DAY TWO

States of Matter
Learning & Revision for the Day

u Classification of Matter u Liquid State u Bragg’s Law and Its

u Gaseous State u Solid State Applications
u Kinetic Theory of Gases u Unit Cell and Lattices

Classification of Matter
Anything which has mass and occupies space is called matter. Three states of matter are
as follows
1. Solids have definite volume, a definite shape and are rigid.
2. Liquids have definite volume, but not definite shape and are non-rigid.
3. Gases have neither definite shape, nor definite volume and are non-rigid. It is the
simplest state and shows great uniformity in behaviour.
l
Besides the three states of matter, two more states of matter have been found to exist.
These are plasma and Bose-Einstein condensate (predicted by Albert Einstein and
Indian physicist Satyendra Nath Bose).
l
If plasma are super-hot and super-excited atoms (a mixture of electrons and positively
charged ions formed by superheating, e.g. in the sun), the Bose-Einstein condensate are
total opposite, i.e. super-cold and super- unexcited atoms formed by super-cooling to
such an extent that the atoms lose their individual identity and condensate to form a
single super-atom.
Following two factors determine the physical state of matter:
1. Thermal agitation due to kinetic energy of the particles, atoms [or molecules] of a
matter are in a state of continuous vibration and agitation. This increases with
increase in temperature due to increase in their kinetic energy.
2. Cohesive forces (intermolecular forces) may be attractive or repulsive. Attractive
intermolecular forces are called van der Waals’ forces.
The nature of intermolecular forces, molecular interactions and effect of thermal
energy on the motion of particles helps to determine the state of a substance.
Attractive intermolecular forces are known as van der Waals’ forces. The different
types of van der Waals’ forces are as follows:
(i) Dispersion or London forces are the forces that exists between non-polar
molecules possessing temporary dipole moments. The interaction energy of these
forces is proportional to 1 / r 6. [where, r is the distance between two particles].
(ii) Dipole-dipole forces are forces that exists between dipole ends of polar
molecules and are strongest of all van der Waals’ forces.
 Dipole-dipole interaction energy between stationary
polar molecules is proportional to 1 / r 3 and that
Measurable Properties of Gases
between rotating polar molecules is proportional to The characteristics of gases are described fully in terms of
1 / r 6. four parameters, i.e. pressure (p), volume (V), temperature (T )
and mass or mole, which are termed as measurable
(iii) Dipole-induced dipole forces are forces that exists
properties.
between the polar molecules having permanent
dipole and the molecules lacking permanent dipole. (i) Mass is expressed in gram or kilogram and is equal to
Permanent dipole of the polar molecule induces the difference in masses of empty vessel and vessel
dipole on the electrically neutral molecule by containing gas.
deforming its electron cloud. (ii) Volume is equal to the volume of the container and is
In dipole-induced dipole interactions, the interaction expressed in terms of litre (L), millilitre (mL), cubic
energy is proportional to 1 / r 6. centimetre (cm3 ), cubic metre (m3 ) or cubic decimetre
(iv) Ion-dipole and ion-Induced dipole forces are similar (dm3 ).
to dipole-dipole and induced-dipole interactions but 1 L = 1000 mL = 1000 cm3 = 1 dm3
involves only ions, instead of only polar and 1 m3 = 103 dm3 = 10 6cm3 = 10 6 mL = 103 L
non-polar molecules. These forces are stronger than
(iii) Pressure is defined as force per unit area. The greater
dipole-dipole interactions because the charge of any ion
is much greater than the charge of a dipole moment. the force acting on a given area, the greater is the
pressure. The origin of the force exerted by a gas is the
(v) Hydrogen bond it is a special case of dipole-dipole
continuous collisions of the molecules against the walls
interaction.
of the container.
(a) In a solid, the cohesive forces predominate the
The units of pressure are atm, mm Hg, torr etc.
effect of thermal agitation. Consequently, the
particles are held together in rigid, highly-oriented 1 atm = 76 cm of Hg = 760 mm of Hg = 760 torr
and close-packed structure. 1 atm = 101.325 kPa = 101325 Pa = 101.325 Nm–2
(b) In a liquid, the cohesive forces are no longer = 1.01325 bar
strong enough, however, these are still sufficient, 1 bar = 10 5 Pa = 0.987 atm
so that particles cannot escape each others
environment, they have sufficient mobility. (iv) Temperature is the measurement of hotness or coldness
(c) In a gas, the thermal agitation dominates the effect of an object. It is measured in Celsius scale or absolute
of cohesive forces, thus the gas molecules acquire scale (Kelvin scale). Celsius scale was earlier known as
the unrestricted and independent mobility of the the centigrade scale.
vapour state.
Gas Laws
Gaseous State Various types of gas laws are as follows:
It is the most disordered state of matter. In this state, matter
neither have fixed volume nor fixed shape. It takes the shape 1. Boyle’s Law (1662)
and volume of the container in which it is placed. At constant temperature, the pressure of a fixed amount of gas
Gases exhibit the following characteristic properties: varies inversely with its volume.
Gases expand indefinitely. 1
At constant temperature (T ), p ∝
l

l
Gases are highly compressible. V
pV = constant (for given moles and T )
l
Gases intermix freely with one another or move from one
place to other without any difficulty. This is known as or p1V1 = p2V2 = constant
diffusion. The two conventional ways of graphically representing
l
Pure gases or their mixtures are all homogeneous in Boyle’s law are as follows:
composition.
l
Gases possess very low density. The density of gas when
compared to that of hydrogen is termed as relative density. p p
l
Due to collision of molecules on the walls of container,
gases exert pressure which obviously increases due to
increase in temperature. 1/V
V
l
Gaseous molecules move very rapidly in all directions in a p vs V plot p vs 1/V plot
random manner, i.e. gases have highest kinetic energy.
2. Charles’ Law (1787) 4. Avogadro’s Law
At constant pressure, the volume of a fixed mass of a gas is It states that equal volumes of all gases at same pressure and
directly proportional to its absolute temperature. temperature contain equal number of molecules.
At constant pressure ( p), V ∝ T V ∝n (at given T and p)
V V1 V2
= constant (for given n and p) or =
T n1 n2
V1 V2
or =
T1 T2
Ideal Gas Equation
l
Charle’s found that for all gases at given pressure, graph
The Boyle’s law, Charle’s law and Avogadro’s law can be
of V vs T is a straight line.
combined together in a single equation known as ideal gas
equation.
p1 nT
p1<p2<p3<p4 V ∝
p2 p
w
p3 pV = nRT or pV = RT
Volume

M
p4  w
∴ number of moles n =
 M 
or pM = dRT
where, w = mass of gas,
–300 –200 –100 0 100 M = molecular weight of gas
Temperature (°C) d = density of gas,
V vs T graph at different constant pressures p = pressure of gas
l
Charles’ obtained experimentally that for 1°C change in T = temperature, V = volume
temperature of a gas, the volume get changed by a R = universal gas constant.
fraction of
1
. Hence, if V0 be the volume of a gas at 0°C Values of R = 0. 0821 L atm K −1 mol−1
273
= 8 . 314 J K −1 mol−1
and it is recorded to be V at t ° C then
1 = 1 . 987 cal K −1 mol−1
V = V0 + t V0
273.15 = 8 . 314 kPa dm3 K −1 mol−1
 t  V0 = 0 . 083 bar dm3 K −1 mol−1
= V0 1 + = T
 273.15 273.15 NOTE Standard temperature and pressure (STP or NTP) means 273.15 K
If temperature is lowered, the volume decreases at (0°C) temperature and 1 bar (i.e. exactly 105 pascal) pressure. At
constant pressure and become zero at − 273.15 ° C. STP, molar volume of an ideal gas is 22.71098 L mol −1 .

