States of Matter (Synopsis)

Gaseous State
 In Gaseous State, the particles move rapidly in all the directions and have large voids
 Boyle’s Law. The volume of a fixed mass of a gas is inversely proportional to the pressure at constant
temperature. (At constant T, n) V 1/P or P1V1 = P2V2
P-V Curve at constant temperature: A rectangular hyperbolic curve
P-1/V curve at constant temperature: A straight line passing through the origin.
PV-P curve at constant temperature: A straight line parallel to pressure axis
Charle’s Law. The volume of fixed mass of a gas is directly proportional to the Absolute temperature at
constant pressure. (At constant P, n) VT or V1/T1 = V2/T2
n1T1 = n2T2 (for open vessel; pressure and volume of open vessel is constant)
Coefficient of volume expansion () = 1/273
 Absolute Zero. The hypothetical temperature at which all the gases are supposed to occupy zero volume.
Its numerical value of Celsius scale is -273.15oC.
 Kelvin scale of temperature (Absolute scale of temperature): On the basis of Charle’s law, a new scale
of temperature called Kelvin scale or absolute scale of temperature has been prepared. The zero on this
scale, called absolute zero of temperature . It corresponds to -273.15oC on the Celsius scale. i.e,
-273.15 (or roughly -273) = 0K
In general, Kelvin or Absolute Temp.T= (toC+ 273). It is also called thermodynamic scale of temperature.
 Gay Lussac’s Law. The pressure of fixed mass of gas at constant volume is directly proportional to its
temperature in Kelvin. (At constant V, n) PT or P1/T1 = P2/T2
 Avogadro’s Law. Under similar conditions equal volumes of various gases contain equal number of
molecules. (At constant T, P) Vn
 Ideal gas equation: It is given as PV = nRT or P1V1/T1 = P2V2/T2
Where R is called gas constants. Some useful relations derived from ideal gas equations are
P = wRT/MV; P = dRT/M , P1/P2 = d1T1 / d2T2
 Units of R (i)0.0821 L atm K mol (ii)0.0831 dm bar K mol (iii) 8.314 J K-1 mol-1 (iv) 1.99 Cal K-1 mol-1.
-1 -1 3 -1 -1

 Dalton’s Law. The pressure of the mixture of non-reacting gases is equal to the sum of their partial
pressure when enclosed in the same volume under similar conditions. P = p1 + p2 + p3
 Partial pressure of a particular gas in a mixture of non reacting gases is given by the relation
Partial pressure of a component = Mole fraction of the component x Total pressure
 Aqueous tension: The partial pressure of water vapour at particular temperature is called the aqueous
tension at that temperature On the basis of Dalton’s law of partial pressure, the pressure of dry gas
(Pgas) can be calculated even when it is collected over water.
Pdry = Pmoist. – aqueous tension.
Partial pressure of water in air
% Relative Humidity = ×100
Vapour pressure of water
 Graham’s Law of Diffusion. The rate of diffusion of gases (V/t) is inversely proportional to square root of
their densities under similar conditions. r 1 or r1 d2 M2
 
d r2 d1 M1
Volume diffused Moles diffused
Rate of diffusion  
Time Taken Time Taken
Pressure Drop Distance travelled by the gas
 
