Chapter 02 Thermal Properties of Matter (PP 19-58)

CH 02 THERMAL PROPERTIES OF MATTER 19
CHAPTER 02
THERMAL PROPERTIES OF MATTER

2-1 BOYLES LAW
Problem 2-1
A perfect gas undergoes isothermal compression, which
reduces its volume by
3 3
10 20 . 2 m
. The final pressure and

volume of the gas are Torr
3
10 78 . 3 and
3 3
10 65 . 4 m

respectively. Calculate the original pressure of the gas.
Solution
According to Boyles law

2 2 1 1
V p V p =
|
|
\
|
+
=
|
|
\
|
=

) 10 65 . 4 ( ) 10 20 . 2 (
10 65 . 4
) 10 78 . 3 (
3 3
3
3
1
2
2 1
V
V
p p
Torr p
3
1
10 57 . 2 =
Pa Pa p
5 3
1
10 43 . 3 ) 32 . 133 )( 10 57 . 2 ( = =
Pa Torr 32 . 133 1 =

Problem 2-2
A sample of air occupies litre 0 . 1 at C
0
25 and atm 0 . 1 . What
pressure is needed to compress it to
3
100 cm at this
temperature?
Solution

1 1 2 2
V p V p =
|
|
\
|
=
|
|
\
|
=
6
3
5
2
1
1 2
10 100
10 1
) 10 013 . 1 (
V
V
p p
atm m N or Pa p 10 / 10 013 . 1
2 4
2
= =

Problem 2-3
A bubble rises from the bottom of a tall open tank of water
that is at uniform temperature. Just before it bursts at the
surface the bubble is three times its original volume.
Determine the absolute pressure at the bottom of the tank.
Solution

1 1 2 2
V p V p =
|
|
\
|
=
|
|
\
|
=
0
0 5
2
1
1 2
3
) 10 013 . 1 (
V
V
V
V
p p

2 5
2
/ 10 039 . 3 m N or Pa p =


2-2 CHARLESS LAW
Problem 2-4
To what temperature must a sample of a perfect gas of
volume
3
500 cm be cooled from C
0
35 in order to reduce its
volume to
3
150 cm ?
Solution
According to Charless law

f
f
i
i
T
V
T
V
=
|
\
|
+ =
|
|
\
|
=
500
150
) 273 35 (
i
f
i f
V
V
T T
C K T
f
0
6 . 180 4 . 92 = =
Problem 2-5
A given mass of an ideal gas occupies mL 50 at C
0
20 . If its
pressure is held constant, what volume does it occupy at a
temperature of C
0
50 ?
Solution
According to Charless law

f
f
i
i
T
V
T
V
=
mL
T
T
V V
i
f
i f
1 . 55
273 20
273 50
) 50 ( = |
\
|
+
+
=
|
|
\
|
=


2-3 GAY-LUSSACS LAW
Problem 2-6
A container of helium gas at STP is sealed and then raised
to a temperature of K 730 . What will be its new pressure?
Solution
According to Gay-Lussacs law
.
1
1
2
2
const
T
p
T
p
= =

|
|
\
|
=
1
2
1 2
T
T
p p
Now Pa atm p
3
1
10 013 . 1 1 = =
K C T 273 0
0
1
= =
K T 730
2
=
Therefore
Pa p
5 5
2
10 709 . 2
273
730
) 10 013 . 1 ( = |
\
|
=

Problem 2-7
An aerosol can of whipped cream is pressurized at kPa 440
when it is refrigerated at C
0
3 . The can warms against
temperature in excess of C
0
50 . What is the maximum safe
pressure of the can?
Solution
Under these conditions
.
1
1
2
2
const
T
p
T
p
= = (Gay-Lussacs Law)
|
\
|
+
+
=
|
|
\
|
=
273 3
273 50
) 10 440 (
3
1
2
1 2
T
T
p p
Pa p
5
2
10 149 . 5 =

Problem 2-8
One mole of oxygen gas is at a pressure of atm 6 and a
temperature of C
0
27 . (a) If the gas is heated at constant
volume until the pressure triples, what is the final
temperature? (b) If the gas is heated until both the pressure
and volume are doubled, what is the final temperature?
Solution
(a) Now
2
21
1
1
T
p
T
p
= (Gay-Lussacs Law)
K T
p
p
T 900 ) 273 27 )( 3 (
1
1
2
2
= + =
|
|
\
|
=
(b) Now
2
2 2
1
1 1
T
V p
T
V p
= (The General Gas Law)
K T
V
V
p
p
T 1200 ) 273 27 )( 2 )( 2 (
1
1
2
1
2
2
= + =
|
|
\
|
|
|
\
|
=
Problem 2-9
A sample of hydrogen gas was found to have a pressure of
kPa 125 when the temperature was C
0
23 . What its
pressure be expected to be when the temperature is C
0
11 ?
Solution
The relation between pressure and temperature at constant
volume is given by

i
i
f
f
T
p
T
p
=
Pa
T
T
p p
i
f
i f
5 3
10 183 . 1
273 23
273 11
) 10 125 ( = |
\
|
+
+
=
|
|
\
|
=


2-4 THE IDEAL GAS LAW
Problem 2-10
If
3
00 . 3 m of a gas initially at STP is placed under a
pressure of atm 20 . 3 , the temperature of the gas rises to
C
0
0 . 38 . What is the new volume?
Solution
According to general gas equation
.
2
2 2
1
1 1
const
T
V p
T
V p
= =
3
1
2 2
1 1
2
068 . 1 ) 00 . 3 (
) 273 )( 20 . 3 (
) 38 273 )( 1 (
m V
T p
T p
V =
)
`
+
=
|
|
\
|
=

Problem 2-11
Calculate the volume occupied by one mole of an ideal gas
at STP conditions.
Solution
For an ideal gas T R n V p =
p
T R n
V =
Now mol n 1 = ,
1 1
314 . 8

= K mol J R
K C T 273 0
0
= = , Pa atm p
5
10 013 . 1 1 = =
Therefore
litres m V 4 . 22 10 24 . 2
10 013 . 1
) 273 )( 314 . 8 )( 1 (
3 2
5
= =
=

litres m
3 3
10 1 1 =
Problem 2-12
A mol 5 . 2 sample of an ideal gas at atm 00 . 1 pressure has a
temperature of C
0
20 . What is the volume occupied by the
gas?

