Solid State Final

24
Solid State
1. IIT–JEE Syllabus
2. Differences Between Crystalline
and Amorphous Substances
3. Unit Cells
4. External features of Crystals
5. Crystal Systems
The outstanding macroscopic properties of
6. Bravais Lattices
6.1 Primitive Cubic Unit Cell gases are compressibility and fluidity.
6.2 Body Centered Cubic Unit Cell
6.3 Face Centered Cubic Unit Cell
6.4 Hexagonal Primitive Unit Cell
In contrast, the most noticeable macroscopic
7. Close Packing of Spheres features of crystalline solids are rigidity,
8. Octahedral and Tetrahedral Voids incompressibility and characteristic geometry.
9. Radius Ratio Rules We shall find that the explanation of these
9.1 Co-ordination Number 3
9.2 Co-ordination Number 4 macroscopic properties in terms of the atomic
10. Classification of Ionic Structures theory which involves the idea of lattice: a
10.1 Rock Salt Structure permanent ordered arrangement of atoms held
10.2 Zinc Blende Structure
10.3 Fluorite Structure together by forces of considerable magnitude.
10.4 Anti–Fluorite Structure
10.5 Cesium Halide Structure
10.6 Corundum Structure Thus the extremes of molecular behaviour
10.7 Pervoskite Structure
10.8 Spinel & Inverse Spinel Structure occur in gases and solids. In the former we
11. Imperfections in a Crystal have molecular chaos and vanishing
11.1 Stoichiometric Defects
11.2 Non-stoichiometric Defects intermolecular forces, and in the latter we have
12. Solution to Exercises an ordered arrangement in which the
13. Solved Problems interatomic forces are large.
13.1 Subjective
13.2 Objective
14. Assignments
(Subjective Problems)
15. Assignments
(Objective Problems)
16. Answers to Subjective
Assignments
17. Answers to Objective
Assignments
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1. IIT–JEE Syllabus
Classification of solids; crystalline state, seven crystal systems (only cell parameters:
a, b, c, ,  and ); packing fcc, bcc, hcp; nearest neighbours, simple ionic
compounds, point defects.
2. 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 is different direction. different directions
4. They undergo a 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)
2.1 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.
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3. 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 Fig.2. Unit cells arranged together
unit of the solid. Any amount of the solid can be
constructed by simply putting as many unit cells as
required.
4. External Features of Crystals

Crystals are bounded by surfaces which are usually planar and referred as faces. Edge is
formed by the intersection of our adjacent faces. The angle between any two faces is called
an interfacial angle. Although the size of the faces or even shapes of the crystals of one and
the same substance may vary widely with conditions of formation etc., but the interfacial
angles between any two corresponding faces of the crystal remain invariably the same
throughout.
5. Crystal Systems
From external appearance we come across a variety of crystal forms in many shapes. But on
the basis of length of axes and the axial angles, it has been possible to classify the various
crystal forms into only seven fundamental systems. These are:
1. Cubic
2. Orthorhombic
3. Tetragonal
4. Monoclinic
5. Triclinic
6. Hexagonal
7. Rhombohedral
The crystals belonging to any one system may differ in shape, in size, etc., but their axial
ratios as also the axial angles will always be the same. The intercepts on the three axes are
denoted by a, b and c and the axial angles by ,  and .
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Seven crystal systems : The seven crystal systems are given below.
Crystal System Bravais Lattices Parameters of Unit Cell
Intercepts Crystal angle Example
1. Cubic Primitive, Face Centered, a=b=c  =  =  = 90o Pb,Hg,Ag,Au
Body Centered = 3 Diamond, NaCl, ZnS
2. Orthorhombic Primitive, Face Centered, abc  =  =  = 90o KNO2, K2SO4
Body Centered, End
Centered = 4
3. Tetragonal Primitive, Body Centered =2 a=bc  =  =  = 90o TiO2,SnO2
4. Monoclinic Primitive, End Centered = 2 abc  =  = 90 ,o CaSO4,2H2O
  90o
5. Triclinic Primitive = 1 abc       900 K2Cr2O7,
CaSO45H2O
6. Hexagonal Primitive = 1 a=bc  =  = 90 ,  =0
Mg, SiO2, Zn, Cd
120o
7. Rhombohedral Primitive = 1 a=b=c  =  = 90o,   As, Sb, Bi, CaCO3
90o
Total = 14
6. Bravais Lattices
Bravais (1848) showed from geometrical considerations that there are only seven shapes in
which unit cells can exist. 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.
6.1 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
Fig. 3 (a). Primitive Cubic unit cell
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
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manner as shown in the figure. Four atoms are

r r
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
a
of a unit cell can be understood by calculating
Figure 3(b)
the packing fraction. It is defined as ratio of
the volume occupied by the spheres in a unit
cell to the volume of the unit cell and void
fraction is given as = (1 – Packing fraction).
4 3
r
Therefore, PF = 3 0.52 . (This implies
(2r )3
that 52 % of the volume of a unit cell is
occupied by spheres).
Fig. 3(c) Each atom is shared by eight unit cells
VF  0.48
6.2 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 else.
This 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 Fig. 4 (a) Body Centered Cubic unit cell
atoms in a Body Centered Cubic Unit Cell is 2 B
(One from all the corners and one at the
center of the unit cell). Moreover, since in r
BCC the body centered atom touches the top a
2r
four and the bottom four atoms, the length of
the body diagonal ( 3 a ) is equal to 4r. The a r
C
a
packing fraction in this case is
Figure 4(b)
4
2 r 3
= 3  0.68 VF  0.32
4r 3
( )
3
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6.3 Face Centered Cubic Unit Cell
In a fcc unit cell, the same atoms

A
are present at all the corners of
the cube and are also present at
the centre of each square face
C
and are not present anywhere
else. The effective number of
C
atoms in fcc is 4 (one from all the  
corners, 3 from all the face B B
centers since each face centered
atom is shared by two cubes).
Since, here each face centered A
atom touches the four corner
atoms, the face diagonal of the CUBIC CLOSE PACKING (CCP)
 FACE-CENTRED CUBIC (FCC)
cube ( 2 a ) is equal to 4r.
Figure 5(a)
4 a
4 r 3
a
 packing fraction 3 0.74
4r 3 4r
( )
2
VF  0.26
Figure 5(b)
6.4 Hexagonal Primitive Unit Cell
Each corner atom would be common to 6

other unit cells, therefore their contribution to A
one unit cell would be 1/6. Therefore, the
A
total number of atoms present per unit cell
effectively is 6.
F
D B 
C B
a h/2
a
E G
A
A B
r
a/ 3
A
A E
Figure 6(b)
ABCD is the base of hexagonal unit cell HEXAGONAL CLOSE PACKING (HCP)
AD=AB=a. The sphere in the next layer has Figure 6(a)
its centre F vertically above E it touches the
three spheres whose centres are A,B and D.
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2 3 a 2r
 AE   a 
3 2 3 3
2
h  2r 
Hence FE = = (2r )  
2

2  3
2
 The height of unit cell (h) = 4r
3
3
The area of the base is equal to the area of six equilateral triangles, = 6× (2r ) 2 . The
4
3 2
volume of the unit cell = 6× (2r )2 ×4r .
4 3
Therefore
4
6 πr 3
PF = 3  0.74 ; VF  0.26
3 2
6 (2r ) 4r
2
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
=
NA  V
Illustration 1: Iron (-Fe) crystallizes in a b.c.c. system with a = 2.86Å. Atomic weight of
iron is 55.85 g mol–1. Calculate the density of iron.
n  Atomic w eight
Solution: Since, density  =
Volume  Av. No.
Hence n = 2, Atomic weight = 55.85
Volume = V = a3 = (2.861 × 10–8 cm)3, Av. No. = 6.023 × 1023
Putting the values  = 7.92 g/cm
Exercise 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.
7. 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:
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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 Fig. 7 (a)' A' layer of spheres.
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 sense
that it eclipses the spheres of the A layer.
This arrangement (i.e., ABAB……) is called ‘x’ type void ‘y’ type voide
the hexagonal close packing (hcp) or Fig. 7(b)' A' and 'B' layer of spheres.
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 (c)' A' and 'B' & 'C' layer of spheres
Exercise 2: 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?
8. Octahedral and Tetrahedral Voids
Octahedral hole
Tetrahedral hole
(Figure 8(a) Voids in FCC unit cell)

