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KINETIC THEORY OF GASES

1. ASSUMPTION OF KINETIC THEORY


Assumptions of Kinetic theory :
(i) Assumptions regarding the molecule :
(a) Every gas consists of extremely small particles
known as molecules. The molecules of a given
gas are all identical but are different than those
another gas.
(b) The molecules of a gas are identical, spherical,
rigid and perfectly elastic point masses.
(c) Their size is negligible in comparison to inter
molecular distance (109 m)
(ii) Assumptions regarding volume :
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
gas.)
(iii) Assumptions regarding motion :
(a) Molecules of a gas keep on moving randomly in
all

possible

direction

with

all

possible

velocities.
(b) The speed of gas molecules lie between zero
and infinity (very high speed).
(c) The number of molecules moving with most
probable speeds is maximum.
(iv) Assumptions regarding collision :
(a) The gas molecules keep on colliding among
themselves as well as with the walls of
containing vessel. These collision are perfectly
elastic. (i.e. the total energy before collision =
total energy after the collisions).
(b) Molecules move in a straight line with constant
speeds during successive collisions.
(c) The distance covered by the molecules between
two successive collisions is known as free path
and mean of all free paths is known as mean
free path.
(d) The time spent is a collision between two
molecules is negligible in comparison to time
between two successive collisions.
(e) The number of collisions per unit volume in a
gas remains constant.
(v) Assumptions regarding force :
(a) No attractive or repulsive force acts between
gas molecules.

(b) Gravitational attraction among the molecules is


ineffective due to extremely small masses and
very high speed of molecules.
(vi) Assumptions regarding pressure :
Molecules constantly collide with the walls of
container due to which their momentum
changes. This change in momentum is
transferred to the walls of the container.
Consequently pressure is exerted by gas
molecules on the walls of container.
(vii)Assumptions regarding density :
The density of gas is constant at all points of
the container.
2. SOME DEFINITIONS
Definition :
(i) Gram mol. or Kilogram mol. :
(a) The quantity of matter in which the number of
molecules is equal to the Avogadro's number,
is defined as gram mol.
(b) The molecular weight of any substance
expressed in kilogram is defined as 1 kilogram
mol of that substance.
(c) The molecular weight of any substance
expressed in grams is defined as 1 gram mol of
that substance.
(d) 1 Kg mol of H2 = 2 kg.,
1 Kg mol of N2 = 28 kg.
1 Kg mol of O2 = 32 kg.,
1 Kg mol of CO2 = 44 kg.
(e) No. of molecules in 1 mol
=

Total number of molecules


Number of mols.

(f) Number of moles =

Mass of gas
Molecular wt. of gas

m
M
(g) The mass of 1 mol of a gas is equal to its
molecular weight.
or

n=

(ii) Avogadro's Number (NA ) :


(a) The number of molecules present in 1 mol of a
gas is defined as Avogadro's number.
(b) NA = 6.01 1023 per gm. mol.
= 6.02 1026 per Kgm. mol.

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KINETIC THEORY OF GASES

48

(iii) Molar volume and Molar mass (Vm ) :


(a) Molar volume Vm : The volume of 1 mol of gas
is known as molar volume (Vm).
(b) Vm =

V
n

(c) The unit of Vm is m3/mol.

Molecular weight (M) :


(a) The quantity in 1 mol of matter is its molecular

3. DIFFERENT VELOCITIES OF MOLECULES


OF A GAS

(1) Instantaneous velocity ( v ) : Velocity of


molecule at any instant of time.

(2) Instantaneous

< v > = v=

(4) Average speed (| v |) :

(b) Pressure at NTP = 76 Cm of Hg - column

<| v |> = |v|=

= 1.013 105 Newton/meter2 or Pascal


= 1 atmosphere.

(c) Volume of 1 mol of gas at NTP = 22.4 litre.

| v | | v 1 | + | v 2 |+ ... | v N |
=
N
N

8RT
RT
kT
=1.59
=1.59
M
M
m

(5) Most probable speed (vmp) : This is defined as


the speed with which maximum number of

(a) The minimum possible temperature at which all

molecules travel.

the gas molecules come to rest, is defined as


absolute zero temperature (i.e. 0 K).

vmp =

(b) The temperature at which the kinetic energy of

2RT
=
M

2kT
m

(6) Mean square velocity ( v 2 ) : Average of the


squares of instantaneous velocities of all the

absolute zero temperature.

molecules.

