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Introduction

The classification of matter into three different states, namely solid, liquid and
gaseous state is termed as the physical classification of matter. Most properties of
solid, liquid and gases that can be observed with our sense organs are called as
'macroscopic' properties. The description of the behaviour of the three states of
matter in terms of atomic theory is called 'microscopic' description of matter. From
the study of the observable properties of different states of matter one can
understand the microscopic nature of matter in terms of the behaviour of constituent
particles.

The important characteristics of the three states are listed out below:

Solid state

A solid possesses a definite size (volume) and a definite shape under ordinary
conditions; and tends to maintain these even under deforming conditions. The
substances in solids are closely packed and bound by strong inter particle attraction,
making them rigid and geometrical. Some common examples of solids are iron, silver,
common salt, etc.

Liquid state

A liquid possesses a definite volume but not definite shape. The substances in liquids
have particles, which are loosely packed and bound to each other by forces weaker
than those of solids. This makes a liquid mobile and shapeless resulting in its taking
up the shape of the container in which it is placed. A liquid also has a tendency to
flow. For example, water, alcohol, milk, oil, etc.

Gaseous state

A gas neither possesses a definite volume nor a definite shape. The substances in a
gas have particles that are separated by great distance, having virtually no force of
attraction between them. A gas occupies the whole of the volume of the vessel in
which it is placed. It also takes up the shape of the container. For example, air,
carbon dioxide, oxygen, hydrogen, etc.

The three states of matter are inter-convertible. This can be done by heating or
cooling. Heating increases the inter particle spacing and kinetic energy of the
particles. So, a solid on heating gets converted into a liquid, and a liquid into a gas.

The various points of distinction between the three states


The Gaseous State
Of the three states of matter, the gaseous state is the simplest and shows greatest
uniformity in behaviour. Gases show almost similar behaviour irrespective of their
chemical nature. This state is characterized by:

Gases maintain neither the volume nor the shape. They completely fill the
container in which they are placed.

They expand appreciably on heating.

Gases are highly compressible. The volume of the gas decreases when the
pressure increases.

They diffuse rapidly into space.

Gases exert equal pressure in all directions.

All gases are colourless except a few e.g. chlorine (greenish yellow) bromine
(reddish brown), nitrogen dioxide (reddish brown)

The behaviour of gases can be described by certain quantitative relationships called


gas laws. They give the relationship between mass, pressure, volume and
temperature.

Measurable Properties of Gases

The important fundamental properties of gases are mass, volume, pressure and
temperature. These are discussed below:

Measurement of mass

The mass of a gas can be measured by direct weighing. The container in which the
gas is enclosed is first weighed. Then the weight of the container, after removing all
the gas, is measured again. The difference between the two weights gives the mass
of the gas.

Units of mass

The most common unit for mass is expressed in grams (g) or kilogram (kg) (1 kg =
103g).

In chemical measurement, IUPAC prescribes that the mass of a gas (m) be expressed
in terms of the number of moles (n). The number of moles can be obtained from the
mass of the gas using the relationship

Measurement of volume

The volume of a substance is the space occupied by it. A gas occupies the entire
volume of the container available to it. The measurement of the volume of a gas only
requires the measurement of the volume of the container enclosing it.

Units of volume

Generally, volume is expressed in units of litres (L), millilitre (mL) or cubic


centimetres (cm3). The different units are related as

1 mL= 1 cm3

1 L = 103 mL or 1 dm3

The SI unit of volume is m3. As this unit is too large, volume is generally expressed in
smaller units of cubic decimetre (dm3) or cubic centimetre (cm3). These are related to
each other as:

1 m3 = 103 dm3 = 106 cm3

The volume of the gas depends upon its amount, temperature and pressure V = f
(amount, temperature, pressure).

Measurement of Pressure

Gases exert uniform pressure in all the directions on the walls of the container in
which they are confined. As pressure is force per unit area, the pressure of the gas is
the force exerted by the gas per unit area on the walls of the container.

Atmospheric pressure

Air is pulled towards the surface by gravity and this exerts pressure on the Earth's
surface. The pressure exerted by the gases of the atmosphere on the surface of the
Earth is called atmospheric pressure.

Measurement of atmospheric pressure

Atmospheric pressure is measured by an instrument known as barometer. This


consists of a glass tube closed at one end and filled with pure mercury. The tube is
then inverted into an open vessel of mercury. The mercury level in the tube drops
until the pressure due to the column of mercury in the tube becomes equal to the
atmospheric pressure acting outside the tube. The region above the mercury in the
tube is almost a perfect vacuum, therefore, the pressure due to mercury column is
equal to atmospheric pressure.

The pressure (P) is expressed as:

P = h. .g

where 'h' is the height of mercury column in the barometer

'' is the density of mercury

'g' is the acceleration due to gravity.


Fig: 2.1 - Mercury barometer

Units of atmospheric pressure

The maximum height of mercury, which can be supported by the atmospheric


pressure provides a measure of that pressure.

A standard pressure of one atmosphere (1 atm) is defined as the pressure that will
support a column of mercury of 76 cm height at 0°C (density of mercury (13.5951
gcm-3) and at standard gravity

= 980.665 cm-2.

One atmosphere is also referred to as 760 torr. This unit is named after the scientist
Torricelli, who invented the Barometer. Thus

1 atm = 76.0 cm of mercury (cm Hg)

= 760 mm of mercury (mm Hg)

= 760 torr.

The S.I. unit of pressure is pascal (Pa), which is the pressure exerted when a force of
Newton (1 N) acts on 1m2 area. Pascal is related to atmosphere as:

1 atm = 101.326 x 103 N m-2

= 101.325 kPa

However, for approximate work, one atmosphere is taken to be equal to 102 kPa or
105 Pa or Nm-2.

The pressure of gases are measured by a device known as manometer that can be
either open end manometer or closed end manometer. These manometers consist of
'U' tube partly filled with a non-volatile liquid like mercury. During measurement, the
difference in the levels of the mercury in the two limbs gives the difference in
pressure on the two sides.

Measurement of Temperature
Temperature is a measure of hotness or coldness of a body. It is a measure of kinetic
energy possessed by the molecules. A hot body is said to be at a higher temperature
and a cold body is said to be at a lower temperature. The devices used to measure
temperature are called Thermometers. The substance commonly used in the
thermometers is mercury.

Temperature is commonly measured in Celsius scale (centigrade scale). In this scale,


the freezing point of water (0°C) and the boiling point of water (100°C) at one
atmospheric pressure are taken as reference points. The range between 0° to 100° is
divided into one hundred equal parts, each division corresponding to 1°C.

Unit of temperature

The S.I. unit of temperature is degrees Kelvin (K) and this scale is known as Kelvin
scale. The zero point on the Kelvin scale is known as absolute zero, which is equal to
-273.15°C.

