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pat;

Killcl,

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Thermal physics.

Bibliography:p.
Includes

index.

!.

Herbert.1928QC3H.5.K52
ISBN

Statistical

tiicrmodyn;miics.
joiiii

I.
II.

Kroe/n
Tillc.

aullior.

1930

536'.?

79-16677

O-7167-IO8S-9

Copyright No pan of mechanical,


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\302\260 this

I9B0

by W. may

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Twenty-first printing, 2000

About the Authors

Charles

Kiitel since

has

laught
1951,

solid
having

at

Berkeley

undergraduate

work

in

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

Laboratory

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

University.

iferbcrt

Kroemcr

is

Professor

of Electrical

Engineering at the
mid

University

of

California

at Santa
I

liurhara.
a I'lt.D.
a

His background

training

nre

in solid
of

state

liliy^ics.

!c received
with

in Germany
in

thesis

in physics in I'J52 from on hot electron effects


several

the University
in

Gulling

lhc

then

new research

transistor. laboraProfessor

Prom 1952 through


laboratories

I96S tie workedin


and

semiconductor

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,

Germany

the

United

Preface

This book

gives

an

elementary are

account powerful,

simple,
applications.

the

methods

Probably

no

other

physical

physics. The subject is and the results have broad applicatheory is used more widely throughout
of thermal
students

science

and

engineering.
of

We have written for undergraduate and for electrical engineering students

physics These

and

generally. notably

fields

astronomy, for our

purposes have strong common bonds,most mcmls, gases, whether in semiconductors,

a concern

with

Fermi
well

stars,

or ituclci.

We develop
that

methods
suited

(not

original,

but

not

easily

accessible

elsewhere)

are

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 mechanics would make the course more difficult than we believe a course should be. Also, we have avoided the use of combinatorial first
methods

where

they
not

are unnecessary.
We

Notation and units;

generally

parallel.
the

We

do

use

the calorie.

fundamental

temperature

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 con(he ance of grants of California. Edward M. PurceSl University by review of the from 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,

t by

r =

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


kBT,

and

the

conventional

entropy

F.

E.

O'Meara,

Norman

E. Phillips,

B. Roswclt Russell, T. M.

Preface

Sanders. Wichmann.

B.

Stoeckly,
We

John Carol

thank

John Wheatley, and Eyvind Verhoogen, for the Tung typed manuscript and Sari
of the

Wilde
An atmosphere

for

her help with


treatment added

the index.
greenhouse
page added adopted

elementary was

effect in the Earth's


argument

atmoon the use, a

in

1994

on page
A

115, following an
on to the

suggested

by

Professor

Richard

Muiier.

aioinic page

Bose-Eitistein condensationwas For instructors who have

gas experiments 223 in 2000. for

course

classroom
(http:/Avhfreenian.

solutions

manual

is

available

via

the freeman

web site

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

to Fundamental Definitions
References

xiii

General
Introduction

xv

1
1

Chapter

States

of

a Model

System

5
27

Chapter 2
Chapter

Eittropy and Temperature


Boltzmann

Distribution

and Hdmholtz

Free Energy 55

4 Chapter
Chapter 5
Chapter

Thermal

Radiation

and

Planck

Distribution

87
1 i

Chemical Potential and Gibbs Distribution


Ideal

Gas

151

Chapter 7
Chapter

Fermi and Bose Gases


tHeaZahd

181
261

Work

225

Chapter

Gibbs Free Energy and ChemicalReactions


Phase

Chapter10
Chapter

Transformations

275

il

Binary

Mixtures

309

Chapter 12
Chapter

Cryogenics 333
Semiconductor

13

Statistics

353

Chapter

14

Kinetic Theory 389


Propagation

Chapter15
Appendix

423

Some

Integrals

Containing

Exponentials

439

Appendix B

TemperatureScales 445

Appendix

Poisson

Distribution

453

Appendix

Pressure

459
Temperature

AppendixE
Index

Negative

460

465

Guide

to

Fundamental

Definitions

Absolute
Accessible

activity,

exp(/i/t)

139

state

29
ka

Boltzmann constant,
Boltzmann Boson

25

factor, 183

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

61'

