DALTONS ATOMIC THEORY

All matter is formed of atoms.

The atoms are indivisible and invisible particles.
All atoms of a given chemical element are identical in all chemical properties.
Different chemical elements are composed of different atoms of different masses.
Atoms are indestructible. They retain their identities in a chemical reaction.
A compound is formed from its elements through the combination of atoms of
elements in small whole number ratios.

IDEAL AND REAL GASES

Ideal (or perfect) gas is one which rigidly obeys Boyles and Charle's laws for all
value of temperature and pressure. Its main characteristics are:
(i)
The product of pressure and volume of an ideal gas at constant temperature is
constant, i.e., if product PV is plotted against P at constant temperature, the curve
is a straight line.
(ii)
The compressibility factor of an ideal gas is "one", i.e., z (compressibility factor)= 1,
where PV / nRT=z
(iii)
If ideal gas is cooled at constant pressure, its volume continuously decreases, till
0K
(iv)
If an ideal gas is allowed to expand without doing any external work, it shows no
thermal effect.
Real gas:
(i)
It does not obey the Boyles and Charle's laws, particularly at low temperature and
high pressure.
(ii)
In case of real gases, it is not possible to continuously decrease the volume to zero
at - 273C. In fact, when sufficiently cooled, some real gases get suddenly
converted into liquid state.
(iii)
Real gases like H2, N2, O2, which are difficult to be liquefied differ from an ideal gas
to a greater extent than others like NH3, CO2, SO2, etc., which can be easily
liquefied. However, He shows an ideal behavior to some extent.

DEVIATIONS FROM GAS LAWS

Boyle's law: at constant temperature, the volume of a given mass of a gas is inversely
proportional to pressure.
Charle's law: at constant pressure, the volume of a given mass of a gas is directly
proportional to its temperature on Kelvin scales.
Dalton's law of partial pressure: total pressure exerted by a mixture of gases is equal to
the sum of the partial pressures of the individual gases in the mixture.
Avogadro's hypothesis: equal volumes of all gases under similar conditions of
temperature and pressure contain same number of molecules.
Graham's law of diffusion: the rates of diffusion of a gas depend upon the r.m.s. velocity
(C) of its molecules (i.e., one gas diffuses faster than another, because its molecules move
faster and undergo more collisions per second).

KINETIC THEORY OF GASES

The kinetic theory of gases was developed in an effort to explain the properties of
gases. It is one of the fundamental concepts of science. The major assumptions of kinetic
molecular theory are:
1. A gas consists of a vast number of tiny particles, called molecules.
2. Molecules of a gas are in constant random motion, travelling in straight lines at high
velocities, until they collide with one another or with the walls of the container.
3. The pressure exerted by a gas on the walls of its containing vessel is due to
bombardment by its moving molecules.
4. The collisions between molecules are "perfectly elastic", i.e., the molecule rebound
from collisions with no apparent lost of energy; the speed of a molecule is the same
after a collision, as before, only the direction of motion being changed.
5. Attractive forces between molecules are negligible, because if pressure upon a gas is
released (i.e. lowered), the gas expands.
6. The molecules are so small as compared with the average distance travelled between
consecutive collisions (which is known as the mean free path) that the space actually
occupied by the molecules is negligible as compared to the volume of the gas as a
whole.
7. The average kinetic energy of the molecule is proportional to the absolute
temperature. Thus, at any given temperature, the gaseous molecules have a certain
average kinetic energy.

VAN DER WAAL'S EQUATION OF STATE

Because of the deviation of real gases from the ideal gas law, many attempts have
been made to set up equations of state which will reproduce more satisfactorily the P - V - T
relations of gases. Of these equations, one of the earliest and best known is that of van der
Waals. The van der Waals equation differs from the ideal gas law in that it makes allowance
both for the volume occupied by the molecules themselves and for the attractive forces
between them.
1. Volume correction: Let b be the effective volume of the molecules in one mole of gas
and V be the total volume of n moles of gas. In this total volume, that occupied by the
molecules themselves thus will be nb, and hence, the volume available for compression will
be not V, but (V - nb).
:. Corrected volume or ideal volume= (V - nb)
2. Attraction correction: Consider the wall of a container which is being bombarded by
gaseous molecules. When the gas molecules are not constrained by attractions for each
other, they will bombard the wall with the full force due to their outward motion. If, however,
under the same conditions a molecule moving outward is subjected by molecular attraction,
it will not strike the wall with high force. Consequently, the pressure resulting from the
bombardment will be lessened by an amount Pa. The observed pressure, P, will thus be
less than the ideal pressure, Pi, by the amount Pa, or

Now the inward force Pa exerted on molecules which are about to strike the wall of the
vessel is proportional to:
(i)
the number of molecules in the interior which are attracting it, which is proportional
to the density of gas, and

(ii)

the number of molecules striking the walls of vessel at any instant, which is also
proportional to the density of the gas.

where 'a' is a proportionality constant, which is independent of pressure and temperature.

