Lecture notes on

Physics 18324312
STATISTICAL PHYSICS
Tjipto Prastowo and Mita Anggaryani
Department of Physics
Faculty of Mathematics and Natural Sciences
State University of Surabaya
Physics Department 11 February 2008
TO THE STUDENT WE LOVE
Here it is, lecture notes on Fisika Statistik, a series of lectures taught once a week in
tahun ke tiga, Jurusan Fisika, Fakultas Matematika dan Ilmu Pengetahuan Alam (FMIPA),
Universitas Negeri Surabaya (Unesa). Please note that we do not intend to replace any
standard book of statistical physics as listed in the Bibliography. Rather, we would like to
help students understand materials covered in this course through simple, but systematic
guidance.
To use math and other basic theory needed in this course, you need not just knowledge,
but skill. This can be obtained only through continual practice. You may obtain a supercial
knowledge by listening to lectures in the class, but you cannot reach the skill expected by
that way. It is common to come across student conversation outside the class, for example,
something like I understand it but I cant do the problem ! This student feels uncomfortable
to do some problem although it looks so easy when the lecturers do it in the class.
Such a statement shows lack of practice and hence lack of skill. Our dearest students,
please always study with pencil and paper at hand. You will nd that the more able you
are to choose eective methods of solving problems the easier it will be for you to master
new materials. This costs you nothing but practice, practice and again practice. Please do
remember that the best way to learn to solve problems is to solve them.
We welcome good comments for further improvements because penyusunan materi ajar
ini merupakan salah satu upaya untuk meningkatkan kualitas layanan publik. Semoga hal
ini bermanfaat bagi segenap sivitas akademik di lingkungan Jurusan Fisika FMIPA, Unesa.
Best wishes,
Kampus Ketintang, 12 Mei 2008
/ita /nggaryani, T jipto Trastowo
ii
iii
General Guidance
PHYSICS 18324312: STATISTICAL PHYSICS
Pre-requisites: Fundamental Physics (I and II) and Mathematical Physics (I and II)
Lecturers: Tjipto Prastowo, Mita Anggaryani
References: An Introduction to Statistical Physics for Students (A. J. Pointon)
Time and Place: Monday, 07.00 - 09.40am, D1
Marking Scheme: NA = 20%P + 20%UTS + 30%T + 30%UAS
NA=Final Mark, P=Presence, UTS=Mid-Exam, T=Homework, UAS=Final Exam
Notes:
1. Students are not allowed to join the class for being late (a maximum of 15 minutes
from the starting time), except for reasonable arguments.
2. Each lecturer contributes an equal proportion of mark to the nal mark.
3. P is possibly reduced to a minimum.
4. UTS = 50%Q
1
+ 50%Q
2
Q = Quiz
5. T = 50%T
1
+ 50%T
2
T = Assignment
6. UAS normally contains 4, but possibly has 5 problems.
7. Assignments will be distributed to class members and all students are required to hand
the completed assignments in within a limited time. Various penalties will be given for
any delay, i.e, 25% discounted mark for a one-day delay and 50% for a two-day delay.
There will be no mark given for more than two-day delays.
8. No additional assignments or examinations after Final Exam, except for specied
reasons with very limited permission or medical examination required.
9. Students are allowed to have their own notes (2 pages only), written in a folio paper,
in both Mid-Exam and Final Exam.
10. Other issues will be determined during the course, including details of problems and
exam time-tables. Students are strongly encouraged to be active and well-prepared. If
possible, tutorial is available for a further, detailed description of each topics.
Course Contents:
1. Chapter One: Introduction (Lectures 1 and 2)
overview, system of many particles, distribution function, description of assembly
and phase space, the scope of statistical physics
2. Chapter Two: Maxwell-Boltzmann Statistics (Lectures 3, 4 and 5)
fundamental concepts, classical systems, applications of MB statistics, Boltzmann
partition function
3. Chapter Three: Bose-Einstein Statistics (Lectures 6 and 7)
fundamental concepts, boson systems, applications of BE statistics
4. Chapter Four: Fermi-Dirac Statistics (Lectures 8 and 9)
fundamental concepts, fermion systems, applications of FD statistics
5. Quiz 1: Chapters Two, Three and Four (Lecture 10)
6. Chapter 5: Thermodynamics of Gases (Lectures 11 and 12)
concept of entropy, Gibbs paradox, semi-classical perfect gas
7. Chapter 6: Applications of Statistical Thermodynamics (Lectures 13 and 14)
system of two-energy level, harmonic oscillator, diatomic molecule
8. Quiz 2: Chapters 5 and 6 (Lecture 15)
9. Final Exam Preparation: Discussion on Quiz 1 and 2 (Lecture 16)
iv
Contents
1 Introduction 1
1.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Distribution function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Description of assembly and phasa space . . . . . . . . . . . . . . . . . . . . 3
1.4 The scope of statistical physics . . . . . . . . . . . . . . . . . . . . . . . . . 4
2 Maxwell-Boltzmann Statistics 5
2.1 The speed distribution function . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2 The momentum and energy distribution functions . . . . . . . . . . . . . . . 9
2.3 Applications of Maxwell-Boltzmann statistics . . . . . . . . . . . . . . . . . 10
2.3.1 The mean, rms and most probable velocities . . . . . . . . . . . . . . 10
2.3.2 Equipartition principle of energy . . . . . . . . . . . . . . . . . . . . 11
2.3.3 Specic heats . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.4 The Boltzmann partition function . . . . . . . . . . . . . . . . . . . . . . . . 14
2.5 Exercise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3 Bose-Einstein Statistics 17
3.1 Weight of conguration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2 Population of particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.3 The Bose-Einstein gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.4 Black-body radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.5 The specic heat of solid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.6 Exercise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4 Fermi-Dirac Statistics 29
4.1 Weight of conguration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.2 Population of fermions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.3 The Fermi-Dirac gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.4 The electron gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4.5 Exercise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
5 Termodinamika Gas 35
5.1 Konsep entropi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
5.2 Gas klasik . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
5.3 Paradoks Gibbs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.4 Gas semi klasik . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
5.5 Latihan soal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
v
vi CONTENTS
6 Aplikasi Distribusi Statistik 45
6.1 Sistem dua tingkat energi . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
6.2 Osilator harmonik . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
6.3 Gas diatomik . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
6.4 Latihan soal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Bibliography 55
Chapter 1
Introduction
1.1 Overview
This course is devoted to discuss systems containing very many particles (of order 10
23
),
which include gases, liquids and solids. The inherent problem of these systems appears to
be complex owing to the complexity of interactions of such a large number of particles. The
behaviour of these particles as a whole often reveals dierent qualitative features from that
of each of the individual particles. Since it is not possible to study the detailed behaviour
of each particle, a statistical approach then becomes plausible. The question is that what
kind of statistics is appropriate for describing the dynamics of the system? Can common
statistics handle this problem? Or, do we need to seek for an alternative method? If so,
what should we do then?
At this stage, it is useful to distinguish microscopic systems (i.e., small-scale systems of
order 10
9
m or less), whose description is of fundamental interest, from macroscopic systems
(i.e., large-scale systems of order 10
6
m or greater). In the latter systems, macroscopic
parameters, such as temperature, volume and pressure, are usually used to characterise the
systems. For an isolated, macroscopic system, these parameters may not vary with time
and the associated condition is said to be in equilibrium. Whereas for an open, macroscopic
system where interactions between particles constituting the system and the surroundings are
allowed, macroscopic parameters depend upon time. The time variations of these parameters
lead to mean values over a period of large times corresponding to a nal equilibrium state.
The discipline in which fundamental laws of physics describing the relationship between
macroscopic parameters are examined is the subject of thermodynamics. A fundamental
approach, statistical physics provides insights into macroscopic systems from a microscopic
point of view. In this approach, a wide range of physical principles from basic laws to
advanced methods are used to examine systems under consideration.
1
2 1. Introduction
1.2 Distribution function
In this section, we discuss discrete and continuous distribution functions that represent
a physical system. For any statistical data associated with this system, three important
quantities involved are: the average or mean value, the root-mean-square (rms) value and
the most probable value. If the data are given in a discrete form of x
i
, then these values are
written as x
ave
, x
rms
and x
max
, respectively, and are in general dierent from each other. In
practice, such values are obtained by introducing a discrete distribution function f
i
dened
as f
i
= n
i
/N, where n
i
is the occurrence of the individual data and N is the total number
of the data. The followings are useful denitions associated with this discrete system.

i
f
i
=

i
n
i
N
=
1
N

i
n
i
= 1, (1.1)
x
ave
=

i
x
i
f
i
=
1
N

i
x
i
n
i
, (1.2)
(x
2
)
ave
=

i
x
2
i
f
i
=
1
N

i
x
2
i
n
i
x
rms
=
_
(x
2
)
ave
, (1.3)
x
max
is obtained when f
i
is maximum. (1.4)
Let us examine further the above denitions using an explicit example: 10 students taking
Final Exam on Statistical Physics. The Final Marks are 20, 20, 35, 60, 60, 60, 60, 80, 80
and 90. From these marks we have discrete data in the form of x
i
= 20, 20, 35, 60, 60, 60,
60, 80, 80, 90, and N = 10 for which

i
f
i
=
1
N

i
n
i
=
1
10
_
n
1
+ n
2
+ n
3
+ n
4
+ n
5
_
=
1
10
_
2 + 1 + 4 + 2 + 1
_
= 1,
x
ave
=
1
N

i
x
i
n
i
=
1
10
_
20 2 + 35 1 + 60 4 + 80 2 + 90 1
_
= 56.5,
x
rms
=
1
N

i
x
2
i
n
i
=
1
10
_
20
2
2 + 35
2
1 + 60
2
4 + 80
2
2 + 90
2
1
_
= 61.1,
x
max
= 60 for f
1
= n
1
/N = 0.2, f
2
= n
2
/N = 0.1, f
3
= n
3
/N = 0.4, f
4
= n
4
/N = 0.2 and
f
5
= n
5
/N = 0.1.
As statistical physics deals with systems of very many particles, the above formulations
no longer hold. In these systems, a continuous distribution function f(x) is used to describe
the dynamics of the systems. Hence, (1.1) through (1.4) are replaced by
_
f(x) dx = 1, (1.5)
1.3. Description of assembly and phasa space 3
x
ave
=
_
x f(x) dx, (1.6)
(x
2
)
ave
=
_
x
2
f(x) dx x
rms
=
_
(x
2
)
ave
, (1.7)
x
max
occurs when the rst derivative of f(x) is equal to zero. (1.8)
In addition, a useful quantity, the standard deviation , is introduced as a measure of the
spread of data about the average value (i.e., the scatter of the measurements). The standard
deviation of the distribution is dened as
=
_
(x
2
)
ave
x
2
ave
, (1.9)
where is, by denition, positive since x
rms
x
ave
. For a normal or Gaussian distribution,
two-thirds of the values constituting the data are expected to fall within the range x
ave
.
There will always be random and systematic errors in the measurements. Mean values thus
include some error, which could also be indicated by the standard error of the mean
m
,
dened as

m
=

N
(1.10)
It is therefore possible to write the results of the measurements as x
ave

m
.
1.3 Description of assembly and phasa space
Here an assembly is dened as a group of individual components forming a physical body.
For example, in the case of a gas in a closed container such components are gas atoms or
gas molecules while the assembly is the gas itself. The state of an assembly is determined
by position and momentum of each of individual components in a six-dimensional, space
(known as phasa space). In a Cartesian coordinate system, the phasa space consists of
Euclidean space (x, y, z) and momentum space (p
x
, p
y
, p
z
). Thus, any quantity can be
written in terms of position and momentum coordinates. For example, element volume d
of a single-particle system in phasa space is written as
d = dx dy dz dp
x
dp
y
dp
z
, (1.11)
where dxdydz is element volume in Euclidean space and dp
x
dp
y
dp
z
is element volume in
momentum space. The (non-relativistic) kinetic energy of this system is written as
=
1
2m
_
p
2
x
+ p
2
y
+ p
2
z
_
, (1.12)
4 1. Introduction
where m is the mass of the system, and p
x
, p
y
and p
z
are the components of linear momentum
of the system in x, y and z directions, respectively.
The simple method above could be extended for a system consisting of many particles.
The corresponding element volume d
N
and total kinetic energy E for N particles are
respectively written as
d
N
= dx
1
dy
1
dz
1
dp
x1
dp
y1
dp
z1
dx
N
dy
N
dz
N
dp
xN
dp
yN
dp
zN
=
N

i=1
dx
i
dy
i
dz
i
dp
xi
dp
yi
dp
zi
(1.13)
and
E =
1
+
2
+
3
+
N
=
N

i=1
1
2m
_
p
2
xi
+ p
2
yi
+ p
2
zi
_
,
(1.14)
where i in both (1.13) and (1.14) refers to individual particles.
1.4 The scope of statistical physics
While modern statistical physics in general covers a broad spectrum of materials, the main
theme considered in this course involves classical and quantum statistics, with their simple
applications being introduced. There are fundamental dierences in the basic assumptions
made regarding the distinct behaviour of classical and quantum assemblies. For a classical
assembly, each of individual components is considered to be completely distinguishable. For
a quantum assembly, however, the particles constituting the assembly is considered to be
indistinguishable. Another dierence between the classical and quantum statistics is that
energy and momentum of classical systems spread over a continuum spectrum while in the
quantum systems particles are distributed over discrete energy levels. The quantum systems
studied here are divided into two groups of particles: bosons and fermions. The dierences
between these systems will be detailed in the next chapters.
The main reference to which we refer is Pointon (1978) as this book is much simpler for
undergraduate students without losing basic ideas behind the scene. The students are also
encouraged to have a read the topics considered in other sources from a fundamental level
(Tipler, 1999) to an advance level (Reif, 1985; Huang, 1987), as well as from related materials
in a standard book of modern or quantum physics (Beiser, 1988; Gasiorowicz, 1996).
Chapter 2
Maxwell-Boltzmann Statistics
It is desired to nd a continuous distribution function that characterises classical systems.
These systems are allowed to have arbitrary values of energy and momentum, for which they
obey Maxwell-Boltzmann (MB) statistics. We will derive this statistical distribution using
a simple way, independent of the details of molecular interactions. We rst construct the
classical velocity distribution function for each direction, with which we derive the MB speed
distribution function in 2.1. In order to obtain a full description of a classical assembly,
we then examine the momentum and energy distribution functions in 2.2. This is followed
by the applications of the MB statistical distribution in 2.3. The fundamental concept of
partition function is also introduced in 2.4.
2.1 The speed distribution function
Here we are particularly interested in nding the speed distribution function of a classical
system containing very many particles. Such a system can be an ideal gas in a closed volume.
Once this function is obtained, other distribution functions (i.e., energy and momentum
distribution functions) can be directly derived.
We begin with describing the dynamics of molecules of such a gas using a Cartesian
coordinate system for simplicity. The density
N
of the gas molecules per unit volume in
velocity space is determined by the product of the total number N of the molecules and
velocity distribution function for all motional directions,

