KENYATTA UNIVERSITY

INSTITUTE OF OPEN LEARNING

SPH 203
THERMAL PHYSICS 1

WALTER. K. NJOROGE

DEPARTMENT OF PHYSICS

2005
CONTENTS PAGE

1. What is thermodynamics 1
1.1 Objectives 1
1.2 Introduction 1
1.3 Some definitions 1
1.4 System description 2
1.5 Exercise 3
1.6 Further reading 3

2. Thermal equilibrium and Zeroth law of thermodynamics ..4

2.1 Objectives ..4
2.2 Thermal equilibrium ...4
2.3 Zeroth law of thermodynamics .5
2.4 Further reading. . 5

3. Temperature 6
3.1 Objectives 6
3.2 Definition of temperature 6
3.3 Measurement of temperature 8
3.4 Celsius temperature .10
3.5 Molecular interpretation of temperature
(kinetic theory of gases) 10
3.6 Exercises .. 14
3.7 Further reading.. .. 15

4. Simple thermodynamic systems 16

4.1 Objectives 16
4.2 Introduction 16
4.3 Equation of state of the simplest closed
hydrostatic system 16
4.4 Differential changes of state of simple systems18
4.5 Examples . 21
4.6 Exercises.22
4.7 Further reading 23

5. Work ..24
5.1 Objectives...........................................................................24
5.2 Work done by change in volume .25
5.3 Examples ..27
5.4 Problems. .30
5.5 Further reading .31

6. First law of thermodynamics .. 32

6.1 Objectives .32
6.2 Definition 32
6.3 Examples .34
6.4 Exercises 36
6.5 Further reading ..37

7. Calorimetry .38
 7.1 Objectives 38
7.2 Quantity of heat .38
7.3 Specific heat capacity 38
7.4 Molar heat capacity 39
7.5 Latent heat 39
7.5.1 Molecular theory explanation 40

7.6 Heat capacities of ideal gasses.40

7.7 Heat changes at constant pressure (Enthalpy) 41
7.8 Examples 42
7.9 Exercises 44
7.10 Further reading .44

8. Ideal gas laws ..45

8.1 Objectives45
8.2 Equation of state ..45
8.3 Examples 47
8.4 Exercises .48
8.5 Further reading 49

9. Thermal properties and one dimensional heat flow 50

9.1 Objectives 50
9.2 Thermal expansion 50
9.3 Relation between and 51
9.4 Thermal stress 52
9.5 Heat conduction 53
9.6 Exercises 55
9.7 Further reading........................................................... 56

10. Adiabatic processes 57

10.1 Objectives57
10.2 Adiabatic processes .. 57
10.3 Examples 60
10.4 Exercises .61
10.5 Further reading 61

11. Black body radiation 62

11.1 Objectives .62
11.2 Thermal radiation 62
11.3 Wiens displacement law 63
11.4 Theories on spectral distribution of radiation..64
11.5 Examples..69
11.6 Exercises 73
11.7 Further reading74
CHAPTER 1
WHAT IS THERMODYNAMICS

1.1 Objectives

By the
By the end
end of
of this
this lesson,
lesson, you
you should
should be
be able
able to:
to:
Distinguish between classical and statistical thermodynamics
Distinguish
Define mostbetween classical and used
of the terminologies statistical thermodynamics
in thermodynamics
Define most of the terminologies used in thermodynamics
Distinguish between an open, closed and isolated systems
Distinguish
Write downbetween
examplesanofopen, closed
adiabatic and
and isolated systems
diathermic walls
Write down examples of adiabatic and diathermic walls
Distinguish between macroscopic and microscopic quantities
used in describing a system

1.2 Introduction:

Thermodynamics is the basic science, which deals with heat and other forms of energy, their
transformations and their relationships with properties of substances

There are two classes of thermodynamics namely classical and statistical thermodynamics:
1. Classical thermodynamics: It is a science that is concerned only with the average
characteristics of large aggregates of molecules, not with the characteristics of
individual molecules i.e. classical thermodynamics takes macroscopic point of view
and deals with macroscopic phenomenon.
2. Statistical thermodynamics: It considers the microscopic structure of matter and
adopts the laws of mechanics on the statistical analysis of the individual particles.

1.3 Some Definitions

System: This is a specific portion of matter with definite boundaries on which
attention is focussed. The boundaries are well prescribed and may be either movable
or fixed

Surrounding (Environment): This refers to all space of matter external to the

system, which may or may not interact with the system

Closed system: This is a system of fixed (constant) content (mass) i.e. one in which
no transfer of mass occurs.

Open system: A system in which mass may be transferred between the system and the
surrounding

Universe: System plus its surrounding

Isolated Systems: Systems which can not exchange energy of any kind including
mass with their surroundings, i.e. isolated system is not allowed to exchange heat,
work or mass with its surroundings

A process: Any transformation of a system from one equilibrium state to another over
an interval of time. Work and energy transfer may occur. When any property of a
system changes there is change in the state and the system is said to undergo a process
 Path of a process: The specific series of equilibrium states through which the system
passes during the process

State: The state of a system at any instant is its condition of existence at that instant.
A complete description of a system defines the existing conditions.

Isothermal: Is the locus of all points representing states at which a system is in

thermal equilibrium with one state of another system.

Property: A property of a system is any quantity or characteristic that depends on the

state of the system.

Adiabatic wall: It does not allow heat to pass through (impervious to heat)

Diathermic Wall: It allow heat to pass through

1.4 System Description

We have already defined a system as separation of a restricted region of space or a finite

portion of matter from its surroundings. Everything outside the system, which has a direct
bearing on its behaviour, is known as the surrounding. There are two approaches adopted in
describing a system

1. Macroscopic point of view

2. Microscopic point of view

In macroscopic point of view we are talking of the quantities, which are measurable, and you
can feel their presence while in microscopic point of view, there are a lot of assumptions
because of dealing with imagined quantities. The characteristics of the macroscopic
coordinates are: -
They involve no special assumptions concerning the structure of matter
They are few in number
They are suggested more or less directly by our sense of perception
They can in general be measured.

Some of these quantities are mass M, Volume V, pressure P, temperature T, density,

viscosity, refractive index etc. Characteristics of a microscopic description negates the above
characteristics.

1.5 Exercise

1. Think of a system and draw a well labelled diagram of the system showing its
surroundings. Define the boundaries and specify the contents of the system.
2. Write down examples of adiabatic and diathermic walls
3. Write down more examples of macroscopic and macroscopic quantities in addition
to the ones listed in section 1.4

1.6 Further Reading

1. Sprackling M. (1991) Thermal Physics, chapter 1
2. Sprackling M. (1993) Heat and Thermodynamics, chapter 1
3. Adkins C. J. (1983) Equilibrium thermodynamics, Chapter 1
4. Fink J. L. (1955) Thermodynamics, Chapter 1
 CHAPTER 2
THERMAL EQUILIBRIUM AND ZEROTH LAW OF THERMODYNAMICS

2.1 Objectives

By the end of this lesson, you should be able to:

Explain what is thermodynamic equilibrium
State Zeroth law of thermodynamic

2.2 Thermal equilibrium

In referring to any non-specified system, we will use the symbols Y and X for a pair of
independent variables. A state of a system in which Y and X have definite values that remain
constant so long as the external conditions are unchanged is called equilibrium state. The
existence of an equilibrium state in one system depends on the proximity of other systems and
on the nature of the wall separating them. Walls are either adiabatic or diathermic.

SYSTEM A SYSTEM A
All values of Adiabatic Diathermic
wall Only resrtricted
Y,X possible values of wall
Y,X possible

SYSTEM B
SYSTEM B
All values of
Only resrtricted
Y,X possible
values of
Y,X possible

Figure 1a Figure 1b

Fig 1. Shows two systems A and B separated by a). adiabatic wall and b). Diathermic wall

For adiabatic wall, figure 1a, a state Y, X for system A and Y, X for system B may coexist
as equilibrium states for any attainable values of the four quantities, provided only that the
wall is able to withstand the stress associated with the difference between the two sets of
coordinates. Thick layers of wood concrete, asbestos etc are good approximations to adiabatic
walls. If the two systems are separated by diathermic wall figure 1b, the values of Y, X and
Y, X will change spontaneously until an equilibrium state of the combined system is
attained. The two systems are then said to be in thermal equilibrium with each other. The
most common diathermic wall is a thin metallic sheet. Thermal equilibrium is the state
achieved by two (or more) systems characterized by restricted values of coordinates of the
systems, after they have been in communication with each other through a diathermic wall.

2.3 Zeroth law of thermodynamics

Imagine two systems A and B separated from each other by an adiabatic wall but each in
contact with a third system C through diathermic walls, the whole assembly being surrounded
by an adiabatic wall as shown in figure 2a. The two systems will come to thermal equilibrium
with the third and that no further change will occur if the adiabatic wall separating A and B is
then replaced by a diathermic wall figure 2b. This experimental fact can then be stated
concisely in the following form: Two systems in thermal equilibrium with a third are in
thermal equilibrium with each other. This is the Zeroth law of thermodynamics.

System C System C

Diathermic
A B wall
A B

Figure 2. a). Systems A and B separated from each other by an adiabatic wall but each in
contact with a third system C through diathermic walls. b). Systems A and B after the
adiabatic wall separating them is replaced with diathermic wall but each in contact with a
third system C through adiabatic wall.

2.3 Further Reading

5. Sprackling M. (1991) Thermal Physics, chapter 3
6. Sprackling M. (1993) Heat and Thermodynamics, chapter 1
7. Adkins C. J. (1983) Equilibrium thermodynamics, Chapter 2
 CHAPTER 3: TEMPERATURE

3.1 Objectives

By the end of this lesson, you should be able to:

Define temperature
Describe different types of thermometers
Differentiate between the Celsius and Kelvin scale
3.2 Definition of temperature
Explain molecular interpretation of temperature
Consider two systems A and B each in a state of equilibrium. Let them be brought into
contact by means of a diathermic wall. The two systems are then thermally insulated from the
rest of the universe by surrounding adiabatic wall. This is illustrated by figure 3.

