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Introductory Statistical Thermodynamics
Introductory Statistical Thermodynamics
Introductory Statistical Thermodynamics
by
Leonardo Golubović
West Virginia University, Morgantown, USA
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ISBN: 978-0-12-384956-4
The aim of this book is to discuss basic theoretical results of the statistical physics
and thermodynamics, which cover the fundamental physical concepts used for the
macroscopic description of systems with very large numbers of constituent parti-
cles. The macroscopic concepts used in classical thermodynamics are derived from
the microscopic theories of constituent particles, i.e., quantum mechanics and statis-
tical mechanics. However, in literature, the subject of classical thermodynamics is
frequently introduced from a purely macroscopic point of view. Such an approach is
conceptually more difficult, and its reasoning is often hard to follow by many physics
and engineering students. In particular, the significance and the real physical meaning
of the fundamental concept of entropy are difficult, if not impossible, to explain on
purely macroscopic grounds.
Therefore, we chose to approach the subject from the microscopic point of view.
It is based on the fact that all macroscopic systems consist of microscopic constituent
particles (molecules, atoms, or elementary particles) obeying the laws of quantum
mechanics. Using basic postulates of statistical mechanics and elementary results from
quantum mechanics, we derive the general thermodynamic description of physical
systems at macroscopic level. This description is largely independent on the details of
the microscopic models describing the interactions of the particles in various physical
systems.
Despite the initial microscopic approach to the subject, the central part of the book
consists of physical considerations on a purely macroscopic level. By adopting some
simple quantum-mechanical models of the constituent particles of a system, the book
shows how one can calculate macroscopic thermodynamic quantities on the basis of
the relevant microscopic results. The book is focused on the study of systems in ther-
modynamic equilibrium. However, the statistical approach to the discussion of various
equilibrium situations provides the students with the needed preparation for the exten-
sion to the discussion of nonequilibrium systems.
The basic plan of the book is the following: The first part of the book covers
the microscopic models of constituent particles. It discusses three basic models from
quantum mechanics. Some sections of the first part of the book are of a purely
quantum-mechanical and mathematical significance. Although not directly related to
the traditional subjects of thermodynamics, they are considered in some detail in order
to establish a complete understanding of the quantum description of macroscopic
systems of particles.
The second part of the book is devoted to the detailed derivation of the basic
notions of classical statistical mechanics and the general laws of macroscopic ther-
modynamics that relate various thermodynamic quantities. The third part of the book
xii Preface
covers the application of the general macroscopic laws, derived in the second part, to
the physically interesting cases of the ideal and nonideal gases. Finally, in the fourth
part of the book, a discussion of quantum statistical mechanics and some relativistic
phenomena is presented. The quantum relativistic thermodynamics includes a study of
some macroscopic phenomena in the expanding early universe.
Some sections of the book cover purely mathematical and/or quantum-mechanical
concepts that are not directly related to what is traditionally the scope of courses of
Statistical Physics and Thermodynamics. These sections are marked by an asterisk
and can be omitted by the instructors adopting a less theoretical and mathematical
approach to the subject. These sections can also be omitted by readers who have
already taken a Quantum Mechanics course prior to taking the course in Statisti-
cal Physics and Thermodynamics, and are familiar with the quantum-mechanical and
mathematical concepts covered in these sections.
The book is intended as a text for an introductory one-semester course in thermo-
dynamics for undergraduate students of physical sciences or engineering. However,
it can also be used as material for an introductory graduate course in thermodynam-
ics. The book has evolved from a set of lecture notes originally prepared by one of
the authors, N. Dalarsson, but has been subsequently expanded with a number of new
topics over the last fifteen years.
It is the intention of the book to provide the readers with a high level of detail in
derivations of all equations and results. All algebraic manipulations are outlined in
great detail, such that they can be followed by an interested college student with very
little or no risk of ever getting lost. It is our experience that a common show stopper
for a young college student, trying to master a subject, are the phrases in the literature
claiming that something can be derived from something else by some “straightfor-
ward although somewhat tedious algebra.” If a student cannot readily reproduce that
“straightforward” algebra, which often is the case, the usual reaction under the time
pressure of the studies is to accept the claim as a fact. And from that point on, through-
out the rest of the course, the deeper understanding of the subject is lost.
The book contains a number of solved problems. They have been selected to illus-
trate the theoretical concepts discussed throughout the book. The solutions are given
in detail to help master the theoretical concepts from the book. It is common in the
literature to include the problems at the end of each chapter and to outline the solu-
tions or just provide answers at the end of the book. In the present book, we choose a
different approach and add a number of problems with detailed solutions at the end of
each chapter. Furthermore, a number of detailed theoretical derivations throughout the
book can also be used as homework or exam problems.
There is a number of advanced books on statistical thermodynamics, and we have
benefited from some of those. These sources are listed in the bibliography at the end
of the book, as well as a few other books recommended as suitable further reading.
Regretfully, in an introductory book such as this one, it was neither possible to include
an extensive list of all original references and major textbooks and monographs on the
subject nor to mention all the people that have contributed to our understanding of the
subject.
Preface xiii
We hope that our readers will find that we have fulfilled the objective of providing
a self-contained and self-explanatory book, which provides a smooth introduction to
this important subject and that they will enjoy reading this book as much as we enjoyed
writing it.
In view of this, the fundamental physical laws governing these systems are
understood well. Unfortunately, however, there are some major difficulties of using
the microscopic laws to the systems with a large number of constituent particles. Due
to the presence of an enormous number of degrees of freedom (such as all particle
positions), such systems are analytically and computationally intractable by using the
ordinary methods of classical and quantum mechanics. The major goal of statistical
mechanics is thus to relate this tantalizing quantitative complexity to the apparent
simplicity of the macroscopic description typically involving a small number of data
such as temperature, pressure, particle density, etc. We would like to understand, for
example, how the ordinary concept of temperature emerges from the complexity of
many particle systems.
Let us now define the important concepts of “microscopic” (“small scale”) and
“macroscopic” (“large scale”). A system is called microscopic, if it is of atomic dimen-
sions or smaller (≤10−10 m). Individual atoms and molecules are examples of such
systems. On the other hand, a system is called macroscopic, if it is visible by, for
example, a microscope using ordinary light (≥10−6 m). A macroscopic system con-
sists typically of a large number of constituent particles. Such a system is a visible (by
the microscope) amount of a gas or a liquid. When studying a macroscopic system,
we are not concerned with the detailed behavior of each of the individual particles
constituting the system. Instead, we usually study macroscopic quantities describing
the system like volume, pressure, temperature, etc.
If the macroscopic quantities describing an isolated system are constant in time, we
say that the system is in equilibrium. If an isolated system is not in equilibrium, the
time-dependent macroscopic quantities, describing the system, will change until the
system reaches an equilibrium.
By applying the statistical physics to the systems consisting of a large number of
constituent particles, it is possible to gain a considerable understanding of these sys-
tems by standard mathematical methods. This success of statistical physics may seem
miraculous, since macroscopic systems consist of such a huge number of particles.
Yet, as we are not concerned with the detailed mechanical behavior of every individ-
ual constituent particle, we can apply the statistical laws to the system. In macroscopic
systems such as gases, due to having a very large number of identical particles, the sta-
tistical laws become highly effective and many important problems become tractable.
2 Introduction and Basic Concepts
2.1 Systems of Identical Particles
The subject of the present discussion is the description of systems consisting of a large
number of identical particles. One such system is a gas consisting of a large number
of constituent molecules. Let us assume that the system under consideration occupies
the volume V and contains N noninteracting particles. The system is surrounded by
some medium and in general it is allowed to exchange both energy and particles with
the surrounding medium.
As the constituent particles of the system are microscopic objects, e.g., gas
molecules, their motion is ruled by the laws of quantum mechanics and they can only
occupy certain discrete energy levels. Let ni be the number of particles, which occupy
the energy levels within the energy interval (Ei , Ei + 1Ei ).
If the system is in an equilibrium state, the total number of particles in the system
is given by
X
N= ni , (2.1)
i
where the sum goes over all energy intervals (Ei , Ei + 1Ei ). The energy of each parti-
cle in the system is the sum of its kinetic and potential energies
Ei = Ti + ϑi , (2.2)
and the total internal energy of the system can be written in the form
X
U= ni Ei . (2.3)
i
Above, we consider the so-called ideal systems that consist of mutually noninter-
acting particles. For the ideal systems, the potential energies ϑi = ϑi (Er) of the particles
are due to the influence of some external fields. For example, a gas under considera-
tion is normally under the influence of the Earth’ gravity. If the potential energies due
to external fields are nearly the same for all constituent particles, then such a system
is nearly homogeneous, that is, it has nearly uniform density. Under this condition,
the potential energies due to external fields are inessential for the description of the
where ~ = h/2π and h = 6.626068 × 10−34 Js is the Planck constant. The motion of
such a “matter wave” is described by a complex wave function
The squared magnitude of the wave function (2.5) is then interpreted as the probability
density of finding the particle in the space point Er = (x, y, z) at the time t. Since the
particle is located somewhere in the three-dimensional space, the absolute square of
the wave function (2.5) satisfies the following normalization condition
Z
|ψ(Er, t)|2 d3 Er = 1, (2.6)
V
Introduction and Basic Concepts 7
where the integration is performed over the entire available three-dimensional space.
Unlike the classical mechanics, quantum mechanics can provide only the information
about the probabilities and expectation values of various physical quantities such as
the particle position, momentum, energy, etc. Thus, the expectation value of the energy
E is given by
Z
< E >= ψ ∗ (Er, t)Ĥψ(Er, t)d3 Er, (2.7)
V
where ψ ∗ (Er, t) is the complex conjugate of the wave function ψ(Er, t), and Ĥ is the
energy operator or the Hamiltonian operator. The form of the operator Ĥ will be deter-
mined later. Likewise, the expectation value of the momentum vector pE is given by
Z
< pE >= ψ ∗ (Er, t)pψ(E
Ê r, t)d3 Er, (2.8)
V
where pÊ is the Momentum operator. In order to determine the forms of the energy and
momentum operators, we can use the wave function of a suitable plane wave, given by
i
κ · Er − iωt) = N exp ( pE · Er − Et) .
ψ(Er, t) = N exp(iE (2.9)
~
∂
i~ ψ(Er, t) = Eψ(Er, t) = Ĥψ(Er, t), (2.10)
∂t
and
∂
− i~ ψ(Er, t) = px ψ(Er, t) = p̂x ψ(Er, t)
∂x
∂
− i~ ψ(Er, t) = py ψ(Er, t) = p̂y ψ(Er, t) (2.11)
∂y
∂
− i~ ψ(Er, t) = pz ψ(Er, t) = p̂z ψ(Er, t).
∂z
The results (2.11) can be summarized in the following vector expression
Substituting (2.10) into (2.7) and (2.12) into (2.8), respectively, and using the normal-
ization condition (2.6), we obtain
Z
< E >= E |ψ(Er, t)|2 d3 Er = E, (2.13)
V
8 Quantum Description of Systems
and
Z
< pE >= pE |ψ(Er, t)|2 d3 Er = pE, (2.14)
V
as expected. In the simple case of the plane wave, the expectation values of the energy
and the momentum of the particle are equal to their exact classical values. From (2.10)
and (2.12), we can now identify the operators Ĥ and pÊ as follows:
∂
Ĥ = i~ , pÊ = −i~ ∇. (2.15)
∂t
Since the wave functions ψ(Er, t) are the functions of Er and t, i.e., we are working in the
ordinary three-dimensional representation, the operators of the coordinates and time
are simply equal to the coordinates and time. Thus, we have
x̂ = x, ŷ = y, ẑ = z, t̂ = t. (2.16)
Let us now recall the classical expression for the total energy of a single nonrelativistic
particle moving in the field of some general potential V = V(Er, t), i.e.,
p2
E= + V(Er, t). (2.17)
2m
Multiplying both sides with the wave function ψ(Er, t), we obtain
p2
Eψ(Er, t) = ψ(Er, t) + V(Er, t)ψ(Er, t). (2.18)
2m
Substituting the dynamical variables with their quantum-mechanical operators, we
obtain the following operator equation
p̂2
Ĥ ψ(Er, t) = ψ(Er, t) + V̂(Êr, t̂)ψ(Er, t). (2.19)
2m
Substituting the operator definitions (2.15) and (2.16), we obtain the most general
time-dependent Schrödinger equation, in the following form
∂ψ ~2
i~ = − ∇ 2 ψ + V(Er, t)ψ, (2.20)
∂t 2m
where ψ = ψ(Er, t). The Schrödinger equation (2.20) is the fundamental equation of
quantum mechanics. In case of a stationary potential V(Er, t) = V(Er), i.e., a potential
that is constant in time, the wave function can be written in the form
iEt
ψ(Er, t) = ψ(Er) exp . (2.21)
~
Introduction and Basic Concepts 9
~2 2
− ∇ ψ(Er) + V(Er) ψ(Er) = E ψ(Er). (2.22)
2m
In this book, we will only analyze the stationary phenomena, and we will, therefore,
use the time-independent Schrödinger equation (2.22) only.
h i
Calculate the commutators x, pˆx and Ĥ, t .
Solution
The commutator x, pˆx applied to an arbitrary wave function ψ gives
∂
x, pˆx ψ = −i~ x, ψ,
(2.23)
∂x
or
∂ψ ∂
x, pˆx ψ = −i~ x − (xψ) = i~ ψ.
(2.24)
∂x ∂x
Thus, we finally obtain the commutator
x, pˆx = i~.
(2.25)
h i
Similarly, the commutator Ĥ, t applied to an arbitrary wave function ψ gives
∂
h i
Ĥ, t ψ = i~ , t ψ, (2.26)
∂t
or
∂ ∂ψ
h i
Ĥ, t ψ = i~ (tψ) − t = i~ ψ. (2.27)
∂t ∂t
Thus, we finally obtain the commutator
h i
Ĥ, t = i~. (2.28)
3 Kinetic Energy of Translational
Motion
1
Ei = mv2i . (3.1)
2
p2i 1 2
Ei = = pix + p2iy + p2iz . (3.2)
2m 2m
For the sake of simplicity, at this point, we can drop the label of the particle and write
p2 1 2
E= = px + p2y + p2z . (3.3)
2m 2m
V = a3
y
a
a
0 a x
In quantum mechanics, the kinetic energy (3.3) is replaced by the Hamiltonian operator
Ĥ as follows:
p̂2 1 2
Ĥ = = p̂x + p̂2y + p̂2z . (3.4)
2m 2m
∂ ∂ ∂
p̂x = −i~ , p̂y = −i~ , p̂z = −i~ . (3.6)
∂x ∂y ∂z
~2 ∂2 ∂2 ∂2 ~2 2
Ĥ = − + + =− ∇ . (3.7)
2m ∂x2 ∂y2 ∂z2 2m
~2 2
− ∇ ψ = Eψ, (3.8)
2m
or using (3.7)
1 ∂ 2ψ 1 ∂ 2ψ 1 ∂ 2ψ 2mE
+ + =− 2 . (3.9)
ψ ∂x2 ψ ∂y2 ψ ∂z2 ~
where the functions X(x), Y( y), and Z(z) are the functions of a single variable x, y, and
z, respectively. The equation (3.9) then reduces to
1 d2 X 1 d2 Y 1 d2 Z 2mE
+ + =− 2 . (3.11)
X dx2 Y dy2 Z dz2 ~
Kinetic Energy of Translational Motion 13
By examination of the equation (3.11), we see that the first term on the left-hand side
of the equation is a function of the co-ordinate x only. Analogously, the second term on
the left-hand side of the equation (3.11) is a function of the co-ordinate y only, and the
third term on the left-hand side of the equation (3.11) is a function of the co-ordinate z
only. Thus, the equation (3.11) has the form
The equality (3.12) is possible only if each of the three functions f (x), g( y), and h(z)
is a constant. Otherwise, since x, y, and z are independent variables, by their arbitrary
change, we could always spoil the equality (3.12). Thus, we can write
1 d2 X 1 d2 Y 1 d2 Z
= −k 2
x , = −k 2
y , = −kz2 , (3.13)
X dx2 Y dy2 Z dz2
2mE
kx2 + ky2 + kz2 = . (3.14)
~2
From the equation (3.14), we see that if we know the three quantities kx , ky , and kz , we
can easily calculate the translational energy of a constituent particle in our system as
follows:
~2 2
E= kx + ky2 + kz2 . (3.15)
2m
The three differential equations (3.13) are ordinary differential equations which can be
written in the form
d2 X
+ kx2 X = 0, (3.16)
dx2
d2 Y
+ ky2 Y = 0, (3.17)
dy2
d2 Z
+ kz2 Z = 0. (3.18)
dz2
In order to solve these three differential equations, we need to specify the bound-
ary conditions for our system in the cubic box. In quantum mechanics, the quantity
π(x, y, z) = |ψ(x, y, z)|2 is interpreted as the probability of finding a constituent parti-
cle at the point in space specified by the co-ordinates (x, y, z). According to our initial
assumption, all of the constituent particles of the system are confined to the interior of
the cubic box with impenetrable walls, and no particle can be found outside the box.
Thus, the probability π(x, y, z) and thereby the complex function ψ(x, y, z) must be
equal to zero for any point in space which lies outside the cubic box, i.e., where x, y,
14 Quantum Description of Systems
or z are less than zero or larger than the side of the cube a. The boundary conditions
for our problem are, therefore, specified as follows:
But since the function ψ(x, y, z) must be a continuous function, we must have
The set of conditions (3.25), (3.26), and (3.27) is the set of the required boundary
conditions for the three differential equations (3.16), (3.17), and (3.18), respectively.
They are called the boundary conditions, since they specify the behavior of our solu-
tions at the boundaries of the cubic box. The three differential equations, given by the
equations (3.16), (3.17), and (3.18), have the following general solutions
and
Za Za Za
|ψ(x, y, z)|2 dx dy dz = 1. (3.36)
0 0 0
Za n π Za Za
2 ny π
n π
x z
2 2
A sin x dx sin y dy sin2 z dz = 1. (3.37)
a a a
0 0 0
aaa 3/2
2
A 2
=1 ⇒ A= . (3.39)
2 2 2 a
3/2
2 nx π ny π nz π
ψ(x, y, z) = sin x sin y sin z . (3.40)
a a a a
16 Quantum Description of Systems
~2 π 2 2
E= 2
nx + n2y + n2z , (3.41)
2ma
or using ~ = h/2π
h2 2
E= nx + n 2
y + n 2
z . (3.42)
8ma2
The volume of the cubic box is equal to V = a3 , and we can finally write
h2 2
E= n x + n 2
y + n 2
z = E 0 n 2
x + n 2
y + n 2
z , (3.43)
8mV 2/3
h2
E0 = . (3.44)
8mV 2/3
The order of magnitude of E0 can be calculated using the result for the Planck con-
stant h = 6.626068 × 10−34 Js. A typical microscopic gas particle has a mass of the
order m ∼ 10−27 kg, and our system is assumed to be contained in a cubic box of a
macroscopic size V ∼ 1 m3 . Thus, we obtain
10−67
E0 ∼ ∼ 10−40 J. (3.45)
10−27 × 1
The result for the energy of translation of constituent particles (3.43) will be used
to calculate the thermodynamic properties of an ideal gas. This result shows that the
energy levels of a particle are spherically distributed and that the particles can only
occupy a discrete spectrum of energy eigenvalues, i.e.,
Solution
(a) The energy eigenvalues are given by
h2 2
E= 2/3
nx + n2y + n2z = E0 n2 , (3.47)
8mV
where
h2
E0 = ≈ 6 × 10−34 J, (3.48)
8mV 2/3
and
(nx , ny , nz ) n2 E
(b) The degeneracy of the above quantum states is given by the number of arrange-
ments of the numbers (nx , ny , nz ) corresponding to the same value of E (or n2 ).
For example, the quantum state with n2 = 6 can be realized by three different
18 Quantum Description of Systems
arrangements of the numbers (nx , ny , nz ), i.e., (1, 1, 2), (1, 2, 1), and (2, 1, 1). Thus,
the degeneracy of the first six quantum states is
(nx , ny , nz ) n2 Degeneracy
(1, 1, 1) 3 1
(1, 1, 2) 6 3
(1, 2, 2) 9 3
(1, 1, 3) 11 3
(2, 2, 2) 12 1
(1, 2, 3) 14 6
For example, the quantum state with n2 = 14 can be realized by six different
arrangements of the numbers (nx , ny , nz ), i.e., (1, 2, 3), (1, 3, 2), (2, 1, 3), (2, 3, 1),
(3, 1, 2), and (3, 2, 1). From the above table, we see that the energy eigenvalues of
an electron in a cubic box are not evenly distributed.
4 Energy of Vibrations
4.1 Hamiltonian of Vibrations
In reality, the constituent particles of systems cannot be exactly modeled as point
particles. They typically have an internal structure. A good example is the common
diatomic molecules such as H2 , O2 , N2 , CO, etc. Such a molecule can not only trans-
late (with its center of mass moving within a confining box) but also execute internal
motions such as rotation around its center of mass (discussed in Chapter 5 “Kinetic
Energy of Rotations”) as well a vibrational motion in which the length of the chemical
bond connecting the two atoms oscillates with angular frequency ω. In this chapter,
we will describe this vibrational motion of a diatomic molecule by means of the sim-
ple harmonic oscillator model with the total energy (i.e., classical Hamiltonian) of the
form
p2 1
EV = + m ω 2 x2 , (4.1)
2m 2
where m = (1/m1 + 1/m2 )−1 is the so-called reduced mass of the molecule (with m1
and m2 being the masses of the two atoms), and x is the deviation of the molecule’s
chemical bond length away from its mechanical equilibrium value. In quantum
mechanics, the energy of the harmonic oscillator (4.1) is replaced by the Hamiltonian
operator HˆV as follows:
p̂2 1
HˆV = + m ω 2 x2 . (4.2)
2m 2
The vibrations of a constituent particle are described by the wave function ψ(x), which
satisfies the Schrödinger equation
∂
p̂x = −i~ . (4.4)
∂x
d2 ψ λ
+ − u ψ = 0.
2
(4.8)
du2 α
In order to solve the equation (4.8), we introduce a new function H = H(u) as follows:
2 /2
ψ(u) = e−u H(u). (4.9)
The second derivative of the wave function (4.9) is given by
d2 ψ
2
−u2 /2 d H dH 2
=e − 2u + u −1 H . (4.10)
du2 du2 du
Substituting (4.9) and (4.10) into (4.8), we obtain
d2 H λ
dH
− 2u + − 1 H = 0. (4.11)
du2 du α
The equation (4.11) is solved by expanding the function H = H(u) into the power
series as follows:
∞
X ∞
X
H= k
ak u = aj u j . (4.12)
k=0 j=0
From the equation (4.15), we obtain the recurrence formula for the coefficients of the
power series (4.12) as follows:
2k + 1 − λ/α
ak+2 = ak . (4.16)
(k + 1)(k + 2)
If we know the boundary conditions a0 = H(0) and a1 = Ḣ(0), the formula (4.16)
allows us to calculate the coefficients of the entire infinite series (4.12). As the squared
magnitude of the wave function ψ = ψ(x) gives the probability density of finding the
vibrating particle at a certain distance x, the appropriate boundary condition for the
wave function is that it must approach zero as x → ∞. However, the wave function
(4.9) with an infinite series (4.12) is divergent for u → ∞ (or x → ∞). The only way
to obtain a proper bound-state wave function is to choose the parameter λ in such a
way to terminate the power series and reduce it to a polynomial. Let us, therefore,
assume that for some integer k = n, we have
λn
= 2n + 1, n = 0, 1, 2 . . . . (4.17)
α
Substituting (4.17) into (4.16), we obtain
(2k + 1) − (2n + 1) 2(k − n)
ak+2 = ak = ak . (4.18)
(k + 1)(k + 2) (k + 1)(k + 2)
From (4.18), it is clear that ak ≡ 0 for any k > n, and the power series is reduced to a
polynomial. The polynomials obtained in this way are known as Hermite polynomials
and they satisfy the Hermite differential equation
d2 H n dHn
− 2u + 2n Hn = 0. (4.19)
du2 du
The equation (4.21) is the celebrated result for the quantized energy levels of the
simple harmonic oscillator used here to model the vibrational motion of diatomic
molecules. In thermodynamics, we are primarily interested in this result for the energy
of vibrations of constituent particles in the system (4.21). However, for the sake of
completeness, we will derive the result for the normalized wave function of the vibrat-
ing constituent particle as well.
Further, if we choose a0 = −2 for H2 (u), a1 = −12 for H3 (u), and a0 = 12 for H4 (u),
respectively, we obtain
H2 (u) = −2 + 4u2
The particular choices of the above boundary conditions were made to fit a practi-
cal formula, which can also be used for calculation of the Hermite polynomials. It is
known as Rodrigues’ formula, and it reads
2 dn −u2
Hn (u) = (−1)n eu e . (4.24)
dun
It is easily shown, by direct calculation, that the Rodrigues’ formula reproduces the
results (4.22) and (4.23). The Hermite polynomials can be generated using the follow-
ing generating function
∞
2 2 −(t−u)2 X Hk (u)
G(u, t) = e2tu−t = eu = t k. (4.25)
k!
k=0
In order to prove that the polynomials Hk (u) in (4.25) are indeed the Hermite polyno-
mials, we calculate the n-th derivative with respect to t of both of its sides. The n-th
Energy of Vibrations 23
∂n u2 ∂
n
−(t−u)2 n u2 ∂
n 2
G(u, t) = e e = (−1) e e−(t−u) , (4.26)
∂t n ∂t n ∂u n
while the n-th derivative of the series expansion of the generating function is obtained
as follows:
∞ ∞
∂n ∂ n X Hk (u) k X Hk (u) dn k
G(u, t) = n t = t . (4.27)
∂t n ∂t k! k! dtn
k=0 k=0
dn k k!
t = t k−n , (4.28)
dt n (k − n)!
∞ ∞
X Hj+n (u)
∂n X Hk (u)
G(u, t) = t k−n = t j. (4.29)
∂t n (k − n)! j!
k=n j=0
∞
2 ∂ n −(t−u)2 X Hj+n (u) j
(−1)n eu e = t. (4.30)
∂un j!
j=0
The equality (4.30) is valid for any value of t. In particular, for t = 0, we obtain
2 ∂ n −u2
Hn (u) = (−1)n eu e , (4.31)
∂un
and it is identical with the Rodrigues’ formula (4.24) above. Thus, we have shown that
the polynomials Hk (u) in (4.25) are the Hermite polynomials.
2 /2
ψn (u) = An e−u Hn (u), (4.32)
24 Quantum Description of Systems
where An is a normalization constant. Using now the generating function for Hermite
polynomials (4.25), we can obtain the normalization condition for the harmonic oscil-
lator wave functions (4.32) and calculate the normalization constant An . Let us begin
with the definition of the generating function (4.25), in the following form
∞ ∞
2 X Hn (u) 2 X Hm (u)
e2tu−t = tn , e2su−s = sm . (4.33)
n! m!
n=0 m=0
Multiplying the two generating functions in (4.33) with each other, we obtain
∞ X
∞ m n
2tu−t2 +2su−s2
X s t
e = Hm (u)Hn (u). (4.34)
m! n!
m=0 n=0
Multiplying now both sides of the equality (4.34) by exp −u2 and integrating from
Z+∞
2 2 2
I= du e−u +2tu−t +2su−s
−∞
∞ X
∞ m n Z +∞
X s t 2
= du e−u Hm (u)Hn (u). (4.35)
m! n!
m=0 n=0 −∞
Z+∞ ∞ m m m
−(u−s−t)2 √ 2st √ X 2 s t
I=e 2st
du e = πe = π . (4.37)
m!
−∞ m=0
∞ m m m ∞ X
∞ m n Z+∞
√ X 2 s t X s t 2
π = du e−u Hm (u)Hn (u), (4.38)
m! m! n!
m=0 m=0 n=0 −∞
or
∞ n Z+∞
√ m m X t 2
π2 t = du e−u Hm (u)Hn (u). (4.39)
n!
n=0 −∞
Energy of Vibrations 25
From the equation (4.39), we immediately see that the only nonzero term in the sum
on the right-hand side is the one with n = m. Thus, we obtain the following orthonor-
mality condition for the Hermite polynomials
Z+∞
2 √
du e−u Hm (u)Hn (u) = δmn π 2n n!. (4.40)
−∞
Using now the results (4.32) and (4.40), as well as the orthonormality of the oscillator
wave functions ψn (x), we can now calculate
Z+∞
δmn = dx ψm (x)ψn (x)
−∞
Z+∞
1 2
= Am An √ du e−u Hm (u)Hn (u)
α
−∞
π n
r
= δmn Am An 2 n!. (4.41)
α
For m = n, we thus obtain
α
r
1
2
An = n , (4.42)
2 n! π
or using (4.7)
1 α 1/4
r r
1 mω 1/4
An = = . (4.43)
2n n! π 2n n! π ~
Substituting (4.43) into (4.32), we obtain the final result for the normalized wave func-
tion of a vibrating constituent particle of our system, which occupies the quantum state
with energy En , in the following form
r
mωx2
r
1 mω 1/4 mω
ψn (x) = exp − H n x . (4.44)
2n n! π ~ 2~ ~
Solution
Since there are no external sources, the total voltage over the closed LC-circuit is equal
to zero, i.e.,
In the above result, we have used the definition of the electric current i(t) = dq(t)/dt
and the characteristic relations for inductors and capacitors
di(t) q(t)
uL (t) = L , uC (t) = . (4.46)
dt C
or
" #
d L dq 2 q2
+ = 0. (4.48)
dt 2 dt 2C
or
p2q
1 1
H= + L ω 2 q2 , ω= √ , (4.50)
2L 2 LC
dq
pq = L . (4.51)
dt
The equation (4.50) is the well-known harmonic oscillator equation, where the induc-
tance L plays the role of the mass m and the capacitor charge q(t) plays the role of the
co-ordinate x(t). Now, we can use the quantum-mechanical prescription to define the
momentum operator
∂
p̂q = −i~ . (4.52)
∂q
Energy of Vibrations 27
ϕ
CM
In (5.4), we use the components of the linear momentum vector pE = mEv = (px , py , pz )
in Descartes co-ordinates. In quantum mechanics, the kinetic energy of the rigid rotator
(5.3) is replaced by the Hamiltonian operator ĤR as follows:
L̂2 1 2
ĤR = = L̂x + L̂y2 + L̂z2 . (5.5)
2I 2I
The rotation of the particle is then described by its wave function ψ(θ, φ), which
satisfies the Schrödinger equation
where (θ, φ) are the two spherical angular co-ordinates, which are suitable for the
description of the rotational motion of the constituent particles. In order to specify the
operator ĤR , we use the quantum-mechanical prescriptions
∂ ∂ ∂
p̂x = −i~ , p̂y = −i~ , p̂z = −i~ . (5.7)
∂x ∂y ∂z
Substituting (5.7) into (5.4), we obtain the three components of the angular momen-
tum operator in Descartes co-ordinates
∂ ∂
L̂x = −i~ y − z , (5.8)
∂z ∂y
∂ ∂
L̂y = −i~ z −x , (5.9)
∂x ∂z
∂ ∂
L̂z = −i~ x −y . (5.10)
∂y ∂x
The inverse expressions for spherical co-ordinates in terms of the Descartes co-ordi-
nates are then given by
q
r = x2 + y2 + z2 , (5.12)
p !
x 2 + y2
θ = arctan , (5.13)
z
y
φ = arctan . (5.14)
x
Kinetic Energy of Rotations 31
(x, y, z)
θ
r
φ y
∂ ∂r ∂ ∂θ ∂ ∂φ ∂
= + + , (5.15)
∂x ∂x ∂r ∂x ∂θ ∂x ∂φ
∂ ∂r ∂ ∂θ ∂ ∂φ ∂
= + + , (5.16)
∂y ∂y ∂r ∂y ∂θ ∂y ∂φ
∂ ∂r ∂ ∂θ ∂ ∂φ ∂
= + + . (5.17)
∂z ∂z ∂r ∂z ∂θ ∂z ∂φ
After the explicit calculation of the derivatives, using the expressions (5.12–5.14), we
obtain
Substituting (5.18–5.20) into (5.8–5.10), we can now derive the results for the com-
ponents of the angular momentum operator in terms of spherical angles (θ, φ). It turns
out that all the dependence on the radial co-ordinate r is canceled and we obtain the
following expressions
∂ cos φ ∂
L̂x = i~ sin φ + , (5.21)
∂θ tan θ ∂φ
∂ sin φ ∂
L̂y = i~ −cos φ + , (5.22)
∂θ tan θ ∂φ
∂
L̂z = −i~ . (5.23)
∂φ
32 Quantum Description of Systems
∂ 2ψ
L̂z2 ψ(θ, φ) = −~2 , (5.24)
∂φ 2
and
L̂x2 + L̂y2 ψ(θ, φ)
∂ cos φ ∂ ∂ψ cos φ ∂ψ
= −~ 2
sin φ + sin φ +
∂θ tan θ ∂φ ∂θ tan θ ∂φ
∂ sin φ ∂ ∂ψ sin φ ∂ψ
+ − cos φ + − cos φ +
∂θ tan θ ∂φ ∂θ tan θ ∂φ
∂ ψ 1 ∂ψ 1 ∂ ψ
2 2
= − ~2 + +
∂θ 2 tan θ ∂θ tan2 θ ∂φ 2
1 ∂ ∂ψ 1 ∂ 2ψ
= −~ 2
sin θ + . (5.25)
sin θ ∂θ ∂θ tan2 θ ∂φ 2
Putting together the results (5.24) and (5.25), we finally obtain the square of the angu-
lar momentum operator as follows:
1 ∂ ∂ 1 ∂2
L̂2 = L̂x2 + L̂y2 + L̂z2 = −~2 sin θ + 2 . (5.26)
sin θ ∂θ ∂θ sin θ ∂φ 2
Substituting the result (5.26) into (5.5), we finally obtain the Hamiltonian operator of
rotations ĤR as follows:
~2 1 ∂ ∂ 1 ∂2
ĤR = − sin θ + 2 . (5.27)
2I sin θ ∂θ ∂θ sin θ ∂φ 2
Substituting the result (5.27) into the result (5.28), we obtain the equation
1 ∂ ∂ψ 1 ∂ 2ψ
sin θ + 2 + λψ = 0, (5.29)
sin θ ∂θ ∂θ sin θ ∂φ 2
Kinetic Energy of Rotations 33
2IER
λ= . (5.30)
~2
Multiplying the equation (5.29) by sin2 θ and separating the terms which depend on θ
and φ, we obtain
∂ ∂ψ ∂ 2ψ
sin θ sin θ + λ sin2 θ ψ = − 2 . (5.31)
∂θ ∂θ ∂φ
In order to find a solution of the equation (5.31), we assume that the solution ψ(θ, φ)
can be written in the form
where the functions P(θ ) and 8(φ) are the functions of a single variable θ and φ,
respectively. The equation (5.31) then reduces to
1 d2 8
1 d dP
sin θ sin θ + λ sin2 θ = − . (5.33)
P dθ dθ 8 dφ 2
By examination of the equation (5.33), we see that its left-hand side is a function of
the co-ordinate θ only, while its right-hand side is a function of the co-ordinate φ only.
Thus, the equation (5.33) has the form f (θ ) = g(φ). Such an equality is possible only
if both of the functions f (θ ) and g(φ) are equal to the same constant. Otherwise, since
θ and φ are independent variables, by their arbitrary change, we could always spoil
the equality. Thus, we can write
1 d2 8
1 d dP
sin θ sin θ + λ sin2 θ = − = m2 , (5.34)
P dθ dθ 8 dφ 2
where m2 is an arbitrary positive constant. The equation for 8(φ) then becomes
d2 8
+ m2 8 = 0. (5.35)
dφ 2
The normalized solutions of the equation (5.35) have the following general form
1
8(φ) = √ exp(imφ). (5.36)
2π
To proceed, we note that (θ, φ) and (θ, φ + 2π ) correspond to the same spatial orienta-
tion in Fig. 5.2. Because of this, the condition 8(φ + 2π) = 8(φ) must be required. It
implies that exp(i2mπ ) = 1, or that the parameter m is an integer (m = 0, ±1, ±2, . . .).
34 Quantum Description of Systems
This means that the eigenstates of the Hamiltonian ĤR , described by the wave function
(5.32), are also the eigenstates of the operator L̂z and that we can use the result (5.36)
to calculate the eigenvalues of the operator L̂z . Thus, we obtain from (5.23)
d 1
L̂z 8(φ) = −i~ √ exp(imφ) = m~8(φ). (5.39)
dφ 2π
Thus, the rotating particle can only have certain quantized values of the angular
momentum vector component in z-direction, i.e., Lz = m~. The elementary quantum
of the angular momentum component Lz is the Planck constant ~. The equation for
P(θ ) is given by (5.34)
1 d dP
sin θ sin θ + λ sin2 θ − m2 = 0, (5.40)
P dθ dθ
m2
1 d dP
sin θ + λ− 2 P = 0. (5.41)
sin θ dθ dθ sin θ
m2
d dP
sin2 θ + λ− P = 0, (5.42)
−sin θdθ −sin θ dθ 1 − cos2 θ
or
m2
d 2 dP
1−µ + λ− P = 0, (5.43)
dµ dµ 1 − µ2
or
d2 P dP
m2
1 − µ2 − 2µ + λ − P = 0. (5.44)
dµ2 dµ 1 − µ2
Kinetic Energy of Rotations 35
In order to solve the equation (5.44), let us first denote the solution of the complete
equation with m 6= 0 by Plm (µ), where l is the yet unspecified parameter, which will
be used to specify the eigenstates of the Hamiltonian operator. The solution of the
equation (5.44), in the special case when m = 0, is then denoted by Pl0 (µ) = Pl (µ).
Thus, the two functions Plm (µ) and Pl (µ) satisfy following differential equations
m2
d 2 dPlm
1−µ + λ− Plm = 0, (5.45)
dµ dµ 1 − µ2
dP
d l
1 − µ2 + λPl = 0. (5.46)
dµ dµ
For this type of differential equations, it is possible to derive a fairly simple formula
that relates the two functions Plm (µ) and Pl (µ), so to solve the equation (5.45), it is
sufficient solve the simpler equation (5.46). In order to derive the formula that relates
the two functions Plm (µ) and Pl (µ), let us first differentiate the equation (5.46) m-
times, assuming that m > 0 as follows:
dm
d 2 dPl
1 − µ + λPl = 0, (5.47)
dµm dµ dµ
or
dm+2 Pl dm+1 dm Pl
2 dPl
− µ + λ = 0. (5.48)
dµm+2 dµm+1 dµ dµm
dn 2 dn y dn−1 y dn−2 y
n
x y = x2 n + 2nx n−1 + n(n − 1) n−2 , (5.49)
dx dx dx dx
we obtain from (5.48)
d2 dm P d dm Pl
l
1 − µ2 m
− 2(m + 1)µ
2
dµ dµ dµ dµm
dm Pl
+ [λ − m(m + 1)] = 0. (5.50)
dµm
dm Pl
Qlm = , (5.51)
dµm
On the other hand, if we introduce the auxiliary function Qlm in the equation (5.45)
using a different definition
m/2
Plm = 1 − µ2 Qlm , (5.53)
we obtain
dP m/2 m/2+1 dQ
lm lm
1 − µ2 = −mµ 1 − µ2 Qlm + 1 − µ2 (5.54)
dµ dµ
and
d dP m/2 d2 Q
lm lm
1 − µ2 = 1 − µ2 1 − µ2
dµ dµ dµ2
m µ
2 2
dQlm
− 2(m + 1)µ + − m Q lm . (5.55)
dµ 1 − µ2
The two equations (5.56) and (5.52) are identical to each other, which proves that the
auxiliary functions Qlm , defined by (5.51) and (5.53) satisfy the same differential equa-
tion. Thus, we can assume that they are identical to each other and use the definitions
(5.51) and (5.53) to write down the formula, which relates the two solutions Plm (µ)
and Pl (µ) as follows:
|m|/2 d|m| P (µ)
l
Plm (µ) = 1 − µ2 , (5.57)
dµ|m|
where we now allow both positive and negative values of the integer m = 0, ±1,
±2, . . . and replace m by |m|.
As we have argued above, if we know the solution Pl (µ) of the equation (5.46), we
can calculate the solution Plm (µ) of the general equation (5.45) using formula (5.57).
The equation (5.46) is solved by expanding the function Pl = Pl (µ) into the power
series as follows:
∞
ak µk .
X
Pl (µ) = (5.58)
k=0
or
∞
{(k + 2)(k + 1)ak+2 − [k(k + 1) − λ]ak }µk = 0.
X
(5.61)
k=0
From the equation (5.61), we obtain the recurrence formula for the coefficients of the
power series (5.58) as follows:
k(k + 1) − λ
ak+2 = ak . (5.62)
(k + 2)(k + 1)
If we know the boundary conditions a0 = Pl (0) and a1 = Ṗl (0), the formula (5.62)
allows us to calculate the coefficients of the entire infinite series (5.58). As the wave
function ψ = ψ(θ, φ) is a measure of the probability of finding the rotating body in
a certain orientation in Fig. 5.2, an obvious boundary condition for the wave function
is that it must be convergent for all values −π ≤ θ ≤ +π or, since µ = cos θ , for all
values −1 ≤ µ ≤ +1. However, the power series (5.58) is divergent for µ = ±1. The
only way to obtain a proper bound-state wave function is to choose the parameter λ
in such a way to terminate the power series and reduce it to a polynomial. Let us,
therefore, assume that for some integer k = l, we have
or
~2
El = l(l + 1), l = 0, 1, 2, . . . . (5.67)
2I
The result (5.67) is the well-known result for the quantized energy eigenstates of the
rotating constituent particle of the system. In thermodynamics, we are primarily inter-
ested in this result for the energy of rotations of constituent particles in the system
(5.67). However, for the sake of completeness, we will derive some results for the
wave functions of the rotating constituent particles as well.
Further, if we choose a0 = −1/2 for P2 (µ), a1 = −12/9 for P3 (µ), and a0 = 3/8 for
P4 (µ), respectively, we obtain
1 2
P2 (µ) = 3µ − 1 ,
2
4 3
P3 (µ) = 5µ − 3µ , (5.69)
9
1
P4 (µ) = 35µ4 − 30µ2 + 3 .
8
The particular choices of the above boundary conditions were made to fit a practical
formula, which can also be used for calculation of the Legendre polynomials. It is
known as Rodrigues’ formula, and it reads
1 dl 2 l
Pl (µ) = µ − 1 . (5.70)
2l l! dµl
It is easily shown, by direct calculation, that the Rodrigues’ formula reproduces the
results (5.68) and (5.69). Using the Legendre differential equation (5.65), it is easily
shown that the Legendre polynomials are orthogonal to each other, i.e., that
Z+1
dµ Pl (µ)Pj (µ) = 0, l 6= j. (5.71)
−1
Kinetic Energy of Rotations 39
In order to prove the orthogonality of the Legendre polynomials, let us rewrite the
equation (5.65) for Pl (µ)and Pj (µ), respectively, as follows:
d h i
1 − µ2 Ṗl + l(l + 1)Pl = 0, (5.72)
dµ
d h i
1 − µ2 Ṗj + j( j + 1)Pj = 0. (5.73)
dµ
Multiplying the equation (5.72) by Pj (µ) and the equation (5.46) by Pl (µ), we obtain
d h i
Pj 1 − µ2 Ṗl + l(l + 1)Pl Pj = 0, (5.74)
dµ
d h i
Pl 1 − µ2 Ṗj + j( j + 1)Pl Pj = 0, (5.75)
dµ
or
d h i
1 − µ2 Pj Ṗl − 1 − µ2 Ṗl Ṗj + l(l + 1)Pl Pj = 0, (5.76)
dµ
d h i
1 − µ2 Pl Ṗj − 1 − µ2 Ṗl Ṗj + j( j + 1)Pl Pj = 0. (5.77)
dµ
d h i
− 1 − µ2 Pj Ṗl − Pl Ṗj = [l(l + 1) − j( j + 1)]Pl Pj . (5.78)
dµ
Z+1
[l(l + 1) − j( j + 1)] dµ Pl (µ)Pj (µ)
−1
Z+1
d h i
= − dµ 1 − µ2 Pj Ṗl − Pl Ṗj
dµ
−1
i +1
h
= − 1 − µ Pj Ṗl − Pl Ṗj = 0,
2
(5.79)
−1
or
Z+1
[l(l + 1) − j( j + 1)] dµ Pl (µ)Pj (µ) = 0. (5.80)
−1
40 Quantum Description of Systems
In order to satisfy the equation (5.80), we see that for any j 6= l, we must have
Z+1
dµ Pl (µ)Pj (µ) = 0, l 6= j, (5.81)
−1
which is identical with the initial assumption (5.71). Thus, the Legendre polynomials
are indeed orthogonal to each other. For j = l, the integral in the equation (5.80) is not
equal to zero, and its value is needed to determine the normalization constant for the
Legendre polynomials. Let us, therefore, as the next step, calculate the integral
Z+1
Il = dµ [Pl (µ)]2 . (5.82)
−1
Z+1
1 dl l dl l
Il = l 2 dµ l µ2 − 1 µ2
− 1 . (5.83)
[2 l!] dµ dµl
−1
dl 2 l dl l
µ − 1 µ2
− 1
dµl dµl
l−1 l dl l
d d
= µ −1
2
µ −1
2
dµ dµl−1 dµl
dl−1 2 l dl+1 l
− µ − 1 µ2
− 1 , (5.84)
dµl−1 dµl+1
and the result
dl−1 2 l
µ − 1 =0 for µ = ±1, (5.85)
dµl−1
we can integrate (5.83) by parts to obtain
Z+1
(−1)1 dl−1 l dl+1 l
Il = l 2 dµ l−1 µ2 − 1 µ2
− 1 . (5.86)
[2 l!] dµ dµl+1
−1
Z+1
(−1)l l d2l l
Il = l 2 dµ µ2 − 1 µ2 − 1 . (5.87)
[2 l!] dµ 2l
−1
Kinetic Energy of Rotations 41
d2l 2 l d2l 2l
µ − 1 = µ = (2l)!, (5.88)
dµ2l dµ2l
Z+1
(−1)l (2l)! l
Il = dµ µ2 − 1 , (5.89)
[2l l!]2
−1
or
Z+1
(−1)l (2l)!
Il = dµ (µ − 1)l (µ + 1)l . (5.90)
[2l l!]2
−1
Let us now drop the constant factor in (5.90) and consider the integral
Z+1
Jl = dµ (µ − 1)l (µ + 1)l . (5.91)
−1
l+1 +1 Z+1
l (µ + 1) (µ + 1)l+1
Jl = (µ − 1) − dµ l(µ − 1)l−1 . (5.92)
l+1
−1 l+1
−1
Z+1
l
Jl = (−1) 1
dµ(µ − 1)l−1 (µ + 1)l+1 . (5.93)
l+1
−1
Z+1
l(l − 1)
Jl = (−1)2 dµ(µ − 1)l−2 (µ + 1)l+2 . (5.94)
(l + 1)(l + 2)
−1
Z+1
l l! (−1)l (l!)2 22l+1
Jl = (−1) dµ(µ + 1)2l = . (5.95)
(2l)!/l! (2l)! 2l + 1
−1
42 Quantum Description of Systems
Z+1
2
dµ [Pl (µ)]2 = . (5.97)
2l + 1
−1
1 |m|/2 dl+|m| l
Plm (µ) = 1 − µ2
µ 2
− 1 . (5.98)
2l l! dµl+|m|
From the result (5.98), we see that Plm (µ) and consequently the wave function
ψlm (θ, φ) vanishes when |m| > l. Thus, we must have −l ≤ m ≤ +l. This implies that
every energy eigenstate with a given quantum number l has g(l) = 2l + 1 substates
with different values of the quantum number m, i.e., different values of the angular
momentum vector component in z-direction Lz .
The wave function for the rotating constituent particle is then given by (5.32), with
(5.36) and (5.98). Thus, we have
1
ψlm (θ, φ) = Alm Plm (cos θ ) √ exp(± i |m| φ), (5.99)
2π
where Alm are the normalization constants for the functions Plm , given by (5.98). In
order to calculate the normalization constants Alm , we need to calculate the integral
Z+1
Ilm = dµ[Plm (µ)]2 . (5.100)
−1
Let us first recall the definition (5.57) with |m| = m > 0, i.e.,
m/2 dm P (µ)
l
Plm (µ) = 1 − µ2 . (5.101)
dµm
or
1/2 dP (m−1)/2 dm P (µ)
lm l
1 − µ2 = −mµ 1 − µ2
dµ dµm
(m+1)/2 dm+1 P
l
+ 1 − µ2 m+1
, (5.103)
dµ
or
dP 2 dPlm m2 µ2 2
lm
P2lm+1 = 1 − µ2 + 2mµPlm + P . (5.106)
dµ dµ 1 − µ2 lm
Z+1 Z+1 dP dP
lm lm
Ilm+1 = dµ [Plm+1 (µ)] = dµ 1 − µ2
2
dµ dµ
−1 −1
Z+1 Z+1
dPlm m2 µ2 2
+ dµ 2 mµPlm + dµ P . (5.107)
dµ 1 − µ2 lm
−1 −1
dP dP
lm lm d dPlm
1 − µ2 = 1 − µ2 Plm
dµ dµ dµ dµ
dP
d lm
− Plm 1 − µ2 , (5.108)
dµ dµ
and
dPlm d d
2mµPlm = mµ P2lm = mµP2lm − mP2lm , (5.109)
dµ dµ dµ
44 Quantum Description of Systems
as well as the fact that 1 − µ2 = 0 and mPlm = 0 for µ = ±1, we can integrate the
first and the second integral on the right-hand side of the equation (5.107) by parts, to
obtain
Z+1 dP
d lm
Ilm+1 = dµ Plm − 1 − µ2
dµ dµ
−1
m2 µ2
+ −m + P lm . (5.110)
1 − µ2
m2 µ2 m2
−m + = −m(m + 1) + , (5.111)
1−µ 2 1 − µ2
Z+1
d 2 dPlm
Ilm+1 = dµPlm − 1−µ
dµ dµ
−1
m2
+ −m(m + 1) + Plm . (5.112)
1 − µ2
m2
dP
d lm
l(l + 1)Plm = − 1 − µ2 + Plm . (5.113)
dµ dµ 1 − µ2
Z+1
Ilm+1 = [l(l + 1) − m(m + 1)] dµ [Plm ]2
−1
Z+1
= (l + m + 1)(l − m) dµ [Plm ]2 . (5.114)
−1
Z+1 Z+1
dµ[Plm+1 (µ)] = (l + m + 1)(l − m) dµ[Plm ]2 .