(c) At this temperature the volume of the gas


becomes zero.

< v2 > = v 2 =

Symbols used in this chapter

v 2 v12 + v 22 + ...v 2N
=
N
N

(7) Root mean square speed (RMS speed ) (vrms) :

= 0.082 Lit-atm/mol-K = 1.986 cal /mol-K

vrms =

M = Molecular wt in Kg = mass of 6.023 1023


molecules of the gas

m = Mass of each molecule in Kg = M/N0


N0 = Avogadro's constant = 6.023 1023

v
v + v + ... v N
= 1 2
=0
N
N

(a) Temperature at NTP = 0 C = 273 K

R = Universal gas constant = 8.314 J/mol-K

of

because molecules are in random motion

(iv) Meaning of NTP : NTP means normal

gas molecules become zero is defined as

Speed

(3) Average velocity ( v ):

(b) M = mNA (m = mass of a single molecule)

(v) Absolute zero temperature (0 K) :

(| v |):

molecule at any instant of time

weight.

temperature and pressure.

speed

v2
=
N

v12 + v 22 + ...v 2N
N

3RT
3kT
3PV
=
=
=
M
m
nM

3P
d

(8) Velocity of sound in the gas :

k = Boltzman's constant =R/N0 =1.381023J/K

vs =

P = Pressure of the gas in N/m2

C
RT
, where = P
M
CV

T = Temperature in Kelvin
N = Total number of molecules
d = Density of gas = nM/v
n = No. of moles

Examples
based on

Ex.1

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Different velocities of gas molecules


What is the rms speed of Helium gas molecules
at STP.
KINETIC THEORY OF GASES

49

Sol.

Ex.4

vrms is given by
3RT
M

vrms =

At STP, T = 273K,
M = 4 gm/mol = .004 kg/mol
R = 8.31 J/molK.

Crms

1.7 10 6

= 1.3 103 m/s.


The rms speed of oxygen at room temperature is
about 500 m/s. The rms speed of Hydrogen at
the same temperature is about
(A) 125 m/s
(B) 2000 m/s
(C) 8000 m/s
(D) 31 m/s
Sol.[B] RMS speed is given by
Ex.2

vrms =

Ex.5

3RT
M
1
M

Ratio of vrms. of oxygen and hydrogen.


( v rms ) 0
=
( v rms ) H

(C rms )T

= (C rms )T =

(C rms )T

(C rms )T

= 2

(T2 / T1 )

480
= 2
120

The root mean square (rms) speed of oxygen


molecules (O2) at a certain temperature T

3RT / M

When temperature is doubled,


the new temperature T' = 2T
and oxygen (O2) dissociates in atomic oxygen,
then molecular weight M' = M/2
The new rms speed

(vrms)H = 2000 m/s

v' =

The velocities of four molecules of a gas are


3 , 3, 4, 6 m/s, the root mean square velocity

will be(A) 4

(B) 16

(C) 8

(D) 13 3 /4

Sol.[A] Q vrms =

Sol.[B] Root mean square speed v =

MH
M0

1
500
2
=
=
( v rms ) H
32
4

Ex.3

(degree absolute) is . If the temperature is


doubled and oxygen gas dissociates in to
atomic oxygen. Is the rms speed remains
unchanged
(A) Yes
(B) No.
(C) Nothing can be said
(D) None of these

At constant temperature
vrms

3RT
M

Sol.[B] Q Crms =

3 8.31 273
.004

vrms=

The temperature of an ideal gas increased from


120 K to 480 K. The root mean square velocity of
the gas molecules is '', at 480K it becomes
(A) 4
(B) 2
(C) /2
(D) /4

v12 + v 22 + v 32 + v 24
4

4.

1/ 2

vrms =
vrms =

64
4

= 4m/s

3R 2T
M/2

3RT
M

v' = 2v

( 3 ) 2 + (3) 2 + (4) 2 + (6) 2


4
1/ 2

v' = 2

3RT '
=
M'

1/ 2

MAXWELL'S LAW OF
VELOCITY DISTRIBUTION

MOLECULAR

(a) Molecules can have all possible velocities in


the range from 0 to .
(b) The curve between number of molecule per
unit velocity range and velocity at different
temperature is as shown.

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KINETIC THEORY OF GASES

50

4.