A
Diatherm ic

B wall

Figure 3. Systems A and B separated from each other by a diathermic wall and separated from
the rest of universe by adiabatic wall.

If the two are not in mutual equilibrium, their properties will change until eventually they are.
When the two systems are in thermal equilibrium the property, which shows that we are in
that state is called temperature. Two systems are in thermal equilibrium if they have the same
property called temperature i.e. two systems have equal temperatures if when brought into
thermal contact, their properties do not change.

Mathematically

Let us consider two systems A and C with initial state coordinates X, Y and X, Y
respectively. When these two systems are brought in thermal contact, the final state of
thermal equilibrium is denoted by a relation among the coordinates, which may be written as
follows:

f AC ( X , Y , X ' , Y ' ) = 0 (3.2.1)

i.e. for gasses obeying Boyles law

 PV P 'V ' = 0 (3.2.2)

Thermal equilibrium between systems B and C can also be expressed as

f AC ( X ' , Y ' , X ' ' , Y ' ' ) = 0 (3.2.3)

where X and Y are the coordinates of system B.

Suppose we solve for Y

Y ' = g CA ( X , Y , X ' )
Y ' = hBC ( X ' , X ' ' , Y ' ' ) (3.2.4)

Therefore

g CA ( X , Y , X ' ) = hBC ( X ' , X ' ' , Y ' ' )

(3.2.5)

By Zeroth law A and B are in thermal equilibrium i.e.

f AB ( X , Y , X ' ' , Y ' ' ) = 0 (3.2.6)

Hence

h A ( X , Y , ) = hB ( X ' ' , Y ' ' )

(3.2.7)

When the three systems A, B and C are in thermal equilibrium then

h A ( X , Y , ) = hB ( X ' ' , Y ' ' ) = hc ( X ' , Y ' ' ) (3.2.8)

The common value t of the functions is the empirical temperature common to all the systems

t = h A ( X , Y , ) is the equation of an isothermal of the system A.

Note:
Isothermal Is the locus of all points representing states at which a system is in thermal
equilibriumofwith
3.3 Measurement one state of another.
temperature

Let us consider a system with coordinates X, Y (thermometer). A numerical value of the

temperature can be assigned to each of its isotherms and the same applies to other systems in
thermal equilibrium with the thermometer. Figure 4 shows isotherms of system which can be
described using coordinates X,Y.
 Y

re
.

em t the
atu
Y=Y'

per
a
trip erm
th
le t
Iso

XTP X

Figure 4: Isotherms of system which can be described using coordinates X,Y.

A convenient path is chosen in the XY plane, as shown in figure 4 above which intersects the
isotherms at points each of which has the same Y coordinate but a different X coordinate. The
temperature associated with each isotherm is then taken to be a convenient function of the X
at this intersection point. The X is called the thermometric property, and the form of the
thermometric function (X) determines the temperature scale.
There are six important kinds of thermometers. Table 1 summarizes these thermometers and
their thermometric properties.

Table 1. Thermometers and their thermometric properties

Thermometer Thermometric property Symbol

Gas (constant volume) Pressure P
Electric resistor (constant tension) Electric Resistance R
Thermocouple (constant tension) Thermal e.m.f
Helium vapour (saturated) Pressure P
Paramagnetic salt Magnetic Susceptibility
Blackbody radiation Radiant emittance RB

X stand for any one of the thermometric properties. The temperature scale is defined so that
the temperature is directly proportional to X. Thus, the temperature common to the
thermometer and all systems in thermal equilibrium with it is given by

( x) = ax (3.3.1)

The value of a should be established for one to have a numerical relationship between the
temperature (X) and the thermometric property X. The temperature at triple point is
normally taken as 273.16. Therefore
 273.16 K
a= (3.3.2)
X TP

Thus (X) =aX becomes

X
( X ) = 273.16 K (3.3.3)
X TP

For the first three thermometers listed in table 1 we get the functions listed below

Gas at constant volume

P
( P) = 273.16 K (3.3.4)
PTP
Electric resistor

R
( R) = 273.16 K (3.3.5)
RTP

and for

the thermocouple

( ) = 273.16 K (3.3.6)
TP

3.4 Celsius temperature scale

The Celsius temperature scale employs a degree of the same magnitude as that of ideal gas
scale, but its zero is shifted so that the Celsius temperature of the triple point of water is 0.01
degree Celsius, abbreviated 0.01C, thus, if t denotes the Celsius temperature then

t (C ) = ( K ) 273.15 (3.4.1)

3.5 Molecular interpretation of temperature (kinetic theory of gases)

The variables pressure (P), volume (V) and temperature (T) that are used to describe the
behaviour of gases are macroscopic variables. The treatment of gases at microscopic scale
(state) requires definition of coordinates and velocities of all molecules. The microscopic state
of gases is also referred to as kinetic theory of gases.

As the gas molecules collide, the pressure of the gas increases. This pressure can be calculated
by determining the rate of change of momentum due to collision of molecules with the walls
of the container. By Newton second law, rate of change of momentum equals the force F
exerted by the walls on the molecules.
r
r dP
F= (3.5.1)
dt

By Newtons third law, this force equals the force exerted by the molecules on the wall. The
force per unit area is pressure. The following assumptions have been made in the kinetic
theory of gases:

1. The gas consists of a large number of molecules that make elastic collisions with each
other and with the walls of the container.
2. The molecules are separated, on the average, by distances that are large compared to
their diameters and exert no force on each other exert when they collide.
3. In the absence of the external forces (the molecules are moving fast enough that we
can neglect gravity), there is no preferred direction for the velocity vector.

The 2nd assumption (assumption that the molecules are far apart) is equivalent to assuming
that the gas density is low. This is equivalent to assuming that the gas is an ideal one. Since
momentum is conserved, the collisions the molecules make with each other have no effect on
the total momentum in any direction so that these collisions can be ignored.

Let us assume a rectangular box of volume V with N molecules, each of mass m and having
speed v.

We wish to calculate the force exerted by these molecules on the right wall, which is
perpendicular to the x-axis. The x-component of the molecule momentum before it hits the
wall is +mvx and after making an elastic collision with the wall it is -mvx. The magnitude of
change of momentum during collision of one molecule with the wall is thus

P = 2mv x (3.5.2)
The total change of the momentum of all molecules during some time interval t is

2mvx(number of molecules that hit the wall during the interval)

The number of molecules that hit the right wall of area A is the number that is within the
distance (vx)t and are moving to the right. This is the number of molecules per unit volume
(N/V) times the volume (vx)tA. Therefore

1N
P = (v x tA)2mv x .(3.5.3)
2V

The factor suggests that on the average, half the molecules will be moving to the right and
half to the left. Therefore the total change in momentum P from equation (3.5.3) above is

1N N 2
P = (v x tA)2mv x = mv x At ..(3.5.4)
2V V
The force exerted by the wall on the molecules and by the molecules on the wall is F and thus
P is given by

F 1 P
P= = 3.5.5)
A A t

From equations (3.5.4) and (3.5.5)

N 2
P= mv x .(3.5.6)
V
and
2
PV = Nmv x (3.5.7)

Since all the molecules do not have the same speed, we take average value so that ( average
speed v 2 )

2 2
PV = Nmv x = 2 N ( 1 2 mv x )
2
..(3.5.8)
PV = 2 N ( 1 2 mv x )

Comparing equation (3.5.8) with

PV= kNT (derived elsewhere)(3.5.9)

Then

2
1mv x = 1 2 kT ..(3.5.10)
2

Thus, the average kinetic energy associated with motion along the x-axis is kT.

(v x ) 2 = (v y ) 2 = (v z ) 2 and

2 2 2 2 2
v = v x + v y + v z = 3v x .(3.5.11)

2 2
Writing v x = 1
3 v and the kinetic energy K.E = Kav
 K av = 1
2 mv 2 = 3
2 kT (3.5.12)

The average kinetic energy of the molecules is 3 2 kT .

The total translational kinetic energy of n moles of gas containing N molecules is

K .E = N ( 1 2 mv 2 ) = 3 2 NkT = 3
2 nRT ..(3.5.13)
Thus, the translational K.E is

( K .E ) trans = 3
2 kT (per molecule)

( K .E ) trans = 3
2 nRT (per mole)

The average value of v2 is

3kT 3 N A kT 3RT
v2 = = =
m N Am M
where M = NAm is the molar mass. The root mean square (rms) speed is

3kT 3RT
v rms = v 2 = = .(3.5.14)
m M

3.6 Exercises

1. a). System A is a paramagnetic salt with co-ordinates H.M while system B is a

chemical cell with co-ordinates .Z. System C is a gas with co-ordinates P.V.
When A and C are in thermal equilibrium the equation
HM + nB' HM
PV = 0 is found to hold. When A and B are in thermal
V
equilibrium, the relation Z nb HM = 0 is satisfied. What are the three
equations that are equal to one another at thermal equilibrium? (the symbols n,
b, and B are constants).
PV 2
Answer:[ ( Z nb) , , HM]
V nB'

2. For nitrogen the molar volume at S.T.P is 0.0224 m3 and the relative molecular
mas is 28. Calculate
a). the mass of one mole of nitrogen;
b). the mass of one molecule of nitrogen;
c). the number of molecules in one cm3 of nitrogen at S.T.P;
d). the root mean square molecular speed at S:T.P.
Answers: [28*10-3 kg; 4.65 * 10-26 kg; 2.69 * 1019; 493 m s-1]

3. Determine the value of the molar gas constant R, given that the value of one
kilomole of all gases aat S.T.P ( a pressure of one atmosphere and a
temperature of 273.15 K) is 22.4 m3.
 Answer: [ 8.31 J K-1 mol-1]

3.7 Further Reading

8. Sprackling M. (1991) Thermal Physics, chapter 3
9. Adkins C. J. (1983) Equilibrium thermodynamics, Chapter 2
10. Fink J. L. (1955) Thermodynamics, Chapter 5
 CHAPTER 4
Simple thermodynamic Systems
4.1 Objectives

By the end of this lesson, you should be able to:

Write equations of state for some simple thermodynamics systems

Compute differential changes of state
Relate the differential changes of state to physical quantities like
linear expansivity, volume expansivity, isothermal compressibility,
Youngs Modulus etc

4.2 Introduction

When the conditions for mechanical, thermal and chemical equilibrium are satisfied, a system
is said to be in a state of thermodynamic equilibrium. In this chapter the behaviour of some
simple thermodynamics systems will be considered. For each of the systems the coordinates
descriptive of the equilibrium states will be given

4.3 Equation of state of the simplest closed hydrostatic system

We consider a gas of constant mass in a vessel having coordinates P. V and . Once P and V
are chosen arbitrary the value of is determined by nature. The same is so when two of the
values are chosen, the other is determined by nature. This implies that there exists an equation
of equilibrium which connects the thermodynamic coordinate and which robs one of them off
its independence. Such an equation is called equation of state. Figure 5 below shows
isotherms of a pure substance.

