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SECTION A
1.1 Define the term ‘amorphous’. Give a few 1.2 What makes a glass different from a solid such
examples of amorphous solids. as quartz? Under what conditions could quartz
Sol. Amorphous solids are those substances, in be converted into glass?
Sol. Glass is made up of SiO4 tetrahedral units. These
which there is no regular arrangement of its
constituent particles have short range order only.
constituent particles, (i.e., ions, atoms or Quartz is also made up of SiO4 tetrahedral units.
molecules). The arrangement of the constituting On heating it softens and melts over a wide range
particles has only short range order, i.e., a regular
and periodically repeating pattern is observed
over short distances only, e.g., glass, rubber and
i r
of temperature. It is a crystalline solid having
long range ordered structure. It has a sharp
melting point.
Quartz can be converted into glass by first
plastics.
S
melting and then rapidly cooling it.
1.3 Classify each of the following solids as ionic, metallic, molecular, network (covalent) or amorphous:
(i) Tetra phosphorus decoxide (P4O10)
(ii) Ammonium phosphate, (NH4)3PO4
(iii) SiC
(iv) I2 A G (vii) Graphite
(viii) Brass
(ix) Rb
(x) LiBr
(v) P4 (xi) Si
(vi) Plastics
Sol. Ionic Metallic Molecular Network Amorphous
(covalent)
(NH4)3PO4 Brass P4O10 Graphite Plastics
LiBr Rb I2 SiC
P4 Si
1.4 (i) What is meant by the term ‘coordination Sol. Let the edge length of a unit cell = a
number’? Density = d
(ii) What is the coordination number of atom Molar mass = M
(a) in a cubic close packed structure? Volume of the unit cell = a3
(b) in a body centred cubic structure? Mass of the unit cell
Sol. (i) The number of nearest neighbours of a = No. of atoms in unit cell × Mass of each atom
particle are called its coordination number. = Z×m
(ii) (a) 12 (b) 8 Mass of an atom present in the unit cell
1.5 How can you determine the atomic mass of an
M
unknown metal if you know its density and the =m =
dimensions of its unit cell? Explain. Na
2 Chemistry
aligned. If we continue packing in this
Mass of unit cell Z ×m Z ×M
\ d= = 3 = 3 manner, then the packing obtained would be
Volume of unit cell a a Na called ABAB....... pattern or hexagonal close
d × a3 × Na packing.
\ Atomic mass, M = (ii) Crystal lattice: It is a regular arrangement
Z of the constituent particles (i.e., ions, atoms
1.6 ‘Stability of a crystal is reflected in the or molecules) of a crystal in three
magnitude of its melting points’. Comment. dimensional space.
Collect melting points of solid water, ethyl Unit cell: The smallest three dimensional
alcohol, diethyl ether and methane from a data portion of a complete space lattice which
book. What can you say about the intermolecular when repeated over and over again in
forces between these molecules? different directions produces the complete
Sol. Higher the melting point, greater are the forces crystal lattice is called the unit cell.
holding the constituent particles together and (iii) Tetrahedral void: A simple triangular void in
thus greater is the stability of a crystal. Melting a crystal is surrounded by four spheres and
points of given substances are following. is called a tetrahedral void.
Solid water = 273 K, Ethyl alcohol = 155.7 K,
Octahedral void: A double triangular void is
Diethylether = 156.8 K, Methane = 90.5 K.
surrounded by six spheres and is called a
The intermolecular forces present in case of water
octahedral void.
and ethyl alcohol are mainly due to the hydrogen
bonding which is responsible for their high 1.8 How many lattice points are there is one unit
melting points. Hydrogen bonding is stronger in
case of water than ethyl alcohol and hence water
has higher melting point then ethyl alcohol.
i r
cell of each of the following lattices?
(i) Face centred cubic
(ii) Face centred tetragonal
Dipole-dipole interactions are present in case of
diethylether. The only forces present in case of
methane is the weak van der Waal’s forces (or
Sol. S
(iii) Body centred cubic
(i, ii) Lattice points in face centred cubic
London dispersion forces).
A
1.7 How will you distinguish between the following
pairs of terms:
(i) Cubic close packing and hexagonal close
G and face centred tetragonal
= 8 (at corners) + 6 (at face centres) = 14
(iii) Lattice points in body centred cubic
= 8 (at corners) + 1 (at body centre) = 9
packing? 1.9 Explain:
(ii) Crystal lattice and unit cell? (i) The basis of similarities and differences
(iii) Tetrahedral void and octahedral void? between metallic and ionic crystals.
Sol. (i) Cubic close packing: When the third layer (ii) Ionic solids are hard and brittle.
is placed over the second layer in such a Sol. (i) Metallic and ionic crystals
way that the spheres cover the octahedral Similarities:
voids, a layer different from first (A) and
(a) There is electrostatic force of attraction in
second (B) is produced. If we continue
both metallic and ionic crystals.
packing in this manner, then a packing is
obtained where the spheres in every fourth (b) Both have high melting points.
layer will vertically aligned. This pattern of (c) Bonds are non-directional in both the cases.
packing spheres is called ABCABC..... Differences:
pattern or cubic close packing. (a) Ionic crystals are bad conductors of
Hexagonal close packing: When a third layer electricity in solids state as ions are not free
is placed over the second layer in such a to move. They can conduct electricity only
manner that the spheres cover the in the molten state or in aqueous solution.
tetrahedral void, a three dimensional close Metallic crystals are good conductors of
packing is obtained where the spheres in electricity in solid state as electrons are free
every third or alternate layers are vertically to move.
Solid State 3
(b) Ionic bond is str ong due to strong No. of spheres per unit cell = 2
electrostatic forces of attraction. 4 8
Metallic bond may be strong or weak \ Volume of two spheres = 2 × pr 3 = pr 3
3 3
depending upon the number of valence \ Packing efficiency
electrons and the size of the kernels. 8 3 pr 3
(ii) Ionic solids are hard and brittle. Ionic solids = = 0.68, i.e., 68%
64r 3 3 3
are hard due to the presence of strong
(iii) In fcc: Let the edge length of unit cell = a
electrostatic forces of attraction. The A a
brittleness in ionic crystals is due to the non-
directional bonds in them. B
C
1.10 Calculate the efficiency of packing in case of a
metal crystal for (i) simple cubic, (ii) body centred
fcc
cubic, and (iii) face centred cubic (with the
assumptions that atoms are touching each Let the radius of each sphere = r
other). \ length of face diagonal AC = 4r
Sol. Packing efficiency: It is the percentage of total From right angled triangle ABC,
space filled by the particles. AC = AB2 + BC2 = a 2 + a2 = 2a2 = 2a
(i) In simple cubic lattice :
Let the edge length of the cube be ‘a’ and A
Top
the radius of each particle be ‘r’.
\ a = 2r
No. of spheres per unit cell = 1
i
a
r view
Volume of the occupied unit cell = pr 3

Volume of cube = a3 = (2r)3 = 8r3
4
3
\
S B
a C
\ Packing efficiency =
volume of
one particle
volume of cubic A G \
4r
2
a=
2a = 4r
unit cell \ Volume of the unit cell

4 / 3 pr 3 æ 4 ö
3
64r 3
=
8 r3
= 0.524, i.e., 52.4%. = a3 =
ç r÷ = = 16 2r 3
è 2 ø 2 2
(ii) In bcc : Length of body diagonal AD = 4r
No. of unit cell in fcc = 4
C
A 4 16
B \ Volume of four spheres = 4 × πr3 = πr3
3 3
D \ Packing efficiency
16pr 3 / 3
From right angled triangle ABC, = = 0.74, i.e., 74%
16 2 r 3
AC= AB2 + BC2 = a 2 + a 2 = 2a
1.11 Silver crystallises in fcc lattice. If edge length of
Body diagonal, AD the cell is 4.07 × 10–8 cm and density is 10.5 g
= AC2 + CD2 = 2a 2 + a 2 = 3a 2 = 3 a cm–3, calculate the atomic mass of silver.
\ 3 a = 4r a = 4r 3 d × a3 × Na 10.5 ´ (4.07 ´ 10 -8 )3 ´ 6.023 ´ 10 23
Sol. M = =
3 Z 4
æ 4r ö 64r 3
\ Volume of unit cell = a3 = çè ÷ø = = 106.5 g mol–1.
3 3 3
4 Chemistry
1.12 A cubic solid is made up of two elements P and ( 2 R )2
Q. Atoms of Q are at the corners of the cube Þ = (R + r)2
and P at the body centre. What is the formula of 2
the compound? What are the coordination ( 2 R ) = ( R + r )2
2
numbers of P and Q? Þ 2 R=R+r

