5.

STATES OF MATTER
Intermolecular forces are the forces of attraction and repulsion between interacting particles
(atoms and molecules). This term does not include the electrostatic forces that exist between
the two oppositely charged ions and the forces that hold atoms of a molecule together i.e.,
covalent bonds.
Attractive intermolecular forces are known as vander Waals forces.
1) Dispersion Forces or London Forces Atoms and non-polar molecules are electrically
symmetrical and have no dipole moment. But in an atom, at a particular moment, the nucleus
is shifted towards one side and the electrons, to the other side. So a temporary dipole
(momentarily dipole) is created. This results in the development of instantaneous dipole on
the adjacent atom for a very short time. These temporary dipoles of atoms attract each other.
This force of attraction between temporary dipoles is termed as London forces or dispersion
forces. These forces are important only at short distances. The interaction energy is inversely
proportional to the sixth power of the distance between the interacting particles.(1/r 6).

2) Dipole - Dipole Forces Dipole-dipole forces act between the molecules possessing
permanent dipole (polar molecules). These molecules interact with the neighbouring
molecules. This interaction is stronger than the London forces but is weaker than ion-ion
interaction because only partial charges are involved. The attractive force decreases with the
increase of distance between the dipoles. E.g.: HCl

3) Dipole–Induced Dipole Forces This type of attractive forces operates between the polar
molecules and the non-polar molecules. Permanent dipole of the polar molecule induces
dipole on the electrically neutral molecule by deforming its electronic cloud. Thus an induced
dipole is developed in the other molecule. The attraction between these molecules is termed
as dipole – induced dipole force. The interaction energy is inversely proportional to the sixth
power of the distance between the interacting particles.(1/r6).

Hydrogen bond: Hydrogen bond is represented by a dotted line (– – –) while a solid line
represents the covalent bond. Thus, hydrogen bond can be defined as the attractive force
which binds hydrogen atom of one molecule with the electronegative atom (F, O or N) of
another molecule this is special case of dipole-dipole interaction.
Themalenergy : The energy of the body arising from motion of its atoms or molecules.It is
directly proportional to the temperature of the substance.
1
Factors Deciding Physical State of a Substance
For gaseous state, Forces of attraction << thermal energy
For liquid state, Forces of attraction > Thermal energy
For solid state, Forces of attraction >> Thermal energy
The Gaseous State
This is the simplest state of matter. Characteristics of this ‘state of matter are
1. In gases, the intermolecular forces are weakest.
2. Gases are highly compressible.
3. Gases exert pressure equally in all directions.
4. Gases have much lower density than the solids and liquids.
5. The volume and the shape of gases are not fixed.
6. Gases mix evenly and completely in all proportions without any mechanical aid

Gas Laws
These are some relationships connecting the measurable properties of gases like pressure (P),
temperature (T), volume (V) and number of moles (n).
These are:
1) Boyle’s Law (Pressure – Volume Relationship)
It states that at constant temperature, the volume of a fixed mass of gas is inversely
proportional to its pressure.
1
Mathematically, P α
V
1
P=kx , where k is the proportionality constant.
V

Or, PV = k, a constant
Consider a fixed amount of gas at constant temperature T.
Let V1& P1 are its initial volume and pressure respectively. Let the gas undergoes expansion,
so that its final volume and pressure becomes V2 and P2. Then according to Boyle’s law,
P1V1 = P2V2
If we plot graphs between pressure against volume, pressure against 1/volume and PV
against P at constant temperature, the graphs obtained are as follows:

2
These graphs are obtained at constant temperature and are called isotherms.
We know that density = mass/volume i.e., d = m/V
If we put value of V in this equation from Boyle’s law equation, we get the relationship,
d = (m/k) x p
i.e. At constant temperature, pressure is directly proportional to the density of a fixed mass of
the gas.
2) Charles’ Law (Temperature – Volume Relationship)
It states that at constant pressure, volume of a fixed mass of gas is directly proportional to its
temperature.
Mathematically, V α T
Or, V=kxT
V
Or , = k, a constant
T

