3 7

a 3 7
r+ + r– = =
2 2

1.69 + r– = 3.5
r– = 3.5 – 1.69 = 1.81 Å

PAGE - 20
CHEMISTRY SOLID STATE

Ex.24 In a cubic closed packed structure of mixed oxides the lattice is made up of oxide ions, one eighth of
tetrahedral voids are occupied by divalent ions (A 2+) while one half of the octahedral voids occupied
trivalent ions (B3+). What is the formula of the oxide ?
Sol. Total tetrahedral voids = 8
1
A2+ occupied = 8  =1 tetrahedral void
8

Total octahatral void = 4

4
B3+ Occupy = =2
2
A2+ = 1, B3+ = 2, O2– = 4
formula = AB2O4
Ex.25 A solid A+ and B– has NaCl type closed packed structure. If the anion has a radius of 250 pm, what
should be the ideal radius of the cation ? Can a cation C + having a radius of 180 pm be slipped into
the tetrahedral site of the crystal of A+B–? Give reasons for your answer.
r
Sol.  2  1 for ideal NaCl crystal
r

r r
 0.414  r =
r – 0.414

r+ = 103.55 pm
tetrahdral sites
for tetrahedral voids
r
0.225  r < 0.414


r 180
   0.72
r 2.50

no can’t slipped

Ex.26 If the radius of Mg2+ ion, Cs+ ion, O2– ion, S2– ion and Cl– ion are 0.65 Å, 1.69 Å, 1.40 Å, 1.84 Å, and
1.81 Å respectively. Calculate the co-ordination numbers of the cations in the crystals of MgS, MgO
and CsCl.
r 0.65
Sol. for MgS r  1.84  0.353


coordination no = 4
tetrahedral void

PAGE - 21
CHEMISTRY SOLID STATE

r 0.65
MgO  r = = 0.464 Octahedral voids coordination no. = 6
 1.40

 r 1.69
CsCl = r  1.81  0.934 BCC coordination no. = 8


Ex.27 In a cubic crystal of CsCl (density = 3.97 gm/cm 3) the eight corners are occupied by Cl – ions with Cs+
ions at the centre. Calculate the distance between the neighbouring Cs + and Cl– ions.

 M 
1  
Sol. 3.94 =  N A   168.5
a3 6.022  1023  a3

3 168.5
 a 
6.022  1023  3.97
a3 = 7.05 × 10–23 cm3
a = 4.13 × 10–8 cm
a 3
r+ + r– = = 3.577 × 10–8
2
= 3.577 × 10–10 cm = 3.577 Å

Ex.28 Calculate the value of Avogadro's number from the following data :
Density of NaCl = 2.165 cm –3
Distance between Na+ and Cl– in NaCl = 281 pm.
ZM
Sol. d=
a3N A

4  58.5
2.165 =
(562  10 10 )3 NA

 NA = 6 × 1023
r
Na  r
Na 
Ex.29 KCl crystallizes in the same type of lattice as does NaCl. Given that  0.5 and  0.7 Calculate
r
Cl – r
K
:
(a) The ratio of the sides of unit cell for KCl to that for NaCl and
(b) The ratio of densities of NaCl to that for KCl
rN  rN  aKC 2[rk   rC ]
Sol.
a a
(a) = 0.5 = 0.7, aNaCl = 2[rNa  rC ] ....(i)
rC  rK 

rNa rNa  rC–

rC + 1 = 1 + 0.5, rC – = 1.5 ....(ii)

PAGE - 22
CHEMISTRY SOLID STATE

rNa rNa 5 rk  5 rk  5 rk   rC 12

rC–  r = , rC – = , r + 1 = + 1, r = ....(iii)
k  7 7 C – 7 C – 7
From eq. (i)

akC 12 / 7 1.714
aNaCl = 1.5 = 1.5 = 1.143

3
[Link] [Link] dNaCl MNaCl  akCl  58.5
(b) dNaCl = , dkCl = 3 , d = M .  
 = . (1.143)3 = 1.172
 aNaCl 
3
(aNaCl ) NA (akCl ) NA KCl KCl 74.5

Ex.30 An element A (Atomic weight = 100) having bcc structure has unit cell edge length 400 pm. Calculate
the density of A and number of unit cells and number of atoms in 10 gm of A.
Sol. a = 400 pm = 4 × 10–8 cm
z=2
ZM 2  100 200
d= = = = 5.188 gm/cc
a3N A 8 3
( 4  10 )  6.023  10 23 38.54
In 100 gm  6.023 × 1023 atoms
In 10 gm  6.023 × 1022 atoms

