Solid State PDF

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Classification of Solids
Solids are divided into two classes, namely crystalline and amorphous solids. A solid is said to be
crystalline if the constituents arrange themselves in regular manner throughout the
three−dimensional network. The ordered arrangement of building constituents extends over a
large distance. On the other hand, in amorphous solids, the arrangement of building constituents
is not regular. Although amorphous solids possess rigidity, incompressibility, refractive index
etc., but do not have characteristic shapes of geometrical forms.
Difference between Crystalline and Amorphous Solids: The substances

which show same electrical and optical properties in all directions are called isotropic and the
substances exhibiting directional differences in properties are called anisotropic.
Amorphous solids like liquids and gases are said to be isotropic while crystalline solids are called
anisotropic.
Due to the definite ordered state a crystalline solid tends to melt at a very short range of
temperature or in other words, these have sharp melting points. While amorphous solids melt at
larger range of temperatures.
Crystals are bound by plane faces. The angle between any two faces is called interfacial angle.
For a given crystalline solid, it is definite angle and remains always constant no matter how the
face develops. On the other hand, amorphous solids do not have well defined planes. When an
amorphous solid is broken, the surfaces of the broken pieces are generally not flat and they
intersect at random angles.
Space Lattice and Unit Cell: A crystal can be considered to be generated from the
repetition of some basic unit of pattern such as atoms, molecules or ions. In other words, a well
ordered and regular arrangement of constituents in the three dimensional space is called crystal
lattice. A space lattice can be sub−divided into a number of small cells known as unit cells. It can
be defined as the smallest block from which entire crystal can be built up by its translational
repetition in three dimensions.
Lattice Points
c
c
X
O b b
X
a a
Z
Z
Space lattice and a Unit cell
Types of Lattices
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Chemistry : Solid States - 2
Primitive Unit Cells: In a primitive unit cell, the same type of particles are present at all
the corners of the unit cell.
However, it has been observed that the particles may be present not only at the corners but also at
some other special positions within the unit cells. Such unit cells are called ‘non−primitive unit
cells’. There are three types of non−primitive unit cells as follows:
i) Face Centred: When atoms are present in all 8-corners and six face centres in a cubic
unit cell then this arrangement is known as FCC.
ii) End−Centred: When in addition to particles at the corners, there are particles at the
centres of the end faces.
iii) Body Centred: When atoms are present at 8 corners as well as in the body centre in a
cubic unit cell then this arrangement is known as BCC.
Seven Crystal Systems: The seven crystal systems are given below.
Parameters of Unit Cell
Crystal System Bravais Lattices Example
Intercepts Interfacial angle
1. Cubic Primitive, Face Centered, a = b = c α = β = γ = 90o Pb,Hg,Ag,Au
Body Centered = 3 Diamond, NaCl,
ZnS
2. Orthorhombic Primitive, Face Centered, a ≠ b ≠ c α = β = γ = 90o KNO2, K2SO4
Body Centered, End
Centered = 4
3. Tetragonal Primitive, Body Centered =2 a = b ≠ c α = β = γ = 90o TiO2,SnO2
4. Monoclinic Primitive, End Centered = 2 a≠b≠c α = γ = 90o, CaSO4,2H2O
β ≠ 90o
5. Triclinic Primitive = 1 a≠b≠c α ≠ β ≠ γ ≠ 900 K2Cr2O7,
CuSO45H2O
6. Hexagonal Primitive = 1 a=b≠c α = β = 90 , Mg, SiO2, Zn, Cd
0
γ = 120o
7. Rhombohedral Primitive = 1 a=b=c α = γ = 90o,β≠ 90o As, Sb, Bi, CaCO3
Total = 14
Seven Crystal Systems and Fourteen Bravais Lattice
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CUBIC
a
c
a
a
Simple Face Centred Body Centred α
b
ORTHORHOMBIC β
a π−γ
c angles between the planes
b
a Simple End Centred Body Centred Face Centred
TETRAGONAL MONOCLINIC
c c
a
b
a a
Simple Body Centred End Centred
Simple
RHOMBOHEDRAL TRICLINIC HEXAGONAL
c
c
a
a a a
b 120°
a a
Close Packing in Crystals

In order to understand the packing of the constituent particles in a crystal, it is assumed that these
particles are hard spheres of identical size. The packing of the crystals is done such that they
occupy the maximum available space and hence the crystal has maximum density.
There are two common ways in which spheres of equal size can be packed as shown below:
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Arrnagement (I) Arrnagement (II)
In arrangement (I), the spheres are packed in such a

way that their centres are at the centres of an
equilateral triangle. Each sphere is surrounded by six
other similar spheres.
This arrangement can be extended in three dimensions by adjusting spheres on the top of hollows
or voids of the two dimensional layers.
A A
A A A A A A A A
b b b b
a a a a a a
A A A A c c
b b b d d d
a a a a a a a a
A A A A A A A A A A
Fig. (a) Fig. (b)

Fig. (a) Fig. (b)
In the base layer shown in fig. (a), the spheres are marked as A and the two types of voids
between the spheres are marked as ‘a’ and ‘b’. Both voids are identical and similar arrangement
can be generated (of two layers) by placing next layer on either ‘a’ or ‘b’. Let us fill void ‘a’to
make the 3rd layer.
There are two types of voids in the second layer i.e. ‘c’ and ‘d’. The ‘a’ and ‘b’ voids in the first
layer are triangular while only ‘c’ voids of the second layer are triangular. The ‘d’ voids are
combination of two triangular voids (one each of first and second layer) with the vertex of one
triangle upwards and the vertex of other triangle downwards.
The void surrounded by four spheres and placed at an angle of 109° 28′ is known as tetrahedral
voids. ‘c’ void are known as tetrahedral voids ‘d’ voids and known as octahedral voids.
Octahedral voids are surrounded by six spheres.
Now, there are two ways to build up the third layer:

i) When the third layer is placed over the second layer so as to cover the tetrahedral or ‘c’
voids, a three−dimensional closest packing is obtained where the spheres in every third
layer are vertically aligned to the first layer. This arrangement is called ABAB.,… pattern
or hexagonal (HCP) close packing (calling first layer as A and second layer B).
ii) When the third layer is placed over the second layer such that the spheres cover the
octahedral or ‘d’ voids, a layer C different from A and B is formed. This pattern is called
ABCABC……pattern or cubic close packing (CCP).
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In both HCP and CCP methods of packing, a sphere is in contact with six other spheres in its own
layer. It touches three spheres in the layer above and three spheres in the layer below. Thus a
sphere is in direct contact with 12 other spheres. In other words, the coordination number of that
sphere is 12. Coordination number is the number of closest neighbours of any constituent
particle.
In CCP unit cell there are 8 tetrahedral voids and 4 octahedral voids.
No. of tetrahedral voids in an unit cell = No. of octahedral voids × 2
The HCP and CCP arrangements can also be shown as below.
b b
(a) (b)
(a) (b)
Fig : Cubic closest packing of spheres : (a) generation of
Hexagonal closest packing of spheres: (a) normal unit from closest packed layers and (b) rotation to show
and (b) exploded view cubic symmetry.
Radius Ratio Rules: The structure of many ionic solids can be accounted by considering the
relative sizes of the cation and anion, and their relative numbers. By simple calculations, we can
work out as how many ions of a given size can be in contact with a smaller ion. Thus, we can
predict the co−ordination number from the relative size of the ions.
Calculation of some limiting radius ratio values
a) Co−ordination Number 3: The adjacent figure shows the A
smaller positive ion of radius r+ in contact with three larger