2
(5.115)
−1 −1
Kinetic Energy of Rotations 45
Z+1 Z+1
dµ[Plm (µ)] = (l + m)(l − m + 1) dµ [Plm−1 ]2
2
−1 −1
Z+1 Z+1
dµ[Plm−1 (µ)] = (l + m − 1)(l − m + 2) dµ [Plm−2 ]2
2
−1 −1
..
.
Z+1 Z+1
dµ[Pl1 (µ)] = (l + 1)l dµ [Pl0 ]2 .
2
(5.116)
−1 −1
Combining all of the results (5.116) and using (5.97), we can write
Z+1
dµ[Plm (µ)]2 = [(l + m)(l + m − 1) · · · (l + 1)]
−1
Z+1
× [(l − m + 1)(l − m + 2) · · · l] dµ[Pl ]2
−1
Z+1
(l + m)! l!
= dµ[Pl ]2
l! (l − m)!
−1
Z+1
(l + m)! (l + m)! 2
= dµ[Pl ]2 = . (5.117)
(l − m)! (l − m)! 2l + 1
−1
Finally, if we now allow both positive and negative values of the integer m = 0,
±1, ±2, . . . and replace m by |m|, we obtain the following result
Z+1
(l + |m|)! 2
dµ [Plm (µ)]2 = . (5.118)
(l − |m|)! 2l + 1
−1
The normalization constant Alm in (5.99) is now obtained from the condition
Z+1
(l + |m|)! 2
dµ [Alm Plm (µ)]2 = A2lm = 1, (5.119)
(l − |m|)! 2l + 1
−1
46 Quantum Description of Systems
and it is given by
s
(l − |m|)! 2l + 1
Alm = . (5.120)
(l + |m|)! 2
Finally, the complete result for the normalized wave function of the rotating con-
stituent particle is given by
s
1 (l − |m|)! 2l + 1 |m|/2
ψlm (θ, φ) = l 1 − cos2 θ
2 l! (l + |m|)! 2
dl+|m| l 1
× l+|m|
cos2 θ − 1 √ exp(± i |m| φ). (5.121)
d(cos θ ) 2π
The wave functions (5.121) are called the spherical harmonics and are usually denoted
by Ylm (θ, φ). These functions are of importance in both quantum mechanics and clas-
sical field theories.
peculiar property of the spin quantum number σ is that it is not necessarily an integer,
i.e., there are particles with both integer and half-integer spins. The electrons have
σ = 1/2 and their states are twofold degenerate, i.e., they have two spin states. The
two spin states of an electron, i.e., the two z-projections of the spin angular momentum,
are usually called “spin up” (σz = +1/2) and “spin down” (σz = −1/2).
For microscopic particles with spin, the quantum-mechanical description of a state
by means of the wave function must include both the probability to find a particle in
different positions in the ordinary three-dimensional space and the probability of the
possible orientations of the spin. The wave function is then a function of the three
continuous space co-ordinates (x, y, z) and a discrete spin variable σ , i.e.,
where Er = (x, y, z) is the position vector in the three-dimensional space. For example,
for the “spin down” state, the spin part ψσ (σ ) of the full wave function in (5.122) is
zero for σz = +1/2 whereas it is one for σz = −1/2.
Solution
The operator R̂(α) can be written in the form of the Taylor series
!j
∂ j
∞ ∞
L̂z
X 1 X 1
R̂(α) = i α = α . (5.125)
j! ~ j! ∂φ
j=0 j=0
∂ j 1
∞
X 1
R̂(α)8(φ) = α √ exp(imφ), (5.126)
j! ∂φ 2π
j=0
48 Quantum Description of Systems
or
∞
1 X1
R̂(α)8(φ) = √ exp(imφ) (imα) j , (5.127)
2π j!
j=0
or
1
R̂(α)8(φ) = √ exp(imφ) exp (imα), (5.128)
2π
or finally
Thus, the function 8(φ) indeed satisfies the equation (5.124), and it is an eigenfunction
of the operator R̂(α). From the result (5.129), we see that the eigenvalue of the operator
R̂(α) is given by
There is an alternative solution to this problem that emphasizes the more general prop-
erties of the operator R̂(α). We first note that the standard Taylor expansion of any
function f (φ + α), about the value α = 0, can be written as
∂ j
∞ ∞
1 ∂ j f (φ) j X 1
X
f (φ + α) = α = α f (φ). (5.131)
j! ∂φ j j! ∂φ
j=0 j=0
Using now the equation (5.125), we can identify the operator R̂(α) in the second sum
on the right-hand side of (5.131). Thus, for any function f (φ), we have
In view of the equation (5.132), the operator R̂(α) is known as the shift operator.
Its effect is to “shift” by α the argument of any function f (φ). Let us apply the equa-
tion (5.132) to our particular function 8(φ) = √1 exp(imφ). By equation (5.132) and
2π
simple algebra, we obtain
1
R̂(α)8(φ) = 8(φ + α) = √ exp(im(φ + α))
2π
1
= exp(imα) √ exp (i m φ) = R(α, m) 8(φ). (5.133)
2π
Thus, we find again the relation (5.124), telling us that the the function 8(φ) is the
eigenfunction of the shift operator R̂(α), with the eigenvalue equal to
W 1. (6.1)
To elucidate this quantity, let us consider two thermodynamic systems that do not inter-
act with each other in any way. Let us assume that the number of accessible states of
the first system is W1 and the number of accessible states of the second system is W2 .
The two systems are independent of each other (due to the absence of mutual interac-
tion), so the first system can be in any of its accessible microstates while the second
system is in any of its accessible microstates. Thus, the total number of accessible
states of the entire system consisting of both of these systems is simply the product
W = W1 W2 . (6.2)
Since the numbers W1 and W2 are extremely large numbers (making their product
enormous), it is convenient to introduce an additive property of the thermodynamic
systems called the entropy (S), using the following definition
S = k · ln W, (6.3)
where k is some yet unspecified constant. The total entropy of a system consisting of
the two noninteracting thermodynamic systems described above is then equal to the
sum of the entropies of the two constituent systems
S = k · ln W = k · ln(W1 W2 ) = k · ln W1 + k · ln W2 , (6.4)
or
S = S1 + S2 . (6.5)
where ρ = (Er, σ ) is the label for all the variables needed to fully specify the state of the
constituent particle. These include both the three-dimensional space position variables
Er and the internal spin variable σ .
Our ideal system consists of N such noninteracting particles in translational motion
within the cubic box. Let us first consider the system in the classical limit, in particular,
let us ignore the spin. Due to the absence of mutual interactions, the wave function for
the entire system might be written as the product of the single-particle wave functions
(6.6), for all N particles of the system, i.e.,
N
Y
9(rE1 , rE1 . . . rEN ) = ψa (rEa ). (6.8)
a=1
By the equation (6.8), it is obvious that in such a state the particles would be dis-
tinguishable: the value of the wave function (6.8) changes if we exchange the posi-
tions of any two particles. So one can distinguish any particle from other particles by
performing measurements on a system that would be described by the wave func-
tion (6.8). However, the actual quantum-mechanical description of identical parti-
cles requires that they are indistinguishable in any measurement performed on the
many particle systems. Two identical particles such as, for example, two out of N
electrons in a metal, cannot be distinguished from each other, and the correct many-
particle wave functions must reflect this requirement. That is, exchanging any two
particles co-ordinates and spin variables must not change the value of the squared
magnitude of the wave function. Thus, in the many-body quantum mechanics, the
result (6.8) is not applicable to identical particles, and the wave function for the entire
system
9 = 9(ρ1 , ρ2 . . . ρN ) (6.9)
is a more complex combination of the single-particle wave functions (6.7), which sat-
isfies the above permutational symmetry requirements from the many-body quantum
mechanics. These symmetry requirements are related to the spin of the constituent
particles. With regard to their spin, there are two kinds of microscopic particles in
quantum mechanics:
1. Particles with integral spin (0, 1, 2, . . . ) called bosons.
2. Particles with half-integral spin (1/2, 3/2, . . . ) called fermions.
The symmetry requirements on these two types of microscopic particles are the
following:
1. The total wave function (6.9) for bosons (e.g., He4 -atoms or photons) must be sym-
metric with respect to the exchange of any two particles of the system, i.e., the wave
function (6.9) must remain unchanged when we interchange any two particles of
the system. In mathematical terms, this means
9( . . . ρa . . . ρb . . . ) = 9( . . . ρb . . . ρa . . . ). (6.10)
54 Thermodynamics of Systems
In the special case of the exchange of two particles in the same single-particle state
(ρa = ρb ), the condition (6.10) is an identity, and there are no restrictions on how
many particles can be in the same single-particle state.
2. The total wave function (6.9) for fermions (e.g., He3 -atoms or electrons) must be
antisymmetric with respect to the exchange of any two particles of the system, i.e.,
the wave function (6.9) changes sign when we exchange any two particles of the
system. In mathematical terms, this means
9( . . . ρa . . . ρb . . . ) = −9( . . . ρb . . . ρa . . . ). (6.11)
In the special case of the exchange of two particles in the same single-particle state
(ρa = ρb ), we must obviously have
9( . . . ρa . . . ρb . . . ) = 9( . . . ρb . . . ρa . . . ), (6.12)
which contradicts the condition (6.11). For ρa = ρb , the conditions (6.11) and (6.12)
can be both valid only if the total wave function is equal to zero. In the language of
quantum mechanics, the probability of finding the two fermions in the same single-
particle state is equal to zero (9 = 0). Thus, there can be no more than one fermion
in a single-particle state of the system. This conclusion is known as Pauli exclusion
principle.
From the above discussions, we expect that there are three different ways to count
the number of accessible states W of the system, i.e., (1) classical count of acces-
sible states, (2) quantum-mechanical count of accessible states for fermions, and
(3) quantum-mechanical count of accessible states for bosons.
In order to illustrate the differences between these three different approaches, let
us consider a simple example of arranging of two (ni = 2) particles, denoted by the
letters A and B, into three (gi = 3) possible sublevels denoted by the integers 1, 2,
and 3. Based on the analysis of this simple example, we will reach the general results
for the numbers of possible ways to distribute ni particles into the gi sublevels. These
results will help us to calculate the number of accessible states W in the above three
distinct cases.
vi = gni i . (6.13)
However, all of the variations (6.13) do not necessarily represent different physical
states if the particles (such as A and B in Fig. 6.2) are identical. For the variations
Number of Accessible States and Entropy 55
counted in (6.13), any permutation of the ni identical particles will not produce a new
state. In other words, the number of variations vi must be divided by the number of
permutations of the ni particles, which is equal to ni ! Thus, the number of the actual
classical arrangements that give rise to the different states is given by
gni i
wi = . (6.14)
ni !
The division by ni ! is a correction of the classical count (6.13) to account for the fact
that the exchange of the identical constituent particles of the system does not produce
a new physical state. However, since this correction factor did not emerge from an
actual count of states, the result (6.14) is not necessarily an integer. For example, for
the above simple case of two particles distributed into three states, by equation (6.14),
we obtain wi = 9/2 = 4.5.
The arrangements counted in (6.14) are for the ni identical particles with energies
within the interval (Ei , Ei + 1Ei ) in which there are gi states. If there is only one
energy level Ei in this interval, then gi is simply the degeneracy of this level (recall
the Problem in Section 3.6, “Problems with Solutions *)” in Section 3.6). The next
question to ask is, how many different arrangements does one have for all identical
particles distributed in all different energy intervals of this system? We can easily
answer this question for the important case when the numbers ni , counting particles
with energies within the interval (Ei , Ei + 1Ei ), are given for all the intervals. Indeed,
the arrangements of the particles occupying different energy intervals are independent
from each other, so the total number of arrangements is obtained simply by multiplying
the quantities wi given by (6.14). Thus, for a macrostate specified by given occupation
numbers ni , we obtain the following result for the number of accessible microstates
(of the entire system)
Y gni
i
W= . (6.15)
ni !
i
bosons into gi = 3 sublevels are shown in Fig. 6.3. Note that more than one boson can
be found in the same sublevel, i.e., in the same one-particle state.
From Fig. 6.3, we see that there are
(3 + 2 − 1)! 4!
= =6 (6.16)
(3 − 1)! 2! 2! 2!
possible arrangements of two bosons into three sublevels. In general, for arbitrary ni
and gi , the number of possible arrangements is given by
(gi + ni − 1)!
wi = . (6.17)
(gi − 1)! ni !
The arrangements counted in (6.17) are for the ni identical particles occupying the
energy level with energy Ei and degeneracy gi . The next question to ask is, how many
different arrangements one has for all identical particles distributed on all different
energy levels of this system? We can easily answer this question for the important case
when the numbers ni , counting the particles occupying the energy levels Ei , are given
for all the levels. Indeed, the arrangements of the particles occupying different energy
levels are independent from each other, so the total number of arrangements is obtained
simply by multiplying the quantities wi given by (6.17). Thus, for a macrostate speci-
fied by given occupation numbers ni , we obtain the following result for the number of
accessible microstates (of the entire system)
Y (gi + ni − 1)!
W= . (6.18)
(gi − 1)! ni !
i
elements, ni = 2 at the time. In general, for arbitrary ni and gi , the number of possible
arrangements is given by
g gi !
wi = i = . (6.20)
ni ni !(gi − ni )!
The arrangements counted in (6.20) are for the ni identical particles occupying the
energy level with energy Ei and degeneracy gi . The next question to ask is, how many
different arrangements does one have for all identical particles distributed on all differ-
ent energy levels of this system? We can easily answer this question for the important
case when the numbers ni , counting the particles occupying the energy levels Ei , are
given for all the levels. Indeed, the arrangements of the particles occupying differ-
ent energy levels are independent from each other, so the total number of arrange-
ments is obtained simply by multiplying the quantities wi given by (6.20). Thus, for a
macrostate specified by given occupation numbers ni , we obtain the following result
for the number of accessible microstates (of the entire system)
Y gi !
W= . (6.21)
ni !(gi − ni )!
i
Solution
The problem can be solved using the equation (6.3), with the given proportionality
constant (Boltzmann constant). The initial entropy of the system is given by
S0 = k ln W0 , (6.22)
58 Thermodynamics of Systems
where W0 is the initial number of accessible microstates. After the amount of heat 1Q
is added, the entropy increases to
or
S = S0 + 6 k ln 10. (6.24)
1S = S − S0 = 6 k ln 10. (6.25)
The heat that has to be added to achieve this entropy change is then given by
or
Our macroscopic equilibrium state may be thus specified by giving the values of
the constants U and N. Notably, by equations (7.1) and (7.2), there are many choices
of the occupation number ni that would satisfy these two conditions. They correspond
to various states for which we calculated the entropy S = k · ln W in Chapter 6 in terms
of the occupation numbers. All these states are in principle accessible in the given (by
U and N) macrostate. In the course of time, the equilibrium system exhibits transitions
between all these states (by maintaining constant U and N). However, the macroscopic
system spends most of its time by fluctuating about the state that can be realized with
the largest possible number of microstates. This special state will determine the aver-
age values of the occupation numbers ni . Thus, to find the average values of the occu-
pation numbers ni , we need to solve the following maximization problem: for given
values of U and N in (7.1) and (7.2), find the set of the occupation numbers ni that
maximizes the value of the entropy S = k · ln W calculated in Chapter 6 (for any given
set of ni ). We will denote this entropy maximization condition briefly as
Let us denote by dni the variations of the occupations numbers ni around their
average values maximizing the entropy. Because U and N are fixed [by equations (7.1)
and (7.2)] in this maximization problem and because the entropy is at its maximum (for
dni = 0), we arrive at the following three conditions, in differential form
X X X
dU = d(ni Ei ) = Ei dni + ni dEi = Ei dni = 0, (7.4)
i i i
X
dN = dni = 0, (7.5)
i
dS = k · d(ln W) = 0, (7.6)
for small variations dni of the occupation numbers. In equation (7.4), we note that
the energy levels Ei as well as the number of sublevels gi remain constant regardless
of the changes in their occupation numbers ni . Ei and gi have the same values for
all microstates, hence they are simply constants in the present maximization problem.
We, therefore, have dEi = 0 and dgi = 0. In order to calculate d(ln W), we need the
result for the number of accessible states W obtained in Chapter 6. In this chapter and
the Part Three of this book, we are concerned with the systems that are well described
by classical physics, e.g., ordinary gases in normal conditions. Thus, we will use the
classical result for the number of accessible states (6.15), to obtain
Y gni gni i X
i
X
ln W = ln = ln = ni ln gi − ln (ni !). (7.7)
ni ! ni !
i i i
The occupation number ni is typically a large number and we can use the so-called
Stirling approximation for the expression ln(n!), i.e., we can calculate
n
Y n
X Zn
ln(n!) = ln k= ln k ≈ ln k dk =
k=1 k=1 1
Zn
n
= k ln k − 1
dk = n ln n − n + 1 ≈ n ln n − n. (7.8)
1
where the last step follows by recalling that ln(e) = 1, and using the standard proper-
ties of the ln-function. The differential of the ln(W) in (7.9) is then given by
X
d ln W = d [ni ln gi − ni ln ni ] + dni , (7.10)
i
Equilibrium States of Systems 61
where, as noted above, the numbers gi are to be treated as constants. Thus, each of the
terms in the sum in (7.10) can be transformed as follows:
Using here the identity ni ln gi − ni ln ni = ni ln (gi /ni ), we obtain our final result for
d(ln W) as
X gi
d ln W = dni ln . (7.13)
ni
i
X 1
Ei dni = 0 /· , (7.14)
θ
i
X
dni = 0 / · λ, (7.15)
i
X gi
dni ln =0 / · (−1). (7.16)
ni
i
X Ei gi
+ λ − ln dni = 0. (7.17)
θ ni
i
On the other hand, the constituent particles of a thermodynamic system are free to
move between levels. Thus, in general, dni 6= 0. In order to satisfy the equation (7.17),
we must, therefore, have
gi Ei
ln = λ+ , (7.18)
ni θ
62 Thermodynamics of Systems
or
Ei
ni = gi exp − λ + . (7.19)
θ
The result (7.19) gives the occupation number of levels within the energy interval
(Ei , Ei + 1Ei ), within which there are gi sublevels. In particular, if there is only one
energy level Ei within this interval, then gi is simply the degeneracy of this level. To
apply (7.19) to concrete macrostate, we need to specify the two Lagrange multipliers
λ and θ . Let us first observe that the total number of particles in the system is given by
Ei
X X
−λ
N= ni = e gi exp − = e−λ Z, (7.20)
θ
i i
Using here (7.1) and (7.2), we finally obtain the result for the entropy of the system
k Z
S= U + k N ln + kN. (7.27)
θ N
The two systems are assumed to exchange energy with each other only, and they do
not exchange energy with the surroundings. Therefore, the change in the total energy
is assumed to be zero, i.e.,
dU1 dU2
dU = dU1 + dU2 = + dt = 0, (7.29)
dt dt
S1, θ1
64 Thermodynamics of Systems
or
dU2 dU1
=− . (7.30)
dt dt
∂S1 ∂S2
dS dU1
= − > 0. (7.31)
dt dt ∂U1 ∂U2
∂S k
= . (7.32)
∂U θ
Using the result (7.33), we can make the analysis of the two possible cases as follows:
1. If we had θ1 > θ2 before the two systems were merged then, in order to satisfy the
inequality (7.33), we must have
dU1
< 0, θ1 > θ 2 . (7.34)
dt
2. On the other hand, if we had θ1 < θ2 before the two systems were merged, then, in
order to satisfy the inequality (7.33), we must have
dU1
> 0, θ1 < θ 2 . (7.35)
dt
The results (7.34) and (7.35) show that the internal energy of the system with the lower
value of θ increases while the internal energy of the system with the higher value of θ
decreases. By comparison with common experience, we see that the parameter θ , with
the dimension of energy, behaves in the same way as temperature of physical macro-
objects. In fact, the parameter θ is proportional to the temperature of a thermodynamic
system, and we can write
J
θ = kT, k = 1.3807 · 10−23 , (7.36)
K
where the constant k is called the Boltzmann constant. The relation (7.36) was estab-
lished by comparing the phenomenological ideal gas law with the corresponding sta-
tistical mechanics result, which will be derived in Chapter 11, “Ideal Monoatomic
Equilibrium States of Systems 65
Gases.” The final result in (7.24) for the probability of finding a constituent particle in
the state with energy (Ei , Ei + 1Ei ), is thus given by
gi Ei
ωi = exp − . (7.37)
Z kT
Now, we can identify the constant of proportionality in the definition of entropy (6.3)
as the Boltzmann constant specified by (7.36). Substituting now (7.36) into (7.27), we
obtain the following expression for the entropy of the system
U Z
S= + kN ln + kN. (7.40)
T N
Solution
The partition function for this simple system is given by
Ei E
X
Z= gi exp − = 1 + exp − . (7.41)
kT kT
i
N E2 N E
n2 = g2 exp − = exp − , (7.42)
Z kT Z kT
or
N
n2 = E
. (7.43)
exp kT +1
66 Thermodynamics of Systems
or
NE
U= E
. (7.45)
exp kT +1
U Z
S= + kN ln + k N, (7.46)
T N
or
E
NE 1 1 + exp − kT
S= E
+ k N ln + kN. (7.47)
T exp kT N
+1
Problem 2
Calculate the partition function Z, the internal energy U, and the entropy S for a system
consisting of N indistinguishable constituent particles, which can only occupy two
nondegenerate quantum levels with energies E1 = −E and E2 = +E.
Solution
The partition function for this simple system is given by
Ei E E
X
Z= gi exp − = exp + exp − , (7.48)
kT kT kT
i
or
E
Z = 2 cosh . (7.49)
kT
N E N E
n1 = exp , n2 = exp − . (7.50)
Z kT Z kT
NE E E
U= − exp + exp − , (7.52)
Z kT kT
or
NE E
U = −2 sinh , (7.53)
Z kT
or
E
U = −NE tanh . (7.54)
kT
U Z
S= + kN ln + kN, (7.55)
T N
or
E
NE E 2 cosh
kT
S=− tanh + kN ln + kN. (7.56)
T kT N
Problem 3
Consider a system with only two accessible energy levels E1 and E2 at a constant
temperature T = 150 K. The energy gap between the two levels is 1E = E2 − E1 =
3.2 × 10−21 J. The lower level is nondegenerate, while the upper level is twofold
degenerate. Determine the probability that the lower level is occupied.
Solution
The partition function for this system is given by
E1 E2
Z = exp − + 2 exp − , (7.57)
kT kT
where E2 = E1 + 1E and the factor of 2 in the second term is due to the twofold
degeneracy of the upper energy level. Thus, we have
E1 E1 + 1E
Z = exp − + 2 exp − , (7.58)
kT kT
or
E1 1E
Z = exp − 1 + 2 exp − . (7.59)
kT kT
68 Thermodynamics of Systems
Thus, by equation (7.24), the probability that the lower level is occupied is
E1
exp − kT 1
P1 = = ≈ 0.696. (7.60)
Z 1 + 2 exp − 1E
kT
Problem 4
The number of accessible states W of a system with internal energy U occupying the
volume V is given by
√
W = a exp b UV , (7.61)
Solution
The entropy, as a function of internal energy U and volume V, is readily obtained from
the definition S = k ln W, yielding here
√
S = k ln a + bk UV. (7.62)
∂S 1
= , (7.63)
∂U T
we obtain
∂S
r
1 bk V
= = . (7.64)
T ∂U 2 U
Using the result (7.64), we can express the internal energy U as a function of temper-
ature T as follows:
2
bkT
U=V . (7.65)
2
b2 k 2
S = k ln a + TV. (7.66)
2
Equilibrium States of Systems 69
Problem 5
The entropy of a system, consisting of N constituent particles within a volume V hav-
ing the internal energy U, is given by the expression
N2V 2
S(N, U, V) = a − b , (7.67)
U3
where a and b are constants. Derive the expression for internal energy U as a function
of temperature T, volume V, number of particles N, and the constants a and b.
Solution
Using the result (7.63), we have
1 ∂S N2V 2
= = 3b 4 . (7.68)
T ∂U U
Rearranging the result (7.68), we obtain the following expression for internal energy
U as a function of temperature T, volume V, number of particles N, and the constants
a and b:
√
U = (3bT)1/4 NV. (7.69)
8 Thermodynamic Variables
8.1 Free Energy and the Partition Function
The equation (7.40) in Chapter 7, “Equilibrium States of Systems,” specified the
entropy S as the function of the internal energy U, temperature T, the partition function
Z, and the total number of particles N. Unlike the internal energy U and the tempera-
ture T, the partition function Z and the total number of particles N are not best suited
quantities for the macroscopic description of a thermodynamic system. In thermo-
dynamics, it is, therefore, customary to introduce a new macroscopic variable called
the free energy F. For an ideal system of N indistinguishable particles discussed in
Chapter 6, “Number of Accessible States and Entropy,” and Chapter 7, the free energy
is defined as follows:
Z
F = −NkT ln − NkT. (8.1)
N
Substituting the definition (8.1) into (7.40) and rearranging, we obtain an important
macroscopic definition of the free energy of a thermodynamic system as follows:
U F U−F
S= − = ⇒ F = U − TS. (8.2)
T T T
Free energy F in (8.1) has a significant dependence on the number of particles N. Of
special interest for the forthcoming discussions is the change of the free energy upon
changing N by 1N = 1, i.e., upon adding one particle to the system, 1F = F(N +
1) − F(N). For a large N 1, one can approximate this change as follows:
∂F ∂F
1F = 1N = = µ, (8.3)
∂N ∂N
where we define the so-called chemical potential µ by µ = ∂F/∂N. For the case of
ideal systems, with the free energy as in (8.1), a simple differentiation gives
∂F Z 1 Z
µ= = −kT ln + NkT − kT = −kT ln . (8.4)
∂N N N N
From (8.4), we readily obtain
µ
Z = N exp − . (8.5)
kT
Substituting (8.5) into (7.37), we obtain an alternative result for the probability of
finding a constituent particle with energy within the interval (Ei , Ei + 1Ei ) as follows:
ni gi µ − Ei
ωi = = exp . (8.6)
N N kT
µ − Ei
ni = gi exp . (8.7)
kT
ni µ − Ei
n̄i = = exp . (8.8)
gi kT
The result (8.8) is known as the Maxwell–Boltzmann formula. We remark that the
chemical potential µ is of particular significance for studying the systems with variable
numbers of particles. Such systems will be discussed in more detail in Chapter 10,
“Variable Number of Particles.”
The free energy F of a thermodynamic system can also be defined in a more general
way, which is suitable for the analysis of the systems of interacting particles. In order
to obtain such a generalized definition of the free energy, let us rewrite the equation
(8.1) as follows:
F = −kT ln Z N − N ln N + N .
(8.9)
ZN
F = −kT ln Z N − ln N! = −kT ln .
(8.10)
N!
The partition function Z = Z1 was derived as a sum over the states of a single con-
stituent particle of the system. On the other hand, the states of the N noninteracting
constituent particles of the system are independent of each other. The quantity Z N is
a potential candidate for the partition function ZN , which takes into account the entire
system of N noninteracting particles. To see this, consider the case N = 2, i.e.,
"
#
Ei Ej
X X
Z2 = gi exp − × gj exp −
kT kT
i j
Ei + Ej
XX
= gi gj exp − . (8.11)
kT
i j
Thermodynamic Variables 73
By equation (8.11), we see that Z 2 is essentially a sum over two-particle states, with
the first particle at the level Ei and the second particle at the level Ej . However, for the
indistinguishable particles, the two-particle state with the first particle at the level Ei
and the second particle at the level Ej is physically the same as the two-particle state
with the first particle at the level Ej and the second particle at the level Ei . Because of
this, the equation (8.11) makes an overcount of the two-particle states. To correct for
this overcount, the two-particle partition function is defined by
Z2
Z2 = , (8.12)
2!
where the factor 2! corrects the overcount of states. Analogously, for the thermody-
namic system consisting of N particles, the product Z N must be divided by the number
of permutations N! in order to obtain the corrected N-particle partition function. Thus,
the N-particle grand partition function ZN for the system of noninteracting particles is
defined by
ZN
ZN = . (8.13)
N!
Substituting the definition (8.13) into (8.10), we obtain the most general definition of
the free energy of the system
F = −kT ln ZN . (8.14)
The definition (8.14) is applicable even to the nonideal systems of particles with arbi-
trary interparticle interactions, where the partition function ZN is not given by the
simple definition (8.13). In the this discussion, we are concerned with the ideal sys-
tems of non-interacting particles, and the expression (8.1) for the free energy of the
N-particle system, employing the one-particle partition function Z, is sufficient for the
complete analysis of the system.
It should also be noted that there are some exceptions from the result (8.13), i.e., the
physical situations where ZN = Z N and no division by N! is required. This applies par-
ticularly to the heavy particles (atoms) that form a solid. The wave functions of such
heavy particles are sharply peaked at lattice sites, while they are practically zero at the
position of the neighboring lattice sites. Thus, the probability of the exchange permut-
ing such particles between any two sites is negligible. Thereby, the particles of the sys-
tem, although indistinguishable in principle, become distinguishable by being local-
ized to distinguishable lattice sites. For such situations, the division by N! in (8.13) is
not appropriate. Thus, ZN = Z N , and for such systems, the free energy becomes
The free energy F and consequently the entropy S for such systems is simply propor-
tional to the number of constituent particles N. The physical systems, for which the
result (8.15) is directly applicable, include the mutually noninteracting spins localized
74 Thermodynamics of Systems
h2 2
Ei = n ix + n2
iy + n2
iz , (8.16)
8mV 2/3
we see that the partition function Z is also a function of the volume V of the system. In
other words, the quantities Ei and gi , and consequently the partition function Z, change
if the volume of the system changes. Thus, we can write
and
∂ ∂
d (ln Z) = (ln Z)V dT + (ln Z)T dV. (8.18)
∂T ∂V
The result (8.18) will be useful in the practical calculations of the thermodynamic
quantities in the following section.
1X ∂ Ei 1 X Ei Ei
= gi exp − = gi 2 exp −
Z ∂T kT V Z kT kT
i i
N Ei
1 X
= Ei gi exp − . (8.19)
NkT 2 Z kT
i
N Ei
ni = gi exp − , (8.20)
Z kT
we obtain
∂ 1 X U
(ln Z)V = Ei ni = . (8.21)
∂T NkT 2 NkT 2
i
∂
U = NkT 2 (ln Z)V . (8.22)
∂T
Using the result for the entropy of the system (7.40), i.e.,
U
S= + Nk ln Z − Nk ln N + kN, (8.23)
T
and the assumption that in our system the total number of constituent particles is con-
stant (N = Constant), we obtain the following result for the differential of the entropy
of the system
dU U
dS = − 2 dT + Nk d(ln Z). (8.24)
T T
dU U ∂ ∂
dS = − 2 dT + Nk (ln Z)V dT + Nk (ln Z)T dV, (8.25)
T T ∂T ∂V
or
dU dT ∂ ∂
dS = − 2 [U − NkT 2 (ln Z)V ] + Nk (ln Z)T dV. (8.26)
T T ∂T ∂V
76 Thermodynamics of Systems
By the equation (8.22), the second term on the right-hand side of (8.26) vanishes and
the differential of the entropy of the system becomes
dU ∂
dS = + Nk (ln Z)T dV. (8.27)
T ∂V
∂
dU = T dS − NkT (ln Z)T dV. (8.28)
∂V
On the other hand, we know that the internal energy of the system U can be expressed
as a function of entropy S and volume of the system V, i.e., we can write U = U(S, V).
Therefore, the differential of the internal energy can also be written in the following
form
∂U ∂U
dU = dS + dV. (8.29)
∂S V ∂V S
Comparing the expressions (8.28) and (8.29), we can readily derive the following two
important relations between the thermodynamic quantities
∂U ∂U ∂
= T, = −NkT (ln Z)T . (8.30)
∂S V ∂V S ∂V
A
Thermodynamic Variables 77
shown in Fig. 8.1, requires a convention regarding the sign of the mechanical work.
A commonly adopted convention is that if the external force G E performs work on the
system (i.e., the system is compressed by an external force), then the mechanical work
has a negative sign. Conversely, if the system performs work on the surroundings (i.e.,
the system expands), then the mechanical work has a positive sign.
When the piston moves for some distance dx, as indicated in Fig. 8.1, the mechan-
ical work performed by the external force is given by
dL = G dx. (8.31)
The pressure p on the piston, with the total area A, is defined as the force acting on unit
area of the piston. As the force GE acts along the direction of motion and it is evenly
distributed over the area of the piston, we have
G
p= ⇒ G = pA. (8.32)
A
dL = pA dx = p dV. (8.33)
dL
p= . (8.34)
dV
To proceed, let us consider a thermally insulated system that cannot exchange any
thermal energy (heat) with its environment. By energy conservation, the work done
by such system is done at the expense of its internal energy, dL = −dU. Thus, if the
system expands, then internal energy will decrease and a positive amount of work
will be done by the system. Conversely, when the system is compressed, it performs
negative work and its internal energy increases. Thus, we have
Here, we are interested in the processes that proceed very slowly so that the system is
in a thermodynamic equilibrium at any time. If such a process is done infinitely slowly,
quantum-mechanical considerations show that there are no changes of the occupation
numbers ni of the energy levels in an insulated system. On the other hand, the entropy
is generally expressible in terms of these occupations numbers; see the equations giv-
ing entropy discussed in Chapters 6 and 7, such as the equation (7.25). This leads to
the following important theorem: If a thermodynamic process is done infinitely slowly
in a thermally insulated system, then its entropy S must be constant in time. This result
is known as the adiabatic theorem, so the processes going on with constant entropy
78 Thermodynamics of Systems
are called adiabatic processes. On the other hand, by equation (8.23) with constant
entropy (dS = 0), we have
∂U
dU = dV. (8.36)
∂V S
In the function U = U(S, V), the entropy and the volume of the system are independent
variables. Thus, by comparison of the equations (8.36) and (8.35), we obtain
∂U
p=− . (8.37)
∂V S
Using now (8.30), we finally obtain the thermal-state equation in the following form
∂U ∂
p = p(T, V) = − = NkT (ln Z)T . (8.38)
∂V S ∂V
Substituting (8.38) into (8.28), we obtain the general result for the differential of the
internal energy as follows:
dU = T dS − p dV. (8.39)
The equation (8.39) represents one of the fundamental laws of thermodynamics, and
its physical significance will be further emphasized in the coming chapters. Using the
definition of the free energy (8.1), i.e.,
Z
F = −NkT ln − NkT. (8.40)
N
we obtain
∂F ∂
− = NkT (ln Z)T = p, (8.41)
∂V T ∂V
or
∂F
p=− . (8.42)
∂V T
The equation (8.42) defines the pressure of the system p in terms of the free energy F.
Let us put the above result for the pressure in a broader context that will allow us to
derive another important equation expressing the entropy S of the system in terms of
the free energy F. Using the equation (8.2), we have
dF = T dS − p dV − S dT − T dS = −p dV − S dT. (8.44)
∂F ∂F
dF = dV + dT. (8.45)
∂V T ∂T V
∂F ∂F
p=− , S=− . (8.46)
∂V T ∂T V
Note that the equation (8.46) reproduces the above result for the pressure in equation
(8.42), and, in addition, provides a relation that can be used to calculate the entropy
S in terms of the free energy F. By using (8.46), the internal energy U can also be
expressed purely in terms of the free energy F, via the equation
∂F
U = F + TS = F − T . (8.47)
∂T V
We would like to stress that in writing the above derivatives, we assumed that the
number of particles N is fixed. It is, however, easy to generalize the above discussion
to the case of a variable number of particles N. Indeed, the differential of F(V, T, N),
∂F ∂F ∂F
dF = dV + dT + dN, (8.48)
∂V T,N ∂T V,N ∂N V,T
dF = −p dV − S dT + µ dN (8.49)
generalizing the above equation for dF to the case of variable number of particles,
which is discussed in more detail in Chapter 10.
2. The second group of thermodynamic variables includes the so-called extensive state
variables. The extensive state variables (e.g., volume V, internal energy U, and
entropy S) are proportional to the mass of the system. Thus, we can write
V = v · m, U = u · m, S = s · m, (8.50)
∂U ∂U
T= , p=− . (8.51)
∂S V ∂V S
Solution
The free energy is given by
Z
F = −NkT ln − NkT = −NbkT 4 V − NkT. (8.52)
N
The pressure of the system is given by
∂F
p=− = NbkT 4 . (8.53)
∂V T
∂F
S=− = 4NbkT 3 V + kN. (8.54)
∂T V
Thermodynamic Variables 81
The internal energy is obtained as U = F + TS. Substituting the results for free energy
F and entropy S, we obtain
or finally
U = 3NbkT 4 V. (8.56)
Problem 2
Calculate the free energy F for a system consisting of N constituent particles, which
can only occupy two nondegenerate quantum states with energies E1 = −E and
E2 = +E. Using the obtained result for the free energy F, calculate the entropy S and
the internal energy U = F + TS of the system.
Solution
The partition function for this simple system is given by
E E E
Z = exp + exp − = 2 cosh . (8.57)
kT kT kT
or finally
E
2 cosh NE E
kT
S = kN ln − tanh + kN. (8.61)
N T kT
The internal energy is obtained as U = F + TS. Substituting the results for free energy
F and entropy S, we obtain
E
U = F + TS = −NE tanh . (8.62)
kT
82 Thermodynamics of Systems
The results obtained here, by means of the thermodynamic relations, agree with the
results obtained using the generic definitions in the Problem 2 of the Chapter 7.
Problem 3
Consider a system consisting of N constituent particles, which can occupy four spin- 32
quantum states, with energies:
E1 = − 23 E
E2 = − 12 E
(8.63)
E3 = + 12 E
E4 = + 32 E
Solution
The partition function of the system is given by
E E
3E
Z = exp + 3 exp + 3 exp −
2kT 2kT 2kT
3
E E
3E
+ exp − = exp + exp − , (8.64)
2kT 2kT 2kT
or finally
3
E
Z = 2 cosh . (8.65)
2kT
Z
F = −NkT ln − NkT, (8.66)
N
or finally
E
F = −3NkT ln 2 cosh + NkT ln N − NkT. (8.67)
2kT
Thermodynamic Variables 83
The entropy of the system is obtained from the free energy as follows:
∂F E
S =− = 3Nk ln 2 cosh
∂T V 2kT
∂ E
+ 3NkT ln 2 cosh − Nk ln N + kN, (8.68)
∂T 2kT V
or finally
E
S = 3Nk ln 2 cosh − Nk ln N−
2kT
E
3NE
− tanh + kN. (8.69)
2T 2kT
The internal energy is obtained as U = F + TS. Substituting the results for free energy
F and entropy S, we obtain
E
3
U = F + TS = − NE tanh . (8.70)
2 2kT
Problem 4
A crystal, consisting of N heavy noninteracting spin- 12 ions, is in a thermal equilibrium
at the temperature T = 1 K and under the influence of a uniform magnetic field with
magnetic induction B = 10 T. The presence of the magnetic field gives rise to a two-
level quantum system, with energies E1 = −µB and E2 = +µB.
(a) Derive the expressions for the partition function ZN and the entropy S of this
system.
(b) If the magnetic induction is adiabatically (1S = 0) reduced to B = 10−2 T, what is
the final temperature of the spins?
Solution
The partition function for a single ion in a two-level quantum-mechanical system is
given by
µB µB
Z = exp + exp − . (8.71)
kT kT
In this case, we have a crystal consisting of heavy ions at very low temperatures.
Thus, the exchange of particles between the lattice sites is practically impossible, and
we have a physical situation, where the partition function for N particles is given by
ZN = Z N , and the formula (8.15) for the free energy is applicable. Thus, for the system
84 Thermodynamics of Systems
µB µB N
ZN = exp + exp − . (8.72)
kT kT
The free energy F = −kT ln ZN is then given by
µB µB
F = −NkT ln exp + exp − , (8.73)
kT kT
or
µB
F = −NkT ln 2 cosh . (8.74)
kT
The entropy S can be calculated as follows:
∂F µB
S=− = Nk ln 2 cosh
∂T V kT
∂ µB
+ NkT ln 2 cosh , (8.75)
∂T kT V
or
µB µB µB
S = Nk ln 2 cosh − tanh . (8.76)
kT kT kT
Introducing here a new variable x = µB/kT, we see that the entropy is a function of
the variable x only, i.e.,
Since the entropy is a function of x only, and it is assumed to be constant in the adia-
batic process of reducing the magnetic field, it implies that the quantity x must remain
constant during the process. Therefore, we must have
µB1 µB2
x1 = = = x2 = Constant. (8.78)
kT1 kT2
Thus, the final temperature of the spins is
B2 10−2 T
T2 = T1 = × 1K = 10−3 K. (8.79)
B1 10 T
Problem 5
The partition function of a system, as a function of temperature T, volume V, and
particle number N, is given by
Z = NbV(kT)5/2 , (8.80)
Thermodynamic Variables 85
where b is a constant. Calculate the free energy F, pressure p, entropy S, and the
internal energy U of the system.
Solution
The free energy is given by
Z h i
F = −NkT ln = −NkT ln bV(kT)5/2 − NkT. (8.81)
N
∂F NkT
p=− = . (8.82)
∂V T V
∂F
h i 5
S=− = Nk ln bV(kT)5/2 + Nk + kN. (8.83)
∂T V 2
The internal energy is obtained as U = F + TS. Substituting the results for free energy
F and entropy S, we obtain
5
U = F + TS = NkT. (8.84)
2
It will be shown later that this partition function describes the classical diatomic ideal
gas with five degrees of freedom. Three degrees of freedom are the usual translational
degrees of freedom, while the remaining two degrees of freedom correspond to the
rotations of the diatomic molecules of the gas.
9 Macroscopic Thermodynamics
9.1 Changes of States. Heat and Work
In practical engineering thermodynamics, one is usually less interested in the
equilibrium states of thermodynamic systems. The most interesting phenomena are
thermodynamic processes, namely, the changes of the state of a macroscopic, thermo-
dynamic system. If this change is sufficiently slow, it can be considered as a passage
through a continuous succession of equilibrium states. Such a change of state is called
the quasi-static change. A quasi-static change of state is often also a reversible change
of state, since after such a change, it is possible to return to the initial state passing
through the same succession of intermediate states in reversed order. It should, how-
ever, be noted that there are thermodynamically irreversible quasi-static processes,
e.g., a slow motion of an object on a rough surface in which the work done against
friction transforms into irreversibly lost heat energy. In reality, all thermodynamic
processes are to some extent irreversible. In practice, however, many quasi-static pro-
cesses in nature are nearly reversible and the thermodynamics of reversible processes
is sufficient for the description of such processes.
Let us now consider an arbitrary thermodynamic process, where the state of the
system changes from an initial state (1) to some final state (2), as depicted in the p-V
plane shown in Fig. 9.1. The change of the internal energy in this process isgiven by
!
X X X
dU = d ni Ei = Ei dni + ni dEi . (9.1)
i i i
The second term on the right-hand side of the equation (9.1) is zero for processes going
on at constant volume. For them, we have dEi = 0.
Indeed, recall that energy levels depend on the volume occupied by the system;
see, for example, the equation (3.43), for the case of an ideal gas. When the volume
of a system changes, the energy levels Ei also change, i.e., dEi is nonzero making the
second term in the equation (9.1) nonzero. This part of the internal energy change in
(9.1) is closely related to the work performed by the system discussed in Chapter 8,
“Thermodynamic Variables.” In an infinitesimal change of state, the mechanical work
performed by the system is given by
X
dL = pdV = − ni dEi , (9.2)
i
( p1, V1)
( p2, V2)
0 V
or
!
X ∂Ei
∂U
dL = − ni dV = − dV. (9.3)
∂V ∂V S
i
Above, we used the fact that ni = Constant at S = Constant (recall the Adiabatic theo-
rem discussed in Section 8.3, “Pressure: Thermal-state Equation”) such that the varia-
tion of internal energy U at constant S comes only from the variation of energy levels
Ei . The equations (9.2) and (9.3) above are in accordance with the equations (8.34)
and (8.35) of Chapter 8. The work performed during a finite change of state is given
by
Z2
L12 = pdV. (9.4)
1
in accordance with the first equation (8.28). By the equations (9.1), (9.2), and (9.5),
we obtain the general relation
As it stands, this relation, known as the first law of thermodynamics, states that the
heat energy dQ added to a system is in part used to increase its internal energy by
the amount dU, whereas the remaining part of the added heat energy is used by the
Macroscopic Thermodynamics 89
system to perform the work dL. The heat exchanged during a finite change of state is
given by
Z2
Q12 = TdS. (9.7)
1
Using the equations (9.4) and (9.6), that is, by simply integrating the above displayed
relation dU = dQ − dL, we obtain the total change of the internal energy of the system
during a finite change of state as follows:
where we have used the usual convention for the sign of the mechanical work, as
in the equation (8.39). The result (9.8) is the mathematical statement of the energy
conservation in the First Law of Thermodynamics.
a thermodynamic process, the heat energy added to a system is the sum of its internal
energy change and the work performed by the system.
In the application of the second law to a system composed of several parts (objects), it
should be stressed that the S in (9.9) is the entropy of the entire system, whence the law
states that this entropy must not decrease. In contrast to this, the entropy of individual
parts of this system can in principle decrease (or increase). A simple example for
this is the thermal equilibration process involving two objects of initially different
temperatures (one warmer and one colder) placed in contact with each other. This
composite system eventually reaches a final temperature such that the final entropy
of the entire system is higher than the initial entropy (in accordance with the second
law). However, the entropy of the initially warmer object still decreases during this
process simply because its temperature decreases during its cooling toward the final
temperature (which is in-between the initial temperatures of the two objects).
S = k · ln W + S0 . (9.10)
Interestingly enough, quantum mechanics suggests that the natural choice of the con-
stant S0 in the equation (9.10) is simply zero. That is, quantum mechanics suggests that
the expression for entropy should be written simply as we did before, just by writing
S = k · ln W. (9.11)
The reason for this preferred choice stems from a fundamental fact that realistic physi-
cal systems can occupy only a single microstate at zero absolute temperature, T = 0
(as discussed hereafter). Thus, W = 1 at T = 0, so the entropy, as defined in (9.11),
vanishes at T = 0.
Macroscopic Thermodynamics 91
N Ei
ni = gi exp − . (9.12)
Z kT
The number of constituent particles of the system in the state with the lowest energy
E = E0 (ground state) is then equal to
N E0
n0 = g0 exp − . (9.13)
Z kT
ni gi Ei − E0
= exp − . (9.14)
n0 g0 kT
On the other hand, since E0 is the lowest energy level, one has Ei − E0 > 0 for every
other level. Because of this, the exponential on the right-hand side of the equation
(9.14) approaches zero as the temperature approaches the absolute zero (T → 0). In
other words, for T = 0, we have
ni
= 0, (9.15)
n0
for any state other than the ground state. The result (9.15) shows that all of the con-
stituent particles of the system are in the ground state, i.e., in a single state at T = 0.
That is, W = 1 at T = 0, as argued above. Thus, by equation (9.11), we have the con-
clusion
lim S = 0, (9.16)
T→0
the working substance to enter the engine, the work p1 · V1 < 0 must be performed. On
the other hand to extract the working substance from the engine, it must perform the
work p2 · V2 > 0. The total change of the internal energy of the system is then given by
where Le12 is the technologically useful work extracted from the engine.
The equation (9.17) is just the energy conservation law. The increase of the internal
energy of the system during the change of state from 1 to 2 is equal to the heat added to
the engine Q12 reduced by the technologically useful work extracted from the engine
Le12 and the total work performed by the engine to extract and enter the working sub-
stance L12 = p2 V2 − p1 V1 . The equation (9.17) can be rewritten in the following way
H = U + pV. (9.19)
dH = dQ − dLe . (9.21)
The differential of the technologically useful work can now be calculated as follows:
dLe = dQ − dH = dQ − d (U + pV)
= (dQ − pdV) − dU − Vdp = −Vdp, (9.22)
where we have used the result dU = dQ − pdV. The total technically useful work
extracted from the engine during the change of state from 1 to 2 is then given by
Z2
Le = − Vdp. (9.23)
1
Macroscopic Thermodynamics 93
p2 2
1
L = ∫ p dV
2
0 V1 V2 V
The p − V diagram, which illustrates the meaning of the technically useful work, is
shown in the Fig. 9.3.
∂T ∂T
dT = dp + dV. (9.24)
∂p V ∂V P
Using the equation (9.24), we can consider a number of different processes and define
the corresponding thermal coefficients suitable for the description of these processes.
∂V
dV = dT = αV0 T, (9.25)
∂T P
∂V
1
α= . (9.26)
V0 ∂T P
94 Thermodynamics of Systems
Let us now assume that u = u(x, y) is an arbitrary thermodynamic state function of two
independent variables x and y. Using (9.33), we can write
∂u ∂u
∂(u, y) ∂x ∂y ∂u ∂u
∂u
= = ∂x ∂y = . (9.34)
∂(x, y) ∂y ∂y 0 1 ∂x y
∂x ∂y
The Jacobian determinant, defined by (9.33), has the following mathematical proper-
ties
∂(u, v) ∂(v, u) ∂(u, v) ∂(u, v)
=− , =− , (9.35)
∂(x, y) ∂(x, y) ∂(x, y) ∂(y, x)
and
∂(u, v) ∂(u, v) ∂(t, s)
= . (9.36)
∂(x, y) ∂(t, s) ∂(x, y)
and
∂(u, v) ∂(x, y) −1
= . (9.38)
∂(x, y) ∂(u, v)
Using now the mathematical results (9.34–9.38), we can rewrite the equation (9.32) as
follows:
∂(T, V) ∂(V, p) ∂(V, T)
dV = − dp = dp, (9.39)
∂( p, V) ∂(T, p) ∂( p, T)
or finally
∂V
dV = dp = −γ V0 dp, (9.40)
∂p T
1 ∂V
γ =− . (9.41)
V0 ∂p T
∂V
1V = 1p = −γ V0 1p. (9.42)
∂p T
96 Thermodynamics of Systems
or
1 1
· αV0 · − = −1. (9.45)
βp0 γ V0
α = βγ p0 . (9.46)
∂U ∂U
dU = dT + dV. (9.47)
∂T V ∂V T
Since for the system with the mass m, the internal energy U = u · m and the volume
V = v · m are the extensive state variables, we also have
∂u ∂u
du = dT + dv. (9.48)
∂T V ∂v T
The equation (9.48) defines the differential of the internal energy per unit mass, and
it is valid for a system of an arbitrary mass. This is convenient in the present section
because we want to define the caloric coefficients per unit mass using a mass inde-
pendent thermodynamic analysis. Similarly to the thermal coefficients defined in the
Section 9.4.4, “Relation between Thermal Coefficients,” here we define the caloric
coefficients, which are usually called the specific heats.
