Sample Chemistry Chapter Without Branding

17.
Solid State
1. General Introduction
The solids are the substances which have definite volume and definite shape. In terms of kinetic molecular model, solids have regular order of their constituent
particles (atoms, molecules or ions). These particles are held together by fairly strong forces, therefore, they are present at fixed positions. The properties of the
solids not only depend upon the nature of the constituents but also on their arrangements.
2. Types of Solids
2.1. Types
Solids can be broadly classified into following two types: Crystalline solids/ True solids and Amorphous solids/ Pseudo solids
Table: Comparison of Solids
Crystalline Solids Amorphous Solids

They have long range order i.e., regular pattern of particles They have short range order i.e., regular arrangement of particles
over the entire crystal. over a short distance (one or two atom spacings).
They have definite melting point. They do not have definite melting point.
They have a definite heat of fusion. They do not have definite heat of fusion.
They are rigid and incompressible. They do not get compressed to any appreciable extent.
They give regular cleavage i.e., they break into two pieces They give irregular cleavage i.e., they break into two pieces
with plane surfaces. with irregular surface.
They are anisotropic because these substances show different They are isotropic because these substances show same property
property in different direction. in all directions.
There is a sudden change in volume when it melts. There is no sudden change in volume on melting.
These possess symmetry. They do not possess any symmetry.
These possess interfacial angles. They do not possess interfacial angles.
Crystalline solids are also called true solids. Amorphous solids are also called supercooled liquids.
Examples: all regular solids Examples: glass, polymers (plastic, rubber etc.), gels.
2.2. Quasicrystals
A quasi–crystal is a structure that is ordered but not periodic. It is formed when certain metallic alloy is allowed to cool down slowly from molten state.
The range of order is normally short, but a few crystals can have long–ordered range.
Quasicrystals are found most often in aluminium alloys (examples, Al-Li-Cu, Al-Cu-Fe, etc.) but numerous other compositions are also known
(examples, Zn-Mg-Ho, Pd-U-Si, etc.).
2.3. Examples
(1)
Crystalline and Amorphous Silica (SiO2)
Silica occurs in crystalline as well as amorphous states. Quartz is a typical example of crystalline silica. Quartz and the amorphous silica differ
considerably in their properties.
Table: Difference between Quartz and Amorphous Silica
Quartz Amorphous Silica
It is crystalline in nature. It is light (fluffy) white powder.

All four corners of SiO4 tetrahedron are shared by others to The SiO4 tetrahedra are randomly joined, giving rise to
4 4
give a network solid polymeric chains, sheets or three-dimensional units.
It has high and sharp melting point (1710°C). It does not have sharp melting point.
Chemistry Solid State | 1

(2)
Diamond and Graphite
Diamond and graphite are two allotropes of carbon. Diamond and graphite both are covalent crystals. But they differ considerably in their
properties.
Table: Difference between Diamond and Graphite
Diamond Graphite
It occurs naturally in free state. It occurs naturally, as well as manufactured artificially.
It is the hardest natural substance known. It is soft and greasy to touch.
It has high relative density. (about 3.5) Its relative density is 2.3.
It is transparent and has high refractive index. (2.45) It is black in colour and opaque.
It is non-conductor of heat and electricity. Graphite is a good conductor of heat and electricity.
It burns in air at 900°C to give CO2. It burns in air at 700°C to give CO2.
It occurs as tetrahedral crystals. It occurs as hexagonal crystals.
2.4. Classification of Crystalline Solids

Table: Some Characteristics of Different Types of Crystalline Solids
Types of Physical Electrical

Constituents Bonding Examples M.P. B.P.
Solid Nature Conductivity
Conductor
Positive and negative ions Coulombic NaCl, KCl, CaO,
Hard but High (≃1000 High (≃2000 (in molten state and in
Ionic network systematically MgO, LiF, ZnS,
brittle K) K) aqueous solution)
arranged BaSO4 and K2SO4 etc.
SiO2 (Quartz), SiC,

Covalent / Atoms connected in Electron sharing Hard Very high Very high Insulator except
Network covalent bonds C (diamond), (≃4000 K) graphite
(≃5000 K)
C(graphite) etc.
I2, S8, P4, CO2, CH4, Low

(i) Molecular CCl4 etc. Insulator
Low (≃300 K (≃ 450 K to
interactions (inter- Soft
Polar or non-polar to 600 K) 800 K)
Molecular molecular forces)
molecules Starch, sucrose, water,
(ii) Hydrogen Low
dry ice or drycold (solid
bonding Low(≃400K) (≃373 K to
CO2) etc. Insulator
500 K)
Cations in a sea of Sodium , Au, Cu, High High

Metallic Ductile
Metallic electrons magnesium, metals and (≃800 K to (≃1500 K Conductor
malleable
alloys 1000 K) to 2000 K)
Poor thermal and

London dispersion
Atomic Atoms Noble gases Soft Very low Very low electrical conductors
force
3. Space Lattice (Crystal Lattice) and Unit cell
Crystal is a homogeneous portion of a crystalline substance, composed of a regular pattern of structural units (ions, atoms or molecules) by plane surfaces
making definite angles with each other giving a regular geometric form.
3.1. Space Lattice
(1) A regular array of points (showing atoms/ions) in three dimensions is commonly called as a space lattice or crystal lattice.
(2) Each point in a space lattice represents an atom or a group of atoms.
(3) Each point in a space lattice has identical surroundings throughout.

3.2. Unit Cell
Space
A three dimensional group of lattice points which when repeated in space
generates the crystal called unit cell. c

(1) Parameters 
The unit cell is described by the lengths of its edges, a, b, c  b Unit
(which are related to the spacing between layers) and the a
angles between the edges, ,, . Unit cell Space lattice and unit cell
Fig: Unit
(2) Types of Lattices (Unit cells)
Cell
Crystals have four kinds of lattices depending on the shape of the unit cells.
 Simple or Primitive Unit Cell
Atoms are arranged only at the corners of the unit cell.
 Body Centered Unit Cell
Atoms are arranged at the corners and at the centre of the unit cell.
 Face Centered Unit Cell
Atoms are arranged at the corners and at the centre of each faces of the unit cell.
 End Centered Unit Cell
Atoms are arranged at the corners and at the centre of any two opposite faces of the unit cell.
 Edge Centered Unit Cell
Atoms are arranged at the corners and at the centre of each edge of the unit cell.
4. Crystal Systems
Bravais (1848) showed from geometrical considerations that there can be only 14 different ways in which similar points can be arranged. Thus, there can be
only 14 different space lattices. These 14 types of lattices are known as Bravais Lattices. These 14 types of lattices are divided into seven types of
crystal systems based on the parameters.
Table: Bravais Lattices Corresponding to Different Crystal Systems

Crystal System Space Lattice Examples
Cubic Simple: Lattice points at the eight Body centered: Points at the Face centered: Points at Pb, Hg, Ag, Au, Cu,
a = b = c, corners of the unit cells. eight corners and at the body the eight corners and at the Zns, diamond, KCl
centred. six face centres. CsCl, NaCl,
      90o
Cu2O,CaF2 and
c alums. etc.
 

b
a
Tetragonal Simple: Points at the eight corners Body centered: Points at the eight corners and at the body SnO2, TiO2,
a = b  c, of the unit cell. centre.
ZnO2, NiSO4
      90o ZrSiO4 . PbWO4 ,
c
white Sn etc.
 

a b
Orthorhombic Simple: Points at the End centered: Also called Body centered: Face centered: KNO3,K2SO4 ,
(Rhombic) eight corners of the side centered or base Points at the eight Points at the eight
PbCO3,BaSO4 ,
a  b  c, unit cell. centered. Points at the eight corners and at the corners and at the six
corners and at two face centres body centre. face centres. rhombic sulphur,
      90o opposite to each other. MgSO4. 7H2O etc.
c
 

b
a

Rhombohedral Simple: Points at the eight corners of the unit cell. NaNO3, CaSO4,
or Trigonal calcite, quartz,
a = b = c, As, Sb, Bi etc.
      90o
Hexagonal Simple: Points at the twelve corners of the unit or Points at the twelve corners of the hexagonal ZnO, PbS, CdS,
a = b  c, cell out lined by thick line. prism and at the centres of the two hexagonal faces. HgS, graphite, ice, Mg,
Zn, Cd etc.
    90
  120o
Monoclinic Simple: Points at the eight corners of the unit cell. End centered: Point at the eight corners and at two Na2SO4.10H2O,
a  b  c, face centres opposite to the each other.
Na2B4O7.10H2O,
    90o,  90o CaSO4.2H2O,
monoclinic sulphur etc.
Triclinic Simple : Points at the eight corners of the unit cell. CaSO4.5H2O,
a  b  c, K2Cr2O7, H3BO3
      90o etc.
5. Crystallography
The branch of science that deals with the study of structure, geometry and properties of crystals is called crystallography.
5.1. Symmetry in Crystal
A crystal possess following three types of symmetry:
(1) Plane of Symmetry
It is an imaginary plane which passes through the centre
of a crystal and divides it into two equal portions which are Plane of symmetry Rectangular plane of Diagonal plane of
exactly the mirror images of each other. symmetry symmetry
(2) Axis of Symmetry Fig: Plane of Symmetry
An axis of symmetry or axis of rotation is an imaginary line, passing through the crystal such that when the crystal is rotated about this line,
it presents the same appearance more than once in one complete revolution i.e., in a rotation through 360°. Suppose, the same appearance of crystal
is repeated, on rotating it through an angle of 360°/n, around an imaginary axis, is called an n-fold axis, where, n is known as the order of axis.
by order is meant the value of n in 2/n so that rotation through 2/n , gives an equivalent configuration.
Axis of two fold symmetry Axis of three fold symmetry Axis of four fold symmetry Axis of six fold symmetry
Fig: Axes of Symmetry
(3) Centre of Symmetry

It is such an imaginary point in the crystal that any line drawn through it intersects the surface of the crystal at equal distance on either side.

Y
5.2. Elements of Symmetry
The total number of planes, axis and centre of symmetries possessed by a crystal is termed as
elements of symmetry. Centre of
symmetry of a
Example: Cubic system
cubic crystal
Only simple cubic system has one centre of symmetry. Other system does not have centre of symmetry.
A cubic crystal possesses total 23 elements of symmetry. Z X
Plane of symmetry ( 3 + 6) =9
Fig: Center of Symmetry
Axis of symmetry ( 3 + 4 + 6) = 13
Centre of symmetry (1) =1
Total elements of symmetry = 23
5.3. Miller Indices
Planes in crystals are described by a set of integers (h, k and l) known as Miller indices.
Miller indices of a plane are the reciprocals of the fractional intercepts of that plane on the various crystallographic axis. For calculating Miller indices, a
reference plane, known as parametral plane, is selected having intercepts a, b and c along x, y and z-axis respectively. Then, the intercepts of the
unknown plane are given with respect to a, b and c of the parametral plane.
Thus, the Miller indices are:
a b c
h  intercept of the plane along x-axis ; k  intercept of the plane along y-axis ; l  intercept of the plane along z-axis
The distance between the parallel planes in crystals are designated as dhkl . For different cubic lattices these interplanar spacing are
a
given by the general formula d(hkl) 
h2  k2  l2
Where a is the length of cube side while h, k and l are the Miller indices of the plane.
(1) When a plane is parallel to an axis, its intercept with that axis is taken as infinite and the Miller indices will be zero.
(2) Negative sign in the Miller indices is indicated by placing a bar on the intercept. All parallel planes have same Miller indices.
6. Bragg’s Law
Study of internal structure of crystal can be done with the help of X-rays. The distance of the constituent particles can be determined from
diffraction value by Bragg’s equation. n  2d sin
where,  = Wavelength of X-rays, n = order of reflection,  = Angle of reflection, d = Distance between two parallel surfaces
The above equation is known as Bragg’s equation or Bragg’s law. The reflection corresponding to n = 1 (for a given family of planes) is called first
order reflection; the reflection corresponding to n = 2 is the second order reflection and so on. Thus, by measuring n (the order of reflection of the X-
rays) and the incidence angle , we can know d/.
d n
  2 sin 
Y
 P 
A B
Q S
d
CD
R
d
EF
From this, d can be calculated if  is known and vice versa. In X-ray reflections, n is generally set as equal to 1. Thus, Bragg’s equation
may alternatively be written as,   2d sin = 2dhkl sin
Where dhkl denotes the perpendicular distance between adjacent planes with the indices hkl.

7. Analysis of Cubic System
7.1. Number of Atoms Per Unit Cell

The total number of atoms contained in the unit cell for a simple cubic called the unit cell content.
No. of effective atoms N nc n f  ne ni

eff =  
8 2 4 1
Where
nc  Number of atoms at the corners of the cube
nf  Number of atoms at six face centers of the cube
ne  Number of atoms at twelve edge centers of the cube

ni  Number of atoms inside the cube
If atoms are present in all the possible locations then:
nc  8, nf  6, ne  12 and ni  1
Table: Effective number of Atoms per Unit Cell
Cubic Unit Cell nc nf ne ni Neff

Simple cubic 8 0 0 0 1
Body centered cubic (bcc) 8 0 0 1 2
Face centered cubic (fcc) 8 6 0 0 4
End centered cubic 8 2 0 0 2
Edge centered cubic 8 0 12 0 4
7.2. Co-ordination Number (C.N.)