anion of radius r–. D
In this figure, AB = BC = AC = 2r– B E C

BE = r–
BD = r+ + r–
∠ABC = 60° ⇒ ∠BDC = 120° or ∠BDE = 60°
∴ ∠DBC = 30°
BE r− r−
BD = ⇒ r+ + r– = = = 1.155r–
cos30° cos30° 0.866
∴ r+ = 1.155r– – r+ = 0.155r–
r+
= 0.155
r−
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b) Co−ordination Number 4: (tetrahedron) B
Angle ABC is the tetrahedral angle

1
⇒ ∠ ABC = 109° 28’ ⇒ ∠ ABD = (109° 28′) = 54° 44′
2 D
− A C
AD r
sin (∠ABD) = 0.8164 = = + −
AB r + r
r+ + r− 1 r+
⇒ = = 1.225 ⇒ = 0.225
r− 0.8164 r−
c) Co−ordination Number 6: (Octahedron): A cross

section through an octahedral site is shown in the adjacent
figure and the smaller positive ion touches six larger negative
ions. (Only four negative ions are shown in the figure but there A
is one sphere above and the below the plane of paper).
In this figure
B C
AB = r+ + r– and BD = r– D
BD r−
∠ABC = 45° ⇒ cos(∠ABD) = 0.7071 = = + −
AB r + r
r+
Solving, we get = 0.414
r−
 r+  Co−ordination
Limiting radius ratio  −  Shape Examples
number
r 
< 0.155 2 Linear BeF2
0.155 – 0.225 3 Trigonal planar B2O3
0.225 – 0.414 4 Tetrahedral ZnS, SiO44–
0.414 – 0.732 4 Square planar PtCl42–
0.414 – 0.732 6 Octahedral NaCl
0.732 – 0.999 8 Body centred cubic CsCl
Illustration 3: Iron crystallises in a body centred cubic structure. Calculate the radius of Fe
atom if edge length of unit cell is 286 pm.
Solution: Edge length, a = 286 pm
3 3 1.732 × 286
For BCC, radius of atom, r = a = × 286 = = 123.8 pm
4 4 4
Calculation of density of a cubic crystal from its edge: If we know the type
of crystal structure possessed by the cubic crystal, so that the number of particles per unit cell are
known and the edge length for it is known by X−Ray studies, the density of the crystal can be
determined.
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Case I: For cubic crystals of elements:

Let the edge of the unit cell = a pm
No. of atoms present per unit cell = Z
Atomic mass of the element = M
∴ Volume of the unit cell = (a pm)3 = a3 pm3 = a3 × 10–30 cm3
a
Density of the unit cell,
Mass of the unit cell
ρ=
Volume of the unit cell
=
( No. of atoms in its unit cell ) × ( Mass of each atom )
a 3 × 10−30
M
Z×
NA Z× M
= 3 g / cm3 (NA – Avogadro’s number) = g/cm3
a × 10 −30
N A × a × 10
3 −30
Case II: For cubic crystals of ionic compounds: Here, Z is the number of formula units
present in one unit cell and M is the formula mass. The formula will remain the
same viz.
Z× M
ρ= g./ cm3
N A × 10−30
Illustration 4: Lithium borohydride (LiBH4), crystallises in an orthorhombic system with 4

molecules per unit cell. The unit cell dimensions are a = 6.81 A, b = 4.43A,
c = 717 A. If the molar mass of LiBH4 is 21.76 g mol-1. What is the density of
the crystal ?
Solution: We know that,
ZM 4 × (21.76 g mol −1 )
ρ= =
NV (6.023 × 1023 mol −1 ) (6.81× 4.43 × 7.17 × 10−24 cm3 )
= 0.668 g cm-3
Classification of Ionic Structures

Simple ionic compounds are of the type AB or AB2 where A and B represent the positively and
negatively charged ions respectively. (In any solid of the type AxBy, the ratio of co−ordination
number of A to B would be y :x.
Structures of Type AB: Ionic compounds of the type AB means compounds having the
positively and negatively charged ions in the ratio 1:1. These compounds can have following
three type of structures.
1. Rock salt (NaCl) type

2. Cesium chloride (CsCl) type
3. Zinc blende (ZnS) type
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1. Rock Salt (NaCl) type Structure: Cl– is

forming a FCC unit cell in which Na+ is in the octahedral +
voids. The co−ordination number of Na+ is 6 and that of Na
Cl– would also be 6. Moreover, there are 4 Na+ ions and 4 Cl
-
Cl– ions per unit cell. The formula is Na4Cl4 i.e. NaCl.
Other examples for this type of structure are all halides of
alkali metals except CsCl and all oxides of alkaline earth
metals except BeO.
2. Zinc Blende Structure (ZnS): Sulphide ions

Zn2 +
are face centred and zinc is present in alternate tetrahedral S 2−
voids. Formula is Zn4S4, i.e. ZnS. Coordination number
S2− ion surrounded
of Zn is 4 and that of sulphide is 4. Other substance that tetrahedrally by four
exists in this kind of a structure is BeO. Zn 2+ ions
3. Cesium Chloride (CsCl) type structure:

CsCl has body−centred cubic (bcc) arrangement. Each
Cs+ ion is surrounded by 8 Cl– ions and each Cl– ion is +
Cs ion surrounded b
-
surrounded by 8 Cs+ ions i.e. this structure has 8:8 by 8 Cl ions
co−ordination. A unit cell of CsCl consists of only one

unit of CsCl i.e. One Cs+ ion and one Cl– ion. Few
examples of compounds having CsCl structure are CsBr,
CsI, CsCN, TlCl, TlBr, TlI and TlCN.
Structure of Ionic Compounds of the Type AB2: These are the ionic
compounds having cations/anions or anions/cations in the ratio 1:2. Most of these compounds
have calcium−fluorite (CaF2) type structure. These compounds have cubic close packing (CCP)
arrangement in which Ca2+ ions are present at the corners and the centre of each face of the cube.
Each Ca2+ ion is surrounded by 8F– ions i.e. it has a