Sol. As atoms Q are present at the eight corners of
r= 2 R–R
the cube, therefore, the contribution of atoms of
r = R ( 2 - 1)
1
Q in the unit cell = ´ 8 = 1 . r = R (1×414 – 1)
8
As atom P is present at the body centre, therefore, r = 0×414 R
the contribution of atoms of P in the unit cell = 1. 1.15 Copper crystallises into a fcc lattice with edge
\ Ratio of atoms of P : Q = 1 : 1 length 3.61 × 10–8 cm. Show that the calculated
Hence, the formula of the compound = PQ density is in agreement with its measured value
The coordination number of both P and Q = 8. of 8.92 g cm–3.
1.13 Niobium crystallises in a body centred cubic Z´M
Sol. d =
structure. If density is 8.55 g cm–3, calculate a3 ´ N a
atomic radius of niobium, using its atomic mass
93u.
4 ´ 63.5
= -8 3
Sol. Density of Niobium (d) = 8.55 g cm–3 (3.61´10 ) ´ 6.023 ´1023
Atomic mass (M) = 93 g mol –1 {Atomic mass (M) = 63.5 for Cu}
As the lattice is bcc type, the number of atoms
per unit cell, Z = 2
i r
= 8.96 g cm–3.
This calculated value of density is closely in
\ d=
ZM
a3 N A S
agreement with its measured value of 8.92 g cm3.
1.16 Analysis shows that nickel oxide has the formula
Ni0.98O1.00. What fractions of nickel exist as
a3 =
M ×Z
=
93 ´ 2
G
d × N a ´ 10 -30 8.55 ´ 6.02 ´ 1023 ´ 10 -30
= 3.61 × 107 A
Ni2+ and Ni3+ ions?
Sol. The formula Ni0.98O1.00 implies that 98 Ni atoms
are associated with 100 O atoms.
Let out of 98 Ni atoms present, x atoms are present
\ a = (3×61 × 107)1 / 3 = (36×1 × 106)1 / 3 as Ni2+ ions and (98 – x) are present as Ni3+ ions.
= 3×304 × 102 pm = 330×4 pm \ Total charge on x Ni2+ ions and (100 – x) Ni3+
1.14 If the radius of the octahedral void is r and radius ions should balance the charge on 100 O2– ions.
of the atoms in close-packing is R, derive Hence, x × 2 + (98 – x) × 3 = 100 × 2
relation between r and R. 2x + 294 – 3x = 200 x = 94.
Sol. A sphere is fitted into the octahedral void as \ Fraction of Ni atoms present as
shown in the diagram. 94
Ni2+ = × 100 = 95.92%
DABC is a right angled triangle. 98
and fraction of Ni atoms present as
98 - 94 4
Ni3+ = ´ 100 = × 100 = 4.081%.
r Ar 98 98
R R
1.17 What is a semiconductor? Describe the two main
BR RC types of semiconductors and contrast their
conduction mechanism.
\ BC2 = AB2 + AC2
Sol. Semiconductors are those substances whose
(2R)2 = (R + r)2 + (R + r)2
conductance lies between that of conductors and
(2R)2 = 2 (R + r)2 insulators. Semiconductor are of two types:
Solid State 5
(a) n-type: When group 14 elements like Cu2O shows that some cuprous (Cu+) ions have
silicon and germanium (having four been replaced by cupric (Cu2+) ions. In order to
electrons in the valence shell) are doped maintain electroneutrality, every two (Cu+) ions
with group 15 element like phosphrous or will be replaced by one Cu2+ ion thereby, creating
arsenic (having five electrons in the a hole. As the conduction will be due to the
valence shell), few lattice sites in Si or Ge presence of these positive holes, hence it is a
are substituted by atoms of P or As. As p-type semiconductor.
group 15 atoms have five electrons in the 1.19 Ferric oxide crystallises in a hexagonal close
valence shell, after forming four covalent packed array of oxide ions with two out of every
bonds with neighbouring four Si atoms, three octahedral holes occupied by ferric ions.
fifth extra electron is free and gets Derive the formula of the ferric oxide.
delocalized. These delocalized electrons Sol. Let the number of oxide ions (O2–) in the packing
increases the conductivity of Si or Ge. As
=x
the increase in conductivity is due to the
negatively charged electrons, the silicon \ Number of octahedral voids = x
or ger m a n i um cr ysta l s dop ed wit h As out of every three octahedral holes, two are
electron-rich impurities are called n-type occupied by ferric ions, therefore, the number of
semiconductors. 2 2x
(b) p-type : When group 14 elements like silicon ferric ions present = ´x=
3 3
or germanium, having four electrons in the
valence shell, is doped with group 13 2x
elements like boron, aluminium or gallium,
few sites of Si or Ge atoms are substituted
by atoms of B, Al or Ga. As group 13 atoms
i r
\ Ratio of Fe+3 : O2– =
3
: x 2x : 3x = 2 : 3
Hence, the formula of ferric oxide is Fe2O3.

have three electrons in the valence shell,
they form three covalent bonds with the
neighbouring three Si or Ge atoms. Thus, a
S
1.20 Classify each of the following as being either a
p-type or n-type semiconductor:
(i) Ge doped with In (ii) B doped with Si.
hole is created at the site where fourth
A G
electron is missing (called electron hole or
electron vacancy). As electron from the
neighbouring atom can jump to fill up this
Sol. (i) In belongs to group 13, hence an electron
deficient hole is created and therefore, it is a
p-type semiconductor.
(ii) B belongs to group 13 and has 3 electrons in
electron hole than a hole is created at the
site from where electron has jumped. As valence shell. When doped with Si, having
this continues, the electron holes will move 4 electrons in valence shell an electron
in a direction opposite to that of the flow deficient hole is created and therefore, in this
of electrons. When electricity in applied, case also a p-type semiconductor is formed
the electrons move towards the postively 1.21 Gold (atomic radius = 0.144 nm) crystallises in
charged plate and electron holes move a face centred unit cell. What is the length of a
towards the negatively charged plate as if side of the cell?
they carry positive charge. Hence, electron
deficit doped Si or Ge are called p-type Sol. In case of fcc, a = 2 2r = 2 × 1×414 × 0×144 nm
semiconductors. = 0×407 nm
1.18 Non-stoichiometric cuprous oxide, Cu2O can be Hence, length of a side of the cell = 0.407 nm
prepared in the laboratory. In this oxide, copper
1.22 In terms of band theory, what is the difference
to oxygen ratio is slightly less than 2 : 1. Can
you account for the fact that this substance is a (i) between a conductor and an insulator.
p-type semiconductor? (ii) between a conductor and a semiconductor?
Sol. The stoichiometric ratio slightly less than 2 : 1 in Sol. (i) In case of conductor, the energy gap between
the valence band and the conduction band
6 Chemistry
is very small or there is overlapping between occupied by electrons are called F-centres.
valence and conduction band whereas in Alkali halides like NaCl, KCl and LiCl show
case of insulator the energy gap between this type of defect.
the valence band and the conduction band 1.24 Aluminium crystallises in a cubic close–packed
is very large. structure. Its metallic radius is 125 pm.
(ii) In case of conductor, there is very small (i) What is the length of the side of the unit
energy gap or there is overlapping between cell?
valence and conduction band but in a (ii) How many unit cells are there in 1.00 cm3
semiconductor there is always a small energy of aluminium?
gap between valence and conduction band. Sol. Aluminium crystallises in ccp structure which is
1.23 Explain the following terms with suitable same as fcc structure.
examples: (i) For fcc, a = 2 2r
(i) Schottky defect (ii) Frenkel defect
= 2 × 1×414 × 125 pm = 354 pm
(iii) Interstitials and (iv) F-centres
Sol. (i) Schottky defect occurs when a pair of ions (ii) Volume of one unit cell = a3 = (354 × 10–12 m)3
of opposite charges, i.e., cations and anions, = (354 × 10–10 cm)3
are equally missing from the ideal lattice. In = 4.44 × 10–23 cm3
NaCl, there are approximately 106 schottky
1
pairs per cm3 at room temperature. There is
one schottky defect for 1016 ions. The
presence of a large number of schottky
i r
Number of unit cells in 1 cm3 =
4.44 ´10-23
= 2×25 × 1022.
defects in a crystal lowers its density.
Schottky defect is shown by ionic
substances in which cation and anion are of
S
1.25 If NaCl is doped with 10–3 mol % SrCl2, what is
the concentration of cation vacancies?
CsCl and AgBr.

