Thi s mol ecul e colli des wi th the shaded wal l ) (
1
A wi th veloci ty
x
v and
rebounds wi th veloci ty
x
v .
The change i n momentum of the molecule
x x x
mv mv mv P 2 ) ( ) ( = = A
As the moment um r emai ns conser ved i n a col l i si on, t he change i n
moment um of t he wal l A1 i s
x
mv P 2 = A
After rebound thi s molecule t ravel toward opposi te wall A2 with veloci ty
x
v , colli de to i t and agai n
rebound wi th vel oci ty
x
v towards wall A1.
(1) Ti me between t wo successi ve col li si on wi th the wal l A1.
molecule of Velocity
collision successive two between molecule by travelled Distance
= At
x
v
L 2
=
Number of col li si on per second
L
v
t
n
x
2
1
=
A
=
(2) The momentum i mparted per uni t t i me to the wall by t hi s mol ecul e
2
2
2
x x
x
v
L
m
mv
L
v
P n = = A
Thi s i s also equal to the force exerted on the wall
1
A due to thi s molecule
2
x
v
L
m
F = A
(3) The t otal force on the wall
1
A due to all the mol ecules
=
2
x x
v
L
m
F
(4) Now pressure i s defi ned as force per uni t area
= = =
2 2
x x
x
x
v
V
m
v
AL
m
A
F
P Si mi larl y
=
2
y y
v
V
m
P and
=
2
z z
v
V
m
P
So
+ + = + + ) (
2 2 2
z y x z y x
v v v
V
m
P P P
=
2
3 v
V
m
P [ As P P P P
z y x
= = = and
2 2 2 2
z y x
v v v v + + = ]
......) ( 3
3
3
2
2
2
1
+ + + = v v v
V
m
P
Y
X
Z
L
vx
vx
4 Kinetic Theory of Gases
or


.

\
 + + + +
=
N
v v v v
V
mN
P
....
3
2
4
2
3
2
2
2
1
or
2
3
rms
v
V
N m
P =
+ + + +
=
N
v v v v
v
rms
.....
2
4
2
3
2
2
2
1
or
2
3
1
rms
v
V
N m
P =
I mpor t ant poi nt s
(i )
2
3
1
rms
v
V
N m
P = or
V
T N m
P
) (
[ As T v
rms
2
]
(a) I f volume and temperat ure of a gas are constant P mN i .e. Pressure (Mass of gas).
i .e. i f mass of gas i s i ncreased, number of molecules and hence number of colli si on per second i ncreases
i .e. pressure wi ll i ncrease.
(b) I f mass and temperature of a gas are constant. P (1/ V), i.e., if volume decreases, number of coll i si ons
per second wi l l i ncrease due to lesser effecti ve di stance between the wall s resul ti ng i n greater pressure.
(c) I f mass and volume of gas are constant, T v P
rms
2
) (
i .e., i f temperature i ncreases, the mean square speed of gas mol ecul es wi ll i ncrease and as gas mol ecul es
are movi ng faster, they wi ll col li de wi th the walls more often wi th greater momentum resulti ng i n greater
pressure.
(i i )
2
3
1
rms
v
V
N m
P =
2
3
1
rms
v
V
M
= [ As M = mN = Total mass of the gas]
2
3
1
rms
v P =
=
V
M
As
(i ii ) Relati on between pressure and ki neti c energy
Ki neti c energy
2
2
1
rms
v M = Ki neti c energy per uni t volume
2 2
2
1
2
1
) (
rms rms
v v
V
M
E = 
.

\

= ..(i )
and we know
2
3
1
rms
v P = ..(i i )
From (i ) and (i i ), we get E P
3
2
=
i .e. the pressure exerted by an ideal gas i s numericall y equal to the two thi rd of the mean ki neti c energy of
translati on per uni t volume of the gas.
Sample Pr oblems based on Pr essur e
Pr oblem 1. The root mean square speed of hydrogen molecules of an i deal hydrogen gas kept i n a gas chamber at 0C
is 3180 m/ s. The pressure on the hydrogen gas is
(Densi ty of hydrogen gas is
3 2
/ 10 99 . 8 m kg
, 1 atmosphere
2 5
/ 10 01 . 1 m N = ) [ MP PMT 1995]
(a) 0.1 atm (b) 1.5 atm (c) 2.0 at m (d) 3.0 at m
Kineti c Theory of Gases 5
Sol uti on : (d) As atm m N v P 0 . 3 / 10 03 . 3 ) 3180 ( ) 10 99 . 8 (
3
1
3
1
2 5 2 2 2
rms
= = = =
Pr oblem 2. The temperature of a gas is raised while i ts vol ume remains constant, the pressure exerted by a gas on the
walls of the contai ner i ncreases because its molecul es
(a) Lose more kinetic energy to the wal l
(b) Are in contact with the wall for a shorter ti me
(c) Stri ke the wall more often with hi gher vel ocities
(d) Collide wi th each other less frequency
Sol uti on : (c) Due to increase i n temperature root mean square vel ocity of gas molecul es i ncreases. So they strike the
wall more often with higher veloci ty. Hence the pressure exerted by a gas on the wal ls of the contai ner
increases.
Pr oblem 3. A cyl inder of capacity 20 li tr es is filled wi th
2
H gas. The total average ki netic energy of translatory motion
of i ts mol ecules i s J
5
10 5 . 1 . The pressure of hydrogen i n the cyl i nder is [ MP PET 1993]
(a)
2 6
/ 10 2 m N (b)
2 6
/ 10 3 m N (c)
2 6
/ 10 4 m N (d)
2 6
/ 10 5 m N
Sol uti on : (d) Ki netic energy E = J
5
10 5 . 1 , vol ume V = 20 l i tr e =
3 3
10 20 m
Pressure
V
E
3
2
=
2 6
3
5
/ 10 5
10 20
10 5 . 1
3
2
m N =


.

\

=
.
Pr oblem 4. N mol ecul es each of mass m of gas A and 2N molecul es each of mass 2m of gas B are contai ned i n the
same vessel at temperature T. The mean square of the vel ocity of mol ecules of gas B i s v
2
and the mean
square of x component of the vel ocity of molecules of gas A is w
2
. The ratio
2
2
v
w
is
(a) 1 (b) 2 (c)
3
1
(d)
3
2
Sol uti on : (d) Mean square veloci ty of molecul e
m
kT 3
=
For gas A, x component of mean square veloci ty of mol ecule
2
w =
Mean square veloci ty
m
kT
w
3
3
2
= = ..(i)
For B gas mean square veloci ty
m
kT
v
2
3
2
= = ..(ii)
From (i ) and (i i)
1
2 3
2
2
=
v
w
so
3
2
2
2
=
v
w
.
Pr oblem 5. A flask contai ns
3 3
10 m
.
6 Kinetic Theory of Gases
Pr oblem 6. A gas at a certai n volume and temperature has pressure 75 cm. I f the mass of the gas is doubled at the
same volume and temperature, its new pressure is
(a) 37.5 cm (b) 75 cm (c) 150 cm (d) 300 cm
Sol uti on : (c)
2
3
1
rms
v
V
M
P =
V
MT
P
At constant vol ume and temperature, i f the mass of the gas is doubled then pressure wil l become twice.
11.4 I deal Gas Equati on.
A gas whi ch stri ctly obeys the gas laws i s called as perfect or an i deal gas. The si ze of the molecule of an
i deal gas i s zero i .e. each mol ecule i s a poi nt mass wi th no di mensi on. There i s no force of att racti on or
repul si on amongst the molecule of the gas. Al l real gases are not perfect gases. However at extremel y l ow
pressure and hi gh temperature, the gases l i ke hydrogen, ni trogen, heli um etc. are nearly perfect gases.
The equati on whi ch relates the pressure (P), volume (V) and temperature (T) of the gi ven state of an i deal
gas i s known as gas equati on.
I deal gas equations
For 1 mole or NA molecule or M gram or 22.4 l i tr es of gas PV = RT
For mol e of gas PV = RT
For 1 molecule of gas
kT T
N
R
PV
A
=


.

\

=
For N molecul es of gas PV = NkT
For 1 gm of gas
rT T
M
R
PV = 
.

\

=
for n gm of gas PV = nr T
(1) Universal gas constant ( R) : Di mensi on ] [
1 2 2
T ML
re Temperatu moles of No.
done Work
re Temperatu moles of No.
Volume Pressure
= =
T
PV
R
Thus uni versal gas constant si gni fi es the work done by (or on) a gas per mole per kel vi n.
S.T.P. value :
kelvin mole
atm litre
kelvin mole
cal
kelvin mole
Joule
8221 . 0 98 . 1 31 . 8
(2) Boltzman's constant ( k) : Di mensi on ] [
1 2 2
T ML
23
10 023 . 6
31 . 8
= =
N
R
k kelvin Joule/ 10 38 . 1
23
=
(3) Specific gas constant ( r ) : Di mensi on ] [
1 2 2
T L
M
R
r = ; Uni t :
kelvin gm
Joule
Si nce the value of M i s di fferent for di fferent gases. Hence t he value of r i s di fferent for di fferent gases.
Sample Pr oblems based on I deal gas equation
Ki netic Theory of Gases 7
Pr oblem 7. A gas at 27C has a vol ume V and pressure P. On heating i ts pressure i s doubled and volume becomes
three times. The resulting temperature of the gas will be
(a) 1800C (b) 162C (c) 1527C (d) 600C
Sol uti on : (c) From i deal gas equation RT PV = we get 6
3 2
1
1
1
1
1
2
1
2
1
2
=


.

\



.

\

=


.

\



.

\

=
V
V
P
P
V
V
P
P
T
T
300 6 6
1 2
= = T T . 1527 1800 C K = =
Pr oblem 8. A balloon contai ns
3
500 m of heli um at 27C and 1 atmosphere pressure. The volume of the helium at
3C temperature and 0.5 atmosphere pressure will be
(a)
3
500 m (b)
3
700 m (c)
3
900 m (d)
3
1000 m
Sol uti on : (c) From RT PV = we get
5
9
5 . 0
1
300
270
2
1
1
2
1
2
= 
.

\


.

\

=


.

\



.

\

=
P
P
T
T
V
V
3
2
900
5
9
500 m V = =
Pr oblem 9. When vol ume of system i s increased two ti mes and temperature i s decreased half of i ts i ni tial
temperature, then pressure becomes
(a) 2 ti mes (b) 4 ti mes (c) 1 / 4 times (d) 1 / 2 ti mes
Sol uti on : (c) From RT PV = we get
4
1
2
2 /
1
1
1
1
2
1
1
2
1
2
=


.

\



.

\

=


.

\



.

\

=
V
V
T
T
V
V
T
T
P
P
4
1
2
P
P =
Pr oblem 10. The equati on of state correspondi ng to 8g of
2
O i s [ CBSE PMT 1994; DPMT 20 00]
(a) RT PV 8 = (b) 4 / RT PV = (c) RT PV = (d) 2 / RT PV =
Sol uti on : (b) As 32 gm
2
O means 1 mol e therefore 8 gm
2
O means 1 / 4mole i .e.
4
1
=
So from RT PV = we get RT PV
4
1
= or
4
RT
PV =
Pr oblem 11. A flask is fil led with 13 gm of an ideal gas at 27C and its temperature is raised to 52C. The mass of the
gas that has to be released to maintai n the temperature of the gas i n the fl ask at 52C and the pressure
remai ni ng the same is [ EAMCET ( Engg.) 20 00]
(a) 2.5 g (b) 2.0 g (c) 1.5 g (d) 1.0 g
Sol uti on : (d) PV Mass of gas Temperature
I n this problem pressure and volume remai ns constant so
1 1
T M = M2T2 = constant
13
12
325
300
) 273 52 (
) 273 27 (
2
1
1
2
= =
+
+
= =
T
T
M
M
gm gm M M 12
13
12
13
13
12
1 2
= = =
i .e. the mass of gas released from the flask = 13 gm 12 gm = 1 gm.
Pr oblem 12. Ai r is fill ed at 60C i n a vessel of open mouth. The vessel is heated to a temperature T so that 1 / 4
th
part of
air escapes. Assumi ng the volume of vessel remai ni ng constant, the value of T is
(a) 80C (b) 444C (c) 333C (d) 171C
Sol uti on : (d) M M =
1
, K T 333 273 60
1
= + = ,
4
3
4
2
M M
M M = = [ As 1 / 4
th
part of air escapes]
I f pressure and vol ume of gas remai ns constant t hen MT = constant
2
1
1
2
M
M
T
T
=
3
4
4 / 3
= 
.