A specific heat with respect to some parameter X, which is to be kept constant, is
defined as follows:
dq
cX = , (9.49)
dT X
Macroscopic Thermodynamics 97
we can write
dq = du + pdv. (9.52)
The result (9.58) is often very useful in practical calculations of caloric changes of
state of thermodynamic systems.
98 Thermodynamics of Systems
h = u + pv, (9.60)
we have
dh = dq + vdp. (9.62)
On the other hand, from the equation h = h(T, p), we can also write
∂h ∂h
dh = dT + dp. (9.63)
∂T P ∂p T
Using (9.62) taken at constant pressure, we have dq = dh. Thus, by the equation (9.63),
at constant pressure (dp = 0), we obtain
∂h
dq
cP = = . (9.64)
dT P ∂T P
∂s
dq = cP dT + T dp. (9.68)
∂p T
∂p ∂p
dp = dT + dv. (9.69)
∂T V ∂v T
∂s ∂p ∂p
dq = cP dT + T dT + dv . (9.70)
∂p T ∂T V ∂v T
∂q ∂s ∂p
cV = = cP + T , (9.71)
∂T V ∂p T ∂T V
or
∂s ∂p
cp − cV = −T . (9.72)
∂p T ∂T V
Thus, we have obtained the relation between the two specific heats. However, in order
to be able to use this relation in practice, we need to express the first partial deriva-
tive on the right-hand side of the equation (9.72) in terms of some easily measurable
thermodynamic parameters. We can rewrite this partial derivative as follows:
Here, we need to calculate the Jacobian ∂(T, s)/∂( p, v). It is done by using the equa-
tion for the differential of the internal energy per unit mass of a thermodynamic
system
The left-hand side of the equation (9.74) is the total differential of the function u =
u(s, v), whereas the right-hand side of the equation (9.74) is not necessarily a total
differential. The general expression
is a total differential of some function w = w(x, y), if the functions A(x, y) and B(x, y)
have the following form
∂w(x, y) ∂w(x, y)
A(x, y) = , B(x, y) = . (9.76)
∂x ∂y
∂A ∂B ∂ 2w ∂A ∂B
= = ⇒ = . (9.77)
∂y ∂x ∂x∂y ∂y x ∂x y
Consequently, the condition that the expression du = Tds − pdv is a total differential
is given by
∂T ∂p ∂(T, s) ∂( p, v)
=− ⇒ =− . (9.78)
∂v s ∂s v ∂(v, s) ∂(s, v)
By the equation (9.78) and the properties of Jacobians discussed in Section 9.4.3,
“Isothermal Expansion.” we have
∂(T, s)
= 1. (9.80)
∂( p, v)
∂s ∂v
=− . (9.81)
∂p T ∂T P
∂v ∂p
cp − cV = T , (9.82)
∂T P ∂T V
or
1 ∂v 1 ∂p
cp − cV = pvT . (9.83)
v ∂T P p ∂T V
Macroscopic Thermodynamics 101
∂v ∂p
1 1
α= and β= , (9.84)
v ∂T P p ∂T V
cp − cV = pvTαβ. (9.85)
Using the relation between the thermal coefficients (9.46) in the form β = α/γ p, we
finally obtain the relation between the two specific heats, in terms of the easily mea-
surable thermodynamic quantities, as follows:
α2
cp − cV = vT . (9.86)
γ
T2 2 p2 2
0 S1 S2 S 0 V1 V2 V
102 Thermodynamics of Systems
rectangular array
∂p
∂v ∂T
∂p ∂T v ∂v p
T
∂s ∂T
∂v
∂T v ∂v s ∂s T
.
∂s
∂T ∂p (9.88)
∂T p
∂p s ∂s T
∂v ∂p ∂s
∂p s ∂s v ∂v p
Here, it can be shown that only 3 of these 12 coefficients are independent. In other
words, there are nine equations that relate these 12 coefficients to each other. In order
to find these nine equations, we first note that the array (9.88) is formed in such a way
that the product of the three coefficients in each row of the array is equal to −1. For
example, the product of the three coefficients in the first row of the array (9.88) is
equal to
∂(v, T) ∂( p, v) ∂(T, p)
∂( p, T) ∂(T, v) ∂(v, p)
∂(v, T) ∂( p, v) ∂(T, p)
= = (−1)3 = −1. (9.89)
∂(T, v) ∂(v, p) ∂( p, T)
Thus, we immediately obtain the first four relations between the twelve coefficients
listed in (9.88)
∂v ∂p ∂T
= −1 (9.90)
∂p T ∂T v ∂v p
∂s ∂T ∂v
= −1 (9.91)
∂T v ∂v s ∂s T
∂s ∂T ∂p
= −1 (9.92)
∂T p ∂p s ∂s T
∂v ∂p ∂s
= −1. (9.93)
∂p s ∂s v ∂v p
In order to find the remaining four relations between the thermodynamic coefficients,
we use the result (9.80) in combination with the properties of Jacobians discussed in
Macroscopic Thermodynamics 103
We have now finally established all nine relations (9.90–9.98) between the thermody-
namic coefficients listed in the array (9.88), and thereby proven that there are only
three independent thermodynamic coefficients. These three independent thermody-
namic coefficients can be determined either experimentally (phenomenological ther-
modynamics) or using the partition function Z (statistical thermodynamics).
For example, we can choose the three coefficients in the upper left corner of the
array (9.88), i.e.,
∂v ∂p ∂s
, and , (9.99)
∂p T ∂T v ∂T v
as the three independent thermodynamic coefficients. We can then use the thermal-
state equation (8.38) in the form
NkT ∂
p = p(T, v) = (ln Z)T (9.100)
m ∂v
to determine the first two thermodynamic coefficients from (9.99)
−1
∂p ∂v ∂p
, = . (9.101)
∂T v ∂p T ∂v T
NkT 2 ∂
u = u(T, v) = (ln Z)V (9.102)
m ∂T
and the result (9.55) to determine the remaining thermodynamic coefficient in (9.99)
∂s 1 ∂u
1 dq
= = . (9.103)
∂T v T dT v T ∂T v
As a final remark, it should be noted that it is not possible to choose the three coeffi-
cients from the same row of the array (9.88) as independent quantities, since they are
104 Thermodynamics of Systems
related by the equations (9.90–9.93). In other words, if we know the two coefficients
from a given row, the third coefficient from the same row is uniquely determined by
the equations (9.90–9.93).
Solution
(a) According to the first law of thermodynamics, we can write
where cw is the specific heat at constant volume for water. Thus, we can write
dT T
dSw = mcw , 1Sw = mcw ln . (9.106)
T T0
373
1Sw = 1 kg × 4186 J/kg K × ln = 1306.5 J/K. (9.107)
273
Since the entire system is assumed to be thermally insulated from the surround-
ings, the change of the internal energy of the reservoir is given by
1Ur T0
Z
dUr
1Sr = = = −mcw 1 − . (9.110)
T T T
T T0
1S = 1Sw + 1Sr = mcw ln + −1 . (9.112)
T0 T
Problem 2
A quantity of water with mass m = 1 kg at the initial temperature T0 = 273 K is heated
to T2 = 373 K by first bringing it in contact with one large heat reservoir with constant
temperature T1 = 323 K and then bringing it in contact with another large heat reser-
voir with constant temperature T2 = 373 K. What is the change in entropy of the entire
system consisting of the water and the two heat reservoirs?
Solution
During the first heating process from T0 = 273 K to T1 = 323 K, the entropy of the
second heat reservoir at T2 = 373 K remains unchanged. The entropy change of the
entire system is then equal to the entropy change of the water and the first heat reservoir
at T1 = 323 K. Using the result (9.112) obtained in the solution of Problem 1, we have
T1 T0
1S1 = mcw ln + −1 . (9.114)
T0 T1
During the second heating process from T1 = 323 K to T2 = 373 K, the entropy of the
first heat reservoir at T1 = 323 K remains unchanged. The entropy change of the entire
system is then equal to the entropy change of the water and the second heat reservoir
at T2 = 373 K. In analogy with the result (9.114), we obtain
T2 T1
1S2 = mcw ln + −1 . (9.115)
T1 T2
106 Thermodynamics of Systems
The total entropy change during the entire heating process is then equal to
or
T1 T0 T2 T1
1S = mcw ln + − 1 + mcw ln + −1 . (9.117)
T0 T1 T1 T2
1
Tj+1 Tj
X
1S = mcw ln + −1 . (9.118)
Tj Tj+1
j=0
The numerical value of the entropy change is obtained from (9.117) as follows:
T2 T1 T0
1S = mcw ln + + −2 , (9.119)
T0 T2 T1
or
373 323 273
1S = 1 kg × 4186 J/kg K × ln + + − 2 = 97.4 J/K. (9.120)
273 373 323
Comparing the numerical result (9.120) with the numerical result (9.113) obtained
in Problem 1, the lesson is that the total entropy change decreases when the heating
process is divided into two steps.
Problem 3
Using the result of the Problem 2, show that a quantity of water with mass m = 1 kg at
the initial temperature T0 = 273 K can be heated to T = 373 K with no entropy change
of the entire system by dividing the heating process into a very large, number of very
small heating steps.
Solution
Let us first recall the result for the total entropy change (9.118) generalized to an
arbitrary number of n steps, i.e.,
n−1
Tj+1 Tj
X
1S(n) = mcw ln + −1 . (9.121)
Tj Tj+1
j=0
Macroscopic Thermodynamics 107
As the number of steps becomes very large, the ratio Tj+1 /Tj approaches unity, and
we can use the mathematical approximation
ln(1 + x) → x, x → 0, (9.122)
to obtain
Tj+1 Tj Tj
ln = − ln = − ln 1 + −1
Tj Tj+1 Tj+1
Tj Tj
≈− −1 = − + 1. (9.123)
Tj+1 Tj+1
Thus, the entropy change for the entire system tends to zero, when the heating process
is divided into a very large number of very small heating steps.
Problem 4
At normal atmospheric pressure p0 and the temperature T0 = 273 K, a liquid has
the specific heat at constant pressure equal to cP = 28 J/mol K and a molar vol-
ume equal to vM = 14.72 × 10−6 m3 /mol. The volume expansion coefficient of the
liquid is α = 1.81 × 10−4 1/K and its isothermal compressibility coefficient is γ =
3.88 × 10−11 m2 /N. What is the specific heat at constant volume cV and the ratio
κ = cP /cV for this liquid.
Solution
Let us start with the obvious identity
∂(T, v) ∂( p, v) ∂( p, T)
= −1, (9.125)
∂(v, T) ∂( p, v) ∂( p, T)
or
∂( p, v) ∂( p, T) ∂(T, v)
= −1, (9.126)
∂( p, T) ∂(v, T) ∂( p, v)
or
∂v ∂p ∂T
= −1, (9.127)
∂T p ∂v T ∂p V
108 Thermodynamics of Systems
or
−1
∂p ∂v ∂v α
1 1
= − = . (9.128)
∂T V v ∂T p v ∂p T γ
∂s ∂s
ds = dT + dv, (9.129)
∂T V ∂v T
or
∂s ∂s ∂s ∂v
= + , (9.130)
∂T p ∂T V ∂v T ∂T p
or
" #
∂s ∂s ∂s 1 ∂v
T =T + Tv , (9.131)
∂T p ∂T V ∂v T v ∂T p
or
∂s
cp = cV + Tvα . (9.132)
∂v T
∂( p, v)
≡ 1, (9.133)
∂(T, s)
we obtain
∂s ∂(T, s) ∂( p, v) ∂p α
= = = . (9.134)
∂v T ∂(T, v) ∂(T, s) ∂T V γ
Thus, we obtain
α2
cp = cV + Tv , (9.135)
γ
or
Tvα 2
cV = cp − . (9.136)
γ
Macroscopic Thermodynamics 109
and
cp 28
κ= = = 1.888. (9.138)
cV 14.83
Problem 5
The pressure of a thermally insulated solid sample is slowly increased by a small
amount 1p. Calculate the resulting temperature change 1T of the sample as a function
of the pressure change 1p, the initial temperature T0 , the specific heat at constant
pressure cp , the density ρ, and the volume expansion coefficient α.
Solution
Since the sample is thermally insulated, one has dq = Tds = 0, i.e., this process goes
at constant entropy. Thus, we can write
∂s ∂s
ds = dT + dp = 0, (9.139)
∂T p ∂p T
or
∂s
dT
cp =− dp. (9.140)
T ∂p T
∂( p, v)
≡ 1, (9.141)
∂(T, s)
we obtain
∂( p,v)
∂s ∂(T, s) ∂(T, s) ∂( p, v) ∂( p, v)
∂(T,s)
= = = ∂(T,p)
= (9.142)
∂p T ∂(T, p) ∂(T, p) ∂(T, s) ∂(T, p)
∂(T,s)
∂s ∂( p, v) ∂v
=− =− = −vα. (9.143)
∂p T ∂( p, T) ∂T p
110 Thermodynamics of Systems
dT α
= vdp. (9.144)
T cp
p0Z+1p
T0 + 1T α
ln = vdp, (9.145)
T0 cp
p0
or
p0 +1p
α
Z
1T = T0 exp vdp − 1. (9.146)
cp
p0
p0Z+1p
α α0
vdp ≈ v0 1p, (9.147)
cp cp0
p0
where the quantity α0 /cp0 is taken for the initial state of the solid sample. Thus, we
obtain
α0
1T = T0 exp v0 1p − 1 . (9.148)
cp0
α0
1T = T0 v0 1p. (9.149)
cp0
Problem 6
A substance at pressure p and constant temperature T has the specific heat at con-
stant pressure (per mole) denoted by cp and a molar volume v. Let us assume that the
temperature dependence of the volume expansion coefficient α = α(T) is a known
function. Find the derivative of cp with respect to the pressure p as a function of T and
v as well as α = α(T) and its derivatives with respect to T.
Macroscopic Thermodynamics 111
Solution
The objective of the problem is to calculate
" #
∂cp ∂ ∂s
= T . (9.150)
∂p T ∂p ∂T p
T
∂cp ∂ ∂s ∂ ∂(T, s)
=T =T , (9.151)
∂p T ∂T ∂p T p ∂T ∂(T, p) p
or by equation (9.143),
" #
∂cp ∂ ∂( p, v) ∂ ∂v
=T = −T , (9.152)
∂p T ∂T ∂(T, p) p ∂T ∂T p
p
or
∂cp ∂
= −T [vα(T)]p , (9.153)
∂p T ∂T
or
∂cp ∂v ∂α
= −T α − Tv , (9.154)
∂p T ∂T p ∂T p
or
∂cp
dα
= −Tvα 2 − Tv . (9.155)
∂p T dT
Finally, we obtain
∂cp
dα
= −Tv α 2 + . (9.156)
∂p T dT
Problem 7
The tension force of an elastic rod is, around the temperature T, related to the length
of the rod L by the expression F = aT 2 (x − x0 ), where a and x0 are positive constants
and F is the external force acting on the rod. The heat capacity at constant volume
(i.e., at constant length) of an unstretched rod (x = x0 ), is given by cX = bT, where b
is a positive constant.
112 Thermodynamics of Systems
(a) Write down the first law of thermodynamics for the rod.
(b) Using S = S(T, x), calculate (∂S/∂x)T .
(c) If we know S (T0 , x0 ), calculate S(T, x) at any other T and x.
(d) If we stretch a thermally insulated rod from x = xI at T = TI to x = xF at T = TF ,
calculate TF . Compare TF with TI .
(e) Calculate cX = cX (T, x) for an arbitrary length x, instead of for the length x = x0 .
Solution
(a) The general form of the first law of thermodynamics is
dU = dQ − dL. (9.157)
In our case, we have dQ = TdS and dL = −Fdx, with F as written above in the
problem text. The minus sign here is related to the fact that above (in the problem
text), F actually is the external force (a force of an external agent) acting on the
rod. This force is in equilibrium with the internal force Fint of the rod molecules,
which is thus negative of F, that is, Fint = F. Just as for the case of a gas (for which
the work dL = Fint dx is done by the internal force of pressure of gas molecules),
the work done by the internal force of the rod molecules is also given by dL =
Fint dx = −F dx. Thus, the first law of thermodynamics for the rod is represented
by the standard form
or
dU − Fdx dU
dS = = − aT (x − x0 ) dx. (9.159)
T T
∂(T, s)
= −1, (9.160)
∂(F, x)
we obtain
∂(T,s) ∂S
∂(T, s) ∂(T, s) ∂(T, x) ∂(T,x) ∂x T
−1 = = = ∂(F,x)
= ∂F
, (9.161)
∂(F, x) ∂(T, x) ∂(F, x) ∂T x
∂(T,x)
or
∂S ∂F
=− = −2aT (x − x0 ). (9.162)
∂x T ∂T x
Macroscopic Thermodynamics 113
(c) In order to calculate S(T, x) at some T and x, it is suitable to calculate the change
of entropy with temperature at constant length x = x0 , where we know the heat
capacity cX = bT. Thus, we have
∂S ∂S
cX = bT = T ⇒b= , (9.163)
∂T x=x0 ∂T x=x0
or
∂S S (T, x0 ) − S (T0 , x0 )
= = b. (9.164)
∂T x=x0 T − T0
Thus, we obtain
∂S
= −2aT (x − x0 ), (9.166)
∂x T
or
S(T,x)
Z Zx
dS = −2aT (x − x0 ) dx, (9.167)
S(T,x0 ) x0
or
(d) Since the thermally insulated rod undergoes a constant-entropy change, we have
or
Thus, we obtain
b − a (xI − x0 )2
TF = TI . (9.172)
b − a (xF − x0 )2
Thus, we see that for LF > LI , we have TF < TI , whereas for LF < LI , we have
TF > TI .
114 Thermodynamics of Systems
∂cX ∂ ∂S ∂ ∂S
=T =T . (9.173)
∂x T ∂x ∂T x T ∂T ∂x T x
∂S
= −2aT (x − x0 ), (9.174)
∂x T
we obtain
∂cX ∂
=T [−2aT (x − x0 )]x = −2aT (x − x0 ). (9.175)
∂x T ∂T
Thus, we have
cXZ(T,x) Zx
dcX = −2aT (x − x0 ) dx, (9.176)
cX (T,x0 ) x0
or
cX (T, x) = bT − aT (x − x0 )2 . (9.178)
Problem 8
A substance has the volume expansion coefficient α and the isothermal compressibility
coefficient γ given by
∂V ∂V a
1 2bT 1
α= = and γ = − = , (9.179)
V ∂T P V V ∂p T V
respectively, where a and b are constants. Determine the change of pressure of the
substance when its temperature is changed from T1 to T2 within a constant volume.
Express the result in terms of the constants a and b, as well as the temperatures T1
and T2 .
Macroscopic Thermodynamics 115
Solution
From the definition of γ in (9.179), we readily obtain
∂V
= −a ⇒ V( p, T) = −ap + f (T). (9.180)
∂p T
∂V
= f 0 (T) = 2bT ⇒ f (T) = bT 2 + C, (9.181)
∂T P
where C is an unspecified constant. Thus, when the volume of the substance is kept
constant [V( p, T) = Constant], we have
From (9.182), we readily obtain the pressure change in the process as follows:
b 2
1p = p2 − p1 = T2 − T12 . (9.183)
a
Problem 9
A substance has the volume expansion coefficient α and the isothermal compressibility
coefficient γ given by
∂V
1
α= = A(1 − ap) (9.184)
V ∂T P
and
∂V
1
γ =− = K[1 + b(T − T0 )], (9.185)
V ∂p T
respectively, where we introduce A = 4.2 × 10−4 1/K, a = 1.2 × 10−9 1/Pa, K = 2.52
× 10−10 1/Pa, and b = 2 × 10−3 1/K as given constants.
(a) Derive the thermal equation of the state of the substance and express the constant a
in terms of the constants A, K, and b. Check the above given numerical values for
consistency.
(b) Calculate the required temperature change to increase the pressure in the sub-
stance to p = 107 Pa, if at the initial temperature of T0 = 273 K, the pressure is
p0 = 105 Pa.
116 Thermodynamics of Systems
Solution
(a) As both the volume expansion coefficient α and the isothermal compressibility
coefficient γ are defined as partial derivatives of V divided by V, let us consider
the total derivative of ln V, i.e.,
1 ∂V 1 ∂V
d[ln V] = dp + dT. (9.186)
V ∂p T V ∂T P
or
Thus, we have
∂(ln V) ∂(ln V)
= −K [1 + b (T − T0 )], = A(1 − ap), (9.189)
∂p ∂T
or
∂ 2 (ln V) ∂ 2 (ln V)
= −Kb, = −Aa. (9.190)
∂T∂p ∂p∂T
Since the two second partial derivatives in (9.190) are equal to each other, we must
have Aa = Kb, or
∂(ln V)
= −K [1 + b (T − T0 )] , (9.192)
∂p
to obtain
ln V = −K [1 + b (T − T0 )] p + f (T). (9.193)
Substituting the result (9.193) into the second equation in (9.189), we get
∂(ln V)
= −Kbp + f 0 (T) = A(1 − ap). (9.194)
∂T
Macroscopic Thermodynamics 117
where C is a yet unspecified constant. Thus, the thermal equation of state has the
form
ln V = −K [1 + b (T − T0 )] p + AT + C. (9.196)
V
ln = −K [p − p0 + b (T − T0 ) p] + A (T − T0 ). (9.199)
V0
(b) Using the equation of state (9.199) for p = 100p0 and V = V0 , we obtain
or
99Kp0 99p0
T − T0 = = ≈ 6 K. (9.202)
A − 100Kbp0 b a−1 − 100p0
10 Variable Number of Particles
10.1 Chemical Potential
In our discussion so far, we have assumed that the number of the constituent particles
of a given thermodynamic system is constant (N = Constant). Let us now consider
a thermodynamic system with a variable number of particles. In other words, let us
assume that the number of constituent particles of a system is not constant, for exam-
ple, due to creation and annihilation of the constituent particles occurring in the sys-
tem. The creation and annihilation of the constituent particles of the system can be
realized in various ways. One common mechanism for creation and annihilation of
the constituent particles of the system is chemical reactions of the matter in the sys-
tem. Creation and annihilation of particles occur also in all common semiconductors,
where quasi-particles, namely, electrons and holes, are created and annihilated in pairs.
Another situation with a variable number of particles occurs in considering thermo-
dynamic equilibrium between an open system and its environment. If the system is
separated by a permeable membrane from its environment that can let particles in and
out of the system, then the number of particles of the system N would fluctuate in time
around some average equilibrium value. In all of the above examples, the number of
particles is not constant in time.
For the systems with variable number of particles, it is convenient to introduce a
new thermodynamic variable µ, which determines the energy increase in the system
due to the creation of a single particle in the system. The variable µ is usually called the
chemical potential of the system. In the course of a thermodynamic process, in which
creations and annihilations of constituent particles occur, the infinitesimal change of
the internal energy is defined by a generalization of the equation (8.39) of the form
dU = T dS − p dV + µ dN. (10.1)
Now, we need to relate the chemical potential µ to the other thermodynamic quantities
(e.g., p, V, T, S, . . . ). The equation (10.1) suggests that in the case of a thermodynamic
system with a variable number of particles, we have three pairs of canonically conju-
gated variables ( p, V), (T, S), and (µ, N). Obviously, the left-hand side of the equation
(10.1) is a total differential of the internal energy. The internal energy U here is a
three-variable function. The first variable can be either V or p, the second variable can
be either T or S, and the third variable can be either µ or N. Thus, there are 23 = 8
possible choices for the three variables that can be used to express U or other state
functions. Whatever choice is made, the three pairs of variables must be related to
each other in such a way that the right-hand side of the equation (10.1) is also a total
differential. The general expression
is a total differential of some function w = w(x, y, z), if the functions A(x, y, z),
B(x, y, z), and C(x, y, z) have the following form:
∂w(x, y, z) ∂w(x, y, z)
A(x, y, z) = , B(x, y, z) = ,
∂x ∂y
∂w(x, y, z)
C(x, y, z) = . (10.3)
∂z
Thus, the three conditions that the expression (10.2) is a total differential are
∂A ∂B ∂ 2w ∂A ∂B
= = ⇒ = , (10.4)
∂y ∂x ∂x∂y ∂y x,z ∂x y,z
∂A ∂C ∂ 2w ∂A ∂C
= = ⇒ = , (10.5)
∂z ∂x ∂x∂z ∂z x,y ∂x y,z
∂B ∂C ∂ 2w ∂B ∂C
= = ⇒ = . (10.6)
∂z ∂y ∂z∂y ∂z x,y ∂y x,z
∂(A, x) ∂(B, y)
= , z = Constant, (10.7)
∂( y, x) ∂(x, y)
∂(A, x) ∂(C, z)
= , y = Constant, (10.8)
∂(z, x) ∂(x, z)
∂(B, y) ∂(C, z)
= , x = Constant. (10.9)
∂(z, y) ∂( y, z)
∂(A, x)
= −1, z = Constant, (10.10)
∂(B, y)
∂(A, x)
= −1, y = Constant, (10.11)
∂(C, z)
∂(B, y)
= −1, x = Constant. (10.12)
∂(C, z)
Variable Number of Particles 121
Using the general results (10.10–10.12), the conditions that the right-hand side of the
equation (10.1) is a total differential are
∂(T, S)
= 1, N = Constant. (10.13)
∂( p, V)
∂(T, S)
= −1, V = Constant, (10.14)
∂(µ, N)
∂( p, V)
= 1, S = Constant. (10.15)
∂(µ, N)
The results (10.13–10.15) are some of the relations between the chemical potential
µ and the other thermodynamic variables in a system with the variable number of
particles. Clearly, there are many more relations between these six thermodynamic
variables ( p, V, T, S, µ, N), analogous to the nine relations derived in the Chapter 9,
“Macroscopic Thermodynamics.” In fact, in the case of systems with the variable num-
ber of particles, we have 60 thermodynamic coefficients and a systematic mathemati-
cal approach to the relations between all of these coefficients is very complex and not
necessary for the present analysis.
8 = N · µ. (10.16)
d8 = µ dN + N dµ. (10.17)
On the other hand, from the equation (10.1), it is clear that when all the other thermo-
dynamic quantities are kept constant, we have dU = µ dN. At this point, we require
that the change of internal energy of the system dU, caused by the change of the num-
ber of particles in the system dN only, is equal to the change of the thermodynamic
potential of the system. In other words, when all the other thermodynamic quantities
are kept constant, we require that
dU = d8 = µ dN (10.18)
or
Z Z
d8 d8 d8
8= dN = dN = N = µ N. (10.19)
dN dN dN
122 Thermodynamics of Systems
In order to satisfy the equation (10.19), the function µ = d8/dN must be an intensive
quantity, independent of the number of particles (i.e., the mass of the system), and
consequently it cannot be a function of any extensive thermodynamic quantity. The
only way this can be realized is if µ is a function of two other intensive quantities such
as the pressure p and temperature T, that is, µ = µ(T, p). We can now calculate the
differential of the chemical potential µ = µ(T, p) as follows:
∂µ ∂µ
dµ = dT + dp. (10.20)
∂T p ∂p T
∂(µ, N)
= −1, V = Constant, (10.21)
∂(T, S)
or
∂µ ∂µ ∂µ
0
= ∂µ ∂N
∂T ∂S ∂T
∂N = = −1, (10.22)
∂N ∂N ∂N ∂T P,V ∂S V
∂T ∂S ∂T ∂S
or
∂µ ∂S
=− = −s0 , (10.23)
∂T P,V ∂N V
∂(µ, N)
= 1, S = Constant, (10.25)
∂( p, V)
or
∂µ ∂µ ∂µ
0
= ∂µ ∂N
∂p ∂V ∂p
∂N = = 1, (10.26)
∂N ∂N ∂N
∂p T,S ∂V S
∂p ∂V ∂p ∂V
or
∂µ ∂V
= = v0 , (10.27)
∂p T,S ∂N S
Variable Number of Particles 123
∂V
v0 = . (10.28)
∂N S
d8 = µ dN − N s0 dT + N v0 dp, (10.30)
or
d8 = µ dN − S dT + V dp. (10.31)
d8 = − T dS − S dT + p dV + V dp + T dS − p dV + µ dN, (10.32)
Thus, we finally obtain the relation between the thermodynamic potential 8 and the
other thermodynamic functions as
8 = U − TS + pV, (10.34)
8 = F + pV. (10.35)
From the result (10.35) with (10.31), we can calculate the differential of the free energy
for a system with a variable number of particles, as follows:
dF = d8 − d( pV) = µ dN − S dT + V dp − V dp − p dV (10.36)
or finally
dF = −S dT − p dV + µ dN. (10.37)
124 Thermodynamics of Systems
Recall that we already met this relation in Section 8.3, “Pressure: Thermal-State
Equation.” In earlier chapters we have considered the thermodynamic systems with
fixed number of particles inside a variable volume. In chemical systems, we usually
have an entirely different situation with a variable number of particles within the fixed
volume. In chemical thermodynamics, it is, therefore, useful to introduce a new ther-
modynamic variable called the Helmholtz thermodynamic potential as follows:
= F − 8 = F − µ N = −pV, (10.38)
where we made use of the result (10.35). Using the result for the free energy F = U −
TS, we obtain an alternative expression for the Helmholtz thermodynamic potential
= U − TS − µ N. (10.39)
Using the definition (10.38) and the result (10.37), we can calculate the differential of
the Helmholtz thermodynamic potential as follows:
d = dF − µ dN − N dµ = −S dT − p dV + µ dN − µ dN − Ndµ, (10.40)
or finally
d = −S dT − N dµ − p dV. (10.41)
The number of particles in a chemical system considered in the above discussion can
then be calculated from the Helmholtz thermodynamic potential as follows:
∂
N=− . (10.42)
∂µ T,V
T1 = T2 = T
p1 = p2 = p (10.43)
µ1 (T, p) = µ2 (T, p)
Variable Number of Particles 125
qL = h2 − h1 . (10.44)
By convention, the latent heat qL is positive if the heat is absorbed by the matter that
undergoes the phase transition. Conversely, the latent heat qL is negative if the heat
is produced within matter that undergoes the phase transition and absorbed by the
surroundings. By definition of enthalpy (9.19), we obtain from (10.44)
qL = T (s2 − s1 ). (10.46)
∂µ ∂µ
= −s0 , = v0 . (10.48)
∂T P ∂p T
dp dp
−s01 + v01 = −s02 + v02 , (10.49)
dT dT
or
dp s02 − s01
= . (10.50)
dT v02 − v01
126 Thermodynamics of Systems
Multiplying the right-hand side of the equation (10.50) by unity expressed as N/N,
and using S = N s0 and V = Nvo , we obtain
dp s2 − s1
= . (10.51)
dT v2 − v1
Using now (10.46), we obtain the Clausius–Clapeyron formula for phase transitions
in the following form
dp qL
= . (10.52)
dT T (v2 − v1 )
The phase transitions are, of course, possible at various pressures and corresponding
temperatures. However, the two phases cannot exist in equilibrium with each other
at arbitrary pressures and temperatures, since T and p are related to each other along
the phase transition (coexistence) line in the (T, p) plane. We have already used this
observation while differentiating the equilibrium condition for chemical potentials in
the equation (10.47).
The latent heat qL varies from one pressure (and corresponding temperature) to
another, and this variation can be analyzed by calculating the rate of change of the
latent heat with temperature. Using (10.44), we obtain
Using here the definition of the specific heat at constant pressure given by (9.64), we
further obtain
∂h2 ∂h1
dqL dp
= cP2 − cP1 + − . (10.55)
dT ∂p T ∂p T dT
∂h ∂s
=T + v. (10.56)
∂p T ∂p T
∂s ∂T
= −1, (10.57)
∂p T ∂v p
Variable Number of Particles 127
we obtain
∂s ∂v
=− . (10.58)
∂p T ∂T p
∂h ∂v
= −T + v. (10.59)
∂p T ∂T p
The rate of change of the latent heat with temperature (10.61) is constant for many
substances, and, for example, in case of the phase transition between water and ice, it
can be calculated to give
dqL J cal
≈ 2730 ≈ 0.65 . (10.62)
dT kg K gK
Zn + Cu SO4 ↔ Cu + Zn SO4 .
During this chemical reaction, the cell performs the amount of work
dL = dqε = Ze dNε,
128 Thermodynamics of Systems
where Z is the number of valence electrons of copper (Cu). The first law of thermo-
dynamics in this case reads
dU = T dS − µ dN, µ = Zeε.
If we work with the number of moles dn = dN/NAV , we introduce the molar Gibbs
thermodynamic potential
8 = NAV µ = ZNAV eε = Zf ε,
where f = NAV e = 96488.5 C/mol is the Faraday constant. Thus, the first law of ther-
modynamics, becomes
dU = T dS − 8 dn, 8 = Zf ε.
Use the first law of thermodynamics to calculate the change of the internal energy of
the cell at the fixed temperature T and pressure p, when 1 mole of copper is produced.
Prove that the change of the internal energy (i.e., the heat of chemical reaction) can be
determined by measuring the electromotive force ε only.
Solution
From the first law of thermodynamics, we obtain
∂U ∂S
=T − 8. (10.63)
∂n T ∂n T
∂(T, S)
= 1, (10.64)
∂(8, n)
we can write
∂(T, S) ∂(8, n) ∂S ∂8
= ⇒ = . (10.65)
∂(T, n) ∂(T, n) ∂n T ∂T n
Thus, we have
∂U ∂8
=T − 8, (10.66)
∂n T ∂T n
or
U(T,1) Z1
∂8
Z
1U = dU = T − 8 dn, (10.67)
∂T n
U(T,0) 0
Variable Number of Particles 129
or
Z1
∂ε
1U = Z f T − ε dn. (10.68)
∂T n
0
The change of ε during the production of 1 mole of copper is very slow, and we can
write
∂ε
1U = Z f T −ε . (10.69)
∂T n
Furthermore, the temperature dependence of the electromotive force at fixed n is
insignificant, and we finally obtain
|1U| = Z f ε. (10.70)
Thus, by measuring ε, we directly measure the heat of the chemical reaction 1U.
Problem 2
A thermally insulated copper can of mass M = 0.75 kg with specific heat cM = 418 J/K
contains mw = 0.2 kg of water in equilibrium at the temperature Tw = 293 K. Let us
now place mI = 0.03 kg of ice at the temperature T0 = 273 K into the can. The latent
heat of melting the ice is qLI = 3.33 × 105 J/kg and the specific heat of water is cw =
4.186 kJ/kg K. When all the ice has melted, a new equilibrium state is reached.
(a) Calculate the temperature of the water in the new equilibrium.
(b) Calculate the total entropy change in this process.
(c) Calculate the work that has to be performed on the system in the new equilib-
rium in order to restore the temperature of the water in the copper can back to
T = 293 K.
Solution
(a) Let us denote the final temperature of the system after this process by TF . The
change of the internal energy of the copper can, when it is cooled from Tw = 293 K
to TF , is given by
ZTF
1UM = dUM = McM (TF − Tw ). (10.71)
Tw
The change of the internal energy of the water, when it is cooled from Tw = 293 K
to TF , is given by
ZTF
1Uw = dUw = mw cw (TF − Tw ). (10.72)
Tw
130 Thermodynamics of Systems
The change of the internal energy of the ice cube, when it is melted and then
warmed from T0 = 273 K to TF , is given by
McM Tw + mw cw Tw − mI qLI + mI cw T0
TF = . (10.75)
McM + mw cw + mI cw
dT
dS = mcV . (10.77)
T
The change of the entropy of the copper can, when it is cooled from Tw = 293 K
to TF , is then given by
ZTF
TF
1SM = dSM = McM ln . (10.78)
Tw
Tw
The change of the entropy of the water in the can, when it is cooled from Tw =
293 K to TF , is given by
ZTF
TF
1Sw = dSw = mw cw ln . (10.79)
Tw
Tw
Variable Number of Particles 131
The entropy change of the ice cube, when it is melted at constant temperature T0
and then warmed from T0 = 273 K to TF , is given by
qLI TF
1SI = mI + mI cw ln . (10.80)
T0 T0
The total entropy change of the system is given by
TF TF qLI TF
1S = McM ln + mw cw ln + mI + mI cw ln . (10.81)
Tw Tw T0 T0
Inserting the numerical values, we obtain 1S = 1193 J/K.
(c) The work necessary to restore the temperature of the water in the copper can back
to T = 293 K is given by
ZTw ZTw
1L = 1U = McM dT + (mw + mI ) cw dT, (10.82)
TF TF
or
Problem 3
A mixture of water and ice at the freezing temperature T0 = 273 K is put into a
refrigerator in order to freeze the remaining m = 0.1 kg of water. The heat from the
refrigerator is used to warm up a body of mass M = 1 kg and constant heat capacity
c = 2.5 kJ/kg K, initially at temperature equal to T0 = 273 K. The latent heat of freez-
ing the ice is equal to qL = 3.33 × 105 J/kg. Use the second law of thermodynamics to
calculate the minimum amount of heat that must be removed by the refrigerator in the
process.
Solution
The change in entropy of the mixture of water and ice during the freezing process at
constant temperature is
mqL
1SWI = − . (10.84)
T0
The change in entropy of the body is given by
ZTF
Mc dT TF
1SB = = Mc ln . (10.85)
T T0
T0
132 Thermodynamics of Systems
mqL TF
1S = 1SWI + 1SB = − + Mc ln ≥ 0. (10.86)
T0 T0
Thus, we have
TF mqL
ln ≥ , (10.87)
T0 McT0
or
mqL
TF ≥ T0 exp . (10.88)
McT0
On the other hand, the quantity of heat transferred to the body is given by
mqL
TF = T0 exp . (10.90)
McT0
Thus, we obtain
mqL
1QBmin = McT0 exp −1 . (10.91)
McT0
Problem 4
Use the definition of the Helmholtz thermodynamic potential for a system with the
variable number of particles to prove the following relation
V dp − S dT − N dµ = 0. (10.93)
Variable Number of Particles 133
Solution
From the definition of the Helmholtz thermodynamic potential, we have
= U − TS − µ N = −pV, (10.94)
or
U − TS − µ N + pV = 0. (10.95)
dU − T dS − S dT − N dµ − µ dN + p dV + V dp = 0. (10.96)
−S dT − N dµ + V dp = 0. (10.97)
Problem 5
Consider a model of the Earth’s atmosphere, where the air pressure in the atmosphere
P(z) is the following function of the altitude z
mgz
p(z) = p(0) exp − . (10.98)
kT
(a) Show that the rate of change of the boiling point of the water, due to the variation
of the air pressure, can be expressed by the following equation
where ρL = 103 kg/m3 is the mass density of the liquid water, ρG = 0.6 kg/m3
is the mass density of water vapor at the boiling temperature of T = 373 K, and
qLG = 2.4 × 106 J/kg is the latent heat of vaporization of water per unit mass.
(b) Given the mass density of air at the Earth’s surface ρA = 1.29 kg/m3 , calculate the
rate of change of the boiling point of the water with altitude expressed in degrees
Kelvin per kilometer.
Solution
(a) The rate of change of the boiling point can be written in the form
dTB dp dTB
= . (10.100)
dz dz dp
134 Thermodynamics of Systems
dp mg mgz mgp(z)
= − p(0) exp − =− . (10.101)
dz kT kT kT
we can write
dTB TB TB M M
= (VG − VL ) = − , (10.103)
dp MqLG MqLG ρG ρL
or
dTB TB (ρL − ρG )
= . (10.104)
dp ρL ρG qLG
Substituting the results (10.101) and (10.104) into (10.100) gives the required
result
dTB mgp(z) dTB mgp(z) TB (ρL − ρG )
=− =− . (10.105)
dz kT dp kT ρL ρG qLG
dTB K K
≈ 0.0033 = 3.3 . (10.106)
dz m km
Problem 6
The partition function for a system with a variable number of particles, as a function
of temperature T, volume V, and the number of particles N, is given by the expression
3 2
bT V
Z(N, V, T) = N exp , (10.107)
N2
where b is a constant. Derive the expression for the chemical potential µ of the system.
Solution
The free energy of this system, by definition, is given by
Z bkT 4 V 2
F = −NkT ln − NkT = − − NkT. (10.108)
N N
Variable Number of Particles 135
dF = −S dT − p dV + µ dN, (10.109)
we obtain the following result for the chemical potential µ of the system
2
∂F
V
µ= = bkT 4 − kT. (10.110)
∂N T,V N
Problem 7
The internal energy for a system with variable number of particles, as a function of
entropy S, volume V, and the number of particles N, is given by the expression
2/7
N 2S
U(S, V, N) = aNk exp , (10.111)
V 7Nk
where a is a constant. Derive the thermal and caloric-state equations for the system
and calculate the specific heat of the system at constant volume cV .
Solution
Let us first assume that N and V are kept constant. Then, the derivation of the expres-
sion for U, given by (10.111), with respect to U itself involves only the derivative of
entropy with respect to U on the right-hand side of the equation (10.111). Thus, we
obtain
∂U ∂S
2
1= = · U. (10.112)
∂U N,V 7Nk ∂U N,V
dU = T dS − p dV + µ dN, (10.113)
we see that
∂S
1
= . (10.114)
∂U N,V T
Substituting (10.114) into (10.112), we obtain the caloric equation of state of the sys-
tem in the form
2U 7
1= ⇒ U = NkT. (10.115)
7NkT 2
136 Thermodynamics of Systems
Using equations (10.111) and (10.113), we obtain the pressure of the system as
follows:
∂U
2U
p=− = . (10.116)
∂V N,S 7V
Substituting U from (10.115) into (10.116), we obtain the thermal equation of state of
the system in the form
NkT
p= . (10.117)
V
As it will be discussed in a later chapter, this system is a diatomic ideal gas with trans-
lational, rotational, and vibrational degrees of freedom. The specific heat at constant
volume cV is then given by
∂U
7
cV = = Nk. (10.118)
∂T V,N 2
11 Ideal Monatomic Gases
11.1 Continuous Energy Spectrum
The objective of the present chapter is to apply the general thermodynamic concepts
developed in previous chapters to the special case of an ideal monatomic gas. The
ideal monatomic gas considered here satisfies the following requirements:
1. The gas consists of a large number of identical monatomic constituent particles
(monatomic molecules);
2. The separation between the constituent particles is large enough, so that there are
no substantial interactions, nor statistical and quantum correlations between the
particles. The ideal gas concept thus represents an approximation that is valid in
dilute limit of realistic gases. In this limit, interparticle interactions are substantial
only during infrequent collisions between the constituent particles (assumed here
to be elastic in nature);
3. The particles are of very small sizes and can be treated as point-like objects with-
out an internal structure. Such objects have zero moments of inertia, and thus they
carry zero internal rotational energy. Their “zero sizes” cannot vibrate, and thus
the particles carry no internal vibrational energy. In reality, monatomic molecules
of noble, inert gases (He, Ne, Ar, etc.) do behave approximately in this way, in the
sense that the effects of their internal structure can be, to a good approximation,
ignored under normal conditions ( p ∼ 1 atm, T ∼ room temperature).
In view of the above assumptions, the constituent molecules can be treated as mutu-
ally noninteracting particles confined in a box with volume V, each having only the
translational kinetic energy, given by
h2 2
Ei = 2/3
nx + n2y + n2z , (11.1)
8mV
θ
n
φ ny
nx
h2
Ei = n2 . (11.3)
8mV 2/3
From the estimate (3.45), one can see that the spacing between the adjacent energy
levels is extremely small. One can therefore assume that the energy levels are contin-
uously distributed in the n-space, much like in classical physics. The discrete energy
levels (11.3) can then be replaced by classical continuum representation, that is,
h2 p2
E1 (n) = n 2
= , (11.4)
8mV 2/3 2m
where p is the magnitude of the linear momentum vector of a constituent particle, not
to be confused with the pressure p of a thermodynamic system. Also, the speed v of
a constituent particle, defined by p = mv, should not be confused with the volume per
unit mass v of a thermodynamic system. The two conflicting notations will never be
used in the same context in this book, so there is no risk for confusion. Furthermore,
it should be noted that the subscript 1 in E1 (n) is not a label of the first energy state,
but merely an indicator that the energy (11.4) is the translational energy of a single
constituent particle. The significance of this notation will become clear from the below
discussion.
Because the positive numbers nx , ny , and nz in (11.1) are integers, each energy
state occupies the volume equal to 1 × 1 × 1 = 1 in the n-space in Fig. 11.1. Thus, the
number of states (sublevels), dg(n) that are within the spherical shell with radii n and
n + dn, is simply equal to the volume of this shell in the first octant of the n-space,
1 π n2
dg(n) = (4π n2 dn) = dn. (11.5)
8 2
Using the equation (11.4), we obtain the following relation between the number n and
the momentum p of the constituent particle
2V 1/3 2V 1/3
n= p ⇒ dn = dp. (11.6)
h h
Ideal Monatomic Gases 141
3
2V 1/3 πp2
dg( p) = dp, (11.7)
h 2
or
V
dg( p) = 4πp2 dp. (11.8)
h3
Ei E1 (n)
X Z
Z= gi exp − ≈ dg(n) exp − . (11.9)
kT kT
i
Z∞ Z∞
E1 ( p) V E1 ( p)
Z = dg( p) exp − = 3 exp − 4π p2 dp. (11.10)
kT h kT
0 0
Z∞ Z∞ Z∞ Z∞
2
4π p dp = dpx dpy dpz , (11.12)
0 −∞ −∞ −∞
E1
Z
1
Z= 3 exp − dx dy dz dpx dpy dpz . (11.13)
h kT
01
142 Ideal and Nonideal Gases
The integral on the right-hand side of the equation (11.13) is over the entire six-
dimensional phase space denoted by 01 , covering all three spatial co-ordinates of the
ordinary space (x, y, z), within the confining box, and the three co-ordinates in the
fictitious p-space, i.e., the three components of the linear momentum vector ( px , py ,
pz ) of a single constituent particle. Introducing here the dimensionless infinitesimal
element of the six-dimensional phase space for a single particle as follows:
1
d01 = dx dy dz dpx dpy dpz , (11.14)
h3
we obtain a compact formal notation for the partition function Z in the following form
E1
Z
Z= exp − d01 . (11.15)
kT
01
The partition function Z defined by (11.15) can be defined in the same way for each of
the N constituent particles of the system by integrating over the six-dimensional phase
space of each of these N particles.
Using the definition (8.13), we can now define the grand partition function for all
N particles of the system as follows:
N
!
ZN
Z
1 1 X
ZN = = exp − Ea d01 d02 . . . d0N . (11.16)
N! N! kT
0 a=1
Thus, the grand partition function for the entire system can be written in the following
compact form
EN
Z
1
ZN = exp − d0, (11.17)
N! kT
0
where
N N
X X p2a
EN = Ea = (11.18)
2m
a=1 a=1
is the sum of the energies of all the constituent particles of the system, i.e., the total
energy of the system. The quantity,
N
Y
d0 = d0a = d01 d02 . . . d0N , (11.19)
a=1
is the infinitesimal element of the 6N-dimensional phase space of the entire thermo-
dynamic system with N constituent particles.
Ideal Monatomic Gases 143
Z∞
V p2
Z= 3 exp − 4π p2 dp, (11.20)
h 2m k T
0
Z∞
V 2
Z = 3 (2m k T)3/2 4π w2 e−w dw, (11.22)
h
0
or
3/2
2π m k T
4
Z=V √ I2 , (11.23)
h2 π
Z∞ Z∞ Z∞
2 −w2 1 −w2 1 2
I2 = w e dw = we d(w ) =
2
w d(−e−w ). (11.24)
2 2
0 0 0
Z∞ √ √
1 2 2 1 π π
I2 = −w ∞
−we |0 + e −w
dw =
= . (11.25)
2 2 2 4
0
Substituting (11.25) into (11.23), we obtain the final result for the partition function of
an ideal monatomic gas
3/2
2π m k T
Z=V . (11.26)
h2
144 Ideal and Nonideal Gases
In the limit of a continuous distribution of the energy levels in the n-space, the number
of particles with linear momenta p within an infinitesimal range ( p, p + dp) is given
by
N E( p)
dn( p) = dg( p) exp − . (11.28)
Z kT
The probability for a particle to have the momentum p in the interval ( p, p + dp) is
thus given by
dn( p) dq( p) p2
dω( p) = = exp − . (11.29)
N Z 2m k T
Substituting the results (11.8) for dg( p) and (11.26) for Z into the equation (11.28), we
obtain
h3 V p2
1 2
dω( p) = 4π p dp exp − (11.30)
V (2π m k T)3/2 h3 2m k T
or finally
4π p2 dp p2
dω( p) = exp − = ν( p)dp. (11.31)
(2π m k T)3/2 2m k T
m3 4π v2 dv m v2
dω(v) = exp − , (11.32)
(2π m k T)3/2 2k T
or finally
m 3/2
mv2
dω(v) = 2
4π v dv exp − = ν(v)dv, (11.33)
2π kT 2kT
Ideal Monatomic Gases 145
where
m 3/2
mv2
ν(v) = 4π 2
v exp − , (11.34)
2πkT 2kT
is the probability density that a particle in an ideal monatomic gas has the speed v. The
distribution function in (11.34) is called the Maxwell–Boltzmann speed distribution.
dν(v)
= 0, (11.35)
dv
where
mv2
ν(v) = Constant × v2 exp − . (11.36)
2kT
mv2
dν(v) 2mv
= 2v − v2 exp − = 0, (11.37)
dv 2kT 2kT
or
mv3P 2kT
2vP − =0⇒ = v2P . (11.38)
kT m
The final result for the most probable speed of particles in an ideal monatomic gas is
then given by
r
2kT
vP = . (11.39)
m
Z∞
< v > = v ν(v) dv, (11.40)
0
146 Ideal and Nonideal Gases
or
m 3/2 Z∞
mv2
< v >= 4π v3 dv exp − . (11.41)
2πkT 2kT
0
Z∞
2 m 3/2 2πkT 2
< v >= t e−t dt
π 2π kT m
0
1/2 Z∞
2 2πkT
= t d(−e−t ). (11.44)
π m
0
The final result for the average speed of particles in an ideal monatomic gas is then
given by
r
8kT
< v >= . (11.46)
πm
or
m 3/2 Z∞
mv2
<v >=
2 4
4π v dv exp − . (11.48)
2πkT 2kT
0
we obtain
or
Z∞
2 m 3/2 2kT 5/2
2
<v >=√
2
w3 d −e−w . (11.51)
π 2kT m
0
∞ Z∞
kT 4 2 2
< v2 > = √ −w3 e−w + 3w2 e−w dw,
(11.52)
m π 0
0
or
Z∞
3kT 4 2 3kT 4
<v >=
2
√ w2 e−w dw = √ I2 , (11.53)
m π m π
0
√
where the integral I2 was calculated in (11.25) as I2 = π/4.
