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Library of Congress Cataloging in Publication pat;

Killcl, Clmrlcs.
Thermal physics.

Bibliography:p.
Includes index.
!. Statistical tiicrmodyn;miics. I. Kroe/n
Herbert.1928- joiiii aullior. II. Tillc.
QC3H.5.K52 1930 536'.? 79-16677
ISBN O-7167-IO8S-9

Copyright
\302\260
I9B0 by W. H. Freeman and Company

No pan of this bor.k may be reproduced by any

mechanical, plioiographic, or electronic process,or in
liic form of a phonographic recording,nor may it be
sioreti in a retrieval system, transmitted, orotherwisc
copiedfor public or private use, without wriiicn

permission from the publisher.

Pcimcti in ilie United State of America

Twenty-first printing, 2000

9
About the Authors

Charles Kiitel has laught solid slate physics at the University of California
at Berkeley since 1951, having previously been at [he Bell Laboratories.His
undergraduate work in physics was done at M.I.T. and at the Cavendish

Laboratory of Cambridge His Ph.D. research was in theorclicai

University.
nuclear physics with Professor Gregory Breit at the University of Wisconsin.
He has been awarded three Guggenheim fellowships, the Oliver Buckley Pme
for Solid State Physics, and, for contributions to teaching, the Oersted Medal
of the American Association of Physics Teachers. He is a member of \"he
National Academy of Science and of the American Academy of Arts ;i id
Sciences. His research has been in magnetism, magnetic resonance, semio n-
ductors, and the statistical mechanics o f soiids.

iferbcrt Kroemcr is Professor of Electrical Engineering at the University of

California at Santa liurhara. His background mid training nre in solid state
liliy^ics. I !c received a I'lt.D. in physics in I'J52 from the University of Gulling
in Germany with a thesis on hot electron effects in lhc then new transistor.
Prom 1952 through I96S tie workedin several semiconductor research labora-
laboratories in Germany Stales. In I96S lie became
and the United of Professor

[ilixirieul Engineering at ltic University of Colorado; lie came to UCStt in

1976. His research has been in the physics and technology of semiconductors
and semiconductor devices, including high-frequency transistors, negative-
mass effects in semiconductors, injection lasers,the Gunn effect, electron-hole

drops, and semiconductor hetcrojunctions.

Preface

This book gives an elementary account of thermalphysics. The subject is

simple, the methods are powerful, and the results have broad applica-
applications. Probably no other physical theory is used more widely throughout

science and engineering.

We have written for undergraduate students of physics and astronomy,
and for electrical engineering students generally. These fields for our
purposes have strong common bonds,most notably a concern with Fermi
gases, whether in semiconductors, mcmls, stars, or ituclci. We develop
methods (not original, but not easily accessible elsewhere) that are well
suited to these fields. We wrote the book in the first place because we
were delighted by the clarity of the \"new\" methods as compared to (hose
we were taught when we were students ourselves.
We have not emphasized several traditioual topics, some because they
are no longer useful and some because their reliance on classical statisn-
cai mechanicswould make the course more difficult than we believe a
first course should be. Also, we have avoided the use of combinatorial
methods where they are unnecessary.
Notation and units; We
generally use the SI and CGS systems in

parallel. We do not use the calorie. The kclvin temperatureT is related to

the fundamental temperature t by r = kBT,

and the conventional entropy
S is reialed lo the fundamental entropy a by 5 = ka(j. The symbol log
will denote natural logarithm throughout, simply because In is less ex-
expressive when set in type. The notafion A8) refers lo Equation A8) of
the current chapter, but C.18) refers to Equation A8) of Chapter 3.
Hie bookis ihe successor to course notes developed with the assisf-
ance of grants by (he University of California. Edward M. PurceSlcon-
contributed many ideas to the first edition. We benefited from review of the
second edition by Seymour Geller, Paul L. Richards, and Nh.-holns
Wheeler- Help was giveii by Ibrahim Adawi, Bernard Black, G. Domo-
kos, Margaret Geller, Cameron Hayne, K. A. Jackson, S. Justi, Peter
Kittel, Richard Kittler, Martin J. Klein, Ellen Leverenz, Bruce H. J.
McKellar, F. E. O'Meara, Norman E. Phillips, B. Roswclt Russell,T. M.
Preface

Sanders. B. Stoeckly, John Verhoogen, John Wheatley, and Eyvind

Wichmann. We thank Carol Tung for the typed manuscript and Sari
Wilde for her help with the index.
An
elementary treatment of the greenhouse effect in the Earth's atmo-
atmosphere was added in 1994 on page 115, following an argument suggested
by Professor Richard Muiier. A page on aioinic gas experiments on the
Bose-Eitistein condensationwas added to page 223 in 2000.
For instructors who have adopted the course for classroom use, a
solutions manual is available via the freeman web site (http:/Avhfreenian.

com/thermaiphysics).

Berkeley and Santa Barbara Charles K'tttel

Herbert Kroemer
Note to the Student

For minimum coverage of the concepts presented in each chapier, the authors
recommend the following exercises.Chapter 2: 1,2, Chapter 3; 3: 1,2, 3,4, 8,
11; Chapter 4: 1,2,4, 5,6, 8; Chapter 5: 1,3,4, 6,8; Chapter 6: 1,2,3,6,12,
14, 15;Chapter7: 2, 3,5,6,
7, 11; Chapter 8: 1, 2, 3, 5, 6, 7; Chapter 9: 1, 2, 3;

Chapter 10: 1,2,3; Chapter 11: 1,2,3;Chapter 12: 3,4.5; Chapter 13: 1,2,
3,7,8,10; Chapter 14: 1,3,4,5; Chapter 15: 2,3,4,6.
Contents

Guide to Fundamental Definitions xiii

General References xv

Introduction 1

Chapter 1 States of a Model System 5

Chapter 2 Eittropy and Temperature 27

Chapter
3 Boltzmann Distribution and Hdmholtz
Free Energy 55

Chapter4 Thermal Radiation and Planck Distribution 87

Chapter 5 Chemical Potential and Gibbs Distribution 1 i 7

Chapter 6 Ideal Gas 151

Chapter 7 Fermi and Bose Gases 181

Chapter
8 tHeaZahd Work 225

Chapter 9 Gibbs Free Energy and ChemicalReactions 261

Chapter10 Phase Transformations 275

Chapter il Binary Mixtures 309

Chapter 12 Cryogenics 333

Chapter
13 Semiconductor Statistics 353

Chapter 14 Kinetic Theory 389

Chapter15 Propagation
423

Appendix A Some Integrals Containing Exponentials 439

Appendix B TemperatureScales 445

Appendix C Poisson Distribution 453

Appendix D Pressure 459

AppendixE Negative Temperature
460

Index 465
Guide to Fundamental Definitions

Absolute activity, X ~
exp(/i/t) 139

Accessible state 29
Boltzmann constant, ka
25

Boltzmann factor, exp\302\243~~ \302\243/t)

61'

Boson 183

Chemical potential, /; 119

Classicalregime, n \302\253
nQ
74

Ensemble of systems 31

Enthalpy, H = U + pV
246

Entropy, a 40

Fermion 1S3

Gibbs factor, exp[(Nji- t)/i] 138

Gibbs free energy, G = U \342\200\224

\\a + p^

Gibbs or grand sum, \342\226\240% 138

Heat capacity, C 63

Heat, Q 68, 227

\342\200\224 t
HelmhoHz free energy, F \342\200\224
U xa

Landau free energy function, FL 298

Multiplicity,g 7
Orbital 9
Partition function, Z 61
Guide to Fundamental Definitions

Quantum concentration,
=
hq
Reversible process 64

Temperature, t 41
Thermal
average 62

Thermal equilibrium 39

Work, W 227
General References

Thermodynamics
A. B. Pippard, Elements of classical thermodynamics, Cambridge University Press,
1966.
M. W. Zemansfcy and R. H. DiEEman, Heat anil thermodynamics: an intermediate
textbook, 6ih ed., McGraw-Hill, 198!.

Sitttisiical Afcchanics

U. K, Agarwal and M. Eisner, Statistical mechanics, Wiicy, 1988.

T. L. Hit), Statistical mechanics:principlesand selected applications, Dover Pubtica-
iions, 1987, cl956.
C. Kittct, Elementary statistical physics, Wiicy, 1958. Parts 2 and 3 treat applications
to noise and to elemeniary transport Eheory. Part 1 has been expanded ioEo the
present Eext.
R. Kubo, Statistical mechanics, North-Holland, 1990, cI965.
R, Kubo, M. Toda, N. Hashitsume, Statistical physics !! (NanequHibrium), Springer,
1985.
L D. Landau and E. M. Lifshitz, Statistical physics, 3rd cd. by K. M. Lifshitz and L. P.
Piiaevskii, Pcrgamon, 1980, part 1.

Shang-Keng Ma, Statistical mechanics. World Scientific, 1985.

M. Toda, R. Kubo, N. Saito,Statisticalphysics ! (Equilibrium), Springer, 1933,

Mathematical tables
H. B. Dwight, Tables of integrals and other mathematical data, 4ih ed., MacmUton,
1961. A widely useful smati collection.

Applications

Asirophysics
R. J. Taylor, The stars: their structure and evotitiioit. Springer, 1972.
S. Weinbcrg, The first three minutes: a modern v:\\-w of the origin of the universe, new
ed., Bainam Cooks, 1984.

Biophysics and macromolccules

T. L. Hill, Cooperathity theory in biochemistry: steady stale and equilibrium systems,

Springer, 1985.
General Refer,

Cryogenicsand low lempcrature physics

G. K. White, Experimental techniques in low-temperature physics, 3rd ed., Oxford
University Press, 1987, ct979 . . pa.
J. Wilks and D. S. Betis, An introduction to liquid helium, 2nd ed , Oxford Univesity
Press, 1987.

Irreversible thermodynamics
J. A. McLennan,Introduction to non-equilibrium statistical mechanics, Prentice-Hall,
1989.
I. Prigogine and I. Stcngers, Order out of chaos: man's new dialog with nature.
Random House, 1934.

Kjnclic theory and transport phenomena

S. G. Brush, The kind of motion we call heal, North-Holland, 1986, cI976.

H. Smith and H. H. Jensen, Transport phenomena,Oxford University Press, 19S9.

Plasma physics
I... Spitzer, Jr., Physical processes in the interstellar medium, Wiley, 197S.

Phase transitions . .
P. PfeiHy and G. Touiouse, Introduction to the renormalizat'ton group and to critical
phenomena, Wiley, 1977.
H. E. Stanley, Introduction to phase transitions and critical [ihenomena, Oxford Uni-
University Press, 1987.

Metais and affoys

P. Haasen, Physical metallurgy, 2nd ed., CambridgeUniversity Press, 1986. Superb.

Boundary value problems

H. S- Carslaw and J. C. Jaeger, Conduction of heat in solids, 2nd ed., Oxford Univer-
sily Press, 19S6,ci959.

Semiconductor devices

R. Introduction to applied solidstate physics,

Datven, Plenum, t990.
K. Seeger, Semiconductor physics:an introduction, 5th ed., Springer, 1991,
S. M. Sze,Physics of semiconductor devices, 2nd ed., Wiley, t981.

Solid state physics

C. Kittel, Introduction to solid state physics, 6th ed., Wiley, 1986. Referred to ssISSR
Thermal
Introduction

Our approachto thermal physics differs from the tradition followed in beginning
physics courses. Therefore we provide this introduction 10set oul what we are

going to do in the chapters that follow. We show the main lines of the logical
structure: in this subject all the physics comes from the logic. In order of lhcir

appearance,the leadingcltaracters in our story are the entropy, the temporaiure,

the Boltzmann factor, the chemical potential, the Gibbs factor, and the disiribu-
tion functions.
The entropy measures the number of quantum states accessible to a system.
A closed system might be in any of these quantum states and (we assume)with
equal probability. The statistical element, ihe fundamental
fundamental logical

assumption, is that
quantum states are either accessible o r inaccessible to the

system, and the system is cquaiiy likely to be in any one accessible slate as in

any olher accessible slate. Given g accessible states, the cniropy is defined as
a = logg. The entropy lhtis defined will be a function of ihe energy U, lhe
number of particles N, and the volume V of the system, because theseparam-
parameters ciilcr the dctcrminaiion of y; other para meters may enter as wirii. The

use of the logarithm is a mathematical convenience: it is easier to write 1010

than expA020), and it is morenatural for two systems to speak of a-y + o, lhan
ofg,3j.
When two systems, each of specified energy, are brought into thermal coniact
ttiey may transfer energy; their total energy remains constant,but the comlraints

on their individual energies are lifted. A transfer of energy in one direction, or

perhaps in the other, may increase the product g^g, that measures the tiumber of
accessiblestates of the combined
systems. The fundamental assumption biases
the outcome in favor of that allocation of the total energy that maximizes the

number of accessible states: more is better, and more likely. This statement is
the kernel of the law of increase of entropy, which is the general expression of
the second law of thermodynamics.
We havebrought two systems into thermal contactso that they may transfer
energy. What is the most probableoutcome ofthe encounter? One system will
gain energy at lhe expense of the other, and meanwhile the lotal entropy of the

two systems will increase. Eventually the entropy will reach a maximum for
the given total energy. It is not difficult to show (Chapter 2) that the maximum
is atiained when ihe value o((ca/cU}K_y for one system is equal to the value of
ihe same quantity for the Second system. This equality property for Iwo systems
in ihermai coniaa is just the property we expect of the icmperat lire. Accordingly,
we define the fundamental lemperaiure i by the relation

1
U)
CUJ

The use of 1/r assuresthat energy will flow from high x to low r; no more com-
complicated rclaiion is needed. it will foilow'that ihe Kelvin temperature T is
directly proportional to t, with i =
Ayr, where kB is the Boltzmann constant.
5 is -
The conventional entropy given by .S\" kRa.
Now consider a very MiiipJe csampli? uf ibe Dolt/nvnm factor treau-d in

Uiajner 3. i.ti a Miiall sysicm wiih uiily iwn sinies, i.fie :it cnorj>y tl :iml une :n
energy c, be pjaeed in thermal coniaci with u large system Uial we eaH the
reservoir. The loia! energy of the combined systems is UQ; when the small
system is in ihe stale of energy 0. the reservoir has energy Uo and wiil have
g{U0) states accessibleto it. When the small sysiem is in the slate of energy e, the
reservoirwill have energy Uo
\342\200\224
and
\302\243 wiii have g{U0 \342\200\224
e) slates accessible lo
it. By the fundamental assumpiion, the ratio of tbe probability of finding [he
smali system with energy s to the probability of finding it with energy 0 is

, - c)
B)
^@) gWo) exp[<*(f o)]

The reservoir entropy a may be expanded in a Taylor series:

g{U0 - e)
~
a{Ua)
~
\302\243{ca/tV0)
=
c(t/0)
- e/r , C)

by the definition A) ofthe temperature. Higher order terms in the expansion

may be dropped. Cancellation of the term exp[_a{U0)], which occurs in the

numerator and denominator of B) after the substitution of C), leaves us with

This is Boitzmantt's result. To show its use, we calculate the thermal average
energy (e) of the two state system in thermal contact with a reservoir at tem-
temperature t;

E)
where we have imposed the normalization conditionon the sum of the prob-
probabilities:

P@) + P{e) - 1. F)
The argument can be generalized immediately to find the average energy of a
harmonic oscillator at temperature r, and we do this in Chapter 4 as the first

step in the derivation of the Planck radiationlaw.

The most important extension of the theory is to systems that can transfer

particles ns well as energy with ttie reservoir. For two systems in diffusive and
thermal contact, the entropy will be a maximum with respect the transfer to
of particles as well as to the transfer of energy. Not only must {ca/cU)\\- be
%\342\226\240

eqtuti for Hie two systems, btil (f it/jW)^,. must also be equal, where N refers to
the mmilKr of particles of ;i {uwn spevk's.Tin-* ih'w cttii:tiity coiutiiion is Hio

For two systems in thermal and diffusive contact, r, <=

r2 and jt1
= \\it. The

sign in G) is chosen to ensure thai the direction of particle flow as equilibrium

is approachedIs from high chemicai potential to low chemical potential.
The Gibbsfactorof Chapter 5 is an extension of Ihe Bolizmann factor and

ailows treat systems ilia! can transfer particles.The simplestcx:unpie

us to is a
system with two states, one witli 0 panicles and 0 energy, and one with 1 parltcie

and energy e. The system is contact

in with a reservoir at temperature r and
chemicalpotential;i. We extend C) for the reservoir entropy:

tf(f/0
-
t;HQ
- 1) = 0(r/o;A'o)
-
z{ca/dUo) - l-{ca/dNo)
~ o(U0;NQ)
~
c/r + ^/r. (S)

By anaiogy with D), we have

=\302\273 -
P{U)/P@,Q) cxp[{/( \302\243)/r] , (9)

for the probability the system

ratio ofihe is occupied bv J particle at energy z
to the probability the system ts unoccupied, with energy 0. The result (9)after
normalization is readily expressed as

A0)
This particular result is known as the Fermi-Dirac distribution function and
is used particularly in the theory of metals to describe the electron gas at low

temperature and high concentration (Chapter 7).

The classicaldistribution function used in the derivation of the ideal gas law-
is just the limit of A0) when the occupancyPA,e) is much lessthan 1:

The properties of the ideal gas are developedfrom this result in Chapter 6.
The HeSmholtzfree energy F= V \342\200\224
to appears as an important computa-
computational function, because the relation {5F/cx)s v
= \342\200\224
a offers the easiest method
for finding the entropy, once we have found out how to calculate F from the

energy eigenvalues (Chapter 3). Other powerful tools for the calculation of
thcnnodyiumic functions arc developed the text. Most
in of the reiftaiiuier of
the tcxl concerns applications that are useful in their own right and that illumi-
illuminate the meaning and utility of the principal thermodynamic functions.
Thermal physics connects the world of every iky objects, of astronomic;*!
objects, and of chemical and biological processes with the world of moiecular.
atomic, and electronic systems. It unites the two parts of our world,the micro-

microscopic and the macroscopic.

Chapter 1

States of a Model System

BINARY MODEL SYSTEMS 10

Enumeration of States and the Multiplicity Function U

Binary Alloy System 16
Sharpness of the Multiplicity Function 18
AVERAGE VALUES :\342\226\240 22

of ihe
'' --. -3
Energy Binary Magnetic System
Example: Multiplicity Function for Harmonic Oscillators 24

SUMMAItY 26
Chapter !: States of a ModelSystei.

Bul although, as a matter of history, statisticalmechanics

owes its origin to
investigations in thermodynamics, it seems eminently worthy of an independent
development, both on account of the elegance and simplicity of its principles,
and becauseit yields new results and places old truths in a new light in

departments quite outside of thermodynamics,

J. W. Cibbs

A theory is the more impressive the greater the simplicity of its premises, the
more different kinds of things it relates, and the more extendedits area of
applicability. Therefore the deep impression that classical thermodynamics made
upon me. It is ihu only physical theory of universal content which I am convinced
mil never be overthrown, within the framework of applicability of its basic
concepts.
A. Einstein
 Chapter 1: States of a ModelSyster,

Thermal physics is the fruit of the union ofslatistica! and mechanical principles.
Mechanicstells us the meaning of work; thermal physics tells us the meaning of
heat. There are three new quantities in thermal physics that do not appear in
ordinary mechanics:entropy, temperature, and free energy. We shall motivate
their definitions in the first three chapters and deduce their consequences
thereafter.

Our point of departure for the developmentofthermal physics is the concept

of thestationary quantum statesofa system of particles. When we can count
the quantum states accessibleto a system, we know the entropy of the system,
for the entropy is defined as the logarithm of the number of states (Chapter 2).
The dependenceof the entropy on the energy of the system defines the tempera-
temperature.From rhe entropy, the temperature, and the free energy we find the pressure,
the chemical potential,and all other therm odynamic properties of tlie system.
Fora system in a stationary quantum state, all observable physicalproperties
such as the energy and the number of particlesare independentofthe time.For
brevity we usually omit the word stationary; the quantum slates that we treat
are stationary exceptwhen we discuss transport processes in Chapters 14-55.

The systems we discuss may be composedof a single particle or, more ofi^n,
of many particles. The theory is developed to handle genera! systems of inter-
interacting particles, but powerful simplilicarions can be made in special problems
for which the interactions may be neglected.
Each quantum slate has a definite energy. Stales with identical energies arc
said to belong to the same energy level. The multiplicity or degeneracy of an
energy level is the number of quantum states wiih very nearly the some energy,
it is the number of quantum slates that is important in thermal physics, not
tlte number of energy levels. We shall frequently deal fti'th sums over all quantum
states. Two states at the same energy must always be counted as two slates,

not as one level.

Let us look antic qiu.Umusuresam! eitcryy lewis uOveia! alomic s>^u-ms.
The simpler is hydrogen, with oik electron and one proron. The !u.\\-I>iiig
energy levels of hydrogen are shown in Figure !.!. The zero of energy in the
figure is taken at the state of lowest energy. Tlte number of quantum stales
belonging to the sameenergy level is in parentheses, in lite figure we overlook
that the prolon has a spin of \\h and has two independent orientations, parallel
Chapter 1; States of a Model SyMm

Hydrogen Lithium Boron

lergy levelsof atomic

Low-tying ei hydrogen, lithium, ant! boron. The
energiesare given votis, with t eV = 1.602 x tO\0211 erg. The numbers \302\243
in electron

parentheses give ihe number of quantum stales having the same energy, with no ac
lakenofthe spinoflhe nucleus. The zero of energy in the figure is taken forcouvei
ai die lowest energy slaie of each aiom.

or antiparaliel to the direction of an arbitrary external axis,such as the direction

of a magnetic field.To takeaccount of the two orientations we should double
the values of the multiplicities shown for atomic hydrogen,
An atom of lithium has three electrons which move about the nucleus. Each
electron interacts with the nucleus,and eachelectronalsointeracts with ail the
 Chapter I: Statesofa Model Systet

30
IUpresc
Mill lip liciiy diq

4 3 1
25
4 2 2

4 2
20
3 3 i

4 1

J 3 2 2

i 15
3 2

2 2
3 1 1
5 to -
3 2 1 \\

' 1
_

1 1

Figure 1.2 Energy levels, multiplicities, and quanlum numbers

\302\253_,,
jjj,, n, ofa particle confined to a cube.

other electrons.The energiesofthe levels of lithium shown in the figure are the
collective energies of the entire system. The energy leveis shown for boron, which
has five electrons, are also the energies of the entire system.
The energy ofa system isthe total energy ofal! particles, kinetic plus potential,
with account taken of interactions between particles. A quantum state of the
system is a state ofall particles. Quantum states ofa one-pariicie system are
called orbitals. The low-lying energy levels ofa single particle of mass M con-
confined to a cube of stde are
\302\243 shown in Figure 1.2. We shall find in Chapter 3
Chapter 1: State* of a Model System

that an orbital of a free particlecan be characterized by three positive integral

quantum numbers nf, nyi
n,. The energy is

The multiplicities of the levelsare indicated tn the figure. The three orbitals
wiih(HJl^>.fi.)equ.iltoD,l,l),(l,4,]),and{l,l,4)ai!l!aveii/ + nr2 + n.1 = 18;
the corresponding energy level has multiplicity 3. the

To describe the statistical properties of a system of A' particles, it is essemial

to know these!of values of the energy \302\243S(N),where c is theenergy of the quantum
siaie soTthejV particle system. Indices such as s may be assigned lo the quantum
states in any convenient arbitrary way, bul two different states should not be
assigned the same index.
It is a good idea to siart program by studying the properties of simple
our

model for which

systems the energies A') can be calculated e.vacily. We choose Ej{

as a modela simple system because the genera! statisiical propenies

binary

found for are believed to appiy equally

the model system well to any realistic
physical system. This assumptionleadsto predictions that always agree with
experiment. What general statistical properties are of concern will become clear

as we go along.

BINARY MODEL SYSTEMS

The binary model syslern is illustrated in Figure 1.3. N

We assume there are
separate and distinct sites fixed in space, shown for convenience on a line-
Attached to each site is an elementary magnet titat can point only up or down,
corresponding to magnetic To understand tlie system means to
moments \302\261n>.

count the slates.This requites no of magnelism: an element of the

knowledge

system can be site capable of two states, labeled as

any or no, red or blue, yes

occupied or unoccupied,zeroor one, one or minus one. The sites are plus

numbered, sties with dtSFercni

and numbers are supposed to overlap in not

physical space. You might even tltink of the sites as numbered parking spaces in

a car parking lot, as in Figiire 1A Cacti parking spuce has two states, vacant or

occupied by one car.

Whatever llic milure of otlr objects, we may desigreiic the two slates by
arrows that can only point straight up or straight down. If (he magnet points
up, we say thai ilie magnetic moinenr is -Hii.If the magnet points down, the
magnetic moment is -m.
 Binary Model Syster

123456789 10
Number of the site

Ffgure 1.3 Mode! system composedof 10elementary

magnets at fixed sites on a line, each having magncric
moment The
\302\261m. numbers shown arc aflachcd to ihc silcs;
each sire has ils own magnet We assume there are no

magne'ic field.Each magnetic moment may be oriented in

two up or down, so ihai there are 210disiincl
ways,
arrangements of the 10 magnetic moments shown in the

figure. If ihe arrangements arc selectedin a random process,

(he probability of finding tile particular arrangement shown
is 1/210.

Figure 1.4 State ofa parking lot with 10 numbered parking

spaces. TiseO's denotespaces occupied by a car; theO's
denote vacant spaces. This particular state is equivalent to that

shown in Figure (.3.

Now consider N different sites, each of which bears n moment thai may
assume the values +\302\253i. Each moment may be oriented in two ways with a

probability independent of the orientation ofa!! other moments. The total

number of arrangements nf the N moments is 2 x 2 x 2 x \342\226\240

\342\226\240
\342\200\242
2 *= 2\\ A
state of the system h sjveitiedUy yiviiig the orient at ion of the moment oil c:k!i

site; there are 2'v states. We may use ilio following simplettotation for a single

state of the system of N sites:

nuimrr- B)
 States
\342\226\240rl: of a Model Syst

Figure 1,5 The four diflercnl Males of a

s> stem of two elements numbered | and 2,
vs here ench clctnetit can hsvc two conditions
The element is a magnel which can be in

condition f orcondiiion [.

The sites themselves are assumed to be arrangedin a definite order. We may

numbcr4hem in sequence ftom left to right, as we did in Figure1.3.According
to this convention the state {2}also can be wriitcn as

C)

Both symbols B) and {3}denotethe same state of the system, the slate
sets of
in which the magnetic moment on site 1 is +m; on site 2, the moment is -t-m;

on site 3, the moment is -m; and so forth.

It is not hard to convince yourself that every distinct state of the system is
contained a symbolic
in
product of N factors:

U)(U D)

The multiplication ruie is defined by

(Tt + liXti + li) ti + till + UU + E)

The function D) on muitipltcation generatesa sum of 2*v terms, one for each of
the 2'v possible states. Each term is a product of N individual magnetic moment

symbols, with one symbol for each elementary magnet on the line.Each term
denotes an
independent state of the system and is a simpleproductof the form
''\" f\302\260r
T1T3I3 t\\i example.
For a system of two elementary magnets, we multiply (}x + li)by(t2 + |j)
to obtain the four possible states of Figure 1.5:

(Ti + I1KT2+ ii) Till itTa + I1I2. F)

The sum is not a state but is a way of listingthe four possible states of the system.
The product on the left-hand side of the equation is calleda generatingfunction:
\342\226\240
it generates the states of the system. . \342\226\240 \342\226\240
.
 Binary Model Systems

The generating function for the slates of a system of three magnetsis

(Ti + li)(?2+ IjHTj + U)-

This expressionon multiplication generates21 = S different states:

Three magnets up: T1T1T3

Two magnets up: T1T2I3 T1I2T3 lihti

Onemagnctup: tihli IJ2I3 lilif3

None
up: lilils-

The totat magnetic moment of our model system of N magnets each of

magnetic moment m will be denoted by Mt which we will relate to the energy
in a magnetic field. The value of M varies from Nm to -- Nm. The set of possible
values is given by

- (N - - \342\200\242
\342\200\242
M \302\253
Nm, {N 2)m, 4>n, (N 6)m, -A'\302\273i-
\342\200\242, G)

The set ofpossible values of M is obtainedif we start with the state for which all
magnets up (M
are = Nm) and reverseone at a time. We may reverse iV magnets
to obtain llie ultimate state for which al! magnets are down (A/ = - Nm).
There are N + ] possible values of the total moment, whereas there are 2s
states.When N \302\273!, we have 2N \302\273N + 1. There are many more states than
values of [he total moment. !fW = 10,there are 210= ! 024 states distributed

among 11 different values of the total magnetic moment. For large N many
different states of the system may have the same value of the total moment ft/.

We will calculate in the next section how many states have a given value of M.

Only one state of a system has the moment M = Nm;that state is

-
TTTT- -TTTT- (S)

There arc N ways to form a slate with one magnet down:

mt \342\200\242\342\226\240\342\226\240mt AJ)

is one sue! 1 state; another is

\"

tin \342\226\240\342\226\240.\342\226\240tin, do)

Chapter 1: Slates of a Mode!System

and the other slates with one magnet down are formedfrom (S) by reversing
any single magnet. The states (9) and have
\302\243!0) lot.il moment M = Nw - 2w.

Enumeration of Stales and the Multiplicity Function

We use the word spin as a shorthand for
elementary magnet. It is convenient lo
assume that N is an need a mathematical expressionfor the
even number. We
with W, = {W + s magnets up and Nl = jN
number of states \342\200\224
s magnets

down, where sis an integer. When we turn one magnet from Ihe up [he down
to
orientation, {.V + 5 goes to jW + s - I and ?N
- s goes to jiV ~ 5 + I.
The difference (number up \342\200\224 number down) changes from 2s to 2a \342\200\224
2. The

difference

W, - /V,
= 25 (ID

is called ihc spin excess. The spin excess of the 4 states in Figure 1.5 is 2,0, 0, \342\200\224
2,

from left to right. The facior of 2 in (I!} appears to be a nuisance at this stage,
but it will prove to be convenient.
The productin D) may be written symbolically as

(T
\342\226\240.
+ if-

We may drop the site labels {thesubscripts) from D) when we are interested
only in how many of the magnets in a state are up or down, and not in which

particular sites have magnets up or down, ft we drop the labels and neglect
the order in which the arrows appear in a given product, then E) becomes

-
(t II;

further,

(t + I)' = Itt + 3ItJ + 3IJJ + jjj.

We find (I + |)v for arbitrary iV by the binomial expansion

A2)
 Enumeration of Stales and the Multiplicity Function

We may write the exponents of x and y in a slightly different, but equivatem,

form by replacing t with \\N
\342\200\224
s:

With ihis result ihe symbolic expression{| + |)'v becomes

4- ivv =* y tj-v+j M*V\"J

A4)

The coefficient of the term in

iA-+*
of stittes having M*\"' is the number
f

W,
=
$N + 5 magnets up and N, = i.V s magnets down. This class of -
states lias spin excess JV, \342\200\224
JVj
= 2s and net raagneiic moment 2sm.Let us

denote the number of states tn this class by g{N,s), for a system of N magnets:

,n\342\202\254>T

(IS)

Thus A4) is written as

(I + i)'v= I stJMT^l1\"\" A6)

We shall call g(N,s) ihe multiplicity function; it is ihe number of slates having
llie same value of 5. The reason for our deltnttion emerges when a magnetic
field is applied to the spin system: in a magnetic field, stales of different values of

s have different values of the energy, so that 9 is equal

\302\260ur multiplicity to the
of an energy level tn a magnetic field. Until we introduce a magneticfield, all
states of the model system have the same energy, which may be taken as zero.
Note from A6) that the total number of states is given by

'
L g{Nts) = A + l)-v = 2-v (H)

Examples related to g{h',s)for A' ~ \\Q are given in Figures 1.6 and 1.7. For a
coin, \"heads\" could stand for \"magnet upland \"tails\" could stattd for \"magnet

down.\"
 Chapter t: Slatesofa Model System

Figtorc 1.6 Number of distinct arrangements

of 5 -f j- spins up and 5 ~ 5 spins down.
Values of yf Npi) are for N - 10, when: 2.v h
tUc spin oixss N \\ - K I. Tlic toul numtwt of
stales is

TTic values of the 9's arc taken fro

the binomial coefficients.

I -8 I -4 j 0 2 4 6
-10 -6 -2
Spin excess 2s

Binary Alloy System

To illustrate that the exact nature of the two states on each site is irrelevant to
the result, we consider an alternate system\342\200\224an
alloy crystal with N distinct
sites, numbered from 1 through 12 in Figure 1.8. Each siteis occupiedby either
an atom of chemical species A or an atom of chemical species B, with no provi-
provision for vacant sites. In brass, A could be copper and B zinc. In analogy to C),
a single state of the alloy system can be written as

-
A8)
 nry Allay Sya,m

\342\226\240=
o

S 3 20

01 23456789 10
Number of heads

Figure 1,7 An experiment Was done in which 10 pennies

were thrown NX) times. The number of heads in each
throw was recorded.

0\302\25100
I 2 3 A

Fijutc 1.8 A binary alloy syslcm of two

chemical A and 1!,whoseatoms
\302\251 0 componenls
5 6 7 S

0
II
012
10
Every distinct state of a binary alloy system on N sites is contained in the
symbolic product of N factors:

(A, + B1)(A3 4- B2)(A3 + Bj)---(A.V +BN) , A9)

in analogy to The Liverage composition of a binary

D). alioy is specified con-
conventionally by the chemical formula A1_1B1, which means thai out of a tola!
of N atoms, the number of A atoms is NA ~ A ~x)N and the number of B
atoms is NB ~ .\\JV. Here .v lies between Oand 1.
The symbolic expression

is analogous to the result A2). The coefficient of the term in A'v\"' B' gives the
number g{i\\\\f) of possible arrangements or states of N ~ atoms
\302\243 A and /
atoms B on N sites:

which is identical to the result A5) for the spin model system, except for notation.

Sharpnessof ihe Multiplicity

Function

We know from common experience that systems held at constanttemperature

usually have well-defined properties; this stability of physical propertiesis a
major prediction of thermal physics. The stability follows as a consequenceof
the exceedingly bharp peak in the multiplicity function and of the steep variation
of that function away from the peak. We can show explicitly thai for a very

large system, the function <j(Af,s) defined by A5) is peaked very sharply about
the value 5 = 0. We look for an approximation that allows us to examine the
form of g(S,s) versus 5 when jV \302\273
i and
js| N.
\302\253 We cannot (ook up these
values in tables: common tables of factorials do not go above N = 100, and we
may be interested in Af =^ 10'\302\260,of the order of the number of atoms in a soiid
specimen big enoueli to be seen and felt. An approximation is clearly needed,
and a good oneis available.
It is convenient to work with log*/, f-xccpl where .-ilierwise specified, till
logarithms are understood to be loy base*?,written here as log. The international
standard usage is In for log base c, but it is clearer to write log when there is no

ambiguity whatever. When you confront a very, very large number such ;is
 Sharpnessof the Multiplicity Function

2iV, where iV ~ lG:o,it is a simplification to look at the logarithmoft he number.

We take the logarithm of both sidesof A5) lo obtain

\\ogcj(N,s) = logN! - logfrV + 5)! - log&N

-
s)l , B2)

by virtue of ihe characteristicproperlyofthe logarithm of a product:

logxy = logx + logy; log(.\\-/_v)

= log.v
~ logy. {23)

With the notation

jV, = \\N 4- 5; A', =\302\253

\\N
~ s B4)

for the number of magnetsup and down, B2) appears as

logg(N,s) - logW! - logiV,!- logW,!. B5)

We evaluate the logarithm of N\\ in B5) by use of die Stirling approximation,

accordingto which 1 ZjTi'Go
s-t\\Q\\ \\

.V! a BrtN)ti:iNNcxpl~N + IJ[12N) + \342\226\240

\342\200\242
,
\342\226\240] B6)

for N \302\273
1. This result is derived in Appendix A. For sufficiently large N, the
terms 1,A2iV) +
\" \342\226\240
in the argument may be neglected in comparison with N.

We take the logarithm of both sidesof B6)to obtain

logN! S I log 2k + (N + |) log N ~ N. B7)

Similarly

!ogjVt! s I log 2?r + (JV, + JJlogN,

- jV,; BPJ

logN,! s iiog2* + (,Vi + J)log.V,

- Nu B9)

After rearrangement of B7),

S '.- f.V, + + -V, + i)logJV

- (.V, + CUf
log.Y! Ito\302\243B!r/A') \\ Nj) ,

wlK'i'ciwcliaVcuscilW = .V, I- .Vt. \\VL-siil>ii;iLl{2S);iiKM2'J)froin{.!U)loobl:iiii

for B5):

tog</ S ilog(l/2;r,V) - (.V, + iJlogty./.Y)

- (,V, -f i)Uui(.V,/.V). C1)
This may be simplified because

logOV,/iV) = log^l 4- 2s/jV)

= -iog2 + iog(i -f- 2s/S)

~
-iog2 + Bs/,V) - I2s2/N2) C2)

by virtue of the expansion logfl + x) = .v

-
jx2 +
\342\200\242
\342\226\240
-, valid for x \302\253
I.

Similarly,

!og(W,/A') = logld - 2s/N) = -log2 - B5/N)

-
Qs2/,\\'!). C3)

On subsliiuiion in C!) we obtain

s |logB/;E/V) + -
iogg Wiog2 2s!/N. C4)

We write this result as

C5)

WnH)\"*?1. C6)

Such a distribution of values of sis caiicda Gaussian distribution. The integral*

of C5) over the range \342\200\224
co to + co for s gives the correctvalue 2*for the total

number of states. Several useful integrals are treated in Appendix A.

The exact value of y(N,0) is given by A5) with s = 0;

C7\302\273

\342\200\242
The replacement of a slim by an iniegrai, such as \302\243
{. - \342\226\240)
by f{_. .)Js, usually does
errors. For example, ihc rai io of '
significanl

Ts./s = IN2
X s to
=-- +
i{N2 N)
\302\273^o

is equal io 1 + A/N), which approaches i as N approaches co.

 10

\\
Figure 1.9 Tlie Gaussian approsimaiion (o
X.
(he binomial cocfficicnis g{!OO,s) plotted on a
\"
6 1 \342\200\224 iinearscaie. On this scale ii is not possible io

\\ distinguish on ihc drawilig the approximation

plotted The entire range of s is from - 50 to

4 \\ 4- SO. Thedashed lines ai\302\253

points at t/e or (he maximum
drawn from
vaiuc or
the
y.

n
0 y
-20 -10 0

For N = 50, the value of sE0,0) is 1.264 x 101*,from C7).The approximate

vylue from C6) is 1.270 x 1014.Thedistribution plottedin Figure t.9 is centered
in a maximum at s = 0. When s1 =
{N, the value of g is reduced to e~' ofthe
maximum value. That is, when

s/N = A/2NI'2 , CS).

the value of gise\021 of g(N,0).The quantity A/2NI'1 is Ihus a reasonable mea-

measure of the width of the distribution. For N =s 1022, the fractional
fractional
width is of the order of 10\"u. When N is very large, ihc distribution is exceed-

exceedingly sharply defined, in a relative sense. It is this sharp peakand the continued
sharp variation of the multiplicity function far from the peak that will lead to a

prediction that properties of systems in thermal equilibrium

the physical are

well defined. We now consider one such property, the mean value of s1.
ChapterI: Stales of a Modal System

AVERAGE VALUES

The averagevalue, or mean vaiue, of a function f(s) taken over a probability

distribution function P(s) is defined as

</> = Z/<*m*), 09)

provided that Uic distribution function is normalized to unity;

!. D0)
\302\243?(*)-

The binomial distribution A5) has lite property A7) that

\302\253
2W
Zs(iV,5) , D1)

and is nol normalized lo unity. If all states are equally probable, ihen P(s) ~
g{N,s)/2s, and we have \302\243J'($)
- t. Tfic average of/(s) over this distribution

will be

D2)

Consider tile function f{s) = s2.In the approximation that led to C5) and
\342\200\242
\342\226\240 ~- co
C6), we replace in D2) the sum over
\302\243
s by an integral J
\342\226\240
ds between

and + co.Then

- [2/nNI'3 (jV/2)J'J
J^Jxx^\"'*

= {2/7r,V)\"!{.V/2):i'J (jt/4)\022 ,

whence

<i-J>
= iiV; <B,y> = ,V. D3)

The quantity <{2i);> is the mean square spin excess.The root mean square

spin excess is

-
<B5}2>';J =>yfN t D4)
 <uy Magnetic Sys

and the fractional fluctuation in 2s is defined as

D5)

The larger N is, the smaller is the fractional fluctuation. This means that the
central peak of the distribution function becomes relatively more sharply
defined as the size of the system increase;, the size being measured by ihe
number of sites N. For 10:oparticles, $F - 10\0210,which is very small.

Energy of the Binary Magnetic System

The thermal properties of the model system become physically relevant when
the elementary magnets arc placedin a magnetic ticid, for ihen the energies of
the different states ate no longer all equal. If the energyof the system is specified,

ihen only the suites having this energy tn;ty occur. The energy ink-net
\302\273f ion
ofa single magnetic moment m with a fixed external magnetic field B is

\302\273
-m-B.
V H6)

This is the potential energy of the magnet m in the field B.

For the model system of Ar elementary mngncts, each with two allowed
orientations in a uniform magnetic field 1J, the tola! potentialenergy U is

m,- =Q.
- MB , D7)
2smB}=

using ihe expression M for the toial magnetic moment 2s/n.In this example lite

spcclnttn of values of ihe encrcy U is discrete. We shall con-

sec later (hat a
continuous or quast-conttnuous spectrum will creafe no difficulty. Furthermore,
ihe spacing between adjacent energy levels of (his model is constant, as in
Figure t.tO. Constant spacing is a special feature of the particular tnodcl, but
this feature will not restrict the generality of (he argument that is developedm
ihe Following sections.
The value ^f (he energy for moments ihat inferact only with the exicnial

magnetic field ?.; ^ornrfcicly ridennined by the value of s. This funcitotutl

dependence is, i..ucaka by wrtitng U{s). Reversing a single moment lowers
2s by -2, lowers the total magnetic moment by ~2m, and raises the energy
by 2mB.The energy difference bsiween adjacent levels is dcnotcJ by Ac, where

Ae = DS)
Chopset

UM./mB s(.) log g(

+ 10' 1 0
+ S
\342\226\240
10 2.30
+ 6 45 3.81
+ 4 120 4.79
+2 210 5.35
0 252 5.53
__2 210 S.3S

+2 \342\226\240
-4 120 4.79

+ 3 -6 45 3.81

+ 4 -8 10 2.30

+5 -10 1 0

magnetic nmmersis field S. The levels

m m a magnetic
are labeled by where 2s is ihe spin excess
their s values,
and \\N + s ==\342\226\240
5 + i isihe number of tip spins. The
energies UD ititd muliiplictlics g(>) ^fe showti. Tor this

Example: Multiplicity function for harmonic oscillators. The problem of tlic binary model
system is the
simplest problem for which an exact solution for the multiplicity function is
known. Another exactly solvable problem is the harmonic oscillator, for which the solution
was originally given by Max Planck. The original derivation is often felt to be not entirely
simple. The beginning Sludent need nol worry about this derivation. The modern way to

do the problem is given in Chapter 4 and is simple.

The quantum slates ofa harmonic oscillator have the energy eigenvalues

es = sho) , D9)
where the quantum number s is a positive integer or zero, and to is the angular frequency of
the oscillator. The number of states is infinite, and the multiplicity of each is one. Now
consider a system of N such oscillators,all of the same frequency. We want to find the
number of ways in which a given total excitation energy
can be distributed among the oscillators. That is, we want the multiplicity function g{N,n)
for tlie Af oscillators. The oscillator multiplicity function is not the same as the spin mufti-
pitcitv function fount! e^rher.
We begin the analysis by going back to tlie multiplicity function for a single oscillator,
forwm'chff(i,\302\253)
= 1 for ail values of the quantum numbers, here identical to m. To sojve the
problem of E3) below, we need a function to represent or generate ihe scries

E1)

AS! Y,fl!!1 from ^ co-

S\302\260 ^CfC ' 's a temporary
Jusl tool that will help us find the result
(S3), but t docs not appear in the final result. The answer is

(S2)

provided we assume\\i\\ < |. For the problem of JV oscillators, the generating function is

E3)

becausetlie number of w;iys n term i\" can ;\\\\i\\Kai in the N-fold pftiJuct is picciscly ihe
number of onSctedwuys in which the integer n c;m be foiuicJ as the sum of iV non-iicg.nive

We observe that

tj{N,n)

2) - \342\226\240
\342\200\242
(W + n - 1). E4)

Thus for the system of oscillators,

ES)

This result will be needed in solving a problem in the next chapter.

Chapter 1: States of a Mode!System

SUMMARY

1. The multiplicity function for a syslem of N magnets with spin excess 2s =

N, - N't is

In ihe limit s/N \302\253

1, with A' \302\273
1, we have the Gaussian approximation

g[N,s) * {2/rlN)m2xexp{~2s2/\\').

2. Ifal! states of the mode! spin system are equally likely, the average value of
2

52> =
j''^JsstgtN,s) p

in the Gaussian approximation.

3. The fractional fluctuation of s2 is defined as (s2yll2/N and is equal to

S/2N\022.
4. The energy of the modelspin syslem in a siaie of spin excess 2s is

where in is the magnetic moment of one spin and B is the magnetic field.
Chapter 2

Entropy and Temperature

FUNDAMENTAL ASSUMPTION 11

PROBABILITY 3'\\

Example: Construction of ;in Ensemble 3-

Most ProbableConfiguration 33

Example: Two Spin Systems in Thermal Contact 3?

THERMALEQUILIBRIUM 39
TEMPERATURE

ENTROPY -\342\226\240!

Example: Entropy Increase On Heat Floiv 41

Law of increase of Entropy 45

LAWS OF THERMODYNAMICS -iS

Entropy as a Logarithm 50
Example: Perpetual Motionof the Second Kind 50

SUMMARY 51

PROBLEMS 5:
1. Entropy and Temperature 52
2. Paramagnetism 52
3. Quantum HarmonicOscillator 52

4. The Meaning of \"Never\" 53

5. Additivity of the Entropy for Two Spin Systems 53
6. Integrated Deviation 54

Note on problems: The melhoJ of fhis chapter c

we Jo iitil cinplusi^e problem soKing dl lliis siu

Chapter 2; Entropy and Temperatui

One shouldno! imagine thai two gases in a 0.1 liter container,initially unmixed,
will mix, then again after a few days separate, then mix again, and so forth. On

the contrary,
\302\260
one finds .., ilia!not until a time enormously long compared to

W10 years will there by any noticeable unmixing of the gases. One may
recognize that this is practically equivalent to never. . . .

ff we wish to find in rational mechanicsan a priori foundation for the principles

of thermodynamics, we must seek mechanicaldefinitions of temperature and

entropy.
J. W. Gibbs

The genera} between energy and temperaturemay

connection only be established

by probability considerations. {Twosystems] are in statistical equilibrium when

a transfer of energy does not increase the probability.

M. Planck
We slart this chapter with that enables us to
a definition of probability
define the
average physical property
value of a
of a system.We then consider
systems in thermal equilibrium, the definition of entropy, and the definition of

temperature. The second law of thermodynamics appear

will as the taw of
increase of entropy. This chapter is perhapsthe most abstract in the book. The
chapters th;it follow wilt apply the concepts to physical problems.

' \" -
ASSUMPTION
FUNDAMENTAL \342\226\240

The fundamental assumption of thermal physicsis ttt;tt a closed system is equally

likely to be in any of the quantum states accessible to it. All accessible quantum
states arc assumed to be equally probable\342\200\224there is no reason to prefer some
accessible states over other accessible states.
A closed system will have constant energy, a constant number of particles,
constant volume, and constant values of all external parameters that may

influence including gravitational, electric, and magneticfields.

the system,
A quantum state is accessible if its properties arc compatiblewith the physical
specification of the system: the energy of the stale must be in the range within
which the energy of the system is specified, and the number of particles must be
in the range within which the number of parlictcs is specified. Wtlh large systems
we can never know either of theseexactly, but it will suffice to have.SU/l/ 1
\302\253

tmd&N/N \302\253
I.

Unusual properties of a system may sometimes make it impossible for

certain states to be accessible
during the time the system is under observation.
Fof example,the states form of SiO2 are inaccessible
of the crystalline at low

temperatures in any observation

that starts with the glassy or amorphous
form: fused to quartz in our lifetime
silica will not convert in a low-tcmpcraturc
experiment. You will recognize many exclusions of this type by commonsense.
We treat all quantum states as accessible unless they are excluded by the
specification of the system (Figure2.1)and the time scale of the measurement
process.Statesthat are not accessible are said to have zero probability.
Of course,it is possible to specify the configuration of a closedsystem to a

point that its statistical properties as such are of no interest. If we specify that ihe
Chapter 2; Enxropy and Temperature

I imtt of
spcMftcation of ihe sjstcn

V\\uil- 2, t A iwdy symbolic Ji:iKr;ihi: L-:idi solid s|x'

represents an accessible quantum slate of a closed sysn

fundymema! assumption of statistical pliysics is tliat a
system is equally likely to be in any of tlic quantum si;
accessible to it. \"Die empty circles represent some of thi
that are not accessible because their properties do nc
the specification of the system. IlovG vjfju -1 ,-/<_

system is exactly in a stationary quaniurn state s, no statistical aspect is left in

the problem.

PROBABILITY

Suppose we have a closed sysiem that we know is equally likely to be tn any

of they accessiblequantumstates.Let s be a genera] state label (a\302\273dnot one-half

ihe spin excess). The probabtHty P(s) of finding ihe sysiem in this slate is

P(s) = \\fg (t)

if the state 5 is accessible and P[s) = 0 otherwise, consistent with ihe fun-
fundamental assumption. We shall be concerned taier with systems that are not

dosed, for which the energy V and panicle number vary. For these
N may
systems P(s) wtH not be a constant as in A), but wilt have a functional dependence
on [/and on A'.
 Probubitiiy

The sum \302\243P(s) of the probability over alt states is always equal to unity,
because the total probability that the sysiem is in some state is unity:

_, . . B)

The probabilities tead to ihe definition of the averagevalue

defined by (I) of

any physical properly. Suppose iliat the physical property X has the value
X{s) when the is
system in the state s. Here X might denote magnetic moment,
energy, square of the energy, charge density near a point r, or any property that
can be observed wlien the system is in a quaniumstate.Then the average of the
observations of the quantity X taken over a system described by the proba-
probabilities I'{s) is

This defines the average value of X. HereP(s] is the probability

equation that
the sysiem is in the state s. The angular brackets are
\342\226\240>
<-\342\226\240 used to denote
average value.
For a dosed system, the average value of A' is /\"i>-'-f >':
' !' i -

D]

because now alt g accessible slates are equally likely, with P(s) = \\jg. The

average in D) elementary exampleof

is an what may be called an ensemble
average; we imagineg simitarsyslems, in one each accessible quantum stale.
Such a group of systems constructed alike ts catted an ensemble of syslems.The
averageof any properly over the group is catted ihc ensembleaverageof that
' \342\226\240'
'\342\200\242\342\226\240>-
\342\226\240',
.\342\226\240>.
property. _1_

An ensemble is composed of many

of systems systems, all consfrueled alike.
Each system in the ensemble is a replica of the actual system in one of the

quanium states accessible to the system. If there are g accessible stales, then
there wilt be g systems in the ensemble, one system for each stale Each system
in the ensemble is equivalentfor all practical purposes to the actual sysiem.
Each sysiem satisfies all external requirements placed on the original system
and in this sense is \"jus! as good\"as the actual system. Every quantum stale
 \342\200\242
\342\200\242 Y t : t t
\"U.:'j\\ Tit

* t
'[!\".;\"*'\342\226\240\342\231\246 -rrrt \302\273'.\"*

'';\"(:!' t t t
:\302\273\":;'\302\273''\342\226\240: t';t ;i

'[in :y t: r;jt t i t

/[r;i t t 'nrt yi t

sT'\"\302\273 t i rn; t -t t t

/.:Y:t I t fit Y \\ [\\ Y.

-\342\200\242Tit
t t rft t t t t

i'YY t t :t:;Y \\ ;m I

l;ij;ure 2.2 Tliis cuscmbJc \302\253

iJirotijiJij icpresciiis ;l
of lOspiiw wiih etwujy -Sui/Jimd spin excess 2.v

n!Litij]>]iciiy !/{.\\'.n) is yUU,4) |0, so tliut

Tlic = ilic

rcpfcscutiiiive cl]sv-]I]!iIc iiium ^inlnin Hi syML-ins,

order in which Uic vuriou^ sy>(cnis Mi tlie cusciubl
listed has no sighificance.

accessible lo the actualsystem is represented in the ensemble by one system in a

slaiionary quantum stale, as in Figure 2.2. We assume that the ensemble
representsthe real system\342\200\224this is implied in the fundameniat assumption.

Example; Construction of an ensemble- We conslruci in Figure 2.3 an ensctnMe to

represent a dosedsystem of five spins, each system with spin excess 2s = {.The energy of
each in a magnetic field is -mB. |Do not confuse !he use of s in spin excess with our
frequent use of s as a stale index or label.) Each system represents one of the muliiptes of
 t tl'OutibiC K.O[ij\\j}U\\iilI0

i\\ tj jTIT: f\\ t'T

Figure 2.3 The enscmbie represents a system with N = 5 spins and spin excess 2i - i.

\342\200\236 R\302\253ute2.4 With A' = 5 and 2s - 5,a singie

| f t .! I
\342\226\240\342\200\242! ! t Sy^m may represent ti1Ca\302\273embio.ThiS is .o!
ii ii

i states at tin's enetcy.Tlic number ofsuch slatesis given by tlic multiplicity function

Tile 10 systems shown m Figure 23 make up ttic cuwnibk.

If the energy in llie tiiLiitueliefieid weic siidi lli^t 2.\\- \342\226\240=
5r ltn-'ii n sinylc sysitm tomjiriscs

5 systems have 2s = 3; |Q sysiems have 7s = I: 10 systems have 2s = -1; 5 systems

have 2s - -3; and t system has 2j = - 5.

Most ProbableConfiguration
Let two systems 5, and be
\302\243t brought into contact so that energy can be
transferred freely from one to tttc other. This is called (hermnl contact (Figure
2.5).The two systems in contact form a larger closed system & ~ Sx + \302\243z

with constant energy U =. Ut

+ U2. a
Whai determines whether there will be
net flow ofenergy from one system to another? The answerleadsto the concept
of temperature. The direction of energy flow js not simply a matter ofwhethef
the energy of one system is greater than the energy of the other, because the
 r 2: Entropy anil Temperature

Two closed

in eomacl

s= + ut
The ure u\\ +\342\226\240
f/; ul
systems in

thermal contact

sulaliiin Thermal conduclor allows

exchange of energy

Figure 2.5 Establishment of Micrmal contact between [wo systems &, and

systems can be dificrcin in size and constitution. A constant lotal energy can be
sbared in many ways between two systems.
The most probabledivision of the t6tal energy is that for which the combined
system has the maximum number of accessible states. We shall enumerate the
accessible slates of two model systems and then study what characterizes the
systems when in thermal contact. We first solve in detail the problem of thermal
contact between two spin systems, 1 and 2, in a niagoetic fieldwhich isintroduced
in order to define the energy. The numbersof spins N u N2 maybe different, and
the values of the spin excess2s,, 2sz may be different rOr the two systems. All
spins have magnetic moment m, Tlie actual exchangeof energy might take place
via some weak (residual) couplingbetween the spins near the interface between
the two systems. We assume that the quantum states of the total system & can
be represented accurately by combination of any state of 3, with
a any state of
S2. We keep N,, N2 constant, but the values of the spin excess are allowedto
change.Thespin excess of a state of ilie combinedsystem will be denoted by 2s,
where s = sx + sz. The energy of ihe combinedsystem is dirccily proportional
to the total spin excess:

= ~2inBs. E)
U{s) s2)

The tola] number of particlesisN =

A'( + .Vj.
 Most ProbableConfiguration

We the energy splittings betweenadjacentenergy

assume that leveh are equal
to 7n\\B in
systems, so that the magneticenergy
both given up by system I when
one spin is reversedcan bo taken itp by the reversal of one spin of systctn 2 in
the opposite sense.Any large physical system will have enough diverse modes of
energy storage so that
energy exchange with another system is always possible.
The value of s = st + s2 is constant because t he total energy is constant, but

when the two systems are brought into thermal contact a redistributionis
permitted in ihe separate values of s,, s3 and thus in the energies I/,, Uz.
The multiplicity function g{N,s) of the combined system & is related to the

product of the multiplicity functions of the individual systems 5[ and 5Z by

the relation;

H2(Nj,s - s,) , F)

where the multiplicity functions gx, g2 are given by expressions of the form of
A.15). The range of s, in the summation is from -fiY, to %Nt, if Nl < N2.
To see how F) comesabout,considerfirst that configuration of the combined
system for which the first system has spin excess2sj and the second systetn has
spin excess 2s2. configuration
A is defined as the set of all states with specified

values of s( and sz. The first system hasg^N^s,) accessible states, each ofvvhich
may occur togeiher with any of the g1(N2,Si) accessible stales of ihe second

system. The total number of states in one configuration of the combined system

is given by the product gl{N1,sl)g2{N1,Si) of the multiplicity functions of Sk

and &2. Because s2 ~ ~

s sit the product of the g's may be written as

This product forms one term of the sum F).

Different configurations of Uie combined system are characterized by different

values of j{. We sum over a!!possiblevalues ofs( to obtain the total number of
suitesof all ihe configurations with fixed s or fixed energy. We thus obi a in F),
where y{N,s) is the numberof accessible states of the combined system. In the
sum we hold s, N,, and N2 constant, as part of the specification of therma!
contact.
The result F) is a sum of products of the form G). Such a product\\sill be a

maximum for some value of s,, say sL, to be read us \"st hat\" or \"si caret\".
The configuration for which glg1 is a maximum is called the most probab!e
cmtfigurntiun; ilie number of states in it is

gxiN1.Sl)g2[Nl.s
- 5,). . (8)
Chapter 2: Entropy am! Temper

A*. 0

Thermal equilibrium

Figure 2.6 Sclicmalic repressaiion of Ihe dependence of the

coiifiguralioji multiplicity on [he division of ihe tola! energy
belwcen two syslems.-S, and Sj.

!f ihe systems are large, the maximum with respect to changes in Sj will be
extremely sharp, as in Figure 2.6. A relatively of configurations
small number
will dominate the statistical properties of the combined system. The most
probable configuration alone will describe many of these properties.
Such a sharp maximum is a property of every realistic type of large system
for which exact solutions are available; we postulate that it is a genera! property
of all largesystems- From the sharpness properly it follows that'fluctuations

about the most probable configuration are small, in a sense ihat we will define
The imporlani result follows l hat the values of the average physicalproperties
of a large system in thermal contact with another large system are accurately
described by the properties nf the most probable configuration, the configura-
for
configuration which the number of accessible st3tes is a maximum.Such average

values (used in either of these two senses)are called thermal equilibrium values.

Because of the sharp maximum, we may replace the average of a physical

quantity over all accessibleconfigurations F) by an average over only ihe most
probable configuration (8). In the example below we estimate ihe errorinvolved
in such a replacement and find the error lo be negligible.
 Most Prabahte ConfiSui

Example: Tn-o sprn systems in thermal contact. We investigate for lUc modd spin syslem
tfiL- sharpness of the produci G) near the maximum (8) as follows. We form the product of
Ilie muliiplicity functions for(j,(W,.s,) and g^i-^J- ^olh ofiho form of|U5):

white ?i(Q)denotesjj,(:V,.G) and ^@} denotes ffsf.Vj.Q). We replace s, by s - *,:

- (jo)
--^- -l^iiLj.

This product* gives the number of statesaccessibleto the combined system when the spin
excess of the combined system is 2s, and the spin excess of ihc first system is 2s,.
We find the maximum value of(tO}as a function of s, when the total spin esccss 25 ishd.l
constant; that is, when the energy of the combined systems is constant, it is convenient
to use the properly that the maximum of fog.m) occurs at the same \\atue of x as the
maximum of >'{.y). The calculation can be done eilher way. From f !0|,

) ^~-. (II)
~^T-~

uy be a maximum! a minimuni, or z point of inflection. The e\\tr\302\243nuim is a

if the second derivative of the function is negative, so that the curve bends
downward.
Ai the cxt

where Nt, N2. and s are held constant as s, is varied. The second derivative c1/csi1o(

Equation A1) U

* The fund ion of two Gaussian fund ions is always a Gaussian.

product
and is negative, so thai the extremum is a maximum. Tims the most probable configuration
of the combined system is thai for which A2) is satisfied:

t
The two systems arc in to interchange ofenergy
equilibrium with
when the fractional
respect
spin excess of system to the fractional spin excess of system
1 is equal 2.

We prove itiat nearly alt the accessible stales of ttic combined systems satisfy or very
nearly satisfy (U). if s, and 52 denote the values of s, and sj at the maximum, then A3}

o find iiic number of slates in the most probjble configuration, we insert A4} in {9} to

(-25I/N). A5)

To investigate the sharpness of i of gigl at a given value of s, introduce &

such that

-
s, + <5; sj
=
s2
- 5. A6)

Hcre^ measures the deviarion of su st from their values Su Sx at the maximum o(g,gi.
Square j,,ij to fonn

which we substitute in {9} and A5) to obtain the number of sialcs

/ 45,^ 2Sl 4s2S 2d2

We know from (H) thai s,/jVj

\302\253
.'.\\'u
V.vi.so so !ii;it the
that number of
the number slatesin
of slates a configuration of
ot
deviation ii from equilibrium is
\\

l(N2J2 - 3) = te.ffiU.e ~ ~

;v~

As a numerical example in wliidi the fraciionat devbiion from equilibrium is very smalt,
let Ni \302\253
,V. = !0:i and 5 = 10'2; ilia! is, <5/A'i = !O\0210. Tlien,2ii!,'iVi = ^00, and the
 Thermal Equilibrium

product g,^i is reduced lo g\"\02100 = lO\0217* of its maximum value. This is an extremely
laigc reduction, so that g,g, is truly a very sharply peaked function of st. Tiic probability
that tlie fractional deviation will be 10\"'\302\260or larger is found by integrating {17} from
& = I0u out lo a value of (he order of s or of N, thereby including ihc area under the wings
of the probability distribution. Tiits is the subject of Problem 6. An upper limit to the
integrated probability is given by N x tO\"t14 =
10~i!2,si ill very smalt. When two
systems are in ihermal contact, the values ofsi, Sj thai occur most often will be very close to
the values off,, S] for w hich ihe product g]g1 is a maximum. It is e.Uremely rare io (ind
systems with values of*,, s, perceptiblydifferent from st.
?\342\200\236

What does it mean to say that the probability of ftitding the system wjlh a fractional

deviation larger limn 5 .V, = \\Q~10 is Only \\0'!ii of the probability of finding the system
ill equilibrium? We mean that the system wilt never be found with a deviation as much as

1 part in tO10, smalt as this deualion seems. We would have to sample !0IJ2similar systems
lo have a reasonable chance of successin such an experiment. If we satnptc one system every
10'1 s, which is prctlv Usi sunk, we would iuive to sample for 101J\"s. The age of the
universe is only 1O'Bs. Thereforewe say with great surely that lite deviation described wilt
never be observed. The estimate is rough, but the message is correct. The quotation from

Uoli/iitaun given at iUi beginning of this chapter is relevum here.

We may expect to ob>mc substantial fractional deviations only in the properties of it
imiili system in thermal contact with a targe system or reservoir. The energy of a small

system, say a system of 10 spins, in thermal contact with a large reservoir may undergo
fluclualions lhat are largi! in a fractional sense, as (lave beenobservedin experiments on ihc
Brown tan motion of small particles in suspension in liquids. The average energy of a small

system ill contact with a targe system can altvays be determined accurately by observations
a! one time on a tatgc number of identical smart systems or by observations on one sronlt
sysicm over a long period of lime.

THERMAL EQUILIBRIUM

The result for ihe number of accessible stales of two model spin systems in

thermal contact generalized to any two systems

may be in thermal contact, with
constant toial energy U - Ul +\342\226\240
U2. By direct extension of the earlier argu-
argument, the multiplicity g(S, V) of the combiited system is:

summed over all values of Us < V. Wzxz g X{N itU %) is the number of accessible
states of system 1 at Jiicrgy Ux. A coniigiiratioit of the combined system is

specified by ihe value of together

(.\342\226\240',. with the constants U,Nt, -V2. The number
ofaccesstblcstates is lite
~ Ut).
in a configuration product gt{N],Ui)()i(Nz,U
The sum o\\er :nl configuraiioits gi
 The largest term in the sum in (!S) governs the propertiesof the total system
ill thermal equilibrium. For an extremuni tt is necessary that ihe differential* of
g{N,U) be zero for an infinitesimal exchange of energy:

dg = (-\342\200\224] g2t!Ul +
9i(^~\\d
lV, + dU2 - 0. A9}

We divide by glgl and use the result dV2 =

~tiUx to obtain the thermal
equilibrium conciiiion:

Lflfs
which we may write as

B0b)

We defitie the quanttiy a, calledIhe entropy, by

a{N,U) s \\

where a is the Greek letter sigm:i.We now write B0) in the iimii form

B1)

means lhai Ns is held consiam in ihe differttiljalion o(g,{Nt,U,) with tespeel lo U,. Thai is, ili=

panial dcrivalivc wiih respect to 0, is defined as

 Teutperutute

This is the condition for thermal equilibrium for two systems in thermal

contact. Here Afi ant! /V2 may symbolize not only the numbers of particles,
but

ail constraints on the systems.

TEMPERATURE

The last equality B2) leads us immediately to the concept of temperature.We

know the everyday rule: in thermal equilibrium the temperatures of the two

systems are equal:

r, = t2. B3)
This rule must be equivalent to B2), so that T must be a function of (ro/f V)s.
If T denotes ttie ahsohite temperature in ketvin, this function is simply iSie

inverse relationship

B4)

The proportionality constant ku is ;i universal constant called the ilott/iiumu

L-on^mnt. As determined experimentally,

kn
\302\273
U81 x 10~\"joulcs/ke1vin
\302\253
1.3X1 x 10\"Ulcrgs/kelvin. B5)

We defer the discussionto Appendix B becausewe prefer 10 use a more natural

temperature scale:we define the fundamental temperature r by

B6)

This temperaturediffers from ihc Kelvin temperature by the scale factor, kB:

r - kBT. | B7)

Becausea isa pure number,thefundamental temperature t has the dimensions

of energy. We can use as a iemperature scale the energy scale,in whatever unit
C/iapier 2; Entropy and Temperature

may be employed for the latter\342\200\224joule or erg. This procedure is much simpler
than the introduction of the Kelvin scale in which the unit of temperature is
arbitrarily selected so that the triple point of wmer is exactly 273.16K.Thctriple
point of water is the unique tcmperaiurc at which water, ice, and water vapor
coexist.
Historically, the conventional scale dates from an age in possiblewhich it was
to build accurate thermometerseven though theof temperature
relation to
quantum states was as yet not understood. Even at present, it is still possible to
measure temperatures with thermometers calibrated in kelvin to a higher
precision than the wit h which tlie conversion factor kB iiself
accuracy is known\342\200\224
about 32 parts per million. of
Questions praciical thermomeiry are discussed in

Appendix B.

permissible to take the reciprocal of both sides to

B8)

The iwo expressions B6) and B8} have a slightly diOcrcu leaning, in B6). the entropy <r

was given as a function of theindependent variables U id M as a = a{U,X).Hencei

determined from B6) has the same indcpendeiu variab] r \342\204\242
t(U,N). In B8). however,
differentiation of U with respect lo a with N consiant mpties V =
V(a,N), so that t =
V). The definition of Eemr^caiufe is die same in both cases, but it is expressed
function of different independent variables. The q in \"What areihc independent
variables?\" arises frequently in lhermal phy. because in some experiments we coniroi
some variabtcs, and in oilier ej.pcrinicnts we itrot other variables.

ENTROPY

Tile quantity as logg was introduced in B1) as ihe entropy of the system:the
entropy ts defined as the logarithm of the number of slates accessible to the
system. As defined, the entropy is a pure number. In classical thermodynamics
the entropy i'is defined by

129)
 Entropy

Figure 2.7 if the temperature r, is higher

than t2, the transfer of a positive amount of

energy & U from system t to system 2 v.itt

increase the total entropy a, -f a2 of ihe
combinedsystemsover ihe initiat value
<j,(initia!) + ^(initiat). In oiher words, the
finat system wiii bt: in a more probable
condition if energy flows from the wanner b
to the cooler body when lhermat contact is
U2+8U established.This is an otamptc of the Saw of
increasing cm ropy.

Energy transfer

o,(final) + cMXinai) > o^iniiia!) + oa(iniiiai)

As a consequence of B4), we see that 5 and o are connected by a scale factor:

130)

We wilt call S the conventional entropy.

The more statesthat are accessible, the greater the entropy, fn the definition

of a{N,U) we have indicated a functional dependence of the entropy on the

number of particlesin the system and on the energy of the system. The entropy

may depend on additional independent variables: the entropy of a gas(Chapter

3) depends on (he volume.
in Uic early history of thermal physics the physical significance of the cm ropy
was not known. Thus the author of the article on thermodynamics in the

Encyclopaedia Britaiiuka, t lih ed. A905), wrote: \"The utility of ihe conception
of entropy ... is limited by the fact that it does not correspond directly to any
directly measurable property, but is merely a mathematical function
physical

of the definitionof absolutetemperature.\" now know v.hat absolute physical We

properly the entropy measures, example of the comparison of the experi- An

experimental determination and theorctic.il calcutiition of the entropy is discussed in

Chapter 6.
Consider the tot;il entropy changeAa when we remove a positive amount of
energy All from 1 and add the same amount of energy to 2, ;is in Figure 2.7.
Clmptcr 2: Entropy urn! Tehtjter

The tolnl entropy change is

When t, > r2 ihe quantiiy in p;ireniheses on ihe righ>hand side is positive,

so that the Loial change of entropy is positive when the direction of energy flow
is from the system with the higher temperature to the system with the lower

temperature.

Example: Entropy increase on heiitjlow. This example makesuse of ihc rentier's previous
fansitiariiy with heal and specific heat.
(aj a 10-g specimen
Let of copper at a temperatureof 350 K be placed in thermal contact
with an identical specimenat a temporal tire of 290 K. Lei us find the quantiiy of energy
transferred when ihe iwo specimens arc ptaced m contact and come Lo equilibrium at ihe
final temperature Tf, Ttie specific hc;ii of meiaitic copper over ihe LempcraLure range 15:C
to t007C is approxiinaieiy O.3S9Jg~! K~l, according Lo a standard handbook.
The energy increase of the second specimen i> cmiai Lo the energy loss of ihc first) ihus
the energy increase of ihz second specimen is, in joules,

AV = C.89J K-'HTV
- 290K) - C.89JK-')C5OK ~
Tf) ,

where ihe tempcraiures are in kcMn. Ttie linat temperature after contact is

\302\253
|C5O + 290JK = 32OK.
Tj

Thus

At/, \302\253
C.89JK~!)(~3OK)
= -11.7 J ,

and

At/3 = -At/, = U.7J.

(b) What is the change of entropy of the two specimens when a transfer pf 0.1J has
taken place, almost immediately after initial con'act? Notice that this transfer is asmall
fraction of ihe final transfer as calculated above.Becausethe energy
energy transfer con-
considered is small,we may suppose the specimens are approximately at their initial tempera-
of
temperatures 350 and 290 K. The entropy of the firsi body is decreased by
 Lan of Imrrrmc of Enlnpy

Tile cnlropy of iiic second hody is increased by

S2
=
,7~
= 3.45 x

Tile iotal enlropy increases by

AS, + AS, = (-2.S6 + 3.45)x 10-4JK-' = 0.59 x 1CTJJK~

In fundamental, units the increase of entropy *s

where tjisihe Botl/.ma\302\253n constant. This resuil mcaaS thai (lie number of accessible st;it

of the two systems increases by (he factor exp{M - enp@.43x 10l9>.

Law oflncrease of Eniropy

We can show thai ihc loial ctttrapy always increases when two systems ;trc
broughi into thermal contact. We have jusi demonstrated this in a special case.
If (he total energy V ~
V% + U2 is consiant, the lotal multiplicity after the

systems arc in thermal contact is

- t/,) , C3)
ff(t/)\302\273=
^0,A/^A/

by A8). This expressioncontains the term gi(EAo)i/i(^

~~
^to^ ^or l^e i-XiiiVd^

niuitiplicuy before contact and terms besides.Here ViQ is the

many osher
initial energy ofsystem 1 and V l/lois the initial energy ofsyslem 2. Because
~~

all termsin C3) are positive numbers, ihe muitipliciiy is always increased by
establishmenl of ihermal conlaci bclween two systems. This is a proof of Ihe
taw of increase of entropy for a weli-definedoperalion.
Thesignificant effect of conlact, the effect that slands out even after lakingthe
logarithm of ihe multiplicity, is not just that Ihe number of tcims in iiic summa-
summationis large, but that the largest single term in the summationmay be very, very
much larger than the initial muilipiicity. That is,

(Mi).,, = 9i(O,)gJiU - 0.) C4)

Chapter 2: Entropy and Teniperatur

with Ut
= 0 anJ U, * U. Exchange of energy takes piao; between h
parts and presently the syucm will be found in or dose 10 tlie most
probable con figuration. Hie cm ropy increases as the jysicm attains
conftgL rat ions ofincreasirtg muhiplicily or probabilhy. The entropy
eventually reaches ihe entropy a{U) oflhe moit probable configuratic

may be very, very much larger than ihe initial term

9iiVtMU'~ Vl0). C5)

Here 0s denotesthe value of Vl for which ihe product g^x is a maximum.

The essential effect is lhat the syslems after contacl cvoive from iheir initial
configurations lo their final configurations. The fundamental assumption
implies thai evoluiion in this operation will always lake place, with ali accessible
final states eqtutlly probable.
The statement

fffjnil C6)

is a statement of the law of increaseofcnlropy:the entropy of u closed system

[ends to remain constant or to iucreasewhen a constraint iniernul to she sjstem
is removed.The operationofebtabitsliiiig thermal contact is equivalent to ihe
removal of the constraint that Vu V2 each be constant; after contact only

Ux + U, need be constant.
The evolution of the combined system lowards ihe final thermal equilibrium

configuration takes a certain time. If we separate ihe two systems before they
 Add
energy

Decompose molecules

Let a linear polymer curl up

Figure 2.9 Operations thai lend io increase the entropy ofa syslcm.

reach (his cotifiguraiion, we will obtain an intermediate configuration with

intermediate energies and an intermediate entropy. Ii is ihesefore meaningful io

view the entropy as a function of the lime tli.i' lias elapsed since removal of the
constraint, called (he lime of evolution in
Figure 2.8.

Processes that lend lo increase the eniropy ofa system are shown in Figure

2.9; the arguments in support of each process will be developed in the chapters
that follow.
Chapter 2: Entropy and Temperature /

For a largesysiem* (in thermal with another large sysiem)ihere will

coniaci
never occur spontaneously significant differences belween the actual value of the
entropy value of the entropy of the most probableconfiguration
and ihc of the

system. We showed ihis for ilie model spin sysiem in the argument following A7);
we used \"never\" in ihe sense of not once in ilie entire age of the universe. 10's s.
We can only find a significant difference beiwcen Ihc actual entropy asid ihe

entropy of ihe most probable configuration of the macroscopic system very

shortly afier we have changed the nature of ihe contactbetween two systems,
which implies that we had prepared the system initially in some special way.
Special preparation couldconsistof lining up all the spins in one system parallel
to one another or collectingall the molecules in the air of the room into the

system formed by a small volume m one corner of the room. Such extreme
situations never arise naturally m systems left undisturbed, but arise from
artificial operations informed on the system.
Consider ihc gas in a room: the gas in one half of the room might be prepared

initially wjiti a low value of the average energy per molecule, while the gas in ihc
other half of the room might be prepared initially with a higher value of the

average energy per molecule. If the gas in the two halves is now allowed to
interact by removal of a partition, the gas molecules will come very quickly'
to a most probable configuration m which ihe molecules m both halves of the
room have the same average energy. Nothing else will ever be observed to
happen. We will never observe the sysiem to leave ihe most probable configura-

and
configuration reappear later in the initial specially prepared configuration.This is true
even ihough the equations of motion of physics are reversiblein time and do not

distinguish past and failure.

LAWS OF THERMODYNAMICS

When is studied as a nonslatisticaisubject,four posluiales

thermodynamics
are introduced. Tiicse postulates are caiied ihe laws of thermodynamics, in
essence, these laws are containedwithin our statistical formuiaiion of thermal
physics, bul it is useful to exhibit Ihem as separate slatemenis.
Zeroth law. If two sysleins are in thermal equilibrium with a third sysiem,
Ihey must be in thermal equilibrium with each olher. This iaw isa consequence

1
The calculation of Ihe lime required for Ihe process is largely a problem in hydrodyna
 Laws of Thtentotiynamks

of the condition B0b)for equilibrium in thermal comact:

(e\\oSgt\\ * feioSg3\\ /cloggA /cloggA

{~\342\204\242rk {-furl: {imX= {~7urk
in oilier words, r,
=
t3 and r3
= t3 imply rj
=
r2.
Heat is a form of energy. This law is no more than a slaicment
First law. of
liie principle of conservationof energy.Chapter 8 discusses wliat form of energy
heat is.
Second law. There are many equivalent statements of ihe second law. We
shali use the statisiicai statement, which we have called ilie law of increase of

entropy, applicablewhen a constraim iniernal lo a dosed systemis removed. The

commonly used statement of the law of increase of entropy is: \"Ifa closedsystem
is ill :l configuration tluit is not (he equilibrium cotiliyitnilton.ilicmosi |>rubnble
consequence will be lhat ihc enlropy of the system will increase monoiotiic;ilty
in successive instants of time.\"Tins is a looser siaicineiil ilian I he one we gave
wilh Eq. C6} above.
The traditional thermodynamic statementis the Kelvin-Pianck formulation
of second iaw of thermodynamics; \"it is impossible for any cyclic process to
occur whose soie effect is the extraction of heal from a reservoir and the per-
performance of an equivalent amount of work.\"An engine that vioiaies lhe second
iaw by extractingthe energy of one heat reservoir is said to be performing

perpeiual motion ofthe second kind. We will see in Chapter 8 that the Kelvin-
Pianck formulationis a consequence oflhe statistical statement.

Third iaw. The entropy of a system approachesa constant value as the

temperature approaches zero. The ear!

test statement of this law, due loNemst, is
that at ihe absolute zero the entropy difference disappears between all those
configurations of a system which are in internal thermal equilibrium. The third
iaw follows from the statistical definition entropy, provided ihat the
of the
ground stateof the system has a weii-defined multiplicity. If lhe ground stale
multiplicity is g@), the corresponding entropy is o{0) = iogy@) as t -* 0.
From a quantum point of view, the law does not appear to say much that is

not implicit in the definition of enlropy, provided, however, the system is

that

in its lowest se! of quantum states at absolute zero. Except for glasses, there
would not be any objection to affirming that (j{0) is a small numberand c{0)

is essentially zero. Glasses have a frozen-in disorder, and for them o{0) can be

substantial,of the order of [he number of atoms N. What the third law tells us
in real life is that curves of many reasonable physical quantities plotted against x
must come in flat as r approaches 0.
Chapter 2: Entropy and Temperature 1

Entropy as a Logarithm
Several useful properties follow from ihe definition of (he cmropy as the ioga-
rithm of the number of accessible states, hut cad of as the number of accessible
stales itself.First, the entropy of two independent systems is liie sum of lhe
separateentropies.
Second, the entropy is entirely insensitive\342\200\224for ali practical purposes\342\200\224-to

the precision 6U with wiiich the energy of a closedsystem is defined. We have

never meant to imply that tite
system energy is known exactly, a circumstance
that for a discrete spectrum of energy eigenvalues would make the number of
accessible stales depend erraticallyon ttie energy. We have simply not paid
much attention io lhe precision,wlicthcr ii be determined by the uncertainly
principle <5U 5{time) - h, or determined otherwise. Define <0{U)as the number
of accessible srates per unit energy range; O{U) can be a suilablesmoothed
average centered at V. Then y{U) ~ i>{UNU is lhe number of accessible
stales in the range SU al V. The cmropy is

a{U) logO(t/) -t- \\ C7)

Typieally, as for the system of N spins, the total number of states will be of ihc

order of 2V. If lhe tola! energy is of the order of N times same average one-
particle energy A, then C(l')
- 2;7jVA. Thus

. . a{V) =* Nlog2 --'logNA + log^C. C8)

Let N ~ IO20;A = IO\021* erg; and 5U \302\273
10^' erg.

a(U) *\302\273
0.69 x 10:o - 13-82- 2.3. C9)
We see from this that the value
exam pie of the entropy is dominated overwhelm-
by
overwhelmingly the lhe precision dU is without
value of N; perceptible effect on the
result. 1 n the problem of A' Tree particles in a box, the number of stales is propor-

proportional io something like U*dU, whence a - JVIogf + \\ogSU. Again lhe

term in N is dominant, a conclusion independentof even the system of units

used for lhe energy.

Example: Perpetual iiuxion o Early in our study of physics we came to

lion machine, a machine ilui wjli gi\\c forth
more energy in.in ii absorbs.
 Equally impossible is a perpetual motion machine of the second kind, as it is called, in
which heat is exiracicd from part of the environment and deliveredto another part of ihc
environment the difference in temperature ihus established being usedto power a heat

engine that delivers mechanicalwork available for any purpose at no cost to us.In brief, we
cannot propel a ship by cooling tlic surrounding ocean lo extract the cnefgy necessary to
propel ihe ship. The Spontaneous transfer of energy from ihe low temperature ocean 10 a
higher temperature boiler on the ship would decrease ihe total entropy of the combined
systems and would thus be in violation of the law of increase of entropy.

SUMMARY

1. The fundamental assumption is that a cioscd system is equally likely to be

in any of !Oit.
lite quantum slates accessible
2, ifPfi) is the probability that a system is in the stale s, the average value ofa
quanliiy X is

3. An ensemble of systems is composedof very many systems, all constructed

alike.
4. The numberofaccessible
states of the combined systems 1 and 2 is ,^ ^

*
where + = s.
^'
s, s2

5. The entropy a(N,U) =

to$g{N,U). Tiie relation S = kBa connects the

conventional entropy S with the fundamental entropy o.

6. The fundamental temperature r is defined by

1/t s [ca;cV)sx.

The relation r = kgT connectsthe fundamental temperature and the con-

conventional temperature.

7. The law of increase of entropy states that the entropy ofa closed sysicni
tends to remain constant or lo increase when a constraint intorn.il lo llic
system is removed.
Chapter 2: Entropy and Temperature j

8. The thermal equilibriumvalues the physical properties of a system are

of

defined as averagesaccessible when the system is in contact

over all states
with a large system or reservoir.If the first system also is large, the thermal
equilibriumpropertiesare given accurately by consideration of the states in
the most probableconfiguration alone.

PROBLEMS

1. Entropy and temperature. SupposegW) =

CUiNn, wiiere C is ;t constant

and N is tile number of particles, {a}Show thai U *=

{Nt. (b) Show that
{c^a/rU2)* is negative.Tliis form of y( U) ;iciii;tlly applies hi an ideal gits.

2. Ptirtitttagiwtisni. Find the equilibrium value ui ictn|KT;tit:rc i of ilie (Vac*

lional mngntrlizalion

M \\'m =
2<s>/N

of the sysiem of h' spinseachofmagnetic momem in in a magnelic field B. The

spin excess is 2s. Take the eniropy as lhe iogarlhilhmof lhc muliipliciiy g(N,s)
as given in A.35):

c(s) =logg(Ar.O)- 2s2/N , D0)

for |s| iV.

\302\253 Him: Show that in this approximation

g{U) = c0- U2/2m2B2N, D1)

wtih oQ
-
1og(/{N,0). Further, show thai \\jx
~
-U/)\302\2732B2N, where U denotes
<t/>, the lhermai averageenergy.
3. Quantum hartitonic oscillator, (a) Find the enlropy of a sel of N oscillators
of frequency m as a fund ion of the loiai quanlum number n. Use the muiiipiicily
funciion A.55) and make lhe Sliding approximalion iogiV!= iViogiV \342\200\224
iV.

Replace JV 1 by iV. (b) Let U denote lhc tola!energy

\342\200\224 of
\302\273/itu the oscillators.
Express the entropy as a(U,N).Show that the total energy at temperature x is

,42)
\342\200\224
1
exp{/itu/r)

This !S the PSanck result; it is derived again tn Chapter 4 by a powerful method

that does not requireus to find ihemuilipiicity function.

where used !ogl0 44 = 1.64345.
we have
{b} Show that the probability that a monkey-Hamlet will be typed in the age
of the universe is approximately 10\"'64316. The probability of Hamlet is
thereforezero in any operational sense of an event, so that the original statement
at the beginning of this problem is nonsense: one book, mudi less a library,
will never occur in the total literary produclion of the monkeys.

5. Addith-ity of entropy far two spin systems. Given two systems of JV, =s
A', = 1012spins with multiplicity functions g^x^i) and g2{N2.s - ss), the
product gig2 as a functtonofsj is relatively sharply peakedat s( = s,.ForSj=
ss + I012, the product #sj72 is reduced by jO\02174 from its peak value. Use the
Gaussian approximationto the multiplicity function: the form A7) may be
useful.
(a) Compute gigz/{9-i9z)m3X for s,
=
s, + lOn and s = 0.
(b) For s = 1O10, by what factor must you multiply (gijh),,,a!l fo make it

to ~ \302\247've l^e ^ctor to the nearest order of

equal Yai9'it^i*5i)9i{^i's 5i)\">

magnitude.

' j. Jeans, htysteriota utirerst, Cambridge Universily Press, 1930, p. 4. The slalenuill is attributed
to Huxley.
' For a rctaicd
malhematfco-iherary study, sec'The Libtary of Babel,\" by ihe fascinating Argentine

Clarke in 2001. We arc gralcfut to the Population Reference Bureau and to Dr. Rosier Revcttc for
explanations of the evidence. The cumulative number of man-secondsis 2 x iO10. if we take ihe
average trretrme as 2 x 10 s 3nd tl^c number of lives as I ^ 10 , i he cumu*ai[\\c numoc^ oi
m an-seconds ii njocti ksi than the'numbcr of monkey \342\200\242sccondi
(t0\"> iaken in the problem.
Cliapter2; Entropy and Tcmperatur

(c) How iarge is the fractional error in the entropy when you ignore this
factor?
6, Integrated deviation. For the example lhat gave ihe result A7), calculate
approximately the probability that the fractional deviation from equilibrium
is 10\"l0
\342\226\2405/JVj or larger. Take iVj
=
JV2
= IO2Z. You will find it convenient to
use an asymptotic expansion for the complementary error function. When
x \302\273i,

xp(x2) (\"\"e x 1 + small terms.