\

=
M
M
C K T T = = = = 171 444 333
3
4
3
4
1 2
Pr oblem 13. I f the i ntermolecular forces vanish away, the vol ume occupied by the molecules contai ned i n 4.5 kg water
at standard temperature and pressure will be given by
8 Kinetic Theory of Gases
(a)
3
6 . 5 m (b)
3
5 . 4 m (c) 11.2 li tr e (d)
3
2 . 11 m
Sol uti on : (a) 250
10 18
5 . 4
of water wt. Molecular
of water Mass
3
=
= =
kg
kg
, T = 273 K and
2 5
/ 10 m N P = (STP)
From RT PV =
3
5
66 . 5
10
273 3 . 8 250
m
P
RT
V =
= =
.
Pr oblem 14. The pressure P, volume V and temperature T of a gas in the jar A and the other gas i n the jar B at pressure 2P,
volume V/ 4 and temperature 2T, then the ratio of the number of mol ecules i n the jar A and B will be[ AI I MS 1982]
(a) 1 : 1 (b) 1 : 2 (c) 2 : 1 (d) 4 : 1
Sol uti on : (d) I deal gas equati on RT
N
N
RT PV
A


.

\

= = where N = Number of mol ecule, NA = Avogadro number


.

\



.

\



.

\

=
1
2
2
1
2
1
2
1
T
T
V
V
P
P
N
N
1
4 2
4 / 2
= 
.

\



.

\


.

\

=
T
T
V
V
P
P
.
Pr oblem 15. The expansi on of an ideal gas of mass m at a constant pressure P is given by the straight li ne D. Then the
expansi on of t he same i deal gas of mass 2m at a pressure P/ 2 is gi ven by the straight li ne
(a) E
(b) C
(c) B
(d) A
Sol uti on : (d) From PV MT or T
P
M
V ; Here 
.

\

P
M
represents the sl ope of curve drawn on volume and temperature
axis.
For first conditi on sl ope 
.

\

P
M
graph is D (gi ven i n the probl em)
For second condition slope 
.

\

=
P
M
P
M
4
2 /
2
i.e. slope becomes four time so graph A is correct in this conditi on.
Pr oblem 16. I f the value of molar gas constant i s 8.3 J/ mol eK, the n specifi c gas constant for hydrogen i n J/ mol eK
wil l be
(a) 4.15 (b) 8.3 (c) 16.6 (d) None of these
Sol uti on : (a) Specifi c gas constant 15 . 4
2
3 . 8
) ( gas of weight Molecular
) ( constant gas Universal
= = =
M
R
r Joule/ moleK.
Pr oblem 17. A gas i n contai ner A is in thermal equil ibrium wi th another gas i n contai ner B. both contain equal masses
of the two gases i n the respecti ve contai ners. Which of the following can be true
(a)
B B A A
V P V P = (b)
B A B A
V V P P = = , (c)
B A B A
V V P P = = , (d)
B
B
A
A
V
P
V
P
=
Sol uti on : (b, c) Accordi ng to probl em mass of gases are equal so number of mol es wil l not be equal i .e.
B A
=
From i deal gas equation RT PV =
B
B B
A
A A
V P V P
= [ As temperature of the contai ner are equal]
From this rel ation i t i s clear that if
B A
P P = then 1 = =
B
A
B
A
V
V
i .e.
B A
V V =
A
B
C
D
E
8
6
4
2
1
Vol ume
Temperature
Kineti c Theory of Gases 9
Similarl y i f
B A
V V = then 1 = =
B
A
B
A
P
P
i .e.
B A
P P = .
Pr oblem 18. Two identical glass bul bs are i nterconnected by a thi n gl ass tube. A gas i s fil led in these bul bs at N.T.P. If
one bul b is placed i n ice and another bul b i s pl aced i n hot bath, then the pressure of the gas becomes 1.5
times. The temperature of hot bath wil l be
(a) 100C
(b) 182C
(c) 256C
(d) 546C
Sol uti on : (d) Quanti ty of gas in these bulbs is constant i .e. I niti al No. of mol es in both bul b = fi nal number of moles
'
2
'
1 2 1
+ = +
) (
5 . 1
) 273 (
5 . 1
) 273 ( ) 273 ( T R
PV
R
PV
R
PV
R
PV
+ = +
T
5 . 1
273
5 . 1
273
2
+ = C K T = = 546 819 .
Pr oblem 19. Two containers of equal volume contai n the same gas at pressures
1
P and
2
P and absolute temperatures
1
T and
2
T respecti vel y. On joi ni ng the vessels, the gas reaches a common pressure P and common
temperature T. The ratio P/ T i s equal to
(a)
2
2
1
1
T
P
T
P
+ (b)
2
2 1
2 2 1 1
) ( T T
T P T P
+
+
(c)
2
2 1
1 2 2 1
) ( T T
T P T P
+
+
(d)
2
2
1
1
2 2 T
P
T
P
+
Sol uti on : (d) Number of moles i n first vessel
1
1
1
RT
V P
= and number of moles i n second vessel
2
2
2
RT
V P
=
I f both vessels are joi ned together then quanti ty of gas
remai ns same i .e
2 1
+ =
2
2
1
1
) 2 (
RT
V P
RT
V P
RT
V P
+ =
2
2
1
1
2 2 T
P
T
P
T
P
+ =
Pr oblem 20. An ideal monoat omic gas is confined in a cyli nder by a springloaded pi ston i f crosssection
2 3
10 8 m
.
I nitiall y the gas is at 300K and occupi es a volume of
3 3
10 4 . 2 m
+ = + =
A
kx
P P
From i deal gas equation
2
2 2
1
1 1
T
V P
T
V P
=
2
3 5 3 5
10 2 . 3 10 2
300
10 4 . 2 10
T
=
K T 800
2
=
Pr oblem 21. Two i dentical contai ners each of vol ume
0
V are j oi ned by a small pi pe. The contai ners contain i dentical
gases at temperature
0
T and pressure
0
P . One contai ner i s heated to temperature
0
2T while maintaining
the other at the same temperature. The common pressure of the gas is P and n is the number of moles of
gas in container at temperature
0
2T
(a)
0
2P P = (b)
0
3
4
P P = (c)
0
0 0
3
2
RT
V P
n = (d)
0
0 0
2
3
RT
V P
n =
Sol uti on : (b, c) I nitiall y for container A
0 0 0 0
RT n V P =
For contai ner B
0 0 0 0
RT n V P =
0
0 0
0
RT
V P
n =
Total number of moles
0 0 0
2n n n = + =
Since even on heati ng t he total number of moles i s conserved
Hence
0 2 1
2n n n = + ......(i)
I f P be the common pressure then
For contai ner A
0 1 0
2T R n PV =
0
0
1
2RT
PV
n =
For contai ner B
0 2 0
RT n PV =
0
0
2
RT
PV
n =
Substi tuti ng the val ue of
1 0
, n n and
2
n in equati on (i ) we get
0
0 0
0
0
0
0
. 2
2 RT
V P
RT
PV
RT
PV
= +
0
3
4
P P =
No. of mol es i n contai ner A (at temperature
0
2T ) =
0
0
1
2RT
PV
n =
0
0
0
2 3
4
RT
V
P 
.

\

=
0
0 0
3
2
RT
V P
=
=
0
3
4
As P P
Pr oblem 22. At the top of a mountai n a thermometer reads 7C and a barometer reads 70 cm of Hg. At the bottom of
the mountai n these read 27C and 76 cm of Hg respecti vel y. Comparison of density of air at the top with
that of bottom is
(a) 75/ 76
(b) 70/ 76
(c) 76/ 75
(d) 76/ 70
Sol uti on : (a) I deal gas equati on, in terms of density = =
2 2
2
1 1
1
T
P
T
P
constant
1
2
2
1
2
1
T
T
P
P
=
76
75
280
300
76
70
Top
Bottom
Bottom
Top
Bottom
Top
= = =
T
T
P
P
11.5 Vander Waal's Gas Equati on.
Al l real gases do not obey the i deal gas equati on. I n order to explai n the behavi our of real gases foll owi ng
two modi fi cati on are consi dered i n ideal gas equati on.
n0, V0
P0, T0
I ni ti al l y
n0, V0
P0, T0
(A) (B)
n1, V0
P, 2T0
Fi nal l y
n2, V0
P, T0
(A) (B)
7
o
C, 70 cm of Hg
27
o
C, 76 cm of Hg
Kineti c Theory of Gases 11
(i ) Nonzer o size of molecule : A certai n porti on of volume of a gas is covered by the molecules
themsel ves. Therefore the space avai lable for the free moti on of molecules of gas wi ll be sli ghtly less than the
volume V of a gas.
Hence the effecti ve volume becomes (V b)
(i i ) For ce of attr action between gas molecules : Due to thi s, molecule do not exert that force on the
wall whi ch they would have exerted i n the absence of i ntermol ecular force. Therefore the observed pressure P
of the gas wi ll be l ess than that present i n the absence of i ntermol ecul ar force. Hence the effective pressure
becomes 
.

\

+
2
V
a
P
The equati on obtai ned by usi ng above modi fi cati ons i n i deal gas equati on i s call ed Vander Waals equati on
or real gas equati on.
Vander Waal's gas equations
For 1 mole of gas
RT b V
V
a
P = 
.

\

+ ) (
2
For moles of gas
RT b V
V
a
P
=


.

\

+ ) (
2
2
Here a and b are constant called Vander Waal s constant.
Di mensi on : [ a] = ] [
2 5
T ML and [ b] = [L
3
]
Uni ts : a = N m
4
and b = m
3
.
11.6 Andr ews Cur ves.
The pressure (P) versus volume (V) curves for act ual gases are called Andrews curves.
(1) At 350C, part AB represents vapour phase of water, i n thi s
part Boyles law i s obeyed 
.

\

V
P
1
. Part BC represents the co
exi stence of vapour and l i quid phases. At poi nt C, vapours compl etely
change to li quid phase. Part CD i s parallel to pressure axi s which shows
that compressi bi li ty of the water i s negli gible.
(2) At 360C porti on representi ng the coexi stence of li qui d
vapour phase i s shorter.
(3) At 370C thi s porti on i s further decreased.
(4) At 374.1C, i t reduces to poi nt (H) call ed cri tical poi nt and the temperature 374.1C i s called cri ti cal
temperature (Tc) of water.
(5) The phase of water (at 380C) above the cri ti cal temperature i s cal led gaseous phase.
Cr iti cal temper atur e, pressur e and volume
The poi nt on the PV curve at whi ch the matter gets converted from gaseous state to l iqui d state i s known
as cri ti cal poi nt. At thi s poi nt the di fference between the liquid and vapour vani shes i .e. the densi ti es of li qui d
and vapour become equal.
G
Gas
380C
370C
360C
350C C
F
A
Vapour
Li qui d
Li qui d
vapour
r egi on
374.1C
P
V
H
Andr ews curve for water
B
E
D
12 Kineti c Theory of Gases
(i ) Cr itical temper atur e ( Tc) : The maxi mum temperature bel ow whi ch a gas can be li quefi ed by
pressure alone i s call ed cri ti cal temperature and i s characteri sti c of the gas. A gas cannot be li quefi ed i f i ts
temperature i s more than cri ti cal temperature.
CO2 (304.3 K), O2 (118C), N2 (147.1C) and H2O (374.1C)
(i i ) Critical pr essure ( Pc) : The mi ni mum pressure necessary to li qui fy a gas at cri ti cal temperature i s
defi ned as cri tical pressure.
CO2 (73.87 bar ) and O2 (49.7atm)
(i ii ) Critical volume ( Vc) : The volume of 1 mole of gas at cri ti cal pressure and cri ti cal temperature i s
defi ned as cri tical volume.
CO2 (95 10
6
m
3
)
(i v) Relation between Vander Waals constants and Tc, Pc, Vc :
Rb
a
T
c
27
8
= ,
2
27b
a
P
c
= , b V
c
3 = ,
c
c
P
T R
a
2 2
64
27
= ,


.