Thus, the final result for the average of the square of the particle speed in an ideal
monatomic gas is given by
3kT
< v2 > = . (11.54)
m
1 3
< E > = m < v2 > = k T. (11.56)
2 2
3
U = N < E > = NkT. (11.57)
2
In the next section, we will show that this result from the kinetic theory agrees with the
thermodynamic result obtained from the caloric-state equation (8.22) with the partition
function (11.26).
yielding,
m 3/2 mv2
dω vx , vy , vz = dvx dvy dvz exp − , (11.59)
2πkT 2kT
or
where
mv2j
!
m 1/2
ν vj = , j = x, y, z.
exp − (11.61)
2πkT 2kT
Z∞
ν vj dvj = 1, j = x, y, z.
(11.62)
−∞
Ideal Monatomic Gases 149
Z∞ m 1/2 Z∞ mv2j
!
ν vj dvj =
exp − dvj
2π kT 2kT
−∞ −∞
m 1/2 Z∞ mv2j
!
< v2j >= 2
vj exp − dvj . (11.65)
2πkT 2kT
−∞
or
Z∞ Z∞ √
2 −w2 1 2 −w2 π
I2 = w e dw = w e dw = . (11.68)
2 4
0 −∞
Using the result (11.69), we can calculate the average kinetic energy of a single particle
(11.56) using the following definition
1
< E > = m < v2x > + < v2y > + < v2z > . (11.70)
2
kT kT kT
1 3
< E >= m + + = k T. (11.71)
2 m m m 2
kT kT kT
3
U = N < E >= N + + = NkT. (11.72)
2 2 2 2
From the result (11.72), we see that each of the three translational degrees of freedom
makes the same contribution, equal to 12 NkT, to the internal energy of the system.
This observation is a special case of the so-called equipartition theorem in classical
thermodynamics.
According to the equipartition theorem, each term in a nonrelativistic expression
E = E(x, y, z, px , py , pz ) for the energy of a constituent particle that is quadratic in
a dynamical variable contributes the amount of 21 NkT to the internal energy of the
system.
For example, for N classical simple harmonic oscillators with classical energy
p2x 1
EV (x, px ) = + m ω 2 x2 , (11.73)
2m 2
there are, by (11.73), two such quadratic terms. By the equipartition theorem, we thus
expect that the internal energy of any system with N classical harmonic oscillators
is given by U = 2 × 12 NkT = NkT. This result for the vibrational degrees of freedom
in the classical limit, will be derived from quantum statistical physics in Chapter 12,
“Ideal Diatomic Gases.” In Section 11.6.2, “Harmonic and Anharmonic Oscillators,”
we will derive this result from the classical statistical physics of oscillators in thermal
equilibrium.
(11.26) into the caloric-state equation (8.22), we obtain the internal energy of the sys-
tem as follows:
∂
U = NkT 2 (ln Z)V , (11.74)
∂T
with
3/2
2π m k
ln Z = ln V + ln T 3/2
+ ln . (11.75)
h2
∂
d 3 3
(ln Z)V = ln T = . (11.76)
∂T dT 2 2T
Substituting (11.76) into (11.74), we obtain the result for the internal energy of an ideal
monatomic gas
3 3
U = NkT 2 = NkT. (11.77)
2T 2
The result (11.77) is in agreement with the results (11.57) and (11.72) obtained from
the kinetic theory of ideal monatomic gases.
Z
F = −NkT ln − NkT. (11.78)
N
Substituting (11.26) into (11.78), we obtain
" 3/2 #
V 2π m k T
F = −NkT ln − NkT. (11.79)
N h2
or
2 V 2π m k T
3
F = − NkT ln + ln − NkT. (11.80)
2 3 N h2
From the result (8.2), we can calculate the entropy of an ideal monatomic gas
U−F 3 2 V 2π m k T
S= = Nk 1 + ln + ln + k N. (11.81)
T 2 3 N h2
152 Ideal and Nonideal Gases
Using now the result (8.42), we obtain the thermal-state equation for an ideal mon-
atomic gas
∂F ∂
p=− = NkT [ln V + f (T, N)], (11.82)
∂V T ∂V
or finally
NkT
p= ⇒ pV = NkT. (11.83)
V
This important result for the pressure of a classical ideal gas is known as the ideal
gas law. Here, we derived it for an ideal monatomic gas; however, it holds also for
ideal gases of polyatomic molecules, provided that N in (11.83) is understood as the
total number of molecules (see Chapter 12). The equation (11.83) applies also to a
mixture of several different ideal gases, provided that N is understood as the total
number of molecules (of whatever sort) in the mixture. It should be stressed that the
equation (11.83) is exact for classical ideal gases only. However, the classical ideal
gas concept does correspond to the physically significant dilute limit of realistic gases,
in which one can ignore the interparticle interactions (discussed in Chapter 13, “Non-
ideal Gases”) and quantum correlations (discussed in the Part Four of this book). The
enthalpy for an ideal monatomic gas is then given by (9.19), i.e.,
3 5
H = U + pV = NkT + NkT = NkT. (11.84)
2 2
N mgas
Nk = NAV k = NAV k. (11.87)
NAV M
Let us now introduce the universal gas constant, denoted by R, using the following
definition
R = NAV k, (11.88)
or
J J
R = 6.023 · 1023 × 1.3807 · 10−23 = 8.314 . (11.89)
K K Mole
R
Rg = , (11.90)
M
which is different for different gases. Using (11.89) and (11.90), we finally obtain
mgas
Nk = R = mgas Rg . (11.91)
M
3 mgas U 3
U= RT ⇒ u = = Rg T, (11.92)
2 M mgas 2
where u = U/mgas is the internal energy per unit mass. Similarly the thermal-state
equation (11.83) becomes
m
pV = R T ⇒ pV = Rg T, (11.93)
M
where v = V/mgas is the volume per unit mass. The enthalpy (11.84) is given by
5 mgas 5
H= R T ⇒ h = Rg T, (11.94)
2 M 2
∂u
3
cV = = Rg . (11.95)
∂T V 2
The specific heat at constant pressure (9.64) for ideal monatomic gas becomes
∂h
5
cP = = Rg . (11.96)
∂T p 2
The relation between the specific heats for ideal monatomic gas is now given by
cV − cP = R g . (11.97)
The volume expansion coefficient (9.26) for ideal monatomic gas is calculated as
follows:
1 ∂v 1 ∂ Rg T Rg
1
α= = = = . (11.98)
v0 ∂T P v0 ∂T p0 p0 v0 T0
T T
v = v0 1 + = v0 1 + , (11.99)
T0 273.16
1 ∂p 1 ∂ Rg T Rg
1
β= = = = . (11.100)
p0 ∂T V p0 ∂T v0 p0 v0 T0
T T
p = p0 1 + = p0 1 + , (11.101)
T0 273.16
1 α 1
γ= = . (11.102)
p0 β p0
p
v = v0 1 − . (11.103)
p0
Ideal Monatomic Gases 155
N N 2
p
a
X X
EN = Ea = + V (Era ) , (11.104)
2m
a=1 a=1
where (Era , pEa ) = (xa , ya , za , pxa , pya , pza ) specifies the position and momentum of the
a-the particle. For example, in a uniform gravitational field along the z-direction, one
has the familiar result V(Era ) = m g za . Let us rewrite the equation (11.104) as
N
X N
X
EN = H1 (Era , pEa ) = H1 xa , ya , za , pxa , pya , pza ,
(11.105)
a=1 a=1
Note that H1 (Era , pEa ) = Ea is the energy of the a-th particle. Because there are no inter-
actions between particles, the N-particle partition function still has the form as in the
equation (11.16),
ZN
ZN = , (11.107)
N!
156 Ideal and Nonideal Gases
with Z being the one-particle partition function that, by the equation (11.13), can be
written as
1
Z= Zclassical , (11.108)
h3
with
Z Z Z Z Z Z
Zclassical = dx dy dz dpx dpy dpz
" #
H1 x, y, z, px , py , pz
× exp − . (11.109)
kT
Introducing here the infinitesimal element of the classical six-dimensional phase space
for a single particle as follows:
we obtain a compact formal notation for the partition function Zclassical in the following
form
H1 (Er, pE)
Z
Zclassical = exp − d0C1 . (11.111)
kT
0C1
The internal energy of the gas is, by the equation (8.22), given by U = N U1 , with U1
being the internal energy per particle,
∂ ∂
U1 = k T 2 (ln Z) = k T 2 (ln Zclassical ). (11.112)
∂T ∂T
Note that, by the equation (11.112), our result for U1 does not depend on the Planck
constant, hence it represents a prediction based purely on classical physics. By the
equation (11.112),
1 ∂Zclassical
U1 = k T 2 . (11.113)
Zclassical ∂T
Using here
H1 (Er, pE)
Z
1
U1 = d0C1 exp − H1 (Er, pE), (11.115)
Zclassical kT
0C1
or in a brief form, as
Z
U1 = d0C1 F1 (Er, pE) H1 (Er, pE), (11.116)
0C1
with
H1 (Er, pE)
1
F1 (Er, pE) = exp − . (11.117)
Zclassical kT
By the equation (11.117), the function F1 (Er, pE) is positive and satisfies the condition
H1 (Er, pE)
Z Z
1
d0C1 F1 (Er, pE) = d0C1 exp −
Zclassical kT
0C1 0C1
or
Z
d0C1 F1 (Er, pE) = 1. (11.119)
0C1
In view of these facts and the form of the equation (11.116), the F1 (Er, pE) has the
meaning of a single-particle probability density such that the quantity d3 r d3 p F1 (Er, pE)
represents the probability to find the particle within the six-dimensional phase-space
volume element d0C1 = d3 r d3 p around the phase-space point (Er, pE). In view of this, it
is natural to write the equation (11.116), as
Z
U1 = < H1 (Er, pE) > = d0C1 F1 (Er, pE) H1 (Er, pE), (11.120)
0C1
for the average value of any single particle quantity b1 (Er, pE). For example, the average
kinetic energy of the particle is given by
( pE )2 ( pE )2
Z
< >= d0C1 F1 (Er, pE) , (11.122)
2m 2m
0C1
whereas the average value of the potential energy of the particle is given by
Z
< V(Er) > = d0C1 F1 (Er, pE) V(Er). (11.123)
0C1
Since d3 r d3 p F1 (Er, pE) represents the probability of finding any of the N particles within
the six-dimensional phase-space volume element d0C1 = d3 r d3 p around the phase-
space point (Er, pE), the quantity,
must be the average number of particles present within the six-dimensional phase-
space volume element d0C1 = d3 r d3 p around the phase-space point (Er, pE). By adding
all these dN’s over the entire phase-space volume, we must get N, i.e.,
Z Z
dN = N d0C1 F1 (Er, pE) = N. (11.125)
0C1 0C1
Indeed, note that the equation (11.125) is equivalent to the equation (11.119). By
d0C1 = d3 r d3 p, let us rewrite (11.125) in the following form
Z Z
d3 r d3 p N F1 (Er, pE) = N, (11.126)
Er pE
or as
Z
d3 r n(Er) = N, (11.127)
Er
R R
where the symbols Er and pE denote triple integrals over the volume of the ordinary
Er-space and the pE-space, respectively. In the equation (11.127), we introduced a field
like variable n(Er) via
Z
n(Er) = d3 p N F1 (Er, pE). (11.128)
pE
Ideal Monatomic Gases 159
Note that, since the integration in the equation (11.128) is carried over pE only, the result
is a function of Er only. As suggested by the equation (11.127), the quantity n(Er) is the
average number of all particles that are within the ordinary three-dimensional volume
element d3 r around the three-dimensional space point Er. In view of this, the field n(Er)
is the local particle number density at the space point Er.
In the applications to N-particle systems, the quantity,
Likewise, the internal energy of the ideal gas in an external field can also be written in
terms of f1 (Er, pE). Indeed, by U = N U1 and equations (11.116) and (11.129), we have
Z
U = N · U1 = N · d0C1 F1 (Er, pE) H1 (Er, pE), (11.131)
0C1
Note that, since the integration in the equation (11.134) is carried over pE only, the result
is a function of Er only. As suggested by the equation (11.133), the quantity d3 r ũ(Er)
is the internal energy of all particles that are within the ordinary three-dimensional
volume element d3 r around the three-dimensional space point Er. In view of this, the
160 Ideal and Nonideal Gases
field ũ(Er) is the local energy density (per unit volume) at the point Er. Likewise, for
the total internal kinetic energy of the gas, we have
N
X p2a ( pE )2
UK = < > = N· < >
2m 2m
a=1
( pE )2 ( pE )2
Z Z
=N· d0C1 F1 (Er, pE) = d0C1 N F1 (Er, pE)
2m 2m
0C1 0C1
( pE )2
Z
= d0C1 f1 (Er, pE) . (11.135)
2m
0C1
( pE )2
Z
ũK (Er) = d3 p f1 (Er, pE) . (11.137)
2m
pE
Much like in the previous examples, it is easy to see that ũK (Er) is the local density of
the kinetic energy.
The above concept of the one-particle distribution function is applicable even to
systems that are out of equilibrium, in which case f1 (Er, pE) is also a function of time t.
Interactions between particles also do not modify any of the ideas expressed in the
equations (11.125) through (11.135), as they all stem from the idea behind the equation
(11.124), i.e., the equation
giving the number of particles within the six-dimensional phase-space volume ele-
ment d0C1 = d3 r d3 p around the phase-space point (Er, pE). Studying the time evolu-
tion of f1 (Er, pE, t) was one of the first tasks of the nonequilibrium statistical mechanics
undertaken by Ludwig Boltzmann, who proposed the first transport equation for the
one-particle reduced distribution function for dilute gases. The Boltzmann transport
equation and its successors generally predict that the system evolves into the ther-
mal equilibrium state. In this state, f1 (Er, pE) is, for very dilute (ideal) gases, given by
equations (11.117) and (11.129) yielding
N H1 (Er, pE)
f1 (Er, pE) = N · F1 (Er, pE) = exp − , (11.139)
Zclassical kT
Ideal Monatomic Gases 161
with Zclassical as given in the equation (11.109) or (11.111). With the one-particle
Hamiltonian in (11.106), being the sum of a kinetic and a potential energy, one has
H1 (Er, pE)
Z Z
Zclassical = d3 r d3 p exp − , (11.140)
kT
Er pE
or
p2 V(Er)
Z Z
Zclassical = 3
d p exp − 3
d r exp − . (11.141)
2m k T kT
pE Er
Thus,
p2
Z
3
ZKIN = d p exp −
2m k T
pE
+∞ 3
p 2
Z
= dpx exp − x = (2π m k T)3/2 , (11.143)
2m k T
−∞
V(Er)
Z
ZPOT = 3
d r exp − . (11.144)
kT
Er
Thus,
F1 (Er, pE) = FKIN ( pE) · FPOT (Er) ⇒ f1 (Er, pE) = N · FKIN ( pE) · FPOT (Er), (11.145)
with
p2 p2
1 1
FKIN = exp − = exp − , (11.146)
ZKIN 2m k T (2π m k T)3/2 2m k T
162 Ideal and Nonideal Gases
and
V(Er)
1
FPOT = exp − . (11.147)
ZPOT kT
The one-particle reduced distribution function f1 (Er, pE) in the equation (11.145) is
known as the Maxwell–Boltzmann equilibrium distribution. It does not contain the
Planck constant at any place, so it is a classical distribution. The major feature of the
probability density F1 (Er, pE) for the position Er and the momentum pE of a single particle
is that Er and pE are statistically independent because of the product form of F1 (Er, pE)
in the equation (11.145). The main consequence of that is that if, for example, one
considers the functions b1 ( pE) of one-particle momentum only, then, by equations
(11.121) and (11.148), one has
Z Z
< b1 ( pE) > = d3 r d3 p F1 (Er, pE) b1 ( pE)
Er pE
Z Z
= d3 r d3 p FPOT (Er) FKIN ( pE) b1 ( pE)
Er pE
Z Z
= d3 r FPOT (Er) d3 p FKIN ( pE) b1 ( pE)
Er pE
Z
= d3 p FKIN ( pE) b1 ( pE)
pE
p2
Z
1
= 3
d p exp − b1 ( pE). (11.149)
ZKIN 2m k T
pE
From the equation (11.149), we see that this result is completely insensitive to the
form of the external potential V(Er). So, the final result for the average calculated in the
equation (11.149) is the same as for the particles confined in a box. Thus, for example,
for the average kinetic energy of a single particle, for whatever V(Er), we have the same
result as the one in the equation (11.71),
p2 d3 p p2 p
Z 2
3
< >= exp − = k T. (11.150)
2m ZKIN 2m k T 2m 2
pE
Ideal Monatomic Gases 163
Thus, within classical physics, the equilibrium probability density distribution of par-
ticle momenta is universal, and it is, by the equation (11.146), given by the Maxwell
formula
p2
1
FKIN ( pE) = exp − . (11.151)
(2π m k T)3/2 2m k T
It should be stressed that the content of the equation (11.151) is the same as that of the
velocity distribution (11.59), as can be seen by using pE = m Ev, i.e.,
where for the last step we employed the equation (11.148). From the equation (11.153)
with (11.147), we obtain
N V(Er)
n(Er) = N FPOT (Er) = exp − . (11.154)
ZPOT kT
The result (11.154) is well known as the Boltzmann formula. It shows that the local
gas density crucially depends on the external potential through the second, exponential
term in the equation (11.154), the so-called Boltzmann factor. By writing the equation
(11.154) at two different points, Er and Er0 , we obtain
For example, in a uniform gravitational field along the z-direction, one has the familiar
result V(Er) = V(x, y, z) = mgz, so by the equation (11.154), n(Er) will depend on z only.
Thus, by (11.155), we easily find
or with z0 = 0,
mgz
n(z) = n(0) exp − , (11.157)
kT
showing that the local density n(Er) exponentially decreases with increasing height. As
another example, consider a gas in a container with volume V, of whatever shape. If
the walls of the container are impenetrable, the container can be modeled as a particle
in a box potential, with
V(Er)
V(Er) = 0 ⇒ exp − = 1, (11.158)
kT
V(Er)
V(Er) = +∞ ⇒ exp − = 0, (11.159)
kT
outside the box. From the equations (11.158) and (11.159), one can easily see that the
potential partition function (11.144) is, for this case,
V(Er)
Z Z
3
ZPOT = d r exp − = d3 r = V, (11.160)
kT
Er Er∈inside
i.e., it is equal to the volume V of the space inside the container. The Boltzmann
formula (11.154) with (11.158) and (11.160), thus, gives
N
n(Er) = , (11.161)
V
for an Er inside the container, and, by equations (11.159) and (11.160),
n(Er) = 0, (11.162)
( pE )2
Z
ũK (Er) = d3 p f1 (Er, pE) (11.164)
2m
pE
Ideal Monatomic Gases 165
( pE )2
Z
ũK (Er) = d3 p N FKIN ( pE) FPOT (Er)
2m
pE
( pE )2
Z
= N FPOT (Er) d3 p FKIN ( pE)
2m
pE
3 3
= N FPOT (Er) k T = n(Er) k T, (11.165)
2 2
where we made use of equations (11.145), (11.146), (11.150), and (11.154). Thus, the
local kinetic energy density is given by
3
ũK (Er) = n(Er) k T, (11.166)
2
with n(Er) given by the Boltzmann formula. Note that the equation (11.166) is of the
same form as the equation (11.163) for a uniform gas with, however, the uniform
density replaced by the local particle density. Though not so obvious, the result in
the equation (11.166) is not surprising, in view of the previous observation that the
presence of the potential does not affect the average kinetic energy of a particle (it
is still = 32 k T), and, as there are n(Er) molecules per unit volume, the energy density
must be given by the equation (11.166). Finally, in view of the result (11.166), one
may expect that the nonuniform gas may be assigned a nonuniform pressure field,
following the local density in the same way as for uniform gases, in the form
2
p(Er) = n(Er) k T = ũK (Er). (11.167)
3
We will prove the validity of this guess in the Problem 8 of this chapter. In combination
with the Boltzmann formula (11.154) applied to the Earth’s atmosphere gases in the
equation (11.157), the equation (11.167) yields the well-known Barometric formula
mgz
p(z) = k T n(z) = k T n(0) exp −
kT
mgz
= p(0) exp − , (11.168)
kT
showing that the local pressure p(z) exponentially decreases with increasing height.
p2
H1 (x, p) = + V(x). (11.169)
2m
166 Ideal and Nonideal Gases
The discussion of the classical equilibrium statistics of this system is in large part
similar to that of the previous section for the particle moving in three dimensions. Of
special interest is the harmonic oscillator case, corresponding to the potential
m ω2 2
V(x) = x . (11.170)
2
Here, ω is the angular frequency of the harmonic oscillator. For the one-dimensional
system, the one-particle partition function can be written as follows:
1
Z= Zclassical , (11.171)
h
with
H1 (x, p)
Z Z
Zclassical = dx dp exp − . (11.172)
kT
The internal energy of this single-particle system is, by the equation (8.22), given by
∂ ∂
U1 = k T 2 (ln Z) = k T 2 (ln Zclassical ). (11.173)
∂T ∂T
Note that, by the equation (11.173), our result for U1 does not depend on the Planck
constant, hence it represents a prediction based purely on classical physics. Similarly
to the case of a particle moving in three dimensions, here we find that
Z Z
U1 = < H1 (x, p) > = dx dp F1 (x, p) H1 (x, p), (11.174)
H1 (x, p)
1
F1 (x, p) = exp − . (11.175)
Zclassical kT
Again, we have
Z Z
< b1 (x, p) > = dx dp F1 (x, p) b1 (x, p), (11.176)
for the average value of any single particle quantity b1 (x, p). For example, the average
kinetic energy of the particle is given by
p2 p2
Z Z
< >= dx dp F1 (x, p) , (11.177)
2m 2m
Ideal Monatomic Gases 167
whereas the average value of the potential energy of the particle is given by
Z Z
< V(x) > = dx dp F1 (x, p) V(x). (11.178)
Z+∞
p2
ZKIN = dp exp − = (2π m k T)1/2 , (11.180)
2m k T
−∞
Z+∞
V(x)
ZPOT = dx exp − . (11.181)
kT
−∞
Thus,
with
p2
1
FKIN = exp −
ZKIN 2m k T
p2
1
= exp − , (11.183)
(2π m k T)1/2 2m k T
and
V(x)
1
FPOT = exp − . (11.184)
ZPOT kT
Z+∞ Z+∞
dp ZKIN ( p) = 1, dx ZPOT (x) = 1. (11.185)
−∞ −∞
As in the case of a particle in three dimensions, the probability density in the equation
(11.182) is of the Maxwell–Boltzmann type, with the position and momentum being
independent random variables, with probability densities given in equations (11.183)
168 Ideal and Nonideal Gases
and (11.184). In relation to this, inserting (11.182) into the equations (11.177) and
(11.178), gives the results
Z+∞
p2 p2 p kT
2
dp
< >= exp − = (11.186)
2m ZKIN 2m k T 2m 2
−∞
and
Z+∞
V(x)
dx
< V(x) > = exp − V(x). (11.187)
ZPOT kT
−∞
Z+∞ 1/2
α z2
2π
dz exp − = , (11.188)
2 α
−∞
whereas, in evaluating the integral in the equation (11.186), we used the result
Z+∞ 1/2
α z2
2π 1
2
z dz exp − = . (11.189)
2 α α
−∞
For the case of the harmonic oscillator potential in the equation (11.170), we have
Z+∞
m ω 2 x2 2π k T 1/2
ZPOT = dx exp − = . (11.190)
2k T m ω2
−∞
So, by (11.187),
Z+∞ 1/2
m ω 2 x2 m ω2
< V(x) > = < >= dx
2 2π k T
−∞
m ω 2 x2 m ω 2 x2 kT
× exp − = . (11.191)
2k T 2 2
In evaluating the integrals in equations (11.190) and (11.191), we again used the results
(11.188) and (11.189). In summary, by equations (11.186) and (11.191), for the classi-
cal harmonic oscillator, there is an equipartition of energy, with
p2 m ω 2 x2 kT
< >=< >= . (11.192)
2m 2 2
Ideal Monatomic Gases 169
p2 m ω 2 x2
U1 = < H1 (x, p) > = < >+< > = k T. (11.193)
2m 2
By equations (11.179) and (11.190), we have for the case of the harmonic oscillator,
1/2
2π k T 2π k T
Zclassical = ZKIN × ZPOT = (2π m k T)1/2 × = . (11.194)
m ω2 ω
So,
Zclassical 2π k T kT
Z= = = . (11.195)
h hω ~ω
Thus, by the equation (11.173),
∂ ∂ kT
U1 = k T 2 (ln Z) = k T 2 ln = k T, (11.196)
∂T ∂T ~ω
in accordance with the result (11.193) for the same quantity, obtained in a different
way. A notable feature of this classical result is that the internal energy of a single
harmonic oscillator does not depend on the oscillator frequency ω. Thus, for a classical
system composed of N mutually noninteracting oscillators with whatever frequencies,
the net vibration internal energy is simply given by
Note that the equation (11.197) applies even if the N oscillators have different fre-
quencies ω. By virtue of the classical result (11.193), any information about the actual
oscillators, frequencies are completely washed out in the classical limit.
Eα
X
ZQM = exp − . (11.198)
α
kT
The sum in (11.198) is done over all states α, and if there are degenerate states, then a
term is written for each of the degenerate states. In this way, we do not need to employ
the degeneracy factor gα , simply because the states with the same energy are, by con-
vention, repeated in the sum in (11.198). The energy levels are obtained by solving
the Schrödinger equation, as discussed in the Part One of this book. For example,
for the one-dimensional harmonic oscillator discussed in Section 11.6.2, “Harmonic
170 Ideal and Nonideal Gases
and Anharmonic Oscillators,” the energy levels are given by the equation (4.20). In
general, by equations (11.198) and (8.22), the one-particle internal energy is
∂ 1 ∂ZQM
U1 (T) = k T 2 ln ZQM = k T 2
∂T ZQM ∂T
" #
∂ X Eα
2 1
= kT exp −
ZQM ∂T α kT
Eα Eα
1 X
= k T2 exp −
ZQM α k T k T2
Eα
X
X 1
= Eα exp − = Eα Pα , (11.199)
α
ZQM kT α
that is,
X
U1 (T) = Eα Pα , (11.200)
α
with
Eα
1
Pα = exp − . (11.201)
ZQM kT
The equation (11.201) suggests that the quantity Pα is the probability of finding the
quantum-mechanical system in the state with energy Eα . In accordance with the quan-
tities Pα being a set of probabilities, are the facts that these quantities are obviously
positive [see (11.201)], and that their sum is
Eα ZQM
X 1 X
Pα = exp − = = 1. (11.202)
α
ZQM α
kT ZQM
Eα
Pα ∼ exp − . (11.204)
kT
That is, the probability to find the system in the state α is proportional to the quantum-
mechanical Boltzmann factor exp[−Eα /kT]. In the limit T → 0, the probability of
finding the system in the ground state (minimum energy state, with energy E0 )
Ideal Monatomic Gases 171
approaches 1, whereas the probabilities of all other, excited states (with energies
Eα > E0 ) approach 0. Indeed, by the equation (11.201), we have
Pα (T) Eα − E0
= exp − → 0, (11.205)
P0 (T) kT
−1
Eα − E0
X
P0 = 1 + exp − → 1, (11.207)
kT
α6=0
whereas Pα (T) → 0 for all excited states with α 6= 0. Thus, by the equation (11.203),
X X
U1 (T) = < Eα > = Eα Pα = E0 P0 + Eα Pα → E0 , (11.208)
α α6=0
that is, the internal energy approaches the ground-state energy for T → 0.
In view of the above discussions, it is clear that the exact quantum-mechanical treat-
ment is essential at low enough temperatures, when one needs to handle the sum over
the discrete quantum states carefully. This situation, however, changes with increasing
temperatures. For large enough temperatures, the terms in the quantum-mechanical
partition function (11.198) will vary slowly with increasing energy. This suggests that,
at large enough temperatures, the sum over all states α in the equation (11.198) may be
replaced by an integral. To see this, let us consider the one-dimensional system with
the Hamiltonian H1 (x, p). In Section 11.6.2, “Harmonic and Anharmonic Oscillators,”
we already wrote the approximate partition function for this system, in the form of the
integral
H1 (x, p)
Z Z
dx dp
Z= exp − . (11.209)
h kT
In the equation (11.209), there is a division by the Planck constant, yet, as illustrated in
Section 11.6.2, “Harmonic and Anharmonic Oscillators,” this feature does not affect
any of the interesting quantities, such as the internal energy U1 (T) = < Eα >. Let us
now try to understand the approximate result in the equation (11.209) in terms of the
exact quantum-mechanical partition function in the equation (11.198). For this pur-
pose, it is useful to think of the classical physics as of quantum mechanics taken in the
172 Ideal and Nonideal Gases
limit of zero Planck constant h → 0. Indeed, in this limit, the Heisenberg uncertainty
relation would tell us that
1x · 1p = h → 0. (11.210)
meaning that one would be able to simultaneously measure the position x and momen-
tum p with infinite precisions, i.e., 1x → 0 and 1p → 0, just as in classical physics.
In this limit, one can think of quantum states as of small cells in the two-dimensional
(x, p) phase space, each having the
Ecell
X
ZQM ≈ exp − . (11.212)
kT
cells
For a small h, the number of cells within the phase-space area element dx dp around
the point (x, p) is
dx dp
, (11.213)
h
and the energy of each of these states around the point (x, p) is
By the equation (11.213), we can replace the sum of cells by the integral
Z Z
X dx dp
⇒ . (11.215)
h
cells
Ecell
X
ZQM ≈ exp −
kT
cells
H1 (x, p)
Z Z
dx dp
≈ exp − . (11.216)
h kT
Ideal Monatomic Gases 173
Thus, we arrive at the important conclusion, that in the classical limit (formally for
h → 0), one has the approximation
Eα
X
ZQM = exp −
α
kT
H1 (x, p)
Z Z
dx dp
≈Z= exp − . (11.217)
h kT
This proves the validity of using the approximate partition function in the equation
(11.209) to study the classical limit in the one-dimensional case discussed in Section
11.6.2, “Harmonic and Anharmonic Oscillators.” For the three dimensional case, we
had, in Section 11.6.1, “General Maxwell–Boltzmann Distribution,”
d3 r d3 p H1 (Er, pE)
Z Z
Z= exp − . (11.218)
h3 kT
Er pE
This result can be derived in the classical limit along the same lines as the one for
the one-dimensional case. The only difference is that here the phase-space is six-
dimensional, and that, by the uncertainty relations, we have
Hence, in the equation (11.218), we have the division by h3 to count the number of
cells in the classical phase-space volume element
It should be stressed that the above conclusions about the classical limit do not depend
on the form of the Hamiltonian. Rather, they are all based on the equations such as
(11.210) or (11.219), which determine the cell volume in the appropriate phase space.
The classical limit of the N-particle problem with whatever form of the Hamiltonian
HN = HN (Er1 , pE1 ,Er2 , pE2 , ...,ErN , pEN ), can be handled in exactly the same way. In this
case, the cell volume is hd·N , for the particles moving in a d-dimensional space. The
classical limit of the exact quantum mechanical N-particle partition function is thus
given by
N Z Z d d
d ra d pa HN
Y
ZN = C exp − , (11.222)
hd kT
a=1 Er pE
a a
174 Ideal and Nonideal Gases
or
N Z
C HN
Z
d d
Y
ZN = d·N d ra d pa exp − . (11.223)
h kT
a=1 Er pE
a a
Here, the pre-factor C = 1, if the particles are not identical to each other, i.e., if one
deals with N different particles. If one deals with N identical particles, then, by the
discussions of Section 8.1, “Free Energy and Partition Function,” C = 1/N!. By a
similar discussion for a mixture of N1 particles of one kind with N2 particles of another
kind, one finds C = 1/(N1 ! N2 !), etc. In Chapter 13, we will use the equation (11.223)
to discuss nonideal classical gases of N interacting monatomic molecules in d = 3,
described by the Hamiltonian
N
X p2a
HN = + U (Er1 ,Er2 , . . .ErN ), (11.224)
2m
a=1
where the second term is a potential energy term dependent on all particle positions.
Finally, we note that the classical limit commonly coincides with the high-
temperature limit, as illustrated in the following chapters. Typically, there exists a
certain system dependent characteristic “quantum” temperature T ∗ , such that for the
temperatures T T ∗ one can ignore quantum effects and treat thermodynamics clas-
sically by means of partitions functions such as those in equations (11.209), (11.218),
or (11.223). Frequently, a more complex situation is realized, with several different
quantum temperatures. This is the case, for example, for diatomic gases discussed in
Chapter 12.
Solution
(a) Using the first law of thermodynamics, we can write
dQ = T dS = dU + p dV = m cV dT + p dV, (11.225)
Ideal Monatomic Gases 175
or
dT p
dS = m cV + dV. (11.226)
T T
Using now the thermal-state equation for the ideal monatomic gas
p Rg
=m , (11.227)
T V
we obtain
dT dV
dS = m cV + m Rg . (11.228)
T V
The entropy change in this process is then given by
ZTF ZVF
dT dV
1S = m cV + m Rg , (11.229)
T V
TI VI
or
TF VF
1S = m cV ln + m Rg ln . (11.230)
TI VI
(b) The result for the entropy change (11.230) is path-independent. Although the dif-
ferential dQ is an inexact differential, when it is multiplied by its integration factor
1/T, we obtain an exact differential dS = dQ/T. Thus, our result for the entropy
change is path-independent. This feature reflects the fundamental fact that the
entropy is a state function, S(N, V, T), so the entropy change can be expressed
purely in terms of the initial and final state (N, V, T). In particular, the above
result in the equation (11.230) can be obtained also from the expression for the
ideal gas entropy S(N, V, T) given by (11.81), simply by taking the difference
1S = S(N, VF , TF ) − S(N, TI , VI ) and using the elementary properties of the ln-
function.
Problem 2
A closed cylinder of total length L = 0.8 m is divided into two compartments by a
very light piston initially fixed at l1 = 0.3 m from the left cylinder base, as shown in
the Fig. 11.2.
In the left compartment, there is 1 mole of a monatomic ideal gas with pressure
p1 = 5 × 105 N/m2 , while in the right compartment there is some unspecified quantity
of another monatomic ideal gas with pressure p2 = 105 N/m2 . The cylinder is sub-
merged into the water, and the entire system is thermally insulated at the uniform
initial temperature TI = 298 K. If we release the piston, it moves to a new equilibrium
176 Ideal and Nonideal Gases
0.3 m 0.5 m
Gas 1 Gas 2
Water (H2O)
position. Assume that the walls of the cylinder are perfectly rigid, so the cylinder has
a constant volume. Also, assume that the volume occupied by the water is constant,
i.e., that the water confining container has perfectly rigid walls.
(a) Calculate the final temperature of the water.
(b) Calculate the final position of the piston.
(c) Calculate the increase of the total entropy of the system.
Solution
(a) Both gases are ideal monatomic gases and their thermal equation of state is given
by
m
pV = R T. (11.231)
M
Thus, for 1 mole of the first gas (n1 = 1), we obtain the initial volume
R TI 8.314 × 298
V1I = = = 0.00485 m3 . (11.232)
p1I 5 × 105
On the other hand, the geometry of the system gives that the volume of the second
gas is
5
V2I = V1I = 0.00808 m3 . (11.233)
3
From the equation of state, we find the number of moles of the second gas
This defines the initial state of the system. In the final state of the system, the
pressures of both gases are the same and the volume of the first gas must be three
times the volume of the second gas. The final temperature of both gases is also
equal (T1F = T2F = TF ).
Ideal Monatomic Gases 177
The next question to ask is, what is the final temperature of this entire system
made of two gases and the water? To answer this, let us apply the first law of ther-
modynamics to the entire system, 1Q = 1U + L. The entire system is thermally
insulated. Thus, 1Q = 0. Also, the entire system has a constant volume fixed by
the outer rigid walls of the water container (see the Fig. 11.2). So, the entire system
does zero work on its environment, and thus L = 0. So, 1U = 1Q − L = 0 − 0 =
0, i.e., the total internal energy of the entire system is constant in this process.
Next, our entire system here is composed of the two ideal gases and water, so
the net internal energy can be written as
3 3
U= N1 k T1 + N2 k T2 + Uw (Tw , Vw ) (11.235)
2 2
for any temperatures and volumes of the three parts of this entire system. A notable
feature of the above internal energy is that it does not depend on the volumes of the
ideal gases (which do change in this process). This feature (applying to ideal gases
only) gives rise to the above simple form for the entire system’s internal energy,
which is just a function of three variables (T1 , T2 , Tw ) that can (in principle) change
in this system (recall that the water volume is fixed). Thus, the result found above
1U = 0, i.e., UF = UI , can (by means of the above result for the entire system’s
internal energy) be written as
3 3
(N1 + N2 ) k TI + Uw (TI , Vw ) = (N1 + N2 ) k TF + Uw (TF , Vw ). (11.236)
2 2
V1 l1
= = 3, (11.237)
V2 l2
or
l1 l1 + l2 L L
+1 = = = 4 ⇒ l2 = = 0.2 m. (11.238)
l2 l2 l2 4
ZV2F ZV2F
p2 dV2
Z
dQ2 dV2
1S2 = = =R , (11.239)
T T2 3V2
V2I V2I
178 Ideal and Nonideal Gases
or
1 V2F
1S2 = R ln . (11.240)
3 V2I
V1F
Z
dQ1
1S1 = = R ln . (11.241)
T V1I
Thus, we obtain
1 V2F V1F
1S = 1S2 + 1S1 = R ln + R ln , (11.242)
3 V2I V1I
or
1 2 6 J
1S = R ln + R ln = 3.22 . (11.243)
3 5 3 K
Problem 3
An ideal monatomic gas of volume V is subject to an infinitesimal quasi-static process.
Derive the result for the heat transferred in this process and show that it equals to
cV cP
dQ = V dp + p dV, (11.244)
nR nR
N m
where n = NAV = M is the number of moles of the gas.
Solution
For an ideal monatomic gas we have pV = nRT and thereby
1
p dV + V dp = nR dT ⇒ dT = ( p dV + V dp). (11.245)
nR
Using (11.245), we obtain the change of the internal energy of the gas dU due to the
temperature change dT as follows:
cV
dU = cV dT = ( p dV + V dp). (11.246)
nR
cV
dQ = dU + p dV = ( p dV + V dp) + p dV, (11.247)
nR
Ideal Monatomic Gases 179
or
cV cV + nR
dQ = V dp + p dV. (11.248)
nR nR
On the other hand, for ideal monatomic gas, we have CP = CV + nR and the result
(11.248) finally becomes
cV cP
dQ = V dp + p dV, (11.249)
nR nR
Problem 4
Calculate the fraction of hydrogen molecules at zero altitude and at T = 300 K with
sufficient speed to escape the gravitational field of the Earth.
Solution
The so-called escape velocity is the initial speed ve of a massive particle required to
go from an initial point r in a gravitational potential field to infinity r → ∞ with a
residual speed equal to zero vf = 0. Thus, the final mechanical energy of the particle
is equal to zero. From the energy conservation law, we can write
mv2e GMm
− = 0, (11.250)
2 r
where g = 9.81 ms−2 . The probability density for speeds of molecules of an ideal
monatomic gas is given by (11.33), i.e.,
m 3/2
mv2
dω(v) = 4π v2 dv exp − = ν(v)dv. (11.253)
2π kT 2kT
180 Ideal and Nonideal Gases
The fraction of molecules having speeds larger than the escape velocity is then given
by
m 3/2 Z∞
mv2
f= 4π v2 dv exp − . (11.254)
2πkT 2kT
ve
we obtain
where
m
r
ve ≈ 6.9647. (11.257)
2kT
Z∞
4 2
f=√ w2 e−w dw ≈ 1.5 × 10−20 , (11.258)
π
6.9647
where we see that a very tiny fraction of all molecules have a sufficient speed to escape
the gravitational field of the Earth.
Problem 5
Calculate the average reciprocal speed < v−1 > of the molecules of mass m in an ideal
monatomic gas.
Solution
Using the probability density for speeds of molecules of an ideal monatomic gas, given
by (11.33), i.e.,
m 3/2
mv2
dω(v) = 4π v2 dv exp − = ν(v)dv, (11.259)
2π kT 2kT
Ideal Monatomic Gases 181
we obtain
m 3/2 Z∞
mv2
<v −1
>= 4π v dv exp − . (11.260)
2π kT 2kT
ve
m 3/2 Z∞
2kT 2
<v −1
>= 4π w e−w dw, (11.262)
2π kT m
0
or
m 1/2 Z∞ 2
<v −1
>= 2 e−w d(w2 ), (11.263)
2πkT
0
or finally
m 1/2 2m 1/2
<v −1
>= 2 = . (11.264)
2πkT π kT
Problem 6
In an absorption refrigerator, the cooling is obtained by mixing two gases at constant
pressure. Calculate the maximum reduction of the temperature that can be achieved by
mixing the same amounts of two ideal monatomic gases with pressure p and tempera-
ture T to a mixture with total pressure p.
Solution
The maximum reduction of the temperature is calculated using the second law of ther-
modynamics 1S ≥ 0. The entropy of an ideal monatomic gas is given by the result
(11.81), i.e.,
V 3 2π m k T
S = Nk ln + Nk 1 + ln + k N. (11.265)
N 2 h2
Using the thermal equation of state pV = NkT, we can rewrite (11.265) as follows:
kT 3 2π m k T
S = Nk ln + Nk 1 + ln + k N, (11.266)
p 2 h2
182 Ideal and Nonideal Gases
or
2π m k
5 3 2
S = Nk ln T − Nk ln p + Nk 1 + ln k + ln + k N. (11.267)
2 2 3 h2
In case of an ideal monatomic gas, the specific heat at constant pressure per constituent
particle is equal to cP = 5/2 k, and we can rewrite (11.267) as follows:
S( p, T ) = N cP ln T − Nk ln p + C, (11.268)
In the final state, after the mixing of the two gases the total pressure of the mix-
ture is still equal to p, and each of the gases contributes with equal partial pressure
( p1 = p2 = p/2). The temperature has changed to a new temperature TN . Since the
two components in the mixture still have the same pressure ( p/2) and the same tem-
perature TN , their contribution to the total entropy of the mixture is still the same.
Thus, the final state entropy is just double the entropy of any of the two components
p
SF = 2N cP ln TN − 2Nk ln + 2C. (11.270)
2
TN
1
1S = SF − SI = 2N cP − 2Nk ln ≥ 0. (11.271)
T 2
2/5
TN
1 1
cP ≥ k ln ⇒ TN ≥ T ≈ 0.76 T. (11.272)
T 2 2
The maximum reduction of the temperature is obtained when the entropy change is
zero (1S = 0) and in such a case TN ≈ 0.76 T, or 1Tmax = TN − T ≈ 0.24 T.
Ideal Monatomic Gases 183
Problem 7
Joule–Kelvin cooling describes the temperature change of a gas or liquid when it is
forced through a heat-insulated valve so that no heat is exchanged with the environ-
ment. This process is sometimes called a throttling process. During Joule–Kelvin cool-
ing, the enthalpy of the substance remains constant.
Consider an ideal monatomic gas (e.g., a noble gas like Helium or Neon at room
temperature) that is throttled through a heat-insulated valve so that its pressure is
reduced from p1 = 2 × 105 Pa to p2 = 5 × 104 Pa. If the initial temperature of the gas
was equal to TI = 300 K, calculate the new temperature TN .
Solution
The enthalpy for an ideal monatomic gas is given by the result (11.84), i.e.,
3 5
H = U + pV = NkT + NkT = NkT. (11.273)
2 2
Now, we see that the enthalpy is not dependent on the pressure of the gas and depends
only on its temperature. The condition that the enthalpy remains constant in the Joule–
Kelvin cooling process (H = Constant) therefore implies that the temperature of the
gas remains constant. Thus, the new temperature is TN = TI = 300 K.
Problem 8
Consider an ideal gas inside a vertical cylinder with the height L and the base area
AB . So, for the N molecules inside the cylinder, their z-co-ordinates are within the
range 0 < z < L. The molecules move in an external potential V(Er) = V(z) acting on
all molecules. Note that this potential depends on the z-co-ordinate only.
Use general thermodynamic principles to calculate the local pressure exerted by the
gas on the upper base of the cylinder. Show that this pressure can be expressed as
p(z = L) = n(z = L) · k T, (11.274)
Solution
The force and the pressure exerted on the piston can be obtained from the general
result (8.42) by noting that V = AB · L. Thus, we have
1 ∂FN k T ∂ ln ZN
p(z = L) = − = . (11.275)
AB ∂L T AB ∂L T
184 Ideal and Nonideal Gases
Here, the gas free energy is given by FN = −k T ln ZN , with the N-particle partition
function ZN as in the equation (11.107), i.e.,
ZN
ZN = ⇒ ln ZN = N ln Z − ln(N!). (11.276)
N!
By the equations (11.275) and (11.276), we thus have
NkT ∂ ln Z
p(z = L) = . (11.277)
AB ∂L T
By noting that ZKIN in the equation (11.143) is a function of temperature only and does
not depend on L, by equations (11.277) and (11.278), we have
NkT ∂ ln ZPOT
p(z = L) = , (11.279)
AB ∂L T
or
NkT 1 ∂ZPOT
p(z = L) = . (11.280)
AB ZPOT ∂L T
ZL
V(Er) V(z)
Z Z Z
3
ZPOT = d r exp − = dx dy dz exp −
kT kT
Er 0
ZL
V(z)
= AB dz exp − . (11.281)
kT
0
ZL
V(z)
ZPOT = AB dz exp − . (11.282)
kT
0
ZL
∂
dz f (z) = f (z = L), (11.283)
∂L
0
Ideal Monatomic Gases 185
we obtain
ZL
∂ZPOT ∂ V(z) V(z = L)
= AB dz exp − = AB exp − . (11.284)
∂L ∂L kT kT
0
NkT 1 ∂ZPOT
p(z = L) =
AB ZPOT ∂L T
NkT 1 V(z = L)
= exp − . (11.285)
AB ZPOT kT
That is,
NkT 1 V(z = L)
p(z = L) = exp − . (11.286)
AB ZPOT kT
On the other hand, for V(Er) = V(z), by the Boltzmann formula (11.154), we have
N V(z)
n(z) = exp − , (11.287)
ZPOT kT
yielding
N V(z = L)
n(z = L) = exp − . (11.288)
ZPOT kT
From the equations (11.286) and (11.188), it is obvious that the local pressure in
(11.286) can be expressed as
Thus, we have proved the equation (11.274), and in this way, we also confirmed the
statement made in the equation (11.167).
12 Ideal Diatomic Gases
In this chapter, we consider the statistical thermodynamics of very dilute (ideal) gases
of diatomic molecules, such as, for example, CO or HCl molecules. For such gases,
the contributions from the rotational and vibrational degrees of freedom of the gas par-
ticles should be taken into account in the calculations of the thermodynamic quantities
such as the experimentally significant specific heats. For simplicity, we will ignore the
presence of the spins of the two nuclei constituting the molecule. Also, we will con-
sider the nuclei as two distinguishable particles, as appropriate for the heteronuclear
molecules, such as CO or HCl, and comment on the situation for the homonuclear
molecules, such as O2 or N2 . As discussed below, a single diatomic molecule partition
function can be represented as the product of three terms,
Here, ZTR originates from the molecule’s center of mass translation, and it has the same
form as for monatomic molecules discussed in Chapter 11, “Ideal Monatomic Gases.”
On the other side, the terms ZROT and ZVIB in the equation (12.1) originate, respec-
tively, from the molecules’ rotations and vibrations. To derive the equation (12.1), we
recall the discussions of Chapters 3 through 5, by which a diatomic molecule made
of two atoms with masses m1 and m2 can be envisioned as composite system consist-
ing of a particle with total mass mmolecule = m1 + m2 (moving along with molecule’s
center of mass) combined with an internally moving subsystem executing rotational
and vibrational motions. Energy states of this composite system are labeled by the six
quantum numbers: nx , ny , nz (describing the translational motion of the molecules
center of mass), l, m (describing the molecules rotational motion, see Chapter 5,
“Kinetic Energy of Rotations”), and n (describing bond vibrations of the molecule, see
Chapter 4, “Energy of Vibrations”). The energy of this state is, by the discussions of
Chapters 3 through 5, given by
with
h2 2
ETR nx , ny , nz = 2 2
,
n x + n y + n z (12.3)
8mV 2/3
~2
1
EROT (l, m) = l(l + 1), EVIB (n) = ~ω n + . (12.4)
2I 2
The corresponding molecule’s partition function Z is a sum over all possible states,
i.e., over all possible values of the quantum numbers nx , ny , nz , l, m, and n, of the
form
∞ X ∞ X ∞ X ∞ X +l X ∞
" #
X E nx , ny , nz , l, m, n
Z= exp − . (12.5)
kT
nx =0 ny =0 nz =0 l=0 m=−l n=0
Using the standard manipulations with multiple sums, and the above additive form
of E nx , ny , nz , l, m, n , in which the contributions from translations, rotations, and
vibrations simply add to each other, one can easily see that the partition function Z
indeed has the multiplicative form displayed in (12.1), with
∞ X
∞ X
∞
" #
X ETR nx , ny , nz
ZTR = exp − , (12.6)
kT
nx =0 ny =0 nz =0
∞ X
+l ∞ X
+l
EROT (l, m)
X 2
X ~ l(l + 1)
ZROT = exp − = exp −
kT 2IkT
l=0 m=−l l=0 m=−l
∞ 2
X ~ l(l + 1)
= (2l + 1) exp − , (12.7)
2IkT
l=0
and
∞ ∞
EVIB (n) ~ω
X
X 1
ZVIB = exp − = exp − n+ . (12.8)
kT kT 2
n=0 n=0
Combining the above relation with the equation (8.22), we readily obtain that the inter-
nal energy of an ideal diatomic gas has the additive form
with
∂
UX = NkT 2 (ln ZX )V , (12.11)
∂T
where X ∈ {TR, ROT, VIB}. Obviously, the diatomic gas internal energy per unit mass
and the gas specific heat also have the additive forms
and
We note that the above translational partition function ZTR is identical to the one dis-
cussed in the Chapter 11, and displayed in the equation (11.26). It can be thus directly
adopted here,
3/2
2πmmolecule kT
ZTR = V , (12.14)
h2
with mmolecule = m1 + m2 , the total mass of the diatomic molecule. In this chapter, we
thus focus our attention on the here derived rotational ZROT and the vibrational ZVIB
partition functions, and their corresponding contributions to the specific internal ener-
gies and specific heats in the equations (12.12) and (12.13). From the above expres-
sions for ZROT and ZVIB , it is clear that these two partition functions do not depend on
the system volume V. This is physically unsurprising, in view of the fact that these two
partition functions originate from the molecule’s microscopic internal motions, which
are unaffected by the macroscopic quantities such as the gas container volume V. On
the other hand, the translational motion of the molecule’s center of mass does sense
the magnitude of V, and because of this, the above-displayed translational partition
function ZTR does depend on the gas volume. There is an important consequence of
these facts: molecular vibrations and rotations do not affect the pressure exerted by an
ideal diatomic gas on the walls of its confining container. In other words, the thermal
equation of state of an ideal diatomic (and, for that mater, polyatomic) gas has exactly
the same form as for the monatomic gas, that is,
pV = NkT, (12.15)
where N stands for total number of molecules, no matter whether they are monatomic,
diatomic, or, in general, polyatomic with whatever number of atoms. This fact is
easily derived from the general formula for an ideal gas free energy F in (8.1), by
calculating the gas pressure p via the general formula (8.42) that expresses p in
terms of the derivative of F with respect to V. Using these formulas with ln Z =
ln ZTR + ln ZROT + ln ZVIB and recalling that ZROT and ZVIB do not depend on the sys-
tem volume V, whereas ZTR has the same form as for monatomic gases, one easily
deduces that the pressure of a polyatomic gas must be given by the same law we had
before for monatomic gases. This law can then be written as
p = nkT, (12.16)
with n = N/V, the molecular number density. A notable feature of this result is that the
pressure does not depend on how large individual molecules are. That is, the pressure
does not depend on the molecular mass. Rather, for the pressure of dilute molecular
gases, the only decisive factor is the number of molecules per unit volume, n = N/V,
and, of course, the gas temperature T.