Chemical

potential,
n

/;
\302\253

119
nQ

Classicalregime,
Ensemble

74

of systems

31
pV

Enthalpy, H = U
Entropy,

246

40

Fermion

1S3

Gibbs factor, exp[(NjiGibbs

t)/i]
U
\342\200\224

138

free

energy,

G =

\\a

p^

Gibbs
Heat

or grand
capacity,

sum,
C

\342\226\240%

138

63

Heat, Q
HelmhoHz

68, 227
free

energy,

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

Landau

free energy

function, FL

298

Multiplicity,g

Orbital

9
function,

Partition

61

Guide to Fundamental

Definitions

Quantum

concentration,

hq

Reversible

process

64

Temperature, t
Thermal

41
62

average

Thermal

equilibrium
W

39

Work,

227

General

References

Thermodynamics A. B. Pippard,
Elements

of classical

1966. M. W.
Sitttisiical
Zemansfcy

thermodynamics,
Heat 198!.

Cambridge University Press,


an intermediate

and

R. H.

DiEEman,

anil

thermodynamics:

textbook, 6ih

ed., McGraw-Hill,

Afcchanics

U. K,
T. L.

and M. Eisner, Statistical 1988. Agarwal mechanics, Wiicy, and selected Dover PubticaHit), Statistical mechanics:principles 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.

present Eext.
R.

Kubo,

Statistical
M.

mechanics,

R, Kubo,
1985.

Toda,

N. Hashitsume,

North-Holland, 1990, cI965. Statistical physics !! (NanequHibrium),


Statistical

Springer,

L D.

Landau and E. M. Lifshitz,

physics,

3rd cd. by
1985.

K. M. Lifshitz

and

L. P.

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

Scientific,

! (Equilibrium),

Springer,

1933,

Mathematical

tables
Tables
widely

H. B. Dwight,
1961. A

of integrals
useful

and other
collection.

mathematical data, 4ih

ed.,

MacmUton,

smati

Applications

Asirophysics

R. J. Taylor,
S. Weinbcrg,
ed.,

The

stars:

their
three

structure
minutes:

and

evotitiioit. v:\\-w

Springer, of the

1972.

The first

a modern

origin

of the

universe, new

Bainam

Cooks,

1984.

Biophysics and macromolccules

T. L. Hill,
Springer,

Cooperathity

theory

in biochemistry:

steady stale

and equilibrium

systems,

1985.

General Refer,

Cryogenicsand
G. K.
White,

low

lempcrature

physics
techniques

Experimental

J.

University
Wilks

Press, D. S.

1987, ct979
An

. .

in low-temperature

pa.
to liquid

physics, 3rd ed., Oxford

and

Betis,

introduction

helium, 2nd

ed , Oxford

Univesity

Press,

1987.

Irreversible

thermodynamics
to

J. A. McLennan, Introduction 1989.

non-equilibrium

statistical
chaos:

mechanics, Prentice-Hall, new dialog


with

I.

Prigogine

and

I. Stcngers,

Order

out

of

man's

nature.

Random

House,

1934.

Kjnclic theory and transport phenomena S. G. Brush, The kind of motion we call heal, North-Holland, 1986, cI976. H. Smith and H. H. Jensen, Transport phenomena,Oxford University Press,
Plasma

19S9.

physics
processes

I... Spitzer, Jr., Physical


Phase

in the

interstellar medium,
. . renormalizat'ton
and

Wiley,

197S.

transitions

P. PfeiHy and G.
phenomena,

Touiouse, Introduction
Wiley,

to

the

group and to

critical

1977. critical

H. E.

Stanley, Introduction to phase transitions


Press,

[ihenomena,

Oxford Uni-

University

1987.

Metais
P.

and

affoys

Haasen,

Physical

metallurgy,

2nd ed.,

CambridgeUniversity

Press,

1986.

Superb.

Boundary

value problems
in solids,

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

2nd ed.,

Oxford Univer-

Semiconductor

devices

R.

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
Datven, state

Solid

physics
to solid

C. Kittel, Introduction

state physics, 6th

ed.,

Wiley,

1986.