Further lowering is not possible thus, it is called the lowest

possible temperature or absolute zero of temperature. Scale Dalton’s Law of Partial Pressures
of temperature based on this choice of zero is called l
Total pressure exerted by the mixture of non-reacting gases is
absolute scale of temperature or thermodynamic scale of equal to the sum of the partial pressures of individual gases.
temperature. pTotal = p1 + p2 + p3 + p4 + K (at constant T, V)

T (K) = t (° C) + 273.15
l
Partial pressure of a gas (p) = mole fraction (χ) × total pressure
exerted by the mixture ( ptotal )
3. Gay-Lussac’s Law l
Percentage of a gas in the mixture
At constant volume, pressure of a fixed amount of a gas partial pressure of gas
= × 100
varies directly with the temperature. total pressure
At constant volume (V ), p ∝ T = mole fraction of that gas × 100
p
= constant l
When a gas is collected over the water, the pressure of the gas
T pobserved or moist = pressure of dry gas + aqueous tension or water
(for given n and V) vapour pressure.
p1 p2 Relative humidity (RH ) is given by RH = partial pressure of
=
l
or
T1 T2 water in air/vapour pressure of water.
 Different kind of velocities of molecules are as follows:
Graham’s Law of Diffusion
(i) Root mean square velocity
According to this law “if a gas is allowed to escape from its
container through a small hole into vacuum, the process is 3 RT 3p 3KT
(urms ) = = =
called effusion. On the other hand, diffusion is the passage of M d M
gas through a porous partition. For the same gas at two different temperatures, the ratio
1 of RMS velocities will be
l
Rate of diffusion or effusion ∝
molecular weight u1 T
= 1
[QMolecular weight = 2 × vapour density ⇒ M ∝ d] u2 T2
1 For two different gases, the ratio of the RMS velocities
Rate of diffusion or effusion ∝
density u1 M2
will be =
l
Rate of diffusion or effusion (r) u2 M1
volume diffused or effused 8 RT 8 KT
= (ii) Average velocity (uav ) = =
time taken πM πM
r1 t 2 d M2
Hence, = = 2 = 2RT 2 pV 2p
r2 t 1 d1 M1 (iii) Most probable velocity (ump) = = =
M M d
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If p is not constant r ∝ p. Relation between different molecular velocities are as
r1 p1 M2 follows:
∴ =
r2 p2 M1 8
(i) ump : uav : urms : : 2 : : 3 =1 : 1.128 : 1.224
π
Kinetic Molecular Theory of Gases (ii) uav = urms × 0.9213
It is based on the following postulates: (iii) Kinetic energy of molecules
3
l
A gas consists of extremely small discrete molecules. These KE (per molecule) = K T
molecules are so small and so far apart that actual volume 2
of the molecules is negligible as compared to the total  R 
where, K = N  , K is Boltzmann constant
volume of the gas.  A 
R
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Gas molecules are in constant random motion with high = 1.38 × 10 −23 J K −1 molecule
velocities that moves in a straight line and changes their N0
directions on collision with other molecules or walls of 3 3
KE (per mol) = pV = RT
container. 2 2
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The intermolecular forces of attraction are negligible and At absolute zero, the kinetic energy of gas molecules
the effect of gravity on them is also negligible. become zero.
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The collisions are perfectly elastic, therefore, there is no
loss of kinetic energy during collision. However, there may Real Gases
be redistribution of energy during such a collision. The gas which does not obey gas laws at all conditions of
l
The pressure of a gas is caused by the bombardment of temperature and pressure is called real gas. Real gases obey
moving molecules against the walls of container. the gas laws under moderate conditions of temperature and
pressure.
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In a gas, different molecules have different kinetic energies
but the average kinetic energy of molecules is proportional Deviation from Ideal Behaviour
to absolute temperature of the gas.
At very low temperature and high pressure, real gases
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On the basis of these assumptions, the following show deviation from the ideal gas behaviour.
mathematical expression for kinetic gas equation is derived.
The causes of deviation are:
1
pV = mNu2 (i) At low temperature and high pressure, volume of a
3
real gas is larger than that predicted for an ideal gas
1
or pV = Mu2 as the molecules of gas have their own volume.
3
(ii) Intermolecular forces are not negligible.
(QM = m × N , for one mole m = 1)
The deviations from ideal gas behaviour are expressed in
where, u = rms velocity. terms of compressibility factor (Z ).
 pV 3. When Temperature is High At high temperature, V is
Compressibility factor (Z ) = =1 (for ideal gas)
nRT a
very large, the terms 2 and b can be neglected thus,
Different conditions of compressibility factor (Z ) for real gases V
are as follows: pV = RT .
l
Z < 1 (as for CH4 , NH3 , CO2 ) can be attributed to 4. When Temperature is Low At low temperature, both p
predominance of attractive forces among the molecules of and V are small thus, both pressure and volume
these gases at the temperature of experimentation. corrections are appreciable.
The values of van der Waals’ constant ‘a’ and ‘b’ do not
l
Z > 1 (for H2 , He) can be attributed to the dominance of
remain constant over the entire range of temperature
strong repulsive forces among the molecules. Boyle
and pressure. Hence, van der Waals’ equation is valid
temperature is the characteristic temperature of the gas at
only over specific range of temperature and pressure.
which it obeys ideal gas nature. Below this temperature, the
value of Z at first decreases, approaches a minimum and
then increases as the pressure increases continuously.
Liquefaction of Gases
and Critical Constants
van der Waals’ Equation l
The phenomenon of converting a gas into liquid is known
To rectify the errors caused by ignoring the intermolecular as liquefaction at particular temperature, pressure and
forces of attraction and the volume occupied by molecules,
volume. When a gas changes into liquid, these conditions
Johannes van der Waals’ proposed following equation, which
are known as critical conditions e.g. Tc , Vc , pc etc.
is valid for real gases upto a large range of temperature and
pressure. l
Critical Temperature (Tc ) is the maximum temperature at
 n a
2 which a gas can be liquefied. Critical pressure ( p c ) is the
 p + 2  (V − nb ) = nRT minimum pressure which is required to liquefy a gas.
 V 
Critical volume (Vc ) is the volume of one mole of a gas
where, n = number of moles, a = constant (measure of
which is occupied at critical temperature.
magnitude of attractive forces between the molecules)
8a
b = constant (due to occupied volume of gaseous molecules Critical temperature (Tc ) =
= co-volume or excluded volume). 27 Rb
a
Units of ‘a’ are atm L2 mol−2 or atm m6 mol−2 or Nm4 mol−2 and Critical pressure ( pc ) =
that of ‘b’ are L mol−1 or dm3 mol−1 . 27 b 2
Critical volume (Vc ) = 3 b
van der Waals’ equation get reduced at different conditions of
pressures and temperatures. These are shown below: 3
NOTE l Relation between critical p, V and T is pcVc = RTc
1. When Pressure is Low At low pressure, V is very large, 8
thus, (V − b ) ≈ V as b is neglected in comparison to V , pcVc 3
or = Z < 1 at critical point.
therefore equation becomes: RTc 8
 a a l At critical point, there is no distinction between gaseous
 p + 2  V = RT or pV + = RT state and liquid state as densities of a substance in gaseous
 V  V
and liquid states are same.
pV a pV a
⇒ =1− ⇒ Z= =1−
RT VRT RT VRT Liquid State
a
At extremely low pressures, is very small as V is very It is the state of matter in which the molecules are held close to
V each other and execute random motion through intervening
large. Thus, it can be neglected. spaces.
∴ pV = RT Liquids have definite volume. They can move past one
2. When Pressure is High At high pressure, V is quite another freely. They can flow, can be poured and can assume
small, thus, the term (V − b ) cannot be neglected while the shape of the container in which these are stored.
a
the term 2 is quite large but in comparison to high
V Physical Properties of Liquid
a
p, 2 can be neglected. 1 Vapour Pressure
V
l
Inside a closed vessel, the liquid and its vapours are in
∴ p(V − b ) = RT
dynamic equilibrium. The pressure exerted by the vapours
⇒ pV = RT + pb on the walls of the container increases. After sometime, it
pV pb pb becomes constant, an equilibrium is established between
=1+ or Z =1 +
RT RT RT liquid phase and vapour phase. Vapour pressure at this
stage is known as equilibrium vapour pressure.
 Since, the vapour pressure is a kinetic phenomena, it is
Bragg’s Law and Its Applications
l

