Kinetic Theory of Gases 81
Chapter
Kinetic Theory of Gases
Gas
In gases the intermolecular forces are very weak
and its molecule may fly apart in all directions. So the
gas is characterized by the following properties.
(i) It has no shape and size and can be obtained in
a vessel of any shape or size.
(ii) It expands indefinitely and uniformly to fill the
available space.
(iii) It exerts pressure on its surroundings.
(iv) Intermolecular forces in a gas are minimum.
(v) They can easily compressed and expand.
Assumption of Ideal Gases (or Kinetic Theory of
Gases)
Kinetic theory of gases relates the macroscopic
properties of gases (such as pressure, temperature etc.)
to the microscopic properties of the gas molecules (such
as speed, momentum, kinetic energy of molecule etc.)
Actually it attempts to develop a model of the
molecular behaviour which should result in the observed
behaviour of an ideal gas. It is based on following
assumptions :
13
(1) Every gas consists of extremely small particles
known as molecules. The molecules of a given gas are
all identical but are different than those of another gas.
(2) The molecules of a gas are identical, spherical,
rigid and perfectly elastic point masses.
(3) Their size is negligible in comparison to
intermolecular distance (10–9 m)
(4) The volume of molecules is negligible in
comparison to the volume of gas. (The volume of
molecules is only 0.014% of the volume of the gas).
(5) Molecules of a gas keep on moving randomly in
all possible direction with all possible velocities.
(6) The speed of gas molecules lie between zero
and infinity
(7) The gas molecules keep on colliding 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.
(9) The number of collisions per unit volume in a
gas remains constant.
(10) No attractive or repulsive force acts between
gas molecules.
(11) Gravitational attraction among the molecules is
ineffective due to extremely small masses and very high
speed of molecules.
(12) Molecules constantly collide with the walls of
container due to which their momentum changes. The
 82 Kinetic Theory of Gases
change in momentum is transferred to the walls of the
container. Consequently pressure is exerted by gas
molecules on the walls of container.
(13) The density of gas is constant at all points of (2) Charle's law : If the pressure remaining
the container. constant, the volume of the given mass of a gas is
directly proportional to its absolute temperature.
Gas Laws P
P
(1) Boyle’s law : For a given mass of an ideal gas
at constant temperature, the volume of a gas is Increase
volume
inversely proportional to its pressure.
P1 P2
T2 > T1
Increase Decrease V2
pressure T1 V1 volume

(A) (B)
Decrease
V1 Fig. 13.3
pressure V2
V V1 V2
i.e., V  T   constant 
(A) (B) T T1 T2
Fig. 13.1
V m m
1 (i)   constant(As volume V  )
i.e. V  or PV = constant  T T 
P
or T  constant  1T1   2T2
P1V1  P2V2
(ii) If the pressure remains constant, the volume of
 m P the given mass of a gas Vt
(i) PV = P 
    constant   constant
   increases or decreases by
P1 P2 1
of its volume at V0
or  273.15
1  2 0°C for each 1°C rise or fall
m in temperature. t(°C)
– 273.15 O
(As volume  and m =
 (Densityof thegas) Fig. 13.4
constant)
N P  1 
(ii) PV = P    constant  constant or Vt  V0  1  t .
n n  273.15 
 
P1 P2 This is Charle’s law for centigrade scale.

n1 n2 (v) Graphical representation: If m and P are constant
(iii) As number of molecules per unit volume
N
n
V
N V 1/V V
V  also N = constant
n
(iv) Graphical representation : If m and T are
constant V/T V/T
T T 1/T
PV PV
(A) (B) (C)

T or 1/T V or 1/V
P (D) (E)
P V Fig. 13.5
(B) (C) (3) Gay-Lussac’s law or pressure law : The
P V volume remaining constant, the pressure of a given
mass of a gas is directly proportional to its absolute
V
temperature.
(A)