Referred

to ssISSR

Thermal

Introduction

Our approach to
physics

thermal

courses.

Therefore
the

going

to do
in

in

chapters subject

structure:
tion

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

cltaracters in our are the entropy, the temporaiure, appearance,the leading story the Boltzmann the chemical factor, potential, the Gibbs factor, and the disiribufunctions.

The entropy
A

measures the number of quantum


might The

states

accessible

to a

system.

closed

system probability.

be

in

any

of these

quantum

states and

with (we assume)

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
equal

fundamental

is that

ofg,3j.

When two systems, each of


ttiey

specified

energy,

are brought of energy

into thermal
the one
in

coniact
or

may

transfer

energy;

their total
lifted.

energy remains constant,but


A

comlraints direction,

individual energies are perhaps in the other, may increase


on their

transfer

the

product
The

g^g, that measures the tiumber of


fundamental

accessiblestates of the combined systems.

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


We have

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

is atiained when

ihe for

value

ihe same
in ihermai

quantity

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

coniaa is just the

property we
lemperaiure

we define the fundamental

system is equal to the value of This equality property for Iwo systems of the icmperat lire. Accordingly, expect
for one
i by the

relation

CUJ

U)
to

The use of 1/r assures that


complicated

energy

will

flow from high

low

r; no
temperature

more comT

rclaiion

is

needed.

it will foilow'that
with

ihe

Kelvin

is

directly
The

proportional

to t,

Ayr,
.S\"

where kB is
-

the Boltzmann constant.


factor
tl

conventional

Now consider
Uiajner

3. i.ti

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

5 is

kRa.
ibe

Dolt/nvnm

treau-d
:iml

in

sinies,

i.fie :it cnorj>y

une

:n

energy
system

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

with

u large

the

combined

system Uial we eaH the systems is UQ; when the small


Uo slate
e)

is in ihe stale of energy 0. the reservoir has energy in states it. When the small is the accessibleto sysiem g{U0)

and

wiil

have

of energy accessible

e, the
lo

reservoirwill
it. By

have

energy

Uo
assumpiion,

\342\200\224 \302\243 and

wiii

have

g{U0

\342\200\224 slates

the

fundamental

smali system

with

energy

s to

the ratio of tbe probability of finding [he 0 is the probability of finding it with energy

,
^@)

- c)
exp[<*(f

B)
o)] in a

gWo)

The reservoir

entropy a

may

be

expanded

Taylor series:
=

g{U0 by

~
e)

a{Ua)

\302\243{ca/tV0)

c(t/0)

- e/r ,
the

C)
expansion

the

definition

A) of

may

be dropped.

the temperature. Higher order terms in which Cancellation of the term exp[_a{U0)],
the

occurs

in the
with

numerator

and denominator of B) after

substitution

of C),

leaves us

This

is Boitzmantt's

result.

To show its
system

use, we

calculate

the

thermal

average

energy (e) of the two state


temperature

in

thermal

contact

with a

reservoir at tem-

t;

E)

where
probabilities:

we have

imposed the normalization conditionon the


+

sum

of the

prob-

P@)

P{e)

- 1.
to find the
this

F)
average energy
4 as the
can
of
first

The
step The

argument

can

be

generalized

immediately

harmonic
in the most

oscillator derivation
important

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


extension
ttie

in Chapter

of the
be a

theory is to
For

systems

that

transfer

particles

ns well

as energy with
the

reservoir.

two systems in
to

diffusive and

thermal contact,
of particles
eqtuti

entropy as

will

as

well

to

the

transfer
(f it/jW)^,.

the

for Hie two systems, btil mmilKr of particles of ;i

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

Tin-* {uwn spevk's.

cttii:tiity

coiutiiion

is Hio

For two
sign

systems in

thermal

and

diffusive
the

contact,

r,

<=

r2

and

jt1

\\it.

The

is approachedIs from
ailows

in G)

is chosen to

ensure thai
high
Chapter

direction

chemicai
5 is

potential an extension

of particle flow to low chemical

as equilibrium

The Gibbsfactorof
us to

of Ihe

potential. and Bolizmann factor

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:
tf(f/0

t;HQ

- 1) =

0(r/o;A'o)

z{ca/dUo)
c/r

- l-{ca/dNo)
(S)

~
By anaiogy
with

o(U0;NQ)

+ ^/r.

