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Compositor:

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Library

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Frank

Cataloging

in

pat;

Publication

Clmrlcs.

Killcl,

Thermal physics.

Bibliography:p.
index.

Includes

Statistical

!.

Herbert.1928-

536'.?

\302\260

I9B0

Copyright
No pan of
mechanical,

79-16677

by W.

bor.k

may

plioiographic,

H. Freeman and
be reproduced

or electronic

copiedfor
permission

in

Company
by

any

process,or in

phonographic recording,nor

may

it be

system, transmitted, orotherwisc

wriiicn
or
private use, without
public
from the publisher.

a retrieval

in

Pcimcti

this

of a

form

sioreti

ilie

United

State of

America

Twenty-first printing, 2000

Kroe/n
Tillc.

II.

aullior.

O-7167-IO8S-9

ISBN

liic

joiiii

1930

QC3H.5.K52

I.

tiicrmodyn;miics.

About the Authors

Charles

at

has

Kiitel
since

Berkeley

1951,

having
in

work

undergraduate

solid

laught

physics

slate physics at the University of California

been at [he Bell Laboratories.His
previously
was done at M.I.T. and at the
Cavendish

His Ph.D. research was in theorclicai

nuclear
Professor
Breit at the University of Wisconsin.
physics with
Gregory
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
;i id
National
of
of
Arts
Science
and
of
the
American
Academy
Academy
semio nSciences. His research has been in magnetism,
resonance,
magnetic
and
the
statistical
mechanics
o
f
soiids.
ductors,
of Cambridge

Laboratory

Kroemcr

iferbcrt

is

liliy^ics.

a I'lt.D.

!c received

in Germany

with

Professor

liurhara.

at Santa

California

University.

Prom 1952 through

thesis

of Electrical

Engineering at the

His background

mid

in physics in I'J52 from

on hot electron effects

I96S tie workedin

several

nre

training

the University
in

lhc

semiconductor

then

of

University

in solid
of

state

Gulling

transistor.

new
research

labora-

of
Stales. In I96S lie became
in
to
UCStt
at ltic University of Colorado; lie came
[ilixirieul
Engineering
of semiconductors
and technology
1976. His research has been in the physics
and semiconductor devices, including
transistors,
negativehigh-frequency
electron-hole
mass effects in semiconductors, injection lasers,the Gunn
effect,
and
semiconductor
hetcrojunctions.
drops,

laboratories

in

Germany

and

the

United

Professor

Preface

This book

an

gives

simple,

other

no

Probably

and

science

are

methods

the

applications.

physics. The subject is

and the results have broad applicatheory is used more widely
throughout
of thermal

account

elementary

powerful,

physical

engineering.

We have written for undergraduate

and for electrical engineering students

(not

but

original,

not

easily

physics

and

These

generally.

purposes have strong common bonds,most

mcmls,
gases, whether in semiconductors,

methods

of

students

notably

a concern

stars,

or ituclci.

accessible

elsewhere)

astronomy,
for our

fields

Fermi

with

We develop
that

are

well

to these fields. We wrote the book in the first place

because
we
as compared
to (hose
were delighted by the clarity
of the \"new\"
methods
we were taught
when
we
were students
ourselves.
some
because
We have not emphasized several traditioual
they
topics,
classical
on
statisnare no longer useful and
some
because
their reliance
cai mechanicswould
make
the
course
more difficult than we believe a
course
should
be. Also,
we have avoided the use of combinatorial
first

suited

methods

where

they

are unnecessary.

Notation and units;

parallel.
the

do

We

fundamental

not

use

We

generally

the calorie.

temperature

t by

use
the SI and CGS systems in
to
The kclvin temperatureT is related

r =

kBT,

and

the

conventional

entropy

S is reialed lo the fundamental

a by 5 = ka(j. The symbol log
entropy
will
denote
natural
logarithm
throughout,
simply because In is less exlo Equation
refers
A8) of
A8)
expressive when set in type. The notafion
of
3.
the current chapter, but C.18)
refers
to Equation A8)
Chapter
with the assisfto course
notes developed
Hie bookis ihe successor
(he
ance of grants
of California. Edward M. PurceSlconUniversity
by
from review of the
to
We
benefited
ideas
the
contributed
first
edition.
many
and Nh.-holns
L. Richards,
Paul
second edition by Seymour
Geller,
Wheeler- Help was giveii by Ibrahim Adawi, Bernard Black, G. DomoK. A. Jackson, S. Justi, Peter
Cameron
kos, Margaret
Geller,
Hayne,
Martin
Ellen Leverenz, Bruce H. J.
J. Klein,
Kittel, Richard
Kittler,
McKellar,

F.

E.

O'Meara,

Norman

E. Phillips,

B. Roswclt Russell,T. M.

Preface

B.

Sanders.

An

by

in

added

was

the index.

treatment

elementary

atmosphere

Carol

thank

her help with

for

Wilde

Professor

Richard

John Wheatley, and Eyvind

Verhoogen,
for
the
Tung
typed manuscript and Sari

John

Stoeckly,
We

Wichmann.

1994

of the

on page

Muiier.

Bose-Eitistein condensationwas
For instructors who have

solutions

manual

is

available

115, following an

page

on

added

to

adopted

via

effect in the Earth's

greenhouse

the

aioinic
page

suggested

argument

gas experiments
223 in 2000.

on the

classroom

use, a

course

the freeman

atmo-

for

web site

(http:/Avhfreenian.

com/thermaiphysics).

Berkeley

and

Santa

Barbara

Charles
Herbert

K'tttel

Kroemer

Note

to

the

Student

For minimum
of the concepts
the authors
coverage
presented in each chapier,
recommend the following exercises.Chapter 2: 1,2, Chapter
3:
1,2, 3,4,
8,
6: 1,2,3,6,12,
5:
11; Chapter 4: 1,2,4, 5,6, 8; Chapter
6,8;
1,3,4,
Chapter
9:
8:
14, 15;Chapter7: 2,
1,
2,
3,
5,
6,
7;
1, 2, 3;
7,
11;
Chapter
Chapter
12:
13:
3,4.5;
1,2,
Chapter
Chapter 10: 1,2,3; Chapter 11: 1,2,3;Chapter

3;

3,5,6,

3,7,8,10; Chapter 14: 1,3,4,5; Chapter

15:

2,3,4,6.

Contents

Guide

xiii

to Fundamental Definitions

General

xv

References

Introduction

Chapter

1
States

a Model

System

Eittropy and Temperature

Chapter 2
Chapter

of

Distribution

Boltzmann

27

and Hdmholtz

Free Energy 55

Chapter4

Thermal

Chapter 5

Chemical Potential and Gibbs Distribution

Chapter

Ideal

Chapter

il

Chapter

Binary

309

Mixtures

Cryogenics 333
Statistics

14

Kinetic Theory 389

Appendix B

261

275

Transformations

Semiconductor

353

423

Propagation

Some

225

13

Chapter15
Appendix

Phase

1 i

181

Gibbs Free Energy and ChemicalReactions

Chapter 12
Chapter

87

Distribution

Planck

151

Work

tHeaZahd

Chapter10
Chapter

Gas

Fermi and Bose Gases

Chapter 7
Chapter

and

Radiation

Integrals

Containing

TemperatureScales 445

Exponentials

439

Appendix

Appendix

Poisson

Pressure

AppendixE
Index

465

Distribution

453

459

Negative

Temperature

460

Absolute

activity,

Accessible

Definitions

Fundamental

to

Guide

29

state

Boltzmann constant,

25

ka

Boltzmann

factor,

Boson

183

Chemical

119

/;

Classicalregime,
n

74

\302\253

nQ

31

of systems

Enthalpy, H = U

246

pV

40

Entropy,

1S3

Fermion

Gibbs factor, exp[(NjiGibbs

free

Gibbs

or grand

Heat

61'

exp\302\243~~ \302\243/t)

potential,

Ensemble

139

exp(/i/t)

sum,

\342\200\224

\\a

\342\226\240%

138

p^

138

63

capacity,

68, 227

Heat, Q

free

HelmhoHz

Landau

G =

energy,

t)/i]

free energy

Multiplicity,g

energy,

\342\200\224
\342\200\224
U
xa

function, FL

Orbital

Partition

function,

61

298

Guide to Fundamental

concentration,

Quantum

Reversible

64

41
62

Thermal

average

Thermal

equilibrium
W

hq

process

Temperature, t

Work,

Definitions

227

39

References

General

Thermodynamics
A. B. Pippard,

of classical

Elements

1966.
M. W.

R. H.

and

Zemansfcy

textbook, 6ih

anil

Heat

DiEEman,

ed., McGraw-Hill,

Cambridge University Press,

thermodynamics,

an intermediate

thermodynamics:

198!.

Afcchanics

Sitttisiical

U. K,

and
M. Eisner, Statistical
1988.
Agarwal
mechanics, Wiicy,
Dover
PubticaHit), Statistical mechanics:principlesand selected
applications,
iions, 1987, cl956.
C. Kittct, Elementary
statistical
applications
physics, Wiicy, 1958. Parts 2 and 3 treat
1 has been expanded
ioEo the
Part
to noise and to elemeniary transport Eheory.

T. L.

present Eext.
R.

Kubo,

R, Kubo,

Statistical
M.

mechanics,

North-Holland, 1990, cI965.

Statistical physics !! (NanequHibrium),

N. Hashitsume,

Toda,

Springer,

1985.

L D.

Landau and E. M. Lifshitz,

Statistical

K. M. Lifshitz

and

L. P.

1985.

Scientific,

! (Equilibrium),

Springer,

1933,

tables

Mathematical

H. B. Dwight,

Tables

1961. A

3rd cd. by

physics,

1.
Piiaevskii, Pcrgamon, 1980, part
Ma, Statistical mechanics. World
Shang-Keng
M. Toda, R. Kubo, N. Saito,Statisticalphysics

and other

of integrals

mathematical data, 4ih

ed.,

MacmUton,

collection.

smati

useful

widely

Applications

Asirophysics

R. J. Taylor,

The

S. Weinbcrg,

The first

ed.,

Bainam

structure

their

stars:

three

Cooks,

minutes:

and

evotitiioit.

a modern

v:\\-w

1972.

Springer,
of the

origin

of the

universe, new

1984.

Biophysics and macromolccules

T. L. Hill,
Springer,

Cooperathity

1985.

theory

in biochemistry:

steady stale

and equilibrium

systems,

General Refer,

Cryogenicsand
G. K.

low

J.

D. S.

and

Wilks

. .

Betis,

An

pa.

helium, 2nd

to liquid

introduction

physics, 3rd ed., Oxford

ed , Oxford

Univesity

1987.

Press,

Irreversible

thermodynamics

J. A. McLennan,Introduction
1989.

I.

in low-temperature

techniques

1987, ct979

Press,

University

physics

lempcrature

Experimental

White,

I. Stcngers,

and

Prigogine

Random

to

statistical

non-equilibrium

Order

out

of

mechanics, Prentice-Hall,

man's

chaos:

new dialog

with

nature.

1934.

House,

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,
Plasma

physics

I... Spitzer, Jr., Physical

in the

interstellar medium,

Touiouse, Introduction
Wiley,

phenomena,

H. E.

and

Haasen,

Boundary

the

critical

and

critical

[ihenomena,

Oxford Uni-

1987.

Press,

affoys

Physical

metallurgy,

2nd ed.,

CambridgeUniversity

Press,

1986.

Superb.

value problems

and
J. C. Jaeger, Conduction of heat
H. S- Carslaw
Press,
sily
19S6,ci959.

Semiconductor

group and to

renormalizat'ton

1977.

Stanley, Introduction to phase transitions

University

Metais

to

197S.

Wiley,

P. PfeiHy and G.

P.

processes

transitions

Phase

19S9.

in solids,

2nd ed.,

Oxford Univer-

devices

Introduction to applied solidstate physics,

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

R.

Datven,

Solid

state

physics

C. Kittel, Introduction

to solid

state physics, 6th

ed.,

Wiley,

1986.

Referred

to ssISSR

Thermal

Introduction

Our approachto
physics

to do

going

structure:
in

in

thermal

the

this

differs
from the tradition followed in beginning
we provide this introduction 10set oul what
we are
that follow. We show the main lines of the logical
all the physics comes from
In order of lhcir
the
logic.
physics

Therefore

courses.

chapters
subject

in our
are the entropy, the temporaiure,
appearance,the leadingcltaracters
story
the Boltzmann
the chemical
factor,
potential, the Gibbs factor, and the disiribu-

functions.

tion

The entropy
A

closed

system

measures the number of quantum

might

be

in

any

of these

states

quantum

to a

accessible

states and

system.

(we assume)with

statistical element, ihe fundamental

logical
o
r
states
are
inaccessible
to the
either
accessible
assumption,
quantum
and the system is cquaiiy likely
to be in any one accessible slate as in
system,
olher
slate.
is defined
accessible
as
Given
accessible
states, the cniropy
any
g
=
a
lhtis
defined
will be a function of ihe energy
U, lhe
logg. The entropy
V of the system, because theseparamnumber of particles N, and the volume
as wirii. The
parameters ciilcr
enter
the dctcrminaiion
of y; other para meters may
is a mathematical
use of the logarithm
convenience: it is easier to write 1010
than expA020), and it is morenatural
to speak of a-y + o, lhan
for two
systems
The

probability.

equal

fundamental

is that

ofg,3j.

When two systems, each of

ttiey

may

transfer

energy;

energy,

specified

their total

individual energies are

perhaps in the other, may increase
on their

are brought

into thermal

energy remains constant,but

A

lifted.

the

transfer

product

accessiblestates of the combined

systems.

The

of energy

in

the
one

coniact

comlraints
direction,

or

g^g, that measures the tiumber of

fundamental

assumption

biases

maximizes
the
the outcome in favor
of that
allocation
of the total energy that
and
more likely. This statement is
number
of accessible states: more is better,
is the
the
kernel
of the law of increase of entropy, which
general
expression of

the second law

of

thermodynamics.

brought two systems into thermal contactso that they may transfer
One
ofthe encounter?
system will
energy. What is the most probableoutcome
of the
of the other, and meanwhile the lotal entropy
gain energy at lhe expense
two systems will
increase.
will reach a maximum for
the entropy
Eventually
It
is
not
the
total
difficult
to
show
2) that the maximum
given
energy.
(Chapter
We have

is atiained when

ihe same

for

quantity

in ihermai

system is equal to the value of

This equality property for Iwo systems
of the icmperat lire. Accordingly,
expect
for one

value

ihe

o((ca/cU}K_y
the Second
system.

coniaa is just the

we define the fundamental

property we

relation

by the

lemperaiure

U)

CUJ

The use of 1/r assuresthat

needed.

complicated

directly

proportional

to t,

3. i.ti

c, be pjaeed in thermal
reservoir. The loia! energy

.S\"

the

of

the Boltzmann constant.

i.fie :it cnorj>y

sinies,

the

have

fundamental

smali system

with

Uo

energy

assumpiion,

s to

energy

entropy a

g{U0 by

may

definition

the

be dropped.

This

may

~
e)

is Boitzmantt's

\342\200\224
slates

e, the
lo

accessible

e)

B)
exp[<*(f

be

a{Ua)

in a

expanded

o)]

Taylor series:
=

\302\243{ca/tV0)

c(t/0)

- e/r ,

the temperature. Higher order terms in

which
Cancellation of the term exp[_a{U0)],

result.

have

wiil

of energy

A) of

energy (e) of the two state

temperature

g{U0

and

Uo
slate

- c)

and denominator of B) after

numerator

have

gWo)

^@)

:n

the ratio of tbe probability of finding [he

0 is
the probability of finding
it with
energy

The reservoir

wiii

:iml

in

une

system Uial we eaH the

systems is UQ; when the small

is in ihe stale of energy 0. the reservoir has

energy
in
states
it.
When
the
small
is
the
accessibleto
sysiem
g{U0)

it. By

tl

u large

system

reservoirwill

treau-d

factor

Dolt/nvnm

ibe

combined

\342\200\224
\302\243
and

is

temperature

kRa.

with

coniaci

energy

more com-

r; no

low

to

Kelvin

where kB is

Ayr,

entropy
given by
a very MiiipJe csampli? uf
iwn
Miiall sysicm wiih uiily

Now consider
Uiajner

with

ihe

it will foilow'that
5 is

conventional

The

flow from high

will

energy

is

rclaiion

the

To show its
system

in

substitution

use, we

thermal

calculate

contact

the

with a

expansion

occurs

of C),

the

C)

in the

leaves us

thermal

with

average

reservoir at tem-

t;

E)

imposed the normalization conditionon the

we have

where

of the

sum

prob-

probabilities:

P@)

The

derivation

in the
most

The

as energy with
the

as

eqtuti

the

transfer

the

to

For two
sign

systems in

in G)

is chosen to

the

chemicai

high

The Gibbsfactorof

maximum with
the transfer
respect
be
of energy. Not only
must
%\342\226\240
{ca/cU)\\also
be
N
refers
to
must
equal, where

diffusive

ensure thai

ih'w

r,

<=

and

r2

of particle flow
to low chemical

direction

potential

is Hio

coiutiiion

cttii:tiity

contact,

jt1

\\it.

The

as equilibrium

potential.
and
Bolizmann factor

of Ihe

an extension

5 is

Chapter

diffusive and

to

{uwn spevk's.Tin-*

and

thermal

is approachedIs from

(f it/jW)^,.

first

transfer

can

two systems in

For

of

4 as the

that

systems

be a

will

for Hie two systems, btil

mmilKr of particles of ;i

average energy

in Chapter

this

theory is to

reservoir.

ttie

entropy
as

well

of the

extension

thermal contact,
of particles

F)

to find the

immediately

generalized

important

ns well

particles

- 1.

at temperature r, and we do
of the Planck radiationlaw.

oscillator

harmonic
step

be

can

argument

P{e)

is a
treat systems ilia! can transfer particles.The simplestcx:unpie
1 parltcie
with two states, one witli
0 panicles
and 0 energy, and one with
system
The
in
at
e.
a reservoir
and
with
temperature r and
energy
system is contact
chemicalpotential;i. We extend C) for the reservoir entropy:
ailows

us to

tf(f/0

t;HQ

- 1) =

~
By anaiogy

with

D),

we

0(r/o;A'o)

=\302\273

cxp[{/(

ratio ofihe

is readily

(S)

have

probability the system

ts unoccupied,
to the probability the system
normalization

- l-{ca/dNo)

+ ^/r.

c/r

o(U0;NQ)

P{U)/P@,Q)
for the

z{ca/dUo)

expressed

\302\243)/r]

is occupied

with

(9)

bv

particle

energy 0. The

at

energy

result (9)after

as

A0)

This particular result is known as the

is used

particularly

the

theory

The classicaldistribution
the limit

is just

The

of the

properties

The HeSmholtzfree

energy

for finding the entropy,

eigenvalues

energy

thcnnodyiumic
the

tcxl

illuminate

the

concerns
meaning

Thermal

objects,

and

physics

of

and

the

derivation

in the

F=

low

of the ideal gas law-

occupancyPA,e) is much lessthan

the relation

\342\200\224
to

appears

{5F/cx)s

once we have

found

out

this

result

as an
\342\200\224
a

offers

how

1:

6.

in Chapter

important computamethod

the easiest

to calculate

from

the

of
3). Other powerful tools for the calculation
arc
the
in
of
functions
reiftaiiuier of
developed the text. Most
that are useful in their own right and that illumiapplications
and utility of the principal thermodynamic functions.
connects
the world
of every iky objects, of astronomic;*!

(Chapter

chemical

and

atomic, and electronic systems.

microscopic

used

ideal gas are developedfrom

because

computational function,

electron gas at

(Chapter 7).

function

of A0) when the

to describe the

and

function

distribution

Fermi-Dirac

of metals

high concentration

and

temperature

in

macroscopic.

biological
It

unites

processes
the two

with

the

world

of moiecular.

parts of our world,the

micro-

Chapter

of a Model

States

MODEL

BINARY

AVERAGE

Energy
Example:

Function

16

System

Alloy

Sharpness

10

SYSTEMS

of States and the Multiplicity

Enumeration
Binary

System

of the Multiplicity
VALUES

of ihe

SUMMAItY

22

:\342\226\240

Binary Magnetic

Multiplicity

18

Function

Function

System
for Harmonic

''

--.

Oscillators

-3
24

26

Bul

of a

!: States

Chapter

as a

although,

investigations
development,

in

and becauseit

matter of history, statisticalmechanics

owes
it seems

thermodynamics,

both on account of the

new

yields

quite

departments

ModelSystei.

outside

results

eminently
and

elegance

and places

old truths

is the more

more different
applicability.

upon me. It

kinds

is ihu

impressive the

only

mil never be overthrown,

the

the

greater

it relates,

of things

Therefore

independent

light

in

of thermodynamics,

J.
A theory

to

principles,

a new

in

origin

of its

worthy

simplicity

its
of an

physical
within

theory

simplicity

and the more

deep impression

that

classical

of universal

the framework

W.

of

Cibbs

of its

premises, the

extendedits area of
made

thermodynamics

content

which

I am

convinced

applicability of its basic

concepts.
A.

Einstein

1: States

Chapter

Thermal

is the

physics

Mechanicstells

us

the

are three

heat. There

of

fruit

of work;

meaning
new

in

quantities

ordinary mechanics:entropy,
their definitions
the
in
first

and mechanical

ofslatistica!

union

the

temperature,

principles.

thermal physics tells us the meaning

of
that
do
not
thermal
physics
appear in
and free energy. We shall motivate

deduce their consequences

chapters and

three

of a ModelSyster,

thereafter.

Our

for the developmentofthermal physics

of departure

point

stationary quantum statesofa

the quantum states accessibleto a

of the

of

system

the

for

as the logarithm of the

is defined

entropy

The dependenceof the entropy

energy

of the

of states

number

of the system
energy

concept

count

we can

the entropy

and the free

the temperature,

rhe entropy,

temperature.From

the

on

particles.

know

we

system,

is the

When

system,

(Chapter

2).

defines the temperawe find

the pressure,

the chemical potential,and

Fora
as

such
brevity

in

system

the

energy

we

usually

other
therm odynamic properties of tlie system.
all
a stationary
quantum state, all observable physicalproperties
and the number of particlesare independentofthe time.For
omit the word stationary; the quantum
slates
that we treat

are stationary exceptwhen

14-55.
we
discuss
transport
processes in Chapters
The systems we discuss may be composedof a single
more
or,
ofi^n,
particle
of
interof many particles. The theory
to handle genera! systems
is developed
but
be
can
made
in
particles,
powerful
special problems
interacting
simplilicarions
for

interactions

the

which

Each quantum
said to

has

slate

may be neglected.
a definite energy.

belong to the same energy

The

level.

Stales

with

multiplicity

energy level is the number of quantum states wiih very

it is the number of quantum slates that is important
tlte

of energy

number

states. Two states at

not

as one

shall frequently

levels. We
the

same

deal

must always

energy

levels

is taken

figure

of

hydrogen

at the

are shown

state of lowest

belonging to the sameenergy

that

the

energies

arc

or degeneracy of an
the some energy,
nearly

physics, not
over all quantum

in thermal

fti'th

sums

be counted as

two

slates,

level.

Let us look antic qiu.Umusuresam! eitcryy

The simpler is hydrogen, with oik electron
energy

identical

prolon

has

a spin

level

of

\\h

and

in

Figure

energy.

is in
has

lewis

and
!.!.
Tlte

parentheses,

uOveia!

alomic

s>^u-ms.

one proron. The !u.\\-I>iiig

The zero of energy in the
of quantum stales
number

figure we overlook
orientations, parallel

in lite

two independent

of a Model

1; States

Chapter

SyMm

Hydrogen

Boron

Lithium

ant! boron. The

lithium,
lergy levelsof atomic
hydrogen,
votis, with t eV = 1.602 x tO\0211 erg. The numbers \302\243
stales
the same energy, with no ac
give ihe number of quantum
parentheses
having
is taken
forcouvei
lakenofthe
spinoflhe nucleus. The zero of energy in the figure
ai die lowest energy slaie of each aiom.
ei

Low-tying

energiesare

to the

or antiparaliel

of a

direction of an arbitrary external axis,such

magnetic field.To takeaccount

the values
An

in electron

given

atom

of

the

multiplicities

of lithium

has three

electron interacts with the

of

shown

the

two

for atomic

electrons which

orientations

as

the

direction

we should

double

hydrogen,
move

about

the

nucleus,and eachelectronalsointeracts

nucleus.
with

Each
ail

the

Chapter

I: Statesofa Model

Systet

IUpresc

30
Mill

diq

lip liciiy

25

20

4
3

\\

'

15

5 to 3

_
1

Figure
\302\253_,,
jjj,,

1.2
n, ofa

and
Energy levels, multiplicities,
particle confined to a cube.

quanlum

numbers

other electrons.The energiesofthe levels of lithium shown in the figure are the
collective energies of the entire system.
The
leveis shown for boron, which
energy
has five electrons,
are also the energies of the entire
system.
The energy ofa system isthe total energy
ofal!
kinetic plus potential,
particles,
with

account

taken

of interactions

between particles.

system is a state ofall particles.

Quantum
called orbitals. The low-lying
levels
energy
confined

to

a cube

of stde

are
\302\243

shown

states

ofa

in Figure

ofa

state

quantum

system

one-pariicie

are

of mass M con-

single particle

1.2. We shall

of the

find

in

Chapter

Chapter

1: State* of a Model

free particlecan be characterized

of a

an orbital

that

numbers nf,

quantum

The multiplicities

System

The

n,.

nyi

by

three

integral

positive

is

energy

of the levelsare indicated

tn

the

orbitals

The three

figure.

wiih(HJl^>.fi.)equ.iltoD,l,l),(l,4,]),and{l,l,4)ai!l!aveii/ +
the corresponding energy level has
3.
multiplicity

nr2

n.1

18;

the

to know these!of values

siaie soTthejV
states

in

any

assigned

the

of

arbitrary

such as

c is

s may

it is

A' particles,

of

\302\243S(N),where

energy
Indices

system.

particle

convenient

theenergy

be

assigned

essemial

of the quantum
lo the quantum

states should not

way, bul two different

be

index.

same

the

properties of a system

the statistical

To describe

It is a good idea to siart

the properties of simple
program
by studying
model
which
the energies
for
can
be
calculated
A')
e.vacily. We choose
as a modela simple
because
the genera! statisiical propenies
system
our

systems

Ej{

binary

are believed to appiy equally

This
physical system.
assumptionleadsto predictions

found

for

the

model

experiment. What
as we go along.

statistical

general

are of

properties

to any

well

system

that

always

concern will

realistic

agree
become

with
clear

BINARY MODEL SYSTEMS

The

model

binary

separate

and

Attached

to

syslern

distinct

each

site

sites

is an

is illustrated
fixed

in

N
shown for convenience on a line1.3.

Figure

in space,

elementary magnet

titat

can

We assume

point

only

there are

up or

down,

tlie system means to

To
understand
corresponding to magnetic
an element of the
no
of
count the slates.This requites
magnelism:
or no,
red or blue,
site
of two states, labeled as
system can be
capable
one
or
one.
The
sites are
minus
occupied or unoccupied,zeroor one,
dtSFercni
to
in
sties
with
numbers are supposed
numbered,
overlap
moments

\302\261n>.

knowledge

any

yes

plus

and

not

of the sites as numbered parking spaces in

space. You might even tltink
vacant
or
1A
Cacti
as
in
a car
lot,
Figiire
parking spuce has two states,
parking
occupied by one car.
the two slates
of otlr objects, we may
milure
Whatever
llic
by
desigreiic
down. If (he magnet points
arrows that can only point straight up or straight
the
up, we say thai ilie magnetic moinenr is -Hii.If the magnet
down,
points
magnetic moment is -m.

physical

Model

Binary

123456789

10
Number of the

1.3

Ffgure
moment

numbers

The
\302\261m.

sire

each

Mode! system
sites on a

at fixed

magnets

has

Syster

ils own

site

composedof 10elementary
magncric
line, each having
shown arc aflachcd to ihc silcs;

magnet

assume

We

there

are no

magne'ic field.Each

moment
may be oriented in
magnetic
up or down, so ihai there are 210disiincl
of the 10 magnetic moments shown in the
arrangements
arc selectedin a random process,
figure. If ihe arrangements
two

ways,

(he probability
is 1/210.

1.4

Figure

State

of finding

ofa

tile

parking

spaces. TiseO's denotespaces

denote

vacant

shown

in Figure

spaces.

independent

probability

of arrangements

state of

site;

there

state of

2'v states.

10 numbered

with

particular

sites,

each

parking
theO's

by a car;

occupied

This

moment

state is equivalent

nf the
We may

bears
be oriented

of which
may

orientation

of the

the system h sjveitiedUy

are

lot

shown

arrangement

to

that

(.3.

Now consider N different

assume the values +\302\253i. Each
number

particular

thai

moment

in two

ways

may

ofa!! other moments.

N moments is

The

2 x

2 x

\342\226\240
\342\226\240
\342\200\242
*=

with

total

2\\

the orient at ion of the moment oil c:k!i

yiviiig
for
a single
use ilio following simplettotation

the system of N sites:

nuimrr-

B)

of a

\342\226\240rl:
States

Model Syst

four diflercnl Males of a

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

Figure

1,5

s> stem

of two

numbcr4hem
to

We may
are assumed to be arrangedin a definite
order.
ftom
left to right, as we did in Figure1.3.According
sequence
the state {2}also can be wriitcn
as

sites themselves

The

in

convention

this

C)

symbols B) and {3}denotethe same state of the system, the slate

in
the magnetic
which
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
distinct
state of the system is
every
in
N
contained a symbolic
of
factors:
product
sets of

Both

D)

U)(U

The

is defined

ruie

multiplication

by

ti + till

liXti + li)

(Tt +

UU

The function D) on muitipltcation generatesa sum of 2*v

the 2'v possible
states.
Each term is a product of N individual
symbols,

denotes
an

T1T3I3
For

one

with

magnetic

of

moment

elementary magnet on the line.Each term

the system and is a simpleproductof the form

of

state

example.

of two elementary

to obtain the four

possible

states

(Ti + I1KT2+
is not

but

a state

The product on the

it generates

for each

one

terms,

f\302\260r

t\\i

a system

The sum

E)

for each

symbol

independent

''\"

the states

of the

of Figure

side

of listingthe four
of the

system.

(}x

li)by(t2

+ |j)

1.5:

Till

ii)

is a way

left-hand

magnets, we multiply

itTa

possible

F)

I1I2.

of the

states

system.

equation is calleda generatingfunction:

\342\226\240

\342\226\240
\342\226\240

Model

Binary

function

The generating

the

for

(Ti

of a

slates

system of

This expressionon multiplication generates21 =

Three
Two

magnets up:

Onemagnctup:
None

The
in

is

given

T1I2T3

lihti

tihli

IJ2I3

lilif3

lilils-

up:

be denoted

will

field. The

a magnetic

values

T1T2I3

totat magnetic moment of our

magnetic moment

states:

S different

T1T1T3

up:

magnets

three magnetsis

+ U)-

IjHTj

li)(?2+

Systems

model system

by Mt

value of M varies

from

of

which we will
to --

Nm

each

magnets
to

relate

Nm. The

of

the energy

set of possible

by

\302\253

Nm,

{N

2)m,

(N -

(N

4>n,

6)m,

\342\200\242
\342\200\242
-A'\302\273i\342\200\242,

G)

possible values of M is obtainedif we start with the state for which all
= Nm) and reverseone at a time. We may reverse iV magnets
magnets
up (M
to obtain
llie ultimate state for which
are down (A/ = - Nm).
al! magnets
There are N + ] possible
of the total moment, whereas there are 2s
values
states.When N \302\273!, we have 2N \302\273N + 1. There are many more states than
states
! 024
distributed
values
of [he total moment. !fW = 10,there are 210=
For
N many
moment.
11
different
values
of
the
total
large
among
magnetic
the
total
moment
ft/.
of
the
the
value
different states of
have
same
system
may
a given value of M.
have
in the next section how many
states
We
will calculate

The

set of

are

Only

state

one

of a

system has the moment

TTTT-

There arc N

is one

sue!

ways

state;

to form

another

a slate

with

M = Nm;that

magnet

is

(S)

-TTTT-

one

state

down:

mt

\342\200\242\342\226\240\342\226\240mt

tin

\342\226\240\342\226\240.\342\226\240tin,

AJ)

is
\"

do)

1: Slates

Chapter

with one

slates

other

the

and

of a Mode!System
magnet down are formedfrom

magnet. The states (9)

any single

of

Enumeration

moment

lot.il

have
\302\243!0)

by

reversing

- 2w.

M = Nw

Function

the Multiplicity

and

Stales

and

(S)

spin as a shorthand for

even number. We

It is convenient lo
elementary
magnet.
need a mathematical expressionfor the
\342\200\224
s magnets
number
of states
with W, = {W + s magnets
up and Nl = jN
where
sis
an
When
we
turn
one
from
to
Ihe
down,
integer.
magnet
up [he down
+ s
s goes to jiV ~ 5 + I.
I and
orientation,
{.V + 5 goes to jW
?N
The difference (number up \342\200\224
from 2s to 2a \342\200\224
2. The
number
down)
changes
word

the

use

We

assume that

is an

difference

W,

ihc spin

is called

spin

excess of

right. The facior of 2 in

prove to be convenient.

left to

from
but

The

excess.

it

will

The productin

D)

may

be written

only

in

many

the order in

of the

magnets

have magnets

sites
which

the

arrows

(ID

the 4 states in
to be

in

\342\200\224

2,

a nuisance at this stage,

if-

from

are

a state

up or down,
in a

appear

2,0, 0,

1.5 is

Figure

as

symbolically

drop the site labels {thesubscripts)

how

particular

25

appears

(I!}

(T
\342\226\240.

We may

/V,

ft

D)

up or
we

drop

we are

when

interested

down, and not

the

labels

in

which

and neglect

given product, then E) becomes

-

(t

II;

further,

(t +

We

find

(I

|)v for

I)' = Itt +
arbitrary

iV

by

3ItJ + 3IJJ + jjj.

the

binomial

expansion

A2)

We

may
by

With

ihis result

t with

replacing

W,
states

denote

\\N

expression{| +

|)'v

ivv =* y

becomes

tj-v+j

iA-+*

M*V\"J

A4)

of stittes having
s magnets down. This class of
$N + 5 magnets up and N, = i.V
\342\200\224
=
lias
excess
2s and net raagneiic moment 2sm.Let
us
JV,
spin
JVj
the number of states tn this class by g{N,s), for a system of N magnets:

coefficient
=

but equivatem,

different,

a slightly

in

Function

Multiplicity

\342\200\224
s:

ihe symbolic

4-

The

exponents of x and y

write the

form

and the

of Stales

Enumeration

of the term

in

is the number

M*\"'

,n\342\202\254>T

(IS)

Thus

is written

A4)

as

I stJMT^l1\"\"

(I + i)'v=
We

call g(N,s)

shall

llie same

of

value

ihe

field is applied to the spin

s have

states

Note

tn

in a

system:

different values of the

of an energy level

for our

reason

5. The

deltnttion

a magnetic

of different

of

values

to the

field. Until

\302\260ur
9 is equal
multiplicity
we introduce a magneticfield, all

model system have the same energy, which

the total number of states is given
that
A6)

of the
from

of slates having
when

emerges

field, stales

magnetic

energy, so that

a magnetic

ihe number

it is

function;

multiplicity

A6)

may

be

taken

as zero.

by

'

Examples related to g{h',s)for

coin, \"heads\"
down.\"

could

stand

g{Nts) =

A'

for \"magnet

\\Q are

l)-v =

given

upland

in

\"tails\"

(H)

2-v

Figures
could

1.6 and
stattd

1.7. For

for \"magnet

Chapter t: Slatesofa Model

Figtorc 1.6 Number

of 5 -f j- spins
up and
Values

of yf Npi)

tUc spin
stales is

oixss

TTic values of the

the

binomial

of distinct
arrangements
5 ~ 5 spins down.

are for N - 10, when: 2.v

K I. Tlic toul numtwt
\\ -

9's

System

arc taken

h
of

fro

coefficients.

-10

-8

-4

Spin

To illustrate that

the

the result, we consider

sites, numbered from
atom

provision

single

excess

2s

Alloy System

Binary

an

-2

-6

for

exact
an

alternate

1 through

of chemical

species A

sites.

In brass,

vacant
state

of the

of the two states

nature

on each site is irrelevant to

with N distinct
alloy
crystal
1.8. Each siteis occupiedby either
chemical species B, with no provicopper and B zinc. In analogy to C),

system\342\200\224an

12 in Figure
of
or an atom
A

alloy system

could

be

can be written

as

A8)

nry

Allay

Sya,m

\342\226\240=
o

20

Number

Figure

were
throw

1,7

An

experiment

NX) times.

thrown

10

23456789

01

of

heads

Was done in
The number of

10 pennies

which

heads

in

each

was recorded.

0\302\25100
3

Fijutc

\302\251
5

chemical

0
6

10

II

012

1.8

A binary
componenls

alloy syslcm of two

A and 1!,whoseatoms

of a

state

distinct

Every

system on

binary alloy

in the

is contained

sites

symbolic product of N factors:

(A, +
in

conventionally
N

B2)(A3

+BN) ,

+ Bj)---(A.V

A9)

The Liverage composition of a binary

is specified
conalioy
the chemical
formula A1_1B1, which means thai out of a tola!
by
the
number
of A atoms
is NA ~ A ~x)N
and
the number of B

to

analogy

of

4-

B1)(A3

atoms,

atoms is NB

D).

.v lies

.\\JV. Here

between Oand 1.

The symbolic

expression

is

of

g{i\\\\f)

B on

which

is identical

prediction

of

B' gives the

in A'v\"'

term

of N ~

\302\243
atoms

and

result A5) for

to the

the

spin

model

system, except

for notation.

Function

Multiplicity

experience that systems held at constanttemperature

well-defined
this stability of physical propertiesis a
properties;
The
of thermal
physics.
stability follows as a consequenceof

have

exceedingly

bharp

function

that

the

from common

know

major
the

of

or states

arrangements

possible

Sharpnessof ihe
usually

The coefficient

N sites:

atoms

We

result A2).

to the

analogous

number

peak

in the

from

away

the steep

of
and
multiplicity function
can show explicitly

the peak. We

large system, the function <j(Af,s)

the value 5 = 0. We look for an

defined

by

A5)

thai

us

allows

a very

sharply about

is peaked very

approximation that

variation
for

to examine

the

jV \302\273
\302\253
We cannot
(ook up these
i and
N.
form of g(S,s) versus 5 when
js|
tables of factorials do not go above N = 100, and we
values in tables:
common
may be interested in Af =^ 10'\302\260,of the order of the number of atoms in a soiid
is clearly needed,
felt.
An approximation
specimen
big enoueli to be seen and

and a good oneis available.

It

to work with
to be
understood

is convenient

logarithms

are

standard usage is In for

ambiguity

whatever.

log

When

base

where

f-xccpl

log*/,

loy base*?,written
c, but

it

is clearer

you confront a

very,

here

.-ilierwise
as log.

to write
very

specified, till
The international

log when

there is

number

such

large

no

;is

Sharpnessof the
2iV, where

iV

is a

lG:o,it

simplification to look at the logarithmoft he

of both sidesof A5)

the logarithm

take

We

by virtue of ihe characteristicproperlyofthe

logxy =
the

With

logx + logy;

4-

\\N

number of magnetsup

and

of a

B2)

s)l ,

product:

~ logy.

log.v

in

N\\

\\N

B2)

down,

=\302\253

A',

5;

{23)

by use

B5)

of die

\302\273
1.

terms

\" \342\226\240
in the
1,A2iV) +

result

This

Stirling approximation,
1

ZjTi'Go

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

s-t\\Q\\

argument

\\

B6)

N,
large
Appendix A. For sufficiently
may be neglected in comparison with

is derived in

for N

B5)

logW,!.

+ IJ[12N)

BrtN)ti:iNNcxpl~N

B4)

as

appears

logiV,!-

which

.V!

the
N.

of both sidesof B6)to obtain

the logarithm

take

of

the logarithm

evaluate

accordingto

We

log&N

logarithm

log(.\\-/_v)

logg(N,s) - logW! We

number.

notation

jV, =

for the

Function

obtain

lo

- logfrV + 5)! -

= logN!

\\ogcj(N,s)

Multiplicity

logN!

(N + |) log

2k +

I log

N.

B7)

Similarly

!ogjVt! s

I log

(JV, +

2?r

logN,! s iiog2* +
After

- jV,;

BPJ

J)log.V,

- Nu

B9)

of B7),

rearrangement

log.Y!

(,Vi

JJlogN,

wlK'i'ciwcliaVcuscilW

Ito\302\243B!r/A')

= .V,

'.- f.V,

I-

.Vt.

\\

-V, +

i)logJV

- (.V, +

Nj)

CUf

\\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

because

be simplified

may

logOV,/iV) =
~

by

log^l

4-

-iog2

+ Bs/,V)

the

expansion

!og(W,/A')

= logld

of

virtue

2s/jV)

-f-

2s/S)

- I2s2/N2)

x) =

logfl +

+ iog(i

-iog2

.v

C2)
for x

\342\200\242
\342\226\240

jx2 +

valid

-,

\302\253
I.

Similarly,

On subsliiuiion in

C!)
iogg

We write this

-log2 -

- 2s/N) =

B5/N)

Qs2/,\\'!).

C3)

obtain

we

s |logB/;E/V)

Wiog2

C4)

2s!/N.

result as

C5)

C6)

WnH)\"*?1.

Such

of values of sis

a distribution

of C5)
number

over the range

of states. Several useful
\342\200\224
co to

The exact value of y(N,0)

caiicda

+ co

for s gives the correctvalue

integrals

is given

are

by A5)

with

The

distribution.

Gaussian

treated
s =

2*for

in Appendix
0;

integral*
the total

A.

C7\302\273

\342\200\242

The

replacement
errors.

significanl

of a

slim

by

For example,

X s

=--

such as \302\243
by f{_.
{. - \342\226\240)

an iniegrai,
ihc rai io of

i{N2

N)

to

Ts./s

\302\273^o

is equal

io

+ A/N),

which approaches i

.)Js,

usually

'

as N

approaches

co.

= IN2

does

10

\\
1.9

Figure
(he

X.

\"

\\

\342\200\224

plotted

\\

cocfficicnis

iinearscaie. On this
on

distinguish

The

approsimaiion (o

Tlie Gaussian

binomial

ihc

entire

scale

g{!OO,s) plotted on a
ii is not possible io

drawilig
range

the approximation
of s is from

dashed lines ai\302\253

drawn
from
vaiuc or
points at t/e or (he maximum
4- SO. The

n
y

-10

-20

For N = 50, the

in

C6) is

from

vylue

value

is 1.264

x 101*,from C7).The approximate

1.270 x 1014.Thedistribution plottedin Figure

t.9 is centered
= 0. When
=
to e~' ofthe
s1
value
is
reduced
the
of
g
{N,

at s

a maximum

value.

maximum

of sE0,0)

That

is, when

s/N = A/2NI'2 ,

CS).

meaise\021 of g(N,0).The quantity

is Ihus a reasonable
A/2NI'1
width of the distribution. For N =s 1022, the fractional
width
is of the order of 10\"u. When
N is very large, ihc distribution is exceeda
in
It is this sharp peakand the continued
relative
sense.
defined,
exceedingly sharply
to a
of the multiplicity function
from
the peak that will lead
far
sharp variation

the

measure

of g

value
of

the

prediction
well

defined.

fractional

properties of systems in thermal equilibrium

We now consider one such property,
the
value of s1.
mean

that

the physical

are

50

the
y.

to

ChapterI: Stales

Modal System

of a

AVERAGE VALUES

The averagevalue,

mean

or

function

distribution

of a

vaiue,
is defined

P(s)

function f(s) taken over a probability

as

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

normalized lo

is nol

we

and

g{N,s)/2s,

D0)

distribution A5) has lite property

have

If

unity.

\302\243J'($)

D1)

are equally

states

all

that

A7)

\302\253
2W

Zs(iV,5)

and

unity;

!.

\302\243?(*)-

The binomial

to

is normalized

function

distribution

Uic

that

provided

09)

probable, ihen P(s) ~

average of/(s) over this

t. Tfic

distribution

be

will

D2)

Consider tile function

C6),

we

and +

in

replace

f{s) = s2.In

D2) the sum

over

\302\243

the

led to

that

approximation

s by

an integral

\342\200\242
\342\226\240
\342\226\240

ds

between

C5) and
~- co

co.Then

- [2/nNI'3

(jV/2)J'J

J^Jxx^\"'*

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

(jt/4)\022

whence

<i-J>

The

quantity

spin

excess

<{2i);>

= iiV;

is the mean

<B,y> =

,V.

D3)

square spin excess.The root mean

square

is

<B5}2>';J =>yfN

D4)

Sys

<uy Magnetic

and the fractional

2s is

in

fluctuation

as

defined

D5)

The larger N

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

of

Energy

System

Magnetic

Binary

The thermal properties of the model system

when
become
relevant
physically
the elementary magnets arc placedin a magnetic
for
the
energies
of
ihen
ticid,
the different
states
ate no longer all equal. If the energyof the system
is specified,
ihen only the suites having
this
ion
occur.
The
\302\273f
ink-net
energy
tn;ty
energy
ofa single magnetic moment m with
a fixed
external
magnetic field B is
\302\273
-m-B.

the potential energy

of
For the model system of

This is

orientations in

a uniform

the
Ar

H6)

magnet

in

field 1J, the

magnetic

ihe

- MB ,

toial magnetic moment

2s/n.In this

or

Following

sections.

The value

^f (he

field ?.;

magnetic

dependence
2s

by

-2,

is,

spacing

for

energy

special

i..ucaka

by wrtitng

bsiween

Ae

the

by

inferact
the

lite

example

moment

adjacent

by

tnodcl,

particular

only

but

is developedm

with

of s.

value

U{s). Reversing a

magnetic

difference

of

feature

ihat

moments

D7)

concreafe no difficulty. Furthermore,

of (his model is constant, as in

of (he argument that

^ornrfcicly ridennined

lowers the total

by 2mB.The energy

is a

the generality

restrict

not

will

will

is

sec later (hat a

We shall

discrete.

levels

energy

adjacent

Constant

t.tO.

this feature
ihe

between

is

spectrum

quast-conttnuous

ihe spacing
Figure

of ihe encrcy U

of values

spcclnttn
continuous

M for the

expression

tola! potentialenergy
2smB}=

m,- =Q.

using

two allowed

with

each

mngncts,

elementary

B.

field

the

exicnial

the

This funcitotutl

single moment lowers

~2m,

levels is

and

raises

the energy

dcnotcJ by

Ac,

where

DS)

Chopset

UM./mB

s(.)

+ 10'

10

2.30

+ 6

45

3.81

+ 4

120

4.79

+2

210

5.35

252

5.53

210

S.3S

\342\226\240

__2

+2

\342\226\240

log g(

120

-4

4.79

+ 3

-6

45

3.81

+ 4

-8

10

2.30

+5

-10

field S. The levels

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

magnetic nmmersis

are labeled by

Example:

Multiplicity

system is

the

given

by Max
Sludent

problem is given

The quantum

slates

problem is the

solvable

exactly

simple. The beginning

do the

magnetic

s values,

oscillators.
The problem of tlic
function for harmonic
for which an exact solution for the multiplicity
problem

simplest

known. Another
was originally

m m a

their

in

ofa

Chapter

harmonic

the

quantum

the oscillator.
consider

a system

number of ways

number

The number

of N such
in which

states

is

infinite,

oscillators,all

a given

total

derivation.

energy

The

excitation

of

modern

way

to

eigenvalues

D9)

or

zero,

and

the

the

is

solution
entirely

sho) ,

s is a positive integer
of

this

oscillator have the

es =

where

for which the

oscillator,
is often felt to be not
derivation

nol worry about

4 and is simple.

model

function

harmonic

Planck. The original

need

binary

and to is the

angular

multiplicity

of each is one. Now

same frequency.

energy

We want

of

frequency
to

find

the

can
for

be distributed
tlie

among

e^rher.
pitcitv function fount!
We begin the analysis by
=

forwm'chff(i,\302\253)

problem of E3) below,

we

the

function

multiplicity

the same

as the

spin

g{N,n)
mufti-

function for a single oscillator,

here identical to m. To sojve the

numbers,

quantum

a function

need

the

is not

to tlie multiplicity

back

of

want

function

multiplicity

going

ail values

for

is, we

That

oscillators.

the

The oscillator

Af oscillators.

to represent or generate

ihe

scries

E1)

AS! Y,fl!!1 from

(S3),

but

^CfC

coS\302\260

not appear

t docs

' 's
the

in

a temporary
tool that
result.
The
answer
is
final
Jusl

will

help

us find

the result

(S2)
provided we assume\\i\\

<

|. For

the problem

of JV

oscillators,

the

generating

function is

E3)

becausetlie

of w;iys n term
in which
the

number

number of onSctedwuys
We observe

i\"

can

integer

;\\\\i\\Kai in the N-fold

n c;m be foiuicJ
as the

pftiJuct

sum

is picciscly
ihe
of iV non-iicg.nive

that

tj{N,n)

2) Thus

for the

\342\226\240
\342\200\242

(W

- 1).

E4)

system of oscillators,

ES)
This

result

will be

needed

in

solving

a problem

in the

next

chapter.

1: States

Chapter

of a Mode!System

SUMMARY

1.

The

In

function for a

multiplicity

N, -

N't

limit

ihe

syslem of N

with

magnets

spin

excess

2s =

is

s/N

A'

with

\302\253
1,

\302\273
1,

we

have

the Gaussian

approximation

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

2. Ifal!

of

states

the

mode!

spin system

are equally likely,

the

average

value

of

equal

to

52>

in the

3.

The

j''^JsstgtN,s)

Gaussian approximation.

fractional

of s2

fluctuation

is defined

as (s2yll2/N and

is

S/2N\022.

4. The

where

energy of the modelspin

in

is the

magnetic

syslem

in a

siaie of

moment of one spin

and

spin excess 2s is

B is

the magnetic

field.

Chapter

and Temperature

Entropy

11

ASSUMPTION

FUNDAMENTAL

PROBABILITY

3'\\

of ;in

Construction

Example:

3-

Ensemble

Most ProbableConfiguration

33

Spin Systems in

Two

Example:

Thermal Contact

3?

39

THERMALEQUILIBRIUM
TEMPERATURE

-\342\226\240!

ENTROPY

41

Floiv

On Heat

45

of Entropy

increase

of

Law

Increase

Entropy

Example:

LAWS OF THERMODYNAMICS
as

Entropy

-iS

50

a Logarithm

Example: Perpetual Motionof the

Second

Kind

50

SUMMARY

51

PROBLEMS

5:

1.

Entropy

and

52

Temperature

2. Paramagnetism

52

3. Quantum HarmonicOscillator

52

4.

5.

The
Additivity

53

of \"Never\"

Meaning
of

the

Entropy

for Two

6. Integrated

Spin Systems

54

Deviation

Note

we Jo

on problems: The
iitil

cinplusi^e

53

melhoJ of fhis

problem

chapter

soKing dl

lliis

siu

Chapter

2; Entropy

and Temperatui

One shouldno! imagine

will

mix,

the

one

contrary,
\302\260

W10

will

years

recognize that

ff

we

thai

two

wish

there
is

this

to find

of thermodynamics,

in

in a

gases

after a few days

finds .., ilia!not

then again

0.1 liter

separate,
until

a time

by any noticeable unmixing

equivalent to
practically

rational

we must

then

container,initially
mix again,

unmixed,

and so forth.

long compared
One may

enormously

On

to

the gases.

of

never. . . .

an a priori foundation for the

seek mechanicaldefinitions
of temperature

mechanics

principles

and

entropy.

J.

W.

Gibbs

between energy and temperaturemay

are
considerations.
in statistical
{Twosystems]
by probability
a transfer
does
increase
the
not
probability.
of energy
The

genera}

connection

M. Planck

only

be established

equilibrium

when

We slart

this chapter

that enables us to
a
of
average
physical property
system.We then consider
in thermal equilibrium, the definition of entropy, and the definition
of
systems
The
of
will
as
the
taw
second law
of
temperature.
thermodynamics appear
increase of entropy. This chapter is perhapsthe most abstract
in the book. The
chapters th;it follow wilt apply the concepts to physical problems.
a

with

value

the

define

definition

'

FUNDAMENTAL
ASSUMPTION
fundamental

The

assumption of thermal
of the quantum
states

likely to be in any
arc assumed to

be equally

states

accessible

states

closed

constant

system
volume,

over

of

probability

\"

\342\226\240
-

of a

ttt;tt

a closed

accessible to it. All

probable\342\200\224there

accessible

other

physicsis

system

accessible

is equally
quantum

to prefer

is no reason

some

states.

energy, a constant number of particles,

values of all external parameters that
may

will

have constant

and

constant

including gravitational, electric, and magneticfields.

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

influence

tmd&N/N
Unusual

the system,

\302\253
I.

properties

of a

system

certain states to be accessible

during

may

the

sometimes

time

make

the system

it

impossible

is under

for

observation.

at
form of SiO2 are inaccessible
low
or
starts
with
the
that
temperatures
glassy
amorphous
fused
form:
in a low-tcmpcraturc
to quartz in our lifetime
of this type by commonsense.
exclusions
experiment. You will recognize
many
We
treat
are
excluded
all quantum
states as accessible unless they
by the
the
scale
of
the
measurement
of
the
time
specification
system (Figure2.1)and
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
If we specify that ihe
are of no interest.
point that its statistical properties as such

Fof example,the

states

of

the crystalline

in any observation
silica will not convert

2; Enxropy

Chapter

and Temperature

I imtt

of

of ihe

spcMftcation

sjstcn

2, t
A iwdy symbolic Ji:iKr;ihi:
L-:idi solid s|x'
slate
of a closed sysn
represents an accessible quantum
fundymema!
of statistical pliysics is tliat a
assumption
is equally likely
to be in any
of tlic quantum
si;
system
accessible to it. \"Die empty circles represent some of thi
that
are not accessible because their
do nc
properties
the specification of the system.
vjfju -1 ,-/<_
IlovG

V\\uil-

system

is exactly

in a

stationary quaniurn state s, no statistical

is left

aspect

in

the problem.

PROBABILITY
to be tn any
likely
Suppose we have a closed sysiem that we know is equally
of they accessiblequantumstates.Let s be a genera] state label (a\302\273dnot one-half
ihe
in this slate is
ihe spin excess). The probabtHty P(s) of finding
sysiem

P(s) =
if

the

fundamental

dosed,
systems

state

5 is
assumption.

accessible and P[s) =

We

shall

on [/and on

A'.

panicle
A),

consistent

otherwise,

be concerned

for which the energy V and

wtH not be a constant as in
P(s)

(t)

\\fg

but

taier

systems

that

ihe

fun-

are not

vary. For these

have a functional dependence

number
wilt

with

with

N may

Probubitiiy

sum

The

the

of

\302\243P(s)

the total

because

over alt

probability

probability

that

the

sysiem

_,

states is

is in

equal

always

to

unity,

is unity:

some state

B)

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

defined

probabilities

probabilities

by (I)

is

I'{s)

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

is
are
to
the sysiem
in the state s. The angular
brackets
used
\342\226\240>
<-\342\226\240

This

that

equation

average value.

For a dosed system,

the

average

of A' is

value

!'

'

>':

/\"i>-'-f

denote

D]

alt g

because

now

average

in D)

accessible slates are

likely,

equally

elementary exampleof
we imagineg simitarsyslems, in
is an

what

average;
Such a group of systems

averageof

any

_1_

property.

one

constructed

over

properly

the

alike

ts

may

each

be

P(s) =
an
called

accessible

\\jg.

The

ensemble
stale.
quantum

catted an ensemble of syslems.The

is catted

group

with

ihc ensembleaverageof that

'
\342\226\240'
'\342\200\242\342\226\240>\342\226\240',
.\342\226\240>.

alike.
all consfrueled
is composed of many
systems,
of the
in one
is a replica of the actual system
Each system in the ensemble
If there
are g accessible stales, then
quanium states accessible to the system.
Each system
for
each
stale
there wilt be g systems in the ensemble, one system
to the actual sysiem.
in the ensemble is equivalentfor all practical
purposes
ensemble

An

Each
and

in

sysiem

this

of systems

satisfies

sense

all

external

is \"jus! as

requirements

good\"as

the

actual

placed on the
system.

Every

original system
quantum

stale

Tit

'[!\".;\"*'\342\226\240\342\231\246

'';\"(:!'

-rrrt

\302\273'.\"*

t
:\302\273\":;'\302\273''\342\226\240:

t';t

t: r;jt

:y

'[in

sT'\"\302\273

rn;

/.:Y:t

fit

rft

:t:;Y

i'YY
2.2

l;ij;ure

cuscmbJc

Tliis

of lOspiiw wiih

\302\253
iJirotijiJij

of an

Construction

represent a dosedsystem
each
frequent

in

a magnetic
use

of s

of

field is

as a

Mi

;m

I
;l
2.v

tlie

cusciubl

as

in

is

ensemblefive spins,

implied

or

in

We conslruci
each system with

-mB. |Do

stale index

2.2.

Figure

ensemble by one system in a

We assume
that the ensemble
the fundameniat assumption.

in the

is represented

representsthe real system\342\200\224this

Example;

\\

sighificance.

stale,

quantum

Y.

[\\

ilic
|0, so tliut
Hi syML-ins,

accessible lo the actualsystem

slaiionary

spin excess

sy>(cnis

icpresciiis

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

cl]sv-]I]!iIc iiium ^inlnin
rcpfcscutiiiive
Uic vuriou^

\\

Tlic

order in which
listed has no

-t

-Sui/Jimd

etwujy

yi

-\342\200\242Tit

;i

'nrt

/[r;i

: t

\342\200\242
\342\200\242

\"U.:'j\\

not

label.)

confuse

!he

Each system

in

spin

2.3

Figure

2s =

excess

use of

in

spin

an

ensctnMe

to

{.The energy of
excess

represents one of the

with our

muliiptes

of

t tl'OutibiC

represents a system

enscmbie

The

2.3

Figure

at tin's

states

Tile 10 systems
If the

have

2s

2s

have

and

2s

= 3;
t

|Q sysiems
has

system

have

2j =

7s

- 5.

- i.

- 5,a singie

ti1Ca\302\273embio.ThiS is

by tlic

I: 10

systems have 2s =

into

contact

-1;

.o!

function

multiplicity

m Figure 23 make up ttic cuwnibk.

5r ltn-'ii n sinylc sysitm
tiiLiitueliefieid weic siidi lli^t 2.\\- \342\226\240=

in llie

- -3;

number ofsuch slatesis given

enetcy.Tlic

shown

energy

5 systems

\342\226\240\342\200\242!
t

and spin excess 2i

A' = 5 and

Sy^m may represent

ii ii

! t

.! I

5 spins

With

R\302\253ute2.4

\342\200\236

| f

with

t'T

f\\

jTIT:

tj

i\\

K.O[ij\\j}U\\iilI0

tomjiriscs

systems

Most ProbableConfiguration
Let

two

systems

transferred

freely

2.5).The
with

net

two

constant
flow

from
systems

ofenergy

of

and
one
in

be

\302\243t

to

tttc

contact

U =. Ut

brought

This

other.

form a

is called

so that energy
(hermnl contact

larger closed

system

& ~

can be
(Figure

Sx +

\302\243z

a
+ U2.
from
one system to another? The answerleadsto the concept
The direction of energy flow js not simply a matter ofwhethef
of the other,
because the
one system
is greater than the energy

energy

of temperature.

the energy

5,

Whai

determines

whether

there

will be

r 2: Entropy

anil

Temperature

closed

Two

eomacl

in

The

ure

systems

u\\

in

of

Establishment

2.5

Figure

systems can be dificrcin

in

maximum

the

has

slates of two

systems when

in

contact
order

thermal
two

between

to define

spin

exchange of

and constitution.
two systems.
of

systems,

the energy.

&, and

lotal

energy

constant

of accessible states.

number

model systems
contact.

[wo systems

energy is that for

t6tal

the

energy

between

contact

Micrmal

size

sbared in many ways between

The most probabledivision

in

+ ut

Thermal conduclor allows

sulaliiin

accessible

ul

contact

thermal

system

s=
+\342\226\240
f/;

We
1

then

and
solve

first

and

2,

study
in detail

in a niagoetic

The numbersof spins N

which the combined

shall

We

can be

enumerate

what characterizes

the

the

the problem of thermal

fieldwhich isintroduced
maybe

u N2

different,

and

the values of the spin excess2s,, 2sz may be different rOr the two systems. All
take
have
moment m, Tlie actual exchangeof energy
spins
magnetic
might
place
the
interface
between
via some weak (residual) couplingbetween
near
the
spins
the two systems. We assume
states of the total system & can
that
the quantum
be represented
a
state
of
accurately
any
by combination of any state of 3, with
We
but
the
of
the
excess
are
allowedto
values
constant,
S2.
keep N,, N2
spin
change.Thespin excess of a state of ilie combinedsystem will be denoted by 2s,
is dirccily
where s = sx + sz. The energy of ihe combinedsystem
proportional
to the total spin excess:
s2)

U{s)

The tola]

number of particlesisN

A'(

+ .Vj.

~2inBs.

E)

Most ProbableConfiguration
the energy splittings betweenadjacentenergy
leveh
are equal
so that the magneticenergy
systems,
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
that

assume

We

to

both

in

7n\\B

The

is always possible.
another
energy exchange with
system
+
is
because
is constant,
but
constant
t
he
total
st
s2
energy
systems are brought into thermal contact a redistributionis

two

the

when

s =

of

value

that

so

storage

energy

permitted

ihe

in

s3 and

of s,,

values

separate

the

in

thus

The multiplicity function

of the combined
g{N,s)
product of the multiplicity functions of the individual
the relation;

system

H2(Nj,s where

the

A.15).

The

To see

of s,

range

the

in

5Z by

F)

s,) ,

given by expressions of the form of

< N2.
if Nl
-fiY, to %Nt,

gx, g2 are

functions

multiplicity

and

5[

systems

to the

related

is

&

Uz.

I/,,

energies

is from

summation

how F) comesabout,considerfirst

that

of the

configuration

combined
systetn has

the first system

has spin excess2sj and the second
system for which
A
as the set of all states with
excess
is
defined
2s2. configuration
specified
spin
values
of s( and sz. The first
accessible
states, each ofvvhich
system
hasg^N^s,)
of the g1(N2,Si) accessible stales of ihe second
any
may occur togeiher with
The
total
number
of states in one configuration of the combined
system
system.
of Sk
functions
the
is given
of
the
multiplicity
product gl{N1,sl)g2{N1,Si)
by
~
~
s sit the product
of the g's may be written as
and &2. Because s2

This

Different

values

one

forms

product

term of
of Uie

configurations

of j{.

suitesof

all

We sum
ihe

sum we

hold

with

s, N,,

to obtain

ofs(

fixed s

states

N2 constant, as

the total

or fixed energy. We

numberof accessible
and

characterized by

system are

combined

over a!!possiblevalues

configurations

where y{N,s) is the

the sum F).

part

of

the

combined

of

the

specification

thus

different

number of
obi a in

F),

system. In the
of therma!

contact.

The result F) is a sum

of

for some value

maximum
The configuration for which
cmtfigurntiun;

ilie

number

of the

products

of s,,
glg1

of states

to

sL,

say

is a
in

it

gxiN1.Sl)g2[Nl.s

form G).
be read

maximum

Such a product\\sill

us

\"st

hat\"

is called the

or

be

\"si caret\".

most probab!e

is

- 5,).

(8)

am! Temper

2: Entropy

Chapter

A*.

Thermal

of Ihe dependence of the

repressaiion
on [he division of ihe tola! energy
multiplicity

Sclicmalic

2.6

Figure

coiifiguralioji

!f ihe

are

systems

and Sj.

two syslems.-S,

belwcen

equilibrium

large,

extremely sharp, as in

the maximum

with

to

respect

in Sj will

changes

be

of configurations
will
dominate
the
statistical
of the combined system. The most
properties
alone
will
describe
probable
configuration
many of these properties.
Such
a sharp
of large
maximum
is a property of every realistic type
system
for which exact solutions are available;
that it is a genera! property
we postulate
that'fluctuations
of all largesystemsthe sharpness
From
properly it follows
about the most probable configuration
a
sense
ihat
we will define
in
are small,
The imporlani
result follows l hat the values of the average physicalproperties

of

contact

in thermal

system

large

described by the properties nf

which

configuration
for

values

(used

Because

number

the

in either

of the

A relatively

2.6.

Figure

the

in

such

a replacement

(8).

and

the configura-

by an

the

equilibrium

average

average over

of a

average

values.

physical

only ihe most

example below we estimate ihe errorinvolved

the error
lo be negligible.

In the
find

replace

F)

are accurately

is a maximum.Such
thermal

may

system

configuration,

of these two senses)are called

sharp maximum, we

configuration

large

probable

of accessible st3tes

quantity over all accessibleconfigurations

probable

another

with

most

small number

Most Prabahte

Example:
tfiL-

sharpness

Tn-o sprn systems in thermal

contact.
We investigate for
of the produci G) near the maximum
(8) as follows.

functions for(j,(W,.s,)

Ilie muliiplicity

white ?i(Q)denotesjj,(:V,.G)

and

and

ffsf.Vj.Q). We

denotes

^@}

--^This

gives

product*

We

find

the

is,

properly

of

maximum

of statesaccessibleto
is 2s,

and the

spin

excess

replace s,

of ihc first

- *,:

(jo)

-l^iiLj.
system when

combined

the

by

spin syslem
of
product

the

spin

system is 2s,.

value of(tO}as a function

of s, when the total spin esccss 25 ishd.l
the energy of the combined
is constant, it is convenient
systems
that the maximum of fog.m) occurs at the same \\atue of x as the
From
The calculation
can be done eilher way.
f !0|,

the maximum

constant; that
to use

the number

combined system

of the

excess

modd

lUc

We form the
ofiho form of|U5):

^olh

g^i-^J-

ConfiSui

>'{.y).

when

uy

be

if the

a minimuni,
second derivative of

a maximum!

or
the

z point of inflection.
is negative,

function

^~-.

~^T-~

The

so

that

(II)

e\\tr\302\243nuim

is

curve

bends

the

downward.
Ai

the

cxt

Nt, N2. and

where
Equation

* The

product

s are

held

as s, is

constant

varied. The second derivative

A1) U

fund

ion of two

Gaussian

fund

ions

is always a

Gaussian.

c1/csi1o(

and is negative, so thai

of the combined
system

the

Tims the

is a maximum.

extremum

is thai for

which

most

configuration

probable

is satisfied:

A2)

t
to interchange ofenergy
when
the fractional
to the fractional spin excess of system
2.
spin excess of system
alt the accessible stales of ttic combined
We prove itiat
nearly
satisfy or very
systems
then A3}
of s, and sj at the maximum,
nearly
satisfy
(U). if s, and 52 denote the values
two

The

arc

systems

in

with

equilibrium

respect

1 is equal

of slates

number

iiic

find

most

the

in

we

configuration,

probjble

insert

A4}

in {9}

A5)

(-25I/N).

To

the

investigate

of

sharpness

of gigl

s, introduce &

that

such

the deviarion

measures

Hcre^

Square

to

j,,ij

s,

of su

<5;

sj

st from

their

in {9} and

A5) to obtain

deviation

from (H)
ii

from

thai

\302\253

V.vi.so
.'.\\'u

s,/jVj

As a numerical
let Ni

values

- 5.

A6)

Su Sx at

the

maximum

o(g,gi.

equilibrium

so

of sialcs

45,^

2Sl

4s2S

slatesin
!ii;it the
the number
number of
of slates
that

2d2

a configuration

is

l(N2J2

\302\253
,V.

s2

number

the

know

fonn

we substitute

which

We

value of

a given

at

to

of
ot
\\

- 3) =

te.ffiU.e

;v~

the fraciionat
devbiion from equilibrium is very smalt,
example in wliidi
= ^00, and the
=
!0:i and 5
10'2; ilia! is, <5/A'i = !O\0210. Tlien,2ii!,'iVi

Thermal

Equilibrium

product g,^i is reduced lo g\"\02100 = lO\0217* of its maximum value. This is an

so that g,g, is truly a very sharply
function of st. Tiic
laigc reduction,
peaked
tlie fractional
that
deviation will be 10\"'\302\260or larger is found by integrating
&

out lo a value

I0u

of the

probability

of (he order of
Tiits

distribution.

of N, thereby
is the subject of
s or

by N x

including

ihc area

Problem 6. An

tO\"t14 =

extremely
probability

{17} from

under

the

limit

upper

wings

to the

10~i!2,si ill very smalt. When two

ihermal contact, the values ofsi, Sj thai occur most often will be very close to
rare io (ind
the
values
It is e.Uremely
off,,
S] for w hich ihe product g]g1 is a maximum.
with values of*,, s, perceptiblydifferent
from
systems
?\342\200\236
st.
to say that the probability
a fractional
What does it mean
the system wjlh
of ftitding
deviation larger limn 5 .V, = \\Q~10 is Only \\0'!ii
of the probability
of finding the system
as
We mean that the system wilt never
be found with a deviation as much
ill equilibrium?
in tO10, smalt as this deualion
1 part
seems. We would have to sample !0IJ2similar
systems
lo have a reasonable chance of successin such an experiment.
If we satnptc one system
every
is prctlv
Usi sunk, we would
10'1
iuive
to sample for 101J\"s. The age of the
s, which
is only 1O'Bs. Thereforewe say with great surely that lite deviation
described wilt
universe
be observed. The estimate is rough,
from
never
the message is correct. The quotation
but
Uoli/iitaun
is relevum here.
given at iUi beginning of this chapter
We may expect to ob>mc substantial fractional
deviations
only in the properties of it
of a small
imiili
in thermal contact with
a targe
system
system or reservoir. The energy
of 10 spins, in thermal contact with
reservoir may undergo
a large
system, say a system
on ihc
lhat are largi! in a fractional
fluclualions
sense, as (lave beenobservedin experiments
of small particles in suspension
in liquids. The average energy of a small
Brown tan motion
be determined
with a targe system can altvays
accurately
by observations
system ill contact
on one sronlt
a! one time on a tatgc number of identical smart systems
or by observations
are in

systems

over

sysicm

result

period of lime.

a long

THERMAL

The

is given

probability

integrated

EQUILIBRIUM

for

of accessible

number

ihe

stales of two model spin

systems

in

in thermal
contact, with
generalized to any two systems
constant toial energy U
extension
of the earlier arguBy direct
U2.
Ul +\342\226\240
is:
the
argument,
g(S, V) of the combiited system
multiplicity

may be

contact

thermal

summed

over all

values of

states of system 1
specified

by ihe

at

in

The

sum

o\\er

Jiicrgy

value of

ofaccesstblcstates

Us < V. Wzxz
Ux. A

:nl configuraiioits

the

is lite

a configuration

gi

itU

%)

is the

number

of accessible

is
of the combined system
The
number
constants
U,Nt, -V2.

coniigiiratioit
with

(.\342\226\240',.
together

g X{N

product gt{N],Ui)()i(Nz,U

~ Ut).

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
be
zero
for
an
infinitesimal
of
g{N,U)
energy:
exchange

dg =

(-\342\200\224]

divide

We

g2t!Ul

by glgl

lV, +

9i(^~\\d

and use the

result dV2

~tiUx

dU2 -

to obtain the

0.

A9}

thermal

equilibrium conciiiion:

Lflfs
we

which

may

write

as

B0b)
We defitie the quanttiy

a, calledIhe entropy,
a{N,U)

where

a is

the Greek

letter sigm:i.We

by

\\

now

write

B0)

in the iimii form

B1)

Ns is held

means

lhai

panial

dcrivalivc

wiih

consiam
respect

in

ihe

to 0,

differttiljalion

is defined

as

o(g,{Nt,U,)

with

tespeel

lo U,.

Thai

is,

ili=

Teutperutute

is the

This

condition

Here

contact.

ant!

Afi

two

for

equilibrium

symbolize

not only the

us immediately

to the

/V2 may

on the

constraints

ail

thermal

for

systems

in

thermal

numbers of particles,
but

systems.

TEMPERATURE

The last equality

the

know
systems

rule:

everyday
are

leads

B2)

thermal

in

If T

of the

temperatures

two

equal:

be

must

denotes

inverse

the

equilibrium

= t2.

r,

This rule

concept of temperature.We

ttie

so that T

to B2),

equivalent
ahsohite

B3)
must be a function

in ketvin,

temperature

this function

of

V)s.

(ro/f

is simply

iSie

relationship

B4)

The proportionality
L-on^mnt.

As

constant

determined

\302\273
U81

10~\"joulcs/ke1vin

\302\253
1.3X1

10\"Ulcrgs/kelvin.

discussionto Appendix B becausewe

temperature scale:we

called the

ilott/iiumu

experimentally,
kn

We defer the

constant

;i universal

is

ku

define

the

fundamental

B5)

prefer

temperature

10 use

a more

natural

r by

B6)

This temperaturediffers

from

ihc

Kelvin

temperature

kBT.

by the

scale factor, kB:

B7)

t has the dimensions

Becausea isa pure number,thefundamental
temperature
unit
of energy. We can use as a iemperature scale the energy scale,in whatever

2;

C/iapier

and

Entropy

Temperature

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
selected so that the triple point of wmer is exactly 273.16K.Thctriple
arbitrarily
of
water
is the unique tcmperaiurc at which
water,
ice, and water vapor
point
may

be employed

coexist.

Historically,

the

to build

accurate thermometerseven

quantum states was

measure

though

understood.

not

yet

temperatures

thermometers

with

age in

it was

possible
of temperature
to
Even at present, it is still possible to
in kelvin
to a higher
calibrated
which

relation

the

wit h which tlie conversion factor kB iiself

is known\342\200\224
million.
of
discussed
in
are
per
Questions praciical thermomeiry

precision

the

than

32 parts

about

as

from an

dates

scale

conventional

accuracy

B.

Appendix

permissible to take

the

of both

reciprocal

sides to

B8)

The iwo
was

B6)

expressions

given as a

determined

U with

of

differentiation

V). The
function of

of

definition
different

respect lo a

with

Eemr^caiufe

is die

oilier

in lhermal

ej.pcrinicnts

same

in

The

other

itrot

\"What
some

in

B6).

the entropy

<r

= a{U,X).Hencei
In B8).
V(a,N),

but

cases,
in

in

as a

\342\204\242
t(U,N).

mpties
both

because

phy.
we

id M

variab]

N consiant

variables.

independent

in

leaning,

diOcrcu

variables U

independent
the same indcpendeiu

variables?\" arises frequently

some variabtcs, and

have a slightly

the

has

B6)

from

and B8}
of

function

it

is

however,

so that t

expressed

ihc independent
we coniroi
experiments
are

variables.

ENTROPY

Tile quantity
entropy

ts

as

defined

logg

introduced

was

as the

in B1)

logarithm of

system. As defined, the entropy

the entropy i'is defined
by

is a pure

the

as ihe

number

number.

entropy of the system:the

of

slates

In classical

accessible

to the

thermodynamics

129)

Entropy

Figure 2.7
than

&

energy

if the

increase

U from

of a positive

system

total

the

condition if
the

cooler

energy

body

established.This

U2+8U

of ihe
value

words,

is

cm ropy.

increasing

Energy transfer

o,(final) +
As a

>

cMXinai)

+ oa(iniiiai)

o^iniiia!)

consequence of B4), we

see

o are

5 and

that

connected by

scale

factor:

130)
We
of

wilt

call

S the

conventional

number of particlesin
may
3)

the

on

depends

the

definition

on the
of the entropy
The
of
the
system.
entropy
energy
variables: the entropy of a gas(Chapter
dependence

independent

of

thermal

... is

limited

by

the physical

physics

author

the

Thus

Britaiiuka,

Encyclopaedia

of entropy

fn

(he volume.

known.

not

the entropy,

the greater

on the

and

system

on additional

depend

in Uic early history

was

entropy.

The more statesthat are accessible,

a{N,U) we have indicated a functional

lih

the

ed.

fact

significance of the cm ropy

of the article on
wrote:

A905),

that

\"The

it

does

not

in

thermodynamics

of

utility

correspond

ihe

the

conception

directly

to any

is merely a mathematical function

but
directly measurable
property,
of the definitionof absolutetemperature.\" now know v.hat absolute physical
of the experiof the comparison
properly the entropy measures, example
physical

We

An

experimental

Chapter

and

determination

theorctic.il

of the

calcutiition

entropy

is

discussed

in

6.

Consider the

energy All

from

tot;il entropy changeAa

1 and

add

the same

when

we

remove

the

more probable
flows from the wanner b
when lhermat contact is
an otamptc
of the Saw of

wiii bt: in a

system

to

2 v.itt

-f a2

a,

entropy

of

amount

to system

combinedsystemsover ihe initiat

<j,(initia!) + ^(initiat). In oiher
finat

is higher

r,

temperature

the transfer

t2,

a positive

amount of energy to 2, ;is in

amount of
Figure

2.7.

2:

Clmptcr

The

ihe quantiiy in

> r2

t,

p;ireniheses on ihe righ>hand

Loial change of entropy

so that the
the

from

Tehtjter

change is

tolnl entropy

When

is

urn!

Entropy

system

the

with

is

higher

when

positive

to the

temperature

is positive,

side

the direction

system

of energy flow
lower

the

with

temperature.

Example:

heal

with

fansitiariiy

This example makesuse

on heiitjlow.
and specific heat.

increase

Entropy

of

ihc rentier's

previous

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

(aj

Let

with an

AV

where

C.89J

ihe tempcraiures

- 290K)

K-'HTV

are

in

Tj

\302\253

|C5O

linat temperature

Ttie

kcMn.

- C.89JK-')C5OK

290JK

after

contact

Tf)

is

= 32OK.

Thus

At/,

\302\253

C.89JK~!)(~3OK)

-11.7 J ,

and

At/3 = -At/,
(b)

What

is the

taken place, almost

fraction of ihe final
considered
temperatures
of

change of entropy
immediately

after

of

the

initial

two

= U.7J.
specimens

con'act?

when a transfer pf

Notice

that

this

transfer

0.1J has
small

is a

contransfer
transfer as calculated above.Becausethe energy
at their
initial temperawe may suppose the specimens are approximately
of the firsi body is decreased by
350 and 290 K. The entropy

is small,

energy

Lan

Tile cnlropy of iiic

second

S2

iotal

Tile

increases

enlropy

AS, +

of the

= 3.45

,7~

of Enlnpy

by

by

10-4JK-' = 0.59

AS, = (-2.S6 + 3.45)x

units the increase

In fundamental,

where

is increased

hody

of Imrrrmc

of entropy

1CTJJK~

*s

Botl/.ma\302\253n
constant.
This resuil mcaaS thai
(lie number
of accessible
tjisihe
- enp@.43x 10l9>.
two systems increases by (he factor exp{M

st;it

Law oflncrease of Eniropy

We

can

ihc loial

thai

show

broughi
If (he total energy V
into

systems

arc

thermal

in

contact.
~

ctttrapy

two

jusi demonstrated this in

U2 is consiant, the lotal multiplicity

V% +

systems
a special
after

;trc
case.
the

is

contact

thermal

when

increases

always

We have

ff(t/)\302\273=

^0,A/^A/

by A8). This expressioncontains the

term

t/,)

gi(EAo)i/i(^

C3)

~~

^to^

^or l^e

i-XiiiVd^

terms besides.Here ViQ is the

the initial energy ofsyslem 2. Because
initial energy ofsystem 1 and V
l/lois
increased
all termsin C3) are positive numbers, ihe muitipliciiy is always
by
This
is a proof of Ihe
establishmenl
of ihermal conlaci bclween two systems.
taw
of increase
of entropy for a weli-definedoperalion.
effect
of conlact,
the effect that slands out even after lakingthe
Thesignificant
of tcims in iiic summaof ihe multiplicity,
is not just that Ihe number
logarithm
be very,
summationis large,
but that the largest single term in the summationmay
very

niuitiplicuy

before

contact

and

many osher

~~

much larger than

the

initial

muilipiicity.

(Mi).,,

That

is,

= 9i(O,)gJiU

- 0.)

C4)

2:

Chapter

and Teniperatur

Entropy

with

Ut

= 0

parts and
probable
conftgL

the

presently

con figuration.
rat ions

be very, very

Hie cm ropy

in or

found

increases
or

muhiplicily

much larger than

ihe

moit

initial

essential

The

value

is lhat

effect

of

for which

Vl

the syslems

states

term

C5)

ihe product g^x is a

cvoive

contacl

after

configurations lo their final

configurations.
implies thai evoluiion in this operation will
final

configuratic

probable

Vl0).

9iiVtMU'~

Here 0s denotesthe

The entropy

probabilhy.

a{U) oflhe

ihe entropy

takes piao; between h

dose 10 tlie most
as the jysicm attains

of energy

will be

syucm

ofincreasirtg

reaches

eventually

may

* U. Exchange

anJ U,

maximum.
iheir

initial

fundamental

The
lake

always

from

place,

assumption
with ali accessible

probable.

eqtutlly

The statement

C6)

fffjnil

statement of the law of increaseofcnlropy:the entropy

when
a constraint
[ends to remain constant or to iucrease

of

is a

is removed.The operationofebtabitsliiiig
removal of the constraint that
Vu
Ux

U,

need be

configuration

V2

each

contact

be constant;

u closed

to she

is equivalent

system

sjstem
to ihe

after contact

only

constant.

The evolution of the

takes

thermal

iniernul

combined

a certain

system

time. If

we

lowards
separate

ihe

final

ihe two

thermal

equilibrium

systems before they

Add

energy

molecules

Decompose

Let a

2.9

Figure

(his cotifiguraiion,

reach
intermediate

view

and

energies

the entropy

constraint,

called

Processes
2.9;

Operations

function

(he lime

that lend

the arguments

that follow.

as a

in

we

io increase

lend

thai

will

an

obtain

an intermediate
of

the

lime

of evolution

in

of each

ofa

entropy

intermediate

up

syslcm.

configuration

with

io
entropy. Ii is ihesefore meaningful
tli.i' lias elapsed since removal of the

2.8.

Figure

lo increase the eniropy

support

the

linear polymer curl

process

ofa
will

system
be

are

developed

shown
in the

in

Figure

chapters

2:

Chapter

For a largesysiem*
occur

never

and Temperature

Entropy

with another large sysiem)ihere will

differences
belween the actual value of the
significant

thermal

(in

spontaneously

coniaci

value of the entropy of the most probableconfiguration

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
10's
s.
universe.
We can only find a significant
difference
beiwcen Ihc actual entropy asid
ihe

entropy

and ihc

entropy

of ihe

shortly
which

most probable
have

we

afier

implies

that

the nature

changed
we

had

the

of

configuration

the system

prepared

system

macroscopic

of ihe contactbetween
initially

in

two

some

very

systems,

special

way.

Special preparation couldconsistof lining

parallel
system
up all the spins in one
or
to one another
in the air of the room into the
collectingall the molecules
a small
volume m one corner of the room.
Such
extreme
by
system formed
situations
artificial

never arise
operations

naturally

on the

informed

left

systems

but

undisturbed,

arise from

system.

Consider ihc gas in a room: the gas in one half of the room might
be prepared
wjiti a low value of the average
initially
energy
per molecule, while the gas in ihc
other
half of the room might
be prepared
with a higher value
of
the
initially
average
energy per molecule. If the gas in the two halves is now allowed to
interact
of a partition, the gas molecules will come
by removal
very
quickly'
to a most probable configuration
m which
ihe molecules m both halves of the
to
room have the same average energy. Nothing else will ever be observed
the
We
will
observe
to
leave
most
never
ihe
sysiem
configurahappen.
probable
configuration
and

reappear

later

in the

even ihough the equations

distinguish past and failure.

LAWS

OF

initial

specially

of motion

prepared

of physics

is true

configuration.This

are reversiblein

time

and

do not

THERMODYNAMICS

is studied as a nonslatisticaisubject,four posluiales

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

The

thermodynamics

calculation

of Ihe lime

required

for

Ihe

process

is largely a

problem

in

hydrodyna

Laws

condition B0b)for

of the

(e\\oSgt\\

{~\342\204\242rk

in oilier

words,

r,

comact:

in thermal

equilibrium

of Thtentotiynamks

feioSg3\\

/cloggA

/cloggA

{-furl:

{imX=

{~7urk

= t3

t3 and r3

rj

imply

r2.

Heat is a form of energy. This law is no more than a slaicment

of
liie principle of conservationof energy.Chapter
8 discusses
wliat form of energy
First law.

heat is.

Second

entropy, applicablewhen
is ill :l

of the

tluit is not

configuration

of ihe second law. We

ilie law of increase of

of

law

(he equilibrium

consequence

will

in successive

instants of time.\"Tins is

wilh Eq.

called

lo a dosed systemis removed.

The
increase of entropy is: \"Ifa closedsystem

ihc enlropy of the

be lhat

have

iniernal

a constraim

used statement

commonly

statements

equivalent

many

statement, which we

the statisiicai

use

shali

are

There

law.

cotiliyitnilton.ilicmosi |>rubnble
system will increase
monoiotiic;ilty
siaicineiil

a looser

ilian

he

one

we gave

C6} above.

The traditional
of

is the Kelvin-Pianck
formulation
is
for
\"it
to
any
cyclic
process
impossible
of heal from a reservoir and the perextraction
statement

thermodynamic

of second iaw

thermodynamics;

whose soie effect

is the
of
performance
an equivalent amount of work.\"An engine
that vioiaies
lhe second
iaw by extractingthe energy
of one heat reservoir is said to be performing
motion
ofthe
second kind. We will see in Chapter
8 that the Kelvinperpeiual

occur

statement.
Pianck formulationis a consequence
oflhe statistical
as the
Third
iaw.
The entropy of a system approachesa constant
value
due
zero.
The
ear!
test
of
this
statement
temperature
law,
loNemst, is
approaches
at
that
ihe absolute
zero the entropy difference disappears between all those

iaw follows

is

multiplicity

the

system

g@),

the

in

has

thermal

internal

definition

statistical

the

from

ground stateof

which are

a system

of

configurations

corresponding

zero. Glasses

is essentially

substantial,of
in

real

life is

to

objection

the

order

that curves

must come in

flat

as

affirming

have a

of [he

The third

entropy, provided ihat the

multiplicity. If lhe ground stale
as
t -* 0.
entropy is o{0) = iogy@)
is
that
does not appear to say much
of the

a weii-defined

From a quantum point of view, the law

not implicit in the definition of enlropy, provided,
in its lowest se! of quantum
at absolute
states

would not be any

equilibrium.

frozen-in

number

of many

r approaches

reasonable

0.

the system is
for
zero. Except
glasses, there
that (j{0) is a small numberand
c{0)
for them o{0) can be
and
disorder,
the
third
law tells us
of atoms N. What
plotted against x
quantities
physical
however,

that

Chapter 2: Entropy
as a

Entropy

and

Logarithm

Several

useful

stales itself.First,

the

ihe definition

from

follow

properties

number of

of the

rithm

Temperature

accessible states, hut

two

of

entropy

of (he cmropy as the iogathe number of accessible

systems is liie sum of lhe

of as

cad

independent

separateentropies.

Second,
the

the

never meant to
for

that

entirely

imply that

a discrete

tite

practical

purposes\342\200\224-to

We have

defined.

is

exactly, a circumstance

is known

energy

system

of energy

spectrum

ali

insensitive\342\200\224for

the energy of a closedsystem

with wiiich

6U

precision

is

entropy

eigenvalues would

of

number

the

make

We have
depend erraticallyon ttie energy.
simply not paid
much attention io lhe precision,wlicthcr
ii be determined
by the uncertainly
h, or determined otherwise. Define <0{U)as the number
principle <5U 5{time)
of accessible
srates
unit
per
energy
range; O{U) can be a suilablesmoothed
of
V. Then y{U) ~ i>{UNU is lhe number
accessible
centered
at
average
stales in the range SU al V. The cmropy is

accessible stales

a{U)

of

order

the system

as for

Typieally,

2V.

tola!

lhe

If

particle energy

then

A,

.
Let N

logO(t/)
of N

energy
C(l')

. a{V) =*

~ IO20;A

*\302\273
0.69

\\

C7)

of states

number

total

the

order of N

is of the

times

same

be

of ihc

average

one-

will

2;7jVA. Thus

and 5U
x

\302\273
10^'

10:o

C8)

+ log^C.

--'logNA

Nlog2

IO\021* erg;

a(U)

spins,

-t-

erg.

- 13-82-

2.3.

C9)

is dominated overwhelmof the entropy

that the value
effect
on the
the
lhe precision dU is without
perceptible
overwhelmingly
by
is
of
stales
of A' Tree particles
result. 1 n the problem
in a box, the number
proporlhe
+
like
a
proportional
io
whence
\\ogSU.
Again
U*dU,
JVIogf
something
of
units
the
term in N is dominant, a conclusion independentof even
system
used for lhe energy.

We

see

Example:

from

exam pie
of N;
value

this

iiuxion

Perpetual

Early
lion

more energy

in.in

ii

absorbs.

in our

machine,

study

of

a machine

we came

physics

ilui

wjli

gi\\c

to

forth

motion
of the second kind, as it is called, in
Equally impossible is a perpetual
machine
which heat is exiracicd from part of the environment and deliveredto another
of ihc
part
a heat
in temperature
environment the difference
ihus established being usedto power
we
available
for any purpose at no cost to us.In brief,
engine that delivers mechanicalwork
cannot
tlic surrounding
to
ocean lo extract the cnefgy
propel a ship by cooling
necessary
ocean
10 a
transfer
of energy from ihe low temperature
propel ihe ship. The Spontaneous
higher temperature boiler on the ship would decrease ihe total entropy of the combined
and would thus
be in violation
of the law of increase of entropy.
systems

SUMMARY

1. The

fundamental

2,

ifPfi)

is the

a cioscd

that a

probability

system is in

system is equally
s, the

stale

the

to

be

average value

ofa

likely

is

quanliiy

is that

assumption

lite quantum slates accessible

!Oit.

in any of

ensemble of
alike.

3. An

systems is composedof very

4. The numberofaccessible
states

the

of

combined

all constructed

systems,

many

1 and

systems

2 is

*
where

5. The

s,
entropy

conventional

= s.

s2

a(N,U)

entropy

6. The fundamental

with

the

conventional

7.

fundamental

entropy

kBa

connects

^'
the

o.

temperature r is defined by
1/t

The relation r

S =

relation

Tiie

to$g{N,U).

,^ ^

= kgT connectsthe

[ca;cV)sx.
fundamental

and

temperature

the con-

temperature.

law of increase of entropy states that

tends to remain constant or lo increase

The

system is removed.

the
when

entropy
a constraint

ofa

closed sysicni
intorn.il lo llic

2:

Chapter

and Temperature

Entropy

thermal equilibriumvalues

the physical
of a system are
properties
accessible when the system is in contact
with
a large system or reservoir.If the first system
also is large, the thermal
of the states in
equilibriumpropertiesare given accurately
by consideration

8. The

as

defined

of

all states

over

averages

the most probableconfiguration

alone.

PROBLEMS

and temperature. SupposegW)

tile number of particles, {a}Show

1. Entropy
N is

and

is negative.Tliis

{c^a/rU2)*

2.

Find

Ptirtitttagiwtisni.

of

form

the

y( U)

wiiere

CUiNn,
U

thai

*=

{Nt.

C is
(b)

;t

constant

that

Show

;iciii;tlly applies hi an ideal gits.

value

equilibrium

ui

ictn|KT;tit:rc

i of

ilie (Vac*

lional mngntrlizalion

M \\'m
sysiem of

of the
spin

is 2s.

excess

as given in

2<s>/N

h' spinseachofmagnetic
momem
in in a magnelic field B. The
the
as
Take
lhe iogarlhilhmof lhc muliipliciiy
g(N,s)
eniropy

A.35):

c(s) =logg(Ar.O)for |s|

\302\253
iV.

Him:

Show

that

in

g{U)
wtih

oQ

1og(/{N,0).

this

2s2/N

D0)

approximation

c0-

D1)

U2/2m2B2N,

Further, show thai

\\jx

-U/)\302\2732B2N, where

U denotes

<t/>, the lhermai averageenergy.

oscillator,
(a) Find the enlropy of a sel of N oscillators
n. Use the muiiipiicily
a fund ion of the loiai quanlum
number
\342\200\224
iV.
and
lhe
make
A.55)
Sliding approximalion iogiV!= iViogiV
\342\200\224
\302\273/itu
the
of
JV
1 by iV. (b) Let U denote lhc tola!energy
oscillators.
the total energy at temperature x is
the entropy as a(U,N).Show
that

3.
Quantum
of frequency
funciion

Replace

Express

hartitonic

m as

exp{/itu/r)

This

!S the

that

does

PSanck result; it
us to

not require

is derived
find

again

ihemuilipiicity

,42)

\342\200\224
1

tn Chapter
function.

4 by a

powerful

method

used !ogl0 44 = 1.64345.

a monkey-Hamlet
{b} Show that the probability that
we have

where

of the

universe

thereforezero

in

approximately

any

operational

of an

sense

the age
of Hamlet is

be typed in

will

The

10\"'64316.

probability

event, so that

the

statement

original

one
mudi less a library,
book,
beginning of this problem is nonsense:
occur
in the total literary produclion of the monkeys.

at the

never

will

5.

is

of

Addith-ity

A', =

ss +

as a

gig2

product

the

I012,

far

entropy

1012spins with

two spin

multiplicity

product

#sj72 is

(a) Compute
(b)

s =

For

to

equal

1O10, by what

Yai9'it^i*5i)9i{^i's

two

jO\02174

s,

s, +

factor must
~

5i)\">

the

lOn and s =

you

\302\247've l^e

^ctor

form

to

value. Use

the

A7) may be

0.

(gijh),,,a!l

multiply

JV, =s

- ss), the

= s,.ForSj=

its peak

from

function:

multiplicity

of

systems

and g2{N2.s

g^x^i)

reduced by

the

for

gigz/{9-i9z)m3X

Given

is relatively sharply peakedat s(

functtonofsj

Gaussian approximationto
useful.

systems.
functions

fo make

it

nearest order of

the

magnitude.

' j.

Jeans,

htysteriota

utirerst,

Cambridge

Universily

Press,

1930, p. 4. The

slalenuill

is

attributed

to Huxley.

' For a rctaicd

Clarke in

malhematfco-iherary

2001.

explanations

sec'The

We arc gralcfut to the Population

evidence.
The cumulative
as 2 x 10 s 3nd
tl^c number
njocti ksi than the'numbcr of

of the

average trretrme
m an-seconds ii

study,

Libtary of Babel,\"

by ihe

fascinating Argentine

Revcttc
for
Bureau and to Dr. Rosier
Reference
number of man-secondsis 2 x iO10. if we take ihe
oi
numoc^
of lives as I ^ 10 , i he cumu*ai[\\c
iaken in the problem.
\342\200\242sccondi
(t0\">
monkey

Cliapter2; Entropy
(c)

How

and

Tcmperatur

iarge is the fractional

error

in

the

entropy

when

you

ignore this

factor?

6, Integrated

approximately
the

is 10\"l0
\342\226\2405/JVj

use an

probability

or larger.

calculate

lhat gave ihe result A7),

example
the fractional
deviation from equilibrium
that
=
=
You
find
it convenient
to
will
IO2Z.
iVj
JV2
the

For

deviation.

Take

asymptotic expansion for

the

complementary

error

\302\273i,

xp(x2)

(\"\"e

1 +

small terms.

function.

When

Chapter

and

Distribution

Boltzmann

Helmholtz Free Energy

FACTOR

BOLTZMANN

58

61

Function

Partition

Example: Energy and Heat Capacityof a

Definition; Reversible Process

Two

State

System

64

PRESSURE

6-1
;>7

identity

Tlicrmodynaimc

Example: Minimum
ParamagneticSystem

6S

ENERGY

KttEE

HELMHOLTZ

of

Property

the Free

70

7!

Maxwell Relation

Calculationof f
IDEAL

GAS:

One Atom
Example;

71

from

72

LOOK

FIRST

72

a Box

in
Af

in a

Atoms

74

Box

76

Energy

Example:

of

Equipartition

Example:

Energy of ;i
69

Relations

Differential

62

77

Energy

7$

Entropy of Mixing

SUMMARY

SO

PROBLEMS

81

1. Free
2.

Energy of a Two State Sysiem

Susceptibility

Magnetic

3. Free Energy
of a Harmonic
4. Energy Fluctuations
5.

Effect

Overhauser

6. Rotation
7.

Zipper

O.ollaior

of DiatomicMolecules

Problem

S. Quantum

Concentration

85

Si
S3
S3

S4
84

S5

S3

9.

auJ

Bol

ChapfcrS:

Partition

10. Elasticity

Function
of

for Two

Polymers

11. One-Dimensional

Gas

lleliiiiioiiz

Systems

Free

Energy

Chapter3; BolRinattn

The

laws

statistical

We

are

of thermodynamics

mechanics,

able

of

to distinguish

which

on anotherfrom lhai which

to specify
cases
of thermal

in

and

Distribution

lleimkoitz

may easily be obtainedfrom the principles

are the incomplete
they
expression.
Gibbi
terms

mechanical

we call

mechanical

action and

the thermal
in

the

narrower

Energy

of

action of one system

sense . , . so as

cases of mechanicalaction.
Glbbf

Free

this

In

of the

properties

physical

sysiem

iarge sysiem (ft,

called

system

as

particular,

in

of

reservoir.