N
= N f(v
x
) f(v
y
) f(v
z
), (2.1)
where f(v
x
), f(v
y
) and f(v
z
) are velocity distribution functions, and v
x
, v
y
and v
z
are the
speeds of the molecules in x, y and z directions, respectively.
5
6 2. Maxwell-Boltzmann Statistics
The total derivative d
N
of (2.1) with respect to v
x
, v
y
and v
z
is
d
N
=

N
v
x
dv
x
+

N
v
y
dv
y
+

N
v
z
dv
z
, (2.2)
which can be, due to (2.1), rewritten as
d
N
= N
_
f

(v
x
) f(v
y
) f(v
z
) dv
x
+ f(v
x
) f

(v
y
) f(v
z
) dv
y
+ f(v
x
) f(v
y
) f

(v
z
) dv
z
_
. (2.3)
It is expected to have separated parameters for each of the terms on the RHS of (2.3). Thus
we divide (2.3) by
N
, resulting in
d
N

N
=
f

(v
x
)
f(v
x
)
dv
x
+
f

(v
y
)
f(v
y
)
dv
y
+
f

(v
z
)
f(v
z
)
dv
z
.
As the density is constant, i.e., d
N
= 0, the above equation becomes
0 =
f

(v
x
)
f(v
x
)
dv
x
+
f

(v
y
)
f(v
y
)
dv
y
+
f

(v
z
)
f(v
z
)
dv
z
. (2.4)
We assume that the gas molecules are separated by distances that are suciently large
compared with the molecule diameters and that there is no external forces acting on the
molecules except when they collide. In the absence of such forces, there is no preferred
direction for the velocity of each molecule and the speed is, of course, constant. We can then
write
v.v = v
2
= v
2
x
+ v
2
y
+ v
2
z
= constant,
which can be derived with respect to v
x
, v
y
and v
z
to obtain
v
x
dv
x
+ v
y
dv
y
+ v
z
dv
z
= 0, (2.5)
as a restrictive condition for (2.4). Thus, we have so far a set of two-dierential equations,
(2.4) and (2.5). The solution of these equations can be obtained by introducing a constant
parameter , to be determined later, by which we multiply (2.5) to obtain
v
x
dv
x
+ v
y
dv
y
+ v
z
dv
z
= 0. (2.6)
We then add (2.6) to (2.4) to obtain
_
f

(v
x
)
f(v
x
)
+ v
x
_
dv
x
+
_
f

(v
y
)
f(v
y
)
+ v
y
_
dv
y
+
_
f

(v
z
)
f(v
z
)
+ v
z
_
dv
z
= 0,
where dv
x
, dv
y
and dv
z
are all not zero for non-trivial solutions. Instead, a system of
2.1. The speed distribution function 7
homogeneous dierential equations below are required,
f

(v
x
)
f(v
x
)
+ v
x
= 0,
f

(v
y
)
f(v
y
)
+ v
y
= 0,
f

(v
z
)
f(v
z
)
+ v
z
= 0,
for which f(v
x
), f(v
y
) and f(v
z
) will be determined. For the x-component, the above
expression means
df(v
x
)
dv
x
= v
x
f(v
x
) or
df(v
x
)
f(v
x
)
= v
x
dv
x
,
which can be easily solved. Integrating both sides and applying simple calculus yield
nf(v
x
) =
1
2
v
2
x
+ nC = nCe

1
2
v
2
x
.
We thus have
f(v
x
) = Ce

1
2
v
2
x
, (2.7)
where C is an integration constant, and will be determined below. The next step is thus to
determine the exact value of C by normalising (2.7) such that
_

f(v
x
) dv
x
= 1 or C
_

1
2
v
2
x
dv
x
= 1. (2.8)
As e

1
2
v
2
x
is an even function, (2.8) can then be written as
2 C
_

0
e

1
2
v
2
x
dv
x
= 1
(see Appendix 6 of Pointon, 1978 for the details of the properties of function integrals).
We here refer to
_

0
x
n
e
ax
2
dx =
1
2a
(n+1)/2

_
n + 1
2
_
(2.9)
and use (1/2) =

to calculate C as
C
_
2

_
1/2

= 1 or C =
_

2
.
Hence, (2.7) becomes
f(v
x
) =
_

2
e

1
2
v
2
x
. (2.10)
8 2. Maxwell-Boltzmann Statistics
Using (2.10), we can calculate the mean square velocity as
(v
2
x
)
ave
=
_

v
2
x
f(v
x
) dv
x
=
_

v
2
x
_

2
e

1
2
v
2
x
dv
x
=
1

, (2.11)
where we have again used (2.9) and a simple relation, (n + 1) = n(n).
According to the kinetic theory of a perfectly ideal gas, for every degree of freedom in
each direction translational kinetic energy is equal to the thermal energy of kT/2 such that
1
2
m(v
2
x
)
ave
=
1
2
kT,
1
2
m(v
2
y
)
ave
=
1
2
kT,
1
2
m(v
2
z
)
ave
=
1
2
kT, (2.12)
where m is the total mass of molecules, k is the Boltzmanns constant (1.38 10
23
J K
1
)
and T is the equilibrium temperature of the molecules. We thus have
(v
2
x
)
ave
=
kT
m
(2.13)
for the x-component of the velocity. Combining both (2.11) and (2.13) yields = m/kT
and similar results are obtained for the y and z directions. We can therefore rewrite the
x-component of the velocity distribution function in (2.10) as
f(v
x
) =
_
m
2kT
e

1
2
mv
2
x
/kT
. (2.14)
In the same manner, the velocity distribution function for the other degrees of freedom can
be obtained,
f(v
y
) =
_
m
2kT
e

1
2
mv
2
y
/kT
and f(v
z
) =
_
m
2kT
e

1
2
mv
2
z
/kT
. (2.15)
Having derived the velocity distribution function for each direction, we are now ready to
derive the corresponding speed distribution function by dening the molecule density
N
,
previously given in (2.1), as

N
=
dN
v
x
v
y
v
z
dv
x
dv
y
dv
z
, (2.16)
where dN
v
x
v
y
v
z
is the number of gas molecules having velocity components in the range v
x
to v
x
+ dv
x
in the x-direction, v
y
to v
y
+ dv
y
in the y-direction, v
z
to v
z
+ dv
z
in the
z-direction, and dv
x
dv
y
dv
z
is element volume in velocity space in a Cartesian coordinate
system. Substituting (2.16) into (2.1) gives
dN
v
x
v
y
v
z
dv
x
dv
y
dv
z
= N f(v
x
) f(v
y
) f(v
z
) (2.17)
2.2. The momentum and energy distribution functions 9
or
dN
v
x
v
y
v
z
= N
_
m
2kT
_
3/2
e

1
2
m(v
2
x
+v
2
y
+v
2
z
)/kT
dv
x
dv
y
dv
z
. (2.18)
Equation (2.18) can be written in a spherical coordinate system as follows
dN
v
r
v

= N
_
m
2kT
_
3/2
e

1
2
mv
2
/kT
v
2
sin d ddv. (2.19)
Integrating (2.19) over the whole space and using (2.17) written in terms of v yield
dN
v
= N f(v) dv = N
_
m
2kT
_
3/2
e

1
2
mv
2
/kT
v
2
dv
_

0
sin d
_
2
0
d,
or
dN
v
= N f(v) dv = 4 N
_
m
2kT
_
3/2
e

1
2
mv
2
/kT
v
2
dv, (2.20)
where dN
v
is the number of gas molecules having speed in the range v to v + dv. It is clear
from (2.20) that
f(v) = 4
_
m
2kT
_
3/2
e

1
2
mv
2
/kT
v
2
, (2.21)
which is known as the MB speed distribution function. This function is more convenient to
use than the velocity component distribution functions, dened in (2.14) and (2.15), in that
it is taken independent of direction.
2.2 The momentum and energy distribution functions
As previously mentioned, the speed distribution function dened in (2.21) can be used to
derive other forms of distribution function. For convenience, we will rst derive momentum
distribution function, then energy distribution function. But rst, we rewrite (2.21) as
f(v) dv = 4
_
m
2kT
_
3/2
e

1
2
mv
2
/kT
v
2
dv, (2.22)
where f(v) dv is the MB probability speed distribution function. Integral of this function
over the whole space is, by denition, unity since such integral describes the total probability
to nd a molecule with speed in the range v to v + dv in the velocity space. The Euclidean
volume V of each molecule is absent in the present discussion. It follows that the properties
of the molecules of ideal gases are independent of the geometry of the molecules.
Using a simple relation from classical physics p = mv and its associated dierential form
dp = mdv, we can write an expression for the MB probability momentum distribution
10 2. Maxwell-Boltzmann Statistics
function f(p) dp as
f(p) dp = 4
_
1
2mkT
_
3/2
e
p
2
/2mkT
p
2
dp, (2.23)
which characterises classical assemblies having momentum in the range p to p + dp. As is
the case of the probability speed distribution function given in (2.22), the integral of (2.23)
over the whole space equals to one. It is understood that
f(p) = 4
_
1
2mkT
_
3/2
e
p
2
/2mkT
p
2
, (2.24)
where f(p) is known as the MB momentum distribution function.
Again, using a simple formula from classical physics but this time relating momentum to
kinetic energy p =

2m and its associated dierential form dp =

_
m/2 d, we can write
an expression for the MB probability energy distribution function f() d as
f() d = 2
_
1
kT
_
3/2
e
/kT

1/2
d, (2.25)
where f() d describes classical assemblies with energy in the range to + d. Again, as is
the case of the probability speed and momentum distribution functions given in (2.22) and
(2.23), respectively, the integral of (2.25) over the whole space equals to one. It then follows
that
f() = 2
_
1
kT
_
3/2
e
/kT

1/2
, (2.26)
where f() is known as the MB energy distribution function.
2.3 Applications of Maxwell-Boltzmann statistics
2.3.1 The mean, rms and most probable velocities
As mentioned in 1.2, there are three dynamic quantities that can be drawn from a given
distribution function. These quantities are the mean, rms and most probable values. For
example, we will use the MB speed distribution function given in (2.21) to derive the mean,
rms and most probable velocities of an ideal gas in a closed container having total volume V
and N molecules. It is expected that maximum information can be obtained by calculating
such values.
Here we calculate the mean velocity v
ave
, which is by denition written as
v
ave
=
_

0
v f(v) dv = 4
_
m
2kT
_
3/2
_

0
e

1
2
mv
2
/kT
v
3
dv. (2.27)
2.3. Applications of Maxwell-Boltzmann statistics 11
Using (2.9) and a simple relation, (n+1) = n!, the above equation yields
v
ave
=
_
8kT
m
, (2.28)
where m and T are the mass and temperature of such a gas, respectively. The rms velocity
can be derived in a similar manner to that used for the mean velocity. Thus, we have
(v
2
)
ave
=
_

0
v
2
f(v) dv = 4
_
m
2kT
_
3/2
_

0
e

1
2
mv
2
/kT
v
4
dv. (2.29)
Again, applying (2.9) and (n + 1) = n(n) to (2.29) yields
(v
2
)
ave
=
3kT
m
, v
rms
=
_
(v
2
)
ave
=
_
3kT
m
. (2.30)
The above result for the rms velocity is in line with the sum of the equations in (2.12). To
make this clear, we here rewrite it as
1
2
m(v
2
)
ave
=
1
2
m(v
2
x
)
ave
+
1
2
m(v
2
y
)
ave
+
1
2
m(v
2
z
)
ave
=
3
2
kT. (2.31)
The most probable velocity occurs when the the speed distribution function f(v) dened
in (2.21) is maximum, i.e., the rst derivative of this function is zero. Thus, we have
df(v)
dv
= 4
_
m
2kT
_
3/2
_
2v
mv
3
kT
_
e

