K.T.

G
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 :
(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.

1
 K.T.G
(12) Molecules constantly collide with the walls of container due to which their momentum
changes. The 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 the container.
Gas Laws
(1) Boyle’s law : For a given mass of an ideal gas at constant temperature, the volume of a
gas is inversely proportional to its pressure.
P1 P2
Increase
pressure

Decrease
V1 pressure V2

(A) (B)
1
i.e. V or PV = constant  P1 V1  P2 V2
P
m  P P1 P2
(i) PV = P    constant   constant or 
  1 2
m
(As volume  and m = constant)
 (Density of the gas)

(ii) PV = P    constant   constant or 1  2

N P P P
n n n1 n2
N
(iii) As number of molecules per unit volume n 
V
N
V  also N = constant
n
(iv) Graphical representation : If m and T are constant
P PV P V
PV

1/V 1/P
V P V
(D) (E)
(A) (B) (C)

(2) Charle's law : If the pressure remaining constant, the volume of the given mass of a gas
is directly proportional to its absolute temperature.
P
P
Increase
volume

T2 > T1
Decrease
T1 V2
V1 volume

(A) (B)

2
 K.T.G

V V1 V2
i.e., V  T   constant  
T T1 T2
V m m
(i)   constant (As volume V  )
T T 
or T  constant  1 T1   2 T2
(ii) If the pressure remains constant, the volume of the given mass of a Vt
1
gas increases or decreases by of its volume at 0°C for each 1°C rise
273 .15
V0
or fall in temperature.
 1 
Vt  V0  1  t . t(°C)
 273 . 15  – 273.15 O

This is Charle’s law for centigrade scale. Fig. 13.4

(v) Graphical representation: If m and P are constant

V 1/V V V/T V/T

T T 1/T T or 1/T V or 1/V

(A) (B) (C) (D) (E)

(3) Gay-Lussac’s law or pressure law : The volume remaining constant, the pressure of
a given mass of a gas is directly proportional to its absolute temperature.
P P1 P
P  T or  constant   2
T T1 T2

(i) The volume remaining constant, the pressure of a given mass of a gas increases or decreases
1
by of its pressure at 0°C for each 1°C rise or fall in temperature. Pt
273 .15
 1 
Pt  P0 1  t P0
 273 . 15 
t(°C)
This is pressure law for centigrade scale.
– 273.15 O
(ii) Graphical representation : If m and V are constants Fig. 13.5
P P/T P/T 1/P P

T 1/T
T T or 1/T P or 1/P
(D) (E)
(A) (B) (C)

3
 K.T.G

(4) Avogadro’s law : Equal volume of all the gases under similar conditions of temperature
and pressure contain equal number of molecules i.e. N 1  N 2 .
(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 inversely proportional to the
1 1
square root of the density of the gas i.e. r   (M is the molecular weight of the gas) 
 M

r1 2 M2
 
r2 1 M1

If V is the volume of gas diffused in t sec then

V r1 V1 t2
r   
t r2 V2 t1
(6) Dalton’s law of partial pressure : The total 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.
For n gases P  P1  P2  P3  ..... Pn
where P = Pressure exerted by mixture and P1 , P2 , P3 , ...... Pn  Partial pressure of component
gases.
Equation of State or Ideal Gas Equation
The equation which relates the pressure (P) volume (V) and temperature (T) of the given state
of an ideal gas is known as ideal gas equation or equation of state.
PV
For 1 mole of gas R (constant)  PV = RT
T
where R = universal gas constant.
Table 13.1 : Different forms of gas equation
Quantity of gas Equation Constant

1 mole gas PV = RT R = universal gas constant

 mole gas PV = RT

1 molecule of gas  R  k = Boltzmann's constant
PV    T  kT

 NA 

N molecules of gas PV = NkT

1 gm of gas  R
PV    T  rT
r = Specific gas constant
M

m gm of gas PV = mrT

4
 K.T.G

(1) Universal gas constant (R) : Universal gas constant signifies the work done by (or on)
a gas per mole per kelvin.
PV Pressure  Volume Work done
R  
T   Temperatu re   Temperatu re
(i) At S.T.P. the value of universal gas constant is same for all gases R =
J cal ~ 2 cal
8 .31  1 .98
mole  kelvin mole  kelvin mol  kelvin
litre atm
 0 .8221 .
mole  kelvin
(ii) Dimension : [ML2T 2 1 ]
(2) Boltzman's constant (k) : It is represented by per mole gas constant i.e.,
R 8 .31
k   1 .38  10 23 J / K
N 6 .023  10 23