\

=
c
c
P
T R
b
8
and R
T
V P
c
c c
8
3
=
Sample pr oblems based on Vander Waal gas equati on
Pr oblem 23. Under which of the foll owing conditi ons is the law PV = RT obeyed most cl osel y by a real gas
[ NCERT 1974; MP PMT 1994, 97; MP PET 1999; AMU 2001]
(a) Hi gh pressure and high temperature (b) Low pressure and l ow temperature
(c) Low pressure and high temperature (d) High pressure and l ow temperature
Sol uti on : (c) At low pressure and high temperature real gas obey PV = RT i.e. they behave as ideal gas because at hi gh
temperature we can assume that there is no force of attracti on or repulsi on works among the molecules
and the volume occupied by the molecules is negligi ble in comparison to the volume occupied by the gas.
Pr oblem 24. The equati on of state of a gas is gi ven by ) (
2
b RT V
V
aT
P
c
+ =


.

\

+ , where a, b, c and R are constants. The
isotherms can be represented by
n m
BV AV P = , where A and B depend only on temperature then
[ CBSE PMT 1995]
(a) c m = and 1 = n (b) c m = and 1 = n (c) c m = and 1 = n (d) c m = and 1 = n
Sol uti on : (a) b RT V
V
aT
P
c
+ =


.

\

+
2
c c
bV RTV V aT P
+ = +
1 2
1 2
) ( ) (
+ = V aT V b RT P
c
By compari ng this equation with gi ven equati on
n m
BV AV P = we get c m = and 1 = n .
Pr oblem 25. An experi ment is carried on a fixed amount of gas at different temperatures and at hi gh pressure such that
it deviates from the i deal gas behavi our. The variation of
RT
PV
wi th P is shown i n the diagram. The correct
variation will correspond to
(a) Curve A
(b) Curve B
(c) Curve C
PV/ RT
P (at m) 0, 0
A
B
C
D
1.0
2.0
20 40 60 80 100
Kinetic Theory of Gases 13
(d) Curve D
Sol uti on : (b) At lower pressure we can assume that gi ven gas behaves as ideal gas so =
RT
PV
constant but when pressure
increase, the decrease i n volume wil l not take pl ace i n same proporti on so
RT
PV
wi ll i ncreases.
Pr oblem 26. The conversi on of i deal gas i nt o soli ds is
(a) Possi bl e only at l ow pressure (b) Possible only at l ow temperature
(c) Possi bl e only at l ow volume (d) I mpossi ble
Sol uti on : (d) Because there is zero attracti on between the molecules of ideal gas.
11.7 Var i ous Speeds of Gas Molecules.
The moti on of molecules i n a gas i s characteri sed by any of the foll owi ng three speeds.
(1) Root mean squar e speed : I t i s defi ned as the square root of mean of squares of the speed of
di fferent molecules i .e.
N
v v v v
v
rms
....
2
4
2
3
2
2
2
1
+ + + +
=
(i ) From the expressi on for pressure of i deal gas
2
3
1
rms
v
V
N m
P =
gas of Mass
3 3 PV
N m
PV
v
rms
= =
P 3
=
=
V
gas of Mass
As
(i i )
gas of Mass
3PV
v
rms
=
M
RT
M
RT 3 3
= =
(i ii )
m
kT
M N
kT N
M
RT
v
A
A
rms
3 3 3
= = = [ As M = NAm and R = NAk]
Root mean square veloci ty
m
kT
M
RT P
v
rms
3 3 3
= = =
I mpor t ant poi nt s
(i ) Wi th ri se i n temperature r ms speed of gas molecules i ncreases as T v
rms
.
(i i ) Wi th i ncrease i n mol ecul ar wei ght r ms speed of gas mol ecule decreases as
M
v
rms
1
.
e.g., r ms speed of hydrogen mol ecules i s four ti mes that of oxygen molecules at the same temperature.
(i i i ) r ms speed of gas mol ecul es i s of the order of km/ s
e.g., At NTP for hydrogen gas s m
M
RT
v
rms
/ 1840
10 2
273 31 . 8 3 3
) (
3
=
= = .
(i v) r ms speed of gas molecules i s
3
ti mes that of speed of sound i n gas
[ As i f M i s the mol ecul ar wei ght of
gas
PV = RT and Mass of gas = M ]
14 Kineti c Theory of Gases
As
M
RT
v
rms
3
= and
M
RT
v
s
=
s rms
v v
3
=
(v) r ms speed of gas mol ecules does not depends on the pressure of gas (i f temperature remai ns constant)
because P (Boyles law) i f pressure i s i ncreased n ti mes then densi ty wi ll al so i ncreases by n ti mes but vr ms
remai ns constant.
(vi ) Moon has no atmosphere because vr ms of gas molecules i s more than escape vel oci ty (ve).
A planet or satell i te wi ll have atmosphere onl y and only i f
e rms
v v <
(vi i ) At T = 0; vr ms = 0 i .e. the r ms speed of molecules of a gas i s zero at 0 K. Thi s temperature i s called
absol ute zero.
(2) Most probabl e speed : The parti cles of a gas have a range of speeds. Thi s i s defi ned as the speed
whi ch is possessed by maxi mum fracti on of total number of molecules of the gas. e.g., i f speeds of 10 mol ecul es
of a gas are 1, 2, 2, 3, 3, 3, 4, 5, 6, 6 km/ s, t hen the most probabl e speed i s 3 km/ s, as maxi mum fraction of t otal
molecules possess thi s speed.
Most probable speed
m
kT
M
RT P
v
mp
2 2 2
= = =
(3) Average speed : I t i s the arithmeti c mean of the speeds of mol ecul es i n a gas at gi ven t emperature.
N
v v v v
v
av
.....
4 3 2 1
+ + + +
=
and accordi ng to ki neti c theory of gases
Average speed
m
kT
M
RT P
v
av
8 8 8
= = =
N ot e : vr ms > vav > vmp (order rememberi ng tri ck) (RAM)
vr ms : vav : vmp = 2 : 5 . 2 : 3 2 :
8
: 3 =
For oxygen gas mol ecul es vr ms = 461 m/ s, vav = 424.7 m/ s and vr ms = 376.4 m/ s
Sample Pr oblems based on Var i ous speeds
Pr oblem 27. At room temperature, the r ms speed of the molecules of certain diatomi c gas is found to be 1930 m/ s. The
gas is
(a)
2
H (b)
2
F (c)
2
O (d)
2
Cl
Sol uti on : (a) Root means square vel ocity s m
M
RT
v
rms
/ 1930
3
= = (given)
gm kg
RT
M 2 10 2
1930 1930
300 31 . 8 3
) 1930 (
3
3
2
= =
= =
i .e. the gas is hydrogen.
Kinetic Theory of Gases 15
Pr oblem 28. Let A and B the two gases and given :
B
B
A
A
M
T
M
T
. 4 = ; where T is the temperature and M is the molecular
mass. I f
A
C and
B
C are the rms speed, then the ratio
B
A
C
C
will be equal to [ BHU 2003]
(a) 2 (b) 4 (c) 1 (d) 0.5
Sol uti on : (a) As
M
RT
v
rms
3
= 2 4
/
/
= = =
B A
B A
B
A
M M
T T
C
C
= given 4 As
B
A
B
A
M
M
T
T
Pr oblem 29. The r ms speed of the mol ecules of a gas i n a vessel is 400 ms
1
. I f half of the gas l eaks out at constant
temperature, the r ms speed of the remai ning molecules wi ll be [ Ker al a ( Engg.) 2002]
(a) 800 ms
1
(b)
1
2 400
ms (c) 400 ms
1
(d) 200 ms
1
Sol uti on : (c) Root mean square vel ocity does not depends upon the quantity of gas. For a gi ven gas and at constant
temperature it al ways remains same.
Pr oblem 30. The root mean square speed of hydrogen molecules at 300 K is 1930 m/ s. Then the root mean square
speed of oxygen mol ecules at 900 K wi ll be [ MH CET 20 02]
(a) s m / 3 1930 (b) 836 m/ s (c) 643 m/ s (d) s m /
3
1930
Sol uti on : (b)
M
RT
v
rms
3
=
2
2
2
2
2
2
O
O
H
H
O
H
T
M
M
T
v
v
=
900
32
2
300 1930
2
=
O
v
s m v
O
/ 836
4
3 1930
2
=
= .
Pr oblem 31. At what temperature is the root mean square vel oci ty of gaseous hydrogen mol ecules is equal to that of
oxygen molecules at 47C [ CPMT 1985; MP PET 1997; RPET 1999; AI EEE 200 2]
(a) 20 K (b) 80 K (c) 73 K (d) 3 K
Sol uti on : (a) For oxygen
2
2
2
3
O
O
O
M
RT
v = and For hydrogen
2
2
2
3
H
H
H
M
T
R v =
Accordi ng to probl em
2
2
3
O
O
M
RT
=
2
2
3
H
H
M
T
R =
2
2
2
2
H
H
O
O
M
T
M
T
=
2 32
273 47
2
H
T
=
+
K T
H
20 2
32
320
2
= = .
Pr oblem 32. Cooki ng gas contai ners are kept i n a lorry movi ng with uniform speed. The temperature of the gas
molecules i nsi de wi ll [ AI EEE 2002]
(a) I ncrease (b) Decrease
(c) Remai n same (d) Decrease for some, whi le increase for others
Sol uti on : (c) I f a lorry is moving with constant velocity then the
rms
v of gas molecul e i nsi de the contai ner will not
change and we know that
2
rms
v T . So temperature remai ns same.
Pr oblem 33. The speeds of 5 mol ecules of a gas (i n arbi trary units) are as follows : 2, 3, 4, 5, 6. The root mean square
speed for these mol ecules i s [ MP PMT 2000]
(a) 2.91 (b) 3.52 (c) 4.00 (d) 4.24
Sol uti on : (d)
5
6 5 4 3 2
5
2 2 2 2 2 2
5
2
4
2
3
2
2
2
1
+ + + +
=
+ + + +
=
v v v v v
v
rms
24 . 4 20
5
100
= = =
16 Kineti c Theory of Gases
Pr oblem 34. Gas at a pressure
0
P in contained as a vessel . I f the masses of al l the molecul es are halved and thei r
speeds are doubl ed, the resul ting pressure P wil l be equal to
[ NCERT 1984; MNR 1995; MP PET 1997; MP PMT 1997; RPET 1999; UPSEAT 1999, 20 00]
(a)
0
4P (b)
0
2P (c)
0
P (d)
2
0
P
Sol uti on : (b)
2
3
1
rms
v
V
mN
P =
2
rms
v m P so 2
2 2 /
2
1
1
1
1
2
1
2
1
2
1
2
=


.

\

=


.