Ex.31 The composition of a sample of wustite is Fe0.93 O1.0. What percentage of iron is present in the form of
Fe(III) ?
Sol. Fe : O = 93 : 100
Let Fe (III) = x
then Fe (II) = (93 – x)
Balancing charge, We have
x × 3 + (93 – x) × 2 = 100 × 2
x = 200 – 186 = 14
14
% Fe (III) = × 100 = 15.05 %
93

Ex.32 BaTiO3 crystallizes in the prevoskite structure. This structure may be described as a cubic lattice
with barium ions occupying the corner of the unit cell, oxide ions occupying the face-centers and
titanium ion occupying the center of the unit cell.
(a) If titanium is described as occupying holes in BaO lattice, what type of holes does it occupy?
(b) What fraction of this type hole does it occupy ?
Sol. (a) Ti is present at the dbody centre i.e.
it occupies octahedral hole.
(b) No. of octahedral in c.c.p. = 4
1
Fractional of octahedral hole occupied =
4
Ex.33 Rbl crystallizes in bcc structure in which each Rb+ is surrounded by eight iodide ions each of radius
2.17 Å. Find the length of one side of RbI unit cell.

PAGE - 23
CHEMISTRY SOLID STATE

rRb
Sol. = 0.732  rRb = 0.732 × 2.17 = 1.59 Å
rI

2
a 3 = 2 [ rRb + rI ] a= [1.59 + 2.17] = 4.34 Å
2
Ex.34 Find the size of largest sphere that will fit in octahedral void in an ideal FCC crystal as a function
of atomic radius 'r'. The insertion of this sphere into void does not distort the FCC lattice. Calculate
the packing fraction of FCC lattice when all the octahedral voids are filled by this sphere.
Sol. If Radius of shpere is r
Radius of largest sphere that will fit in the octahedral void is 0.414 r
2[r + 0.414 r] = a
2.828 r = a
4 3 4 16 3
Volume of spheres = 4 × r + 4 × (0.414r)3 = r [1+ 0.071]
3 3 3

16 3
r x 1.071   1.071
Volume of unit cell = a3 = (2 2 r)3 = 16 2 r3 , = 3 = = 0.793  79.3%
16 2 r 3 3  1.414

Ex.35 NaH crystallizes in the same structure as that of NaCl. The edge length of the cubic unit cell of NaH
is 4.88 Å.
(a) Calculate the ionic radius of H–, provided the ionic radius of Na+ is 0.95 Å.
(b) Calculate the density of NaH.
Sol. a = 4.88 Å = 4.88 × 10–8 cm
4.88
(a) rNa + rH– = , rH = 2.44 – 0.95 = 1.49 Å
2

ZM 4  24
(b) d= =
a3NA ( 4.88  10 8 3
)  6.023  10 23
= 1.37 gm/cm3

Ex.36 Metallic gold crystallises in fcc lattice. The length of the cubic unit cell is a = 4.07 Å
(a) What is the closest distance between gold atoms.
(b) How many "nearest neighbours" does each gold atom have at the distance calculated in (a).
(c) What is the density of gold ?
(d) Prove that the packing fraction of gold is 0.74.
Sol. a = 4.07 Å
(a) 4r = a 2

a 2 4.07  1.414
r= = = 1.44 Å
4 4
Closest distance between An atoms = 2.88Å
(b) C.N. = 12

PAGE - 24
CHEMISTRY SOLID STATE

ZM 4  196
(c) d= 3 = 8 3
a NA ( 4.07  10 )  6.023  10 23
= 19.4 gm/cc
Ex.37 Graphite in an example of -
(A) Ionic solid (B) Covalent Solid
(C) Vander waal’s Crystal (D) Metallic crystal
Sol. (B)
Graphite is a covalent solid having sp2 hybridised carbon atoms.
Ex.38 Which is amorphous solid -
(A) Rubber (B) Plastic (C) Glass (D) All
Sol. (D)
Amorphus solids neither have ordered arrangement (i.e. no definite shape) nor have sharp melting point
like crystals, but when heated, they become pliable until they assume the properties usually related to
liquid. It is therefore they are regarded as super cooled liquids.
Ex.39 Xenon crystallizes in face centre cubic lattice and the edge of the unit cell is 620 PM, then the
radius of Xenon atom is-
(A) 219.20 PM (B) 438.5 PM (C) 265.5 PM (D) 536.94 PM
Sol. (A)
1
For fcc lattice ; r  a
2 2
where a = 620 PM
On solving r = 219.20 PM.
Ex.40 The edge length of cube is 400 PM. Its body diagonal would be-
(A) 500 PM (B) 693 PM (C) 600 PM (D) 566 PM
Sol. (B)
Since in body centre cubic, the body diagonal
= 3 a = 3  400 PM = 692.82 PM or say 693 PM