Ca 2+
co−ordination number of 8 whereas each F– ion is surrounded
by 4 Ca2+ ions i.e. has a co−ordination number of 4. Thus this F−
structure has 8:4 co−ordination. Few examples of such
compounds having CaF2 structure are BaF2, BaCl2, SrF2,
SrCl2, CdF2, PbF2 and ThO2.
In Na2O each oxide ion is co−ordinated to 8 Na+ ions and each Na+ ion to 4 oxide ions. Hence it
has 4:8 co−ordination. This is called anti−fluorite structure. Others examples being Cl2O, K2O,
Li2O, K2S, Na2S etc.
Ionic Radii: The internuclear distance between the ions at the adjacent corners of a unit cell
can be taken as the sum of the radius of the cation and the radius of the anion.
But it’s not simple to assign different values to constituting ions because it’s not possible to
calculate the radius of one ion without knowing the radius of other one.
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It has been observed that radius of a cation is smaller than that of the corresponding atom. The
reason is that with the removal of one (or more) electrons from the valence shell of the atom, the
effective nuclear charge increases because now, it is acting on a smaller number of electrons,
making the electron cloud pulled more inward towards the nucleus than before.
On the other hand, the radius of an anion is larger than that of the corresponding atom, reason
being, with addition of one (or more) electrons to the valence shell, effective nuclear charge
decreases because the same nuclear charge is now acting on a larger number of electrons.
Consequently, the force of attraction on the electron cloud decreases and hence the ionic radius
increases.
Ionic radius increases in a group with increase in atomic number as:

Li+ < Na+ < K+ < Rb+ < Cs+
Similarly, in the halogens, the ionic radius increase as:
F– < Cl– < Br– < I–
The reason for this increase is the increase in the principal quantum number though the number
of electrons in the valence shell remains the same. In the same period, the radius of isoelectronic
ions (having same number of electrons) decreases with the increase in charge of the ions. e.g.
Na+<Mg2+< Al3+.
Imperfection in Solids
An ionic crystal which has the same unit cell containing the same lattice points throughout the
crystal is known as ideal crystal but crystals tend to have a perfectly ordered arrangement at only
absolute zero. This arrangement corresponds to state of lowest energy. And as the temperature
increases, the crystals start deviating from the perfectly ordered arrangement. This defect may
appear at a point, along a line or over a surface.
A point defect could arise due to the absence of a particle (vacancy), presence of some foreign
particle at a lattice site, presence of a foreign particle at the interstitial site or displacement of a
particle to the interstitial site.
Two main defects in crystals which are discussed as follows are Schottky and Frenkel defects
Schottky Defect: This defect is caused when some of the lattice points are unoccupied and
those points are called vacancies or holes fig. (a). The number of missing positive and negative
ions is the same so that the crystal remains neutral in all. Schottky defects are more common in
ionic compounds with high co−ordination number, and where the sizes of positive and negative
ions are almost equal for example, NaCl, KCl, CsCl and KBr.
The number of defects increases with increase in temperature. The number of defects increases to
one in 106 sites at 775 K and one in 104 sites at 1075K. The presence of large number of
Schottky defects in crystal results in significant decrease in its density.
Frenkel Defect: This defect is caused when some of the ions leave their lattice sites to
occupy an interstitial site fig. (b). Frenkel defects are more common in ionic compounds with
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low co−ordination number and where there is large difference in size between positive and
negative ions for example, ZnS, AgCl, AgBr and AgI.
In pure alkali metal halides, these defects A+ B- A+ B- A+ B- A+ B-
are not very common because the ions

cannot get into interstitial positions due to B- B- A+ B- A+ B- A+
their large sizes. A +
A+ B- A+ B- B- A+ B-
B- A++
A A+ B- A+ B- A+
Fig. (a): Schottky Defect Fig. (b): Frenkel Defect
Metal Excess Defect: This may occur in two different ways
F-Centres: A negative ion may be absent from its lattice site leaving a hole which is occupied
by an electron, thereby maintaining the electrical balance. This type of defect is formed by
crystals which would be expected to form Schottky defects. When compounds such as NaCl,
KCl, are heated with excess of their constituent metal vapours, or treated with high energy
radiation, they become deficient in the negative ions and their formulae may be represented by
AX1–δ, where δ 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
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+δX. 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.
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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+
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, non-stoichiometric KCl is lilac.
Metal Deficiency Defect: This defect is caused by A++

A B- A++
A B-
the missing cation from its lattice site. The extra negative
charge may be balanced if the adjacent metal ion has higher B- B- A+
positive charge. This can be possible by compounds of
transition metals (variable valency). Crystals of FeO, FeS
A+ B- A2+ B-
and NiO show this defect.
B- A+ B- A+
Metal deficiency due to cation vacancy
Properties of Solids
Electrical Properties: Solids can be broadly classified into three types, on the basis of
electrical conductivity.
a) Metals (conductors)
b) Insulators
c) Semi−conductors
Electrical conductivity of metals is very high and is of the order of 106 – 108 ohm–1 cm–1 whereas
for insulators, it is of the order of 10–12 ohm–1 cm–1. Semi−conductors have intermediate
conductivity in the range of 102 – 10–9 ohm–1 cm–1. Electrical conductivity of solids may arise
through the motion of electrons and holes (positive) or through the motion of ions. The
conduction through electrons is called n−type conduction and through (positive) holes is called
p−type conduction. Pure ionic solids where conduction can take place only through movement of
ions are insulators. The presence of defects in the crystal structure increases their conductivity.
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The conductivity of semi−conductors and insulators is mainly due to the presence of interstitial
electrons and positive holes in the solids due to imperfections. The conductivity of
semi−conductors and insulators increases with increase in temperature while that of metals
decrease.
Magnetic Properties
Diamagnetic Materials: Those materials which are weakly repelled by the magnetic field
are called diamagnetic materials. e.g. Cu+, TiO2, NaCl and benzene. They do not have unpaired
electrons.
Paramagnetic Materials: The materials which are weakly attracted by magnetic field are
called paramagnetic materials. These materials have permanent magnetic dipoles due to presence
of atoms, ions or molecules with unpaired electron. e.g. O2, Cu2+, Fe2+ etc. But these materials
lose their magnetism in the absence of magnetic field.
Ferromagnetic Materials: The materials which show permanent magnetism even in the
absence of magnetic field are called ferromagnetic materials. These materials are strongly
attracted by the magnetic field. e.g. Fe, Co, Ni and CrO2. Ferromagnetism arises due to
spontaneous alignment of magnetic moments of ions or atoms in the same direction.
Alignment of magnetic moments in opposite directions in a compensatory manner and resulting

in zero magnetic moment gives rise to anti−ferromagnetism
↑↑↑↑↑↑↑ ; ↑↓↑↓↑↓↑ ; ↑↓↓↑↓↓↑