1/V 1/P
(D) (E)
Fig. 13.2
 Kinetic Theory of Gases 83

P P1 P2 For n gases P  P1  P2  P3  .....Pn

P  T or  constant  
T T1 T2 where P = Pressure exerted by mixture and
(i) The volume remaining constant, the pressure of a P1 , P2 , P3 ,......Pn  Partial pressure of component
given mass of a gas Pt gases.
increases or decreases by
Equation of State or Ideal Gas Equation
1 P0
of its pressure at The equation which relates the pressure (P) volume
273.15
(V) and temperature (T) of the given state of an ideal
0°C for each 1°C rise or fall t(°C)
gas is known as ideal gas equation or equation of state.
in temperature. – 273.15 O
Fig. 13.5 PV
 1  For 1 mole of gas  R (constant)  PV = RT
Pt  P0 1  t T
 273.15 
where R = universal gas constant.
This is pressure law for centigrade scale.
Table 13.1 : Different forms of gas equation
(ii) Graphical representation : If m and V are
constants Quantity of Equation Constant
gas
P P/T P/T
1 mole gas PV = RT R = universal gas
constant
 mole gas PV = RT
1 molecule of
 R  k = Boltzmann's
T T or 1/T P or 1/P
gas PV    T constant
  kT
(A) (B) (C)  NA 
N molecules of PV = NkT
gas
1 gm of gas r = Specific gas
 R
PV    T constant
rT
1/P P M
m gm of gas PV = mrT

(4) Avogadro’s law : Equal volume of all the gases (1) Universal gas constant (R) : Universal gas
T temperature and pressure
under similar conditions of 1/T constant signifies the work done by (or on) a gas per
(D) (E)
Fig. 13.6 i.e. N1  N 2 .
mole per kelvin.
contain equal number of molecules
PV Pressure Volume
(5) Grahm’s law of diffusion : When two gases at R 
T   Temperature
the same pressure and temperature are allowed to
diffuse into each other, the rate of diffusion of each gas Workdone

is inversely proportional to the square root of the   Temperatu
re
1 1 (i) At S.T.P. the value of universal gas constant is
density of the gas i.e. r   (M is the same for all gases R =
 M
J cal
8.31  1.98
r1 2 M2 mole kelvin mole kelvin
molecular weight of the gas)   
r2 1 M1
~ cal
2
If V is the volume of gas diffused in t sec then mol kelvin
V r1 V1 t2
r    litre atm
t r2 V2 t1  0.8221 .
mole kelvin
(6) Dalton’s law of partial pressure : The total
(ii) Dimension : [ML2T 2 1]
pressure exerted by a mixture of non-reacting gases
occupying a vessel is equal to the sum of the individual
pressures which each gases exert if it alone occupied
the same volume at a given temperature.
 84 Kinetic Theory of Gases
(2) Boltzman's constant (k) : It is represented by

R 8.31
per mole gas constant i.e., k 
N 6.023 1023
 1.38 1023 J / K

It's dimension : [ML2T 2 1

]
(3) Specific gas constant (r) : It is represented by (6) A real gas behaves as ideal gas most closely at
low pressure and high temperature. Also can actual gas
R can be liquefied most easily which deviates most from
per gram gas constant i.e., r . It's unit is
M ideal gas behaviour at low temperature and high
pressure.
Joule
and dimension [L2T 2 1
] (7) Equation of state for real gases : It is given
gm kelvin by Vander Waal's with two correction in ideal gas
Since the value of M is different for different gases. equation. The it know as Vander Waal's gas equation.
Hence the value of r is different for different gases. e.g. (i) Volume correction : Due to finite size of
molecule, a certain portion of volume of a gas is
R covered by the molecules themselves. Therefore the
It is maximum for hydrogen rH 2 
2 space available for the free motion of molecules of gas
will be slightly less than the volume V of a gas. Hence
Real Gases the effective volume becomes (V – b).
(1) The gases actually found in nature are called (ii) Pressure correction : Due to intermolecular
real gases. force in real gases, molecule do not exert that force on
(2) They do not obeys gas Laws. the wall which they would have exerted in the absence
of intermolecular force. Therefore the observed
PV pressure P of the gas will be less than that present in
(3) For exactly one mole of an ideal gas  1.
RT the absence of intermolecular force. Hence the effective