Solution
For an ideal gas
T R n V p =

p
T R n
V =
litres m V 60 060 . 0
10 013 . 1
) 273 20 )( 314 . 8 )( 5 . 2 (
3
5
= =
+
=
Problem 2-13
Calculate the volume occupied by 5 moles of an ideal gas at
100 kPa and 300 K.
Solution
According to ideal gas law
T R n V p =
3
3
125 . 0
10 100
) 300 )( 314 . 8 )( 5 (
m
p
T R n
V =
= =
Problem 2-14
The boiling point of helium at one atmosphere is K 2 . 4 .
What is the volume occupied by the helium gas due to
evaporation of g 100 of liquid helium at atm 1 pressure and
a temperature of K 300 ?
Solution
According to ideal gas law T R n V p =

p
T R n
V =
Now mol n 25
4
100
= =

1 1
314 . 8

= K mol J R
K T 300 =
Pa atm p
5
10 013 . 1 1 = =
Hence
litres m V 616 616 . 0
10 013 . 1
) 300 )( 314 . 8 )( 25 (
3
5
= =
=
Problem 2-15
Calculate the density of oxygen at S.T.P. using the ideal gas
law. The mass of one mole of oxygen is 32 g.
Solution
T R n V p =
3 2
5
10 241 . 2
10 013 . 1
) 273 )( 314 . 8 )( 1 (
m
p
T R n
V

=
= =
As mass of one mole of oxygen ) (
2
O is equal to g 32 ) 16 ( 2 = ,
therefore
kg kg g m
2 3
10 2 . 3 10 32 32

= = =
The desired density of oxygen at S.T.P. conditions is
3
2
2
/ 428 . 1
10 241 . 2
10 2 . 3
m kg
V
m
=
= =

Problem 2-16
For an ideal gas at temperature K 300 and atm 1 pressure,
what are dimensions of a cube that contains 1000 particles
of the gas?
Solution
Now
T k N V p =

3 23
5
23
10 090 . 4
10 013 . 1
) 300 )( 10 381 . 1 )( 1000 (
m
p
T k N
V

= =
If x is the side of the cube, then
V x =
3

nm m V x 34 . 0 10 445 . 3 ) 10 090 . 4 (
8 3 / 1 23 3 / 1
= = =

Problem 2-17
What is the pressure of an ideal gas if moles 5 . 3 occupy
litres 0 . 2 at a temperature of C
0
150 ?

Solution
T R n V p =

V
T R n
p =
Pa p
6
3
10 79 . 1
) 10 0 . 2 (
) 273 150 )( 314 . 8 )( 5 . 3 (
=
+
=

Problem 2-18
A sample of mg 255 of neon occupies litres 0 . 3 at K 122 .
Calculate the pressure of the gas.
Solution
Now
T R n V p =

V
T R n
p =
As 20.18 g of neon is equal to 1 mol, therefore
n mol mol g mg = =
= =

2
3
3
10 264 . 1
18 . 20
10 255
10 255 255
Hence
Pa p
3
3
2
10 274 . 4
10 3
) 122 )( 314 . 8 ) 10 264 . 1 (
=

atm atm p
2
5
3
10 219 . 4
10 013 . 1
10 274 . 4

=
=

Problem 2-19
The temperature in outer space is about K 7 . 2 and the
matter there consists mainly of isolated hydrogen atom with
a density of
3
/ 3 . 0 m atoms . What is the pressure of this gas?
Solution
T k N V p =
Pa T k
V
N
p
23 23
10 119 . 1 ) 7 . 2 )( 10 381 . 1 )( 3 . 0 (

= =
|
\
|
=
Problem 2-20
A storage tank at S.T.P. contains kg 5 . 18 of nitrogen (
2
N ).
(a) What is the volume of the tank?
(b) What is the pressure if an additional kg 0 . 15 of nitrogen
is added without changing the temperature?
The mass of one mole of nitrogen is g 28 .
Solution
(a) According to ideal gas law
T R
M
m
T R n V p
|
\
|
= =

M p
T R m
V =
3
3 5
8 . 14
) 10 28 )( 10 013 . 1 (
) 273 )( 314 . 8 )( 5 . 18 (
m V =

=

(b) Now T R
M
m
T R n V p |
\
|
= =
1
1

V M
T R m
p
1
=
Pa p
5
3
10 835 . 1
) 8 . 14 )( 10 28 (
) 273 )( 314 . 8 )( 15 5 . 18 (
=
+
=

atm atm p 811 . 1
10 013 . 1
10 835 . 1
5
5
=
=
Problem 2-21
Estimate the mass of air in a room whose dimensions are
m m m 4 5 8 high at S.T.P. The mass of one mole of air
is g 29 .
Solution
T R
M
m
T R n V p
|
\
|
= =

T R
M V p
m =
kg m 207
) 273 )( 314 . 8 (
) 10 29 )( 4 5 8 )( 10 013 . 1 (
3 5
=

=

Problem 2-22
Consider an ideal gas at C
0
20 and a pressure of MPa 00 . 2
in a
3 2
10 00 . 1 m
tank. Determine the gram moles of gas

present.
Solution
T R n V p =
moles
T R
V p
n 21 . 8
) 273 20 )( 314 . 8 (
) 10 00 . 1 )( 10 00 . 2 (
2 6
=
+

= =

Problem 2-23
An industrial firm supplies compressed air cylinders of
volume
3
25 . 0 m filled to a pressure of MPa 20 at C
0
17 .
Calculate the contents of the cylinder in (a) moles (mol) (b)
kilograms. The molar mass of air is
1
029 . 0

mol kg .
Solution
(a) T R n V p =
mol
T R
V p
n
3
6
10 074 . 2
) 273 17 )( 314 . 8 (
) 25 . 0 )( 10 20 (
=
+
= =
(b) mol n
3
10 074 . 2 =
kg n 60 ) 029 . 0 )( 10 074 . 2 (
3
= =
Problem 2-24
Calculate the number of moles in one
3
m of an ideal gas at
C
0
20 and atmospheric pressure.

