States of Matter

(Gaseous & Liquid)

JEE Syllabus
3
CHAPTER
Gaseous State : Measurable properties of gases; Gas laws - Boyle's law,
Charle's law, Graham's law of diffusion, Avogadro's law, Dalton's law of
partial pressure; Concept of Absolute scale of temperature; Ideal gas
equation, Kinetic theory of gases (only postulates); Concept of average,
root mean square and most probable velocities; Real gases, deviation
from Ideal behaviour, compressibility factor, van der Waals equation,
liquefaction of gases, critical constants. Liquid State : Properties of liquid
- vapour pressure, viscosity and surface tension and effect of temperature
on them (qualitative treatment only).

THIS CHAPTER
GASEOUS STATE INCLUDES
BOYLE’S LAW
 Boyle's law
1
P at constant n and T..
V  Charle's law
P = 1.0 atm P = 2.0 atm
 Avogadro's law
 Dalton's law of
partial pressures
Increase
Pressure  Graham's law of
Boyle's Law representing
Pressure-Volume relation diffusion

V = 1.0 L Decrease  Kinetic theory of

Pressure V = 0.5 L gases
 Distribution of
molecular speeds
Graphical Representation
 Deviation from ideal
behaviour
V PV (van der Waal's
equation)
 Liquid state
P P

1/V logP

P log1/V
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CHARLE’S LAW
V  T at constant n and P.

 t 
Vt  V0 1  
 273 

V V/T logV V
Constant P

V0

–273°C 0°C T log T 1/T

T

AVOGADRO'S LAW
V  n (P and T constant); 1 mole of every gas at STP occupies volume = 22.4 lit.

Ideal Gas Equation

On combining the Boyle’s law, Charles law and Avogadro’s law we get an equation known as ideal gas
equation which correlate P, V, T, of a gas.

PV = nRT ideal gas equation where R is a constant known as universal gas constant or molar gas
constant.
Numerical value of R
R = 0.0821 litre atm K–1 mol–1
= 8.314 J K–1 mol–1
= 1.987  2 cal K–1 mol–1
Other form of ideal gas equation.

PV = nRT

W
 PV = RT
M

dRT
 P=
M

DALTON’S LAW OF PARTIAL PRESSURE

The total pressure exerted by a mixture of two or more non-reacting gases in a definite volume is equal to
the sum of individual pressures which each gas would exert if it occupies the same volume at a constant
temperature
P = p1 + p2 + p3 . . . .,

RT
P = (n1 + n2 + .......)
V
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Pgas = Mole fraction of gas × Total pressure.

no. of moles of gas

= × Total pressure
Total no. of moles of all gases

Note : P (moist) = P (dry gas) + P (H2O vapours)

P (dry gas) = P (moist) – aq. tension.

GRAHAM’S LAW OF DIFFUSION

(a) Diffusion is the ability of gas to spread and occupy the whole volume.

(b) Under identical conditions of temperature and pressure, the rate of effusion/diffusion of a gas is inversely
proportional to square root of its density.

(c) Rate of diffusion/effusion for two gases are related as

r1 V /t n t M2 d2
 1 1  1 1  
r2 V2 / t 2 n 2 t 2 M1 d1

where V = volume , t = time, M = molar mass, d = density, n = number of moles

KINETIC THEORY OF GASES

The postualates

(1) The gaseous molecules are considered to be the point masses.

(2) The volume of a molecule is negligible as compared to total volume of the gas.

(3) The molecules do not posses appreciable attraction.

(4) The collisions are perfectly elastic i.e. there is no loss of energy during the molecular collisions.

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

(6) The effect of gravity on molecular motion is negligible.

