Kinetic Theory of Gases

Gas (2) The molecules of a gas are identical,

In gases the intermolecular forces are spherical, rigid and perfectly elastic point
very weak and its molecule may fly apart in masses.
all directions. So the gas is characterized by (3) Their size is negligible in comparison
the following properties. to intermolecular distance (10–9m)
(i) It has no shape and size and can be (4) The volume of molecules is negligible
obtained in a vessel of any shape or size. in comparison to the volume of gas. (The
(ii) It expands indefinitely and uniformly to volume of molecules is only 0.014% of the
fill the available space. volume of the gas).
(iii) It exerts pressure on its surroundings. (5) Molecules of a gas keep on moving
(iv) Intermolecular forces in a gas are randomly in all possible direction with all
minimum. possible velocities.
(v) They can easily compressed and (6) The speed of gas molecules lie
expand. between zero and infinity

Assumption of Ideal Gases (or Kinetic Theory of (7) The gas molecules keep on colliding
Gases) among themselves as well as with the walls
of containing vessel. These collisions are
perfectly elastic.

(8) The time spent in a collision between

two molecules is negligible in comparison to
time between two successive collisions.

Kinetic theory of gases relates the (9) The number of collisions per unit
macroscopic properties of gases (such as volume in a gas remains constant.
pressure, temperature etc.) to the (10) No attractive or repulsive force acts
microscopic properties of the gas molecules between gas molecules.
(such as speed, momentum, kinetic energy (11) Gravitational attraction among the
of molecule etc.) molecules is ineffective due to extremely
Actually it attempts to develop a model of small masses and very high speed of
the molecular behaviour which should result molecules.
in the observed behaviour of an ideal gas. It (12) Molecules constantly collide with the
is based on following assumptions : walls of container due to which their
(1) Every gas consists of extremely small momentum changes. The change in
particles known as molecules. The molecules momentum is transferred to the walls of the
of a given gas are all identical but are container. Consequently pressure is exerted
different than those of another gas. by gas molecules on the walls of container.
 (13) The density of gas is constant at all
points of the container.
Gas Laws
(1) Boyle’s law :For a given mass of an (2) Charle'slaw :If the pressure
ideal gas at constant temperature, the remaining constant, the volume of the given
volume of a gas is inversely proportional to mass of a gas is directly proportional to its
P1 P2
its pressure. absolute temperature.
Increase pressure

P
P

Decrease pressure Increase volume

V1 V2

(A) (B) T2>T1

Fig. 13.1 Decrease volume V2
T1 V1

(A) (B)
1 Fig. 13.3
V∝
i.e. P orPV = constant  P1 V 1 =P2 V 2 V V1 V2
=constant =
T1 T2
(i) PV =
P ( mρ )= constant  P
ρ
=constant
or
i.e., VT  T
V m m
= =constant V=
P1 P2 (i) T ρT (As volume ρ)
=
ρ1 ρ2
or ρT =constant  ρ1 T 1= ρ2 T 2
m
=
(As volume ρ( Density of the gas) and m = (ii) If the pressure remains constant, the
Vt
constant) volume of the given
mass of a gas V0

(ii) PV =
P ( )
N
n
=constant P =constant
n or increases or
t(°C)
1 – 273.15 O
P1 P2
=
n1 n2 decreases by 273 .15 of Fig. 13.4

(iii) As number of molecules per unit its volume at 0°C for each 1°C rise or fall in
N temperature.
n=
volume V

V=
N (
V t =V 0 1+
1
273 . 15
t ).
 n alsoN = constant
This is Charle’s law for centigrade scale.
(iv) Graphical representation : If m and T
(v) Graphical representation: If m and P
are constant
are constant
P PV PV
V 1/V V

V P V
(A) (B) (C) T T 1/T
(A) (B) (C)

P V

V/T V/T

1/V 1/P
(D) (E) T or 1/T V or 1/V
 (5) Grahm’s law of diffusion : When
two gases at the same pressure and
temperature are allowed to diffuse into each
other, the rate of diffusion of each gas is

(3) Gay-Lussac’s law or pressure inversely proportional to the square root of

law :The volume remaining constant, the 1 1

r∝
pressure of a given mass of a gas is directly the density of the gas i.e. √ ρ  √ M (M is
proportional to its absolute temperature.