Solution
T R n V p =
moles
T R
V p
n 6 . 41
) 273 20 )( 314 . 8 (
) 1 )( 10 013 . 1 (
5
=
+
= =
Problem 2-25
A sample of an ideal gas occupies a volume of litres 4 at
C
0
20 with a pressure of atm 3 . How many moles are present
in the sample?
Solution
T R n V p =

T R
V p
n =
Now
Pa Pa atm p
5 5
10 039 . 3 ) 10 013 . 1 ( 3 3 = = =

3 3
10 4 4 m litres V

= =

1 1
314 . 8

= K mol J R
K K C T 293 ) 273 20 ( 20
0
= + = =

Hence
moles n 499 . 0
) 293 )( 314 . 8 (
) 10 4 )( 10 039 . 3 (
3 5
=

=

Problem 2-26
A tyre is filled with air at C
0
15 to a gauge pressure of
kPa 220 . If the tyre reaches a temperature of C
0
38 , what
fraction of the original air must be removed if the original
pressure of kPa 220 is to be maintained?
Solution
As volume and pressure remains same, therefore the fractional
change in number of moles can be written as
2
2 1
1
1 2
) / (
) / ( ) / (
T
T T
T R V p
T R V p T R V p
n
n
=

% 4 . 7 074 . 0
) 273 38 (
) 273 38 ( ) 273 15 (
= =
+
+ +
=
n
n

Hence 7.4 % of original air must be removed to maintain the
same pressure i.e. kPa 220 in the tyre.
Problem 2-27
A quantity of ideal gas at C
0
0 . 12 and a pressure of kPa 108
occupy a volume of
3
47 . 2 m . (a) How many moles of the gas
are present? (b) If the pressure is now raised to kPa 316
and the temperature is raised to C
0
0 . 31 , how much volume
will the gas now occupy? Assume there are no leaks.
Solution
T R n V p =
moles
T R
V p
n 113
) 273 12 )( 314 . 8 (
) 47 . 2 )( 10 108 (
3
=
+
= =
(b) Now
1 1 1
T R n V p =

1
1
1
p
T R n
V =
litres or m V 904 904 . 0
10 316
) 273 31 )( 314 . 8 )( 113 (
3
3 1
=
+
=
Problem 2-28
A tank of volume
3
5 . 0 m contains oxygen at an absolute
pressure of
2 6
/ 10 5 . 1 m N and at a temperature of C
0
20 .
Assume that oxygen behaves like an ideal gas.
(a) How many kilomoles of oxygen are there in the tank?
(b) Find the pressure if the temperature is increased to
C
0
500 . B.U. B.Sc. 2008S
Solution
T R n V p =

) 273 20 )( 314 . 8 (
) 5 . 0 )( 10 5 . 1 (
6
+
= =
T R
V p
n
kilomoles moles n 308 . 0 10 08 . 3
2
= =
(b) Now .
1
1
2
2
const
T
p
T
p
= = for constant V.
) 10 5 . 1 (
273 20
273 500
6
1
1
2
2
|
\
|
+
+
=
|
|
\
|
= p
T
T
p

2 6
2
/ 10 96 . 3 m N p =

Problem 2-29
Oxygen gas having a volume of
3
1130 cm at C
0
42 and a
pressure of kPa 101 expands until its volume is
3
1530 cm
and its pressure is kPa 106 . Find
(a) the number of moles of oxygen in the system and
(b) its final temperature.
Solution
(a) For an ideal gas

i i i
T R n V p =
mol
T R
V p
n
i
i i 2
6 3
10 36 . 4
) 273 42 )( 314 . 8 (
) 10 1130 )( 10 101 (

=
+

= =
(b) Now
f
f f
i
i i
T
V p
T
V p
=

i
i
f
i
f
f
T
V
V
p
p
T
|
|
\
|
|
|
\
|
=
K T
f
6 . 447 ) 273 42 (
1130
1530
101
106
= +
|
\
|
|
\
|
=

Problem 2-30
Calculate the value of gas constant if one mole of an ideal
gas at S.T.P. conditions occupies litres 41 . 22 .
Solution
T R n V p =
1 1
3 5
316 . 8
) 273 0 )( 1 (
) 10 41 . 22 )( 10 013 . 1 (

=
+

= = K mol J
T n
V p
R

Problem 2-31
Write the ideal gas law in terms of the density of the gas.
Solution
The ideal gas law is
T R
M
m
T R n V p
|
\
|
= =
where m and M are mass and molecular weight of the gas
respectively. The above equation can be rewritten as
M
T R
M
T R
V
m
p

=
|
\
|
=
Problem 2-32
Calculate the density of oxygen at S.T.P. using the ideal gas.
The molecular weight of oxygen is mol g / 32 .
Solution

M
T R
p

=

T R
M p
=
3
3 5
/ 428 . 1
) 273 )( 314 . 8 (
) 10 32 )( 10 013 . 1 (
m kg =

=

Problem 2-33
How many molecules are in ideal gas sample at K 350 that
occupies litres 5 . 8 when the pressure is kPa 180 ?
Solution
According to gas law
T k N V p =