Chapter 3

Boltzmann Distribution and

Helmholtz Free Energy

BOLTZMANN FACTOR 58

Partition Function 61
Example: Energy and Heat Capacityof a Two State System 62
Definition; Reversible Process 64
PRESSURE 6-1
Tlicrmodynaimc identity ;>7

HELMHOLTZ KttEE ENERGY 6S

Example: Minimum Property of the Free Energy of ;i

ParamagneticSystem 69

Differential Relations 70
Maxwell Relation 7!
Calculationof f from 2 71

IDEAL GAS: A FIRST LOOK 72

One Atom in a Box 72

Example; Af Atoms in a Box 74

Energy 76
Example: Equipartition of Energy 77

Example: Entropy of Mixing 7$

SUMMARY SO

PROBLEMS 81

1. Free Energy of a Two State Sysiem 85

2. Magnetic Susceptibility Si
3. Free Energy of a Harmonic O.ollaior S3
4. Energy Fluctuations S3

5. Overhauser Effect S4
6. Rotation of DiatomicMolecules 84

7. Zipper Problem S5
S. Quantum Concentration S3
ChapfcrS: Bol auJ lleliiiiioiiz Free Energy

9. Partition Function for Two Systems

10. Elasticity of Polymers
11. One-Dimensional Gas
 Chapter3; BolRinattn Distribution and lleimkoitz Free Energy

The laws of thermodynamics may easily be obtainedfrom the principles of

statistical mechanics, of which they are the incomplete expression.
Gibbi

We are able to distinguish in mechanical terms the thermal action of one system
on anotherfrom lhai which we call mechanical in the narrower sense . , . so as
to specify cases of thermal action and cases of mechanicalaction.
Glbbf
In this chafer we develop the principles that permit us to calculate the values
of the physical properties of a system as a ftinciion of ihe temperature. We
assume that the sysiem & of interest io us is in thermal equilibrium wiih a very
iarge sysiem (ft, called [he reservoir. The system and the reservoirwill have a
common temperature r because ihcy are in thermal contact.
The iota! system (ft + & is a closed sysiem, insuiaicd from u!! external

influences, as in Figure 3.1. The total energy Uo =*

U^ + is
\302\243/j constant. In

particular, if the sysiem is in a staleof energy Ea, tltcn Uo

- r,x is ihe energy of
the reservoir.

Toial sysiem

. Constant energy Vo

J.I Rcprcs illation of a cioscd loiat syst n decomposed iisioa

irOtiiUhcn a! coniaci with a sjsieni S.

BOLTZMANN FACTOR

A central problem of thermal physics is 10 find the probability iltai ihe system
5 \302\253iilbe in a specific quantum siaiu s of energy t,. This probability is propor-
proportional to the Boitzmann factor.
When we specify that S should be in ihe state s, ihe number of accessible

Slates of the louil sysiem is reduced10the number of accessible states of ihe

reservoir (H, ai ihe appropriate energy. That is, ihe number j
g\302\256t of siaies
 Figure 3.2 The change of cnlropy when ihe
nsetvoit u&nsfcssenergy t la (he system. The
fractional effec! of itie transfer on ihe reservoir

laigc TCMivoii vil\\ luua high ci\302\253iop>.

of the reservoir -
Energy

accessibleto (ft -

A)

because for our present purposes we have specified the state of .S ,

If the system energy is the reservoir
\302\243\342\200\236 energy is Uo \342\200\224 The
\302\243,. number of
stales accessible to the reservoir in this condition is^f/o
- as
\302\243,}, in Figure 3.2.
The ratio of the probability that the system is in quantum stale I al energy
to
\302\243, Ihe probability that the system is in quantum state 2 at energy Ei is Ihe

ratio of Ihe two multiplicities:

Multiplicity of <R at energy Uo

- r.t
-
ei)
_ \302\243a(^o
B)
\342\200\224
Multiplicity of (ft at energy [/q \342\200\224
\302\2432 91s(^'o e2)

This result ts a direct consequence of what we have called the fundamental

assumption. The two situations are shown in Figure 3.3. Although questions
about the system depend on the constitution of the reservoir, we shall seeihat
the dependence is only ow the temperature of the reservoir.
if the reservoirsare very large, the multiplicities arc very, very l.-irgcnumbers.
We write B) in terms of the entropy of the reservoir:

-
\302\273 E.)
- ff\302\253(t/0
- f C)
Chapters: Bohzmnnn Distribution and Helmholtz Free Energy'

Oi 01

E
ergy -',
(/\342\200\236 En \302\253gy (/\342\200\236
-\302\253,

yo
-
',) stale ;\302\260
-
'=' slates

8 i
Sta tc I State 2
Ene
gy\302\253> Energy c.

Fi\302\273urc3.3 The system in (a),(b) is in quantum slate t, 2. The reservoir

has a,,(U0 - t,}, -
c,) acccisiblc quanluin
(,\302\273(()\342\200\236 slates, in (a) and (b)
id

D)

the probability ratio for the two states 1, 2 of the syslem is simply

E)

Let us expand the entropies in D) in a Taylor series expansion about

The Taylor seriesexpansion
off[x)about /(x0)
is

- t)
0)

where 1/t
=
(S^/cCV^ gives the temperature. The partial derivative is taken
al energy Uo. The higher order termsin liie expansion vanish in the limit of

an infinitely large reservoir.*

Therefore Acr^ defined by D) becomes

Affffl= -(\302\243, -\302\2432)/T. (8)

The final result of E) and C) is

'
P{ez) expft/r)'

A term of the form exp( is

\342\200\224e/t) known ,as 3 Boltzmann factor. This result is
ofvust utility. It gives the ratio of Hie probability of finding the system in a
single: quantum state I to ttie probability of finding ihc system in :i single

quantum state 2.

Partition Function

h is helpfui to consider the function

Z(r) =
5>p(~Ei/T) , A0}

ealied the partition function. The summation is over the Boltzmann factor
exp(-e,/t) for a!! states 5 of the system. The partition function is the pro-
proportionality factor between the probability p[Et) and (he Boltzmann factor

We see that =
\302\243?(\302\243,) ZjZ = 1: is unity.
the sum of all probabilities
The result (II) is one of the most useful results of statistical physics. The
average energy of the system is V = (e) = X^fo). or
'
U =, = T^logZ/ct). A2)
Zh^Zh!A

oft'j, ~ [he cupansion of ihc tatter quanliiyimmcdiatcty

\342\200\242 ~
We expand \342\202\254)andnolg({/B e) because
gives convergence difficulties.
 ChapterS: Battvnanti Distribution and Helmholtz Free Energy

0.5

0.4 A
J-\342\200\224\342\200\224

Energy and heat capacity of a V

ystcm as functions ofthe temperature J
rgy is plotteJ in units ol t.

0.1
\342\226\240

0 u

The average energy refers to those statesof a system that can exchange energy
with a reservoir. The notation \342\226\240
) denotes
<\342\226\240 such an average value and is
called the thermal average or ensembie average. In A2) the symbol U is used
for (e) in conformity with common practice; U will now refer to the system
and not, as earlier,to the system -f reservoir.

Exwiiplc? licut cupticiiy of a two itatt

Energy uiid systexn. We trc^l a sy^lcm ofonc pitrti-
clc wftli two
slates, one of energy 0 and one of energy e. 11w partide is in iltcmut contact
wiiti a reservoir at temjKrature t. We want lo find the energy and ttie heat cupaciiy of ihe
system as a function of the temperature i. The pat lit ion function for tin iwo stales of

Z = exp(-G/t) + exp(~\302\243/r)
= i -f expf-s/t). A3)

\"fhe average energy is

This function is plotted in Figure 3.4.

If we shift iliczcro of energy and lak^: W.c energies of the two states as -\\e and +\\e,
instead ofas 0 and e, the results appear different ty. We have

=
\302\253p(-\302\243/2r) 2cosh(fi/2t) , A5)
 Partition Function

and

= A6)
-jctanh(c/2c).

The heat capacityCv of a syslem at conslant volume is defined as

Cv s x(iajdx)r , A7a)

which by the ihermodynamic identity C4a) derived below is equivalent lo the allcmate
definition

Cr s (SU/dt)y. A7b)

We hold V conslant because the values of the energy arc calculaied for a syslem at a specified
volume. From A4) and (!?b},

C - a ' -fEY eXp(E/t)

A8a)

The same resull follows from A6).

In conventional unils C, is defined as VfSIST), or gU/dT),. ivliencc

dimensions of energy per kcivin. Tim siicctfic heat is drfmed us itio deal capacity per unil

ri^i-immp in ]Ilc pio! of Iicii]cnpiiciiy versus icmpcjiiiurc \\\\\\ t'iiHirc3 is Ciiiic^l

\"\342\226\240 ^ jLtiOiiKy

anomaly. For i i, the

\302\273 heat capacuy A8a) becomes

Cr^(E/2iJ. A9)

N'oiicc ihat Cy cc r\"\": in ihis high tempcraiufe limit. Iii ilie low teraperaiuie limil ihc
lemperaiuie is small in comparison whh llic energy level spacing e. For i e we
\302\253 have

Cy ^ {c/lJ^Xpl-E/lX CO}

factor \342\200\224rcJuces
Cv rapidly as r decreases, because exp[
~ 1/v) -> 0
The exponen'.ial exp[ r,'t}
as a- - 0.
Chapter}: Boltzmann Distribution and Hdmhoki Free Energy

Definition: Reversible is reversible if carried

process, A process out in such a
way ihai ihe system is always
infmiiesimally close to the equilibrium condition.
Forexample, if the entropy is a function of the volume, any change of volume
must be carried out so slowly ihat the entropy at any volume V is closely equal
lo the equilibrium entropy a{V), Thus, the entropy is well defined at every
stage of a reversible process, and by reversing the direction of the change the
system will be returned to its initial condition. In reversible processes, the
condition of the system is welt defined at ail times, in contrast to irreversible
processes,where usually we wilt not know what is going on during the process.
We cannot apply the mathematical methods of thermal physics 10 systems

whose condition is undefined.

A volume change that leaves the system in the same quantum state is an
exampleof an isentropic
reversible process. If the system always remains in the
same state the entropy change will be zero between any two stages of the pro-
process, because the number of states in an ensemble (p. 31) of similar systems does
not change. Any process in which the entropy change vanishes is an isentropic
reversible process. But reversible processes are not limited to isentropic pro-
processes, and we shaHhave a special interest also in isothermal reversible processes.

PRESSURE

Consider a system in the quantum state s of energy e,. We assume e, to be a

function of the volume of the syslem.The volume is decreased slowly from V
to V - AV by applicalron of an external force. Let the volumechange take
place sufTkrenliy slowly that the system remains in the same quantum state s
throughout the compression. The \"same\" stale may be characterized by its

quantum numbers (Figure 3.5) or by the number of zeros in the wavefunclion.

The energy of the state s after the reversible volume change ts

t\302\243V
-
&V)~ eJ^V) -(dtJdV)bV + \342\226\240\342\226\240-. B1)

Consider a pressure p, applied normal to all facesof a cube. The mechanical

work done on the system by the pressure in a contraction (Figure 3.6) of the
cube volume from Kto V \342\200\224
AKappears as the change of energy of the system:

U(V
-
Af) - U(V) .=* At/
-
-(deJdVyLV. . B2)
 \342\226\240\342\200\224-\342\200\224_

O.S i.O t.S

Volume, relative scale

Figure 3.5 Dependence of energy on volume, for the energy levels of a free
particle- connned 10a cube. Ttie curves arc labeled oy m ^\342\200\224 i^ -j- . t -%- n_\\

as in Figure t.2. The niuhtpltctties g are also given. The volume ch; nge here
^s isolropier a cub1\" remains & cube, i he criercy ranfie oc of ]tic stat1

represented in an ensemble of systems will increase in a revcrsibk

of ilie energy ranee iiself is of no practical impottance. ti is )he cha

llu: av cragc energy lhal is impotlaiU.

Tigure 3.6 Volume cliangc - AI' i

compression of a cube.
Chapter i; Batiziriann Distribution and Ihtmhottz Free Energy

Here V denotes the energy of the system. Let A be the area of one face of ihe
cube;then
A{Ax + Ay + Az) = AV , B3)

if ail increments =s - taken as

A V and Ax Ay Az are positive in the compres-
The
compression. wotk done in the compression is

AV =
psA(&x + + = , B4)
Ay Az) PiAV

so that, on comparisonwith B2),

P,
= -thjdv B5)

is the pressure on a system in the stale s.

We average B5) over all states of the ensemble to obtain the average pressure
<\302\243>,usually written as p:

B6)

where U m <t>. The entropy a is held constant in ihc tlcrivaiivi; because ihc
number of states in the ensemble is uuclianged in the reversible compression
we have described. We hove a collection of systems, each in some stme, and
each remains in fhis _st:ile in ihe compression.
The result B6) correspondsto our mechanic! picture of the pressure on a
system lhat is maintained in some specific state. Appendix D discusses the
result moredeeply.For applications we shall need also the later result E0) for
the pressure on a system maintained at constant temperature.
We look for other expressions for the pressure. The numberof statesand thus
the entropy depend only on U and on V, for a fixed number of particles, so
that only the two variables U and V describe the system. The differential of
the entropy is

da[U.V) B7)
Uu

This gives the differential change of the entropy Tor arbitrary independent
differential ch;i:v:_\342\226\240\342\226\240.
JU and dV. Assume now that we select dV and dV inter-
dependency, in such a way th;it the two terms on the right-hand sideof B7}
 Thermodyaamie Identity

cancel. The overall entropy change da will be zero. If we denote these inter-
interdependent values of dll and dV by {W)a and {&V}at the entropy change will
be zero:

B8)

) B9)

Bui ratio
\302\273he (*5[/)\342\200\236/(<)F), is the partial Jerivative of U wilh respect to V at

constant o:

(iV)J(SV), s ldU/dV),. C0)

With this and the dcfiniiion l/i s (So/5!/),.,Eq.B9)becomes

\302\273\342\226\240-<\302\243).-

By B6) the kft-h;ll)d side of C1) is equal to -ft whence

Therniodynaniic Identity
Consider again the differential B7) of the entropy; substitute the new result for
ihe pressure and the definition of i to obtain

Ttla = dU -f pdV.
Chapter3: Bohynaaa Distribution and Helmbohi Free Energy

This useful relation will be called the thcrtnodjnsmk identity, The form with
variable will appear in E.38). A simple transposition gives

dU = TVS -
pdV. C4b)

If the actual process of change of stateof the system is reversible, we can

identify xda as the heal addedto the system and -pdV as the work done On
the system. The increase of energy is caused in part by mechanical work and
in part by (he transfer of heal. Heat is defined as the transfer of energy be!ween
two systems brought into thermal contact (Chapter 8).

HELMHOLTZ FREE ENERGY

The function

C5)

is called the Hclmhoitz free energy. This function plays the part in thermal
physics at constant temperature that the energy V plays in ordinary mechanical
processes, which arc always understoodto be at constant entropy, because no

internal changes of state are allowedThe free energy tells us how to bulance
tiic conflicting demands of a system for minimum energy and maximum en-
entropy. The Helnihoitz free energy will be a minimum for a system S in thermal
contactwith a reservoir (R, if the volume of the systemis constant.
We first show that F is an cxtrcmum in equilibrium ;it constant r and V.
By definition, for infinitesimal reversible transfer from 01 to &,

C6)

at constaot so that
temperature. But 1/t h {das/cUi)yi dUL

stant volume. Therefore C6) becomes

dFt *= 0 , C7)

which is the condition for F to be an extremum with respect to all variations

at constant volume and temperature.We like F because we can calculate it from

the energy eigenvalues e, of the system (seep. 72).

 tfehuitoh: Free Energy

Comment. We can show that the extiemum is a minimum. The total energy is V ==

i',R + Us Then
\342\226\240 ihe tola! eniropy is

* e^U) - UtfffJtVrivji + ffsiUj). C3)

We know that

(\302\253*A'^),,v
* i/t , C9)

so thai C8) becomes

a^a^iV)
- FJx , D0)
-
where Fj \302\273
L/j w^ is ihc free energy of the system.-Now <rlk(Lr) is consiant; and we
rewll thai a = o, + ^ in equilibrium is a maximum with respect to Us . It follows from
D0) lha) Ft mus) be a minimum vviiii respect lo Vs when the system is in ihc mosi probable
configuraiion. The free energy of the system at constant r, V will increase for any deparluce

hxti'iiplc: Slltthnuiii property vf the free parcmti^nctic

energy tifaiyswin, Coilsklef tliC
model sy^tcfn of tliaptcr I. \\viUi spins
N't up *uid Ni spins down. Let N = A1? -+- N^',

the spin excess is 2s = A't

-
W(. Tlie entropy in the SUHiiig approximmion is found
with tlicliclpofan approximate form of A.31}:

,4,,

The energy in a magnetic field Bis.- 2\\tttfl, w licrc m is ilic magnetic woniciilofan elemen-

magnet.
elementary Tile fice cncigy funaion (to be called ldc lapdau function in Chapter tO) is
FJjaB) & V{s,m
-
io(s),or

D2)

Al ihc of Ft{r,*.B) with respeel

minimum io s, this function becomes cquat lo the equilibrium

free energy F[i.B). Thai f

is, Jt.<5>,BJ F(r,B), because <s> is a function - of z and B. The
minimum of FL with respect io the spin excess occurs when

= 0 = -JmB +
tlog^4-|- D3)
Thus in the magnetic field B lhe thermal equilibrium value ofihe spin excess Is i

or, on dividing numerator and denominator by exp(/\302\273B/r),

\302\273
<2s> Ntanh(mi?/r). D5)

The magnetization ,U is the magnetic momeni per unit volume. If n is the number ofspins
per unii volume, the magnetizalion in thermal equilibrium in the magnetic field is

M = <2s>m/K = Hi\302\273wnh{mB/r). D6)

The free energy of ihe system in equilibrium can be obtained by substituting D5) in D2).
It is easier, however, to obtain F directly from the partition function for one magnet:

Z = exp(\302\273iB/r) + expt-niB/r)
\302\253
2cosh(mB/t). D7)

Now use the relation F =

\342\200\224ilogZ as derived below. Multiply by N to obtain the result
for N magneis. (The magnetization is derived more simply by the method of Problem 2.)

Differential Relations
The differential off is

dF = dU - xda - oiit,
or, with use of the thermodynamic identity C4a),

dF = -adt \342\200\224fdV
\342\226\240

for which

D9)

These relations are widely used.

The free energy F in the result p =\302\273
-(rf/^K), acts as the eilecttvc energy
for an isvihcnwil change of volume; contrast this result witii B6). The result
 Calculation of Ffrom Z

may be written as

' - \342\231\246 \342\226\240

-($. <D,

by use of F = U ~ to. The two terms on the right-hand side of E0) represent
what we may call the energy pressure and the entropy pressure.The energy
pressure ~-(cU/dV)f is dominant in most solids and the entropy pressure

x(?a/3V)t is dominant in gases and in elastic polymerssuelias rubber {Problem

10). The contribution

enlropy is testimony of the importanceof the
entropy:

Ihe natve feeling from simple mechanics that -JUjdV must tell everything
about the pressure is seriously incompletefor a process at constant temperature,
because the entropy can changein response to she volume change even if the
energy is independent of volume, as for an ideal gas at constant temperature.

Maxwell relation* We can now derive one of a group of useful tliermodynamic relations
called Maxwell relations.Form the cross-derivauvirscV/^l\" Hx and ^FfcxcV,which must

be equat 10 each other. It follows from D9) that

(ca/dV)t *{ep;eT)y , E!)

a relation that is not at all obvious. Other Maxwell relations will be derived later at

appropriate points, by similar arguments. The methodology of obtaining thermody-

namic relations is discussed by R. Gtlmore, L Chem. Phys. 75, 5964 A981).

Calculation of F from Z

Because F = U - %a and a = -{cFjdi)Vt we have the differential equation

F = U + i{SF/dt)Vt or ~x2c(F/z)Jcx \302\253

U. E2S

Wo show thul this equation is satisfied, by

F/x - -log^ . E.1)

where Z is the partition fund ton. On substitution.
Chapter3: Bollzittnnn Distribution and Hchniipliz Free Energy

by A2). This proves that

F= -riogZ E5)

satisfies the required differential equafion E2).

It would appear possible for Fjx to contain an additive constant a such that
F = -riogZ + ar. However, the entropy must reduce to \\oggQ when the

temperature is so low that only the cj0 coincident states at the lowest energy \302\2430
are occupied. In that limit logZ -* logg0~ W*. s0 thai a = -cFjcr \342\200\224

= a ~ 0.
g{t log Z)fct logg0 only if

We may write the result as

Z- cxp{-f/t); E6)
and the Boftzmann factor (II) for the occupancy probability of a quantum

state s becomes

E7)

IDEAL GAS: A FIRST LOOK

One atom in a box. We calculate the partition function Zx of one atom of

mass M free to move in a cubical box of volume V ~ L1. The orbitals of the

free particle wave equation -{/iJ/2.U)V:^ == ei/i are

= Asia(nxitx , E8)
\\p{x,y,z) L)sm{iiyity}L)sin{n.iiz}L)

where ir,, nyt n. are any positive integers, as in Chapter 1. Negative integers do
not give independent orbitals,and a zero does not give a solution. The energy
values are

We neglect the spin and all otherstructure of the atom, so that a state of the
system is entirely specified by the values of nlt nft n:.
 Ideal Cm: A First Look

The partiiion function is ihe sum over the states E9);

Provided the spacing of adjacent energy values is small in comparisonwiih t,

we may replace the summations by integrations:

2] = I t!nx I
dnf (/ji,cxp[
\342\200\224
*2{nx2 + ny2 + 'u2)]. F1)

The notation a\" & Azji2/2A/12t is introduced for convenience. The exponential
may
be written as ihe product of Ihrec factors

F2)

in ierms of ihe concentration ji ~ XjV.

Here

F3!

is catted the quantum concentration. It is the conccnlration associated with one

atom in a cube of side equal to die thermal average lie Broglie wavelength,
which is a length roughly equal to /i/M<i\302\273> h'{Mi)ul. Here <r> is a thermal
-

averagevelocity. This concentration will keep turning up in ihe thermal physics

of gases,in semiconductor theory, and in the theory of chemical reactions.
For helium at atmospheric pressure at room lemperature, n. s= 2.5 x
lO^cnr3 and uQ = 0.8 x I02scrrT3. Thus, ii/iiq
*3x I(T6, which is very
small compared 10 unity, so ihat helium is very dilute under normal conditions.
Whenever n/nQ \302\2531 we say ihat the gas is in the ctassieai regime. An ideal gas
is defined us a gas of noninteractingatoms in the classical regime.
The thermal average energy of the alom in the box is, as in (]2),

F4)

becauseZj\"' exp{- eJx) is (he probability the system is in the state it. From F2),

log^i = \342\200\224
jlog(I/i) -f- terms independent of t ,

so that for an ideal gas of one atom

F5)

If t =*
kaT, where kB is :Iic Boltzmann constant, then U =
lkHT, the well-
known result for the energy per atom of an ideal gas.
The thermal average occupancy of'a free particle orbital satisfies the in-

equiility

which sets an upper limit of 4 x !0\026 for the occupancy of an orbital by a

helium atom at standard concentration and temperature. For the classical
regimeto apply, this occupancy must be 1.
\302\253 We note that as defined
\302\243\342\200\236 by E9)
is always positive for a free atom.

temporarily tiiitil ac develop in Chapter 6 a powerful meihod 10 deal with the problem of

many noniulcmaing identical a box. We iitsi ireai an ideal gas of .V aioms

atoms i\302\273 in a
box, all atoms of different species or different isotopes. This is a simple extension of the

one utoni result. We then discuss the major correction factor that arises when ail atoms are
identic!!, of ik b.unc isotope of ihe same specks.
 Ideal Gas; A First Look

\342\226\241 !\342\226\241
I 2 1

Figure 3.7 An .V particle system of free particles with one panicle in each
of.V bo\\es. The energy is N limesthat for one particlein one box.

*
o Figure 3.8 Atoms of different species in a

If we have cfne atom in each of iV distinct boxes (Figure 3.7), the partition funciion is fhe
product of ihc separateone aiom partition funclioiis:

= , F6)
ZXha*\302\273 Zt{l)Z1B)---Zl(N)

because ihe product on !he right-hand sido includesevery independent state of llic N

':,(!) f- r.^2) + ,
\342\200\242\342\200\242\342\200\242r^N) F7)

where 3, fi.... Cdenotethe orbital indices oUlotm in ihc suewssive boxes. The result F6)
also gives lite pjiiiiioit function of iV itottmiontciJng aiuiits all ordilTcrctii speciesin a

single box (Figure 3.S):

iliis bang problem bseauic the energy eigenvalues

the same are iliesameas for F7). If i!ic
musses of all thsic dilTercni atoms hapjiened lo be lite same, ihe lotal partiiion funciion
would be Z,-\\ whsrc Zl is given by F2).
When we consider ihe more common pfublem of N identical panicles in one box, we
have to correct Zts~ because it overcounts the disiincl siaics of the ,V idutitic.tl parliclc

lion numbers. For mo hbded particles and

\302\251 - in a single bos, the siate ^(O) + M*l
and ihe Male \302\243,(\342\200\242)
+ cfrtO|;irc tlisiinct Mates, and both combiti.tttons tmibi be counted i\302\253
lite pmtiuon function. Bui for hs'o tdetiitccil pitritclcs lHc st.iie of energy c, + \302\243*
Ij Hie

idcmicai siate as c^ + \342\202\254\342\200\236

and only one cnlry is to be made in tfte si.ite sum in the p.irtiiioti

futiciion.
Chapter 3: BoHzmann Distribution ami Hdmhohz Free Energy

If tlicorbiial indices are alt diffrfem, each cniry wilt occur S< limes iti Zts, whereas llic
entry slsould occur onlj once if ihe panicles are identical. Thus, Z,v ovcrcounisthe Stales by
a faclor of ,V!, ;md the correct partition function for N identical particles is

F8)
\342\226\240mz'\"-*]<\302\273>**\"
|

in iheclassical regime.Here nQ = {\\(zi2nk3)yl from F3).

There isaslep in ihe argitmcni whcii we assume iliat ail jV occupied orbiuis arc always

diticrcnt oEotla's- It i\302\243

no Simple rnallei lo cvaltsaie o^rccily {lieerror tmrouuecci by ih^S
^pproxitnaiiorij but laicr %sfg v,'il\\ cotifj^ni by another rnctliod the validiiy of FSJ in (lie
tlassicai regime n <i na. Tile ft'! fjcior changesihe result for the entropy of !hc ideal gas.
The enlropy is an cxpaimemalty measurablequaniily, and i! lias been confirmed ihat the

jV! facior is corrcci in this low concentration irmit.

Energy, The energy of {he ideal gas follows from {he N particle partition
funciion by use of{l2):

l/ = T3^l0gZ.v/(}T}=^T
, F9)
consistent with {65} for one panicle. The free energy is

F = -ilogZy - -i]ogZi'v + ilogN!. G0)

With {he earlier result Zt = naV = (Mr/2n/!2K'i2KandtheStirlingappfoxima-

tionlogN! c=
NlogN
\342\200\224we
N, have

F = -tNIog[{.Ui/2n/i2K'2K] + rNtogN - xN. {71}

From the free energy we can calculateihe entropy and the pressure of the ideal
gas of N aioms. The pressure follows from {49}:

p - -BF/3K), = NxjV , {72}

= Nr, G3)
PK
I
 IdtalGas: A first Look

which is called the iJcal gas law.In conventional units,

1>V = NkuT. G-1)

The entropy follows from D9};

a = -{CF/?z)r = W!og[{Afr/2\302\253/r}3';F] + \\N

-
NlogN + S , G5}

G6)

with (he concentration n \342\200\224

NjV, This result is known as the Sackur-Tctrodc
equation for the entropy of a monatomtc ideal gas.It agreeswith experiment.
The result involves h through the term hq, so even for the classical ideal gas
the entropy involves a quantum concept. We shall derive these results again tn
Chapter 6 by a direct method that does not explicitly involve the N\\ or identical

particle argument. The energy {69}also follows from U *= F + xa; with use of
{7!}and {76}we have V = \\Nr.

Example! of energy.
Equipanlihn The energy U = |j\\'r from F9} is ascribed to a contri-
contribution each \"degree of freedom\"
i* from of each panicle, where the number of degrees of
freedom is tlic number of dimensions of the spsce in which ttie slonis move: 3 in Itus
example. In ihe classical focm of siatisiicat mechanics, the partition function contains the
kinetic energy of the particles in an iniegral over the momentum components p,. pt, p,.
For one free particle

( pI1)/2Mx']dpIdpfilp. , {77}
Jjjexp[~

a result similar to Ft). The limits of integration are fat

\302\261ao each component. The thermal
average energy may be calculated by use of A2) and is equal wfr.
The result ts generalized in the classical theory. Whenever the Kamiltonian of the system
is homogeneous of degree2 in a canonical momentum component, the classical limit of the
thermal averagekinetic energy associated with thai momentum wilt be Further,
\302\243r. if the
hamiltonian is homogeneous of degree 2 in a posilion coordinate component, theihermal
average potential energy associated with that coordinate will also be Jr. The resull thus
 !

3
Vibt
- ^\342\200\224\302\273

2
lion

T,\302\273s

I
0
25 50 75100 250 500 1000 2500 5000
Temperature.
K

Figure 3.9 Heat capacity at constant volume of one molecule of Hj in

the gas phase. The vertical scale is in fundamental units; !o obtain a value
in conventional units, multiply by kB. The contribution from the three
transnational degrees of freedom is j; the contribution at high temperature
from the two rotational degrees of freedom is 1; and the contribution
from ihe potential and kineiic energy of the vibrattonal motion in the
high icinpciaturc limit is I. The classicallimits are attained wlicn
i \302\273
relevant energy level separations.-.

applies to ihe harmonic oscillator in the classical limit. The quantum results for the har-
harmonic oscillator and for the diatomic roiator are derived in Problems 3 and 6, respectively.
At high temperatures the dais teal limits are attained, as in Figure 3.9,

Example: Entropy ofttuxia*. In Chapter 1 we calculated the number of possible arrange-

arrangementsof A and 8 in a solid made up of ,V - ( atoms A arid t atoms B. We found in A.20)
for the number of arrangements:

A/i
G3)

The crtiopy associated with these arrangements is

c{A',0 = logflMf) - bg,V! - !og{iV

-
r)!
~ logti , G9)

and is piotied in Fi^me 3.10for jV

~ 20. This contribution to the total entropy of ;tn alloy
 itfcalGas; A First lj>ak

\\

4 4\342\200\224-~

vj
7
0 0.2 0-4 0.6 0.S 1.0

Alloy composition At_x Br

Figure 3.10 Nftxing entropy ora random binary alloy as a function of

ihe proportions or the constituent atoms A and B. The curve plotted
was calculated for a total of 20atoms. We see that this entropy is a
maximum when A and B are present in equal proportions (x \302\273
0.5),
anci trie entropy is zero For pure A or pure H.

system iscalled the entropy of mining. The result G9) may be put in a more convenient u
by use of the Sliding approximation:

=* NlagN - N - -
i)\\ag{N
- i) + N - t ~ rlogt + r
a(N,i) (N

= NlogN
- (N - !)\\og(N
-
t)~~ l\\agl
= -(,V - t)Iog(l - //N)
- l Iog(f/jV) ,

.viih x = t/N,

- -v)Iog(I - -v) .vlog.v].

This result gives the entropy of mi\\iug of an n'loy A^^B, treated as a random (homo-

(homogeneous} soiici solmx^i. TIic problem is J^dopjd in detail in Chapter 11.

We ask i Is the homogeneous solid solution ihe equilibrium condition of a mixture of A
and B atoms, or is the equilibrium a two-phase system, sudi as a miMure ofcrysi2l!::i*s of

pure A and crystallitesof pure B?The complete answer is the basis of much of the science

of metallurgy: the answer will depend on the temperature and on the imcniioiTiic ii;;;r-
action energies t/M, f/EB,and UAa. In the special case iluit tltc iiue faction energies bciw.vn
A A., BB, and AB neighbor pairs are all equal, ihe homogeneous solid solution will have a
lower free energy than Hie corresponding mb-lure ofc/yitatlilci of the pure elements. The
free energy of the solid solution A [ -^B, is

F = Fo - tct(.v)
\302\273
Fo + A't[A
- .\\)Iog{l - a) + , (81)
xlogx]

which we must compare with

F = A
-
x)F0 + xF0 - Fo (82)

Tor the mixture of and B crystals in the - The entropy of mixing

to x.
A
proportion A .vj

is always positive\342\200\224all entropies arc positive\342\200\224so that the solid soiution has ihe lower
free energy in this special case.
There is a tendency for at least a very small proportion of any element B to dissolve in
any other element A, evert if a strong repulsive etlergy exists between a B atom and ihe
sutroundiug A atoms. Let this repulsive energy be denoted by U, a positive quantity. If a

very small proportion -\\ t of

\302\253 B aioms is present, the Iota! repulsive energy is xi\\U, wlk-re
xN is ihe number of B atoms.Tlic mixing eniropy (SO) is approximately

a = ~.\\N\\ogx (83)

- N(sU + txiog.v) , (84)

Fix)

which has a minimum when

BFfBx \302\273
N(U + xiog-v + t) = 0 , {85}

x =
exp(~!}exp(-t//T}. (86)

This shows there is a natural impurity content in all crystals.

SUMMARY

1. The factor

=
?{\302\243j) expf-e./tJ/Z

. is the probabiHty of finding a system in a slate s of energy c, when the system

 is in thermal comaei with a large reservoir ai temperature r. The numberof
particles in the system is assumed constant.
2. The partition function is

3. The pressure is given by

p = ~{cUldV)a = x$gIc\\')v.
4. The Hejmltoltz free energy is defined as F ^ U ~ xa. H is a mittimum in

equilibrium for a system held at constant i, V.

'
5. a - -i?F/dT)y; p \302\273
~{8F/dV)r

6. ss -tlogZ.Tltisrcsulitsvcry
}\342\226\240 ttscru! incilcuhitiansorf and ofquuniiiics
such as p and o derived from F.

7. For an ideal monatomicgas of N atoms of spin zero,

ZH = (nQVf/N\\ ,

if u ~ N/V \302\253
\302\273a.The quantum concentration nQ s (A/r/2n/t2K/I. Further,

pV
- JVt; o = W[log(iic/H)
+ 5]; Q = fW.

8. A process is reversible if the sysiem remainsinfinitesimally close to ihe

equilibrium state at all times during ihe process.

PROBLEMS
/. Free energy of a two state systenu (a) Find an expression for the free
energy as a function of t of a system with two states, one at energy 0 and one
in
energy c. (b)fro; ettcrgy, find
From ihe expressions for the energy itnd entropy
of the system. Tttc entropy is plotted in Figure 3.11.

2. Magnate susceptibility. 00 Use ihe pitriiiion function io find nn exaci

expression for ihe tnagiteliAUiou M end tltu susceptibility x s ilM/tlB as a

function of temperature and magnetic field for the model system of magnetic
moments in a magnetic field. The result for the magnetization is M ~

mutanli^jiB/i}, as derived in {46}by another method. Here n is the particle

Chapter Si Bolizmann Distribution and tjelinholt; Free Energy

-
OR 2

0.6

0.4 A-
/

0.2 /

/ ]

ft
0 0.5 1.0 1.5 2.0

Figure 3.12 Plot of ihe loui macaeiicmoment as a function

ofmfl'r. Notice thai 31 lou mB/x the momeni is a U.icarfunciio

of HiiJ/r, bul Ai high hiS r the manicnl Sends 10 salurale.

contciiiraitot!. Tlie result is plottcJ in Hgure 3.12. (b) Find ihe free energy and

express the result as a function only ofr and the parameicr.v s M/tuu, (c) Show

thul the sust;eptibiltty is x \342\200\224 in the

j\302\253\302\273V ttniit \302\253
/\302\273B r.

i. /Vcc energy of a harmonic oscillator. A one-dt'mcnsian;il liurmonic oscil-

oscillator has an infinite series of equally spacedenergy states, with =
\302\243, sho, where
 Figure 3.13 Enin
osciliuSor of frequency

s is a positive imegeror zero, and to is tlic classical frequency of she oscillaior.

Wu have chosen the zero of energy at the state s = 0. (;s) Show that for a
harmonic oscillator the free energy is

(S7)

Note that at high temperatures such ihal x fitu

\302\273 we may expand the argument
of the logarithm to obtain F^i !og(/itu/t). (b) From (87) show thai the entropy

($8}

The entropy is shown in Figure 3.13 and the heat capacity in Figure 3.1-i.

4. Energy fluctuations. Consider a systemof fixed volume ta thermal contact

wiiis a reservoir- Show that the mean square fluctuation ia she esiemyof lhc
syslcin is

Here U isthe conventtooai symbol for <e). Hint: Use the partition fitnctwn Z

to relate c-U/ci to ihc mean square fluctuation. Also, multiply out the :crm
\342\226\240
J. Note:
(\342\226\240 The temperature t of a system is a quantity that by delirsiiion does
 Chapter 3: Bohzmnn Distrihut mJ IIcIihUoUz Free Energy

S\302\273re3.S4
Heal capacity Versus u-mperatufe ^
r harmonic oscillator of frequency u>. The

ifiiontal scale is in units of i/fiw, whkh is

unncal wilh T flE. \302\253herc0, is calkd rhc
mlcln Icniperamte. \\n the high temperature
iiit Cv
- kB.ot 1 in run<iamciiia! miiis. This
iluc is k^own 'as \\\\\\t c^issic^I V'^Iv:;. i\\i low

mpcratures C(- decreases csponeniially.

y
0.5 1.0
t r

not fluctuate v,\\ value \\shcn the system is in thermal contact with a reservoir.
Any otltcr attiiude would be inconsibletit with our definition of the temperature
of a system.The energy may fiuetijiitc, but the temperature
of such a system
do^s ltot. Sorr.c workers do not acllterc to a rigorous definition of temperature.

Thus Landau arid Ltfshttz etve Hie result

\302\253AtJ>
=> t2/Cv , (90)
but this should be viewed as just another form of (89) with At equal to
AV;CV. We know that AU = Cy At, whence (90) becomes <(Ak - r=C,.,
which is our result (89).

5. Ovcrhaussr effect. Suppose suitable external mechanicalor

that by a
electrical arrangement add ae
one to
can the energy of 'he heat reservoir

whenever the reservoir passes to the system the quantum of energy e. The net
increase of er.eray of the reservoir is (a \342\200\224
l}e. Here a ts some numerical factor,
positive or negative. Show that the effective Boltzmantifactor for this abnormal
system is given by

This reasoninggives the statistical basts of the Ovcrhattsereffect whereby the

nuclear polarization in a magnetic field can be enhanced above the thermal
equilibrium polarization. Such a condition requires the active supply of energy
to the system from an external source. The system is not in equilibrium, but ts
said to be in a steady state. Cf. A. W. Overhauser, Phys. Rev. 92, 411 A953).

6. Rotation of diatomic molecules. In our first look at the ideal gas we con-
considered only the translationa! energy of the particles. But molecules can rotate,
with kinetic energy. The rotational motion is quantised; and the energy levels
of a diatomic molecule arc or the form

ft;} = jlj + l)\302\243o (92}

where; is any posilive integer includingzero:/ = 0, I,2,.. .. The multiplicity

of e;ich rotational level is </(;) - 2; + I. (a) Find the partition Zk(t) function
for the rotational states of one molecule. Remeniber Z is a sum over all
that
stiitcs,not over all le\\cls\342\200\224this makes a difference, jb) Evaluate ZH(x) approxi-

approximately for r the sum to an integral, (c) Do the same

\302\273
e0, by converting for
r \302\253
sOl by after the second term,(d) Give expressions
truncating the sum for
the energy V and the heat capacity C, as functions oft, tn both limits. Observe
that the rotational contribution to the heat capacity of a diatomicmolecule
approaches 1 {or, in conventional units, A-,,)\\Uv?n r \302\273
r.0.lc) Sketch the behavior
of L'(t) nnd C{x),showing the limiting behaviors for r -\302\273
ro and r -* 0.
7. Zipper pruhh'W. A zipper h:is N links; each link has n state tti which it is
closed with citefgy 0 and u siate in which ii is open with energy t:. We require,
however, zipperthat only im/jp from the left end,
the can and that site link
mmiher s can only open if all links to jhe left {1,2,.. .,s - 1} are already open,
(a) Sliow ihat the parution fuiicliotl can be summed tn the form

193}

{b) In the i, find

e \302\273
iirnii the average number of open links.The modelis a

very simplified model of lhe unwinding ofnvo-siraiided DNA molecules\342\200\224see

C. Kittel, Arner. J. Physics 37, 917A969).

5, Quantum concentration. Consider one particle confined to a cube of side

L; lhe concern rai ion in effect is n = 1/L3. Find the kineiic energy of i he particle
when in the ground orbtial. There will be a value ofthceoticentraiioii for which
lhis zero-poini quantum kineiic energy is equal to the temperature r. (At this

concern ration the occupancy of the lowestorbitalis of the order of unity; ihe
lowest orbital always has a higheroccupancyilian any oilier orbiial.) Show thai
the concentration nQ thus defined is equal to the quantum eoticcntraitonnQ
defined by {63), wtthtti a facior of ihe orderof utitiy.

9. Partition function for two systems. Show thai the partition function
Z(l 4-2) of two independent sysiems I and 2 in thermal contaci at a common
temperature t is equal 10ihe produci of ihe paniUon funciions of the separate
systems:

Z(I + 2)
= Z(I)ZB). (94)
ChaptcrS: Boltzntann Distribution and Heimhaltz free Energy

10. Elasticity of potythevs. The lhermodyiiamic identity for a One-dimensional

system is

zda = dU ~ fdi (95)

when / is the external forceexertedon the line and ill is the extension of the
line. By analogy witSi C2) we form the derivative to find

.-Ha-

The direction of the force is opposite to the conventional direction of the

pressure.
We consider a polymeric chain of N links each of length />, with each link
equally likely to be directedto the right and to the left, (a)Show ihat the number
of arrangementsthat give a head-ioiail length of / =
2js|p is

'
q(N,-s) + q(N,s) = -T-
\342\200\224~
(97)
4- 5)! -
(kN (\302\243N s)\\

(b) For \\s\\

JV
\302\253 show that

(98)

(c) Show that the force at extension / is

/ = h/Np1. (99)

The force temperature. The forcearises

is proportional to the because the

polymer wants to cur! up: the entropy is higher in a random coil than iti ati
uncoiled configuration. Warming a rubber band makesit contract; warming a
steel wire makes tt expand. The theory of rubber elasticity is discussed by

H. M. James and E. Guilt, Journal of ChemicalPhysics II, 455 A943); Journal

of Polymer Science4, 153A949); seealsoL. R. G. Treloar, Physics of rubber
elasticity, Oxford, 1955.
II. Ouc'dimcmionaigas. Consideran idea! gas of A' particles, each of mass
M, confined to a one-dimcsisional line oflcnath L. Find the entropy at tempera-

temperaturer. The pti5tides have spin zero.

Chapter 4

Thermal Radiation and

Planck Distribution

PLANCK DISTRIBUTION FUNCTION

PLANCK LAW AND STEFAN-EOLTZMANN LAW

Emission and Absorption: KirchhorT Law 96

Estimation of SurfaceTemperature 97
Example: Cosmic Black Body Background Radiation 93
ELECTRICAL NOISE

PHONONSIN SOLIDS: DEBYE THEORY 102

Numberof Phonon Modes 104
109
no
Number of Thermal Photons 110
Surface Temperature of Ike Sun
Average Temperature of the interior of the Sun 111
Age of the Sun 111

Surface Temperature of tlte Earth 111

Pressure of Thermal Radiation 111

Free Energy of a Photon Gas 112
Heat Shields 112
Photon Ga: in One Dimension 112
Heat Capai ty ol\" intergalactic
Space 113
HeatCapa' ty of Solids in High Temperature Limit 113
HeatCapai;ty of Photons and Phonons 113
Energy Flu> tuations in a Solid at Low Temperatures 113
HeatCapai ty of Liquid 4He at Low Temperatures 113
Angular D: tribution of Radiant Energy Flux 114
image of a Radiant Object
and 114
Entropy Occupancy
Isentropic Expansion of Photon Gas 114

Reflective Heat Shield and Kirchhoff's Law 115

SUPPLEMENT: GREENHOUSE EFFECT

Chapter's: Thermal Radio

[We consider] the distribution of the energy U among N oscillators of frequency

v, // U is viewed as divisiblewithout limit, then an infinite number of
distributionsare possible.We consider however\342\200\224wUl this is the essential point
of the whole calculation\342\200\224Vas made up of an entirely determined nimiber of

finite equal parts, and we make use of the natural constant h = 6.55 x fO~21
erg-sec.This constant when multiplied by the common frequency v of the
oscillators gives the element of energy e in ergs ....

M. Planck
 Planck Distribution Fu

PLANCK DISTRIBUTION FUNCTION

The Planck distribution describesthe spectrum of the electromagnetic radiation

in thermal equilibrium within a cavity. Approximately, it describes the emission

spectrum of the Sun or of meta! h eated by a welding torch. The Planck distribu-
distributionwas the first appHcation of quantum thermal physics. Thermal electro-
electromagnetic radiation is often caHed black body radiation. The Planckdistribution
also describes the thermal energy spectrum of lattice vibrations m an clastic
solid.
The word \"mode\"characterizes a particularoscillation
amplitude pattern in
the cavity or in the solid. We shall always refer low = 2nf as the frequency of

the radiation. The characteristic feature of the radiationproblemis that a mode

of oscillation of frequency w may be excited only in units of the quantum of

energy hio. The energy of
\302\243, the state with s quanta in the mode is

e, U)

where s is zero or any positive integer (Figure 4.!). We omit the zero point
energy \\hai.

These energies are the same as the energies ofa quantum harmonic oscillator
of frequency to, but there is a difference between the concepts.A harmonic

Figure 4.1 Stales of an oscillator that

represents a mode of frequency tu of an

to s photons in the mode.

(-haptcr 4- Thtftjml Radiation and Planck Distribution

modes a and b, of frequency and \302\253>t.

&>\342\200\236 The amplitude
magnetic field is suggested in the figures for one pliotor
occupancy ofeach mode.

oscillator is a iocasizedosciiiator.whereas the electric and magnetic energy of

an electromagneticcavity mode is distributed throughout the: interior of the
cavity (Figure 4.2). For problems the energy eigenvaluesare integral
both
multiples of ho, and this is the reason for the similarity in the thermal physics of
the two problems. The language used to describe an excitationis different; s for

the oscillator is called the quantum number, and s for the quantized electro-

electromagnetic mode is called the number of photons in the mode.

We first calculate the thermal average of the number of photonsin a mode,
when these photo ns are in thermal equilibrium with a reservoir at a temperature
t. The partitionfunction C.10) is the sum over the states A):

}{~shia/r}. B)

This sum is of ihc form TV, with .\\- s exp{-/i<y/0- Because .\\- is smaller than 1,
the infinite scries may be summed and has the value 1/A -- x), whence

C)
1 -exp(-tou/T)
 Planck Lax and Slefan-BohimannLt*

The probability that the system is in the state s of energy slim is given by the
Bohzntann factor:
\342\200\224
exp( shci/x)
P(s)

The thermalaverage value of s is

E)

With >' = ftej/r, the summation on the rmht-hand side has the form:

-cxpt-v)/

From C) and E) we find

I -exp(->.)'

F)

This is the Planck distribution function for the thermal average number of
photons(Figure 4.3) in a singie mode of frequency w. Equally, it is the average
number of phonons in the mode.The result applies lo any kind of wave field

with energy in the form of (!).

PLANCK LAW AND STEFAN-BOLTZMANN LAW

The thermal average energy in the modeis

G)
\342\200\224
) 1*
 Chapter 4: Thermal Radiation and Planck Disiribttlio

+
*(\302\253)

Figure 4.3 Planck distribution as a function

ofihe reduced temperature i./rw. Here <s(w)>

is Hie thermal average of the rmniber of
photons in the mods: of frequency en. A plot of
0.5
O(o)> + i is also given, where $ is the effective /
7ciopoint occupancy of ihc mode; the dashed
line is i!ie classical asymptote.Noie that we

A
0.5

The
high temperature limit t \302\273
ha) is often called the classical limit. Here
*
lna/r 4-
\342\200\242
exp{frfcj/t) may be approximated as 1 4- whence
\342\226\240, the classical
average energy is

^
<\302\243> T. (8)

There is an infinite number of electromagnetic modes within any cavity. Each

mode n has its own frequency wn. For radiation confined within a perfectly
conducting cavity in the form of a cube of edgeL, there is a set of modes of the
form

=
Ex ExOitn wtcos(fiJji.v/L)sin(iiyjij'/L)sin(fi.Jiz/L) , (9a)

ID sin(fl=Tiz/L) , (9b)

Et = E-0 (9c)

Here Ex, Er and Ex are the three electric field components, and \302\243lQ,Ey0 and
are
\302\243;0 the corresponding amplitudes. The three components are not indepen-

independent,because the field must be divergence-free:

A0)
 Planck Law and Slcfan-Bolwtann Law

When we insert {9}into A0} and drop ail common factors, we find the condition

\302\243,0\", + E^nr 4- E:Qn: -. Eo \342\226\240

n \302\2730- A1)

This states rhar the field vectors must be perpendicular to the vector n with

the components nx, ny

and >l, so that the electromagnetic field in the cavity is a

transversely polarized field.The polarization

direction is defined as the direction
of Eo.
For a given triplet n,, nft can choose two
n. we mutually perpendicular

polarization directions, so rhat rhere are mo distinct modes for each iriplei

On substitution of (9) in the wave equation

V'-v1 i:y trJJ. '. .(V

wilh c the velocity of light, we find

cWnJ 4- + n;2)
= w3L2. A3)
Hya

This determinesthe frequency of

\302\253) the mode in terms of Hie triplet of integers
>h< \"y if we
\";\342\226\240 define

= (rtj[2
\342\200\236 + ,,/ + ,
rta\302\273)\302\273'i A4)

then the frequencies are of the form

w.
= mrc/L. A5)

The total energy of the photons in the cavity is, from G),

The sum is over the triplet of integers nx, integers alone will
ny,
n.. Positive
describe all independent modes of tlic form (9). We replace the sum over nx,
ny, iij by an integral over the volume clementditx dny dnx in the space of the mode
indices. That is, we set
Chapte

where the factor | =h arises

(\302\243K because only the positive octant of the Spaceis
involved. We now multiply the sura or integral by a factor of 2 because Ihere are
two independent polamations of the electromagnetic field (two independent
setsof cavity modes). Thus

1, = ji ft hu)n

Jo

(nVic/L) r dnn* \342\200\224

A8)
\302\273\302\260 ex

with A5) for Standard

\302\253\342\200\236. practice is to transform the definite integral to one
over a dimensionless variable. We set x = nhcn/LT, and A8) becomes

A'J)

The definite integral has the value z*/l5; it is found in good standard tables
such as Dwight (cited in the general references}. Tlie energy per unit volume is

B0)
\\Shs

with the volume V = L1. The result that the radiant energy density is propor-
lional !olhe fourth power oflhe lemperalure is known as theStefan-Boltzmann
law of radiation.

For applications of this theory

many we decompose B0) into the spectral
density of the radiation.The spectraldensity is defined as the energy per unil
volume per unit frequency range, and is denoted as \302\253\342\200\236,.
We can find \302\273u
from

(IS) resvritlen in terms of w:

U/V B1)

so that the spectral density is

B2)
 Planck Law andSufan-Boltzmam Law

1.2
\\
1.0 / \342\200\224

/
0.6 /
1

0.4 /
\\

\\

0.2 /
\342\200\224 \342\200\224

0/

Figure-1.4
~ l)willi.v = bttf/t. T\\\\h
Ploiof.vJ/(c*
runciion h involved in the Planck radiation law for llic
spectral density uw. flic temperature of a black body may
be found from ilie frequency tjmil ai which the radiant
energy density is a maximum, per unit ffequency range.
This frequency is directly proportional so ihe tempera sure.

This result is the Planck radiation law; It gives the frequency distribution of
thermal radialion (Figure4.4).Quantum theory began here.
The entropy of the thermal photonscan be found from the relation A34a)
at constant volume:da ~ dUfr, whence from B0),

Thus the entropy is

B3)

The constantofintegration is zero, from C.55) and the relation belsvecnF and a.
Chapter 4: Thermal Radiation and Planck Distribution

gy y v gy p
The flux density is of the order of the energy contained in a column of unit

area and length equal to the velocity of light times the unit of time. Thus,

The geometrical factor is equalto \302\243;

the derivation is (he subject of Problem 15.
The final result for the radiant energy flux is

by use of B0) for the energy density U/V. The result is often written as

B6)
Jv \302\253

aB s= b2V/60AV B6a)

has the vahie 5.670 x 10~8 W m~2 K~* or 5.670x 10\"* erg cm\022 s~' K~\".
(Here cts is not the entropy.) A body that radiates at this rate is said to radiate
as a black body. A small hole in a cavity whose walls are in thermal equilibrium
at temperature as a blackbody at the
T will radiate rate given in B6). The rate
is independent of the physical constitutionof the walls of the cavity and de-
depends only on the temperature.

Emission and Absorption; Ktrchhoff Law

The ability of a surface to emit radiationis proportional to the ability of the

surface to absorb radiation. We demonstrate this relation, first for a black body
or biack surface and, second, for a surface with arbitrary properties. An object
is defined to be blacktn a given frequency electromagnetic radiation
range if all
incident upon it in that range is absorbed. By this definition a ho!e in a cavity is
biack if the hole is small enough that radiation incident through the hole will
 t oj Sutj

reflect enough times from the cavity walls lo be absorbed in the cavity with

negligible loss back through the hole.

The radiant energy flux a black surfaceat temperature
density Jv from x is

equal to the radiant energy

density Jv flux from a small hole
emitted in a cavity
al the same temperature. To prove this, let us close the hole wilh the black
surface,hereaftercalledthe object, in thermal equilibrium the thermal average
energy fiux from the black object to the interiorof the cavity must be equal,
but opposite, to the thermal average energy flux from the cavity to the black

object.
We prove the following: If a non-black object at
temperature t absorbs a
fraction a of the radiation incidentupon it, the radiation by the flux emitted
object will be a ttnies the radiation flux emitted by a black body at the same
temperature. Let a denote the absorptivity and e the emisstviiy, where the
cmissi\\ity is defined so that the radiation flux emitted by the object is e times
the fiux emitted by a black body at the sametemperature. Theobjectmust emit
at the same rate as it absorbs if equilibrium is to be mainiamed. H follows that

a~e. This is the Kirchhoir law. For the special case of a perfectreflector,
a is

zero, whence e is zero. A perfect reflector docs not radiate.

The argumentscanbe generalized to apply to the radiation at any frequency,
as betsveen <o and w + ito. We insert a filter between the object and the hole in
the black body. Let the filter reflect perfectly outside this frequency range, and
let it transmit perfectly within this range. The flux equality arguments now

apply to the transmitted spectral band, so that a(w)

= eM for any surface
in thermal equilibrium.

Estimation of Surface Temperature

One way to estimate the surface of a hot body such as a star is

temperature
from the frequency Ihe maximum
at which emission of radiant energy takes

place (see Figure 4.4). What this frequency is depends on whether we look at the

energy fiux per unit frequency range or per unit wavelength range. For if,,,, the

energy density per unit frequency range, the maximum is given from the Planck

law, Eq. B2), as

\342\226\240\342\200\242
0 ,

3 - 3exp(-x) = x.
Chapter 4: Thermal Radiation and Planck DiVnfmrion

This equation may be solved numerically. The rool is

kca^JkgT = xm ^ 2.82 , B?)

as in Figure 4.4.

Example:Cosmicblack body background radiation. A major recentdiscovery is that the

universe accessible to us is filicd with cudutian approximately like thai of a black body
at 2.9K. Tlic existence of lliis radiation [Figure 4.5) is important evidence Tor big bang
cosmotogiol modelswhich assume ltw! tli^ unhorse is expanding and cooling wiitl liliic.

so ihaf Ihc nimicr ;uid itie bhiirk body radiaiion were in Itiaiipl cqtiitilirium. IJy ihe lime
itic universe h;id coo ted lo 300A K,! tie m;iiUv Mas primarily in she farm of atomic liydrogen.

This irucructs with bLjck body r^diLitJi^Ji only si the fic^ucOci^b of jlic liydro^jcti &fH:ctriJ
lines. Most of llie biack body r;idi;ition clergy thus was cffctiutty docouptoti from itie
mancr. Tftcrcafier ihe radiaiion evotved with \302\273mcin a very siinpte way: llic plioion gas
was cooled by expansion al constani cniropy io a icmpcraiure of 2.9 K. Tlic pfioion gas will

remain at consent cniropy if Ihe frequency of each mode is towered during ihc expastsion
of tnc universe wilfa llic nuoi^er of pljotons it\\ c>icti mooe Kept con^JunlL We show in ^joj
below that ihe entropy is constant if lhe number of pholons in each mode is consiant\342\200\224the
occupancies determine ihe eniropy.
After lhe decoupling Urn evoluiion of tnaucr inlo atoms (which are organized
heavier
inlo galaxies, stars, and ciuSl clouds) was more complicated lhan before decoupling.
Electromagnelicradiaiion, such as slarliuM, radiated by the maiter since lhe decoupling
is superimposedon the cosmic black botiy radiation.

ELECTRICAL NOISE

As an important exampleof the Planck law in one dimension, we consider the

sponMucousthermal fluctuations tn voltage across a resistor. These fluctuations,
which are called noise, were discovered by J. B. Johnsonand explained by
H. Nyquisi.* The characteristic property of Johnson noise is that ihc mean*
square noisevoltage ts proportional lo llic value of the resistance R, as shown

by Figure 4.6. We shall sec that <K:) is also directly proportional to tlie tem-

\342\226\240
H. N!jquisi,p!:js R
lical jijsus, Wiley, !
 [ Microwave

| Interstellar CN
Q IR measuremeni

2.9 K Black body-

Frequency (cm\"!)

Figure 4.5 Experimental me surememsof lhe spcclrum of the cosmic W

body radiation. Observations nf the flux were made with microwave heicr

oflhe speclrum ofinlcrslettac ; neiir lhe peak, unJ vvere rneusi

wiih a bulbon-borne infrared s ai frequencies abo\\c lhe peak.
Caurlesy of P. L. Richards.

pcrature r and tlie band'-vidili A/of the circuit. (Tliis secifon presumes a knov.1-
edge of cLvironuignetic wave propagation at Hk inicrtncdiiitc level.)
Tlie Nyquist tlicorcm gives a quanlhative. expression for ihe llicrma!noise
voltage generated by a resisior in thermai equilibrium. The theorem is lhcr^fore
uccded in any estimate of Hie iinnting signal-io-uoise ratio of an experirr.cnial
Chapter 4: Thermal Radiation and Planck

Zl

\342\200\242
Carbon filamen
~
+ Advance wire
xCuSO, m H,O
vNaCi in H..O

0 0.1 0.2 0.3 0.4 0.5

RcMblancu component, in Mil

kinds of conductors,including electrolytes. Afiei

J.B.Johnson.

apparatus. In ihe original form the Nyqutst theorem states that ihe mean
square voltage across a resistor of resistance ft in thermal equilibrium at
temperature t is given by

B8)

where A/ is the frequency* bandwidth within which the voltage fluctuations

are measured; all frequency components ouisidethe given range are ignored.
We show below that the ihermal noise power per unit frequency range delivered

by a resistor to a matched loadis x; the facior4 enters where it does because in

the circuit of Figure 4.7, the power deliveredto an arbitrary resistive load R' is

' ' B9)

(R + Rf

which al maich (R' = R) is <1\">/4J!.

' In this section the word frequency refers to cycles per unit time, and not to radians per unit till
 Noise generator

Figure 4.7 Equivalent ciicuii for a resistance ft with

a generatot oftliermal noise that delivers power to a
load R'. The cilrrenl

which is a maximum wiih respcel to R' when R' = R.

hi this condition the ioad is said to bo matched lo the
power supply. At match, & - (Yi)f4R. The filter
enables us to limit the frequency bandwidth under
consideration; ihal is. [lie bandwidth 10 whicii the mean

square voiiagc fluciuaiion applies.

Consider as in Figure 4,8 a losslesstransmission line of lenglh L and charac-

characteristic impedance Zc
~ R terminated at eachend by a resistance R. Thus the
line is matched at eachend, in the sense that ail energy traveling down the line
will be absorbed wiihoui reficciion in the appropriate resisiance. The entire
circuit is maintained at temperature t.
A transmission line is essentiallyan electromagnetic sysiemin one dimension.
We follow ihe argument given above Tor the distribution ofphoions in thermal
equilibrium, but now in a space of one dimension instead of three dimensions.
Thetransmission line has two photon modes (one propagating in eachdirection}
of frequency 2nfa
= 2nn/L from A5), so shat ihere are iwo modes in the fre-

frequency range

Sf~c'lL, C0)
where c' is the propagation velocity on the line. Each mode has energy

C1)
exp(ftwAJ
Figure 4.8 Transmission Hue oficiijjtli L with

derivation of ihc Nyquist liieorcm. The

aclerislic impedance 7,c of ihe [ ra us mission
line has ihe vaiuc R. According lo ihc
mdamcniai theorem of Iransrnission iines, [he
erminai resistors are matched to the line ivlicn
heir resistance has ihc same value R.

in equilibrium, according to the Planck distribution. We are usually concerned

with circuits in the classical limit hw z
\302\253 so that the thermal energy per mode
is r. It follows that the energy on the line in the frequency range A/ is

C2)

The rale at which energy comes off the line in one direction is

C3)

The powercoming off the line al one end is all absorbed in the terminal

impedance R at that end; there areno reflections when the terminal impedance
is matched to the line.In thermal equilibrium the load must emit energy to the
line at the same rate, or elseitstemperature would rise. Thus the power input
to the load is

9 = </2>R
\302\273
iA/ , C4)

but V ~
2R1, so that B8) is obtained. The result has been used in low tempera-
temperature(hermomctry, itt temperature regions {Figure 4.9) where it is more con-

convenient to measure (V1} than t. Johnson noise is the noiseacross a resistor

when no dc current is flowing. Additional noise discussed here) {not appears

when a dc current flows.

PHONONS IN SOLIDS; DEBYE THEORY

So I calculate the spectraldistribution

decided to of the possible fvee vibrations
for a continuous solidand to consider this distribution as a good enough
approximationto the actual distribution. The sonic spectrum of a lattice must,
 j in Solids: Dcbye Theory

Figure 4.9 Mean square noise \\ o'uge

flucluations observed cxperimcn::i))y from a
3 jiO resistorin ihe mixing chamber of a
dilution refrigerator as a function of magnetic

icmpcralurc indicated by a CMN' powder

tlidrmometer. After R. R. GiiTarJ, li. A- Webb,
and C Wheailey, J.
J. Low Tcnir Physics 6,
533 A972).

100
T

of course,deviatefront its soon

this its t!ie wavelength becomes comparable to
t/ie disittuees of the atoms. . .. The only thing which had to be lione was lo
adjust to she fact that every solid ofjunta dimensions contains ajiuite numfrc'r
of atoms and therefore has a finite mint her of free vibrations.... At low L'uoiujh

temperatures, and ttt perfect analogy to the radiation htw of Stefan-

Boltzmann ..., the vibrational energy contentof it solid will be proportional

P. Dcbye

The energy of an elastic wave in a solid is quantized just as the energy of an

electro magnetic wave in a cavity is quantized.The quantum of energy of an

clastic wave is calleda phovwn. The thermal average number of pitonons in an
elastic wave of frequency oj is given by the Planck distribution function, just

;is for photons:

1
C5}

We assume that t!ie frequency ofan elastic wjive is independent of theamiMttmle

ofthe elastic sixain. We want and heat capacityofiheelastic
to find the energy
waves in solids. Several of the resiiks obtained for photons may be carried
over to plionons. The resultsare simple if we assume th:tt the velocities of ail
elasticwaves are equal\342\200\224independent of frequency, direction of propagaiion,
and directionof polarization. Thisassumption is not very accurate, but it helps
account the general trend of the observed results in many
for solids, with a
minimum of computation.
Therearetwo important features of the experimental results: the heat capacity
of a nonmctallic solid varies as tJ at low temperatures, and at high temperatures
the heat capacity is independentof the temperature. In metals there is an extra
contribution from the conduction electrons, treated in
Chapter 7.

Number of Plionon Modes

There is no limit to the number of possible electromagnetic modes in a cavity,

but the number of elastic modesin a finite solid is bounded. If the solid consists
of N atoms, each with three degrees of freedom, lite total number of modesrs
3A?. An elastic wave has three possible po! matrons, a two transverse and one
longitudinal, in contrast polarizations of an electromagnetic
to the two possible
wave.In a transverseclasticwave the displacement of the atoms is perpendicular
to the propagationdirectionof the wave; in a longitudinal wave the displace-
displacement is paraiicl to the propagation direction. The sum of a quantity over all

modes may be written as, includingthe factor 3,

| JW ,
<*\302\253(\342\200\242*\342\200\242) C6)

by extension of A7). Here n is defined in terms of the triplet of integersnxt i\\yt iu,
exactly as for photons. We want to find ;iralI such that the total number of
elasticmodes ts equal to 3JV:

C7)

In the photon problem there was no cor espondinglimitationon the total

number of modes. It is customary to write D, after Debye, for nraaI. Then C7)
becomes

in\302\273D3
=
3;V; nD = FW/7!I'3. C8)

The thermalenergy of the phonons is, from A6),

 ,\\umbcr ofPho

or, by C6) and CS),

D0)

By analogy with the evaluation of A9), with the velocity of sound v written in

place of the velocity of light r,

V = .
{'in2twf2L)(xL/n!n-)-i J*V* D1)
\342\200\224~~^

where X =
ji/irii/Lr. For L3 we write the volume V. Here, with C8), the upper
limit of integration is

usually written as

,vfl
-
0/7
= fcsO/'t . D3)

where6 is called the Dcbye temperature:

0 = (hv/kB)Fn2N/VI \\ D4)

The result D1) for special interest at low temperaturessuch

the energy is of
that T \302\253
0. Here the limit .xD on the integral is much larger than umly, and .vo
may be replacedby infinity. We note from Figure 4,4 that there is little contri-
contribution to the integrand out beyond x = 10.For the definite integral we have

f\"^ __\302\243_-?- , D5)

Jo exp.x- 1 15

as earlier. Thus the energy in the low temperaturelimitis

proportionalto The
T4\302\273 heat capacity is, for i \302\253
kB0 or T \302\253
0,

D7a)
Chapter 4: Thermal Radiation ami Planck Distribution

T 17.78 - A
-\342\226\240\342\226\240
\342\200\224

E 13.33 A
i
A

^ 4.44
Y

0
\\A
3.99 5.32

r3, in K3

Figure 4.10 Low tempcralure heat capaciiy of solid argon, pioiicd against
TJ10 show Ihc cxcettent agreement whh !tie Debyc T1 law. The value of 0
from these daia is 92 K. Courlesyof L.1 Fincgold and N. E. Phiiiips.

In conventional units,

D7b)

This result h known as the Debye T1 !aw.*Ex peri menta! results for argon are
plotted in Figure 4.10.Representative experimental values of the Debye tem-

temperature are given in Table 4.1. The calculated variation of Cv versus T/6 is

plotted in Fig-jrc 4.11. The high temperaturelimit T\302\273 0 is the subject of

Problem II. Several related tiiermodymmiic
functions for a Debyc solid are
given in TabL* 4.2 and are plotted in Figure 4.12.

13.297 A912): 14,65 A9K).

 Aiimitr of Photon Modes

Lu 210

Jjg
7.

UJ 1

X UJ

EQ

pT <
UJ

e a.

(J
 Chapter 4: Thermal RaJhtion ami Planck Dim

25
i
^\342\200\224^\342\200\224

- 20 -

/
Figure-5.11 Heal capacity Cv of a solid,
according10ihc Dcbye approximation. The
vertical scale is in J mol~' K\"'. The
Iiori^onla! scaieis ihc temperature
normalized to the Debye temperature 0.The L\342\200\224

region of ihc TJ law is below 0.10.The

asymptotic value al high values of 7\"/1? is
24.943 Jmor1 K\021.
/

0 0.2 0.4 0.6 0.8 1.0 1.2

'able 4.2 Values of C,, S, U, ai id F on the Debye ihc ory. in unlls J moI\021 K\"

IT Cv S = k^o U,0 170

0 24.943 CO X
0.1 24.93 90.70 2402 - 666.8
0.2 24.89 73.43 115.6 -251
0.3 24.83 63.34 74.2 -137
0.4 24.75 56.21 53.5 -87
0.5 24.63 50.70 41.16 -60.3
0.6 24.50 46.22 32.9 -44.1
0.7 24.34 42.46 27.1 -33.5
0.8 24.16 39.22 22.8 -26.2
0.9 23.96 36.38 19.5 -209

1.0 23.74 33.87 16.82 -17.0:

1.5 22.35 24.49 9.1 -7.2:

2 20.59 18.30 5.5 -3.6.
3 16.53 10.71 2.36 -1.2
4 12.55 6.51 1.13 -0.4!
5 9.20 4.08 0.58 -0.2
6 6.23 2.64 0.323 -0.1
7 4.76 1.77 0.1S7 -0.0
8 3.45 1.22 0.114 -0.0
9 2.53 0.874 0.073 -0.0
10 1.891 0.643 0.048 -0.0
15 0.576 0.192 0.0096 -0.0
 Summary

20

0
10

-10

-20

-30

\024\302\2600 0.5 1.0 1.5

FiKiire^.12 Energy t/and free energy f s= I/- roof a

solid, according to tiit DcbyC theory. Tlic Dcbye temperature
of tlic solid is 0.

SUMMARY

1. The Planck distributionfunction is

for the thermal average number of photons in a cavity mode of frequency a

2. The Stefan-Boltzmannlaw is

'
V 15/iV

for the radiant energy density in a cavity at temperature t.

Chapter 4: Thermal Radiuiwn and Planck Distribution

3. The Planck radiation law is

h \302\2533

\342\200\224
r2c3 exp(/io)/t) i

for the radiation energy per unit volume per unit range of frequency.
4. The flux density of radiant energy is Ju \342\200\224
oBTA, where aB is the Stefan-
Boitzmann constantn1ks*/(i0hici.
5. The
Debye low temperature limit of the heat capacity of a dielectricsolid
is, in conventional uniis,

where the Debye temperature

0 s (hvjkB)Fn2$fvy'\\

PROBLEMS
1. Number of thermal photons. Show that the number of photons XXs\") in

equilibrium at temporal ure x in a cavity of volume V is

N = 2.404n~2K(t/Ac)s. D8)

i-rom B3) the entropy is a = Dn2F/45)(r//icK, whence <r/N

=s 3.602. It is
believed that the total number of photonsin the universe is 109 larger than the
total numberof titiclcons(protons,neutrons). Because both entropies are of
the order of the respective number of particles (sec Eq. 3.76), the photons
provide the dominantcontributionto the entropy of the universe, although
the particles dominau- ., c total energy. We believe that the entropy of the
pllotonsis essentially constant, so that Mie entropy of the universeis approxi-

approximately constant with time,

7. Surface temperature ofthi! Sun. The value of the total radiant energy Hilx
density at the Earth from the Sun normal (o the incident rays is called the solar
constant of the Earth. The observed value integrated over all emissionwave-
wavelengths and referred to the mean Eanh-Sim disiance is:

solar constant = 0.136 J s D9)

(a) Show thai the total rate of energy generation of the Sun is 4 X 10\026 J S\" *.
(b) From this result and .the Stefan-Boltzmann constant <rB = 5.67 x
10\"12J s~' cm'2 K\"\"\\ show thai the effective temperature of the surface of the
Sun treated asa black body is T ~ 6000 K. Take the distanceofthe Earth from

theSunasl.5 x 10!3 cm and the radius of the Sun as 7 x 10l\302\260cm.

3. Average temperature of t/te interiorof the Sun, (a) Estimate by a dimen-

dimensional argument or otherwise (he order of magnitude of the gravitationalself-
energy of the Sun, with AiQ = 2 x !033g and RQ => 7 x 1010 cm. The gravi-
gravitational constant G is 6.6 x iQ\"8 dyne cm2g~2,Theself-energy will be negative
referred to atoms at rest at infinite separation, (b) Assume ihat ihe total thermal
kineticenergy of the atoms in the Sun is equal to \342\200\224 limes
\302\243 the gravitational
energy. This is the resultof the virial theorem of mechanics. Estimate the average
temperature of ihe Sun. Take the number of particles as 1 x IG*7.This csUmaie
gives somewhat too low a temperature, because the density of tlie Sun is far
from uniform. \"The range in central temperature for different stars, excluding
only those composed of degenerate matier for which the Saw of perfect gases
does not hold (white dwarfs) and those which have excessively sniall average
densities(giants and supergiants), is between 1.5 and 3.0 x iO7 degrees.\"
(O. Siruve, B. Lynds, and H. Pillans,Elementary astronomy, Oxford, 1959.)

4. Age of the Sun. Suppose4 x lQ;6Js~! is the total rate at which the Sun
radiates energy at the present time, (a) Find i he total energy of the Sun available
for radiation, on the rough assumptions that the energy sourceis ihe conversion
of hydrogen (atomic weight L0Q7S)to helium(atomicweight 4.0026) and that
the reactionstops when 10percentof the original hydrogen has been converted
to helium. Use Einstein relation the =
\302\243 (AAf)c\\ (b) Use (a) to estimate the
life
expectancy of the Sun. It is believed ihat [lie age of the universe is about
10 x 109 years. (A good discussion is given in ihe books by Peebles and by
Wcinberg, died in the generalreferences.)
5. Surface temperature Earth.
of the Calculate the iemperatureofl hesurface
ofthe Earth, on the assumpiion ihat as a black body in thermal equilibrium it
renijiates us much thermal radiationas it receives from the Sun. Assume also
that ihe sin face of the Earth is ;it a constant jemporiittini over ihe day-night

cycle. Use 7\"o

- 5S00K; RQ = 7 x 10locm; and ihe I2arih-Sundislanwof
1.5 x IOlJcm.

6. Pressure of thermal variation. Show for a photon gas thai:

(a) p = -(cUfcV), - -^s/iiiluij/ilV)

, E0)
 l Radiat and Planck Oiildbnti,

where s; is the number of photons in the moJej;

(b) dojjfilV
=
-mjyV; E1)
(c) p = U/iV. E2)
Thus the radiation to 3 x (energy density).
pressure is equal
(d) Compare pressure the radiation with the kinetic pressure of a
of thermal

gas of H atomsat a concentration of t mote cm'3 characteristic of the Sun.

At what temperature (roughly) are the two pressures equal? The average
temperature of the Sun is believed to be near2 x tOT K. The concentration is
highly nonuniform and rises to near rOQmoiecm.\023 at the center, where the
kinetic pressure is considerablyhigher than the radiation pressure.
7. Free energyof a p/iot on gas. (a) Show that the parlhion function of a
photon gas is given by

where ihe product is over the modes \302\273.

(b) The Helmholtz free energy is found
direclly from E3) as

F-T][tog[t-exp(-AuiA/T)]. E4)

Transform the sum to an integral; integrateby parls to find

F = -n E5)

5. Heatshields. A black (nonreflective) plane at temperature Tu is parallel

to a black plane at temperature T(. The net energy flux
density in vacuum be-
between the two planes is Jv = aB{Tf - T*), where aB is the Stefan-Boltzmann
constant used in B6). A third black plane is inserted between the other two and
is allowedto come to a steady state temperature Tm. Find Tm in terms of 7'B
and T,, and show that the net energy flux density is cut in half because of the

presence of this plane. the heat shield and is widely

This is the principle of
used reduce
to radiant heat transfer. Comment:The result for N independent
heat shields floating in temperature between the pianes TM and T, is that the
net energy flux density is Jy = ciT^ - T,4)/(N + !)-
9. Photon gas in one transmission line of length
dimension. Consider a
L on

which electromagnetic waves satisfy the onc-dimcnsional wave equation

v2d2Ef3x1 =s c2E/ct2l where E is an electricfield component- Find the heat

capacity of the photons on the line,
w hen in thermal equilibrium at temperature
r. The emiiiicrulioiiof modes proceeds in ihe usual way for one dimension:
lake ilic soiulions siundmg waves as with zero amplitude ai cacli cud of ilic
line.
10. Hcitt capacity of iniergalaciic space. Sntcrgalactic space is believedto be
occupied hydrogen by atoms in a concentration =laionim~\\ The space is
alsooccupied thermal by radiaiion al 2.9 K, from the Primitive Fireball. Show
thai ilic ralio of ilic hcai capacity of mailer lo lhal of radiaiionis ~- 10'9.

//. of solidsin high temperature

Heat capacity limit. Show lhal in ihe iimil
T 0
\302\273 liie
capacity of a solid
heal goes towards die limit Cy \342\200\224\342\226\240
3A'\302\243B, in

conventional units. To obtain higher accuracy when T is only moderately

larger than 0, the heat capacity can be expanded as a power seriesin 1/T, of
the form

E6}

Determine the first nonvanishing term in the sum. Check your result by inserting
- 0 and
T comparing with Table 4.2.

/2. Heat capacity of photons andpltonotts. Considera dtelcciricsolid with a

Dcbye temperature equal to 100K atid with 10\" atoms cm ~3. Estimate the
lemperature at which the photon contribution to the heat capacity would be
equal to the phononcontributionevaluated at 1 K.

13. Energy fluctuations in a solid ai low temperatures. Consider a solid of N

atoms in the temperature region in which ihe Dcbye Ti law is vaiid. The solid
is in ihermal contact with a heat reservoir. Usethe resultson energy fluctuations

from Chapter 3 to show that the root mean square fractional energy fluctuation
IF is given by

(
E7)

Suppose that T = I0~2K;0 = 200K;and N * 1O1S for a particle 0.01cm on

a side; then $F p= 0.02. At !0\025 K the fractional fluctuation in energy is of ihe
order of uniiy for a dielectric particle of volume 1 cm3.

14. Heal capacity of liquid *He at low temperatures. The velocity of longitu-
longitudinal sound waves in liquid 4He at temperatures bctaw 0.6 K is 2.383 x 104cm
s\"'. There are no transverse sound waves in the liquid. The density is

0.145gcm~3. (a) Calculate the Debyc temperature, (b) Calculate the heat

capacity per gram on the Dcbye theory and compare with the experimental
value CK
=\342\226\240
0.0204 x T\\tn Jg\021 K*1. The T3 dependence of the experimental
Chapter 4: Thermal Radiation and Pfanek Distribution

value suggests thai phonons are Hit; most important excitations in liquid 4He
below 0.6 K. Note that the experimental value has been expressed per gram of
liquid.The experimems are due to J. Wiebes, C. G. Niek-Hakkenberg,and
H. C Kramers, Physica 32, 625 f !957}.

15. distribution
Angular of radiant energy flux, (a) Show that the spectra!
density of the radiant energy flux that arrives in the solid angle i!Q is
fuucos0*</n/47r,where 0 is the angle the normal to the unit area makes with
the incident ray, and i^ is the energy density per unit frequency range, (b) Show
that the sum of this quamity over all incident rays is \\aiu.

16.Image radiant object. Let

of a a lens image the hole in a cavity of area

An on a black object of area Ao. Use an equilibrium argument to relate the

product AuQtl QQare the solidanglessubtendedby the
to AaQ0 where Qtl and
leas as viewed hole from the
the object. This general property of
and from

focusingsystemsis easily derivedfrom geometrical optics. It is also true when

diffraction is
important. Make the approximation that all rays are nearly
parallel {al! axial angles small).
17. Entropy and occupancy. We chapter that the entropy of the
argtted in this
cosmic bodyblack radiation with time because the number
has not changed
of photons in each mode has not changed with time, although the frequency of
each mode has decreasedas the wavelength has increased with the expansion
of the universe. Establish the implied connection between entropy and oc-
cupattcy ofthe modes,by showing that for one mode of frequencyw the entropy
is a function of the photon occttpancy<<(s) only;

a = <s + l)log<5 + !) - <s)log<s). ES)

It is convenient to start from the partition function.

18. haxiropic expansion of photon gas. Consider the gas of photons of the
thermal equilibrium radiation in a cube of volume V at temperature r. Let the
cavity volume increase;the radiation pressure performs work during the expan-
expansion, and the temperature of the radiation wit] drop. From (he result for the

entropy we know titat an expatision. (a) Assume

iV1'3 is constant in such that

the temperature cosmic of lite

black-body radiation was
decoupled from the

temperature of the mutter when both were at 3000K..What was the radius of
the universe at that time, compared to now? If the radtus has increasedlinearly
with time, at wltat fraction of the present age of the universe did the decoupling
take place?(b) Show that the work done by the photons during the expansion

The subscripts i and / refer to the initial and final siatcs.

19, Reflective heat shieldand Kircbhoff's (aw. Consider a plane sheet of mate-
material of absorptivity it, e-mtssjvtty e, and rcllecttvjty r ~ \\ \342\200\224
a. Let the sheet be
suspended between and parallel with two black sfieets maintained at tempera-
temperaturesru und t,. Show that the net flux density of thermal radiation between the
black sheetsis (I - r) times the flux density when tiie intermediate sheet is
also black as in Probfem 8, which means with a = e = I; r - 0. Liquid helium

dewars are often insulated by many, perhaps 100,layers of an alumtntzed

Mylar film called Superinsulation.

SUPPLEMENT: GREENHOUSE EFFECT

The Greenhouse Effect describes the wanning of the surface of the Earth

caused by the interposition of an infrared absorbentlayer of water, as vapor

and in clouds, and of carbondioxidein the atmosphere between the Sun and
the Earth. The water may contribute as much 90 percent of the warming
effect.
Absent such a layer, the temperature of the surface of the Earth is
determined by the requirement of energybalancebetween
primarily the flux
of solar incident on the Earth
radiation and the flux of reradiation from the
Earth; the reradiationflux is proportional to the fourth power of the tempera-
temperatureof the Earth, as in D.26). This energy balance is the subject of Problem

4.5 and leads to the result Ts \342\200\224

{RsI^seV^Ts, where 7'\302\243is the temperature
of the Earth and Tsis that of the Sun; here/fjis the radius of the Sun and DSE
is the Sun-Earthdistance.
The result of that problem is TE \342\200\224
280 K, assuming T,=\302\273 5800 FC The
Sun is much hotter than the Earth, but the geometry (the smali solid angle
subtended by the Sun) reduces the solar iiux density incidentat ihe E;irth by a
factor of roughly (i/20)*.
We assume that the atmosphere is a perfectgreenhouse,
as an example
defined as anlayer that transmits al! of the visible
absorbent radiation that
falls oa it from the Sun, but absorbs and re-emits a!! the radiation (which lies
in the infrared), from the surface of the Earth. We may idealize the problem

by neglecting the absorption by the layer of the infrared portion of the

incident solarradiation,because the solar spectrum lies almost entirely at
higher frequencies,as evident from Figure 4.4. The layer will emit enerry flux

tL up and IL down; the upward Oux will balance the suiur i!ux 1$, Su UiJi

ft Is- The net downward flux will be the sum of the solarflux Is and the
**

flux lL down from the layer. The latter increases the net thermal Oux incident

at the surface of the Earth. Thus

lEt^h + h-ns. E9)

where
l\302\243g
is the thermal Oux from the Earth in the presenceof the perfect
greenhouse effect. Because the thennal flux varies as T4, the new temperature
of the surfaceof the Earth is

=
T\302\243s
\302\253=
2\302\273/\302\253rfi A.19) 280 K ~ 333 K, F0)
so that the greeahouse warming of the Earth is 333 K \342\200\224
280 K = 53 K for
this extreme example.*

\342\200\242
For detailed discussions see Climale change and Climate change 1992, Cambridge U.P., 1990
end 1992: i. T. Houghton ct aJ, editors. .
Chapter 5

Chemical Potential and

Gibbs Distribution

DEFINITION OF CHEMICAL POTENTIAL 119

Example: Chemical Potential of the Idea! Gas 120

Internal and Total Chemical Potential 122
Example: Variation of Barometric Pressure with Altitude 125
Example: ChemicalPotentialof Mobile
\"'\"
Magnetic Panicles

in a Magnetic Field 127

' -
\342\226\240
Example; Batteries 129
Chemical Potential and Entropy 131
Thermodymtmic Identity 133

GIBBS FACTOR AND GIBBS SUM 134

Numberof Particles 139

Energy 140

Example: Occupancy Zero or One 140

Example: Impurity Atom !omz;ition in a Semiconductor 143

SUMMARY 144

PROBLEMS 145

1. Centrifuge 145
2. Moleculesin the Earth's Atmosphere 145
3. Potential Energy of Gas in a Gravitational Field 145
4. Active Transport 145
5. Magnetic Concentration 145

6. Gibbs Sum for a Two LevelSysSem 146

7. States of Positive and Negative Ionization 146

8. Carbon Monoxide Poisoning 146
9. Adsorption of O2 in a MagneticField 147

10. Concentration Fluctuations 147

11. Equivalent Definition of ChemicalPotential 148

12. Ascent of Sap in Trees 148

13. Isentroptc Expansion
148

14. Multiple Binding of O2 148

15. ExternalChemical Potential .... 149
 Potential
\342\226\240al and Gibbs Distribution

(H. We found earlier thai Tor a single system S in thermal equilibrium with a
reservoir <2t, ihe Helmholtz free energy of & will assume the minimum value
compatible wiih the commontemperature x and wiiii oiher restraints on the
system,
y, such as the volume and the number of pparticles. This result pp
applies

equally to ihc combined\302\243,+ S: in equilibrium with (R. in diiTusive equilib-

equilibrium between S, .mdpaiii^lc diaiiibution
^2, the N,,.V\302\273 between ihi5 sysicms

makes t!io toial Hchulioltz free energy

F= h\\ + F2 - t/( + t/2 - T(ff, + <T>) A)

a minimum, subject to N = jV, + jV2

= constant. Because N is constant,She
Heimholtz free energy of the combined system is a minimum with respect to
 Definition of Chemical Potential

System .Sj

t*\"Ener\302\260y exchange\"\"}

Figure Example of Iwo systems,Sx ;mdX., in ihcrmal

5.1 conlacl with each oihcr
and wiih a large reservoir Of, forming a closed total system- I)y opening the take,
S{ and ^j can be brouglit in tlillusive contact wliilc remaining at the common
tcmpcraiurc r. Ttie arrows at tlm valve liave been drawn for a net panicle transfer
from \302\243j
lo S2.

variations 5Nt = -5N2. At the minimum,

tlF - (cFi/cN^^lNi = 0,
+ lcF2/dN2)sc!N2 B)

with K[, K2, also held constant. With (!Nt

= ~-tlN2, WG have

(/F =
[(cfj/t'iV,),
- (SF2/cNl),yNl - 0, C)

so Hutt at cqutlibriuni

((Tj/oV,), - (cF3/cN2)t. (\342\226\240\30

DEFINITION OF CHEMICALPOTENTIAL
We define the chemical potential as
(/;0

I I

E)
Chapter 5: ChemicalPotential and Gibhs Distribution

where ji is ihe Greek letter niu. Then

'-
/'I t'l

expresses ihe condition for ditTusive equilibrium. If/(, > ;i2, we sec from C)

thai elF will be negative when diVt is negative: When panicles are transferred
from 5, to 5j, ihe value of dN \\ is negative, and tlN2 is positive. Thus the
free energy decreases us particles flow from ^i to &2; ilitit 's. particles (low
from the system of high chemicalpotentialto the system of low chemical
potential. The strict definition of /i is in terms of a difference and not a deriva-
derivative, because particles are not divisible;

)
=
F(t,V,N)
- F{x.V,N- 1). F)
The chemical potential regulates between systems
the particle transfer
in

contact, and it is
fully importantas which rcguhucs the
as the temperature,

energy transfer. Two systems ihat can exchange both energy and particles are

in combined thermal and ditTusive equilibrium when their temperaturesand

chemical potentials are eqtial: i[ = t2;/i; = ji%.
A difference in chemical potential acts as a driving forcefor the transfer of

particles just as a differencein temperatureacisas a driving force for the transfer

of energy.
If several chemicalspeciesare present, each has its own chemical potential.
For species
j,
G)

wherein the differentiation! TTumbcrs of all particles are held constant except
for the species j.