1
2
mv
2
/kT
= 0, (2.32)
for which we obtain
v
max
=
_
2kT
m
. (2.33)
The results for the mean, rms and most probable velocities conrm that they are in general
dierent. The rms velocity is the one, which is directly related to the mean energy of a
system having expression for energy in a special form that will be discussed below.
2.3.2 Equipartition principle of energy
In this section, we discuss the equipartition principle for systems having energy in the
form of quadratic terms. Such systems can be an ideal gas with the same probability of
translational movements in all directions, in which molecular interactions are negligible, or
a harmonic oscillator where potential interactions between individual components exist. For
convenience, we rst examine the application of the principle to an ideal gas, and later
extend the result to a harmonic oscillator.
12 2. Maxwell-Boltzmann Statistics
The mean energy of a perfectly ideal gas having energy between and + d can be,
with the help of (2.26), calculated as

ave
=
_

0
f() d = 2
_
1
kT
_
3/2
_

0
e
/kT

3/2
d. (2.34)
Using a functional approach of function below,
_

0
x
n
e
ax
dx =
1
a
n+1
(n + 1), (2.35)
we obtain

ave
= 2
_
1
kT
_
3/2
_
kT
_
5/2
3
4

=
3
2
kT. (2.36)
When the gas is in equilibrium, the total mean energy will be equally distributed among
the translational kinetic energies associated with momentum in the x, y and z directions.
This is well described by (2.12) and (2.31). Thus, we have

ave
=
1
2
m(v
2
)
ave
= 3
1
2
m(v
2
x
)
ave
=
3
2
kT, (2.37)
and hence
1
2
m(v
2
x
)
ave
=
1
2
kT. (2.38)
The result shows that each component of momentum that appears as a squared term in the
expression for the energy will contribute
1
2
kT per molecule.
When an equilibrium system is in rotational and vibrational motions as well, the total
energy of the system is the sum of all possible forms of the energy associated with types
of motions. Potential interaction between the individual particles may lead to vibrational
motion, where the corresponding potential energy is in the form of a quadratic term. For
example, the energy of a one-dimensional harmonic oscillator can be written as
=
p
2
x
2m
+
1
2
x
2
, (2.39)
where denotes the restoring force per unit displacement. Now we introduce a symbol ),
which is actually the same as ( )
ave
used before. Thus, we have
)
x
=
_
p
2
x
2m
_
+
_
1
2
x
2
_
=
1
2
kT +
1
2
kT = kT.
(2.40)
Notice that the LHS of (2.40) describes the mean energy corresponding to the x-component
2.3. Applications of Maxwell-Boltzmann statistics 13
of momentum of 1-D harmonic oscillator. For 3-D harmonic oscillator, we have
)
xy z
=
_
p
2
x
2m
_
+
_
p
2
y
2m
_
+
_
p
2
z
2m
_
+
_
1
2
x
2
_
+
_
1
2
y
2
_
+
_
1
2
z
2
_
=
1
2
kT +
1
2
kT +
1
2
kT +
1
2
kT +
1
2
kT +
1
2
kT = 3kT.
(2.41)
2.3.3 Specic heats
In this section, we derive a useful quantity, namely specic heat, by dening the total energy
of a classical system of N particles as E = N ). The specic heat discussed here is that of
perfectly ideal gases. For the ideal gas with total N molecules and the mean energy ), as
given in (2.36), we have
E = N ) =
3
2
NkT =
3
2
nN
o
kT =
3
2
nRT, (2.42)
where n denotes the number of moles, N
o
= 6.02 10
23
mole
1
is the Avogrados number
and R = 8.314 J mole
1
K
1
is the universal gas constant. We generalise this result for a
given system with total f degrees of freedom at temperature T to calculate the total energy
for the system as follows,
E = f
1
2
NkT = f
1
2
nRT. (2.43)
It is useful to introduce the molar specic heat at constant volume V , dened as the heat
capacity per unit mole. Unlike the heat capacity, the molar specic heat depends only on
the nature of the system under consideration. The specic heat at constant volume c
V
is
thus written as
c
V
=
1
n
_
E
T
_
V
= f
1
2
N
o
k = f
1
2
R. (2.44)
For monoatomic molecules, c
V
=
3
2
R, as directly measured from classical thermodynamics.
For diatomic molecules, there are two additional degrees of freedom regarding rotational
motions. Therefore, the diatomic gases have a total of 5 degrees of freedom, for which their
specic heat at constant volume c
V
=
5
2
R. Another quantity, the molar specic heat at
constant pressure P is dened as
c
P
=
1
n
_
E
T
_
P
= c
V
+ R, (2.45)
by which c
P
is always greater than c
V
.
The above relation is of practical importance as calculations by statistical physics are
usually performed for a xed volume, while experimental measurements are carried out
under conditions of constant pressure. Therefore, c
V
is a theoretically calculated value and
14 2. Maxwell-Boltzmann Statistics
c
P
is an experimentally measured parameter. The determination of these quantities provides
information about internal energy, and hence molecular structure. When heat is added to
a gas at constant volume, there will be no work done and so the amount of heat added is
converted to increase internal energy of the gas. When the heat is added at constant pressure,
work is done. Hence, less amount of heat is used to increase the internal energy, resulting in
a smaller increase in temperature change, compared with that at constant volume.
2.4 The Boltzmann partition function
In this section, we introduce a special function that links statistical expression for microscopic
systems to the corresponding thermodynamic functions. The detailed properties of this
function, together with the discussion of the Helmholtz free energy, will be later discussed in
Chapter 5. But for now, it is sucient to state that the Boltzmann partition function Z
describes how energy is distributed among systems in the classical assembly. This function
is dened as
Z =
_

0
g() e
/kT
d, (2.46)
where g() d is the number of states having energy between and + d, and e
/kT
is
known as the Boltzmann factor. Based on physical argument, g() d can be expressed as
the product of the density of states B and element volume d in phasa space, or simply
g() d = B d. Thus, (2.46) can be written as
Z =
_

0
Be
/kT
d =
_

Be
(p
2
x
+p
2
y
+p
2
z
)/2mkT
dx dy dz dp
x
dp
y
dp
z
= BV
_
e
p
2
/2mkT
p
2
sin d ddp = 4BV
_

0
e
p
2
/2mkT
p
2
dp
= BV
_
2mkT
_
3/2
.
(2.47)
The above partition function can be used to calculate pressure P, a measured quantity
of thermodynamic functions. With the help of this function, the total pressure of a classical
system containing N particles is written as
P = NkT
_
nZ
V
_
T
= NkT
d nV
dV
=
NkT
V
.
(2.48)
The last expression for P is well-known as the equation of state of a perfectly ideal gas,
PV = NkT = nRT, as frequently found in standard books of fundamental physics.
2.5. Exercise 15
2.5 Exercise
1. Diketahui fungsi distribusi untuk sistem kontinu sebagai berikut:
f(x) =
4x

2
e

x
for x 0
(a) Tunjukkan bahwa total peluang adalah 1.
(b) Hitunglah nilai x rata-rata, rms dan yang paling mungkin dari sistem tersebut.
2. Hitunglah kecepatan rms untuk atom gas Helium pada suhu 300 K.
3. Hitunglah pada suhu berapa molekul gas Hidrogen memiliki kecepatan yang sama.
4. Diketahui fungsi distribusi untuk sistem kontinu sebagai berikut:
f(v) = Av
2
e

1
2
mv
2
/kT
, A adalah konstanta
(a) Tentukan A untuk atom yang tiap mol-nya memiliki massa sebesar 36 gram pada
suhu 0

Celcius.
(b) Tentukan laju rata-rata partikel.
(c) Tentukan waktu bebas rata-rata, bila diketahui lintasan bebas rata-rata partikel
adalah 60

A.
5. Satu mol gas Neon bermassa 20,15 gram dan berjari-jari 1,25

A. Pada suhu 27

Celcius,
tekanannya 1,013 10
4
Nm
2
.
(a) Tentukan jarak rata-rata antara 2 atom Neon.
(b) Tentukan jumlah tumbukan rata-rata per detik yang dialami oleh satu atom Neon.
6. Diketahui satu mol gas beratom tunggal berjari-jari atom 1,05

A bermassa 4 gram
pada volume 17,5 liter, tekanan 1,01 10
5
Nm
2
dan suhu 27

Celcius.
(a) Tentukan jarak rata-rata antar atom.
(b) Tentukan jarak bebas rata-rata.
(c) Tentukan waktu bebas rata-rata
(d) Jika terdapat lubang seluas 10
2
mm
2
, tentukan jumlah atom persatuan waktu
yang menerobos keluar dari lubang tersebut.
7. Gas ideal terperangkap dalam ruang tertutup berupa silinder homogen dengan luas
penampang A dan tinggi L (searah terhadap sumbu z). Tentukan energi rata-rata
molekul gas ideal tersebut. Bagaimana bila energi potensialnya diperhitungkan?
16 2. Maxwell-Boltzmann Statistics
8. A ux of 10
12
neutrons/m
2
emerges each second from a port of nuclear reactor. If these
neutrons have a Maxwell-Boltzmann energy distribution corresponding to temperature
T = 300 K, calculate the density of neutrons in the beam (taken from Beiser, 1988,
Ch.15, problem 7).
9. By direct integration of
_

0
n() d with n() taken from equation 2.59, show that the
total energy of the assembly is
3
2
RT where R = Nk (taken from Pointon, 1978, Ch.2,
problem 2).
10. Calculate the mean values of v
x
and v
2
x
(taken from Pointon, 1978, Ch.3, problem 2).
11. Show that the integration of equation 3.10 over all polar angles leads to distribution
in equation 3.8 (taken from Pointon, 1978, Ch.3, problem 3).
12. Derive the variation of pressure with height in a column of a gas at temperature T
(a) using the fact that the change in pressure over a height dh is -g dh, where is the
density of the gas
(b) using the Boltzmann factor to give the concentration gradient of the molecules
(taken from Pointon, 1978, Ch.3, problem 1).
13. By what factor must the absolute temperature of a gas be increased to double the rms
speed of its molecules? (taken from Tipler, 1999, Ch.18, p.563, problem 35).
14. A mole of He molecules is in one container and a mole of CH
4
molecules is in a second
container. Both are in standard conditions. Which molecules have the greater mean
free path? (taken from Tipler, 1999, Ch.18, p.563, problem 37).
15. The molecules of a monoatomic ideal gas are escaping by eusion through a small hole
in a wall of an enclosure maintained at absolute temperature T.
(a) By physical reasoning (without actual calculation) do you expect the mean kinetic
energy
o
) of a molecule in the eusing beam to be equal to, or greater than, or less
than the mean kinetic energy
i
) of a molecule within the enclosure?
(b) Calculate
o
) for a molecule in the eusing beam
(taken from Reif, 1985, Ch.7, p.287, problem 7.30).
Chapter 3
Bose-Einstein Statistics
In this chapter, we discuss Bose-Einstein (BE) statistics. This statistics is used to describe
the statistical behaviour of bosons - quantum systems having integer or zero spin. As the
spin classication of particles determines the nature of the energy distribution over the
available energy states, the bosons do not obey the Pauli exclusion principle. Thus, there
is no restriction for how many bosons are allowed to occupy the same quantum state. This
chapter is outlined as follows. The concept of weight of conguration, or the number of ways
of distributing particles over the available states, is rst introduced in 4.1. The number
of particles occupying a certain state is derived in 3.2, followed by the discussion of the
condition under which a gas could be considered as a classical gas, or as a Bose-Einstein
gas in 3.3. As real examples, the applications of the BE statistics in boson systems, such
as electromagnetic radiation in space and elastic waves in solid, are discussed. The classical
Plancks radiation formula is derived in 3.4 while the Debye theory for specic heats of solid
is examined in 3.5.
3.1 Weight of conguration
There are two principal dierences between classical and boson systems. In the MB statistics,
the basic assumption made is that particles are distinguishable. Thus, the interchange of
two classical particles leads to a new arrangement. Whilst, in the BE statistics the assembly
consists of indistinguishable particles, hence the interchange of two identical particles gives
no new conguration. Another dierence between these systems arises from the nature of
the available energy states. Rather than a continuous form of energy, bosons are distributed
over discrete levels of energy.
Before further discussing bosons in detail, it is necessary to calculate the number of
ways of arranging particles within the available energy states. Let us consider two classical
particles, labelled as a and b, occupying two energy states. Based on the MB statistics, there
17
18 3. Bose-Einstein Statistics
will be four possible arrangements for these particles,
[ a [ b [
. .
arrangement 1
[ b [ a [
. .
arrangement 2
[ ab [ [
. .
arrangement 3
[ [ ab [
. .
arrangement 4
However, the rst two arrangements are, according to the BE statistics, completely identical.
Thus, they are considered to be united, resulting in only three arrangements for the system.
[ a [ a [
. .
arrangement 1
[ aa [ [
. .
arrangement 2
[ [ aa [
. .
arrangement 3
How about if such particles are distributed over three energy states. You will nd easily
that 9 congurations are possible for classical arrangements while only 6 are found for boson
arrangements. The details of these are left for students for exercise. This dierence in the
number of arrangements between classical and boson systems is associated with dierent
statistical formulations for calculation of possible congurations within each assembly. For
classical statistics, the number of possible congurations W (also known as the weight of
conguration) is given by
W = N !