independent of the amount of a liquid. It only depends on

the temperature. The fundamental relation among the wavelength of the
X-rays, the inter-planar distance in the crystal and the angle
l
When a liquid is heated in an open vessel, the liquid of reflection is known as the Bragg’s law.
vapourises from the surface. The temperature at which vapour
2d sin θ = nλ
pressure of the liquid becomes equal to the external pressure,
where,
vaporisation can occur throughout the bulk of the liquid is
called boiling point and the condition is called boiling. λ = wavelength of X-ray used
θ = angle between incident X-rays and the plane of the crystal
2 Viscosity d = distance between planes of the constituent particle in a
l
The ease with which a fluid can flow is determined by its crystal
property, called viscosity. It arises due to the internal n = an integer (1, 2, 3, 4, …) which represents the serial
friction between layers of fluids. order of diffracted beams.
l
Viscosity of liquid decreases with increase in temperature Various applications of Bragg’s law are as follows:
because rise in temperature increases the kinetic energy l
Structure of solids are determined by X-ray diffraction
of molecules, this results in decrease in inter-layer methods.
friction. l
Structures of complex substances such as proteins and
nucleic acids are also determined by this method.
3 Surface Tension
l
The force acting along the surface of a liquid at right angle
to any line per unit length is called surface tension. The unit of Unit Cell and Lattices
surface tension is Nm −1 . Surface tension decreases with An array of lattice points showing arrangement of
l

rise in temperature. It is different for different liquids due constituent particles in different position in three
dimensional space, is known as space lattice or crystal
to different intermolecular forces.
lattice.
l
Due to surface tension, the small drops of liquids are l
Unit cell is the smallest group of lattice points which when
spherical as the liquid tends to have a minimum surface
repeated in all directions develop the entire lattice.
area. Due to surface tension, liquids rise or fall in capillary
tube.
l
A unit cell is characterised by its dimensions (a, b and c)
and angles (α, β, γ). These parameters of a typical unit cell
are tabulated as follows:
Solid State Seven crystal system and their unit cell parameters
It is defined as that form of matter which has rigidity and due
to which it possesses a definite volume and a definite shape. Crystal systems and Bravais lattices Unit cell parameters
These characteristics are due to the existence of very strong Cubic [primitive, face centred, body a = b = c , α = β = γ = 90°
forces of attraction among the constituent species of the solid. centred]
e.g. NaCl, KCl, diamond, copper, zinc
On the basis of the arrangement of their atoms or ions or blende etc.
molecules, solids are broadly classified into two groups:
Rhombohedral or trigonal [primitive] a = b = c , α = β = γ ≠ 90°
1. Crystalline Solids They have systematic and regular e.g. NaNO3 ,CaCO3 , HgS, etc.
arrangement of particles and sharp melting
Orthorhombic [primitive, face centred, a ≠ b ≠ c , α = β = γ = 90°
point.Crystalline solids are anisotropic, i.e. their body centred, end centred]
physical properties have different values in different e.g. Rhombic sulphur, BaSO 4 (baryta),
directions. On the basis of types of bond present, they PbCO3 etc.
are further divided into four groups. Triclinic (most asymmetric) [primitive] a ≠ b ≠ c , α ≠ β ≠ γ ≠ 90°
(a) Molecular crystals or van der Waals’ crystals, e.g. K2Cr2O7 , H3 BO3 ,CuSO 4 ⋅ 5H2O etc.
e.g. I2(s), H2O (s) etc. Monoclinic [primitive, end centred] a ≠ b ≠ c,
(b) Atomic crystals or (covalent crystals), e.g. graphite, e.g. Na 2SO 4 ⋅ 10H2O, Na 2 B2O7 ⋅ 10H2O, α = γ = 90° ,β ≠ 90°
diamond etc. monoclinic S etc.
(c) Metallic crystals, e.g. all metallic solids etc. Tetragonal [primitive, body centred] a = b ≠ c , α = β = γ = 90°
(d) Ionic crystals, e.g. NaCl, CsCl, ZnS etc. e.g. Cassiterite, white tin, rutile etc.

2. Amorphous Solids They are unsystematic and irregular Hexagonal [primitive] a = b ≠ c,

e.g. Mg, beryl, ZnO (zincite), PbI2 , α = β = 90° , γ = 120°
arrangement of particles. These are isotropic, i.e. their
physical properties have same values in different graphite etc.
directions.
Various types of unit cells are as follows: (ii) Hexagonal Close Packing (HCP) The particles in every
1. Simple unit cell or primitive unit cell in which particles next row are placed in the depression between the particles
are present only at corners. of the first row. The particles in the third row will be
1 vertically aligned with those in the first row.
∴ Number of atoms per unit cell = × 8 = 1
8
1 2
2. Face centred cell in which the particles are present at
the corners as well as at the centre of each face. 6 2 3
∴ Number of atoms per unit cell 5 4
1 1
= ×8+ ×6 = 4 Coordination number is 6 (HCP)
8 2 Hexagonal close packing
3. Body centred unit cell in which the particles are present
at the corners of the cube as well as one particle is 3. Three Dimensional Packing
present at the centre within the body.
It can be obtained by stacking two dimensional layers one
1
∴ Number of atoms per unit cell = × 8 + 1 = 2 above the other.
8
It is of two types:
Coordination Number (i) Hexagonal Closed Packing (HCP) The first layer as
The number of atoms in a crystal which surrounds particular
layer A and second layer as layer B, the arrangement is
atoms as its nearest atoms in its neighbour is called its called AB AB K pattern or hexagonal closed packing (hcp).
coordination number. Each coordination number corresponds to (ii) Cubic Close Packing (CCP) When the third layer is
a fixed radius ratio (the ratio of radius of cation to that of anion). placed over the second layer in such a way that spheres
cover the octahedral voids, a layer different from layers
r  Coordination
Radius ratio  +  Structure A and B is produced. Let us call it as layer C. This
 r–  number
pattern of stacking spheres is called ABC ABCK pattern
< 0.155 2 Linear or cubic close packing (ccp). It is similar to face centred
0.155 − 0.225 3 Planar triangle cubic (fcc) packing.
0.225 − 0.414 4 Tetrahedral
0.414 − 0.732 6 Octahedral Voids
0.732 − 1 8 Cubic In closely packed structures, the empty space is called
interstitial site or void. The void can be a simple triangular
space in the case of two dimensional packing and called the
Packing in Solids trigonal void.

The packing of spheres of equal size in solids takes place as

follows:

1. One Dimensional Packing

When the spheres are placed in horizontal row, touching each
other, an edge of the crystal is formed.

Close packing of spheres in one dimension Trigonal void

In three dimensional close packing patterns, the voids can be

2. Two Dimensional Packing of two types:
It is done in two different types:
1. Tetrahedral Void It is a simple triangular space
(i) Square Close Packing (SCP) The particles, when placed surrounded by four spheres.
in the adjacent rows show a horizontal as well as vertical
alignment and form squares.

1 Coordination number is 4
(SCP)
4 2

Square close packing Tetrahedral void

 2. Octahedral Void It is a double triangular void Coordination number Ca2 + = 8, F− = 4, e.g. CdF2 , PbF2 ,
surrounded by six spheres. BaCl2 , SrCl2 .
5. Anti fluorite ( A 2 B) type It has ccp arrangement. The
cation occupy half of the tetrahedral voids.
Coordination number Na + = 4,O2 − = 8, e.g. Na2O.
6. On applying pressure, NaCl structure
(6:6 coordination) changes into CsCl
(8 : 8 coordination) and reverse of this occurs at high
temperature.
Octahedral void

