ALTITUDE

Chapter -CLASSES
15

15 THE SOLID STATE

SOLIDS Crystalline solids :

Solids are characterised by the state of matter in which particles A crystalline solid usually consists of a large number of small
are closely packed and held together by strong intermolecular crystals, each of them having a definite characteristic geometrical
attractive forces. shape.
Types of Solids : Amorphous solids :
A solid can be classified as
Solids Amorphous solids have no precise melting point but when heated,
become increasingly pliable until they assume the properties usu-
ally associated with liquids.
Crystalline Solids Amorphous Solids

Difference Between Crystalline and Amorphous Solids :

Property Crystalline Solids Amorphous Solids

Shape Definite, Characteristic geometrical shape Irregular shape
Melting Point Melt at a sharp and characteristic Gradually soften over a range of
temperature temperature
Cleavage property Give plain and smooth surfaces on cutting Give irregular surfaces when cut with a
with a sharp edged tool sharp edged tool
Heat of fusion Definite and characteristic Not definite
Nature True solids Pseudo solids or supercooled liquids

Order in arrangement of Long range order Only short range order

particles
Anisotropy and Isotropy Anisotropic in nature, crystalline solids show Isotropic in nature, Amorphous solids
different values of physical properties along are isotropic in nature because some
different directions and hence they are of their properties like electrical
anisotropic in nature. resistance, refractive index, thermal
exapansion, etc., are same in all the
directions.
Examples Crystalline solids:- All solids elements Amorphous solids:- rubber, glass,
(metals and non-metals) and compounds fused silica, plastics, etc.
exist in this form.
 ALTITUDE CLASSES
CHEMISTRY
Note : (c) Amorphous silicon is one of the best photovoltaic material
(a) Glass is considered a super cooled liquid because glass is a available for conversion of sunlight into electricity.
amorphous solid and hence, it shows the property to flow, CLASSIFICATION OF CRYSTALLINE SOLIDS
though slowly. This is supported by the fact that glass panes
fixed to windows or doors of old buildings are invariably Crystalline solids are classified on the basis of nature of
found to be slightly thicker at the bottom than at the top. intermolecular forces operating in them into four categories, viz.
(b) Any material can be made amorphous or glassy either by molecular, ionic, metallic and covalent solids. The different
rapidly cooling its melt or freezing its vapours. For example : properties of the four types of solids are given in the table below:
Silica (SiO2) which crystallises as quartz can be converted
into amorphous silica (i.e. silica glass) by melting and rapid
cooling.

Type of Nature of Physical Electrical Melting

Constituent Examples
Solid Binding Nature Conductivity Point
Particles Forces
(1) Molecular Solids Atoms of noble Dispersion or Ar, H2, I2, Soft Insulator Very low
gas or non-polar London forces CH4, Solid CO2
(i) Non-Polar
molecules
(ii) Polar Polar molecules Dipole-dipole HCl, SO2 Soft Insulator Low
interactions

(iii) Hydrogen Molecules Hydrogen H2O (ice), NH3 Hard Insulator Low
bonded containing H bonding
linked to F,
O or N
(2) Ionic Solids Ions Coulombic or NaCl, LiF, Hard but Insulators in solid High
electrostatic Zns, CaF2, brittle state but conductors
forces MgBr2 in molten state and
in aqueous solution
state
(3) Metallic Solids Positive ions Metallic All metals and Hard but Conductors in Fairly High
in a sea of bonding alloys malleable solid as well
delocalised and as in molten state
electrons ductile

(4) Covalent or Atoms Covalent SiO2 (quartz), Hard Insulators

Network Solids bonding SiC, C(diamond), Very High
Soft Conductor
AlN, C(graphite) (exception)

Note : CRYSTAL LATTICES AND UNIT CELLS

(a) Ionic solids are insulators in the solid state because ions are
Crystal :
not free to move. However, in the molten state, when
dissolved in water, the ions become free to move about and A crystal is a homogeneous portion of a solid substance made by
they conduct electricity. regular pattern of structural units bonded by plane surface making
(b) Exceptional behaviour of graphite : definite angles with each other.
Graphite is soft, conductor of
Space Lattice :
electricity and a good solid
lubricant because of its typical The arrangement of constituents particles like atoms, ions or
structure. Carbon atoms are molecules in different sites in three dimensional space is called
arranged in different layers and space lattice.
each atom is covalently bonded to There are only 14 possible three dimensional lattices and these are
three of its neighbouring atoms in called Bravais Lattices. The characteristics of a crystal lattice are:
the same layer. The fourth valence (i) Each point in a lattice is called lattice point or lattice site.
electron of each atom is present (ii) Each point in a crystal lattice represents one constituent
between the layers and is free to
particle which may be an atom, a molecule or an ion.
move. This imparts graphite the
(iii) Lattice points are joined by straight lines to bring out the
above mentioned properties.
Structure of graphite geometry of the lattice.
 ALTITUDE CLASSES
THE SOLID STATE
Unit Cell : bcc unit cell :
It is the smallest portion of the crystal lattice which when repeated Total number of atoms per unit cell
in different directions, generates the entire lattice. A unit cell is (i) Eight Corner atoms contribute one atom per unit cell.
characterised by six parameters, i.e., a, b, c, , and ; where a, b (ii) Centre atom contribute one atom per unit cell.
and c are its dimensions along the edges while , and are the (iii) So, total 1 + 1 = 2 atoms per unit cell.
angles between the edges. These are depicted in the figure given
below:
1
Z=8 × + 1=2
8

fcc unit cell :