Based on Kinetic-Molecular Theory

1
PV  mNu2
3

m = Mass of one molecule

N = Number of molecules in the container

u = Root mean square velocity

3 3
KE of n moles = nRT,, for n = 1 KE  RT
2 2

3 RT 3
Average KE per molecule =  kT , k = Boltzmann’s constant
2 N0 2

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DISTRIBUTION OF MOLECULAR SPEEDS

3RT
(i) Root mean square velocity (rms) =
M

8RT
(ii) Average velocity(av) =
M

2RT
(iii) Most probable velocity (mp) =
M

Note : rms : av : mp : : 1.7 : 1.6 : 1.04 : : 1.224 : 1.128 : 1

Hence rms > av > mp

DEVIATION FROM IDEALITY (van der Waal’s EQUATION)

A plot of PV- P at constant temperature for a number of gases shows deviations from ideal behaviour. Therefore
PV = nRT can not be applied to these gases. Thus another equation must be sought in order to correlate P,V, T
for these gases; which is van der waal’s equation.

 2 
 P  n a V  nb   nRT
 V 2 


H2
He N2
Fraction of Molecule

Co
2

Ideal

P
Causes of Deviation
There are two objectionable postulates in the kinetic theory of gases.
(1) The volume of a molecule is negligible as compared to total volume of the gas. Actually gases molecules
do posses some volume which account for the deviation.
(2) There is no intermolecular force of attraction between gaseous molecules.
(There exists force of attraction between gaseous molecules otherwise liquefaction of gases would be
impossible).
By correcting these two postulates, we get an equation which can be applied to the gases which deviate
from ideal behaviour. The deviation of a gas from ideal behaviour can also be expressed in term of
compressiblity factor (Z).
PV
Z [for 1 mole]
RT
for ideal gas Z = 1
for real gas Z > 1 or Z < 1

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LIQUID STATE
A liquid is composed of molecules that are constantly moving about at random, each undergoing billions of
collisions per second. However strong attractive forces of the dipole-dipole, H-bonds, prevent them from moving
as freely and as far apart as in a gas.
(a) Viscosity : Liquids flows as if they were divided into layers flowing over one another. Resistance offered
to this flow is due to friction between two liquid layers and is called viscosity. Reciprocal of viscosity is
called fluidity. Viscosity of a liquid decreases with rise of temperature.
(b) Coefficient of viscosity : The force in newtons per square metre required to maintain a difference of velocity
of one metre per second between two parallel layers of the liquid at a distance of one metre from each other.
It is expressed in Kg m–1 s–1. Liquids having stronger attractive forces are more viscous.
(c) Surface tension : The force that acts at right angles to an imaginary line of unit length at the surface
of the liquid at rest. It is expressed in J m–2 or N m–1. Surface tension generally decreases with the rise
of temperature. Liquids exhibit capillary action and make spherical drops. This can be explained on the
basis of surface tension.

IMPORTANT POINTS
(1) Critical temperature (T c) :
It is the temperature above which a real gas can not be liquefied whatever applied pressure may be

8a
Tc =
2 7R b

(2) Critical pressure (Pc) :

It is the minimum pressure required to liquefy the gas at critical temperature

a
PC 
27b 2
(3) Critical volume (Vc) :
The volume occupied by 1 mole of the gas at critical temperature and critical pressure is known as
critical volume.

VC  3b

Vc  3  4 Vm  12 Vm (Since b = 4Vm)

(4) Critical coefficient of a gas :

RTc
It is ratio of P V which is equal to 2.66 and remain constant for all the gases.
c c

(5) Boyle's temperature (TB) :

The temperature at which a real gas obey ideal gas equation at very low pressure is known as Boyle’s
temperature.

a
TB 
Rb
Boyle's temperature of a gas is always higher than its critical temperature (Tc)

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(6) Inversion temperature (Ti)

If a compressed gas is allowed to pass through a fine hole, it may show cooling or heating or no change
in temperature depending up on the temperature of the gas. For each gas there exists a characteristic
temperature known as inversion temperature (Ti)
If T > Ti heating is produced
If T < Ti cooling is produced
If T = Ti neither heating nor cooling

2a
Ti   2TB
Rb



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