Example: Chemical potential of the Ideal gas. In C.70} showed that ihe free
of Ihe monatomic ideal gas is

- (8)
/logZi logN!] ,
 Definition of Chemical Potential

is the partition function for a single panicle. From (8),

A0)

If we use the Stirling approximation for A\"! and assume tlutt v,e can differentiate the
factorial,we fold

= log A\" + [N + -1)-- - 1 = togtf + \342\200\224

. (II)

which approaches log iV for large values of \\. llcttcc the chemical potential of the ideal
gas is

,< = -rUogZ,
- log.V)

or, by (9),

A2a)

2 ts
where n \342\200\224
NjV is the concentration of particles ami na
= (A/r/2nfi2K the quantum
concentration defined by C.63).
Ifweuseji = F{N) - F{N
-
i)froin.{6)as the definition af/j, we do not need to use the
From (S) we obtain = - with
Stirling approximution. ji -i[log2, logjV], which agtces
A2). The result depends on the concentrationof particles, not on their total numheror on
the system volume separately. By use of ths ideal gas law p = nr we can write A2} as

= A2b)
/t Ttog(p/tiiti).

The chemicalpotential increases concent mi ion of particles increases.

as the This is what

we expect intuitively: particles to

flow from
higher lower chemical potential, from higher to
lower concentration. Figure 5.2 shows the dependence on concentration of an ideal gas
composedof electrons or of helium atoms, for two temperatures, the boiling temperature
Chapter 5: Chemical Potential andGibbs Distribution

Figure 5.2 The concentration dependenceof/*, in units o! r, of an ideal gas

composedof dectroio.jrhelium atoms, at 4.2 K and 300 K..To be in the classical
regime with n \302\253
nQ, a ^as must have a value of - ^i at least t. For electrons this is

satisfied oulv for concentrations apprccwhly le\302\253lluin those in metals, as in ihe

range of lypical semiconductors. For gasesit is always satisfied under normal
conditions.

of liquid licimin ill atmospheric pressure, 4.2 K, and room icmpcraturc, 300 K. Atomic
and tnolccubr jtascs aiwjjs lave ncgaiivcchemical potentials unJer plijiically tciilii^blc
condiiioas: at classical concernrations such ihnt nfnQ \302\253
!, we soe from A2) iliat /i is

ncgaiive.

Internal and Total Chemical Potential

The best way to understand the chemical potential is to discuss diffusive
equilibrium in Ihe presence of a potential step that acts on Ihe particles. This
 Internal and Total Chemical Potential

Figure 5.3 A potential step between two

systems of chargedpaniclescan be established

tiie voltage polarity shown, the potential

energy of positive parlic'es with charge q > 0

in system i, would be raised by qAY wild

respect !o J2. The potential energy of negative

particles would be loweredin 3, with cespect

problem has wide application and includesthe semiconductor p

\342\200\224
n junction
discussed in Chapter 13. We again consider hvo systems, Sx und &->t al the

same temperature and capable of exchanging particles,but not yel in diffusive

equilibrium. We assume that initially fix > /(j, and we denote the iniiial non-

equilibriumchemical potential difTcrence by A/j(iimial) = ;/2 - ^i- Now let a

difference in potential energy be establishedbetweenthe two systems, such

iliat the potential energy of each panicle sysiem

in
Si is raised by exactly
Af[(im'tial) above its ininal value, if Ihe particles carry a charge qt one simple
way to establish this potentialstepisto apply between the two systems a voltage
A I' such lhat

A3)

with the polarity shown in Figure 5.3. A difference in gravitational potential

also can serve asa potentialdifference: when we raise a system of particles each
of mass M by the height /i, we establish a potential differenceMgh, where g is
the gravitational acceleration.
Once a potentialstepispresent, the potential energy of ihe patrides produced
by this sfcp is included in (he energy U and in the free energy F of the system.

If in Mgurc 5.3 we keep the free

energy system of step raises the
S2 fiNed, ihe
free energy of Sx by /Vs A;i(mitial) *=
AV/ A!7 relative to its initial value. In
ihe language of energy states, to the energy of each suite of .Si the potential
energy ,Yt A/i(initial) has been added. The \"insertion of the potential b^rier
Hveificd by (B) mises ilie chemical potential of $x by A/i(!il!ti;il). to male the
fin::!i.-hciiiiL:;il puk-ntuil of ^, c\302\253i\302\273:il
to ih:lt oi\\S,:

/affinal) = ;(,(initial) -f [,..(initial) - /i,(inilial)]

A4)
When the barrier was inserted, pj was held fixed.Thus the barrier gA
systems into diffusive
\342\200\224
/^(initial) /(i(initial) brings the two equilibrium.

The chemical potential is equivalent to a true potential energy; the

difference in chemical potential between two systems is equal to the
potential barrier that will bring the two systemsinto diffusive equilibrium.

This statement a feeling for the physical

gives us effect of the chemical poten-

potential, and it forms for the measurement of chemicalpotentialdifferences

the basis
between two systems. To measure ft2 - /<,, we establish a potential step
betweentwo systems that can transfer particles, and we determine the step
height at which the net particle transfer vanishes.

Only differences of chemical potential have a physical meaning. The absolute

value of the chemical potential dependson the zero of the potential energy
scale. The idealgas result A2) depends on the choice of the zero of energyof a
free particle as equal to the zero of the kinetic energy.
When external potential steps arc present, we can expressthe total chemical

potential of a system as the sum of two parts:

/' = iv = +ft,,-
;\342\226\240\342\200\236, A5)

Here /jtM is the potential energy per particle in the external potential,and jiial

is the internal chemical potential* definedas the chemical potential that would
be present if the external potential were zero. The term /iCM nmy be mechanical,
electrical, magnetic, gravitational, etc. in origin. The equilibriumcondition
Pi \342\200\224ca'i
Hi be expressed as

Apeil = -A A6)

Unfortunately, the distinctionbetween external and internal chemica! potential

sometimes is not made in the literature.Somewriters, particularly those working
with charged particles in the fieldsof electrochemistry and of semiconductors,

often mean the internal chemical potential when they use the words chemical
potential without a further qualifier.

The total chemical potential may be called the electrochemical potential if

the potential barriers of interest are electrostatic.

Although the term electro-

potcnsjal. He recognized
\342\226\240
Gibbs called n the potential and it,*, ihe intrinsic that a voltmeter mea-
'
measures differences in fi. .
 Internal and Total Chemical Potential

SysicmB)

Figure 5.4 A model of ihe variation

aimcispliericpressure\\>.iih altitude: i
\\olumcs of gas at different heights in
gravitaiiona! field, jn iherma! and di!
con wet.

System (!)

chemicalpotential is clear unambiguous, and we shall tisc \"total chemical

potential.\"The use of \"chemical potential\"' without an adjective should be
avoided tit situations in which any confusion about tis meaningcouldoccur.

Example; Variation of barometric

pressure whhahhutte. The simplest example of the
diffusive equilibrium bciwccn
sysiems in difTcrcm external potentials is itte equilibrium
bciwccn layers ;lt different llcigliis of ihe Canh'satmosphere, assumed lo be isothermal.
Tim rcul uimosplicfc is in imperfect equilibrium: ii is'cunstaiiily upsa by Hitititoroloeicut
processes, faoih in the form of macroscopic air movemems and of strong temperature

grudiunis from clouii fonn;uion, ;inii becauso of heal input from liiil ground. We may
make ;in ;ippro.\\imaic model of the aimosphcrc by KtMliiia the dilL-iem air layers as
syslemsof idea! gases in ilierilia! and diftusive eiiuilihrium ^iih each oilier, in diHerem
exieroul poicnlials (Figure 5.4}.If we place ihe zero of the poieinul energy ai ground \\c\\c\\,
the poiemial energy per moleculeai heighi Ji is Afyfi,whcrc.\\f is ihe particle massand g ihe
gravitational acceleialion. The internal chemical potential of ihe parlidesis given by A2}.
The loial diemical poiemial is

{17}
In equilibrium, this musi be independent of {he hcidil. Thus

+ - ,
Tlog[i.(/t)/H0] A/y/i rlog[ii@)/nQ]

and ihc conceniralion \302\253(/t).alhcijjlU h satisfies

(IS)
 Chapter 5.-Chemical Potential and Gibls Dhtnliution

1.0 1

0.5
\\

0.2

o.i
\\
V
i
2 0.0S
figure 5.5 Decrease of atmospheric pressure
v-iih ahiiude. The crosses represent Ihc average
atmosphere as sampled on rocket fliyhis.
The concerting siraight Vine lias a slope
corresponding lo a icmpcraiure T = 227 K. h
X

\\

\342\200\224

M
0-10 20 30 40 50
in km
Heighi,

The pressure of an ideal gas is proportional lo llieconcenlration; therefore Ihe pressure

aullilude li is

p(/i) =.
p@)exp(-.V9li/t) = p@)exp(-/i/'iJ- A9)

Thl^ &s itio uuromoLrtc conation Ti i*i\\ os ^Jtc ilc^czitjciicc 01 liic pressiifcon uli^iLide
pressure
in an isoihermat anuoipliere of a single chemical species. Al ilie cliaracierisiic Mght hc =
t/A/g ihe .-.unospi^er-c pressure decreases fay ihe fraciion e~l =3 0.37. To esiimaie Hie
characteristic fietght, consider an isoihermal atTuosphere composed of nitrogen nioiccuies

wiLliiinioiecular weigh! of 28.Tliema^orail .V^ niolecuie is 48 x 10\" \"gill. At a teiliper.l-

iureof :90KiIic value of r = kBT is 4.0 x 10\" l4crg. \\W\\nj = 9K0L1HS\021. the d1.1r.1t-
icrisiic iieiijlii Jit is S.5tm, approximately 5 mites. Li^Uiermolecules, H, and He, will
t\\ictul fatthcr dp, iiut these Ivavc hrgeiy cscipctl from ilic iiiiiinspUufc: see Probicm 1.
11UC.U1-.C ll.o UanhS LiiiiiO^pticrc i> not ;n;tiir.ittly iwitlicniiiit, ni/i)ft;is ;i iitoic a'ttipliaital
behavior. Fiyuie 5.5 is :i loyatiifunic jjloi oi\" pressure tfatj bciv^un 10 and 4QKiloiMcttrs,
iaken on rocket flights. The data potnis f;i!i near a siraighi fine, suggesting roughfy iso-
 vtl and total Chemical Pot

thermal behavior. Tlie straight line connecting the data points of Figure 5.5 spans a pressure
range jj{/ij):pl/i,J
= 1000:1, over an altitude range from ft, = 2km io A, = 43km. New,
from A9),

so that the slope of the line is Mg/x, which leads to T ~ x,'kB

\302\253
227 K. The non-intersection
of tltc observed eurve wish !hc point k ~ 0, p(li),'p{0) \302\253
I, is caused by the higher tempera-
at
temperature lower aliiiudes.
Tlic atmosphere consistsof
one species of gas. In atomic
more than percent, the com-
composition of dry air at ica A'j. 21 pet Oz. and 0.9 pet Ar; oilier constiiuems
fevel is TS pet
account for pci each. The water
iess than 0.1 vapor content of tlie aimosphcre may be

appreciable: at T ~ 300K B7\"C}_ a relative humidity of 100 pet corresponds to 15 pet

H,O. The carbon dioxide concentration varies about a nominal value of 0.03 pet. In an
ideal static Uolhenrtal atmosphere eadi gas would be in equilibrium wftli iisclf. The con-
concentration of each would fall off with a separaie Boltzmann factorof the form cxp(
- -\\/y/i/t},

with M the appropriate molecular mass. Becauseof tlie JiiTerences in mass, ihe difTcrcnt

p^insiTrii^itic T *}\\ tiff u\\ /iifrprcnl nk*c

Example: Chemical potential of mobile magnetic field. Consider

magnetic particles in a
a system of .V identical particles each m. For simplicity
with a magnetic
suppose moment
each moment is directed cither parallel f or antiparalld [ io an applied magnetic field B.
Then the poiential energy of a f particle is - iufl, and the potential energy of a 1 particle is

We may treat the particles as belonging

4-ii]\302\243i. to the two distinct chemical specieslabelled t

and i, one vhh external chemical potential ;in,(|J = -mB and the other with jjm,U) = \"iB.
The particles f and 1 are as distinguishable as Uvo difTerent isotopes of an clement or as two
different elements; we speak of f and 1 as distinct species in equilibrium with each other.
The internal chemical potentials of the particles viewed as ideal gases with concentrations

n, and iij are

ill potentials are

If iltcrti:iM\302\273\302\253:lK-|k-lJ !t\\:nivs iintwi'iiittKlfovcrtbtf vo!ui\302\273c^iltcsyslciH.llici-.-:-.vt.ij.H

it. mtht vary out \\\\w \\ wlumc in unlcr to ut:tintaii) j cotiMjisl unal clicnnt.it i- \342\226\240\342\226\240
Mi ,i

out i|ic volume irigmo 5.6).(Tlie total chemical potential of a species is eoitstam iiiJc
dent of posiiion, if there is free diffusion of particles within the volume,) Becausethe
Chapter 5: Chemical Potential and G'thhs Dhtribut

---

\342\200\224\342\200\224\"

Iff' 1GIU
\342\200\242
ion (i, in particles ciir3

Figure 5.6 Dependence ofihe chemical potential of a gas of magnetic

pari ides on ihe concentration, at several values of the magnetic field

intensity. Ifn = 2 x iO7 cm\021 for I! ~ 0, ihcn ai a point \302\253here B \342\226\240=
20
kilofiauasl2iesb)ihccona:nlraiionwillbe2 x !09cm\023.

species in equilibrium have equal diemioil poientiais,

lUl) = consiant - ;i,01(|). B3)

The desired solutions of {22)and B3) are easily seen fay substitution to be:

\302\253,{B)
-
in{0)exp(mB/t); n^B) = ^\302\253@)exp{-)nB/i) , B4)

where ti@} is tiie total concentration ii[ 4- nt at a point where the field B = 0. The total
concentrationat a poini at magnetic field S is

n{B) \302\253
n,{B) + ji,(B) = Jn@)[exp{jHB/T) + exp{-\302\273)B/T)];

n(B)
=
n{0)cosh{mB/T) * n{0)M 4- + \342\200\242
\342\200\242
-Y B5)
^-

The result shows [he tendency of magnetic panicles to concentrate in regions of high

magnetic Held intensity- The fujictionai form of ihc result is not limited to atoms wi[h two

magnetic orientauons, but is applicable to fine fecromagncfic particles in suspension in 3

colloidal solution. Such suspensions are used the laboratory in the siudy in of f he magneiic

flux strucfure of superconductorsand fhe domain strucfure of ferromagnetic materials.In

engineering, the suspensions ace used to tcsf for fine structural cracks in high strength sfcel,
such as furbine blades and aircraft landing gear. When fhese arc coated with a ferromagnetic
 Internal and Total ChemicalPotential

suspension and placed in a magnetic field, flic particle concentration becomes enhanced at
ttie intense fields at the edges of the crack.
In the preceding discussion we added to /<\342\200\236,the internal chemical potential of ihe
particles. If the
particles were ideal gas atoms, /iml would be given by A2). Tlie logarithmic
form for /iinl is not restricted to id^al gases,but is a consequence of the conditions iliat the
particles do not interact and that their concentration ii sufficiently low. Hence, A2) applies
to macroscopic particles as well as to atoms that satisfy these assumptions. The only
difference is the s;tlne of the quantum concentration n,,. We can thereforewrite

= t log it -f constanl
/'iM , B6}

where the constant \342\200\224 does

t log \302\273,,)
(\342\226\240= not depend on the concentration of the puctielcs.

Example; Batteries. Oneof

vivid examples of chemicalpotentials
the most and potential
steps w the hi the familial lead-acidbattery
electrochemical battery, the negative electrode
consists of metallic lead, Pb, and the positive electrode is a layer of reddish-brownlead
oxide. PbOj, on a Pb substrate. The eltclroiics ari: ininwisiid in ditulod sutfurie acid,
H.SCU, which is partially ionUai into H* ions (protons) and SG4~~ ions (Figure 5.7}.

in the discharge process both tlie metallic Pb of the negative electrode and the PbO.

of the positive electrode arc converted to Ie;td sulfate, PbSO4, via the two reactions;'

Negative electrode:

Pb + SO4\"\" -+ PbSO.,+ 2e~; B7a)

Positive electrode:

PbO2 + 2H+ + HjSO- + 2e\"-+ PbSO4 + 2H2O. B7b)

\"
Because of B7a)the negative electrode acts as a sink for SO*~ ions, keeping the internal
chemical potential ji(S04\"\"\") of the sulfafe ions at the surface of the negative electrode
lower than inside the electrolyte (sec Figure 5.7b). Similarly, because of B7b) the positive
electrode acts as a sink ions, keeping the internal
for H+ chemical potential /((H1\") of 'tie
hydrogen ions lower at the surface of ihe positive electrodethan inside the electrolyte. The
chemical potential gradients drive the tons towards the electrodes, and they drive the
electrical currents during the discharge process.
If the battery terminals arc not connected, electrons are depleted from the
positive
electrode and accumulate in the negative electrode, thereby charging both. As a result,

electrochennca! potential steps develop at the electrode-electrolyte interfaces, steps of

exactly the correct magnitude to equalize the chemical potential steps and to stop the
diffusion of ions, which stops the chemical reactions from proceeding further. If an external

current is permitted to flow, the reactions resume. Electron fiow directly through the
electrolyte is negligible, because of a negligible electron concentration in the electrolyte.

\342\200\242
The reactions given are net reactions. The actual reaction steps are more complicated.
 clcclrodc
(\342\226\240f)

PbO, i l>b

I
T T
(b).

5-igurc 5.7 (ajThekjJ-aciJ bailcry coniists of a Pb anj a PbO2 cicctrotic ilnmclsed in

parlialiy ioni/cd U^SOj. One SOI\" ion coii\\crfs one Pb atom into PbSOt + 2e~;
T
two H ions plus one im-ionizcd HjSO^ molecule convert one PbOj moltrcul^ imo
\"
PbSO4 + 2HjO,Lii isiirning Iwo ciccirons. (b) The eiectrociiemicaipokntials for SOI
and H* before the development ofimcfiia! poltnltai barriers thai slop the dilTuston
and ihe chemical reaction, (c) The eicctroiuticpoieuliai y(.\\) after the formation of the
barrier.
 Chemical Potential and Entropy

During I he
process the reactions opposile lo B7a,b)
charging take place, because now an
cMornai voiUigc Eliai generates elect rostalk [wicin
is ;i}>[i!ied b I steps ;H ihc surfiigc t'f Use
ei^mMc of such mugnituilti us lo reverse ihc s!ytl of Hie (toUi!)ciieiiik;ii poiciiliiit gradients,
ami Iwik-u the diction of ion How,
U'c denote by A K_ and A f. the difTcrenccsin dectcostaitc polcmial of the negative and
posilncclcclrodcsrelative to ihc common ciectroiyie. Because the suifute ions curry two
negative charges,diffusion will slop when

\342\200\224 =
2gAK_ A/i(SO4\"\.") BSaJ

DifTusion of the H+ ions wi!i stop when

+ ^AK+ \302\253
A/i(//'). B8b)

The two polemics AK_ and Al'+ are called ha!f-cc!i potentials or half-eeil EMF's

(electromotive forces); their magnitudes are known:

AV_ = -0.4voll; Aft \302\273

+1.6volt.

Tiic lolai electroslalic polcnliai difference developed across one full cell of ihc bniicry,
as required to stop the diffusion reaclion. is

AK = AK+
- AK_ \302\253
2.0voli. B9)

This is ihc opcn-drcuitioitage of EMFof the battery. Il drives ihc electrons from the ncca-

live lenninal lo the positiveicnr.ma!,when ihc iwo are connected.

We have ignored free electrons in tha electroljle. The polenlial steps tend to drive
electrons from the negative elecirodesinto the electrolyte, and from the cleciroiyie into ihe
posilive electrode. Such an electron current is present, but the magnitude is so small as to be
practically negligible, because the concentration of elcclrons in the electrolyte is many
orders of magnitude less than lhal of the ions. The only effective electron (low path is

through the external connection between ihe electrodes.

Chemical Potential and Entropy

In E) we defined the chemicalpotentialas a dertvathe of the Hclmlioltz free

energy. Here we detivc an alternate relation, needed later:

C0)

This expressesihe raliopi/x as a derivative of ihe entropy, similar to tlte way

1/r was defined in Chapier 2.
Clmpler5; Chemical Potential and Cibbs Distribution

To derive C0), considerthe entropy as a [unction of the independent variables

U, V, and N. The differential

+ ^ <w C1)
cU

gives the differentialchange ofthe entropy Tor arbitrary, independent differential

changes </t/, t/K, and rfJV. Let dV = 0 for the processes under consideration.
Further,select the ratios of rf<r, c!U, and i/N in such a way that the overall
temperature change dx will be zero. IT we denote these interdependent values
otda, dV, and dN by {&a)t, FU)t and (<5N)rl then dx = 0 when

After division by {5N)r,

C2)

The ralio {Sa)J(SN)lis (fo/5N),,and D[/),/(JW), is (dU/dN),, all at conslant

volunie. With the original definition of 1/t, we have

C3)
dNj,,
This expresses derivative a at constant U in terms oTderivatives at constantt
By the original definition of the chemical potential,

\023 ~ C4)
[H, w.,

and on comparison with C3) we obtain

C5)

The two expressionsE) and C5) represent two differentways to express the
same quantity ft. The difference between them is the following.In E), F is a
 Chemical Potential am! Entropy

Table 5.1 Summary of relations expressing ti-.c temperature

partial derivatives of liic cm ropy cr, liic energy U, and liic free
energy F, witii a, U, and F given as functions of their itatur.il

independent variables

o(U.V,N)

(IU\\ , is independent
variable
\\ia)rtl

y,,

function of its natural independent

variables x, V, and N, so that n appears as
a function of the same variables. In C1) we assumed a = a(U,V,N), so that

C5) yields n as a function of U, V, N. The quantity fi is the same in both E)

and C5), but expressedin terms of different variables. The object of Problem1i
is to find a third relation for p:

C6)

and in Chapter 10 we derive a relation for p asa function of t, p, and N. Table 5.1
compilesexpressions Tor i, p, and ^ as derivatives of o, U, and F. All forms
have their uses.

Tlicvmodynamic identity. We can generalize the statement of the Ihermo-

dynamic identity given in C.34a) lo include systems in which the number of

particles is allowed lo change. As in C1),

C7)

By use of the definition B.26)of i/r, the relation C.32) for p/r, and the relation
fi/i, we write da as .
-
C0) for

da = dU/x + pdV/x
- pdN/x. C8)
Chapter 5: Chemical Potential and Gibbs Distribution

This may be rearranged lo give

dV = xJs - pdV + ;u|jv , I C9)

which is a broader statement of the ihermodynamic identity than we were able

to developin Chapter 3.

GIBBS FACTOR AND GIBBS SUM

The Boltzmannfactor, derived in Chapter 3, allows us lo give the ratio of the

probability that a system will be in a state of energy Et (o the probability the

system will he in a state of energy t2, for a system ii\\ thermal contact with a
reservoir at temperature t:

P(z2)

This is
perhajtls
the best known resuh of statistical mechanics. The Gibbs factor
is thegenecauzauon of the BoHxmann factor lo a system in thermal and diffusive
contact with a reservoir at temperature j and chemical potential p. The argu-
argument retraces much of that presented in Chapter 3.
We consider a very large body with constant energy Uo and constant particle
number N0.The body is composed of two parts, the very large reservoir <R and

the system &, in thermal and diffusive contact (Figure 5-8), They may exchange
particles and energy.Thecontact assures that the temperature and the chemical
potentialof the system are equal to those oftiie reservoir.When the system has
. iV
particles, the reservoir has Nu - M particles; when ihe system lias energy e,
the reservoir has energy C/o
\342\200\224
To
e. obtain the statistical properties of the
system, we make observations on identical copies of the system
as before +

reservoir, copy one accessible Tor each

quantum slate of the combination. What
is the probability in a given observation that ihc system will be round to con-
contain N particles and to be in a stale s of energy \302\243j?
The stale s is a state of a system having some specified number of panicles.
The energye](iV) is the energy of the state s of the A'-particIc system; sometimes
we write only e,, if ihe meaning is clear. When can we wriie ihe energy of a

system having A' particles in an orbital as -V times ihe energy of one pur tide
in the orbital'.' Only when so
interactions between Ihe particles are neglected,
ihat the particles may be treated as independentofeachother.
 Figure 5.8 A system
iit thermal and diffusive conlacl wiill
a large of energy anti of panicles.
reservoir Tile total system
<H + S is tnsulaicd from the external world, so thai ihe

total energy and the total number of particlesare consianl.

The icmperamre ofihc syslcm is equal to tile lempcrature
oflhc reservoir, and i lie chemical potential of the sysiem is
equal to the chemical potential of Ihe reservoir. The syslcm
may bs as small as one atom or it may be macroscopic, bui
ihe reservoiris always to be thought of as much larger lhan
lite system-

Let P[NtEs}denote the probability the system has that

particles and is in jY

a particular stale s. This probabilityis proportional to number of accessible the

stales of the reservoir when the stateof sysiem is exactly specified. That
the

is, ir we specify the state of \302\243,

the number oraccessible states of (H + ^ is just

the number of accessibleslatesofO?:

\302\273((H+ S) = gift) x 1. {41)

The factor ! reminds us that we are looking at ilic sysiem S in a single spiciixd
stale, The y(<Jl)
stales of the reservoir have No - N particles and Ikivc energy
Uo - e,. Because
the system probability P{N,i:J is proportional to Ihe number
stalesof
of accessible the reservoir.

-
NtU0 - zt).
Chapter 5: Chemical Potential and Gibbs Diitrihufit

fit

Particles
- -
i\\'o ,V, Panicles ,VU

\342\200\224 -
Energy UQ Ft Energy Uo

Panicles A\\ Particles

Enemy r, Energy ,
(a) (b)
and dirTusive contact with the system. In (a) tile

to it. In {b] the system is in quantum state 2, and the reservoir has g{N0 - A'j, Uo
-
\302\243;

stales accessible to it. Because we have specifiedthe exact state of the system, the total
number of states accessible 10 01 + i k just the number ofsiulcs accessible tool

Here g refers to the rcsetvoiraloneand depends on the number of particles

in the reservoir and on the energy of the reservoir.

We can express D2) as a ratio of two probabilities, one that the system is in
state 1 and the other lhat the system is in state 2:

g(N0 --JV,,[/0 - e,) D3)

j

where g refers to the state of the reservoir.

The situation is shown in Figure 5.9.
By definition of the entropy

s(N0,y0)
=
ejpOfNo.f,,)] , D4)

so that the probability ratio hi D3) may be written as

D5)

= eXp[\"(N\302\253
\"
N\"y\302\260
>ffel)
D6)
Here, Act is the eniropy difference:

Ac h a(N0 ~ NUUO
-
e,) - a[N0 - N2,U0
-
e2). D7)

The reservoir is very large in comparison with the system, and Ac may be
approximated quite accurately by the firsl order lerms tn a series expansion in
the [wo quantities N and that
\302\243 relate to the system. The entropy of the reservoir
becomes

-
N,U0 ~i) D8)

For A<? defined by D7) we have, to the first order in iVE

\342\200\224
N2 und in e, \342\200\224
c->t

E0a)

by our original defmilion of the temperature. This is written for the reservoir,
bin the system will have the same temperature. Also,

K
(?e'
E0b)

by C0).
The entropy difference D9) is

(N,
- Nt)n (t, - E1)

Here Aa refers to the reservoir, but Nit A'^, \302\243lt

t] refer to the system. The central
result of statistical mechanicsis found on combining D6) and E1):

E2)
Chapter 5; Chemical Potential and Gibbs Distribution

The probability ratio of two exponential factors, c;ichof the

is the form

cxp[(A'/j e)/t],
-
A term of this form is calleda Gibbsfuctor. The Gibbs factor

is proportional to the probability that the system is in a state 5 of energy e,

and number of particles N. The result was first given by J. YV. Gibbs, who
referred to it as the grand canonical distribution.
The sum of Gibbs factors,taken overall states of the system for al! numbers
of particles,is normalizing the facior that converts relative probabilities to
absoluteprobabilities:

. exp[(A'/i
-
E],VJ). r]. E3}

This is called the Gibbs sum, or the grand sum, or the grand pan it ion function.

The sum is to be carried out over all states of the system for all numbers of
particles: this defines the abbreviation ASN. We have written e, as eJ(:V, to

emphasize the stale on the number

dependence of the
of part icles .V. That is,

c,|.v,is ihe energy state s(N) of ihe exact A'-particie

of the hamiitonian. The
term N = 0 must be
included; if we assign its energy as zero, then ihe first
term in ^ w'-' be 1.

The absoluteprobability that the system will be. found in a state Nlt e, is
given by ihe Gibbs facior divided by lite Gibbs sum:

E4}

This applies temperaturet

lo a system chemical lhat is ai and poieinial ji. The
ratio of any two P's is consistent our cenlral result with E2} for lite Gibbs
factors. E2} gives ihe correct
Thus relative probabilities for the stales A',, s,
and jV2,\302\2432.Thesum of ihe probabilities of all stales for al! numbers of par* icles
of tlte system is unity:

- 1 155)
\342\226\240
f

by ihe definition of 0-. Thus E4) gives the correci iibsuime probability.*

p.iiiictiljrl)- IicIpM. The nuriliod us,cil there to ikme the Potion dimibuiion impends on I
 6744s Factor and Gibbs Sum

Average v;i!ucs over ihe sybiems m diffusive and thermal contact with a

reservoir are easily found. If X{N,s) ts ilie value of -V when ihe sysiem lias N
particles and is in ihe quantum slate s, then ihe thermal average of .V over all
N and all s ts

{56)

We shiill use this result to calculate thermal averages. ,

Number of particles, The number of panicles in the system can vary because

the system is in diffusive contact with a reservoir. The thermal average of the
number of particlesin ihe system is

according lo E6). To obtain tile numerator, each term in ihe Gibbs sum has
been multiplied by liie appropriaie value of N. More convenient forms of <N>
can beobtaftied from the definition of# :

whence

<,V>
- l-ll = r^-1 E9)

Tile tiicrma! average number of particles is easily found from the Gibbs sum
When no confusion arises, we shall write jV for the
J by direct use of E9).
thermal average <N>. Wlicn we speak later of the occupancy of an orbital,
for </> will be written interchangeably for ,V or <.V>.
We often eniploy the handy notaiion

F0)

where k is called the absolute activity. Here /. is Ihe Greek letter lambda. We

see from A2) that for an ideal gas ). is directly propcrliona! to ihe concentration.
Chapter5: Chcutkul Potential and Gibbs Distribution

The Gibbs sum is wriiien as

F1}
A ' A5S

and ihe ensemble average numberof particlesE7) is

F2}

This relaiior. is useful, because in many actual problems we determine /. by

finding ihe value ihat will make <N> come out equal to the given number of
panicles.
Energy, The thermal average energy of the system is

v - <E>
- ^i F3)

where we ha\\elemporarilyintroducedthe notation /J = 1/t. We shall usually

write V for Observe
<\302\243>. that

so that E9} and F3} may be combined lo give

- ;r-\302\253 toi F5}

A simpler expression that is more widely used in calculations was obtained in

Chapter 3 in terms of the partition function Z-

Example:Occupancy zero or one. A red-blooded example of a syslcm ihat may be

occupiedby zero molecules or by one molecule is the heme group, which may be vacant or
may be occupied by one Oz molecule\342\200\224and never than one Oz molecule(Figure
by more
5.10). A single heme group occurs in the prolein myogiobin, which is responsible for the
red colorof meal.Ife is ihe energy of an adsorbed molecule of O2 relative to Oa at rest at
 Figure 5.10 Adsorpiion of an Oj by a hemc
where c is ihe energy of an adsorbed O; rctal
10 an Oi al infinite sepatuiion from ihe site.
If energy musi be supplied10detacri llie O3
from ihe heme, then c will be negative.
D

infinite distance, ihen the Gibbs sum is

\302\243~
I +;.cxp(-\302\243/r). F6)

If energy musl be added io remove the atom from, tile heme, t wilt be negative. The term t
in ihe sum arises from occupancy zero; ihe lerm Aexpf-c/i) arises from single occupancy.
Theseare itjc only possibiliiies. We have Mb 4- O2 or MbO2 present, where Mb denoies
myoglobin.a protein of molecular weighi 17 000.

Experimental results for Ihe fractional occupancy versus ihe conceniraiion of oxygen
arc show a in Figure 5.t t. We compare ihe observed oxygen saturation curves ofmyoglobin
and hemoglobin in Figure 5-12. Hemoglobin is ihe oxygen-carrying component of blood,
ti is made up of four molecular strands, each slrand nearly identical wiih ihe single sirand of

myogiobin,and each capable of binding a single oxygen molecule, Hisiorically, ihe classic
work on ihe adsorpiionof oxygen by hemoglobin was done by Chilian Bohr, the father of
Niels Bohr.The oxygen saturation curve for hemoglobin (Hb) lias a slower rise at low
pressures, because ihe binding energy of a single O, Io a moleculeof Hb is tower Ihan for
Mb. A! higher pressures of oxygen ihe Hb curve has a region lhat is concave upwards,
because trie binding energy per Oj increases after the first O2 is adsorbed.
The Oj molecules on hemes are in equilibrium with the Oj in ihe surrounding liquid, so
thai the chemical potentials of Oj are equal on ihe myoglobin and in solution:

/i(MbO2)
\302\273
/i(O2); /(MbO2) = ?.{O2) F7)

where e From Chapter 3 we find the value of / in icrnis of the gas pressure
A exp(/i/i}.
by the retalion

A = n/nQ - p/t\302\253Q. F3)

We assume ihe ideal gas resuit applies io C), in sotulion. At conslant temperature /(Oj) is
direclly proporiiomUto tjic pressure p.
The fraction/of Mb occupiedby O^ is found from {66}to be

1
_ Ac\302\273pl-t/i)
= ' Fg)
I + r'exp(\302\243/t)+ 1
/.exp(-\302\243/t)
Figure 5.11 The reaction o( u nvyoglobm
(Mb) molecule with oxygen may be viewed as
(he adsorptionof a molecule of Gj at a site
on ihe large mjoglobin molecule. Tlie
results follow 3 Langmujr isotherm <{tiitc
accutaiely. Each myoglobin molecule can
adsorb one Oj molecule.These curves show

(he fraction of myogtobin with adsorbed O.

as a function of ihe partial pressure of Oj.
The curves are for human myoglobin in
solution. Mvogiobin is found in niuidcs; it is

responsible for the color of slKtfc. After A.

Rosst-Fanellt and E. Antoiiini. Archives of

Btoihciittsiry and Biophysics77, 47\302\253 (tySK).

Concentration of O3, rcbt

Fi\302\273ure5-12 Saturation curves of O. bound

lo nijoglobin (Nib) and
iKmoglobtn (J-ib)
molccuks in soluiion in wmer. The partiat

pressure of 0. is plotted as the Iiorizonl;i!

;t\\is. Tiie vertical a.\\is gives ihe fraction of
the molecules of Mb which lus one bound
0, mokcuk, or the ft action suarnis of
of the
lib which have one bouiid Qt innlcutle.
Hunioglabm h;is a much Uirgcr change in

oxygen cotitem in ihe pressure range bensecu

ttw nuerks and the veins. Ihis circumstance
facilitates ihe aciion of ihe heart, viewed as :i
pump. The curve for myoglobin has the
pioitual lonn (or the reaction Mb + O2 \342\200\224\342\200\242

MbO.. The curve for lienio^lobin Itits ;t

uiiiCicm forrn because of ifsicracironsbenveen

O, molecules bound to ilic four si rands of ihe
lib niolccule.The dr^Atntjis after J. S. Fruton
and S. Siminondi, Gvm-J bioJtaniMry. Wiley,
1961.
 G'tbbi Factor and Gtbbs Sut.

which is [he same as the Fcrmi-Dirac distribution function derived in Chapter 7. We

subsiiiute F8) in F9| to obtain

G0}
} 4- I \302\273iurexp(E/r}
+ p

or. with p0 \302\256

jiqtcxp(\302\243/i).

'
Po +P

whac !>0 is constant wiih respect to prcsfi re, but depends on the temperature. The result
G1} is known as the Langmuir adsorption is ndtrm when used to dcicribc the adsorptioiiof
easts on the surfacesof solids.

Example;Impurity atom ionizatian in a semiconductor. Atoms of numerous chemical

elements when present as impurities in a semiconductor may iose an electron by ionizalion

to the conduction band of the semiconductor crystal- In the conduction band the electron

may oikn be treated as an idea! gas. The impurity atoms are small systems S in thermal
and diffusive equilibrium with the large reservoir fanned by the rest of the semiconductor:
the atoms exchange electrons and energy with lite semiconductor.
Lei / be the ionizalion energy of the impurity atom. We suppose that one, but only one.
electron can be bound to an impurity atom; either orientation t or i of the electron spin
is accessible.Therefore the system & has three allowed states\342\200\224one without an electron,
one with an electron attached spin f, and one
with with an electron attached with spin ].
When ^ has zero electrons, the impurity atom is ionized. We choose tiic zero ofenergy of &
other two stales thereforefiave ihc common energy c =
\342\200\224 accessible
as this stale; the /. The

stales of \342\226\240$
are summarized below.

Suite number Description

Electron detached

Electron alladicd, s
1-kcifoti ijjnjLlicJ. s

The Gibbs sum is given by

G2)
The probability tliat & is ionized ((V
\302\273
0) is

P(ioaized) \302\253
P(O.O)
= \342\200\224
= -\342\200\224-1- \342\200\224. G3)

The probability tliat $ is neutral (im-ionized) is

P(neutral) = /'(It,-/) + P(U,~/) , G4)

which is just t - PtO.O).

SUMMARY

1. The chemicalpotential is defined as h{t,V,N) = {tF/tN). v and may also bo

found from /*
\342\200\224
{cUJcN)a v
-
\342\200\224
i{cojvN}v_v. Two systems are in difl'usive

equilibrium if jtx = }tz.

2. Tl^c chemicaipotentialis made up of two parts, external ittid internal. The

external part is the potential energy of a particle in an external field of force.
The internal part is ofthermalorigin; for an ideal mooaiomic gas ;t(int)
-
Tlog(u/iiy),where is the concentration it and nQ ^{Mi'lnh2)*'2 is the quan-
quantum concentration.

3. The Gibbs factor

gives the probability that a system at chemical potential ;i and temperaturei

will have N particles and be in a quantum state s of energy ts.

4, TheGibbs sum

is taken over all states for all numbers of particles.

The absolute ~
5. activity X is defined by X expQi/r).

6. The thermal averagenumber of particles is

<A')J kg \302\243
PROBLEMS

1. Centrifuge. A circular cylinder of radius R rotaies about the ions axis with

angular velocity to. The cylinder contains an ideal gas of atomsof niass SI al

temperature i. Find an expression for lhe dependence of the concentraiion

j[(r) on the radialdisiance from
<\342\226\240 the axis, in terms of *i\302\2430)on the axis. Take
H as for an ideal gas.
2. Moleculeshi die Earth'satmosphere. If a is the concentration of mofcculcs
at the surfaceof the Earth, Al lhe mass of a molecule, and g lhe gravitational
acceleration at lhe surface, show that at constant temperature tlic total number
of molecules in the atmosphereis

= - f75)
N
4nn(K)Cxp(-A/yR/t).Jjti </rrJcxp(A/yKV<'0

wifh r iiuMstirtiJ from ihc center of flic l-yrih; here R is the railing of ihe liarili.
The integral diverges ttf (he tipjwr limit, so that N cannot be bounded and the
aimosphere cannoi be in equilibrium. Molecules, particularly light molecules,
are always escapingfrom ihe atmosphere.

3. I'ntuiitiul em-i'ity of gas fa gravitational Jield. Consider a column of moms

each of mass M at temperature t in a uniform gravitational field y. Find the
thermal average potential energy per atom.Thethermal average kinetic energy
density is independent of height. Find the total heat capacity per atom. The
total heat capacityis the sum of contributions from the kinetic energy and from

the potential energy. Take the zero of the gravitational energy at lhe bouom
~ 0 of the column. = 0 to h ~ oo.
h
Integrate from h

4. Active transport. The concentrationof potassiumK+ ions in lhe internal

sap of a plant cell(for example, a fresh water alga) may exceed by a factor of !04
the concentration of K+ ions in the pond water in which the cell is growing.
The chemical potential of the K* tons is higher in the sap because their con-
concentration it is higher there. Estimate the difference in chemicalpotential at

300 K. and show that it is equivalent to a voltage of 0.24V across ihe cell wall.
Take ;i as for an ideal gas. Because the values of the chemicalpoiemials are

different, ihe ions in the cell and in the pond are not in diffusive equilibrium. The
plant cell membrane is highly impermeable to the passive leakage of ions
ihrough tt. Importantquestionsin cell physics include ihese: How is ihe high
concentrationofionsbuilt up within the cell? How is metabolic energy applied
10 energize the aciive ion transpon?

5. Afaguctic concentration. Determine the ratio m/x for which Figure5.6is

drawn. If T = 300K, how many Bohr magnetonsfiB = eh/Zinc ivould the
particles contain to give a magnetic concentration effect of the magnitude
shown? .\"-\342\226\240..\342\226\240
 6, Gibbs sum for a two level system, (a) Considera system that may be un-
unoccupied
whh energy zero or occupied by one particlein either of two states,
one of energy zeroand oneofenergy s. Show that the Gibbs sum for ihis system is

= i + X + ;.exp(-E/r). G6)
3-

Our assumption excludes the possibility of one particle in each state at the same
time. Notice ttuitn c include in the sum a term forN \302\253=
Oasa particular state of a
system of a variable numberof particles,
(b) Show that the thermal average occupancy of the system is

G7)

(c) Show that the thermal average occupancy of the state at energye is

(d) Find an expression for the thermal average energy of the system.
(e) Allow the possibility that the orbitalat 0 and ate may be occupied each by
one particle at the same time; show that

3.
= 1 + I + Aexp(-\302\243/i) + A2exp(-\302\253/t>-\302\253 A + /.)[! + Aexp(-e/i)]. G9)

Because ^- can befactored as shown, we have in effect two independent systems.

7, Statesof uitd negative posttiw iotuzation. Consider a lattice of fixed hy-

diogen atoms;suppose each tliat atom can exist in four states:

Stale Number of electrons Energy

Ground i -JA
Posiiivc ion 0 -if)

Negative ion 2 J3
E\\cii<.-d 1 U

FioU rlic conUiiion that the Livci;t^^ number of electrons per mom be unity.
The condition will involve 5,)., and r.

X. Cmtitm mtmoxitle luihuning. lu catbon monoxide poisoning the CO

replaces the O2 ad^oibed on hanoglohin (lib) mulcculcs in ilic Wuoil. To hhnw

tl-.e clTect, consider a model for which each adsorption a heme may
site on be

vacant or may be occupied either with energy ea by one molecule O2 or with

energy eh by one molecule CO. Let A' fixed home sites be in equilibrium with
 Froblcn

O2 and CO in the gas phases at concentrations such that the activities are
X(OZ) = 1 x SO\025 and X(CO) - 1 x 10\021, all at body tempcraiure 3TC.
Neglect any spin muhiplicity factors, (a) First consider the system t\" the absence
of CO. Evaluate \302\243A such that 90 percent of the Hb sites are occupiedby O2.
Express the answer in eV per O2. (b) Now admit the CO under the specified
conditions. Find Sgsuch that only 10 percent of the Hbsitesare occupied by O2.

9. Adsorption ofO2 in a magnetic

field. Suppose that at most one O2 can be
bound to a heme group (see Problem 8), and that when /.{O2)~ iO\025 we have
90 percent of the hemes occupiedby Oj. Consider O2 as having a spin of i
and a magneticmomentof i (ts.How strong a magnetic field is needed to chance
the adsorption by 1 percental T = 300 K.? (The Gibbssumin the limit of zero
magnetic field will differ from that of Problem 8 because there the spin muhi-

muhiplicity of the bound slate was neglected.)

10. Concentration
fluctuations. The number of particles is not constant in a

system in diffusive contact with a reservoir. We have seen that

\342\200\242
re:
<,v>

from E9). (a) Show lhat

<lY!>=LLi. (81)
3- ^
The mean-square deviation ((AWI) of N from <iV> is defined by

<(ANJ> = <(N - <.V\302\2732>

=
(N>)
- 2<N><N> + (N}' = </V!>
-
<,V>:;

(b) Show that this may be written as

<(A.V)'> = tc<,V>/c> (83)

In t'liaptcr fi xvi: ;u>rly iliis n-iilt in llio i.K'iil u:is to liiul liial

is the mean square fractional fluctuation in the population of an idea! gas in

diffusive contact with a reservoir. If <A'> is of the order of \\02Q atoms, then ihe
Chapter 5: ChemicalPotential and Gibbs Distribution

fractionalfluctuation is exceedingly smalt. In such a system the number of

is
panicles well defined even though it cannot be rigorously conslatil because
diffusivecontacr is allowed wirh ihe reservoir. When <iV) is low, this relation
can be usedin the experimental determination of the molecular weight of large
molecules such as DNA of MW 103 - [O10;see M. Weissman, H. Schindler,
andG. Feher, Proc. Nat. Acad. Sci.73, 2776A976).

11. Equivalent definition of chemical potential* The chemical potential was

defined by E) as (cF/cN)tiy. An equivalent expression listed in Table 5.1 is

*=
fi (cU/cN)ay. (S5)

Prove ihat this relation, which was used by Gtbbs to define ji, is equivalent to
the definition {5}that we have adopted. It will be convenient to make use of the
resultsC1) and C5). Our reasons for treating {5}as the definition of/i, and (85) as
a mathematical consequence, are two-fold. In practice, we need the chemical
potential moreoften as a function of the temperature tihanasa funciion of the

entropy a. Operationally, a process in which a particle is added to a system

while the temperature of the system is kept constant is a more natural process
shan one in which the entropy is kept constant;Adding a particle to a system at
a finite temperature tends to increase its entropy unless we can keep eachsystem
of the ensemble in a definite, although new, quantum state.There is no natural

laboratory process by which this can be done.Hcnee the defmtiton E) or F),

in which the chemical potential is expressed as the change in free energy per
added particle under conditions of constant temperature, is operationally the

simpler. We point out that (85) will not give U ~ /tN on integration,because
H{N,c,V) is a function of N; compare with {9.13}.

12. Ascent of sap in trees. Fitsd the maximum height to which water may rise
in a iree under the assumption lhal the rools stand in a pool of water and Ihe
uppermost leaves are in air containing waier vapor at a relative humidity r =

0.9. The temperature is 25\"C.If the relative humidity is r, the actual concentra-
concentration
of water vapor air at the uppermost
in the leavesis rii0,where n0 is the
concentration in ihe saturated air lhal slands immediatelyaboveIhe poo!of
water.

13. hentropic expansion, (a) Show thai Ihe entropy of an idea! gas can be

expressed as a function only of the orbital occupancies, (b) From this result
show ihat xVin is constant in an isentropic expansion of an idea! monatomic
gas.
14. Multiple binding of Oi. A hemoglobin molecule can bind four O2

molecules. Assume lhal e is the energy ofeach bound O2, relalive to Oaat rest at
infinite distance. Lei / denote the absolute activity exp(ji/T} of the free Oi (in
. solution), (a) What is the probability that one and only one O2 is adsorbedon a
hemoglobin moiecule? Sketch the result qualitatively as a functionof/.,(b) What

ts the probabiiity Uiui four and only four O2 arc adsorbed? Sketch this result

also.

15. External chemical potential. Consider a system at temperature t. with

N atoms of mass M in volume V. Let }i[Q) denote the value of thechemical
potentialat the surface of the earth, (a) Prove carefully atid honestly that the

value of the tola! chemical potential for the identical system when translated
to altitude h is

p(h) = y Mgh ,

where g is the acceleration of gravity, (b) Why is this result different from that

applicable to the barometric equation of an isothermalatmosphere?

Chapter 6

Ideal Gas

FERMI-DIRAC DISTRIBUTION FUNCTION 153

BOSE-EINSTEIN DISTRIBUTION FUNCTION 157

CLASSICALLIMIT 160
Chemicai Potential 161
Free Energy 163
Pressure 16-\",

Energy 164

Entropy 165
Heat Capacity 165
Example:Experimental Testsof the Sackur-Tetrode Equation 167
Chemtcai Potential of Ideal Gas with internal Degrees of Freedom 169
Example: Spin Entropy in Zero Magnetic Field \342\226\240 J70

Reversible Isothermal Expansion 17'i

Reversible Expansion at ConstantEntropy IT.t

Sudden Expansion into a Vacuum i \025

SUMMARY 176

PROBLEMS 177

1. Derivative of Fenni-DiracFunction 177

2. Symmetry of Filled and Vacant Orbilals 177

3. Distribution Function for Double Occupancy Statistics 177
4. Energy of Gasof Extreme Relativistic Particles 177
5. Integration of the Thcrmodynamic Identity for an Ideal Gas 177
6. Entropy of Mining 17S

7. Relation of Pressure and Energy Densily i 7S

8. Time for a Large Fluctuation 17S

<J, Gas of Atoms with Internal Degree of Freedom 17')
10. Isentropic Relations of Ideal Gas 179
11. Convcelive isentropic Equilibrium of the Atmosphere J~0
\\2. Ideal Gas iit Two Piitu'itsiuns 1^'
13. Gibbs Sum for Ideal Gas 1SU
14. Idcai Gas Calculations ISO

15. Diesel Engine Compression ISO

Chapter 6: IdealGai

The ideal gas of noninteracting atomsin the limit of low concentration.

gas is a
The limit is defined below in terms of the thermal average value of the number
of particleslh;it occupy an orbital. The thermal average occupancy is calledthe
distribution function, usually designated as /(ej./i), where t is ihc energy of
the orbital.
An orbital is a stale of [he Schrodingcr equation for only one particle. This
terns is widely usedparticularly by chemists. !fthc interactions between particles
are weak,Ihc orbitalmodel allows us to approximate sin exact quantum state
of the Schi'6'tlingcr equation of a system of A' particles in terms of an approxi-
approximate quantum state thai we construct by assigning the N panicles lo orbituls,
with each orbital a solution of a one-particleSchroOinger equation.There are
usually an infinite number of orbitals available for occupancy. The term
\"orbital\" is used even when there is no analogy lo a classical orbit or to a
Bohr orbit.Theorbitalmodel gives an exact solution of ihe N-particlc problem
only if there are no interactions between the particles.
It is a fundamental result of quantum mechanics (ihe derivation of which
would lead us astray here) thai ail species of particles fail into two distinct
classes, fermions and bosons. Any particle with half-integrai spin is a Fermion,
and any particle with zero or integral spin is it boson. There are no interme-
intermediate classes. Composite particles follow the same rule: an atomof Hie is
composed of an odd number of particles\342\200\2242 electrons, 2 protons, I neutron-
each of spin j, so that Hie must have half-integral spin and must be a fermion.
An aloin of 4He has one more neutron, so ihcreare an even number of panicles
of spin |-, and 4Hemust be a boson.

The fermion or boson nature of the particlespeciesthat make up a many-

body system has a profound and important effect on the states of the system.
The resultsof quantum theory as applied to the orbital model of noninleracting
particles appear as occupancy rules:

1. An orbital can be occupied by any integral number of bosons of the same

species, including zero.

2. An orbital can be occupied by 0 or! fermion of the same species.

The second rule is a statement of the Pault exclusionprinciple.Thermalaverages
of occupancies need not be integral or half-integral,
but the orbital occupancies
of any individual system must conformto one or the other rule.
 Fa-mt-Dirac Distribution Function

The two different occupancy rules give rise to two different Gibbs sums for
each orbital: there is a boson stun over all integral values of the orbital occu-

occupancy A', and fermion sum in which

there is a N = 0 or N = ! Different
only.

Gibbs sums lead to different quantum distributionfunctions /{e.t./i) for the

thermal average occupancy. Ifconditions are such that/ \302\253
1, it will notmaitcr
whether the occupancies N = 2, 3,... are excluded or are allowed. Thus when
/ <:< I the fermion and boson distribution functions must be similar. Thislimit
in which the orbital occupancy is small in comparison with unity is c;ii!cd the
classical regime.
We now treat the Fcrmi-Dimc distribution function for the thermal average
occupancy of an orbital by fcrmtonsand the Bose-Einstein distribution function
for the thermal average occupancyof an orbital by bosotis. We show the
equivalence of the two functions in the limit of low occupancy, and we go on

to treat the properties of a gas in this limil.-ln Chapter treat the properties
7 we
of famioit and bosoti g;ises in the opposite limit, where the nature of the
particlesis absolutely cruchi for the properties of the gas.

FERMI-DIRAC DISTRIBUTIONFUNCTION
We consider a system composed of a single orbital that may be occupied by a
fermion. The is placed
system in thermal and diffusive contact with a reservoir,
as in Figures 6.i and 6.2. A real system may consist of a large numberNo of
fcrmions, but it is very helpful to focuson one orbitaland call it the system.

All other orbitalsofthe real system are thought of as the reservoir. Our problem
is to find the thermal averageoccupancyof the orbital thus singled out. An
orbital can be occupiedby zero or by one fermion. No other occupancyis
allowed by the Pault exclusion principle. The energy ofthe system will be taken

to be zero if the orbital is unoccupied. The energy is c if the orbiial is occupied

by one fermion.
The Gibbs sum now is simple: from (he definition in Chapter 5 we have

\302\243=
1 + ;.exp(~f./r). (I)

The term 1 comes from the configuration with occupancy A' = 0 and energy
= 0. The term -Uxp(-~-\302\243/r)
\302\243 comes when the orbital is occupied by one fermion,
so that N *= 1 and the energy is e. The thermalaveragevalue of the occupancy
of the orbital is the ratio of the term in (he Gibbs sum with N = 1 to the entire
Gibbs sum:

B)
 Chapter 6: Ideal Gm

Occupied

,VQl Wo)
=
log G,,)
\302\243<*,\342\200\236 o(/V0
_ I, Uu
-
*) = a{A'u. UJ _(|\302\243^-t(J^

Figure 6.1 We consider as the system a single otbhai that may be occupied a! most by one

fermion. The system is in thermal and diflusixc contact v-uh ihe reservoir at temperature t. The
energy e of the occupied orbital might be the kinetic encigy of a free electron of a definite

spin orientation and confined to a fixed volume- Other allowed quantum states may be
considered as forming the reservoir. The reservoir will contain JVO fcrmions if the sysiem is
-
unoccupiedand JVD i fermions if the system is occupied by one fermion.

We introduce for the average oecupancythe conventional symbol /(e) that

denotes the thermal averagenumberof particlesin an orbital of energy e:

fie) s <.V(\302\253)>. C)

Recaii from Chapter 5 that /. = cxp(/i/i), where p is the chemical potential.

We may write B) in the standard form

D)
\"exp[(\302\243 -,0/r] + 1\"

Tills result as the Fenm-Dirac distributionfunction.*

is known Equation D)

gives Ihe average number of fermions in a single orbital of energy e. The value

O2 119261, and P. A. M. Dirac, Proceedings of i!:c Royal Sociciy of London AI12. 661[

iicovcrcd. The paper by Dirac is concerned with ihe new quantum meclianits a'ld cont

general itaicmenl of lln: form assumed b>- iht P^ulj principle on ihis iheory.
 Fertni-Dhac Distribution Functlor

System

Figure 6.2 (a) Tlic obvious method of viewing a system of noninicracling panicles
shown here. The energy levels each refer to an orbital thai is a solution of a single-

parliclc Sclirodinger equation. Ttic loial energy of the sysiem is

where JVB is ihc of panicles in the orbital n of energy \302\253\342\200\236.

number For fcrmtons .V. = 0
or 1.(b) Ii is much
simpler ihan (a), and equally valid, to treai n single orbital as the

system. The system in this scheme may be itic orbital a of energytn. All other orbitals
are viewed as ihe reservoir. The lotal energy of this o\302\273e-orbital system is jVoca. whert

Nn is the number of panicles in the orbital, This device of using one orbital as ihe
system works becauseihe particles are supposedto interact only weakly with each
oiher. If we think of the fennion sysiem associated with the orbital n, these arc two
possibilities: dsher the system h;is 0 panicles and energy 0, or the system lias t pariki--
and enesgy \302\243\342\200\236,
Thus, the Gibbs sum consists of only {wo terms:

3- ~ I + Acxp{~ejti
Tltc firsi scrm arises from the orbital occupancy JVH = 0, aad the second tcnti arises

from ;Vq = 1.

of/always lies between zero and one.The Fermi-Dirac distribution function

is plotted in Figure 6.3.

In the field of solid siaie physics the chemical potential <* is often called the
Fermi level. Tlie chemicalpotentialusually depends on the temperature. Th\302\243

value of ft at zero temperature is often written as ef; ihai is,

Mi
- 0) & fi(Q)
=
Ef. E)

We call cF the Fermi energy, not to be confused* uiih the Fermi level which

*
En ilie semiconduUor liseraiure ihe symbol cF is often used for ;( a! any lempfniurt.-. a:-d ef i
ihen called she Fennt level.
Chapter 6; Ideal Gus

I 1

1 N

\\

A'

\\

........ \342\226\240~m.

-7 _6 -5 -4 -3 -2 -1 0 I 2 3 4 5 6
e \342\200\224
ji, in units of t

Figure 6.3 Plot of the Fermi-Dkac distribution function /(e) versus e - p in unils of
the temperature r. Tlie value of/(c) gives of orbitals at a given energy
the fraction
which are occupiedwhen the system is in thermal equilibrium. When tlfe system is
heated from absolute zero, fcrmions are transferred from the shaded region at E/p < 1

to the shaded region at c/ji > 1.Forconduction electrons in a metal, ji might

correspond lo 50 000 K.

is !he temperaturedependent /t(t). Consider a system of many independent

orbiials, as in Figure6.4.At the temperature orbitals of energy below
t = 0, ali
!he Fermi energy are occupied by exactly one fermion each, and ail orbitals
of higher energy are unoccupied. At nonzero temperatures the value of the
chemicalpotential departs /i from Ihe Fermi energy, as we will see in Chapter 7.
If there is an orbilalof energy equal to the chemical potential (e *=
//), the

orbital is exactly half-filled, in ihe sense of a thermal average:

F)

Orbitalsof lower energy are more ihan half-filled, and orbilals of higher energy

are less than half-filled.

We shall discussthe physical consequences of the Fermi-Dirac distribution
in Chapter 7. Righi now we go on to discussthe distribution function of non-
 -I Distribution function

Figure 6.-1 A convenient pictorial way to

think of a system composed of independent
orbitalslliat do not interact with eutli oilier
but iutecacl with 3 common tcservoir.

interacting bosons, and then we establish ihe ideal gas law for boih fcrmions
and bosons in the appropriate limit.

BOSE-EINSTEIN DISTRIBUTION FUNCTION

A boson is a particle wtjh an integral spin. The occupancyrule
value of the
for bosons is thai an orbitalcan be occupiedby any number of bosons, so lhat
bosons have essentially an different quality than fermions. Systems of bosons
can have rather different physical properties than systems of fermions. Atoms
of 4Hc are bosons;atoms of 3He are fermions. The remarkable superfluid
properties of the low temperature (T < 2.17 K) phase ofliquid heliumcan be
attributed to the properties of a boson gas. There is a sudden increasein the
fluidity and in ihe heat conductivity of liquid JHe below this temperature- In

experiments by Kapitza ihe flow viscosity of 4He below 2.17 K was found to

be iess than IO~7 of the viscosity of the liquid above 2.17K.

Photons(the quanta of the electromagnetic field) and phonons (the quanta

of elastic waves in solids) can be considered10be bosonswhose number is

not conserved, but it is simpler to think of photons and phonons as excitations

of an osciiiator, as we did in Chapter 4.
We consider the distribution function for a system of noninteracting bosons
in thermal and diffusive contact with a reservoir. We assume the bosonsare
all of the same species. Let \302\243
denote the energy of a single orbital when occupied
by one particle; when there arc N particles in ihe orbital,the energy is N\302\253,
as m Figure 6.5. We ireat one orbital as the system and view all other orbitals
Chapter 6: IdealGo:

as pan ofIhe reservoir. Any arbitrary number of particles may be in i : orbital

The Gibbs sum taken for the orbital is

G)

The upper limit on tola! numberof paniclesin the combined

N should be the
system and reservoir. However, the reservoir may be arbitrarily large, so that
N may run from zero to infinity. The series G) may be summed in dosed form.

Let x s Aexp(~E/t);then

i i

(8)
\342\200\224
A\" i -
;.cxp(-\302\243/t)

provided that kcx.p{~t/z) < 1. In

all applications,/,exp(\342\200\224e/i)will satisfy this
inequality; otherwise the number of bosonsin the system would not be bounded.
The thermal averageof !henumber of panicles in the orbital is found from

the Gibbs sum by use ofE.62):

A0)
-
-(\342\226\240)/<]

L\342\204\242-___ __
 Bosc-\302\243insicin Distribution Funclio

Figure 6.6 Comparison of Bose-Einsicin and Fenni-Dirac

dislribuiion funclions. Tlie classical regimeis aiiafoeii for

(e
\342\200\224
/i) \302\273
r, where ihe two distributions become nearly idciuit
We shall see in Ciiapier 7 that in the degenerate regime ai low
temperature ihe chemical potenijai ft for a FD distribution is
postnve, and changes 10 negative at high lemperaiure.

This defines the Bosc-Efnstcindistribution function, Et differs malhcmaticaHy

from the Fermi-Dirac distribution function only by having -1 tnsicad of + i
in the denominator.Thechange can have very significant physical consequences,
as we shall sec in Chapter 7. The two distribution funclions are comparedin
Figure 6.6. The ideal gas represents the limit e \342\200\224 r in which
/i \302\273 the two distri-
distribution functions are approximately equal, as discussed below. The choiceof ihe
zero of ihe energy e is always arbitrary. The particularchoicemade in any

problem wiU affect ihe \\a\\uc of the dieniic.il potential /i, buE the vaU:e of ihe
difference e \342\200\224
/; has to be independent of the choice of the zeroofe.This point

is discussed iuriher in B0) below.

A gas is in the classical regime when the average number of atomsin each

orbital is much less than one. The averageorbitaloccupancy for a gas at room

temperature and atmosphericpressureisof the order of only 10\026, safely in the

classical regime. Differences between fcrmions (half-integral spin) and bosons
Chapter 6: Ideal Gas

and liicq Uau iuiu reg imcs

Class of T!Krma! it i*: o CCup.iticy

Regime parlic Ic ny
___ \342\200\224
\342\200\224\"~

III
Boson Aluays much less lhan one

Quantum Fcfmioii Close 10 bul less ihan one.

Boson Orbital of lowesi energy lias
an occupancy much greater than one.

arise for occupancies of the order of one or more,

oniy so that in the dassieai

regiir.e their equilibrium properties are identical. The quantum regime is lhe
opposite of the classical regime. These characteristic features are summarized
in Table 6.L

CLASSICAL LIMIT

An ideal gas as a systemof free nomuteracting

is defined particlesin ttie classical
regime. \"Free\" means confined in a box with no restrictions or e>uernaiforces
acting within the box. We develop the properties of an idea! gas with the use

of the powerful method of the Gibbssum.in Chapter3 we treated the ideal gas

by use of the partition function, buE the identical panicle problem encountered
there was resolved by a method whose validity was not perfectly clear.

The Fermi-Dirac and Bosc-Einstein distribution functions in the classical

limit iead to the identical result for the average number of atoms in an orbital

Write /(e) for the average occupancy of an orbital at energy e. Here e ts the

energy of an orbital occupiedby one particle; it is not the energy of a system of

N particles. The Fermi-Dirac (FD) and Bosc-Einstcin(BE) distribution func-

functions are

where lhe plus sign is for the FD distribution and the minus sign for the BE
distribution.In orderthal/(c) be much smaller th;m unity for ail orbitals, we
must have in this classical regime

; exp[(e-//)/r]\302\273l.,- . . . A2)
for all e. When this inequality is satisfied we may neglect the term +! in the

denominator of (tt). Then for either fermionsor bosons,the average occupancy

of ail orhiiat of energy r. is

/(i.) * cxp[{/i
- f

wiih /. hs exp(/j/r). The limiting result A3) is called dfstnbulion

the classical
function. !t is the limit of the Fcrmi-Dirac and Bosc-Einstein distribution
functions when the average occupancy /(s) is very small in comparison with

unity. Equation A3), although called classical,is still a result for particles
described by quantum mechanics: we shall find that the expression for A or /.i

always involves the quantum constant /i.'Any theory which, contains h cannot
be a classical theory.
We use the classical distribution function /(r) = Aexp(-r/i) to study the

thermal properties of the ideal gas. There aremany topics of importance: the
entropy, chemical potential, heat capacity, the prcssure-volumc-temperaiure
relation, and the distribution of atomic velocities.To obtain results from the
classical distribution function, we need first to find the chemical potential in

terms of ihc concentration of atoms.

Chemical Potential
The chemical potential is found from the condition that the thermal average
of total number
the of atoms equals the number of atomsknown to be present.
This number must be the sum over all orbitalsof the distribution function/(eJ:

N = A4)

where s is the indexof an orbitalof energy es. We start with a monatornic gas

of N identical atoms of zero spin, and later we include spin and molecular
mocksofmotion. The total number of atoms is the sum of the averagenumber
of atoms in each orbital. We useA3) rn A4) to obtain

JV-/yexp(-\302\243,/T). AS)

To evaluate this sum, observe that the summation over free particle orbitals
is just the partition function Zx for a single free atom in volume V, whence
Chapter 6: Idea!Gils

In Chapter 3 it was shown that Zt = HqV,

where nQ s (Mrjlnh2K11 rs the
quantum concentration.Thus

A' =
;.Z, =
/.,,QK; ;. = W/i?QK
=
i?/hq , A6)

in terms of the number density n = NJV. Finally,

/ \302\253=
exp(/i/T)
=
nftiQ , A7)
j

which is equal to the number of atoms in the quantum volume l/nQ. in the
classicalregime n;nQ
is \302\253I. The chemical potential of the ideal monatomic
gas is

P =\302\273
T
tog(n/iiQ) , (IS)

in agreement wiih E.12a) obtained in another way. The result may he written
out to give

\302\253 - log V -
Jiogt + *SogBn/i2/A-/)]- A9)
i[)ogN

We see that the chemical potential increases as the concentrationincreasesand

decreases as the temperature increases.

Comment: The simple expression (IS) for (lie chemica!polentiaf can be subject lo sevcra!
modifications.We mention four examples.

(a) If the zero of ihe energy scale is shifted by an energy A so that (he zero of the kinetic
energy of an orbila! falls ill e0 = A instead of at e0 = 0, then

=. + Tlog(n/nQ).
i A B0)

(b) If lite atoms \\\\;i\\e spin S, the number of orbiiafs in ihe sum in(iS) i\302\273
mufliplicd by ihe
spin ;:iuliipiidiy^S 4- I. For s.pin \\ il isdiJublcdLlhevalucof iheparlition fund ion Z^
is JoublcJ; nQ will be replaced t\\eryw[icre by and
2\302\273G,
Ihe nght-hand side of{18)
wifl h3\\c an added ferm -rlog2. Tile tfTctt of Shi: spin on She enSropy is Srcalcd
below.
fc) If the &3s is not fTiOnatonuc, t^e iiitern^J energy sS^ies associated with ro^itionaj -ind
vibraiional moiion wifl enter ihe partition function, and tfic chemical potential wilt
 free Energy

have an added - t log Zjni, per D8) below, where 2ial is the
term partition function of
the internal degrees of freedomof one molecule.

K the gas is nonideal, the resuK for /t may be considerably more complicated;sec

Chapter 10 for tk relatively simple van der Waals approximation to j g;is of inter-

Free Energy

The chemical potential is related to the free energy by

(CF/dhr)t_y = n , B1)

according to Chapter 5. From this,

F{N,t,V) = = [log <V + B2)

\342\200\242\342\226\240\342\226\240],
j*JN}j{N,t,V} tJ^N

where the integrand is found in brackets in A9). Mow Jt/.vlog.v = xlog x \342\200\224
x,

so [hat

F - iVi[logW - I -
fog V - Jlogr + JlogBn/iVA')] . C3)

F =
Wr[iog(n/nQ)
-
1]. B-t)

Tile free energy increaseswith concentration and decreases with temperature.

Comment: The integral in B2) should strictly be a sum, because A' is a discrete variable.
Thus, from E.6),

f(N,r,l') - Ji(-V) . B5)

f

which differs from Ihe integral only in ihc lenn in log ,V in A9), for

f. log.V
= Iog(l x 2 x 3 x \342\226\240
x N) = iog/V!
\342\226\240\342\226\240
, B6)
ChapM6:UtaICai

\342\200\224
wHcfg the inic^EiiI A1
\302\2433\\e log A' _V in B3). Bui for targe N she Stifling approximation

log,V! ~ MogN - N , B7)

may be used, and now B5) is ihc same as B3).

Pressure

The pressure is relatedto the free energy by C.49):

With B3) for F we ha

=
Nt/V; pV Nz , B9)

which is the idea! gas law, as derived in Chapter 3.

Energy
The thermal energy U is found from F s U ~ iff, or

U-F + ta-F~ t(cFi<\"t)|.,\302\273

= -t: C0)

With B3) for F we have

2t
' CD

so that for an ideal gas

C2)

The factor | arises from the exponent of x in

\302\253Q
because the gas is in three
dimensions; if iiq or two dimensions, the factor would be of 1,
were in one |
respectively. The average kinetic energy of translational motionin the classical
limit Is equal to ^c or %kBT per translaiional degree of freedom of an atom.
The principleofequipartitionofenergy among degrees of freedom was discussed
in Chapter 3.
 Heat Capacity

A polyatomic molecule has rotational degrees of freedom,

and the average
energy relational degree of freedomis%r when ihe lemperature
of each is high
in comparison with the energy differencesbelwcenlhe roialiorta! energy |e\\els

of ihe molecule. The rolaliona! energy is kinetic.A linear molecule has two
degrees of rolationa! freedom which can be exciled;a nonlinear molecule has
tliree degrees of rotalional freedom.

Enlropy

The enlropy is related to the free energy by

a = [33)
-(oFJdT)v,K.

From B3) for F we have the entropy of an ideal gas:

This is idenlica! with our earlier result C.76). In the classical regime h/uq h
\302\253
1, so lhiil \\o^n0/n) is positive. The result C4) is known as lhe Siickur-Tflrode
equation for the absolute entropy of a monatomic idea! gas. It is imporiani
historically and is in thermodynamics of chemical reactions. Even
essential the

though the equation containsh, the result was inferred from experiments on
v;ipor pressureand on equilibrium in chemical rcaclions iong before the
quantum-mechanicalbasiswas fuliy understood, it was a greal challenge to
theoretical physicists to explain the Sackur-Tetrode equation, and many
un-

unsuccessful attempts to do so were made in the early years of this century. We

shall encounter applicationsof the result in later chapters.
The entropy of the idealgas is directlyproportional to the number of particles
N if their concentration n is constant, as we see from C4). When two identical
gases at identicalconditions are placed side by side, each system having entropy

ffj, the total entropy is 2al because JV is doubled. Jf a valve that connects the
systems is opened,the entropy is unchanged. We see that the entropy scalesas
the size of the system: the entropy islinear in the numberofparticles, at constant

concentration- If the gases are not identical,the entropy increases when the
valve is opened (Problem6).

Heat Capacity

The heat capacity at constant volume is defined in Chapter 3 as

C5)
Chapter6: IdealGos

We can calculate the derivative directly from the entropy C4) of an idea! gas
wlien the expression for nQ
is wn'tien out:

IE

From this, for an idea! gas

C6)

or Cy = %NkB in conventional units.

The heat capacity at constant pressure is largerihan because
C\302\245 additional

heat must be added to perform the work needed to expand the volume of the
gas againstthe constant pressure p, as discussed in detail in Chapter 8. We use
lhe thermodynamicidentity xda = dU -f pdV to obtain

/eu
p C7)

The energy of an only on Hie temperature,so tliat ldU/i)z)p

ideal gas depends
will have the same value \342\226\240dSidU/di}^, whieh isjust Cy by the argument of C.17b).
By lhe ideal gas law V - Nt/p, so that the terra p(dVldt\\ = N. Thus
C7)
becomes

C, = Q. + N C8a)

in fundamental uniis, or

C, =
C, + Nk, C8b)

in conventional units. We notice again the different dimensions that heat

capacities have in the two systems of units. For one mole,NkB is usually written

as R, called the gas constant.

The resultsC8a,b) are written for an ideal gas without spin or otherinlernal
decrees of freedom of a molecule. For an alom Cy \342\200\224
:N, so that

c,
= In + n = |,v C8c)
 Heat Capacity

in fundamental units, or

\302\273
Cp $NkB C8d)

in conventional units. The ratio CpjCv is written as 7, the Greek letter gamma.

Example; Experimental tests of the Sackur-TeiroJc equation. Experimental values of ihe

entropy are oflen found from experiment! values of Ct by numerical integration of C7)

C9)

Here <j@) denotes ihe entropy at the lowest temperature attained in rhe measurements
of C,,. The fhird law suggests rhat o@) may be set equal ro icta unless
of thermodynamics
fhcre are mullipliritics not removed at the lowest temperature attained.
We can calculate the entropy of a monatomic: ideal gas fay use of rhe Sackur-Teirodc
equation C4). The value thus calculated at a selected temperature and pressure may be
compared with the experimental value of the entropy of ihc gas. The experimental value
is found by summing ihe follow ing confributions:

1. Enlropy increase on healing solid from absolufe zero to the melling point.
2. Entropy increase in ihe solid-to-liquid transformation (discussedin Chapter 10).

.1. Entropy increase on hearing liquid from niching [mini to ihe boiling point.
4. Lntropy increase in ihe liquid-to-gas transformation.
5. Enlropy change on heating gas from the boiling point to ihe selected temperature and
pressure.
There may further be a slight corrctiion lo C4) for ihe nonidcalilyoflhe gas.Comparisons
of experimental and theoretical values have now been out for many gases,and
carried very

We give delails of the comparison for neon, afler ihe measurements of Clusius.The
enlropy is given in terms oflhe conventionalentropy S =s kua.

I. The heat capacity of ihe solid was measured from 12.3K to the melting point M.55 K
under one atmosphereof pressure. The heat capacily of ihe solid below I2.3K was
eslimaicd by a Debyc law (Chapier 4) extrapolation to absolute zero of the me^iuc-
menlsaboie IJJK.Theeniiopy of ihe solid at the melting point is found bj nuir.e.'tcal

inlcgralion of UlTiCp/T) 10be

=, i4.29Jmor'K~t.
5lolid

\342\200\242
A classic vtudy is \"The heal rapacity of oxygen from 12 K to its boding point ,ind its hiat of

ihe American Chemical Society 51.2300 A939).

Chapter 6: idcutGa:

1 able
xaluaot uropy ullli c boilin

wide iiosph

Enlropy in Jmol\" 'K\"

Gas r.lp,lnK E Nperimenia I Ca Iculalo

Nl- 212 96.40 96.45

Ar 87.29 129.75 12924
Kr 119.93 144.56 14506
sul'rce: From Lumhh BonMvin labics, 6lh cd., Voi
Pan 4, pp. 394-399.

. 2. The hc.it inpul required to mc!l the solid ai 24.55 K is observed lo be 335 J mol\"'. The
associated enlropy of melling is

3. The heat capacilv of the liquid was measured from the inching poim [o ihe boiling

point of 27.2 K under one atmosphereof pressure. The entropy increase was found 10 be

ASIJ4Uid
- a.SSJmol-'K-1.

4. The heat input required to vaporize ihe liquid at 27.2K was observed lo be 1761J
mol\021. The associaied enlropy of vaporization is

The cxpertmenlal value oflheeniropy of neon gas a! 27.2K af a pressure ofoneafmo-

sphere adds up to
= ^.oiid + + + \302\253
96.40Jmor'K\021.
sK3i ASmelling &SUvAi ASViPQliMlion

The calculafed value of the entropy of neon under ihe same condifions is

5g\302\273,
= 96.45 Jmor'K\021 ,

from ihe Sackur-Tefrodeequation. The excellent agreemenl with fhe experimental value
gives us confidencein the basis of the entire theoreticalappamlus that led to the Sackur-
Tctrodc equation. The rcsuh <31) coutd Unrstly l[:ivc been guessed; to find it verified by
observation is a real experience. Results for argon and krypton are given in Table 6.2.
 Chemical Potential of IdealGas with Infernal Degrees of FreeJoin

Chemical Potential of Ideal Gaswith

Internal Degrees of Freedom

We consider now an idealgas of identical polyaiomic molecules. Each molecule

has rotational and vibrational degreesof freedom in addition to the transla-
tional degrees of freedom.
Thetotal energy e of the molecule is the sum of two
independent parts,

\302\253 +
\302\243 en eifli , D0)

where einl refers to the rotational and vibrational degrees of freedomand r.n

to the translations! motion of the center of massofthe molecule. The vibrational

energy problem ts the harmonic oscillator problem treated earlier. The rota-
rotational energy was the subject of Problem '3.6.
In the classical regime the Gibbs sum for the orbital n is

\302\243\302\253
1 + ;.exp(-\302\243fl/t) . D1)

where terms in higher powers of ), are omitted because the averageoccupancy

ofthe orbital is assumed to n be I. That
\302\253 is, we neglect the terms in 3- which
to
correspond occupancies greater than unity. In the presence of internal energy
states Gibbs sum associated
the with the orbital n becomes

D2)

D3)

The summation is just the partition function of the internal states:

(\024)

which is related to the internal free energy of the one molecule by /\"in,
=

~tlogZ;ol. From D3) the Gibbssum is

D5)
Chapter 6: Idea! Gas

The probability that the transtationat orbita! n is occupied, irrespective of

the state of internal motion of the molecule, is given by the ratio of the term
in X to the Gibbs sum 3-:

The classical regimewas defined earlier as i. The

\302\253
/(\302\243\342\200\236) result D6) is entirely
analogous to A3) for the monatomic ease, but XZinl now plays the role of A.
Several of the results derived for the monatomie ideal gas are different for

tlie polyatomic ideal gas:

(a) Equation A7) for,* is replaced by

D7}

with <iq
defined exactly as before (We shall always use ne as defined for the

monatomic ideal gas of atoms with zero spin.) Because X = e\\p(/i/i) we

have

p. = r[log(ri/nQ)
~
IogZiol]. D8)

(b) The free energy is increasedby, for JV molecules.

D9)

(c) Thecniropy is increasedby

E0)

The former resuU U \342\200\224

jh'z applies 10 die iranslalional energy alone.

Example: Spin enmtpy in zero ntasnrtic field. Consider an atom of Spin /, where / may

represcnl boih electronic and nuclear spins. TIic iniernal partition funciion associaied
 Reversible Isothermal Expansion

with the spin alone is

ZiM = {2/ + t) , E1)

this being the number of independent spin siaics.The spin contribution to the free energy is

Fial = -tlogB/+ 1) , E2)

and the spin entropy is

=
\302\273,., logB/ + 1) . E3)

by E0). TheefTec! of the spin entropy on the chemicalpotential is found with the help of D8):

}i = T[Iog(n/ii0)- logBi + I)]. E4)

Reversible Isothermal Expansion

Consider as a model example1 x 1022 atoms of 4He at an initial volume of
!03cm3 at 300K. Let the gas expand slowly at constant temperature until the

volume is 2 x !0Jcm\\ The temperature is maintained constant by thermal

contact with a large reservoir.In a reversible expansion the system ai any
instant is in its most probableconfiguration.

What is the pressure after expansion?

The final volume is twice the initial volume; the final temperature
is equal

to the initial temperature. From pV

\342\200\224
S'x we see that the final pressure is
one-half the initial pressure.

What is the increase of entropy an expansion?

The entropy of an ideal gas at constant temperature depends on volume as

a(V) = A'log V 4- constant , E5)

= jVIog2 = (ix l0\{0.69?)") *= 0.069 x 1033. E6)

Notice that the entropy is larger at the largervolume, because the system h.TS
more accessible states in the largervolume than in the smaller volume at the
same temperature.
 Figure 6.7 Work is done by (he gas in an isothermal
expansion.Herethe gas docs work by raising llic weights.
Under isothermal conditions pi' is constant for an ulcal gas,
so thai the pressure mus! be reduced to affow !hc volume to
expand. The pressure is reducedby removing llio load of

weights a little at a time.

How much work is done by the gas ht the expansion ?

When the gas expands isothermally, it does work against a piston, as in

Figure 6.7. The work done on the piston when the volumeis doubledis
= E7)
H\\NxjV)dV
Ntlog2.

We evaluate/Vt directly as4.!4 x 30serg= 43.4J. Thus the work done on the
pistonis, from E7),

=
Ni!og2 \302\253
DJ.4J){0.693) 2S.7J. E8)

The assumption that the process is reversibleentersin E7) when we assume

that a knowledge of Vat every stage determines p at every stage of the expansion.
We define W as the work done on the gas by external agencies. This is the
negative of the work done by the gas on the piston. From E8),

w=
-jpdV= -28.7J. E9)
 ruble Expai mt Entropy

What is the changeof energy in ihe expansion?

The energy of an idea! monatomicgas is U *=
jNx and does not change in

an expansion at constant temperature. However, the Helmhoitz free energy

decreases by Afilog2, which is the work done.The connectionis discussed in

Chapter S.

How flowed inio the gasfrom the reservoir?

much heal
We that ihe energy ofihc idea!gas remained
have seen constant when the

gas did work on the pision. By conservation of energy it is necessary thai a

(low of energy in ihe form of heat into the gas occur from ihe reservoir through
the walls of the container.The quantity Q of heat added to the gas must be
equal, but be opposite in sign, to the work done by the piston, because
Q + W = 0. Thus

Q = 28.7 J , F0)
from the result E9).

Reversible Expansion at Constant Entropy

We considered above an expansion at constant temperature. Supposeinstead
that the gas expands reversibly from I x 103cmJ to 2 x 10Jcm3in an in-
insulated container. No heal flow to or from is permitted, so that Q = 0.
the gas
The entropy is constant in a system isolated from the reservoir if the expansion

processis carried out

reversibly (slowly). A process without a cluvnge of entropy

is called an isentroplc process or an adiabaticprocess. The term \"adiabalic\"

has the specific meaning that there is no heat transfer in the process. For
simplicity, we shall stick wilh\"isentropic.\"

What is the temperatureof the gas after expansion ?

The entropy of an ideal monatomicgas depends on the volume and ihe
temperature as

a{z,V)- N{iogT3;I + logK + constant) , F1)

so that the entropy remains constant if

Iogt3/2K= constant; t3/2K = constant. F2)

In an expansion at constant eniropy from V1 to V% we have

'
Tl3'2f, = rivlV1 F3)
for an ideal monatomic gas. . .
Chapter6: IdealGas

We use the idea! gas law pV = Nz to obtain two alternate forms. We insert
V -
Nxjp into F3) and cancelN on both sidestoobtain

F4)

Similarly, we insert r = pV/N in F3) to obtain

F5)

BothF4) and F5) hold only for a monatomic gas.

It is ihe subjectof Problem 10 to generalize an ideal gas of
these results for
molecules with internal degrees of motion {rotations, vibrations). We obtain
for an iscnlropic process

t.'\"'\"\"'V. =r2\"\"- F7)

Here'/ s Cp/Cy
is the ratio of the heat capacities at constant pressureand
constant volume.
With Tx - 300K and Vs/V2
=
|- we find from F3):

\302\253 K.
189 F9)

Tt\\k is ihe final temperature after the expansion at constant entropy. The gas
is cooled in the expansion process by

Tt - Tt = 300 K
- 189 K - !!IK. G0)

Expansionat constant entropy

is an important method of refrigeration.

What is ihe change hi energy in ihe expansion?

The energy change is calculatedfrom the temperature change G0). For an
ideal monatomicgas

U2 \302\243/,= Cy{x2
- r2 - r,) , G1)
 fi Expansion into

or, in conventional units,

a2- ut =ivA-B{ra- r,)

\302\273i(l x 10IZ)(j.38 x JO\0216ergK\"!){-IHK)
-2.3
=\302\273 x 108erg \302\273
-231 G2)

The energy decreases in an expansion at constant entropy. The work done by

the gas is equal to the decrease in energy the gas, which is Ul - U2 = 23 J.
of

Sudden Expansion inlo a Vacuum

Let the gas expand suddenly into a vacuum from an initial volume of I liter to
a Hn:t!vohmicof 2 liters.Thisis an excellent cxiimpfe of an irreversible process.
When a hole is opened in the partition to permit ihc expansion, the first moms

rush through and strike ihc oppositewall. If no heal How through the
the hole
walls is permitted, is no way for the atoms to lose their kinetic
there energy.
The subsequent flow may be turbulent (irreversible), with different parts of tht!

gas at different values of the energy density. Irreversible energy flow between

regions will eventually equalize conditions throughout the gas. We assume the
whole process occurs rapidly enough so that no heat flows in through the walls.

Hois1much work is done in the expansion ?

No meansof doing external work is provided, so that the work done is zero-
Zero work is not necessarily of all irreversibleprocesses,but
a characteristic
the work is zero for expansion into a vacuum.

What is the temperature after expansion?

No work is doneand no heat is added in the expansion: W = 0, Q ~ 0, and

U2
~
t/j = 0. Because the energy is unchanged,the temperature of the ideal

gas is unchanged. The energy of a real gas may change in the process because
the atoms are moved farther apart, which affects their interaction energy.

What is the change of entropy in the expansion ?

The increase of entropy when the volumeis doubled at constant temperature
is given by E6):

Au w
a2
~
a, - Nlog2 = 0.069 x 1023. G3)

For into a
the expansion vacuum 2 = 0.

Expansion into a vacuum is not a reversible process: the system is not in the

most probable (equilibrium) configuration at every stage of the expansion.

