KINETIC THEORY

MADE BY-MEGHA PATEL

AND PALLAVI JOSHI
 INTRODUCTION
 The actual atomic theory got established more
than 150 years later.
 Kinetic theory explains the behaviour of gases
based on the idea that the gas consists of rapidly
moving atoms or molecules.
 The kinetic theory was developed in the
nineteenth century by Maxwell,Boltzmann and
others.
 It gives a molecular interpretation of pressure and
temperature of a gas laws and Avagadro’s
hypothesis.
 It also relates measurable properties of gases
such as viscosity,conduction and diffusion .
 It correctly explains specific heat capacities of
many gases.
BEHAVIOUR OF GASES
From above fig.we come to know that
properties of gases are easier to understand
. than those of solids and liquids. This is
mainly because in a gas ,molecules are far
from each other and their mutual interactions
are negligible except when two molecules
collides
EXPANSION OF GASES &GAS LAWS
In the case of gases,thermal expasion is
very large as compared to that of solids
and liquids.It is found that the volume of
a solid or liquid practically remains the
same,even when a large pressure is
applied.however,the volume of a gas
changes appreciably,when it’s pressure is
changed even by a small amount.
Therefore to describe the condition of a
gas its volume,pressure and temperature
must be specified. A change of one affects
the others
The gas laws are the study of the relation
between any two of these quantities,when
the third kept constant.The three Gas laws
are the studies of
(1)effect of pressure on the volume of a
given mass of a gas at constant
temperature.
(2)effect of temperature on the volume of a
given mass of a gas at constant pressure
and
(3)effect of temperature on the pressure of
a given mass of gas at constant volume.
 BOYLE’S LAW
 This law was discovered by Robert Boyle in
1662 and it is most fundamental laws
 It states-”the temperature remaining
constant,the volume of a given mass of a
gas is inversely proportional to the
pressure.It is called Boyle’s law
 mathematically, if temperature of the gas
is constant,then
PV =CONSTANT OR
V=1
P
In general if P1 and V1 are the initial
pressure and volume of a gas and P2
and V2,their final values,then
P1V1=P2V2

Fig1.01 shows graphs between P and

V at constant temperatures T1 and T2,
SUCH THAT T2>T1
 CHARLES LAW
 Around 1787,A.C.Charles studied the
variation in volume of a gas with
temperature and formulated the following
law:
“The pressure remaining constant, the
volume of a given mass of a gas increases
or decreases by a constant fraction of it’s
volume at 0 C for each rise or fall of 1 C in
temperature.”

V T=CONSTANT
The above equation tells that the graph betweenV
and T for a given mass of gas at constant pressure
must be straight line as shown dotted in fig.
 GAY LUSSAC’S LAW

Joseph Gay Lussac studied the variation of

pressure of a gas with temperature and
arrived at the following result:
“The volume remaining constant ,the
pressure of a given mass of a gas increases
or decreases by a constant fraction of its
pressure at 0 C for each rise or fall of 1 C in
temperature”.
p/t = constant
 PERFECT GAS
EQUATION
In practice, the gases do not obey the gas laws at all values of
pressure and temperature. It is because of the intermolecular
forces between the gas molecules.
Perfect gas equation

consider one mole of a perfect gas.