The temperature on the Celsius scale is converted to temperature on Kelvin scale by


the addition of 273.15°. Thus,

°C + 273.15 = K

Standard temperature and pressure

The properties of a gas depends upon the temperature and pressure. Hence, it is
convenient to specify a particular temperature and pressure for comparison of
different gases. The standard conditions of temperature and pressure are abbreviated
as S.T.P. (Standard Temperature and Pressure) and N.T.P. (Normal Temperature and
Pressure).

Standard Temperature and Pressure (S.T.P. or N.T.P.) values are:

Temperature = 0°C or 273.15 K

Pressure = 1 atm or 760 mm Hg or 760 torr or 101.325 kPa (S.I. units)

Gas Laws - Boyle's Law


The study of behaviour of gases has led to the formulation of a few important
generalisations called as Gas Laws.

Boyle's Law

Robert Boyle proposed this law in the year 1662, giving the relationship between
pressure and volume of given mass of a gas at constant temperature. This law states
that volume (V) of a given mass of gas is inversely proportional to the pressure (P) at
constant temperature.

Mathematically it can be expressed as,

or PV = k = constant
At a given temperature, when the pressure of the gas is changed from

P1 to P2 the relation becomes

P1 V1 = P2 V2 = constant

where, V2 is the new volume of the gas. The product of volume and pressure for a
given mass of a gas at constant temperature is constant. This aspect can be
experimentally verified by taking the pressure volume data for a gas like 10g of
oxygen at 25oC. It is observed that with the increase in pressure the volume
decreases and the product 'PV' remains constant. This data when plotted with 'P'
along the x-axis and 'V' long the y-axis gives a curve.

Fig: 2.2 - Variation of P and V at constant T

The curve shows the inverse relation of 'P' and 'V'. When the pressure is P1, the
volume is V1and when the pressure is increased to P2, the volume V2 is smaller than
V1. If the graph is plotted between 'P' and

1 / V, a straight line passing through the origin is obtained. On plotting the product
'PV' along y-axis and Pressure 'P' along x-axis, a horizontal line is obtained, indicating
'PV' to be constant even if we change pressure.
Fig: 2.3 - Plot of P versus 1/V

The P-V curve for a given gas is different at different temperatures. The plot of 'PV'
against 'P' at different temperature is known as Isotherms. The higher curve
corresponds to higher temperature. Boyle's law expresses the compressible nature of
gas, which gives a measure of its increased density.

Problem

1. A gas occupies a volume of 250 mL at 745 mm Hg and 25oC. What additional


pressure is required to reduce the gas volume to 200mL at the same concentration?

Solution

P1 = 745 mm Hg V1 = 250 mL

P2 = ? V2 = 200mL

P1V1 = P2V2

The additional pressure required is 931.25 - 745 = 186.25 mm.

Charles' Law
Charles formulated this law in 1787 giving the relationship between volume and
temperature of a gas. This law stated that at constant pressure, the volume of a
given mass of gas increases or decreases by 1/273 of its volume at 0oC for every one
degree rise or fall.
or

A plot of volume along x-axis and temperature along y-axis gives a straight line
intercepting the y-axis. When this line is extrapolated to lower temperature, it cuts
the x-axis, which represents the zero volume.

Fig: 2.4 - Plot of volume versus temperature (P constant)

The temperature at which the volume of the gas becomes zero is found to be -273oC,
which is independent of the nature and pressure of the gas. The lowest temperature
below which volume does not exist (negative), is called the absolute zero.
Temperature measurements based on the absolute zero is known as absolute scale of
temperature or Kelvin temperature scale.

Charles' law is mathematically represented as:

273 + t = T (K) and 273 =T0 which corresponds to 0oC on absolute temperature scale

Thus, V/T constant = k'


The volume of a given mass of a gas is directly proportional to the absolute
temperature at constant pressure. If V1 is the volume of a certain mass of gas at
temperature T1 and V2 is the volume of the same mass of the same gas at
temperature T2 at constant pressure, then,

The validity of Charles' law can be determined by measuring the volumes of a given
mass of a gas at different temperatures, at constant pressure. The value of V/T
remains to be constant in this study. The curves obtained by plotting volume
temperature ratio against different pressures are called isobars. Charles described
the expansive nature of gases with lower density.

Problem

2. A sample of helium has a volume of 520 cm3 at 100oC. Calculate the temperature
at which the volume will become 26cm3. Assume that pressure is constant?

Solution

V1 = 520 cm3 V2 = 260 cm3

T1 = 100 + 273 = 373K T2 = ?

or

T2 = 186.5 K

t = 186.5 - 273 = 86.5oC.

Avogadro's Law
The relationship between the volume of a gas to the number of molecules at constant
temperature and pressure is known as Avogadro's law. It states that equal volumes of
all gases under similar conditions of temperature and pressure contain equal number
of molecules. 22.4 litres of any gas at STP contains 6.023 x 1023 number of molecules
irrespective of its nature. Therefore, the volume of a gas is directly proportional to the
number of molecules N.

V N (at constant T and P)

The number of moles 'n' of a gas is also proportional to the number of molecules.
n = N/No

Where, No represents the Avogadro number and is constant. So,

n N,

V N or V n.

Thus, it can be concluded that the volume of gases at constant temperature and
pressure is directly proportional to their number of moles.

Dalton's Law of Partial Pressures


Dalton proposed this law on the pressure exerted by a mixture of non-reacting gases
in an enclosed vessel. The law of partial pressure states that the total pressure
exerted by a mixture of two or more non-reacting gases in a definite volume is equal
to the sum of the individual pressures, which each gas would exert if it occupies the
same volume at a constant temperature. If p1, p2, p3 are the individual partial
pressures of the known gases, then the total pressure 'P' of the mixture of gases at
the same temperature and pressure is given by the relation:

P = p1 + p2 + p3 + …….

Partial pressure is the pressure exerted by the gas if present alone in the vessel at
the same conditions of temperature.

For example,

A gas 'A' having a pressure of 300 mm Hg is contained in a vessel and another gas 'B'
with a pressure of 400 mm Hg is contained in another vessel, are mixed in the third
vessel at the same temperature. The total pressure in the third vessel is,

P = PA + PB

= 300 + 400 = 700 mm Hg


Fig: 2.5 - Dalton's law of partial pressures

Dalton's law is used to calculate the pressure of a gas.

Problem

3. A 10 L flask at 298 K contains a gaseous mixture of CO and CO2 at a total pressure


of 1520 mm of Hg. If 0.20 mole of CO is present, find the partial pressure of CO and
that of CO2?

Solution

According to Dalton's Law: pCO + pCO2 = P = 1520 mm of Hg

= 0.49 atm.