A G
almost similar sizes. For example, NaCl, KCl,
(ii) Frenkel defects is a combination of two basic

Sol. Doping of NaCl with 10–3 mol % SrCl2 means that
100 moles of NaCl are doped with 10–3 mol of
SrCl2.
types of point defects : Schottky and
\ 1 mole of NaCl is doped with SrCl 2
interstitial. It occurs when an ion leaves its
position in the lattice and occupies an 10 -3
= mole = 10–5 mole.
interstitial site leaving a gap in the crystal. It 100
is shown by ionic substances having large Each Sr 2+ introduces one cation vacancy,
difference in the size of oppositly charged therefore, concentration of cation vacancies
ions, For example, ZnS, AgCl, AgBr and AgI
= 10–5 × NA
due to small size of Zn2+ and Ag+ ions. It
may be noted that AgBr shows both Frenkel = 10–5 mol × 6×023 × 1023 mol–1 = 6×023 × 1018 .
as well as schottky defects. 1.26 Explain the following with suitable examples:
(iii) Interstitials are the atoms or ions which (i) Ferromagnetism
occupy the normally vacant interstitial sites (ii) Paramagnetism
in a crystal. Non ionic solids are examples of (iii) Ferrimagnetism
this defect. The density of a substance (iv) Anti-ferromagnetism
increases because of this defect. (v) 12-16 and 13-15 group compounds
(iv) When there is an excess of metal ions in non-
Sol. (i) Ferromagnetism is the phenomenon shown
stoichiometric compounds, the crystal lattice
has vacant anion sites. These sites are by substances which are strongly attracted
occupied by electrons. The anion sites by magnetic field. These substances show
Solid State 7
magnetism even in the absence of a magnetic (iv) Anti-ferromagnetism is the phenomenon
field. Examples are Fe, Co, Ni and CrO2. shown by substances in which equal number
(ii) Paramagnetism is the phenomenon shown of magnetic moments are aligned in opposite
by substances which are attracted by a directions so as to give net zero magnetic
magnetic field but they lose their magnetism moment.
in the absence of a magnetic field. Examples are MnO, MnO2 and Mn2O3.
Examples are Cu2+, Fe3+, O2, NO and CuO. (v) 12-16 compounds : Compounds formed
(iii) Ferrimagnetism is the phenomenon shown between elements of group 12 and group 16
by substances in which the number of are called 12-16 compounds e.g., ZnS, HgTe,
magnetic moments aligned in parallel and CdSe, etc.
antiparallel directions are unequal in 13-15 compounds : Compounds formed
numbers. Examples are Fe3O4 and ferrites of between elements of group 13 and group 15 are
formula MFe2O4, where M = Mg, Cu and Zn. called 13-15 compounds e.g., GaAs, AlP, etc.
1.1. Why are solids rigid? cleavage property?

Ans. The constituent particles in solids have fixed Ans. As the solid has same value of refractive index
positions and can oscillate about their mean
positions. Hence, they are rigid.
i r
along all directions, it is isotropic in nature and
hence the solid is amorphous. Being amorphous
solid, it will not show a clean cleavage and when
1.2. Why do solids have a definite volume?
Ans. The constituent particles of a solid have fixed
positions and are not free to move about, i.e.,
S
cut, it will break into pieces with irregular
surfaces.
1.6. Classify the following solids in different
definite volume.
1.3. Classify the following as amorphous or
A G
they possess rigidity. That is why they have
crystalline solids: Polyurethane, naphthalene,

categories based on the nature of
intermolecular forces operating in them:
Potassium sulphate, tin, benzene, urea,
ammonia, water, zinc sulphide, graphite,
benzoic acid, teflon, potassium nitrate, rubidium, argon, silicon carbide
cellophane, polyvinyl chloride, fibre glass, Ans. Potassium sulphate = Ionic
copper Tin = Metallic
Ans. Crystalline solids: Benzoic acid, potassium Benzene = Molecular (non-polar)
nitrate, copper, naphthalene. Urea = Molecular (polar)
Amorphous solids: Polyurethane, teflon, Ammonia = Molecular (H-bonded)
cellophane, polyvinyl chloride, fibre glass. Water = Molecular (H-bonded)
1.4. Why is glass considered a supercooled liquid? Zinc sulphide = Ionic
Ans. Glass is an amorphous solid. Like liquids, it has Graphite = Covalent or network solid
a tendency to flow, though very slowly. This Rubidium = Metallic
can be seen from the glass panes of windows or Argon = Molecular (non-polar)
doors of very old buildings which are thicker at Silicon Carbide = Covalent
the bottom than at the top. Therefore, glass is 1.7. Solid A is a very hard electrical insulator in
considered as a supercooled liquid. solid as well as in molten state and melts at
extremely high temperature. What type of solid
1.5. Refractive index of a solid is observed to have
is it?
the same value along all directions. Comment
Ans. It is a covalent or network solid.
on the nature of this solid. Would it show
8 Chemistry
1.8. Ionic solids conduct electricity in molten state 1.14. What is the two dimensional coordination
but not in solid state. Explain number of a molecule in square close-packed
Ans. In solid state, the ions cannot move, they are layer?
held by strong electrostatic forces of attraction. Ans. In two dimensional, square close packed layer,
So, ionic solids do not conduct electricity in an atom touches 4 nearest neighbouring atoms.
solid state. However, in the molten state, they Hence, its coordination number is 4.
dissociate to give free ions and hence conduct
1.15. A compound forms hexagonal close-packed
electricity.
structure. What is the total number of voids in
1.9. What type of solids are electrical conductors,
0.5 mol of it? How many of these are tetrahedral
malleable and ductile?
voids?
Ans. Metallic solids
1.10. Give the significance of a ‘lattice point’. Ans. No. of atoms in close packing = 0.5 mol
Ans. Each lattice point represents one constituent = 0.5 × 6.022 × 1023
particle of the solid. This constituent particle = 3.011 × 1023
may be an atom, a molecule or an ion. No. of octahedral voids
1.11. Name the parameters that characterise a unit = No. of atoms in packing
cell. = 3.011 × 1023
Ans. A unit cell is characterized by following
No. of tetrahedral voids
parameters :
= 2 × No. of atoms in packing
(i) The dimensions of unit cell along three
edges: a, b and c.
(ii) The angles between the edges: a (between
b and c); b (between a and c) and g
i r = 2 × 3.011 × 1023 = 6.022 × 1023
Total no. of voids
= 3.011 × 1023 + 6.022 × 1023
(between a and b)
1.12. Distinguish between
(i) Hexagonal and monoclinic unit cells
S = 9.033 × 1023
1.16. A compound is formed by two elements M and
(ii) Face-centred and end-centred unit cells.