Ex.41 What is the simplest formula of a solid whose cubic unit cell has the atom A at each corner,
the atom B at each face centre and a C atom at the body centre-
(A) AB2C (B) A2BC (C) AB3C (D) ABC3
Sol. (C)

An atom at the corner of a cube is shared among 8 unit cells. As there are 8 corners in a cube, number
1
of corner atom (A) per unit cell = 8 × = 1.
8
A face-centered atom in a cube is shared by two unit cells. As there are 6 faces in a cube, number of
1
face-centered atoms (B) per unit cell = 6 × = 3.
2
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CHEMISTRY SOLID STATE

An atom in the body of the cube is not shared by other cells.

 Number of atoms (C) at the body centre per unit cell = 1.
Hence, the formula of the solid is AB3C.
Ex.42 A compound alloy of gold and copper crystallizes in a cube lattice in which the gold atoms
occupy the corners of a cube and the copper atoms occupy the centres of each of the cube
[Link] formula of this compound is-
(A) AuCu (B) AuCu2 (C) AuCu3 (D) None
Sol. (C)
One-eighth of each corner atom (Au) and one-half of each face-centered atom (Cu) are contained with
in the unit cell of the compound.
1
Thus, the number of Au atoms per unit cell = 8 × = 1 and the number of Cu atoms per unit cell =
8
1
6× = 3. The formula of the compound is AuCu3.
2
Ex.43 Select the correct statement (s)-
(a) The C.N. of cation occupying a tetrahedral hole is 4.
(b) The C.N. of cation occupying a octahedral hole is 6.
(c) In schottky defects, density of the lattice decreases.
(A) a, b (B) b, c (C) a, b, c (D) a, c
Sol. (C)
Since tetrahedral holes are surrounded by 4 nearest neighbours. So, the C.N. of cation occupying
tetrahedral hole is 4. Since octahedral hole is surrounded by six nearest neighbours. So, C.N. of cation
occupying octahedral is 6. In schottky a pair of anion and cation leaves the lattice. So, density of lattice
decreases.
Ex.44 Lithium borohydride (LiBH4), crystallises in an orthorhombic system with 4 molecules per unit
cell. The unit cell dimensions are : a = 6.81 Å, b = 4.43 Å , c = 717 Å. If the molar mass of
LiBH4 is 21.76 g mol–1 . The density of the crystal is -
(A) .668 g cm–3 (B) .585 g cm–3 (C) 1.23 g cm–3 (D) None
Sol. (A)
We know that,
ZM
 = ; where V = a × b × c
NV
. gmol 1 )
4  ( 2176
= (6.023  10 23 mol 1 ) (6.81  4.43  7.17  10 24 cm 3 )
= 0.668 g cm– 3
Ex.45 The unit cell of a metallic element of atomic mass 108 and density 10.5 g/cm3 is a cube with
edge length of 409 PM. The structure of the crystal lattice is -
(A) fcc (B) bcc (C) hcp (D) None of these
Sol. (A)
Z M

N  a3

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CHEMISTRY SOLID STATE

Here, M = 108, NA = 6.023 x 1023

Put on these values and solving we get-
a = 409 PM = 4.09 x 10–8 cm,
 = 10.5 g/cm3
n = 4 = number of atoms per unit cell
So, The structure of the crystal lattice is fcc.
Ex.46 Among the following types of voids, which one is the largest void-
(A) Triangular system (B) Tetragonal system
(C) Monoclinic system (D) Octahedral
Sol. (D)
The vacant spaces between the spheres in closed packed structure is called void. The voids are of two
types, tetrahedral voids and octahedral voids. Also radius of tetrahedral voids and octahedral voids are
rvoid = 0.225 × rsphere and rvoid = 0.411 × rsphere respectively. Thus, octahedral void is larger than
tetrahedral void.
Ex.47 Close packing is maximum in the crystal which is-
(A) Simple cube (B) bcc (C) fcc (D) None of these
Sol. (C)
The close packing in the crystal is 0.52, 0.68 and 0.74 for simple cubic, bcc, and fcc respectively.
i.e the close packing is maximum is fcc.
Ex.48 Bragg’s equation is-
(A) n = 2 sin  (B) n = 2d sin  (C) 2n = d sin  (D)  = (2d/n) sin 
Sol. (B)
Bragg’s equation is n = 2d sin .