c Total number of atoms per unit cells

b 1
(i) The eight corners atoms contribute for of an atom and
a 8
thus one atom per unit cell.
(ii) Each of six face centered atoms is shared by two adjacent
Unit cells can be broadly divided into two categories: unit cells and therefore one face centred atom contribute half
Primitive unit cells : of its share. Means
Unit cell in which constituent particles are present only on the
corner positions of a unit cell.
Centred or non-primitive unit cells : 1
6× = 3 atom per unit cell.
Unit cell in which constituent particles are present at positions 2
other than corners in addition to those at corners
(iii) So, total Z = 3 + 1 = 4 atoms per unit cell.
Types of Non-Primitive Unit Cells :
(i) Body-centred unit cells(bcc) : CLOSE PACKING IN CRYSTALS :
Unit cell in which besides corners, one constituent particle is Close-packing of particles results in two highly efficient lattices,
present at the body-centre. hexagonal close packed (hcp) and cubic close packed (ccp). The
(ii) Face-centred unit cells (fcc) : latter is also called face centered cubic (fcc) lattice.
Unit cell in which besides corners, one constituent particle is Hexagonal Close Packing :
present at the centre of each face. In hcp, the pattern of spheres is repeated in alternate layers and is
(iii) End-centred unit cells : often written as ABAB _ _ _ _ pattern.
Unit cell in which besides corners, one constituent particle is
present at the centre of any two opposite faces.
Contribution of Atoms Present at Different Lattice
Sites :
In a crystal, atoms located at the corners and face-centre of a unit
cell are shared by other cells and only a portion of such an atom
actually lies within a given unit cell
(i) A point that lies at the corner of unit cell is shared among
eight unit cells and thus, it contributes for 1/8 of each such
point to unit cell.
(ii) A point along an edge is shared by four unit cells and thus
contribute for 1/4 of each such point to unit cell.
(iii) A face-centred point is shared by two unit cells and thus
contributes for 1/2 of each such point to unit.
(iv) A body-centred point lies entirely within the unit cell and
thus contributes for one each such point to unit cell.
Calculation Number of Atoms in a Unit Cell
Primitive cubic/simple cubic unit cell :
1
Total number of atoms in one unit cell is 8 = (1)
8 Here each atom is surrounded by 12 others and is said to have
(8 corners × each corner is shared by 8 particles) co-ordination number of 12.
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CHEMISTRY
The hcp arrangement of atoms occupies 74% of the available space If the number of close packed spheres is N, then the number
and thus has 26% vacant space. of octahedral voids generated = N and, the number of
It has only one set of parallel close packed layers. tetrahedral voids generated = 2N
Hexagonal close packed structure is found in Be, Cd, Li, Ca, Cr, Note : In ionic compounds anions are present in the packing
Mo, V, Mg, Zn, Ce, Zr, Os, Ru, He, etc. whereas cations occupy the voids if the cations are small,
Cubic Close Packing : they may occupy tetrahedral voids while if cations are large
they occupy octahedral voids. Further, it is not necessary
In ccp, the pattern of layers is often written as ABCABC _ _
that all voids must be occupied. The formula of the compound
A can be calculated by knowing the fraction of voids occupied.
COORDINATION NUMBER :
In every ionic compound, positive ions are surrounded by negative
ions and vice versa. Normally each ion is surrounded by the largest
C possible number of oppositely charged ions. This number of
oppositely charged ions surrounding each ion is termed its
coordination number. The coordination number of positive and
negative ions of a compound are same when the two types of ions
are equal in number (e.g., NaCl, ZnS, etc.). On the other hand,
B when an ionic compound contains different number of positive
and negative ions (as in CaCl2 , Na2S etc.), the coordination
numbers of positive and negative ions are different. For example,
in CaCl2 since Cl– ions are twice the number of Ca2+ ions, the
coordination number of calcium ion is twice the coordination
A number of chloride ion.
As in hcp, each atom in ccp arrangement has 12 nearest RADIUS RATIO RULES :
neighbours. In other words, the co-ordination number of the atom
The ratio of the radii of the cation to the anion in crystal lattice
is 12.
is called radius ratio.
The ccp arrangement of atoms occupy 74% of the available space
and thus has 26% vacant space. r Radius of the cation
Radius ratio
It has four sets of parallel close packed layers. Hence the chances R Radius of the anion
for slipping of one layer over the other are more in the ccp Table shows the relationship of radius ratio, co-ordination num-
arrangement than in the hcp arrangement. Hence metals having ber and the geometrical shapes of some ionic crystals.
ccp structure (e.g. Cu, Ag, Au and Pt) are highly malleable and
ductile.
Cubic close-packed structure is found in Al, Cr, Co, Cu, Au, Ag, Limiting radius ratio C.N. Shape
Fe, Pb, Mn, Ni, Ca, Sr, Pt, all noble gases except He. (r+) / (r–)
Type and Number of Voids < 0.155 2 Linear
Close-packing of particles in hcp or ccp results in two types of 0.155 – 0.225 3 Planar triangle
voids : octahedral and tetrahedral. 0.225 – 0.414 4 Tetrahedral
(i) Tetrahedral void : Tetrahedral voids are formed when centres 0.414 – 0.732 4 Square planar
of four spheres are joined, i.e, 0.414 – 0.732 6 Octahedral
0.732 – 0.999 8 Body-centred cubic
Tetrahedral EFFECT OF PRESSURE AND TEMPERATURE ON
void CRYSTAL STRUCTURE
Effect of Pressure
Increase of pressure increases the co-ordination number during
If the number of close packed spheres is N, then the number crystallization e.g., by applying high pressure, the NaCl crystal
of tetrahedral voids generated = 2 N structure having 6 : 6 co-ordination number changes to CsCl
(ii) Octahedral void : A void surrounded by six spheres (i.e. crystal structure having co-ordination number 8 : 8.
when triangular voids in the second layer are above the
high pressure
triangular voids in the first layer) is called octahedral void, NaCl type crystal CsCl type crystal
i.e., heat, 760 K
Octahedral (6 : 6 co-ordination) (8 : 8 co-ordination)
void Effect of Temperature
Increase of temperature, however, decreases the co-ordination
number e.g., upon heating to 760 K, the CsCl crystal structure
having co-ordination of 8 : 8 changes to NaCl crystal structures
having co-ordination 6 : 6.
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THE SOLID STATE
PACKING EFFICIENCY Points defect is of 3 types :
It is the percentage of total space filled by the particles. (i) Stoichiometric Defects :
Those point defects that do not disturb the stochiometry of
Relation between 'a 'and ' r ' the solid.
Type of Packing
a : edge length (a) Vacancy defect : This defect arises when some lattice
structure Efficiency sites are vacant. Thus generally arises due to absorption
r : radius of sphere
of heat from the surroundings. It decreases the density
hcp and a of a substance.
r 74% (b) Interstitial defect : This defect arises when some
ccp fcc 2 2
constituent particles occupy an interstitial site. It
3 increases the density of the substance.
bcc r a 68% The above two types of defects are generally shown by
4
Simple
non-ionic solids. Ionic solids do not show simple vacancy
a and interstitial defects. Instead, they show these defects
cubic r 52.4% as Schottky and Frenkel defects, as explained below:
2 (c) Frenkel defect : This defect arises when an ion is missing
lattice
from its lattice site and it occupies the interstitial site. It
Relationships between the nearest neighbour distance (d) and does not change the density of the crystal.
the edge (a) of unit cell of a cubic crystal. Frenkel defects are common in ionic compounds which
Simple Face-centred Body-centred have low co-ordination number and in which there is
large difference in size between positive and negative
a 3 ions.
d=a d= d= a
2 2 + – + – +
A B A B A
= 0.707 a = 0.866 a
+
A
DENSITY OF A UNIT CELL – – + –
For cubic crystals of elements B B A B
Z M
g/cm3
a N 0 10 30
3 + – + – +
A B A B A
For cubic crystals of ionic compounds
ZM g/cm3 or kg m–3 B
–
A
+
B
–
A
+ –
B
3
a NA
Fig. Frenkel defect
where density of the unit cell Eg. ZnS, AgCl, AgBr, AgI etc.
Z no. of atoms present in one unit cell (d) Schottky defect : This defect arises when equal number