Ans. (i) Hexagonal unit cell
a=b¹c
Monoclinic unit cell
a¹b¹c A G N. The element N forms ccp and atoms of M
occupy 1/3rd of tetrahedral voids. What is the
formula of the compound?
Ans. Atoms of N form ccp, therefore, if the lattice
a = b = 90° a = g = 90°
g = 120° b ¹ 90° points are n, then
(ii) Face-centred unit cell End-centred unit cell Number of atoms of N = n
has particles at the has particles at the Number of octahedral voids = n
corners and one particle corners and one particle Number of tetrahedral voids = 2n
at the centre of each face. each at the centre of
1
any two opposite faces. The number of atoms M = ´ tetrahedral voids
1.13. Explain how much portion of an atom located at 3
(i) corner and (ii) bodycentre of a cubic unit cell 1 2n
is part of its neighbouring unit cell. = ´ 2n =
3 3
Ans. (i) An atom at the corner is shared by eight
adjacent unit cells. Hence, portion of the Ratio of number of M to that of N =
atom at the corner that belongs to one unit 2
1 = n :n
cell = 3
8
(ii) An atom at the body centre is not shared = 2n : 3n
by any other unit cell. Hence, it belongs =2:3
fully to unit cell i.e. its contribution to unit Thus the formula of compound is M2N3
cell is 1.
Solid State 9
1.17. Which of the following lattices has the highest 1.21. Explain how vacancies are introduced in an ionic
packing efficiency (i) simple cubic (ii) body- solid when a cation of higher valence is added
centred cubic and (iii) hexagonal close-packed as an impurity in it.
lattice? Ans. Let us take an example where NaCl is doped with
Ans. Packing efficiency of : SrCl2 impurity. When SrCl2 is added to NaCl solid
as an impurity, two Na+ ions will be replaced and
Simple cubic = 52.4%
one of their sites will be occupied by Sr2+ while
bcc = 68% the other will remain vacant. Thus, we can say
hcp = 74% that when a cation of higher valence is added as
\ hcp lattice has the highest packing efficiency. an impurity to an ionic solid, two or more cations
1.18. An element with molar mass 2.7×10–2 kg mol–1 of lower valency are replaced by a cation of
forms a cubic unit cell with edge length 405 higher valency to maintain electrical neutrality.
pm. If its density is 2.7 × 103 kg m–3 , what is the Hence, some cationic vacancies are created.
nature of the cubic unit cell? 1.22. Ionic solids, which have anionic vacancies due
to metal excess defect, develop colour. Explain
Ans.
Z ´M with the help of a suitable example.
d= Ans. Let us take an example of NaCl. When NaCl
a3 N A
crystal is heated in presence of Na vapour, some
Given: Density, d = 2.7 × 103 kg m–3
a = 405 pm
= 405 × 10–12 m
r
Cl– ions leave their lattice sites to combine with
Na to form NaCl. The electrons lost by Na to
i
form Na+ (Na+ + Cl– ® NaCl) then diffuse into
d a3 N A
M = 2.7 × 10–2 kg mol–1
S
the crystal to occupy the anion vacancies. These
sites are called F-centres. These electrons
absorb energy from visible light, get excited to
ÞZ=
=
M
A G
(2.7 ´ 103 ) (405 ´10 -12 )3 (6.022 ´10 23 )
higher energy level and when they fall back to
ground state, they impart yellow colour to NaCl
crystal.
2.7 ´ 10-2 1.23. A group 14 element is to be converted into
= 4.004 ; 4 n-type semiconductor by doping it with a suitable
Therefore, it is a fcc unit cell. impurity. To which group should this impurity
1.19. What type of defect can arise when a solid is belong?
Ans. Impurity from group 15 should be added to get
heated? Which physical property is affected by
n-type semiconductor.
it and in what way?
1.24. What type of substances would make better
Ans. When a solid is heated, vacancy defect is
permanent magnets, ferromagnetic or
produced in the crystal. On heating, some atoms ferrimagnetic. Justify your answer.
or ions leave the lattice site completely, i.e., lattice Ans. Ferromagnetic substances make better
sites become vacant. As a result of this defect, permanent magnets. This is because when
density of the substance decreases. placed in magnetic field, their domains get
1.20. What type of stoichiometric defect is shown by: oriented in the directions of magnetic field and a
(i) ZnS (ii) AgBr strong magnetic field is produced. This ordering
Ans. (i) ZnS shows Frenkel defect of domains persists even when external magnetic
(ii) AgBr shows Frenkel as well as Schottky field is removed. Hence, the ferromagnetic
defect. substance becomes a permanent magnet.
10 Chemistry
SECTION B
VERY SHORT ANSWER QUESTIONS (Atomic mass of Nb = 93 u; NA = 6.02 × 1023

mol–1)
1. Define the ‘forbidden zone’ of an insulator.
OR
[All India 2008] Explain with suitable examples the following :
2. What is the coordination number of each (a) n-type and p-type semiconductors
type of ions in a rock-salt type crystal (b) F-centres
structure? [Delhi 2008] (c) Ferromagnetism [All India 2008]
3. Which point defect in crystals of a solid does 2. What is a semiconductor? Describe the two main
not change the density of the solid? types of semiconductors and explain
[Delhi 2009, 2010] mechanisms for their conduction. [Delhi 2008]
4. Write a distinguishing feature of metallic solids. 3. The density of copper metal is 8.95 g cm–3. If
[All India 2010] the radius of copper atom is 127.8 pm, is the
5. What type of semiconductor is obtained when copper unit cell a simple cubic, a body centred
silicon is doped with arsenic? [All India 2010] cubic or face centred cubic structure (Given
6. What type of interactions hold the molecules atomic mass of Cu = 63.54 g mol –1 and
together in a polar molecular solid? NA = 6.02 × 1023 mol–1)
[All India 2010, Delhi 2010]
7.
[All India 2010]
How do metallic and ionic substances differ in
conducting electricity? [Delhi 2010]
4.
i r
Silver crystallises with a face-centered cubic unit
cell. Each side of unit cell has length of 409 pm.
What is the radius of an atom of silver?
8.
9.
‘Crystalline solids are anisotropic in nature’.
What does this statement mean? [Delhi 2011]
How can the conductivity of an intrinsic semi-
5. S [All India 2010, 2009]
How are the following properties of crystals
affected by schottky and Frenkel defects?
10.
conductor be increased?
A G
[All India 2012]
How many atoms constitute one unit cell of a
face-centered cubic crystal? [Delhi 2013] 6.
(i) Density
(ii) Electrical conductivity[Delhi 2009, 2010]
A well known mineral fluorite is chemically
calcium fluoride. It is known that in one unit cell
11. What type of stoichiometric defect is shown by
AgCl ? [Delhi 2013] of this mineral there are 4 Ca2+ ions and 8 F–
12. What type of substances would make better ions and that Ca2+ ions are arranged in a fcc
lattice. The F– ions fill all the tetrahedral holes in
permanent magnets, ferromagnetic or
fcc lattice of Ca2+ ions. The edge of the unit cell
ferrimagnetic? [Delhi 2013] is 5.46 ´ 10–8 cm in length. The density of the
13. What is the formula of a compound in which the solid is 3.18 g cm–3. Use this information to
element Y forms ccp lattice and atoms of X calculate Avogadro’s number. (Molar mass of
occupy 1/3rd of tetrahedral voids? [Delhi 2015] CaF2 = 78.08 g mol–1) [Delhi 2010]
14. Give an example each of a molecular solid and 7. Calculate the packing efficiency of a metal crystal
an ionic solid. All India 2016] for a simple cubic lattice. [All India 2011]
15. What type of magnetism is shown by a 8. Define the following terms in relation to
substance if magnetic moments of domains are crystalline solids.
arranged in same direction? [Delhi 2016] (i) Unit cell
SHORT ANSWER QUESTIONS (ii) Coordination number
Give one example in each case.[All India 2011]
1. Niobium (Nb) crystallises in a body-centred 9. Explain how you can determine the atomic mass
cubic (bcc) structure. If its density is 8.55 g of an unknown metal if you know its mass
cm–3, calculate the atomic radius of niobium. density and the dimensions of unit cell of its
crystal? [All India 2011]
Solid State 11
10. Silver crystallizes in face centred cubic unit cell. (c) What type of point defect is produced
Each side of this unit cell has a length of 400 pm. when AgCl is doped with CdCl2?
Calculate the radius of the silver atom. (Assume [Delhi 2013]
the atoms just touch each other on the diagonal 19. An element with density 2.8 g cm–3 forms of
across the face of the unit cell. That is each face f.c.c. unit cell with edge length 4 × 10–8 cm.
atom is touching the four corner atoms). Calculate the molar mass of the element.
[Delhi 2011] (Given: NA = 6.022 × 1023 mol–1)
11. Copper crystallises with face centred cubic unit [All India 2014]
cell. If the radius of copper atom is 127.8 pm, 20. (i) What type of non-stoichiometric point
calculate the density of copper metal. (Atomic defect is responsible for the pink colour
mass of Cu = 63.55 u and Avogadro’s number, of LiCl?
NA = 6.02 × 1023 mol–1) [All India 2012] (ii) What type of stoichiometric defect is
12. Iron has a body centered cubic unit cell with shown by NaCl?
an edge length of 286.65 pm. The density of OR
iron is 7.87 g cm –3 . Use this information How will you distinguish between the following
to calculate Avogadro’s number. (At. mass of pairs of terms:
Fe = 56 g mol–1) (i) Tetrahedral and octahedral voids
[All India 2012, 2009; Delhi 2012, 2009] (ii) Crystal lattice and unit cell
13. Tungsten crystallises in a body centered cubic [All India 2014]
unit cell. If the edge of the unit cell is 316.5 pm, 21. (i) Write the type of magnetism observed
when the magnetic moments are
14.
what is the radius of tungsten atom?
Account for the following :

[Delhi 2012]
(i) Schottky defects lower the density of

r
oppositely aligned and cancel out each
i
other.
(ii) Which stoichiometric defect does not
related solids.
(ii) Conductivity of silicon increases on
doping it with phosphorus. 22.
S change the density of the crystal?
[All India 2014]
(a) Write the type of magnetism observed
15. Aluminium crystallizes in an fcc structure.