The system

of

the values

calculate

Figure

3.1.

The

total

temperature.
wiih
equilibrium

a very

and the reservoirwill

energy Uo

sysiem is in a staleof energy

We

ihe

r because ihcy are in thermal contact.

(ft + & is a closed sysiem, insuiaicd from

The iota!

if the

&

[he

temperature

influences,

us to

permit

a system as a ftinciion
interest
io us is in thermal

of

assume that the

common

the principles that

we develop

chafer

=*

Ea, tltcn

U^

Uo

u!!

external

constant.

is
\302\243/j

ihe

r,x is

have

energy

In

of

the reservoir.

Toial sysiem

Constant

J.I

energy

Vo

Rcprcs illation of a cioscd

a! coniaci with a

irOtiiUhcn

BOLTZMANN
A

central

problem

\302\253iilbe

proportional

to

in a
the

loiat
sjsieni

syst
S.

iisioa

n decomposed

FACTOR
of thermal

specific quantum
Boitzmann
factor.

10 find
siaiu s of energy

physics is

the

probability
t,.

This

ihe system
is propor-

iltai

probability

be in ihe state s, ihe number

When we specify that
S should
number
of accessible
Slates of the louil sysiem is reduced10the
reservoir (H, ai ihe appropriate
energy. That is, ihe number

of

accessible

states
g\302\256t
j

of

of ihe
siaies

Figure 3.2 The change

nsetvoit u&nsfcssenergy

fractional effec!

of

laigc TCMivoii

accessibleto (ft

the reservoir

of

Energy

of cnlropy
t la

itie transfer

vil\\

luua

high

A)

for our

because

If the system

to
\302\243,

Ihe

ratio

of Ihe

the

the

system

dependence

Multiplicity

of

<R

at

Multiplicity

of

(ft

at

write

B)

on the

depend

is only
in terms

are

situations

two

ow

if the reservoirsare very

We

system

system is in

is^f/o

is

in

number

of

in Figure

3.2.

\342\200\224 The
\302\243,.

as

\302\243,},

I al

stale

quantum

2 at

state

quantum

energy
energy

direct consequence of what

assumption. The

about

that the

condition

the

is Uo

energy

.S ,

state of

the

specified

energy

energy
Ei

is

Ihe

two multiplicities:

ts a

result

this

that

probability

probability

have

the
reservoir
\302\243\342\200\236

to the reservoir in

of the

The ratio

is

energy

stales accessible

This

present purposes we

the
large,

of the

shown

constitution

temperature
the

Uo

r.t

\342\200\224
\302\2432

[/q

have

we

ei)

\302\243a(^o

\342\200\224

called

B)

e2)

91s(^'o

the fundamental

3.3. Although questions

of the reservoir, we shall seeihat

in Figure

reservoir.

of the

arc very,

multiplicities

very l.-irgcnumbers.

entropy of the reservoir:

-

\302\273

E.)

ff\302\253(t/0

C)

when ihe

(he system.

The

on ihe reservoir
ci\302\253iop>.

Bohzmnnn

Chapters:

Distribution and Helmholtz Free Energy'

Oi
E

ergy
yo

01

-',
stale

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

(/\342\200\236

',)

;\302\260

'='

slates

Ene

Fi\302\273urc3.3

has a,,(U0 id

The

State 2

tc I

Sta

Energy c.

gy\302\253>

system

in

t,},

(b) is in quantum
c,) acccisiblc quanluin

(a),

slate

t, 2. The

slates,

(,\302\273(()\342\200\236

reservoir

in (a) and

(b)

D)
the probability ratio for

two

the

1, 2

states

of the syslem is simply

E)
Let

us

expand

in D)

the entropies

in

a Taylor

The Taylor seriesexpansion

off[x)about

/(x0)

series

expansion

about

is

t)

0)
where

1/t

(S^/cCV^

gives the

temperature. The partial derivative

is taken

Uo. The higher order termsin

large reservoir.*

al energy
an

infinitely

Therefore

defined

Acr^

-(\302\243,

ofvust

form exp(

the

of

term

It

utility.

ttie

to consider the

ealied the

exp(-e,/t)

in a

system
in

:i

single

for

a!!

We see that

result

(II)

is one

average energy of the

= 1:

ZjZ

\302\243?(\302\243,)

probability

is V

useful

= (e)

oft'j, ~

convergence

\342\202\254)andnolg({/B

difficulties.

partition

p[Et)

and

is

function

(he

results

= X^fo).

of

the

Boltzmann

statistical

pro-

factor

e) because

[he cupansion

physics.

The

or

= T^logZ/ct).

=,

Zh^Zh!A

We expand

the Boltzmann factor

is unity.
the sum of all probabilities

of the most

system

is over

system. The

the

5 of

states

A0}

5>p(~Ei/T)

summation

The

function.

partition

proportionality factor between the

gives

system

function

Z(r)

\342\200\242

the

Function

is helpfui

The

This result is

Boltzmann factor.

of Hie probability of finding

of finding ihc
probability

ratio

to

'

,as 3

known

is
\342\200\224e/t)

the

gives

single: quantum state

state 2.
quantum

Partition

(8)

-\302\2432)/T.

expft/r)'

P{ez)

of

limit

E) and C) is

result of

final

in the

vanish

expansion

D) becomes

by

Affffl=
The

liie

of ihc

'

A2)

tatter quanliiyimmcdiatcty

Battvnanti

ChapterS:

Helmholtz

and

Distribution

Free Energy

0.5

0.4

J-\342\200\224\342\200\224

Energy
ystcm
rgy

and

heat

as functions
is plotteJ

capacity of a
ofthe temperature

in units

ol t.

0.1
\342\226\240

The
with

called
for

(e)

refers to

energy

average

reservoir.

The

thermal

the

notation

average

in conformity

those statesof a

with

and not, as earlier,to the

can

that

system

\342\226\240
) denotes
<\342\226\240

exchange

an average

such

energy

value and is

average. In A2) the symbol U is used

U will now refer to the system
practice;

or ensembie
common
system

-f reservoir.

We trc^l a sy^lcm ofonc pitrtilicut cupticiiy of a two itatt

systexn.
0
and
of
contact
one
one
e.
11w
of energy
slates,
energy
partide is in iltcmut
wiiti a reservoir at temjKrature
t. We want
of ihe
lo find the energy and ttie heat
cupaciiy
as
a
tin
iwo
of
i.
The
lit
ion
function
for
stales
function
the temperature
of
system
pat

Exwiiplc?
clc

Energy

uiid

wftli two

Z =
\"fhe average

exp(-G/t) +

exp(~\302\243/r)

-f

A3)

expf-s/t).

energy is

This function
is plotted
in Figure 3.4.
we
shift
iliczcro
If
of energy and lak^: W.c
instead ofas 0 and e, the results appear different

energies

of the

two

as

states

-\\e

and +\\e,

ty. We have

\302\253p(-\302\243/2r)

2cosh(fi/2t)

A5)

Partition

Function

and

A6)

-jctanh(c/2c).

The heat capacityCv

of a

at conslant

syslem

by the

ihermodynamic

as

s x(iajdx)r ,

Cv
which

is defined

volume

below

derived

C4a)

identity

A7a)

is

lo

equivalent

allcmate

the

definition

s (SU/dt)y.

Cr
hold

We

because the values of the

V conslant

volume. From

and

A4)

In

of energy

dimensions

ri^i-immp

in ]Ilc

anomaly. For

for a syslem

at a

specified

-fEY

per kcivin.

A8a)

Tim

as VfSIST), or gU/dT),. ivliencc

siicctfic

pio! of Iicii]cnpiiciiy

\302\273
i, the

eXp(E/t)

A6).

C, is defined

unils

conventional

'

same resull follows from

The

arc calculaied

(!?b},

energy

A7b)

versus

heat

is drfmed
\\\\\\

icmpcjiiiurc

us

itio

t'iiHirc3

deal

capacity

\"\342\226\240
is Ciiiic^l

per

^ jLtiOiiKy

A8a) becomes

heat capacuy

Cr^(E/2iJ.
ihat

N'oiicc

lemperaiuie

Cy cc

r\"\":

is small

in
in

ihis

as a-

exponen'.ial

0.

factor

A9)

high tempcraiufe limit. Iii ilie low teraperaiuie

whh llic energy level spacing e. For i

comparison

Cy ^
The

exp[

\342\200\224rcJuces

r,'t}

unil

limil
\302\253
e we

CO}

{c/lJ^Xpl-E/lX
Cv rapidly

as r

decreases,

ihc
have

because

exp[

~ 1/v) -> 0

Chapter}:

and Hdmhoki

Distribution

Boltzmann

Free

Energy

is reversible if carried
out in such a
to
the
close
equilibrium condition.
infmiiesimally
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
is well defined at every
the entropy
Thus,
a{V),
of a reversible
the
of the change the
and
direction
stage
by
process,
reversing
Reversible

Definition:

is always

to its

returned

be

will

system

A process

process,

ihe system

way ihai

reversible

In

condition.

initial

the

processes,

defined
at ail times, in contrast
to irreversible
the
processes,where usually we wilt not know what is going on during
process.
We cannot
10 systems
apply the mathematical methods of thermal physics

condition of the system is welt

is undefined.

condition

whose

volume

the system

leaves

that

change

reversible
exampleof an isentropic

same

state

process,

because

not

the entropy

change.

reversible
processes,

change

the

number

of states

Any

process

in which

process.

and

process.

in

a special

an

If the

state

quantum

is an

system always remains in the

any two stages of the pro(p. 31) of similar systems does

between

ensemble

the entropy

But reversible

we shaHhave

zero

be

will

same

the

in

change vanishes is

processes are

interest also in

to

limited

not

an

isentropic

reversible

isothermal

isentropic

pro-

processes.

PRESSURE

Consider a

system in

the

state

quantum

s of

energy e,. We

assume

e, to

be a

function of the volume of the syslem.The volume

is decreased
from V
slowly
V - AV
of an external force. Let the volumechange take
to
by applicalron
that the system remains in the same quantum state s
place
slowly
sufTkrenliy
the
The \"same\" stale may be characterized by its
throughout
compression.
of zeros in the wavefunclion.
numbers
(Figure 3.5) or by the number
quantum
volume
The energy of the state s after
the
reversible
change ts
-

t\302\243V

eJ^V) -(dtJdV)bV

&V)~

a pressure p, applied normal

done on the system by the pressure

Consider
work

cube

volume

Kto

from

U(V

\342\200\224

Af)

AKappears

- U(V) .=*

\342\226\240\342\226\240-.

to all facesof a cube.

The

B1)

mechanical

(Figure 3.6) of the

change of energy of the system:

in a contraction
as the

At/

-(deJdVyLV.

B2)

\342\226\240\342\200\224-\342\200\224_

t.S

i.O

O.S

Volume,

relative scale

3.5
of energy on volume, for the energy levels of a free
Figure
Dependence
-%- n_\\
-j- . t
particle- connned 10a cube. Ttie curves arc labeled oy m ^\342\200\224
i^
as in Figure t.2. The niuhtpltctties
ch; nge here
g are also given. The volume
^s isolropier
a cub1\" remains
oc of ]tic stat1
& cube,
i he criercy ranfie

represented in
of ilie energy
llu: av cragc

an

ranee

energy

ensemble

of systems

will

increase

in a revcrsibk

iiself is of no practical impottance.

lhal is impotlaiU.

ti

is )he

Tigure

cha

3.6

compression

Volume
of a

cliangc

cube.

- AI'

Chapter i;

Free

Ihtmhottz

of the system. Let A

the energy

V denotes

Here

and

Distribution

Batiziriann

Energy

be

face of ihe

of one

area

the

cube;then
+

A{Ax

if ail

increments

AV

Ay

Az are

psA(&x

so that, on comparisonwith

AV

B3)

taken as

positive in

the

compres-

Ay

Az)

PiAV

B4)

B2),

-thjdv

stale

s.

P,

is the pressure on a system

in
We average B5) over all states

the

ensemble

the

of

B5)

to obtain

the average pressure

as p:

written

<\302\243>,usually

+ Az)

compression is

in the

done

wotk

compression.
The

=s

Ax

V and

Ay

B6)

where U

The

<t>.

of states

number

we have

in

described.

each remains

in

fhis

a is

entropy
the
We

ensemble
hove

_st:ile

held constant in ihc tlcrivaiivi;

is uuclianged

in ihe

in

reversible

the

of systems,

a collection

each

in

ihc

because

compression
some

stme,

and

compression.

The result B6) correspondsto our

mechanic!

of the

picture

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
on a system maintained at constant temperature.
the
pressure
We
look
for other
for the pressure. The numberof statesand thus
expressions
U
and on V, for a fixed number of particles, so
the entropy
depend only on
that

only

the

two

variables

U and

the

describe

system.

of

The differential

the entropy is
da[U.V)

This gives the differential

differential ch;i:v:_\342\226\240\342\226\240.
JU
and
in
such
a
dependency,
way

B7)

Uu

change of
dV.
th;it

the

Assume
the

two

entropy

Tor

arbitrary

independent

now that we select dV and dV interterms on the right-hand sideof B7}

Identity

Thermodyaamie

overall

The

cancel.

of dll

values

interdependent

entropy change

da

be

will

and dV by {W)a

and

zero.
{&V}at

denote

If we
the

entropy

these interchange

will

be zero:

B8)

B9)

)
Bui

\302\273he
ratio

(*5[/)\342\200\236/(<)F),

is

the

wilh respect to

at

o:

constant

s ldU/dV),.

(iV)J(SV),
With

of U

Jerivative

partial

and

this

the dcfiniiion

l/i

C0)

s (So/5!/),.,Eq.B9)becomes

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

By B6)

Therniodynaniic

pressure

and

to

equal

-ft

whence

Identity

Consider again the

ihe

side of C1) is

the kft-h;ll)d

differential

the

B7)

of the

entropy; substitute the new

definition of i to obtain

Ttla

dU

-f pdV.

result for

Chapter3: Bohynaaa
relation

useful

This

variable

will

appear

will be
in

Free

and Helmbohi

Distribution

called the

E.38).

Energy

thcrtnodjnsmk identity,

A simple

with

transposition gives

dU =
process of change of stateof the

If the actual

form

The

TVS

is

system

C4b)

pdV.
reversible,

we can

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

brought

systems

into

thermal

HELMHOLTZ FREE
The

contact (Chapter

8).

ENERGY

function

C5)

the Hclmhoitz free

is called

physics

at

constant

temperature

energy.

that

This

function

the energy

plays the
plays

part in thermal

in ordinary

mechanical

no
because
processes, which arc always understoodto be at constant entropy,
state
are
allowedThe
free
tells
us
how
to
bulance
internal
of
energy
changes
and maximum entiic conflicting demands of a system
for
minimum
energy
The
a
Helnihoitz
free
will
be
a
minimum
for
system S in thermal
entropy.
energy
contactwith a reservoir (R, if the volume of the systemis constant.
r and V.
We
that F is an cxtrcmum in equilibrium
;it constant
first
show
01
to &,
reversible transfer from
for infinitesimal
By definition,

C6)

at constaot
stant

volume.

so that
temperature. But 1/t h {das/cUi)yi
Therefore C6) becomes
dFt

*=

C7)

the condition for F to be an extremum with

at constant volume and temperature.We like F because
the energy
eigenvalues e, of the system (seep. 72).
which is

dUL

respect

we can

to

all variations

calculate

it

from

Free

tfehuitoh:

We can show

Comment.
i',R

\342\226\240
Then

Us

ihe tola!

is a minimum.

extiemum

the

that

- UtfffJtVrivji +

(\302\253*A'^),,v

L/j

Ft

w^ is ihc free energy of

+

be a

The

hxti'iiplc:

with

o,

mus)

configuraiion.

the

\302\273

Fj
thai

model

ffsiUj).

C3)

in

excess is 2s

respect

the

C9)

I.
A't

<rlk(Lr)

with

when the
constant r, V

respect

is in

system
will

and we

is consiant;

. It follows from
ihc mosi probable
for any deparluce

to Us
increase

Coilsklef tliC
iyswin,
parcmti^nctic
= A1? -+- N^',
Let
N
*uid
down.
Ni
spins
spins
up
is found
in
Tlie
the
SUHiiig
approximmion
W(.
entropy

\\viUi

approximate

D0)

system.-Now

lo Vs
at

system

vf the

property

of tliaptcr

tlicliclpofan

vviiii

of

the

is a maximum

equilibrium

minimum

free energy

Slltthnuiii

sy^tcfn

spin

i/t

- FJx ,

a^a^iV)

D0) lha)

==

becomes

C8)

rewll

is V

energy

that

We know

where

total

eniropy is

* e^U)

so thai

The

Energy

free

energy

tifa

N't

form of A.31}:

,4,,
The

in a magnetic field
Tile fice cncigy

energy

elementary
magnet.

FJjaB)

&

V{s,m

Bis.- 2\\tttfl,
funaion (to

w licrc

be called

m is ilic
ldc

magnetic woniciilofan

lapdau

function

in

elemen-

Chapter

tO) is

io(s),or

D2)
becomes
of Ft{r,*.B) with respeel
io s, this function
cquat
f
because
Thai
free energy
<s> is a function
F[i.B).
is, Jt.<5>,BJ F(r,B),
excess occurs when
of FL with respect io the spin
minimum
Al

ihc

minimum

= 0

= -JmB +

tlog^4-|-

lo the
of z

equilibrium

and B. The

D3)

Thus

in the

or,

on dividing

magnetic

and denominator

numerator

the

volume,

free energy of
however,

The
is

easier,

for

the

D5)

<2s>m/K =

exp(\302\273iB/r)

D6)

Hi\302\273wnh{mB/r).

can

be obtained
the

from

by

D5) in

substituting

function

partition

for

one

\302\253

D7)

2cosh(mB/t).

expt-niB/r)

D2).

magnet:

F =

below. Multiply by N to obtain the result

\342\200\224ilogZ as derived
of Problem 2.)
(The magnetization is derived more simply
by the method

relation

N magneis.

exp(/\302\273B/r),

Ntanh(mi?/r).

ihe system in equilibrium

to obtain F directly
=

Z
Now use

momeni
If n is the number ofspins
per unit volume.
in thermal equilibrium in the magnetic
field is

magnetizalion

M =

It

Is

excess

,U is the magnetic

The magnetization
unii

by

ofihe spin

\302\273

<2s>

per

equilibrium value

thermal

B lhe

field

Differential Relations

The

is

off

differential

dF =

or,

use

with

of the

dU - xda -

thermodynamic

identity C4a),

dF = -adt
for

oiit,

\342\200\224fdV

\342\226\240

which

D9)

These

relations are

The free
for

an

energy

isvihcnwil

widely used.
F

in

change

the

result

of volume;

=\302\273

-(rf/^K),

acts

as the eilecttvc

contrast this result witii

B6).

The

energy
result

Calculation of Ffrom Z

may be written

as

' -

what

= U

of F

use

by

we

~ to. The two

pressure

~-(cU/dV)f

x(?a/3V)t

is dominant

in gases

\342\226\240

<D,
the

on

terms

the energy pressure and

is dominant
in most

call

may

\342\231\246

-($.

right-hand

side of E0)

represent

the entropy pressure.The energy

solids and the entropy
pressure

and in elastic polymerssuelias rubber

is testimony of the importanceof the

{Problem

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

enlropy

Maxwell
relation*
We can now derive one of a group of
called Maxwell relations.Form
the cross-derivauvirscV/^l\"
be equat
10 each other. It follows from
that
D9)

E!)

*{ep;eT)y

(ca/dV)t

relations
tliermodynamic
must
Hx and ^FfcxcV,which

useful

a relation
is not at all obvious. Other Maxwell
will be derived later at
that
relations
similar
The
of
obtaining thermodyappropriate points, by
arguments.
methodology
L
Chem.
5964
namic relations is discussed
A981).
Phys. 75,
by R. Gtlmore,

from Z

of F

Calculation

Because F =
F

Wo show

thul

this

%a and

U +

equation

a =

-{cFjdi)Vt we have the

or

i{SF/dt)Vt
is satisfied,

F/x
where

is the

partition

fund ton.

differential

~x2c(F/z)Jcx

\302\253
U.

equation

E2S

by

- -log^ .

On substitution.

E.1)

Chapter3:

This

A2).

by

and Hchniipliz

Distribution

Bollzittnnn

the

F =

+ ar.
is so

temperature
are

log

g{t

Z)fct

We may

the

However,

low

that

the

only

limit logZ

that

In

occupied.

equafion E2).
for Fjx to contain an

possible

appear

-riogZ

logg0 only

if

a ~

state

must

cj0 coincident

that

reduce to \\oggQ
when
the
states at the lowest energy \302\2430

-* logg0~ W*.

s0

thai

a =

-cFjcr

\342\200\224

write the result as

factor

Boftzmann

the

entropy

a such

constant

additive

0.

Zand

E5)

-riogZ

differential

required

would

It

Energy

that

proves

F=

satisfies

Free

(II)

E6)

cxp{-f/t);
probability of a

for the occupancy

quantum

s becomes

E7)

GAS:

IDEAL
One atom

mass

free

free

in

FIRST

a box.

We

move

to
wave

particle

LOOK

calculate

in a

equation

\\p{x,y,z)

cubical box
-{/iJ/2.U)V:^

= Asia(nxitx

of

volume

== ei/i

We
system

are

L)sm{iiyity}L)sin{n.iiz}L)

where ir,, nyt n. are any positive integers, as in

not give independent orbitals,and a zero does
values

function Zx of one atom of

V ~ L1. The orbitals of the

the partition

1. Negative

Chapter

not give

E8)

,
integers

do

a solution. The energy

are

neglect
is

the spin

entirely

and all otherstructure

specified

by the

of

values of nlt

the
nft

atom,
n:.

so that

a state of

the

Ideal Cm:

The

the

Provided

we

function is ihe sum

partiiion

may

replace

the summations

2] =
The notation a\"
may

be

of adjacent

spacing

&

t!nx

First

Look

over the states E9);

energy values

is small in comparisonwiih

t,

by integrations:
\342\200\224

*2{nx2

(/ji,cxp[

dnf

ny2 +

for convenience.

is introduced

Azji2/2A/12t

as ihe

written

'u2)].

F1)

The exponential

product of Ihrec factors

F2)
in

of ihe

ierms

concentration

ji

XjV.

Here

F3!

is catted the

atom

in

quantum

cube

concentration.

of side

equal to

It is

the conccnlration

die thermal average

lie

associated with one

Broglie

wavelength,

Here <r> is a thermal

which is a length
to /i/M<i\302\273>
h'{Mi)ul.
equal
roughly
will keep turning up in ihe thermal physics
This
concentration
averagevelocity.
of gases,in semiconductor
and in the theory of chemical reactions.
theory,
For helium
at
at room lemperature, n. s= 2.5 x
atmospheric
pressure
*3x
lO^cnr3
and uQ = 0.8 x I02scrrT3.
I(T6, which is very
Thus,
ii/iiq
-

10 unity, so ihat helium is very

dilute
under
normal
conditions.
compared
Whenever n/nQ \302\2531 we say ihat the gas is in the ctassieai
An
ideal
regime.
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),

small

F4)

becauseZj\"' exp{-

is (he

eJx)

log^i =
so that for an

the system

probability

\342\200\224

terms

-f-

jlog(I/i)

is in

it. From

state

the

F2),

of t ,

independent

ideal gas of one atom

F5)
If t

=*

known result for

The

thermal

:Iic Boltzmann constant, then

per atom of an ideal gas.
energy

kB is

where

kaT,

the

of'a

occupancy

average

free particle

lkHT,

the well-

orbital satisfies the

in-

equiility

an upper limit

sets

which

standard

at

atom

helium

regimeto

apply,

is always

positive

temporarily
many

tiiitil

noniulcmaing

box, all atoms

one

utoni

result.

identic!!, of ik

this

of 4 x

a free

must

the

of an

occupancy

and temperature.

concentration

occupancy

for

for

!0\026

be

\302\253
1.

We

note

that

orbital by a

For the classical

as defined
\302\243\342\200\236

by E9)

atom.

meihod
10 deal with the problem of
in Chapter 6 a powerful
in a
a box. We iitsi ireai an ideal gas of .V aioms
atoms i\302\273
of the
extension
or different isotopes. This is a simple
of different
species
correction
factor that arises when
ail atoms
are
We then discuss the major
same
of
ihe
b.unc
specks.
isotope
ac

develop

identical

Ideal Gas; A

!\342\226\241

\342\226\241
I

Figure 3.7 An .V particle

of.V bo\\es. The energy is

Figure

of different

Atoms

3.8

iV

on

in each

':,(!)

3.7), the

f-

sido includesevery

r.^2)

partition

is fhe

funciion

F6)

Zt{l)Z1B)---Zl(N)

indices
of

boxes (Figure
funclioiis:

distinct

!he right-hand

where 3, fi.... Cdenotethe orbital

also gives lite pjiiiiioit function
single box (Figure 3.S):

species in

partition

ZXha*\302\273

product

of free particles with one panicle

for one particlein one box.

system

N limesthat

If we have cfne atom

in each of
product of ihc separateone aiom

because ihe

Look

First

of llic N

state

independent

F7)

\342\200\242\342\200\242\342\200\242r^N)

oUlotm

iV itottmiontciJng

in

ihc

suewssive

aiuiits

boxes. The

all ordilTcrctii

result

F6)

speciesin

for F7). If i!ic

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

iliis

bang

the same

+ M*l
- in a single bos, the siate
lion numbers. For mo hbded particles
\302\251
and
^(O)
and ihe Male \302\243,(\342\200\242)
combiti.tttons
tmibi be counted i\302\253
+ cfrtO|;irc
tlisiinct Mates, and both
Ij Hie
lite
function. Bui for hs'o tdetiitccil
lHc st.iie of energy c, + \302\243*
pitritclcs
pmtiuon
and only one cnlry is to be made in tfte si.ite sum in the p.irtiiioti
idcmicai siate as c^ + \342\202\254\342\200\236
futiciion.

Chapter 3:

indices are alt

onlj once

If tlicorbiial

entry

occur

slsould

a faclor

of ,V!, ;md the

Free

ami Hdmhohz

Distribution

BoHzmann

ihe

correct

llic
cniry wilt occur S< limes iti Zts, whereas
are identical. Thus, Z,v ovcrcounisthe Stales by
is
function for N identical
particles

each

diffrfem,
if

Energy

panicles

partition

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

classical regime.Here nQ
There isaslep in ihe argitmcni

in ihe
diticrcnt

oEotla's-

It

i\302\243
no

Simple

from F3).
{\\(zi2nk3)yl
whcii we assume iliat ail jV occupied
orbiuis
rnallei lo cvaltsaie o^rccily {lieerror tmrouuecci

arc

always

by

but laicr %sfg v,'il\\ cotifj^ni by another rnctliod the validiiy

of FSJ in
^pproxitnaiiorij
tlassicai
regime n <i na. Tile ft'! fjcior changesihe result for the entropy of !hc ideal
The enlropy is an cxpaimemalty measurablequaniily,
and
i! lias been confirmed ihat
jV! facior is corrcci in this low concentration
irmit.

The energy of

Energy,

{he ideal gas

from

follows

{he

N particle

ih^S
(lie
gas.
the

partition

funciion by use of{l2):

l/ = T3^l0gZ.v/(}T}=^T
,
with

consistent

{65} for

F =

With

{he

earlier

tionlogN!

c=

result
NlogN

F =

From

the free

gas of

aioms.

one panicle.

The

free

energy

is

- -i]ogZi'v + ilogN!.

-ilogZy

G0)

= (Mr/2n/!2K'i2KandtheStirlingappfoxima-

Zt = naV
\342\200\224we

have

N,

-tNIog[{.Ui/2n/i2K'2K]

+ rNtogN

energy we can calculateihe entropy

The
follows from {49}:
pressure

p -

F9)

-BF/3K), =

PK

Nr,

NxjV

and

xN.

the pressure

{71}

of the

ideal

{72}

G3)

IdtalGas:

the iJcal gas law.In conventional

is called

which

1>V =

The entropy follows

a =

from

-{CF/?z)r

first

Look

units,

G-1)

NkuT.

D9};

W!og[{Afr/2\302\253/r}3';F]

\\N

+ S , G5}

NlogN

G6)

the

for

equation

the entropy

method

that

a direct

through

The energy

argument.

{7!}and {76}we

NjV,

of a

entropy

involves

6 by

Chapter

particle

a quantum

\342\200\224

involves

result

The

result is known as the Sackur-Tctrodc

This
monatomtc ideal gas.It agreeswith experiment.
the term
ideal gas
hq, so even for the classical
shall
derive
these
results
We
again tn
concept.

concentration

(he

with

have

not

does

explicitly

{69}also follows

from

involve the
U

*=

N\\

or

identical

xa; with use

of

= \\Nr.

The energy U = |j\\'r from F9} is ascribed to a contriof energy.

each \"degree of freedom\"
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
In ihe classical focm of siatisiicat
the
function
contains
example.
mechanics, the partition
kinetic energy of the particles
in an iniegral over the momentum
p,.
components
pt, p,.

Example!
contribution

Equipanlihn

i* from

For one free

particle

Jjjexp[~

a result

to Ft).

similar

average energy may

The

result

The limits of integration

be

ts generalized

in the

of degree2 in
thermal averagekinetic
energy
is homogeneous
hamiltonian

is

average potential

homogeneous
energy

by use

calculated

are

fat
\302\261ao

momentum

with

component.

The thermal

in

a posilion

component,

will

the

wilt

coordinate

that coordinate

of the system
limit of the
if the
Further,
\302\243r.

Kamiltonian

the

with thai momentum

associated
of degree

each

{77}

of A2) and is equal wfr.

classical theory. Whenever

a canonical

associated

pI1)/2Mx']dpIdpfilp.

also

classical
be

component, theihermal
be Jr. The resull thus

3
Vibt

^\342\200\224\302\273

2
lion

T,\302\273s

50

25

250

75100

500 1000 2500 5000

K

Temperature.

Heat capacity at constant volume

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

Figure
the

3.9

gas phase.

applies to ihe
At

arrangementsof
the

and

temperatures

high

Example:

for

harmonic

oscillator

harmonic

in the classical limit. The quantum

diatomic roiator are derived
in Problems
the dais teal limits
as in Figure
are attained,
oscillator

for the

Entropy ofttuxia*. In Chapter

8 in a solid made up of ,V

A and

number

1 we

calculated

the

A arid t

atoms

number

for the

results

3 and

har-

6, respectively.

3.9,

of possible

atoms B. We

found

arrangein A.20)

of arrangements:

A/i

G3)

The crtiopy associated

c{A',0 =
and

is piotied

in Fi^me

with

these

arrangements

logflMf) 3.10for

jV

~ 20.

is

bg,V! This

!og{iV

contribution

r)!

to the

~ logti

G9)

total entropy

of ;tn

alloy

itfcalGas;

A First

lj>ak

\\

4\342\200\224-~

vj

At_x

composition

Alloy

0.S

0.6

0-4

0.2

1.0

Br

as a function
of
ora random binary alloy
Figure 3.10 Nftxing
entropy
ihe proportions or the constituent
atoms A and B. The curve
plotted
for a total of 20atoms. We see that this entropy is a
was calculated
maximum when A and B are present in equal proportions
0.5),
(x \302\273
anci trie entropy is zero For pure A or pure H.

system iscalled the

by use of the Sliding
a(N,i)

entropy

.viih

result

G9)

be put

may

a more

in

convenient

approximation:

=* NlagN

- N -

- (N

NlogN

= -(,V

The

of mining.

(N

i)\\ag{N
-

!)\\og(N

- t)Iog(l -

//N)

- i) +
t)~~

t ~

rlogt

l\\agl

l Iog(f/jV)

= t/N,

- -v)Iog(I -

-v)

.vlog.v].

treated as a random
of an n'loy A^^B,
(homogives the entropy of mi\\iug
11.
solmx^i.
TIic
in
detail
in
Chapter
(homogeneous} soiici
problem is J^dopjd
of a mixture of A
condition
We ask i Is the homogeneous solid solution ihe equilibrium
of
and
B atoms, or is the equilibrium
a two-phase
ofcrysi2l!::i*s
system, sudi as a miMure
of the science
answer is the basis of much
pure A and crystallitesof pure B?The complete
of metallurgy: the answer
will depend on the temperature
and on the imcniioiTiic ii;;;raction
case iluit tltc iiue faction energies bciw.vn
energies
t/M, f/EB,and UAa. In the special
This

result

A., BB, and AB neighbor pairs are all equal, ihe

lower free energy
than
Hie corresponding
mb-lure
free energy
of the solid solution A [ -^B,
is

F =

which

we

must

Fo

\302\273

is

of

the mixture
always

in

There is a
any

other

tendency

very small
xN is ihe

if a

evert

A atoms.

sutroundiug

Let this

proportion -\\
number of B

\302\253
t of

strong

The

(81)

xlogx]

have

a minimum

atoms.Tlic

.vj

the

The entropy of mixing

solid soiution has ihe lower
to x.

of any

eniropy

mixing

(SO) is

dissolve in
atom and ihe

B to

element

between

exists

etlergy

a B

a positive

quantity.

energy is

xi\\U,

approximately

(83)

~.\\N\\ogx

+ txiog.v)

N(sU

If

wlk-re

(84)

= 0 ,

{85}

when

BFfBx

x
This shows there is a

that

(82)

repulsive energy be denoted by U,

B aioms is present, the Iota! repulsive

Fix)

has

small proportion

repulsive

a =

which

proportion

positive\342\200\224so

at least a very

for

A,

will

elements.

pure

case.

this special

element

a)

solution

- Fo

+ xF0

x)F0

in the
arc

entropies

positive\342\200\224all

free energy

- .\\)Iog{l -

A't[A

B crystals

and

ofc/yitatlilci of the

with

compare

F =
Tor

Fo

tct(.v)

solid

homogeneous

natural

\302\273

N(U

impurity

+ t)

xiog-v

(86)

exp(~!}exp(-t//T}.
content

in all crystals.

SUMMARY

1. The factor
=

?{\302\243j)

is the

probabiHty of finding

a system

expf-e./tJ/Z
in a

slate s of energy c, when

the

system

comaei

is in thermal

particles

the

in

2. The partition

The

3.

is

function

is given by

pressure

~{cUldV)a = x$gIc\\')v.

p =

4.

free

Hejmltoltz

The

is defined

energy

held at

a system

for

equilibrium

6.

ss -tlogZ.Tltisrcsulitsvcry
}\342\226\240

-i?F/dT)y;

such as p

constant i,
ttscru!

in

\302\253
\302\273a.The

N/V

o =

JVt;

state at all

of spin

atoms

zero,

(nQVf/N\\ ,

concentration

quantum

is reversible

process

equilibrium

and ofquuniiiics

incilcuhitiansorf

from F.

o derived

and

pV

mittimum

is a

~{8F/dV)r

ZH =

8.

xa.

V.

\302\273

7. For an ideal monatomicgas of N

as F ^ U ~
'

5.

if

r. The numberof

constant.

is assumed

system

ai temperature

reservoir

a large

with

s (A/r/2n/t2K/I.

nQ

W[log(iic/H)

5];

Further,

fW.

if the sysiem remainsinfinitesimally

times during ihe process.

close

to

for

the

ihe

PROBLEMS

/.

Free

energy as a

function

of

a two
of

state systenu (a) Find

of a system with
two

fro; ettcrgy, find

energy
the system. Tttc entropy is plotted in
c. (b)

in

of

energy

2.

function

moments

of

for

ihe

tnagiteliAUiou

temperature

in

a magnetic

and

magnetic

one

states,

for

end

function

pitriiiion
tltu

for

io
x

susceptibility

field for the

another

at energy

the energy

itnd

free

0 and one
entropy

3.11.

Figure

field. The result

mutanli^jiB/i}, as derived in {46}by

expression

expressions

00 Use ihe

susceptibility.

Magnate

expression

From ihe

an

model system

the

method.

of

magnetization

Here

find nn exaci
s ilM/tlB as a

magnetic

is M ~
the
is
particle

Si

Chapter

and

Distribution

Bolizmann

OR 2

tjelinholt;

Free

Energy

0.6

0.4

A/

0.2

ft

Figure

3.12

i.
oscillator

/Vcc
has

as a function
loui macaeiicmoment
is
the
momeni
a
U.icarfunciio
mB/x
r the manicnl Sends 10 salurale.

ofmfl'r.

Notice thai

31 lou

of HiiJ/r,

bul

hiS

Ai

high

contciiiraitot!. Tlie result

express
thul the

of ihe

Plot

the result

is x

sust;eptibiltty
energy of
an

is

plottcJ

as a function

infinite

only

in Hgure 3.12. (b) Find

and the parameicr.v

series of

ihe

ofr

\342\200\224
in the
j\302\253\302\273V

harmonic

2.0

1.5

1.0

0.5

oscillator.

ttniit

free

energy

M/tuu,

(c)

and
Show

\302\253
/\302\273B
r.

A one-dt'mcnsian;il

equally spacedenergy

states,

with

liurmonic
=

\302\243,

sho,

oscilwhere

s is a

of frequency

positive imegeror zero,

the

chosen

have

Wu

Enin

3.13

Figure

osciliuSor

and

frequency of she oscillaior.

for
a
0. (;s) Show that

tlic classical

to is

of energy

the

at

s =

state

the free energy is

oscillator

harmonic

zero

(S7)

Note

at

that

high

such ihal

temperatures

of the logarithm to obtain F^i

!og(/itu/t).

\302\273
fitu

(b)

we

From

may expand

the argument

(87) show thai the

entropy

($8}

The
4.

entropy

Energy

is

shown

in Figure

fluctuations.

wiiis a

reservoir- Show that

syslcin

is

3.13 and the heat

Consider a systemof fixed

the

mean

square

capacity in
volume

fluctuation

Figure

ta thermal

3.1-i.

contact

ia she esiemyof lhc

Z
the conventtooai symbol for <e). Hint: Use the partition fitnctwn
out
the
:crm
to
ihc
mean
fluctuation.
Also,
c-U/ci
square
multiply
\342\226\240
The temperature t of a system is a quantity
that by delirsiiion does
(\342\226\240
J. Note:

Here

to

U is

relate

3:

Chapter

S\302\273re3.S4
r

harmonic

ifiiontal

wilh

unncal
mlcln
iiit
iluc

capacity
oscillator
of

flE.

Cv

is k^own

mpcratures

'as

Energy

u>.

The

of i/fiw, whkh
is calkd rhc

is

\302\253herc0,

\\n the high

Icniperamte.

- kB.ot

frequency

units

in

Free

IIcIihUoUz

Versus u-mperatufe

Heal

scale is

mJ

Distrihut

Bohzmnn

temperature
miiis. This
V'^Iv:;. i\\i low

in run<iamciiia!

\\\\\\t

c^issic^I

C(- decreases

csponeniially.

1.0

0.5

not fluctuate

attiiude

otltcr

Any

v,\\

value

would

of a system.The energy
do^s

Thus

\\shcn

is

the system

be inconsibletit

in

thermal

with

contact

of the

definition

our

a reservoir.

with

temperature

may fiuetijiitc, but the temperature

Sorr.c workers
ltot.
do not acllterc to a rigorous definition
of temperature.
Landau arid Ltfshttz etve Hie result
of

a system

such

\302\253AtJ>

=> t2/Cv

(90)

this should be viewed as just another form

of (89)
with At
becomes
AV;CV. We know that AU = Cy At, whence
(90)
<(Ak
which is our result (89).

but

5.

effect.

Suppose

one

whenever
increase
positive

system

- r=C,.,

suitable external mechanicalor

to
add ae
the energy of 'he heat
reservoir
arrangement
the reservoir passes to the system the quantum of energy e. The net
of er.eray
of the reservoir is (a \342\200\224
Here
a ts some numerical factor,
l}e.
or negative.
Show that the effective Boltzmantifactor for this abnormal

Ovcrhaussr

electrical

equal to

that

by a

can

is given by

This reasoninggives the statistical basts of the Ovcrhattsereffect whereby

the
be
thermal
nuclear
in
field
can
enhanced
above
the
a magnetic
polarization
Such
a condition
polarization.
equilibrium
requires the active supply of energy
to the system from an external source. The system is not in equilibrium,
but ts
be
to
in
a
state.
Cf.
A.
W.
Rev.
411
said
92,
Overhauser, Phys.
A953).
steady
6.

Rotation

considered

only

of diatomic molecules.
the translationa!
energy

In our
of the

first

look

particles.

at
But

the ideal
molecules

gas we
can

con-

rotate,

energy. The rotational motion is quantised; and the energy

molecule arc or the form

with kinetic
of a diatomic

= jlj

ft;}

posilive integer includingzero:/ =

level is </(;) - 2; + I. (a) Find
rotational

of e;ich

for the rotational states

of

stiitcs,not over all le\\cls\342\200\224this

0, I,2,.. ..

a difference,

makes

The

multiplicity

function

Zk(t)
Z is a sum over all
jb) Evaluate ZH(x)
approxi-

the

partition

that

Remeniber

molecule.

one

(92}

l)\302\243o

is any

where;

levels

the sum to an integral, (c) Do the same

for
after the second term,(d) Give expressions
for
the energy V and the heat capacity C, as functions
tn both limits. Observe
oft,
that the rotational contribution to the heat capacity of a diatomicmolecule

approximately for

truncating

\302\253
sOl

by

\302\273

by

e0,

of L'(t) nnd

C{x),showing

7. Zipper pruhh'W.
with

units,

in conventional

{or,

approaches

closed

converting

the sum

the
A

citefgy

h:is N

zipper

u siate

0 and

and

links; each link

has n

state

ii is

which

in

for

behaviors

-\302\273
ro

limiting

open

with

that

can

the

r -*

0.

and

1}

are

it is

tti which
t:. We

energy

zipper
only im/jp from the left end,
mmiher s can only open if all links to jhe left {1,2,.. .,s tn the
(a) Sliow ihat the parution fuiicliotl can be summed

however,

the behavior

Sketch

r \302\273
r.0.lc)

A-,,)\\Uv?n

require,

site link

that

open,

already

form

193}

e \302\273
the average number of
i, find
of
model
lhe
ofnvo-siraiided
unwinding
very simplified
C. Kittel,
Arner. J. Physics 37, 917A969).

{b) In the

5,

iirnii

Quantum

L;

in the

when

one

Consider

concentration.

rai ion in

concern

lhe

effect is n

ground orbtial. There

lhis zero-poini quantum

kineiic

open links.The modelis

particle

DNA

confined to a

cube of side

of

1/L3. Find the kineiic energy

will
be a value
ofthceoticentraiioii
is equal

energy

to the

molecules\342\200\224see

he

particle

for which

temperature r. (At

this

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

9.

Partition

function

Z(l 4-2) of two

for

independent

two

thai

Show

systems.

I and

sysiems

temperature t is equal 10ihe produci

of

ihe

in

thermal

paniUon

the

partition
contaci

at a

funciions

of the

function
common

separate

systems:

Z(I +

2)

Z(I)ZB).

(94)

ChaptcrS:

10.

identity for

a One-dimensional

is

system

dU ~ fdi

zda =
when

Energy

The lhermodyiiamic

of potythevs.

Elasticity

free

Heimhaltz

and

Distribution

Boltzntann

(95)

the external forceexertedon the line and

witSi C2) we form the derivative to
analogy

/ is

line. By

ill is

the extension of the

find

.-Ha-

The direction of

the

force

is

to the

opposite

conventional direction of the

pressure.
We

a polymeric

consider

of N

chain

equally likely to be directedto the right

of arrangementsthat give a head-ioiail

\302\253
JV

\\s\\

show

of

/>, with

each

link

(a)Show ihat the number

2js|p

is

'
-T-

(kN

(b) For

to the left,

length

+ q(N,s)

q(N,-s)

links each of length

and

\342\200\224~

4- 5)!

(\302\243N

(97)

s)\\

that

(98)

(c) Show

that

the

/ is

at extension

force

/ = h/Np1.

(99)

because
the
temperature. The forcearises
wants to cur! up: the entropy is higher in a random
coil than iti ati
polymer
uncoiled
a rubber band makesit contract;
a
warming
configuration.
Warming
of
rubber
is
discussed
steel wire makes tt expand.
The
by
theory
elasticity
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
at temperaline oflcnath L. Find the entropy
confined
to a one-dimcsisional
M,

The

force

temperaturer.

The

is proportional

pti5tides

to the

have spin

zero.

Chapter

and

Radiation

Thermal

Planck Distribution

PLANCK

DISTRIBUTION

PLANCK

LAW
and

Emission

FUNCTION

AND STEFAN-EOLTZMANN

96

Law

KirchhorT

Absorption:

LAW

Estimation of SurfaceTemperature
Black

Cosmic

Example:

97

Background

Body

Radiation

93

ELECTRICAL NOISE

PHONONSIN SOLIDS:

104

Modes

Phonon

Numberof

102

THEORY

DEBYE

109
Thermal Photons

Number of
Surface

no
110

Ike Sun

of

Temperature

Average Temperature of the interior of the

Age

111

Sun

of the Sun

111

Surface Temperature of tlte

Free Energy of a Photon
Heat

111

112

Gas

112

Shields

Heat Capai

ty

HeatCapa'

ty of Solids in

HeatCapai;ty
HeatCapai

of

Photons

High Temperature

Limit

and Phonons

Flux

Energy

113

113

113

113

114

Radiant Object

and

114

Occupancy

Isentropic

Expansion

Reflective

Heat

SUPPLEMENT:

113

Space

tribution of Radiant

D:
of a

Entropy

ol\" intergalactic

tuations in a Solid at Low Temperatures

4He at Low Temperatures
ty of
Liquid

Flu>

Energy

Angular

112

Ga: in One Dimension

Photon

image

111

Earth

Radiation

of Thermal

Pressure

Shield

of Photon
and

GREENHOUSE

Gas

Kirchhoff's

114

Law

EFFECT

115

Chapter's: Thermal

[We
v,

//

Radio

the distribution of
consider]
U is viewed as divisiblewithout

distributionsare possible.We
of the
finite

whole

equal

gives the element

N oscillators

U among

energy

then

limit,

an infinite
this

however\342\200\224wUl

of frequency

number of
is the

essential point

an entirely determined nimiber

of
natural
constant
h = 6.55 x fO~21

made up of

and we make use of the

erg-sec.This constant when

oscillators

consider

calculation\342\200\224Vas

parts,

the

multiplied

by

of energy e in

the common
ergs

frequency

....

M. Planck

of

the

Planck

Fu

Distribution

FUNCTION

PLANCK

DISTRIBUTION

The Planck

distribution describesthe

of

spectrum

radiation

the electromagnetic

a cavity. Approximately, it describes

within
the emission
equilibrium
of
the
Sun
or
of
meta!
h
eated
a
torch.
The
Planck
distribuspectrum
welding
by
distributionwas
the first appHcation
of quantum thermal physics. Thermal electroradiation
is
often
caHed
black body radiation. The Planckdistribution
electromagnetic
also
describes
the thermal
energy spectrum of lattice vibrations m an clastic
in

thermal

solid.

The word

\"mode\"characterizes a particularoscillation
amplitude
pattern
low = 2nf as the frequency

the cavity or in the solid. We shall

refer
always
the radiation.
The characteristic feature of the
of oscillation
hio.

energy

of frequency w
The

energy

of
\302\243,

may

be

the

state

excited

with

radiationproblemis
only

of the

in units

s quanta

that

is

U)

e,

where s is zero or any

integer

(Figure

4.!). We omit the

zero point

\\hai.

energy

These

of

positive

of

a mode

quantum of

mode

the

in

in

harmonic
as the energies ofa quantum
to, but there is a difference between the concepts.A

energies

frequency

are the same

Figure

4.1

represents

to s

oscillator
harmonic

Stales of an oscillator
a mode of frequency

photons in

the

mode.

that
tu of

an

(-haptcr

4-

modes a and
magnetic

b, of

Distribution

and Planck

Radiation

Thtftjml

and \302\253>t.
The
&>\342\200\236

frequency

field is suggested

in

the

figures

occupancy ofeach mode.

amplitude
for one pliotor

oscillator is a iocasizedosciiiator.whereas
the
an electromagneticcavity
mode
is distributed

and

electric

of

magnetic

energy
the: interior of

throughout

the

(Figure
problems the energy eigenvaluesare integral
of ho, and this is the reason for the similarity
in the thermal physics of
multiples
the two problems.
The
used to describe an excitationis different;
s for
language
the oscillator
is called the quantum number, and s for the quantized
electromode
is called
the number of photons in the mode.
electromagnetic
We
calculate
the thermal
first
average of the number of photonsin a mode,
a reservoir
at a temperature
when these photo ns are in thermal equilibrium
with
t. The partitionfunction
is the sum over the states A):
C.10)

both

For

4.2).

cavity

B)

}{~shia/r}.
This

sum

is of

ihc form

the infinite scries

may

TV,
be

with

.\\-

and

summed

exp{-/i<y/0-

Because

has the value 1/A

.\\-

is smaller

than

1,

-- x), whence

C)
1

-exp(-tou/T)

Planck Lax and

The

the

that

probability

state s of energy slim

is in the

system

Slefan-BohimannLt*

is

by the

given

factor:

Bohzntann

P(s)

The thermalaverage

of

value

exp(

\342\200\224

shci/x)

s is

E)

With

ftej/r, the summation on the

>' =

the

has

side

rmht-hand

form:

-cxpt-v)/

From C)

and E) we

find

-exp(->.)'

F)

This is the Planck distribution

photons(Figure

4.3)

number of
with

energy

PLANCK
The thermal

in

for

function

a singie

mode of

AND

average

frequency w. Equally,

phonons in the mode.The result

in the form of (!).
LAW

thermal

the

lo

applies

any

it is

number of
the average

kind of

wave

field

LAW

STEFAN-BOLTZMANN

average energy in the modeis

\342\200\224
)

1*

G)

4: Thermal Radiation

Chapter

Disiribttlio

Planck

and

+
*(\302\253)

as a function
Figure 4.3 Planck distribution
ofihe reduced temperature i./rw. Here <s(w)>
is Hie thermal average of the
of
rmniber
photons in the mods: of frequency en. A plot of
where
O(o)> + i is also given,
$ is the effective
7ciopoint occupancy
of ihc mode; the dashed
line is i!ie classical asymptote.Noie that
we

0.5

/
A

The

high

be

may

exp{frfcj/t)

limit

temperature

0.5

as

approximated

often

is

\302\273
ha)

lna/r 4-

1 4-

limit. Here

the classical

called

*
\342\200\242
whence
\342\226\240,

the

classical

average energy is
^
<\302\243>

There
mode

is an
has

own

conducting cavity

in

frequency
the

form

wn.

of a

For

(8)

modes

of electromagnetic

number

infinite

its

T.

radiation

within

cube of edgeL, there

is

cavity.

any

Each

a perfectly
of modes of the

within

confined

a set

form

Ex

ExOitn

wtcos(fiJji.v/L)sin(iiyjij'/L)sin(fi.Jiz/L)

ID
Et

Here Ex, Er and

are
\302\243;0

the

independent,because

sin(fl=Tiz/L)

(9a)

(9b)

= E-0
Ex

are

(9c)
the

three electric

field components, and

The three

corresponding
amplitudes.
the field must be divergence-free:

components are

\302\243lQ,Ey0
not

and

indepen-

A0)

When we insert {9}into A0}

and

\302\243,0\",

the

field vectors must

rhar the

states

This

nx,

components

4- E:Qn:

E^nr

ny

transversely polarized

be

condition

the

find

-. Eo \342\226\240
0n \302\273

A1)

vector

to the

perpendicular

the electromagnetic field

>l, so that

and

Law

Slcfan-Bolwtann

factors, we

ail common

drop

and

Law

Planck

field.The polarization
direction

is defined

in

the

as the

with

is a

cavity

direction

of Eo.

For a

given

n,,

triplet

directions,

polarization

can choose two

so rhat rhere are mo distinct
nft

n. we

On substitution of (9) in the wave

c the

wilh

velocity

of light, we

if we
\";\342\226\240

\"y

>h<

4-

are of the

The total energy of the

iij

independent

by an integral

indices.

That

n;2)

mode

the

is,

over

we set

,,/

photons in the

= w3L2.
in terms

A3)
of Hie triplet

of integers

A4)

,
rta\302\273)\302\273'i

A5)

mrc/L.
is, from

cavity

G),

integers alone will

the sum over nx,
modes of tlic form
(9). We
replace
the volume clementditx dny dnx in the space of the mode

The sum is over the triplet of

ny,

Hya

form

w.

all

iriplei

define

the frequencies

describe

each

.(V

'.

trJJ.

\302\253)
of

= (rtj[2
\342\200\236

then

perpendicular
for

find

cWnJ

This determinesthe frequency

modes

equation

i:y

V'-v1

mutually

integers nx,

ny,

n..

Positive

Chapte

where the factor

We

involved.
two

now

the sura

the positive

only

or integral by

a factor

of the electromagnetic

polamations

octant of the Spaceis

of 2 because Ihere are
field (two independent

Thus

modes).

cavity

because

arises
(\302\243K

multiply

independent

setsof

=h

1, = ji ft

hu)n

Jo

with

A5) for

over

a dimensionless

Standard
\302\253\342\200\236.

dnn*

(nVic/L)

\302\273\302\260

is to

practice

We set

variable.

\342\200\224

A8)

ex

transform

x =

the definite integral to one

and

nhcn/LT,

A8)

becomes

A'J)

integral has the value z*/l5; it

The definite

such as Dwight

in the

(cited

general

is

in good

found

references}. Tlie

standard

energy per unit

the

volume

lional !olhe
of

law

fourth

V =

L1. The

power

oflhe

result that
lemperalure

is

B0)

\\Shs

with

volume

tables

the

radiant

is known

energy

density

is propor-

as theStefan-Boltzmann

radiation.

we
B0) into the spectral
decompose
applications of this theory
as
the energy per unil
of
the
radiation.The
is
defined
density
spectraldensity
We
find \302\273u
from
and is denoted as \302\253\342\200\236,.
can
volume per unit frequency
range,
in terms of w:
(IS) resvritlen

For

many

B1)

U/V

so

that

the

spectral

density

is

B2)

Planck

Law

andSufan-Boltzmam

Law

\\

1.2

1.0

\342\200\224

0.6

0.4

0.2

\\

\\
\342\200\224 \342\200\224

0/

~ l)willi.v = bttf/t. T\\\\h

runciion
h involved in the Planck radiation law for llic
of a black body may
spectral density uw. flic temperature
be found
from ilie frequency tjmil ai which the radiant
Figure-1.4

Ploiof.vJ/(c*

is a maximum,
energy density
per
This frequency is directly
proportional

unit

ffequency

so ihe

range.

tempera sure.

of
distribution
This result is the Planck radiation
the frequency
law; It gives
thermal radialion (Figure4.4).Quantum
here.
theory
began
the relation
The entropy of the thermal photonscan be found
from
A34a)
~
at constant volume:da
from
B0),
dUfr, whence

Thus

the entropy is

B3)

The constantofintegration

is zero,

from

C.55) and the

relation belsvecnF and

a.

4: Thermal

Chapter

gy

flux density

area

and

length

is of the order of the

of
equal to the velocity

factor is equalto \302\243;

the

The geometrical

The

by

for

result

final

use of

gy

The

Distribution

Planck

and

Radiation

the

radiant

the energy density

B0) for

light

the

is (he

time.

of

unit

of

Thus,

subject of Problem 15.

The

is often written

result

as
B6)

\302\253

aB s= b2V/60AV

has the

5.670

vahie

10~8

W m~2

(Here cts is not the entropy.) A

as

black

A small

body.

body

the

on

10\"*

K~* or 5.670x
that

a cavity

radiates
whose

walls are
rate
walls

in

is said to radiate

thermal

given
of

K~\".

s~'

cm\022

erg

at this rate

as a blackbody at the
of the physical constitutionof the

is independent
only

in

B6a)

T will radiate

at temperature

depends

hole

unit

is

flux

U/V.

Jv

times

derivation

energy

a column

in

contained

energy

equilibrium
in

B6).

the cavity

The

rate

and de-

temperature.

Emission and

Law
Absorption; Ktrchhoff
to the ability of the
The
of a surface to emit radiationis proportional
ability
surface to absorb radiation. We demonstrate
this relation,
first for a black body

or biack

surface

is defined to

incident

upon

biack if

the

and,

second,

be blacktn
it

hole

for a

surface

with

arbitrary

properties.

An object

electromagnetic radiation
a ho!e
in a cavity is
in that range is absorbed. By this definition
small
incident
the
hole will
is
enough that radiation
through
a given

frequency

range if all

reflect

times from the cavity

through the hole.

enough

in the

be absorbed

lo

walls

cavity

with

back

loss

negligible

oj Sutj

The radiant

a black surfaceat temperature

x is
from
a
small
hole
a
in
equal
density
Jv
cavity
al the same temperature. To prove this,
let
us close
the hole wilh the black
in thermal
the thermal average
surface,hereaftercalledthe object,
equilibrium
fiux
from
the black object to the interiorof the
be equal,
must
energy
cavity
but opposite, to the thermal average energy
flux
from
the cavity to the black
to the

energy

flux

radiant energy

Jv from

density

emitted

flux

object.
We

the

prove

following:

fraction a of the

non-black object

If a

radiation incidentupon

at

temperature

absorbs

by the
emitted
by a black body at the same
and
e the emisstviiy, where the
flux emitted by the object is e times
it,

the

radiation

flux emitted

object will be a ttnies the radiation flux

temperature. Let a denote the absorptivity
cmissi\\ity is defined so that the radiation
the fiux emitted
Theobjectmust emit
by a black body at the sametemperature.
at the same rate as it absorbs
that
if equilibrium
is to be mainiamed. H follows
a is
law.
For the special case of a perfectreflector,
a~e.
This is the Kirchhoir

whence
e is zero. A perfect
docs not radiate.
reflector
The argumentscanbe generalized
to apply to the radiation at any frequency,
<o and
as betsveen
w + ito. We insert a filter
between
and the hole in
the object
black
outside
this frequency
the
range, and
body. Let the filter reflect perfectly
now
this
The
flux
let it transmit
within
arguments
perfectly
range.
equality
=
for any surface
eM
a(w)
apply to the transmitted spectral band, so that
in thermal equilibrium.

zero,

of

Estimation

Surface

Temperature

of a hot body such as a star is

emission
takes
from
the
Ihe maximum
of radiant energy
frequency
is depends on whether we look at the
this
(see Figure 4.4). What
frequency
place
For if,,,, the
fiux
range.
range or per unit wavelength
per unit frequency
energy
the
Planck
the maximum
is given from
energy density per unit frequency
range,

One

way

to

estimate

the

surface

temperature

at which

law,

Eq. B2),

as

\342\226\240\342\200\242
0

- 3exp(-x)

= x.

This

be solved

may

equation

and Planck

Radiation

Thermal

4:

Chapter

DiVnfmrion

numerically. The rool is

kca^JkgT = xm

2.82

B?)

Figure 4.4.

as in

is that the
Example:Cosmicblack body background radiation. A major recentdiscovery
universe accessible to us is filicd with cudutian
like
a
thai
of
black
approximately
body
Tor big bang
at 2.9K. Tlic existence
evidence
of lliis radiation
[Figure 4.5) is important
assume
ltw! tli^ unhorse is expanding
and cooling
wiitl liliic.
cosmotogiol modelswhich

so

h;id coo

universe
irucructs

This

Most

lines.

mancr.

Tftcrcafier ihe radiaiion evotved with \302\273mcin a very siinpte way: llic plioion gas
of 2.9 K. Tlic pfioion gas will
al constani cniropy io a icmpcraiure
by expansion
at consent
ihc expastsion
during
cniropy if Ihe frequency of each mode is towered
universe
wilfa llic nuoi^er of pljotons it\\ c>icti mooe Kept con^JunlL We show in ^joj
that ihe entropy
is constant
if lhe number of pholons in each mode is consiant\342\200\224the

cooled

was

remain

of

;uid itie bhiirk body radiaiion were in Itiaiipl

cqtiitilirium.
IJy ihe lime
ted lo 300A K,! tie m;iiUv Mas primarily
in she farm of atomic liydrogen.
with bLjck body r^diLitJi^Ji
si the fic^ucOci^b of jlic liydro^jcti
&fH:ctriJ
only
itie
of llie biack body r;idi;ition
thus was cffctiutty docouptoti
from
clergy

nimicr

Ihc

ihaf

itic

tnc

below

lhe

After
inlo

ihe eniropy.
Urn evoluiion

determine

occupancies

decoupling

and

stars,

galaxies,

Electromagnelicradiaiion,
is superimposedon the

black

cosmic

As an important exampleof the

sponMucousthermal
called

H. Nyquisi.*

noise,

H. N!jquisi,p!:js

lical jijsus,

ts

4.6. We

\342\226\240

Wiley,

botiy radiation.

shall

R
!

sec

across

that

by J.

property of
lo llic

proportional

<K:)

dimension, we

in one

law

Planck

were discovered

The characteristic

square noisevoltage
by Figure

atoms (which are organized

lhan before decoupling.
complicated
radiated by the maiter since lhe decoupling
heavier

inlo

more

tn voltage

fluctuations

are

tnaucr

NOISE

ELECTRICAL

which

of

ciuSl clouds) was

as slarliuM,
such

a resistor.

B. Johnsonand

Johnson

value of the

is also

noise

consider the

These fluctuations,
explained

resistance

by

ihc mean*

is that
R,

as shown

directly proportional to tlie tem-

Microwave

Interstellar CN

measuremeni

IR

2.9

K Black

body-

Frequency (cm\"!)
4.5

Figure

me surememsof lhe spcclrum

Observations nf the flux were made with

Experimental

body radiation.

speclrum ofinlcrslettac

oflhe

infrared

a bulbon-borne

wiih

Caurlesy of P. L. Richards.

pcrature r and tlie band'-vidili

edge of
Tlie
voltage

A/of
wave

cLvironuignetic

tlicorcm

Nyquist

generated

uccded in

any

gives

by a resisior
estimate

of

neiir

lhe peak,

ai frequencies

the

circuit.

propagation

a quanlhative.
in

thermai

Hie iinnting

cosmic

of the
microwave

heicr

unJ vvere rneusi

abo\\c lhe peak.

(Tliis secifon presumes a knov.1at Hk inicrtncdiiitc

level.)

expression

equilibrium.

signal-io-uoise

The

for ihe llicrma!noise

theorem

is lhcr^fore

ratio of an experirr.cnial

and Planck

Radiation

Thermal

4:

Chapter

Zl
~

\342\200\242
Carbon

filamen

+ Advance wire

xCuSO, m H,O

vNaCi

RcMblancu

Mil

in

component,

kinds of conductors,including

0.5

0.4

0.3

0.2

0.1

H..O

in

Afiei

electrolytes.

J.B.Johnson.

In ihe

apparatus.

square

original
a

across

voltage

the

form

resistor

states

theorem

Nyqutst

of resistance

in

ft

ihe mean

that

thermal

at

equilibrium

temperature t is given by

B8)
where A/

is

the

frequency*

bandwidth

the

which

within

circuit

the

of Figure

4.7, the

power deliveredto an
'

al

which

'

In

this

maich

section

(R' =
the word

(R + Rf

fluctuations

voltage

are measured; all frequency components ouisidethe given

We show below that the ihermal
noise power per unit
frequency
a
to
where
resistor
a
the
facior4
enters
matched
loadis
x;
by
arbitrary

are

range

range

it does
resistive

ignored.
delivered

because
load

'

in

R' is

B9)

R) is <1\">/4J!.

frequency

refers

to cycles

per

unit

time,

and not

to

radians

per

unit till

Noise generator

4.7

Figure

load R'. The

which
this

hi

power
enables

oftliermal noise that

Consider
characteristic

as in

impedance

is a maximum wiih
condition
the ioad
At

supply.

us to

the

limit

voiiagc

be

absorbed

circuit is maintained

power

said

at

= R.

when R'

lo the

to bo matched

- (Yi)f4R. The

filter

bandwidth under
[lie bandwidth
10 whicii
the mean

fluciuaiion

applies.

line
Figure 4,8 a losslesstransmission
~
R
terminated
at
eachend
Zc
by

wiihoui

with

to a

frequency

is.

ihal

to R'

respcel
is

&

match,

line is matched at eachend, in

will

resistance ft

delivers

cilrrenl

consideration;
square

ciicuii for a

Equivalent

a generatot

sense

the

reficciion

in

that
the

ail energy
appropriate

of lenglh
a resistance

L and

charac-

R. Thus

the

traveling down the line

resisiance.

The

entire

t.

temperature

line is essentiallyan electromagnetic

sysiemin one dimension.
We follow ihe argument given
above
the
distribution
Tor
ofphoions in thermal
but now in a space of one dimension instead of three dimensions.
equilibrium,
has two photon modes (one propagating in eachdirection}
Thetransmission
line
= 2nn/L
of frequency
in
the
from A5), so shat
freihere
are iwo modes
2nfa
A transmission

frequency range

C0)

Sf~c'lL,

where c' is the

propagation

velocity

on the

line. Each

mode has energy

C1)

exp(ftwAJ

Figure 4.8

Transmission

Hue

derivation of ihc Nyquist

aclerislic
line

has

ihe

heir

The

liieorcm.

impedance 7,c of ihe [ ra us mission

vaiuc R. According lo ihc
of Iransrnission
iines, [he
matched to the line ivlicn

theorem

mdamcniai
erminai

L with

oficiijjtli

resistors

resistance

are

same value R.

has ihc

in

is r. It

in

the

that

follows

hw

limit

classical

the

Planck distribution.

to the

according

equilibrium,

with circuits

on the

energy

\302\253
z

so

line

in

the

are

We

energy per mode

A/ is

range

frequency

concerned

usually

the thermal

that

C2)

The rale at which

line in one

off the

comes

energy

direction is
C3)

The powercoming

off

the

al

line

end is

one

that end; there areno reflections

impedance

R at

is matched

to the line.In thermal

line at the same rate, or elseitstemperature

to the load is

9 =
but

2R1,

itt

temperature(hermomctry,

dc current

when

no

when

a dc

iA/

the power input

C4)
used

been

{Figure 4.9)

where

in low
it

is

tempera-

{not

con-

more

than t. Johnson noise is the noiseacross

(V1}
discussed
is flowing. Additional noise
here)

resistor

appears

current flows.

PHONONS IN SOLIDS;

DEBYE

THEORY

calculate the spectraldistribution

of
this distribution
for a continuous solidand to consider
So I

energy to the

The result has

regions

temperature

impedance

measure

to

convenient

B8) is obtained.

so that

\302\273

Thus

rise.

terminal

the

terminal

must emit

load

would

</2>R

the

when

the

equilibrium

all absorbed in

decided to

approximationto

the

actual

distribution.

The

the

possible

as a

fvee vibrations

good enough
of a lattice must,

sonic spectrum

j in

Solids:

Dcbye Theory

square noise \\ o'uge

flucluations
observed cxperimcn::i))y from a
3 jiO resistorin ihe mixing chamber of a
dilution
as a function of magnetic
refrigerator
4.9

Figure

Mean

icmpcralurc indicated by
tlidrmometer.

After

R.

C Wheailey, J.
533 A972).

and

J.

a CMN'

R. GiiTarJ,
Low

powder

li.

Tcnir

Physics

100

of course,deviatefront

its soon
its t!ie wavelength becomes comparable to
. .. The only thing which had to be lione was lo
to she fact that every solid ofjunta dimensions
numfrc'r
contains
adjust
ajiuite
atoms
and
a
At
low
has
mint
her
vibrations....
of
therefore
L'uoiujh
finite
of free
and ttt perfect analogy to the radiation htw
temperatures,
of StefanBoltzmann
..., the vibrational energy contentof it solid will be proportional

t/ie

disittuees

this

of the atoms.

P. Dcbye

The energy of an elastic wave

electro

elastic
;is for

wave in a cavity

magnetic

clastic wave

is calleda
of

wave

in

oj is

is quantized

just as the energy

is quantized.The quantum
thermal

The

phovwn.

frequency

a solid

average

number

of

energy

of an

of pitonons in

Planck distribution function,

given by the

an

of

an

just

photons:
1

We assume

that

t!ie

frequency

ofan

elastic

wjive is independent

C5}

of theamiMttmle

and heat capacityofiheelastic

be carried
of the resiiks obtained for photons
waves
in
solids.
Several
may
th:tt the velocities of ail
over to plionons. The resultsare simple
if we assume
elasticwaves are equal\342\200\224independent of frequency, direction of propagaiion,
but it helps
Thisassumption
is not
and directionof polarization.
very accurate,

ofthe elastic

sixain.

We

want

to find

the energy

A-

Webb,

6,

the general trend of the observed results in many

with a
solids,
of computation.
Therearetwo important
of the experimental results: the heat capacity
features
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
for

account

minimum

contribution
Number

the

from

conduction

There is no limit to the number

of
but the number of elastic modesin
with

each

3A?.

An

wave

elastic

in

Chapter

7.

Modes

of Plionon

of N atoms,

treated

electrons,

three

possible
a finite

modes

in

a cavity,

If the solid consists

lite total number of modesrs

of freedom,

degrees

has three

electromagnetic
is bounded.

solid

possible po! matrons,

a

two

transverse

and one

polarizations of an electromagnetic
of the atoms is perpendicular
displacement
a
wave the displacein
wave;
longitudinal
displacement is paraiicl
over
all
to the propagation
direction. The sum of a quantity
modes
3,
may be written as, includingthe factor

longitudinal,

in

two possible

to the

contrast

wave.In a transverseclasticwave the

to the propagationdirectionof the

| JW
of A7). Here n
as for photons. We

by extension
exactly

elasticmodes

ts

to

equal

C6)

of the triplet of integersnxt i\\yt iu,

;iralI such that the total number of

in terms

is defined

to

want

<*\302\253(\342\200\242*\342\200\242)
,

find

3JV:

C7)

In the
number

photon problem there was no cor espondinglimitationon the total

of modes. It is customary to write D, after Debye, for nraaI. Then C7)

becomes
in\302\273D3

The thermalenergy

of

the

3;V;

phonons

nD =

is, from

FW/7!I'3.

A6),

C8)

,\\umbcr

by C6)

or,

ofPho

and CS),

D0)
with

analogy

By

place

where
limit

of

usually

of A9),

the evaluation

{'in2twf2L)(xL/n!n-)-i

For

ji/irii/Lr.

the

velocity

of sound

written

in

L3 we

J*V*

D1)

\342\200\224~~^

write the volume V.

with

Here,

C8),

the upper

is

integration

written as
-

,vfl

where6 is

the

called

Dcbye

0/7

= fcsO/'t .

D3)

temperature:

0 =

The

with

velocity of light r,

of the

(hv/kB)Fn2N/VI \\

D4)

special interest at low temperaturessuch

than
that
T \302\253
0. Here
the limit .xD on the integral is much
umly, and .vo
larger
4,4
is
little contrithat
there
be
We
note
from
may
Figure
replacedby infinity.
=
we have
to
10.For the definite
the integrand
out beyond x
contribution
integral
result

for

D1)

is of

the energy

f\"^

Jo
as earlier.

Thus

the energy in the

proportionalto

T4\302\273
The

heat

__\302\243_-?-

exp.x-

D5)

15

low temperaturelimitis

capacity

is, for

\302\253
kB0

or

\302\253
0,

D7a)

4: Thermal

Chapter

Radiation ami

Distribution

Planck

17.78

-\342\226\240\342\226\240
\342\200\224

a
E 13.33

4.44

Y
\\A

3.99
in

r3,

Figure 4.10
show

TJ10

these

from

Low tempcralure

heat

Ihc cxcettent
daia

is 92

agreement
K. Courlesyof

capaciiy
whh

!tie

5.32

K3

of solid
Debyc

and

L.1 Fincgold

argon, pioiicd against

The value of 0
N. E. Phiiiips.

T1 law.

In conventional units,

D7b)

This

h known

result

as the

Debye T1 !aw.*Ex

plotted in Figure 4.10.Representative

temperature

plotted

Problem
given in

are

given

in Fig-jrc

in Table

4.1. The

13.297 A912):

values

calculated variation of

4.11. The high temperaturelimit

functions

tiiermodymmiic

4.2

and

14,65 A9K).

are

plotted

in

for argon are

of the Debye tem-

results

menta!

experimental

II. Several related

TabL*

peri

Figure

4.12.

T\302\273 0

for

Cv

is

versus

the

a Debyc

T/6

is

of
solid are

subject

Aiimitr

Lu

of

210

Jjg

7.

UJ

UJ

EQ

pT

UJ

<

(J

a.

Photon

Modes

4: Thermal RaJhtion

Chapter

ami

Dim

Planck

25

i
^\342\200\224^\342\200\224

20 -

/
Heal

Figure-5.11

according10ihc

capacity

solid,
The

approximation.

Dcbye

vertical scale is in

Cv of a

J mol~'

K\"'.

The

Iiori^onla! scaieis ihc temperature

to the Debye temperature 0.The
normalized
TJ law is below 0.10.The
of
ihc
region
value
al high values of 7\"/1? is
asymptotic
24.943

Jmor1

L\342\200\224

K\021.

0.2

'able

4.2

Values of

C,, S, U,

ai

id F on the
S =

k^o

Debye

0.6

0.4

ihc ory.

0.8

in unlls J

U,0

moI\021

1.0

K\"

IT

Cv

24.943

0.1

24.93

90.70

X
2402

- 666.8

0.2

24.89

73.43

115.6

-251

0.3

24.83
24.75
24.63

63.34

74.2

56.21

53.5

50.70

41.16

24.50

46.22

32.9

27.1

0.4

0.5

0.6

CO

0.7

24.34

0.8

24.16

0.9

23.96

1.0

23.74

42.46
39.22
36.38
33.87

1.5
2
3

22.35

24.49

20.59

18.30

16.53

10.71

4
5

12.55

6
7

9.20
6.23

-87

-60.3

-44.1

-33.5

-26.2
-209

16.82

-17.0:

9.1
5.5
2.36

6.51

1.13

4.08

0.58

2.64

0.323

0.1S7

0.114

2.53

10

1.891

0.643

0.048

15

0.576

0.192

0.0096

-137

19.5

1.22
0.874

3.45

170

22.8

1.77

4.76

1.2

0.073

-7.2:

-3.6.

-1.2

-0.4!

-0.2

-0.1

-0.0

-0.0

-0.0

-0.0

-0.0

Summary

20
0

10

-10

-20

-30
1.5

1.0

0.5

\024\302\2600

FiKiire^.12

Energy

solid, according

of tlic

solid

to tiit

free energy

t/and

theory.

DcbyC

s=

I/-

Tlic Dcbye

roof

temperature

is 0.

SUMMARY

Planck distributionfunction

1. The

for

the thermal

2. The

is

average number of

photons in a cavity

mode

Stefan-Boltzmannlaw is

for the

radiant energy density

15/iV

in

a cavity

'

at temperature

t.

of

frequency

3.

Planck

The

and Planck

Radiuiwn

Thermal

4:

Chapter

Distribution

law is

radiation

\302\2533

r2c3

the radiation

for

energy per

unit

volume

The

low

Debye

is,

in

where

limit of

temperature

conventional

unit

per

4. The flux density

of radiant
energy is Ju
Boitzmann constantn1ks*/(i0hici.

5.

\342\200\224

exp(/io)/t)

range

\342\200\224

of frequency.
aB is

where

oBTA,

the Stefan-

the heat capacity of a dielectricsolid

uniis,

the Debye

temperature
0 s (hvjkB)Fn2$fvy'\\

PROBLEMS

1.

Number

of

thermal

at temporal

equilibrium

Show

photons.

ure

a cavity

in

that the number

of volume V is

of photons XXs\")

= 2.404n~2K(t/Ac)s.

in

D8)

i-rom B3) the entropy

is a = Dn2F/45)(r//icK,
believed that the total number of photonsin the

whence

<r/N

=s

3.602.

It

is

universe
is 109 larger than the
both
are of
total numberof titiclcons(protons,neutrons).
Because
entropies
the
the order of the respective
of
number
(sec Eq. 3.76),
photons
particles
of the universe,
provide the dominantcontributionto the entropy
although
the particles dominau- ., c total energy.
believe
that
the entropy of the
We
so that Mie entropy of the universeis approxipllotonsis essentially
constant,
approximately

7. Surface
density

with

constant

at

temperature ofthi! Sun. The value

from the Sun normal (o the

the Earth

constant of the
wavelengths

and

time,

Earth.

referred

The

observed

value

of

the

incident

integrated

total
rays

radiant energy Hilx

is called the solar

over all emissionwave-

mean Eanh-Sim disiance is:

to the

solar

constant

0.136

J s

D9)

(a) Show thai the total rate

(b) From this result and

10\"12J s~' cm'2 K\"\"\\

Sun treated asa black
x

theSunasl.5

thai

body

is T

Sun is 4

10\026 J S\"

<rB =

constant

Stefan-Boltzmann

.the

show

10!3 cm

generation of the

of energy

*.

5.67 x

the effective temperature of the surface of the

~ 6000 K. Take the distanceofthe Earth
from

and the radius of the Sun as 7

10l\302\260cm.

of the Sun,
(a) Estimate
by a dimenof magnitude of the gravitationalselfof the
Sun, with AiQ = 2 x !033g and RQ => 7 x 1010 cm. The gravienergy
gravitational
G is 6.6 x iQ\"8 dyne cm2g~2,Theself-energy
constant
be negative
will
referred to atoms at rest at infinite
ihe
total
thermal
Assume
ihat
(b)
separation,
kineticenergy
of the
in the Sun is equal to \342\200\224
atoms
limes
the
gravitational
\302\243
theorem
of mechanics.
Estimate the average
energy. This is the resultof the virial
temperature of ihe Sun. Take the number of particles as 1 x IG*7.This csUmaie
too
low a temperature,
somewhat
because the density of tlie Sun is far
gives
from
\"The range in central temperature for different
uniform.
stars,
excluding
of
of
those
for
which
Saw
matier
the
only
composed
degenerate
perfect gases
and
does not hold (white
those which have excessively sniall average
dwarfs)
and
is between
densities(giants
1.5 and 3.0 x iO7 degrees.\"
supergiants),
B. Lynds, and H. Pillans,Elementary
Oxford,
1959.)
(O. Siruve,
astronomy,
3.

of t/te interior
temperature
or otherwise
(he order

Average

dimensional

argument

4. Age

radiates

of the Sun. Suppose4

at

energy

for

on

radiation,

of hydrogen

Find

the present
time, (a)
the rough assumptions

(atomic weight

the

the

of

he

Sun. It is

(AAf)c\\

temperature

Surface

us much

renijiates
ihe

that

1.5

(a) to

books

converted

estimate the

universe

by

that

Peebles

is about

and by

Calculate the iemperatureofl hesurface

Earth.
it
ihat
a black body in thermal
as
equilibrium
assumpiion
from
the Sun. Assume also
thermal radiationas it receives
of the

over
ihe day-night
Earth is ;it a constant jemporiittini
5S00K;
RQ = 7 x 10locm; and ihe I2arih-Sundislanwof

of the

face
7\"o

ihe

and

4.0026)

IOlJcm.

6.

sin

Use

cycle.

the

on

Earth,

in

conversion

ihe

has been

(b) Use

available

of the Sun

believed ihat [lie age of the

109 years. (A good discussion

is given
died
in
the
Wcinberg,
generalreferences.)

5.

energy

hydrogen

original

=
\302\243

10 x

ofthe

total

L0Q7S)to helium(atomicweight

the

expectancy

which the Sun

total rate at

that the energy sourceis

stops when 10percentof

to helium. Use
Einstein
relation

the reaction
life

is the

lQ;6Js~!

Pressure

(a)

of thermal

variation.

Show for

p = -(cUfcV),

a photon

gas thai:

- -^s/iiiluij/ilV)
,

E0)

and Planck

l Radiat

where s; is the

in the

of photons

number

(b)

Oiildbnti,

dojjfilV

p =

(c)

moJej;
-mjyV;

E1)

U/iV.

E2)

to 3 x (energy density).
with the kinetic pressure of a
(d) Compare pressure
radiation
of t mote cm'3 characteristic of the Sun.
gas of H atomsat a concentration
At
what
the two pressures equal? The average
are
temperature
(roughly)
of
the
Sun
is
believed
to
be
near2 x tOT K. The concentration
is
temperature
at
where the
the
highly nonuniform and rises to near rOQmoiecm.\023
center,
kinetic pressure is considerablyhigher
the
radiation
than
pressure.
radiation

the

Thus

is equal

pressure

of thermal

the

7. Free

energyof a p/iot

photon gas is given

where

ihe

the parlhion

that

Show

(a)

gas.

function of a

by

is over

product

direclly from

on

the modes \302\273.

(b)

free energy

Helmholtz

The

is found

as

E3)

E4)

F-T][tog[t-exp(-AuiA/T)].

Transform

the sum to an

integral; integrateby
F =

5. Heatshields.

to a
between

black

the

constant

at

plane

two

black

planes

is allowedto come
and T,, and show
presence of this

to
that

net

energy
where

is inserted

temperature

energy flux density

is the principle of

Tu is parallel

at temperature

- T*),

plane

state

a steady
the

plane

T(. The net

black

third

find

E5)

is Jv = aB{Tf

used in B6). A

to

-n

(nonreflective)

temperature

parls

flux

aB

density

is the

in

vacuum

be-

Stefan-Boltzmann

between the other two and

Tm. Find Tm in terms of 7'B
is cut in half because of the

the heat shield and is widely

used
reduce
radiant heat transfer. Comment:The result for N independent
heat shields floating in temperature between the pianes TM and
T, is that the
- T,4)/(N + !)is Jy = ciT^
net energy flux density
plane.

This

to

9.

L on
transmission line of length
wave
waves satisfy the onc-dimcnsional
electromagnetic
equation
=s c2E/ct2l where E is an electricfield
Find
the heat
v2d2Ef3x1
componentof
the
on
thermal
at
the
w
hen
in
capacity
photons
line,
equilibrium
temperature

which

Photon

gas

in one

dimension.

Consider a

r. The emiiiicrulioiiof modes

lake ilic soiulions siundmg
waves

ihe usual
way for
zero amplitude ai

in

proceeds

with

as

line.

10.

Hcitt

radiaiion

by

hcai capacity of mailer lo lhal of radiaiionis ~-

of ilic

ralio

ilic

thai

in a

atoms

by

Sntcrgalactic space is believedto be

concentration
=laionim~\\
The space is
al 2.9 K, from the Primitive Fireball. Show

space.

of iniergalaciic

capacity

occupied hydrogen
alsooccupied thermal

one dimension:
cacli cud of ilic

10'9.

limit.
Show
lhal in ihe iimil
of solidsin high temperature
a
solid
towards
die
limit
of
capacity
Cy \342\200\224\342\226\240
goes
3A'\302\243B, in
conventional
units.
To obtain higher accuracy when
T is only moderately
can be expanded as a power seriesin 1/T, of
larger than 0, the heat capacity

Heat capacity

//.
T

heal

liie

\302\273
0

the form

E6}

Determine the first nonvanishing

- 0 and
T
comparing with
temperature

Dcbye

in the

lemperature at which the photon contribution

equal to the phononcontributionevaluated
13.

Energy fluctuations

atoms
is

in

from

the

in

ihermal

contact

with

3 to

show

at

ai low

region

in which

a heat
the

that

IF is given by

inserting

dtelcciricsolid

with

the

cm ~3. Estimate

heat

the

to

a solid

in

temperature

Chapter

your result by

sum. Check

4.2.

of photons andpltonotts. Considera

10\"
atoms
equal to 100K atid with

Heat capacity

/2.

term
Table

capacity

would be

1 K.

temperatures.
ihe Dcbye

Consider a solid of N

Ti

law

is

vaiid.

The

solid

fluctuations
reservoir. Usethe resultson energy
root
mean square fractional energy fluctuation

E7)

T =

that

Suppose

a side;

$F

then

order of uniiy
14.

Heal

longitudinal

p=

0.02.

in liquid

waves

(a)

0.145gcm~3.

transverse

no

are

gram

capacity

per

value

=\342\226\240
0.0204

Calculate

on the
x

T\\tn

= 200K;and N

1O1S for

the fractional
particle of volume

!0\025 K

of liquid

capacity

sound

At

a dielectric

for

s\"'. There

CK

I0~2K;0

the Debyc

waves

0.01cm on
is of

energy

ihe

cm3.

*He at low temperatures.

4He at temperatures bctaw
sound

in

fluctuation
1

a particle

in the

The
0.6

of longituvelocity
K is 2.383 x 104cm

liquid. The

is

density

temperature, (b) Calculate

the

heat

with the experimental

and
compare
K*1.
The
T3
Jg\021
dependence of the experimental

Dcbye theory

value

thai

suggests

the

Physica

Distribution

most

Hit;

due

32,

625

to
f

excitations

important

value

experimental
are

experimems

Kramers,

are

phonons

below 0.6 K. Note that

liquid.The
H. C

and Pfanek

Radiation

Thermal

4:

Chapter

in liquid

4He

expressed per gram of

C. G. Niek-Hakkenberg,and

has been

J. Wiebes,

!957}.

distribution
that
the spectra!
of radiant energy flux, (a) Show
of the radiant energy flux that arrives
in the solid angle i!Q is
0 is the angle
the normal to the unit area makes
with
fuucos0*</n/47r,where
the incident ray, and i^ is the energy
unit
Show
density
per
frequency range, (b)
that
the
sum
of this quamity over all incident rays
is \\aiu.

15.

Angular

density

16.

Image
An on a

radiant object. Let

black object of area Ao.
of a

lens
an

Use

the hole in

image

cavity

argument

equilibrium

of

area

to relate the

QQare the solidanglessubtendedby the

the
hole
This general property of
object.
It is also true when
focusingsystemsis easily derivedfrom geometrical
optics.
is
diffraction
the
that
all
Make
important.
approximation
rays are nearly

product

to

AuQtl

axial

{al!

parallel

Qtl and

where

AaQ0

from the

as viewed

leas

from

and

small).

angles

17. Entropy and occupancy. We

chapter that the entropy of the

time because the number
with
body
the frequency
in
of
each
mode
has not changed with
time,
although
each mode has decreasedas the wavelength
with the expansion
has increased
of the universe. Establish the implied
between
and occonnection
entropy
that
for one mode of frequencyw the entropy
cupattcy ofthe modes,by showing
is a function of the photon occttpancy<<(s)
only;

cosmic
of photons

<s +

to start

from

is convenient

It

18.

haxiropic

expansion

not changed

l)log<5 + !)
the

and

the

Consider

of photon gas.

temperature

a cube

- <s)log<s).

ES)

function.

partition

thermal equilibrium radiation in

cavity volume increase;the radiation
expansion,

in this

argtted

has

radiation

black

the

of volume

pressure

performs

of the radiation wit]

in such
is constant

drop.

gas
at

of

temperature

photons

of the
r. Let the

work during the expanFrom

(he result for the

an expatision. (a) Assume

that
was
the
radiation
from
cosmic
black-body
decoupled
temperature
was
the radius
of
of the mutter when both were at 3000K..What
temperature
to now? If the radtus has increasedlinearly
the universe at that time, compared
with
at wltat fraction of the present
time,
age of the universe did the decoupling
take place?(b) Show that the work done by the photons during the expansion

entropy we know

of lite

the

The

iV1'3

titat

subscripts

i and

/ refer to

the

initial

and

final

siatcs.

19, Reflective heat shieldand Kircbhoff's

Consider
(aw.
material of absorptivity
it, e-mtssjvtty e, and rcllecttvjty r

suspended between and parallel with

temperaturesru und
t,. Show that the net flux

black sheetsis (I

also

often

are

dewars

film called

Mylar

by the

and in clouds,

alumtntzed

an

of

the wanning
of the surface of
of water,
of an infrared absorbentlayer

describes

interposition

and of carbondioxidein

the Earth. The water may

a

such

e =

GREENHOUSE EFFECT

the

as

contribute

much

layer,

the

90 percent

as vapor

and

of the warming

of the surface of

temperature

Earth

the

the Sun

between

atmosphere

effect.
Absent

between the

intermediate sheet is
helium
I; r - 0. Liquid

by many, perhaps 100,layers

Superinsulation.

Effect

Greenhouse

caused

with

at tempera-

when tiie

density

means

8, which

sheet of matethe sheet be

maintained
radiation
thermal

of

density

flux

the

times

\342\200\224
a. Let

insulated

SUPPLEMENT:

The

r)

in Probfem

as

black

a plane
\\

sfieets

black

two

is

Earth

the

flux
the
by the requirement of energybalancebetween
incident on the Earth
and
the flux of reradiation
from the
to the fourth power of the temperaEarth; the reradiationflux is proportional
of Problem
temperatureof
the Earth,
as in D.26). This energy balance is the subject
the
where
4.5 and leads to the result Ts \342\200\224
temperature
7'\302\243is
{RsI^seV^Ts,
of the Sun and DSE
of the Earth and Tsis that of the Sun; here/fjis the radius

determined
of solar

primarily

radiation

is the Sun-Earthdistance.

The
Sun is

that

of

result

\342\200\224

much hotter than the Earth, but

subtended by

the

Sun)

of roughly

factor

is TE

problem

the solar

reduces

280

the

K, assuming
geometry

T,=\302\273

(the

FC The

5800

smali

solid angle

iiux density incidentat ihe E;irth

by

(i/20)*.

that the atmosphere is a perfectgreenhouse,

radiation
that
that
transmits al! of the visible
layer
falls oa it from the Sun, but absorbs
and
re-emits
a!! the radiation (which lies
idealize
the problem
in
the
from the surface of the Earth. We
may
infrared),
of the infrared
layer
portion of the
by neglecting the absorption by the
the
solar
lies
almost
incident solarradiation,because
entirely at
spectrum
from
4.4. The layer will emit enerry flux
Figure
higher frequencies,as evident
Oux
will
balance
and
the
the suiur i!ux 1$, Su UiJi
tL up
IL down;
upward
**
ft Is- The net downward flux will be the sum of the solarflux Is and the
incident
The latter increases the net thermal Oux
flux lL down from
the
layer.
at the surface
of the Earth. Thus
We

defined

as

assume

as

an

an

example

absorbent

lEt^h + h-ns.
where

is

l\302\243g

the

thermal

Oux from

the Earth in the

E9)

presenceof

the

perfect

effect.

greenhouse

the

that

greeahouse

flux

as

varies

T4, the

new temperature

is

Earth

T\302\243s

so

the thennal

Because

of the surfaceof the

\302\253=
2\302\273/\302\253rfi A.19)

warming

of the

280

K ~

333 K,

Earth is 333 K \342\200\224

280

F0)
K =

53 K

for

this extreme example.*

\342\200\242

For

end

detailed discussions
i. T. Houghton

1992:

see Climale change and

ct aJ, editors.

Climate

change

1992, Cambridge

U.P., 1990

Chapter

and

Potential

Chemical

Gibbs Distribution

CHEMICAL

OF

DEFINITION

Example: Chemical Potential of the Idea!

Internal and Total Chemical Potential
Example:

Barometric

of

Variation

119

POTENTIAL

122
with Altitude

Pressure

Magnetic
Example: ChemicalPotentialof Mobile
\"'\"

in a

Field

Magnetic

Example;

Batteries

Chemical

Potential

120

Gas

Panicles
127

'

\342\226\240

129

131

and Entropy

Thermodymtmic Identity

Numberof

133

134

GIBBS SUM

AND

FACTOR

GIBBS

125

139

Particles

140

Energy

Example:

Occupancy

Example:

Impurity

140

Zero or One
!omz;ition

Atom

in a

Semiconductor

143

SUMMARY

144

PROBLEMS

145

145

1. Centrifuge

2. Moleculesin the Earth's Atmosphere

3. Potential Energy of Gas in a Gravitational
4. Active Transport

5.

Magnetic

6.

Gibbs

7.

States

8.

Carbon

Monoxide

146

146
146

Poisoning

of O2 in a MagneticField

147

147

Fluctuations

Concentration

Ascent

145

Sum for a Two LevelSysSem

of Positive and Negative Ionization

11. Equivalent
12.

145

Concentration

9. Adsorption
10.

145
145

Field

Definition of ChemicalPotential

of Sap in

148

148

Trees

13. Isentroptc

148

Expansion

14.

Multiple

Binding

148

of O2

15. ExternalChemical

Potential

....

149

\342\226\240al
Potential

(H. We found earlier thai

reservoir <2t, ihe Helmholtz

and

Gibbs

Tor

Distribution

free

&

will

assume

and

wiiii

number
equilibrium

with

a minimum,

subject
free

energy

h\\

to N

of the

F2

jV,

- t/( + t/2
+

jV2

the minimum

value

restraints

on the
applies
pp

oiher

N,,.V\302\273

T(ff,

This

in

result

diiTusive

equilib-

ihi5 sysicms

between

A)

<T>)

Because N is constant,She

= constant.

combined system is

(R.

with

equilibrium

of pparticles.

^2, the

F=

Heimholtz

thermal

in

paiii^lc diaiiibution
S,
t!io toial Hchulioltz free energy
.md

between

makes

of

energy

compatible wiih the commontemperature

such as the volume
and
the
system,
y,
equally to ihc combined\302\243,+ S: in
equilibrium

system

single

minimum

with

respect

to

of

Definition

System

Chemical

Potential

.Sj

t*\"Ener\302\260y

exchange\"\"}

conlacl
with each oihcr
Example of Iwo systems,Sx ;mdX., in ihcrmal
and wiih a large reservoir Of, forming a closed total system- I)y opening the take,
contact
wliilc remaining at the common
S{ and ^j can be brouglit in tlillusive
transfer
for a net panicle
tcmpcraiurc r. Ttie arrows at tlm valve liave been drawn
lo S2.
from \302\243j
Figure

5.1

variations

= -5N2.

5Nt

tlF
with

K2, also

K[,

Hutt

at

the

minimum,

- (cFi/cN^^lNi

held constant.
(/F

so

At

With

= 0,
+ lcF2/dN2)sc!N2
(!Nt

~-tlN2,

WG

- (SF2/cNl),yNl

[(cfj/t'iV,),

B)

have

- 0,

C)

cqutlibriuni

- (cF3/cN2)t.

((Tj/oV,),

(\342\226\240\30

DEFINITION OF CHEMICALPOTENTIAL
We

define

the

chemical

potential
I

as
(/;0
I

E)

Chapter 5:

ChemicalPotential

where ji is

Distribution

Gibhs

and

ihe Greek letter niu.

Then

'-

/'I

for ditTusive
when diVt
5j, ihe value of dN \\

ihe condition
expresses
elF will be negative
thai
from

to

5,

free

energy

is

we sec from
C)
are
transferred
panicles
tlN2 is positive. Thus the

If/(,

equilibrium.
is

negative:

When

negative,

and

> ;i2,

^i to &2; ilitit

flow from

us particles

decreases

t'l

the system of high chemicalpotentialto the system

potential. The strict definition of /i is in terms of a difference
are not divisible;
derivative, because
particles

particles

of

low

chemical

and

not

a deriva-

from

F(t,V,N)

- F{x.V,N-

(low

's.

F)

1).

between systems
in
which
the
contact,
rcguhucs
important
fully
transfer.
are
Two
ihat can exchange both energy and particles
energy
systems
in combined
thermal
and ditTusive equilibrium when their temperaturesand
chemical
are eqtial: i[ = t2;/i; = ji%.
potentials
of
A difference
in chemical
potential acts as a driving forcefor the transfer
force
for the transfer
particles just as a differencein temperatureacisas a driving
of energy.
has its own chemical potential.
If several chemicalspeciesare present,
each
The

chemical

and

regulates

potential

it is

as

the particle transfer

as the temperature,

For species
j,
G)

the

wherein

for the

Example:
of

Ihe

differentiation!

TTumbcrs

of

all

particles

are held

constant except

species j.

Chemical

monatomic

potential

of the

Ideal gas. In

C.70}

showed

that

ihe

free

ideal gas is

/logZi

logN!] ,

(8)

of

Definition

is the

for a single

function

partition

Chemical

Potential

panicle. From (8),

A0)

If

which

approximation for

the Stirling

use

we

factorial,we

tlutt v,e

assume

and

A\"!

can differentiate the

fold

approaches

log

iV

log

for

large

A\"

[N

llcttcc the

of \\.

values

- 1 = togtf

-1)--

chemical

\342\200\224

potential

(II)

of the

ideal

gas is
=

,<

or,

by

- log.V)

-rUogZ,

(9),

A2a)

where

\342\200\224

NjV

is the

defined

concentration

F{N

From

approximution.

system

volume

(S) we obtain
By use

separately.

The chemicalpotential

composedof

electrons

of

ths

definition

ji

concentrationof

/t

we expect intuitively:
lower concentration.

the

i)froin.{6)as

A2). The result depends on the

the

na

(A/r/2nfi2K

2 ts

the

quantum

by C.63).