The sizes of above voids can be seen in the increasing order as: Imperfections in Solids or Defects
Trigonal < tetrahedral < octahedral are N sphere Any departure from perfectly ordered arrangement of atoms
(atoms or ions) in the packing then. in a crystal is called imperfection or defect.
Number of octahedral voids = N The defects are of two types:
Number of tetrahedral voids = 2 N (i) Line defects are the irregularities or deviations from
ideal arrangement in entire rows of lattice points.
Calculations Involving Unit Cell Parameters (ii) Point defects are the irregularities or deviations from
1. Relation between Edge Length and Radius of Sphere ideal arrangement around a point or an atom in
crystalline substance.
(i) Simple cubic, r = a /2
Points defects are classified into three types. These are as
Percentage of packing fraction = 52 % follows:
a
(ii) Face centred cubic for ccp and hcp structures r = 1. Stoichiometric Defects are the point defects that do not
2 2 disturb the stoichiometry of the solid.
Percentage of packing fraction = 74% l
These are of two types: Vacancy and interstitial
3 defects.
(iii) Body centred cubic r = a
4 l
Schottky and Frenkel defects are vacancy and
Percentage of packing fraction = 68% interstitial defects respectively.
M ×Z
2. Density of unit cell d =
N A × a3 Schottky Defect Frenkel Defect
where, d = density It is mainly a vacancy defect It is mainly an interstitial defect
M = molecular weight arises due to equal number of arises due to the missing of ions
cations and anions missing (usually cations) from the lattice
Z = number of atoms per unit cell from the lattice sites. sites and they occupy the
N A = Avogadro number interstitial sites.
a = edge length of unit cell This results in the decrease It has no effect on the density of
in density of crystal. crystal.
Structures of Some Ionic Solids This type of defect is found in This type of defect is found in
highly ionic compounds with crystals, where the difference in the
1. Rock salt (NaCl) type It has fcc arrangement and
high coordination number, e.g. size of cations and anions is very
coordination number Na + = 6,Cl− = 6, e.g. LiCl, AgF, NaCl, CsCl, AgBr etc. large, e.g. AgCl, AgBr, ZnS etc.
AgCl, NH4 Br etc.
2. CsCl type It has the bcc arrangement with Cs + at the 2. Non-Stoichiometric Defects contain the constituent
body centre and Cl− ion at corners of a cube or elements is non-stoichiometric ratio due to defects in
vice-versa. Coordination number Cs + = 8, Cl− = 8, their crystal structures. These defects result in either
excess of metal atom or deficiency of metal atom.
e.g. CsCN, TiCl, TiCN etc.
In metal excess defect due to anionic vacancies, a
3. Zinc blende (ZnS) type It has ccp or fcc arrangement.
negative ion may be missing from its lattice site, leaving
Coordination number Zn2 + = 4 ,S2− = 4. Structure of ZnS
a hole which is occupied by an electron, thereby
is identical to diamond, e.g. CuCl, AgI etc. maintaining the electrical balance. The electrons, thus
4. Fluorite (CaF2 ) type It has ccp arrangement. F − ions trapped in the anion vacancies are called F-centres
occupy all the tetrahedral voids. because they are responsible for imparting colour to the
crystals.
 3. Impurity Defects is a common method of germanium show this type of behaviour and are called intrinsic
introducing defects in ionic solids. It is done by semiconductor (undoped).
adding impurity ions having different charge than
host ion.
—–Si—–Si—–Si—–Si—–
These foreign atoms are present at lattice site in Free electron s
substitutional solids and at vacant interstitial sites in
—–Si-⊕-Si—–Si—–Si—–
interstitial solids.
⊕ Hole
—–Si—–Si—–Si—–Si—–
Electrical Properties of Solids s s
Solids are classified into three groups on the basis their —–Si—–Si-⊕-Si—–Si—–
conductivity. These are as follows:
(i) Conductors are the solids with conductivity range Electrical conductance
of the order of 10 4 to 107 Ω −1 m −1 , e.g. metals.
l
The conductivity of intrinsic semiconductors is too low. So,
(ii) Semiconductors are the solids with conductivity
their conductivity is increased by adding an appropriate
range 10 −6 − 10 4 Ω −1 m −1 , e.g. semi-metals.
amount of suitable impurity. This process is called doping.
(iii) Insulators are the solids with conductivity range l
Introduction of impurities in the form of electrons of 13 and 15
10 −20 − 10 −10 (Ω m)−1 , e.g. non-metals. group of periodic table in perfect crystal. Such conductors is
1. In conductors, the conduction band is almost called extrinsic conductors. Depending upon the nature of the
overlapping with the valence band, i.e. there is no elements used for doping, the extrinsic semiconductor can be
energy gap present between these two bands or of two types, viz, n-type semiconductors and p-type
valence band is not completely filled. Electrons can semiconductors.
flow easily under the influence of electric field, in both (i) n-type semiconductors The group Mobile electron
the cases. 15 elements have 1 electron excess
to Si or Ge, after forming 4 covalent
As
Conduction bonds with group 14 member (Si or
band Ge). This excess free electron is
Overlapping responsible for electrical
band conductivity in them. Group 14
Partially filled Valence band elements when doped with group n-type semiconductor
valence band 15 elements are called n-type Position hole (no electron)
Conductors semiconductors. Here, n specifies
that negative charge flows in them.
2. In semiconductors, the gap between valence band and B
(ii) p-type semiconductors The group
conduction band is small and therefore, some of the
electrons may jump from valence band to conduction 13 elements have 1 electron short to
band and some conductivity is observed. group 14 elements, thus giving rise
to electron deficient band or a hole.
The conductivity here increases with increase in p-type semiconductor
temperature due to lowering of energy gap as shown in Here, such holes are responsible for
the figure. electrical conductivity.
Thus, group 14 elements when doped with elements of
group 13 are called p-type semiconductors.
Conduction
band 3. In case of insulators, the energy gap between valence band and
conduction band is so large that it cannot even covered up by
Small
supplying energy in the form of heat.
energy gap
Valence Conduction Valence
Large
band band band
energy gap
Semiconductors

l
Electrical conductivity of semiconductors increases
with rise in temperature, since more electrons can jump
Insulator
to the conduction band. Substances like silicon and
 5. Ferrimagnetic substances have a net dipole moment
Magnetic Properties of Solids due to unequal parallel and anti-parallel alignment
l
The origin of magnetic properties lies in the electrons. Each of magnetic moments. e.g. Fe3O 4, ferrites Mg Fe2O 4
electron in an atom behaves like a tiny magnet. Its magnetic and Zn Fe2O 4 etc.
moment originates from two type of motions (i) its orbital
motion around the nucleus and (ii) its spin around its own
axis.
Dielectric Properties of Solids
l
Electron being a charged particle and undergoing these These are seen in insulators. Insulators show generation
motions can be considered as a small loop of current which of dipoles in them, when they are placed in an electric
possesses a magnetic moment. field. These dipoles are given below:
(i) May align themselves in an order manner, so that
l
Each electron has a permanent spin and an orbital magnetic
there is a net dipole moment in the crystal.
moment associated with it whose magnitude is very small and
is measured in the unit called Bohr magneton, µ B . It is equal to (ii) May align themselves in such a manner that
9 . 27 × 10 −24 Am2 . dipole moments may cancel each other.
(iii) It is also possible that there are no dipoles in the
Solids can be divided into different classes depending on their crystal but only ions are present.
response to magnetic field. These are as follows :
Some other important dielectric properties of solids are:
1 Diamagnetic substances are the substances that are weakly
repelled by the magnetic field and do not have any unpaired 1. Piezoelectricity It is produced on applying
electron. e.g. TiO2 , V2O 5, C 6H6, NaCl etc. mechanical stress on polar crystals.

2 Paramagnetic substances are the substances that are 2. Pyroelectricity It is produced on heating some polar
attracted by the magnetic field and have unpaired electrons. crystals.
They lose magnetism in the absence of magnetic field. e.g. 3. Ferroelectricity Piezoelectric crystals with
O2 , Cu2+, Fe3+ etc. permanent dipoles are said to have ferroelectricity.
e.g. BaTiO3 , KH2 PO 4 etc. All ferroelectric solids are
3 Ferromagnetic substances are attracted by the magnetic piezoelectric but all piezoelectric solids are not
field and show permanent magnetism even in the absence ferroelectric, e.g. quartz is piezoelectric but not
of magnetic field. e.g. Fe, Co, Ni and CrO2 . Ferromagnetic ferroelectric.
property decreases from iron to nickel because number of
unpaired electrons decreases. 4. Antiferroelectricity In antiferroelectric crystals, the
dipoles in alternate polyhedra point up and down in
4 Antiferromagnetic substances have net magnetic moment such a way that the crystal does not possess any net
zero due to compensatory alignment of magnetic moments. dipole moment.
e.g. MnO, MnO2 , FeO, NiO, Cr2O3 etc.