190 Ideal and Nonideal Gases
Finally, we note that, because the ZTR has the same form as for monatomic gases,
one easily deduces, by (12.11), that the translational contribution to the internal energy
of a polyatomic gas must be given by the same law we had before for monatomic gases,
that is,
3
UTR = NkT. (12.17)
2
This yields the specific internal energy due to translations given by
UTR 3
uTR = = Rg T, (12.18)
mgas 2
indicating that the translational contribution to the specific heat at constant volume is
the constant,
∂uTR
3
cVTR = = Rg , (12.19)
∂T V 2
~2
TROT = . (12.21)
2Ik
Because of the (relative) smallness of the Planck constant, this temperature is typically
small for realistic diatomic gases. For example, for the HCl molecule, TROT = 15.2 K,
whereas for the N2 molecule, TROT = 2.86 K. In practical applications, one is thus typ-
ically interested in the high-temperature regime T TROT . In this regime, the terms in
the above-written partition function sum change slowly with increasing l, so the sum
can be calculated accurately by replacing it with an integral over l,
Z∞
TROT
ZROT ≈ dl(2l + 1) exp − l(l + 1) . (12.22)
T
0
Ideal Diatomic Gases 191
Z∞
TROT T
ZROT ≈ dλ exp − λ = . (12.24)
T TROT
0
As noted in the introductory part of this chapter, the rotational contribution to the
internal energy of the system is
∂
UROT = NkT 2 [ln (ZROT )], (12.25)
∂T
or
∂
T
UROT ≈ NkT 2 ln = NkT, (12.26)
∂T TROT
in the high-temperature limit T TROT . Note that the above result for UROT does
not depend on the value of the Planck constant. In view of this, the high-temperature
limit represents also the classical limit. In this respect, it is illuminating to note that
in the formal limit of zero Planck constant (reducing quantum to classical mechanics),
the above-defined TROT would also go to zero, meaning that the classical results for
UROT in (12.26) would hold at any temperature (as has to be expected, since quantum
mechanics reduces to classical mechanics for zero Planck constant). In reality, the
Planck constant is not zero, yet it is relatively small, giving rise to typically small
values of TROT , as mentioned above.
In the high-temperature limit, the specific internal energy due to rotations is given
by
UROT
uROT = = Rg T, (12.27)
mgas
indicating that the rotational contribution to the specific heat at constant volume is a
constant,
∂uROT
cVROT = = Rg . (12.28)
∂T V
We note that equations (12.26) through (12.28) apply also to polyatomic molecules
gases, in the classical limit. In this limit, nuclear spins and the effects of indistinguish-
ability of identical nuclei in homonuclear diatomic molecules (as discussed in Section
6.1, “Introduction and Definitions”) disappear. Thus, in the classical high-temperature
limit, the equations (12.26) through (12.28) apply both to heteronuclear (e.g., HCl,
CO) and homonuclear (e.g., N2 , O2 ) diatomic gases.
192 Ideal and Nonideal Gases
~ω
TVIB = . (12.30)
k
Due to relatively large angular frequencies ω, this temperature is typically large for
realistic diatomic gases (in spite the “smallness” of the Planck constant). For example,
for the HCl molecule, TVIB = 4140 K, whereas for the N2 molecule, TVIB = 3340 K.
In practical situations, we are normally interested in the temperatures T < TVIB . Thus,
one is frequently interested in the low-temperature behavior of the vibrational par-
tition function ZVIB . On the other side, much like in the discussions we had in the
Section 12.1, “Rotations of Gas Particles,” the high-temperature limit T TVIB is the
classical limit in which we can replace the sum in ZVIB by an integral to obtain
Z∞ Z∞
TVIB 1 TVIB TVIB
ZVIB ≈ dn exp − n+ = exp − dn exp − n
T 2 2T T
0 0
TVIB T T
= exp − ≈ , (12.31)
2T TVIB TVIB
where we used the fact that exp(x) ≈ 1 for x 1. Thus, in the high-temperature limit,
T TVIB ,
T
ZVIB ≈ . (12.32)
TVIB
With TVIB as in (12.30), we see that the equation (12.32) agrees with the classical pre-
diction for the single harmonic oscillator partition function in the equation (11.195)
of Section 11.6.2, “Harmonic and Anharmonic Oscillators.” As noted in the intro-
ductory part of this chapter, the vibrational contribution to the internal energy of the
system is
2 ∂ 2 ∂
T
UVIB = NkT [ln (ZVIB )] = NkT ln = NkT (12.33)
∂T ∂T TVIB
Ideal Diatomic Gases 193
in the high-temperature limit T TVIB . Note that the above result for UVIB does not
depend on the value of the Planck constant. In view of this, the high-temperature limit
represents also the classical limit. In fact, the above result has been anticipated before
in Sections 11.4.6, “Equipartition Theorem,” and 11.6.2, “Harmonic and Anharmonic
Oscillators,” on the basis of equipartition theorem applied to the system of N classical
harmonic oscillators.
In the high-temperature limit, the specific internal energy due to vibrations is
given by
UVIB
uVIB = = Rg T, (12.34)
mgas
indicating that the vibrational contribution to the specific heat at constant volume
approaches the constant,
∂uVIB
cVVIB = = Rg , (12.35)
∂T V
∞
X 1
al = , |a| < 1, (12.36)
1−a
l=0
the vibrational partition function ZVIB can be calculated exactly at any temperature T
as follows:
TVIB l
TVIB X
ZVIB = exp − exp −
2T T
l
exp − T2T
VIB
exp T2T
VIB
= = . (12.37)
1 − exp − TVIB
T exp TVIB
T −1
As noted in the introductory part of this chapter, the vibrational contribution to the
internal energy of the system is
∂
UVIB = NkT 2 [ln (ZVIB )]. (12.38)
∂T
194 Ideal and Nonideal Gases
Substituting here the exact ZVIB from (12.37), we obtain the exact UVIB as follows:
TVIB
∂ exp 2T
UVIB = NkT 2 ln
∂T
TVIB
exp T − 1
∂ TVIB
TVIB
= NkT 2 − ln exp −1
∂T 2T T
T exp TVIB
T
T
VIB VIB
= NkT 2 − 2 − − 2
2T TVIB
exp T − 1 T
exp TVIBT 1
= NkTVIB − , (12.39)
exp TVIB
T −1 2
exp(x) 1 1 1
− = + , (12.41)
exp(x) − 1 2 2 exp(x) − 1
where
~ω ~ω
Uosc = + (12.43)
2 exp ~kTω − 1
~ω ~ω ~ω
Uosc ≈ + ~ω exp − → for T → 0, (12.44)
2 kT 2
Ideal Diatomic Gases 195
meaning that, in the zero-temperature limit, the internal energy reduces to the
quantum-mechanical ground-state energy of the harmonic oscillator. In this limit, the
probabilities of all excited states (n = 1, 2, 3, . . .) [with the energies En = (n + 1/2)~ω]
approach zero, and the system approaches its ground state with n = 0. On the other
hand, in the high-temperature limit T TVIB , or equivalently ~ω kT, by using
exp(x) ≈ 1 + x + x2 /2, for x = ~ω/kT 1, one finds by the equation (12.43) that
Uosc ≈ kT. This means that the single-oscillator internal energy approaches its clas-
sical value predicted by the equipartition theorem (see Section 11.6.2, “Harmonic and
Anharmonic Oscillators”). So, the high-temperature limit is also the classical limit. In
view of the form of the energy levels for the harmonic oscillator in the equation (4.21),
~ω
En = + n · ~ω, (12.45)
2
it is illuminating to write the equation (12.43) as
~ω
Uosc =< En >= + < n > ·~ω, (12.46)
2
with
1
< n >= . (12.47)
~ω
exp kT −1
The equations (12.46) and (12.47) best relate the oscillator thermodynamics to our
discussions of photons or phonons in Chapter 17, “Photon Gas in Equilibrium,” and
Chapter 18, “Other Examples of Boson Systems,” respectively. Indeed, the n-th state
of the oscillator may be interpreted as a state with n photons (or phonons) present, each
having the energy ~ω, such that the total energy is n · ~ω. The average number of these
photons (or phonons) < n > is given by the equation (12.47), so they contribute to the
internal energy of the system by the amount equal to < n > ·~ω corresponding to the
second term in the equation (12.46). The first term in the equation (12.46), emerging
from the oscillator ground-state energy
~ω
En=0 = , (12.48)
2
is frequently called the vacuum energy (or zero-point energy), as it corresponds to
the zero-temperature situation with no photons (or phonons) present. This seem-
ingly strange contribution to the internal energy may be of interest in some physical
problems (see Chapters 17 and 18).
Let us now return to our N diatomic molecules ideal gas and calculate the vibra-
tion energy contribution to the gas specific heat. It is obtained from uVIB using the
definition
∂uVIB
cVVIB = . (12.49)
∂T V
196 Ideal and Nonideal Gases
or finally
TVIB
2 exp TVIB
T
cVVIB (T) = Rg i2 . (12.51)
T
h
TVIB
exp T − 1
From the equation (12.51), we see that the vibrational contribution to the specific heat
is not constant, but rather a function of temperature. At low temperatures, the vibra-
tional specific heat tends to zero, i.e., we have
2
TVIB TVIB
cVVIB (T → 0) → Rg exp − → 0. (12.52)
T T
Thus, the vibrational effects in ideal polyatomic gases are significant only at higher
temperatures. In the high-temperature limit, we can put exp(TVIB /T) → 1 in the
numerator of the equation (12.21) and exp(TVIB /T) → 1 + TVIB /T in the denomi-
nator of the equation (12.21). Thus, we obtain the classical limit for the vibrational
contribution to the specific heat as follows:
2
TVIB 1
cVVIB (T) = Rg 2 = Rg , T TVIB . (12.53)
T
TVIB
T
This result is in accordance with the previously discussed result for this quantity in the
classical limit, whence the result UVIB = NkT applies.
Finally, let us consider the diatomic molecules ideal gas at realistic temperatures
above the typically low rotational temperature TROT . By using the equation (12.13)
(additivity of specific heats) and the results for the translational, rotational, and vibra-
tional specific heats discussed in this chapter, the total specific heat at constant volume
for an ideal diatomic gas is given by
5
TVIB
2 exp TVIB
T
cV (T) = Rg + i2 , (12.54)
2 T
h
exp TVIB
T −1
Unlike diatomic molecules, polyatomic molecules with more than two nuclei (e.g.,
CH4 or NH3 , or polymers) have more than one vibrational mode. Different vibrational
modes have different frequencies and, by the equation (12.13), different characteristic
quantum temperatures. For the case of polyatomic molecules, the last term in (12.54)
is simply replaced by a sum of such terms, over all modes. Thus, in the classical
high-temperature limit, the specific heat at constant volume is given by cV = (5/2 +
NVIB )Rg , where NVIB is the total number of the vibrational modes of the polyatomic
molecule.
p21 p2 mω2 2
H= + 2 + x1 + x22 . (12.55)
2m 2m 2
(a) Derive the expression for the energy levels of the system.
(b) Derive the expression for the partition function of the system, if the two particles
are bosons.
(c) Derive the expression for the partition function of the system, if the two particles
are fermions.
Solution
(a) The total energy of the two uncoupled harmonic oscillators is given by
1 1
En1 n2 = ~ω n1 + + ~ω n2 + (12.56)
2 2
or
(b) The partition function of the system, if the two particles are bosons, is given by
X En1 n2
ZB = exp − , (12.58)
n1 ≤n2
kT
or
~ω
X
ZB = exp − (n1 + n2 + 1) , (12.59)
n1 ≤n2
kT
198 Ideal and Nonideal Gases
where both particles are allowed to be in the same state (n1 = n2 ). By dividing the
sum into two parts, one with n1 = n2 and the other with n1 < n2 , we can write
~ω ~ω
X X
ZB = exp − (n1 + n2 + 1) + exp − (n1 + n2 + 1) ,
n =n =n
kT n <n
kT
1 2 1 2
(12.60)
or
∞
~ω ~ω
X X
ZB = exp − (2n + 1) + exp − (n1 + n2 + 1) , (12.61)
kT n <n
kT
n=0 1 2
or
∞
~ω X 2~ω n ~ω
ZB = exp − exp − + exp −
kT kT kT
n=0
∞ ∞
~ω n1 ~ω n2
X X
× exp − exp − , (12.62)
kT kT
n1 =0 n2 =n1 +1
or
exp − ~kTω
~ω
ZB = + exp −
~ω kT
1 − exp − 2kT
∞ ∞
~ω n1 X ~ω j+n1 +1
X
× exp − exp − , (12.63)
kT kT
n1 =0 j=0
or
exp − ~kTω
2~ω
ZB = + exp −
~ω kT
1 − exp − 2kT
∞ ∞
~ω 2n1 X ~ω j
X
× exp − exp − , (12.64)
kT kT
n1 =0 j=0
or
exp − ~kTω
2~ω
ZB = + exp −
~ω kT
1 − exp − 2kT
1 1
× × , (12.65)
~ω
1 − exp − 2kT 1 − exp − ~kTω
Ideal Diatomic Gases 199
or
exp − ~kTω exp − ~kTω
ZB = × 1 + . (12.66)
~ω
1 − exp − 2kT 1 − exp − ~kTω
(c) The partition function of the system, if the two particles are fermions, is given by
X En1 n2
ZB = exp − , (12.68)
n1 <n2
kT
or
~ω
X
ZB = exp − (n1 + n2 + 1) , (12.69)
n1 <n2
kT
where the two particles are now not allowed to be in the same state (n1 6= n2 and
n1 < n2 ). Thus, we can write
∞ ∞
~ω X ~ω n 1 ~ω n2
X
ZB = exp − exp − × exp − ,
kT kT kT
n1 =0 n2 =n1 +1
(12.70)
or
∞ ∞
~ω X ~ω n 1 X ~ω j+n1 +1
ZB = exp − exp − × exp − ,
kT kT kT
n1 =0 j=0
(12.71)
or
∞ ∞
2~ω X ~ω 2n1 X ~ω j
ZB = exp − exp − × exp − . (12.72)
kT kT kT
n1 =0 j=0
Problem 2
Consider a thermodynamic system with two modes of vibration with vibration fre-
quencies ω and 2ω at a fixed temperature T. Determine the probability that the energy
of the system is lower than 4~ω.
Solution
The two modes of vibration have the energy spectra
1 1
En1 = ~ω n1 + , En2 = 2~ω n2 + . (12.74)
2 2
3
E00 = ~ω. (12.76)
2
3 5 7
E00 = ~ω, E10 = ~ω, E01 = E20 = ~ω. (12.77)
2 2 2
Thus, the probability that En1 n2 < 4~ω is the sum of probabilities for each of these
four states, i.e.,
The probability of an arbitrary state of the system Pn1 n2 is the probability of the
simultaneous occurrence of the two modes of vibration, given by the following product
1 En 1 En
Pn1 n2 = Pn1 · Pn2 = exp − 1 · exp − 2 . (12.79)
Z1 kT Z2 kT
On the other hand, for a single mode of vibration of frequency ω, the partition function
Z is given by
∞ ∞
~ω
X
X En 1
Z= exp − = exp − n+ , (12.80)
kT kT 2
n=0 n=0
Ideal Diatomic Gases 201
or
∞
~ω X ~ω n
Z = exp − exp − , (12.81)
2kT kT
n=0
or
~ω
exp − 2kT
Z= . (12.82)
1 − exp − ~kTω
Thus, we have
~ω ~ω
1
= 1 − exp − exp (12.83)
Z1 kT 2kT
and
2~ω ~ω
1
= 1 − exp − exp . (12.84)
Z2 kT kT
~ω ~ω
1
Pn1 n2 = exp − n1 + exp − (2n2 + 1)
kT 2 kT
~ω ~ω 2~ω ~ω
× 1 − exp − exp × 1 − exp − exp ,
kT 2kT kT kT
(12.85)
or
~ω ~ω 2~ω
Pn1 n2 = exp − (n1 + 2n 2) 1 − exp − × 1 − exp − .
kT kT kT
(12.86)
Thus, the final result for the probability that the energy of the system is lower than
4~ω is
where Era = (xa , ya , za ) is the position vector of the constituent particle labeled by index
a. The classical partition function for the N-particle system is given by (11.222), i.e.,
Z
1 EN
ZN = exp − d0, (13.2)
N! kT
0
where the dimensionless infinitesimal element of the 6N-dimensional phase space of
the entire system, with N constituent particles, is given by
" N #" N #
Y 4π p2 dpa Y
d0 = a
d xa dya dza . (13.3)
h3
a=1 a=1
Substituting (13.1) into (13.2), we obtain
N
!
p2a
Z
1 X U
ZN = exp − − d0, (13.4)
N! 2mkT kT
0 a=1
or
Z0N
ZN = Z0N × ZIN = × ZIN. (13.5)
N!
In the equation (13.5), the quantity Z0N = Z0N/N! is the partition function for the ideal
gas without particle interactions (U = 0), defined by
N N
!
VN p2a 4π p2 dpa
Z X Y
Z0N = exp − a
, (13.6)
N! 2mkT h3
0p a=1 a=1
or
N
Z∞
2 ZN
1 V p
Z0N = 3
exp − a 4πp2a dpa = 0 , (13.7)
N! h 2mkT N!
0
where
Z∞
p2 2πmkT 3/2
V
Z0 = 3 exp − a 4π p2a dpa = V . (13.8)
h 2mkT h2
0
Introducing the volume elements dVa = dxa dya dza for each particle, we obtain
Z
1 U
ZIN = N exp − dV1 dV2 . . . dVN . (13.10)
V kT
0V
From the equation (13.10), we see that for the ideal gas model, in which the U is set to
zero, we have ZIN = 1. Thus, in the absence of interparticle interactions, the N-particle
partition function in the equation (13.5) reduces to the ideal gas partition function in
the equation (13.11).
or
Z0N
F = −kT ln − kT ln ZIN , (13.12)
N!
or
or
Z0
F = −NkT ln − NkT − kT ln ZIN . (13.15)
N
Thus, the free energy of nonideal gases with particle interactions is given by
Z0
F = F0 + FI = −NkT ln − NkT − kT ln ZIN , (13.16)
N
where
" 3/2 #
V 2πmkT
F0 = −NkT ln − NkT (13.17)
N h2
is the free energy of the ideal gas and FI = −kT ln ZIN is the contribution to the free
energy emerging from the interactions of the constituent particles. For this contribu-
tion, by the equation (13.10), we have
Z
1 U
FI = −kT ln N exp − dV1 dV2 . . . dVN . (13.18)
V kT
0V
Using (13.19), we can add unity and subtract V N/V N within the logarithm on the right-
hand side of the equation (13.18), to obtain
Z
1 U
FI = −kT ln 1 + N exp − − 1 dV1 dV2 . . . dVN . (13.20)
V kT
0V
For weak interactions (with U12 = U12 (Er1 ,Er2 ) kT), and/or dilute gases (with a small
particle number density N/V), the first, unity term under the logarithm in the equa-
tion (13.23) dominates over the second term therein. Thus, we can use the approxima-
tion ln(1 + x) ≈ x, valid for x 1, to obtain
N 2 kT 1
Z
U12
FI = − exp − − 1 dV1 dV2 , (13.24)
V 2V kT
V1 ,V2
Nonideal Gases 207
or
N 2 kT
FI = B(T), (13.25)
V
where
Z
1 U12
B(T) = 1 − exp − dV1 dV2 . (13.26)
2V kT
V1 ,V2
Let us now assume that the interaction potential U12 = U12 (r) is a function of the
relative distance r = |Er2 − Er1 | between the two interacting particles only. In such a
case, we can express the coordinates of the two interacting particles Er1 and Er2 in terms
of the co-ordinates of their mutual center of mass ErCM and the co-ordinates of their
relative distance Er. Thus, we can write
∂(Er1 ,Er2 )
dV1 dV2 = dVCM dV, (13.29)
∂(ErCM ,Er)
where
∂Er ∂Er1
1 1 − 1
∂(Er1 ,Er2 ) ∂ErCM ∂Er 2
= 1.
= = (13.30)
∂(ErCM ,Er) ∂Er2 ∂Er2
1 + 1
∂ErCM ∂Er 2
Thus, we have dV1 dV2 = dVCM dV, and the equation (13.26) can be rewritten as
Z Z
1 U12 1
B(T) = 1 − exp − dV dVCM , (13.31)
2 kT V
V V
1
R
or, as V V dVCM = 1,
Z∞
1 U12
B(T) = 1 − exp − 4π r2 dr. (13.32)
2 kT
0
208 Ideal and Nonideal Gases
The equation (13.25) for FI in combination with the result (13.32), giving the so-called
second virial coefficient B(T), are the central results of the above-described perturba-
tive calculation of the nonideal gas free energy. For ideal gases, in the absence of
interparticle interactions, B(T) = 0, and the first-order perturbative correction to the
gas free energy displayed in (13.25) vanishes. In order to calculate B(T), we need to
know the detailed form of the interparticle interaction potential U12 = U12 (r). How-
ever, from some sound physical arguments, one can derive a very illuminating approx-
imation for B(T) in the equation (13.32) even without specifying the detailed form of
the interaction potential U12 = U12 (r). Indeed, realistic molecules are much like hard,
impenetrable balls with the radius r0 (hard-core radius). The centers of two such balls
cannot be brought to each other to a distance r smaller than 2r0 . This corresponds to a
positive repulsive U12 (r), which is essentially infinite for r less than 2r0 . Thus, in the
equation (13.32), we can set,
U12
exp − → 0, r ≤ 2r0 . (13.33)
kT
On the other hand for r > 2r0 , one typically has a relatively weak negative (attractive)
potential. Indeed, realistic molecules generally attract each other via the van der Waals
interactions with U12 (r) ∼ −1/r6 , for a large r. In the region r > 2r0 , for a weak U12 ,
we can use the approximation 1 − exp(−x) ≈ x, to obtain
U12 U12
1 − exp − ≈ , r > 2r0 . (13.34)
kT kT
Using the approximations (13.33) and (13.34), we can rewrite the result (13.32) as
follows:
Z2r0
1 U12
B(T) = 1 − exp − 4π r2 dr
2 kT
0
Z∞
1 U12
+ 1 − exp − 4π r2 dr, (13.35)
2 kT
2r0
or
Z2r0 Z∞ Z2r0 Z∞
1 2 1 U12 2 2 2π
B(T) ≈ 4π r dr + 4πr dr = 2π r dr + U12 r2 dr
2 2 kT kT
0 2r0 0 2r0
Z∞
r3 1 2π a
= 16π 0 − − U12 r2 dr = b − . (13.36)
3 T k T
2r0
Nonideal Gases 209
Since the interaction potential is negative U12 < 0 for r > 2r0 , the integral
Z∞
2π
a=− U12 r2 dr > 0 (13.37)
k
2r0
r03 r3
b = 16π = 4 × 4π 0 , (13.38)
3 3
i.e., the b is four times the volume of a constituent particle. Substituting (13.36) into
(13.25), we obtain
N 2 kT a N2k
FI = b− = (bT − a), (13.39)
V T V
or finally
Nb N 2 ka
FI = NkT − . (13.40)
V V
Equation (13.40) gives our final result for the free-energy contribution coming from
interactions in a dilute nonideal gas.
N 2 ka
Nb
− NkT ln V − − . (13.41)
V V
For a dilute nonideal gas, the total volume per particle V/N is much larger than four
times the volume of a single constituent particle b = 4 × 4π r03 /3. Thus, we have b
V/N or
Nb
1. (13.42)
V
210 Ideal and Nonideal Gases
The thermal-state equation for nonideal gases is now obtained using (8.42) as follows:
∂F N 2 ka
NkT
p=− = − 2 . (13.45)
∂V T V − Nb V
After rearranging the terms in the equation (13.45), we finally obtain the so-called van
der Waals thermal-state equation for nonideal gases in the form
N 2 ka
p + 2 (V − Nb) = NkT. (13.46)
V
In the absence of interactions, i.e., with no long-range attraction and with zero hard-
core radius r0 = 0, by equations (13.37) and (13.38), the constants a and b in (13.46)
vanish, and the van der Waals equation reduces to the familiar ideal gas law.
∂
U = kT 2 (ln ZN )V , (13.47)
∂T
or, in terms of the free energy F = −kT ln ZN ,
∂ F
U = −kT 2 . (13.48)
∂T kT V
U = U0 + UI , (13.49)
Nonideal Gases 211
∂ F0
3
U0 = −kT 2 = NkT, (13.50)
∂T kT V 2
∂ FI
UI = −kT 2
. (13.51)
∂T kT V
∂ 1 Nb N 2 ka N 2 ka
UI = −kT 2
NkT − =− . (13.52)
∂T kT V V V V
Thus, the caloric equation for dilute nonideal gases has the form
3 N 2 ka
U = U0 + UI = NkT − , (13.53)
2 V
where the second term is the energy contribution coming from interactions. Note that
UI /U0 ∼ N/V = particle number density, so for dilute (low-density) gases, the ideal
gas contribution U0 dominates over the interaction contribution UI .
3 Na
u = Rg T − Rg , (13.54)
2 V
where we used the relation Nk = mRg . The specific heat at constant volume, defined
by (9.55), is then calculated as follows:
∂u
3
cV = = Rg . (13.55)
∂T V 2
Thus, the specific heat at constant volume for dilute nonideal gases (13.55) is the same
as in the case of the ideal gas (11.95). The specific heat at constant pressure cP is a
more complex function of temperature and volume of the system and is not constant
as in the case of ideal gas. However, using the van der Waals thermal-state equation,
we can derive the relation between the two specific heats of a nonideal gas, described
212 Ideal and Nonideal Gases
by the van der Waals equation. Let us recall the general result (9.86) for a gas of an
arbitrary mass m, i.e.,
α2
m(cp − cV ) = TV , (13.56)
γ
and the definitions of the parameters α and γ , given by (9.26) and (9.41), respectively,
i.e.,
1 ∂V 1 ∂V
α= , γ =− . (13.57)
V ∂T P V ∂p T
we obtain
∂V ∂(V, T) ∂( p, V) ∂V ∂p
=− =− , (13.59)
∂T P ∂( p, T) ∂(T, V) ∂p T ∂T V
or
∂V ∂V ∂p
1 1
=− . (13.60)
V ∂T P V ∂p T ∂T V
∂p
α=γ . (13.61)
∂T V
Thus, we obtain
2
∂p
m(cp − cV ) = TVγ , (13.62)
∂T V
or
2
∂V ∂p
m(cp − cV ) = −T . (13.63)
∂p T ∂T V
The relation (13.63) is an alternative general relation between the two specific
heats, suitable for the analysis of nonideal gases. Using the thermal-state equation
for nonideal gases (13.45), we have
∂p
Nk
= , (13.64)
∂T V V − Nb
Nonideal Gases 213
and
−1 −1
∂V ∂p 2N 2 ka
NkT
= =− − . (13.65)
∂p T ∂V T (V − Nb)2 V3
−1 2
2N 2 ka
NkT Nk
m(cp − cV ) = T − . (13.66)
(V − Nb)2 V3 V − Nb
Rg
cp − cV = . (13.67)
1 − 2Na(V − Nb)2 /(TV 3 )
From the result (13.67), we see that, when the interaction potential tends to zero
U12 → 0 (a → 0), the relation between the two specific heats approaches the result
for an ideal gas (11.97), i.e.,
cp − cV = R g . (13.68)
Combining the results (13.55) and (13.67), we obtain the result for the specific heat at
constant pressure in the form
3 Rg
cp = Rg + . (13.69)
2 1 − 2Na(V − Nb)2 /(TV 3 )
where A = N 2 ka and B = Nb. If the gas expands freely with no heat exchanged with
the surroundings from the volume V to volume 2V, determine the temperature change
1T of the gas as a function of the initial volume V, the constant specific heat at con-
stant volume cV , and the two constants A and B in the thermal equation of state.
214 Ideal and Nonideal Gases
Solution
The gas is expanding freely, which means that it does not perform any work to the
surroundings (1L = 0), and it does not exchange any heat with the surroundings
(1Q = 0). From the first law of thermodynamics (1U = 1Q − 1L), we conclude that
the internal energy of the gas remains constant (1U = 0) during the expansion. Using
the differential formulation of the first law of thermodynamics (8.39), we can write
∂U ∂S
dU = TdS − pdV ⇒ =T − p. (13.71)
∂V T ∂V T
∂(T, S) ∂(S, T)
= = 1, (13.72)
∂( p, V) ∂(V, p)
we can calculate
∂S ∂(S, T) ∂(V, p) ∂p
= = = . (13.73)
∂V T ∂(V, T) ∂(V, T) ∂T V
Substituting (13.73) into (13.71) and using the equation of state (13.70), yields
∂U ∂p
RT A
=T −p = −p = 2. (13.74)
∂V T ∂T V V −B V
A
U(T, V) = − + f (T), (13.75)
V
where the unknown function f (T) is determined from the definition of the molar heat
capacity (since we have here 1 mole) at constant volume cV , i.e.,
∂U
cV = = f 0 (T) ⇒ f (T) = cV T + Constant. (13.76)
∂T V
A
U(T, V) = − + cV T + Constant. (13.77)
V
Unsurprisingly, the equation (13.77) is (after setting the Constant = 0) identical to
equation (13.53). The initial state (T1 , V) and the final state (T2 , 2V) have the same
internal energy, and we can write
A A
− + cV T 1 = − + cV T 2 . (13.78)
V 2V
Nonideal Gases 215
A
1T = T2 − T1 = − . (13.79)
2cV V
Problem 2
Consider 1 mole (Nk = R) of a nonideal gas described by the van der Waals equation
of state
A
p + 2 (V − B) = RT, (13.80)
V
Solution
Using again the identity (9.80), i.e.,
∂(T, S) ∂(S, T)
= = 1, (13.81)
∂( p, V) ∂(V, p)
∂S ∂(S, T) ∂(V, p) ∂p
R
= = = = . (13.82)
∂V T ∂(V, T) ∂(V, T) ∂T V V −B
R
dS = dV. (13.83)
V −B
Z6B Z6B
RT 6B − B
Q = TdS = dV = RT ln , (13.84)
V −B 3B − B
3B 3B
5
Q = RT ln . (13.85)
2
216 Ideal and Nonideal Gases
Problem 3
Consider 1 mole (Nk = R) of a nonideal gas described by the van der Waals equation
of state
A
p + 2 (V − B) = RT, (13.86)
V
where A = N 2 ka and B = Nb. The curves in p − V plane, for various values of T, have
a maximum and a minimum at the two points where (∂p/∂V)T = 0. At some critical
temperature T = TC , the maximum and the minimum merge into a single critical point
( pC , VC , TC ), where both (∂p/∂V)T = 0 and (∂ 2 p/∂V 2 )T = 0.
(a) Express A and B in terms of TC and VC .
(b) Express pC in terms of TC and VC .
(c) Write the van der Waals equation in terms of the dimensionless variables p1 =
p/pC , V1 = V/VC , and T1 = T/TC .
Solution
(a) From the equation of state (13.86), we can write
RT A
p= − 2. (13.87)
V −B V
Thus, we obtain
∂p
RTC 2A
=− + 3 = 0, (13.88)
∂V T=TC (VC − B)2 VC
and
∂ 2p
2RTC 6A
= − 4 = 0. (13.89)
∂V 2 T=TC (VC − B)3 VC
Hence, we have
2A RTC
= , (13.90)
VC3 (VC − B)2
and
6A 2RTC
= . (13.91)
VC4 (VC − B)3
9RTC 2VC
pC + = RTC , (13.95)
8VC 3
or
!
VC2
p + 3pC 2 (3V − VC ) = 3RT, (13.97)
V
or
!
V2
p V 3RTC T
+ 3 C2 3 −1 = , (13.98)
pC V VC pC VC TC
or
!
3 3RTC
p1 + 2 (3V1 − 1) = T1 . (13.99)
V1 pC VC
Problem 4
The free expansion of a gas is a process where the internal energy of the gas remains
constant. Consider 1 mole (Nk = R) of a nonideal gas described by the van der Waals
equation of state
!
VC2
p + 3pC 2 (3V − VC ) = 3RT, (13.101)
V
Solution
In order to calculate the temperature change 1T = T2 − T1 , we need to derive the
general result for (∂T/∂V)U of the freely expanding gas. From the first law of thermo-
dynamics
we obtain
∂U ∂S
=T − p. (13.103)
∂V T ∂V T
∂S ∂(T, s) ∂( p, V) ∂p
= = = , (13.104)
∂V T ∂(T, V) ∂(T, V) ∂T V
and
∂U ∂p
=T − p. (13.105)
∂V T ∂T V
to obtain
∂T 1 ∂U ∂p
1
=− =− T −p . (13.107)
∂V U cV ∂V T cV ∂T V
Nonideal Gases 219
3RT V2
p= − 3pC C2 , (13.108)
3V − VC V
and
∂p
3R
= . (13.109)
∂T V 3V − VC
Thus, we have
∂p V2
3RT 3RT
T −p = − + 3pC C2 , (13.110)
∂T V 3V − VC 3V − VC V
or
∂p VC2
T − p = 3pC . (13.111)
∂T V V2
∂T 3pC VC2
=− . (13.112)
∂V U cV V 2
3pC VC2
dT = − dV, (13.113)
cV V 2
or
ZT2 ZV2
3pC VC2 dV
dT = − . (13.114)
cV V2
T1 V1
Finally, we have
3pC VC2
1 1
1T = − < 0. (13.115)
cV V2 V1
From the result (13.115), we see that the temperature of the gas decreases (1T < 0) in
the course of the free expansion from volume V1 to a larger volume V2 .
220 Ideal and Nonideal Gases
Problem 5
The inversion curve for a nonideal gas, described by the van der Waals equation of
state, is obtained from the condition that the so-called Joule–Kelvin coefficient is equal
to zero, i.e.,
∂T
= 0, (13.116)
∂p H
where H = U + pV is the enthalpy of the gas. Derive the inversion curve for a van der
Waals gas, expressed in terms of the dimensionless variables p1 = p/pC , V1 = V/VC ,
and T1 = T/TC . Find p1 = p1 (T1 ) along the inversion curve.
Solution
The Joule–Kelvin coefficient can be calculated as
∂T ∂(T, H) ∂(T, H) ∂( p, T)
= =− , (13.117)
∂p H ∂( p, H) ∂(T, p) ∂( p, H)
or
" #−1
∂T ∂H ∂H ∂H
1
=− =− . (13.118)
∂p H ∂p T ∂T p cP ∂p T
∂H ∂S
=T + V. (13.119)
∂p T ∂p T
∂S ∂(T, S) ∂(V, p) ∂V
= =− =− , (13.120)
∂p T ∂(T, p) ∂(T, p) ∂T p
we obtain
∂H ∂V
= −T + V. (13.121)
∂p T ∂T p
∂V
T
− 1 = 0, (13.123)
V ∂T p
or
−1
∂V ∂p ∂p
T T
=− = 1, (13.124)
V ∂T p V ∂T V ∂V T
or
−1
∂p ∂p
V
− = 1, (13.125)
T ∂V T ∂T V
or
" #−1
∂p1 ∂p1
V1
− = 1. (13.126)
T1 ∂V1 T1 ∂T1 V1
8T1 3
p1 = − , (13.127)
3V1 − 1 V12
and
" #−1 −1
∂p1
8 3V1 − 1
= = , (13.128)
∂T1 V1 3V1 − 1 8
and
∂p1
24T1 6
=− + 3. (13.129)
∂V1 T1 (3V1 − 1)2 V1
or
3V1 3(3V1 − 1)
− = 1, (13.131)
3V1 − 1 4T1 V12
222 Ideal and Nonideal Gases
or
or
or
or
r
3V1 − 1 T1
=2 . (13.135)
V1 3
1
V1 = √ , (13.136)
3 − 2 T1 /3
or
√ p
p1 = −27 + 24 3 T1 − 12T1 , (13.139)
or
√ p
p1 = 9 − 12 3 − 2 3 T1 + T1 . (13.140)
Problem 6
Consider 1 mole (Nk = R) of a nonideal gas described by the van der Waals equation
of state
!
VC2
p + 3pC 2 (3V − VC ) = 3RT, (13.142)
V
where pC = ka/27b2 , VC = 3Nb, and TC = 8a/27b and determine the critical point,
where both (∂p/∂V)T = 0 and (∂ 2 p/∂V 2 )T = 0.
(a) Show that the pressure function p(V, T) can be expanded about the critical point
( pC , VC , TC ) as follows:
p = pC + c1 (T − TC ) + c2 (T − TC )(V − VC ) + c3 (V − VC )3 (13.143)
p − pC = c3 (V − VC )δ , (13.144)
and determine δ.
(c) When p lies on the phase boundary line near the critical point, defined by p − pC =
c1 (T − TC ), show that we have
Solution
(a) From the equation of state (13.142), we can write
3RT V2
p(V, T) = − 3pC C2 . (13.146)
3V − VC V
Developing this function in Taylor series about the critical point, we obtain
∂p ∂p
p(V, T) = p(VC , TC ) + (V − VC ) + (T − TC )
∂V C ∂T C
1 ∂ 2p ∂ p
2
+ (V − VC ) +
2
(T − TC )(V − VC )
2 ∂V C2 ∂V∂T C
1 ∂ 2p 1 ∂ 3p
+ (T − TC ) +
2
(V − VC )3 + · · · .
2 ∂T 2 C 6 ∂V 3 C
(13.147)
224 Ideal and Nonideal Gases
p = pC + c1 (T − TC ) + c2 (T − TC )(V − VC ) + c3 (V − VC )3 (13.148)
∂p ∂ p 1 ∂ 3p
2
c1 = , c2 = , c3 = . (13.149)
∂T C ∂V∂T C 6 ∂V 3 C
∂p ∂p
3R 3R
= ⇒ = (13.150)
∂T V 3V − VC ∂T C 2VC
∂ p
2
9R 9R
= − =− 2, (13.151)
∂V∂T C (3V − VC )2 C 4VC
and
∂p 6pC VC2
9RT
=− + , (13.152)
∂V T (3V − VC )2 V3
∂ 2p 18pC VC2
54RT
= − , (13.153)
∂V 2 T (3V − VC )3 V4
∂ 3p 72pC VC2
486RT
=− + . (13.154)
∂V 3 T (3V − VC )4 V5
At the critical point, we have RTC = 8pC VC /3, and the result (13.154) becomes
3R 9R 3pC
c1 = , c2 = − 2 , c3 = − 3 . (13.156)
2VC 4VC 2VC
p − pC = c3 (V − VC )3 ⇒ δ = 3. (13.157)
Nonideal Gases 225
0 = c2 (T − TC )(V − VC ) + c3 (V − VC )3 , (13.158)
or
r
c2
(V − VC ) = (TC − T)1/2 . (13.159)
c3
Problem 7
Consider the result for the free energy of the van der Waals model
" 3/2 #
N 2 ka
1 2π mkT
F = −NkT ln − NkT ln(V − Nb) − . (13.161)
N h2 V
T
n(1 − bn)2 = . (13.163)
2a
(c) Find the maximum of the expression on the left-hand side of the equation (13.163)
with respect to n, and show that it determines the critical temperature TC =
8a/27b.
Solution
(a) From the equation (13.161), we obtain
" 3/2 #
F N 2πmkT N V − Nb N 2
f = = − kT ln − kT ln − 2 ka, (13.164)
V V h2 V N V
226 Ideal and Nonideal Gases
or
" 3/2 #
2π mkT 1 na
f = −nkT ln − nkT ln − b nkT . (13.165)
h2 n T
(b) The pressure of a nonideal gas is obtained from the free energy as follows:
∂F N 2 ka
NkT
p=− = − 2 . (13.167)
∂V T V − Nb V
∂p ∂ 2F 2N 2 ka
NkT
= =− + = 0, (13.168)
∂V T,N ∂V 2 T,N (V − Nb)2 V3
∂ 2p ∂ 3F 6N 2 ka
2NkT
= = − = 0, (13.169)
∂V 2 T,N ∂V 3 T,N (V − Nb)3 V4
or
T 2Na T
= 3 ⇒ n(1 − bn)2 = , (13.170)
(V − Nb)2 V 2a
T 3Na T
= 4 ⇒ n(1 − bn)3 = . (13.171)
(V − Nb)3 V 3a
The first equation of the critical point (13.171) is identical to the equation that will
be derived in the following from the condition d2 f/dn2 = 0. Thus, the physical
significance of the condition (∂ 2 f/∂n2 )T = 0 is that it is an analog of the usual
condition (∂ 2 F/∂V 2 )T,N = 0. Similarly, the condition (∂ 3 f/∂n3 )T = 0 could also
be expected to be an analog of the condition (∂ 3 F/∂V 3 )T,N = 0. Thus, the two
conditions d2 f/dn2 = 0 and d3 f/dn3 = 0 are the conditions for the critical point in
this density-based formulation of the theory. Let us now show that the condition
d2 f/dn2 = 0 indeed leads to the result (13.171). We rewrite the result (13.166) as
follows:
3/2
2πmkT
f = −nkT ln + nkT ln n
h2
− nkT ln(1 − bn) + n2 ka. (13.172)
Nonideal Gases 227
2πmkT 3/2
df
= −kT ln + kT ln n + kT
dn h2
nbkT
− kT ln(1 − bn) + − 2nka. (13.173)
1 − bn
d2 f kT 2bkT nb2 kT
= + + − 2ka, (13.174)
dn 2 n 1 − bn (1 − bn)2
or
d2 f kT
= − 2ka = 0, (13.177)
dn2 n(1 − bn)2
or
T
n(1 − bn)2 = , (13.178)
2a
which is identical to the result (13.170) as required.
(c) Let us now examine the condition d3 f/dn3 = 0. Using (13.177), it becomes
d3 f kT d
3
=− 2 2
[n(1 − bn)2 ] = 0. (13.179)
dn [n(1 − bn) ] dn
It is easily seen that the condition d3 f/dn3 = 0 is equivalent to the condition that
the left-hand side of the equation (13.170), i.e., n(1 − bn)2 , has a maximum. Thus,
we obtain
d
[n(1 − bn)2 ] = (1 − bn)2 + 2n(1 − bn)(−b) = 0, (13.180)
dn
or
Since n 6= 1/b, we obtain the critical density nC = 1/3b. Substituting the result for
critical density nC into (13.178), we obtain
1 2 TC
1 8a
1−b = ⇒ TC = . (13.182)
3b 3b 2a 27b
Thus, we have obtained the correct result for the critical temperature.
Problem 8
An unknown substance has the thermal equation of state
pV = AT 3 , (13.183)
Solution
Using the general result (13.74) obtained in Problem 1, i.e.,
∂U ∂S ∂p
=T −p = T − p, (13.185)
∂V T ∂V T ∂T V
we obtain
∂U 3AT 3 2AT 3
= −p = . (13.186)
∂V T V V
∂U BT n
= . (13.187)
∂V T V
Comparison of the two results (13.186) and (13.187) shows that we must have n = 3
and B = 2A.
14 Quasi-Static Thermodynamic
Processes
Using here the first law of thermodynamics, i.e., du = dq − pdv, we further obtain
dh = dq = cP dT. (14.2)
In the p-V plane, an isobaric process is represented by a straight line parallel to the
V-axis, as shown in Fig. 14.1.
The quantity of heat exchanged in the process is then given by
Z2 Z2
l12 = pdv = p dv = p (v2 − v1 ). (14.4)
1 1
1 2
0 V1 V2 V
0
S
and the total change in the internal energy during an isobaric process is obtained as
follows:
dT
dq = Tds = cP dT ⇒ ds = cP . (14.7)
T
Integrating the equation (14.7), we obtain
T2 s2 − s1
s2 − s1 = cP ln ⇒ T2 = T1 exp . (14.8)
T1 cP
Z2
l12 = pdv ≡ 0. (14.9)
1
Thus, by the first law of thermodynamics, the change in the internal energy of the
system is equal to the heat added to the system,
p2 2
p1 1
0 V
232 Ideal and Nonideal Gases
For an ideal gas, the internal energy is a function of its temperature but not of its
volume (in the absence of the quantum effects discussed in Part Four of this book).
Thus, for such a system, the change of its internal energy during an isothermal process
is zero. As an example, for an ideal monatomic gas, we have u = 3/2 Rg T (in classical
limit). When T = Constant, we have u = Constant (du = 0). Thus, we may write
du = cV dT = 0 ⇒ du = dq − dl = 0. (14.14)
0 S
1 2
0 S1 S2 S
Quasi-Static Thermodynamic Processes 233
Thus, for ideal classical gases, the work performed during an isothermal process is
equal to the exchanged quantity of heat, and we have
For an isothermal process in the p-V plane, by the thermal-state equation T = T( p, v),
we have
∂T ∂T
dT = dp + dv = 0, (14.16)
∂p V ∂v P
∂p ∂T ∂( p, v) ∂(T, p)
dp = − dv = − dv
∂T V ∂v P ∂(T, v) ∂(v, p)
∂( p, T) ∂p
= dv = dv (14.17)
∂(v, T) ∂v T
as, of course, expected for T = Constant, from the thermal-state equation written in
the form p(T, V). Obviously, for any fluid, the function p = p(v) describing an isother-
mal process in the p-V plane is just the thermal-state equation p = p(v, T) with T =
Constant. For example, for ideal gases (in the absence of quantum effects discussed in
Part Four), an isothermal curve is given by
Rg T Constant
p = p(v) = = , T = Constant, (14.18)
v v
even for polyatomic ideal gases, as discussed in Chapter 12, “Ideal Diatomic Gases.”
On the other hand, for nonideal gases, isothermal curves can be frequently well
described by approximate state equations such as the van der Waals equation (13.45).
The function p = p(v) is shown in Fig. 14.6.
p1 1
p2 2
0 V1 V2 V
234 Ideal and Nonideal Gases
The work performed by an ideal classical gas during an isothermal process is easily
calculated as follows:
Z2 Z2
Rg T v2
l12 = pdv = dv = Rg T ln . (14.19)
v v1
1 1
dq = Tds = 0. (14.20)
Using the first law of thermodynamics for an ideal gas, with the result (14.20), we
obtain
Rg T
du = cV dT = −pdv = − dv, (14.21)
v
or
dT Rg dv dT cP − cV dv
+ = + = 0, (14.22)
T cV v T cV v
where we have used the result cP − cV = Rg valid for the classical ideal gas. Introduc-
ing here the ratio of the two specific heats of an ideal gas
κ = cP /cV , (14.23)
T
Figure 14.7 The adiabatic process in the T-S plane.
T2 2
T1 1
0 S
Quasi-Static Thermodynamic Processes 235
or
v p dT v p
dT = dp + dv ⇒ = dp + dv, (14.26)
Rg Rg T Rg T Rg T
or
dT dp dv
= + . (14.27)
T p v
dp dv dv dp dv
+ + (κ − 1) = + κ = 0. (14.28)
p v v p v
Thus, we finally obtain the equation of the adiabatic curve in the p-V plane as follows:
or
Constant
p = p(v) = , S = Constant. (14.30)
vκ
This curve in the p-V plane is similar to the one obtained in the case of an isothermal
process, but the adiabatic curve is steeper since, generally, κ = cp /cv > 1 (e.g., for
monatomic gases κ = 5/3). There is a simple physical reason for this: during an adia-
batic expansion (volume increase), the positive work done L > 0 must be accompanied
by a decrease of internal energy
1U = 1Q − L = −L < 0. (14.31)
Since U is an increasing function of T only (for classical ideal gases), the temperature
T must decrease during an adiabatic volume increase. This is possible only if the adi-
abatic curve is steeper than any member of the family of isothermal curves in the p-V
plane. The adiabatic curve in the p-V plane is shown in Fig. 14.8.