Let P1,V1,T1,be its initial pressure,volume and
temperature respectively and P2,V2,andT2 be their
final values. The change of the state of gas from the
state (P1,V1,T1,)to(P2,V2,T2)may be supposed to be
taking place in the following two steps:
STEP 1
 Suppose that the temperature of the
gas remains constant at T1 and the
pressure is changed from P1 to P2 so
that volume of the gas changes from
V1 to, say V’.Since the temperature of
the gas remains constant , from
Boyle’s law, we have
P1V1=P2V2 ………….. (1.09)
STEP 2
 Now,the pressure,volume and the
temperature of the gas are P2,V’,and T1
respectively.Suppose that the pressure
of the gas is kept constant at P2 and
temperature of the gas is changed from
T1 to T2,so that volume changes from
V’ to V2.Since the pressure of the gas
remains constant, from charles’ law , we
have
V’/T1=V2/T2
OR V’=V2*T1/T2
 Substituting for V’in the equation(1.09),
we have
P1V1=P2*(V2*T1/T2) OR
P1V1/T1=P2V2/T2 OR
PV/T=constant …….(1.10)
in above equation,for 1 mole of gas, the
constant is denoted by R and is called
universal gas constant.
PV=RT ………..(1.11)
this equation called perfect gas equation.
KINETIC THEORY OF GASES
 A gasis a collection of a large number of a
molecules,which are in continuous rapid
motion. The gas molecules have a size of
two into ten rest to minus ten meters.But it’s distance
between gas molecules is much bigger than it’s
size.Therefore the gas molecules can be considered
as to be moving freely with respect to each other.Due
to change in velocities the gas molecules collides.
Rudolph Claussius and JamesClark Maxwell developed
the Kinetic theory of gases in order to explains gas laws
in terms of the motion of the gas molecules.
The theory is based on following assumptions as regards
to the motion of molecules and the nature of gases:
All gases consist of molecules.The molecules of a gas
are all alike and differ from those of other gases.
The molecules of a gas are very small in size as
compared to the distance between them.
The molecules of a gas behaves as perfect spheres
The molecules are always in random motion.
The molecules do not exert any force on each other
except during collisions.
PRESSURE OF A IDEAL GAS

A gas exerts pressure on the walls of the

containing vessels due to continuous
collisions of the molecules against the
wall.
consider a gas enclosed in a cube
.suppose that the edges OA,OC,OE of
the vessels are along X,Y,andZ axis
respectively shown in fig
FIG.13.4 Elastic collision of a gas molecule with the wall of
the container.
 A molecule with velocity (VX.VY,VZ) hits the planer
wall parallel to yz-plane of area A.Since the collision
is elastic,the molecule rebound with the same
velocity;its y and z components of velocity does not
change in the collision but the x-component
reverses sign. That is, after collision is (-VX,
VY,VZ).The change in momentum of the molecule is:
-mvx-(mvx)=-2mvx.By the principle of conservation of
momentum, the momentum imparted to the wall in
the collision=2mvx.
To calculate the force on the wall,
we need to calculate momentum imparted to the
wall per unit time.In small interval t
A molecule with x-component of velocity Vx will
the wall if it is within the distance Vx t from the
wall.That is ,all molecules within the volume
AVx t only can hit the wall in time.But ,on the
average,half of these are moving towards the
wall and the other half away from the wall.Thus
the number of molecules with
velocity(Vx,Vy,Vz)hitting the wall in time t is
1/2AVx tn where n is the no. of
molecules per unit volume.The totol
momentum transferred to the wall by these
molecules in t is:
 Q=(2mVx)(1/2nAVx t)……….(13.10)
The force on the wall is the rate of
momentum transfer Q/ t and pressure is
force per unit area:
P=Q/(A t)=nmVx2……………………(13.11)
P=nmV2x……………….(13.12)
where V2x is the average of V2x.
Now gas is isotropic.
V2x=V2y=v2z=(1/3)v2x+V2y+v2x=(1/3)v2
Where V is the speed and V2x denotes the
mean of squared speed.Thus
P=1/3nmv2
 KINETIC INTERPRITATION OF
TEMPERATURE
 Equation (13.14) can be written as
PV=(1/3)nVmV2………..(13.15A)
PV=(2/3)NX1/2mV2………(13.15B)
Where N(=nV)is the number of
molecules in the sample.
The quantity in the bracket is the average
translational kinetic energy of the molecules in
the gas . Since the internal energy E of an ideal
gas is purely kinetic,
E=N*(1/2)mv2…………………..(13.16)
 Equation (13.15) then gives:
PV=(2/3)E…………(13.17)
we now ready for the kinetic interpritation of
temperature. Combining Eq(13.17) with the ideal
gas Eq(13.3), we get
E=(3/2)KbNT …..(13.18)
i.e., the average kinetic energy of a molecule
is proportional to the the absolute temperature of
the gas.The two domains are connected by the
Boltzmann constant.
we note that eq(13.18) tell us that internal energy
of an ideal gas depend upon only on temperature,
not on volume or pressure.
For a mixture of non reactive ideal gases,the total
pressure gets contribution from each gas in the
mixture.Eq(13.14) becomes
P=(1/3)[n1m1V21+n2m2v22+…]
(13.20)
1/2m1v21=1/2m1v22=(3/2KbT)
SO THAT P=(n1+n2+…)KbT………(13.21)
Which is Dalton’s Law of Partial pressures.
 LAW OF EQUIPARTITON OF
ENERGY
 The kinetic energy of a single molecule is
ET=1/2mv2x+1/2mv2y+1/2mv2z
(13.22)
For a gas in thermal equilibrium at
temperature T the average value of
energy denoted by<ET>IS