Partial pressure of CO2, pCO2= P - (pCO)

= 2.0 - 0.49 = 1147.6 mm of Hg

Graham's Law of Diffusion


Gases have the tendency to spontaneously intermix and form a homogenous mixture
without the help of external agency. This is due to the presence of large amount of
empty space between the gas molecules that makes their movement rapid into each
other. The gases move from a region of higher concentration to a region of lower
concentration until the mixture attains uniform concentration.

Graham studied the rate of diffusion of various gases and gave this law. It states that
under similar conditions of temperature and pressure, the rates of diffusion of gases
are inversely proportional to the square roots of their densities.

If r1 and r2 are the rates of diffusion of two gases 'A' and 'B' and 1 and 2 are their
densities, then
Molecular mass is twice the vapour density, substituting this in the above equation,
we have

where M1 and M2 are the molecular masses of the two gases. Thus, the rate of
diffusion of gases are inversely proportional to the square root of their molecular
masses.

Rate of diffusion is also equal to the volume of the gas, which diffused per unit time,

If V1 and V2 are the volumes of the gases diffusing in time t1 and t2 respectively, then

Therefore,

If the volume diffused is the same, (V1 = V2)

Then,

Graham's law is useful in:

Separation of gases having different densities by diffusion.

Determining the densities and molecular masses of unknown gases by comparing


their rates of diffusion with known gases.

Separating the isotopes of some of the elements.


Effusion

When the gases contained in a vessel are allowed to escape through a small
aperature, it is effusion.

Fig: 2.6 - Process of diffusion and effusion

Problem

4. An unknown gas diffuses four times as quickly as oxygen. Calculate the molecular
mass of the gas.

Solution

Let the rate of diffusion of oxygen be r(O2) = r1

The rate of diffusion of the unknown gas r (x) = 4r

Molecular mass of O, M(O) = 32

Molecular mass of unknown gas M (x) = M

From Graham's Law of diffusion,

or

Squaring on both sides,


Ideal Gas Equation
By combining Boyle's and Charles' laws, an equation can be derived that gives the
simultaneous effect of the changes of pressure and temperature on the volume of the
gas. This is known as combined Ideal Gas Equation. A simple and direct method of
deriving this equation is as follows:

According to Boyle's law, for a given mass of a gas at constant temperature

According to Charles' law,

Combining (i) and (ii)

or

or

Now, if V1 is the volume of a gas at temperature T1 and pressure P1. V2 is the volume
of same amount of gas at temperature T2 and pressure P2, then

The above relationship is very useful for converting the volume of a gas from one set
of conditions to another.

The numerical value of the constant of proportionality (K) depends upon the quantity
of gas. The volume of a gas is directly proportional to the number of moles of gas at
constant temperature and pressure (Avogadro's law). This means that 'K' is directly
proportional to the number of moles, 'n', i.e.,
K n

or K = nR,

where 'R' is the universal gas constant of proportionality. The value of 'R' is same for
all gases.

However, the numerical value of 'R' varies with the units in which pressure and
volume are expressed. Therefore the Ideal gas Equation is derived as:

For one mole (n = 1),

PV = RT (Ideal Gas Equation)

The Ideal Gas Equation is also known as the equation of state for gases as it
expresses the quantitative relation ship between the four variables that describe the
state of the gas. The word 'ideal' is used here because in reality no gas obeys the
above condition and the gases, which deviate from ideality are called as real gases.

Universal gas constant (R)

From the above ideal gas equation:

The universal gas constant is a measure of energy change (work done) per mole of
the gas for one degree change in its temperature.

Numerical Value of R

The magnitude and unit of 'R' depends upon the units in which pressure, volume and
temperature are expressed.

Conditions and problems

I)When pressure is expressed in atmosphere and volume in litres

Under standard condition of temperature and pressure i.e., when

P = 1 atm

T = 273.15 K
V = 22.414 L mol-1

This gives,

II) When pressure is expressed in atmosphere, and volume in mL

Here,

P = 1 atm

T = 273.15 K

V = 22414 mL mol-1

This gives,

III) R in energy units

When,

If 'R' is to be expressed in CGS units, the unit of pressure should be dyne cm-2 and
volume in cm3 mol-1. Then,

Normal temperature T = 273.15 K

Normal pressure, P = (1 x 76 x 13.6 x 981) dyne cm-2

Molar volume under normal temperature and pressure

= 22414 cm3mol-1

Therefore,

= 8.314 x 107 erg deg-1 mol-1

Since, 4.182 x 107erg = 1calorie

Hence,
IV) In SI units

In the SI system of units, under NTP conditions,

P = 101325 N m-2

T = 273.15 K

V = 22.414x10-3 m3

Therefore,

= 8.314 J mol-1 K-1

The value of Gas constant R in different units

Problems

5. Calculate the number of moles of hydrogen (H2) present in a 500 cm3 sample of
hydrogen gas at a pressure of 760 mm of Hg and 27°C.

Solution

According to ideal gas equation, PV = nRT

T = 27 + 273 = 300 K, R=82.1 cm3 atm K-1 mol-1


n = 0.0203 mol = 2.03 x 10-2 mol.

6. About 200 cm3of a gas is confined in a vessel at 20°C and 740 mm Hg pressure.
How much volume will it occupy at S.T.P.?

Solution

We are given

P1 = 740 mm Hg P2 = 760 mm Hg

T1 = 20 + 273 = 293K T2 = 273 K

V1 = 200 cm3 V2 = ?

According to gas equation,

Substituting the values, we get

= 181.4 cm3.

7. Calculate the volume occupied by 2 moles of an ideal gas at

2.5 x 105 Nm-2 pressure and 300 K temperature.

Solution

According to ideal gas equation,

n = 2 mol, T = 300 K, P = 2.50 x 105 Nm-2

R = 8.314 Nm K-1 mol-1

= 19.95 x 10-3m3=19.95dm3.

Ideal and Real Gases


An ideal gas is one, which obeys the general gas equation of PV = nRT and other gas
laws at all temperatures and pressures. A real gas, does not obey the general gas
equation and other gas laws at all conditions of temperature and pressure.

Effect of pressure

All gases are known to exist as real gases and show ideal behaviour only to some
extent under certain conditions. When PV = nRT for ideal gases, then the ratio

For real gases Z may be less or more than one. If Z<1 then it is called negative
deviation which means that the gas is more compressible. If Z>1 then the gas is less
compressible and it is called positive deviation. It is observed that the deviations are
low at low pressures. At high pressures the deviations depends on the nature of the
gas.

A plot of versus P for some common gases are shown in the figure.

Fig: 2.7 - Plot of compressibility factor as a function of P

For H2 and He, 'Z' is greater than one while for N2, CH4 and CO2 'Z' is lesser than one.
This means that these gases are more compressible at low pressures and less
compressible at high pressures than expected from ideal behaviour.

Effect of temperature

The effect of temperature on the behaviour of real gases is studied by plotting the
value of 'PV' against temperature. It is observed that the deviations from ideal
behaviour is less with the increase in temperature.