The work performed in an adiabatic process for an ideal gas is calculated using the
result
p1 vκ1
pvκ = p1 vκ1 = Constant ⇒ p = . (14.32)
vκ
236 Ideal and Nonideal Gases
p1 1
p2 2
0 V1 V2 V
Thus, we obtain
Z2 Z2
dv p1 vκ1 1−κ
l12 = pdv = p1 vκ1 = v − v1−κ
, (14.33)
vκ 1−κ 2 1
1 1
or finally
p1 vκ1 1−κ
l12 = v1 − v1−κ . (14.34)
κ −1 2
where n is an arbitrary constant. All the other quasi-static processes described thus far
are special cases of the polytropic process, i.e.,
1. For n = 0, the polytropic process is the isobaric process.
2. For n → ∞, the polytopic process is the isochoric process.
3. For n = 1, the polytropic process is the isothermal process.
4. For n = κ, the polytropic process is the adiabatic process.
The polytropic process concept is motivated by the following interesting mathematical
problem: in the p-V diagram, find the shape of the process curve along which the added
Quasi-Static Thermodynamic Processes 237
heat is given by
dq = cn dT, (14.36)
where cn is an arbitrarily given constant, the so-called polytropic specific heat. Let
us solve this problem for ideal classical gases. Using now the caloric-state equation
dq = du + pdv, with du = cV dT, we obtain for an ideal gas
Rg T
dq = cn dT = cV dT + pdv = cV dT + dv. (14.37)
v
Using Rg = cP − cV and rearranging, we obtain
dT dv
(cn − cV ) = (cP − cV ) , (14.38)
T v
or
dT (cP − cV ) dv
= . (14.39)
T (cn − cV ) v
Using here the general result (14.27), we have
dT dp dv (cP − cV ) dv
= + = , (14.40)
T p v (cn − cV ) v
or
cP − cV dv
dp
+ 1− = 0, (14.41)
p cn − cV v
or
dp cn − cP dv dp dv
+ =0⇒ + n = 0, (14.42)
p cn − cV v p v
The work performed in a polytropic process for an ideal gas is calculated using the
result
p1 vn1
pvn = p1 vn1 = Constant ⇒ p = . (14.45)
vn
238 Ideal and Nonideal Gases
Thus, we obtain
Z2 Z2
dv p1 vn1 1−n
l12 = pdv = p1 vn1 n
= v1 − v1−n
2 . (14.46)
v n−1
1 1
The meaning of the equation (14.47) is that the positive work extracted from the sys-
tem is equal to the net heat added to the system during the Carnot cycle. Since there
is no heat exchange with the surroundings during the two adiabatic processes, the net
heat added to the system during the Carnot cycle is equal to the difference between
the heat added to the system Q2 (during the isothermal process at T = T2 ) and the
heat removed from the system Q1 (during the isothermal process at T = T1 ), i.e.,
a Q2 b
T2
Q1
T1
d c
0 S1 S2 S
Quasi-Static Thermodynamic Processes 239
1QC = Q2 − Q1 . On the other hand, for these two isothermal processes depicted in
the T-S diagram, we can write down following the two relations as follows:
The thermal efficiency of any cyclic process is defined as the ratio between the
extracted work from the system 1LC and the heat added to the system Q2 , i.e.,
1LC Q2 − Q1
η= = , (14.50)
Q2 Q2
i.e.,
Q1
η = 1− . (14.51)
Q2
In the special case of the Carnot cycle, we can use the results (14.48), to obtain
T1
η = 1− . (14.52)
T2
Thus, the thermal efficiency of the Carnot cycle is fully determined by the constant
temperatures T1 and T2 of the two isothermal processes.
The major feature of any cyclic process is that there is no change of internal energy
U of the system after completing the full cycle. It is because the system returns to its
initial state. Thus, 1U = 0, and the first law of thermodynamics then predicts that the
work done by the system is equal to the net heat added to the system,
1L = 1Qnet . (14.53)
For any cyclic process, the net added heat energy can be written as
hence
Tmax
Tmin
0 Smin Smax S
done along the upper part of the loop in Fig. 14.10 (from Smin to Smax ). On the other
side, 1Q1 is the heat energy released from the system, given by the integral
Z
1Q1 = TdS, (14.57)
lower
done along the lower part of the loop in Fig. 14.10 (from Smin to Smax ). It is, thus,
obvious that the net work done by the system during any cyclic process,
Z Z
1L = 1Qnet = 1Q2 − 1Q1 = TdS − TdS, (14.58)
upper lower
is in general equal to the area enclosed by the cycle loop in the T-S diagram.
Any cyclic process is characterized by two important temperatures labeled in
Fig. 14.10 by Tmax and Tmin , being a maximum and a minimum temperature occuring
along the cycle, respectively. As T > Tmin , we have
Z SZmax
yielding the following fundamental result for the efficiency of any cycle as follows:
1Q1 Tmin
η = 1− < 1− . (14.65)
1Q2 Tmax
dU = 1U = 0,
H
or, as
I I
TdS = pdV = 1L. (14.68)
The above two loop integrals are nothing else but the areas enclosed by the loops in
the (T, S) and (p, V) planes,
Z Z Z Z
dTdS = dpdV = 1L. (14.69)
loop loop
242 Ideal and Nonideal Gases
The above areas, equality holds for any choice of loop. This can be true only if the
Jacobian of the mapping (T, S) ↔ ( p, V) is 1. Indeed, by the above equation,
∂(T, S)
Z Z Z Z Z Z
dTdS = dpdV = dpdV, (14.70)
∂( p, V)
any loop any loop any loop
or
∂(T, S)
Z Z
− 1 dpdV = 0. (14.71)
∂( p, V)
any loop
Since the equation (14.71) holds for any choice of the loop, we must have
∂(T, S)
= 1. (14.72)
∂( p, V)
Hence, the equation (9.80) follows from the first law of thermodynamics applied to
the cyclic processes.
Solution
This cyclic process can be represented by the p-V diagram shown in Fig. 14.11.
ΔL1
p1
a b
0 V1 V2 V
The initial and the final states of the gas in a cyclic process are the same. Thus, the
change in the internal energy is equal to zero (1U = 0). Using here the first law of
thermodynamics, we have
In the equation (14.73), the work 1LS is by convention work done by the gas on the
surroundings. The work done on the gas by the surroundings, i.e., by external agents,
is the same with the opposite sign (1LEXT = 1LG = −1LS ), and we can write
Thus, the heat that the gas gains after the above cyclic process is equal to minus the
work done on the gas, i.e.,
1Q = −1LEXT . (14.75)
In order to find the work done on the gas 1LEXT , we first note that the work done in
an isochoric process (dV = 0) is equal to zero. The work done by external agents on
the gas during the entire cyclic process is then equal to the sum of the work done on
the gas during the two isobaric processes
So, a positive amount of work is done by the external agent on the gas. Finally, the net
heat added to the gas during the above cyclic process is equal to
1Q = −1LEXT = − ( p1 − p2 ) (V1 − V2 )
= − ( p2 − p1 ) (V2 − V1 ) < 0. (14.77)
From the equation (14.77), we see that this heat is negative. This fact is associated
with the fact that the cycle loop is here oriented counter-clockwise in the p-V diagram.
Such systems operate as time-reversed engines, i.e., as heat pumps. They can thus be
used in home heating systems.
Problem 2
One mole of a monatomic ideal gas is subject to the cyclic process shown in Fig. 14.12.
4
B
3
A C
2
1
D
0 1 2 3 4
V (× 10−3 m3)
244 Ideal and Nonideal Gases
(a) Calculate the net work done by the gas during one cycle.
(b) Calculate the internal energy difference between states C and A.
(c) Calculate the heat absorbed by the gas moving between states A and C via the path
ABC.
Solution
(a) The equation of the circle describing the cyclic process in Fig. 14.12 is given by
p V
(σ − 2)2 + (ν − 2)2 = 1, σ= ,ν= , (14.78)
p0 V0
where p0 = 105 N/m2 and V0 = 10−3 m3 . The work done by the gas in one cycle
is defined by
I I
1L = p dV = p0 V0 σ dν. (14.79)
or
3
Z1
Z p p
1L = p0 V0 2 + 1 − (ν − 2)2 dν + 2 − 1 − (ν − 2)2 dν ,
1 3
(14.81)
or
Z3 Z3 p Z3 Z3 p
1L = p0 V0 2 dν + 1 − (ν − 2)2 dν − 2 dν + 1 − (ν − 2)2 dν .
1 1 1 1
(14.82)
Thus, we obtain
Z3 p
1L = 2p0 V0 1 − (ν − 2)2 dν. (14.83)
1
Quasi-Static Thermodynamic Processes 245
Z1 p
1L = 2p0 V0 1 − x2 dx. (14.84)
−1
Zπ/2
1L = 2p0 V0 cos2 θdθ, (14.85)
−π/2
or
Zπ/2
1
1L = 2p0 V0 (1 + cos 2θ ) dθ = π p0 V0 . (14.86)
2
−π/2
There is a much simpler way to calculate the net work done by the gas during one
cycle, if we remember that it is equal to the area of the cycle in the p − V plane.
Then, we can write
1L
= π r2 = π, (14.88)
p0 V0
or
(b) In the state A, we have the pressure pA = 2 × 105 N/m2 and the volume VA =
10−3 m3 . Using the equation of state, we obtain
pA VA 200 J
TA = = = 24 K. (14.90)
R 8.314 J/K
In the state B, we have the pressure pC = 2 × 105 N/m2 and the volume VC =
3 × 10−3 m3 . Using the equation of state, we obtain
pC VC 600 J
TC = = = 72 K. (14.91)
R 8.314 J/K
The internal energy difference between states C and A is then given by
ZC ZTC
1UAC = dU = cV dT = cV (TC − TA ) = 598 J. (14.92)
A TA
246 Ideal and Nonideal Gases
Z3 p
1LABC = p0 V0 2 + 1 − (ν − 2)2 dν, (14.94)
1
or
Z3 Z3 p
or finally
π
1LABC = p0 V0 4 + = 557 J. (14.96)
2
Problem 3
One mole of an ideal diatomic gas undergoes a quasi-stationary change of state from
A to C as shown in Fig. 14.13.
6
A
4
C
2
0 1 2 3 4
V (× 10−3 m3)
Solution
(a) Since we have one mole of the gas (m = M), we have Rg = R. Thus, for a diatomic
gas with five (3 + 2) degrees of freedom, we have
∂Q ∂U
5 J
cV = = = R = 20.785 . (14.98)
∂T V ∂T V 2 K
(b) The work done by the gas in the process ABC is given by
Z Z Z
1LABC = p dV = p dV + p dV. (14.99)
ABC AB BC
σ = 2ν + 4. (14.103)
or
(c) In the state A, we have the pressure pA = 6 × 105 N/m2 and the volume VA =
10−3 m3 . Using the equation of state, we obtain
pA VA 600 J
TA = = = 72 K. (14.108)
R 8.314 J/K
In the state B, we have the pressure pC = 4 × 105 N/m2 and the volume VC =
3 × 10−3 m3 . Using the equation of state, we obtain
pC VC 1200 J
TC = = = 144 K. (14.109)
R 8.314 J/K
ZC ZTC
1UAC = dU = cV dT = cV (TC − TA ) = 1497 J. (14.110)
A TA
Using the first law of thermodynamics, the heat absorbed by the gas in the process
ABC is given by
(d) The entropy change for 1 mole of an ideal gas in the reversible change of state is
given by
TF VF
1S = cV ln + R ln , (14.112)
TI VI
or
TC VC
1SAC = cV ln + R ln = cV ln 2 + R ln 3. (14.113)
TA VA
J
1SAC = 23.54 . (14.114)
K
Problem 4
An electric heat pump absorbs heat from the surrounding earth at the lower temper-
ature TO = 273 K and then delivers heat to the interior of a building at the higher
temperature TI = 298 K, as shown in Fig. 14.14.
Calculate the maximum energy supplied to the building per 1 joule of electrical
energy needed to operate the heat pump.
Quasi-Static Thermodynamic Processes 249
ΔQO
TO
2 3
0 SO SI S
Solution
The maximum energy supplied to the building is obtained if we assume that our pro-
cess is reversible, i.e.,
1QO 1QI
1S = + = 0. (14.115)
TO TI
By convention, the heat supply to the interior of the building is given by QS = −1QI ,
and we can write
Q23 QS
1S = − = 0. (14.116)
TO TI
The work performed by the electric motor of the heat pump is equal to the electric
energy spent in the process, i.e.,
Thus, we obtain
and
QS − δL QS δL
1 1
1S = − = QS − − = 0. (14.119)
TO TI TO TI TO
TI 298
QS = δL = δL ≈ 12 δL. (14.120)
TI − TO 298 − 273
Theoretically, for every joule of electric energy, we can expect 12 joules of heat sup-
plied to the building.
250 Ideal and Nonideal Gases
Problem 5
Two identical bodies, with heat capacity at constant pressure equal to cP , are used as
heat reservoirs for a heat engine. Initially, the temperatures of the two bodies are T1
and T2 , respectively. As a result of the operation of the heat engine, the bodies remain
at a constant pressure and reach a common final temperature TF .
(a) Calculate the work done by the engine in terms of the specified quantities cP , T1 ,
T2 , and TF .
(b) Using the second law of thermodynamics, derive the inequality relating the final
temperature TF to T1 and T2 .
(c) For given T1 and T2 , calculate the maximum work that can be obtained from the
engine.
Solution
(a) At constant pressure, the amounts of heat energy released from the two reservoirs
are
1Q1 = cP (T1 − TF ),
(14.121)
1Q2 = cP (T2 − TF ).
Because of the cyclic nature of heat engines’ operation, the first law of thermody-
namics is that the total heat energy released to an engine (after an integer number
of cycles) is equal to the work done by the engine. Thus,
(b) Because of the cyclic nature of heat engines’ operation, the change of the entropy
of the system is equal to the change of the entropy of the two reservoirs. It can be
calculated as follows:
ZTF ZTF
dQ1 dQ2 TF TF
1S = + = cP ln + cP ln . (14.123)
T T T1 T2
T1 T2
TF2
1S = cP ln ≥ 0, (14.124)
T1 T2
or
TF2 p
≥ 1 ⇒ TF ≥ T1 T2 . (14.125)
T1 T2
Quasi-Static Thermodynamic Processes 251
(c) The maximum work from the engine is obtained in case of a reversible process,
i.e., when the entropy change is equal to zero 1S = 0. In such a case, we have an
equality in the equation (14.125). Substituting (14.125) into (14.122), we obtain
p p p 2
1Lmax = cP T1 + T2 − 2 T1 T2 = cP T1 − T2 . (14.126)
Problem 6
A gasoline engine can be described by the idealized cyclic process shown in Fig. 14.15.
d
⇒ Q1
b ⇒ Q2
0 V1 V2 V
Solution
The efficiency of a process is defined as the ratio between the work performed by the
process 1L = Q1 − Q2 and the heat intake Q1 , i.e.,
Q1 − Q2 Q2
η= = 1− . (14.127)
Q1 Q1
Td − Ta
η = 1− . (14.130)
Tc − Tb
Thus, we have
κ−1 κ−1
Vc V1
Td = Tc = Tc , (14.132)
Vd V2
and
κ−1 κ−1
Vb V1
Ta = Tb = Tb . (14.133)
Va V2
Thus, we have
κ−1
V1
Td − Ta = (Tc − Tb ) . (14.134)
V2
Substituting (14.134) into (14.130), we finally obtain the efficiency of the cyclic pro-
cess described by Fig. 14.15, in terms of the quantities V1 , V2 , and κ = cP /cV as
follows:
κ−1
V1
η = 1− . (14.135)
V2
Problem 7
Determine the temperature T(z) of the Earth’s atmosphere as a function of altitude z
using the following assumptions:
1. The atmosphere can be described as an ideal gas with molar mass of M =
0.028 kg/mol and the ratio between the specific heats κ = CP /CV = 1.4.
2. There is a mechanical equilibrium, i.e., we have dp(z) = −n(z)mgdz, where n(z) is
the number density of the constituent particles and g = 9.81 m/s2 .
3. There is no heat transport in z-direction.
Quasi-Static Thermodynamic Processes 253
Solution
Using the thermal equation of state for an ideal gas, i.e.,
N
pV = NkT ⇒ p = kT ⇒ p(z) = n(z)kT(z), (14.136)
V
dp(z) mgdz
= d[ln p(z)] = − . (14.137)
p(z) kT(z)
The third condition of the problem implies that the entropy per particle is indepen-
dent on the altitude. In other words, the temperature change with the altitude can be
described as an adiabatic change such that the result (14.30) is valid, and we have
where C denotes a constant independent on any state variables. Using again the ther-
mal equation of state for an ideal gas, we get
or
κ mgdz
d[ln p(z)] = d[ln T(z)] = − , (14.141)
κ −1 kT(z)
or
dT(z) κ − 1 mgdz
=− , (14.142)
T(z) κ kT(z)
or
dT(z) κ − 1 mg
=− . (14.143)
dz κ k
Assuming that at the surface of the Earth (z = 0), we have T = T0 , we obtain the
temperature T(z) of the Earth’s atmosphere as a linear function of altitude z
κ − 1 mgz
T(z) = T0 − , (14.144)
κ k
254 Ideal and Nonideal Gases
or
κ − 1 Mgz
T(z) = T0 − . (14.145)
κ R
Using the actual values of the given numerical parameters κ = 1.4, M = 0.028 kg/mol,
g = 9.81 m/s2 , and R = 8.314 J/K mol, we obtain
K
T(z) = T0 − 0.0094395 × z. (14.146)
m
From the numerical result (14.146), we see that, in this model, the temperature of the
Earth’s atmosphere falls approximately 1 K every 100 m.
Problem 8
A cartridge of a volume V1 = 2 × 10−7 m3 contains 6 × 10−3 moles of gun powder.
When the rifle is fired, the temperature of the combustion gases is T1 = 4000 K, and
the volume is assumed to be that of the cartridge. Estimate the speed of a bullet of mass
equal to m = 5 × 10−3 kg leaving the rifle with the pipe volume of V2 = 2 × 10−5 m3 .
The combustion gases are described as an ideal gas with cP /cV = 1.5 undergoing the
reversible adiabatic expansion.
Solution
In the initial state, the combustion gases occupy the volume V1 = 2 × 10−7 m3 at the
temperature T1 = 4000 K, while in the final state, the combustion gases occupy the
volume V2 = 2 × 10−5 m3 at some unknown temperature T2 . In order to determine T2 ,
we can use the result (14.25), with κ = 1.5, to obtain
s
κ−1 V1
Tv 1/2
= Tv = Constant ⇒ T2 = T1 . (14.147)
V2
As V1 /V2 = 1/100, the final temperature is 10 times lower than the initial temperature
and we have T2 = 400 K. According to the first law of thermodynamics, for an ideal
gas undergoing adiabatic change (1Q = 0), we have
1U = cV 1T = 1Q − 1L = −1L. (14.148)
cP cV + nR
= = 1.5 ⇒ cV = 2nR. (14.149)
cV cV
The work done by the expanding gas is converted into the kinetic energy of the bullet
leaving the pipe of the rifle, and we can write
r
1 2 21L m
mv = 1L ⇒ v = ≈ 380 . (14.151)
2 m s
The speed of the bullet is thereby estimated at v ≈ 380 m/s, which is reasonably close
to the actual bullet’s speed.
Problem 9
The work required to change the surface area of a liquid drop by dA at a constant vol-
ume (V = Constant) is equal to dL = γ dA, where γ (T) = aT + b is the temperature-
dependent positive surface tension coefficient with a and b being constants. Calculate
the temperature change in the process where a spherical liquid drop of radius r is
divided into two identical smaller liquid drops. The process is assumed to be adia-
batic and reversible, and the specific heat per unit volume cV at constant volume of the
liquid is assumed to be constant.
Solution
The differential of the internal energy is in this case given by
∂(T, S)
dU = TdS + γ dA ⇒ = −1. (14.152)
∂(γ , A)
∂S ∂(S, T) ∂(A, γ ) ∂γ
= =− =− = −a. (14.153)
∂A T ∂(A, T) ∂(A, T) ∂T A
∂S
T = Tf 0 (T) = cV V. (14.155)
∂T V
T2 a1A
−a1A + cV V ln = 0 ⇒ T2 = T1 exp . (14.157)
T1 cV V
Since the volume of the two resulting smaller drops is V1 = 1/2V, the radius of these
two drops is r1 = (1/2)1/3 r. Thus the area change in the process is equal to 1A =
2 × 4πr12 − 4π r2 , or
" 2/3 #
1
1A = 4π 2r1 − r = 4π r 2 ×
2 2 2
−1 . (14.158)
2
Y (gi + ni − 1) !
W= , (15.2)
(gi − 1)!ni !
i
we can write
X
ln W = ln (gi + ni − 1) ! − ln ni ! − ln (gi − 1) !
i
X
≈ ln (gi + ni ) ! − ln ni ! − ln gi !. (15.3)
i
or
X
ln W = (gi + ni ) ln (gi + ni ) − ni ln ni − gi ln gi . (15.5)
i
Recalling that gi here are constants, the differential d ln W is now calculated as follows:
X dni dni
d ln W = dni ln (gi + ni ) + (gi + ni ) − dni ln ni − ni , (15.6)
gi + ni ni
i
or finally
X gi + ni
d ln W = dni ln . (15.7)
ni
i
or
X
ln W = ln gi ! − ln ni ! − ln (gi − ni ) !, (15.10)
i
or
X
ln W = gi ln gi − ni ln ni − (gi − ni ) ln (gi − ni ). (15.12)
i
Recalling that gi here are constants, the differential d ln W is now calculated as follows:
X dni
d ln W = −dni ln ni − ni
ni
i
dni
+ dni ln (gi − ni ) + (gi − ni ) , (15.13)
gi − ni
or finally
X gi − ni
d ln W = dni ln . (15.14)
ni
i
Above (and in the following), the upper sign applies to bosons and the lower sign
applies to fermions. The three differential equilibrium conditions (7.4–7.6), stated for
the classical distribution in Chapter 7, are also valid in the quantum statistics. The only
difference is that we now use the exact quantum-mechanical result for the differential
of entropy (15.16). Thus, we have
X 1
dU = Ei dni = 0 /· , (15.17)
T
i
X µ
dN = dni = 0 /· − , (15.18)
T
i
X gi ± ni
dS = k dni ln =0 / · (−1). (15.19)
ni
i
262 Quantum Statistical Physics
Using now the method of Lagrange multipliers, as indicated in the equations (15.17–
15.19), we get
X Ei − µ gi ± ni
− k ln dni = 0. (15.20)
T ni
i
The Lagrange multipliers in the equations (15.17–15.19) are now chosen in advance
to secure the classical limit, given by the equation (8.8). From the result (15.20), we
obtain
gi ± ni Ei − µ
ln = , (15.21)
ni kT
or
Ei − µ
gi ± ni
= exp . (15.22)
ni kT
Ei − µ
gi = ni exp ∓1 , (15.23)
kT
or
gi
ni = , (15.24)
Ei −µ
exp kT ∓1
where, as before, the upper sign applies to bosons and the lower sign applies to
fermions. The occupation number ni is the equilibrium number of quantum particles
distributed into gi sublevels of the energy level Ei . Thus, the mean occupation number
of a sublevel within the energy level Ei is given by
ni 1
ñi = = . (15.25)
gi Ei −µ
exp kT ∓ 1
The result (15.25) is, for the case of bosons (− sign), known as Bose–Einstein formula,
whereas for the case of fermions (+ sign), as Fermi–Dirac formula, giving the mean
(average) number of identical particles occupying a given sublevel, i.e., a one-particle
state that is specified by a full set of quantum numbers, such as, for example, the four
numbers (Ep, σz ) telling the three components of the particle momentum vector and the
z-component of the particle spin. In the limit, when
Ei − µ
exp 1, (15.26)
kT
Quantum Distribution Functions 263
µ − Ei
ni
ñi = = exp . (15.27)
gi kT
Substituting (15.28) into (15.27), we obtain the classical result for the mean occupation
number as follows:
ni N Ei
ñi = = exp − . (15.29)
gi Z kT
The classical limit (15.29) is identical to the classical result (8.20) obtained earlier. Let
us now discuss the limit (15.26). It is fulfilled when
Ei − µ
1. (15.30)
kT
In the classical limit, when the condition (15.26) is fulfilled, we can use (15.28) in the
form
µ
Z
− = ln . (15.31)
kT N
Using now the classical result (11.26) for the partition function Z of an ideal gas, we
obtain
" #
Ei V 2π mkT 3/2
+ ln 1. (15.33)
kT N h2
Since the energy levels of the system can be small and even approach zero, the condi-
tion (15.33) becomes
" 3/2 #
V 2π mkT
ln 1, (15.34)
N h2
264 Quantum Statistical Physics
or
3/2
V 2π mkT
1. (15.35)
N h2
Thus, we finally obtain the condition for validity of the classical approximation in the
form
2πmkT 3/2
N
V h2
2/3
h2 N
⇒ T Tquantum = . (15.36)
2πmk V
From the condition (15.36), we see that the classical approximation is valid for systems
of relatively low density N/V and relatively high temperature T that needs to be much
higher than a characteristic quantum temperature Tquantum . By the equation (15.36),
Tquantum increases with decreasing mass of constituent particles, and for light particles
such as electrons in metals (with N/V ≈ 1028 m−3 ), this characteristic temperature is
very high, Tquantum ≈ 104 − 105 K. Thus, under normal conditions (T ≈ room temper-
ature), classical statistical physics is inapplicable to the electron gas in metals, which
is dominated by quantum effects discussed in Chapter 16, “Electron Gases in Met-
als.” On the other hand, for heavy constituent particles such as atoms in molecules,
the Tquantum in the equation (15.36) is very small under normal conditions (densities)
realized in ordinary gases. Thus, the quantum distribution functions (15.25) for bosons
or fermions are not needed for these gases, and they are quantitatively well described
by the classical distribution function (15.29). The quantum-temperature scale Tquantum
for these gases is not accessible because it is well in the sub-Kelvin range. Well before
this range is reached, typical gases undergo condensation into liquids due to inter-
molecular forces.
Let us now elucidate the physical meaning of the classicality condition (15.36).
Recall that the quantum de Broglie wavelength associated with a particle moving with
velocity v is given by
h
λ= . (15.37)
mv
As particles move with different velocities (see Section 11.4, “Kinetic Theory of Ideal
Monatomic Gases”), the relevant quantity is
h 1
< λ >= < >. (15.38)
m v
The average < 1/v > in the above equation was calculated in Problem 5 of Chapter 11,
“Ideal Monatomic Gases.” By using this result, we find,
1/2
h2
< λ > = Constant × (15.39)
mkT
Quantum Distribution Functions 265
so that the condition (15.36) for the applicability of classical statistical mechanics can
be written simply as,
1/3
V
< λ > d = . (15.40)
N
As V/N is the volume per particle, the length-scale d in the above relation is essen-
tially the distance between the nearest neighbor particles in the gas. For the classical
physics to work well, the above condition, < λ > d, has to be required. It implies
that a given particle is seen by other particles of the gas as a classical object. Hence,
the classical physics is applicable to such ideal gases. On the other hand, in the oppo-
site case (which occurs for T < Tquantum ), a particle is seen by other particles as a
genuine quantum-mechanical object. The results of this are nontrivial quantum corre-
lations between identical particles occurring in ideal gases, even without any interpar-
ticle interaction. Their origin is in the symmetry requirements imposed on N-particle
wave functions, discussed in Section 6.2, “Calculation of the Number of Accessible
States.” Due to these requirements, a particle can affect other particles even with-
out any interparticle interaction. These effects become strong only if < λ > exceeds
d, which occurs when the gas temperature T is decreased below Tquantum . Thus, for
T < Tquantum , the above quantum correlation effects dominate and give rise to interest-
ing phenomena present both in fermionic systems (such as the so-called linear specific
heat, cv ∼ T, of electron gases in metals) and in bosonic systems (such as the Bose–
Einstein condensation). These phenomena are discussed in the following chapters.
The upper sign applies to bosons and the lower sign applies to fermions. On the other
hand, using the result (10.42), we can express the total number of particles of a quan-
tum system in terms of the Helmholtz thermodynamic potential as follows:
∂
N=− . (15.42)
∂µ T
µ − Ei
X
= ±kT gi ln 1 ∓ exp . (15.43)
kT
i
266 Quantum Statistical Physics
In order to verify that the above result for the Helmholtz thermodynamic potential
is correct, we substitute (15.43) into (15.42) to obtain
∂ ∂ µ − Ei
X
N=− ln 1 ∓ exp
= ∓kT gi
T ∂µ ∂µ kT
i
µ−E
X ∓ exp kT i 1
= ∓kT gi
1 ∓ exp µ−Ei kT
i kT
X gi
= . (15.44)
Ei −µ
i exp kT ∓1
Comparing the results (15.44) and (15.42), we see that the expression (15.43) for the
Helmholtz thermodynamic potential indeed reproduces the correct result for the
total number of particles in the quantum system (15.42).
p2 1 2
E( p) = = px + p2y + p2z , (15.45)
2m 2m
where again p is the magnitude of the linear momentum vector of a constituent particle,
which should not be confused with the pressure p of a thermodynamic system. The
two conflicting notations will not be used in the same context, and there should be no
risk for confusion here. The number of the continuously distributed momentum states
dg( p), inside a thin spherical shell ( p, p + dp), is obtained by multiplying the classical
Quantum Distribution Functions 267
result (11.8) with the number of possible spin states g(σ ) = 2σ + 1. Thus, we can
write
V
dg( p) = g(σ ) 3 4π p2 dp. (15.46)
h
Using (15.45), we can write
√
r
m
p = 2mE ⇒ dp = dE. (15.47)
2E
Substituting (15.47) into (15.46), we obtain
r
V m
dg(E) = g(σ ) 3 3 4π2mE dE, (15.48)
8π ~ 2E
or
m3/2 V √
dg(E) = g(σ ) √ EdE. (15.49)
2π 2 ~3
The continuous limit of the result (15.24) with (15.49) gives the continuous energy
distribution function
dg(E)
dnE = , (15.50)
exp E−µ
kT ∓1
or
√
m3/2 V EdE
dNE = g(σ ) √ . (15.51)
2 3
2π ~ exp E−µ ∓ 1
kT
Thus, we obtain the caloric-state equation for the quantum gas, consisting of elemen-
tary particles, in the following form
Z∞
m3/2 V E3/2 dE
U(V, T) = g(σ ) √ . (15.54)
2π 2 ~3 exp E−µ ∓ 1
0 kT
268 Quantum Statistical Physics
The upper sign in the above results applies to bosons and the lower sign applies to
fermions. The Helmholtz thermodynamic potential (15.43) in the continuous limit is
given by
Z∞√
m3/2 VkT µ−E
= ±g(σ ) √ E ln 1 ∓ exp dE. (15.55)
2π 2 ~3 kT
0
The integral on the right-hand side of the result (15.55) can be integrated by parts as
follows:
Z∞√
µ−E
I= E ln 1 ∓ exp dE
kT
0
∞ ∞
Z ∓ exp µ−E − 1 2 E3/2 dE
2 3/2
3 E kT kT 3
= −
µ−E
exp E−µ
kT ∓ 1 0
1 ∓ exp kT
0
Z∞ 2 3/2
1 3E dE
=∓ . (15.56)
kT E−µ
exp kT ∓ 1
0
Z∞
2 m3/2 V E3/2 dE
= − g(σ ) √ . (15.57)
3 2π 2 ~3 exp E−µ ∓ 1
0 kT
2
= −pV = − U. (15.58)
3
Thus, we obtain the thermal-state equation for the quantum gas, consisting of elemen-
tary particles, in the following form
2
pV = U. (15.59)
3
This is an exact result, which remains valid in the classical limit. Indeed, if we
use the classical result for the internal energy of an ideal gas U = 3/2NkT, the
equation (15.59) reduces to the classical thermal-state equation for the ideal gas, i.e.,
pV = NkT. (15.60)
Quantum Distribution Functions 269
The enthalpy (9.19) for the quantum gas, consisting of elementary particles, is now
calculated as follows:
2 5
H = U + pV = U + U = U. (15.61)
3 3
This is also an exact result. If we substitute here the classical result for the internal
energy of an ideal gas U = 3/2NkT, we obtain the classical result for enthalpy of an
ideal gas, i.e.,
5
H = NkT. (15.62)
2
From the above results, we see that if we want to calculate the thermodynamic vari-
ables of the quantum gas, we need to calculate the integral
Z∞
E3/2 dE
IE = . (15.63)
E−µ
0
exp kT ∓1
When the chemical potential µ is not equal to zero, the integral (15.63) cannot be
solved in the closed form and we can only find approximate solutions. Some physically
interesting solutions will be discussed in the following chapter.
Z∞
wx−1 dw
I(x) = , (15.64)
ew ∓ 1
0
where x > 1 is a real number. In order to solve the integral (15.64), we first use the
geometric series
∞ ∞
1 X 1 X
= an (a < 1) ⇒ = (±1)n e−nw (15.65)
1−a 1 ∓ e−w
n=0 n=0
to calculate
∞
1 e−w X
w
= −w
= (±1)n e−(n+1)w . (15.66)
e ∓1 1∓e
n=0
270 Quantum Statistical Physics
∞
X Z∞
I(x) = (±1) n
wx−1 e−(n+1)w dw. (15.67)
n=0 0
where 0( j) = ( j − 1)! is the gamma function of an integer argument. The result (15.68)
can easily be verified for integer j ( j = 1, 2, 3 . . .), by elementary partial integration.
Furthermore, the result (15.68) can be generalized to the case of noninteger j = x as
follows:
Z∞
0(x)
wx−1 e−αw dw = x . (15.69)
α
0
where
∞
X 1
ζ (x) = , (x > 1), (15.73)
nx
n=1
On the other hand, the difference of the two series for bosons and fermions only
includes the even terms (n = 2j), and we have
∞ ∞ ∞ ∞
X 1 X (−1)n+1 X 1 + (−1)n X 1
− = = 2 , (15.75)
n x n x n x (2j)x
n=1 n=1 n=1 j=1
or
∞ ∞ ∞
X 1 X (−1)n+1 X 1
− = 21−x
. (15.76)
nx nx jx
n=1 n=1 j=1
or
∞
X (−1)n+1
= (1 − 21−x )ζ (x). (15.78)
nx
n=1
Substituting (15.78) into (15.74), we finally obtain the result for fermions
Z∞
w x−1 dw
I(x) = = 1 − 2 1−x
0(x)ζ (x). (15.79)
ew + 1
0
In the special case, when x = 2j is an even integer, the Riemann zeta functions can be
expressed in terms of Bernoulli numbers B2 j , and we obtain for bosons
Z∞
w2j−1 dw (2π )2j B2j
I(2j) = = 0(2j)ζ (2j) = , (15.80)
ew − 1 4j
0
Z∞
w3 dw (2π )4 B4 π4
I(2j = 4) = w
= = , (15.83)
e −1 8 15
0
Z∞
w3 dw 7 π4 7π 4
I(2j = 4) = = × = . (15.84)
ew + 1 8 15 120
0
The above integrals are important for calculation of thermodynamic variables for all
quantum gases.
Solution
(a) Recall that S = k ln W. The number of microstates W satisfies the inequalities,
W ≥ 1 ⇒ ln W ≥ 0, (15.85)
hence
S = k ln W ≥ 0. (15.86)
Thus, the entropy cannot be negative. At best, entropy can approach zero and this
happens only if W → 1. For example, in thermodynamic equilibrium of quantum
systems, the limit W → 1, i.e., S = k ln W → 0, is reached only in the limit of
zero temperature T → 0 (see Section 9.2.4, “Third Law of Thermodynamics”). On
the other hand, for any nonzero temperature, W > 1, i.e., S = k ln W > 0. Thus, in
thermodynamic equilibrium, entropy is positive at any finite temperature, and it
approaches zero value only in the limit T → 0.
Quantum Distribution Functions 273
(b) Consider the classical statistical mechanics result for the entropy of an ideal gas,
given by the equation (11.81). It can be rewritten as follows:
3 2 V 2πmkT
S = Nk 1 + ln + ln +Nk
2 3 N h2
3 5 2 V 2πmkT
= Nk + ln + ln
2 3 3 N h2
3 5/3 2 V 2π mkT
= Nk ln e + ln + ln
2 3 N h2
" 2/3 #
3 5/3 V 2πmkT
= Nk ln e . (15.87)
2 N h2
By the above result, the classical result for the entropy of an ideal gas, can be
written shortly as,
3 T
S = Nk ln , (15.88)
2 T∗
By the above, we see that the classical statistical physics predicts entropy that
is positive for T > T ∗ , vanishes at a nonzero temperature T = T ∗ , and then it
becomes negative for the temperatures T < T ∗ (and, moreover, it approaches nega-
tive infinity as the temperature goes to zero). In view of our discussions in the item
(a) above, the exact expression for an entropy cannot be negative. Thus, it is obvi-
ous that the classical physics dramatically fails at low temperatures, below the
above-defined characteristic temperature T ∗ . It is easy to see that this patholog-
ical behavior of classical entropy at low temperatures is because of the quantum
effects discussed in Section 15.2, “Quantum Equilibrium Distribution.” Indeed, by
the equation (15.36), one can see that T ∗ is (up to inessential numerical constant
e−5/3 ) the same as Tquantum .
Problem 2
Consider a general quantum-mechanical system in equilibrium at temperature T. Its
partition function is, as usual, given by the sum over the energy states
X Eα
Z(T) = exp − , (15.90)
α
kT
274 Quantum Statistical Physics
∂
U(T) = kT 2 ln Z(T) (15.92)
∂T
to show that the internal energy U(T) is given by the sum
X
U(T) = Eα Pα , (15.93)
α
with
1 Eα
Pα (T) = exp − . (15.94)
Z(T) kT
What is the value of the sum α Pα ? What is the physical meaning of Pα (T)?
P
(b) Show that the system entropy,
U(T) − F(T) ∂
S= = − F(T), (15.95)
T ∂T
can be written as
X
S(T) = −k Pα ln Pα . (15.96)
α
∂
C(T) = U(T), (15.97)
∂T
satisfies the so-called fluctuation–dissipation theorem
< [Eα − U(T)]2 > = < (Eα )2 > − < Eα >2 . (15.100)
Solution
(a) By using the chain rule for the derivative, we have
∂ 1 ∂
U(T) = kT 2 ln Z(T) = kT 2 Z(T)
∂T Z(T) ∂T
∂ X
2 1 Eα
= kT exp −
Z(T) ∂T α kT
1 X2 Eα Eα
= kT exp −
Z(T) α kT kT 2
X
X 1 Eα
= Eα exp − = Eα Pα . (15.101)
α
Z(T) kT α
This proves the equation (15.93). Its form is telling us that the quantity Pα is the
probability to find this quantum-mechanical system in the state with energy Eα . In
accord with the quantities Pα being a set of probabilities, are the facts that these
quantities are obviously positive [see the equation (15.94)], and that their sum is
X 1
X Eα Z(T)
Pα = exp − = = 1. (15.102)
α α
Z(T) kT Z(T)
(b) We have
P
U(T) − F(T) α Eα Pα + kT ln Z(T)
S= = . (15.103)
T T
or
X
S = −k Pα ln Pα . (15.106)
α
This proves the equation (15.96) for the entropy of a general quantum-mechanical
system. From this result, it is easy to see that the entropy S cannot be negative.
Indeed, all state probabilities satisfy the condition 0 ≤ Pα ≤ 1 or ln Pα ≤ 0, hence,
for all states,
X
−Pα ln Pα ≥ 0 ⇒ S = −k Pα ln Pα ≥ 0. (15.107)
α
This proves that entropy S cannot be negative, for any quantum-mechanical sys-
tem. By the equation (15.107), the entropy can be either positive or zero. For
the entropy to be zero, a very special condition needs to be satisfied. Indeed, by
(15.107), the entropy is the sum of nonnegative terms −Pα ln Pα , so S can van-
ish if and only if each of the terms in the sum vanishes. That is, S vanishes only
if −Pα ln Pα = 0 for all states. Recall now that the only solutions to the equa-
tion x ln x = 0 are x = 0 and x = 1. So, if entropy is zero, the probabilities Pα are
boundPto be either 0 or 1. Recall, however, that these probabilities add up to 1,
i.e., α Pα = 1. It is then easy to see that, if entropy is zero, then only one of
these probabilities can be 1, whereas all remaining probabilities are 0. Thus, zero
entropy corresponds to essentially the non-random situation in which the quantum-
mechanical system occupies with certainty (probability = 1) one of the energy
states, whereas the probabilities to find the system in any of the other states are
zero. Such a situation, however, can never happen at a nonzero temperature, as
can be easily seen from the form of the probabilities in (15.94). By this equation,
for any finite T, all Pα (T) are nonzero; hence, the entropy cannot be zero for a
nonzero temperature. The condition for the entropy to vanish is, however, satis-
fied in the limit T → 0, in which the probability to find the system in the ground
state (minimum energy state, with energy E0 ) indeed approaches unity, whereas
the probabilities of all other excited states (with energies Eα > E0 ) approach 0.
Indeed, by equation (15.94), we have
Pα (T)
Eα − E0
= exp − → 0 for T → 0. (15.108)
P0 (T) kT
Quantum Distribution Functions 277
whereas Pα (T) → 0 for all excited states. So, in thermodynamic equilibrium, the
condition to have zero entropy is satisfied only in the limit T → 0.
(c) For the heat capacity, equation (15.97) with (15.93) gives
∂U ∂ X X ∂
C(T) = = Eα Pα = Eα Pα (T). (15.111)
∂T ∂T α α
∂T
Here,
∂ ∂
1 Eα
Pα (T) = exp −
∂T ∂T Z(T) kT
∂ Eα ∂
1 Eα
= exp − Z(T) − exp − Z(T)
[Z(T)]2 ∂T kT kT ∂T
Eα ∂
1 Eα Eα
= exp − Z(T) − exp − Z(T)
[Z(T)]2 kT kT 2 kT ∂T
1 ∂
1 1 Eα
= 2 exp − Eα − kT 2 Z(T) . (15.112)
kT Z(T) kT Z(T) ∂T
Using equations (15.92) and (15.94), we can rewrite the equation (15.112) in a
simple form,
∂ Pα Pα
Pα (T) = 2 [Eα − U(T)] = 2 [Eα − < Eα >]. (15.113)
∂T kT kT
Inserting (15.113) into (15.111) yields
1 X
C(T) = Eα Pα [Eα − < Eα >]
kT 2 α
1 X h 2 i
= Pα E α − < E α > Eα
kT 2 α
( )
1 X 2 X
= 2 Eα Pα − < Eα > Eα Pα . (15.114)
kT α α
278 Quantum Statistical Physics
and from this form of the fluctuation–dissipation theorem, it is obvious that C(T)
cannot be negative C(T) ≥ 0, and we expect it to be, in general, a positive quan-
tity. This has an interesting implication on the behavior of entropy with changing
temperature. Indeed, recalling the equation (15.95), i.e.,
∂F
U(T) = F + TS = F − T , (15.118)
∂T
gives
∂U ∂ ∂F
C(T) = = F−T
∂T ∂T ∂T
2 2
∂F ∂T ∂F ∂ ∂
= − −T F = −T F
∂T ∂T ∂T ∂T ∂T
∂ ∂F ∂
=T − = T S. (15.119)
∂T ∂T ∂T
Quantum Distribution Functions 279
∂
T S = C(T) ≥ 0. (15.120)
∂T
From the equation (15.120), we see that the entropy S(T) cannot decrease with
increasing temperature T. That is, S(T) is, in general, an increasing function of
temperature T.
(f) By the equation (15.120), it is obvious that for quantum-mechanical systems,
C(T) = T∂S/∂T → 0, as T → 0. Recall that, for example, the classical monatomic
ideal gas violates this property. For it, C(T) = 3/2Nk = Constant, i.e., C(T) is
a constant. This behavior with constant C(T) will be present only in the high-
temperature classical regime, for T above the characteristic quantum tempera-
ture Tquantum defined in (15.36). On the other hand, for the temperatures below
Tquantum , by the above results, we expect a genuinely quantum-statistical behavior
in which C(T) → 0 as T → 0.
Problem 3
A two-dimensional ideal gas is confined to a two-dimensional square box with area
A = a2 , and its quantum energy levels are given by the two-dimensional analog of the
equation (3.42), i.e.,
h2 2 h2 2
E= 2
nx + n2y = nx + n2y , (15.121)
8ma 8mA
where nx , ny = 1, 2, 3, 4 . . . are the quantum numbers labeling the energy states. Deter-
mine the chemical potential µ of the gas if the particles are fermions, bosons, and
classical particles. Verify that the quantum results obtained for fermions and bosons
have the classical result as a high-temperature limit.
Hint: The following integral is useful for the solution of the present problem
Z∞
dw
= ± ln(1 ± 1/b). (15.122)
bew ± 1
0
Solution
In order to calculate the chemical potential, we need to find the density of states for
the two-dimensional gas. We use the two-dimensional analog of the equation (15.46)
that reads
A
dg( p) = g(σ ) 2π pdp, (15.123)
h2
280 Quantum Statistical Physics
where g(σ ) = 2σ + 1 is the spin factor. Using the definition of the kinetic energy E =
p2 /2m, we can write
√
r
m
p = 2mE ⇒ dp = dE. (15.124)
2E
2π mA
dg(E) = g(σ ) dE, (15.125)
h2
whereby we show that the density of states of a two-dimensional gas is a constant. The
number of particles in a fermion gas is then
Z∞
2π mA dE
N = g(σ ) 2 , (15.126)
h exp E−µ
+1
0 kT
or
Z∞
2π mA dE
N = g(σ ) 2 −µ E
. (15.127)
h exp kT exp kT + 1
0
Z∞
2π mAkT dw
N = g(σ ) −µ w , (15.128)
h2 exp kT e + 1
0
or
Z∞
Nh2 dw
= . (15.129)
2π g(σ )mAkT exp −µ w
kT e + 1
0
Nh2
T0 = . (15.130)
2π g(σ )mAk
Z∞
T0 dw
= −µ w . (15.131)
T exp kT e + 1
0
Quantum Distribution Functions 281
Z∞
T0 dw
= −µ w . (15.134)
T exp kT e − 1
0
T0 µ Z∞ µ
= exp e−w dw = exp . (15.137)
T kT kT
0
The final result for the chemical potential µ for classical particles is
T0
µ = kT ln . (15.138)
T
Let us now check the limit of the expressions (15.133) and (15.136) when T T0 .
The expression (15.133) yields
T0 T0
µ ≈ kT ln 1 + − 1 = kT ln , (15.139)
T T
Thus, the results for both fermions and bosons have the correct classical limit.
282 Quantum Statistical Physics
Problem 4
The equation (15.25) actually gives the average number of identical particles (bosons
or fermions) occupying a given sublevel with the energy Ei ,
1
n̄i = < ñi > = , (15.141)
Ei −µ
exp kT ∓ 1
with upper (lower) sign applying for bosons (fermions). In thermodynamic equilib-
rium, the actual number of these particles fluctuates around the average given by the
equation (15.141). The probability to find ñi particles occupying the sublevel with the
energy Ei is given by the expression
µ − Ei
1
Pi (ñi ) = exp ñi . (15.142)
4i kT
The equation (15.142) applies to both bosons and fermions. Here, ñi = 0, 1, 2, . . . ,
ñmax , where ñmax = ∞ for bosons, whereas, because of the Pauli exclusion principle,
ñmax = 1 for fermions.
(a) Calculate the value of the normalization factor 4i in the equation (15.142).
(b) Show that
∂
< ñi > = − i , (15.143)
∂µ
where
i = −kT ln 4i . (15.144)
(c) Use the equations (15.142) and (15.144) to rederive the equation (15.141) for both
bosons and fermions.
(d) Consider the average of the total number of particles
X X
< N >= gi n̄i = gi < ñi > . (15.145)
i i
∂
< N >= − , (15.146)
∂µ
with
X
= gi i . (15.147)
i
Show also that the above coincides with the Helmholtz potential (15.43).
Quantum Distribution Functions 283
Solution
(a) Since Pi (ñi ) must satisfy the condition
ñX
max
Pi (ñi ) = 1, (15.148)
ñi=0
ñX ñmax
max
µ − Ei
1 X
1= Pi (ñi ) = exp ñi
4i kT
ñi =0 ñi =0
ñX
max
µ − Ei
⇒ 4i = exp ñi . (15.149)
kT
ñi =0
For bosons, with ñmax = ∞, the equation (15.149) is a standard geometric series
of the form
∞
µ − Ei
X 1
4i = n
, < 1.
a = |a| = exp
(15.150)
1−a kT
n=0
The convergence of the series requires that Ei > µ for all states of bosonic sys-
tems. This will be obviously assured if this condition is satisfied for the minimum
energy state (ground state) with energy, Emin > µ. Thus, for bosons,
µ − Ei −1
4i = 1 − exp . (15.151)
kT
For fermions, with ñmax = 1, the sum (15.149) contains only two terms, ñi = 0 and
ñi = 1, so
+1
µ − Ei µ − Ei
4i = 1 + exp = 1 + exp . (15.152)
kT kT
The results (15.151) and (15.152) can be combined into one formula
µ − Ei ∓1
4i = 1 ∓ exp , (15.153)
kT
∂ ∂ 1 ∂
− i = kT ln 4i = kT 4i
∂µ ∂µ 4i ∂µ
ñmax
1 ∂ X µ − Ei
= kT exp ñi
4i ∂µ kT
ñi =0
ñmax
µ − Ei
1 X ñi
= kT exp ñi
4i kT kT
ñi =0
ñX
max
µ − Ei
1
= exp ñi ñi
4i kT
ñi =0
ñX
max
= Pi (ñi ) ñi = < ñi > . (15.154)
ñi =0
∂ ∂
< ñi > = − i = kT ln 4i . (15.155)
∂µ ∂µ
∂ ∂ µ − Ei ∓1
< ñi > = kT ln 4i = kT ln 1 ∓ exp
∂µ ∂µ kT
∂ µ − Ei
= ∓kT ln 1 ∓ exp
∂µ kT
−1
µ − Ei ∂ µ − Ei
= ∓kT 1 ∓ exp 1 ∓ exp
kT ∂µ kT
−1
µ − Ei µ − Ei
1
= ∓kT 1 ∓ exp ∓ exp
kT kT kT
−1
µ − Ei µ − Ei
= 1 ∓ exp exp
kT kT
1
= . (15.156)
Ei −µ
exp kT ∓1
that is,
∂ X
< N >= − with = gi i . (15.158)
∂µ
i
This proves the equation (15.146). Let us finally show that the above coin-
cides with the Helmholtz potential (15.43). Indeed, by the equations (15.144) and
(15.153), we have
X X
= gi i = −kT gi ln 4i
i i
µ − Ei ∓1
X
= −kT gi ln 1 ∓ exp
kT
i
µ − Ei
X
= ±kT gi ln 1 ∓ exp , (15.159)
kT
i
Problem 5
For fermions,
(a) Show that, in the notations of Problem 4,
1
Pi (ñi = 1) = 1 − Pi (ñi = 0) = < ñi > = . (15.160)
Ei −µ
exp kT + 1
Solution
(a) For fermions, i.e., ñmax = 1, we can have only ñi = 0 and ñi = 1, so
ñX
i =1
< ñi > = Pi (ñi ) ñi = Pi (0) · 0 + Pi (1) · 1 = Pi (1). (15.161)
ñi =0
286 Quantum Statistical Physics
1
Pi (ñi = 1) = < ñi > = , (15.162)
Ei −µ
exp kT + 1
or
exp µ−E
i
kT · 1
Pi (ñi = 1) = . (15.163)
µ−Ei
exp kT + 1
ñX
i =1
1 =< 1 >= Pi (ñi ) · 1 = Pi (0) + Pi (1) (15.164)
ñi =0
so that
= 1− = , (15.165)
exp EikT
−µ
+ 1 exp EikT
−µ
+1
or
exp µ−E
i
kT · 0
Pi (ñi = 0) = . (15.166)
µ−Ei
exp kT + 1
The final forms of Pi (1) and Pi (0) written in equations (15.163) and (15.166),
respectively, are results of simple algebra. The results in equations (15.163) and
(15.166) are written in such a way to emphasize that they coincide with the general
result in equation (15.142), for the special case of fermions.