Ifweuseji = F{N) -

Stirling

of particles ami

concentration

-i[log2,
particles,

ideal

Ttog(p/tiiti).

gas

we do

af/j,

not

logjV],

not need to
which

on their total

law p

nr

we

can

agtces

use the
with

numheror on
write A2} as
A2b)

This
is what
concent mi ion of particles increases.
chemical
from
to
to
lower
higher
particles
higher
potential,
on
of
an
the
concentration
ideal
gas
dependence
Figure 5.2 shows
the boiling temperature
or of helium atoms, for two temperatures,

increases

as the

flow from

Chapter 5: Chemical

Potential

The concentration dependenceof/*,

Figure 5.2

composedof dectroio.jrhelium
regime

with n

\302\253

nQ,

a ^as

at 4.2

atoms,

must have a value

of -

of

least

at

^i

concentrations apprccwhly le\302\253lluin

semiconductors.
For gasesit is always
lypical

of an ideal gas
K..To be in the classical

o! r,

units

in

K and 300

oulv for

satisfied
range

Distribution

andGibbs

t. For

electrons this
as in ihe
normal

is

in metals,
satisfied under

those

conditions.

of

and

liquid

pressure, 4.2 K,
lave ncgaiivcchemical

ill atmospheric

licimin

tnolccubr

jtascs aiwjjs

condiiioas: at classical concernrations

such

ihnt

and

room

unJer

potentials

nfnQ

300 K. Atomic
tciilii^blc
plijiically
soe from A2) iliat
/i is

icmpcraturc,

\302\253
!,

we

ncgaiive.

Internal

and Total

The best
equilibrium

way

in

Chemical Potential

to

understand

Ihe

presence

the

of a

chemical

potential

potential step that

acts

is to discuss diffusive
on

Ihe

particles.

This

Internal and

Potential

Chemical

Total

Figure 5.3

tiie voltage polarity shown,

of positive parlic'es
energy
in

be

the

potential
charge

!o J2. The potential

energy
particles would be loweredin 3,
respect

has wide

problem

13.

in Chapter

discussed
same

application and includesthe

We

\342\200\224
n

Sx und

systems,

junction
al

&->t

the

and capable of exchanging particles,but not yel in diffusive

We assume that initially
> /(j, and we denote the iniiial nonfix

equilibriumchemical

difTcrence

potential

the potential

iliat

above

Af[(im'tial)

way to

by

- ^i-

= ;/2

A/j(iimial)

Now

let

such
energy be establishedbetweenthe two systems,
of
each
in
is
raised
energy
by exactly
panicle sysiem
Si
its ininal
value, if Ihe particles carry
one
a charge
qt
simple

in potential

difference

I'

temperature

equilibrium.

hvo

consider

again

semiconductor

establish this potentialstepisto apply

the

between

two

a voltage

systems

lhat

such

A3)

the

with

shown

polarity

also can

in Figure

serve asa potentialdifference:

of mass

by

the gravitational

the

height

/i, we

by

sfcp

in

difference

when

we

raise

potential

gravitational

a system

of particles each

establish a potential differenceMgh,

where

g is

acceleration.

Once a potentialstepispresent,
this

5.3.

is included

in (he

the

potential

energy

of ihe

patrides produced

energy U and in the free energy F of the

keep the free

system.

step raises the

energy
system
*=
free
of
Sx by /Vs A;i(mitial)
energy
AV/ A!7 relative to its initial value. In
to
the
ihe language
of energy
states,
energy of each suite of .Si the potential
has been added. The \"insertion
of the
b^rier
potential
energy
,Yt A/i(initial)
ilie
to
male
the
chemical
of
Hveificd by (B) mises
potential
$x by A/i(!il!ti;il).
of ^, c\302\253i\302\273:il
to ih:lt
fin::!i.-hciiiiL:;il
oi\\S,:
puk-ntuil
If in

Mgurc

5.3 we

/affinal)

= ;(,(initial) -f

of

S2 fiNed, ihe

[,..(initial) -

established

with

i, would be raised by

system

two

between

step

potential

systems of chargedpaniclescan

/i,(inilial)]
A4)

qAY

q >
wild

of negative
with

cespect

was

barrier

the

When

/^(initial)

chemical

difference

equilibrium.

is equivalent to a true potential energy; the

between
two systems is equal to the
potential
will bring the two systemsinto diffusive
equilibrium.

that

barrier

potential

gA

potential
chemical

in

barrier

the

the two

brings

/(i(initial)

The

pj was held fixed.Thus

systems into diffusive

inserted,

\342\200\224

a feeling for the physical

effect of the chemical potenfor the measurement of chemicalpotentialdifferences
two
between
To measure ft2 - /<,, we establish a potential step
systems.
that
can transfer
betweentwo systems
particles, and we determine the step
at
which the net particle transfer
vanishes.
height
The absolute
differences
of
chemical
Only
potential have a physical
meaning.
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
as equal
to the zero of the kinetic energy.
particle
When
total
chemical
external
potential
steps arc present, we can expressthe
gives us
the basis

statement

This

it forms

potential, and

of a

potential

system as the sum of two

= iv

/'

Here

/jtM

is the

internal

be present
electrical,

Pi

the

is

if

chemical potential*
external

the

magnetic,

\342\200\224ca'i

Hi

definedas the
were zero.

potential

A5)

+ft,,;\342\226\240\342\200\236,

per particle in the

energy

potential

parts:

external potential,and

chemical

The term /iCM

gravitational, etc. in origin. The

be expressed

total

the potential
\342\226\240

Gibbs

measures

called

differences

further

chemical

in

fi.

potential

mechanical,

-A

A6)
chemica!

potential

those
of

the

working

semiconductors,

chemical

words

qualifier.

potential

may be

called the

electrochemical

barriers of interest are electrostatic.

Although
n the

be

equilibriumcondition

and
internal
external
Unfortunately, the distinctionbetween
sometimes is not made in the literature.Somewriters,
particularly
and
with charged particles in the fieldsof electrochemistry
when
use
often mean the internal chemical potential
they

The

nmy

jiial

would

as
Apeil =

potential without a

that

potential

and
.

ihe intrinsic
it,*,
'

if

potential
the

that
potcnsjal. He recognized

term

electro-

a voltmeter

mea-

Chemical Potential

and Total

Internal

SysicmB)

5.4

Figure

A model

of ihe variation

aimcispliericpressure\\>.iih

altitude:

of gas at different
gravitaiiona!
field, jn iherma!
\\olumcs

heights

and

con wet.

System (!)

chemicalpotential is clear
unambiguous,
The
use of \"chemical
potential.\"

we

and

without

potential\"'

avoided

tit

situations

in

which

shall

any confusion about

an

tisc \"total
adjective

chemical
should

be

tis meaningcouldoccur.

The
of the
simplest
example
pressure whhahhutte.
external
is itte equilibrium
sysiems in difTcrcm
potentials
bciwccn
lo be isothermal.
assumed
layers ;lt different llcigliis of ihe Canh'satmosphere,
Tim rcul uimosplicfc
is in imperfect equilibrium: ii is'cunstaiiily
upsa
by Hitititoroloeicut
temperature
processes, faoih in the form of macroscopic air movemems and of strong
We may
from clouii fonn;uion, ;inii becauso
of heal input from liiil ground.
grudiunis
make ;in ;ippro.\\imaic
the dilL-iem
air layers as
model
of the aimosphcrc by KtMliiia
^iih
each oilier, in diHerem
syslemsof idea! gases in ilierilia! and diftusive
eiiuilihrium

of barometric

Example;

Variation

diffusive

equilibrium

exieroul

\\c\\c\\,
(Figure 5.4}.If we place ihe zero of the poieinul energy ai ground
is ihe particle massand g ihe
energy per moleculeai heighi Ji is Afyfi,whcrc.\\f
acceleialion.
The internal chemical potential of ihe parlidesis given
by A2}.

poicnlials

the poiemial
gravitational

The loial

bciwccn

diemical poiemial is

{17}
In

equilibrium,

this

musi be

independent of {he

Tlog[i.(/t)/H0]
and

ihc

conceniralion

\302\253(/t).alhcijjlU

A/y/i

hcidil.

Thus

rlog[ii@)/nQ]

h satisfies

(IS)

in

di!

Chapter 5.-Chemical

and

Potential

Dhtnliution

Gibls

1.0

0.5
\\

0.2
\\

o.i

i
5.5

figure
v-iih

atmosphere

The

of atmospheric
The crosses represent

Decrease

ahiiude.

concerting

as

on rocket

sampled

corresponding lo a

pressure
Ihc average

0.0S

fliyhis.

a slope

lias

Vine

siraight

icmpcraiure T =

K.

227

\\

\342\200\224

20

0-10

Heighi,

The pressure

aullilude

li

of an ideal gas is proportional

lo

llieconcenlration;

40

30
in

50

km

Ihe pressure

therefore

is

p(/i)

=.

= p@)exp(-/i/'iJ-

p@)exp(-.V9li/t)

A9)

conation Ti i*i\\ os ^Jtc ilc^czitjciicc 01 liic pressiifcon uli^iLide

of
a single chemical
Al ilie cliaracierisiic Mght hc =
anuoipliere
species.
ihe
e~l =3 0.37.
Hie
decreases
ihe
fraciion
To esiimaie
t/A/g
.-.unospi^er-c pressure
fay
characteristic fietght,
consider
an isoihermal
nioiccuies
atTuosphere composed of nitrogen
wiLliiinioiecular
is 48 x 10\" \"gill.
At a teiliper.lweigh! of 28.Tliema^orail .V^ niolecuie
iureof :90KiIic value of r = kBT is 4.0 x 10\" l4crg. \\W\\nj = 9K0L1HS\021.
the d1.1r.1tand
will
icrisiic iieiijlii
5
mites.
He,
Li^Uiermolecules,
Jit is S.5tm,
H,
approximately
&s

Thl^

in an

itio

fatthcr dp,

t\\ictul

11UC.U1-.C

pressure

ll.o

UanhS

iiut

these

Ivavc

LiiiiiO^pticrc

Fiyuie 5.5 is :i loyatiifunic

on rocket flights. The data

behavior.
iaken

uuromoLrtc

isoihermat

hrgeiy
i>

not

;n;tiir.ittly

jjloi
potnis

cscipctl from ilic

oi\"

f;i!i

pressure

near

iiiiiinspUufc:

see

iwitlicniiiit, ni/i)ft;is ;i iitoic

tfatj bciv^un
10 and
a siraighi

fine, suggesting

Probicm

1.

a'ttipliaital

4QKiloiMcttrs,
roughfy

iso-

vtl and

Tlie straight
= 1000:1,

behavior.

thermal
range

jj{/ij):pl/i,J

line connecting the data points

over an altitude range from ft,

total Chemical Pot

of Figure 5.5 spans a pressure

2km io A, = 43km. New,

from A9),

so that
of

the

of the

slope

at
temperature

which leads to

is Mg/x,

line

wish !hc point k ~

eurve

observed

tltc

T ~

0, p(li),'p{0)

\302\253
227

x,'kB

\302\253

I, is

caused

K. The

non-intersection

by the higher

tempera-

aliiiudes.

lower

one species of gas. In atomic

the compercent,
A'j. 21 pet Oz. and 0.9 pet Ar; oilier constiiuems
account for
of tlie aimosphcre may
be
content
pci each. The water
vapor
at T ~ 300K B7\"C}_
to
15
a relative
100
of
appreciable:
corresponds
pet
humidity
pet
The carbon dioxide concentration varies about
a nominal
value of 0.03 pet. In an
H,O.
be in equilibrium
wftli
iisclf.
The conideal static Uolhenrtal atmosphere eadi gas would
of each would fall off with a separaie Boltzmann factorof the form
concentration
cxp(
-\\/y/i/t},

Tlic atmosphere

M the

with

consistsof

dry air at ica

iess than
0.1

of

composition

appropriate

p^insiTrii^itic

T *}\\

tiff

than

more
is

fevel

TS pet

molecular mass. Becauseof

tlie

JiiTerences

in mass, ihe

difTcrcnt

nk*c

u\\ /iifrprcnl

magnetic field. Consider

m. For simplicity
suppose
f or antiparalld
[ io an applied magnetic field B.
is
Then the poiential energy of a f particle
is - iufl, and the potential
energy of a 1 particle
We may treat the particles as belonging
to the two distinct chemical specieslabelled
4-ii]\302\243i.
t
and i, one vhh external chemical potential ;in,(|J = -mB and the other with jjm,U) = \"iB.
of an clement or as two
The particles
1 are as distinguishable as Uvo difTerent
isotopes
f and
we speak of f and 1 as distinct species in equilibrium
with each other.
different
elements;
with concentrations
of the particles viewed as ideal
chemical
The internal
gases
potentials
Example: Chemical potential of mobile
a system of .V identical particles each
each moment is directed cither parallel

n, and

iij

If

particles

a magnetic

in a

moment

are

ill

iltcrti:iM\302\273\302\253:lK-|k-lJ

it. mtht

magnetic

with

vary

out

are

potentials

!t\\:nivs

iintwi'iiittKlfovcrtbtf

\\\\w \\ wlumc

in unlcr

out

i|ic volume irigmo

5.6).(Tlie

dent

of posiiion,

if there

is free

total
diffusion

to

ut:tintaii)

potential of a species is eoitstam iiiJc

within the volume,) Becausethe
particles

chemical
of

vo!ui\302\273c^iltcsyslciH.llici-.-:-.vt.ij.H
Mi ,i
unal clicnnt.it i- \342\226\240\342\226\240

j cotiMjisl

Potential and

5: Chemical

Chapter

Dhtribut

G'thhs

---

\342\200\224\342\200\224\"

Iff'

ion (i,
5.6

Figure
pari

in

1GIU

of a gas of magnetic
ofihe chemical potential
values of the magnetic field
concentration, at several
= 2 x iO7 cm\021 for I! ~ 0, ihcn ai a point \302\253here B \342\226\240=
20

Dependence

on ihe

ides

Ifn

intensity.

kilofiauasl2iesb)ihccona:nlraiionwillbe2

species in

have

equilibrium

equal

desired

\302\253,{B)

where

ti@}

is tiie

concentrationat
n{B)

n(B)

The result

magnetic
magnetic
colloidal

Held

such

as

= consiant B3) are easily

total concentration
a poini
at magnetic

\302\253

n,{B)

n^B) =
ii[ 4field

intensity-

The

at

nt

a point

of

to be:
,

where

the

field

B =

B4)

0. The total

S is

* n{0)M

form of ihc

but is applicable to

fine

exp{-\302\273)B/T)];

4-

^-

panicles

magnetic

fujictionai

B3)

^\302\253@)exp{-)nB/i)

= Jn@)[exp{jHB/T)

ji,(B)

n{0)cosh{mB/T)

shows [he tendency

;i,01(|).
fay substitution

seen

in{0)exp(mB/t);

orientauons,
solution. Such

\342\200\242
\342\200\242

-Y

to concentrate

result

fecromagncfic

is not

limited
particles

B5)

in

regions

to atoms

of high
wi[h

in suspension

two
in

in the siudy
suspensions are used the laboratory
of superconductorsand fhe domain strucfure of ferromagnetic materials.In
ace used to tcsf for fine structural
cracks in high strength
the suspensions
sfcel,
When
fhese
arc
coated
a
furbine blades and aircraft
with
gear.
landing
ferromagnetic

flux strucfure
engineering,

of {22)and

solutions

!09cm\023.

diemioil poientiais,

lUl)
The

\342\200\242

ciir3

particles

in

of

he magneiic

Internal

and

suspension

fields

intense

ttie

field,

placed in a magnetic
at the edges of the

flic

and Total ChemicalPotential

becomes

concentration

particle

enhanced at

crack.

discussion we added to /<\342\200\236,

the
internal
chemical
potential of ihe
were
ideal
would
be
particles
gas atoms, /iml
particles.
given by A2). Tlie logarithmic
for /iinl is not restricted to id^al gases,but
form
of the conditions
is a consequence
iliat the
do
not
interact
and
their
concentration
low.
that
ii sufficiently
Hence,
particles
A2) applies
to macroscopic particles as well as to atoms that satisfy these assumptions. The only
is the s;tlne of the quantum
difference
concentration
n,,. We can thereforewrite
the preceding

In

the

If

/'iM

where the constant

t log

\342\200\224
does
t log \302\273,,)
(\342\226\240=

Oneof

Example; Batteries.

it

not

-f

constanl

on

depend

B6}
of the

concentration

the

puctielcs.

vivid examples of chemicalpotentials

and
potential
hi the familial lead-acidbattery
the negative
electrode
consists of metallic lead, Pb, and the positive electrode is a layer of reddish-brownlead
ari: ininwisiid
in
ditulod
on a Pb substrate. The
eltclroiics
sutfurie
oxide.
acid,
PbOj,
which
ions
is
into
H*
ions
and
ionUai
H.SCU,
SG4~~
(Figure 5.7}.
(protons)
partially
steps

in

of

electrochemical

the

the

both

process

discharge

the positive

most

the

battery,

electrode arc

Pb +

Because of B7a)the negative

chemical potential ji(S04\"\"\")
inside

than

two

the

the

PbO.

reactions;'

SO4\"\" -+ PbSO.,+

2e~;

B7a)

electrical currents
If the battery
electrode

the electrolyte

(sec Figure

5.7b).

B7b)

2H2O.

\"

acts as a sink
the sulfafe ions at

electrode
of

PbSO4

for

SO*~

the

surface

ions,

the internal

keeping

of the negative
because of B7b) the

Similarly,

electrode
positive

chemical
ions, keeping the internal
potential
/((H1\") of 'tie
ions lower at the surface of ihe positive electrodethan inside the electrolyte. The
the
tons towards
the electrodes, and they drive the
potential gradients drive

acts as

hydrogen
chemical

and

exactly the

sink

for

the

during

potential

correct

H+

in

not

the

net

electrode,

negative

are depleted

from

thereby charging both.

the

positive

As

a result,

the
interfaces,
electrode-electrolyte
steps of
to stop
to equalize the chemical potential steps and
the
If an external
the chemical reactions from proceeding further.

steps develop at

magnitude

given are

electrons

connected,

diffusion of ions, which

stops
current is permitted to flow,
the
is
of
because
electrolyte
negligible,
reactions

process.

discharge

terminals arc

accumulate

electrochennca!

The

PbSO4, via

+ HjSO- + 2e\"-+

+ 2H+

PbO2

\342\200\242

electrode and

of the negative
sulfate,

electrode:

Positive

electrode

Ie;td

to

electrode:

Negative

lower

Pb

metallic

tlie

converted

reactions.

resume.

reactions
a negligible

The

Electron fiow directly

concentration in

electron

actual reaction steps

through
the

electrolyte.

are more complicated.

the

clcclrodc
(\342\226\240f)

PbO,

l>b

T
(b).

5.7

5-igurc

parlialiy
two

(ajThekjJ-aciJ
ioni/cd

ions

U^SOj.

plus one

PbSO4 + 2HjO,Lii
before the

and

H*

and

ihe chemical

barrier.

bailcry coniists of a Pb anj a PbO2

One SOI\" ion coii\\crfs one Pb atom

im-ionizcd HjSO^ molecule

isiirning

Iwo

ciccirons.

development ofimcfiia!

one

convert

(b) The
poltnltai

reaction, (c) The eicctroiuticpoieuliai

cicctrotic
into

PbSOt

PbOj

ilnmclsed

moltrcul^ imo

eiectrociiemicaipokntials for
barriers
y(.\\)

thai
after

in

+ 2e~;

slop the dilTuston

the formation

\"

SOI

of the

and

Potential

Chemical

Entropy

take place, because now an

process the reactions opposile lo B7a,b)
Eliai generates elect rostalk [wicin
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,
Iwik-u
the diction
ami
of ion How,
U'c denote
of the negative and
by A K_ and A f. the difTcrenccsin dectcostaitc
polcmial

During

I he

charging

cMornai voiUigc

is ;i}>[i!ied

posilncclcclrodcsrelative

to

negative charges,diffusion

will

2gAK_

of

H+ ions wi!i

the

stop

two polemics
forces);

(electromotive

ions

curry

two

BSaJ

A/i(SO4\"\.")

\302\253

B8b)

A/i(//').

are called

Al'+

and

AK_

suifute

when

+ ^AK+

The

the

when

slop

\342\200\224

DifTusion

ciectroiyie. Because

ihc common

ha!f-cc!i potentials or

half-eeil

EMF's

their magnitudes are known:

AV_

Aft

-0.4voll;

electroslalic polcnliai difference

as required to stop the diffusion
reaclion.

Tiic lolai

AK =

AK+

developed

\302\273

+1.6volt.

across

one

full

cell

of

ihc bniicry,

is
-

AK_

\302\253
2.0voli.

B9)

the nccaIl drives ihc electrons from

opcn-drcuitioitage of EMFof the battery.
lo the positiveicnr.ma!,when ihc iwo are connected.
in tha electroljle.
We have ignored free electrons
The polenlial steps tend to drive
electrons from the negative elecirodesinto the electrolyte,
and from the cleciroiyie into ihe
is so small as to be
the
Such
an
current
is
but
electrode.
electron
magnitude
present,
posilive
is many
the
the
concentration
elcclrons
in
because
of
electrolyte
practically
negligible,
is
ions.
The only effective electron (low path
less
than lhal of the
orders of magnitude
ihe
electrodes.
the
external
connection
between
through

This is ihc

live lenninal

Chemical

Potential

and Entropy

of
we defined the chemicalpotentialas a dertvathe
an alternate
relation, needed later:
energy. Here we detivc

In E)

the

Hclmlioltz

free

C0)
This expressesihe raliopi/x
1/r

was

defined

in Chapier

as

2.

a derivative

of ihe

entropy, similar to tlte way

Clmpler5; Chemical
To derive

U, V,

C0), considerthe entropy

N.

and

Cibbs Distribution

and

Potential

a [unction

as

of the

independent variables

differential

The

cU

<w

C1)

differential
change ofthe entropy Tor arbitrary,
independent
=
and
rfJV.
Let
dV
0
consideration.
for
the
under
</t/,
t/K,
changes
processes
Further,select the ratios of rf<r, c!U, and i/N in such a way that the overall
values
these interdependent
temperature
change dx will be zero. IT we denote
otda, dV, and dN by {&a)t, FU)t and (<5N)rl then dx = 0 when
gives

After

the differential

division

by {5N)r,

C2)

The ralio {Sa)J(SN)lis (fo/5N),,and

volunie. With

the

definition

original

is (dU/dN),,

D[/),/(JW),

of 1/t,

all at

conslant

we have

C3)

dNj,,
This expresses derivative

at

By

the

original

of the

definition

\023
and on

comparison with

oTderivatives at constantt

U in terms

constant

chemical potential,
C4)

[H,

w.,
we

C3)

obtain

C5)

The two expressionsE)

same

quantity

ft. The

and

difference

C5)

represent

between

two

ways to express the

the following.In E), F is a

different

them is

Table 5.1

of liic cm

partial derivatives

a, U, and F

F, witii

energy

relations

of

Summary

expressing
cr, liic

ropy

as

given

am! Entropy

Potential

Chemical

ti-.c temperature

free

U, and liic

energy

of their

functions

itatur.il

variables

independent

o(U.V,N)

, is independent

(IU\\

variable

\\ia)rtl

y,,

function of

of

function

C5)

its natural independent

variables
the

variables.

same

yields n as a function of

and C5), but expressedin

is to

a third

find

we

In C1)

U,

terms

x,

N.

V,

The

assumed a =

quantity

fi

is

that n appears as
that

so

a(U,V,N),

the

in both

same

The object

variables.

of different

N, so

V, and

E)

of Problem1i

for p:

relation

C6)

and in

derive

10 we

Chapter

compilesexpressions

Tor

have their

i,

a relation for p asa function

p, and
^ as derivatives

of

t, p,

and N.

of o, U, and

F.

Table 5.1
forms

All

uses.
identity.

Tlicvmodynamic
dynamic

identity

particles

is allowed

given

We

can

in C.34a)

lo change. As

generalize

lo include
in

the statement

of the Ihermo-

systems in which the

number

of

C1),

C7)

By use

C0)

for

of the definition B.26)of i/r, the

fi/i, we write da as .

da =

dU/x

relation

pdV/x

C.32)

- pdN/x.

for p/r,

and the

relation

C8)

This

Potential and Gibbs

Chemical

5:

Chapter

lo give

be rearranged

may

Distribution

dV = xJs

statement of the

broader

is a

which

to developin

;u|jv

C9)

we were

than

identity

ihermodynamic

able

3.

Chapter

GIBBS SUM

AND

FACTOR

GIBBS

pdV

The Boltzmannfactor,

in

derived

3, allows

Chapter

us lo

probability that a system will be in a state of energy Et (o the

ii\\ thermal
system will he in a state of energy t2, for a system

of the

ratio

the

give

the

probability

with

contact

reservoir at temperature t:

P(z2)

is

This

contact

of the BoHxmann
of that

much

argument retraces

a very

We consider

presented

large body

number N0.The

is

body

&, in thermal and diffusive

the system

particles and energy.Thecontact

.

potentialof

the

system

iV

the

reservoir

particles,

are

has Nu
C/o

Chapter

that

to those

energy

(Figure

e.

Uo and

diffusive

constant particle

obtain

<R and

reservoir

large

may exchange
and the chemical

5-8), They

the temperature

oftiie reservoir.When

- M particles; when

\342\200\224
To

factor

Gibbs
and

thermal

3.

parts, the very

contact
assures

equal

the reservoir has energy

in

of two

composed

system

in

j and chemical potential p. The arguconstant

with

The

mechanics.

lo a

factor

at temperature

reservoir

with

known resuh of statistical

the best

perhajtls

is thegenecauzauon

ihe

the

system

the statistical

system

lias

energy

has

e,

properties of the

+
on identical copies of the system
accessible
slate of the combination. What
reservoir,
copy
quantum
will be round to conis the
in
a
that
ihc
observation
given
system
probability
N particles
contain
and to be in a stale s of energy \302\243j?
number of panicles.
stale
s is a state of a system
The
some
having
specified
The energye](iV) is the energy of the state s of the A'-particIc
sometimes
system;
When can we wriie ihe energy of a
we write only e,, if ihe meaning
is clear.
A' particles
ihe energy
of one pur tide
in
an
orbital
as -V times
system
having

system,

make

we

observations

one

in
ihat

orbital'.'

the
the

particles

Tor

Only
may

as before

each

so
interactions between Ihe particles are neglected,
be treated as independentofeachother.

when

iit thermal
and diffusive conlacl wiill
of energy anti of panicles.
Tile total system
S is tnsulaicd from the external world, so thai
<H +
ihe
total energy and the total number of particlesare consianl.
The
ofihc
icmperamre
syslcm is equal to tile lempcrature
and
is
oflhc
i lie chemical
reservoir,
potential of the sysiem
to
the chemical potential of Ihe reservoir.
The syslcm
equal
may bs as small as one atom or it may be macroscopic, bui
ihe reservoiris always
lhan
to be thought
of as much
larger
lite system-

A system

Figure

5.8

a large

reservoir

is in
and
the probability the system has
particles
of accessible
to number
a particular stale s. This probabilityis proportional
is exactly
stales of the reservoir when the stateof
specified. That
sysiem

Let P[NtEs}denote

jY

that

the

the

of \302\243,
the
state
the
number
is, ir we specify
the number of accessibleslatesofO?:

\302\273((H+

The factor ! reminds

stale,

The

y(<Jl)

us

stales

the
Uo - e,. Because

stalesof
of accessible

of

that

the

system
the

S)

gift)

P{N,i:J

in

is proportional

reservoir.

NtU0

is just

{41)

looking at ilic sysiem S

reservoir
have No - N particles

(H

x 1.

we are

probability

of

states

oraccessible

zt).

a single

and

spiciixd

Ikivc

energy

to Ihe number

Potential and Gibbs Diitrihufit

5: Chemical

Chapter

fit
Particles

i\\'o

Energy

UQ

Panicles

,V,
\342\200\224

Ft

Enemy

Uo

Energy

Panicles

,VU

Particles

A\\

Energy ,

r,

(b)

(a)

dirTusive

and

to

it. In

stales
number

{b] the

system

is in

quantum state

2, and

with the

contact

the

system. In (a) tile

has g{N0

reservoir

- A'j,

of

Uo

to it. Because we have specifiedthe exact state of the system, the

ofsiulcs accessible tool
states accessible 10 01 + i k just
the number

accessible

Here g refers to the rcsetvoiraloneand

in
and on the energy of the
reservoir
the
We can express D2) as a ratio of two

state 1 and the

lhat

other

the

number

one

that

\302\243;

of particles

reservoir.
probabilities,

is in state

the system

on

depends

total

the system

is in

2:

g(N0 --JV,,[/0 -

e,)

D3)

where

g refers

to the

By definition of the

state of the reservoir.

The

in Figure

5.9.

entropy

s(N0,y0)

so that the

is shown

situation

probability ratio hi

D3)

ejpOfNo.f,,)]

may

be written

D4)

as

D5)

>ffel)

\"
eXp[\"(N\302\253

N\"y\302\260

D6)

Act is the

Here,

eniropy difference:

Ac h a(N0 ~
The reservoir is very

NUUO

approximated

and

\302\243
that

N2,U0

D7)

e2).

system, and Ac may be

tn a series expansion in

lerms

order

firsl

to the

relate

with the

in comparison

large

quite accurately by the

the [wo quantities N

- a[N0

e,)

system. The

entropy of the reservoir

becomes

N,U0

For A<?

defined

~i)

by D7)

D8)
we have,

to the

first

in

order

iVE

\342\200\224

N2

in e,

und

\342\200\224

c->t

E0a)

original defmilion of the temperature. This is written

the system will have the same temperature.
Also,

by our
bin

for

the

reservoir,

(?e'

E0b)

by C0).

The entropy difference

D9)

is

(N,

Here

Aa

refers

to the

- Nt)n

(t, -

reservoir, but Nit A'^, \302\243lt

t]

result of statistical mechanicsis found

on

refer

combining

E1)
system. The
and E1):

to the
D6)

central

E2)

5;

Chapter

and Gibbs Distribution

Potential

Chemical

ratio of two exponential factors, c;ichof the

form
A
term
of
this
is
The
Gibbs
factor
form
calleda
Gibbsfuctor.
cxp[(A'/j
e)/t],
is proportional
to the probability
is in a state
5 of energy e,
that the system
and
number
of particles
YV.
N. The result was first
who
J.
Gibbs,
by
given
referred
to it as the grand canonical
distribution.

The

the

is

probability

The sum of Gibbs factors,taken

of particles,is
normalizing
absoluteprobabilities:

that

facior

the

of the

states

overall

converts

.
This is called the Gibbs sum, or the grand
sum,
The sum is to be carried out over all states

particles:

the

of

exp[(A'/i

or the

ASN.

abbreviation

the

defines

this

system for al! numbers

relative probabilities to

grand pan

it

for all

system

E3}

E],VJ). r].

function.

ion

numbers of

written e, as eJ(:V,

We have

to

of part
icles .V. That is,
stale on the number
hamiitonian.
The
state
s(N) of ihe exact A'-particie
= 0 must be
N
term
included; if we assign its energy as zero, then ihe first
in ^ w'-' be 1.
term
The absoluteprobability
the
will be. found in a state Nlt e, is
that
system
Gibbs
facior divided by lite Gibbs sum:
by ihe
given

the

emphasize

of the

dependence

c,|.v,is ihe energy

of

the

E4}
chemical
temperaturet
result
our
cenlral
ratio of any two P's is consistent
ihe correct
factors.
relative probabilities
E2}
gives

This

applies

a system

lo

lhat is ai

and

E2} for

with

Thus

and

of

jV2,\302\2432.Thesum

of tlte

system

ihe

probabilities

of all

stales

for

al!

p.iiiictiljrl)-

lite Gibbs

stales

the

for

A',,

of par*

numbers

s,

icles

is unity:

f
by ihe

ji. The

poieinial

definition

IicIpM.

of 0-. Thus

The

nuriliod

E4)

us,cil

gives

there

the

correci

to ikme

iibsuime

the Potion

\342\226\240
155)

probability.*

dimibuiion

impends

on

6744s

and Gibbs

Factor

m diffusive
and thermal
contact
Average v;i!ucs over ihe sybiems
are easily found. If X{N,s) ts ilie value
ihe sysiem
of -V when
and
is
in
ihe
slate
then
ihe
thermal
particles
quantum
s,
average of .V
s
N and all
ts

Sum

with

lias N

reservoir

all

over

{56)

Number

the

of

The

particles,

is in diffusive

system

number of particlesin

ihe

contact

with

system

is

been multiplied
can beobtaftied

liie

by

from

of N.

definition

in ihe

term

each

because

average of the

thermal

The

reservoir.

value

appropriaie
the

in the system can vary

of panicles

number

To obtain tile numerator,

lo E6).

according

thermal averages.

to calculate

result

this

use

shiill

We

Gibbs sum

has

More convenient forms of <N>

of#

whence

<,V>

Tile
J

by

tiicrma!

number

average

use

direct

of E9).

will

We often

be

written

l-ll

we

E9)

= r^-1
is easily found from the

of particles

When no

thermal average <N>. Wlicn

for </>

confusion arises, we

speak

of the

later

for

interchangeably

,V

or

shall

write

Gibbs sum
jV for

the

occupancy of an orbital,

<.V>.

eniploy the handy notaiion

F0)
where

see from

is called

the absolute

A2) that for an

activity. Here /. is Ihe Greek letter

ideal gas ). is

directly

propcrliona!

to ihe

lambda.

We

concentration.

Chapter5: Chcutkul

and Gibbs

Potential

Distribution

The Gibbs sum is wriiien as

F1}
'

A5S

ensemble average numberof particlesE7)

and ihe

is

F2}

is useful, because in

This relaiior.
finding

many

actual

problems

<N> come out

will make

ihat

value

ihe

we determine

/. by

equal to the given number of

panicles.
thermal

The

Energy,

v -

of the

energy

average

^i

<E>

system is

F3)

where we ha\\elemporarilyintroducedthe notation /J

write

E9} and

so that

F3} may
-

Chapter 3

in

terms

Example:Occupancy
occupiedby
may

be

5.10).
A

zero

occupied
single

usually

be

lo give

combined

F5}

toi

more widely used in

partition function Z-

that is
of the

zero

molecules

by one
heme

We shall

;r-\302\253

expression

simpler

1/t.

that

Observe
<\302\243>.

for

or one.

A red-blooded

or by one

molecule is the

red colorof meal.Ife is ihe energy

in

the

of an

example of
heme

group,

syslcm

obtained

in

may be
be vacant or

ihat

which may

than one Oz molecule(Figure

which is responsible for the
myogiobin,
prolein
to Oa at rest at
adsorbed molecule of O2 relative

Oz molecule\342\200\224and

group occurs

was

calculations

never

by more

5.10

Figure

where c is

the Gibbs sum is

ihen

distance,

\302\243~

musl be added io remove

If energy

sum arises from

in ihe

Theseare itjc

only

occupancy zero; ihe

We have

possibiliiies.

from, tile heme,

atom

the

F6)

+;.cxp(-\302\243/r).

lerm

The term t
wilt be negative.
arises from single occupancy.
where Mb denoies
present,

Aexpf-c/i)

Mb 4- O2 or MbO2

17 000.
myoglobin.a protein of molecular
weighi
ihe conceniraiion
versus
of oxygen
occupancy
Experimental results for Ihe fractional
arc show a in Figure 5.t t. We compare ihe observed oxygen saturation curves ofmyoglobin
and
in Figure 5-12. Hemoglobin is ihe oxygen-carrying component
of blood,
hemoglobin
ti is made up of four molecular
wiih ihe single sirand of
identical
each slrand nearly
strands,
ihe classic
myogiobin,and each capable of binding a single oxygen molecule,
Hisiorically,
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
because ihe binding
of a single O, Io a moleculeof Hb is tower Ihan for
pressures,
energy
Mb. A! higher
lhat
is concave
of
ihe
Hb curve has a region
pressures
upwards,
oxygen
because trie binding
the
first
is
adsorbed.
increases
after
O2
energy
per Oj

The Oj
thai

molecules

chemical

the

on

are

hemes

by

the

exp(/i/i}.

in

potentials

the Oj

find

ihe

the

value

liquid, so

surrounding

and

in

solution:

= ?.{O2)

/(MbO2)

/i(O2);

From Chapter 3 we

in

ihe myoglobin

on

\302\273

of /

in

F7)
of the

icrnis

gas pressure

retalion
A =

We

with

equilibrium

are equal

of Oj

/i(MbO2)

where

assume

Oj

adsorbed

by

a hemc

O;

rctal

10 an Oi al infinite
from ihe site.
sepatuiion
If energy musi be supplied10detacri
llie O3
from ihe heme, then c will be negative.

infinite

of an

Adsorpiion

ihe energy of an

ihe ideal gas resuit

F3)

p/t\302\253Q.

sotulion.

conslant

At

temperature

/(Oj)

is

p.
O^

is found

Ac\302\273pl-t/i)
I

io C), in

applies

direclly proporiiomUto tjic pressure

Mb occupiedby
The fraction/of

n/nQ

/.exp(-\302\243/t)

from {66}to

be

1
'
r'exp(\302\243/t)+

Fg)

Figure 5.11 The

molecule with

reaction o( u

(Mb)

nvyoglobm

may

oxygen

(he adsorptionof a molecule

of
on ihe large mjoglobin
molecule.
results

Gj

at a

as

site

Tlie

isotherm

3 Langmujr

follow

be viewed

<{tiitc

molecule
can
accutaiely. Each myoglobin
adsorb one Oj molecule.These curves
show
(he fraction of myogtobin with
adsorbed
O.
as a function of ihe partial pressure of Oj.
are for human myoglobin in
The
curves
solution.
is found in niuidcs;
it is
Mvogiobin
for
the
color
of
slKtfc.
After
A.
responsible
Rosst-Fanellt
and E. Antoiiini.
Archives
of
and
Btoihciittsiry
Biophysics77, 47\302\253
(tySK).

Concentration

curves

Saturation

Fi\302\273ure5-12

lo nijoglobin

bound

of O.

and

iKmoglobtn
(Nib)
(J-ib)
in wmer. The partiat
molccuks in soluiion
pressure of 0. is plotted as the Iiorizonl;i!
Tiie

;t\\is.

the

vertical

molecules

a.\\is gives

of Mb

0, mokcuk, or the

which

ihe fraction of
lus

one

bound

suarnis of
lib which have one bouiid Qt innlcutle.
h;is a much Uirgcr change in
Hunioglabm
cotitem
in ihe pressure range bensecu
oxygen
ttw
nuerks
and the veins. Ihis circumstance
facilitates
ihe aciion
of ihe heart, viewed as :i
The

pump.

curve

for myoglobin

pioitual lonn (or the

The

MbO..

of the

ft action

curve for

reaction

has the
Mb

lienio^lobin

+ O2
Itits

\342\200\224\342\200\242

;t

forrn because of ifsicracironsbenveen

molecules
bound to ilic four si rands of ihe
niolccule.The dr^Atntjis
after J. S. Fruton

uiiiCicm
O,

lib
and

S. Siminondi,

1961.

Gvm-J

bioJtaniMry.

Wiley,

of O3,

rcbt

as

[he same

is

which

subsiiiute F8)

in

the

with

in

7. We

Chapter

to obtain

F9|

} 4- I

or.

derived

function

distribution

Fcrmi-Dirac

Gtbbs Sut.

and

Factor

G'tbbi

G0}

\302\273iurexp(E/r}

\302\256
jiqtcxp(\302\243/i).

p0

'
+P

Po

whac

G1}

is

!>0

wiih respect

is constant

easts on the surfacesof

Example;Impurity

oikn

ionizatian

in a

as impurities

in

the atoms exchange

Lei / be the

bound

is accessible.Therefore
one

an

with

When

the

with

to

large

and

electrons

ionizalion

can be

electron

semiconductor.

of the impurity
energy
an impurity
atom;

the

system

fanned

with lite

& has

by

the

attached

as this stale; the

stales of \342\226\240$
are summarized

the electron

rest

semiconductor.
We suppose

atom.

that one, but only one.

i of the electron spin

either orientation t or
three allowed states\342\200\224one

with

ionizalion

by

band

systems S in thermal
of the semiconductor:

small

are

atoms

reservoir

energy

electron

conduction

the

In

chemical

numerous

may iose an

crystal-

with

has zero

Suite

result

the adsorptioiiof

without

attached

spin
f, and one
atom is ionized. We choose tiic
electrons, the impurity
other two stales thereforefiave ihc common
energy c =

electron

The

temperature.

of

Atoms

a semiconductor

the semiconductor

of

diffusive equilibrium

and

the

to dcicribc

used

when

as an idea! gas. The impurity

be treated

on

but depends

solids.

atom

elements when present

to the conduction band
may

to prcsfi re,

Langmuir adsorption is ndtrm

as the

known

an

electron

zero

an

electron,

with spin
ofenergy

\342\200\224
/. The

].

of &

accessible

below.

number

Description

Electron

detached

Electron alladicd, s

1-kcifoti ijjnjLlicJ.
The

Gibbs

sum is given

by

G2)

The

tliat

probability

&

is ionized

tliat

probability

0) is

\302\253

P(ioaized)

The

\302\273

((V

P(O.O)

$ is

neutral

is just

\342\200\224.

G3)

is

(im-ionized)

= /'(It,-/)

P(neutral)
which

-\342\200\224-1-

\342\200\224
=

+ P(U,~/) ,

G4)

- PtO.O).

SUMMARY

1. The chemicalpotential
found from

/*

equilibrium

if jtx

is

{cUJcN)a

\342\200\224

i{cojvN}v_v.

parts, external ittid

in an external
particle

of two
of

The internal part is ofthermalorigin;

Tlog(u/iiy),where is the concentration
it

3.

The

Gibbs

have

and

^{Mi'lnh2)*'2

nQ

at chemical

a system

that

N particles

and be

state

a quantum

in

sum

5.

taken

over

The absolute

6. The

The

field of force.

gas ;t(int)
is the quan-

potential ;i and temperaturei

s of energy ts.

4, TheGibbs

is

mooaiomic

internal.

factor

gives the probability

will

ideal

an

for

concentration.

bo

also
difl'usive

= }tz.

2. Tl^c chemicaipotentialis made

up
external
part is the potential energy

quantum

= {tF/tN). v and may

Two systems are in

as h{t,V,N)

defined

\342\200\224

for all numbers

all states

activity

is

thermal averagenumber

defined
of

of

by

particles

<A')J

particles.

expQi/r).
is

kg

\302\243

PROBLEMS

1.

velocity

angular

j[(r) on the
for

as

an expression

i. Find

temperature

A circular cylinder of radius

to. The cylinder contains an

Centrifuge.

radialdisiance

<\342\226\240
from

an ideal

for

the

axis

the ions

about

rotaies

ideal gas of atomsof niass

lhe

dependence

axis,

in terms

with

SI

al

the concentraiion
of *i\302\2430)on the axis. Take
of

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
at lhe surface, show that
acceleration
at constant
tlic total number
temperature
of molecules in the atmosphereis
=

wifh

r iiuMstirtiJ

The

integral

ttf (he

diverges

aimosphere cannoi be in
are always escapingfrom
3.

I'ntuiitiul

each of mass

at

tipjwr

flic

limit, so

ihe

R is

here

l-yrih;

the railing of

ihe liarili.
and the

be bounded

cannot

that

Molecules,

equilibrium.

em-i'ity of gas

of

ihc center

from

f75)

</rrJcxp(A/yKV<'0

4nn(K)Cxp(-A/yR/t).Jjti

light molecules,

particularly

atmosphere.
fa

t in

temperature

a uniform

of moms

a column

Consider

Jield.

gravitational

gravitational

field

average
average potential energy per atom.Thethermal
is
of
Find
the
total
heat
density
height.
capacity
independent
total heat capacityis the sum of contributions
from the kinetic
the potential
energy. Take the zero of the gravitational
energy
~ 0 of the column.
= 0 to h ~ oo.
h
h
from
Integrate

thermal

the

Find

y.

kinetic

energy

per atom. The

energy and
at lhe

from

bouom

transport. The concentrationof potassiumK+ ions in lhe internal

of !04
of
a
a fresh water alga) may exceed by a factor
sap
plant cell(for example,
the concentration of K+ ions in the pond water in which the cell is growing.
The
chemical
of the K* tons is higher in the sap because their conpotential
at
concentration
it is higher
there. Estimate the difference in chemicalpotential
300 K. and show that it is equivalent
ihe cell wall.
to a voltage of 0.24V across
are
Take ;i as for an ideal gas. Because the values of the chemicalpoiemials
The
ihe
ions
in
the
cell
in
are
not
in
diffusive
and
the
different,
equilibrium.
pond
to the passive
impermeable
leakage of ions
plant cell membrane is highly
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?
4. Active

5.
drawn.

If

= 300K,

particles contain to

shown?

Determine

concentration.

Afaguctic

how many
give

.\"-\342\226\240..\342\226\240

magnetic

the

ratio

m/x for

Bohr magnetonsfiB
concentration

effect

which Figure5.6is
the

eh/Zinc

ivould

of the

magnitude

whh

unoccupied

that
system, (a) Considera system
one
in
either
by
particle

a two level

sum for

Gibbs

6,

energy

one of energy zeroand oneofenergy

= i +

3-

time.

in the

c include

ttuitn

Notice

excludes the possibility

Our assumption

that

s. Show

the Gibbs

be un-

may

or occupied

zero

of two

sum for

ihis

states,

G6)

;.exp(-E/r).
of

one

is

system

state at

in each

particle

sum a term forN

\302\253=
Oasa

particular

system of a variable numberof particles,

Show
that
the thermal
(b)
average occupancy of the system

the same
state

of a

is

G7)

(c)

Show that

(d)

Find

an

(e) Allow
one

3.

particle
=

for the

expression

thermal average energy

the possibility that the orbitalat

at the same time; show that

I +

1 +

average occupancy of the state at energye is

the thermal

Aexp(-\302\243/i)

Because ^- can befactored

as

uitd
7, Statesof
negative
diogen atoms;suppose each
tliat

atom

can

Stale

Number

of

-JA

-if)

ion

conUiiion that the

will

involve

5,).,

and

replaces

the

O2

lu
luihuning.
ad^oibed
on hanoglohin

tl-.e clTect, consider a model for which

vacant
or may be occupied either with
energy

eh

by one molecule

CO. Let

J3

U
of

per mom

electrons

be unity.

r.

mtmoxitle

Cmtitm

number

Livci;t^^

hy-

Energy

Posiiivc ion

The condition
X.

electrons

E\\cii<.-d

FioU rlic

a lattice of fixed
exist in four states:

Ground

Negative

G9)

+ Aexp(-e/i)].

/.)[!

Consider

iotuzation.

posttiw

each by

in effect two independent systems.

we have

shown,

system.

be occupied

ate may

0 and

A2exp(-\302\253/t>-\302\253

the

of

A'

catbon monoxide
(lib) mulcculcs in
each
energy
fixed

adsorption
ea
home

poisoning the CO
ilic

Wuoil.

To hhnw

a heme may
one molecule O2 or

by
sites

site on

be in equilibrium

be
with
with

Froblcn

CO in the gas phases at concentrations such

that
the
are
activities
=
1
x
SO\025
and
1 x 10\021,
all
at body
3TC.
X(OZ)
X(CO)
tempcraiure
factors,
the system t\" the absence
Neglect any spin muhiplicity
(a) First consider
of CO. Evaluate \302\243A
such
that
90 percent
of the Hb sites are occupiedby O2.
the
answer
in
eV
Now
admit the CO under the specified
Express
per O2. (b)
conditions.
Find Sgsuch that only 10 percent of the Hbsitesare occupied
by O2.
and

O2

field.
Suppose that at most one O2 can be
Problem
and
that when /.{O2)~ iO\025 we have
8),
group (see
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
T = 300 K.? (The Gibbssumin the limit of zero
the
adsorption
by 1 percental
field
will
differ
from
that
muhiof Problem 8 because there the spin
magnetic
the
was
of
bound
slate
neglected.)
muhiplicity

9. Adsorption
to

bound

ofO2

in

a magnetic

a heme

10. Concentration
fluctuations.
contact

in diffusive

system

We have

a reservoir.

with

is not

of particles

number

The

constant

in

seen that

\342\200\242

re:

<,v>
from E9).

(a) Show lhat

(81)

<lY!>=LLi.

3- ^

The

deviation

mean-square

= <(N

<(ANJ>

(b) Show

<.V\302\2732>

that this may

be

of N from

((AWI)
=

is the
diffusive

fi

xvi:

;u>rly

iliis

n-iilt

</V!>

<,V>:;

= tc<,V>/c>

in llio

i.K'iil u:is to liiul

(83)
liial

square fractional fluctuation in the population

with a reservoir. If <A'> is of the order of
contact

mean

by

as

<(A.V)'>

In t'liaptcr

defined

is

- 2<N><N> + (N}'

(N>)

written

<iV>

of an
\\02Q

atoms,

idea! gas
then

in

ihe

Chapter 5:

ChemicalPotential

and

Distribution

Gibbs

fluctuation is exceedingly smalt. In

is
it cannot
panicles well defined even though

fractional

such
a system
be rigorously

contacr
wirh ihe reservoir. When
is allowed
is
<iV)
can be usedin the experimental
determination
of the molecular
103 - [O10;see M. Weissman,
molecules such as DNA
of
MW
andG.
Feher, Proc. Nat. Acad. Sci.73, 2776A976).

diffusive

11.

of chemical

definition

Equivalent

defined

E) as (cF/cN)tiy.

by

An

fi

ihat this relation, which

Prove

the definition {5}that

resultsC1)

and

C5).

have

we

potential moreoften

a function

as

Schindler,

was

5.1 is
(S5)

(cU/cN)ay.

to

Gtbbs

It will be convenient
for treating {5}as the definition
In

two-fold.

of the

to make use of the

and

of/i,

we need

practice,

to

ji, is equivalent

define

adopted.

consequence, are

a mathematical

in Table

listed

expression

was used by

reasons

Our

*=

H.

The chemical potential

potential*

equivalent

the number of
conslatil because
low, this relation
weight of large

temperature tihanasa

(85) as

the chemical
of

funciion

the

a particle
is added to a system
a process in which
entropy
a
while
the
is
constant
is
more natural
of
the
temperature
system
process
kept
one in which the entropy is kept constant;Adding
a particle
to a system at
shan
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
defmtiton
the
E) or F),
laboratory
process by which this can be done.Hcnee
in
which
the chemical
is
as
the
in
free
expressed
energy
per
change
potential
added particle under conditions of constant temperature,
is operationally
the
~
We point out that
will not give U
(85)
simpler.
/tN on integration,because
is a function
of N; compare with
H{N,c,V)
{9.13}.

a. Operationally,

12.

of sap in trees. Fitsd

iree under the assumption

Ascent

in a

uppermost
0.9. The
concentration
of

in air

are

leaves

maximum

the

lhal

the

containing

water may rise

of
water and Ihe
pool

to which

height
stand

rools

in a

waier vapor at a

relative humidity

is 25\"C.If the relative humidity

is r, the actual
concentraair
at
the
leavesis
where
n0 is the
vapor
uppermost
rii0,
in ihe saturated air lhal slands immediatelyaboveIhe poo!of

temperature

in the

water

concentration
water.

13.

(a) Show

expansion,

hentropic

as a function only of
show ihat xVin is constant in an

expressed

the

thai Ihe entropy of an

orbital

expansion

gas

(b) From

occupancies,

isentropic

idea!

of an

can

be

this result

idea! monatomic

gas.

14.
infinite

of

binding

Multiple

molecules.

Assume
distance.

. solution), (a) What

Oi.

is

the

molecule can bind four

O2
at
rest
relalive
to
Oaat
O2,

A hemoglobin

lhal e is the energy

the
Lei / denote
probability

bound

ofeach

absolute

activity

that one

exp(ji/T}

of

the

free Oi (in

and only one O2 is adsorbedon a

ts the

Sketch

moiecule?

hemoglobin

probabiiity

four

Uiui

the result qualitatively as a functionof/.,(b)

and
only four O2 arc adsorbed? Sketch this

What
result

also.

15.

chemical potential.

External

N atoms

of mass M

potentialat
value

of the

the

surface

in

volume
of

tola! chemical

Consider a

t.

temperature

with

chemical
the
(a) Prove carefully atid honestly that

V. Let

the earth,

at

system

potential for

}i[Q) denote the value of the

the

identical

system

when

translated

to altitude h is

p(h) =
where
applicable

g is

Mgh

the acceleration of gravity,

is this result different from
(b) Why
to the barometric equation of an isothermalatmosphere?

that

Chapter

Ideal Gas

DISTRIBUTION

BOSE-EINSTEIN

153

FUNCTION

DISTRIBUTION

FERMI-DIRAC

157

FUNCTION

CLASSICALLIMIT
Potential

Chemicai

Free

160
161

163

Energy

Pressure

16-\",

Energy

164

Entropy

165

Heat Capacity

165

Testsof
Example:Experimental
Chemtcai
Potential of Ideal Gas

Sackur-Tetrode

the

with

Example: Spin Entropy

Reversible

in

Isothermal

Zero

internal

167

Equation
Degrees

\342\226\240

Field

Magnetic

169

of Freedom

J70

17'i

Expansion

Reversible Expansion at ConstantEntropy

into a Vacuum
Sudden
Expansion

IT.t
i \025

SUMMARY

176

PROBLEMS

177

1. Derivative

of Fenni-DiracFunction

2.

of Filled

3.

Symmetry

177

and Vacant Orbilals

for

Function

Distribution

177

Double

Occupancy

Relativistic
Particles
4. Energy of Gasof Extreme
for
an
5. Integration of the Thcrmodynamic Identity
6. Entropy of Mining
7. Relation
of Pressure and Energy Densily
8. Time
for a Large Fluctuation
Gas
of Atoms
with Internal Degree of Freedom
<J,

10. Isentropic

Relations

11. Convcelive
\\2.

Ideal

Gas

of

Ideal

isentropic Equilibrium

iit Two

Piitu'itsiuns

13. Gibbs Sum for Ideal Gas

14. Idcai Gas Calculations
15.

Diesel

Engine

Compression

Gas
of

the

177

Statistics

Atmosphere

177
Ideal

Gas

177
17S
i

7S

17S
17')
179
J~0

1^'
1SU
ISO

ISO

Chapter 6: IdealGai

gas of noninteracting atomsin the limit of low concentration.

The limit is defined below in terms of the thermal average value of the number
ideal

The

is a

gas

of particleslh;it

distribution
the orbital.

function,

An
orbital
is a stale of [he
terns is widely usedparticularly

Schrodingcr equation for

by chemists.

are weak,Ihc orbitalmodel

allows
of the Schi'6'tlingcr equation of a

!fthc

one

only

to approximate
of A' particles
system

particle.

sin

exact

quantum

in

terms

of an

by assigning the

This

between particles

interactions

us

we construct

thai

state

approximate quantum

as /(ej./i),

designated

usually

average occupancy is calledthe

where t is ihc energy of

The thermal

orbital.

an

occupy

panicles

state

approxi-

lo

orbituls,

orbital a solution of a one-particleSchroOinger

equation.There are
an
infinite
of
number
orbitals
available
for
term
The
usually
occupancy.
\"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
if there
are no interactions between the particles.
only
with each

It is a fundamental result of quantum

of which
mechanics
derivation
(ihe
lead
us
into
would
thai
ail species of particles fail
two
distinct
astray
here)
fermions
with
is
and
bosons.
a
Fermion,
classes,
Any
particle
half-integrai
spin
with
There
are no intermeand any particle
zero or integral spin is it boson.
the
an
intermediate classes.
same
rule:
atomof Hie is
follow
Composite
particles

composed

an

of

each of spin j,
An

aloin

of 4He

odd

so

of

number

must

Hie

that

has one

particles\342\200\2242

have

2 protons,

electrons,

spin and

half-integral

more neutron, so ihcreare

an

even

I neutron-

must be a fermion.
number

of panicles

of spin |-, and 4Hemust

be a boson.
The fermion or boson nature of the particlespeciesthat
make
up a manyon
the states
of the system.
body system has a profound and important effect
as applied
to the orbital model of noninleracting
The resultsof quantum
theory
1.

as

appear

particles

An

can

orbital

be occupied

species,
An orbital

The second

rule

of

occupancies

of any

by any integral

number of bosons of the same

zero.

including

2.

rules:

occupancy

can be
is a

need

occupied by

statement

not be

0 or!

of the

fermion

same species.

of the

Pault exclusionprinciple.Thermalaverages

but
integral or half-integral,

individual system must conformto one or

the

the
other

orbital
rule.

occupancies

Distribution

Fa-mt-Dirac

The

different

two

rules give rise to two

stun over all integral

occupancy

there

each orbital:

boson

is

Function

sums

Gibbs

different

values of the

for

occu-

orbital

= 0 or N = !
N
fermion sum in which
Different
only.
Gibbs
sums
lead to different quantum distributionfunctions
for the
/{e.t./i)
thermal average occupancy. Ifconditions are such
\302\253
it
will
notmaitcr
that/
1,
whether the occupancies N = 2, 3,... are excluded
or are allowed.
Thus when
<:<
I
the
and
fermion
functions
must
be
similar.
Thislimit
boson
distribution
/
in which
the orbital
with
unity is c;ii!cd the
occupancy is small in comparison

there

and

A',

occupancy

is a

classical regime.
now

We

occupancy

treat

the Fcrmi-Dimc

of an

orbital by

the

fcrmtonsand

for the thermal average occupancyof an

equivalence of the
to treat

two

of famioit

particlesis

bosoti

and
absolutely

in the

functions

the properties of a

gas in

Bose-Einstein
orbital

opposite

thermal

the

for

average

function
distribution
bosotis.
We show the

occupancy, and

we

go

on

treat the properties

limit, where the nature of the
of the gas.

Chapter

the properties

for

by

limit of low

limil.-ln

this

in the

g;ises
cruchi

function

distribution

7 we

FERMI-DIRAC DISTRIBUTIONFUNCTION
We

a system

consider

fermion. The

single orbital that

of a

composed

be

may

occupied

by a

is placed
and diffusive contact with a reservoir,
in thermal
A
6.i
and
6.2.
real
Figures
system
may consist of a large numberNo of
call
it the system.
but it is very helpful to focuson one orbitaland
fcrmions,
Our
are
of
as
the
reservoir.
All
other
orbitalsofthe
real system
problem
thought
thus
out. An
is to find the thermal averageoccupancyof the orbital
singled
No
orbital can be occupiedby zero or by one fermion.
other occupancyis
be taken
will
allowed
Pault exclusion
by the
principle. The energy ofthe system
to be zero if the orbital
is occupied
The energy is c if the orbiial
is unoccupied.
one
fermion.
by
5 we have
The Gibbs sum now is simple: from (he definition in Chapter
system

as in

\302\243=

The term 1 comes from

the
= 0. The term -Uxp(-~-\302\243/r)
\302\243

so

that

of the

*= 1 and

1 +

configuration
comes

the energy

orbital is the ratio of the

(I)

;.exp(~f./r).

when

A' = 0 and energy

occupancy
the orbital is occupied by one fermion,
with

is e. The thermalaveragevalue
term

in

(he Gibbs

sum

with

of
N

the

occupancy

1 to

the entire

Gibbs sum:

B)

Ideal Gm

6:

Chapter

Occupied

,VQl

Figure

Wo)

6.1

fermion.
energy

log

G,,)
\302\243<*,\342\200\236

We consider
as the
The system is in thermal
of the occupied orbital

spin orientation and

considered as forming

confined to

unoccupiedand

JVD

We

be

might

the

Uu

if the

reservoir

ihe

will

contain

system is occupied

JVO
by

one

average oecupancythe

5 that

Chapter

write B) in

the

a! most

by

one

at temperature
of a definite
states
may be
if the

fcrmions

t. The

sysiem is

fermion.

conventional
an

symbol
orbital

that

/(e)

of energy

e:
C)

<.V(\302\253)>.

/. = cxp(/i/i), where

is the

chemical

potential.

form

standard

-,0/r]

\"exp[(\302\243

D)
1\"

as the Fenm-Dirac distributionfunction.*

D)
Equation
of energy e. The value
Ihe average number of fermions in a single orbital
is known

result

Tills

gives

O2

be occupied

may

thermal averagenumberof particlesin

from

We may

UJ _(|\302\243^-t(J^

encigy of a free electron

Other allowed quantum

fie) s
Recaii

*) = a{A'u.

kinetic

The reservoir

for the

introduce

I,

volume-

a fixed

fermions

denotes the

system a single otbhai that

and diflusixc contact v-uh

reservoir.

the
i

o(/V0

119261,

iicovcrcd.
general

and
The

itaicmenl

P. A.

M. Dirac, Proceedings

of

i!:c Royal

Sociciy of London AI12. 661[

ihe new quantum

meclianits
is concerned with
paper by Dirac
of lln: form assumed b>- iht P^ulj principle on ihis iheory.

a'ld

cont

Functlor

Distribution

Fertni-Dhac

System

Figure

6.2

shown

here.

(a) Tlic obvious method of viewing

The energy levels each refer to an

Sclirodinger

parliclc

equation. Ttic

loial

of noninicracling
a system
orbital
thai is a solution of
of

energy

panicles
a

single-

is

the sysiem

of panicles in the orbital n of energy \302\253\342\200\236.

For
fcrmtons
.V. = 0
ihan
treai
n
orbital
as
the
to
simpler
(a), and equally
valid,
single
The system in this scheme may
a of energytn. All other orbitals
be itic orbital
system.
is jVoca. whert
are viewed as ihe reservoir.
The
lotal energy of this
o\302\273e-orbital
system
is the number
one
orbital
as ihe
of panicles in the orbital,
This device of using
Nn
only weakly with each
system works becauseihe particles are supposedto interact
oiher. If we think of the fennion sysiem associated with the orbital n, these arc two
dsher
the system h;is 0 panicles and energy
0, or the system lias t pariki-possibilities:
the Gibbs sum consists of only
and enesgy \302\243\342\200\236,
{wo terms:
Thus,
where

JVB

or 1.(b)

is ihc

number

much

Ii is

3- ~ I
Tltc

firsi

from the orbital

arises

scrm

+ Acxp{~ejti
=

occupancy JVH

0, aad

the second

tcnti

arises

;Vq = 1.

from

function
distribution
lies between zero and one.The Fermi-Dirac
is plotted in Figure 6.3.
In the field of solid siaie physics the chemical potential <* is often called the
Th\302\243
on the temperature.
Fermi level. Tlie chemicalpotentialusually
depends
is often written as ef; ihai
of ft at zero temperature
is,
value

of/always

Mi

We call
*

En

ilie

cF

the

Fermi

semiconduUor

ihen called she

Fennt

energy,

liseraiure
level.

- 0) &
not

fi(Q)

to be

ihe symbol

cF

E)

Ef.

confused* uiih

is often

used for

the

;( a! any

Fermi

lempfniurt.-.

level

which

a:-d ef i

6; Ideal Gus

Chapter

\\

A'

\\
1

........

6.3

Figure

of the

Plot

Fermi-Dkac

r. Tlie value

the temperature

function

distribution

Fermi

higher

energy
energy

/t(t).
the

are

occupied

are

unoccupied.

chemicalpotential departs
If there is an orbilalof
orbital

is exactly

by

energy

half-filled,

in

electrons

Consider

ihe

in a

a system

- p in

of

unils

metal,

ji

might

of many independent

orbitals of energy below

exactly one fermion each, and ail orbitals
At nonzero temperatures the value of the
t =

temperature

from

/i

versus e

/(e)

the fraction

which are occupiedwhen

the system
is
heated from absolute zero, fcrmions
are
to the shaded region at c/ji > 1.Forconduction
lo 50 000 K.
correspond

!he
of

of orbitals at a given energy

tlfe system
in thermal equilibrium. When
is
from the shaded region at E/p <
transferred

gives

of/(c)

is !he temperaturedependent
orbiials, as in Figure6.4.At

\342\226\240~m.

-4 -3 -2 -1 0
e \342\200\224
of t
ji, in units

-5

_6

-7

Ihe Fermi
equal

to

sense

of

0, ali

energy, as we will see

the chemical
potential
a thermal average:

7.

in Chapter

(e

*=

//),

the

F)

Orbitalsof
are

lower

less than

energy

are

more

ihan half-filled,

and orbilals of higher

energy

half-filled.

We shall discussthe physical

of
consequences
in Chapter 7. Righi now we go on to discussthe

the

Fermi-Dirac

distribution

distribution

function

of non-

-I

Figure
think

6.-1
of

interacting bosons, and

in the

bosons

and

ihe ideal

establish

we

then

convenient

do

with

pictorial

gas law for boih fcrmions

FUNCTION

DISTRIBUTION

spin. The occupancyrule

of bosons, so lhat
for
bosons
can be occupiedby any number
is
an
bosons have essentially
different
than fermions.
Systems of bosons
quality
can have rather different physical properties than systems of fermions. Atoms
of 4Hc are bosons;atoms
of
3He
are fermions.
The remarkable superfluid
<
of
the
2.17
low
(T
K) phase ofliquid heliumcan be
properties
temperature
of a boson gas. There is a sudden increasein the
to the
attributed
properties
In
and
in
ihe
heat
this
temperaturefluidity
conductivity of liquid JHe below
to
2.17 K was found
of 4He below
experiments
viscosity
by Kapitza ihe flow
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
number
is
of elastic
waves
in solids) can be considered10be bosonswhose
is a

boson

not
of

an
We

of the
one

the

consider

all

it

is

as we

osciiiator,

thermal

as

but

conserved,

in

by

particle wtjh
thai an orbital

and

Figure

of the

of photons

to think

and phonons as excitations

did in Chapter 4.

distribution

contact

Let \302\243
denote

function
with
the

bosons
for a system of noninteracting
a reservoir. We assume the bosonsare
of a single orbital when occupied
energy

is N\302\253,
there arc N particles in ihe orbital,the energy
ireat one orbital as the system
and
view all other orbitals

when

6.5. We

value

integral

simpler

diffusive

same species.
particle;

an

way to

composed of independent
not interact with eutli oilier
3 common tcservoir.

limit.

appropriate

BOSE-EINSTEIN

iutecacl

a system

orbitalslliat
but

function

Distribution

Chapter 6: IdealGo:

as pan ofIhe
The Gibbs

reservoir.

sum

taken

for

the orbital

of particles may

number

arbitrary

Any

be in i : orbital

is

G)

The

tola! numberof paniclesin the combined

and reservoir. However, the reservoir may
be arbitrarily
large, so that
system
N may run from zero to infinity.
form.
The
series
G) may be summed in dosed
Let x s Aexp(~E/t);then
upper

limit

on

N should

be the

\342\200\224
A\"

provided

inequality;
Gibbs

(8)
;.cxp(-\302\243/t)

< 1. In

all applications,/,exp(\342\200\224e/i)will satisfy this

otherwise the number of bosonsin the system would not be bounded.

that

kcx.p{~t/z)

The thermal averageof !henumber

the

sum by use

of

in the

panicles

orbital is

found

from

ofE.62):

-(\342\226\240)/<]
L\342\204\242-___

__

A0)

Distribution

Bosc-\302\243insicin

Funclio

and
Fenni-Dirac
Comparison of Bose-Einsicin
for
funclions. Tlie classical regimeis aiiafoeii
\342\200\224
\302\273
where
ihe
two
distributions
become
(e
r,
/i)
nearly idciuit
We shall see in Ciiapier 7 that
in the degenerate
regime ai low

Figure 6.6
dislribuiion

chemical

ihe

temperature

potenijai

postnve, and changes 10 negative

ft

at

for

high

a FD

distribution

is

lemperaiure.

Et differs
Bosc-Efnstcindistribution
function,
malhcmaticaHy
tnsicad of + i
-1
from the Fermi-Dirac distribution function
having
only
by
can
have
in the denominator.Thechange
very significant
physical consequences,
7. The
as we shall sec in Chapter
two distribution
funclions are comparedin
the two distri6.6. The ideal gas represents the limit e \342\200\224
r in which
/i \302\273
Figure
distribution
are
The
choiceof ihe
functions
approximately
equal, as discussed below.
in any
e is always arbitrary. The particularchoicemade
zero
of ihe energy

This

defines the

wiU affect

problem

ihe

difference e

\342\200\224
has

is discussed

iuriher

in

the

classical

A gas
orbital

is

/;

in

is much

\\a\\uc

to be
B0)

less than

of

dieniic.il

the

independent

/i,

potential

buE

the

of ihe

vaU:e

of the choice of the zeroofe.This

point

below.

regime

when

the average

number of atomsin

one. The averageorbitaloccupancy

for

a gas

each

at room

temperature and atmosphericpressureisof the order of only 10\026, safely in the

classical
Differences
between fcrmions (half-integral spin) and bosons
regime.

6: Ideal

Chapter

and

Gas

Uau iuiu

liicq

reg

imcs

Class

of

parlic

Ic

Regime

___

T!Krma!

it

o CCup.iticy

i*:
ny

\342\200\224
\342\200\224\"~

III

Boson

Aluays

Fcfmioii

Close

10 bul

Boson

Orbital

of

Quantum

much

less

lhan one

less ihan one.

energy lias

lowesi

an occupancy much

greater than

one.

so
that
for occupancies of the order of one or more,
in the dassieai
is lhe
their
are
identical.
The
regime
quantum
regiir.e
equilibrium properties
These characteristic
features are summarized
opposite of the classical
regime.

arise

oniy

6.L

Table

in

LIMIT

CLASSICAL

as a systemof free nomuteracting

particlesin ttie classical
\"Free\" means confined in a box with no restrictions or e>uernaiforces

ideal

An

gas

regime.

acting

is defined

the

within

We develop

box.

the properties

of an idea! gas with

the

use

the ideal gas

powerful method of the Gibbssum.in Chapter3 we treated
use
the
the
of
buE
identical
by
partition function,
panicle problem encountered
there was resolved
clear.
by a method whose validity was not perfectly
The
Fermi-Dirac
and Bosc-Einstein distribution functions in the classical
limit
in an orbital
to the identical
iead
result for the average number of atoms
Write /(e) for the average occupancy of an orbital at energy
e ts the
e. Here
of
it is not the energy of a system
energy of an orbital occupiedby one particle;

of the

particles.

functions

where

The Fermi-Dirac

(FD) and Bosc-Einstcin(BE)

func-

distribution

are

lhe plus

sign is

for

the

FD

distribution.In orderthal/(c)
must have in

this

classical

be

distribution
much

smaller

and
th;m

the minus sign for the BE

unity for ail orbitals, we

regime

exp[(e-//)/r]\302\273l.,-

A2)

of ail

of (tt).

orhiiat of energy r.

/. hs

wiih

is satisfied we may neglect

Then for either fermionsor bosons,the

this inequality

e. When

all

for

denominator

exp(/j/r).

function. !t is
functions when

the

always

be a

occupancy

average

/(i.)

The

limiting

cxp[{/i

result

the

of

A3)

Fcrmi-Dirac
/(s)

occupancy

average

dfstnbulion
and Bosc-Einstein distribution
the classical

is called

is very

small

in

with

comparison

although called classical,is still a result

mechanics: we shall find that the expression
the quantum constant /i.'Any theory which,
contains

Equation
A3),
unity.
described
by quantum
involves

the

in

is

limit

the

+!

term

the

for

particles

for

or

/.i

h cannot

classical theory.

thermal

entropy,

ideal gas. There aremany

= Aexp(-r/i) to
of

topics

study

classical
of

the

the

importance:

chemical potential, heat capacity,

the
prcssure-volumc-temperaiure
distribution of atomic velocities.To obtain
results
from
distribution function, we need first to find the chemical potential
ihc concentration
of atoms.
and the

relation,

terms

of the

properties

function /(r)

distribution

classical

the

use

We

the
in

Chemical Potential

The chemical
of total number

is

potential

of atoms

the

that the

the condition

from

found

equals the

number of atomsknown

be the sum over all orbitalsof the

This number must

distribution

thermal average
to

be

present.

function/(eJ:

N =

A4)

start with a monatornic gas

where s is the indexof an orbitalof energy
es. We
N
we
include
atoms
of
identical
of zero spin, and later
spin and molecular
of atoms is the sum of the averagenumber
The
number
mocksofmotion.
total

of atoms

in

each

orbital.

We useA3)

rn

A4)

to obtain

AS)

JV-/yexp(-\302\243,/T).

To evaluate
is

just

the

this

partition

sum,

observe

function

that

the summation

Zx for a

single

free

over free particle orbitals

atom

in

volume

V, whence

Chapter 6: Idea!Gils
In

shown that Zt

3 it was

Chapter

where

HqV,

nQ

rs the

(Mrjlnh2K11

quantum concentration.Thus
A'

;.Z,

number

of the

terms

in

density

is

n;nQ

\302\253I.

out to

A7)
j

volume
quantum
of the ideal
potential

=\302\273
T

l/nQ. in the

monatomic

(IS)

tog(n/iiQ)

result

The

may

he written

give

i[)ogN

see

as

log

(IS) for

atoms

\\\\;i\\e

spin

spin ;:iuliipiidiy^S
is JoublcJ; nQ will
an

added

lo sevcra!

be subject

can

examples.

h3\\c

as the concentrationincreasesand

(lie chemica!polentiaf

If the zero of ihe energy scale is shifted

by
energy of an orbila! falls ill e0 = A instead

wifl

A9)

the temperature

Comment: The simple expression

modifications.We mention
four

(b) If lite

+ *SogBn/i2/A-/)]-

Jiogt

potential increases
increases.

the chemical

that

decreases

(a)

A6)

the

chemical

The

i?/hq

obtained in another way.

wiih E.12a)

\302\253

We

nftiQ

in

atoms

P
in agreement

exp(/i/T)

of

W/i?QK

Finally,

NJV.

\302\253=

number

to the

is equal

classicalregime
gas is

which

;. =

/.,,QK;

S, the

=.

an energy
of at

\\

ferm -rlog2.

(he

zero

of the

in ihe

sum in(iS)
and

by

Tile tfTctt

kinetic

B0)

il isdiJublcdLlhevalucof

t\\eryw[icre

be replaced

that

+ Tlog(n/nQ).

number of orbiiafs

4- I. For s.pin

A so

e0 = 0, then

2\302\273G,

of

Shi: spin

Ihe

i\302\273
mufliplicd

iheparlition
nght-hand

by ihe

fund ion Z^
side of{18)

on She enSropy is

Srcalcd

below.
fc)

the &3s is not fTiOnatonuc,

moiion wifl
vibraiional
If

t^e
enter

ihe

iiitern^J

partition

sS^ies associated with

function, and tfic chemical

energy

ro^itionaj

potential

-ind

wilt

free

Energy

- t log Zjni, per D8) below, where 2ial is the

of
partition function
the internal degrees of freedomof one molecule.
K the gas is nonideal, the resuK
for /t may be considerably more complicated;sec
10
tk
for
to j g;is of interChapter
relatively simple van der Waals approximation

have

Free

an added

term

Energy

chemical

The

is related to

potential

free

the

= n ,

(CF/dhr)t_y

according to Chapter 5. From

F{N,t,V)

where
so

the integrand

by

energy

B1)

this,

is found

B2)
\342\200\242\342\226\240\342\226\240],

Mow Jt/.vlog.v

in A9).

brackets

in

[log <V

tJ^N

j*JN}j{N,t,V}

= xlog x

\342\200\224

x,

[hat

- iVi[logW -

Tile free energy increaseswith

Comment:
Thus, from

The

integral

Wr[iog(n/nQ)

concentration

should

in B2)

- Jlogr + JlogBn/iVA')]

fog V

be

strictly

C3)

B-t)

1].

and

decreases

a sum,

because

with

A'

is a

temperature.

discrete

variable.

E.6),

f(N,r,l')

which differs from Ihe

integral

f. log.V

only

in ihc

= Iog(l x 2

lenn

in

log

B5)

Ji(-V)

,V in

A9), for

= iog/V!

\342\226\240
\342\226\240\342\226\240

N)

B6)

ChapM6:UtaICai
the

wHcfg

A1
\302\2433\\e

inic^EiiI

\342\200\224
_V in

log A'

B3).

log,V! ~
may be

used, and now B5) is ihc

Bui for

MogN -

she Stifling

targe

approximation

B7)

as B3).

same

Pressure

The pressure

is relatedto the

With B3)

F we

for

free

by C.49):

energy

ha

Nt/V;

which

is the

pV

idea! gas law, as derived

in

Chapter

Nz

B9)

3.

Energy

energy U is found

The thermal

U-F

With B3)

for F

we

ta-F~

from

U ~

t(cFi<\"t)|.,\302\273

-t:

C0)

'

CD

have

2t

so that for

or

iff,

an ideal gas

C2)
The

factor

| arises

from

the

exponent

of x

in

because

\302\253Q

the

gas

is in three

or two dimensions, the factor would be of 1,

The average kinetic energy of translational motionin the classical
respectively.
of freedom of an atom.
limit Is equal to ^c or %kBT
translaiional
degree
per
The principleofequipartitionofenergy
of freedom was discussed
degrees
among

dimensions;

if

in Chapter 3.

iiq

were

in one

Heat

has rotational

molecule

polyatomic

and
degrees of freedom,

the

Capacity

average

relational degree of freedomis%r when ihe lemperature

is high
in comparison
with the energy differencesbelwcenlhe roialiorta!
|e\\els
energy
of ihe molecule.
The rolaliona! energy is kinetic.A linear
molecule
has two
molecule
has
degrees of rolationa! freedom which can be exciled;a nonlinear
tliree degrees of rotalional freedom.
of each

energy

Enlropy

The

is related

enlropy

to the free

From B3)

for

This is idenlica!
lhiil

so

\\o^n0/n)

for the

equation

C.76).

In the

The result C4) is known

is positive.

absolute

historically and is

of an ideal gas:

result

earlier

our

with

\302\253
1,

[33)

-(oFJdT)v,K.

the entropy

have

we

energy by

of

entropy

classical regime h/uq

as

lhe

idea! gas. It is

a monatomic

Siickur-Tflrode

imporiani

in
of chemical reactions. Even
thermodynamics
though the equation containsh, the result was inferred from experiments on
in chemical
rcaclions iong before the
v;ipor pressureand on equilibrium
it was a greal challenge to
quantum-mechanicalbasiswas fuliy understood,

theoretical
unsuccessful

the

essential

physicists

to

attempts

to do

explain

the

Sackur-Tetrode

so were made in

the

equation,

early

years

and

many

un-

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
are
side by side, each system having
gases at identicalconditions
placed
entropy
JV
that
connects
the
is doubled.
Jf a valve
ffj, the total entropy is 2al because
is unchanged.
We see that the entropy scalesas
systems is opened,the entropy
the

of the

size

concentration-

valve is

at constant
system: the entropy islinear in the numberofparticles,
increases
when the
If the gases are not identical,the
entropy

opened (Problem6).

Heat

Capacity

The

heat

capacity

at constant

volume is defined

in

Chapter

3 as

C5)

Chapter6: IdealGos

for

the expression

wlien

derivative

the

calculate

can

We

is

nQ

from the entropy C4) of an

directly

idea!

gas

out:

wn'tien

IE

From this,

idea!

an

for

gas

C6)

or Cy

to perform the work

be added

must

units.

conventional

capacity at constant pressure is largerihan

The heat
heat

in

%NkB

gas againstthe constant

lhe thermodynamicidentity

discussed

p, as

pressure

xda

to

needed

because
C\302\245

expand
in

detail

in

additional

the volume of
8. We
Chapter

the
use

-f pdV to obtain

dU

/eu

C7)

only on Hie temperature,so tliat ldU/i)z)p

will have the same value \342\226\240dSidU/di}^, whieh
Cy by the argument of C.17b).
isjust
= N. Thus
lhe
ideal
By
gas law V
C7)
Nt/p, so that the terra p(dVldt\\
becomes

The

of

energy

ideal

an

gas depends

Q. + N

C, =
in

fundamental

or

uniis,

C,
in

capacities

have

as R,

We

units.

conventional
in

the

two

notice

systems

C,

again
of units.

C8b)

Nk,

the different dimensions that heat

For one mole,NkB

is

usually

written

called the gas constant.

The resultsC8a,b)

are

decrees

C8a)

of freedom

of a

for

written

an

ideal gas

without spin or otherinlernal

molecule. For an alom Cy

c,

= In + n

= |,v

\342\200\224

:N,

so

that

C8c)

Heat

units, or

in fundamental

Cp
units. The

in conventional

Example;

from

found

\302\273

C8d)

$NkB

ratio CpjCv is written as 7,

of the

tests

Experimental

are oflen

entropy

Capacity

Sackur-TeiroJc

gamma.

equation. Experimental values

of Ct by numerical
integration

values

experiment!

letter

Greek

the

ihe

of

of C7)

C9)

Here <j@)

ihe

denotes

at the lowest

entropy

temperature attained

in

rhe

measurements

suggests rhat o@) may be set equal ro icta unless

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
and
pressure
may be
equation C4). The value thus calculated at a selected temperature
value of the entropy
of ihc gas. The experimental value
compared with the experimental
is found
ihe follow ing confributions:
by summing

of C,,. The fhird

Enlropy increase on

1.

2.

of thermodynamics

law

solid

healing

Entropy

increase

in ihe

.1.

Entropy

increase

on hearing

4.

Lntropy

increase

in ihe

5.

Enlropy

change

absolufe

from

transformation (discussedin

solid-to-liquid
liquid

zero to the melling

from

niching

[mini to ihe

point.
10).

Chapter

boiling point.

liquid-to-gas transformation.

on heating

gas from

the

point

boiling

to ihe

selected temperature and

pressure.
There

may

further

of experimental

We
enlropy

I.

be a

give delails of the

is given in terms

lo C4)

corrctiion

slight

and theoretical

values have

comparison

for

for ihe

now

been

nonidcalilyoflhe gas.Comparisons
out for many gases,and

carried

afler ihe measurements

neon,

oflhe conventionalentropy

very

of Clusius.The

=s kua.

M.55 K
The heat capacity of ihe solid was measured from 12.3K to the melting
point
The heat capacily of ihe solid below I2.3K was
under one atmosphereof pressure.
zero of the me^iuceslimaicd
by a Debyc law (Chapier 4) extrapolation to absolute
found
of
ihe
at
is
menlsaboie IJJK.Theeniiopy
solid
the melting point
bj nuir.e.'tcal
of UlTiCp/T) 10be
inlcgralion
5lolid

\342\200\242

A classic

ihe American

=,

vtudy is \"The heal rapacity of

Chemical

Society

i4.29Jmor'K~t.

oxygen

51.2300 A939).

from

12 K to

its

boding

point

,ind

its hiat

of

Chapter 6:

idcutGa:
1

able

xaluaot
wide

uropy ullli c

Enlropy

r.lp,lnK

Gas

Nl-

212

Ar

87.29

Kr

119.93

sul'rce:

hc.it

associated enlropy

The

3.

point

to mc!l

required

inpul

The

of melling

heat capacilv of the

of 27.2 K under one

heat

The

mol\021.

associaied

The cxpertmenlal
sphere adds up to
sK3i

The

^.oiid

calculafed

value

14506

labics, 6lh

cd.,

Voi

was

liquid

the

measured

atmosphereof

pressure.

K is observed

lo be 335

J mol\"'.

The

from

&SUvAi
of neon

entropy

the

poim

inching

[o ihe

increase was

The entropy

found

boiling

10 be

- a.SSJmol-'K-1.

of neon

oflheeniropy

ASmelling

value of

ai 24.55

solid

the

is

5g\302\273,

from ihe

96.45

12924

at
to vaporize ihe liquid
enlropy of vaporization is

required

input

96.40

129.75

BonMvin

ASIJ4Uid

4.

Iculalo

Ca

144.56

Lumhh

From

The

E Nperimenia

'K\"

Jmol\"

in

4, pp. 394-399.

Pan

. 2.

boilin

iiosph

96.45

gas a! 27.2K

af a

pressure

same condifions

Jmor'K\021
agreemenl

lo be 1761J

ofoneafmo-

\302\253
96.40Jmor'K\021.

ASViPQliMlion

under ihe

Sackur-Tefrodeequation. The excellent

was observed

27.2K

is

,
with

fhe experimental value

led to the Sackurfind
it verified by
6.2.
in Table

gives us confidencein the basis of the entire theoreticalappamlus that

Tctrodc equation. The rcsuh
<31) coutd
Unrstly l[:ivc been guessed; to
observation is a real experience.
Results
for argon
and krypton are given

of IdealGas

Chemical Potential

Infernal

with

of FreeJoin

Degrees

Chemical Potential of Ideal Gaswith

Internal

of Freedom

Degrees

We consider now an idealgas of identical

polyaiomic
has rotational and vibrational degreesof freedom

tional degrees of freedom.

Thetotal energy

\302\253
\302\243
en

to

motion of the

problem

rotational

In

classical

oscillator

is the

the transla-

sum of two

regime

of Problem '3.6.
sum for the
1

terms

in

ofthe orbital is assumed

to
to
correspond occupancies
states Gibbs sum associated
n

greater

the

be

degrees of freedomand
molecule.

treated

r.n

vibrational

earlier. The rota-

n is

orbital

;.exp(-\302\243fl/t)

The

D1)

because the averageoccupancy

\302\253
I. That
is, we neglect the terms in 3- which
than
In the presence of internal energy
unity.
with the orbital n becomes

of ),

powers

higher

D0)

problem

the Gibbs

\302\243\302\253

where

eifli

center of massofthe

harmonic

the subject

was

energy
the

the

ts

and vibrational

rotational

the

to

refers

einl

the translations!

energy

to

addition

in

the molecule

parts,

independent

where

e of

molecule

Each

molecules.

are omitted

D2)

D3)

The

is

summation

just

the partition

function of the

internal states:
(\024)

which

is

~tlogZ;ol.

related

to the

From D3)

internal free energy of the

one

molecule

by

/\"in,

the Gibbssum is

D5)

Gas

6: Idea!

Chapter

The probability

the state of
in

the

to

the

that

of

The classical regimewas

of

Several

tlie

(a)

the molecule,

sum 3-:

Gibbs

analogous to

n is occupied, irrespective of
is given by the ratio
of the term

orbita!

transtationat

motion

internal

the

for

A3)

\302\253
i. The
/(\302\243\342\200\236)

ease, but

monatomic

derived for the

results

the

as

earlier

defined

XZinl

now

D6) is entirely
the role of A.

result
plays

monatomie ideal gas are different

for

ideal gas:

polyatomic

Equation

is replaced

for,*

A7)

by

D7}

with

<iq

defined

as before

exactly

ideal gas

monatomic

(We shall

of atoms with

zero

always use ne as defined

spin.)

Because

for

e\\p(/i/i)

the

we

have

p. =

(b)

The free

~
r[log(ri/nQ)

energy is increasedby,

for

IogZiol].

D8)

JV molecules.

D9)

(c)

Thecniropy

is increasedby

E0)

The former

Example:

Spin

represcnl

boih

resuU U

enmtpy

\342\200\224

jh'z

10 die

energy alone.

iranslalional

ntasnrtic field. Consider an

and nuclear spins. TIic iniernal

in zero

electronic

applies

of Spin /,
funciion
partition
atom

where /

may

associaied

Reversible Isothermal Expansion

the

with

is

alone

spin

ZiM =
this

the number

being

of independent

{2/ + t) ,

spin siaics.The

the

entropy

spin

E0).

TheefTec!

of the spin

Isothermal

The
to the

is the

x !0Jcm\\

gas

the

What
The

initial

of D8):
E4)

I)].

pV

at an initial volume of

of 4He

at constant

The temperature is

temperature
constant

maintained

reversible

the

expansion

\342\200\224
S'x

we

see

final

until

by
system

the

thermal
ai

any

is equal

temperature

the final pressure

that

is

pressure.

increase of entropy
an
an
of
ideal
at
entropy
gas

is the

a(V) =

expansion?

constant
A'log

= (ix

4-

constant

on

volume

as
E5)

l0\{0.69?)")

entropy is larger at the largervolume,

states in the largervolume
than
in

same temperature.

depends

temperature

= jVIog2

Notice that the

more accessible

slowly

expand

initial temperature. From

one-half

with the help

is found

after expansion?
is twice
the initial volume; the

pressure
volume

final

E3)

logBi

atoms

1022

contact with a large reservoir.In a

instant is in its most probableconfiguration.
What

1) .

Expansion

!03cm3 at 300K. Let the

is 2

E2)

entropy on the chemicalpotential

Consider as a model example1

volume

1) ,

logB/

}i = T[Iog(n/ii0)-

Reversible

free energy is

is

\302\273,.,

by

to the

contribution

spin

Fial = -tlogB/+
and

E1)

*=

0.069

because

the smaller

the

1033.

E6)

system

h.TS

volume at the

Work

6.7

Figure

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
llio load of
expand. The pressure is reducedby removing
weights a

work is done by

How much
When

Figure

at

little

the

gas

the

ht the

gas

isothermally,

expands

work done

The

6.7.

a time.

expansion ?
it

work

does

from

directly as4.!4 x

30serg=

W as

the work

negative of the work done by

\302\253

DJ.4J){0.693)

The assumption that the process

that a knowledge of Vat every
stage
define

the work

Thus

43.4J.

done on the

E7),

Ni!og2

We

in

E7)

Ntlog2.

H\\NxjV)dV

pistonis,

as

on the piston when the volumeis doubledis

We evaluate/Vt

a piston,

against

is reversibleentersin
determines

p at

done on the gas by

the

w=

2S.7J.

gas

on the

E8)
E7)

when

we assume

every stage of the expansion.

external

piston. From

-jpdV= -28.7J.

agencies.

This

is the

E8),
E9)

ruble

What is the

in ihe
changeof energy
expansion?
of an idea! monatomicgas is U

The energy
an

at constant

expansion

decreases

temperature.
which is the work

by Afilog2,

*=

mt Entropy

Expai

and

jNx

not change

does

However, the Helmhoitz free

in

energy

done.The connectionis discussed

in

S.

Chapter

flowed inio the gasfrom the reservoir?

that ihe energy ofihc idea!gas remained
the
constant
when
of energy
it is necessary thai a
gas did work on the pision. By conservation
(low of energy in ihe form of heat into the gas occur from ihe reservoir
through
the walls of the container.The quantity
heat
added
to
be
of
the
must
Q
gas
but
be
in
because
equal,
opposite
sign, to the work done by the
piston,
How

much heal

Q +

seen

have

We

0. Thus

Q =
result

the

from

Reversible
We

the

at Constant

Expansion

expands

insulated container.

at constant temperature. Supposeinstead

from I x 103cmJ to 2 x 10Jcm3in an in-

reversibly

No heal

to

flow

is constant in a system

The entropy

processis

Entropy

an expansion

above

gas

F0)

E9).

considered

that

28.7 J ,

out

carried

or

isolated

(slowly).

reversibly

is permitted, so that Q = 0.
the reservoir if the expansion
from
of entropy
A process without a cluvnge
the gas

from

is called

adiabaticprocess.

has

is

an isentroplc process or an
the specific meaning that
there
we

simplicity,

stick

shall

term

The

no

heat

transfer

in the

\"adiabalic\"

process. For

wilh\"isentropic.\"

What is the temperatureof the gas after expansion ?

The entropy of an ideal monatomicgas depends

on

volume

the

and ihe

temperature as

a{z,V)so that the entropy

constant

remains

at

constant

eniropy
'

Tl3'2f,
for

an

ideal

monatomic

gas.

+ constant)

logK

F1)

if

t3/2K =

constant;

Iogt3/2K=

In an expansion

N{iogT3;I

from

V1

to

V%

constant.

F2)

have

we

= rivlV1

F3)
.

Chapter6: IdealGas

idea! gas

the

use

We
V

law pV =

forms. We

alternate

two

obtain

to

Nz

insert

F3) and cancelN on both sidestoobtain

Nxjp into

F4)
r =

insert

we

Similarly,

to obtain

pV/N in F3)

F5)
BothF4)

and

hold

F5)

for

an iscnlropic

monatomic gas.

an ideal gas of
motion {rotations, vibrations). We obtain

to

10

Problem

internal

with

molecules

for a

only

It is ihe subjectof

of

degrees

these

generalize

results for

process

F7)

t.'\"'\"\"'V. =r2\"\"-

Here'/ s

is

Cp/Cy

the

ratio

heat capacities at constant pressureand

of the

volume.

constant

With

Tx

- 300K and

Vs/V2

find from

|- we

F3):

\302\253
189

Tt\\k is

ihe

is cooled

in

final

the

expansion

Tt

Expansionat constant
What

is

ihe

change

the

after

temperature

hi energy

300

is

entropy

in ihe

an

\302\243/,=

189 K

at constant

entropy. The gas

- !!IK.
method

important

G0)

of refrigeration.

expansion?

The energy change is calculatedfrom

ideal monatomicgas
U2

F9)

by

process

- Tt =

expansion

K.

Cy{x2

the

temperature

r2 -

change

r,) ,

G0). For

an

G1)

fi

or, in

conventional

Expansion

into

units,

ut =ivA-B{ra- r,)

a2-

\302\273i(l

=\302\273
-2.3

10IZ)(j.38

JO\0216ergK\"!){-IHK)

\302\273
-231

108erg

G2)

decreases in an expansion
at constant
entropy. The work done by
to
the
decrease
in
of
equal
energy the gas, which is Ul - U2 = 23 J.

The energy
the

is

gas

Sudden Expansion inlo a

the

Let

Vacuum

suddenly into a vacuum

gas expand

a Hn:t!vohmicof 2 liters.Thisis an
is opened

a hole

When

in

the

excellent

an

from

of an

cxiimpfe

to
process.

of I liter

irreversible

ihc expansion,

to permit

partition

volume

initial

the first

moms

and strike ihc oppositewall. If no heal How through the

is no way for the atoms to lose their kinetic
permitted,
energy.
The
flow may be turbulent (irreversible),
of tht!
with
different
subsequent
parts
values
of the energy
between
gas at different
density. Irreversible energy flow
will
the
assume
the
regions
eventually equalize conditions throughout
gas. We
whole process occurs rapidly enough so that
the walls.
flows in through
no heat
rush

the hole

through

walls is

there

Hois1much work is done in the expansion ?

No meansof doing external
is provided,
work
is not

work

Zero

work

the

is

What

is zero
the

so that the

work done is zero-

of all irreversibleprocesses,but
for expansion into a vacuum.
a characteristic

necessarily

after expansion?

temperature

No work is doneand no heat is added in the expansion:

W = 0, Q ~ 0, and
~
=
0. Because the energy is unchanged,the temperature
of the ideal
U2
t/j
is
The
in
the
because
of
a
real
gas
unchanged.
process
energy
gas may change
the atoms are moved farther
affects their interaction
which
energy.
apart,
is

What

the

change

The increase

of entropy

the

in

expansion

of entropy when the volumeis

at constant

doubled

temperature

is given by E6):
Au

a2

into a
Expansion into a vacuum

For

most

the expansion
probable

(equilibrium)

a,

vacuum

is

- Nlog2 =
2

not

0.069

1023.

G3)

= 0.

a reversible

configuration

process: the

system is not

in

the

at every stage of the expansion.

Only

'

Gas

Idea!

ChapterS:

Reversible ]
isothermal

t-

y
0

expansion j

I-

A'rtog-

-.Vtlog-^

Nlog^

Reversible

]
]

isentropic
expansion

-J.Vt,I-(\302\243)
L.
\\vi/

Irreversible

\021

into

expansion

y
0

vacuum

Wlog

\342\200\224

'

before removal of the partition and the final conare most probable configuraiions. Al intermediate
configuration
equilibration
the distribution
in concentration
and kinetic energy
of atoms
between
stages
the two regions into which
the
divided
does
is
not
system
correspond to an
distribution.
The central
results of these calculationsare sumequilibrium
the

initial

configuraiion

after

6.3.

in Table

summarized

LAW

GAS

(a) /(e) =

LEADING TO THE

STEPS

SUMMARY:

GAS

MONATOMIC

SPINLESS

FOR

IDEAL

Aexp(-\302\243/r)

of an

Occupancy

limit

classical

(b)

(c)

=\342\200\224-\342\200\224-\342\200\224~~~

Given

e*P(-\302\243nA)

=
-\342\200\224-177x73

Energy

'j

X!CXP(\342\200\224\302\243JT)
\"

this

N,

-[n the

dassical
of a

Ik

'/ii
j

n2

exp(\342\200\224e/t)

Transformation

equation

determines

limit.

free particle
n

number

quantum

volume
(d)

of/(\302\243)

the

in

\302\253
1.

En

orbital

orbital of

in a

cube of

V.

of the

sum to

an

integral.

(e)

X =

N/nQV

Result of the integration

subsitution

(f)

nQ

= {Mi/27rfi2K/2

(d) after

in (b).

Definitionof the qaantam

. concentration.

(g)

T!og(ll,'!!Q)

(h) F

(i) p

- -icFfcV)t,N-

J(/,V/i(.V,t,K)

1]

NiDog(tr/HU)

Nt/K

PROBLEMS

Show

Derivative of Fermi-Dirac function.

Fermi level e = ji has the value
Dt)~'.
7.

steeperthe slopeof
2.

Symmetry
as

appears

the

Thus

f{fi

of 'filled and vacant

i5). Show that

e = /i

Let

orbitah.

probability an orbital6 below

known as a hole.

to the

ihc

at

evaluated

the temperature, the

Fermi

the

that

ap-

/(c)

G4)

is equal
is
orbital

is occupied

is vacant.

level

so

+ 5,

fin + 5) = 1 -'/(/< - 3).

an orbital 5 above the Fermslevel

that

probability

\342\200\224cf/vc

function.

Fermi-Dirac

the

that

the lower

Thus

vacant

sometimes

3.

