STATES OF MATTER

INTERMOLECULAR FORCES
• Forces of attraction and repulsion between interacting particles
(atoms and molecules)
• Attractive intermolecular forces are known as van der Waals
forces.
Types:
• Dispersion Forces or London Forces
• Dipole - Dipole Forces
• Dipole–Induced Dipole Forces
• Hydrogen bond
 Dispersion Forces or London Forces
• Operate bet. Atoms and non-polar
molecules
• Force of attraction between two temporary
dipoles.
• Always attractive.
• Inversely proportional to the sixth power
of the distance between two interacting
particles (i.e., 1/r6 where r is the distance
between two particles).
• Important at short distances (~500 pm)
• magnitude depends on the polarizability of
the particle.
 Dipole - Dipole Forces
• Act between the molecules
possessing permanent dipole.
• Stronger than the London forces.
• Decreases with the increase of
distance between the dipoles.
• Inversely proportional to distance
between polar molecules.
• 1/r3 in solids and 1/r6 in liquid and
gases
 Dipole–Induced Dipole Forces
• Operate between the polar molecules
having permanent dipole and the molecules
lacking permanent dipole.
• Interaction energy is proportional to 1/r 6
• Depends upon the dipole moment present
in the permanent dipole and the
polarizability of the electrically neutral
molecule.
 Hydrogen bond
• Found in the molecules in which highly polar N–H, O–H or H–F
bonds.
• Hydrogen bonds are powerful force in determining the structure
and properties of many compounds.
• Strength determined by the coulombic interaction between the
lone-pair electrons of the electronegative atom of one molecule
and the hydrogen atom of other molecule.
 THERMAL ENERGY

• Energy of a body arising from motion of its atoms or molecules.

• Directly proportional to the temperature of the substance.
• Measure of average kinetic energy of the particles of the matter.
INTERMOLECULAR FORCES vs THERMAL
INTERACTIONS
 THE GASEOUS STATE
• Simplest state of matter
• only eleven elements exist as gases
under normal conditions
 Physical properties of gases
• Gases are highly compressible.
• Gases exert pressure equally in all directions.
• Gases have much lower density than the solids and liquids.
• The volume and the shape of gases are not fixed. These assume volume and
shape of the container.
• Gases mix evenly and completely in all proportions without any mechanical
aid.
• forces of interaction between their molecules are negligible.
Behaviour is governed by same general laws, which were discovered as
a result of their experimental studies.
 Gas laws
• Boyle’s Law (Pressure – Volume Relationship)
• Charles’ Law (Temperature – Volume Relationship)
• Gay Lussac’s Law (Pressure- Temperature Relationship)
• Avogadro Law (Volume – Amount Relationship)
 Boyle’s Law (Pressure – Volume Relationship)
At constant temperature, the pressure of a
fixed amount (i.e., number of moles n) of
gas varies inversely with its volume p vs. Volume

Isotherm plot
or

k1 is the proportionality constant. The value

of constant k1 depends upon the amount of
the gas, temperature of the gas and the units
in which p and V are expressed.
At constant temperature, If fixed amount of gas having volume V1 at pressure
p1 undergoes expansion, so that volume becomes V2 and pressure becomes p2,
then according to Boyle’s law :
p1V1= p2V2 = constant

Volume of the gas doubles if pressure is halved.

At high pressures, gases deviate from Boyle’s law and under such
conditions a straight line is not obtained in the graph.
 Question

A balloon is filled with hydrogen at room temperature. It

will burst if pressure exceeds 0.2 bar. If at 1 bar pressure
the gas occupies 2.27 L volume, up to what volume can
the balloon be expanded ?
 Relationship bet. Density and pressure
by using Boyle’s law

• We know that:

• If we put value of V in this equation from Boyle’s law equation:

• At a constant temperature, pressure is directly proportional to the

density of a fixed mass of the gas
Charles’ Law (Temperature – Volume Relationship)
Pressure remaining constant, the volume of a fixed mass of a gas is directly
proportional to its absolute temperature.
For each degree rise in temperature, volume of a gas increases by 1/273.15
of the original volume of the gas at 0°C. Thus if volumes of the gas at 0°C
and at t°C are V0 and Vt respectively, then
If Tt= 273.15+t and T0= 273.15 then