M molar mass of cations and anions are missing from their lattice sites.
a edge length of the unit cell It decreases the density of substance.
NA Avogadro’s number Schottky defect is more common in ionic compounds
BRAGG EQUATION : with high co-ordination number and where the size of
According to Bragg, a crystal (composed of series of equally positive and negative ions are almost equal.
spaced atomic planes) could be employed not only as a – –
+ + +
transmission grating (as suggested by Laue) but also as a A B A B A
reflection grating. When X-rays are incident on a crystal face,
these penetrate into the crystal and strike the atoms in successive – – + –
planes. From each of these planes the X-rays are reflected like the B B A B
reflection of a beam of light from a bundle of glass plates of equal
thickness. Based on this model, Bragg derived a simple relation + – + +
between the wavelength ( ) of the X-rays used, the distance (d) A B A A
between the successive atomic planes and the angle of incident
X-rays or the angle of reflection ( ). – + – + –
B A B A B
n 2d sin (where n = 1, 2, 3, ......)
The equation is known as Bragg’s equation or Bragg’s law. The Fig. Schottky defect
reflection corresponding to n = 1 (for a given family of planes) is Eg. NaCl, KCl, CsCl, KBr etc.
called first order reflection; the reflection corresponding to n = 2 Note : AgBr shows both i.e., Frenkel and Schottky defect.
is the second order reflection and so on. (ii) Impurity defects :
IMPERFECTIONS IN SOLIDS These defects arise when foreign atoms are present at lattice
Point Defects and Line Defects : site (in place of host atoms) or at vacant interstitial sites.
Broadly the defects in crystals are of two types point and line (iii) Non-stoichiometric defects :
defects. Point defects are irregularities from ideal arrangement As a result of these defects, the ratio of cations to anions
around a point or an atom in lattice. However, when the deviation becomes different from that indicated by ideal chemical
from the ideal arrangement exist in the entire row of lattice points, formula.
the defect is called line defect. Example : VOx (where x can vary between 0.6 to 1.3)
 ALTITUDE CLASSES
CHEMISTRY
Two types of non-stoichiometric defects are : Thus, the impurities added may be electron rich or electron deficit.
(a) Metal excess defect : Each of these is briefly described below :
Metal excess defects due to anion vacancies (i) Doping with electron rich impurities : Group 14 element like
It occurs due to anionic vacancies i.e. anions diffuse to the silicon or germanium has 4 electrons in the valence shell.
surface of the crystal resulting in anionic sites which are When it is doped with Group 15 element like P or As, the
occupied by unpaired electrons. These sites are called silicon or germanium atoms at some lattice sites are
F-centres. The e–1s absorb energy from the visible light and substituted by atoms of P or As. Now, as these atoms have
impart colour to crystal 5 electrons in the valence shell, after forming normal four
Examples : covalent bonds with the neighbouring silicon atoms, the fifth
(1) The excess sodium in NaCl makes the crystal appears extra electron is free and gets delocalized. These delocalized
yellow. electrons increase the conductivity of silicon or germanium,
(2) Excess potassium in KCl makes it violet. the silicon or germanium crystals doped with electron rich
(3) Excess lithium in LiCl makes it pink. impurities are called n-type semiconductors.
Note : Greater the number of F-centres, greater is the intensity (ii) Doping with electron deficit impurities : When Group 14
of colour. element like Si or Ge is doped with Group 13 element like B, Al
Metal excess defects due to interstitial cations : or Ga, the Si or Ge atom at some lattice sites are substituted
It may occur if an extra positive ion is present in an interstitial by those of B, Al or Ga. Now, as Group 13 elements have only
site. Electrical neutrality is maintained by the presence of an three valence electrons, they can form three covalent bonds
electron in the interstitial site. with the neighbouring silicon atoms. Thus, a hole is created
Example : When ZnO is heated, it loses oxygen and turns at the site where fourth electron is missing. This is called
yellow due to: electron hole or electron vacancy. Electron deficit doped
2+ 1 – silicon or germanium are called p-type semiconductors.
ZnO Zn + O2 + 2e
2 MAGNETIC PROPERTIES OF SOLIDS
The excess of Zn2+ ions get trapped into vacant interstitial
sites. Magnetic properties of materials are studied in terms of magnetic
(b) Metal Deficiency defect : moments which arise due to orbital motion and spinning motion
It occurs due to missing of cation from its lattice site and of electrons.
presence of higher charge cation in adjacent site. It occurs Based on their behaviour in the external magnetic field, substances
when metals show variable valency, Example : FeO, FeS and are classified as below :
NiO. Diamagnetic Substances :
Those substances which are weakly repelled by external magnetic
ELECTRICAL PROPERTIES OF SOLIDS field. It is shown by substances which contain fully-filled orbitals.
On the basis of conductivity, solids are classified as: For ex: TiO2, H2O, NaCl, benzene, etc.
(i) Conductors : The solids having conductivities ranging Paramagnetic Substances :
between 104 to 107 –1 m–1. Metals are good conductors. Which are weakly attracted by external magnetic field. It is shown
(ii) Insulators : The solids having very low conductivities ranging by substances which contain unpaired e–1s. Example : O2, Cu2+,
between 10–20 to 10–10 –1 m–1. Example : plastic, rubber, Fe3+, Cr3+. However, they loose their magnetism in the absence
non-metals etc. of magnetic field.
(iii) Semiconductors: The solids having conductivities in the Ferromagnetic Substances:
intermediate range from 10–6 to 104 –1 m–1. The substances which are strongly attracted by magnetic field are
Band Theory : termed as ferromagnetic substances. This type of substance has
The behaviour of conductors, insulators and semiconductors are alignment of all the unpaired electrons in the same direction
explained on the basis of band theory. The atomic orbitals of (orientation) These substances are permanently magnetised i.e.
metals overlap to form a large number of molecular orbitals and these substances show magnetism even in the absence of
this set is called a band. Two bands are formed: magnetic field. Examples are Ni, Fe, Co and CrO2.
Valence band (lower energy) and conduction band (higher energy) Anti-Ferromagnetic Substances :
If valence band is partially filled or overlaps with higher energy Substances which possess zero net magnetic moment. It is due to
conduction band, e–1s can easily flow under the influence of presence of equal number of electrons in opposite directions. For
electric field. Thus, metals conduct electricity. ex: MnO, Mn2O3. Their magnetic moment will compensate each
If gap between filled valence band and unoccupied conduction others magnetic moment.
band is large, e–1s cannot jump from valence band to conduction Ferrimagnetic Substances :
band. Hence, the substance has extremely low conductivity and it When unequal number of unpaired electrons are aligned in
behaves as an insulator. opposite directions, the net magnetic moment is not zero. Such
If the gap between valence band and conduction band is small, substances are termed as ferrimagnetic substances e.g., ferrite
some e–1s may jump from valence band to conduction band. Hence, Fe2O3.
the substance shows some conductivity and it acts as a semi Note :
conductor. Electrical conductivity of semiconductor increases with (i) All magnetically ordered substances, i.e., ferromagnetic and
temperature as more electrons can jump to conduction band. Pure anti-ferromagnetic solids change into paramagnetic at high
substances like Si and Ge show this type of behaviour and are temperature. This is due to randomisation of domains (spins)
called intrinsic semiconductor. on heating. For ex: ferrimagnetic substance, Fe3O4, becomes
Extrinsic semiconductors are obtained by adding impurity to a paramagnetic at 850 K.
semiconductor so as to increase its conductivity. (ii) Each ferromagnetic substance has a characteristic
The process of adding impurities to a crystalline substance so as temperature above which no ferromagnetism is observed.
to change its properties is called doping. This is known as Curie temperature.
 ALTITUDE CLASSES
THE SOLID STATE