D),

we

have \302\243)/r]

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

=\302\273

cxp[{/(

(9)

probability the system ts unoccupied, to the probability the system


ratio ofihe
normalization

is occupied

bv

particle

at

energy

with

energy 0. The

result (9)after

is readily

expressed

as

A0)

This particular result is known as the


is used
temperature

Fermi-Dirac

distribution

function

and
low

particularly
and

in

the

theory

of metals

to describe the
in the

electron gas at

high concentration
function

(Chapter 7).
used

The classical distribution


is just

derivation

of the ideal gas law1:

the limit

of A0) when the

occupancyPA,e) is much lessthan

The

properties

of the
because

ideal gas are developed from


energy

this

result

in Chapter the easiest

6. method
from

The HeSmholtzfree
computational function,

F=

\342\200\224 to

appears
v

as an
\342\200\224 a

important computaF
the

the relation

{5F/cx)s
found

offers

for finding the entropy,


energy

once we have

out

how

to calculate

eigenvalues concerns
meaning
physics

thcnnodyiumic
the

tcxl
the

illuminate

Thermal

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

objects,
microscopic

and

of

chemical

and

biological
It

processes
the two

with

the

world

of moiecular.
micro-

atomic, and electronic systems.


and

unites

parts of our world,the

the

macroscopic.

Chapter

States

of a Model

System

BINARY

MODEL

SYSTEMS

10

Enumeration
Binary

of States and the Multiplicity


System

Function

U
16

Alloy

Sharpness
AVERAGE

of the Multiplicity
VALUES

Function
:\342\226\240

18
22

Energy
Example:

of ihe

Binary Magnetic
Function

System
for Harmonic

''

--.

-3
24

Multiplicity

Oscillators

SUMMAItY

26

Chapter

!: States

of a

ModelSystei.

Bul

although,

as a
in

matter of history, statisticalmechanics owes


it seems
elegance

its of an

origin

to

investigations development,

thermodynamics,

eminently
and

worthy

independent

and because it
departments

both on account of the


yields

simplicity
in

of its

principles,
in

new

results

and places

old truths J.

a new

light

quite

outside

of thermodynamics,
W.

Cibbs

A theory

is the more
kinds Therefore

impressive the
of things the

greater

the

simplicity
classical

of its

premises, the
made

more different
applicability.

it relates, theory

and the more


that

extendedits area of
thermodynamics
which

deep impression
the framework

upon me. It

is ihu

only

physical
within

of universal of

content

I am

convinced

mil never be overthrown,

applicability of its basic


A.

concepts.
Einstein

Chapter

1: States

of a ModelSyster,

Thermal

physics

is the
us

fruit

of

the

union

ofslatistica!
in

and mechanical

principles.

Mechanics tells
heat. There

the

meaning
new

of work;

are three

quantities temperature,

ordinary mechanics: entropy, their definitions the in first


thereafter.

thermal physics tells us the meaning of that do not thermal physics appear in and free energy. We shall motivate

three

chapters and

deduce their consequences


is the

Our

point

of departure

for the developmentofthermal physics


system

concept

of the

stationary quantum statesofa the quantum states accessible to a


for

of we

particles.

When

we can

count
2).

system,

know

the entropy
of states

of the

system,

the

entropy

is defined

as the logarithm of the


on

number

(Chapter

The dependenceof the entropy


temperature. From

the

energy

of the system
energy

defines the temperawe find

rhe entropy,

the temperature,

and the free

the pressure,

the chemical potential,and

Fora
such brevity

system

in

as

the
we

energy
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 composed of a single particle or, more ofi^n, of interof many particles. The theory to handle genera! systems is developed but be can made in particles, powerful special problems interacting simplilicarions
for

which

the

interactions
slate

Each quantum
said to

has

may be neglected. a definite energy.


level.