Ex.49 Copper metal has a face-centred cubic structure with the unit cell length equal to 0.361 nm.
Picturing copper ions in contact along the face diagonal, The apparent radius of a copper ion
is-
(A) 0.128 (B) 1.42 (C) 3.22 (D) 4.22
Sol. (A)
For a face-centred cube, we have,
2a 2  0.361
radius = = nm = 0.128.
4 4
Ex.50 The rank of a cubic unit cell is 4. The type of cell as-
(A) Body centred (B) Face centred (C) Primitive (D) None
Sol. (B)
The number of atoms present in sc, fcc and bcc unit cell are 1, 4, 2 respectively.
Ex.51 At room temperature, sodium crystallises in a body centred cubic cell with a = 4.24 Å. The
theoretical density of sodium is –( Atomic mass of sodium = 23.0 g mol–1)
(A) 2.05 g cm–3 (B) 3.45 g cm –3 (C) 1.00 g cm–3 (D) 3.55 g cm–3
Sol. (C)
The value of Z for a bcc unit cell is 2.

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CHEMISTRY SOLID STATE

Volume V = (4.24 A)3

ZM 2  23
  = =
NV (6.023  10 )  (4.24  10 8 ) 3
23

= 1.00 g / cm3

Solved Subjective Problems

Ex.1 A face-centred cubic solid of an element A has a largest sized guest atom B at the body centre
octahedral hole if insertion of B doesn't affect the original unit cell dimension; determine the
packing fraction of the solid.
Sol. In the given solid, there is one B and four A per unit cell.

Also, under the condition of largest possible size of B, it will be in contact of A present at the face centres only
and the following relatinship will exist :
4rA  2 and 2(rA + rB) = a
rB
solving  0.414
rA
Now, packing fraction
4 1 4 1
( 4rA3  rB3 )  3  3 ( 4rA  rB ) 
3 3
( ) 
3 a 1 2rA3

  r 
3

 4   B     [ 4  (0.414 )3 ]  0.7536
 r 
12 2   A   12 2

Ex.2 An element A has BCC structure and another guest atom

B, of largest possible size are present at each edge
centres of unit cell of A but without disturbing the
original unit cell dimension. Determing the void
percentage of this solid.

Sol. Since B is closer to corner than to face centre,

in close contact, A B
2(rA + rB) = a

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CHEMISTRY SOLID STATE

rB
4rA  3 a  r  0.155
A

1
In a unit cell, there are two A and 12 × = 3B
4
4 1
 Packing fraction () = ( 2rA3  3rB3 )  3
3 a

3 
3
r 
 2  3 B    0.684  Void space = 31.6%
16  r 
  A  
Ex.3 An element A has a BCC structure and another guest atoms B, of largest possible size, are present at
the face centres, but wihtout disturbing the unit cell dimension. Determine the packing fraction of
this solid.
A

Sol. In the above solid, face centres are closer to body centre, therefore, the relationship.
2(rA + rB) = 0
rB
4rA  3a  r  0.155
A

3 
3
4 1 r 
Now, packing fraction () = ( 2rA3  3rB3 )  3  2  3 B   = 0.684
16  r 
3 a   A  
Ex.4 Calcium has face-centred cubic lattice and radius of calcium atom is 195.6 picometre. Determine
the number of Ca atoms present on surfaces of a mm 3 block of calcium metal assuming that atoms in
the closest packing calcium metal assuming that atoms are in the closest packing.
Sol. In FCC, the relation is
4r  2a  a  2 2 r = 553.24 × 10–9 mm.
 Area of a face of unit cell = a3 = 3.06 × 10–13 mm2
 Surface area of metal block = 6 mm2
 Total number of faces of unit cells present on surface
1 1/4
6
= = 1.96 × 1013
3.06  10 –13
Each face contributes two Ca atoms on surface as shown in diagram.
 Total number of Ca atoms present on surface
= 2 × 1.96 × 1013 = 3.92 × 1013
Ex.5 An atom crystallises in hexogonal closed pack arrangement. Determine dimensions (radius and
length) of a large cyclindrical atom that can be accommodated in the centre of HCP, in terms of
radius of host atom.
Sol. The cylinder will pass through centre of middle layer and will lie between the face centres.