Distribution

of

values
and

siaiist'tcs.
Let us imaginea new
an
are 0, I, and 2. The
of
orbital
occupancies
lo be 0, e,
the energy associated with
are assumed
these
occupancies

It,

which

double

for

function

in

mechanics

occupancy

the allowed

respectively.

(a) Derive

an expression for

system composed of

ensemble
is

orbital

this

at temperature
now
to the

reservoir

the

in

t and chemical
usual quantum

average

thermal

(N>, when the

occupancy

contact

and diffusive

with

potential/t.

mechanics, and derive an expression

of
an
energy level which is doubly deaverage occupancy
the
e. If both orbitals are
identical
degenerate; that is, two orbhals have
energy
Return

(b)

for

the

ensemble

occupied

the

4. Energy
particles

have

total

is 2e.

energy

of gas of extreme
p such

momenta

relativistk

that

pc

particles.
\302\273
Me2,

where

Extreme
M

is the

relativistic

parti-

rest mass of the

/. =
particle.Thede Broglie
h/p Tor the quantum wavelength continues
to apply.
ideal
that
the mean
energy per particle ofan extreme
nonrclativistic
the
(An interesting
gas is 3t ift S pc, in contrastto ir
problem.
in Notes on Thermoby E. Fermi
variety of relativisticproblems discussed
of
wul
Suiiisiks,
Chicago Press, 1966,paperback.)
University
relation

relativistic

Show

Tor

are

ttynumU-s

5,

Integration

modynamic

of

identity

the

tlwrntodynanric

at constant

identity

for an

ideal gas. Fromthe

number of particleswe

thcr-

have

^.
X

G5,

Gas

6; Ideal

Chapter

Show by integration thai

6.

if

Relation

pressure

N log

a system

at

G6)

V.

and

of

a system

that

jV

of N atomsof type

diffusive

after

atoms
B at

A is placed
same
the
temperature
of type

the total entropy

is reached

equilibrium

known

in

{A

The difference

is established.

contact

and

pressure

of

(a) Show

density,

energy

contact

in thermal

a system

in

logT

results

the

in

has

ihc Gibbs paradox.

been called

7.

Cv

2. The

diffusive

when

entropy

a =

entropy is

as [he entropy
eniropy increase2N log2is
ihe atoms are identical s B), show that there is no increase

by 2N log

increased

ofmixing.

gas the

Suppose

with

contact

and volume. Showthat

is

ideal

of mixing.

Entropy
diffusive

in

an

a constant, independentof t

crj is

where

for

reservoir

a heat

with

ihat

ihe

average

pres-

is given by

G7)

where the sumis over all states

of

the

(b) Show

system,

for a gas offree particles

that

result of the boundary conditionsof the

whether es refersto a stateofJV noninteracting
that for a gas of free npnrelativistic particles
as a

G8)

-r77

problem.

particles

The

result

or to an

hoids equally

orbital (c) Show

p= WjlV ,
thermal

is the

where

average energy of

to the classical

regime;

long as

nonrelativistic.

8.

they

Time for

cases

in

a 0.1

are

it

holds

liter

container

wiH

We

unmix

the system. This result

Tor fermion

equally

a large fluctuation.

G9)

Boitzmann

quoted

only

in a

is

and boson

to ihe

lime enormously

not

limited

particles, as

effect that

two

long compan^

problem: we let a gas of atomsof

\"'\"'years.
of 1 aim,
volume
liter
at
300 K and a pressure
a
container
of
ofOJ
occupy
and we ask how long it will be before the atoms assume a configuration in
all are in one-half
of the container..
which
initial
accessible
to the system in this
of states
(a) Estimatethe number

to 10\"
JHe

condition.

We

shall

investigate

a related

(b) The gas is compressed isothermallyto a volume

stales are accessiblenow?
the

For

(c)

system
of

number

for which

states

number of states

ofthe

frequency

(e)

Estimale

are

with

the
of

one-half

in

9. Gasof
atomicgas,
energy

l-'nut ttic (a)

system

iutermil

has two internal energystales,one

the atom

There ;ire H aiomsin

chemical puk'iiljai; (h)

an

tdcal

of ideal

in an

gas

isentropic

gas.

an ideal man-

Consider

of freedom.

degree

which

for

[he oiher.

relations

hentropic

of

total number

is Ihe

of the

live

volume

V at

(c)

entropy;

energy;

(o) heat capacity;it constant pressure.

10-

'

as a crude estimate
system changes.
number
of years you would expectto wait
before
all atoms
the volume,
starting from ihc equilibriumconfiguration.

one

but

A above

volume

We use this

a year?

in

the slate

which

m'th

atoms

in the

what

10lC)s\"',

volume

the

of

one-half

are anywhere

atoms

an atom is %

in the

atoms

all

are in

all atoms

the value of the ratio

estimate

container,

the

which

for

rate of

collision

the

If

(d)

collisionsof

liter

0.1

the

in

How many

liter.

0.05

of

an

r.

temperature

(t|> pic.^uic;

(a) Show that the differential

changes for

process satisfy

(SO)

where

=
these relations apply even
CpjCv\\
of
freedom,
(b)The isentropicand isothermal
degrees
y

BB

Show

for

that

given by

ideal gas of
Here p
//.

the

at

constant

Bs =*

~V{cp!cV)a;

idea!

gas Ba

(Ba/p)\022; ihcre
of

molecules

mass

= yp; B,

is very
M

iittie

= p.
heat

we have

is the massdensity.

Convcaire

of

an

iscntropk

troposphere\342\200\224is

atmosphere\342\200\224the

entropy,

equilibrium of the

not

constant

The

if

bulk

internai
are defined as
have

molecules

the

moduli

(81)

-V(dp/dV)t.
of

velocity

transfer

sound

in a sound

p = pi/M,

so

that

in a gas is
wave. For an
=

(yr/'A/I''

atmosphere. The iower iO-15km

often
in a convccijve sieady state

temperature.

\\\\\\

such

equilibrium

p\\\"'

is

Use the condition of mechanical

independent of altitude, where
CplCr.
field to: (a)Show that dTjdz = constant,
equilibriumin a uniform gravitational
where
r is the altilude.
This quantity, important in meteorology,is calledthe
was
relation
that
adiabatic
pressure
dry
lapse rate. (Do not use ihe barometric
derived in Chapter 5 for an isothermal
(b) Estimate JT/i/r, in
atmosphere.)
=
mass density.
CC per km, Take y
7/5. (c) Show that p x p1,where
p is the
=
-,\342\226\240

Chapter6: IdealGas
gradient is greater than the isentrapic
temperature
be
unstabic
with respect to convection.
may

actual

the

If

atmosphere

12. Idealgas ttro

monatomicgas
in

in

Gibbi

13.

Chapter

is 3in

an

(b) Find

sum for ideal sas.

3, show that the

{a)

V in

diffusive

With

coniact

P(N} =

Hie

expression

a. The
the

(c)

X P(N) = 1

r.

Zs ^

of

help

ideal
there

probability

gas

of

arc

;V

from

(i>QV)sf,\\\\

atoms

identical
atoms

<N/exp(-<N\302\273/N!

is just ihe Poisson distribution function

thermal average number of atoms in ihe
XVnQ,

temperature is

in

Hie gas

wiih a reservoir is

which

previously as <N) =

confined to a square of area

for the energy
V of the gas.

N atonis

Gibbs sum for an

exp(;.iiQK).(b) Show that

volume

an

the entropy

for

expression

with

the

potential of an ideal

ihe chemical

Find

(a)

dimensions,

spin is zero,

L2. The

(c) Find

dimensions,
two

gradient,

Confirm

that

and

(82)

Here

<jY> is the

we have

evaluated

C).

{Appendix

volume,

which

P[N) above satisfies

NP{N)
\302\243

<N>.

ideal monatomic
of an
gas ai
gas calculations. Consider one mole
300K and 1atm. First,let the gas expand
and
to
twice
isothermally
revcrstbly
an
let
the initial
Hits be followed by
volume;
second,
iseniropic expansionfrom
io four limes ihe initial volume, (a) How much
heat
is added io
iwice
(in joules)
at ihe end of
the gas in each of these two processes? (b) Whai
is ihe temperature
is replaced
the second process?Supposethe first process
by an irreversible
a
(c) What
expansioninto a vacuum, to total volume twice the initial volume,
in joules per kelvin?
is ihe increase of emropy in ihe irreversible
expansion,

14, Ideal

15, Diesel

engine

in

engine

so

which,

compression.

fuel is

compressed

highly

initial temperature of
maximum
y

diesel

engine

is an

internal combustion

sprayed into the cylinders after ihe air chargehas been

!o tgntte
it has attained a temperature sufficient
the
that

i sen tropically
from an
that the air in the cylindersis compressed
If
ratio
is
what
is the
the
27\302\260C C00
15,
compression
K).
the
is
healed
\302\260C
to
which
air
in
the
by
compression?
temperature

fuel. Assume

Take

1.4.

Chapter

and Bose Gases

Fermi

183

GAS

FERMI

Fermi Gas in Three Dimensions

Slale of

Ground
Density

of Electron Gas

Heal Capacity

FermiGas

IS9
194

Metals

in

Stars

Dwarf

White

185
1S6

Simcs

of

Nuclear Mailer

BOSON

of

Spacing

199

199

Near Absolute Zero

Chemical Potential
Example:

19S

CONDENSATION

EINSTEIN

AND

GAS

196

'

and Second

Lowest

Lowest Orbilals

of FreeAtoms
Orbital

201

Versus

Occupancy

202

Temperature

205

Einstein CondensationTemperature

207

\"He

Liquid

Quasiparticles

and

212

*He

Superfluidity,

Phases of

Superfluid

210

of Helium

Relations

Phase

217

3He

SUMMARY

217

PROBLEMS

218

1. Density
2. Energy

3.

of Orbitals in One and Two

of Relativists Fermi Gas
and

Pressure

Versus

Potential

Mass-Radius

for

Relationship

Heat

Energy,

Gas

Boson

219

Fermi Gas

219

Temperature

White

7. Photon Condensation

8.
9.

218
219

as a Fermi Gas

5. Liquid'He

6.

of Degenerate

Entropy

4. Chemical

218

Dimensions

Capacity,
in One

and

Entropy

Dwarfs

219

of Degenerate Boson Gas

221
221
222

Dimension

Stars
10. Relativistic White
Dwarf
!!. Fluctuationsin a FermiGas

222

12.

222

Fluctuations

13. Chemical

14.

Two

Orbital

in

222

a Bose.Gas

222

Potentia! VersusConcentration
Boson

System

223

It is

a fundamental result of quantum

and molecules,areeither

regime

the

which

in

They behave

bosons.

or

fermions

is small

concentration

all particles,

that

theory

in

including

atoms

alike in the classical

with

comparison

the

quantum

concentration,
(i

Whenever n >

the

iiq

gas

\302\253

ifQ

to be

is said

A)

(Mt/2tt/ijK'2.
the

in

regime

quantum

is called a

and

quaniutn
gas.
properties between a quantum gas of
ions
a gas in the classical
lemi
and one of bosons is dramatic, and boih are unlike
A
low
has a high kineticenergy,
low
heal
regime. Fermi
gas or liquid
capacity,
a high
and
exerts
magnetic susceptibility, low interparticle collisionrate,
at
absolute
zero,
A Bose gas or liquid has a
pressure on the container, even
\342\200\224
of
concentration
in the ground orbital, and these particles
high
panicles

Bose

the

called

in physical

difference

The

a superfluid,

as

act

condensate-\342\200\224may

with

practically

zero

viscosity.

For many

systems the concentration

important variable.The

is

obtains

regime

quantum

fixed,

is
the temperature
when
the temperature

and

the
is

below

t0 s
n ~

by the

condiiion

is often

said to

be a degenerate gas*.

realized

defined

was

by

Nernst

iiq. A

that

B)

{2nh2/M)n213,

gas

in

theentropy

the

quantum

regime

with r

\302\253
ro

of a classical gas divergesas logr

both
fermion
boson
and
theory removes the difficulty:
-+
a
the
i
so
that
0,
gases approach
unique ground stateas
entropy goes to
zero.We say that ilie entropy is squeezed out on cooliuga quantum
(see
gas
3 and S).
Problems
in the classical regime{Chapter6) the thermal
number
of particles
average
as

t -*

in

an

0. Quantum

orbital

of energy

\302\243
h

given

by

Wilh Ihe result for^

appropriateto

this

regime,

J{z)

with

the usual

choice of the origin of eat zero

The

form

assures

D)

<it/nQt which is

is any

fcrniion

spin.
occupancy

low

0 or

of

I,

it is

temperatures

by ihe

zero

the classicalregime.
a half-iniegra!

composite\342\200\224with

low-iying orbiials will

all orbitals

energy below

<

with

are

there

which

just

fermitm

one

have

eF will be

e <

occu-

orbital

these limits. Ai

between

anywhere

is always

orbital

Pauli exclusion principle to an

occupancy

average

lowest orbital.

of the

energy

picture of

original
or

dear that many

orbital. At absolute
I. Here ef is the

in each
with

an

with

D)

occupancy of any

panicle\342\200\224elementary

is limited

fermion

our

with

\302\253!,consistent

the

for

the average

us that

(n/HG)exp(-\302\243/i)

occupied
orbitals

enough

system. This energy is calledihe

= Oiit r = 0. As t increases the
Fermi
will
orbiusls
t-iierfiy. Abo\\cr-fall
have/
a high energy mil, as in Figure
distribution
function
will develop
7.3.
Bosons have integral or zero spin. They
or composite;
be elementary
may
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
of half-integers.
The Pauli principle does not appiy
to bosons,
so there
immber
is no limit
on
the ground
ihe occupancy
zero
of any orbital. At absolute
in the
orbital
of lowest
orbital\342\200\224the
energy\342\200\224is
occupied
by all the particles
the
is
increased
the
ioscsits
As
lowest
orbital
temperature
populasystem.
single

to hold the

number

population only

contain

each excited

and

slowly,
a

of

orbital

orbital\342\200\224any

small number

relaiively

to the

assigned

ofparticles

of particles.

We

higher

energy\342\204\242will

this

discuss

shall

feature,
carefully. Above r = r0 the ground orbital losesits special
becomes much like that
of any
excited orbital.
occupancy
low-lying

Fermi

is called

gas
Fermi

ihe

with

energy.

energy lower than

orbitals of higher
wlicrt

regime

the

ihe

in

will

Chapter

The

compared

The

most

striking

vacant.

entirely
Fermi
with

gas
the

is said

Fermi

is occupied

orbital

An

to be

energy,

as

no udegenerate
in

the

classical

6.

of tlie theory of degenerateFermi

gases
the wliiie
dwarf stars; liquid 3He; and
of 3 fermion gas is the high
kinetic
property

unportam
applications
conduction
electrons in metals,
matter.

be almost

one fermton.
ishigli

temperature

treated

degeuerate when the temperature is low in comparison

the orbitals of
When the inequality i \302\253
e^ is satisfied
and the
be almost
Fermi energy ef will
entirely
occupied,

energy

it contains

when

fully

its

GAS

FERMI
A

point
;md

include

nuclear
energy

level f, for

Fermi

16 eleclrons;in

60
\342\226\240|

gTOUnd

\"a

slalc

Hie

the

louesi eight levels

(!6orbilals) are
occupied

(a)

(a) The
to a fine of

7.1

Figure

confined

spin up and one for

Orbitals above the

energiesof
spin

down,

n = i,2
10for an etecfron
level correspondsto two orbitafs, one for
The ground siaicof a system
of t6 electrons.
orbhals

the

L. Each

lenglh

(b)

shaded region

in the

vacant

are

Slate.

ground

that
it Is necessary
ground state of the system at absolutezero.Suppose
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?

of the

In a one-dtmenstonal
is a positive
form

the

crystal

integer

stn{fJ7ix/L)

number ms

If the
(i

other

Any

filling

we

and

3, 4

1, 2,

fill

higher

tire

with

in,

orbitals

in Figure

then

7.1.

electrons
in

the

ground

and

fiHed,

a higher

from

starting
with

the

in

are
\302\261\302\243

gives

arrangement
orbitals

The orbitais that are filled

shown

by

supplemented

it,

the

spin

quantum

spin down.

up or

spin

8 electrons,

has

system

empty.
state

\342\200\224 for
\302\261
j-

free electron orbitalof

of a

number

quantum

it
until

ground

all

the orbttais

state

the orbitais

of higher n are

energy. To constructthe
at

the

botiom,

N electrons

with

and we

ground

continue

are accommodated.

state of a systemof 16electrons

are

Ground Sttite of Fermi

Ground Slate of

Fermi Gas in

in Thtee

G&s

Dimensions

Dimensions

Three

be a eube of sideL and volume

V = L3. The orbilais have
the
of C-58) and their energy is given by C.59).
The
is
form
the
Fermi
energy Ef
of the highest filled orbiiai at absolutezero;it is determined
energy
by the
that
the
N
in the
stale Iioid
requirement
system
ground
electrons, with each
filled wiih one electron up to the energy
orbital
the system

Let

E)
<5)

Here

the

radius

filled

and

is

tiF

separates

of a

sphere (tn the space

empty orbitals. For the

orbitais must be filled

to

up

nF determined

of the
system

factor|
in

because

arises

the

n, = {lNfn)ll\\

F)

has two possiblespin orientations.The

nx, ny, nz in the positive octant of the sphere

triplets

only

to be

are

space

ihai
\302\273r)

tty,

an electron

because

2 arises

factor

nx,

N electrons

hold

by

The

integers
to

counted. The volumeof the

sphere

We may

is 4nn//3.

then write E) as

This

Fermi

the

relates

so-called \"Fermi
total

The

energy

[/\342\200\236

with

En

with

F),

have

e,
\302\243

2 x

conversion

N/V

n. The

| x

In (8)

471

\\^r

eln n2

eB *= --1

j j

P'

(in

\302\273a
,

(S)

and (9),n is an integerand isnot N/V.Consistent

let

21
in the

electron concentration

temperature\"tf is definedas t> s ef.

of the system in the ground state is

(h2/2m)(n}t/LJ.
we

to the

energy

(9)

(\342\226\240\342\226\240\342\226\240)->
2(fcX4n)

of (he sum into an

JdrtirV-)

integral.

Integration

ground state kineticenergy:

l0m\\L

of

(8)

gives

the total

0 10

40

30

20

60

50
in

Volume,

Total ground stale energy

7,2

Figure

elecirons,

80

70

90 100

cm3

Uo

of one

mole of

volume.

versus

and is f of
The average kinetjcenergy
is UJN
per
particle
the Fermienergy
N the energy increasesas the volume
decreases
cF. At constant
so
the
to the
that
Fermi
a
contribution
(Figure
7.2),
energy
gives
repulsive
in most
metals and in white dwarf and neutron stars
binding of any material;
it is the
most
tends
important
repulsive interaction. That is, the Fermienergy
the volume. It is balanced in metals
to increase
the
Coulomb
iiltraction
by
between decuoos and ionsand in she stars by gniviimicurjS attraction.
using

and F).

E)

Density of States

Thermal

averages

rr denotes

where

the

n; and

orbita!

distribution

orbital

function,
energy

for

independent

the

quantum

problems

particle

orbital;

XR

is

the

have the

value

form

of the

quantity

A'

in

f(t:a>T,!i.)is the thermal averageoccupancy,calledthe disof the orbital n. We often express

<.Y) as an integral over the

\302\243.
Then

A1)

becomes

A2)

Density of States

where

transformed to an integral by

has been

orbitais

over

sum

the

the

sub-

substitution

(\342\226\240\342\226\240\342\226\240)->
*>(eH'
\342\226\240\342\226\240)\342\226\240

A3)

Jrfs

of energy betweent and t 4- dt. The

cailed
the density of slates, although it is more
always
accurate
to call it the density
of a
of orbitais
because it refers
Jo the solutions
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
or equal lo some e is
than
Here

of orbitais

number

is the
<D(\302\243}^\302\243

quantity 'D(e)is nearly

N{e)

=>

V. Take

for volume

A4)

(V/in2)BM/h2)il2til2

the iogarithm of both sides:

logN
and take differentials

of

The quantity dN =

log

s=

N and

(iN/lsjdt is

A5)

+ constant,

flogs

loge:

the

number

of

of energy

orbifals

between c

and e + (/e,so that

~dNltlt

C(e)

is

the

counted

write

density

of

\302\251(e)as

a function

two spin orientations of an electronhave

this derivation because they were counted in F). We
of e

been

can

alone because

JV(\302\243)A

from A4). ThenC 7)

A7)

ZN{t)llt

The

orbitais.

throughout

(V/3n2){2m/h2)y'2F.in

(IS)

becomes

A9i

Chapter

7.3

Figure

of energy,

dimensions.
densiiy

and BaseGm

Density of orbitals as a function

for a free electron gas in three
The dashed curve represents the
of occupied orbilals ai a finile

/(eVD(e)

temperature,

bm

comparison

wiih

the

7: Fermi

occupied

is small

such thai r

in

cF. The shaded area rcprcsetus

orbiiah
ai absolute zero.

Energy, e

When

*D(e)

total

function (Figure 6.3), the densiiy of

orbilals (Figure 7.3).The
becomes
of occupied
<D(\302\243)/{e), ihe
dens'ny
of electrons
in a sysiem may now be written
as
by

multiplied

orbilals
number

*\"\342\226\240

the disiribulion

B0}

described
Fcrmi-Dirac distributionfunction
of
probkms where we know the total number
patiides,
from
ihal
the
total
of
calculated
number
requiring
particles
value.
The total kinetic energy of ihe electrons
is
correct

where

is Ihe

f{t)

If Jhe

sysiem is
which

above

in

they

the

ground

are vacani.

in

we
B0)

Chapier

determine
be

equal

6. In
}t

by

to

Ehe

B1)

stale,

all orbitais

are filled up to

the

energy

\302\24

The number ofekcirons is equalto

B2
and

ihe

energy

is

B3)

Heat Capacityof Electron

Heat

Gas

of Eleciron

Capacity

a quanliiaiive
for the
expression
of electrons
in three dimensions. The

derive

We

gas

impressive accomplishment
ideal monalomic gas the
much

lower

agreement

wiih

heal capacity of a degeneraie

calcufaiionis

heat capacity is \302\247W,bui

The calculation that

for

The increase

results.

theexperimemal

of N electronswhen

0 10

from

healed

i is

(he

in a

denoted

meial

an
very

agree-

of a

energy
AU

by

im-

For

excellent

gives

total

most

gas.

elecirons

follows

in

Fermi
the

perhaps

of the theory of (he degenerateFermi

are found.

values

Gas

U{x)

system
\342\200\224

L'(Q),

whence

f{c)

is (he

energy

range.

Here
unit

AU

JjVcrfWO:)

Fermi-Dirac fimetion, and O(c) is

We multiply
the identity

N \"

B4)

J0\"<fcrf>(E).

of orbilals

number

the

</e/WW

B5*

J^W

Jo\342\204\242

per

by tf to obtain

{jo
use

We

The

first

electrons

fo rewrite

AU

from

- tr\\n^y0{c)+

Je(b
on

integral

B6)

B4) as

B6)

JJ

- f/dttfiiz).

ifjAttrfteW

side of

the right-hand

ef to the

bring

contributionsto !he

energy

ihe
are

eiecirons
positive.

W)

fW&iz)-

B7) gives the energy neededlo take

orbitals of energy \302\243

>

ihe energy neededto

- $0

fc'M*r

The

the

and
\302\243f,

to ef

second

from orbifals
product

integral

gives

below ef. Both

f(c)'D{c)de in the

firsi

of electrons elevated to orbitals in ihe energy

is the number
range
ihe
in
the
is
an energy e.The factor [1 \342\200\224
second
integral
probability
/(\302\243}]
thai an elecironhas been removed
from an orbilal c. The function A (/is
plotted
versus
function
7.5
we
ihe
distribution
Fermi-Dirac
in Figure 7.4. In Figure
plot
of the Fernii
for
six values
of the lemperalure. The electronconcenlration
\302\243,
was laken such that tfjkB ~ 50000K, characteristic
ihe
of
conduction
gas
electrons in a meial.

integral

dc at

The heat
respect

to r.

capacity

of

the

electron

gas is

found on

The only temperature-dependentterns

in

differentiating

B7)

is /(e),

AU

with

whence we

Figure

7.4

of the energy of
dependence
The
fermian gas in three dimensions.
in normalized form as AU/NeT,

Temperature

a noninteracting
is plotted

energy

uhere

N is the

is ploued

number of decirons.The temperature

\302\243\342\226\240

S; 05
^

as xjtF.

0.4

3
e/A'b,
Figure

Fermi-Dirac

7.5

graph as

the

was
energy

calculated

at which/

in uniis

of 104

for
lempcraiures,
in
ihreedimensions.Th
gas
The chemical
of temperature.
with the help of Eq.B0)and may be read

disiribuiion

= J.

ai

function

TF = \302\243F/kB= 50000 K. The resuhs apply

number of particlesis constani,
independent

each temperature

0.6

various

10 a

Courtesy of

B. Feldman.

Heat

-Region of UcMsieraic

quantum

Capacity of

ElectronGas

gas

Rc\302\253ion

\342\200\224-^

of classic-,

\\

Figure

gas of

7.6
Piol of ihe chemical poiemiai /i versus
noninteraaing fcrmions in ihrcc c!iincisions.

can group

units of

ihc

plotting,

ji

i arc

and

temperature

for

For convenience

a
in

0.763cf.

terms to obtain

B8)
At

(he

that the
approximation

derivative df/dx
to

nseiats x/eF < 0.01,and we see from Figure 7.5

only at energies near er. It is a goodapproxiof orbitais <O(e) at sf and take it outside
of the

of interest in

lures

tempera

the

evaluate

is

large

density

integral:

Ccl S

Examinationof
suggests

that

potential ji
constant

the

when t
in

cF. We

the

graphs
\302\253
we
\302\243f

Fermi-Dtrac

B9)
hi

Figures

ignore

the

7.7 of the variation of/i with x

temperature
dependence of thechemica!
7.6 and

distribution

function

and

replace ;i

by

the

have then:

C0)

7;

Chapter

thai

;i is

calculated
for the

Gas

of she

free electron Fermi

and three dimensions. In common
a= 0.01 at room (empcraiure, so

potential

gasesin one
meials t/nF

and Bost

with temperature

V&riaiiors

1.1

Figure
chemical

Ftrmi

ji, for

lo cF.Thesecurves
expansions of the

closely equal
from series

number of particles in

ihe

were
integral

system.

We set

x a
follows

and

it

We

may

from

safely

B9) and

C0)

replace the

(e.- e,)/t ,
\"

that

lower limit

integrand is already negligibleat

such that cF/x -~ f 00
temperatures

by

x = -ef/r
or

more.

The

inicgta!

is not

demciuary,

but

may

p,

ondilTeremhuion

of bsjih

sides uiih

rcspcci

be cvafua^d

-V

lo ihc

if

are

we

The integral*

+ iI

\342\200\242

because

-co

from ihe
it2

parameter a.

the factor
concerned

becomes

Heat Capacity
we have for

whence

she heat capacityof an

when

gas,

\302\253

xf,

C4)

units,

C5)

Ctl
of orbitajs at the

the density

that

found

We

\302\253(\302\243,)

electron

free

for

if

is not

For r

gas,

the temperature
\302\253
xF

Gas

'

- WUEfU.

Cel

In conventional

electron

Electron

of

the

with

xF

eF. Do

06)

not be deceivedby

gas, hut

for r

is degenerate;

gas

= 3iV/2tf

3N/lcf

ofthe Fermi

Fermi energy i,

only

\302\273

if

(he

reference

a convenient

is in the

gas

notation

the

rF:

point.

classical regime.

Thus C4) becomes

C7)
in

units

conventional

there

is an

extra factor kBl

so

that

C8)

C\\,

where

A'flTF

sF. Again,

TF is

but
not an actual temperature,

only

a reference

point.

We can give a

physical explanationof the

form

of

the

result

{37). When the

those
electrons
in states within
specimen is heatedfrom absolutezero,chiefly
because
an energy range r ofthe Fermi level
are
excited
the FD
thermally,
over
a region
distribution function is affected
of the order of r in width, illusisofthe order
illustrated
electrons
7.3 and 7.5. Thus the number ofexcited
by Figures
r. The
of A'i/\302\243F, and
each
of these has its energy increasedapproximately
by
as
total electronic
thermal energy is thereforeofthe order
of Uci
Ni2/eF. Thus
the electronic contributionto the heat capacityis given
by

C9)

A'r/rF

is directly

which
with

the

experimental

proportional to t,
results.

in

agreement

with

the exact

result C4)

and

Chapter 7:

Bos

and

Fctmi

Fermi energy parameters for

Cuiculaied

Table l.\\

free

eleciroi

Comiuciion

Fermi

eieclron

concemralion

NiV.

of

1.1

3.S

K
Rb

1.34

0.85

2t

2.4

1.0S

0.79

1.8

0.56

2.1

Cs
Cu

0.73

1.5

8.50

1.56

Ag

5.76

1.38

Au

5.90

1.39

7.0
5.5
5.5

the

4.7

and copper, silver,and

64
6.4

electron per

valence

one

have

gold

the conduction

becomes

electron

valence

the

electron in

the

metal.

of conduction electrons is equa! to the concentration

the
be
evaluated eilher from
and ihc atomic
densiiy
may

concentration
which

lattice
dimensions.
weight or from the crystal
If the conduction electronsact as a free
eF

1.8
8.2

In Metals

atoms,

energy

5.5 x 10J
3.7

2.5

10\"

[. k,

inK

4.6

atom, and
Thus

1.3 x

x 10\"

T., =

in eV
\302\243F,

Na

alkali metals

The

s~'

SV, in cm

cm'3

in

iempcratur

energy

Li

Gas

Fermi

Velocity

Fermi

gas,

the value

of she Fermi

from G):

be calculated

may

fermion

ef = {hl12m)Cn2uI!\\

Valuesof

vF at

velocity
kinetic

the

given in Table

ef are

of

and

surface is also given

equal to ef:

is

^ttuy3

where
eFjkB

nt is
for

\302\253
TF

the mass of the

in

it is

defined so that

HO

.
\302\243f

of (he

Fermi \\emperatureTF ~

the order of 5 x l04K,so that

(he derivation of C5) is an excellent
approxima(ion

The heat capacity of

Sow

\\ab!e;

electron

are of

the

assumption
at

room

and below.

temperature

the sum of

(he

tn

values

The

electron.

metals

ordinary
used

7.1 and in Figure 7.8.The

the Fermi

energy

D0)

an

temperatures

many

electronic

the sum

constant

at

metals

and

contribution

a lattice

volume

may be written

as

vibration contribution. At

has the form

Cv

yi

+ At3

D2)

Na

a functio
Rb

monovaienl mclals. The siraighl line is dra

whh iiin
!brEf ^ 5.835 x 10\023'n1/J
ergs,

Eleciron

Figure 7.9
TK

After

where

from C7),

capacity

Lien and N.

E. PhiJHps,

A are

Ii is

helpful

10\302\260

in cm~3

concentration,

values
Phys.

characteristic

constants

for polnssium, plolled as

133, AI37O A964}.

to

display

as a plot

and

of the material. Here y

is dominant

the experimental

discussed

at sufficiently

values of the

in

Chapter

jn2N/iF

4, The

iow temperatures.

heat capacity for a given

of Cvjx versus t2:

Cy/t

y + Ax2

The intercept
the points should lieon a straight
line.
the value of y. Such a plot is shownfor potassium
in
7.9.
Figure
of y are given in Tables 7.2 and 7.3.

for then

C/Tv

Rev.

and the lattice vibration term-4i3was

electronic term is linear in

material

Expcrimcnlalheal

W. H.

and

10\"

D3)
at t
Observed

\342\200\224
0

gives

values

7.2

Table
heat

of monovalent

capacities

eteciron eSecironic

and free

Experiment!

metals
e electron},

Cexp),

mJmol\"'K\"

y/y0

Li

1.63

0.75

2.17

Na

1.38

1.14

1.21

2.08

1.23

Rb

2.41

1.69

1.22

Cu

3.20
0.695

197
2.36

0.50

1.39

Ag

0.646

0.65

Au

0.729

0.65

Cs

1.35

1.00

1.13

The values of \342\226\240/

nud yo arc in i
iUlU u: Oluilcsy
of N. li. 1'hillim.

oni:

Table

7.3

values of

ExpenmenUt

Li

Be

1.63

0.17

Na

mb

declronic heat capaciiy consiain

y of

mcials

I Al

1.38 1.3
K
Ca
2.08 2.9
Rb

Sr

Cr

9.26

t.40 9.2

2r

Nb

Mo

2.80

7.79

2.0

Sc

Ti

107

3.35

10.2

\021

Mr

Cs

Ba

La

Ht

T*

2.7

10.

2.16

5.9

1.3

value of y

Cu
0.695

Ni

4.73

Tc

3.6

sOTE;Thc

Si

Gc

As

1.35

2.41

[3.20

7.02

Zn

Cra

0.64

0.596

In

Rh

P<!

Ae

4.9

9.42

0.646

0.638 1.69

Re

lr

Pt

Au

He

2.3

3.1

6.8

0.729

0.19

Tl

1.79 1.47

Sn

Sb

1.78

0.11

jpb

Bi

2.98 o.oos

is in
,s

fuiniihed

White Dwarf
White

dwarf

by R

Phillips

and

N. Pear

Stars
have

slars

masses

comparable

to

that

of

the

mass and

The

Sun.

radius of Itic Sun arc

Q

2.0

x 10!3

g;

Ko = 7.0 x

dwarfs are very small, perhaps

of
the
which
is a normal star, is of the
Sun,
density
of water on the Earth. The densitiesof white
dwarfs
The

radii

of white

10'\302\260cm.

O.Oi
order

are

of the

that
of

D4)

gem\023,

exceedingly

Sun. The
like

that

high, of

the

White

are

107gem\023.

oflO'1 to

order

into

ionized

entirely

degenerategas,as
Besselobserved

that

its predicted

2.0 x

3O33

estimated

as 2

radiant

energy

in

shown

below.

the

of the

path

dwarf

white

and the electron gas is a

In 1844

discovered.

to be

star Siritis oscillatedslightly

a straight

about

x 109cm by a
flux,

comparison of the

the

using

surface

of thermal

properties

temperature

ts

the

and

radiant energy developed

4.

Chapter

mass and

The

and

dwarfs

prevalent in white

invisible companion.The companion, SiriusB,was discovered

position by Clark in 1862.ThemassofSiri us B was determined
on the orbits. The radius of Sirius B
g by measurements

lincasifithadan

to be

free electrons,

nuclei

of Sinus was the first

The companion

near

be

will

the densities

under

Atoms

Stars

Dwarf

radius of Sirius B

to

lc;id

the mean

density

D5)

This extraordinarilyhigh
following words; \"Apart
reason

particular

times

100

atoms at a

10~6A3peratom.
order of 0.01 A, as

molecule

electrons
form

graviiational

In

the

temperature

the
no

dwarfs

white

has a mean

density

a volume

10\" atoms

The average

per

atom

equal

\\o

iO~30cni3pcratorn

mol\021)

nearest-neighbor separation is ihen

of

of 0.74 A in a
separation
compared with the internuclcar
atomic
the
of hydrogen. Under conditions of such high
density
ionized
are
electrons
The
are no longer attachedto individual
nuclei.
is held togetherby
in
dwarfs
an
electron
matter
the
white
gas. The
which is the binding forcein all stars.
attraction,
the
interior
of white
dwarf stars* the electron gas is degenerate;
The
Fermi
is much
less than the Fermi energy
energy of au
ef.

cr *

discussion
\302\243ood

WinHon,

No. 2

density of 106gcni~3have

electron gas at a concentration

of 1

'

Other

suspicion.\"

Maanen

=s

(I06molcm\023){6

and

Van

named

the

incredibility

the calculation with

that

by Eddington in 1926 in
of the result, there was

appraised

higher.

Hydrogen

or

the

from

to view

densities;

have higher

was

density

1973.

as
(h2/2i}i){3n2nI13

of while

dwaif siais

is

0.5

given

is given

103Oelcetronscm~3

10~6erg

by W. K

as i

x 10s eV

Rose, Aitropkvsics,

Hotf.

by
,

D6)

characierisiic

Liquid

energy of

Fermi

7.4

\"able

of mailer

Particles

3Hc

atoms

Metal
dwarf stars

While

degenerate fsmiion

values)

Tf, in

0.3

demons

electrons

\302\253
!09

Nuclear

matter

nuctcons

Ncujron

stars

neutrons

tQ1

3 x \302\2730u
3 x 10!I

about 10' higher than in a typieal metal. The Fermi temperature zFikB of the
m the interior
electrons
is =s 3 x 109K, as in Table
7,4. The actual temperature
of a while dwarf
be
order
I0\021
K.
The
is believed
of
the
of
electron
to
gas in the
interior of a white dwarf is highly
because
the thermal energy is much
degenerate

lower

Fermi

the

than

energy.

energies in the relativistie regime?This question arises

because
our
nonrelativistic
of the Fermi gas has used the
theory
expression
the
an
kinetic
electronof
momentum
The
energy
p2/2m for
p.
equienergy of
equivalence of the rest mass of an electronis
the electron

Are

\302\243Q

This

will

\302\273
A

of

is

energy

effects

me2

* 1.

x I010cins-!):

10\"\"g)C

D7)

order as the Fermi energy D6).Thus

relativistic
densities
but not dominant. At higher
the Fermi gas

same

the

be significant,

is reiativistic.

NuelearMatter
We

which

state

the

consider

matter

nuclear

of matter

within nuclei.

is composed

qualiiaiively. We

estimate

here

of a

contains

A nucleons

that

nucleus

Accordingto
volume

goes

b nuclear

this

relation

as R3,

the

gas, at

fermton

degenerate

of

least

energy of

x Al!\\

x ltT13cm)

average

protons

tbenucleongas;The radius
is given by the empirical relation

the Fermi

A.3

form

The neutronsand

volume

which is proportional to

per particle
A.

The

D8)
is constant,for the
of nucleons

concentration

matter is
?

0.11

x 1039cm-3

D9)

Potential

Chemical

about

103 times higher than

Star.Neutrons
the neutronsneed
and

concentration
of

one

protons
not

not

the

Fermi

equal

Absolute

in a

white dwarf

particles. The Fermi energy of

energy of the protons. The concentra-

identical

are

oilier, but not

Or the

of nudeons

concentration

the

Zero

Near

both, enters the

familiar

relation

E0)

\302\243,=\342\204\242C>r'\302\273)M

let
simplicity
number
of neutrons.
For

us suppose that the number of protonsis equal

Theit

from D9)

as obtained

a
cm\023
\302\253\342\200\236\302\253\342\200\236\342\200\236(,\302\253

on dividing

\302\243C.17
\302\243f

x 1039

0.05

'W>n>

2. The

by

Fermi

energy is
Mev.

kinetic energy of a particlein a degenerate

Fermi
gas is
is
energy, so that in nuclear matter the averagekineticenergy

The average
Fermi

the

{51}

x 10\024erg \302\253
27

10\023>1/3a;0.43

to

E2)

-J

of

ihe

16 Mev

per nucleon.

BOSON
A very

GAS

remarkable

CONDENSATION

EINSTEIN

AND

effect occurs in

transitiontemperature,
of particles the system will
below

gas

of nonintcmcting

a substantial

which

fraction

bosons at a certain
of the total number

called
occupy the single orbital of lowestenergy,
the orbital of second lowest
the
other
orbital. Any
ground
orbital,
including
the
will be occupied by a relatively
same temperature
at
negligible
energy,
be
number
of particles. The total occupancy of all orbitalswill
always
equal to
the specified number of particlesin the system.
effect ts
The ground-orbital
called the Einstein
condensation.
stale
be nothing surprising to us in this result for the ground
would
There
occ
ccupaney if it were valid only below I(T14K.. This temperature is comparable
in a system
whh
orbitals
the energy spacing between the lowestand next lowest
of volume 1 cm3,as we show below. But the Eitistein condensation temperature
of
for
a gas
of fictitious
noninteracting helium atoms at the observeddensity
most
familiar
is the
is very much higher, about 3K. Helium
helium
liquid
example of Einstein condensationin action.
in

Potential

Chemical

The key

to

the

of a boson

system

Near Absolute

Einstein
at

Zero

condensation
low

temperatures.

is the

behavior of the chemicalpotential

potential is responsible

The chemical

of a large population of particlesin the ground

a
orbital.
system composedof a hrgc number N of nonintcractmg
is at absolute zero all particlesoccupythe
the
bosons.When
lowestsystem
and
orbital
the system is in the state of minimum energy. It is ceriainiy
energy
should
be in the orbital
of lowest
noi surprising dim at i ~ 0 ail particles
We
can show
orbila!
that a substantial fraction remains in the ground
energy.
at low, although experimentally obtainable,leniperaturcs.
our energy
on
If we
scale, then
put the energy of the ground orbital at zero
from the Bose-Einstein distribution function
for

the

stabilization

apparent

We consider

<53)

the occupancy

e obtain

i\342\226\240-+
0 the

When

Here

we

have

dial

know

the total

made

.v, which

in the

use

ground orbital at e =

of the

occupancy

of particles

number

of the

0as

ground orbital becomesequal to the

total

system, so ihal

of the

*s
series expansion cxp{\342\200\224
x)

hji/x, must be smallin

wiih

comparison

number of particles N could not

be

large.

unity,

From

x +

\342\226\240
\342\200\242
\342\200\242.
We

for otherwise

this result

we

find

E5)

asT

ForN = 1022at

-.0.

T = IK,

we

have

/i

-1.4 x lO'38 erg.We

noic

that

fromE5)

E6)

as i

~+

0.

The

chemical

energy than the ground

b\302\243
non-nesative.

potential

in a

boson system must

state orbiral, in order

tirar

rhc

occupancy

always

be

of every

lower

in

orbital

Cxampte;Spacingoflonat

of an atom free to move

where

n,,

n>4

are
\302\273,

integers.

positive

of free

('

of volume

a cube

in

ttrbiiuh

lowest

second

and

orbital

=\302\273
/-1

The energy e(I 11)of

the

energy

eB1 i)

of one of

set of

the

atoms. The

Zcr

of

energy

an

is

orbital

lowest

ihe

is

E8)

1) ,

+ 1 +

ind

Near Absolute

Potential

Chemical

next lowest orbitais is

E9)

+ 1+1).
W

energy of

excitation

lowest

The

is

atom

the

As =*\302\243BH)e(III)

lfA/{4tie}

- 6.6 x lO'^gandi, =
= C){8.4

Ae

In

is extremely

spiining

ijtK,

iO\0211

closer to

/i]/r}

is

\342\200\224

F0)

cm,

= 2.4S x

NT30erg.

F1)

- 1.S0x KT1*K.
small,

tiiRtcuU to

it is

conceive that

it can play unimportant

accessible
temperatures such as
reasonably
I mK
{55} gives )i ^ -1.4 x
temperature
zero
of energy.Titus /i is
orbital
ES) as the
than is the nexl lowest orbital E9), and cxp{[t(J 11)dominates
the disso that t(Ill)
ap{[t[2li}~n\\h}t

and

ntucit

the

orbjia!

ground

closer

io

than

is

function.

distribution

Boltnnann

factor

exp{~A\302\243/i)

exp(-1.8
which is essentially unity.
would
first excited orbit;il
gi\\cs

physical problem even at the lovvest

is I0\021 K. However, at the
whicli
= \\0:i aiouts, referred to the
for
N
erg

much

The

(-)

x IO-3!)(9,S6)

in a

part
1

Ae/*8

units,

temperature
This

=*

an

entirely

By D)

vuluti

mK.

x 10-\")
we would

is

s I expeel that

1.S

even

I0\0211

\302\253cilte

if/t

F2)

occupancy

of tlie

the
order
However, ihe nosc-Eiiliit-'itidis.tr ibutioii
ofhii;il:
of ihe first exched
for the occupancy

only be of

dilfctcni

at

of 1.

Ae

because

\302\273
p..

of

the occupation

Thus

the

orbiial

exciied

fust

ai

mK

i:

F4)

so thai

the

5 x 10\" 13t

of

which

is very

is [datively

temperatures

simple

low

called

from

thai

are

in this

small. We see thai

the

occupancy

particles
much

very

F2).

lower

in

is

is quiie
in

left

as

orbiial,
in ihe

exciied

be expeciedat

distribution

ihe greatest part of tlie population

The particles in ihe ground
temperatures.
the Bose-Einsicin condensate. The atoms

the atoms

orbital is/.iV
of the first

than would

The Bose-Einstein

in which

situation
are

factor

Boltzmann

cienily

the N

fraction

first

long

condensate

as

iheir

low

oibiialai

from the

sight

strange;

the ground

10i0v 10ir

ii

favors

orbiiai at sufi'lnumber is \302\2731,

act quiie

differently

stales.

excited

do we understand the existence of the condensate?

Suppose ihe aioms were
for holding
distribution (Chapter 4), which
makes
no provision
by ihe Planck
of photons
consiani the loial number
of particles;
instead, the thermal average number
increases wiih temperature ai i\\as found
restricted
ihe
4.1.
If
lav.
s
of
in Problem
the
nature
of photons
loiiil *iumbcr
to *i vliIuc $i we wotild suy thitt the i^rousid orbital of ii\\c plioion
the difference No = S* ~ N(r) between the number aiioued and ihe number
gas contained
excited.
The ,V0 noncxciK'd
tjic
would be described as condensco1
into
thermally
photons
but
becomes
zero
at
such
;ill
,V
a
that
orbital,
A'o
ground
essentially
photons
temperature i,
arc excited. There is no actual
on the totiil
number
of photons;
constraint
however, there
is a constrain! on the total number A' of material bosons,sucli as MIe atoms, in n sysiem.
of the condensation into the ground
The diiTcrctKc
This consiniint is tht' origin
oibiul.
between the Planck distribution
and
the Bosc-Einstein
h
the laner
will
lliat
distribution
of
so
conserve the tot;tl
number
none\\ciicd
(hat
particles, independent of icmperaiurc,
are really in the ground
atoms
ilalc condensate.
How

governed

Orbital Occupancy
We

fora
and

saw

in A9)

VersusTemperature

that the

number of free particle orbitalsper unit

particle of spin zero.The total

exciied orbitals is given
by the

of atoms

number

sum

of the

have

for

/@,t),

integral

in

F6)

the

ground

F6)
the

separated

the

in

occupancies of all orbitals:

N .
We

ofheliutn-4

is

range

energy

number
gives

sum over

of atoms

in

the

number

into
the

two

parts.

ground

of atoms

Here N0(t) has been written

orbital
at temperature t. The

NJ,i) in all excitedorbitals,with

\\

\\
\\r

= 0.5

/(\342\200\242.

-\342\200\224\342\200\224
\342\200\224\342\226\240\342\200\224__

o!

7-10
Plot of Ihe boson distribution
particles present to ensure ). a I. The integral
Figure

slates
arc

gives

condensed

the

funciion

wilh sufficient
two temperatures,
of
times the density
distribution
the rest ofthe particles present
orbitals;
on
value
of No is loo large to be shown
for

ofthe

number
N. of particles in exciied
into the ground slate orbital. The

Hie plot.

The
/(e,i) as the Bose-Einstetndistributionfunction.
integral
gives only the
number of atoms in excited
orbttals
and excludes
the atoms in the ground
=
because
0.
the
function
is zero at e
To count the atoms correctly
orbital,
D(t)
we must count separately the occupancyNa of the orbital
with
e = 0. Although
in a gas of
of No may be very
the
value
large
only a singleorbitalis involved,
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

in energy

at low

to the

temperatures the chemicalpotentialp is very

ground state orbital than

ground state orbital.ThisCloseness

the

population

of

the system

into the

of

p to

the

first

excited

the ground

much

orbital

closer

is to the

orbital loads most of

ground orbital (Figure7.10).

7:

Chapter

Fermi

and Base

Gases

The Bose-Einstein distribution function

when

written

e - 0 is

NM=V^~,
where

as

in

E4),

in

all

excited

or, with

will

orbitals

on

depend

for

the

at

orbilal

F7)

the temperature

x. The numberof particles

as tm:

increases

e/z.

Nolice the facfor

zil2 which

of Nc.
dependence
of
in
Ihe
si ale
low
sufficiently
ground
temperatures
particles
a very large number. EqualionF7) tellsus that / must be very close to
wiUbe
/ is very accurately constant, becausea macwhenever
1. Then
unity
No is \302\273
to
be
for the validity
value
of
forces
closeto unity. The condition
/.
macroscopic
;V0
of the calculation is that No \302\273I, and it is not required that Ne\302\253 N, When
to small
g s\302\273
i in the integrand,
deviathe value of the integrandis insensitive
-'
deviations of a from
1 tn F8), although not in F7).
1, so that we can set /.
Ihc

gives

The value of the integral*in

The

temperature

the number

At

infiniic

= U1 10
>\342\226\240

gi

F8)

is, when

). =

1,

it ton

Thus ihe numberof atomsin

ts

states

excited

Temperature

\\.IO6VB\\H\\3;:i

..

G0)

where

/iQ

N to

(Af r/2rr/i2)a/2

is again the quantum

obtain the fractionof atomsin

=

N./N

The

value

We

concentration.

divide

Nf by

orbitals:

excited

2.6l2nqV/N

G1)

2.6l2na,'n.

which
fed to G!) is valid as long as a large
\\/N
are in the ground state. A!I particles
have
to be in some
in an excited orbital or in the ground
The number in
orbital=

or

\342\200\224

of atoms

number

either

orbital,

to small
excited Orbitais is relatively
insensitive
changes in X. but the rest of
this
we must
take /.
tlie particles have to be in the ground orbital.To assure
very close to 1 as long as NQ is a large number. Even 103 is a large numberfor
Yet witliin
ihc occupancyof an orbital.
Ar/rE = 10\"fi of the transition,where
is > !015 a loins
is defined
orbilal
r\302\243
by {72) below, [he occupancy of the ground
at the concentration
of liquid 4He. Thus our argument
is highly
cm\023
accurate

at

Ar/r\302\243

10~5.

Condensation

Einstein
We

Ihe

define

Tcmperaiure
condensation

Einstein

number of aionis in

which the

atoms.

That

is,

A^frJ

\302\253
N.

temperature*
states

excited

Above

ilie
r\302\243

as

i\302\243

for

(cmperaiure

total number of
of the ground orbital is
is macroscopic. From G0)

is equal

occupancy

(he

to (he

not a macroscopicnumber;below
n the occupancy
A7 for Ne we find for the condensation temperature
witli

G2)

M \\2.6I2k
Now

Gt)

rimy

be written

as

G3)

wlicrc

is

v;irtes ;is

ii:2 a I

jV

value

of

tlic

tola!

Atademic

of atoms.
below

Ictuperiitures

T^foralomsof

in,

number
4Hc

The numberofatoms

if;, as

sliown in Figure

in

excited

orNuils

7.11. Tlic uik'iilaled

is a=3 K.

dcr W'issenschaficn,

Berlin, Siuunesbcricliie 152-1,261;1925.3.

aid

Fermi

7:

Chapter

Hose G:

1.0
\"n

0.8
\\

Superfluid

component'

\\

/
ormal

flui

\\

omponen

/
y

of the
of

ihc

i.o

0.8

gas: tempcraiuce dependence

in ihe ground orbiial and
of aloms in all exciled orbilals. We
boson

Condensed

Figure7\302\273tl

\\|

0,6

0.4

0.2

proportion

No/N

pfoponion

NJN

ofaioms

as normal and superftuid

have labeledihe two components
wilh the cusiomary description of liquid
!o agree
helium.
arc intended
!o be zero at
The slopes of all Hucc curves

The

number

of particles
No

that

note

We

N may

the

in

have

phase

said

or the

that

be

the particles in

in the

ground

temperature

VM

is

G4)

even

slightly

the ground orbitalbelowt

in

is given

k'elvin

the

molar

volume

in cm3

For liquid helium Vu~ 27.6cm3

mol\021

mol\021

and

less

than te

orbital, as we see in Figure7.11.

M)

where

from {73):

form

superfluid phase.

The condensation

= 0.

{x/x\302\243?ir\\.

be of the order of 102\\Forx

large numberof particleswill

We

- Ne =
N[l

is found

orbital

ground

and

by the

the

condensed

numerical relation
G5)

= 4;

is the

molecular

weight.

thus TE = 3.1K.

Liquid4

Liquid

He

4He

tempera! ure of 3 K is suggesiivelycloselo j he actual tempera Jure

a! whicha transitionlo a new stale of matter is observed to Jakeplace
in
helium
liquid
(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
of a gas to a liquid. Evidently
ihe
iit the condensation
j'nicrspace that occurs
of4Heat 4.2 K under a pressure of
alomic
forces that lead to ihe liquefaction
one atmosphereare too weak
to destroy
the major effects of the boson concondensation
at 2.17 K. In this respect tlte liquid behavesas a gas.
The
condensaof bosons.
condensation
into
the ground
orbital is certainly connected with
the
properties

The calculated

of 2.17K

2.5

2.0
\"\302\253,

t.o

0.5

1.6 1.8 2.0

u;

Tempera!

Heat capacity

Figure 7.12

peak near

2.17

K is

of

liquid

evidence of an

*He. The

vanishingly

viscosity

by rate
small,

above

of flow

through

sharp
transition

important

nature of the liquid. The viscosity

above the transition temperature is typical
liquids, whereas the viscosity belowtlic
in the

determined

of

the liquid
of normal

merely becauseof
et al.

as

transition

narrow

slits is

at least I06 times smaller than

the transition. The transition
is

called a lambda transition

of the graph. After
Kccsom

2.6

2.4

2.2

tlte

the

often
shape

Chapter It Fermi

is normally not

condensation

The

Gases

Base

twd

may act as bosons,as in

in metals. A

different

superconductivity

type

of transition

been observed

has

properties

permitted for

the

in

but

fennions,

of electron

to complex

of fermions

pairs (Cooper

phases

with

pairs)

superflutd

Atoms of

3mK.

below

3He

liquid

pairs

3He have

of 5Hc atomsact as bosons.

can
several
of liquid
as a
in support of our view
helium
give
arguments
of
this
is
a
drastic
A
t
first
oversimplification
sight
gas
noninteracling particles.
of fite problem,
bur
there
are some important features of liquid helium for
are fermions,

\\ and

spin

but pairs

We

the

which

is correct.

view

{a) The molar volume

absolute zero is 3.1 timesthe volume

[hat we calculate
from
the known interactions of helium atoms.Titeinteraction
between
forces
of helium atoms are we!!known
aud
pairs
experimentally
and from these forces by standard
methods
of solid
theoreticaily,
elementary
state physics we can calculate
the equilibrium
volume of a static lattice of
to be 9 cm3
helium
atoms.
In a typical
volume
calculation we find the molar

mo!~', as
the

atoms

helium

tn

structure

expanded

distances.

appreciable

responsible
for

the

liquid

4He at

mo!\"l. Thus the kineticmotion

leads to an exhas a large elTccton ihe liquid
siale
and
which
the aloms to a certain extentcan move freely
over
motion
We can say ihat ihe quantum zero-point
is

with

compared

of

of

the

27.6 cm3

observed

volume.

of ifie inoiar

expansion

ofliquid helium in ihe normal state are not very

(b) The transport properties
a
ihosc of
normal classical gas. In particular,the ratio
of the
different
from
thermal conductivity K to the product ofthe \\iscosity
heat
times
the
tj
capacity
per unit mass has the values
~_

JC__
JJCV

[3.2,

These vaiues are quite closeto

ihose

The

values

Table

temperature\342\200\224see
selvesin

gas

the

at the

liqirid

14.3-

are with

same denstly.

in

an

at

2.SK

at

4.0 K

|16,

for

observed

order

Normal liquids

of

gases

at

room

the transport coefficientslliem-

of magnitude
act

normal

quite

of those

calculated

for

the

differently.

are relalively weak, and I be liquid

does not exist
(c) The forces in [he liquid
above the critical temperaiureof 5.2K, which is itie maximum boiling pouit
ten limes stronger in Ihe
observed. The binding
vvotiki
be perhaps
energy
:i
si:uic lull ice, hul the expansion
of ilte molar
of
equilibriumconfijjuralion
volumeby the quanlum
motion of the atoms is responsiblefor tile
zero-poml
The value of ihe critical
value.
reduction
in the binding energy to the observed

io binding energy.
iemperaliireis dirccliyproportional
(d) The ikjuid is slablc at absolutezero
pressures
25 aim the solid is more stable.
the

ai

muter

25atnt;

nbuvc

'He

Liquid

1
as

g
I

T,
Fi\302\253iire7.13

Comparison

uuder

4He

iiqujd

onset of high

gravify

fluidify

in

K-

of rales of flow
through a fine

and B.M.

3He and

of liquid
hole.

Abraham,

fhc suddcr

Noiice

in \"He. After

or superfluidity

B. Weinsiock,

Osborne,

'lie

r'Hz

\\

D.

Pliys.

W.

Rev.75,

9S8 A949).

The new stale of ntallcr

2.17

has

K.

quhe

inio

asionishing

which

liquid

4He enters

The viscosity

properlies.

when cooled beiow

as measuredin

flow

is
zero (Figure 7J3), and the [hernia!
conduciiviiy
is
a
supervery high. We say thai liquid 4He below Ihe [ransilion icmperalure
fluid.
we
More
denole
*He
below
ihe
transiUon
lempcralurc
precisely,
liquid
as liquid
and
He U, and we say llial liquid
He II is a mixlurc of normal Huid
of
Hie
helium
Tlte normal fluid component consisfs
Supcriiuid
coniponcnls.
of
consisis
aloms
excited
in thermally
orbiials, and the superfluid
component
life helium atoms condensed into the
orbital.
It is known lhat liie
ground
tat:e
in Ihe
in liquid 4He does not
radioacljve boson 6He in solution
part
in
3Hc
in solution
supijrflow of the latter; neither, of course,doesthe fermion
4llc kike part in ihe super/low.
We speak of liquid \"Mle
as liquid ik i.
;ihovc
liie
iransilion
leniper^lnrc
Thereis no supcrdnid
in Ikjuid
lie 1, for here the grama! oihii;il
coiliponcnt
of uKiyuiiude as ihe oct.'up:mt;y
is ucgti^ihlc,
order
ot-vupiuicy
being uf l\\ic suim:

experiment*

fliii.ls

ofiliirftciil

Bic.isufi;

is essenlially

visttiMlics,

the .ivct.igc of

K'ii,

sums
i)f 'be

c\\fKfinn:liii

aierjgt*

iiicisuic
lluidiiy.

ifJiraif(Jj;t;

i imnily.

.t\302\273Juliet

l'vjil'Ijjjk'j

Kjurc

7.14

The mcUing

curve of liquid

and

helium (*Hc). and the transition

curve
between itie two forms oftiquid
He I
helium,
and He II. The liquid
He ll form exhibits
solid

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

this gcaph

boiling

curve is

as ii would

pressuic line.After
19,626E950).

C.

in

included

not

[he zcco

wjih

ractgc

Phys. lev.

A. Swenson,

of any other

in which

temperature

liquid

seen. The

we have

as

orbital,

low-iying

He { and

({ exisl are shown

regions of pressureand
in

7,14.

Figure

The development of superftuid propertiesis no[ an automatic

consequence
A
dvanced
of [he Einstein condensation of aloms into the ground orbira!.
interaction

aloms

among

aloms

[he

existence of some form (almost

form) of interany
[hat leads [o the development of superfluid properties in
in the ground orbital.

that il is [he

show

calculations

cal-

condensed

Phase Relationsof Helium

The

phase

of

diagram

4He

was shown

can be followed

from

any appearance

of the solid. Al

called He I, makes
II.

He

A temperature

Ihe

transit

ion

called

the/

in

Figure

poinl of 5.2 K

crilical

ihe

transilion

to the

The

7.14.
down

to

discussion of solid heli

1967, pp. 85-95. Solid 'He

An tnlercsring

August

poinl is the triple point al which

by B. Bertram and
in three crysral structures

is given

:xisis

curve
without

liquid,
form wilh superfluid properties,called

who
first solidified
and vapor coexist.Keesom,
the solid* did not existbeiowa pressureof 25alm.Another

can,

zero

Ihe normal

temperature

liquid He ii,

\342\200\242

iiquid-vapor

absoiule

hciium,
triple

R. A.

liquid

He

point

exists

Guyed Scientific Am
ro rhc condili

according

(,

found that

'He

of Helium

/
Solid

\342\226\240i

Liquid

40

Gas

7.15

Figure

Pliase

kelvin and (b) in

slopeshown
a

in (a)

'he

lo

for

liquid

In rhc

on ihc phase boundary

liie liquid, and we

liquid io

[he

has

soiid

have io add

it. Superfluid

solidify

(a) in

3He,

region of negaiive

ihan

eniropy

higher

heal

diagrams

miKikeivin.

properiics

JHc.
The
appear in(b) in ihc A and B phases of liquid
A phase is double\342\200\224in a magnetic
field [lie phase divides
imo
hvo componenls
wiih opposiie nuclear magnciic
momenis.

at

K:

1.743

He I and
regions

here the

He II.The

of existence

The
of4He.

Figure

negaiive

two

7.15

slope

triple

of He
of

phasediagram

ihe

soiid is in equilibriumwiih

3He

exhibiis

of ihe

poinis

are connecicd

II and He I.
differs

in a

ihe

iwo

by a

liquid

modifications.

line !ha!separatesihe

remarkable way from the phasediagram

of ihe fermion nature of 3He.Note

the importance

coexistence curve at low temperatures.As

explained

in

negative slope means thai

10, the

Chapter

ISlower lhan !heentropy

the

purposes

many

!hc

ground orbila! by
when

only

laboratory reference frame\342\200\224as

Ilie

when

supcrfluid
for the

energy,

superfluidhas energy
to tlic

relative

a velocity

is set

superfltiid

of the

atoms

exeitation

superfluid is given

of the

of mass

center

he

No

energy. The

no excitation

has

definition

il behaves as

of liquid helium

component

superfluid

were

it

liquid phase

phase.

a vacuum,
as ifi! were not thereat all.The
are condensed into the groundorbila!and have no
if

of! he

entropy

and Superfluidity, 4He

Qunsipariieies

For

solid

the

of

inlo

to

relative

flow

the laboratory.

component of Na

The condensed

as

flow

the

in tile

cxcitatiosis

ereate

not

does

atoms make transitions bctwecilthe

Such iransitions might

in

irregularities

the

The

transitions,

loss

from

can

occur.

of the

wall

the

relationshipof

and the

superfluidity

excitations

free

between the energy e and

show

that

superfluidity

of helium

atoms

cause of energy loss and

the

is

flow

!!. If

resistanceless

not

the

involves

He

in liquid

orbilais of freeatoms,with

so

is,

as no

long

orbitals.

with

irregu-

tube through which the helium atoms are Rowing.

the moving fluid,

The criterion for

viseosity so long

!ho excited

and

orbital

ground

occur, are a

if they

with zero

superfluid\342\200\224that

by collisions

caused

be

flow

will

atoms

collisions

such

were

orbitals

excited

the

if

relationreally like the

Momentum

and

energy

momentum

of

relation

parliele

= -_(/,/,-)*

l\\.ivi

Mo

momentum

G6)

or /ik

Here
would not be expected.

of an atom,
k =

then

we

can

But

^/wavelength.

atoms
the low energy
the
bceause of the existence of interactions between
but are longitudinal sound
excitations do not resemblefree particle
excitations,
waves, longitudinalphonons(Chapter4).After all, it is not unreasonable that a
in any liquid, even though we have
longitudinal sound wave should
propagate
no
A

of

has

language

many

of superliquids,

experience

previous

grown

These

atoms.

up to

describe the low-lyingexciiedstatesofa

slates are called elementary

excitations

articles.
particie aspect the states are called
the elementary excitations of liquid He II.
shall

Longitudinal

(jiiasip

We

menial evidence
superfluidity.

This

for

condition

this,

but

will

first

show

elementary excitations leads to the

we derive

us
superfluid

wiiy

give

and

phonons

the clear-cut

a necessary conditionfor
the

phonon-tfke

behavior

of liquid

system

in their

nature

He II.

are

experisuper-

of the

Quaupanhlts andSuptrJluMty,

V down

velocity

He

Body of mass Mo
a cylinder th;it
at absolute zero.
7. [$

Figure
\342\226\240\342\200\242a

'lie

It

a steel ball or a neutron, of

with
V
mass
down
a column
of liquid helium aJ rest at
falling
Mo
velocity
absolute zero,so that initially
are excited, if the
no
excitations
elementary
Jhere will be a damping
nioliou of the body generates
excitations,
elementary
forceon Jhe body, in order to generate an elementary excitation of energy ck
alid
momentum
hk, we must satisfy the law of conservationof energy:
We consider

in

Figure

7.16

\\M0V2

where

V is

Furthermore,

a body,

*=

perhaps

|A/0F'2

the velocity of the body after creationof the elementary

we must sarisfy the law of conservation
of momentum
=

Ma\\\"

conservation taws cannot always

direction
of Jhe excitation
created in

the

hk.

The two
if

G7)

,
\302\243k

be
the

satisfied
process

excitation.

(IS)
at the

same time even

is unrestricted.

To show

7; Fermi

Chapter

and Base Gases

this we rewrite G8)as

A/0V

and lake the

On multiplication

by

Af0V

we

l/2Af0

G9)

from

+ h2k2

2A/0/iV-k

/V

|A-/K2

subtract

square of boihsides:
M02V2

We

G7) to

= MQ2V'2.

have

k +

\\M0V'\\

G9)

obtain
'

\342\226\240

(SO)
2mTq

V for
this
lowest value of the magnitudeof the velocity
which
will occur
when the direction of k
value
equation can be satisfied.The lowest
is parallel
to that of V. This critical velocity
is given
by

There is a

-h2k2
Vs

The conditionis a
become

very

large,

little

minimum

simpler

of-

(81)
if we let the

to express

mass Mo of the body

for then

(82)

body

with

moving

in the liquid,so that

to

be zero.

body

a lower
the

velocity than

motion

moving

will be
with

Vc

will

not

be able

to create

resistance less. The viscosity

higher

velocity

will encounter

excitations
will

appear

resistance

and

Quusipartfctes

*lle

Superfluidity,

from below. The slopeof this line is equal to the critical velocity, if
as for the esciiation of a free atom, [he straight line has zero
h2k2/2M,

the curve
ck

s=

slope

crilical

the

and

Free atoms:

The

Vs

of

energy

is zero:

velocity

a low

minimum

phonon

energy

frequencyregionofsound
is equal to
of sound
velocity
product of vs

Phonons:

The

wavevector

the

times

Vc

He

liquid

the

t'a, or

the

to [he

in

where

waves

= 0.

oUik/2M

product

II is

(83}
=

\302\243k

tui>k =

of wavelcnglh

tusk in [lie
and frequency

where the circular frequency mk

k. Now the critical velocity
is

= minimum

is

equal

= v,.

offtr^/hk

(84)

velocity of sound if (84} is valid for ;ill

wavcveciors, which it is not in liquid helium ii. The observed criticalflow
arc indeed
velocities
nonzero, but considerably lower than the velocity of sound
and
lower
than the solid straight line in Figure
7.i 7, presumably
beeause
usually
the plot of Ek versus lik may turn downward at very high hk.
The actual spectrum of elementary excitationsin liquid
helium
II has been
of
slow
neutrons.
determined by the observations on the inelastic
scattering
7.17. The solid straight line is the
The experimentalresultsareshown
in Figure
Landau
for the range of wavevectots coveredby the neutron
critical
velocity
and
for
this
line the critieal velocity
is
experiments,
critical

Vc is

velocity

Vc

A and k0

where

ions

Charged

\302\253

&/hk0

5 x

arc identified on the figure.

of helium in solution in
of

conditions

experimental

to the

equal

pressure

and

I03 cm

closely
conditions

motion

the

of

temperature

Sueh vortex rings are transverse

appear

longitudinal

the

(85)

modes

covered

have been observed*to move

*
near
5 x 103 cm s\"
veloeity

modes
by

eertain experi-

11 under

have a limiting drift

value of (85).Underother
the ions is limi(ed at a lower velocity

vortex rings.
in

helium

liquid

free partieles and to

to the calculated
equal

like

almost

s\021

Figure

condi-

experimental

the

by

of

motion

ercation

and

of

do not

7.17.

is more
(84) for a neeessary condition for the critieal
velocity
that
demonstrates
general than the calculation we have given.Our calculation
II
if
He
at
zero
a body
will move whhout resistance through liquid
absolute
at
the velocity V of the body is less than the critieal velocity
Vc. However,
Our

* L.

Meyer

result

and

F. Reif, Phys.

Rev.' 123,727

U96t|;

G. W.

Rajfiekt, Ph)s. Rev.

Lcllcrs

16,934

A966).

in

WavevccioT,

Energy ck versus
in liquid helium ai

7.17

Figure

exciiaiioHS

of 50s

units

cm\021

wavevecior i of elementary
t.JJK. The paraboliccurve

represents the iheoreiicaiiycalculated

helium aioms ai absolutezero. Tlic open circles
lhe otigin

from

free
the

3.0

2-0

1.0

and

energy

momentum

curve has beendrawn

rising

wfili

from

iineariy

of the

exciutions.

measured

rising

for

curve

lo
correspond
A smoosh

Hie broken curve

she tiieorcsiealphonon
brynch
m s\"'. The solid straight
line

ihe poinls.

through

lhe origin is

of sound of 237
gives
uniii:
Ttie
line
imxnin
jh\302\253
vdocily,
gi\\e$
appropri^se
in ihcse expcrimenls. After
ofij/A\" over ihe region of k covered
Hcnshaw
Rev. t2l. 1266A960and A. D. B. Woods.
Phis.

a vclodfy

the crmcai
mum
D.G.

femperutures above
wili be a normal fluid

exciied.The

of

the

body.

fluid

The

supcrflow

component

ihrough a
may

remain

aspect
fine

appears first

lube

behind

the

in
in

lhe

that are

thermally
resistance to the motion
in

experiments

which

side of a container. The

container

component leaks out without resistance.The derivation

there

temperature,

excitations

source of

is the

component

Einstein

the

below

of demcnlary

component

normal

liquid flows out

fluid

absolute zero, but

while
we

have

the

the

normai

superfluid
given of the

critical velocity also holds for

the velocity of the superis the

niass of the fluid. Excitations
A/o
interaction
between the flow of the liquid

this

V as

with

situation,

the tube;

walls of

the

to

relative

fluid

would be createdabove
the
V( by
and any mechanical irregularity in the walls.
of

Phases

Supcrfluid

Three

phases of liquid

superfluid
to

contrast

3He

liquid

3He

transition

4He\342\200\224with

of electrons

slate

surface form a

[he Fermi

known*

be

to

In

in

Uvo

so

of particlesin

type of bound siaie

as

known

a diatomic
like
molecule,
pair is qualitatively
is much larger than the average
iniereleciron
mlerparticle spacing in liquid 3He.

but\342\200\224in

a few milhkelvin.
similar to the super-

qualitatively

where pairs

in metals,

7.15b),

(Figure

of only

temperatures

The superfluid phases are beiieved

superconducting

are

pair. Such a

the radius of the

but
spacing

in

a metal

near

orbiials

a Cooper

molecule

or the

average

[he two electrons [hat form

a Cooper
pair are
3He
the
siates
the
staie.
In
of
nonmagnetic
superfiuid
liquid
(singlet)
spin
aioms [hat form a pair are in the triplet
spin states of the two JHe nuclei,
metallic

superconductivity

ihree

thai

orientations

M,

1, 0,

and

-1, or mixturesof these

both

the

magnetic

magnetic

\302\243nd

been confirmed.

have

properties

The

states.

three

have been explored experimentally,

and

superfluids
superfiuid

corresponding to spin orienta-

are possible,

supcrfiuids

magnetic
~

SUMMARY

1. Comparedto a classicalgas,a

energy,
is zero

in

ground

the

The

ground

state of a free

lota!

kinezic

For

elementary

energy

Wll

roif^s,

Ph

lias high kinetic

heat capacity. The entropy of

The energy of the highest filled
of spin
j is
particle gas of ferniions

in

the

ut\\
ground

see j. C. U heat icy,

311
J. R. Hook,
ii97j|;aritt
PU)sicsfluiic!tn25.
\342\200\242

temperature

slate.

' ~
2,

at low

gas

low

and

pressure,

high

Fermi

the Fermigas
orbiial

\342\226\240
v

stale

is

ly/b.
Physics Today, February
p. i
For
Bulletin
29.
5i3A97SJ.
i%sici
R
\\d
Ph

in

the

Chapter 7:
.3. The

Cases

Base

and

Fermi

density of orbitats at

is

r,f

\"D{Cf)

A. The

heat capacity of an

at r

gas

is

\302\253
i>

units.

in fundamental

5. For a Boscgas at r

fi. The

electron

3,V/2c^.

<

rE

of atoms

fraction

the

temperature of a fj;iS

Einstein condensation

__2nftV

excited

in

of

is

orbitiiis

bosons

nuniiitenicthig

Y>

PROBLEMS

i.

of

Density

of orbiiafs of a

hi one

orh'ttah
free

electron

and

O,(e)
where i.

of area

dimensions,

two

(a)

=\302\273

(t,/rc)t2*rt/Aa\302\243I

is the length of the line,(b)

the density

(86)

in two

thai

Show

that

Show

is

dimension

in une

dimensions,

for a square

A,

\302\251i(e)

^tiii/Tcft2

(87)

independent o(e.

2.
where

of

Energy

in is

refarivistic

the rest

Fentu

For
p is [he momentum.
is of [he
(nh/L),
multiplied
limit, (a)

of

Show [hat

in

energy of a gas ofN electronsis given

zr

this

+ it/

by (n/

form

with

an

energy

is given
by e
volume V = i.3 the

energy

a cube

in

electrons

nonrelativistic

For electrons

gas.

mass of the electron,the

n:2)ll2>

relativistic

extreme

exactly

\302\273
me1,

= pc, where
momentum
as

limit the

for

the

Fermi

by

\302\273

AncCii/n)\025

(88)

Problems

where

the total

(b) Show that

N/V.

(/\342\200\236

The general

problem is
and entropy

3. Pressure
electron

In a

gas

Ireaied

the

in

by

the

(S9)

Fermi

gas.

furPhysik47,542({928).

(a) Show

uniform

that

Notice

\"/.

a -*

Chemical

-a

verms

potential

where

different,

the integral
the behavior

electron

Fermi

temperature.

is upward

*D, is

given

in

for

downward in three dimensions

(Figure
are

that

Fermi

gas

has

orbital
or

to

in the

i!s energy

(b) Kind

l/f/2|J.

region

\302\253

t>.

Oast-0.

of p. versus t

curvature

of

Use entropy

for

expression

gas is

J,Vef.

decrease
of the volume
of a cube every
The
of
is
raised;
to XjL1
energy an orbital proportional
tin

stale uf ihc

ground

exerts a pressure

stale

ground

of

F.Jutlner,Zeilsduifl

degenerate

of

ener\302\273y

Explain graphically why the initial

gas in one dimension and
The C,(e) and *D3(e)
Him:
curves
useful
So set up
t. It wiii be found

fermion

7.7).

Problem

of particles, and to
the
number
N,
of the integrand betweenzerotemperature

for

consider from
and

a finite

the

graphs

temperature.

5. Liquid 3He as a Fermigas. The atom 3He has spin 1 = \\ and is a fermion.
7.1 the Fermi
(a) Calculate as in Table
sphere parameters vF, ef, and TF for
3He at absolute zero, viewed
as a gas of nan interacting fermions. The density
of the liquid
at low temperatures
is 0.081 g cm\" \\ (b) Calculatethe heat capacity
=
T \302\253TF and compare
as observed
with the experimental value
2.89NfcBT
Cr
W. Reese, and J. C. Wheatley,
Rev.
for T < 0.1K by A. C. Anderson,
Fhys.
7.18.
of
of
495
see
also
Excellent
the
130,
properties
A963);
Figure
surveys
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 temThe
Journal
of Physics 36, 181-210A968).
American
temperatures,\"
principles
of refrigerators
12 on
on
3He-*He
mixtures
are
reviewed
based
in Chapter
to 0.01 K.
down
cryogenics; such refrigerators produce steady
temperatures
in

acting

continuously

6. Mass-radius

operation.

relationship for

M and radiusR.Let the

are nondegenerate. Show

self-energyis -GM2jR,
(a)

where

density

is

constant

within'the

white

of mass
protons
order of magnitude of the gravitational
the gravitational
constant. (If the mass
of radius R, the exact
energy is
potential
dwarfs.

be degenerate

electrons

the

that
G

sphere

is

a white dwarf
Consider
the
but nonrelativistic;

Chapter 7: Fermi

and

Sose

Gases

5.0

SO

20
Temperature,

Figure

3He in

7.18

Heat

liquid

*Hc

the

fegion

theoretical

T. Thus for

pure 3Heis
slight slope. The curve

taken
for

gas in the

a Fermi

of C/T

cufves

The curve for

the

percent solution of

3He and of a 5
capacity of liquid
The quansisy plotSed on she vcrSica!

she horizontal axis is

200

$00

in K

at constant

at constant
the solution

axis

is C/T,

and

degenerate temperature

volume

pressure,
of Hie in

are
which

liquid

horizontal.
accounts

4He

fof

indicates

at low
3He sis solution
acts as a Fermi gas; she degenerafe
region
over
to
the
at
temperature goes
higher temperature.
nondegene/ate
region
The
Sine through
she experimental possHsfor the solution
solid
is drawn
if the
hrTf - 0.331K, which agrees with the calculation for free atoms
effective mass is taken as 2.38times
the mass
of an atom of 3He.Curves
J. C. Wlicatley, Amer. J. Physics36 A968).
after

thai she

-3GM2f5R). (b)Showthat
in the

electrons

m is

here

lhai
(;ss

ground

she

gravitational

by ihe

if

order

of magnitude

of the

kiiicsic esiergy of the

mass of a proton, (c) Show

the
same orderof magnitude
and kitsctic energies are of
virsal theo/esiiofsnechanics), Mll3R ~ 10;ogW2cm.{d)Iflhe

she mass

required

the

state is

of an clcclrosiand

Mit

is

the

Figure

Eimtcin

mass is equal to
dwarf?
gas

H ss

(e)
of

believed thai
Show

neuUons.

she value of the

Express

she

Sun

she

of

that

Heal

gas ut

capacity

of

lQ33g), what is the density of the while

ofa colddegenerate
pulsars ate starscomposed
neutron star Mll3R =s 10!7 g\023ciyi. What is
neutron
star with a mass equal so that of the Sim?

tn km.

resuls

7. Photon condensation. Considera science

in which
she
universe
ftclton
The number
number of photonsN is constant,at a concentration
of I0Iocm\"s.
excited
of thermally
we assume is given by the result of Problem4.1,
photons
=
is Ne
2.404 Kt3/*2/] V. Find the criticaltemperature
in
K below
which
which
\342\200\224 will
<
JV.
The
excess
N
of
lowest
be
in
mode
the
jVe
frequency;
Nr
photon
there
is a large
the excess
might be described as a photon condensatein which
concentration of photonsin the lowest mode. In reality there is no such principle
that
loui!
the
number
of photons be constant, hence there is no photon

A1.

sions

heat

Energy,

op.idiy,

;mii

to ;i volume

cn[[opy
V.

ami entropy

capacity,

;is ;i function
Put

of tcmpcf.ifun; in
of ;i
the

y;is

del'milc

o\\

of degenerate bosongas.
the

in

region

dim

ex prcs-

th for the cne-igy. hc;il

of hpiil zero confiiial
bosons
be
not
ion less form; it need
x <

,V noniiilcMlcling

imegnil

Find

ens

The calculated heat capacity above and below r\302\243is

evaluated.
was
in Figure
7.12. The
shown
Figure 7.19. The experimental curve

;tn

cortilam volume.

tot a

that

radius for

B x

7.19

shown

in

dilTcrcnce

7:

Chapter

Gases

and Base

Fermi

between the two curves is marked;It is ascribedlo the

between the atoms,

9. Bosongasin
dimensional

bosons, and show

gas of noninteracting

not converge. This result suggeststlial a

not form in one dimension. Take/. ~ I for

really be treated by

of

white dwarf

Relativhtk

10.

means

of rest mass m
such that the

great

the

the

that

ground

(The

on a finite

The de

momentum.

is the

does

integral

does

should

problem

each
dwarfs are

A' electrons
white

kinetic

relativislic

extreme

have

electrons

onc-

line.)

Consider a Fcrnii gas of

radius R. Conditions in certain
of

for

condensaie

stale

calculation.

over orbitats

a sum

majority

energies e = pc, where

boson

stars.
of

a sphere

in

for Nt{x)

the integral

Calculate

dimension.

one

interactions

of

effect

Broglie relationremains

A1 electrons
of the
ground stale kineticenergy
on the assumption that
pc for ali elecrrons. Treat the sphere as a cube
of equal volume,
viria! theorem argumentto predictthe
(a) Use the standard
of N. Assume
value
that the whole star is ionizedhydrogen,
the
but
neglect
of the
kinetic energy of the protons comparedto that
electrons,
(b) Estimate
the value of N. A careful
treatment
leads not to a single
by Chandrasekhar
value of N, but lo a limil above which a stable while dwarf
cannot
see
exist:
D. D. Claylon, Principlesof stellarevolution
and
McGraw-Hill,
nucleosynthesis,
M1973.
1968, p. 161;
Harwii,Astrophysicat
concepts,
Wi!ey,
).

Inhjp.

2 gives the

Problem

e =

11. Fluctuations

in a

Fcwri gas.

Show

of a

orbisa!

a single

for

fermion

system

that

- <N>A -

<(ANJ>

if

is
\342\226\240GAO

fluciuation

of a

single

orbiial

of

a boson

If

as

</V)

<JV>(I

enough

deep

N ~
in

below

the

the Fermi

<N).
is the

(I!)

system, fhen from

<(ANJ> =

(91)

in thai orbiial. Notice that

number
of fermions
average
vanishes
for orbitals with
energies
= I. By definition, AN
s
thai
<N>
the

energy so
12. Fluctuationsin a Basegas.

<N\302\273

average occupancy

E.83) show iiiat

(92)

<JV\302\273.

are
if fhe occupancy
is large, with <N> \302\273I, ihe fractional
fluctuafions
of the order ofuntty; <(ANJ>/<N>2\302\2531, so mat the actual fluctuations can
Thus

be enormous.It
been
said
that \"bosons
of thrs text has an elementarydiscussion
of

travel

has

13, Chemical

the

potential versusconcentration*

potential versus the number of

for

flocks.\"

fluctuations

Sketch

(a)

particles

in

boson

The

first

edition

of photons.

carefully
gas in

the chemical
volume

at

both classical and quantum

icmpcraiure

r. Include

for a syssem

of fermions.

14.

at

orbitals

with

/x, and the

of

boson

orbilai

Two

(he

Consider

systent.

a system of

0 and e.

particle energies

single

temperature is r.

Find

such,

fegimes. (b) Du

The

chemical

the fhefma!

that

is

twice

rE

spin

same

zero,
is

potential

average population

the population of the orbital

JV 3>
| and make what approximations
are reasonable.
If the atoms
in a gas have integral
spin (counting the sum
and nuclear spins), they
can
form
a boson condensate when the
below the Einstein condensation temperature te given
G2):
by
orbital

lowest

the

of

bosons

A'

the

e.

at

of

Assume
electronic
is cooled

gas

~ BTTh2iM){Ni2.6\\2VJ/\\

For atoms in the vapor phase she Einstein'condensation

is very
temperature
In
Sow because the number densities are very
low\";
A995)
early successful
and elsewhere. Such experiMIT,
experiments were carried out at Boulder,
are
of
which
mark the exciting forefront
the
experiments,
extraordinarily
complex,
field.
A
on
BEC
and
is
literature
on
gas
large
quantum
experiments
theory
the Web.

set of experiments (MIT) started

a beam
of sodium atoms
with
an
of
SO14
oven
at
600K
at
a
N/V
cm\023.
Whas
concentration
exiting
happens
next is the result of a number of clever
with
laser beams directed on
tricks
one pint or another of the beam of atoms. First file atoms are slowed by one
laser bcum from
an
exit
of 800 in jt1 to about
30 in s~'. This is
velocity
slow eiioug.lifor !0!\" ntonis to be trapped within
a
magneto-optical
trap.
of
Fusthcr tricks, including evaporation, reducedthe
the
temperature
gas to
2 /nK, the uhraiow
condensate
was
formed.
The
at
whieli
the
rE
temperature
at rE was again !014atoms/cmJ.
concentration
The atoms in the condensed
are in tlie ground orbital and expand
phase
states
released
the
move
once
from
Giiiy
slowly
trap. The atoms in excited
The
out
of
their
of
the
relatively
steady-state positions.
positions
rapidly
a
asoms can be recorded as a funcsion
laser beam.
of sime
after release, using
One

The

law, G3).
she

of

number

sudden

decreased
condcusase;
orbitals.

With

asoms
this

appearance

in excited
sechnique

of

orbitals

is

in

with

agreement

good

she t3

signasure of Bose'Einssein condensation is

is
a sharp peak of atoms as the
semperature
the

through
rE. The peak comes from
she wings of she line from
light

lighs

scattered

scattered

by
by

atoms

atoms

in

in

excited

the

Chapter

and Work

Heat

OF HEAT

DEFINITION

AND

2-7

WORK

CONVERSION

ENGINES:

HEAT

TRANSFER:

ENTROPY

AND

ENERGY

OF HEAT INTO WORK

2IS

OirnOl

2-S

Inequality

Sources of

252

Irrevcrsibiliiy

233

Refrigeraiors
Heat

and

Condiu'oners

Air

255

Pumps

2?6

Carnot Cycle

Example:Carnol

an

for

Cycle

Idea!

Energy Conversion and the Second

Palh Dependence of Heat and Work

of Thermodynamics

242

Example: Sudden Expansion of an

Gas

245

PRESSURE

245

Ideal

AT CONSTANT

AND WORK

CONSTANT

OR

TEMPERATURE

245

Work

Isothermal

IsobaricHeal

245

Work

and

and Fuel

Elecirolysis

Example:

237
240
240

Work

Irreversible

HEAT

Gas
Law

Cells

Chemical

247
250

Work

Example:

Chemical

Magnetic

Work

Work

and

for an

Ideal Gas

25!
2--

Superconductors

SUMMARY

257

I'UOBLEMS

2?

1.

Heat

2.

Absorption

).

I'lwicm

:::

Pump

4. I leal

2!:<

ReiYigerator

Carnol

6. Room Air

25S

Hnginc

Engine\342\200\224Kel'rigcralor

5. Thermal

Pollution
Condilioner

Cascade

25S

258
258

7. Light

Bulb in a

8. Gcotlierrnal

259

Refrigerator

259

Energy

9.

Cooling

Solid to

of Nonmetallic

10. Irreversible

Expansion

of

a Fermi

T= 0
Gas

259
259

and

Energy

AND

ENERGY

and

of

to a
The

system by thermalcontactwith a
system by a change in the external

The most
the

civilizationis

combustion

physical

conversion

of heat

device to convert heat

of the steam enginegave
Energy

most

because

The

fundamental

da

transfer

it

reservoir

~ dU/x

is accompanied

in external

of

is a

limitations

the

understanding

com-

of the

much

to

rise

Consider

2. This

of Chapter

made

was

development of thermodynamics.
central applications of thermalphysics
electrical
energy is generated from heat.
difference
between
heal and work is the difference in the

the

which

with

modern energy-intensive civiliza-

into work. The IndustrialRevolution

to work.The problem
of the

one

remains

transfer.

entropy

in. a

The
internal
engine, which converts heal to work.
to dominate man as much as It serves
seems
him,

which

conversion

the

magnetic field, electric field,or

heal from work will be clear

volume,

process

important

engine,

transfer

that describe

para meters

energy conversion processes.

by the steam

possible

reservoir.

transfer

is the

Work

we distinguish

reason

The

potential.

we discuss

when

include

may

parameters

gravitational

energy transfer.Heat is the

forms of

different

two

are

to a

system.

TRANSFER:

ENTROPY

work

of energy
energy

Work

OF HEAT AND WORK

DEFINITION

Heat

of Heat and

Definition

Transfer:

Entropy

a reservoir
the energy transfer dtl from
is/in thermal contacl at tcmperaiure

energy transfer is what

we

transfer- Work,
as

parameters\342\200\224such

t; an

ihe energy transfer, accordingto the

accompanies
by entropy

to a

the

position

argument

and we see

as heal,

above

defined

being energytransfer by
of a

piston\342\200\224does

not

system

entropy

a change

transfer

any

from when only

to come
system.There is no placefor entropy
work is performedor transferred.
we must
be careful; the toial energy of two systems brought into
However,
contactis conserved,but their total entropy is not necessarily conserved and
increase.
The
iransfer between two systems in ihermal contactis
may
entropy
wcl!
of one system increasesby as much as the entropy
defined
only if theenlropy

entropy

of

the

lo the

other

processes such

we

heat

processes

in

the

that

constant.Later

are

Let

decreases.

will

which

flow example

us restrict

combined
generalize

the total

in Chapter

2.

ourselves

of
entropy
the discussion

entropy

for

the

present

the interacting
to irreversible

to

reversible

systems remains
processes which

of the two systems increases,as in

the

CkapterS:Heat
We

Work

and

a quantitative expressionto the distinction

between
heat
and
dU be the energy
of a system during a reversible
change
process;da
and t is ihe icmperitture. We define
entropy
change,
can give

work. Let

is

the

as the heatreceived
by

of

the

xda

i!Q

process. By the

in the

system

(I)

principleof conservation

energy,

dV

which says thai the

and

energy

ihe System

t1W =

is (be work performed

designatingheat and
For da

below.

\342\200\224
we

HEAT

of

~ zda

dV

reversible

the

dW rather

0)
process.

reasons for

Our

ihan dQ and

d\\V

roles

energy

arc

explained

for dV = xda, pure heat.

pure work;

sysictn

Then

CONVERSION

INTO WORK

of the

because

consequences

work doneon the

reservoir.

the

(tQ

in

by iftjand

Catnotinequality. Heat
processes

dU ~

B)

partly by

from

the system

have

0,

ENGINES:

HEAT

OF

on
work

+ dQ ,

is caused

change

by heal added to

partly

aw

different

Have

work

and

difference in

in

entropy

conversion

conse-

two

Consider

transfer.

difference:

the

(a) All types

of work are

each other, becausethe

is zero.

transfer

entropy

ideal

An

electrical

electricalresistance,is device
ideal
electrical
work.
generator
of work
mechanical work into electricalwork. Because forms
to
are
each
convertible, they
thermodynamically equivalent
(o
denotes
mechanical work. The term
equivalent
particular,

mechanical friction or
electrical work into mechanical
without

and into

work

mechanical

into

convertible

freely

motor,
convert

to

converts

An

are

all

other

work

freely

and,

all

types

in

of

work.

(b)
heat

Work

cannot

be

can

be

completely

but docs

the beat,

work from

completely

heal

necessarily

converted to work. The entropy

be pennittedto
ultimately

be

removed

pile

up

from

inside

work.

the

with

strip the entropy

removed

the

the device.

device

from

from

way

to

do

system

with

A device that

generates

that

has been

the

the converted

indefinitely;

The only

inverse is not irue:

Entropy entersthe

into work.

converted

not leave the system

must

into heat, but the

converted

heat

input heat

cannot

this eniropy must ultithis is to provide more

Heal\302\243itgines:

of Heat

Conversion

into Work

Entropy

Figure 8.1 Eniropy and energy

reversible devicegencralmg
work
must equal ihc entropy inflow.

as waste

heat

is given

that only

and outpul
eittropy

ail

the
A

there

input
prohibition

all

the

heat

input

.it which

the

be ejected

need

of the input heat. Only

the entropy

heal can be convened

must

thai

iransfer

heat

reversible

by the temperature

part of the

;t\\\\ay

cany

\\\\ca.t.

heat, at a tempcrat ure lowerthan

BecauseiiQ/ifc = r,
entropy

in any

from

operating

continuously
The

outflow

entropy

converted to work, and 10 ejectthe

the amount

than

heat

input

flow

be some

output

to

work.

To

excess

input

input heal (Figure 8.1).

of
one unit
accompanying
It follows
is transferred.
heat
of the

at the
the

lower temperatureio
bctv^^.i

difference

prevent

input

of

ihc accumulation

heat; therefore h is impossibleto convert

heal to work!
against

unlimited

entropy

accuniLiiaiion

tn

mean entropy cannot accumulate temporarily,

that
provided
removed. Many practical energy-conversion
devicesoperatein

device
it

does

not

is ultimately

cycles,

and

the

contained

entropy

deviceis calleda heat

The entropy
contained
a value

is

There
the

stroke

intake

the

What

in each

not

is at a

cylinder

minimum near the beginning

of

pile up indefinitely.

of the

fraction

The

engine.

Such a cyclic
is an example:

and a maximum near the beginningof the exhaust stroke.

of the entropy eontent to which the devicereturns cyclically;

does

entropy

with time.
periodically
internal
co'rnDiisTion engine

varies

device

the

in

input heat Qh taken in

convened
into work.?

one

during

cyele

at ihe

fixed higher

The input entropy associatedwith

QjTh.
inpui
confusing signs, we define in this discusdiscussion all
is into
heat, and entropy flows as positive whether the flow
or
energy,
out of the system, rather than
ihe
usual
convention
following
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
fixed
;j{
the
lower
per
cycle
temperature t,.
= Qjxy In a reversibleprocessthis output
the output
entropy
per eyclc is as

temperatureth
heal

the

is equal

entropy

be

can

is ak

\342\200\224

To

avoid

to the input entropy:

Q,fa = QJik ,

Qi

14)

E)

ir,/rh)Qh.

generated during one eyeleof a reversibleprocessis the

the heat added and the waste heat extracted:

The work
between

ratio of

The

ealled

the

Qh

- Q, = [1 -

the work generatedto the

Carnot

QA

-\302\261\342\200\224>-

F)

Qh.

in the

added

heat

difference

reversible process

is

efficiency:

G)

is named in

This quantity

a remarkable feat: the

Carnot*s

form of

derivation

of

concept

entropy

by some 15

preceded

derived

it in

1824. It

was

not yet been invented,and

the
recognitionthat heat is
years
had

energy.

The Carnot efficiency

efficiency

honor of SadiCarnot,who

ij

W/Gh,

is

the

the output

highest

value of the

possible

work per unit

of

input

heat,

energy conversion
in any

cyclic heat

Heat

Ens'\"\":

Conversion

of Heat

into

Work

input

Output

Figure 8.2

Entropy

and

irreversibilities ihal generate

outflow

entropy
inflow

at

ihe

energy

(low

new

in

entropy

lower temperature
higher temperature.
at the

heat engine containing

inside the device. The
is larger
than the entropy

a teal

t,, and t,. Actual heat engines

operates betweenthe temperatures
have lowerefficiencies
becausethe processes
taking
place within the device are
not perfectly
reversible.
will be generated inside the device by irreversEntropy
8.2.
flow diagram is modified as in Figure
irreversibleprocesses.
The
energy-entropy
We now have three inequalities

engine that

ft S:

&(r,/Tfc);

(9)

A0)

actual

The

energy conversion efficiency j;

obeys the Carnal inequality

W/Qk

ijc only in the limit of reversible

i; =

have

can

We

takes in heat at ih and ejectsheal at rt.

The Carnot
inequality is the basic limitationon any heat
in
a cyclic
The result te!!s us that
it is impossible
process.

heat tnto work. For a

is

efficiency

with

increases

increasing

tJt, -* go.
The

waste

usually
Th high compared
limited

which

are

is

by

materials

an

in

temperatures

constraints.

the

below

all input

conversion

be

ultimately

environmental

input

temperature

are unfortu-

practice

In power plant

steam turbines,

operate
continuously for years, the upper temperature
willi
the strength
to about
and corrosion
600 K\"by
problems
300 K and Th = 600 K, the Carnot efficiency
is i;c =
$, or

limited

of steel.With
=
r,
50 percent. Lossescausedby unavoidable
irreversibiliiies
to
40
about
eilicicncies
T
oobtain
typically
percent.
Higher

reduce
is a

this ellkicticy
problem

in

high

metallurgy.

temperature

Sources

operates

to

expected

currently

heist engine must

K. Higheilicieney
requires

to 300 K. The usable

various

to convert

that

inoperation. The limiting efficiency

!00 percent efficiency only when
attain

of any

heat

that

engine

the highest

tJt,

so thai r, c;innoi be

about 300

temperature,

we

but

the environment,

into

unfortunately

reversible

xhfxit

low-temperature

ejected

temperature

given

under

obtained

ratio

a device

of

operation

Figure S.3 illustratesseveral

of UreversibHity.

common

sources

of

irrevcrsibility:

(a)

Part of the
bypassing

cylinder

the

heat

input

actual

walls

Qh may

energy

duriiig

to the low temperature,byprocess, as in the heat flow into the

flow directly

conversion

the combustion cycle of the

combustion

internal

engine.

(b)

Part of
temperature
the

r, way not be availableas temthe actual energy conversion process,because

resistances in the path of the heat
thermal
across

the temperature differencex,,

in

diflcrencc

tesnperature

drop

of

flow.

(c)

part

of ilic

work generated may

be convertedbackto heat

by

mechanical

friction.