Stales

with

identical

energies

arc

belong to the same energy

The

multiplicity

energy level is the number of quantum states wiih very it is the number of quantum slates that is important
tlte

or degeneracy of an the some energy, nearly


in thermal sums

number

of energy

levels. We
the

shall frequently
energy

deal

fti'th

physics, not over all quantum


two

states. Two states at


not

same

must always
lewis

be counted as
uOveia!

slates,

as one

level.
alomic

Let us look antic qiu.Umu suresam! eitcryy The simpler is hydrogen, with oik electron
energy

s>^u-ms.

and
!.!. Tlte

levels

of

hydrogen

are shown
level

in

Figure

figure

is taken

at the
has

state of lowest
of
\\h

energy.

one proron. The !u.\\-I>iiig The zero of energy in the of quantum stales number in lite

belonging to the sameenergy


that

is in has

parentheses,

the

prolon

a spin

and

two independent

figure we overlook orientations, parallel

Chapter

1; States

of a Model

SyMm

Hydrogen
Low-tying

Lithium

Boron

energiesare

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 given

in electron

or antiparaliel

to the
the

direction of an arbitrary external axis,such


of

as

the

direction

of a

magnetic field.To takeaccount


of

the

two

orientations

we should
the

double
Each
ail

the values
An

multiplicities

shown

for atomic

hydrogen,
move

atom

of lithium

has three

electrons which

about

nucleus.
with

electron interacts with the

alsointeracts nucleus,and eachelectron

the

Chapter

I: Statesofa Model

Systet

30
Mill

IUpresc
lip liciiy

diq
3 2
1

25
4 2

20
3 J 3
1

4 3

15
3
2

2
3

2
1 1

5 to 3
2 1
\\

_
1

'

Figure
\302\253_,, jjj,,

1.2
n, ofa

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

quanlum

numbers

other electrons. The energies ofthe 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.
states

quantum

state

of the

system is a state ofall particles. Quantum called orbitals. The low-lying levels energy
confined

ofa

one-pariicie

system
in

are
3

ofa

single particle

of mass M confind

to

a cube

of stde

are \302\243

shown

in Figure

1.2. We shall

Chapter

Chapter

1: State* of a Model
of a

System

that

an orbital

free particlecan be characterized


nyi

by

three

positive

integral

quantum

numbers nf,

n,.

The

energy

is

The multiplicities

of the levelsare indicated


the

tn

the

figure.

The three
nr2

orbitals
=

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


To describe

n.1

18;

the statistical
of particle

to know these!of values

properties of a system
the

of

A' particles,

it is

essemial

siaie soTthejV
states
in

system.

energy Indices

where \302\243S(N),

c is

theenergy
assigned

such as

s may

be

of the quantum lo the quantum

any
the

convenient
same

arbitrary

way, bul two different

states should not

be

assigned

index.
our

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
systems Ej{ binary found

are believed to appiy equally This physical system. assumptionleadsto predictions


for

the

model

system

well that

to any

realistic with
clear

always

agree
become

experiment. What as we go along.

general

statistical

properties

are of

concern will

BINARY MODEL SYSTEMS

The
Attached

binary and

model distinct

syslern sites

is illustrated fixed

in

Figure

separate

in space,

N shown for convenience on a line1.3.

We assume

there are

to

each

site

is an

elementary magnet
moments \302\261n>. knowledge

titat

can

point

only

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
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

Binary

Model

Syster

123456789 Number of the


Ffgure
magnets site

10

1.3

at fixed
sire

Mode! system sites on a


numbers

moment
each

The \302\261m.

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

has

ils own

magnet

assume

there

are no

magne'ic field.Each
two

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 ways,

(he probability is 1/210.

of finding

tile

particular

arrangement

shown

Figure

1.4

State

ofa

parking
This

lot

with

10 numbered by a car;

spaces. TiseO's denotespaces denote


shown
vacant

occupied

parking theO's

spaces.

particular

state is equivalent

to

that

in Figure

(.3.