Figure 5: Isotherms of a pure substance.

The pressure and the volume at the critical point are known as the critical pressure and
volume respectively. Above the critical point isotherms are continuous curves that at large
volume and low pressures approach the isotherms of an ideal gas. Figure 6 shows a P verses
temperature diagram for a substance such as water.
Figure 6: Pressure against temperature diagram for a substance such as water.

Equations of state

1. For ideal gas

PV = R (4.3.1)
This equation holds only at low pressures in the vapour and gas regions. (The
symbols have their usual meaning)

2. Van der Waals equation

a
p + 2 (V b ) = R (4.3.2)
V

This equation holds fairly well in the liquid region, the vapour
region and near and above the critical point. a and b are constants
while the other symbols have their usual meaning.

3. Beathie- Bridgman equation

R (1 )
P= 2
(V + B ) A2 (4.3.3)
V V

where A =Ao(1-a/V), B =Bo(1-b/V) and = C/V3

This equation holds fairly well in the whole range above the triple point. This is because of
its five adjustable constants.

In all these equations R is a constant called the universal gas constant, V is the molar volume
(V/n), and n is the number of moles of gas.

4.4 Differential changes of state of simple systems:

1. Gas

If f(P,V,) then V(P,) hence

V V
dV = dP + d (4.4.1)
P P

Physical meanings of the differentials

 = Change in volume per unit volume divided by the change in temperature.
Therefore

1 V
= (4.4.2)
V P

Isothermal compressibility

1 V
K = (4.4.3)
V P

If the equation of state is solved for P, then P=f(,V)

P P
dP = d + dV (4.4.4)
V V

and so for

d = dP + dV (4.4.5)
P V V P

The differentials dP,dV and d are exact differentials of actual functions.

There are two useful theorems to be used. If f(x,y,z) =0, then x= g(y,z)

x x
dx = dy + dz (4.4.6)
y z z y

also y= h(x,z)

y y
dy = dx + dz (4.4.7)
x z z x

Substituting the second equation into the first

x y y x
dx = dx dz dy + dz
y z x z z x z y
(4.4.8)
x y x y x
= dx + + dz
y z x z y z z x z y

If dz =0 and dx is not equal to zero

 x y
= 1 (4.4.9)
y z x z

or

x 1
= (4.4.10)
y z y
x z

If dx=0 and dz is not equal to zero

x y x
+ = 0 (4.4.11)
y z z x z y

therefore

x y x
=
y z z x z y
(4.4.12)
x y z
= 1
y z z x x y

In case of a hydrostatic system the above equations give

P V P
= (4.4.13)
V P V
But the volume expansivity and the isothermal compressibility K were defined as

1 V 1 V
= and K =
V P V P

Therefore

P
= K (4.4.14)
V

If there is change in pressure

P P
dP = d + dV
V V
 or using the physical quantities

dP =
1
d dV (4.4.15)
K KV

At constant volume

dP = d This implies, if there is small change in temperature the corresponding change

K
in pressure will be given by

2
Pf Pin = d (4.4.16)
K
1

2. Stretched wire

The coordinates of a stretched wire are ( , L, ) representing the tension, length and
temperature of the wire respectively.
L L
dL = d + d (4.4.17)

Linear expansivity is defined as

1 L
= (4.4.18)
L
while isothermal Youngs modulus is

L
= (4.4.19)
A L

3. Surface film

The coordinates of a surface film are (, A, ) representing the tension, Area and temperature
of the surface respectively. The equation of state

n

= 0 1 1 (4.4.20)

where o is surface tension at 0C, 1is a temperature within a

few degrees of the critical temperature and n is a constant that lies
between 1 and 2. This equation implies that the surface tension
decreases as increases and become zero when = 1.
4.5 Examples.

1. A mass of mercury at standard atmospheric pressure and a temperature of 0C is kept at

constant volume. If the temperature is raised to 10C, what will be the final pressure? Given
that = 1.81 * 10 4 K-1 and K = 3.82 *10-11 Pa 1 of mercury.
2
Pf Pin = d =
( 2 1 )
K K
1
4 1
1.81 * 10 K
= (283K 273K )
3.82 * 10 11 Pa 1
= 473 * 10 5 Pa

Pf = 473 * 10 5 Pa + 1.0 * 10 5 Pa
= 474 * 10 5 Pa

2. An approximate equation of state of a real gas at moderate pressure, devised to take

into account the finite size of molecules is P(V-b) = R, where b is a constant. Show
1
1
that a) =
and b) k= P where and k are defined as in section ..
Pb Pb
1+ 1+
R R
Solution
P(v-b) = R (i)
1 V
= (ii)
V
1 V
k = (iii)
V p
a). Making V the subject from equation (i)

R + Pb V R
V = =
P P

1 V 1 R P R R 1
= = = = =
V V P R + Pb P R + Pb 1 + Pb
R

V bP ( R + Pb) R
b). = =
P P2 P2

1
1 V 1 R RP R P
k= = = = =
V p V P
2
P ( R + Pb) PR + P b
2 2
Pb
1+
R
4.6 Exercises

1. The equation of state of an ideal gas is PV = R. Show that a) = 1/ and b) k=1/P

2.
A block of copper is under a pressure of 1.01 * 105 Pa ( 1 atmosphere) at a
temperature of 293 K. The temperature of the block is then raised to 305 K. If the
volume of the block is maintained constant during this process, calculate the final
pressure acting on the block. For copper, cubic expansivity = 50.4 * 10-6 K-1 and
isothermal compressibility = 7.20 * 10-12 Pa-1.
[Answer: 605* 105 Pa]

3. The equation of state of a certain perfectly elastic material in the form of a rod, is
subjected to an axial load F, is
F=CT(L-Lo)2
Where Lo is the unstretched length, L is the length under a load F at a temperature T
and C is a constant. Derive expressions for the linear expansivity and the youngs
modulus of the material.

4. A steel wire is in equilibrium at a temperature of 300 K and has a length of 1.00 m and
an area of cross-section of 2.0 * 10-6 m2 under zero load. The load is increased
reversibly at constant temperature to a value of 100 N. Calculate the work done on the
wire in this process and the heat absorbed by the wire. For steel, Youngs modulus =
2.00 * 1011 Pa and linear expansivity = 1.20*10 5 K-1.
[Answers: 0.013 J; 0.360 J]

4.7 Further Reading

11. Sprackling M. (1991) Thermal Physics, chapter 5
12. Adkins C. J. (1983) Equilibrium thermodynamics, Chapter 8
13. Fink J. L. (1955) Thermodynamics, Chapter 5
14. Sprackling M. (1993) Heat and Thermodynamics, chapter 8
 CHAPTER 5: WORK

5.1 Objectives

By the end of this lesson, you should be able to:

Differentiate between positive and negative work

Differentiate between reversible and irreversible processes and give
examples of such processes
Calculate work done by change in volume

By convection-
Positive work is work done by the system while negative is work done on the system

Quasi-static process
During a quasi-static process, the system is at all times infinitesimally near a state of
thermodynamic equilibrium, and all the state through which the system passes can be
described by means of thermodynamic co-ordinates referring to the system as a whole.

A reversible process
This is a quasi-static process in which all means of energy dissipation are absent. Reversible
processes are ideal and are used for comparison purposes only. During a reversible process,
the system goes through a series of equilibrium states. In this process the system is always in
equilibrium.

Irreversible process (not reversible)

All naturally occurring (spontaneous) processes are non-equilibrium or non- quasi-static, and
therefore irreversible. An irreversible process cannot be reversed without leaving the
surrounding changed, e.g. a fast moving bullet.

Question: Why are radioactive processes irreversible.

Answer: Because they are spontaneous i.e. they are getting on, shows that there is no
equilibrium, hence irreversible.

The path of a reversible process can be shown on a graph with suitable axes. We cannot do
the same for irreversible process. It is only in the reversible process that maximum work
output could be released. The following are some examples of reversible and irreversible
processes

Table 2. Examples of reversible and irreversible

Reversible Processes Irreversible processes
Changing from a metastable phase to a stable
Extension of a spring balance phase e.g. freezing of a super cooled liquid,
condensation of a supersaturated vapour
Mixing of substances
Chemical reaction of an electrochemical cell All naturally occurring process
 Transportation across a phase boundary e.g.
osmosis, dissolution of a liquid.

5.2 Work done by change in volume

Consider a fluid in a cylinder with frictionless piston as shown in the figure 7. The fluid may
do work on the surrounding by expansion.

dx

Fig 7 Expansion of fluid in a cylinder.