PV  a 
Plotting the experimentally determined value of pressure becomes  P  .
RT  V2 
for exactly one mole of various real gases as a function (iii) Vander Waal's gas equations
of pressure P, shows a deviation from identity.
 a 
PV For 1 mole of gas  P   (V  b)  RT
(4) The quantity is called the compressibility  V2 
RT
factor and should be unit for an ideal gas.  a 2 
For  moles of gas  P   (V  b)   RT
 V 2 
2 CH4 Here a and b are constant called Vander Waal’s
N2
H2 constant.
1.5 Dimension : [a] = [ML5 T 2 ] and [b] = [L3]
PV CO2 Units : a = N  m4 and b = m3.
RT 1 (8) Andrews curves : The pressure (P) versus
Ideal
gas volume (V) curves for actual gases are called Andrews
0.5 curves.
D G
P Gas
380°C
0 200 400 600 800 100
H Liquid vapour
0
P (atm) region
374.1°C
Fig. 13.7
Liquid 370°C
(5) Deviation from ideal behaviour as a function of
F 360°C E
temperature
2 Vapour
200 K 500 K C 350°C B
A V
Andrews curve for
1.5 water
1000 K Fig. 13.9
PV
RT 1 Ideal gas

0.5

0 300 600 900 1200 P(atm)

Fig. 13.8
 Kinetic Theory of Gases 85
(i) At 350°C, part AB represents vapour phase of Y
Y
 1
water, in this part Boyle’s law is obeyed  P   . Part 
vx
 V vy v
BC represents the co-existence of vapour and liquid 
vx X
X vx
phases. At point C, vapours completely change to liquid vz
phase. Part CD is parallel to pressure axis which shows L Z
that compressibility of the water is negligible. Z
(A) (B)
(ii) At 360°C portion representing the co-existence Fig. 13.10
of liquid vapour phase is shorter. (1) Instantaneous velocity : Any molecule of gas

(iii) At 370°C this portion is further decreased. moves with velocity v in any direction
 ˆ  v  v2  v2  v2 . Due
(iv) At 374.1°C, it reduces to point (H) called critical where v  vxˆ i  vy ˆj  vz k x y z
point and the temperature 374.1°C is called critical
to random motion of molecule vx  vy  vz 
temperature (Tc) of water.
v2  3vx2  3vy2  3vz2
(v) The phase of water (at 380°C) above the critical
temperature is called gaseous phase. (2) Time during collision : Time between two
successive collision with the wall A1.
(9) Critical temperature, pressure and
volume : The point on the P-V curve at which the Distance
travelled
by molecule betweentwosuccess
matter gets converted from gaseous state to liquid state t 
Velocityof molecule
is known as critical point. At this point the difference
between the liquid and vapour vanishes i.e. the 2L

densities of liquid and vapour become equal. vx
(i) Critical temperature (Tc) : The maximum (3) Collision frequency (n) : It means the number
temperature below which a gas can be liquefied by 1 v
of collision per second. Hence n  x
pressure alone is called critical temperature and is t 2L
characteristic of the gas. A gas cannot be liquefied if its
(4) Change in momentum : This molecule collides
temperature is more than critical temperature. with the shaded wall (A1) with velocity vx and rebounds
CO2 (31.1°C), O2 (–118°C), N2 (–147.1°C) and H2O with velocity vx .
(374.1°C) The change in momentum of the molecule
(ii) Critical pressure (Pc) : The minimum pressure p  (mvx )  (mvx )  2mvx
necessary to liquify a gas at critical temperature is
As the momentum remains conserved in a
defined as critical pressure CO2 (73.87 bar) and O2
collision, the change in momentum of the wall A1 is
(49.7atm) p  2mvx
(iii) Critical volume (Vc) : The volume of 1 mole of
After rebound this molecule travel toward opposite
gas at critical pressure and critical temperature is
wall A2 with velocity vx , collide to it and again
defined as critical volume CO2 (95 10–6 m3)
rebound with velocity vx towards wall A1.
(iv) Relation between Vander Waal’s
constants and Tc, Pc, Vc (5) Force on wall : Force exerted by a single
molecule on shaded wall is equal to rate at which the
8a a momentum is transferred to the wall by this molecule.
Tc  , Pc  , Vc  3b ,
27Rb 27b2 p 2mvx mvx2
i.e. FSinglemolecule  
t (2L / vx ) L
27R 2 Tc2 R  Tc 
a , b   and
64 Pc 8  Pc  The total force on the wall A1 due to all the