It is defined as the number of nearest neighbours or touching particles with other particle present in a crystal is called its co-ordination number. It depends
upon structure of the crystal.
For simple cubic system, C.N. = 6.
For body centred cubic system, C.N. = 8
For face centred cubic system C.N. = 12.
7.3. Density of the Unit Cell ()
It is defined as the ratio of mass per unit cell to the total volume of unit cell.
ZM
 g/cm3 [volume  a3
a3  NA for cubic cell]
Where Z = Number of particles per unit cell M =
Atomic mass or molecular mass (g/mol) N A 
Avogadro number (6.023 1023mol1)
The density of the substance is same as the density of the unit cell.
7.4. Packing Fraction (P.F.)
It is defined as ratio of the volume of the unit cell that is occupied by spheres of the unit cell to the total volume of the unit cell. Let radius
of the atom in the packing = r, Edge length of the cube = a, Volume of the cube, V = a 3
Volume of the atom (spherical) v  4 r 3

3
4
r3 Z
vZ
Packing density   3
V a3

Table: Packing Fraction of Cubic Systems
Structure r related to a Volume of the atom (v) Packing density % of void

Simple cubic a  100-52 = 48%
r 4a 3
 0.52
 
2 6
3 2
Face-centred cubic a 4a

3
2 100-74 = 26%
r    0.74
22 3 2 2 6
3
Body-centred cubic 4 3a  3 100-68 = 32%
3a  0.68
r 4  
3  4  8
8. Close Packing in Crystalline Solids

In the formation of crystals, the constituent particles (atoms, ions or molecules) get closely packed together. The closely packed arrangement is that in
which maximum available space is occupied. This corresponds to a state of maximum density. The closer the packing, the greater is the stability of
the packed system.
8.1. Close Packing in One Dimension
There is only one way in which the particles (spheres) can be arranged in one dimensional
close packing structure. In this arrangement, each sphere is in contact
with 2 other spheres. Hence, in one dimensional close packed arrangement, the coordination Fig: One Dimensional Close Packing
number is 2.
8.2. Close Packing in Two Dimensions
There are two possible arrangement of close packing in two dimensions:
11
12
4 2
6 3
3 54
Fig: Square Close Packing Fig: Hexagonal Close Packing
(1) Square Close Packing

The spheres in the adjacent row lay just one over the other and show a horizontal as well as vertical alignment and form square. In this
arrangement each sphere is in contact with four spheres.
(2) Hexagonal Close Packing
The spheres in every second row are seated in the depression between the spheres of first row. The spheres in the third row are vertically aligned
with spheres in first row. The similar pattern is noticed throughout the crystal structure. In this arrangement each sphere is in contact with
six other spheres.
8.3. Close Packing in Three Dimensions
In order to develop three-dimensional close packing, let us retain the hexagonal
a a a a a
close packing in the first layer. For close packing, each spheres in the second layer
rests in the hollow at the centre of three touching spheres in the layer as shown bbb
in figure. The spheres in the first layer are shown by solid lines while those in aaaa
second layer are shown by broken lines. It may be noted that only half of the ccc
triangular voids in the first layer are occupied by spheres in the second layer (b).
aa a a a
The unoccupied hollows
or voids in the first layer are indicated by (c) in figure. Fig: Close Packing in Three Dimensions
There are two alternative ways in which species in third layer can be arranged
over the second layer:

(1) Hexagonal Close Packing A
The third layer lies vertically above the first and the spheres in third layer rest in A
B A
one set of hollows on the top of the second layer. This arrangement is called B
A
ABAB …. type and 74% of the available space is occupied by spheres. This B
B
arrangement is found in Be, Mg, Zn, Cd, Sc, Y, Ti, Zr, Tc, Ru. A A
A
(2) Cubic Close Packing
Fig: Hexagonal Close Packing (hcp) in Three
When the third layer (C) is placed above the second layer in such a way that it Dimensions
covers the octahedral voids then it is different from below two layers. This
B
arrangement is called ABCABC….. type or cubic close packing (ccp) and in A B
CB
this also 74% of the available space is occupied by spheres. It is similar to face A
centred cubic (fcc) unit cell. This arrangement is found in Cu, Ag, Au, Ni, A
C
Pt, Pd, Co, Rh, Ca, Sr.
(3) Body Centred Cubic

C
This arrangement of spheres (or atoms) is not exactly close Fig: Cubic Close Packing (ccp or fcc) in Three
packed. This structure can be obtained if spheres in the first Dimensions
layer (A) of close packing are slightly opened up. As a result none
of these spheres are in contact with each other. The second layer of A A
A A A A
spheres (B) can be placed on top of the first layer so that each A A
sphere of the second layer is in contact with four spheres of the BBB B
layer below it. Successive building of the third will be exactly AAAA BBB
like the first layer. If this pattern of building layers is repeated A
infinitely we get an arrangement as shown in figure. This A A
arrangement is found in Li, Na, K, Rb, Ba, Cs, V, Nb, Cr, Mo, A
A A A A
Fe.
Fig: Body Centred Cubic (bcc) Close Packing in
Three Dimensions
Table: Comparison of hcp, ccp and bcc
Property hcp ccp bcc
Arrangement of packing Close packed Close packed Not close packed
Type of packing AB AB A... ABC ABC A... AB AB A...
Available space occupied 74% 74% 68%
Coordination number 12 12 8
Malleability and ductility Less malleable, hard, brittle Malleable and ductile
Note: (i) Close packing of atoms in cubic structure = fcc > bcc > sc.
(ii) All noble gases have ccp structure except He (hcp structure)
Li Be
Na Mg Al
Mn Fe CoNiCu Zn
CaScTi
Rb Sr M TcRu RhPdAg Cd
YZn N
Cs Hexagonal Simple cubic Face centred Body centred
Ba
close packed
Fig: The Crystal Structures of Some Metals at Room Temperature and Pressure

8.4. Effect of Temperature and Pressure on C.N.
On applying high pressure NaCl structure having 6 : 6 co-ordination changes to CsCl structure having 8 : 8 co-ordination. Thus, increase in pressure
increases the co-ordination number.
Similarly, CsCl structure on heating to about 760 K, changes to NaCl structure. In other words, increase of temperature decreases the co-ordination
number.
NaCl Pressure CsCl
(6 : 6) (8 : 8)
Temp
9. Interstitial Sites in Close Packing
Even in the close packing of spheres, there is left some empty space between the spheres. This empty space in the crystal lattice is called site or void or hole.
Voids are of following types:
9.1. Trigonal Void
This site is formed when three spheres lie at the vertices of an equilateral triangle.
Size of the trigonal site is given by the following relation, r = 0.155 R
where ‘r’ is radius of the spherical trigonal void and R is radius of closely packed spheres
9.2. Tetrahedral Void
A tetrahedral void is developed when triangular voids (made by three spheres in one layer touching each other) have contact with one sphere either in
the upper layer or in the lower layer.
The number of tetrahedral voids is double the number of spheres in the crystal structure. Size of the trigonal site is given by the following relation r =
0.255 R
where, r is the radius of the tetrahedral void or atom occupying tetrahedral void and R is the radius of spheres forming tetrahedral void.
9.3. Octahedral Void
This type of void is surrounded by six closely packed spheres, i.e. it is formed by six spheres. The
number of octahedral voids is equal to the number of spheres.
r 0.414 R
where, r is the radius of octahedral void or atom occupying octahedral void and R is the radius of spheres farming octahedral void.
9.4. Cubic Void
This type of void is formed between 8 closely packed spheres which occupy all the eight corners of cube.
r = 0.732 R
where, r is the radius of cubic void or atom occupying cubic void and R is the radius of spheres farming cubic void. The decreasing
order of the size of the various voids is:
Cubic > Octahedral > Tetrahedral > Trigonal
Triogonal
Fig: Triogonal Fig: Tetrahedral Void Fig: Octahedral Void Fig: Cubic Void
10. Radius Ratio
Ionic compounds occur in crystalline forms. Ionic compounds are made of cations and anions. These ions are arranged in three dimensional array to form an
aggregate of the type (A+B–)n . Since, the coulombic forces are non-directional, hence the structures of such
crystals are mainly governed by the ratio of the radius of cation (r ) to that of anion (r  ). The ratio r to r (r / r  ) is called as radius ratio.

r
Radius ratio 
r
Table: Limiting Radius Ratios and Structure
Limiting radius ratio (r+)/(r–) C.N. Type of void occupied Examples of ionic compound
< 0.155 2 Linear
0.155 – 0.225 3 Planar triangle BN
0.225 – 0.414 4 Tetrahedral ZnS
0.414 – 0.732 6 Octahedral NaCl
0.732 – 1.000 8 Body-centered cubic CsCl

11. Classification of Ionic Crystal
Table: Types of Ionic Crystal with Description
Crystal Brief description Examples Co-ordination Number of

structure number formula units
type per unit cell
Type AB It has fcc arrangement in which Cl− ions occupy Halides of Li, Na, K, Rb, AgF, AgBr, Na  6 4
Rock salt the corners and face centres of a cube while Na ions
+
NH4Cl, NH4Br, NH4I etc.
Cl− = 6
are present at the body and edge of centres.
(NaCl) type
Zinc blende It has ccp arrangement in which S2− ions form fcc CuCl,CuBr,CuI, AgI,BeS Zn2  4 4
(ZnS) type and each Zn ion is surrounded tetrahedrally by
2+
four S2− ions and vice versa. S2  4
Type AB2 It has arrangement in which Ca2+ ions form BaF2,BaCl2,SrF2 Ca2  8 4
Fluorite (CaF2) fcc with each Ca2+ ions surrounded by 8F  SrCl2,CdF2,PbF2

F  4
type ions and each F− ions by 4Ca2+ ions.
Antifluorite Here negative ions form the ccp arrangement so Na2O Na  4 4
type that each positive ion is surrounded by 4 negative
ions and each negative ion by 8 positive ions O2  8
(A2B)
Caesium It has the bcc arrangement with Cs+ at the body CsCl,CsBr,CsI,CsCN, TlCl, Cs  8 1
chloride (CsCl) centre and Cl ions at the corners of a cube or
−
TlBr, TlI and TlCN Cl− = 8
type vice versa.
12. Spinel and Inverse Spinel Structure

12.1. Spinel Structure
Spinel is a mineral (MgAl O ) . Generally, they can be represented as
2 4 M2+M3+O2 . Where M2+ is present in one-eighth of
2
tetrahedral voids in a fcc lattice of oxide ions and M present in half of the octahedral voids. M2+ is usually Mg, Fe, Co, Ni, Zn and
3+
Mn, M3+ is generally Al, Fe, Mn, Cr and Rh. Examples, ZnAl2O4 , FeCr2O4 etc.
12.2. Inverse Spinel Structure
In inverse spinel type of structure, in the fcc arrangement of oxide ions, dipositive ions are present in octahedral holes and tripositive ions are equally
distributed between tetrahedral and octahedral holes. The most common example of this type is lead stone or magnetite (Fe3O4 ). Other examples :
MgFe2O2 , MgIn2O4 etc.
13. Defects or Imperfections in Solids

Any deviation from the perfectly ordered arrangement constitutes a defect or imperfection. These defects are sometimes called thermodynamic defects
because the numbers of these defects depend on the temperature.
13.1. Electronic Imperfections
Generally, electrons are present in fully occupied lowest energy states. But at high temperatures, some of the electrons may occupy higher energy state
depending upon the temperature. For example, in the crystals of pure Si or Ge some electrons are released thermally from the covalent bonds at
temperature above 0 K. These electrons are free to move in the crystal and are responsible
for electrical conductivity. This type of conduction is known as intrinsic conduction. The electron deficient bond formed by the
release of an electron is called a hole. In the presence of electric field, the positive holes move in a direction opposite to that of the electrons and
conduct electricity. The electrons and holes in solids give rise to electronic imperfections.

13.2. Atomic Imperfections/ Point Defects
When deviations exist from the regular or periodic arrangement around an atom or a group of atoms in a crystalline substance, the defects are called
point defects. Point defect in a crystal may be classified into following three types.
(1) Stoichiometric Defects
The compounds in which the number of positive and negative ions are exactly in the ratios indicated by their chemical formulae are called
stoichiometric compounds. The defects which do not disturb the stoichiometry, (the ratio of numbers of positive and negative ions) are called
stoichiometric defects. These are of following types:
 Interstitial Defect
This type of defect is caused due to the presence of ions in the normally vacant interstitial sites in the crystals.
 Schottky Defect
A+ B– A+ B–
This type of defect occur when equal number of cations and anions are missing from their lattice sites
so that the electrical neutrality is maintained.
(a) Condition: This type of defect occurs in highly ionic compounds which have high co- B– A+ A+
ordination number and cations and anions of similar sizes.
Examples: NaCl, KCl, CsCl and KBr etc. B– A+ B–
(b) Consequences: Presence of large number of Schottky defect lowers the density of
the crystal. Fig: Schottky Defect
 Frenkel Defect
A+ B– A+ B–
A+
B– A+ B– A+
B– A+ B–
Fig: Frenkel Defect

This type of defect arises when an ion is missing from its lattice site and occupies an interstitial
position. The crystal as a whole remains electrically neutral because the number of anions and cations
remain same. Since cations are usually smaller than anions, they occupy interstitial sites.
(a) Condition: This type of defect occurs in the compounds which have low coordination
number and cations and anions of different sizes.
Examples: ZnS, AgCl and AgI etc.
Frenkel defect are not found in pure alkali metal halides because the cations due to
larger size cannot get into the interstitial sites. In AgBr both Schottky and Frenkel defects occur simultaneously.
(b) Consequences:
(i) When Frenkel defect alone is present, there is no decrease in density.
(ii) The closeness of the charge brought about by Frenkel defect tends to increase the dielectric constant of the crystal.
(iii) Compounds having such defect conduct electricity to a small extent. When electric field is applied, an ion moves from its lattice site
to occupy a hole, it creates a new hole. In this way, a hole moves from one end to the other. Thus, it conducts electricity
across the crystal.
(iv) Due to the presence of holes, stability (or the lattice energy) of the crystal decreases.
(2) Non-stoichiometric Defects
The defects which disturb the stoichiometry of the compounds are called non-stoichiometry defects. These defects are either due to the presence
of excess metal ions or deficiency of metal ions.
 Metal Excess Defects
(a) Metal Excess Defects Due to Anion Vacancies A+ B– A+ B–

A compound may have excess metal ion if a negative ion is absent from its
lattice site, leaving a ‘hole’, which is occupied by electron to maintain
B– A+ B– A+
electrical neutrality.
The ‘holes’ occupied by electrons are called F-centres (or colour
A+ e– A+ B–
centres).
This type of defects is found in crystals which are likely to possess Schottky defects.
Fig: Metal Excess Defect Due to Anion Vacancy
Anion vacancies in alkali metal halides are reduced by heating the alkali metal halides crystals in an atmosphere of alkali metal vapours.

(b) Metal Excess Defects Due to Extra Interstitial Cations
Another way in which metal excess defects may occur is, if an extra positive ion is
A+ B– A+ B–
present in an interstitial site.
Electrical neutrality is maintained by the presence of an electron in the interstitial A+
site.
B– A+ B– A+
This type of defect is exhibit by the crystals which are likely to exhibit
e–
Frenkel defects.
When ZnO is heated, it loses oxygen reversibly. The excess is accommodated A+ B– A+ B–
in interstitial sites, with electrons trapped in the neighbourhood. The yellow colour
and the electrical conductivity of the non- stoichiometric ZnO is due to these Fig: Metal Excess Defect due to Extra
trapped electrons. Cation
 Consequences of Metal Excess Defects
(a) The crystals with metal excess defects are generally coloured due to the presence of free electrons in them.
(b) The crystals with metal excess defects conduct electricity due to the presence of free electrons and are semiconductors.
As the electric transport is mainly by “excess” electrons, these are called n-type (n for negative) semiconductor.
(c) The crystals with metal excess defects are generally paramagnetic due to the presence of unpaired electrons at lattice sites.
(d) When the crystal is irradiated with white light, the trapped electron absorbs some component of white light for excitation from ground
state to the excited state. This gives rise to colour. Such points are called F-centres (German word Farbe which means colour)
(e) Sometimes excess ions are accompanied by positive ion vacancies. These vacancies serve to trap holes in the same way as the anion
vacancies trapped electrons. The colour centres thus produced are called V-centres.
 Metal Deficiency Defects
(a) Metal Deficiency Defect by Cation Vacancy
A+ B– A+ B– Cation vacancy
In this type of defect, a cation is missing from its lattice site. To
maintain electrical neutrality, one of the nearest metal ion acquires
two positive charge.
B– B– A+
Condition: This type of defect occurs in compounds where metal Metal having higher
charge
can exhibit variable valency.
Example: Transition metal compounds like NiO, FeO, FeS etc. A+ B– A+2 B–
(b) By having Extra Anion Occupying Interstitial Site
B– A+ B– A+
In this, an extra anion is present in the interstitial position. The extra
negative charge is balanced by one extra positive charge on the adjacent Fig: Metal deficiency defect by cation vacancy
metal ion.
Condition: Since anions are usually larger it could not occupy an interstitial site. Thus, this structure has only a theoretical
possibility. No example is known so far.
 Consequences of Metal Deficiency Defects
Due to the movement of electron, an ion A+ changes to A+2 ions. Thus, the movement of an electron from A+ ion is an apparent of
positive hole and the substances are called p-type semiconductor.
(3) Impurity Defect
These defects arise when foreign atoms are present at the lattice site (in place of host atoms) or at the vacant interstitial sites. In the former case, we
get substitutional solid solutions while in the latter case, we get interstitial solid solution. The formation of the former depends upon the
electronic structure of the impurity while that of the later on the size of the impurity.
14. Electrical Properties of Solids
14.1. Types of Solids

Solids are classified into following classes depending on the extent of conducting nature.
(1) Conductors
The solids which allow the electric current to pass through them are called conductors. The electrical conductivity of these solids is high in the
range 104  106 ohm1cm1 .