It's dimension : [ML2 T 2 1 ]

R
(3) Specific gas constant (r) : It is represented by per gram gas constant i.e., r  . It's
M
Joule
unit is and dimension [L2 T 2 1 ]
gm  kelvin

Since the value of M is different for different gases. Hence the value of r is different for
R
different gases. e.g. It is maximum for hydrogen rH 2 
2
Real Gases
(1) The gases actually found in nature are called real gases.
(2) They do not obeys gas Laws.
PV
(3) For exactly one mole of an ideal gas  1. Plotting the experimentally determined value
RT
PV
of for exactly one mole of various real gases as a function of pressure P, shows a deviation
RT
from identity.
PV
(4) The quantity is called the compressibility factor and should be unit for an ideal gas.
RT

2 CH4
N2
H2
1.5

PV CO2
RT 1
Ideal gas

0.5

0 200 400 600 800 1000

Fig. 13.7
P (atm)
5
 K.T.G

(5) Deviation from ideal behaviour as a function of temperature

2 200 K 500 K

1.5
1000 K
PV
RT 1 Ideal gas

0.5

0 300 600 900 1200 P(atm)

Fig. 13.8

(6) A real gas behaves as ideal gas most closely at low pressure and high temperature. Also
can actual gas can be liquefied most easily which deviates most from ideal gas behaviour at low
temperature and high pressure.
(7) Equation of state for real gases : It is given by Vander Waal's with two correction in
ideal gas equation. The it know as Vander Waal's gas equation.
(i) Volume correction : Due to finite size of molecule, a certain portion of volume of a gas
is covered by the molecules themselves. Therefore the space available for the free motion of
molecules of gas will be slightly less than the volume V of a gas. Hence the effective volume
becomes (V – b).
(ii) Pressure correction : Due to intermolecular force in real gases, molecule do not exert
that force on the wall which they would have exerted in the absence of intermolecular force.
Therefore the observed pressure P of the gas will be less than that present in the absence of
intermolecular force. Hence the effective pressure becomes  P  2  .
a
 V 
(iii) Vander Waal's gas equations
For 1 mole of gas  P  2  (V  b)  RT
a
 V 

a 2 
For  moles of gas  P  2  (V  b)   RT
 V 
Here a and b are constant called Vander Waal’s constant.
Dimension : [a] = [ML5 T 2 ] and [b] = [L3]
Units : a = N  m4 and b = m3.
(9) Critical temperature, pressure and volume : The point on the P-V curve at which
the matter gets converted from gaseous state to liquid state is known as critical point. At this point
the difference between the liquid and vapour vanishes i.e. the densities of liquid and vapour
become equal.

6
 K.T.G
(i) Critical temperature (Tc) : The maximum temperature below which a gas can be
liquefied by pressure alone is called critical temperature and is characteristic of the gas. A gas
cannot be liquefied if its temperature is more than critical temperature.
CO2 (31.1°C), O2 (–118°C), N2 (–147.1°C) and H2O (374.1°C)
(ii) Critical pressure (Pc) : The minimum pressure necessary to liquify a gas at critical
temperature is defined as critical pressure CO2 (73.87 bar) and O2 (49.7atm)
(iii) Critical volume (Vc) : The volume of 1 mole of gas at critical pressure and critical
temperature is defined as critical volume CO2 (95 10–6 m3)
(iv) Relation between Vander Waal’s constants and Tc, Pc, Vc
8a a
Tc  , Pc  , Vc  3b ,
27 Rb 27 b 2

27 R 2 Tc2 R  Tc  Pc Vc 3
a , b   and  R
64 Pc 8  Pc 
 Tc 8

Pressure of an Ideal Gas

Consider an ideal gas (consisting of N molecules each of mass m) enclosed in a cubical box of
side L.
Y
Y

v vy
x
v
 X
v vx
x
X vz

L Z
Z
(A) (B)
Fig. 13.10


(1) Instantaneous velocity : Any molecule of gas moves with velocity v in any direction

where v  v x ˆi  v y ˆj  v z kˆ  v  v x2  v y2  v z2 . Due to random motion of molecule v x  vy  vz 
v 2  3v x2  3vy2  3vz2
(2) Time during collision : Time between two successive collision with the wall A1.
Distance travelled by molecule between two successive collision
t 
Velocity of molecule
2L

vx
(3) Collision frequency (n) : It means the number of collision per second. Hence
1 v
n  x
t 2 L
(4) Change in momentum : This molecule collides with the shaded wall (A1) with velocity
vx and rebounds with velocity v x .
The change in momentum of the molecule
p  (mv x )  (mv x )  2mv x