Thus, real gases show ideal behaviour at low pressures and high temperatures.

Causes for deviations


In order to know the causes for deviations from ideality, Van der Waal pointed out the
faulty assumption that were made in formulating the kinetic molecular model of
gases.

The assumption that the volume occupied by the molecular mass is negligible as
compared to the total volume of the gas is invalid. Although this volume is 0.1%
volume of the total volume of the gas, the volume of the molecules of gas remain
same as compared to the decrease in the total volume of the gas. The decrease in
volume occurs with the decrease in temperature and increase in pressure, but the
volume of the molecules cannot be neglected.

The forces of attraction between the gas molecules were considered to be


negligible. This assumption is only valid at low pressures and high temperatures
because in these conditions the molecules lie far apart. But at high pressures and low
temperatures the volume of the gas is small and so the attractive forces though very
small, exist between them.

Hence, Van der Waal who incorporated the idea of finite molecular volume and
intermolecular forces modified the Ideal Gas Equation as follows:

Volume correction was made stating that the free volume of the gas is actually less
than the observed volume. A suitable volume term 'b' is subtracted from the
observed volume known as the excluded volume or correct volume. The correction
term, 'b' is a constant depending upon the nature of the gas. For 'n' moles of gas, the
correction term is 'nb' and so the corrected volume is given by,

Vcorrected = (V-nb) for 'n' moles.

Correction due to intermolecular forces is considered in terms of the pressure. A


molecule at the wall of the container experiences an inward pull due to attractive
intermolecular force of the neighbours. The molecules strike the wall with a lesser
force and so the observed pressure is less than the ideal pressure. The pressure
correction term

Substituting these values for pressure and volume, the ideal gas equation can now be
written as:

This equation is Van der Waal's equation of state. Here, the constant 'a' measures the
forces of attraction between the molecules of the gas and 'b' relates to the
incompressible volume of the molecules, measuring the size of the gas molecules.

One can now summarize the differences between ideal and real gases as follows:
Kinetic Molecular Theory of Gases
In order to explain the observed behaviour of gases, a model was proposed based on
the molecular and kinetic concept of gas molecules. This model takes into account
the particulate nature of matter and the constant movement of particles.

Postulates of Kinetic Theory

All gases are made up of large number of minute particles called molecules.

Large distances separate the molecules so that the actual volume of the molecules
is negligible as compared to the total volume of the gas.

The molecules are in a state of constant rapid motion in all directions, colliding with
one another and also with the walls of the container.

The molecular collisions are perfectly elastic with no loss of energy and only
redistribution of energy during collision.

There are no attractive or repulsive forces between the molecules.

The pressure exerted by the gas is due to the bombardment of its molecules on the
walls of the container per unit area.

The average kinetic energy of the gas molecules is directly proportional to the
absolute temperature.

On the basis of these postulates an equation for the pressure of the gas is derived
as

This is called the Kinetic gas equation where 'N' is the number of molecules in
volume 'V', 'm' is the mass of the

molecule and 'u' is the root mean square velocity of the molecules.
Liquefaction of Gases
There are large empty spaces (voids) separating the tiny molecules of gases from one
another. Each molecule enjoys an almost independent existence. Molecules are in a
state of continuous rapid motion and have negligible attractive forces between them
due to wide separation. This is particularly so, when temperature is high and pressure
is low. When the temperature of the gas is lowered, both the volume of the gas and
the kinetic energy of the molecules decrease. The molecular motion becomes slow
and molecules become sluggish. The progressive decrease of temperature brings the
molecules closer and closer because they are unable to resist the attractive force that
starts operating between them. Ultimately, at sufficiently low temperature, the voids
between the molecules become less than 10-5cm and the gas changes into liquid
state.

This process of liquefaction by bringing gas molecules closer can also be achieved by
increasing the pressure of the gas: this also decreases the volume of the gas. For
example, sulphur dioxide can be liquefied at 265 K if pressure is 760 mm of Hg. It can
also be liquefied at 293K if the pressure is increased to 2470 mm of Hg.

Thus, liquefaction of gases can be achieved by either decrease of temperature or by


increase of pressure.

Concept of critical temperature

Experimental observations have shown that effect of temperature is more significant


in achieving liquefaction than that of pressure. This is due to the fact that for every
gas there is a certain temperature above which it cannot be liquefied how so ever
high the pressure may be. The kinetic energy of gas molecules above this
temperature is sufficient enough to overcome the attractive forces. This temperature
is referred to as the critical temperature of the gas. It may be defined as the
temperature above which a gas cannot be liquefied by application of pressure. A gas
will remain as gas above critical temperature and in order to liquefy it by
compression, it has to be cooled to its critical temperature. Critical temperature is
denoted by Tc.

For example,

Tc of CO2 = 304.1 K.

Critical pressure (Pc)

The pressure required to liquefy the gas at its critical temperature is called critical
pressure.

For example, the value of Pc for CO2 = 55328 mm of Hg.

Critical volume (Vc)

The volume of one mole of the gas at critical temperature and critical pressure is
called critical volume.

For example, value of Vc for CO2 = 94.0 cm3 mol-1

The parameters Tc, Pc and Vc for a gas are collectively called 'critical constants'.
Relationship between Critical Constant and Van der Waal's Constants
The relationship between critical constants of the gases and their Van der Waal
constants is as follows:

(i) Vc = 3b

(ii) Pc = a/27b2

(iii) Tc = 8a/27Rb

(iv) The critical compressibility factor Zc is given by,

These relations have been derived from the calculations based on Van der Waal's
equation.

Boyle's Law

When the volume of the gas is reduced, the molecules move with the same speed but
in lesser space. As a result, the frequency of collisions with the walls of the container
increases and a pressure increase is noticed. This is the statement of Boyle's law and
this can be deduced from the kinetic gas equation,

and the number of molecules N remain constant. Thus,

Charle's Law

When a gas is heated the molecules move faster increasing the pressure. But to
maintain the pressure constant, the force of collision is compensated with an increase
in volume. So, at constant pressure the volume of the gas increases with
temperature. By kinetic gas equation we have,
substituting this we have,

This is the statement of Charles' law.

Dalton's Law

When more than one type of molecule is present (at constant T) then, the total
pressure exerted by the mixture should be equal to the sum of their individual
pressures when present alone. The pressure exerted by each gas is

where 1 and 2 are the average molecular kinetic energies of the two gases
containing N1and N2 molecules per unit volume. Since the molecules behave
independent of each other,1 and 2 =  , hence

= p1 + p2

The total pressure is equal to the sum of the pressures, which each gas would exert if
allowed to occupy the entire space. This is Dalton's law of partial pressures.

Graham's Law of Diffusion

From kinetic theory,


Since the rate of diffusion of a gas is determined by the molecular speed,

The rate of diffusion of a gas depends inversely on the square root of its density. This
is Graham's law of diffusion.