(d)

Gas may

expand irreversibly without

expansion of an idealgas into n vacuum.

doing

work,

as in Ihe

irreversible

Irreversible
wfthout

expansion
or

work

heal

bypass

Four sources of trreversihilily

in heal engines:
the
conversion
ihermai
resislance
b> passing
energy
process,
of tile heal flow, frtclional
and
losses,
entropy generation
Figure

8.3

irreversible

heal

How

in the

palh

during

expansions.

Refrigerators
to move
work
consume
engines in reverse.Refrigerators
low temperature r, to a higher temperature
the energyConsider
rA.
no
in
8.1. Because
entropy flow diagram of a reversibleheat engine
Figure
its operaiion
can be reversed, with an
enlropy is generatedinsidethe device,
e*act reversal of the energy
and
Ot>-\\i.
F)
Equations
D)
ihrough
entropy

Refrigerators
i'^ai from a

remam valid

are heat

for

the

reversed

flows.

Chapter S: I hat

The

but

G),
to

temperature

of interest

ratio

energy

efficiency

Work

and

the

ratio

tlic

work

value

reversible

in

with

i;

<

i always,

consumed

f\302\260r
'he

W;Qh

y can

be > 1 or

of

tem-

low
refrigerator

the Carnot

confuse*/ =

0,/W
heat engine;although
W = Qh - Qh the work

yc. Do not

efficiency of a

conversion

energy

by

conversion

tlic

at

is called

operation

coefficient of refrigeratorperformance,
denoted
52
\302\273;

tile energy

is itot

refrigerator

Q,/W of iho heat extracted

This ratio is calledthe coefficient

consumed.

its limiting

performance;

in

< 1.

From

E)

Eq.

and

is

A2)

The Carnot coefficientof refrigerator

performance

is

Th

This ratio can be larger

Actual refrigerators,
that generate entropy

or

smaller

than

A3]

T,'

unity.

like actual heat engines,

inside the device.In a

always

irreversibilities

contain

as
in the
ejected at the higher temperature,
ettcrgy-entropy
that all energy and entropy flows
Figure 8.4.With the convention

we now

place

are

positive,

have
ah >

in

is
of

excess eniropy
flow diagram

this

refrigerator

of (8).

e, ,

Further,

& 2 (V'Jfl

A4)

Qt

- Q, >

\342\200\224

1]Q,

Q,iW

=\342\200\242

< yc.

A5)

Q,

\302\273

Q,/yc

A6)

Air

ami

Conditioners

Heal Pum

Ouipui

Input
Figure 8.4

The Carnot coefficient

yc

energy conversion
Both heat engines

refrigerator.

limit to the actual coefficient

ofrefrigerator
upper
Carnot efficiency t\\c is an upper limit to the actual
;; of

efficiency
and

flow in a

energy

is an

as the

y, just

performance

and

Entropy

a heat

refrigerators

are

engine.
subject

to restrictions

imposed by the

but the

device designproblemsare totally

the design of refrigerators to operateat the temperature
In particular,
helium or below is a challengingproblemin thermal
(Chapter
physics
law

of

of entropy,

increase

Air Conditioners
Air

automobile;

inside
during

the

ofliquid

12).

and Heat Pumps

or an autothe inside of a
the
environment.If
outside
interchange
a building
connections, an air conditionercan beusedto
If
Such a device Is calleda heat
t|
xk a beat

are

conditioners

different.

heat

and outside
the winter,

refrigerators

is ejected

that cool

building

lo the

we

heat

pump.

\342\200\224\302\253
r\302\273

Hear and

Chapter Si

heat the

can

pump

Work

on the

limitations

The

much more costly

Heat

air

a lower

with

of energy

consurnption

than by direct

I).

(Problem

healing

building

and

install

to

economic

make

pumps

use of heat pumps

is required

conditioning

are

economical,

largely

They

are

than are simpleheatersor furnaces.

sense primarily in eiimatic conditions in which
to main tain

anyway.

Carnot Cycle

The

of

coefficient

refrigerator

realize process
refrigeration
is

Carnot

the

of

derivation

by which

achieved.

The

energy

conversion
made

performance

work is

generated

and best

simplest

efficiency and of the Carnot

no statement about how to

from

heat,

or

about

how refrigera-

known such processis the

Carnot

cycle.

Carnot cycle a gas\342\200\224or another

substance\342\200\224is
and
working
expanded
in four stages, two isothermal and two
as in Figure
8.5.
isentropic,
compressed
1
has
and
The
is
At
the
the
the
gas expanded
point
gas
entropy
aL.
temperature xk
at
r until
2. In the
at constant
the entropy
has increased to the value
a,,,
point
In the

second stage the gasis further

now at constant
a, until the temperature
expanded,
to
has dropped
to the value r,, at point 3. The gas is compressed
isothermally
4 and then compressed isentropically to !heoriginals!a!eI. We
write
aL
point
contained
in
the
and c,, for the low and high
the
values
of
working
entropy
are
the
to distinguish these values from
and
which
substance,
ch,
entropy
a,
tlic Carnot cycle,
at !hc low and high temperatures r, and
rv For
per
cycle
flows
G\\

~
The

\302\260h

&I1

\"
\302\260L-

done

work

by the

system in one cycle is

W~{Th

of the

rectangle

in

\342\226\240\342\226\240=
0 =<\302\243uta

where jjklV is the work done by

the first phase
is
T = ts during

combine

described
substance.

T,)(tfn

- ffj.

A3)

from

follows

SdU

We

area

8.5:

Figure

whicii

[he

(IS) and A9) to

the

system

-SpJV

in one

cycle. The

obtain the Carnot efficiency

boat taken up

;/c.

Any

by Figure 8.5 is calleda Carnot cycle,regardlessof the

process
working

at

,lCyd.

Figure 8-5

into
work,
cycle, for the conversion of heat
of entropy
versus
for
an
arbiirary
temperature,
working subsiance. The cycle consistsof two expansion
phases
4 and 4 -+ 1).
(t -* 2 and 2-<3) and wo compression
phases <J \342\200\224\302\273
Cjnc of the expansion
ano one of ihc compressionolsascs
iire

B -> 3 and 4

iscntropic

loop.The

rather than

Even

and outputs
such

where

reservoirs.

The

Carnot

healing

Caettot

Example:

cycle-

reservoir

<i\\h

initially

at

is

kind

done is ihc

area surrounded by

area of ihc
ilic

the

energy

conversion

need a

cycles

temperature output of heal, bu!

gas

as

exist,

cooling

cycle for an
ihc

All

in principle

could

what

(lie

often

are not well-definedreservoirsat constanttemperatures.

presenl

and

is done.

fact

a low

and

reservoirs

difference

temperature

in

what

input

temperature

inputs

of each

phase
work

cycle is a point of reference!o indicate

The Carnol

be done,

at r^ is the

consulted

heal

one
nei

line.

broken

heat

- 2 and 3 - 4), and

-* 1}.The

(I

isothermal

high

Carnot

as a plot

illustrated

between

steam

the

occupies

We

carry

is invariably

(here

turbines,

working substance and

processes are

idea!gas.

high temperature

in

never truly

an

ideal

;s

reser-

the

reversible.

monaionjic

a volume t', and is in thermal

tv The gas is expanded isolherlttally

gas

equilibrium
to

through

the

with j
volume

K, as
\\vo[k
heai

in

Qh

This

work is

furlhcr

:,.

Ihe

In

is delivered by

now

Afler

F.63).

ciioscnlo

=.

the addilional

The volume

gas.

\"

V3

the

the

at

from

(SI* and

low

tem-

iseniropic expansionis related

lo

the

VJVj.

into contact

(tJt,}*2

B2}

a temperature

with

reservoir

<Slf

satisfy

\342\200\224

f,.

i'j,-

Kj/V'4

the

gas is

initial

has returned

this

from

CH,

ncl work

areas in Figures
curves in the p-V

delivered

value

initial

8.6a

cancels

by

the

and 8.6b,

diagram

as

<R,

heai:

= ^34-

and

jy4!

on ihe gas; this

-*
2
3, by B1).
expansion

the work

B5)

until its temperaiseniropicatly

of the choice B3}of K4l the gas volume
and the cyde is completed,in this last slage

recompressed

i*. Because

temperature

is performed

to

B3)

VJV2

compression,

is ejected

work,

to its

= (t*A,K'2

To accomplish

disconnected

to ihe

liseii

at this point
the work

The

end of ihe

or

ft

temperature
has

B0}

disconnect!
has dropped to

ihe temperalure

is brought

gas

ust be done on ihe gas.This

Finally,

as
the

work

= TftV22'3 ,

point

A'r

the gas is

Next,

\0212

until

iscntropically,

Nr^dV/V

labeled

KfVx
so thai

JpJK
area

the

process

the

ii

reservoiris

by

TlV32:3

from

n^cdmmcal

II'l3

indicated

expanded,

peralure

the gas absorbs Die heal Q, from (Rt and delivers

sy ^Icm conncclco to Die pislon. i~or an sdcaiQas

Hie process

\302\243.6a.
In

Figure

*jj 10 ^n c\\lern>ii
absorbed from (he

the

Vlt

|N(rh

work

gas during
is the

which

\302\253

B6)

T()

W2i done

by

the

the cycle is given

enclosed area in

are steeper lhan the

gas

by

during

ihe difference
8.6c.

Figure

isothermalcurves,

the iseniropic

so

thai

in shaded

The isenfropic
Ihe area of the

y3

Figure 8.6
and

> r,}.
\342\226\240t,(xk
(a)

the

work

an ideal gas, as a p-V plot. An ideal gas is expanded

Two
of them are isothermal, at the temperature I* and
stages.
back. The shaded areas show
ofthem arc isentropic,ffomtt to ti.and

The Camot cycle

riicompressed

for

in four

Two
done during

compression stages,

and

two expansion
stages,
the
net work done during
(c)
the

(b) the
the

work

cycle.

done

during

the two

2nd

is nnitc

loop

and Work

8: Heat

Chapter

i^

to trie

ctintii

relation

Camot

the

of

We

of heai from

reversible

All

have

peratures

so, We

ihe

~-

is jusi

which

r,)/Tj,,

and on the performance

law of increaseof entropy.

of

Q{\\n)

devices

ihe lower

I with

d\302\243\\
ice

different

with

(hat mows not only ihe

2 back io

the

The

li^otit), uiihout

ihe annihilationof entropy

would

and

any

qt <

efficiencies,

ij2,

efficiency is operaied in

entire wasteheat Ql2

th,

iemperaiure

higher

The overall

as well.

heai

Q{in) to work

heal

- (ij

into work

of ihe

reversible

(Figure 8.7)ihat

refrigeralor
efficient device

amouni

of heat

consequences

as a

more

W/Qj,

of Thermodynamics

Law

conversion

two

combine

could

in such a way
reverse

so that

B0),

B7)

usually is formuiaiedwiihom memion of

Kelvin-Planck
formulation in Chapter 2:
for any cyclic process lo occurwhose
effcci
is ihe exiraction
sole
reservoir
and the performance ofan equivalent amount of work.\"
conversion devices thai operaie beiweenihe same
ienienergy
= W/Qh- Were ihis not
the same energy conversionefficiency
;j

is impossible

\"Ii

of ihermodynamics
stated
ihe classical

law

eniropy,

in

Second

the

direct

are

refrigerators

second

given

Imvc

iVc

G).

limiis on the

The Carnoi

m F^Rurc 8,3.

jtic rccmn^lc

TjloaflV^).

Cftk was

Conversion and

Energy

W(rfc

The heat absorbed from

of
3r\302\243*i

but

ihe

from

an additional

result would be ihe conversion

net

violate

waste

ihe law

heai.

This

of

would require

of increase of entropy.

jhai all reversibledevicesIhat operatebeiween

ii is sufficient
same
temperatures
energyconversionefficiency,
to calculate this cfiiciency for any particular
device
to find the common value.
~
=
The Carnot cycledeviceleadsloi;c (xh
ri)/rft for the common value.
eslablished

we have

thai

Now

the

have the

same

of
Path Dependence
We have
processes,

and

Meat

Work

carefully used the words heat and work to characterizeenergy

iiself.
and not to characterize properties of the system

We look
plane,

returned

It

is not

to spe;ik of the heat content or of the work

system.
in
the
Around
a
closed
the
Cinnot
once
more:
p-V
loop
cycle
a net amount of work is generatedby the system,
and a net amount of

meaningful

heat

transfer

is

content

of a

around

Ihe

at

But

consumed.

to

precisely

changed.This

means

the

system\342\200\224on

the

initial

that

there

being

once

loop\342\200\224is

no property of the system has

exist two functions Q{a,V) and W{a,V)

condition;
cannot

taken

Path

and

of I hat

Dependence

Work

different reversible energy conversiondevicesoperating

between
the
same temperatures tj, and r, coutd have diiTercni
efiiciencies f'jj > >ji
conversion
energy
h would
he possible to combine them
100 pd cfikictio
into
a single device wilti
'\342\226\240>\342
the lessdiicienl
deuce ! us a refrigerator that moves not only ihc eniire w;i>:c
using
ficas
ofstie
more efficient device 2 backto the higher
bui an addiriotiii
Qti
semporaiure,
would
shcii be completely converted
amount
Q[in) of licaE us wt;il. Tlifs additionat huat
Figure

8.7

If uvo

to work.

sudi th;n the heal Q^ and

siSilc(aa,VB)toa slate {ab,Yb)

If such

loop

the
are

fimcitons extsicd, the

necessarily

would

be

nut

zero,

work
given

Wub

by the

transfers

;md we

to

required

differences

of heat

the system

curry

and of

h:ivc shown that

in

from a

W:

and

work aroumla closed

transfers

the

;tre

not

zero.

The transfers of hc:itand work

between
state
(a) ;ittd slate (b) depend on the
the two states. This path-dependence
is expressedwhen
taken
between
path
we say (hat
hwt and work' are noi siaic functions.
Unlike
entropy,
temperature,
energy, heat and work are not
increments dO and (fIS'that we introduced
and free

inlrtnsic

atlributes

in (l)and

of

B) cannot

(he

system.

The

bedillerentials

8:

Chapter

and Work

that

Twotrr

Figure 8.8

sibie proceisesin

or electrical

mechanical

which

potemial

For
this reason we designated
of mathematical functions Q(a,V)and \\V(o,Vy
the increments by dQ and d\\V, rather than by itQ and dW. Without
the
path
not
exist
that
of heat and work there would
dependence
cyclical
processes

permit the generationof work

Work

Irreversible

We consider the
is

heal.

from

energy transfer

or electrical

mechanical

a purely

of

processes

8.8. In

Figure

system that

delivers

or

friction

same as if the energy

of &2 is increased by

Processes

no

way

to

If newly
irreversible

the

reverse

to heat, either by

that

dU

reversible
this

change

work
in

in order

process

the

at
led

and

in energy

entropy

tfWtev

the

S2

The

^ J^e

entropy

created entropy.

are irreversible because there is

to deslroy the newly

conversion

place.

is newly

entropy

is created

of

state

of work

created

to heat,

entropy.

we say that

been performed.

has

work

If we look only

This

ilU2fc-

entropy arises by

created

the process

\302\253

do2

new

which

in

transferred
to &2 is converted
The finai
electrical
resistance.
by
had been added as heat in the first

with zero

work

pure

entropy change. The eneray

mechanical

each process &i

to
i\\a

net change
this change

in

entropy,

as

the

a reversible

irreversible, the actual

work

in

a system,

there

is no

way to tell whether

was reversible or irreversible.For a

we can define a reversible heat dQICV

change
and

of heat and work that would accomplish

If
process.
part of the work done on the system is
a given change is larger
to accomplish
required
amount

Work

Ineveniblt

the

than

reversible

work,
tn\\'il

of energy

conservation

By

dU =

if\\Viim

that

so

actual heal
reversible heat.

The

Example:Sudden

ideal gas. As an example of an irreversible processwe

expansion of an ideal gas info a vacuum. Neither heal nor
*= 0 and dx = 0- The
stale is identical with
the stale
final

is transferred,
so thai ttU
that refills from a reversibleisothermai
with a reservoir. The work
IV,,, done

work

i\\

:o

Vj is,

equai

to

the

gas is negative;the gas

transfer
into the system:

heal

change

is equal

W[cy

lo Q,cJt,

a1-al'=

agreement

in

Ihermai

expansion

equilibrium

from volume

with

B8) and

B9)-

C0)

posittve work

does

>

Wtet <

0;

on the piston

in

an

amount

0.

C1)

or
~Wlcy/x

In the ineversible process of expansion into

because neiiher heat nor work Rows
entropy
= 0- From C1) we obtain
Qi\302\253c.

in

reversible

the

-Nilog(^/K,).

on the

Q[cy=
The entropy

in

from F.57).

done

work

gas

the gas

with

expansion

on the

\\V,n=
The

the

ihan

less

be

of an

expansion

more llic sudden

once

consider

transferred hi the irreversibleprocessmust

the
into

C2)

NlogfiyV,).

this enlropy
from the
system

vacuum
the

is newly
outside:

created
lVitltt

*=

Chapter 8: Heat and

Work

Systems between

8.9

Figure

heat is transferred

need not

which

be

at the

but no

work

on!)'

same temperature

for the process to be reversible.

In our discussionof irreversible

is created insidethe
This

systems.

heat transfer,

work

ai

In this

2.
lower

the

process

heat
t2.

temperature

transferred

fs

= (I/I,
is from high to

heal flow
so

but

actual
reversible

They

entropy

energy

other

Pure

transfer.

place between
out an example in
worked
a system a! rt to a system
if it takes

=\342\226\240

that

chitT >

low

0.

<fQt

C4)

remain

processes

constitute

generation.

natural

i!Qt

temperature;

is negative;

r3

- ri

is

transfer

energy

C5)

-ii.re..

1/I2)rfe,

0.

The energy transfer between two

not be irreversibleif only work but
AH

system by

created entropy is

The newly

negative,

from

in

entropy

We have.'.

i!U2

The

of work Jo the

We

temperatures.

the new

that

assumed

is nol she only source of irreverstbility

nol involvingany work, is irreversible

iwo systems having different

Chapter

the delivery

during

system

we

systems

no heat

with

different

need

is transferred (Figure8.9).

are invariably somewhat irreversible,

processes
the backbone of the theory of thermalphysics.
which is the equilibrium limit
assume hereafterthat the words

limit,

We shall

temperatures

without a further qualifier, referto reversible

processes.

of

heat

vanishing

and work,

Pressure

TEMPERATURE

AT CONSTANT

WORK

AND

HEAT

Temperature or Constant

at Constant

Work

and

Heal

OR CONSTANT PRESSURE
isoiherma!

F ~

energy

the ioia! work performed on a system

in
is
io
Ihe
in
Heimlioltz
increase
the
free
equai
process
For a reversible process tfQ = ida ~ d{ia),
ihe system.
show

We

work.

Isothermal

a reversible

\342\200\224
za
of

because dx =

0, so

that

dW

in

additional

system to

terms

of

work

that

the

the

work

(he

done

dU

Hclrnholiz

is required

reservoir.

the

ideal

for

appropriate than

ftiuciion, more

process

dV

- d(za) \302\253dF.

processes the Helmhoitz free energy

in such

Thus

ihai

Often

gas the energy V

is equal
lo the

Isobaricheat

and

work.

Many

the

the

energy

When

V.

free energy,

to make up
heat

does

noj

is

C6!

ihe

natural

we treat

encrgc:;';

an isotEicrltui

we automatically include
for

transfer is

the

heat

transfer

ihe

from the

ihe major part of the work;

isothermal process, and

in an

change

heat transfer.
energy

transfer

processes\342\200\224isothermal

or

not\342\200\224

take
place
pressure, particularly those processes that
is
said
to be
the
A
to
at
constant
pressure
open
atmosphere. process
an isobaricprocess.
A
is the boiling of a liquid as in Figure
8.10,
example
simple

lake

place

at constant

in systems

Figure

displacing

8.10

=/<\342\200\236<<

a liquid boils under aimospheru: pressure,the vapor

the aimosplierc does work againsi ihe atmospheric
pressure.
When

Heal and Work

ChapterS:

where the

pressure on the
its

changes

system

environment

If positive,

system.

sense \"free.\" if

this

in

is

and

and is not extractablefrom

thjs reason it

is

thus obtain the

appropriate

eflccthe work

ilW =

itW

the

the

energy

enthalpy

which

V plays isi

itU +

d{pV)

for other

~d(pV)
the system,
=

itQ

the

from

of the
is part
environthe
to

delivered

is

work

system

d{pV) -

\342\200\224

the

purposes.

For

work.

We

total

defined as
~ HQ ,

till

C7)

function

new

called

the

on

performed

d{PV)

where we have defineda

is provided by

this work

io subtract

pressure. If (he

atmospheric

negative, the

environment

often

external

by dV, the work -pdV

volume

total work doneon the

is the

piston

plays

= V

+ pV ,

the role in

processes at constant

C8)

processes at constant pressurethai

volume. The term/it7in

is the

C8)

to displace the surrounding atmospherehi order

to
to be occupiedby the system.
is
in
these
definitions the idea
Implicit
there
that
are other
kinds of work besides ihut due to volume
changes.
Two
classes
of the constant pressure processesare particularly
important:
in whichiiodTcctive
work is done. The hcattransfcr
ist7Q ~ <///,
(a) Processes
from C7). The evaporation of a liquid {Chapter 10) from
vessel is
an open
a
no
such process, because effective
work
is done,
The heal of vaporization
is ihe enthalpy
difference
between
the vapor phase and the liquid phaseconstant
and
(b) Processesat constant
temperaiure
pressure. Then iJQ =*
~
and
if/a
work
the effective
d{xa),
performedon the system is, from C6) and
C7),

work

vacate

required

the space

d\\V

=> dF

where we have defined another new

G

the
at

Gibbs
constant

free

energy.

temperature

~ F

+ pV

+ d{pV)

used

energy

\302\253
U

pV

10.

- xa ,

D0)

effective work performed in a reversibleprocess

and pressure
is equal to the change in the Gibbs

The

of the

in Chapter

C9)

function

system. This is particularly

where the volume changes as the reaction
The Gibbs free energy
ts used
extensively
free

=> dG ,

in

useful

proceeds

in

at

chemical

a constant

reactions

pressure.

Chapter 9, and Ihe enthalpy

is

Heat and

isobaric

an

Consider

electrodes

ant) SO4~

H+

ciccHoiylc

noi re net

ilia t do

w&in

of dilulc sutfurie
lnc acid [r igtirc

where

s. 11J.

\302\253
2H+

positive electrodes
gas and clocirons: _.
+

the

net

H2O-\302\273

Whch carried out

An

sulfurtc
and

in

slowly

a vessci

temperature.

prcsburcaiKicoitMiiiil

hydrogen

move

electrolysis

acid.
oxygen.

cell

The overall

to lhe

negaihe clecirode

g;is:

D2)
water

decompose

they

with the

- H3SO4+'iOj + 2c!^.

H;O

above liircc stepsis

of the

Figure 8.11

in i o

H2.

where

the

SO4~

as dilute

^titfiir

D!)

ions
through the ceil lhe hydrogen
up electrons and form molecular hydrogen

lake

The sulfatc ions move

to
release of molecular
oxygen

sum

Tnc

arc immersed philiiuiin

tc sci^i dissocjaics

SO.,\"\"

-+

The

which

iti

is passed

current

llicy

acid

ions:

H2SOa
When a

Constant Pressure

Temperature or

at Constant

Work

rcucikm
H2

ctttuiluin

in lite

D3)

cell;
{44}

1O3.

open to lhc almosplicrt!, ihc prticessis at

power
negligible
pjft of the olcciricul injml

An electrical
result

The process is an

temperature and constant pressure.

is the

current

passes

decomposition

example of work

being

through

goes

an electrolyte,

ofwaterinto
done

conslain

gaseous

at constant

iulo

such

resistance

of the electrolyte. The effective work required to

to the molar Gibbs free energies
of Use reactants:

heating

is related

water

AG

G(Hj) -

G(H2O)

\\G{02).

Gibbs free energy differenceAG

list the

tables

Chemical

=>

decompose1moleof

- 237 kJ

as

D5)

per mole at

room

temperature.

In electrolysis tins work is performed by a

one
Vo. If I is the time required to decompose

(not

the

of water.

male

flows under an external

I x I is lhe total
Q \302\273

voltage
charge

the cell, and we have

tlirough

flowing

heat!)

/ that

current

W ~QV0.
to

According

are

there

D3),

one water molecule,

in decomposing

involved

electrons

two

D6)

llcnce

Q
We

D5) 10obiain

D6) to

equate

minimum

because

VQ

merely

If V

<

reaction

the

Vo,

the

simplesetupof Figure
al all.

happen

Ev

8.11

is possible,

and oxygen

hydrogen

f'o between

voltage

arrangement
on board the

sources

for

water
The

focced

cell are shown

to J.

under

through

and,

tf

Apollo

O. M.

1969.

(V

VQ)

lhc

/will

(Figure 8-12). Such adevice producesa

arc connected, eucnwl current will
fuel cell. Fuel cells were used as power

pcessure
the

electrodes

hydrogeci-osygen

Gemini and Apoilo* ipacccta.fiand

technological limitation of
cell the current density
Apollo

the

\342\200\242

excess power

on

dtinking

produced

incidentally

astronauts.

the

of an

characterise

Va, the

flow,

the systems

gaseous

principal
In

V >

current

finite

between

from

proceed

is called a

elecirode areas are required

The

will

the electrodes

This

obtain a

poierciuit

is
right to Icfl provided gaseoushydrogen
at lhc negative electrode. In lhe
oxygen
will
the gases are permitted to escape,and
for V < Vo nothing
however, lo construct the electrodes as poroussponges,wiih

D4)

positive electrodeand

at the

available

D8}

be applied
to
barrier

must

reaction equationD4).When.
dissipaicd as heat in trie electrolyte.

area.

place.This requiresa

~AC/2NAe

larger lhan Vo
reduces to zero

voltage

alone

Vo

of the

sides

{law.

lo take

for electrolysis

D7)

voltage

or 1.229volts.

be

condition

the

two

x 10scoulomb.

= -1.93

~2/v>

lo

ceil

clearochcmi'cal
in

K.I

Figure

End criU used

Bockrisand

produce

Ni

in

was

only

few

current,

hundred

currents. The

reasonable

Us two

low

is their

cells

fuel

operating

ranges as

fuel

per

unit

electrode

hence

mA/cmJ;

large

current-voltage characcell

and

as electrolytic

3.

and

NiO

S. Sriili^asan,

uniict ibn
fwf cells:

Pt

Their

as decltoiici.

electrochemistry,

ami K.OH racier

McGraw-Hill,

sVian

H .SO\302\253

New York,

Porous electrodes
ecl! is an electrolysis cell operated in
and oxygen supplied as fuels. The
reverse,
hydrogen
fuels arc forced under prow tin: through
dmroOes
porous
an
The
and
oxygen rea
electrolyte
hydrogen
sqwratcJ by
Tree
is
delivered
to
form
the
excess
Gibbs
waicr;
energy
Water
forms at the positive
outside as electrical
energy.
Figure

A fuel

8.12

with

electrode and

is removed

there.

Elcnrolysis

Figure

8.13

celt or

fuel

Tliecui

ic of

indie

anges.

cell,

\342\200\224

aa electroiyiic

Heal and Work

ChaptcrS;

Chemical Work

Work performed by
it is

because

work,

independent variableson which

a reversible

for

then

chemical

the

derivatives by their
lerm

zdo

xda -

familiar

represents

The -pdV.termis

mechanical

the

transfer

reservoir,

both

from

systems.

system

&x to

dN2

\342\200\224
\342\204\242

dN =i

dN,

*=

(dV1

= 0),

The result
summarize

{a} The
particle

(b)

and

~pdV

of heat,

fidN

terms

be reversible:

to

E0}

pJN.

pdN

term is

the chemical work:

.

ftdN.

0. All

d\\Vcl

and

if

all

chemical

into

fadNt

processes

E2) gives art

the

be supplied to the

that must

dVi

our definition

E1}

the Work

system .&;. The chemicalpotentialsare /it and p2. If

is the number
of particles transferred, the total chemical

= OWcl

dWc

work

the

and

the partial

replaced

is

performed

The

have

is chemical,
arc usually
two systems involved, both in contact
there
is the sum of the contributions
and the total chemicalwork
In the arrangement of Figure 8.14a pump
transfers
particles

In particle
a heat

= U(atV,N),

If U

D9}

understood

-pJV+

work;

volume change, dV

is no

is one

system

5.1). By

of heal

dWc

work

fidN

(Table

equivalents

Ihe transfer

<tW ~

from

pdV

represent the performance of work, ali

If there

the

U depends.

energy

thermodynamic identity of Chapter 5. Herewe

by tlie

with

potential.

process

dU =

the

the

with

particles are transferred, the number of particlesin

When

of the

associated

system is called chemical

to a

of particles

transfer

the

additional

of ihe

propcriics

potential

the

system,

The difference in

+ pldN2

pump

= (p2 -

is a\\Vr if

{52}

nt)dN.

there is

no volume work

arc reversible
meaning

of the

chemical potential.

We

chemical potential:

system is the
from a reservoir at

of a

work required to transfer one

chemical

zero

chemical potential between two

net work requiredto movea particle

from

one

systems

system

potential.
is equal

to the

other.

to the

8.t4

Figure

chemical

chemical

{c} If ihe

work is the work performed

when particles arc moved
one system to another, with the two systems having different
ITilie two volumes do not change,
ihe work is pure
potentials.
Chemical

from

rcs'ersibly

work

two

the

amount

potential;no

in diffusive

are

systems

is

work

per pariicie is

required

the

in chemical

difference

equilibrium ihey have the

move a particle from

io

potentials.

same chemical
one

syslem

10

the other,

{d} The difference in internal chemicalpotential

to the potential
systems is equal but opposite

systems in diffusive

5}

{Chapter

barrier thai

two

between

maintains the

equilibrium.

gas. We considerlhc work per particle required to

monatomic
idea! gas from -Sj wuh concentration
t\\^. to -S.
with concentritiion n2 > ii,, both sysiems being al the same leinpcrntnre
tFtgure 8.151 If
\302\253 the work
dV
cati be calculated
from ihe
contains only a chemical work term, which
0,
difference in chemical
no matter how
is actually performed. The
the process
potential,
chemical
with
concentrations
is
difference
between two ideal gassystems
different
potential

Example

i Chemical

move revcrsibly ins

02
This

rcs\\ih

isothciniiiily

compressN
W

work

/fl

the

of a

t[10gOl2/\302\273iQ)

logOlj/Hfl)] =

E3)

Tlog0l2/Jl,}.

io lite n\\cch:tnit;tl
work
per particle required io compress the gas
from the concentration \302\253j
to the concern mi ion
ux. Tltc work
required io
of
ideal
from
an
initial voluitw i\\ to a littal volume ''. is
an
particles
g;ts

is cqtial

=
-\302\247pdV

Hence

an ideal

for

atoms

mechanical

-Nx^tiVjV^

work per

NTlog{IV^}

particle is iSogtoj/iij),identical

= WtlogfHj/ii,}.
to

the

result

{5A}

E3). The

ChapterSt Heat and

Work

Reservoir'

ilnergy

exchanges-

8.15
Isothermal
diemiciit work. The amount of chemical
does not change
if the process is performed isoihermally with
thermal equilibrium wiih a common
targe reservoir.

work

Figure

work

chemical

the

ideniiiy

of

lence or

convcriibiiiiyof

Magnetic Work
An

and

form

important

the

wiih

kinds

dilferem

Superconductors

of work

isoihcrmal

,-

is magnetic work.Themostimportant

is to

conductivity

to

in

illustrates the equi-

compress

that

electrical

per panicle

sysiems

of work.

superconductors, and
Below some critical temperature Tc
is
electrical conductorsundergo transition
from
work

of magnetic

both

a superconducting

this

application

their

than

less

usually

application

here.

is treated

state wiih a

normal

slate wiih an

many

20K,

finite

infinite

apparently

conductivity.
superexpel magnetic fields from their interior. If the
into a
cooled below the critical temperatureand ihen inserted
would shield the
the
infinite
magnetic field, we might expect that
conductivity

Superconductors

is first

superconductor

interior from
even

8.16).

ir i|ie

This

duciivity

shielding

the

penetration

by a

occurs
magnetic field. However, ihe expulsion

is cooled below Tc while in a magneticfield (Figure

superconductor
that
active expulsion, called ilic Metssncreffect,shows
supefcon-

ilian an infinite conductivity.The Mcissncreffect

the
currents lhat are spontaneouslygeneratednear
surface,

is more

about lG~5cm iliick. The magnetic

field

expulsion
field.

by

in a

layer

is not

expulsion

Superconductors are said tobeof type It if the

in a range
of fields above some low
nonzero,

is caused

We

always complete.
is incomplete, but stilt

shall

restrict

ourselves

ark

and

Superconductors

8-16

Hgure
in

a constant

transition
the

Mcissner

applied
temperature

supercon6tiding sphere cooled

ihe
magnetic field; on passingbelow
tlic iiiics of induciion B arc ejectedfrom
effect in a

sphere.

Thresholdcurves

Figure 8,17
fidd

versus

lempcratui;:

conductors. A
below

In

TiX

Temperature,

in

specimen

ihe curve and

for scv
\342\226\240i
;jpe

noiii..;! iib

,-->I[-lOUl

fill

111

and Superconductors

I Curt

Magnetic

Figure 8.19
arcu

A in

produces

transition
that

it

electronic

is the

The superconductingstaleis a
by differences

The
of

iicai

in

the

with the

field,

iower

capacity
8.1 S)
-di

superconducifvhy

magnetic

heat
(Figure

capactiy

superconductor

sol

superconducting

a magnetic Ikld

crystai structureof the

B.

metai

x =

energy.

distinct

.<hermodynamic

phase,

as confirmed

of the normai and the supcrconduciingstales.

cxiiibhs a pronounced discontinuity at ihe onset
xt; when superconductivity is desiroyed by a

ihe discontinuiiy
free

rather than the

transition.

a phase

undergoes

system

Beiow

disappears. The stable phasewill

t =

of liie superconductingphaseis lower

tc
than

in

zero

magnetic

that

of the

fieid

normal

be

the

phase

the free

energy
phase. The free
field, as we show

energy of the superconduciingphaseincreasesin the magnetic

beiow. The free energy
the normal
of
phase is approximately independent of
the field. Eventually,
as
the
the free energy of the superfieid is increased,
is
will exceed
that of the normal phase. The normaiphase
superconducting
phase
ihen
the stable phase, and superconductivity is destroyed.
of
is
The increase
the
free energy of a superconductor in a magneticfield
in the interior
calculated
as the work required to reduce the magnetic
field
to zero
the Meissner
the
is
account
for
of
to
required
superconductor; the zero value
in
the
effect. Considera superconductor
form
of a long rod of uniform crosssectioninsidea long solenoid that produces a uniform field B, as in Figure 8.19.
is
The work required to reduce the field to zeroinsidethe
superconductor
a counteracting
the
equai to the work required to create within
superconductor
field
We know from electromagnetic
B thai exactlycancelsthe solenoid
fteld.
B is given
the
work
by
theory that
per unit volume required to create a field
(SI)

(CGS)

B2/2{t0\\

E5a)

E5b)

Figure 8.20

Tlic free

noi\\ti\\^i

t\\otii\\3.t meiat

syndic

melai

energy

Al a
$\342\200\236.

fkUi

magnetic

and Work

dcnsiiy

F* of

is

in

x <

zero

SI

unite

land by BBJ/8n

lhai Fs(r,/iJ
larger

=\342\226\240

deiisiiy is lower

ihe

in

siiperconduciing
si ale is ide siabic

vertical se;ilc in
ftgute

equally

so

uniis),

Ba3/2j@. If Bu is
BM ihe free energy
siaic than in
normal
field

st,iie. The

ilic

Bj/l/i,,,

Fs by

CGS

siaic, and

the

An

F^i.O).

F5(r,0)

criikjil

liian ihe

in

the

xt

magnate

dial Fsti,O)is lower

than
field
increases
applied magnetic

field, so
in

applied

temperature

is a superconductor

appcox.iiv\\u.lcty

intensity of the

of [he

independent

Heal

Si

Chapter

of i tic

f Jr-O)-The

is ai

drawiiij;

10 U5

applies

no* ihc nornmt

origin

und

ii\\

Us

= 0.

Tiiis is the amount by

is raised by
constant

magnelic field Ba

Applied

which

free energy

the

density

application of an externalmagnetic

the

in

bulk

in an

field,

superconductor

experiment

at con-

temperature.

There

because

is no

free energy increase for

comparable

there is no

screeningof

the

normal

conductor,

Thus

field.

applied

the

(SI)

E6a)

{CGS)

E6b)

the
field
magnetic
energy density of both phasesversus
tne
free
will
rise
of
the
energy
superconductingphase
ultimately
{Figure 8.20),
above
that of the normal phase,sothat in high fields the specimen will be in the
normal phase, and the superconducting
is no longer the stable phase
phase
This is the explanationof the destruction
of superconductivity
by a critical
En

plot

of

the free

magnetic field
Wiih

Bf.

increasing

superconducting

decreases. Everything

the free

temperature

phase decreases as
else

being

equal,

superconductor will lead to boili a high

field. The highestcriticalfields are found
highest

crilical

temperatures,

energy differencebeI ween

--\302\273

rr,

and

high

critical

amongst

and \\ice versa.

the

stabilization

temperature

critical

normal

magnetic

energy

and

and

field

type I
a high critical

the superconductors

in a

with

the

SUMMARY

1. Heat is

contact

by thermal

energy

process dQ = xda,

reversible

2.

of

transfer

the

only

by a change in theexEerna!
parameters
the system. The entropy transfer in a reversibleprocessiszero
is performed and no heat is transferred
work

The

Carnot

the

is

Work

of energy

transfer

that

describe

3.

t!ie ratio WjQh

limit to

4.

limit to

upper

of

5. Thetotal

work

the

efficiency,
j;c = (zH
to the
work generated

the ratio

on

performed

the

of

QijW

&

roof

6.

the

the

Hclmholtz

is the

upper

system.

effective work performed on a system

pressure in a reversible process is equal

The

energy

7. The

tJ/tj,

in a reversible
temperature
free energy F se U - ro-

at constant

system

process is equal to the changein

\342\200\224

when

heat added.
~
- r,), is the
performance, -,'c t,/(ta
heat extracted
to the work consumed

of refrigerator

coefficient

Carnot

The

conversion

energy

In

reservoir.

with

to

particles

the

8. Tlic changein
by an

external

the

to

change

- w + pK.

work

chemical

constant

at

system
the

on

performed

free

a system

in

the

reversible

and

temperature

in the

Gibbs

transfer

of

free

t.lN

is pdN.
energy

density

of a

superconductor {oftype

in
magnetic field B is B2/2{i0

SI

and

S2,8;i

{) caused

in CGS.

PROBLEMS

/. Heat pump,

per

unit

of

heat

(a)

Show

delivered

that

inside

fora reversible heal pump tile energy required

the building is given by the Carnoi
F):
efficiency

Chapter S: Heat and Work

2.

In absorption
refrigerator.
not as work, but as heal

Absorption

process

is

fuel,

supplied

home and

xh. Mobile

>

i(,h

(a) Give an

refrigerators the energy driving the

a gas
from
flame at a tempenisure

cabin refrigeratorsmay

energy-entropy

flow

be

diagram

this type,

of

similar

to Figures

with

propane

8.2 and

involving no work at all, but with energy and entropy

> ta > ij. (b) Calculate the ratio QJQhh,
three temperatures
rfch
at r \302\253r,, where QM is the heat input at r = xhh. Assume
heat extracted
a refrigerator,

such

Hows

the

at

8.4 for
for

ihe

reversible

operation.

Camot engine. Considera Carnotengine

uses as the working
that
substance a photon gas. (a) Given
V2, delerwne
i,, and
r, as well as Vl and
and
is
heat
the
work
done
What
the
taken
and
Vi
VA. (b)
Qh
up
by the gas during
the
first isothermal
Are they equal to each other,as for the ideal gas?
expansion?
Do
the
two
(c)
isentropic stagescanceleach other, as for the ideal gas? (d) Calcuit with
the
total
work
done by the gas during one cycle.Compare
the heat
Calculate
is the
Carnot
taken up at rh and show that the energy conversion efficiency
3, Photon

efficiency.

4. Heat

The

cascade.

engine\342\200\224refrigerator

of a

efficiency

heat engine is to be

tow-temperature reservoirto a
temperature
r,, by means of a refrigerator. The
consumes
of the work produced
part
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

valuer,.,
refrigerator
below

in

this

the

lowering

by

improved

the

of its

temperature

environmental

way?

5. Thermal

pollution.

a water

with

river

temperature

T} =

2CTC

is

to

be

the low temperature reservoirof a large power

with a steam
plant,
=
of
500JC.
If
the
amount of
temperature
Th
ecological considerations limit
heat that can bedumped
the rtver to \\ 500 MW,
into
what is the largest electrical

used as

output that the plant can deliver?If improvements

would

permit raising

Th

by

what

lOQ'Q

in

effect would

hot-steam

this have

technology

on the plant

capacity?
air conditioner operatesas a Carnot
cycle
between an outside temperature Th and a room at a lower temperarefrigerator
\342\200\224
this heat
room gains heat from the outdoors at a rate A[Th
temperature7\"j. The
T,);
is P.
T
he
to
the
unit
the
air
is removed by
condilioner.
cooling
power
supplied
(a) Showthat the steady state temperature of the room is

6.

Room

ah

A room

conditioner.

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
A of the room
in W K\021.A good
power of 2kW, find the heat losscoefficient

Amer. J. Physics
2S2 K

air conditioners

of room

discussion

and the

7. Light bulb

Carnoi

In a

19 A978).

46,

is given by

a refrigerator,

in

that draws

S.

Gcoihermal

to

generate

to drive

steam

energy.

electricity

rockdrops,

to

according

dQh

W. D.

Teeters,

bulb is

100 W light
Can

tOOW.

be

at

the

left

inside

burning

below room

cool

refrigerator

mass M of porous hot rock is to be

hot
by injecting water and utilizing the resulting
the temperature of ihe
result
of heat extraction,
= -~MCdTh,
where C is the specificheat
of the

very

a turbine. As

LefT and

K.

378

tempera!ure?
uiilized

S.

realistic unit the cooling coils may

outdoor heat exchanger

at

refrigerator

H.

large

assumed to be temperature independent.If the plain operatesat the Carnoi

ihe tola! amount W of electrical
estractable
from the
limit, calculate
energy
of the rock was initially Th = T,, and if the plant is to
rock, if the temperature
be shut down when the temperature has dropped to Th = Tf. Assume that the
rock,

lower reservoirtemperature
T,stays
end of

At the

the

calculation,

give

-.

constant.

a numerical

(about 30km3). C=Hg\"!K\"\"', T,-= 600 77

the units and explain all steps! For comparison:
The
Watch
in the world in 1976was between1 and 2 times
10!4
produced
9. Cooling of nonmetatlic
capacity

to Ti,

\302\253
0

as

by

means

solid

to

We saw in

T~Q.

solids

spin

\\

fermions

C.

electricity

kWh.

Chapter 4 that the heat

at sufficiently

(varying.) low-temperaturereservoir,and for

reservoir has a fixed temperature 1\\equal to the
solid. Find an expressionfor the electrical
energy
10, ltrerersibte

7\",

total

10u kg
\302\273
20

low temperatures is proportional

to cool a piece of such a solid to
Assume it were
possible
the solid
as its
uses
of a reversible refrigerator that
specimen

nonmetallic
~ aT3.
C

of

value, in kWh. for M

- 110 C,
C,

which
initial

tile

required.

a gas
of
expansionof a Fermtgas. Consider
at
a
volume
in
A/, initially
temperature
V;

of mass

gas expandirreversibly

into

a vacuum,

wiihout

high-temperature
Tj of the

temperature

N noninteractiilg,
if

doing work, to a

~ 0.
final

Lei the
volume

large
temperature of the gas after expansionif Vf is sufficiently
for the classicallimit
to apply?
Estimate
the factor by which the gas should be
value.
Give
numerical
for its temperature
to settle to a constant final
expanded
in kelvin
for two cases: (a) a particle massequal
values for ihe final temperature
=
mass
to the electron
as in metals;
and
(b) a particle
10\"cm\023,
mass,
NjV
=
stars.
white
dwarf
equal to a nucleon,and N/V
10JO,as in
V}. What

is the

Chapter

Gibbs

Free

Energy

and Chemical Reactions

FREE

GIBBS

Example:

262

ENERGY

Comparison

of G whh

265

266

IN REACTIONS

EQUILIBRIUM

Equilibriumfor IdealGases
Example:

of Atomie

Equilibrium

Example;pH

and

the

Ionszatton

Example: Kinetic Model of Mass

267

and Molecular
of Water

Hydrogen

269
265
270

Action

SUMMARY

272

PROBLEMS

272

1. Thermal ExpansionNearAbsolute
2. Thermal
lonization of Hydrogen

3. lonizationofDonor

Impurities

4. Hiopolynicr

5.

Patticlu-Antiparticle

Growth
Equilibrium

in

Zero

272

273
Semiconductors

2 73

2/3
274

Free Energy

9: Gibbs

Chapter

The Helmholtzfree energy

constant

and

volume

chemical

many

introduced

are performed

system at
many experiments, and in particular
at constant pressure, often one aimo

to introduce another function

at eonslant pressure ;tnd temperature.

define the Gibbs free energy

thermodynamie

- xa +

the

treat
As

in

equilibrium
Chupicr
8, we

A)

pV.

energy, and

this the free

call

to

as

G a

often

3 describes a

in Chapier

useful

configuration

Chemists

Reactioi

But

temperature.

reactions,
is

spherc,

Chemical

ENERGY

FREE

GIBBS

and

often

physicists

call

potential.

The most importantproperty

of the Gibbs
free energy is thai it is a
for a system S in equilibriumat constant pressurewhen
in thermal
a
(H.
G
with
reservoir
The differential
is
of
dU ~ ida

dG =

a system {Figure9.1)in

Consider
at

temperature

so

that

t and

the

differential

The thermodyiiamicidentity
zdds

B) becomes

cdx

pdV

contact

Vdp.
with

contact

minimum

a heat

reservoir

contact wilh a pressure reservoir<R2

<Rl

that

= 0 and
dt
p, but cannot exchangeheat. Now
dp = 0,
becomes
dG oflhe system in the equilibrium configuration

dGi

so that

thermal

in mechanical

the pressure

maintains

the

tt

dUs

B)

C)

is

E.39)

= dUi

dG^ \302\253ndNx.

xdax + pdV*

But

dGj

ttdNi

dNs

\302\273
0

= 0,

pdVs,

wh

ence

i eser

System

rese rvoir

Hea

\342\226\240oir

\342\226\240\342\226\240\342\226\240v\"'Jif

m,

a heat

v.hh

NPSu

qualiz

Pressure

whkh

reservoir

ger lo

on Hie

e pressure

and

reservoir

in

mechanical

barysiai or pressure
maintains
a constant pic

with a

equilibrium

system.

The

is

barysial

insuSalcd.

cserv

is tlic

which

condition for

at

constant

therefore, the

natural

variations

irreversible

change

G3

sign associated
place entirely wiihin

laking

respect

w'Hh

&

to system

varia-

number. Theseare,thereraiher

a minimum,

be

musi

wilh

and particle

minus

the

from

direciiy

extrcmum

temperature,
for G(N,z,p).

pressure,
variables

That ihe extremumof

follows

Gj to be ;m

the

will

than a maximum,
eniropy

in (i);

increase

a and

Any

ihus

decrease Gs.
With

B),

The

difierentiai

E)

may

Comparison of{5)and

be writicn

F)

gives

adx +

E)

as

the relations

0)

(8)

thermally

Chemical Reactions

Free Energy and

Gibbs

9:

Chapter

, = V.

Three
see

Maxwell

relations

from these

be obtained

may

E)
by cross-differentiation;

1.

Problem

In the

Gibbs

free energy G

\342\200\224
za

pKthevariabfesr

and pare

intensive

are
two identical systems
pui together.
But U, a, V, and G are linear in the number of particlesA':their value
doubles
We
when
effects,.
two identical
interface
systems are put togeiher,apart from
one particle
say that V, a, V, A7 and G are extensive quantities. Assume that
only
species is present. If G is directlyproportionalto N, we must be able to write

quantities: they

not

do

value when

change

G=
ep is

where

quantitiespand r. If
wjih

temperature,c;idi

does

not

of N because it

independent

identical

molecules,

j.V

in

change

two

the

A0)

Nip(p,x)

is

function

only

of the

intensive

and temperaiire |>ui together, the Gibbs free energy

volumes

process.

of gas at

It follows

equal pressure

from this argument that

(II)

We

in G)

saw

that

A2)

so that

<p

must

be

identical

with ;j,

G(,V,p,t)

and (iO) becomes

A3)

is equal
to 'h
for s single-componentsystem
I or
G for an ideal gas, sec B1) below.
Gibbs free energy per particle,G'/A'.
If more than one chemical species is present, A3) is replacedby a sum ov

Thus

the

chemical

poiemiaf

all species:

A4)

Gibbs FreeEnergy

The

becomes

identity

ihermodynamic

xda = dV

pdV

A5)

^e/INy,

and E) becomes

shall

We

the

develop

G ss: YJ^jfif

that

ts

reacting

\302\243njdNj

(!6)

+ Vdp.

adz

of chemical

the property
equilibria by exploiting
with respect to changes in the distributionof
in a
t, p. No new atoms comeinto the system

theory

a minimum
at

molecules

\302\253

dG

constant

themselves
reaction; the atoms that are presentredistribute
snucics to another molecular species.

ti
\302\273f

Omipurhtw

iiiutupfri

Let

F.

with

sttf

its

is Jitiacut

wluit

molecular

one

from

:ihuuJ

\\\\vi

rd.ttions

iwo

= p(iVrT,K)

{cFfdN)tty

A7)

and

*=

$G/dN)tiP

We found

lM

in F.18)

for an ideal

(IS)

fi{T,p).

gas

MN.r.F) -Tlog(WKnQ) ,
so

that

ti(N,z,l')

is

not

and therefore

of N

independent

She iaiegra!of{S7).
Thai
is, f is not direciiy proportional lo N
number of particles is increased. Instead,from
F(t,V,N)^

But

she

Gibbs

free energy for

C(r,/\302\273,N)

t-he

\302\273
F

if ilie

system

we cannot
is kept at

PK

gas

potential

in

the form

cotislanl volume

ihc

as

B0J

is

N/V

- l] +

Arr[!og(p/rny)

==

p/r.

-Vr

PO

NrIog(;j/THQ)

of ihe ideal gas Saw

JV;i(r,f) .is

- I].

\302\273.

by use

F =

write

F.24),

Ni[\\og(NJVnQ)
ideaJ

A9)

We readily

identify

in B1)

the

chemical

us

/((t,p)

= i

lo\302\243(pJxnQ)

B2)

9; Gibbs Free Energy

Chapter

Reactions

Chemical

and

G \302\253
in sit.V) in
We see [hat N appears
by reference to the result
iVjih.pV
unavoidably
but not in /j(t,p)
in B2). The chemical potential is the Gibbs
free energy per particic,
A9),
but
il isnol
ihcHctnihoHz
free energy
Of course, we are free lo wrile p its cilher
pet panicle.

A9) or

122},as is convenient.

IN

EQUILIBRIUM

We may write the

REACTIONS

equation of a chemicalreactionas
v,A,

v2A2

= 0

\342\226\240
- \342\226\240

v,A,

B3)

B4)

species
Hj

in

the

reaction

equation.

species, and the Vj are the coefficients

Here v is the Greek lettermi. For the

of the
reaction

Clj = 2HC1 we lave

+
=

Ai

the chemical

Aj denote

the

where

- Clj;

A,

H,;

Aj

fj=l;

Vi=l;

HC1;

\302\273j=-2.

B5)

of chemical

discussion

The

conditions

of constant pressureand

energy isa minimumwith

The

differential

of

respect

constant

presented

In

temperature.

in the

to changes

for

equilibrium

proportions

reactions

under

the Gibbs free

of the reaclants.

G is

dG

Here//j

equilibria is usually

- Z fj^i

adz

Vi!p.

B6)

is the chemical potentialof species

j, asdefined by \\is = {BGJdNj)s-p. At
= 0;then B6) reduces
pressure
dp = 0 and at constant temperaturefa

to

07)

rfC-1/,/W,.

The changein

the

potentials of the
zero.

Gibbs

free

re\302\243tctbnts\302\273
Xti

energy
comlit^rtufii

in

reaction

depends

is &i cxtrcmum

on the chemical
tjo
uu musl
miu

for

Equilibrium

The change
coefficient

dN} in

the

the chemical

v,m

of species/

of molecules

number

equation

]>>/.; - 0.

We

may

Ideal

Gases

is proportionalto the
dN} in

Write

the form

\"

JNj
dfif indicates

where
in

how many

\302\253

rjd$

B8)

timesthe reactionB4)

takes

place.

The

change

dG

becomes

B7)

dG

In equilibriumdG

0, so

\302\273

dft-

vjfi

B9)

that

C0)

This is the conditionfor

pressure

and

for Ideal

0 when

utilize

We

F.48)

nj

is the

concentration

which

is

the

depends
internal

Uul ihcmull

when

p and

genera!

the constituents

equilibrium condition
acts as an ideal gas.

potential of speciesj as

of species j

logc;) ,

C1)

and

\302\253QJZ/int)

C2)

on ttie temperalure but not on ttie concentration.HereZ/int)

function,
F.44). Then C0) can be rearrangedas
partition
5\302\273gnj

of

rflogMj

cj a

the

of

form

useful

we assume that each

lo write the chemical
fij

where

constant

Gases

simple and

We obtain a
Y^Vjf-j

of matter at

temperature.*

Equilibrium

transformation

in a

equilibrium

is moregencrat; onceequilibrium

t arc specified..

\342\226\240

$>,!(*<:,

is reached,

ihe rcaclion

C3a)

does nol proceedfurihi:r,

Chapter 9: Gibbs

Free

and Chemical

Energy

Rcactia

C3b)
The left-hand sidecan berewritten

as

C3c)
side can

the right-hand

and

be expressedas
C3d)

Here

the equilibrium

called

K(t},

constant, is a function only of the

temperature.

Wiih{32)\\vehave

K{t)

free energy

internal

the

because

C4)

nil\302\253/'

is Ffim) =

-TiogZj{int).

From

and

C3c,d)

we have

C4)

C5)

Fk-Vj

law of mass action.The result

as the

known

concentrations of the reactanlsis

in

of any one

the conceniraison

concentration of one or moreofthe

the equilibrium

To calculate

a consistent
on our

choice of the

without

happen
l\\2

a conscious

2H, ilie simplest

is

It

effort

not
on

the

of the dissociatedpanicles(here

2H)

of

the

ground

state

of the

change

equilibrium

it is

essential

to choose in

partition

function

The

depends

Zji'mi)

different

need

zeros

properly the energy or free

for the
energy

to arrange ibis, but it docs

not
part. For a dissociation reaction such
clioosethe zero of the internal energy

diilicuh
our

procedure is to

of each compositeparticle(here

C4),

eigenstales.

to give

be related

reaction.

in ihe

difference

as

must

reactants

different

in the

energy of each reactant.We

internal

zero of the energy

a change

reaclants.

other

the value of each

because

consistency

alone.

temperature

force

constant K(x}in

of the

zero

the

way

here

of the

a function

reaciam will

product of the

the indicated

that

says

H2
a!

molecule}
res!.

to coincide

we piacc

Accordingly,

composiie particle at

~\302\243fl,

with the

where

is
\302\2433

energy
the energy
the

energy

Equilibrium for

required

in

to be

laken

is

and

positive.

Examplei Equilibrium

of

atomic

rcacuon Hj

for the

aciioil

mass

hydrogen imo

particle into its constituents

the composite

to dissociate

reaction

the

Ideal Gases

atomic hydrogen

and molecular hydrogen.

= 2H ttz ~ 2H = 0

or

The siatcmcnl of ihe

for

the

dissociaiion

law

of molecul

is

C6)

denotes ihc concenmuion of nlolecutar

Here [llj]
atomic

of

li

h>drogen.

hydrogen,

and

fjt]

foltov-sihai

l37)
[h^tpo17^'

lhai is, the relume concentration

proportional lo the square rooi of
K is

equilibriumcon:.lani

given

logK

in

of the

terms

of

atomic

ihe

concent

at a given
is inversely
temperature
hydrogen
ration of molecular hydrogen. The equilib-

by

log^tHj)

internal free energy of

2IognQ(H) -

H,. per

molecule.

Spin

F(U2)/i,
factors are

C8)

absorbed

in

F(H,}.

is H,, the
of energy is laken for an H atom at rest. The more lightly
bound
is Kt leading
of Hj in ihe
10 a higher
more negative is F{Ht), and ihe higher
proportion
al absolute zero.
eV per molecule,
mixture.
The energy to dissociate Ht is 4-476
be said lhai ihe dissociationof molecular
into atomic hydrogen is an
It may
hydrogen
of
dissociaiion:
The
En
associated
wiih ihe decomposition
example entropy
gain
entropy
[he
It is believed
of Hj into two independent
in
loss
particles compensates
binding
energy.
reaction
in
not
The
that
most
the
is
H
and
of
Ht:
intergalactic
hydrogen
space
present as
in the direction
of H by the low values of ilie concentration of Hj.
equilibrium is thrown
Here

[he zero

Hjdrogcn

is very dilute

Example:

pi! and ihe limitation of water.

in

intergalactic

space.

In

liquid

waicr

ihe ioni^lion

process

09}

H2O*~>H+ + OH\"
eeds

to

o.ximalcly

txicnt. Al room
tcinpcraluic
she coiiccmraikm product

a slight
by

the reaciion

cquilibfium

D0}

where ihc jonac

^nefcasco

aGGin&

oy

lo

as required

can

ions

decrease

of

z\\t\\

iictu

ionizaiion

be increased

\342\200\224

fOH

^=

\021

of H* ions is

wai^r

\302\273^ntJ
ihe concentration
of C3i 1 tons wtll decrease
constant. Similarly, ihe concentration
[H*][O!!']
*
a hase lo ihe water,
and ihe H
concentration will
adding

by

siaie oi wafer

The physical
process

prolon

product

is more

ions ate

H*

suggests\342\200\224ihc

of H2O molecules.This

with groups*

per liicr. inpurcualcr\302\243H*l

donor.
The concentration

moles

in

lo aa as a

to llic

the

accordingly.

ihe

is said

mainiain

\"

of OH

arc given

concentrations

An acid

!0\021molr''.

Chemical Reactions

Free finersy and

Gibbs

9;

Chapter

protons,

affect ihe

not sigiltficantry

does

than ihe equation

complicated

not bare

associated

are

but

of

ihe reaction

letmsof

ihe

vulidily

equation.
it

convenient

is ofien

lo express theacidily

oraikalinii) otasolulionin

pti,

defined as

pH s -log10[H+].

The

pH

concentration
in
The

base ten of iht; hydrogen

ion concentrais ihe negative of the togarilhm
=
liier
The
of
water
7
because
!CT7mair'.
oCsolution.
is
per
pH pure
[H*]
acidic sotuiions have pH near 0 oi even
have
an
negative;
apple may
pH - 3.
lo
is
basic.
has
a
of
73
it
7-5;
slightly
plasma
pH

solution

ota
moles

slrongesi
blood

Human

Kttictic

Kxati\\ple2

nB,

action.

modelof/nms

AB. We suppose that

t!ie concentrations

moieculc

nAB denote

is

AB

of A,

where the me constant C describes

rale constant D describesthe reverse
atoms A and B. in thermal equilibrium
= Oand
so that du.a:di

the

B combine to form a
collision of A and B. Let ha,
formed in a biaiomic
of nAB is
B, and AB respectively. The rale of change
Suppose

formation

a function

of

temperature

derived earlier by
Suppose

\"

The

by

o[AB

some

ptolon.

505A958).

catalytic

in

a collision

of A

result

is consistent

law

ihe

its component
ace constant,

D3)

D/C

with ihe

B, and

with

process, the ihemiat decay of AB into

the concermaiions
of all consiiiutents

only. This

action

of mass

that we

thermodynamics.

AB is noi formed

dominant

one
surrounding

standard

A and

atoms

that

nAB

formed

D!)

principally

by

the bimolecular

collision of

and

B, but

is

process such as

species present
A [cvie* is given

is

most
by

molecules
surroundlikely it*1 4HjO, acomplc*of4 water
P(oc_ Roy. Soc tLondon) A147.
M. Eigcn and L. Dc Macycr,

\342\226\240
.

Here E is ihe

So long as ttie

catalyst which
intermediate

to its original slate

AE ts so short lived that

is returned

product

up as AE, ihc ratio iiaiiu/iUb in equilibrium

direct
above.
process A + B<--AB treated

is lied
the

actually
The

proceeds, ihc equilibrium must

in equilibrium of the direct
equality

of detailed

be

the

and

ai ihe

end

IdealCases

for

Equilibrium

seeond step.
quantity of A

of the

no significant

us if AB were formed
what
route Hie reaction
by
same.
The rates, however, may differ.
inverse reaction rate's is culled the principle
must

No

be

the same

in

rnaiier

balance.

Comment: Reactionrates. The law of mass action expresses ihc condition

satisfied
by ihe
concentrations once a reaction
aboui
how fasi
lias gone to equilibrium,
li iclis us nothing
AH as it proceeds,
ihc reaction proceeds. A reaciion
A + B = C may
bat
evolve
energy
before the reaction can occur A and B may have 10 negotiate a potential
as in
barrier,
is called the activation energy. Only moleculeson the high
Figure 9.2. The barrier
heigh!
will not be able to get
end of their
will be able to read; others
distribution
energy
energy
over the potential hill. A catalyst speeds up a reaction by offeritig an alternate reaction path
a lower energy of activation, but it does not change the equilibrium
with
concentrations.

Schematic

AH measures
ihe energy evolved in the reaction
the equilibrium concentration ratio [A][B]/[C]. The
barrier to be negotiated
is the height
of the potential
energy
the
reaction
it
determines
the rate at which
the
can proceed, and
takes place.

Figure 9.2

The quantity

nnd determines
activation
before

reaction

coordinate

Chapter 9: Gibbt FreeEnergy

Reactions

Chemical

and

SUMMARY

1. The

Gibbs free energy

G3
is a minimum

thermal

in

2. (cG/3r)H,= -a;

= W,,(r,ri

ofmass

law

for a

action

of

the

pV
temperature and pressure.

V;

= p.

(SG/SN),.P

chemical reaction is that

IK'

a function

iff +

at constant

equilibrium

tfG/cph.,

3. C(r,p,W)
The

- -^w.

alone.

temperature

PROBLEMS

/. Thermal expansion near absolutezero,

(a)

the

Prove

three

Maxwell

rela-

relations

(dV/di)P

-{dts/dp),

(aVldN)p = +(ap/ap)^ ,
(Qj/cr)jV

two

omit

(lie help
Coefficient

of

subscripts

of D5a)
tjicrniiti

approaches

D5c)

appear similarly in D5b) and D5c).It is commonto

that occur on both sides of theseequalities,
Show
wilh
(b)
the third law of thermodynamics
tjiat the volume Coeffi-

should

subscripts

those

~Ea/dN)x.

D5b)

D5a) should be written

Strictly speaking,

and

D5a)

and

expansion

zero as t

-* 0.

2.

Thermal

ionization

in

hydrogen

c +

wheree isad

H*ftH,

electron on a proton H*. (a)

of the reactants satisfy
the relation
of an

the

that

Show

of atomic

the; formation

Consider

of hydrogen.

the reaction

the

as

eicutron,

concentrations

equilibrium
I

D7)

[e][H+J/[HJs\302\253acxp(-//T),

/ is

where

(he energyrequited to tontze

refers to the electron.Negiecithe

not aSTed

and

electrons

concentration

atomic

of

spins

and

the

{im/2zh2K11
this assumption does

hydrogen,

particles;

tiQ

is known as the Saha equation.Ifall the

arise from the ionization of hydrogen
the
then
protons
atoms,
of protons is equal to that
and
the
of
the
electron
Electrons,

concentration is

The result

result.

final

the

by

given

D8)

0]~[H]\"V'3\302\253p(-//iT).

problem arises in

A similar

thermal ionization

semiconductor

of impurity

The

is

electronic

excited

[H(exc)]
andT -

with

[e]

/ is

a simple

the ionization

proportional

energy,
the square root of the

to
!

electrons to the system, then (He

state,
conditions

for

ts not

this

that

shows

which

concentration.

atom

(b) Let [H(exc)]denotethe

first

/,

Here

problem.

concentration

elccjron

If we add excess
will decrease.

C)

^1 and not

involves

\"Boltzmannfactor\"
hydrogen

the

exponent

B) The

u-jth

connection

of electrons.

are donors

that

atoms

in

physics

No lice lhat:
A)

hy-

adsorption

which
atthe

of

concentration

equilibrium

the
is \\l above
ground
surface of the Sun,with

5000K.

of protons

concentration

H atoms in the
state. Compare

[H]

1023 cm~

|
I

3,

of donor

hnization

impurities in semiconductors.

\\ A

pentavalent

impurity

atom
in crystalline
silicon
introduced in place ofa tetravalent
the role of
in free space, but with
silicon acts likea hydrogen
atom
e2/e
playing
e2 and an effective
mass
m* playing
the role of the electron mass m in the
state
of the
of *hc kmizalion energy and radius o( the
ground
description
the
diclctltic
consta.t\\t
free
silicon
electron.
For
impurity atom, and alsofor the
e ~ 11.7 and, 0pproxima!e!y,
m*
=0.3
m. U there are 10\" donors p^r
cmJ,
K.
100
electronsat
cent
ration
of
conduction
estimate
the con

(called

4.

a donor)

monomer

polymers

4-

the

Consider

Siopotymergrowth.

of linear

A'mer

made

= (A'

up

of

chemical

identical

-f l)mer.

of a sotution
basic reaction step is

equilibrium

units. The

Let K^ denote liieequilibrium

constant

for

Chapter

9: Gibbs free

this reaction,

Reactions

Chemical

and

Energy

(a) Show from the law

mass

of

\342\200\242
[\342\226\240
\342\226\240]

lhat the concentrations

action

satisfy

[N

from the

(b) Show

1]

[If \"/K.KjKj

Iheory of reactionsthai

\342\200\242
\342\200\242
\342\226\240

K.v

ideal

for

gas

D9)

conditions

(an ideal

solution):

where
iVmer

MN is

^Bnti2/M,^rm

wQ(W)

the mass of the Nmer molecule,and

molecule,

(c)

Assume

ratio [N

concentration

4-

N
t]/[N]

\302\273
j,

at

so

thai

room

FN

E1)
is the

nQ{N) =

Hq{N

free energy
+

if there

temperature

1),

of one

Find

is zero

the
free

basic reaction siep: that is, if AF = FKi.l ~ Fs ~ fj =-0.

=
in
a bacteria!
Assume
as for ammo acid molecules
ceil. The
10aocm~3,
[I]
molecular weight of the monomer is 200.(d) Show that for the reaction to go in
the
direction
of long molecules we need AF
<
This
~0.4cV,
approximately.
condition is not satisfied in Nature, but an ingenious
is
followed that
pathway
simulates the condition. An elementary
is given by C. KiUel, Am.
discussion
J.
energy

Phys.

in the

change

40,60A972).

for the
expression
equilibrium, (a) Find a quantitative
=
=
n+
n~ in the particle-antiparticle
concentration n
reactionA+ 4- A\" = 0. The reactants may be electronsand positrons;
protons
Let the mass of
and antiprotons;
or electrons and hoies in a semiconductor.
the
either particle be M; neglect
of the particles. The minimum
energy
spins
A\"
is A-Take
the zero of the energy scaleas the
release
when A* combines with
with
no particles
energy
present, (b) Estimate n in cm\023 for an electron (or a
300
that
K. with a A such
A/t = 20. The hole is
hoie) in a semiconductor T \302\253*
viewedas the antiparticic
to the electron.
Assume that the electronconcentration

5. Pavtkte-antipartkk
thermal
equilibrium

is equai to

the

hoie

concentration;

assume

aiso

titat

the

particles

are in

of (a) to let each particle have a spin of

classical regime, (c) CorrectIheresult
Particles
that have amiparticfes
are usually fermions with spins of \\.

the
3.

10

Chapter

Transformations

Phase

PRESSURE

VAPOR

276

EQUATION

the Coexistence Curve,p Versus

Derivation
of
Point
Triple

278

284

Latent Heat and Enthalpy

Model

Example:

System

WAALS

DER

VAN

284

for Gas-Solid

285

Equilibrium

287

OF STATE-

EQUATION

Mean Field Method

CriticalPoints

288

the

for

Gibbs Free Energy

van

der

the

van

of

2S9

Gas
der Waals Gas
Waals

291

Nucieation

Fe

from

agnet

295

298

OF PHASE TRANSITIONS

THEORY

LANDAU

302

Ferromagnets

Example:

First

294
ism

Order

302

Transitions

305

PROBLEMS

1.

2. Calculationof
3. Heat
4.

and

Energy,

Entropy,

for

dTjdp

Gas-Soltd

7. Simplified

Note: tn

305
305

Water

Order

the

305

305

Equilibrium

305

Equilibrium

of
6. Thermodynamics
First

der Waals Gas

of Vaporization of Ice

5. Gas-Solid

8.

of van

Enthalpy

the

Superconducting

306

Transition

Model of the SuperconductingTransition

Crystal

first section

307

307

Transformation

s denotes c/iV,

the

entropy

per atom.

In

the

section

on fcr

Chapter 10: Phaie Transformations

PRESSURE

VAPOR

of pressure versus

The curve

EQUATION

by

together

appropriate conditions can

of a system
is a portion
phase

and under

or solid

a liquid

in

energy

another

one

with

interact

of matter at constant
substance. The curve is
a real gas in which the atoms

of the

isoihcrmsof

the

We

or molecules
associate

free

the

a quantity

for

volume

temperature is determined
calledan isotherm. consider

phase,

that is uniform in composition.

Two phases
real

ofa
in

atoms

the

in

and

solid

we say

As

There

are isotherms at

in

isothermsfor

and gas

soiid

which

holds also

equilibrium

liquid-gas

low icmperaturcsfor
for

the

which

coexist. Everything
equilibrium

solid-gas

solid-liquid equilibrium.
and

on a

coexist

may

vapor*

section of an isotherm only

the
the

phase\342\200\224exists,
only a single phase\342\200\224the
the pressure. There is no more reason to cali this phase a gas than
we avoid the issueand callit a fluid. Values of the critical temperature

great
so

no

fluid

temperaiure

a liquid,

if

isotherm lies below a critical temperaturerc. Above

of the

temperature

how

the

other.

coexist and

the

Liquid
critica!

phase.

gas

liquid
for

and the

each

with

boundary between them. An isotherm

p-V
plane in which liquid and gas coexist
10.1, part of the volume contains
Figure

a definite

show a region in

gas may

equilibrium

with

coexist,

may

for severalgasesare
Liquid and gas

iO.t.

in Table

given

matter

extent of an isotherm
a
to
from zero pressure
infinite
along
they coexist at most only
pressure;
of atoms,
fixed number
section
of the isotherm. For a fixed
and
temperature
the
there will be a volume above which all atoms present are in
gas
phase.
at
room
bell
an
sealed
A small drop ofwater placedin
evacuated
temperature
jar
will
A

water

of

entirely.
the

evaporate
the

from

atoms

relations

are

by

suggested

for

the

the entire

along

the bell jar

filled

with

gas at

H2O

some pressure.

may
already saturated with moisture
There is a concentration of water, however,above which
into a liquid drop. The volume
vapor will bind themselves

exposed

The thermodynamic

conditions

coexist

never

leaving

entirely,

evaporate
drop

will

to air not

Figure

JO.i.

conditions

equilibrium

for

of two

the

coexistence

of two

systems that are

in

phases are the

thermal,

diffusive,

Vapor Pressure

IO.I

Figure

is constant, but
Efiei^

is only

and its

<t

the
s^nclc

vapor are in

of a

isotherm

Pressure-volume

such that liquid

temperature
is, t < tc. in the two-phase

and

Gas

+ gas

Liquid

Liquid

gas phases

region of

Hquid

reyj

gas

at a

may coexist,that
4- gas the pressure

may change. At a given lempcrature

a Jjtjuiu
v*iluc of tltc ptcssurc for Vvh^cri
at
we
move
the
Jf
this pressure
equilibrium.

volume

some of the gas is condensed

to liquid, but
remains unchanged as Jong as any gas remains.

down,

piston

pressure

Table 10.1 Critical temperatures

T,.

of

gases
Tt, in

in

He

5.2

H2

Nc

414

N.

Ar

151

210

Oj

Kr

Xc

289

CO,

33.2

126.0

1543
647.1

the

.W.2

Equatio

10: Phase

Chapter

Transformations

and mechanical contact. Thesecondilions

are
for

or,

18\\

Ml

the

phases

pressure

temperature

the
general point in the p-x plane
alone is stable, and if
liquid
phase

At a

Metastablephases

may

may

phase

have

a lower

by

occur,

be the pressure for

which
that

dp;iQ

the

divides

It is a

pl

and

liquid

A)
phases.

gas

in the

species

Note

that

the

two phases must be

B)

/ijl

two
ns

coexist: If /i, < ng

the gas phase alone is stable.

phases
<

Pi

do not

or superheating.

supercooling

metastable
a

chemical potential.

temperaturez0.Suppose
Pa

p2;

a transient existence, sometimesbrief, sometimes

long,at
another and ntore stable phaseof the same
subslance

Derivationof the CoexistenceCurve,

Let pQ

for which

temperature

has

fit

potentials are evaluatedat the common

of the liquid and gas, so that

/l,(p,T)

the

t2:

The chemical

coexist.

common

and

Pi = Pg

/Jj,;

where the subscripts / and g denote the

chemical potentials of the same chemical
if

tj

and gas,

liquid

*j

equal

that

+ rfi.Thecurve

p, t plane into a

the

two
two

in thep.T

Versus

phases,
phases

liquid and
also coexist

gas, coexist at the

at the nearby point

plane along which the two

phase diagram, as

given

in

Figure

phasescocxist

10.2

for H2O.

condition of coexistencethat
C)

D)

dt).

We

relationship betweendp
a series expansion of each sideof D) to

C) and

Equations

make

D) give a

and

dx.

obtain

-.

E)

ion

Cot

ojthc

Figure

10.2

relationships

the

jiB in

and

Phase diagram of H.O. The

chemical poienmls /t,. ;i,.
solid, liquid, and gas phases ate
of the

shown.The phase

here

boundary

bciwcen

ice

and water is not cxacily vertical; the slope is

actually negative,although
large. After
very
Iniemalionat Critical Tobies.Vol. 3. and P. \\V
Proc. Am. Acad. Sci.47, 4-i| A912)
Qridgman,
forms of ice. see Zemamky,
for
the several
p.

-100

100

200

Temperature,in
In

the

limit

as dp

300

375.

400

\302\260C

and dz approach zero,

F)

by

C)

which

and

E). This

result may

is the differential

be rearrangedto give

curve
equation of the coexistence

or

vapor

pressure

curve.

The derivatives of the chemicalpotentialwhich

in terms ofquantities

accessible

to

measurement.

occur

In the

may be

expressed
treatment of the Gibbs

in G)

Chapter 10: Phase Transformations

free

With

9 we

in Chapter

energy

the definitions
s

the volume

for

relations

the

found

per moleculein

and entropy

1 (cG\\

5 =

V/N,

o/W

(9)

each

we have

phase,

(dp\\

)JJ
Then

for

G)

becomes

dp/dt

01)
~

Here

sa

st is

moleculefrom

of entropy

the increase
the

gas, and

the

to

liquid

the

of

ihc

is

t\\

vg

we transfer one
increase of volume

when

system
\342\200\224

from the liquid to the gas.

It is essential
to
understand
thai the derivative dp/dz in (I!)
ts not simply
taken from
the
of state of the gas. The derivative
refers
to the very
equation
of
i
in
which
the
and
and
special interdependent change p
gas
liquid continue

of the system

we

when

to coexist.The number
varied, subject only
The
be

of
to

of molecules

numbers

quantity

added

sa

to the

one molecule

transfer

the

s, is

when

decrease

added

in the

the

system

as

vary

Here

constant.

moiecule

is

volume

the

Ns and

outside

in the

is transferred

reYersibly

the

of

temperature

from

molecule

one

transfer

(Va

the

are

system

from

constant.

process, the

must

that

the liquid

(If heat is

temperature

to the gas.)The quantity

of

will

heat

transfer is
l1Q ~

by virtue

will

gas phases, respectively.

liquid
related directly to She quantity of heat

sysfern to

the

A\\

phase

and

to the gas, while keepingthe

not addedto

+ Na

N,
in

in each

molecules

\"
TE*

of the connectionbetween

5'}'

and

heat

A2)
the

change

of entropy in a

reversible process.The quantity

L

tEs

A3)

of the

Dcritaiion

defines She latent heat of

Coexistence

vaporization, and is easily

measured

Cur

by

elementary

calonmetry.

We let
A*\302\253

the change

denote

to

she

We

gas.

of volumewhen

combine

A1), U3),

A4}

i-g-v,

is transferred

molecule

one

from the

liquid

and A4) to obtain

A5)

Clausius-Clapcyron equationor the vapor pressure

equation
of this equation was a remarkableearly
The derivation
of
accomplishment
Bo!li
sides
of
and
are
determined
thermodynamics.
(!5)
easily
experimentally,
the equation has been verified
to high
precision.
We obtain a particularly useful
form
of A5} if we make two approximations:
that
volume
the
(a) We assume
by an atom in the gas
I'j:
occupied
vg \302\273
is known

This

phaseis
replace

as the

much

very

larger

in the

than

liquid (or solid)phase,so that

pressure

atmospheric

(b)

so

that

may

Av by vg:

A6)

may

the ideal
written as

that

assume

We

i'9/i;( ^

be

!03, and the

approximation is very

gas law pVg

Av

With these

{16)

vt/yr

Avsva=
At

we

Ngz

applies

to the

good.

gas phase,
A7)

zip.

approximations the vapor pressureequationbecomes

of temperature,
molecule. Given L as a function
curve.
this equation
may be integrated to find the coexistence
the
the
heat L is independent of temperature over
latent
if, in addition,
Thus
the
of interest, we may take L = l.,Q outside
integral.
range
temperature
when we integrate (IS) we obtain
where

is the

latent

heat per

r
/dp

(lv

A9)

10: Phase

Chapter

logp

Traasfortnat

\342\200\224Z-0/i+

where p0 is a constant.We

one

where

LQ as

defined

to one

instead

refers

If Lo

nioiecuie.

) =

constant;

p0CXp(-L0/T)

the latent

heat of vaporization of

mole, then

A'cta, where No is t!ie Avogadro constant. For

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.
as !ogp
The vapor pressure of water and of ice is plottedtn Figure
!0.3
R

is the

versus 1/T.

gas constant,

R =

The curve is linear over

substantial

-Crit

ca! p

with

consistent

regions,

the

Jin.

\\
id

wa

er

X 103 \342\200\224
1 atm

pressure

Vapor

ofwaier

and of

The vertical scale is

dashed
line b a straiglif

\\

\342\226\240-

102

\"

is 1/T.
The

ice

iine.

\\

10

Si*\"

vc

\\ s
\342\200\242Ice

\\

1.5

2.0

2.5

3.0 3.5 4.0

lO'/T,

in

K~\302\273

4.5

5.0

Tcmperamre,
Figure

3
in

Vapor pressure versus iemperaiurcfor 4He. After H. van Dijk

Research
offheNauonal
Bureau of Standards 63A, \\2

10.4

eial.. Journal of
A959)-

10-4,
vapor pressure of 4He, plottedin Figure
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
a normal
should be so similar,
because
liquid is much more disordered than a
of a normal liquid is considerably higherthan
that
solid, so that the entropy

result

approxmiate

is widely

used

in

the

B0). The

measurement

10: Phase

Chapter

Transformations

of a normal solid. But

3He,

the

slope

is a

4He

the

of

liquid. For another quantum liquid,

curve is negative at low temperatures

quanhim

liquid-solid

entropy of the liquid is lessthan the entropy

solid has more accessible
statesthan the liquid! Liquid 3He
a Fermi gas,
has a relatively low entropy for a liquid
it approximates
because
has
a low enSropy when t \302\253
which
a large proportion
generally
zF because
of the atoms have
Sheir
momenta
ordered
the
Fermi
into
sphere of Chapter 7.

(Figure

region the

in this

and

7.15),

of the

solid. The

Triple

point.

The

poin!

triple

of

is that

a substance

point p,, t,

in

She

p~z

all three phases, vapor, liquid,and solid,

are
in equilibrium.
plane
=
=
solid
Here ng
/i(
/js. Consider an equilibrium mixture ofliquidand
phases
in
a
volume
enclosed
that
somewhat larger than
occupied
by the mixture
alone. The remaining volume will contain
in
the
vapor,
equilibrium wish
only
bo!h condensed phases,and at a pressure equal to the common equilibrium
at which

The

of

of

pressure

vapor

both

temperature

point

iriple

at

substance

She

This pressure is the triplepointpressure.

is not identical wish the melting temperature

phases.

somewhaton pressure; triple

under
common
equilibrium
the

the

For

the

water

defined

that

such

Latent

the

pressure of the two condensedphases.

is 0.01 K above the atmospheric
temperature
=
273.16K.
The Kelvin scale is
O.Oi\302\260C =
T,
vapor

point, of

triple

water is exactly273,16K; seeAppendix

ofa

Tile latent heat

and enthalpy.

heat

phase to she gas phase,is equal

the liquid

of the

temperature;

melting

pressure

point

triple

two

phases

difference

of

enthalpy.

The

at

constant

-f

pV

= dU -f

On the coexistencecurve jig

L
Values

of//

at coiisnint

are

\302\253
tAa

tabulated;

dV

-f- pdV

//,. Thus

\302\273
At/

phases, where H is

Hr-

difference

When

called

the

we cross the

applies:

ihey are found

\342\200\224-

Vtlp.

\302\273
Ml

B2)

jt,)dN

at constant

pressure:

pdV

(}tg

pAV

from

latent heat is also equal to the

coexistence curve,the thermodynamic

identity
Tito

the entropy

t times

B.

as

transformation,

phase

to

The
pressure.
the
two
between
is dH

differential

is the

lemperaSure

point

temperatures depend
meiSing temperature

Melting

pressure.

atmospheric

pressure
Ha

- llt.

by integrationof the

B3}
heat

capacity

of the

Derivation

Coexistence

Curve, p

Ver

B5)

jc,,

Example: Model system for

a solid in equilibrium

gas-sotidequilibrium.

We

construct

a simple model
can
derive ihe
easily
a
to
apply
liquid.

io de-

as in Figure 10-5.
vapor
Roughly the same model would
of N atoms, each bound as a harmonic
oscillator
of freImagine the solid to consist
u to 3 fixed
ol force. The binding
center
oleach
atom in ihe ground siaicis
frequency
energy
that
is, ihe energy of an atom in its ground
to a free atom at rest.
\302\243fl;
state is \342\200\224
co referred
\342\200\224where
The energy states of a single oscillator arc ntioi
h
a
or zero
is
r.o,
positive integer
in o:.e
we suppose itial each ntom can oscillaiconly
(Figure 10.6). For the sake of simplicity
dimension. The result for oscillators in [hrce dimensions
is left as a problem.
ol a single oscillaior in llie solid is
The
Junction
pariiiion

describe

pressurecurve

Z, =

for

ihis

with

a gas,

We

model.

\302\243\302\253p[-(n/10>

= expOWt)

eo)/r]

=
\302\243\302\253p(--,,Aa./T)

B6)
The Ziee energy

F, is

F* = u* ~
The Gibbs free

energy

in the

Gs

Tff,

B7)

-tlogZ,.

solid is, per atom,

\302\253

Vt

to-, +

pt',

=>

Fs

pvx =

//,.

Figure

10.S

wiih

aionis

pressureis a
energy ol the
in

than

aioms

in a

Aloms

in the

in

cqmSibn

gas phase. The equilibri

ol temperature.

function

The

solid phase is

in [he

atoms

ihe

solid

phase, bm the cmiopy of

gas
lo be
lends

in

higher

the

at
may

temperature

high

be

in ihe

iIk

atoms

all ot

gas.

\\

gas phase. . The

equilibrium configmaiion is dfiietiiiiacd

of the iwo ciTccls.A! low
cotmtcrpkiy

lanpemSurc most of

lo

;src in ll

most of

ihe a

ihe

10: Phase Transformation

Chapter

(u. The
lor of frequency
ssumed 10 be % below that

in!he

o(a

gas phase.

Ground Male <

aloui

bound

The pressure

volume

i>i

per

in

in ihe

gas phase: c, \302\253

vr

that

o[

solid phase is much

[he gas with

than

smaller

but Uie
which il is in contact,
atom
in [he
the volume vt per

\342\226\240

neglect the term

absolute activity is

If we

the

is equal to

solid

the

atom

pv, we have

(or

the chemical

potential of

,/t) =

[hesolidp, S

We

to be

'
with

equilibrium

we

insert

nQ from

gas

phase,

and we

take Ihe spin of

C0)
\302\253q

The gas is in

B9)

gas approximation to describethe

zero. Then, [rom Chapter 6,

the ideal

make

atom

whence
\342\200\236

exp(-logZJ

<stp(-to/i)[l -

the

the solid

t\\

'\"a

when

inQexp(-E0/t)[l

).f

or
).\342\200\236

- exp(-/1<0/t)].

C1)

C.63J:

C2)

(j^j

The

mode!

simplest

interactions

the

he was

below,

liquid-gas phase transition is that ofvander Waals,\\vho

gas equation pV = Nx to take into accounlapproximately
between
we
atoms or molecules. By the argument that
of a

ideal

the

modified

led to a modified equation of stateof the

(p

van

the

as

known

- Nb) = Nx ,

+ N2a/V2)(V

der Waals

equation of state. Tliis is written

molecules, and the constant /' is a measureof their

of
(Figure
10.7). We shall derive C3) \\vitli..tlie
help
We
shall
then
trcal
~-(SF/DV)liN.
in order to exhibitthe liquid-gas
For an ideal gas we have, from

The hard core

the

b is

had

gas

at

repulsion

To

we

now

add a

volume

-NT{log[)fQ(V

correction

a is

between

two

repulsion

range

=
properlics of the model
relation p

general

V,

be treated

can

distances
but

the

the volume per molecule.

We
replace
~
of
instead
Nb). Thus,
C4),we
N/{V

this

in

constant

for

the

C4|

+ i].

-NT[log(na/n)

in C4) by

atoms

F.24),

free

approximately as

volume

the concentration

therefore

short

tlic

the ihcrmodynamic

short

not the

available

for

transition.

F(idealgas)

if

C33

the
a, b are interactionconstantsto be defined;
of the long range attractivepart
the
of
mieraeiion

a measure

give

form

V. The

volume

of State

Equation

OF STATE

DER WAALS EQUATION

VAN

Waats

Der

Van

when

Sb,
n

N/V

have

- Nb)/N] +
intermolecular

C5}

1}.
attractive

forces.

Figure 10.7

The

iiucraaion

energy

between

The
repulsion plus a long range aiiracHou.
short
range repulsion can be described
that each molecule
by saying
approximately

has a hard, impeneirable

coie.

10: Phase Transformation*

Chapter

Mean Field

Method

There exists

taking

the effect

of weak long range

particles
system.The most
gases and to ferromagnets.Let
of two atoms separated a distance

of a

known

widely
tp(r)

the average value of

at r = Ois

is n,

gas

the

atom

interactions

potential

for

the

among

method are to
energy of interaction

the concentration

r. When

method,

of the

applications
the

denote

by

the

the mean field

called

method,

approximate

simple

account

inio

of atoms in

ihe total interactionof all other

on

atoms

C6)

where -2a denotes

value

the

of

ihe

We exclude the

convention.

useful

integral \\dVip{r). The factor of two

hard core sphereof voiume
b from

is

of integraiion. In writing C6) we assume

that
the concentration
ihe
volume accessible to the moleculesof the gas. That
ihroughout
we use the mean value of n. Tins assumption
essence
is the
of the mean

volume
constant

approximation.
of concentration

in

we

language

energy

say

the

\"

molecules.

interacting
From

regions

thaS

it follows

C6)

of a

that

The

factor

exact

s MJ =

is

Heimholu

free

of a

energy

F(vilW) =

The

pressure

*=

obiain

the

the

free

C7)

-N2a/V.

it arranges

problems;

only once in

|-N(N - I), which

We add C7) to C5) to

change the energy and

-\\BNna)

is counted

molecules

of bonds

number

is,

V by

volume

j is common to self-energy

\"bond\"between two

is

\342\226\240

the interactions

gas of N moleculesin
AF

field
we ignore the increase
concentration
uniform
of strong
attractive
potential energy. In modern
mean field method neglectscorrelationsbetween

assuming

By

the

we

der

v;m

approximate

Waais

that an

interaction

the total energy.The

as |N2.

approximation

for the

yas:

-.Vi{log[\302\273u(l'r

Sh)/N~\\

+ 1}

- Nza/V.

0$)

is

C9)
'\342\226\240-^\302\253'\027^5-F

Critical Pawls for

the

Figure

suggests

pressure
be

used

of intermolecular
near ihe boundary
Y. The van dci Waats argument
lhal ihcse forces contribute art internal
Nxa!Vl which Is lo be addedlo ihe

10.8

forces that
of a volume

Direciions

on molecules

ad

as ihe

pressure

in

gas taw.

the

o
o

of volume Khas N
not
b.
The volume
molcculcSi
V
S'b.
Intuition
by molecules is
occupied
suggests that iHis fece volume should be used in
V.
llic gas law in place
of the coiiiaincr Volume

Figure

each

O
0

O
o

(p

Waals

10.8

and

coniainer

of volume

\302\251

der

Hie

10.9

+ N2a/V2){V

equatum of

~ Nb)

\302\253
A'l

staSe. The terms in

D0)

and

b arc

interpreted

in

10.9.

Points

for She van

ne the

quantities

der

Gas

Waals

pc ^ a!21b2\\

Vc

3Nb;

xc

^ 8a/27b.

D1)

Chapter

10:

Phase

Trans/or,

. -

0.95tt

P/Pc

Figure

In termsof

these

der Waals

Tile van

10.10

critical

the

van der

the

quantities

equation of

Waals equation

\\(V

f7HJAH

This equation is plotted in

temperature tc. The equation

stal

Courtesy of R. Cahn.

temperature.

Figure
may

10-10
be

l\\

8t

3/

3t/

for

written

becomes
D2)

near the
temperatures
in terms of the dimensionless

several

variables
ps

9sVfV.\\

pjPc\\

e t/tc ,

D3)

D4)

This
si!

gases

result

!ook

ts

known
alike\342\200\224if

as the
they

correspondingstates. In termsof p, V, t,
the van der Waals equation. Valuesof a

law of
obey

Free

Gibbs

usually obtained

and b are

Realgasesdo
one

At

same p,

at the

substances

not

the

obey

P~V

curve

phases.

and

coincide,

At a

horizontal

corresponding

local

the

Here

and

tc the critical

Above

tt

of the

van

der

gives

N.

of pressure

function

as

a function

we

cannot

by

gas

of

Nt{log[\302\273u(K

V,

t,

N;

It is

want

Nb)/N]

the natural

put G

conveniently

(9.13).

the characteristics
With G = F + pV,

of

exhibits

pressure.

instead ofvolume.We

obtain ;i(t,p)as G(z,p,N)/N

relation

Waals

-^

-\342\200\224^

This equation
p, t, Unfortunately

Vet

Gas

constant

pc,

\342\226\240-

Waals

der

the !iquici-gasphase transition

at
have
from C8) and C9) the result

G(x,VtN)

respectively.

exists.

free energy of the van

The Gibbs

liquid

9 = 1;i 1. We call
critical volume,and criticaltemperature,
p = 1;

by D4) if

pressure,
separation

Energy

of the

@i-

no phase

Free

Gibbs

and minimum

maximum

f has

constant

at

is no separation between the vapor and

of
inflection
point

satisfied

are

conditions

ihe subsiances.

there

aThese

states of

point, the curve of p versus

horizontal point of inflection.

tc. States of two

pc and

observed

Gas

M'aah

(let

van

to high accuracy.

equation

the critical

point,

called

Vy x are

the

to

fitting

by

of the

Energy

variables

into an

G(z,p,N)

+ 1],

analytic

because

we

D6)

for G are
form

we can

as

/i that determines the phase coexistence

temperature

results of numerical calculationsof G versus

plotted
pare
10.! 1 for temperatures
below
and at ihe critical temperature. At any
the lowest branch represents the stable phase; the otherbranches

represent

unstable

ft,

in Figure

then

fig. The

phases.

The pressure

at which the branchescrossdetermines

gas and liquid; this pressure is calledthe equilibrium

!0.12.
for
G versus t are plottedin Figure
vapor
pressure.
V < Vs In which only ihe
10.13 shows, on a p-V diagram,
the
Figure
region
and
the
V > V2 in which
liquid phase exists
region
only the gas phase exists.
between
and
The
value
or
The phasescoexist
of
V2 is determined
Vx
V^.
Kj
by
the condition that /i](r,p)== }ia{x,p) along the horizontal line between Vx and
the

transition

between

Results

V2- This

will occur if the

shaded area belowthe Jine

is equal

to the

shaded area

10;

Chapter

Phase

Ttansfo

-0.40

t\342\200\224

--

rasure

,-Vapor[

/
\\

Figure 10.11

der

Waals

(a) Gibbs free

of stale:

equaiion

(b) Gibbs

free energy

versus

stale;i = %..

above

the

To see

line.

have

difference

dG

versus

pressure

i = 0.95tc. Courtesy

pressure

for van der

of

for van
R.

Cahn.

Waals equation of

ihis, consider
dG

We

energy

Vdp at

\302\253
~adx

Vdp +

constant i and constanttola!number

of G between V\\

and

D7)

pdN.
of

particles.

The

V1 is

G,-G,=

fWp,

D8)

1
~p

0.95

nqb =

LiqutaS^

\302\273bic

G/Nrc

'

0.990

0.988

0.986

0.984

\342\226\240

't/t,
(a)

Figure

versus temperature
of A. Manoliu.

Gibbs free energy

10.12a

of slale a! p

0.95 pe. Courlesy

for

van

der Waals

=
p

nqb

equalio

1.0

\\

\\

\\oas

-2.70

0.90

I.OO

1.10

1.05

t/t,

(b)
Figure

of slate

10.12b

a! the

Gibbs
crilical

free energy
pressure

pc.

versus temperature for van

der

Waais

cquatiO!

Chapter

Id: Phase

Transformations

conslan

- ^Liquid
-Cocx

\\

fir

Stetice

<\302\243

as

|\\
s.

v.t

10.13 Isotherm
of van
lemperafure belowliie critical
Figun e
less

than

above

lliegas
phase exisls. Between
in stable equilibrium lies along the

line

and is

liquid

and

liquid

and

volumes

bul ihe
When

equals

the volume

/^{r,p)along

Hie

we require
Nuclcatiou.

of the

magnitudes

j.tg

Let

that

and

V2

coexistence

is available.

shaded

areas,

areas are

equal,
line

coexistence

horizontal

Vx

an inhomogencousmixture
of two phases. The
gas phases coexist. The proportion of liic
be such
lhai ihe sum of fheir
gas phases must

integral isjust ihesum ofthe

Ihe

volumes

only

Kj

Ihe system

volumes

For

phase exisls; for

!hc liquid

Vt only

der Waalsgasat
lempcralure.

one

G?(t,/>)

drawn

in

and one positive.

Gj(t,p) and [is{x,p}=

negalive

the

figure.

In equilibrium

/*,.
Aji

\342\200\224 \342\200\224be

;i,

ftg

ihe

chemical

potential

difTerence between

the vaporsurroundinga smallliquid

and the liquid in bulk (an infinitely
droplet
is
if A/i
iarye
drop),
positive, Ihe buik liquid will have a lower free energy than
the gas and thus
the
will be more stable than the gas. However,the
liquid
surface
the free
free
of a liquid drop is positiveand
tends
lo increase
energy
Al
the
of'he
small
radii
the
surface
can
be
dominantand
energy
liquid.
drop
can be unstable
the change
with respect to the gas.We calculate
in Gibbs
drop
of molecules
is the concentration
R forms.
freecnergy when a drop of radius
If\302\273,
in the liquid,
AG

G,

=
G9

-{

+ 4nR2y

D9)

Ferromagtutism

the surface

y is

where

drop

will

grow

free energy per unit

Gt <

when

An

Gr

0 =

ti&G/dR

This

is the

fend

to

critical radius

R tlie

larger

drop

will

to

tend

E1)

that

because that,

drop

will

energy.

too, will

At

lower

free energy.

the

must
that
energy barrier (Figure10.14)
fluctuation in order fora nucleusto grow
beyond
in
E1) D9):

The free

(&G)C

to

free

the

Jower

will

spontaneously

grow

R the

At smaller

a drop-

of

because

spontaneously

evaporaie

E0)

\302\2532y/H,A/i.

nuclcation

for

when

+ SnRy ,

-4nR2iii&n

Rc

The liquid

is attained

of AG

maximum

unstable

tension.

surface

or

area,

If we

assume [hat

express

Aji as

the

vapor

for

-r

the vapor pressure tn

of the bulk liquid (R ~*

Kcrro

300 K

at

water

and p

E2)

like an

behaves

p is

pressure

by a ihcrni.i!
substitution
of
by

overcome

R,. is found

(lenPW/nMl*I}.