\

=
v
v
m
m
v
v
m
m
P
P
0 1 2
2 2 P P P = =
Pr oblem 35. Let
rms
v v, and
mp
v respecti vely denote the mean speed, root mean square speed and most probable
speed of the molecules in an i deal monoatomi c gas at absol ute temperature T. The mass of a molecule is
m. Then
[ I I TJEE 1998]
(a) No molecule can have speed greater than
rms
v 2
(b) No molecule can have speed less than 2 /
mp
v
(c)
rms mp
v v v < <
(d) The average ki netic energy of a mol ecule i s
2
4
3
mp
mv
Sol uti on : (c, d) We know that
M
RT
v
rms
3
= ,
M
RT
v
av
8
= and
M
RT
v
mp
2 =
2 : 5 . 2 : 3 : : =
mp av rms
v v v so
rms av mp
v v v < <
and
2
3
=
mp
rms
v
v
or
2 2
2
3
mp rms
v v = Average ki neti c energy
2 2
2
3
2
1
2
1
mp rms
v m v m = =
2
4
3
mp
mv = .
Pr oblem 36. The root mean square speed of the molecules of a di at omic gas is v. When the temperature i s doubl ed, the
molecules dissociate into two atoms. The new root mean square speed of the atom is
(a) v 2 (b) v (c) 2v (d) 4v
Sol uti on : (c)
M
RT
v
rms
3
= . According to problem T will becomes T/ 2 and M will becomes M/ 2 so the val ue of
rms
v wil l
increase by 2 4 = times i .e. new root mean square vel oci ty wil l be 2v.
Pr oblem 37. The mol ecules of a gi ven mass of a gas have a r ms vel oci ty of 200 m/ sec at 27C and
2 5
/ 10 0 . 1 m N
pressure. When the temperature is 127C and pressure i s
2 5
/ 10 5 . 0 m N , the r ms vel ocit y i n m/ sec wi ll
be
[ AI I MS 1985; MP PET 1992]
(a)
3
2 100
(b) 2 100 (c)
3
400
(d) None of these
Sol uti on : (c) Change in pressure will not affect the r ms velocity of molecules. So we will calculate only the effect of
temperature.
As T v
rms
4
3
400
300
400
300
= =
o
o
v
v
4
3 200
400
=
v
s m v /
3
400
3
2 200
400
=
= .
Pr oblem 38. Which of the fol lowi ng statement is true [ I I TJEE 1981]
(a) Absolute zero degree temperature is not zero energy temperature
(b) Two different gases at the same temperature pressure have equal root mean square vel ociti es
Kinetic Theory of Gases 17
(c) The rms speed of the mol ecules of different i deal gases, maintai ned at the same temperature are the
same
(d) Given sampl e of 1cc of hydrogen and 1cc of oxygen both at N.T.P.; oxygen sample has a large number
of mol ecules
Sol uti on : (a) At absolute temperature ki neti c energy of gas molecules becomes zero but they possess potential energy
so we can say that absolute zero degree temperature is not zero energy temperature.
Pr oblem 39. The ratio of r ms speeds of the gases in the mixture of ni trogen oxygen will be
(a) 1 : 1 (b) 1 : 3 (c) 7 : 8 (d) 7 : 6
Sol uti on : (c)
M
RT
v
rms
3
=
7
8
28
32
2
2
2
2
= = =
N
O
O
N
M
M
v
v
Pr oblem 40. A vessel i s partiti oned i n two equal hal ves by a fixed diathermic separator. Two di fferent i deal gases are
fil led in left (L) and right (R) hal ves. The r ms speed of the molecules in L part is equal to the mean speed
of molecules in the R part. Then the ratio of the mass of a molecul e in L part to that of a molecule i n R
part is
(a)
2
3
(b) 4 /
(c) 3 / 2
(d) 8 / 3
Sol uti on : (d) Root means square vel ocity of molecul e i n left part
L
rms
m
KT
v
3
=
Mean or average speed of molecul e in right part
R
av
m
KT
v
8
=
Accordi ng to probl em
R L
m
KT
m
KT
8 3
=
R L
m m
8 3
=
8
3
=
R
L
m
m
.
Pr oblem 41. An ideal gas ( = 1.5) i s expanded adiabati cal l y. How many ti mes has the gas to be expanded to reduce the
root mean square vel oci ty of molecul es 2 ti mes
(a) 4 ti mes (b) 16 ti mes (c) 8 ti mes (d) 2 ti mes
Sol uti on : (b) To reduce the r ms veloci ty two times, temperature should be reduced by four ti mes (As T v
rms
)
T T =
1
4
2
T
T = , V V =
1
From adiabatic law =
1
TV constant we get 4
2
1
1
1
2
= =


.

\

T
T
V
V
1
1
1
2
) 4 (
=
V
V
[ = 3/ 2 gi ven]
1 2 / 3
1
1 2
) 4 (
= V V
2
1
) 4 ( V =
1
16 V = 16
1
2
=
V
V
11.8 Ki neti c Ener gy of I deal Gas.
R
L
18 Ki netic Theory of Gases
Molecules of i deal gases possess onl y translati onal moti on. So they possess onl y translati onal ki neti c
energy.
Quantity of gas Kinetic ener gy
Kineti c energy of a gas mol ecule (Emolecule)
2
2
1
rms
v m = 
.

\

=
m
kT
m
3
2
1
kT
2
3
=
m
kT
v
rms
3
As
Kineti c energy of 1 mol e (M gr am) gas (Emole)
2
2
1
rms
v M =
M
RT
M
3
2
1
= RT
2
3
=
=
M
RT
v
rms
3
As
Kineti c energy of 1 gm gas (Egr am)
T
N m
N k
T
M
R
A
A
2
3
2
3
= = rT T
m
k
2
3
2
3
= =
Here m = mass of each molecule, M = Mol ecul ar wei ght of gas and NA = Avogadro number = 6.023 10
23
I mpor t ant poi nt s
(1) Ki neti c energy per molecule of gas does not depends upon the mass of the molecule but only depends
upon the temperature of the gas.
As kT E
2
3
= or E T i.e. molecules of di fferent gases say He, H2 and O2 etc. at same temperature wi l l
have same transl ati onal ki neti c energy though their r ms speed are different.
=
m
kT
v
rms
3
(2) Ki neti c energy per mole of gas depends only upon the temperature of gas.
(3) Ki netic energy per gr am of gas depend upon the temperature as wel l as molecular wei ght (or mass of
one molecule) of the gas.
T
m
k
E
gram
2
3
=
m
T
E
gram
From the above expressi ons i t is clear that hi gher the temperature of the gas, more wi ll be the average
ki neti c energy possessed by the gas molecules at T = 0, E = 0 i .e. at absolute zero the mol ecular moti on stops.
Sample Pr oblems based on Kinetic ener gy
Pr oblem 42. Read the gi ven statements and deci de which is/ are correct on the basis of ki netic theory of gases[ MP PMT 200 3]
(I ) Energy of one molecule at absol ute temperature is zero
(I I ) rms speeds of di fferent gases are same at same temperature
(I I I ) For one gram of al l i deal gas kineti c energy is same at same temperature
(I V) For one mole of al l ideal gases mean ki netic energy is same at same
temperature
(a) All are correct (b) I and I V are correct (c) I V is correct (d) None of these
Sol uti on : (c) I f the gas i s not i deal then its mol ecule wi ll possess potential energy. Hence statement (I ) is wrong.
rms speed of different gases at same temperature depends on its molecular weight


.

\

M
v
rms
1
. Hence
statement (I I ) also wrong.
Kinetic Theory of Gases 19
Kineti c energy of one gr am gas depends on the mol ecular wei ght 
.

\

M
E
gm
1
. Hence statement (II I) also
wrong.
But K.E. of one mol e of i deal gas does not depends on the molecular wei ght 
.

\

= RT E
2
3
. Hence (IV) is
correct.
Pr oblem 43. At whi ch of the fol lowing temperature woul d the molecules of a gas have twice the average ki netic energy
they have at 20C [ MP PET 1992; BVP 20 03]
(a) 40C (b) 80C (c) 313C (d) 586C
Sol uti on : (c) T E
1
2
1
2
T
T
E
E
=
) 273 20 (
2
2
1
1
+
=
T
E
E
C K T = = = 313 586 2 293
2
.
Pr oblem 44. A vessel contai ns a mixture of one mole of oxygen and two moles of nitrogen at 300 K. The rati o of the
average rotational ki netic energy per
2
O molecul e to that per
2
N mol ecule is [ I I TJEE 1998; DPMT 2000]
(a) 1 : 1
(b) 1 : 2
(c) 2 : 1
(d) Depends on the moments of i nert ia of the two molecul es
Sol uti on : (a) Ki netic energy per degree of freedom kT
2
1
=
As diatomi c gas possess two degree of freedom for rotati onal moti on therefore rotati onal
K.E. kT kT = 
.

\

=
2
1
2
I n the problem both gases (oxygen and ni trogen) are diatomic and have same temperature (300 K)
therefore ratio of average rotati onal kinetic energy wil l be equal to one.
Pr oblem 45. A gas mixture consists of molecul es of type 1, 2 and 3 with mol ar masses
3 2 1
m m m > > .
rms
v and K are
the r ms speed and average ki netic energy of the gases. Which of the foll owi ng i s true
(a)
3 2 1
) ( ) ( ) (
rms rms rms
v v v < < and
3 2 1
) ( ) ( ) ( K K K = = (b)
3 2 1
) ( ) ( ) (
rms rms rms
v v v = = and
3 2 1
) ( ) ( ) ( K K K > =
(c)
3 2 1
) ( ) ( ) (
rms rms rms
v v v > > and
3 2 1
) ( ) ( ) ( K K K > < (d)
3 2 1
) ( ) ( ) (
rms rms rms
v v v > > and
3 2 1
) ( ) ( ) ( K K K < <
Sol uti on : (a) The rms speed depends upon the molecular mass
M
v
rms
1
but kinetic energy does not depends on it
0
M E
I n the problem
3 2 1
m m m > >
3 2 1
) ( ) ( ) (
rms rms rms
v v v < < but ) ( ) ( ) (
3 2 1
K K K = =
Pr oblem 46. The kinetic energy of one gram mole of a gas at normal temperature and pressure is (R = 8.31 J/ moleK)
[ AFMC 1998; MH CET 1999; Pb. PMT 2000]
(a) J
4
10 56 . 0 (b) J
2
10 3 . 1 (c) J
2
10 7 . 2 (d) J
3
10 4 . 3
Sol uti on : (d)
3
10 4 . 3 273 31 . 8
2
3
2
3
= = = RT E Joule
Pr oblem 47. The average translational ki netic energy of
2
O (molar mass 32) molecul es at a particular temperature is 0.048
eV. The translati onal ki netic energy of
2
N (mol ar mass 28) molecules in eV at the same temperature is
[ I I TJEE 1997 ReExam]
(a) 0.0015 (b) 0.003 (c) 0.048 (d) 0.768
20 Kinetic Theory of Gases
Sol uti on : (c) Average translational kineti c energy does not depends upon the molar mass of the gas. Di fferent gases wi ll
possess same average translati onal kineti c energy at same temperature.
Pr oblem 48. The average translati onal energy and the r ms speed of molecul es in a sample of oxygen gas at 300 K are
J
21
10 21 . 6
and 484 m/ s respecti vel y. The corresponding val ues at 600 K are nearly (assuming i deal
gas behavi our) [ I I TJEE 1997 Cancelled]
(a) s m J / 968 , 10 42 . 12
21
(b) s m J / 684 , 10 78 . 8
21
(c) s m J / 968 , 10 21 . 6
21
(d) s m J / 684 , 10 42 . 12
21
Sol uti on : (d) T E but T v
rms
i .e. if temperature becomes twice then energy will becomes two ti me i .e. 2 6.21 10
21
= 12.42 10
21
J
But r ms speed will become 2 times i .e. s m/ 684 2 484 = .
Pr oblem 49. A box contai ni ng N mol ecules of a perfect gas at temperature
1
T and pressure
1
P . The number of
molecules i n the box i s doubled keepi ng the total ki netic energy of the gas same as before. I f the new
pressure is
2
P and temperature
2
T , then
(a)
1 2
P P = ,
1 2
T T = (b)
1 2
P P = ,
2
1
2
T
T = (c)
1 2
2P P = ,
1 2
T T = (d)
1 2
2P P = ,
2
1
2
T
T =
Sol uti on : (b) Ki netic energy of N molecul e of gas NkT E
2
3
=
I nitiall y
1 1 1
2
3
kT N E = and final ly
2 2 2
2
3
kT N E =
But accordi ng to problem
2 1
E E = and
1 2
2N N =
2 1 1 1
) 2 (
2
3
2
3
kT N kT N =
2
1
2
T
T =
Since the kinetic energy constant
2 2 1 1
2
3
2
3
kT N kT N =
2 2 1 1
T N T N = NT = constant
From i deal gas equation of N molecule NkT PV =
2 2 1 1
V P V P =
2 1
P P =
2 1
As [ V V = and NT = constant]
Pr oblem 50. Three closed vessel s A, B and C are at the same temperature T and contai n gases which obey the
Maxwell ian distributi on of veloci ties. Vessel A contai ns onl y
2
O , B only
2
N and C a mixture of equal
quanti ties of
2
O and
2
N . I f the average speed of the
2
O mol ecules in vessel A is
1
V , that of the
2
N
molecules i n vessel B is
2
V , the average speed of the
2
O mol ecules in vessel C i s (where M i s the mass of
an oxygen molecul e) [ I I TJEE 1992]
(a) 2 / ) (
2 1
V V + (b)
1
V (c)
2 / 1
2 1
) ( V V (d) M kT / 3
Sol uti on : (b) Average speed of gas molecul e
m
kT
v
av
8
= . I t depends on temperature and molecular mass. So the
average speed of oxygen wil l be same in vessel A and vessel C and that is equal to
1
V .
Pr oblem 51. The graph which represent the vari ati on of mean ki neti c energy of mol ecules wi th temperature tC is
(a) (b) (c) (d)
E
t
E
t
E
t
E
t
Kinetic Theory of Gases 21
Sol uti on : (c) Mean K.E. of gas mol ecule kT E
2
3
= ) 273 (
2
3
+ = t k where T = temperature i s i n kelvin and t = is in
centi grade
k t k E 273
2
3
2
3
+ = k = Boltzmann's constant
By compari ng this equation with standard equati on of straight line c mx y + =
We get k m
2
3
= and k c 273
2
3
= . So the graph between E and t will be straight line with posi ti ve i ntercept
on Eaxis and posi ti ve slope with taxis.
11.9 Gas Laws.
(1) Boyles law : For a gi ven mass of an i deal gas at constant temperature, the volume of a gas i s
i nversely proporti onal to i ts pressure.
i .e.
P
V
1
or PV = constant or
2 2 1 1
V P V P = [ I f m and T are constant]
(i ) PV = =


.