Only
 '
ChapterS: Idea! Gas

Reversible ] y t- I-
isothermal V 0
Nlog^ -.Vtlog-^ A'rtog-
expansion j
Reversible
]
isentropic ]

expansion
-J.Vt,I-(\302\243)
L. \\vi/ j
J

Irreversible \021
y
expansion into V 0 Wlog
\342\200\224

vacuum '
J

the initial before removal of the partition and the final con-
configuraiion
configuration after
equilibration are most probable configuraiions. Al intermediate
stages the distribution in concentration and kinetic energy of atoms between
the two regions into which the system is divided does not correspond to an
equilibrium distribution. The central results of these calculationsare sum-
summarized in Table 6.3.

SUMMARY: STEPS LEADING TO THE IDEAL

GAS LAW FOR SPINLESS MONATOMIC GAS

(a) /(e) = Aexp(-\302\243/r) Occupancy of an orbital in the

classical limit of/(\302\243)

\302\253
1.

N
= =\342\200\224-\342\200\224-\342\200\224~~~ Given this determines
(b) X N, equation
i e*P(-\302\243nA)
x -[n the dassical limit.

(c) En
= Energy of a free particle orbital of
-\342\200\224-177x73
^ 'j quantum number n in a cube of
volume V.

(d) X!CXP(\342\200\224\302\243JT)
= Ik j
'/ii n2 exp(\342\200\224e/t) Transformation of the sum to an
\"
integral.

(e) X = N/nQV Result of the integration (d) after

subsitution in (b).

(f) nQ
= {Mi/27rfi2K/2 Definitionof the qaantam
. concentration.
 =
(g) H T!og(ll,'!!Q)

(h) F = = -
1]
J(/,V/i(.V,t,K) NiDog(tr/HU)

(i) p - -icFfcV)t,N- Nt/K

PROBLEMS

Derivative of Fermi-Dirac function.

7. Show that
\342\200\224cf/vc
evaluated at ihc
Fermi level e = ji has the value Dt)~'. Thus the lower the temperature, the
steeperthe slopeof the Fermi-Dirac function.

2. Symmetry of 'filled and vacant orbitah. Let e = /i + 5, so that /(c) ap-

appears as f{fi + i5). Show that

fin + 5) = 1 -'/(/< - 3). G4)

Thus the probability that an orbital 5 above the Fermslevel is occupied is equal
to the probability an orbital6 below the Fermi level is vacant. A vacant orbital is
sometimes known as a hole.
3. Distribution function siaiist'tcs.
for Let us imaginea new
double occupancy
mechanics in which the allowed
occupancies of an orbital are 0, I, and 2. The
values of the energy associated with these occupancies are assumed lo be 0, e,
and It, respectively.
(a) Derive an expression for the ensemble average occupancy (N>, when the
system composed of this orbital is in thermal and diffusive contact with a

reservoir at temperature t and chemical potential/t.

(b) Return now to the mechanics, and derive an expression
usual quantum
for the ensemble
average occupancy of an energy level which is doubly de-
degenerate; that is, two orbhals have the identical energy e. If both orbitals are
occupied the total energy is 2e.

4. Energy of gas of extreme relativistk particles. Extreme relativistic parti-

particles have momenta p such that pc \302\273
Me2, where M is the rest mass of the
particle.Thede Broglie /. = h/p Tor the quantum wavelength continues
relation

to apply. that the mean

Show energy per particle ofan extreme ideal relativistic

gas is 3t ift S pc, in contrastto ir the nonrclativistic problem. (An interesting

Tor

variety of relativisticproblems discussed by E. Fermi in Notes on Thermo-

are

ttynumU-s wul Suiiisiks, University of Chicago Press, 1966,paperback.)

5, Integration of the tlwrntodynanric identity for an ideal gas. Fromthe thcr-

modynamic identity at constant number of particleswe have

+ ^. G5,
X
Chapter 6; Ideal Gas

Show by integration thai for an ideal gas the entropy is

a = Cv logT + N log V + at , G6)

where crj is a constant, independentof t and V.

6. Entropy of mixing. Suppose that a system of jV atoms A is placed

of type
in diffusive contact with a system of N atomsof type B at the same temperature
and volume. Showthat after diffusive equilibrium is reached the total entropy
is increased by 2N log eniropy increase2N log2is
2. The as [he entropy known

ofmixing. if ihe atoms are identical s B), show that there is no increase
{A in

entropy when diffusive contact is established. The difference in the results has
been called ihc Gibbs paradox.
7. Relation of pressure and energy density, (a) Show ihat ihe average pres-
pressure in a system in thermal contact with a heat reservoir is given by

G7)

where the sumis over all states of the system, (b) Show for a gas offree particles
that

;
-r77 , G8)

as a result of the boundary conditionsof the problem. The result hoids equally
whether es refersto a stateofJV noninteracting particles or to an orbital (c) Show
that for a gas of free npnrelativistic particles

p= WjlV , G9)

where U is the thermal average energy of the system. This result is not limited
to the classical regime; it holds equally Tor fermion and boson particles, as
long as they are nonrelativistic.

8. Time for a large fluctuation. We quoted Boitzmann to ihe effect that two
cases in a 0.1 liter container wiH unmix only in a lime enormously long compan^
to 10\" \"'\"'years.
We shall problem: we let a gas of atomsof
investigate a related
JHe occupy a container of volume ofOJ liter at 300 K and a pressure of 1 aim,
and we ask how long it will be before the atoms assume a configuration in
which all are in one-half of the container..
(a) Estimatethe number of states accessible to the system in this initial

condition.
 (b) The gas is compressed isothermallyto a volume of 0.05 liter. How many
stales are accessiblenow?
(c) For the system in the 0.1 liter container, estimate the value of the ratio

number of states for which all atoms are in one-half of the volume
'
number of states for which the atoms are anywhere in the volume

(d) If the collision rate of an atom is % 10lC)s\"', what is Ihe total number of
collisionsof all atoms in the system as a crude estimate
in a year? We use this
ofthe frequency with which the slate
system changes. of the
(e) Estimale the number of years you would expectto wait before all atoms
are in one-half of the volume, starting from ihc equilibriumconfiguration.
9. Gasof atoms m'th iutermil degree of freedom. Consider an ideal man-
atomicgas, but one for which the atom has two internal energystales,one an

energy A above [he oiher. There ;ire H aiomsin volume V at temperature r.

l-'nut ttic (a) chemical puk'iiljai; (h) live energy; (c) entropy; (t|> pic.^uic;
(o) heat capacity;it constant pressure.
10- hentropic relations of ideal gas. (a) Show that the differential changes for
an tdcal gas in an isentropic process satisfy

(SO)

where =
CpjCv\\ these relations apply even
y if the molecules have internai
degrees of freedom, (b)The isentropicand isothermal bulk moduli are defined as

BB
=
~V{cp!cV)a; Bs =* -V(dp/dV)t. (81)

Show that for an idea! gas Ba = yp; B, = p. The velocity of sound in a gas is
given by c - (Ba/p)\022; ihcre is very iittie heat transfer in a sound wave. For an
ideal gas of molecules of mass M we have p = pi/M, so that c = (yr/'A/I'' .
Here p is the massdensity.
//. Convcaire iscntropk equilibrium of the atmosphere. The iower iO-15km
of the atmosphere\342\200\224the troposphere\342\200\224is often in a convccijve sieady state
at constant entropy, not constant temperature. \\\\\\ such equilibrium p\\\"' is
independent of altitude, where CplCr. Use the condition of mechanical =
-,\342\226\240

equilibriumin a uniform gravitational field to: (a)Show that dTjdz = constant,

where r is the altilude. This quantity, important in meteorology,is calledthe
dry adiabatic lapse rate. (Do not use ihe barometric pressure
relation that was
derived in Chapter 5 for an isothermal atmosphere.) (b) Estimate JT/i/r, in
CC per km, Take y =
7/5. (c) Show that p x p1,where p is the mass density.
Chapter6: IdealGas

If the actual temperature gradient is greater than the isentrapic gradient, the

atmosphere may be unstabic with respect to convection.

12. Idealgas ttro in dimensions, (a) Find ihe chemical potential of an ideal
monatomicgas in two dimensions, with N atonis confined to a square of area
A = L2. The spin is zero, (b) Find an
expression for the energy V of the gas.
(c) Find an expression for the entropy a. The temperature is r.

13. Gibbi sum for ideal sas. {a) With the help of Zs ^ (i>QV)sf,\\\\
from

Chapter 3, show that the Gibbs sum for an ideal gas of identical atoms
=
is 3- exp(;.iiQK).(b) Show that Hie probability there arc ;V atoms in Hie gas
in volume V in diffusive coniact wiih a reservoir is

P(N} = <N/exp(-<N\302\273/N! , (82)

which is just ihe Poisson distribution function {Appendix C). Here <jY> is the
thermal average number of atoms in ihe volume, which we have evaluated
previously as <N) = XVnQ, (c) Confirm that P[N) above satisfies

X P(N) = 1 and NP{N)

\302\243
= <N>.

14, Ideal gas calculations. Consider one mole of an ideal monatomic gas ai
300K and 1atm. First,let the gas expand isothermally and revcrstbly to twice
the initial volume; second, let Hits be followed by an iseniropic expansionfrom
iwice io four limes ihe initial volume, (a) How much heat (in joules) is added io
the gas in each of these two processes? (b) Whai is ihe temperature at ihe end of
the second process?Supposethe first process is replaced by an irreversible
expansioninto a vacuum, to total volume twice the initial volume,
a (c) What
is ihe increase of emropy in ihe irreversible expansion, in joules per kelvin?

15, Diesel engine compression. A diesel engine is an internal combustion

engine in which, fuel is sprayed into the cylinders after ihe air chargehas been
so highly compressed that it has attained a temperature sufficient !o tgntte the
fuel. Assume that the air in the cylindersis compressed i sen tropically from an
initial temperature of 27\302\260C C00 K). If the compression ratio is 15, what is the

maximum temperature in to
\302\260C which the air is healed by the compression?
Take y
= 1.4.
Chapter 7

Fermi and Bose Gases

FERMI GAS 183

Ground Slale of Fermi Gas in Three Dimensions 185

Density of Simcs 1S6
Heal Capacity of Electron Gas IS9
FermiGas in Metals 194
White Dwarf Stars 196
'
Nuclear Mailer 19S
BOSON GAS AND EINSTEIN CONDENSATION 199

Chemical Potential Near Absolute Zero 199

Example: Spacing of Lowest and Second Lowest Orbilals
of FreeAtoms 201

Orbital Occupancy Versus Temperature 202

Einstein CondensationTemperature 205
Liquid \"He 207
Phase Relations of Helium 210
Quasiparticles and Superfluidity, *He 212
Superfluid Phases of 3He 217
SUMMARY 217

PROBLEMS 218

1. Density of Orbitals in One and Two Dimensions 218

2. Energy of Relativists Fermi Gas 218
3. Pressure and Entropy of Degenerate Fermi Gas 219
4. Chemical Potential Versus Temperature 219
5. Liquid'He as a Fermi Gas 219
6. Mass-Radius Relationship for White Dwarfs 219
7. Photon Condensation 221
8. Energy, Heat Capacity, and Entropy of Degenerate Boson Gas 221
9. Boson Gas in One Dimension 222
10. Relativistic White Dwarf Stars 222
!!. Fluctuationsin a FermiGas 222
12. Fluctuations in a Bose.Gas 222
13. Chemical Potentia! VersusConcentration 222
14. Two Orbital Boson System . 223
It is a fundamental result of quantum theory that all particles, including atoms
and molecules,areeither fermions or bosons. They behave alike in the classical
regime in which the concentration is small in comparison with the quantum
concentration,

(i \302\253
ifQ
s (Mt/2tt/ijK'2. A)

Whenever n > iiq

the gas is said to be in the quantum regime and is called a
quaniutn gas. The properties between a quantum gas of
difference in physical
lemi ions and one of bosons is dramatic, and boih are unlike a gas in the classical

regime. Fermi A gas or liquid has a high kineticenergy, low heal capacity, low
magnetic susceptibility, low interparticle collisionrate, and exerts a high

pressure on the container, even at absolute zero, A Bose gas or liquid has a
high concentration of panicles in the ground orbital, and these particles \342\200\224

called the Bose condensate-\342\200\224may act as a superfluid, with practically zero

viscosity.
For many systems the concentration n is fixed, and the temperature is the
important variable.The quantum regime obtains when the temperature is
below
t0 s {2nh2/M)n213, B)

defined by the condiiion n ~ iiq. A gas in the quantum regime with r \302\253
ro
is often said to be a degenerate gas*.
h was realized by Nernst that theentropy of a classical gas divergesas logr
as t -* theory removes the difficulty:
0. Quantum both fermion and boson
gases approach a unique ground stateas i -+ 0, so that the entropy goes to
zero.We say that ilie entropy is squeezed out on cooliuga quantum gas (see
Problems 3 and S).
in the classical regime{Chapter6) the thermal average number of particles
in an orbital of energy h
\302\243 given by
Wilh Ihe result for^ appropriateto this regime,

J{z)
- ,
(n/HG)exp(-\302\243/i) D)

with the usual choice of the origin of eat zero for the energy of the lowest orbital.
The form D) assures us that the average occupancy of any orbital is always

<it/nQt which is \302\253!,consistent with our original picture of the classicalregime.

A fcrniion is any panicle\342\200\224elementary or
composite\342\200\224with a half-iniegra!

spin. A fermion is limited by ihe Pauli exclusion principle to an orbital occu-

occupancy of 0 or I, with an average occupancy anywhere between these limits. Ai

low temperatures it is dear that many low-iying orbiials will have one fermitm
in each orbital. At absolute zero all orbitals with 0 < e < eF will be occupied
with /
= I. Here ef is the energy below which there are just enough orbitals
to hold the number ofparticles system. This energy is calledihe
assigned to the
Fermi t-iierfiy. Abo\\cr-fall orbiusls will have/ = Oiit r = 0. As t increases the
distribution function will develop a high energy mil, as in Figure 7.3.

Bosons have integral or zero spin. They may be elementary or composite;

if composite, they must be made up of an even number of elementary particles
if these have spin \\, for there is no way to arrive at an integer from un odd
immber of half-integers. The Pauli principle does not appiy to bosons, so there
is no limit on ihe occupancy of any orbital. At absolute zero the ground
orbital\342\200\224the orbital of lowest energy\342\200\224is occupied by all the particles in the
system. As the temperature is increased the lowest single orbital ioscsits popula-
population only slowly, and each excited orbital\342\200\224any orbital of higher energy\342\204\242will

contain a relaiively small number of particles. We shall discuss this point

carefully. Above r = r0 the ground orbital losesits special feature, ;md its

occupancy becomes much like that of any low-lying excited orbital.

FERMI GAS

A Fermi gas is called degeuerate when the temperature is low in comparison

with ihe Fermi energy. When the inequality i \302\253
e^ is satisfied
the orbitals of
energy lower than ihe Fermi energy ef will be almost entirely occupied, and the
orbitals of higher energy will be almost entirely vacant. An orbital is occupied

fully when it contains one fermton. A Fermi gas is said to be no udegenerate

wlicrt the temperature ishigli compared with the Fermi energy, as in the classical

regime treated in Chapter 6.

The
unportam applications of tlie theory of degenerateFermi gases include

conduction electrons in metals, the wliiie dwarf stars; liquid 3He; and nuclear
matter. The most striking property of 3 fermion gas is the high kinetic energy
 Fermi level f, for
60
\342\226\240|
16 eleclrons;in Hie

\"a gTOUnd slalc the

louesi eight levels
(!6orbilals) are
occupied

(a)

Figure 7.1 (a) The energiesof the orbhals n = i,2 10for an etecfron
confined to a fine of lenglh L. Each level correspondsto two orbitafs, one for
spin up and one for spin down, (b) The ground siaicof a system of t6 electrons.

Orbitals above the shaded region are vacant in the ground Slate.

of theground state of the system at absolutezero.Suppose that it Is necessary

to accommodate N nomnteracting electronstn a length L in one dimension.
What orbitals will be occupied in the ground state of the N electron system?
In a one-dtmenstonal crystal the quantum number of a free electron orbitalof
form is a positive
stn{fJ7ix/L) integer it, supplemented by the spin quantum
number ms \342\200\224 for
j-
\302\261 spin up or spin down.
If the system
has 8 electrons, then in the ground state the orbttais with
(i = 1, 2, 3, 4 and with in,
= are
\302\261\302\243 fiHed, and the orbitais of higher n are
empty. Any
other arrangement gives a higher energy. To constructthe ground

state we fill tire orbitals starting from it = 1 at the botiom, and we continue
filling higher orbitals with electrons until all N electrons are accommodated.
The orbitais that are filled in the ground state of a systemof 16electrons are

shown in Figure 7.1.

 Ground Sttite of Fermi G&s in Thtee Dimensions

Ground Slate of Fermi Gas in Three Dimensions

Let be a eube of sideL and volume

the system V = L3. The orbilais have the

form of C-58) and their energy is given by C.59). The Fermi energy Ef is the

energy of the highest filled orbiiai at absolutezero;it is determined by the

requirement that the system in the ground stale Iioid N electrons, with each
orbital filled wiih one electron up to the energy

E)
<5)

Here tiF is the radius of asphere (tn the space of the integers nx, tty,
ihai
\302\273r)

separates filled and empty orbitals. For the system

to hold N electrons the
orbitais must be filled up to nF determined by

n, = {lNfn)ll\\ F)
y

The factor 2 arises because an electron has two possiblespin orientations.The

factor| arises because only triplets nx, ny, nz in the positive octant of the sphere
in n space are to be counted. The volumeof the sphere is 4nn//3. We may
then write E) as

This relates the Fermi energy to the electron concentration N/V

= n. The
so-called \"Fermi temperature\"tf is definedas t> s ef.
The total energy of the system in the ground state is

=
[/\342\200\236 2 e,
\302\243
= 2 x | x 471
\\^r
eln n2 eB *= --1 j j
P' (in \302\273a
, (S)

with En
= (h2/2m)(n}t/LJ. In (8) and (9),n is an integerand isnot N/V.Consistent
with F), we have let

21 2(fcX4n)
(\342\226\240\342\226\240\342\226\240)-> (9)
JdrtirV-)

in the conversion of (he sum into an integral. Integration of (8) gives the total
ground state kineticenergy:

l0m\\L
 0 10 20 30 40 50 60 70 80 90 100
Volume, in cm3

Figure 7,2 Total ground stale energy Uo of one mole of

elecirons, versus volume.

using E) and F).The average kinetjcenergy per particle is UJN and is f of

the Fermienergy cF. At constant N the energy increasesas the volume decreases

(Figure 7.2), so that the Fermi energy gives a repulsive contribution to the
binding of any material; in most metals and in white dwarf and neutron stars
it is the most important repulsive interaction. That is, the Fermienergy tends

to increase the volume. It is balanced in metals by the Coulomb iiltraction

between decuoos and ionsand in she stars by gniviimicurjS attraction.

Density of States
Thermal averages for independent particle problems have the form

where rr denotes the quantum orbital; XR is the value of the quantity A' in

the orbita! n; and f(t:a>T,!i.)is the thermal averageoccupancy,calledthe dis-

distribution function, of the orbital n. We often express <.Y) as an integral over the
orbital energy
Then
\302\243. A1) becomes

A2)
 Density of States

where the sum over orbitais has been transformed to an integral by the sub-

substitution

X *>(eH'
(\342\226\240\342\226\240\342\226\240)-> \342\226\240\342\226\240)\342\226\240 A3)
Jrfs

Here is the
<D(\302\243}^\302\243 number of energy betweent and t 4- dt. The
of orbitais
quantity 'D(e)is nearly always cailed the density of slates, although it is more
accurate to call it the density of orbitais because it refers Jo the solutions of a
one particleproblemand not to the states of the N particlesystem.
Consideran example of Ihe calculalion of \302\251(e). We see from G) thai the
number N of free electronorbitaisofenergy iess than or equal lo some e is

N{e) =>
(V/in2)BM/h2)il2til2 , A4)

for volume V. Take the iogarithm of both sides:

logN s=
flogs + constant, A5)

and take differentials of log N and loge:

The quantity dN = (iN/lsjdt is the number of orbifals of energy between c

and e + (/e,so that

C(e) ~dNltlt = ZN{t)llt A7)

is the density of orbitais. two spin orientations of an electronhave

The been

counted throughout this derivation because they were counted in F). We can

write \302\251(e)as a function of e alone because

= , (IS)
JV(\302\243)A (V/3n2){2m/h2)y'2F.in

from A4). ThenC 7) becomes

A9i
 Chapter 7: Fermi and BaseGm

Figure 7.3 Density of orbitals as a function

of energy, for a free electron gas in three
dimensions. The dashed curve represents the
densiiy /(eVD(e) of occupied orbilals ai a finile
temperature, bm such thai r is small in

comparison wiih cF. The shaded area rcprcsetus

the occupied orbiiah ai absolute zero.

Energy, e *\"\342\226\240

When multiplied by the disiribulion function (Figure 6.3), the densiiy of

orbilals *D(e) becomes <D(\302\243)/{e), ihe dens'ny of occupied orbilals (Figure 7.3).The
total number of electrons in a sysiem may now be written as

B0}

where f{t) Fcrmi-Dirac distributionfunction

is Ihe described in Chapier 6. In

probkms where we know the total number of patiides, we determine }t by

requiring ihal the total number of particles calculated from B0) be equal to Ehe

correct value. The total kinetic energy of ihe electrons is

V = B1)

If Jhe sysiem is in the ground stale, all orbitais are filled up to the energy \302\24

above which they are vacani. The number ofekcirons is equalto

B2

and ihe energy is

B3)
 Heat Capacityof Electron Gas

Heat Capacity of Eleciron Gas

We derive a quanliiaiive expression for the heal capacity of a degeneraie Fermi

gas of electrons in three dimensions. The calcufaiionis perhaps

the most im-
impressive accomplishment of the theory of (he degenerateFermi gas. For an
ideal monalomic gas the heat capacity is \302\247W,bui for elecirons in a meial very

much lower values are found. The calculation that follows gives excellent agree-
agreement wiih theexperimemal results. The increase in (he total energy of a system
of N electronswhen healed from 0 10 i is denoted by AU ~
U{x) \342\200\224
L'(Q),

whence

AU = - B4)
JjVcrfWO:) J0\"<fcrf>(E).

Here f{c) is (he Fermi-Dirac fimetion, and O(c) is the number of orbilals per
unit energy range. We multiply the identity

N \" </e/WW
~ B5*
Jo\342\204\242 J^W

by tf to obtain

+ - f/dttfiiz). B6)
{jo ifjAttrfteW
We use B6) fo rewrite B4) as

AU = Je(b - tr\\n^y0{c)+
fc'M*r
- $0 ~
fW&iz)- W)
JJ

The first integral on the right-hand side of B7) gives the energy neededlo take
electrons from ef to the orbitals of energy \302\243
> and
\302\243f,
the second integral gives
ihe energy neededto bring ihe eiecirons to ef from orbifals below ef. Both
contributionsto !he energy are positive. The product f(c)'D{c)de in the firsi

integral is the number of electrons elevated to orbitals in ihe energy range

dc at an energy e.The factor [1 \342\200\224
/(\302\243}]
in the second integral is ihe probability
thai an elecironhas been removed from an orbilal c. The function A (/is plotted
in Figure 7.4. In Figure 7.5 we plot ihe Fermi-Dirac distribution function versus
for
\302\243, six values of the lemperalure. The electronconcenlration of the Fernii
gas was laken such that tfjkB ~ 50000K, characteristic of ihe conduction
electrons in a meial.
The heat capacity of the electron gas is found on differentiating AU with

respect to r. The only temperature-dependentterns in B7) is /(e), whence we

Figure 7.4 Temperature dependence of the energy of \302\243\342\226\240
a noninteracting fermian gas in three dimensions. The S; 05
energy is plotted in normalized form as AU/NeT,
^
uhere N is the number of decirons.The temperature
is ploued as xjtF.

0.4 0.6

3 4 5 6 7

e/A'b, in uniis of 104 K

Figure 7.5 Fermi-Dirac disiribuiion function ai various

lempcraiures, for
TF = \302\243F/kB= 50000 K. The resuhs apply gas in ihreedimensions.Th
10 a

number of particlesis constani, independent of temperature. The chemical

each temperature was calculated with the help of Eq.B0)and may be read
graph as the energy at which/ = J. Courtesy of B. Feldman.
 Heat Capacity of ElectronGas

-Region of UcMsieraic quantum gas

/
/ \342\200\224-^ Rc\302\253ion of classic-,

\\

Figure 7.6 Piol of ihe chemical poiemiai /i versus temperature T for a

gas of noninteraaing fcrmions in ihrcc c!iincisions. For convenience in

plotting, ihc units of ji and i arc 0.763cf.

can group terms to obtain

B8)

At (he tempera lures of interest in nseiats x/eF < 0.01,and we see from Figure 7.5
that the derivative df/dx is large only at energies near er. It is a goodapproxi-
approximation to evaluate the density of orbitais <O(e) at sf and take it outside of the

integral:

Ccl S B9)

Examinationof the graphs hi Figures 7.6 and 7.7 of the variation of/i with x
suggests that when t \302\253 we
\302\243f ignore the temperature dependence of thechemica!
potential ji in the Fermi-Dtrac distribution function and replace ;i by the

constant cF. We have then:

C0)
 Chapter 7; Ftrmi and Bost Gas

Figure 1.1 V&riaiiors with temperature of she

chemical
potential free electron Fermi
ji, for
gasesin one and three dimensions. In common
meials t/nF a= 0.01 at room (empcraiure, so
thai ;i is closely equal lo cF.Thesecurves were
calculated from series expansions of the integral
for the number of particles in ihe system.

We set

x a (e.- e,)/t ,
\"
and it follows from B9) and C0) that

We may safely replace the lower limit by -co because the factor
integrand is already negligibleat x = -ef/r if we are concerned

temperatures such that cF/x -~ f 00 or more. The integral* becomes

~
+ iI 3

\342\200\242
The inicgta! is not demciuary, but may be cvafua^d from ihe n

-V it2
p,

ondilTeremhuion of bsjih sides uiih rcspcci lo ihc parameter a.

 Heat Capacity of Electron Gas

whence we have for she heat capacityof an electron gas, when r \302\253
xf,

'
Cel - WUEfU. I C4)

In conventional units,

Ctl C5)

We found that the density of orbitajs at the Fermi energy i,

-
\302\253(\302\243,) 3N/lcf = 3iV/2tf 06)
for a free electron gas, with xF s eF. Do not be deceivedby the notation rF:
if is not the temperature ofthe Fermi gas, hut only a convenient reference point.
For r \302\253
xF the gas is degenerate; for r \302\273
if (he gas is in the classical regime.
Thus C4) becomes

C7)

in conventional units there is an extra factor kBl so that

C\\, C8)
where A'flTF
s sF. Again, TF is not an actual temperature,
but
only a reference

point.
We can give a physical explanationof the form of the result {37). When the
specimen is heatedfrom absolutezero,chiefly those electrons in states within
an energy range r ofthe Fermi level are excited thermally, because the FD
distribution function is affected over a region of the order of r in width, illus-
illustrated
by Figures 7.3 and 7.5. Thus the number ofexcited electrons isofthe order
of A'i/\302\243F, and each of these has its energy increasedapproximately by
r. The

total electronic thermal energy is thereforeofthe order of Uci as Ni2/eF. Thus

the electronic contributionto the heat capacityis given by

A'r/rF C9)

which is directly proportional to t, in agreement with the exact result C4) and
with the experimental results.
Chapter 7: Fctmi and Bos

Table l.\\ Cuiculaied Fermi energy parameters for free eleciroi

Comiuciion Fermi

eieclron Fermi iempcratur

concemralion Velocity energy T., = [. k,
NiV. in cm'3 SV, in cm s~' in eV
\302\243F, inK

Li 4.6 x 10\" 1.3 x 10\" 4.7 5.5 x 10J

Na 2.5 1.1 3.S 3.7
K 1.34 0.85 2t 2.4
Rb 1.0S 0.79 1.8 2.1
Cs 0.56 0.73 1.5 1.8
Cu 8.50 1.56 7.0 8.2
Ag 5.76 1.38 5.5 64
Au 5.90 1.39 5.5 6.4

Fermi Gas In Metals

The alkali metals and copper, silver,and gold have one valence electron per
atom, and the valence electron becomes the conduction electron in the metal.

Thus the concentration of conduction electrons is equa! to the concentration

of atoms, which may be evaluated eilher from the densiiy and ihc atomic

weight or from the crystal lattice dimensions.

If the conduction electronsact as a free fermion gas, the value of she Fermi
energy eF may be calculated from G):

ef = {hl12m)Cn2uI!\\ D0)
Valuesof n and of ef are given in Table 7.1 and in Figure 7.8.The electron

velocity vF at the Fermi surface is also given tn (he \\ab!e; it is defined so that
the kinetic energy is equal to ef:

^ttuy3
- .
\302\243f HO

where nt is the mass of the electron. The values of (he Fermi \\emperatureTF ~
eFjkB
for ordinary metals the order of 5 x l04K,so that
are of the assumption
T \302\253
TF used in (he derivation of C5) is an excellent
approxima(ion
at room

temperature and below.

The heat capacity of many
metals at constant volume may be written as
the sum of an electronic contribution and a lattice vibration contribution. At
Sow temperatures the sum has the form

Cv ~ yi + At3 D2)
 Na
a functio

Rb
monovaienl mclals. The siraighl line is dra
J !brEf ^ 5.835 x 10\023'n1/J ergs, whh iiin

5 10\" 2 5 10\302\260

Eleciron concentration, in cm~3

Figure 7.9 Expcrimcnlalheal capacity values for polnssium, plolled as C/Tv

TK After W. H. Lien and N. E. PhiJHps, Phys. Rev. 133, AI37O A964}.

where y and A are constants characteristic of the material. Here y s jn2N/iF

from C7), and the lattice vibration term-4i3was discussed in Chapter 4, The
electronic term is linear in t and is dominant at sufficiently iow temperatures.
Ii is helpful to display the experimental values of the heat capacity for a given
material as a plot of Cvjx versus t2:

~
Cy/t y + Ax2 D3)

for then the points should lieon a straight line. The intercept at t \342\200\224
0 gives
the value of y. Such a plot is shownfor potassium in Figure 7.9. Observed values
of y are given in Tables 7.2 and 7.3.
 Table 7.2 Experiment! and free eteciron eSecironic
heat capacities of monovalent metals

y Cexp), e electron},
mJmol\"'K\"
1
y/y0

Li 1.63 0.75 2.17

Na 1.38 1.14 1.21
K 2.08 1.69 1.23
Rb 2.41 197 1.22
Cs 3.20 2.36 1.35
Cu 0.695 0.50 1.39
Ag 0.646 0.65 1.00
Au 0.729 0.65 1.13
oni: The values of \342\226\240/
nud yo arc in i
iUlU u: Oluilcsy of N. li. 1'hillim.

Table 7.3 ExpenmenUt values of declronic heat capaciiy consiain y of mcials

Li Be C N

1.63 0.17
Na mb I Al Si P
1.38 1.3 1.35

K Ca Sc Ti \021 V Cr Mr Ni Cu Zn Cra Gc As
2.08 2.9 107 3.35 9.26 t.40 9.2 4.73 7.02 0.695 0.64 0.596 0.19

Rb Sr Y 2r Nb Mo Tc Rh P<! Ae a In Sn Sb
2.41 3.6 10.2 2.80 7.79 2.0 _ 4.9 9.42 0.646 0.638 1.69 1.78 0.11
Cs Ba La Ht T* W Re lr Pt Au He Tl jpb Bi
[3.20
2.7 10. 2.16 5.9 1.3 2.3 3.1 6.8 0.729 1.79 1.47 2.98 o.oos
sOTE;Thc value of y is in
,s fuiniihed by R E Phillips and N. Pear

White Dwarf Stars

White dwarf slars have masses comparable to that of the Sun. The mass and
radius of Itic Sun arc

Q
* 2.0 x 10!3 g; Ko = 7.0 x 10'\302\260cm. D4)

The radii dwarfs are very small, perhaps

of white O.Oi that of the Sun. The
density
of the Sun, which is a normal star, is of the order of 1 gem\023, like that
of water on the Earth. The densitiesof white dwarfs are exceedingly high, of the
 White Dwarf Stars

order oflO'1 to 107gem\023. Atoms under the densities prevalent in white dwarfs
are entirely ionized into nuclei and free electrons, and the electron gas is a
degenerategas,as will be shown below.
The companion of Sinus was the first white dwarf to be discovered. In 1844
Besselobserved that the path of the star Siritis oscillatedslightly about a straight

lincasifithadan invisible companion.The companion, SiriusB,was discovered

near its predicted position by Clark in 1862.ThemassofSiri us B was determined
to be 2.0 x 3O33 g by measurements on the orbits. The radius of Sirius B ts

estimated as 2 x 109cm by a comparison of the surface temperature and the

radiant energy flux, using the properties of thermal radiant energy developed
in Chapter 4.

The mass and radius of Sirius B lc;id to the mean density

D5)

This extraordinarilyhigh density was appraised by Eddington in 1926 in the

following words; \"Apart from the incredibility of the result, there was no

particular reason to view the calculation with suspicion.\" Other white dwarfs
have higher densities; that named Van Maanen No. 2 has a mean density

100 times higher.

Hydrogen atoms at a density of 106gcni~3have a volume per atom equal \\o

A
~ =s 2 x iO~30cni3pcratorn
(I06molcm\023){6 a 10\" atoms mol\021)

or 2 x
10~6A3peratom. The average nearest-neighbor separation is ihen of

the order of 0.01 A, as compared with the internuclcar separation of 0.74 A in a

molecule of hydrogen. Under conditions of such high density the atomic

electrons are no longer attachedto individual nuclei. The electrons are ionized
and form an electron gas. The matter in the white dwarfs is held togetherby
graviiational attraction, which is the binding forcein all stars.
In the interior of white dwarf stars* the electron gas is degenerate; the

temperature is much less than the Fermi energy ef. The Fermi energy of au
electron gas at a concentration
of 1 x 103Oelcetronscm~3 is given by

cr * (h2/2i}i){3n2nI13
as 0.5 x 10~6erg as i x 10s eV , D6)

' A discussion
\302\243ood of while dwaif siais is given by W. K Rose, Aitropkvsics, Hotf. R

WinHon, 1973.
 \"able 7.4 Fermi energy of degenerate fsmiion g
characierisiic values)

of mailer Particles Tf, in K

Liquid 3Hc atoms 0.3

Metal demons 5 x tQ1
While dwarf stars electrons 3 !09
\302\253

Nuclear matter nuctcons 3 x \302\2730u

Ncujron stars neutrons 3 x 10!I

about 10' higher than in a typieal metal. The Fermi temperature zFikB of the
electrons is =s 3 x 109K, as in Table 7,4. The actual temperature m the interior
of a while dwarf is believed to be of the order of I0\021 K. The electron gas in the
interior of a white dwarf is highly degenerate because the thermal energy is much
lower than the Fermi energy.
Are the electron energies in the relativistie regime?This question arises
because our theory of the Fermi gas has used the nonrelativistic expression
p2/2m for the kinetic energy of an electronof momentum p. The energy equi-

equivalence of the rest mass of an electronis

=
\302\243Q me2 \302\273
A x 10\"\"g)C x I010cins-!): * 1. D7)

This energy is of the same order as the Fermi energy D6).Thus relativistic

effects will be significant, but not dominant. At higher densities the Fermi gas
is reiativistic.

NuelearMatter
We consider the state of matter within nuclei. The neutronsand protons of

which nuclear matter is composed form a degenerate fermton gas, at least

qualiiaiively. We estimate here the Fermi tbenucleongas;The radius
energy of
of a nucleus that contains A nucleons is given by the empirical relation

R a A.3 x ltT13cm) x Al!\\ D8)

Accordingto this relation the average volume per particle is constant,for the
volume goes as R3, which is proportional to A. The concentration of nucleons
b nuclear matter is

?
S 0.11 x 1039cm-3 , D9)
 Chemical Potential Near Absolute Zero

about 103 times higher than the concentration of nudeons in a white dwarf
Star.Neutrons and protons are not identical particles. The Fermi energy of
the neutronsneed not equal the Fermi energy of the protons. The concentra-
of
concentration one Or the oilier, but not both, enters the familiar relation

\302\243,=\342\204\242C>r'\302\273)M E0)

For
simplicity let us suppose that the number of protonsis equal to the
number of neutrons. Theit

'W>n>
* a 0.05 x 1039 cm\023
\302\253\342\200\236\302\253\342\200\236\342\200\236(,\302\253 , {51}

as obtained from D9) on dividing by 2. The Fermi energy is

\302\243C.17
\302\243f x 10\023>1/3a;0.43 x 10\024erg \302\253
27 Mev. E2)

The average kinetic energy of a particlein a degenerate Fermi gas is -J of ihe

Fermi energy, so that in nuclear matter the averagekineticenergy is 16 Mev

per nucleon.

BOSON GAS AND EINSTEIN CONDENSATION

A very remarkable effect occurs in a gas of nonintcmcting bosons at a certain

transitiontemperature, below which a substantial fraction of the total number
of particles the system will
in occupy the single orbital of lowestenergy, called

the ground orbital. Any other orbital, including the orbital of second lowest
energy, at the same temperature will be occupied by a relatively negligible

number of particles. The total occupancy of all orbitalswill always be equal to

the specified number of particlesin the system. The ground-orbital effect ts
called the Einstein condensation.

There would be nothing surprising to us in this result for the ground stale
occccupaney if it were valid only below I(T14K.. This temperature is comparable
whh the energy spacing between the lowestand next lowest orbitals in a system

of volume 1 cm3,as we show below. But the Eitistein condensation temperature

for a gas of fictitious noninteracting helium atoms at the observeddensity of

liquid helium is very much higher, about 3K. Helium is the most familiar

example of Einstein condensationin action.

Chemical Potential Near Absolute Zero

The key to the Einstein condensation is the behavior of the chemicalpotential
of a boson system at low temperatures. The chemical potential is responsible
for the apparent of a large population of particlesin the ground
stabilization
orbital. We consider a system composedof a hrgc number N of nonintcractmg
bosons.When the system is at absolute zero all particlesoccupythe lowest-

energy orbital and the system is in the state of minimum energy. It is ceriainiy
noi surprising dim at i ~ 0 ail particles should be in the orbital of lowest
energy. We can show that a substantial fraction remains in the ground orbila!
at low, although experimentally obtainable,leniperaturcs.
If we put the energy of the ground orbital at zero on our energy scale, then
from the Bose-Einstein distribution function

<53)

e obtain the occupancy of the ground orbital at e = 0as

When 0 the
i\342\226\240-+
occupancy of the ground orbital becomesequal to the total

number of particles in the system, so ihal

Here we have made use of the series expansion cxp{\342\200\224

x)
*s I ~ x + \342\226\240
\342\200\242We
\342\200\242.

know dial .v, which hji/x, must be smallin comparison wiih unity, for otherwise
the total number of particles N could not be large. From this result we find

E5)

asT -.0. ForN = 1022at T = IK, we have /i s -1.4 x lO'38 erg.We noic

fromE5) that

E6)

as i ~+ 0. The chemical potential in a boson system must always be lower in

energy than the ground state orbiral, in order tirar rhc occupancy of every orbital
non-nesative.
b\302\243
 Chemical Potential Near Absolute Zcr

Cxampte;Spacingoflonat and second lowest ttrbiiuh of free atoms. The energy of an

orbital of an atom free to move in a cube of volume (' =\302\273
/-1 is

where n,, n>4

are
\302\273, positive integers. The energy e(I 11)of ihe lowest orbital is

+ 1 + 1) , E8)

ind the energy eB1 i) of one of the set of next lowest orbitais is

+ 1+1). E9)
W

The lowest excitation energy of the atom is

As =*\302\243BH)-
e(III) =* 3 x \342\200\224 . F0)
(-)

lfA/{4tie} - 6.6 x lO'^gandi, = I cm,

Ae = C){8.4 x IO-3!)(9,S6) = 2.4S x NT30erg. F1)

In temperature units, Ae/*8 - 1.S0x KT1*K.
This spiining is extremely small, and it is tiiRtcuU to conceive that
it can play unimportant

part in a physical problem even at the lovvest reasonably accessible temperatures such as
1 ijtK, whicli is I0\021 K. However, at the I mK temperature {55} gives )i ^ -1.4 x
iO\0211 erg for N = \\0:i aiouts, referred to the orbital ES) as the zero of energy.Titus /i is
much closer to the ground orbjia! than is the nexl lowest orbital E9), and cxp{[t(J 11)-
/i]/r} is ntucit closer io l than is ap{[t[2li}~n\\h}t so that t(Ill) dominates the dis-
distribution function.

The Boltnnann factor exp{~A\302\243/i) at 1 mK. is

exp(-1.8 x 10-\") s I - 1.S x I0\0211 , F2)

which is essentially unity. By D) we would expeel that even if/t * \302\253cilte occupancy of tlie
first excited orbit;il would only be of the order However, ihe nosc-Eiiliit-'itidis.tr ibutioii
of 1.

gi\\cs an entirely dilfctcni vuluti for the occupancy of ihe first exched ofhii;il:
because Ae \302\273
p.. Thus the occupation of the fust exciied orbiial ai 1 mK i:

F4)

so thai the fraction of the N particles thai are in this orbital is/.iV * 5 x 10i0v 10ir =
5 x 10\" 13t which is very small. We see thai the occupancy of the first exciied oibiialai low
temperatures is [datively very much lower than would be expeciedat first sight from the
simple Boltzmann factor F2). The Bose-Einstein distribution is quiie strange; ii favors a
situation in which ihe greatest part of tlie population is left in the ground orbiiai at sufi'l-
cienily low temperatures. The particles in ihe ground orbiial, as long as iheir number is \302\2731,
are called the Bose-Einsicin condensate. The atoms in ihe condensate act quiie differently

from the atoms in excited stales.

How do we understand the existence of the condensate? Suppose ihe aioms were
governed by ihe Planck distribution (Chapter 4), which makes no provision for holding
consiani the loial number of particles; instead, the thermal average number of photons

increases wiih temperature ai i\\as found in Problem 4.1. If the lav. s of nature restricted ihe
loiiil *iumbcr of photons to *i vliIuc $i we wotild suy thitt the i^rousid orbital of ii\\c plioion
gas contained the difference No = S* ~ N(r) between the number aiioued and ihe number
thermally excited. The ,V0 noncxciK'd photons would be described as condensco1 into tjic
ground orbital, but A'o becomes essentially zero at a temperature i, such that ;ill ,V photons
arc excited. There is no actual constraint on the totiil number of photons; however, there
is a constrain! on the total number A' of material bosons,sucli as MIe atoms, in n sysiem.
This consiniint is tht' origin of the condensation into the ground oibiul. The diiTcrctKc
between the Planck distribution and the Bosc-Einstein distribution h lliat the laner will
conserve the tot;tl number of particles, independent of icmperaiurc, so (hat none\\ciicd

atoms are really in the ground ilalc condensate.

Orbital Occupancy VersusTemperature

We saw in A9) that the number of free particle orbitalsper unit energy range is

fora particle of spin zero.The total number of atoms ofheliutn-4 in the ground
and exciied orbitals is given by the sum of the occupancies of all orbitals:

N . F6)

We have separated the sum over n into two parts. Here N0(t) has been written
for /@,t), the number of atoms in the ground orbital at temperature t. The
integral in F6) gives the number of atoms NJ,i) in all excitedorbitals,with
 \\

\\
\\r = 0.5

t
/(\342\200\242.

-\342\200\224\342\200\224
\342\200\224\342\226\240\342\200\224__

o!

Figure 7-10 Plot of Ihe boson distribution funciion for two temperatures, wilh sufficient
particles present to ensure ). a I. The integral ofthe distribution times the density of
slates gives the number N. of particles in exciied orbitals; the rest ofthe particles present
arc condensed into the ground slate orbital. The value of No is loo large to be shown on
Hie plot.

/(e,i) as the Bose-Einstetndistributionfunction. The integral gives only the

number of atoms in excited orbttals and excludes the atoms in the ground
orbital, becausethe function D(t) is zero at e = 0. To count the atoms correctly
we must count separately the occupancyNa of the orbital with e = 0. Although

only a singleorbitalis involved, the value of No may be very large in a gas of

bosons. We shall call NQ the number of atoms in the condensed phase and Nt
the number of atoms in the normal phase. The whole secret of the result wluch
follows is that at low temperatures the chemicalpotentialp is very much closer

in energy to the ground state orbital than the first excited orbital is to the
ground state orbital.ThisCloseness of p to the ground orbital loads most of
the population of the system into the ground orbital (Figure7.10).
Chapter 7: Fermi and Base Gases

The Bose-Einstein distribution function when written for the orbilal at

e - 0 is

NM=V^~, F7)

as in E4), where X will depend on the temperature x. The numberof particles

in all excited orbitals increases as tm:

or, with x s e/z.

Nolice the facfor zil2 which gives Ihc

dependence of Nc.
temperature
At sufficiently low temperatures of in
the number
particles Ihe ground si ale

wiUbe a very large number. EqualionF7) tellsus that / must be very close to
unity whenever No is \302\273
1. Then / is very accurately constant, becausea mac-

macroscopic value of ;V0 forces /. to be closeto unity. The condition for the validity
of the calculation is that No \302\273I, and it is not required that Ne\302\253 N, When
i in the integrand,
g s\302\273 the value of the integrandis insensitive to small devia-
deviations of a from 1, so that we can set /. -' 1 tn F8), although not in F7).
The value of the integral*in F8) is, when ). = 1,

The infiniic
= U1 10
>\342\226\240 gi
 it ton Temperature

Thus ihe numberof atomsin excited states ts

.. \\.IO6VB\\H\\3;:i
G0)

where /iQ
= (Af r/2rr/i2)a/2 is again the quantum concentration. We divide Nf by
N to obtain the fractionof atomsin excited orbitals:

= = G1)
N./N 2.6l2nqV/N 2.6l2na,'n.
The value X = 1 or
\\/N which
1 fed to G!) is valid as long as a large
\342\200\224

number of atoms are in the ground state. A!I particles have to be in some
orbital, either in an excited orbital or in the ground orbital- The number in
excited Orbitais is relatively insensitive to small changes in X. but the rest of
tlie particles have to be in the ground orbital.To assure this we must take /.
very close to 1 as long as NQ is a large number. Even 103 is a large numberfor
ihc occupancyof an orbital. Yet witliin Ar/rE = 10\"fi of the transition,where
is defined
r\302\243 by {72) below, [he occupancy of the ground orbilal is > !015 a loins
cm\023 at the concentration of liquid 4He. Thus our argument is highly accurate
at = 10~5.
Ar/r\302\243

Einstein Condensation Tcmperaiure

We define Ihe Einstein condensation temperature* as
i\302\243
(he (cmperaiure for
which the number of aionis in excited states is equal to (hetotal number of
atoms. That is, A^frJ
\302\253
N. Above ilie
r\302\243 occupancy of the ground orbital is
not a macroscopicnumber;below n the occupancy is macroscopic. From G0)
witli A7 for Ne we find for the condensation temperature

G2)
M \\2.6I2k

Now Gt) rimy be written as

G3)

wlicrc jV is tlic tola! number of atoms. The numberofatoms in excited orNuils

v;irtes ;is ii:2 a I Ictuperiitures below if;, as sliown in Figure 7.11. Tlic uik'iilaled
value of T^foralomsof 4Hc is a=3 K.

in, Atademic dcr W'issenschaficn, Berlin, Siuunesbcricliie 152-1,261;1925.3.

Chapter 7: Fermi aid Hose G:

1.0

\"n

0.8 /
t
\\
Superfluid
component'
\\

/
ormal flui

omponen \\
/
y

\\|
0 0.2 0.4 0,6 0.8 i.o

Figure7\302\273tl Condensed boson gas: tempcraiuce dependence

of the proportion No/N ofaioms in ihe ground orbiial and
of ihc pfoponion NJN of aloms in all exciled orbilals. We
have labeledihe two components as normal and superftuid
!o agree wilh the cusiomary description of liquid helium.
The slopes of all Hucc curves arc intended !o be zero at x = 0.

The number of particles in the ground orbital is found from {73):

No
= N - Ne =
N[l - {x/x\302\243?ir\\. G4)

We note that N may be of the order of 102\\Forx even slightly less than te a
large numberof particleswill be in the ground orbital, as we see in Figure7.11.
We have said that the particles in the ground orbitalbelowt form the condensed

phase or the superfluid phase.

The condensation temperature in k'elvin is given by the numerical relation

M) . G5)

where VM is the molar volume in cm3 mol\021 and M is the molecular weight.
For liquid helium Vu~ 27.6cm3 mol\021 and M = 4; thus TE = 3.1K.
 Liquid4 He

Liquid 4He

The calculated tempera! ure of 3 K is suggesiivelycloselo j he actual tempera Jure

of 2.17K a! whicha transitionlo a new stale of matter is observed to Jakeplace
in liquid helium (Figure 7.12). We believe that in liquid 4Hebelow2.17K there
is a condensation of a substantial fractionof iheatomsof 4He inlo the ground
orbiial of jhe system. This is different from the condensation in coordinate
space that occurs iit the condensation of a gas to a liquid. Evidently ihe j'nicr-
alomic forces that lead to ihe liquefaction of4Heat 4.2 K under a pressure of
one atmosphereare too weak to destroy the major effects of the boson con-
condensation at 2.17 K. In this respect tlte liquid behavesas a gas. The condensa-
into
condensation the ground orbital is certainly connected with the properties of bosons.

2.5

2.0
\"\302\253,

s t.o

X y
0.5

0
1.6 1.8 2.0 2.2 2.4 2.6

Tempera!
u;

Figure 7.12 Heat capacity of liquid *He. The sharp

peak near 2.17 K is evidence of an important transition

in the nature of the liquid. The viscosity of the liquid

above the transition temperature is typical of normal

liquids, whereas the viscosity belowtlic transition as

determined by rate of flow through narrow slits is
vanishingly small, at least I06 times smaller than the

viscosity above the transition. The transition is often

called a lambda transition merely becauseof tlte shape
of the graph. After Kccsom et al.
Chapter It Fermi twd Base Gases

The condensation is normally not permitted for fennions, but pairs of fermions
may act as bosons,as in the superconductivity of electron pairs (Cooper pairs)
in metals. A different type of transition to complex phases with
superflutd

properties has been observed in liquid 3He below 3mK. Atoms of 3He have
spin \\ and are fermions, of 5Hc atomsact as bosons.
but pairs
Wecan give several arguments in support of our view of liquid helium as a
gas of noninteracling particles. A t first sight this is a drastic oversimplification
of fite problem, bur there are some important features of liquid helium for
which the view is correct.
{a) The molar volume absolute zero is 3.1 timesthe volume
of liquid 4He at
[hat we calculate from the known interactions of helium atoms.Titeinteraction
forces between pairs of helium atoms are we!!known experimentally aud

theoreticaily, and from these forces by standard elementary methods of solid

state physics we can calculate the equilibrium volume of a static lattice of
helium atoms. In a typical calculation we find the molar volume to be 9 cm3
mo!~', as compared with the mo!\"l. Thus the kineticmotion
observed 27.6 cm3
of the helium atoms has a large elTccton ihe liquid siale and leads to an ex-

expanded structure tn which the aloms to a certain extentcan move freely over

appreciable distances. We can say ihat ihe quantum zero-point motion is

responsible for the expansion of ifie inoiar volume.
(b) The transport propertiesofliquid helium in ihe normal state are not very
different from ihosc of a normal classical gas. In particular,the ratio of the

thermal conductivity K to the product ofthe \\iscosity tj times the heat capacity
per unit mass has the values
at 2.SK
JC__ ~_ |16,
JJCV [3.2, at 4.0 K

These vaiues are quite closeto ihose observed for normal gases at room
temperature\342\200\224see Table 14.3- The values of the transport coefficientslliem-
selvesin the liqirid are with in an order of magnitude of those calculated for the

gas at the same denstly. Normal liquids act quite differently.

(c) The forces in [he liquid are relalively weak, and I be liquid does not exist
above the critical temperaiureof 5.2K, which is itie maximum boiling pouit
observed. The binding energy vvotiki be perhaps ten limes stronger in Ihe
equilibriumconfijjuralion of :i si:uic lull ice, hul the expansion of ilte molar
volumeby the quanlum zero-poml motion of the atoms is responsiblefor tile
reduction in the binding energy to the observed value. The value of ihe critical

iemperaliireis dirccliyproportional io binding energy. the

(d) The ikjuid is slablc at absolutezero pressures ai muter 25atnt; nbuvc

25 aim the solid is more stable.
 Liquid 'He

as g

r'Hz 'lie
\\

T, in K-

Fi\302\253iire7.13 Comparison of rales of flow of liquid 3He and

iiqujd 4He uuder gravify through a fine hole. Noiice fhc suddcr
onset of high fluidify or superfluidity in \"He. After D. W.
Osborne, B. Weinsiock, and B.M. Abraham, Pliys. Rev.75,
9S8 A949).

The new stale of ntallcr inio which liquid 4He enters when cooled beiow
2.17 K. has quhe asionishing properlies. The viscosity as measuredin a flow

experiment* zero (Figure 7J3), and the [hernia!

is essenlially conduciiviiy is
very high. We say thai liquid 4He below Ihe [ransilion icmperalure is a super-
fluid. More precisely, we denole liquid *He below ihe transiUon lempcralurc

as liquid He U, and we say llial liquid He II is a mixlurc of normal Huid and

Supcriiuid coniponcnls. Tlte normal fluid component consisfs of Hie helium

aloms in thermally excited orbiials, and the superfluid component consisis of

life helium atoms condensed into the ground orbital. It is known lhat liie
radioacljve boson 6He in solution in liquid 4He does not tat:e part in Ihe

supijrflow of the latter; neither, of course,doesthe fermion 3Hc in solution in

4llc kike part in ihe super/low.
We speak of liquid \"Mle ;ihovc liie iransilion leniper^lnrc as liquid ik i.
Thereis no supcrdnid coiliponcnt in Ikjuid lie 1, for here the grama! oihii;il
ot-vupiuicy is ucgti^ihlc, being uf l\\ic suim: order of uKiyuiiude as ihe oct.'up:mt;y

fliii.ls ofiliirftciil visttiMlics, sums c\\fKfinn:liii iiicisuic ifJiraif(Jj;t; i imnily. .t\302\273Juliet l'vjil'Ijjjk'j
Bic.isufi; the .ivct.igc of K'ii, i)f 'be aierjgt* lluidiiy.
Kjurc 7.14 The mcUing curve of liquid and
solid helium (*Hc). and the transition curve
between itie two forms oftiquid helium, He I
and He II. The liquid He ll form exhibits

sispcrliow ptopciiics as a consequence of Uic

condensarionof aroms into the ground orblial
of the s; stem. Note ihat licl'mm h a liquid at
absolute zero ai pressures below 25aim. The
tiquid-\\apor boiling curve is not included in
this gcaph as ii would ractgc wjih [he zcco
pressuic line.After C. A. Swenson, Phys. lev.
19,626E950).

of any other low-iying orbital, as we have seen. The regions of pressureand

temperature in which liquid He { and ({ exisl are shown in Figure 7,14.
The development of superftuid propertiesis no[ an automatic consequence
of [he Einstein condensation of aloms into the ground orbira!. A dvanced cal-

calculations show that il is [he existence of some form (almost any form) of inter-
interaction among aloms [hat leads [o the development of superfluid properties in
[he aloms condensed in the ground orbital.

Phase Relationsof Helium

The phase diagram of 4He was shown in Figure 7.14. The iiquid-vapor curve
can be followed from Ihe crilical poinl of 5.2 K down to absoiule zero without
any appearance of the solid. Al ihe transilion temperature liquid, Ihe normal
called He I, makes a transit ion to the form wilh superfluid properties,called
He II. A temperature called the/ poinl is the triple point al which liquid He (,

liquid He ii,and vapor coexist.Keesom, who first solidified hciium, found that
the solid* did not existbeiowa pressureof 25alm.Another triple point exists

by B. Bertram and Guyed Scientific Am

\342\200\242
An tnlercsring discussion of solid heli m is given R. A.
can, August 1967, pp. 85-95. Solid 'He :xisis in three crysral structures according ro rhc condili
 ; of Helium

'He
/

Solid
/
\342\226\240i
Liquid

5 40
/
Gas

Figure 7.15 Pliase diagrams for liquid 3He, (a) in

kelvin and (b) in miKikeivin. In rhc region of negaiive
slopeshown in (a) on ihc phase boundary [he soiid has
a higher eniropy ihan liie liquid, and we have io add
heal lo 'he liquid io solidify it. Superfluid properiics
appear in(b) in ihc A and B phases of liquid JHc. The
A phase is double\342\200\224in a magnetic field [lie phase divides
imo hvo componenls wiih opposiie nuclear magnciic
momenis.

at 1.743 K: here the soiid is in equilibriumwiih ihe iwo liquid modifications.

He I and He II.The two triple poinis are connecicd by a line !ha!separatesihe
regions of existence of He II and He I.
The phasediagram of 3He differs in a remarkable way from the phasediagram
of4He. Figure 7.15 exhibiis the importance of ihe fermion nature of 3He.Note
ihe negaiive slope of ihe coexistence curve at low temperatures.As explained
in Chapter 10, the negative slope means thai !hc entropy of! he liquid phase
ISlower lhan !heentropy of the solid phase.

Qunsipariieies and Superfluidity, 4He

For many purposes the superfluid component of liquid helium il behaves as
if a vacuum,
it were as ifi! were not thereat all.The No atoms of the supcrfluid
are condensed into the groundorbila!and have no exeitation energy, for the
ground orbila! by definition has no excitation energy. The superfluidhas energy
only when I he center of mass of the superfluid is given a velocity relative to tlic
laboratory reference frame\342\200\224as when Ilie superfltiid is set inlo flow relative to

the laboratory.
The condensed component of Na atoms will flow with zero viseosity so long
as the flow does not ereate cxcitatiosis in tile superfluid\342\200\224that is, so long as no
atoms make transitions bctwecilthe ground orbital and !ho excited orbitals.
Such iransitions might be caused by collisions of helium atoms with irregu-

irregularities in the wall of the tube through which the helium atoms are Rowing.
The transitions, if they occur, are a cause of energy loss and of momentum

loss from the moving fluid, and the flow is not resistanceless if such collisions

can occur.
The criterion for superfluidity involves the energy and Momentum relation-
relationshipof the excitations in liquid He !!. If the excited orbitals were really like the
orbilais of freeatoms,with a free parliele relation

E = l\\.ivi = -_(/,/,-)* G6)

between the energy e and the momentum Mo or /ik of an atom, then we can

show that superfluidity would not be expected.

Here k = ^/wavelength. But
bceause of the existence of interactions between the atoms the low energy
excitations do not resemblefree particle excitations, but are longitudinal sound

waves, longitudinalphonons(Chapter4).After all, it is not unreasonable that a

longitudinal sound wave should propagate in any liquid, even though we have
no previous experience of superliquids,
A language has grown up to describe the low-lyingexciiedstatesofa system

of many atoms. These slates are called elementary excitations and in their

particie aspect the states are called articles. (jiiasip Longitudinal phonons are
the elementary excitations of liquid He II. shall We give the clear-cut experi-
menial evidence for this, but first we derive a necessary conditionfor super-

superfluidity. This condition will show us wiiy

the phonon-tfke nature of the
elementary excitations leads to the superfluid behavior of liquid He II.
 Quaupanhlts andSuptrJluMty, 'lie

Figure 7. [$ Body of mass Mo

velocity
V down a cylinder th;it
\342\226\240\342\200\242a
He It at absolute zero.

We consider in Figure 7.16 a body, a steel ball or a neutron, of

perhaps
mass Mo falling with velocity V down a column of liquid helium aJ rest at
absolute zero,so that initially no elementary excitations are excited, if the
nioliou of the body generates elementary excitations, Jhere will be a damping
forceon Jhe body, in order to generate an elementary excitation of energy ck
alid momentum hk, we must satisfy the law of conservationof energy:

*= + , G7)
\\M0V2 |A/0F'2 \302\243k

where V is the velocity of the body after creationof the elementary excitation.

Furthermore, we must sarisfy the law of conservation of momentum

= Ma\\\" + hk. (IS)

The two conservation taws cannot always be satisfied at the same time even
if the direction of Jhe excitation created in the process is unrestricted. To show
Chapter 7; Fermi and Base Gases

this we rewrite G8)as

- l
A/0V Af0V 0

and lake the square of boihsides:

M02V2
-
2A/0/iV-k + h2k2 = MQ2V'2.

On multiplication by l/2Af0 we have

|A-/K2 /V k + \\M0V'\\ G9)

We subtract G9) from G7) to obtain

\342\226\240

'
1
(SO)
2mTq

There is a lowest value of the magnitudeof the velocity V for which this
equation can be satisfied.The lowest value will occur when the direction of k
is parallel to that of V. This critical velocity is given by

-h2k2

Vs
- minimum of- (81)

The conditionis a little simpler to express if we let the mass Mo of the body
become very large, for then

(82)

A body moving with a lower velocity than Vc will not be able to create excitations
in the liquid,so that the motion will be resistance less. The viscosity will appear
to be zero. A body moving with higher velocity will encounter resistance
 Quusipartfctes and Superfluidity, *lle

the curve from below. The slopeof this line is equal to the critical velocity, if
ck
s=
h2k2/2M, as for the esciiation of a free atom, [he straight line has zero

slope and the crilical velocity is zero:

Free atoms: Vs
= minimum oUik/2M = 0. (83}

The energy of a low energy phonon in liquid He II is =

\302\243k tui>k = tusk in [lie
frequencyregionofsound waves where the product of wavelcnglh and frequency
is equal to velocity of sound the
t'a, or where the circular frequency mk is equal
to [he product of vs times the wavevector k. Now the critical velocity is

Phonons: Vc
= minimum offtr^/hk = v,. (84)
The critical velocity Vc isvelocity of sound if (84} is valid for ;ill
equal to the
wavcveciors, which it is not in liquid helium ii. The observed criticalflow
velocities arc indeed nonzero, but considerably lower than the velocity of sound
and usually lower than the solid straight line in Figure 7.i 7, presumably beeause
the plot of Ek versus lik may turn downward at very high hk.
The actual spectrum of elementary excitationsin liquid helium II has been
determined by the observations on the inelastic scattering of slow neutrons.
The experimentalresultsareshown in Figure 7.17. The solid straight line is the
Landau critical velocity for the range of wavevectots coveredby the neutron

experiments, and for this line the critieal velocity is

Vc
\302\253
&/hk0
~ 5 x I03 cm s\021 , (85)

where A and k0 arc identified on the figure.

Charged ions of helium in solution in liquid helium 11 under eertain experi-
experimental conditions of pressure and temperature have been observed*to move
5 x 103 cm s\"
*
almost like free partieles and to have a limiting drift veloeity near

closely equal to the calculated value of (85).Underother experimental condi-

conditions the motion of the ions is limi(ed at a lower velocity by the ercation of
vortex rings. Sueh vortex rings are transverse modes of motion and do not
appear in the longitudinal modes covered by Figure 7.17.

Our (84) for a neeessary condition for the critieal

result velocity is more
general than the calculation we have given.Our calculation demonstrates that

a body will move whhout resistance through liquid He II at absolute zero if

the velocity V of the body is less than the critieal velocity Vc. However, at

* L. Rev.' 123,727 G. W. A966).

Meyer and F. Reif, Phys. U96t|; Rajfiekt, Ph)s. Rev. Lcllcrs 16,934
 1.0 2-0 3.0
WavevccioT, in units of 50s cm\021

Figure 7.17 Energy ck versus wavevecior i of elementary

exciiaiioHS in liquid helium ai t.JJK. The paraboliccurve rising
from represents the iheoreiicaiiycalculated
lhe otigin curve for
free helium aioms ai absolutezero. Tlic open circles correspond lo
the energy and momentum of the measured exciutions. A smoosh
curve has beendrawn through ihe poinls. Hie broken curve
rising iineariy from lhe origin is she tiieorcsiealphonon brynch
wfili a vclodfy of sound of 237 m s\"'. The solid straight
gives line

the crmcai vdocily, in appropri^se uniii: Ttie line gi\\e$ imxn-

jh\302\253

mum ofij/A\" over ihe region of k covered in ihcse expcrimenls. After

D.G. Hcnshaw and A. D. B. Woods. Phis. Rev. t2l. 1266A960-

femperutures above absolute zero, but below the Einstein temperature, there
wili be a normal fluid component of demcnlary excitations that are
thermally
exciied.The normal fluid component is the source of resistance to the motion
of the
body. The supcrflow aspect appears first m experiments in which the

liquid flows out ihrough a fine lube in the side of a container. The normai
fluid component may remain behind in lhe container while the superfluid
component leaks out without resistance.The derivation we have given of the
critical velocity also holds for this situation, with the velocity of the super-
V as
fluid relative to the walls of the tube; A/o is the niass of the fluid. Excitations
would be createdabove V( by the interaction between the flow of the liquid
and any mechanical irregularity in the walls.

Supcrfluid Phases of 3He

Three superfluid phases of liquid 3He are known* (Figure 7.15b), but\342\200\224in

contrast to liquid 4He\342\200\224with transition temperatures of only a few milhkelvin.

The superfluid phases are beiieved to be qualitatively similar to the super-
superconducting slate of electrons in metals, where pairs of particlesin orbiials near

[he Fermi surface form a type of bound siaie known as a Cooper pair. Such a
pair is qualitatively like a diatomic molecule, but the radius of the molecule
is much larger than the average iniereleciron spacing in a metal or the average
mlerparticle spacing in liquid 3He.
In metallic [he two electrons [hat form
superconductivity a Cooper pair are
in a nonmagnetic (singlet) spin staie. In the superfiuid siates of liquid 3He the

Uvo aioms [hat form a pair are in the triplet spin states of the two JHe nuclei,
so thai ihree magnetic supcrfiuids are possible, corresponding to spin orienta-
orientations M,
~ 1, 0, and -1, or mixturesof these three states. The magnetic
superfluids have been explored experimentally,
and both the magnetic \302\243nd

superfiuid properties have been confirmed.

SUMMARY

1. Comparedto a classicalgas,a Fermi gas at low temperature lias high kinetic

energy, high pressure, and heat capacity. The entropy of
low the Fermigas
is zero in the ground slate. The energy of the highest filled orbiial in the

ground state of a free particle gas of ferniions of spin j is

' ~ \342\226\240

ut\\ v
)

2, The lota! kinezic energy in the ground stale is

\342\200\242
For elementary see j. C. U heat icy,
roif^s, Physics Today, February ly/b. p. i
PU)sicsfluiic!tn25. 311ii97j|;aritt J. R. Hook, i%sici Bulletin 29. 5i3A97SJ. For

C Wll f Ph R \\d Ph
Chapter 7: Fermi and Base Cases

.3. The density of orbitats at r,f is

\"D{Cf)
~ 3,V/2c^.

A. The heat capacity of an electron gas at r \302\253

i> is

in fundamental units.
5. For a Boscgas at r < rE the fraction of atoms in excited orbitiiis is

fi. The Einstein condensation temperature of a fj;iS of nuniiitenicthig bosons

N Y>
__2nftV

PROBLEMS

i. Density of orh'ttah hi one and two dimensions, (a) Show that the density
of orbiiafs of a free electron in une dimension is

2
O,(e) =\302\273
(t,/rc)t2*rt/Aa\302\243I , (86)

where i. is the length of the line,(b) Show thai in two dimensions, for a square
of area A,

= (87)
\302\251i(e) ^tiii/Tcft2 ,

independent o(e.
2. Energy of refarivistic Fentu gas. For electrons with an energy e \302\273
me1,
where in is the rest mass of the electron,the energy is given by e = pc, where
p is [he momentum. For electrons in a cube of volume V = i.3 the momentum
is of [he (nh/L), form
multiplied by (n/ + it/ + n:2)ll2> exactly as for the
nonrelativistic limit, (a) Show [hat in this extreme relativistic limit the Fermi
energy of a gas ofN electronsis given by

\302\273
zr AncCii/n)\025 , (88)
 Problems

where u =
N/V. (b) Show that the total ener\302\273y of the ground stale uf ihc gas is
=
(/\342\200\236 J,Vef. (S9)

The general problem is Ireaied by F.Jutlner,Zeilsduifl furPhysik47,542({928).

3. Pressure and entropy of degenerate Fermi gas. (a) Show that a Fermi
electron gas in the ground stale exerts a pressure

In a decrease
uniform of the volume of a cube every orbital has i!s energy
raised; The is
energy an orbital proportional
of to XjL1 or to l/f/2|J. (b) Kind
tin expression for Use entropy of -a Fermi electron gas in the region r \302\253
t>.
Notice that a -* Oast-0.

\"/. Chemical potential verms temperature. Explain graphically why the initial
curvature of p. versus t is upward for a fermion gas in one dimension and
downward in three dimensions
(Figure 7.7). Him: The C,(e) and *D3(e) curves
are different, where *D, is given in Problem t. It wiii be found useful So set up
the integral for N, the number of particles, and to consider from the graphs
the behavior of the integrand betweenzerotemperature and a finite temperature.

5. Liquid 3He as a Fermigas. The atom 3He has spin 1 = \\ and is a fermion.
(a) Calculate as in Table 7.1 the Fermi sphere parameters vF, ef, and TF for
3He at absolute zero, viewed as a gas of nan interacting fermions. The density

of the liquid is 0.081 g cm\" \\ (b) Calculatethe heat capacity at low temperatures
T \302\253TF and compare with the experimental value Cr
= 2.89NfcBT as observed
for T < 0.1K by A. C. Anderson, W. Reese, and J. C. Wheatley, Fhys. Rev.

130, 495 A963); see also Figure 7.18. Excellent surveys of the properties of
liquid 3He are given by J. Wilks, Properties of liquid and solid helium,Oxford,
1967,and by J. C. Whealley, \"Dilute solutions of JHe in \"Heat low tem-
temperatures,\" American Journal of Physics 36, 181-210A968). The principles
of refrigerators based on 3He-*He mixtures are reviewed in Chapter 12 on
cryogenics; such refrigerators produce steady temperatures down to 0.01 K.
in acting
continuously operation.

6. Mass-radius relationship for white dwarfs. Consider of mass

a white dwarf
M and radiusR.Let the electrons be degenerate but nonrelativistic; the
protons
are nondegenerate. Show (a) that the order of magnitude of the gravitational
self-energyis -GM2jR, where G is the gravitational constant. (If the mass
density is constant within'the sphere of radius R, the exact potential energy is
Chapter 7: Fermi and Sose Gases

5.0

20 SO $00 200

Temperature, in K

Figure 7.18 Heat capacity of liquid 3He and of a 5 percent solution of

3He in liquid *Hc The quansisy plotSed on she vcrSica! axis is C/T, and
she horizontal axis is T. Thus for a Fermi gas in the degenerate temperature
fegion the theoretical cufves of C/T at constant volume are horizontal.
The curve for pure 3Heis taken at constant pressure, which accounts fof
the slight slope. The curve for the solution of Hie in liquid 4He indicates
thai she 3He sis solution acts as a Fermi gas; she degenerafe region at low

temperature goes over to the nondegene/ate region at higher temperature.

The solid Sine through she experimental possHsfor the solution is drawn
hrTf - 0.331K, which agrees with the calculation for free atoms if the

effective mass is taken as 2.38times the mass of an atom of 3He.Curves

after J. C. Wlicatley, Amer. J. Physics36 A968).

-3GM2f5R). (b)Showthat the order of magnitude of the kiiicsic esiergy of the

electrons in the ground state is

w here m is she mass of an clcclrosiand mass of a proton, (c) Show

Mit is the
lhai if she gravitational and kitsctic energies are of the same orderof magnitude
(;ss required by ihe virsal theo/esiiofsnechanics), Mll3R ~ 10;ogW2cm.{d)Iflhe
 Figure 7.19 Heal capacity of ;tn

Eimtcin gas ut cortilam volume.

mass is equal to that of she Sun B x lQ33g), what is the density of the while
dwarf? (e) H ss believed thai pulsars ate starscomposed ofa colddegenerate
gas of neuUons. Show that tot a neutron star Mll3R =s 10!7 g\023ciyi. What is
she value of the radius for a neutron star with a mass equal so that of the Sim?
Express she resuls tn km.

7. Photon condensation. Considera science ftclton universe in which she

number of photonsN is constant,at a concentration of I0Iocm\"s. The number
of thermally excited photons we assume is given by the result of Problem4.1,
which is Ne = 2.404 Kt3/*2/] V. Find the criticaltemperature in K below which
jVe < JV. The excess N \342\200\224 will
Nr be in the photon mode of lowest frequency;

the excess might be described as a photon condensatein which there is a large

concentration of photonsin the lowest mode. In reality there is no such principle
that the loui! number of photons be constant, hence there is no photon

A1. Energy, heat capacity, ami entropy of degenerate bosongas. Find ex prcs-

sions ;is ;i function of tcmpcf.ifun; in the region x < th for the cne-igy. hc;il
op.idiy, ;mii cn[[opy of ;i y;is o\\ ,V noniiilcMlcling bosons of hpiil zero confiiial
to ;i volume V. Put the del'milc imegnil in dim ens ion less form; it need not be
evaluated. The calculated heat capacity above and below r\302\243is shown in
Figure 7.19. The experimental curve was shown in Figure 7.12. The dilTcrcnce
Chapter 7: Fermi and Base Gases

between the two curves is marked;It is ascribedlo the effect of interactions

between the atoms,

9. Bosongasin one dimension. Calculate the integral for Nt{x) for a onc-
dimensional gas of noninteracting bosons, and show that the integral does
not converge. This result suggeststlial a boson ground stale condensaie does
not form in one dimension. Take/. ~ I for the calculation. (The problem should
really be treated by means of a sum over orbitats on a finite line.)

10. Relativhtk white dwarf stars. Consider a Fcrnii gas of A' electrons each
of rest mass m in a sphere of radius R. Conditions in certain white dwarfs are
such that the great majority of electrons have extreme relativislic kinetic
energies e = pc, where p is the momentum. The de Broglie relationremains
). ~
Inhjp. Problem ground stale kineticenergy
2 gives the of the A1 electrons
on the assumption that pc for ali elecrrons. Treat the sphere as a cube
e =

of equal volume, (a) Use the standard viria! theorem argumentto predictthe
value of N. Assume that the whole star is ionizedhydrogen, but neglect the
kinetic energy of the protons comparedto that of the electrons, (b) Estimate
the value of N. A careful treatment by Chandrasekhar leads not to a single
value of N, but lo a limil above which a stable while dwarf cannot exist: see
D. D. Claylon, Principlesof stellarevolution and nucleosynthesis, McGraw-Hill,
1968, p. 161; M- Harwii,Astrophysicat concepts, Wi!ey, 1973.

11. Fluctuations in a Fcwri gas. Show for a single orbisa! of a fermion system
that

<(ANJ> - <N>A - <N\302\273 , (91)

if is
\342\226\240GAO the average number of fermions in thai orbiial. Notice that the

fluciuation vanishes for orbitals with energies deep enough below the Fermi
energy so thai <N>
= I. By definition, AN s N ~ <N).
12. Fluctuationsin a Basegas. If </V) as in (I!) is the average occupancy
of a single orbiial of a boson system, fhen from E.83) show iiiat

<(ANJ> = <JV>(I + <JV\302\273. (92)

Thus if fhe occupancy is large, with <N> \302\273I, ihe fractional fluctuafions are
of the order ofuntty; <(ANJ>/<N>2\302\2531, so mat the actual fluctuations can
be enormous.It been said that \"bosons
has travel in flocks.\" The first edition
of thrs text has an elementarydiscussion of the fluctuations of photons.

13, Chemical potential versusconcentration* (a) Sketch carefully the chemical

potential versus the number of particles for a boson gas in volume V at
icmpcraiure r. Include both classical and quantum fegimes. (b) Du the same
for a syssem of fermions.
14. Two orbilai boson systent. Consider a system of A' bosons of spin zero,
with orbitals at (he single particle energies 0 and e. The chemical potential is
/x, and the temperature is r. Find r such, that the fhefma! average population
of the lowest the population of the orbital
orbital is twice at e. Assume
JV 3> | and make what approximations are reasonable.
If the atoms in a gas have integral
spin (counting the sum of electronic
and nuclear spins), they can form a boson condensate when the gas is cooled
below the Einstein condensation temperature te given by G2):

~ BTTh2iM){Ni2.6\\2VJ/\\
rE

For atoms in the vapor phase she Einstein'condensation temperature is very

Sow because the number densities are very low\"; In A995) early successful
experiments were carried out at Boulder, MIT, and elsewhere. Such experi-
experiments, which are extraordinarily complex, mark the exciting forefront of the

quantum gas field. A large literature on BEC experiments and theory is on

the Web.
One set of experiments (MIT) started with a beam of sodium atoms
exiting an oven at 600K at a concentration N/V of SO14 cm\023. Whas happens
next is the result of a number of clever tricks with laser beams directed on
one pint or another of the beam of atoms. First file atoms are slowed by one
laser bcum from an exit velocity of 800 in jt1 to about 30 in s~'. This is
slow eiioug.lifor !0!\" ntonis to be trapped within a magneto-optical trap.
Fusthcr tricks, including evaporation, reducedthe temperature of the gas to
2 /nK, the uhraiow temperature rE at whieli the condensate was formed. The
concentration at rE was again !014atoms/cmJ.
The atoms in the condensed phase are in tlie ground orbital and expand
Giiiy slowly once released from the trap. The atoms in excited states move
relatively rapidly out of their steady-state positions. The positions of the
asoms can be recorded as a funcsion of sime after release, using a laser beam.
The number of asoms in excited orbitals is in good agreement with she t3
law, G3). With this sechnique signasure of Bose'Einssein condensation is
the
she sudden appearance of a sharp peak of atoms as the semperature is
decreased through rE. The peak comes from lighs scattered by atoms in the

condcusase; she wings of she line from light scattered by atoms in excited

orbitals.
Chapter 8

Heat and Work

ENERGY AND ENTROPY TRANSFER:

DEFINITION OF HEAT AND WORK 2-7

HEAT ENGINES: CONVERSION

OF HEAT INTO WORK 2IS

OirnOl Inequality 2-S

Sources of Irrevcrsibiliiy 252
Refrigeraiors 233
Air Condiu'oners and Heat Pumps 255
Carnot Cycle 2?6
Example:Carnol Cycle for an Idea! Gas 237
Energy Conversion and the Second Law of Thermodynamics 240
Palh Dependence of Heat and Work 240

Irreversible Work 242

Example: Sudden Expansion of an Ideal Gas 245

HEAT AND WORK AT CONSTANT

TEMPERATURE OR CONSTANT PRESSURE 245

Isothermal Work 245

IsobaricHeal and Work 245

Example: Elecirolysis and Fuel Cells 247

Chemical Work 250

Example: Chemical Work for an Ideal Gas 25!

Magnetic Work and Superconductors 2--

SUMMARY 257

I'UOBLEMS 2? 7

1. Heat Pump :::

2. Absorption ReiYigerator
2!:<

). I'lwicm Carnol Hnginc 25S

4. I leal Engine\342\200\224Kel'rigcralor Cascade 25S

5. Thermal Pollution 258

6. Room Air Condilioner 258
7. Light Bulb in a Refrigerator 259
8. Gcotlierrnal Energy 259
9. Cooling of Nonmetallic Solid to T= 0 259
10. Irreversible Expansion of a Fermi Gas 259
 Energy and Entropy Transfer: Definition of Heat and Work

ENERGY AND ENTROPY TRANSFER:

DEFINITION OF HEAT AND WORK

Heat and work are two different forms of energy transfer.Heat is the transfer

of energy to a system by thermalcontactwith a reservoir. Work is the transfer

of energy to a system by a change in the external para meters that describe the
system. The parameters may include volume, magnetic field, electric field,or
gravitational potential. The reason we distinguish heal from work will be clear
when we discuss energy conversion processes.
The most important physical process in. a modern energy-intensive civiliza-
civilizationis the conversion of heat into work. The IndustrialRevolution was made

possible by the steam engine, which converts heal to work. The internal com-
combustion engine, which seems to dominate man as much as It serves him, is a
device to convert heat to work.The problem of understanding the limitations
of the steam enginegave rise development of thermodynamics.
to much of the
Energy conversion remains central applications of thermalphysics
one of the
because most electrical energy is generated from heat.
The fundamental difference between heal and work is the difference in the

entropy transfer. Consider the energy transfer dtl from a reservoir to a system
with which the reservoir is/in thermal contacl at tcmperaiure t; an entropy

transfer da ~ dU/x accompanies ihe energy transfer, accordingto the argument

of Chapter 2. This energy transfer is what we defined above as heal, and we see
it is accompanied by entropy transfer- Work, being energytransfer by a change

in external parameters\342\200\224such as the position of a piston\342\200\224does not transfer any

entropy system.There is no placefor entropy
lo the to come from when only
work is performedor transferred.
However, we must be careful; the toial energy of two systems brought into
contactis conserved,but their total entropy is not necessarily conserved and
may increase. The entropy iransfer between two systems in ihermal contactis
wcl! defined only if theenlropy of one system increasesby as much as the entropy
of the other decreases. Let us restrict ourselves for the present to reversible
processes such that the combined entropy of the interacting systems remains
constant.Later we will generalize the discussion to irreversible processes which
are processes in which the total entropy of the two systems increases,as in the

heat flow example in Chapter 2.

CkapterS:Heat and Work

We can give a quantitative expressionto the distinction between heat and

work. Let dU be the energy of a system during a reversible
change process;da
is the entropy change, and t is ihe icmperitture. We define

i!Q s xda (I)

as the heatreceived
by the system in the process. By the principleof conservation
of energy,

= aw + dQ ,
dV
B)

which says thai the energy change is caused partly by work doneon the sysictn
and partly by heal added to ihe System from the reservoir. Then

t1W = dU ~ (tQ
= dV ~ zda
0)

is (be work performed on the system in the reversible process. Our reasons for
designatingheat and work by iftjand dW rather ihan dQ and d\\V arc explained
below. For da \342\200\224
0, we have pure work; for dV = xda, pure heat.

HEAT ENGINES: CONVERSION

OF HEAT INTO WORK

Catnotinequality. Heat and work Have different roles in energy conversion

processes because of the difference in entropy transfer. Consider two conse-

consequences of the difference:
(a) All types of work are freely convertible into mechanical work and into
each other, becausethe entropy transfer is zero. An ideal electrical motor,
without mechanical friction or electricalresistance,is device a to convert
electrical work into mechanical work. ideal electrical generator An converts
mechanical work into electricalwork. Because forms of work all are freely
convertible, they are thermodynamically equivalent to each other and, in

particular, equivalent (o mechanical work. The term denotes work all types of
work.
(b) Work can be completely converted into heat, but the inverse is not irue:
heat cannot be completely converted into work. Entropy entersthe system with

the beat, but docs not leave the system with the work. A device that generates
work from heal must necessarily strip the entropy from the heat that has been
converted to work. The entropy removed from the converted input heat cannot
be pennittedto pile up inside the device indefinitely; this eniropy must ulti-
ultimately be removed from the device. The only way to do this is to provide more
 Heal\302\243itgines: Conversion of Heat into Work

Entropy

Figure 8.1 Eniropy and energy flow in any continuously operating

reversible devicegencralmg work from \\\\ca.t. The entropy outflow
must equal ihc entropy inflow.

input heat than the amount converted to work, and 10 ejectthe excess input
heat as waste heat, at a tempcrat ure lowerthan thai of the input heal (Figure 8.1).
BecauseiiQ/ifc = r, the reversible heat iransfer accompanying one unit of

entropy is given by the temperature .it which the heat is transferred. It follows
that only part of the input heat need be ejected at the lower temperatureio
cany ;t\\\\ay all the entropy of the input heat. Only the difference bctv^^.i input
and outpul heal can be convened to work. To prevent ihc accumulation of
eittropy there must be some output heat; therefore h is impossibleto convert
ail the input heal to work!
A prohibition against unlimited entropy accuniLiiaiion tn a device does not
mean entropy cannot accumulate temporarily,provided
that it is ultimately
devicesoperatein
removed. Many practical energy-conversion cycles, and the
entropy contained in the device varies periodically with time. Such a cyclic
deviceis calleda heat engine. The internal co'rnDiisTion engine is an example:
The entropy contained in each cylinder is at a minimum near the beginning of

the intake stroke and a maximum near the beginningof the exhaust stroke.
There is a value of the entropy eontent to which the devicereturns cyclically;
the
entropy does not pile up indefinitely.
What fraction of the input heat Qh taken in during one cyele at ihe fixed higher
temperatureth can be convened The input entropy associatedwith
into work.?
the inpui heal is ak
QjTh. confusing signs, we define in this discus-
\342\200\224 To avoid
discussion all energy, heat, and entropy flows as positive whether the flow is into or
out of the system, rather than following ihe usual convention according to
which a flow is positive into the system and negative out of the system. If Q, is
the waste heat leaving the system per cycle ;j{ the fixed lower temperature t,.
the output entropy per eyclc is as
= Qjxy In a reversibleprocessthis output
entropy is equal to the input entropy:

Q,fa = QJik , 14)

= E)
Qi ir,/rh)Qh.

The work generated during one eyeleof a reversibleprocessis the difference

between the heat added and the waste heat extracted:

W =
Qh
- Q, = [1 - ( QA
= -\302\261\342\200\224>-
Qh. F)

The ratio of the work generatedto the heat added in the reversible process is
ealled the Carnot efficiency:

G)

This quantity is named in honor of SadiCarnot,who derived it in 1824. It was

a remarkable feat: the concept of entropy not yet been invented,and
had
Carnot*s derivation preceded by some 15 years the recognitionthat heat is a
form of energy.
The Carnot efficiency is the highest possible value of the energy conversion
efficiency ij
=
W/Gh, the output work per unit of input heat, in any cyclic heat
 Heat Ens'\"\": Conversion of Heat into Work

input

Output

Figure 8.2 Entropy and energy (low in a teal heat engine containing
irreversibilities ihal generate new entropy inside the device. The
entropy outflow lower temperature
at the is larger than the entropy
inflow at ihe higher temperature.

engine that operates betweenthe temperatures t,, and t,. Actual heat engines
have lowerefficiencies becausethe processes taking place within the device are
not perfectly reversible. Entropy will be generated inside the device by irrevers-
irreversibleprocesses. The energy-entropy flow diagram is modified as in Figure 8.2.

We now have three inequalities

ft S: &(r,/Tfc); (9)

A0)
The actual energy conversion efficiency j; obeys the Carnal inequality

W/Qk

We can have i; = ijc only in the limit of reversible operation of a device that
takes in heat at ih and ejectsheal at rt.
The Carnot inequality is the basic limitationon any heat engine that operates
in a cyclic process. The result te!!s us that it is impossible to convert all input
heat tnto work. For a given temperature ratio tJt, the highest conversion
efficiency is obtained under reversible operation. The limiting efficiency in-

increases with increasing xhfxit but we attain !00 percent efficiency only when
tJt, -* go.
The
low-temperature waste heat of any heist engine must ultimately be

ejected into the environment, so thai r, c;innoi be below the environmental

temperature,usually about 300 K. Higheilicieney

requires an input temperature
Th high compared to 300 K. The usable temperatures in practice are unfortu-
unfortunately limited by various materials constraints. In power plant steam turbines,
which are expected to operate continuously for years, the upper temperature
is currently limited to about 600 K\"by problems willi the strength and corrosion
of steel.With r, = 300 K and Th = 600 K, the Carnot efficiency is i;c =
$, or
50 percent. Lossescausedby unavoidable irreversibiliiies reduce this ellkicticy
typically to about 40 T
percent. oobtainHigher eilicicncies is a problem in
high

temperature metallurgy.