(Effective number of octahedral holes = 4, Effective number of tetrahedral holes = 8)
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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
(¼,¼,¼)
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).
Fig. 8(b) An atom occupying a tetrahedral
void
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 then
the number of octahedral voids. Therefore, Fig. 8(c) Center of eight small cubes behave
the number of tetrahedral voids in hcp is 12. as tetrahedral voids for bigger cube.
9. 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 size can be in contact with a smaller ion. Thus, we
can predict the coordination number from the relative sizes of the ions.
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The adjacent fig. 9(a) shows the smaller positive ion

of radius r+ is in contact with three larger negative ions A
of radii r-. It can be seen that AB = BC = AC = 2r-,
BD = r- + r+. Further, the angle ABC is 60o, and the
D
angle DBE is 30o. By trigonometry Cos 30o = (BE /
E
BD). B C
BD = (BE / cos 30o), r+ + r- = r- / cos 30o Fig. 9(a)

= (r- / 0.866) = r-  1.155, r+ = (1.155 r-) - r- Cross Section Through Planar Triangle Site
= 0.155 r-, Hence (r+ / r-) = 0.155.
9.2 Co-ordination Number 4 (Tetrahedron)
Angle ABC is the tetrahedral angle of 109o 28' and B

hence the angle ABD is half of
this, that is 54o64'. In the triangle ABD, sin ABD
r A C
= 0.8164 = AD / AB =   . D
r r
r  r  1
Taking reciprocals, 
 1.225 , Fig. 9(b)
r 0.8164 Cross Section Through Tetrahedral Site
r
rearranging, we get,  0.225 .
r
9.3 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
A
four negative ions are shown in this section and one is above
and one below the plane of the paper). B C
D
It is obvious that AB = r+ + r- and BD = r-. The angle ABC is
45o in the triangle ABD. cos ABD = 0.7071 = (BD / AB) = Fig. 9(c):
Cross Section Through Octahedral Site
r r
. Rearranging, we get,  = 0.414
r  r r
r
Limiting radius ratio x Co – ordination
r Shape Example
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
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Exercise 3: The radius of a calcium ion is 94 pm and of an oxide ion is 146 pm. Predict the
crystal structure of calcium oxide.
10. Classification of Ionic Structures

In the following structures, a black circle would denote a cation and a white circle would
denote an anion.In any solid of the type AxBy, the ratio of the coordination number of A to that
of B would be y : x.
10.1 Rock Salt Structure
Cl- is forming a fcc unit cell in which Cl

–
+
Na
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
Figure 10 Unit cell structure of NaCl
alkaline earth metals except beryllium
oxide.
10.2 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.
10.3 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.
Unit cell representation of CaF2 structure Fig

ure 12
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10.4 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.
Figure 13
Anti-fluorite structure
10.5 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.
Figure 14
Cesium halide structure
10.6 Corundum Structure
The general formula of compounds crystallizing in corundum structure is Al2O3. 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.
10.7 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.
Figure 15
Pervoskite structure
10.8 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
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substances of the type M4  M22  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
tetrahedral voids and one-fourth of the octahedral voids.
Illustration 2: A solid compound AB has NaCl structure. If the radius of the cation is 95 pm.
What is the radius of anion (B–)?
 r 
Solution: Radius into    for octahedral co-ordination = 0.414
r 
95
Hence radius of the anion (B–) = pm = 229.46 pm
0.414
Exercise 4: 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 5: The co-ordination number of the barium ions, Ba2+, in barium chloride (BaF2) is
8. What must be the co-ordination number of the fluoride ions, F  .
11. 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.
11.1 Stoichiometric Defects
Stoichiometric compounds are those where the numbers of the different types of atoms or
ions present are exactly in the ratios indicated by their chemical formulae. They obey the
law of constant composition that “the same chemical compound always contains the same
elements in the same composition by weight”. Previously these were called Daltonide
compounds.
Two types of defects may be observed in stoichiometric compounds, called Schottky and
Frenkel defects respectively. At absolute zero, crystals tend to have a perfectly ordered
arrangement. As the temperature increases the amount of thermal vibration of ions in their
lattice sites increases and if the vibration of a particular ion becomes large enough, it may
jump out of its lattice site. The higher the temperature, the greater the chance that lattice
sites may be unoccupied. Since the number of defects depends on the temperature, these
are sometimes called thermodynamic effect.
Schottky Defects: The defects rise 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. Thus a Schottky defects consists of a pair
of holes in the crystal lattice.
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+ –
Na missing Cl missing
Figure 16
Schottky defects appear generally in highly 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
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.
11.2 Non-Stoichiometric Defects
In non-stoichiometric or Berthollide compounds the ratio of the number of atoms of one kind
to the number of atoms of the other kind does not correspond exactly to the ideal whole
number ratio implied by the formula. Such compounds do not obey the law of constant
composition. There are many examples of these compounds particularly in the oxides and
sulphides of the transition elements. Thus in FeO, FeS or CuS the ratio of Fe : O, Fe : S or
Cu : S differs from that indicated by the ideal chemical formula. If the ratio of atoms is not
exactly 1 : 1 in the above cases, there must be either an excess of metal ions or a deficiency
of metal ions. Electrical neutrality is maintained either by having extra electrons in the
structure or changing the charge on some of the metal ions. This makes the structure
irregular in some way i.e., it contains defects.
RSM24-P6-CH-SS-14
Metal Excess: This may occur in two different ways
F-Centres: A negative ion may be absent from its lattice site leaving a hole which is
occupied by an electron, thereby maintaining the electrical balance. This type of defect is
formed by crystals which would be expected to form Schottky defects. When compounds
such as NaCl, KCl, are heated with excess of their constituent metal vapours, or treated with
high energy radiation, they become deficient in the negative ions and their formulae may be
represented by AX1–, where  is a small fraction. The crystal lattice has vacant anion sites
which are occupied by electrons. Anion sites occupied by electrons in this way are called F
centres (F is an abbreviation Farbe, the German word for colour).
+ –
Na Cl
–
e
F Centre
F-centre in a Sodium chloride crystal

Figure 18
Interstitial ions and electrons: Metal excess defects also occur when an extra positive ion
occupies an interstitial position in the lattice and electrical neutrality is maintained by the
inclusion of an interstitial electron. Their composition may be represented by general
formula A1+X. This kind of metal excess defect is much more common than the first and is
formed in crystals which would be expected to form Frenkel defects. Examples include ZnO,
CdO, Fe2O3.
+ – + – +
A B A B A
A+
– + – + –
B A B A B
e–
+ – + – +
A B A B A
– + – + –
B A B A B
+ – + – +
A B A B A
Figure 19: Metal excess defects caused by interstitial cations.
Crystals with either type of metal excess defect contain free electrons, and if these migrate
they conduct an electric current. These free electrons may be excited to higher energy
levels, giving absorption spectra and in consequence their compounds are often coloured
e.g. non-stoichiometric NaCl is yellow, nonstoichiometric KCl is lilac.
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
RSM24-P6-CH-SS-15
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.
Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+ O2–
O2– Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+
Fe2+ O2– Fe2+ O2– Fe2+ O2– O2– Fe2+ O2–
O2– Fe2+ O2– Fe2+ O2– Fe+3 O2– Fe+3 O2– Fe2+
Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+ O2– Fe2+ O2–
Figure 20
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.
RSM24-P6-CH-SS-16
12. Solution to Exercises