ferromagnetism Anti − ferromagnetism Ferrimagnetism
for example, MnO, Mn2O3 and MnO2.
Alignment of magnetic moments in opposite directions resulting in a net magnetic moment due
to unequal number of parallel and anti−parallel magnetic dipoles give rise to ferri−magnetism
e.g. Fe3O4.
Ferromangetic and ferrimagnetic substances change into paramagnetic substances at higher
temperature due to randomisation of spins. Fe3O4, is ferrimagnetic at room temperature and
becomes paramagnetic at 850 K.
Dielectric Properties: The electrons in insulators are closely bound to the individual atoms
or ions and thus they do not generally migrate under the applied electric field. However, due to
shift in charges, dipoles are created which results in polarisation. The alignment of these dipoles
in different ways i.e. compensatory way (zero dipole) or non−compensatory way (net dipole)
impart certain characteristic properties to solids.
If the dipoles align in such a way that there is net dipole moment in the crystals, these crystals are
said to exhibit piezoelectricity or piezoelectric effect i.e. when such crystals are subjected to
pressure or mechanical stress, electricity is produced. Conversely, if an electric field is applied to
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such a crystal, the crystal gets deformed due to generation of mechanical strain. This is called
inverse piezoelectric effect.
Some crystals which on heating, acquire electric charges on opposite faces, are said to exhibit
pyroelectric effect.
The solids, in which dipoles are spontaneously aligned in a particular direction, even in the
absence of electric field are called ferroelectric substances and the phenomenon is known as
ferroelectricity. If the alternate dipoles are in opposite direction, then the net dipole moment will
be zero and the crystal is called anti−ferroelectric.
Ferroelectric solids – Barium titanate (BaTiO3), sodium potassium tartrate (Rochelle salt) and
potassium hydrogen phosphate (KH2PO4). Anti−ferroelectric – Lead Zirconate (PbZrO3).
Super Conducting Materials: The material which offer no resistance to the passage of
electricity is called superconductor or super conducting material. In this state, the materials
become diamagnetic and are repelled by the magnets. Most of the metals become super
conducting at low temperatures (2 – 5K). Highest temperature at which super conductivity is
known is 23K in alloys of niobium (e.g. Nb3Ge). Many complex metal oxides have been found to
possess super−conductivity at somewhat higher temperatures.
Material Temperature
Nb3Ge 23K
Bi2Ca2Sr2Cu3O10 105K
Ti2Ca2Ba2Cu3O10 125K
Amorphous Solids: Solids, which do not have an ordered arrangement of their constituent
atoms or ions but have a disordered or random arrangement are called amorphous solids e.g.
ordinary glass.
Properties of Amorphous Solids

i) Short range order: Amorphous solids have a short range order like liquids i.e. the order
does not extend to large three dimensional network.
ii) No sharp melting point: These solids melt over a range of temperature. This property
is used in moulding and giving desired shape to the articles of glass.
iii) Conversion into crystalline form on heating: Amorphous solids, when heated
and cooled slowly, become crystalline at certain temperature.
Use of Amorphous Solids
i) Amorphous solids, in the form of inorganic glasses, find application in construction,

house−ware, laboratory ware etc.
ii) These solids are used in making tyres, shoe soles etc., in the form of rubber.
iii) Large number of plastics are being used in articles of daily use.
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iv) These are used in photo voltaic cells (for converting sunlight into electricity).
Points to Remember
Amorphous substance are isotropic, while crystalline substances are said to be
anisotropic.
The reverse of crystallisation is the fusion or melting of the solid.
A crystal may have one or more planes and one or more axes of symmetry, but it has only
one centre of symmetry. A cubic crystal, such as NaCl possesses a total of 23 elements of
symmetry.
The unit cell is the smallest unit of a crystal, which when repeated, in three dimensions,
will generate the crystal.
In a cubic system of crystals, there are three types of Bravais lattices, depending upon the
shapes of the unit cell viz., simple cubic, face centred and body centred lattices.
Close packing means an arrangement in which a given number of equal spheres occupy
the minimum amount of space.
Limiting radius ratio (r+/r–) −ordination number
Co−
< 0.155 2
0.155 – 0.225 3
0.225 − 0.414 4
0.414 – 0.732 4
0.414 – 0.732 6
0.732 – 0.999 8
Structural relationship for cubic lattices
Simple BCC FCC
Lattice points per unit cell 1 2 4
No. of nearest neighbours 6 8 12
Distance between nearest neighbours a 3a a
2 2
Atomic radius a 3a a
2 4 2 2
Occupied volume (P.F.) 52.3% 68% 74%
Density of cubic crystal is given by
M×Z
ρ=
NA × a3
M – molecular mass of the substance
Z – no. of formula units per unit cell of the crystal
NA – Avogadro’s number
a − edge length of the cubic cell
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Schottky defect is observed in the crystals, of KCl, NaCl, CsCl, KBr etc. Frenkel defect is
observed in crystals of CaF2, ZnS, AgI and AgBr etc. and is less common than Schottky
defect. Metal excess defect because of anion vacancies, occurs e.g. in yellow coloured
NaCl and due to cation vacancies, occurs in NiO, FeO and FeS etc. Metal excess defect
due to interstitial cation occurs in Zinc oxide (ZnO).
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Solved Problems
Objective
Problem 1: 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: (a) 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
Problem 2: 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 (Y3+), then
the formula of the oxide is:
(a) XY2O4 (b) X2YO4
(c) X4Y5O10 (d) X5Y4O10
Solution: (c) In CCP anions occupy primitives of the cube while cations occupied voids.
In CCP there are two tetrahedral voids and one octahedral hole.
For one oxygen atom there are two tetrahedral holes and one octahedral hole.
Since one fifth of the tetrahedral voids are occupied by divalent
cations (X2+).
1
∴ number of divalent cations in tetrahedral voids = 2 ×
5
Since half of the octahedral voids are occupied by trivalent cations (Y3+)
1
∴number of trivalent cations = 1 ×
2
So the formula of the compound is X2/5Y1/2O or X4Y5O10
Problem 3: 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: (a) 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
[Type text]
Problem 4: Fraction of total volume occupied by atoms in a simple cubic cell is

π 3π
(a) (b)
2 8
2π π
(c) (d)
6 6
Solution: (d) 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
πr πr
3 3 π
= 3
= 3
=
a (2r) 6
Problem 5: The limiting radius ratio of the complex [Ni(CN)4]2–is

(a) 0.225 – 0.414 (b) 0.414 – 0.732
(c) 0.155 – 0.225 (d) None
Solution: (b) The complex [Ni(CN)4]–2 is square planar. So, it has limiting radius ratio
as octahedral structure i.e. 0.414 – 0.732
Problem 6: 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/yQ1/z (d) None
Solution: (b) 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
Problem 7: 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: (b) For fcc lattice

4r = √2a where a = 620 pm
1
r, r = ×a
2 2
1
× 620 m = 219.20 pm
2 2
Problem 8: The arrangement of Cl- ions in CsCl structure is