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CHEMISTRY SOLID STATE

Therefore,
Height of cylinder (h) = height of hexagon (h) = 2r
2
Since, in HCP : H  4 r , where r = radius of atoms.
3
 2 
 h  4 – 2  r = 1.266 r
 3 
 
Also, if R is the radius of cylinder, then in the case of closet contact :
R
 0.155  R = 0.155 r,  h = 1.266 r
r

Ex.6 A uniform cylindrical, polymer molecule crystallizes in body centred cubic array. Determine the
packing fraction of this polymer in solid state assuming that molecules are in their closest contact.
Sol. The arrangement of molecules can be represented as follows :
Here, 4r  2 l  I  2 2r

2r 2 l 2r 2
Packing fraction () =  2
I3 I

=  0.785
4
A
Ex.7 Show the following arrays of atoms on a plane in an atomic FCC.

(A) (B) (C) (D)

Sol. (A) (B)

(C) (D)

Ex.8 Cesium bromide crystallizes in cubic arrangement like CsCl. Given the ionic radii of Cs + and Br–
are 1.88 Å and 1.82 Å respectively, determine the packing fraction.
Sol. Here Cs+ ion is at body centre and Br– at the corners, therefore the relationship is
2(r+ + r–) = 3 a = 2 (1.88 + 1.82) Å,  a = 4.27 Å

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CHEMISTRY SOLID STATE

4  r3  r–3  4  (1.88 )3  (1.82)3 

Packing fraction () = 3  a 3   
 3  ( 4.27 )3
  0.6807

  
Ex.9 Titanium metal crystallises in a BCC arrangement and radius of an atom is 142 picometre. Determine
atomic weight of titanium if density is 16.6 g/cm 3. Also determine the number of unit cells present in
a 5 cm3 block of titanium metals.
Sol. In BCC arrangement of atoms the relatioship between edge length radius of atom is
4r  3a
NM
Density () = N V
A

Where, N = Number of atoms per unit cell,

M = Molar mass, NA = Avogadro's number
V = Volume of unit cell

 16.6  2M
3
 4 
6.023  10 23   142  10 –10 
 3 
Here, radius is taken in cm unit since, density is in g/cm3 unit.
Solving : M = 176. Also mass of 5 cm3 block = 5 × 16.6 = 83 g
83
 Number of atoms is 5 cm3 block = × 6.023 × 1023
176

No. of atoms 83  6.23  10 23

 Number of unit cells = = = 1.42 × 1023
2 176  2

Ex.10 Copper metal crystallizes in face-centred cubic arrangement and surface of adjacent atoms along
the edge of unit cell are 106 picometre apart. Determine the density of metal. Atomic mass of copper
metal is 63.5 u.
Sol. According to the given information, a view of one face of the unit cell will be as shown below.
In FCC; 4 2 a 106 picometer
a
The given distance is a – 2r = a –
2

 2 – 1
 a   106 pm
 2 
 a = 362 pm = 3.62 × 10–8 cm
4  63.5
 Density ()  = 8.89 g/cm3
6.023  10 23 (3.62  10 – 8 )3

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CHEMISTRY SOLID STATE

Ex.11 Potassium crystallizes in "body centred cubic" arrangement and the surfaces of adjacent atom
along the edges of unit cells are 71.4 picometre apart. Determine the density of metal. Atomic weight of
K = 39.
Sol. In BCC, the relationship between edge length and radius of atom is
4r  3 a
Also, given a – 2r = 71.4 × 10–10 cm
3 2 – 3 
 a– a  a  = 71.4 × 10–10 cm
2  2 
 a = 5.329 × 10–10 cm
2  39
 Density () = 6.023  10 23 (5.329  10 – 8 )3 = 0.855 g/cm3

Ex.12 Magnesium oxide has the NaCl structure and radii of Mg 2+ and O2– ions are 0.86 A and 1.24 A.
Determine the density of magnesium oxide solid.
Sol. In a unit cell, there are four unit of MgO and edge-length of the unit cell is
a = 2 (radius of cation + radius of anion)
= 2 (0.86 + 1.24) = 4.2 Å
4  40
Density () = 6.023  10 23 ( 4.2  10 – 8 )3  3.585 g / cc