Sources of UreversibHity. Figure S.3 illustratesseveral common sources of

irrevcrsibility:

(a) Part of the input heat Qh may flow directly to the low temperature,by-
bypassing the actual energy conversion process, as in the heat flow into the
cylinder walls duriiig the combustion cycle of the internal combustion

engine.
(b) Part of the temperature differencex,, r, way not be availableas tem-
-

temperature diflcrencc in the actual energy conversion process,because of

the
tesnperature drop across thermal resistances in the path of the heat
flow.

(c) part of ilic work generated may be convertedbackto heat by mechanical

friction.

(d) Gas may expand irreversibly without doing work, as in Ihe irreversible
expansion of an idealgas into n vacuum.
 Irreversible expansion
wfthout work or heal

bypass

Figure Four sources of trreversihilily

8.3 in heal engines: heal How

b> passing the energy conversion process, ihermai resislance in the palh
of tile heal flow, frtclional losses, and entropy generation during

irreversible expansions.

Refrigerators

Refrigerators engines in reverse.Refrigerators

are heat consume work to move
i'^ai from alow temperature r, to a higher temperature rA. Consider the energy-

entropy flow diagram of a reversibleheat engine in Figure 8.1. Because no

enlropy is generatedinsidethe device, its operaiion can be reversed, with an
e*act reversal of the energy and entropy Ot>-\\i. Equations D) ihrough F)
remam valid for the reversed flows.
Chapter S: I hat and Work

The energy ratio of interest in u refrigerator is itot tile energy conversion

efficiency G), but tlic ratio y
s Q,/W of iho heat extracted at tlic low tem-
temperature to the work consumed. This ratio is calledthe coefficient of refrigerator
performance; its limiting value in reversible operation is called the Carnot
coefficient of refrigeratorperformance,
denoted by yc. Do not confuse*/ =
0,/W
with 52
\302\273; W;Qh 'he
f\302\260r
energy conversion efficiency of a heat engine;although
i; < i always, y can be > 1 or < 1. From Eq. E) and W = Qh - Qh the work
consumed is

A2)

The Carnot coefficientof refrigerator

performance is

- A3]
Th T,'

This ratio can be larger or smaller than unity.

Actual refrigerators, like actual heat engines, always contain irreversibilities
that generate entropy inside the device.In a refrigerator this excess eniropy is
ejected at the higher temperature, as in the ettcrgy-entropy flow diagram of
Figure 8.4.With the convention that all energy and entropy flows are positive,
we now have

ah > e, , A4)

in place of (8). Further,

& 2 (V'Jfl , A5)

W =
Qt
- Q, > \342\200\224
1]Q,
=\342\200\242 - Q, \302\273
Q,/yc . A6)

Q,iW < yc.

 Air Conditioners ami Heal Pum

Ouipui

Input

Figure 8.4 Entropy

and energy flow in a refrigerator.

The Carnot coefficient

yc is an upper limit to the actual coefficient ofrefrigerator
performance y, just as the Carnot efficiency t\\c is an upper limit to the actual
energy conversion efficiency ;; of a heat engine.
Both heat engines and refrigerators are subject to restrictions imposed by the
law of increase but the
device designproblemsare totally
of entropy, different.

In particular, the design of refrigerators to operateat the temperature ofliquid

helium or below is a challengingproblemin thermal physics (Chapter 12).

Air Conditioners and Heat Pumps

Air conditioners are refrigerators the inside of a
that cool or an auto- building

automobile; the heat is ejected outside environment.If

lo the interchange the we

inside and outside connections, an air conditionercan beusedto a building heat

during the winter, Such a device Is calleda heat If t| xk a beatpump.

\342\200\224\302\253
r\302\273
Chapter Si Hear and Work

pump can heat the building with a lower

consurnption of energy than by direct
healing (Problem I).
The limitations on the use of heat pumps are largely economical, They are
much more costly to install and to main tainthan are simpleheatersor furnaces.
Heat pumps make economic sense primarily in eiimatic conditions in which
air conditioning is required anyway.

Carnot Cycle
The derivation of the Carnot energy conversion efficiency and of the Carnot
coefficient of refrigerator performance made no statement about how to
realize process a by which work is generated from heat, or about how refrigera-
is
refrigeration achieved. The simplest and best known such processis the Carnot cycle.
In the Carnot cycle a gas\342\200\224or another working substance\342\200\224is expanded and

compressed in four stages, two isothermal and two isentropic, as in Figure 8.5.
At point 1 the gas has the temperature xk and the entropy aL. The is
gas expanded
at constant r until the entropy has increased to the value a,,, at point 2. In the
second stage the gasis further expanded, now at constant a, until the temperature
has dropped to the value r,, at point 3. The gas is compressed isothermally to

point 4 and then compressed isentropically to !heoriginals!a!eI. We write aL

and c,, for the low and high values of the entropy contained in the working
substance, to distinguish these values from a, and ch, which are the entropy
flows per cycle at !hc low and high temperatures r, and rv For tlic Carnot cycle,
~ = \"
G\\ \302\260h &I1 \302\260L-

The work done by the system in one cycle is [he area of the rectangle in

Figure 8.5:

W~{Th
~
T,)(tfn
- ffj. A3)

whicii follows from

SdU \342\226\240\342\226\240=
0 =<\302\243uta -SpJV ,

where jjklV is the work done by the system in one cycle. The boat taken up at

T = ts during the first phase is

We combine (IS) and A9) to obtain the Carnot efficiency ;/c. Any process
described by Figure 8.5 is calleda Carnot cycle,regardlessof the working

substance.
 ,lCyd.

Figure 8-5 cycle, for the conversion of heat

A Carnot into work,
illustrated of entropy
as a plot versus temperature, for an arbiirary
working subsiance. The cycle consistsof two expansion phases
(t -* 2 and 2-<3) and wo compression 4 and 4 -+ 1).
phases <J \342\200\224\302\273
Cjnc of the expansion ano one of ihc compressionolsascs iire

isothermal (I - 2 and 3 - 4), and one phase of each kind is

iscntropic B -> 3 and 4 -* 1}.The nei work done is ihc area of ihc
loop.The heal consulted at r^ is the area surrounded by ilic

broken line.

The Carnol cycle is a point of reference!o indicate what could in principle

be done, rather than what in fact is done. All energy conversion cycles need a
high temperature input and a low temperature output of heal, bu! often (lie

heat inputs and outputs are not well-definedreservoirsat constanttemperatures.

Even where such reservoirs exist, as in steam turbines, (here is invariably ;s

temperature difference presenl between the working substance and the reser-

reservoirs. The healing and cooling processes are never truly reversible.

Example: Caettot cycle for an idea!gas. We carry an ideal monaionjic gas through a

Carnot cycle- initially ihc gas occupies a volume t', and is in thermal equilibrium with j
reservoir <i\\h at the high temperature tv The gas is expanded isolherlttally to the volume
K, as in Figure In
\302\243.6a. Hie process the gas absorbs Die heal Q, from (Rt and delivers ii as
\\vo[k *jj 10 ^n c\\lern>ii n^cdmmcal sy ^Icm conncclco to Die pislon. i~or an sdcaiQas the
heai absorbed from (he reservoiris

Qh
=
II'l3 =. = = A'r B0}
JpJK Nr^dV/V
\"
This work is indicated by the area labeled \0212 Next, the gas is disconnect! from (SI* and
furlhcr expanded, now iscntropically, until ihe temperalure has dropped to the low tem-
peralure :,. In Ihe process the addilional work

is delivered by the gas. The volume V3 at the end of ihe iseniropic expansionis related lo

TlV32:3 = TftV22'3 , or VJVj.

= (tJt,}*2 . B2}

from F.63). Afler point 3 the gas is brought into contact with a temperature reservoir <Slf

ciioscnlo satisfy

KfVx = (t*A,K'2 - VJV2 , B3)

\342\200\224
so thai Kj/V'4 i'j,- f,. To accomplish this compression, the work

ust be done on ihe gas.This work, is ejected to <R, as heai:

ft
= ^34- B5)

Finally, the gas is disconnected from CH, and recompressed iseniropicatly until its tempera-
has
temperature liseii to ihe initial temperature i*. Because of the choice B3}of K4l the gas volume
at this point has returned to its initial value Vlt and the cyde is completed,in this last slage
the work

_
jy4! \302\253
|N(rh T() B6)

on ihe gas; this

is performed cancels the work W2i done by the gas during the iseniropic
expansion2 -* 3, by B1).
The ncl work delivered by the gas during the cycle is given by ihe difference in shaded
areas in Figures 8.6a and 8.6b, which is the enclosed area in Figure 8.6c. The isenfropic
curves in the p-V diagram are steeper lhan the isothermalcurves, so thai Ihe area of the
 y3
v

Figure 8.6 The Camot cycle an ideal gas, as a p-V plot. An ideal gas is expanded
for
and riicompressed in four
stages. Two of them are isothermal, at the temperature I* and
> r,}.
\342\226\240t,(xk Two ofthem arc isentropic,ffomtt to ti.and back. The shaded areas show
(a) the work done during the two expansion stages, (b) the work done during the two
compression stages, and (c) the net work done during the cycle.
Chapter 8: Heat and Work

loop is nnitc 2nd i^ ctintii to trie of

3r\302\243*i jtic rccmn^lc m F^Rurc 8,3. iVc Imvc

- - .
W(rfc TjloaflV^). B7)

The heat absorbed from Cftk was given in B0), so that W/Qj, - (ij ~-
r,)/Tj,, which is jusi
the Camot relation G).

Energy Conversion and the Second Law of Thermodynamics

The Carnoi limiis on the conversion of heat into work and on the performance
of refrigerators are direct consequences of ihe law of increaseof entropy. The

second law of ihermodynamics usually is formuiaiedwiihom memion of

eniropy, We stated ihe classical Kelvin-Planck formulation in Chapter 2:
\"Ii is impossible for any cyclic process lo occurwhose sole effcci is ihe exiraction
of heai from a reservoir and the performance ofan equivalent amount of work.\"
All reversible energy conversion devices thai operaie beiweenihe same ieni-

peratures have the same energy conversionefficiency ;j

= W/Qh- Were ihis not

so, We could combine two reversible devices with different efficiencies, qt < ij2,
in such a way (Figure 8.7)ihat ice
d\302\243\\ I with ihe lower efficiency is operaied in
reverse as a
refrigeralor (hat mows not only ihe entire wasteheat Ql2 from ihe

more efficient device 2 back io the

higher iemperaiure th, but an additional
amouni Q{\\n) of heai as well. The overall result would be ihe conversion of

ihe heal Q{in) to work li^otit), uiihout any net waste heai. This would require
ihe annihilationof entropy and would violate ihe law of increase of entropy.
Now thai jhai all reversibledevicesIhat operatebeiween
we have eslablished
the same
temperatures same energyconversionefficiency,
have the
ii is sufficient

to calculate this cfiiciency for any particular device to find the common value.
The Carnot cycledeviceleadsloi;c (xh = ~
ri)/rft for the common value.

of
Path Dependence Meat and Work

We have carefully used the words heat and work to characterizeenergy transfer

processes, and not to characterize properties of the system iiself. It is not

meaningful to spe;ik of the heat content or of the work system. content of a

We look the
at Cinnot cycle once more: Around a closed loop in the p-V

plane, a net amount of work is generatedby the system, and a net amount of

heat is consumed. But the system\342\200\224on being taken once around Ihe loop\342\200\224is

returned to precisely the initial condition; no property of the system has

changed.This means that there cannot exist two functions Q{a,V) and W{a,V)
 Path Dependence of I hat and Work

Figure 8.7 If uvo different reversible energy conversiondevicesoperating between the

same temperatures tj, and r, coutd have diiTercni energy conversion efiiciencies f'jj > >ji
h would he possible to combine them into a single device wilti 100 pd cfikictio '\342\226\240>\342

using the lessdiicienl deuce ! us a refrigerator that moves not only ihc eniire w;i>:c
ficas Qti ofstie more efficient device 2 backto the higher semporaiure, bui an addiriotiii
amount Q[in) of licaE us wt;il. Tlifs additionat huat would shcii be completely converted
to work.

sudi th;n the heal Q^ and the work Wub required to curry the system from a
siSilc(aa,VB)toa slate {ab,Yb) are given by the differences in Q and W:

If such fimcitons extsicd, the nut transfers of heat and of work aroumla closed
loop necessarily would be zero, ;md we h:ivc shown that the transfers ;tre not
zero.
The transfers of hc:itand work between state (a) ;ittd slate (b) depend on the
path taken between the two states. This path-dependence is expressedwhen
we say (hat hwt and work' are noi siaic functions. Unlike temperature, entropy,
and freeenergy, heat and work are not inlrtnsic atlributes of (he system. The
increments dO and (fIS'that we introduced in (l)and B) cannot bedillerentials
Chapter 8: that and Work

Figure 8.8 Twotrr sibie proceisesin which mechanical or electrical potemial

of mathematical functions Q(a,V)and \\V(o,Vy For this reason we designated

the increments by dQ and d\\V, rather than by itQ and dW. Without the path
dependence of heat and work there would not exist cyclical processes that
permit the generationof work from heal.

Irreversible Work

We consider the energy transfer processes of Figure 8.8. In each process &i
is a purely mechanical or electrical system that delivers pure work with zero
entropy change. The eneray transferred to &2 is converted to heat, either by
mechanical friction or by electrical resistance. The finai state of S2 ^ J^e
same as if the energy had been added as heat in the first place. The entropy
of &2 is increased by do2
\302\253
ilU2fc- This entropy is newly created entropy.
Processes in which new entropy is created are irreversible because there is
no way to reverse the process in order to deslroy the newly created entropy.
If newly created entropy arises by the conversion of work to heat, we say that
irreversible work has been performed.
If we look only at the net change in a system, there is no way to tell whether
the process that led to this change was reversible or irreversible.For a change

dU in energy and i\\a in entropy, we can define a reversible heat dQICV and a

reversible work tfWtev as the amount of heat and work that would accomplish
this change in a reversible process. If part of the work done on the system is
irreversible, the actual work
required to accomplish a given change is larger
 Ineveniblt Work

than the reversible work,

tn\\'il

By conservation of energy

dU = if\\Viim +

so that

The actual heal transferred hi the irreversibleprocessmust be less ihan the

reversible heat.

Example:Sudden expansion of an ideal gas. As an example of an irreversible processwe

consider once more llic sudden expansion of an ideal gas info a vacuum. Neither heal nor
work is transferred, so thai ttU *= 0 and dx = 0- The final stale is identical with the stale

that refills from a reversibleisothermai expansion with the gas in Ihermai equilibrium
with a reservoir. The work IV,,, done on the gas in the reversible expansion from volume
i\\ :o Vj is, from F.57).

\\V,n= -Nilog(^/K,). C0)

The work done on the gas is negative;the gas does posittve work on the piston in an amount
equai to the heal transfer into the system:

Q[cy= - W[cy > 0; Wtet < 0. C1)

The entropy change is equal lo Q,cJt, or

a1-al'= ~Wlcy/x
=
NlogfiyV,). C2)

In the ineversible process of expansion into the vacuum this enlropy is newly created

entropy because neiiher heat nor work Rows into the system from the outside: lVitltt
*=

= 0- From C1) we obtain

Qi\302\253c.

in agreement with B8) and B9)-

Chapter 8: Heat and Work

Figure 8.9 Systems between which on!)' work but no

heat is transferred need not be at the same temperature
for the process to be reversible.

In our discussionof irreversible work we assumed that the new entropy

is created insidethe system during the delivery of work Jo the system by other

systems. This is nol she only source of irreverstbility in energy transfer. Pure
heat transfer, nol involvingany work, is irreversible place between
if it takes
iwo systems having different temperatures. We worked out an example in
Chapter 2. In this process heat fs transferred from a system a! rt to a system
ai the lower temperature t2. We have.'.

=\342\226\240 0.
i!U2 <fQt C4)

The newly created entropy is

= (I/I, - 1/I2)rfe, -ii.re.. C5)

The heal flow is from high to low temperature; i!Qt is negative; r3 - ri is

negative, so that chitT > 0. .

The energy transfer between two systems with different temperatures need
not be irreversibleif only work but no heat is transferred (Figure8.9).
AH actual energy transfer processes are invariably somewhat irreversible,
but reversible processes remain the backbone of the theory of thermalphysics.

They
constitute a natural limit, which is the equilibrium limit of vanishing

entropy generation. We shall assume hereafterthat the words heat and work,
without a further qualifier, referto reversible
processes.
 Heal and Work at Constant Temperature or Constant Pressure

HEAT AND WORK AT CONSTANT TEMPERATURE

OR CONSTANT PRESSURE

Isothermal work. We show the ioia! work performed on a system

ihai in

a reversible isoiherma! process is equai io Ihe increase in the Heimlioltz free

energy F ~ V \342\200\224
za of ihe system. For a reversible process tfQ = ida ~ d{ia),
because dx = 0, so that

dW = dV ~ dU - d(za) \302\253dF. C6!

Thus in such processes the Helmhoitz free energy is ihe natural encrgc:;';
ftiuciion, more appropriate than the
energy V. When we treat an isotEicrltui
process in terms of (he Hclrnholiz free energy, we automatically include ihe

additional work that is required to make up for the heat transfer from the
system to the reservoir. Often the heat transfer is ihe major part of the work;
for the ideal gas the energy V does noj change in an isothermal process, and
the work done is equal lo the heat transfer.
Isobaricheat and work. Many energy transfer processes\342\200\224isothermal or not\342\200\224

lake place pressure, particularly those processes that

at constant take place
in systemsopen to the atmosphere. process
A at constant pressure is said to be
an isobaricprocess.A
simple example is the boiling of a liquid as in Figure 8.10,

F =/<\342\200\236<<

Figure 8.10 When a liquid boils under aimospheru: pressure,the vapor

displacing the aimosplierc does work againsi ihe atmospheric pressure.
ChapterS: Heal and Work

where the pressure on the piston is the external atmospheric pressure. If (he
system changes its volume by dV, the work -pdV = \342\200\224
d{pV) is part of the
total work doneon the system. If positive, this work is provided by the environ-

environment and is in this sense \"free.\" if negative, the work is delivered to the
environment and is not extractablefrom the system for other purposes. For
thjs reason it is often appropriate io subtract ~d(pV) from the total work. We
thus obtain the eflccthe work performed on the system, defined as

ilW = itW + d{PV)

= itU + d{pV) - itQ
= till ~ HQ , C7)

where we have defineda new function

H = V + pV , C8)

called the
enthalpy which plays the role in processes at constant pressurethai
the energy V plays isi processes at constant volume. The term/it7in C8) is the

work required to displace the surrounding atmospherehi order to vacate

the space to be occupiedby the system. Implicit in these definitions the idea
is
that there are other kinds of work besides ihut due to volume changes.
Two classes of the constant pressure processesare particularly important:

(a) Processes in whichiiodTcctive work is done. The hcattransfcr ist7Q ~ <///,

from C7). The evaporation of a liquid {Chapter 10) from an open vessel is
such process, because effective
a no work is done, The heal of vaporization
is ihe enthalpy difference between the vapor phase and the liquid phase-
(b) Processesat constant temperaiure and constant pressure. Then iJQ =*
if/a ~
d{xa), and the effective work performedon the system is, from C6) and
C7),

d\\V => dF + d{pV) => dG , C9)

where we have defined another new function

G ~ F + pV \302\253
U + pV
- xa , D0)

the Gibbs free energy. The effective work performed in a reversibleprocess

at constant temperature and pressure is equal to the change in the Gibbs
free energy system. This is particularly
of the useful in chemical reactions
where the volume changes as the reaction proceeds at a constant pressure.
The Gibbs free energy ts used extensively in Chapter 9, and Ihe enthalpy is

used in Chapter 10.

 Heat and Work at Constant Temperature or Constant Pressure

isobaric Consider an ciccHoiylc of dilulc sutfurie acid iti which arc immersed philiiuiin
electrodes ilia t do noi re net w&in lnc acid [r igtirc s. 11J. Tnc ^titfiir tc sci^i dissocjaics in i o
~
H+ ant) SO4~ ions:

H2SOa 2H+
\302\253 + SO.,\"\" D!)

When a current is passed through the ceil lhe hydrogen ions move to lhe negaihe clecirode
where llicy lake up electrons and form molecular hydrogen g;is:

-+ H2. D2)

The sulfatc ions move to the positive electrodes where they decompose water with the
release of molecular oxygen gas and clocirons: _.

SO4~ + H;O - H3SO4+'iOj + 2c!^. D3)

The sum of the above liircc stepsis the net rcucikm ctttuiluin in lite cell;

H2O-\302\273 H2 + 1O3. {44}

Whch carried out slowly in a vessci open to lhc almosplicrt!, ihc prticessis at conslain
prcsburcaiKicoitMiiiil temperature. A negligible pjft of the olcciricul injml power goes iulo

Figure 8.11 An electrolysis cell An electrical current passes through an electrolyte, such
as dilute sulfurtc acid. The overall result is the decomposition ofwaterinto gaseous
hydrogen
and oxygen. The process is an example of work being done at constant
temperature and constant pressure. . .
resistance heating of the electrolyte. The effective work required to decompose1moleof
water is related to the molar Gibbs free energies of Use reactants:

W => AG =
G(H2O)
-
G(Hj) - \\G{02). D5)

Chemical tables list the Gibbs free energy differenceAG as - 237 kJ per mole at room

temperature.
In electrolysis tins work is performed by a current / that flows under an external voltage
Vo. If I is the time required to decompose one male of water. I x I is lhe total
Q \302\273 charge
(not the heat!) flowing tlirough the cell, and we have

W ~QV0. D6)
According to D3), there are two electrons involved in decomposing one water molecule,
llcnce

Q
=
~2/v> = -1.93 x 10scoulomb. D7)

We equate D6) to D5) 10obiain the condition for electrolysis lo take place.This requiresa
minimum voltage

. = , D8}
Vo ~AC/2NAe

or 1.229volts. A voltage larger lhan Vo must be applied to obtain a finite current flow,
because VQ alone merely reduces to zero the poierciuit barrier between the systems on lhc

sides reaction equationD4).When.

of the V > excess power - x /will
two Va, the (V VQ)

be dissipaicd as heat in trie electrolyte.

If V < Vo, the reaction D4) will right to Icfl provided gaseoushydrogen
proceed from is

available at the positive electrodeand oxygen at lhc negative electrode. In lhe

gaseous

simplesetupof Figure 8.11 the gases are permitted to escape,and for V < Vo nothing will

happen al all. Ev is possible, however, lo construct the electrodes as poroussponges,wiih

hydrogen and oxygen focced through under pcessure (Figure 8-12). Such adevice producesa
voltage f'o between the electrodes and, tf the electrodes arc connected, eucnwl current will
{law. This arrangement is called a hydrogeci-osygen fuel cell. Fuel cells were used as power

sources on board the Gemini and Apoilo* ipacccta.fiand incidentally produced dtinking
water for the astronauts.

The principal technological limitation of fuel cells is their low current, per unit electrode
area. In the Apollo cell the current density was only a few hundred mA/cmJ; hence large
elecirode areas are required lo produce reasonable currents. The current-voltage charac-
characterise of an clearochcmi'cal ceil in Us two operating ranges as fuel cell and as electrolytic
cell are shown in Figure K.I 3.

\342\200\242
The Apollo End criU used Ni and NiO uniict ibn Pt as decltoiici. ami K.OH racier sVian H .SO\302\253

to J. O. M. Bockrisand S. Sriili^asan, fwf cells: Their electrochemistry, McGraw-Hill, New York,

1969.
 Porous electrodes

Figure 8.12 ecl! is an electrolysis cell operated in

A fuel
reverse, withhydrogen and oxygen supplied as fuels. The
fuels arc forced under prow tin: through porous dmroOes
sqwratcJ by an electrolyte The hydrogen and oxygen rea
to form waicr; the excess Gibbs Treeenergy is delivered
outside as electrical energy. Water forms at the positive
electrode and is removed there.

\342\200\224
Elcnrolysis

Figure 8.13 Tliecui ic of aa electroiyiic

celt or fuel cell, indie anges.
ChaptcrS; Heal and Work

Chemical Work
Work performed by the transfer of particles to a system is called chemical
work, because it is associated with the chemical potential.
When particles are transferred, the number of particlesin the system is one
of the independent variableson which the energy U depends. If U = U(atV,N),
then for a reversible process

dU = xda - pdV + fidN , D9}

by tlie thermodynamic identity of Chapter 5. Herewe have replaced the partial

derivatives by their familiar equivalents (Table 5.1). By our definition of heat,
the zdo lerm represents Ihe transfer of heal and the ~pdV and fidN terms
represent the performance of work, ali understood to be reversible:

<tW ~ -pJV+ pJN. E0}

The -pdV.termis mechanical work; the pdN term is the chemical work:

= .
dWc ftdN. E1}

If there is no volume change, dV is chemical,

= 0. All the Work
In particle transfer there arc usually two systems involved, both in contact
with a heat reservoir, and the total chemicalwork is the sum of the contributions

from both systems. In the arrangement of Figure 8.14a pump transfers particles
from system &x to system .&;. The chemicalpotentialsare /it and p2. If
dN =i dN2 \342\200\224
\342\204\242
dN, is the number of particles transferred, the total chemical
work performed is

dWc = OWcl + d\\Vcl

= fadNt + pldN2 = (p2 - nt)dN. {52}

The work that must be supplied to the pump is a\\Vr if there is no volume work
(dV1
*=
dVi = 0), and if all processes arc reversible
The result E2) gives art additional meaning of the chemical potential. We

summarize the propcriics of ihe chemical potential:

{a} The chemical potential of asystem is the work required to transfer one
particle into the system, from a reservoir at zero chemical potential.
(b) The difference in chemical potential between two systems is equal to the
net work requiredto movea particle
from one system to the other.
 Figure 8.t4 Chemical work is the work performed when particles arc moved
rcs'ersibly from one system to another, with the two systems having different
chemical potentials. ITilie two volumes do not change, ihe work is pure
chemical work ; the amount per pariicie is the difference in chemical potentials.

{c} If ihe two systems are in diffusive equilibrium ihey have the same chemical
potential;no work is required io move a particle from one syslem 10
the other,

{d} The difference in internal chemicalpotential {Chapter 5} between two

systems is equal but opposite to the potential barrier thai maintains the
systems in diffusive equilibrium.

Example i Chemical work gas. We considerlhc work per particle required to

for an ideal
move revcrsibly ins monatomic
atoms idea! gas from -Sj wuh concentration
of a t\\^. to -S.
with concentritiion n2 > ii,, both sysiems being al the same leinpcrntnre tFtgure 8.151 If
dV \302\253 the work
0, contains only a chemical work term, which cati be calculated from ihe
difference in chemical potential, no matter how the process is actually performed. The
chemical potential difference between two ideal gassystems with different concentrations is

02 - /fl
=
t[10gOl2/\302\273iQ)
-
logOlj/Hfl)] = Tlog0l2/Jl,}. E3)

This rcs\\ih is cqtial io lite n\\cch:tnit;tl work per particle required io compress the gas
isothciniiiily from the concentration \302\253j to the concern mi ion ux. Tltc work required io
compressN particles of an ideal g;ts from an initial voluitw i\\ to a littal volume ''. is

W - = NTlog{IV^} = WtlogfHj/ii,}. {5A}

-\302\247pdV -Nx^tiVjV^

Hence the mechanical work per particle is iSogtoj/iij),identical to the result E3). The
ChapterSt Heat and Work

Reservoir'

-
ilnergy exchanges-

Figure 8.15 Isothermal diemiciit work. The amount of chemical work per panicle
does not change if the process is performed isoihermally with both sysiems in
thermal equilibrium wiih a common targe reservoir.

ideniiiy of the chemical work wiih the isoihcrmal compress illustrates the equi-
lence or convcriibiiiiyof dilferem kinds of work.

Magnetic Work and Superconductors ,-

An important form of work is magnetic work.Themostimportant application

of magnetic superconductors, and

work is to this application is treated here.
Below some critical temperature Tc is that usually less than 20K, many
electrical conductorsundergo transition from a their normal state wiih a finite

electrical conductivity to a superconducting slate wiih an apparently infinite

conductivity.

expel magnetic fields from their interior. If the

Superconductors super-

superconductor cooled below the critical temperatureand ihen inserted

is first into a

magnetic field, we might expect that the infinite conductivity would shield the
interior from the penetration by a magnetic field. However, ihe expulsion
occurs

even ir i|ie superconductor is cooled below Tc while in a magneticfield (Figure

8.16). This active expulsion, called ilic Metssncreffect,shows that supefcon-

duciivity is more ilian an infinite conductivity.The Mcissncreffect is caused by

shielding currents lhat are spontaneouslygeneratednear the surface, in a layer

about lG~5cm iliick. The magnetic field expulsion is not always complete.
Superconductors are said tobeof type It if the expulsion is incomplete, but stilt
nonzero, in a range of fields above some low field. We shall restrict ourselves
 ark and Superconductors

(
)

Hgure 8-16 Mcissner effect in a supercon6tiding sphere cooled

in a constant applied magnetic field; on passingbelow ihe

transition temperature tlic iiiics of induciion B arc ejectedfrom

the sphere.

Figure 8,17 Thresholdcurves

fidd versus lempcratui;: for scv
conductors. A specimen \342\226\240i
;jpe
below ihe curve and noiii..;! iib
In

TiX

Temperature, in K
 fill 111
,-->I[-lOUl
 Magnetic I Curt and Superconductors

Figure 8.19 A superconductor

arcu A in n superconducting sol
produces a magnetic Ikld B.

transition it is the electronic system rather than the crystai structureof the metai

that undergoes a phase transition.

The superconductingstaleis a distinct .<hermodynamic phase, as confirmed
by differences in the heat capacity of the normai and the supcrconduciingstales.
The iicai capactiy (Figure 8.1 S) cxiiibhs a pronounced discontinuity at ihe onset
of superconducifvhy -di x = xt; when superconductivity is desiroyed by a
magnetic field, ihe discontinuiiy disappears. The stable phasewill be the phase
with the iower free energy. Beiow t = tc in zero magnetic fieid the free energy
of liie superconductingphaseis lower than that of the normal phase. The free
energy of the superconduciingphaseincreasesin the magnetic field, as we show
beiow. The free energy of the normal phase is approximately independent of
the field. Eventually, as the fieid is increased, the free energy of the super-
superconducting phase will exceed that of the normal phase. The normaiphase is

ihen the stable phase, and superconductivity is destroyed.

The increase of the free energy of a superconductor in a magneticfield is

calculated as the work required to reduce the magnetic field to zero in the interior
of the superconductor; the zero value is required to account for the Meissner
effect. Considera superconductor in the form of a long rod of uniform cross-
sectioninsidea long solenoid that produces a uniform field B, as in Figure 8.19.
The work required to reduce the field to zeroinsidethe superconductor is

equai to the work required to create within the superconductor a counteracting

field - B thai exactlycancelsthe solenoid fteld. We know from electromagnetic

theory that the work per unit volume required to create a field B is given by

(SI) B2/2{t0\\ E5a)

(CGS) E5b)
 Chapter Si Heal and Work

Figure 8.20 Tlic free energy dcnsiiy F* of a

noi\\ti\\^i syndic t\\otii\\3.t meiat is appcox.iiv\\u.lcty

independent of [he intensity of the applied

magnetic fkUi Al a
$\342\200\236. temperature x < xt the
melai is a superconductor in zero magnate
dial Fsti,O)is lower
field, so than F^i.O). An
applied magnetic field increases Fs by Bj/l/i,,,
in SI unite land by BBJ/8n in CGS uniis), so
lhai Fs(r,/iJ =\342\226\240
F5(r,0) + Ba3/2j@. If Bu is
larger liian ihe criikjil field BM ihe free energy
deiisiiy is lower in ihe normal siaic than in
the siiperconduciing siaic, and no* ihc nornmt
si ale is ide siabic st,iie. The origin of i tic
vertical se;ilc in ilic drawiiij; is ai f Jr-O)-The
10 U5 t = 0.
ftgute equally applies und Us ii\\
Applied magnelic field Ba

Tiiis is the amount by which the free energy density in the bulk superconductor
is raised by application of an externalmagnetic field, in an experiment at con-
constant temperature.

There is no comparable free energy increase for the normal conductor,

because there is no screeningof the applied field. Thus

(SI) E6a)

{CGS) E6b)

En a plot energy density of both phasesversus

of the free the magnetic field

{Figure 8.20), tne free energy of the superconductingphase will ultimately rise

above that of the normal phase,sothat in high fields the specimen will be in the
normal phase, and the superconducting phase is no longer the stable phase
This is the explanationof the destruction of superconductivity by a critical
magnetic field Bf.

Wiih increasing temperature the free energy differencebeI ween normal and

superconducting phase decreases as t --\302\273

rr, and the critical magnetic field
decreases. Everything else being equal, a high stabilization energy in a type I
superconductor will lead to boili a high critical temperature and a high critical
field. The highestcriticalfields are found amongst the superconductors with the

highest crilical temperatures, and \\ice versa.

SUMMARY

1. Heat is the transfer of energy by thermal contact with a reservoir. In a

reversible process dQ = xda,
2. Work is the by a change in theexEerna!
transfer of energy parameters that
describe the system. The entropy transfer in a reversibleprocessiszero when

only work is performed and no heat is transferred

3. The Carnot energy conversion efficiency, j;c = (zH \342\200\224

tJ/tj, is the upper
limit to t!ie ratio WjQh of the work generated to the heat added.
4. The Carnot coefficient of refrigerator ~
performance, -,'c t,/(ta
- r,), is the
upper limit to the ratio QijW of the heat extracted to the work consumed
5. Thetotal work
performed on & system at constant temperature in a reversible
process is equal to the changein the Hclmholtz free energy F se U - ro-
roof the system.

6. The effective work performed on a system at constant temperature and

pressure in a reversible process is equal to the change in the Gibbs free

energy C = U - w + pK.
7. The chemical work performed on a system in the reversible transfer of t.lN

particles to the system is pdN.

8. Tlic changein the free energy density of a superconductor {oftype {) caused

by an external magnetic field B is B2/2{i0

in SI and S2,8;i in CGS.

PROBLEMS

/. Heat pump, (a) Show that fora reversible heal pump tile energy required
per unit of heat delivered inside the building is given by the Carnoi efficiency F):
Chapter S: Heat and Work

2. Absorption refrigerator. In absorption refrigerators the energy driving the

process is supplied not as work, but as heal from a gas flame at a tempenisure
i(,h > xh. Mobile home and cabin refrigeratorsmay be of this type, with propane
fuel, (a) Give an energy-entropy flow diagram similar to Figures 8.2 and 8.4 for
such involving no work at all, but with energy and entropy
a refrigerator, Hows

at three temperatures
the rfch > ta > ij. (b) Calculate the ratio QJQhh, for ihe
heat extracted at r \302\253r,, where QM is the heat input at r = xhh. Assume reversible

operation.

3, Photon Camot engine. Considera Carnotengine that uses as the working

substance a photon gas. (a) Given i,, and r, as well as Vl and V2, delerwne
Vi and VA. (b) What is the heat Qh taken up and the work done by the gas during
the first isothermal expansion? Are they equal to each other,as for the ideal gas?
(c) Do the two isentropic stagescanceleach other, as for the ideal gas? (d) Calcu-
Calculate the total work done by the gas during one cycle.Compare it with the heat
taken up at rh and show that the energy conversion efficiency is the Carnot
efficiency.
4. Heat engine\342\200\224refrigerator cascade. The efficiency of a heat engine is to be
improved by lowering tow-temperature reservoirto a
the temperature of its
valuer,., below the
temperature r,, by means of a refrigerator. The
environmental

refrigerator consumes part of the work produced by the heat engine.Assume

that both tlie heat engine and the refrigerator operatereversibly.Calculate the

ratio of the net (available) work to the heat Qh supplied to the heat engine at

temperature ift. Is it possible to obtain a higher net energy conversionefficiency

in this way?

5. Thermal pollution. A river with a water temperature T} = 2CTC is to be

used as the low temperature reservoirof a large power plant, with a steam
temperature of Th
= 500JC. If ecological considerations limit the amount of
heat that can bedumped into the rtver to \\ 500 MW, what is the largest electrical
output that the plant can deliver?If improvements in hot-steam technology
would permit raising Th by lOQ'Q what effect would this have on the plant
capacity?
6. Room ah air conditioner operatesas a Carnot
conditioner. A room cycle

refrigerator between an outside temperature Th and a room at a lower tempera-

temperature7\"j. The room gains heat from the outdoors at a rate A[Th \342\200\224
T,); this heat

is removed by the air T

condilioner. he power supplied to the cooling unit is P.
(a) Showthat the steady state temperature of the room is
- -
T, \302\253
(Th + PjlA) [<Tfc
4- P/2AJ T,,2]1'2.

(b) ir the outdoorsis at 3VC and the room is maintained at 17\302\260Cby a cooling
power of 2kW, find the heat losscoefficient A of the room in W K\021.A good
discussion of room air conditioners is given by H. S. LefT and W. D. Teeters,
Amer. J. Physics 46, 19 A978). In a realistic unit the cooling coils may be at
2S2 K and the outdoor heat exchanger
at 378 K.

7. Light bulb in a refrigerator, A 100 W light bulb is left burning inside a

Carnoi refrigerator that draws tOOW. Can the refrigerator cool below room
tempera!ure?
S. Gcoihermal energy. A very largemass M of porous hot rock is to be
uiilized to generate electricity by injecting water and utilizing the resulting hot
steam to drive a turbine. As a result of heat extraction, the temperature of ihe
rockdrops, according to dQh
= -~MCdTh, where C is the specificheat of the

rock, assumed to be temperature independent.If the plain operatesat the Carnoi

limit, calculate ihe tola! amount W of electrical energy estractable from the
rock, if the temperature of the rock was initially Th = T,, and if the plant is to
be shut down when the temperature has dropped to Th = Tf. Assume that the
lower reservoirtemperature
T,stays constant. -.
At the end of the calculation, give a numerical value, in kWh. for M - 10u kg
(about 30km3). C=Hg\"!K\"\"', T,-= 600 77 C,
- 110 C, 7\",
\302\273
20 C.
Watch the units and explain all steps! For comparison:The total electricity
produced in the world in 1976was between1 and 2 times 10!4 kWh.

9. Cooling of nonmetatlic solid to T~Q. We saw in Chapter 4 that the heat

capacity
of nonmetallic solids low temperatures is proportional
at sufficiently
to Ti, as C
~ aT3.
Assume it were possible to cool a piece of such a solid to
T \302\253
0 by means of a reversible refrigerator that uses the solid specimen as its
(varying.) low-temperaturereservoir,and for which tile high-temperature
reservoir has a fixed temperature 1\\equal to the initial temperature Tj of the
solid. Find an expressionfor the electrical energy required.
10, ltrerersibte expansionof a Fermtgas. Consider a gas of N noninteractiilg,
a volume ~ 0. Lei the
spin \\ fermions of mass
A/, initially in V;
at temperature if
gas expandirreversibly into a vacuum, wiihout doing work, to a final volume

V}. What temperature of the gas after expansionif Vf is sufficiently

is the large
for the classicallimit to apply? Estimate the factor by which the gas should be
expanded for its temperature to settle to a constant final value. Give numerical
values for ihe final temperature in kelvin for two cases: (a) a particle massequal
to the electron mass, and NjV = 10\"cm\023, as in metals; (b) a particle mass
equal to a nucleon,and N/V = 10JO,as in white dwarf stars.
Chapter 9

Gibbs Free Energy

and Chemical Reactions

GIBBS FREE ENERGY 262

Example: Comparison of G whh F 265

EQUILIBRIUM IN REACTIONS 266

Equilibriumfor IdealGases 267

Example: Equilibrium of Atomie and Molecular Hydrogen 269

Example;pH and the Ionszatton of Water 265
Example: Kinetic Model of Mass Action 270

SUMMARY 272

PROBLEMS 272
1. Thermal ExpansionNearAbsolute Zero 272

2. Thermal lonization of Hydrogen 273

3. lonizationofDonor Impurities in Semiconductors 2 73
4. Hiopolynicr Growth 2/3
5. Patticlu-Antiparticle Equilibrium
274
Chapter 9: Gibbs Free Energy and Chemical Reactioi

GIBBS FREE ENERGY

The Helmholtzfree energy F introduced in Chapier 3 describes a

system at
constant volume and temperature. But many experiments, and in particular
many chemical reactions, are performed at constant pressure, often one aimo
spherc, h is usefulto introduce another function to treat the equilibrium
configuration at eonslant pressure ;tnd temperature. As in Chupicr 8, we
define the Gibbs free energy G as

G a U - xa + pV. A)

Chemists often call this the free energy, and physicists often call tt the
thermodynamie potential.
The most importantproperty of the Gibbs free energy is thai it is a minimum
for a system S in equilibriumat constant pressurewhen in thermal contact
with a reservoir (H.The differential of G is

dG = dU ~ ida - cdx + pdV + Vdp.

Consider a system {Figure9.1)in thermal contact with a heat reservoir <Rl

at temperature t and in mechanical contact wilh a pressure reservoir<R2 that

maintains the pressure p, but cannot exchangeheat. Now dt = 0 and

dp = 0,
so that the differential dG oflhe system in the equilibrium configurationbecomes
dGi =
dUs
- xdax + pdV* B)

The thermodyiiamicidentity E.39) is

zdds
= dUi - ttdNi + pdVs, C)

so that B) becomes dG^ \302\253ndNx. But dNs = 0, wh ence

\302\273
0
dGj ,
 .
System
i eser \342\226\240oir Hea rese rvoir
\342\226\240\342\226\240\342\226\240v\"'Jif

m, v.hh a heat reservoir and in mechanical

equilibrium with a barysiai or pressure

reservoir whkh maintains a constant pic
NPSu ger lo on Hie system. The barysial is
qualiz
e pressure thermally
insuSalcd.

Pressure cserv

which is tlic condition for Gj to be ;m extrcmum wilh respect to system varia-

variations at constant pressure, temperature, and particle number. Theseare,there-
therefore, the natural variables for G(N,z,p).
That ihe extremumof G3 musi be a minimum, raiher than a maximum,
follows direciiy from the minus sign associated w'Hh the eniropy in (i); Any

irreversible change laking place entirely wiihin & will increase a and ihus
decrease Gs.
With B),

- adx + E)

The difierentiai E) may be writicn as

Comparison of{5)and F) gives the relations

0)

(8)
Chapter 9: Gibbs Free Energy and Chemical Reactions

, = V. E)
Three Maxwell relations may be obtained from these by cross-differentiation;
see Problem 1.

In the Gibbs free energy G = V \342\200\224

za + pKthevariabfesr and pare intensive
quantities: they do two identical systems
not change value when
are pui together.
But U, a, V, and G are linear in the number of particlesA':their value doubles

when two identical systems are put togeiher,apart from interface effects,. We

say that V, a, V, A7 and G are extensive quantities. Assume that only one particle

species is present. If G is directlyproportionalto N, we must be able to write

G= Nip(p,x) , A0)

where ep is independent of N because it is a function only of the intensive

quantitiespand r. If two identical volumes of gas at and tempera-
equal pressure
temperature,c;idi wjih j.V molecules, iire |>ui together, the Gibbs free energy

does not change in the process. It follows from this argument that

(II)

We saw in G) that

A2)

so that <p must be identical with ;j, and (iO) becomes

G(,V,p,t) A3)

Thus the for s single-componentsystem

chemical poiemiaf is equal to 'h

Gibbs free energy per particle,G'/A'. I or G for an ideal gas, sec B1) below.

If more than one chemical species is present, A3) is replacedby a sum ov

all species:

A4)
 Gibbs FreeEnergy

The ihermodynamic identity becomes

xda = dV + pdV
-
^e/INy, A5)

and E) becomes

~
dG \302\253
\302\243njdNj
adz + Vdp. (!6)

We shall develop the theory of chemical equilibria by exploiting the property

that G ss: YJ^jfif ts a minimum with respect to changes in the distributionof

reacting molecules at constant t, p. No new atoms comeinto the system in a

reaction; the atoms that are presentredistribute

themselves from one molecular
snucics to another molecular species.

iiiutupfri Omipurhtw ti
\302\273f with F. Let its sttf wluit is Jitiacut :ihuuJ \\\\vi iwo rd.ttions

{cFfdN)tty
= p(iVrT,K) A7)
and

*= (IS)
$G/dN)tiP fi{T,p).

We found in F.18) lM for an ideal gas

MN.r.F) -Tlog(WKnQ) , A9)

so that ti(N,z,l') is not independent of N and therefore we cannot write F = JV;i(r,f) .is
She iaiegra!of{S7).
Thai is, f is not direciiy proportional lo N if ilie system is kept at cotislanl volume as ihc

number of particles is increased. Instead,from F.24),

F(t,V,N)^
- I]. B0J
Ni[\\og(NJVnQ)

But she Gibbs free energy for t-he ideaJ gas is

\302\273
F + = - l] + -Vr
C(r,/\302\273,N) PK Arr[!og(p/rny)
\302\273. , PO
NrIog(;j/THQ)

by use of ihe ideal gas Saw in the form N/V ==

p/r. We readily identify in B1) the chemical

potential us

/((t,p) = i , B2)
lo\302\243(pJxnQ)
Chapter 9; Gibbs Free Energy and Chemical Reactions

by reference to the result G \302\253

iVjih.pV We see [hat N appears unavoidably in sit.V) in
A9), but not in /j(t,p) in B2). The chemical potential is the Gibbs free energy per particic,
but il isnol ihcHctnihoHz free energy pet panicle. Of course, we are free lo wrile p its cilher
A9) or 122},as is convenient.

EQUILIBRIUM IN REACTIONS

We may write the equation of a chemicalreactionas

v,A, + v2A2 + \342\226\240

- \342\226\240
+ v,A,
= 0 , B3)

B4)

where the
Aj denote the chemical species, and the Vj are the coefficients of the
species in the reaction equation. Here v is the Greek lettermi. For the reaction

Hj + Clj = 2HC1 we lave

Ai
=
H,; A, - Clj; Aj
= HC1; Vi=l; fj=l; \302\273j=-2.

B5)

The discussion of chemical equilibria is usually presented for reactions under

conditions of constant pressureand temperature. In equilibrium the Gibbs free
energy isa minimumwith respect to changes in the proportions of the reaclants.
The differential of G is

dG - Z fj^i - adz + Vi!p. B6)

Here//j is the chemical potentialof speciesj, asdefined by \\is = {BGJdNj)s-p. At

constant pressure dp = 0 and at constant temperaturefa
= 0;then B6) reduces
to

rfC-1/,/W,. 07)
j

The changein the Gibbs free energy in a reaction depends on the chemical
potentials of the Xti
re\302\243tctbnts\302\273 comlit^rtufii G is &i cxtrcmum miu uu musl tjo
zero.
 Equilibrium for Ideal Gases

The change dN} in the number of molecules of species/ is proportionalto the

coefficient v,m the chemical equation ]>>/.; - 0. We may Write dN} in the form
\"
\302\253
JNj rjd$ , B8)

where dfif indicates how many timesthe reactionB4) takes place. The change dG
in B7) becomes

dG \302\273
I vjfi dft- B9)

In equilibriumdG = 0, so that

C0)

This is the conditionfor equilibrium in a transformation of matter at constant

pressure and temperature.*

Equilibrium for Ideal Gases

We obtain a simple and useful form of the genera! equilibrium condition
Y^Vjf-j
= 0 when we assume that each of the constituents acts as an ideal gas.
We utilize F.48) lo write the chemical potential of speciesj as
-
fij
-
rflogMj logc;) , C1)
where
nj
is the concentration of species j and

cj a \302\253QJZ/int) , C2)

which depends on ttie temperalure but not on ttie concentration.HereZ/int)

is the internal partition function, F.44). Then C0) can be rearrangedas

\342\226\240
= , C3a)
5\302\273gnj $>,!(*<:,

*
Uul ihcmull is moregencrat; onceequilibrium is reached, ihe rcaclion does nol proceedfurihi:r,

when p and t arc specified..

Chapter 9: Gibbs Free Energy and Chemical Rcactia

C3b)

The left-hand sidecan berewritten as

C3c)
and the right-hand side can be expressedas

C3d)

Here K(t}, called the equilibrium constant, is a function only of the temperature.

Wiih{32)\\vehave

K{t) s nil\302\253/' C4)

because the internal free energy is Ffim) = -TiogZj{int). From C3c,d) and

C4) we have

Fk-Vj C5)

known as the law of mass action.The result says that the indicated product of the
concentrations of the reactanlsis a function of the temperature alone. A change
in the conceniraison of any one reaciam will force a change in the equilibrium
concentration of one or moreofthe other reaclants.

To calculate the equilibrium constant K(x}in C4), it is essential to choose in

a consistent way the zero of the internal energy of each reactant.We need

consistency here because the value of each partition function

Zji'mi) depends
on our choice of the zero of the energy eigenstales. The different zeros for the
different reactants must be related to give properly the energy or free energy

difference in ihe reaction. It is not diilicuh to arrange ibis, but it docs not

happen without a conscious effort on our part. For a dissociation reaction such
as l\\2 ^ 2H, ilie simplest procedure is to clioosethe zero of the internal energy
of each compositeparticle(here the H2 molecule} to coincide with the energy
of the dissociatedpanicles(here 2H) a! res!. Accordingly, we piacc the energy
of the
ground state of the composiie particle at ~\302\243fl, where is
\302\2433 the energy
 Equilibrium for Ideal Gases

required in the reaction to dissociate the composite particle into its constituents
and is laken to be positive.

Examplei Equilibrium of atomic and molecular hydrogen. The siatcmcnl of ihe law

mass aciioil for the rcacuon Hj = 2H ttz ~ 2H = 0

or for the dissociaiion of molecul
hydrogen imo atomic hydrogen is

C6)

Here [llj] denotes ihc concenmuion of nlolecutar hydrogen, and fjt] i

of atomic h>drogen. li foltov-sihai

l37)
[h^tpo17^'

lhai is, the relume concentration of atomic hydrogen at a given temperature is inversely

proportional lo the square rooi of ihe concent ration of molecular hydrogen. The equilib-
equilibriumcon:.lani K is given by

logK
=
log^tHj)
-
2IognQ(H) - F(U2)/i, C8)
in terms of the internal free energy of H,. per molecule. Spin factors are absorbed in F(H,}.

Here of energy is laken for an H atom at rest. The more lightly

[he zero bound is H,, the
more negative is F{Ht), and ihe higher is Kt leading 10 a higher proportion of Hj in ihe
mixture. The energy to dissociate Ht is 4-476 eV per molecule, al absolute zero.
It may be said lhai ihe dissociationof molecular hydrogen into atomic hydrogen is an
of
example entropy dissociaiion: The gain En entropy associated wiih ihe decomposition
of Hj into two independent particles compensates [he loss in binding energy. It is believed
that most of the hydrogen in intergalactic space is present as H and not Ht: The reaction
equilibrium is thrown in the direction of H by the low values of ilie concentration of Hj.
Hjdrogcn is very dilute in intergalactic space.

Example: pi! and ihe limitation of water. In liquid waicr ihe ioni^lion process

H2O*~>H+ + OH\" 09}

eeds to a slight txicnt. Al room tcinpcraluic the reaciion cquilibfium i

o.ximalcly by she coiiccmraikm product

D0}
Chapter 9; Gibbs Free finersy and Chemical Reactions

where ihc jonac concentrations arc given in moles per liicr. inpurcualcr\302\243H*l \342\200\224
fOH \021 ^=

!0\021molr''. An acid is said lo aa as a prolon donor. The concentration of H* ions is

^nefcasco oy aGGin& z\\t\\ iictu to llic wai^r ihe concentration
\302\273^ntJ of C3i 1 tons wtll decrease
as required lo mainiain the product [H*][O!!'] constant. Similarly, ihe concentration
\" *
of OH ions can be increased by adding a hase lo ihe water, and ihe H concentration will
decrease accordingly. The physical siaie oi wafer is more complicated than ihe equation
of ihe ionizaiion process suggests\342\200\224ihc H* ions ate not bare protons, but are associated
with groups* of H2O molecules.This does not sigiltficantry affect ihe vulidily of ihe reaction

equation.
it is ofien convenient lo express theacidily oraikalinii) otasolulionin letmsof ihe pti,
defined as

pH s -log10[H+]. D!)

The pH ota solution is ihe negative of the togarilhm base ten of iht; hydrogen ion concentra-
in
concentration moles per liier oCsolution. The pH pure
of water is 7 because [H*] = !CT7mair'.
The slrongesi acidic sotuiions have pH near 0 oi even negative; an apple may have pH - 3.
Human blood plasma has a pH of 73 lo 7-5; it is slightly basic.

Kxati\\ple2 Kttictic modelof/nms action. Suppose that B combine to form a

atoms A and
moieculc AB. We suppose that AB is formed in a biaiomic collision of A and B. Let ha,
nB, nAB denote t!ie concentrations of A, B, and AB respectively. The rale of change of nAB is

where the me constant C describes the formation o[AB in a collision of A with B, and ihe
rale constant D describesthe reverse process, the ihemiat decay of AB into its component
atoms A and B. in thermal equilibrium the concermaiions of all consiiiutents ace constant,
so that du.a:di = Oand

nAB
= D/C , D3)

a function of temperature only. This result is consistent with ihe law of mass action that we
derived earlier by standard thermodynamics.
Suppose AB is noi formed principally by the bimolecular collision of A and B, but is
formed by some catalytic process such as

\"
The dominant species present is most likely it*1 4HjO, acomplc*of4 water molecules surround-
one
surrounding ptolon. A [cvie* is given by M. Eigcn and L. Dc Macycr, P(oc_ Roy. Soc tLondon) A147.
\342\226\240
505A958). , .
 Equilibrium for IdealCases

Here E is ihe catalyst which is returned to its original slate ai ihe end of the seeond step.
So long as ttie intermediate product AE ts so short lived that no significant quantity of A
is lied up as AE, ihc ratio iiaiiu/iUb in equilibrium must be us if AB were formed
the same in

the direct process A + B<--AB treated above. No rnaiierby what route Hie reaction
actually proceeds, ihc equilibrium must be the same. The rates, however, may differ.
The equality in equilibrium of the direct and inverse reaction rate's is culled the principle
of detailed balance.

Comment: Reactionrates. The law of mass action expresses ihc condition satisfied by ihe
concentrations once a reaction lias gone to equilibrium, li iclis us nothing aboui how fasi
ihc reaction proceeds. A reaciion A + B = C may evolve energy AH as it proceeds, bat
before the reaction can occur A and B may have 10 negotiate a potential barrier, as in
Figure 9.2. The barrier heigh! is called the activation energy. Only moleculeson the high
energy end of their energy distribution will be able to read; others will not be able to get

over the potential hill. A catalyst speeds up a reaction by offeritig an alternate reaction path
with a lower energy of activation, but it does not change the equilibrium concentrations.

Schematic coordinate

Figure 9.2 The quantity AH measures ihe energy evolved in the reaction
nnd determines the equilibrium concentration ratio [A][B]/[C]. The
activation energy is the height of the potential barrier to be negotiated
before the reaction can proceed, and it determines the rate at which the

reaction takes place.

Chapter 9: Gibbt FreeEnergy and Chemical Reactions

SUMMARY

1. The Gibbs free energy

G3 U - iff + pV

is a minimum in thermal equilibrium at constant temperature and pressure.

2. (cG/3r)H,= -a; tfG/cph., =
V; (SG/SN),.P
= p.

3. C(r,p,W) = W,,(r,ri
4 The law ofmass action for a chemical reaction is that

IK'
- -^w.

a function of the temperature alone.

PROBLEMS

/. Thermal expansion near absolutezero, (a) Prove the three Maxwell rela-
relations

= ,
, (dV/di)P -{dts/dp), D5a)

(aVldN)p = +(ap/ap)^ , D5b)

= D5c)
(Qj/cr)jV ~Ea/dN)x.

Strictly speaking, D5a) should be written

and two subscripts should appear similarly in D5b) and D5c).It is commonto
omit those subscripts that occur on both sides of theseequalities,(b) Show wilh
(lie help of D5a) and the third law of thermodynamics tjiat the volume Coeffi-
Coefficient of tjicrniiti expansion

approaches zero as t -* 0.
2. Thermal ionization of hydrogen. Consider the; formation of atomic hy-

hydrogen in the reaction c + H*ftH, wheree isad eicutron, as the adsorption

of an electron on a proton H*. (a) Show that the equilibrium concentrations
of the reactants satisfy the relation I

[e][H+J/[HJs\302\253acxp(-//T), D7)

where / is (he energyrequited to tontze and ~

atomic hydrogen, tiQ{im/2zh2K11
refers to the electron.Negiecithe spins of the particles; this assumption does
not aSTed the final result. is known as the Saha equation.Ifall the
The result
electrons and protons arise from the ionization of hydrogen atoms, then the
concentration of protons is equal to that of the
Electrons,
and the electron
concentration is given by ]

0]~[H]\"V'3\302\253p(-//iT). D8)

A similar problem arises in semiconductor physics in connection u-jth the

thermal ionization of impurity atoms that are donors of electrons.
No lice lhat: I

A) The exponent involves ^1 and not /, which shows that this ts not a simple
\"Boltzmannfactor\" problem. Here / is the ionization energy,
B) The elccjron concentration is proportional to the square root of the
hydrogen atom concentration. !

C) If we add excess electrons to the system, then (He concentration of protons

will decrease.

(b) Let [H(exc)]denotethe equilibrium concentration of H atoms in the

first excited electronic state, which is \\l above the ground state. Compare
3
[H(exc)] with [e] for conditions atthe surface of the Sun,with [H] = 1023 cm~
andT - 5000K. |
I

3, hnization of donor impurities in semiconductors. \\ A pentavalent impurity

(called introduced in place ofa tetravalent
a donor) silicon atom in crystalline
silicon acts likea hydrogen atom in free space, but with e2/e playing the role of
e2 and an effective mass m* playing the role of the electron mass m in the
description of *hc kmizalion energy and radius o( the ground state of the

impurity atom, and alsofor the free electron. For silicon the diclctltic consta.t\\t

e ~ 11.7 and, 0pproxima!e!y, m* =0.3 m. U there are 10\" donors p^r cmJ,

estimate the con cent ration of conduction electronsat 100 K.

4. Siopotymergrowth. Consider the chemical equilibrium of a sotution
of linear polymers made up of identical units. The basic reaction step is
monomer 4- A'mer = (A' -f l)mer. Let K^ denote liieequilibrium constant for
Chapter 9: Gibbs free Energy and Chemical Reactions

this reaction, (a) Show from the law of mass action lhat the concentrations \342\200\242
[\342\226\240
\342\226\240]
satisfy

[N + 1]
= [If \"/K.KjKj
\342\200\242
\342\200\242
\342\226\240
K.v D9)

(b) Show from the Iheory of reactionsthai for ideal gas conditions (an ideal
solution):

wQ(W) ^Bnti2/M,^rm , E1)

where MN is the mass of the Nmer molecule,and FN is the free energy of one
iVmer molecule, (c) Assume N \302\273
j, so thai nQ{N) = Hq{N
+ 1), Find the
concentration ratio [N 4-
t]/[N]
at room temperature if there is zero free

energy change basic reaction siep: that is, if AF = FKi.l ~ Fs ~ fj =-0.

in the
Assume [I]
= 10aocm~3, as for ammo acid molecules in a bacteria! ceil. The
molecular weight of the monomer is 200.(d) Show that for the reaction to go in
the direction of long molecules we need AF < ~0.4cV, approximately. This
condition is not satisfied in Nature, but an ingenious pathway is followed that
simulates the condition. An elementary discussion is given by C. KiUel, Am. J.

Phys. 40,60A972).

5. Pavtkte-antipartkk equilibrium, (a) Find a quantitative expression for the

thermal equilibrium concentration n = n+ = n~ in the particle-antiparticle
reactionA+ 4- A\" = 0. The reactants may be electronsand positrons; protons
and antiprotons; or electrons and hoies in a semiconductor. Let the mass of
either particle be M; neglect the
spins of the particles. The minimum energy

release when A* combines with A\" is A-Take the zero of the energy scaleas the
energy with no particles present, (b) Estimate n in cm\023 for an electron (or a
hoie) in a semiconductor T \302\253* 300 K. with a A such that A/t = 20. The hole is
viewedas the antiparticic to the electron. Assume that the electronconcentration
is equai to the hoie concentration; assume aiso titat the particles are in the
classical regime, (c) CorrectIheresult of (a) to let each particle have a spin of 3.

Particles that have amiparticfes are usually fermions with spins of \\.
Chapter 10

Phase Transformations

VAPOR PRESSURE EQUATION 276

Derivation of the Coexistence Curve,p Versus t 278

Triple Point 284

Latent Heat and Enthalpy 284

Example: Model System for Gas-Solid Equilibrium 285

VAN DER WAALS EQUATION OF STATE- 287
Mean Field Method 288
CriticalPoints for the van der Waals Gas 2S9
Gibbs Free Energy of the van der Waals Gas 291
Nucieation 294
Fe from agnet ism 295

LANDAU THEORY OF PHASE TRANSITIONS 298

Example: Ferromagnets 302
First Order Transitions 302

PROBLEMS 305
1. Entropy, Energy, and Enthalpy of van der Waals Gas 305
2. Calculationof dTjdp for Water 305
3. Heat of Vaporization of Ice 305

4. Gas-Soltd Equilibrium 305

5. Gas-Solid Equilibrium 305
of
6. Thermodynamics the Superconducting Transition 306
7. Simplified Model of the SuperconductingTransition 307

8. First Order Crystal Transformation 307

Note: tn the first section s denotes c/iV, the entropy per atom. In the section on fcr
Chapter 10: Phaie Transformations

VAPOR PRESSURE
-
EQUATION

The curve of pressure versus volume for a quantity of matter at constant

temperature is determined by the free energy of the substance. The curve is
calledan isotherm. consider We the isoihcrmsof a real gas in which the atoms
or molecules interact with one another and under appropriate conditions can
associate together in a liquid or solid phase, A phase is a portion of a system
that is uniform in composition.
Two phases may coexist, with a definite boundary between them. An isotherm
ofa real gas may show a region in the p-V plane in which liquid and gas coexist
in equilibrium with each other. As in Figure 10.1, part of the volume contains
atoms in the gas phase. There are isotherms at low icmperaturcsfor which

solid and liquid coexist and isothermsfor which soiid and gas coexist. Everything
we say for the liquid-gas equilibrium holds also for the solid-gas equilibrium
and the solid-liquid equilibrium.
Liquid and vapor* may coexist on a section of an isotherm only if the

temperature of the isotherm lies below a critical temperaturerc. Above the

critica! temperaiure only a single phase\342\200\224the phase\342\200\224exists, fluid no matter

how great the pressure. There is no more reason to cali this phase a gas than
a liquid, so we avoid the issueand callit a fluid. Values of the critical temperature
for severalgasesare given in Table iO.t.
Liquid and gas will extent of an isotherm
never coexist along the entire
from zero pressure to infinite pressure; they coexist at most only along a

section of the isotherm. For a fixed temperature and fixed number of atoms,
there will be a volume above which all atoms present are in the gas phase.
A small drop ofwater placedin an evacuated sealed bell jar at room temperature
will
evaporate entirely, leaving the bell jar filled with H2O gas at some pressure.
A drop of water exposed already saturated with moisture
to air not may

evaporate entirely. There is a concentration of water, however,above which

the atoms from the vapor will bind themselves into a liquid drop. The volume
relations are
suggested by Figure JO.i.
The thermodynamic conditions for the coexistence of two phases are the
conditions for the equilibrium of two systems that are in thermal, diffusive,
 Vapor Pressure Equatio

Liquid Liquid + gas Gas

Figure IO.I Pressure-volume isotherm of a reyj gas at a

temperature such that liquid and gas phases may coexist,that

is, t < tc. in the two-phase region of Hquid 4- gas the pressure
is constant, but the volume may change. At a given lempcrature
Efiei^ is only <t s^nclc v*iluc of tltc ptcssurc for Vvh^cri a Jjtjuiu

and its vapor are in equilibrium. Jf at this pressure we move the

piston down, some of the gas is condensedto liquid, but the

pressure remains unchanged as Jong as any gas remains.

Table 10.1 Critical temperatures of gases

T,. in K Tt, in K

He 5.2 H2 33.2
Nc 414 N. 126.0
Ar 151 Oj 1543
Kr 210 647.1

Xc 289 7 CO, .W.2

Chapter 10: Phase Transformations

and mechanical contact. Thesecondilions

are that tj = t2: fit
=
p2; pl =

or, for liquid and gas,

*j
=
18\\ Ml
=
/Jj,; Pi = Pg . A)

where the subscripts / and g denote the liquid and gas phases. Note that the
chemical potentials of the same chemical species in the two phases must be
equal if the phases coexist. The chemical potentials are evaluatedat the common
pressure and common temperature of the liquid and gas, so that

/l,(p,T)
= B)
/ijl

At a general point in the p-x plane the two phases coexist: If /i, < ng
do not
the liquid phase alone is stable, and if ns
< Pi the gas phase alone is stable.
Metastablephases may occur, by supercooling or superheating. A metastable

phase may have a transient existence, sometimesbrief, sometimes long,at a

temperature for which another and ntore stable phaseof the same subslance

has a lower chemical potential.

Derivationof the CoexistenceCurve, p Versus r

Let pQ be the pressure for which two phases, liquid and gas, coexist at the
temperaturez0.Suppose that the two phases also coexist at the nearby point
Pa + dp;iQ + rfi.Thecurve in thep.T plane along which the two phasescocxist

divides the p, t plane into a phase diagram, as given in Figure 10.2 for H2O.
It is a condition of coexistencethat

C)

dt). D)

Equations C) and relationship betweendp

D) give a and dx.

We make a series expansion of each sideof D) to obtain

-. E)
 ion ojthc Cot

Figure 10.2 Phase diagram of H.O. The

relationships of the chemical poienmls /t,. ;i,.
and
jiB in the solid, liquid, and gas phases ate
shown.The phase boundary here bciwcen ice
and water is not cxacily vertical; the slope is
actually negative,although very large. After
Iniemalionat Critical Tobies.Vol. 3. and P. \\V
Qridgman, Proc. Am. Acad. Sci.47, 4-i| A912)
for the several forms of ice. see Zemamky,
p. 375.

-100 0 100 200 300 400

Temperature,in \302\260C

In the limit as dp and dz approach zero,

F)

by C) and E). This result may be rearrangedto give

which is the differential equation of the coexistence

curve or vapor pressure
curve.
The derivatives of the chemicalpotentialwhich occur in G) may be
expressed
in terms ofquantities accessible to measurement. In the treatment of the Gibbs
Chapter 10: Phase Transformations

free energy in Chapter 9 we found the relations

With the definitions

v s V/N, 5 = o/W (9)

for the volume and entropy per moleculein each phase, we have

1 (cG\\ V
(dp\\

)JJ
Then G) for dp/dt becomes

01)

Here
sa
~
st is the increase of entropy of the system when we transfer one
moleculefrom the liquid to the gas, and vg
\342\200\224
t\\ is ihc increase of volume
of the system when we from the liquid to the gas.
transfer one molecule
It is essential to understand thai the derivative dp/dz in (I!) ts not simply
taken from the equation of state of the gas. The derivative refers to the very

special interdependent change p of and i in which the gas and liquid continue
to coexist.The number of molecules in each phase will vary as the volume is
varied, subject only to N, + Na = A\\ a constant. Here Ns and (Va
are the

numbers of molecules in the liquid gas phases, respectively.

and
The quantity sa
~
s, is related directly to She quantity of heat that must

be added to the sysfern to transfer one moiecule reYersibly from the liquid
to the gas, while keepingthe temperature of the system constant. (If heat is
not addedto the
system from outside in the process, the temperature will

decrease when the molecule is transferred to the gas.)The quantity of heat

added in the transfer is

l1Q ~ TE*
\"
5'}'
A2)

by virtue of the connectionbetween heat and the change of entropy in a

reversible process.The quantity

L = - A3)
tEs
 Dcritaiion of the Coexistence Cur

defines She latent heat of vaporization, and is easily measured by elementary

calonmetry.
We let
A*\302\253 A4}
i-g-v,

denote the change of volumewhen one molecule is transferred from the liquid
to she gas. We combine A1), U3), and A4) to obtain

A5)

This is known Clausius-Clapcyron equationor the vapor pressure

as the equation
The derivation of this equation was a remarkableearly accomplishment of

thermodynamics. Bo!li sides of (!5) are easily determined experimentally, and

the equation has been verified to high precision.
We obtain a particularly useful form of A5} if we make two approximations:

(a) We assume that vg \302\273

I'j: the volume occupied by an atom in the gas
phaseis very much larger than in the liquid (or solid)phase,so that we may

replace Av by vg:

Avsva= vt/yr {16)

At atmospheric pressure i'9/i;( ^ !03, and the approximation is very good.

(b) We assume that the ideal gas law pVg =

Ngz applies to the gas phase,
so that A6) may be written as

Av S zip. A7)

With these approximations the vapor pressureequationbecomes

where L is the latent molecule. Given L as a function

heat per of temperature,

this equation may be integrated to find the coexistence curve.

if, in addition, the latent heat L is independent of temperature over the

temperature range of interest, we may take L = l.,Q outside the integral. Thus
when we integrate (IS) we obtain

r (lv
A9)
/dp
 Chapter 10: Phase Traasfortnat

logp =
\342\200\224Z-0/i+ constant; ) = p0CXp(-L0/T) ,

where p0 is a constant.We defined LQ as the latent heat of vaporization of

one nioiecuie. If Lo refers instead to one mole, then

where R is the A'cta, where No is t!ie Avogadro constant. For

gas constant, R =
water the latent heat at the iiqufd-gas transition is 2485J g~' at O'Cand 2260
J g~' at lOO'C.a substantial variation with tcmpcraiure.
The vapor pressure of water and of ice is plottedtn Figure !0.3 as !ogp
versus 1/T. The curve is linear over substantial regions, consistent with the

-Crit ca! p Jin.

\\

id wa er

X 103 \342\200\224
1 atm

\342\226\240-
\\
Vapor pressure ofwaier and of ice 102
\"
is 1/T. The vertical scale is
The dashed line b a straiglif iine. S
10 \\
I
Si*\"
vc
\\ s
\342\200\242Ice
V 1

\\
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

lO'/T, in K~\302\273
 2 3 4
in K
Tcmperamre,

Figure 10.4 Vapor pressure versus iemperaiurcfor 4He. After H. van Dijk
eial.. Journal of Research offheNauonal Bureau of Standards 63A, \\2
A959)-

approxmiate result B0). The vapor pressure of 4He, plottedin Figure 10-4,
is widely used in the measurement of temperatures between I and 5 K.
The phasediagram of 4He at low temperatures was shown in Figure 7.14.
Notice tUat the liquid-soHd eoexistence curve is closely horizontal below 1.4K.
We infer from this and (I!) [hat the entropy of the liquid is very nearly equal
to the entropy of the solidin this region. It is remarkable that the entropies
should be so similar, because a normal liquid is much more disordered than a
solid, so that the entropy of a normal liquid is considerably higherthan that
Chapter 10: Phase Transformations

of a normal solid. But 4He is a quanhim liquid. For another quantum liquid,
3He, the slope of the liquid-solid curve is negative at low temperatures
(Figure 7.15), entropy of the liquid is lessthan the entropy
and in this region the
of the solid has more accessible
solid. The statesthan the liquid! Liquid 3He
has a relatively low entropy for a liquid because it approximates a Fermi gas,
which generally has a low enSropy when t \302\253
zF because a large proportion
of the atoms have Sheir momenta ordered into the Fermi sphere of Chapter 7.
Triple point. The triple poin! t of a substance is that point p,, t, in She p~z

plane all three phases, vapor, liquid,and solid,

at which are in equilibrium.
Here ng =
/i(
= /js. Consider an equilibrium mixture ofliquidand solid phases
enclosed in a volume somewhat larger than that occupied by the mixture
alone. The remaining volume will contain only the vapor, in equilibrium wish
bo!h condensed phases,and at a pressure equal to the common equilibrium
vapor pressure of both phases. This pressure is the triplepointpressure.
The iriple point temperature is not identical wish the melting temperature
of She substance at atmospheric pressure. Melting temperatures depend
somewhaton pressure; triple the
point lemperaSure is the meiSing temperature
under common the
equilibrium vapor pressure of the two condensedphases.
For water the triple point temperature is 0.01 K above the atmospheric
pressure melting temperature; T, = O.Oi\302\260C = 273.16K. The Kelvin scale is
defined such that the triple point, of water is exactly273,16K; seeAppendix B.

Latent heat and enthalpy. Tile latent heat ofa phase transformation, as from
the liquid phase to she gas phase,is equal to t times the entropy difference
of the two
phases at constant pressure. The latent heat is also equal to the
difference of H s V -f pV between the two phases, where H is called the

enthalpy. The differential is dH = dU -f pdV + Vtlp. When we cross the

coexistence curve,the thermodynamic
identity applies:

Tito = dV -f- pdV - (}tg

-
jt,)dN , B2)

On the coexistencecurve jig ~

//,. Thus at constant pressure

L \302\253
tAa \302\273
At/ + pAV \302\273
Ml =
Ha
- llt. B3}
Values of// are tabulated; ihey are found by integrationof the heat capacity
at coiisnint pressure:

\342\200\224- =
T Hr- 1
 Derivation of the Coexistence Curve, p Ver

jc,,
B5)

Example: Model system for gas-sotidequilibrium. We construct a simple model io de-

a solid in equilibrium
describe as in Figure 10-5.
with a gas, We vapor
can easily derive ihe
pressurecurve for ihis Roughly the same model would
model. apply to a liquid.
Imagine the solid to consist of N atoms, each bound as a harmonic oscillator of fre-
frequency u to 3 fixed center ol force. The binding energy oleach atom in ihe ground siaicis
that
\302\243fl; is, ihe energy of an atom in its ground state is \342\200\224
co referred to a free atom at rest.
The energy states of a single oscillator arc ntioi \342\200\224where
r.o, h is a positive integer or zero

(Figure 10.6). For the sake of simplicity we suppose itial each ntom can oscillaiconly in o:.e

dimension. The result for oscillators in [hrce dimensions is left as a problem.

The pariiiion Junction ol a single oscillaior in llie solid is

Z, = \302\243\302\253p[-(n/10>
-
eo)/r]
= expOWt)
\302\243\302\253p(--,,Aa./T)
=

B6)

The Ziee energy F, is

F* = u* ~ Tff,
-
-tlogZ,. B7)

The Gibbs free energy in the solid is, per atom,

-
Gs
\302\253
Vt to-, + pt', =>
Fs + pvx = //,.

Figure 10.S Aloms in a solid in cqmSibn

wiih aionis in the gas phase. The equilibri
pressureis a function ol temperature. The
energy ol the atoms in [he solid phase is lo
than in ihe gas phase, bm the cmiopy of \\

aioms lends lo be higher in the gas phase. . The

equilibrium configmaiion is dfiietiiiiacd y ihe

cotmtcrpkiy of the iwo ciTccls.A! low

lanpemSurc most of iIk atoms ;src in ll

at high temperature all ot most of ihe a
may be in ihe gas.
 Chapter 10: Phase Transformation

lor of frequency (u. The

ssumed 10 be % below that o(a

in!he gas phase.

Ground Male <

bound aloui

The pressure in the solid is equal to that o[ [he gas with which il is in contact, but Uie
volume i>i per atom in ihe solid phase is much smaller than the volume vt per atom in [he
gas phase: c, \302\253
vr
\342\226\240

If we neglect the term pv, we have (or the chemical potential of [hesolidp, S f whence
\342\200\236
the absolute activity is

,/t) = exp(-logZJ

<stp(-to/i)[l - B9)

We make the ideal gas approximation to describethe gas phase, and we take Ihe spin of
the atom to be zero. Then, [rom Chapter 6,

' \302\253q '\"a t\\

C0)

The gas is in equilibrium with the solid when

).f
= or
).\342\200\236

p =
inQexp(-E0/t)[l
- exp(-/1<0/t)]. C1)
K we insert nQ from C.63J:

V
= C2)
(j^j
 Van Der Waats Equation of State

VAN DER WAALS EQUATION OF STATE

The simplest mode! of aliquid-gas phase transition is that ofvander Waals,\\vho
modified the ideal gas equation pV = Nx to take into accounlapproximately
the interactions between atoms or molecules. By the argument that we give
below, he was led to a modified equation of stateof the form

(p + N2a/V2)(V - Nb) = Nx , C33

known as the van der Waals equation of state. Tliis is written for N atoms in
volume V. The a, b are interactionconstantsto be defined; the constant a is
a measure of the long range attractivepart of the mieraeiion between two
molecules, and the constant /' is a measureof their short range repulsion
(Figure 10.7). We shall derive C3) \\vitli..tlie help of tlic general =relation p
~-(SF/DV)liN. We shall then trcal the ihcrmodynamic properlics of the model
in order to exhibitthe liquid-gas transition.

For an ideal gas we have, from F.24),

= + i]. C4|
F(idealgas) -NT[log(na/n)

The hard core repulsion

at short distances can be treated approximately as
if the gas had available not the volume V, but the free volume V ~
Sb, when
b is the volume per molecule. We replace therefore the concentration n =
N/V
in C4) by N/{V ~ Nb). Thus, insteadofC4),we have

F =
-NT{log[)fQ(V
- Nb)/N] + 1}. C5}
To this we now add a correction for the intermolecular attractive forces.

Figure 10.7 The iiucraaion energy between

repulsion plus a long range aiiracHou. The

short range repulsion can be described
approximately by saying that each molecule
has a hard, impeneirable coie.
Chapter 10: Phase Transformation*

Mean Field Method

There exists a
simple approximate method, called the mean field method, for

taking inio account the effect of weak long range interactions among the
particles system.The most
of a widely known applications method are to
of the
gases and to ferromagnets.Let tp(r) denote the potential energy of interaction
of two atoms separated a distance by r. When the concentration of atoms in
the gas is n, the average value of ihe total interactionof all other atoms on

the atom at r = Ois

C6)

where -2a denotes the value of ihe integral \\dVip{r). The factor of two is a
useful convention. We exclude the hard core sphereof voiume b from the
volume of integraiion. In writing C6) we assume that the concentration n is

constant ihroughout ihe volume accessible to the moleculesof the gas. That is,
we use the mean value of n. Tins assumption is the essence of the mean field
approximation. By assuming uniform concentration we ignore the increase
of concentration in regions of strong attractive potential energy. In modern
language
we say thaS the mean field method neglectscorrelationsbetween
\" \342\226\240
interacting molecules.

From C6) it follows that the interactions change the energy and the free

energy of a gas of N moleculesin volume V by

AF s MJ = -\\BNna) *=
-N2a/V. C7)

The factor j is common to self-energy problems; it arranges that an interaction

\"bond\"between two molecules is counted only once in the total energy.The
exact number of bonds is |-N(N - I), which we approximate as |N2.
We add C7) to C5) to obiain the v;m der Waais approximation for the
Heimholu free energy of a yas:

F(vilW) = - + 1} - Nza/V. 0$)

-.Vi{log[\302\273u(l'r Sh)/N~\\

The pressure is

C9)
'\342\226\240-^\302\253'\027^5-F
 Critical Pawls for the

Figure 10.8 of intermolecular

Direciions
forces that ad near ihe boundary
on molecules
of a volume Y. The van dci Waats argument

suggests lhal ihcse forces contribute art internal

pressure Nxa!Vl which Is lo be addedlo ihe

be used as ihe pressure in the gas taw.

Q
o
o o

V
Figure 10.9 Hieof volume Khas N
coniainer
molcculcSi each b. The volume
of volume not
O occupied by molecules is V - S'b. Intuition
0 suggests that iHis fece volume should be used in
llic gas law in place of the coiiiaincr Volume V.
O
o
o
\302\251
Q

(p + N2a/V2){V ~ Nb) \302\253

A'l . D0)

der Waals equatum of staSe. The terms in a and b arc interpreted in

10.8 and 10.9.

Points for She van der Waals Gas

ne the quantities

pc ^ a!21b2\\ Vc
s 3Nb; xc
^ 8a/27b. D1)
Chapter 10: Phase Trans/or,

. - 0.95tt
P/Pc

Figure 10.10 Tile van der Waals equation of stal

the critical temperature. Courtesy of R. Cahn.

In termsof these quantities the van der Waals equation becomes

3 l\\ 8t
\\(V D2)
f7HJAH 3/ 3t/

This equation is plotted in Figure 10-10 for several temperatures near the
temperature tc. The equation may be written in terms of the dimensionless
variables

ps pjPc\\ 9sVfV.\\ t e t/tc , D3)

D4)

This result ts known as the law of correspondingstates. In termsof p, V, t,

si! gases !ook alike\342\200\224if they obey the van der Waals equation. Valuesof a
 Gibbs Free Energy of the van (let M'aah Gas

and b are usually obtained by fitting to the observed pc and tc. States of two
substances at the same p, Vy x are called corresponding states of ihe subsiances.
Realgasesdo not obey the equation to high accuracy.
At one point, the critical point, the curve of p versus V at constant f has a
horizontal point of inflection. Here the local maximum and minimum of the
P~V curve coincide, and is no separation between the vapor and
there liquid

phases. At a horizontal point of inflection

a- @i-
These conditions are satisfied by D4) if9 = 1;i 1. We call
p = 1; =
pc, Vet

and tc the critical pressure, critical volume,and criticaltemperature, respectively.

Above tt no phase separation exists. \342\226\240-

Gibbs Free Energy of the van der Waals Gas

The Gibbs free energy of the van der Waals gas exhibits the characteristics of
the !iquici-gasphase transition at constant pressure. With G = F + pV, we

have from C8) and C9) the result

G(x,VtN)
= - - -
Nb)/N] + 1], D6)
-\342\200\224^ -^ Nt{log[\302\273u(K

This equation gives G as a function of V, t, N; the natural variables for G are

p, t, Unfortunately
N. we cannot conveniently put G into an analytic form as a
function of pressure instead ofvolume.We want G(z,p,N) because we can then
obtain ;i(t,p)as G(z,p,N)/N by (9.13). It is /i that determines the phase coexistence
relation ft,
= results of numerical calculationsof G versus
fig. The pare plotted
in Figure 10.! 1 for temperatures below and at ihe critical temperature. At any

temperature the lowest branch represents the stable phase; the otherbranches

represent unstable phases. The pressure at which the branchescrossdetermines

the transition gas and liquid; this pressure is calledthe equilibrium
between

vapor pressure. for G versus t are plottedin Figure

Results !0.12.

Figure 10.13 shows, on a p-V diagram, the region V < Vs In which only ihe

liquid phase exists and the region V > V2 in which only the gas phase exists.
The phasescoexist between Vx and V^. The value of Kj or V2 is determined by
the condition that /i](r,p)== }ia{x,p) along the horizontal line between Vx and
V2- This will occur if the shaded area belowthe Jine is equal to the shaded area
Chapter 10; Phase Ttansfo

-0.40 t\342\200\224

--
,-Vapor[ rasure

/
\\

Figure 10.11 (a) Gibbs free energy versus pressure for van
der Waals equaiion of stale: i = 0.95tc. Courtesy of R. Cahn.
(b) Gibbs free energy versus pressure for van der Waals equation of
stale;i = %..

above the line. To see ihis, consider

dG \302\253
~adx + Vdp + pdN. D7)

We have dG = Vdp at constant i and constanttola!number of particles. The

difference of G between V\\ and V1 is

G,-G,= fWp, D8)

 j 1
- 0.95
~p

nqb = !
LiqutaS^

\302\273bic

-
G/Nrc
k

i t i
'
0.984 0.986 0.988 0.990
\342\226\240
't/t,
(a)

Figure 10.12a Gibbs free energy versus temperature for van der Waals equalio
of slale a! p = 0.95 pe. Courlesy of A. Manoliu.

= 1.0
p

nqb
= 1

\\
- \\
\\oas

-2.70
0.90 I.OO 1.05 1.10
t/t,
(b)

Figure 10.12b Gibbs free energy versus temperature for van der Waais cquatiO!
of slate a! the crilical pressure pc.
Chapter Id: Phase Transformations

T ~ conslan

- ^Liquid
-Cocx Stetice fir c
\\ <\302\243 X
i
a as

|\\
s.

v.t

10.13 Isotherm
Figun e of van der Waalsgasat a
lemperafure belowliie critical lempcralure. For volumes
less than Vt only !hc liquid phase exisls; for volumes

above Kj only lliegas phase exisls. Between Vx and V2

Ihe system in stable equilibrium lies along the coexistence

line and is an inhomogencousmixture of two phases. The

liquid and gas phases coexist. The proportion of liic

liquid and gas phases must be such lhai ihe sum of fheir
volumes equals the volume V that is available.

bul ihe integral isjust ihesum ofthe shaded areas, one negalive and one positive.
When Ihe magnitudes of the areas are equal, G?(t,/>)
- Gj(t,p) and [is{x,p}=
/^{r,p)along Hie horizontal coexistence line drawn in the figure. In equilibrium
we require j.tg
= /*,.

Nuclcatiou. Let Aji

\342\200\224 \342\200\224be
ftg ;i, ihe chemical potential difTerence between
the vaporsurroundinga smallliquid droplet and the liquid in bulk (an infinitely

iarye drop), if A/i is positive, Ihe buik liquid will have a lower free energy than
the gas and thus the liquid will be more stable than the gas. However,the
surface free energy of a liquid drop is positiveand tends lo increase the free
energy of'he liquid. Al small drop radii the surface can be dominantand the

drop can be unstable with respect to the gas.We calculate the change in Gibbs

freecnergy when a drop of radius R forms. is the concentration

If\302\273,
of molecules
in the liquid,

AG =
G,
- =
-{ + 4nR2y D9)
G9
 Ferromagtutism

where y is the surface free energy per unit area, or surface tension. The liquid
drop will grow when Gt < Gr An unstable maximum of AG is attained when

ti&G/dR
= 0 = -4nR2iii&n + SnRy , E0)

Rc \302\2532y/H,A/i. E1)

This is the critical radius for nuclcation of a drop- At smaller R the drop will

fend to evaporaie spontaneously because that will Jower the free energy. At

larger R tlie drop will tend to grow spontaneously because that, too, will lower

the free energy.

energy barrier (Figure10.14)

The free that must be overcome by a ihcrni.i!
fluctuation in order fora nucleusto grow beyond R,. is found by substitution of
in
E1) D9):

=
(&G)C (lenPW/nMl*I}. E2)

If we assume [hat the vapor behaves like an ideal gas, we can use Chapter5
to express Aji as

-r ,
Aft tlog{p/peq)

where p is the vapor pressure tn the gas phase and pe<l

the equilibrium vapor
pressure of the bulk liquid (R ~* co). We use y
~
72erg cm\022 to estimate Rt
for water at 300 K and p = l.J^tobel x !0~6cm.