m
molecules Fx  vx2 =
Pc Vc 3 L
 R
Tc 8 m 2 mN 2
(vx1  vx22  vx23  ...)  vx
M L
Pressure of an Ideal Gas
2
vx  mean square of x component of the velocity.
Consider an ideal gas (consisting of N molecules
each of mass m) enclosed in a cubical box of side L.
 86 Kinetic Theory of Gases
(6) Pressure : Now pressure is defined as force per The motion of molecules in a gas is characterised by
unit area, hence pressure on shaded wall any of the following three speeds.
Fx mN 2 mN 2 (1) Root mean square speed : It is defined as the
Px   vx  vx
A AL V square root of mean of squares of the speed of different
For any molecule, the mean square velocity molecules
v2  vx2  vy2  vz2 ; by symmetry vx2  vy2  vz2 
v12  v22  v32  v42  ....
v 2 i.e. vrms   v2
vx2  vy2
 vz2 N
3
Total pressure inside the container 1 2
(i) From the expression of pressure P   vrms
1 mN 2 1 m N 2 3
P v  vrms (where
3 V 3 V 3P 3PV 3RT 3kT
 vrms    
vrms  v2 )  Massof gas M m
(7) Relation between pressure and kinetic Massof gas
1 mN 2 1M 2 where   Densityof thegas, M
energy : As we know P  vrms  vrms  V

1 2
3 V 3 V
=   (mass of gas), pV  RT , R = kNA ,
P   vrms ... (i)
3 k  Boltzmann’s constant,
M M
[As M = mN = Total mass of the gas and   ] m= = mass of each molecule.
V NA
1 M  2 1 2 (ii) With rise in temperature rms speed of gas
 K.E. per unit volume E    vrms   vrms
2 V  2 molecules increases as vrms  T .
...(ii)
(iii) With increase in molecular weight rms speed of
2
From (i) and (ii), we get P  E 1
3 gas molecule decreases as vrms  . e.g., rms
M
i.e. the pressure exerted by an ideal gas is speed of hydrogen molecules is four times that of
numerically equal to the two third of the mean kinetic oxygen molecules at the same temperature.
energy of translation per unit volume of the gas.
(iv) rms speed of gas molecules is of the order of
(8) Effect of mass, volume and temperature on
km/s e.g., at NTP for hydrogen gas
1 mN 2 (m N)T
pressure : P  vrms or P 3RT 3  8.31 273
3 V V (vrms)    1840m / s .
2
[As vrms T] M 2 103

(i) If volume and temperature of a gas are constant 3

P  mN i.e. Pressure  (Mass of gas). (v) rms speed of gas molecules is times that of

i.e. if mass of gas is increased, number of molecules
and hence number of collision per second increases i.e. 3RT
speed of sound in gas, as vrms  and
pressure will increase. M
(ii) If mass and temperature of a gas are constant. P RT 3
vs   vrms  vs
 (1/V), i.e., if volume decreases, number of collisions M 
per second will increase due to lesser effective distance (vi) rms speed of gas molecules does not depends
between the walls resulting in greater pressure. on the pressure of gas (if temperature remains
(iii) If mass and volume of gas are constant, constant) because P   (Boyle’s law) if pressure is
P  (vrms)2  T increased n times then density will also increases by n
times but vrms remains constant.
i.e., if temperature increases, the mean square
(vii) Moon has no atmosphere because vrms of gas
speed of gas molecules will increase and as gas
molecules is more than escape velocity (ve).
molecules are moving faster, they will collide with the
walls more often with greater momentum resulting in A planet or satellite will have atmosphere only if
greater pressure. vrms  ve
Various Speeds of Gas Molecules
 Kinetic Theory of Gases 87
(viii) At T = 0; vrms = 0 i.e. the rms speed of
3RT 8RT 2RT
molecules of a gas is zero at 0 K. This temperature is    
M M M
called absolute zero.
RT RT RT
(2) Most probable speed : The particles of a gas 1.77  1.6  1.41
M M M
have a range of speeds. This is defined as the speed
which is possessed by maximum fraction of total Area bonded by this curve with speed axis
number of molecules of the gas. e.g., if speeds of 10 represents the number of molecules corresponds to that
molecules of a gas are 1, 2, 2, 3, 3, 3, 4, 5, 6, 6 km/s, velocity range. This curve is asymmetric curve.
then the most probable speed is 3 km/s, as maximum Effect of temperature on velocity distribution :
fraction of total molecules possess this speed. dN
With temperature rise the vsv . Curve shift
Most probable speed dv
2P 2RT 2kT towards right and becomes broader.
vmp   
 M m dN T1
dv T2
(3) Average speed : It is the arithmetic mean of
the speeds of molecules in a gas at given temperature. T2 > T1