Consider a fixed amount of gas at constant pressure P. Let V1 be its volume at a temperature
T1 and V2 be its volume at a temperature T2. Then according to Charle’s law: V1/T1 = V2/T2
If volume is plotted against temperature at constant pressure, the graph obtained is as follows

3
Since the graph is obtained at constant pressure, it is called isobar.
If we extend the graph to temperature axis (X-axis), the graph will meet at -273.15 0 C. At this
temperature, the volume of the gas becomes zero. This lowest hypothetical or imaginary
temperature at which gases are supposed to occupy zero volume is called Absolute zero of
temperature and the scale of temperature based on absolute zero is called Absolute scale of
temperature. All gases become solid or liquid before reaching this temperature.
Another form of Charle’s law
The volume of the given mass of a gas increases or decrease by 1 / 273 of its volume at 0 0C
at constant pressure.
At 00 C, Volume = V0
1
At 10 C, Volume V1 = V0 + V
273 0

2
At 20 C, Volume V2 = V0 + V
273 0

t
At t0 C, VolumeVt = V0 + V
273 0

−273
At -2730 C, Volume V-273 = V0 + V0 = 0
273

Absolute zero is the theoretically possible temperature at which the volume of the gas
becomes zero. It is equal to 0 K or -273.150 C

3) Gay Lussac’s Law (Pressure - Temperature Relationship)

It states that at constant volume, pressure of a fixed amount of a gas is directly proportional
to the temperature.
Mathematically, P α T

4
Or, P = a constant x T
P
Or, = a constant
T

If we plot a graph between pressure and temperature of a fixed mass of gas at constant
volume, the graph obtained is as follows:

The above is obtained at constant volume and is termed as an isochore

4) Avogadro Law (Volume – no. of moles or Amount Relationship)
It states that equal volumes of all gases under the same conditions of temperature and
pressure contain equal number of moles or molecules. This means that at constant
temperature and pressure, the volume of a gas is directly proportional to its number of moles
(n) or molecules (N).
i.e., V α n, the number of moles
or, V = k x n, where k is a constant
We know that number of moles (n) = mass in gram (m)/molar mass (M)
i.e., n = m/M
So the above equation becomes:
V = k x m/M
Or, M = k x m/V
Or, M= k x d
Or, M α d
i.e., the density of a gas is directly proportional to its molar mass.
Standard Temperature and Pressure (STP)
Standard temperature and pressure (also called NTP, the normal temperature and pressure)
means 273.15 K (0°C) temperature and 1 bar pressure. At STP molar volume of an ideal gas
or a combination of ideal gases is 22.71 L mol–1 .
5
 IDEAL GAS EQUATION: The combination of the three gas laws (Boyle’s law, Charles’
and Avogadro law) give a single equation which is known as ideal gas equation.
According to Boyle’s law: V α 1/P (At constant T and n)
According to Charles’ Law: V ∝ T (At constant p and n)
According to Avogadro Law: V ∝ n (At constant p and T)
On combining these three laws
we get: V ∝ n x T x 1/P
Or, V = R x n x T x 1/P (where R is a constant called universal gas constant)
Or, PV = nRT ………………….. (1) This equation is known as ideal gas equation.
From equation (1), R = PV/nT The value of R depends upon units in which P, V and T are
measured.
Values of R in different units
1. L atm/K/mol 0.0821
2. L bar/K/mol 0.08314 (8.314x10-2 )
3. Pa m3 /K/mol 8.314
4. J/K/mol 8.314

Ideal gas equation is a relation between four variables and it describes the state of any gas,
therefore, it is also called equation of state.
Combined Gas Law
From ideal gas equation
PV = nRT,
PV/T = nR
If temperature, volume and pressure of a fixed amount of gas vary from T1, V1 and P1 to T2,
V2 and P2 then we can write, P1V1/T1 = P2V2/ T2This equation is known as combined gas law.
By knowing the values of any 5 parameters, we can determine the sixth one.
PV = nRT
PV = mass RT
Molarmass