T = 300 K
T = 1000 K
T = 2000 K

dn
dv

5.
vmp

vmp

vmp

2L
vx

t =

(c) The number of molecules belonging to finite


velocity range is constant however the velocity
of each molecule is changing.

Results :
(a) Different molecules have different velocities.
(b) As the temperature increases, the number of
molecules having higher velocities increases.
(c) At a given temperature, the velocity which
maximum number of molecules possess, is
called most probable velocity (vmp).
(d) With the increase in the temperature, the most
probable velocity increases.
(e) Area under the curve represent the total number
of molecules.
5. CALCULATION OF PRESSURE OF GAS

By the law of conservation of momentum


change in momentum of the wall = equal in
magnitude but opposite in direction to that of
molecule P = 2mvx
The distance travelled parallel to the
x-direction = L. Thus, the time between two
successive collisions with the shaded wall is

number of collisions per second (n) is


vx
2L
The momentum imparted per unit time to the

n=

6.

wall by this molecule is


F = nP =
7.

The total force on the wall


=F=

8.

vx
mv 2x
2mvx =
2L
L
m 2 m
vx =
L
L

2
x

Assuming average velocity in all direction to


be equal, we have

v 2x = v 2y = v 2z =

1
( v 2x + v 2y + v 2z )
3

1
1 m 2
v
= v2 F =
3
3 L
9.

sample, F =

X
L

Consider a molecule moving with velocity v in


any direction

1 mN v 2
3 L N

Pressure on the wall = Force /Area

L
Z
1. Consider an ideal gas enclosed in a cubical
vessel of edge 'L'

2.

If N is the total number of molecules in the

v = v x i + v y j+ v z k

3.

This molecule collides with the shaded wall


with velocity vx.
(a) momentum before collision = mvx
(b) momentum after collision = mvx
(assuming elastic collision)
change in momentum of the molecule
= mvx mvx = 2mvx

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1 mN v 2
3 L3
N
L
2
1 m0 v
P=
3 V N
where,m0 = Total mass of the gas = mN
P=

V = Volume of the vessel


m = mass of each molecule

P=

m
1 v2
(d = density = 0 )
d
3
N
V

P=

1
d v 2rms
3

or PV =

Q (vrms =

v2
)
N

1
1
m0 v 2rms or PV = Nm v 2rms
3
3
KINETIC THEORY OF GASES

51

10. As we know , energy of each molecule


=

Sol.[A] Pressure of the gas

1 mN 2
v rms
3 V
1
Energy E = v 2rms
2

1
m v 2rms
2

Total energy = E0 =

P=

1
Nm v 2rms
2

Nm v 2rms = 2E0
PV =

2
2
E0 or P = E
3
3

1
1
1
mv12 + mv 22 + .... + mv 2n
2
2
2
So energy is basically the sum of energies of
all molecules which represents translational
kinetic energy.

where E = Energy per unit volume


11. Dependence of pressure :
(a) P n (Total number of moles)
(b) P m ( Total mass of the gas)
(c) P v 2rms
(d) P 1/V (V = Volume)
(e) P d (d = Density)
(f) P E (E = Energy per unit volume)
Examples
based on

Ex.6

Sol.

Which of the following parameters is the same


for molecules of all gases at a given
temperature ?
(A) Mass
(B) Speed
(C) Momentum
(D) Kinetic energy
Sol.[D] Kinetic energy according to kinetic theory of
gases is given by,
Ex.8

Calculation of pressure of gas


A flask of 103 m3 volume contains 3 1022
molecules of oxygen at a certain temperature.
The mass of one molecule of oxygen is
5.3 1026 Kg and rms velocity of its molecules
at the same temperature is 400 m/s. Calculate
the pressure of the gas.
Pressure of the gas
P=
Here

3
RT
2
R is a universal constant and temperature
remains same for all gases. So kinetic energy is
same for molecules of all gases at a given
temperature.
E=

Ex.9

1 mN 2
v rms
3 V

V = 103m3 N = 3 1022
m = 5.3 1026 Kg vrms = 400 m/s
1 5.3 10 26 3 10 22 (400) 2
P=
3
10 3

2E
. Here E refers to
3V

(A) Translational kinetic energy

(D) 4P0/ 2

1 Nm 2
v rms (m = mass of each molecule,
3 V
V = volume of the gas)
Now , m' = 1/2 m
v'rms = 2vrms

Sol.[B] P0 =

The pressure of an ideal gas is written as


P=

A gas is filled in a container at pressure 'P0' . If


the mass of each molecule is halved and speeds
are double, then resulting pressure will be (B) 2P0
(A) 4P0
(C) P0

= 8.48 104 N/m2.