7
 K.T.G
As the momentum remains conserved in a collision, the change in momentum of the wall
A1 is p  2mv x
After rebound this molecule travel toward opposite wall A2 with velocity v x , collide to it and
again rebound with velocity v x towards wall A1.
(5) Force on wall : Force exerted by a single molecule on shaded wall is equal to rate at
which the momentum is transferred to the wall by this molecule.
p 2mv x mv x2
i.e. FSingle molecule   
t (2 L / v x ) L

v
m m 2 mN 2
The total force on the wall A1 due to all the molecules Fx  2
x = (v x  v x22  v x23  ...)  vx
L M 1 L
v x2  mean square of x component of the velocity.
(6) Pressure : Now pressure is defined as force per unit area, hence pressure on shaded wall
Fx mN 2 mN 2
Px   vx  vx
A AL V
For any molecule, the mean square velocity v 2  v x2  vy2  vz2 ; by symmetry v x2  v y2  v z2 
v2
v x2  v y2  v z2 
3
Total pressure inside the container
1 mN 2 1 m N 2
P v  vrms (where vrms  v 2 )
3 V 3 V
1 mN 2 1 M 2
(7) Relation between pressure and kinetic energy : As we know P  v rms  v rms
3 V 3 V
1
 P  v rms
2
... (i)
3
M
[As M = mN = Total mass of the gas and   ]
V

 K.E. per unit volume E    vrms

1 M 2 1
  vrms
2
...(ii)
2V  2
2
From (i) and (ii), we get P  E
3
i.e. the pressure exerted by an ideal gas is numerically equal to the two third of the mean
kinetic energy of translation per unit volume of the gas.
1 mN 2
(8) Effect of mass, volume and temperature on pressure : P vr m s or
3 V
(m N )T
P [As v rms
2
T]
V
(i) If volume and temperature of a gas are constant P  mN i.e. Pressure  (Mass of gas).
i.e. if mass of gas is increased, number of molecules and hence number of collision per second
increases i.e. pressure will increase.
(ii) If mass and temperature of a gas are constant. P  (1/V), i.e., if volume decreases, number
of collisions per second will increase due to lesser effective distance between the walls resulting
in greater pressure.
(iii) If mass and volume of gas are constant, P  (v rms ) 2  T

8
 K.T.G
i.e., if temperature increases, the mean square speed of gas molecules will increase and as gas
molecules are moving faster, they will collide with the walls more often with greater momentum
resulting in greater pressure.
Various Speeds of Gas Molecules
The motion of molecules in a gas is characterised by any of the following three speeds.
(1) Root mean square speed : It is defined as the square root of mean of squares of the
speed of different molecules
v12  v 22  v32  v 42  ....
i.e. vrms   v2
N
1
(i) From the expression of pressure P   v rms
2
3
3P 3 PV 3 RT 3 kT
 vrms    
 Mass of gas M m
Mass of gas
where    Density of the gas , M =   (mass of gas), pV  RT , R = kN A , k Boltzmann’s
V
constant,
M
m= = mass of each molecule.
NA

(ii) With rise in temperature rms speed of gas molecules increases as v rms  T .
1
(iii) With increase in molecular weight rms speed of gas molecule decreases as v rms  . e.g.,
M
rms speed of hydrogen molecules is four times that of oxygen molecules at the same temperature.
(iv) rms speed of gas molecules is of the order of km/s e.g., at NTP for hydrogen gas
3 RT 3  8 . 31  273
(vrms )    1840 m / s .
M 2  10 3

3 3 RT
(v) rms speed of gas molecules is times that of speed of sound in gas, as v rms  and
 M

RT 3
vs   v rms  vs
M 
(vi) rms speed of gas molecules does not depends on the pressure of gas (if temperature
remains constant) because P   (Boyle’s law) if pressure is increased n times then density will
also increases by n times but vrms remains constant.
(vii) Moon has no atmosphere because vrms of gas molecules is more than escape velocity (ve).
A planet or satellite will have atmosphere only if vrms  ve
(viii) At T = 0; vrms = 0 i.e. the rms speed of molecules of a gas is zero at 0 K. This temperature
is called absolute zero.
(2) Most probable speed : The particles of a gas have a range of speeds. This is defined as
the speed which is possessed by maximum fraction of total number of molecules of the gas. e.g.,
if speeds of 10 molecules of a gas are 1, 2, 2, 3, 3, 3, 4, 5, 6, 6 km/s, then the most probable speed
is 3 km/s, as maximum fraction of total molecules possess this speed.