i
g
N
i
i
N
i
!
, (3.1)
where g
i
and N
i
are the number of states and the number of particles in the ith sheet,
respectively, and N is the total number of particles. For boson statistics, this quantity is
written as
W =

i
(N
i
+ g
i
1) !
N
i
! (g
i
1) !
. (3.2)
We can then calculate the number of ways of arranging particles using the above formulations.
3.2 Population of particles
Having discussed the weights of congurations for both the MB and BE statistics, it is now
necessary to nd an expression for the number of particles distributed over a particular sheet.
We begin with the classical case by writing (3.1) and taking a natural logarithm of it,
nW = nN ! + n

i
g
N
i
i
N
i
!
= nN ! +

i
n
g
N
i
i
N
i
!
= nN ! +

i
_
N
i
ng
i
nN
i
!
_
(3.3)
3.2. Population of particles 19
It is useful to apply Stirlings approximation: nN ! N nN N to the above equation.
Equation (3.3) becomes
nW = N nN N +

i
_
N
i
ng
i
N
i
nN
i
+ N
i
_
= N nN +

i
_
N
i
ng
i
N
i
nN
i
_
,
where we have used

N
i
= N.
The most probable conguration corresponds to the condition under which nW reaches
maximum. This is simply written as d nW = 0, or
0 = d(N nN) +

i
d
_
N
i
ng
i
N
i
nN
i
_
= nN dN + N
dN
N
+

i
_
ng
i
dN
i
nN
i
dN
i
N
i

dN
i
N
i
_
=

i
_
ng
i
nN
i
_
dN
i
,
(3.4)
where

dN
i
= d

N
i
= dN = 0 because N is constant (see also below). It is important
to mention here that the above condition goes together with the imposed limitations on the
values of total particle N and total energy E, respectively, for which the followings hold,

i
N
i
= N = constant

i
dN
i
= d

i
N
i
= dN = 0

i
N
i

i
= E = constant

i
d(N
i

i
) = d

i
N
i

i
= dE = 0
(3.5)
Thus we can write
d nW + dN + dE = 0, (3.6)
where and are Lagrange multipliers that are to be later determined. Now we have all
ingredients needed to develop Lagrangian method using (3.4), (3.5) and (3.6). Equation (3.6)
becomes

i
_
ng
i
nN
i
+ +
i
_
dN
i
= 0, (3.7)
which requires
ng
i
nN
i
+ +
i
= 0.
After several simple steps, we obtain the particle population N
i
in the ith sheet,
N
i
=
g
i
e
(+
i
)
. (3.8)
20 3. Bose-Einstein Statistics
From the discussion of the Boltzmann partition function in 2.4 we have Z in a continuous
form,
Z =
_

0
g() e
/kT
d.
Rewriting this Boltzmann partition function into a discrete form gives
Z =

i
g
i
e

i
/kT
. (3.9)
Dividing both sides of (3.9) by N results in
Z
N
=

g
i
e

i
/kT

N
i
. (3.10)
In order to derive the number of particles occupying a particular sheet, we here dene
N
Z
e

(3.11)
and substitute it into (3.10) to obtain
N
i
=
g
i
e
(
i
/kT)
. (3.12)
It is clear from (3.8) and (3.12) that
=
1
kT
. (3.13)
The same result can also be obtained from thermodynamics. It is important to keep it
in mind that either (3.8) or (3.12) is frequently referred to as classical distribution (also
known as classical population number), which describes population of particles within
each sheet in the classical assembly.
In a similar manner to the above steps, we can derive the number of bosons, or boson
population number, occupying available quantum states by rst taking a natural logarithm
of (3.2),
nW = n

i
(N
i
+ g
i
1) !
N
i
! (g
i
1) !
=

i
_
N
i
+ g
i
1
_
n
_
N
i
+ g
i
1
_
N
i
nN
i
(g
i
1) n(g
i
1),
(3.14)
where we have applied Stirling approximation to the above derivation.
The most probable conguration for boson distribution is obtained when (3.14) reaches
3.3. The Bose-Einstein gas 21
maximum, or d nW = 0. Again, using (3.5) and (3.6) we can write
0 = d nW + dN + dE
=

i
_
n(N
i
+ g
i
1) nN
i
+ +
i
_
dN
i
.
(3.15)
The solution of (3.15) requires
0 = n(N
i
+ g
i
1) nN
i
+ +
i
= n(N
i
+ g
i
) nN
i
+ +
i
,
(3.16)
where we have again used Stirling approximation, i.e., N
i
1 to simplify calculation. After
simple algebra, we obtain the population number of bosons in the form of
N
i
=
g
i
e
(
i
/kT)
1
, (3.17)
where we have used = 1/kT. Equation (3.17) is frequently referred to as quantum
distribution for bosons (also known as boson population number), which describes
population of bosons within each sheet in the boson system. It can then be shown easily
that (3.17) approaches to (3.12) when g
i
N
i
. It follows that the number of states is much
larger than the population of particles. Note that has not been yet determined, and that
it is the purpose of the next section to derive the actual form of .
3.3 The Bose-Einstein gas
In this section, we examine conditions under which a gas may obey either the MB or BE
statistics. In doing so, we need to assume that each available energy state in the quantum
assembly occupies a denite volume in phasa space. From the discussion of the Boltzmann
partition function in 2.4, it is dened that g() d = Bd, where g() d denotes the number
of available energy states having energy in the range to + d and B is a unique constant
associated with the denite volume, which will be determined below.
For a single allowed energy state (i.e., g = 1) occupying element volume d in phasa
space, we can write
1 = Bd
= Bdx dy dz dp
x
dp
y
dp
z
= Bdx dp
x
dy dp
y
dz dp
z
.
Assume that the changes in position and momentum in each direction are nite, the above
22 3. Bose-Einstein Statistics
expression can then be written as
1 = B x p
x
. .
h
y p
y
. .
h
z p
z
. .
h
= Bh
3
,
for which B = 1/h
3
. Here we have taken x p
x
= h from the Heisenbergs uncertainty
principle. Similar expressions for the other two directions also hold. Thus, equation (2.47)
can be written as
Z =
V
h
3
_
2mkT
_
3/2
. (3.18)
Hence, equation (3.11) becomes
N
Z
=
Nh
3
V
_
2mkT
_
3/2
= e

= A, (3.19)
where A is constant. The necessary condition under which the gas can be considered as a
classical gas is closely related to the value of A. In most cases, this value is suciently small
(i.e., A
1
1) such that A
1
e
/kT
1 A
1
e
/kT
. If this condition is satised then boson
population (3.17) approaches to the classical distribution (3.12).
Consider here, for example, Helium gas with molar mass of 4 gram per mole
1
at standard
atmospheric pressure of 1 atm. The value of A for the He gas is approximately 3 10
6
at T = 300 K, drops to 0.15 at T = 4 K. Thus, the He gas at room temperature obeys
classical distribution, and even at low temperature of T = 4 K, the He gas will behave, to
some degree, as a classical gas.
3.4 Black-body radiation
Here we consider electromagnetic radiation within an enclosure of volume V with enclosure
walls being maintained at temperature T. The radiation can be considered as a collection of
photons, and is assumed to obey the BE statistics. When the photons set in motion within
the container, some of them are continuously absorbed and reemitted by the walls. In this
context, the number of photons inside the enclosure is not conserved. Because (3.6) must
hold, it follows that must be zero, leading to A = 1. Thus, (3.17) can be rewritten in the
form of
N() d =
g() d
e
/kT
1
, (3.20)
where we have invoked e

= A
1
= 1. N() d and g() d denote the number of photons
and the number of available states with energy in the range to + d, respectively.
3.4. Black-body radiation 23
Note that the energy of a photon depends on the frequency or equivalently on the
wavelength of the radiation, i.e., = h = hc/, and that it is radiated in space over the
whole values of either frequency or wavelength. Thus, equation (3.20) can be written in two
forms,
N() d =
g() d
e
h/kT
1
N() d =
g() d
e
hc/kT
1
,
(3.21)
where N() d and g() d denote the number of photons and the number of available states
with frequency in the range to + d, respectively. Similar denitions hold for N() d
and g() d in the second equation of (3.21).
The energy distribution of the photons can be obtained by rewriting the number of
available energy states g as
g = 2
d
h
3
= 2
dx dy dz dp
x
dp
y
dp
z
h
3
= 2
V 4p
2
dp
h
3
, (3.22)
where the multiplier 2 in front of element volume d arises from the fact that there are
two independent directions of spin orientation, that is parallel and anti-parallel to the photon
linear momentum.
Another physical argument based on which the multiplier 2 is derived is that according
to the particle-wave duality, a photon with a denite spin state corresponds to a propagating
electromagnetic wave having two independent directions of polarisation, with each direction
being perpendicular to the wave propagation. For simplicity, it is assumed that photons are
linearly polarised.
The number of available states having wavelength in the range to + d can be derived
with the help of the De Broglies hypothesis, p = h/. Substituting this relation into (3.22)
yields
g() d = V
8

4
d. (3.23)
Here we dene the density of states ( having wavelength between and + d as the
number of available states g() d per unit volume V such that (3.23) becomes
(() d =
8

4
d. (3.24)
The photons are distributed over the available states, in which the associated energy density
c in the range of wavelength between and + d is dened as the product of the photon
energy and the density of photons ^ (i.e., the number of photons per unit volume, N/V )
24 3. Bose-Einstein Statistics
as follows,
c() d = ^
=
hc

(() d
e
hc/kT
1
=
8hc

5
d
e
hc/kT
1
.
(3.25)
The above expression is known as the Plancks radiation formula for the spectral distribution
of radiant energy within a thermal equilibrium enclosure at temperature T.
Two possible, interesting approximations can be directly derived from the last expression
of (3.25). At suciently long wavelengths, or when hc/ kT, we have
e
hc/kT
1 = 1 +
hc
kT
+ 1
e
hc/kT
1 +
hc
kT
for which (3.25) becomes
c() d =
8kT

4
d, (3.26)
which is known as the classical Rayleigh-Jeans formula for the spectral distribution of
radiant energy within an enclosure. On the other extreme, at suciently short wavelengths,
or when hc/ kT, we have
e
hc/kT
1 e
hc/kT
for which (3.25) becomes
c() d =
8hc

5
d
e
hc/kT
, (3.27)
which is known as the classical Wiens formula for the distribution of radiant energy within
an enclosure.
Thus, it has been shown that the Plancks formula (3.25) for black-body radiation is valid
over the whole spectrum of wavelengths, or accordingly frequencies. The formula covers the
empirically observed ndings of the spectral distribution of electromagnetic radiation that
are previously unexplained by classical electrodynamic and thermodynamic theories.
Let us now assume that there is a small hole in the enclosure wall, giving a way for the
photons to radiate out. The number of photons emitted per unit time per unit area of the
hole (i.e., the ux of photons crossing the hole) is written as
^
rad
() d =
1
4
c ^() d, (3.28)
because the photon is always in move with the velocity of light c in free space.
3.4. Black-body radiation 25
By analogy, the energy radiated out per unit time per unit area of the hole is then given
by
c
rad
() d =
1
4
c c() d. (3.29)
Substituting the Plancks formula (3.25) into (3.29) results in
c
rad
() d =
2hc
2

5
d
e
hc/kT
1
. (3.30)
Integrating both sides of (3.30) gives
_

0
c
rad
() d =
_

0
2hc
2

5
d
e
hc/kT
1
,
and arranging the integral leads to
E
rad
=
2k
4
T
4
h
3
c
2
_

0
(hc/kT)
3
e
hc/kT
1
d
_
hc
kT
_
,
where E
rad
denotes the total energy radiated out of the hole per unit time per unit area.
Now let us introduce x = hc/kT as a variable of integration such that
E
rad
=
2k
4
T
4
h
3
c
2
_

0
x
3
e
x
1
dx. (3.31)
The integral can be evaluated with the help of some steps (see Gasiorowicz, 1996, p.5),
_

0
x
3
e
x
1
dx =
_

0
x
3
dx e
x

n=0
e
nx
=

n=0
1
(n + 1)
4
_

0
y
3
e
y
dy = 6

1
1
n
4
=

4
15
.
Equation (3.31) then becomes
E
rad
=
_
2
5
k
4
15h
3
c
2
_
T
4
= T
4
, (3.32)
where is called the Stefans constant (5.7 10
8
Watt m
2
K
4
). The above equation is
known as the Stefan-Boltzmann law for the energy density of electromagnetic radiation at
temperature T. It is found empirically that an additionally constant e, the emissivity of a
substance should be added to the RHS of (3.32). The magnitude of this quantity depends on
the characteristics (or surface) of the object, which is valued between 0 and 1. Objects that
are grouped into perfect heat absorbers (or heat radiators) have unit emissivity. Conversely,
imperfect heat absorbers (or heat radiators) correspond to the value of emissivity between
0 and 1. Black holes in the universe are considered as perfect black-body.
26 3. Bose-Einstein Statistics
3.5 The specic heat of solid
As previously discussed in 3.4, electromagnetic radiation is quantised as photons. In this
section, the energy of elastic waves propagated in solids is quantised as phonons, which obey
the BE statistics. The energy of a phonon also depends upon frequency. For convenience,
we use the phonon frequency as a dynamic variable. Thus, the phonon population having
frequency between and + d is written as
N() d =
g() d
e
h/kT
1
. (3.33)
Here we use Debye approximation, g() d = C
2
d for
m
, where C is a constant
and
m
is the maximum frequency corresponding to three modes of vibration, that is one
longitudinal polarisation and two transverse relative to the direction of propagation of the
waves. It should be noted that the former polarisation is associated with a compressional
wave and the latter corresponds to shear waves. Hence, for a solid having N atoms, there
exists a total of 3N allowed states. It follows that
3N =
_

m
0
g() d = C
_

m
0

2
d,
for which C = 9N/
3
m
. Thus, equation (3.33) becomes
N() d =
9N

3
m

2
d
e
h/kT
1
for
m
. (3.34)
The total energy of phonons in solid is determined by the energy of a phonon = h and
the number of phonons N() d with frequency in the range to + d,
E =
_

m
0
N() d =
9Nh

3
m
_

m
0

3
d
e
h/kT
1
. (3.35)
In the same manner as the denition in (2.44), the specic heat of solid can be derived with
the help of (3.35),
c
V
=
1
n
_
E
T
_
V
=
9N
o
h
2

3
m
1
kT
2
_

m
0

4
e
h/kT
d
_
e
h/kT
1
_
2
. (3.36)
We introduce a new variable, x = h/kT and a new parameter, namely Debye temperature
= h
m
/k to replace (3.36) by
c
V
= 9N
o
k
_
T

_
3
_
/T
0
x
4
e
x
dx
_
e
x
1
_
2
. (3.37)
3.6. Exercise 27
There will be two regions of temperature for which (3.37) is evaluated. For a region of
high temperatures, it is understood that /T 1 and e
x
1 + x 1. In this condition,
equation (3.37) becomes
c
V
= 9N
o
k
_
T