Aft

where

be

ideal gas, we can use Chapter5

tlog{p/peq)

the

gas

co).

phase

and

use

We

pe<l

72erg

the

equilibrium

cm\022 to

vapor

estimate Rt

x !0~6cm.

= l.J^tobel

ism

magnet

means
a magnetic
has a spontaneous magneticmoment,which
field approxithe mean
moment even in zero applied magneticfield.We develop
defined
as the
of ihe magnetization,
approximation
SO the
temperature
dependence
each
moment
niagnelic
magnetic
per unit volume. Tlie centra! assumptionis that
alom experiences
an effective fieid BE proportional to she magnetization:

A ferromagnet

BE

where

I is

a conslans. We

take

the

\302\253
AM

external

E3)

applied

field as

zero.

Chapter

10:

Phase

Tram/or

barn

Critical
*\"

or

t for growH,

3n nuclei

cortdcnsut

fx

'

ondensation

\\

nuclei

__

evaporate

\342\226\240'\342\226\240\342\226\240-

Figure 10.14
of

function

Excessfree

drop

radius

energy

of drop

relative lo

gas, as

R, both m reduced units. The

gas

is

because the iiquid has the lower free energy for

but the surface energy ofsmaii dropscreates
an energy
of nuclei of the liquid
barrier ihat inhibits
the growth
fluctuations eventually may carry nuclei over ihe
phase. Thermal

supersaturated
this

curve

as drawn,

barrier.

a system with

Consider

a concentration h of magneticatoms,

magnetic moment fi. In Chapter3 we

magnetization in a field B:

and of

In the mean field

approximation

an

found

each

exact

of spin

E3)

Me
.
\342\226\240\"\342\226\240_\342\226\240_\342\226\240

this

for a

becomes,

n/nanh(/dMA)

for the

result

= HjitanhOiB/t).

E4)

ferromagnet,
'..

'.

E5)

Fcrromu^cth,

1.0

0.8

0.6

0.4

0.2

soiuiion of \302\243q.
for the
Graphical
E6)
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
10.15

Figure

The right-hand side is tanh(m/0

and
is
three
difierenl
of
for
values
the
reduced
plotted
t = r/n;i'^ *= i/tt. The three curves
temperature
to
the temperatures 2x,,zt, and Q.5rt. The
correspond
with unit slope.

versus

curve for

in

the

2 intersects

as appropriate for ihe

is no externai applied magneiic

m s= 0,
t =

(or
this

it) is

murks

ictnpetalure
for

Curve

lo

tangent

i =

0.5 is in

tmersccts ihc straight

1

-\342\200\242
0 the

magneiic

we write it
temperature

iiie

tn
f

line

moments

are

Figure

and

10.15. The

versus

shall

We

M.

left

of

sides

and
n/i. As

0.94

l.so

that all

absolute zero.

see that

E6)

ianh{Hi/r).
this

equation

separately

intercept of the two curvesgives

temperature of interest.The critical

curvesof

up at

iined

in

region
s=
\302\273i

whence

z/n[i2X,

We plot the right

in

ferromagnciic
in at about

moves up to

hi

as

the suatght
Sine m at ihc origin;
ilic onset of fcrroiiiagnetisiu.The

solutions of this equation

M exist in the temperature range between0 and
v To solve E5)
terms
of the reduced magnetization ??i \302\253
and
the reduced
M/h/i

nonzero

with

region (iherc
curve for / = i

paramagnetic
The
fieid).

intercept

a transcendental equation for

al

in only

iine

straight

x obtained

in ihis

temperature

ts

way reproduce

the

I,

;is functions of \302\273t,

value
of m at Ihe
=
or zt
h/i^L The

roughly the featuresofthe

10;

Chapter

Phase

Transformation

of
Figure 10.16 Saiuration magnetization
as
a
nickel
function of temperature,together
with
ihc theoretical
curve fci spin \\ on ihe

mean fieid theory.

resuiis, as

experimental

in

shown

magnetizationdecreases

smoothly

OF

THEORY

LANDAU

Landau gave a systematic

transitions

consider

free

to

applicable

at

systems

F =

energy

with

minimum

\302\243,

system,

electrons
bonds

have

can

a certain

be indepaideally

mean

field theory

the

It isnot helpful

system

can

to

all possible

consider

by a single order

be described

might be the magnetization in a ferromagneti

in a ferroelectric
system, the fraction of
polarization
in a superconductor,
or the fraction of neighborA-B

in ait

value

alloy
c,

specified,

equilibrium the order parameter

the Landau iheory we imagine Ihat \302

AB. In thermal
cc{c).

In

and we consider the LandauTree

FL(\302\243.x)

(\"unction

energy

the energy and entropy are taken when the

value \302\243
no!
necessarily
c0. The equilibrium
specified
where

of phase transi-

xi, which

Greek

bondstotola!
will

to what variables?

dielectric

superconducting

of the

variety of systems exhibitingsuch transitions.We

their
Heimholtz
constant volume and temperature, so that
\342\200\224
in
The
ta is a minimum
big questionis,a
equilibrium.

suppose here that

parameter the

TRANSITIONS

a large

respect

variables. We
the

at z

zero

PHASER

formulation

for nickel As t increases the

= rc, called the Curie temperature

10.16

Figure
to

E7)

order
value

has

parameter

\302\2430{t)is

the

value

the

of

Landau

Transitions

of Phase

Theory

makes FL a minimum, at a given

the actual Hdmholtz
t, and
f(r) of the system at i is equal lo thai minimum:

c, that

F(t)
Plotted as a function
than one minimum.

\302\273

Fl($0,t)

of

for
\302\243

r, ilic

constant

The lowest of these

transition
another
phase
i is increased.
of

function
ferroelectric

are

systems

exam

well-behaved function
something

this.

We

that
\302\243

it

can

not be

lowest

In a

state.

equilibrium
the

becomes

more

as

minimum

Landau (\"unction
is an even
applied fields. Most ferromagneticand ferro-

pies of
of

should

that

of

absence

the

in
\302\243

the

have

for which Ihe

to systems

ourselves

E8)

Co-

Landau free energy may

minimum

restrict

*
\302\243

determines

first order
We

if

FL(\302\243r)

free energy

taken

also

that

assume

be expanded

for

For

granted.

F 1(^,1) is a

in a

sufficiently

power series in

\302\243\342\200\224

function of

an even

as
\302\243,

assumed,

entire

The

dependence of

temperature

coefficients

g6- These

g2,gx,

ga\\

FL(\302\243,x)

is

are matters

coefficients

in the

contained
for

expansion
or theory.

experiment

changes
sign at
^(x)
example of a phase transitionoccurswhen
a temperature i0, with y4 positive and the higher terms negligible.For simplicity

The simplest
take

we

linear

g2(t)

in i:
~

<72(r)

the

over

these

Witli

The

temperature

The

which

of interest,

F0)

and we take g4

as

in that

constant

range.

idealizations,

form F0)

certainly

range

temperature

- to)* .

(r

fails
is not

and
cannot be accurateover a very wide temperature
range,
on tembecause such a linear dependence
at low temperatures
consistent

equilibrium

has the

with

value of

the
is
\302\243

law.

third

found

it

at the

minimum of

FL{$

;t)

with

respect

roots

f~Q

and

= (to

- r)(a/g4).

F3)

Phase

Chapter

iff;

With a

and ga positive, the root c,

energy

function

Transformations

above i0;

at temperatures

F1)

0 corresponds

J=Xt) =

The other root, c,2

energy

of

FdZ'J-)

as

of F(r) with

in Figure

ihe

for
\302\243:

temperature

minimum of the free

here the HelinhoHzfreeenergy

is

F4)

0g(l).

t) corresponds to the minimum of the free

below t0; here the Helmhoitz
is
free energy

temperature

of

a function

Figure 10.18,and
shown

(a/gj(to

at temperatures

function

The variation

to the

10.17. The variation

ihree
is shown in
temperatures
representative
is
of the equilibrium value of \302\243
dependence
is shown

in Figure

10.19.

Our model describesa phasetransition

elergoes

to

continuously

Figure
for an

zero

as the

in

which

temperature

the value of the order paratnis increased to t0. The entropy

10.17
Temperature dependence of (he free energy
of the second order.
ideatized phase t ransition

Figure

10.18

free energy

Landau

function

As the
reprcscniaLivc
temperatures.
the equilibrium
value of \302\243
gradually
posiiion

of the minimum

Figure

10.19

temperature,
curve is not realisticat
use Of Eq. F0): the third
thatdf/rfr

increases,

polarization

a second-order

->0asi-*0.

at
\302\2432

;is tic fined

by

t0
the

of the tree energy.

Spontaneous
for

versus

temperature drops below

low

law

versus

phase transition. The

because of the
temperatures
of thermodynamics

requires

Chapter

10: Phase

\342\200\224

Transformations
at t

is continuous

dFfdz

temperature f0.

Such

Transitions

nonzero

with

latent

The real

second order transitions;

is no

there

latent

heat at the

transition

definition a second order transition.

order
heat are called first
we
transitions;
a remarkable
world
contains
of
diversity
arc ferromagnels
and superexamples
is by

transition

them presently.

discuss

= rQ,so that

best

the

superconductors.

Example:

Landau
which

In the mean field approximation, ferromagnets

the
satisfy
To
show
moment
a
field
consider
a
n
atom
of
theory.
this,
3,
pin magnetic
magnetic
we shall set equal to ihe tijean
field
>M as in E3). The interaction energy density is
Ferromagnets.

V(M) =

j iscommon to self-energy

ihe factor

where

F6)

-\302\261

g{M) = constant in Ihe

regime

in

FL{M) ~

At

transition

Ihe

which

\302\253

n/j.

Thus

constant -

temperature

\\M2(/.'~

the coefficient of M*

with

First Order

Transitions

latent

lion
order

at

heat

constant
transitions

in metals
transformations

the

discussion

density is given approxi-

F7)

fursciion

\342\200\224A+

entropy

M2J2nn2

the free energy

i0
in agreement

The

problems.

per

lermsof

vanishes,

unit

volume

higher

is

order.

so ihat

F9}

\302\273}i2>.,

following

F8)

E6).

transiphase transition. The liquid-gas

In ihe physics of solids first
transition.
is a first order
pressure
and in phase transformaare common
in
ferroelectric
crystals
a first order iransition
describes
and alloys. The Landau function

characterizes

a first order

when the expansion coefficientg*

is

negative

and

gb Is

positive.

We

consider

first

l(K20

Figure
first

Landau

free energy

at representative
function has equal minima
For t below rf the
as shown.
\302\243

order

versus

function

transition,

i1

temperatures.

Order

Transitions

m a
At

xc

at a
is
minimum
finite
absolute
is
a
there
iatger values of ^; as r passes
through
tc
in the position
of the absolute
disconimuouschcinge
minimum.
The
artows
mark the minima.
the Landau

The extrema of

this

function

are

given

by

at

\302\243

0 and

the roots

FigureJ0.20:
G1)
-

Either

\302\243

0 or

G2)
At
with

transition

the
c,

0 and

temperature

with the

rc the

root c^O.

free energies will

The

value

of

be

xc will

equal

for

not be

the phases

equal to r0,

Chapter

Phas

10;

and the

order parameter\302\243
(Figure

weui
earlier, where \302\243
transformation

show

may

those

differ from

results

These

xc.

at
continuously
as in supercooling

zero

to

hysteresis,

hysteresis exists in

t0 -

coexistencecurve in the p-x planebetween

Clausius-Clapeyron equation:
dp

L is

the two
2.

The

the latent heat and

van

heat L

order

transfor-

but

supcrsaturation,

no

is the

An

two

phases

must

satisfy tiic

der

Waais

volume

difference per

pV is the

the energy

'

is a minimum

of state

(P +

atom between

necessarily

V +

enthalpy.

is
-

N2a!V2){V

Nb) =

Nx.

function

energy

and entropy

not
value \302\243,,

where

equation

free

Landau

- Hlt

~ H,

4. In the

first

phases.

latent

3. The

tf.

or

1. The

where

continuously to zero at
phase transition treated

transition.

order

a second

rrt in K

order

second

the

in

not go

does

10.21}

-20

-40

_60

are

the

taken

when

thermal

with respect to

when
\302\243

parameter has the specified

The
function
Fl
equilibrium value \302\2430.
the order

the

system

is

in

thermal

equilibrium.

A first

5,

phase transition is characterizedby

order

Intent

heal

and

that

the

by

hysteresis.

PROBLEMS

/,

dcr

van

ofthe

entropy

and

energy,

Entropy^

(c)

the

enthalpy//

//(r./>)
arc

results

given

2. Calculationof
equation

U =

INi.-

= U

+ pV

|Nt

-jNr +

to first order

near p

the

for

G6)

terms o, h.

\\V;ials correction

the vapor

from

Calculate

G5)

2N2ajV\\

2NuPfx.

der

van

~ 1 atm

G4)

i%

NhP

the

in

heat of vaporizational

wmcr. The

G3)

N2.ii!V.

+ N2bx/V

water.

for

(IT{dp

of elT/dp

value

the

en-

+ 1}.

Nb)JN]

N[log[nQ(V

H{i,V)

All

Show

is

energy

the

thai

Show

(a)

gas is

Waats

o(b) Showthat

IVaah gas.

of van der

enthalpy

Hquid-vypor

100Xis 2260

Express

Jg\021.

pressure equaof
in

equilibrium
the
result

keivin/atm.

3. Heat of vaporization
Hgal
of
vaporization

ice

4.

Gas-solid

we

let the

at

ice.

of

the

latent

soiid move in
\302\273
haS)

heat

the

range

the heat

Jmol\"'

of vaporiza-

of interest.

of the exampleB6}-C2)
in
dimensions,

three

vapor

per atom

pressure

is tQ

which

(a) Show that in

the

is

\342\200\224

\\i.

the gas-solid equilibrium under the exof the solidmay be neglected

over the temthe
ofthe
be
cohesive
Let -e0
solid,per atom.
energy

Consider
equilibrium.
that the entropy
assumption

GaS'SoU'd

temperature

a version

Consider

equilibrium.

osciSiators in the

(b) Explain why

extreme

vapor over iceis3,SSmm

of water

pressure

~l\302\260C.

high temperatureregime(t

5.

The

mniHgai OX. Estimatein

and 4.58

~2=C

10: Phase

Chapter

Transformatio

Treat the gas as idea!and

of ihe

energy

system

minimum

of

ihe

+ F,

number

total

the

the

independent

container,

thai the

(a) Show

volume

of the much

total HeimhoHzfree

is

F = F,
where

that the

the approximation

Make

monatomic.

accessible to the gas is the volume V of

Smaller Volume occupied by the Solid,

free energy

\"

that in ihe

G8)

(b) Find

constant,

is

Ng

to N^show

respect

- I] ,

N,r[!og(N,/l'il0)

N = N,

of atoms,
with

-Ufa

the mini-

equilibrium condition
09)

(c) Find the equilibrium

vapor

6.

of the

Thermodynamics

pressure.

superconducting transition, (a) Show

th

2/i0

SI
units
for Be. Because Bc decreases with
side is negative. The superconducting
phase

temperature,

increasing
has

(SO)

[i0 ih

in

that

the

lower

entropy:

it

the

right

is the

more

ordered phase. As t ~+ 0, the entropy'in

both phases will go to zero, consistent
r?
with the third law. What
for the sliapc of the curve of Bt versus
docs
this imply
=
=
this
ihe
SIiow
llutt
result
hits
0
and
hence
(b) At r = xtt we have
Bt
a^ aN.
following consequences: A) The two free energy curves do not cross ;if tt but
are the same:
as shown in Figure 10.22.B) The two
energies
merge,
Usfr,.) =
heat
with
the transition at r \342\200\224
associated
tt.
U.vW- C) There is no Intent
What
is the latent heat of the transition when
out
carried
in a magnetic field,

at r < i{7 (c)

related

that

Show

Cs and

CN, the

heat capacitiesper unit

volume,

are

by

(81)

Figure S.iS is a
than

linearly

dominated

plot of Cj'T

with

by Cs.

T1

vs

decreasing

Show that

and

r, while
Hiis

implies

shows

that

Cs decreases

Cs decreasesas yz.

For

much
\302\253

tc>

faster

AC

is

_-

-0.2

X. Normal

.1

Superconductor

*STC=1.180K

0.5

lure.

Temper;

of
Experimental values of the Tree energy as a function
in the superconducting state and in the normal
stale. Below the transition
is lower
temperature
T, = 1.180 K (he free energy
in !he
transition
slate.
The
(wo
curves
at
the
supcrcondtiding
merge
heat
is second order {(hereis no laient
tempcra(ure, so thai the phase transition
a! Tc). The curve
and
of transiiion
in
zero
is
measured
FN is
magnetic field,
Fs
normal
slaie.
measured
in a magnetic
to
in
(he
field suftkien!
pu! the specimen

Figure 10.22

temperature

Tor aluminum

Courtesy of

N.

E. Phillips.

model of the superconducting

transition. TheBc(i}curves
that
iutve shapes close to simple paraboias.Suppose

7, Simplified
superconductors

Bt(i)

that

Cs

linear in r,

as for

Assume

and plot

calculate

heat

8.

crystal

of

order

two.structures,

siable
form

low

of the

than linearly as
(Chapter
7}. Draw

gas

the i dependencesof

and ihe latent

First

Fermi

of

the transition.

temperalure

substance.

separated atomsat

form

by a
and

he

then

(83}

also
t -* 0.
on the resultsof

the two

heat capacities,

Cs(rc)/Cv(r(}= 3.
crystal that

can existin

'hat
and /?. We suppose
the /J structure is the stable high

the

energy

6 to

Problem

the

energy

Cs is

that

Assume

entropies,

Consider.'!

If the zero of the

infinity,

two

Show that

transformation.

denoted

most

d/r(}2].

faster

vanishes
a

Bt0[l

of

scale

density

is

taken

eilher

is the

a slrucmre
semperalure

as the

1/@) at r

==

stale of
uill

be

Chapter 10:

Pha:

negative. The phasestable

velocity of sound ve
U?@).
to lower values
phase, corresponding

thermal excitationsin

phase.The
!he
energy.

the

larger

Soft

free

by the

is

thermal

excitation,

tend

systems

the

of

the

-~rc2r'i/3Oi;3/i3,

by

given

velocity of

all phonons.(b)

Show

value of U{0);thus

amplitudes than in the a

the entropy and the lower

stabie at high tempera!ures,hard

to be

low.

in the

the lower

/J phase is lower than vx in the

clastic
moduli for /?, then the

have larger
the larger

will

phase

in

the
(a) Show from Chapter 4 that
phonons in a solid at a temperature much
at

systems

the

have

\342\200\224
0 will

If the

<

Ux@)

at

free

energy

density

icssthan the Debye temperature

Debye approximation
that
at the transformation

with

will

a finite

actual

is

transformation

defined

real solution if t'p

phase

<

transformations

as the

trans-

thermal energy

(85), U

refers to unii volume.

that

must

the

that

L = 4[U,@)and

(84)

This example is a simplified model

in solids, (c) The latent heat of

Show

(84)

as the

iv

system through the transformation.

In

taken

temperature

>-v.-').

There be
ofa classof

contributed

t/,@

be

latent

to carry the
heal for this model is
supplied

(85)

11

Chapter

Mixtures

Binary

310

SOLUBILITY GAPS
OF

ENTROPY

AND

ENERGY

MIXING

wrth
Interactions
Nearest-Neighbor
Example: Binary Alloy
of
Structures
Mixture
Two
Solids
with
Different
Crystal
Example:
Low
3Hc-\"He
Mixturesat
Temperatures
Example: Liquid
for Simple Solubility Gaps
Phase Diagrams
PHASE

EQUILIBRIA

AND

SOLID

BETWEEN

31-1
318
319
320

321

LIQUID

322

MIXTURES

Advanced Treatment: Eutectics

325

SUMMARY

330

PROBLEMS

330

Potentials in Two-Phase Equilibrium

Energy in 3He-4He and Pb-Sn Mixtures

1. Chemical
2.

3.

Mixing
Segregation

Coefficient

of

Impurities

4. Solidification Range of Binary

5. Alloying
of Gold into Silicon

Alloy

330

330
331
331

33i

11:

Chapter

Mixtures

Binary

of materials science,and large parts

of
applications
chemistry
are
concerned
of
with
the
biophysics,
properties multicomponentsystems

and

Many

phases in coexistence.Beautiful, unexpected,and important

occur in such systems. We treat
the fundamentals
of the subject

or more

two

have

effects

physical

in this chapter, with

Mixturesarc

of

systems

Mixtures

ternary and quaternary mixtures.If

molecules,
A

to form

three

and

mixtures

are called

four constituents

\"oii

expression

phases, such as oil and

their
and water do not niix\" means
[hat

or

more

mole-

and not

arc atoms,

constituents

when its constituents are intermixedon an

A mixture is heterogeneous
phase, as in a solution.

a single

two

contains

with

the

species.Birjury

is homogeneous

mixture

scale

situations.

an ailoy.

is called

mixture

the

simple

different chemical

or more

two

two constituents.

only

from

drawn

examples

GAPS

SOLUBILITY

have

that

distinct

The

water.

atomic

when

it

everyday

does not form

mixture

a single homogeneousphase.

Thepropertiesof

differ

mixtures

solidification

and

melting
Heterogeneous

Consider

mixtures

may

a gold-silicon

from

the properties

ofmixturesareofspeciai
at lower temperatures than

properties
melt

alioy: pure Au

melisat

lO63cCand

substances. The

of pure

interest. Heterotheir

pure

constituents.

Si at

I404X,

at 37OCC. This is not

but an ailoy of 69pet Au and 31 pet Si melts (and solidifies}
ihc result of ihe formationof any low-melting
Au-Si
microscopic
compound:
a two
mixture of almost
phase
investigation of the solidified mixtureshows
pure

Au

side

by

side

with

almost

pure Si (Figure I I.I}.Mixtures

with

such

because
and they are of practicalimportance
precisely
of their lowered
melting points.
What
determines
whether
two substances
form a homogeneous or a heteroare
in equilibrium
mixture?
What
is ihe composition of ihe phaseslhat
heterogeneous
can be
of mixtures
with each osher in a heterogeneous mixture?The properties
at a fixed semperaiure will
underslood
from the principle that any system
evolve
to the
of minimum free energy. Two subsiances wiil
configuration
is the configuradissoive
in each oilier and form a homogeneous mixtureif that
will
free energy accessible to the components. The subsiances
of
iowest
configuration

properties

are common,

Gaps

Solubility

SO/tm
When
a mixture
of 69 pci Au and 31 pet
Figure II.I Heterogeneousgold-silicon
alloy.
Si is melted and then solidified,
the mixture
Au
a
into
segregaies
pure
phase of almost
\302\253iih
a
almost
coexistent
of
Si
aboui
phase
(Sight phase)
pure {darkphase).Magnified
is that of the lowest-melting Au-Si mixture,
the
800 times. The composinon given
eutectic
a
later
so-called
mixture, concept explained
in she text. Photograph
courtesy

ofStephan Justi.
a

form

side by side is

phases

then we say I hat

A

if [he

tnixlure

heterogeneous

the

mixture
miMure

hclerogeneous

free energy of

combined

tower ihaii the free energy

exhibits
will

of

the

Uvo

the

separate

mixture:

homogeneous

a solubility

melt at

gap.
a lower [cmperalurethan

the

separate

free energy of the homogeneousmeltis lower

than
the
two
combined
free
of
solid
energies
separate
phases.
ihis
we assume
for simplicity that the external
Throughout
chapter
be
and we sel pV = 0. Then volume changesdo not
neglected,
may

substances

work,

and

if I he

the appropriate

Ilian the Gibbs free

We

discuss

compounds

the

energy

free energy is
G.

We

tire

will usually

HelmhoUz

free

the

pressure
involve

F rather

energy

simply speak of

com-

free

energy.

well-defined
binary mixtures of constituents Ihat do no! form
with each other. Our principal interestis in binary
Consider
alloys.

Chapter H: Binary

Altitun

or more

two

have

concerned

are

biophysics,

science, and large parts of chemistry

with the properties of multicomponent systems

materials

of

applications

Many

phases

coexistence.

in

Beauiiftil,

that

and important

unexpected,

Ihe fundamentals
physical
systems.
in this chapter, with examples drawn from simplesituations.
We treat

in such

occur

effects

and

of

the

subject

SOLUBILITYGAPS
are

Mixtures

or more

of two

systems

molecules,
A

is homogeneous

mixture

Binary
species.
four constituents

and

three

are

constituents

an alloy.
when its constituents

is called

mixture

the

chemical

different

constituents. Mixtureswith
ternary and quaternary mixtures.If the

have only two

atoms,

arc intermixedon an

a Single phase, as in a solution.

A mixture
two
water.
contains
or more distinct phases, such as oil and
\"oil and water do no! mix\"
that
means
their mixture
expression
a single

melting

solidification

and

mixtures

may

an

of 69

alloy

from

the

properties

side

by

alloy:

pet Au

side

are common,

properties

of their loweredmelfing
What
heterogeneous

determines
mixture?

and

evolve
dissolve
configuration
of

with

they

two

compound:
phase

mixture

pure Si (Figure 11.1).Mixtures

almost

and

Au-Si

are

of practical

importance

microscopic

of almost
with

such

precisely because

points.

whether two substances form a homogeneousor 3 heteroWhat is the composition of the phasesthat
are
in equilibrium

be
other in a heterogeneousmixture?Theproperties
ofmixtures
can
wiil
from the principle that
at
a
fixed temperature
any
system
to the configuration
of minimum free energy. Two substanceswill
in each other and form a homogeneousmixture
if that
is the configurawill
lowest
to
the
free energy accessible
components. The substances

with each
understood

substances. The

of pure

of mixtures
are of special interest.Heterolower temperatures than their constituents.
Si at 1404\302\260C,
pure Au melts at 1063\302\260C and pure
31 pet Si melts (and solidifies}
at 370\302\260C This is not

of the formationof any iow-me!ting

investigation of the solidified mixture shows
Au

form

at

melt

the result

pure

everyday

does iiot

properiies

Consider gold-silicon
but

The

it

phase.

homogeneous

The properties of mixtures differ

Heterogeneous

atomic

is heterogeneous when

to form

scale

mixtures

are called
and not mole-

Solubility

10/mi

H.I
Figure
jure 11.1
Siisn
is melted

Heterogeneous gold-siliconalloy. When a mixture of 69 pet Au and 31 pet

and ihen solidified,!hemixiure
into a phase of almost pure Au
segregates
a
codxisieni
of
almost
Si
aboui
wiih
(dark
(lighi phase)
phase
pure
phase). Magnified
800 limes. The composition given
is !hal of ihe towesi-melting Aii-Si mixiure,
ihc
eulectk: mixture, a concept explainedtater
so-called
in ihe texi. Photograph
courtesy

ofSiephanJusii.
mixture
if the combined free energy of the two
separate
is
free
of
the
lower than the
by side
phases
homogeneous mixture:
energy
we say that
the mixture exhibiis a solubility gap.
then
A hcierogeneous
mixture
will melt at a tower temperature than the separate
comif the
free energy of the homogeneous melt is lowerthan
ilie
substances
free
of the two separate solid phases.
combined
energies
Ihis
we assume for simplicity that the external pressure
Throughout
chapter
and we set pV ~ 0. Then volume changesdo not involve
be
neglected,
may
a heterogeneous

form

side

and

work,

than

the

appropriate

We

compounds

discuss

free eneryy

free energy G. We

the Gibbs

binary
wiih

each

mixtures

will

is the Hetmlioltzfree energy

usually

of constituents

other. Our

simply

speak

rather

of the free

energy.

that do not form weil-defined

principal interest is in

binary

alloys.

Consider

Chapter Hi

a mixture

Binary

Mixtures

of

aloms

JVA

the composition of the system

We express

x
the sysiem

Suppose

per atom

in

\302\273

A'b/N;

Suppose

further

curves
shape.

B}

jVa/N.

an

average

free energy

with

C)

two

homogeneous

Any

respect

to

two

separate

<

at

points,

of this shape are common,and

mixture

in

derivative

second

ihe

x, <
is unstable

\302\273

form shown

the functional

lias

that/(.\\)

we can draw a line tangent to the curve at

cause this

x of B aioms;

= F/N.

contains a range in which

energy

the fraciion

iermsof

forms a homogeneous solution,wiih

Free

B.Thetotal

by

given

this curve

NB atoms of substance

A and

ofsubsiance

is

atoms

of

number

in the

we

wilt

Figure

11.2.

Because

d2f/dx2 is negative,
x = xx and x \342\204\242
x^.
see

later what

composition range
D)

xp

phases of

may

composition x, and x^. We

is
that ihe average free energy per atomof the
mixture
segregated
a
the
i\"
line
and
in
ihe
on
the
Thus
the straight
given by
connecting
points
[}.
point
a lower
has
free energy than
entire composition range D) the segregatedsystem
shall

show

the homogeneoussystem.

Proof

The

free

energy

of a
F

where ,V,

Nfi are

and

=>

the total

segregated mixture of the two phasesa and

NJix,)

NfJ\\xfi)

numbers of atoms in

j$ is

E)

.
phasesa

and

ji, respectively.

These numbers satisfy the relations

which may

be

solved

for .V,

and Ny.

0)

Gaps

Solubility

Free energy per alom as a function

for a
of composition,
a
aiom
of
system
gap. tf the free energy
per
has a shape such that
a tangent
can be drawn
homogeneous mixture
touches
the
two
x
and
that
curve at
diftereiit
/?, (lie composition
points
the two points is unstable. Any
mixture
with a
range between
in this
two phases
with the
composition
range will decompose into
composition _v, arid ,\\f. The free energy of the two phase mixture is
It.
given by the point / on the straight
line, below the point
tl.2

Figure

with

E) we

From

a solubility

obtain

fjix)

(S)
JV

for

the

free energy

straight line
through

the

the point i

in

thef-x

points

of the

two

plane.
a and

system.

phase

If we

/?. Thus/

set
in

.v.

(he

is linear in x and is a
v,c
see (hat the line docsgo
A'3 or.v^,
result

This

between

interval

on the straight lineconnectinga and

p.

.y4 and

xfi

is given

by

Binary Mixtures

II:

Chapter

We have not yet

made useof

(he

that

assumption

(he straight

line is tangentto

3 and /J, and therefore our result holds for any straight
line
points
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
on opposite sides of a-. The lowest
wiih/(-v),
possible
line
the
is
shown.
The
and
straight
(wo-pointtangent
x3
compositions
x? are

f{x)

the

at

that has

the limits of the solubility

of (he system.
gap
Once (he system has reachedits lowest
free
(he (wo phases must be in
energy,
to
diffusive
with
both
atomic species,so thai their chemical
equilibrium
respect
satisfy

potentials

/*a> =
We show

point tangent with

as in Figure 11.2.

the

two

/jB

are

(9)

Pb*-

given

by (he

of the two-

intercepts

plot at x

edges of thc/(x)

vertical

*=

and

a ~

1,

MIXING

OF

ENTROPY

AND

ENERGY

jja and

i that

Problem

in

Pb\302\273

/*\302\253;

The Heimhoitz free energy F ~ U ~ to has contributions from Ihe energy and
from
the
A and B on
We treat the effect of mixing two
components
entropy.
both terms. Let uA and \302\273a
be the energy
per atom of the pure substancesA and B,
referred

atoms

to separated

at

Tlie

infinity.

energy

average

per atom of the

constituents is
u

(uANA

+ vsyn)/N

which defines a straight line in

the

per

mixture

atom

separate
homogeneous

of

the

homogeneous

constituents.
is

niixture

u~x

nA

4-

(\302\253B

A0)

uA)x ,

Figure 11.3. The average energy

be
may
larger or smallerthan for the

plane.

In (he example of Figure11.3,(he energy

than the energy of the separate
larger

of

the homoge-

constituents.The

of mixing.
If (he re term in the free energy is negligible,asat 1 = 0,a positive
mixing
mixture
not
will
that
a
is
stable.
mixture
means
such
energy
homogeneous
Any
in the
the \342\200\224ia
then separate into two phases. But at a finite temperature
term
free energy of the homogeneous
the
tends
to
lower
mixturealways
free energy.
a contribution,
the
ofa
called
mixturecontains
entropy of mixing,
Theentropy
of the separate components. The mixing
that is not present in (he entropies
the
different
arises
when
of
atoms
species are interchangedin position;
entropy
of such interthis
a different state of (he system.Because
operation
generates

energy

excess

is called

\342\200\224

the energy

and Entropy

Energy

11,3

Figure

in a

sysicm

Energy
with

per atom

a positive

as a function

of composition

energy.

mixing

of Mixing

simple

a solubiliiy gap may occur is thai of a

in
which
the
system
energy per atom of the homogeneous
mixilire
Him of ihe separate phases, so that
is greater than
1
s. The
0 for att c mposi
ing e rgy i
e bci
differ
een the u[x) curve and the straight
line.
example

for which

states
a mixture has more accessible
and hence the mixturehas the higher
entropy.
In C.80) we calculated the mixing entropy
A, ^B,. to find

changes

two

tlie

than

erM

of

separate

substances,

a homogeneous

alloy

(ID

as

plotted

in Figure

11.4. The

that the slope at the ends of the

N dx
which

goes

to

+ co

as x

curve of aM

range

composition

X)

the important property

is vertical. We have

x has

versus

bgx

-+ 0 and to \342\200\224
co as

- ioj

x -*

I.

A2)

Chapter II:

Binary

Mixtures

da^/elx

Ffgure

11.4

Mixing entropy.

interchange of two

atoms

Tn

species leads to a new

system. The logarithm of liie number of

mixing

Consider

is the

slate

in this

related

slates

way

of the
is the

entropy.

now the

quantity

u[x)

which

of two constii uenis an

mixture

any

of different

\342\200\224
X

free energy

per atom without

(a

the

A3)

ffjtf

mixing

entropy

contribution.

The

is usually nearly the same for (he

an,
non-mixing part of the entropy,<j \342\200\224
\342\200\224
a linear
is nearly
mixture
as for (he separate components, so that
{er
cM)r
function of the composition x. If we assume
the /0(.v) cuive has the same
this,
but offset vertically.
curve,
u{x)
shape as
contribution
If we add the mixing
various temperatures the f{x)
shown
figure we have ignored the temperature
the

entropy

curves

dependence

to fo(x),

~-zaM/N
in

Figure
of/0(.v)

we obtain at

11.5. In drawing
itself,

because

the
for

Energy

Free energy
temperatures.The curve
Figure 11.5

per

atom

fQ is the

versus composition,
free energy per atom

und

Entropy

of Mixing

at three
without

the

a parabolic
mixing entropy contribution. For ilHistraiion
composition
dependence is assumed, and the temperaturedependence
of/0 is
The tliree solid curves represcnl the free energy
neglected.
including
the mixing
for the temperatures
0.8 rM, 1.0 tM, and 1.2 rM,
entropy,
where
there
is a solubility
rw is the maximum temperature for which
gap.

our

The

this is

argument

construction

separation

phase

at 0.8 rw

is apparent.

follow
irrelevant. Three importantdeductions

of the/(x)

from

the

curves:

(b)

f{x) turns up at both ends of the composition

contribution.
infinite
range,
entropy
slope of the mixing
Below a certain temperature rM there
which
is a com position
range within
than
is
ihe
the
second
derivative of the fo[x) curve
stronger
negative
second
it
derivative
of
the
positive
-taM contribution,thereby
making
values of x.
to draw a common tangent to f(x) at two different
possible

(c)

Above Ty

(a)

At

all

finite

temperatures

because

the

of the

curve

has

a positive

second derivative at al! composilions.

Binary Mixtures

11:

Chapter

We conclude that the A-B system

with
below
the
solubility
gap
temperature tM.

widens with
composition

only

range

solubility of A

in

B and

as t -*
of B

in

The

0.

At

A,

a result

finite

any

energy

can reach the

gap

edgesof

there

temperature

earlier

obtained

exhibii

of the

will

range

composition

the gap

but

temperature,

decreasing

mixing

positive

in

the

finite

is a

3. The

Chapter

below
Positive
is that the mutual solubility is limited only
tw.
We now discuss three examples.
mixing energies arise in different
ways.

new result

Consider
an alloy A^jB,
with nearest-neighbor interact'ionSi
in
than
the attractive
interinteraction between unlike atoms is weaker
interaction between
as bonds. There are
like atoms. For simplicity we speakof the interactions
be
ihe potential
three
different
bonds:
energies of
A-A, A-B, and B-B. Let uAA) uAB and uBB
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
of ihe bonds surrounding
an A alom is
energy
Binary

Example:

alloy

(he attractive

which

uA

where (t - x)is ihe propoition

mean field approximationof

of A and x is the

The total energy is obtained by summing

the average energy per atom
neighbors,

The

factor^

can be written

ip[(l

Figure

mixing

II.5.

proportion of B.This
for B atoms,

X)HAD

result

is wiiucn

in ihe

over

both

A5)

N\"UD.

atom

types. Ifeach

atom has

p nearest

is

xJUAA

2jcA

aiises because eachbond is sharedby

- *Kb +
the

two

atoms

A6)

*3\302\253db]-

it

The

connects.

result A6)

as

u =

is the

A4)

tO. Similarly,

Chapter

\"a

xuAa

x)uAA

energy.

On this

ip[(l

model

the

x)uAA

mixing

xum]

energy

as a

+ uM.

function

A7)

ofx

is a

parabola, as

in

Energy

A solubility gap

occurs whenever (/'//dx1

< 0, that

= -2P[fAB

^r

and

Entropy

of

Mixing

is, when

i(\302\253AA

B0)

O3-

From A2),

x{l -

N dx2
The

sign holds

equal

for

,x =

$. Wilh

T*i

x)

these results{19)yields

M\302\253ab

iO'AA

+ ^a)]

B2)

as die lower

of the temperature for a solubility

limit
gap.
are many reasons why mixed bonds may be weaker than
ihe bonds
of the sepafaic
constituents.If the constituent
in radius,
the difference introduces
atom* of an alloy differ
clasticstrains
that
water molecules
raise the energy. Water and oil \"do not mix\"' because
There

carry a large
water

strong

electric

molecules.

as

the

moment

dipole

This attraction

weaker

oil-oil

Example: Mixture of two

that leads to a strong electrostatic attraction

which are only
is absent in water-oil
bonds,

between
about

as

bonds.

solids

with different

crystal structures.

Consider a homoge-

of gold is the facesilicon. The stable crystal

centeredcubic structure
in which
nearest
equidistant
every atom is surrounded by twelve
of silicon is the diamond structure in which
structure
every
neighbors. The stable crystal
aiom is surrounded by only four equidistant
nearest neighbors, if in pure Au we replace a
wiih the
small fraction xof the atoms by Si, we obtain a homogeneousmixture
Au^.Si.,
1 fee crystal structure
fraction
x of the
of Au. Similarly,
if in pure Si we replace a small
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
range, or else pure Au and
11.6).The two curves must cross somewhere in the composition
curve
consists of the lower
Si would not crystallize in different
The
structures.
equilibrium
a sotubility
with a kink at the crossover point. Such a system
exhibits
of the two curves,
in
the
on
side
of
the
curves
shown
either
crossover
The
figure are schegap
composition.
to
the
in the actual
extends
so close
Au~Si system the unstable range
schematic;
edges of the
from x = 0 to x = 1.
that it cannot be representedon a fult-scale
extending
plot
diagram
homogeneouscrystalline

mixture

of gold and

structure

Chapter

11;

Binary

Mixture

\\/

Figure

11.6

Tree

energy versus

homogeneousmisiuresfor
mixture

crystallize

free energy curves

which

in ^ilfcrem

composition for cryslallinc

[he [wo constituents of the

crystal

are involved,

one

Two

structures.

for each

differe

crystal structure

Different crystal structures for the pureconstiiucmsarean

cause or solubility
important
in crystalline
solid mixiures. Our a/gument
to mixtures of ihis kind, provided
gaps
applies
the two structures
do not transform coniiriuously
into
each other wilh changing composicomposition.
This
when
is a tacit assumption in our discussion,
an assumption not always
satisfied
the two crystal
structures
are closely similar. The other
we make throughout
assumption
this
is that no stable compound formation
occur,
should
in the presence of comchapter
the behavior of the mixture
be
more
formation
compound
complex,
may

vs^~7cz:\":\"s'.\".r:'~
Exampk:
mixture

with

Liquid

SIU-*

a solubility

-..,.-,...

-\342\226\240\342\226\240\342\226\240
---\342\200\224.-.\342\200\224
--...-..
...
\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

He m*.Uuivi

gap is the

at W

miMuniof

liquid mix-

tanpcraiures.

The

ilie two iiefium

isotopes JHeand JHe, atoms

moat

interesting

;-.-,,

of

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
have
a
must be positi\\e to
The origin of the
solubility
gap.
{Chapter 12). Tito mi.\\ing
energy
low temperais tht! folio\" ing: 4Hc aloiiisarc bosons.At suliieiently
positive mixing
encray
temperatures
almost
jli \342\226\240*!
le afoins
have
state
orbii;tl
of the sysicm, vvherc
occurs) the ground
they

tiie Toruicr

30

20

10

40

Phaie

Diagrams for

50

60

.70

SimpleSolubility

80

Gaps

100

90

\342\226\240\"
Atomic

Figure

11.7

Liquid

percent

mixtures of

JHe and

He

pure

\342\226\240'He

4Hc.

kinetic
energy. Almost trie entire
energy of the mixture is contribuicd by t!ie
which
are
fermions.The
of a degenerate Fermi
atoms,
energy
per atom
gas increases
v,ilh concentration
7. This energy has a negative secondderivative
as n1'*,as in Chapter

kinetic

zero

3He

Pltase

Diagrams

Tor Simple

Solubility Gaps

dependence of solubiiily gaps,as in

the
11.8.
The
two compositions
xx and xf arc plaited horizontally,
Figure
The .v^ and xf branches
merge at the
vertically.
corresponding
temperature
maximum temperaturet,m for which a solubility gap exists. At a given temperatemperature,
overall composition falls within the raoge enclosed
mixture
whose
by
any
of actual
curve
is unstable
the
as a homogeneous mixture.The phasediagrams

phase

mixtures

form of

diagram

represents

with solubility

the temperature

according
gups may be more complex,

(he free energy relation/(.v),

but

the

underlying

principles

to

the

aclual

are ihesamc.

II;

Chapter

Binary Mlxtur

Slabk

Decomposilion

\\

1
1
1

Uns

Figure 11.8 Phase diagram

gap. A homogeneous mixture
i if

temperature

the point

curve. The mixture

will

curve

boundary

system

PHASE

(*,i)

a solubility

be unstable
stability boundary

tlic

ai

form two

separate phasesof the

the intersections of the stability
boundary
line

for

with

temperature

r. The

stability

calculated quantitatively

a parabolic

BETWEEN

EQUIUBRIA

with

x will

below

Tails

shown here was

of Figure lt.5,

system

oCcomposition

then

given by
curve with the horteontal
compositions

a binary

for

the

for

fo{x).

LIQUID

AND SOLID MIXTURES

a small

When

of

the

fraction

phenomenonis
mixtures.

of a

solid that forms

We

the
homogeneous liquid mixturefreezes,

is almost always

readily

understood

consider

a simple

different

from

that

composition

of the liquid.

The

liquid and solid

model, under two assumptions; (a) Neitherthe
from

the free

energies for

Phase

solid nor she liquid has a solubility

constituenl

is

The free energies

melting

temperature

ta or pure

Semperature tb of pure constituentB.

and
ta
ra.
Tor the solid and fL(x) Tor the liquid,
are

between
fs{x)

atom,

per

(b) The

gap.

Solid Mixtures

Between Liquid and

the melsing

Jhan

lower

a SemperaSure

consider

We

Equilibria

11.9a. The two curves

intersect
at some comLeSus
draw
a
commonlo
boSh
aS .\\ ~ xs
posision.
jangenS
curves,
touching/j
=
and fL a! x
xL.We can define three composision ranges, each with differcnS
shown

in Figure

qualitatively

internal

equilibria:

x < xL, the

(a) When

in

system

is a

equilibrium

homogeneous

liquid.

a
system in equilibrium consistsof two phases,
solid phase of composition xs and a liquid phaseof composition
xL.
x > xs the system in equilibriumjs a homogeneous
When
solid.
(c)
a
arc
The
and
of
and
a
so!id
in
compositions
xs
xL
liquid
equilibrium
phase
of the
temperature dependent. As ihc temperature decreasesthe free energy
solid decreases more rapidly
tlKll of the liquid. The Ungctitiai points in
than
Figure 11.9amove to the Icfi, Tliis behavior is rcprcscnScdby a phase diagram
stinihlr to the earlier representationof the equilibrium
curves for
composition

(b)

When

mixtures

xL<

with

xs, the

x <

11.9b the curve

In Figure

separation.

phase

for

xL

is called

the

curve.
Hquidus curve; the curve for xs is the soltdus
have been determined experimentallyfor vast numbers
The
phase diagrams
of binary mixtures. Those for most
of the possible binary alloys are known.*

For

Figure
phase diagrams are more complicatedthan
for
a
11.9b,
simple system,
germanium-silicon.
When
is lowered in a binary liquid mixturewith
the
the temperature
phase
of Figure lj.9b, solidification takes placeover
a finite
diagram
temperature
a liquid with
the
range, not just at a fixed temperature.To see this, consider
is lowered,
initial
composition
xiL shown in Figure 11.10.As the temperature
\342\200\224
of the solid formed is given
solidification begins at t
composition
x,. The
is changed.
'hat
of
the
In the
so
the
remaining liquid
by
xtsi
composition
the
example xiS > xiL, so that the liquid moves towards lowervaluesof x, where
if
solidification
is lower. The temperature has to be lowered
temperature
the
of
the
moves
solidification
is to continue. The composition
along
liquid
=
at
t
The
solid
formed
the
curve
until
solidification
is
compleied
tA.
liquidus
metal

most

homogenizeafterward

in

for

a long

slandard

Constitution

iabutatlons

of

binary

arc

by

solids

many

M.

in

atomic

solid

may homoge-

temperature remains
is too slow, and the

if lhe
diffusion

\"

indcnniieiy.

Hansen,

of binary alloys, firsi

second supplement,
alloys,

Constitution

Edioti,

for

''frozen

The

equilibrium.

particularly

diffusion,

time. But
remains

\342\200\242

The

atomic

by

homogeneity

R. P.

and is not in

in composition

is nonuniform

high

the

alloys

was drawn

which

Coitsilxatlon of binary
supplement,

allays,

McGraw-Hill,

McGraw-Hill, 1969. .

McGraw-Hill.

1965; R

A.

1958;
Shunfc,

11.9

Figure

ihis example

Phase

equilibrium

neither phase

cxhibhs

btiwccn

liquid

a solubiliSy

and

solid

mixtures.

In

gap. We assume

the free energies for i|ie two plxiscs;

The upper figure
(a) shows
The curves xL
ihc lower figure (b) shows ihc corresponding
diagram.
phase
and xs in She phase diagram are called ihe liquid us and She solid us curves.
= 940cC and
The phasediagram
is She Gc-Si phase diagram, wish
TCt

tA

x < xlt.

<

I412\"C

7\342\204\2425i

324

Phase

Figure

Mosi

11.10

Scmperalurc,

but

liquid
over

higher-nwiliiig

consiiluenl

lower-mching

consliSucnt

solidification

lemperalure

Advanced Treatment;

mixiuresdo

a finite

not

temperature

liquid

at a

range

from

and Solid

Mixtm

sharp
t,

'o ta.

The

first, thereby enriching the

liquid phase and thus lowering She
of ific liquid.
precipilaSes

in ihc

down

tower meltingtemperatureof the

system: a mixture of 69pet An and
solidification

Liquid

solidify

Eutecltcs. There are many

liquid phase remainsa

compositions

Between

Equilibria

to

temperatures

constituents.

31 pet

starts at a

binary

The

Si starts to

in which

systems

the

below the
alloy is such a

significantly
go!d-si!icon

solidify at

higher temperature.When

370\302\260C.

we

At

plot

other

the

of alloy
oflhe onset of solidificationas a Function
composition,
obtain
Mixtures
with two
we
the two-branch liqutdus
curve
in Figure
11.11.

temperature

solidification
minimum
temperature
liquidus branchesare calledcutectics.The
is She eutectic
is the eutectic SemperaSure,where She composition
composition.
is a two phase solid, wiih
The solidifiedsolid at the eutecticcomposition
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
oFthe
for
the
free
occurs
eutectic composision becausethe
homogeneous
energy
melt is lower than the free energy of the two
for
at
solid,
temperatures
phase
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
for the solid as in Figure 11.6,
assuine_/^(.\\\")

11:

Chapter

Mixtures

Binary

1600
404\302\260

1400

1200

1063\302\260

1000

/
\\

/
\\
0\302\260

1/

-31

Pure

11.11

Figure

Au

Euieciic

and

range

Figure

but

II.12a

below

10

iempctaiure
indicaie

37OX

complcic

80

90

100

Pure Si

silicon

percent

go!d-siljconalloys.The

iogeihcr ai ihe euieciic

daia poinls ai
ihe mixiurc docs noi

to difTcrcnt

corresponding

temperature

diagram of

ihe experimcnial

composiiion

constituents.

phase

60

50

40
Atomic

branches ihai come

line

30

20

10

Hquidus

iwo

consisisof

T, = 37O;C.The horizonial
ihai ihroughoul the eniirc

iis solidificalion

unlit

ihe

euieciic

crystal structures a and ^ for the two pure confor a temperature above the cutectic

is constructed

the melting

iemperature of cither consihuent,

so

that

to
energy of the liquid reachesbelow the common
tangent
phase curves. We can draw two new two-point tangents tltat give even lower free
energies. We now distinguishfive different
ranges:
composition
is a
(a) and (e). For x < xaS or x > x^, the equilibrium state of the system
solid. In the first range
the solid
will have the crystal structure a;
Homogeneous
in
the
second
the
structure
is
range
($.
(c). For xlL < x < XpL, the equilibrium state is a homogeneousliquid.
and
For
is in
a liquid
(b)
(d).
x^ < x < xaL or x^L < x < Xp$,
phase
equilibrium with a solid phase.
the
As
is lowered, faS and fa decreasemorerapidly
than/L,
temperature
and
of
the
the range
H.12b
homogeneous liquid becomesnarrower.
Figure
shows
the corresponding
the
two
curves.
solidus
phase diagram, including
tUe free

the solid

Figure 11.12 Free energies(a)and

sysiem.

At

to

the

theeulecltc

common

t, Jhe

temperature

tangent

to f^

energy fL

a homogeneous

A mixture

meits at a

above

(he

and fps, as in

tangent,

of Jhe liquid phase is tangential

free energy

which fL touches the tangent is the

iies

(bj in a

diagram

phase

Figure

eutcctic

although

11.13.

The

composition
At x < xt, the

composition.

fL may be beiowthe free energy

at

free
of

solid.

of composition equal to

single temperature,just like

the

eutectic

pure

composition

substance.

solidifies

The solidification

and

of

Chapter 11: Binary

Mixtures

FiCe energies

Figurel!.!3

compositions

away

From

and

ends

at

the eutecttc

and

ends

at

a higher

in

a euseclic

system at t

, andati

< xr.

starls at a

higher temperature
at
the
starts
eulectic
temperature. Melting
temperature
the

euieciic

composition

temperature.

The minimum properly of the

utilized. The Au-Si
eutectic
plays

melting

a large

temperature

role

in

of eutectics

semiconductor

is widely
device

tech-

welding of electrical contact

wires madeofgoldtosilicon
devices.
Lead-tin
exhibit
a euieciic (Figure
alloys
at
a
i83\302\260C
solder
below
that of pure tin,
to
11.14)
give
melting temperature
232;C.
is
to whether a sharp melting temperature or a melting
range
According
comor
a different
citlicr the exact cutectie compositionB6pet lead)
desired,
Salt
the
because
of the low
is
on
ice
melts
ice
composition
employed.
sprinkled

technology:

eutectic

the

cutectie

temperature

permits

-2L2\"Cof

low temperature

the H2O~NaC!

eutecttcat 8.17moipet

NaO.

The
in character,
solfdus
curves of eutectic systems vary
for the
greatly
die
ioclt
Pb-Sti system (Figure Il.M) die solid phases
in equilibrium
with
contain
:tn appreciable fraction of tltc minority
const
[merit, and this fraction
in
other
increases with decreasing
systems this fraction may be
temperature,
small or may decrease
with
or both. The Au-Si system
decreasing
temperature,
with
is an example:
The relative concentration of Au in solid Si ill equilibrium
of only
an Au-Si melt reaches a ma\\imum value
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
the
lite composition
tltat
at which the liquid phasefree energy
touches

10

\020

20

pure Sn

30

40
Atomic

50

60

percent

lead

70

90

100

pure Pb

10/tm
Figure

of [he
Jackson.

11.14
Pb-Sn

diagram of the Pb-Sn s> stem, after Hatlicn.{b) Microphotngrapf;

of J. D. Hunt and K. A.
magnified about S0Otimes.Courtesy

{a} Ptiasc
eutmic,

S29

11:

Chapter

Mixtures

Binary

curves lies between the

solid phase

tangent

to the

In some

systems this point lies outsidethe

and

were

fL

iti Figure

interchanged

interval,

Such

.\\2a.

and

compositions

xlS

as

and/t

if either/aS

arc caiied

systems

xfiS.

or/flS

peritectic

systems.

SUMMARY

1.

side by side is lowerthan

phases

separate

the combinedfreeenergy

gap when

a solubility

exhibits

mixture

free

the

of the

energy

two

of

homogeneous

mixture.

2, The
in

the alloy

For

position.

3. The mixing

for

energy

uM

for

p nearest

4. The

5. Mixtures

minimum

we have

A} _IBI,

px(l

is

interactions

nearest-neighbor
=

species are interchanged

of different

atoms

j(uAA +

uBB)]

.xL versus

x)[uAB

neighbors.
is

Hquidus

equilibrium
for a solid

when

arises

entropy

mixing

the

curve

composition

with a solid.

for

The solidusis the compositioncurve

phase in equilibriumwith

in

phase

liquid
Xs

versus

liquid.

two branches to the liquidus curve

solidification temperature is called
the

with

The

eutectics.

called

are

eutectic

temperature.

PROBLEMS

L Chemicalpotentialsm two-phase

[eniials ;iA and /jB of

phase mixtureare given
with
1.
liquid

the vertical
Mixing
3He-4He

energy

die two
by

the

intercepts

B of

and

oFthe two-point

edges oFthe diagramat x

=0

and

the chemical
an equilibrium

tangent

mixtures

in

in

the

Similarly,

solubility

oFPb

11-2

Figure

andPb-Sn mixtures. The phasediagram

of 3He
Figure 11.8 shows that the solubility

-> 0.

potwo

\342\200\224
1.

in 3He~*He

finite (about 6 pet) as r

residual
Figure.11.14 shows a finite
remains

that

Show

equilibrium.

atomic species A

Pb-Sn

in solid

phase

oF

liq-

in 4He

diagram

of

Sn with decreasing

t.

do

What

such

residual

finite

solubilities

about

inipty

the

Form

of the

Function

u(.x)?

3.

Segregation

In

this limit the

1to A, wish A' \302\253

Let B be an impurity
the
oF
can
be
as
linear
Free
non-mixing parts
expressed
energy
both
solid phases.
of x, as fQ(x) = /0@) + x/0'@),for
and
functions
liquid
Assume thai the liquidmixtureis in equilibrium
with
the solid mixture. Calculate
concentration
the
coefficient.
ratio k ~ xs/xL, called the segregation
equilibrium
For
k
\302\253
then
a
and
substance
be
many
systems
may
I,
purified by melting
and partial
resolidificatioti,
discarding a small FractionoFthe meit.Thisprinciple
used in the purification of materials,as m the zone
is widely
of semirefining
\342\200\224 =
=
\302\243
!
T
1000K.
Give
a
numerical
value
for
eV
and
semiconductors.
for/os'
/Dt'

4.

of impurities.

coefficient

of a

range

Solidification

binary

alloy.

Consider the solidificationofa

binary

of the
that,
regardless
diagram of Figure.' 11.10.Show
B
in component
initial
the melt will always become fully
composition,
depleted
ion
the
id i Seas
the
time
remnant
That
sol
the
last
of
the
meit
solidifies.
is,
by
will not be complete until
the
has dropped
to TA.
temperature

alloy

5.

wish

Alloying

the phase

of gold

hto

silicon,

(a) Suppose a

and
onto a Si crystal,
subsequently
diagram, Figure 11.11,estimate how

silicon crystal.
the estimate

The

for

densities

800\302\260C.

of Au

heated
deep

and Si

1000A

to
she

400\302\260C-

gold

layer
From

will

of Au
the

is evaporated
Au-Si
phase

penetrate

are 19.3and 2.33gcm\"\023.

into the
(b)

Redo

12

Chapter

Cryogenics

COOLING BY EXTERNAL
IN

AN

Gas Liquefactionby

WORK

334

ENGINE

EXPANSION

for

Effect

337

Effect

Joule-Thomson

the

Example: Joule-Thomson

van

der

Waals

Helium,

Pumped

Cooling:

to 0.3

HeliumDilution Refrigerator;

341
342

Miilidegrees

DEMAGNETIZATION:

ISENTROPIC

QUEST

333

339

Liride Cycle
Evaporation

Gas

346

ZERO

FOR ABSOLUTE

NuclearDemagnetization

348

SUMMARY

350

PROBLEMS

350

1. Helium

2. Ideal

as a

van

der

Waals

359

Gas

35i

Carnot Liquefier

3. Claude

Cycle

4. Evaporation

Helium

35!

Liquefier

352

Cooling Limit

for
5. Initial Temperature

Demagnetization

Cooling

352

physics and techiioiogyofthe productionoftow temperatures.

the physical principles of the most important cooling methods,

is the

Cryogenics
discuss

We

lowest

the

to

down

cooling

a gas

of

temperatures.

principle oflow temperature

generation

The dominant

by kiting it do work
be a conventional
may

against

is the

lOmK

to

down

during an expansion. The

a force

gas; the free electron gas in a semiconatoms

dissolvedin liquid 4He. The force
semiconductor;
or internal
to the gas. Below
be
external
against which work is done may
10mK the dominant
cooling
principle is the iscntropic demagnetizationof a

gas

employed

or

the

ihe cooling methods

chain lhat starts
cooling

discuss

We
laboratory

to the

Household

cooling

evaporation

liquid helium

below its

COOLING

BY

In the

method
boiling

EXTERNAL

EXPANSION

AN

in

the

they occur

in which

order

by liquefying helium and

in

from

proceeds

1 ;iK.
sometimes
lowest laboratory temperatures,usually
lOmK,
and automobile air conditioners utilize the
cooling
appliances

same

IN

gas of 3Hc

substance.

paramagnetic

there

virtual

that

temperature,

is used

in

the

to about

for

laboratory
1

cooling

K.

WORK

ENGINE

isentropic expansion

of a monatomicidealgas

lower pressurep2, the temperaturedropsaccording

from

to a

pi

pressure

to

(i)

by F.64).
temperature
working

process

and Ti = 300K; then the temSuppose p, = 32atm; p2 = iatm;

will drop to T; \342\200\224
75 K.
We are chiefly interested in helium as the
and for helium A) is an excellentapproximation
if the
cooling
gas,
is reversible.

The problems in implementingexpansioncoolingarise

of actual expansion processes.The problems
irreversibility
of good low temperature
lubricants.
by the nonexistence
and
cooling cycles follow Figure 12.1.The compression

the

from
are

partial

compounded

Actual
expansion

expansion
parts

of

itisng

by

Work in on

External

Heal

{Expansion

ejection

Expansion

ngine

Working\342\200\224

volume

gas ts
Simple expansion refrtgeraior.A working
is
the
heat
of
into
the
compressed;
compression ejected
environment.
The compressed room temperature
gas is
heat
counleriiow
further in the
exchanger. It then
precooled
to a
does work in an expansion engine, where it cools
volume.
Afkr
extracting
temperature below that of the working
hea{ from the working
the gas returns to the compressor
volume,

FEgure

via

{he

I2.I

heat

exchanger.

Ens

Chapter 12:

Cryogenics

separated.The compressionis

the cycle arc

exchanger by contact

flow heat

temperatureof
the

in

cooling

the

on

the

expansion

of the

design

The

work

done the
The total

by

plus the work

She

{Ul

on the

performed

important

fij and

the expansion

work p{Vl
gas.

the displacement

plus

gas

into

flowing

difference

enthalpy

Vx

a given

to

refer

mass of

is the energy
U2
the
the gas against
pressurep2-

with

engine

the gas

of

the

gas

work

The

is the difference

For a monatomic ideal

work

the

of

boih

to move

V% required

p2

by ihe engine

extracted

exchangeris as

is the

engine

expansion

where

leaving

energy

im-

requirements

cooling

gas: The iota!energy

and output

compressor,

by

the

iruernat energy U^

engine is the

heat

the

via

compressor

expansion engine.

extracted

the input

between

the

the

reduces

The design of Sheheat

engine.

counter-

in a

precooled

return
gas stream at the low
cooled to itslowesttemperature
a low friction turbine.The cold gas extracts

The heat exchanger greatly

exchanger.
imposed

usually

temperature

gas is then

load and then returns to

the cooling

from

room

near

room

above

cold

the

with

The

load.

engine,

expansion

heat

as

the

or

at

performed

The hot compressedgas is cooled to

temperature.
by ejecting heat into the environment. The gasis further

- {Uz +

4- PlVt)

gas

j=

pV =

and

|Nr

PlV1)

Hs

~~

B)

H2.

Nr, hence H =

The

\\Nx.

engine by the gas is

-

\302\273

|N{t,

C)

r2).

The countefHowheat exchangeris an enthalpy

device:
it is an
exchange
expansion engine which extractsno externalwork.
Most
use expansion
engines to prccool the gas closeto its
Hquefiers
gas
It is impractical
to carry She expansion cooling to
temperature.
liquefaction
of
of
a liquid
the point liquefaction:
the
formation
phase inside expansion

enginescauses

mechanical

is

usually

Joule-Thomson

liquefiers

usually

temperatures,

with

multiple

The principle of

to

the

electron

potential
potentials.

cooling by

gas

in

or

more

stage

expansion
expansion

of an

below.

exchangers.
isentropic

semiconductors.

When

ideal gas

electrons How

is applicable

from

semi-

high electron concentration into a semiconductor

she
the electron gas expands and does work
concentration,
against
barrier
between the two substances that equalizesthe two chemical
is used
electronic cooling, called the Peltiereffect,
The
resulting

semiconductor wuh
electron

heat

final liquefaction

Helium and hydrogen

engines at successive tem-

discussed

stage,
two

eontain

The

difficulties.

operating

with

a lower

Gas Liquefaction by

down

to about

So 135K
Gas

195 K quite routinely;in

by the

Liquefaction

units

multistage

12.2.The work

~plt(Vj doneon

Here

dVt

the

is

in

gas

pushing

it through

is negative

The overall processis at constant

expansion valve acts as an expansion
= 0 in
If
B), we have H\\ ~ li2 in the

11

\342\204\242

ideal

\\Nr,

so

that

down

\342\200\224in

ts

r2

of

al! gases.

causes

significant

will condense.

gas

lower

pressure

p2,

the displacement
and
{he expansion valve

work

engine

sec this,

that extracts
effect.

Joule-Thomson

There is

the expansion.

the

gas on the downstreamside.

To

enthalpy.

At
are

interactions

the

between

difference

{he

+p2(\"/2 recovered from the

and dV2 is positive.

work

displacement

temperatures

pressure p, is forcedthrough

valve into space with

an expansion

called

constriction

as in Figure

Gas at

is simple.

implementation

practical

Effect

Joule-Thomson Effect

Intcrinolccular attractive interactionscausethe condensation

icmpcratures slightly above the condensation
temperature
that
work
strong enough
against them during
expansion
of the
cooling of the gas. If the coolingis sufficient,
part
This process is Joule-Thomsonliquefaction.

The

Joule-Thomson

achieved.

been

hnvc

the

notice that the

zero work. With

For an ideal gas

zero coolingeffect

for

an

gas.

gases a small temperaturechange

work done by the molecules
duriiig
expansion.
in real

|2,2

The Joule-Thomson

through an expansion value. If

be a temperature
change during

done against
initially

will cool

the

below

The sign

the

eflccl.A

the
the

gas

is pushed

notlflieal. ihere will

because of work
expansion

gas is

forces.

If the

on Joule-Thomson expansion-

internal

of the temperature

temperature is
inversion temperature, riB,, the gas

intermolecuhtr

a certain

of

because

valve

Expansion

Figure

occurs

12:

Chapter

Cry

Liquefaclion dala

U.I

Table

n.

CO,

195

cm

112

902
77.3
20.4

o,

N,

H,
\342\200\242He

4.SS

JHe

3.20

the

The las

liquid.
Jrti

T( ano\" oot

T,,.,

Tt,

(jas

lo

for

U/mol

304

B050)

25.2

191

A290)

155
126
33.3
5.25
3.35

umn,

measured

em'/mol

223

66

6.82

67

621

5.57

205

0.90

28.1
34.6
28.6

51
B3)

0-082

320

0.025

50.8

n walls

pressure.

mosphcric

der Waais

effect for

have

ran

\302\253=

JWt

gas, where a and

corrections caused by
corrections

opposite

the

short

is

0.14

for

because its lrjple

us LNG
give daia

quamilics for shipping

we
of air. For helium,

signs. The

the critical

far

li'aab

gas.

{S2fV){bx

b are

positive

range repulsion and

initial
such

poinl

fuel.

boih

Liquid
for ihe

temperature.
an expansion

for common

== lab

in

found

gases

A0.75)

that

D)

constants. The
the

= 2/rt,

tempera!urc, defined by A0.46).

lemperature.
iln, is the inversion

We

- 2a)

tola! correciion changes

tinv

where xc

0.7!

12.1.

Table

Joule-Thomson

a van

8.7

'

H
for

45

be la'ken up

can

thai

on the
depends
change during a Joule-Thomsonexpansion
All gases have an inversiontemperature
below
which
TIn,
above
which
heals
(he
it
cools,
gas. inversion
temperatures

Example:

314

893

of natural gas, which

is liquefied
in huge
and niirogen are separaied iu lhe liquefaction
ei isotope
4Hc and for 3He.

in

Mite

34.4

Carbon dioxide solidifies

are listed

wall

8.18

tndkai

Atl/V,

V,.

AH,

long
sign

range
at

last

two

atiraction.

arc the
The correc-

terms

the temperature

E)

at fixed
For t < iin, the enthalpy
here in expansion the work done against the
increases;
temperature increasesas the volume
In a process at consiant enihafpy
attraciive interactions between molecules
is dominani.
this increase
is compensated by a decrease of the \\Nt ierm, that is, by cooling
the gas. For
The

temperature

Gas Liquefactionby
i a

ioIccuIcspenetrate

farther

lhe repulsive

Joutc-Thot

s because now the

anl: ai lhc higher

fixed lemperamre
inio

the

work

done by the

lempcraluie

the

regio

wilh
litjueficrs the Joule-Thomsonexpansioniscombined
heat exchanger, as shown in Figure J2.3.The combination
is
a cycle in 1895
to
called
a Lindc cycle, aficr Carl von Linde who
used
such
air starting from room temperature.In our discussion
we
assume
that
liquefy
is
ihe
same
the expanded
the
heat
at
from
exchanger
gas returning
temperature
as the compressed
it. We neglect any pressure differencebetween
gas entering
the output of the heat exchanger
and the pressure above the liquid.

Linde

cycle.

In gas

a counlerflow

To

and

from

comprcs

Figure
by

12.3

The Lindecycle.Gas

combining

a countcrflow

JT expansionvaJv.

Liquefied

gas

Joule-Thomson

expa

Iieatexchanger.

Figure

as a

Performance of helium
inpui pressure,

12.4

fund

ion ofihe

for various values of

ihc

inierna! refrigeration load available

ii^uciicrand

ihc

ihe

heal

through

See Problem
Plenum,

still

exchanger
A. J.

1971.

p. 1S7.

if

gas boiledoff

rather

Croft

cunes give
at 4.2

coid helium

3. Afier

The solid

in

than

boiled

QiM
(he

=
toad

curvesgive
tfDUl

A&mWL-dcryo&mcs

ihe

Hia, ihe

is placed

by lhc load

oiT into

Liude cycle,

of 1 aim and

pressure

ouiput

temperature.

The broken

coefficient

liquefaciion

input

an

by the

operating

litjueficrs
for

inside ihe

is relumed

liie atmosphere.
(C. A. Baiiey, ed.),

Evaporation Coaling;

The

comhimtiion

hc;\302\273

fraction

is

Constant

liquefied.

Hla

lhe input

of

heat

the

and

output

under lhe pressurepoal.

peraturc

enthalpy
ihat the

suppose

J)H9Ui'

\302\243!

lhe enthalpy

tfHl) is

exchanger-

consimu

\302\2436}

mo!c
of
llou, = H(Tin.pBJare the enlhalpies
per
both
at
lhe
common
pressures,
upper temperature

H(TiMp-a) and

gas at

combination;

to 0.3

requires lhat

cniluilpy
=

Here

Hie

enter

//;\342\200\236 -IWii,

is ;i

valve

exchanger-expansion

arrangement. Let one moleof gas

PumpedHelium,

From

F)

per moleof liquid

its

at

boiling

lcm-

the fraction

we obtain

17)

called

the

coefficient.

liquefaction

when

lakes place

Liquefaction

>

//\342\200\236\342\200\236,
Hia;

> H{Tia,p-J.

HiT^J
the

Only

Joule-Thomson

will

take place.

with

rapidly

If

Figure 12.4 shows lhe

experimentally.
from
them Tor helium. The liquefaction

known

are

G)

calculated

coefficient

coefficientdrops

numerator

lemperalure of lhe heat exchangermaHer.

at this temperature cools the gas, liquefaction

expansion

The three enthalpiesin

liquefaction

(8)

at the input

enthalpies

the

is, when

thai

Tiat

increasing

decrease of the

of the

because

denominator. To obtain useful liqueinversion

;. > 0.!, input temperatures below one-thirdof the
liquefaction, say
For
are
this
usually required.
temperature
many gases
requires precedingof
and
the
engine. The combination of an expansionengine
gas
by an expansion
is invariably
a Linde
engine
cycle is called a Claude cycle. The expansion
12.1preceded
by another heat excitauger, as in Figure
in

Coofing:

Evaporatfon
from

Starting

evaporation
latent

and

G)

heat

liquid

the

Pumped Helium, lo 0.3 K

helium, the
of !hc liquid

simplest route lo lower temperaturesis

helium, by
cooling
of
the
of vaporization
liquid Iteltum

The heat extractioncauses

ihc

:itonu'c

ihc

forces

of the

increase

that

cnuscJ

Tltomson cooling tlte initial

initial state is a liquid.

further

cooling:

helium
staie

is

pumping
is extracted

work

io liquefy in
a gas, while in

lieiium

away

along

is done
the

first

evaporation

vapor,

with the

y
'

vap,-..

against the interpi;>ce.

hi JouL-

cooling

the

17:

Chapter

Table

Cryogenics

12.2

3Hc reach

Tempera turds,

in

which

kctvifi.at

1 he

vapor

of 4He and

pressures

values

specified

p(lorr)

The

lowest
in

helium

0.79

0.28

0.36

vacuum

1.27

1.74

2.64

0.47

0.66

1.03

1-79

cooling of

by evaporation

technology

pressure

vapor

gas and

0.98

liquid helium
14). As the ternperalure drops,the
(Chapter
(Table 12.2} and so docsthe raie ai which
can
be extracted
from the liquid helium

accessible

tempcralure

isa problem
equilibrium

0.66

drops

its heat ofvaporization

bath.
cooling

Evaporation

Helium

in

such a5

Dilution

classical

K io

of

pressure

refrigeration

principles

0.0! K. is

dominated

evaporation refrigeratorin a
We saw in Chapter 7 that

cooling

everyday
ait

conditioners.

Militdegrees

Refrigerator:

Once the equilibriumvapor

0.6

cooling principle

household refrigerators and freezersant! in

is in the workingsubstance.
difference
only

devices
The

dominant

ts the

lose their
by

very

clever

dropped to

I0\023

torr,

range
utility. The temperaiure

dilution

helium

the

3He has

liquid

from

which is an

refrigerator,

disguise.*
quantum
are bosons, while

3He atoms are fermions.

is not important at temperatures appreciably higher
distinction
This
of \"fie, 2.17 K. However,the two
than
transition
the
temperature
superfluid
Below
as altogether different substances at lowertemperatures.
behave
isotopes
like
0.87
K. liquid
3He and 4He are immiscibleovera wide
composition
range,
in Chapter
11 and is shown in the phase
oil and water. This was
discussed
*He

of 3He-4He mixtures in
diagram
the range labeled unstable wil!

atoms

11.7.

Figure

A mixture

decomposeinto

two

with

in

composition

whose

phases

separate

area.
that
are given by the two brandies of the curve enclosing
compositions
3He phase.
3He phase floats on top of the dilute
The
concentrated
3He
to about
3He
in
As T -\302\273
the
concentration
of
the
dilute
drops
0,
phase
6 pet, and the phaserich in 3He becomes
essentially
pure 3He. Consider a liquid

For good reviews, sec D. S. Belts.Contemporary

36, 181A968);for a general review or cooling

Physics
techniques

9.97 {1968): IC.

1 K see W.

below

Lounasmaa, Repts. Prog, Phys. 36, 423 A973);

O. V. Lounasmaa,
below t K, AcademicPress,Hew York, 1974. A very elementary

methods
Scientific

American

221,26

(t%9).

\342\226\240

Wheatley.

Am-1

J. Huiskamp

Experimental
accoun!

and
principles

Phys.
O. V.
and

Is O. V. Lounasmaa,
.

12.5

Figure

dilution
Cooling principle of ilm helium
wiih a JHc-4He nmiure. When
from
ihc pure ]He fluid
and

Hlc is in equilibrium
mixiure, sHe evaporaics

3He-4He

mixture wiih more than 6 pet 3Hea*

range, near the bottomof Figure11.7.At

atoms have condensedinto

these

refrigerator.
Liquid
is added io the
absorbs
heat in ihc

4He

a temperature

temperatures

in the
almost

millidcgree
all the 4He

Their entropy is negligible

which then behave as if they were
of the mixture.
If the 3He concenalone, as a gas occupying the volutne
present
the excess condenses into concentrated liquid 3He and
exceeds
concentration
6pct,
heat
If concentrated liquid 3He is evaporatedimo the 4He
latent
is liberated.
the latent heat is consumed.The principle
rich
of evaporation
phase,
cooling
can again be applied: this is the basts of the heliumdilution
refrigerator.
To
to
obtain
see how the solution of 3He can be employed
refrigeration,

comparedto

that

of

the

the

remaining

ground

state

orbital.

3He atoms,

the equilibrium between the concentrated3Heliquidphase

the
and
tile
lliai
JHc:4lic
nilio
of
dilute
gas-like plliise (Figure 12.5).Suppose
with
the dilute phase is decreased,as by dilution
pure *He. In order to restore
3He
aiomswil!
the equilibrium
from the concentrated
concentration,
evaporate

consider

iHc

3He liquid.Coolingwill

result.

be
a cyclic process the 3He-4He mixturemust
again.
separated
is
tile
different
common
method
Tile most
distillation,
equilibrium
using
by
12.6
shows
a
schematic
3He
and
*Hc
of
12.2).
(Table
Figure
vapor pressures
on these principles. The diagram is highly
built
diagram of a refrigerator
In
in
actual
refrigerators titehcat exchangerbetween
oversimplified.
particular,
An
alternate
chamber
and the still has an elaborate multistagedesign.
the
mixing
of 4He
method*
to separate
the. 3He--4He mixture utilizes tile superfluidity
of
reasons
it is less commonly used,
below 2.17 K. For a variety,
practical

To

obtain

although

Us

performance

is excellent.

\342\226\240
.

Chapter

12:

Cryogenics

3He pump

loop

Key:
Liquid
\342\226\240
I 'lie

Dilution Refrigerator:

Helium

AtitliJegre

Hdium dliulion refrigerator. Prccooledliquid

a mixing
3He enters
chamber a( (he tower cud of the assembly,
wlicrc cooling takes place by ihe quasiof the 3He atoms into the denser JHc-Jf1cmixed
cvaporaiion
underneath.
phase
12.6

Figure

The quast-gas of JH atoms dissolvedin liquid

*He then diffuses through
heat exchanger into 3 still. There the JHe is disiilledfrom
the 3Hc-4Hc

a countcrfiow

mixture

a useful
3He evaporation and circulation
selectively, and is pumped olf.To obtain
heat
must be added to the still, 10 raiseUs temperature
to about 0.7 K, at which

rate,

vapor pressure is ssiH much smaller. Thus, the 4He does not
a nearly stationary
appreciable extent; ihe *Hc moves
riirough
JHe is returned to ihe system and is condensed
background of 4Hc.The pumped-off
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
the *He

temperature

lo any

circulate

circulation
in rhe

first

pump over ihe pressure in

siill. ihcn in the counter/low

still. The liquified JHe is cooled further,

heat exchanger, beforere-entering
tlic miung

the

chamber.

In the convendilution refrigerator has a low temperaturelitnft.

conventional evaporaiioii
this limit arose because of the disappearance of
refrigerator
the
but the quasi-gas phase of 3Hepersists
down
to t = 0, However,
phase,
gas
ihe heat of quasi-vaporizationof JHe vanishes
to x2, and as a
proportionally
Ihe
rate
heat
removal
from
the mixing chamber vanishes as i1. TI'S
result,
low
device;*
limit is about 10 mK, In one representative
temperature
practical
was capable
of
a temperature
of 8.3 mK has been achieved:ihe
same
device

The helium

removing 40/AVat 80mK.

ihe

design

there is

SmK

below

Temperatures

of Figure

2.6,

no needto cooi the

mixingchamberdrops
removed from
The

dilution

the

off the

3He

incoming
its

below

single shot operation. If,

3He supplyafter some time of opeiation,

be ncltievcu by

can

we shut

sleady

itself,
state

and

value,

of the

ihe temperature
until

has

3He

all

in

been

chamber.

refrigerator

is not the

oniy cooiingmethodin

the

inillikelvin

known
the peculiar propertiesof JHe.An alternate
method,
in Figas Pomcranchsik cooling, utilizes the phasediagramof 3He,as shown
and
between
Figure 7.15,
with
its negative
liquid
slope of the phase boundary
ant!
solid 3He, The interested reader is referredto the reviews
by Huiskamp
Lounasmaa, and by Lounastnaa, citedearlier.

that utilizes

range

'

N.

H.

Pcnnings,

84, 102A976}.

R. de

Bruyn

Ouboicr,

K. \\V. Tacoois.

Phjiica 8

SI. !0! A976).

and

Physiea

DEMAGNETIZATION:

ISENTROPIC

QUEST FOR ABSOLUTEZERO

0.01

Below

doniimim

K the

cooling process

is the isciitropic(adiabaiic)

dcm;ig-

paramagnetic substance. By this process, temperaturesof I niK

have
been attained
with electronic paramagnetic systems and j /(K with nuclear
systems. The method dependson tlie fact that at a fixed temperaparamagnetic
temperaturethe
of a system of magnetic momentsisloweredby application
of a
entropy
slates
are
to
because
accessible
the system
fewer
magnetic
field\342\200\224essentially
small.
when ilic level splitting
is large than when the level
is
splitting
Examples
of the dependence of the entropy
2
on tlie magnetic
field were given in Chapters
of a

iictizatioii

3.

and

We first apply a
will

magnetic field

a value

attain

without

will

then
flow

remain

t2
into

to the

appropriate

reducedto B2

the

changing

the

tj-

the spin

specimen

system only

of

value

entropy

means

which

unchanged,
<\342\226\240<
When

at constant

Bt

temperature
ij. The spin excess
If the magnetic field is then
Bj/tj.
the
of
spin system,the spin excess

that B2/z2

will

is demagnetized

from

the

system

#i/ri-

equa'

12.7-

can

vibrations, as in

of interest the

the temperatures

At

Bi,

isentropically,entropy

of lattice

entropy of the
will
be
usually negligible; thus the entropy ofthe spin system
during isentropie demagnetization of the specimen.
Figure

\302\253

HBz

lattice

essentially

constant

\\Latttce

Total

Spin

Lattice

Time\342\200\224-

Before
Time

Figure

12.7

cooling

of

Time\342\200\224\342\200\242

Before
Time

New

equilibr:

at which

magnetic field
js removed

field

removed

demagnetization the total entropy of the S

in
of the lattice should be small
entropy
with the entropy of the spin system in order to obtain significant
the lattice.
During

isentropie

specimen is constant. The

comparison

equilibrium

at which

magnetic
is

New

Fig-

vibrations

initial

is

Quest for

Demagnetization:

lsentropic

Zer

Absolute

as a function of Icmpcralure.assum
Entropy fora spin \\ sysiem
of
field
100
Bx
gauss. The specimenis magnetiz
magnetic
Thu cxlcrna! ntagnctit
insulated
isothermaiiy
ihcrmaMy.
along ah, and is then
field
is 1 timed
on a reasonable
off along/>c. Ill order to keep the figure
sculc
llic initial temperature
tlie
field
are
lower
woi
and
external
than
magnetic
Tj

12.8

Figure

inicrna!

an

used

in

The

random

practice.

steps

out in the

carried

cooling processarc shown

field is

applied at temperaturetx

the

the

with

giving

surroundings,
{At? ~ 0)

insulated

and the field

with

the

specimen

isothermal

in

thermal

in good

removed; the specimenfollows

6c, ending up at temperature t2. The thermal

contact
is broken
helium
provided by
gas, and the thermal

gas with
The

the
contact

constant
ai

is

t,

by removing the

a pump.

population

of a

magnetic subievelis a function

is the magnetic momentof a

ofthe

contact

path ab. The specimenis ihen

path

entropy

12.8. The

Figure

population

spin.

distribution;

The

spin-system

hence the

only

entropy

of

ntB/x,

is a

spin entropy is a function

function

only

where
only

oimBjx.

localinteractions
is theeffeclive field that corresponds to thediverse
among
temperature
r2 reached in an
spins or ofthe spins with the lattice, the final

If SA
the

isenlropic demagnetization experimentis

(9}
rt the initial temperature.Results
which
as CMN,
Figure IZ9 for the paramagnetic salt known
.
.
magnesium nitrate,
where

is the

initial

field and

are

denotes

shown

in

cerous

Final

Figure 12.9

removed

as

cniirciy,
and

fields

iiiiiial

field

magaclic

bul

0.6

0.5

in K

temperature,

Bf versus

experiments ihe magnetic

In fhese

nil rale.

After

Final

0.4

0.3

0.2

0.1

final

field

was

not

indicated values. The

were idcnliait in all inns.
S. Still and J. H. Milncr.

m tfic

only

icmpcraiurcs

unpublished results 61\" J.

6,
by N, Kuril, Kuovo Cimcnio (Supplement)

cilcd

1109A957).

The processdescribed
so
into a cyclicprocess thermally

is

far

a single

shot

disconnecting,

by

demagnetized
working substance from
at t,, and repeating the process.*

converted

process. It is easily
in one

way

or

it to
the load, reconnecting

the

another,
the

reservoir

Nuclear

Dcmagnelizalion

nuclear

Because
much

are

weaker

paramagnet.

\342\200\242

C.

similar

lhan
100 limes lower with a nuclear
paramagnet
in
The initial temperature of the nuclearstage

temperature

C. B.

V. Hctr.

Rosenblum,

lhan

arc weak, nuclear magneticinteractions

a
to reach
electronic interactions. We expect

moments

magnetic

W.

Barnes,and

A. Slcyerl.

and i.

Daunt.

J.

G.

A.

Barclay.

Rev. Scj, insi. 25. IGS8 j|954);

17, 3S! A977).

OHgcnics

electron

with

an

nuclear

spin-

W. p. PraH,

S. S.

t\\'uc!ear Demagnetization

Iniiial magnetic

0.6

in

Held

KG

Initial

B/T'm

\\QS

G/K

Nuclear demagnctizaflons of copper

skirting from 0.012 K and various
fields. After M. V. Hobdcn
imd N. Kuril. Phil. Mag.

Figure

I2J0

in

nuclei

the

metal,

-1.1902!1959).

must
be lower
than in an
cooling
=
=
lfwestartatB SOkGandT, 0.01
10 percent
decrease on magnetization
is
experimen!

over

This is

to

sufficient

ihe

overwhelm

T2 ss 10\027K.The

temperature

electron spin-cooling experiment.

* 0.5, and the entropy
K,then/fiB/*87\\
of the maximum
spin entropy.
a final
lattice and from (9) we estimate
nuclear

first

oui by Kurli and coworkers on Cu nuclei

at about
0.02 K as attained by electron
stage

the

B\302\261

moments

of

3.1

the

and

I0~6K.
reached in this experimen!was 1.2
so
line
of Ihe form of (9): 7\\ = T|C.1/B)
Bin
wilh
^auss,
of the magnetic mointeraction
field
gauss. This is the ciTcctive

Cu nueiei.

nuclei

Temperatures

cooling

first

The

cooling.

demagneltzallon

load was

The motivation
conduction

at

below

the

electrons

temperature

1//K

for

have been

using

help

of the

first

nuclei

ensure

in a

metal rather than

rapid thermal

contact

stage.

achieved in experiments in

the system of nuclearspinsitself,

results

The

in an insulatoris that

of lattice

from a

starting

metal,

lowest temperature
in Figure 12-10fil a
llial

was carried

experiment

cooling
in

particulatly

in

which

experiments

the

combinations of cooling experimentsand

that were

nuclear

resonance

magnetic

experiments.*

SUMMARY

1. The

dominant

two

a gas

of

cooling

of the

principles

by letting

work

do

it

of low temperaturesarc ihe

a force during an expansion

production

and the iscntropicdcmagncii/atioii

of a

against

substance.

paramagnetic

is done
work
cooling is an irreversible process in which
interatomic
forces
in
a
It
is
used
as
last
the
attractive
against
gas.
cooling

Joule-Thomson

2.

stage

in

gases.

low-boiling

liquefying

3. In evaporation cooling the work is also doneagainst

but starting from the liquid phaserather than
the

the
5.

dilution

helium

of magnetic

system

moments,

an

when

external

moments
may
magnetic
nuclear
moments,
temperatures

using

devices

cooling device in

which

4He.

lowering of the

utilizes the

The

strength.
By

evaporation

household

of
cooling

laboratory

gas of 3He atomsdissolvedin

demagnetization

Isentropic

is an

refrigerator

gas is the virtual

basis

the

forces,

Using different

phase.

gas

working substances, evaporation coolingforms

and
cooling devices, automobile air conditioners,
(in the range 4 K down to SGmK).

4. The

interatomic

the

magnetic

temperature

of

field is

reduced

be electronic or nuclearmoments.
in the microkelvin range may

a
in

be

achieved.

PROBLEMS

L Helium
for

as a

helium

Use

of
the

and

liquid

data

in

it as
such

in

helium
Table

for
\342\200\242See,

example,

der

van

Waals

tlte liquefaction coefficient X

gas. Select the van der Waals

a way that Tor one

and that 2a/b is the

12.!. Approximate the

Hout

849A970).

(a) Estimate

H'aafcgas.

by treating

coefficientsa
volume

der

van

M. Chapcllier,

Hi(q

M. Goldman,

AH

4- f(rin

V.

mole 2Nb is the actual molar

actual inversion temperature.

denominator in G) by setting
-

H. Chau

xliH)

A0)

and A.

-.-._...\342\226\240

Abragara,

Appl.

Phys-41,

where All is the latent heat of vaporizationof liquid

how this
helium.
(Explain
arises
if
one
treats
the
as
an
ideal gas). The
approximation
expanded
gas
/. as a function of the molar volumes Yin and
resulting
expression
gives
Vatll.
Convert
to pressures by approximating the l\"s via the ideal gas law. (b) Inaert
numerical values
T = 15 K and compare with
for
12.4.
Figure
Carnot liquefier. (a) Calculatethe work
mole
of a monstomic
ideal gas if the
liquefy
Assume that the gas is suppliedat roomtemperature

2. Ideal

one

pressure p0 at whidi the liquefied

7\\ be the boiling temperature of the

of vaporization.Show

that

under

gas
gas

these

\\VL thai

iiqticfier
To.

be required to
operated
rcversibiy.
the same
and
under

would

is removed,

1 atmosphere.
typically
and A// the latent
at this pressure,
conditions

Let

heat

A1)

To derive A1) assumethat the gas is first cooled at fixed pressure p6 from
To
the fixed
between
to Tfc, by means
of a reversible refrigeratorthat
operates
upper temperature Tb ~ To attd a variable lower temperatureequalto the gas
~ 1\\.After reaching
Tb the
Initially
temperature.
T, = To, and at the end T,
at
the
lower
the
latent
heat
of
fixed
extracts
temperavaporization
refrigerator
of
temperature Tb.
(b) Insert
To = 300 K and values for Tb and AH characteristic
liter
of liquid
helium.
helium. Re-express the result as kilowatt-hours
per
Actua! helium liquefiersconsume5 to lOkWh.
liter.
1 mols\021
in which
cycle helium Hqucfier. Considera heliumliquefier
enters the Lrnde stage at T(o = 15 K and at a pressure pla = 30 aim.
all the
in liter hr\"'. Suppose that
liquefied
(a) Calculate the rate of liquefaction,
helium is withdrawn to cool an externalexperimental
the
releasing
apparatus,
load
in
boiled-off
helium vapor into the atmosphere. Calculate the
cooling
the
the
it
is
this
watts sufficient to evaporate
heliumat
rate
liquefied. Compare
if the liquefier is operated as a closed-cycle
with
the
load obtainable
cooling
the apparatus into the liquid collectionvesselof the
refrigerator
by placing
the
heat
so
lhat
the
still
cold boiled-off helium gas is returnedthrough
liquefier,
and
ex(b) Assume that the heat exchangerbetween
exchangers,
compressor
ideal
that
return
is
the
(Figure
12.1)
sufficiently
expanded
gas
expansion engine
the same temperature Tc as the
that
leaves
it with pressure
is at essentially
pout
compressedgasenteringit with pressure pc. Show that under ordinary liquefier
must extract the work
operationthe expansion
engine

3.

Claude

of gas

Te -

TJ ,

A2)

Chapter

12:

per mole

Cryogenics

of compressed gas. HereTin,

pin,

pBUt, and

have

the

same

meaning

Undo cycle sectionof this chapier.

Assume
the expansion
engine
between
ihe
and
operates isemropically
pressure-temperature
pairs
{pc,Tc)
Estimate
(Pia>Ti(l). From A2) and the given values of (pia,Tia),calculate(pc,Te).
(c)
the minimum
compressor
power required to operate the iiquefier,by assuming
the compression
is isothermal from
to pc at temperature
that
Tc ~ 50\"C.
poai
Combinethe result with {hecooling loads calculated under (a) into a coefficient
of refrigerator
for both
the
modes of operation. Compare with
performance,

as in ihe

Carnot

iimit.

cooling limit. Estimate the lowest temperatureTmia that can

if the cooling
load is 0.1 W
4He
evaporation cooling of liquid
=
and
the vacuum
I02filers\021.
Assume
(hat
the
pump has a pump speed S
helium vapor pressure above the boiling
is equal to the equilibrium
helium
lo TBliJ1, and
assume that ilic helium gas warms
vapor pressurecorresponding
the
to
roorn
and expands accordingly before it enters
tip
temperature
ptunp.
Nota: Tlte molar volume of an ideul
and atmospheric
at room
gas
icmpcramrc
pressure G60torr) is about 24 liters. Repeat the calculation for a mtjch smaller
heat load (I0~3 W) and a faster puinpA0J
is defined
liter s\"\021). Puntp
in
speed
4. Evaporation
be achieved
by

Chapter

14.

temperature far demagnetizationcoaling, Considera paramagnetic

field
ofiOOkG
with
a Dcbyc temperature {Chapter 4) of 100K. A magnetic
or lOtcsia is available in the laboratory.
the temperature to which the
Estiniate
that
salt must be prccoolcd
other
means
order
cooling
by
in
significant
magnetic
process. Take
may subsequently be obtained by !he isentropic
demagnetization
5. Initial
salt

to be I Bohr
ion
the magnetic momentofa paramagnetic
By signifimagneton.
0.1
of
the
initial
we
to
understand
temperature.
cooling
may
cooling

significant

13

Chapter

Statistics

Semiconductor

ENERGY

FERMI

BANDS;

LEVEL;

355

AND HOLES

ELECTRONS

358

ClassicalRegime
of

Law

362

Action

Mass

362

intrinsic Fermi Level

363

/r-TVPE AND
Donors

Fermi

SEMICONDUCTORS

P'TYVE

363

and Acceptors

364

Semiconductors

Extrinsic

in

Level

365

Semiconductors

Degenerate

368

Impunly Levels

Occupationof Donor

369

Levels

Example:

Gallium

Semi-Insulating

Arsenide

373

p-n JUNCTIONS

Reverse-Biased

p-n

NONEQUIUBRIUM

SEMICONDUCrORS

Abrupt

377

Junction

Quasi-Fermi

Drift and

Flow:

379

Diffusion

Example:Injection

381

Laser

Example:

Carrier

379
379

Levels

Current

372

Through an Impurity Level

Recombination

383

SUMMARY

385

PROBLEMS

387

1. Weakly

2.

Intrinsic

387

Doped .Semiconductor
and

Conductivity

Minimum

Conductivity

387

3. Resistivity and Impurity Concemraiiou

4. Mass Action Law for High Electron Concentrations

387

5. Electron

387

and

Hole

Concentrations

in InSb

6. Incomplete lonizationof Deep

Impurities
7. Built-in Field for Exponential Doping Profile

8.

Einstein

Relation

for

High

Electron

Concentrations

387
3S7

388
388

13:

Chapter

Ha

ht
n,

Carrier

conduct
v\302\273'ilti

conccnlration

= cffcciivc
=

effective

38S

Lifetime

388

Pair Generation

Electron-Hole

iiiiiiui^zny

388

Laser

9. Injection

10. Minority
11.

Statistics

Semiconductor

[tin xind valence b jfiu\302\243

\\ elects oeis snd

of holes

hoics^ donors

*inu

3cccplovs.

I he

c^uantiiEn

conccnlnU/on

for condudion

quamum

coiKcntralion

for

ctccirons;

holes.

densities
of states for the conduction
In the semieonductoi tileralurc
n,. and % ate called ihe effective
and valence bands. Notice
iKal we use ;i fo( tin; chemical
potential or Fcimi level, and we use Ji foi

cai-iicr mobilities.

ENERGY

The
is

FERMI LEVEL;

BANDS;

ELECTRONS

HOLES

AND

of the Fermi-Dirac disiributionto eiecirons

in
semiconductors
application
central
to the design and operation of all semiconductor
and
devices,

to much of modern electronics.We

of semiconductorsand

treat

devices

semiconductor

of the physics
thermal physics.
of the physics of

those

below

thus

aspects
are parts of

that

is familiar wjlh the basic

ideas
as
'n
texts
on solidslatephysics
the
crysialline
soiids,
treated
in
and
on semiconductor
the
We assume the
devices cited
references.
general
of
bands
and
of
conduction
electrons
and
hotcs.
Our principal
by
concept energy
aim is to understand the dependence
of the alt-important
concentrations of
conduction electronsand of holesupon
the
concentration
and the
impurity
that

assume

We

eleclrons

the

reader

in

temperature.
A

semiconductor

band
t

and

0 al!

is a

system

with

electron

orbitats

grouped

into two

energy

energy
gap (Figure 13.1). The lower band is the valence
at
the upper band is the conductionband.* In a pure semiconducior
valence band orbitats are occupied
and
alt conduction
band orbitals

bands separatedby

an

are empty. A full band cannot carry any current, so that a pure
in a semiconductor
at r = 0 is an insulator.Finite conductivity

semiconductor

follows either

in the conduction
from the presence of electrons,catled
conduction
electrons,
orbitats
in the valence band, called notes.
band or from unoccupied
Two different
electrons and holes:
mechanisms
rise to conduction
give
of electrons
from the vatencc band to the conduction band,
Thermalexcitation
of
or the presence
that change the balance between the number
impurities
of electrons
available
to fill them.
of orbitats
in the valence band and the number
and
the energy
the
band
We denote
valence
the energy of the top of
by \302\243,.,
rence
of the bottom of the conductionband
by e{. The differed

is the energygap of the semiconductor.Fortypical

eV.
0.1 and 2.5 electronvolts.In silicon,e, ^ 1.1
\342\200\242
We tieai both bands
of bands wtih additional

as single

for out (imposes it

bands;
gaps wiihtn each gioup.

does

semiconductors
Because

t ^

noi mailer thai

Eg

is between

1/40 eV at
boih

may

room

be groups

Chapter 13: Semiconductor

Statistics

Empiy

band

Conduction

Energy

atr =0

gap

Filled

air =0

t3.1

Figure

Energy

Air =
conduct
the

structure of

band

orbilajs occur in

a puic semiconductor

bands

\\vhjch

we usually

havec,, \302\273t. Substances

2.5 eV are usually insulators. Table 13.1 gives
semiconductors, together with other properties
Let

nt

ihe

denote

concentration of

insulator.

exlerid

gap.

energy

temperature,

or

through the crystal.