Maxwell's Distribution of Molecular Speeds

On plotting a fraction of molecules having different speeds against the speeds


of the molecules (along x-axis) a curve known as Maxwell's distribution curve is
obtained. The important features of which are:

The fraction of molecules with very low or very high speeds is very small.

The fraction of molecules possessing higher and higher speeds goes on increasing
till it reaches a peak and then starts decreasing.

The maximum fraction of molecules possess a speed, corresponding to the peak in


the curve which is referred to as most probable speed.

Fig: 2.8 - Maxwell-Boltzmann's distribution of speeds

The increase in temperature of the gas results in increase in the molecular motion.
Consequently, the value of the most probable speed increases with increase in
temperature. It may be noted that as long as the temperature of a gas is constant,
the fraction having the speed equal to most probable speed remains the same but
the molecules having this speed may not be the same. In fact, the molecules keep on
changing their speed as a result of collisions.

Molecular motions may be described in terms of different types of molecular speeds.


These are defined and described below.

Most probable speed

The most probable speed of a gas is the speed possessed by the maximum fraction of
gas molecules at a given temperature denoted by .

where, R is the gas constant

T is the absolute temperature and

M is the molecular mass.

Average speed

This is the average of speeds possessed by the molecules in a sample of any gas.
This is defined as,

It can be shown that

Root mean square speed

The root mean square speed is expressed by the relationship,

Root mean square speed in any gas is given by the relationship,

The root mean square speed is commonly used and can be calculated from the
following relations:

Relation between most probable, average and root mean square speeds

The three molecular speeds are expressed as

Thus for gases, the root mean square speed is directly proportional to , and
inversely proportional to . Therefore heavier molecules move slower.

Average kinetic energy of a gas

From the kinetic model of gases,

For 1 mole of the gas, this equation becomes,

For an ideal gas,


or

Since PV = RT for 1 mole of gas

Therefore

For 'n' moles of gas, the kinetic energy is

The units of Ek depend upon the units of R. Hence the following point holds true:

The assumption of kinetic theory that the average kinetic energy or molecular
velocity of any gas is directly proportional to its absolute temperature.

K.E  u2

or

Problem

8. Calculate the kinetic energy of 2g of oxygen at -23°C.

Solution

Kinetic energy is given as

R = 8.314 JK-1mol-1, T= 273 - 23 = 250 K

9. Calculate the root mean square speed of methane molecules at 27°C.


Solution

Root mean square speed,

T = 27+ 273 = 300 K, M= 16. R= 8.314 x 107 erg k-1 mol-1

= 683.9 ms-1

The Liquid State


The liquid state lies between the gaseous and the solid state. Liquids are neither
completely disordered nor completely ordered. The cohesive forces between the
liquid particles are strong enough to keep them together but these particles do not
occupy fixed lattice sites and are relatively more free as compared to the particles in
solids.

In terms of kinetic molecular model, the nature of the liquid state can be described as
follows:

Liquids are composed of molecules that are relatively closer than gases.

Appreciable intermolecular forces hold the molecules of liquids together.

Due to weak intermolecular forces, the molecules are in constant random motion.

The average kinetic energy of molecules in a given sample is proportional to the


absolute temperature.

It may be noted that the nature and magnitude of intermolecular forces decide the
structure of a liquid and also its characteristic properties.

Properties of Liquids - I
The important properties of liquids are:

Volume

Liquids have a definite volume under given temperature and pressure conditions.
Though they take the shape of the container, they maintain their volume. The
intermolecular forces in liquids are strong and therefore, they do not expand to
occupy all the space available (as gases do). A given mass of liquid has a fixed
volume. For example, 10 cm3 of water always occupies 10 cm3 whether it is placed in
a beaker, a conical flask or a large round bottom flask.

Shape

Liquids have no shape of their own. The molecules in the liquid state are not rigidly
fixed to their own sites and take the shape of the container in which they are placed.
Density

The higher density of liquids compared to gases is due to the fact that molecules of
liquids are more closely packed than gases. In general, the density of liquids is higher
than gases and it decreases with increase in temperature. It has been found that the
densities of liquids are about 1000 times greater than the densities of gases under
similar conditions. For example, the density of water at 100oC and 1 atm is 0.958 g
cm-3 while the density of water vapours at the same temperature and pressure is
0.000588 gcm-3.

Compressibility

Liquids are 105 times less compressible than gases but are about 10 times more
compressible than solids. This is due to the fact that the molecules in liquid state are
not as closely packed as in solids but are closer to each other as compared to gases.
Moreover in the case of liquids, the repulsive forces between molecules prevent the
compressibility of liquids. Therefore, large pressure is needed to reduce the volume
of a liquid to a significant extent. For example, at 25oC, an increase in pressure from
1 atm to 2 atm decreases the volume of an ideal gas by about 50%, whereas the
same change in pressure decreases the volume of water by only 0.0045%.

Fluidity

Liquids flow with greater ease as compared to solids. The ease of flow of liquids
depends on the strength of the intermolecular attractive forces e.g. liquids with
hydrogen bonding are more viscous and therefore less fluid.

Surface tension

Due to strong intermolecular cohesive forces in the liquid, the interior of the liquid
holds the molecules on the surface inwards. This property is described in terms of
surface tension and the free surface of the liquid acts as a stretched membrane.

Diffusion and miscibility

Like gases, liquids also diffuse but they diffuse slowly than the gases. The diffusion of
liquids is defined as the process of intermixing of the molecules of two or more
liquids to form homogeneous mixture solution. This is also the movement of solute
particles from higher concentration to lower concentration in a medium.

The rate of diffusion is much slower in liquids than in gases. In the liquid state,
molecules are quite close to each other. Therefore, a molecule of the liquid has to
undergo a number of collisions with the neighbouring molecules. Thus, there is more
obstruction for the movement of the molecules of a liquid. As a result, diffusion takes
place slowly. In contrast, in gases, there is very less obstruction to the moving
molecules because of large empty spaces available for their movement. Moreover, in
liquids there are forces of attraction between individual molecules which hold them
together. In other words, this slows down the process of diffusion. However raising
the temperature increases the kinetic energy of the molecules. This increase the rate
of diffusion of a liquid.

Quasilattice structure

The partially ordered structure of liquids is called the quasilattice structure. They do
not have a long-range order. Due to the cohesive forces between the molecules in
liquids, molecules appear to be under the influence of each other for short-range
order.

Evaporation and volatility

Evaporation is the process of conversion of a liquid into its vapours at room


temperature. When a liquid is placed in an open vessel, it gradually evaporates and is
converted into its vapours. The molecules of liquids escape from the surface inspite
of strong intermolecular cohesive forces among themselves. The process of
evaporation can be explained on the basis of kinetic molecular theory.