Exercise 1: Since
n  mol . w t
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,  = 
2.154  10  22  6.023  10 23
= 0.6708 gm/cm3
Exercise-2: HCP is of the ABAB… type and FCC is of ABCABC… type. In HCP and FCC
both, the layers are formed of same atoms of the same type in the same
arrangement (each sphere surrounded by six) but the placement of the layers
on top of each other is different.
both will have same packing fraction.
This is the highest packing fraction possible because in both types, maximum
number of atoms of the same size are present around the atom (namely six).
r 94
Exercise-3: The ratio 
  0.644 . The prediction is an octahedral arrangement of
r 146
the oxide ions around the calcium. 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.
Exercise-4: The formula, AgI, tells us that the ratio of silver atoms to iodine atoms is 1:1.
Hence, if there are four iodine atoms in the unit cell, there must be four silver
atoms.
Exercise-5 The co-ordination number of barium ions tells us that it is surrounded by

eight fluoride ions (charge 8  (-1) = -8). In order to balance out the eight
negative charges, we need four barium ions (charge 4  (+2) = +8). Hence,
the co-ordination number of the fluoride ions must be 4. You will find that the
co-ordination number and the charge on ions always
balance out to neutralify.
RSM24-P6-CH-SS-17
13. Solved Problems

13.1 Subjective
Problem 1: Copper has the fcc crystal structure. Assuming an atomic radius of 130pm for
copper atom (Cu = 63.54):
(a) What is the length of unit cell of Cu?
(b) What is the volume of the unit cell?
(c) How many atoms belong to the unit cell?
(d) Find the density of Cu.
Solution: As we know
n  Mm
= ,
NA  a 3
a) for fcc structure
4r = 2 a
a =2 2 r
= 2 2  130 pm
= 367.64 pm
n  Mm
b) volume of unit cell = a3 = o
Na  
4  63.54
= g/m3
6.023  10 23  8.54
= 4.94  10–23 cm3
c) n = 4
4  63.54
d)  = = 8.54 gm / cm3
6.023  10  (3.67  10 8 cm3 )3
23
Problem-2: Compute the percentage void space per unit volume of unit cell in zinc-fluoride
structure.
Solution: Since anions occupy fcc positions and half of the tetrahedral holes are
occupied by cations.
Since there are four anions and 8 tetrahedral holes per unit cell, the fraction
of volume occupied by spheres/unit volume of the unit cell is
4  1 4 
4   ra3    8   rc3 
   rc  
3
 3  2  3 
= = 1    
16 2ra3 3 2   ra  
 
 for tetrahedral holes,
rc
= 0.225
ra

= {1 + (0.225)3}
3 2
= 0.7493
RSM24-P6-CH-SS-18
 Void volume = 1 – 0.7493

= 0.2507/unit volume of unit cell
% void space = 25.07%
Problem 3: The density of CaO is 3.35 gm/cm3. The oxide crystallises in one of the cubic
systems with an edge of 4.80 Å. How many Ca++ ions and O–2 ions belong to
each unit cell, and which type of cubic system is present?
Solution: From equation

(density) = 3.35 gm/cm3
a = 4.80 Å
Mm of CaO = (40 + 16) gm = 56 gm CaO
nMm
= 3 where n = no. of molecules per unit cell
a  NA
3.35  ( 4.8  10 8 )3  6.023  10 23
n= = 3.98
56
or n  4
So, 4-molecules of CaO are present in 1 unit cell
So, no. of Ca+ + ion = 4
No. of O– – ion = 4
So, cubic system is fcc type.
Problem 4: A metal crystallizes in two cubic phases, face centered cubic (fcc) and body
centered cubic bcc whose unit cell length are 3.5 and 3.0A° respectively.
Calculate the ratio of density of fcc and bcc. [IIT JEE ‘99]
n  Mm
Solution: =
NA  a 3
For face center cubic (fcc)
n = 4, a = 3.5 Å
4  Mm
(fcc) = --------------- (I)
NA  (3.5)3
For bcc lattice
N = 2, a = 3.0 Å
2  mm
bcc = ---------------- (ii)
NA  (3.0)3
From equation (i) equation (ii)
 4 33 4333
 ( fcc)    = 1.259
(bcc) 2 (3.5) 3
2  3.5  3.5  3.5
Problem 5: A compound formed by elements X & Y, Crystallizes in the cubic structure,

where X is at the corners of the cube and Y is at the six face centers. What is
the formula of the compound? If side length is 5A°, estimate the density of the
solid assuming atomic weight of of X and Y as 60 and 90 respectively.
Solution: From eight corner atoms one atoms (X) contributes to one unit cell.
From six face centres, three atoms (Y) contributes to one unit cell.
So, the formula of the compound is XY3.
RSM24-P6-CH-SS-19
As we know that,
n  Mm
= , here n = 1
NA  a 3
Molar mass of XY3
Mm = 60 + 3  90 = 330 gm
1 330
= gm/cm3
6.023  10 23  (5  10  8 )3
a = 5Å = 5  10–8 cm
330
= gm/cm3 = 4.38 gm / cm3
6.023  10  125  10  24
23
Problem 6: In LiI Crystal, I– ions form a cubical closest packed arrangement and Li+ ions
occupy octahedral holes. What is the relationship between the edge-length of
the unit cells and the radii of the I – ions? Calculate the limiting ionic radii of Li+
and I–- if a= 600pm.
Solution: From question

2r+ + 2r– = 600 pm
 r+ + r– = 300 pm------------- (i)
Since, Li+ ions occupy octahedral hole
So, for octahedral hole
r
= 0.414 -------------------- (ii)
r
From equation (I) and equation (ii)
 r 
r     1 = 300
r 
r–  (0.414 +1) = 300
300 r
 r– = = 212.164 (  = 0.414)
1.414 r
 r+ = 212.164  0.414 = r+ = 87.84 pm
Problem 7: Calculate the atomic volume of an element whose atoms have a radius 1.414A°
when atoms are cubic closed structure. What is the length of an edge of the
unit cell?
Solution: Since atoms are cubic closed structures i.e., for fcc structure
 4r = 2 a
Given r = 1.414Å
r= 2Å
4 2 Å= 2a
 a = 4Å
= 4  10–8 cm = 4Å
Since volume of a unit cell = a3
= (410–8)3
= 64 10–24
= 6.4 10–23
RSM24-P6-CH-SS-20
Since one unit cell contains 4 atoms

i.e.,  4 atoms corresponds to volume 6.4  10–23 cm3
64
 1– atom corresponds to volume  10–23 cm3
4
= 1.6  10–23 cm3
Problem 8: Prove that void space in fluorite structure per unit volume of unit cell is 0.251.
Solution: Cations form cubical closest packing and anions occupying the tetrahedral
holes.
There are 4 cations per unit cell.
There are 8 anions per unit cell.
Here, face diagonal.
4r+ = 2a
where, r+= radius of cation
a = 2 2r+
a3 = (2 2 r+)3
Volume of unit cell = 16 2r+3
Fraction of volume occupied per unit voume of unit cell
4 3 4 3
4× π r+ + 8 × πr
3 3 _ π   2r3 
i.e. Packing fraction = 3
= 1   3 
16 2r+ 3 2   r 
Here in fluorite structure, for tetrahedral hole
radius of anion r
=   0.225
radius of cation r
π
PF = {1 + 2(0.225 )3 }
3 2
= 0.7577
 void space = 1 – 0.7577
VF = 0.2422/unit volume of the unit cell
Problem 9: 5.35 g of a salt ACl (of weak base AOH) is dissolved in 250 ml of solution. The
pH of the resultant solution was found to be 4.827. Find the ionic radius of A+
and Cl– if ACl forms CsCl type crystal having 2.2 g/cm3. Given Kd(AOH) = 1.8 
10–5
r
= 0.732 for this cell unit
r
Solution: ACl(s)  A+(aq) + Cl–(aq)