(2) Insulators
12 22
The solids which do not allow the current to pass through them are called insulators. The electrical conductivity of these solids is 10  10
1 1
ohm cm .
(3) Semiconductors
The solids whose electrical conductivity lies between those of conductors and insulators are called semiconductors. The conductivity of these solid is
109  102ohm1cm1
14.2. Band Theory
On the basis of band theory, the conductivity of metals, conductors, insulators and semiconductors are explained as follows:
(1) Metals
In metals, the valance band is partially filled or it
Conduction bands
overlaps with a conduction band. Then electrons can flow Conduction bands
Conduction bands
under an applied electric field and the metals show Empty
band Empty
conductivity.
Forbidden zone band
(2) Conductors (Large energy gap) Small energy gap
A conductor is a matter whose valence band is Filled band
partially filled and the conduction band overlaps with the Ener
Partially Overlapping
valence band. In the case of conductors, the filled band bands
energy gap Eg  0. Therefore, conductor shows Metal Insulator Semiconductor (c)
(a) (b)
conductivity. Fig: Energy Diagrams of Valence Band and Conduction Band
(3) Insulators
A solid with completely occupied valence band is an insulator and the band gap between valence band and conduction band (empty) is large (Eg 
3eV). So electrons cannot move to conduction band. Therefore, there is no electrical conductivity.
In case of insulators, the forbidden gap is very large and the electrons are unable to excite to the conduction band.
(4) Semiconductors
In semiconductor, the energy gap is small (Eg  3 eV). Due to small energy gap; some electrons can jump to conduction band and can show
conductivity.
In case of semiconductors, forbidden gap is small. Therefore, some electrons may jump to conduction band and show some conductivity.
Electrical conductivity of semiconductors increases with rise in temperature, since more electrons can jump to the conduction band.
 Intrinsic Semiconductors
Electrical conductivity of some semiconductors increases with rise in temperature because more electrons can jump to the conduction band.
Elements like silicon and germanium show this type of behaviour and are called intrinsic semiconductors.
 Extrinsic Semiconductors or Doping
The conductivity of these intrinsic semiconductors is very low for any practical use. Their conductivity can be increased by adding an
appropriate amount of suitable impurity. This process is called doping. Doping is done with an impurity which is either electron rich or
electron deficient as compared to the intrinsic semiconductor silicon or germanium. Such impurities introduce electronic defects in them.
Thus, two types of semiconductors are obtained: n-type and p-type semiconductors.
(a) n-type Semiconductor
Silicon and germanium (group 14) have four valence electrons. In their crystals each atom forms four covalent bonds with its
neighbours. When doped with a group 15 element like P or As, which contains five valence electrons, they occupy some of the
lattice sites in silicon or germanium crystal.

Four out of five electrons are used in the formation of four covalent bonds with the four neighbouring silicon atoms. The fifth electron is
extra and becomes delocalized.
Mobile electron Positive hole

Silicon atom (no electron)
Perfect Crystal n-type p-type (c)

(a) (b)
Fig: n-type and p-type Semiconductor
These delocalised electrons increase the conductivity of doped silicon (or germanium). Here the increase in conductivity is due to the negatively
charged electrons, thus silicon doped with electron-rich impurity is called n-type semiconductor.
(b) p-type Semiconductor
Silicon or germanium can also be doped with a group 13 element like B, Al or Ga which contains only three valence electrons. The
place where the fourth valence electron is missing is called electron hole or electron vacancy.
An electron from a neighbouring atom can fill the electron hole, but in doing so it would leave an electron hole at its original position.
In that case, it would appear as if the electron hole has moved in the direction opposite to that of the electron that filled it.
Under the influence of electric field, electrons would move towards the positively charged plate through electronic holes, but it would appear as
if electron holes are positively charged and are moving towards negatively charged plate. Thus, these types of semiconductors are
called p-type semiconductors.
(c) Types of Extrinsic Semiconductors:
(i) Diode: It is a combination of n-type and p-type semiconductors and is used as a rectifier.
(ii) Transistors: They are made by sandwiching a layer of one type of semiconductor between two layers of the other type of
semiconductor. The npn and pnp type of transistors are used to detector amplify radio or audio signals.
The 12- 16 compounds: These compounds are formed by the combination of group 12 and group 16 compounds. They possess an
average valency of 4. Examples: ZnS, CdS, CdSe and HgTe.
The 13- 15 compounds: These compounds are formed by the combination of group 13 and group 15 compounds. They possess an
average valency of 4. Examples: InSb, AlP and GaAs.
Every substance has some magnetic properties associated with it. The origin of these properties lies in the electrons. Each electron in an
atom behaves like at in tiny magnet. Its magnetic moment originates from two types of motions:
 Its orbital motion around the nucleus and
 Its spin around its own axis.
14.3. Superconductivity
When any material loses its resistance for electric current, then it is called superconductor. Kammerlingh Onnes (1913) observed this phenomenon at 4
K in mercury. The materials offering no resistances to the flow of current at very low temperature (2-5 K) are called superconducting materials and
phenomenon is called superconductivity.
(1) Applications
Electronics, Building supermagnets, Aviation transportation, Power transmission etc.
(2) Superconducting Transition Temperature
The temperature at which a material enters the superconducting state is called the superconducting transition temperature,
(Tc ).
Examples: Nb3 Ge alloy, La1.25Ba0.15CuO4 , YBa2Cu3O7
Superconductivity was also observed in lead (Pb) at 7.2 K and in tin (Sn) at 3.7 K. The phenomenon of superconductivity also occurs in other
materials such as polymers and organic crystals. Examples are (SN)x, polythiazyl, the subscript x indicates a large number of variable size.
(TMTSF)2PF6, where TMTSF is tetra methyl tetra selena fulvalene.

15. Dielectric Properties of Solids
A dielectric substance is that which does not allow the electricity to pass through them but on applying the electric field, induced charges are produced on its
faces. In an insulator, the electrons are strongly held by the individual atoms. When an electric field is applied polarization takes place because nuclei are
attracted to one side and the electron cloud to the other side. As a result, dipoles are created. Such type of crystals shows the following properties:
15.1. Piezoelectricity
In some of the crystals, the dipoles may align themselves in an ordered way so as to give some net dipole moment. When mechanical stress is applied in
such crystals, so as to deform them, electricity is produced due to the displacement of ions. The electricity thus produced is called piezoelectricity
and the crystals are called piezoelectric crystals.
Examples: Quartz, Rochelle’s salt (sodium potassium tartarate), Lithium tantalate (LiTaO3).
Applications: Piezoelectric crystals act as mechanical-electric transducer. These crystals are used as pick-ups in record players where they produce
electric signals by application of pressure.
15.2. Pyroelectricity
On heating, some polar crystals produce a small electric current. The electricity thus produced is called pyroelectircity.
Examples: Gallium nitride, Lithium tantalate (LiTaO3)
Applications: Heat sensors, power generation
15.3. Ferroelectricity
In some of the piezoelectric crystals, a permanent alignment of the dipoles is always there even in the absence of the electric field. However, on
applying field the direction of polarization changes. This phenomenon is called ferroelectricity and the crystals as ferroelectric crystals.
Examples: Potassium hydrogen phosphate (KH2PO4 ) , Barium titanate (BaTiO3) .
Applications: capacitors with tunable capacitance, medical ultrasound machines, high quality infrared cameras, fire sensors, sonar, vibration sensors
15.4. Antiferroelectricity
In some crystals, the dipoles in alternate polyhedra point up and down so that the crystals does not possess any net dipole moment. Such crystals are said to
be antiferroelectric.
Example: Lead zirconate (PbZrO3) .
Applications: Small sized capacitors of high capacitance in transistors, telephone, computer etc.
16. Magnetic Properties of Solids
Based on the behaviour of substances when placed in the magnetic field, they are classified into five classes.
Table: Magnetic Properties of Solids
Alignment of Magnetic
Properties Description Examples Applications
Dipoles
Diamagnetic Feebly repelled by the magnetic fields. Non- All paired electrons TiO2, V2O5, NaCl, Insulator
metallic elements (except O2, S), inert gases C6H6 (benzene)
and species with paired
electrons are diamagnetic.
Paramagnetic Attracted by the magnetic field due to the O 2 , Cu 2+, Fe 3+, TiO, Electronic appliances
presence of permanent magnetic dipoles
Ti2O3, VO, VO2 ,
(unpaired electrons). In magnetic field, these
tend to orient themselves parallel to the CuO
At least one unpaired electron
direction of the field and thus,
produce magnetism in the substances.
Ferromagnetic Permanent magnetism even in the absence Dipoles are aligned in the Fe, Ni, Co, CrO2 CrO2 is used in
of magnetic field. Above a temperature called same direction audio and video
Curie temperature, there is no tapes
ferromagnetism.
Antiferromagnetic This arises when the dipole alignment is MnO, MnO2, Mn2O, –
zero due to equal and opposite alignment. FeO, Fe2O3, NiO,
Cr2O3, CoO, Co3O4,
Ferrimagnetic This arises when there is net dipole Fe3O4, ferrites –
moment.

17. Solid State – Multiple Choice Questions
1. Types of Solid and their Properties 10. The ability of a given substance to assume two or more
crystalline structure is called
1. Which of the following is ferroelectric compound (a) Amorphism (b) Isomorphism
(a) (c) Polymorphism (d) Isomerism

BaTiO3 (b) K 4 [Fe(CN)6]
(c) 11. Certain crystals produce electric signals on application of
Pb2O3 (d) PbZrO3
pressure. This phenomenon is called
2. The property of crystalline solid is not (a) Pyroelectricity (b) Ferroelectricity
(a) Anisotropic (b) Isotropic (c) Peizoelectricity (d) Ferrielectricity
(c) Hard (d) Dense 12. What is the energy gap between valence band and
3. Given: conduction band in crystal of insulators
(a) Both the bands are overlapped with each other

Column A Column B
(b) Very small
A Ionic Solid I NaCl
B Metallic Solid II Fe (c) Infinite
C Covalent Solid III C (graphite) (d) Very large
D Molecular Solid IV Dry ice 13. Crystals of covalent compounds always have
(a) A-II, B-I, C-IV, D-III (b) A-I, B-II, C-III, D-IV (a) Atoms as their structural units
(c) A-III, B-II, C-I, D-IV (d) A-II, B-IV, C-I, D-III (b) Molecules as structural units
4. Among solids the highest melting point is established by (c) Ions held together by electrostatic forces
(a) Covalent solids (b) Ionic solids (d) High melting points
(c) Pseudo solids (d) Molecular solids 14. Wax is an example of
5. Crystalline solids are (a) Ionic crystal (b) Covalent crystal
(a) Glass (b) Rubber (c) Metallic crystal (d) Molecular crystal
(c) Plastic (d) Sugar 15. Which of the following conditions favours the existence of
a substance in the solid state
6. Which one of the following metal oxides is
(a) High temperature (b) Low temperature
antiferromagnetic in nature
(c) High thermal energy (d) Weak cohesive forces
(a) MnO2 (b) TiO2
16. Which of the following arrangements shows schematic
(c) VO2 (d) CrO2 alignment of magnetic moments of antiferromagnetic
substances
7. Malleability and ductility of metals can be accounted due (a) Silica (b) Sodium silicate
to
(c) Silicon carbide (d) Silicon
(a) The capacity of layers of metal ions to slide over the
other
(b) The interaction of electrons with metal ions in the
other
(c) The presence of electrostatic force
(d) The crystalline structure in metal
8. Which of the following is not correct for ionic
crystals
(a) They possess high melting point and boiling point
(b) All are electrolyte
(c) Exhibit the property of isomorphism
(d) Exhibit directional properties of the bond
9. Quartz is a crystalline variety of
(a)
(b)
(c)
(d)
17. The sharp melting point of crystalline solids is due to…..