v1  v2  v3  v4  .....
vav 
N v
Fig. 13.12
and according to kinetic theory of gases
(Because with temperature rise average molecular
8P 8 RT 8 kT speed increases).
Average speed vav   
  M  m
Mean Free Path.
Maxwell’s Law (or the Distribution of Molecular (1) The distance travelled by a gas molecule
Speeds between two successive collisions is known as free path.
(1) The vrms gives us a general idea of molecular Total distance
travelled
bya gasmolecule between suc
speeds in a gas at a given temperature. This doesn't 
Total numberof collisions
mean that the speed of each molecule is vrms. Many of
the molecules have speed less than vrms and many have During two successive collisions, a molecule of a
speeds greater than vrms. gas moves in a straight line with constant velocity and

(2) Maxwell derived as equation given the Let 1, 2, 3..... be the distance travelled by a
distribution of molecules in different speed as follow gas molecule during n
3/ 2 mv2 collisions respectively, then
 m  2

the mean free path of a gas
dN  4N   ve 2kT dv
 2kT  molecule is given by
where dN = Number of molecules with speeds 1   2   3  ....  n
between v and v + dv.

dN n
At a particular
dv 1
temperature
(Number of (2)  
molecules at a 2nd2
particular Fig. 13.13
where d = Diameter of
speed)
v(m/s) the molecule,
vmp vav vrms
n = Number of molecules per unit volume
Fig. 13.11
N P
dN (3) As PV =  RT =  NkT    n  Number
(3) Graph between (number of molecules at a V kT
dv
particular speed) and v (speed of these molecules). 1 kT
dN of molecule per unit volume so   2 .
From the graph it is seen that is maximum at 2 d P
dv
most probable speed.
This graph also represent that vrms  vav  vmp
(Order remember trick RAM)
 88 Kinetic Theory of Gases

1 m (i) Translational degree of freedom

(4) From  
2nd2 2 (mn)d 2 (ii) Rotational degree of freedom
(iii) Vibrational degree of freedom
m

General expression for degree of freedom
2d 2 
f = 3A – B ; where A = Number of independent
[As m = Mass each molecule, mn = Mass per unit
particles,
volume = Density = ]
B = Number of independent restriction
(5) If average speed of molecule is v then
(1) Monoatomic gas : Molecule of monoatomic gas
t
  v  v T can move in any direction in y
N space so it can have three vy
[As N = Number of collision in time t, T = time independent motions and hence v vx
interval between two collisions]. 3 degrees of freedom (all x
vz
1 translational)
(i) As   and   m i.e. the mean free path is z
 Fig. 13.16
inversely proportional to the density of a gas and
directly proportional to the mass of each molecule. (2) Diatomic gas : Molecules of diatomic gas are
made up of two atoms joined y
rigidly to one another through
a bond. This cannot only move
bodily, but also rotate about x
  one of the three co-ordinate
axes. However its moment of z
Fig. 13.17
inertia about the axis joining
1 kT the two atoms is negligible compared to that about the
(ii) As    . For constant volume mand other two axes.
(A)2 d 2 P (B)
Fig. 13.14 Hence it can have only two rotational motion. Thus
P a diatomic molecule has 5 degree of freedom : 3
hence constant number density n of gas molecules,
T translational and 2 rotational.
is constant so that  will not depend on P and T. But if (3) Triatomic gas (Non-linear) : A non-linear
volume of given mass of a gas is allowed to change with molecule can rotate about any y
1 of three co-ordinate axes.
P or T then   T at constant pressure and   at
P Hence it has 6 degrees of
constant temperature. freedom : 3 translational and 3 x
rotational.
z Fig. 13.18