Gallorbitaisuplothe top of the valence band are filled,and ihe
the bands is called
ion bantl
is empty. The energy interval
between

The electron

the

pure semiconductorthe
ii, =

crystal is electrically neutral.

Most semiconductorsas usedn\\ devices
impurities that may become
thermally

gap of more than

later.

electrons and
two

about

for selected

gaps

energy

needed

of conduction

concentration

holes. In a

with a

wiH

nh

the

con-

be equal:

B)

\302\253*.

if the

\342\226\240temperature.

positively

tiiat

Impurities

charged

in the

give

an

have

ionized

electron

been

In the

inteniionaiiy

doped with

semiconductor

to the

crystal

process) are called donors.Impurities

(and
that

at room
become
accept

Bands; Fermi

Energy

data

structure

Band

13.1

Table

Lml; Elec

Energy

ions and

c Idea

at

gaps

300 K

itions

effective

olcs

li

free

1300K

\",.

eV

'

2.7 x 10

Cc

0.67

1.0 x !O 9

GaAs

1.43

Let

4.6 X

!he

\302\253j+be

'

10

10\"

0.58

11.7

0.35
0.71
0.42

0.07

0.073

15.8

13.13

12.37

0.39

0.015

band (and become negatively

of positively

concentration

charged acceptors.
An

ts called

1.06

0.56

17.S8

the

in

charged

acceptors.

of negatively

concentration

to

vacuum

ilia

10\"

6.9 x 10'*
6.2x 10\"

the valence

are called

process)

relative

cicctr on mass

x to'a

1.5 x

4.9 x 10 '

from

electron

an

1.1 x
5-2

4.6 x 10 '

0.18

of the

t.[4

1.35

masses,

constants

in/ftn

Si

,,p
InSb

units

in

Dielectric

f-statcs

Dcnslty-

i concentr

antun

/[/

charged donors and

The difference
C)

na~

donor concentration.The electrical

neutrality

the net ionized

the

na~

condition

becomes

which

specifies
The electron

distribution

the difference
concentration

[i is

the chemical potentialof the

electrons. In semiconductor
theory
the
Fermilevel.
called
Further,
almost

level

always

reserved

is designated

of a meia!

which

in

ihe

limil

r -*

by ef
we

for ihe

or

by

at

The

electrons.

To
\302\243.

theory

temperature.

confusion

avoid

as cf
our

and

with

the

the Fermi

Fermi

energy

which stands for tile Fermi

previous

usage

to

is always
potential
is
the character
fi

chemical

semiconductor

e refers

subscript

electron and hole mobilities,and

designated

any

E)
/

electron

the
in

0, we shall maintain

chemicalpotential

D)

no~~t

betweenelectronand hole concentrations.

may be calculated from the Fermi-Diracdis-

exp[(e where

\342\200\224

Hj*

6:

of Chapter

function

An

of the

level

letter /j for the

;i and

Given

the distribution

The

t, the number of conductionelectronsis obtained

function /,(e) over all conduction band orbitals:

of

number

[l
\302\243

- /.(*)]

= I

ftU).

V)

VI!

VB

is overall valenceband

the summation

summing

is

holes

*\\ =

where

by

Here

orbitals.

we have

introduced

the quantity

at energy e is unoccupied.We say

a hole\";
that
is the distribution
[hen/h(e)
function for holes just as f\302\243t) is the distribution
function for electrons. Comof
with
shows
that
the
involves
hole occupation probability
Comparison
(8)
E)
\342\200\224
e where
the electron
y.
y.
occupation probability involves c
p.
=
=
The concentrations
and nh
nt
NJV
NJV
depend on the Ferm't level.
But what
is the
value
of the Fermi level? It ts determined
by the electrical
\342\200\224
=
as
An. This is an
neutrality requirement D), now written
nh{y)
nt{y)
the
must
for
to
solve
we
determine
the
functional
implicit equation y.;
equation

which

that an orbital
probability
the unoccupied
orbital is \"occupiedby
the

is

ne{y) and

dependences

nh{y}.

Classical Regime
We

assume

that

by the

defined

regime

concentrations are

and hole

electron

both

requirements

that

\302\253
1

fr

and

fh

in

as

\302\253
I,

the

classical

in Chapter

This will be true if, as in Figure 13.2, the Fermi level lies insidethe energy
and ts separated from both band edgesby energies
that
large
enough
-

exp[-(\302\243c

To
few

satisfy
times

inequalities

are

satisfied

(9) both
larger
(9)

\342\200\224

place

n)

(gc

than

in many

/i)/t]

\302\253
1;

and

(/t

exp[-0*

eu)

to

have

ej/t]

\302\253
1.

be positive

6.
gap

(9)

and al

least a

The
a semiconductor is callednondegenerate.
and
limits on the electron and hole concentrations

t. Such
upper

applications.

/J.E.)and /h(g)reduceto classical

With

distributions:

(9)

the

two

occupation

probabilities

Classical

':.-\"-\\~'\\

Regi

Conduciion
I

band

13.2 Occupancy oforbiials as a finite temperaiure,

to the Fermiaccording
The conduclion
and valence bands may be represented
Dirac disSribution
function.
numbers
in terms of temperature-dependenteffedive
Nc, Nc of degenerate orbiials
The
located aS the iwo band edges e,, \302\243\342\200\236.
n(, n( arc ihe corresponding quantum

Figure

We

use

F)

and

exp[-(e

A0) to

write

=>

the

total

number

cxp[-(,,

of conduction

A0)
electrons in the

form

N,

A1)

Statistics

13: Semiconductor

Chapter

where we define

N, \342\200\224
\302\243
is
\302\243c

Here

band

the

A2)

ej/r].

conduction electron referred to

of a

energy

\302\243exp[~(s
Cfl

conduction

the

ec as origin.

edge

The expression for

lias
the maihematical
fomt of a partition function
a similar
conduction band. In Chapter3 we evaluated
sum denoted there by Zlt and we can adapt
that rcsuil lo the prescuJ problem
with
an
for
modificalion
band siructure effects. Because of the
approximate
rapid decrease of cxp[-{\302\243 - e()/i] as c increases above its minimum value
for

one

at ee,only

Nc

in the

electron

ihe

of orbitals

distribution

within

range

of a few

above

cc really

evaluation of the sum in A2). The orbitalshigh in the band

make a negligible contribution. The important
is that near the band edge
point
the electronsbehave very much like free particles. Not only arc the electrons
of the semiconductor, but the energy
mobile,which causes the conductivity
distributionofihe orbitalsnear the band edge usually differs from that of free
in the
particles
only by a proportionality factor in the energy and eventually
matters

sum

in ihe

for Z%.

We can arrange for a suitable proponionaliiyfactor by use of a device

we calculated the
called the densify-of-sfates effective
For
free particles
mass.
in C.62),
but for zero spin. For particlesof spin
| the
partition function
Z\\
result is larger by a factor of 2, so that A2) becomes

Nc = Zj

this gives

Numerically,

NJV =- 2.509 x
where

Tis

1019
x

dependenceas
this

Nt
A3),

formally

for
but

ihe same temperature

a
by
proportionality facior. We
exhibits

semiconductors

actual
differs

by wriiing,

in magnitude
in

io

analogy

A3),

Nc *= 2(mSz/2nti2K'2V

where
Experimental

is more

(H)

G/300KK'2cm\023

in kelvin.

The quantity

express

A3)

2(mx/2nh2)i!iV.

2nQV=

me*

is

values

than

called

the

arc

given

a formality.

effective mass for

denshy-of-btates
in Table 13.1. The introduction

In the theory

of

electrons

A5)

,
electrons.

Experi-

of effective

masses

in crystals

it

is

shown

that

Classical Regime

Ihe dynamical behavior of electrons

and

forces such as electricfields,

free electron

the

from

Ihe density-of-staJes
We

the

define

that

is

holes,

the influence
of external
effective
wilh
masses different

under

of particles

dynamical massesusually
masses, however.
mass. The

quantum

coticetilralion

for
??\302\243

eleclrons

conduction

from

different

are

as

NJV -

nc =

A6)

By A0 the conductionelectronconcentration

ne

NJV

becomes

A7)

Jo the assumption
The earlier assumption (9) is equivaleni
that n,. \302\253
nc, so
that the conduction
electrons act as an ideal gas. As an aid to memory, we may
level at ;i. IVanriiuj:
think
as
wiili
the Fermi
of Ne
arising from N( orbilalsat \302\243\302\243,
In
is invariably
called
the effective density of
the semiconduclor
literature
nt

statesof

conduction

the

Similar

reasoning

band.

gives the

number of holesin

valence

ihe

band:

- e)/t]

wiih

the

definition

A9)

We define

the quantum concentrationnv

where

wk*

concentration/^

is

llns

NJV

dcnsity-of-sJaJcs

for

holes

as

2{in^z/2jihi)m.

effective

mass for

holes.

By

(IS)

ihe

hole

s NJV is

nh

\342\200\224
aBexp[\342\200\224(/(

\342\200\224

e,-)

B1)

gives the carrier concentrationin

A7), this

Like

positionof

ceniraiion and the

edge.

In

of the

valeuce

is

of the

independent

'V'k = 'Wexpf-fE,.where the

and

energy gap

the common

concentration

t^

Fermi level so longas the

concentrations

Then

classical regime.

in the

valeuce band
effective density of states

Action

The productn^nh
are

the

called

con-

quantum

to the

band.

of Mass

Law

is

nu

(he

of

terms

relative

level

Fermi

literature

semiconductor

(he

the

s=

\302\2439

ec

eff.

In

O/r]

s=

ncnuexp(~

we have

semiconductor

a pure

B2a)

eJz)

value of the two concentrations is called the

of the semiconductor. By B2a),

\342\200\224

>ibt

ut.

carrier

intrinsic

B2b)

The Fermi level independence of the

retains its value even when ne <\302\243
nh, as
atoms,

impurity
We

then

may

both

provided

product
in the

concentrations

means

n^iij,

this

that

product

presence of electrically charged

remain in the classical regime.

B2a) as

write

B2c)

The
mass

of

value

action

the

depends

product

law of

only on

the temperature.This result

semiconductors, similar to

chemical

the

mass

action

is

the

law

(Chapter 9).

Intrinsic FermiLevel
For

an

intrinsic

sidesof A7)

and

semiconductor

eB

= e^

nh

and

we

may

equate

the right-hand

B2b):

neexp[-(ec
Insert

ne =

\342\200\224
and

eB

divide

- ^)/r] =
by n,.exp(

(vO\022exp(-\302\243/>*).

\342\200\224\302\243(/r):

ej/2r].

B3)

and Acceptors

Donors

logarithms to obtain

We lake

/i

{U,

+
\302\243,.)

= l(cc

|t Iog(u,/u,)

of A6) and B0). The Fermilevel

(he middle of lhe forbidden gap, but
by use

is usually

that

amount

Pure

an

semiconductor
lies near
the exact middle by an

intrinsic
from

displaced

B4)

3rlog(\302\273ifc7\302\273i,*),

small.

AND p-TYPE SEMICONDUCTORS

w-TYPE
and

Donors

for

+ e,) +

Acceptors

are an

semiconductors

idealization of Httle

Semicon-

interest.

practical

to
usually have impurities intentionally added in order
semiconthe concentration of either conductionelectrons
A
more
with
conduction
electrons
than holes is called \302\273i-type; a semiin devices

used

Semiconductors

or holes.

increase
semiconductor

n and
electrons is called p-type.The letters
p
and
in
carriers.
Consider
a
silicon
positive
signify negative
majority
crystal
atoms.
which some of the Si atoms have
been
substituted
by phosphorus
hence each P has
Phosphorus is just to the right of Si in the periodic
table,

semiconductor with

fit

into

the

Si it replaces.
valence band; hence a Si crysial

filled

than the

more

electron

one

exactly

more holes than

do not
electrons
P atoms wiil contain

extra

These
some

with

more conduction electronsand, by the law of muss action, fewer holes than \302\253
Si crystal
Next consider aluminum atoms. Aluminum
is just
to the left
pure
of Si in the periodic
fewer
than
the Si
table, hence Al lias exactly one electron
it replaces.
As a result, Al atoms
increase
of holes and decreasethe
the number
of

number

electrons.

conduction

Most impurities in the same columnsof the periodic

behave in St just as P and Al behave.
What
matters

electrons

relative

from

Impurities

Similar reasoning
For the presentwe
may

enter

assume

that

is the

to
Si
not the total number of
other columns of the periodic table will

and

can be appliedto other

lhat

assume

band or

the conduction

each acceptor

fill

one

and Al will

number of valence

electronson
behave

not

for

semiconductors,

donor

each

as P

table

the

atom.

so simply.

example

GaAs.

atom contributes one electronwhich

hole
also
in the valence band. We

atom removes one electron,either

the

from

valence

are
called
the approxifrom the conduction band.Theseassumptions
all impurities when ionized are either
approximation of
posiimpurities:
fully ionized
A\".
donors
D+ or negatively charged acceptors
positively
charged
electrical
The
condition
D) told us that
neutrality

band or

An

nt

\342\200\224~
nfc

nj+

\342\200\224

na~.

B5)

J3; Semiconductor

Chapter

Becausenh

Statistics
aciioti law,

mass

the

m,V\302\273*from

equation for

we secthat

B5)

to a

leads

quadratic

nc\\

B6)

V-\".^!-^1.

root is

The positive

i{[{A'O2

\302\273*

because

and

nh

\302\253
\302\273* l([(AnJ

Most

the

often

+ V]1''2

- An],

nr or

either

is much

ft*

[(AnJ +

an n-type

An*]\"*

=x

A/i

+ nffAn

p-typc semicondiiclor

Ji. ^
The

majority

n?/\\An\\

proportionalto
Level

Fcrmf

By use

An

the

B9)

ln*l\\bt\\.

B7) becomes

nh

An;

** n^/An

and B7)

is negative

\302\253
n,;

while

extrinsic

the

carrier

mmoriiy

C0)

becomes

{A/i| +

nk ^

\302\253
n,.

h;V1A*i1

limit

B8)

C1)

jAffj.

is nearly

concentration

equal to

is inversely

jAnj.

in Extrinsic

of the massaction

having to calculate

the

solving

m +

carrier concent ration in

the magnitude of An,

/ij,by

B7)

+ (hj&nJ]1'2

|^[i

&n is positive and

semiconductor
nt

In a

B8)

nt.

In

than n,:

larger

be expanded:

then

can

B7b)

extrinsic semiconductor.
The squarerootsin

defines an

Condition

B7a)

\302\273

\\An\\

This

An}

compared to the intrinsic con-

is Urge

concentration

doping
that

so

concentration,

have

we

An

+ V]1/J

A7) or

Semiconductor
law
Fermi

concentrations without
Tlic Fermi level is obtained from
n, or

we calculated
level

B1) for/c

first.

the carrier

Scum

Degenerate

Figure
various

the

13.3

The Fermi icvet in

doping

band edges.

sniaii

silicon

as a function

The Fernifleveis

concentrations.
decrease

of liic energy

of lempcraturc,

are expressed
relative

gap

wiih

icmperaiure

for

Ic

has

been negieaed.

now use B7)

We may

to

find

ft as

a function of

temperature and doping level

13,3 gives numerical results for Si. With decreasing

Figure
eiiher
Fermi level in an extrinsic semiconductorapproaches
She valence band edge.

ths

temperature

An.

the

cr

conduction

DegenerateSemiconductors
one

When
quantum

of

concentration,

carrier.

the carrier
we

The calculation

is increasedand approachesthe
use
the classicaldistribution
no longer
A0)

concentrations
may

of the carriorconcenir.iiion
now

Fermi gas in Chapter 7. The sum

is written
equal to [he number of electrons,
states times the distributionfunction:
of the

over
as

follows

all

occupied

an

iiiteura!

the

quan-

for

iliiit

treatment

orbitais, which n
over the density yf

IS:

Chapter

Statistics

Semiconductor

where for free

llie
panicles of mass \302\273j

is

of stales

densily

C4)

Thai is, \302\251(\302\243)(&

is ihe
make ihe
by

in

n,V;

Lei x

of orbitals

number

in

the

transition to conductionelectronsin
\342\200\224
oblain
by m,*; and \302\243
by e
ec. We

s (e -

and

er)/r

ij

(fi

et)/t. We

interval

energy

+
(\302\243,e

we

semiconductors

use the definition A6)

of

To

ck).

iV

replace

obtain

J(c to

C6)

The integral /(;;)in

When

ee

p.

as the

is known

C6)

\302\273
x

we

have

\302\273
1,
\342\200\224ij

Ferml-Dirac integral.
so

that

cxp(x

jj)

\302\273
1.

In

this

limit

C7)

the

result

familiar

for

the ideal

gas.

several
limes
electron concentrationrarely
exceeds
the quantum concentration nc.The deviation
between
the value
of/i from C5)
and the approximation
then can be expanded into a rapidly
C7)
converging
=
series
the
r
of
ratio
power
njn^ calledthe Joyce-Dixon
approximation:*

In semiconductors the

\342\226\240
\",/\"\342\200\236

C8)

\302\253-\342\200\224i-S-f)
t3.4

Figure

compares

the exact

relation C6) witll

the

approximations

C7)

and

C8).
\342\200\242

W.

B. Joyce

1.483S6

and B. W.

x lO\"*:^,

Dixon.

App!.

- -4A2561x

Phys. Lclt.

1Q-6.'

31,354 A977).

If the

right side

of C8) is

wrine

Slmicomlitct

Dtgcncnitt

-6

-5

-4

-3 -2

-I
i)

above

conduciion

band

edge Er. The

Joycc-Dixon approximation

C8).

(|.

- i,)h

dashed curve reprcsenisihc firsi

icrm

of ihc

When

Sta

Semiconductor

13:

Chapter

longer small comparedto n(,

neisno

law must be modified.In Problem4

ask

we

Ihe

ihe

of the

expression

io show

reader

mass action

ihat

C9)
If

the

Itself

gap

here

will

on

depend

Impurity

carrier concentrations, the value

on the

depends

localized

atom

be used

n, to

concentration.

Levels

The addition of impuritiesto a

conduction or valenceband into

as

of

Ihe

where the

gap,

energy

from

orbitals

some

moves

semiconductor

the

orbiials now appear

in a silicon crystal.If the

electron to the Si conductionband,
the
atom
as a positively charged ion. The positiveion attractsthe electrons
in
appears
the conduction
an
electron
band, and the ton can bind
just as a proton can
bind an electronin a hydrogen
atom.
the
However,
binding energy in the
phosphorous

iis extra

released

has

consider

We

states.

bound

semiconductoris severalordersof
the
energy is to be
by
square
paniy

column

V donors

donor

corresponds

in

the binding

of the static dielectric constant, and

for
13-2 gives the ionizationenergies
Si and
a
Ge. The lowest orbital of an electron bound
to
\342\200\224
=
to an energy level Asd
below
the edge of the
st
st

effects. Table

mass

of

because

because

mostly

lower,

magnitude

divided

conduction band (Figure13.5).

There

is

one

set

orbitals

of bound

for

every

donor.

argument applies to
'he valence band, as in Figure

A parallel
from

set ofbotmdorbitals
as

Aej. Ionization

ionization

an

wiih

6rrteV.

For

zinc,

T:.Mc 13.2
column

energy

Asa ~

\342\200\224

il!

the

all

for

most

acceptor,

!uiiu..iio.i encr^e*ofcuhmm
acceptors

in Si

arui

Ge,

are

listed

VI donors

column

important

\302\243,,,ofthesameorder

Ea

in Si
energies for column III acctipcors

In GaAs the ionizationenergies

closeto

holes and acceptors.Orbiialsare split off

For each acceptor atom there is one
13.5.
in Table

except oxygen are

=

&\302\243a

24meV.

V <j

in mcV

Ace

11

AI

13.2.

cp OIS

Ga

In

16

49

45

57

65

12.7

10.4

10?

iOS

11.2

Some

of

Occupation

'

\"'

!'

At,

Letch

Donor

\302\261

Donor

13.5

Figure

and acceptor

impurities generate orbitals deep inside the forbidden

ionization
multiple orbitals corresponding to different
of Donor

Occupation
A

level

donor

can

Hence there are [wo

different

occupationsof these
level is occupied one

two

by

spin.

opposite

gap,

energy

with

sometimes

states.

Levels

be occupied

As a

in Uic

levels

impurity

orbitals

electron,

result, the

by an electronwith
with

orbitals
are

not

the donor

either

spin

nt

spin down.

energy. However, the

the same

independe

up or

of

each

other;

Once

the

cannot bind a second electron with

occupation probability

for

donor

level

is not

but
function,
by a function
given by the simple Fcrmi-Diracdistribution
is vacant,
the
the
orbital
treated in Chapter 5. We write
that
donor
probability
so that the donor is ionized, in a form slightly different
from
E.73):

the origin
to
singly occupied donor orbital relative
that
of the energy. The probability
the donor
orbital is occupied by an electron,
the
is
is
so thitt
donor
neutral,
given by E.74):

Here

Ed

is

the

energy

of a

Statistics

Semiconductor

13;

Chapter

In the ionized conditionA\"

Acceptors
require extra thought.
each of the chemical bonds between

ihe

atom

acceptor

of

and the

the

acceptor,

surrounding

semiconductor atomscontainsa pair of electrons

with
There
antiparaliel
spins.
is only one such state, hencethe ionized
contributes
one
condition
term,
only
exp[(/i - cJ/t], to the Gibbs sum for the acceptor, lit the neutral condition A
the

of

one electron

acceptor,

the missing electron may

is missing

the

from

up or

haveeithcrspin

bonds.

surrounding

spin down, the

is representedtwice in the Gtbbs sum for the acceptor, by

Hence the thermalaverageoccupancy
is
'

condition

neutral

The

exp[{^ ~

2 +

A,

the

with

\"\021+2

Efl)/i]

exp[(Efl

orbityl

acceptor

Because

neutral condition
term
2 x J ~ 2.

\"}

{~

$x]\"

unoccupied,

occurs

with

probability

______

The

of

value

From

An

\342\200\224

== nd+

or D2)

D0)

_ __________

is the

na~

difference

D3)

of concentrations of D*

arid

A\342\204\242.

we have

D4)

D5)
The

condition

neutrality

This expressionmay
of

functions

the

position

represent the
positive

four

visualized

be

in

and all negative

posicivechargesequal

by a

Fermi

of the
terms

be rewritten

may

D)

D6);

logarithmic

level

(Figure

the two

charges.The actual
total

the

negative

as

plot of n\" and n*

13.6}.

The

solid lines representthe

Fermi

level

as

four dashed

occurs

sum

func-

lines
of

aii

where the total

charges.

holes can be neglected;for

electrons
can be neglected. If one of the two impurity
nu~
\024*
\"i 'he
be
the
can
neglected,
species
majority carrier concentrationcan be calculated
in
The
closed
formConsider
an it-type semiconductor with
no
acceptors.
For

nd+

-^

jio~

\302\273

nh

as

in

Figure

13.6, the

Occupation of

Figure

13.6

intersection
approximation

with

will
A7)

the

be

13.6 is now given by the intersection point of the n*

the
interdonor concentration is not too high,
the
the straight portion of the incurve, alongwhich
approxiWe rewrite this as

in Figure

point

neutrality

curve

of Fermi teve!and eteciroi

coniaining both donors and acceptors.

determinaiion

Graphical

sciniconducior

an n-1ypc

DonorLetch

?!e curve,

on

holds.

U ihe

cxp(/</T)exp[(^

\302\243i)/t]

\302\2537>

(\302\273A)\302\253PfcA);

(\302\273>Jexp[(\302\243,

tj/t]

= njn*

D8)

nc*

Is

electron

the

neexp[~(et

the

with

be present

would

that

concentration

the Fermi level coincided

Eli)/i] = ;i,exp(-A^/t)

donor

level.

nd* to

the

in

Here

if

conduction

band

the donor

ec

Aed

. {49}
Ej is

iontzacton energy.
insert

We

set

D4) and

into

D8)

nt

obtain

E0)

nf3

is a

llus

shallow

weak that

donor

8\302\273j\302\253
\302\273/, the

for

-v

\302\253
i.

x ~

With

large and

=? 1 +

xI1*

we

8\302\273d/He*

ionization.For
Table 13.2, so

the

for

that il.4 pet of the donorsremain

the subjectof

Problem

-ix2

;tj(l

gives
P

=s 0M5nc

ne*

expanded by use of

\302\253

2it//ne*

parentheses

example,

that

\\x

is sufficiently

doping

\342\226\240\342\226\240\342\226\240

E3)

obtain

^ \302\253\342\200\236
\302\273\342\200\236

The secondtermin

E2)

I}-

close to nc.ffthe

may be

root

square

is

solution

+ (S\",,//)/)]1'3-

V([l

nt* is

levels,

E1)

i\302\273rfn,*.

quadratic equation in n,; ihe positive

\302\273\342\200\236

For

\\n,nt*

in

the first

order departure from complete

300 K, we
=
from D9). If \302\253j
Si at

un-ionized.

E4)

2<td/ite*).

The

have

Ae,j

0.0!nf,

limic

Eq.

of weak

t.74r
E4)

from

predicts

ionization is

6.

gallium anaiM*.: Could pure GaAs be prepared, it would have

catikt concciUfdtioita! room temperature
10'cm\023.
Wjih such a tow
of\302\273,<
!O art
conceuiraiion
of carriers,
bs; closer
@~\" less than a nicial, the conductivity would
an
as
would
be
useful
than
to
a
sciniconductor.
G;iAs
insulator
conveniiona!
[<itn'iisk
devices.
substiatc
lEiin
of
GaAs
as
nee
Jed
for
on whidi
to prepare
\302\273isulat:n\302\243
layers
doped
em1.
There
Joes no! exist a technology
to purify
per
any substance to 101 wnpuriircs
Example:

an intrinsic

StuM-itiiHtuting

p-n

However, ic
with

is possible

concentra

high

near tnerinste
carrier
Cm-3) of oxygen
impuriiy levels near the middle
to achieve

lions (tOi5-IO17

in GaAs by

concentrations
and

Junctions

chromium

doping

two impu-

together,

have iticir
of ihe energy gap. Oxygen enters
an
and is a donor in GaAs,
as expecicd
from the posiiion of O in the periodic
Cable
relative to As; the energy
is an acceptor
v> i'h an
level* is about 0.7 eV belowts. Chromium
level
about
Q.S4eV
below
energy
et.
a GaAs
Consider
boih
and chromium. The ratio of liiS two
crysiai doped with
oxygen
conceniraiions
is not critical; anything
with
an O:Cr raiio between abouc 1:10and
10:1
will do. If the conccitiraiions of all olher
are small compared with those of O and
impurities
Cr, (he position of ihc Fermi level will be governed
by ihe equilibrium betweenelm -ons
on O and holes on Cr. The
of Figure
construction
t3.6 applied io tliis system
shows
that
over the indicated concentration raiio rangedie Fermi
is pinned io a range between
level
t.5i
above
the O fevel and l.5r below (he Cr level.
With
ihe Fermi level pinned near the
imrinsic
middle of the energy gap, the crysiai must act as nearly
Gallium
arsenide doped in this way is called semi-insulating GaAs and is used extensively
to to10 il cm\\ substrate
as a tiijjh-resisiivity
for GuAs devices. A similar
[!0a
prodoping
procedure
is possible
in inP, with
iron
ihe
taking
place of chromium.
impurities

ttiat

As site

p-n JUNCTIONS

Semiconductors

are almost
never uniformly doped. An underan
semidoped
requires
understanding of nonuniformiy
of structures called p-n junctionsin which
the doping
semiconductors, particularly
to n-type within 'he samecrystal.We consider
ton from /vtype
changes with
posi!
a semiconductor
at
.v = 0
which
the doping changesabruptly
crystal inside
from a uniform
donor
concentration
nd to a uniform acceptor concentration
as in Figure
i3.7a. This is an exampleof a p~i\\ junction.
More complicated
na,
a
device structures are made up from
simple
bipolar transistor h.-is
junctions:
used

devices

understanding of devices

iwo closely spacedp-n junctions,

ofthe sequence
or n~p-n.
p-i\\~p
in the
built-in
electrostaticpotential
Vbi, even
step
p~n junctions contain a
With
no externally
absence of an externally applied voltage
13.7b).
(Figure
the
are
in
of
diffusive
junction
applied voltage, the electrons on the two sides
of tlic two
which means that the chemical potentials(Fermilevels)
equilibrium,
within
Fenni
level
ihe band
sides are the same. Because ihe posiiionof the
level forces :i
of
the
Fermi
siructurc depends on the localdoping,constancy
shift

in

the

shift

is

eVN.

electron
The

energy

potential

bands
stop of

in

ihe

crossing

height eVbii%

required to equalize the total chemical

intrinsic chemicalpotentialsare unequal,

an

junction
example

potential

as

discussed

of

two

(Figure 13.7c).
of the potential
systems

in Chapter

5.

The
step

when ihc

A p-n junclion. (a) Dopingdislribulion.!l is assumed

13.7
the
that
from
doping changes abruptly
n-type to p-type. The two
levels arc usually different,
doping
(b) Electrosiaiic
poteniiat. The
Figure

buitl-in
two

voltage
sides

wilh

concentrations,
shifted

relaiivc

generate the

diffusive
between ihe
equilibrium
electron concenlralions as wet! as hole
level must be
(c) Energy bands. Becauseihe Fermi
Vbl

ealabtishes

differenl

to each
buitl-in

other, (d) Spacecharge

voltage

and

to

shift

the

dipolc

energy

required

bands.

to

We assume that

the two doping concentrationsnd,

nondegenerate range, as

defined

Hf

are

If the

donors

the p

side, then the

\302\253
nd

\302\253
\302\273c;

\302\253
\302\273(
na

the n

side and

on

the

from
\302\261

side

Jij,

\302\253
\302\273t.

E5}

the acceptorsfully

on

ionized

electron and ho!econcentrations

satisfy
=z vd\\

ne

one on

extrinsic but

by

ionized

fully

in the

lie

tta

and

the other

on thep
band

The
conduction
\302\273\342\200\236.)

s:

nh

E6)

na,

side. (We have droppedthe

on the

energies

i\\

p sides

and

superscripts

follow

from

A7):
E7)

\302\253\302\253-/*-xlbgl^/nj;

H~ xlo&{nJnc) =

ccp =
by

eVtf

For doping concentrationsnd

A

is 0.91

eV in silicon

in electrostatic

step

E8)

must

satisfy

the

at room

temperature.
to shift

is required

potential
Poisson

to

other.

each

find eHi
band

the

The

= es -~9.2t,

edge

electrostatic

energies

on

potential

equation

(SI)

Hfl=s0.0inL.,we

0.0inrand

E9)

Tlog(W>,2)

\302\243CJ. e\302\253

the two sides of the junction relative

<p{x)

tlogK1/\"^).

Hence

B2c).

which

;1-

= ~~ ,

F1)

of the semiconductor.
space charge density and e the permittivity
varies.
must
be
whenever
In
the
vicinity of the junction
<p
Space charge
present
material.
the
carriers
no Songer neutralize the impurities as in the bulk
charge
the
h side and negative on the p side
on
The space charge must be positive

where

is the

(Figure 13.7d}.
concentration is less
Positive

space
than

the

charge
donor

on

the

concentration,

side

means

indeed,

that

as the

the electron

conduction

Statistics

Semiconductor

13:

Chapter

raised relative to the fixed Fermi

decreaseof the electronconcentration
ie.
band edge ts
the

Take
Then

ofthe

origin
=

ec(x)

electrostatic
\342\200\224

and

e<p{x),

\302\243c(~-a))

ne{x) =

ThePoisson

potential at

x = -co.soihai

</

d.x i/x^

(/.x \\il\\-J

dx
=

x =

i6d\\

, ,1

0:

F5)

\\dxj
interface

F3)

AM2

oc)
Integrate uiih the initial condition<p{\342\200\224

the

F2)

to obtain

_</WV

At

<p(-00}= 0.

ntcxp[e<p[x)/T].

]
Jdtpfdx

by

an exponential

becomes

A7)

^
Multiply

predicts

A7)

is

F1)

equation

level,

0 we assume that'

F6)
Vn is

where

the n side.

part of

that

the built-in electrostaticpotentialdropthat

The exponential

on the right-handsideofF5)can

be

on

occurs

and

neglected,

we obtain

E for the

-v

ofthe

component

[peii,/c)(K,-

electric

field E

F7)

*/e)Vn

= -dipjdx. at the interface.Similarly,

FS)

\302\243=[{2eMB/\342\202\254)(^-t/e)]\022,

where

ihepstdcTlie
we

potential
drop
part of ilie built-inelectrostatic
be the same; from this and from
two \302\243
fields
must

I-; is that

that
Vn

on

occurs
-V

Vp

Vbi

find

(\302\243^')\022

F9)

rse-BiasedAbrupt
is the Sameas if On

field E

The

lite

from

to a

junction

the

Junction

been depleted

electrons had

side all

ii-type

p~n

distance

, G0)

-(Vw-2r/f)

no

with

at

depletion

>

\\x\\

theory as a measureofthe

layer into

on the

p side,

The totaldepletion

width

1f

we assume

- 4.25
\302\243

\302\273o

wK

nd =

i0licm\023;e

and w

x 104VcmwI

Reverse-Biased
Let

of penetration

depth

a voltage

be

4.70

the

to a

applied

p side
n

to the

p side

in bulk
contains

side

law. As

action

holes,

and

increased

\302\273
side,

contains a very
a very

by the

are

2z/e

== 1 volt,

we lind

iO^5cm.

p-n junction,

holes

and
low

which

of such sign that

that

means

voltage

raises

p side
the

cond uction

drive

will

the

of

concentration

little

current

approximately

applied voltage,Figure

ihe same
13.S.

The

as

if

built-in

the

field

at

electrons

side to the p side.But

conduction
electrons, and

The distributions

flows.

is at

potential

from the ;i

low concentration of holes,consistentwith

a result, very

potential

Vbi

Junction

p-n

Abrupt

~ l(ko;aiid

negative vohagerelativeto the n side,

energy of the electronson the p side.This
from

used in semiconductor device

of the space charge transition

n side.

the

Similarly,

wa is

distance

The

\\vK.

the

the
ifie

mass

of electrons,
voltage

were

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.

mi .->
13.8

Figure

Reverse-biased

p-?i

tfic cjuast-Fcrmi

showing

junaion,

levels fi, and//P.

and the junction thicknessis given

by

G4)

In the

semiconductor

device liierature we

term 2t/e, becausecertain

charge and
correct

field

electron

distribution;

distribution

approximations

we

F2).

have

often

have

solved

find

beea

and G4) without the

made about the space

G3)

the Poisson

equation

with

the

Currtrni

Flow:

Drift

and Diffus

SEMICONDUCTORS

NONEQUILIBRIUM

Quasl-Fcrmi Levels
When

is illuminated

semiconductor

than !he energy gap, electronsarc

with

light

from

raised

of

energy greater
txind to the conduc-

quantum

the valence

concentrations created by iliumination

arc larger
than their equilibrium concentrations. Similarnonequiiibrium
conconcentrations
arise when a forward-biased p-n junction injectselectrons
a
inio
semiconductor.
The
semiconductor
or
holes
into
an
eiectric
ii-type
ptype
allracis
oppositely
charged
charge associated with the injected carrier lype
carriers from the external electrodesof the semiconductor
so thai
bolh carrier
concentrations increase.
recombine
with each otlier. The recombination
The excesscarriers
eventually
with
the
timesvary greatly
from less than lo~9s to longerthmi
semiconductor,
10\" 3s. Recombination
Even
the
shortest
tiniesin high purity Si are near 10~35.
recombination
times are much longer than the times (-^ lG~l2s)
at
required
room temperature
for the conduction electronsto reachthermal
equilibrium
with
each
other tn the conduction
and for the holes to reach thermal
band,
with
each
other
in
the
valence
band. Thus the orbital occupancy
equilibrium
distributionsofelectrons
and
of holes are very close to equilibrium Fermi-Dirac
in
distributions each band separately,
but the tola! number of holesis not in
with
the
total
of
nuniber
electrons.
equilibrium
We
can
this steady state or quasi-equilibrium condition by saying
express
that at tthere
are di fierent Fermi levels;<c and ;iv for the two bands, called quasiconduction band.

and

electron

The

the hole

ii levels:
levels:
emii

7\021\"

levels

Quasi-Fermi

Current Flow: Drift

are used

and

+exp[(t-\342\200\236\342\200\236)/,]\342\200\242

extensively

in

the

analysis

of semiconductor

devices.

Diffusion

band quasi-Fermi level is at a constant energy

a
throughout
semiconductor
crystal, the conduction electrons throughout the crysta!are in
and
and no electron current wjl! flow. Any
thermal
diffusive equilibrium,
conduction
must
be
electron flow in a semiconductor at a uniform
temperature
If the

caused

conduction

by a

position-dependence

of. the conductionband

quasi-Fermi

level.

15; Semiconductor

Chapter

Statistics

If the gradient of this level is sufficiently

of

contribution

conduction

to this

proportional

we

weak,

that the

total electrical current

to ihe

electrons

assume

may

gradient:

current

electrical

an

carries Ihe

electron

we
\342\200\224e,

x
(\342\204\242e)

where the electronilux density

potential,
electrons

the

density.

Because

each

have

flux density),

{electron

as the

defined

G7)

number of conduction

electrons

Fora

given

driving

conduction

is
charge, the associated electricalcurrent density
force for this current.
of grad fic. We view grad jj\302\243
as the driving
the
current
is
force,
density
proportional to the concentration
electrons.
Thus we write

a negative

carry

the direction

constant

the proportionality

where

should
If

not

the

be

confused

with

fi't

in lerms

is

\302\253
nf

band quasi-Fermi level

of the eleclronconcentration
ut

G8)

the

electron

mobility.

The symbol

pt

band quasi-Fermi level,/jc.

in the extrinsic but nondegenerate range,

n,
cottduclion

is

the conduction

concentration

electron

G8)

~.

Jt_

Thus

flux

in

area

unit

the

particle

in Chapter

treated

of

is

G6)

is
unit time. The ciose connection of G6) to Ohm'sSaw
14. Because the flow of particies
from
to
low
chemical
is
high
to grad nc, but because
flux is opposite
conduction
electron

crossing

nt

not a

density,

charge
5

in

is

density

J, cc grad/*(.

HereJe is

con-

\302\253
nc

G9)

is given by

A5),

which

can

be written

as

+ Tlog(it7\302\253A
\302\243c

(80)

become:

(81)
A

gradient

in the

conduction

band edge arises from

potential and thus from an electricfield:

a gradient

in the

electrostatic

Flaw:

Current

electron

We introduce an

diffusion

coefficient

Dt -

- eptntE 4-

J,
There arc two different
field and one caused by
Analogous

a concentration

in the

electrous

the

io the right

valence b;ind.

is really an

grad

eDe

form

final

the

(84)

by

an

electric

gradient.

to holes,with

Fermi levelis not ihc chemicalpotential

for

(83)

contributions to the current:one caused

results apply

relation

Einstein

the

pex/e

now write (?S) or (8i) in

14. We

in Chapter

discussed

by

Dc

and Diffusion

Drift

one
for

The

difference.
holes,

but

valence

is the

chemical potential

Holes arc missingelectrons;a

electron current to the left. But

band quasi-

carry

holes

hole

current

a positive

and we may view

negative charge.Thetwo sign reversals
cancel,
for
of
the
total
electrical
force
the
contribution
holesto
driving
Jh
density. We write, analogously to G8),

rattier than a
j.iv as the

grad

current

Jh

as

the rest

through

Carrying

the

of

analog

sign in

diffusion

the

but

concentrations,

hole
holes

because

current,

(84),

Example:Injection

laser.

\302\273

(85)

jvifcgradjv

of the argument leadsto

Einstein relation Df, = ji^fe- Note the different

term:
Holes, like electrons, diffuse from high to low condiffusion
makes the opposite contribution to the electric
carry lhe opposite charge.
with the

The

highest

nonequilibrium

carrier concenlrations

in

semi-

ifie occiipaiion f&c) of

in injection lasers. When
injection
by efectron
Ihc towesi conduciion
band orbital becomes higher than
lhe occupalioii/XeJofthe
highesl
iclls
us ihai lighi
valence band orbiial, the population
is said lo be invened. Laserilieory
emission.
The
=
ihtn be amplified by siimulylcd
Vvilh
a quantum
energy ec \342\200\224
\302\243\342\200\236
&f can

semiconductors occur

condiiion

for

populaiion

inversion

is ihat

/Me) >
Wiih

ilie

quasi-Fernii

distributions

G5)

this

(S?)

fM

condition

is expressed

us

(88)

13.9

Figure

laser. Electrons Row from the

eieciron gas. The
layer,
they
on
the
the
t!ic
wide
p side prevents
by
energy gap
provided
ihc
flow
from
Icfi
iiiio
ihe
aciive
to
the
left.
Holes
escaping
to the right.
When
(83) is attained, laser aciion
escape

Double-heterostructtirc

right into the active

barrier

potential

electrons

layer,

but

from

cannot

injection
form

where

a degenerate

becomespossible.

For laser
to
An

which

levels must be separated by more ihan ihe energy gap.

quasi-Fermi
levels lie inside ihe band
at
least one of the quasi-Fermi
that
(88) requires
it refers. This is a necessary,bui not a sufficient condiiion for laser operation.
action

The condition

important

the

additional

condition

is

that

the

energy

a direct gap rather

physics texts. The most
gap is

than

an

state
distinction is treated
in solid
important
direct gap are GaAs and inP.
The population
in the double hcterostructtire
of Figinversion is most easily achieved
Figure 13.9;
two wider-gap
semiconductor
here ihe lasing semiconductor is embeddedbetween
In such a structure
is GaAs embedded in A!As.
regions of opposite doping.An example
there is a potential
to the p-type region,and
barrier
of electrons
that prevents the outflow
an opposiic
barrier ihat prevents
ihe outflow of hoies to then-type region.
poieniial

indirect

gap. The

semiconductors

with a

itself, the electrons in the waive liiy\302\253r

caused by tlic recombination
arc
in diffusive equilibrium
wilh
ana\" the electron quasitlic electrons
in the n contact,
level in then contact. Similarly,
the
level
Fermi
in the active layer lines up with
the Fermi
valence
band quasi-Fermi level lines up with
level in the p coniact. inversion
the Fermi
can be achieved
than
ihe votlage equivalent of the active
if we apply
a bias voltagelarger
double
this
layer
energy
heierostf uciure principle.
gap. Most injection lasers utilize
Except

for

the current

rent

Example; Canter
eiiher

combine

recombination

an iaipsiriiy

throush

by an electron

falling

inio

dircciiy

Flow:

Drift

and Diffusion

Electrons and holes can reemission of a photon,

ihe energy gap. The impuciiy
process
level,

a hole

with itic

can recombine ihrough

an impurity
level in
is dominant in silicon.
We discuss ihe process as an insiruciivc
ium
example
ofquasi-equilibf
semiconducior
statistics. Consider an impurity
ut energy t, in
recombination
orbiiai
13.10. Four transition processes are indicated
in the figure. We assume that
Figure
ihe
rate Rc, at which
electrons
conduction
fail into the recombination orbiiais is described
by
a law of the form

or ihey

*\342\200\236-(!

w here

fr is the fraction of

Itcnce not

and

available),

(89)

recombinationorbitais already
occupied
characteristic time constant for the
ai

by an
capture

electron (and
process. We

tiie rate

Kc =
\302\253hcrcit'

\342\200\242

t. is a

iissume the reverse processproceeds

concentration

~/>A

/,'lj'e'

(90)

time constant forttie reverse process. We tnke R,, independent

of conduUion ekurons, becausewe assume
that i\\e < nt 1 he time

is the

Figure 13.10
impurity

Electron-hole

recombination

recombination

ihrough

orbitais at t, inside ihe energy

\342\226\240

gap-

of

the

con-

consiaitts

r.

Statistics

Semiconductor

13;

Chapter

and r,' arc related, becausein

wiihf,
ihc

and

in thermal

evaluated

n,

distribution

we use
ihe

Wiih

cancel Thus

A7) for h,. We

ignore

Fcnni-Dirac

equilibrium

we have

for/,

(91)

Rcr musi

and

Rrt

means

which

equilibrium,

= exp[~{^~e,)/r].

A -/,)//,
Thus

raies

of the rccombinaiion levels,

muitipiiciiy

spin

ilie two

equilibrium

(92)

becomes

=
^
ne' is

where

defined as ihe conduction

level

Fermi

equilibrium

arc insenedinto

and

(89)

in

ft

coincided

A7)

Rcr

Re,

Tor

%,\302\273/,

te

f,)nt

-* Rh,

flh,

(94)

/,\302\273/].

by ihe subsiituiions

is obtained

holes

ihc

(93)

rale becomes

recombinalion

- ~ [A'-

be present if

level, if (92) and

recombination

the

wjlh

electron

R,c

rate

recombinaiion

analogous

net

lhal would

conceniralion

electron

(90), ihe

Re =

The

(93)
^exp[~fc-\342\200\236)/!]\302\273\"\302\243.

!h;

nh*,

and

Here

fk

is the

lifetime

and

n,,* is,

eiecirons,

of holes
by

these substiiutioiis

Iiisteady

in

ihe

limit

thai ail

(95)

recombination ceniersare occupiedby

definiiion,

ah*
With

1 -/,-/,.

~Jr\\

/-I

nBexp[-(\302\243,

the net hole

ej/i]

rccombiiiationrale

is

staieUicuvorecombinaUonfaiesmusibcequaS:R,
ions for ihe two
unknowns
equal
f, and /?.

and (97) arc iwo

C96>

;i,V\302\273.*-

=
W'i.

Hft

eiiminalc

R.Equations
/, to

194)

find

(9S)

basic rcsuli of ihe

is the

This

are developed

recombination
Hail-Siiockley-Read

10 and

Problems

In

Applications

iheory.'

I).

SUMMARY

!. In semiconductors
(completelyoccupied
band (complelely
empty

Electrons

gap.

energy

electrons;

orbitals

empty

2. The
by

of

probability

Here
3. The

\\i

is

Here

ne

An

is

negatively

4.

\302\253
nv.

efTecItve
and

valence

R. N.

energy e is governed

electrons, called the

level

in

an

ievei.

Fermi

neutral

eleclrically

semi-

condition

eiecirons and holes,

of positively charged impuritiesover
of condiiction

concentrations
Concentration

impuriiies.

is said to be

in

the

classical

regime

when

ne

\302\253
nt

and

Here

and
concentratioi)s for electrons
holes;
hi/ and \302\253?/arc
for eiecjrons and Ijoles. In the semiconductorHteralure,
masses
the effective densities
of states for the conduction;:nd
are
called
\302\273\342\200\236

the quantum

are

nc

the

excess

A semiconductor
nh

the

Fermi

by the neutrality

i\\h are

charged

of ihe

potential

governed

and

band orbital with

function

location of the

energetic

semiconductor

and

distribution

chemical

the

is

of a

occupancy

Fermi-Dirac

ihe

grouped

\342\200\224

at

an

into a

valence band
and a conduction
0 in a pure semiconductor)
r
al
x = 0 in a pure semiconductor), separated by
in the conduction band are calledconduct:-:1'
in the valence
band are called holes.
are

orbilals

electron

the

Hall,

bands.

Phys.

Rev.

87, 387{i952);

\\V.

Shockley

and W.

T. Read. Jr.. Phys.

Rev.S7.

S35{!952).

ihe classical

. In

regime

where \302\243\302\243
and
eu

are the

energies of

ihe edgesof the

valence

and

conduction

bands.

mass action law

6. The

in the

that

stales

\"\302\273\302\273*
'I.-1

is

The

The intrinsicconcentration

intrinsic

( \342\200\224
pure)

dominate;

electrons)

the

sign

carriers {- conpositive charge

the dominant charge carriersis

sign of
dominant
ionized
The

dominate.

(wholes)

oppositeto

of the

impurities.

structure

is a rectifying semiconductor
from p-typc to n-typi. A p-n junction

junction

p-n

transition

Here

is

the

concentrations,

9. The

electric

permittivity,
and

current

| V\\

and

nu
Vbi

are

densities

JB =

Jp ~
Here

% and

ihe
are
\302\243\342\200\236

electron

Mj are

and

the

due

ionized

applied

to electron

and donor

and hole

the

con-

built-in reverse bias.

and hole flow

ePsgrad

electric

junction

abrupt

are

e/yi,E + eDegmdne,
ephnkE

internal

internal

acceptor

and the

nn

with

contains

fields even in the absence of an appliedvoltage.Foran

field at the p-n interfaceis

semiconductor.

Ji-type when negative charge

it is called p-type when

called

is

semiconductor

carriers

an

energy gap.

conduction

S,

in

quantity

is the
A

nh

product

'M'uexp(-\302\243a/i)

impurity concentration.

value of n{ and

common

the

is

n,

7.

of the

independent

classical regime the

nh,

mobilities, and

\342\226\240

given

by

diffusion coefficients.

and hole

electron

ihe

are

PROBLEMS

1.

concentration,

\302\253
nt.

jAnj

Intrinsic

2,

the electron and hole concenlrais small coinpared to the intrinsic

concentration

donor

net

the

when

Caiculale

semiconductor.

doped

Weakly

tjons

and

conductivity

ininimuni

conduc-

electrical

The

conductivity.
\342\226\240
-.

conductivity is

+ njh)

e{ntpe

(99)

and hole mobilities.For most semiconductors

net ionized impurity
for
conccntral/on
An ~ na* \342\200\224
/ia~
for
this
is a minimum.Give a mathematics!expression
is
minimum
what
factor
lower
lhan
the
of
an
it
(b) By
conductivity,
conductivity
which
the
intrinsic semiconductor?(c) Give numerical
K
for
Si
for
values at 300
are jie = 1350 and pk = 4S0cm3
mobilities
and for InSb, for which
V~*s~l,
the
mobilities
are p# = 77000 and jih = 750cm2V\"Is\021.
Calculate
missing
from
Table
d;itu
13.1.

where Jit

ph are

and

the electron

fl( > Jfj,. (a) Find the

which the conductivity

3.

concentration.
A manufacturer
impurity
specifies the
=
Ge
of
a
as
20
ohm
cm.
Take
3900 cm2 V\021
resistivity
I/a
p
crystal
pc
and
V\021
s~l.
What
is the net impurity concentration a) if
/Zk=s 1900cm1
is n-type; b) if the crystal is p-type?
crystal
and

Resistivity

5.

of Ihe

is the
law for high electron concentrations. DeriveC9),which
no
is
small
law of mass aclionwhen
longer
ne
compared to ne.

InSb at

concentrations

hole

and

Electron

n-type

300K, assuming nd+

high ratio njn,. and the

narrow

\342\200\224

4.6

nc

Use

applicable.

transcendental

for

equation

the generalized
nc by

6. incomplete

iont'zation

donor impurities
doi

if the

than

t }og(nJ8nd) by

large

impurity

tonization

o/

donor

iteration or

gap,

energy
nor

\302\253

Calculate

in InSb.

negligible under theseconditions,

ne

the

action

Mass

4.

form

res\021

is

the

Saw

\342\200\224
for

Et

C9).

approximation
Ihe tran-

Solve

graphically.

Find
imparities.
tontzalton energy fs large

several times t. The result

remain

/i

= ne.

nondegsnerate

mass action

deep

energies

and

Because of the
is not
hole concentration

1016cm\"\"J
the

nc, nh,

explains

insulators,

the fraction of ionized

enough lhat Aed

why

substances

even if impure.

is larger

with

Statistics

13 s Semiconductor

Chapter

7. Built-in

field for exponentialdoping

semiconductor the ionizedacceptorConcentration

and

eiecuic

= I0~
103 and Xj \342\200\224
X[
as this occur in the base

aids

8.

in

driving

Einstein

that

in

the
relation

electrons

injected
for

C8)to
approximation
concentrations

region of

approaching

series

a
or

n-p-n

across the

transistors.

The

the

/!s//ii

built-in

such

field

base.
Use the Joyce-Dixon
of the ratio DJfic for electron

concentrations.

electron

high
give

many

a .P-type

<- \302\273%
\302\253
at x = xt is \302\273\342\200\236\"
\302\273\342\200
=
=
n2 \302\273
ns at X
x2. What is
~
Give
values
for

to a value na~
interval (xtlJCj)?
nurnerica!
5 cm. Assume T = 300K.
distributions
Impurity

off exponentially
field in the

falls

built-in

Suppose

profile.

expansion

exceeding

itc,

9. Injection laser. Use the Joyce-Dixonapproximation

at
T =
to calculate
300 K the electron-hole pair concentration
in
GaAs
the inversion
that
satisfies

condition (88).assumingno ionizedimpurities.

Assume both electron and hole concentrations

in a semiconductor
by 6n above their equilibriumvalues.Definea net
R =* Sn/i. Give expressions
carrier
f
for i in terms of the
lifetime
by
minority
the
I
lie
recombination
as
carriereonccniraiions
and
level,
i\\h;
ne
energy of
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-

10.

Minority

independentof

carrier

lifetime.
are raised

ditt

pair generation. Inside a reversebiasedp-n junctionboth

electrons
and
lides
have been swept.out.
(a) Calculate the elcciron-holepair
rate
under
these
generation
conditions,
assuming ne* = nfc* and te ~ th = t.
tin's generation
rate is higher than the generation
(b) Find ihe factor by which
rate in an \302\253-type semiconductor
from
which
the holes have been swept out,
but
in which
concentration
remains equal to itd+ \302\273'i,-. (c) Give a
the electron
= 10Ificm~3.
numerical value for this ratio for Si with
ji/
11.

Electron-hole

14

Chapter

Kinetic

Theory

GAS LAW

IDEAL

THE

OF

THEORY

KINETIC

392

MaxwellDistribution of Velocities

394

Verification

Experimental

Collision

Cross Sections

TRANSPORT

PROCESSES

Particle

391

and Mean FreePaths

395
397

399

Diffusion

Thermal Conductivity

40!

Viscosity

402

404

Forces

Generalized

406

Einstein Relation

KINETICSOF

407

BALANCE

DETAILED

TREATMENT;

ADVANCED

TRANSPORT EQUATION

BOLTZMANN

Particle

409

Diffusion

4!0

Distribution

Classical

4!

Fermi-Dirac Distribution

LAWS

OF RARF.FIED

Flowof

Molecules

of

Speed

413

GASES

414

a Hole

Through

Example: Flow

413

Conductivity

Electrical

408

Through a LongTube

4!6
417

a Pump

SUMMARY

419

I'KOIiUCMS

1.

Mean

Speeds

in a

Maxwcllian

Distribution

in a Beam
2. Mean KineticEnergy
to
ElectricalConductivity
3. Ratio of Thermal

4.

Thermal

5.

Boitzmann

Conductivity
Equation

Thermal

420
420

420

of Metals
and

419

Conductivity

421

Chapter14: Kinetic
6.

Flow

Theory

421

a Tube

Through

421

7. Speedof a Tube

ant

conscious

of time.

of being

But if still

the theory

only an individual

remains

in

my

power

of gases is againreviled,not

struggling weaklyagainstthe

to contribute
too

much

in

such

a way

will have to be

L, Betiynann

stream

thai, when

rediscovered.

Kinetic

Ideal

of the

Theory

Ga>

we give a kinetic derivationof dieideal

law, the distribution
gas
of gas molecules,and transport
in gases:
diffusion,
processes
thermal conductivity, and viscosity.
The
Bohzmaim
is
transport
equation
discussed. We also treat gases at very low pressures, with referenceto vacuum
The
is essentially classical physicsbecauseIhequantum
pumps.
chapter
theory

!n

this

chapter

of velocities

of transport

is difficult.

KINETIC

THEORY OF THE
the kinetic

We apply
~

law, pV
container. Let v,

as

in

Nx.

14.1.

Figure

from the

GAS

IDEAL

method to obtain an
molecules

Consider
the

denote

If a

velocity

molecule of

LAW

of the

derivation

elementary

that strike a
area
normal
to
the
component
unit

mass M

is

of
wall, the changeof momciitum

the

reflected

the

of

ideal gas
wall of a

plane of the wall.

(mirror-likcj

specularly
is

molecule

\342\200\224

A)

2A/|i-x|.

This

gives an

pressureon

impulse 2M|i>.|to the wall,

_ /momentum
\\

second

law of

motion. The

is

wall

the

Newton's

by

per

cliangc\\/number

molecule

)\\

unit

of molecules strikmgN
area

per

unit

lime

pj

of molecules per unit volume with

the 2 component
be the number
\342\200\224
= n. The
+
Here
the velocity between i>, and
v2
dii2.
NjV
\302\247a{v.)dvz
a unit area of the wall in unit
time
is
number in this velocity range that strike
so
is
of
molecules
these
-2Mi-.fl(i'.)iyf[i;,
a(vJ)vIdDx. The momentum change

. Let a(vI)ilv1
of

that

the

totai

pressure

is

= M f\"
p = JO
{a>2Mv1la{t\\)dv1
J-a
The integralon the right
so that p ~ Afn<yI2>,

is
The

the

thermal

average

C)

v.la{vMv..

average of v22 times

value of JjMi-e2 is |t,

the
by

concentration,
equipartition

of

change
ily

of momentum of a
is reftecied from

v which

ntaincris

~-2M\\vz\\.

3). Thus

(Chapter

energy

p=

is

the pressure

iiAf<ps2>

= (NfV)z;

'it

D)

This is the idealgas law.

The

result.

assum

ption

What

comes

We now

must go

back,

with

immaterial

it is

same

the

to the

distribution,

of Velocities

Distribution

Maxwell

reflection is convenient,but

t!:e surface

into

equilibrium is to be maintained.

if thermal

transform the energy distribution

classical velocity
say

of specular

as

\"velocity\",

In Chapter 6 we

this

is the

found

the

tradition

when we

Often

function.

distribution

in

physics

function

distribution

of

function

when

of an

an

ideal

gas

mean \"speed\"we shall

no confusion
is caused.

ideal gas to be

Ati =
is

where/(cn)

tltc

E)

of occupancy

probability

into a

of an orbital of energy

\342\200\242

ui\\l

in a
number

cube of volume
between

probability

it and

V
n

Li,
+

number of atoms with quantum

x (the
(tlie number of orbilals in this range)

The average

tin is

such an orbital is occupied).Tltenumberof orbitals

in

the

positive

octant of a sphericalshellof
product is

{{nn2dn)f{zK)=
the spin

take

We

To obtain
a

find

connection

the

consider

from

with
G)

and

the desired

G)

&/.n*exp(-\302\243jz)dn.

of

distribution

probability

the quantum

between

particle in the orbital

quantum energyF) by

atoms

whence

of the atom as zero.

of a

We

of t'ekctlies

is ^Dnn2)(Int

tin

thickness

MaxwellDistribution

classical
The
\302\243\342\200\236.

the classical

number

kineticenergy

and

velocity, we must

the

classical

\\Mvz is

velocny

related to the

be the number
of
particles in volumeV.Let NP{i)ili}
in
velocity magnitude, or speed, the range dv at v. This is evaluated
,!>: - (iln/ilijib - (\\lL/hn)il\302\273.
We
have
(8) by setting
a system

of N

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

fiidor staiidiiig to the left

of

that

}.

n/\302\273Q

(.V/L^^lnt^fMTK'2,

so that

the

v1 becomes

Thus

(ll)

\342\226\240!n(A//2j[i)lV<:.\\p(-A/rV2r).

Maxwell velocity iIis(ribulion(Figure14.2).The quantity

values
probability that a particie has its speedin i/r at i\". Numerical
and
the mean
mean square thermal velocity
speed are given in
=
andf
Problem
(Sr/irU)\022from
using the results \302\273,\342\200\236
Ci/.W)\022

Tin's

is the

P(i

Mr

of the
Table

!.

is (lie

root
!4.I,

\\

\\

Figure t-l.2
function of

Mawveil velocity distribution

the

speed

probable

speed tm(,

arc the

mean speed

velocity

of

in units

shown

mean square

loot

ttie

\\

most

the

* {2t/A/I\". Also

c and

as

\\

i-AK1.

1/

Table

4.1

Gas

ofcculat \342\226\240
*e!ocilies
31273
?

\".\342\200\236,

16.9

Oi

4.6

13.1

12.1

Ar

4.3

H,n

6.2

5.7

2.86

Ne

5.8

53

Kr
Xe

N,

4.9

4.5

in

below;

14.3

Figure

theagreement

of atoms

distribution
from

the

of an

distribution

velocity

in

those

at

\342\200\242

P. M.

low

velocity.

Marcus and

Press, 1959.

to thetr

In proportion

J. H. McFee,Recent

research

1 In such experimenls a round bole is said io be small

of an aiom in ihe oven, tf the bole ti not smalt In tbis

\342\226\240\"\342\226\240

by

lhetawsofbydrodynamic

Marcus

and

McFee.*

experimental results with the prediction

We need an expressionfor the velocity
smatf
hole1 in an oven. This distributionis
within

an extra

involves

by

of potassium

the
compares
is excehent.

factor, the
The exit beam is weighted favor of atoins
ho^e

1013.

of atoms

oven has beenstudied

that exit from

velocity

2.63
2.09

1100.

distribution

velocity

40

2.27

Free electron

The

the slit

from

The curve

the

4.2

18.4

exit

different

\342\226\240\342\226\240,.,

He

verification.

of A2)

Gas

H,

Experimental
which

10*01115\"'

iin

K,

Bow and

not

by

the oven,
component

of high

because the flux

normal

watt.

velocity at the expenseof

concentration in the oven,fast

in molecular

through

to the

fceanw,

ed.

}. Esterman,

atoms

Academic

diameicr is less than a mean free paih

flow
of gas from it will be governed
[be
sense,
gas kinetics.
if ihe

i SecUtms and Me

10
9
>?

-?*

zj

Measured

14.3

Maxwell transmission

an oven al

traiistnissio\302\273

curve for

a temperature

U 12 13

time

Tiansit

figure

10

and

points

potassium

that exit
is Ihe

axis

homontal

E?\302\260C.The

calculated

atoms

from
transit

is in arbitrary
utoms iransmiitcd. The inicnsity
units;
the curve attd fhe points are normalized to the same maximum
value.
After Marcus and McFce.

of the

lime

stitke the walis more often

slow

ihan

atoms

Ihe walls.

strike

The weightfactor

to the plane of ihe hole.The average

is
J. The
of cos 0 over ihe forward hemisphere
namely
jusl a numericalfactor,
thai an atom which leavesthe hole will have a velocity between
probability

is

the

and

wiih

dv deftnes

v +

P,,(,Iwett given

ihe quantity

by (H).

hole is calledihe Maxwell

We

can

estimate

aioms of

eachother.

From

has traversed

The distributionA2)

Figure

will

of

ihe

transmission

through

distribution

and Mean FreePaths

ihe collision

diameter d

where

PbciJ,v)iSv,

transmission

Cross Sections

Collision

normal

ucosf?

component

velocity

collide

14.4

rates of

gas atoms viewed

if their

we see

centers

thai one

as

rigid

spheres.

Two

pass wiihin ihe distance4 of

collision will

occur

when

an atom

an averagedistance

A3)

(a) Two

Figure

14.4

if their

centers pass

cacliother,
travels

(b) An

a long

K'tnaic

14:

Chapter

rigid spheres

arom of

distance L

collide

will

d of

a distance

within

Theory

each

diameter d which

will

oul

sweep

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
of ajoms
in this volume is
averagenumber
i\\r,dlL.
This
is the number of collisions.Tlie
dkwnCt
between
collisions
is
average

where

>i

the

is

freepath:it is
result
We
diameter

the

d is

at=

of the

velocity

the

estimate

2.2 A

The coiicenEration

volume.

unit

traveled

as for

Tiie

by an

/is called

length

If tlie atomic

of the mean free path.

crosssectionac
[ielium, then die collision

C.14)B.2 x KT'crnJ

of moleculesofan

idea!

gas

the mean

atom between collisions.Our

target atoms.

of magnitude

order

nit2 =

per

distance

average

the

neglects

of atoms

number

\302\253=
15.3

atO:Cand

is

lO-i6cm2.

atm

A4)
is given

by the

Losclimidt number
=

m0

defined as the Avogadro

The
volume

Avogadro

is the

number

number

is

the

2.69

A5)

x IOi9atumscnrJ.
divided

number

by the

molar volume at

of molecules in

volume occupied by one mole.We

combine

O'C and 1aim

one mole; tUe

(M)

a ad

molar

A5) to obtain

Processes

Transport

under standard conditions:

free path

mean

the

tttz

\342\200\2243\342\200\224

This

1000 times larger than

is about

length

= 2M *

1\302\260\"i Cm'

lO*7\"\"\"\"^

2\\rT9

]7pT6

atom. The

of an

diameter

the

^16a'

associated collisionrateis

or Idynecm\022, the concentration of atorr.: s

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
that
the meaii free
below
also called the Knudscn region. We
assume
region,
a

At

path

in

small

is

a system

Consider

a constant

with

we may create a

opposite endsin
system
the

not in thermal equilibrium,but

How from one end of tiic system
state

steady

is

at

the

from reservoir 1 to reservoir2. Energy

entropy of reservoir 1 -f reservoir

gradient

the

in

There

is

directly

the

through
a

linear

proportional

specimen

in

region

to the
s=

flux

most

noiogicai

law,

of

the

flux density

transport

(coefficient)

3A

law for

as Ohm's

of a

quantity

= flux density

system by placing

will

How

direction

tempera'

the

through
will

increase

+ system. The temperature

that

quantity

is trans-

processes in which the

flux

is

driving force;

provided the force is not too large.Such

such

in this

flow

steady
For example,

at two different

driving force; the physical

in this process is energy.

is the

system

in a

energy

temperature,

higher

otUer.

the

to

large reservoirs

with

total

transported

apparauis,

a nonequilibrium

in

condition

noncquilibrium

contact

thermal

If reservoir

tures.

the

laws of rarefiedgases.

PROCESSES

TRANSPORT

state

dimension of

the relevant

with

comparison

section on

in the

except

I0~6atm

of

pressure

of

x (driving

force) ,

relation

is called

A7}
a linear

phenome-

Thedefinition
the conduction of electricity.

is:

net

quantity

unit area in

oM transported
unit

time.

across
(IS)

Table 14.2

Summary

of

laws

transport

phcnomenologica!

Flux of

particle
Effect

Number

Diffusion

Coefficient

Gradient

property

J,

DifTusmty/)

dz

Viscosity

Transverse

Thermal

Energy

conductivity

ictricai
Electrical

Charge

conductivity
n

dv.
M ~~

\342\200\224
= Ct
\"

-~
a:

Thermal
\"z

JB
K

conductiviiy

Conductiviiy

E,

xx number
of panicles per unit volume
= <Ji'J>
Z = mtan thermal
speed
/ \342\226\240=
free path
mean
C|- heat capacity per unit volume
thermal
pu \302\253=
energy per unit volume
*2- shear
force per unit area
Fx/A

bols:

i;

Viscosity

ip *=\302\273
elccirosuiicpolcniial

E = electricfield intensity
q = elcciticchdrgt;

M
p

^=

mass

\342\200\224
mass

p ^

of parucle
per unit volume

momentum

J.

The net

transport is the transport in

direction

one

opposiie direction.Varioustransportlaws
Particle
In

14.5 we

consider a

system with one end in

potential /ij; the other end is in

reservoir

at chemical

reservoir

at chemical potentialft2.

is at the higher

chemical
1 to

reservoir

entropy
Consider
particle
by

H-

the

particles
2 -f
the

when

first

system.
difference

urea

a'uait

taken

contact

with

diffusive

contact

with

If
is constant.
wili flow through

flux

reservoir I
the system
the

increase

will

of chemical

Tile

concentration.

in particle

diffusive

flow in this direction

reservoir

number of particles p;isshigthrough

of isothermaldiffusion
is usually
concentration
along

temperature

then

2. Particle

diffusion,

difference

The

potential,

reservoir

of reservoir 1

total

caused

summarized

are

the

Diffusion

Figure

from

the transport in
in Table 14.2.

minus

density

potential is
Jn

is the

time. Tltc driving force

of the particle concentra-

in unit

as thc\"gradicnt

system;

-,)n =

The relation ts

called

Fick's

law;

-Dgradti.

here D

ts

the

A9)
putt

tele

diffusion

constant

or

diffusivity.

of the order of the mean free path /

at position z the particles
before
tn a collision
they collide. We assume that
come into a local equilibrium
at the local chemicalpotentialjt{z) and
condition
local
of the aiean free path. Across
concentration
>\\{:). Let /. be the z component
to
the plaaeat z there is a particle flux density to the positive z direction
equal
\342\200\224
+
a flux density
in the negative z direction equal to ~-{n{z
4>j(z
/;)\302\243(and
~
\342\200\224The
net
at
z
Here
means
the
concentration
particle
/,.
particle
L]cI. n(z L)
Particles

travel

freely

Figure 14.5
contact

over distances

\342\226\240

Opposite

with reservoirs

of the system are in

at chemicalpotentials
/it

ends

-. temperature is constant everywhere.

diffusive

and/ij.

The

Kinetic

14i

Chapter

flux density

Theory

is the averageoverail

of

a hemisphere

on

directions

B0)
to

want

We

ts the

value of cjg

the average

express

projection of the meanfree

speed on the z axis.The

beca
becauseall
directions

is

average

are

forward

c.

and

path,

it =

of?/.

Here

is the

projection

IcosO
of the

of a hemisphere,
likely. The eletnent of surface area
the surface

over

taken

equally

is 2xs'm0i}9.

terms

tn

\342\200\224
?cos<?

Thus

B1)

B2)

On

with A9)

comparison

The particle

particle

we

with

are

of charge

tile

by

in

particles;

are proportional to the particledilTusivity

denote the concentration of ihe physical quantity

processes
Let

pA

density of A

in

the

has

(i';)

is the

value for

same

tile

conductivity

with

the

with

the

describe

that

D,
A.
molecules,

the

thermal

viscosity

If A

is a
then

quantity
the flux

p;irtidcs in

velocity is zero in thermal

equilibrium.
If /{ is a quantity like energyor momentum
find

a similar

\342\226\240>/

(-\342\200\242')

e,<\302\273,>.

mean drift velocity of the

a molecule, then we always

all

In

problems.

is

z direction

j;
ulierc

transport

The linear transport coefficients

by particles.

like charge or :r.:issthat

by

transport of particles;in
in electrical

and

particles;

other

for

model

of energy

the transport

is given

diiTusivtty

with the

coneerncd

transport of momentum by
transport

the

diffusion problemis the

dilTusioii

conductivity

we see that

that

tlie

depends

z directioii.'!

on the

lie drift

velocity of

expression;

IaPa<v.)

B5)

Thermal Conductivity
The
exact
value o(fA
magnitude of the orderof unity.
the
of
A
on
and
be
calculated
the
method
depends
dependence
velocity
may
by
of the Boltztnann
transport equation treated at the end of this chapter. For
we
set
with A9) for particle
simplicity
fA~lin this discussion.
By analogy
the
law
for
the
of
A
is
diffusion,
phenomenologt'cal
transport

a factor with

fA is

where

126)

with

diffusjvity D given

the particle

by B2).

Thermal

Conductivity

faw

Fourier's

Ju

the energy llux

describes

density Ju

\342\200\224

B7)

^Cg

the temperaturegradient (Figure14.6).

This

transport of
additional

The

is transported

energy

under the

not

but

energyt

flux

^o,i> is
within

diffusion

K and

conductivity
that

assumes

form

there

is a

term must be addedif

of particles.

Another

by means

of particle

in the z

density

flow,

as

addi-

flow

electrons

v,hen

nci

direction is

JJ

valid

thermal

influence of an eiectricfield.

energy

where

the

of

terms

in

the mean

velocity;

of the

factor

equation,

drift

=s

128)

/>\342\200\236<!\342\200\242->
,

pu

is the

energy density.

order of unity, as discussed.By

This result is

analogy

with

the

the right-hand side is equalto

-DdpJAx = -D(tV,/cr)(i/t/i/x).

Reservoir

Reservoir

Figure 1-1.6

Opposiie endsof the

conijci

reservoirs

wiih

system

at lempcratures

arc in thermal
r, and ij.

B9)

Chapter 14: Kinetic

Theory

per

unit

of energy. Now

the diffusion

describes

This

denoted

volume,

by

-Ju

on comparison with

is just

dpjet

the heat

capacity

Cy. Thus
-

-.DCYgradr;

C0)

B7) the thermalconductivity

is

C1)

at very
low
conductivity of a gas is independentof pressureuntil
of the apparapressures the mean free path becomeslimited by the dimensions
are
low
than
collisions. Until very
apparatus, rather
pressures
by intermolecular
attained
there is no advantageto evacuating
a Dewar
vessel, because the heat

The thermal

losses are independentof pressureas

as C1)

long

applies.

Viscosity

Viscosity is a measureof the

and transverseto

the

velocity

viscosity coefficient tj

of

gradient

in the .x direction,
is

of momentum

diffusion

with

the

defined

by

the
Slow

parallel

to the How velocity

flow velocity. Consider

gradient in the
velocity

a gas with
z direction.

flow

The

C2)

Here

vx

is

the

x component

of momentum;

component

by the gas

on a unit

of the flow velocity

of the gas; px denotes
the
exerted
and X. is the x componentofthe shearforce

urea of thexj' plane

to

normal

direction. By Newton's
if the plane receives
plane

tlte z

acts on the xy
a net flux density
of x momentum
J:{ps), because this flux density
rate of change of the momentum of the plane,per unit area.

second law

of

motion

a shear

.v

stress X.

measures

the

is given by the number

n times
drift
so that Jn: =
density
<i--> in the z direction,
velocity
= \342\200\224Ddnjdz. In the viscosity
h<Uj>
equation the transverse momentum density
is nMvx;
Is (hMdJO-)its flux density in the z direction
B6)
By analogy with
flux density equals \342\200\224Dit(nMvxl'tlz,
a factor
this
of the Order of unity.
within
= nM as the mass density,
With
p
In

diffusion

the particle
the mean

flux

density

in the

-Dp

z direction

daJds

-n

C3)

Thus, with

by B3),

given

rj

gives the coefficientof viscosity.

The

free

mean

n is

and

path

the con

is / =

cent rat ion.

Dp

= y-c!

from

\\jnd2n

of viscosity
where d is the

A3),

Thus the viscosity

=

rt

which is independentof the

may

be

molecular diameier

expressed

as

htcfiml1

Tlie

pressurp.

gas

is called the poise.

unit

CGS

The

C4)

C5)
independence

fails at

arc nearly always in contact or

molecules

pressures

when

the

pressures

when

the mean free

path

is

longer

than

the

at

dimensions

very

very

high

low

of the

apparatus.

Robert

the

of

independence

1660

In

Boyle

reported

of a

damping

an early

pendulum

in

observation on the pressureindeair:

also that when the Receiver was full of Air,

its Recursions about fifteen minutes (or a
an
U
quarterof hour) before
left off swinging; and ikat after the t'xsnciionof
the
ihe
Vibration
the
same Pendulum
Air,
{being
put into motion)
of
fresh
a
the
event
minutes
Walch) to last sensiblylonger.Sothat
of
appeared not (by
we expected,
scarce afforded us any oiher
this experiment being other than
satisfaction,than that of our not haviiuj umitleil to try it.
26

Experiment
the

Pendulum

included

We observd
continud

With
understood.
implausible, this result is readily
btit
decreasing
pressure the rate of momentum-transfer collisionsdecreases,
each
the
comes from farther away. The largerthe distance,
colliding
particle
collision
larger the momentum difference; the increasingmomentumtransfer
per
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

at

Although

first glance

The observed

of

values

higher
Improved

than

the

calculations

value
of

- nCyfp.

C6)

14,3 are somewhat

unity predicted by our approximate calculations.Imthe kinetic coefficients K, D, i] take
account
of minor,
the

ratio

Kp/rjCy

given in Table

Chapter 14: Kinetic

14,3

Tabie

Gas

but

Theory

values of K, D,ij, and

Experimental

K,

in

K~l

mWcm\"'

He

1.50

0.18

0.158

Hi

1.82

1.28

N,

0.26

Oj

0.27

at

0rC

and

2.40
2.49

210.

1.91

84.

1.91

167.

have

1.90

189.

see the works cited

neglected;

l atm

we.

;\302\273poise

186.

we

effects

/, in

incm*sM

D,

Ar

difficult,

Kp/tjCy

in

the

general

references.

is directly proportional to iheir viscosity.

The
a
different
!hc
probian:
viscosiiy of
diffusivily
suspended in a liquid or gas is
D
oc
tile sojvent opposes !hc diffusion
of ihe suspended
l/i;, where D
particle. We find
refersto ihe particles and r\\ refers to the liquid. The Stokes-Einstcinrebiion for suspended
is D = r/6n^R, where
R is Ihe radius of !tie spherein suspension.
particles

The

Comment,

of

dilTusivity

gas

atoms

of a parliclc

Tlie quaniily

Comment,

to ihe
Reynold'snumber

be equal

tj/p

D. The

diffusii-ify

raiio

for taminar

criierion

kinemaiic viscosiiy;if

is caJlcdrlIie
i\\/p

eiiicrs

into

C4)

iiotds,

v should

iheory and into the

iiydrodynamic

flow.

Generalized Forces

The transfer of entropy

of

any

transport

from

process.

We

system to another is a consequence

to
ihe
can relate the rate of changeof entropy

one

of a

pars

and of energy. By
identity at constant volume,

flux

density

of particles

da = -c\\Vwe write

the entropy

current

density

Ja

with

analogy

}~

(IN

the

thcrmodynaniic

C7)

as

C8)

denote the entropy density; let cafdt denote the

entropy density at a fixed position r. Then,
by the equation
Let a

of

rate

net

of continuity,

C9)

divjo.

cajdt

o(

change

volume
is equal
to the
element the net rate of appearanceof entropy
rate of productionga minusthe loss - div Jo attributed to the transportcurrent.
In

In

unit

a transfer

the energy

density u

The
N are conserved.

U and

process
is

\342\226\240=

D0)

-divju;

of continuity for the

the equation

for

of continuity

equation

particle concentrationti

is

{41)

Let us

take the divergenceof Jo in

= idivJ.

divJa

Let C7)

to

obtain

refer to
the

net

unit

+ Ju-grad{l/t)
div

(tt/x)

take

we

volume;

rate

C8);

of entropy

~~

ct

use

D0H43)

to

D2)

grader).

derivative with respect to

a partial

1 cu

i\\

t ci

tot'

C9) in a

rearrange

\342\226\240

time

change:

dd

We

- Jn

Ja

form

en

D3)

suggestive

of

the

ohntic

power

dissipation:

3. = J.

Here

Fu and

Fa are

grailUM

W)

F, = grad(-;</r).

D6)

generalized forcesdefined
F.

s grad(Vr);

\342\226\240

J,

gradi-;</r)

by

14:

Chapter

In an

Kinetic

Theory

isothermal processF, iii D6) may be written as

of ihe internal and externalparts of the chemical

Fn

lit terms

Fn =

For an ideal gas

electrostatic

==

n,Rt

potential

the

grad/jjni

q gradtp

-gE]

the mobility,

as

D9)

which is the drift

to E

of

coefficients
be

an

D8)

written

terms,

-i>ngrad\302\253 4- uflE

p. is

and

for

qE.

also has two

unit eleciricfield.The raiio of the

and
rfnq in D8). These ratios must

= {r'n)gradn;

\342\200\224
\302\273
Thus

-UAJO^gradn

>=

dtfTusjvity

that

so

<=

gfad^\302\2431,

3\302\253

where D, is the

as

potential,

D7)

xlog{n/nQ),

flux density

particle

or,

{-I/t)grad/i

-\"{i/t

Fn

How

==

gradn
so that

equal,

velocity per
is Djnp. in D9)

E0)

which is calledihe Einsiein

for

a classical

Comment.
irreversible
processes,

processes. We

Onsager

diffusivity

and the

mobility

gas.

We gain an advantage,for
if we

use

FM

FH in

and

reasons

relalcd

D6) as

the

to the

driving

thermodynamics of irrevers-

forces

linear transport

for the

write

Ju

The

ihe

between

relation

relation

=\342\200\242

Z,aiF,

of irreversible

Jn =

L12FB;

t2tF,,+L22F,

E1)

thermodynamics is that
L^B)

Lj,i-B)

E2)

=
where 8 is the magneiic
For E2) to hold,
field intensity. If B = 0, then
L;J
Ljf always.
are perfcclly
the driving
forces
F must be defined as in D6). Other definitions of the forces
L that
valid, such as the pair grad i and grad n, but do not necessarily lead lo coefficients
cited
see the book by Landau and Lifshiiz
saiisfy the Onsagcr relation.For a derivation
in the general references.

of Detailed
BALANCE

DETAILED

OF

KINETICS

Bohr.

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
sonic
exbt
mechanism
Consider
the rate equaiion
whereby syslems can pass belwecnihe two stales.
for transitions into and out of the upperstate:
=

dN+/(lt

wherea,

/J

ts directly

transition

rate

of the

functions

be

may

-1-

\342\200\224
is

to

\342\200\224

the

in

\342\200\224
to

transi-

The

state.

number of systems in the

to the

proportional

directly

E3)

temperature. The transitionrate from

to the number of systems

proportional

from

- PK+ ,

uN~

state.

4-

thermal

In

afp =

the Boltzmann

<N

result

expresses
mechanism

an example, suppose that the

of a harmonic oscillatorfrom

oscillator
-+

s +

1)

__

quantum 'heory.The value of (s) isfound

J

W
W

\342\200\224J
\302\253
<*\342\200\242>
<*>

so thai, with

=
\302\243

<sy
W
W

\342\200\242

<sy

exp(e/r)- P

2A to

I)e;

In

the

derived

result

the

from

=
+ i =
+

of energy
(s
to (s \342\200\224
i)e.

that

is shown

it

the excitation

with

proceeds

and de-excitation of the oscillator,a

the excitation

texts on

\342\200\224

that

/J(t)

transitions. As

in the

assists

se to a state
goes from se

oscillator

Prob{s

__

between a(rj and

a relation
that

E4)

exp(~2A/r)

of energy

state

* +
inverse process
the
mechanical theory of the
quantum

only if

be satisfied

can

+ -+

transition

in the

for

>/<N\">

by any and every

This

factor.

be satisfied

must

= 0, which

(i/JV*/i/i)

equilibrium

exp(e/t)

most

distribution;

Planck

exp(E/T)

in

'

conserve energy,

aft -

<5>/<s

1)

exp(-2A/r).

E5)

This satisfies the conditionE4).

The
in

thermal

principle

equilibrium

emerges as a generalization ofthisargument:

leads
to a given state must
rate of any process that

balance

of detailed

the

Chapter14t Kinetic

Theory

of the inverse process that

the rate

exactly

equal

from

leads

state.

the

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
a
solid
will also be emitted
by
the
would
heat
because
it
could
not come
into
strongly\342\200\224othenvise
specimen
up
thermal equilibrium wi!h the radiation.

ADVANCED TREATMENT:
TRANSPORT

BOLTZMANN

theory of

classical

The

equation.

v. Tiie

velocity

transport processesis

Tlie

Boltzmann

the

flowline

dt

absence

the

+ i!t,r -+

us

that

following argument.
function.

distribution

if we

We

consider

The Liouville

follow a volumeelementalong

tle,\\ +

dt.T

d\\) =

tk.v

E7)

/(f.r.v) ,

With collisions

of collisions.

fit +

on

the

E6)

is conserved:

distribution

f(t
in

by the

is derived

equation

displacement
mechanics
rells
theorem of classical

transport

of particles in drdv.

= number

of a time

effect

the Boltzmann

space of Cartesian coordinatesr mul

function /{r,v) is defined by ihe relation

distribution

classical

f{t,\\)thdv

the

on

based

the six-dimensional

in

work

We

EQUATION

dv)

- f(t,r.v) =

E8)

dt(ff/ct\\mijoni,

Thus

dt(cf/c!)
a denote

Let

+ dr-

the acceleration dv/tli;

cflct +
This

In

is the
many

of
introduction

gradv/ = (/t(f//^)Mu-

gradr/+(/v

\342\226\240

grad,

/+

E9)

ihen

\342\226\240

gradv

F0)

\302\253

{df/ct)tM.

Bohzmann transport equation.

problems

a relaxation

the

collision

lerm (cf/ct)eolJ

time rc{r,v\\ defined by

may be treatedby

the equation

the

introduc-

ParticleDiffusion
is the

Here/0

with

time

relaxation

for

of

distribution

The decay

function in thermal equilibrium.

t for temperature. Suppose thai

distribution
velocities

up by external forceswhieh

is set

of the distribution towards equilibriumis then

- f0)

we

if

note

that

dfo/dt

has the

equation

are

= 0 by

Do not confuserc
a noncquilibrium
removed.

suddenly

(torn

obtained

f ~fo

definition of the

as

F1)

F2)
distribution.

equilibrium

This

solution

F3)
ft

is

We combine
iu

the

that xc may

exeluded

not

E6), \302\24360),and
time

relaxation

be a

to obtain

F1)

r and

of

function

v.

the Boitzmanu

transport equa

approximation:

F4)

In the
Particle

steady state cf/ct =

definition.

by

Diffusion

Consider an isotliermalsystem

The steady-stateBoltzmann
approximation

of the particle
in the relaxation

a gradient

with

equation

transport

concentration.
time approxi-

becomes

F5)

-(/-/0)/i{,

v.dffdx*

where the nonequiltbritim distributionfunction/ varies

as
We may write {65)to first order

along

x direciion.

the

F6)

^fo-vsMJx,
/\302\273

where

we have

solutions

when

replaced cf/'dxby
desired.

Thus

necessary

for

the

vj^lfjdx

/\342\200\236

treatment

can

iterate

order solution

the second

fi= fo- o^M'lx =

The iterationis

We

dfojJx.

to obtain

higher order

is

-f vxlr*tllfalilx\\

of nonlinear

effects.

F7)

Kinetic

14:

Chapter

Theory

Distribution

Classical

Let/0 be the distribution function

in

/0 =

as

in

linear

in

function

/ and f0.

exp[(/* -

e)/i],

F8)

art; ai Iibeny io take whatever

is most convenient becausethe

We

6.

Chapter

distribution

ijmil:

classical

the

the

take

can

We

is

equation

iransport

as in

normalization

the

for

normalization

than

rather
\302\24368)

as in

E6). Then

dfoftlx and the

solution

order

first

for the

F6)

/ = /o The

flux density

particle

(ilfofduWtifdx)

in the

ifoh){dn/dx)

F9)

nonequilibrium distribution becomes

G0)

(^J0/x)(dti/dx).

x directionis

G1)

J/-$vxff>ie)de,
is the
\342\226\240Dfc)

where

density

per unit volume per unit

of orbitals

energy

range:

G2,

\302\273,

as

in G.65)

for a

J/

The first

integral

particle of spin
=

Thus

zero.

JuI/01D(\302\243)f/E

vanishes

because

idn/dx)

v3 is

G3)

jiuJxJohM^k

an odd

function

and

fQ is

an even

func-

confirms that the net particle

The
secondintegralwill not vanish.
fa.
Before
the second integral, we have an opportunity to makeuse
evaluating
time
of what we may know about the velocity dependence of the reiaxatton
icof
is
for
the
sake
of
we
that
assume
constant,
independent
Only
example
r{
velocity; rc may then be taken out of the integral:

function

of

vx. This

distribution

flux

vanishes

for

the equilibrium

Fermi'DiracDistribution
The

as

be written

may

integral

i JV/oO(E)<fe= ~j

because ihe integralis just the kinetic

density
energy
= n is the concentration. The
particleflux
J/0\342\202\254){\302\243)(/e
J'
because

fi

equation

*=

the

with

of the

|nt
density

particles. Here

-{z(z/M)(dn/(lx)

The result G6) is of the

G5)

is

\302\253

-{nxJKtyiflnldx)

+ constant.

xlagn

,n/M

J(iMi'!)/0O(e)\302\253fe

G6)

of

form

the

diffusion

diffustvity

= Vr/A/.=

G7)

K\022>V

time
is that it is inversely
Another possibleassumptionabout the relaxation
~
as in rc
l/v, where the meanfreepalh 1isconstant.
proportional to the velocity,
Instead

of

we have

G4)

J* =

G8)

~(dft/dx)(l/T)j(vx2/v)focD(\302\243)dB

and

now the

integral may be written as

J
where

c is the

\302\273

-i(^\302\273A)W/V^)

G9)

~\\mdn/dx)

(80)

is

=
\302\243>

Fermt-Dlrac

average speed. Thus

J.x
and t!:e diffusivity

i>ic

(81)

lie.

Distribution

The distributionfunction

is

- ^_
;XP[(\302\243

WAJ +

'

(82)
\342\200\242
\342\226\240

Kinetic

14:

Chapter

Theory

dfo/dx as in

To form

the derivative

need

we

F9)

x 6{e-'y)

'tfJdH

at low temperaturesr
a general

for

property

large for

ft.

function

the integral

consider

Now

=^ n

and

F[c)

lhat

bciow

argue

(83)

Dirac delta

function, which has the

that

At low

F{c){dfOl'dii)j\302\243.
j\302\243

ts smail

near n we may

varying

5 is the

Here

\302\253

dfo/dfi. We

elsewhere. Unlessthe function

take F{e)outside

the

dfQ/dfi is very

temperatures
F(\302\243)is

with

integral,

very

the value

rapidly

Fin):

(85)
where we

used

have

dfo/dn

=*

temperatures /@) =

At low

consistent

the

with

1;

fiux

particle

density

is, from

S(e

also used
side

right-hand

approximation.

dfoftlx

The

the

thus

function

delta

have

We

~df0/dz.

= co.
f0 = 0 for \302\243
of (85) is just F[}i),

Thus

- v)d[i/dx.

(86)

Giy

(87)

wheret{ is
has

integral

by
defines

use

the

at the

surface e

M3n/2cf)

time

relaxation

the Vaiue
nlm

zero ii@)

Jlt/ilx

G.!7),

\302\253

-(m,;i\302\273)Jii!Jx.

JM'

At absoluie

(88)

~ 3;i/2ef at absolulczero,from
velocity
vf ort the Fermi surface.Thus

of Q([t)
tile

= /( of the Fermisphere.The

{h2j2in)Cji2n}2

where

zF =

\\mvF2

(S9)

J, whence

= {ilftV-mKJii')''1/\"\021}''\"/*

5(\302\243r/\302\273),/ii.V/.v,

(90)

Laws

Gaits

of Rartfitd

so that (S7) becomes

//=
The diffusivity

~Bxt/3m)t:Fdn/dx

is the coefficientotdn/dx:
-

closely similarin

time is

classicaldistributionofvelocities.

to be taken at the

Fermi

can solve transport problemswhere

as in metals, as easily as where
the
classical

applies,

Electrical

energy.
Fermi-Dirac

distribution

approximation

applies.

the

Conductivity

The isothermalelectricalconductivity
we

when

difiusivity

the

replace

cfdq>fdx

electric

field intensity.

ihe

~-<j\302\243i of

dji/dx of the

external

from the result for ihe panicle

flux density by the particle chargeq

follows

the particle

muliiply

gradient

potential,

chemical potential by the

where Ex is the .v component

The electriccurrentdensity
J,

for a classical gas with

from

(92)

see we

We

and

\\vF\\

{77} for the

the resuh

to

form

relaxation

{92} the

In

(91)

~\\ve\\dnfdx.

H\\/'\302\273)E;

time

relaxation

from

follows

xc. For

gradient
of the

{76}:

(93)

uqhjni

the Fermi-Dirac

distribution,

(89},

J,

Thus

far

this

in

free path

apparatus.

At

pressure

gas

ofa molecule

system conneciionmay
free path. We may usefully
1

10~6atm

10~6kgcm~2

region

of

discussion

as high

pressures

is much grealer than

or

*=

of transport has assumed that

of

the order

draw

a line

The

is understood
dimensions

of a

diameter

of 25 cm, thus

of

the

of the
free

mean

vacuum
mean

laboratory
order

the

of ihe

here and denote pressureslower

vacuum. This pressure

7.6 x 30\"\"*mmHg or
the

(94)

nq'xjm.

is short in comparisonwith the dimensions

of i(T6atm
at room temperature,the

is of the order of 25cm.

be

GASES
the

chapter

mean

molecular

path

RAREFIED

OF

LAWS

(nq2xc/m)E;

is approximately0.1Nra\021

7.6 x I(T4torr. The

to be the regionin
of the

than

the

which

apparatus.

mean

knowledge

or

Knudsen

free path
of

the

of gases

behavior

this

in

is important

region

pressure

use

the

in

vacuum

of high

pumps and allied equipment.

The

of torr,

terms

where

here

1333dynecm~3;

American

;= 1 mm

torr

bar

Then:

torr

iO~3-i(T6

vacuum

high

very high vacuum

3O~6-3O~9 torr

ultra high vacuum

below

torr.

3G~9

Molecules Through a Hole

Flow of

in ilic Knudsen

we

regime

to get

in order

moleculesdo

strike

of

solve a hydrodynamic

flow

problem

because the
to
the
calculate
rale Jfl at
have merely
molecules

through

a hole,

time. We

per unit

of surface

area

unit

gas

We

other.

each

sec

not

need to

do not

the rate of efflux

molecules

which

Vacuum Society is expressed

=
x
1.333
3O\"~3bar=133.3Nnf2 =
Hg
= 0.9S7 standard atmospheres.
!06dynecm~2
by the

recommended

terminology

in

tlie

for

find

flux

density

(95)

where

is

(95),

prove

the

and c is the
cube containing

concentration

consider

a unit

the + z face ofthe cubejct times

strike unit

unit

time,

Each

molecules.

so thattn

strikes

molecule

unit time^nc,

molecules

require the

average of

area.

solve

We

per

mean speed of a gas molecule.To

cos#

for ?, in

terms of c. Becausec. *=

c cos

0, we

a hemisphere:

over

2*
=

J^2

~2n

Therefore

?,

the basis

\302\253
\\c,

for many

and

(95) is

cos 8 sin 1(8

of gas

(96)

1'

[\"\\\\aedf

obtained. The

calculations

\"\"

expression (95)for

flow in vacuum

the

flux

forms

physics in the Knudsen

regime.

If

is

the

area

moleculesper

unit

of the
time,

hole,

the

iota!

particle

flux,

which

is the

number of

is

nS ,

(97)

Flow

S =

The conductances
of
the hole,

through

conductance

is usually

moleculeat T
10cm

the

with

is defined

hole

the

expressed in

Molecules

300

diameter,

K we

have c

a Hols

(98)

volume of gas per unit

at the actual pressure p of

as the

liters

For

second.

per

x 4.7 x

lQ4cms~';
leads
a
to conductanceof 917
(98)

=>

Through

l-ic.

taken

volume

of

for

lime

the

flowing

gas. The

the average

air

hole

of

circular

roughly

liter/sec,

1000

liter/sec.

For a

hole

a given

with

the concentration

Here-

we

have

or,

the total

conductance
~ m,
p

because

to the

particle

flux

is

proportional

pressure p:

the quantity

defined

A00)

Q~pS,

A01)

Thecondition

for

zero

net

flux is

using the proportionality of c io t1'2.In the

do not imply zero net flux tf the temperatures
At
flow

equal
requires

pressures

to

gas

a higher

will

flow

pressure

from

the

on the hot

Knudsen

regime

equal

pressures

two sides are different.

cold side to the hot side; zerogas

side.

on the

...

Kinetic

!4:

Chapter

Theory

- t2, Eq.A01)can

Eft,

be

\\

- p2)S =

-(p,

~AQ

C03)

where

Example; Flow

We assume

molecules
which strike the inner
is
is, the reflection at [he surface
assumed
to be diffuse. Thus when
there
is a net momentum transfer to
is a net flow
there
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
that
transfer
to the waii
on the assumption
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)
of

wail

through

tube

the

tube.

a hns

are rc-emittcd

in

ali

that

must

diameter

L the

and'

the force due

equal

to the

of the

length

for tile

solve

flow velocity

(u) to

A05)

momentum transfer to

the

tube

&p:

=* AAp.

{nLMcM(u}
We

lube. The

differential

pressure

\\nld)ic

whered is the

the

that

directions;

A06)

obtain

A07)
<u>--\302\243w:ln\302\260'\302\245mr

The net

flux

is

AO

- n(u)A

Ap

\342\200\224

A0$)

wher

S =

A09)

tA\302\253/Ap=
\342\200\224j-

is the

conductance

of the lube, defined

analogously

to the

conductance

of a hole, Eq.(97).

of a

Speed

detailed

more

with averages

calculation,

lo a

arefully, leads

conductance

differing

xAi

of a tube

conductance

The

(98),A10), and A21)below.

This

ratio

that

every

will be larger
molecule hits

valid we must
compared to uniiy,
to be

than

for

unity

1L <

that

the

of a

that

4d.