T k
V p
N =
molecules N
23
23
3 3
10 165 . 3
) 350 )( 10 381 . 1 (
) 10 5 . 8 )( 10 180 (
=

Problem 2-34
An auditorium has dimensions m m m 30 20 0 . 10 . How
many molecules of air fill the auditorium at C
0
0 . 20 and a
pressure of atm 1 ?
Solution
T R
N
N
T R n V p
A
= =
A
N
N
n =

T R
N V p
N
A
=
) 273 20 )( 314 . 8 (
) 10 022 . 6 )( 0 . 30 0 . 20 0 . 10 )( 10 013 . 1 (
23 5
+

= N

29
10 50 . 1 = N molecules

Problem 2-35
A sealed flask of volume
3
80 cm contains argon gas at a
pressure of kPa 10 and a temperature of C
0
27 . Calculate
the number of molecules of argon gas in the vessel.
Solution
T k N V p =

T k
V p
N =
molecules N
20
23
6 3
10 93 . 1
) 273 27 )( 10 381 . 1 (
) 10 80 )( 10 10 (
=
+

=

Problem 2-36
A certain vacuum pump is capable of reading the gas
pressure in a sealed container is 001 . 0 standard pressure if
the temperature is maintained at K 300 . Calculate the
number of molecules per
3
m in the container at this
pressure and temperature.
Solution
T k N V p =
) 300 )( 10 381 . 1 (
) 10 013 . 1 ( 001 . 0
23
5

= =
T k
p
V
N

3 22
/ 10 45 . 2 m molecules
V
N
=
Problem 2-37
Calculate the number of molecules / m
3
in an ideal gas at
S.T.P.
Solution
T k N V p =
3 25
23
5
/ 10 687 . 2
) 300 )( 10 381 . 1 (
) 10 013 . 1 (
m molecules
T k
p
V
N
=
= =

Problem 2-38
The best vacuum attainable in the laboratory is about
Pa
18
10 0 . 5

at K 293 . How many molecules are there per
3
m in such a vacuum?
Solution
T R
N
N
T R n V p
A
= =
A
N
N
n =

T R
N p
V
N
A
=
3
23 18
/ 1236
) 293 )( 314 . 8 (
) 10 022 . 6 )( 10 0 . 5 (
m molecules
V
N
=

=

Problem 2-39
One mole of helium gas is at room temperature ( K 300 )
and one atmospheric pressure. Calculate the number of
helium atoms per unit volume.
Solution
For an ideal gas
T R
N
N
T R n V p
A
= =
A
N
N
n =

T R
N p
V
N
A
=
3 25
23 5
/ 10 45 . 2
) 300 )( 314 . 8 (
) 10 022 . 6 )( 10 013 . 1 (
m atoms
V
N
=

=
Problem 2-40
A measured amount of heat is added to mol
3
10 2

of a
particular ideal gas to change its volume from
3
0 . 63 cm to
3
0 . 113 cm at constant pressure of atmosphere 1 . Calculate
the change in temperature. P.U. B.Sc. 2006
Solution
For an ideal gas at constant pressure

1 1
T R n V p = (1)

2 2
T R n V p = (2)
Subtract Eq.(1) from Eq.(2)
) ( ) (
1 2 1 2
T T R n V V p =

R n
V V p
T T T
) (
1 2
1 2
= =
K T 305
) 314 . 8 )( 10 2 (
} 10 ) 63 113 ){( 10 013 . 1 1 (
3
6 5
=


2- 5 THE INTERNAL ENERGY OF AN IDEAL GAS
Problem 2-41
At what temperature the relation eV
T k
00 . 1
2
= holds?
Solution
Now J eV
T k
19
10 602 . 1 00 . 1
2
= =
J eV
19
10 602 . 1 00 . 1

=
19
23
10 602 . 1
2
) 10 381 . 1 (

=
T

K T
4
23
19
10 32 . 2
10 381 . 1
) 10 602 . 1 ( 2
=

Problem 2-42
What is the average kinetic energy of a molecule of a gas at
K 300 ?
Solution
The average kinetic energy of a molecule is given by
T k K
2
3
= > <
J K
21 23
10 215 . 6 ) 300 )( 10 381 . 1 (
2
3

= = > <

Problem 2-43
What is the total random kinetic energy (in Joules) of the
molecules in one mole of a gas at temperature C
0
27 .
Solution
The total random kinetic energy of one mole of a monoatomic
gas is given by
T R E
2
3
=
J E 3741 ) 273 27 )( 314 . 8 (
2
3
= + =
Problem 2-44
Find the average translational kinetic energy of individual
nitrogen molecule at K 1600 , in electron volts.
P.U. B.Sc. 2004
Solution
The average translational kinetic energy of a nitrogen molecule
is given by
T k K
2
3
= > <
J K
20 23
10 3144 . 3 ) 1600 )( 10 381 . 1 (
2
3

= = > <
eV K 207 . 0
10 602 . 1
10 3144 . 3
19
20
=
= > <

J eV
19
10 602 . 1 1

=
Problem 2-45
What is the total translational kinetic energy of mol 2 of
2
O molecule at C
0
20 ?
Solution
The average translational kinetic energy of a molecule of a gas
is given by
T k K
2
3
= > <
J K
21 23
10 069 . 6 ) 273 20 )( 10 381 . 1 (
2
3

= + = > <
As there are
A
N 2 molecules in mol 2 of
2
O , therefore total
translational kinetic energy is
) 10 069 . 6 )( 10 022 . 6 ( 2 2
21 23
= > < = K N K
A TOTAL

J K
TOTAL
7310 =
Problem 2-46
The mean kinetic energy of hydrogen molecule at C
0
0 is
J
21
10 62 . 5

. Calculate the value of Avogadros number.