 
Table 13.2 ; Degree of freedom for different
gases

Atomicity Example A B f=3 Figure

P T
Degree of Freedom of gas A–B
(A) (B) A
Monoatomi He, Ne,
The term degree of Fig. 13.15 of a system refers to
freedom 1 0 f=3
c Ar
the possible independent motions, systems can have.
H2, O2 ,
or A B
A Diatomic N2, Cl2 2 1 f=5
The total number of independent modes (ways) in etc.
which a system can possess energy is called theA degree
of freedom (f). B B Triatomic
H2O 3 3 f=6
non linear
The independent motions can be translational,
A B A
rotational or vibrational or any combination of these.
Triatomic CO2, 3 2 f=7
So the degree of freedom are of three typesA: linear BeCl2
A A
B B
 Kinetic Theory of Gases 89
say He, H2 and O2 etc. at same temperature will have
same translational kinetic energy though their r.m.s.
The above degrees of freedom are shown at room speed are different.
temperature. Further at high temperature, in case of
diatomic or polyatomic molecules, the atoms with in the (2) For two gases at the same temperature
molecule may also vibrate with respect to each other. In m1(vrms)12  m2(vrms)2
2
such cases, the molecule will have an additional
degrees of freedom, due to vibrational motion. (3) Kinetic energy per mole of gas depends only
An object which vibrates in one dimension has two upon the temperature of gas.
additional degree of freedom. One for the potential (4) Kinetic energy per gram of gas depend upon the
energy and one for the kinetic energy of vibration. temperature as well as molecular weight (or mass of
A diatomic molecule that is free to vibrate (in 3 k
addition to translation and rotation) will have one molecule) of the gas. E gram  T 
2m
7 (2  3  2) degrees of freedom.
T
E gram 
Kinetic Energy of Ideal Gas m
In ideal gases, the molecules are considered as (5) From the above expressions it is clear that
point particles. For point particles, there is no internal higher the temperature of the gas, more will be the
excitation, no vibration and no rotation. The point average kinetic energy possessed by the gas molecules
particles can have only translational motion and thus at T = 0, E = 0 i.e. at absolute zero the molecular
only translational energy. For an ideal gas the internal motion stops.
energy can only be tranlational kinetic energy. Law of Equipartition of Energy
Hence kinetic energy (or internal energy) of 1
According to this law, for any system in thermal
mole ideal gas
equilibrium, the total energy is equally distributed
1 2 1 3RT 3 among its various degree of freedom. And each degree
E Mvrms  M  RT 1
2 2 M 2 of freedom is associated with energy kT (where
2
Table 13.3 : Various Translational kinetic
k  1.38 1023 J / K , T = absolute temperature of
energies
the system).
Quantity of gas Kinetic energy (1) At a given temperature T, all ideal gas molecules
3 no matter what their mass have the same average
1 mole gas
RT ; R = Universal gas
2 3
constant translational kinetic energy; namely, kT. When
2
3 measure the temperature of a gas, we are also
 mole gas RT
2 measuring the average translational kinetic energy of it'
3 s molecules.
1 molecule
k T ; k = Boltzmann’s
2 (2) At same temperature gases with different
constant degrees of freedom (e.g., He and H2) will have different
3
N molecule N kT f
2 average energy or internal energy namely kT. (f is
2
3 different for different gases)
1 gm gas
rT ; r = Specific gas
2
(3) Different energies of a system of degree of
constant
freedom f are as follows
3
m gm gas mrT (i) Total energy associated with each molecule =
2
f
kT
(1) Kinetic energy per molecule of gas does not 2
depends upon the mass of the molecule but only (ii) Total energy associated with N molecules =
depends upon the temperature of the gas. As
f
NkT
3 2
E  kT or E  T i.e. molecules of different gases
2
 90 Kinetic Theory of Gases