(a) hcp (b) fcc
(c) bcc (d) Simple cubic
[Type text]
Solution: (d) 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.
Problem 9: In closest packing of A type of atoms (radius, rA), 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: (c) For octahedral void
rB
= 0.414
rA
or, rB = 0.414 rA
Problem 10: In α-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: (b)
In α-WCl6, Cl– ions are arranged in cubic close packing, so, there is only one
Cl–ion in 1-unit cell. So, the formula can be written W1/6Cl, i.e. 1/6 of the
octahedral hole is filled by W.
Problem 11. Tetragonal crystal system has the following unit cell dimensions
(a) a = b = c & α = β = γ = 900 (b) a = b ≠ c and α = β = γ = 900
(c) a ≠ b ≠ c & α = β = γ = 900 (d) a = b ≠ c and α = β = 900, γ = 1200
[MP PMT 1993]
Solution: (b) Tetragonal system has the unit cell dimension a = b ≠ c, α = β = γ = 900 .
Problem 12. The maxium radius of sphere that can be fitted in the octahedral hole of
cubnical closed packing of sphere of radius r is
(a) 0.732 r (b) 0.414 r
(c) 0.225 r (d) 0.155 r
[KCET 2002]
Solution: (b)
Problem 13. The crystal system of a compound with unit cell dimensions a = 0.387,
b = 0.387 and c = 0.504 nm and α = β = 900 and γ = 1200 is
(a) Cubic (b) Hexagonal
(c) Orthorhombic (d) Rhombohedral
[AIIMS 2004]
Solution: (b)
[Type text]
Problem 14. The number of tetrahedral voids in the unit cell of a face centred cubic
lattice of similar atoms is
(a) 4 (b) 6
(c) 8 (d) 10
[Kerala PMT 2004]
Solution: (c)
Problem 15. If ‘Z’ is the number of atoms in the unit cell that represents the closest
packing sequence ---ABC ABC - - -, the number of tetrahedral voids in the
unit cell is equal to
(a) Z (b) 2Z
(c) Z/2 (d) Z/4
[AIIMS 2005]
Solution: (b) Number of tetrahedral voids in the unit cell = 2 × number of atoms = 2Z
Problem 16. The intermetallic compound LiAg crystallizes in cubic lattice in which both
lithium and silver have coordination number of eight. The crystal class is
(a) Simple cube (b) Body-centred cube
(c) Face – centred cube (d) None of these
[CBSE PMT 1997]
Solution: (b) In body centred cubic, each atom/ion has a coordination number of 8.
Problem 17. A solid is made of two elements X and Z. The atoms Z are in CCP
arrangement while the atom X occupy all the tetrahedral sites. What is the
formula of the compound .
(a) XZ (b) XZ2
(c) X2Z (d) X2Z3
[UPSEAT 2004]
Solution: (c) Tetrahedral sites one double comparable to octahedral sites then ratio of X
and Z respectively 2 : 1 since formula of the compound X2Z.
Problem 18. An ionic compound has a unit cell consisting of A ions at the corners of a
cube and B ions on the centres of the faces of the cube. The empirical
formula for this compound would be
(a) AB (b) A2B
(c) AB3 (d) A3B
[CBSE PMT 2004, AIEEE 2005]
Solution: (c) A atoms are at eight corners of the cube. Thereofre, the no. of A atoms in
the unit cell = 8/8 = 1. B atoms are at the face centre of six faces. Therefore,
its share in the unit cell = 6/2 = 3. The formula is AB3.
[Type text]
Problem 19. For an ionic crystal of the general formula AX and coordiantion number 6,
the value of radius ratio will be
(a) Greater than 0.73 (b) In between 0.73 and 0.41
(c) In btween 0.41 and 0.22 (d) Less than 0.22
[MP PMT 1993]
Solution: (b) The structural arrangement of co-ordination number ‘6’ is octahedral and
its radius ratio is 0.414 – 0.732. The example of octahedral is KCl and NaCl.
Problem 20. In the crystals of which of the following ionic compouds would you expect
maxium distance between centres of cations and anions
(a) Li F (b) CsF
(c) CsI (d) LiI
[CBSE PMT 1998]
Solution: (c) Cs+ and I− have largest sizes.
Problem 21: The ionic radii of Cs and Cl are 0.165 and 0.181 nm respectively. Their
atomic weights are 133 and 35.5. Then,
(a) The lattice parameter is 0.4 nm
(b) The lattice parammter can not be determined from this data.
(c) The density of CsCl is 4.37 × 103 kg/m3.
(d) The CsCl structure has a bcc structre with a bsis.
Solution: (a, c, d)
Problem 22: The unit cell of aluminum is face centred with a lattice constant 0.405 nm.
An aluminum foil of thickness 0.005 cm and side 25 cm square weights
0.0085 kg. Then,
(a) The number of unit cells in the foil is 4.22 × 1022. cm3
(b) the number of atoms present in the foil is 1.9 × 1023.
(c) The density of aluminum is 2720 kg/cm3
(d) The number of atoms in each into cell is 4.
Solution: (a, b, c, d)
Problem 23: In an NaCl structure, all the

(a) Octahedral sites are occupied
(b) Tetrahedral sites are unoccupied
(c) Octahedral as well as the tetrahedral sites are occupied
(d) Octahedral as well as the tetrahedral sites are unoccupied.
Solution: (a, b)
Problem 24: The radius of an atom is r. The mximum radius of the interstitial sphere
that can just fit into the void at the body centre of a
[Type text]
(a) FCC structure is 0.155 r. (b) BCC structure is 0.155 r.

(c) FCC structure is 0.414 r. (d) BCC structure is 0.414 r.
Solution: (b, c)
Problem 25: 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: (a), (b), (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.
Problem 26: Match List I and List II
Column I Column II
(a) Schottky defect (p) NaCl + SrCl2
(b) Frenkel defect (q) Reacting Na vapour in NaCl
(c) F – centres (r) NaCl
(d) Metal excess defect (s) AgCl
Solution : (a – r), (b – s), (c – q), (d – p)
Write-up – I
Perovskite, a mineral containing calcium, oxygen & titanium crystallizes in the given unit
cell
Calcium
Oxygen
Titanium
[Type text]
1. Total number of atom present in a unit cell is

(a) 3 (b) 4
(c) 5 (d) 6
2. The formula of perovskite is

(a) CaTiO (b) CaTiO2
(c) CaTiO3 (d) CaTiO4
3. The oxidation number of titanium in the perovskite is

(a) 5 (b) 4
(c) 3 (d) 2
4. If oxygen atom is removed from alternate position then the formula of perovskite is
(a) CaTiO (b) CaTi2O
(c) CaTiO2 (d) Ca3Ti2O
Solution:
1. (c)
1
No. of Ca atom = 8 × = 1
8
1
No. of O–atom = 6 × = 3
2
No. of Ti – atom = 1 × 1 = 1
Total no. of atom = 5
2. (c) The formula of perovskite is CaTiO3
3. (b) CaTiO3
2+x–6=0
x=4
4. (a) If no. of O–atom is removed from alternate position (face)