If at pressure P, the fluid expands by dV, the piston move by dx against an opposing pressure
Popp

Work done = F dx
= (F/A) A dx dW =P dV (5.2.1)

Work done in going from state 1 (P1V1T1) to state 2 (P2V2T2)

2
W = Pdv (5.2.2)
1

To evaluate this equation we need to know how pressure varies with volume. The volume
pressure relationship can be represented graphically on a diagram called PV diagram.
 P
P1

P2

V1 V2 V
Figure 7. Variation of P against volume during expansion (work done is equal to the shaded
area)

The area under the curve gives work done when the gas expands from V1 to V2.

V2

Work = Area = Pdv > 0

V1
(5.2.3)

P
P
P2

P1

V V1 V2
V
V2 V1

Figure 8a: P verses V during expansion; Figure 8b: Expansion at constant pressure

The area under the curve (figure 8a) gives work done when the gas is compressed from V1 to
V2
 V2

Work = Area = Pdv < 0

V1
(5.2.4)

while figure 8b shows a curve, for expansion when pressure is kept constant, which gives

W= P (V2-V1) (5.2.5)

Note:
Work done by any infinitesimal expansion must be less or equal to PdV
depending on whether the process is reversible or irreversible.

I
dW PdV
5.3 Examples R

Examples 1

An ideal gas of volume V= 0.1 m3 at a temperature of 273.15 K and a pressure of 105 Nm-2
expands reversibly to 3 times its volume. Calculate work done:
a). At constant pressure
b). At constant temperature

Solution
a). Pressure constant

W = P (V2-V1) = 105 Nm-2 (0.3-0.1) m3 = 2 *104 Joules

b). In general the work done is given by w = PdV . This equation cannot be integrated
directly. It is not known how the pressure varied during the expansion T = constant. However,
substituting for P and using the equation of state. PV = nRT for an ideal gas

nRT
w = PdV PV = nRT P =
V
v
nRT 2
dV V V 0.3
w= dV =nRT = nRT ln 2 = P1V1 ln 2 = 10 5 * 0.1 = 1.098 *10 J
4

V v1
V V1 V1 0.1

Example 2
How much work is required to compress isothermally 2 g of oxygen initially at STP to half its
original volume? (Assume that oxygen behaves as an ideal gas)

Solution
From

V
w = nRT ln 2
V1
Molecular weight of oxygen = 32. Thus number of moles n = m/M where m = mass of
oxygen and M is Molecular weight (mass)

N = 2/32 = 0.0625
V
W = (0.0625mol )(8.31J / mol.k )(273k ) ln
0.5V
1
Thus, W = (0.0625mol )(8.31J / mol.k )(273k ) ln
2
W = 98.3J

The negative sign verifies that the work done by some external agent on the gas. No
temperature change implies no change in internal energy

Example 3.

Suppose the gas in example 3 (initially at STP) is isobarically compressed to half its original
volume.

a). How much work is done for the compression

b). What temperature change occurs.

Solution

In principle if pressure remains constant, then temperature must also change so that the
change in volume occurs according to

PV = nRT

Work done by the system to external world is

V2 V2

W = PdV = P dV = P(V2 V1 )
V1 V1

V1 V PV
V2 = W = P( 1 V1 ) = 1
2 2 2

To get the initial volume of the oxygen at STP

nRT1
P1V1 = nRT1 V1 =
P1
PV1 PnRT1 nRT1
W = = =
2 2P 2

2 8.31J / mol.k
W = mol (273k )
Therefore 32 2
W = 70.9 J
 P1V1 PV
b). = Cons tan t = 2 2
n1T1 n2T2

P2 V2 n2 T2
=
P1 V1 n1 T1

But P1 = P2 and n2 = n1

V2 T2
=
V1 T1

1
T1 = T2
2
1
T2 = (273k ) = 137 K
2

5.4 Problems

1.Calculate the work done when 1 mole of a gas at 300 K expands isothermally from 0.002
m3 to 0.005 m3, in the following
a). Quasistatically and isothermally
b). By expanding freely irreversible.

2. Consider one mole of an ideal gas undergoing

1. a reversible process consisting of an isothermal expansion from (P1V1T1) to
double its volume.
2. The gas is then compressed isobarically to its original volume and
3. then heated at constant volume to its original pressure.
For each of the processes, calculate

a). Change in internal energy

b). Heat added to the gas
c). Work done by the gas
d). The net change in internal energy
e). Work done by the gas
f). Total heat added to the gas

3. One mole of an ideal gas is carried through a reversible cyclic process described by the PV
diagram below, operating between T1 and T2.
 P
a
3Po
2T=
o T1

Po b
d
c
T=
o T2

Vo 3Vo
V
Processes ab and cd are isothermal while bc and da are isochroric.

a). What is the work done by the gas in process ab?

b). Determine the heat Q added to the system during process ab.
c). What is the work done during processes bc and da?
d). Calculate the work done by the gas during the isothermal compression
e). Calculate the network done by the system
f). How much heat is removed from the system during cd?
g). Is there any heat lost or gained by the system during processes bc and da? Explain
h). Determine the heat given up by the system during process bc.
i). What is the heat added to the system during process da?
j). Calculate the thermal efficiency of the engine operating in this cycle

5.5 Further Reading

15. Sprackling M. (1991) Thermal Physics, chapter 4
16. Sprackling M. (1993) Heat and Thermodynamics, chapter 2
17. Adkins C. J. (1983) Equilibrium thermodynamics, Chapter 3
 CHAPTER 6
FIRST LAW OF THERMODYNAMICS

6.1 Objectives

By the end of this lesson, you should be able to:

State first law of thermodynamics both mathematically and

qualitatively
Show that the internal energy of a system is a point function and it is
a property of the system.
Solve problems involving internal energy, heat and work done

6.2 Definition
The first law of thermodynamics is essentially the law of conservation of energy applied to
thermodynamic system. It states

Heat Work
Mathematically

dw 0 i.e. in a cyclic process the work done is not equal to zero.

This implies that

dq 0 heat is not equal to zero.

Thus
dw = dq (dq dw) = 0
Let U be internal energy function (function of state)

dU = dq dw = dU = 0

First law of thermodynamics states that if heat is added to the system so as to increase the
internal energy by dU and also give rise to an amount of work dw, then dq = dU + dw

First law applies to any process; reversible or irreversible. Let consider a system that absorbs
heat Q and does work W and its internal energy change by U from U1 to U2 . From
conservation of energy Q =U +W, U = U2-U1.

Note
Sign convention
Heat absorbed by system (positive)
Heat rejected by system (negative)
Work done by system (positive)
Work done on the system (negative)
Consider a system which changes from state 1 to state 2 by the process A and returns to state
1 by process B or C (figure 6.1). For the cycle composed of A and B we have

A
1 C

2
B
Figure 6.1 A cyclic process

2 1

(dQ dW ) + (dQ dW ) = 0
1A 2B
.(6.2.1)

and for the cycle composed of process A and C.

2 1

(dQ dW ) + (dQ dW ) = 0 ..(6.2.2)

1A 2C

Comparing equations (6.2.1) and (6.2.2) we find that

1 1

(dQ dW ) = (dQ dW )
2B 2C

Since B and C are arbitrary functions then

(dQ dW ) is equal for both processes and is independent of the path taken,
is a point function and it is a property of the system.

(dQ dW ) = dU
By definition dU = cv T
Therefore, while working with first law of thermodynamics we are concerned with U, W and
Q or

Q = U + W.......................................(6.2.3)

6.3 Examples
Example 1

P
8* 104 Pa
b d

4
3* 10 Pa a c

-3 3 V
2* 10 m -3 3 5* 10 m
The diagram shows a series of thermodynamic processes. In process ab, 150 J of heat are
added to the system. In bd, 600 J of heat are added. Find
a). Internal energy change in process ab
b). Internal energy change in process abd.
c). The heat added in process acd.

Solution
a). No volume change occurs during process ab so;
Wab=0 and Uab = Qab = 150 J
b). bd is a constant pressure process

Wab = P(V2-V1)
= 8*104 Pa (5-2)10-3 m3 = 240 J
Total work done for process abd is
Wabd = Wab + Wbd = 0+ 240 J
Wabd = 240 J

From Q = U + W

Uabd = Qabd Wabd = 750J 240 J

Uabd= 510 J

c). Since U is path independent, the internal energy change is the same for path acd as for
the path abd.
Therefore Uacd= Uabd = 510 J.
Total work done for the path acd is

Wacd = Wac + Wcd = P(V2-V1) + 0

= 3* 104 Pa ( 5-2) 10 3 m3
= 90 J

Qacd = Uacd +Wacd = 510 J + 90 J

Qacd = 600 J
Example 2.
One gram (1g) of water (1 cm3) becomes 1671 cm3 of steam when boiled at constant pressure
at 1.013 * 105 Pa. The latent heat of vaporization at this pressure is Lv = 2.256 * 106 J/kg.

Find;
a). Work done by water when it vaporizes
b). Its increase in internal energy

Solution
a). For constant pressure process,

W = P(V2-V1)
= 1.013* 105 Pa (1671-1)10-6 m3
= 169 J

b). Heat added to water is the heat of vaporization

Q = mLv =10-3 kg ( 2.256 * 106 J/kg)

= 2256 J
From first law of thermodynamics

U = Q- W = ( 2256- 169 ) J
= 2087 J

6.4 Exercises

1. In an adiabatic process between two equilibrium states a certain system does work
of amount 400J on its surroundings. Calculate the corresponding change in internal
energy of the system.
[Answer:-400J]

2. A mole of water vapour at 100 oC and 1 atmosphere of pressure is compressed at

constant pressure to form liquid at 100oC. The heat of vaporization of water is 540
Cal/g. compute V, W, Q and U (in Joules) for the system. (the symbols have their
usual meanings)

3. A system proceeds from an equilibrium state i to an equilibrium state f by a path A

and returns to equilibrium state i by a different path B. Along path A the system
extracts heat of amount 40 J from the surroundings and does 20 J of work on the
surroundings. Along path B the system has 10 J of work performed on it by the
surroundings. Calculate the amount of heat absorbed by the system along path B.
[Answer: -30J]

6.5 Further Reading

18. Sprackling M. (1991) Thermal Physics, chapter 4
19. Sprackling M. (1993) Heat and Thermodynamics, chapter 4
20. Adkins C. J. (1983) Equilibrium thermodynamics, Chapter 3
 CHAPTER 7: CALORIMETRY

7.1 Objectives

By the
By the end
end of
of this
this lesson,
lesson, you
you should
should be
be able
able to:
to:
Distinguish between classical and statistical thermodynamics
Define
Define specific
most of heat capacity, latent
the terminologies heat,
used heat of vaporization and
in thermodynamics
heat of fusion
Distinguish between an open, closed and isolated systems
Differentiate between the
Write down examples two specific
of adiabatic andheat capacities
diathermic of gasses
walls
Explain why Cp >Cv
Relate the change in internal energy to Cv
Work out problems which involves change in temperature.