f or 1 K. Hence no heat, what so ever, is spent in

(iii) Total energy associated with  mole = RT expansion of the gas.
2
(iv) Total energy associated with  molen = It means that heat supplied to the gas increases its
internal energy only i.e. (Q)V  U  C V T
f
RT …..(i)
2
(2) While in case of CP the heat is used in two ways
f
(v) Total energy associated with each gram = rT (i) In increasing the temperature of the gas by T
2
(ii) In doing work, due to expansion at constant
f pressure (W)
(iv) Total energy associated with m gram = mrT
2 So (Q)P  U  W   C P T
Specific Heat (CP and CV) of a Gas …..(ii)
The specific heat of gas can have many values, but From equation (i) and (ii)
out of them following two values are very important  CP T   CV T  W
(1) Specific heat at constant volume (CV) : The   T(CP  CV )  PV 
specific heat of a gas at constant volume is defined as PV
the quantity of heat required to raise the temperature of C P  CV  =R
 T
unit mass of gas through 1°C or 1 K when its volume is
[For constant pressure, W = PV also from PV =
(Q)V RT,
kept constant, i.e., cV 
mT PV = RT]

If instead of unit mass, 1 mole of gas is considered, This relation is called Mayer’s formula and shows
the specific heat is called molar specific heat at that C P  C V i.e. molar specific heat at constant
constant volume and is represented by capital Cv. pressure is greater than that at constant volume.
M (Q)V 1 (Q)V Specific Heat in Terms of Degree of Freedom
CV  McV  
mT  T (1) CV : For a gas at temperature T, the internal
f
 m energy U RT  Change in energy
 As   M  2
 
f
U  RT ... (i)
(2) Specific heat at constant from (CP) : The 2
specific heat of a gas at constant pressure is defined as Also, as we know for any gas heat supplied at
the quantity of heat required to raise the temperature of constant volume (Q)V  CV T  U
unit mass of gas through 1 K when its pressure is kept ... (ii)
(Q)p 1
constant, i.e., cP  From equation (i) and (ii) CV  fR
mT 2
(2) CP : From the Mayer’s formula C p  Cv  R
If instead of unit mass, 1 mole of gas is considered,
the specific heat is called molar specific heat at f  f 
 CP  CV  R  R  R    1 R
constant pressure and is represented by Cp. 2  2 
M (Q)p 1 (Q)p (3) Ratio of Cp and Cv ( ) :
C p  MC p  
mT  T f 
  1 R
C 2  2
 m   P   1
 As   M  CV f f
  R
2
Mayer's Formula (i) Value of  is different for monoatomic, diatomic
and triatomic gases.
(1) Out of two principle specific heats of a gas, CP is
5 7 4
more than CV because in case of CV, volume of gas is  mono   1.6,  di   1.4,  tri   1.33
kept constant and heat is required only for raising the 3 5 3
temperature of one gram mole of the gas through 1°C (ii) Value of  is always more than 1. So we can say
that always CP > CV .
 Kinetic Theory of Gases 91

Gaseous Mixture 1CP1   2CP2


If two non-reactive gases are enclosed in a vessel of 1CV1   2CV2
volume V. In the mixture 1 moles of one gas are mixed
   1     
with 2 moles of another gas. If NA is Avogadro’s number
1  R   2 2  R
then    1  1     1 
 2  

Number of molecules of first gas N1   1 N A   R   R 
1    2 
   1 
   1  1 
and number of molecules of second gas
N2   2N A  2 

(1) Total mole fraction   ( 1   2 ) .
1 1 
(2) If M 1 is the molecular weight of first gas and  2 2
  1  2  1 1 1( 2  1)   2 2( 1  1)
M 2 that of second gas.  mixture 1 
1 2 1( 2  1)   2( 1  1)
Then molecular weight of mixture 
1  1  2  1
1M1   2M 2
M
1   2
(3) Specific heat of the mixture at constant volume
will be
m1 m
CV1  2 CV2
1CV1   2CV2 M M2
CVmix   1  The cooking gas cylinder contains L.P.G. (Liquid
1   2 m1 m2 Petroleum gas) which is saturated. And as pressure

M1 M 2 of saturated vapours is independent of volume
(4) Specific heat of the mixture at constant pressure
(at constant temperature). the pressure of gas
will be
1CP1   2CP2 coming out of the cylinder remains constant
CPmix  till the cylinder becomes empty.
1   2
 If the number of molecules in a gas increases,
     
1 1  R   2 2  R then the temperature, kinetic energy and pressure of
  1   2  1 the gas increases because P  n, T  n and kinetic
  1 energy  T  n.
1   2
 At constant volume if T increases then v , vrms, P
R   1    
  1    2 2   and collision frequency increases.
1   2    1  1     1
 2    If two gases are filled in vessel then nothing can
be predicted about the pressure of gases. However
R  m1   1  m2   2 
      their mean molecular energies will be same but their
m1 m2  M1   1  1  M 2   2  1  rms velocities will be different.
  