\

m
P constant [ As volume
m
= ]
constant =
P
or
2
2
1
1
P P
= [ As m = constant]
(i i ) PV = constant = 
.

\

n
N
P [ As number of molecules per unit volume
V
N
n =
n
N
V = ]
constant =
n
P
or
2
2
1
1
n
P
n
P
= [ As N = constant]
(i ii ) Accordi ng to ki neti c theory of gases
2
3
1
rms
v
V
mN
P =
T
V
P
gas of mass
[ As T v
rms
and mN = Mass of gas]
I f mass and temperature of gas remai n constant then
V
P
1
. Thi s i s i n accordance wi th Boyles l aw.
(i v) Graphi cal representati on : I f m and T are constant
PV
V
P
1/ V
V
1/ P
P
V
PV
P
22 Kinetic Theory of Gases
Sample Pr oblems based on Boyle's law
Pr oblem 52. At constant temperature on i ncreasing the pressure of a gas by 5% wil l decrease its volume by[ MP PET 200 2]
(a) 5% (b) 5.26% (c) 4.26% (d) 4.76%
Sol uti on : (d) I f P P =
1
then + = P P
2
5% of P = 1.05 P
From Boyl es law PV = constant
P
P
P
P
V
V
05 . 1
2
1
1
2
= =
105
100
=
Fracti onal change i n vol ume
1
1 2
V
V V
V
V
=
A
=
105
5
105
105 100
=
=
Percentage change i n volume % 76 . 4 % 100
105
5
% 100 = =
A
V
V
i .e. volume decrease by 4.76%.
Pr oblem 53. A cyl inder contai ned 10 kg of gas at pressure
2 7
/ 10 m N . The quanti ty of gas taken out of cyli nder i f final
pressure is m N / 10 5 . 2
6
is (assume the temperature of gas i s constant) [ EAMCET ( Med.) 1998]
(a) Zero (b) 7.5 kg (c) 2.5 kg (d) 5 kg
Sol uti on : (b) At constant temperature for the gi ven vol ume of gas
2
1
2
1
m
m
P
P
=
2
6
7
10
10 5 . 2
10
m
=
kg m 5 . 2
10
10 10 5 . 2
7
6
2
=
=
The quantity of gas taken out of the cyl inder = 10 2.5 = 7.5 kg.
Pr oblem 54. I f a given mass of gas occupies a volume of 10 cc at 1 atmospheric pressure and temperature of 100C
(373.15 K). What wil l be i ts volume at 4 atmospheri c pressure; the temperature being the same[ NCERT 1977]
(a) 100 cc (b) 400 cc (c) 2.5 cc (d) 104 cc
Sol uti on : (c)
V
P
1
2
1
1
2
P
P
V
V
= cc V 5 . 2
4
1
10
2
= 
.

\

=
Pr oblem 55. An air bubble of vol ume
0
V i s released by a fi sh at a depth h i n a lake. The bubble rises to the surface.
Assume constant temperature and standard atmospheric pressure P above the lake. The volume of the
bubbl e just before touchi ng the surface will be (density of water is )
(a)
0
V (b) ) / (
0
P gh V (c)

.

\

+
P
gh
V
1
0
(d) 
.

\

+
P
gh
V
1
0
Sol uti on : (d) Accordi ng to Boyles l aw mul ti pl icati on of pressure and volume wi ll remains constant at t he bottom and
top.
I f P is the atmospheric pressure at the top of the lake and the
volume of bubble i s V then from
2 2 1 1
V P V P =
PV V g h P = +
0
) (
0
V
P
g h P
V 
.

\
 +
=
P2V2
(P1 V1)
h
Ki netic Theory of Gases 23
+ =
P
gh
V V
1
0
Pr oblem 56. The adj oi ning figure shows graph of pressure and volume of a gas at two temperatures
1
T and
2
T . Whi ch
of the foll owi ng i nterferences i s correct
(a)
2 1
T T >
(b)
2 1
T T =
(c)
2 1
T T <
(d) No interference can be drawn
Sol uti on : (c) For a gi ven pressure, volume will be more i f temperature is more (Charles law)
From the graph it is clear that V2 > V1
T2 > T1
(2) Char le's law
(i ) I f the pressure remai ns constant, the volume of the gi ven mass of a gas i ncreases or decreases by
15 . 273
1
of i ts volume at 0C for each 1C ri se or fall i n temperature.

.

\

+ = t V V
t
15 . 273
1
1
0
. Thi s is Charles l aw for centi grade
scale.
(i i ) I f the pressure remai ni ng constant, the volume of the gi ven mass of
a gas i s di rectly proporti onal to i ts absolute temperature.
V T or constant =
T
V
or
2
2
1
1
T
V
T
V
= [ I f m and P are constant]
(i ii ) =
T
V
constant =
T
m
[ As volume
m
V = ]
or constant = T or
2 2 1 1
T T = [ As m = constant]
(i v) Accordi ng to ki net i c theory of gases
2
3
1
rms
v
V
mN
P =
or T
V
P
gas of Mass
I f mass and pressure of the gas remai ns constant then V T. This i s i n accordance wi th Charles law.
(v) Graphi cal representati on : I f m and P are constant
1/ V
T
V/ T
T or 1/ T
V/ T
V or 1/ V
V
T
V
1/ T
[ Al l temper at ure T are i n
kel vi n]
273.15 O
t(C)
V0
Vt
T1
T2
P
V
p
V1 V2
24 Kinetic Theory of Gases
Sample pr oblems based on Char le's l aw
Pr oblem 57. A perfect gas at 27C is heated at constant pressure t o 327C. I f ori gi nal volume of gas at 27C is V then
volume at 327C i s [ CPMT 2002]
(a) V (b) 3V (c) 2V (d) V/ 2
Sol uti on : (c) From Charles law T V
1
2
1
2
T
T
V
V
= 2
300
600
273 27
273 327
= =
+
+
= . 2
2
V V =
Pr oblem 58. Hydrogen gas is filled in a balloon at 20C. I f temperature i s made 40C, pressure remaini ng same, what
fraction of hydrogen wil l come out [ MP PMT 2002]
(a) 0.07 (b) 0.25 (c) 0.5 (d) 0.75
Sol uti on : (a) As T V
1
2
1
2
T
T
V
V
=
1 2
293
313
V V 
.

\

=
Fracti on of gas comes out 07 . 0
293
20 293
313
1
1 1
1
1 2
= =

.

\

=
=
V
V V
V
V V
.
Pr oblem 59. The expansion of unit mass of a perfect gas at constant pressure i s shown in the diagram. Here
(a) a = volume, b = C temperature
(b) a = volume, b = K temperature
(c) a = C temperature, b = vol ume
(d) a = K temperature, b = volume
Sol uti on : (c) I n the gi ven graph l i ne have a positi ve slop wi th Xaxis and negati ve i ntercept on Yaxis.
So we can wri te the equation of li ne y = mx c ...... (i )
Accordi ng to Charles law
0
0
273
V t
V
V
t
+ = , by rewri ti ng thi s equati on we get
273
273
0


.

\

=
t
V
V
t ......(ii )
By compari ng (i) and (ii ) we can say that ti me i s represented on Yaxis and volume in Xaxis.
Pr oblem 60. A gas is fi lled i n the cylinder shown in the fi gure. The two pi stons are j oi ned by a string. I f the gas is
heated, the pistons will
(a) Move towards l eft
(b) Move towards ri ght
(c) Remai n stati onary
(d) None of these
a
b
O
Gas
Ki netic Theory of Gases 25
Sol uti on : (b) When temperature of gas increases i t expands. As the crosssectional area of ri ght pi ston is more,
therefore greater force will work on i t (because F = PA). So piston will move towards right.
Pr oblem 61. An i deal gas is i ni tially at a temperature T and volume V. I ts vol ume is increased by AV due t o an i ncrease
in temperature AT, pressure remaini ng constant. The quanti ty
T V
V
A
A
= vari es wi th temperature as
(a) (b) (c) (d)
Sol uti on : (c) From i deal gas equation PV = RT ..(i)
or T R V P A = A ..(ii)
Divi di ng equati on (ii) by (i) we get
T
T
V
V A
=
A
= =
A
A
T T V
V 1
(gi ven)
T
1
= . So the graph between and T will be rectangular hyperbol a.
(3) GayLussacs l aw or pr essure law
(i ) The volume remai ni ng constant, the pressure of a gi ven mass of a gas i ncreases or decreases by
15 . 273
1
of i ts pressure at 0C for each 1C ri se or fall i n temperature.
+ = t P P
t
15 . 273
1
1
0
Thi s i s pressure law for centi grade scale.
(i i ) The volume remai ni ng constant, the pressure of a gi ven mass of
a gas i s di rectly proporti onal to i ts absolute temperature.
P T or constant =
T
P
or
2
2
1
1
T
P
T
P
= [ I f m and V are constant ]
(i ii ) Accordi ng to ki neti c theory of gases
2
3
1
rms
v
V
N m
P = [ As T v
rms
2
]
or T
V
P
gas of mass
I f mass and volume of gas remai ns constant then P T. Thi s i s i n accordance with Gay Lussacs law.
(4) Gr aphical repr esentation : I f m and V are constants
273.15 O
t(C)
P0
Pt
P
T
P/ T
T or 1/ T T
1/ P P/ T
P or 1/ P 1/ T
P
[ Al l temper at ure T are i n
kel vi n]
T + AT T
(Temp. K)
T + AT T
(Temp. K)
T + AT T
(Temp. K)
T + AT T
(Temp. K)
26 Kinetic Theory of Gases
Sample pr oblems based on Gay Lussac's law
Pr oblem 62. On 0C pressure measured by barometer i s 760 mm. What wil l be pressure on 100C [ AFMC 20 02]
(a) 760 mm (b) 730 mm (c) 780 mm (d) None of these
Sol uti on : (d) From Gay Lussacs law
273
373
273 0
273 100
1
2
1
2
= 
.

\

+
+
= =
T
T
P
P
mm P 1038 760
273
373
2
= 
.