(a) A regular arrangement of constituent particles
observed over a short distance in the crystal
lattice
(b) A regular arrangement of constituent particles
observed over a long distance in the crystal lattice
(c) Same arrangement of constituent particles in
different directions
(d) Different arrangement of constituent particles in
different directions

18. Which of the following is not the characteristic of ionic 26. Which of the following is an amorphous solid
solids
(a)
Graphite (C) (b) Quartz glass (SiO2)
(a) Very low value of electrical conductivity in the molten state
(b) Brittle nature (c) Chrome alum (d) Silicon carbide (SiC)
(c) Very strong forces of interactions
27. Which of the following is true about the value of refractive
(d) Anisotropic nature index of quartz glass
19. Which of the following statements is not true (a)
Same in all directions
(a) Paramagnetic substances are weakly attracted by (b)
Different in different directions
magnetic field. (c)
Cannot be measured
(b) Ferromagnetic substances cannot be magnetised (d)
Always zero
permanently
28. Iodine molecules are held in the crystals lattice
(c) The domains in antiferromagnetic substances are
by…..
oppositely oriented with respect to each other
(a)
London forces (b) Dipole-dipole interactions
(d) Pairing of electrons cancels their magnetic moment in
the diamagnetic substances. (c) Covalent bonds (d) Coulombic forces
20. A ferromagnetic substance becomes a permanent magnet 29. Which of the following is a network solid
when it is placed in a magnetic field because (a) SO2(solid) (b) I2
…….
(a)
All the domains get oriented in the direction of (c)
Diamond (d) H2O(ice)
magnetic field
(b)
All the domains get oriented in the direction opposite 30. Which of the following solids is not an electrical conductor
to
the direction of magnetic 1. Mg(s) 2. TiO(s) 3. I2 4. H2O(s)
field (s)
(c) Domains get oriented randomly

(a) Only 1 (b) Only 2
(d) Domains are not affected by magnetic field
(c) 3 and 4 (d) 2, 3 and 4
21. Which of the following represents correct order of
31. Graphite is a good conductor of electricity due to the presence
conductivity in solids
of…….
(a)
Kmetals  Kinsulators  Ksemiconductors (a) Lone pair of electrons (b) Free valence electrons
(b)
Kmetals  Kinsulators  Ksemiconductors (c) Cations (d) Anions
(c)
Kmetals , Ksemiconductors  Kinsulators  zero
(d)
Kmetals  Ksemiconductors  Kinsulators 
zero
22. The substance which does not show sharp melting point is sp2 hybridised
carbon
(a) KCl (b) Glass
(c) Ice (d) Diamond
23. Which of the following statements about amorphous
solids is incorrect
(a) They melt over a range of temperature
(b) They are anisotropic
(c) There is no orderly arrangement of particles
32. Which of the following oxides behaves as conductor or
(d) They are rigid and incompressible insulator depending upon temperature
24. Which of the following substance possess (a)
TiO (b) SiO2
antiferromagnetic property
(c) (d)
(a) Fe O (b)
CrO2 TiO3 MgO
3 4

(c) H2O (d) MnO 33. Which of the following oxides shows electrical properties
25. Which is the most stable allotrope of like metals
sulphur
(a) Octahedral sulphur (b) Monoclinic (a) SiO2 (b) MgO
sulphur
(c) SO2(s) (d) CrO2
(c) Plastic sulphur (d) Colloidal sulphur

34. Graphite cannot be classified as ……. r 
c
7. For tetrahedral coordination number, the radius is
(a) Conducting solid (b) Network ra
ratio
solid
(c) Covalent solid (d) Ionic solid
(a) 0.7321.000 (b) 0.414  0.732
35. Which of the following is not true about the ionic
solids (c) 0.225  0.414 (d) 0.155  0.225
(a) Bigger ions form the close packed structure
8. The number of nearest neighbour particles around each
(b) Smaller ions occupy either the tetrahedral or the particle in a face centred cubic lattice/unit cell is
octahedral voids depending upon their size
(a) 4 (b) 6
(c) Occupation of all the voids is not necessary
(c) 8 (d) 12
(d) The fraction of octahedral or tetrahedral voids
occupied depends upon the radii of the ions occupying 9. An fcc unit cell of aluminium contains the equivalent of
the voids how many atoms
2. Crystallography and Lattice (a) 1 (b) 2

(c) 3 (d) 4
1. Which of the following is correct
10. The edge lengths of the unit cells in terms of the radius of
Crystal Axial Axial Examples spheres fcc , bcc and simple cubic unit cells are
system distance angles constituting
(a) Cubic ab=c  =    = Cu, KCl respectively…….
90o 4r
4r
(b) Monoclinic ab=c = =  PbCrO2, (a) 2 2r ,2 (b) ,2 2r ,2r
= 90o PbCrO4 , r 3
3
(c) Rhombohe a= b=c = =  CaCO3,
dral  90o HgS 2r
(c) 2r,
2r , 34r
4r 3 (d) 2r, ,2
(d) Triclinic a= b=c = K2Cr2O7,
2
 90o CuSO4.
5H2O
11. The number of tetrahedral voids in the unit cell of a face
centered cubic lattice of similar atoms is
(a) 4 (b) 6
2. How many space lattices are obtainable from the different
crystal systems (c) 8 (d) 10
(a) 7 (b) 14 12. Which metal crystallizes in a simple cubic structure

(c) 32 (d) 230
(a) Polonium (b) Copper
3. Example of unit cell with crystallographic dimensions
(c) Nickel (d) Iron
a  b  c,     90,   90 is
13. If at cubic cell, atom A presents all corners and atom B at
(a) Calcite (b) Graphite
the centre of each face. What will be the molecular
(c) Rhombic sulphur (d) Monoclinic Sulphur formula of the compounds, if all the atoms present on one
4. The number of close neighbour in a body-centred cubic body diagonal are replaced by atom C
lattice
of identical sphere (a) ABC3 (b) A3 B12C4
is
(a) 8 (b) 6
(c) A3B12C (d) AB12C3
(c) 4 (d) 2
5. The Lattice site in a pure crystal cannot be occupied 14. The metal that crystallises in simple cubic system is
by
(a) Po (b) Na
(a) Molecule (b) Ion
(c) Cu (d) Ag
(c) Electron (d) Atom
6. The correct statement in the following is 3. Crystal Packing
(a) The ionic crystal of AgBr has Schottky defect 1. The arrangement ABC ABC ABC ….. is referred as
(b) The unit cell having crystal parameters, a  b  c,
(a) Octahedral close packing (b) Hexagonal close packing
    90,   120 is hexagonal
(c) Tetragonal close packing (d) Cubic close packing
r
(c) In ionic compounds having Frenkel defect the ratio is 2. The ratio of close-packed atoms to tetrahedral holes in
r cubic close packing is
high
(a) 1 : 1 (b) 1 : 2
+
(d) The coordination number of Na ion in NaCl is 4 (c) 1 : 3 (d) 2 : 1

3. Three elements A, B and C crystallize into a cubic solid 11. The number of octahedral sites per sphere in a fcc structure is
lattice. Atoms A occupy the corners, B atoms, the cube
(a) 8 (b) 4
centres and C atoms, the edge centres. The formula of
the compound is (c) 2 (d) 1
(a)
ABC (b) ABC2 12. A solid is made of two elements X and Z . The atoms Z are
(c) ABC3 (d) ABC4 in CCP arrangement while the atom X occupies all the
tetrahedral sites. What is the formula of the compound
4. The contribution of particle at the edge centre of a
particular unit cell is
(a) XZ (b) XZ2
1 1
(a) (b) (c) X Z (d) X Z
2 4 2 2 3
1
(c) 1 (d)
8
13.
Given that the radius of Na ion is 0.95 Å and that of Cl
5. In face centred cubic unit cell, what is the volume ion is 1.81 Å, hence in the close packed lattice of Cl ions
occupied
(a) 4 3 8 3 
r (b) r Na ions prefer to occupy
3 3
(a) Tetrahedral site (b) Octahedral site
(c) 64r 3
16 3 (d) 3 3 (c) Cubic site (d) Trigonal site
3 r
6. In which pair most efficient packing is present 14. In NaCl unit cell, all the ions lying along the axis as shown
in
(a) hcp and bcc (b) hcp and ccp
the figure are removed. Then the number of Na and Cl
(c) bcc and ccp (d) bcc and simple cubic cell ions remaining in the unit cell are
7. Which of the following statement is not true about the
hexagonal close packing
(a) The coordination number is 12
(b) It has 74% packing efficiency
(a) 4 and 4 (b) 3 and 3
(c) Tetrahedral voids of the second layer are covered by
the spheres of the third layer (c) 1 and 1 (d) 4 and 3
(d) In this arrangement spheres of the fourth layer are 15. Total no. of voids in 0.5 mole of a compound forming
exactly aligned with those of the first layer hexagonal closed packed structure are
8. The correct order of the packing efficiency in different (a) 6.022  1023 (b) 3.011 1023
types of
unit cells is……. (c) 9.033  1023 (d) 4.516  1023
(a) fcc  bcc  simplecubic (b) fcc  bcc  simplecubic
16. In the cubic close packing, the unit cell has…….
(c) fcc  bcc simplecubic (d) bvv  fcc simplecubic
(a) 4 tetrahedral voids each of which is shared by four
9. Suppose the mass of a single Ag atom is ‘m’. Ag metal adjacent unit cells
crystallizes in fcc lattice with unit cell of length ‘a’. The
density of Ag metal in terms of ‘a’ and ‘m’ is (a) 4 tetrahedral voids within the unit cell
(a) 4m
(b) 2m (c) 8 tetrahedral voids each of which is shared by four
a 3
a3 adjacent unit cells
(b) m
(d) m (d) 8 tetrahedral voids within the unit cells
a 3 4a3
10. Which is not the correct statement for ionic solids in which 17. In metallic solids, the number of atoms for the face-
positive and negative ions are held by strong electrostatic centered and the body-centered cubic unit cells, are
respectively
attractive (a) 2, 4 (b) 2, 2
forces
r / r increases as coordination number
(c) 4, 2 (d) 4, 4
(a) The radius
increases
(b) As the difference in size of ions increases, coordination 18. An ionic compound is formed between a metal M and a
number increases non- metal Y . If M occupies half the octahedral voids in

the cubic
(c)
When coordination number is eight, the r  / close-packed arrangement formed by Y, the chemical
ratio lies
r formula of the ionic compound is
between 0.225 to 0.414
(d)
In ionic solid of the type AX (ZnS, Wurtzite) the
(a) MY (b) MY2
2 2
coordination number of Zn and S respectively are
(c) M2Y (d) MY3
4 and 4

19. In a cubic close packed structure, fractional contributions 4. Radius ratio of an ionic compound is 0.93. The structure
of an atom at the corner and at the face in the unit cell of the above ionic compound is of
are, respectively (a) NaCl type (b) CsCl type
(a) 1/8 and 1/2 (b) 1/2 and 1/4 (c) ZnS type (d) None of these
5. In the closest packed structure of a metallic lattice, the
(c) 1/4 and 1/2 (d) 1/4 and 1/8 number of nearest neighbours of a metallic atom is
(a) Twelve (b) Four
4. Mathematical Analysis of Cubic System and
Bragg’s Equation (c) Eight (d) Six
6. The ionic radii of Rb and I are 1.46 Å and 2.16 Å. the
 
1. Bragg's law is given by the equation most probable type of structure exhibited by it is
(a) CsCl type (b) ZnS type
(a)
n  2sin (b) n  2d sin
(c) NaCl type (d) CaF2 type
 d
(c) 2n  d sin (d) n  sin
2 2 7. In which of the following structures coordination number
for cations and anions in the packed structure will be
2. To obtain a diffraction peak, for a crystalline solid with same
inter plane distance equal to the wavelength of incident
(a) Cl ions form fcc lattice and Na ions occupy all
X–ray
octahedral voids of the unit cell
radiation, the angle of incidence should
be (b) Ca2 ions form fcc lattice and F ions occupy all the
(a) 90o (b) 0o eight tetrahedral voids of the unit cell

(c) (c) O2 ions form fcc lattice and Na ions occupy all the eight
30
o (d) 60o
tetrahedral voids of the unit cell
3. If the angle of incidence of X-ray of wavelength 3 Å which (d) 2 ions form fcc lattice and Zn2 ions go into alternate
produces a second order diffracted beam from the tetrahedral voids of the unit cell
(100) planes in a simple cubic lattice with interlayer spacing
o 8. What is the coordination number in a square close packed
a  6 Å is 30 , the angle of incidence that produces a first-
structure in two dimensions
order diffracted beam from the (200) planes (a) 2 (b) 3
is
(a) o (c) 4 (d) 6
15 (b) 45o
(c) 9. Which of the following statements is not true about NaCl
o
30 (d) 60o structure
5. Crystal Structure and Coordination Number
(a) Cl ions are in fcc arrangement
(b) Na ions has coordination number 4
1. The interionic distance for cesium chloride crystal will
(c) Cl ions has coordination number 6
be
(d) Each unit cell contains 4 NaCl molecules
a
(a) a (b) 10. Which set of characteristics of ZnS crystal is correct
2
(a) Coordination number (4 : 4); ccp; Zn ion in the
3a 2a
(d) alternate tetrahedral voids
(c) 3
2 (b) Coordination number (6 : 6); hcp; Zn ion in all
2. A solid has a structure in which ' W ' atoms are located at tetrahedral voids
the corners of a cubic lattice ' O' atoms at the centre of (c) Coordination number (6 : 4); hcp; Zn ion in all
edges and ' Na' atoms at the centre of the cube. The octahedral voids
formula for the compound is (d) Coordination number (4 : 4); ccp; Zn ion in all
(a) NaWO (b)
NaWO3 tetrahedral voids
2
(c)
Na2WO3 (d) NaWO4 per unit cell is
3. The unit cell of a binary alloy composed of A and B

metals, has a ccp structure with A atoms occupying the
corners and B atoms occupying centres of each face of
the cube. If during the crystallization of this alloy, in the
unit cell two A atom are missed, the overall composition
11.
In Na2O having antifluorite structure (b) Oxide ions have a cubic close packed arrangement and
(a) Oxide ions have a cubic close packed arrangement and Na occupy all the octahedral voids
Na occupy all the eight tetrahedral voids (c) Na ions have a cubic close packed arrangement and
(a) AB (b) AB4 O2 occupy all the octahedral voids
6
(c) (d) Na ions have a cubic close arrangement and

AB8 (d) AB24 O2
occupy all the tetrahedral voids

12.
A unit cell of calcium fluoride has four calcium ions. The 8. The following is not a function of an impurity present in a
number of fluoride ions in the unit cell is crystal
(a) 2 (b) 4 (a) Establishing thermal equilibrium
(c) 6 (d) 8 (b) Having tendency to diffuse
13.
A mineral consists of a cubic close-packed structure (c) Contributing to scattering
formed by O2 ions where half the octahedral voids are (d) Introducing new electronic energy levels
occupied by Al 3 and one eight of the tetrahedral voids are
9. If a non-metal is added to the interstitial sites of a metal
occupied by Mn2 . The chemical formula of the mineral is then the metal becomes
(a) (b) MnAl2O4 (a) Softer (b) Less tensile
Mn3Al2O6
(c) MnAl4O7 (d) Mn2Al2O5 (c) Less malleable (d) More ductile
6. Defects in Crystal 10. In AgBr crystal, the ion size lies in the order Ag  Br.
The AgBr crystal should have the following characteristics
1. Due to Frenkel defect, the density of ionic solids (a) Defectless (perfect) crystal
(a) Increases (b) Decreases (b) Schottky defect only
(c) Does not change (d) Changes (c) Frenkel defect only
2. When electrons are trapped into the crystal in anion (d) Both Schottky and Frenkel defects
vacancy, the defect is known as 11. Which of the following defect is seen in FeO
(a) Schotky defect (b) Frenkel defect (a) Metal excess defect (b) Metal deficiency defect
(c) Stoichiometric defect (d) F-centres (c) Displacement defect (d) Impurity defect
3. Which of the following is true about the charge acquired 12. To get a n-type semiconductor from silicon, it should be
by doped with a substance with valency……
p-type semiconductors
(a) 2 (b) 1
(a) Positive
(c) 3 (d) 5
(b) Neutral
13. Which one of the following crystals does not exhibit
(c) Negative Frenkel defect
(d) Depends on concentration of p impurity (a) AgBr (b) AgCl
4. Which of the following defects is also known as dislocation (c) KBr (d) ZnS
defect
14. Which kind of defects are introduced by
(a) Frenkel defect doping
(b) Schottky defect (a) Dislocation defect (b) Schottky defect
(c) Non-stoichiometric defect (c) Frenkel defect (d) Electronic defect
(d) Simple interstitial defect 15. Silicon doped with electron rich impurity forms…….
5. Schottky defects occurs mainly in electrovalent (a) p-type semiconductor (b) n-type semiconductor
compounds where (c) Intrinsic semiconductor (d) Insulator
(a) Positive ions and negative ions are of different size 16. The defect that is more likely to occur in almost all types
(b) Positive ions and negative ions are of same size of ionic crystals is
(c) Positive ions are small and negative ions are big (a) Non-stoichiometric defects
(b) Schottky defect
(d) Positive ions are big and negative ions are small
(c) Frenkel defect
6. The white ZnO turns yellow on heating because of
(d) All the above
(a) Frenkel defect (b) Metal excess defect
17. Schottky defect in a crystal arises due to
(c) Metal deficiency defect (d) Schottky defect
(a) Creation of equal number of cation and anion vacancies
7. Schottky defect generally appears in
(b) Creation of unequal number of cation and anion
(a) NaCl (b) KCl vacancies
(c) Migration of cations to interstitial voids
(c) CsCl (d) All of these
(d) Migration of anions to interstitial voids