_
3
_
/T
0
x
2
dx = 3R, (3.38)
where R replaces N
o
k. The above result is the same as that derived from the classical
equipartition of energy.
At low temperatures, however, /T 1 hold and the upper limit approaches to innity.
Thus, equation (3.37) becomes
c
V
= 9R
_
T

_
3
_

0
x
4
e
x
dx
_
e
x
1
_
2
. (3.39)
The integral can be evaluated with the help of some steps below,
_

0
x
4
e
x
dx
_
e
x
1
_
2
= 24

1
1
n
4
=
4
4
15
.
Substituting the above expression into (3.39) results in
c
V
=
12
5

4
R
_
T

_
3
. (3.40)
Note that the above results for high and low temperatures derived from (3.37) are in good
agreement with experimental measurements of the specic heat of solids. The equation is
therefore usually referred to as the Debye theory for the specic heat of solid, and is applicable
to most metals.
3.6 Exercise
1. Jelaskan dengan dua cara pendekatan dalam hal apa Distribusi Bose-Einstein (3.17)
menuju ke Distribusi Maxwell-Boltzmann (3.12).
2. Persamaan radiasi elektromagnetik Planck untuk foton dalam ruang tertutup pada
temperatur T dinyatakan oleh
c() d =
8hc

5
d
e
hc/kT
1
(a) Carilah bentuk persamaan radiasi Planck dalam variabel frekuensi .
28 3. Bose-Einstein Statistics
(b) Jika
m
menyatakan besarnya panjang gelombang radiasi pada kerapatan energi
maksimum, tunjukkan dari persamaan radiasi Planck bahwa
m
T = 2, 9 10
3
mK.
(c) Kerapatan energi maksimum cahaya matahari terjadi pada panjang gelombang
radiasi 4,84 10
7
m. Dengan menganggap matahari sebagai benda hitam, berapakah
temperatur permukaan matahari ?
3. Using equation (4.20) of Pointon (1978), or alternatively the equation below
^() d =
8

4
d
e
hc/kT
1
show that the total number of photons per unit volume of an enclosure at temperature
T is given by
16
_
kT
hc
_
3

n=1
1
n
3
where the ns are positive integers (taken from Pointon, 1978, Ch.4, problem 1).
Chapter 4
Fermi-Dirac Statistics
In this chapter, we examine a group of quantum particles having half-integer spin which
obey the Pauli exclusion principle. Such particles are called fermions and the quantum
statistics used to describe the fermions is commonly known as Fermi-Dirac (FD) statistics.
This chapter is outlined as follows. The number of ways of arranging fermions or the weight
of conguration is shortly introduced in 4.1, followed by the discussion of the fermion
population in 4.2. The discussion of these sections is mostly similar to that for the BE
statistics, and thus many details are left for students. The concepts of the Fermi energy
and Fermi function, as well as their properties under ideal conditions, are examined in 4.3.
Finally, the application of the Fermi distribution to real cases is discussed. Because of the
high concentration of conduction electrons in a metal, an electron gas cannot be treated as
a classical gas. It will be later shown in 4.4 that the FD statistics is appropriate for the gas
in a metal.
4.1 Weight of conguration
Let us consider an isolated, quantum assembly containing N non-interacting fermions with
total energy E. These fermions are distributed over energy sheets, which include all available
states g
i
. As with bosons, fermions are indistinguishable particles, hence any rearrangement
of these particles within the available states will make no conguration. Unlike bosons, the
number of fermions occupying a single state is limited by the exclusion principle. It follows
that there exists only one particle or no particle per unit state. Thus, the number of possible
conguration for fermions can be written as
W =

i
g
i
!
N
i
! (g
i
N
i
) !
, (4.1)
where N
i
is the number of particles in the sheet i, which will be derived in the next section.
29
30 4. Fermi-Dirac Statistics
4.2 Population of fermions
Recall again that in the Lagrange method (3.6), we have
d nW + dN + dE = 0,
where and are the Lagrange multipliers. In a manner similar to the steps discussed in
Chapter 3, we derive the fermion population by rst taking the natural logarithm of (4.1),
and then applying (3.5) to the above expression. After several simple algebra, we obtain
N
i
=
g
i
e
(+
i
)
+ 1
. (4.2)
The above expression is called the Fermi-Dirac distribution or fermion population
number, which may be written in the form of
N() d =
g() d
e
(+)
+ 1
= f() g() d, (4.3)
where f() is
f() =
1
e
(+)
+ 1
. (4.4)
Here = 1/kT as before, but this time is dened as
F
/kT (dierent from that for
bosons), where
F
is known as the Fermi energy. With this new denition for , we can
rewrite (4.4) as
f() =
1
e
(
F
)/kT
+ 1
, (4.5)
which is generally called as the Fermi function. This function provides the probability of
nding fermions with energy in the given sheets.
4.3 The Fermi-Dirac gas
It is widely known that the absolute zero of temperature has never been achieved, and so
the condition under which the Fermi-Dirac gas behaves at T = 0 K is considered to be an
ideal case. Therefore, we here examine the behaviour of the Fermi function and derive the
Fermi energy at this temperature for comparison. We begin with analysing f() at T = 0 K
as follows.
f() =
1
e

+ 1
= 1 for <
F
(0)
and
f() =
1
e

+ 1
= 0 for >
F
(0)
4.3. The Fermi-Dirac gas 31
The above values for f() at T = 0 K imply that all states with energy smaller than
F
(0)
are occupied while those having energy greater than
F
(0) are empty. These values are used
to evaluate the Fermi energy at T = 0 K.
In doing so, we rst write explicitly the number of available states for fermions and to
relate it to the volume occupied by these states in phasa space. Recall again that the relation
between the number of states g() d and element volume in phasa space d is given by
g() d = Bd
= 2
dx dy dz dp
x
dp
y
dp
z
h
3
= 2
V 4p
2
dp
h
3
,
where the multiplier 2 arises from the fact that for fermions there are two independent
directions of spin orientation. Based on classical linear momentum-kinetic energy relation
p
2
= 2m, the above expression can be rewritten as
g() d =
4 V
h
3
(2m)
3/2

1/2
d. (4.6)
Now integrating both sides of (4.3) and inserting (4.6) yields
_

0
N() d =
_

0
f() g() d,
where the LHS of the above integral denotes the total number of fermions and the RHS can
be separated into two parts as follows.
N =
_

F
(0)
0
f() g() d +
_

F
(0)
f() g() d
Substituting the values of Fermi function f() at T = 0 K and equation (4.6) to the above
expression results in
N =
4 V
h
3
(2m)
3/2
_

F
(0)
0

1/2
d
= 4 V
_
2m
h
2
_
3/2
2
3

F
(0)
3/2
,
from which we obtain the Fermi energy at T = 0 K below,

F
(0) =
_
3N
8V
_
2/3
h
2
2m
(4.7)
32 4. Fermi-Dirac Statistics
Fermi-Dirac gas
F
(0) in eV T
F
in K
Helium-3 atoms 0.94 10
3
10
electron gas in Lithium 4.7 5.4 10
3
electron gas in Potassium 2.1 2.4 10
3
Table 4.1: The values of the Fermi energies at T = 0 K and Fermi temperatures for
some Fermi-Dirac gases.
We may equate the Fermi energy at T = 0 K to thermal energy kT to derive a Fermi
temperature T
F
as follows,
T
F
=
_
3N
8V
_
2/3
h
2
2mk
. (4.8)
We here provide examples of the values of
F
(0) and T
F
for some dierent Fermi-Dirac gases
in Table 4.1. It is clear from Table 4.1 that molecular gases, such as He-3 atoms which
consist of fermions, have a low Fermi temperature compared with room temperature.
However, it has been already shown in 3.3 that the He-4 gas behaves as a classical gas
at T = 300 K. It means that the energy distribution of the gas molecules at ordinary (room)
temperature will approximate to the classical, MB statistics. The condition under which
molecular gases obey classical distribution does not hold for an electron gas in a metal. It
is therefore necessary to discuss the electron gas in the next section.
4.4 The electron gas
The fact that the Fermi temperature for the electron gas in a metal is high (see Table 4.1)
leads to a fundamental idea: an increase in temperature from absolute zero to a value around
room temperature may only aect the electrons with the energy near the Fermi energy. This
can be shown below,
for =
F
kT f() =
1
e
1
+ 1
= 0.73
for =
F
f() =
1
e
0
+ 1
= 0.50
for =
F
+ kT f() =
1
e
1
+ 1
= 0.27
The mean values of dynamics properties of the electrons can then be evaluated easily.
For example, the mean energy of the electron gas at T = 0 K is given by

(0)
_
=
_

0
N() d
_

0
N() d
, (4.9)
4.5. Exercise 33
where N() d is given in (4.3). After several simple steps, we obtain
3
5

F
(0) for the mean
energy at T = 0 K. In a similar manner to the above steps, the mean velocity of the electron
at T = 0 K can also be evaluated using

v (0)
_
=
_

0
v N() d
_

0
N() d
, (4.10)
and the result is
3
4
v
F
, where v
F
is the velocity of the electron at the Fermi energy.
Note that equations (4.7) and (4.9) hold for T = 0 K only. In fact, the Fermi energy and
the mean energy of the gas electrons are a function of temperature. Thus, it is necessary to
nd the general form of the Fermi energy
F
and the mean energy of the electrons ) at
temperature T. The details of calculations are left for students (see Appendix 7 of Pointon,
1978 for help), but the main results are here presented. The Fermi energy is

F
=
F
(0)
_
1

2
12
_
T
T
F
_
2
_
(4.11)
and the mean energy of the electrons is
) =
F
(0)
_
3
5
+

2
4
_
T
T
F
_
2
_
. (4.12)
The second terms in the bracket of both (4.11) and (4.12) are considered as the correction
terms that are in fact relatively small compared with the rst terms in each equation.
4.5 Exercise
1. Jelaskan dengan dua cara pendekatan dalam hal apa Distribusi Fermi-Dirac (4.2)
menuju ke Distribusi Maxwell-Boltzmann (3.12).
2. Jelaskan perbedaan antara Statistik Bose-Einstein and Statistik Fermi-Dirac.
3. Gas isotop Helium-3 mengikuti Statistik Fermi-Dirac dengan fungsi distribusi sebagai
berikut
N
i
=
g
i
e
(
F
)/kT
+ 1
(a) Turunkan energi Fermi pada temperatur 0 K.
(b) Tunjukkan bahwa energi rata-rata elektron pada temperatur 0 K adalah
3
5

F
(0).
(c) Hitunglah energi rata-rata elektron pada temperatur 0 K.
34 4. Fermi-Dirac Statistics
4. Perak mempunyai rapat massa 10,5 10
3
kgm
3
dan pada temperatur 0 K, 1 mol
atomnya mengandung 107,88 gram. Elektron logam perak tunduk pada Statistik
Fermi-Dirac.
(a) Hitunglah kerapatan elektron logam perak pada temperatur 0 K.
(b) Hitunglah energi Fermi pada temperatur 0 K.
(c) Hitunglah energi rata-rata elektron pada temperatur 0 K.
(d) Hitunglah energi Fermi pada temperatur 300 K.
5. Show that the mean velocity of an electron in an electron gas at the absolute zero of
temperature is
3
4
v
F
, where v
F
is the velocity of an electron at the Fermi energy (taken
from Pointon, 1978, Ch.5, problem 1).
6. Show that, for a gas in which the molecules behaves as fermions, the value of the Fermi
energy is approximately