\

= .
Pr oblem 63. I f pressure of a gas contai ned i n a cl osed vessel is i ncreased by 0.4% when heated by 1C, the ini tial
temperature must be [ NCERT 1982; EAMCET ( Engg.) 1995; RPMT 1996; MP PET 1999]
(a) 250 K (b) 250C (c) 2500 K (d) 25C
Sol uti on : (a) P P =
1
, T1 = T , + = P P
2
(0.4% of P)
250 100
4 . 0 P
P P P + = + = 1
2
+ = T T
From Gay Lussac's law
2
1
2
1
T
T
P
P
=
1
250
+
=
+
T
T
P
P
P
[ As V = constant for cl osed vessel]
By solvi ng we get T = 250 K.
Pr oblem 64. Pressure versus temperature graph of an i deal gas of equal number of moles of different vol umes are
plotted as shown i n fi gure. Choose the correct al ternati ve
(a)
4 3 2 1
, V V V V = = and
3 2
V V >
(b)
4 3 2 1
, V V V V = = and
3 2
V V <
(c)
4 3 2 1
V V V V = = =
(d)
1 2 3 4
V V V V > > >
Sol uti on : (a) From i deal gas equation RT PV = T
V
R
P
=
Compari ng this equation with mx y =
Slope of li ne
V
R
m
= = tan i .e.
tan
1
V
I t means li ne of smaller sl ope represent greater volume of gas.
For the given problem figure
Point 1 and 2 are on the same li ne so they wil l represent same vol ume i .e.
2 1
V V =
Similarl y poi nt 3 and 4 are on the same l ine so they wi ll represent same vol ume i .e.
4 3
V V =
But
3 1
V V > (=
4
V ) or
3 2
V V > (=
4
V ) as slope of li ne 12 i s l ess than 34.
(5) Avogadr os law : Equal vol ume of all the gases under si mi lar condi ti ons of temperature and
pressure contai n equal number of molecules.
Accordi ng to ki neti c theory of gases
2
3
1
rms
v N m PV =
For fi rst gas,
2
) 1 ( 1 1
3
1
rms
v N m PV =
..(i )
P
T
V = constant
P
T
1
3 2
4
Kinetic Theory of Gases 27
For second gas,
2
) 2 ( 2 2
3
1
rms
v N m PV = ..(i i )
From (i ) and (i i )
2
2 2 2
2
1 1 1 rms rms
v N m v N m = ..(i i i )
As the two gases are at the same temperature kT v m v m
rms rms
2
3
2
1
2
1
2
2 2
2
1 1
= =
2
2 2
2
1 1 rms rms
v m v m = ..(i v)
So from equati on (i i i ) we can say that
2 1
N N = . Thi s i s Avogadros law.
(i ) Avogadr os number ( NA) : The number of molecules present i n 1 gm mol e of a gas i s defined as
Avogadro number.
23
10 023 . 6 =
A
N per gm mole
26
10 023 . 6 = per kg mol e.
(i i ) At S.T.P. or N.T.P. (T = 273 K and P = 1 at m) 22.4 l itr e of each gas has
23
10 023 . 6 molecule.
(i ii ) One mole of any gas at S.T.P. occupy 22.4 l i tr e of volume
Example : 32 gm oxygen, 28 gm ni trogen and 2gm hydrogen occupy the same vol ume at S.T.P.
(i v) For any gas 1 mol e = M gr am = 22.4 li t r e = 6.023 10
23
molecule.
Sample problems based on Avogadr o's Law
Pr oblem 65. Temperature of an i deal gas is T K and average ki neti c energy is
23
10 07 . 2
= E T Joule/ molecul e.
Number of molecules in 1 l i tr e gas at S.T.P. wil l be [ CPMT 1994]
(a)
22
10 68 . 2 (b)
25
10 68 . 2 (c)
28
10 68 . 2 (d)
22
10 68 . 1
Sol uti on : (a) As we know t hat at S.T.P. 22.4 li tre of gas contains
23
10 023 . 6 mol ecules
1 l i tr e of gas contain
22
23
10 68 . 2
4 . 22
10 023 . 6
=
P
v
rms
3
= or
rms
v
and rate of di ffusi on of a gas i s proporti onal to i ts r ms vel oci ty i .e.,
rms
v r
1
r or
1
2
2
1
=
r
r
(7) Daltons law of partial pressur e : The total pressure exerted by a mi xture of nonreacti ng gases
occupyi ng a vessel i s equal to the sum of the i ndi vi dual pressures whi ch each gases exert i f it al one occupi ed the
same volume at a gi ven temperature.
For n gases
n
P P P P P .....
3 2 1
+ + + =
where P = Pressure exerted by mi xture and =
n
P P P P ...... , , ,
3 2 1
Parti al pressure of component gases.
Sample pr oblems based on Dalton's law
Pr oblem 68. The capaci ty of a vessel is 3 l i tr es. I t contains 6 gm oxygen, 8 gm nitrogen and 5 gm
2
CO mixture at 27C.
I f R = 8.31 J/ mol e kelvi n, then the pressure i n the vessel i n
2
/ m N wil l be (approx.)
(a)
5
10 5 (b)
4
10 5 (c)
6
10 (d)
5
10
Sol uti on : (a) Daltons l aw
+ + = + + = + + = + + =
3
3
2
2
1
1
3 2 1
3 2 1
3 2 1
] [
M
m
M
m
M
m
V
RT
V
RT
V
RT
V
RT
V
RT
P P P P
2 5 3 3
3
/ 10 5
~
10 500
~
10 498
44
5
28
8
32
6
10 3
300 31 . 8
m N = = =
+ +
=
.
Pr oblem 69. Two gases occupy two containers A and B the gas i n A, of volume
3
10 . 0 m , exerts a pressure of 1.40 MPa
and that in B of volume
3
15 . 0 m exerts a pressure 0.7 MPa. The two contai ners are united by a tube of
negli gi bl e volume and the gases are all owed to i ntermi ngl e. Then it the temperature remai ns constant, the
final pressure i n the contai ner wi ll be (in MPa)
(a) 0.70 (b) 0.98 (c) 1.40 (d) 2.10
Sol uti on : (b) As the quanti ty of gas remains constant = +
B A
RT
V V P
RT
V P
RT
V P
B A B B A A
) ( +
= +
15 . 0 1 . 0
15 . 0 7 . 0 1 . 0 4 . 1
+
+
=
+
+
=
B A
B B A A
V V
V P V P
P MPa P 98 . 0 = .
Pr oblem 70. The temperature, pressure and vol ume of two gases X and Y are T, P and V respecti vel y. When the gases
are mixed then the vol ume and temperature of mixture become V and T respecti vely. The pressure and
mass of the mixture will be
(a) 2P and 2M (b) P and M (c) P and 2M (d) 2P and M
Sol uti on : (a) From Dal tons law, Pressure of mi xture P P P P P 2
2 1
= + = + =
Similarl y mass also wi ll become double i .e. 2M.
Ki netic Theory of Gases 29
Pr oblem 71. A closed vessel contains 8g of oxygen and 7g of ni trogen. The total pressure i s 10 atm at a given
temperature. I f now oxygen is absorbed by i ntroduci ng a suitable absorbent the pressure of the remai ni ng
gas in atm wil l be
(a) 2 (b) 10 (c) 4 (d) 5
Sol uti on : (d) From Dal tons law fi nal pressure of the mi xture of nitrogen and oxygen
2 1
P P P + =
V
RT
V
RT
2 1
+ =
V
RT
M
m
V
RT
M
m
2
2
1
1
+ =
V
RT
V
RT
V
RT
2 28
7
32
8
= + =
V
RT
2
10 = ..(i)
When oxygen i s absorbed then for ni trogen let pressure i s
V
RT
P
28
7
=
V
RT
P
4
= ..(ii )
From equati on (i) and (ii ) we get pressure of the nitrogen 5 = P atm.
(8) I deal gas equation : From ki neti c theory of gases
2
3
1
rms
v
V
mN
P =
V
T
P
) gas of mass (
[ As T v
rms
2
]
I f mass of gas i s constant then PV T or PV = RT. Thi s is ideal gas equati on.
11.10 Degr ee of Fr eedom.
The term degree of freedom of a system refers to the possi bl e i ndependent moti ons, 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 i ndependent moti ons can be translati onal, rotat i onal or vi brati onal or any combi nati on of these.
So the degree of freedom are of three types : (i ) Translati onal degree of freedom
(i i ) Rotati onal degree of freedom
(i i i ) Vi brati onal degree of freedom
General expressi on for degree of freedom
f = 3A B ; where A = Number of i ndependent parti cl es, B = Number of i ndependent
restri cti on
(1) Monoatomic gas : Mol ecul e of monoat omi c gas can move i n any di recti on
i n space so i t can have three i ndependent moti ons and hence 3 degrees of freedom (all
translati onal )
(2) Diatomic gas : Molecules of di atomi c gas ar e made up of two atoms j oi ned
ri gidly to one another through a bond. Thi s cannot onl y move bodi ly, but also rotate
about one of the three coordi nate axes. However i ts moment of i nerti a about the axi s
j oi ni ng the two atoms i s negli gi ble compared to that about the other two axes. Hence
i t can have only two r otati onal moti on. Thus a di atomi c molecule has 5 degree of
freedom : 3 translati onal and 2 rotati onal.
z
vz
vx
x
y
vy
v
z
x
y
30 Kinetic Theory of Gases
(3) Tr iatomic gas ( Nonlinear) : A nonli near mol ecul e can rotate about any
of three coordi nate axes. Hence i t has 6 degrees of freedom : 3 translati onal and 3
rotati onal.
(4) Tabular display of degr ee of fr eedom of different gases
Atomicity of gas Example
A
B f = 3A B Figur e
Monoatomi c He, Ne, Ar 1 0 f = 3
Diatomi c H2, O2 2 1 f = 5
Triatomic non li near H2O 3 3 f = 6
Tri atomic linear CO2, BeCl2 3 2 f = 7
N ot e : The above degrees of freedom are shown at room t emperature. Further at hi gh temperature, in case
of diatomic or polyatomic molecules, the atoms wi th i n the molecule may also vibrate with respect to
each other. I n such cases, the molecule wi ll have an addi tional degrees of freedom, due to vibrational
moti on.
An obj ect whi ch vi brates i n one di mensi on has two addi ti onal degree of freedom. One f or the
potenti al energy and one for the ki neti c energy of vi brati on.
A diatomi c molecule that is free to vibrate (in additi on to translati on and rotati on) will have 7 (2 + 3 +
2) degrees of freedom.
An atom i n a soli d though has no degree of freedom for translati onal and rotati onal moti on, due
to vi brati on al ong 3 axes has 3 2 = 6 degrees of freedom (and not l i ke an ideal gas molecule).
When a di atomi c or polyat omi c gas di ssoci ates i nt o atoms i t behaves as monoat omi c gas whose
degree of freedom are changed accordi ngly.
11.11 Law of Equi par ti ti on of Ener gy.
For any system i n thermal equi libri um, the total energy i s equally distributed among i ts vari ous degree of
freedom. And the energy associ ated wi th each mol ecul e of the syst em per degree of freedom of the system i s
kT
2
1
.
where K J k / 10 38 . 1
23
= , T = absolut e temperature of the syst em.
I f the system possess degree of freedom f t hen
Total energy associated wi th each mol ecule kT
f
2
Total energy associated wi th N mol ecules kT
f
N
2
Total energy associated wi th each mol e RT
f
2
x
z
y
A
A A
B
A
A A B
B
B
A
A
B B
A
Kinetic Theory of Gases 31
Total energy associated wi th mole RT
f
2
Total energy associated wi th each gram rT
f
2
Total energy associated wi th M0 gram rT
f
M
2
0
Sample pr oblems based on Law of equipar tition of ener gy
Pr oblem 72. Energy of all molecules of a monoatomi c gas having a volume V and pressure P is PV
2
3
. The total
transl ational ki netic energy of all molecules of a diatomi c gas as the same volume and pressure is
(a) PV
2
1
(b) PV
2
3
(c) PV
2
5
(d) 3 PV
Sol uti on : (b) Energy of 1 mole of gas PV
f
RT
f
2 2
= = where f = Degree of freedom
Monoatomic or diatomi c both gases posses equal degree of freedom for translati onal motion and that is
equal to 3 i .e. f = 3 PV E
2
3
=
Al though total energy will be di fferent, For monoatomic gas PV E
2
3
total
= [ As f = 3]
For diatomic gas PV E
2
5
total
= [ As f = 5]
Pr oblem 73. The temperature of argon, kept i n a vessel is rai sed by 1C at a constant vol ume. The total heat suppli ed to
the gas is a combi nati on of transl ational and rotati onal energi es. Thei r respecti ve shares are [ BHU 2000]
(a) 60% and 40% (b) 40% and 60% (c) 50% and 50% (d) 100% and 0%
Sol uti on : (d) As argon i s a monoatomi c gas therefore i ts mol ecule wil l possess onl y translatory ki netic energy i .e. the
share of translati onal and rotati onal energies wil l be 100% and 0% respecti vel y.
Pr oblem 74. ) (
2
O C O CO i s a tri atomi c gas. Mean ki net i c energy of one gram gas wi l l be (I f NAvogadro's
number, kBol tzmann's constant and mol ecul ar wei ght of 44
2
= CO )
(a) NkT 88 / 3 (b) NkT 88 / 5 (c) NkT 88 / 6 (d) NkT 88 / 7
Sol uti on : (d) Mean ki netic energy for mole gas RT
f
2
. =
RT E
2
7
= NkT
M
m
2
7

.

\

= NkT 
.