(b) We have
ñX
i =1
< (ñi )137 > = Pi (ñi ) · (ñi )137 = Pi (0) · 0137 + Pi (1) · 1137
ñi =0
1
= Pi (1) = < ñi > = . (15.167)
Ei −µ
exp kT + 1
By a similar reasoning, < (ñi )m > = < ñi > for any positive m.
16 Electron Gases in Metals
Metals are well known to be very good electric current conductors. Conductivity of
metals comes from a fraction of all electrons in metals, the so-called conducting elec-
trons, that are nearly free to move in the background of the crystalline lattice of posi-
tively charged ions. The system consisting of a large number of these free electrons
in a metal specimen can be described as an electron gas. The electrons are elemen-
tary particles with half-integer spin (σ = 1/2) and they obey the quantum statistics for
fermions. In this analysis, the electron–electron interactions and the influence of the
periodic potential of the ions in the crystal lattice on the motion of free electrons are
neglected. In such an approximation, the electron gas can be treated as an ideal quan-
tum gas. If the metal specimen is surrounded by nonconducting environment (e.g.,
air), the electrons cannot escape from the metal. Assuming that the metal specimen is
a cube with the side a, we can describe the electron gas as a system consisting of N
noninteracting point-like particles, enclosed in the cubic box with impenetrable walls,
having the volume V = a3 . Apart from their spin, the electrons have only the trans-
lational degrees of freedom. The quantum-mechanical problem is thereby the same
as the one studied in Chapter 3, “Kinetic Energy of Translational Motion,” and the
translational energy of a single electron is given by the result (3.41), i.e.,
~2 κ 2 ~2 π 2 2
E= = 2
nx + n2y + n2z , (16.1)
2m 2ma
where
2π
κE = nE, nE = nx , ny , nz
(16.2)
a
is the wave vector of the electron. From the above result for the energy E of free elec-
trons in the electron gas, we see that the electron gas is a regular nonrelativistic quan-
tum gas. Thus, the general results for such quantum gases, obtained in the previous
chapter, are applicable to the electron gas. In particular, the number of electrons with
energies within the interval (E, E + dE) is given by the result (15.49) with g(σ ) = 2,
i.e.,
3/2
m3/2 V √
1 2m
dg(E) = 2 √ EdE = VE1/2 dE. (16.3)
2π 2 ~3 2π 2 ~2
Z 3/2 ZEF
1 2m
N= dg(E) = V E1/2 dE, (16.4)
2π 2 ~2
E<EF 0
or
3/2
1 2mEF
N= V. (16.5)
3π 2 ~2
The Fermi energy, in terms of the density of the electron gas, is given by
~2 2 2/3
EF = 3π n . (16.7)
2m
The so-called Fermi temperature TF is obtained from EF = kTF , and we have
EF ~2 2 2/3
TF = = 3π n . (16.8)
k 2mk
By the equation (16.8), we see that TF is (up to an inessential numerical constant) the
same as the characteristic quantum temperature Tquantum in the equation (15.36). Thus,
the classical statistical thermodynamics should be applicable for T TF , whereas
quantum effects discussed in Chapter 15, “Quantum Distribution Functions,” become
dominant at temperatures below TF . In order to calculate the density of the electron
gas, we first look at the crystal lattice of a metal with atomic mass A (kg/mole) and
mass density ρm (kg/m3 ). The crystal lattice of a metal consists of a large number of
unit cells with volume VC (m3 ). In this analysis, we consider only metals with one
atom per unit cell. In such a case, the mass of a single atom can be obtained either
as ρm VC or A/NA , where NA (atoms/mole) is the Avogadro number given by (11.85).
Thus, we can write
A A
mA = ρ m VC = ⇒ VC = . (16.9)
NA ρm NA
Electron Gases in Metals 289
Each metal atom has Z valence electrons, i.e., free electrons that constitute the electron
gas. The density of the electron gas in the metal specimen is then given by
Z ρm electrons
n= = ZNA ∼ 1029 . (16.10)
VC A m3
From the order-of-magnitude estimate given in (16.10), we see that the density of the
electron gas is very high compared with the densities of the ordinary gases. Substitut-
ing the estimate (16.10) into (16.8), we obtain TF ∼ 90,000 K. The condition for the
classical statistics to be applicable to the case of an electron gas is T TF . Obviously,
for realistic metals, T TF . Indeed at T ∼ TF , all known metals would evaporate.
Thus, the electron gas in realistic metals is a strongly degenerate quantum gas, and the
quantum statistics must be applied. The ground-state internal energy of the electron
gas is given by
Z 3/2 ZEF
1 2m
U0 = Edg(E) = V E3/2 dE, (16.11)
2π 2 ~2
E<EF 0
or
3/2 3/2
1 2m 5/2 3 1 2mEF
U0 = VEF = VEF . (16.12)
5π 2 ~2 5 3π 2 ~2
3
U0 = NEF . (16.13)
5
dg(E)
dnE = . (16.14)
exp E−µ
kT +1
In the ground state for T = 0, we have used the energy distribution function
1 E < EF
dnE = dg(E) × (16.15)
0 E > EF
290 Quantum Statistical Physics
to calculate the total number of particles (16.4) in the ground state. On the other hand,
in the limit T → 0, the equation (16.14) becomes
1 E<µ
dnE = dg(E) × . (16.16)
0 E>µ
Comparing the results (16.15) and (16.16), we see that in the ground state, we have
µ(T = 0) = EF . Furthermore, even at relatively low finite temperatures, the distribu-
tion function (16.14) is close to the ground-state limit (16.16). Thus, we can often use
the approximation µ ≈ EF at low temperatures T TF .
Using the results (15.52) and (15.54) with g(σ ) = 2 and the correct sign for fermion
gas, we obtain the total number of electrons
3/2 Z∞
E1/2 dE
1 2m
N= V , (16.17)
2π 2 ~2
0
exp E−µ
kT +1
3/2 Z∞
E3/2 dE
1 2m
U= V . (16.18)
2π 2 ~2
E−µ
0
exp kT +1
We proceed to calculate the integrals on the right-hand sides of the equations (16.17)
and (16.18), respectively. Let us first introduce a new variable w as follows:
3/2 Z∞
(µ + kTw)1/2 kTdw
1 2m
N= V , (16.20)
2π 2 ~2 ew + 1
−µ/kT
or
3/2 Z∞
(w + µ/kT)1/2 dw
1 2m
N= V(kT) 3/2
. (16.21)
2π 2 ~2 ew + 1
−µ/kT
Substituting (16.19) into (16.18), we obtain the internal energy of the electron gas
3/2 Z∞
(µ + kTw)3/2 kTdw
1 2m
U= V , (16.22)
2π 2 ~2 ew + 1
−µ/kT
Electron Gases in Metals 291
or
3/2 Z∞
(w + µ/kT)3/2 dw
1 2m
U= 5/2
V(kT) . (16.23)
2π 2 ~2 ew + 1
−µ/kT
The integrals on the right-hand side of the equations (16.21) and (16.23) are of
the type
Z∞
f (w + µ/kT)dw
I= , (16.24)
ew + 1
−µ/kT
Thus, we have
Z0 Z∞
f (w + µ/kT)dw f (w + µ/kT)dw
I= + . (16.26)
ew + 1 ew + 1
−µ/kT 0
Changing the sign of the variable w → −w in the first integral on the right-hand side
of (16.26), we obtain
µ/kT Z∞
f (−w + µ/kT)dw f (w + µ/kT)dw
Z
I= + . (16.27)
e−w + 1 ew + 1
0 0
In the first integral on the right-hand side of (16.27), we use the identity
1 1
= 1− w (16.28)
e−w + 1 e +1
to obtain
µ/kT µ/kT Z∞
f (−w + µ/kT)dw f (w + µ/kT)dw
Z Z
I= f (−w + µ/kT)dw − + .
ew + 1 ew + 1
0 0 0
(16.29)
In the first integral on the right-hand side of (16.29), we can introduce a new variable
λ = −w + µ/kT. Thus, we obtain
µ/kT
Z Z0 µ/kT
Z
f (−w + µ/kT)dw = f (λ)d(−λ) = f (λ)dλ. (16.30)
0 µ/kT 0
292 Quantum Statistical Physics
Let us now expand the functions f (w + µ/kT) and f (−w + µ/kT) as the Taylor series
in powers of w as follows:
µ µ µ
f w+ =f + f (1) w
kT kT kT
1 µ 1 µ
+ f (2) w2 + f (3) w3 + · · · (16.32)
2! kT 3! kT
and
µ µ µ
f −w + =f − f (1) w
kT kT kT
1 µ 1 µ
+ f (2) w2 − f (3) w3 + · · ·. (16.33)
2! kT 3! kT
Thus, we can write
µ µ µ 1 µ
f w+ − f −w + = 2f (1) w + 2 f (3) w3 + · · ·. (16.34)
kT kT kT 3! kT
Substituting (16.34) into (16.31), we obtain
µ/kT
Z µ Z∞ wdw 1 (3) µ
Z∞ 3
w dw
(1)
I=+ f (λ)dλ + 2f w
+ f . (16.35)
kT e +1 3 kT ew + 1
0 0 0
The solutions of the two integrals on the right-hand side of the equation (16.35) are
obtained using the significant integral (15.81). Thus, we have
Z∞ Z∞
wdw π2 w3 dw 7π 4
= , = . (16.36)
ew + 1 12 ew + 1 120
0 0
or
3/2
2 5/2 π 2 k2 T 2 7π 4 k4 T 4
1 2m
U= V µ + − . (16.47)
2π 2 ~2 5 4 µ−1/2 960 µ3/2
Thus, we have obtained the approximate results for the number of constituent particles
and internal energy of the electron gas. These results will be used in the next two
sections to calculate some important thermodynamic quantities of the electron gas.
Zµ ZEF Zµ
λ
1/2
dλ = λ dλ + λ1/2 dλ.
1/2
(16.49)
0 0 EF
3/2
!
2m 3/2 2EF
1 1/2
n= + EF (µ − EF )
2π 2 ~2 3
3/2 2 2 2
1 2m π k T
+ 2 2
, (16.51)
2π ~ 12 E1/2
F
where we used the approximation µ ≈ EF in the last term of the equation (16.51).
After some algebra, we obtain
3/2 3/2 !
µ π 2 k2 T 2
1 2mEF 1 2mEF
n= + 2 −1+ . (16.52)
3π 2 ~2 2π ~2 EF 12 EF2
Electron Gases in Metals 295
If we now recall the result for the density n of the electron gas (16.16), we see that the
first term on the right-hand side of the equation (16.52) cancels the left-hand side of
that equation. Thus, we may write
3/2 !
µ π 2 k2 T 2
1 2mEF
0= −1+ . (16.53)
2π 2 ~2 EF 12 EF2
By the equation (16.53), we obtain the approximate result for the chemical potential
of the degenerate electron gas in the following form
!
π 2 k2 T 2
µ = EF 1− . (16.54)
12 EF2
µ/kT
3/2
π2 k2 T 2
Z
1 2m
U= V λ3/2 dλ + , (16.55)
2π 2 ~2 4 E−1/2
0 F
where we used the approximation µ ≈ EF in the last term of the equation (16.55). Let
us now calculate the integral
Zµ ZEF Zµ
λ
3/2
dλ = λ dλ + λ3/2 dλ.
3/2
(16.56)
0 0 EF
Zµ 5/2 Zµ 5/2
2E 3/2 2EF 3/2
λ
3/2
dλ ≈ F + EF dλ = + EF (µ − EF ). (16.57)
5 5
0 EF
π 2 k2 T 2
µ − EF = − . (16.58)
12 EF
296 Quantum Statistical Physics
Zµ 5/2
2EF π 2 k2 T 2
λ3/2 dλ = − . (16.59)
5 12 E−1/2
0 F
or
5/2
3/2 !
π 2 k2 T 2
1 2m 2EF
U= V + . (16.61)
2π 2 ~2 5 6 E−1/2
F
If we now recall the result for the ground-state internal energy U0 of the electron gas
(16.12), we finally obtain
!
5π 2 k2 T 2 3
U = U0 1 + , U0 = NEF . (16.63)
12 EF2 5
∂U π 2 kT
msample cV = = Nk . (16.64)
∂T V 2 EF
On the other hand, the specific heat at constant volume for the classical ideal gas
is given by msample cVC = 3/2Nk. Thus, the ratio between the quantum and classical
specific heats at realistic temperatures (T ∼ 1000 K) is
cV π 2 kT π2 T
= = ∼ 10−2 . (16.65)
cVC 3 EF 3 TF
Using now the significant integral (15.59), we obtain the approximate thermal-state
equation for the degenerate electron gas in the following form
!
2 2 5π 2 k2 T 2
pV = U = NEF 1 + . (16.66)
3 5 12 EF2
Electron Gases in Metals 297
Solution
The Fermi energy, in terms of the density of the electron gas, is calculated as follows:
~2 2 2/3
EF = 3π n = 5.13 × 10−19 J. (16.71)
2m
π 2 NAV k2 T J
cV = = 0.33 . (16.72)
2EF K mol
298 Quantum Statistical Physics
Problem 2
Calculate the isothermal compressibility coefficient γ for a free electron gas at T = 0
in terms of the density n of the gas.
Solution
The isothermal compressibility coefficient is defined by
1 ∂V ∂p
γ =− ⇒ γ = −V−1
. (16.73)
V ∂p T ∂V T
Using now the result for pressure p in terms of the free energy F, i.e.,
∂F
p=− , (16.74)
∂V T
we obtain
∂ 2F
γ −1
=V . (16.75)
∂V 2 T
∂ 2U
γ −1 = V . (16.76)
∂V 2 T
3N ~2 N 2/3
3
U = NEF = 3π 2 = AV −2/3 , (16.77)
5 10 m V
3N ~2 2 2/3
A= 3π N . (16.78)
10 m
Thus, we can calculate
∂ 2 −2/3 10 −5/3
γ −1 = V AV = AV , (16.79)
∂V 2 9
or finally
10U 2NEF 2
γ −1 = = = nEF . (16.80)
9V 3V 3
Electron Gases in Metals 299
Problem 3
An ideal gas of spin- 12 fermions, of density n = N/V at a temperature T has the zero
kinetic energy state half-filled (for each of the two spin orientations). Determine the
chemical potential µ and the temperature T of the gas exactly.
Solution
The probability of finding a fermion in the zero kinetic energy state, i.e., the mean
occupation number of the zero kinetic energy state (for each of the two spin orienta-
tions), is given by the equation (15.25) with the positive sign in the denominator and
with E = 0
1 1
n̄0 = = , (16.81)
exp 0−µ
kT +1 2
and in this case is equal to 1/2 since this state is said to be exactly half-filled. From
the equation (16.81), we see that at this particular temperature, the chemical potential
of the fermion gas must be equal to zero µ = 0. The temperature T is now determined
using the definition of the number of spin- 21 fermions (16.17), which for µ = 0 reads
3/2 Z∞
E1/2 dE
1 2m
N= V E
. (16.82)
2π 2 ~2
exp kT +1
0
The integral in (16.83) is solved using (15.79) for x = 3/2, and we have
2mkT 3/2
1 3 3
N= V(1 − 2 −1/2
)0 ζ , (16.84)
2π 2 ~2 2 2
√
where 0(3/2) = π /2 and ζ (3/2) ≈ 2.612. Introducing all dimensionless numerical
constants and dividing by V, we obtain
mkT 3/2
N
n= = 0.09715 × . (16.85)
V ~2
Finally, the expression for the temperature of the fermion gas reads
~2 n2/3
T = 4.732 × . (16.86)
mk
17 Photon Gas in Equilibrium
17.1 Planck Distribution
One of the most important applications of the quantum statistics for bosons is the
description of the electromagnetic radiation, i.e., a photon gas in thermal equilibrium.
This radiation is usually called the black-body radiation. Maxwell’s equations describ-
ing electromagnetic field dynamics equations are linear equations, which imply that
there are no interactions between photons in media that can be modeled by linear elec-
tric and magnetic susceptibilities, e.g., in vacuum. Thus, a photon gas typically fulfills
the requirements for an ideal gas. Photons are bosons with integral spin σ = 1. From
the usual rule for spin angular momentum, we would thus expect g(σ ) = 2σ + 1 = 3
different spin states for photons. However, due to a symmetry of the electromagnetic
field equations (related to the fact that photon has zero rest mass), the state with zero-
spin projection onto the direction of photon motion turns out to be forbidden. Thus,
there are only two allowed spin states, i.e., we have g(σ ) = 2.
Unlike the ordinary gases, the photon gas does not have a constant number of con-
stituent particles (dN 6= 0). The equilibrium of a photon gas is maintained by constant
absorption and emission of photons by the surrounding matter, e.g., by the walls of
a closed container (cavity). The total number of photons inside the cavity is thus not
constant in time. Because of this, the condition (15.18) does not apply to the photon
gas and has to be omitted. Using the method of Lagrange multipliers, the two remain-
ing equilibrium conditions (15.17), with the + sign, as appropriate for bosons and
(15.19) are, i.e.,
X 1
dU = Ei dni = 0 / · , (17.1)
T
i
X gi + ni
dS = k dni ln =0 / · (−1), (17.2)
ni
i
X Ei gi + ni
− k ln dni = 0. (17.3)
T ni
i
Eq. (17.3) has to be valid for any choice of dni , so the prefactor of each dni therein has
to vanish. This yields the result,
gi
ni = . (17.4)
Ei
exp kT −1
Comparing the result (17.4) with the general result (15.24), we conclude that the pho-
ton gas is a boson gas with zero chemical potential (µ = 0). Assuming that the volume
of the photon gas is large, we can use the continuum from the result (17.4) to obtain
the number of photons within the energy interval (E, E + dE),
dg(E)
dnE = E
. (17.5)
exp kT − 1
V
dg( p) = g(σ ) 4πp2 dp. (17.6)
h3
It should be noted here that photons are massless (m = 0) relativistic particles and that
the relation between energy E and momentum pE is not given by the result (15.45)
used in the general analysis of quantum gases in Chapter 15, “Quantum Distribution
Functions.” The relation between energy E and momentum pE of the gas particles has
an impact on the general thermodynamic behavior of the quantum gas. It is, therefore,
not possible to apply the limit µ → 0 of the general results obtained in Chapter 15,
to the photon gas. In other words, for the extremely relativistic photon gas, we need
to redo some of the analysis made in Section 15.4, “Thermodynamics of Quantum
Systems.” The relativistic relation between energy E and momentum pE of a massive
particle is given by
q
E = p2 c2 + m2 c4 . (17.7)
For massless particles, we obtain a very simple relation E = pc. If we now apply this
relation to the general quantum–mechanical result (2.4), we can write
h
pE = ~κE = κE , E = ~ω = ~|E
κ |c = ~κc. (17.8)
2π
Using g(σ ) = 2 and the equations (17.6) and (17.8), we obtain
3
V h
dg(κ) = 2 3
4π κ 2 dκ, (17.9)
h 2π
or
V ω2 dω V
dg(ω) = 2 4π 3 = 2 3 ω2 dω. (17.10)
(2π) 3 c π c
Photon Gas in Equilibrium 303
Substituting E = ~ ω and (17.10) into (17.5), we obtain the number of photons in the
interval of frequencies (ω, ω + dω) corresponding to the energy interval (E, E + dE)
as follows:
dg(ω) V ω2 dω
dnω = = 2 3 . (17.11)
exp ~kTω − 1 π c exp ~kTω − 1
The contribution to the internal energy of the photon gas dUω from photons in the fre-
quency range (ω, ω + dω) is then obtained as a product of the number of photons dnω
in this range and the energy of an individual photon in this range E = ~ ω. Thus, we
obtain the Planck formula for the spectral energy distribution of black-body radiation
V~ ω3 dω
dUω = . (17.12)
π c exp ~ ω − 1
2 3
kT
1 kT
≈ . (17.13)
~ω
~ω
exp kT −1
V ~ kT 3 VkT
dUω = ω dω = 2 3 ω2 dω. (17.14)
π 2 c3 ~ ω π c
If we now recall the result (17.10), we see that the classical formula (17.14) can be
rewritten as follows:
V
dUω = ω dω kT = dg(ω)kT.
2
(17.15)
π 2 c3
The physical meaning of this result is that the contribution to the internal energy of
the photon gas dUω from photons in the frequency range (ω, ω + dω) is obtained as a
product of the number of radiation modes (i.e., the “vibrational degrees of freedom”)
in this frequency range and the average classical internal energy per mode kT. This
result can be obtained from the classical equipartition theorem, proviso each mode
is interpreted as a classical harmonic oscillator with internal energy Uosc = kT (see
Section 11.4.6, “Equipartition Theorem”). On the other hand, we already know that
the correct internal energy of a single quantum-mechanical oscillator is given by the
equation (12.43), i.e.,
~ω 1
Uosc = + . (17.16)
2 ~ω
exp kT − 1
304 Quantum Statistical Physics
Here, the first term, the so-called vacuum-energy, is temperature independent. Such
term would not affect, for example, the constant volume specific heat. If one leaves
the vacuum energy term in the above quantum–mechanical expression for Uosc and
then uses it to replace the kT term (the classical Uosc ) figuring in the equation (17.15),
one regains the exact Planck formula as written in the equation (17.12). In fact, his-
torically, this was the line of thinking pursued by Planck himself, who considered the
above formula for Uosc without the vacuum energy term. From our previous derivation
of the Planck formula based on the concept of photon gas (rather than on the oscilla-
tor picture), one can see that the vacuum energy term simply did not appear in the
course of this theory. It should be stressed though that in various physical problems,
the vacuum energy of this sort may play a certain role, as evidenced, for example, by
modern cosmological studies of inflatory universe.
Going back to our discussions, we finally note that in the high-frequency limit
(ω → ∞), we can use the approximation exp(x) 1 to obtain the so-called Wien for-
mula in the form
~ω 3
V~
dUω = exp − ω dω. (17.17)
π 2 c3 kT
The formulae (17.14) and (17.17) had been suggested before the development of the
quantum theory. They were applicable in their respective frequency limits, but they
failed to provide an acceptable explanation of the entire frequency spectrum. The
excellent agreement of the Planck formula (17.12) with the experimental data over
the entire frequency spectrum was one of the early proofs of the validity of the quan-
tum hypothesis.
= F − 8 = F − Nµ ⇒ F = . (17.18)
As the chemical potential for the photon gas is equal to zero (µ = 0), we see that the
free energy F of the photon gas is equal to its Helmholtz thermodynamic potential .
The total number of particles in the photon gas is equal to
Z∞
ω2 dω
Z
V
N= dnω = 2 3 . (17.19)
π c
~ω
0
exp kT −1
Photon Gas in Equilibrium 305
On the other hand, using the result (10.42), we can express the total number of particles
of the photon gas in terms of the Helmholtz thermodynamic potential as follows:
∂
N=− . (17.20)
∂µ T
Z∞
~ω
VkT
F== 2 3 ln 1 − exp − ω2 dω. (17.21)
π c kT
0
~ω kT kT
=w⇒ω= w ⇒ dω = dw. (17.22)
kT ~ ~
Z∞
VkT kT 3
F== 2 3 ln 1 − e−w w2 dw,
(17.23)
π c ~
0
or
Z∞
Vk4 T 4
F== 2 3 3 ln 1 − e−w w2 dw.
(17.24)
π c ~
0
The integral on the right-hand side of the equation (17.24) can be integrated by parts
as follows:
Z∞
∞
3
−w
2 w −w
I = ln 1 − e w dw = ln 1 − e
3 0
0
Z∞ Z∞
1 w3 e−w dw 1 w3 dw
− −w
=− . (17.25)
3 1−e 3 ew − 1
0 0
Z∞
Vk4 T 4 w3 dw
F==− 2 3 3 . (17.26)
3π c ~ ew − 1
0
306 Quantum Statistical Physics
On the other hand, from the Planck formula, we obtain the following result for the
total internal energy of the photon gas
Z∞
V~ ω3 dω
U= 2 3 . (17.27)
π c
0
exp ~kTω − 1
Z∞ 3
V ~ kT 4 w dw
U= 2 3 , (17.28)
π c ~ ew − 1
0
or
Z∞
Vk4 T 4 w3 dw
U(T, V) = 2 3 3 . (17.29)
π c ~ ew − 1
0
The equation (17.29) is the caloric-state equation for the photon gas. Comparing the
results (17.26) and (17.29), we see that
U 1
= −pV = − ⇒ pV = U. (17.30)
3 3
Thus, for an extremely relativistic gas like the photon gas, the thermal-state equation
(15.59) is replaced by the equation (17.30). The value of the constant integral on the
right-hand side of the equation (17.29) is given by (15.82), i.e.,
Z∞
w3 dw π4
I(4) = = . (17.31)
ew − 1 15
0
Substituting (17.31) into (17.29), we obtain the caloric-state equation for the photon
gas in the form
π 2 Vk4 T 4
U(T, V) = . (17.32)
15c3 ~3
It is customary to introduce here the Stefan–Boltzmann constant, defined by
π 2 k4 2π 5 k4 kg
σSB = 3 2
= 3 2
= 5.667 × 10−8 . (17.33)
60~ c 15h c s K4
3
4σSB VT 4
U(T, V) = . (17.34)
c
Photon Gas in Equilibrium 307
1 ∂U 16σSB VT 3
cV = = . (17.35)
m ∂T V mc
From the results (17.30) and (17.34), we obtain the thermal-state equation for the
photon gas
4σSB VT 4
pV = . (17.36)
3c
4σSB VT 4
F = = −pV = − . (17.37)
3c
The entropy S of the photon gas is obtained using the general result U = F + TS as
follows:
U − F −3F − F 4F 16σSB VT 3
S= = =− = . (17.38)
T T T 3c
dV dO
du(ω, θ, φ) = dUω , (17.39)
V 4π
or
Thus, we have
The total rate of the radiation energy emerging from the black body is obtained by
integrating the result (17.41) over the entire range of frequencies and space angles,
i.e.,
Z∞ Zπ/2 Z2π
dQ Ac
= dUω cos θ sin θdθ dφ, (17.42)
dt 4πV
0 0 0
or
dQ Ac
= U(V, T). (17.43)
dt 4V
Substituting the caloric-state equation for the photon gas (17.34) into (17.43), we
obtain the Stefan–Boltzmann law in the form
dQ Ac 4σSB VT 4
= = AσSB T 4 . (17.44)
dt 4V c
Thus, the total radiant energy per second of a black body is obtained using the result
(17.44).
8π hc dλ
dUλ = u(λ)dλ = . (17.45)
λ5 exp hc − 1
λkT
(a) Find the value of the wavelength λm , where the function u(λ) has its maximum
value.
(b) If we treat the Sun as a black body with λm = 480 nm, calculate the temperature
of the Sun.
Solution
(a) The maximum of the function u(λ) is obtained from the condition
hc
du exp
8π h2 c2 λkT 8πhc 5
= 7 i2 − 6 = 0, (17.46)
λ kT λ
dλ
h hc
hc exp λkT − 1
exp λkT −1
Photon Gas in Equilibrium 309
or
hc
8πhc 1 exp λkT
hc − 5 = 0, (17.47)
λ6 exp hc − 1 λkT exp hc − 1
λkT λkT
or
hc
hc exp λkT
= 5, (17.48)
λkT exp hc − 1
λkT
or
hc hc
= 5 1 − exp − . (17.49)
λkT λkT
hc
Introducing here a new variable w = λkT , we obtain the equation
w = 5 1 − e−w .
(17.50)
In order to find a numerical solution of this equation, we use the following iteration
formula
wj+1 = 5 1 − exp(−wj ) , w0 = 5.
(17.51)
hc
T= = 6037 K. (17.54)
4.965λm k
Problem 2
The Sun can be treated as a black body with an approximate surface temperature
T = 5800 K. The radius of the Sun is RS ≈ 7 × 108 m and the distance from Sun–Earth
is RSE ≈ 1.5 × 1011 m.
(a) Calculate the radiant energy per second (power) emitted by the Sun.
(b) Calculate the energy rate (power) per unit area that reaches the Earth’s atmosphere.
310 Quantum Statistical Physics
Solution
(a) Using the Stefan–Boltzmann Law, we have
dQ
= AσSB T 4 = 4π R2S σSB T 4 = 3.95 × 1026 W. (17.55)
dt
(b) The energy rate per unit area that reaches the Earth’s atmosphere is obtained as
dQE 1 dQ kW
= 2
= 1.40 2 . (17.56)
dt 4π RSE dt m
Problem 3
The light from an ordinary lamp can approximately be treated as a black-body radi-
ation. If the light from the lamp has a maximum intensity at a wavelength of λm =
1200 nm, calculate the temperature of the lamp.
Solution
Using the formula (17.53) for the wavelength λm , i.e.,
hc
λm = , (17.57)
4.965kT
we obtain
hc
T= = 2415 K. (17.58)
4.965λm k
Problem 4
Just below the surface of the Sun, photons are in thermal equilibrium at a temperature
T = 6000 K. The radiation into a certain space angle can be described as a radiation
through a surface A = r2 , where at the surface of the Sun, we have r = RS = 7 ×
108 m, being the radius of the Sun. Calculate the linear momentum of the photons
radiated into the solid angle per unit time. Assume that 4π . If the radiation is
totally reflected from an object covering this solid angle, calculate the force exerted
by photons on the object. Assume that the object is a perfect reflector and that it is
flat. Also assume that the photons strike the object perpendicularly. If a spaceship at
the distance r = RSE = 1.5 × 1011 m from the Sun wants to use such an object (solar
sail) for acceleration, how large of an area of the solar sail needs to be in order to
generate the acceleration a = 0.01 g? Total mass of the solar sail and the spaceship is
M = 1000 kg.
Photon Gas in Equilibrium 311
Solution
The total radiant energy per second of the Sun is obtained using the result (17.44),
i.e.,
dQ
= AS σSB T 4 = 4π R2S σSB T 4 . (17.59)
dt
dE
= 4π R2S σSB T 4 = R2S σSB T 4 . (17.60)
dt 4π
The linear momentum of a single photon is related to its energy by p = E/c. Thus, the
momentum of radiation into a solid angle per unit time is
dp R2 σSB T 4
= S . (17.61)
dt c
If the photons are totally reflected from an object, the linear momentum transferred
from the photons to the object per unit time is twice the momentum given by (17.61).
The force on the object caused by the total reflection of the photons is equal to this
momentum transfer per unit time, i.e.,
2R2S σSB T 4
F = Ma = . (17.62)
c
At a distance r = RSE , the solid angle of such a solar sail with irradiated surface A is
= A/R2SE . The equation (17.62) then gives
2R2S σSB T 4 A
Ma = . (17.63)
c R2SE
The area of the solar sail needed to generate the given acceleration is thus
MacR2SE
A= = 9200014 m2 ∼ 3 km × 3 km. (17.64)
2R2S σSB T 4
18 Other Examples of Boson Systems
18.1 Lattice Vibrations and Phonons
The atoms or molecules in a solid-state specimen are frequently arranged in a periodic
structure called the crystal lattice. In conducting materials, e.g., metals, the conducting
electrons are free to move. They are delocalized from the lattice sites and they con-
stitute an electron gas in the metal. The properties of the free electron gas have been
studied in Chapter 16, “Electron Gases in Metals,” using Fermi–Dirac statistics. The
remaining positively charged ions are localized at the lattice sites. At zero temperature
(T = 0), the ions are frozen in their equilibrium positions in the crystal lattice. How-
ever, at finite temperatures (T > 0), the ions are not at rest and they vibrate about their
equilibrium positions.
The magnitude of displacements of ions from their equilibrium position is typically
small compared with the lattice constant (the size of the unit cell of the lattice) so that
the ion vibrations are approximately harmonic. In quantum theory, lattice vibrations
can be described in terms of the particle-like objects (quasi-particles) called phonons.
Conceptual relation between phonons and classical lattice vibrations is the same as the
one between photons and classical electromagnetic fields. In both cases, the classical
field can be represented as set of modes each modeled by a simple harmonic oscillator.
The quantization of this field reduces thus to the quantization of these oscillators (see
Chapter 4, “Energy of Vibrations,”). The n-th energy state of each of these oscillators,
with energy E = E0 + n~ω, can be depicted as a state occupied by n bosons each with
energy ~ω. In the case of lattice vibrations, these bosonic quasi-particles are called
phonons, whereas in the case of electromagnetic fields, we call them photons. By being
bosonic, both photons and phonons have to obey Bose–Einstein statistics discussed in
Chapter 15, “Quantum Distribution Functions.” Unlike the ordinary gases and simi-
larly to the photon gas, the phonon gas does not have a constant number of constituent
particles (dN 6= 0). Thus, similarly to the case of the photon gas, the chemical potential
for phonons is equal to zero (µ = 0).
Like a photon, a single phonon has the energy E = ~ω, so the number of phonons in
the interval of frequencies (ω, ω + dω), corresponding to the energy interval (E, E +
dE), can be obtained using the result (17.11), obtained in the previous chapter for
photons as follows:
dg(ω)
dnω = , (18.1)
~ω
exp kT −1
where dg(ω) is the number of states in the energy interval (E, E + dE) corresponding
to the interval of frequencies (ω, ω + dω). In order to determine the number of states
dg(ω) for phonons, we need to determine the dispersion relation ω = ω(E κ ) for the
lattice vibrations, where κE = pE/~ is the wave vector (related to the momentum) of
phonons.
where j is the label of a particular unit cell. Here, 1 ≤ j ≤ N, where N is the total
number of unit cells in the one-dimensional lattice.
Much like for photon states, where wave functions are plane-wave solutions to
Maxwell’s equations, the wave functions of phonon states are plane wave solutions of
the equations (18.2) that can be written as
where Rj = j a is the position of the j-th unit cell, and κ and ω are the wave vector and
(angular) frequency of the mode, respectively. By the above equations, it is easy to see
that
uAj+1 (t) = e−iκa uAj (t), uBj−1 (t) = e+iκa uBj (t), (18.5)
üAj (t) = −ω uAj (t),
2
üBj (t) = −ω uBj (t).
2
(18.6)
MA MB MA MB MA MB
Other Examples of Boson Systems 315
Inserting the above results into the equations (18.2) yields [after canceling the common
factor exp(−iκRj + iωt)]
−MA ω2 + 2g uA (κ) − g 1 + eiκa uB (κ) = 0,
(18.7)
− g 1 + e−iκa uA (κ) + −MB ω2 + 2g uB (κ) = 0,
(18.8)
2g 2 2g2
ω4 − ω + (1 − cos κa) = 0, (18.14)
M MA MB
or finally
2g 2 4g2 κa
ω4 − ω + sin2 = 0. (18.15)
M MA MB 2
The two solutions of this equation represent the dispersion relations for the two vibra-
tion modes ω±2 = ω2 (κ) , and they are given by
±
1/2
( )
g 4M 2 2 κa
ω± (κ) =
2
1± 1− sin . (18.16)
M MA MB 2
316 Quantum Statistical Physics
√
In the limit of small κ, we can use 1 − x ≈ 1 − x/2 as well as sin x ≈ x to obtain
g 1 4M 2 κa 2
ω−
2
(κ) ≈ 1− 1− , (18.17)
M 2 MA MB 2
or
g
ω−
2
(κ) ≈ a2 κ 2 ⇒ ω− (κ) ≈ cS κ, (18.18)
2(MA + MB )
g
r
cS = a. (18.19)
2 (MA + MB )
Using here the Euler formula (eix = eix+i2π ), and the fact that, by equations (18.16)
and (18.17),
2π
ω(κ) = ω κ + , (18.22)
a
meaning that uj (t, κ) is periodic in κ , with the period 2π/a. Thus, the modes with
wave vectors κ and κ + 2π/a are identical to each other. The modes, i.e., the phonon
states that are different from each other, are to be confined within one period of uj (t, κ)
as a function of κ, e.g., the range
π π
− ≤κ ≤+ . (18.24)
a a
Other Examples of Boson Systems 317
This range in the wave vector space is known as the first Brillouin zone. Thus, the wave
vectors of all physically different modes, i.e., of the phonon states, must be confined
within the first Brillouin zone. Its existence is a direct consequence of the discreteness
imposed by the presence of the crystal lattice. Indeed, in the continuum limit of zero
lattice constant a → 0, the size of the first Brillouin zone diverges, so it would cover
the entire wave vector space. Such a situation is actually realized for photons, since the
physical space can be thought of as a continuum limit of a three-dimensional lattice.
In this limit, there are no restrictions on the magnitudes of photon wave vectors, as we
tacitly assumed in Chapter 17, “Photon Gas in Equilibrium.” Phonons, however, live
on a crystalline lattice and the first Brillouin zone has always a finite size. Its existence
must be taken into account, as done in our discussions in the following.
Another restriction on the possible values of wave vectors comes from a finite size
of the crystalline sample, such as the length L = Na of the one-dimensional crystal
in our example above. Such restrictions are due boundary conditions imposed on
the wave functions. In statistical physics, we are usually interested in large systems
(L a), and the significant extensive quantities (e.g., internal energy) are insensitive
to detailed form of boundary conditions. For the wave functions such as (18.21), the
mathematically convenient form is the so-called periodic boundary condition,
These wave vectors are uniformly distributed in the κ-space and within the interval
(κ, κ + dκ), there are
dκ L
2π
= dκ, (18.29)
L
2π
The above discussions can be easily generalized to lattices in any number of spe-
cial dimensions d, in which atomic vibration displacements uE(R
E , t) are d-dimensional
vectors. The vibration modes are again plane waves of the form,
uE(R
E , t) = C κ ·R
E exp −iE E + iω(κ)t .
(18.30)
In this case, the allowed wave vectors κE are d-dimensional vectors in a d-dimensional
κE -space. For a d-dimensional crystal shaped as a cube with side L, periodic boundary
conditions demand that each component κE satisfies the equation (18.26). Due to this,
the allowed wave vectors form, in the d-dimensional κE -space, a cubic lattice with
the lattice constant 2π/L [just as in equation (18.27)], so the d-dimensional κE -space
volume that comes per each allowed wave vector is the volume of a cube with side
2π/L, i.e.,
d
(2π)d
2π
= , (18.31)
L V
where V = Ld is the volume of the crystal. Thus, the number of allowed wave vectors
in the κE -space volume element dd κ is
dd κ V
= dd κ. (18.32)
(2π )d (2π)d
V
Due to this, for example, for d = 3, the number of allowed wave vectors within the
spherical shell with radii κ and κ + dκ is
shell volume V
dg(κ) = = 4π κ 2 dκ. (18.33)
(2π)3 (2π ) 3
V
For the so-called cubic d-dimensional lattices, the lattice cells are cubes with side a (=
the lattice constant). For these lattices, the first Brillouin zone in wave vector space is
a d-dimensional cube with the side 2π/a [just as in equation (18.24)], and its κE -space
volume is thus
d
(2π )d (2π )d
2π
VBZ = = = , (18.34)
a ad vcell
with vcell = ad , the real-space lattice cell volume. Thus, by equations (18.30) and
(18.34), the total number of allowed wave vectors is
(2π )d
VBZ vcell V
= = = N. (18.35)
(2π )d (2π )d vcell
V V
Other Examples of Boson Systems 319
So, the number of allowed wave vectors is equal to the number of the crystal lattice
cells N.
For noncubic lattices, the shape of the Brillouin zone is more complicated; however,
the number of allowed wave vectors is still equal to the number of the crystal lattice
cells N. Thus, the equation (18.35) applies to whatever lattice and in general,
(2π)d N
VBZ = = (2π )d . (18.36)
vcell V
The Brillouin zone is never spherical for realistic crystals; however, as done for the first
time by the Dutch physicist Peter Debye, it is sometimes convenient to approximate it
by a spherical shape. Such a spherical Brillouin zone is called the Debye sphere, and
its radius is chosen to respect the general rule stated in equation (18.36). For example,
for d = 3, the radius κD of the Debye sphere is determined from the equation
ZκD
4π N
4πκ 2 dκ = (κD )3 = VBZ = (2π )3 . (18.37)
3 V
0
for a d-dimensional crystal of N lattice cells with ν atoms per cell. The corresponding
heat capacity is
∂U
CV = = d · ν · Nk = d · Natoms k. (18.39)
∂T V
CV = 3ν · Nk = 3Natoms k (18.40)
shell volume V
dg(κ) = = S(d)κ d−1 dκ (18.41)
(2π )d (2π )d
V
with V, the volume of the d-dimensional system (e.g., V = Ld , for a cubic sample
with the side L). In the equation (18.41), the S(d) labels the surface area of the
d-dimensional sphere with unit radius, given by the formula
(2π)d/2 21−d/2
S(d) = , (18.42)
0(d/2)
reproducing the familiar results S(3) = 4π, S(2) = 2π , and S(1) = 2. The equation
(18.42) is, however, meaningful even for noninteger d! By using it, one can, for exam-
ple, generalize the equation (18.37) for the volume of the Debye sphere to any, even
noninteger d,
ZkD
S(d) N
S(d)κ d−1 dκ = (κD )d = VBZ = (2π )d . (18.43)
d V
0
~ωα (E
κ)
Uα (E
κ) = + < nα (E
κ ) > ~ωα (E
κ ), (18.44)
2
or
~ωα (E
κ) ~ωα (E κ)
Uα (E
κ) = + . (18.45)
ω α )
(E
κ
2 exp ~
−1 kT
Here, the first term is the ground-state contribution, the so-called zero-point (“vac-
uum”) energy. The second term in the equation (18.45) can be interpreted as the con-
tribution of the phonons occupying the state labeled by κE and α. Each of them carries
the energy ~ωα (Eκ ), and their average occupation number for this state is
1
< nα (E
κ ) >= . (18.46)
~ωα (Eκ )
exp kT −1
The equation (18.46) coincides with the Bose–Einstein statistics expression in the
equation (15.25), with zero chemical potential. Phonons can be thus interpreted as
bosons, which actual total number is fixed by temperature, much like we found for
photons in Chapter 17.
The total vibrational internal energy is obtained by summing the contributions in
the equation (18.45) over all modes. This involves summing the equation (18.45) over
all N allowed values of κE within the first Brillouin zone, as well as summing over all
values of α = 1, 2, . . . , d · ν. The number of allowed states within the d-dimensional
κE -space element is given by (18.32). Using this, we can sum the single-mode contri-
butions in the equation (18.45) over all modes, to find the internal vibration energy of
the crystal in the form,
d·ν
dd κ
X Z
UVIB (T) = V Uα (E
κ ) = U0 + Uphonon (T). (18.47)
(2π )d
α=1 BZ
322 Quantum Statistical Physics
Above, the integrals are done over the first Brillouin zone. The vibration internal
energy in the equation (18.47) is written as a sum of the term
d·ν
dd κ ~ωα (E
κ)
X Z
U0 = V d
(18.48)
(2π ) 2
α=1 BZ
d·ν
dd κ
X Z
Uphonon (T) = V < nα (E
κ ) > ~ωα (E
κ)
(2π )d
α=1 BZ
d·ν
dd κ ~ωα (Eκ)
X Z
= V d
, (18.49)
(2π ) exp ω α )
(E
κ
~
α=1 BZ kT −1
representing the contribution coming from thermally excited phonons. By the equa-
tion (18.49), this contribution vanishes for T → 0, so the net vibration energy
UVIB (T) → U0 for T → 0. The zero-point energy is thus a vibrational contribution to
the systems ground-state energy. The zero-point energy U0 ∼ ~ is of purely quantum-
mechanical origin, yet it may be significant for a crystal comprised of lighter atoms
such as helium or argon. Being temperature independent, U0 does not affect the exper-
imentally significant constant volume heat capacity, which is governed by the phonon
contribution given in the equation (18.49), i.e.,
In the high-temperature limit, by using exp(x) ≈ 1 + x valid for x 1, we can see that
the integrands in the equation (18.49) are all approximated by kT (the classical expres-
sion for the harmonic oscillator internal energy). Thus, for high enough temperatures,
we have
d·ν
dd κ
X Z
UVIB (T) ≈ Uphonon (T) ≈ V kT
(2π )d
α=1 BZ
V
= d·ν VBZ kT = d · ν · N · kT, (18.51)
(2π)d
where we used the equation (18.36), for the first Brillouin zone volume, to calculate
N
Z
dd κ = VBZ = (2π )d . (18.52)
V
BZ
Other Examples of Boson Systems 323
coinciding with the classical Dulong–Pettit law in the equation (18.40), obtained from
the equipartition theorem. Thus, the high-temperature limit of our quantum theory is
the classical limit. Notably from the above derivation, detailed forms of the disper-
sion relations ωα (Eκ ) simply disappear in the classical limit. It is thus clear that the
dispersion relations ωα (E κ ) will play a significant role as the temperature decreases
and quantum effects become prominent. In the following, we will show that the dif-
ference between the dispersion relations for the acoustic (ωα (E κ ) → 0 as κ = |Eκ | → 0)
and the optical modes (ωα (E κ = 0) 6= 0) plays a significant role at low temperatures.
For d-dimensional crystals with ν atoms per lattice cell, for each κE , there are d acous-
tic modes and d · (ν − 1) optical modes, as exemplified in Section 18.1.1, “Vibration
Modes,” for the case d = 1 and ν = 2. Thus, in crystals with only one atom per cell
(ν = 1), all d modes are acoustic. These are essentially modes of sound, with the veloc-
ities cα , i.e.,
ωα (E
κ ) = cα |E
κ | = cα κ, α = 1, 2, . . . , d, (18.54)
κ | = κ π/a, i.e., close to the center of the first Brillouin zone. On the
for small |E
other hand, the remaining d · (ν − 1) optical modes have
ωα (E
κ ) = ωα (E
κ = 0) 6= 0, α = d + 1, d + 2, . . . , d · ν, (18.55)
κ | = κ π/a. By the equation (18.49), one can separate the internal energy
for small |E
contributions coming from acoustic and optical modes,
d
dd κ ~ωα (E κ)
X Z
Uac (T) = V d
, (18.57)
(2π ) exp ω α )
(E
κ
~
α=1 BZ kT −1
d·ν
dd κ ~ωα (Eκ)
X Z
Uopt = V . (18.58)
(2π )d exp ~ωα (Eκ ) − 1
α=d+1 BZ kT
In the so-called Einstein model, motivated by the equation (18.55), the disper-
sion of optical modes is completely ignored, so in the equation (18.58), one sets
ωα (E
κ ) = ωα (E
κ = 0) throughout the first Brillouin zone. With this, integrands in the
324 Quantum Statistical Physics
equation (18.58) become κE -independent and the integrals can be calculated exactly as
follows:
d·ν
dd κ ~ωα (0)
X Z
Uopt = V
(2π )d exp ~ωα (0) − 1
α=d+1 BZ kT
d·ν
~ωα (0) V
Z
dd κ
X
=
~ωα (0) (2π )d
α=d+1 exp kT −1 BZ
d·ν
X ~ωα (0) V
= V
d BZ
~ωα (0)
− 1 (2π )
α=d+1 exp kT
d·ν
X ~ωα (0)
=N , (18.59)
~ωα (0)
α=d+1 exp kT −1
where we used the equation (18.36), for the first Brillouin zone volume, to calculate
N
Z
dd κ = VBZ = (2π )d . (18.60)
V
BZ
Thus, as temperature goes to zero, the optical mode contributions go to zero rapidly,
in an exponential fashion. By the equation (18.61), the associated heat capacity also
rapidly goes zero , as
d·ν
∂Uopt (T) ~ωα (0) 2 ~ωα (0)
X
Copt = ≈ Nk exp − . (18.62)
∂T V kT kT
α=d+1
On the other hand, as it will be shown in the following, the low-temperature contribu-
tion coming from acoustic modes yields a contribution of the form
∂Uac (T)
Uac ∼ T d+1 ⇒ Cac = ∼ Td, (18.63)
∂T V
which approaches zero only as a power law of temperature and thus dominates over the
optical mode contribution in the equations (18.61) and (18.62). Thus, at low enough
temperatures,
Uphonon (T) = Uac (T) + Uopt (T) ≈ Uac (T) ∼ T d+1 , (18.64)
Other Examples of Boson Systems 325
and
The result in the equation (18.63) [for d = 3] and the special role played by acous-
tic phonons were revealed by Debye in early years of quantum-statistical physics.
He observed that, at low temperatures, the dominant contribution to the integrals in
the equation (18.57) comes from a range of short wave vectors such that ~ωα (E κ) =
~cα κ ∼ kT, i.e.,
kT
κ∼ . (18.66)
~cα
Indeed the integrands in the equation (18.57) are exponentially depressed for wave
vectors much larger than those in (18.66). Since the wave vector scale in the equa-
tion (18.66) becomes small at low temperatures, Debye further realized that one can
obtain asymptotically correct results (for the T → 0 limit), just by using in the equa-
tion (18.57), the short wave vector (long wavelength) form of the acoustic modes
dispersion relation,
ωα (E
κ ) = cα |E
κ | = cα κ, α = 1, 2, . . . , d. (18.67)
Indeed, consider the temperatures much smaller than the characteristic temperature
(the so-called Debye temperature), defined by
~cα
Tα = κD , (18.68)
k
with κD , the radius of Debye sphere (serving here just as a measure of the first Brillouin
zone size). By the equation (18.68), we see that, for T Tα , the dominant wave-vector
range in the equation (18.66) satisfies
kT kTα
κ∼ = κD ⇒ κ κD . (18.69)
~cα ~cα
In fact, by equations (18.66) and (18.68), for the dominant wave-vectors, we find
κ kT T T κ T
∼ = = ⇒ ∼ 1. (18.70)
κD ~cα κD ~cα κD /k Tα κD Tα
Thus, for T Tα , the integrals in the equation (18.57) are dominated by a small por-
tion of the first Brillouin zone, which is close to its center, where the approximation
(18.54) is valid. Thus, in the calculation of the acoustic-phonons internal energy in
(18.57), at low enough temperatures, one can employ the simple dispersion relations
in the equation (18.67), as eventually Debye did. In view of the conclusion in the
equation (18.70), the contributions to the integrals in (18.57) coming from the outer
326 Quantum Statistical Physics
boundaries of the first Brillouin zone are expected to be small. So, at low enough
temperatures, one can simply assume that the Brillouin zone has infinite size in the
wave vector space. This corresponds to a crystalline lattice with zero lattice constant.