Solution
The mean kinetic energy is given by
T
N
R
T k K
A
|
|
\
|
= = > <
2
3
2
3

23
21
10 058 . 6
) 10 62 . 5 ( 2
) 273 )( 314 . 8 ( 3
2
3
=
=
> <
=
K
T R
N
A

Problem 2-47
Calculate the total kinetic energy of the molecules of one
gram of helium gas at C
0
0 .
Solution
The mean kinetic energy of a gas molecule is given by
T k K
2
3
= > <
As molar mass of helium is 4 g / mole, therefore the number of
molecules in one gram of helium gas will be
4
A
N
N =
Hence the total kinetic energy of molecules of the given gas
sample will be
|
\
|
= > < = T k
N
K N K
A
TOTAL
2
3
4

T R T N k K
A TOTAL
8
3
) (
8
3
= =
J K
TOTAL
851 ) 273 )( 314 . 8 (
8
3
= =

Problem 2-48
Calculate the total rotational kinetic energy of all the
molecules in one mole of air at C
0
25 .
Solution
The internal energy of air molecules has rotational, vibrational
and translational kinetic energies, therefore on average the
rotational kinetic energy will be
INTERNAL
E
3
1
at a given
temperature. Hence for polyatomic gas

INTERNAL ROTATIONAL
E E K
3
1
.) . ( =
J E K
ROTATIONAL
2478 ) 273 25 )( 314 . 8 (
3
1
.) . ( = + =
Problem 2-49
Calculate the internal energy of one mole of an ideal gas at
C
0
250 .
Solution
The internal energy of monoatomic gas is given by
T R n T k N E
INTERNAL
2
3
2
3
= =
J E
INTERNAL
6522 ) 273 250 )( 314 . 8 )( 1 (
2
3
= + =

Problem 2-50
Calculate the internal energy of an ideal gas of volume
3 4
10 4 . 3 m
when its pressure is kPa 100 .

The internal energy of monoatomic gas is given by
T R n T k N E
INTERNAL
2
3
2
3
= =
V p E
INTERNAL
2
3
= T R n V p =
J E
INTERNAL
51 ) 10 4 . 3 )( 10 100 (
2
3
4 3
= =

Problem 2-51
What is the internal energy of mol 50 . 4 of an ideal diatomic
gas at K 600 , assuming that all degrees of freedom are
active?
Solution
A diatomic molecule free to translate, rotate and vibrate will
have seven degrees of freedom. The internal energy of such
diatomic gas will be
T R n E
INTERNAL
2
7
=
J E
INTERNAL
4
10 857 . 7 ) 600 )( 314 . 8 )( 50 . 4 (
2
7
= =
Problem 2-52
Certain excited state of hydrogen atom is found to have
energy of J
18
10 632 . 1

above the lowest (ground) state. At
what temperature would the average translational kinetic
energy be equal to the energy of the excited state?
(Given that K eV k / 10 6 . 8
5
= ) P.U. B.Sc. 2007
Solution
The average translational kinetic energy is given by
T k K
2
3
= > <
Now J K
18
10 632 . 1

=
K J K eV k / ) 10 602 . 1 ( ) 10 6 . 8 ( / 10 6 . 8
19 5 5
= =
K J k / 10 378 . 1
23
=
Hence
T ) 10 378 . 1 (
2
3
10 632 . 1
23 18
=
K T
4
23
18
10 9 . 7
) 10 378 . 1 ( 3
) 10 632 . 1 ( 2
=

Example 2-53
A mole of an ideal at K 300 is subjected to a pressure of
Pa
4
10 and its volume is
3
025 . 0 cm . Calculate
(a) the molar gas constant R
(b) the Boltzmann constant k and
(c) the average translational kinetic energy of a molecule of
the gas.
Solution
T R n V p =
1 1
5
33 . 8
3
25
) 300 ) 1 (
) 025 . 0 )( 10 (

= = = = K mol J
T n
V p
R
(b) The Boltzmann constant is related to gas constant as

A
N k R =
1 23
23
10 38 . 1
10 022 . 6
) 3 / 25 (

=
= = K J
N
R
k
A

(c) The average translational kinetic energy of gas
molecules is given by
T k K
2
3
>= <
J K
21 23
10 21 . 6 ) 300 )( 10 38 . 1 (
2
3

= >= <


2-6 THE KINETIC THEORY OF GASES
Problem 2-54
Twelve molecules have the following speeds, given in
arbitrary units:
. 8 7 , 3 , 5 , 8 , 1 , 4 , 0 , 6 , 4 , 2 , 6 and
Calculate (a) the mean speed and (b) the r.m.s. speed.
Solution
(a)
12
8 7 3 5 8 1 4 0 6 4 2 6 + + + + + + + + + + +
= =

N
v
v
mean

s m v
mean
/ 5 . 4
12
54
= =
(b)
N
v
v
rms
=
2

12
8 7 3 5 8 1 4 0 6 4 2 6
2 2 2 2 2 2 2 2 2 2 2 2
+ + + + + + + + + + +
=
rms
v

s m v
rms
/ 16 . 5
12
320
= =
Problem 2-55
The speeds of ten particles in m/s are
0 . 6 0 . 5 , 0 . 4 , 0 . 4 , 0 . 3 , 0 . 3 , 0 . 3 , 0 . 2 , 0 . 1 , 0 and
Find (a) the average speed (b) the root-mean-square speed
and (c) the most probable speed of these particles.
K.U. B.Sc. 1999, 2006
Solution
(a) The average speed is calculated as
N
v
v
average
=
10
0 . 6 0 . 5 0 . 4 0 . 4 0 . 3 0 . 3 0 . 3 0 . 2 0 . 1 0 + + + + + + + + +
=
average
v
s m v
average
/ 1 . 3
10
31
= =
(b) The mean square speed is defined as
N
v
v
rms
=
2