1
No. of O–atom remain = ×2=1
2
∴ Hence formula of perovskite is CaTiO
Write-up – II
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.
[Type text]
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.
1. 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%
2. 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
3. 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
Solution :
1. (c)
Let iron present in +3 oxidation state is x, then
3 × x + 2 × (0.95 – x) = 2 ⇒ x = 0.1
0.1
% of Fe in +3 oxidation state = ×100 = 10.5%
0.95
2. (a)
3. (b)
[Type text]
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
ρ= ,
NA × a3
a) for fcc structure
4r = 2 a
a = 2 2 r = 2 2 × 130 pm
= 367.64 pm
b) volume of unit cell = a3
(3.67 × 10–8 cm)3 = 4.94 × 10–23 cm3
c) n = 4
4 × 63.54
d) ρ = −8
= 8.54 gm / cm3
6.023 × 10 × (3.67 ×10 cm )
23 3 3
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 ×  πra3  + × 8 ×  πrc3 
π   rc  
3
 3  2  3 
= = 1 +   
16 2ra3 3 2   ra  
Q for tetrahedral holes,
rc
= 0.225
ra
π
= {1 + (0.225)3} = 0.7493
3 2
∴ 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?
[Type text]
Solution: From equation

ρ(density) = 3.35 gm/cm3
a = 4.80 Å
Mm of CaO = (40 + 16) gm = 56 gm CaO
n×Mm
Qρ= 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: In a close packed structure of mixed oxides, the lattice is composed of oxide
ions, one eighth of tetrahedral voids are occupied by divalent cations while
one half of octahedral voids are occupied by trivalent cations. What is the
formula of the oxide?
Solution: For per oxide ion in unit cell:

Number of tetrahedral voids per ion in lattice = 2
1 1
∴ Number of divalent cation (A) = × 2 =
8 4
Number of octahedral voids per ion in lattice = 1
1 1
∴ Number of trivalent cations (B) = 1 × =
2 2
∴ Formula = A1/ 4 B1/ 2 O = AB2 O 4
Problem 5: A compound formed by elements A and B crystallizes in cubic structure

where A atoms are at the corners of a cube and B atoms are at the face
center. What is the formula of the compound?
Solution: A atom are eight corners of the cube.
8
Therefore, the number of A atoms in the unit cell = = 1
8
B atoms are at the face centre of six faces
6
Therefore, its share in the unit cell = =3
2
The formula is AB3
[Type text]
Problem 6: NH4Cl crystallizes in a body centred cubic lattice, with a unit cell distance of
387 pm. Calculate (a) the distance between the oppositively charged ions in
the lattice, and (b) the radius of the NH4+ ion if the radius of the Cl– ion is
181 pm.
Solution: a) In a body centred cubic lattice, oppositely charged ions touch each other
along the cross−diagonal of the cube. So, we can write,
2r+ + 2r– = 3a
3 3
r+ + r– = a= (387 pm)
2 2
= 335.15 pm
b) Now, since r– = 181 pm
We have, r+= (335.15 – 181) pm
= 154.15 pm
Problem 7: 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.
Solution: In a body centred unit cell, atoms touch each other along the cross diagonal.
Hence, 4r = 3a
4 4
⇒ a= r = (124 pm) = 286.4 pm
3 3
for BCC lattice, Z = 2, Hence
ZM 2 × 55.8
ρ= =
a 3NA (286.4 × 10−12 )3 × 6.023 × 1023
= 7.887 × 106 gm–3 = 7.886 g cm–3
In a face centred unit cell, atoms touch each other along the face diagonals.
Hence, 4r = 2a
4 4
a= r= (124 pm) = 350.7 pm
2 2
For FCC lattice, Z = 4, hence,
4 55.8
ρ= ×
(350.7 × 10 ) 6.023 × 1023
−12
= 8.89 × 106g m–3 = 8.89 g cm–3
Problem 8: Silver has a cubic unit cell with a cell edge of 408 pm. Its density is
10.6 g cm–3. How many atoms of silver are there in the unit cell? What is
the structure of silver?
Solution: Length of the edge of unit cell = 408 pm

Volume of unit cell = (408 pm)3 = 67.92 × 10–24 cm3
Mass of unit cell = Density × Volume
= 10.6g cm–3 × 67.92 × 10–24 cm3 = 7.20 × 10–24g
[Type text]
Mass of unit cell = No. of atoms in unit cell × Mass of each atom
Atomic mass 108
Now, mass of each atom = = = 1.79 × 10–22g
Avogadro number 6.023 × 10 23
Let the unit cell contains ‘n’ atoms, so that

Mass of unit cell = n × 1.79 × 10–22 = 7.20 × 10–22
7.20 × 10−22
n= = 4.02
1.79 × 10−22
∴ Number of atoms present in a unit cell = 4
Since the unit cell contains 4 atoms per unit cell, silver has face centred cubic
lattice.
Problem 9: If NaCl is doped with 10–3 mol percent of SrCl2, what is the concentration of
cation vacancy?
Solution: Na+ Cl– Na+ Cl–

Cl– Cl– Na+
Sr2+ Cl– Na+ Cl–
Cl– Na+ Cl– Na+
10−3 × 6.023 × 1023
Number of cationic vacancies per mol =
100
= 6.023 × 1018 vacancies per mole
Problem 10: A solid A+ B– has NaCl type close 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
A+ B–? Give reason for your answer.
Solution: As A+ B– has NaCl structure, A+ ions will be present in the octahedral voids.
Ideal radius of the cation will be equal to the radius of the octahedral void
because in that case it will touch the anions and the arrangement will be close
packed. Hence
Radius of the octahedral void = rA+ = 0.414 × rB− = 0.414 × 250 = 103.4 pm
Radius of the tetrahedral site = 0.225 × rB− = 0.225 × 250 pm = 56.25 pm
As the radius of the cation C+ (180 pm) is larger than the size of the tetrahedral
site, it cannot be slipped into it.
Problem 11: Calculate the void space in a primitive unit cell and also the fraction of the
total volume occupied.
Solution: r r a = 2r
Volume of the cube = a3 = (2r)3 = 8r3
4 3
 πr 
=  3 
Volume of one atom 3
Packing fraction =
Volume of the cube 8r
[Type text]
π
= = 0.52
6
∴ Void fraction = 1 – 0.52 = 0.48
∴ Void space = 48%
Problem 12: The density of solid argon is 1.65 g/mL at –233°C. If the argon atom is
assumed to be sphere of radius 1.54 × 10–8 cm, what percentage of solid
argon is apparently empty space? (At. wt. of Ar = 40).
4
Solution: Volume of one atom of Ar = πr 3
3
1.65
Also, No. of atoms in 1.65g = × 6.023 × 1023
40
∴ Total volume of all atoms of Ar in solid state
4 1.65
= πr 3 × × 6.023 × 1023
3 40
4 22 1.65
= × × (1.54 × 10 –8 )3 × × 6.023 × 1023
3 7 40
= 0.380 cm3
Volume of solid argon = 1 cm3
[1 – 0.380]
∴ % empty space = × 100 = 62%
1
Problem 13: An element crystallizes as body centred cubic lattice. Its density is
7.12 g cm–3 and the length of the side of the unit cell is 2.88 Å. Calculate the
number of atoms present is 288 g of the element.
Solution: Volume of unit cell = a 3 = (2.88Å)3 = (2.88 × 10 –8 cm)3