EXERCISE - 1
1. Frenkel and Schottky defects are : 13. A solid has a structure in which ‘W’ atoms are located at the
(a) nucleus defects (b) non-crystal defects corners of a cubic lattice ‘O’ atoms at the centre of edges
(c) crystal defects (d) nuclear defects and Na atoms at the centre of the cube. The formula for the
2. Which of the following compounds is a good conductor of compound is
electricity in solution state ? (a) Na2WO3 (b) Na2WO2
(a) Covalent (b) Molecular (c) NaWO2 (d) NaWO3
(c) Metallic (d) Ionic 14. A solid is made of two elements X and Z. The atoms Z are in
3. Most crystals show good cleavage because their atoms, ions ccp arrangement while the atoms X occupy all the tetrahedral
or molecules are sites. What is the formula of the compound?
(a) weakly bonded together (a) XZ (b) XZ 2
(b) strongly bonded together
(c) X2Z (d) X 2 Z3
(c) spherically symmetrical
(d) arranged in planes 15. The radius ratio in CsCl is 0.93. The expected lattice structure
4. Certain crystals produce electric signals on application of is
pressure. This phenomenon is called : (a) tetrahedral (b) square planar
(a) pyroelectricity (b) ferroelectricity (c) octahedral (d) body-centred cubic
(c) piezoelectricity (d) ferrielectricity 16. In NaCl crystal each Cl– ion is surrounded by
5. A solid with high electrical and thermal conductivity is (a) 4 Na+ ions (b) 6 Na+ ions
(a) Si (b) Li (c) 1 Na+ ions (d) 2 Na+ ions
(c) NaCl (d) Ice 17. Edge length of a cube is 400 pm, its body diagonal would be
6. Solid CH4 is (a) 566 pm (b) 600 pm
(a) ionic solid (b) covalent solid (c) 500 pm (d) 693 pm
(c) molecular solid (d) does not exist 18. In stoichiometric defects, the types of compound exhibit
7. An example of a covalent crystalline solid is: Frenkel defects have/has
(a) Si (b) Al (a) Low co-ordination nos.
(c) NaF (d) Ar (b) High co-ordination.
8. The pure crystalline substance on being heated gradually (c) Small difference in the size of cations and anions
first forms a turbid liquid at constant temperature and still at (d) None of these.
higher temperature turbidity completely disappears. The 19. For orthorhombic system axial ratios are a b c and the
behaviour is a characteristic of substance forming axial angles are
(a) Allotropic (b) Liquid
(a) 90 (b) 90
(c) Isomeric (d) Isomorphous
9. Na and Mg crystallize in the bcc and fcc type crystals (c) 90 , 90 (d) 90
respectively, then the number of atoms of Na and Mg present 20. In the fluorite structure, the coordination number of Ca2+
in the unit cell of their respective crystal is : ion is :
(a) 4 and 2 (b) 9 and 14 (a) 4 (b) 6
(c) 14 and 9 (d) 2 and 4 (c) 8 (d) 3
10. For fcc if AB is just like the rock salt like structure then, A+ 21. Na and Mg crystallize in bcc and fcc type crystals
and B– are located at – respectively, then the number of atoms of Na and Mg present
(a) A+ - Tetrahedral voids ; B– - Corner in the unit cell of their respective crystal is
(b) A+ - Corner and faces ; B– - Octahedral voids (a) 4 and 2 (b) 9 and 14
(c) A+ - Octahedral voids ; B– - Corner and faces (c) 14 and 9 (d) 2 and 4
(d) A+ - Corner and faces ; B– - Octahedral and tetrahedral 22. In the solid state, MgO has the same structure as that of
voids sodium chloride. The number of oxygens surrounding each
11. The ionic radii of X+ and Y– ions are 146 and 216 pm magnesium in MgO is
respectively. The probable type of structure shown by it is (a) 6 (b) 1
(a) CsCl type (b) Rock salt type (c) 2 (d) 4
(c) Zinc blend type (d) CaF2 type 23. Equal number of atoms or ion missing from normal lattice
12. The element which is used as semiconductor is point creating a vacancy due to
(a) Al (b) Bi (a) Frenkel defect (b) Mass defect
(c) Cr (d) Si (c) Schottky defect (d) Interstitial defect
 ALTITUDE CLASSES
CHEMISTRY
24. When molten zinc is converted into solid state, it acquires 36. CsBr crystallises in a body centered cubic lattice. The unit
hcp structure. The number of nearest neighbours of Zn will cell length is 436.6 pm. Given that the atomic mass of Cs =
be 133 and that of Br = 80 amu and Avogadro number being
(a) 6 (b) 12 6.02 × 1023 mol–1, the density of CsBr is
(c) 8 (d) 4 (a) 0.425 g/cm3 (b) 8.5 g/cm3
(c) 4.25 g/cm 3 (d) 82.5 g/cm3
25. Hexagonal close packed arrangement of ions is described as
(a) ABC ABA (b) ABC ABC 37. The pyknometric density of sodium chloride crystal is
2.165 × 103 kg m–3 while its X-ray density is 2.178 × 103 kg m–3.
(c) ABABA (d) ABBAB
The fraction of unoccupied sites in sodium chloride crystal
26. CsBr has bcc structure with edge length 4.3. The shortest is
interionic distance in between Cs+ and Br– is
(a) 5.96 × 10–3 (b) 5.96 × 104
(a) 3.72 (b) 1.86 –2
(c) 5.96 × 10 (d) 5.96 × 10–1
(c) 7.44 (d) 4.3 38. Potassium fluoride has NaCl type structure. What is the
27. Schottky defect generally appears in : distance between K+ and F– ions if cell edge is ‘a’ cm.
(a) NaCl (b) KCl (a) 2a cm (b) a/2 cm
(c) CsCl (d) all of these (c) 4a cm (d) a/4 cm
28. How many unit cells are present in a cube-shaped ideal 39. In the Bragg’s equation for diffraction of X-rays, n represents
crystal of NaCl of mass 1.00 g ? for
[Atomic masses : Na = 23, Cl = 35.5] (a) quantum number (b) an integer
(a) 5.14 × 1021 unit cells (b) 1.28 × 1021 unit cells (c) Avogadro’s numbers (d) moles
(c) 1.71 × 1021 unit cells (d) 2.57 × 1021 unit cells 40. The edge length of unit cell of a metal having molecular
29. In a solid ‘AB’ having the NaCl structure, ‘A’ atoms occupy weight 75 g/mol is 5Å which crystallizes in cubic lattice. If
the corners of the cubic unit cell. If all the face-centered the density is 2g/cc then find the radius of metal atom.
atoms along one of the axes are removed, then the resultant (NA = 6 × 1023). Give the answer in pm.
stoichiometry of the solid is (a) 217 pm (b) 210 pm