This equation of state is known as van der Waals equation of state for real gases.
Explanation of behavior of real gases on the basis of van der Waal's Equation:

LIQUEFACTION OF GASES
Liquefaction may be defined as a process in which a gas changes into a liquid state.
Thus liquefaction is the reverse of vaporization, i.e.,

Liquefaction is brought about by:

(i) Cooling (lowering temperature): All gases are composed of molecules which are in a
state of constant rapid motion. If the temperature is increased, they would move more
rapidly and kinetic energy of the gas would increase. On the other hand, if the temperature
is lowered, the kinetic energy of the gas molecules decreases and as a result molecules
move close to each other. Consequently, the volume occupied by the gas also decreases. If
this lowering of temperature is continued, at some stage, the molecules will come so close
together that they change into the liquid state.
(ii) Compressing (by increasing pressure): On compressing, the molecules come closer
and closer. The experiments, however, reveal that during the liquefaction of gases, the
change of temperature is more important than the change of pressure; and many of them
cannot be liquefied at the atmospheric temperature by compressing. This is due to the
kinetic energy of the molecules which, being high, prevents the attractive forces to hold the
molecules together.
Thus, for every gas there is a certain characteristic temperature above which it cannot be
liquefied, whatever the pressure may be applied. This temperature is called the critical
temperature of the gas. Below this temperature, the gas can be liquefied by the application
of pressure. Thus, the critical temperature may also be defined as the temperature to
which a gas must be cooled so that it may be liquefied on applying pressure. The minimum
pressure, at which a gas liquefies at the critical temperature, is called the critical pressure.
The volume occupied by one mole of a gas at its critical temperature, is called the critical
volume. Critical temperature, critical pressure and critical volume of a gas, are collectively
known as critical constants of the gas. They are represented as TC, PC and VC respectively.

A solution is a single phase homogeneous system, containing two or more

substances. The compositions of a solution may vary within wide limits. Examples of
solutions are common salt in water, alcohol in water, sugar in water, etc.
The component of a solution forming the larger proportion is referred to as solvent;
while the other component which is present in minor proportion in solution is called solute.
A solution in water is called aqueous solution (e.g., cane-sugar dissolved in water); while a
solution in a solvent other than water is called non-aqueous solution (e.g., iodine in carbon
disulphide).

IDEAL AND NON-IDEAL SOLUTIONS

Ideal solutions are those which obey Raoult's law exactly over a wide range of
composition and temperature. Moreover, in the formation of an ideal solution, the total
volume of solution formed is exactly equal to the sum of the volumes of the individual
components. Also during the formation of ideal solution, no heat change takes place, i.e.,
no heat is given out or absorbed; when constituents of an ideal solution are mixed. Dilute
solution behave almost as ideal solution.

Non-ideal solution is one which does not obey Raoult's law strictly. Concentrated
solutions are mostly non-ideal. Non-ideal solutions involve change in volume and enthalpy.

RAOULT'S LAW
When a non-volatile solute is dissolved in a solvent, then the vapor pressure of
solution is always less than that of pure solvent at the same temperature.
When volatile solute is dissolved in a solvent, then the vapor pressure of solution
(i)
increases if the solute is more volatile than the solvent
(ii)
decreases if the solute is less volatile than the solvent.
Raoult's law : (i) For non-volatile solutes : "The relative lowering of vapor pressure of a
solution containing a non-volatile solute is equal to the mole fraction of solute in solution".
(ii) For volatile solutes: "The partial vapor pressure of a component of solution containing
volatile liquids (or a volatile solvent and a volatile solute) at a given temperature is equal to
the vapor pressure of that component in the pure state multiplied by its mole fraction in
solution"
Limitations of Raoult's law: The law is applicable only
(1) To dilute solutions,
(2) When there is no change in the molecular state of solvent or solute due to association or
dissociation of solute or interaction of solute and solvent molecules,
(3) Solute is non-volatile and
(4) Solute is completely soluble in the solvent.

HENRY'S LAW
Gases dissolve in liquids to form true solutions, which are examples of two
component systems. The solubility of a gas depends on:
(i) the natur of the gas;
(ii) the temperature of the solution ;
(iii) the pressure of the gas over the solution, and
(iv) the nature of the solvent.
Le-Chatelier's principle predicts that with the increase of pressure, the solubility of a
gas should increase. William Henry (in 1803) made a systematic study of the solubilities of
gases in liquids and gave the Henry's law, which stales that the mass of gas (m) dissolved
by a unit volume of a solvent at constant temperature is directly proportional to the pressure
(p) of the gas in equilibrium.

Limitations of Henry's law: Henry's law is valid only for an ideal gas and for real gases, it
holds provided:
(i) The pressure is low. At high pressures, the law becomes less exact and the
proportionality constant shows a considerable variation;
(ii) The temperature is not low;
(iii) The solubility of the gas is low;
(iv) The dissolved neither reacts with solvent, nor dissociates or associates in the solvent.

MODES OF EXPRESSING CONCENTRATION OF SOLUTIONS

(1)
Percentage of a solution can be expressed as:
(i)
Mass percentage is the number of parts by mass of the solute per hundred
parts by mass of solution. If w g of solute is dissolved in W g of solvent, then
mass percentage of solute
100
(ii)

Volume percentage is the number of parts by volume of solute per hundred

parts by volume of solution. If VA and VB be the respective volumes of
component A and B of a solution, then volume percentage of A
100

(2)

Normality of a solution is the number of gram equivalents of the solute dissolved

per litre of the solution. Thus, normality (N)

(3)

Molarity is defined as the number of moles (molecular weight expressed in grams)

of the solute present in one litre of the solution. Thus, molarity (M)

(4)

Molality is defined as the number of moles of the solute dissolved in 1,000 g (or 1
kg) of the solvent (not solution). Thus, molality (m)

(5)

Mole fraction (X) of any component in a solution is the ratio of the number of moles
of that component to the total number of moles of solute plus solvent in the solution.

(6)

Mass fraction of any component in a solution is the ratio of the mass of that
component and the total mass of both (or all) components of the solution. Thus