OR
 Question
On a ship sailing in Pacific Ocean where temperature is 23.4°C, a balloon is
filled with 2 L air. What will be the volume of the balloon when the ship
reaches Indian ocean, where temperature is 26.1°C ?
 Charles’ Law (Temperature – Volume Relationship)
• For all gases, at any given pressure, graph of volume vs
temperature (in celsius) is a straight line and on
extending to zero volume, each line intercepts the
temperature axis at – 273.15 °C.
• Each line of the volume vs temperature graph is called
isobar.
• Volume of the gas at – 273.15 °C will be zero. This
means that gas will not exist. In fact all the gases get
liquified before this temperature is reached.
• The lowest hypothetical or imaginary temperature
at which gases are supposed to occupy zero
Isobar plot
volume is called Absolute zero.
• All gases obey Charles’ law at very low pressures
and high temperatures.
 Gay Lussac’s Law (Pressure- Temperature Relationship)

At constant volume, pressure of a fixed amount of a gas varies directly with

the temperature.
Mathematically:
 Avogadro Law (Volume – Amount Relationship)
• It states that equal volumes of all gases under the same conditions of temperature
and pressure contain equal number of molecules.
i.e Vά n where n is the number of moles of the gas

• Number of moles of a gas can be calculated as follows

Where m = mass of the gas under investigation and M = molar mass

Or M= k4 m/V = k4d
Density of a gas is directly proportional to its molar mass.
 Some important points
• Number of molecules in one mole of a gas has been determined to be 6.022
×1023 and is known as Avogadro constant.
• Since volume of a gas is directly proportional to the number of moles; one
mole of each gas at standard temperature and pressure (STP)* will have same
volume. Standard temperature and pressure means 273.15 K (0°C)
temperature and 1 bar (i.e., exactly 105 pascal) pressure. At STP molar
volume of an ideal gas or a combination of ideal gases is 22.71098 L mol–1.
• A gas that follows Boyle’s law, Charles’ law and Avogadro law strictly is called
an ideal gas. Such a gas is hypothetical.
• Real gases follow these laws only under certain specific conditions when forces
of interaction are practically negligible.
IDEAL GAS EQUATION (equation of state)

where R is proportionality constant. On rearranging the equation

Ideal gas equation.

R is called gas constant. It is same for all gases. Therefore it is also

called Universal Gas Constant. R (at STP)= 8.314 J K–1 mol–1
 Combined gas law
• 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
 Question
At 25°C and 760 mm of Hg pressure a gas occupies 600 mL volume. What
will be its pressure at a height where temperature is 10°C and volume of the
gas is 640 mL.
Trick to remember gas laws

C G
P V
T
B
Density and Molar Mass of a Gaseous Substance
 Dalton’s Law of Partial Pressures

• The total pressure exerted by the mixture of non-reactive gases is

equal to the sum of the partial pressures of individual gases

• Gases are generally collected over water and therefore are moist.
Pressure of dry gas can be calculated by subtracting vapour
pressure of water from the total pressure of the moist gas which
contains water vapours also
 Partial pressure in terms of mole fraction
• Suppose at the temperature T, three gases, enclosed in the volume V, exert
partial pressure p1, p2 and p3 respectively, then,
Thus, expression for total pressure will be

where n1 n2 and n3 are number of moles of these gases.

 Question
A neon-dioxygen mixture contains 70.6 g dioxygen and 167.5 g neon. If
pressure of the mixture of gases in the cylinder is 25 bar. What is the partial
pressure of dioxygen and neon in the mixture ?
 KINETIC ENERGY AND MOLECULAR SPEEDS

• If there are n number of molecules in a sample and their individual speeds

are u1, u2,…….un, then average speed of molecules uav can be calculated as
follows:
 Maxwell-Boltzmann distribution
• The maximum in the curve represents
speed possessed by maximum number of
molecules. This speed is called most
probable speed, ump.
• This is very close to the average speed of
the molecules.
• On increasing the temperature most
probable speed increases.
• At the same temperature, gas molecules
with heavier mass have slower speed than
lighter gas molecules.
 Different speeds of gases
Most probable speed(ump ) : Speed possessed by maximum number of molecules
Average speed: Average value of speed of molecules.