<ET>=<1/2mV2X>+<1/2mV2Y>+<1/2mv2
z>=3/2KbT (13.23)
<1/2mV2Z>=1/2KbT
Molecules of monoatomic gas like argon
have only translational degrees of
freedom.But what about a diatomic gas
such as o2 or N2?A molecule of o2 has
three translational degrees of freedom.
But in addition it can also rotate about it’s
centre of mass.Fig 13.6 shows two
independent axes of rotation 1 and
2,normal to the axis joining the two
oxygen atoms about which the molecule
can rotate.
Eachquadratic term occuring in the
expression for the energy is a mode of
absorption of energy by the molecule .We
have seen that in thermal equilibrium at
absolute temperature T,for each
translation mode of motion,the average
energy is 1/2kbT. A most elegant principle
of classical statistical mechanics states
that this is so for each mode of
energy:translational,rotational and
vibrational.that is equally distributed with
all energy modes this is known as law of
equipartition of energy.
 SPECIFIC HEAT CAPACITY

MONOATOMIC GASES
The molecule of monoatomic
gas has only three translational
degrees of freedom. Thus ,the
average energy of a molecule at
temperature T is (3/2)KbT.The total
internal energy of a mole of such a
gas is
U=3/2KbT*Na=3/2RT
The Molar specific heat at constant
volume,Cv is
Cv(monoatomic gas=
dU/dT=3/2RT
for an ideal gas
Cp-Cv=R
where Cp is the molar specific heat
at constant pressure,thus,
Cp=5/2R
 DIATOMIC GASES
As explained earlier ,a diatomic molecule
treated as a rigid rotator like a dumbbell
has 5 degrees of freedom: 3 translational
and 2 rotational.
using the law of equipartition of
energy, the total internal energy of a mole
of such a gas is
U=5/2KbT*Na=5/2RT
THE molar specific heat is given by
Cv=5/2R,Cp=7/2R
 POLYATOMIC GASES
 Ingeneral a polyatomic molecule has
3 translational,3 rotational degrees of
freedom and a certain number(f) of
vibritional modes. According to law of
equipartition of energy,it is easily
seen that one mole of such a gas has

U=(3/2kbT+3/2KbT+FKbT)NA
Predicted values of specific
heat capacities of gases
Nature Cv Cp Cp-Cv ?
of (j/mol/k (j/mol/k
gases (j/mol/k )
Monoat )12.5 20.8 8.31 1.67
omic
diatomi 20.8 29.1 8.31 1.40
c
triatomi 24.93 33.24 8.31 1.33
c
 SPECIFIC HEAT CAPACITY OF
SOLIDS
 We can determine the law of equilipartition of
energy to determine specific heat of solids.
Consider a solid of Natoms, each vibrating
about in its mean position. For a mole of
solid,N=Na,the total internal energy is
 U=3KbT*Na=3RT
 Now at constant pressure
c=deltaQ/deltaT=deltaU/deltaT=3R
SPECIFIC HEAT CAPACITY OF
SOLIDS
SUBSTAN SPECIFIC MOLAR
CE HEAT SPECIFIC
<J/KG/K> HEAT(J/K
G/K)
ALUMINIU 900.0 24.4
M
CARBON 506.5 6.1

LEAD 127.7 26.5

COPPER 386.4 24.5

 MEAN FREE PATH
 Molecules in a gas have rather large
speeds of the order of the speed of
sound.The top of a cloud of smoke
holds together for hours.this happens
because molecule in a gas have a
finite though small size so they are
bound to undergone collisions.as a
result move straight unhindered their
path keep getting incessantly
deflected.