Ex.7

v 2 + v 22 + ... + v 2n
1
mN 1
2
N

P' =
Ex.10

(B) Rotational kinetic energy


(C) Vibrational kinetic energy
(D) Total kinetic energy

1 Nm 2
1 Nm.4v 2rms
= 2.
v rms = 2P0
3 V
3
2V

The ratio of number of collisions per second at


the walls of containers by H2 and Ne gas
molecules kept at same volume and
temperature is
(A) 10 : 1
(B) 1 : 10
(C) 1 : 10

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(D) 10 : 1
KINETIC THEORY OF GASES

52

Sol.[D] Let's consider the wall perpendiculars to x-axis


number of collisions per second are given by

2.

vx
Now, vx = vrms/ 3
2L
'L' and 'T' is same of both. Then, Ratio of speed
given by
v rms,H 2
v rms, Ne

M Ne
=
M H2

20
=
2

10 :1

Two containers of equal volumes contain H2


and O2 at same temperature. If the number of
molecules of these gases is also equal then the
ratio of pressure exerted by these will be (A) 1 : 1
(B) 4 : 1
(C) 8 : 1
(D) 16 : 1
Sol.[A] Pressure of the gas
1 nM 2
1 nM 3RT nRT
P=
=
v rms =
.
3 V
3 V
V
M
Given, nH = nO TH = TO
Ex.11

VH = VO
2

PH = PO
2

The density of carbon dioxide gas at 0C and at


a pressure of 1.0 105 newton/metre2 is
1.98kg/m3. Find the root mean square velocity
of its molecules at 0C. Pressure is constant
(A) 39 metre/sec
(B) 3.09 metre/sec
(C) 389 metre/sec (D) 38.9 metre/sec
Sol.[C] We know that
1
P = v2
3
Ex.12

7. DEGREE OF FREEDOM

Number of modes in which a gas molecule can


store energy is called degrees of freedom. It can
also be referred as the number of modes in which
motion of gas molecule takes place.
Degree of Freedom
Translational Rotational Vibrational Total
Monatomic

Diatomic
Triatomic /
Triangular

Triatomic Linear

8. MAXWELL'S LAW OF EQUIPARTITION OF


ENERGY

1.

2.

3.

1/ 2

3P

Given that = 1.98kg/m3 and


P = 1.0 105 N/m2
vrms =

4.

6. CONCEPT OF ABSOLUTE TEMPERATURE

For a given gas, vrms T


3PV
1 nM 2
v rms or v2rms =
P=
3 V
nM
(n = no. of moles)
Q PV = nRT
v2rms =

3PV
or vrms =
M

According to this law, for a system in thermal


equilibrium all its energy is divided equally
among it's all possible degrees of freedom.
At temperature T K, each degree of freedom
contributes on an average 1/2 KT of energy per
molecule and 1/2 RT of energy per mole.
If 'f' is the number of degrees of freedom, mean
energy of a molecule at temperature T is
fRT
fKT
and Total energy per mole =
E=
2
2
Total internal energy
U = Potential energy + Kinetic energy

(Q For an ideal gas, potential energy = 0)

3 1.0 105
vrms =
1.98
vrms = 389 m/s

1.

It is clear that, at T = 0 K, vrms = 0 i.e. the RMS


speed of molecules of a gas is zero at 0 K.A
temperature less than 0 K is not possible
because at this temperature velocity becomes
an imaginary quantity. So, the temperature at
which rms speed of gas molecule is zero is
called absolute zero or zero Kelvin.

3PV
M

U = Kinetic energy
fRT
=
(per mole)
2
5. For translatory motion of any gas, f = 3
Mean translatory KE per molecule = (3/2) KT
Mean translatory KE per mole = (3/2) RT
Mean translatory KE per gram = (3/2) (RT/M)
6.

As we already have
P = (2/3) E
Where E Energy per unit volume = (3/2) P
Mean translatory KE in unit volume of a gas is
(3/2)P, where 'P' is the pressure of the gas.

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KINETIC THEORY OF GASES

53

7.

Total energy
E0 = (3/2) PV ......... (for volume V)

9. DIFFERENT KINETIC ENERGIES OF A GAS


1.