P
=constant
P1 P2
=
the molecular weight of the gas) 
r1
r2
=
√ρ2
ρ1

√
T T T2 M2
PT or  1
=
M1
(i) The volume remaining constant, the
pressure of a given
Pt If V is the volume of gas diffused in tsec

mass of a gas then

P0
increases or decreases V r1 = V 1 × t 2
t(°C) r=
1 t  r2 V 2 t 1
– 273.15 O

by 273 .15 of its

Fig. 13.5
(6) Dalton’s law of partial
pressure at 0°C for each 1°C rise or fall in pressure :The total pressure exerted by a
temperature. mixture of non-reacting gases occupying a

[
Pt =P0 1+
1
273 .15
t ] vessel is equal to the sum of the individual
pressures which each gases exert if it alone
This is pressure law for centigrade scale. occupied the same volume at a given
(ii) Graphical representation :If m and temperature.
V are constants P=P1 + P2 + P3 +.. . .. Pn
For n gases
P P/T P/T
whereP = Pressure exerted by mixture
P1 , P2 , P3 , ...... Pn =
and Partial pressure of
component gases.
T T or 1/T P or 1/P
(A) (B) (C) Equation of State or Ideal Gas Equation
The equation which relates the pressure
(P) volume (V) and temperature (T) of the
1/P P
given state of an ideal gas is known as ideal
gas equation or equation of state.
T 1/T PV
(D) (E)
=R
Fig. 13.6 For 1 mole of gas T (constant) PV
= RT
(4) Avogadro’s law :Equal volume of all
whereR = universal gas constant.
the gases under similar conditions of
Table 13.1 : Different forms of gas
temperature and pressure contain equal
equation
N 1 =N 2
number of molecules i.e. .
 Quantity Equation Constant R Joule
r=
M . It's unit is gm×kelvin and dimension
of gas
[ L2 T −2 θ−1 ]
1 mole gas PV = RT R = universal
gas constant Since the value of M is different for
different gases. Hence the value of r is
 mole gas PV = RT
different for different gases. e.g. It is
1 molecule
of gas
PV =
( )
R
NA
T =kT
k = Boltzmann's
constant
rH =
2
R
2
maximum for hydrogen
N PV = NkT Real Gases
molecules
(1) The gases actually found in nature are
of gas
called real gases.
1
gas
gm of PV =( )
R
M
T =rT r = Specific gas
constant
(2) They do not obeys gas Laws.
(3) For exactly one mole of an ideal gas
mgm of PV = mrT PV
=1 .
gas RT Plotting the experimentally determined
PV
value of RT for exactly one mole of various
(1) Universal gas constant
real gases as a function of pressure P, shows
(R) :Universal gas constant signifies the
a deviation from identity.
work done by (or on) a gas per mole per
PV
kelvin. RT
(4) The quantity is called the
PV Pressure ×Volume Work done compressibility factor and should be unit for
R= = =
μT μ× Temperature μ× Temperature
an ideal gas.
(i) At S.T.P. the value of universal gas
constant is same for all gases R =
2
J cal ~ cal N2 CH4
8 . 31 =1. 98 −¿ 2 ¿ H2
mole×kelvin mole×kelvin mol ×kelvin
1.5
litre×atm
=0. 8221 PV CO2
mole×kelvin . RT 1
Ideal gas

2 −2 −1
(ii) Dimension :[ ML T θ ] 0.5

(2) Boltzman's constant (k) :It is

0 200 400 600 800 1000
represented by per mole gas constant i.e., P (atm)
Fig. 13.7
R 8 .31
k= =
N 6 . 023×1023 =1.38×10−23 J/ K
2 −2 −1 (5) Deviation from ideal behaviour as a
It's dimension :[ ML T θ ]
function of temperature
(3) Specific gas constant (r) :It is
represented by per gram gas constant i.e., 2 200 K 500 K

1.5
1000 K
PV
RT 1 Ideal gas

0.5
 5 −2
Dimension : [a] = [ ML T ] and [b] = [L3]
Units :a = Nm4 and b = m3.
(8) Andrews curves :The pressure (P)
versus volume (V) curves for actual gases
(6) A real gas behaves as ideal gas most are called Andrews curves.
closely at low pressure and high D G
P Gas
380°C
temperature. Also can actual gas can be Liquid vapour region
H
liquefied most easily which deviates most 374.1°C