Atomic radius of the metal is 125 pm. What is
G
[All India 2013]
A
the length of the side of the unit cell of the metal?
when the magnetic moments are aligned
in parallel and anti-parallel directions in
unequal numbers.
(b) Which stoichiometric defect decreases
[All India 2013] the density of the crystal?
16. (a) Why does presence of excess of lithium [All India 2014]
makes LiCl crystals pink? 23. An element with density 11.2 g cm–3 forms a
(b) A solid with cubic crystal is made of two f.c.c. lattice with edge length of 4 × 10–8 cm.
elements P and Q. Atoms of Q are at the Calculate the atomic mass of the element.
corners of the cube and P at the body- (Given : NA = 6.022 × 1023 mol–1)
centre. What is the formula of the [Delhi 2014]
compound? [All India 2013] 24. Examine the given defective crystal
17. (a) What change occurs when AgCl is doped A+ B– A+ B– A+
B – 0 B – A + B–
with CdCl2?
A + B – A + 0 A+
[All India 2013]
B – A + B – A + B–
(b) What type of semiconductor is produced
when silicon is doped with boron? Answer the following questions :
18. (a) What type of semiconductor is obtained (i) What type of stoichiometric defect is
when silicon is doped with boron? shown by the crystal ?
(b) What type of magnetism is shown in the (ii) How is the density of the crystal affected
following alignment of magnetic moments? by the defect ?
(iii) What type of ionic substances show
such defect ? [Delhi 2014]
12 Chemistry
25. Define the following terms. (c) Why do ferrimagentic substances show
(i) Primitive unit cells better magnetism then antiferromagnetic
(ii) Schottky defect substances? [All India 2017]
(iii) Ferromagnetism [All India 2015]
26. An element with molar mass 27 g mol–1 forms a LONG ANSWER QUESTIONS
cubic unit cell with edge length 4.05 × 10–8 cm. 1. (a) An element has atomic mass 93 g mol–1 and
If its density is 2.7 g cm–3, what is the nature of density 11.5 g cm–3. If the edge length of its
the cubic unit cell? [Delhi 2015] unit cell is 300 pm, identify the type of unit
27. An element crystallizes in a bcc lattice with cell cell.
edge of 500 pm. The density of the element is 7.5 (b) Write any two differences between
g cm–3. How many atoms are present in 300 g of amorphous solids and crystalline solids.
the element ? [All India 2016] OR
28. An element crystallizes in a f.c.c. lattice with cell (a) Calculate the number of unit cells in 8.1 g
edge of 250 pm. Calculate the density if 300 g of of aluminium if it crystallizes in a f.c.c
this element contains 2 × 1024 atoms. structure. (Atomic mass of Al = 27 g mol–1)
[Delhi 2016] (b) Give reasons :
29. Calculate the number of unit cells in 8. 1 g (i) In stoichiometric defects, NaCl exhibits
of aluminium if it crystallizes in a face-centred Schottky defect and not Frenkel defect.
cubic (f.c.c) structure. (Atomic mass of (ii) Silicon on doping with Phosphorus
Al = 27 g mol–1) [All India 2017] forms n-type semiconductor.
30. (a) Based on the nature of intermolecular
forces, classify the following solids:
Sodium sulphate, Hydrogen
i r
(iii) Ferrimagnetic substances show better
magnetism than antiferromagnetic
substances. [All India 2017]
(b) What happens when CdCl2 is doped with
AgCl?
S
Very Short Answer Questions
G
PAST YEARS SOLUTIONS
A 7. Conductivity of metals is due to free electrons
1. The difference of energy between conduction while that of ionic substances is due to ions
band and valence band is called forbidden zone which move in solution.
and for insulator its value is averaging 8. Crystalline solids are anisotropic in nature. This
between 3–6 eV. means that some of their physical properties like
2. Coordination number of Na+ ion = 6 resistance or refractive index show different
Coordination number of Cl– ion = 6 values when measured along different
3. Frenkel defect is due to dislocation of ion from directions.
its usual site to interstitial position. Density 9. The conductivity of an intrinsic semi-conductor
remains the same. can be increased by doping i.e. adding an
4. Metallic solids consist of positively charged impurity from outside i.e. either from group 13 or
kernels and valence electrons. Thus due to group 15.
presence of valence electrons metallic solids are
good conductors of electricity. Metallic solids 10. In face-centered cubic crystal, there are 8 atoms
are also malleable and ductile. at the corners and 6 at face-centres.
5. As the impurity added is pentavalent (As) \ total no. of atoms per unit cell
therefore n-type semiconductor is obtained. 1 1
6. The molecules of a polar solid are held together =8´ + 6´ = 4
8 2
by dipole-dipole interactions.
Solid State 13
11. Frenkel defect. 1/3
æ 930 ö
12. Ferromagnetic substances would make better \ log x = log ç ÷
permanent magnets because when the è 8.55´ 3.01 ø
ferromagnetic substance is placed in a 1
= (log 930 - log 8.55 - log 3.01)
magnetic field, all domains get oriented in the 3
direction of magnetic field and a strong 1
= (2.9685 - 09320 - 0.4786)
magnetic effect is produced. 3
13. Let the number of atoms of element Y present in 1
ccp = x log x = (1.5579) = 0.5193
3
Therefore, the number of tetrahedral voids = 2x x = Antilog (0.5193)
As 1/3rd of tetrahedral voids are occupied by x = 3.306
atoms of element X, therefore, number of atoms \ a = 3.306 × 10–8 cm
1 2x 3
of X present = ´ 2 x = .
Now r = a
3 3
4
2x 3 1.732 ´ 3.306 ´10-8
\ Ratio of Y : X = x : = 3x : 2x = 3 : 2 \r= ´ 3.306 ´10-8 =
3 4 4
\ The formula of the compound will be = Y3 X2 r = 1.4315 ´10-8 cm = 143.15 ´10 -10 cm
14.
or X2Y3.
The examples of molecular solids are ice (H2O)
and solid ammonia. (a)
i r
r = 143.15 pm
OR
The examples of ionic solids are sodium chloride

(NaCl), magnesium oxide (MgO) and zinc
sulphide (ZnS).
S n-type semiconductor: When a silicon or
germanium crystal is doped with group 15
element like P or As, the dopant atom forms
15. Ferromagnetism is shown by the substances for