P= mass RT
V Molarmass
P= ρ RT
Molarmass
PM = ρ RT
6
5) Dalton’s Law of Partial Pressures
This law states that at constant temperature, the total pressure exerted by a mixture of non-
reacting gases is equal to the sum of the partial pressures of the individual gases. The partial
pressure of a gas in a mixture of gases is the pressure that the gas would exert, when it alone
occupies the whole volume.
Mathematically, PTotal = P1+P2+P3+...... (at constant T, V) where PTotalis the total pressure
exerted by the mixture of gases and P1,P2,P3 etc. are partial pressures of gases.
Application of Dalton’s law:Dalton’s law can be used to calculate the pressure of a gas
collected over water surface. Here the gas is always moist. Therefore, pressure of dry gas can
be calculated by subtracting vapour pressure of water from the total pressure of the moist gas.
Pressure exerted by saturated water vapour is called aqueous tension.
PDry gas = PTotal – Aqueous tension
Partial pressure in terms of mole fraction
Consider three gases at constant temperature T and constant volume V, exert partial pressures
P1, P2 and P3.
From ideal gas equation, P =nRT/V
n1 RT
So, P1 =
V
n2 RT
P2 = and
V
n3 RT
P3 =
V

The total pressure exerted by the mixture,

n1 RT n2 RT n3 RT
PTotal = P1+P2+P3 = + +
V V V
RT
= ( n1+n2+n3)
V

On dividing P1 by PTotal, we get, P1/PTotal = n1/( n1+n2+n3)

Or, P1/PTotal = x1
Or, P1 = x1.PTotal
Similarly, P2 = x2.PTotal and P3 = x3.PTotal
In general, Pi = xi.PTotal where Pi and xi are partial pressure and mole fraction ofi th gas
respectively.

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KINETIC MOLECULAR THEORY OF GASES
In order to explain the gas laws theoretically Maxwell, Boltzmann, Claussius etc. put
forward a theory called kinetic molecular theory of gases or microscopic model of gases. The
important postulates of this theory are:
1. Every gas contains a large number of minute and elastic particles (atoms or molecules).
The actual volume of the molecules is negligible compared to the volume of the gas.
2. There is no force of attraction between the gas particles.
3. The particles of a gas are in constant and random motion in straight line. During this
motion they collide with each other and also with the walls of the container.
4. The pressure of a gas is due to the wall collisions of the particles.
5. All collisions are perfectly elastic. i.e. the total energy of particles before and after
collisions remains the same.
6. At any particular time, different particles of a gas have different speed and hence different
kinetic energy.
7. The average kinetic energy of gas molecules is directly proportional to absolute
temperature.
Behaviour of real gases – Deviation of real gases from ideal behavior
Gases which do not obey ideal gas equation at all conditions of temperature and pressure are
called real gases. This can be understood from the PV against P graphs for different gases.

For ideal gases, PV is constant for any pressure. So the graph obtained is a straight line
parallel to the pressure axis (X – axis).
For H2 and He, PV increases with increase of pressure.

8
But for CO and CH4, the value of PV first decreases, reaches a minimum value and then
increases.
At high pressure the measured volume is more than the calculated volume.
At low pressure the measured and the calculated volume approach each other.
From the graph it is clear that all gases behave ideally at low pressure. As the pressure
increases the deviation from ideal behaviour also increases.
The deviation from real gases from ideal behaviour is due to two wrong assumptions of
kinetic theory of gases. They are:
1. The actual volume of the molecules is negligible compared to the volume of the gas.
2. There is no force of attraction between the gas particles.
These two assumptions become wrong at high pressure and low temperature. When the
pressure increases, the volume of the gas decreases. Then the volume of the gas molecule is
also considered. At this condition, there arises intermolecular forces of attraction.
Thus real gases obey ideal gas equation at low pressure and high temperature. Or, real gases
deviate from ideal behaviour at high pressure and low temperature.
Equation for real gas
By considering the above two assumptions, van der Waal proposed an equation, which is
applicable to real gases. The equation is known as van der Waal’s equation and is given
as:

Where P is the pressure of the gas, V is the volume, R is

the universal gas constant, T is the absolute temperature, n is the no. of moles, ‘a’ and ‘b’ are
called van der Wall’s constants. ‘a’ is a measure of magnitude of inter molecular attractive
forces within the gas and ‘b’ is related to the volume (size) of the particles. The unit of ‘a’ is
L2atm mol-2 and that of ‘b’ is Lmol-1. The term an2/V2 is related to pressure correction and
term ‘nb’ is related to volume correction.

9
Compressibility factor (Z)
The deviation from ideal behaviour can be measured in terms of compressibility factor Z,
which is the ratio of product PV and nRT.
Mathematically, Z = PV /nRT
For ideal gas Z = 1 at all temperature and pressures.
So the graph of Z vs P will be a straight line parallel to pressure axis.
For real gases value of Z deviates from unity.

At high pressure Z ¿ 1, ie repulsive forces exist between the molecues. The gases are less
compressable than ideal gases.
When Z ¿ 1, ie attractive forces exist between the molecues. The gases are more easily
compressable.

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Boyle Temperature or Boyle Point
The temperature at which real gases obey ideal gas equation over an appreciable range of
pressure is called Boyle temperature or Boyle point. It depends on the nature of the gas.
Above Boyle Temperature , Z ¿ 1
Z = pV
nRT
For real gases Z = pVreal ----------------- (1)
nRT

For ideal gases Z = pVideal -------------------- (2)

nRT

Z= 1 for ideal gases, nRT = pVideal -------------------- (3)

eqn (3) substitute in eqn (1)

Z = Vreal
Videal
Compressibility factor (z ) is the ratio of actual molar volume of a gas to the molar volume
of it, if it were an idel gas at that temperature and pressure.

Liquifaction of gases
Gases can be liquified by applying pressure at low temperature.
The temperature below which a gas can be liquified by the application of pressure is called
Critical Temperature (Tc).
The pressure that must be applied at the critical temperature to liquify a gas is called Critical
Pressure (Pc).
The volume of 1 mole of a gas at its critical temperature and critical pressure is called
Critical Volume (Vc).
Tc, Pc and Vc are called Critical constants.
*Gases with higher Critical Temperature liquify faster than other gases.
* Gases with higher Critical Temperature possess high molecular attraction.
*Liquifaction of permanent gases require cooling and compression.
*A gas below its critical temperature can be liquified by applying pressure and is called the
vapour of the gas.CO2 gas below its critical temperature is called CO2 vapour.
THE LIQUID STATE
In liquids the particles are loosely packed and so there is some inter molecular force of
attraction. But this force is not strong enough to bind the molecules together. So liquids have

11
a definite volume but nodefinite shape. Due to the weak force of attraction, the molecules can
move and so liquids can flow.
Some of the important properties of liquids are:
1. Vapour pressure :. It is defined as the pressure exerted by the vapour of the liquid in
equilibrium with its own liquid at constant temperature. It depends on the following factors.
a)Nature of the liquid :More volatile liquids have high vapour pressure.
b) Temperature: As the temperature increases, the vapour pressure also increases.
2. Boiling Point :The vapour pressure of a liquid increases with temperature. At a particular
temperature, the vapour pressure becomes equal to atmospheric pressure. At this temperature,
the liquid boils. This temperature is called boiling point.
At 1 atm pressure the boiling point is called normal boiling point.
If pressure is 1 bar then the boiling point is called standard boiling point of the liquid.
The normal boiling point of water is 100 °C (373 K), its standard boiling point is 99.6 °C
(372.6 K).
*At high altitudes (heights) atmospheric pressure is low. Therefore liquids at high altitudes
boil at lower temperatures than at sea level. Since water boils at low temperature on hills, the
pressure cooker is used for cooking food.
3. Surface Tension
It is defined as the force acting per unit length perpendicular to the line drawn on the surface
of liquid. It is denoted by Greek letter γ (Gamma). Its SI unit is N m–1 .
The energy required to expand the surface of a liquid by unit area is called surface energy. Its
SI unit is Jm-2 .
Surface tension reduces the surface area of a liquid. Every liquid tries to reduce their energy
by decreasing the surface area. For a given volume sphere has the minimum surface area. So
liquid drops assume spherical shape.
The magnitude of surface tension of a liquid depends on the attractive forces between the
molecules and the temperature. When the attractive forces are large, the surface tension is
large.
As temperature increases, surface tension decreases. Increase in temperature increases the
kinetic energy of the molecules and the attractive forces between the molecules decreases.
4. Viscosity
When a liquid flows over a fixed surface, we can assume that there are a large number of
layers.
The layer of molecules which is in contact with the surface is stationary. The velocity of
upper layers increases as the distance of layers from the fixed layer increases. This type of