Liquid 370°C
from ideal gas behaviour at low temperature F 360°C E
and high pressure. Vapour
C 350°C B
A V
(7) Equation of state for real gases: It Andrews curve for water
Fig. 13.9
is given by Vander Waal's with two correction
in ideal gas equation. The it know as Vander
(i) At 350°C, part AB represents vapour
Waal's gas equation.
phase of water, in this part Boyle’s law is
(i) Volume correction :Due to finite size
of molecule, a certain portion of volume of a
obeyed
( P∝ )
1
V . Part BC represents the co-
gas is covered by the molecules themselves.
existence of vapour and liquid phases. At
Therefore the space available for the free
point C, vapours completely change to liquid
motion of molecules of gas will be slightly
phase. Part CD is parallel to pressure axis
less than the volume V of a gas. Hence the
which shows that compressibility of the
effective volume becomes (V – b).
water is negligible.
(ii) Pressure correction : Due to
(ii) At 360°C portion representing the co-
intermolecular force in real gases, molecule
existence of liquid vapour phase is shorter.
do not exert that force on the wall which
(iii) At 370°C this portion is further
they would have exerted in the absence of
decreased.
intermolecular force. Therefore the observed
(iv) At 374.1°C, it reduces to point (H)
pressure P of the gas will be less than that
called critical point and the temperature
present in the absence of intermolecular
374.1°C is called critical temperature (Tc) of
force. Hence the effective pressure becomes
water.
( P+ Va ).
2
(v) The phase of water (at 380°C) above

(iii) Vander Waal's gas equations the critical temperature is called gaseous
phase.

For 1 mole of gas

( P+
a
V2 )
(V −b )=RT
(9) Critical temperature, pressure
and volume :The point on the P-V curve at

For  moles of gas

( P+
aμ 2
V2 )
(V −μb)=μ RT
which the matter gets converted from
gaseous state to liquid state is known as
Here a andb are constant called Vander
critical point. At this point the difference
Waal’s constant.
between the liquid and vapour vanishes i.e.
the densities of liquid and vapour become (1) Instantaneous velocity : Any
equal. molecule of gas moves with velocity ⃗
v in any

(i) Critical temperature (Tc) :The direction

maximum temperature below which a gas
can be liquefied by pressure alone is called where √
⃗v =v x ^i +v y ^j+v z k^  v= v x +v y +v z . Due to
2 2 2

critical temperature and is characteristic of v x =v y=v z

random motion of molecule 
the gas. A gas cannot be liquefied if its v 2=3 v 2x =3 v 2y=3 v 2z
temperature is more than critical
(2) Time during collision :Time
temperature.
between two successive collision with the
CO2 (31.1°C), O2 (–118°C), N2 (–147.1°C) wall A1.
and H2O (374.1°C) Distance travelled by molecule between two successive collision
Δt =
(ii) Critical pressure (Pc) :The minimum Velocity of molecule
2L
pressure necessary to liquify a gas at critical =
vx
temperature is defined as critical pressure
(3) Collision frequency (n) :It means
CO2 (73.87 bar) and O2 (49.7atm)
the number of collision per second. Hence
(iii) Critical volume (Vc) :The volume of
1 v
n= = x
1 mole of gas at critical pressure and critical Δt 2 L
temperature is defined as critical volume CO2 (4) Change in momentum : This
(95 10–6m3) molecule collides with the shaded wall (A1)
(iv) Relation between Vander Waal’s with velocity vx and rebounds with velocity
constantsand Tc, Pc, Vc −v x
.
8a Pc =
a
T c= The change in momentum of the
27 Rb , 27 b2 , V c =3 b ,
molecule
T 2c
( ) and
R Tc Pc V c
2
27 R 3
a= b= = R Δp=(−mv x )−(mv x )=−2mv x
64 Pc 8 Pc Tc 8
,
As the momentum remains conserved in
Pressure of an Ideal Gas
a collision, the change in momentum of the
Consider an ideal gas (consisting of N
Δp=2 mv x
wall A1 is
molecules each of mass m) enclosed in a
cubical box of side L. After rebound this molecule travel toward
−v x
opposite wall A2 with velocity , collide to it
vx
and again rebound with velocity towards

Y
wall A1.
Y (5) Force on wall :Force exerted by a
vx vy v single molecule on shaded wall is equal to
X
vx
X vz
vx rate at which the momentum is transferred

L Z to the wall by this molecule.