7. JEE Mains
9.
The correct statement for the molecule, CsI3, is [2014]
(a) It is a covalent molecule

1. Which of the following is an example of covalent crystal
solid
(b) It contains Cs and I
[2013] 3
(a)
Si (b) NaF (c) It contains Cs3 and I ions
(c) Al (d) Ar
(d) It contains Cs  , I and lattice I2 molecule
2. Na and Mg crystallize in bcc and fcc type crystals
respectively, then the number of atoms of Na and Mg
10.
The packing efficiency of the two-dimensional square unit
present in the unit cell of their respective crystal is [2002] cell shown below is
(a)
4 and 2 (b) 9 and 14
(c) 14 and 9 (d) 2 and 4
3. In a face centred cubic lattice, atom A occupies the corner
positions and atom B occupies the face centre position. If
[2010]
one atom of B is missing from one of the face centred
points, the formula of the compound is [2011]
(a) (a) 39.27% (b) 68.02%

A2B (b) AB2
(c) (c) 74.05% (d) 78.54%

A2 (d) A2
B3 B5
4. Sodium metal crystallizes in a body centred cubic lattice 11. Total volume of atoms present in face-centred cubic unit
with a unit cell edge of 4.29 Å. The radius of sodium atom cell of a metal is (r is atomic radius) [2006]
is approximately [2015]
(a) 1.86 Å (b) 3.22 Å (a) 22 r3 (b) 24 r3

3 3
(c) 5.72 Å (d) 0.93 Å
16
5. Lithium forms body centred cubic structure. The length of
(c) 12 r3 (d) r3
the side of its unit cell is 351 pm. Atomic radius of the 3 3
lithium will
be [2012] 12. The edge length of unit cell of a metal having molecular
(a) 75 pm (b) 300 pm weight 75 g/mol is 5 Å which crystallizes in cubic lattice. If
(c) 240 pm (d) 152 pm the density is 2 g/cc then find the radius of metal atom.
(NA  6 1023 ) . Give the answer in pm [2006]
6. CsCl crystallizes in body centred cubic lattice. If 'a' its
edge length then which of the following expressions is
(a) 217 pm (b) 210 pm
correct
[2014] (c) 220 pm (d) 205 pm
3a
(a) r  r   3a (b) r  r  
Cs Cl Cs Cl
13. How many unit cells are present in a cube-shaped ideal crystal
3 2
(c) r  r  a (d)
 r   3a of NaCl of mass 1.00 g [Atomic masses: Na  23,Cl  35.5]
r
 Cs Cl
Cs Cl
2 [2003]
7. In which of the following crystals alternate tetrahedral

voids are occupied [2005] (a) 2.57 × 1021 unit cells (b) 5.14 × 1021 unit cells
(a) NaCl (b) ZnS (c) 1.28 × 1021 unit cells (d) 1.71 × 1021 unit cells
(c) CaF2 (d) Na2O
14. A metal crystallizes in a face centred cubic structure. If
8. In a compound, atoms of Y form ccp lattice and those of the edge length of its unit cell is 'a', the closest approach
element X occupy 2/3rd of tetrahedral voids. The formula of
between two atoms in metallic crystal will be [2017]
the compound will be [2008]
(b)2a
(a)
X2Y3 ( a) 2 2a
(b) X2Y
(c)
X3 Y4 (d) X4 Y3 a
(c) (d) 2a
2

15. A compound MP Xq has cubic close packing (ccp) 22. Which primitive unit cell has unequal edge lengths (a  b  c)
arrangement of X. Its unit cell structure is shown below. and all axial angles different from 90 [2019]
The empirical formula of the compound is [2012]
(a) Monoclinic (b) Triclinic
M=
X= (c) Hexagonal (d) Tetragonal
23. A compound of formula A2 has the hcp lattice. Which
B3
atom forms the hcp lattice and what fraction of
tetrahedral voids is occupied by the other atoms : [2019]
(a) MX (b) MX2
2
(c) M X (d) M X (a) hcp lattice  A, Tetrahedral voids-B
2 5 14 3
16.
In a solid ‘AB’ having the NaCl structure, ‘A’ atoms occupy
the corners of the cubic unit cell. If all the face-centered (b) hcp lattice  B, Tetrahedral voids-A
1
atoms along one of the axes are removed, then the
resultant stoichiometry of the solid is [2001] 3
Tetrahedral voids-A
(c) hcp lattice  B,
2
(a) AB2 (b) A2 B 3
(c) A B
4 3 (d) A3 (d) hcp lattice  A, Tetrahedral voids-B
B4 1
17.
What type of crystal defect is indicated in the diagram 3
below
[2004] 24. A solid having density of 9  103 kg m3 forms face centred
Na Cl Na Cl Na Cl cubic crystals of edge length 200 2 pm. What is the molar
Cl  Cl Na  Na
mass of the solid [2019]
Na Cl  Cl Na Cl
(Avogadro constant  6 1023 mol1,  
Cl Na+ Cl Na+  3)
Na+
(a) Interstitial (a) 0.0432 kg mol1 (b) 0.0305 kg mol1
defect
(b) Schottky defect (c) 0.4320 kg mol1 (d) 0.0216kg mol1
(c) Frenkel defect
(d) Frenkel and Schottky defects
25. The radius of the largest sphere which fits properly at the
18. Experimentally it was found that a metal oxide has formula
centre of the edge of body centred cubic unit cell is : (Edge
2 3
M0.98O. Metal M, present as M and M in its oxide. length is represented by ‘a’) [2019]
3
Fraction of the metal which exists as M would be [2013]
(a) 0.047 a (b) 0.027a
(a) 7.01% (b) 4.08%
(c) 6.05% (d) (c) 0.134 a (d) 0.067a
5.08%
19. Which type of ‘defect’ has the presence of cations in the
26. Element ' B' forms ccp structure and ' A' occupies half of
interstitial sites [2018]
the octahedral voids, while oxygen atoms occupy all the
(a) Frenkel defect (b) Metal deficiency defect
tetrahedral voids. The structure of bimetallic oxide is
(c) Schottky defect (d) Vacancy defect
20. The one that is extensively used as a piezoelectric material [2019]
is:
[2019] (a) A2BO4 (b) A2B2O
(a) Tridymite (b) Amorphous
silica
(c) Quartz (d) Mica (c) AB2O4 (d) A4 B2O
21. At 100C , copper (Cu) has fcc unit cell structure with cell
27. The statement that is INCORRECT about the interstitial
edge length of x Å . What is the approximate density of compounds is [2019]
Cu (in g cm ) at this temperature ?
3
(a) They are chemically reactive

[Atomic mass of Cu=63.55 u] [2019]
(b) They have metallic conductivity
(a) 205 105
(b) (c) They are very hard
x3 x3
422 211 (d) They have high melting points
(c) (d)
3 3
x x

28. Consider the bcc unit cells of the solids 1 and 2 with the 2. If a is the length of the side of a cube, the distance
position of atoms as shown below. The radius of atom B is between the body centered atom and one corner atom in
twice that of atom A. The unit cell edge length is 50% the cube will be
more [2014]
in solid 2 than in 1. What is the approximate packing 3 3
efficiency in solid 2 [2019] (a) a (b) a
4 2
A A
A A A A 2 4
A A (c) 3 a (d) 3 a
A B 3. If 'a' stands for the edge length of the cubic systems:

A A simple cubic, body centred cubic and face centred cubic,
A
A A then the ratio of radii of the spheres in these systems will
A
A Solid 2 be respectively
A
Solid 1 [2008]
(a) 65% (b) 45% 1 3 2
(a) a a: a (b) 1a 3 a:2 a
(c) 90% (d) 75% 2 2
: :
2
29.
10 mL of 1mM surfactant solution forms a monolayer 1 1
(c) 1 a : 3 a : 1 a (d) a 3 a: a
2 : 2
covering 0.24 cm on a polar substrate. If the polar head is 2 4 2 2
approximated as a cube, what is its edge length [2019] 4. The number of carbon atoms per unit cell of diamond unit
(a) 1.0 pm (b) 2.0 nm cell is [2013]
(a) 1 (b) 4
(c) 0.1nm (d) 2.0 pm
(c) 8 (d) 6
30.
The amorphous form of silica is [2019]
5. The vacant space in bcc lattice cell is [2015]
(a) Quartz (b) Tridymite
(a) 26% (b) 48%
(c) Cristobalite (d) Kieselguhr
(c) 23% (d) 32%
31.
An element has a face-centred cubic (fcc) structure with a
6. An ionic compound has a unit cell consisting of A ions at
cell edge of a. The distance between the centres of two
the corners of a cube and B ions on the centres of the
nearest tetrahedral voids in the lattice is [2019]
faces of the cube. The empirical formula for this
(a)2a (b)
a compound would be
[ 2005]
(a) AB (b) A B
3 a 2
(c)
a (d)
(d) A B
2 2 (c) AB
3 3
32. The ratio of number of atoms present in a simple cubic,

7. The number of octahedral void (s) per atom present in a
body centered cubic and face centered cubic structure are
cubic close-packed structure is [2012]
respectively [2019]
(a) 1 (b) 3
(a) 4 : 2 : 1 (b) 8 : 1 : 6
(c) 2 (d) 4
(c) 4 : 2 : 3 (d) 1 : 2 : 4
8. Copper crystallises in fcc with a unit cell length of 361 pm.
33. Which of the following compounds is likely to show both What is the radius of copper atom [2015]
Frenkel and Schottky defects in its crystalline form?
(a) 108 pm (b) 127 pm
[2020]
(c) 157 pm (d) 181 pm
(a) CsCl (b) KBr
9. AB crystallizes in a body centred cubic lattice with edge length
(c) AgBr (d) ZnS ' a' equal to 387 pm. The distance between two oppositively
(a) 8 (b) 4
8. NEET (c) 2 (d) 6
1. In a face-centered cubic lattice, a unit cell is shared equally

by how many unit cells [2005]
charged ions in the lattice is [2010]
(a) 300 pm (b) 335 pm
(c) 250 pm (d) 200 pm
10. A metal crystallizes with a face-centered cubic lattice.
The edge of the unit cell is 408 pm. The diameter of
the metal atom is
[2012]
(a) 288 pm (b) 408 pm
(c) 144 pm (d) 204 pm

11. The edge length of face centred unit cubic cell is 508 pm. 18. Lithium has a bcc structure. Its density is 530 kg m−3 and
If the radius of the cation is 110 pm, the radius of the its atomic mass is 6.94 g mol−1 Calculate the edge length
anion is of a
[2010] unit cell of Lithium metal. (NA  6.02 1023 [2016]
(a) 285 pm (b) 398 pm mol1)
(c) 144 pm (d) 618 pm
(a) 154 pm (b) 352 pm
12. Structure of a mixed oxide is cubic close-packed (c.c.p). (c) 527 pm (d) 264 pm
The cubic unit cell of mixed oxide is composed of oxide 19. Percentages of the free space in cubic close packed
ions. One fourth of the tetrahedral voids are occupied by structure and in body centered packed structure are
divalent metal A and the octahedral voids are occupied by respectively [2008]
a monovalent metal B. The formula of the oxide is [2012]
(a) 48% and 26% (b) 30% and 26%
(c) 26% and 32% (d) 32% and 48%
(a) ABO2 (b) A2BO2 20. The pyknometric density of sodium chloride crystal is
(c) A B O (d) AB2O2 2.165 103 kg while its X-rays density is
2 3 4
m3
13. Which of the following statements is not correct [2008]
2.178 10 3 kg m3 . The fraction of unoccupied sites in
(a) The number of carbon atoms in an unit cell of Diamond
sodium chloride crystal is [2003]
is 4 3
(a) 5.96 10 (b) 5.96
(b) The number of Bravais lattices in which a crystal can
be categorized is 14 (c) 5.96 102 (d) 5.96 101
(c) The fraction of the total volume occupied by the 21.
A solid compound XY has NaCl structure. If the radius of the
atoms in a primitive cell is 0.52 cation is 100 pm, the radius of the anion (Y  ) will be [2011]
(d) Molecular solids are generally volatile
(a) 241.5 pm (b) 165.7 pm
14. Iron exhibits bcc structure at room temperature. Above
(c) 275.1 pm (d) 322.5 pm
900 , it transforms to fcc structure. The ratio of density
C 22.
The ionic radii of A and B ions are 0.98 1010 and
of
m
iron at room temperature to that at 900 (assuming molar
C 1.81 1010 m. The coordination number of each ion in AB
mass and atomic radii of iron remains constant with
temperature) is [2018] is [2016]
(a) 6 (b) 4
3 4 3
(a) (b)
2 3 2 (c) 8 (d) 2
23.
1 In calcium fluoride, having the fluorite structure, the
(c) (d) coordination numbers for calcium ion (Ca2+) and fluoride
3 3 2
4 2
15. The fraction of total volume occupied by the atoms ion (F) are [2016]
present in a simple cube is [2007]
(a) 6, 6 (b) 8, 4
(a)   (c) 4, 4 (d) 4, 8

(b)
6 32 24. The correct statement regarding defects in crystalline solid is
(c)  
(d) [2015]
42 4 (a) Schottky defects have no effect on the density of
16. CsBr crystallises in a body centred cubic lattice. The unit crystalline solids
cell length is 436.6 pm. Given that the atomic mass of Cs
(b) Frenkel defects decrease the density of crystalline solids
= 133 and that of Br =80 amu and Avogadro number
being (c) Frenkel defect is a dislocation defect
 6.023 1023 mol1. CsBr , the density of CsBr is [2006] (d) Frenkel defect is found in halides of alkaline metals
(a) 8.25 g/cm3 (b) 4.25 g/cm3 g/cm3
(c) 42.5 g/cm3 (d) 0.425