Kcrro magnet ism

A ferromagnet has a spontaneous magneticmoment,which means a magnetic

moment even in zero applied magneticfield.We develop the mean field approxi-
approximation SO the temperature dependence of ihe magnetization, defined as the
magnetic moment per unit volume. Tlie centra! assumptionis that each niagnelic
alom experiences an effective fieid BE proportional to she magnetization:

\302\253
AM E3)
BE ,

where I is a conslans. We take the external applied field as zero.

Chapter 10: Phase Tram/or

Critical barn t for growH,

*\"
or cortdcnsut 3n nuclei

fx
1
'
1

L ondensation , \\
| nuclei __

evaporate

\342\226\240'\342\226\240\342\226\240-

Figure 10.14 Excessfree energy of drop relative lo gas, as

function of drop radius R, both m reduced units. The gas is

supersaturated because the iiquid has the lower free energy for
this curve but the surface energy ofsmaii dropscreates
as drawn,
an energy barrier ihat inhibits the growth of nuclei of the liquid
phase. Thermal fluctuations eventually may carry nuclei over ihe
barrier.

Consider a system with a concentration h of magneticatoms, each of spin j

and of magnetic moment fi. In Chapter3 we found an exact result for the
magnetization in a field B:

M = HjitanhOiB/t). . E4)

In the mean field approximation E3) this becomes, for a ferromagnet,

. . . Me n/nanh(/dMA)
\342\226\240\"\342\226\240_\342\226\240_\342\226\240 , . '.. '. E5)
 Fcrromu^cth,

0 0.2 0.4 0.6 0.8 1.0

Figure 10.15
Graphical soiuiion of \302\243q.
E6) for the
reduced magnetization ,,i as a function of temperature.
The reduced magnetization is defined as m = M/n/t. The
left-hand side of Hq. E6) is piolicd as a straight line in
with unit slope. The right-hand side is tanh(m/0 and is

plotted versus
for three difierenl
in values of the reduced

temperature t = r/n;i'^ *= i/tt. The three curves

correspond to the temperatures 2x,,zt, and Q.5rt. The
curve for i = 2 intersects the straight iine in only al
m s= 0, as appropriate for ihe paramagnetic region (iherc
is no externai applied magneiic fieid). The curve for / = i
(or t = it) is tangent lo the suatght Sine m at ihc origin;
this ictnpetalure murks ilic onset of fcrroiiiagnetisiu.The
Curve for i = 0.5 is in iiie ferromagnciic region and
tmersccts ihc straight line in at about s=
\302\273i 0.94 n/i. As
1 -\342\200\242
0 the intercept moves up to in - l.so that all
magneiic moments are iined up at absolute zero.

a transcendental equation for solutions of this equation

M. We shall see that
with nonzero M exist in the temperature range between0 and v To solve E5)
we write it tn terms of the reduced magnetization ??i \302\253
M/h/i and the reduced

temperature f s z/n[i2X, whence

hi = E6)
ianh{Hi/r).

We plot the right and left sides of this equation separately ;is functions of \302\273t,
as in Figure 10.15. The intercept of the two curvesgives the value of m at Ihe
temperature of interest.The critical temperature ts f = I, or zt = h/i^L The
curvesof M versus x obtained in ihis way reproduce roughly the featuresofthe
 Chapter 10; Phase Transformation

Figure 10.16 Saiuration magnetization of

nickel as a function of temperature,together

with ihc theoretical curve fci spin \\ on ihe
mean fieid theory.

experimental resuiis, as shown in Figure 10.16 for nickel As t increases the

magnetizationdecreases smoothly to zero at z = rc, called the Curie temperature

LANDAU THEORY OF PHASER TRANSITIONS

Landau gave a systematic formulation of the mean field theory of phase transi-
transitions applicable to a large variety of systems exhibitingsuch transitions.We
consider systems at constant volume and temperature, so that their Heimholtz

free energy F = U ta is a minimum

\342\200\224 in equilibrium. The big questionis,a
minimum with respect to what variables? It isnot helpful to consider all possible
variables. We suppose here that the system can be described by a single order
parameter the \302\243, Greek xi, which might be the magnetization in a ferromagneti
system, the dielectric polarization in a ferroelectric system, the fraction of
superconducting electrons in a superconductor, or the fraction of neighborA-B
bondstotola! bonds in ait alloy AB. In thermal equilibrium the order parameter
will have a certain value c,
=
cc{c). In the Landau iheory we imagine Ihat \302
can be indepaideally specified, and we consider the LandauTree energy (\"unction

FL(\302\243.x)
= E7)

where the energy and entropy are taken when the order parameter has the

specified value \302\243

no! necessarily c0. The equilibrium value \302\2430{t)is the value of
 Landau Theory of Phase Transitions

makes FL a minimum, at a given

c, that t, and the actual Hdmholtz free energy
f(r) of the system at i is equal lo thai minimum:

F(t) \302\273
Fl($0,t) S FL(\302\243r) if *
\302\243 Co- E8)

Plotted as a function of for

\302\243 constant r, ilic Landau free energy may have more
than one minimum. The lowest of these determines the equilibrium state. In a
first orderphase transitionanother minimum becomes the lowest minimum as
i is increased.
We restrict ourselves to systems Landau (\"unction
for which Ihe is an even

function of in
\302\243 the absence of applied fields. Most ferromagneticand ferro-
ferroelectric systems are exam pies of this. We also assume that F 1(^,1) is a sufficiently
well-behaved function of that
\302\243 it can be expanded in a power series in \302\243\342\200\224

something that should not be taken for granted. For an even function of as
\302\243,

assumed,

The entire temperature dependence of FL(\302\243,x) is contained in the expansion

coefficients ga\\ g2,gx, g6- These coefficients are matters for
experiment or theory.

example of a phase transitionoccurswhen

The simplest ^(x) changes sign at
a temperature i0, with y4 positive and the higher terms negligible.For simplicity
we take g2(t) linear in i:

<72(r)
~ (r
- to)* . F0)
over the temperature range of interest, and we take g4 as constant in that range.
Witli these idealizations,

The form F0) cannot be accurateover a very wide temperature range, and it

certainly fails at low temperatures because such a linear dependence on tem-

temperature is not consistent with the third law.
The equilibrium value of is
\302\243 found at the minimum of FL{$ ;t) with respect

which has the roots

f~Q and ? = (to - r)(a/g4). F3)

Chapter iff; Phase Transformations

With a and ga positive, the root c, = 0 corresponds to the minimum of the free
energy function F1) at temperatures above i0; here the HelinhoHzfreeenergy is

J=Xt) = 0g(l). F4)

The other root, c,2 ~

(a/gj(to
- t) corresponds to the minimum of the free
energy function at temperatures below t0; here the Helmhoitz free energy is

The variation of F(r) with temperature is shown 10.17. The variation

in Figure
of FdZ'J-) as a function of for
\302\243: ihree representative temperatures is shown in
Figure 10.18,and ihe temperature dependence of the equilibrium value of \302\243
is

shown in Figure 10.19.

Our model describesa phasetransition in which the value of the order paratn-
elergoes continuously to zero as the temperature is increased to t0. The entropy

Figure 10.17 Temperature dependence of (he free energy

for an ideatized phase t ransition of the second order.
Figure 10.18 Landau free energy function versus at
\302\2432

reprcscniaLivc temperatures. As the temperature drops below t0

the equilibrium value of \302\243
gradually increases, ;is tic fined by the

posiiion of the minimum of the tree energy.

Figure 10.19 Spontaneous polarization versus

temperature, for a second-order phase transition. The
curve is not realisticat low temperatures because of the
use Of Eq. F0): the third law of thermodynamics requires
thatdf/rfr ->0asi-*0.
Chapter 10: Phase Transformations

\342\200\224
dFfdz is continuous at t = rQ,so that there is no latent heat at the transition
temperature f0. Such a transition is by definition a second order transition.
Transitions with a nonzero latent heat are called first order transitions; we
discuss them presently. The real world contains a remarkable diversity of
second order transitions; the best examples arc ferromagnels and super-
superconductors.

Example: Ferromagnets. In the mean field approximation, ferromagnets satisfy the

Landau theory. To show this, consider a n atom of magnetic moment a
pin magnetic field 3,
which we shall set equal to ihe tijean field >M as in E3). The interaction energy density is

V(M) = -\302\261 F6)

where ihe factor j iscommon to self-energy problems. The entropy density is given approxi-

g{M) = constant - M2J2nn2 , F7)

in Ihe regime in which M \302\253

n/j. Thus the free energy fursciion per unit volume is

FL{M) ~ constant - \\M2(/.'~ \342\200\224A+ lermsof higher order. F8)

At Ihe transition temperature the coefficient of M* vanishes, so ihat

i0 - \302\273}i2>., F9}

in agreement with the discussion following E6).

First Order Transitions

A latent heat characterizes phase transition. The liquid-gas
a first order transi-

lion at constant pressure is a first order transition. In ihe physics of solids first
order transitions are common in ferroelectric crystals and in phase transforma-
in metals
transformations and alloys. The Landau function describes a first order iransition

when the expansion coefficientg* is negative and gb Is positive. We consider

 first Order Transitions

Figure l(K20 Landau free energy function versus i1 m a

first order at representative
transition, temperatures. At xc
the Landau function has equal minima at a
at =
\302\243 0 and
finite as shown.
\302\243 For t below rf the
absolute minimum is
iatger values of ^; as r passes through tc there is a
disconimuouschcinge in the position of the absolute
minimum. The artows mark the minima.

The extrema of this function are given by the roots o

FigureJ0.20:

G1)

Either - 0 or
\302\243

G2)

At the transition temperature rc the free energies will be equal for the phases
with c,
~ 0 and with the root c^O. The value of xc will not be equal to r0,
Chapter 10; Phas

_60 -40 -20

~
T rrt in K

and the order parameter\302\243

(Figure 10.21} does not go continuously to zero at
xc. These results differ from those in the second order phase transition treated
earlier, where \302\243
weui to zero continuously at t0 - tf. A first order transfor-
transformation may show hysteresis, as in supercooling or supcrsaturation, but no
hysteresis exists in a second order transition.

1. The coexistencecurve in the p-x planebetween two phases must satisfy tiic
Clausius-Clapeyron equation:

dp L
_

where L is the latent heat and An is the volume difference per atom between
the two phases.

2. The latent heat L ~ H, - Hlt where H ~ V + pV is the enthalpy.

3. The van der Waais equation of state is
'
. (P + N2a!V2){V
- Nb) = Nx.

4. In the Landau free energy function

the energy and entropy are taken when parameter has the specified
the order
value \302\243,,
not necessarily the thermal equilibrium value \302\2430.
The function Fl
is a minimum with respect to when
\302\243 the system is in thermal equilibrium.
5, A first order phase transition is characterizedby a Intent heal and by
hysteresis.

PROBLEMS

/, Entropy^ energy, and enthalpy of van der IVaah gas. (a) Show that the en-
entropy ofthe van dcr Waats gas is

o- N[log[nQ(V
-
Nb)JN] + 1}. G3)

(b) Showthat the energy is

U = INi.- N2.ii!V. G4)

(c) Show thai the enthalpy// = U + pV i%

H{i,V)
=
|Nt + N2bx/V - 2N2ajV\\ G5)

- ~
//(r./>) -jNr + NhP 2NuPfx. G6)

All results arc given to first order in the van der \\V;ials correction terms o, h.
2. Calculationof (IT{dp for water. Calculate from the vapor pressure equa-
equation the value of elT/dp near p ~ 1 atm for the Hquid-vypor equilibrium of
wmcr. The heat of vaporizational 100Xis 2260 Jg\021. Express the result in
keivin/atm.
3. Heat of vaporization of ice. The pressure of water vapor over iceis3,SSmm
Hgal ~2=C and 4.58 mniHgai OX. Estimatein Jmol\"' the heat of vaporiza-
of
vaporization ice at ~l\302\260C.

4. Gas-solid equilibrium. Consider a version of the exampleB6}-C2)

in which

we let the osciSiators in the soiid move in three dimensions, (a) Show that in the
high temperatureregime(t \302\273
haS) the vapor pressure is

(b) Explain why the latent heat per atom is tQ \342\200\224

\\i.

5. GaS'SoU'd equilibrium. Consider the gas-solid equilibrium under the ex-

extreme assumption that the entropy of the solidmay be neglected over the tem-

temperature range of interest. Let -e0 be the cohesiveenergy ofthe solid,per atom.
Chapter 10: Phase Transformatio

Treat the gas as idea!and monatomic. Make the approximation that the volume
accessible to the gas is the volume V of the container, independent of the much
Smaller Volume occupied by the Solid, (a) Show thai the total HeimhoHzfree
energy of ihe system is

F = F, + F, \"
-Ufa + - I] ,
N,r[!og(N,/l'il0) G8)

where the total number of atoms, N = N, + Ng

is constant, (b) Find the mini-
minimum of ihe free energy with respect to N^show that in ihe equilibrium condition

09)

(c) Find the equilibrium vapor pressure.

6. Thermodynamics of the superconducting transition, (a) Show that

(SO)
2/i0 th . [i0 ih

in SI units for Be. Because Bc decreases with increasing temperature, the right
side is negative. The superconducting phase has the lower entropy: it is the more
ordered phase. As t ~+ 0, the entropy'in both phases will go to zero, consistent
with the third law. What docs this imply for the sliapc of the curve of Bt versus r?

(b) At r = xtt we have Bt = 0 and hence =

a^ aN. SIiow llutt this result hits ihe
following consequences: A) The two free energy curves do not cross ;if tt but
merge, as shown in Figure 10.22.B) The two energies are the same: Usfr,.) =
U.vW- C) There is no Intent heat associated with the transition at r \342\200\224 tt.

What is the latent heat of the transition when carried out in a magnetic field,
at r < i{7 (c) Show that Cs and CN, the heat capacitiesper unit volume, are

related by

(81)

Figure S.iS is a plot of Cj'T vs T1 and shows that Cs decreases much faster

than linearly with decreasing r, while Cs decreasesas yz. For t \302\253

tc> AC is
dominated by Cs. Show that Hiis implies
 _- -0.2

.1 X. Normal

Superconductor

*STC=1.180K

0.5

Temper; lure. K

Figure 10.22 Experimental values of the Tree energy as a function of

temperature in the superconducting state and in the normal

Tor aluminum
stale. Below the transition temperature T, = 1.180 K (he free energy is lower
in !he supcrcondtiding slate. The (wo curves merge at the transition
tempcra(ure, so thai the phase transition is second order {(hereis no laient heat

of transiiion a! Tc). The curve Fs is measured in zero magnetic field, and FN is

measured in a magnetic field suftkien! to pu! the specimen in (he normal slaie.
Courtesy of N. E. Phillips.

7, Simplified model of the superconducting transition. TheBc(i}curves of most

superconductors iutve shapes close to simple paraboias.Suppose that

= - (83}
Bt(i) Bt0[l d/r(}2].

Assume that Cs vanishes faster than linearly as t -* 0. Assumealso that Cs is

linear in r, as for a Fermi gas (Chapter 7}. Draw on the resultsof Problem 6 to

calculate and plot the i dependencesof I he two entropies, the two heat capacities,
and ihe latent heat of the transition. Show that Cs(rc)/Cv(r(}= 3.

8. First order crystal transformation. Consider.'! crystal that can existin eilher

of two.structures, denoted by a and /?. We suppose 'hat the a slrucmre is the

siable low temperalure form and the /J structure is the stable high semperalure

form of the substance. If the zero of the energy scale is taken as the stale of
separated atomsat infinity, then the energy density 1/@) at r == 0 uill be
Chapter 10: Pha:

negative. The phasestable at t \342\200\224

0 will have the lower value of U{0);thus
Ux@) U?@). < velocity of sound ve If the in the /J phase is lower than vx in the
a phase, corresponding to lower values of the clastic moduli for /?, then the
thermal excitationsin the $ phase will have larger amplitudes than in the a
phase.The larger the thermal excitation, the larger the entropy and the lower
!he free
energy. Soft systems tend to be stabie at high tempera!ures,hard
systems (a) Show from Chapter 4 that
at low. the free energy density contributed
by the phonons in a solid at a temperature much icssthan the Debye temperature
is given by -~rc2r'i/3Oi;3/i3, in the Debye approximation with v taken as the
velocity of all phonons.(b) Show that at the transformation temperature

>-v.-'). (84)
There be will a finite real solution if t'p < iv This example is a simplified model
ofa classof actual phase transformations in solids, (c) The latent heat of trans-
transformation is defined as the thermal energy that must be supplied to carry the
system through the transformation. Show that the latent heal for this model is

L = 4[U,@)- t/,@ (85)

In (84) and (85), U refers to unii volume.

Chapter
11

Binary Mixtures

SOLUBILITY GAPS 310

ENERGY AND ENTROPY OF MIXING 31-1

Example: Binary Alloy wrth Nearest-Neighbor Interactions 318

Example: Mixture of Two Solids with Different Crystal Structures 319
Example: Liquid 3Hc-\"He Mixturesat Low Temperatures 320

Phase Diagrams for Simple Solubility Gaps 321

PHASE EQUILIBRIA BETWEEN LIQUID
AND SOLID MIXTURES 322
Advanced Treatment: Eutectics 325

SUMMARY 330

PROBLEMS 330

1. Chemical Potentials in Two-Phase Equilibrium 330

2. Mixing Energy in 3He-4He and Pb-Sn Mixtures 330

3. Segregation Coefficient of Impurities 331
4. Solidification Range of Binary Alloy 331

5. Alloying of Gold into Silicon 33i

Chapter 11: Binary Mixtures

Many applications of materials science,and large parts of chemistry and

biophysics, are concerned with the of
properties multicomponentsystems that

have two or more phases in coexistence.Beautiful, unexpected,and important

physical effects occur in such systems. We treat the fundamentals of the subject
in this chapter, with examples drawn from simple situations.

SOLUBILITY GAPS

Mixturesarc systems of two or more different chemical species.Birjury mixtures

have only two constituents. Mixtures with three and four constituents are called
ternary and quaternary mixtures.If the constituents arc atoms, and not mole-
molecules, the mixture is called an ailoy.
A mixture is homogeneous when its constituents are intermixedon an atomic

scale to form a single phase, as in a solution. A mixture is heterogeneous when it

contains two or more phases, such as oil and

distinct water. The everyday
expression \"oii and water do not niix\" means [hat their mixture does not form
a single homogeneousphase.
Thepropertiesof mixtures differ from the properties of pure substances. The
melting and solidification properties ofmixturesareofspeciai interest. Hetero-
Heterogeneous mixtures may melt at lower temperatures than their constituents.

Consider a gold-silicon alioy: pure Au melisat lO63cCand pure Si at I404X,

but an ailoy of 69pet Au and 31 pet Si melts (and solidifies}at 37OCC. This is not
ihc result of ihe formationof any low-melting Au-Si compound: microscopic
investigation of the solidified mixtureshows a two phase mixture of almost
pure Au side by side with almost pure Si (Figure I I.I}.Mixtures with such

properties are common, and they are of practicalimportance precisely

because

of their lowered melting points.

What determines whether two substances form a homogeneous or a hetero-
heterogeneous mixture? What is ihe composition of ihe phaseslhat are in equilibrium

with each osher in a heterogeneous mixture?The properties of mixtures can be

underslood from the principle that any system at a fixed semperaiure will
evolve to the configuration of minimum free energy. Two subsiances wiil
dissoive in each oilier and form a homogeneous mixtureif that is the configura-

of
configuration iowest free energy accessible to the components. The subsiances will
 Solubility Gaps

SO/tm

Figure II.I Heterogeneousgold-silicon alloy. When a mixture of 69 pci Au and 31 pet

Si is melted and then solidified, the mixture segregaies into a phase of almost pure Au

(Sight phase) coexistent a

\302\253iih phase of almost Si
pure {darkphase).Magnified aboui

800 times. The composinon given is that of the lowest-melting Au-Si mixture, the

so-called eutectic a
mixture, concept explained later in she text. Photograph courtesy
ofStephan Justi.

form a heterogeneous tnixlure if [he combined free energy of the Uvo separate

phases side by side is tower ihaii the free energy of the homogeneous mixture:
then we say I hat the mixture exhibits a solubility gap.
A hclerogeneous miMure will melt at a lower [cmperalurethan the separate
substances if I he free energy of the homogeneousmeltis lower than the com-
combined free energies of the two separate solid phases.
Throughout ihis chapter we assume for simplicity that the external pressure
may be neglected, and we sel pV = 0. Then volume changesdo not involve

work, and the appropriate free energy is tire HelmhoUz free energy F rather
Ilian the Gibbs free energy G. We will usually simply speak of the free energy.
We discuss binary mixtures of constituents Ihat do no! form well-defined

compounds with each other. Our principal interestis in binary alloys. Consider
Chapter H: Binary Altitun

Many applications of materials science, and large parts of chemistry and

biophysics, are concerned with the properties of multicomponent systems that

have two or more phases in coexistence. Beauiiftil, unexpected, and important

physical systems.
effects Ihe fundamentals
occur in such We treat of the subject
in this chapter, with examples drawn from simplesituations.

SOLUBILITYGAPS
Mixtures are systems of two or more different chemical species. Binary mixtures
have only twoconstituents. Mixtureswith three and four constituents are called
ternary and quaternary mixtures.If the constituents are atoms, and not mole-
molecules, the mixture is called an alloy.
A mixture is homogeneous when its constituents arc intermixedon an atomic

scale a Single phase, as in a solution.

to form A mixture is heterogeneous when it

contains two or more distinct phases, such as oil and water. The everyday
expression \"oil and water do no! mix\" means that their mixture does iiot form

a single homogeneous phase.

The properties of mixtures differ from the properties of pure substances. The
melting and solidification properiies of mixtures are of special interest.Hetero-
Heterogeneous mixtures may melt at lower temperatures than their constituents.
Consider gold-silicon a
alloy: pure Au melts at 1063\302\260C and pure Si at 1404\302\260C,
but an alloy of 69 pet Au and 31 pet Si melts (and solidifies} at 370\302\260C This is not
the result of the formationof any iow-me!ting Au-Si compound: microscopic
investigation of the solidified mixture shows a two phase mixture of almost
pure Au side by side with almost pure Si (Figure 11.1).Mixtures with such

properties are common, and they are of practical importance precisely because
of their loweredmelfing points.

What determines whether two substances form a homogeneousor 3 hetero-

heterogeneous mixture? What is the composition of the phasesthat are in equilibrium

with each other in a heterogeneousmixture?Theproperties ofmixtures can be

understood from the principle that any system at a fixed temperature wiil

evolve to the configuration of minimum free energy. Two substanceswill

dissolve in each other and form a homogeneousmixture if that is the configura-
of
configuration lowest free energy accessible to the components. The substances will
 Solubility

10/mi

H.I
jure 11.1
Figure Heterogeneous gold-siliconalloy. When a mixture of 69 pet Au and 31 pet
is melted
Siisn and ihen solidified,!hemixiure segregates into a phase of almost pure Au
(lighi phase) codxisieni wiih a phase of almost pure Si (dark phase). Magnified aboui

800 limes. The composition given is !hal of ihe towesi-melting Aii-Si mixiure, ihc

so-called eulectk: mixture, a concept explainedtater in ihe texi. Photograph courtesy

ofSiephanJusii.

form a heterogeneous mixture if the combined free energy of the two separate

phases side by side is lower than the free energy of the homogeneous mixture:
then we say that the mixture exhibiis a solubility gap.
A hcierogeneous mixture will melt at a tower temperature than the separate
substances if the free energy of the homogeneous melt is lowerthan ilie com-

combined free energies of the two separate solid phases.

Throughout Ihis chapter we assume for simplicity that the external pressure

may be neglected, and we set pV ~ 0. Then volume changesdo not involve

work, and the appropriate free eneryy is the Hetmlioltzfree energy F rather

than the Gibbs free energy G. We will usually simply speak of the free energy.
We discuss binary mixtures of constituents that do not form weil-defined
compounds wiih each other. Our principal interest is in binary alloys. Consider
Chapter Hi Binary Mixtures

a mixture of JVA aloms ofsubsiance A and NB atoms of substance B.Thetotal

number of atoms is

We express the composition of the system in iermsof the fraciion x of B aioms;

x \302\273
A'b/N; 1 - x \302\273
jVa/N. B}

Suppose the sysiem forms a homogeneous solution,wiih an average free energy

per atom given by

/ = F/N. C)

Suppose further that/(.\\) lias the functional form shown in Figure 11.2. Because
this curve contains a range in which ihe second derivative d2f/dx2 is negative,
we can draw a line tangent to the curve at two
points, at x = xx and x \342\204\242
x^.
Free energy curves of this shape are common,and we wilt see later what may
cause this shape. Any homogeneous mixture in the composition range

x, < x < xp D)

is unstable with respect to two separate phases of composition x, and x^. We

shall that ihe average free energy per atomof the
show segregated mixture is

given by the point i\"on the straight line connecting the points a and [}. Thus in ihe
entire composition range D) the segregatedsystem has a lower free energy than
the homogeneoussystem.
Proof i The free energy of a segregated mixture of the two phasesa and j$ is

F =>
NJix,) + NfJ\\xfi) . E)

where ,V, and

Nfi are the total numbers of atoms in phasesa and ji, respectively.
These numbers satisfy the relations

which may be solved for .V, and Ny.

0)
 Solubility Gaps

Figure Free energy per alom as a function

tl.2 of composition, for a
system with gap. tf the free energy
a solubility per aiom of a
homogeneous mixture has a shape such that a tangent can be drawn
that touches the curve at two diftereiit points x and /?, (lie composition
range between the two points is unstable. Any mixture with a
composition in this range will decompose into two phases with the
composition _v, arid ,\\f. The free energy of the two phase mixture is
given by the point / on the straight line, below the point It.

From E) we obtain

fjix) (S)
JV

for the free energy of the two phase system. This is linear in x and is a
result
straight line in thef-x plane. If we set .v. = A'3 or.v^, v,c see (hat the line docsgo
through the points a and /?. Thus/ in (he interval between .y4 and xfi
is given by
the point i on the straight lineconnectinga and p.
Chapter II: Binary Mixtures

We have not yet made useof (he assumption that (he straight line is tangentto
f{x) at the
points 3 and /J, and therefore our result holds for any straight line
that has two points 2 and/Jin commonwith/(.v). Bui fora given vaiue of x, (he
lowest free energy is obtainedby drawing (he lowest possible straight line that
has (wo points in common wiih/(-v), on opposite sides of a-. The lowest possible
straight line is the (wo-pointtangent shown. The compositions x3 and x? are
the limits of the solubility gap of (he system.

Once (he system has reachedits lowest free energy, (he (wo phases must be in
diffusive equilibrium with respect to both atomic species,so thai their chemical
potentials satisfy

/*a> = /*\302\253;
=
Pb\302\273 Pb*- (9)

We show in Problem i that jja and /jB

are given by (he intercepts of the two-
point tangent with the two vertical edges of thc/(x) plot at x *= 0 and a ~ 1,
as in Figure 11.2.

ENERGY AND ENTROPY OF MIXING

The Heimhoitz free energy F ~ U ~ to has contributions from Ihe energy and
from the entropy. We treat the effect of mixing two components A and B on

both terms. Let uA and \302\273a

be the energy per atom of the pure substancesA and B,
referred to separated atoms at infinity. Tlie average energy per atom of the
constituents is

u =
(uANA + vsyn)/N - nA 4- -
(\302\253B uA)x , A0)

which defines a straight line in the u~x plane. Figure 11.3. The average energy
per atom of the homogeneous mixture may be larger or smallerthan for the
separate constituents. In (he example of Figure11.3,(he energy of the homoge-
homogeneous niixture is larger than the energy of the separate constituents.The
energy excess of mixing.
is called the energy
If (he re term in the free energy is negligible,asat 1 = 0,a positive
\342\200\224
mixing

energy means that a homogeneous mixture is not stable. Any such mixture will
then separate into two phases. But at a finite temperature the \342\200\224ia
term in the

free energy of the homogeneous mixturealways tends to lower the free energy.
Theentropy ofa mixturecontains a contribution, called the entropy of mixing,
that is not present in (he entropies of the separate components. The mixing

entropy arises when atoms of the different species are interchangedin position;
this operation generates a different state of (he system.Because of such inter-
 Energy and Entropy of Mixing

Figure 11,3 Energy per atom as a function of composition

in a sysicm with a positive mixing energy. A simple

example for which a solubiliiy gap may occur is thai of a

system in which the energy per atom of the homogeneous
mixilire is greater than Him of ihe separate phases, so that
1
0 for att c mposi s. The ing e rgy i
differ e bci een the u[x) curve and the straight line.

changes a mixture has more accessible states than tlie two separate substances,
and hence the mixturehas the higher entropy.
In C.80) we calculated the mixing entropy erM of a homogeneous alloy
A, ^B,. to find

(ID

as plotted in Figure 11.4. The curve of aM versus x has the important property
that the slope at the ends of the composition range is vertical. We have

- X)
-
bgx - ioj A2)
N dx

which goes to + co as x -+ 0 and to \342\200\224

co as x -* I.
Chapter II: Binary Mixtures

da^/elx
= \342\200\224
X

Ffgure 11.4 Mixing entropy. Tn any mixture of two constii uenis an

interchange of two atoms of different species leads to a new slate of the
system. The logarithm of liie number of slates related in this way is the

mixing entropy.

Consider now the quantity

u[x)
-
(a
- ffjtf A3)

which is the free energy per atom without the mixing entropy contribution. The
non-mixing part of the entropy,<j \342\200\224
an, is usually nearly the same for (he
mixture as for (he separate components, so that {er
\342\200\224
cM)r is nearly a linear
function of the composition x. If we assume this, the /0(.v) cuive has the same

shape as the
u{x) curve, but offset vertically.
If we add the mixing contribution
entropy ~-zaM/N to fo(x), we obtain at
various temperatures the f{x) shown curves in Figure 11.5. In drawing the
figure we have ignored the temperature dependence of/0(.v) itself, because for
 Energy und Entropy of Mixing

Figure 11.5 Free energy per atom versus composition, at three

temperatures.The curve fQ is the free energy per atom without the
mixing entropy contribution. For ilHistraiion a parabolic composition
dependence is assumed, and the temperaturedependence of/0 is
neglected. The tliree solid curves represcnl the free energy including
the mixing entropy, for the temperatures 0.8 rM, 1.0 tM, and 1.2 rM,
where rw is the maximum temperature for which there is a solubility
gap. The phase separation at 0.8 rw is apparent.

our argument this is irrelevant. Three importantdeductions

follow from the

construction of the/(x) curves:

(a) At all finite f{x) turns up at both ends of the composition
temperatures
range, because infinite slope of the mixing
of the entropy contribution.

(b) Below a certain temperature rM there is a com position range within which

the negative second derivative of the fo[x) curve is stronger than ihe
positive second derivative of the -taM contribution,thereby making it

possible to draw a common tangent to f(x) at two different values of x.

(c) Above Ty the curve has a positive second derivative at al! composilions.
Chapter 11: Binary Mixtures

We conclude that the A-B system with positive mixing energy will exhibii a

solubility gap below the temperature tM. The composition range of the gap
widens with decreasing temperature, but the gap can reach the edgesof the

composition range only as t -* 0. At any finite temperature there is a finite

solubility of A in B and of B in A, a result obtained earlier in Chapter 3. The
new result is that the mutual solubility is limited only below tw. Positive
mixing energies arise in different ways. We now discuss three examples.

Example: Binary with nearest-neighbor interact'ionSi

alloy Consider an alloy A^jB, in

which (he attractive interaction between unlike atoms is weaker than the attractive inter-
interaction between like atoms. For simplicity we speakof the interactions as bonds. There are
three different bonds: A-A, A-B, and B-B. Let uAA) uAB and uBB be ihe potential energies of
each bond.These binding energies will usually be negativewith respect to separated aloms.
We assume the atoms are randomly distributed among the lattice sites.The average
energy of ihe bonds surrounding an A alom is

uA
=
A
- x)uAA + xuAa , A4)

where (t - x)is ihe propoition of A and x is the proportion of B.This result is wiiucn in ihe
mean field approximationof Chapter tO. Similarly, for B atoms,

\"a
= A
- X)HAD + N\"UD. A5)

The total energy is obtained by summing over both atom types. Ifeach atom has p nearest

neighbors, the average energy per atom is

- ip[(l
- xJUAA + 2jcA
- *Kb + *3\302\253db]- A6)

The factor^ aiises because eachbond is sharedby the two atoms it connects. The result A6)
can be written as

u = ip[(l
- x)uAA + xum] + uM. A7)

is the mixing energy. On this model the mixing energy as a function ofx is a parabola, as in

Figure II.5.
 Energy and Entropy of Mixing

A solubility gap occurs whenever (/'//dx1 < 0, that is, when

= -2P[fAB - i(\302\253AA + O3- B0)

^r

From A2),

N dx2 x{l - x)

The equal sign holds for ,x = $. Wilh these results{19)yields

T*i
- -
iO'AA + ^a)] B2)
M\302\253ab

as die lower limit of the temperature for a solubility gap.

Thereare many reasons why mixed bonds may be weaker than ihe bonds of the sepafaic
constituents.If the constituent atom* of an alloy differ in radius, the difference introduces
clasticstrains that raise the energy. Water and oil \"do not mix\"' because water molecules
carry a large electric dipole moment that leads to a strong electrostatic attraction between

water molecules. This attraction is absent in water-oil bonds, which are only about as
strong as the weaker oil-oil bonds.

Example: Mixture of two solids with different crystal structures. Consider a homoge-
homogeneouscrystalline mixture silicon. The stable crystal
of gold and of gold is the face-
structure

centeredcubic structure in which every atom is surrounded by twelve equidistant nearest

neighbors. The stable crystal structure of silicon is the diamond structure in which every
aiom is surrounded by only four equidistant nearest neighbors, if in pure Au we replace a
small fraction xof the atoms by Si, we obtain a homogeneousmixture Au^.Si., wiih the
fee crystal structure of Au. Similarly, if in pure Si we replace a small fraction 1 - x of the
aioms by Au, we obtain a homogeneous mixture Au, -,5^, but with the diamond crystal
siructure of Si.There are two different free energies, one for each crystal structure (Figure
11.6).The two curves must cross somewhere in the composition range, or else pure Au and
Si would not crystallize in different structures. The equilibrium curve consists of the lower
of the two curves, with a kink at the crossover point. Such a system exhibits a sotubility

gap on either side of the crossover composition. The curves shown in the figure are sche-
schematic; in the actual Au~Si system the unstable range extends so close to the edges of the
diagram that it cannot be representedon a fult-scale plot extending from x = 0 to x = 1.
Chapter 11; Binary Mixture

\\/

Figure 11.6 Tree energy versus composition for cryslallinc

homogeneousmisiuresfor which [he [wo constituents of the
mixture crystallize in ^ilfcrem crystal structures. Two differe
free energy curves are involved, one for each crystal structure

Different crystal structures for the pureconstiiucmsarean important cause or solubility

gaps in crystalline solid mixiures. Our a/gument applies to mixtures of ihis kind, provided
the two structures do not transform coniiriuously into each other wilh changing composi-
This
composition. is a tacit assumption in our discussion, an assumption not always satisfied when
the two crystal structures are closely similar. The other assumption we make throughout
this chapter is that no stable compound formation should occur, in the presence of com-
compound formation the behavior of the mixture may be more complex,
--...-..
-\342\226\240\342\226\240\342\226\240
---\342\200\224.-.\342\200\224 ... -..,.-,... ~
vs^~7cz:\":\"s'.\".r:'~ ;-.-,,
\342\226\240\342\200\242\342\226\240-\342\226\240->\342\226\240\342\226\240-\342\226\240\342\226\240\342\226\240-\342\226\240\342\200\224

Exampk: Liquid SIU-* He m*.Uuivi at W tanpcraiures. The moat interesting liquid mix-
mixture with a solubility gap is the miMuniof ilie two iiefium isotopes JHeand JHe, atoms of

tiie Toruicr ocmii fcimjon^ unti of the 'aHer bosons, 1 lie re js a soluoiltty u\302\273io sn the mtx turc

oclow 0.S7rCj ii1/ in i igure 11.\027. 1 Ins property ss utilised m the Iicliuitt cJj'tiiion refftccr^tor

{Chapter 12). Tito mi.\\ing energy must be positi\\e to have a solubility gap. The origin of the
positive mixing encray is tht! folio\" ing: 4Hc aloiiisarc bosons.At suliieiently low tempera-
almost
temperatures jli \342\226\240*!
le afoins occurs) the ground state orbii;tl of the sysicm, vvherc they have
 Phaie Diagrams for SimpleSolubility Gaps

10 20 30 40 50 60 .70 80 90 100
\342\226\240\"
He
Atomic
percent \342\226\240'He pure

Figure 11.7 Liquid mixtures of JHe and 4Hc.

zero energy. Almost trie entire

kinetic kinetic energy of the mixture is contribuicd by t!ie
3He atoms, which are fermions.The energy per atom of a degenerate Fermi gas increases
v,ilh concentration as n1'*,as in Chapter 7. This energy has a negative secondderivative

Pltase Diagrams Tor Simple Solubility Gaps

A phase diagram represents dependence of solubiiily gaps,as in
the temperature
Figure 11.8. The two compositions xx and xf arc plaited horizontally, the

corresponding temperature vertically. The .v^ and xf branches merge at the

maximum temperaturet,m for which a solubility gap exists. At a given tempera-
temperature,
any mixture whose overall composition falls within the raoge enclosed by

the curve is unstable as a homogeneous mixture.The phasediagrams of actual

mixtures with solubility gups may be more complex,

according to the aclual
form of (he free energy relation/(.v), but the underlying principles are ihesamc.
Chapter II; Binary Mlxtur

Slabk

/ Decomposilion \\

1
1

Uns

Figure 11.8 Phase diagram for a binary system with a solubility

gap. A homogeneous mixture oCcomposition x will be unstable ai

temperature i if the point (*,i) Tails below tlic stability boundary
curve. The mixture will then form two
separate phasesof the
compositions given by the intersections of the stability boundary
curve with the horteontal line for temperature r. The stability

boundary curve shown here was calculated quantitatively for the

system of Figure lt.5, with a parabolic fo{x).

PHASE EQUIUBRIA BETWEEN LIQUID

AND SOLID MIXTURES

When a small fraction of a homogeneous liquid mixturefreezes,

the composition

of the solid that forms is almost always different from that of the liquid. The
phenomenonis readily understood from liquid and solid
the free energies for
mixtures. We consider a simple model, under two assumptions; (a) Neitherthe
 Phase Equilibria Between Liquid and Solid Mixtures

solid nor she liquid has a solubility gap. (b) The melting temperature ta or pure
constituenl A is lower Jhan the melsing Semperature tb of pure constituentB.
We consider a SemperaSure between ta and ra.
The free energies per atom, fs{x) Tor the solid and fL(x) Tor the liquid, are
shown 11.9a. The two curves
qualitatively in Figure
intersect at some com-
posision. LeSus draw a jangenScommonlo boSh curves, touching/j aS .\\ ~ xs
and fL a! x = xL.We can define three composision ranges, each with differcnS
internal equilibria:
(a) When x < xL, the system in equilibrium is a homogeneous liquid.
(b) When
system in equilibrium consistsof two phases,
xL< x < xs, the a

solid phase of composition xs and a liquid phaseof composition xL.

(c) When x > xs the system in equilibriumjs a homogeneous solid.

The compositions xs and xL of a so!id and a liquid phase in equilibrium arc
temperature dependent. As ihc temperature decreasesthe free energy of the
solid decreases more rapidly than tlKll of the liquid. The Ungctitiai points in

Figure 11.9amove to the Icfi, Tliis behavior is rcprcscnScdby a phase diagram

stinihlr to the earlier representationof the equilibrium composition curves for
mixtures with phase separation. In Figure 11.9b the curve for xL is called the
Hquidus curve; the curve for xs is the soltdus curve.

The phase diagrams have been determined experimentallyfor vast numbers

of binary mixtures. Those for most of the possible binary alloys are known.*

For most metal phase diagrams are more complicatedthan

alloys the Figure

11.9b, which for

was drawn a simple system, germanium-silicon.

When the temperature is lowered in a binary liquid mixturewith the phase

diagram of Figure lj.9b, solidification takes placeover a finite temperature

range, not just at a fixed temperature.To see this, consider a liquid with the

initial composition xiL shown in Figure 11.10.As the temperature is lowered,

solidification begins at t \342\200\224
x,. The composition of the solid formed is given
by xtsi so 'hat the composition of the remaining liquid is changed. In the

example xiS > xiL, so that the liquid moves towards lowervaluesof x, where the

solidification temperature is lower. The temperature has to be lowered if

solidification is to continue. The composition of the liquid moves along the

liquidus curve until the solidification is compleied at t = tA. The solid formed
is nonuniform in composition and is not in equilibrium. The solid may homoge-
homogenizeafterward by atomic diffusion, particularly if lhe temperature remains
high for a long time. But for many solids atomic diffusion is too slow, and the
\"
in homogeneity remains ''frozen in indcnniieiy.

\342\200\242
The slandard iabutatlons arc by M. Hansen, Coitsilxatlon of binary allays, McGraw-Hill. 1958;
R. P. Edioti, Constitution of binary alloys, firsi supplement, McGraw-Hill, 1965; R A. Shunfc,
Constitution of binary alloys, second supplement, McGraw-Hill, 1969. .
Figure 11.9 Phase equilibrium btiwccn liquid and solid mixtures. In
ihis example neither phase cxhibhs a solubiliSy gap. We assume
tA < x < xlt.
The upper figure (a) shows the free energies for i|ie two plxiscs;
ihc lower figure (b) shows ihc corresponding phase diagram. The curves xL
and xs in She phase diagram are called ihe liquid us and She solid us curves.
The phasediagram is She Gc-Si phase diagram, wish TCt
= 940cC and
- I412\"C
7\342\204\2425i

324
 Phase Equilibria Between Liquid and Solid Mixtm

Figure 11.10 Mosi liquid mixiuresdo not solidify at a sharp

Scmperalurc, but over a finite temperature range from t, 'o ta. The
higher-nwiliiig consiiluenl precipilaSes first, thereby enriching the
lower-mching consliSucnt in ihc liquid phase and thus lowering She
solidification lemperalure of ific liquid.

Advanced Treatment; Eutecltcs. There are many binary systems in which the
liquid phase remainsa liquid down to temperatures significantly below the
tower meltingtemperatureof the constituents. The go!d-si!icon alloy is such a
system: a mixture of 69pet An and 31 pet Si starts to solidify at 370\302\260C. At other

compositions solidification starts at a higher temperature.When we plot the

temperature oflhe onset of solidificationas a Function of alloy composition,

we obtain the two-branch liqutdus curve in Figure 11.11. Mixtures with two
liquidus branchesare calledcutectics.The minimum solidification temperature
is the eutectic SemperaSure,where She composition is She eutectic composition.
The solidifiedsolid at the eutecticcomposition is a two phase solid, wiih
nearly pure gold sideby side wiih nearly pure silicon, as in Figure 11.1.In the
solidAu-Si mixture shcre h a very wide solubility gap. The low mching point
occurs for the eutectic composision becausethe free energy oFthe homogeneous
melt is lower than the free energy of the two phase solid, for temperatures at
or above She cutectie temperature.
Such behavior is common among systems thai exhibita solubilitygap ill the
solid but not in the liquid. The behavior of eutccjj'cs can be understood from the
free energy plotsin Figure11.12a. We
assuine_/^(.\\\") for the solid as in Figure 11.6,
Chapter 11: Binary Mixtures

1600

404\302\260
1400

1200
U 1063\302\260

E 1000

/
/
\\ /

\\

0\302\260
1/
-31

0 10 20 30 40 50 60 10 80 90 100
Pure Au Atomic percent silicon Pure Si

Figure 11.11 Euieciic phase diagram of go!d-siljconalloys.The Hquidus consisisof iwo

branches ihai come iogeihcr ai ihe euieciic iempctaiure T, = 37O;C.The horizonial
line and ihe experimcnial daia poinls ai 37OX indicaie ihai ihroughoul the eniirc
composiiion range ihe mixiurc docs noi complcic iis solidificalion unlit ihe euieciic

corresponding to difTcrcnt crystal structures a and ^ for the two pure con-
constituents. Figure II.12a is constructed for a temperature above the cutectic
temperature but below the melting iemperature of cither consihuent, so that

tUe free energy of the liquid reachesbelow the common tangent to the solid
phase curves. We can draw two new two-point tangents tltat give even lower free
energies. We now distinguishfive different composition ranges:
(a) and (e). For x < xaS or x > x^, the equilibrium state of the system is a

Homogeneous solid. In the first range the solid will have the crystal structure a;
in the second range the structure is ($.
(c). For xlL < x < XpL, the equilibrium state is a homogeneousliquid.
(b) and (d). For x^ < x < xaL or x^L < x < Xp$, a liquid phase is in
equilibrium with a solid phase.
As the temperature is lowered, faS and fa decreasemorerapidly than/L,

and the range of the homogeneous liquid becomesnarrower. Figure H.12b

shows the corresponding phase diagram, including the two solidus curves.
 Figure 11.12 Free energies(a)and phase diagram (bj in a
sysiem.

At theeulecltc temperature t, Jhe free energy of Jhe liquid phase is tangential

to the common tangent to f^ and fps, as in Figure 11.13. The composition at
which fL touches the tangent is the eutcctic composition. At x < xt, the free
energy fL iies above (he tangent, although fL may be beiowthe free energy of

a homogeneous solid.
A mixture of composition equal to the eutectic composition solidifies and
meits at a single temperature,just like a pure substance. The solidification of
Chapter 11: Binary Mixtures

Figurel!.!3 FiCe energies in a euseclic system at t , andati < xr.

compositions away From the euieciic composition starls at a

higher temperature
and ends at the eutecttc temperature. Melting starts at the eulectictemperature
and ends at a higher temperature.
The minimum properly of the melting temperature of eutectics is widely
utilized. The Au-Si eutectic plays a large role in semiconductor device tech-

technology: the cutectie permits low temperature welding of electrical contact

wires madeofgoldtosilicon devices. Lead-tin alloys exhibit a euieciic (Figure
11.14) at i83\302\260C to give solder a melting temperature below that of pure tin,
232;C. According to whether a sharp melting temperature or a melting range is

desired, citlicr the exact cutectie compositionB6pet lead) or a different com-

composition is employed. Salt sprinkled on ice melts the ice because of the low
eutectic temperature -2L2\"Cof the H2O~NaC! eutecttcat 8.17moipet NaO.

The solfdus curves of eutectic systems vary greatly in character, for the
Pb-Sti system (Figure Il.M) die solid phases in equilibrium with die ioclt

contain :tn appreciable fraction of tltc minority const [merit, and this fraction
increases with decreasing temperature, in other systems this fraction may be
small or may decrease with decreasing temperature, or both. The Au-Si system
is an example: The relative concentration of Au in solid Si ill equilibrium with

an Au-Si melt reaches a ma\\imum value of only 2 x !G~6s.-ound i 300\" C, and

it drops off rapidly at lower temperature.
In our discussionof the free energy curves of Figures 31.12 and 11.13we
assumed tltat lite composition at which the liquid phasefree energy touches the
 \020 10 20 30 40 50 60 70 90 100
pure Sn Atomic percent lead pure Pb

10/tm

Figure 11.14 {a} Ptiasc diagram of the Pb-Sn s> stem, after Hatlicn.{b) Microphotngrapf;
of [he Pb-Sn eutmic, magnified about S0Otimes.Courtesy of J. D. Hunt and K. A.

Jackson.
S29
Chapter 11: Binary Mixtures

tangent to the solid phase curves lies between the compositions xlS and xfiS.
In some systems this point lies outsidethe interval, as if either/aS and/t or/flS
and fL were interchanged iti Figure i i .\\2a. Such systems arc caiied peritectic
systems.

SUMMARY

1. A mixture exhibits a solubility gap when the combinedfreeenergy of two

separate phases side by side is lowerthan the free energy of the homogeneous
mixture.
2, The mixing entropy arises when atoms of different species are interchanged
in position. For the alloy A} _IBI, we have

3. The mixing energy for nearest-neighbor interactions is

uM
=
px(l
- x)[uAB
-
j(uAA + uBB)] ,

for p nearest neighbors.

4. The Hquidus is the composition curve .xL versus t for a liquid phase in
equilibrium with a solid. The solidusis the compositioncurve Xs versus i
for a solid phase in equilibriumwith a liquid.

5. Mixtures with two branches to the liquidus curve are called eutectics. The
minimum solidification temperature is called the eutectic temperature.

PROBLEMS

L Chemicalpotentialsm two-phase equilibrium. Show that the chemical po-

[eniials ;iA and /jB of die two atomic species A and B of an equilibrium two
phase mixtureare given by the intercepts oFthe two-point tangent in Figure 11-2

with the vertical edges oFthe diagramat x =0 and x \342\200\224

1.

1. Mixing energy in 3He~*He andPb-Sn mixtures. The phasediagram oF liq-

liquid 3He-4He mixtures in Figure 11.8 shows that the solubility of 3He in 4He
remains finite (about 6 pet) as r -> 0. Similarly, the Pb-Sn phase diagram of
Figure.11.14 shows a finite residual solubility oFPb in solid Sn with decreasing
t. What do such finite residual solubilities inipty about the Form of the Function
u(.x)?
3. Segregation coefficient of impurities.Let B be an impurity to A, wish A' \302\253 1-

In this limit the non-mixing parts oF the Free energy can be expressed as linear
functions of x, as fQ(x) = /0@) + x/0'@),for both liquid and solid phases.
Assume thai the liquidmixtureis in equilibrium with the solid mixture. Calculate
the equilibrium concentration ratio k ~ xs/xL, called the segregation coefficient.

For many systems k \302\253

I, and then a substance may be purified by melting
and partial resolidificatioti, discarding a small FractionoFthe meit.Thisprinciple
is widely used in the purification of materials,as m the zone refining of semi-
semiconductors. Give a numerical value for \302\243
for/os'
\342\200\224 =
/Dt' ! eV and T = 1000K.
4. Solidification range of a binary alloy. Consider the solidificationofa binary

alloy wish the phasediagram of Figure.' 11.10.Show that, regardless of the

initial composition, the melt will always become fully depleted in component B
by the time the last remnant of the meit solidifies. That is, the sol id i Seas ion
will not be complete until the temperature has dropped to TA.
5. Alloying of gold hto silicon, (a) Suppose a 1000A layer of Au is evaporated
onto a Si crystal, and
subsequently heated to 400\302\260C- From the Au-Si phase
diagram, Figure 11.11,estimate how deep she gold will penetrate into the
silicon crystal. The densities of Au and Si are 19.3and 2.33gcm\"\023. (b) Redo

the estimate for 800\302\260C.

Chapter 12

Cryogenics

COOLING BY EXTERNAL WORK

IN AN EXPANSION ENGINE 334

Gas Liquefactionby the Joule-Thomson Effect 337
Example: Joule-Thomson Effect for van der Waals Gas 333
Liride Cycle 339
Evaporation Cooling: Pumped Helium, to 0.3 K 341
HeliumDilution Refrigerator; Miilidegrees
342

ISENTROPIC DEMAGNETIZATION:
QUEST FOR ABSOLUTE ZERO 346
NuclearDemagnetization 348
SUMMARY 350

PROBLEMS 350

1. Helium as a van der Waals Gas 359

2. Ideal Carnot Liquefier 35i
3. Claude Cycle Helium Liquefier 35!
4. Evaporation Cooling Limit 352
for
5. Initial Temperature Demagnetization Cooling 352
Cryogenics is the physics and techiioiogyofthe productionoftow temperatures.
We discuss the physical principles of the most important cooling methods,
down to the lowest temperatures.
The dominant principle oflow temperature
generation down to lOmK is the
cooling of a gas by kiting it do work against a force during an expansion. The
gas employed may gas; the free electron gas in a semicon-
be a conventional

semiconductor; or the atoms

virtual dissolvedin liquid 4He. The force
gas of 3Hc
against which work is done may be external or internal to the gas. Below
10mK the dominant cooling principle is the iscntropic demagnetizationof a
paramagnetic substance.

We discuss ihe cooling methods in the order in which they occur in a

laboratory cooling chain lhat starts by liquefying helium and proceeds from

there to the lowest laboratory temperatures,usually lOmK, sometimes 1 ;iK.

Household cooling appliances and automobile air conditioners utilize the

same evaporation cooling method that is used in the laboratory for cooling
liquid helium below its boiling temperature, to about 1 K.

COOLING BY EXTERNAL WORK

IN AN EXPANSION ENGINE

In the isentropic expansion of a monatomicidealgas from pressure pi to a

lower pressurep2, the temperaturedropsaccording to

(i)

by F.64). Suppose p, = 32atm; p2 = iatm; and Ti = 300K; then the tem-

temperature will drop to T; \342\200\224
75 K. We are chiefly interested in helium as the
working gas, and for helium A) is an excellentapproximation if the cooling

process is reversible.
The problems in implementingexpansioncoolingarise from the partial

irreversibility of actual expansion processes.The problems are compounded

by the nonexistence of good low temperature lubricants. Actual expansion

cooling cycles follow Figure 12.1.The compression and expansion parts of
 itisng by External Work in on {Expansion Ens

Heal ejection

Expansion
ngine

Working\342\200\224

volume

FEgure I2.ISimple expansion refrtgeraior.A working gas ts

compressed; the heat of is
compression ejected into the
environment. The compressed room temperature gas is

precooled further in the counleriiow heat exchanger. It then

does work in an expansion engine, where it cools to a

temperature below that of the working volume. Afkr extracting

hea{ from the working volume, the gas returns to the compressor
via {he heat exchanger.
Chapter 12: Cryogenics

the cycle arc separated.The compressionis performed at or above room

temperature. The hot compressedgas is cooled to near room temperature
by ejecting heat into the environment. The gasis further precooled in a counter-
flow heat exchanger by contact with return
the gas stream at the low
cold

temperatureof the
cooling load. The cooled to itslowesttemperature
gas is then
in the expansion engine, usually a low friction turbine.The cold gas extracts
heat from the cooling load and then returns to the compressor via the heat
exchanger. The heat exchanger greatly reduces the cooling requirements im-
imposed on the expansion engine. The design of Sheheat exchangeris as important

as the design of the expansion engine.

The work extracted by the expansion engine is the enthalpy difference

between the input and output gas: The iota!energy flowing into the expansion
engine is the iruernat energy U^ of the gas plus the displacement work p{Vl
done the by compressor, where boih fij and Vx refer to a given mass of gas.
The total energy leaving She engine with is the energy
the gas U2 of the gas
plus the work p2 V% required to move the gas against the pressurep2- The work
extracted by ihe engine is the difference

W =
{Ul 4- PlVt) - {Uz + PlV1)
=
Hs
~~
H2. B)

For a monatomic ideal gas U j= |Nr and pV = Nr, hence H = \\Nx. The

work performed on the engine by the gas is

\302\273 - C)
W
|N{t, r2).

The countefHowheat exchangeris an enthalpy exchange device: it is an

expansion engine which extractsno externalwork.

Most gas Hquefiers use expansion engines to prccool the gas closeto its
liquefaction temperature. It is impractical to carry She expansion cooling to
of
the point liquefaction: the formation of a liquid phase inside expansion
enginescauses mechanical operating difficulties. The final liquefaction stage
is usually a Joule-Thomson stage, discussed below. Helium and hydrogen
liquefiers usually eontain two or more expansion engines at successive tem-
temperatures, with multiple heat exchangers.
The principle of cooling by isentropic expansion of an ideal gas is applicable
to the electron gas in semiconductors. When electrons How from a semi-

semiconductor wuh high electron concentration into a semiconductor with a lower

electron concentration, the electron gas expands and does work against
she

potential barrier between the two substances that equalizesthe two chemical
potentials. The resulting electronic cooling, called the Peltiereffect, is used
 Gas Liquefaction by the Joule-Thomson Effect

down to about 195 K quite routinely;in multistage units temperatures down

So 135K hnvc been achieved.

Gas Liquefaction by the Joule-Thomson Effect

Intcrinolccular attractive interactionscausethe condensation of al! gases. At
icmpcratures slightly above the condensation temperature the interactions are
strong enough that work against them during expansion causes significant
cooling of the gas. If the coolingis sufficient, part of the gas will condense.
This process is Joule-Thomsonliquefaction.
The practical implementation is simple. Gas at pressure p, is forcedthrough
a constriction called an expansion valve into space with a lower pressure p2,
as in Figure 12.2.The work is {he difference between the displacement work
~plt(Vj doneon the gas in pushing it through {he expansion valve and the

displacement work +p2(\"/2 recovered from the gas on the downstreamside.

Here dVt is negative and dV2 is positive.
The overall processis at constant enthalpy. To sec this, notice that the
expansion valve acts as an expansion engine that extracts zero work. With
If = 0 in
B), we have H\\ ~ li2 in the Joule-Thomson effect. For an ideal gas
11 \342\204\242
\\Nr, so that ts \342\200\224in
r2 the expansion. There is zero coolingeffect for an

ideal gas.
gases a small temperaturechange
in real occurs because of the internal
work done by the molecules duriiig expansion. The sign of the temperature

Expansion
valve

Figure |2,2 The Joule-Thomson eflccl.A gas is pushed

through an expansion value. If the gas is notlflieal. ihere will

be a temperature change during the expansion because of work
done against the intermolecuhtr forces. temperature is
If the
initially below a certain inversion temperature, riB,, the gas
will cool on Joule-Thomson expansion-
Chapter 12: Cry

Table U.I Liquefaclion dala for lo

n. Tt, T,,., AH, V,.

(jas K K K U/mol em'/mol wall Mite

CO, 195 304 B050) 25.2 223 314

cm 112 191 A290) 8.18 34.4 66
o, 902 155 893 6.82 28.1 67
N, 77.3 126 621 5.57 34.6 45
H, 20.4 33.3 205 0.90 28.6 8.7
\342\200\242He 4.SS 5.25 51 0-082 320 0.7!
JHe 3.20 3.35 B3) 0.025 50.8 0.14

the liquid. The las umn, Atl/V, tndkai n walls thai can be la'ken up for

Jrti T( ano\" oot measured '

Carbon dioxide solidifies mosphcric pressure. because its lrjple poinl c

of natural gas, which is liquefied in huge quamilics for shipping us LNG fuel. Liquid
and niirogen are separaied iu lhe liquefaction of air. For helium, we give daia boih for ihe
ei isotope 4Hc and for 3He.

change during a Joule-Thomsonexpansion depends on the initial temperature.

All gases have an inversiontemperature TIn, below which such an expansion
cools, above which it heals (he gas. inversion temperatures for common gases
are listed in Table 12.1.

Example: Joule-Thomson effect for ran far li'aab gas. We found in A0.75) that

H \302\253=
JWt + {S2fV){bx
- 2a) D)
for a van der Waais gas, where a and b are positive constants. The last two terms arc the
corrections caused by the short range repulsion and the long range atiraction. The correc-
corrections have opposite signs. The tola! correciion changes sign at the temperature

tinv
== lab = 2/rt, E)

where xc is the critical tempera!urc, defined by A0.46).

The temperature For t < iin, the enthalpy
iln, is the inversion lemperature. at fixed
temperature increasesas the volume increases; here in expansion the work done against the
attraciive interactions between molecules is dominani. In a process at consiant enihafpy
this increase is compensated by a decrease of the \\Nt ierm, that is, by cooling the gas. For
 Gas Liquefactionby the Joutc-Thot

i a fixed lemperamre s because now the work done by the

anl: ai lhc higher lempcraluie the
ioIccuIcspenetrate farther inio lhe repulsive regio

Linde cycle. litjueficrs the Joule-Thomsonexpansioniscombined

In gas wilh

a counlerflow heat exchanger, as shown in Figure J2.3.The combination is

called a Lindc cycle, aficr Carl von Linde who used such a cycle in 1895 to

liquefy air starting from room temperature.In our discussion we assume that

the expanded gas returning from the heat exchanger is at ihe same temperature
as the compressed gas entering it. We neglect any pressure differencebetween
the output of the heat exchanger and the pressure above the liquid.

To and from comprcs

Figure 12.3 The Lindecycle.Gas

by combining Joule-Thomson expa
a countcrflow Iieatexchanger.

JT expansionvaJv.

Liquefied gas
Figure 12.4 Performance of helium litjueficrs operating by the Liude cycle,
as a fund ion ofihe inpui pressure, for an ouiput pressure of 1 aim and
for various values of ihc input temperature. The solid curvesgive ihe

liquefaciion coefficient The broken cunes give QiM

=
tfDUl
-
Hia, ihe
inierna! refrigeration load available at 4.2 K if (he toad is placed inside ihe
ii^uciicrand ihc still coid helium gas boiledoff by lhc load is relumed
through ihe heal exchanger rather than boiled oiT into liie atmosphere.
See Problem 3. Afier A. J. Croft in A&mWL-dcryo&mcs (C. A. Baiiey, ed.),
Plenum, 1971. p. 1S7.
 Evaporation Coaling; PumpedHelium, to 0.3 K

The comhimtiion hc;\302\273

exchanger-expansion valve is ;i consimu enthalpy
arrangement. Let one moleof gas enter Hie combination; suppose ihat the
fraction X is liquefied. Constant cniluilpy requires lhat

= + -
//;\342\200\236 -IWii, \302\243! J)H9Ui' \302\2436}

Here Hla
=
H(TiMp-a) and llou, = H(Tin.pBJare the enlhalpies per mo!c of
gas at lhe input and output pressures, both at lhe common upper temperature
of the heat exchanger- tfHl) is lhe enthalpy per moleof liquid at its boiling lcm-
peraturc under lhe pressurepoal. From F) we obtain the fraction

17)

called the
liquefaction coefficient.

Liquefaction lakes place when > Hia;

//\342\200\236\342\200\236, thai is, when

HiT^J > H{Tia,p-J. (8)

Only the enthalpies at the input lemperalure of lhe heat exchangermaHer. If

the Joule-Thomson expansion at this temperature cools the gas, liquefaction

will take place.
The three enthalpiesin G) are known experimentally. Figure 12.4 shows lhe
liquefaction coefficient calculated from them Tor helium. The liquefaction
coefficientdrops rapidly with increasing Tiat because of the decrease of the
numerator in G) denominator. To obtain useful lique-
and the increase of the
liquefaction, say ;. > 0.!, input temperatures below one-thirdof the inversion

temperature are usually required. For many gases this requires precedingof
the gas by an expansion engine. The combination of an expansionengine and

a Linde cycle is called a Claude cycle. The expansion engine is invariably

preceded by another heat excitauger, as in Figure 12.1-

Evaporatfon Coofing: Pumped Helium, lo 0.3 K

simplest route lo lower temperaturesis
f
Starting from liquid helium, the y
'
evaporation cooling of !hc liquid
helium, by pumping away lieiium vapor, j

latent heat of vaporization of the liquid Iteltum is extracted along with the vap,-..
The heat extractioncauses ihc further cooling: work is done against the inter-
:itonu'c forces that cnuscJ ihc helium io liquefy in the first pi;>ce. hi JouL-

Tltomson cooling tlte initial staie is a gas, while in evaporation cooling the

initial state is a liquid.

Chapter 17: Cryogenics

Table 12.2 Tempera turds, in kctvifi.at which 1 he vapor pressures of 4He and
3Hc reach specified values

p(lorr)

0.66 0.79 0.98 1.27 1.74 2.64

0.28 0.36 0.47 0.66 1.03 1-79

The lowest tempcralure accessible by evaporation liquid helium

cooling of
isa problem in vacuum technology (Chapter 14). As the ternperalure drops,the
equilibrium vapor pressure drops (Table 12.2} and so docsthe raie ai which
helium gas and its heat ofvaporization can be extracted from the liquid helium
bath.
Evaporation cooling ts the dominant cooling principle in everyday cooling
devices household refrigerators and freezersant! in
such a5 ait conditioners.
The only difference is in the workingsubstance.

Helium Dilution Refrigerator: Militdegrees

Once the equilibriumvapor pressure of liquid 3He has dropped to I0\023 torr,

classical refrigeration principles lose their utility. The temperaiure

range from

0.6 K io 0.0! K. is dominated by the helium dilution refrigerator, which is an

evaporation refrigeratorin a very clever quantum disguise.*
We saw in Chapter 7 that *He atoms 3He atoms are fer-
are bosons, while
mions. This distinction is not important at temperatures appreciably higher
than the superfluid transition temperature of \"fie, 2.17 K. However,the two
isotopes behave as altogether different substances at lowertemperatures. Below

0.87 K. liquid 3He and 4He are immiscibleovera wide composition range, like
oil and water. This was discussed in Chapter 11 and is shown in the phase
diagram of 3He-4He mixtures in Figure 11.7. A mixture with composition in

the range labeled unstable wil! decomposeinto two

separate phases whose

compositions are given by the two brandies of the curve enclosing that area.

The concentrated 3He phase floats on top of the dilute 3He phase.

As T -\302\273
0, the 3He concentration of the phase dilute in 3He drops to about
6 pet, and the phaserich in 3He becomes essentially pure 3He. Consider a liquid

*
For good reviews, sec D. S. Belts.Contemporary Physics 9.97 {1968): IC. Wheatley. Am-1 Phys.
36, 181A968);for a general review or cooling techniques below 1 K see W. J. Huiskamp and O. V.
Lounasmaa, Repts. Prog, Phys. 36, 423 A973); O. V. Lounasmaa, Experimental principles and
methodsbelow t K, AcademicPress,Hew York, 1974. A very elementary accoun! Is O. V. Lounasmaa,
Scientific American 221,26 (t%9). . \342\226\240
.
 Figure 12.5 Cooling principle of ilm helium dilution refrigerator. Liquid
Hlc is in equilibrium wiih a JHc-4He nmiure. When 4He is added io the
mixiure, sHe evaporaics from ihc pure ]He fluid and absorbs heat in ihc

3He-4He mixture wiih more than 6 pet 3Hea* a temperature in the millidcgree
range, near the bottomof Figure11.7.At these temperatures almost all the 4He
atoms have condensedinto the ground stateTheir entropy is negligible
orbital.
comparedto that of the remaining which then behave as if they were
3He atoms,
present alone, as a gas occupying the volutne of the mixture. If the 3He concen-
concentration exceeds 6pct, the excess condenses into concentrated liquid 3He and
latent heat is liberated. If concentrated liquid 3He is evaporatedimo the 4He
rich phase, the latent heat is consumed.The principle of evaporation cooling
can again be applied: this is the basts of the heliumdilution refrigerator.

To see how the solution of 3He can be employed to obtain refrigeration,

consider the equilibrium between the concentrated3Heliquidphase and the

dilute gas-like plliise (Figure 12.5).Suppose

iHc lliai tile JHc:4lic nilio of
the dilute phase is decreased,as by dilution with pure *He. In order to restore
the equilibrium concentration, 3He aiomswil! evaporate from the concentrated
3He liquid.Coolingwill result.

To obtain a cyclic process the 3He-4He mixturemust be separated again.

Tile most common method is by distillation, using tile different equilibrium
vapor pressures of 3He and *Hc (Table 12.2). Figure 12.6 shows a schematic
diagram of a refrigerator built on these principles. The diagram is highly

oversimplified. In particular, in actual refrigerators titehcat exchangerbetween

the mixing chamber and the still has an elaborate multistagedesign. An alternate

method* to separate the. 3He--4He mixture utilizes tile superfluidity of 4He

below 2.17 K. For a variety, of practical reasons it is less commonly used,

.
although Us performance is excellent. \342\226\240
.
Chapter 12: Cryogenics

3He pump loop

Key:
Liquid
\342\226\240
I 'lie
 Helium Dilution Refrigerator: AtitliJegre

Figure Hdium dliulion refrigerator. Prccooledliquid

12.6 3He enters a mixing
chamber a( (he tower cud of the assembly, wlicrc cooling takes place by ihe quasi-
cvaporaiion of the 3He atoms into the denser JHc-Jf1cmixed phase underneath.
The quast-gas of JH atoms dissolvedin liquid *He then diffuses through a countcrfiow

heat exchanger into 3 still. There the JHe is disiilledfrom the 3Hc-4Hc mixture
selectively, and is pumped olf.To obtain a useful 3He evaporation and circulation
rate, heat must be added to the still, 10 raiseUs temperature to about 0.7 K, at which
temperature vapor pressure is ssiH much smaller. Thus, the 4He does not
the *He
circulate appreciable extent; ihe *Hc moves
lo any riirough a nearly stationary
background of 4Hc.The pumped-off JHe is returned to ihe system and is condensed
in a condenser that is cooled to about I K by contact with a pumped 4He bath. The
constriction below the condenser takes up the excess pressuregenerated by the
circulation pump over ihe pressure in the still. The liquified JHe is cooled further,
first in rhe siill. ihcn in the counter/low heat exchanger, beforere-entering tlic miung

chamber.

The helium dilution refrigerator has a low temperaturelitnft. In the conven-

conventional evaporaiioii refrigerator this limit arose because of the disappearance of

the
gas phase, but the quasi-gas phase of 3Hepersists down to t = 0, However,

ihe heat of quasi-vaporizationof JHe vanishes proportionally to x2, and as a

result, Ihe heat removal rate from the mixing chamber vanishes as i1. TI'S
practical
low temperature limit is about 10 mK, In one representative device;*

a temperature of 8.3 mK has been achieved:ihe same device was capable of

removing 40/AVat 80mK.
Temperatures
below SmK can be ncltievcu by single shot operation. If, in

ihe design of Figure I 2.6, we shut off the 3He supplyafter some time of opeiation,
there is no needto cooi the incoming 3He itself, and ihe temperature of the
mixingchamberdrops below its sleady state value, until all 3He has been
removed from the chamber.

The dilution refrigerator is not the oniy cooiingmethodin the inillikelvin

range the peculiar propertiesof JHe.An alternate

that utilizes method, known
as Pomcranchsik cooling, utilizes the phasediagramof 3He,as shown in Fig-

Figure 7.15, with its negative slope of the phase boundary between liquid and

solid 3He, The interested reader is referredto the reviews by Huiskamp ant!

Lounasmaa, and by Lounastnaa, citedearlier.

' N. H. Pcnnings, R. de Bruyn Ouboicr, K. \\V. Tacoois. Phjiica 8 SI. !0! A976). and Physiea B
84, 102A976}.
ISENTROPIC DEMAGNETIZATION:
QUEST FOR ABSOLUTEZERO
Below 0.01 K the doniimim cooling process is the isciitropic(adiabaiic) dcm;ig-
iictizatioii of a paramagnetic substance. By this process, temperaturesof I niK
have been attained with electronic paramagnetic systems and j /(K with nuclear
paramagnetic systems. The method dependson tlie fact that at a fixed tempera-
temperaturethe entropy of a system of magnetic momentsisloweredby application of a

magnetic field\342\200\224essentially because fewer slates are accessible to the system

when ilic level splitting is large than when the level splitting is small. Examples
of the dependence of the entropy on tlie magnetic field were given in Chapters 2

and 3.
We first apply a magnetic field Bt at constant temperature ij. The spin excess
will attain a value appropriate to the value of Bj/tj. If the magnetic field is then
reducedto B2 without changing the entropy of the spin system,the spin excess
will remain unchanged, which means that B2/z2 will equa' #i/ri- HBz \302\253
Bi,

then t2 When
<\342\226\240<
tj- the specimen is demagnetized isentropically,entropy can

flow into the spin system only from the system of lattice vibrations, as in Fig-
Figure 12.7- At entropy of the
the temperatures of interest the lattice vibrations is

usually negligible; thus the entropy ofthe spin system will be essentially constant
during isentropie demagnetization of the specimen.

\\Latttce

w Total 1
Spin
Lattice Time\342\200\224- Time\342\200\224\342\200\242

Before New equilibrium Before New equilibr:

Time at which Time at which
magnetic field magnetic field
is removed js removed

Figure 12.7 During demagnetization the total entropy of the S

isentropie
specimen is constant. The of the lattice should be small
initial
entropy in

comparison with the entropy of the spin system in order to obtain significant
cooling of the lattice. - - .
 lsentropic Demagnetization: Quest for Absolute Zer

Figure Entropy fora spin \\ sysiem

12.8 as a function of Icmpcralure.assum
an inicrna! random
magnetic field Bx of 100 gauss. The specimenis magnetiz
isothermaiiy along ah, and is then insulated ihcrmaMy. Thu cxlcrna! ntagnctit
field is 1 timed off along/>c. Ill order to keep the figure on a reasonable sculc
llic initial temperature Tj and tlie external magnetic field are lower than woi
used in practice.

The steps carried out in the cooling processarc shown in Figure 12.8. The
field is applied at temperaturetx with the specimen in good thermal contact
with the surroundings, giving the isothermal path ab. The specimenis ihen
insulated {At? ~ 0) and the field removed; the specimenfollows the constant

entropy 6c, ending up at temperature t2. The thermal

path contact ai t, is
provided by helium gas, and the thermal contact is broken by removing the
gas with a pump.

The population of a magnetic subievelis a function only of ntB/x, where m

is the magnetic momentof a spin. The spin-system entropy is a function only

ofthe population distribution; hence the spin entropy is a function only oimBjx.
If SA is theeffeclive field that corresponds to thediverse localinteractions among

the spins or ofthe spins with the lattice, the final temperature r2 reached in an
isenlropic demagnetization experimentis

(9}

where B rt the initial temperature.Results

is the initial field and are shown in

Figure IZ9 for the paramagnetic salt known as CMN, which denotes cerous
magnesium nitrate, . .
 0 0.1 0.2 0.3 0.4 0.5 0.6

Final temperature, in K

Figure 12.9 Final magaclic field Bf versus final

nil rale. In fhese experiments ihe magnetic field was not

removed cniirciy, bul only m tfic indicated values. The
iiiiiial fields and icmpcraiurcs were idcnliait in all inns.
After unpublished results 61\" J. S. Still and J. H. Milncr.
as cilcd 6,
by N, Kuril, Kuovo Cimcnio (Supplement)
1109A957).

The processdescribedso far is a single shot process. It is easily converted

into a cyclicprocess thermally by disconnecting, in one way or another, the

demagnetized working substance from the load, reconnecting

it to the reservoir
at t,, and repeating the process.*

Nuclear Dcmagnelizalion

Because nuclear magnetic moments arc weak, nuclear magneticinteractions

are much weaker lhan similar electronic interactions. We expect to reach a

temperature 100 limes lower with a nuclear paramagnet lhan with an electron

paramagnet. The initial temperature of the nuclearstage in a nuclear spin-

\342\200\242
C. V. Hctr. C. B. Barnes,and J. G. Daunt. Rev. Scj, insi. 25. IGS8 j|954); W. p. PraH, S. S.
Rosenblum, W. A. Slcyerl. and i. A. Barclay. OHgcnics 17, 3S! A977).
 t\\'uc!ear Demagnetization

Iniiial magnetic Held in KG

0.6 1

Initial B/T'm \\QS G/K

Figure Nuclear demagnctizaflons of copper

I2J0
nuclei in skirting from 0.012 K and various
the metal,
fields. After M. V. Hobdcn imd N. Kuril. Phil. Mag.
-1.1902!1959).

cooling must be lower

experimen! than in an electron spin-cooling experiment.
=
lfwestartatB SOkGandT, 0.01 = K,then/fiB/*87\\
* 0.5, and the entropy

decrease on magnetizationis 10 percent over of the maximum spin entropy.

This is sufficient to overwhelm ihe lattice and from (9) we estimate a final

temperature T2 ss 10\027K.The first nuclear cooling experiment was carried

oui by Kurli and coworkers on Cu nuclei in the metal, starting from a first

stage at about 0.02 K as attained by electron demagneltzallon cooling. The

lowest temperature reached in this experimen!was 1.2 I0~6K. x The results
in Figure 12-10fil a line of Ihe form of (9): 7\\ = T|C.1/B) wilh Bin ^auss, so
llial =
B\302\261 3.1 gauss. This is the ciTcctive interaction field of the magnetic mo-
moments of the Cu nueiei. The motivation for using nuclei in a metal rather than
in an insulatoris that conduction electrons help ensure rapid thermal contact
of lattice and nuclei at the temperature of the first stage.

Temperatures below 1//K have been achieved in experiments in which the

cooling load was the system of nuclearspinsitself, particulatly in experiments

that were combinations of cooling experimentsand nuclear magnetic resonance

experiments.*

SUMMARY

1. The two dominant principles of the production of low temperaturesarc ihe

cooling of a gas by letting it do work against a force during an expansion
of a
and the iscntropicdcmagncii/atioii paramagnetic substance.

2. Joule-Thomson cooling is an irreversible process in which work is done

against interatomic attractive forces in a gas. It is used as the last cooling
stage in liquefying low-boiling gases.

3. In evaporation cooling the work is also doneagainst the interatomic forces,

but starting from the liquid phaserather than the gas phase. Using different
working substances, evaporation coolingforms the basis of household
cooling devices, automobile air conditioners,
and laboratory cooling devices
(in the range 4 K down to SGmK).
4. The helium dilution refrigerator is an evaporation cooling device in which

the gas is the virtual gas of 3He atomsdissolvedin 4He.

5. Isentropic demagnetization utilizes the lowering of the temperature of a

system of magnetic moments, when an external magnetic field is reduced in

strength. The magnetic moments may be electronic or nuclearmoments.

By using nuclear moments, temperatures in the microkelvin range may be

achieved.

PROBLEMS

L Helium as a van der H'aafcgas. (a) Estimate tlte liquefaction coefficient X

for helium by treating it as a van der Waals gas. Select the van der Waals
coefficientsa and 6 in such a way that Tor one mole 2Nb is the actual molar
volume of liquid helium and that 2a/b is the actual inversion temperature.
Use the data in Table 12.!. Approximate the denominator in G) by setting

Hout
- Hi(q
- AH 4- f(rin - , A0)
xliH)

for
\342\200\242See, example, M. Chapcllier, M. Goldman, V. H. Chau and A. Abragara, Appl. Phys-41,
849A970). . -.-._...\342\226\240
where All is the latent heat of vaporizationof liquid helium. (Explain how this
approximation arises if one treats the expanded gas as an ideal gas). The
resulting expression gives /. as a function of the molar volumes Yin and Vatll.
Convert to pressures by approximating the l\"s via the ideal gas law. (b) Inaert
numerical values for T = 15 K and compare with Figure 12.4.

2. IdealCarnot liquefier. (a) Calculatethe work \\VL thai would be required to

liquefy mole
one of a monstomic ideal gas if the iiqticfier operated rcversibiy.
Assume that the gas is suppliedat roomtemperature To. and under the same
pressure p0 at whidi the liquefied gas is removed, typically 1 atmosphere. Let

7\\ be the boiling temperature of the gas at this pressure, and A// the latent heat
of vaporization.Show that under these conditions

A1)

To derive A1) assumethat the gas is first cooled at fixed pressure p6 from To
to Tfc, by means of a reversible refrigeratorthat operates between the fixed
upper temperature Tb ~ To attd a variable lower temperatureequalto the gas
temperature. Initially T, = To, and at the end T,
~ 1\\.After reaching Tb the
refrigerator extracts the latent heat of vaporization at the fixed lower tempera-
temperature Tb. (b) Insert To = 300 K and values for Tb and AH characteristic of
helium. Re-express the result as kilowatt-hours per liter of liquid helium.
Actua! helium liquefiersconsume5 to lOkWh. liter.

3. Claude cycle helium Hqucfier. Considera heliumliquefier in which 1 mols\021

of gas enters the Lrnde stage at T(o = 15 K and at a pressure pla = 30 aim.
(a) Calculate the rate of liquefaction, in liter hr\"'. Suppose that all the liquefied
helium is withdrawn to cool an externalexperimental apparatus, releasing the
boiled-off helium vapor into the atmosphere. Calculate the cooling load in
watts sufficient to evaporate the heliumat the rate it is liquefied. Compare this
with the cooling load obtainable if the liquefier is operated as a closed-cycle
refrigerator by placing the apparatus into the liquid collectionvesselof the
liquefier, so lhat the still cold boiled-off helium gas is returnedthrough the heat

exchangers, (b) Assume that the heat exchangerbetween compressor and ex-

expansion engine (Figure 12.1) is sufficiently ideal that the expanded return gas
that leaves it with pressure pout is at essentially the same temperature Tc as the
compressedgasenteringit with pressure pc. Show that under ordinary liquefier
operationthe expansion engine must extract the work

Te - TJ , A2)
Chapter 12: Cryogenics

per mole of compressed gas. HereTin, pin, pBUt, and X have the same meaning
as in ihe Undo cycle sectionof this chapier. Assume the expansion engine
operates isemropically between ihe pressure-temperature pairs {pc,Tc) and

(Pia>Ti(l). From A2) and the given values of (pia,Tia),calculate(pc,Te). (c) Estimate

the minimum compressor power required to operate the iiquefier,by assuming

that the compression is isothermal from poai to pc at temperature Tc ~ 50\"C.
Combinethe result with {hecooling loads calculated under (a) into a coefficient
of refrigerator performance, for both modes of operation. Compare with the

Carnot iimit.

4. Evaporation cooling limit. Estimate the lowest temperatureTmia that can

be achieved by evaporation cooling of liquid 4He if the cooling load is 0.1 W
and the vacuum pump has a pump speed S = I02filers\021. Assume (hat the
helium vapor pressure above the boiling helium is equal to the equilibrium
vapor pressurecorresponding lo TBliJ1, and assume that ilic helium gas warms
tip to roorn temperature and expands accordingly before it enters the ptunp.
Nota: Tlte molar volume of an ideul gas at room icmpcramrc and atmospheric
pressure G60torr) is about 24 liters. Repeat the calculation for a mtjch smaller
heat load (I0~3 W) and a faster puinpA0J liter s\"\021). Puntp speed is defined in

Chapter 14.

5. Initial temperature far demagnetizationcoaling, Considera paramagnetic

salt with a Dcbyc temperature {Chapter 4) of 100K. A magnetic field ofiOOkG
or lOtcsia is available in the laboratory. Estiniate the temperature to which the
salt must be prccoolcd by other means in order that significant magnetic cooling
may subsequently be obtained by !he isentropic demagnetization process. Take
the magnetic momentofa paramagnetic ion to be I Bohr magneton. By signifi-
significant
cooling we may understand cooling to 0.1 of the initial temperature.
Chapter 13

Semiconductor Statistics

ENERGY BANDS; FERMI LEVEL;

ELECTRONS AND HOLES 355
ClassicalRegime 358
Law of Mass Action 362
intrinsic Fermi Level 362
363
/r-TVPE AND P'TYVE SEMICONDUCTORS

Donors and Acceptors 363

Fermi Level in Extrinsic Semiconductors 364
Degenerate Semiconductors 365
Impunly Levels 368
Occupationof Donor Levels 369

Example: Semi-Insulating Gallium Arsenide 372

p-n JUNCTIONS 373

Reverse-Biased Abrupt p-n Junction 377

NONEQUIUBRIUM SEMICONDUCrORS 379

Quasi-Fermi Levels 379

Current Flow: Drift and Diffusion 379

Example:Injection Laser 381

Example: Carrier Recombination Through an Impurity Level 383

SUMMARY 385

PROBLEMS 387

1. Weakly Doped .Semiconductor 387

2. Intrinsic Conductivity and Minimum Conductivity 387
3. Resistivity and Impurity Concemraiiou 387
4. Mass Action Law for High Electron Concentrations 387
5. Electron and Hole Concentrations in InSb 387
6. Incomplete lonizationof Deep Impurities 3S7

7. Built-in Field for Exponential Doping Profile 388

8. Einstein Relation for High Electron Concentrations 388
Chapter 13: Semiconductor Statistics

9. Injection Laser 388

10. Minority Carrier Lifetime 38S
11. Electron-Hole Pair Generation 388

iiiiiiui^zny conduct
v\302\273'ilti [tin xind valence b jfiu\302\243
\\ elects oeis snd hoics^ donors *inu 3cccplovs. I he

Ha
^ conccnlration of holes ^

ht
= cffcciivc conccnlnU/on for condudion ctccirons;
c^uantiiEn

= effective coiKcntralion holes.

n, quamum for

In the semieonductoi tileralurc n,. and % ate called ihe effective densities of states for the conduction
and valence bands. Notice iKal we use ;i fo( tin; chemical potential or Fcimi level, and we use Ji foi
cai-iicr mobilities.
ENERGY BANDS; FERMI LEVEL;
ELECTRONS AND HOLES

The application of the Fermi-Dirac disiributionto eiecironsin semiconductors

is central to the design and operation of all semiconductor devices, and thus
to much of modern electronics.We treat below those aspects of the physics
of semiconductorsand semiconductor devices that are parts of thermal physics.
We assume that theis familiar wjlh the basic
reader ideas of the physics of
eleclrons in
crysialline soiids, as treated 'n the texts on solidslatephysics
and on semiconductor devices cited in the general references. We assume the
of
concept energy bands and of conduction by electrons and hotcs. Our principal
aim is to understand the dependence of the alt-important concentrations of
conduction electronsand of holesupon the impurity concentration and the
temperature.
A semiconductor is a system with electron orbitats grouped into two energy
bands separatedby energy gap (Figure 13.1). The lower band is the valence
an

band and the upper band is the conductionband.* In a pure semiconducior at

t = 0 al! valence band orbitats are occupied and alt conduction band orbitals
are empty. A full band cannot carry any current, so that a pure semiconductor
at r = 0 is an insulator.Finite conductivity in a semiconductor follows either
from the presence of electrons,catled conduction electrons, in the conduction
band or from unoccupied orbitats in the valence band, called notes.
Two different mechanisms give rise to conduction electrons and holes:
Thermalexcitation of electrons from the vatencc band to the conduction band,
or the presence of impurities that change the balance between the number
of orbitats in the valence band and the number of electrons available to fill them.
We denote the energy of the top of the valence band and
by \302\243,., the energy

of the bottom of the conductionband by e{. The differed rence

is the energygap of the semiconductor.Fortypical semiconductors Eg

is between

0.1 and 2.5 electronvolts.In silicon,e, ^ 1.1 eV. Because t ^ 1/40 eV at room

\342\200\242
We tieai both bands as single bands; for out (imposes it does noi mailer thai boih may be groups

of bands wtih additional gaps wiihtn each gioup.

Chapter 13: Semiconductor Statistics

Conduction band
Empiy
atr =0

Energy gap

Filled
air =0

Figure t3.1 Energy band structure of a puic semiconductor or insulator.