A+(aq) + H2O AOH(aq) + H+(aq)
at equilibrium C(1–)
Kw
For salts of weak base and strong acid  =
K bc
Kw  C
H+ = C =
Kb
RSM24-P6-CH-SS-21
1 10 4 5.35  1000
antilog (–4.827) = 
1.8  10 5
M  250
M = 53.5
For CsCl type structure
zM
= 3
a  6.0923  10 23
1 53.5
1/ 3
 
a=  23 
= 3.43Å
 2.2  6.023  10 
3
rA  rCl =  a = 0.866 a = 0.866  3.43 Å = 2.97 Å
2
ro
 A
= 0.732
rCl
on solving rA  = 1.255 Å
rCl
= 1.715 Å
Problem 10: In a face centred lattice with all the positions occupied by A atoms the
body centred octahedral hole in it is occupied by an atom B of an
appropriate size for such a crystal, calculate the void space per unit
volume of unit cell. Also predict the formula of the compound.
Solution: Let a be the edge of the cube so that

4rA = 2 a
a = 2 2rA
No since the atoms B has occupied the body central octahedral hole
B atom
2rA  2rB = a
2rA  2rB = 2 2 rA

2rB = 2 2  2rA 
rB
 2 1
rA = 1.414 – 1 = 0.414
Volume of the cube a3 = 16 2rA3
Volume occupied by A and B=
 4 3 4 3 4
4  3 rA    3 rB   3 4rA  rB 
3 3
   
RSM24-P6-CH-SS-22
Volume occupied per unit volume of unit cell

4 / 34rA3  rB3     rB  
3
=  
4    
16 2rA3 12 2   rA  
=
3.14
4  (0.414) 3   3.14  4.071
1.2  1.414 12  1.414
= 0.75
13.2 Objective
Problem 1: In a fcc arrangement of A & B atoms, where A atoms are at the Corners of the
unit cell, B atoms at the face centers, two atoms are missing from two corners
in each unit cell, then the simplest formula of the compound is
(A) A7B6 (B) A6B7
(C) A7B24 (D) AB4
Solution: Since there are six atoms (A) in the corner of the unit cell. So, contribution of
6
atoms in 1 unit cell is .
8
Since 3 face-centered atoms (B) contributes to one unit cell
So, formula is A6/8 B3
or A6 B24, or AB4
(D)
Problem 2: In fluorite structure (CaF2)

(A) Ca++ ions are ccp & F  ions are present in all the tetrahedral voids
(B) Ca++ ions are ccp & F  ions are present in all the octahedral voids
(C) Ca++ ions are ccp & F  ions are present in all the octahedral voids and half
of ions are
(D) None
Solution: Ca2+ ions are ccp and F– ions are present in the tetrahedral voids. So, the no.
of Ca2+ ions is 4 and no. of F– ions is 8.
So, the formula of the Calcium fluoride Ca4F8 or, the simplest formula of
calcium fluoride is CaF2
 (A)
Problem 3: 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 Schotky defects, density of the lattice decreases.
(D) In Frenkel defects, density of the lattice increases.
Solution: 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.
(A), (B), (C)
RSM24-P6-CH-SS-23
Problem 4: A solid is made of two elements P&Q. Atoms P are in ccp arrangement and
atoms Q occupy all the octahedral voids and half of the tetrahedral voids, then
the simplest formula of the compound is
(A) PQ2 (B) P2Q
(C) PQ (D) P2Q2
Solution: Four atoms (P) contributes to one unit cell from ccp arrangement and 4-
atoms (Q) from the all octahedral voids and 4-atoms (Q) from the half of the
tetrahedral void contributes one unit cell.
So, formula of solid is P4Q8 so, the simplest formula of the solid is PQ2
(A)
Problem 5: Fraction of total volume occupied by atoms in a simple cubic cell is

 3
(A) (B)
2 8
2 
(C) (D)
6 6
Solution: In simple cubic arrangement, no. of atoms = 1

a = 2r
Volume occupied by one atom
Packing fraction =
Volume of unit cell
4 3 4 3
r r

= 3 3  3 3 
a (2r ) 6
 (D)
The limiting radius ratio of the complex Ni(CN ) 4  is

2
Problem 6:
(A) 0.225 – 0.414 (B) 0.414 – 0.732
(C) 0.155 – 0.225 (D) None
Solution: The complex [Ni(CN)4]–2 is square planar. So, it has limiting radius ratio as
octahedral structure i.e. 0.414 – 0.732
 (B)
Problem 7: If the ratio of co-ordination no. P to that of Q be Y:Z, then the formula of
the solid is
(A) PyQz (B) PzQy
(C) P1/ y Q1/ z (D) None
Solution: Since the ratio of the co-ordination no. P to that of Q is Y : Z

i.e. P is surrounded by Y atoms of Q and Q is surrounded by Z atoms of P
i.e. no. of atoms of P is Z
& no. of atoms of Q is Y
So, the formula is PZQY
 (B)
RSM24-P6-CH-SS-24
Problem 8: 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) 438.5 pm (B) 219.20 pm
(C) 536.94 pm (D) 265.5 pm
Solution : For fcc lattice

4r = 2a where a = 620 pm
1
or, r  a
2 2
1
 620 pm
2 2
= 219.20 pm
 (B)
Problem 9: The arrangement of Cl- ions in CsCl structure is

(A) hcp (B) fcc
(C) bcc (D) Simple cubic
Solution: Arrangement of atoms or, ions in the corner of the unit cell is simple cubic. So
in body centered cubic arrangement, Cl– ions are arranged in the corner of
the cube. So, it is a simple cubic.
(D)
Problem 10: In closest packing of A type of atoms (radius, r A), the radius of atom B that can
be fitted into Octahedral void is
(A) 0.155 rA (B) 0.125 rA
(C) 0.414 rA (D) 0.732 rA
Solution: For octahedral void

rB
 0.414
rA
or, rB = 0.414 rA
 (C)
Problem 11: In -WCl6

(A) all Cl- ions are present in cubic close packing
(B) W occupies, 1/6th of the octahedral holes.
(C) W occupies 1/3rd of the tetrahedral holes.
(D) All Cl- ions are present in all octahedral
Solution: In -WCl6, Cl– ions are arranged in cubic close packing, so, there is only one
1
Cl–ion in 1-unit cell. So, the formula can be written W 1/6Cl, i.e. of the
6
octahedral hole is filled by W.
(A), (B)
Problem 12: The edge length of a cube is 400 pm. Its body diagonal would be
(A) 600 pm (B) 566 pm
(C) 693 pm (D) 500 pm
RSM24-P6-CH-SS-25
Solution: Since in body center cubic, the body diagonal = 3a.

= 3  400 pm = 692.82 pm
= 693 pm
 (C)
Problem 13: The mass of unit cell of CaF2 (fluorite structure) corresponds to
(A) mass of 8Ca++ ions & 4 F– ions (B) mass of 4Ca++ ions & 8 F– ions
(C) mass of 4Ca++ ions & 4 F– ions (D) mass of 1Ca++ ions & 2 F– ions
Solution: In CaF2 (Calcium fluorite) structure 1-unit cell contains 4-Ca2+ ions and 8F–
ions.
So, mass of unit cell of CaF2
= mass of 4 Ca2+ ions + mass of 8F ions
 (B)
Problem 14: Close packing is maximum in the Crystal which is

(A) Simple cube (B) bcc
(C) fcc (D) none
Solution: The close packing in the crystal is 0.52, 0.68 and 0.74 for simple cubic, body
centered cubic, and face-centered cubic respectively.
i.e. the close packing is maximum in fcc.
(C)
Problem 15: An ionic compound AB has ZnS type of structure, if the radius A + is 22.5pm,
then the ideal radius of B- is
(A) 54.35pm (B) 100pm
(C) 145.16pm (D) None
Solution: Since ionic compound AB has ZnS type of structure, therefore it has
tetrahedral holes, for which,
radius of cation
= 0.225
radius of anion
r
= 0.225
r
22.5
= 0.225
r
Hence, r– = 100 pm
(B)
RSM24-P6-CH-SS-26
14. Assignments (Subjective Problems)