Ex.13 An unknown substance that uses gas at room temperature can be condensed to a solid at –80°C. As
a solid, it is found to have cubic unit cell, 5.15 Å on each side, containing four molecules. The
density of solid is 0.73 g/cm3. What is the density of the substance as a gas at 27°C and at a pressure
of 1.00 atmopshere ?
Sol. For a cubic unit cell :
nM
Density () = N a 3
A

Where, n : No. of molecules per unit cell,

M = Molar mass
NA = Avogadro's constant,
a = Edge length of unit cell.
4M
 0.73 g / cm 
3

6.023  10 23 (5.15  10 – 6 cm)3

M = 15 g/mol M
Molar mass of a substance is independent of state.
pM 1.05  15
 As a gas, Density () =  = 0.6097 g/L.
RT 0.082  300

Ex.14 Aluminium crystallizes in a cubic lattice with an edge of 404 pm and density of metal is 2.70 g/cm 3.
What type of cubic is formed by aluminium ?

PAGE - 32
CHEMISTRY SOLID STATE

Sol. If there is "n" aluminium atoms per unit cell :

nM
Density () 
NA a3

n  270
 2.70 
6.023  10 23 ( 4.04  10 – 8 cm)3
 n = 6.023 × 1022 (4.04 × 10–8)–3 = 3097  4
Hence, Al forms face-centred cubic (FCC) lattice.
the coordination number of Al in FCC is 12 i.e., each Al atom has twelve other Al atoms in its nearest neighbour.

An atom of aluminium (solid black) present on the centre of middle vertical face is equidistant from the twelve
adjoining atoms, hence, coordination number of an atom in FCC arrangement is twelve.

Ex.15 Except helium, all the noble gases crystallize with cubic close packed structures. Derive an equation
relating atomic radius to the density of cubic close packed solid of given mass and apply it to deduce
the relative size of Ar and Xe if their densities are 1.4 g/cm and 2.83 g/cm 3 respectively.
nM
Sol. For a CCP solid :  = n a 3
A

Where,  = Density, n = No. of atoms/unit cell

M = Molar mass, NA = Avogadro constant,
and a = Edge length
3
4M M  xe 2.83 131  rAr  rXe  131 1.4 
1/ 3

            1.174
N A ( 2 2 r )3 4 2 NA r 3  Ar 1.40 40  rXe  rAr  40  2.83 

Ex.16 All alkali metals crystallize into BCC strucutres.

(a) Find an equation relating the metallic radius to the density of a BCC solid in terms of its molar
mass.
(b) Determine the relative size of Cs atom compared to a Li atom, if their densities are 1.87 g/cc and
0.53 g/cc, respectively.
Sol. (a) For a BCC solid of an element, there are two atoms per unit cell.
2M
 Density () = 6.023  10 23 a 3
Also; in BCC of an atomic solid,

PAGE - 33
CHEMISTRY SOLID STATE

2M  3 3 M
 = 2.696 × 10–23 3
6.023  10 23  64 r 3 r
3
 Cs 1.87 133  rLi 
(b)   0.53  7  r 

Li  Cs 

rCs
  1.753  rCs = 1.753 rLi
rLi

Ex.17 Some of the metals with BCC structures are not close packed. Therefore, their densities would be
greater if they were to change to a cubic close packed structure. What would be density of a metal if
it had a cubic close packed structure rather than BCC? Its actual density is 19.3 g/cc.
3
4M 2M  CCP a 
Sol.  CCP  and BCC  ,   2 BCC  : Also in FCC 4r  2 a

N A a 3CCP 3
N A aBCC BCC  a CCP  CCP

in BCC, 4r  3 aBCC
3/2
 CCP 2
  2   1.08867  CCP  21g / cc
19.3 3

Ex.18 How many unit cells of KBr are present in a 1.00 mm 3 of KBr, KBr crystallizes in NaCl type of
crystal lattice and its density is 2.75 g/cm 3.
Sol. In a unit cell of KBr, there are four formula units of KBr.
4  119
Therefore, density () =  2.75 ,  a3 = 2.778 × 10–22 cm3 = 2.778 × 10–19 mm3
6.023  10 23  a 3

1019
 No. of unit cells per mm3 = = 3.6 × 1018
2.778

PAGE - 34