2.
3.

Mean molar kinetic energy : (E) : Translatory


kinetic energy of one mole of a gas
(6.023 1023 molecules)
E = (1/2) Mv2rms = (3/2) RT
Mean translatory KE of one molecule = (3/2) KT
If 'M' is the molecular wt in kg, i.e. mass of one
mole of gas, then mean KE of one gram of gas

Ex.15

At what temperature does the average


translational kinetic energy of a molecule in a
gas equal to the kinetic energy of an electron
accelerated from rest through a potential
difference of 5 volt.
(B) 3.865 103K
(A) 386.5 103K
(D) 38.65 103 K
(C) .38 103K
Sol.[D] K.E. of the electron is
5 eV = 5 1.6 1019J
But K.E. = 3/2 KT

5 1.6 1019 = 3/2 (1.38 1023) T

3 RT 3 KT
=
=
2 m
2 M
Where m = mass of each molecule in kg.
Examples
based on

Ex.13

3
1
Sol.[A] KT = mve2
2
2
Where ve = escape velocity of earth = 11.1 km/sec
m = mass of 1 molecule of oxygen
= 5.34 1026

T=

T=

3 1.38 10 23

T = 38. 65 103 K

Different kinetic energy of gas


At what temperature will the root mean square
velocity of oxygen molecules be sufficient so as
the escape from the earth ?
(B) 16 105K
(A) 1.6 105 K
5
(D) 160 105 K
(C) .16 10 K

5 1.6 10 19 2

T=

10. DIFFERENCE BETWEEN IDEAL GAS &


REAL GAS
Ideal Gas

Real Gas

(i) These gases obey the


ideal gas equation

These gases do not obey


the ideal gas equation

(ii) These gases obey the


Boyle's, Charle's and

These gases do not these


laws.

pressure laws in every


state of pressure and
temperature

mv e2
3K

(iii) For these the equation

5.32 10 26 (11.1 10 3 )

of state is PV = RT

3 (1.38 10 23 )

For these the equation of


state is
P+

T = 1.6 10 K
Ex.14

The first excited state of hydrogen atom is


10.2 eV above its ground state. What
temperature is needed to excite hydrogen atoms
to first excited level
(B) .788 104 K
(A) 7.88 104
4
(C) 78.8 10 K
(D) 788 104 K
Sol.[A] K.E. Per atom = 3/2 KT
K.E. of the hydrogen atom = 10.2 eV
10.2 eV = 10.2 (1.6 1019) Joule
2 K.E. per atom
T=
3
K
2 10.2 1.6 10 19

3
1.38 10 23
Where k = 1.38 1023 J/mole. K
T = 7.88 104 K

T=

(iv) Their specific heat is

(V b) = RT

V2

Their

specific

heat

is

proportional

to

independent of

directly

temperature

temperature (Cv T)

(v) Their internal energy


depends

upon

only

temperature

Their

energy

depends upon temperature


as

dU = CvdT

internal
well

dU = CvdT +

as
a
V2

volume
dV

(vi) At high temperature

At low temperature and

and low pressure these

high pressure these gases

gases

behave like real gases.

behave

like

ideal gases

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KINETIC THEORY OF GASES

54

Graphically

11. GAS LAWS


1.

Boyle's Law : At a given temperature, the


pressure of a given mass of gas is inversely

P/T

1/P

proportional to it's volume.


i.e. P

or PV = Constant.

P/T

Graphically,

1/T

T
P

V
1/V

1/P

PV

P or 1/P

Ideal Gas Equation :


Using all the laws above, an equation for n
moles of an ideal gas can be written in the
form.

PV = nRT also PV = NKT


Where, n = No. of moles
N = No. of molecules = N0n
N0 = Avogadro's constant
K = Botzmann's constant = (R/N0)

PV
V

2.

4.

PV

t(C)

T or 1/T

1
(T = Constant)
V

Charle's Law : At a given pressure, the volume

m
M
m = Total mass of the gas
M = Molecular wt.

of a given mass of a gas is proportional to it's

No. of moles =

absolute temperature.
i.e. V T (P = Constant) Temperature is in
Kelvin.