2 / 1
2 2 2 2
2 2 2 2 2 2
) 0 . 6 ( ) 0 . 5 ( ) 0 . 4 ( ) 0 . 4 (
) 0 . 3 ( ) 0 . 3 ( ) 0 . 3 ( ) 0 . 2 ( ) 0 . 1 ( ) 0 (
10
1
(
(
+ + + +
+ + + + +
=
rms
v
s m v
rms
/ 54 . 3
10
125
= =
(c) As the entry 3.0 has the highest frequency in the given
data, therefore the most probable speed is
s m v
prob
/ 0 . 3 =
Problem 2-56
Calculate the root-mean-square speed of hydrogen molecule
at C
0
0 and atm 1 pressure assuming hydrogen to be an ideal
gas. Under these conditions for hydrogen
3 2
/ 10 99 . 8 m kg
= . P.U. B.Sc. 2000, 2009

Solution
The root-mean square speed is defined as
p
v
rms
3
=
Now Pa or m N atm p
2 5
/ 10 013 . 1 1 = =

3 2
/ 10 99 . 8 m kg
=
Therefore
s m v
rms
/ 1839
10 99 . 8
) 10 013 . 1 ( 3
2
5
=

Problem 2-57
At C
0
0 . 44 and atm
2
10 23 . 1

the density of a gas is
3 5
/ 10 32 . 1 cm g
. Find
rms
v for the gas molecule.
P.U. B.Sc. 2001, 2008
Solution
The root-mean-square speed is defined as
p
v
rms
3
=
Now atm p
2
10 23 . 1

=
Pa Pa or m N p
3 2 5 2
10 24599 . 1 / ) 10 013 . 1 )( 10 23 . 1 ( = =

3 5
/ 10 32 . 1 cm g
=
3 2 3
3 2
3 5
/ 10 32 . 1 /
) 10 (
) 10 )( 10 32 . 1 (
m kg m kg

=
Hence
s m v
rms
/ 532
10 32 . 1
) 10 24599 . 1 ( 3
2
3
=

Problem 2-58
Calculate the root mean square velocity of Nitrogen at C
0
0 .
Given that the density of Nitrogen at N.T.P. is
3
/ 25 . 1 m kg .
B.U. B.Sc. 2002A
Solution
The
rms
v is given by
s m
p
v
rms
/ 493
25 . 1
) 10 013 . 1 ( 3 3
5
=
= =

Problem 2-59
A cylindrical container of length cm 0 . 56 and diameter
cm 5 . 12 holds mol 350 . 0 of nitrogen gas at a pressure of
atm 05 . 2 . Find the r.m.s. speed of nitrogen molecule.
Solution
The root-mean-square speed of nitrogen molecule is defined as

p
v
rms
3
= (1)
Now Pa atm p ) 10 013 . 1 )( 05 . 2 ( 05 . 2
5
= =
Pa p
5
10 077 . 2 =
For calculation of density we proceed as under.
1 mol of nitrogen gas has mass kg g
3
10 28 28

= =
0.350 mol of nitrogen gas has mass kg ) 10 28 )( 350 . 0 (
3
=
kg m
3
10 8 . 9

=
The volume of the cylinder is given by

2 2
) 2 / (D r V = =
3 3 3 2
2
2
10 872 . 6 ) 10 0 . 56 (
2
10 5 . 12
m m V

=
|
|
\
|
=
The density is defined as
3
3
3
/ 426 . 1
10 872 . 6
10 8 . 9
m kg
V
m
=
= =

Substitute the values of p and in Eq.(1)
s m v
rms
/ 661
426 . 1
) 10 077 . 2 ( 3
5
=
=

Problem 2-60
What is the average speed and root-mean-square speed of
oxygen molecule at K 300 ? Molar mass of oxygen
mole kg / 032 . 0 = . K.U. B.Sc. 2007
Solution
The average speed is defined as

M
T R
v
average
8
=
s m v
average
/ 5 . 445
) 032 . 0 (
) 300 )( 314 . 8 ( 8
= =

The root mean square velocity is defined as

M
T R
v
rms
3
=
s m v
rms
/ 6 . 483
032 . 0
) 300 )( 314 . 8 ( 3
= =
Problem 2-61
Root mean square velocity of the gas molecules (of certain
density and pressure) if found to be
1
531

s m at a
temperature of C
0
44 . Find the molecular mass of the gas.
P.U. B.Sc. 2005
Solution
The root mean square velocity is defined as

M
T R
v
rms
3
=

M
T R
v
rms
3
2
=

2
3
rms
v
T R
M =

2
) 531 (
) 273 44 )( 314 . 8 ( 3 +
= M
mol g mol kg M / 28 / 10 80 . 2
2
= =

Problem 2-62
The temperature in interstellar space is K 7 . 2 . Find the
root-mean-square speed of hydrogen molecule at this
temperature. The molar mass of hydrogen is g 2 .
Solution

M
T R
v
rms
3
=
s m v
rms
/ 5 . 183
10 2
) 7 . 2 )( 314 . 8 ( 3
3
=

Problem 2-63
At what temperature do helium atoms have an r.m.s. speed
equal to the escape speed from the surface of Earth
( s km v
ESCAPE
/ 2 . 11 = )?
Solution

M
T R
v
rms
3
=

M
T R
v
rms
3
2
=

R
M v
T
rms
3
2
=
Now s km v v
ESCAPE rms
/ 2 . 11 = =
s m s m v
rms
/ 10 12 . 1 / 10 2 . 11
4 3
= =
mol kg mol g M / 10 4 / 4
3
= =

1 1
314 . 8

= K mol J R
Therefore
K T
4
3 2 4
10 01 . 2
) 314 . 8 ( 3
) 10 4 ( ) 10 12 . 1 (
=