Different molecules in a liquid have different speeds and therefore, have different
kinetic energies. There is a certain fraction of the molecules at the surface, which
have very high kinetic energies. These molecules can readily overcome the attractive
forces in the liquid and escape from the liquid surface into vapours. This process of
escaping of molecules spontaneously from the surface of the liquid to vapour state is
called evaporation.

It may be noted that during the process of evaporation, cooling always occurs. This is
because during evaporation the molecules of higher kinetic energy escape. The slow
moving molecules are left behind and therefore, the average kinetic energy of the
molecules left in the liquid state is lowered, assuming that no heat is supplied from
some outside source. The lowering of the average kinetic energy results in a
temperature drop in the liquid.

The conversion of a liquid into its vapour at its boiling point is called as vaporization.

The tendency of molecules in the liquids to escape from its surface is called volatility.
The liquids whose molecules have very little tendency to leave the surface are called
non-volatile liquids. Conversely, the liquids whose molecules leave the surface easily
are volatile liquids. Volatile liquids evaporate faster.

Factors Affecting the Rate of Evaporation

Rate of evaporation depends upon the following factors:

Factors and Heat of Vapourisation

Temperature

The rate of evaporation increases as the temperature of a liquid is increased, as it is


an endothermic process. For example, a glass of hot water evaporates more rapidly
than a glass of cold water.

Strength of intermolecular forces

The ease of evaporation of a liquid is related to the strength of the attractive forces
between the molecules in the liquid. In polar liquids cohesive forces are strong while
in non-polar liquids the cohesive forces are very weak and the molecules escape
easily. For example, ether evaporates more rapidly than ethyl alcohol while ethyl
alcohol evaporates quicker than water.

Surface area
The larger the exposed surface area of the liquid the greater is the number of
molecules escaping from its surface.

Heat of vapoursation

The amount of heat required to evaporate 1 mole of a given liquid at a constant


temperature is known as the heat of evaporation or heat of vapourisation.

For example, when one mole of water is completely vapourised at 25C, it absorbs
44.180 kJ of energy. This may be written as:

Thus, the molar heat of vapourisation of water at 25oC is 44.18 kJ. The heat of
vapourisation depends upon the strength of attractive forces between the molecules
of a liquid. The relatively high molar heat of vapourisation of water (44.18 kJ mol-1)
suggests strong attractive forces in liquid water.

Vapour pressure

If a liquid is placed in an open vessel, there is complete escape of molecules from the
liquid to the atmosphere. If a liquid is allowed to evaporate in a closed vessel, the
molecules escaping from the liquid surface are collected in a vapour state, above the
surface of the liquid within the container. Due to vapoursation the level of liquid
decreases. After some time, the level of liquid does not change further and becomes
constant.

Fig: 2.9 - Attainment of equilibrium in evaporation of liquid

This behaviour of liquid can be explained as follows. Initially, the system contains
only liquid, and air above it. The air above the liquid is completely evacuated and the
vessel is sealed, so there is nothing above the liquid. As evaporation starts, the
molecules from the surface of liquid escape into vapour state, in the confined space
above. Therefore, the level of liquid falls.

Then starts the process of


. This is the reconversion of vapour into liquid. Initially, escaped molecules move
randomLy in all directions and collide with one another within the confine of the walls
and liquid surface of the container. As more and more molecules enter the confined
space, some slow-moving molecules are pushed back. They collide with the surface
of the liquid and get recaptured by the intermolecular attraction, to reconvert into
liquid.
In the initial stages, the rate of evaporation is more than the rate of condensation
because only small number of molecules are present in the gaseous state. The rate
of condensation thereafter gradually increases as the number of molecules in the
gaseous phase increases. Finally, a stage is reached when the rate of the two
opposing processes is the same.

The state where the rate of evaporation becomes equal to the rate of condensation is
called a state of dynamic equilibrium. In such a state, although the amount of liquid
level in the vessel does not change, evaporation has not stopped and the system is
not at rest. In fact, the number of molecules, which escape from the liquid to the
gaseous phase (due to evaporation), becomes equal to the number of vapour
molecules that return to the liquid.

The molecules in the vapour phase begin to exert pressure. As evaporation reaches
the equilibrium state, the concentration of the molecules in the vapour state
becomes constant. The pressure exerted by the molecules in the gaseous phase in
equilibrium with its liquid is called equilibrium vapour pressure of the liquid or its
vapour pressure.

may be defined as 'the pressure exerted by the vapours in equilibrium with its liquid
at a given temperature'. Vapour pressure is a characteristic property of a liquid at a
given temperature. It does not depend upon the amount of the liquid or the vapour
phase. The magnitude of vapour pressure depends upon the following three factors:

Nature of liquid

The vapour pressure of a liquid depends upon the nature of the liquid. When
intermolecular forces are weak, the molecules tend to escape readily and therefore,
the equilibrium vapour pressure is high. Vapour pressure of liquids provides an
indication of the magnitude of intermolecular forces. Ether and alcohol evaporate
faster than water. Hence, ether and alcohol have higher vapour pressure than water
at a given temperature. The higher vapour pressure of ether and alcohol as
compared to water is due to the fact that there are weaker attractive forces in ether
and alcohol.

Temperature of the liquid

The vapour pressure of a liquid increases with increasing temperature. As the


temperature increases, the number of molecules, which have larger kinetic energy to
overcome the intermolecular cohesive forces, increases. As a result more molecules
escape from the surface of the liquid and concentration of molecules in the vapour
phase increase. Hence, vapour pressure of the liquid increases.

Presence of impurities

Impurities affect the vapour pressure of a liquid appreciably. The non-volatile


impurities lower the vapour pressure of a liquid.

Properties of Liquids - II
Boiling

Vapour pressure measures the tendency for the molecules to escape from liquid to
the gas phase. At lower temperatures the vapour pressure of a liquid is much lower
than the pressure on the surface of the liquid. When the temperature of the liquid is
gradually increased, its vapour pressure also increases. Ultimately a stage is reached
when the vapour pressure of the liquid equals the pressure of the air above it. At this
point, molecules and vapours formed within the liquid can easily rise through the
liquid in the form of bubbles and escape into the air. This phenomenon is known as
boiling and the temperature at which this occurs is known as boiling point.

Boiling point is the temperature at which the vapour pressure of a liquid becomes
equal to the atmospheric pressure. The boiling point, therefore, depends upon the
atmospheric pressure and it changes with the change in the pressure above the
liquid. As the atmospheric pressure increases, it is necessary to heat the liquid to a
higher temperature to make its vapour pressure equal to atmospheric pressure. At
high altitudes like Ooty, having lower atmospheric pressure, water boils at a much
lower temperature than in the plains like Bangalore where atmospheric pressure is
higher.

Generally, boiling points for most of the liquids are specified as normal boiling points.
The normal boiling point of a liquid is the temperature at which the vapour pressure
of the liquid becomes equal to one atmospheric pressure (standard pressure).