DAY PRACTICE SESSION 1

FOUNDATION QUESTIONS EXERCISE

1 The intermolecular interaction that is dependent on the inverse 4 Equal weights of ethane and hydrogen are mixed in
cube of distance between the molecules is ª JEE Main 2015 an empty container at 25°C. The fraction of the total
(a) ion-ion interaction (b) ion- dipole interaction pressure exerted by hydrogen is
(c) London force (d) hydrogen bond (a) 1 : 2 (b) 1 : 1 (c) 1 : 16 (d) 15 : 16
2 A certain mass of the oxygen gas occupies 7 L volume 5 Through the two ends of a glass tube of length
under a pressure of 380 mm Hg. The volume of the same 200 cm HCl gas and NH3 are allowed to enter. At
mass of the gas at standard pressure with temperature what distance, the white ring of ammonium chloride
remaining constant shall be will first appear?
(a) 26.60 L (b) 54.28 L (c) 3.5 L (d) 7 L (a) 81.1 cm from HCl end (b) 81.1 cm from NH3 end
3 A bubble of gas released at the bottom of a lake increases (c) 118.9 cm from HCl end (d) The ring will not form
to eight times its original volume when it reaches the 6 At STP, 0.48 g of O 2 diffused through a porous
surface.Assuming that atmospheric pressure is equivalent to partition in 1200s. What volume of CO 2 will diffuse in
the pressure exerted by a column of water 10 m high, what is the same time and under the same conditions?
the depth of the lake? (a) 286.6 mL (b) 346.7 mL
(a) 90 m (b) 10 m (c) 70 m (d) 80 m (c) 112.2 mL (d) 224.8 mL
 235
7 What are the relative rates of diffusion for UF6 and 17 The compressibility of a gas is less than unity at STP.
238
UF6? Therefore,
(a) 1.0043 (b) 2.540 (c) 1.503 (d) 1.119 (a)Vm > 22.4 L (b)Vm < 22.4 L
(c)Vm = 22.4 L (d)Vm = 44.8 L
8 Assuming the same pressure in each case, what is the
mass of hydrogen required to inflate a balloon to a 18 If Z is a compressibility factor, van der Waals’ equation at
certain volumeV at 100°C, if 3.5 g helium is required to low pressure can be written as ª JEE Main 2014
inflate the balloon to half the volumeV at 25°C? RT a
(a) Z = 1 + (b) Z = 1 −
(a) 3.8 g (b) 2.8 g (c) 4.2 g (d) 4.0 g pb VRT
pb pb
9 Helium atom is two times heavier than a hydrogen (c) Z = 1 − (d) Z = 1 +
molecule at 298 K. The average kinetic energy of helium is RT RT
(a) two times that of hydrogen molecule 19 In van der Waals’ equation of state for a non-ideal gas,
(b) same as that of hydrogen molecule the term that accounts for intermolecular force is
(c) four times that of hydrogen molecule (a) (V − b) (b) (RT )−1
(c)  p + 2 
(d) half that of hydrogen molecule a
(d) RT
 V 
10 For a monoatomic gas, kinetic energy = E . The relation
with rms velocity is 20 For one mole of a van der Waals’ gas when b = 0 and
1 1 1
T = 300 K, the pV vs plot is shown below. The value of
(a) u =  2 (b) u =  2
2E 3E
  V
M   2M 
1 1
the van der Waals’ constant a (atm L mol −2) is
(c) u = 
E 2
(d) u = 
E 2 ª AIEEE 2012
 
 2M   3M 
24.6
11 At what temperature, the rms velocity of SO 2 be same as 23.1
that of O 2 at 303 K? 21.6
(a) 273 K (b) 606 K (c) 303 K (d) 403 K 20.1
12 The ratio between the root mean square velocity of H 2 at
pV (L atm mol–1)

50 K and that of O 2 at 800 K is

(a) 4 (b) 2 (c) 1 (d) 1/4
13 As the temperature is raised from 20°C to 40°C, the
0 2.0 3.0
average kinetic energy of neon atoms changes by a
factor of which of the following? 1/V (mol L–1)
1 313 313 (a) 1.0 (b) 4.5
(a) (b) (c) (d) 2
2 293 293 (c) 1.5 (d) 3.0
14 To an evacuated vessel with movable piston under 21 a and b are van der Waals’ constants for gases. Chlorine
external pressure of 1 atm, 0.1 mole of He and 1.0 mole is more easily liquefied than ethane because
of an unknown compound (vapour pressure 0.68 atm at (a) a and b for Cl 2 > a and b for C 2H6 ª AIEEE 2011
0°C) are introduced.
(b) a and b for Cl 2 < a and b for C 2H6
Considering the ideal gas behaviour, the total volume
(c) a for Cl 2 < a for C 2H6 but b for Cl 2 > b for C 2H6
(in litre) of the gases at 0°C is close to ª AIEEE 2011
(d) a for Cl 2 > a for C 2H6 but b for Cl 2 < b for C 2H6
(a) 3 (b) 5 (c) 7 (d) 9
22 The value of compression factor, Z for critical constants
15 If 10−4 dm 3 of water is introduced into a 1.0 dm 3 flask at
is
300 K, how many moles of water are in the vapour phase
1 3
when equilibrium is established? (a) (b)
2 4
(Given, vapour pressure of H2O at 300 K is 3170 Pa; 2 3
(c) (d)
R = 8.314 J K −1 mol −1) ª AIEEE 2010 3 8
(a) 5.56 × 10−3 mol (b) 1.53 × 10−2 mol
23 Which of the following exists as crystals in the solid
(c) 4.46 × 10−2 mol (d) 1.27 × 10−3 mol state? ª JEE Main 2013
16 The compressibility factor for a real gas at high pressure (a) Iodine (b) Silicon
is ª AIEEE 2012 (c) Sulphur (d) Phosphorus
RT
(a) 1 + (b) 1 24 The number of hexagonal faces that are present in
pb
truncated octahedron is ª AIEEE 2011
pb pb
(c) 1 + (d) 1 − (a) 2 (b) 4 (c) 6 (d) 8
RT RT
25 The first order diffraction of X-rays from a certain set of 34 How many unit cells are present in a cube shaped ideal
crystal planes occur at an angle of 11.8° from the planes. crystal of NaCl of mass 1.00 g?
If the planes are 0.281 nm apart, what is the wavelength (a) 2.57 × 10 21 (b) 5.14 × 10 21
of X-rays? (c) 1.28 × 10 21 (d) 1.71 × 10 21
(a) 0.281 nm (b) 0.2044 nm
(c) 0.1149 nm (d) 0.1180 nm 35 Iron crystallises in a bcc system with a lattice parameter
of 2.861 Å. Calculate the density of iron in the bcc system
26 In diamond, the coordination number of carbon is (atomic weight of Fe = 56, NA = 6.02 × 10 23 mol −1)
(a) four and its unit cell has eight carbon atoms (a) 7.94 g mL−1 (b) 8.96 g mL g −1
(b) four and its unit cell has six carbon atoms (c) 2.78 g mL−1 (d) 6.72 g mL−1
(c) six and its unit cell has four carbon atoms
(d) four and its unit cell has four carbon atoms 36 Calcium crystallises in a face centred cubic unit cell with
a = 0.556 nm. Calculate the density, if it contained 0.1%
27 Sodium metal crystallises in a body centred cubic lattice Schottky defects.
°
with a unit cell edge of 4 . 29 A . The radius of sodium (a) 1.5463 g / cm3 (b) 1.4962 g / cm3
atom is approximately ª JEE Main 2015 (c) 1.5448 g / cm3 (d) 1.5943 g / cm3
° ° 37 To get n-type semiconductor from silicon, it should be
(a) 1. 86 A (b) 3 . 22 A
° ° doped with a substance with valence
(c) 5 .72 A (d) 0. 93 A
(a) 1 (b) 2
28 Lithium forms body centred cubic structure. The length of (c) 3 (d) 5
the side of its unit cell is 351 pm. Atomic radius of the 38 Which type of ‘defect’ has the presence of cations in the
lithium will be ª AIEEE 2012 interstitial sites? ª JEE Main 2018
(a) 75 pm (b) 300 pm (c) 240 pm (d) 152 pm (a) Schottky defect (b) Vacancy defect
29 CsCl crystallises in body centred cubic lattice.If ‘a’ its (c) Frenkel defect (d) Metal deficiency defect
edge length, then which of the following expressions is 39 Which of the following compounds is metallic and
correct? ª JEE Main 2014 ferromagnetic? ª JEE Main 2016
3a
(a) r +r = 3a (b) r +r = (a) CrO2 (b) VO2
Cs + Cl − Cs + Cl − 2 (c) MnO2 (d) TiO2
3
(c) r +r = a (d) r +r = 3a
Cs+ Cl − 2 Cs+ Cl − Direction (Q. Nos. 40-43) In the following questions
Assertion (A) followed by a Reason (R) is given. Choose the
30 In a face centred cubic lattice, atom A occupies the
correct answer out of the following choices.
corner positions and atom B occupies the face centre
(a) Both A and R are true and R is correct explanation of A
positions. If one atom of B is missing from one of the
(b) Both A and R are true but R is not correct explanation of A
face centred points, the formula of the compound is
(c) A is true but R is false
ª AIEEE 2010
(d) Both A and R are false
(a) A2B (b) AB 2 (c) A2B 2 (d) A 2B 5
40 Assertion (A) Average speed of molecules, if a gas in a
31 An element having an atomic radius of 0.14 nm container moving only in one direction, will be zero.
crystallises in an fcc unit cell. What is the length of a side
Reason (R) The molecules of gas are not collected in one
of the cell? ª JEE Main 2013
direction.
(a) 0.56 nm (b) 0.24 nm (c) 0.96 nm (d) 0.4 nm
+ − 41 Assertion (A) The temperature at which vapour pressure
32 If the distance between Na and Cl ion in NaCl crystal
of a liquid is equal to the external pressure is called
is ‘a' pm. What is the length of the cell edge?
a boiling temperature
(a) 4 a pm (b) pm Reason (R) At high altitude atmospheric pressure is high.
4 ª JEE Main 2013
a
(c) 2 a pm (d) pm 42 Assertion (A) Liquids tends to have maximum number of
2 molecules at their surface.
33 A metal crystallises in a face centred cubic structure. If Reason (R) Small liquid drops have spherical shape.
the edge length of its unit cell is ‘a’ the closest approach
between two atoms in metallic crystal will be 43 Assertion (A) Solids containing F-centres are
ª JEE Main 2017 paramagnetic.
a Reason (R) F-centres solids possess holes occupied by
(a) 2a (b) 2 2 a (c) 2 a (d)
2 unpaired electrons.
24 40 DAYS ~ JEE MAIN CHEMISTRY DAY TWO