which magnetic moments of domains are
arranged in the same direction. A G four covalent bonds like a Si or Ge atom
but the fifth electron, not used in bonding,
becomes delocalised and contribute its
share towards electrical conduction. Thus
silicon or germanium doped with P or As is
Short Answer Questions called n-type semiconductor, n indicative
of negative, since it is the electron that
1. d = 8.55 g / cm3, M = 93 g / mol conducts electricity.
For bcc, z = 2, a = ? NA = 6.02 × 1023 p-type semiconductor: When silicon or
z´M germanium is doped with group 13 element
d= like B or Al, the dopant has only with three,
a3 ´ NA
valence electrons. An electron vacancy or
Substituting the values a hole is created at the place of the missing
2 ´ 93 fourth electron. Here, this hole moves
8.55 = through the crystal like a positive charge
a ´ 6.02 ´ 1023
3
giving rise to electrical conductivity. Thus
2 ´ 93 Si or Ge doped with B or Al is called p type
a3 =
8.55 ´ 6.02 ´ 10 23 of semiconductor, (P stands for positive
1/3
hole) since it is the positive hole that is
æ 930 ö responsible for conduction.
a=ç ÷ 10-8
è 8.55 ´ 3.01 ø (b) F-centres: Electrons trapped in anion
1/3 vacancies are called F-centres. They impart
æ 930 ö characteristic color to the compound and
Let x = ç ÷
è 8.55 ´ 3.01 ø increase electrical conductivity.
14 Chemistry
(c) Ferromagnetism : Ferromagnetic 3. According to question
substances are those substances which are d = 8.95 g cm–3 = 8.95 ×106 g m–3
strongly attracted by external magnetic
field, e.g., (iron, cobalt, nicle and CrO2 etc.] r = 127.8 pm = 127.8 × 10–12 m
Ferromagnetism arises due to spontaneous M = 63.54 g mol–1
alognment of magnetic moments in the NA = 6.02 × 1023 mol–1
same direction.
by assuming that Cu crystallises in fcc unit cell
4r æ 2 ×a ö
Edge length, a = çr = ÷
Alignment of magnetic moments in ferromagnetic substance. 2 çè 4 ÷ø
2. Semiconductor: These are the solids with 4 ´127.8 ´ 10-12
conductivities in the intermediate range from 10– = m
6 to 104 ohm–1 m–1. 2
Semiconductors are of two types 3
(i) n-type of semiconductors (ii) p-type of æ 4 ´127.8 ´ 10-12 ö

a =ç
3
m÷
semiconductors è 2 ø
n-type semiconductor: When a silicon or = 4.725 × 10-29m3
germanium crystal is doped with group 15
element like P or As, the dopant atom forms four Rank of a unit cell
covalent bonds like a Si or Ge atom but the fifth
electron, not used in bondin g, becomes
delocalised and contribute its share towards i r Z=
d × a3 × N A
M
electrical conduction. Thus silicon or germanium

doped with P or As is called n-type S =
8.95 ´106 ´ 4.725 ´10-29 ´ 6.02 ´1023
63.54
p-type semiconductor: When silicon or

A
germanium is doped with group 13 element like
G
semiconductor, n indicative of negative, since
it is the electron that conducts electricity.
= 4.006 » 4
Hence, copper unit cell is a face centred cubic

structure.
B or Al, the dopant has only with three, valence
4. Edge length, a = 409 pm
electrons. An electron vacancy or a hole is
created at the place of the missing fourth a
electron. Here, this hole moves through the Radius of fcc unit cell, r = = 0.3535 a
2 2
crystal like a positive charge giving rise to
electrical conductivity. Thus Si or Ge doped with r = 0.3535 ´ 409
B or Al is called p type of semiconductor, (P r = 144.58 pm
stands for positive hole) since it is the 5. (i) Schottky defect arises when some ions are
positive hole that is responsible for missing from their normal sites thereby
conduction. decreasing density of the substance while
Silicon atom Mobile electron Positive hole
(no electron)
in Frenkel defect ions do not leave the
lattice but occupy positions else where in
the crystal lattice thus density of the
As B substance remains the same.
(ii) Electrical conductivity of the crystal is
increased in both Schottky and Frenkel
defects.
Perfect crystal n-type p-type
Solid State 15
6. For fcc, Z=4 10. According to question
M = 78.08 g mol–1 Edge length a = 400 × 10–12 m
a = 5.46 ´ 10–8 cm For fcc
d = 3.18 g cm–3
Z.M 2a
Using formula, d = r=
a 3 .N A 4
Z.M
Þ NA = 1.414 ´ 400 ´10 -12 m
a 3 .d =
4
4 ´ 78.08 = 141.4 ´ 10 -12 m
=
(5.46 ´10-8 )3 ´ 3.18 11. Given, r = 127.8 pm = 127.8 × 10–12m
= 6.022 ´ 1023 mol–1 M = 63.55 g mol–1
7. Packing efficiency in simple cubic lattice. NA = 6.02 × 1023 mol–1
Let the radius of atom in packing = r For fcc,
Atoms are present at the corners of the cube, 4r 4 ´127.8 ´10 -12
each of the eight atoms present at the eight a= = m
2 1.414
corners shared amongst eight unit cells. Hence
3
number of atoms per unit cell = 8 × (1/8) = 1 æ 4 ´127.8 ´ 10-12 ö
a3 = çç ÷÷
a 1.414
Again, r =
4 3
pr
2
therefore, è
r
= 4.725 × 10–29m3
i
ø
8.
P.F. =
3
(2r) 3 =
p
6
= 0.52, % P.F. = 52%,
(i) Unit cell : The smallest repeating unit in
S
Density of a unit cell,
d=
ZM
=
4 ´ 63.55
a N A 4.725 ´ 10-29 ´ 6.02 ´ 1023
G
3
space lattice which when repeats over and
A
over again, results in a crystal of the given
substance called unit cell. Thus it defines
the repeating pattern in the crystal in all
directions.
= 8.936 × 106 g cm–3
12. Given: a = 286.65 pm = 286.65 ´ 10–10 cm
d = 7.87 g cm–3
e.g., primitive unit cells and centred unit M = 56
cells. for bcc, Z = 2
(ii) Co-ordination number : The number of Using the formula,
nearest neighbours of a particle in a crystal
structure is called its coordination number Z.M
d=
e.g, coordination number of each sphere is a 3 .N A
8 in body centred cubic structures. Z.M
9. Density of a crystal can be given as Þ NA =
a 3 .d
ZM
r= 3 2 ´ 56
a .N A
Þ NA =
(286.65 ´10 -10 )3 ´ 7.87
r . a3 .N A
M= 112
Z =
where r, is the density in g cm–3, Z is number of 23.63 ´ 7.87´10-24
24
atoms in a unit cell, a3 is the volume of a unit = 0.6022 ´ 10
cell, NA is Avogadro’s number and M is molar
atomic mass. N A = 6.022 ´1023
16 Chemistry
13. Given: bcc unit cell i.e., P : Q = 1 : 1
a = 316.5 pm \ formula of the compound = PQ.
17. (a) Two Ag+ ions are replaced by one Cd2+ to
3 maintain electrical neutrality. Thus, a hole
For fcc, r = a
4 is created at the lattice site for every Cd2+
introduced.
1.732 ´ 316.5 (b) Boron is a trivalent atom it has three
= = 137.04 pm
4 electrons in its valence shell. Boron shares
14. (i) In Schottky defect, equal number of cations three electrons with three neighboring
and anions are missing from their lattice silicon atoms in the lattice, the fourth
sites. As a result number of ions decreases silicon atom demands an electron but the
and thus mass decreases but volume trivalent atom has no more electron to
remains same. Thus causes decrease in share. This creates a void or hole in lattice.
Thus p-type extrinsic semiconductor is
æ mass ö formed.
density çè density = ÷ of the solids
volume ø 18. (a) Boron is a trivalent atom it has three
having Schottky defect. electrons in its valence shell. Boron shares
(ii) Phosphorus is a group 15 element and has three electrons with three neighboring
five electrons in its valence shell. Upon silicon atoms in the lattice, the fourth
doping silicon with phosphorus four out silicon atom demands an electron but the
of 5 valence electrons forms four covalent
bonds with neighbouring silicon atoms, the
fifth extra electron is free and gets
i r
trivalent atom has no more electron to
share. This creates a void or hole in lattice.
Thus p-type (Positive type) extrinsic
delocalised which increases the
conductivity of the silicon. S semiconductor is formed.
(b) Given alignment of magnetic moments is
for ferromagnetic substance.
15. For fcc edge length a = 2 2r
= 2 ´ 1.414 ´ 125
= 353.5pm A G (c) Two Ag+ ions are replaced by one Cd2+ to
maintain electrical neutrality. Thus, a hole
is created at the lattice site for every Cd2+
introduced.
16. (a) When crystals of LiCl is heated in presence 19. Given: Density, d = 2.8 g cm–3
of excess of lithium, Cl– ions from crystal edge length, a = 4 × 10–8 cm
diffuse on surface and combine with ionised fcc unit cell, \ Z = 4
Li to form LiCl. The released unpaired To find: molar mass, M = ?
electrons occupy the anionic sites known Z .M
as F-centres. The pink colour results by Solution: d =
excitation of these electrons when they N A . a3
absorb energy from visible light falling on 4´ M
them. 2.8 g cm–3 =
( )
3
6.022 ´1023 mol -1 ´ 4 ´ 10-8 cm
(b) Given Q are present at the corner of the
cube 2.8 g cm -3 ´ 6.022 ´ 1023 mol-1 ´ 64 ´ 10 -24 cm3
\ No. of atoms of Q in one unit cell M=
4
1 M = 269.785 × 10–1 = 26.97 gmol–1
=8× = 1 (at corners) \ molar mass = 26.97 g mol–1
8
Also given that atoms of P are present at 20. (i) Metal excess defect caused by anionic
the body centre vacancies is responsible for pink colour of
\ No. of atoms of P in one unit cell LiCl.
= 1 (at body centre)
Solid State 17
(ii) Schottky defect is the stoichiometric defect 11.2g cm -3 ´ (4 ´10-8 cm)3 ´ 6.022 ´1023 mol
shown by NaCl. ÞM=
4
OR Þ M = 1079.14 × 10–24 × 1023 g
(i) Tetrahedral Voids Octahedral Voids M = 107.9 g
1. It is a simple 1. It is a double M ; 108 g
triangular void triangular void 24. (i) The given crystal shows schottky defect.
surrounded by surrounded by (ii) The density of the crystal decreases.
four spheres. six spheres. (iii) Schottky defect is shown by ionic
2. 2. substances in which the cation and
anion are of almost similar sizes for ex :
NaCl, KCl, AgBr.
25. (i) Primitive unit cells are defined as the unit
(ii) Crystal lattice Unit cell cells in which the constituent particles are
1 It is a regular 1 It is the smallest 3D present only at the corner positions.
arrangement of space portion of a complete (ii) Schottky defect: It occurs when equal
lattice which when constituent particles number of cations and anions are missing
repeated over and in a 3D space. from the lattice sites. It decreases the
again in different density of the solid.
directions produces For example: NaCl, KCl.
the space lattice. (iii) Ferromagnetism : Ferromagnetism is the
21. (i) The type of magnetism observed when
magnetic moments are oppositely aligned r
phenomenon shown by substances which
are strongly attracted by magnetic field.
i
These substances show magnetism even
and cancel out each other is Anti
ferromagnetism.
(ii) In Frenkel defect, there is no change in the
S in the absence of a magnetic field. Examples
are Fe, Co, Ni and CrO2.
26. Given: Density, d =2.7 × 103 kg m–3
a = 405 pm
A G
density of the crystal because there is no
ion missing from the crystal. There is only
a dislocation of ion from its normal site to
an interstitial site.
= 405 × 10–12 m
M = 2.7 × 10–2 kg mol–1
Density of a unit cell is given as
22. (a) Ferrimagnetism arises when magnetic Z ´M