Z
(A) (B)
Δp 2mv x mv 2
Fig. 13.10 F Single molecule= = = x
Δt (2 L/ v x ) L
i.e.
 A1 (8) Effect of mass, volume and
The total force on the wall due to all
m 1mN 2
P= v
L ∑ x=
Fx= v2 3 V rms
the molecules temperature on pressure: or

m 2 mN 2 (m N )T
( v x + v 2x 2 + v 2x3 +. .. )= P∝ 2
[As v rms ∝ T ]
v V
M 1 L x

v 2x = (i) If volume and temperature of a gas are

mean square of x component of the
constant PmNi.e. Pressure  (Mass of gas).
velocity.
i.e. if mass of gas is increased, number of
(6) Pressure : Now pressure is defined as
molecules and hence number of collision per
force per unit area, hence pressure on
second increases i.e. pressure will increase.
F mN 2 mN 2
P x= x = v = v (ii) If mass and temperature of a gas are
shaded wall A AL x V x
constant. P (1/V), i.e., if volume decreases,
For any molecule, the mean square
number of collisions per second will increase
v 2=v 2x +v 2y +v 2z v 2x =v 2y=v 2z
velocity ; by symmetry due to lesser effective distance between the
2
v walls resulting in greater pressure.
v 2x =v 2y=v 2z =
 3
(iii) If mass and volume of gas are
Total pressure inside the container
P∝( v rms )2 ∝T
constant,
1 mN 2 1 m N 2
P= v= v
3 V 3 V rms (where i.e., if temperature increases, the mean
square speed of gas molecules will increase
v rms=√ v )
2

and as gas molecules are moving faster, they

(7) Relation between pressure and will collide with the walls more often with
1mN 2 greater momentum resulting in greater
P= v
kinetic energy :As we know 3 V rms
pressure.
1M 2 1
= v P= ρ v 2rms
3 V rms  3 ... (i) Various Speeds of Gas Molecules

[As M = mN = Totalmass of the gas and The motion of molecules in a gas is

M characterised by any of the following three
ρ=
V ]
speeds.

 K.E. per unit volume

E=
1 M 2
2 V
1
v rms = ρ v 2rms
2 ( ) (1) Root mean square speed :It is
defined as the square root of mean of
...(ii)
squares of the speed of different molecules
2
P= E
From (i) and (ii), we get 3

i.e. the pressure exerted by an ideal gas i.e.

v rms=
√
v 21 + v 22 + v 23 + v 24 +.. . .
N
= √ v2

is numerically equal to the two third of the (i) From the expression of pressure
1
mean kinetic energy of translation per unit P= ρ v 2rms
3
volume of the gas.


v rms=
√ √
3P
ρ
=
3 PV
Mass of gas
=
3 RT 3 kT
M
=
m √ √
 Mass of gas (2) Most probable speed :The particles
where ρ= =Density of the gas
V , M = μ׿ ¿ of a gas have a range of speeds. This is

(mass of gas), pV =μ RT , R = kN A , k = defined as the speed which is possessed by

Boltzmann’s constant, maximum fraction of total number of

M molecules of the gas. e.g., if speeds of 10

NA molecules of a gas are 1, 2, 2, 3, 3, 3, 4, 5, 6,
m= = mass of each molecule.
6 km/s, then the most probable speed is 3
(ii) With rise in temperature rms speed of
km/s, as maximum fraction of total
v rms ∝ √ T
gas molecules increases as . molecules possess this speed.
(iii) With increase in molecular weight rms Most probable speed

√ √ √
1
v rms ∝ 2 P 2 RT 2 kT
√M v mp= = =
speed of gas molecule decreases as ρ M m
. e.g., rms speed of hydrogen molecules is (3) Average speed :It is the arithmetic
four times that of oxygen molecules at the mean of the speeds of molecules in a gas at
same temperature. given temperature.
(iv) rms speed of gas molecules is of the v 1 + v 2 + v3 +v 4 +. . .. .
v av =
order of km/se.g., at NTP for hydrogen gas N

√ √
3 RT 3×8 .31×273 and according to kinetic theory of gases
(v rms )= = =1840 m/s
M 2×10 3