In physical terms, it means that the asymptotic law gives the low-temperature phonon
internal energy density
Uphonon
ũphonon = (18.71)
V
will eventually come out in a form that does not depend on the microscopic details
such as the lattice constant. In other words, we expect this quantity to depend only
on the temperature, but it should be independent of the lattice cell sizes, in the T → 0
limit. This situation is dramatically different from the one we have in the classical
high-temperature limit, where, by the equation (18.38), we have the result
d · ν · NkT d · ν · kT d · ν · kT
ũphonon = = = , (18.72)
V V/N vcell
in which the dependence on the crystal lattice cell vcell volume is manifest. With
decreasing temperature, dependence on microscopic details will simply disappear, in
the asymptotically valid laws giving the internal energy density at low temperatures.
To show this, we fulfill the program outlined above, by importing the dispersion
relations (18.67) into the equation (18.57). A nice feature of this step is that the inte-
grands in (18.57) become functions of the magnitude of the wave vector only, so one
can replace the d-dimensional integrals therein with the integrals over κ only, via
Z ZκD
d
d κ → S(d)κ d−1 dκ. (18.73)
BZ 0
In the equation (18.73), we anticipated that, in our calculation, we will replace the
original Brillouin zone with a “spherical Brillouin zone,” i.e., the Debye sphere dis-
cussed in Section 18.1.1, “Vibration Modes.” We recall that this approximation does
not change the volume of the Brillouin zone. Because of this, it is assured that our final
result will have the correct classical (high-temperature) limit for the acoustic-phonon
contributions,
which relies only on the volume of the Brillouin zone but not on its shape or on the
form of dispersion relation [see, e.g., our derivations in (18.52)]. In addition, by the
above discussions (18.71), we also expect that our result will be asymptotically exact
also in the low-temperature limit. In this limit, the actual shape and size of the first
Brillouin zone does not matter. It may thus be set to be of infinite size, corresponding
to setting κD → ∞ in the equation (18.73). Yet, to obtain a theory working also in the
classical regime, one needs to keep κD finite, to assure that the equation (18.74) holds.
Other Examples of Boson Systems 327
It should be stressed though that in the intermediary temperature range (in between
the quantum and classical regimes), the quantitative validity of applying the con-
cept of Debye sphere and simple dispersion relations (18.67) is questionable. In the
intermediary regime, the detailed forms of dispersion relations and of the Brillouin
zone do matter. However, here, we are primarily interested in the low-temperature
limit in which the theory results are asymptotically exact. Thus, we import equations
(18.67) and (18.73) into the equation (18.57) to obtain the major equation of the Debye
theory,
d ZκD
X S(d)κ d−1 dκ ~cα κ
Uac = V . (18.75)
(2π )d ~cα κ
α=1 0 exp kT −1
d ZκD
X S(d)κ d−1 dκ
Uac = V kT
(2π )d
α=1 0
d ZκD
V
S(d)κ d−1 dκkT
X
=
(2π )d
α=1 0
V
=d· VBZ kT = d · N · kT, (18.76)
(2π)d
where we used the equation (18.60) for the last steps. Thus, as expected, the Debye
theory has the correct classical, high-temperature limit given by the equation (18.74).
At low temperatures, the equation (18.66) suggests the following change of variable κ
into a variable w, via
kT
κ= w, (18.77)
~cα
d Zwα d
X (kT)d+1 S(d) w dw
Uac = V . (18.78)
(~cα )d (2π )d ew − 1
α=1 0
~cα ~cα κD /k Tα
wα = κD = = , (18.79)
kT T T
328 Quantum Statistical Physics
where we recalled the definition of the Debye temperatures in the equation (18.68).
The integrals in (18.78), all converge in the low-temperature limit, i.e., when
Tα
wα = → ∞, (18.80)
T
which is, by the equation (18.79), equivalent to the formal limit κD → ∞, in accor-
dance with our previous discussions. In this limit, any information on microscopic
details, such as the size of the Debye sphere, i.e., lattice constant, simply disappear,
and the equation (18.78) yields the universal form for the internal vibration energy
density
d
Uac (T) (kT)d+1 X 1
ũac (T) = = K(d) , (18.81)
V ~d (cα )d
α=1
and the associated heat capacity per unit volume, c̃ac = Cac /V, i.e.,
d
∂ ũac (kT)d X 1
c̃ac (T) = = (d + 1) · K(d)k d . (18.82)
∂T ~ (cα )d
α=1
The results in equations (18.81) and (18.82) are asymptotically valid for T Tα , for
whatever shape and size of the first Brillouin zone. In equations (18.81) and (18.82),
Z∞
S(d) wd dw
K(d) = (18.83)
(2π)d ew − 1
0
as anticipated before in the equation (18.63). So, the acoustic modes contribution
indeed dominates over that optical modes, as argued in the equation (18.65). Whereas
independent of microscopic (atomic) details such as lattice constants, the results
(18.81) and (18.82) do depend only on macroscopic properties of the system, such
as the temperature and experimentally measurable velocities cα (α = 1, 2, . . . , d) of
the d-long-wave length acoustic (sound) modes. We note that, for high-symmetry
(“isotropic”) crystals and glasses, there is one longitudinal acoustic mode, with the
velocity cL , and d − 1 transverse acoustic modes, all with the velocity cT , so in the
equations (18.81) and (18.82), we have
d
X 1 1 d−1
= + . (18.85)
(cα )d (cL )d (cT )d
α=1
Other Examples of Boson Systems 329
For such system, there are thus only two Debye temperatures as defined by the equa-
tion (18.68),
~cL ~cT
TL = κD , TT = κD , (18.86)
k k
whereas the equation (18.78) gives
ZwL d ZwT d
Uac (kT)d+1 S(d) 1 w dw d−1 w dw
ũac = = + . (18.87)
V ~d (2π )d (cL )d ew − 1 (cT )d ew − 1
0 0
~cL TL ~cT TT
wL = = , wT = = . (18.88)
kT T kT T
Even though rarely realized in realistic systems, the above results are sometimes sim-
plified by the assumption that cL ≈ cT . Within this, “single sound velocity” approxi-
mation (cL = cT = cS ), there is only one Debye temperature,
~cS ~cS TD
TD = κD ⇒ wD = = . (18.89)
k kT T
Thus, the equations (18.75) and (18.78) give
ZκD ZwD
S(d)κ d−1 dκ ~cS κ (kT)d+1 d · S(d) wd dw
ũac = d · = . (18.90)
(2π )d cS κ (~cS )d (2π)d ew − 1
0
exp ~kT −1 0
The equation (18.90) is frequently displayed in the d = 3 form (see Problem 1), in
which case, we use S(d = 3) = 4π . The d = 2 and d = 1 cases are also experimentally
interesting. For them, S(d = 2) = 2π and S(d = 1) = 4π can be used to write down the
equations such as the equation (18.75) and other equations in the above discussion. The
theory can be extended even to noninteger dimensions d, by using the general result
for S(d) displayed in the equation (18.42), i.e.,
(2π)d/2 21−d/2
S(d) = . (18.91)
0(d/2)
Z∞ Z∞
S(d) wd dw 21−d/2 wd dw
K(d) = w
= . (18.92)
(2π)d e − 1 (2π )d/2 0(d/2) ew − 1
0 0
330 Quantum Statistical Physics
Z∞
wd dw
= 0(d + 1)ζ (d + 1), (18.93)
ew − 1
0
For the case d = 3, the integral in the equation (18.93) has already been calculated
in (15.82), and by the same procedure, one can also calculate the integral (18.93) for
d = 1, by using the equation (15.80), and the Bernoulli number in the equation (15.82).
Thus, one finds
Z∞
w1 dw (2π )2 π2
= 0(1 + 1)ζ (1 + 1) = I(2) = B2 = , (18.95)
ew − 1 4·1 6
0
which
√ can be combined with the equation (18.92), to find (by recalling that 0(1/2) =
π),
21−1/2 π2 π
K(d = 1) = = . (18.96)
(2π) 0(1/2)
1/2 6 6
Z∞
w3 dw (2π )4 π4
= 0(3 + 1)ζ (3 + 1) = I(4) = B4 = (18.97)
ew − 1 8 15
0
21−3/2 π4 π2
K(d = 3) = = . (18.98)
(2π)3/2 0(3/2) 15 30
is the so-called Apery’s constant, for which only the above numerical value is known.
Thus, numerically,
ζ (3)
K(d = 2) = = 0.38262659603 . . . . (18.101)
π
d
d X 1
d
= , (18.102)
(cS ) (cα )d
α=1
or, for the case of isotropic solids, by the equation (18.85), via
d 1 d−1
d
= d
+ . (18.103)
(cS ) (cL ) (cT )d
The low-temperature universal results for the acoustic-phonon internal energy density
ũac (T) and heat capacity per unit volume c̃ac (T) = Cac /V in the equations (18.81) and
(18.82), can thus be written in the simple forms
and
∂ ũac (kT)d
c̃ac (T) = = d · (d + 1) · K(d)k , (18.105)
∂T (~cS )d
respectively. Combining equations (18.104) and (18.105), with the above results for
K(d), we find the following:
For d = 1,
and
∂ ũac π kT
c̃ac (T) = = k ∼ T. (18.107)
∂T 3 ~cS
For d = 2,
and
∂ ũac 6ζ (3) kT 2
c̃ac (T) = = k ∼ T 2. (18.109)
∂T π ~cS
For d = 3,
and
∂ ũac 2π 2 kT 3
c̃ac (T) = = k ∼ T 3. (18.111)
∂T 5 ~cS
It should finally be stressed that these results, as they stand, apply only if all d acoustic
modes are in the quantum regime. It means, for T min(Tα ), that is, by the equation
(18.68), for
~ min(cα )
T min(Tα ) = κD . (18.112)
k
In other words, the acoustic mode with the smallest sound velocity imposes the upper
temperature limit for the applicability of the above universal results. Typically, this is
the transverse mode, so min(cα ) = cT .
p2 ~2 κ 2
E(κ) = = . (18.113)
2m 2m
Unlike the classical ideal gases, the ideal gases of fermions have a nonzero kinetic
energy even at zero absolute temperature, i.e., in their N-particle ground state (see
Chapter 16). The reason for this is the Pauli exclusion principle, which states that not
more than one fermion can occupy the same quantum state. Because of this principle,
the fermion gas ground state cannot be formed by putting all N fermions into the single
state with zero kinetic energy [with E(κ = 0) = 0]. Rather, all energy states up to the
Fermi energy level must be occupied. Unlike the case of fermions, any number of
bosons can occupy a single quantum state. Because of this, the boson gas ground state
can be formed simply by putting all N bosons into the state with zero kinetic energy
[with E(κ = 0) = 0]. Thus, at T = 0, there is a macroscopic fraction (= 1) of bosons
occupying a single quantum state. In this section, we will discuss a closely related
Other Examples of Boson Systems 333
(but not really obvious) phenomenon of the so-called Bose–Einstein condensation that
starts to occur already at nonzero temperatures. It turns out that a finite macroscopic
fraction of bosons starts to occupy the κ = 0 state already below a certain nonzero
critical temperature TC . At TC , this fraction is zero, and, as the temperature decreases
from TC down to 0, this fraction continuously increases from 0 to 1.
Much like in our discussion of phonons, the phenomenon of Bose–Einstein con-
densation can be studied in any number of spatial dimensions d, such as d = 3 (e.g., N
bosons in a cubic box with the volume V = L3 ), d = 2 (e.g., N bosons in a square with
the area A = L2 ), and d = 1 (e.g., N bosons confined to a line segment with the length
L1 ). Here, we will focus on the case d = 3, whereas a general d case is discussed in the
Problem 2 of this chapter. Here, we note that for d = 2 and any d < 2 (in particular, for
d = 1), the critical temperature TC of the Bose–Einstein condensation is depressed to
zero. Thus, in these dimensions, TC = 0, i.e., there is no real Bose–Einstein condensa-
tion. On the other hand, for any d > 2 (in particular, for d = 3), the critical temperature
TC of the Bose–Einstein condensation is nonzero. Thus, for any d > 2, there is a real
Bose–Einstein condensation. In order to study the phenomenon of Bose–Einstein con-
densation in d = 3, let us consider the equation (15.52) in the case of spinless bosons,
i.e.,
Z∞ √
m3/2 V EdE
N=√ . (18.114)
2π 2 ~3
0
exp E−µ
kT − 1
It should be noted that the chemical potential µ for bosons is either negative or in some
cases (e.g. for massless photons), it is equal to zero. A positive chemical potential
cannot occur for ideal gases of bosons. It is because the state occupation numbers
must be positive for all states, whereas a negative µ would mean that these numbers
are negative in the range Ei < µ for (positive) single-particle kinetic energies Ei , i.e.,
ni 1
n̄i = = < 0, Ei < µ. (18.115)
gi
E −µ
exp ikT − 1
Let us now consider the process of lowering the temperature of a boson system at
constant particle density N/V. In order to keep the particle density N/V constant, the
integral on the right-hand side of the equation (18.114) must remain constant as T is
decreasing. This requires that |µ| also decreases when the temperature T is decreasing.
Interestingly, for the bosons in d = 3, the equation (18.115) predicts that µ approaches
zero at a nonzero temperature TC . The critical temperature TC is determined from
the condition that µ → 0 from the negative values. Using (18.114) with T = TC and
µ = 0, we have
Z∞ √
m3/2 V EdE
N=√ . (18.116)
2π 2 ~3
0
exp kTEC − 1
334 Quantum Statistical Physics
3/2 Z∞
V w1/2 dw
2mkTC
N= , (18.117)
4π 2 ~2 ew − 1
0
or
3/2
2mkTC 3 3
2
4π n = 0 ζ , (18.118)
~2 2 2
√
where n = N/V , 0(3/2) = π /2, and ζ (3/2) ≈ 2.612. Thus, we obtain the following
result for the critical temperature TC , as a function of the density of the boson system
~2 2/3
TC = 3.3128 × n . (18.119)
mk
Note that, up to a numerical factor, the critical temperature TC in the equation (18.119)
is the same as the gas quantum temperature in the equation (15.136).
Let us now consider an ideal boson gas at temperatures below the critical temper-
ature (T < TC ), where µ = 0. As discussed in Problem 2, for T < TC , the equation
(18.114), with µ = 0, actually gives the total number of particles in the excited states,
i.e., the ones having kinetic energies E > 0. Their state occupation numbers are as in
the equation (18.115), with, for T < TC , the chemical potential set to zero. All the other
particles are in the state with E = 0. Let us denote the number of these “condensed”
particles, with E = 0, by N0 . So the total number of particles in the excited states, with
E > 0, is N − N0 . As the equation (18.114) with µ = 0 is valid only for these N − N0
particles in the excited states, we can write
Z∞ √
m3/2 V EdE
N − N0 = √ E
. (18.120)
2π 2 ~3 exp kT −1
0
3/2 Z∞
V w1/2 dw
2mkT
N − N0 = , (18.121)
4π 2 ~2 ew − 1
0
or
3/2 3/2 Z∞
V T w1/2 dw
2mkTC
N − N0 = . (18.122)
4π 2 ~2 TC ew − 1
0
Other Examples of Boson Systems 335
3/2
T
N − N0 = N . (18.123)
TC
From the result (18.123), we obtain the number of condensed bosons N0 at some tem-
perature T < TC , in the form
" 3/2 #
T
N0 = N 1 − . (18.124)
TC
From the equation (18.124), we see that a finite macroscopic fraction (= N0 /N) of
bosons starts to occupy the E = 0 state already below the nonzero critical temperature
TC . By (18.124), at T = TC , this fraction is zero and, as the temperature decreases
from TC down to 0, this fraction continuously increases from 0 to 1. For example, at
T = TC /22/3 , using the equation (18.124), we find that N0 /N = 1/2, that is, the 50 %
of all bosons are in the zero kinetic energy state with E = 0. Thus, the Bose–Einstein
condensation is an example of the so-called macroscopic quantum phenomena. Other
notable examples are superfluidity and superconductivity. Historically, however, the
Bose–Einstein theory outlined here, for an ideal boson gas, has served as a some-
what academic yet very important paradigm preceding the theories of all other macro-
scopic quantum phenomena. Typical values of TC in the equation (18.119) are in the
sub-Kelvin regime, where interparticle interactions would have to be included in the
discussion. Typically, with cooling a gas, the interactions preclude the Bose–Einstein
condensation, by causing an ordinary condensation of the gas into a liquid, well before
the above TC is reached.
Finally, let us now discuss the internal energy and pressure of an ideal boson gas
below the critical temperature. Since the condensed N0 particles all have E = 0, only
the noncondensed fraction of bosons (in the states with E > 0) contributes to the
internal energy of the system. Their state occupation numbers are as in the equation
(18.115), with, for T < TC , the chemical potential set to zero. Therefore, we can use
the result (15.54) with µ = 0 in the case of spinless bosons, to obtain the internal
energy of a partly condensed boson system
Z∞
m3/2 V E3/2 dE
U(V, T) = √ E
. (18.125)
2π 2 ~3 exp kT −1
0
3/2 Z∞
VkT w3/2 dw
2mkT
U(V, T) = , (18.126)
4π 2 ~2 ew − 1
0
336 Quantum Statistical Physics
or
3/2
VkT
2mkT 5 5
U(V, T) = 0 ζ ∼ T 5/2 . (18.127)
4π 2 ~2 2 2
Thus, the specific heat at constant volume for any T < TC is given by an exact result
as follows:
∂U
cV = , (18.128)
∂T V
or
3/2
5Vk 2mkT 5 5
cV = 0 ζ ∼ T 3/2 . (18.129)
8π 2 ~2 2 2
We see that the specific heat at constant volume at T < TC obeys a T 3/2 law. It should
be noted here that the pressure of the system by the equation (15.59), i.e.,
3/2
2U 2kT 2mkT 5 5
p(T) = = 0 ζ , (18.130)
3V 12π 2 ~2 2 2
is not dependent on the density N/V of the system, and it is a function of temperature
only for T < TC . Thus, an isothermal compression (or expansion) of the system does
not cause any change of the pressure of the system for T < TC . This striking behavior
of the system pressure for T < TC is in sharp contrast to the behavior for T > TC when
the pressure depends on both the density and the temperature of the system. Recall,
for example, that for T TC ∼ Tquantum , we have the ideal gas law p = (N/V)kT,
exemplifying the pressure dependence on the particle density.
ZωD
V~ ω3 dω
U= . (18.131)
2π c3S
0
exp ~kTω − 1
Determine the energy of the phonons that make the largest contribution to the internal
energy of a silicon crystal at T1 = 30 K and at the Debye temperature of silicon T2 =
TD = 625 K.
Other Examples of Boson Systems 337
Solution
Up to a multiplicative constant, the integrand in the equation (18.131) can be written
in the form
3
~ω
kT w3 ~ω
f (w) = = w , w= . (18.132)
kT
~ω
exp −1 e −1
kT
The energy of the phonons that make the largest contribution to the internal energy of
a crystal is obtained from the maximum of the function f = f (w), which is obtained
from the condition
3w2 w3
f 0 (w) = − ew = 0, (18.133)
ew − 1 (ew − 1)2
or
w2 w w
f 0 (w) = we
3(e − 1) − = 0, (18.134)
(ew − 1)2
or
Problem 2
Consider a d-dimensional problem of N zero-spin bosons in a d-dimensional hyper-
cube with the side L and the hypervolume V = Ld . For d = 1, this hypercube is just
a line segment of length L; for d = 2, it is a square of area L2 , and for d = 3, it is an
ordinary three-dimensional cube of the volume L3 . Let n = N/V denote the particle
number density. The bosons are nonrelativistic with kinetic energies,
|Ep|2 κ |2
~2 |E
κ |) =
E(|E = . (18.139)
2m 2m
338 Quantum Statistical Physics
The energies in (18.139) are obtained by solving the Schrödinger equation with peri-
odic boundary conditions, in which case the solutions are plane waves, with allowed
wave vectors κE forming a hypercubic lattice with the lattice constant 2π/L, as dis-
cussed in Section 18.1.1, “Vibration Modes.” The state with the wave vector κE is (on
κ ) bosons, given by the Bose–Einstein formula
average) occupied with n̄(E
1 1
κ) =
n̄(E = , (18.140)
E(κ)−µ E(κ)
exp kT −1 Y exp kT − 1
2π ~2 2/d
TC = Q(d)Tquantum , Tquantum = n . (18.141)
mk
Here, the Tquantum is the same as the characteristic quantum temperature defined in
the equation (15.136), expressed there in terms of h = 2π ~. Show that the numerical
factor Q(d) in the equation (18.141) is given by a simple formula
∞
1 X 1
Q(d) = , ζ (x) = , (x > 1), (18.142)
[ζ (d/2)]2/d nx
n=1
where we note that the Zeta function in (18.142) is finite only for x = d/2 > 1, and it
diverges for x = d/2 → 1, as
1
ζ (x) = + finite terms. (18.143)
x−1
Z∞ ∞
w x−1 dw X 1
I(x) = w
= 0(x) = 0(x)ζ (x), (18.144)
e −1 nx
0 n=1
d−2 d−2
Q(d) = ⇒ TC = Tquantum → 0, (18.145)
2 2
for d → 2. Thus, TC → 0 for d → 2 from above. This implies the physically important
conclusion that real Bose–Einstein condensation, with TC > 0, occurs only for d > 2,
Other Examples of Boson Systems 339
for example, for d = 3. On the other hand, for d = 2 and for any d < 2 (such as d = 1),
the critical temperature is depressed to zero, TC = 0, so there is no real Bose–Einstein
condensation at nonzero temperatures.
(b) For d > 2 and T < TC , show that the number of the bosons occupying the lowest
κ = 0),
energy state (E E i.e.,
1
κ = 0)
N0 = n̄(E E = , (18.146)
Y −1
Further, show that, for T < TC , the gas internal energy density (per unit volume), as
well as the corresponding heat capacity (per unit volume), do not depend on the gas
density n but only on its temperature T, as
U ∂ ũ
ũ = ∼ T 1+d/2 , c̃V = ∼ T d/2 . (18.148)
V ∂T
Remark: It can be shown that for any d and any temperature T (along the lines of
Section 15.4, “Thermodynamics of Quantum Systems,” done there for d = 3), the
pressure p satisfies p = d2 ũ. So, by the result (18.148), for T < TC , the pressure does
not depend on the density n , but only on the temperature T, as
(c) Next, consider the system for d = 2 and for any d < 2. By the above discus-
sion, there is no finite-temperature Bose–Einstein condensation. In other words, in
the limit N = nV → ∞, at fixed density n and temperature T, the quantity Y [entering
the equation (18.140)] must be given by an expression, which approaches 1 only for
T → 0, i.e., Y → 1 only for T → 0. By definition, Y = exp(−µ/kT) and the fact that
ln(x) ≈ x − 1 for |x − 1| 1, we have
Thus, we also expect that µ → 0 only for T → 0 (for d = 2 and for any d < 2).
In order to verify the above expectations
(a) Show that, for d = 2, the quantity Y is given by the following exact expression
1
Y= , (18.151)
T
1 − exp − quantum
T
340 Quantum Statistical Physics
T
exp − quantum
T
Tquantum
Y −1 = ≈ exp − → 0, (18.152)
T T
1 − exp − quantum
T
which in view of the equation (18.150), indeed shows that Y → 1 and that
Tquantum
µ ≈ −kT(Y − 1) = −kT exp − → 0, (18.153)
T
Solution
(a) By the equation (18.140),
X X 1
N= κ) =
n̄(E . (18.156)
κ |)
κE κE Y exp E(|E
kT − 1
For T ≥ TC , the above sum is possible to handle as an integral, using the equations
(18.32) and (18.41) of Section 18.1.1, “Vibration Modes.” Thus, we obtain
Z∞
dg(κ)
N=
0
Y exp E(κ)
kT −1
Z∞
V κ d−1 dκ
= S(d) , (18.157)
(2π)d
0
Y exp E(κ)
kT − 1
Other Examples of Boson Systems 341
with
√
~2 κ 2 2mE 1 m 1/2
E(κ) = ⇒κ = ⇒ dκ = dE. (18.158)
2m ~ ~ 2E
By changing the variable κ into the variable E in the equation (18.157), as suggested
by (18.158), we obtain
Z∞
md/2 E−1+d/2 dE
N = V ·2 −1+d/2
S(d) E
. (18.159)
(2π ~)d Y exp kT
−1
0
Changing further the variable E into the variable w, via E = kTw, yields
Z∞
(mkT)d/2 w−1+d/2 dw
N = V ·2 −1+d/2
S(d) . (18.160)
(2π ~)d Yew − 1
0
Z∞
(mkTC )d/2 w−1+d/2 dw
N = V ·2 −1+d/2
S(d) . (18.161)
(2π ~)d ew − 1
0
Using the result (18.144), we can calculate the integral in the equation (18.161) as
follows:
Z∞
w−1+d/2 dw
= 0(d/2)ζ (d/2), (18.162)
ew − 1
0
(2π)d/2 21−d/2
S(d) = . (18.163)
0(d/2)
Substituting the results (18.162) and (18.163) into the equation (18.161), we obtain
d/2
mkTC
N=V ζ (d/2). (18.164)
2π ~2
where we used the definition of Tquantum in the equation (18.141) and introduced the
notation
1
Q(d) = . (18.166)
[ζ (d/2)]2/d
Thus, the result (18.165) with (18.166) proves the anticipated expressions (18.141)
and (18.142). For x = d/2 slightly above 1, we have by the equation (18.143),
1 2
ζ (d/2) = + finite terms = + finite terms. (18.167)
d/2 − 1 d−2
1 d−2
Q(d) ≈ h i2/2 = . (18.168)
2 2
d−2
d−2
TC = Q(d)Tquantum ≈ Tquantum → 0 for d → 2. (18.169)
2
Thus, we have derived the equation (18.145) implying the major effect here that TC →
0 for d → 2 from above.
(b) Let us consider the case d > 2 at T < TC . The equation (18.156) can be written as
X X 1
N = n̄(0) + κ ) = N0 +
n̄(E . (18.170)
κ |)
E(|E
κE 6=0 κE 6=0 Y exp kT −1
Here, the second term represents the total number of bosons in the excited states, with
κE 6= 0.
E For d > 2 and T < TC , this term has the same value as the expression on the
right-hand sides of equations (18.157), (18.159), and (18.160), with Y = 1 set therein
(see the Comment at the end of this problem). Thus,
Z∞
(mkT)d/2 w−1+d/2 dw
N = N0 + V · 2 −1+d/2
S(d) , (18.171)
(2π ~)d ew − 1
0
or
Z∞
(mkT)d/2 w−1+d/2 dw
N − N0 = V · 2 −1+d/2
S(d) . (18.172)
(2π ~)d ew − 1
0
Other Examples of Boson Systems 343
Z∞
−1+d/2 (mkTC )d/2 w−1+d/2 dw
N = V ·2 S(d) (18.173)
(2π ~)d ew − 1
0
and dividing the equation (18.172) by the equation (18.173), we easily see that
d/2 d/2
N − N0 N0 T N0 T
= 1− = ⇒ = 1− (18.174)
N N TC N TC
at T < TC for d > 2 whence TC > 0. This proves the equation (18.147).
It is worthwhile noting that the statement Y = 1 is actually true in the limit
N = nV → ∞, at fixed density n and temperature T < TC . This can be seen from the
equation (18.140) with E = 0, by which
1 1
κ = 0)
N0 = n̄(E E = ⇒ Y = 1+ . (18.175)
Y −1 N0
1 1
Y −1 = ∼ →0 for N → ∞. (18.176)
N0 N
X X κ |)
E(|E
U= κ )E(|E
n̄(E κ |) = . (18.177)
κ |)
E(|E
κE κE Y exp kT −1
κ = 0|)
Note that the E(|E E = 0, so only the bosons in the excited states contribute to the
internal energy (at any temperature). For T < TC , we can set Y = 1 in the equation
(18.177) and handle the sum in (18.177) in the same way as we handled the sum in
(18.156) [see the equations (18.157) through (18.160)]. The final result is
Z∞
U (mkT)d/2 wd/2 dw
ũ = = 2−1+d/2 S(d)kT . (18.178)
V (2π ~)d ew − 1
0
U ∂ ũ
ũ = ∼ T 1+d/2 , c̃V = ∼ T d/2 . (18.179)
V ∂T
344 Quantum Statistical Physics
(c) To proceed, let us simplify the form of the result (18.160), by writing the tempera-
ture therein as T = yTquantum . With this, and by the equation (18.141), we get
Z∞
d/2 S(d) w−1+d/2 dw
1=y , (18.180)
2π d/2 Yew − 1
0
or
Z∞
2π d/2 −d/2 w−1+d/2 dw
y = , (18.181)
S(d) Yew − 1
0
Using here the form of S(d) from (18.163), the equation (18.181) assumes a very
simple form
Z∞
w−1+d/2 dw
0(d/2)y−d/2 = , (18.182)
Yew − 1
0
or as y = T/Tquantum ,
d/2 Z∞
Tquantum w−1+d/2 dw
0(d/2) = . (18.183)
T Yew − 1
0
The equation (18.183), with Y = 1, is [in combination with the equation (18.144)]
easily shown to yield our result for the critical temperature in the equation (18.141).
The result shows that TC vanishes for d = 2 and d < 2. Going with this are the results
(18.151) and (18.154), which we will prove in the following:
(a) Case d = 2: The equation (18.183) reduces to
Z∞
Tquantum dw
= . (18.184)
T Yew − 1
0
Z∞ Z∞ Z∞
dw e−w dw d(Y − e−w )
= =
Yew − 1 Y − e−w Y − e−w
0 0 0
Y
= ln(Y − e−w )|∞
0 = ln . (18.185)
Y −1
Other Examples of Boson Systems 345
This proves the equation (18.151), which by the equations (18.152) and (18.153)
shows that Y → 1 and µ → 0 only in the limit T → 0.
(b) Case d < 2: In this case, we will evaluate the integral in the equation (18.183) in
the asymptotic limit Y → 1 whence Y − 1 = 1. This is possible because the inte-
gral is dominated by small values of w ∼ (this w-range actually causes a divergence
of this integral for Y − 1 = → 0 ). One can thus expand the ew in the denominator of
the integral in the equation (18.183) just to the first-order ew ≈ 1 + w and then do the
change of variables w = x, as displayed below
Z∞ Z∞ Z∞
w−1+d/2 dw w−1+d/2 dw w−1+d/2 dw
≈ =
Yew − 1 Y(1 + w) − 1 Y − 1 + Yw
0 0 0
Z∞ Z∞
w−1+d/2 dw (x)−1+d/2 d(x)
≈ =
Y −1+w + x
0 0
Z∞
x−1+d/2 dx
= −1+d/2
. (18.188)
1+x
0
The result (18.188) is asymptotically exact for = Y − 1 → 0 and any d < 2. Here, it
remains to calculate the integral in (18.188). It can be done, by the following change
of variables y = 1/(1 + x) or x = −1 + 1/y, so dx = −dy/y2 . With this change of vari-
ables, one easily obtains
Z∞ Z1
x−1+d/2 dx d d
= dyy−d/2 (1 − y)−1+d/2 = B 1 − ,
1+x 2 2
0 0
0(1 − d/2)0(d/2) π
= = . (18.189)
0(1) sin(π d/2)
Above, we employed the standard definition of the Beta function,
Z1
B(u, v) = dyyu−1 (1 − y)v−1 , (18.190)
0
346 Quantum Statistical Physics
which are used above for the case u = 1 − d/2 and v = d/2. Substituting the result
(18.188) with (18.189) into the equation (18.183), we obtain for d < 2
d/2
Tquantum π
0(d/2) = −1+d/2 . (18.192)
T sin(π u)
Thus, for d < 2 and T Tquantum , the quantity = Y − 1 is given by the expression
d/(2−d)
T
Y − 1 ≈ A(d)
Tquantum
d/(2−d)
T
⇒ µ ≈ −kTA(d) , (18.193)
Tquantum
Thus, we have proved the result in the equation (18.154). It holds for any d < 2, in
particular for the experimentally interesting case d = 1, for which,
2/(2−1) 2
π π
A(1) = = √ = π. (18.195)
0(d/2) sin(π d/2) π sin(π/2)
T T
Y −1 ≈ π ⇒ µ ≈ −kTπ . (18.196)
Tquantum Tquantum
Comment on the equation (18.172): For T < TC , the total number of bosons in the
excited states, with κE 6= 0,
E can be written as follows:
X X 1
N − N0 = κ) =
n̄(E
κ |)
E(|E
κE 6=0 κE 6=0 exp kT −1
Z∞
V κ d−1 dκ
= S(d) . (18.197)
(2π)d
E(κ)
κmin
exp kT −1
Other Examples of Boson Systems 347
In the above integral, the lower limit κmin ∼ 1/L reflects the fact that the κE = 0E state
is excluded from the sum over the allowed values of κ (recall that the allowed val-
ues form a cubic lattice with the lattice cell size ∼ 1/L). Since κmin ∼ 1/L → 0 for
macroscopic systems of interest here, it would be tempting to simply set κmin = 0 in
the integral of the equation (18.197) [as done in solving the item (b) of this Problem].
It is, however, important to note that this step is justified only for d > 2 [as was the
case in the item (b)]. To see this, note that, for small energies, i.e., for small κ, we have
From (18.199), by elementary integration rules, it is easy to see that one can indeed
set κmin ∼ 1/L → 0, but only for d > 2, when the integral (18.199) has a finite value
in the limit κmin ∼ 1/L → 0. On the other hand, for d < 2,
Z d−1
κ dκ (κmin )d−2
= − + finite terms, (18.200)
κ2 d−2
κmin
κ dκ
Z 2−1 Z
dκ 1
= = ln( ) + finite terms, (18.202)
κ2 κ κmin
κmin κmin
κ dκ
Z 2−1
= ln(L) + finite terms → ∞, (18.203)
κ2
κmin
for L → ∞. So for any d < 2 and d = 2, one is not allowed to set κmin ∼ 1/L → 0
in the integral (18.199), i.e., in the integral (18.197). On the other hand, recall that,
for solving the item (b), only the case d > 2 was relevant, since only then the critical
temperature is positive (nonzero) and one has a real Bose–Einstein condensation. So,
by the above discussion, we were allowed to set the κmin ∼ 1/L → 0 in the item (b)
calculations.
19 Special Topics
19.1 Ultrarelativistic Fermion Gas
In this section, we study a gas consisting of the so-called ultrarelativistic fermions,
having very high energies E mc2 , where m stands for the fermion rest mass. Such
gases are encountered in some extreme physical conditions, e.g., during the early days
of the present universe. When the fermion gas is compressed to a high density, the
average energy of the constituent fermions may become very large, due to Pauli exclu-
sion principle (see Chapter 17, “Photon Gas in Equilibrium”). When it becomes com-
parable or larger than mc2 , the relativistic effects become significant. In this discussion,
we will assume that the energy of the fermions is large compared to mc2 . Thus, the
relation of the energy and momentum of an ultrarelativistic fermion is given by
q
E = p2 c2 + m2 c4 ≈ pc. (19.1)
It should be noted that the equation (19.1) is exactly valid for massless fermions, like
neutrinos. In such a case, by using the relation E = pc, we do not make any approx-
imation. As for the nonrelativistic fermion gas, in the ground state (T = 0), we have
the following fermion distribution over energies,
1 E < EF
dnE = dg(E) × . (19.2)
0 E > EF
In order to calculate dg(E), we recall the result (15.46), i.e.,
V
dg(p) = g(σ ) 4π p2 dp. (19.3)
h3
For fermion gases consisting of ultrarelativistic fermions, we can use the approxima-
tion (19.1) to obtain
V
dg(E) = g(σ ) 4πE2 dE. (19.4)
c3 h3
Using the results (19.2) and (19.4), we can calculate the total number of relativistic
fermions in the form
Z ZEF
V
N= dg(E) = 4π g(σ ) 3 3 E2 dE, (19.5)
c h
E<EF 0
or
3
4π EF
N= g(σ )V . (19.6)
3 ch
Thus, the Fermi energy for an ultrarelativistic relativistic fermion gas is given by
1/3
3n
EF = hc . (19.8)
4π g(σ )
Z ZEF
V
U0 = Edg(E) = 4πg(σ ) 3 3 E3 dE, (19.9)
c h
E<EF 0
or
3
4π EF 3 3
U0 = g(σ )V EF = NEF . (19.10)
3 ch 4 4
For the ultrarelativistic fermion gas at finite temperatures, the fermion distribution
over energies is given by
dg(E)
dnE = . (19.11)
exp E−µ
kT + 1
V E2 dE
dnE = 4π g(σ ) . (19.12)
c3 h3
exp E−µ
kT + 1
The total number of particles in the ultrarelativistic fermion gas is now obtained as
follows:
Z∞
V E2 dE
N = 4π g(σ ) 3 3 , (19.13)
c h exp E−µ
+1
0 kT
Special Topics 351
or
3 Z∞
4π EF 3 E2 dE
N= g(σ )V 3
. (19.14)
3 ch EF exp E−µ
+ 1
0 kT
Z∞
3 E2 dE
N=N . (19.15)
EF3
0
exp E−µ
kT +1
Thus,
Z∞
3 E2 dE
= 1. (19.16)
EF3
0
exp E−µ
kT + 1
The equation (19.16) is an implicit equation, which determines the chemical potential
µ of the ultrarelativistic fermion gas. It can be rewritten as follows:
3
kT
3 IN = 1, (19.17)
EF
where
Z∞
1 E2 dE
IN = . (19.18)
(kT)3
E−µ
0
exp kT +1
Z∞
V E3 dE
U = 4πg(σ ) , (19.19)
c3 h3
0
exp E−µ
kT + 1
or
3 Z∞
4π EF 3 E3 dE
U= g(σ )V . (19.20)
EF3
3 ch exp E−µ
+ 1
0 kT
Z∞
3N E3 dE
U= , (19.21)
EF3
0
exp E−µ
kT + 1
352 Quantum Statistical Physics
or
4
kT
U = 3NEF IE , (19.22)
EF
where
Z∞
1 E3 dE
IE = . (19.23)
(kT)4
E−µ
0
exp kT +1
In order to solve the integrals (19.18) and (19.23), we introduce a new variable w as
follows:
Thus, we obtain
Z∞
(w + µ/kT)2 dw
IN = , (19.25)
ew + 1
−µ/kT
and
Z∞
(w + µ/kT)3 dw
IE = . (19.26)
ew + 1
−µ/kT
The Helmholtz thermodynamic potential (15.55) for the ultrarelativistic fermion gas
is given by
Z∞
µ−E
VkT
= −4πg(σ ) 3 3 E2 ln 1 + exp dE. (19.27)
c h kT
0
Integrating the right-hand side of the equation (19.27) by parts, in the same way as for
the nonrelativistic quantum gas, we obtain
Z∞
4 V E3 dE
= − πg(σ ) 3 3 . (19.28)
3 c h exp E−µ +1
0 kT
Comparing the results (19.28) and (19.19), we obtain the thermal-state equation of the
relativistic fermion gas as follows:
U 1
= −pV = − ⇒ pV = U. (19.29)
3 3
Special Topics 353
Thus, for an extremely relativistic fermion gas, the thermal-state equation (15.59) is
replaced by the equation (19.29). This equation is identical with the equation (17.29)
valid for extremely relativistic boson gas, i.e., the photon gas.
From the above results, we see that if we want to calculate the thermodynamic
variables of the ultrarelativistic fermion gas, we need to calculate the integrals IN and
IE defined by the equations (19.18) and (19.23), respectively.
µ/kT Z∞
[(w + µ/kT)2 − (−w + µ/kT)2 ]dw
Z
IN = λ dλ +
2
. (19.30)
ew + 1
0 0
On the other hand, the integral IN , with f (λ) = λ3 , can be rewritten as follows:
µ/kT Z∞
[(w + µ/kT)3 − (−w + µ/kT)3 ]dw
Z
IE = λ dλ +
3
. (19.31)
ew + 1
0 0
Unlike their counterparts for the nonrelativistic fermion gas, the integrals (19.30) and
(19.31) can be solved exactly. By expanding the binomial expressions in the numera-
tors of these integrals, they are significantly simplified, and we obtain
µ/kT Z∞
µ
Z
wdw
IN = λ dλ + 4
2
, (19.32)
kT ew + 1
0 0
and
µ/kT
Z µ 2 Z∞ wdw Z∞ 3
w dw
IE = λ dλ + 6
3
+2 . (19.33)
kT ew + 1 ew + 1
0 0 0
The values of the two numerical integrals left in the two equations (19.32) and (19.33)
are given by
Z∞ Z∞
wdw π2 w3 dw 7π 4
w
= , w
= . (19.34)
e +1 12 e +1 120
0 0
354 Quantum Statistical Physics
1 µ 3 µ
IN = + π2 , (19.35)
3 kT kT
and
1 µ 4 π 2 µ 2 7π 4
IE = + + . (19.36)
4 kT 2 kT 60
Substituting (19.35) and (19.36) into (19.17) and (19.22), respectively, we obtain
3 2
µ µ
kT
+ π2 = 1, (19.37)
EF EF EF
and
" 4 2 2 4 #
µ µ 7π 4
3 kT kT
U = NEF + 2π 2
+ . (19.38)
4 EF EF EF 15 EF
and
" 4 2 2 4 #
µ µ 7π 4
3 T T
U = NEF + 2π 2
+ . (19.40)
4 EF TF EF 15 TF
In this case, it is possible to find the exact solution of the equation (19.39) for the
relative chemical potential x = µ/EF , and then substitute that solution into the caloric-
state equation (19.40). The equation (19.39) has the form of the exactly solvable cubic
equation
T
x3 + a2 x − 1 = 0, a=π 1. (19.41)
TF
(19.43)
Substituting (19.43) into (19.40), we can obtain the “almost exact” caloric-state equa-
tion. However, the solution (19.43) is quite complicated and not useful for practical
calculations. It is included here primarily to illustrate the possibility of solving the
implicit equation for the chemical potential (19.16). In order to obtain a simpler result
for the chemical potential, we can use the fact that T/TF 1.
Using here the approximation
√ x
1+x ≈ 1+ , x 1, (19.44)
2
we can write
6 !1/2 6
π6 1 π6
T 1 T
+ ≈ + . (19.45)
27 TF 4 2 27 TF
Substituting (19.47) into (19.40) and keeping only terms of second order in the small
quantity T/TF 1, we obtain the approximate caloric-state equation
" #
3 2 2 kT 2
U = NEF 1 + π . (19.48)
4 3 EF
∂U
kT
mcV = = π 2 Nk . (19.49)
∂T V EF
356 Quantum Statistical Physics
Using here the definition of the fermion number density n = N/V, we obtain the pres-
sure of the ultrarelativistic fermion gas
" #
1 2 2 kT 2
p = nEF 1 + π . (19.51)
4 3 EF
Z∞ Z∞
(w + µ/kT)3 dw w3 dw 7π 4
IE = ≈ = . (19.53)
ew + 1 w
e +1 120
−µ/kT 0
Comparing the result (19.54) for the relativistic massless fermion gas with the result
(17.31) for the relativistic massless boson gas (photon gas), we see that they are iden-
tical except for the ratio between the fermion and boson integrals, defined by the equa-
tion (15.81), i.e.,
7
γF = 1 − 21−2j = 1 − 2−3 = , j = 2. (19.55)
8
Thus, the massless relativistic fermion gas, for T/TF 1, has the same behavior as
the black-body radiation, except for the factor of γF = 7/8 in calculating the thermo-
dynamic variables like the internal energy or the specific heat.
Special Topics 357
g(σ ) V E2 dE
dnE ≈ 2 3 3 E
, (19.56)
2π c ~ exp kT ∓1
where, as before, the upper sign applies to bosons and the lower sign applies to fer-
mions. For notational simplicity, let us now introduce a new constant, which includes
both the spin factor g(σ ) and the constants c and ~ as follows:
g(σ )
g= . (19.57)
c3 ~3
Thus, we obtain
g E2 dE
dnE ≈ 2
V E
. (19.58)
2π exp kT ∓1
Z∞
N g E2 dE
n= ≈ E
. (19.59)
2π 2
V exp kT ∓1
0
Z∞
U g E3 dE
ρ= ≈ E
. (19.60)
2π 2
V exp kT ∓1
0
Using the thermal-state equation (19.29), we obtain the pressure of the relativistic
quantum gas
U ρ
p= = . (19.61)
3V 3
358 Quantum Statistical Physics
Z∞
g w2 dw
n= (kT)3 , (19.62)
2π 2 ew ∓ 1
0
and
Z∞
g w3 dw
ρ= (kT)4 . (19.63)
2π 2 ew ∓ 1
0
Using the results for the integrals (15.80) and (15.81), we obtain the particle density
ζ (3)/π 2 g(kT) 3
Bosons
n= , (19.64)
(3/4) ζ (3)/π g (kT)3
2
Fermions
(π /30)g(kT)4
2
Bosons
ρ= . (19.65)
(7/8) π 2 /30 g(kT)4 Fermions
π2 π2
ρR = gR (kT)4 , pR = gR (kT)4 , (19.66)
30 90
where gR is the effective constant, which measures the total number of relativistic
(massless) species, with the appropriate factors to account for the different equilibrium
temperatures for different species, as well as for the difference between bosons and
fermions. The constant gR is given by
4 4
X Ti 7 X Ti
gR = gi + gi . (19.67)
T 8 T
i = bosons i = fermions
Special Topics 359
For lower energies (kT 1 MeV), the only relativistic species are photon and the
three neutrino species, in which case we have gR ≈ 3.36 c−3 ~−3 . At intermediate ener-
gies (100 MeV ≤ kT ≤ 1 MeV), the additional relativistic species are the electron and
positron, and we have gR ≈ 10.75 c−3 ~−3 . For high energies (kT ≥ 300 GeV), all the
species in the standard model of the elementary particle physics are relativistic, and
we have gR ≈ 106.75 c−3 ~−3 .
or
1 V
dS = d[(ρ + p)V] − dp. (19.70)
T T
Using the general result (9.77), we obtain the condition that the expression (19.70) is
a total differential, in the following form
∂ ∂
1 V
= − , (19.71)
∂p T ∂[(ρ + p)V] T
or
1 ∂T 1 ∂V
− =− . (19.72)
T ∂p
2 T ∂[(ρ + p)V]
dp ρ +p
T = ρ + p ⇒ dp = dT. (19.73)
dT T
Substituting (19.73) into (19.70), we obtain
1 dT
dS = d[(ρ + p)V] + [(ρ + p)V] − 2 , (19.74)
T T
360 Quantum Statistical Physics
or
(ρ + p)V
dS = d + S0 . (19.75)
T
(ρ + p)V (ρ + p)R3
S= = = Constant. (19.76)
T T
If we now define the entropy density sV = S/V, we obtain
ρ + p ρ + ρ/3 4 ρ
sV = = = . (19.77)
T T 3T
Substituting (19.66) into (19.77), we obtain
2π 2 k
sV = gS (kT)3 , (19.78)
45
where
3 3
X Ti 7 X Ti
gS = gi + gi . (19.79)
T 8 T
i = bosons i = fermions
During a part of the expansion of the universe, the different ultrarelativistic species
in thermal equilibrium have had the same temperature. Due to this, gS was equal to
gR . The conservation of the entropy S = sV V implies that sV ∼ R−3 . Thus, the adia-
batic process of the expansion of the universe has VT 3 = Constant. This is the same
conclusion as the one we made in Chapter 18, “Other Examples of Boson Systems,”
for the adiabatic process in the photon gas. Thus, the quantity R3 T 3 remains constant
as the universe expands. This is an important physical conclusion, which shows that
as the universe expands, its temperature decreases according to the following qualita-
tive relation
−1/3 −1
T ∼ gS R . (19.80)
If the quantity gS would be a constant, we would obtain the simple result T ∼ R−1 .
The factor gS is of significance when the energy of a species decreases and it even-
tually becomes nonrelativistic. Their contribution to the above thermodynamic vari-
ables disappears (their entropy is transferred to lower energy species forming a thermal
plasma). This effect causes a decrease of gS , and by the equation (19.80), it causes the
temperature to decrease less slowly. This, however, does not apply to the massless
particles that become decoupled from the thermal plasma, when the temperature drops
below the mass threshold of the species. The temperature of such a massless species
scales as T ∼ R−1 .
Special Topics 361
Solution
(a) The total number of photons in the universe is given by
Z∞
V ω2 dω
N= 2 3 . (19.81)
π c
~ω
0
exp kT −1
~ω kT kT
=w⇒ω= w ⇒ dω = dw, (19.82)
kT ~ ~
we obtain
Z∞
Vk3 T 3 w2 dw Vk3 T 3
N= 2 3 3 = 2 3 3 0(3)ζ (3), (19.83)
π c ~ e −1 π c ~
w
0
or finally
Vk3 T 3
N = 2.4 = 2.3 × 1087 , (19.84)
π 2 c3 ~3
π 2 Vk4 T 4
U= = 2.6 × 1065 J. (19.85)
15c3 ~3
Problem 2
In a given volume of the expanding universe, the number of photons N is, on average,
109 times larger than the number of nucleons (protons or neutrons), which are assumed
to comprise most of the rest mass of the universe. This ratio of the number of photons
and the number of nucleons are constant during the expansion of the universe. In a
362 Quantum Statistical Physics
certain phase of the expansion of the universe, the energy of the background electro-
magnetic radiation has dominated all the other energy types. Calculate the temperature
at which the energy of the background radiation is equal to the energy 10−9 Nmc2 cor-
responding to the total rest mass of the universe, where m ≈ 1, 67 × 10−27 kg is the
nucleon mass and c = 2.9979 × 108 m/s is the speed of light.
Solution
Using the result (19.83), we know that the number of photons in the universe is
Vk3 T 3
N= 0(3)ζ (3). (19.86)
π 2 c3 ~3
The number of nucleons is then equal to 10−9 × N, and the rest energy of the nucleons
is given by
Vk3 T 3
EN = 10−9 × mc2 × 0(3)ζ (3). (19.87)
π 2 c3 ~3
On the other hand, using the result (19.85), the total energy of the photons in the
universe is
π 2 Vk4 T 4
U= . (19.88)
15c3 ~3
Vk3 T 3 π 2 Vk4 T 4
10−9 × mc2 × 0(3)ζ (3) = . (19.89)
π 2 c3 ~3 15c3 ~3
Problem 3
A dense white-dwarf star contains a gas of ultrarelativistic electrons of mass me at a
temperature T TF , where TF is the Fermi temperature of the electron gas.
(a) Calculate
√ the density of the star, for which the Fermi momentum is equal to pF =
3/2me c.
(b) Calculate the pressure of the star under such conditions.
Special Topics 363
Solution
(a) The Fermi energy for a relativistic electron gas, with g(σ ) = 2, is given by the
following expression
1/3
3n
EF = pF c = hc . (19.91)
8π
or finally
N
p = 6.75 × 1021 . (19.98)
m2
A Physical Constants
Atomic mass unit a.m.u. 1.6605 × 10−27 kg