PV = m

Graphically

R
T = mrT
M

R
M
Note : If mass of gas is also changed, then
Boyle's, Charle's and Gay-Lussac's laws cannot
be applied. However we can use the relation,

Where r = specific gas constant =


V

1/V
T

V
T

1/T

V
V/T

P1V1
PV
= 2 2
n1T1
n 2 T2

V/T

5.
T or 1/T

V or 1/V

t(C)

Dalton's Law of partial pressure :


" The pressure exerted by a mixture of several
gases equals the sum of pressures exerted by

3.

Gay-Lussac's Law : At a given volume, the

each gas occupying the same volume as that of

pressure of a given mass of a gas is proportional

the mixture" for n gases

to it's absolute temperature.

i.e. P = P1 + P2 + P3+ ..... Pn .

i.e P T(V = Constant)

Where P = pressure exerted by mixture

or

P1 P2
=
T1 T2

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P1 ,P2 , P3, .......... Pn = partial pressure of the


component gases
KINETIC THEORY OF GASES

55

6.

Avogadro's Law :
At the same temperature and pressure, equal
volumes of all gases contain equal number of

Examples
based on

Ex.17

molecules or moles

Imp. Facts :
(a) At = T = 273 K and P = 1atm, (STP), 22.4 litre
of each gas has N0 = 6.023 1023 molecules or

Sol.

22.4 liter of volume"

T1
[Here T1 = 273 + 37 = 310 K and
T2
T2 = 273 + 23 = 296 K]
310
= 1500
296
= 1570.95 litre

(b) This means, that at STP mass of 22.4 litre of a

V2 = V1

gas is equal to it's mol. wt.


(c) This implies that 32 gm oxygen (O2), 28 gm
Nitrogen (N2), 2 gm Hydrogen (H2) etc. occupy
the same volume = 22.4 litres at STP.

Grahm's Law of diffusion :


When two gases at the same pressure and
temperature are allowed to diffuse into each

Examples
based on

Ex.18

other, the rate of diffusion of each gas is


inversely proportional to the square root of the
density of the gas
i.e. D

1
d

Sol.
Where, D = Rate of diffusion, d =

Examples
based on

Ex.16

2
300 [Here T1 = 273 + 27 = 300 K]
1
= 600 K
= 600 273
= 327C

A sample of oxygen with volume 1000 cc at a


900 cc. What pressure is needed to do this if the
temperature is kept constant ?

Examples
based on

Ex.19

Here temperature is constant, so


P1V1 = P2V2
V1
V2

= (1 atm)

P2
T1
P1

Boyle's law

P2 = P1

A sample of helium gas is at a pressure of


1 atm when the volume is 100 ml and its
temperature is 27C. What will be the
temperature of the gas if the pressure becomes
2 atm and volume remains 100 ml.
Here volume remains constant, so

T2 =

D1
d1
=
D2
d2

pressure of 1 atm is compressed to a volume of

Sol.

Gay-Lussac's law

P1 P2
=
T1 T2

density of gas.

1500 ml of a gas at a room temperature of 23C


is inhaled by a person whose body temperature
is 37C, if the pressure and mass stay constant,
what will be the volume of the gas in the lungs
of the person.
Here pressure and amount of the gas are kept
constant. Therefore,
V1 V2
=
T1 T2

in other words. "One mole of gas at STP occupy

7.

Charle's law

Sol.
1000
900

= 1.11 atm
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Dalton's law of partial pressure


A vessel of volume 2 103 m3 contains
0.1 mol of hydrogen gas and 0.2 mol of
helium. If the temperature of the mixture is
300 K calculate the pressure due to component
gases and the mixture
According to Dalton law
Pmixture = PH + PHe
RT
(nH + nHe )
=
V
8.31 300
=
(0.1 + 0.2) = 3.75 105 N/m2
2 10 3
KINETIC THEORY OF GASES

56

Examples
based on

Ideal gas equation

PV
represents
KT
(A) Mass of the gas
(B) Kinetic energy of the gas
(C) Number of moles of the gas
(D) Number of molecules in the gas
Sol.[D] By ideal gas equation
PV = nRT
But R = NAK
PV = nNAKT
and N = nNA represent number of molecules

Ex.20

Sol.

total distance travelled


total number of collisions

The quantity

so

Ex.21

(iii) Mean free path =

PV
=N
KT

A sample of organ gas is at a pressure of 1 atm.