25. h rance of colour in solid alkali metal halides is generally
T e appea due to [2006]
17. A metal has a fcc lattice. The edge length of the unit cell is (a) Frenkel defect (b) Interstitial positions
404 pm. The density of the metal is (c) F-centres (d) Schottky defects
2.72 g cm3 . The
molar
mass of the metal is [2013] 26. With which one of the following elements silicon should be
doped so as to give p-type of semiconductor [2008]
(a) 20 g mol1 (b) 40 g
(a) Selenium (b) Boron
mol1
(c) 30 g mol1 (c) Germanium (d) Arsenic
(d) 28 g
mol1

27. If NaCl is doped with mol% of SrCl2 , the 36. What is the coordination number of sodium in Na 2O [2003]
104
concentration of cation vacancies will be [2007]
(a) 6 (b) 4
23 1
(NA  6.02 10 mol )
(c) 8 (d) 2
(a) 6.02 1015 (b) 6.02 1016 37. A compound is formed by cation C and anion A . The anions
mol1 mol1 form hexagonal close packed (hcp) lattice and the cations
(c) occupy 75% of octahedral voids. The formula of the
6.02 1017 (d) 6.02 1014
mol1 mol1
28. Which is the incorrect statement [2017] compound is [2019]
(a) (a) C4 A3 (b) C2 A3

FeO0.98 has non stoichiometric metal deficiency
defect
(b) Density decreases in case of crystals with Schottky's
(c) C3 A2 (d) C3 A4
defect
(c) NaCl(s) is insulator, silicon is semiconductor, silver is
conductor, quartz is piezo electric crystal 9. Numerical Based Questions
(d) Frenkel defect is favoured in those ionic compounds in 1. The number of atoms in 100 g of an fcc crystal with density
which sizes of cation and anions are almost
d  10 g/cm3 and cell edge equal to 100 pm, is equal to
equal
29. The crystal system of a compound with unit cell x 1025. Find out the value of x.
dimensions
a  0.387 , b  0.387 and c  0.504nm and     90o
and   120o is [2004] 2. The second order Bragg's diffraction of X  rays with   1 Å
(a) Cubic (b) Hexagonal

from a set of parallel planes in a metal occurs at an angle of 60 o .
(c) Orthorhombic (d) Rhombohedral The distance between the scattering planes in the crystal is
30. If ‘Z’ is the number of atoms in the unit cell that
represents the 3. Potassium has a bcc structure with nearest neighbour
closest packing sequence   A B C A B C   , the distance 4.52 Å. Its atomic weight is 39. Its density
number of tetrahedral voids in the unit cell is equal to
[2005] (in kg m3 ) will be
(a) Z (b) 2 Z
4. Body centered cubic lattice has a coordination number of
(c) Z/2 (d) Z/4
31. An AB type structure is found in [2002]
2 5. Iron crystallizes in a bcc system with a lattice parameter of
(a)
NaCl (b) Al2O3 2.861 Å. Calculate the density of iron in the bcc system.
(c) 6. Li forms a body centered cubic lattice. The edge length of

CaF2 (d) N2O
the lattice is 3.5 ×10–10m and the observed density is
32.
The Ca2+ and F– are located in CaF2 crystal, respectively at
5.3 × 102 kg m–3. Calculate percentage occupancy of
face centred cubic lattice points and in [2006]
lattice points by Li metal.
(a) Tetrahedral voids (b) Half of tetrahedral voids
7. Calcium crystallizes in a face-centered cubic unit cell with
(c) Octahedral voids (d) Half of octahedral voids
a = 0.556nm. Calculate the density if It contains 0.1%
33.
If AgI crystallises in zinc blende structure with I ions at Frenkel defects
lattice points. What fraction of tetrahedral voids is
8. Calculate the percentage of void volume in the face-
occupied by Ag  ions [2007]
centred cubic metallic crystals.
(a) 25% (b) 50%
9. Compute the percentage void per unit volume of unit cell
(c) 100% (d) 75% of Corundum.
34.
An element (atomic mass 100 g/mol) having bcc structure
10. KCl crystallizes in the same type of lattice as dose NaCl. Given
has unit cell edge 400 pm. Then density of the element is
r  r 
[2015] that Na  5.0 and Na  0.7
r  r 

Cl K
(a) 10.376 (b) 5.188
g/cm3 g/cm3 Calculate (a) the ratio of side of the unit cell for KCl to that for
(c)
NaCl, and (b) ratio of density of NaCl to that of KCl.
7.289 g/cm3 (d) 2.144
g/cm3
35. If the pressure on a NaCl structure is increased, then its
11. A metallic element crystallizes into a lattice containing a
coordination number will [2015]
sequence of layers of ABABAB….. Any packing of spheres
(a) Increase (b) Decrease leaves out voids in the lattice. What percentage by volume
(c) Remain the same (d) Either (b) or (c) of this lattice is empty space?

17. Solid State – Answers Keys
1. Types of Solid and their Properties 6. Defects in Crystal
1 a 2 b 3 b 4 b 5 d 1 c 2 d 3 b 4 a 5 b
6 a 7 a 8 d 9 a 10 c 6 b 7 d 8 a 9 b 10 d
11 c 12 d 13 a 14 d 15 b 11 b 12 d 13 c 14 d 15 b
16 d 17 b 18 a 19 b 20 a 16 b 17 a
21 a 22 b 23 b 24 d 25 a
7. JEE Mains
26 b 27 a 28 a 29 c 30 c
1 a 2 d 3 d 4 a 5 d
31 b 32 c 33 d 34 d 35 d
6 c 7 b 8 d 9 b 10 d
2. Crystallography and Lattice
11 d 12 a 13 a 14 c 15 b
1 c 2 b 3 d 4 a 5 c 16 d 17 b 18 b 19 a 20 c
6 b 7 c 8 d 9 d 10 a 21 c 22 b 23 b 24 b 25 d
11 c 12 a 13 c 14 d 26 c 27 a 28 c 29 d 30 d
31 d 32 d 33 a
3. Crystal Packing
8. NEET
1 d 2 b 3 c 4 b 5 c
6 b 7 d 8 b 9 a 10 c 1 d 2 b 3 c 4 c 5 d
11 d 12 c 13 b 14 b 15 c 6 c 7 a 8 b 9 b 10 a
16 d 17 c 18 b 19 a 11 c 12 d 13 a 14 c 15 a
16 b 17 d 18 b 19 c 20 a
4. Mathematical Analysis of Cubic System and
Bragg’s Equation 21 a 22 a 23 b 24 c 25 c
26 b 27 c 28 ad 29 b 30 b
1 b 2 c 3 c
31 c 32 a 33 b 34 b 35 a
5. Crystal Structure and Coordination Number
36 b 37 d
1 c 2 b 3 b 4 b 5 a 9. Numerical Based Questions

6 c 7 a 8 c 9 b 10 a
1 4 2 1.2 3 91 4 8 5 7.9
11 a 12 d 13 b
6 97.8 7 1.5 8 26 9 22.4 10 1.2
11 26.1

17. Solid State – Answers and Solutions
1. Types of Solid and their Properties 17. (b) Crystalline solid has regular arrangement of
constituent particles observed over a long distance in
the crystal lattice. Due to this regular arrangement,
1.
(a) BaTiO3 is a ferroelectric compound.
crystalline solid have sharp melting point.
2.
(b) Not isotropic actually refers to anisotropic here.
3.
18. (a) Ionic solids easily dissociated into its ions in molten
(b) As per different types of forces. state and show high electrical conductivity. While
4.
(b) Ionic solids have highest melting point due to strong ionic solids are anisotropic and brittle linked with very
electrostatic forces of attraction. strong force of interactions.
5.
(d) Sugar is a crystalline solid while glass, rubber and 19. (b) Ferromagnetic substances can be magnetised by
plastic are amorphous solids. applying magnetic field to it and magnetic property
6.
(a) MnO2 is antiferromagnetic. persist within it even after removal of magnetic field.
7. 20. (a) When a ferromagnetic substance is placed in a
(a) When a metal is beaten, it does not break but is
magnetic field it becomes a permanent magnet
converted into sheet. It is said to possess the
because all the domains get oriented in the direction
property of malleability. Due to ductile nature, metals
of magnetic field even after removal of applied
can be drawn into wires. These two properties of
magnetic field.
metals can be accounted due to the capacity of layers
21. (a) Conductivity of metal, insulator and semiconductors
of metal ions to slide over the other.
8.
(d) Ionic crystals exhibit non-directional properties of the can be represented in the term of k (Kappa) which
bond. depends upon energy gap between valence band and
9. conduction brand.
(a) Quartz is a covalent crystal having a framework of
Conduction band
silicates or silica, i.e. a three dimensional network
when
all the four oxygen atoms of each of SiO4 tetrahedron Empty
band Empty
are shared. Forbidden zone band
10. (c) Polymorphism is an ability of a substance which (Large energy gap)
Small
shows two or more crystalline structure. Energy
Ener
Filled
11. (c) When polar crystal is subjected to a mechanical gap
band
stress, electricity is produced a case of Partially Overlapping
piezoelectricity. Reversely, if electric field is applied, filled bands
mechanical stress is developed. Piezoelectric crystal band
acts as a mechanical electrical transductor. Metal Insulator Semiconductor
12. (d) When insulators (non-metal atoms) interact to form a 4 6 4
solid, their atomic orbitals mix to form two bunches
Value of k 10  107 1020  10  10
of orbitals, separated by a large band gap. Electrons (in 1 m1) 1010
cannot therefore be promoted to an empty level,
Hence, correct order
where they is
could move freely.
13. (a) Constituent particles of covalent compounds are
atoms.
14. (d) Wax crystals are molecular crystals, in which Schematic arrangement of
constituent particles are molecules having antiferromagnetic substance
interparticle forces are Vander Waal’s forces.
15. (b) At low temperature existence of a substance in solid
state is due to
(i) Slow molecular motion and
(ii) Strong cohesive forces
These two forces hold the constituent particles
together thus causes existence of substance in solid
state.
16. (d) The substances which have domain structure are
oppositely oriented and cancel each other’s magnetic
field are known as antiferromagnetic substances.
Chemis Solid State – Answers and Solutions |

Kmetals  Kinsulators  Ksemiconductors .
22. (b) Amorphous or non-crystalline solids do not have
sharp melting point.
23. (b) Amorphous solids are isotropic, because
these substances show same
properties in all directions.
24. (d) MnO; this aries when the dipole alignment is zero
due to equal and opposite alignment.
25. (a) Octahedral sulphur /  sulphur / Rhombic sulphur is
the
most stable allotrope of sulphur.
26. (b) Quartz glass (SiO2) is an amorphous solid due to
its short range order of constituent particles.
27. (a) Since, quartz glass is an amorphous solid having
short range order of constituents. Hence, value of
refractive index is same in all directions, can be
measured and not be equal to zero always.
28. (a) Iodine molecules are a class of non-polar
molecular solid in which constituents molecules
are held together by London or dispersion forces.
These solids are soft and non-conductor of
electricity.

29. (c) Diamond is a giant molecule in which constituent
atoms are held together by covalent bond. Hence,
2. Crystallography and Lattice
this is a network solid.
1. (c) Rhombohedral crystal system
a  b  c ,       90o
Examples, NaNO3 , CaSO4 , calcite CaCO3 , HgS
2. (b) There are 14 Bravais lattices (space lattices).
3. (d) Monoclinic sulphur is an example of Monoclinic crystal
system.
4. (a) Atom ' A ' is touching 4 unit cells in one layer and 4 on
top of these so the no. of shared unit cells by a
corner atom in a bcc lattice is  4  4  8 . Atom X is
inside the unit cell so it is shared by only one-unit
cell.
Network structure of atom
Atom ' A ' is touching 5 atoms in its layer (B, D, E, N
30. (c) Iodine is a non-polar molecular solid in which iodine and I) and one atom in the layer above it. So, atom '
molecules are held together by London force or
A ' has next coordination no. as 6 (nearest next
dispersion force. This is soft and non-conductor of
neighbours).
electricity.
Atom X can touch all corner atoms of its unit cell, so the
Water is a hydrogen bonded molecular solid in which no. of close neighbours is 8 (coordination no.).
H and O are held together by polar covalent bond I
and each water molecule held together by hydrogen J M
bonding. Due to non-ionic nature, they are not B N
A
electrical conductor.
31. (b) Graphite is a good conductor of electricity due to D O
C
K
presence of free valence electrons in graphite, each R
L
carbon is sp2 hybridized having one free electron X
F
which Q
E
makes graphite a good conductor of electricity.
G H P
32. (c) Certain metal oxides like

VO2, VO, VO3 an TiO3 bcc lattice
d
show metallic or insulating property depending upon 5. (c) Each point in a lattice is known as lattice point which
temperature. As temperature varies metallic or is either atom or molecule or ion crystal constituents
insulating property varies. This is due to variation in are arranged in fixed stoichiometric ratio.
energy gap between conduction band and valence Hence, existence of free electrons are not possible, it
band. is possible on in case of imperfection in solid.
33. (d) CrO2 , TiO and ReO3 are some typical metal oxides 6. (b) A crystal system is hexagonal if its unit cell having
which show electrical conductivity similar to metal.
While
SiO2, MgO and SO2 are oxides of metal, semimetal a  b  c axial ratio and     90,   120 axial
and non-metal which do not show electrical atoms (r) as

properties.
Radius of octahedral void (R0)  0.414r
34. (d) Graphite can’t be classified as ionic solid as graphite
is not made up of ions. It is made up of carbon atoms Radius of tetrahedral void (Rt )  0.225r
covalently bonded to three carbon atoms so, it is a Where, r  radius of bigger atom involved.
covalent solid.
Since, the formation of covalent bond occurs
throughout the crystal therefore, it is a type of
network solid. Due to presence of free electron,
graphite is also classified as conductor solid.
35. (d) The fraction of octahedral or tetrahedral voids
occupied depends upon the radii of the ions present
at the lattice points. As we know the radii of
octahedral or tetrahedral void is related to radii of
angles.
7. (c) For tetrahedral arrangement co-ordination
number is 4 and radius ratio (r /r) is 0.225 

0.414 .
8. (d) If we consider a face–centered particle ' F ' as
shown in the figure then F is connected to 4
particles in its face, 4 particles in the adjacent
faces of unit cell A and 4 particles in the adjacent
faces of unit cell B. So, the number of nearest
neighbour particles =4+4+4=12.
A B
Trick: The coordination number of fcc structure is 12.