(a) AB2 (b) A2B (c) 220 pm (d) 205 pm
(c) A4B3 (d) A3B4 41. An element occuring in the bcc structure has 12.08 × 1023 unit
cells. The total number of atoms of the element in these cells
30. A solid AB crystallises as NaCl structure and the radius of
will be
the cation is 0.100nm. The maximum radius of the anion can
(a) 24.16 × 1023 (b) 36.18 × 1023
be: 23
(c) 6.04 × 10 (d) 12.08 × 1023
(a) 0.137 nm (b) 0.241 nm
42. The number of atoms in 100 g of an fcc crystal with density,
(c) 0.274 nm (d) 0.482 nm
d = 10 g/cm3 and cell edge equal to 100 pm, is equal to
31. Edge length of a cube is 400 pm. Its body diagonal would be
(a) 1 × 1025 (b) 2 × 1025
(a) 500 pm (b) 566 pm (c) 3 × 10 25 (d) 4 × 1025
(c) 600 pm (d) 693 pm 43. Pottasium has a bcc structure with nearest neighbour
32. In the calcium fluoride structure, the coordination number distance 4.52 Å. Its atomic weight is 39. Its density (in kg m–3)
of the cation and anion are respectively will be
(a) 6, 6 (b) 8, 4 (a) 454 (b) 804
(c) 4, 4 (d) 4, 8 (c) 852 (d) 910
33. The limiting radius ratio for tetrahedral shape is: 44. The radii of Na+ and Cl– ions are 95 pm and 181 pm
(a) 0 to 0.155 (b) 0.225 to 0.414 respectively. The edge length of NaCl unit cell is
(c) 0.155 to 0.225 (d) 0.414 to 0.732 (a) 276 pm (b) 138 pm
34. The second order Bragg diffraction of X-rays with = 1.00 Å (c) 552 pm (d) 415 pm
from a set of parallel planes in a metal occurs at an angle 60º. 45. The cubic unit cell of a metal (molar mass = 63.55g mol–1) has
The distance between the scattering planes in the crystal is an edge length of 362 pm. Its density is 8.92g cm–3.
(a) 0.575 Å (b) 1.00 Å The type of unit cell is
(c) 2.00 Å (d) 1.15 Å (a) primitive (b) face centered
(c) body centered (d) end centered
r 46. Coordination numbers of Zn2+ and S2– in the crystal structure
35. For a cubic geometry the limiting is :
r– of wurtzite are
(a) 0.414 (b) 0.155 (a) 4, 4 (b) 6, 6
(c) > 0.731 (d) 0.731 (c) 8, 4 (d) 8, 8
 ALTITUDE CLASSES
THE SOLID STATE
47. Each of the following solids show, the Frenkel defect except 60. The fraction of total volume occupied by the atoms present
(a) ZnS (b) AgBr in a simple cube is
(c) AgI (d) KCl
48. Doping of silicon (Si) with boron (B) leads to : (a) (b)
(a) n-type semiconductor (b) p-type semiconductor 3 2 4 2
(c) metal (d) insulator
49. Schottky defect defines imperfection in the lattice structure (c) (d)
4 6
of
(a) solid (b) gas 61. If ‘a’ stands for the edge length of the cubic systems : simple
(c) liquid (d) plasma cubic, body centred cubic and face centred cubic, then the
50. On doping Ge metal with a little of In or Ga, one gets ratio of radii of the spheres in these systems will be
(a) p-type semi conductor (b) n-type semi conductor respectively,
(c) insulator (d) rectifier 1 3 1 1 1
51. If Z is the number of atoms in the unit cell that represents the (a) a: a: a (b) a : 3a : a
2 4 2 2 2 2
closest packing sequence ..... ABC ABC ......, the number of
tetrahedral voids in the unit cell is equal to : 1 3 3
(a) Z (b) 2Z (c) a: a: a (d) 1a : 3a : 2a
2 2 2
(c) Z/2 (d) Z/4
52. Schottky defect in crystals is observed when 62. With which one of the following elements silicon should be
doped so as to give p-type of semiconductor ?
(a) an ion leaves its normal site and occupies an interstitial
site (a) Germanium (b) Arsenic
(b) unequal number of cations and anions are missing from (c) Selenium (d) Boron
the lattice 63. AB; crystallizes in a body centred cubic lattice with edge
(c) density of the crystal increases length ‘a’ equal to 387 pm. The distance between two
(d) equal number of cations and anions are missing from oppositely charged ions in the lattice is :
the lattice (a) 335 pm (b) 250 pm
53. The appearance of colour in solid alkali metal halides is (c) 200 pm (d) 300 pm
generally due to 64. Among the following which one has the highest cation to
(a) Schottky defect (b) Frenkel defect anion size ratio?
(c) Interstitial positions (d) F-centre (a) NaF (b) CsI
54. The crystal system of a compound with unit cell dimensions (c) CsF (d) LiF
"a = 0.387, b = 0.387 and c = 0.504 nm and = = 90° and 65. A solid compound XY has NaCl structure. If the radius of
= 120°" is the cation is 100 pm, the radius of the anion (Y–) will be :
(a) cubic (b) hexagonal (a) 275.1 pm (b) 322.5 pm
(c) orthorhombic (d) rhombohedral
(c) 241.5 pm (d) 165.7 pm
55. Crystal defect indicated in the diagram below is
66. A metal crystallizes with a face-centered cubic lattice. The
Na Cl Na Cl Na Cl Cl– Cl– Na+ Na+
edge length of the unit cell is 408 pm. The diameter of the
+
Na Cl – – +
Cl Na Cl – – +
Cl Na Cl Na – + Na+ metal atom is :
(a) Interstitial defect (a) 288 pm (b) 408 pm
(b) Schottky defect (c) 144 pm (d) 204 pm
(c) Frenkel defect 67. In a compound, atoms of element Y form ccp lattice and
(d) Frenkel and Schottky defects those of element X occupy 2/3rd of tetrahedral voids. The
56. Schottky defect generally appears in : formula of the compound will be
(a) NaCl (b) KCl (a) X4Y3 (b) X2Y3
(c) CsCl (d) all of these
(c) X2Y (d) X3Y4
57. Which defect causes decrease in the density of crystal
68. Copper crystallises in fcc with a unit cell length of 361 pm.
(a) Frenkel (b) Schottky
What is the radius of copper atom?
(c) Interstitial (d) F – centre
(a) 127 pm (b) 157 pm
58. What is the coordination number of sodium in Na2O?
(c) 181 pm (d) 108 pm
(a) 6 (b) 4
(c) 8 (d) 2 69. The edge length of a face centered cubic cell of an ionic
59. If NaCl is doped with 10– 4 mol % of SrCl2, the concentration substance is 508 pm. If the radius of the cation is 110 pm, the
of cation vacancies will be (NA = 6.02 × 1023 mol–1) radius of the anion is
(a) 6.02 × 1016 mol–1 (b) 6.02 × 1017 mol–1 (a) 288 pm (b) 398 pm
(c) 6.02 × 1014 mol–1 (d) 6.02 × 1015 mol–1 (c) 618 pm (d) 144 pm
 ALTITUDE CLASSES
CHEMISTRY