DAY PRACTICE SESSION 2

PROGRESSIVE QUESTIONS EXERCISE

1 A mixture of NH3(g ) and N2H4(g) is placed in a sealed (a) For the gas A , a = 0 and its dependence on p is linear at
container at 300 K. The total pressure is 0.5 atm. When all pressures
the container is heated to 1200 K, both substances (b) For the gas B, b = 0 and its dependence on p is linear at
decompose completely according to the equations : all temperatures
2NH3 (g) → N2 (g) + 3H2 (g) (c) For the gas C, which is typical real gas for which neither
and N2H4 (g) → N2 (g) + 2H2 (g) a = 0 nor b = 0, by knowing the minima and the point of
After decomposition, the total pressure at 1200 K is intersection, with Z = 1, a and b can be calculated
found to be 4.5 atm. What is the per cent of N2H4(g ) in (d) At high pressure, the slope is positive for all real gases
the original mixture? (assuming ideal behaviour)
7 At 100°C and 1 atm, if the density of liquid water is
(a) 35% (b) 40% (c) 75% (d) 25% 1.0 g cm −3 and that of water vapour is 0.0006 g cm −3, the
2 For gaseous state, if most probable speed is denoted by volume occupied by water molecules in 1 L of steam at
C * , average speed by C and mean square speed by C, that temperature is
then for a large number of molecules, the ratio of these (a) 6 cm 3 (b) 60 cm 3 (c) 0.6 cm 3 (d) 0.06 cm 3
speeds are :
8 Experimentally, it was found that a metal oxide has
(a) C *: C : C = 1.128 : 1.225 : 1(b) C *:C :C = 1 : 1.128 : 1.225 formula M 0.98 O. Metal M is present as M 2+ and M 3+ . It
(c) C *:C :C = 1 : 1.125 : 1.128 (d) C *:C :C = 1.225 : 1.128 : 1 oxide fraction of the metal which exists as M 3+ would be
3 When 3.2 g sulphur is vaporised at 450°C and (a) 4.08% (b) 6.05% (c) 5.08% (d) 7.01%
723 mm Hg pressure, the vapours occupy a volume of 9 Which of the following order of root mean square speed of
780 mL. What is the molecular formula of S vapours? different gases at the same temperature is true?
(a) S2 (b) S4 (c) S6 (d) S8 (a) (µ rms )H2 > (µ rms )CH4 > (µ rms )NH3 > (µ rms )CO2
4 What is the difference in the density of dry air at 1 atm (b) (µ rms )H2 < (µ rms )CH4 < (µ rms )NH3 < (µ rms )CO2
and 25°C and moist air with 50% relative humidity (c) (µ rms )H2 < (µ rms )CH4 > (µ rms )NH3 > (µ rms )CO2
under the same condition? The vapour pressure of (d) (µ rms )H2 > (µ rms )CH4 < (µ rms )NH3 < (µ rms )CO2
water at 25°C is 23.7 torr and dry air has 75.5% N 2 and 10 The behaviour of a real gas is usually depicted by plotting
24.5% O 2 . compression factor ( Z ) versus p at a constant
(a) 0.005 kg m−3 (b) 0.007 kg m−3 temperature. At low temperature and low pressure, Z is
(c) 0.01 kg m−3 (d) 0.05 kg m−3 usually less than one. This fact can be explained by
van der Waals’ equation when
5 In a spinel structure, oxide ions are cubical closed
packed whereas 1/8th of tetrahedral voids are occupied (a) the constant a is negligible and not b
by A ions and 1/2 of octahedral voids are occupied by B (b) the constant b is negligible and not a
(c) both the constant a and b are negligible
ions. The charge present on A and B ions will be
(d) both the constant a and b are not negligible
(a) A 2 + , B 3 + (b) A 3+ , B 2+ (c) A 4 + , B 2 − (d) A −1, B 2 −
11 When a capillary tube of diameter 0.4 mm is dipped in a
6 The given graph represents the variation of Z
pV liquid having density 800 kg m −3, then the height of liquid
(compressibility factor = ) versus p, for three real in the capillary tube rises to 4 cm. The surface tension of
nRT
liquid is (g = 9.8 m / s 2 ).
gases A, B and C. Identify the only incorrect statement.
. × 10−2 Nm−1
(a) 16 (b) 5.6 × 10−2 Nm−1
C (c) 6.3 × 10−2 Nm−1 (d) 7.3 × 10−2 Nm−1
A
12 When a sample of gas is compressed at constant
temperature from 15 atm to 6 atm, its volume changes
A from 76 cm 3 to 20.5 cm 3. Which of the following
Ideal gas statements are possible explanations of this behaviour?
B Z
C
I. The gas behaves non-ideally.
II. The gas dimerises.
III. The gas is absorbed into the vessel walls.
B (a) I, II and III (b) I and II only
p (atm) (c) II and III (d) Only I
13 For a crystal, the angle of diffraction ( 2 θ ) is 90° and the (a) 2.57 × 1021 (b) 5.14 × 1021
second order line has a d value of 2.28 Å. The . × 1021
(c) 128 . × 1021
(d) 171
wavelength (in Å) of X-rays used for Bragg’s diffraction is 15 Schottky defects occur mainly in electrovalent
(a) 1.612 (b) 2.00 compounds where
(c) 2.28 (d) 4.00
(a) positive ions and negative ions are of different size
14 How many unit cells are present in a cube shaped ideal (b) positive ions and negative ions are of same size
crystal of NaCl of mass 1.00 g? (Atomic mass of Na = 23, (c) positive ions are small and negative ions are big
Cl = 35.5) (d) positive ions are and negative ions are small