F
kT n
_
Nh
3
V (2mkT)
3/2
_
for reasonably high temperatures (taken from Pointon, 1978, Ch.5, problem 3).
Chapter 5
Termodinamika Gas
Distribusi statistik klasik (MB) maupun statistik kuantum (BE dan FE) melibatkan dua
besaran makroskopik, yaitu energi total E dan temperatur mutlak T. Pembahasan kedua
macam distribusi statistik tersebut (klasik dan kuantum) mengasumsikan bahwa tidak ada
interaksi antara sistem dan lingkungan, sedemikian sehingga jumlah total partikel N dan
energi total E dapat dianggap tetap, jadi berlaku dN = 0 dan dE = 0. Namun seperti
telah dibahas pada Bab 3 untuk radiasi elektomagnetik yang menembus lubang pada ruang
tertutup, jumlah partikel (foton) berubah setiap saat, jadi dN = 0 tidak lagi berlaku.
Pembahasan lebih jauh memberikan kemungkinan interaksi antara sistem dan lingkungan,
sedemikian sehingga bisa saja berlaku dN = 0 tetapi dE ,= 0, atau bisa juga berlaku dN ,= 0
tetapi dE = 0, atau keduanya dN ,= 0 dan dE ,= 0.
Rincian topik bahasan Bab 5 ini adalah sebagai berikut. Konsep entropi untuk sistem
tertutup diperkenalkan pada pasal 5.1, diikuti dengan pembahasan penerapan entropi pada
gas klasik pada pasal 5.2. Salah satu contoh gejala sis yang tidak dapat dijelaskan dengan
konsep statistik gas klasik adalah peristiwa yang dikenal sebagai Paradoks Gibbs, yang akan
dibahas pada pasal 5.3. Konsep statistik gas semi klasik akan dibahas pada pasal 5.4 sebagai
alternatif solusi untuk mengatasi masalah Paradoks Gibbs.
5.1 Konsep entropi
Satu dari dua pengali Lagrange, yaitu telah diturunkan (lihat kembali persamaan 3.13),
dimana diperoleh = 1/kT. Besaran ini digunakan untuk merumuskan ulang bentuk
persamaan diferensial Lagrange (3.6) yang diterapkan untuk sistem tertutup, dimana jumlah
partikel N dan volume V dapat dianggap tetap, jadi berlaku dN = 0 dan dV = 0. Hukum
pertama Termodinamika dalam bentuk diferensial menyatakan bahwa
dQ = dE + P dV, (5.1)
35
36 5. Termodinamika Gas
dimana dQ adalah perubahan panas yang terjadi pada sistem, dE adalah perubahan energi
total sistem (energi total E juga dikenal sebagai energi dalam U dalam ilmu termodinamika)
dan P dV adalah kerja luar akibat adanya perubahan volume dV . Mengingat tidak ada
perubahan volume (dV = 0) pada sistem tertutup, maka berlaku dQ = dE. Jadi persamaan
diferensial Lagange (3.6) berikut,
d nW + dN + dE = 0,
berubah menjadi
d nW + dQ = 0. (5.2)
Pada tahap ini, konsep entropi diperkenalkan sebagai derajat keteraturan sistem. Seperti
halnya temperatur mutlak T dan energi total E, maka entropi sistem S juga merupakan
fungsi keadaan yang nilainya secara umum berbeda untuk keadaan yang berbeda. Dalam
hal ini, perubahan entropi dS merupakan besaran penting yang menggambarkan dinamika
sistem, dimana nilainya hanya ditentukan oleh keadaan awal dan keadaan akhir (dikenal
sebagai diferensial eksak). Perubahan entropi dS dari satu keadaan ke keadaan yang lain
dirumuskan sebagai
dS =
dQ
T
atau S = S
akhir
S
awal
=
_
dQ
T
(5.3)
Pembahasan detil tentang perubahan entropi dapat dipelajari dalam kuliah termodinamika,
dimana dibahas perubahan entropi berbagai macam proses, baik proses reversibel maupun
non-reversibel.
Dengan bantuan denisi dan persamaan diferensial (5.3) di atas, maka persamaan (5.2)
dapat diubah menjadi
d nW
1
k
dS = 0,
dengan mana kita bisa memperoleh
S = k nW. (5.4)
Perumusan entropi di atas sering dikenal sebagai relasi Boltzmann, yang menghubungkan
peluang termodinamik W (besaran mikro) dan fungsi termodinamik entropi S (besaran
makro). Pada kuliah ini, pembahasan ditekankan pada kegunaan (5.4) untuk menjelaskan
beberapa gejala makroskopis dari kacamata mikroskopis. Akan ditunjukkan bahwa (5.4)
memberikan hasil yang sama dengan pengamatan makroskopis untuk sistem gas klasik.
Bagaimanapun keberhasilan persamaan ini bergantung pada bentuk perumusan peluang
termodinamik W yang dibangun berdasarkan asumsi-asumsi dasar tertentu.
5.2. Gas klasik 37
5.2 Gas klasik
Pada bagian ini, akan ditunjukkan bahwa persamaan keadaan gas ideal dapat diturunkan
dengan bantuan perumusan peluang termodinamika klasik (3.1),
W = N!

i
g
N
i
i
N
i
!
,
yang disubstitusikan ke dalam persamaan (5.4). Kita akan peroleh bentuk seperti di bawah
ini,
S = k n
_
N!

i
g
N
i
i
N
i
!
_
= k
_
nN! + n

i
g
N
i
i
N
i
!
_
= k
_
NnN N +

i
n
g
N
i
i
N
i
!
_
= k
_
NnN N +

i
ng
N
i
i

i
nN
i
!
_
= k
_
NnN N +

i
N
i
ng
i

i
N
i
nN
i
+

i
N
i
_
= k
_
NnN +

i
N
i
ng
i

i
N
i
nN
i
_
.
Kemudian kita substitusikan persamaan (3.10) berikut
N
i
=
N
Z
g
i
e

i
/kT
untuk memunculkan secara eksplisit fungsi partisi Z, energi total (dalam) E dan temperatur
mutlak T, sedemikian sehingga perumusan entropi di atas menjadi
S = k
_
NnN +

i
N
i
ng
i

i
N
i
n
N
Z
g
i
e

i
/kT
_
= k
_
NnN +

i
N
i
ng
i

i
N
i
nN +

i
N
i
nZ

i
N
i
ng
i
e

i
/kT
_
= k
_

i
N
i
ng
i
+ N nZ

i
N
i
ng
i

i
N
i
ne

i
/kT
_
= k
_
N nZ +

i
N
i

i
/kT
_
= k
_
N nZ + E/kT
_
.
Adalah sangat jelas dari bentuk terakhir di atas bahwa
S = Nk nZ +
E
T
. (5.5)
38 5. Termodinamika Gas
Sekarang kita siap untuk menurunkan persamaan keadaan gas ideal. Langkah pertama
adalah mengalikan kedua ruas persamaan (5.5) dengan T, kemudian mengatur suku-suku
persamaan tersebut sedemikian sehingga diperoleh bentuk berikut ini,
E TS = NkT nZ.
Dalam ilmu termodinamika, ruas kiri dari bentuk perumusan di atas dikenal sebagai fungsi
bebas Helmholtz F. Jadi kita sekarang punya bentuk berikut,
F = NkT nZ. (5.6)
Dengan mensubstitusikan fungsi partisi Boltzmann (2.47), Z = BV
_
2mkT
_
3/2
, ke dalam
persamaan (5.6) di atas, kita akan peroleh bentuk eksplisit dari energi bebas Helmholtz,
yaitu
F = NkT nBV
_
2mkT
_
3/2
. (5.7)
Persamaan keadaan gas ideal dapat diperoleh dengan memanfaatkan salah satu denisi
yang diturunkan dari hukum pertama Termodinamika, yaitu
P =
_
F
V
_
T
= NkT
_
nZ
V
_
T
= NkT
d nV
dV
=
NkT
V
.
Bentuk ungkapan di atas tidak lain merupakan persamaan keadaan gas ideal, PV = NkT.
Selain persamaan keadaan gas ideal tersebut di atas, kita bisa juga menurunkan ungkapan
energi total (dalam) gas ideal E dengan memanfaatkan denisi berikut,
E = T
2
_
F/T
T
_
V
= NkT
2
_
nZ
T
_
V
=
3
2
NkT
2
T
=
3
2
NkT.
Sekali lagi kita bisa membuktikan keampuhan perumusan entropi sistem S pada (5.5)
yang menjelma menjadi energi bebas Helmholtz F pada (5.7), sebelum digunakan untuk
menurunkan beberapa kuantitas gas ideal. Namun demikian, perumusan entropi pada (5.5)
tidak dapat digunakan untuk menjelaskan gejala pencampuran gas dalam ruang tertutup
bersekat. Gejala sis ini akan kita bahas pada pasal berikutnya.
5.3. Paradoks Gibbs 39
5.3 Paradoks Gibbs
Untuk menguji lebih lanjut apakah perumusan entropi sistem pada (5.5) berlaku umum,
maka pada bagian ini dibahas situasi sis dimana dua gas klasik dengan jumlah partikel
masing-masing N
1
dan N
2
, massa total masing-masing m
1
dan m
2
mula-mula ditempatkan
pada dua buah ruang terpisah bersekat yang masing-masing volumenya adalah V
1
dan V
2
.
Misalkan bahwa temperatur T kedua ruang dijaga tetap. Adalah menarik untuk dipelajari
apa yang akan terjadi bila sekat pemisah kedua ruang dibuka, dengan demikian memberikan
kemungkinan interaksi antara partikel-partikel dari kedua gas tersebut. Dalam konteks ini,
pembicaraan ditekankan pada nilai entropi sistem dua gas tersebut sebelum dan sesudah
sekat dibuka.
Marilah kita mulai pembahasan dengan menghitung nilai entropi total sebelum sekat
dibuka. Dengan mensubstitusikan fungsi partisi Boltzmann pada (2.47), Z = BV
_
2mkT
_
3/2
,
ke dalam persamaan (5.5), kita akan peroleh bentuk eksplisit entropi sistem, yaitu
S = Nk nB + Nk nV + Nk n
_
2mkT
_
3/2
+
E
T
. (5.8)
Berdasarkan persamaan (5.8) di atas, kita bisa tuliskan entropi masing-masing gas sebelum
sekat dibuka, yaitu
S
1
= N
1
k nB + N
1
k nV
1
+ N
1
k n
_
2m
1
kT
_
3/2
+
E
1
T
S
2
= N
2
k nB + N
2
k nV
2
+ N
2
k n
_
2m
2
kT
_
3/2
+
E
2
T
.
(5.9)
Dengan demikian entropi total sistem dua gas tersebut sebelum sekat dibuka adalah
S = S
1
+ S
2
= (N
1
+ N
2
) k nB + (N
1
+ N
2
) k nV + N
1
k n
_
2m
1
kT
_
3/2
+ N
2
k n
_
2m
2
kT
_
3/2
+
E
1
+ E
2
T
, (5.10)
dimana telah diasumsikan bahwa V
1
= V
2
= V .
Sekarang kita akan menghitung nilai entropi sistem pada saat sekat telah dibuka. Perlu
diketahui bahwa sesudah sekat dibuka, volume total menjadi V
1
+V
2
= 2V , jumlah partikel
masing-masing gas tetap N

1
= N
1
dan N

2
= N
2
, massa total masing-masing gas tetap
m

1
= m
1
dan m

2
= m
2
, energi dalam masing-masing gas tetap E

1
= E
1
dan E

2
= E
2
.
Dengan demikian entropi total sistem dua gas sesudah sekat dibuka adalah
S

= (N
1
+ N
2
) k nB + (N
1
+ N
2
) k n2V + N
1
k n
_
2m
1
kT
_
3/2
+ N
2
k n
_
2m
2
kT
_
3/2
+
E
1
+ E
2
T
. (5.11)
40 5. Termodinamika Gas
Dari kedua persamaan (5.10) dan (5.11) tersebut di atas jelas bahwa perubahan entropi
total sistem adalah
S = S

S = (N
1
+ N
2
) k (n2V nV ). (5.12)
Misalkan bahwa kedua gas yang kita bicarakan adalah berjenis sama (dengan kerapatan
jenis
1
=
2
= ), maka perubahan entropi total sistem adalah S = 2Nk n2. Hasil
ini sangat menarik mengingat tidak sesuai dengan akal sehat yang menyatakan bahwa de-
rajat keteraturan suatu sistem semestinya sama berapapun volume ruang yang ditempati
oleh sistem tersebut. Dengan kata lain, jika kedua jenis gas yang mengisi masing-masing
ruang adalah sama maka semestinya tidak boleh ada perubahan entropi pada saat sekat
dibuka, atau secara matematis diharapkan S = 0. Tetapi bila hal ini diterima, maka
timbul pemikiran bahwa seolah-olah entropi sistem bukan saja bergantung pada keadaan
awal dan akhir, melainkan juga bergantung pada riwayat sistem tersebut. Dalam hal ini,
apakah sistem sis yang ditinjau terdiri atas gas-gas berjenis sama ataukah tidak. Hal inilah
yang merupakan paradoks, karena bertentangan dengan prinsip dasar termodinamika yang
menyatakan bahwa entropi adalah fungsi keadaan saja.
5.4 Gas semi klasik
Gibbs adalah orang pertama yang mengamati paradoksial entropi sistem dua gas dalam
ruang tertutup bersekat, dan mengajukan usulan perumusan ulang peluang termodinamika
untuk mengatasi masalah paradoks tersebut. Untuk lebih jelasnya, kita ingat kembali bahwa
perumusan entropi (5.5)
S = Nk nZ +
E
T
diperoleh dari perumusan peluang termodinamika klasik (3.1) sebagai berikut
W = N!

i
g
N
i
i
N
i
!
.
Nampaknya perumusan peluang termodinamika klasik tersebut di atas yang menjadi
biang keladi masalah. Perumusan tersebut berdasarkan asumsi dalam Distribusi Statistik
Klasik yang menyatakan bahwa gas klasik terdiri dari partikel-partikel yang dapat dibedakan.
Beliau mengusulkan jumlah cara untuk mengatur sistem ke dalam tingkat-tingkat energi yang
tersedia, atau yang dikenal sebagai peluang termodinamik W seharusnya N! kali lebih kecil
dari yang diberikan oleh persamaan (3.1). Jadi seharusnya
W =

i
g
N
i
i
N
i
!
. (5.13)
5.4. Gas semi klasik 41
Hal ini hanya akan bisa dipenuhi bila gas terdiri atas partikel-partikel yang tak terbedakan.
Gas semacam ini yang memiliki peluang termodinamik yang mirip dengan persamaan (3.1)
kemudian dikenal dengan istilah gas semi klasik dan persamaan (5.13) disebut dengan
peluang termodinamik semi klasik.
Sekarang saatnya untuk menghitung entropi sistem dengan menggunakan perumusan
peluang termodinamik semi klasik (5.13). Perlu diketahui bahwa relasi Boltzmann (5.4) yang
menghubungkan besaran makro entropi sistem S dan besaran mikro peluang termodinamik
W adalah bentuk dasar perumusan entropi sistem, dan oleh karena itu manjur digunakan
untuk semua situasi baik jenis gas yang ditinjau adalah gas klasik maupun semi klasik.
Substitusi persamaan (5.13) ke dalam persamaan (5.4) menghasilkan
S = k n

i
g
N
i
i
N
i
!
= Nk + Nk nB + Nk n
V
N
+ Nk n
_
2mkT
_
3/2
+
E
T
= Nk Nk nN + Nk nB + Nk nV + Nk n
_
2mkT
_
3/2
+
E
T
.
(5.14)
Jelas sekali terlihat bahwa dua suku pertama pada ruas kanan persamaan (5.14) merupakan
pembeda yang membedakan persamaan entropi semi klasik (5.14) dari persamaan entropi
klasik (5.8).
Berdasarkan persamaan (5.14) tersebut di atas, maka entropi masing-masing gas sebelum
sekat dibuka adalah
S
1
= N
1
k N
1
k nN
1
+ N
1
k nB + N
1
k nV
1
+ N
1
k n
_
2m
1
kT
_
3/2
+
E
1
T
S
2
= N
2
k N
2
k nN
2
+ N
2
k nB + N
2
k nV
2
+ N
2
k n
_
2m
2
kT
_
3/2
+
E
2
T
(5.15)
Dengan demikian entropi total sistem gas semi klasik sebelum sekat dibuka adalah
S = 2Nk 2Nk nN + 2Nk nB + 2Nk nV + 2Nk n
_
2mkT
_
3/2
+
E
1
+ E
2
T
, (5.16)
dimana sekali lagi telah diasumsikan V
1
= V
2
= V dan N
1
= N
2
= N serta m
1
= m
2
= m
(untuk jenis gas yang sama).
Analogi dengan gas klasik, sekarang kita menghitung entropi total sistem gas semi klasik
sesudah sekat dibuka sebagai berikut,
S