EXERCISE - 2
1. The correct statement regarding F– centre is 12. A match box exhibits
(a) electron are held in the voids of crystals (a) Cubic geometry
(b) F – centre produces colour to the crystals (b) Monoclinic geometry
(c) conductivity of the crystal increases due to F – centre (c) Orthorhombic geometry
(d) All of these (d) Tetragonal geometry
2. The anions (A) form hexagonal closest packing and the 13. Olive oil when allowed to cool slowly gets solidified and
cations (C) occupy only 2/3 of octahedral holes. The simplest forms a solid over a wide range of temperature. Best
formula of the ionic compound is : description of the solid based on above observation is
(a) CA (b) C3A2 (a) Ionic solid (b) covalent network solid
(c) C4A3 (d) C2A3 (c) metallic solid (d) molecular solid
3. Certain crystals produce electric signals on application of 14. A crystalline solid
pressure. This phenomenon is called (a) changes abruptly from solid to liquid when heated
(a) Pyroelectricity (b) Ferroelectricity (b) has no definite melting point
(c) Piezoelectricity (d) Ferrielectricity (c) undergoes deformation of its geometry easily
r (d) has an irregular 3-dimensional arrangements
4. For a cubic geometry the limiting is :
r– 15. Which of the following statements about amorphous solids
(a) 0.414 (b) 0.155 is incorrect ?
(c) > 0.731 (d) 0.731 (a) They melt over a range of temperature
5. Which of the following has maximum value of cation/anion (b) They are anisotropic
ratio? (c) There is no orderly arrangement of particles
(a) KCl (b) NaCl (d) They are rigid and incompressible
(c) CaF2 (d) MgCl2 16. To get a n- type semiconductor, the impurity to be added to
6. What is the number of tetrahedral voids per atom in a crystal? silicon should have which of the following number of valence
(a) 1 (b) 2 electrons
(c) 6 (d) 8 (a) 1 (b) 2
7. Fe 3O 4 contains the magnetic dipoles of cations oriented as (c) 3 (d) 5
17. Which set of following characteristics for ZnS crystal is
(a) (b) correct?
(c) (d) (a) Coordination number (4 : 4); ccp; Zn++ ion in the
8. The intermetallic compound LiAg crystallizes in a cubic alternate tetrahedral voids
lattice in which both lithium and silver atoms have (b) Coordination number (6 : 6); hcp; Zn++ ion in all
coordination number of eight. To what crystal class does tetrahedral voids.
the unit cell belong (c) Coordination number (6 : 4); hcp; Zn++ ion in all
(a) Simple cubic (b) Face-centred cubic octahedral voids
(c) Body-centred cubic (d) None of these (d) Coordination number (4 : 4); ccp; Zn++ ion in all
9. A compound is formed by elements A and B. The crystalline tetrahedral voids.
cubic structure has the A atoms at the corners of the cube 18. In p-type semiconductor, the added impurity to silicon is ---
and B atoms at the body centre. The simplest formula of the -and conduction of electric current is due to the movement
compound is of -----
(a) AB (b) A6B (a) As, electrons (b) P, holes
(c) AB6 (d) A8B4 (c) Ga, holes (d) Ga, electrons & holes
10. A compound formed by elements X and Y crystallizes in a 19. In an antifluorite structure, cations occupy
cubic structure in which the X atoms are at the corners of a (a) octahedral voids (b) centre of cube
cube and the Y atoms are at the face centres. The formula of (c) tetrahedral voids (d) corners of cube
the compound is 20. In the hexagonal close packed structure of a metallic lattice,
(a) XY3 (b) X3Y the number of nearest neighbours of a metallic atom is
(c) XY (d) XY2 (a) twelve (b) four
11. Na and Mg crystallize in bcc and fcc type crystals (c) eight (d) six
respectively, then the number of atoms of Na and Mg present 21. The Ca2+ and F– are located in CaF2 crystal, respectively at
in the unit cell of their respective crystal is face centred cubic lattice points and in
(a) 4 and 2 (b) 9 and 14 (a) tetrahedral voids (b) half of tetrahedral voids
(c) 14 and 9 (d) 2 and 4 (c) octahedral voids (d) half of octahedral voids
 ALTITUDE CLASSES
THE SOLID STATE
22. KCl crystallises in the same type of lattice as does NaCl. structure, called hexagonal close-packed (hcp), is constituted of a
Given that r /r 0.55 and rK / rCl 0.74. sphere on a flat surface surrounded in the same plane by six
Na Cl
Calculate the ratio of the edge length of the unit cell for KCl identical spheres as closely as possible. These spheres are then
to that of NaCl. placed over the first layer so that they touch each other and
(a) 1.123 (b) 0.891 represent the second layer. Each one of these three spheres
(c) 1.414 (d) 0.414 touches three spheres of the bottom layer. Finally, the second
23. Percentages of free space in cubic close packed structure layer is covered with third layer that is identical to the bottom
and in body centered packed structure are respectively layer in relative position. Assume radius of every sphere to be 'r'.
(a) 30% and 26% (b) 26% and 32% 28. The number of atoms in the hcp unit cell is
(c) 32% and 48% (d) 48% and 26% (a) 4 (b) 6
24. Lithium forms body centred cubic structure. The length of (c) 12 (d) 17
the side of its unit cell is 351 pm. Atomic radius of the lithium 29. The volume of this hcp unit cell is –
will be : (a) 24 2r 3 (b) 16 2r 3
(a) 75 pm (b) 300 pm 64 3
(c) 240 pm (d) 152 pm (c) 12 2r 3 (d) r
25. The packing efficiency of the two-dimensional square unit 3 3
cell shown below is : 30. The empty space in this hcp unit cell is
(a) 74% (b) 47.6%
(c) 32% (d) 26%
DIRECTIONS for Qs. 31 to 37 : These are Assertion-Reason
type questions. Each of these question contains two statements:
Statement-1 (Assertion) and Statement-2 (Reason). Answer these
questions from the following four options.
L (a) Statement-1 is True, Statement-2 is True; Statement-2 is a
(a) 39.27% (b) 68.02% correct explanation of Statement-1
(c) 74.05% (d) 78.54% (b) Statement-1 is True, Statement-2 is True; Statement-2 is
26. A compound M p X q has cubic close packing (ccp) NOT a correct explanation of Statement-1
arrangement of X. Its unit cell structure is shown below. The (c) Statement-1 is True, Statement-2 is False
empirical formula of the compound is (d) Statement-1 is False, Statement-2 is True
31. Statement-1 : In crystal lattice, the size of the tetrahedral
hole is larger than an octahedral hole.
Statement-2 : The cations occupy less space than anions in
crystal packing.
32. Statement-1 : In any ionic solid (MX) with Schottky defects,
M
the number of positive and negative ions are same.
X Statement-2 : Equal number of cation and anion vacancies
are present.
33. Statement-1 : Space or crystal lattice differ in symmetry of
the arrangement of points.
Statement-2 : n 2d sin , is known as Bragg’s equation.
34. Statement-1 : Crystalline solids have long range order.
Statement-2 : Amorphous solids have short range order.
(a) MX (b) MX2 35. Statement-1 : In close packing of spheres, a tetrahedral void
(c) M2X (d) M5X14 is surrounded by four spheres whereas an octahedral void
27. Which of the following exists as covalent crystals in the is surrounded by six spheres.
solid state ? Statement-2 : A tetrahedral void has a tetrahedral shape
(a) Iodine (b) Silicon whereas an octahedral void has an octahedral shape.
(c) Sulphur (d) Phosphorus 36. Statement-1 : Electrical conductivity of semiconductors
increases with increasing temperature.
DIRECTIONS for Qs. 28 to 30 : Read the passage given below
Statement-2 : With increase in temperature, large number of
and answer the questions that follow :
electrons from the valence band can jump to the conduction
In hexagonal systems of crystals, a frequently encountered band.
arrangement of atoms is described as a hexagonal prism. Here, the 37. Statement-1 : On heating ferromagnetic or ferrimagnetic
top and bottom of the cell are regular hexagons and three atoms substances, they become paramagnetic.
are sandwiched in between them. A space-filling model of this Statement-2 : The electrons change their spin on heating.
 ALTITUDE CLASSES
CHEMISTRY