=

Problem 2-64
At what temperature, pressure remaining unchanged, will
the speed of hydrogen molecules be double of its value at
S.T.P.?
Solution
For a given mass of gas
T v
rms

Let
1
v and
2
v be the r.m.s. speeds of hydrogen molecules at
1
T and
2
T respectively, then
1 1
T v
2 2
T v
Divide second relation by first relation
1
2
1
2
T
T
v
v
=
Substituting the given values in above equation

273
2
2
1
1
T
v
v
=

273
2
2
T
=

273
4
2
T
=
K T 1092 ) 273 ( 4
2
= =
Problem 2-65
Calculate the temperature of oxygen molecules to have the
same root mean square speed as that of hydrogen molecules
at C
0
100 .
Solution

M
T R
v
rms
3
=
Now
rms
v of oxygen molecule at
1
T =
rms
v of oxygen molecule at
2
T
2
2
1
1
3 3
M
T R
M
T R
=
2
2
1
1
3 3
M
T R
M
T R
=
2
2
1
1
T
M
M
T
|
|
\
|
=
As the molecular weights of oxygen and hydrogen are 32 and 2
respectively, therefore
16
2
32
2
1
= =
M
M

and K K C T 173 ) 273 100 ( 100
0
2
= + = =
Hence
K T 2768 ) 173 )( 16 (
1
= =
Problem 2-66
At what temperature do atoms of helium have an r.m.s.
speed equal to 1.00 % of the speed of light?
Solution

M
T R
v
rms
3
=

M
T R
v
rms
3
2
=

R
M v
T
rms
3
2
=
Now
c c of v
rms
01 . 0 % 00 . 1 = =
s m s m v
rms
/ 10 998 . 2 / ) 10 998 . 2 )( 01 . 0 (
6 8
= =
mol kg mol g M / 10 4 / 4
3
= = ,
1 1
314 . 8

= K mol J R
Therefore
K T
9
3 2 6
10 441 . 1
) 314 . 8 ( 3
) 10 4 ( ) 10 998 . 2 (
=

=

Problem 2-67
To increase the r.m.s. speed of a gas by 1 %, by what
percentage must the temperature increase?
Solution

M
T R
v
rms
3
= (1)
Let T T + be the temperature at which the r.m.s. speed is

rms rms
v of v % 1 +
rms rms rms
v v v 01 . 1 01 . 0 = + =
Hence

M
T T R
v
rms
) ( 3
01 . 1
+
= (2)
Divide Eq.(2) by Eq.(1)

T
T T +
= 01 . 1
Square both sides of above equation

T
T
T
T T
+ =
+
= 1 0201 . 1
0201 . 0 1 0201 . 1 = =
T
T

01 . 2 100 0201 . 0 100 = =
T
T

The desired percentage increase in temperature is 2.01 %.
Problem 2-68
At what temperature do the atoms of helium gas have same
root mean square speed as molecules of hydrogen gas at
C
0
27 ? The molar mass of helium is double that of
hydrogen. K.U. B.Sc. 2002
Solution

M
T R
v
rms
3
=
where M is the molar mass. Now
rms
v of helium gas atom =
rms
v of hydrogen gas molecule

2
2
1
1
3 3
M
T R
M
T R
=

2
2
1
1
M
T
M
T
=

2
2
1
1
M
T
M
T
=

|
|
\
|
=
2
1
2 1
M
M
T T
C K
M
M
T
0
2
2
1
327 600
2
) 273 27 ( = =
|
|
\
|
+ =
Problem 2-69
Calculate the root-mean-square speed of smoke particles of
mass g
14
10 2 . 5

in air at C
0
14 and atm 1 pressure.
Solution
The root-mean-square speed is given by
m
T k
v
rms
3
=
Now K J k / 10 381 . 1
23
=
K K C T 287 ) 273 14 ( 14
0
= + = =
kg g m
17 14
10 2 . 5 10 2 . 5

= =
Therefore
s m v
rms
/ 10 521 . 1
10 2 . 5
) 287 )( 10 381 . 1 ( 3
2
17
23
=
Problem 2-70
Calculate the root mean square speed of hydrogen at C
0
127 .
The mass of hydrogen molecule is kg
27
10 34 . 3

.
Solution
The root-mean-square speed is given by
m
T k
v
rms
3
=
Now K J k / 10 381 . 1
23
=
K K C T 400 ) 273 127 ( 127
0
= + = =
kg m
27
10 34 . 3

=
Therefore
s m v
rms
/ 10 23 . 2
10 34 . 3
) 400 )( 10 381 . 1 ( 3
3
27
23
=


2-7 THE MEAN FREE PATH
Problem 2-71
What is the average distance between nitrogen molecules at
S.T.P.?
Solution
The ideal gas law can be used to calculate the molecular density
(i.e. number of molecules per m
3
) for nitrogen at S.T.P. as
under.
T k N V p =

T k
p
V
N
=
3 25
23
5
/ 10 687 . 2
) 273 )( 10 381 . 1 (
10 013 . 1
m molecules
V
N
=

Assuming that nitrogen molecule has a spherical shape of
diameterd, then

6 2 3
4
3
4
3
3
3
d d
r
N
V
=
|
\
|
= =

) / (
6 6
3
V N N
V
d

= =

3 / 1
) / (
6
)
`
=
V N
d

nm m d 142 . 4 10 142 . 4
) 10 687 . 2 (
6
9
3 / 1
25
= =
)
`

the desired distance between nitrogen molecules.
Problem 2-72
The mean free path of
2
CO molecules at S.T.P. is measured
to be about
8
10 6 . 5