12
flow in which there is a regular change of velocity in passing from one layer to the next is
called laminar flow.
Viscosity is a measure of internal resistance offered by the different layers of a liquid. If the
velocity of the layer at a distance dz is changed by a value du, then velocity gradient is given
by the amount du/dz.
A force is required to maintain the flow of layers. This force is proportional to the area of
contact of layers and velocity gradient.
i.e. F α A (Where A is the area of contact).
Fα du/dz (Where du/dz is the velocity gradient. i.e. the change in velocity with distance)
or, F α A. du /dz
or, F = η.A. du /dz
The proportionality constant ‘ η ’ is called coefficient of viscosity.
It is defined as the force when velocity gradient and the area of contact are unity. Thus
‘ η ’ is measure of viscosity.
SI unit of viscosity coefficient is newton second per square metre (N s m–2) or pascal second
(Pa sec). In cgs system the unit of coefficient of viscosity is poise.
Greater the viscosity, the more slowly the liquid flows. i.e. viscosity is inversely proportional
to fluidity.
The presence of Hydrogen bonding and van der Waals forces, increases viscosity.
Glass is a very viscous liquid. So it has a tendency to flow though very slightly. Hence the
windowpanes of old buildings are thicker at the bottom than at the top.
Viscosity of liquids decreases as the temperature increases because at high temperature,
molecules have high kinetic energy and can overcome the intermolecular forces to slip past
one another between the layers.

Maxwell-Boltzmann Distribution of molecular speeds

According to Kinetic molecular theory of gases, the molecules of a gas are in continuous
random motion and they collide with each other. So the speed and the kinetic energy of the
molecules are different at any particular time. Thus we can obtain only an average value of
speed of molecules.
The distribution of molecular speeds was first studied by Maxwell and Boltzmann by
applying the theory of probability. This is known as Maxwell-Boltzmann Distribution of
molecular speeds. They plotted a graph between number of molecules having different
speeds against molecular speeds as follows

13
The following conclusions are obtained from the graph:
1. The number of molecules having very low and very high speed is very small.
2. Most of the molecules have a particular speed called most probable speed (ump) which
denotes the maximum in the curve.
3. On increasing the temperature, the curve broadens and the ump increases.
The speed distribution also depends on mass of molecules. At a constant temperature, heavier
gas molecules have slower speed than lighter gas molecules.
Different types of molecular speeds
1. Average speed (uav): It is the arithmetic mean of the different speeds of molecules in a
given sample of gas. If there are ‘n’ molecules in a sample and u1, u2, u3 …….. un are their
individual speeds, then average speed is given by,
uav = u1+ u2+ u3+ ……… + un
n
2. Root mean square (rms) speed: It is the square root of the mean of the squares of the
different speeds of the gas molecules. It is given by:

√ u12+ u22+ u32+ ……… + un2

urms = n

3. Most probable speed (ump): It is the speed possessed by maximum number of gas
molecules.
The three types of molecular speeds are related as: urms > uav > ump.

The ratio between the three speeds is:

Ump: Uav: Urms = 1: 1.128: 1.224

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