ANSWERS
SESSION 1 1 (d) 2 (c) 3 (c) 4 (d) 5 (a) 6 (a) 7 (a) 8 (b) 9 (b) 10 (a)
11 (b) 12 (c) 13 (c) 14 (c) 15 (d) 16 (c) 17 (b) 18 (b) 19 (c) 20 (c)
21 (d) 22 (d) 23 (b) 24 (d) 25 (c) 26 (a) 27 (a) 28 (d) 29 (c) 30 (d)
31 (d) 32 (c) 33 (d) 34 (a) 35 (a) 36 (c) 37 (d) 38 (c) 39 (a) 40 (a)
41 (c) 42 (d) 43 (a)

SESSION 2 1 (d) 2 (b) 3 (d) 4 (b) 5 (a) 6 (c) 7 (c) 8 (a) 9 (a) 10 (b)
11 (c) 12 (d) 13 (a) 14 (a) 15 (b)

Hints and Explanations

SESSION 1
1 lon-ion interaction is dependent on the square of distance, i.e. 5 Let a cm from HCl end, white fumes of NH4Cl are noticed.
1
ion-ion interaction ∝ 2
. P
r
1
Similarly, ion-dipole interaction ∝ . HCl NH3
r2
a (200 – a)
1
London forces ∝ 6
and dipole-dipole interactions
r rHCl MNH 3
1 From Graham’s law; =
[H-bonds] ∝ 3
. Thus, H-bonds being dipole-dipole rNH 3 MHCl
r
interactions is dependent on the inverse cube of distance a t 17
or × =
between the molecules. t (200 − a) 36.5
2 At constant temperature, [QTime of diffusion in tube for both is same.]
p1V1 = p2 V2 (Boyle’s law) ∴ a = 811. cm from HCl end.
380 × 7 = 760 × V2 22400 × 0.48
380 × 7 6 Volume of O 2 diffused = = 336 mL
V2 = = 3.5 L 32
760 Let the volume of CO 2 diffused be x mL.
3 By using Boyle’s law, 336
Rate of diffusion of O 2 = mL s −1
p × 8 V = p1 × V; 8 p = p1 1200
p1 = atmosphere pressure + pressure due to water in lake x
Rate of diffusion of CO 2 = mL s −1
∴ Pressure of water in lake = 7 p 1200
Since, p = pressure exerted by 10 m of water, the depth of the rO 2 VO 2 / t MCO 2
= =
lake = 70 m. rCO 2 VCO 2 / t MO 2
w w
4 nC 2 H 6 = , n(H 2 ) = 336
30 2
w /2 1 15 1200 = 44
pH 2 = ⋅p= = ⋅p or
x 32
w w 1
+ 1+ 16
1200
2 30 15
Hence, (d) option is correct. ∴ x = 286.6 mL
 0.1 × 0.082 × 273
7 According to Graham’s law of diffusion, = =7L 21 van der Waas’ constant a is due to force
r1 M2 0.32 of attraction and b is due to finite size of
= −3 molecules. Thus, greater the value of a
r2 M1 pV 3170 × 10
15 n = = and smaller the value of b, larger the
r235 RT 8.314 × 300
352 liquefaction.
∴ UF 6
= = 1.0043 = 1.27 × 10−3 mol
r238 349 Thus, a (Cl 2 ) > a (C 2H6 ) and
UF 6
16 van der Waals’ equation for one mole b (Cl 2 ) < b (C 2H6 ).
w
of real gas is  p + 2  (V − b ) = RT
8 For H2 : p × V = × R × 373 a a
22 We know that, pc = , VC = 3 b
2  V  27 b 2
V 3.5
For He : p × = × R × 298 When pressure is high p >> 2 such
a
8a
2 4 V and Tc =
27 Rb
that  p + 2  = p
Hence, wH 2 = 2.8 g a
 V  pc Vc a × 3b × 27 Rb 3
9 Average kinetic energy depends only = = = R
Thus, p ( V − b ) = RT ⇒ pV = RT + pb Tc 27 b 2 × 8 a 8
on temperature and does not depend
pV
upon the nature of gas. ∴Compressibility factor, Z = pc Vc 3
RT Compression factor, Z = =
3 pV RTc 8
=  1 +
10 urms = pb 

M  RT  23 Silicon exists as covalent crystal in solid
pV = nKT (K = Boltzmann’s constant) state. (Network like structure, like
pV pV
For a molecule, n = 1 17 Z = , i.e. < 1 or pV < nRT diamond).
nRT nRT
3KT
pV = KT ⇒ urms = ( p = 1 atm at STP) 24 The truncated octahedron is the 14
M
3 2 V < 1 × 0.0821 × 273 or V < 22.4 L faced Archimedean solid, with 14 total
Kinetic energy (E ) = KT or KT = E faces : 6 squares and 8 regular
2 3 18 To solve this problem, the stepwise hexagonals. The truncated octahedron
approach is required, i.e. is formed by removing the six right
2 (i) Write the van der Waals’ equation,
3× E square pyramids one from each point of
urms = 3 = 2E then apply the condition that at low a regular octahedron.
M M pressure, volume become high,
i.e. V − b ≈ V
urms (SO 2 ) T (SO 2 ) M (O 2 ) (ii) Now, calculate the value of
11 = ×
urms (O 2 ) M (SO 2 ) T (O 2 ) compressibility factor (Z).
[Z = pV / RT ]
T (SO 2 ) 32 According to van der Waals’
i.e. 1= × or,
equation,  p + 2  (V − b ) = RT
64 303 a Truncated Truncated octahedron

T(SO 2 ) = 606 K  V 
octahedron unfolded in two dimensions

At low pressure, 25 Given, n = 1, d = 0.281 × 10−9 m,

3RT u 3RT1 M2
12 urms = ∴ 1 = ×  p + a  V = RT⇒ pV + a = RT θ = 11. 8°
M u2 M1 3RT2  
 V2  V 2 × 0.281 × 10−9 × sin 11.8
a ∴ λ=
T1M 2 50 × 32 pV = RT −
= = =1 V
1
T2 M1 800 × 2 = 2 × 0.281 × 10−9 × 0.2044
Divide both side by RT,
pV a = 01149
. nm
13 Average KE = RT/N0
3 = 1−
2 RT RTV
26 The space lattice of diamond is fcc. The
(KE) 313 313
KE ∝ T ⇒ = 19 Intermolecular forces are given by the primitive basis has two identical atoms
term  p + 2  . (0,0,0),  , ,  associated with each
(KE) 293 293 a 1 1 1
 V   4 4 4
14 Since, the external pressure is 1.0 atm,
point of the fcc lattice. Thus, the
20  p + 2  V = RT ⇒pV = RT − …(i)
the gas pressure is also 1.0 atm as a a
conventional unit cube contains eight
piston is movable. Out of this 1.0 atm,  V  V atoms. Also, diamond is tetrahedral.
partial pressure due to known Eq. (i) is a straight line equation
compound is 0.68 atm. Therefore, 1
partial pressure of He between pV and where slope is − a.
V
= 1.00 − 0.68 = 0.32 atm Equating with slope of the straight line
n(He) RT given in the graph
Volume =
20.1 − 21.6
p(He) −a= = − 1.5, a = 1.5
3− 2
 4 × 0.14
a= = 0.396 nm = 0.4 nm 39 Only three elements iron (Fe), cobalt
27 D 2 (Co) and nickel (Ni) show
r ferromagnetism at room temperature.
32 Length of the edge of NaCl unit cell
a CrO 2 is also a metallic and
= 2 × distance between Na + and Cl −
2r ferromagnetic compound which is used
C = 2 × a = 2 a pm
to make magnetic tapes for cassette
r 33 For fcc arrangement, 4r = 2 a recorders.
a