Now consider N different assume the values +\302\253i. Each


probability number

sites,

each

of which may

moment

bears be oriented
2

moment

thai

may
with

in two 2 x

independent of arrangements
2'v states.

of the

orientation

ofa!! other moments.


x

ways
The

total

nf the
We may

N moments is

2 x

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

2\\

state of

the system h sjveitiedUy


are

site;

there

the orient at ion of the moment oil c:k!i yiviiig for a single use ilio following simplettotation

state of

the system of N sites:

nuimrr-

B)

\342\226\240rl: States

of a

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 [.
Figure

1,5

The

s> stem

of two

The

sites themselves
in

numbcr4hem
to

this

convention

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

C)

Both

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

U)(U

D)
by

The

multiplication

ruie

is defined

(Tt +

liXti + li)

ti + till

UU

E)
one magnetic

a sum of 2*v The function D) on muitipltcation generates the 2'v possible states. Each term is a product of N individual
symbols,
an with

terms,

for each moment

of

one independent

symbol state

for each of

denotes
T1T3I3 For

elementary magnet on the line.Each term the system and is a simpleproductof the form

''\"
t\\i

f\302\260r

example.

a system

of two elementary
possible

magnets, we multiply
of Figure

(}x

li)by(t2

+ |j)

to obtain the four

states

1.5:

(Ti + I1KT2+
The sum
it generates

ii)
side

Till
of listingthe four
of the

itTa

I1I2.

F) of the

is not

a state

but
left-hand

is a way

possible

states

system.

The product on the

function: equation is calleda generating

the states

of the

system.

\342\226\240

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

Binary

Model

Systems

The generating

function

for

the

slates

of a

system of
+ U)-

three magnetsis

(Ti

li)(?2+

IjHTj

This expressionon multiplication generates 21 =


Three
Two

S different

states:

magnets up:
magnets

T1T1T3

up:

T1T2I3

T1I2T3

lihti

Onemagnctup:
None

tihli

IJ2I3
lilils-

lilif3

up:

The
in

totat magnetic moment of our


m

model system
from

of

magnets
to

each

of

magnetic moment
a magnetic is
values

will

be denoted

by Mt

which we will
Nm

relate

the energy

field. The by

value of M varies

to --

Nm. The

set of possible

given

M
set of

\302\253

Nm,

{N

2)m,

(N -

4>n,

(N

6)m,

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

G)

The

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 N \302\273 states. 2N \302\273 N + 1. There are many more states than When !, we have = = 210 states ! 024 distributed values of [he total moment. !fW 10,there are 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
are
Only

one

state

of a

system has the moment


TTTT-

M = Nm;that

state

is

-TTTTmagnet

(S)
down:

There arc N

ways

to form

a slate

with

one

mt
is one

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

AJ)

sue!

state;

another

is
\"

tin

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

do)

Chapter

1: Slates

of a Mode! System
with one
from magnet down are formed

and

the

other

slates

(S)

by

reversing

any single

magnet. The states (9)


of

and

have \302\243!0)

lot.il

moment

M = Nw

- 2w.

Enumeration

Stales

and

the Multiplicity

Function

assume that

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
We

use

the

word
N

is an

spin as a shorthand for even number. We

difference

W,

/V,

25

(ID

is called
from
but

ihc spin

excess.

The

spin

excess of
(I!}

the 4 states in
to be

Figure

1.5 is

2,0, 0,

\342\200\224

2,

left to
it

will

right. The facior of 2 in prove to be convenient.


D)

appears

a nuisance at this stage,

The productin

may

be written

symbolically
+

as

(T \342\226\240.

if-

We may

drop the site labels {thesubscripts)


many

from

D)

when

we are labels

interested
in

only

in

how

of the

magnets

in

a state

are
ft

up or
we

down, and not


the

which

particular

sites
which

have magnets
the

up or down,
appear in a

drop

and neglect

the order in

arrows

given product, then E) becomes


-

(t

II;

further,

(t + |)v for

I)' = Itt + arbitrary


iV

3ItJ + 3IJJ + jjj.


the

We

find

(I

by

binomial

expansion

A2)

Enumeration

of Stales

and the

Multiplicity

Function

We
form

may
by

write the

exponents of x and y
\\N \342\200\224 s:

in

a slightly

different,

but equivatem,

replacing

t with

With

ihis result

ihe symbolic
ivv =* y

expression{| +

|)'v

becomes

4-

tj-v+j

M*V\"J

A4)