= 23.887 × 10−24 cm3
Mass 288 g
Volume of 288 g of the element = = = 40.449 cm3
Density 7.12 g cm –3
Number of unit cells in the given volume of the element
volume of the element 40.449
= = = 1.693 × 1024
volume of the unit cell 23.887 × 10 –24
Q Each unit cell of b.c.c. lattice contains 2 atoms

∴ Number of atoms in 288 g of element
= No. of unit cells × no. of atoms per unit cell =1.693 × 1024 × 2 = 3.386 × 1024
Problem 14: Calculate the value of Avogadro number from the internuclear distance of
adjacent ions in NaCl, 0.282 nm and the density of solid NaCl is
2.17 × 103 kg/m3. A unit cell contains 4 NaCl formula units.
Solution: To calculate Avogadro number, that is, number of NaCl formula units per mol,
let us assume 1 mole of NaCl.
mass of 1 mole 58.5 × 10 –3
Volume of 1 mole of NaCl = = = 2.7 × 10 –5 m3
density 2.17 × 103
[Type text]
Volume of 1 unit cell = a 3 = (0.564 × 10 –9 )3 = 1.79 × 10 –28 m3

2.7 × 10 –5
∴ Number of unit cells per mol = = 1.51 × 1023
1.79 × 10 –28
Since 1 unit cell of NaCl has 4 NaCl formula units,

Avogadro number (formula units per mol) = 4 × (1.51 × 1023 )
= 6.04 × 1023
Problem 15: An ionic solid A+ B– crystallizes as a body centred cubic structure. The
distance between cation and anion in the lattice is 338 pm. Calculate the
edge length of the unit cell.
Solution: In a body centred cubic unit cell, the distance between the cation and anion
(r+ + r– ) is related to the edge length (a) by
a
r+ + r– = 3 ×
2
2 +
∴ a= (r + r – )
3
It is given that (r + + r – ) = 338 pm
2 676
∴ a= × 338 pm = = 390.3 pm
3 1.732
KVPY
1. An electron is accelerated from rest through a potential (V) and then diffracted on a Ni crystal to
measure its
wavelength ( ). The wavelength is related to V as – (2007)
1/2 1/2
(A) V (B) 1/V (C) V (D) 1/V
Ans:D
[Type text]
Assignments
SECTION – I Single Choice Questions
1. In a solid lattice, cation is absent from lattice site and present at an interstitial position, the
lattice defect is:
(a) Frenkel (b) Interstitial
(c) Schottky (d) None of these
2. The number of molecules present in 100 gm of a FCC crystal are (density of crystal
= 10.0 gm/cm3 and cell edge of crystal = 100 pm):
(a) 3 × 1025 (b) 4 × 1025
(c) 1 × 1025 (d) 2 ×1025
3. The arrangement ABCABCABC………is referred as

(a) octahedral close packing (b) hexagonal close packing
(c) tetrahedral close packing (d) cubic close packing
4. Frenkel defect is caused due to

(a) an ion missing from the normal lattice site creating a vacancy
(b) an extra positive ion occupying an interstitial position in the lattice
(c) an extra negative ion occupying an interstitial position in the lattice
(d) the shift of a positive ion from its normal lattice site to an interstitial site
5. The edge length of face centered unit cubic cell is 508 pm. If the radius of the cation is
110 pm, the radius of the anion is
(a) 144 pm (b) 288 pm
(c) 618 pm (d) 398 pm.
6. Schottky defect in crystals is observed when

(a) unequal number of cations and anions are missing from the lattice
(b) equal number of cations and anions are missing from the lattice
(c) an ion leaves its normal site and occupies an interstitial site
(d) density of the crystal is increased.
7. The number of unit cells in 58.5 g of NaCl is approximately

(a) 6 × 1020 (b) 1.5 × 1023
(c) 6 × 1023 (d) 0.5 × 1024 .
8. A compound is formed by elements A and B. This crystallizes in the cubic structure
where the A atoms are at the corners of the cube and B atoms are at the body centres. The
simplest formula of the compound is
(a) AB (b) A 2 B
(c) AB2 (d) AB6 .
[Type text]
9. For an ionic crystal of the general formula AX and coordination number 6, the value of
radius ratio will be
(a) greater than 0.73 (b) in between 0.73 and 0.41
(c) in between 0.41 and 0.22 (d) Less than 0.22
10. Na and Mg crystallize in BCC and FCC crystals respectively, then the number of atoms
of Na and Mg presenting the unit cell of their respective crystal is
(a) 4 and 2 (b) 9 and 14
(c) 14 and 9 (d) 2 and 4.
11. The mass of a unit cell of CsCl corresponds to

(a) 8Cs+ and 1 Cl– (b) 1Cs+ and 6Cl–
+ –
(c) 1Cs and 1 Cl (d) 4Cs+ and 4Cl–
12. A compound formed by elements A and B crystallizes in a cubic structure where A atoms
are at the corners of a cube and B atoms are at the face centre. The formula of the
compound is:
(a) AB3 (b) AB2
(c) AB4 (d) None of these
13. A solid XY has NaCl structure. If radius of X+ is 100 pm. What is the radius of Y– ion:
(a) 120 pm (b) 136.6 to 241.6 pm
(c) 136.6 pm (d) 241.6 pm
14. The co-ordination number of metal crystallizing in a hexagonal close packed structure is
(a) 12 (b) 4
(c) 8 (d) 6
15. The unit cell with crystallographic dimensions

a = b ≠ c, α = β = γ = 90° is
(a) Cubic (b) Tetragonal
(c) Monoclinic (d) Hexagonal
16. 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
17. 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
18. The limiting radii ratio rNi / rCN in the complex [Ni(CN)4]2– is
2+ −
(a) 0.255 – 0.414 (b) 0.155 – 0.225

(c) 0.414 – 0.732 (d) none of these
[Type text]
19. In Na2O structure:

(a) O2– ions constitute ccp and Na+ ions occupy all the octahedral holes
(b) O2– ions constitute ccp and Na+ ions occupy all the tetrahedral holes
(c) O2– ions constitute ccp and Na+ ions occupy 50% of tetrahedral holes and 100%
octahedral holes
(d) Na+ ions constitute ccp and O2– ions occupy half of octahedral holes
20. The hcp and ccp structure for a given element will have:
(a) The same density (b) The same fraction of unoccupied space
(c) The same coordination number (d) All of the above
SECTION – II Single Choice Questions
1. The density of KCl is 1.9893 g cm–3 and the length of a side of unit cell is 6.29082Å as
determined by X−Ray diffraction. The value of Avogadro’s number calculated from these
data is:
(a) 6.017 × 1023 (b) 6.023 × 1023
(c) 6.03 × 1023 (d) 6.017 × 1019
2. The density of KBr is 2.75 gm cm–3. Length of unit cell is 654 pm, K = 39, Br = 80, then
what is true about the predicted nature of the solid:
(a) Solid has face centred cubic system with co−ordination number = 6
(b) Solid has simple cubic system with co−ordination number = 4
(c) Solid has face centred cubic system with co−ordination number = 1
(d) None
3. 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 ra (b) 0.155 ra
(c) 0.414 ra (d) 0.732 ra
4. 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
5. A substance AxBy crystallizes in a face centred cubic (FCC) lattice in which atoms ‘A’
occupy each corner of the cube and atoms ‘B’ occupy the centre of each face of the cube.
Identify the correct composition of the substance AxBy.
(a) AB3 (b) A4B3
(c) A3B (d) Can’t be predicted
[Type text]
6. In a soslid AB having NaCl strucutre, ‘A’ atoms occupy the corners of the cubic unit cell.
If all the face-centred atoms along one of the axes are removed, then the resultant
stoichiometry of the solid is
(a) AB2 (b) A2B
(c) A4B3 (d) A3B4
7 In a solid AB having the NaCl structure, A atoms occupy the corners of the cubic unit
cell. If all the face centred atoms along one of the axes are removed, then the resultant
stoichiometry of the solid is
(a) AB2 (b) A2B
(c) A4B3 (d) A3B4
8. The intermetallic compound LiAg crystallises in cubic lattice in which both Li and Ag
have co-ordination number of eight. The class of crystal is
(a) simple cubic (b) Body centred cubic
(c) Face centred cubic (d) none of these
9. A binary solid (A+B-) has a zinc blende structudre with B- ions constituting the lattice and
A+ ions occupying 25% tetrahedral holes. The formula of solid is
(a) AB (b) A2B
(c) AB2 (d) AB4
10. 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 presenct at body centre, the alloy has a
formula
(a) Cu4Ag2Au (b) Cu4Ag4Au
(c) Cu4Ag3Au (d) CuAgAu
SECTION – III May be more than one choice
1. Select the correct statements:-

3
(a) For CsCl unit cell (edge-length = a), rc + ra = a
2
l
(b) For NaCl unit cell (edge-length = l ), 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
(a) Substitutional cation vacancy (b) Frenkel’s defect
(c) Schottky defect (d) Decrease of density
[Type text]
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
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–
[Type text]
10. Select the correct statement(s):

(a) Schottky defect is shown by CsCl
(b) Frenkel defectis 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
Answers to Assignments
SECTION - I
Level - I
1. (a) 2. (b) 3. (d) 4. (d) 5. (a)
6. (b) 7. (b) 8. (a) 9. (b) 10. (d)
11. (c) 12. (a) 13. (b) 14. (a) 15. (b)
16. (c) 17. (c) 18. (c) 19. (b) 20. (d)
Level - II
1. (a) 2. (a) 3. (a) 4. (c) 5. (a)
6. (d) 7. (c) 8. (b) 9. (c) 10. (c)
SECTION - III
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)
[Type text]

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Difference between Crystalline and Amorphous Solids: The substances

Seven Crystal Systems and Fourteen Bravais Lattice

c angles between the planes

Close Packing in Crystals

Arrnagement (I) Arrnagement (II)

In arrangement (I), the spheres are packed in such a

Fig. (a) Fig. (b)

Now, there are two ways to build up the third layer:

The HCP and CCP arrangements can also be shown as below.

Calculation of some limiting radius ratio values

a) Co−ordination Number 3: The adjacent figure shows the A

smaller positive ion of radius r+ in contact with three larger

In this figure, AB = BC = AC = 2r– B E C

b) Co−ordination Number 4: (tetrahedron) B

Angle ABC is the tetrahedral angle

c) Co−ordination Number 6: (Octahedron): A cross

Solution: Edge length, a = 286 pm

Case I: For cubic crystals of elements:

Illustration 4: Lithium borohydride (LiBH4), crystallises in an orthorhombic system with 4

Solution: We know that,

Classification of Ionic Structures

1. Rock salt (NaCl) type

1. Rock Salt (NaCl) type Structure: Cl– is

2. Zinc Blende Structure (ZnS): Sulphide ions

3. Cesium Chloride (CsCl) type structure:

co−ordination. A unit cell of CsCl consists of only one

Each Ca2+ ion is surrounded by 8F– ions i.e. it has a

Ionic radius increases in a group with increase in atomic number as:

In pure alkali metal halides, these defects A+ B- A+ B- A+ B- A+ B-

are not very common because the ions

their large sizes. A +

Fig. (a): Schottky Defect Fig. (b): Frenkel Defect

Metal Excess Defect: This may occur in two different ways

Metal excess defects caused by interstitial cations.

Metal Deficiency Defect: This defect is caused by A++

Metal deficiency due to cation vacancy

Alignment of magnetic moments in opposite directions in a compensatory manner and resulting

↑↑↑↑↑↑↑ ; ↑↓↑↓↑↓↑ ; ↑↓↓↑↓↓↑

for example, MnO, Mn2O3 and MnO2.

Properties of Amorphous Solids

Use of Amorphous Solids

i) Amorphous solids, in the form of inorganic glasses, find application in construction,

Problem 1: In fluorite structure (CaF2)

Problem 4: Fraction of total volume occupied by atoms in a simple cubic cell is

Solution: (d) In simple cubic arrangement, no. of atoms = 1

Problem 5: The limiting radius ratio of the complex [Ni(CN)4]2–is

Solution: (b) Since the ratio of the co-ordination no. P to that of Q is Y : Z

Solution: (b) For fcc lattice

Problem 8: The arrangement of Cl- ions in CsCl structure is

Problem 10: In α-WCl6

Solution: (c) Cs+ and I− have largest sizes.

Problem 23: In an NaCl structure, all the

(a) FCC structure is 0.155 r. (b) BCC structure is 0.155 r.

Problem 25: Select the correct statement(s)

Problem 26: Match List I and List II

Solution : (a – r), (b – s), (c – q), (d – p)

1. Total number of atom present in a unit cell is

2. The formula of perovskite is

3. The oxidation number of titanium in the perovskite is

2. (c) The formula of perovskite is CaTiO3

4. (a) If no. of O–atom is removed from alternate position (face)

2. Yellow form of ZnO shows enhanced electrical conductivity due to