LEVEL – I
1. A solid has a bcc structure, if the distance of closest approach between the two
atoms is 1.73Å, what is the edge length of the cell?
2. The unit cell of a metal of atomic mass 108 and density 10.5 gm/cm 3 is a cube with
edge-length of 409pm. Find the structure of the crystal lattice.
3. A compound alloy of gold and copper crystalizes in a cube lattice in which the gold
atoms occupy the lattice points at the corners of a cube and the copper atoms
occupy the centres of each of the cube faces determine the formula of this
compound.
4. The unit cube length of LiCl (NaCl structure) is 5.14A°. Assuming anion-anion
contact, Calculate the ionic radius of Cl- ion.
5. Calculate the value of Avogadro’s number from the following data:

Density of NaCl = 2.165gm/cm3
Distance between Na+ & Cl- ion in NaCl Crystal = 281pm
6. Aluminium forms face centered cubic crystals. The density of Al is 2.7 gm/cm 3.
Calculate the length of the side of the unit cell of Al [Al –27]
7. The compound CuCl has ZnS structure. Its density is 3.4 gm/cm3. What is the edge-
length of unit cell? (Cu – 63.5, Cl – 35.5)
8. An unknown metal is found to have a specific gravity of 10.2 at 25°C. It is found to

crystallize in a body-centered cubic lattice with a unit cell edge length of 3.147Å.
Calculate the atomic weight.
9. Polonium crystallizes in a simple cubic unit cell. It has atomic mass 209 and density
= 91.5 kg m-3. What is the edge-length of the unit cell?
10. 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.
11. Look at the sodium chloride structure and use it to calculate r+/r–.
12. RbI crystallizes in bcc structure in which each Rb+ is surrounded by eight iodide ions
each of radius 2.17A°. Find the length of one side of RbI unit cell.
13. An element A (Atomic wt – 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.
14. Potassium metal crystallizes in a face-centered arrangement of atoms where the

edge of the unit cell is 0.574 nm. What is the shortest separation of any two nuclei?
15. The density of CaF2 is 3.18 gm/cm3 at 20°C. Calculate the dimensions of the unit
cube of the substance.
RSM24-P6-CH-SS-27
LEVEL – II
1. The CsCl has cubic structure of ions in which Cs+ ion is present in body centere of
the cube. Its density is 4.50gm/cm3.
i) Calculate the edge-length of unit cell.
ii) What is the distance between Cs+ and Cl- ions?
ii) What is the radius of Cl- ions, if the radius of Cs+ ion is 200pm.
2. A metallic element crystallizes into a lattice containing a sequence of layers of

ABABAB… Any packing of spheres leaves out voids in the lattice. What percentage
by volume of this lattice is empty space?
3. Chromium metal crystallizes a body centered cubic lattice. The length of the unit cell
is found to be 287pm. Calculate the atomic radius. What would be density of
Chromium in gm/cm3?
4. Potassium metal crystallizes in a face centred arrangement of atoms, where the

edge of unit cell is 0.574nm. What is the shortest separation of two potassium nuclei.
5. The density of solid argon is 1.65gm per ml at – 233°C. If the Ar-atom is assumed to
be a sphere of radius 1.54 x 10-8cm, what percentage of solid argon has apparently
empty space [Ar = 40]
6. The molar mass of NaCl which crystallises with FCC lattice is 58.46 (in grams per
mole). The density of the crystal is 2.164 g/cm3. Calculate the distance between Na+
and Cl.
7. Calculate the void space as a fraction of the volume of the unit cell for FCC and BCC
lattices. Calculate the void space for metallic silver crystallizing in the FCC system,
the edge length of the unit cell being 4.07 Å. Calculate also the radius of the silver
atom.
8. In fcc arrangement of A & B atoms, where A atoms are at corners of the unit cell, B
atoms at the face-centers, one of the atoms are missing from the corner in each unit
cell then find the percentage of void space in the unit cell.
9. Silver iodide crystallizes in the cubic close packed Zinc blende structure. Assuming
that the iodide ions occupy the lattice points, what fraction of the tetrahedral sites is
occupied by silver ions?
10. a) Ferric oxide crystallizes in a hexagenal close – packed aray of oxide (O2–) ions
with two out of every three octahedral holes occupied by iron ions. What is the
formula of ferric oxide?
b) In cadium iodide every alternate octahedral hole in an HCP array of iodide I – ions
is occupied by a cadmium ion. What is the formula of cadium iodide.
11. The metal nickel crystallizes in a face centered cubic structure. Its density is 8.90
gm/cm3. Calculate (a) the length of the edge of a unit cell. (b) the radius of nickel
atom. (atomic weight of Ni = 58.89)
RSM24-P6-CH-SS-28
12. Compute the percentage void per unit volume of unit cell of Corundum.
13. KCl Crystallizes in the same type of lattice as does NaCl.

 r r 
Given that, Na = 0.5 and Na = 0.7
rCl  r 
K
Calculate:
a) The ratio of the side of unit cell for KCl to that for NaCl and
b) The ratio of density of NaCl to that for KCl.
14. An element crystallizes into a structure which may be described by a cubic type of
unit cell having one atom in each corner of the cube and two atoms on one of its face
diagonals. If the volume of this unit cell is 24 x 10 -24cm3 and density of the element is
7.20gm/cm3, calculate no. of atoms present in 200gm of the element.
15. Titanium has hexagonal close packing with cell edge length a = b = 295.3 pm, height
= c = 472.9 pm. Calculate its density.
RSM24-P6-CH-SS-29
LEVEL – III
1. If NaCl is doped with 10-3 mole % of SrCl2, what is the concentration of cation
vacancy?
2. A tetrahedron can be drawn within a cube. The centre of cube constitutes a

tetrahedral void. In closest packing two anions touch each other along the face
diagonal of the cube and one one cation (occupying a tetrahedral void) and two
anions (occupying two remote corners) touch each other along the body diagonal of
the cube show that r/r– = 0.225.
3. The ZnS Structure is cubic. The unit cell be described as a face-centered sulphide
ion sub-lattice with Zinc ions in the centers of alternating minicubes made by part on
the main cube into eight equal parts.
a) How many nearest neighbours does each Zn2+ have?
b) How many nearest neigbours does each S2– have?
c) What angle is made by the lines connecting any Zn++ to any two of its nearest
neigbours?
r
d) What minimum  ratio is needed to avoid anion-anion contact? Closest cation-
r
anion is assumed to touch.
4. Prove that the void space percentage in zinc blende structure is 25%.
5. 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.
If titanium is described as occupying holes in the BaO lattice, what types of hole
does it occupy?
What fraction of this type of hole does it occupy?
Can you suggest a reason why it has certain holes of this type but not other holes of
the same type?
6. NH4Cl crystallizes in a body centered cubic lattice with a unit cell distance of 387 pm.
Calculate
a) the distance between oppositely charged ions in the lattice and
b) the radius of the NH4+ ion if the radius of Cl– ion is 181 pm.
7. In a cubic crystal of CsCl (density = 3.97 gm/cm3) the eight corners are occupied by
Cl- ions with Cs+at the centre and visa-versa. Calculate the distance between the
neighbouring Cs+ and Cl- ions. What is the radius ratio of two ions?
8. 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.
RSM24-P6-CH-SS-30
9. CsCl crystallises in a cubic and that has a Cl– at each corner and Cs+ at the centre of
unit cell. If rCs  = 1.69Å and rCl  = 1.81Å, what is the value of edge-length ‘a’ of the
cube? Compare this value of ‘a’ (calculated) from the observed density of CsCl, 3.97
gm/cm3 [M(CsCl) = 168.5]
10. The composition of a sample of wurtsite is Fe0.93O1.0 What percentage of iron is