\

=
2
7
44
1
NkT
88
7
= [ As f = 7 and M = 44 for
2
CO ]
Pr oblem 75. At standard temperature and pressure the densi ty of a gas i s 1.3 gm/ m
3
and the speed of the sound in gas
is 330 m/ sec. Then the degree of freedom of the gas wil l be
(a) 3 (b) 4 (c) 5 (d) 6
Sol uti on : (c) Gi ven veloci ty of sound
sec
330
m
v
s
= , Density of gas
3
3 . 1
m
kg
= , Atomic pressure
2
5
10 01 . 1
m
N
P =
32 Kinetic Theory of Gases
Substi tuti ng these value i n
P
v =
sound
we get 41 . 1 =
Now from
f
2
1 + = we get . 5
1 4 . 1
2
1
2
=
f
11.12 Mean Fr ee Path.
The mol ecul es of a gas move wi th hi gh speeds at a gi ven temperature but even then a molecule of the gas
takes a ver y l ong ti me t o go from one poi nt to anot her poi nt i n the contai ner of the gas. Thi s i s due to the fact
that a gas molecule suffers a number of colli si ons wi th other gas molecules
surroundi ng i t. As a result of these coll i si ons, the path foll owed by a gas
molecule i n the contai ner of the gas i s zi gzag as shown i n the fi gure. Duri ng
two successi ve coll i si ons, a mol ecul e of a gas moves i n a strai ght li ne wi th
constant vel oci ty and the di stance travelled by a gas molecule between two
successi ve coll i si ons i s known as free path.
The di stance travell ed by a gas molecule between two successi ve colli si ons i s not constant and hence the
average di stance travelled by a molecule duri ng all coll i si ons i s to be calculated. Thi s average di stance travelled
by a gas molecule i s known as mean free path.
Let
n
,... , ,
3 2 1
be the di stance travelled by a gas molecule duri ng n col li si ons respecti vel y, t hen the
mean free path of a gas molecule i s gi ven by
n
n
+ + + +
=
....
3 2 1
(1)
2
2
1
nd
= ; where d = Di ameter of the molecule, n = Number of mol ecul es per uni t volume
(2) As PV = RT = NkT = = = n
kT
P
V
N
Number of molecule per uni t volume
So
P d
kT
2
2
1
=
(3) From
2 2
) ( 2 2
1
d mn
m
nd
= =
2
2 d
m
= [ As mn = Mass per uni t volume = Densi ty = ]
(4) I f average speed of molecul e i s v then
N
t
v = T v = [ As N = Number of colli si on i n ti me t, T = ti me i nterval between t wo
col li si ons]
I mpor t ant poi nt s
(i )
2
2
As
d
m
=
1
i.e. the mean free path i s i nversely proporti onal to the densi ty of a gas.
Ki netic Theory of Gases 33
(i i ) As
P d
kT
2
2
1
= . For constant volume and hence constant number densi ty n of gas mol ecules,
T
P
i s
constant so that wi ll not depend on P and T. But i f volume of gi ven mass of a gas i s all owed to change wi th P
or T then T at constant pressure and
P
1
at constant temperature.
Sample Pr oblems based on Mean fr ee path
Pr oblem 76. I f the mean free path of atoms i s doubled then the pressure of gas will become
(a) 4 / P (b) 2 / P (c) 8 / P (d) P
Sol uti on : (b) As
P d
kT
2
2
1
1
P i .e. by increasing two ti mes pressure will become half.
Pr oblem 77. The mean free path of ni trogen molecules at a pressure of 1.0 atm and temperature 0C is m
7
10 8 . 0
. I f
the number of density of molecul es is
3 25
10 7 . 2 perm , then the molecular di ameter is
(a) nm 2 . 3 (b) 2 . 3 (c) m 2 . 3 (d) mm 3 . 2
Sol uti on : (b) Mean free path = 0.8 10
7
m number of mol ecules per unit vol ume
25
10 7 . 2 = n per m
3
Substi tuti ng these value i n
2
2
1
nd
= we get m d
10 19
10 2 . 3 10 04 . 1
= = 2 . 3 =
11.13 Speci fic heat or Speci fi c Heat Capaci ty.
I t characteri ses the nature of the substance i n response t o the heat suppli ed to t he substance. Speci fic heat
can be defi ned by two followi ng ways : Gram speci fi c heat and Mol ar speci fi c heat.
(1) Gr am specific heat : Gram speci fi c heat of a substance may be defi ned as the amount of heat
requi red to rai se the temperature of uni t mass of the substance by uni t degree.
Gram speci fi c heat
T m
Q
c
A
A
=
Uni ts :
C gm
cal
,
kelvin gm
cal
,
kelvin kg
Joule
Di mensi on : ] [
1 2 2
T L
(2) Molar specific heat : Molar speci fi c heat of a substance may be defi ned as the amount of heat
requi red to rai se the temperature of one gram mole of the substance by a uni t degree, i t i s represented by
capital (C)
T
Q
C
A
=
Uni ts :
C mole
calorie
,
kelvin mole
calorie
or
kelvin mole
Joule
34 Kinetic Theory of Gases
I mpor t ant poi nt s
(1)
T
Q
m
M
Mc C
A
A
= =
T
Q
A
A
=
=
M
m
As
i.e. molar specific heat of the substance is M times the gram specific heat, where M is the molecular weight of that
substance.
(2) Speci fic heat for hydrogen i s maxi mum
C gm
cal
c
= 5 . 3 .
(3) I n li qui ds, water has maxi mum speci fi c heat
C gm
cal
c
= 1 .
(4) Specifi c heat of a substance also depends on the state of substance i.e. soli d, li qui d or gas.
Example :
C gm
cal
c
= 5 . 0
ice
,
C gm
cal
c
= 1
water
,
C gm
cal
c
= 47 . 0
steam
(5) Speci fi c heat also depends on the condi ti ons of the experi ment i.e. the way i n whi ch heat i s suppli ed to
the body. I n general, experi ments are made ei ther at constant volume or at constant pressure.
I n case of soli ds and li quids, due to small thermal expansi on, the di fference i n measured values of speci fic
heats i s very smal l and i s usually neglected. However, i n case of gases, speci fi c heat at constant vol ume i s qui te
di fferent from that at constant pressure.
11.14 Speci fi c Heat of Gases.
I n case of gases, heat energy suppli ed t o a gas i s spent not only i n rai si ng t he temperature of the gas but
also i n expansi on of gas agai nst atmospheric pressure.
Hence speci fic heat of a gas, whi ch i s the amount of heat ener gy requi red to rai se the temperature of one
gram of gas through a uni t degree shal l not have a si ngle or uni que value.
(i ) I f the gas i s compressed suddenly and no heat i s suppli ed from outsi de i .e. AQ = 0, but the temperature
of the gas rai ses on the account of compressi on.
0
) (
=
A
A
=
T m
Q
C i .e. C = 0
(i i ) I f the gas is heated and allowed to expand at such a rate that rise i n temperature due to heat suppli ed
i s exactly equal to fall i n temperature due to expansi on of the gas. i .e. AT = 0
=
A
=
A
A
=
0 ) (
Q
T m
Q
C i .e. C =
(i ii ) I f rate of expansi on of the gas were sl ow, the fal l i n temperature of the gas due to expansi on would be
smaller than the rise i n temperature of the gas due to heat suppli ed. Therefore, there wi ll be some net rise i n
temperature of the gas i .e. AT wi ll be posi ti ve.
= =
) ( T m
Q
C
A
A
posi ti ve i .e. C = posi ti ve
Ki netic Theory of Gases 35
(i v) I f the gas were to expand very fast, fall of temperature of gas due to expansi on would be greater than
ri se i n temperature due to heat suppli ed. Therefore, there wi l l be some net fal l i n temperature of the gas i .e. AT
wi ll be negati ve.
=
=
) ( T m
Q
C
A
A
negati ve i .e. C = negati ve
Hence the speci fic heat of gas can have any posi ti ve value rangi ng from zer o to i nfi ni ty. Further i t can
even be negati ve. The exact value depends upon the mode of heati ng the gas. Out of many val ues of speci fi c
heat of a gas, two are of speci al si gni fi cance.
(1) Specific heat of a gas at constant volume ( cv) : The speci fi c heat of a gas at constant vol ume i s
defi ned as the quanti ty of heat requi red to rai se the temperature of uni t mass of gas through 1 K when i ts
volume i s kept constant, i.e.,
T m
Q
c
v
v
A
A
=
) (
I f i nstead of uni t mass, 1 mol e of gas i s consi dered, the speci fi c heat i s call ed molar speci fi c heat at
constant volume and i s represented by capi tal Cv.
T
Q
T m
Q M
Mc C
v v
v v
A
A
=
A
A
= =
) ( 1 ) (
=
M
m
As
(2) Specific heat of a gas at constant pr essure ( cp) : The speci fi c heat of a gas at constant pressure
i s defi ned as t he quanti ty of heat requi red to rai se the temperature of uni t mass of gas through 1 K when i ts
pressure i s kept constant, i .e.,
T m
Q
c
p
P
A
A
=
) (
I f i nstead of uni t mass, 1 mol e of gas i s consi dered, the speci fi c heat i s call ed molar speci fi c heat at
constant pressure and i s represented by Cp.
T
Q
T m
Q M
MC C
p p
p p
A
A
=
A
A
= =
) (
1
) (
=
M
m
As
11.15 Mayer 's For mula.
Out of two pri nciple speci fi c heats of a gas, Cp i s more than Cv because i n case of Cv, volume of gas i s kept
constant and heat i s requi red only for rai si ng the temperature of one gram mole of the gas through 1C or 1 K.
No heat, what so ever, i s spent i n expansi on of the gas.
I t means that heat suppli ed to the gas i ncreases i ts i nternal energy only i .e.
T C U Q
v v
A = A = A ) ( ..(i )
whi le i n case of Cp the heat is used i n two ways
(i ) I n i ncreasi ng the temperature of the gas by AT
(i i ) I n doi ng work, due to expansi on at constant pressure (AW)
So T C W U Q
p p
A = A + A = A ) ( ..(i i )
From equati on (i ) and (ii ) W T C T C
v p
A = A A
36 Kinetic Theory of Gases
V P C C T
v p
A = A ) ( [ For constant P, AW = PAV]
T
V P
C C
v p
A
A
=
\

= RT
f
dT
d
C
v
2
R
f
2
=
R
f
C
v
2
=
From the Mayers formula R C C
v p
= R R
f
R C C
v p
+ = + =
2
R
f

.

\

+ = 1
2
R
f
C
p

.

\

+ = 1
2
Rati o of Cp and Cv :
f
R
f
R
f
C
C
v
p 2
1
2
1
2
+ =

.

\

+
= =
f
2
1 + =
I mpor t ant poi nt s
(i ) Value of i s always more than 1. So we can say t hat al ways Cp > Cv .
(i i ) Value of i s di fferent for monoat omi c, di atomic and tri atomi c gases.
Kinetic Theory of Gases 37
(i ii ) As
f
2
1 + = 1
2
=
f
1
1
2
=
f
1 2
= =
R
R
f
C
v
and R R
f
C
p


.

\

+
= 
.

\

+ = 1
1
1
1
2
R


.

\

=
1
Specific heat and kinetic energy for differ ent gases
Monoatomi
c
Diatomic Triatomic
non
linear
Tr iatomic
linear
Atomici ty A 1 2 3 3
Restri ct ion B 0 1 3 2
Degree of freedom f = 3A B 3 5 6 7
Molar specific heat
at constant volume 1 2
= =
R
R
f
C
v
R
2
3
R
2
5
3R R
2
7
Molar specific heat
at constant pressure
R R
f
C
p


.

\

= 
.