d=
moments are aligned in parallel and anti- a3 N A
parallel directions in unequal numbers. d a3 N A
(b) In Schottky defect, density of the crystal ÞZ=
M
decreases. This is because equal number
of cations and anions are missing from their (2.7 ´ 103 ) (405 ´10 -12 )3 (6.022 ´10 23 )
=
lattice sites. 2.7 ´ 10-2
23. Given: density (d) = 11.2 g cm–3 = 3.99 ~ 4
Therefore, it is a fcc unit cell.
fcc lattice Þ Z = 4
edge length (a) = 4 × 10 cm
–8 27. Given :
To find : atomic mass, M = ? a = 500 pm = 500 × 10–10 cm
ZM z=2
Solution: We know, d = 3
a NA m = 300 g
3
d.a .N A M
ÞM= m = N (M is molar mass)
Z A
18 Chemistry
unit cell is 4
2´M
Density, d = a 3 N Number of unit cells in 8.1 g of aluminimum
A
1 6 .0 23 ´1 0 23
2´ M = ´ ´ 8.1 = 4.5 × 1022
7.5 = (500)3 ´10-30 ´ 6.02 ´ 1023 4 27
Hence, the number of unit cells in 8.1 g of
3
7.5 ´ (500) ´10 -30
´ 6.02 ´10 23 aluminium if it crystallizes in a face-centred cubic
M= = 282.1g / mol (f.c.c.) structure is 4.5 × 1022.
2
30. (a) Sodium sulphate is lonic solid
Mass of compound ´ N A
Molar mass, M = Number of atoms Hydrogen is Molecular solid (Non-polar
molecular solid)
300 ´ 6.02 ´1023 (b) When CdCl2 is doped with AgCl impurity
282.1 = defect arises. Cd2+ is divalent and Ag+ is
Number of atoms
univalent so there will be cationic vacan-
Number of atoms = 6.4 × 1023
cies when CdCl2 will be added.
Therefore, the number of atoms present in 300g
(c) In Antiferromagnetic substances equal
of compound is 6.4 × 1023.
number of magnetic moments are aligned
28. Given :
a = 250 pm = 250 × 10–12 m
z= 4 r
in opposite directions so as to give zero
net magnetic moment whereas in
i
Ferrimagnetic substances unequal number
m = 300 g
m=
M
(M is molar mass.)
S of magnetic moments are aligned in
opposite directions so the net magnetic
moment is not zero. Hence, ferromagnetic
NA
Molar mass, M =
300 ´ 6.02 ´ 10 23
2 ´ 10 24 A G
= 90.3 g/mol
substance show better magnetism than
antiferromagnetic substance.
Long Answer Questions
zM Z´M
Density, d = 1. (a) d=
3
a NA a3 N A
Given,
4 ´ 90.3 3
d= = 38.4g/cm d = 11.5 g cm–3
(250)3 ´ 10-36 ´ 6.02 ´ 1023
a = 300 pm = 300 × 10–10 cm
Therefore, the density of the given element is NA = 6.022 × 1023
38.4 g/cm3
M = 93 g mol–1
29. Number of Al atoms present in 27 g (1 mol) of Al
= 6.023 × 1023 d × a3 × N A
Z=
Number of Al atoms present in 8.1 g (1 mol) of Al M
6 .0 23× 1 0 23 11.5 ´ (3 ´10 -8 )3 ´ 6.022 ´1023
= × 8 .1 = =2
27 93
Since, aluminium crystallizes in a face-centred Therefore it is a bcc unity cell.
cubic (f.c.c.) structure the number of atoms per
Solid State 19
(b) (b) (i) Frenkel defect is show by ionic substance
in which there is large difference in the size
Crys talline s olids Amorphous s olids of ions, whereas Schottky defect is shown
(a) They h ave a d efinite (a) Th ey do n ot hav e by the ionic solids having very small
geo metrical s hap e an ord erly difference in the size of ions. In NaCl, there
due to the definite arrang ement of is a very small difference in their ionic
and ord erly particles and radius as a result NaCl shows Schottky
arrangement o f therefore, do no t defect.
particles in th e th ree po s s es s a definite
dimens ion al s pace. geometrical s hap e. (ii) Phosphorus is a group 15 element and is
electron rich. When it is doped with element
(b) They h ave s h arp (b) Th ey do n ot hav e of gp 14 e.g. Si, an n-type semiconductor
melting po int. s h arp melting po int.
will form because here conductivity is due
to presence of extra electrons.
OR
(iii) In Antiferromagnetic materials, the
8.1 magnetism from magnetic atoms or ions
(a) No. of moles of Aluminium = oriented in one direction is cancelled out
27
by the set of magnetic atoms or ions that
= 0.3 moles are aligned in the reversed direction.
Q No. of atoms present in 1 mole of Whereas in ferrimagnetic substances,
Al = 6.023 × 1023 atoms or ions aligned in an antiparallel
\ No. of atoms present in 0.3 mole of Al
= 6.023 × 1023 × 0.3
i r
arrangement such that the moments do not
completely cancel out and a net
magnetization remain even when there is
FCC unit cell contains 4 atoms therefore
number of unit cells present S no applied field.
=
6.022 ´1023 ´ 0.3
4 G
= 4.51´ 1022 unit cell
A Antiferromagnetic
substances
Ferrimagnetic
substances
SECTION C
SHORT ANSWER QUESTIONS 7. Why does the electrical conductivity of