When the volume is 100 mL and the
temperature is 35C. What must be its
temperature if the pressure become 720 mm of
Hg and its volume 200 mL.
Here PV = RT
PV
= R (constant)
T

or

P1V1
PV
= 2 2
T1
T2

so

Given P1 = 1 atm = 760 mm of Hg,


V1 = 100 mL,T1 = 35C = 273 + 35 = 308 K
P2 = 720 mm of Hg,V2 = 200 mL
Substitute the above values in the equation,
we get
760 100 720 200
=
308
T2
720 200 308
760 100
= 584 K
= 584 273
= 311C

T2 =

(iv) If a molecule travels distance 1, 2, 3 ...... 4


in N different collision during time t. Mean
free path will be -

(v) If the average velocity of a molecule is v , then


=

mean free path. It is represented by .

vt
N

(vi) From kinetic theory the mean free path


1

2 2 n

where is diameter of a molecule and n is the


number of molecules in a unit volume of the
gas.
(vii) If m is the mass of a molecule, then
=

2 2 mn

but mn = = density of the gas

2 2

(viii) Mean free path is related to the temperature


and the pressure as
=

kT
2 2 P

where T = temperature, k = Boltzman constant,


P = pressure.

12. MEAN FREE PATH


(i) The path traversed in a straight line by a
molecule of a gas before it collides with another
molecules is called free path.
(ii) The average distance travelled in between two
successive collisions by a molecule is called

1 + 2 + 3 + ... + N
N

(ix) Therefore

1
i.e. the mean free path is

inversely proportional to the density of a gas.


(x) For constant volume and hence constant
P
is
number density n of gas molecules,
T
constant so that will not depend on P and T.

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KINETIC THEORY OF GASES

57

But if volume of given mass of a gas is allowed


to change with P or T then
1
i.e. T at constant pressure and at
P
constant temperature.
On increasing the temperature at constant
pressure the mean free path increases and on
increasing the pressure at constant temperature
the mean free path decreases.
Examples
based on

Ex.22

Mean free path


The relation between mean free path of
molecules of a gas and its density is 1
(A)
(B)

(C)

Sol.[B]

m
2

(D)

i.e.

13. REAL GAS - VANDER WALL GAS EQUATION

(i) Real gases do not obey ideal gas equation.


(ii) In order to explain the behaviour of real gases
following two modification are considered in
ideal gas equation :
(A) Non- zero size of molecules : A certain portion
of volume of a gas is covered by the molecules
themselves. Therefore the space available for
the freely motion of molecules of a gas will be
slightly less than the volume V of a gas. This
decreases in volume of a gas will be (V b). b
is about four times the actual volume occupied
by the molecules.
(B) Intermolecular force : Attractive force acts
between molecules of real gases. Due to this
molecules do not exert that force on the wall
which they would have exerted in absence of
intermolecular force. Therefore the observed
pressure P of the gas will be less than the
pressure in absence of intermolecular force.
This decrease in pressure is assumed to be
a
equal 2 , where 'a' is a constant.
V
Therefore pressure of a real gas will be
a
RT
, where P is observed
P =

( V b)
V2
pressure.

(iii) The equation obtained by using above


mentioned modifications in ideal gas equation
is called Vander wall's equation or real gas
equation. It is as follows :
P+

a
V2

(V b) = RT

(iv) Real gases at low pressure and high


temperatures behave like ideal gases.
(v) a and b are constants and value are different for
different gases.
(vi) a is a constant for a gas.
Unit of a = (pressure volume2)
= (N m4)
Dimensions of a = M1 L5 T2
(vii) b is a constant for a gas. The value of b is four
times the volume occupied by the molecules.
Unit of b is unit of volume = m3
Dimensions of b = M0 L3 T0
(viii) Pressure exerted by real gases is less then the
pressure exerted by ideal gases.
(ix) Specific heat of real gas increases with
increases of temperature.
14. CRITICAL POINT OR CRITICAL CONSTANT
(i) Critical temperature (TC) : Temperature below
which a gas can be liquefied only by increase in
pressure and above which no liquification is

possible whatever the pressure P be :


(ii) Critical pressure (PC): The minimum pressure
required to liquefy a gas when it is at critical
temperature (TC)
(iii) Critical (specific) volume (VC) : The volume of
unit mass of a gas at critical pressure and
temperature.
(iv) Triple point : The temperature at which all the
three states of matter coexist in equilibrium

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8a
TC =
27Rb
8a 2
b and VC = 3b
PC =
27
(Where a and b are constant)

KINETIC THEORY OF GASES

58