= 2Nk 2Nk nN + 2Nk nB + 2Nk nV + 2Nk n

_
2mkT
_
3/2
+
E
1
+ E
2
T
. (5.17)
Jelas sekali terlihat dari kedua persamaan (5.16) dan (5.17) tersebut di atas bahwa tidak
42 5. Termodinamika Gas
ada perubahan entropi sistem sebelum dan sesudah sekat dibuka. Secara matematis, hal ini
dituliskan sebagai S = 0. Tidak adanya perubahan entropi total sistem gas semi klasik
pada saat sekat dibuka dikarenakan specic volume V/N sistem tersebut bernilai sama
sebelum dan sesudah sekat dibuka.
Menarik untuk dibicarakan di sini bahwa perumusan entropi sistem gas semi klasik pada
(5.14) dapat dituliskan dalam bentuk
S = Nk
_
n
V
_
2mkT
_
3/2
Nh
3
+
5
2
_
. (5.18)
Perumusan di atas dikenal sebagai persamaan Sackur-Tetrode, yang diperoleh dengan
jalan mensubstitusikan B = 1/h
3
dan E =
3
2
NkT ke dalam persamaan (5.14).
Juga menarik untuk dikaji bahwa tidak ada cara untuk memahami secara klasik mengapa
kita harus membagi perumusan peluang termodinamik klasik (3.1) dengan N! agar diperoleh
perhitungan entropi total sistem dua gas dengan benar. Bagaimanapun secara kuantum,
hal tersebut dapat dimengerti mengingat atom-atom gas tersusun oleh partikel-partikel tak-
terbedakan yang dibentuk oleh fungsi gelombang yang simetri dan anti-simetri terhadap
pertukaran dua partikel. Detil matematis pembahasan masalah ini adalah di luar cakupan
kuliah Fisika Statistik.
5.5 Latihan soal
1. Gas yang terdiri atas N buah partikel dengan massa per partikelnya adalah m memiliki
temperatur T dan menempati ruang dengan volume V . Partikel-partikel gas tersebut
mengikuti hukum Distribusi Semi Kasik.
(a) Carilah bentuk fungsi energi bebas Helmholtz.
(b) Turunkan bentuk persamaan keadaan gas tersebut.
(c) Turunkan ungkapan entropi gas tersebut.
(d) Turunkan ungkapan kapasitas kalor gas tersebut.
2. (a) Jelaskan perbedaan antara Statistik Klasik (Maxwell-Boltzmann), Statistik Semi
Klasik dan Statistik Kuantum (Bose-Einstein dan Fermi-Dirac).
(b) Jelaskan secara sis apa yang dimaksud dengan Paradoks Gibbs, dan bagaimana
cara mengatasi masalah tersebut.
3. Show that, when two dierent gases A and B of volumes V
A
and V
B
and total molecules
of N
A
and N
B
, respectively, are mixed together at constant temperature T to form a
5.5. Latihan soal 43
total volume of V
A
+V
B
, there is an increase in the total entropy given by the mixing
term as follows
k
_
(N
A
+ N
B
) n(V
A
+ V
B
) N
A
nV
A
N
B
nV
B
_
.
Hence deduce that, when V
A
= V
B
and N
A
= N
B
= N, the mixing term is 2Nk n2
(taken from Pointon, 1978, Ch.7, problem 1).
4. Derive the equation of state and the total energy of a semi classical perfect gas from
the expression for the entropy for such a gas. Explain why the results obtained are the
same as those for a classical perfect gas (taken from Pointon, 1978, Ch.7, problem 3).
5. Show that the total partition function derived from equation (7.45) of Pointon (1978)
on the assumption that the energy of the N sub-systems is
E =
p
2
x1
2m
+
p
2
y1
2m
+
p
2
z1
2m
+ +
p
2
xN
2m
+
p
2
yN
2m
+
p
2
zN
2m
agrees with that obtained by substituting (7.28) into (7.31) of Pointon (1978), i.e.,
Z =
V
N
N ! h
3N
_
2mkT
_
3N/2
(taken from Pointon, 1978, Ch.7, problem 5).
44 5. Termodinamika Gas
Chapter 6
Aplikasi Distribusi Statistik
Bab ini merupakan bab terakhir dari rangkaian pembahasan pada kuliah Fisika Statistik,
yang meliputi aplikasi sika statistik pada beberapa sistem sis sederhana, dimana jumlah
partikel dan energi totalnya dapat dianggap tetap (dN = 0 dan dE = 0). Sistem sis dengan
partikel-partikel yang saling berinteraksi tidak ikut dibahas pada bab ini. Namun demikian,
hasil penurunan matematis untuk sistem sis yang ditinjau akan berlaku secara umum.
Adapun rincian topik bahasan Bab 6 adalah sebagai berikut. Model sis dengan dua
tingkat energi akan diperkenalkan terlebih dahulu pada pasal 6.1, kemudian diikuti dengan
pengenalan konsep osilator harmonik menurut distribusi statistik kuantum pada pasal 6.2.
Pembahasan molekul diatom dengan melibatkan gabungan gerak translasi, rotasi dan vibrasi
akan diberikan pada pasal 6.3.
6.1 Sistem dua tingkat energi
Bagian ini membahas sistem N partikel yang terdistribusi ke dalam dua tingkat energi
1
dan
2
yang tak-terdegenerasi (g
1
= g
2
= 1), dimana
2
-
1
= . Misalkan bahwa tingkat
energi
1
ditetapkan berisi N
1
partikel dan tingkat energi
2
ditetapkan berisi N
2
partikel,
maka dapat dituliskan N
1
+ N
2
= N.
Berikut akan ditunjukkan bahwa distribusi partikel pada masing-masing tingkat energi
merupakan fungsi dari e
/kT
. Langkah-langkah untuk menurunkan fungsi distribusi partikel
tersebut adalah sebagai berikut. Mula-mula kita mengasumsikan bahwa partikel-partikel
yang menghuni kedua tingkat energi adalah partikel-partikel yang terbedakan, agar N
1
dan
N
2
bersifat tetap. Jadi, distribusi statistik yang digunakan untuk memecahkan masalah
ini adalah Distribusi Maxwell-Boltzmann, dimana jumlah cara untuk mengatur partikel ke
dalam tingkat-tingkat energi yang tersedia dinyatakan menurut persamaan (3.1).
Karakteristik termodinamik sistem tersebut di atas digambarkan oleh fungsi entropi
45
46 6. Aplikasi Distribusi Statistik
melalui relasi Boltzmann (5.4) sebagai berikut,
S = k nW = k n
N !
N
1
! N
2
!
. (6.1)
Dengan memanfaatkan pendekatan Stirling, persamaan (6.1) berubah menjadi
S = k
_
N nN N
1
nN
1
N
2
nN
2
_
. (6.2)
Seperti telah dibahas pada pasal 5.2, fungsi energi bebas Helmholtz dituliskan sebagai
F = E TS. Dengan demikian energi bebas Helmholtz sistem tersebut adalah
F = E kT
_
N nN N
1
nN
1
N
2
nN
2
_
= N
1

1
+ N
2

2
kT
_
N nN N
1
nN
1
N
2
nN
2
_
.
(6.3)
Agar sistem dalam keadaan setimbang, maka nilai energi bebas Helmhotz haruslah minimum.
Dengan kata lain, turunan parsial dari energi bebas Helmholtz (6.3) terhadap N
1
atau N
2
di atas haruslah berharga nol. Jadi,
F
N
1
= 0 atau
F
N
2
= 0. (6.4)
Substitusi persamaan (6.3) ke dalam salah satu persamaan (6.4) menghasilkan
0 =
2

1
kT
_
nN
1
nN
2
_
=
2

1
kT
_
n
N
1
N
2
_
.
Dengan mengatur suku-suku pada persamaan di atas, maka akan diperoleh
n
N
1
N
2
=

2

1
kT
n
N
1
N
2
= ne
(
2

1
)/kT
N
1
N
2
= e
(
2

1
)/kT
= e
/kT
.
Bentuk perumusan di atas adalah seperti yang diharapkan pada temperatur yang cukup
tinggi, dimana partikel cenderung mengisi tingkat energi yang lebih tinggi (N
1
N
2
).
Substitusi N
1
= N N
2
ke dalam perumusan tersebut di atas dan mengatur suku-suku
sehingga akan diperoleh populasi partikel pada tingkat energi
2
sebagai berikut
N
2
=
N
1 + e
/kT
. (6.5)
6.2. Osilator harmonik 47
Energi total sistem dapat diturunkan dengan mudah dengan bantuan (6.5), yaitu
E = N
1

1
+ N
2

2
= (N N
2
)
1
+ N
2

2
= N
1
+ (
2

1
) N
2
= N
1
+
N
1 + e
/kT
.
(6.6)
Berbekal persamaan (6.6) dapat ditunjukkan dengan mudah bahwa kapasitas panas zat yang
terdiri atas sistem dua tingkat energi pada volume tetap adalah
C
V
=
_
E
T
_
V
=
N
2
kT
2
e
/kT
(1 + e
/kT
)
2
. (6.7)
6.2 Osilator harmonik
Banyak sekali masalah sika yang dapat dipelajari dengan pemodelan sistem sis yang
memanfaatkan osilator harmonik untuk menggambarkan sifat dinamik dari sistem yang
bersangkutan. Perlu diketahui di sini bahwa pendekatan osilator harmonik dapat dilakukan
dengan dua cara, yaitu mekanika klasik dan mekanika kuantum.
Ingat kembali pembahasan ekipartisi energi pada sub-pasal 2.3.2, dimana ditemukan
energi rata-rata osilator harmonik satu dimensi adalah kT (persamaan 2.40). Hal ini berarti
energi kinetik osilator dapat berharga berapa saja (terdistribusi secara kontinu) bergantung
pada besarnya temperatur. Sebaliknya, pendekatan mekanika kuantum memberikan batasan
harga untuk energi osilator yaitu

n
=
_
n +
1
2
_
h, (6.8)
dimana n = 0, 1, 2, ......, dan adalah frekuensi osilator. Jadi, menurut mekanika kuantum
energi osilator terdistribusi secara diskrit dalam tingkat-tingkat energi yang diperbolehkan
(merupakan kelipatan setengah dari h). Tingkat energi terendah diperoleh untuk n = 0,
yaitu =
1
2
h. Tingkat energi terendah ini disebut dengan tingkat energi keadaan dasar.
Tingkat-tingkat energi lain yang lebih tinggi berkaitan dengan harga n > 0 disebut dengan
tingkat energi keadaan eksitasi.
Dalam paragraf berikut akan dicoba diturunkan energi rata-rata osilator harmonik satu
dimensi menurut mekanika kuantum dengan memanfaatkan persamaan (6.8) di atas. Hasil
yang diperoleh akan dibandingkan dengan hasil menurut mekanika klasik. Langkah pertama
48 6. Aplikasi Distribusi Statistik
adalah menuliskan kembali persamaan (3.9),
Z =

i
g
i
e

i
/kT
. (6.9)
Mengingat tingkat-tingkat energi osilator harmonik adalah tak-terdegenerasi (g = 1) dan
dengan bantuan persamaan (6.8), maka persamaan (6.9) di atas dapat dituliskan ulang
dalam bentuk
Z =

n=0
e
(n+1/2)h/kT
= e

1
2
h/kT

n=0
e
nh/kT
. (6.10)
Substitusi deret berikut

x
n
= (1 x)
1
dimana x = e
h/kT
ke dalam persamaan (6.10)
di atas akan menghasilkan
Z =
e

1
2
h/kT
1 e
h/kT
. (6.11)
Energi rata-rata osilator harmonik dapat dengan mudah dihitung melalui perumusan yang
telah diperkenalkan sebelumnya pada bagian akhir pembahasan pasal 5.2,
) = kT
2
_
nZ
T
_
V
= kT
2