Time Taken Time Taken
 Effusion: When a gas is allowed to escape through a fine orifice or a pin hole, the phenomenon is termed
as effusion. The effusion of gases also follows Graham’s law of diffusion.
PA
Rate of effusion =
2 RTm
Where, P = Partial pressure of gas, A = Area of cross section of an orifice , m = molecular mass of gas.
 Vapour Density of a Gas. It is the ratio of the mass of certain volume of gas to the mass of same volume
of hydrogen under similar conditions. Molecular mass of gas = 2  vapour density
 Kinetic gas equation: PV = 1/3mnu2,
where P = pressure of the gas, V = volume of the gas, m = mass of a single molecule of the gas, n =
number of molecules present in volume V, and u = root mean square (RMS) velocity of the gas molecules.
Total kinetic energy of one mole of a gas (E k) = Ek = 3/2RT For n moles of a gas Ek = 3/2nRT
Average kinetic energy of a single molecule of a gas E’k = 3/2kT
Where k is constant called Boltzmann constant. k = R/NA = 1.3807 x 10-23 JK-1
 Different types of molecular velocities: Three different types of molecular velocities are most probable
velocity (), average velocity (v) and root mean square velocity (u). These are given by the relation
2 RT 8RT 3RT 3PV
 ;  ; u or
M M M M
  Ideal and real gases: A gas is termed as ideal if its obeys gas laws and gas equation under all conditions
of temp. and pressure. A gas which does not obey gas laws and gas equation under all conditions of temp.
& pressure is called a real gas.
 Deviation of real gases from ideal gas behaviour: it can be expressed in terms of Compressibility
factor (Z): It is defined as Z = PV/nRT.
For an ideal gas, Z = 1, For real gas Z is either greater than or less than unity (i.e., either Z > 1 or Z < 1)
The behaviour of real gases under different conditions of temperature and pressure is as follows:
(i) At very low pressure: Z = 1.Thus at very low pressures (upto apprx. 10 atm); the real gases exhibit
nearly ideal behaviour.
(ii) At low pressure: Z < 1 (except for H2 and He). Thus, at low pressures, all the real gases except H2 and
He show negative deviation. H2 and He show a continuous increase in Z with increase in pressure. For
most of other gases, the value of Z first decreases and then increases.
(iii) At high pressures: Z > 1 for all real gases (positive deviation)
(iv) Effect of temperature on the deviation of real gases: Deviation from ideal behaviour is more
pronounced at lower temperatures. The deviations become less and less with increase in temperature.
The temperature at which a real behaves like an ideal gas over an appreciable range of pressure is called
Boyle point or temperature.
Boyle’s Temperature TB = a/Rb Inversion temperature Ti = 2TB = 2a/Rb
 Cause of deviation from ideal behaviour: The deviation of real gases from ideal behaviour is due to
following faulty assumptions in the kinetic theory of gases.
(i) The actual volume of the molecules is negligible as compared to the total volume of the gas.
(ii) the molecules of a gas do not attract one another and move independently of each other.
 Van der Waal’s equation: In order to explain the behaviour real gases, van der waals derived an
equation known as van der Waal’s equation. The equation is as follows
For one mole of a gas (P + a/V2)(V – b) = RT For n moles of a gas (P + an2/V2)(V – nb) = nRT
 Van der Waal’s constants (a and b): Both the constants a and b depend upon the nature of the gas.
(i) The constant ‘a’: Larger the value of ‘a’ for a gas, greater is the magnitude of forces of attraction (van
der Waals forces) between its molecules and more easily the gas gets liquefied.
(ii) The units ‘a’ are atm L2 mol-2. The SI units of ‘a’ and Nm4 mol-2
(iii) The constant ‘b’: It refers to the excluded volume or co volume of gas. The excluded volume is four
times the actual volume of the molecules. Thus ‘b’ can be regarded as a measure of the effective size
of the gas molecules. Higher the value of b, greater is the actual vol. of the molecules of a gas. The units
of ‘b’ are L mol-1. The SI units of ‘b’ are m3mol-1.
 Critical constants: Critical temp.(Tc), critical pressure (Pc) & critical volume (Vc) are referred to as critical
constants of gas.
(i) Critical temperature: The maximum temperature at which (or below which) a gas can be liquefied by
applying pressure on it is called the critical temperature. A gas cannot be liquefied above its critical
temperature, whatever be the value of pressure applied. It is given by T c = 8a/27bR
Where a and b are van der Waal’s constants and R is the gas constant
(ii) Critical pressure (Pc): The minimum pressure required to liquefy a gas at critical temperature is called
critical pressure. It is given by Pc = a/27b2
(iii) Critical volume (Vc): The volume occupied by 1 mole of gas at its critical temperature and critical
pressure is called critical volume. It is given by V c = 3b
 Intermolecular forces: intermolecular forces common in different types of substances are
(a) Dipole dipole interactions (Keesom forces) (b) Dipole induced dipole interactions (Debye forces)
(c) London forces (d) Hydrogen bonding
Liquid State
 In liquid state particles are loosely packed. The voids & molecular motion much smaller than those in gases.
 Vapour Pressure. The pressure exerted by the vapours of the liquid in equilibrium with the liquid at
particular temperature. Vapour pressure of a liquid depends upon temperature and nature of liquid. Volatile
liquids have higher vapour pressure.
 Boiling Point of Liquid. The temperature at which the vapour pressure of the liquid becomes equal to the
atmospheric pressure (or pressure applied on the surface of the liquid) is called boiling point of the liquid .
The boiling point of a liquid remains constant during boiling.
According to Trouton’s rule Hvap/Tb = 21 cal K-1 mol-1
Normal boiling point of liquid = 2/3 x Critical temperature
 Surface Tension. The force acting perpendicular to the surface of the unit length. It is expressed in dynes
cm-1 or Nm-1. It decreases with increase in temperature. The effect of temperature on the surface tension is
given by Eotvos.   k (Tc  T)  d / M 2/3 . Where Tc = Critical Temperature k is constant.
 Viscosity. It is the force of friction which one part of liquid offers to another part of the liquid. It is expressed
in dynes cm-2 sec. This quantity is called 1 poise. Increase in temperature decreases its viscosity.
 Of the three physical states of matter, the gaseous state is most random state & solid state is least random