Mean square speed: mean of square of speeds

Root mean square speed: square root of the mean of the square of speeds
Relation between speeds
 KINETIC MOLECULAR THEORY OF GASES
Postulates of the kinetic molecular theory of gases:
• Gases consist of large number of identical particles (atoms or molecules) that
are so small and so far apart on the average that the actual volume of the
molecules is negligible in comparison to the empty space between them. They
are considered as point masses. This assumption explains the great
compressibility of gases.
• There is no force of attraction between the particles of a gas at ordinary
temperature and pressure. The support for this assumption comes from the fact
that gases expand and occupy all the space available to them.
• Particles of a gas are always in constant and random motion. If the particles
were at rest and occupied fixed positions, then a gas would have had a fixed
shape which is not observed
• Particles of a gas move in all possible directions in straight lines.
During their random motion, they collide with each other and
with the walls of the container. Pressure is exerted by the gas as a
result of collision of the particles with the walls of the container.
• Collisions of gas molecules are perfectly elastic. This means that
total energy of molecules before and after the collision remains
same. There may be exchange of energy between colliding
molecules, their individual energies may change, but the sum of
their energies remains constant. If there were loss of kinetic
energy, the motion of molecules will stop and gases will settle
down. This is contrary to what is actually observed.
• At any particular time, different particles in the gas have different speeds and
hence different kinetic energies. This assumption is reasonable because as the
particles collide, we expect their speed to change. Even if initial speed of all the
particles was same, the molecular collisions will disrupt this uniformity.
Consequently, the particles must have different speeds, which go on changing
constantly. It is possible to show that though the individual speeds are
changing, the distribution of speeds remains constant at a particular
temperature.
• If a molecule has variable speed, then it must have a variable kinetic energy.
Under these circumstances, we can talk only about average kinetic energy. In
kinetic theory, it is assumed that average kinetic energy of the gas molecules is
directly proportional to the absolute temperature. It is seen that on heating a
gas at constant volume, the pressure increases. On heating the gas, kinetic
energy of the particles increases and these strike the walls of the container
more frequently, thus, exerting more pressure.
 BEHAVIOUR OF REAL GASES
• Ideal gas equation: pV = nRT
• Real gases do not follow ideal gas equation perfectly
under all conditions.
• Real gases do not follow, Boyle’s law, Charles law and
Avogadro law perfectly under all conditions.
Why do gases deviate from the ideal behaviour?
Two assumptions of the kinetic theory do not hold good. These are:
– There is no force of attraction between the molecules of a gas.
– Volume of the molecules of a gas is negligibly small in comparison to the
space occupied by the gas
 What are the conditions under which gases deviate from
ideality?
• Real gases show deviations from ideal gas law because molecules interact
with each other.
• At high pressures molecules of gases are very close to each other. Molecular
interactions start operating. At high pressure, molecules do not strike the
walls of the container with full impact because these are dragged back by
other molecules due to molecular attractive forces.
• This affects the pressure exerted by the molecules on the walls of the
container. Thus, the pressure exerted by the gas is lower than the pressure
exerted by the ideal gas.
 • Repulsive forces also become significant. Repulsive interactions are short-
range interactions and are significant when molecules are almost in contact.
This is the situation at high pressure. The repulsive forces cause the
molecules to behave as small but impenetrable spheres. The volume
occupied by the molecules also becomes significant because instead of
moving in volume V, these are now restricted to volume (V–nb) where nb is
approximately the total volume occupied by the molecules themselves.
• Therefore, Ideal gas equation PV= nRT becomes:

known as van der Waals equation. In this equation n is number of moles of the gas.
Constants a and b are called vander Waals constants and their value depends on the
characteristic of a gas.
 Compressibility factor
• Deviation from ideal behaviour can be measured in terms of compressibility factor:

• For ideal gas Z = 1 at all temperatures and pressures

• For gases which deviate from ideality, value of Z deviates from unity.
• At very low pressures, Z~1 and behave as ideal gas.
• At high pressure, Z > 1. difficult to compress.
• At intermediate pressures, Z < 1. Thus gases show ideal behaviour when the
volume occupied is large so that the volume of the molecules can be neglected in
comparison to it.
 Some important points
• Behaviour of the gas becomes more ideal when pressure is very low.
• The temperature at which a real gas obeys ideal gas law over an appreciable
range of pressure is called Boyle temperature or Boyle point.
• Above their Boyle point, real gases show positive deviations from ideality
and Z values are greater than one. Below Boyle temperature real gases first
show decrease in Z value with increasing pressure, which reaches a
minimum value. On further increase in pressure, the value of Z increases
continuously.
If we note the following derivation:

If the gas shows ideal behaviour then

On putting this value

Compressibility factor is the ratio of actual molar volume of a gas to the molar
volume of it, if it were an ideal gas at that temperature and pressure.