HINTS & SOLUTIONS

EXERCISE - 1 15. (d) Since the radius ratio of CsCl is 0.93, it is expected to
have a body centred cubic structure.
1. (c) Frenkel and Schottky defects are crystal defects. It 16. (b) In NaCl crystal, each Cl– ion is surrounded by 6 Na+
arises due to dislodgement of cation or anion from their ions. Similarly, each Na+ is surrounded by 6 Cl– ions.
places in the crystal lattice.
2. (d) Ionic compounds are dissociated in solution state and
form ions. Ions are good carrier of charge which make –
solution conducting. CI
3. (d) Crystals show good cleavage because their constituent
particles are arranged in planes. Na+
4. (c) The phenomenon is called piezoelectricity.
5. (b) Out of the given substances, only Li has high electrical
and thermal conductivity as Li is a metallic solid.
6. (c) Solid CH4 is a molecular solid. In this, the constituent
molecules are held together by van der Waal’s forces.
7. (a) Si is an example of covalent crystalline solid among the 17. (d) For a simple cube, the relation can be obtained as under.
given choices. Si atoms are covalently linked in For a cube, body diagonal = 4 r
tetrahedral manner. (r = radius of sphere)
8. (b) Liquid crystals on heating first become turbid and then
clear. 4
For such a cube, we have a (edge length) r or
9. (d) In a bcc cell eight atoms are located at the corners 3
whereas one lies at the centre.
3
1 r a
n 8 1 2 4
8
Thus, body diagonal
whereas in an fcc cell eight atoms are at the corners and
one atom is located at each of the six faces which is shared 3
by two unit of cell. 4r 4 a
4
1 1
n 8 6 4 3a 3 400 pm
8 2
10. (c) AB is just like NaCl. Thus twelve A+ are at edges and 1 = 1.73 ×400 pm 693 pm.
within body of fcc i.e. in octahedral voids and six B– at 18. (a) In stoichiometric Frenkel defects occurs in those
faces and 8 at corner. compound which have
r 146 (i) Low C.N.
11. (b) The radius ratio 0.675 (ii) Large difference in size of cations and anions
r 216
19. (b) For orthorhombic system 90
It lies between 0.414 – 0.732. Hence, it exhibits rock salt
20. (c) In fluorite structure each F– ion is surrounded by four
type structure. Ca++ ions whereas each Ca++ is surrounded by eight
12. (d) Semiconductors are those solids which are good F– ions, giving a body centred cubic arrangement. Thus
conductors of electricity at room temperature but the co-ordination number of Ca++ and F– are 8 and 4
behave as insulators at room temperature, e.g., silicon respectively.
and germanium. 21. (d) The bcc cell consists of 8 atoms at the corners and one
1 atom at centre. Contribution of each atom at each corner
13. (d) In a unit cell, W atoms at the corner 8 1
8 1
is equal to .
1 8
O-atoms at the centre of edges 12 3
4 1
Na-atoms at the centre of the cube = 1 n 8 1 2
8
W : O : Na = 1 : 3 : 1
Hence, formula = NaWO3 The fcc cell consists of 8 atoms at the eight corners and
14. (c) Let the number of Z atoms in the ccp arrangement one atom at each of the six faces. This atom at the face
= 100 is shared by two unit cells.
Thus the number of tetrahedral sites = 200 1 1
Since all the tetrahedral sites are occupied by X atoms, n 8 6 4
8 2
the number of X atoms = 200
22. (a) Since MgO has a rock salt structure. In this structure
Hence ratio of X : Z = 2 : 1
each cation is surrounded by six anions and vice versa.
Thus the formula is X2Z
 ALTITUDE CLASSES
THE SOLID STATE
23. (c) The vacancy created due to missing of equal no. of 32. (b) In CaF2 , Ca2+ ions
have ccp arrangement and F– ions
atoms or ions form normal lattice point is called Schottky occupy the tetrahedral voids.
defect. In this type of defect electrical neutrality of ionic In ccp arrangement total no. of Ca2+ ions is 4 and
crystal is maintained. no. of tetrahedral voids is always 2n i.e. 8. Hence for
24. (b) hcp is a closed packed arrangement in which the unit every Ca2+ there are 8F– ions as C.N, for F– there are 4
cell is hexagonal and coordination number is 12. Ca2+ions.
25. (c) ABAB...... is hexagonal close packing. 33. (b) For tetrahedral shape radius ratio is 0.225 – 0.414.
34. (d) Order of Bragg diffraction (n) = 2; Wavelength ( ) = 1Å
3
26. (a) For bcc structure, atomic radius, r = a and angle ( ) = 60º.
4 We know from the Bragg’s equation
3 n = 2d sin
= × 4.3 = 1.86 or 2 × 1 = 2d sin 60º
4
Since, r = half the distance between two nearest 3 2
2 1 2.d . d 1.15Å
neighbouring atoms. 2 3
Shortest interionic distance = 2 × 1.86 = 3.72 (where d = Distance between the scattering planes)
27. (d) Schottky defect occurs in ionic crystals of type A+ B– 35. (c) For cubic geometry the limiting ratio is
, when equal number of cations and anions are missing
from their lattice sites so that the electrical neutrality is r
maintained. This defect generally appears in highly 0.731 i.e. (c)
ionic compounds which have high coordination number. r
NaCl, KCl and CsCl all have high coordination numbers 36. (b) For body centred cubic lattice Z = 2
i.e., 6, 6 and 8 respectively. So, Schottky defect appear Atomic mass of unit cell = 133 + 80 = 213 a.m.u
in all of the given compounds. Volume of cell = (436.6 × 10–10)3 cm3
28. (d) Since in NaCl type of structure 4 formula units form a ZM 2 213
cell. Density, =
a3 NA (436.6 10 10 )3 6.02 1023
58.5 gm. of NaCl = 6.023 × 1023 atoms = 8.50 g/cm3
6.023 1023 37. (a) Fraction of unoccupied sites in NaCl crystal
1 gm of NaCl = atoms
58.5 2.165 103
1
4 atoms constitute 1 unit cell 2.178 103
6.023 1023 2.178´103 - 2.165´103 0.13´103
atoms constitute = =
58.5 2.178´103 2.178