√ √ √
. 8 P 8 RT 8 kT
v av = = =
πρ π M π m
√ 3 Average speed

(v) rms speed of gas molecules is γ Maxwell’s Law (or the Distribution of Molecular
times that of speed of sound in gas, as Speeds

v rms=
√ 3 RT
v=
M and s
γ RT
√ 3
v = v
M  rms γ s √ (1) The vrms gives us a general idea of
molecular speeds in a gas at a given

(vi) rms speed of gas molecules does not temperature. This doesn't mean that the

depends on the pressure of gas (if speed of each molecule is vrms. Many of the

temperature remains constant) because P molecules have speed less than vrms and

(Boyle’s law) if pressure is increased n times many have speeds greater than vrms.

then density will also increases by n times (2) Maxwell derived as equation given the
but vrms remains constant. distribution of molecules in different speed

(vii) Moon has no atmosphere because as follow

mv 2
vrms of gas molecules is more than escape
( )
3/2 −
m 2 2kT
dN =4 πN v e dv
velocity (ve). 2 π kT

A planet or satellite will have atmosphere wheredN = Number of molecules with

v rms <v e speeds between v and v + dv.
only if
(viii) At T = 0; vrms = 0 i.e. the rms speed dN
At a particular temperature
dv
of molecules of a gas is zero at 0 K. This
(Number of molecules at a particular speed)
temperature is called absolute zero.

v(m/s)
vmpvav vrms
Fig. 13.11
 λ 1 , λ2 , λ3 . . .. .
Let be the distance travelled by
a gas molecule during n
dN collisions respectively,
(3) Graph between dv (number of
then the mean free path
molecules at a particular speed) and v
of a gas molecule is
(speed of these molecules). From the graph
given by
dN
λ1 + λ2 + λ3 +. . ..+ λ n
it is seen that dv is maximum at most λ=
n Fig. 13.13
probable speed.
1
λ=
This graph also represent that
v rms >v av > v mp (2) √2 π nd 2

(Order remember trick RAM) whered = Diameter of the molecule,

√ √ √ √ √ √
3 RT 8 RT 2 RT RT RT RT n = Number of molecules per unit volume
> > 1.77 >1.6 > 1.41
 M πM M  M M M N P
= =n=
(3) As PV =  RT = NkT V kT
Area bonded by this curve with speed axis
Number of molecule per unit volume so
represents the number of molecules
1 kT
corresponds to that velocity range. This λ=
√2 πd 2 P .
curve is asymmetric curve.
1 m m
Effect of temperature on velocity λ= = =
(4) From √2 π nd √2 π (mn)d √ 2 πd 2 ρ
2 2

distribution :With temperature rise the

dN [As m = Mass each molecule, mn = Mass
vs v
dv . Curve shift towards right and per unit volume = Density = ]
becomes broader. (5) If average speed of molecule is v then
t
λ=v ×
N =v×T
dN T1
dv T2 [As N = Number of collision in time t, T =
T2>T1
time interval between two collisions].
1
v λ∝
Fig. 13.12
(i) As ρ and λ ∝ m i.e. the mean free
(Because with temperature rise average path is inversely proportional to the density
molecular speed increases). of a gas and directly proportional to the mass
Mean Free Path. of each molecule.

(1) The distance travelled by a gas

molecule between two successive collisions
is known as free path.
m
Total distance travelled by a gas molecule between successive collisions (A) (B)
λ=
Total number of collisions Fig. 13.14

During two successive collisions, a

molecule of a gas moves in a straight line
with constant velocity and
 1 kT independent motions and hence 3 degrees of
λ=
(ii) As √2 πd 2 P . For constant volume freedom (all translational)
and hence constant number density n of gas
P
molecules, T is constant so that  will not
(2) Diatomic gas :Molecules of diatomic
depend on P and T. But if volume of given
gas are made up of two atoms joined rigidly
mass of a gas is allowed to change with P or
to one another through a bond. This cannot
1
λ∝
P at only move bodily, but also rotate about one
T then T at constant pressure and
of the three co-ordinate axes. However its
constant temperature.
moment of inertia about the axis joining the
two atoms is negligible compared to that
about the other two axes.
P T Hence it can have only two rotational
(A) (B)
Fig. 13.15 motion. Thus a diatomic molecule has 5
degree of freedom : 3 translational and 2
Degree of Freedom rotational.
The term degree of freedom of a system (3) Triatomic gas (Non-linear) :A non-
y
refers to the possible independent motions, linear molecule can rotate
systems can have. or about any of three co-
x
The total number of independent modes ordinate axes. Hence it
(ways) in which a system can possess energy has 6 degrees of freedom z Fig. 13.18
is called the degree of freedom (f). : 3 translational and 3 rotational.