7.2 Quantity of heat

When a cold body gets into thermal contact with a hot body, the former becomes hotter and
the latter colder. The interaction that causes these thermal changes is fundamentary a transfer
of energy from one body to another. Energy transfer that takes place solely because of
temperature difference is called heat flow or heat transfer and energy transferred in this
manner is called heat.

7.3 Specific heat capacity

The quantity of heat Q required to increase the temperature of a mass m of a certain material
from temperature T1 to T2 is found to be approximately proportional to the temperature
change T2-T1= t . Q is also proportional to the mass m of the material i.e.

Q mT
Q= cmT(7.3.1)
Where c is the specific heat capacity and is different for different materials. For an
infinitesimal temperature change dT then

dQ = mcdT(7.3.2)

Specific heat capacity of a substance is defined as the heat required to raise the temperature of
a unit mass of a substance through 1C. Therefore

Q = CdT .(7.3.3)
C = mc or c = C/m.(7.3.4)

7.4 Molar heat Capacity

Sometimes, it is more convenient to describe the quantity of a substance in terms of the

number of moles (n) rather than mass m. One mole of any pure substance always contains the
same number of molecules. The molecular mass M of any substance is the mass per mole.
The total mass of a material m is equal to

m = nM(7.4.1)
Putting equation (7.4.1) into (7.3.1) we obtain
 Q = nMcdT.(7.4.2)

The quantity Mc is called the molar heat capacity (or molecular specific heat). Putting Mc =
C, then

Q = nCdt.(7.4.3)

From equation (7.3.2)

dQ = nCdT or

1 dQ
C= = Mc ..(7.4.4)
n dt
Molar heat capacity.

7.5 Latent heat

When heat is supplied to a substance, one of the many consequences is change of phase e.g.
Water to ice (fusion- liquid-solid) or Sublimation (solid to gas) or Change of structure e.g.
from one crystalline form to another.

7.5.1 Molecular theory explanation

Increase in temperature of a substance reflects an increase in K.E of molecules. The molecular

vibration increases. When a substance changes from liquid to gas, molecules move further
apart from each other. This implies that work be done against the attractive forces that hold
the molecules together. This energy must be supplied to the molecules to separate them. This
energy goes to increase the P.E of the molecules rather than K.E. Thus the temperature at this
state of transformation of the body does not change. Heat required to melt a substance of mass
m with no change of temperature in the body is

Q = mL f (7.5.1)
where Lf is the latent heat of fusion of the substance. For change of phase liquid to gas

Q = mLv .. (7.5.2)
Lv is latent heat of vaporization.

7.6 Heat capacities of ideal gasses

The specific or molar heat capacity of a substance depends on the conditions under which heat
is added to the system. Heat capacity of a gas determined at constant volume is called molar
heat capacity at constant volume (Cv). The heat capacity obtained at constant pressure is
called molar heat capacity at constant pressure (Cp). We now consider a constant volume
process. If n moles of a gas at temperature T in a rigid container is brought into contact with a
body at slightly higher temperature T + dT then, a quantity of heat dQ flows into the gas. By
the definition of molar heat capacities at constant volume Cv

dQ = nCvdT (constant volume) ...(7.6.1)

Pressure increases during this process but no work is done since dV = 0. From first law of
thermodynamics

dU = dQ dW
we get dU = dQ = nCvdT................................................................ (7.6.2)
This shows that the internal energy dU is only dependent on temperature. For a constant
pressure process,

dQ = nCpdT.(7.6.3)

Work done by the gas is dW=PdV.

From the ideal gas equation, PV=nRT we obtain that PdV = nRdT.
Therefore
dW = nRdT(7.6.4)

From the differential form of the first law of thermodynamics and using the above equations
we obtain

nCvdT = dU + nRdT..................................................(7.6.5)
Since the change in internal energy dU is only a function of temperature, the ideal gas
equation is valid for both equations 4 and 5. Therefore

NCpdT = nCvdt +nRdT

Cp= Cv +R (7.6.6)

Note:
=Cp/Cv, this ratio is an important quantity in adiabatic processes.
For an ideal gas, the change in internal energy dU = nCvdT, whether the
volume is constant or not.

7.7 Heat changes at constant pressure (Enthalpy)

First law of thermodynamics states

dQ= dU + dW(=PdW).

We consider a system that passes from state 1 to state 2. We have

2 2 2

dQ = dU + dW (= PdV ) .................................................(7.7.1).
1 1 1

If we consider that it absorbs heat isoberrically (constant pressure), we get

2 2 2

dQ = dU + P dV
1 1 1
 Q2 Q1 = U 2 U 1 + P(V2 V1 )
............................(7.7.2)
Q = Q2 Q1

Q is the heat absorbed or emitted heat

Rearranging.
Q = (U 2 + PV2 ) (U 1 + PV1 ) ..(7.7.2)

Assigning the U + PV to a quantity H, i.e. H = U+PV we get

Q = H 2 H 1 ..(7.7.3)

Thus the quantity H is an internal property of the system. This quantity is known as enthalpy.
Therefore any heat absorbed or emitted leads to a change in enthalpy, Q =H or dQ=dH. This
holds for any reversible isobaric process.

7.8 Solved Examples

Example 1
A typical room contains 2500 moles of air. Treating the air like an ideal gas, find the change
in internal energy of this air when the room is cooled from 23.9C to 11.6C at a constant
pressure of 1 atmosphere. (take = 1.400).

Solution.
This is a constant pressure process. However, for an ideal gas, the internal energy change dU=
nCvdT for every process whether the volume is constant or not.
Therefore

Cp Cv + R R
= = = 1+
Cv Cv Cv
R 8.315 J / mol.K
Cv = = = 20.79 J / mol.K
+1 1.400 1
Since the change in internal energy for ideal gas is given by dU = nCvdT irrespective of the
volume status,
dU = nC v dT = (2500mol )(20.79 J / mol.K )(11.6 K 23.9 K ) = 6.39 *10 5 J

Example 2

20g ice, initially at 20oC is heated to become water vapour at 100 oC. What amount of heat is
used in this process?

Solution
Temperature first changes from 20C to 0C
Heat required for this temperature rise = MCice = (20 * 10-3kg)(2.0*103 Jkg-1C-1)(20 C)
= 800 J
Heat required for melting the ice = MLf = (20 * 10-3kg)(3.35*105 Jkg-1)
= 6.7*103 J
Heat required for temperature change from 0C to 100 C= MCwater
= (20 * 10-3kg)(4.2*103 Jkg-1C-1)(100 C)
 = 8.4 * 103 J
Heat required to vaporize = MLv
= (20 * 10-3kg)(2.26*105 Jkg-1)
= 4.52 * 103J
Total heat required = 800 J+ 6.7*103 J+ 8.4 * 103 J+ 4.52 * 103J = 20400 J

7.9 Exercises

1. Compute the minimum work required to freeze one litre of water originally at T=20oC.

2. It takes 15 minutes to raise the temperature of a certain amount of water from 0 C to

boiling point using a heater. Then it takes 1 hour and 20 minutes more to convert all
the water into vapour. Find the latent heat of vaporization of water.

3. A substance of mass M1, specific heat C1 and temperature T1 is mixed with a second
substance of mass M2, specific heat C2 and initial temperature T2. Calculate the final
temperature T of the system after the equilibrium is established.

4. 40g of water is heated from 25 to 100oC and then vaporized. The heat of vaporization
of water is 540 cal/g. Calculate the enthalpy change.

5. A rigid cylinder contains a floating piston free to move within the cylinder without
friction. Initially the piston divides the cylinder into . On each side of the piston, the
cylinder holds 1 kmol of an ideal gas at 278 oK and 100 kPa. An electrical resistance
heater is installed in one side of the cylinder (with the gas) so as to cause the
temperature on that side to rise slowly to 445K: If the tank and the piston are perfect
heat insulators, calculate the amount of heat added to the system by resistor ( Cv =
12.56 J/mol.K, Cp= 20.88 J/mol)

7.10 Further Reading

21. Sprackling M. (1991) Thermal Physics, chapter 11
22. Sprackling M. (1993) Heat and Thermodynamics, chapter 4
23. Adkins C. J. (1983) Equilibrium thermodynamics, Chapter 3
 CHAPTER 8: IDEAL GAS LAWS

8.1 Objectives

By the
By the end
end of
of this
this lesson,
lesson, you
you should
should be
be able
able to:
to:
Distinguish between classical and statistical thermodynamics
Show
Definethe equation
most of the of state of an ideal
terminologies usedgas
in thermodynamics
Distinguish between an open,
Apply equation of state of ideal gas.closed and isolated system

8.2 Equation of state

When a gas is compressed at constant temperature then.
1. Volume (V) decreases
2. Pressure (P) increases

Also when the gas is expanded at constant temperature,

1. Volume (V) increases
2. Pressure (P) decreases

That is to say,

PV = constant (constant temperature)

This equation holds approximately for all gases at low densities. At low densities PV is nearly
proportional to temperature T so that

PV =CT where C is a constant. .(8.2.1)

Suppose there are two identical containers each holding the same amount of the same kind of
the gas at the same temperature. Each has a volume V described be equation 8.2.1. If the two
containers are combined, the result is twice the volume of the gas at the same pressure P and
temperature T. It follows then that C in equation 8.2.1 must have increased by a factor 2.
Therefore C is proportional to the amount of the gas

C=kN(8.2.2)
Where N is the number of molecules of the gas and k is a constant.
Therefore equation 8.2.1 becomes

PV = kNT(8.2.3)
Where k is the Boltzmanns constant.