It may be noted that once the boiling starts, the temperature of the liquid remains
constant, until the whole of the liquid has vaporized, even though heating is
continued.

Problem

10. Why does the temperature of the boiling liquid remains constant even though
heating is continued ?

Solution

When a liquid is heated, the heat supplied is consumed to pull the liquid molecules
apart against strong attractive forces, which hold them together in the liquid form.
The heat energy goes to compensate the loss of energy due to escaping molecules,
which have to overcome the attractive forces between the molecules of the liquid. As
a result, there is no change in the average kinetic energy of the molecules remaining
in the boiling liquid. Since the average kinetic energy is proportional to the
temperature (1/2mV2 T), therefore, the temperature of the liquid does not change
till the whole of liquid has been converted into the vapour state.

Effect of change in external pressure on the boiling point

A liquid may be made to boil at any desired temperature by changing the external
pressure.

For example, a liquid may be made to boil at higher temperature by increasing the
pressure on its surface, as is done in a pressure cooker. It may be made to boil at a
lower temperature than the normal boiling point by reducing the external pressure on
it. It is observed that some substances decompose at their normal boiling points and
therefore, they cannot be heated up to their normal boiling points. They are made to
boil at reduced temperatures. This principle is used in purifying less stable liquids by
distillation under reduced pressure. This process is called vacuum distillation.
.

Difference between evaporation and boiling


Although boiling and evaporation are similar processes, yet they differ in few aspects.
The main points of difference between evaporation and boiling are given below:

Surface tension

Surface tension is also related to the intermolecular forces in the liquid. The
molecules in liquids are held closely and hence attract each other. A molecule in the
bulk of the liquid is attracted equally on all sides so that the net attractive pull on the
molecule is zero. However, a molecule at the surface is subjected only to the
attractive forces of the molecules below it, as there are no molecules above it.
Therefore, surface molecules experience a resultant downward attractive force from
within the liquid, which tends to make the surface area of the liquid as small as
possible. This causes the molecules at the surface to be pulled inwards and so there
is always some residual imbalance force acting on the surface of the liquids. This is
called surface tension. Whenever we want to stretch the surface, work has to be done
against surface tension. Surface tension may be defined as:

'Force per unit length acting perpendicular to the tangential line on the surface'. It
may also be defined as 'the work done to increase the free surface area of any liquid
by one unit at constant temperature and pressure.'

The SI unit of surface tension or force per unit length is Nm-1. Since this unit is too big
for any practical purpose we use a smaller unit mN m-1 (millinewton meter-1).

Fig: 2.10 - Forces at the surface and interior of the liquid

Effect of temperature

Surface tension decreases with rise in temperature, almost linearly. The decrease of
surface tension with increase in temperature results because the kinetic energy (or
speeds) of the molecules increases. Thus, the strength of intermolecular forces
decreases resulting in the decrease of surface tension also. For example, clothes are
washed more efficiently in hot water than in cold water due to decreased surface
tension in hot water.

The effect of temperature on surface tension is given by Eotvas equation

where,  = surface tension, k = constant, d = density

M = Molecular mass, Tc = critical temperature; T= temperature

As 'T' approaches critical temperature, the surface tension becomes zero. At this
stage the meniscus between the liquid and vapour disappears.

Nature of liquid

Primarily surface tension of a liquid is governed by the strength of intermolecular


attractive forces. Therefore, the magnitude of surface tension is a measure of
intermolecular attractive forces. For instance the order of strength between inter
molecular forces as well as the surface tensions of water, ethyl alcohol and ether are
in their respective orders:Water (72.8)> Ethyl alcohol (22.3) > Ether (17.0).

Impurities present in the liquid

Impurities affect surface tension appreciably. It is observed that impurities, which


tend to concentrate on the surface of liquids, compared to its bulk lower the surface
tension. Substances like detergents, soaps, alcohol lower the surface tension of
water, while inorganic impurities present in the bulk of a liquid such as NaCl tend to
increase the surface tension of water.

Pressure

Increase of pressure on the surface of a liquid increases the surface tension. Such
effects are not large.

The following two important phenomena are due to surface tension:

Spherical shape of drops

The liquid drops have nearly spherical shapes. Because of surface tension, the free
surface of a liquid tends to attain minimum surface area. Since the sphere has
minimum surface area for a given volume of liquid, the liquid tries to adopt spherical
shape. Examples are water droplets or mercury globules.

Capillary action

When one end of a capillary tube is put into a liquid that wets glass, the liquid rises
into the capillary tube to a certain height and then stops. The rise of liquid in a
capillary is due to the inward pull of surface tension acting on the surface, which
pushes the liquid into the capillary tube. This phenomenon is called capillary action.
The rise of liquid in the capillary is very important. For example, water below the
surface of the Earth rising to the plants through the roots, oil rising into the wick of an
oil lamp, ink rising in a blotting paper, are all examples of capillary action.

Viscosity

Certain liquids flow faster than others. Water and kerosene oil flow rapidly while
honey and castor oil flow slowly. The cause of different rates of flow of liquids may be
easily understood by considering flow of liquid in a beaker. If water is stirred in a
beaker with a rod and left undisturbed for some time, its swirling motion stops after
some time. The faster moving outer layer adjacent to the edge of the beaker comes
to stop first. The slower moving layer near the center, which stops last, is pulling it
back. Different layers in a liquid move over one another with different speeds in the
direction of the flow of the liquid. However, due to intermolecular forces, there is
resistance of one layer to the other layer. These internal self-governing forces tend to
oppose any free motion. This resistance to the flow of a liquid is termed as viscosity.

'The internal resistance to flow in liquids, which, one layer offers to another layer
trying to pass over it is called viscosity'.

The viscosities of liquids are compared in terms of coefficient of viscosity ( ). This is
defined as the tangential force per unit area required to maintain a unit difference in
velocities.

The units of viscosity are poise (P), where 1P = 1 g cm-1 s-1. In S.I. unit, 1P = 0.1 Nsm-
2
.

Viscosity is also related to the intermolecular forces in the liquid. If the intermolecular
forces are large, viscosity will be high. For example, water has higher viscosity than
methyl alcohol because intermolecular forces in water are more than that in methyl
alcohol.

With rise in temperature viscosity of a liquid decreases. This increases the average
kinetic energy and so the intermolecular forces can be easily overcome.

Liquids with extensive hydrogen bonding show higher viscosity due to an increase in
size and mass of the molecule.

For example, glycerol and sulphuric acid show higher viscosity than water due to
hydrogen bonding.

Problem

11. Which of the liquids in each of the following pairs has a higher vapour pressure.

(a) Alcohol, glycerine (b) Mercury, water (c) Petrol, kerosene.

Solution

Liquids having higher vapour pressure are:

(a) Alcohol (b) Water (c) Petrol.