In

bole

with

A06)

writing

the

area. From

same

tioi

we assumed

implicitly

for a

be true

means

which

A12)

\302\273id.

example for the conductanceof a hole, we find ihat the conductance of

is about 122 Jiler/sec, for air at 300 K.
Jong and !0 cm in diameter

our earlier

Using
tube

1 meter

Speed

of a

Pump

The speedofapump

is defined

as the

is defined

it

S/3*:

short tube.For our result

tube is long enough to make the ratio A11] be small

by

take

distribution

velocity
a factor

2t\302\253/J

cannot be larger than

ihc tube wall. This will

suppose

over the

from A09)

Pump

intake pressureof the

pump.

to thecOnductancoofaholeorofa

similarly

volume pumped
The

per
same

unit

time,

symbol

with

S is

the

tube;
taken at the

volume

used as for conductance;

(H3)
just

as

Proof:
denote

of two

i!ie conductance

for
Let

pE

denote

[lie puntp

flux requires that

the

pressure

dectriaii conductorsin series.

al the input

cad of the lube, and

intake pressure at the output end of the

tube.

Continuity

let

p2

of

Chapter 14: Kinetic

Theory

SO that

^i
to

equivalent

connections

A13) for

than

the

between

speed

to Eq.

pump

=
p V

be

connecting

of the pump itself

ihc connecand of

as short

lube makes
be

cannot

poor

larger

aperture.
effective

with

a volume VI From
of pump speedanalogous

S evacuate

speed

Nx, and from the definition

find

we

(99)

of its awn

narrow

and

the speed

Further,

pump.

does a

rapidly

the ideal gas law

to be evacuatedmust

and the vessel

pump

the conductance

How

SJ),
vacuum systems

in high

why

explains

Scft

as largd a diameteras possible.

A long

use ofa high

(ll5)

\\Sp

A13).

relation

The

S,W^

ScS[

Pi

iP^^E^Q^Pl

pump speedis independent

solution
If the

of

pressure,

A16)

di

dt

this

W0-^0)cxp(-(/io);

to

differential

equation has the

\302\253

A17)

V/S.

of! 00 litersconnected
to pump with a speed of 100 liter/sec,the
e
should
decrease
second.
pressure
per
of a
the
of
user
vacuum
technology soon discovers
pumpdown
Any

For

a volume

by

that

vacuum system
than

regions

on the

expected

more
in the high and ullrahigh vacuum
slowly
The
volume.
basis ofpumping speedand system

orders of
gas predominates\342\200\224often
by many
as fast
emits
adsorbed
molecules
gas. The surface
molecules from Uie volume.

ofsurface

desorption
over

proceeds much

volume

evacuates

SUMMARY

1. The

probability

that

P(v)dv

the

Maxwell

velocity

an

atom

has velocity in

\302\273

4;:{.Vf/27rrK'Vexp{~Mi>V2

distribution.

do at

is

magnitude\342\200\224

as

the

pump

2. Diffusion is described
by
=

Jn

wiiere t is the

mean

and

speed

3. Thermal

is

conductivity

(V

4.- The coefficientof viscosity

5.

the

to

According

the mean free

path.

by

K = iC,,ff/ ,

-Kgradr;

is given

by

mass density.

p is the

where

%cl ,

volume.

to unit

refers

I is

described

Ju =*
where

D =

-Dgradtr,

balance, in thermal equilibrium

of detailed

principle

of any process that leads to a givenstatemust

inverse processthai leadsfrom [he state.
rate

Boltzmann

The

6.

of

gmd,

is

-Lzh.

/-

gas is

a Fermi

a
the relaxation

\342\226\240

/+

gradY

7. The electricalconductivity

xc is

o( the

transport equation in the relaxationtimeapproximation

jf

where

the rate

exactly

equal

the

\342\200\224

nqixjm

time.

PROBLEMS

/.

Mean

speeds

velocity

square

<\302\273*>m
\302\253n\302\253

Because
follows

<>3>

<Pjt2>

fa) Show that the

distribution,

Maxwellian
is
vtaa
In a

<w,:>

root

mean

\302\273

<\302\273/>

(MS)

f3t/M)!'2.

and

<^a>

<\302\273/>

<fI2),

it

fol-

that

(_Vx3ylS

(t/M)\023

\302\273

V^JV'1.

A19)

Chapter 14: Kinetic Theory

The results can alsobe obtained

ihe average kineticenergy

of

value

the

speed

ideal

most

probable

as a

distribution

Show that the most probable

gas. (b)

is

vmP

- BT/MI'*.

vmp

By

c
The mean speed may

j^dvvP(v)

i>mp

Maxwell

lhal the

(c) Show

v,mi.

as <juj>. The

written

be

<

= (8T/rcAf)m.

\302\253

also

A20)

mean the maximumof the

vaiue of ihe speed we

function of v. Notice
that

speedc is

Show

that

ratio

velocity of an

A22)

mean of the absolutevalue

?., the

mean

A21)

v,mJZ~ J.0S6.
fd)

3 for

in Chapter

the expression

from

directly

an

of

z component

the

of

of the

is

atom,

\"

?,

2. Mean

kinetic energy in a beam.

ofmoicculcs exits from

now lhal the molecules
are

thai

velocity

the

moiccuies

component

energy? Continent:
thermal

equilibrium

Ratio

particles

of

thermal

in

by a

pass through

A23)

{2t/jiA/)\"\\

[he

Find

(a)

hole

collimated

that

The moiecuiesin

at temperature

second hole farther down the beam,

a small
ihe second hole have
oniy

fast

lo
heat

to electrical

the

moiecuies,

flowing

ihe

The

oven.

ihc

and

residua!

Ehe

the walls

s'u (iirough

Show

conductivity.

is

collide and

do not

beam

have exited from

after they

energy jji a beam

i. (b) Assume

kinetic

mean

oven

an

normal to ihe axisof emission.

What

oven is depleted with

respect
down iCH is not reheatedby

3.

$\302\243

'

a small

that

so

(\\v:{>

for

mean

kinetic

are not in

real

gas left in the

gas will cooi

of the oven.
classical

of

gas

of charge q that

K/ra - 3/2q2,
in conventional

units for

or

K/Ta

Kand T. Thisis known

as

3/:s2/2^2
the

Wiedemann-Franz

\342\226\240

A24)

ratio.

at
or copper
4. Thermal conductivity of metals. The thermal
conductivity
carried
room temperature is largely
electrons, one per atom.
by the conduciion
The mean free path of the electrons at 300K is of the orderof 400x 10~8cm.

electron
concentration
is 8 x 102Ipercm3. Esiimaiefa)
to the heat capacity; (b) the electroniccontribution
contribution
conductivity;
(c) the electrical conductivity. Specify units.

conduction

The

thermal

5.

the

to

electron

Boltzinaun

the

Boltzmann

find

the

a medium with
Consider
conductivity.
The particle concentration is constant,(a) Employ

thermal

and

equation

dx/dx.

gradient

temperature

to
relaxation time approximation

transport
equation in the
classical
nonequiHbrium

distribution:

order

first

the

A25)

(b)

where

vx2

conductivity

the

that

Show

the

Show

a tube.

a liquid

when

that

p between

difference

a pressure

lube

conduc-

thermal

the

Sinijm.

6. Flow through
under

the integral to obtainfor

fc) Evaluate

2e/3m.

x direction is

flux in the

energy

a narrow tube

flows through

the ends, the total volume

ihrough

flowing

time is

in unit

A27)

where)/is

the

L is

viscosity;

laminar and that the

flow

7. Speedof

Show

tube.

is given

second

the length;

velocity

that

at

the

that
a is the radius.Assume
walls of the tube is zero.

at 20eC the speed ofa

for air

ihe

for

end

hole

in

L and

length

effects
series

in

flow

liters

is

per

by, approximately,

(I2S)

L + id
where

tube

the

on a
with

diameicr

tube of
ihe

tube.

finite

J are
length

in

by

centimeters;

treating

we

tried to correct
as two halves of a

have

the ends

15

Chapter

Propagation

CONDUCTION

HEAT

Relation, (n Versus
of Temperature

Dispersion
Penetration

Developmentof
Diffusion

424

EQUATION

with a

425

426

Oscillation

427

Pulse

Fixed Boundary Conditionat x

Time-Independent

Distribution

PROPAGATION

OF

~0

\342\200\242'

SOUND

WAVES IN

429

GASES

Example:

430

432

ThermalRelaxation
in a

Transfer

Heat

429

Sound Wave

434

SUMMARY

435

PROBLEMS

436

1. Fourier

2.

in

Diffusion

Two

and Three

3. TemperatureVariations
4. Cooling of a Slab
5.
6.

436

Analysis of Pulse

junction:
Heat
Diffusion

p~n

7. Critical

Size

in

Dimensions
Soil

Nuclear

437
437

Diffusion from a Fixed SurfaceConcentration

with Internal Sources

of

436

Reactor

437

437
437

The purpose of
the

most

this terminalchapteris to bring

both dassicai

ofsound,

Consider

first

Pick law

A4.19) for

!hc

diffusion equation, which

of the

A, is the

propagation

thermal

physics,

in

found

the

from

flux density:

particle

J, a
where

the

text

EQUATION

derivation

the

of the

compass

propagation of heat and

that
are
subjects
part ofan educationin

CONDUCTION

HEAT

the

in the

problems

important

within

particle diffusivjty

n the

and

(I)

-/?ngrad\302\273

concentration.

particle

The equation

of continuity,
*-'+

assures

that

of A)

substitution

in B)

partial

particle

differential

concentration

Because div grad ss

C)

DnV2n.

describes tlie time-dependent diffusion

equation
n.

The thermal conductivity equation is derivedsimilarly.By

have in a homogeneous
medium
J_ = -/igradr.
The

equation

V2,

gives

y
This

B)

is conserved.

of particles

number

the

- 0,

divJ,

ofcontinuily

for the

A4.27-14.30)

of

the

we

D)

energy density is

+ div.l.

0.

Dispersion Relation,

C is the heat capacity per

the heatconductionequation

where

\302\253

equation is of tbc
is called

as in (i

Comment.
and

particle

The

eddy

F). If 0 is

diffusion

E) to obtain

D) and

combine

F)

K/C.

the temperature.

of

diffusion

time-dependent

ihe

equation

C). The

The
Ds

quantity

fora gasii is approximatelyequalto the

the thermal diffusivity;

diffusivity,

C)

of

form

Ds

Z),V2r;

This equation describesthe

We

volume.

unit

Versus

particle

4.23}.

current

of electromagnetic theory*

equation

(he magnetic field

intensity,

has l\\\\c

then

G)

The constant
is

the magnetic diffusivity

and
in SI is equal to I/ff/i; in CGS,
it itiiS Inc (if n^Cfisiotts (jcnctli) (ttoiej
af^d
is dirccfjy
j^ro^orijoDiiJ to ttic
limes the frequency. When
we have solved one equaiion, say C), we
have
depihK
lhree problems.
DB

may

be called

c j^JZtJ^i,
% \342\200\224

(skin

sohed

Dispersion Relation,
We

look for

to

Versus

solutions of the

equation

diffusiviiy

DV20

= cOJct

{8}

that have the wavclikeform

0

with oj as the angular frequency

an excellent approach 10 this
diffusion waves or heal waves

and kas
problem,
are

so

(9)

tor)] ,

0oexp[i{k-r-

]hc vvavevector.
even

highly

though

damped

Plane

it will

ihai they

wave

turn

analysis

is

out that the

arc hardly

waves

Chapter

IS: Propagation

at all

Substitute (9}in

Dk2

relation

io{k)

for a

between k and to:

[he relation

obtain

to

(S)

ioi.

A0)

plane wave is calleda dispersionrelation.

Penetrationof Temperature

Oscillalion

the

Consider

in the

of temperature

variation

the temperature of the

plane z = 0 is varied
0(<U) =

which

is

the

real

with

periodically

lime

>

0 when

as

0ocosw; ,

of 0oexp(-iw/),

part

semi-infinitemedium z

in ihe

6Q. Then

real

for

A1)
medium z >

the temperatureis
*=

O(z,t)

e0Rc[aip[i(kz

where Re denotes real part

i3'2

and

at)]}

- l}/%/2.Thus,

{i

with

s BDJqiI11,

- iwO)
6(z,i) = 0oRe{exp(-_-/a)exp[i(i/<5)
=

The quantity
characteristic

\342\226\240=

amplitudeof
called
skin
the

the

has

BZ)/u)}\022

depth

penetration

if we

A3)

the
of a lengih and represents

the dimensions

lemperature variation: at this depth the

reduced by e\"J.The characteristic depth is

of the

of 0 is

oscillations

depth

- z/5).

0ocxp(-z/5)cos(w(

are dealing

the

with

in ihe medium\342\200\224the
wave is highly
damped
in a distance equal to a \\vave!ength/2jr.
of soil is taken
If the
thermal
diffusely

wave

amplitude

D s= 1

as

current

eddy

B0/cu}1'1

For the annual cycie,

L(aniiual)

lm.

decreases

x 10\023cm2s'\"',

penetration depth of the diurnal cycie of heatingof the ground

cooling of the ground by the night sky (w s= 0.73 x 10\"\024s\"\"!)is
L(diumal)

equation.

as 5cm.

by

The
'
by e\"

then the

the sun

and

Development of a

of can

tOcm

of

layer

on

10 averageout

cciiar will lend

of a

top

night

day

lontperalure, but liic summer/winterwffxitiofi

of surface

variations

;i!

Pulse

ihc

top

cdi;tr requires several Miclcrs

of earth,
Actual
values of the tliertir.ti
arc sensitive
to the composition and condition of lhc soii or rock.
dtlTustvity
Not'tcc that a figure of merit for cellar
construction
involves
the thermal
of lhc

dilTusivity,

ihe

not

anrf

Development of a

Pulse

In additionto

the

wavelike

severalother

useful

soiution. The

solutions.

of

forms

form (9), the diffusion equal ion has

We confirm by insertion in {8}thai

of the

solutions

0(x,t)
is a

alone.

conductivity

\302\253

A4)

DnDi)~inexp{-x2J4Dt)

proportionality factorhas beenchosen

*~ I.

j*y{x,t)dx

The soiutionA4}
the form

has

ofa Dirac delta function

elsewhere.
The
might
beam

the surface,

A5)
ofa pulse whichat t = 0
localized
at x = 0, and zero

developmenl

S(x}t

sharply

pulse, as

a temperature

be

pulse

electron

the time

to

corresponds

that

so

when a pulsed laser or pulsed

a surface briefly. Let Q be the quantity

unit
area. The temperature
distribution
per
heats

of

heat

on

deposited

is then

given by

A6)

0{x,t)

where Cv

is

heat

the

per

capacity

plotted in Figure15.1.

because

while for the solution

the surface,
Another example of the applicationofA4)

from

inwards

assumed.

material.

of the

volume

2 arises

factor

The

unit

deposited on the surfaceofa semiconductor,

to

all heat

The function

is assumedto flow

is the

diffusion

of impurities

inside ihe

a p-~ujunction

form

was

flow

symmetrical

A4)

is

semiconductor.

The pulse spreads

out

with

increasing

time.

The

mean square

of

value

x is

given by

/X)dx ~2Dit
after

the

evaluating

Gaussian

A-Imi(/)

integrals. The
-

(x1I'1

root mean squarevalue

* (IDty1.

A7)

is

A8)

Chapter

I Si

Propegai

= 1.0

s.b

o.s

,^\\

0.8

\"^

0.6

=4.0
\342\200\224^

0.4

Figure 15.1
from

Eq.

A6).

Piol of spieadof temperature

At i = 0 (he pulse is a delta

pulse

whh

lime. Tor 4nD

= 1,

function.

This result shows thai the width of tile distribution increases as t\022t which is
It is
and
random
walk problems in one dimension.
characteristic of diffusion
a
medium
a
wave
is
unlike
the
molion
of
in
a
which
medium,
quile
pulse
nondisperstve
<o =
motion
for which
rfc, where v is the constant
velocity.The connection with Brownian
the
of
of
a
random
or
random walk problem
each step
follows
if we let t0 be die duration
that
walk; then r = Ni0. Mscre .\\' is the number of iteps. it follows

Comment,

a general

XrBU(i) =

so that
This

the
is

suspensions

the

rnts

dtsplacemcni
result observed
of small

iri

particles

{2Dto)llZN1'2 ,

ts propodional to the square

toot of the number of
of il.c Bfowiiian inolion, the random motion
sludics
in

liquids.

A9)

steps.
of

Diitribution

Time-Independent

Diffusion

a Fixed

with

at x

Condition

Boundary

If a solution of (8) is differentiated

independent variables, the result may
is obtainedby integrating
A4} with

or

~ 0

with
integrated
be a solution.

again

to

respect

of its

any

An important

example

to x;

respect

=*-= [\"dscxpf-s^icrfu,
= x/DDt)U2.

where

Here we

erf\302\253

have introducedthe error function

of the

defined

->
\302\253u
\342\200\224

by

B1}

<feexp(-s2).

jo

Tables

B0)

error function are readily available.The error

the

has

function

properties

erf{0) =
Of

lim erf(x) =

0;

1.

B2)

into
an
diffusion of heat or of particles
solid from a surface at x \342\200\224
the fixed boundary condition 0 = 0o
0, with
~
=*
0 and 0 0 at x co. (For [ < 0 we assume 0=0 everywhere.)The

infinite

at x =

is the

interest

practical

particular

solutionis

0(x,t)

Again

we

proportional

to

into

see

that

DDiI11.

Let us
equation

at which 0(x,t)reachesa specified

of this solution to the dilfusion
application
is discussed in a problem.

The

to lite

that

of

is proporimpurities

a semi-infinite

time. The diffusivily

of the

is independent

Laplace equation
V20

Consider

value

Distribution

look at a solution of (S)

reduces

B3)

the distance

a semiconductor

Time-Independent

- zrf(x/DDt)U2)l

0o[l

=-- 0.

medium bounded by

along the positive z axis.Let the

B4)
the

vary

temperature

plane

2 =

sintisoidaliy

0 and

extending

in the

boundary

plane;
0(x,y\\0) -

0os

B5)

]5:

Chapter

Propagation

ofB4) in the medium is

The solution

0{x,y,z)= 0o5inkxexp[~kz).
The

is damped

variation

temperature

exponentially

boundary plane. The temperaturedistributionin the

must be maintained by constant healsourceson

OF SOUND

PROPAGATION
Results
in

developed

earlier

in

Thermal

effects

are important

gases.

pressure associatedwith

sound

the

this

in

boundary

plane

the

problem
z =

0.

to the study ofsound waves

problem.

the form

wave;

from

distance

time-independent
the

be applied

can

book

ifiis

the

with

GASES

IN

WAVES

B6)

Let

dp(x,t)

of the wave

denote the
be written

may

as

dp =
where

k is

in the

.V

We

p ~

force

is

one

The

Nz

referred

the

to

x component

unit

and

volume

of the

p =

or

NM/V is the mass density,

subject to the

or, in

wave

propagates

of state is that ofan idealgas:

the equasion

equation

The

direction.

pV

Here

B7)

and w is the angular frequency.

the wsvevecior

suppose

where

6poenp[Hkx - on)},

pr/A-f

is the

B8)

mass of a

molecule. The

is

velocity of a volume

element.

The

motion

is

equation of continuity
dp/dt

dp/dt

+ S{pu)/dx

div(py)

= 0 ,

C0)

- 0.

C!)

dimension,

thermodynamic

is

identity

dU

+ pdV

= jda ,

C2a)

of

Propagation

which can

also be written
-_ + p_iV
du

assume

we

If

the

during

of a

passage

is

us define

We

p0,

t0 are
that

assume

three

equatioas

neglect

and

&\\\\d(l/V)[dV/ct)

NMfV

C4)

t ~ T0(l

+ s);

+ 0) ,

C5)

of the sound wave.

and temperature in the absence
- wO].The
a
u, s, Shave the form of travelingwave;exp[t(Jcx
become
B9), C1), C4) that govern the motion now

at

ia)pos

equations
pu ~ po{\\

+ pn)

ik{pous

icu{pfp)p0s

terms
+

reduce

in

the

= 0;

C6)

= 0;

C7)

C8)

0.

wave amplitudes

small

sufficiently

in these

+ (pTofM)O]

4- ik{(?po/M)s

u.s, and 0. For example,

ncgiecicd. The equations thus
p

re-

can

- 0.

{p/p)(ep/ct)

-iwiQt,y0 +
that

We

volume.

unit

the density

to
approximation

per

C3)

deviations s, 0 by

Pod

-iwpu

We assume

thermodynamic identity appears as

the fractional

where

= 0

(p/V)lcV/ct)

Cv(dx/di)

Let

there is no entropy exchange

Eq. C2b) becomes

sound wave,
+

C2b)

Ty.

capacity at constant volume,

term in terms of dp/ct becausep

Now the

-~(\\/p)(dp/dt).

da

heat

the

second

the

rewrite

beiow) that

discussion

(pending

Cy(cr/ui)

where Cv

Waves in Gases

Sound

it

squares

s)u becomes po\\\\

the
to, with

is

a good

and
if

the

approxima-

cross
cross

subscripts

of

products
product

dropped

su is
from

r,

cott

- (kx/M)sas ~

rCyO

ps =

0;

{kxjMH

C9)

0;

ku = 0;
or

CVB

D0)
-

us =

0 ,

D1)

IS;

Chapter

Propagation

n is

where

the concentration. Theseequationshave

y =

n)jCv =

(Cy +

Tiiis

result

to

applies

fyt/M)llik ,
in

\302\243,/\302\243(,

it,

D2)

.
of sound is

The velocity

units.

our

den/dk

D3)
the lowest frequenciesup

gases from

nionatomic

if

only
\"

to =
where

solution

to

high

should
wavelength
frequencies
only by the requirementthai the acoustic
atoms.
This
of the
be much larger than the mean free path
requirement is the
of she hydtodynamic
criterion for the appHcabiiiiy
approach embodied m the

limned

force

B9).

equation

Relaxation

Thermal

gases {43}is

Wiih polyatomic

increasedthere
\342\226\240

sound

is

region belwcen low frequency

with relaxation effects.

is associated

propagation

Thermal relaxationdescribesthe
system.

temperature; the dissipation

coolinghalf-ejcle
in

polyatomicgases

LetthehealcapacityCi

states, while Cy

and

t =:

of

are

period

of the
the

freedom

fre-

in
equilibrium
not at ihesame

system

with

high

lime

of the

heating and
required

for

system. In

are lime delays of the order

internal vibrational stales of a

there

conditions

between the
states.

translation

external

the

and

is comparable
degrees

of energy

transfer

Hie

in

the

when

different

standard

under

of 10~5s
molecule

al! parts ofa

strongest

wave

sound

the

between the

heat exchange

is

and

thermal

of

establishment

results when

dissipation

Energy

the frequency is
of
above which (he velocity
but as

frequencies,
region

frequency

transition

The

increases.

frequency

transition

low

at

valid

and temperature tj = to(\\ -f 0,) refer to the internal

C4)
to(l + 0) refer to the translations! states. Then

becomes

Ct(dxt/dt)

or, in

of

pSacc

thai

the

characteristic

(p/p)(dp/ci)

= 0 ,

D4)

- 0.

D5)

QS),

-kotoCiQi

Suppose

(cz/ct)

\\

the

transfer

tune

ia>x0CvO

of energy

delay

tQ

such

ioj{p/p)pQs

between ihe

internal and externalslateshas

that

t)/t0

D6)

koO, = @
t0 is

Here

tiie relaxation

called

- 0,)/!Q.

time. There will

be

D7)

relaxation

separate

times for

the rotational-iranslational transfer and the vibrationaf-iranslaiionaltransfer.

We
combine
C9),
D0), D5) and D7) to obtain the dispersionrelalion

,48,
where

Cp refer

CV,

(otQ

I
\302\253

to the

-^-i\342\200\224i

ftj*(A//r)

the
the low frequency limit
of
Ct). The low frequency limit of the

y0 is

where

4-

11,@)=
In

the high

frequency limit cur0

\302\273
1

refers

yM

stales

not

of sound

is

are

y\302\273

frequency

limit

only
excited

of y0

of sound

and

E1)

w2(A//yxt).

frequencies the internal

translations! stales; at high

the sound wave. The high frequency

are given in

C\\)/

is

E0)

to the
by

ratio [C^ +

heal capacity

velocity

D9)

(Vqt/A/)\022.

*,(cc) =
Values

low

\342\226\240

w^Af/vor)

total

J =

Here

the

and

k2 =

(O

translational states alone. In

limit

of

E2)

G*t/Af)\022.

Table 15.1;if

no

the velocity

stales

internal

at all

are excited,

The wave

is ai(enua(ed when k

pressure
absorption per

a.

coefficient

attenuation

wavelength

is

From
when

occurs

the imaginary

complex;

part of k gives the

D8) it is found that the maximum

cu = 2n,'t0 and is given approximately

by

C.

~
Cp

,,,.

C,

Cy
Cv

-f

Chapter IS:

Propm

Ralio

15.1

Table

Cp Cy

Gas

for gascS
\342\226\240;

CC

Temperature,

Air

1.403

17

1.324

100

HjO

1.410

15

H2

1.450

-LSI

Oa

1-401

15

1.396

200

1.303

2000

CO,

15

1.304

Ar

15

1.668

He

kois:

For

tof

3nd

as

ftf

tic.

and Hj

for Oj

C,!Ct- =

high

9/7 -

at

lo
1.2S6,

<lrc of v^i spplicsblc

in ihe
ijmil of low
\302\253
5.3
\342\226\240/^

frequencies. For

in agreement

Heat transfer

1.667,

in peruiurc

a!
ni^ii

very

frequency

high

is appftcabk.

a( the relaxation frequency

the intensity is observed to decreaseby

Example:

Ic

ai levnperalufcs
room
(cmpe^aturci
excite also the v?branooal
motion,
as for O, aj 2000=C.The values
given
Eo sound
waives
to slslic processes
miti

CO2 gas

absorption,

- S/J =

Idea! gai,C,/Cr
roi a qj^equuc q&$ sJ 2

imoniiomic

suAicicr\302\273tly

For

1.660

-180

in

with

in about

1/e

standard

under

20kHz

of

wavelengths\342\200\224a

conditions
massive

theory.

Have.

a sound

Equation {33)expressesthe

iserttropic

assump-

which
ncglecis ihe thermal conduciivity
gives rise to some transfer of
thefniat
Within ihc sound wsvc betweensuccessivewsrm and cool half cycles. The
energy
0 musi be modified lo lake account
of heal (low. The heat conduction
assumpiion thai da \302\253=
F) may be wtiuen as
equaiion
assumption:ihe

equation

Kch/cx2
where 8 is

edict

E4)

(he entropy density. Then C4)becomes

Cytftjdt)

- Ktfh/dx2) ,

lpfp)idpjdt)

icaps

-Ktk28.

E5)

we use

When

K/ai. At

With

essentiallythe
of the

length

of

place

low

dispersion

Wk* is

The

wavcveclor

lj{1.) becomes

relation

much Smaller

lhan

Cy,

the sound velocity

so thai

the molecular mean fiec path and

of the pressure oscillation is given
denoted by a. The result from E6) in the
I is

attenuation

and

is

X is
by

the wavethe imag-

low frequency

is that

* =
Ce refers lo unit

where

the

/ \302\253
}., where

condiiion

region Wk1 \302\253

Cr

{4\\\\,

frequencies

sound wave.

of the

pan

imaginary

in

this

f/o ~

E7)

l)pK<a2j2i\\3Cp

volume.

SUMMARY

that
equation is the partial differential
equation
when the phenomenologicaitransport equation(here the Fourier

1. The

heat conduction

combined

with

the

D,

D,V2r;

iavv)

is

We obtain

of continuity.

equation

follows

K/C.

and the eddy current equation have

time-dependent diffusion
equation
the same form,
so that
their solutions may be translated from
the
solutions
familiar
in the
of the heat conduction equation, these being often
more

2. The

Hterature.

3. Frequently H is useful
of plane waves of the

solutions

to construct

the

in

of superpositions

form

form

0^

-tot)}.

0oexp[/(k-r

equation then gives

dispersion relation of the problem.

The differential

the

relation

between

<y

and

k, called

the

of
depends on the rate of exchange
between
the translation^!, rotaUonal, and vibrationai motionsof a
energy
not
and
moiecuie.
A low frequency
sound wave is describedby isentropic,
result
that seems paradoxical
at first sight.
isothermal,
parameters\342\200\224a

4. The

propagation

of

sound

waves

in gases

IS;

Chapter

Propagation

PROBLEMS

/\342\226\240
Fourier

1= 0

form

ihc

a distribution ihat at the initial time

can be
function iSf.v). A delta function

Consider
of pulse.
of a Dirac delta

analysts
has

represented by a Fourier integral:

0{x,0)=

Ik f\"

0{x,t)

D[x,t) =
the

Evaluate

distributionis

The

f{x,0),

time

by the

then

development

at

A4}.TSms

dk exp{ikx

- Dk2t).

F0)

This is a

in

ma

A4). The melhodcan

distribution

any

/(x,0)

of 5{x

- x') is

x',t)

at r ~

given

D7i/)f)^

Jdx'f(x',0)S(x

\302\273

distribution

and

be

0. If

extended

to

the distribu-

- x').

exp[-(.v

F1)

- x'J/4Dt]

F2)

f{x,0) lias evolved to

-

{4nDi)~{

fdx'f{x\\0)cxp[-(x

F3)

x'J/4Dtl

solution-

general

powerful

2. Diffusion

the result

definition of [he delta function

t the

time

fix,!) =

in two

E9)

J^

development of

0(x by

- a)!)},

\342\200\224

to obtain

integral

the time

describe

dktxp[i(kx

\342\200\242)-\"\342\226\240\"

of A0),

use

by

E8)

^~j^<!kcxp{ikxl

times the pulse becomes

At later

or,

Six)

three dimensions,

dimensions admits [he solurion

02{t)

(a) Show that

tlte

diffusion

(C2/!)exp{-~r2/4Dt)

equa

[ion

F4)

and in tlirce dimensions

o,F -

{C3/iin)tsp{~r/4Di);

F5)

constants
C2 and C3. These solutionsare
ihc evoltiuon of a delta function
at t = 0.

the

Evaluate

(b)

and describe

to

analogous

C4)

3. Temperature variations
in soil.
a hypothetical
Consider
climate in which
boih
ihe duiiy and the annual variationsofthe
temperatureare purely sinusoidal,
wiih amplitudes
0d =* IOC. The mean annual temperature0a s= 1OX. Take
x IO~3 cm1 s\021. What
is Uic minimum
[lieihcrmaidifTusivityofthesoiltobel
at
which
water
shouldbe
buried
depih
in
this
climate?
pipes
2a
and
uniform
initial
of a slab. Suppose a hot slab of thickness
of
water
0o < 0u
temperature 8t is suddenly immersed into
temperature
the
the
slab
to
at
the
surface
of
temperature
thereby reducing
80 and
abruptly
in the slab in a Fourier series. After
keeping it iherc. Expandthe temperature
some
time all but the longest wavelength Fouriercomponent
ofihe temperature
will
have
and
becomes
then the temperature distribution
sinusoidal.
decayed,
After
what
lime
will the temperature
difference between the centerof Uie slab
~
and
its surface decay to 0.0! of the initial
difference
0O?
0s

4* Cooling

surface concentration. Suppose a siliof boron

silicon crystal
is /j-type
1016cm~3
doped with a concentration of ua \342\200\224
atoms. If the crystal slab is heated
in an atmosphere
containing phosphorus
the
latter will diffuse as donors with a concentration nd(x) into the semiatoms,
=
will form a p-n junction at [hat depth at which
semiconductor.
na
nd.
They
the phosphorus
concenu:;Assume that the diffusion conditions are such
that
= 10l7cm'\023.
Take the diffusion
lion at the surface is mainiained at nd@)
is the value of ihe constant
coefficient
to beO s= iO~13cm2s\"l,What
of donors
i is
C in the equation
,\\\" =* Ct1'2,
where
.x is ihe depth of the p-n junctionand
5,

from

diffusion

junction:

p~-n

a fixed

ihe lime?

i5. Heat
present,

the

with

diffusion

internal

equation

continuity

internal

When

sources.

E) must be

heat sources are pres-

modified to read

C~ + divju =
ct

gu

Ffi)

rate per unit volume. Examples includeJoule

generation
in a wire;
trace
heat
heat from the radioactive decay
elements
generated
rise
ai die
ihe Eanli or ihe Moon. Givean expression
the
inside
for
temperature
a
on
the
and
center of (a) cylindrical
wire
assumption
(b) iiic spherical Earth,
that
of
and
is
is
constant
with
time.
ga
independent
position
where

7,

gu

is

Critical

the

heat

of

size of

nuclear reactor.

problem to

particle diffusion,

rate

is proportional

i/B

that

and

to the

Extend

the

assume

thai

considerations

there

is a net

of

the preceding

particle generalion

local parsicle concentration,gn

\342\200\224

n/t0,

\302\253
here

characteristic time constant. Suchbehaviordescribesthe neutron

generaof\"SU
reactor. The value off0 depends on die concentraiion
generationin a nuclear
f0 is a

Chapter

nuclei;

IS:

Propagal

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
at zero.
Show that
concentration
=
if
has
term g, n/t0,
solutionsof the form
Eq. C), augmented
by a generation
n(x,y,z,!}

where kxL, kyL and

k:L are

F7)
multiples

integer

of n.

Give the functional

depen-

for at least
klt ky, k. and r0, and show that
time
one of the solutions of the form F7) the neutron concentration grows with
of Dn and @. In
if L exceeds
a criltcal value Ltli(. ExpressLc,-n as a function
because
the neutron
actual nuclear reactors (his increaseis ultimately
halted

dependence

of

generation

the

net

rate

time constant

gn

decreases

i\"; on

with

increasing

temperature.

Appendix

Some

Integrals

Containing

Exponentials

THE GAUSS

INTEGRAL

Let

J -

The

trick is

following

<x>

(i)

JO

used to evaluate /o. Write

(i)

of a

terms

in

different

integration variable:
-

B)

/\342\200\236

j'~mp(-y')cly.

Multiply (i)

V -

and B) and

convert

ihe

to a

result

double integral:

J_>^exp(-xa)*cJ_*\"exp(-.y2)<fy
j\"
J_*Jexp

- (x1 +

y')ilxdy.

C)
is

This
tp,

as

dx dy

an

in Figure

shown

becomes

entire *->\342\226\240
Convert
to polar coordinates r and
plane.
= r1, and the area element dA
=
A.S. Then, x1 \342\200\242}\342\200\242
y1

over the

integral

dA

ritnltp:

= 2i

'\302\2602

Jo

[j\020<=^-r')r'lr\\dif

Becauseof d[exp{~r2)] =

- 2exp(-

the

r2)rjr,

V - -n Jf4exp(-r2)]

integral

over r

is elementary:

\"

- n.

\302\273

-fnexpl-r1)]'
L

J'-\302\260

D)

C iFitc\302\243r@'5 LOfl

area

element

iU =

rrfrtltp.

GAUSS

GENERALIZED

AND

Integralsof

function

not

need

- 2

be an

JoVexp(-x2)(k,
integer, may

The integral

in

\\alues of

F)

>dy

may

be viewed

y,

V(n

2dx

E)

-1)

tabuiatcd

widely

gamrna

y~idy:

- l

(m

I),

as the definition of f(z)

easily obtained for n >

extend the definition F) of
always

0 <

0 from
T{z)

to reduce

possible

z <

the

satisfies

It is

interval

>

for

F)
positive

nonititeger

r.

The gammafunction

is

(m

be reducedJo the

~
V{:), by the substitutions x2
Im

it

INTEGRALS

form

the

Im

where

INTEGRALS,

FUNCTION

GAMMA

!.

to

rdalion

recursion

F)

by

negative

F{z)

for

integration

values
arbitrary

by

parts,

of z. By
argument

and

it

is

used

to

using (?) repeatedly

lo a

value

in

the

The

= 0,11

Form

is

Urn

even

an

Approximation

Stirling

= -J; from D):

integer,

a half-integer, and
the
aid of (8), that

0, n is

\342\200\224
21 >

by repeated application of G), with

i! ~ 1

\342\200\224

},

then

we find

h,

= ry +

/,
in is

an odd

(/

(i -

i) x

j)

\342\200\242
\342\226\240
\342\200\242
x
x
\302\247

= HI)

JoV'<0'

Jo*.xexp(-*!)ifc

integer,
the aid

with

similarly,

(9)

x u\"!.

l.ii -0:

Form -

If

j)

in

2i H- I >:

1, n

is

an

integer,

~ 1.

n = /

A0)

2: 0, and we find

of A0),

'lit i - 2 JoV*lexp(-x')J.\\-

= HI
The gamma

for

function

the

preceding

integer

THE

STIRLING

For large

values

1)

I x

is simply

argument

integer

positive

(HI

1)

(I-

ihe factorialof

the argumeni.

APPROXIMATION

of\302\253, n!

be approximated

can

by

A2a)

logn! *
Here

the

0{i/\302\2732)

term

slands

lj\\og2n

1/12/? is
for

omitted

the

(n

first

higher

J)logH

term

of

+
j\342\200\224

nn expansion

order terms

in

this

by powers
expansion,

of

and
!.'\302\273,

of order

l/\302\273

Some

or higher.

is to

Exponential*

Containing

Integrals

In practice,even
the

on

check

is usually

I/I2n

of the

omitted. Its principalrole

If the effect
of
the
I/12n-

approximation.
a
only
change below the desired

accuracy

introduces

correction

lerm

the

accuracy,

ihe

entire

expression has the desiredaccuracy.

To

derive

we

A2)

in accordance

write,

\"!

with

A1),

\"

\342\200\242

J0\"exP[/(x>]'h

jo\302\260x\"e\"llx

A4)

/(x)=)ilogx-x

We make the

A3>

substituiion

x=

yii*

= n(l

dx - rfdy.

+ j'lr1) ,

A5)

Then

J{X)

= I! lOgl!

9(y) =
With

It

S(j')

npog

A7)

these,

exP[/(-v)]= irV-'e

(IS)

A9)

The

function

expansionof

g(y) has
the

(.y2/\"I'2.

0;

g@) =

0. Using the Taylor

logarithm,

log(l

with

its maximumat

+ s)

= s

we expand

- is' + Js1-

|s\"

B0)

g{y):

B0

The

tile limit n

In

-\342\226\272

a},

integral in A9)

~ 0,

and all but llie

the

If B2)
term

correction

the

for

B1)

and the

vanish,

= On)'11 ,

J\"exp(-j.72)rfi.

of D).

aid

in

becomes

/
with

term

first

Approximation

Stirling

is insertedinto A9)

is a

Its derivation

1/I2n.

to A2a)

is identical

result

the

bit

We

tedious.

B2)

work

except
with

Iogii! and wrile

log/ii = {login +
If we

h by n

replace

Iog(n

+
(\302\253

logn!

B3a)

- 1,
- ^Iog2n +

1)!

sublracl

\342\200\224
\302\260(i)-

(n

We

- ii +

iltog'i

B3b) from

B3a):

- log(n

- 1I

<23b>

\\n

ii

log

loS\"

jj-^-jT;

= (n + J)logn

terms

omitted

where

all

can be

combined:

If this

is

inserted

into

are now

(ii

5)log(il

at least of order I/a3.The

- 1) -

two

terms

in A

B4), we find

4 = (n-i)iog

B6)

Some

Containing

Integrals

For large

the

Exponentials

logarithm

may

be expanded

according io B0),with
+

\342\200\224

\\/n:

B7)

\302\260i

B8)

If this is
We
such

inserted in B6)

are
that

often
the

interested
relative

not

error

decreases with
neglecting all terms in
true value

we see that
in

n\\

but

\\/\\2.

that

Iogu!

in Iog/i!,

oniy

between an

increasing
(I2b)

approximate
an

\302\273.
Such

increase

=s

if

and only to an

log

approximation

less rapidly

ii

value

of

accuracy

Iog/i!

and

is obtained

than linearly

with

the

by
n:

B9)

Appendix

Scales

Temperature

DEFINITION OF THE

SCALE

KELVIN

in terms
of the
temperature*-1 are not expressedin practice
fundamental temperature r, whose
unit
is the unit of energy, but on the (absolute)
scale
is the
thermodynamic
temperature
T, the Kelvin scale, whose unit
kclvin,
as ihe
symbol K. The kelvin was defined in 1954 by international
agreement
fraction 1/273.16of the temperature
T, of the iriple point of pure water.Henr;,
this
s
K above
273.16
is O.GI
the
definition,
by
K, exactly.This temperature
T,
ice poini),
(the
atmospheric-pressure
To ~ 273.15 K.
freezing point of water

Numerical

values of

The triple

point

more

is

and accurately

easily

reproducible

triple point establishes itself automatically tn any

that is partially backfilledwith
water
and cooled
pure
the water is frozen, leadingto an equilibrium
between
and the water vapor above the ice-water
mixture.

The

Celsius

The

temperature

on
Temperatures
Temperature

The

are

scale

this

differences

have

conversion

factor

/ is

scale
a

in

until

poini.

vessel
all of

not

ice, liquid

the

of

but

part

solid

terms

ice

evacuaied

Kelvin

water,

scale, by

- 273.15K.

value on
the

between

(I)

in degrees

expressed

liie same
kB

defined

the

than

clean

both

Celsius, symbol 'C.

and

Kelvin

fundamental

Tem-

scales.

Celsius

i and the

temperature

Kelvin temperature,

t =
*
1

We
The

appreciate
ullimale

ihe assisiance of
survey of the slale

in ihe preparation
E. Phillips
of precise lempcralure
of development

ipks of various

(962- Pc/liapsthc
methods

of tcm

of this

appendix.

measurement

is Ihe

arc published urider

the SiSn.C
proceedings
volume is largely obiolcie. Vol. 2: E. C.
is still
the State of ihe art, this volwnc
ger reflecting
of tc
methods
s of p/tEittpfci
ofvanous

try.

r; Rcitihold,

B)

Norman

liiic. Vol. 1:C O. Fairchild,

Reir ihoU.
editor:
\\<jS5. Although
W.Jfc. editor; Koicltotd,
for ils thorough
4..tfful
inlioductory i!isi
edili

kBT

19-10.

*ii

Tfic

This

c becauseof
letiis. Vol.

its

4 C

tiitroduLioty

pans): H.

nfcU
JisfUiiion uf

H. Plumb,

edilor;

is

called

the

experimentally;

Boiumann constant. Its

[lie best current value*
ka

The value

A.350662

numerical
x

of the BolUniannconstant
whose

is

of k8

determination

(a) Idealgas.

are the

C)

simple
and

fundamental

Examples

the aid

with

determined

states,

The

determined

10~t6ergK\"\\

sufficiently

quantum

=\342\226\240

be

is

\302\261
0.000044)

mode!syslcms
structures
are
the energy distributionof !he
funclion of the energy, a = a(li).
of Ihe energy is i(U) (ca/cU)~l.

must

value

one can

that

it the

from

lemperalure

of mode!

syslems

of certain

calculate

entropy as a
as a function

used

in

!he

following:

particle concentration all gases behave as

idea!gases,satisfying
NkBT. One obiahis/cB by measuring the pV product
pV
to
of a known
amount of gas al a known
kelvin
T, extrapolated
tcmperalure
of the number
of particles N invariably
vanishing pressure. The determination
iti

the

of low

limit

involves the

Avogadro

constanl

body radiation.
dislributionof black body

(A) Black

NA,
can

We

tici>/kBT,

obtain

of known

radialion

independently

known.

k,, by filling Utc measured

Kelvin temperature T to the

spectral
P!;mck

~
4). Because this law involves t through ihe ralioIioj/x
this dcterminalion
requires the independent knowledgeof Planck's

law (Cliapler

constant.

of vanishing interaction the magnetic

field B, at temperature t, is
spins
Various paramagnetic
by
C.46).
salts, such as cerousmagnesium
given
Eq.
nitrate
are good approximations
to nomnieractmg spin systems
if the
(CMN)
is
too
of
not
low.
measured
values
of
M
as
a
function
BjT
By
filling
temperature
to C.46) we can determine Ihe ratio mfkB,
where
in is the intrinsic magnetic
moment of the eleclron,
known
Usually
independently.
only the low-field
which
is
in
which
case
ihe
also
number
of
must
be known,
portion used,
spins
tnvoives
residual
spin
again
A^. Precision results require correctionfor weak
similar to corrections for particle
interactions
in a gas.
interactions,
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
is due
to the difficulty
fundamenial
constants. Most of this uncertainty
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
h
and NA are known.
which
(c)

Spinpammagnetistn.

moment

\342\200\242

E. R.

M of

a syslem of

the limit

In

in

.V

Cohen and B. N. Taylor,

J.

Phys.

Chem.

a magnetic

Reference

Dam 2,

No. 4 A973).

temperature as conventionalKeivin

When expressing
fundamental

than

t,

temperature

it

is

measurable

accurately

Any

transfer and

heat

entropy transfer

E}

THERMOMETERS

SECONDARY

AND

D)

\302\253=
TtlS.

dQ

PRIMARY

entropy

reversible

between

xda

the Bohzmann

absorb
5,

s ksa.

The relation$Q
then becomes

rather

7\"

temperature

to

customary

consiam into the definhionof a conventional

Thermometers

and Secondary

Primary

property

physical

A'

value

whose

is an

accurately

may be used as a therniomelric

temperature
System possessing the property
and
in
.V
of any system
it.
thermal equilibrium with
Used
til this way. the
X is a thermometer. The principles underlying
system with the property
the
niost
used thermometers are listed in Tables
13.1 and 13.2. The
commonly

known

ofthe

function

A' *= X{T],

temperature,

parameter10

of ihc

the

measure

defined
thermometers listed in Table 13.2are called
thermometers,
secondary
as thermometers
whose temperature dependenceX(T)
must
be calibrated
with another thermometer whose calibrationis
by comparison
empirically,
known.
The
of all secondary ihcrmonieicrs must ultimately
calibration
already
be
traceable
to a primary thermometer. But
once
thercalibrated,
secondary
arc
thermometers
easier
to use and arc more reproduciblethan
the
therprimary
thermometersavailable at the sametemperature.
of the
calculable
that can be used to determinethe value
model
Any
system

constant

Boltzmann

model
(TableB.I).
systems

The

at

times

different

uncertainty

AT

of thermometers

same

on

based
in

measurements

For

their

useful

secondary

helium

example,
range

have

thermometers

vary greatly.

Precision is

when the same temperatureis measured

instrument.
is expressed by the
Accuracy

the thermometer

which

Secondarythermometers
achieve a precision of 1 part
mechaniea!pressure
pressures.

primary thermometer, and the three

important primary thermometers

AT observed
the

with

with

as a

the most

are

accuracy

variation

the

by

used

be

ean

above

and

precision

expressed

kB

diseussed

vapor

I05.

reproduces

electrical
The
is

resistance

precision

much

poorer,

the true Kelvin scale.

measurements

of thermometers
particularly

pressure thermometers at the

may

based on

at low

pres-

iower end of

a precision of about 1 part in 103.The accuracy

is limited by the accuracyofthe primary
thermometers

of

Table

B.I

Principles of the

Model

a|
b)

thermomete

utilised

gas

Static pressure ai
of sound
Speed

constam voliim

Magnetic susccplib'iljtyof
spin

primary

sysicm and

propeny
Idea!

mosl important

noninteractm,

sjsii;m

Eiccironic spins
b) Nuclear.spins
a)

Black

body

radiaiion

note: The coiumn

indicates which equation underlies
\"Defining
cquaiion\"
various nuniiicaiiiics uiay be nccilccl. The temperature rjmecsqtiotcd ;iro

and

diluted

CMNii

the

Thcrtt'oJyttanuc

B,2

Table

of

Principles

most

the

Thet

secondary

important

thermometers
Useful

Thermoelectric

400-1400

thermocouples*

votlageof

Thermal

expansion ofliquid

in

200-400

glass

resistance

Electrical

14-700

metals*

0.05-77

semiconductors (germaniumI

0.05-20

resistors'

carbon

commeEciai

pressure of Jiqucfied gas

Vapor
4

range

taK

Physical property

1-5.2

He

0.3-3.2
p

limits.

ltimate
\342\200\242

'

Used

Widely

as interpolating
instrument in the
used
as cryogenic laboratory

calibrated to deliver usable

be individually

must

used lo calibrate Ihem.The accuracy

their

As

1K,

and about

1 part

1 part

give

above

104

0.01

100 K,

about

of simple
three

without

transfers.

around

can

be determined

is hot

The: method

on the theoretisomehow utilizing the

examples.

cycle. Consider a Carnot cycleoperating

poralure '!\\ and the unknown temperature 7\\, Because
the heat transfers at the two
temperatures
satisfy
temperature

103

in

relying

mode! systems, by

(a) Carnot

unknown

1 part

K,

thermometry

primary

properties
We

hy

THERMOMETRY

It is possiblelo perform

relationE).

in

near

102

in

THERMODYNAMIC

theoretically known

is limited

thermometers

primary

different
by residual variations between
precision
of
rough estimate, the present-day accuracy primary

is about

thermometers

of

and

poor

relatively

thermometers.

1PTS.
ihernion

by measuring

tem-

a known

between

of entropy

conservation

\302\253

The

the ratio of the

\\\\\\o

Qt/Tv

Q2/T2.

unhem

very practical.

is initially at a
substance
(b) Magneticcabriinetry. Suppose paramagnetic
known temperature
in a magnetic
field B{. Let the substance be cooled
a

by

7\\,

isentropic

demagnetization

to the

unknown

temperature T2. If now a

known

Scales

Temperature

amount dQ of hem is added to the substance,

its entropy
is raised by
dS = dQjT2. The substanceis then
and ihc
re-magnetized,
isenlropically
is
has returned
the
magnetic field B2 determinedat which
exacily
temperature
to T,. The field B2 will be found siightiy different than Bt:B2 = #i + <l&.

smaii

conservation

Entropy

requires

cIS =

From

the

dQ/T2

\302\253

SG,,Bi)

identity

thermodynamic

= &S/cB)TdB.

5G,,^,)

for the

Hclmholtz

-SdT

- MilB ,

free energy for

F)
a magnetiz-

magnetizable
substance,

dF

one obtains,

usual

the

by

G)
relation

the Maxwell

cross-differentiation,

(cS/dB)T= {dM/3T)B.
F) to

(8) into

insert

We

the

find

72 The

quantities

at

of M

derivative

no assumptions
therefore

been

7\"

T2anddBzlT

JS =

and

T,

about the

[he

of

ideality

at low

used extensively

with

pressure

Chapter10:

The

AV is

been

temperature

method

substance,

paramagnetic

and
Tm of

temperature

melting

makes
it

has

a sub-

A0)

TmAV/&H

the volume change during

fusion.If both quantitieshave

the

The

measured.

to the Clausius-Clapeyron equationof

p according

dTJdp
where

Tt are known,and

temperatures.

thermometry.

varies

(9)

B, is easily

(c) Clausim-Clapeyron
substance

temperature:

UTQ/<lB)(dM/dT)B.

\342\200\224

at

<fQ

the unknown

for

expression

(8)

melting,

and

AH

as functions

measured

heat of
of pressure, A0) can
the latent

be integrated;

7*2/7,

If 7, andp,
temperature

are

known,

a measure

(U)

cxpJPl(AK/AH)rfp.
men!

T2 is the equilibrium
melting

of the

pressure

temperature

p%

at

which

permits

the unknown
calculation

of

Practical

International

T2 from (U). By utilization

solidification pressureof liquid

to magnetic

low

strong
method

the

^He,

at

thermometry

the

of

Scale

{IPTS)

dependence of the
temperature
lias been used as an alternative

temperatures.

TEMPERATURE

PRACTICAL

INTERNATIONAL

Temperature

SCALE (IPTS)
known

Many

the accuracy

than

precisely

equilibrium

phase

can be

temperatures
their

which

with

reproduced

more

far

scale
facilitate practical thermometry,
location

exact

on the Kelvin

can be
To
by primary
thermometry.
a number of
have been
phase
temperatures
reproducible
equilibrium
determined as accuratelyas possible have been assigned
best values to
define an InternationalPractical
Scale
On the IPTS the
(IPTS).
selectedequilibrium
are
treated
as if their temperatures
were known to be
are
determined
exactlyequalto theirassignedvalues.Intermediate
is chosen
to reproduce
the
by a precisely specified interpolation procedure
true Kelvin scale as accuratelyas possible. present
version
of the scale is
IPTS68, adopted 1968 by international
covering temperatures
agreement,
the
of
tlte
triple
point
hydrogen {13.81K) upward.* Table B.3
determined

easily

and

Temperature

points

temperatures

that

The

in

from

gives

for IPTS68.

temperatures

assigned

In the range between 13.81K

a

antimony,

the

range

from

a platinum-piatinum/rhodiuni

body radiation

903.89

K,

thermometer

resistance

platinum

instrument.In

and

which

melting point of
as the interpolating

is the

is used

1337.58 K., the meltingpoint

1337.58
thermocouple is used. Above

903.89

K. to

of

gold,

black

is used.

Below 13.81

K.

no

precisely

defined

procedure

has been

agreed, In the range

of
scales based on the vapor
pressure
down
to
are in practical
use.
Below 5.21 K, the critical point of 4Hc(
hydrogen
used as de facto
are
about
0.3 K, the 1958 and 1962 helium
scales*
widely
extensions of 1PTS68.
The
1958
4He scale relates the vapor pressure of 4Heto
the
T; the 1962 3He scale uses the vapor pressureof 3He.
temperature
As
of primary
the
accuracy
temperature measurements improves, errors in
to revision
scales
such as IPTS become uncovered, leadingeventually
practical
to exist in
of the practical scales. Table B.3 lists someerrors
now
believed
5.2

between

K.

and

13.S1K.

various

IPTS68.

\342\200\242

Sec,

Hcaf,

for eiampte, American Iniiiiuie

of Physics handbook,
M, W\". Zcmansky,
ciiiiot. Contains complete original

3rd cd., McGraw-Hill,1972;Sectio

references-

e Scales

Tempera

Table B.3 Assigned

temperatures
Pracjical Temperature ScaleOf
Equilibrium

of lhe

lnternalional

I96S

poinl

Substance

Type

in K

in K

13.81

6 B50lorr)

17.042
20.28
27.402
54.361

90.188

\342\200\242>

273.16

exact

373-15

0.025

505-tISI

0.044

692.43

0.066

1235.08

1337.58

for the triple poinisand the 17.042 K point, all

Except
*irc
tHosc
at a pressure of one st-mdarti
fG^mlEoriu
airrio^pncre\302\273
= 760iorr).
isihe
The I7.O42K poinl
p0 - l0J,325Nmwi
<
noi-e:

point ot

boiling

tti

and

lhe

freezing

errors

known

(Dec.
1976).
\342\200\242
Alt

at 25OtOff^ llic notations f, bt and

colurnn refer to uiplc poinis* boiling points,
The lasi column
contains
esiimatcs
of
points.*
to exisr, from Physics Today 29, No. 12,p. 19
hydrogen

second

data

from lhe

American

1972;
3rded., McGraw-Hill.
ediior.

luxituie
Seciion

of Phyws handbook,
4: Heat, M. W. Zcmansky,

Appendix

Poisson

Distribution

ThePoisson

law

distribution

is a

result of

famous

probability ihcory.The result

in
design and analysis of countingexperiments
physics,
biology,
w
e
and
The
statistical
m
ethods
have
research,
operations
developed
engineering.
tend themselves
to an elegant derivationof the Poisson
is concerned
law, which
with
the
of small numbers of objects in randomsampting
occurrence
processes,
it is also called the law of small numbers.
If on
the average
there is one bad
will be found in
in a thousand,
what is ihe probability that N bad pennies
penny
was
first
a given sample of one hundred
considered and
The problem
pennies?
the rote of luck, in criminal and civil law
solved in a remarkablestudy
of
trials
In France
in the early nineteenth century.
We
derive
ihe Poisson
distribution
taw with the aid of a mode* system
that

in tUe

Is useful

and diffusive
large number R of independentlatticesitesin thermal
a
wilh
Each
site may adsorb
lattice
gas. The gas servesas a reservoir.

of a

consists

contact

zero or oneatom.We

that a total of 0,
given

to

want

!, 2,....

find

N,....

Ihe probabilities

are

atoms

adsorbed

number <N> of adsorbedatomsover

the average

ou

the R sites,

v/e

if

are

of similar

ensemble

an

systems.

Consider a system composedofa singlesiie.It isconvenient

energy of an atom to the site as zero. The identical form
found if a binding energy is included in the calculation.

where the term

the

term

! is

probability

is

proportional

proportional
ihat ihe site

the probability

to

actual

the

The

set

the binding
is

distribution

Gibbs

sum is

the site is occupied,and

to the probabilliy the she is vacant.Thus

the

absolute

Is occupiedis

J ~
The

to
for

value of /, is delermined

by

{>
1

ihe

-r

/.\"

condition

of the

gas in the

reservoir,

Distribution

Polsson

for diffusive

because

comae! beivveen i\\\\c

by the argument of Chapier 5. The

We now

of

evaluation

ideal gas

for an

/.(gas)

was

6.

in Chapier

given

we must have

the reservoir

and

lattice

extend [he treatment10R

Then

siics.

independent

(<*)

argument used in

By the

{O +

\302\251)Bor

which

occupied,

/ for

term

site

Each

sites.

lhal

know

1 we

Chapter

once
counts once and only
has two alternative states, namely

+ /.)*

(!

corresponds

in

the

Gibbs

of Ihe

stale

every
O

vacant

for

to the term

sum

expansion of

the binomial

for

system of
or

\302\251
for

X\302\260
and

the

)}.

In the low-occupancylimit of/

\302\253
1

we

fR-

have

s /.,whence

},R

E)

atoms.
average total number of adsorbed
concerned with this low-occupancy
limit.We can

is the

Poisson

The
now

write

distribution

is

D) as

F)

Next we

number

average

concerned
we

let

with

increase without limit, while holding the

is
of occupied
sites <N> constant. The Poissondistribution
function
events!
the
definition
of
the
infrequent
By
exponential

the

number

of sites R

have

exp<N>

JM = exp<N>=

Ttie

last step

\302\253p(;j!)

here is the expansion of the

exponential

G)

(}R)N
(8)

I\342\200\224-

funclion

in a

power series.

The term

in

'/!\"

occupied. With
of large l(:

are
limit

in

lo the

is proportional

3\"^,

the Gibbs sum as the

probability F(A') that

Factor

normalisation

we ha\\c

sites

.V

the

in

C)

or, because/.K

<A'> from

E),

A0)

'

This is the Poissondistribution

Particular

interest

is occupied.

From A0)

to the probability P@) that

attaches
we

P@) =

Thus the probability

law.

find,

=
<N>\302\260

is simply

occupancy

0! =

1 and

logP(O)

exp(-<N\302\273;

zero

of

with

of

none

the

sites

I,

(II)

-<

related to ihc averagenumber

the
for
suggests a simpleexperimental
procedure
determination
of <N>: just count the systems
no adsorbed
atoms.
that
have
Values of P(A') for several
in
CM.
Plots
are
values
Table
of <N> are given
C.I for <N> = 0.5,1, 2, and 3.
given in Figure
(N)

of occupied

Table

C.l

Values

0.1

sites. This

of the

Poisson

0.3

disiIribution

ft inction

PIN)

<N>

\302\253p(-W

>)

N!

0.5

0.7

0.9

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

FB)

0.0045

0.0333

0.0758

0.1217

0.0337
0.0842

FC)

0.0002

0.0033

0.0126

0.0003

0.0016

f@)

W)

0.0002

P{5)

0.1647 0.1839 0.2707 0.2240

0.0613 0.1804 0.2240
0.0284 0.0494
0.0153 0.0902 0.16S0
0.0050 0.0111
0.0007
0.0031 0.0361 0.100S
0.0020
0.0001

PG)

0.0003

0.00050.0120 00504
0.0001

F(9)
1

0.1465

0.140
0.1954 0.175

0.1954

0.1563 0.17
0JO42

0.0216

0.0595

0.0O09

0.0081 0.0298

0.0002

0.0027

O.OI32

0.0008

0.0053

0.0034

0.14
0.10
0.06
0.03

0.0S

Tisttibuti

0.6
=

(N>

<,V> = I

0.5

gO.4

0.4

0.2

0.2

0
)

s
)

\302\2430.2

LLjl

Example:Incorrectand

correct

counting

Jwi = 1

of states,
+

)}

(a) The Gibbssum

+ -I3

4- - '

for

the

R sites is nai

' + )*.

{12}

noi?

Why

(b)

suns is

Thccorrcci

A3)

Ji!
[R - W N!

is

lilc

system for a

given

Example: Elementary

number

that tjill.V) is Ihc number of

adsorbed
alor.is .V. The Gibbs sum

Nolc

cocflicicm.

binomial

of

demotion

randoln among L dishes.Each

dish

of P@).
is viewt

I.ei a Iota! of
j as a syslen: of

R
many

states

independent

is a

bacteria
siles

of Ihe

sum over ail stales.

be distribulcd
10 which

at

a bacterium

PohsonDhtributior.
dishes represent an

aiiach.TlieL

may

per dish is

of bacieria

ensemble of Lidcnticalsyslems.
The

number

average

<N> \342\200\224
R/L.
a bacleriumis distributed, ihe

Each time

The probability

is t/L

bacterium

[he

receive

not

will

dish

a given

that

probability

dish

given

{14}

will

the bacterium

receive

thai

is

A5)

The probability

in R

tries lhat

the

dish

given

will receive

~~Y

/><0)

no baderia is

A6)

(l
the

because

(i 5)

faaor

eniers on eachtry.

Wemay\302\253ri(e(l6)as

(.7,
lW-(l
by

use

of<.V>

= R/L.

We know iliai

-<\302\243>)'.
Hie

in

lirail

of large R,

rap(-<N\302\273= limfi

!>y

llie

of Ihc

Jcrmilion

cxpoocnlu! funclron. Thus for

P@)

in aercemcni

wjih

A8)

-\342\200\224)

\302\273
I and

\302\273
I we

have

A9)

cxp(-<N\302\273

(U).

PROBLEMS

/.

Random pulses.

counteda!

an

average

radioactive

rate

of Oiie

counting exactly iO alpha particlesin

in
5 s? The answers
to (a) and

none

source

emus

alpha

per second, (a)

5s?(b)Ofcounting2m

{b}are

not

identical.

What

particles
is

the

which arc

probability

1 s?{c)

of

Of counting

2.

Approach

to Gaussian

\342\226\240(N>'\"'exp{ \342\200\224<W)}/A'!

large

(A'>.

That

distribution.
approaches

closely

is, show when N

PIN)

Showthat

a Gaussian

k closeto <;V>

Aexpt-tyS

the

Poisson

function

function

P{N) ~

in form,

for

thai

- (N}I] ,

to be determined by you. Hint: Work with !oeP{A?};

A, B are quantities
use the Stirling approximation.In the Gaussian
form both A and B are functions
of <N>; in the development of the Poissonfunction
find A, B are
may
you
functions of N, but the two forms of A, B are closelyequivalent over the range in
which
the exponential factor has significant
values.

where

Appendix

Pressure

Let a pressureps

be

liquid in quantum

to ihe

normal

applied

state s.

mechanics

elementary

By

faces of a cube filled

3} the

{Chapter

or

a gas

wilh

pressure

is equal to

Pl~ -dUJdV ,
where

Vs

is tlie

of the

energy

{1}

system in the states.We

also

can

write

the pressure

as

Plwhere

ihe

denotes

(dU/,tV),

expcciaiton

volume

y. Ii

is important that

volume

with

no

we

about

ambiguity

~(dUJdV\\ ,
can

B)
dUfdV over the siatc
p by {2} which is at a

value\" of
calculate

the identity of the

selected

state

s at
fixed

5. whereas

V + dVt with
Kand
some
two
volumes.
following the state through
doubt
whether the state remains ihe same.The ensemble
average
in
is
the
of
over
the
states
the
ensemble:
p
average
p,
represented

(!) involves
possible
pressure

C)

f>W--(Wl,>

Because
the

so that

number

of states

the derivative

in the

ensemble is constant,

is at constant entropy.We

may

the entropy

therefore

is constant,

write

as V(a,V,...};
that is,
D) uses the energy of the system
expressed
a
V
a\342\200\224not
the
function
of
the
volume
and
the
r. It is
as
temperature
entropy
be held constant
to
in
the entropy and not the temperaturethat
is
the

The result

differentiation.

\342\200\242

The

equivalence

of (t)

to a parameter
p. 1192of C. Cohen-Tannoudji,
E. Merzbacher,Quantum
resped

and

X are

B)

is an

example

of

quantur

=>
be found
o
The derivation may
dVfdX
<|A*7<*A|).
and F. Laloc. Quamum
mechanic*,
Wiley, [977; see als
2nd ed., Wiley, 1970; p. 442.

related

by

B. Diu,
mechanics,

of ihe Hellmana-Feynman theorem

Appendix

Temperature

Negative

The

energy
which

in

2.2 for

Problem

of

result

field

magnetic

is negative

Ca/cV)s

of the upper state ts

obtains

condition
Figure

the entropy of a spin system

here in Figure E.I.

is plotted

(Figure E.2).Negative
the population

than

greater

the

we say that

r means

of the

of the

a function

as

Notice

the

that

in

region

the population

lower state. When

population is inverted, as

illustrated

this
in

E.3.

The concept of negative lemperaturets physically

for a system
meaningful
be a finite upper limit
that satisfiesthe following restrictions:(a) There
must
to
the spectrum
of energy states, for otherwise
at a negative temperature
a system
would have an infinite
A freely moving particle or a harmonic oscillator
energy.
cannothave negative temperatures,
for there is no upper boundon theirenergies.
Thus
certain
of freedom of a particle can be at a negative
temperaonly
degrees

\\
\342\226\240

\\
jr

Figure E.1
The

scparaiion

\\
r = -0\\

= +0

0.2
Entropy

of the

0.6

0.4

as

funciion

0.8

1.0

of energy for a iwo siaic sysicm.

In ihe
I in ibis example.

siaiea is c ~

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

+4
/

+3
+2
K

-f

Migy

.\342\200\224\342\200\224
\302\2610
\302\247
5

o 2

0.6
1

-\342\226\240

0\342\200\224\342\200\224

0
^1

-1

-3

!/

-4

_5

E.2

Figure

Noiice
but

is 3

versus energy for

Temperature

stale system.

Ihe two

Here

energy is not a maximum

maximum al i = -0.

tiiai ihe

at

x ~

+ x,

magnetic field is ihe degreeof freedom

most
considered
in experiments at negative temperatures,(b) The
commonly
must be in internal thermal equilibrium. Thismeansihestates
must
have
system
in
for
accord
with
the
taken
the
Bolumann factor
occupancies
appropriate
are
at
be
The
states
a
must
that
negative
temperature,
(c)
negative
temperature
arc at a positive
isolated and inaccessible to those states of the
that
body

ture:

the

nuclear

spiu

in a

orientalion

temperature.

The

ordinary

have an entropy

translations!

and

vibrational

degrees

of freedom of a

body

the energy increases,in contrast

to the two stale or spin system
of Figure
E.I. If a incieases without limit, then i
is always
The
of energy between a system at a negative
positive.
exchange
a
nd
a
that
can
of
temperature
system
only have a positive temperature(because
that

increases

without

limit as

Negative

Temperature

E.3
Possible
spirt distributions for various positive and
fietd is direcied upward. The
negative tempera!ures.The magneiic
Jasi indefinitely
because of weak
negative spin temperaturescannot
coupting betweenspins and the lattice. The lattice can oniy be at a
level spectrum
is unbounded
positive temperature becauseils enefgy
=
on top. The downward-directed
i
turn
over one
as
at
spins,
\342\200\224r^,
Figure

by one,

hereby

equilibrium
nuclear

over a

spin
time

releasing
energy
the lattice
a! a

of

minutes

or hours;

negative temperaturesmay

an unbounded

to

the

lattice

and

approaching

common posiiivctemperature.
at
system
negative temperature may reiax qutie

with

spectrum)

will

during

be carried

iead

always

this

time

experiments

slowly,

at

out.

to an

equilibrium

configuration in

are
which both systems
at a positive temperature.
than
Negative temperatures correspondto higher
energies
temperapositive
a
temperatures. When
a system
at a negative temperature is brought into contact with
at
the
a positive temperature, energy will be transfused
from
system
negative
to
the
hotter
are
temperature
positive temperature.Negative
temperatures
than positive temperatures.
H- go
The temperaturescalefrom coid to hot runs + 0 K,.... 4- 300 K,...,
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
is not 0 K, but is \302\261
co K.
temperature
to negative
and
electron
Nuclear
temperatures
spin systemscanbepromoted
is
resonance
by suitable radio frequency techniques.If a spin
experiment

out on a

carried

spin

at

system

temperature,

negati\\e

energy is obtainedinsteadof resonant

system is useful
be

as

an

absorption.*

in radio

rf amplifier

resonant

emission of

negative

temperature

astronomy where weak signalsmust

amplified.

have carried out an elegantseriesofexperiments

on
with
at
with
a
LiF
calorimetry
negative temperatures.Working
crystal,
systems
they established one temperaturein the system of Li nuclear spins and another
field
temperaturein the system of F nuclear spins. In a strong staiic magnetic
the two
in the
thermal systems are essentially isolated,but
Earth's
magneiic
field the energy levelsoverlapand the two systems rapidly approach equilibrium
It is possible
to determine the temperature of ihc
among themselves(mixing).
the
after
and
Proctor
before
and
systems
systems 3re allowedto mix.Abragam
that if both systems were initially
at positive
attained
found
temperatures
they
tnto
thermal
contact. If boih
a common positive temperatureon being
brought
at
systems were preparedinitially
negative
temperatures,
they attained a
Abragam

and Proctor*

into
contact,
if
common negative temperature on being
thermal
brought
at
the
at
other
a negative temperature,
prepared one a positive temperatureand
on mixing,
warmer than the
then an intermediate temperaturewas attained
the
initial
initial positive temperature and coolerthan
negative
tempcraiure.

REFERENCES

FURTHER

ON NEGATIVE TEMPERATURE
N.

F.

temperature,\"

Physical

M. J.

Review

103,
temperature,\"

M. Puicelland

A. Abragam

R. V. Pound,

mechanics at negative absolute

20A956).

Klein, \"Negativeabsolute

\342\200\242
E.
1

and statistical

\"Thermodynamics

Ramsey,

Physical

Physical

Review

81,279 A951).

and W. G. Proctor,Physical

Review

106.16Q(l<>57);

Review

104, 5S9

109,1441 A958).

(i956).

Index

Abraham, B.
Absolute

463

350,

H..

Abragam,

Hiack

139

activity,

Bolununn

97

Acceptor,

357, 363

Bolutiminn

Born, M..

Accessible state, 29
Activation

reactions,

energy,

Active

Air

Sun, Hi

gold

in

distribution, 157, 159

mixing energy, 3IS.33O

solidification ranee, 33!
16

system,

A.

Anderson,

Atoms,

velocity
Average

199

205

a box,

one

222

222

dimension,

279

P. W.,

Bridgman,

CMN, 348, 448

Carbonmonoxidepoisoning,i46
Camot coefficient,

126,145,179

Atmosphere,
in

C, 219
142

E..

Amonini,

gas,

Boson system, 223

331

silicon,

Camot
394

distribution,

value, 22

cycle, 236

ideal gas, 237

Camot

efficiency, 230

Carnot engine,photon, 258

Camot inequality,
Carnot

Barnes,C. B.,345
Barometric

pressure,

Bertram,

Carrier

electrochemical,

B., 210

Binomial

BiopoJynwr

22

14
growth,

273

scate,

temperature

Centrifuge,

systems, 10

distribution.

expansion.

Catalyst. 271
Celsius

16,310.331

alloy,

Binary model

362

3SS

lifetime.

Carrier recombination, 383

129

Belts, D.S.. 342

Binary

232

228,

Jiqucfier, 351

Carrier concentration,intrinsic.
125

equation, 126
Battery,

449

thcrmomctry,

Ihermodynamic

345

I A.,

234

performance,

refrigerator

74

Avogadro constant, 2S2

Barclay,

202

Condensate,

Bose-Einstein

fluctuation,

331

!6, 310.

binary,

403, 42!

degenerate, 221

235

258

room,

equation.

tOfi

condensation,

conditioners,

Alloy,

transport

446

Bose-EinStcin

Boson

Age,

4i, 45,

Boson,152

145

transport,

constant,

Boiizmann factor. 58, 61

Absorption refrigerator, 25S

Absorptivity,

98

body radiation,

Bockris,J. O. M.,248

M.. 209

4-15

145

Cerium magnesium nitrate,

M, 350
Chapeiiier,

348,

Chauikasekhar limit,

222

Characteristic

atmosphere,

Cliau,

V. H.,

height,

350

448

\\26

Chemical equilibria, 266

Chemical
potential. 118, JJ9, J43, J61
and entropy, J3I
equivalent definition, J4S
external, J49
ideal gas, J20, J69

van

reaction,

Chemical

work,

DNA

281

234

4!3, 421

electrical,

thermal, 401,421
probable, 33, 35

equilibrium, 179
Cooling, demagnetization, 352
.

259

Critical

magnetic

isenttopic, 346
nuclear, 348

Density

of orbitals,

Density

testates,

187,218
186

360

in semiconductors,

360

mass,

407

84

180

engine,

current flow, 379

equation, 437
fixed

boundary,

heat,

437

429

internal

heat

particle,

399,409

Dilution

98

radiation,

253

120

428, 437
helium,
refrigerator,
399,

Dispersion

290

437

sources,

relation,

law of,

field,

365

352

cooling,

Demagnetization,

DtlTustvity,

Countcrflow heat exchanger,336

,.

355.

437
p-n junction,
Diffusive equilibrium,

of slab, 437
Cooper pair, 250, 257

Cosmicbackground

Degeneratesemiconductors,

Diffusion

387

states,

219

!82

Differential relations, 70

electrons,

Corresponding

gas,

Diesel

semiconductors,355

solid,

Fermi gas,

Degenerate

54
Deviation, integrated,
Diatomic molecules, rotation,

Conduction band, 355

nonmctallic

105

Detailed balance,kinetics,
principle of, 271

415

34t
evaporation,
external
work, 334

348

Degenerate

effective

416

most
Configuration,
Convectivc
isentropic

G,

effective,

303

hole,

S3

molecule,

Debye theory, 102

phase,

intrinsic,

298

Dcbyetemperature,

351

Cohen-Tannoudji, C.,459
Collision cross sections, 395
Collision rates, 395
Concentration
fluctuations, 147

Conductivity,

319

mixture,

de Bruyn, R., 345

De Maeyer, L., 270
T1 Saw, 106
Debye

160

Cohen, E. R.,446

Conduction

307

transformation,

Daunt, J.

Closed system, 29
Coefficient,
refrigerator performance,
viscosity, 402
Coefficient,
Coexistence
278
curve,

tube,

333

Crystalline

410

Ciausius-Clapeyron
equation,
Clayton, D. D.,222

Conductance,

340

A. J.,

250

liqucfier,

Condensed

276

Curie temperature,
Cycle, Carnot, 236

Classicalregime, 74, 153,159,358

Claude cycle, 341
helium

size,

Crystal

J6J

function,

Critical

2%9

295
nucleation,
nuclear
reactor, 437

Cryogenics,

266

idea! gas, 25!

Classical distribution,

Classicallimit,

radius,

Croft,

mobile magnetic particles,J27

near absolute zero, 199
loiaj. 122. J24
two phase equilibrium,
330
Chemical

Critical

Crilical temperature,
gases,277

12-4

J22,

internal,

291
point,
dcr
WaaJs gas,

Critical

342

425

Distribution, classical,161,410
Base-Einstein,
Fennt-Dirac,

Dju, B., 459

158
154,411

Dixon,R. W.,

Entropy, 42, 45, 52

366

356, 363

Donor,

and

Donor impurities,
Doping profile,

375

270

lapse rate,

now, 44

heat
Earth,

law

Eddy current equation, 425

Effective

mass,

Effective

Carnot,

Eigen,

M., 270

Einstein

Electrical

406

388

84

polymers, 86
413,

conductivity,

98

Electrochemical

battery,

247

Electrolysis,

380

mobility,
R.

EHiott,

323

P.,

Energy, conversion, 240

efficiency,

degenerate

boson gas, 221

77

113

83,

259

334

engine,

gas, 259

Fertitt

irreversible, 175

264

quantities,

particles, 117

rdativtstic

Extreme

Extrinsic semiconductor,364

420
mixing, 314, 330
kinetic,

thermal

227

van der Waals

gas,

systems,
der

305

31,62

32

31
Waals

gas,

Irreversible

liquid

Ensemble, average,

Enthalpy, 246,

155, 183

183

222

ground slate,

355

construction,

Fermi

fluctuations,
62

gap,

148

Fermi energy,

system,

state

G.,

Feher,

140

average,

transfer,

van

341

cooiing,

352

252

magnetic,

mean

Energy

Euteclic, 325

Extensive

ideal gas, 76

two

77

429

function,

isothermal.171

gas, 185

geothermal,

268

Expansion, cooling, 334

230

conversion

fluctuations,

291

constant,

Equipartition of energy,

limit,

equiparijtion,

330

pressure,

vapor

Evaporation

Etnissivity, 97

Fermi

reactions,

Error

excitations, 212

Elementary

274

266

Equilibrium

Electron-hole pair generation, 388

Electron

gas-solid,285, 305
two phase,

129

287, 289

269

hydrogen,

Equilibrium,
panidc-anttpartide,

421

Waais,

322

phase,

Electrical noise,

424

Equation of stale, van dcr

chemical. 266
Equilibria,
\"

205

solids,

gas, 305

of continuity.

Equation

199

temperature,

Elasticity of

52

227

van der Waals

230

high electron concentrations,

Einstein

114

transfer,

relation,

178, 314

78,

temperature,

246

condensation,

Einstein

50

and occupancy,

and

temperature,

54

increase,

of mixing,

362

360

EfTcctivc work,
Efficiency,

of

as logarithm,

361

of stales,

density

valence band.

2j9

gas,

165

fr\302\253energy.

Sun, 111

from

distance

131

poicniiai.

degenerateFermi

383

adiabatic

Dry

chemical

conventional, 45
degenerate bosongas, 221

273

tonization,

concentrations,

Doping

229

accumulation,

levels,'369

185

expansion.

hdium-3,

259

219

metals. 194
relativistic,

218

level, 155,357
intrinsic, 362

Fermi

284
gas, 305

extrinsic semiconductor,364

Gibbs free energy,246, 262

van dcr WaaU gas, 291
Gibbs sum, 134, 138, 146
ideal gas, 169, 180
two level system, 146
R. R., 103
GifTard,
Goldman,
M., 350
Grand canonical distribution,

411

177,

153,

(unction,

distribution

Fetmi-Dirac

Fcrnfi-Dirac

366

integral,
152

FcrmtOil,

Fer to magnet
First

law,

First

order

302

295,

ism,

Pick's law,

399

49

302

transition,

Grand partition

hole, 415
through
through
tube, 416, 421
speed, 422
Bose
Fluctuations,
gas. 222

Flow,

Grand

138

138

function,

138

sum,

Greenhouse eflect, 115

Guyer, R. A., 210

147

concentration,

83, 113

energy,

Fermi gas, 222

of,

time
Flux

178

Fourier analysis, 436

Ha|I-Shockley-Read
theory,

law, 401
163
energy,
262

246,

Gibbs,

harmonic oscillator, 82
paramagnetic

system,

photon gas, i

12

Free

69

8i

energy
function,
J. S., 142

Landau,

298

247, 248
Fundamental assumption, 29
Fundamental temperature, 41
Gallium arsenide, semt-tnsulating,
Gamma function
integral,
critical

electron

372

440

277

boson, 221
Fermi, 219

86

potential

energy,

145

quantum,

182

Gauss

two

state

Helium

system,

integral, 439

dectron-hoic

Geothermal

energy,

259

t67
134,

counter Row,

336

34S

dilution

pair, 3S8

Heinegroup,

refrigerator,

dec eneray,

6S

140

Hemoglobin.141
D. G., 216
Heitshaw,
vacuum region,
Hill, J. S., 34S
High,

I3S

424

115

Helmholu

20

Generalized forces,404, 405,453

Giauque,W.,

62

Helium liquerler, 351

Generation,

U3

113

reflective,

equilibrium

Gibbs factor,

intergalactic
space, N3
113
liquid helium-4,
and
photons
phononS,

Hecr, C. V.,

430

Gaussiandistribution,

221

Heat flow, 44
Heat transfer, sound wave, 434
Heat pump, 235, 257
Heat shield, 112

rarefied, 413
waves,

gas,

189

Heat exchanger,
337

liquefaction,

Gas-solid

gas,

Heat conduction
equation,
230
Heat engine,
228,
refrigeratorcascade,258

182

one-dimensional,

sounii

boson

degenerate

72

ideal,

63, 165

capacity,

solids,

temperatures,

degenerate
degenerate

Heat

ice, 305

of

vaporization

'

Gas constant,166
degenerate,

isobartc, 245
path dependence,240

...

Fuel cell,

Gas,

227

definition,

two state system,

24

function,

multiplicity

Harwit, M, 219
Heat, 44,68, 237, 240

Helmholu.68

Fmlon,

383

Hansen. M., 323

Harmonic oscillator, 52, 82
free energy, 82

Fourier's
Free

131

Half-cell potentials,
Hall, R. N.. 385

397

density,

397

342

Hobdcn.M. V.,349

Isothermal work, 245

415

concentration, 361

Hook,J. R.,217

James, H. M, 86

}., 342

Huiskamp,

W.

Hydrogen,

equilibrium, 269

H.

305

vaporization,

van

72, 74, 160,169

251

work,

Kelvin

76

Kinetic

iscntropic relations, 179

law,

446

Kirchhoir

law, kinetic

theory,

therm

Impurity

177

atom

Increase

Lambda

of entropy,

law

of,

Landau

45

Landau theory,

Carnot, 232

Internal chemicaipotential,
International

Scale, 451

Fermi level,

donor

362
3S8

143

45
increaseof entropy,
of mass action, 268, 362,
of rarefied gases, 413

Laws

Lcln,

A. J.,
W.

H-,

217
195

339
Liouville theorem, 40S

232

sources,

Irreversible thermodynamics,406

Irreversiblework, 242

346

Iscntropic

expansion,

114, 148

Iscntropic

helium

11, 209

rclalioos,

phases,

supcrliuid

Isentfopic process,173

isobaric process, 245

Liquid

Liquid heIium-3,

Isemropicdemagnetization,
ideal

290

Liquid

hdium-4,

Liquid

3He-4He

217
217

207

heat capacity, 113

gas.

179

mixing energy,

382

48, 49

of thermodynamics,

Linde cycle,

269

Irreversibilily,

states,

corresponding

Legged,

thermal, 273
water,

of

Leff, H. S-,259

273

alum,

45

of entropy,

vaporization,2SI

Laws

deep impurities,
impurities,

impurily

increase

Law

336

temperature,

3S8

284

284

enthalpy,

Law

conductivily,

381,

heat, 281,

298

isotherm, 145

Law of

387

Intrinsic
lonization,

113
124

122,

Practical Temperature

Intrinsic

Inversion

Laser,injection,
Laiem

heat capacity,

space,

Intergalaciic

439

264

298

transitions,

phase

Langmuir adsorption

exponentials,

comaining

Intensive quantises,

210

poinl.heIium-4,

free energy function,

function, 69, 298

Laudau

383

Injection laser, 381,38S

Integrals

348, 349

LaioS, F-, 459

143

ionization,

recombination,

Inequalily,

N-,

Kuril\",

C, 114

180

Impurily level, 368, 383

carrier

397,413

regime,

Kramers, H.

identity,

odynamic

two dimensions,

96, 115

law,

Knudsen

243

expansion,

270

Klein, M. J., 463

391

86

one-dimensional,

mass action,

model,

Kinetictheory,
ideal
gas law, 391
Kinetics, detailed balance,407

77

sudden

41

temperature,

Kinematic viscosity,404
179

of freedom,

degree

Kelvin,

366

approximation,

scale, 445

Gibbssum, 180
internal

gas, 338

366

8-,

JQttner, F.,219

chemical potential, 120,169

chemical

W.

Joyce-Dkon

cycle, 237

energy,

effect, 337

Waais

dcr

Joyce,

ISO

calculations,

Carnot

167

L.,

Joule-Thomson

of

heat

98

Johnson noise,

IPTS,451
Ideal gas,

B., 98

J.

Jfohnson,

Johnston,

Ice,

143

adsorption,

Langmuir

conductance,

quantum

276

Isotherm,

177,355

Hots,

mixlute,

330

320

Uquiduscurve,

323

Lounasmaa,

O,

Low

orbital

free

Low

temperature

semiconductor, 358
Nonequiiihrium semiconductors,379
Normal phase, 203
Nuclear demagnetization, 348

Nondegenerate
201

atoms,

448

thermometry,

Magnetic

concentration,

Magnetic

difliisivHy,

145
437

425,
253

energy,

Magnetic

Nuclear matter,
198
Nuclear reactor,critical
Nucieatton, 294
critical radius, 295

394

J. H.,

McFee,

G., 114
N'iels-Hakkenbcrg.C.

ill

B.,

Lyncis,

-Never,\"

342

V.,

Mapiciic field,

81

susceptibility.

Magneticsystem,

23

252

work.

Magnetic

Mass action, law,

oS^ZlZl^

distribution

Maxwell

relation,

Maxwell

transmission

of velocities,
272

71,

distribution,
distribution
393
velocity
288
method,

Maxwell

Mean field
Mean free path, 395
Mean speeds,Maxweilian
Mean value, 22
Mdssner effect, 252
Merzbachcr, E., 459
Metastable phases, 278

Ovcrhauser efTeci,K4

362, 387

270,

268,

Maxwell

392, 419
395

Paramagnetic system, 69
52, 446
Paramagnetism,
Particic-antipartide
equilibrium,
Particle diffusion, 399, 409
Partition
function, 61
two systems, 85
Pascal
(Pa), back endpaper
240
Path dependence,

419

distribution,

Minority

carrier

Mixing,

energy,

Penetration, temperalure
Pcnnings, N. H., 345
Peritectic systems, 330
Perpetual motion, 50

320

equilibria,322

322

normal,

Mobile magnetic particles,

chemical potential, ]27

relations

Molecules,Earth's
probable

Multiple
Multiplicity,
Multiplicity
harmonic
-

Myoglobin,

binding
7

configuration,
of Oa, 148

helium,

210

321

superconducting,306,307
Phenomcnologicailaws,398
254
Phillips, N. E-, 195,196,

33, 35

102
beat capacity,
mode, 104
\"

Phonon,

function,
oscillator,

140,

of

Phase Iransitions, 298

Landau
Iheory, 298

145

atmosphere,

Monkey-Hamlet,53
Mosl

203

Phase diagram,

380

electron,

Mobility,

203

condensed,

equilibria,

phase

426

Phase,267

319

liquid 3He-4He,

oscillation,

pH, 269

578,314

Mixture, binary, 310

crystalline,

274

152

principle,
336

effect,

Peltier

lifetime, 3S8
3S4, 330

78,

entropy,

exclusion

Pauli

L-, 215
J. H., 34S

Meyer,
Milaer,

369

levels,

Onsajcr relation. 406

fVhhii 9 lV>
Spl,^ ' J

253

in superconductors,
MaSn\302\253ic

Occupation<W

170

entropy

93

theorem,

Nyquist

437

size,

147

of Oj,

adsorption

mobile magnetic particles. 127

spm

460

temperature,
53

Negative

Long tube, Row, 416

Loschmidt number, 396

142

15, 18
'
'
24
\342\226\240
\342\200\242
'.

\342\226\240'
'.
.

solids,

102

113
'\342\226\240
\342\226\240
;

Carnot

Photon,

258

engine,

heal

Read,

thermal, HO
Photon gas, 112, 114

Reese,

one dimension.

89,

function,

91

403

I'ound, R. V., -563

balance, 271

30

463
Proctor,
sound
waves,430
Propagation,

Sackur-Tetrodeequation.77, 165

Semiconductor. 353

degenerate,358,365
donor

73, 85

concentration,

36!

n~ and

JS2

gas,

Quantum

icgime, 182

Radiant

object, 114

fiux,

Shockley.W..
F. A.,

gallium arsenide.
385

323

Simmonds. S., 142

114

R., 425

W.

Smythe,

Soilj temperature

Radiation

background,

98

thermal

thermal, 111

Solar

Ramsey, N. R, 463
Rarefied

379

Semi-insulaiing
Shunk,

energy

358

nonequihbrium,

212

gases,

Reaction,chemical,

laws of,
266

143

p-type, 363

nondegenerate,

379

Radiant

iontzation,

atom

impurity

Quantum

273

impurities,

extrinsic, 364

holes,36!

body

304

331

coefficient,

Segregation

conduction electrons,

black

63

240

Second order transiiion,

Puree!!. E. M., 463

Quasi-Feimilevel,

167

tests,

148

law, 49,

Second

speed. 457

Quasipanicte,

molecules, 84

diatomic

Schotiky anomaly,

457

Quantum

34S
142

A.,

experimental

427

development.

Pump,

S. S.,

Schindler, H.,

Fourier analysis, 436

random,

253

I(J7

K.,

ill

jadiation.

W. G.,

Pulse,

64

gas. 2!9

of detailed

Probability,

process,

expansion. 171

air conditioner.

Rotation,

Fermi

thermal

Principle

Reversible

Rossi-Fanctti,

Pressure. 64. 164

377

junction,

isotherm^

Roionbliiiii.

34g

degenerate

222

58

Rose,W.

460

inversion.

W. P..

433

Reversible
Room

86

elasticity.

21

gas,

dwarfs.

Reverse-biasedp-n

25S

86

Population
Pratt,

Fermi

white

Resistivity. 387

455

tlicnniil.

Potjmer,

Relativistic
Relativistic

Reservoir,

equation, 375

Pollution,

Rcif. F.,215

time,

138.453

Poisson distribution.
law,

342

in, 259

bulb

Relaxation, thermal, 432

reverse-biased,377
distribution

234

helium dilution.
light

Planck distribution
Planck law, 91, 95
p-n junction, 373

234

coefficient.

coefficient,

112

H-, 111

Poision

W., 219*

Carnol

expansion, 114

iscntropic

Poise.

3S5

T.,

Refrigerator performance.

II2

energy,

Pillans.

W.

113

capacity,

free

raw, 371

Reaction

condensation, 321

413

variations, 437

diffusivity,

constant,

427

110

Soiidificaiionrange, 331

Soljduscurve,
Solubility

gap,

323

310, 311

372

Soliduscurve,

323

phase diagram,
Sound

32 i

Thermal

434

430

propagation,

Spin excess, 14

Thermal
Thermal
96

Stefan-Bo!tzjaann

constant,

Stefan-Boltzmann

law. 91,

Stcycrt,

19, 441

Stirling approximation,

Stokes-Ein
stein
O.,

Stmve,
Sudden

94

A., 343

W.

404

relation,
Jl

ideal gas,

expansion,

243

175

vacuum,

Thermal pollution, 258

radiation,

Thermal

relaxation,

temperature,

aad radius,

I j

Thermodynamic
Thermodynamic

identity,

Tliermodynamic

tbermometry,

449

superconducting

Thermodynamics,
306

447

Torr,4J4

1 iO
temperature,
transition,
Superconducting

Superconductor, 252

Triple point, 284

nugnelic,

8!

Teelers, W.

345

v.

critical, 276

van

Earth's surface,

JU

97

effective density of slates, 362

der Waals gas, critical points,

4!

enthalpy,

305

helium,

oscillation,426

Joule-Thomson

445

350

effect,

338

Vapor prcsiurc, equilibrium,

Sun's average,

I! 1

Sun's

HO

surface,
in

2S9

305

negative, 461

variations

413

355

band,

equation of stale, 287, 2S9

Gibbs
free energy, 291

4!

fundamental,

106

Karman.T.,

energy,

of surface,

estimation

of, 110

:erse, entropy

Valence

41

Temperature,

62

capacity,

Vacuum physics,

259

D.,

licat

Un

446

B. N.,

62, SI

system,

free energy, 81

Swcnson, C. A., 2J0

Tacoais,K. W.,

stale

Two

19

Susceptibility,

S6

R. G.,

L.

Treioar,

Superheating, 278
Superinsulation.

processes, 397

Transport

212

Superfluidity,

distiibutton.

395

Maxwell,

217

phases,

Supctfiuid

302

order,

304

second order,
Transmission

278

Supercooling,

first

Transitions,

306

252

work,

magnetic

scales,

177

133,

67,

relations 71,272

Throughput, 415

Ji

surface

Kelvin,

432

Third law, 49

interior

Taylor,

J J J

Thermal

Thermometers,
I i i

mass

272

110

photon,

transition,

Sun

age,

272

expansion,

Thermal ionization of hydrogen,

37. 52

248

Srinivasan, S.,

36

values,

10,

36, 39

Thermal equilibrium,

aclditivity, 53

Spinsystem,

425

427

soil,

170

entropy,

33, 37

contact,

Thermal diflusivity,

lube, 422
Spin

401, 42j

421

Thermal

Speed, pump, 417

62

average,

Thermal conductivity,
metals,

63

heal,

Specific

426, 437

Jieal transfer,

wave,

oscillation, penetration,

Temperature

311

gap, 310,

Solubility

soil,

Vapor

pressure

Vaporisation,

437

ice, 305

291

equation, 276,
latent

heat,

231

281

Velocity of sound, 432

Viiia

theorem,

A. D.

Woods,

Sll

Work,

Viscosity, 402

227,

chemical,
constant

calculation

of dT/dp,

ionization,

269

305

Wheatley, J.C.,
While

dwarf

star,

mass-radius

J., 114

J.,

219

240

dependence,

196

relationship, 2!9

Wicdemaim-Franz ralio, 42!

Wilks,

path

217

222

relalivislic,

Wiebes,

245

magnetic, 252

148

M.,

245

isothermal,

Weinslock, B., 209

Weissman,

227

irreversible,242
isobaric,

A., 103

245

temperature,

definition,

Water

R.

251

constant pressure, 245

kinematic, 404

Webb,

B., 216

240

Zemanskv,

Zerolh law,
Zipper

M. W.,
48

problem,

Zucca, R.,

373

85

279, 45

Ga

ZJ6'\"Y

Unit conversions
Energy

leal
I

cV

kWh

lO'erg

B 4.1S4J
=

1 BTU

hp

kcal

a 1055J

l<r'2crg = 23.061

10'J

3.6 x

Power
I = 1 Js\021
-

= 1.60219 x

x IO'\"J

1.60219

746

s 1
=

550

lO'trgs\021
ft

lbs\021

O.Oi

mbar

7.501

Pressure
1 Pa

= 1 N m~2

10\023 bar

s;

=s 10 dyn

cm\022

10\"JmmHgorlorr

~ 750 mm Hg
a 10'dyn cm\021 \342\200\242=
10'Nm\022
1 raraHgsa 1 iorr= 133.3Nm\023=
1333dyn cm\023

i bar

1 aim

\342\200\242

Al 0'C

760 mm

1,013

where ihs

Hg = 1.013x

x 10s dyn

cm\022

accelerationof gravity

10s

Nm\021

1.013 bar

has

Ihc standard

value 9.8066S in

s\021.

mol'

Table

Quantity

of Values

of light

CGS

Value

Symbol

T1S~1'

2.997925

I0l0ci

Proton cbarge

J. 60219

__\342\226\240

4.80325

[Q-1Q

esu

Planck's constant

io-1T

ergs

10\"iV

ergs

Velocity

number

Avogadro's

mass

Alomic

mass

Proton resl

mass

Proton

consiani

e1/mc2

Electron Compton
radius

h^/me1

Bohr raagnelon ehjlmc

constant

Rydberg

1O-\"JS

10\"*\"

137.036

10~27

kg

10-\"ks

lo-\"kg

\342\200\224

\342\200\224

r.

2.81794

10\021;'cm

3.86159

10\"\0211

r0

5.29177

10\"9

1'*

9.27408

10\021 lergG~'

10\0234JT*

R^ or Ry

2.17991

10\"' 'erg

10~18J

cm

10-** m

10\"IJm

hjmc

wavelength

Bohr

IQ-l*Js

hefe*

radius

Eieclron

1-67265

l/\302\253

}0~2i S

1836-2

fine structure

Reciprocal

. 10\"\"

9JO953

108ms-'

!0IJmor

1,66057

mass

mass/electron

6.02205

amu
m

unit

rest

Electron

hj2n

6.62618
1.05459

St

meij2hl

cm

10\"\"m

13.6058 eV

I eieclron volt

Boitzmann consiani
of free

Permittivity

Permeability
Molar

gas

Molar volume
TQ

= 273-15

po =

1.60219

eV/ft

2.41797x l0uHz

eV/?,c

8.06548

eVA-fl

1.16045

k.

1.38066

10\"' *erg

10* K

e0

space

of freespace

constant

eV

\342\226\240

\342\200\224

fo

Nka

l0*c;

iCl'm-'

\342\200\224

\342\200\224

10\"\"'

sergK-'

|0-..,ri

iO'/^nc2

x
4\302\253

103c

22.41383

lO^rn'mo]

K,

= laliTl
10132SNm\"I

Source: E. R. Cohen

and

B. N.

Taylor,

Journal

of Physical

10\"

107c

8.31441

ideal gas, at

10\"J
\342\200\224

and Chemical

ReferenceData 2D),663

A973).