present in the form of Fe(III)?
11. Pottassium Crystallizes in body centred cubic lattice with a unit cell length a = 5.2Å.
a) What is the distance between nearest neighbours?
b) What is the distance between next nearest neighbours?
c) How many nearest neighbours does each K atom have?
d) How many next-nearest neigbbours does each K atom have?
e) What is the calculated density of crystalline Potassium?
12. Ice crystallizes in a hexagonal lattice. At the low temperature at which the structure
was determined, the lattice constants were a = 4.35 Å, and b = 7.00 Å. How many
molecules are contained in a unit cell?
[density (ice) = 0.92 gm/cm3)
13. Using the data given below, find the type of cubic lattice to which the crystal
belongs.
Fe V Pd
a in pm 286 301 388
 in gm cm-3 7.86 5.96 12.16
14. Iron Crystallizes in several modifications. At about 910°C, the body centered cubic -
form undergoes a transition to the face centered cubic -form. Assuming that the
distance between nearest neighbours is same in the two forms at the transition
temperature. Calculate the ratio of density of -iron to that of -iron at the transition
temperature.
15. Titanium crystallizes in a face centered cubic lattice. It reacts with C or H interstitially,
by allowing atoms of these elements to occupy holes in the host lattice. Hydrogen
occupies tetrahedral holes, but carbon occupies octahedral holes.
a) Predict the formula of titanium hydride and titanium carbide formed by saturating
the titanium lattice with either “foreign” element.
b) What is the maximum ratio of “foreign” atom radius to host atom radius that can
be tolerated in a tetrahedral hole without causing a strain in the host lattice?
RSM24-P6-CH-SS-31
15. Assignments (Objective Problems)

LEVEL – I
Instructions: Only one choice is correct:
1. The co-ordination number of metal crystallizing in a hexagonal close packed

structure is
(A) 12 (B) 4
(C) 8 (D) 6
2. The unit cell with crystallographic dimenions

a = b  c,  =  =  = 90° is
(A) Cubic (B) Tetragonal
(C) Monoclinic (D) Hexagonal
3. The anions (A) form hexagonal closest packing and atoms (C) occupy only 2/3 of
octahedral voids in it, then the general formula of the compound is
(A) CA (B) C2A2
(C) C2A3 (D) C3A2
4. Silver iodide has the same structure as zinc sulfide, and its density is 5.67gcm–3. The
edge length of the unit cell is
(A) 4.50 Å (B) 5.50 Å
(C) 6.50 Å (D) 7.50 Å
5. In the closest packing of atom A of radius ra, the radius of atom B that can be fitted in
tetrahedral void is
(A) 0.225 (B) 0.155 ra
(C) 0.414 ra (D) 0.732 ra
6. If the unit cell length of sodium chloride crystal is 600pm, then its density will be
(A) 2.165gm/cm3 (B) 3.247gm/cm3
(C) 1.79 gm/cm3 (D) 1.082 gm/cm3
7. In a cubic packed structure of mixed oxides, the lattice is made up of oxide ions, one
fifth of tetrahedral voids are occupied by divalent (X++) ions, while one-half of the
octahedral voids are occupied by trivalent ions (Y+++), then the formula of the oxides.
(A) XY2O4 (B) X2YO4
(C) X4Y5O10 (D) X5Y4O10
8. If three elements X, Y & Z crystallized in cubic solid lattice with X atoms at corners, Y
atoms at cube centre & Z-atoms at the edges, then the formula of the compound is:
(A) XYZ (B) XY3Z
(C) XYZ3 (D)X3YZ
9. A compound XY crystallizes in bcc lattice with unit cell edge-length of 480pm, if the
radius of Y- is 225 pm, then the radius of X+ is
(A) 190.70pm (B) 225pm
(C) 127.5pm (D) None
RSM24-P6-CH-SS-32
10. If the edge-length of the unit cell of Sodium chloride is 600pm, and the ionic radius of
Cl- ion is 190pm, then the ionic radius of Na+ ion is
(A) 310pm (B) 110pm
(C) 220pm (D) None
11. In a solid lattice the cation and anion both have left a lattice site. The lattice defect is
known as.
(A) interstitial defect (B) valency defect
(C) frenkel defect (D) schottky defect
12. The number of tetrahedral and octahedral voids in hexagonal primitive unit cell are
(A) 8,4 (B) 2,1
(C) 12,6 (D) 6,12
13. The rank of atoms in the hexagonal until cell is

(A) 4 (B) 3
(C) 5 (D) 6
14 The structure of CsCl Crystal is

(A) bcc lattice (B) fcc lattice
(D) Octahedral (D) None
15. In hexagonal primitive unit cell, the Corner is shared by

(A) 4 Unit cells (B) 6-unit cells
(C) 3 unit cells (D) 5 unit cells
16. An alloy of copper, silver and gold is found to have copper constituting the ccp
lattice. If silver atoms occupy the edge centres and gold is present at body centre,
the alloy has a formula.
(A) Cu4Ag2Au (B) Cu4Ag4Au
(C) Cu4Ag3Au (D) CuAgAu
17. A substance has density of 2 kg dm-3 & it crystallizes to fcc lattice with edge-length
equal to 700pm, then the molar mass of the substance is
(A)74.50gm mol-1 (B) 103.30gm mol-1
-1
(C) 56.02gm mol (D) 65.36gm mol-1
18. A common example of spinel strcuture is

(A) Fe2O3 (B) FeO
(C) Fe3O4 (D) FeCl3
19. In closest packing of atoms

(A) The size of tetrahedral void is greater than that of the octahedral void.
(B) The size of the tetrahedral void is smaller than that of the
octahedral void.
(C) The size of tetrahedral void is equal to that of the octahedral void.
RSM24-P6-CH-SS-33
(D) The size of tetrahedral void may be larger or smaller or equal to that of the
octahedral void depending upon the size of atoms.
20. If a be the edge-length of the unit cell, r be the radius of an atom, then for face
centered cubic lattice, the correct relation is
(A) 4r = 3a (B) 4r = 2a
(C) 4a = 3 r (D) None
21. When an ion leaves its correct lattice site and occupies interstitial sites in its crystal
lattice, it is called
(A) Crystal defect (B) Frenkel defect
(C) Schottky defect (D) None
22. The 8 : 8 type of packing is present in ?
(A) CsCl (B) KCl
(C) NaCl (D) MgF2
23. A face centre atom corner atom in the hexagonal unit cell structure is shared with
(A) 4-unit cells (B) 3-unit cells
(C) 6-unit cells (D) None
24. KBr shows, which of the following defects?

(A) Frenkel defect (B) Schottky defect
(C) Metal excess defeat (C) Metal deficiency
25. If in diamond, there is a unit cell of carbon atoms as fcc and if carbon atom is sp3
what fractions of void are occupied by carbon atom.
(A) 25% Tetrahedral (B) 50% Tetrahedral
(C) 25% Octahedral (D) 50% Octahedral
26. Which of the following doesn’t crystallise in the rock-salt structure?

(A) NaCl (B) KCl
(C) MgCl2 (D) CsCl
LEVEL - II More than one choice
1. Select the correct statements:-

3
(A) For CsCl unit cell (edge-length = a), rc + ra = a
2

(B) For NaCl unit cell (edge-length =  ), rc + ra =
2
(C) The void space in a b.c.c. unit cell is 0.68
(D) The void space % in a face-centered unit cell is 26%
2. Select the correct statements

CaCl2 doped with NaCl solid solution results in
RSM24-P6-CH-SS-34
(A) Substitutional cation vacancy (B) Frenkel’s defect

(C) Schottky defect (D) Decrease of density
3. Select the correct statement(s):-

(A) Schottky defect is shown by CsCl
(B) Frenkel defect is shown by Zns
(C) Hexagonal close packing (hcp) & Cubic close packing (ccp) structure has same co-
ordination no.12
(D) At high pressure, the co-ordination number increases.
4. Select the correct statement(s)

(A) At high pressure, the co-ordination no. increases from 6:6 to 8:8
(B) At high pressure, the co-ordination no. decreases from 8:8 to 6:6
(C) At high temperature, co-ordination number decreases
(D) At 760K temperature, CsCl structure changes into NaCl.
5. In antifluorite structure
(A) oxide ions are face centred
(B) cations are present in all the tetrahedral voids
3a
(C) rLi  rO2  
4
(D) Cations are face centred and anions are present in all the tetrahedral voids
6. Which of the following statements are correct?