T
_
n
e

1
2
h/kT
1 e
h/kT
_
= kT
2

T
_
n e

1
2
h/kT
n
_
1 e
h/kT
_
_
= kT
2
_
1
2
h
kT
2
+
h
kT
2
(e
h/kT
1)
_
= h
_
1
2
+
h
e
h/kT
1
_
.
(6.12)
Pada temperatur cukup tinggi berlaku h kT, sedemikian sehingga
e
h/kT
1 +
h
kT
+
1
2
_
h
kT
_
2
sampai pada suku order kedua. Substitusi deret tersebut di atas ke dalam persamaan (6.12)
akan menghasilkan
) = h
_
1
2
+
kT
h
_
1
h
kT
_
_
= kT. (6.13)
Hasil tersebut di atas menunjukkan bahwa perumusan energi rata-rata osilator harmonik
menurut mekanika kuantum pada temperatur tinggi akan sama dengan perumusan menurut
mekanika klasik.
6.3. Gas diatomik 49
6.3 Gas diatomik
Model sis lain yang dapat digunakan untuk menggambarkan dinamika sistem adalah model
molekul diatomik. Dalam model ini, energi total sistem terdiri dari energi yang berasal dari
gerak translasi, rotasi, vibrasi, orbital dan spin. Gerak orbital yang dimaksud di sini adalah
gerakan elektron disekeliling inti atom, sedangkan gerak spin adalah gerak berputar inti
atom terhadap porosnya. Gerak translasi dapat didekati dengan mekanika klasik, namun
keempat gerak yang lain secara umum mensyaratkan adanya kuantisasi (diskritisasi) energi.
Fungsi partisi total sistem molekul diatomik dapat dituliskan sebagai
Z = Z
t
Z
r
Z
v
Z
e
Z
n
, (6.14)
dimana indeks t, r, v, e dan n masing-masing untuk gerak translasi, rotasi, vibrasi, elektron
dan nuklir. Kita akan turunkan satu per satu kelima bentuk fungsi partisi tersebut dimulai
dari yang paling mudah.
Fungsi partisi untuk gerak translasi adalah yang paling mudah mengingat kita sudah
menurunkan sebelumnya pada persamaan (2.47),
Z
t
= BV
_
2mkT
_
3/2
=
V

3
_
2mkT
_
3/2
. (6.15)
Berikutnya yang juga mudah adalah fungsi partisi untuk gerak vibrasi karena gerak vibrasi
molekul diatomik sebagai satu kesatuan dapat dipandang sebagai osilator harmonik satu
dimensi. Jadi fungsi partisi gerak vibrasi dapat didekati oleh persamaan (6.11),
Z
v
=
e

1
2
h/kT
1 e
h/kT
, (6.16)
dimana menyatakan frekuensi karakteristik vibrasi molekul diatomik.
Kemudian fungsi partisi dari kontribusi gerak orbital elektron dapat ditentukan langsung
dari persamaan (6.9) berikut,
Z
e
=

i
g
i
e

i
/kT
g
o
+ g
1
e

1
/kT
, (6.17)
dimana telah diambil dua suku pertama dari deret fungsi partisi yang bersangkutan sebagai
pendekatan yang cukup baik. Dalam hal ini g
o
menyatakan derajat degenerasi keadaan
dasar molekul diatomik, g
1
menyatakan derajat degenerasi keadaan tereksitasi pertama,
dan
1
menyatakan tingkat energi eksitasi pertama. Pada umumnya tingkat-tingkat energi
tereksitasi berharga jauh lebih besar dari energi termal kT, kecuali untuk temperatur tinggi,
dimana energi termal tersebut menjadi dominan.
50 6. Aplikasi Distribusi Statistik
Perhitungan fungsi partisi gerak rotasi agak sedikit sulit. Kita bayangkan tiap molekul
gas terdiri atas 2 atom bermassa sama m terpisah pada jarak 2a. Momen inersia sistem
ini terhadap sumbu yang melewati titik tengah garis hubung kedua atom tersebut adalah
= 2ma
2
, dimana a adalah jarak dari salah satu atom menuju ke titik pusat sistem. Bila
sistem ini tidak berada dalam pengaruh medan potensial apapun, maka energi totalnya hanya
merupakan energi kinetik rotasi saja. Jadi, kita dapat menuliskan persamaan Hamilton
dalam bentuk operator untuk menggambarkan dinamika rotasi sistem diatomik tersebut
sebagai berikut,

H = (

E +

V ) = (

E + 0) =

E , (6.18)
dimana

H adalah operator Hamiltonian yang menyatakan energi total sistem,

E menyatakan
operator energi kinetik,

V menyatakan operator energi potensial, dan menyatakan fungsi
gelombang sistem yang bersangkutan. Analogi dengan gerak translasi, energi kinetik gerak
rotasi dapat digambarkan oleh

E =

L
2
2
, (6.19)
dimana

L adalah operator momentum sudut orbital, yang bekerja terhadap fungsi gelombang
menurut

L
2
=
2
( + 1) ,
dimana adalah bilangan kuantum momentum sudut orbital ( = 0, 1, 2, ......). Substitusikan
bentuk di atas ke dalam persamaan (6.19) akan diperoleh

E =

2
( + 1)
2
. (6.20)
Koreksi kecil dilakukan untuk perumusan momentum sudut. Dengan mempertimbangkan
momentum sudut spin, maka bilangan kuantum momentum sudut orbital diganti dengan
bilangan kuantum momentum sudut total j. Dengan demikian persamaan 6.20) berubah
menjadi

E =

2
j(j + 1)
2
. (6.21)
Secara implisit, persamaan (6.21) di atas menyatakan bahwa tingkat-tingkat energi rotasi
yang diijinkan adalah

j
=

2
j(j + 1)
2
, (6.22)
dimana j =
1
2
. Perlu diketahui bahwa untuk setiap harga j akan terdapat (2j + 1)
kemungkinan harga m
j
(bilangan kuantum magnetik total), yaitu m
j
= -j,...... 0, ......j.
Kemungkinan sebanyak itu dapat dipandang sebagai akibat degenerasi kuantum. Jadi dalam
hal ini derajat degenerasinya adalah g
j
= (2j+1) sedemikian sehingga persamaan (6.9) dapat
6.3. Gas diatomik 51
dituliskan ulang menjadi
Z
r
=

j=0
g
j
e

j
/kT
=

j=0
(2j + 1) e

j
/kT
=

j=0
(2j + 1) e
j(j+1)K/kT
,
(6.23)
dimana / = h
2
/8
2
.
Fungsi partisi dari kontribusi gerak orbital elektron dikembangkan dari persamaan (6.9)
berikut,
Z
e
=

i
g
i
e

i
/kT
g
o
+ g
1
e

1
/kT
, (6.24)
dimana telah diambil dua suku pertama dari deret fungsi partisi yang bersangkutan sebagai
pendekatan yang cukup baik. Dalam hal ini g
o
menyatakan derajat degenerasi keadaan
dasar molekul diatomik, g
1
menyatakan derajat degenerasi keadaan tereksitasi pertama,
dan
1
menyatakan tingkat energi eksitasi pertama. Pada umumnya tingkat-tingkat energi
tereksitasi berharga jauh lebih besar dari energi termal kT, kecuali untuk temperatur tinggi,
dimana energi termal tersebut menjadi dominan.
Yang terakhir adalah fungsi partisi gerak spin Z
n
dari inti atom. Fungsi partisi ini bukan
merupakan fungsi temperatur, melainkan merupakan konstanta biasa. Tidak begitu penting
membicarakan berapa nilai sebenarnya dari fungsi partisi ini.
Setelah memperoleh kelima bentuk fungsi partisi (lihat kembali persamaan 6.14), maka
fungsi partisi sistem molekul diatomik secara lengkap dapat dituliskan sebagai
Z =
V

3
_
2mkT
_
3/2

1
2
h/kT
1 e
h/kT

j=0
(2j +1) e
j(j+1)K/kT

_
g
o
+g
1
e

1
/kT
_
Z
n
. (6.25)
Perlu dipahami di sini bahwa kita meninjau gas semi klasik yang terdiri dari N buah molekul
diatomik yang identik satu sama lain. Entropi sistem gas semacam ini dinyatakan oleh
persamaan (5.14), yang dapat dituliskan ulang dalam bentuk
S = Nk + Nk nB + Nk n
V
N
+ Nk n
_
2mkT
_
3/2
+
E
T
= Nk + Nk n
Z
N
+
E
T
.
(6.26)
Dengan bantuan persamaan (6.26) dan denisi fungsi energi bebas Helmholtz F = E TS,
maka kita dapat menurunkan fungsi Helmholtz untuk gas semi klasik dalam bentuk
F = kT n
Z
N
N !
. (6.27)
52 6. Aplikasi Distribusi Statistik
Cobalah bandingkan persamaan (6.27) dengan bentuk fungsi Helmholtz untuk gas klasik
pada persamaan (5.6),
F = NkT nZ = kT nZ
N
.
Jelas terlihat sekali lagi bahwa terdapat perbedaan faktor N ! antara besaran makro energi
bebas Helmholtz F menurut distribusi klasik dan semi klasik. Sebelumnya adalah perbedaan
(dengan faktor yang sama N !) antara besaran mikro peluang termodinamik W menurut
distribusi klasik dan semi klasik (lihat kembali pembahasan pasal 5.4).
Dengan membandingkan perumusan energi bebas Helmholtz untuk sistem klasik dan
semiklasik, maka dapat didenisikan besaran fungsi partisi total Z sistem semi klasik sebagai
berikut
Z =
Z
N
N !
. (6.28)
Substitusikan persamaan (6.28) ke dalam persamaan (6.27), akan diperoleh
F = kT nZ. (6.29)
Dengan bantuan persamaan (6.29) kita bisa menghitung besarnya energi total gas diatomik
semi klasik sebagai berikut,
E = T
2
_
F/T
T
_
V
= kT
2
_
nZ
T
_
V
= NkT
2
_
nZ
T
_
V
= NkT
2
_
nZ
t
T
+
nZ
r
T
+
nZ
v
T
+
nZ
e
T
+
nZ
n
T
_
.
Suku terakhir ruas kanan jelas berharga nol mengingat Z
n
adalah konstanta. Keempat suku
pertama ruas kanan memberikan hasil berikut ini,
E =
3
2
NkT + NkT
2

T
n

j=0
(2j + 1) e
j(j+1)K/kT
+ Nh
_
1
2
+
h
e
h/kT
1
_
+
N g
1

1
e

1
/kT
g
o
+ g
1
e

1
/kT
. (6.30)
Pada tahap ini akan sangat bermanfaat bila didenisikan suatu besaran karakteristik,
dengan mana kita bisa membandingkan kontribusi masing-masing gerak dalam persamaan
(6.30) di atas. Besaran karakteristik yang dimaksud adalah temperatur karakteristik rotasi,
vibrasi dan orbital elektronik berturut-turut dinyatakan sebagai berikut,

r
=
/
k
,
v
=
h
k
,
e
=

1
k
. (6.31)
Pada umumnya nilai ketiga besaran karakteristik tersebut di atas memenuhi hubungan
6.4. Latihan soal 53
berikut
r

v

e
. Pada temperatur rendah (T
r
), tiga suku pada ruas kanan
persamaan (6.30) menjadi dominan, yaitu suku pertama
3
2
NkT, suku kontribusi dari energi
keadaan dasar gerak vibrasi
1
2
Nh, dan suku kontribusi dari energi keadaan dasar gerak
orbital elektron Ng
o
. Dari ketiga suku ini, hanya suku pertama saja yang merupakan fungsi
temperatur. Suku ini merupakan kontribusi dari gerak translasi. Jadi kapasitas panas C
V
gas diatomik pada temperatur rendah dinyatakan sebagai
C
V
=
_
E
T
_
V
=
3
2
Nk =
3
2
nN
o
k =
3
2
nR. (6.32)
Dengan kata lain, kalor jenis c
V
gas diatomik pada temperatur rendah dituliskan sebagai
c
V
=
C
V
n
=
3
2
R. (6.33)
Hasil tersebut di atas sama dengan hasil yang diperoleh melalui perhitungan distribusi klasik.
Bagaimanapun, perhitungan semi klasik memungkinkan kita untuk menentukan kapasitas
panas ataupun kalor jenis gas diatomik pada temperatur sedang dan tinggi. Untuk sekedar
diketahui, pada temperatur sedang kalor jenis gas diatomik adalah
5
2
R, sedangkan pada
temperatur tinggi
7
2
R. Detil penurunan tidak diberikan dalam kuliah ini, namun demikian
mahasiswa diharapkan untuk melakukannya buat olahraga ringan.
6.4 Latihan soal
1. Calculate the maximum specic heat for an assembly of systems having two energy
levels separated by an energy h if the upper level is doubly degenerate (taken from
Pointon, 1978, Ch.8, problem 6).
2. Two dierent groups of n fermions are distributed among m states of the same energy
where m > n. Show that the entropy is given by
2k
_
mnmnnn (mn) n(mn)
_
(taken from Pointon, 1978, Ch.8, problem 2).
3. Show that at high temperatures the free energy of an assembly of quantum mechanical,
1D oscillators approximates to kT n(h/kT) per oscillator, corresponding to a mean
thermal energy of kT (taken from Pointon, 1978, Ch.8, problem 3).
4. Evaluate the partition function at temperature T for a classical 1D harmonic oscillator
54 6. Aplikasi Distribusi Statistik
having an energy of
=
p
2
x
2m
+
1
2
x
2
and hence nd the mean energy of such an oscillator at this temperature (taken from
Pointon, 1978, Ch.8, problem 4).
5. Show that the equation of state of a diatomic gas as derived from (8.27) of Pointon
(1978) is the same as that for a monoatomic gas (taken from Pointon, 1978, Ch.8,
problem 5).
6. Write out the partition function for a 3D harmonic oscillator assuming that it obeys
classical and quantum mechanics. Show that both give a mean energy of 3kT at high
temperatures (taken from Pointon, 1978, Ch.8, problem 7).
Bibliography
Beiser, A. 1988 Perspective of Modern Physics. London, UK: McGraw-Hill.
Gasiorowicz, S. 1996 Quantum Physics. New York, US: John Wiley and Sons.
Huang, K. 1987 Statistical Mechanics. New York, US: John Wiley and Sons.
Pointon, A. J. 1978 An Introduction to Statistical Physics. London, UK: Longmann.
Reif, F. 1985 Fundamentals of Statistical and Thermal Physics. Singapore: McGraw-Hill.
Tipler, P. A. 1999 Physics for scientists and engineers. New York, US: W. H. Freemann.
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