The amount of the gas is conveniently written in moles

If there are n moles of a substance, the number of molecules is

N=nNA.(8.2.4)
Where NA is the Avogradros number (number of molecules in a mole).
Therefore equation (8.2.3) becomes

PV= nNAkT=nRT(8.2.5)
Where R = universal gas constant.
We define an ideal gas as one for which PV/nT is a constant for all pressures.

For ideal gas

PV = nRT(8.2.6)

9,0

8,8

8,6 H2
PV/nT (J/mol.k)

8,4

N2
8,2

Co
8,0

7,8
O2

7,6
0 10 20 30 40 50 60
Pressure (atms:)

Figure 8.1: Variation of PV/nT against pressure for different gases

Figure 8.1 shows a plot of PV/nT versus P for real gases. As the density of the gas is reduced,
thereby reducing the pressure, the ratio PV/nT approaches a common value R = 8.314
J/mol.K for all real gases.

8.2 Examples
Example 1

One hundred grams of CO2 occupies a volume of 55 litres at a pressure of 1 atm.

a). Find the temperature
b). If the volume is increased to 80 l and temperature is kept constant, determine the new
pressure.

Solution
A). Molar mass of CO2 = 44 g/mol
Number of moles = n = m/M = 100g/44g/mol.
N= 2.27 moles

PV (1atm.)(55l )
T= =
nR (2.27 mol )(0.0821l.atm / mol.K )
T = 295 K

b) P1V1T2 = P2V2T1 but T1 = T2

V1 55l
P2 = P2 = (1atm.)
V2 80l
P2 + 0.688atm.
Example 2
A spherical bulb A of volume 1.0* 10-3 m3 is connected to a bulb B of volume 0.5 * 10-3 m3
by a short tube and the whole is full of air at a pressure of 1.01 * 105 Pa and a temperature of
273 K. The temperature of the larger bulb is then raised to 373 K while that of the smaller
bulb is unchanged. Calculate:
a). the new equilibrium pressure in the connected bulbs, and
b). the fraction of the original mass of the air in the larger bulb that is transferred to the
smaller one as a result of the change of temperature.

Solution
The system is the total amount of air in both bulbs, hence is a system of constant mass.
We assume that air behaves as an ideal gas.
Let the number of moles of air in the larger bulb be n1 and that of the smaller bulb be n2.
Applying the equation PV =nRT to each bulb separately gives

1.01*105 (Pa)*1.0*10-3(m3)=n1R*273(K) for the larger bulb and

1.01*105 (Pa)*0.5*10-3(m3)=n2R*273(K) for the small bulb
In the final equilibrium state let the pressure be Pf, the number of moles of the air in the larger
bulb be n3 and in the smaller bulb be n4.
Applying the equation PV =nRT to each bulb separately gives

Pf *1.0*10-3(m3)=n3R*373(K) for the larger bulb and

Pf *0.5*10-3(m3)=n4R*273(K) for the small bulb
Conservation of the total amount of air gives
n1+ n2 = n3 + n4.
So that 1.01*105 (Pa)*1.0*10-3(m3)/ R*273(K) + 1.01*105 (Pa)*0.5*10-3(m3)/R*273(K)
= Pf *1.0*10-3(m3)/R*373(K) + Pf *0.5*10-3(m3)/R*273(K)
which give Pf= 1.23*105 (Pa)

b). Since the mass of the gas is proportional to the number of moles of gas, the fraction f of
the original mass of air in the larger bulb that is transferred to the smaller one is given by
f= (n1- n3)/ n1 and therefore

f= {1.01*105 (Pa)*1.0*10-3(m3)/ R*273(K)- 1.23*105 (Pa) *1.0*10-3(m3)/R*373(K)} /

1.01*105 (Pa)*1.0*10-3(m3)/ R*273(K)
= 0.11

8.3 Exercises

1. Calculate the volume occupied by one mole of molecules of an ideal gas at a

temperature of 273 K and a pressure of 1.01 * 105 Pa.
[Answer: 22.4 * 10 3 m3 ]

2. The volume of 100g of carbon dioxide at 1 atmosphere pressure is 55 litres.

i. Calculate the temperature of the gas
ii. If the volume is increased to 80 litres while the temperature remains
constant, determine the new pressure.

3. A 3*10-2 m3 tank contains nitrogen (N2) gas at room temperature (20oC) and a
gauge of 3.0 atmosphere. The tanks valve is opened momentarily and some
nitrogen escapes. After the valve is closed and the gas returns to room temperature,
 the tanks pressure gauge reads 2.40 atmosphere. Calculate the number of moles of
the gas that escaped.

8.4 Further Reading

24. Sprackling M. (1991) Thermal Physics, chapter 6
25. Sprackling M. (1993) Heat and Thermodynamics, chapter 3
 CHAPTER 9
THERMAL PROPERTIES AND ONE DIMENSION HEAT FLOW

9.1 Objectives

By the
By the end
end of
of this
this lesson,
lesson, you
you should
should be
be able
able to:
to:
Distinguish between classical and statistical thermodynamics
Define
Define the
mostdifferent types of coefficients
of the terminologies used in of expansion
thermodynamics
Prove the relation
Distinguish between
between linear
an open, and and
closed volume coefficients
isolated systemsof
expansion
Write down examples of adiabatic and diathermic walls
Explain the cause of thermal stresses
Explain heat transfer through conduction
Solve problems on heat transfer.

9.2 Thermal Expansion

Most solid materials expand when heated. Let us consider a rod of initial length Lo at initial
temperature To. When the temperature changes (increases) by an amount T, the length
increases by L. If T is not large, then
L T
But L Lo
Therefore
L = LoT (9.2.1)
L= Lo + L =(Lo + LoT )
The constant which characterizes the thermal expansion properties of a particular material,
is called temperature coefficient of linear expansion or simply as coefficient of linear
expansion. The unit of this quantity is K-1 or ( C)-1 . For a material having no preferential
direction of expansion, every linear expansion changes according to equation (9.2.1). Thus L
can represent a thickness of a rod, length of a square sheet or a hole in the material. Some
materials are however exceptional because they can have preferential expansion e.g. different
coefficients of expansion in different directions. Equation (9.2.1) holds for sufficiently small
temperature changes and therefore for any temperature, the coefficient of thermal expansion
can be defined by
1 dL
= (9.2.2)
L dT

Example

Find the area of a square having an initial length Lo after a temperature increase of T.

Solution
L= Lo + LoT
Area (A) = L2 = Lo2(1+ T )2 = Lo2[1 +2 T+2(T )2]
A= Lo2 +2 Lo2T+2 Lo2 (T )2
Since
T << 1 then 2 (T )2 can be ignored. Thus
A = Ao + 2 AoT= Ao(1 + 2 T)
= Ao(1 + 2 T) where = 2
A = AoT (9.2.3)
For volume change it can be shown similarly that
 V = VoT (9.2.4)
where is the coefficient of volume thermal expansion

9.3 Relation between and

Let us consider a cube of initial dimensions Lo . As the temperature increases by T, the
length increases by L. Therefore the new volume is given by

V = L3 = ( Lo + L) 3
3 2
= Lo + 3Lo (L) + 3Lo (L) 2 + (L) 3
L L L
2 3

= Lo 1 + 3 + 3 +
3

Lo Lo Lo
Since L/Lo << 1, the higher order terms can be ignored. From L = LoT
V = Vo(1+3T) (9.3.1)
Therefore V = 3VoT (9.3.2)
Comparing equations 4 and 6 we find that
= 3 (9.3.3)

Example
An automobile has a 60liter tank steel tank. The tank is filled with gasoline at 15 oC
from an underground storage tank. If the automobile is then parked in a warm place
until the tank temperature is 37 oC, how much gasoline will spill out of the automobile
tank? (steel = 1.2*10-6 o C-1 and gasoline = 9.5 *10-4 o C-1)

Solution
The gasoline will spill out due to the different volume changes

V = Vgas- Vsteel = Vo( - 3)(Tf-To)

= ( 15 gal)(9.5 * 10-4)-3(12*10-6)(37C-15C)
V = 0.3016 gal

9.4 Thermal stress

If the ends of a small rod are held so as to prevent expansion or contraction and the
temperature of the rod is changed, tensile or compressive stresses, called thermal stress are set
up in the rod. These stresses may become large enough to stress the rod beyond its elastic
limit or even beyond its breaking strength. Suppose a rod of natural length Lo and cross-
sectional area A has its ends rigidly fastened while the temperature is reduced by an amount
T, causing a tensile stress. Fractional change if the rod were to contract freely would be
L
= T (9.4.1)
Lo
Both L and T are negative. Since the rod is not free to contract, the tension must increase
enough to produce equal and opposite fractional change in length. From the definition of
Youngs modulus;
F
= A
L
Lo
 L F
= (9.4.2)
Lo A
The tensile force F is determined by the requirement that the total fractional change in length,
thermal expansion plus elastic strain must be zero.

F
T = =0
AY

F = AYT (9.4.3)
Since T represents a decrease in temperature, it is negative. So F is positive. The tensile
stress F/A in the rod is

F
= YT (9.4.4)
A

If instead, T represents an increase in temperature, The F and F/A becomes negative

corresponding to compressive force and stress respectively.