1
9. (d)  8 (at corners) =1 3. (c) Number of atoms of A per unit cell
8 = 8  1 (at the corners) =1
8
1  6 (at face centre) =3
Number of atoms of B per unit cell
2
= 1 (at the centre) = 1
Z  1  3  4 (total no. of atoms) Number of atoms of C per unit cell
10. (a) Edge length for different types of unit cells can be
= 12  (at the edge centre) = 3
tabulated as 1
4
So, formula of compound ABC3.
Types of unit cell Edge length
4. (b) Each particle at edge centre is surrounded by four
fcc 2 2r unit cells thus, its contribution to each unit cell is 1/4.
bcc 4
5. (c) 16  r3
3r 3
scc 2r Volume occupied by 1 unit cell  Z  volume of 1 atom
11. (c) Fcc unit cell contains 8 tetrahedral voids at centre of Z  number of atom
each 8 smaller cube of an unit cell as shown below in fcc  Z  4
4 3
1 42  Volume will be  4  r
3 16r3
3  3 .
6. (b) Packing efficiency is the percentage of total filled
Tetrahedral space by particles and it can be calculated as packing
void
efficiency
5 Each cube contain one Volumeoccupied by four spheres in the unit cell
6 
7
8 tetrahedral void at its body Total volumeof unit cell
100
Since, packing efficiency for hcp or ccp is calculated to
Each cube represented centre as shown
by numeric 1, 2, 3, 4, 5, above be 74% which is maximum among all type of crystals.
6, 7, 8 contain one 7. (d) Hexagonal close packing can be arranging by two layers
tetrahedral voids.
A and B one over another which can be diagrammatically
Number of atoms in fcc unit cell = represented as
4 Number of octahedral voids = 4
Number of tetrahedral voids = 8.
B
12. (a) Polonium crystallizes in scc. where a  b  c A
      90º. B
A
13. (c)
A B C
At corner At centre of each face At corner Here, we can see easily that 1st layer and 4th layer are not
1 1 1 exactly aligned.
6 6 2
8 2 8 8. (b) Packing efficiency in different types of unit cells can
3 1 be tabulated as
3
4 4 Unit cell Packing efficiency
3 12 1 74%
fcc
So molecular formula  A3 B12C. 68%
bcc
14. (d) Other than Ag, Pb and Hg also exist as simple cubic. 52%
Simple cubic
Hence, correct order is
3. Crystal Packing
fcc (74%)  bcc (68%) simple cubic(52%) .
1. (d) It represents ccp arrangement. 9. (a) Density is defined as the ratio of mass per unit cell to
2. (b) Every constituent has two tetrahedral voids. In ccp the total volume of unit cell.
lattice atoms No. of particle per unit cell for fcc type lattice . Z  4
1 1 Mass of single atom  ' m '
 6 4
 8 2 Volume of unit cell  a3
 Tetrahedral void  4  2  8 , Z  m 4m
Thus ratio  4 : 8 :: 1 : 2 .   3.
a3 a
r
 1 1
10. (c) When coordination number is eight, the radius ratio 17. (c) fcc  8  6  4

r 8 2
lies between 0.732 to 1.000. 1
bcc  8   11  2 .
11. (d) Number of octahedral sites = Number of sphere in the 8
packing. 18. (b) As ccp Z (effective atoms) = 4
 Number of octahedral sites per sphere = 1. Octahedral voids = 4
1
12. (c) Tetrahedral sites are double comparable to octahedral M occupies half O.V.  4   2 atoms
2
sites then ratio of X and Z respectively 2 : 1 since
Y forms ccp  4 atoms
formula of the compound X2Z .
M2Y4
13. (b) r (i.e., radius of Na)  0.95 Å Hence, MY2.
1
r (i.e. radius of Cl)  1.81 Å 19. (a) Corner 
 r 0.95 8
radius ratio   0.524 1
  1.81
Face  .
 r 2

 Na ions fit in octahedral voids.
14. (b) On removing all the ions lying along the axis 4. Mathematical Analysis of Cubic System and
one Na+
Bragg’s Equation
from centre and 2Cl from face centres are
removed
1. (b) Factual.
1
 No. of Na+  12   3 2. (c) From Bragg’s equation
4
n  2d sin

1 1
Cl  8 4 3. d  ,n  1
8  2 
1  2sin
15. (c) No. of effective particles in hcp lattice 1
sin  
 (6  6)1/6  31 21/2  6 2
1   30o .
No. of particles in 1/2 mole   6.022 1023
2 3. (c) According to, Bragg’s equation,
No. of unit cells in mole  1  6.022 1023 n  2d sin
1 2
6 where,
2
The no. of tetrahedral voids is equal to double the no.
n  Integer and order of the reflection
of particles in a unit cell. Thus the no. of tetrahedral
voids d  Scattering planes have a spacing " d "
1  Wavelength
T  2  6   6.022 1023
26  Angle of incidence
If the angle of incidence of X-ray produces a second order
 6.0221023
diffracted beam from the 100 planes is 30 , hence
The no. of octahedral voids is equal to the no. of
angle of incidence that produce a first order diffracted
particles in a unit cell. Thus the no. of octahedral
beam
voids
O6 1
 6.022 from the 200 plane is also 30 .
 2 1023
6
O  3.0111023 5. Crystal Structure and Coordination Number

Total no. of voids  T  1. (c) As CsCl is body-centred, d  3a / 2 .
O

1
 6.022  1023  3.011 1023 2. (b) In a unit cell, W atoms at the corner   8  1
8
 9.033  1023 . 1
O atoms at the centre of edges 12  3
16. (d) In the cubic close packing the unit cell has 8 4 
tetrahedral voids within it and are located at each
Na atoms at the centre of the cube = 1
eight smaller cube of an unit cell.
W : O : Na  1 : 3 : 1, hence formula =NaWO3 .

3. (b) Total no. of A atoms  8  2  6 10. (a) ZnS has zinc blende structure. It has cubic close
Total no. of B atoms  6 packed (ccp) structure. The S 2 ions are present at
Effective no. of A atoms  61 / 8  3 / 4 the corners of the cube and at the centre of each
Effective no. of B atoms  6 1 / 2  3 face. Zinc ions
Composition per unit cell A : B  3 / 4 : 3  occupy half of the tetrahedral sites. Each zinc ion is
1 : 4 or AB4 . surrounded by four sulphide ions which are disposed
towards the corners of a regular tetrahedron.
4. (b) Radius ratio range 0.732 – 0.99 signifies co- Similarly,
ordination number 8. In CsCl, co-ordination number
S2 ion is surrounded by four Zn2+ ions.
ratio is 8 : 8.
11. (a) In antifluorite structure like Na2O, O2 ions occupy half
5. (a) Co-ordination number in hcp and ccp arrangement is
12 of the cubic holes and Na+ ions occupy all the
while in bcc arrangement is tetrahedral voids. Each, O2 ion is surrounded by 8
8.
6. (c) r  1.46 Na ions and each Na ion is surrounded by 4 O2
c
  0.676
r
a
 2.16 ions. It has 4 : 8 coordination.
It permits co-ordination number 6 and octahedral 12. (d) No. of F will be equal to eight since for one Ca2
structure of type NaCl .
there should be two F  ion.
7. (a) NaCl crystal have rock salt structure having fcc lattice 1 1
13. (b) No. of O2 per unit cell  8   6  4
in which Cl ions are present at fcc lattice points and 8 2
3 1
 No. of Al per unit cell  4   2
face centre and Na occupies all the octahedral void of 2
2 1
given unit cell. No. of Mn per unit cell  8   1
8
Where, Coordination number of Na  6
MnAl2O4 .
Coordination number of Cl  6 .
8. (c) Coordination number in a square closed packed 6. Defects in Crystal
structure in two dimensions is equal to 4 as shown 1. (c) Since no ions are missing from the crystal as a whole,
below there is no effect on density.
AAAA 2. (d) F-centres are the sites where anions are missing and
instead electrons are present. they are responsible for
colour.
3. (b) When group 13 elements are doped in group 14
element, it creates a hole in a molecule but the
Cubic closed structure

molecule as a whole remain neutral. Thus, p -type
9. (b) Position of Cl ions: At the corners (8 nos.) and at the
semiconductor is neutral in
face centres (6 nos.).
nature.
Position of Na ions: At the edge centres (12 nos.) Positive hole (no electron)
and at the body centre (1 no.)
(i) Cl ions are in fcc arrangement.
B
(ii) The Na ion at body centre (X) is surrounded by
6Cl atoms, so the C.N. is 6.
(iii) Any Cl ion (say at Y) is surrounded by 5Na+ atoms in Perfect crystal Perfect crystal
this cell and one more from the adjacent cell. So C.N. 4. (a) Frankel defect is also known as dislocation defect
of Cl is 6. because in Frenkel defect, atoms present in crystal
lattice is dislocated to interstitial site.
(iv) Effective no. of Cl ions  8 1 / 8  61 / 2 
5. (b) Schottky defect is caused if some of the lattice points
4 Effective no. of Na+ ion  121 / 4 11  4 are unoccupied. The points which are unoccupied are
So, each unit cell contains 4NaCl molecules. called vacancies or holes. The number of missing
positive and negative ions is the same keeping the
–
Cl crystal neutral. Cations and anions are of similar size.
Na+ 6. (b) Zinc oxide is white in colour at room temperature. On
heating it loses oxygen and turns yellow
1
X ZnO heating Zn 2  O
 2e
2
Y
2
Now there is excess of zinc in the crystal and its formula

becomes Zn2 ions move to
Zn1 xO . The excess
interstitial sites and the electrons to neighbouring
interstitial sites.
NaCl

7. (d) Schottky defects occurs in highly ionic compounds
which have high co-ordination number examples, 4. (a) r  3a  3  4.29  1.86 Å.
4 4
NaCl,KCl,CsCl .
5. (d) For bcc structure 3a  4r
8. (a) Impurity present in a crystal does not establish
thermal
equilibrium. r
3
a  3  351  152 pm.
9. (b) On adding non-metal in metal the metal becomes less 4 4
tensile. 6.
(c) In CsCl, Cl  lie at corners of simple cube and Cs at the
10. (d) In AgBr both schottky and frenkel defects
body centre. Hence. Along the body diagonal, Cs and
occur simultaneously.
11. (b) Metal deficiency defect occurs when metals show Cl touch each other so.
variable 3a
valency. Examples, Transition metals; FeO, FeS and NiO. r r
  Cs Cl
.
12. (d) To get a n-type semiconductor from silicon, it should 2
7.
(b) In ZnS structure, sulphide ions occupy all fcc lattice
be doped with a substance with valence 5.
points while Zn2+ ions are present in alternate
Examples, Si doped with P lead to formation of n-type
tetrahedral voids.
semiconductor as shown below. 8.
(d) Y X
Mobile electron 2
ccp 8
4
3
As X16 Y4 or X16Y12 or X4Y3 .
do pin g
wi th  3
  
P (valency  5) 9. (b) CsI can be written as Cs+ and I  ions. We know that
3 3
Cs atom contain the octet configuration by removal of

Perfect crystal n-type
one electron. Also I  exist as [I  I  I] .
3
13. (c) KBr exhibits Schottky defect and not Frenkel defect. 10. (d)
14. (d) When electron rich or electron deficient impurity is
added to a perfect crystal it introduces electronic R
defect in them.
15. (b) Silicon doped with electron rich impurity such as
phosphorus forms a n-type semiconductor. This is
L
due to presence of mobile electron.
16. (b) Schottky defect is shown by highly ionic compounds, 4R= L2 ,
examples, NaCl,KCl,KBr, AgBr,CsCl etc.
17. (a) In Schottky defect equal number of cations and so, L= 2 2R
anions
leave the crystal lattice to form equal number of Area of square unit cell = 2R)2  8R 2
cationic (2
and anionic Area of atoms present in one-unit cell
vacancies.  R2 
= R2  4  2R2 .
 4 
7. JEE Mains  
so, packing efficiency
1. (a) Silicon is a covalent crystal in which constituent 
particles are atoms. 2R2 100 = 100  78.54% .
= 8R 2 4
2. (d) The bcc cell consists of 8 atoms at the corners and
one
atom at centre. 11. (d) In fcc lattice effectively 4 atoms remain present in a unit
 1 cell.
 n 8  1
  Total volume of atoms present in a fcc unit cell
2. 8
  16
4 3 3
The fcc cell consists of 8 atoms at the eight corners = 4  r .

3
and one atom at each of the six faces. This atom at r
the face 3
is shared by two unit cells. ZM
12. (a)  

NV
1
 1
 n8  6  4 .
NV 2 6 1023 (5
8  2 Z M  108)3
3. (d) A B
75
1 1 n2
8 5
8 3 3
2 r a  5  2.165 Å = 216.5 pm
Formula of A2 B5 4 4
compound . Note: Answer may be 216 pm or 217 pm.

13. (a) 1
 6.0221023  1.029 1022 23. (b) B forms hcp  No. of B  6
58.5 1
A occupies 1  No. of A  12  4
A unit cell contains 4Na ion and 4Cl ions 3
TV
3
 Formula  A4B6  A2B3
Unit 1.029  2.57 unit cell.

1022 ZM
cell 4 1021
24. (b) d A
14. (c) For fcc, 2a  4R N  a3
a
So, 2R  . M0
4
2 9 10  6 1023 (200  2 1012)3
3
1
15. (b) No. of M atoms  41112
4 M
1 1 4
No. of X atoms   6 8  3  1  4 9 10  6 1023
3
2 8  23  2  2 1030
so, formula  M X  MX
9 103  6 1023  24  2 1030
2 4 2 M
4
16. (d) There were 6 A atoms on the face-centres removing
face-centred atoms along one of the axes means  9  6 10 4
 4 2  0.03 kg .
removal of 2 A atoms. a
25. (d) Rr
Now, number of A atoms per unit cell 2
1 1
8 4 3 3a  4R
8 2
0.5 a  0.433a  r
(corners) (face centred)
r  0.067a .
Number of B atoms per unit
cell 26. (c) Effective number of A4
1 + 14
 12 
4 (body centred)
Effective number of B  4  1  2
(edge centred) 2
Hence the resultant stoichiometry is A3 B4

Effective number of O  8
.
17. (b) In this diagram, equal number of cations Formula A4 B2O8 or A2BO4 .
(Na+) and
is
anions (Cl) are missing, so, it shows schottky 27. (a) Interstitial compound are almost inert so [a] is wrong
defect. statement.
18. (b)
M0.98O 28. (c) 3a  2r  2(2r)  6r
6r
consider one mole of the oxide. a 23r
3
Moles of M  0.98, Moles of O2  1
Let moles of M3  x 4 4
 r3  (2r)3
 Moles of M2  0.98  P.F.  3 3
x a3
 Doing charge balance 4 (r3  8r3)

4 9 r3
(0.98  x) 2  3x  2  0  3  3  8  3 3 r3
(2 3 r)3
1.96  2x  3x  2  0

x  0.04 

  0.906
0.04
 % of M3  100  4.08% . electric current when they are placed under mechanical
0.98 stress.
19. (a) Frenkel defect.
20. (c) Piezoelectric material are those that produce an

23
particles
3
% of packing efficiency  0.906100  90.6% . 10 10
 0.24  a2  N
29. (d) Total area = area covered by one particle  Number of
3 A
21. (c) ZM 4  63.55 10
d or, d  or,
NA  a3 6 1023 (x 108)3
a  21010cm  2pm .
422
d g/mL .
30. (d) The amorphous form of silica is kieselguhr.
x3
22. (b) In Triclinic unit cell 31. (d) Nearest distance between two nearest tetrahedral
voids in a fcc lattice is a/2.
a  b  c and       90o .