The independent motions can be

translational, rotational or vibrational or any Table 13.2 ; Degree of freedom for
combination of these. different gases
So the degree of freedom are of three
A
types : A B
Atomici Exam f= Figure
(i) Translational degree of freedom ty of ple 3
(ii) Rotational degree of freedom gas A–
(iii) Vibrational degree of freedom B
General expression for degree of freedom Monoat He, f=
1 0
f = 3A – B ; where A = Number of omic Ne, Ar 3
independent particles, Diatomi H2, B
f= A A
B = Number of independent restriction c O2,N2, 2 1
5
(1) Monoatomic gas :Molecule of Cl2etc.
y
monoatomic gas can move Triatomi H2O 3 3 f= A
vy
B B
in any direction in space so v vx c non 6
x A B A
it can have three vz
linear
z
Fig. 13.16
 3
RT
2 ; R = Universal
1 mole gas
Triatomi
CO2, f= A gas constant
A A
c linear 3 2 B B
BeCl2 7 3
 mole gas 2
μ RT

3
kT
2 ; k = Boltzmann’s
1 molecule
The above degrees of freedom are shown
constant
at room temperature. Further at high
3
N molecule NkT
temperature, in case of diatomic or 2

polyatomic molecules, the atoms with in the 3

rT
2 ; r = Specific gas
molecule may also vibrate with respect to 1 gm gas
each other. In such cases, the molecule will constant

have an additional degrees of freedom, due 3

mgm gas m rT
2
to vibrational motion.
An object which vibrates in one dimension
(1) Kinetic energy per molecule of gas
has two additional degree of freedom. One
does not depends upon the mass of the
for the potential energy and one for the
molecule but only depends upon the
kinetic energy of vibration.
3
A diatomic molecule that is free to vibrate E= kT
temperature of the gas. As 2 or E
(in addition to translation and rotation) will
T i.e. molecules of different gases say He, H2
have 7 (2+3+2) degrees of freedom. and O2etc. at same temperature will have
Kinetic Energy of Ideal Gas same translational kinetic energy though

In ideal gases, the molecules are their r.m.s. speed are different.

considered as point particles. For point (2) For two gases at the same temperature
particles, there is no internal excitation, no m1 ( v rms )12=m2 (v rms )22
vibration and no rotation. The point particles (3) Kinetic energy per mole of gas
can have only translational motion and thus depends only upon the temperature of gas.
only translational energy. For an ideal gas
(4) Kinetic energy per gram of gas
the internal energy can only be tranlational
depend upon the temperature as well as
kinetic energy.
molecular weight (or mass of one molecule)
Hence kinetic energy (or internal 3 k T
E gram= T E gram ∝
energy) of 1 mole ideal gas of the gas. 2m  m

1 1 3 RT 3 (5) From the above expressions it is clear

E= Mv 2rms= M × = RT
2 2 M 2
that higher the temperature of the gas, more
Table 13.3 : Various Translational will be the average kinetic energy possessed
kinetic energies by the gas molecules at T = 0, E = 0 i.e. at
absolute zero the molecular motion stops.

Quantity of gas Kinetic energy Law of Equipartition of Energy

 According to this law, for any system in (iv) Total energy associated with m gram
thermal equilibrium, the total energy is f
mrT
equally distributed among its various degree = 2

of freedom. And each degree of freedom is Specific Heat (CP and CV) of a Gas
1 The specific heat of gas can have many
kT
associated with energy 2 (where values, but out of them following two values
−23
k=1.38×10 J / K , T = absolute temperature of are very important
the system). (1) Specific heat at constant volume
(1) At a given temperature T, all ideal gas (CV) : The specific heat of a gas at constant
molecules no matter what their mass have volume is defined as the quantity of heat
the same average translational kinetic required to raise the temperature of unit
3 mass of gas through 1°C or 1 K when its
kT .
energy; namely, 2 When measure the ( ΔQ )V
cV =
volume is kept constant, i.e., mΔT
temperature of a gas, we are also measuring
the average translational kinetic energy of it' If instead of unit mass, 1 mole of gas is
s molecules. considered, the specific heat is called molar
(2) At same temperature gases with specific heat at constant volume and is
different degrees of freedom (e.g., He and represented by capital Cv.
H2) will have different average energy or
f
kT .
C V =Mc V =
M ( ΔQ )V 1 ( ΔQ )V
mΔT
=
μ ΔT [ As μ=
m
M ]
internal energy namely 2 (f is different for (2) Specific heat at constant from (CP)
different gases) : The specific heat of a gas at constant
(3) Different energies of a system of pressure is defined as the quantity of heat
degree of freedomf are as follows required to raise the temperature of unit
(i) Total energy associated with each mass of gas through 1 K when its pressure is
f ( ΔQ ) p
kT c P=
molecule = 2 kept constant, i.e., mΔT