9.5 Heat Conduction

Let us consider a solid bar of cross-section area A. We keep one end of the bar at high
temperature e.g. steam bath and the other at cold temperature e.g. ice bath. (see figure 9.1)

Cold
x end

Hot A T
end
Figure 9.1

Thermal energy is conducted from hot end to cold end. If we consider a small section x
whose temperature difference is T, then

T
is called temperature gradient. Let Q be the amount of thermal
x
energy conducted through the section in sometime T.

Q
I= is called thermal current I.
t
 T
I A and I
x

Q T
I= = kA (9.5.1)
t x
k is called coefficient of thermal conductivity or thermal conductivity.
From equation (9.5.1)
x
T = I (9.5.2)
kA
or
T = IR (9.5.3)
x
where R = is called thermal resistance.
kA

Combination of Materials

Figure 9.2

Consider two slabs as shown in figure 9.2. Let T1 be temperature of the warm side, T2 the
interface temperature and T3 temperature of the cold side. At steady state conditions, the
thermal current must be the same through both slabs. This follows from energy conservation.
At steady state energy flowing in must equal to energy leaving. If R1 and R2 are the thermal
resistances of the two slabs then; for each slab

T1-T2 = IR1
T2-T3 =IR2
Adding the equations

T = T1 T2 = I (R1+ R2) = ReqI (9.5.4)

Req = R1 + R2 = equivalent resistance .(9.5.5)

This method can be applied to any number of slabs.

9.6 Exercises

1. A window glass 10mm thick and 1.2 m by 1.2 m square separates a room at 25o C
from the outside, at 40 oC. Calculate the amount of heat entering the room through the
 window each day. (thermal conductivity of soda-lime glass, typical of windows is 0.96
W.m-1k-1).
2. A composite bar is made of three uniform cylindrical rods of the same cross-section
joined end-to-end. One rod is of copper and is 0.12 m long, one is of glass and is 0.01
m long and the other is of iron and is 0.04 m long. The parts are bonded together in the
order copper, glass and iron and are in good thermal contact. The free copper end-face
is maintained at a temperature of 373 K and that of the iron is maintained at a
temperature of 273 K. If the whole bar is well lagged, calculate the temperature of the
two faces of the glass rod when conditions have become steady. The values of thermal
conductivities are: copper 4.20 W m-1 K-1, glass 0.9 W m-1 K-1 and iron 82 W m-1 K-1.
[Anwers: 370.6 K, 277.1K]

3. Internal energy is generated at a uniform rate (dQ/dt) in each unit volume of a slab of
material of large surface area and of thickness 2L. The material has a constant thermal
conductivity k. if both surfaces of the slab are maintained at a temperature To, show
that, when conditions are steady, the temperature T at a distance x from the mid-plane
of the slab is given by

T(x) = To + [(dQ/dt)/2k][L2-x2]

9.7 Further Reading

26. Sprackling M. (1991) Thermal Physics, chapter 18
27. Sprackling M. (1993) Heat and Thermodynamics, chapter 14
28. Alan J.C. Heat transfer
 CHAPTER 10: ADIABATIC PROCESSES

10.1 Objectives

By the end of this lesson, you should be able to:

Distinguish between classical and statistical thermodynamics
By the end of this
Define mostlesson,
of theyou should be able
terminologies usedto:in thermodynamics
Distinguish between an open, closed and isolated systems
Write down examples of adiabatic and diathermic walls
Explain adiabatic and isothermal process
Show the importance of the ratio Cp/Cv in adiabatic processes
Calculate work done in adiabatic and isothermal processes
1 1
Show that for adiabatic process T1V1 = T2V2 and P1V1 = P2V2

Adiabatic
Showprocess
that workindone
ideal
forgases
adiabatic process is given by 1
W = (P V P 2 V 2 )
1 1 1
10.2 Adiabatic processes
An adiabatic process is one in which no heat transfer takes place between the system and its
surrounding. The zero heat transfer is an ideal case but a system can approximate so if it is
well insulated. It can also approximate so if the process takes place so fast that there is no
enough time for heat flow to occur. In this process

dQ =0 dU = -dW (10.2.1)

P
P1 a

b
P2

Figure 10.1
V 1 V2 V
As the gas expands from V1 to V2 its temperature drops from T+dT to T. The drop in
temperature causes a decrease in internal energy due to work done by the gas. The change in
internal energy is given by dU= nCvdT while the work done by the gas during the process is
given by dW=PdV. But dU =-dW therefore

nCvdT=-PdV. (10.2.2)

From the ideal gas equation PV = nRT P = nRT/V, equation 2 becomes

 nRT
nC v dT = dV
V
(10.2.3)
dT R dV
+ =0
T Cv V
since R = Cp-Cv

R C p Cv C p
= = 1 = 1
Cv Cv Cv
(10.2.4)
dT dV
+ ( 1) =0
T V

Since >1 then (-1) is positive. From equation (10.2.4) we obtain that dV and dT are always
opposite in signs. Therefore we

Note:
An adiabatic expansion of an ideal gas (dV>0) always occurs with a drop in
temperature (dT<0), and an adiabatic compression (dV<0) always occurs with
rise in temperature (dT>0).

For finite changes in temperature and volume, we can integrate equation (10.2.4) to get

dT dV
T
+ ( 1)
V
=0 (10.2.5)

ln T + ( 1) ln V = cons tan t
(10.2.6)
ln(TV 1 ) = cons tan t
or

TV 1 = cons tan t (10.2.7)

Thus for an initial state (T1V1) and final state (T2V2)

1 1
T1V1 = T2V2 (10.2.8)

Similarly, from PV =nRT T = PV/nR

Therefore
PV 1
V = cons tan t
nR
PV
= cons tan t
nR

or since nR is a constant

PV = cons tan t (10.2.9)

For initial state (P1V1) and final state (P2V2)

P1V1 = P2V2 (10.2.10)

Work done in adiabatic process

W = -U.

For an ideal gas

U= nCv(T2-T1)

W=nCv(T1-T2) But from PV =nRT we get T1=P1V1/nR and

T2=P2V2/nR,
therefore,

P1V 1 PV
W = nC v ( 2 2)
nR nR
Cv
W = n (P1V 1 P2 V 2 ) (10.2.11)
nR
1
W = (P V P 2 V 2 )
1 1 1

10.3 Examples

Example 1.

The compression ratio of a diesel engine is 15:1. This means that air in the cylinder is
compressed to 1/15 of its initial volume. If the initial pressure and temperature are 1.01*105
Pa and 300 K respectively. Find the final pressure and temperature after compression. Take
air=1.40.

Solution:

1 1
From T1V1 = T2V2

1

V1
1 V
T2 = T1 = T1 1
V2 V1

15
= (300 K )(15) = 886 K = 613C
0.40

P1V1 = P2V2

V
P2 = P1 1 = 1.01 * 10 5 atm(15) 0.40
V2
P2 = 4.48 *10 5 Pa

Example 2

If the initial volume of the cylinder in example 1 is 1*10-3 m3, calculate the work done during
the compression.

Solution

P1V1 (1.01 *10 5 Pa)(1.00 *10 3 m 3 )

n= = = 0.0405mol.
RT1 (8.315 J / mol.K )(300 K )

Work done W = nCv(T1-T2)

W = (0.0405mol )(20.8 J / mol.K )(300 K 886 K ) = 494 J

or

1
W = (P1V1 P2V2 )
1

=
1
1.4 1
(
(1.01 *10 5 Pa)(10 3 m 3 ) (44.8 *10 5 Pa)(10
3

15
)
m 3 ) = 494 J

10.4 Exercises

1. If an ideal gas for which Cv=12.56 J/Mol K and Cp= 20.88 J/Mol K expands
reversibly and adiabatically from the initial state T1 = 450 K and V1 = 3 cm3 to a
final volume V2 = 5 cm3, find the temperature T2 and the work done during the
process and then calculate the enthalpy change H.

2. Describe how adiabatic process can be achieved if needed.

3. How much work is required to compress 5.00g of oxygen gas reversibly from 101
m3 to 21 m3 at a constant temperature of 20C. Treat oxygen as an ideal gas.

10.5 Further Reading

29. Sprackling M. (1991) Thermal Physics, chapter 2
30. Sprackling M. (1993) Heat and Thermodynamics, chapter 4
31. Fink J. L. (1955) Thermodynamics, Chapter 10
 CHAPTER 11

BLACK BODY RADIATION

11.1 Objectives

By the end of this lesson, you should be able to:

Explain thermal radiation and especially black body radiation

State and apply Stefans- Boltzman law.
State and apply Wiens displacement law
Describe the different theories on spectral distribution of radiation i.e.
Wiens, Rayleigh-Jeans and the Max-Plank theories.
Compute radiated spectral energy density for a given wavelength range

11.2 Thermal radiation

Radiation is a mechanism of thermal energy transfer in form of electromagnetism waves

(e.m). A good radiator of thermal energy is also a good absorber of thermal energy. The rate
at which an object radiates thermal energy is proportional to the surface area (A) of the
radiating body to the fourth power of its absolute temperature. If I is the rate of radiation in
watts then,

I = eAT 4 (11.2.1)

where e is emissivity of the body is a constant called Stefans constant. For black body e=
1. This law, defined by equation (11.2.1) is called the Stefans- Boltzman law. Emissivity e is
a number that varies between zero and one and depends on the composition of the body.
0 e 1
When radiation falls on an object part of the radiation is absorbed and part is reflected. Light
colored objects reflect most visible radiation while dark colored objects absorb most of it. The
rate at which an object absorbs radiation is given by

I = eAT0
4
(11.2.2)

where To is the temperature of the surrounding. The net power radiated by a body at
temperature T in an environment at temperature To is

I net = eA(T 4 T0 )
4
(11.2.3)
An object that absorbs the entire radiation incident upon it has an emissivity equal to e=1.
This body/object is called a black body. A black body is therefore an ideal radiator. A good
practical approximation of a black body is a cavity with black or rough walls (figure 11.1).
Any radiation that enters the hole has negligible chance of being reflected out through the
same hole
 Figure 11.1

This is called black body radiation or cavity radiation. As all the radiation is absorbed by the
dark rough walls of the cavity, their temperature rises and they begin to radiate. Radiation
continues until thermal equilibrium (i.e. between incident radiation and walls of cavity) is
attained. At this stage the wall starts to radiate electromagnetic energy at the same rate it
absorbs it. The radiation inside is called the black body radiation.