9
 K.T.G
2P 2 RT 2kT
Most probable speed vmp   
 M m

(3) Average speed : It is the arithmetic mean of the speeds of molecules in a gas at given
temperature.
v 1  v 2  v 3  v 4  .....
v av 
N
and according to kinetic theory of gases
8P 8 RT 8 kT
Average speed vav   
  M  m
Maxwell’s Law (or the Distribution of Molecular Speeds
(1) The vrms gives us a general idea of molecular speeds in a gas at a given temperature. This
doesn't mean that the speed of each molecule is vrms. Many of the molecules have speed less than
vrms and many have speeds greater than vrms.
(2) Maxwell derived as equation given the distribution of molecules in different speed as
follow
3/2 mv 2
 m  
dN  4N   2
v e 2 kT dv
 2kT 
where dN = Number of molecules with speeds between v and v + dv.

At a particular
temperature
(Number of
molecules at a
particular speed)

v(m/s)
vmp vav vrms
dNFig. 13.11
(3) Graph between (number of molecules at a particular speed) and v (speed of these
dv
dN
molecules). From the graph it is seen that is maximum at most probable speed.
dv
This graph also represent that vrms  vav  vmp
(Order remember trick RAM)
3 RT 8 RT 2 RT RT RT RT
    1 .77  1 .6  1 . 41
M M M M M M
Area bonded by this curve with speed axis represents the number of molecules corresponds to
that velocity range. This curve is asymmetric curve.
dN
Effect of temperature on velocity distribution : With temperature rise the vs v .
dv
Curve shift towards right and becomes broader.
T1
T2
T2 > T1

v
Fig. 13.12

10
 K.T.G
(Because with temperature rise average molecular speed increases).
Mean Free Path.
(1) The distance travelled by a gas molecule between two successive collisions is known as free
path.
Total distance travelled by a gas molecule between successivecollisions

Total number of collisions

During two successive collisions, a molecule of a gas moves in a straight line with constant
velocity and
Let 1, 2 , 3 ..... be the distance travelled by a gas molecule during n collisions respectively, then
the mean free path of a gas
molecule is given by
1   2   3  ....  n

n
1
(2)  
2nd 2
where d = Diameter of
the molecule,
Fig. 13.13
n = Number of
molecules per unit volume
N P 1 kT
(3) As PV =  RT =  NkT    n  Number of molecule per unit volume so  
2 d P
2
V kT
.
1 m m
(4) From    
2nd 2 2 (mn )d 2 2d 2 

[As m = Mass each molecule, mn = Mass per unit volume = Density = ]

t
(5) If average speed of molecule is v then   v   vT
N
[As N = Number of collision in time t, T = time interval between two collisions].
1
(i) As   and   m i.e. the mean free path is inversely proportional to the density of a gas

and directly proportional to the mass of each molecule.
 

 m
(A) (B)
Fig. 13.14
1 kT
(ii) As   . For constant volume and hence constant number density n of gas
2 d P
2

P
molecules, is constant so that  will not depend on P and T. But if volume of given mass of a
T

11
 K.T.G
1
gas is allowed to change with P or T then   T at constant pressure and   at constant
P
temperature.
 

P T
(A) (B)
Fig. 13.15

Degree of Freedom
The term degree of freedom of a system refers to the possible independent motions, systems
can have. or
The total number of independent modes (ways) in which a system can possess energy is called
the degree of freedom (f).
The independent motions can be translational, rotational or vibrational or any combination
of these.
So the degree of freedom are of three types :
(i) Translational degree of freedom
(ii) Rotational degree of freedom
(iii) Vibrational degree of freedom
General expression for degree of freedom
f = 3A – B ; where A = Number of independent particles,
B = Number of independent restriction
(1) Monoatomic gas : Molecule of monoatomic gas can move in any direction in space so it
can have three independent y

motions and hence 3 degrees of v y

v
freedom (all translational) vx
x
vz
z
Fig. 13.16

(2) Diatomic gas : Molecules of diatomic gas are made up of two atoms joined rigidly to one
another through a bond. This y

cannot only move bodily, but

also rotate about one of the
x
three co-ordinate axes.
However its moment of z
Fig. 13.17
inertia about the axis joining
the two atoms is negligible compared to that about the other two axes.
Hence it can have only two rotational motion. Thus a diatomic molecule has 5 degree of
freedom : 3 translational and 2 rotational.