(ii) Total energy associated with N If instead of unit mass, 1 mole of gas is
f considered, the specific heat is called molar
NkT
molecules = 2
specific heat at constant pressure and is
(iii) Total energy associated with  mole =
represented by Cp.
f
RT
2
(iv) Total energy associated with molen
C p =MC p =
M ( ΔQ) p 1 ( ΔQ ) p
mΔT
=
μ ΔT [ As μ=
m
M ]
f Mayer's Formula
μ RT
= 2
(1) Out of two principle specific heats of a
(v) Total energy associated with each gas, CP is more than CV because in case of CV,
f volume of gas is kept constant and heat is
rT
gram = 2 required only for raising the temperature of
one gram mole of the gas through 1°C or 1 K.
Hence no heat, what so ever, is spent in (3) Ratio of Cp and Cv ():
expansion of the gas.
γ=
Cp
=
f
2 ( )
+1 R
=1+
2
It means that heat supplied to the gas Cv f f
R
2
increases its internal energy only i.e.
( ΔQ )V = ΔU =μCV ΔT (i) Value of  is different for monoatomic,
…..(i)
diatomic and triatomic gases.
(2) While in case of CP the heat is used in 5 7 4
γ mono= =1 .6 , γ di= =1 . 4 , γ tri = =1. 33
two ways 3 5 3

(i) In increasing the temperature of the (ii) Value of  is always more than 1. So

gas by T we can say that always CP>CV .

(ii) In doing work, due to expansion at Gaseous Mixture

constant pressure (W) If two non-reactive gases are enclosed in

( ΔQ ) P=ΔU +ΔW =μ C P ΔT a vessel of volume V. In the mixture 1 moles

So …..(ii)
of one gas are mixed with 2 moles of
From equation (i) and (ii)
another gas. If NA is Avogadro’s number then
μ C P ΔT−μ C V ΔT= ΔW
N 1 =μ1 N A
Number of molecules of first gas
PΔV
C P−C V =
μ ΔT (C P −CV )=PΔV μ ΔT = R and number of molecules of second gas
 
N 2 =μ2 N A
[For constant pressure, W = PV also
from PV = RT, (1) Total mole fraction μ=( μ1 + μ2 ) .

PV = RT] M1
(2) If is the molecular weight of first
This relation is called Mayer’s formula and M2
gas and that of second gas.
C P >C V
shows that i.e. molar specific heat at Then molecular weight of mixture
constant pressure is greater than that at μ1 M 1 + μ2 M 2
M=
constant volume. μ 1 + μ2

Specific Heat in Terms of Degree of Freedom (3) Specific heat of the mixture at
(1) CV :For a gas at temperature T, the constant volume will be
f m1 m
U = μ RT C + 2C
internal energy 2  Change in energy M1 V 1 M 2 V 2
μ1 C V + μ2 C V = m1 m 2
1 2
f C V mix = +
ΔU = μRΔT μ1 + μ2 M1 M2
2 ... (i)
(4) Specific heat of the mixture at
Also, as we know for any gas heat
constant pressure will be
( ΔQ )V =μC V ΔT= ΔU
supplied at constant volume
( ) ( )
γ1 γ2
μ1 R+ μ2 R
... (ii) μ1 C P1 + μ 2 C P2 γ 1 −1 γ 2 −1
C P mix = =
μ1 + μ 2 μ 1 + μ2
1
C V = fR