11.3 Wiens displacement law.

Radiation emitted by a body below 600C is not visible. Most of it is concentrated at

wavelengths much longer than the visible light (visible light is e.m radiation with such that
400 nm 700 nm. Between 600C and 700C, enough of the radiated energy is in the
visible spectrum for the body to grow dull red. At higher temperatures, it becomes bright red
or even white-hot. The wavelength at which the rate of radiation (power) is a maximum
varies inversely proportional to the temperature.

1
max
T
or max T = cons tan t (11.3.1)

The constant is known as Wiens constant = 2.9 *10. This is called Wiens displacement law.

Figure 11.2

As the temperature rises I() becomes higher and shifts to shorter wavelengths. The Wiens
displacement law has a number of applications among them:

Determination of temperature of objects from analysis of their radiation

 Mapping out variation in temperature over different regions of a body surface.
Such a mapping is called thermograph and can be used to detect cancer cells
because cancerous material is at a higher temperature than the surrounding tissue.

11.4 Theories on spectral distribution of radiation

Many theories were advanced to explain the spectral distribution of radiation. We now discuss
some of these theories namely Wiens, Rayleigh- Jeans and Max Plank theory

1. Wiens Theory
This theory was based on the thermodynamic principle.
Assumptions

a) A cavity can be assumed to be a movable piston in a cylinder

b) The radiation exerts force on the walls and so work is done in the process
c) Upon reflection from the moving piston, there is Doppler shift of the
radiation.

The Wiens results were represented in form of the spectral energy density (dU) in (Joules
/m3) for wavelengths between and +d. Thus

C15
dU = f ( , T )d = C2
d (11.4.1)
T
e

where C1 and C2 are constants and are chosen to make the best fit to the experimental data.

Results of the theory:

The curve fits the data well at short wavelengths but deviates from experimental data at long
wavelengths. Wiens curve (values) falls below the experimental values at long wavelengths.
Wiens curve (values) falls below the experimental values at long wavelengths. This is
illustrated by the sketch shown by figure 11.3.

Figure 11.3

3. The Rayleigh Jeans Theory

His theory was based on the following assumptions
a) That the cavity [black body] is a rectangular box with metallic walls and that the
electric charges in the walls are the source of the radiation:
b) The walls behave like simple harmonic oscillators and can radiate and absorb radiation
each with its characteristic natural frequency of oscillation
c) For any sufficiently large enclosure there is such an extremely great number of
oscillators that the resulting negligible difference between adjacent frequencies caused
the radiation to appear continuous over all wavelengths.
d) At a given temperature T constant operation of the oscillators means that standing
waves will be set up in the enclosure
e) With a perfectly conducting wall the standing waves must have nodes at the wall

The spectral distribution function by Rayleigh-Jeans theory is

2CkT
f ( , T ) = (11.4.2)
4

or
The spectral energy density (dU) between and + d is

dU = f ( , T )d = 8kT4

8kT
dU = f ( , T )d = (11.4.3)
4

Results
The theory fits the data at extremely long wavelengths but failed completely elsewhere as
illustrated by figure 11.4.

4. Max Plank Theory

Plank modified the Rayleigh- Jeans theory as follows.

a) Averaging the energy of a SHM oscillator by integrating over all possible energies the
oscillator may have.
b) SHM oscillator with a natural frequency was allowed to have one of the discrete
series of energies i.e.

En = nh where n = 0, 1, 2, 3, .. and h is the Planks constant.

 c) The only amount of energy E an oscillator could emit or absorb is one quantum of
energy i.e. E = h.

Plank then found that the average energy for a collection of oscillators in thermal
equilibrium at absolute temperature T is

h
E av = h
(11.4.4)

e kT
1

Transforming the variable from frequency () to wavelength ()

hc
E av = (11.4.5)
hc
e kT 1

The Planks spectral energy density dU is

8hc
dU = f ( , T )d = (11.4.6)
hckT
e 1
5

The figure below shows the spectral distribution function f(,T) based on different theories.

Plank theory fits the experimental values fully. Planks theory approaches Wiens expression
for short wavelengths while it approaches the Rayleigh- Jeans theory for long wavelengths.
Planks theory bridged the two classical radiation theories by Wiens and Rayleigh.
11.5 Examples

Example 1.
The at the peak of a spectral distribution for a black body at 4300 K is 674 nm. At what
temperature would the peak be at 420 nm.

Solution

From Wiens displacement law

maxT = constant.
Therefore 1T1 = 2T2

(674 *10-9m)(4300 K) = (420*10-9m)(T2)

T2=6900 K.

Example 2

The surface of the sun has a temperature of approximate 5800 K. to a good approximation we
may treat the sun as a black body.
a). What is the peak intensity wavelength max ?
b). What is the total radiated power per unit area?
(Take Wiens constant = 2.90 * 10-3 m.K)

Solution

a). From Wiens displacement law,

maxT = constant.

2.90 * 10 3 m.k
max =
5800k
max = 5 * 10 7 m = 500nm
b). From Stefans-Boltzman law.
For a black body e=1

I = T 4 = (5.67 *10 8 W / m 2 .k 4 )(5800k ) 4 = 64.2 MW / m 2

Example 3

Estimate the intensity of light emitted from the surface of the sun in the wavelength range 600
nm- 605nm, if the temperature of the sun T=5800 K. (Planks intensity distribution function is

2hc 2
I ( ) = , h= 6.626 10-34J.s, c= 3*10 8ms-1, k= 1.381 * 10-23 J/K)
hc

5 e kT 1

Solution:
For an exact solution, we need to integrate the intensity distribution I() between the limits
600nm- 605 nm.

605*10 9 605*10 9
2hc 2
I ( ) d = hc d
600*10 9 600*10 9 5
e kT 1

The integral however cannot be evaluated in terms of familiar functions. We therefore

approximate the area under the curve in the wavelength width range 600-605 nm.

Mean between 600nm and 605 nm m = 602.5 nm. We obtain I() at the mean , i.e.

I(602.5) is the height of the function.

Evaluating

hc (6.626 * 10 34 J .s )(2.998 *10 8 m / s )

= = 4.116
kT (6.025 * 10 7 m)(1.381 *10 23 J / K )(5800 K )

2 (6.626 *10 34 J .s )(2.998 *10 8 m / s ) 2

I ( ) = 7
= 7.81 * 1013 W / m 2
(6.025 * 10 m) (e 5 4.116
1)

But = 5.0 nm, Therefore the intensity in the range is approximate

 I ( ) = (7.81 * 1013 W / m 3 )(5.0 * 10 9 m)
I ( ) = 3.9 * 10 5 W / m 2 = 0.39 MW / m 2

From the estimate value in example 2, Sun intensity I = 64.2 MW/m2.

0.39
Comparing the above, * 100 = 0.6% . Therefore, 0.6% of the total intensity of the sun is
64.2
in the range 600-605 nm.

Example 4

2 5 k 4 4
From the Planks radiation law, show that 0 I ( )d = 15c 2 h 3 T . Use

4
x3 1 2
0 e ax 1 dx = 240 a .

Solution
Expressing I() in terms of frequency
= c =c-1 hence d = -c-2 d.
Therefore

I( )d = I ( )c d
2

0 0

From before

2hc 2
I ( ) =
hc
5 e kT 1

in terms of therefore

2hc 2
I ( ) =
hc
5 c kT

c
e
1
5

2hc 2 5
I ( )d = h
(c 2 d )

c 5 e kT 1

hence

2hc 2 3 2h 3
I ( )d =
hkT
d =
c 2 0 hkT
d
c e 1 e 1
0 0 2


Setting h/kT = a and = x we get

2h 3

0
I ( )d = 2
c 0 (e a
) d
1

From the integral

4
x3 1 2
0 e ax 1 dx = 240 a we get

2h 3 2h 1 2 1 2h 16 4 k 4T 4
c 2 0
d = 2 =
(e a
1) c 240 a 240 c 2 h4

Thus

2 5 k 4 4
I ( ) d =
0 15c 2 h 3
T

Note that this agrees with the Stefans Boltzman law I = T4.

11.6 Exercises

4. Determine the surface area of a lamp filament radiating 100 W, when the filament
temperature is 2400K, assuming it is a black body radiation.
[Answer: 0.127 m2]

5. The solar constant is the total radiant energy falling on unit area in unit time at the
Earth from the Sun, measured over all wavelengths, and has a value 1.367 kW m-2.
Calculate the total rate of radiant energy emission by the Sun and determine a value
for effective temperature of the surface of the Sun, assuming that the Sun radiates as a
black body. The distance from the Earth to the Sun is 1.469* 1011 m and the radius of
the Sun is 6.96*108 m.
[Answers: 3.84*1026 W, 5800 K]

6. The maximum value of the solar spectral emissive power occurs at a wavelength of
0.48*10-6 m and the effective temperature of the Suns surface is 6000 K. If another
star has a maximum in its spectral emissive power at a wavelength of 0.36*10-6 m,
calculate its effective surface temperature.
[Answer: 8000 K]
7. In a tungsten filament lamp it may assumed that, when conditions are steady, all the
energy supplied to the filament is lost to by radiation and that the radiation received
 from the surroundings is negligible. If the diameter of the filament is 0.32 * 10-3 m, the
absorptance of its surface is 0.3 and its operating temperature is 2450 K, estimate the
length of wire needed in a 100 W lamp.
[Answer: 16.2 cm]

11.7 Further Reading

32. Sprackling M. (1991) Thermal Physics, chapter 18
33. Sprackling M. (1993) Heat and Thermodynamics, chapter 14
34. Adkins C. J. (1983) Equilibrium thermodynamics, Chapter 8