12
 K.T.G
(3) Triatomic gas (Non-linear) : A non-linear molecule can rotate about any of three co-
ordinate axes. Hence it has 6 y
degrees of freedom : 3
translational and 3 rotational.
x

z Fig. 13.18

Table; Degree of freedom for different gases

Atomicity Exampl TRANS;ATIONAL ROTATIONAL DEGREE OF Figure

of gas e A FREEDOM

He, Ne,
Monoatomic 3 0 f=3
Ar
H2, O2,
Diatomic N2, Cl2 3 2 f=5 A B A
etc.
A
Triatomic
H2O 3 3 f=6 B B
non linear
A B A

Triatomic CO2, A
3 2 f=5 A A
linear BeCl2 B B

The above degrees of freedom are shown at room temperature. Further at high temperature,
in case of diatomic or polyatomic molecules, the atoms with in the molecule may also vibrate with
respect to each other. In such cases, the molecule will have an additional degrees of freedom, due
to vibrational motion.
An object which vibrates in one dimension has two additional degree of freedom. One for the
potential energy and one for the kinetic energy of vibration.
A diatomic molecule that is free to vibrate (in addition to translation and rotation) will have
7 (2  3  2) degrees of freedom.

Kinetic Energy of Ideal Gas

In ideal gases, the molecules are considered as point particles. For point particles, there is
no internal excitation, no vibration and no rotation. The point particles can have only translational
motion and thus only translational energy. For an ideal gas the internal energy can only be
tranlational kinetic energy.
Hence kinetic energy (or internal energy) of 1 mole ideal gas
1 1 3 RT 3
E 2
Mvrms  M  RT
2 2 M 2

13
 K.T.G
Table: Various Translational kinetic energies

Quantity of gas Kinetic energy

3
1 mole gas RT ; R = Universal gas constant
2

3
 mole gas 2
RT

3
1 molecule kT ; k = Boltzmann’s constant
2

3
N molecule 2
NkT

3
1 gm gas rT ; r = Specific gas constant
2

3
m gm gas 2
m rT

(1) Kinetic energy per molecule of gas does not depends upon the mass of the molecule but
3
only depends upon the temperature of the gas. As E  k T or E  T i.e. molecules of different
2
gases say He, H2 and O2 etc. at same temperature will have same translational kinetic energy
though their r.m.s. speed are different.
(2) For two gases at the same temperature m1 (vrms )12  m 2 (vrms )22

(3) Kinetic energy per mole of gas depends only upon the temperature of gas.
(4) Kinetic energy per gram of gas depend upon the temperature as well as molecular weight
3 k T
(or mass of one molecule) of the gas. E gram  T  E gram 
2m m
(5) From the above expressions it is clear that higher the temperature of the gas, more will be
the average kinetic energy possessed by the gas molecules at T = 0, E = 0 i.e. at absolute zero the
molecular motion stops.
Law of Equipartition of Energy
According to this law, for any system in thermal equilibrium, the total energy is equally
distributed among its various degree of freedom. And each degree of freedom is associated with
1
energy kT (where k  1 . 38  10 23 J / K , T = absolute temperature of the system).
2
(1) At a given temperature T, all ideal gas molecules no matter what their mass have the same
3
average translational kinetic energy; namely, k T. When measure the temperature of a gas, we
2
are also measuring the average translational kinetic energy of it' s molecules.
(2) At same temperature gases with different degrees of freedom (e.g., He and H2) will have
f
different average energy or internal energy namely k T. (f is different for different gases)
2