(A) Halides of all alkali metals and alkaline earth metals have rock salt structure
(B) Cesium halides and beryllium oxides have rock salt structure
(C) In zinc blende structure, sulphide ions are face centered and zinc is present in alternate
tetrahedral voids
(D) In FCC unit cell, void percentage = 26%
7. In face centered cubic unit cell

(A) Rank of unit cell is 3
(B) Face diagonal of the cube which is 2a is equal to 4r
(C) 8 tetrahedral voids per unit cell of FCC

(D) Effective no. of atoms is 4 in FCC
8. If we assume ‘M’ crystallizes in a fcc unit cell and tetrahedral voids are also occupied by ‘M’
atoms. If the edge length of the unit cell is 0.55 nm and the density of ‘M’ is 2.23 g/cc, which
of the following statements are correct
(A) 40% of the tetrahedral voids are occupied by ‘M’-atoms in this lattice
(B) 50% of the tetrahedral voids are occupied by ‘M’-atoms in this lattice
(C) M-M bond length is equal to the sum of radii of 2 ‘M’ -atoms which is equal to
0.24 nm
(D) 20% of tetrahedral voids are occupied by ‘M’ –atoms in this lattice
RSM24-P6-CH-SS-35
9. Which of the following pair of ions have the same scattering power of X-rays
(A) Na+ and Cl– (B) K+ and Cl–
(C) Rb+ and Br– (D) K+ and Br–
10. Select the correct statement(s):

(B) Frenkel defect is shown by ZnS
(C) hcp and ccp structures have the same coordination number 12
(D) On increasing pressure, coordination number of CsCl decreases to that of NaCl
11. Select the correct statements:-

3
(A) For CsCl unit cell (edge-length = a), rc + ra = a
2

(B) For NaCl unit cell (edge-length =  ), rc + ra =
2
(C) The void space in a b.c.c. unit cell is 0.68
(D) The void space % in a face-centered unit cell is 26%
12. Select the correct statement(s):-
(B) Frenkel defect is shown by Zns
(C) Hexagonal close packing (hcp) & Cubic close packing (ccp) structure has same
co-ordination no.12
(D) At high pressure, the co-ordination number increases.
13. Select the correct statement(s)
(A) At high pressure, the co-ordination no. increases from 6:6 to 8:8
(B) At high pressure, the co-ordination no. decreases from 8:8 to 6:6
(C) At high temperature, co-ordination number decreases
(D) AT 760K temperature, CsCl structure changes into NaCl.
14. Select the correct statements
CaCl2 doped with NaCl solid solution results in
(A) Substitutional cation vacancy
(B) Frenkel’s defect
(C) Schottky defect
(D) Decrease of density
LEVEL - III Other Engg. Exams
1. How may unit cells are present in a cube-shaped ideal crystal of NaCl of mass 1.00 g ?
(A) 2.57  1021 unit cell (B) 5.14  1021 unit cells
(C) 1.28  10 unit cell
21
(D) 1.71  1021 unit cells
2. An element having bcc structure has 12.08  1023 unit cells. The number of atoms in these
cells is
RSM24-P6-CH-SS-36
(A) 12.08  1023 (B) 24.16  1023

(C) 48.38  1023 (D) 12.08  1022
3. An element (atomic mass = 100g/mol) having bcc structure has unit cell edge 400 pm.
Then, density of the elements is
(A) 10.376 g/cm3 (B) 5.188 g/cm3
(C) 7.289 g/cm3 (D) 2.144 g/cm3
4. Ionic soids with Schottky defects contain in their structure

(A) equal number of cation and anion vacancies.
(B) Anion vacancies and interstitial anions
(C) Cation vacancies
(D) Cation vacancies and interstitial cations
5. When NaCl is dopped with MgCl2 the nature of defect produced is

(A) Interstitial defect (B) Frenkel defect
(C) Schottky deffect (D) none of these
6. In a hexagonal close packed (hcp) structure of spheres, the fraction of the vaolume
occupied by the spheres is A. In a cubic close packed structure the fraction is B. The
relation for A and B is
(A) A = B (B) A > B
(C) A < B (D) A is equal to the fraction is a simple cubic
lattice
7. When molten Zn is cooled to solid state, it assumes HCP structure. Then the number of
nearest neighbours of Zn atoms will be
(A) 4 (B) 6
(C) 8 (D) 12
8. Due to Frenkel defect the density of ionic solids

(A) Decreases (B) Increases
(D) Does not change (D) changes
9. An ionic compound has a unit cell consisting of A ions at the corners of a cube B ions on the
centres of the faces of the cube. The empirical formula for this compound would be
(A) AB3 (B) A3B
(C) AB (D) A2B
10. Sodium metal crystallizes in a body centred cubic lattice with the cell edge a = 4.29Å. the
radius of sodium atom is :
(A) 1.85744 Å (B) 2.8574 Å
(C) 3.8574 Å (D) none
11. A certain metal fluoride crystallises in such a way that F atoms occupy simple cubic lattice
sites, while metal atoms occypy the body centres of half the cubes. The formula of metal
fluoride is
(A) M2F (B) MF
RSM24-P6-CH-SS-37
(C) MF2 (D) MF8
12. A binary solid (A+B) has a rock salt structure. If the edge length is 400 pm and radius of
cation is 75 pm the radius of anion is
(A) 100 pm (B) 125 pm
(C) 250 pm (D) 325 pm
13. The ionic radii of Rb+ and I are 1.46 and 2.16 Å. The most probable types of structre
exhibited by it is
(A) CsCl type (B) NaCl type
(C) ZnS type (D) CaF2 type
14. Which of the following is not a crystalline solid ?

(A) KCl (B) CsCl
(C) Glass (D) Rhombic sulphur
15. When molten Zn is cooled to solid state, it assumes HCP structre. Then the number of
nearest neighbours of Zn atoms will be
(A) 4 (B) 6
(C) 8 (D) 12
SECTION - III
A Matrix-Match Type
1. Match the following Column I with Column II.

Column – I Column – II
(A) Graphite (p) Planar
(B) Diamond (q) Sheet or layer like structure
(C) Black phosphorus (r) Discrete molecule
(D) White phosphorus (s) 3-dimensional network
2. Match the following Column I with Column II.

Column – I Column – II
(A) SCC (p) a
Z = 4; r 
2 2
(B) BCC (q) 3a
Z = 2; r 
4
(C) FCC (r) Z = 1; r = a/2
(D) HCP (s) Z = 6; r = a/2
RSM24-P6-CH-SS-38
B Linked Comprehension Type
C1–3 : Paragraph for Questions Nos. 1 to 3

Perovskite, a mineral containing calcium, oxygen & titanium crystallizes in the given unit cell
Calcium
Oxygen
Titanium
1. Total number of atom present in a unit cell is

(A) 3 (B) 4
(C) 5 (D) 6
2. The oxidation number of titanium in the perovskite is

(A) 5 (B) 4
(C) 3 (D) 2
3. If oxygen atom is removed from alternate position then the formula of perovskite is
(A) CaTiO (B) CaTi2O
(C) CaTiO2 (D) Ca3Ti2O

Solids are not perfect in structure and there are different types of imperfections in them. These
defects can be stoichiometric (e.g. Schottky and Frenkel) and non-stoichiometric defects. Non-
stoichiometric inorganic solids contain an excess or deficiency of one of the elements. There are
solids which are difficult to prepare in the stoichiometric composition, e.g. pure FeO is difficult to
obtain and normally we get a composition of Fe0.95O but it may range from Fe0.93O to Fe0.96O.
Zinc oxide loses oxygen reversibly at high temperatures and turns yellow in colour. The excess
metal is accommodated interstitially, giving rise to electrons trapped in the neighbourhood.
One of the common method of introduing defects in ionic solids is by adding impurity ions having
different charge than host ions.
4. Fe0.95O can be due presence of iron in +2 and +3 oxidation numbers. Then iron present in
+3 oxidation state will be
(A) 15% (B) 13.5%
(C) 10.5% (D) 8.85%
RSM24-P6-CH-SS-39
5. Yellow form of ZnO shows enhanced electrical conductivity due to