The Solid State


Solids are substances having definite volume and definite shape. In terms of kinetic
molecular model, in solids there is a regular order in the arrangement of the
constituting particles (atoms, molecules or ions) i.e. the particles constituting the
solids occupy fixed positions These particles are held together by fairly strong forces.

Characteristics of Solids

Some of the common properties of solids, which distinguish them from other two
states of matter, are:

Solids are rigid and have definite shapes.

Solids have definite volume irrespective of the size or shape of the container in
which they are placed.

Solids are almost incompressible, having compressibility, which is approximately


106times more than gases.

Many solids have a crystalline appearance and have definite pattern of angles and
planes.

Solids diffuse very slowly as compared to liquids and gases. Constituent particles
are very closely packed in solids permitting very little space for their movement.

Solids have a much higher density (mass to volume ratio) than that of gases and
liquids.

Most solids become liquids when heated. Some undergo sublimation on heating.
The temperature at which a solid changes into liquid is called the melting point and
the process is called as melting. Due to the varying natures of solids their melting
temperatures vary considerably.

Classification of Solids
The above properties suggest that the properties of the solids not only depend upon
the nature of the constituents, but also on their arrangements.

Based on their structural features solids can be classified into three categories:

Crystalline solids

Amorphous solids

Polycrystalline solids

Crystalline Solids

The substances whose constituents are arranged in definite orderly arrangements are
called crystalline solids. Many naturally occurring solid substances occur in the
crystalline form. Some common examples of crystalline solids are sodium chloride,
sulphur, diamond, sugar, etc.

They have the following characteristics:

They posses characteristic geometric shapes. The constituent particles in crystals


are usually held by strong inter atomic, inter-ionic or intermolecular forces. Particles
vibrate about their equilibrium positions and do not posses translational motion.

Crystalline solids have sharp melting points, indicating the presence of a long
range order arrangement in them. The long-range order is due to the regular
arrangement of the constituents (molecules, atoms or ions) throughout the three
dimensional network of crystals. For example, experiments (X-ray diffraction method)
show that in a crystal of sodium chloride, the constituents Na+ and Cl- ions are present
at alternate sites as shown below:

Na+ Cl- Na+ Cl- Na+ Cl-

Cl- Na+ Cl- Na+ Cl- Na+

Na+ Cl- Na+ Cl- Na+ Cl-

Cl- Na+ Cl- Na+ Cl- Na+

Though shown in two dimensions this systematic long-range order is also found in
three dimensions, with each Na+ surrounded by six ions and vice versa. This order is
due to strong coulombic forces of attraction between Na+ and Cl- ions. Similar regular
arrangements are found in other solids too.

Crystalline solids are anisotropic by nature i.e., their mechanical, electrical and
optical properties depend upon the direction along which they are measured.

When cut or hammered gently they show a clean fracture along a smooth surface.

Amorphous Solids

Substances whose constituents are not arranged in an orderly manner are called
amorphous solids. They are also called pseudo solids and differ from crystalline solids
in many respects. The common examples of amorphous solids are glass, rubber,
fused silica, plastics, etc.

They have the following characteristics:

They do not occur in characteristic geometric shapes. They posses properties of


incompressibility and rigidity to some extent.

Their mechanical, electrical and optical properties do not depend upon the
direction along which they are measured. They are isotropic and in this respect
resemble liquids and are sometimes referred to as super cooled liquids.

Amorphous solids do not have sharp melting points. They have some orderly
arrangement but it is not extended to more than a few Angstrom units. Thus,
amorphous solids are said to have short-range order. On heating they melt and begin
to flow like liquids.

When cut or hammered they break in an irregular manner.

Polycrystalline Solids

These are crystalline solids, constituted of very fine crystals, not seen by the naked
eye. These solids appear amorphous but are not so because the fine crystals are
randomly oriented. Thus even though each individual crystal is anisotropic the
polycrystalline materials as a whole appear to be isotropic. Metal powders are
polycrystalline in nature.

Crystalline Solids
Crystalline substances have a definite rigid shape. The shape and size of crystals
(even of the same materials) differs depending upon the conditions under which they
are grown. Crystals of a given substance are bound by plane surfaces called faces.
The angle between any two faces is called interfacial angle. But the angles between
the faces of a given form always remains same. This important characteristic feature
of a given crystalline substance is known as law of constancy of interfacial angles.

Types of Crystalline Solids

Crystalline solids may be classified into four types depending upon the nature of
bonds present in them.

Molecular crystals

In molecular crystals, the constituent particles are molecules. These molecules are
held together by weak forces known as Van der Waal's forces. Common examples are
dry ice, wax, iodine, sulphur, etc.

Characteristic features of molecular crystals are:

Molecular crystals are soft, compressible and can be distorted very easily.

They have low melting and boiling points.

These are bad conductors of electricity and are regarded as electrical insulators.

They are volatile and have low heats of vaporization and low enthalpy of fusion.

Ionic crystals

The ionic crystals consist of positively and negatively charged ions arranged in a
regular fashion throughout the crystal. They form a network of positive and nagative
ions in three dimension in such a way that cations and anions occupy alternate sites.
These are held together by strong electrostatic forces.

The main characteristics of ionic crystals are:

Ionic crystals are very hard and brittle.

They have very high melting and boiling points.

They are poor conductors of electricity and therefore are insulators in the solid
state.

They have high heat of vaporization and so have low vapour pressure.

Have high enthalpy of fusion.

When melted or dissolved in polar solvents, they conduct elecricity.


Common examples of ionic crystals are, salts like NaCl, KNO3, LiF etc.

Covalent crystals

In covalent crystals, the constituent particles are atoms of the same or different kind,
which are bonded to one another by a network of covalent bonds. The important
characteristics of covalent crystals are:

The covalent crystals are incompressible and hard.

They are extremely non-volatile and have very high melting points.

They are poor conductors of electricity at all temperatures.

They have high heat of fusion and high enthalpy of atomization.

The common examples of covalent crystals are diamond, carborundum (silicon


carbide), quartz (SiO2,) etc.

Metallic crystals

In metallic crystals the constituent particles are positive kernels i.e., nuclei where
inner electrons are dispersed in a sea of mobile valence electrons. The forces present
between the constituents are metallic bonds.

The main characteristics of metallic crystals are:

Metallic crystals may be hard as well as soft.

They are good conductors of heat and electricity.

They have metallic luster and high reflectivity.

They are highly ductile and malleable i.e, they can be beaten into sheets and
drawn into wires.

They have moderate heat of fusion.

The properties of metallic crystals vary from metal to metal.

The examples of metallic crystals are common metals such as nickel, copper and
alloys.

Problem

12. The melting point is a rough measure of the attractive forces in solids.

Arrange the following solids in the order of increasing strength of attractive forces.
Solution

The order of increasing strength of attractive forces is: Water phosphorus


naphthalene zinc iodide sodium fluoride.

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