14
 K.T.G
(3) Different energies of a system of degree of freedom f are as follows
f
(i) Total energy associated with each molecule = kT
2
f
(ii) Total energy associated with N molecules = Nk T
2
f
(iii) Total energy associated with  mole = RT
2
f
(iv) Total energy associated with  molen = RT
2
f
(v) Total energy associated with each gram = rT
2
f
(iv) Total energy associated with m gram = mrT
2
Specific Heat (CP and CV) of a Gas
The specific heat of gas can have many values, but out of them following two values are very
important
(1) Specific heat at constant volume (CV) : The specific heat of a gas at constant volume
is defined as the quantity of heat required to raise the temperature of unit mass of gas through
(Q)V
1°C or 1 K when its volume is kept constant, i.e., cV 
m T
If instead of unit mass, 1 mole of gas is considered, the specific heat is called molar specific
heat at constant volume and is represented by capital Cv.
M (Q)V 1 (Q)V  m
CV  McV 
m T

 T  As   M 
 

(2) Specific heat at constant from (CP) : The specific heat of a gas at constant pressure is
defined as the quantity of heat required to raise the temperature of unit mass of gas through 1 K
(Q) p
when its pressure is kept constant, i.e., c P 
m T
If instead of unit mass, 1 mole of gas is considered, the specific heat is called molar specific
heat at constant pressure and is represented by Cp.
M (Q ) p 1 (Q ) p  m
C p  MC p 
m T

 T  As   M 
 
Mayer's Formula
(1) Out of two principle specific heats of a gas, CP is more than CV because in case of CV, volume
of gas is kept constant and heat is 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 expansion of the gas.
It means that heat supplied to the gas increases its internal energy only i.e. (Q)V  U  CV T
…..(i)
(2) While in case of CP the heat is used in two ways
(i) In increasing the temperature of the gas by T
(ii) In doing work, due to expansion at constant pressure (W)

15
 K.T.G
So (Q)P  U  W   CP T …..(ii)
From equation (i) and (ii)  CP T   CV T  W
PV
  T(CP  CV )  PV  C P  CV  =R
 T
[For constant pressure, W = PV also from PV = RT,
PV = RT]
This relation is called Mayer’s formula and shows that CP  CV i.e. molar specific heat at
constant pressure is greater than that at constant volume.
Specific Heat in Terms of Degree of Freedom
f
(1) CV : For a gas at temperature T, the internal energy U  RT  Change in energy
2
f
U  RT ... (i)
2
Also, as we know for any gas heat supplied at constant volume (Q)V  CV T  U
... (ii)
1
From equation (i) and (ii) CV  fR
2
(2) CP : From the Mayer’s formula C p  Cv  R
f f 
 C P  CV  R  R  R    1 R
2  2 
f 
  1 R
CP  2  1 2
(3) Ratio of Cp and Cv () :   
CV f f
R
2
(i) Value of  is different for monoatomic, diatomic and triatomic gases.
5 7 4
 mono   1.6,  di   1 .4 ,  tri   1 .33
3 5 3
(ii) Value of  is always more than 1. So we can say that always CP > CV .
Gaseous Mixture
If two non-reactive gases are enclosed in a vessel of volume V. In the mixture 1 moles of one
gas are mixed with 2 moles of another gas. If NA is Avogadro’s number then
Number of molecules of first gas N 1  1 N A
and number of molecules of second gas N 2   2 N A
(1) Total mole fraction   (1   2 ) .
(2) If M1 is the molecular weight of first gas and M 2 that of second gas.
1 M1  2 M 2
Then molecular weight of mixture M 
1  2
(3) Specific heat of the mixture at constant volume will be
m1 m
C V  2 C V2
1CV1   2 CV2 M1 1 M 2
CVmix  
1   2 m1 m 2

M1 M 2
(4) Specific heat of the mixture at constant pressure will be

16
 K.T.G
 1    
1  R  2  2 R
   1 
1C P1   2 C P2  1 1   2  R   1    
C Pmix    1     2  2 
  
1   2 1   2 1  2    1  1    2  1 
R  m1   1  m 2   2 
    
m1 m 2
    1   M    1 
  M1  1  2  2 
M1 M 2
(1C P1   2 C P2 )
C Pmix 1   2
(5)  mixture  
C Vmix (1C V1   2 C V2 )
1   2
   1     
1   R   2  2  R 
1C P1   2 C P2   1      1  
1   2  
 
1C V1   2 C V2   R   R 
1    2  
   1 
   1  1   2 
1 1 
 2 2
 1  1  2  1 1 1 ( 2  1)   2 2 ( 1  1)
  mixture  
1 2 1 ( 2  1)   2 ( 1  1)

1  1  2  1

17