The electron orbilajs occur in bandsthrough the crystal.
\\vhjch exlerid
Air = Gallorbitaisuplothe top of the valence band are filled,and ihe
conduct ion bantl is empty. The energy interval between the bands is called
the energy gap.

temperature, we usually
havec,, \302\273t. Substances with a gap of more than about

2.5 eV are usually insulators. Table 13.1 gives the energy gaps for selected
semiconductors, together with other properties needed later.
Let nt denote ihe concentration of conduction electrons and nh
the con-

concentration of holes. In a pure semiconductorthe two wiH be equal:

ii, = \302\253*. B)

crystal is electrically neutral.

if the

Most semiconductorsas usedn\\ devices have been inteniionaiiy doped with

impurities that may become thermally ionized In the semiconductor at room
\342\226\240temperature. Impurities tiiat give an electron to the crystal (and become

positively charged in the process) are called donors.Impurities that accept

 Energy Bands; Fermi Lml; Elec

Table 13.1 Band structure data

Dcnslty- f-statcs Dielectric

Energy Q antun i concentr itions effective masses, constants

|
gaps at c Idea ions and li olcs in units of the relative to
300 K 1300K free cicctr on mass vacuum
\",. in/ftn ilia
eV c c

Si t.[4 2.7 x 10 ' 1.1 x 10\" 1.06 0.58 11.7

Cc 0.67 1.0 x !O 9 5-2 x to'a 0.56 0.35 15.8
GaAs 1.43 4.6 x 10 ' 1.5 x 10\" 0.07 0.71 13.13
,,p 1.35 4.9 x 10 ' 6.9 x 10'* 0.073 0.42 12.37
InSb 0.18 4.6 X 10 ' 6.2x 10\" 0.015 0.39 17.S8

an electron from the valence band (and become negatively charged in the

process) are called acceptors.

Let \302\253j+be !he concentration of positively charged donors and na~ the

concentration of negatively charged acceptors. The difference

An
=
/[/
- na~ C)

ts called the net ionized donor concentration.The electrical

neutrality
condition

becomes

= = \342\200\224
An Hj* no~~t D)

which specifies the difference betweenelectronand hole concentrations.

The electron concentration may be calculated from the Fermi-Diracdis-
distribution function of Chapter 6:

E)
exp[(e - /

where [i is the chemical potentialof the electrons. The subscript e refers to

electrons. In semiconductor theory the electron chemical potential is always
called the Fermilevel. Further, in semiconductor theory the character fi is

almost always reserved for ihe electron and hole mobilities,and the Fermi

level is designated by ef or by
To
\302\243. avoid confusion with the Fermi energy
of a meia! which we designated as cf and which stands for tile Fermi level

in ihe limil r -* 0, we shall maintain our previous usage of the letter /j for the
chemicalpotential at any temperature.
 Given ;i and t, the number of conductionelectronsis obtained by summing
the distribution function /,(e) over all conduction band orbitals:

The number of holes is

*\\ = [l
\302\243
- /.(*)] = I ftU). V)
VB VI!

where the summation is overall valenceband orbitals. Here we have introduced

the quantity

which is the
probability that an orbital at energy e is unoccupied.We say
that the unoccupied orbital is \"occupiedby a hole\"; [hen/h(e) is the distribution
function for holes just as f\302\243t) is the distribution function for electrons. Com-
Comparison of (8) with E) shows that the hole occupation probability involves

y.
y.
\342\200\224
e where the electron occupation probability involves c - p.
The concentrations nt
=
NJV and nh =
NJV depend on the Ferm't level.
But what is the value of the Fermi level? It ts determined by the electrical

neutrality requirement D), now written as nt{y)

\342\200\224
nh{y)
= An. This is an

implicit equation y.; for to solve the equation we must determine the functional

dependences ne{y) and nh{y}.

Classical Regime
We assume that both electron and hole concentrations are in the classical

regime defined by the requirements that fr 1

\302\253 and fh \302\253
I, as in Chapter 6.
This will be true if, as in Figure 13.2, the Fermi level lies insidethe energy gap
and ts separated from both band edgesby energies large enough that

- -
exp[-(\302\243c /i)/t] \302\253
1; exp[-0* ej/t] 1.
\302\253 (9)

To satisfy (9) both \342\200\224

and - have to be positive and al least a
(gc n) (/t eu)

few times larger than t. Such a semiconductor is callednondegenerate.The

inequalities (9) place upper limits on the electron and hole concentrations
and

are satisfied in many applications. With (9) the two occupation probabilities
/J.E.)and /h(g)reduceto classical distributions:
 Classical Regi

':.-\"-\\~'\\ I Conduciion
I
band

Figure 13.2 Occupancy oforbiials as a finite temperaiure, according to the Fermi-

Dirac disSribution function. The conduclion and valence bands may be represented
in terms of temperature-dependenteffedive numbers Nc, Nc of degenerate orbiials
located aS the iwo band edges e,, \302\243\342\200\236.
The n(, n( arc ihe corresponding quantum

= - => - A0)
exp[-(e cxp[-(,,

We use F) and A0) to write the total number of conduction electrons in the
form

N, A1)
Chapter 13: Semiconductor Statistics

where we define

N, - \302\243exp[~(s
-
ej/r]. A2)
Cfl

Here \342\200\224
\302\243 is
\302\243c the energy of a conduction electron referred to the conduction

band edge ec as origin.

The expression for lias the maihematical Ncfomt of a partition function
for one electron conduction band. In Chapter3 we evaluated
in the a similar

sum denoted there by Zlt and we can adapt that rcsuil lo the prescuJ problem
with an approximate modificalion for band siructure effects. Because of the
rapid decrease of cxp[-{\302\243 - e()/i] as c increases above its minimum value
at ee,only ihe distribution of orbitals within a range of a few x above cc really
matters evaluation of the sum in A2). The orbitalshigh in the band
in ihe
make a negligible contribution. The important point is that near the band edge

the electronsbehave very much like free particles. Not only arc the electrons
mobile,which causes the conductivity of the semiconductor, but the energy
distributionofihe orbitalsnear the band edge usually differs from that of free
particles only by a proportionality factor in the energy and eventually in the

sum for Z%.

We can arrange for a suitable proponionaliiyfactor by use of a device
called the densify-of-sfates effective mass. For free particles we calculated the
partition function Z\\ in C.62), but for zero spin. For particlesof spin | the
result is larger by a factor of 2, so that A2) becomes

Nc = Zj = 2nQV= 2(mx/2nh2)i!iV. A3)

Numerically, this gives

NJV =- 2.509 x 1019 x G/300KK'2cm\023 . (H)

where Tis in kelvin.

The quantity Nt for actual semiconductors ihe same temperature
exhibits
dependenceas A3), but differs in magnitude by a proportionality facior. We
express this formally by wriiing, in analogy io A3),

Nc *= 2(mSz/2nti2K'2V , A5)

where me* is called the denshy-of-btates effective mass for electrons. Experi-
Experimental values arc given in Table 13.1. The introduction of effective masses

is more than a formality. In the theory of electrons in crystals it is shown that

 Classical Regime

Ihe dynamical behavior of electrons

and holes, under the influence of external
forces such as electricfields, is that of particles wilh effective masses different
from the free electron mass. Thedynamical massesusually are different from
Ihe density-of-staJes masses, however.
We define the quantum coticetilralion for
??\302\243 conduction eleclrons as

nc = NJV - A6)

By A0 the conductionelectronconcentration ne = NJV becomes

A7)

The earlier assumption (9) is equivaleni Jo the assumption that n,. \302\253
nc, so

that the conduction electrons act as an ideal gas. As an aid to memory, we may
think of Ne as arising from N( orbilalsat \302\243\302\243,
wiili the Fermi level at ;i. IVanriiuj:
In the semiconduclor literature nt is invariably called the effective density of
statesof the conduction band.

Similar reasoning gives the number of holesin ihe valence band:

- e)/t]

wiih the definition

A9)

We define the quantum concentrationnv for holes as

e NJV s 2{in^z/2jihi)m.

where wk* is llns dcnsity-of-sJaJcs effective mass for holes. By (IS) ihe hole

concentration/^ s NJV is

\342\200\224 \342\200\224
nh aBexp[\342\200\224(/( e,-) B1)
Like A7), this gives the carrier concentrationin terms of (he quantum con-
ceniraiion and the positionof the Fermi level relative valeuce band
to the
edge. In (he semiconductor literature nu is called the effective density of states
of the valeuce band.

Law of Mass Action

The productn^nh is independent of the Fermi level so longas the concentrations

are in the classical regime. Then

'V'k = 'Wexpf-fE,.- O/r] s=

ncnuexp(~ eJz) , B2a)

where the energy gap s= ec

- In a pure semiconductor we have ut.
\342\200\224
>ibt
\302\2439 eff.

and the common value of the two concentrations is called the intrinsic carrier

concentration t^ of the semiconductor. By B2a),

B2b)

The Fermi level independence of the product n^iij, means that this product
retains its value even when ne <\302\243
nh, as in the presence of electrically charged
impurity atoms, provided both concentrations remain in the classical regime.
We may then write B2a) as

B2c)

The value of the product depends only on the temperature.This result is the

mass action law of semiconductors, similar to the chemical mass action law

(Chapter 9).

Intrinsic FermiLevel
For an intrinsic semiconductor ne = nh and we may equate the right-hand
sidesof A7) and B2b):

neexp[-(ec
- ^)/r] = (vO\022exp(-\302\243/>*). B3)

Insert = e^ \342\200\224
eB and divide by n,.exp( \342\200\224\302\243(/r):
eB

ej/2r].
 Donors and Acceptors

We lake logarithms to obtain

/i
= {U, + +
\302\243,.) |t Iog(u,/u,) = l(cc + e,) + 3rlog(\302\273ifc7\302\273i,*), B4)

by useof A6) and B0). The Fermilevel for an intrinsic semiconductor lies near
(he middle of lhe forbidden gap, but displaced from the exact middle by an
amount that is usually small.

w-TYPE AND p-TYPE SEMICONDUCTORS

Donors and Acceptors

Pure semiconductors are an idealization of Httle practical interest. Semicon-

Semiconductors used usually have impurities intentionally added in order
in devices to

increase the concentration of either conductionelectrons A semicon- or holes.

semiconductor with more conduction electrons than holes is called \302\273i-type; a semi-
semiconductor with electrons is called p-type.The letters
more holes than n and p
signify negative and positive majority carriers. Consider a silicon crystal in
which some of the Si atoms have been substituted by phosphorus atoms.
Phosphorus is just to the right of Si in the periodic table, hence each P has
exactly one electron more Si it replaces.
than the These extra electrons do not
fit into the filled valence band; hence a Si crysial with some P atoms wiil contain
more conduction electronsand, by the law of muss action, fewer holes than \302\253
pure Si crystal Next consider aluminum atoms. Aluminum is just to the left
of Si in the periodic table, hence Al lias exactly one electron fewer than the Si
it replaces. As a result, Al atoms increase the number of holes and decreasethe
number of conduction electrons.
Most impurities in the same columnsof the periodic table as P and Al will
behave in St just as P and Al behave. What matters is the number of valence
electrons relative to Si not the total number of
and electronson the atom.

Impurities from other columns of the periodic table will not behave so simply.
Similar reasoning can be appliedto other semiconductors, for example GaAs.
For the presentwe assume lhat each donor atom contributes one electronwhich
may enter the conduction band or fill one hole in the valence band. We also

assume that each acceptor atom removes one electron,either from the valence
band or from the conduction band.Theseassumptions are called the approxi-
approximation of fully ionized impurities: all impurities when ionized are either posi-

positively charged donors D+ or negatively charged acceptors A\".

The electrical neutrality condition D) told us that

An = \342\200\224~
nj+ \342\200\224 . .
nt nfc na~. . B5)
Chapter J3; Semiconductor Statistics

Becausenh = m,V\302\273*from the mass aciioti law, we secthat B5) leads to a quadratic
equation for nc\\

V-\".^!-^1. B6)

The positive root is

=
\302\273* i{[{A'O2 + V]1/J + An} , B7a)

and because nh
~
^ - An we have

\302\253
\302\273* l([(AnJ + V]1''2 - An], B7b)

Most often the doping concentration is Urge compared to the intrinsic con-
concentration, so that either nr or ft* is much larger than n,:

\302\273
\\An\\ nt. B8)

This Condition defines an The squarerootsin

extrinsic semiconductor. B7)
can then be expanded:

[(AnJ + An*]\"*
=
|^[i + (hj&nJ]1'2
-
m + ln*l\\bt\\. B9)

In an n-type semiconductor &n is positive and B7) becomes

nt =x A/i + nffAn - An; nh ** n^/An \302\253

n,. C0)

In a p-typc semicondiiclor An is negative and B7) becomes

Ji. ^ n?/\\An\\
\302\253
n,; nk ^ {A/i| + h;V1A*i1
^
jAffj. C1)

The majority carrier concent ration in the extrinsic limit B8) is nearly equal to
the magnitude of An, while the mmoriiy carrier concentration is inversely
proportionalto jAnj.

Fcrmf Level in Extrinsic Semiconductor

By use of the massaction law we calculated concentrations without

the carrier
having to calculate the Fermi level first. Tlic Fermi level is obtained from n, or

/ij,by solving A7) or B1) for/c

 Degenerate Scum

Figure 13.3 The Fermi icvet in silicon as a function of lempcraturc, for

various doping concentrations. The Fernifleveis are expressed

relative Ic

the band edges. A sniaii decrease of liic energy gap wiih icmperaiure has
been negieaed.

We may now use B7) to find ft as a function of temperature and doping level
An. Figure 13,3 gives numerical results for Si. With decreasing temperature ths
Fermi level in an extrinsic semiconductorapproaches eiiher the conduction cr
She valence band edge.

DegenerateSemiconductors
When one of the carrier concentrations is increasedand approachesthe quan-

quantum concentration, we may no longer use the classicaldistribution A0) for iliiit

carrier. The calculation of the carriorconcenir.iiion

now follows the treatment

of the Fermi gas in Chapter 7. The sum over all occupied orbitais, which n
equal to [he number of electrons, is written as an iiiteura! over the density yf
states times the distributionfunction:

N
Chapter IS: Semiconductor Statistics

where for free panicles of mass \302\273j

llie densily of stales is

C4)

Thai is, \302\251(\302\243)(&

is ihe number of orbitals in the energy interval +
(\302\243,e ck). To
make ihe transition to conductionelectronsin semiconductors we replace iV

by n,V; in by m,*; and \302\243

by e
\342\200\224
ec. We oblain

Lei x s (e - er)/r and ij

=
(fi
~
et)/t. We use the definition A6) of J(c to obtain

C6)

The integral /(;;)in C6) is known as the Ferml-Dirac integral.

When ee
-
p. x
\302\273 we have \302\273
\342\200\224ij 1, so that cxp(x
- jj) 1.
\302\273 In this limit

C7)

the familiar result for the ideal gas.

In semiconductors the electron concentrationrarely exceeds several limes
the quantum concentration nc.The deviation between the value of/i from C5)
and the approximation C7) then can be expanded into a rapidly converging

power series of the ratio r = njn^ calledthe Joyce-Dixon approximation:*

\342\226\240 C8)
\",/\"\342\200\236

\302\253-\342\200\224i-S-f)

Figure t3.4 compares the exact relation C6) witll the approximations C7) and
C8).

\342\200\242
W. B. Joyce and B. W. Dixon. App!. Phys. Lclt. 31,354 A977). If the right side of C8) is wrine

1.483S6 x lO\"*:^, - -4A2561x 1Q-6.'

 Dtgcncnitt Slmicomlitct

7 -6 -5 -4 -3 -2 -I 0 1 2 3 4 5 6
= - i,)h
i) (|.

above conduciion band edge Er. The dashed curve reprcsenisihc firsi icrm of ihc

Joycc-Dixon approximation C8).

Chapter 13: Semiconductor Sta

When neisno longer small comparedto n(, Ihe expression of the mass action
law must be modified.In Problem4 we ask ihe reader io show ihat

C9)

If the
gap Itself depends on the carrier concentrations, the value of n, to be used
here will
depend on concentration.

Impurity Levels
The addition of impuritiesto a semiconductor moves some orbitals from the
conduction or valenceband into Ihe energy gap, where the orbiials now appear
as localized bound states. in a silicon crystal.If the
We consider phosphorous
P atom has electron to the Si conductionband,
released iis extra the atom

appears as a positively charged ion. The positiveion attractsthe electrons in

the conduction band, and the ton can bind an electron just as a proton can
bind an electronin a hydrogen atom. However, the binding energy in the
semiconductoris severalordersof magnitude lower, mostly because the binding
energy is to be by the square divided of the static dielectric constant, and
paniy because of mass 13-2 gives the ionizationenergies
effects. Table for

column V donors in Si and Ge. The lowest orbital of an electron bound to a

donor corresponds to an energy level Asd =
st
\342\200\224
st below the edge of the
conduction band (Figure13.5).
There is one set of bound orbitals for every

donor.

A parallel argument applies to holes and acceptors.Orbiialsare split off

from 'he valence band, as in Figure 13.5. For each acceptor atom there is one
set ofbotmdorbitals wiih an ionization energy Asa ~ Ea
\342\200\224
\302\243,,,ofthesameorder

as Aej. Ionization energies for column III acctipcors

in Si are listed in Table 13.2.
In GaAs the ionizationenergies for all column VI donors except oxygen are
closeto 6rrteV. For zinc, the most important acceptor, &\302\243a
= 24meV. Some

T:.Mc 13.2 !uiiu..iio.i encr^e*ofcuhmm V <j

column il! acceptors in Si arui Ge, in mcV

Ace cp OIS
11 AI Ga In

49 45 57 65 16
12.7 10.4 10? iOS 11.2
 Occupation of Donor Letch

'
At, !' \"'

\302\261

Figure 13.5 Donor and acceptor impurity levels in Uic energy

impurities generate orbitals deep inside the forbidden gap, sometimes with
multiple orbitals corresponding to different ionization states.

Occupation of Donor Levels

A donor level can be occupied by an electronwith either spin up or spin down.
Hence there are [wo different orbitals with the same energy. However, the
occupationsof these two orbitals are not independe nt of each other; Once the
level is occupied one by electron, the donor cannot bind a second electron with
opposite spin. As a result, the occupation probability for a donor level is not
given by the simple Fcrmi-Diracdistribution function, but by a function
treated in Chapter 5. We write the probability that the donor orbital is vacant,
so that the donor is ionized, in a form slightly different from E.73):

Here Ed is the singly occupied donor orbital relative

energy of a to the origin

of the energy. The probability that the donor orbital is occupied by an electron,
so thitt the donor is neutral, is given by E.74):
Chapter 13; Semiconductor Statistics

Acceptors require extra thought. In the ionized conditionA\" of the acceptor,

each of the chemical bonds between ihe acceptor atom and the surrounding
semiconductor atomscontainsa pair of electrons with antiparaliel spins. There
is only one such state, hencethe ionized condition contributes only one term,
exp[(/i - cJ/t], to the Gibbs sum for the acceptor, lit the neutral condition A
of the acceptor, one electron is missing from the surrounding bonds. Because
the missing electron may haveeithcrspin up or spin down, the neutral condition
is representedtwice in the Gtbbs sum for the acceptor, by a term 2 x J ~ 2.
Hence the thermalaverageoccupancy is

'
exp[{^ ~
A {~ \"}
2 + -
Efl)/i] \"\021+2 exp[(Efl $x]\"

The neutral condition A, with the acceptor orbityl unoccupied, occurs with

probability

______ _ __________ D3)

The value of An == nd+ \342\200\224

na~ is the difference of concentrations of D* arid A\342\204\242.

From D0) or D2) we have

D4)

D5)

The neutrality condition D) may be rewritten as

This expressionmay be visualized by a logarithmic plot of n\" and n* as func-

functions of the position of the Fermi level (Figure 13.6}. The four dashed lines
represent the four terms in D6); the two solid lines representthe sum of aii

positive and all negative charges.The actual Fermi level occurs where the total
posicivechargesequal the total negative charges.
For nd+
-
jio~ \302\273holes can be neglected;for
nh as in Figure 13.6, the
nu~
~
\024* \"i 'he electrons
-^ can be neglected. If one of the two impurity
species can be neglected, the majority carrier concentrationcan be calculated
in closed form- Consider an it-type semiconductor with no acceptors. The
 Occupation of DonorLetch

Figure 13.6 Graphical determinaiion of Fermi teve!and eteciroi

an n-1ypc sciniconducior coniaining both donors and acceptors.

neutrality point in Figure 13.6 is now given by the intersection point of the n*
curve with the ?!e curve, donor concentration is not too high,
U ihe the inter-

intersection will be on the straight portion of the incurve, alongwhich the approxi-
approximation A7) holds. We rewrite this as

cxp(/</T)- (\302\273A)\302\253PfcA); \302\2537>

- - = njn* ,
exp[(^ \302\243i)/t]
=
(\302\273>Jexp[(\302\243, tj/t] D8)
 -
nc* s
neexp[~(et Eli)/i] = ;i,exp(-A^/t) . {49}
Is the electron concentration that would be present in the conduction band if
the Fermi level coincided with the donor level. Here Aed
~
ec
~ Ej is the donor
iontzacton energy.
We insert D8) into D4) and set nt
~
nd* to obtain

E0)

nf3 + \\n,nt*
= i\302\273rfn,*. E1)

llus is a quadratic equation in n,; ihe positive solution is

=
V([l
\302\273\342\200\236 + (S\",,//)/)]1'3- I}- E2)

For shallow donor levels, nt* is large and close to nc.ffthe doping is sufficiently

weak that 8\302\273j\302\253

\302\273/, the square root may be expanded by use of

\342\226\240\342\226\240\342\226\240
A + xI1* =? 1 + \\x -ix2 + , E3)

for -v i.
\302\253 With x ~ 8\302\273d/He* we obtain

-
^ \302\253\342\200\236 - E4)
\302\273\342\200\236 2it//ne* \302\253
;tj(l 2<td/ite*).

The secondtermin the parentheses gives the first order departure from complete
ionization.For example, for P in 300 K, we
Si at have Ae,j ^ t.74r from
Table 13.2, so that ne* =s 0M5nc from D9). If \302\253j
=
0.0!nf, Eq. E4) predicts
that il.4 pet of the donorsremain un-ionized. The limic of weak ionization is
the subjectof Problem 6.

Example: StuM-itiiHtuting gallium anaiM*.: Could pure GaAs be prepared, it would have
an intrinsic catikt concciUfdtioita! room temperature of\302\273,< 10'cm\023. Wjih such a tow
conceuiraiion of carriers, @~\" less than a nicial, the conductivity would bs; closer !O art
insulator than to a conveniiona! sciniconductor. [<itn'iisk G;iAs would be useful as an
substiatc
\302\273isulat:n\302\243 on whidi to prepare lEiin layers of doped GaAs as neeJed for devices.

There Joes no! exist a technology to purify any substance to 101 wnpuriircs per em1.
 p-n Junctions

However, ic is possible near tnerinste

to achieve carrier concentrations in GaAs by doping
with high concentra lions (tOi5-IO17 Cm-3) of oxygen and chromium together, two impu-
impurities ttiat have iticir impuriiy levels near the middle of ihe energy gap. Oxygen enters an
As site and is a donor in GaAs, as expecicd from the posiiion of O in the periodic Cable
relative to As; the energy level* is about 0.7 eV belowts. Chromium is an acceptor v> i'h an

energy level about Q.S4eV below et.

Consider a GaAs crysiai doped with boih oxygen and chromium. The ratio of liiS two
conceniraiions is not critical; anything with an O:Cr raiio between abouc 1:10and 10:1
will do. If the conccitiraiions of all olher impurities are small compared with those of O and
Cr, (he position of ihc Fermi level will be governed by ihe equilibrium betweenelm -ons
on O and holes on Cr. The construction of Figure t3.6 applied io tliis system shows that
over the indicated concentration raiio rangedie Fermi level is pinned io a range between
t.5i above the O fevel and l.5r below (he Cr level. With ihe Fermi level pinned near the
middle of the energy gap, the crysiai must act as nearly imrinsic

Gallium arsenide doped in this way is called semi-insulating GaAs and is used extensively
as a tiijjh-resisiivity [!0a to to10 il cm\\ substrate for GuAs devices. A similar doping pro-
procedure is possible in inP, with iron taking ihe place of chromium.

p-n JUNCTIONS

Semiconductors used are almost

m devices never uniformly doped. An under-
understanding of devices requires an understanding of nonuniformiy doped semi-

semiconductors, particularly of structures called p-n junctionsin which the doping

changes with posi! ton from /vtype to n-type within 'he samecrystal.We consider
a semiconductor crystal inside which the doping changesabruptly at .v = 0

from a uniform donor concentration nd to a uniform acceptor concentration

na, as in Figure i3.7a. This is an exampleof a p~i\\ junction. More complicated
device structures are made up from simple junctions: a bipolar transistor h.-is
iwo closely spacedp-n junctions, ofthe sequence p-i\\~p or n~p-n.

p~n junctions contain a built-in electrostaticpotential step Vbi, even in the

absence of an externally applied voltage (Figure 13.7b). With no externally
applied voltage, the electrons on the two sides of the junction are in diffusive

equilibrium, which means that the chemical potentials(Fermilevels) of tlic two

sides are the same. Because ihe posiiionof the Fenni level within ihe band
siructurc depends on the localdoping,constancy of the Fermi level forces :i
shift in the electron energy bands in crossing ihe junction (Figure 13.7c). The
shift is eVN. The potential stop of height eVbii% an example of the potential step
required to equalize the total chemical potential of two systems when ihc
intrinsic chemicalpotentialsare unequal, as discussed in Chapter 5.
Figure 13.7 A p-n junclion. (a) Dopingdislribulion.!l is assumed
that the doping changes abruptly from n-type to p-type. The two
doping levels arc usually different, (b) Electrosiaiic poteniiat. The
buitl-in voltage Vbl diffusive
ealabtishes equilibrium between ihe
two sides wilh differenl electron concenlralions as wet! as hole
concentrations, (c) Energy bands. Becauseihe Fermi level must be

shifted relaiivc to each other, (d) Spacecharge dipolc required to

generate the buitl-in voltage and to shift the energy bands.
 We assume that the two doping concentrationsnd, tta lie in the extrinsic but
nondegenerate range, as defined by

\302\253 \302\253
\302\273c; \302\253
na \302\253 E5}
Hf nd \302\273( \302\273t.

If the donors are fully ionized on the n side and the acceptorsfully ionized on

the p side, then the electron and ho!econcentrations

satisfy

ne
=z vd\\ nh
s: na, E6)

one on the n side and the other on thep side. (We have droppedthe superscripts

from
\302\261 Jij, The conduction
\302\273\342\200\236.) band energies on the i\\ and p sides follow from
A7):

\302\253\302\253-/*-xlbgl^/nj; E7)

ccp = H~ xlo&{nJnc) = ;1- tlogK1/\"^). E8)

by B2c). Hence

eVtf - -
\302\243CJ. e\302\253
=
Tlog(W>,2) . E9)

For doping concentrationsnd ~

0.0inrand Hfl=s0.0inL.,we find eHi = es -~9.2t,
which is 0.91 eV in silicon at room temperature.
A
step in electrostatic potential to shift
is required the band edge energies on
the two sides of the junction relative to each other. The electrostatic potential
<p{x) must satisfy the Poisson equation

(SI)
~ = ~~ , F1)

where space charge density and e the permittivity

p is the of the semiconductor.

Space charge must be presentwhenever <p varies. In the vicinity of the junction
the charge carriers no Songer neutralize the impurities as in the bulk material.
The space charge must be positive on the h side and negative on the p side

(Figure 13.7d}. Positive space charge on the n side means that the electron
concentration is less than the donor concentration, indeed, as the conduction
Chapter 13: Semiconductor Statistics

raised relative to the fixed Fermi

band edge ts level, A7) predicts an exponential
decreaseof the electronconcentration ie.
Take the origin ofthe electrostatic potential at x = -co.soihai <p(-00}= 0.
Then = \342\200\224
and becomes
ec(x) \302\243c(~-a)) e<p{x), A7)

ne{x) = ntcxp[e<p[x)/T]. F2)

ThePoisson equation F1) is

^ ] ^
F3)

Multiply by Jdtpfdx to obtain

_</WV </
AM2 ^ J f
r
/ , ,1 i6d\\
d.x i/x^ (/.x \\il\\-J t dx { e J

Integrate uiih the initial condition<p{\342\200\224

oc)
= 0:

]
F5)
\\dxj
At the interface x = 0 we assume that'

F6)

where Vn is that part of the built-in electrostaticpotentialdropthat occurs on

the n side. The exponential on the right-handsideofF5)can be neglected, and

we obtain

E - [peii,/c)(K,- */e)Vn F7)

for the -v
component ofthe electric field E = -dipjdx. at the interface.Similarly,

\302\243=[{2eMB/\342\202\254)(^-t/e)]\022,
FS)

where I-; is that part of ilie built-inelectrostatic potential drop that occurs on

ihepstdcTlie two \302\243

fields must be the same; from this and from Vn -V Vp
= Vbi

we find

(\302\243^')\022 F9)
 rse-BiasedAbrupt p~n Junction

The field E is the Sameas if On the ii-type side all electrons had been depleted
from lite junction to a distance

-(Vw-2r/f) , G0)

with no depletion at \\x\\

> \\vK. The distance wa is used in semiconductor device
theory as a measureofthe depth of penetration of the space charge transition
layer into the n side.

Similarly, on the p side,

The totaldepletion width wK

1f we assume \302\273o
=
nd = i0licm\023;e ~ l(ko;aiid Vbi
- 2z/e == 1 volt, we lind
- 4.25
\302\243 x 104VcmwI and w = 4.70 x iO^5cm.

Reverse-Biased Abrupt p-n Junction

Let a voltage V be applied to a p-n junction, of such sign that the p side is at a
negative vohagerelativeto the n side, which means that V raises the potential
energy of the electronson the p side.This voltage will drive cond uction electrons
from the p side to the \302\273
side, and holes from the ;i side to the p side.But the

p side in bulk contains a very low concentration of conduction electrons, and ifie

n side contains a very low concentration of holes,consistentwith the mass

action law. As a result, very little current flows. The distributions of electrons,
holes, and potential are approximately ihe same as if the built-in voltage were
increased by the applied voltage,Figure 13.S. The field at the interface is now
given by

G3)
Chapter 13: Se

..-\342\226\240

\342\200\224
\342\200\2247\342\200\224

//
it

\342\200\224'
\342\200\236._
r. /
/

1
mi .->

Figure 13.8 Reverse-biased p-?i junaion, showing tfic cjuast-Fcrmi

levels fi, and//P.

and the junction thicknessis given by

G4)

In the semiconductor device liierature we often find G3) and G4) without the
term 2t/e, becausecertain approximations have beea made about the space
charge and field distribution; we have solved the Poisson equation with the

correct electron distribution F2).

 Currtrni Flow: Drift and Diffus

NONEQUILIBRIUM SEMICONDUCTORS

Quasl-Fcrmi Levels
When a semiconductor is illuminated with light of quantum energy greater
than !he energy gap, electronsarc raised from the valence txind to the conduc-
conduction band. The electron and the hole concentrations created by iliumination
arc larger than their equilibrium concentrations. Similarnonequiiibrium con-

concentrations arise when a forward-biased p-n junction injectselectrons inio a

ptype semiconductor or holes into an ii-type semiconductor. The eiectric

charge associated with the injected carrier lype allracis oppositely charged
carriers from the external electrodesof the semiconductor so thai bolh carrier
concentrations increase.
The excesscarriers eventually recombine with each otlier. The recombination
timesvary greatly with the semiconductor, from less than lo~9s to longerthmi
10\" 3s. Recombination tiniesin high purity Si are near 10~35. Even the shortest

recombination times are much longer than the times (-^ lG~l2s) required at
room temperature for the conduction electronsto reachthermal equilibrium

with each other tn the conduction band, and for the holes to reach thermal
equilibrium with each other in the valence band. Thus the orbital occupancy
distributionsofelectrons and of holes are very close to equilibrium Fermi-Dirac
distributions each band separately,
in but the tola! number of holesis not in
equilibrium with the total nuniber of electrons.
We can express this steady state or quasi-equilibrium condition by saying
that at tthere are di fierent Fermi levels;<c and ;iv for the two bands, called quasi-
emii levels:
ii levels:

7\021\"
I +exp[(t-\342\200\236\342\200\236)/,]\342\200\242

Quasi-Fermi levels are used extensively in the analysis of semiconductor devices.

Current Flow: Drift and Diffusion

If the conductionband quasi-Fermi level is at a constant energy throughout a

semiconductor crystal, the conduction electrons throughout the crysta!are in

thermal and diffusive equilibrium, and no electron current wjl! flow. Any
conduction electron flow in a semiconductor at a uniform temperature must be
caused by a position-dependence of. the conductionband quasi-Fermi level.
Chapter 15; Semiconductor Statistics

If the gradient of this level is sufficiently weak, we may assume that the con-
contribution of conduction electrons to ihe total electrical current density is

proportional to this gradient:

J, cc grad/*(. G6)
HereJe is an electrical current density, not a particle flux density. Because each
electron carries Ihe charge we
\342\200\224e, have

5 x
(\342\204\242e) {electron flux density), G7)

where the electronilux density is defined as the number of conduction electrons

crossing unit area inunit time. The ciose connection of G6) to Ohm'sSaw is

treated in Chapter 14. Because the flow of particies is from high to low chemical
potential, the conduction electron flux is opposite to grad nc, but because
electrons carry a negative charge, the associated electricalcurrent density is

in the direction of grad fic. We view grad jj\302\243

as the driving force for this current.
Fora given driving force, the current density is proportional to the concentration
nt of conduction electrons. Thus we write

Jt_ ~. G8)

where the proportionality constant fi't is the electron mobility. The symbol pt
should not be confused with the conduction band quasi-Fermi level,/jc.
If the electron concentration is in the extrinsic but nondegenerate range,

n, \302\253
nf \302\253
nc , G9)

the cottduclion band quasi-Fermi level is given by A5), which can be written
in lerms of the eleclronconcentration as

ut - + Tlog(it7\302\253A
\302\243c (80)

Thus G8) become:

(81)

A gradient in the conduction band edge arises from a gradient in the electrostatic
potential and thus from an electricfield:
 Current Flaw: Drift and Diffusion

We introduce an electron diffusion coefficient Dc by the Einstein relation

Dt - pex/e , (83)

discussed in Chapter 14. We now write (?S) or (8i) in the final form

J, - eptntE 4- eDe grad n (84)

There arc two different contributions to the current:one caused by an electric
field and one caused by a concentration gradient.
Analogous results apply to holes,with one difference. The valence band quasi-
Fermi levelis not ihc chemicalpotential for holes, but is the chemical potential
for the electrous in the valence b;ind. Holes arc missingelectrons;a hole current

io the right is really an electron current to the left. But holes carry a positive
rattier than a negative charge.Thetwo sign reversals cancel, and we may view
grad j.iv as the driving force for the contribution Jh of holesto the total electrical

current density. We write, analogously to G8),

\302\273
Jh jvifcgradjv (85)

Carrying through the rest of the argument leadsto

as the analog of (84), with the Einstein relation Df, = ji^fe- Note the different
sign in the diffusion term: Holes, like electrons, diffuse from high to low con-
concentrations, but hole diffusion makes the opposite contribution to the electric
current, because holes carry lhe opposite charge.

Example:Injection laser. The highest nonequilibrium carrier concenlrations in semi-

semiconductors occur in injection lasers. When by efectron injection ifie occiipaiion f&c) of
Ihc towesi conduciion band orbital becomes higher than lhe occupalioii/XeJofthe highesl
valence band orbiial, the population is said lo be invened. Laserilieory iclls us ihai lighi

energy ec \342\200\224
= ihtn be amplified by siimulylcd emission. The
Vvilh a quantum &f can
\302\243\342\200\236

condiiion for populaiion inversion is ihat

/Me) > fM (S?)

Wiih ilie quasi-Fernii distributions G5) this condition is expressed us

(88)
 Figure 13.9 Double-heterostructtirc laser. Electrons Row from the
injection
right into the active layer, where they form a degenerate eieciron gas. The
potential barrier provided by t!ic wide energy gap on the p side prevents the
electrons from escaping to the left. Holes flow from ihc Icfi iiiio ihe aciive
layer, but cannot escape to the right. When (83) is attained, laser aciion
becomespossible.

For laser action the

quasi-Fermi levels must be separated by more ihan ihe energy gap.
The condition (88) requires that at least one of the quasi-Fermi levels lie inside ihe band
to which it refers. This is a necessary,bui not a sufficient condiiion for laser operation.
An important additional condition is that the energy gap is a direct gap rather than an
indirect gap. The distinction is treated in solid state physics texts. The most
important
semiconductors direct gap are GaAs and inP.
with a
The population inversion is most easily achieved in the double hcterostructtire of Fig-
Figure 13.9; here ihe lasing semiconductor is embeddedbetween two wider-gap semiconductor
regions of opposite doping.An example is GaAs embedded in A!As. In such a structure
there is a potential barrier that prevents the outflow of electrons to the p-type region,and
an opposiic poieniial barrier ihat prevents ihe outflow of hoies to then-type region.
Except for caused by tlic recombination
the current itself, the electrons in the waive liiy\302\253r
arc in diffusive equilibrium wilh tlic electrons in the n contact, ana\" the electron quasi-
Fermi level in the active layer lines up with the Fermi level in then contact. Similarly, the

valence band quasi-Fermi level lines up with the Fermi level in the p coniact. inversion
can be achieved if we apply a bias voltagelarger than ihe votlage equivalent of the active
layer energy gap. Most injection lasers utilize this double heierostf uciure principle.
 rent Flow: Drift and Diffusion

Example; Canter recombination throush an iaipsiriiy level, Electrons and holes can re-
combine eiiher by an electron falling dircciiy inio a hole emission of a photon,
with itic
or ihey can recombine ihrough an impurity level in ihe energy gap. The impuciiy process
is dominant in silicon. We discuss ihe process as an insiruciivc example ofquasi-equilibf ium
semiconducior statistics. Consider an impurity recombination orbiiai ut energy t, in
Figure 13.10. Four transition processes are indicated in the figure. We assume that ihe
rate Rc, at which conduction electrons fail into the recombination orbiiais is described by
a law of the form

*\342\200\236-(! ~/>A \342\200\242 (89)

w here fr is the fraction of recombinationorbitais already occupied by an electron (and

Itcnce not available), and characteristic time constant for the
t. is a capture process. We
iissume the reverse processproceeds ai tiie rate

Kc = /,'lj'e' , (90)

\302\253hcrcit'
is the time constant forttie reverse process. We tnke R,, independent of the con-

concentration of conduUion ekurons, becausewe assume that i\\e < nt 1 he time consiaitts r.

Figure 13.10 Electron-hole recombination ihrough

impurity recombination orbitais at t, inside ihe energy
\342\226\240
gap- .
Chapter 13; Semiconductor Statistics

and r,' arc related, becausein equilibrium ilie two raies Rrt and Rcr musi cancel Thus

wiihf, and n, evaluated in thermal equilibrium, which means we use A7) for h,. We ignore
ihc spin muitipiiciiy of the rccombinaiion levels, Wiih ihe equilibrium Fcnni-Dirac
distribution for/, we have

A -/,)//, = exp[~{^~e,)/r]. (92)

Thus (91) becomes

= (93)
^ ^exp[~fc-\342\200\236)/!]\302\273\"\302\243.

where ne' is defined as ihe conduction electron conceniralion lhal would be present if ihc

equilibrium Fermi level ft in A7) coincided wjlh the recombination level, if (92) and (93)
arc insenedinto (89) and (90), ihe net electron recombinalion rale becomes

Re = Rcr
~
R,c - ~ [A'- f,)nt
-
/,\302\273/]. (94)

The analogous recombinaiion rate Tor holes is obtained by ihe subsiituiions

Re, %,\302\273/, te -* Rh, flh, nh*, !h;

and

/-I ~Jr\\ 1 -/,-/,. (95)

Here fk is the lifetime of holes in ihe limit thai ail recombination ceniersare occupiedby
eiecirons, and n,,* is, by definiiion,

ah* s nBexp[-(\302\243,
-
ej/i] - ;i,V\302\273.*- C96>

With these substiiutioiis the net hole rccombiiiationrale is

Iiisteady staieUicuvorecombinaUonfaiesmusibcequaS:R, = Hft

= R.Equations 194)
and (97) arc iwo equal ions for ihe two unknowns f, and /?. W'i. eiiminalc /, to find

(9S)
This is the basic rcsuli of ihe Hail-Siiockley-Read
recombination iheory.' Applications
are developed In Problems 10 and I).

SUMMARY

!. In semiconductors the electron orbilals valence band

are grouped into a
(completelyoccupied at r
\342\200\224
0 in a pure semiconductor) and a conduction
band (complelely empty
al x = 0 in a pure semiconductor), separated by
an energy gap. Electrons in the conduction band are calledconduct:-:1'
electrons; empty orbitals in the valence band are called holes.
2. The probability of occupancy of a band orbital with energy e is governed
by ihe Fermi-Dirac distribution function

Here \\i is the chemical potential of ihe electrons, called the Fermi ievei.

3. The energetic location of the Fermi level in an eleclrically neutral semi-

semiconductor is governed by the neutrality condition

Here ne and i\\h are the concentrations eiecirons and holes,

of condiiction
and An is the excess Concentration of positively charged impuritiesover
negatively charged impuriiies.

4. A semiconductor is said to be in the classical regime when ne \302\253

nt and

nh \302\253
nv. Here

are the quantum concentratioi)s for electrons and holes; hi/ and \302\253?/arc
efTecItve masses for eiecjrons and Ijoles. In the semiconductorHteralure,
nc and are called
\302\273\342\200\236 the effective densities of states for the conduction;:nd
valence bands.

*
R. N. Hall, Phys. Rev. 87, 387{i952); \\V. Shockley and W. T. Read. Jr.. Phys. Rev.S7. S35{!952).
. In ihe classical regime

where \302\243\302\243
and eu are the energies of ihe edgesof the conduction and valence
bands.

6. The mass action law stales that in the classical regime the product
=
'I.-1
\"\302\273\302\273*
- 'M'uexp(-\302\243a/i)

is independent of the impurity concentration. The intrinsicconcentration

n,
is the common value of n{ and nh in an intrinsic ( \342\200\224
pure) semiconductor.

The quantity

is the energy gap.

7. A semiconductor is called Ji-type when negative charge carriers {- con-
conduction electrons) dominate; it is called p-type when positive charge
carriers (wholes) dominate. sign of
The the dominant charge carriersis
oppositeto the sign of the dominant ionized impurities.

S, A p-n junction is a rectifying semiconductor structure with nn internal

transition from p-typc to n-typi. A p-n junction contains internal electric
fields even in the absence of an appliedvoltage.Foran abrupt junction the
field at the p-n interfaceis

Here e is the permittivity, nu and Mj are ionized acceptor and donor con-
concentrations, and
| V\\
and Vbi are the applied and the built-in reverse bias.
9. The electric current densities due to electron and hole flow are given by

JB = e/yi,E + eDegmdne,
Jp ~ ephnkE
-
ePsgrad nh,

. Here % and are ihe

\302\243\342\200\236 electron and hole mobilities, and \342\226\240
 are ihe electron and hole diffusion coefficients.

PROBLEMS
1. Weakly doped semiconductor. Caiculale the electron and hole concenlra-
tjons when the net donor concentration is small coinpared to the intrinsic
concentration, \302\253
nt.
jAnj

2, Intrinsic conductivity and ininimuni conductivity. The electrical conduc-

\342\226\240
. --
conductivity is

a = e{ntpe + njh) , (99)

where Jit and and hole mobilities.For most semiconductors

ph are the electron
fl( > Jfj,. (a) Find the net ionized impurity conccntral/on An ~ na* \342\200\224
/ia~ for
which the conductivity is a minimum.Give a mathematics!expression for this

minimum conductivity, (b) By what factor is it lower lhan the conductivity of an

intrinsic semiconductor?(c) Give numerical values at 300 K for Si for which the
mobilities are jie = 1350 and pk = 4S0cm3 V~*s~l, and for InSb, for which
the mobilities are p# = 77000 and jih = 750cm2V\"Is\021. Calculate missing
d;itu from Table 13.1.
3. Resistivity impurity and concentration. A manufacturer specifies the re-
resistivity p I/a =
of a Ge crystal as 20 ohm cm. Take pc = 3900 cm2 V\021 s\021

and /Zk=s 1900cm1 V\021 s~l. What is the net impurity concentration a) if the

crystal is n-type; b) if the crystal is p-type?

4. Mass action law for high electron concentrations. DeriveC9),which is the

form of Ihe law of mass aclionwhen ne is no longer small compared to ne.

5. Electron and hole concentrations in InSb. Calculate nc, nh, and /i
\342\200\224
Et for

n-type InSb at 300K, assuming nd+ \342\200\224

4.6 x 1016cm\"\"J Because of the
= ne.
high ratio njn,. and the narrow energy gap, the hole concentration is not
negligible under theseconditions, nor is the nondegsnerate approximation
ne \302\253
nc applicable. Use the generalized mass action Saw C9). Solve Ihe tran-
transcendental equation for nc by iteration or graphically.
6. incomplete iont'zation o/ deep imparities. Find the fraction of ionized
donor impurities
doi if the donor tontzalton energy fs large enough lhat Aed is larger

than t }og(nJ8nd) by several times t. The result explains why substances with
large impurity tonization energies remain insulators, even if impure.
Chapter 13 s Semiconductor Statistics

7. Built-in field for exponentialdoping profile. Suppose that in a .P-type

semiconductor the ionizedacceptorConcentration at x = xt is \302\273\342\200\236\"
<- \302\273% \302\253
\302\273\342\200

and falls off exponentially to a value na~ =

ns at X
n2 \302\273 = x2. What is the
built-in eiecuic field in the interval (xtlJCj)? nurnerica! Give values for
~
/!s//ii
103 and Xj \342\200\224 = I0~ 5 cm. Assume T = 300K. distributions such
X[ Impurity

as this occur in the base region of many n-p-n transistors. The built-in field
aids in
driving the injected electrons across the base.
8. Einstein relation for high electron concentrations. Use the Joyce-Dixon
approximationC8)to give a series expansion of the ratio DJfic for electron
concentrations approaching
or exceeding itc,

9. Injection laser. Use the Joyce-Dixonapproximation to calculate at T =

300 K the electron-hole pair concentration
in GaAs that satisfies the inversion
condition (88).assumingno ionizedimpurities.
10. Minority carrier Assume both electron and hole concentrations
lifetime.
in a semiconductor by 6n above their equilibriumvalues.Definea net
are raised
minority carrier lifetime f by R =* Sn/i. Give expressions for i in terms of the
carriereonccniraiions ne and i\\h; the energy of I lie recombination level, as
expressed by ne* and nh*; and the time constantsit and tk, in the limits of very
small and very large values of Sn. Uiider what doping conditionsis f indepen-
independentof ditt

11. Electron-hole pair generation. Inside a reversebiasedp-n junctionboth

electrons and lides have been swept.out. (a) Calculate the elcciron-holepair
generation rate under these conditions, assuming ne* = nfc* and te ~ th = t.
(b) Find ihe factor by which tin's generation rate is higher than the generation
rate in an \302\253-type semiconductor from which the holes have been swept out,
but in which the electron concentration remains equal to itd+ \302\273'i,-. (c) Give a
numerical value for this ratio for Si with ji/ = 10Ificm~3.
Chapter 14

Kinetic Theory

KINETIC THEORY OF THE IDEAL GAS LAW 391

MaxwellDistribution of Velocities 392
Experimental Verification 394
Collision Cross Sections and Mean FreePaths 395
TRANSPORT PROCESSES 397

Particle Diffusion 399

Thermal Conductivity 40!
Viscosity 402

Generalized Forces 404

Einstein Relation 406

KINETICSOF DETAILED BALANCE 407

ADVANCED TREATMENT;
BOLTZMANN TRANSPORT EQUATION 408
Particle Diffusion 409

Classical Distribution 4!0

Fermi-Dirac Distribution 4! I

Electrical Conductivity 413

LAWS OF RARF.FIED GASES 413

Flowof Molecules Through a Hole 414
Example: Flow Through a LongTube 4!6
Speed
of a Pump 417

SUMMARY

I'KOIiUCMS 419
1. Mean Speeds in a Maxwcllian Distribution 419
2. Mean KineticEnergy in a Beam 420
3. Ratio of Thermal to ElectricalConductivity 420

4. Thermal Conductivity of Metals 420

5. Boitzmann Equation and Thermal Conductivity 421
Chapter14: Kinetic Theory

6. Flow Through a Tube 421

7. Speedof a Tube 421

I ant conscious of being only an individual struggling weaklyagainstthe stream

of time. But if still remains in my power to contribute in such a way thai, when
the theory of gases is againreviled,not too much will have to be rediscovered.
L, Betiynann
 Kinetic Theory of the Ideal Ga>

!n this we give a kinetic derivationof dieideal

chapter gas law, the distribution
of velocities of gas molecules,and transport processes in gases: diffusion,
thermal conductivity, and viscosity. The Bohzmaim transport equation is
discussed. We also treat gases at very low pressures, with referenceto vacuum
pumps. The chapter is essentially classical physicsbecauseIhequantum theory

of transport is difficult.

KINETIC THEORY OF THE IDEAL GAS LAW

We apply the kinetic method to obtain an elementary derivation of the ideal gas
~
law, pV Nx. Consider molecules that strike a area unit of the wall of a
container. Let v, denote the velocity component normal to the plane of the wall.
as in Figure 14.1. If a molecule of mass M is reflected specularly (mirror-likcj
from the wall, the changeof momciitum
of the molecule is

\342\200\224
2A/|i-x|. A)

This gives an impulse 2M|i>.|to the wall, by Newton's second law of motion. The
pressureon the wall is

_ /momentum cliangc\\/number of molecules strikmgN pj

\\ per molecule )\\ unit area per unit lime /

. Let a(vI)ilv1be the number of molecules per unit volume with the 2 component

of the velocity between i>, and v2 + dii2. Here \302\247a{v.)dvz

\342\200\224
NjV
= n. The

number in this velocity range that strike a unit area of the wall in unit time is

a(vJ)vIdDx. The momentum change of these molecules is -2Mi-.fl(i'.)iyf[i;, so

that the totai pressure is

p = JO = M f\"
{a>2Mv1la{t\\)dv1 v.la{vMv.. C)
J-a

The integralon the right is the thermal average of v22 times the concentration,
so that p ~ Afn<yI2>, The average value of JjMi-e2 is |t, by equipartition of
 change of momentum of a
ily v which is reftecied from
ntaincris ~-2M\\vz\\.

energy (Chapter 3). Thus the pressure is

p= iiAf<ps2>
= 'it = (NfV)z; D)

This is the idealgas law.

The assum ption of specular reflection is convenient,but it is immaterial to the
result. What comes into t!:e surface must go back, with the same distribution,
if thermal equilibrium is to be maintained.

Maxwell Distribution of Velocities

We now transform the energy distribution function of an ideal gas into a

classical velocity distribution function. Often when we mean \"speed\"we shall
say \"velocity\", as this is the tradition in
physics when no confusion is caused.
In Chapter 6 we found the distribution function of an ideal gas to be

Ati = E)

where/(cn)
is tltc probability of occupancy of an orbital of energy

\342\200\242
ui\\l

in a cube of volume V = Li, The average number of atoms with quantum

number between it and n + tin is (tlie number of orbilals in this range) x (the

probability such an orbital is occupied).Tltenumberof orbitals in the positive

 MaxwellDistribution of t'ekctlies

octant of a sphericalshellof thickness tin is ^Dnn2)(Int whence the desired

product is

{{nn2dn)f{zK)= &/.n*exp(-\302\243jz)dn. G)

We take the spin of the atom as zero.

To obtain the probability distribution of the classical velocity, we must
find a connection between the quantum number n and the classical velocny
of aparticle in the orbital The classical
\302\243\342\200\236. kineticenergy \\Mvz is related to the
quantum energyF) by

We consider a system particles in volumeV.Let NP{i)ili}

of N be the number of
atoms with velocity magnitude, or speed, the range dv at v. This is evaluated
in

from G) and (8) by setting ,!>: - (iln/ilijib - (\\lL/hn)il\302\273. We have

W(*/i> = {-n;ji!exp(-\302\243./T)*i/\302\273

=
(9)
ii.;/^Yi.2cxp(-A/o:1/2i),/i..

From Chapter 6 we know that }. =

n/\302\273Q
=
(.V/L^^lnt^fMTK'2, so that the
fiidor staiidiiig to the left of v1 becomes

Thus

\342\226\240!n(A//2j[i)lV<:.\\p(-A/rV2r). (ll)

Tin's Maxwell velocity iIis(ribulion(Figure14.2).The quantity

is the P(i Mr is (lie

probability that a particie has its speedin i/r at i\". Numerical values of the root
mean square thermal velocity and the mean speed are given in Table !4.I,

using the results \302\273,\342\200\236

=
Ci/.W)\022 andf - (Sr/irU)\022from Problem !.
 i

i \\

\\
Figure t-l.2 Mawveil velocity distribution as a
\\
function of the in units of
probable speed tm(,
speed
* {2t/A/I\". Also
the most

shown
/
_ -
arc the mean speed c and ttie loot mean square \\
velocity i-AK1.

1/

Table I 4.1 M *e!ocilies

ofcculat \342\226\240 31273 K, iin 10*01115\"'

Gas \".\342\200\236, ? Gas \342\226\240\342\226\240,., 1

H, 18.4 16.9 Oi 4.6 4.2

He 13.1 12.1 Ar 4.3 40
H,n 6.2 5.7 Kr 2.86 2.63
Ne 5.8 53 Xe 2.27 2.09
N, 4.9 4.5 Free electron 1100. 1013.

Experimental verification. The velocity distribution of atoms of potassium

which exit from the slit of an oven has beenstudied by Marcus and McFee.*
The curve in Figure 14.3 compares the experimental results with the prediction
of A2) below; theagreement is excehent. We need an expressionfor the velocity
distribution of atoms that exit from a smatf hole1 in an oven. This distributionis
different from the velocity distribution within the oven, because the flux through

the ho^e factor, the

involves an extra velocity component normal to the watt.
The exit beam is weighted favor of atoins in of high velocity at the expenseof
those at low velocity. In proportion to thetr concentration in the oven,fast atoms

\342\200\242
P. M. Marcus and J. H. McFee,Recent research in molecular fceanw, ed. }. Esterman, Academic
Press, 1959.
1 In such experimenls a round bole is said io be small diameicr is less than a mean free paih
if ihe
of an aiom in ihe oven, tf the bole ti not smalt In tbis sense, [be flow of gas from it will be governed
\342\226\240\"\342\226\240
by lhetawsofbydrodynamic Bow and not by gas kinetics.
 i SecUtms and Me

10 -?*
9

7
>?

5
1

3 n
2 zj V
1

5 6 ? 10 U 12 13
Tiansit time

figure 14.3 Measured traiistnissio\302\273 points and calculated

Maxwell transmission curve for potassium atoms that exit from
an oven al a temperature E?\302\260C.The homontal axis is Ihe transit

lime utoms iransmiitcd. The inicnsity

of the is in arbitrary units;
the curve attd fhe points are normalized to the same maximum
value. After Marcus and McFce.

stitke the walis more often ihan slow atoms strike Ihe walls. The weightfactor
is the velocity
to the plane of ihe hole.The average
component ucosf? normal
of cos 0 over ihe forward hemisphere is jusl a numericalfactor, namely J. The

probability thai an atom which leavesthe hole will have a velocity between
v and v + dv deftnes ihe quantity PbciJ,v)iSv, where

wiih P,,(,Iwett given by (H). The distributionA2) of ihe transmission through a

hole is calledihe Maxwell transmission distribution

Collision Cross Sections and Mean FreePaths

We can estimate ihe collision rates of gas atoms viewed as rigid spheres. Two
aioms of diameter d will collide if their centers pass wiihin ihe distance4 of
eachother. From Figure 14.4 we see thai one collision will occur when an atom

has traversed an averagedistance

A3)
 Chapter 14: K'tnaic Theory

Figure 14.4 (a) Two rigid spheres will collide

if their centers pass within a distance d of each
cacliother, (b) An arom of diameter d which
travels a long distance L will sweep oul a
volume n^L, in the sense that it will collide
with any atom whose center lieswithin the

volume. If n is the concentration of atoms, the

averagenumber of ajoms in this volume is
i\\r,dlL. This is the number of collisions.Tlie

average dkwnCt between collisions is

L 1

where >i is the number of atoms per unit volume. Tiie length /is called the mean
freepath:it is the
average distance traveled by an atom between collisions.Our
result neglects the velocity of the target atoms.
We estimate the order of magnitude of the mean free path. If tlie atomic
diameter d is 2.2 A as for crosssectionac
[ielium, then die collision is

at= nit2 = C.14)B.2 x KT'crnJ \302\253=

15.3 x lO-i6cm2. A4)

The coiicenEration of moleculesofan idea! gas atO:Cand 1 atm is given by the

Losclimidt number

m0
= 2.69 x IOi9atumscnrJ. A5)

defined as the Avogadro number divided by the molar volume at O'C and 1aim
The Avogadro number is the number of molecules in one mole; tUe molar

volume is the volume occupied by one mole.We combine (M) a ad A5) to obtain
 Transport Processes

the mean free path under standard conditions:

/ = =
\342\200\2243\342\200\224 tttz = 2M * 1\302\260\"i Cm'
^16a'
]7pT6 2\\rT9 lO*7\"\"\"\"^

This length is about 1000 times larger than the diameter of an atom. The
associated collisionrateis

At a or Idynecm\022, the concentration of atorr.: s

pressure of I0~6atm
reducedby iG\026 and the mean free path is increasedto 25cm.At 10\026aim the
mean free path may not be smallin comparison with the dimensions of any
particular experimentalapparatus.Then we are in wliat is called the high \\ acui:m
region, also called the Knudscn region. We assume below that the meaii free
path is small in comparison with the relevant dimension of the
apparauis,

except in the section on laws of rarefiedgases.

TRANSPORT PROCESSES

Consider a system not in thermal equilibrium,but in a nonequilibrium steady

state with a constant How from one end of tiic system to the otUer. For example,
we may create a steady state noncquilibrium condition in a system by placing
opposite endsin thermal contact with large reservoirs at two different tempera'

tures. If reservoir 1 is at the higher temperature, energy will How through the

system from reservoir 1 to reservoir2. Energy flow in this direction will increase

the total entropy of reservoir 1 -f reservoir 2 + system. The temperature

gradient in the system is the driving force; the physical quantity that is trans-

transported through the specimen in this process is energy.

There is a linear region in most transport processes in which the flux is

directly proportional to the driving force;

flux s= (coefficient) x (driving force) , A7}

provided the force is not too large.Such a relation is called a linear phenome-
noiogicai law, such as Ohm's law for Thedefinition
the conduction of electricity.
of the flux density of a quantity A is:

3A
= flux density of A = net quantity oM transported across
unit area in unit time. (IS)
 Table 14.2 Summary of phcnomenologica! transport laws

Flux of
particle
Effect property Gradient Coefficient

Diffusion Number ~ DifTusmty/) J,

dz

dv.
Viscosity Transverse M ~~ Viscosity i;

\342\200\224
= Ct Thermal
Thermal Energy JB
^ \" \"z
K
conductivity conductiviiy

Electrical
ictricai Charge -~ =
E, Conductiviiy s J.
a:
conductivity

bols: nxx number of panicles per unit volume ip *=\302\273

elccirosuiicpolcniial
Z = mtan thermal speed = <Ji'J> E = electricfield intensity
/ \342\226\240=
mean free path q = elcciticchdrgt;
=
C|- heat capacity per unit volume M ^= mass of parucle
pu \302\253=
thermal energy per unit volume p \342\200\224
mass per unit volume
Fx/A *2- shear force per unit area - p ^ momentum
The net transport is the transport in one direction minus the transport in the
opposiie direction.Varioustransportlaws are summarized in Table 14.2.

Particle Diffusion

In Figure 14.5 we consider a system with one end in diffusive contact with a

reservoir at chemical potential /ij; the other end is in diffusive contact with a
reservoir at chemical potentialft2. The temperature is constant. If reservoir I
is at the higher chemical potential, then particles wili flow through the system
from reservoir 1 to reservoir 2. Particle flow in this direction will increase the

total entropy of reservoir 1 H- reservoir 2 -f system.

Consider particle diffusion, first when the difference of chemical potential is
caused by a difference in particle concentration. Tile flux density Jn is the
number of particles p;isshigthrough a'uait urea in unit time. Tltc driving force
of isothermaldiffusion is usually taken as thc\"gradicnt of the particle concentra-
concentration
along the system;

-,)n = -Dgradti. A9)

The relation ts called Fick's law; here D ts the putt tele diffusion constant or
diffusivity.

Particles travel freely of the order of the mean free path /

over distances
before they collide. We assume that tn a collision at position z the particles
come into a local equilibrium condition at the local chemicalpotentialjt{z) and
local concentration >\\{:). Let /. be the z component of the aiean free path. Across

the plaaeat z there is a particle flux density to the positive z direction equal to

4>j(z \342\200\224
/;)\302\243(and a flux density in the negative z direction equal to ~-{n{z +
L]cI. n(z L)
Here
~ means the particle concentration at z \342\200\224The
/,. net particle

Figure 14.5 \342\226\240

Opposite ends of the system are in diffusive

contact with reservoirs at chemicalpotentials /it and/ij. The

-. temperature is constant everywhere.
Chapter 14i Kinetic Theory

flux density is the averageoverail directions on a hemisphere of

B0)

We want to express the average value of cjg tn terms of?/. Here it = IcosO
ts the projection of the meanfree path, and c. \342\200\224
?cos<? is the projection of the
speed on the z axis.The average is taken over of a hemisphere,
the surface
beca
becauseall directions forward are equally likely. The eletnent of surface area
is 2xs'm0i}9. Thus

B1)

B2)

On comparison with A9) we see that the diiTusivtty is given by

The particle diffusion problemis the model for other transport problems. In
particle dilTusioii we are coneerncd with the transport of particles;in thermal

conductivity with the transport of energy by particles; in viscosity with the

transport of momentum by particles; and in electrical conductivity with the

transport of charge by particles. The linear transport coefficients that describe

tile processes are proportional to the particledilTusivity D,

Let pA denote the concentration of ihe physical quantity A. If A is a quantity

like charge or :r.:issthat has tile same value for all the molecules, then the flux

density of A in the z direction is

j; = e,<\302\273,>. (-\342\200\242')

ulierc
(i';) is the mean drift velocity of the p;irtidcs in tlie z directioii.'! lie drift
velocity is zero in thermal equilibrium.
If /{ is a quantity like energyor momentum that depends on the velocity of
a molecule, then we always find a similar expression;

= , B5)
\342\226\240>/ IaPa<v.)
 Thermal Conductivity

where fA is magnitude of the orderof unity.

a factor with The exact value o(fA
depends on the velocity dependence of A and may be calculated by the method
of the Boltztnann transport equation treated at the end of this chapter. For
simplicity we set fA~lin this discussion. By analogy with A9) for particle
diffusion, the phenomenologt'cal law for the transport of A is

126)

with the particle diffusjvity D given by B2).

Thermal Conductivity

Fourier's faw

Ju = \342\200\224
^Cg B7)

describes the energy llux density Ju in terms of the thermal conductivity K and
the temperaturegradient (Figure14.6).
This form assumes that there is a nci
transport of energyt
but not of particles. Another term must be addedif addi-

additional energy is transported by means of particle flow, as v,hen electrons flow

under the influence of an eiectricfield.
The
energy flux density in the z direction is

JJ =s ,
/>\342\200\236<!\342\200\242-> 128)

where ^o,i> is the mean drift velocity; pu is the energy density. This result is
valid within a factor of the order of unity, as discussed.By analogy with the

diffusion equation, the right-hand side is equalto

-DdpJAx = -D(tV,/cr)(i/t/i/x). B9)

Reservoir t Reservoir 2

Figure 1-1.6 Opposiie endsof the system arc in thermal

conijci wiih reservoirs at lempcratures r, and ij.
Chapter 14: Kinetic Theory

This describes the diffusion of energy. Now dpjet is just the heat capacity
per unit volume, denoted by Cy. Thus

-
-Ju -.DCYgradr; C0)

on comparison with B7) the thermalconductivity is

C1)

The thermal conductivity of a gas is independentof pressureuntil at very low

pressures the mean free path becomeslimited by the dimensions of the appara-

apparatus, rather than by intermolecular collisions. Until very low pressures are
attained there is no advantageto evacuating a Dewar vessel, because the heat
losses are independentof pressureas long as C1) applies.

Viscosity

Viscosity is a measureof the diffusion of momentum parallel to the How velocity

and transverseto the gradient of the flow velocity. Consider a gas with flow

velocity in the .x direction, with the Slow velocity gradient in the z direction. The
viscosity coefficient tj is defined by

C2)

Here vx is the x component of the flow velocity of the gas; px denotes the .v

component of momentum; and X. is the x componentofthe shearforce exerted

by the gas on a unit urea of thexj' plane normal to tlte z direction. By Newton's
second law of motion acts on the xy
a shear stress X. plane if the plane receives

a net flux density of x momentum J:{ps), because this flux density measures the
rate of change of the momentum of the plane,per unit area.
In diffusion the particle flux density is given by the number
in the z direction
density n times the mean drift velocity <i--> in the z direction, so that Jn: =
h<Uj>
= \342\200\224Ddnjdz. In the viscosity equation the transverse momentum density
is nMvx; its flux density in the z direction Is (hMdJO-)- By analogy with B6)

this flux density equals \342\200\224Dit(nMvxl'tlz, within a factor of the Order of unity.
With p
= nM as the mass density,

-Dp daJds = -n C3)

Thus, with D given by B3),

rj
=
Dp
= y-c! C4)

gives the coefficientof viscosity. The CGS unit of viscosity is called the poise.
The mean free path is / = \\jnd2n from A3), where d is the molecular diameier
and n is the con cent rat ion. Thus the viscosity may be expressed as

=
rt htcfiml1 , C5)

which is independentof the gas pressurp. Tlie independence fails at very high

pressures when the molecules arc nearly always in contact or at very low

pressures when the mean free path is longer than the dimensions of the
apparatus.
Robert Boyle In 1660 reported an early observation on the pressureinde-
independence of the damping of a pendulum in air:

Experiment 26 also that when the Receiver was full of Air,

We observd
the included Pendulumits Recursions about fifteen minutes (or a
continud
quarterof hour) before
an U left off swinging; and ikat after the t'xsnciionof
the Air, ihe Vibration of the same Pendulum {being fresh put into motion)
appeared not (by a minutes Walch) to last sensiblylonger.Sothat the event of
this experiment being other than we expected, scarce afforded us any oiher
satisfaction,than that of our not haviiuj umitleil to try it.

Although at implausible, this result is readily

first glance understood. With

decreasing pressure the rate of momentum-transfer collisionsdecreases, btit

each colliding particle comes from farther away. The largerthe distance, the

larger the momentum difference; the increasingmomentumtransfer per collision

cancels the decreasing collision rate.

It is easierto measurethe viscosity than the diffusivity. HD = r\\jp as predicted

by C4), then K is rclaiedto jj by

K - nCyfp. C6)

The observed values of the ratio Kp/rjCy14,3 are somewhat

given in Table
higher than the value unity predicted by our approximate calculations.Im-
Improved calculations of the kinetic coefficients K, D, i] take account of minor,
Chapter 14: Kinetic Theory

Tabie 14,3 Experimental values of K, D,ij, and Kp/tjCy at 0rC and l atm

Gas K, in mWcm\"' K~l D, incm*sM 1/, in ;\302\273poise we.

He 1.50 186. 2.40
Ar 0.18 0.158 210. 2.49
Hi 1.82 1.28 84. 1.91
N, 0.26 167. 1.91
Oj 0.27 _ 189. 1.90

but difficult, effects we have neglected; see the works cited in the general
references.

Comment, The dilTusivity is directly proportional to iheir viscosity.

of gas atoms The

diffusivily suspended in a liquid or gas is

of a parliclc a different probian: !hc viscosiiy of
tile sojvent opposes !hc diffusion of ihe suspended particle. We find D oc l/i;, where D
refersto ihe particles and r\\ refers to the liquid. The Stokes-Einstcinrebiion for suspended
particles is D = r/6n^R, where R is Ihe radius of !tie spherein suspension.

Comment, Tlie quaniily v =

tj/p is caJlcdrlIie kinemaiic viscosiiy;if C4) iiotds, v should
to ihe
be equal diffusii-ify D. The raiio i\\/p eiiicrs into iiydrodynamic iheory and into the
Reynold'snumber criierion for taminar flow.

Generalized Forces
The transfer of entropy from one parssystem to another is a consequence
of a
of any transport process. We can relate the rate of changeof entropy to ihe

flux density and of energy. By

of particles analogy with the thcrmodynaniic
identity at constant volume,

da = -c\\V- }~ (IN , C7)

we write the entropy current density Ja as

C8)
Let a denote the entropy density; let cafdt denote the net rate of change o(
entropy density at a fixed position r. Then, by the equation of continuity,

cajdt divjo. C9)

In a volume
unitelement the net rate of appearanceof entropy is equal to the
rate of productionga minusthe loss - div Jo attributed to the transportcurrent.
In a transfer process U and N are conserved.
The equation of continuity for
the energy density u is

~ \342\226\240=
-divju; D0)

the equation of continuity for the particle concentrationti is

{41)

Let us take the divergenceof Jo in C8);

divJa
= idivJ. + Ju-grad{l/t)

- (tt/x) div Ja
- Jn \342\226\240
grader). D2)

Let C7) refer to unit volume; we take a partial derivative with respect to time
to obtain the net rate of entropy change:

dd 1 cu i\\ en
~~ D3)
ct t ci tot'

We use D0H43) to rearrange C9) in a form suggestive of the ohntic power

dissipation:

3. = J. - \342\226\240
grailUM + J, gradi-;</r) , W)

Here Fu and Fa are generalized forcesdefined by

F. s grad(Vr); F, = grad(-;</r). D6)

Chapter 14: Kinetic Theory

In an isothermal processF, iii D6) may be written as Fn

==
{-I/t)grad/i or,
lit terms of ihe internal and externalparts of the chemical potential, as

Fn = -\"{i/t D7)

For an ideal gas n,Rt

==
xlog{n/nQ), so that grad/jjni = {r'n)gradn; for an

electrostatic <= \342\200\224

\302\273
potential gfad^\302\2431, q gradtp qE. Thus

-
Fn -UAJO^gradn -gE] D8)

How the particle flux density also has two terms, written as

>= ,
3\302\253 -i>ngrad\302\253 4- uflE D9)
where D, is the dtfTusjvity and p. is the mobility, which is the drift velocity per
unit eleciricfield.The raiio of the coefficients ofgradn to E is Djnp. in D9)
and rfnq in D8). These ratios must be equal, so that

E0)

which is calledihe Einsiein relation between ihe diffusivity and the mobility
for a classical gas.

Comment. We gain an advantage,for reasons relalcd to the thermodynamics of irrevers-

irreversible
processes, if we use FM and FH in D6) as the driving forces for the linear transport
processes. We write

Ju
=\342\200\242
Z,aiF, + L12FB; Jn = t2tF,,+L22F, , E1)

The Onsager relation of irreversible thermodynamics is that

~ E2)
L^B) Lj,i-B)

where 8 is the magneiic field intensity. If B = 0, then L;J

=
Ljf always.
For E2) to hold,
the driving forces F must be defined as in D6). Other definitions of the forces are perfcclly
valid, such as the pair grad i and grad n, but do not necessarily lead lo coefficients L that

saiisfy the Onsagcr relation.For a derivation see the book by Landau and Lifshiiz cited

in the general references.

 of Detailed Bohr.

KINETICS OF DETAILED BALANCE

Consider a system whh two states, one at energy A and one at energy -A. In
an ensemble of N such systems,N* are at A and N\" are al \342\200\224A,with \\ ==
N* + N\". To establish thermal equilibrium there must exbt sonic mechanism
whereby syslems can pass belwecnihe two stales. Consider the rate equaiion
for transitions into and out of the upperstate:

dN+/(lt
= uN~ - PK+ , E3)

wherea, /J may be functions of the temperature. The transitionrate from \342\200\224

to

+ ts directly proportional to the number of systems in the \342\200\224

state. The transi-
transition rate from -1- to \342\200\224
is directly proportional to the number of systems in the
4- state.

In thermal equilibrium (i/JV*/i/i) = 0, which can be satisfied only if

afp =
+
<N >/<N\">
=
exp(~2A/r) , E4)

the Boltzmann factor. This result expresses a relation between a(rj and /J(t) that

must be satisfied by any and every mechanism that assists in the transitions. As
an example, suppose that the transition + -+ \342\200\224
proceeds with the excitation
of a harmonic oscillatorfrom a state of energy se to a state of energy (s + I)e;
in the inverse process * + the oscillator goes from se to (s \342\200\224
i)e. In the

quantum mechanical theory of the oscillator it is shown that

-+ s + 1) s + 1
0 __
Prob{s __

for the excitation and de-excitation of the oscillator,a result derived in most
texts on quantum 'heory.The value of (s) isfound from the Planck distribution;

exp(E/T)
J _ W + i =
\342\200\242
W
W
<*\342\200\242>
<*> \342\200\224J
\302\253 <sy
W
<sy + = '
exp(e/r)- P exp(e/t)
- 1

so thai, with =
\302\243 2A to conserve energy,

aft - <5>/<s + 1)
=
exp(-2A/r). E5)

This satisfies the conditionE4).

The principle of detailed balance emerges as a generalization ofthisargument:
in thermal equilibrium the rate of any process that leads to a given state must
Chapter14t Kinetic Theory

equal exactly the rate of the inverse process that leads from the state. One
common application of the principle is to the Kirchhoff law for the absorption
and emission of radiationby a solid, already discussed in Chapter 4: radiation
of a wavelength that is absorbed strongly by a solid will also be emitted

strongly\342\200\224othenvise the specimen would heat up because it could not come into
thermal equilibrium wi!h the radiation.

ADVANCED TREATMENT:
BOLTZMANN TRANSPORT EQUATION

The classical theory of transport processesis based on the Boltzmann transport

equation. We work in the six-dimensional space of Cartesian coordinatesr mul
velocity v. Tiie classical distribution function /{r,v) is defined by ihe relation

f{t,\\)thdv = number of particles in drdv. E6)

Tlie Boltzmann equation is derived by the following argument. We consider

the effect of a time

displacement dt on the distribution function. The Liouville
theorem of classical
mechanics rells us that if we follow a volumeelementalong
a flowline the distribution is conserved:

f(t + i!t,r -+ tk.v + d\\) = /(f.r.v) , E7)

in the absence of collisions. With collisions

fit + dt.T + tle,\\ + dv) - f(t,r.v) = dt(ff/ct\\mijoni, E8)

Thus

dt(cf/c!) + dr- gradr/+(/v gradv/ = (/t(f//^)Mu- E9)

Let a denote the acceleration dv/tli; ihen

cflct + v
\342\226\240
grad, /+ a \342\226\240
gradv / \302\253
{df/ct)tM. F0)

This is the Bohzmann transport equation.

In many problems the collision lerm (cf/ct)eolJ may be treatedby the introduc-

of
introduction a relaxation time rc{r,v\\ defined by the equation
 ParticleDiffusion

Here/0 is the distribution function in thermal equilibrium. Do not confuserc

for relaxation time with t for temperature. Suppose thai a noncquilibrium
distribution of velocities is set up by external forceswhieh are suddenly removed.
The decay of the distribution towards equilibriumis then obtained (torn F1) as

- f0) f ~fo F2)

if we note that dfo/dt = 0 by definition of the equilibrium distribution. This

equation has the solution

F3)
ft is not exeluded that xc may be a function of r and v.
We combine E6), \302\24360),and F1) to obtain the Boitzmanu transport equa
iu the relaxation time approximation:

F4)

In the steady state cf/ct = 0 by definition.

Particle Diffusion

Consider an isotliermalsystem with a gradient of the particle concentration.

The steady-stateBoltzmann transport equation in the relaxation time approxi-
approximation becomes

v.dffdx* -(/-/0)/i{, F5)

where the nonequiltbritim distributionfunction/ varies along the x direciion.

We may write {65)to first order as

^fo-vsMJx,
/\302\273
F6)

where we have replaced cf/'dxby dfojJx. We can iterate to obtain higher order
solutions when desired. Thus the second order solution is

fi= fo- o^M'lx = -

vj^lfjdx
/\342\200\236 -f vxlr*tllfalilx\\ F7)

The iterationis necessary for the treatment of nonlinear effects.

Chapter 14: Kinetic Theory

Classical Distribution

Let/0 be the distribution function in the classical ijmil:

/0 = exp[(/* - e)/i], F8)

as in Chapter 6. We art; ai Iibeny io take whatever normalization for the
distribution function is most convenient becausethe iransport equation is
linear in / and f0. We can take the normalization as in rather
\302\24368) than as in

E6). Then

dfoftlx - (ilfofduWtifdx)
=
ifoh){dn/dx) , F9)

and the first order solution F6) for the nonequilibrium distribution becomes

/ = /o - (^J0/x)(dti/dx). G0)

The particle flux density in the x directionis

J/-$vxff>ie)de, G1)

where is the
\342\226\240Dfc) density of orbitals per unit volume per unit energy range:

\302\273, G2,

as in G.65) for a particle of spin zero. Thus

J/ = - idn/dx) G3)
JuI/01D(\302\243)f/E jiuJxJohM^k

The first integral vanishes because v3 is an odd function and fQ is an even func-
function of confirms that the net particle
vx. This flux vanishes for the equilibrium
distribution fa. The secondintegralwill not vanish.
Before evaluating the second integral, we have an opportunity to makeuse
of what we may know about the velocity dependence of the reiaxatton time ic-

Only for the sake of example we assume that r{ is constant, independent of

velocity; rc may then be taken out of the integral:
 Fermi'DiracDistribution

The integral may be written as

i JV/oO(E)<fe= ~j J(iMi'!)/0O(e)\302\253fe
= ,n/M , G5)

because ihe integralis just the kinetic energy density |nt of the particles. Here
= n is the concentration. The
J/0\342\202\254){\302\243)(/e particleflux density is

J' *=
-{nxJKtyiflnldx)
\302\253
-{z(z/M)(dn/(lx) , G6)

because fi
=
xlagn + constant. The result G6) is of the form of the diffusion
equation with the diffustvity

P = Vr/A/.= K\022>V G7)

Another possibleassumptionabout the relaxation time is that it is inversely

proportional to the velocity, as in rc ~ l/v, where the meanfreepalh 1isconstant.

Instead of G4) we have

J* = , G8)
~(dft/dx)(l/T)j(vx2/v)focD(\302\243)dB

and now the integral may be written as

,
J i>ic G9)

where c is the average speed. Thus

J.x \302\273
-i(^\302\273A)W/V^)
= ~\\mdn/dx) , (80)

and t!:e diffusivity is

=
\302\243> lie. (81)

Fermt-Dlrac Distribution
The distributionfunction is

- ^_
(82)
;XP[(\302\243 WAJ + ' \342\200\242
\342\226\240
Chapter 14: Kinetic Theory

To form dfo/dx as in F9) we need the derivative dfo/dfi. We argue bciow lhat

'tfJdH x 6{e-'y) , (83)

at low temperaturesr \302\253

ft. Here 5 is the Dirac delta function, which has the
for a general function
property F[c) that

Now consider the integral F{c){dfOl'dii)j\302\243.

j\302\243
At low temperatures dfQ/dfi is very
large for s =^ n and ts smail elsewhere. Unlessthe function F(\302\243)is very rapidly
varying near n we may take F{e)outside the integral, with the value Fin):

(85)

where we have used dfo/dn =*

~df0/dz. We have also used f0 = 0 for \302\243
= co.

At low temperatures /@) = 1; thus the right-hand side of (85) is just F[}i),
consistent with the delta function approximation. Thus

dfoftlx
= S(e
- v)d[i/dx. (86)
The particle fiux density is, from Giy

^ (87)

wheret{ is the relaxation time at the surface e = /( of the Fermisphere.The

integral has the Vaiue

M3n/2cf) - nlm , (88)

by use of Q([t) ~ 3;i/2ef at absolulczero,from G.!7), where zF = \\mvF2

defines tile velocity vf ort the Fermi surface.Thus

\302\253
JM' -(m,;i\302\273)Jii!Jx. (S9)

At absoluie zero ii@) = {h2j2in)Cji2n}2 J, whence

Jlt/ilx = {ilftV-mKJii')''1/\"\021}''\"/*

= 5(\302\243r/\302\273),/ii.V/.v, (90)
 Laws of Rartfitd Gaits

so that (S7) becomes

//= ~Bxt/3m)t:Fdn/dx
=
~\\ve\\dnfdx. (91)

The diffusivity is the coefficientotdn/dx:

D - \\vF\\ , (92)

closely similarin form to the resuh {77} for the classicaldistributionofvelocities.

In {92} the relaxation time is to be taken at the Fermi energy.
We see we can solve transport problemswhere the Fermi-Dirac distribution
applies, as in metals, as easily as where the classical approximation applies.

Electrical Conductivity
The isothermalelectricalconductivity a follows from the result for ihe panicle
difiusivity when we muliiply the particle flux density by the particle chargeq
and replace the gradient dji/dx of the chemical potential by the gradient
cfdq>fdx = ~-<j\302\243i of ihe external potential, where Ex is the .v component of the

electric field intensity. The electriccurrentdensity follows from {76}:

J,
- H\\/'\302\273)E; a =
uqhjni , (93)

for a classical gas with relaxation time xc. For the Fermi-Dirac distribution,
from (89},

= a *=
(94)
J, (nq2xc/m)E; nq'xjm.

LAWS OF RAREFIED GASES

Thus far in this chapter the discussion of transport has assumed that the

molecular mean free path is short in comparisonwith the dimensions of the

apparatus. At a gas pressure of i(T6atm at room temperature,the mean free

path ofa molecule is of the order of 25cm. The diameter of a laboratory vacuum
system conneciionmay be of the order of 25 cm, thus of the order of ihemean
free path. We may usefully draw a line here and denote pressureslower than

1 x 10~6atm as high vacuum. This pressure is approximately0.1Nra\021 or

1 x 10~6kgcm~2 or 7.6 x 30\"\"*mmHg or 7.6 x I(T4torr. The Knudsen

region of pressures is understood to be the regionin which the mean free path
is much grealer than the dimensions of the apparatus. A knowledge of the
behavior of gases in this pressure region is important in the use of high vacuum
pumps and allied equipment.
The terminology recommended by the Vacuum Society is expressed
American
in terms of torr, where 3 torr ;= 1 mm Hg = 1.333 x 3O\"~3bar=133.3Nnf2 =
1333dynecm~3; here 1 bar ~
!06dynecm~2 = 0.9S7 standard atmospheres.
Then:

high vacuum iO~3-i(T6 torr

very high vacuum 3O~6-3O~9 torr

ultra high vacuum below 3G~9 torr.

Flow of Molecules Through a Hole

in ilic Knudsen regime we do not need to solve a hydrodynamic flow
problem
in order to get the rate of efflux of gas molecules because the
through a hole,
moleculesdo not sec each other. We have merely to calculate the rale Jfl at
which molecules strike unit area of surface per unit time. We find for tlie flux
density

(95)

where n is the concentration and c is the mean speed of a gas molecule.To

prove (95), consider a unit cube containing n molecules. Each molecule strikes
the + z face ofthe cubejct times per unit time, so thattn unit time^nc, molecules
strike unit area.

We solve for ?, in terms of c. Becausec. *= c cos 0, we require the average of

cos# over a hemisphere:

2* cos 8 sin 1(8 j

=
J^2 \"\"
(96)
~2n 1'
[\"\\\\aedf

Therefore ?, \302\253
\\c, and (95) is obtained. The expression (95)for the flux forms
the basis for many calculations of gas flow in vacuum physics in the Knudsen
regime.
If A is the area of the hole, the iota! particle flux, which is the number of
moleculesper unit time, is

nS , (97)
 Flow of Molecules Through a Hols

S = l-ic. (98)
of
The conductances the hole is defined as the volume of gas per unit lime flowing
through the hole, with the volume taken at the actual pressure p of the gas. The
conductance is usually expressed in liters per second. For the average air
moleculeat T => 300 K we lQ4cms~';
have c x 4.7 x for a circular hole of
10cm diameter, (98) leads to conductanceof 917
a liter/sec, roughly 1000

liter/sec.
For a hole with a given conductance the total particle flux is proportional to
the concentration n or, because p
~ m, to the pressure p:

Here- we have defined the quantity

Q~pS, A00)

) A01)

Thecondition for zero net flux is

using the proportionality of c io t1'2.In the Knudsen regime equal pressures

do not imply zero net flux tf the temperatures two sides are different.
on the
At equal pressures gas will flow from the cold side to the hot side; zerogas
flow requires a higher pressure on the hot side. ...
Chapter !4: Kinetic Theory

Eft, - t2, Eq.A01)can be \\

- -(p, - p2)S = ~AQ , C03)

where

Example; Flow through a hns tube. We assume

molecules which strike the inner
that the
wail of the tube are rc-emittcd in is, the reflection at [he surface
ali directions; that
is
assumed to be diffuse. Thus when there is a net flow there is a net momentum transfer to
the tube, and we must provide a pressure head to supply the momentum transfer. Let u be
the velocity component of the gas moiecuicsparallel to the waii before striking the wall.

We estimate the momentum transfer to the waii on the assumption that every collision
wiih the wall transfers monicmurn Af <n). The rate of ttow down the tube is (M<\302\273>. where
A is the area ofilie opening.The rafe at which molecules strike ihe wall is, from (95)

\\nld)ic , . A05)

whered is the diameter and' L the length of the lube. The momentum transfer to the tube

must equal the force due to the pressure differential &p:

{nLMcM(u} =* AAp. A06)

We solve for tile flow velocity (u) to obtain

A07)
<u>--\302\243w:ln\302\260'\302\245mr

The net flux is

AO - n(u)A - Ap
~ = \342\200\224
S , A0$)

wher

S = tA\302\253/Ap= A09)
\342\200\224j-

is the conductance of the lube, defined analogously to the conductance of a hole, Eq.(97).
 Speed of a Pump

A more detailed calculation, with averages over the velocity distribution take
arefully, leads lo a conductance differing from A09) by a factor S/3*:

8 xAi 2t\302\253/J

The conductance of a tube cannot be larger than that of a bole with the same area. From
(98),A10), and A21)below.

This ratio will be larger than unity for 1L < 4d. In writing A06) we assumed implicitly

that every molecule hits ihc tube wall. This will tioi short tube.For our result
be true for a
valid we must
to be suppose that the tube is long enough to make the ratio A11] be small
compared to uniiy, which means

L \302\273id. A12)

Using our earlier example for the conductanceof a hole, we find ihat the conductance of
a tube 1 meter Jong and !0 cm in diameter is about 122 Jiler/sec, for air at 300 K.

Speed of a Pump
The speedofapump is defined similarly to thecOnductancoofaholeorofa tube;
it is defined as the volume pumped per unit time, with the volume taken at the
intake pressureof the pump. The same symbol S is used as for conductance;

(H3)

just as for i!ie conductance of two dectriaii conductorsin series.

Proof: Let pE denote the pressure al the input cad of the lube, and let p2

denote [lie puntp intake pressure at the output end of the tube. Continuity of

flux requires that

Chapter 14: Kinetic Theory

SO that

^i = (ll5)
S,W^
+
Pi ScS[ \\Sp SJ),
equivalent to A13).
The relation A13) for Scft explains why in high vacuum systems ihc connec-
connections between the pump and the vessel to be evacuatedmust be as short and of
as largd a diameteras possible.
A long and narrow connecting lube makes poor
use ofa high speed pump. Further, the speed of the pump itself cannot be larger
than the conductance of its awn aperture.