[ ( ) ( )]
From equation (i) and (ii) 2 R γ1 γ2
= μ1 + μ2
μ1 + μ 2 γ 1−1 γ 2 −1
(2) CP : From the Mayer’s formula
C p −C v=R
=
R m1
[ ( ) ( )]
γ1
m1 m 2 M 1 γ 1 −1
+
m2 γ2
M 2 γ 2−1

( )
f +
f M1 M 2
C P=C V + R= R + R = +1 R
 2 2
 ( μ1 C P + μ2 C P ) from a planet if the temperature of planet
1 2
CP μ1 + μ2
Mv 2e
mix
γ mixture = =
CV ( μ 1 C V + μ2 C V ) T≤
mix 1 2
3 R ; where v = escape velocity from
(5) μ1 + μ2 e

the planet, R = universal, gas constant and

=
{( ) ( )}
μ1
γ1
γ 1 −1
R+ μ 2
γ2
γ 2 −1
R
M = Molecular mass of the gas.

{ ( ) ( )}
μ1 C P + μ 2 C P2 R R  As f (degree of freedom) increases then
= 1
μ1 + μ2
μ1 CV 1 + μ2 CV 2 γ 1−1 γ 2 −1
CP, CVand .
μ1 γ 1 μ2 γ 2
+  The number of molecules present in 1
γ 1 −1 γ 2 −1 μ1 γ 1 ( γ 2 −1)+ μ2 γ 2 ( γ 1−1 )
γ mixture = =
μ1 μ2 μ1 ( γ 2 −1)+ μ2 ( γ 1−1 ) gmmole of a gas is defined as Avogadro
+
γ 1 −1 γ 2 −1
 number (NA).

N A =6 . 023×1023 =6 . 023×1026 per

pergmmole
Tips & Tricks
kgmole.
 The cooking gas cylinder contains L.P.G.
At S.T.P. or N.T.P. (T = 273 K and P = 1
(Liquid Petroleum gas) which is saturated. 23
atm) 22.4 litre of each gas has 6 . 023×10
And as pressure
molecule
of saturated vapours is independent of
 One mole of any gas at S.T.P. occupy
volume
22.4 litre of volume
(at constant temperature). the pressure of
e.g. 32 gm oxygen, 28 gm nitrogen and
gas
2gm hydrogen occupy the same volume at
coming out of the cylinder remains constant
S.T.P.
till the cylinder becomes empty.
 For any gas 1 mole = Mgram = 22.4 litre
 If the number of molecules in a gas
= 6.023  1023 molecule.
increases, then the temperature, kinetic
energy and pressure of the gas increases
because Pn, Tn and kinetic energy Tn.
 vrms : vav : vmp =
√3:
√ 8
π
: √ 2= √ 3 : √ 2. 5 : √ 2

 For oxygen gas molecules vrms= 461 m/s,

 At constant volume if T increases then
v
vav= 424.7 m/s and vrms= 376.4 m/s
, vrms, P and collision frequency increases.
 An atom in a solid though has no degree
 If two gases are filled in vessel then of freedom for translational and rotational
nothing can be predicted about the motion, due to vibration along 3 axes has 3
pressure of gases. However their mean  2 = 6 degrees of freedom (and not like an
molecular energies will be same but their ideal gas molecule). When a diatomic or
rms velocities will be different. polyatomic gas dissociates into atoms it
 The average distance between two gas behaves as monoatomic gas whose degree
–9
molecules at NTP is 10 m. of freedom are changed accordingly
 The space available for a single gas  In General a polyatmic molecule has 3
molecule at NTP is 37.2  10–2m2. translational, 3 rotational degree of
 The molecules of gases will escape out freedom and a certain number of vibration
 4+ f vib
γ poly =
f vib 3+ f vib
mode . Hence .
 Only average translational kinetic
energy of a gas contributes to its
temperature. Two gases with the same
average translational kinetic energy have
the same temperature even if one has
grater rotational energy and thus greater
internal energy.
 Unsaturated vapours obey gas laws
while saturated vapours don’t.
 For real gases effective volume is

considered as (V – b) where

b=4 N A ( 43 πr ) ; r
3

= radius of each molecule and NA=

avogrado number.
 Variation of degree of freedom of a
diatomic gas (H2) with temperature. At very
low temperature only translation is possible.
as the temperature increases rotational
motion can begin. At still higher
temperatures
CV
vibratory motion can begin.
4R
7R/2
Vibration
5R/2
Rotation
3R/2
Translation

100 1000 10000 Temperature(K)