\

+ =
1
1
2
R
2
5
R
2
7
4R R
2
9
Rati o of Cp and Cv
f C
C
v
p 2
1 + = = 66 . 1
~
3
5
4 . 1
~
5
7
33 . 1
~
3
4
28 . 1
~
7
9
Ki neti c energy of
1 mole
RT
f
E
2
mole
= RT
2
3
RT
2
5
3RT RT
2
7
Ki neti c energy of
1 molecule
kT
f
E
2
molecule
= kT
2
3
kT
2
5
3kT kT
2
7
Ki neti c energy of
1 gm
rT
f
E
2
gram
= rT
2
3
rT
2
5
3r T rT
2
7
Sample Pr oblems based on Specific heat
Pr oblem 78. Fi nd the rati o of specific heat at constant pressure to the specific heat constant volume for
3
NH [ RPMT 200 3]
(a) 1.33 (b) 1.44 (c) 1.28 (d) 1.67
Sol uti on : (c) For polyatomic gas rati o of specific heat < 1.33
Because we know that as the atomi ci ty of gas increases i ts value of decreases.
Pr oblem 79. For a gas 67 . 0 =
v
C
R
. Thi s gas is made up of molecul es which are [ CBSE PMT 1992; JI PMER 20 01, 2002]
(a) Diatomi c (b) Mixture of di atomic and pol yatomi c mol ecules
(c) Monoatomi c (d) Polyatomic
Sol uti on : (c) By compari ng wi th rel ati on
1
=
R
C
v
we get 67 . 0 1 = or = 1.67 i .e. the gas is monoatomi c.
38 Kinetic Theory of Gases
Pr oblem 80. 40 calor i es of heat is needed to raise the temperature of 1 mole of an i deal monoatomic gas from 20C to
30C at a constant pressure. The amount of heat requi red to raise its temperature over the same interval
at a constant volume ) 2 (
1 1
= K mole calorie R is [ UPSEAT 20 00]
(a) 20 cal or i e (b) 40 calor i e (c) 60 calor i e (d) 80 calor i e
Sol uti on : (a) At constant pressure T C Q
p p
A = A ) ( 40 ) 20 30 ( 1 = =
p
C
kelvin mole
calorie
C
p
4 =
R C C
p v
=
kelvin mole
calorie
= = 2 2 4
Now ) 20 30 ( 2 1 ) ( = A = A T C Q
v v
calorie 20 =
Pr oblem 81. At constant vol ume the specific heat of a gas is ,
2
3R
then the value of will be
(a)
2
3
(b)
2
5
(c)
3
5
(d) None of the above
Sol uti on : (c) Specifi c heat at constant volume
2
3
1
R R
C
v
=
(given)
3
2
1 =
3
5
= .
Pr oblem 82. For a gas the difference between the two specific heats is 4150 J/ kg K. What is the specific heats at
constant vol ume of gas i f the ratio of speci fic heat is 1.4
(a) 8475 J/ kg  K (b) 5186 J/ kg  K (c) 1660 J/ kg  K (d) 10375 J/ kg  K
Sol uti on : (d) Gi ven 4150 =
v p
c c ..(i) and 4 . 1 =
v
p
c
c
v p
c c 4 . 1 = ..(ii)
By substituting the value of
p
c i n equati on (i ) we get 4150 4 . 1 =
v v
c c 4150 4 . 0 =
v
c
K kg J c
v
 / 10375
4 . 0
4150
= = .
Pr oblem 83. Two cyli nders A and B fitted with pistons contain equal amounts of an i deal di atomic gas at 300K. The
piston of A i s free to move whi le that of B is held fi xed. The same amount of heat is gi ven to the gas i n each
cylinder. I f the ri se in temperature of the gas i n A i s 30 K, then the rise i n temperature of the gas i n B is[ I I TJEE 1998]
(a) 30 K (b) 18 K (c) 50 K (d) 42 K
Sol uti on : (d) I n both cyli nders A and B the gases are di at omic ( = 1.4). Piston A is free to move i .e. it is isobaric
process. Piston B is fi xed i .e. it is isochoric process. I f same amount of heat AQ i s given t o both then
isochoric isobaric
) ( ) ( Q Q A = A
B v A p
T C T C ) ( ) ( A = A . 42 30 4 . 1 ) ( ) ( ) ( K T T
C
C
T
A A
v
p
B
= = A = A = A
Pr oblem 84. The speci fic heat of a gas [ MP PET 1996]
(a) Has only two values of
p
C and
v
C (b) Has a uni que val ue at a gi ven temperature
(c) Can have any value between 0 and (d) Depends upon the mass of the gas
Sol uti on : (c) Range of specific heat vari es from positi ve to negati ve and from zero to i nfini te. I t depends upon the
nature of process.
Pr oblem 85. The specifi c heat at constant vol ume for the monoatomic argon i s 0.075 kcal / kgK whereas its gram
mol ecular specific heat 98 . 2 =
v
C cal / mole/ K. The mass of the argon atom i s (Avogadros number
23
10 02 . 6 = mol ecul es/ mol e) [ MP PET 1993]
Ki netic Theory of Gases 39
(a) gm
23
10 60 . 6
(b) gm
23
10 30 . 3
(c) gm
23
10 20 . 2
(d) gm
23
10 20 . 13
Sol uti on : (a) Mol ar specifi c heat = Molecular wei ght Gram specifi c heat
v v
c M C =
kelvin kg
kcal
M
kelvin mole
calorie

075 . 0 98 . 2 =
kelvin gm
calorie
M
=
3
3
10
10 075 . 0
molecul ar weight of argon gm M 7 . 39
075 . 0
98 . 2
= =
i .e. mass of
23
10 023 . 6 atom = 39.7 gm mass of si ngl e atom gm
23
23
10 60 . 6
10 023 . 6
7 . 39
=
= .
Pr oblem 86. When an i deal diatomi c gas is heated at constant pressure, the fraction of the heat energy supplied whi ch
increases the i nternal energy of the gas is [ I I TJEE 1990]
(a) 2/ 5 (b) 3/ 5 (c) 3/ 7 (d) 5/ 7
Sol uti on : (d) When a gas is heated at constant pressure then its one part goes to i ncrease the i nternal energy and
another part for work done against external pressure i .e. W U Q
p
A + A = A ) (
V P T C T C
v p
A + A = A
So fraction of energy that goes to increase the internal energy
7
5 1
) (
= = =
A
A
p
v
p
C
C
Q
U
[ As
5
7
= for di atomi c
gas]
Pr oblem 87. The temperature of 5 mol e of a gas whi ch was held at constant volume was changed from 100
o
C to 120
o
C.
The change in i nternal energy was found to be 80 J. The total heat capacit y of the gas at constant volume
wil l be equal to [ CPMT 1988]
(a)
1
8
K J (b)
1
8 . 0
K J (c)
1
4
K J (d)
1
4 . 0
K J
Sol uti on : (c) At constant vol ume total energy wi ll be uti l ised i n increasing the temperature of gas
i .e. T C Q
v v
A = A ) ( 80 ) 100 120 ( = =
v
C
4
20
80
= =
v
C Joul e/ kelvi n. This is t he heat capaci ty of 5 mol e gas.
Pr oblem 88. A gas, is heated at constant pressure. The fraction of heat suppl ied used for external work is
(a)
1
(b)


.

\

1
1 (c) 1 (d)


.

\

2
1
1
Sol uti on : (b) We know fracti on of given energy that goes to i ncrease the i nternal energy
1
=
So we can say t he fraction of gi ven energy that suppl i ed for external work
1
1 = .
Pr oblem 89. A monoatomic gas expands at constant pressure on heati ng. The percentage of heat suppl ied that
increases the i nternal energy of the gas and that is i nvol ved i n the expansi on is
(a) 75%, 25% (b) 25%, 75% (c) 60%, 40% (d) 40%, 60%
Sol uti on : (c) Fracti on of energy suppli ed for i ncrement i n i nternal energy
1
=
5
3
=
= =
Percentage energy % 40 % 100
5
2
= = .
Pr oblem 90. The average degrees of freedom per molecul e for a gas is 6. The gas performs 25 J of work when i t
expands at constant pressure. The heat absorbed by gas i s
(a) 75 J (b) 100 J (c) 150 J (d) 125 J
Sol uti on : (b) As f = 6 (given)
3
4
6
2
1
2
1 = + = + =
f
Fracti on of energy gi ven for external work


.

\

=
A
A
1
1
Q
W

.

\

=
A 3 / 4
1
1
25
Q
4
1
4
3
1 = = Joule Q 100 4 25 = = A
Pr oblem 91. Certain amount of an i deal gas are contained i n a cl osed vessel. The vessel is moving with a constant
veloci ty v. The molecul ar mass of gas is M. The rise i n temperature of the gas when the vessel is suddenly
stopped is ) / (
V P
C C =
(a)
) 1 ( 2
2
+ R
Mv
(b)
R
Mv
2
) 1 (
2
(c)
) 1 ( 2
2
+ R
Mv
(d)
) 1 ( 2
2
+ R
Mv
Sol uti on : (b) I f m is the total mass of the gas then i ts ki netic energy
2
2
1
mv =
When the vessel is suddenly stopped then total kineti c energy will i ncrease the temperature of the gas
(because process wil l be adi abatic) i .e. T C mv
v
A =
2
2
1
T C
M
m
v
A = [ As
1
=
R
C
v
]
2
2
1
1
mv T
R
M
m
= A
R
Mv
T
2
) 1 (
2
= A
.
Pr oblem 92. The density of a pol yatomic gas is standard conditions is 0.795
3
kgm . The specific heat of the gas at
constant vol ume is
(a)
1 1
 930
K kg J (b)
1 1
 1400
K kg J (c)
1 1
 1120
K kg J (d)
1 1
 925
K kg J
Sol uti on : (b) I deal gas equati on for m gr am gas mrT PV = [ where r = Specific gas constant]
or rT
V
m
P = rT = 7 . 466
273 795 . 0
10 013 . 1
5
=
= =
T
P
r
Specifi c heat at constant volume
1
3
4
7 . 466
1
r
c
v
kelvin kg
J
.
1400 =
+


.

\

+


.

\

=
R R
+
+
=
1 1
2
2
1
1
2 1
+
=
1
/
1
/
2
2 2
1
1 1
2
2
1
1
M m M m
M
m
M
m
R
C
mix
V
(i v) Speci fi c heat of the mi xture at constant pressure wi ll be
2 1
2 1
2 1
+
+
=
P P
P
C C
C
mix
2 1
2
2
2
1
1
1
1 1
+


.

\

+


.

\

=
R R
C
mix
P


.

\

+


.

\

+
=
1 1
2
2
2
1
1
1
2 1


.

\

+


.

\

+
=
1 1
2
2
2
2
1
1
1
1
2
2
1
1
M
m
M
m
M
m
M
m
R
C
mix
P
42 Kinetic Theory of Gases
(v)
2 1
2 1
2 1
2 1
mixture
) (
) (
2 1
2 1
+
+
+
+
= =
V V
P P
V
P
C C
C C
C
C
mix
mix
2 1
2 1
2 1
2 1
V V
P P
C C
C C
+
+
=


.

\

+


.

\



.

\

+


.

\

=
1 1
1 1
2
2
1
1
2
2
2
1
1
1
R R
R R
) 1 ( ) 1 (
) 1 ( ) 1 (
1 1
1 1
1 2 2 1
1 2 2 2 1 1
2
2
1
1
2
2 2
1
1 1
mixture
+
+
=
Sample pr oblems based on Mixtur e
Pr oblem 94. I f two moles of diatomi c gas and one mole of monoatomic gas are mixed with then the rati o of speci fic
heats is
[ MP PMT 20 03]
(a)
3
7
(b)
4
5
(c)
13
19
(d)
19
15
Sol uti on : (c) 1
1
= ,
3
5
1
= (for monoatomi c gas) and 2
2
= ,
5
7
2
= (for di atomic gas)
From formula
13
19
5 2 / 3
7 2 / 5
1
5
7
2
1
3
5
1
1
5
7
5
7
2
1
3
5
3
5
1
1 1
1 1
2
2
1
1
2
2 2
1
1 1
mixture
=
+
+
=
Pr oblem 95. 22 gm of
2
CO at 27C i s mixed with 16 gm of
2
O at 37C. The temperature of the mixture is[ CBSE PMT 1995]
(a) 32C (b) 27C (c) 37C (d) 30.5C
Sol uti on : (a) Let t i s the temperature of mixture
Heat gai ned by
2
CO = Heat lost by
2
O
2 2 1 1
2 1
T C T C
v v
A = A
) 37 (
2
5
32
16
) 27 )( 3 (
44
22
t R t R 
.

\

=
) 37 (
2
5
) 27 ( 3 t t =
By solvi ng we get C t = 32 .
Pr oblem 96. A gas mixture consists of 2 mol e of oxygen and 4 mol e of argon at temperature T. Negl ecting all
vibrational modes, the total internal energy of the system is
(a) 4 RT (b) 15 RT (c) 9 RT (d) 11 RT
Sol uti on : (d) Total internal energy of system RT
f
RT
f
U U
2 2
2
2
1
1 argon oxygen
+ = + =
Ki netic Theory of Gases 43
RT RT RT RT RT 11 6 5
2
3
4
2
5
2 = + = + = [ As f1 = 5 (for oxygen) and f2 = 3 (for argon)]
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