6.023 1023 130

= = 5.96 × 10–3
58.5 4 2178
= 2.57 × 1021 unit cells. 1
38. (b) Distance between K+ and F– length of the edge
1 1 2
29. (d) Effective number of ‘A’ atoms = 8 + 4 =3 39. (b) Bragg’s equation is n = 2d sin
8 2 where n is a positive integer i.e., 1, 2, 3, 4 etc. which
1 stands for serial order of diffracted beams
Effective number of ‘B’ atoms = 12 +1=4 ZM
4 40. (a)
Formula of the solid = A3B4. NA V
30. (b) Solid AB crystallizes as NaCl structure, so it has NA V 2 6 1023 (5 10 8 )3
coordination number 6 and its r +/r – ranges from Z
0.414 – 0.732. M 75
Z = 2, which represents bcc structure
For maximum radius of anion, we have to take the lower
3 3
r r a 5 2.165Å 216.5 pm
limit of the range 0.414– 0.732. So, 0.414 4 4
r 217 pm
0.100 41. (a) There are two atoms in a bcc unit cell.
r–= nm = 0.241 nm So, number of atoms in 12.08 × 1023 unit cells
0.414 = 2 × 12.08 × 1023 = 24.16 × 1023 atoms.
31. (d) Body diagonal (d) of a cubic crystal of edge length (a)
is given by, a3 N A 10 30
42. (d) M
d= a 3 Z
putting a = 400 pm, we get
10 (100)3 6.02 1023 10 30
d= 3 400 pm = 692.8 pm 693 pm. 15.05
4
 ALTITUDE CLASSES
HEMISTRY
53. (d) The appearance of colour in solid alkali metal halide is
6.02 1023 due to presence of F-centre found as defect in the
Number of atoms in 100 g = 100
15.05 crystal structure.
= 4 × 1025 54. (b) a b c , 90 , 120
43. (d) For bcc, d 3 2d 2 4.52 These are the characteristics of a hexagonal system.
a or a 5.219Å
2 3 1.732 55. (b) When equal number of cations (Na+) and anions (Cl–) are
= 522 pm missing from their regular lattice positions, we have
schottky defect.
z M
56. (d) Schottky defect occurs in ionic crystals of type A+ B,
3 30
a N A 10 when equal number of cations and anions are missing
from their lattice sites so that the electrical neutrality is
2 39
maintained. This defect generally appears in highly
3
(522) (6.023 1023 ) 10 30
ionic compounds which have high coordination number.
NaCl, KCl and CsCl all have high coordination numbers
0.91g / cm3 910 kg m 3 i.e., 6, 6 and 8 respectively. So, Schottky defect appear
44. (c) In a fcc lattice, the distance between the cation and in all of the given compounds.
anion is equal to the sum of their radii, which is equal to 57. (b) More is the Schottky defect in crystal more is the
half of the edge length of unit cell, decrease in density.
a 58. (b) In Na2O there is antifluorite structure. Here negative
i.e. r r (where a = edge length)
2 ions form the ccp arrangement so that each positive
+ –
r = 95 pm, r = 181 pm ion is surrounded by 4 negative ions and each negative
Edge length = 2r+ + 2r– = (2 × 95 + 2 × 181) pm ion is surrounded by 8 positive ions. So coordination
= (190 + 362) pm = 552 pm. no. of Na+ is 4.
59. (b) Since each Sr++ ion provides one cation vacancy, hence
ZM
45. (b) Concentration of cation vacancies = mole % of SrCl 2
NA V added
= 10–4 mole %
NA V 8.92 6.02 1023 (362)3 10 30
Z 10 4
M 63.55 = 6.023 1023 6.023 10 7
mol–1
=4 100
It has fcc unit cell 60. (d) Number of atoms per unit cell = 1
46. (a) Wurtzite has face centred cubic structure in which each a
Atoms touch each other along edges. Hence r =
Zn2+ ion is attached to four S2– ions and each S2– ion 2
remains in contact with four Zn 2+ ions. Hence ( r = radius of atom and a = edge length)
coordination number of each ion is 4. 4
r
47. (d) In KCl, co-ordination number of cation and anion is 6 3
Therefore % fraction =
and 6 respectively. KCl is highly ionic so Schottky (2 r )3 6
defect is common. 61. (a) Following generalization can be easily derived for
Note : Schottky defect is common in compounds having various types of lattice arrangements in cubic cells
high coordination nummber while Frenkel defect is between the edge length (a) of the cell and r the radius
common in compounds with low coordination number. of the sphere.
48. (b) a
For simple cubic : a = 2r or r
49. (a) Schottky defects are found in solid. 2
50. (a) p-type of semiconductors are produced For body centred cubic :
(i) due to metal deficiency defects 4 3
(ii) by adding impurity containing less electrons (i.e., a r or r a
3 4
atoms of group 13) For face centred cubic :
Ge belongs to Group 14 and In to Group 13. Hence on 1
doping, p-type semicondutor is obtained. a 2 2r or r a
51. (b) In cubic closed pack system (CCP system) .......ABC 2 2
Thus the ratio of radii of spheres for these will be
ABC....... type of arrangement of layers is found. In this simple : bcc : fcc
system, there are atoms at the corners as well as centre 1
of the unit cell. a 3
= : a: a
1 2 4 2 2
No. of atoms per unit cell 8 1 2 i.e. option (a) is correct answer.
8 62. (d) The semiconductors formed by the introduction of
Hence, the no. of tetrahedral voids in a unit cell = 2Z impurity atoms containing one elecron less than the
52. (d) If in an ionic crystal of the type A+, B–, equal number of parent atoms of insulators are termed as p-type
cations and anions are missing from their lattice sites semiconductors. Therefore silicon containing 14
so that the electrical neutrality is maintained. The defect electrons is to be doped with boron containing 13
is called Schottky defect. electrons to give a p-type semi-conductor.
 ALTITUDE CLASSES
THE SOLID STATE
63. (a) For bcc lattice body diagonal = a 3 . 5. (c) Among the three options KCl, NaCl and MgCl2 , the
The distance between the two oppositely charged ions size of anion is same. So larger the cation, larger will be
a the cation/anion ratio i.e., KCl will have larger cation/
= 3
2 anion ratio among the three. So, we left with two options
387 1.732 KCl and CaF2 . Among these two CaF2 will have
= 335pm
2 maximum value of cation/anion ratio because decrease
M in ionic radii of anion from Cl– to F– does not overcome
64. (c) is highest in CsF the effect of decrease in ionic radii of cation from K + to
X
correct choice : (c) Ca2+.
65. (c) Radius ratio of NaCl like crystal 6. (b) Number of tetrahedral voids (VT) in a crystal is twice
the number of atoms (n) in a crystal i.e.,
r
= 0.414 VT = 2n
r So, number of tetrahedral voids per atom is given by
100 VT / n = 2
r 241.5 pm
0.414 7. (b)
66. (a) For ccp 8. (c) A body-centred cubic system consists of all eight
2 a 4r
corners plus one atom at the centre of cube.
2 408 9. (a) Atoms are present in the corners of cube = A and atom
2r (2r = Diameter) present at body centre = B.
2
We know that a cubic unit cell has 8 corners. Therefore
Diameter = 288.5
67. (a) From the given data, we have 1
contribution of each atom A at the corner = . Since
Number of Y atoms in a unit cell = 4 8
2 16 number of atoms per unit cell is 8, therefore total
Number of X atoms in a unit cell 8
3 3 1
From the above we get the formula of the compound as contribution = 8 1 . We also know that atoms in
8
X16 / 3Y4 or X 4 Y3 the body centre, therefore number of atoms of B per
unit cell = 1. Thus formula of the compound is AB.
68. (a) For fcc unit cell, 4r = 2a
10. (a) For a face centred cubic structure,
2 361
r 127 pm No. of X atoms 8 1 1
4 8
69. (d) For an fcc crystal
1
edge length No. of Y atoms 6 3
rcation ranion 2
2
Formula of the compound = XY3
508
110 ranion 11. (d) In bcc - 8 atoms are at corners and one in the centre of
2 the unit cell.
ranion = 254 – 110 = 144 pm
1
Number of atoms per unit cell, n = 8 1 2.
EXERCISE - 2 8
1. (d) All the given statements are correct about F-centres. In fcc - 8 atoms are at the corners and also centre of the
1 six faces of each cell.
2. (d) The number of A ions per unit cell = 12 (corners)
6 1 1
Number of atoms per unit cell , n = 8
6 4.
1 8 2
2 (end centres) + 3 (in the body)
2 12. (c) Match box exhibits orthorhombic geometry i.e.,
Number of octahedral voids per unit cell = 1× 6 = 6. aa bb cc;; 90
90
2 13. (d) It can best be described as molecular solid.
Number of cations (C) per unit cell = 6 4
3 14. (a) In crystalline solid there is perfect arrangement of the
Formula : C4 A6 or C2 A3 constituent particles only at 0 K. As the temperature
3. (c) When polar crystal is subjected to a mechanical stress, increases the chance that a lattice site may be
electricity is produced – a case of piezoelectricity. unoccupied by an ion increases. As the number of
Reversely, if electric field is applied, mechanical stress defects increases with temperature solid changes into
is developed. Piezoelectric crystal acts as a mechanical liquid.
electrical transductor. 15. (b) Amorphous solids are isotropic, because these
4. (c) For cubic geometry the limiting ratio is substances show same properties in all directions.
16. (d) For n-type, impurity added to silicon should have more
r
0.731 i.e., (c) than 4 valence electrons.
r
 ALTITUDE CLASSES
CHEMISTRY
17. (a) ZnS has cubic close packed (ccp) structure. The S2–
ions are present at the corners of the cube and at the
centre of each face. Zinc ions occupy half of the
tetrahedral sites. Each zinc ion is surrounded by four
sulphide ions which are disposed towards the corners
of a regular tetrahedron. Similarly, S2– ion is surrounded
by four Zn 2+ ions.
18. (c)
19. (c) In antifluorite structure the oxide ions (anions) form a
face-centered cubic array and the metal ions (cations)
occupy all the tetrahedral voids. Example : Na2O
20. (a) Co-ordination number in hcp and ccp arrangement
is 12. a
21. (a) Fig. Hexagonal close-packed structure showing set of
r r + parallel planes.
22. (a) Na 0.55 and K 0.74
r r 29. (a) Volume of hcp unit cell
Cl Cl
r r + 6 3 2 6 3 2 2 2
Na
1 0.55 1 and K 1 0.74 1 a h a 2 a h 2 a
r r 4 4 3 3
Cl Cl
r r r + r 6 3 2
Na Cl 1.55 and K Cl 1.74 4r 2 2 2r ( a 2r )
r r 4 3
Cl Cl
Now edge length ratio of KCl and NaCl is 24 2 r 3
1.74 rK r r 30. (d) In a hcp unit cell the space occupied is 74%, as
Cl Cl
1.123. calculated below
1.55 r r r
Cl Na Cl Volume of the atoms in a unit cell
23. (b) Packing fraction is defined as the ratio of the volume Packing fraction
Volume of a unit cell
of the unit cell that is occupied by the spheres to the
total volume of the unit cell. 4 3
6 r 22 1
P.F. for cpp and bcc are 0.74 and 0.68 respectively. 3
= = =
So, the free space in ccp and bcc are 26% & 32% 24 2 r 3 3 2 7 3 2
respectively. = 0.74 or 74 %
24. (d) For bcc structure 3 a 4r Empty space is hcp unit cell = (100–74)%
= 26%
3 3 31. (d) Tetrahedral holes are smaller in size than octahedral
r a 351 152 pm.
4 4 holes. Cations usually occupy less space than anions.
32. (a) Schottky defect is due to missing of equal number of
25. (d) Packing efficiency
cations and anions.
= Area occupied by circles within the square 33. (b) Space or crystal lattice is a regular repeating
Area of square arrangement of points in space and forms the basis of
2 r2 2 r2 classification of all structures.
= 100 100 = 100 78.54% 34. (b) In crystalline solids constituents are arranged in definite
L2 2( 2 r ) 2 4 orderly arrangement. This regular arrangement of
1 constituents extends throughout the three dimensional
26. (b) No. of M atoms = 4+1=1+1=2
4 network of crystal. Thus crystalline substances said to
1 1 have long range order. Whereas amorphous solids have
No. of X atoms = × 6 + × 8 = 3 + 1 = 4 no regular arrangement.
2 8
35. (c) Tetrahedral void is so called because it is surrounded
So, formula = M2X4 = MX2 by four spheres tetrahedrally while octahedral void is
27. (b) Among the given crystals, only silicon exists as a so called because it is surrounded by six spheres
covalent solid. It has diamond like structure. octahedrally.
28. (b) In 1 unit cell of hcp, the number of atoms can be 36. (a) In case of semiconductors, the gap between valence
calculated as follows band and the conduction band is small and therefore
Number of atoms in a unit cell of hcp some of the electrons may jump from valence band to
1 1 conduction band and thus on increasing temperature
12(corner atoms) 2(face atoms)
6 2 conductivity is also increased.
+3(interior atoms) = 6 37. (a) All magnetically ordered solids (ferromagnetic,
i.e., the correct answer is option (b) ferrimagnetic and antiferromagnetic solids) transform
In a hexagonal close packing (hcp) the spheres in the to the paramagnetic state at high temperature due to
first and third layers are vertically aligned. See figure the randomisation of spins.
below