. Estimate the diameter of
2
CO
molecule.
Solution
The mean free path of a gas molecule is given by

p d
T k
2
2
=

p
T k
d
2
2
=

2 / 1
2
)
=
p
T k
d
m d
10
2 / 1
8 5
23
10 868 . 3
) 10 6 . 5 )( 10 013 . 1 ( 2
) 273 )( 10 381 . 1 (

the desired diameter of a
2
CO molecule.
Problem 2-73
The molecular diameter of different kinds of gas molecules
can be found experimentally by measuring the rates at
which different diffuse into each other. For nitrogen,
m d
10
10 15 . 3

= has been reported. What are the mean free
path and average rate of collision for nitrogen at room
temperature ( K 300 ) and at atmospheric pressure?
P.U. B.Sc. 2000, 2008
Solution
The number of molecules per unit volume is given by

T k
p
p T k N
N
V
N
n
= = =
) / (
T k N V p =
3 25
23
5
/ 10 445 . 2
) 300 )( 10 381 . 1 (
10 013 . 1
m molecules
n
=

The mean free path is given by

n
d
2
2
1
=
m
8
25 2 10
10 278 . 9
) 10 445 . 2 ( ) 10 15 . 3 ( 2
1

=

=

The average rate of collision is given by
Rate of collision
M
T R v
rms
3 1

= =

028 . 0
) 300 )( 314 . 8 ( 3
10 278 . 9
1
8
=

1 9
10 572 . 5

= s
Problem 2-74
Calculate the mean free path of a gas if its diameter at
S.T.P. is 2 .
Solution

n
d
2
2
1
=

p d
T k
2
2
=
T k
p
n
=
m
7
5 2 10
23
10 09 . 2
) 10 013 . 1 ( ) 10 2 ( 2
) 273 )( 10 381 . 1 (

Problem 2-75
Calculate the diameter of benzene molecule if there are
3 25
/ 10 79 . 2 m molecules and mean free path for benzene is
m
8
10 2 . 2

.
Solution
The mean free path is given by

n
d
2
2
1
=

n
d
2
1
2
=
2 / 1
) 2 (
1

n
d =
{ }
2 / 1
8 25
) 10 2 . 2 )( 10 79 . 2 ( 2
1
d
06 . 6 10 06 . 6
10
= =

m d
the desired diameter of benzene molecule.
Problem 2-76
A cubic box m 20 . 1 on a side is evacuated so the pressure of
air inside is torr
6
10
. Estimate how many molecular

collisions there are per each collision with a wall ( C
0
0 ). The
diameter of air molecule is m
10
10 3

.
Solution

p d
T k
2
2
=
m 7 . 70
) 10 333 . 1 10 ( ) 10 3 ( 2
) 273 )( 10 381 . 1 (
2 6 2 10
23
=

2 2
/ 10 333 . 1 1 m N torr =
The desired number of molecular collisions is
1 2
10 697 . 1
7 . 70
20 . 1

= = m
a

Problem 2-77
At what frequency would the wavelength of sound be of the
order of mean free path in oxygen at S.T.P.? Take the
diameter of oxygen molecule to be m
10
10 3

and speed of
sound in oxygen equal to s m/ 330 .
Solution
The number of molecules per unit volume is given by

T k
p
p T k N
N
V
N
n
= = =
) / (
T k N V p =
3 25
23
5
/ 10 687 . 2
) 273 )( 10 381 . 1 (
10 013 . 1
m molecules
n
=


n
d
2
2
1
=
m
8
25 2 10
10 305 . 9
) 10 687 . 2 ( ) 10 3 ( 2
1

=

=

The desired frequency is
Hz
v
f
9
8
10 546 . 3
10 307 . 9
330
=
= =

Problem 2-78
At standard temperature and pressure (0
0
C and 1.00 atm)
the mean free path in helium gas is 285 nm. Determine
(a) the number of molecules per cubic metre and
(b) the effective diameter of the helium atoms.
Solution
(c) The number of molecules per unit volume is given by

T k
p
p T k N
N
V
N
n
= = =
) / (
T k N V p =
3 25
23
5
/ 10 687 . 2
) 273 )( 10 381 . 1 (
15 013 . 1
m molecules
n
=

(d) The mean free path is given by

n
d
2
2
1
=

n
d
2
1
2
=

2 / 1
) 2 (
1

n
d =
{ }
2 / 1
9 25
) 10 285 )( 10 687 . 2 ( 2
1
d
nm m d 174 . 0 10 741 . 1
10
=

ADDITIONAL PROBLEMS
(1) Calculate the root-mean-square (r.m.s.) velocity of
nitrogen molecule at S.T.P. conditions. The density
of nitrogen at S.T.P. is
3
25 . 1

m kg .
B.U. B.Sc. 2002A
(2) Calculate the root mean square speed of oxygen
molecule at C
0
27 . The density of oxygen at S.T.P. is
3
43 . 1

m kg .
(3) Calculate the r.m.s. speed of carbon dioxide
molecule at C
0
27 . The molar mass of carbon dioxide
is g 44 .
(4) Calculate the r.m.s. speed of the molecules of
nitrogen gas at C
0
10 . The molar mass of nitrogen
molecule is kg 028 . 0 .
(5) Calculate the number of molecules in a flask of
volume
3
500 cm containing oxygen at a pressure of
kPa 200 and a temperature of C
0
27 .

ANSWERS
(1) s m/ 493 (2) s m/ 5 . 483 (3) s m/ 412 (4) s m/ 502
(5) molecules
22
10 42 . 2

Chapter 02 Thermal Properties of Matter (PP 19-58)

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Chapter 02 Thermal Properties of Matter (PP 19-58)

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CH 02 THERMAL PROPERTIES OF MATTER 19

. The final pressure and

tank. Determine the gram moles of gas

when its pressure is kPa 100 .

= . P.U. B.Sc. 2000, 2009

. Estimate how many molecular

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