How rapidly does a pump with effective speed S evacuate a volume VI From
the ideal gas law p V
= Nx, and from the definition of pump speedanalogous
to Eq. (99) we find

iP^^E^Q^Pl A16)
dt V di V V

If thepump speedis independent of pressure, this differential equation has the

solution

W0-^0)cxp(-(/io); to
\302\253
V/S. A17)

For of! 00 litersconnected

a volume to pump with a speed of 100 liter/sec,the a

pressureshould decrease e per second. by 1

Any user of vacuum technology soon discovers the pumpdown of a that

vacuum system proceeds much more slowly in the high and ullrahigh vacuum

regions than expected on the basis ofpumping speedand system volume. The

desorption ofsurface gas predominates\342\200\224often by many orders of magnitude\342\200\224

over volume gas. The surface emits adsorbed molecules as fast as the pump
evacuates molecules from Uie volume.

SUMMARY
1. The probability that an atom has velocity in do at v is

\302\273
P(v)dv 4;:{.Vf/27rrK'Vexp{~Mi>V2

the Maxwell velocity distribution.

2. Diffusion is described
by

Jn = -Dgradtr, D = %cl ,

wiiere t is the mean speed and I is the mean free path.

3. Thermal conductivity
is described by

Ju =* -Kgradr; K = iC,,ff/ ,

where (V refers to unit volume.

4.- The coefficientof viscosity is given by

where p is the mass density.

5. According to the principle of detailed balance, in thermal equilibrium the

rateof any process that leads to a givenstatemust equal exactly the rate o( the
inverse processthai leadsfrom [he state.
6. The Boltzmann transport equation in the relaxationtimeapproximation is

+ f gradY /+ v \342\226\240
gmd, /- -Lzh.
jf

7. The electricalconductivity of a Fermi gas is

a \342\200\224
nqixjm ,

where xc is the relaxation time.

PROBLEMS

/. Mean speeds Maxwellian

In a distribution, fa) Show that the root mean

square velocity vtaa is

- \302\273
(MS)
<\302\273*>m
\302\253n\302\253 f3t/M)!'2.

Because <>3> - <Pjt2> + <w,:> + <\302\273/> and <^a>

- <\302\273/>
-
<fI2), it fol-

follows that

(_Vx3ylS
- (t/M)\023
\302\273
V^JV'1. A19)
Chapter 14: Kinetic Theory

The results can alsobe obtained directly from the expression in Chapter 3 for
ihe average kineticenergy of an ideal gas. (b) Show that the most probable
value of the speed vmP
is

- BT/MI'*. A20)
vmp

By most probable vaiue of ihe speed we mean the maximumof the Maxwell

distribution as a function of v. Notice that

i>mp
< v,mi. (c) Show lhal the mean
speedc is

c \302\253 = (8T/rcAf)m. A21)

j^dvvP(v)

The mean speed may also be written as <juj>. The ratio

v,mJZ~ J.0S6. A22)

fd) Show that ?., the mean of the absolutevalue of the z component of the
velocity of an atom, is

\"

?, s
(\\v:{>
= $\302\243
=
{2t/jiA/)\"\\ A23)

kinetic energy in a beam.

'
2. Mean (a) Find [he mean kinetic energy jji a beam
ofmoicculcs exits from that a small hole in an oven at temperature i. (b) Assume
now lhal the molecules are collimated by a second hole farther down the beam,
so thai the moiccuies that pass through ihe second hole have oniy a small

velocity component normal to ihe axisof emission.

What is ihe mean kinetic
energy? Continent: The moiecuiesin the beam do not collide and are not in real

thermal equilibrium after they have exited from ihc oven. The gas left in the
oven is depleted with respect lo fast moiecuies, and Ehe residua! gas will cooi
down iCH is not reheatedby heat flowing s'u (iirough the walls of the oven.

3. Ratio of thermal to electrical conductivity. Show for a classical gas of

particles of charge q that

K/ra - 3/2q2, or K/Ta

-
3/:s2/2^2
\342\226\240
A24)

in conventional units for Kand T. Thisis known as the Wiedemann-Franz ratio.

4. Thermal conductivity of metals. The thermal conductivity or copper at

room temperature is largely carried by the conduciion electrons, one per atom.
The mean free path of the electrons at 300K is of the orderof 400x 10~8cm.
The conduction electron concentration is 8 x 102Ipercm3. Esiimaiefa) the
electron contribution to the heat capacity; (b) the electroniccontribution to the

thermal conductivity; (c) the electrical conductivity. Specify units.

5. Boltzinaun equation and thermal conductivity. Consider a medium with

temperature gradient dx/dx. The particle concentration is constant,(a) Employ
the Boltzmann transport equation in the to
relaxation time approximation
find the first order nonequiHbrium classical distribution:

A25)

(b) Show that the energy flux in the x direction is

where vx2
=
2e/3m. fc) Evaluate the integral to obtainfor the thermal conduc-
K =
conductivity Sinijm.

6. Flow through a tube. Show that when a liquid flows through a narrow tube
under a pressure difference p between the ends, the total volume flowing ihrough

the lube in unit time is

A27)

where)/is the viscosity; L is the length; a is the radius.Assume that the flow is
laminar and that the flow
velocity at the walls of the tube is zero.

7. Speedof a tube. Show that for air at 20eC the speed ofa tube in liters per
second is given by, approximately,

L + id
(I2S)

where ihe length L and diameicr J are in centimeters; we have tried to correct
for end effects on a tube of finite length by treating the ends as two halves of a
hole in series with ihe tube.
Chapter 15

Propagation

HEAT CONDUCTION EQUATION 424

Dispersion Relation, (n Versus k 425

Penetration of Temperature Oscillation 426
Developmentof a Pulse 427
Diffusion with a Fixed Boundary Conditionat x ~0 429
\342\200\242'
Time-Independent Distribution 429

PROPAGATION OF SOUND WAVES IN GASES 430

ThermalRelaxation 432
Example: Heat Transfer in a Sound Wave 434

SUMMARY 435

PROBLEMS 436

1. Fourier Analysis of Pulse 436

2. Diffusion in Two and Three Dimensions 436
3. TemperatureVariations in Soil 437
4. Cooling of a Slab 437

5. p~n junction: Diffusion from a Fixed SurfaceConcentration 437

6. Heat Diffusion with Internal Sources 437

7. Critical Size of Nuclear Reactor 437
The purpose of this terminalchapteris to bring within the compass of the text
the most important problems propagation of heat and
in the the propagation
ofsound, both dassicai subjects that are part ofan educationin thermal physics,

HEAT CONDUCTION EQUATION

Consider first the derivation of the diffusion equation, which in found from the
Pick law A4.19) for !hc particle flux density:

J, a -/?ngrad\302\273 , (I)

where A, is the particle diffusivjty and n the particle concentration. The equation
of continuity,

*-'+ divJ, - 0, B)

assures that the number of particles is conserved. Because div grad ss V2,

substitution of A) in B) gives

= C)
y DnV2n.

This partial differential equation describes tlie time-dependent diffusion of the

particle concentration n.
The thermal conductivity equation is derivedsimilarly.By A4.27-14.30) we

have in a homogeneous medium

J_ = -/igradr. D)

The equation ofcontinuily for the energy density is

^ + div.l. =
0. M
 Dispersion Relation, w Versus k

where C is the heat capacity per unit volume. We combine D) and E) to obtain
the heatconductionequation

~ \302\253
Z),V2r; Ds = K/C. F)

This equation describesthe time-dependent diffusion of the temperature. The

equation is of tbc form of ihe particle diffusion equation C). The quantity Ds
is called the thermal diffusivity; fora gasii is approximatelyequalto the particle

diffusivity, as in (i 4.23}.

Comment. The eddy current equation of electromagnetic theory* has l\\\\c

C) and F). If 0 is (he magnetic field intensity, then

G)

The constant DB may be calledthe magnetic diffusivity and in SI is equal to I/ff/i; in CGS,
is % \342\200\224
c j^JZtJ^i,it itiiS Inc (if n^Cfisiotts (jcnctli) (ttoiej af^d is dirccfjy j^ro^orijoDiiJ to ttic
(skin depihK limes the frequency. When we have solved one equaiion, say C), we have

sohed lhree problems.

Dispersion Relation, to Versus k

We look for solutions of the diffusiviiy equation

DV20 = cOJct {8}

that have the wavclikeform

0 ^
0oexp[i{k-r- tor)] , (9)

with oj as the angular frequency and kas ]hc vvavevector. Plane wave analysis is
an excellent approach 10 this problem,
even though it will turn out that the
diffusion waves or heal waves are so highly damped ihai they arc hardly waves
Chapter IS: Propagation

at all Substitute (9}in (S) to obtain [he relation between k and to:

- ioi.
Dk2 A0)

A relation io{k) for a plane wave is calleda dispersionrelation.

Penetrationof Temperature Oscillalion

Consider the variation of temperature in the semi-infinitemedium z > 0 when

the temperature of the plane z = 0 is varied periodically with lime as

0(<U) = 0ocosw; , A1)

which is the real part of 0oexp(-iw/), for real 6Q. Then in ihe medium z > 0
the temperatureis

*= -
O(z,t) e0Rc[aip[i(kz at)]}

where Re denotes real part and i3'2 - {i - l}/%/2.Thus, with S s BDJqiI11,

- iwO)
6(z,i) = 0oRe{exp(-_-/a)exp[i(i/<5)
= - z/5). A3)
0ocxp(-z/5)cos(w(

The quantity 5 \342\226\240=

BZ)/u)}\022 has the dimensions of a lengih and represents
the

characteristic penetration depth of the lemperature variation: at this depth the

amplitudeof the oscillations of 0 is reduced by e\"J.The characteristic depth is
called skin the depth if we are dealing with the eddy current equation. The
'
wave is highly damped in ihe medium\342\200\224the wave amplitude decreases by e\"
in a distance equal to a \\vave!ength/2jr.
If the thermal diffusely of soil is taken as D s= 1 x 10\023cm2s'\"', then the
penetration depth of the diurnal cycie of heatingof the ground by the sun and
cooling of the ground by the night sky (w s= 0.73 x 10\"\024s\"\"!)is

L(diumal)
- B0/cu}1'1 as 5cm.

For the annual cycie,

L(aniiual) k lm.
 Development of a Pulse

A layer of tOcm of can h on top of a cciiar will lend 10 averageout day night
variations of surface lontperalure, but liic summer/winterwffxitiofi ;i! ihc top
of lhc cdi;tr requires several Miclcrs of earth, Actual values of the tliertir.ti
dtlTustvity arc sensitive to the composition and condition of lhc soii or rock.
Not'tcc that a figure of merit for cellar construction involves the thermal
dilTusivity, anrf not ihe conductivity alone.

Development of a Pulse
In additionto the wavelike solutions of the form (9), the diffusion equal ion has
severalother useful forms of solutions. We confirm by insertion in {8}thai

0(x,t) \302\253
DnDi)~inexp{-x2J4Dt) A4)

is a soiution. The proportionality factorhas beenchosen so that

*~ I. A5)
j*y{x,t)dx

The soiutionA4} corresponds to the time developmenl ofa pulse whichat t = 0

has the form ofa Dirac delta function S(x}t sharply localized at x = 0, and zero
elsewhere.
The might
pulse be a temperature pulse, as when a pulsed laser or pulsed
electron beam a surface briefly. Let Q be the quantity
heats of heat deposited on
the surface, per unit area. The temperature distribution is then given by

0{x,t) A6)

where Cv is the heat capacity per unit volume of the material. The function is
plotted in Figure15.1. The factor 2 arises because all heat is assumedto flow
inwards from the surface, while for the solution A4) symmetrical flow was
assumed. Another example of the applicationofA4) is the diffusion of impurities
deposited on the surfaceofa semiconductor, to form a p-~ujunction inside ihe
semiconductor.
The pulse spreads out with increasing time. The mean square value of x is

given by
/-
X)dx ~2Dit A7)

after evaluating the Gaussian integrals. The root mean squarevalue is

. . .
A-Imi(/)
- (x1I'1 * (IDty1. A8)
Chapter I Si Propegai

= 1.0 = o.s
s.b

0.8 ,^\\

\"^
0.6
/ =4.0

\342\200\224^

0.4

Figure 15.1 Piol of spieadof temperature pulse whh lime. Tor 4nD = 1,
from Eq. A6). At i = 0 (he pulse is a delta function.

Comment, This result shows thai the width of tile distribution increases as t\022t which is
a general characteristic of diffusion and random walk problems in one dimension. It is
quile unlike the molion of a wave pulse in a nondisperstve medium, which is a medium

for which <o = rfc, where v is the constant velocity.The connection with Brownian motion
or the random walk problem follows if we let t0 be die duration of each step of a random

walk; then r = Ni0. Mscre .\\' is the number of iteps. it follows that

XrBU(i) = {2Dto)llZN1'2 , A9)

so that the rnts dtsplacemcni ts propodional to the square toot of the number of steps.
This is the result observed iri sludics of il.c Bfowiiian inolion, the random motion of

suspensions of small particles in liquids.

 Time-Independent Diitribution

Diffusion with a Fixed Boundary Condition at x ~ 0

If a solution of (8) is differentiated or integrated with respect to any of its
independent variables, the result may again be a solution. An important example
is obtainedby integrating A4} with respect to x;

=*-= [\"dscxpf-s^icrfu, B0)

where u = x/DDt)U2. Here we have introducedthe error function defined by

->
\302\253u
erf\302\253 = \342\200\224
jo
<feexp(-s2). B1}

Tables of the error function are readily available.The error function has the
properties

erf{0) = 0; lim erf(x) = 1. B2)

Of particular practical interestdiffusion of heat or of particles
is the into an

infinite solid from a surface at x \342\200\224

0, with the fixed boundary condition 0 = 0o
at x = 0 and 0 0 at x co. (For [ < 0 we assume 0=0 everywhere.)The
~ =*

solutionis
0(x,t)
-
0o[l
- zrf(x/DDt)U2)l B3)

Again we see that the distance at which 0(x,t)reachesa specified value is propor-

proportional to DDiI11. The application of this solution to the dilfusion of impurities

into a semiconductor is discussed in a problem.

Time-Independent Distribution

Let us look at a solution of (S) that is independent of the time. The diffusivily
equation reduces to lite Laplace equation

V20 =-- 0. B4)

Consider a semi-infinite medium bounded by the plane 2 = 0 and extending

along the positive z axis.Let the temperature vary sintisoidaliy in the boundary
plane;
0(x,y\\0) - 0os B5)
Chapter ]5: Propagation

The solution ofB4) in the medium is

0{x,y,z)= 0o5inkxexp[~kz). B6)

The
temperature variation is damped exponentially with the distance from the

boundary plane. The temperaturedistributionin the time-independent problem

must be maintained by constant healsourceson the boundary plane
z = 0.

PROPAGATION OF SOUND WAVES IN GASES

Results developed earlier in ifiis book can be applied to the study ofsound waves
in gases. Thermal effects are important in this problem. Let dp(x,t) denote the
pressure associatedwith the sound wave; the form of the wave may be written

as

dp = 6poenp[Hkx - on)}, B7)

where k is the wsvevecior and w is the angular frequency. The wave propagates
in the .V direction.

We suppose the equasion of state is that ofan idealgas:

pV
= Nz , or p = pr/A-f , B8)

where p ~ NM/V is the mass density, and M is the mass of a molecule. The
force equation referred to unit volume is

Here u is the x component of the velocity of a volume element. The motion is

subject to the equation of continuity

dp/dt + div(py) = 0 , C0)

or, in one dimension,

dp/dt + S{pu)/dx - 0. C!)

The thermodynamic identity is

dU + pdV = jda , C2a)

 Propagation of Sound Waves in Gases

which can also be written

da
-_ + p_iV
du
= C2b)
Ty.
If we assume (pending discussion beiow) that there is no entropy exchange
during the passage of a sound wave, Eq. C2b) becomes

Cy(cr/ui) + (p/V)lcV/ct) = 0 , C3)

where Cv is the heat capacity at constant volume, per unit volume. We can re-
rewrite the second term in terms of dp/ct becausep - NMfV &\\\\d(l/V)[dV/ct)
=

-~(\\/p)(dp/dt). Now the thermodynamic identity appears as

Cv(dx/di)
-
{p/p)(ep/ct) - 0. C4)

Let us define the fractional deviations s, 0 by

P
= Pod + s); t ~ T0(l + 0) , C5)

where p0, t0 are the densityand temperature in the absence of the sound wave.
We assume that a
u, s, Shave the form of travelingwave;exp[t(Jcx - wO].The
three equatioas B9), C1), C4) that govern the motion now become

-iwpu 4- ik{(?po/M)s + (pTofM)O] = 0; C6)

- ia)pos + ik{pous + pn) = 0; C7)

-iwiQt,y0 + icu{pfp)p0s
k 0. C8)

We assume that at sufficiently small wave amplitudes it is a good approxima-

to
approximation neglect in these equations terms in the squares and cross products of
u.s, and 0. For example, pu ~ po{\\ + s)u becomes po\\\\ if the cross product su is
ncgiecicd. The equations thus reduce to, with the subscripts dropped from

p and r,

cott - (kx/M)s- {kxjMH

= 0; C9)

as ~ ku = 0; D0)

rCyO
-
ps = 0; or CVB
- us = 0 , D1)
Chapter IS; Propagation

where n is the concentration. Theseequationshave a solution only if

\"
to = fyt/M)llik , . D2)

where y = (Cy + n)jCv = \302\243,/\302\243(,

in our units. The velocity of sound is

it,
= den/dk * D3)

Tiiis result applies to nionatomic gases from the lowest frequenciesup to high

frequencies only by the requirementthai the acoustic

limned wavelength should

be much larger than the mean free path of the atoms. This requirement is the
criterion for the appHcabiiiiy of she hydtodynamic approach embodied m the
force equation B9).

Thermal Relaxation

Wiih polyatomic gases {43}is valid at low frequencies, the frequency is

but as
increasedthere is a transition frequency region above which (he velocity of
\342\226\240
sound increases. The transition region belwcen low frequency and high fre-

frequency propagation is associated with relaxation effects.

Thermal relaxationdescribesthe establishment of thermal equilibrium in a

system. Energy dissipation results when al! parts ofa system are not at ihesame
temperature; the dissipation is strongest when the period of the heating and
coolinghalf-ejcle in the sound wave is comparable with the lime required for
heat exchange between the different
degrees of freedom of the system. In
polyatomicgases under standard conditions there are lime delays of the order
of 10~5s in Hie transfer of energy between the internal vibrational stales of a
molecule and the external translation states.
LetthehealcapacityCi and temperature tj = to(\\ -f 0,) refer to the internal
states, while Cy and t =: to(l + 0) refer to the translations! states. Then C4)

becomes

- = 0 ,
Ct(dxt/dt) \\ (cz/ct) (p/p)(dp/ci) D4)

or, in pSacc of QS),

-kotoCiQi
- ia>x0CvO + ioj{p/p)pQs
- 0. D5)

Suppose thai the transfer of energy between ihe internal and externalslateshas
the characteristic tune delay tQ such that

t)/t0 D6)
 koO, = @ - 0,)/!Q. D7)

Here t0 is called tiie relaxation time. There will be separate relaxation times for
the rotational-iranslational transfer and the vibrationaf-iranslaiionaltransfer.
We combine C9), D0), D5) and D7) to obtain the dispersionrelalion

,48,

where CV, Cp refer to the translational states alone. In the low frequency limit
(otQ I
\302\253 and

k2 = ftj*(A//r) -^-i\342\200\224i =
w^Af/vor) \342\226\240 D9)

where y0 is the low frequency limit of the total heal capacity ratio [C^ + C\\)/

(O 4- Ct). The low frequency limit of the velocity of sound is

11,@)= (Vqt/A/)\022. E0)

In the high frequency limit cur0 1

\302\273 and

J = w2(A//yxt). E1)

Here yM refers only to the translations! stales; at high frequencies the internal
stales are not excited by the sound wave. The high frequency limit of the velocity
of sound is

*,(cc) = G*t/Af)\022. E2)

Values of y0 are given in Table 15.1;if no internal stales at all are excited,
=
y\302\273 I
The wave is ai(enua(ed when k is complex; the imaginary part of k gives the
pressure attenuation coefficient a. From D8) it is found that the maximum
absorption per wavelength occurs when cu = 2n,'t0 and is given approximately

by

~
H C. Cy C, ,,,.
2 Cp Cv -f d
Chapter IS: Propm

Table 15.1 Ralio Cp Cy ~ for gascS

\342\226\240;

Gas Temperature, CC

Air 17 1.403
HjO 100 1.324
H2 15 1.410
Oa -LSI 1.450
15 1-401
200 1.396
2000 1.303
CO, 15 1.304
Ar 15 1.668
He -180 1.660

kois: For imoniiomic Idea! gai,C,/Cr - S/J = 1.667, a!

tof ftf 3nd tic. roi a qj^equuc q&$ sJ 2 Ic in peruiurc ni^ii

as for Oj and Hj at room (cmpe^aturci ai levnperalufcs

suAicicr\302\273tly high lo excite also the v?branooal motion,
C,!Ct- = 9/7 - 1.2S6, as for O, aj 2000=C.The values given
<lrc of v^i spplicsblc to slslic processes miti Eo sound waives
in ihe ijmil of low frequencies. For very high frequency

\302\253
5.3 is appftcabk.
\342\226\240/^

For CO2 gasa( the relaxation frequency of 20kHz under standard conditions
the intensity is observed to decreaseby 1/e in about A wavelengths\342\200\224a massive

absorption, in agreement with theory.

Example: Heat transfer in a sound Have. Equation {33)expressesthe iserttropic assump-

assumption:ihe ncglecis ihe thermal conduciivity
equation which gives rise to some transfer of
thefniat energy Within ihc sound wsvc betweensuccessivewsrm and cool half cycles. The
0 musi be modified lo lake account
assumpiion thai da \302\253= of heal (low. The heat conduction

equaiion F) may be wtiuen as

Kch/cx2 = x edict , E4)

where 8 is (he entropy density. Then C4)becomes

Cytftjdt)
-
lpfp)idpjdt) - Ktfh/dx2) ,

= -Ktk28. .
E5)
icaps
When we use this in place of {4\\\\, the dispersion relation lj{1.) becomes

With W = K/ai. At low frequencies Wk* is much Smaller lhan Cy, so thai the sound velocity

essentiallythe condiiion }., where

/ \302\253 the molecular mean fiec path and
I is X is the wave-
length of the sound wave. The attenuation of the pressure oscillation is given by the imag-
imaginary pan of the wavcveclor k and is denoted by a. The result from E6) in the low frequency
region Wk1 \302\253
Cr is that

* = f/o ~ l)pK<a2j2i\\3Cp , E7)

where Ce refers lo unit volume.

SUMMARY

1. The equation is the partial differential

heat conduction equation that follows
when the phenomenologicaitransport equation(here the Fourier iavv) is
combined with the equation of continuity. We obtain

= D, s K/C.
^ D,V2r;

2. The time-dependent diffusion equation and the eddy current equation have
the same form, so that their solutions may be translated from the solutions
of the heat conduction equation, these being often more familiar in the
Hterature.
3. Frequently H is useful to construct solutions in the form of superpositions
of plane waves of the form

0^ 0oexp[/(k-r -tot)}.

The differential equation then gives the relation between <y and k, called the
dispersion relation of the problem.
4. The propagation of depends on the rate of exchange
sound waves in gases of

energy between the translation^!, rotaUonal, and vibrationai motionsof a

moiecuie. A low frequency sound wave is describedby isentropic, and not
isothermal, parameters\342\200\224a result that seems paradoxical at first sight.
Chapter IS; Propagation

PROBLEMS

Fourier
/\342\226\240
analysts of pulse. Consider a distribution ihat at the initial time
1= 0 has ihc form of a Dirac delta function iSf.v). A delta function can be
represented by a Fourier integral:

0{x,0)= Six)
^~j^<!kcxp{ikxl
E8)

At later times the pulse becomes

~ - a)!)}, E9)
Ik f\"
=
0{x,t) dktxp[i(kx
\342\200\242)-\"\342\226\240\"

or, by use of A0),

D[x,t) = \342\200\224 dk exp{ikx - Dk2t). F0)

J^

Evaluate the integral to obtain the result A4). The melhodcan be extended to
describe the time development of any distribution given at r ~ 0. If the distribu-
distributionis f{x,0), then by the definition of [he delta function

/(x,0) - - x'). F1)

Jdx'f(x',0)S(x

The time development of 5{x - x') is

0(x - x',t) \302\273

D7i/)f)^
+
exp[-(.v
- x'J/4Dt] , F2)

by A4}.TSms at time t the distribution f{x,0) lias evolved to

fix,!) = {4nDi)~{
fdx'f{x\\0)cxp[-(x
-
x'J/4Dtl F3)

This is a powerful general solution-

2. Diffusion in ma and three dimensions, (a) Show that tlte diffusion equa [ion
in two dimensions admits [he solurion

02{t)
- (C2/!)exp{-~r2/4Dt) F4)

and in tlirce dimensions

o,F - {C3/iin)tsp{~r/4Di); F5)

(b) Evaluate the constants C2 and C3. These solutionsare analogous to C4)
and describe ihc evoltiuon of a delta function at t = 0.

3. Temperature variations in soil. Consider a hypothetical climate in which

boih ihe duiiy and the annual variationsofthe
temperatureare purely sinusoidal,
wiih amplitudes 0d =* IOC. The mean annual temperature0a s= 1OX. Take
[lieihcrmaidifTusivityofthesoiltobel x IO~3 cm1 s\021. What is Uic minimum
depih at which water pipes shouldbe buried in this climate?

4* Cooling of a slab. Suppose a hot slab of thickness 2a and initial uniform

temperature 8t is suddenly immersed into water of temperature 0o < 0u
thereby reducing the temperature at the surface of the slab abruptly to 80 and
keeping it iherc. Expandthe temperature in the slab in a Fourier series. After
some time all but the longest wavelength Fouriercomponent ofihe temperature
will have decayed, and then the temperature distribution becomes sinusoidal.
After what lime will the temperature difference between the centerof Uie slab
and its surface decay to 0.0! of the initial difference 0s
~
0O?

5, p~-n junction: diffusion surface concentration. Suppose a sili-

from a fixed
silicon crystal is /j-type doped with a concentration of ua \342\200\224
1016cm~3 of boron

atoms. If the crystal slab is heated in an atmosphere containing phosphorus

atoms, the latter will diffuse as donors with a concentration nd(x) into the semi-
semiconductor. They will form a p-n junction at [hat depth at which na
=
nd.
Assume that the diffusion conditions are such that the phosphorus concenu:;-
lion at the surface is mainiained at nd@) = 10l7cm'\023. Take the diffusion
coefficient of donors to beO s= iO~13cm2s\"l,What is the value of ihe constant
C in the equation ,\\\" =* Ct1'2, where .x is ihe depth of the p-n junctionand i is

ihe lime?

i5. Heat diffusion with internal sources. When internal heat sources are pres-
present, the continuity equation E) must be modified to read

C~ + divju = gu , Ffi)
ct

where gu
is the
generation rate per unit volume. Examples includeJoule
heat
heat generated in a wire; heat from the radioactive decay trace elements of
inside ihe Eanli or ihe Moon. Givean expression for the temperature rise ai die
a
center of (a) cylindrical wire and (b) iiic spherical Earth, on the assumption
that ga is independent of position and is constant with time.

7, Critical size of nuclear reactor. Extend the considerations of the preceding

problem to particle diffusion, and assume thai there is a net particle generalion
rate i/B that is proportional to the local parsicle concentration,gn \342\200\224
n/t0, here
\302\253

f0 is a characteristic time constant. Suchbehaviordescribesthe neutron genera-

generationin a nuclear of\"SU
reactor. The value off0 depends on die concentraiion
Chapter IS: Propagal

nuclei; if no surface losses took place,the neutron concentration would grow

as exp(f/f0}. Consider a reactorin the shape of a cube of volume I? and assume
that surface losses pin the neutron surface concentration at zero. Show that
Eq. C), augmented
if by a generation =
term g, n/t0, has solutionsof the form

n(x,y,z,!} c F7)

where kxL, kyL and k:L are integer multiples of n. Give the functional depen-
dependence of the net klt ky, k. and r0, and show that
time constant i\"; on
for at least

one of the solutions of the form F7) the neutron concentration grows with time

if L exceeds a criltcal value Ltli(. ExpressLc,-n as a function of Dn and @. In

actual nuclear reactors (his increaseis ultimately halted because the neutron
generation rate gn decreases with increasing temperature.
Appendix A

Some Integrals Containing

Exponentials

THE GAUSS INTEGRAL

Let

(i)
J - <x> JO

The following trick is used to evaluate /o. Write (i) in terms of a different
integration variable:

- B)
/\342\200\236
j'~mp(-y')cly.

Multiply (i) and B) and convert ihe result to a double integral:

V - J_>^exp(-xa)*cJ_*\"exp(-.y2)<fy
j\" J_*Jexp
= - (x1 + y')ilxdy.
C)
This is an integral over the entire *->\342\226\240
plane. Convert to polar coordinates r and
tp, as shown in Figure A.S. Then, x1 \342\200\242}\342\200\242
y1
= r1, and the area element dA =

dx dy becomes dA =
ritnltp:

=
'\302\2602
= 2i
Jo
[j\020<=^-r')r'lr\\dif

Becauseof d[exp{~r2)] = - 2exp(- r2)rjr, the integral over r is elementary:

\"
V - -n Jf4exp(-r2)] \302\273
-fnexpl-r1)]'
- n.
L J'-\302\260

D)
 C iFitc\302\243r@'5 LOfl

area element iU = rrfrtltp.

GENERALIZED GAUSS INTEGRALS,

AND GAMMA FUNCTION INTEGRALS

Integralsof the form

Im
- 2 > -1) , E)
JoVexp(-x2)(k, (m

where m need not be an integer, may be reducedJo the widely tabuiatcd gamrna
function V{:), by the substitutions x2
~ y, 2dx
~
y~idy:

Im
= >dy - V(n f I), (m
- l F)

The integral in F) may be viewed as the definition of f(z) for nonititeger positive
\\alues of r.
The gammafunction satisfies the recursion rdalion

to
It iseasily obtained for n > 0 from F) by integration by parts, and it is used

extend the definition F) of T{z) to negative values of z. By using (?) repeatedly

it is always possible to reduce F{z) for arbitrary argument lo a value in the

interval 0 < z < !.

 The Stirling Approximation

Form = 0,11 = -J; from D):

Urn is an even integer, m \342\200\224

21 > 0, n is a half-integer, and i! ~ 1 \342\200\224
}, then we find
by repeated application of G), with the aid of (8), that

h,
= ry + j) =
(/
-
i) x (i - j) x
\342\200\242
\342\226\240
\342\200\242
x x
\302\247 i x u\"!. (9)

Form - l.ii -0:

/, = 2
Jo*.xexp(-*!)ifc
=
JoV'<0'
= HI) ~ 1. A0)

If in is an odd integer, in = 2i H- I >: 1, n is an integer, n = / 2: 0, and we find

similarly, with the aid of A0),

'lit i - 2 JoV*lexp(-x')J.\\-
= HI + 1) = I x (I- 1) (HI

The gamma function for positive integer argument is simply ihe factorialof
the integer preceding the argumeni.

THE STIRLING APPROXIMATION

For large values of\302\253, n! can be approximated by

A2a)

logn! * lj\\og2n + (n + J)logH

- n +
j\342\200\224

Here the term 1/12/? is the first term of nn expansion by powers of and
!.'\302\273,

for omitted order terms this of order

0{i/\302\2732) slands higher in expansion, l/\302\273
Some Integrals Containing Exponential*

or higher. In practice,even the lerm I/I2n is usually omitted. Its principalrole

is to check on the accuracy of the
approximation. If the effect of the I/12n-
correction introduces only a change below the desired accuracy, ihe entire
expression has the desiredaccuracy.
To derive A2) we write, in accordance with A1),

\"! = \" \342\200\242 A3>

jo\302\260x\"e\"llx J0\"exP[/(x>]'h

/(x)=)ilogx-x A4)

We make the substituiion

x= n + yii* = n(l + j'lr1) , dx - rfdy. A5)

Then

J{X)
= I! lOgl! - It + S(j') ,

9(y) = npog A7)

With these,

exP[/(-v)]= irV-'e (IS)

A9)

The function g(y) has its maximumat y

= 0; g@) = 0. Using the Taylor
expansionof the logarithm,

log(l + s) = s - is' + Js1- |s\" B0)

= we expand
with s (.y2/\"I'2. g{y):

B0
 The Stirling Approximation

In tile limit n -\342\226\272

a}, s ~ 0, and all but llie first term in B1) vanish, and the
integral in A9) becomes

= On)'11 , B2)
/ J\"exp(-j.72)rfi.

with the aid of D). If B2) is insertedinto A9) the result is identical to A2a) except
for the correction term 1/I2n. Its derivation is a bit tedious. We work with
Iogii! and wrile

log/ii = {login + +
(\302\253 iltog'i
- ii + \342\200\224
+
\302\260(i)-
B3a)

If we replace h by n - 1,

Iog(n
-
1)! - ^Iog2n + (n
-

A A
<23b>
M
- 1 \\n

We sublracl B3b) from B3a):

logn!
- log(n - 1I - log
ii I
- loS\"
jj-^-jT;

= (n + J)logn - (ii
-
5)log(il
- 1) - 1

where all omitted terms are now at least of order I/a3.The two terms in A
can be combined:

If this is inserted into B4), we find

4 = (n-i)iog B6)
Some Integrals Containing Exponentials

~
For large n the logarithm may be expanded according io B0),with s \342\200\224
\\/n:

r + i + i +
\302\260i B7)

B8)

If this is inserted in B6) we see that A - \\/\\2.

We are often interested not in n\\ but oniy in Iog/i!, and only to an accuracy
such that the relative error between an approximate value of Iog/i! and the
true valuedecreases with increasing Such
\302\273. an approximation is obtained by
neglecting all terms in (I2b) that increase less rapidly than linearly with n:

Iogu! =s if
log ii B9)
Appendix B

Temperature Scales

DEFINITION OF THE KELVIN SCALE

Numerical values of temperature*-1 are not expressedin practice in terms of the

fundamental temperature r, whose unit is the unit of energy, but on the (absolute)

thermodynamic temperature scale T, the Kelvin scale, whose unit is the kclvin,
symbol K. The kelvin was defined in 1954 by international agreement as ihe
fraction 1/273.16of the temperature T, of the iriple point of pure water.Henr;,
by this definition, T, s 273.16 K, exactly.This temperature is O.GI K above the
atmospheric-pressure freezing point of water (the ice poini), To ~ 273.15 K.
The triple point is more easily and accurately reproducible than the ice poini.
The triple point establishes itself automatically tn any clean evacuaied vessel
that is partially backfilledwith pure water and cooled until part but not all of
the water is frozen, leadingto an equilibrium between solid ice, liquid water,
and the water vapor above the ice-water mixture.

The Celsius temperature scale / is defined in terms of the Kelvin scale, by

t a T - 273.15K. (I)

on
Temperatures this scale are expressed in degrees Celsius, symbol 'C. Tem-
Temperature differences have liie same value on both Kelvin and Celsius scales.
The conversion factor kB between the fundamental temperature i and the
Kelvin temperature,

t = kBT , B)

*
We appreciate ihe assisiance of Norman E. Phillips in ihe preparation of this appendix.
1
The ullimale survey of the slale of development of precise lempcralure measurement is Ihe

try. Tfic
proceedings arc published urider the SiSn.C
liiic. Vol. 1:C O. Fairchild, editor: Reir ihoU. 19-10. This volume is largely obiolcie. Vol. 2: E. C.
W.Jfc. editor; Koicltotd, \\<jS5. Although ger reflecting the State of ihe art, this volwnc is still
4..tfful for ils thorough inlioductory i!isi s of p/tEittpfci ofvanous methods of tc
nfcU
edili r; Rcitihold, (962- Pc/liapsthc *ii c becauseof its tiitroduLioty JisfUiiion uf
ipks of various methods of tcm letiis. Vol. 4 C pans): H. H. Plumb, edilor;
is called the Boiumann constant. Its numerical value must be determined
experimentally; [lie best current value* is

= x
ka A.350662 0.000044)
\302\261 10~t6ergK\"\\ C)

The value of the BolUniannconstant is determined with the aid of certain

mode!syslcms structures are
whose
sufficiently simple that one can calculate
the energy distributionof !he quantum states, and from it the entropy as a
funclion of the energy, a = a(li). The fundamental lemperalure as a function
of Ihe energy is i(U) (ca/cU)~l. =\342\226\240
Examples of mode! syslems used in !he

determination of k8 are the following:

(a) Idealgas. iti particle concentration all gases behave as
the limit of low
idea!gases,satisfying pV NkBT. One obiahis/cB by measuring the pV product
=

of a known amount of gas al a known kelvin tcmperalure T, extrapolated to

vanishing pressure. The determination of the number of particles N invariably
involves the Avogadro constanl NA, independently known.

(A) Black body radiation. We can obtain k,, by filling Utc measured spectral
dislributionof black body a of known Kelvin temperature T to the P!;mck

radialion law (Cliapler 4). Because this law involves t through ihe ralioIioj/x ~

tici>/kBT, this dcterminalion requires the independent knowledgeof Planck's

constant.

(c) Spinpammagnetistn. In of vanishing interaction the magnetic

the limit
moment M of a syslem of spins .V field B, at temperature t, is
in a magnetic

given by Eq. C.46). Various paramagnetic salts, such as cerousmagnesium

nitrate (CMN) are good approximations to nomnieractmg spin systems if the

temperature is not too low. By filling measured values of M as a function of BjT

to C.46) we can determine Ihe ratio mfkB, where in is the intrinsic magnetic

moment of the eleclron, known independently. Usually only the low-field

portion used, is in which case ihe number of spins must also be known, which

tnvoives again A^. Precision results require correctionfor weak residual spin
interactions, similar to corrections for particle interactions in a gas.
The kB value given in C) is a weighted average of several deterrninations.

With an uncertainly ofaboui 32 parts per million,it is oneof the least accurately
known fundamenial constants. Most of this uncertainty is due to the difficulty
of the measurements and to the nonideaHty of the systems used for these
measurements.About 5 parts per million are due to the limited accuracywith
which h and NA are known.

\342\200\242
E. R. Cohen and B. N. Taylor, J. Phys. Chem. Reference Dam 2, No. 4 A973).
 Primary and Secondary Thermometers

When expressing temperature as conventionalKeivin temperature 7\" rather

than fundamental temperature t, it is customary to absorb the Bohzmann

consiam into the definhionof a conventional entropy 5,

S s ksa. D)

The relation$Q = xda between reversible heat transfer and entropy transfer
then becomes

\302\253=
TtlS.
dQ E}

PRIMARY AND SECONDARY THERMOMETERS

Any accurately measurable physical property A' whose value is an accurately

known function ofthe may be used as a therniomelric
temperature, A' *= X{T],
parameter10 measure
temperature System possessing the property
the of ihc
.V and of any system in thermal equilibrium with it. Used til this way. the
system with the property X is a thermometer. The principles underlying
the niost commonly used thermometers are listed in Tables 13.1 and 13.2. The
thermometers listed in Table 13.2are called secondary thermometers, defined
as thermometers whose temperature dependenceX(T) must be calibrated

empirically, by comparison with another thermometer whose calibrationis

already known. The calibration of all secondary ihcrmonieicrs must ultimately
be traceable to a primary thermometer. But once calibrated, secondary ther-
thermometers arc easier to use and arc more reproduciblethan the primary ther-
thermometersavailable at the sametemperature.
Any calculable model system that can be used to determinethe value of the

Boltzmann constant kB ean be used as a primary thermometer, and the three

model systems diseussed above are the most important primary thermometers
(TableB.I).
The precision and accuracy of thermometers vary greatly. Precision is
expressed by the variation AT observed when the same temperatureis measured
at different times with the same instrument. Accuracy is expressed by the
uncertainty AT with which the thermometer reproduces the true Kelvin scale.
Secondarythermometers based on electrical resistance measurements may
achieve a precision of 1 part in I05. The precision of thermometers based on
mechaniea!pressure measurements is much poorer, particularly at low pres-
pressures. For example, helium vapor pressure thermometers at the iower end of
their useful range have a precision of about 1 part in 103.The accuracy of

secondary thermometers is limited by the accuracyofthe primary thermometers

 Table B.I Principles of the mosl important primary thermomete

Model sysicm and

propeny utilised

Idea! gas
a| Static pressure ai constam voliim
b) Speed of sound
Magnetic susccplib'iljtyof noninteractm,

spin sjsii;m
a) Eiccironic spins
b) Nuclear.spins
Black body radiaiion

note: The coiumn \"Defining cquaiion\" indicates which equation underlies

various nuniiicaiiiics uiay be nccilccl. The temperature rjmecsqtiotcd ;iro the

and diluted CMNii

 Thcrtt'oJyttanuc Thet

Table B,2 Principles of the most important secondary

thermometers

Useful range
Physical property taK

Thermoelectric votlageof thermocouples* 400-1400

Thermal expansion ofliquid in glass 200-400
Electrical resistance
metals* 14-700
semiconductors (germaniumI 0.05-77
commeEciai carbon resistors' 0.05-20
Vapor pressure of Jiqucfied gas
4
He 1-5.2
0.3-3.2
p
ltimate limits.
\342\200\242
Used as interpolating instrument in the 1PTS.
'
Widely used as cryogenic laboratory ihernion
must be individually calibrated to deliver usable

used lo calibrate Ihem.The accuracy of primary thermometers is limited hy

their relatively poor precision by residual variations between

and different

thermometers. As a of
rough estimate, the present-day accuracy primary
thermometers is about 1 part in 104 above 100 K, about 1 part in 103 around

1K, and about 1 part in 102 near 0.01 K,

THERMODYNAMIC THERMOMETRY

It is possiblelo perform primary thermometry without relyingon the theoreti-

theoretically known properties of simple mode! systems, by somehow utilizing the
relationE). We
give three examples.

(a) Carnot cycle. Consider a Carnot cycleoperating between a known tem-

poralure '!\\ and the unknown temperature 7\\, Because of entropy conservation
the heat transfers at the two temperatures satisfy Qt/Tv
\302\253
Q2/T2. The un-
unknown temperature can be determined by measuring the ratio of the \\\\\\o hem

transfers. The: method is hot very practical.

(b) Magneticcabriinetry. Suppose paramagnetic substance is initially at a a

known temperature in a magnetic field B{. Let the substance be cooled

7\\, by

isentropic demagnetization to the unknown temperature T2. If now a known

Temperature Scales

smaii amount dQ of hem is added to the substance, its entropy is raised by

dS = dQjT2. The substanceis then isenlropically re-magnetized, and ihc
magnetic field B2 determinedat which
is the temperature has returned exacily
to T,. The field B2 will be found siightiy different than Bt:B2 = #i + <l&.
Entropy conservation requires

cIS = dQ/T2 \302\253

SG,,Bi)
-
5G,,^,) = &S/cB)TdB. F)
From the
thermodynamic identity for the Hclmholtz free energy for a magnetiz-

magnetizable
substance,

dF = -SdT - MilB , G)
one obtains, by the usual cross-differentiation, the Maxwell relation

(cS/dB)T= {dM/3T)B. (8)

We insert (8) into F) to find the expression for the unknown temperature:

72 - UTQ/<lB)(dM/dT)B. (9)

The quantities <fQ at T \342\200\224

T2anddBzlT - Tt are known,and the temperature
derivative of M at 7\" =
T, and JS = B, is easily measured. The method makes
no assumptions about the ideality of [he paramagnetic substance, and it has

therefore been used extensively at low temperatures.

(c) Clausim-Clapeyron thermometry. The melting temperature Tm of a sub-
substance varies with pressure p according to the Clausius-Clapeyron equationof
Chapter10:

dTJdp =
TmAV/&H , A0)

where AV is the volume change during melting, and AH the latent heat of
fusion.If both quantitieshave been measured as functions of pressure, A0) can
be integrated;

= (U)
7*2/7,
cxpJPl(AK/AH)rfp.

If 7, andp, are known, a measure men! of the pressure p% at which the unknown

temperature T2 is the equilibrium

melting temperature permits calculation of
 International Practical Temperature Scale {IPTS)

T2 from (U). By utilization of the strong temperature dependence of the

solidification pressureof liquid ^He, the method lias been used as an alternative
to magnetic thermometry at low temperatures.

INTERNATIONAL PRACTICAL TEMPERATURE

SCALE (IPTS)

Many known phase equilibrium temperatures can be reproduced far more

precisely than the accuracy with which their exact location scale
on the Kelvin
can be determined
by primary thermometry. To facilitate practical thermometry,
a number of easily
reproducible phase equilibrium temperatures have been
determined as accuratelyas possible have been assigned best values to
and

define an InternationalPractical Scale (IPTS). On the IPTS the

Temperature

selectedequilibrium are treated as if their temperatures

points were known to be
exactlyequalto theirassignedvalues.Intermediate are determined temperatures

by a precisely specified interpolation procedure is chosen to reproduce the that

true Kelvin scale as accuratelyas possible. present version of the scale is

The

IPTS68, adopted 1968 by international in

agreement, covering temperatures
from the triple point of hydrogen {13.81K) upward.* Table B.3 tlte gives

assigned temperatures for IPTS68.

In the range between 13.81K and 903.89 K, which is themelting point of
antimony, a platinum resistance thermometer is used as the interpolating
instrument.In the range from 903.89 1337.58 K., the meltingpoint
K. to of gold,
a platinum-piatinum/rhodiuni thermocouple is used. Above 1337.58 K black

body radiation is used.

Below 13.81 K. no precisely defined procedure has been agreed, In the range
between 5.2 K. and scales based on the vapor
13.S1K. various pressure of

hydrogen are in practical use. Below 5.21 K, the critical point of 4Hc( down to

about 0.3 K, the 1958 and 1962 helium scales* are widely used as de facto
extensions of 1PTS68. The 1958 4He scale relates the vapor pressure of 4Heto

the temperature T; the 1962 3He scale uses the vapor pressureof 3He.
As the accuracy of primary temperature measurements improves, errors in
practical scales such as IPTS become uncovered, leadingeventually to revision

of the practical scales. Table B.3 lists someerrors now believed to exist in
IPTS68.

\342\200\242
Sec, for eiampte, American Iniiiiuie of Physics handbook, 3rd cd., McGraw-Hill,1972;Sectio
Hcaf, M, W\". Zcmansky, ciiiiot. Contains complete original references-
Tempera e Scales

Table B.3 Assigned temperatures of lhe lnternalional

Pracjical Temperature ScaleOf I96S

Equilibrium poinl
Substance Type in K in K

13.81
6 B50lorr) 17.042
b 20.28
b 27.402
54.361
\342\200\242> 90.188
i 273.16 exact
b 373-15 0.025
505-tISI 0.044
692.43 0.066
f 1235.08
f 1337.58

noi-e: Except for the triple poinisand the 17.042 K point, all
fG^mlEoriu *irc tHosc at a pressure of one st-mdarti airrio^pncre\302\273
p0 - l0J,325Nmwi <
= 760iorr). The I7.O42K poinl isihe
boiling point ot hydrogen at 25OtOff^ llic notations f, bt and
f tti lhe second colurnn refer to uiplc poinis* boiling points,
and freezing points.* The lasi column contains esiimatcs of
errors known to exisr, from Physics Today 29, No. 12,p. 19
(Dec. 1976).
\342\200\242
Alt data from lhe American luxituie of Phyws handbook,
3rded., McGraw-Hill.
1972; Seciion 4: Heat, M. W. Zcmansky,
ediior.
Appendix C
Poisson Distribution

ThePoisson distribution law is a famous result of probability ihcory.The result

Is useful in tUe design and analysis of countingexperiments in physics, biology,

operations research, and engineering. The statistical m ethods w e have developed

tend themselves to an elegant derivationof the Poisson law, which is concerned
with the occurrence of small numbers of objects in randomsampting processes,

it is also called the law of small numbers. If on the average there is one bad
penny in a thousand, what is ihe probability that N bad pennies will be found in
a given sample of one hundred pennies? The problem was first considered and
solved in a remarkablestudy of the rote of luck, in criminal and civil law trials

In France in the early nineteenth century.

We derive ihe Poisson distribution taw with the aid of a mode* system that

consists of a large number R of independentlatticesitesin thermal and diffusive

contact wilh a gas. The gas servesas a reservoir. Each lattice site may adsorb
zero or oneatom.We want to find Ihe probabilities

that a total of 0, !, 2,.... N,.... atoms are adsorbed ou the R sites, if v/e are

given the average number <N> of adsorbedatomsover an ensemble of similar

systems.
Consider a system composedofa singlesiie.It isconvenient to set the binding

energy of an atom to the site as zero. The identical form for the distribution is
found if a binding energy is included in the calculation. The Gibbs sum is

where the term A is proportional to the probability the site is occupied,and

the term ! is proportional to the probabilliy the she is vacant.Thus the absolute

probability ihat ihe site Is occupiedis

J ~ 1 -r /.\"
{>

The actual value of /, is delermined by

ihe condition of the gas in the reservoir,
Polsson Distribution

because for diffusive comae! beivveen i\\\\c lattice and the reservoir we must have

by the argument of Chapier 5. The evaluation of /.(gas) for an ideal gas was

given in Chapier 6.
We now extend [he treatment10R independent siics. Then

(<*)

By the argument used in Chapter 1 we know lhal the binomial expansion of

{O + \302\251)Bor (! + /.)* counts once and only once every stale of Ihe system of
R sites. Each site has two alternative states, namely O for vacant or for
\302\251

occupied, which corresponds in the Gibbs sum to the term ! for and
X\302\260 the

term / for )}.

In the low-occupancylimit of/ 1
\302\253 we have / s /.,whence

fR- },R E)

is theaverage total number of adsorbed atoms. The Poisson distribution is

concerned with this low-occupancy limit.We can now write D) as

F)

Next we let the number increase without limit, while holding the
of sites R
average number of occupied sites <N> constant. The Poissondistribution is

concerned with infrequent events! By the definition of the exponential function

we have

exp<N> , G)

(}R)N
JM = exp<N>= \302\253p(;j!)
-
I\342\200\224- (8)

Ttie last step here is the expansion of the exponential funclion in a power series.
 The term in '/!\" in 3\"^, is proportional lo the probability F(A') that .V sites
are occupied. With the Gibbs sum as the normalisation Factor we ha\\c in the
limit of large l(:

C)

or, because/.K = <A'> from E),

A0)

'
This is the Poissondistribution law.

Particular interest attaches to the probability P@) that none of the sites
is occupied. From A0) we find, with <N>\302\260
= 1 and 0! = I,

P@) = exp(-<N\302\273; logP(O)

- -< (II)

Thus the probability of zero occupancy is simply related to ihc averagenumber

(N) of occupied suggests a simpleexperimental
sites. This procedure for the

determination of <N>: just count the systems that have no adsorbed atoms.
Values of P(A') for several values of <N> are given in Table CM. Plots are
given in Figure C.I for <N> = 0.5,1, 2, and 3.

<N> \302\253p(-W >)

Table C.l Values of the Poisson disiIribution ft inction PIN)
N!

0.1 0.3 0.5 0.7 0.9 1 2 3 4 5

f@) 0.9048 0.740S 0.6065 0.4966 0.4066 0.3679 0.1353 0.0498 0.0183 0.0067
PW 0.0905 0.2222 0.3033 0.3476 0.3659 0.3679 0.2707 0.1494 0.0733 0.0337
FB) 0.0045 0.0333 0.0758 0.1217 0.1647 0.1839 0.2707 0.2240 0.1465 0.0842
FC) 0.0002 0.0033 0.0126 0.0284 0.0494 0.0613 0.1804 0.2240 0.1954 0.140
W) 0.0003 0.0016 0.0050 0.0111 0.0153 0.0902 0.16S0 0.1954 0.175
P{5) 0.0002 0.0007 0.0020 0.0031 0.0361 0.100S 0.1563 0.17
0.0001 0.0003 0.00050.0120 00504 0JO42 0.14
PG) 0.0001 0.0034 0.0216 0.0595 0.10
0.0O09 0.0081 0.0298 0.06
F(9) 0.0002 0.0027 O.OI32 0.03
1 0.0008 0.0053 0.0S
 Tisttibuti

0.6
=
(N> 0.5
<,V> = I
-
gO.4 0.4

0.2
0.2

0 J J - t 1 s , .
) 1 2 3 4 5 )
W _

\302\2430.2

LLjl

Example:Incorrectand correct counting of states, (a) The Gibbssum for the R sites is nai

Jwi = 1 + X + )} + -I3 4- - ' ' + )*. {12}

Why noi?

(b) Thccorrcci suns is

A3)

Ji!
[R - W N!

is lilc binomial cocflicicm. Nolc that tjill.V) is Ihc number of independent states of Ihe

system for a given number of adsorbed alor.is .V. The Gibbs sum is a sum over ail stales.

Example: Elementary demotion of P@). I.ei a Iota! of R bacteria be distribulcd at

randoln among L dishes.Each dish is viewt j as a syslen: of many siles 10 which a bacterium
 PohsonDhtributior.

may aiiach.TlieL dishes represent an ensemble of Lidcnticalsyslems.

The average number
of bacieria per dish is

<N> \342\200\224
R/L. {14}

Each time a bacleriumis distributed, ihe probability that a given dish will receive thai
bacterium is t/L The probability [he given dish will not receive the bacterium is

A5)

The probability in R tries lhat the given dish will receive no baderia is

/><0)
= ~~Y A6)
(l

because the faaor (i 5) eniers on eachtry.

Wemay\302\253ri(e(l6)as

(.7,
lW-(l -<\302\243>)'.

by use of<.V> = R/L. We know iliai in Hie lirail of large R,

rap(-<N\302\273= limfi -\342\200\224)

, A8)

!>y llie Jcrmilion of Ihc cxpoocnlu! funclron. Thus for R I and

\302\273 L I we
\302\273 have

P@) = cxp(-<N\302\273 A9)

in aercemcni wjih (U).

PROBLEMS

/. Random pulses. A radioactive source emus alpha particles which arc

counteda! an average rate of Oiie per second, (a) What is the probability of
counting exactly iO alpha particlesin 5s?(b)Ofcounting2m 1 s?{c) Of counting
none in 5 s? The answers to (a) and {b}are not identical.
2. Approach to Gaussian distribution. Showthat the Poisson function P{N) ~
\342\226\240(N>'\"'exp{ \342\200\224<W)}/A'! closely approaches a Gaussian function in form, for

large (A'>. That is, show when N k closeto <;V> thai

PIN) * Aexpt-tyS
- (N}I] ,

where A, B are quantities to be determined by you. Hint: Work with !oeP{A?};

use the Stirling approximation.In the Gaussian form both A and B are functions
of <N>; in the development of the Poissonfunction you may find A, B are
functions of N, but the two forms of A, B are closelyequivalent over the range in
which the exponential factor has significant values.
Appendix D

Pressure

Let a pressureps be applied normal to ihe faces of a cube filled wilh a gas or
liquid in quantum state s. By elementary mechanics {Chapter 3} the pressure
is equal to

Pl~ -dUJdV , {1}

where Vs is tlie energy of the system in the states.We can also write the pressure
as

Pl- ~(dUJdV\\ , B)
where (dU/,tV), denotes ihe expcciaiton value\" of dUfdV over the siatc s at

volume y. Ii is important that we can calculate p by {2} which is at a fixed

volume with no ambiguity about the identity of the selected state 5. whereas
(!) involves following the state through two volumes. Kand V + dVt with some

possible doubt whether the state remains ihe same.The ensemble average

pressure p is the average of p, over the states represented in the ensemble:

f>W--(Wl,> C)
Because the number of states in the ensemble is constant, the entropy is constant,

so that the derivative is at constant entropy.We may therefore write

D) uses the energy of the system

The result expressed as V(a,V,...}; that is,
as a function of the volume V and the entropy a\342\200\224not the temperature r. It is
the entropy and not the temperaturethat is to be held constant in the

differentiation.

\342\200\242
The equivalence of (t) and B) is an example of ihe Hellmana-Feynman theorem of quantur

resped to a parameter X are related by dVfdX

=>
<|A*7<*A|). The derivation may be found o
p. 1192of C. Cohen-Tannoudji, B. Diu, and F. Laloc. Quamum mechanic*, Wiley, [977; see als
E. Merzbacher,Quantum mechanics, 2nd ed., Wiley, 1970; p. 442.
Appendix E
Negative Temperature

The result of Problem 2.2 for the entropy of a spin system as a function of the
energy in a magnetic field is plotted here in Figure E.I. Notice the region in

which Ca/cV)s is negative (Figure E.2).Negative r means that the population

of the upper state ts greater than the population of the lower state. When this

condition obtains we say that the population is inverted, as illustrated in

Figure E.3.
The concept of negative lemperaturets physically meaningful for a system
that satisfiesthe following restrictions:(a) There must be a finite upper limit to

the spectrum of energy states, for otherwise a system at a negative temperature

would have an infinite energy. A freely moving particle or a harmonic oscillator
cannothave negative temperatures, for there is no upper boundon theirenergies.
Thus
only certain degrees of freedom of a particle can be at a negative tempera-

\\
\342\226\240

\\

= +0 \\
r = -0\\
jr
0 0.2 0.4 0.6 0.8 1.0

Figure E.1 Entropy as funciion of energy for a iwo siaic sysicm.

The scparaiion of the siaiea is c ~ I in ibis example. In ihe
Icfi-liandsideof ihe figure da/cU is posiiive, so ihal r is posiiivc.
On ihe riglii-hand side ca/cU is negaiive and i is negaiive.
 Negmlrt Temp,,

+6

+ 5
1

+4
/
+3
+2
K -f 1

.\342\200\224\342\200\224
Migy 0\342\200\224\342\200\224
\302\2610
\302\247 5 o 2 0 4 0.6 0
1 ^1
-\342\226\240
I

-1

-3 /

-4 !/

_5

Figure E.2 Temperature versus energy for Ihe two

stale system. Here

Noiice energy is not a maximum

tiiai ihe at x ~ + x,
but is 3 maximum al i = -0.

ture: the nuclear spiu magnetic field is ihe degreeof freedom

orientalion in a
most commonly considered in experiments at negative temperatures,(b) The
system must be in internal thermal equilibrium. Thismeansihestates must have

occupancies in accord with the Bolumann factor taken for the appropriate

negative temperature, (c) The states that are at a negative temperature must be
isolated and inaccessible to those states of the body that arc at a positive

temperature.
The ordinary translations! and vibrational degrees of freedom of a body
have an entropy that increasesthe energy increases,in contrast
without limit as
to the two stale or spin system of Figure E.I. If a incieases without limit, then i
is always positive. The exchange of energy between a system at a negative
temperature a nd a system that can only have a positive temperature(because of
Negative Temperature

I I I I I I I I I I

Figure E.3 Possible spirt distributions for various positive and

negative tempera!ures.The magneiic fietd is direcied upward. The
negative spin temperaturescannot Jasi indefinitely because of weak
coupting betweenspins and the lattice. The lattice can oniy be at a
positive temperature becauseils enefgy level spectrum is unbounded
on top. The downward-directed spins, as at i = turn
\342\200\224r^, over one
by one, I hereby releasing energy to the lattice and approaching
equilibrium with the lattice common posiiivctemperature.
a! a A

nuclear spin system at negative temperature may reiax qutie slowly,

over a time of minutes or hours; during this time experiments at
negative temperaturesmay be carried out.

an unbounded spectrum) will iead always to an equilibrium configuration in

which both systems are at a positive temperature.

Negative temperatures correspondto higher energies than positive tempera-

temperatures. When a system at a negative temperature is brought into contact with a

system at a positive temperature, energy will be transfused from the negative

temperature to the positive temperature.Negative temperatures are hotter
than positive temperatures.
The temperaturescalefrom coid to hot runs + 0 K,.... 4- 300 K,..., H- go K,

-03K -300 K,..., -OK. Notethat if a system at -300K b brought

into thermalcontactwith an idem teal system at 300 K, the final equilibrium
temperature is not 0 K, but is \302\261
co K.

Nuclear and electron spin systemscanbepromoted to negative temperatures

by suitable radio frequency techniques.If a spin resonance experiment is
carried out on a spin system at negati\\e temperature, resonant emission of
energy is obtainedinsteadof resonant absorption.* A negative temperature
system is useful as an rf amplifier in radio astronomy where weak signalsmust
be amplified.

Abragam have carried out an elegantseriesofexperiments

and Proctor* on

calorimetry with systems at negative temperatures.Working with a LiF crystal,

they established one temperaturein the system of Li nuclear spins and another
temperaturein the system of F nuclear spins. In a strong staiic magnetic field

the two thermal systems are essentially isolated,but in the Earth's magneiic
field the energy levelsoverlapand the two systems rapidly approach equilibrium
among themselves(mixing). It is possible to determine the temperature of ihc
systems before and after the systems 3re allowedto mix.Abragam and Proctor

found that if both systems were initially at positive temperatures they attained
a common positive temperatureon being brought tnto thermal contact. If boih
systems were preparedinitially at negative temperatures, they attained a
common negative temperature on being brought into thermal contact, if
at
prepared one a positive temperatureand the other at a negative temperature,
then an intermediate temperaturewas attained on mixing, warmer than the
initial positive temperature and coolerthan the initial negative tempcraiure.

FURTHER REFERENCES
ON NEGATIVE TEMPERATURE

N. F. Ramsey, \"Thermodynamics and statistical mechanics at negative absolute

temperature,\" Physical Review 103, 20A956).
M. J. Klein, \"Negativeabsolute temperature,\" Physical Review 104, 5S9 (i956).

\342\200\242
E. M. Puicelland R. V. Pound, Physical Review 81,279 A951).
1 A. Abragam and W. G. Proctor,Physical Review 106.16Q(l<>57); 109,1441 A958).
Index

Abragam, H.. 350, 463 Hiack body radiation, 98

Abraham, B. M.. 209 Bockris,J. O. M.,248
Absolute activity, 139 Bolununn constant, 4i, 45, 446
Absorption refrigerator, 25S Boiizmann factor. 58, 61
Absorptivity, 97 Bolutiminn transport equation. 403, 42!
Acceptor, 357, 363 Born, M.. tOfi

Accessible state, 29 Bose-EinStcin Condensate, 202

Activation energy, reactions, 2 Bose-Einstein distribution, 157, 159
Active transport, 145 Boson,152
Boson gas, 199
Age, Sun, Hi condensation, 205
Air conditioners, 235 degenerate, 221
room, 258 fluctuation, 222

Alloy, binary, !6, 310. 331 one dimension, 222

gold in silicon, 331 Boson system, 223
mixing energy, 3IS.33O Bridgman, P. W., 279
solidification ranee, 33!
system, 16 CMN, 348, 448
Anderson, A. C, 219 Carbonmonoxidepoisoning,i46
Amonini, E.. 142 Camot coefficient,
Atmosphere, 126,145,179 refrigerator performance, 234
Atoms, in a box, 74 Camot cycle, 236
velocity distribution, 394 ideal gas, 237
Average value, 22 Ihermodynamic thcrmomctry, 449
Avogadro constant, 2S2 Camot efficiency, 230
Carnot engine,photon, 258
Camot inequality, 228, 232
Barclay, I A., 345 Carnot Jiqucfier, 351
Barnes,C. B.,345 Carrier concentration,intrinsic. 362
Barometric pressure, 125 Carrier lifetime. 3SS
equation, 126 Carrier recombination, 383
Battery, electrochemical, 129 Catalyst. 271
Bertram, B., 210 Celsius temperature scate, 4-15
Belts, D.S.. 342 Centrifuge, 145
Binary alloy, 16,310.331 Cerium magnesium nitrate, 348, 448
Binary model systems, 10 Chapeiiier, M, 350
Binomial distribution. 22 Chauikasekhar limit, 222

expansion. 14 Characteristic height, atmosphere, \\26

BiopoJynwr growth, 273 Cliau, V. H., 350

Chemical equilibria, 266 Critical point, 291
Chemical potential. 118, JJ9, J43, J61 van dcr WaaJs gas, 2%9
and entropy, J3I Critical radius, nucleation, 295
equivalent definition, J4S Critical size, nuclear reactor, 437
external, J49 Crilical temperature, 276
ideal gas, J20, J69 gases,277
internal, J22, 12-4 Croft, A. J., 340
mobile magnetic particles,J27 Cryogenics, 333
near absolute zero, 199 Crystal transformation, 307
loiaj. 122. J24 Crystalline mixture, 319
two phase equilibrium, 330 Curie temperature, 298

Chemical reaction, 266 Cycle, Carnot, 236

Chemical work, 250
idea! gas, 25! DNA molecule, S3
Classical distribution, 410 Daunt, J. G, 348

function, J6J de Bruyn, R., 345

Classicallimit, 160 De Maeyer, L., 270
Classicalregime, 74, 153,159,358 Debye T1 Saw, 106
Claude cycle, 341 Dcbyetemperature, 105
helium liqucfier, 351 Debye theory, 102
Ciausius-Clapeyron
equation, 281 Degenerate Fermi gas, 219
Clayton, D. D.,222 Degenerate gas, !82
Closed system, 29 Degeneratesemiconductors, 355. 365
Coefficient, refrigerator performance, 234 Demagnetization, cooling, 352
Coefficient, viscosity, 402 isenttopic, 346
Coexistence curve, 278 nuclear, 348
Cohen, E. R.,446 .
Density of orbitals, 187,218
Cohen-Tannoudji, C.,459 Density testates, 186
Collision cross sections, 395 effective, in semiconductors, 360
Collision rates, 395 effective mass, 360
Concentration fluctuations, 147 Detailed balance,kinetics, 407

Condensed phase, 303 principle of, 271

Conductance, hole, 415 Deviation, integrated, 54

tube, 416 Diatomic molecules, rotation, 84

Conduction band, 355 Diesel engine, 180
Conduction electrons, Differential relations, 70
semiconductors,355 Diffusion

Conductivity, electrical, 4!3, 421 current flow, 379

intrinsic, 387 equation, 437
thermal, 401,421 fixed boundary, 429
Configuration, most probable, 33, 35 heat, 437
Convectivc isentropic equilibrium, 179 internal heat sources, 437
Cooling, demagnetization, 352 particle, 399,409

evaporation, 34t . p-n junction, 437

external work, 334 Diffusive equilibrium, 120

nonmctallic solid, 259 DtlTustvity, 399, 428, 437

of slab, 437 Dilution refrigerator, helium, 342
Cooper pair, 250, 257 Dispersion relation, 425

Corresponding states, law of, 290 Distribution, classical,161,410

Cosmicbackground radiation, 98 Base-Einstein, 158
Countcrflow heat exchanger,336 Fennt-Dirac, 154,411
,. Critical magnetic field, 253 . Dju, B., 459
Dixon,R. W., 366 Entropy, 42, 45, 52
Donor, 356, 363 accumulation, 229
levels,'369 and chemical poicniiai. 131
Donor impurities, tonization, 273 conventional, 45
Doping concentrations, 375 degenerate bosongas, 221
Doping profile, 383 degenerateFermi gas, 2j9
Dry adiabatic lapse rate, 270 fr\302\253energy. 165
heat now, 44
Earth, distance from Sun, 111 law of increase, 54
Eddy current equation, 425 as logarithm, 50
Effective density of stales, 361 of mixing, 78, 178, 314
valence band. 362 and occupancy, 114
Effective mass, 360 and temperature, 52

EfTcctivc work, 246 transfer, 227

Efficiency, Carnot, 230 van der Waals gas, 305
Eigen, M., 270 Equation of continuity. 424
Einstein condensation, 199 Equation of stale, van dcr Waais, 287, 289
temperature, 205 Equilibria,
\"
chemical. 266
Einstein relation, 406 phase, 322
high electron concentrations, 388 Equilibrium, hydrogen, 269
Einstein temperature, solids, 84 gas-solid,285, 305
Elasticity of polymers, 86 panidc-anttpartide, 274
Electrical conductivity, 413, 421 reactions, 266
Electrical noise, 98 two phase, 330
Electrochemical battery, 129 vapor pressure, 291
Electrolysis, 247 Equilibrium constant, 268
Electron-hole pair generation, 388 Equipartition of energy, 77
Electron mobility, 380 Error function, 429
Elementary excitations, 212 Euteclic, 325
EHiott, R. P., 323 Evaporation cooiing, 341
Etnissivity, 97 limit, 352
Energy, conversion, 240 Expansion, cooling, 334
conversion efficiency, 230 engine, 334
degenerate boson gas, 221 Fertitt gas, 259
equiparijtion, 77 irreversible, 175
Fermi gas, 185 isothermal.171
fluctuations, 83, 113 Extensive quantities, 264
geothermal, 259 Extreme rdativtstic particles, 117
ideal gas, 76 Extrinsic semiconductor,364
magnetic, 252
mean 420
kinetic, Feher, G., 148
mixing, 314, 330 Fermi energy, 155, 183
thermal average, 140 Fermi gas, 183
transfer, 227 fluctuations, 222
two state system, 62 ground slate, 185
van der Waals gas, 305 Irreversible expansion. 259
Energy gap, 355 liquid hdium-3, 219
Ensemble, average, 31,62 metals. 194
construction, 32 relativistic, 218

systems, 31 Fermi level, 155,357

Enthalpy, 246, 284 intrinsic, 362
van der Waals gas, 305 extrinsic semiconductor,364
Fetmi-Dirac distribution (unction, Gibbs free energy,246, 262
153, 177, 411 van dcr WaaU gas, 291
Fcrnfi-Dirac integral, 366 Gibbs sum, 134, 138, 146
FcrmtOil, 152 ideal gas, 169, 180
Fer to magnet ism, 295, 302 two level system, 146
Pick's law, 399 GifTard, R. R., 103
First law, 49 Goldman, M., 350
First order transition, 302 Grand canonical distribution, 138
Flow, through hole, 415 Grand partition function, 138
through tube, 416, 421 Grand sum, 138
speed, 422 Greenhouse eflect, 115
Fluctuations, Bose gas. 222 Guyer, R. A., 210
concentration, 147

energy, 83, 113

Fermi gas, 222
time of, 178 Half-cell potentials, 131
Flux density, 397 Hall, R. N.. 385
Fourier analysis, 436 Ha|I-Shockley-Read
theory, 383
Fourier's law, 401 Hansen. M., 323
Free energy, 163 Harmonic oscillator, 52, 82
Gibbs, 246, 262 free energy, 82
harmonic oscillator, 82 multiplicity function, 24
Helmholu.68 Harwit, M, 219
paramagnetic system, 69 Heat, 44,68, 237, 240
photon gas, i 12 definition, 227
two state system, 8i isobartc, 245
Free energy function, Landau, 298 path dependence,240
Fmlon, J. S., 142 ... vaporization of ice, 305
Fuel cell,
247, 248 Heat capacity, 63, 165
Fundamental assumption, 29
' boson 221
degenerate gas,
Fundamental temperature, 41 electron gas, 189
intergalactic space, N3
Gallium arsenide, semt-tnsulating, 372 liquid helium-4, 113
Gamma function integral, 440 photons and phononS, U3
Gas constant,166 solids, 113

Gas, critical temperatures, 277 two state system, 62

degenerate, 182 Heat conduction equation, 424
degenerate boson, 221 Heat engine, 228, 230
degenerate Fermi, 219 refrigeratorcascade,258
ideal, 72 Heat exchanger, counter Row, 336

liquefaction, 337 Heat flow, 44

one-dimensional, 86 Heat transfer, sound wave, 434
potential energy, 145 Heat pump, 235, 257
quantum, 182 Heat shield, 112
rarefied, 413 reflective, 115

sounii waves, 430 Hecr, C. V., 34S

Gas-solid equilibrium Helium dilution refrigerator, 342
Gauss integral, 439 Helium liquerler, 351
Gaussiandistribution, 20 Helmholu dec eneray, 6S
Generalized forces,404, 405,453 Heinegroup, 140

Generation, dectron-hoic pair, 3S8 Hemoglobin.141

Geothermal energy, 259 Heitshaw, D. G., 216
Giauque,W., t67 High, vacuum region, 397
Gibbs factor, 134, I3S Hill, J. S., 34S
Hobdcn.M. V.,349 Isotherm, 276
Hots, 177,355 Langmuir adsorption, 143
conductance, 415 Isothermal work, 245
quantum concentration, 361
Hook,J. R.,217 James, H. M, 86
Huiskamp, W. }., 342 Jfohnson, J. B., 98
Hydrogen, equilibrium, 269 Johnson noise, 98
Johnston, H. L., 167
IPTS,451 Joule-Thomson effect, 337
Ice, heat of vaporization, 305 van dcr Waais gas, 338
Ideal gas, 72, 74, 160,169 Joyce, W. 8-, 366
calculations, ISO Joyce-Dkon approximation, 366
Carnot cycle, 237 JQttner, F.,219
chemical potential, 120,169
chemical work, 251 Kelvin temperature, 41
energy, 76 scale, 445
Gibbssum, 180 Kinematic viscosity,404
internal degree of freedom, 179 Kinetic model, mass action, 270
iscntropic relations, 179 Kinetictheory, ideal gas law, 391
Kelvin, 446 Kinetics, detailed balance,407
law, 77 Kirchhoir law, 96, 115
law, kinetic theory, 391 Klein, M. J., 463
one-dimensional, 86 Knudsen regime, 397,413
sudden expansion, 243 Kramers, H. C, 114
therm odynamic identity, 177 Kuril\", N-, 348, 349
two dimensions, 180
Impurity atom ionization, 143 LaioS, F-, 459
Impurily level, 368, 383 Lambda poinl.heIium-4, 210
carrier recombination, 383 Laudau free energy function, 298
Increase of entropy, law of, 45 Landau function, 69, 298
Inequalily, Carnot, 232 Landau theory, phase transitions, 298
Injection laser, 381,38S Langmuir adsorption isotherm, 145
Integrals comaining exponentials, 439 Laser,injection, 381, 3S8
Intensive quantises, 264 Laiem heat, 281, 284
Intergalaciic space, heat capacity, 113 enthalpy, 284
Internal chemicaipotential, 122, 124 increase of entropy, 45
International Practical Temperature vaporization,2SI
Scale, 451 Law of corresponding states, 290
Intrinsic conductivily, 387 Law of increaseof entropy, 45

Intrinsic Fermi level, 362 Law of mass action, 268, 362, 382
Inversion temperature, 336 Laws of rarefied gases, 413
lonization, deep impurities, 3S8 Laws of thermodynamics, 48, 49
donor impurities, 273 Leff, H. S-,259
impurily alum, 143 Legged, A. J., 217
thermal, 273 Lcln, W. H-, 195
water, 269 Linde cycle, 339
Irreversibilily, sources, 232 Liouville theorem, 40S
Irreversible thermodynamics,406 Liquid helium 11, 209
Irreversiblework, 242 Liquid heIium-3, 217
Isemropicdemagnetization, 346 supcrliuid phases, 217
Iscntropic expansion, 114, 148 Liquid hdium-4, 207
Isentfopic process,173 heat capacity, 113
Iscntropic rclalioos, ideal gas. 179 Liquid 3He-4He mixlute, 320
isobaric process, 245 mixing energy, 330
Uquiduscurve, 323 Negative temperature, 460
Long tube, Row, 416 -Never,\" 53
Loschmidt number, 396 G., 114
N'iels-Hakkenbcrg.C.
Lounasmaa, O, V., 342 Nondegenerate semiconductor, 358
Low orbital free atoms, 201 Nonequiiihrium semiconductors,379
Low temperature thermometry, 448 Normal phase, 203
Lyncis, B., ill Nuclear demagnetization, 348
Nuclear matter, 198
McFee, J. H., 394 Nuclear reactor,critical size, 437
Magnetic concentration, 145 Nucieatton, 294
Magnetic difliisivHy, 425, 437 critical radius, 295
Magnetic energy, 253 Nyquist theorem, 93
Mapiciic field, adsorption of Oj, 147
mobile magnetic particles. 127
spm entropy 170 Occupation<W levels, 369

in superconductors, 253 Onsajcr relation. 406

fVhhii 9 lV>
MaSn\302\253ic susceptibility. 81
Spl,^ ' J
Magneticsystem, 23
m
Magnetic work. 252
oS^ZlZl^

Ovcrhauser efTeci,K4
Mass action, law, 268, 270, 362, 387
Maxwell distribution of velocities, 392, 419
Maxwell relation, 71, 272 Paramagnetic system, 69
Maxwell transmission distribution, 395 . Paramagnetism, 52, 446
Maxwell velocity distribution 393 Particic-antipartide equilibrium, 274
Mean field method, 288 Particle diffusion, 399, 409
Mean free path, 395 Partition function, 61
Mean speeds,Maxweilian distribution, 419 two systems, 85
Mean value, 22 Pascal (Pa), back endpaper
Mdssner effect, 252 Path dependence, 240
Merzbachcr, E., 459 Pauli exclusion principle, 152
Metastable phases, 278 Peltier effect, 336
Meyer, L-, 215 Penetration, temperalure oscillation, 426
Milaer, J. H., 34S Pcnnings, N. H., 345
Minority carrier lifetime, 3S8 Peritectic systems, 330
Mixing, energy, 3S4, 330 Perpetual motion, 50
entropy, 78, 578,314 pH, 269
Mixture, binary, 310 Phase,267
crystalline, 319 condensed, 203
liquid 3He-4He, 320 equilibria,322
phase equilibria, 322 normal, 203
Mobile magnetic particles, relations of helium, 210
chemical potential, ]27 Phase diagram, 321

Mobility, electron, 380 Phase Iransitions, 298

Molecules,Earth's atmosphere, 145 Landau Iheory, 298
Monkey-Hamlet,53 superconducting,306,307
Mosl probable configuration, 33, 35 Phenomcnologicailaws,398
Multiple binding of Oa, 148 Phillips, N. E-, 195,196,
254

Multiplicity, 7 Phonon, 102

Multiplicity function, 15, 18 beat capacity, 113
' '
harmonic oscillator, 24 '.
\342\226\240'
\"
mode, 104 '\342\226\240
\342\226\240
- \342\226\240
\342\200\242
Myoglobin, 140, 142 '. . ; solids, 102 ;
Photon, Carnot engine, 258 Reaction raw, 371
condensation, 321 Read, W. T., 3S5
heal
capacity, 113
thermal, HO Reese, W., 219*
Photon gas, 112, 114 Refrigerator performance.
free
energy, II2 Carnol coefficient. 234
iscntropic expansion, 114 coefficient, 234
one dimension. 112 helium dilution. 342
Pillans. H-, 111 light bulb in, 259
Planck distribution function, 89, 91 Rcif. F.,215
Planck law, 91, 95 Relativistic Fermi gas, 21 %

p-n junction, 373 Relativistic white dwarfs. 222

reverse-biased,377 Relaxation, thermal, 432
Poise. 403 time, 433
Poisson distribution. 138.453 Reservoir, 58
distribution law, 455 Resistivity. 387
Poision equation, 375 Reverse-biasedp-n junction, 377
Pollution, tlicnniil. 25S Reversible isotherm^ expansion. 171
Potjmer, 86 Reversible process, 64
elasticity. 86 Room air conditioner. 253
Population inversion. 460 Rose,W. K., I(J7
I'ound, R. V., -563 Roionbliiiii. S. S., 34S
Pratt, W. P.. 34g Rossi-Fanctti, A., 142
Pressure. 64. 164 Rotation, diatomic molecules, 84
degenerate Fermi gas. 2!9
thermal jadiation. ill
Principle of detailed balance, 271
Probability, 30 Sackur-Tetrodeequation.77, 165
Proctor, 463W. G., experimental tests, 167
Propagation, sound waves,430 Schindler, H., 148
Pulse, development. 427 Schotiky anomaly, 63

Fourier analysis, 436 Second law, 49, 240

random, 457 Second order transiiion, 304

Pump, speed. 457 Segregation coefficient, 331

Puree!!. E. M., 463 Semiconductor. 353
degenerate,358,365
donor impurities, 273
Quantum concentration, 73, 85
extrinsic, 364
conduction electrons, 36! 143
impurity atom iontzation,
holes,36!
JS2
n~ and p-type, 363
Quantum gas, 358
icgime, 182
nondegenerate,
Quantum 379
nonequihbrium,
Quasi-Feimilevel, 379
Semi-insulaiing gallium arsenide. 372
212
Quasipanicte,
Shockley.W.. 385

Shunk, F. A., 323

Radiant energy fiux, 114 Simmonds. S., 142
Radiant object, 114 Smythe, W. R., 425
Radiation Soilj temperature variations, 437
black body background, 98 thermal diffusivity, 427

thermal, 111 Solar constant, 110

Ramsey, N. R, 463 Soiidificaiionrange, 331
Rarefied gases, laws of, 413 . Soljduscurve, 323

Reaction,chemical, 266 Solubility gap, 310, 311

Soliduscurve, 323
Temperature oscillation, penetration,
Solubility gap, 310, 311 426, 437
phase diagram, 32 i Thermal average, 62
Sound wave, Jieal transfer, 434 Thermal conductivity, 401, 42j
propagation, 430 metals, 421

Specific heal, 63 Thermal contact, 33, 37

Speed, pump, 417 Thermal diflusivity, 425
lube, 422 soil, 427
Spin entropy, 170 Thermal equilibrium, 36, 39
aclditivity, 53 values, 36

Spin excess, 14 Thermal expansion, 272

Spinsystem, 10, 37. 52 Thermal ionization of hydrogen, 272
Srinivasan, S., 248 Thermal photon, 110
Stefan-Bo!tzjaann constant, 96 Thermal pollution, 258
Stefan-Boltzmann law. 91, 94 Thermal radiation, J J J

Stcycrt, W. A., 343 Thermal relaxation, 432

Stirling approximation, 19, 441 Thermodynamic identity, 67, 133, 177
Stokes-Ein
stein relation, 404 Thermodynamic relations 71,272
Stmve, O., i Jl Tliermodynamic tbermometry, 449
Sudden expansion, ideal gas, 243 Thermodynamics, superconducting
vacuum, 175 transition, 306
Sun Thermometers, 447
age, I i i Third law, 49
interior temperature, I Ji Throughput, 415
mass aad radius, I j r
Torr,4J4
surface temperature, 1 iO Transitions, first order, 302
Superconducting transition, 306 second order, 304
Superconductor, 252 Transmission distiibutton.

magnetic work, 252 Maxwell, 395

Supercooling, 278 Transport processes, 397
Supctfiuid phases, 217 Treioar, L. R. G., S6
Superfluidity, 212 Triple point, 284
Superheating, 278 Two stale system, 62, SI
Superinsulation. 19 free energy, 81
Susceptibility, nugnelic, 8! licat capacity, 62
Swcnson, C. A., 2J0 Un :erse, entropy of, 110
Tacoais,K. W., 345 v. Karman.T., 106
Taylor, B. N., 446 Vacuum physics, 413
Teelers, W. D., 259 Valence band, 355
Temperature, 41 effective density of slates, 362
critical, 276 van der Waals gas, critical points, 2S9
Earth's surface, JU energy, 305
estimation of surface, 97 enthalpy, 305
fundamental, 4!
equation of stale, 287, 2S9
Kelvin, 4! Gibbs free energy, 291
negative, 461 helium, 350

oscillation,426 Joule-Thomson effect, 338

scales, 445 Vapor prcsiurc, equilibrium, 291
Sun's average, I! 1 Vapor pressure equation, 276, 281
Sun's surface, HO Vaporisation, latent heat, 231
variations in soil, 437 ice, 305
Velocity of sound, 432 Woods, A. D. B., 216
Viiia theorem, Sll Work, 227, 240
Viscosity, 402 chemical, 251
kinematic, 404 constant pressure, 245
constant temperature, 245
Water definition, 227
calculation of dT/dp, 305 irreversible,242
ionization, 269 isobaric, 245
Webb, R. A., 103 isothermal, 245
Weinslock, B., 209 magnetic, 252
Weissman, M., 148 path dependence, 240
Wheatley, J.C., 217
While dwarf star, 196
mass-radius relationship, 2!9
relalivislic, 222 Zemanskv, M. W., 279, 45
Wiebes, J., 114 Zerolh law, 48
Wicdemaim-Franz ralio, 42! Zipper problem, 85
Wilks, J., 219 Zucca, R., 373
 ZJ6'\"Y O Ga O

Unit conversions
Energy

I J s lO'erg
leal B 4.1S4J
I cV = 1.60219 x IO'\"J = 1.60219 x l<r'2crg = 23.061 kcal mol'

1 kWh = 3.6 x 10'J

1 BTU a 1055J

Power
I = 1 Js\021
W s 1 lO'trgs\021
1 hp
- 746 W = 550 ft lbs\021

Pressure

1 Pa = 1 N m~2 s O.Oi mbar s; 10\023 bar =s 10 dyn cm\022

= 7.501 x 10\"JmmHgorlorr
i bar a 10'dyn cm\021 \342\200\242=
10'Nm\022 ~ 750 mm Hg

1 raraHgsa 1 iorr= 133.3Nm\023= 1333dyn cm\023

1 aim b 760 mm Hg = 1.013x 10s Nm\021

= 1,013 x 10s dyn cm\022 = 1.013 bar

\342\200\242
Al 0'C where ihs accelerationof gravity has Ihc standard value 9.8066S in s\021.
 Table of Values

Quantity Symbol Value CGS St

Velocity of light c 2.997925 I0l0ci T1S~1' 108ms-'

Proton cbarge e J. 60219 __\342\226\240

4.80325 [Q-1Q esu

Planck's constant h 6.62618 io-1T ergs IQ-l*Js
H =
hj2n 1.05459 10\"iV ergs 1O-\"JS
Avogadro's number N 6.02205 x !0IJmor
Alomic mass unit amu 1,66057 . 10\"\" g 10~27 kg
Electron rest mass m 9JO953 }0~2i S 10-\"ks
Proton resl mass M 1-67265 10\"*\" g lo-\"kg
Proton mass/electron mass 1836-2 \342\200\224 \342\200\224

Reciprocal fine structure l/\302\253 137.036 _ _

consiani hefe*

Eieclron radius e1/mc2 r. 2.81794 10\021;'cm 10-** m

Electron Compton K 3.86159 10\"\0211
i
cm 10\"IJm
wavelength hjmc
Bohr radius h^/me1 r0 5.29177 10\"9 cm 10\"\"m
Bohr raagnelon ehjlmc 1'* 9.27408 10\021 lergG~' 10\0234JT*
Rydberg constant meij2hl R^ or Ry 2.17991 10\"' 'erg 10~18J
13.6058 eV

I eieclron volt eV 1.60219 10\"' *erg 10\"J

eV/ft 2.41797x l0uHz \342\200\224

eV/?,c 8.06548 l0*c; iCl'm-'

eVA-fl 1.16045 x 10* K \342\200\224 \342\200\224

Boitzmann consiani k. 1.38066 10\"\"' sergK-' |0-..,ri

Permittivity of free space e0 I iO'/^nc2
Permeability of freespace \342\226\240
fo
\342\200\224 1 x
4\302\253 10\"
Molar gas constant Nka R 8.31441 107c
Molar volume ideal gas, at 22.41383 103c lO^rn'mo]
= 273-15 K,
TQ

po = = laliTl
10132SNm\"I

Source: E. R. Cohen and B. N. Taylor, Journal of Physical and Chemical ReferenceData 2D),663 A973).