1
32. (d) In sc, Z  8   10. (a) For ccp 2a  4R
8 1 Z1
In bcc, Z  8 1 2  408
 12Z  2R (2R = Diameter)
2
2
8
1 1
In fcc, Z  8  6 Diameter = 288.5 pm
4 Z4 .
 11. (c) Distance between centres of cation and anion
8 2
33. (a) Only AgBr can exhibit both Schottky and Frenkel defect. d 508
   254 pm
2 2
8. NEET
rc  ra  254 pm or 110  ra  254 or ra  144 pm .
1. (d) A cube has 6 faces so, it is shared by 6 unit 1
12. (d) A2  82
cells.
3a 4
2. (b) Half of body diagonal, . A2B4O4
2 B  4 1  4
AB2O2
3. (c) scc: a  2r 1 1
O2  8 6 4
bcc: 3a  4r 8  2 
fcc: 2a 
13. (a) Diamond has ZnS type structure. So, no. of atoms in a
4r
unit cell of diamond is 8.
a 3a 2a
: : .
2 4 4 2M
d a33 N 2 b  bcc
a
4. (c) In the diamond cubic unit cell, there are eight corner 14. (c) b
 b A
 
f
3
df 4M f  fcc
atoms, six face centered atoms and four more atoms 3 ab 4
A
inside the structure. af
Number of atoms present in a diamond cubic unit  3 
cell 4r
 
3  

8134 atoms. 1  a f 1 2 
      3 
5. (d)   2   4r  
68%Packing efficiency in bcc lattice  2 ab
  
  
 vacant space in bcc lattice  100  68  3
32%.
6. (c) A ions are at eight corners of the cube. Therefore, the 3
no. 1 3 1  33  33
8        .
of A ions in the unit cell =  1 . B ions are at the 2 2 2  2 4 2
face
8
15. (a) For simple cube radius (r)  a/2
centre of six faces. Therefore, its share in the unit cell
4
= vol.occupied by theatom ina unit r 3
6 cell
 3 . The formula is AB .
 3
3
2 P.F.
 vol.of unit
a3
cell
7. (a) Number of octahedral voids in ccp, is equal to
4  a 3
effective number of atoms. In ccp, effective number   4 a3
of atoms are 4 so, 4 octahedral voids.  
 3 3 2  3 8 
So, 1 octahedral voids per atom. a a3 6
Z. mol wt.
8. (b) In fcc unit cell, 4r  16. (b) Density 
2a [ r  radius of Cu atom,
a3.NA
a  edge length]
Trick: Z for bcc usually 2 but for this case

2  361
So, r  2a  127 pm Z1
4 r
. because 1 bcc has 2 atoms which here means 1 atom of
4
9. (b) If a molecule AB has bcc lattice then cation (or anion) Cs and 1 atom of Br giving a total of 1 molecule and
is at the body centre and anions (or cations) are at Z is the no. of molecule per bcc.
the corners. So, the distance between cation and
1 213
anion is   (4.366 108)3  6.022
3a
1023

2
 4.25 g/cm3.
3  387
  335 pm . Note: If you take Z  2 then answer will be
2 (a) 8.25 g/cm3. which is wrong.

ZM r 0.98  10
10
17. (d)   22. (a) Radii ratio    0.54
for fcc, Z  4
NA  a3 r 1.81 1010
a  404 pm  404  1010 cm
. radii ratio is in between 0.414 to 0.732 so, coordination
2.72 4 number is 6.
 M
6.021023 (404 1010)3
M  27 g mol1 . 23. (b)The Ca2+ ions are arranged in (ccp) arrangement, i.e.
Ca2+ ions are present at all corners and that the
18. (b) ZM centre of each face of the cube. the fluoride ions

NA  a3
occupy all the tetrahedral sites. This is 8 : 4
For bcc structure arrangement i.e., each
Z  2,   530 kg m3  0.530 g cm3 Ca2+ ion is surrounded by 8F ions and each F ion
by four Ca2+ ions.
0.530  2 6.94
24. (c) Frankel defect occurs when the cations are missing
6.02 1023  a3
from their lattice sites, occupy interstitial sites. So, it
is a
a3  4.348 1023
cm3
dislocation defect. Density remains unchanged. Size
of cations should be small (so that it can occupy
a  3.52 108 cm
interstitial sites) as compared to size of anion. So, it is
a  352 pm . not found in halides of alkaline metals.
19. (c) For fcc or ccp
25. (c) In alkali metal halide, if an anion is absent from its
4r  2a lattice site, which is occupied by electron to maintain
4 electrical neutrality. The holes occupied by electrons
n r 3 are called F-centres.
P.E.  3
a3 When the crystal is irradiated with white light, the
trapped electron absorbs some component of white
n  4 ; a  2 2r light for excitation from ground state to the excited
4 state. This gives rise to colour.
4 r
3
P.E. = 3
(2 2r)3 A+ B– A+ B–
P.E. = 74%
B– A+ B– A+
Free space  100  74  26%
For bcc
A+ e– A+ B–
4r  3a F-centre
4
2 r 26. (b) Boron can easily form positive ion. When silicon is
3 doped with boron, it creates a positive hole and the
P.E.  3 substance are called p-type semiconductor.
3
 4r 
 
3 
27. (c) One cation of Sr++ would create one cation vacancy
P.E. = 68% in NaCl therefore the number of cation vacancies
Free space created in
the lattice of NaCl is equal to the number of Sr++ ions
32%.
added. Concentration of cation vacancy on being
20. (a) Difference  2.178 103  2.165 103  0.013 103 doped with
Fr acti on unoccupied

0.013 103 mole% SrCl2 10
4
 2.178 103 3
104   106 mol
 5.96 10 100
r No. of Sr++ ions, in 106 mol  106  6.022 1023

21. (a) Radius ratio of NaCl like crystal 
r 

100  6.022 1017 Sr ions,
r   241.5 pm
0.414
No. of cation vacancies = 6.022 1017 .

28. (ad) 37. (d) Number of A atoms in one unit cell = 6
75
(a) FeO0.98 has a non-stoichiometric metal excess Number of C atoms in one unit cell = 6
100
defect (Compare this molecule with FeO)
36
(d)Frenkel defect is favoured in those ionic  4
compounds if there is a large difference between
sizes of cation
and anions. C:A
29.
(b) As, a  b not  c and alpha =beta not = gamma. 36
 :6  3 : 4
30.
(b) Number of tetrahedral voids in the unit cell 4
= 2  number of atoms = 2Z.  C3 A 4 .
31. (c) AB2 type of structure is present in
CaF2
 AB2
A2  2B CaF2 Ca2  2F 9. Numerical Based Questions
;
32. (a) Ca2+ ions are in fcc arrangement with a coordination 3 30
1. (4) M   a  NA 10
no. of 8. 8 fluoride ions (C.N.= 4) are inside the unit Z
cell and occupy all tetrahedral voids.
10 (100)3 (6.0221023)1030
  15.05
23
6.02210
Ca2+ No. of atoms in 100 g  100  4 1025
15.05
x4
2. (1.2) 2d sin  = n or 2×d × sin 60 = 2×1Å
F − 2 × d × 0.8660 = 2
3
d = 1.15 Å (sin 60 or 0.8660).
2
33. (b) In AgI crystal, number Ag ions is equal to I ions.
+
=
of
However, the number of tetrahedral voids are twice d 1.
the number of atoms forming the cubic lattice.
3. (91) For bcc,
 Number of tetrahedral voids occupied by Ag+ ion 3 2d
d a or a  2  5.219 Å  522pm
= 50%. 2 3 
4.52
1.732
34. (b)
nM ZM 2  39
  
a3  N0 1030 3
a  NA 10 30 (522) (6.022 1023)1030
3
2100 =0.91 g/cm3 = 910 kg m–3= 10 

 (400)3 (6.02 1023)1030  5.188 g/cm3.
  91 kg m3 .
4. (8) Body centered cubic lattice has a co-ordination number 8.
35. (a) NaCl structure Hig h CsCl structure. ZM
(6:6 coord.)  pr essu (8:8 coord.) 5. (7.9) Density,   . For bcc, Z = 2.
 
re

760 K
36. (b) The compound NAa3

Na2O has anti–fluorite structure. The
O2 ions are arranged in ccp arrangement. The Na+ 2  56.0g mol1
Fe   7.9 g cm3
ions occupy all the tetrahedral holes. Since there are 6.023  1023 mol1 10 8
two cm)3
tetrahedral holes for Z
each O2 ion, there will be two 6. (97.8) Theoretical density obtained is with the
by M
Na+ ions for each O2 ion, thus the stoichiometry of ions. Thus the C.N . Of O2 ion is 8 and that of Na
the compound is 2 : 1 . Each O2 ion is surrounded by ion is 4.
–
8Na ions and each Na ion is surrounded by 4O2 O2

NA  V vacancies. The density obtained considering
assumption that each lattice point is occupied by vacancies is called observed density and is surely less
the constituent particles due to some defect in than the theoretical density.
the crystal lattice. These points are called Theoretical density
3
Na+ 2  7  10
  5.42  102 kg
m3 6.023  1023 (3.5  1010)3
Observed density
% occupancy  100
Theoretical density
5.3  102  100  97.78%

%  5.42 
Na2O occupancy 102
9

7. (1.5) The density of crystal is unaffected due to Frenkel 10. (1.2)NaCl crystallizes in the face-centred cubic unit cell, such
defect as the atom only occupies an interstitial a
that r  r 
position instead of lattice site while Schottky defect
Na  Cl 
changes the density of crystal. 2
Where a is the edge length of unit cell.
The density of crystal containing 0.1% Frenkel Now, since  /  =0.5 and r  / r   0.7
defects, r r
would thus Na Cl Na K
be 4  40 rr
ZM
  Na Cl
 1.5
NA  a3 6.023 1023 (0.556 107)3 r

  1.5455 g/cm3  1.5 r
C
r
1 1
8. (26) No. of atoms per unit cell is: 8 6 4 0.5 0.5
rK 
K/ 0.5   / r  0.7 ;
   rCl Na
r Na K
8 2
rr 1.2 1
Moreover, atoms touch each other along the faces of K Cl
 
the
r   r  0.7 1.5
cube. Hence 4r  2a Na Cl
 4r  3
aKCl /2 1.2 ; aKCl 1.2  1.143
Now, volume of unit cell  a3   16 2r 2 a / 2
0.7 1.5 a  1.05
 NaCl NaCl
2 ZM
4 3 Now since,  
Volume occupied by atoms  4 r  3 
a N A
 3 
 We will have
4
4 r 3

 3 
NaCl
  KCl 3  NaCl  (1.143)3    1.172
  aa M
M 74.5
16 2r 3 32
KCl  NaCl   KCl   
   1.2
Percentage of void volume  1 3 2 100  26%
  
11. (26.1) In case of hcp unit cell, there are 6 atoms per unit
cell. If the radius of metal atom is r1 then
9. (22.4) Anions form hexagonal closest packing and cations Volume occupied by the metal atom
occupy only two thirds of octahedral holes 22
 6  4r3  6 1.33   r3  25.08 r3
Volume of hexagon  24 2r 3 3 7
There are six anions and six cations per unit cell It has been shown geometrically that the base area of hep
Fraction of volume occupied per unit volume of unit 3
unit cell  6 4 r2
cell is 4

  3

 1 2  cr   3.1416 1  20.414   And the height  4r  2 / 3
   or    Volume of unit cell = Area × Height



3  ra  3 1.414  3 
2 2  3
 6  4  r 2  4r   33.94r3
r 2/3
hedral holes, c  0.414] 4
[ for ra
Volume of the empty space of one-unit cell
 = 0.7756
 33.94 r 3  25.08 r 3  8.86 r 3
 volume of void = 1 –  = 1 – 0.7756 =0.2244/unit
volume of unit cell 8.86 r 3
Hence percentage void  100 or 26.1
 % void = 22.44%  33.94 r
3
22.4

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17.

Crystalline Solids Amorphous Solids

Table: Difference between Quartz and Amorphous Silica

Quartz Amorphous Silica

It is crystalline in nature. It is light (fluffy) white powder.

give a network solid polymeric chains, sheets or three-dimensional units.

Chemistry Solid State | 1

2.4. Classification of Crystalline Solids

Types of Physical Electrical

SiO2 (Quartz), SiC,

I2, S8, P4, CO2, CH4, Low

Cations in a sea of Sodium , Au, Cu, High High

Poor thermal and

3. Space Lattice (Crystal Lattice) and Unit cell

Chemistry Solid State | 2

Table: Bravais Lattices Corresponding to Different Crystal Systems

Chemistry Solid State | 3

(3) Centre of Symmetry

Chemistry Solid State | 4

Chemistry Solid State | 5

7.1. Number of Atoms Per Unit Cell

No. of effective atoms N nc n f  ne ni

ne  Number of atoms at twelve edge centers of the cube

Table: Effective number of Atoms per Unit Cell

Cubic Unit Cell nc nf ne ni Neff

7.2. Co-ordination Number (C.N.)

7.3. Density of the Unit Cell ()

Where Z = Number of particles per unit cell M =

Atomic mass or molecular mass (g/mol) N A 

Avogadro number (6.023 1023mol1)

Volume of the atom (spherical) v  4 r 3

Chemistry Solid State | 6

Structure r related to a Volume of the atom (v) Packing density % of void

Face-centred cubic a 4a

8. Close Packing in Crystalline Solids

Fig: Square Close Packing Fig: Hexagonal Close Packing

(1) Square Close Packing

Chemistry Solid State | 7

(3) Body Centred Cubic

Table: Comparison of hcp, ccp and bcc

Property hcp ccp bcc

Arrangement of packing Close packed Close packed Not close packed

Type of packing AB AB A... ABC ABC A... AB AB A...

Available space occupied 74% 74% 68%

Chemistry Solid State | 8

10. Radius Ratio

Chemistry Solid State | 9

Table: Types of Ionic Crystal with Description

Crystal Brief description Examples Co-ordination Number of

four S2− ions and vice versa. S2  4

Fluorite (CaF2) fcc with each Ca2+ ions surrounded by 8F  SrCl2,CdF2,PbF2

12. Spinel and Inverse Spinel Structure

13. Defects or Imperfections in Solids

Chemistry Solid State | 10

Fig: Frenkel Defect

 Metal Excess Defects

(a) Metal Excess Defects Due to Anion Vacancies A+ B– A+ B–

Chemistry Solid State | 12

14. Electrical Properties of Solids

14.1. Types of Solids

range 104  106 ohm1cm1 .

Chemistry Solid State | 13

 Extrinsic Semiconductors or Doping