semiconductors increase with rise in
1. Why are liquids and gases categorised as fluids? temperature?
2. Why are solids incompressible? 8. Explain why does conductivity of germanium
3. Inspite of long range order in the arrangement crystals increase on doping with galium?
of particles why are the crystals usually not 9. In a compound, nitrogen atoms (N) make cubic
perfect? close packed lattice and metal atoms (M) occupy
4. Why does table salt, NaCl sometimes appear one-third of the tetrahedral voids present.
yellow in colour? Determine the formula of the compound formed
5. Why is FeO(s) not formed in stoichiometric by M and N?
composition? 10. Under which situations can an amorphous
6. Why does white ZnO(s) become yellow upon substance change to crystalline form?
heating?
20 Chemistry
LONG ANSWER QUESTIONS 3. How does the doping increase the conductivity
of seminconductors?
1. With the help of a labelled diagram show that 4. A sample of ferrous oxide has actual formula
there are four octahedral voids per unit cell in a Fe0.93O1.00. In this sample, what fraction of metal
cubic close packed structure. ions are Fe 2+ ions? What type of non-
2. Show that in a cubic close packed structure, eight stoichiometric defect is present in this sample?
tetrahedral voids are present per unit cell.
NCERTEXEMPLAR
NCERT EXEMPLAR SOLUTIONS
SOLUTIONS
Short Answer Questions specific colour from the light and emit yellow
1. Liquids and gases have the tendency to flow light.
like fluids. Their molecules can move freely from 7. In case of semiconductors, the gap between
one place to another. Therefore, they are known conduction band and valence band is small.
as fluids. Therefore, electrons from the valence band can
2. In solids, the space between the constituent jump to the conduction band on increasing
particles is very less. On bringing them still temperature. Thus, they become more
closer repulsion will start between electron conducting as the temperature increases.
clouds of these particle. Hence, they cannot be 8. On doping germanium with galium some of the
positions of lattice of germanium are occupied
3.
brought further close togeth er and are
incompressible.
Although crystals have long range repeated
i r
by galium. Galium atom has only three valence
electrons. Therefore, fourth valency of nearby
germanium atom is not satisfied and the place
pattern of arrangement of constituent particles
but in the process of crystallisation some
deviations from the ideal arrangement (i.e., S
remains vacant.
This place is deficient of electrons and is
therefore called electron hole or electron
4.
defects) may be introduced in the crystal
perfect. G
structure. Therefore, crystals are usually not
A
Yellow colour in NaCl is due to metal excess
vacancy. Electron from neighbouring atom
comes and fills the gap, thereby creating a hole
in its original position.
Under the influence of electric field electrons
defect, called F-centres. Due to which unpaired
electrons occupy anionic sites. These electrons move towards positively charged plates through
absorb energy from the visible region for the these holes and conduct electricity. The holes
excitation which makes crystal appear yellow. appear to move towards negatively charged plates.
5. This is due to metal deficiency defect in the 9. Let the number of N atoms in ccp is x.
crystals of FeO. In FeO crystal, some of the Fe2+ \ Number of tetrahedral voids = 2x.
cations are replaced by Fe3+ ions. Three Fe2+ As 1/3rd of tetrahedral voids are occupied by
ions are replaced by two Fe3+ ions to make up atoms of metal M, therefore number of atoms of
the loss of positive charge. Eventually there 1
would be less amount of metal as compared to M present = ´ 2 x
3
stoichiometric composition.
6. On heating ZnO loses oxygen as follows Number of N atoms 3 x 3
= =
1 Number of M atoms 2 x 2
® Zn 2 + + O2 + 2e -
Heat
ZnO ¾¾¾ So, the formula of the compound is M2N3.
2
The excess of Zn2+ ions formed are trapped in 10. On heating, amorphous substances change to
the interstitial spaces and the electrons are also crystalline form at some temperature. For
trapped in the neighbourhood. These electrons example, some glass objects from ancient
absorb radiations corresponding to certain civilisation are found to be milky in appearance
due to crystallisation.
Solid State 21
Long Answer Questions centre of each unit cell. Each unit cell consists
of 8 small cubes.
1. Cubic close packed structure has one atom at
Each small cube contains 4 atoms at its alternate
each of eight corners of a unit cell and one atom
corner when these atoms are joined to each other
at each of six faces.
lead to creation of a tetrahedral void as shown
In case of fcc atom present at body centre is
in the figure below.
surrounded by six identical atoms present at face
centre hence, there is an octahedral void at body
centre of each unit cell.
(a)
Eight tetrahedral voids per unit cell of ccp
structure
Location of octahedral voids per unit cell of fcc

lattic e
There is one octahedral void at centre of each of
12 edges also which is surrounded by six atoms
as shown in the figure below.
i r
S (b)
One tetrahedral void showing the geometry
A G Since, there are total 8 smaller cubes present at

one unit cell and each smaller cube has one
tetrahedral void hence, total number of
tetrahedral void present in each unit cell is equal
to eight.
3. Semiconductors have low conductivity than
metals. Doping is the process of increasing
conductivity of semiconductors by adding a
Octahedral void at centre of each edge. suitable amount of impurity to the perfect crystal.
Each void is shared by 4 unit cell. Therefore, Doping can be done by adding any of the
contribution of octahedral void to each edge of following two types of the impurity to the crystal.
(A) By adding electron rich impurities i.e., by
1
a unit cell = adding group 15 elements to the silicon and
4 germanium of group 14 elements.
Number of octahedral voids at centre of 12 edge Silicon and germanium have four valence
1 electrons. When silicon and germanium
= ´12 = 3 crystal is doped with group 15 elements
4
like P or As, which contain five valence
Number of octahedral voids at body centre = 1
electrons four out of five electrons are used
Therefore, total number of octahedral voids at
in the formation of four covalent bonds with
each ccp lattice = 3 + 1 = 4.
the four neighbouring silicon atoms, while
2. Cubic close packed structure contains one atom
the fifth electron becomes delocalised. This
at each corner of an unit cell and one at face
delocalised electron increases the
22 Chemistry
conductivity of doped silicon and on oxygen.
germanium. This type of semiconductor is Therefore,
known as n-type semiconductor. 2x + 3y = 2 ...(ii)
(B) By adding electron deficient impurities i.e. 3
By adding group 13 elements to the perfect Þ x+ y =1 ...(iii)
2
crystal of silicon and germanium. When
On subtracting equation (i) from equation (iii)
group 13 element is doped with group 14
we have
elements, it lead to create a hole in the ideal
crystal which is known as electron hole or 3
y - y = 1 - 0.93
electron valency. 2
An electron from the neighbouring atom
can come and fill the electron hole at its 1
Þ y = 0.07
original position but in doing so it would 2
leave an electron hole at its original Þ y = 0.14
position. In this way, this hole moves On putting the value of y in equation (i), we get
through the crystal like positive charge, x + 0.14 = 0.93
giving rise to electrical conductivity. This Þ x = 0.93 – 0.14 = 0.79.
type of seminconductor is known as p-type Fraction of Fe2+ ions present in the sample
semiconductor. 0.79
4. Let the formula of the sample be (Fe2+)x(Fe3+)yO. = = 0.849
On looking at the given formula of the compound
x + y = 0.93 ...(i)
Total positive charge on ferrous and ferric ions
0.93
i r
Metal deficiency defect is present in the sample
because iron is less in amount than that required
should balance the two units of negative charge
S
for stoichiometric composition.
A G

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London dispersion forces).

Volume of the occupied unit cell = pr 3

unit cell \ Volume of the unit cell

numbers of P and Q? Þ 2 R=R+r

Hence, the formula of ferric oxide is Fe2O3.

CsCl and AgBr.

(ii) Frenkel defects is a combination of two basic

1.1. Why are solids rigid? cleavage property?

crystalline solids: Polyurethane, naphthalene,

(ii) Face-centred and end-centred unit cells.

VERY SHORT ANSWER QUESTIONS (Atomic mass of Nb = 93 u; NA = 6.02 × 1023

Account for the following :

(i) Schottky defects lower the density of

15. Aluminium crystallizes in an fcc structure.

The examples of ionic solids are sodium chloride

15. Ferromagnetism is shown by the substances for

(i) n-type of semiconductors (ii) p-type of æ 4 ´127.8 ´ 10-12 ö

electrical conduction. Thus silicon or germanium

p-type semiconductor: When silicon or

Hence, copper unit cell is a face centred cubic

space lattice which when repeats over and

22. (a) Ferrimagnetism arises when magnetic Z ´M

SHORT ANSWER QUESTIONS 7. Why does the electrical conductivity of

Location of octahedral voids per unit cell of fcc

A G Since, there are total 8 smaller cubes present at

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