A B where, r = radius and a = edge length

a 40 Both Assertion and Reason are true,
2a a
From this figure, ∴Closest distance = 2 r = = Reason is a correct explanation for
2 2 Assertion. Because motion of gas in one
( AC )2 = ( AB)2 + (BC )2 = a2 + a2 = 2 a2
34 Mass of one unit cell = V × d = a3 × d , direction gives zero average speed.
Also, ( AD)2 = ( AC )2 + (DC )2
Z⋅M 41 Assertion is true but Reason is false.
3 Density =
(4r )2 = 2 a2 + a2 , 16 r 2 = 3 a2 , r =a a3 ⋅ N0 Because at high altitude, atmospheric
4 pressure is low.
a ×Z×M
3
ZM
Now, when Na metal crystallises in bcc Mass of 1 unit cell = =
unit cell with unit cell edge length a3 × N0 N0 42 Both Assertion and Reason are false.
a = 4.29 Å 4 × 58.5 −23 Liquids tends to possess minimum
= = 38.87 × 10 g
3 6.02 × 1023 number of molecules on the surface due
∴ r= × 4.29 Å = 1. 86 Å to surface tension.
4 Number of unit cells in 1g
1 43 Both Assertion and Reason are true.
28 Atomic radius of lithium =
3
a = = 2.57 × 10 21
4 38.87 × 10−23 Reason is a correct explanation for
Assertion. Because F-centre contains
173
.
= × 351 = 1518 . pm ≈ 152 pm 35 d =
ZM
(for bcc, Z = 2) unpaired electron and show
4 NA a3 paramagnetic character.
29 CsCl crystal has bcc structure. (2) × 56.0 g mol −1
d Fe = SESSION 2
(6.02 × 10 mol −1 ) (2.861 × 10 −8 ) 3 cm3
23

D = 7 . 94 g cm−3
1 Let the moles of NH3 and N2H4 in original
mixture are n1 and n2 respectively.
⇒ Z = 4 ×  1 −
rCl – ZM 0.1 
a 36 d =  = 3.996 From given decomposition reactions :
N0 a 3  100 
2 moles of NH3 produce total 4 moles of
2r Cs+ (because it contains 0.1% Schottky N2 and H2 .
C defect) 1 mole of N2H4 produces total 3 moles
rCl – 3.996 × 40 of N2 and H2 .
a d=
6.02 × 1023 × (0.556 × 10−7 )3 Hence, total moles after decomposition
A a B = 2 n1 + 3n2
= 1.5448 g/cm3
Ideal gas equation : pV = nRT
AD2 = AC 2 + CD2 = (a 2 )2 + a2 = 3 a2 37 For the preparation of n-type Now, (0.5 atm) V = (n1 + n2 ) R (300 K)
⇒ AD = a 3 semiconductor from silicon, it should …(i)
be doped with a substance of and (4.5 atm)
Also, AD = r + 2r +r =a 3
Cl − Cs + Cl − 5 valence electrons. V = (2 n1 + 3n2 ) R (1200 K) …(ii)
3
⇒ r +r = a 38 It is the “Frenkel defect” in which On dividing the two equations and
Cs + Cl − 2 cations leave their original site and rearranging
2 n1 + 3n2 9 2 (n1 + n2 ) + n2 9
30 Number of atoms ( A) per unit cell occupy interstitial site as shown below: = or =
1 n1 + n2 4 n1 + n2 4
=8× =1 − −
A+ B A+ B A+ n2 9 1
8 or = −2 =
Number of atoms (B) per unit cell n1 + n2 4 4
A+
1 5 n2
= (6 − 1) × = − − − ∴% of N2H4 is × 100 = 25%
2 2 B B A+ B n1 + n2
(QOne B atom is missing.) 1
or × 100 = 25%
Thus, formula is A 1 B5 / 2 or A2 B5 . 4
− −
A+ B A+ B A+
31 For fcc unit cell, 2 RT 8RT 3RT
2 C* = , C = , C=
r=
2
a M πM πM
− − −
4 B A+ B A+ B ∴ C*: C : C = 1 : 1.128 : 1.225
2
⇒ 0.14 = a 3 Given, p = (723/760) atm, w = 3 . 2 g
4
 T = 273 + 450 = 723 K = 0.007 kg m−3 1
µ rms ∝
⇒ V = (780/1000) L M
5 In cubic closed packing, there will be
w More the mass of the molecule, less is
pV = RT four oxide ions; the µ rms .
Q
M
3.2 × 0.0821 × 760 × 1000 × 723 8×
1 1
= one A ion and 4 × = 2 B ions. 10 At low temperature and low pressure, Z
∴M = 8 2
723 × 780 +2 +3 −2 is usually less than one. This fact can be
= 256 Hence, formula will be A B2 O 4 . explained by van der Waals’ equation
when the constant b is negligible and
Q 32 g sulphur has 1 atom of S. 6 van der Waals’ equation is not a.
∴ 256 g S has 256/ 32 = 8 atoms of S
 p + a  (V − b ) = RT rhdg
∴ Molecular formula = S8   11 T =
 V2  2
4 M(dry air) (4 × 10−4 ) × (0.04) × 800 × 9.8
When a = 0, p (V − b ) = RT =
M1(O 2 ) x1(% of O 2 ) 2
+ M 2 (N2 ) x 2 (% of N2 ) or pV = RT + pb
= pV pb (r = 0.4 mm = 4 × 10−4 m)
x1 + x 2 or , i.e. Z = 1 + .
RT RT = 4 × 10−4 × 0.04 × 400 × 9.8
32 × 24.5 +28 × 75.5
= = 28.98 g mol −1 Thus, Z > 1and increases with increase
100 = 4 × 4 × 4 × 98 × 10−5
of pressure. Hence, (a) is correct.
pM(air) 1 × 28.98 = 6.3 × 10−2 Nm−1
d(dry air) = =
When b = 0,  p + 2  V = RT
a
RT 0.0821 × 298.15  V  12 When a sample of gas is compressed at
= 1.184 g L−1 = 1.184 kgm−3 a pV a
or pV + = RT or , i.e. Z = 1 − . constant temperature from 15 atm to 6
Relative humidity (50 %) V RT VRT atm, its volume changes from 76 cm3 to
partial pressure of H2O in air Thus, Z < 1and decreases with
= 20.5 cm 3 . This behaviour shows that
vapour pressure of H2O increase of pressure. Hence, (b) is gas behaves non-ideally.
p (H2O) = 0.50 × 23.7 torr correct. (d) is also correct and only
11.85 wrong statement is (c). 13 Given, angle of diffraction (2θ) = 90°,
= 11.85 torr = atm
760 7 Mass of 1L steam θ = 45°
= 0.0156 atm = 1000 × 0. 0006 = 0.6 g Distance between two planes,
% of H2O vapour in air = mass of liquid water d = 2.28 Å, n = 2
0.0156 × 100 Volume of water = 0.6 cc
= = 1.56% (d = 1 g cm−3 ). Bragg’s equation is nλ = 2d sin θ
1
2 × λ = 2 × 2.28 × sin 45°
% of N2 and O 2 in air Same volume will be occupied by water
λ = 1.612
= 100 − 1.56 = 98.44% molecules in steam.
M (wet air) 8 Given, metal oxide = M 0. 98O 14 Mass of one unit-cell (m) = volume × density
28.98 × 98.44 (air) +
Let x ions are of M in + 3 states, = a3 × d
18 × 1.56 (water vapour) Therefore, 3x + (0.98 − x ) × 2 = 2,
= MZ
100 x = 0.04 = a3 ×
−1 N0 a3
= 28.81 g mol 0.04
% of M in +3 states = × 100 Mz 58.5 × 4
pM (wet air) 0.98 × m= g
∴ d (wet air) = N0 6.02 × 1023
RT = 4.08%
1 × 28.81 ∴ Number of unit cell in 1 g
= 9 The correct order of root mean square
0.0821 × 298.15 1 6.02 × 1023
−1
speed of different gases at the same = = = 2.57 × 1021
= 1.177 g L temperature is m 584 × 4
= 1.177 kg m−3 (µ rms )H 2 > (µ rms )CH 4 > (µ rms )NH 3 15 Schottky defects occur mainly in
Difference > (µ rms )CO 2 electrovalent compounds where positive
= 1.184 − 1.177 We know that, ions and negative ions are of same size.