M1 M 2  The average distance between two gas molecules
at NTP is 10–9 m.
(1CP1   2CP2 )
 The space available for a single gas molecule at
CPmix 1   2 NTP is 37.2  10–2 m2.
(5)  mixture 
CVmix (1CV1   2CV2 )  The molecules of gases will escape out from a
1   2 Mve2
planet if the temperature of planet T ; where
3R
ve = escape velocity from the planet, R = universal,
gas constant and M = Molecular mass of the gas.
 As f (degree of freedom) increases then CP, CV
and  .
 92 Kinetic Theory of Gases

 The number of molecules present in 1 gm mole of

a gas is defined as Avogadro number (NA).

N A  6.023 1023 per gm mole

 6.023 1026 per kg mole.

At S.T.P. or N.T.P. (T = 273 K and P = 1 atm) 22.4 litre
of each gas has 6.023 1023 molecule

 One mole of any gas at S.T.P. occupy 22.4 litre of

volume
e.g. 32 gm oxygen, 28 gm nitrogen and 2gm
hydrogen occupy the same volume at S.T.P.
Gas Laws
 For any gas 1 mole = M gram = 22.4 litre = 6.023
1. The temperature of a gas at pressure P and
 1023 molecule.
volume V is 27°C. Keeping its volume constant if
8 its temperature is raised to 927°C, then its
 vrms : vav : vmp = 3: : 2 3 : 2.5 : 2
pressure will be [MP PMT 1985]

(a) 2 P (b) 3 P
 For oxygen gas molecules vrms = 461 m/s, vav =
(c) 4 P (d) 6 P
424.7 m/s and vrms = 376.4 m/s
2. 4 moles of an ideal gas is at 0°C. At constant
 An atom in a solid though has no degree of pressure it is heated to double its volume, then its
freedom for translational and rotational motion, due final temperature will be
[MP PET 1990]
to vibration along 3 axes has 3  2 = 6 degrees of
(a) 0°C (b) 273°C
freedom (and not like an ideal gas molecule). When a
(c) 546°C (d) 136.5°C
diatomic or polyatomic gas dissociates into atoms it
3. Every gas (real gas) behaves as an ideal gas
behaves as monoatomic gas whose degree of
[CPMT 1997; RPMT 2000; MP PET 2001]
freedom are changed accordingly
(a) At high temperature and low pressure
 In General a polyatmic molecule has 3 (b) At low temperature and high pressure
translational, 3 rotational degree of freedom and a (c) At normal temperature and pressure
certain number of vibration mode fvib . Hence (d) None of the above
4. Boyle's law holds for an ideal gas during
4  fvib [AFMC 1994; KCET 1999]
 poly  . (a) Isobaric changes (b) Isothermal changes
3  fvib
(c) Isochoric changes (d) Isotonic changes
 Only average translational kinetic energy of a gas 5. S.I. unit of universal gas constant is
contributes to its temperature. Two gases with the [MNR 1988; MP PMT 1994; UPSEAT 1999]
same average translational kinetic energy have the (a) cal/°C (b) J/mol
same temperature even if one has grater rotational (c) J mol1 K 1 (d) J/kg
energy and thus greater internal energy. 6. Molecules of a gas behave like
[J & K CET 2000]
 Unsaturated vapours obey gas laws while
(a) Inelastic rigid sphere
saturated vapours don’t.
(b) Perfectly elastic non-rigid sphere
 For real gases effective volume is considered as (c) Perfectly elastic rigid sphere
 4 3 (d) Inelastic non-rigid sphere
(V – b) where b  4 N A  r  ; r = radius of each
3 
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
Translatio
n
100 1000 1000 Temperature(K
0 )