(A) the electrons trapped in neighbourhood of excess metal accommodated interstitially.
(B) excess of O2– ions
(C) excess of metal ions accommodated interstitially
(D) High temperature
6. If AgCl is doped with 10–4 mol % of CdCl2, then the concentration of cation vacancies per
mol will be
(A) 6.02  1016 (B) 6.02  1017
(C) 6.02  1018 (D) 6.02  1014

In hexagonal systems of crystals, a frequently encountered arrangement of atoms is described as a
hexagonal prism. Here, the top and bottom of the cell are regular hexagons and three atoms are
sandwiched in between them. A space-filling model of this structure, called hexagonal close-packed
(HCP), is constituted of a sphere on a flat surface surrounded in the same plane by six identical
spheres as closely as possible. Three spheres are then placed over the first layer so that they touch
each other and represent the second layer. Each one of thee three spheres touches three spheres
of the bottom layer. Finally, the second layer is covered with a third layer that is identical to the
bottom layer in relative position. Assume radius of every sphere to be ‘r’.
7. The number of atoms in this HCP unit cell is

(A) 4 (B) 6
(C) 12 (D) 17
8. The volume of this HCP unit cell is

(A) 24 2 r 3 (B) 16 2 r 3
64
(C) 12 2 r 3 (D) r3
3 3
9. The empty space in this HCP unit cell is
(A) 74% (B) 47.6%
(C) 32% (D) 26%
RSM24-P6-CH-SS-40
16. Answers to Subjective Assignments

LEVEL – I
1. 1.997Å 2. FCC
3. AuCu3 4. 1.815 Å
5. 6.08  1023 6. 4.045  10–8 cm
7. 5.78Å 8. 95.7
9. 1.559  10–8 cm 10. BCC = 7.887 g/cm3
FCC = 8.59 g/cm3
11. 0.414 12. 5.011 Å
13. 5.188 gm/cm3, 3.01  1022 unit cell 14. 0.406 nm
6.023  1022 atoms of A
15. 5.46 Å
LEVEL – II
1. (i) 85.35 Å, (ii) 73.8275 Å, (iii) 71.82 Å 2. 26%

3. r = 124.27 pm, d = 7.3 g/cm 3 4. 0.406
5. 48.612% 6. 2.820 Å
7. 0.2596, 0.32, 17.54  10–24 cm3, 1.439 Å 8. 43%
9. 50% 10. (a) Fe2O3, (b) CdsI2
11. (a) 3.53 Å, (b) 1.247 Å 12. 22.44%
13. A = 1.143, (b) = 1.172 14. 2.3148  1024 atoms
15. 4.486 gm/c3
LEVEL – III
1. 6.023  1018 2. 0.225

3. a) 4, (b) 4, (c) 109°28, (d) 0.225 5. a) octahedral holes,
b) 1/4th
6. a) 335.15 pm (b) 154.15 pm 7. 0.728
8. a) 2.88 Å, (b) 12, (c) 19.4 g/cc, (d) 0.74
9. 4.13 Å 10. 15.053
11. (a) 4.50 Å, (b) 5.20 Å, (c) 8, (d) 6,
(e) 0.921 g/cm3
12. 4 molecules of H2O 13. Fe - bcc, V - bcc, Pd - fcc
14. 1.0887 15. (a) TiH2,TiC, (b) 0.225, (c) 0.414
RSM24-P6-CH-SS-41
15. 6.3697 Ås
17. Answers to Objective Assignments
LEVEL – I
1. (A) 2. (B)
3. (C) 4. (C)
5 (A) 6. (C)
7. (C) 8. (C)
9. (A) 10. (B)
11. (D) 12. (C)
13. (D) 14. (A)
15. (B) 16. (C)
17. (B) 18. (C)
19. (B) 20. (B)
21. (B) 22. (A)
23. (C) 24. (B)
25. (D) 26. (D)
LEVEL – II
1. (A, B, D) 2. (A, D) 3. (A, B, C, D) 4. (A, C, D)
5. (A, B, C) 6. (C, D) 7. (B, C, D) 8. (B, C)
9. (B, C) 10. (A, B, C) 11. (A), (B), (D) 12. (A), (B), (C), (D)
13. (A), (C), (D) 14. (A), (D)
LEVEL – III
1. (A) 2. (B) 3. (B) 4. (A)
5. (C) 6. (A) 7. (D) 8. (C)
9. (A) 10. (D) 11. (C) 12. (B)
13. (D) 14. (C) 15. (D)
LEVEL – IV
A B
Match the following Write-up
1. (A – p, q), 1. (C)
(B – s), 2. (B)
(C – q), 3. (A)
(D – r) 4. (C)
2 (A – r), 5. (A)
(B – q), 6. (B)
(C – p),
7 (B)
(D – s),
8. (A)
9. (D)

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24

b) Amorphous solids: An amorphous solid differs from a crystalline substance in being

Crystalline solid Amorphous solid

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

4. They undergo a cleavage. 4. They undergo an irregular cut

2.1 What is a crystal

4. External Features of Crystals

6.1 Primitive Cubic Unit Cell

In a primitive cubic unit cell the same type of

manner as shown in the figure. Four atoms are

6.2 Body Centered Cubic Unit Cell

A Body Centred unit cell is a unit cell in which

This unit cell is created by placing four atoms

6.3 Face Centered Cubic Unit Cell

In a fcc unit cell, the same atoms

6.4 Hexagonal Primitive Unit Cell

Each corner atom would be common to 6

Density of crystal lattice

Exercise 1: Lithium borohydride crystallizes in an orthorhombic system with 4

7. Close Packing of Spheres

Place a sphere on a flat surface. Surround it

8. Octahedral and Tetrahedral Voids

(Figure 8(a) Voids in FCC unit cell)

Let us again consider a fcc unit cell. If we

Since there are eight corners, there are eight

9. Radius Ratio Rules

9.1 Co-ordination Number 3

The adjacent fig. 9(a) shows the smaller positive ion

BD = (BE / cos 30o), r+ + r- = r- / cos 30o Fig. 9(a)

9.2 Co-ordination Number 4 (Tetrahedron)

Angle ABC is the tetrahedral angle of 109o 28' and B

9.3 Co-ordination Number 6 (Octahedron) or 4 ( Square Planar)

A cross section through an octahedral site is shown in the

x < 0.155 2 Linear BeF2

10. Classification of Ionic Structures

10.1 Rock Salt Structure

Cl- is forming a fcc unit cell in which Cl

10.2 Zinc Blende Structure

10.3 Fluorite Structures

Calcium ions are face centered and fluoride

Unit cell representation of CaF2 structure Fig

10.4 Anti-Fluorite Structure

10.5 Cesium Halide Structure

Chloride ions are primitive cubic while the cesium ion

10.6 Corundum Structure

10.7 Pervoskite Structure

The general formula is ABO3. One of the cation is bivalent

10.8 Spinel and Inverse Spinel Structure

11. Imperfections in a Crystal

11.1 Stoichiometric Defects

11.2 Non-Stoichiometric Defects

Metal Excess: This may occur in two different ways

F-centre in a Sodium chloride crystal

Figure 19: Metal excess defects caused by interstitial cations.

12. Solution to Exercises

both will have same packing fraction.

Exercise-5 The co-ordination number of barium ions tells us that it is surrounded by

13. Solved Problems

 Void volume = 1 – 0.7493

Solution: From equation

Problem 5: A compound formed by elements X & Y, Crystallizes in the cubic structure,

Solution: From question

Since one unit cell contains 4 atoms

Solution: ACl(s)  A+(aq) + Cl–(aq)