The
W,
states

coefficient
=

denote

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:
of the term
in

iA-+*

M*\"'

is the number

,n\342\202\254>T

(IS)

Thus

A4)

is written

as

(I + i)'v=
We

I stJMT^l1\"\"
function;

A6)

shall

call g(N,s)
value

ihe

multiplicity

it is

ihe number
emerges

of slates having
when

llie same
s have

of

5. The

reason
system:

for our
in a

deltnttion

a magnetic
values

field is applied to the spin

magnetic

field, stales

of different
to the

of

different values of the


tn

energy, so that
field. Until

of an energy level
states

a magnetic

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

of the
from

Note

model system have the same energy, which the total number of states is given that A6)
'

may by

be

taken

as zero.

g{Nts) =

l)-v =

2-v

(H)

for Examples related to g{h',s)

A'

\\Q are

given

in

Figures could

1.6 and stattd

1.7. For

coin, \"heads\"
down.\"

could

stand

for \"magnet

upland

\"tails\"

for \"magnet

Chapter t: Slatesofa Model

System

Figtorc 1.6 Number of 5 -f j- spins up and


Values

of distinct arrangements 5 ~ 5 spins down.


h of

of yf Npi)

tUc spin stales is

oixss

are for N - 10, when: 2.v K I. Tlic toul numtwt \\ -

TTic values of the


the

9's

arc taken

fro

binomial

coefficients.

-8

-4

-10

-6
Spin

-2
excess

4
2s

Binary

Alloy System
the

To illustrate that

exact an

nature alternate

of the two states


system\342\200\224an

on each site is irrelevant to

the result, we consider sites, numbered from


an

1 through

atom
for

of chemical
vacant
state

species A
In brass,

12 in Figure of or an atom
A

provision

sites.
of the

could

be

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

single

alloy system

can be written

A8)

nry

Allay

Sya,m

\342\226\240= o

20

01

23456789
Number

10
which

of

heads

Figure

1,7
thrown

An

experiment

were
throw

NX) times.

Was done in The number of

10 pennies
in

heads

each

was recorded.

0\302\25100
I

Fijutc

1.8

A binary componenls

\302\251 5

0
6

chemical

alloy syslcm of two A and 1!,whoseatoms

10

II

012

Every

distinct

state

of a

binary alloy

system on

sites

is contained

in the

symbolic product of N factors:

(A, +
in

B1)(A3

4-

B2)(A3

+ Bj)---(A.V

+BN) ,

A9)

analogy

to

conventionally

of

atoms,

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
D).
~

atoms is NB

.\\JV. Here
expression

.v lies

between Oand 1.

The symbolic

is

analogous
g{i\\\\f)

to the
of

result A2).
possible

The coefficient

of

the

term

in A'v\"'
\302\243 atoms

number
atoms

arrangements

or states

of N ~

B' gives the


A

and

B on

N sites:

which

is identical

to the

result A5) for


Function

the

spin

model

system, except

for notation.

of ihe Sharpness
We
usually

Multiplicity

know

from common
have

major
the

prediction

experience that systems held at constanttemperature well-defined this stability of physical propertiesis a properties; The of of thermal physics. stability follows as a consequence
bharp away

exceedingly
that

peak from

in the

of

function

the peak. We
defined

of and multiplicity function can show explicitly by

the steep
thai

variation
for

a very

large system, the function <j(Af,s) the value 5 = 0. We look for an

A5)

is peaked very
allows

sharply about
to examine

approximation that

us

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

is convenient are

logarithms

to work with to be understood


log

log*/,

f-xccpl

where
here

.-ilierwise
as log.

written loy base*?,

specified, till The international

standard usage is In for


ambiguity

base

c, but

it

is clearer
very,

to write
very

log when
number

there is
such

no

whatever.

When

you confront a

large

;is

Sharpnessof the
2iV, where We
iV

Multiplicity

Function

lG:o,it

is a

take

the logarithm
\\ogcj(N,s)

of both sidesof A5)


= logN!

simplification to look at the logarithmoft he


lo

number.

obtain

- logfrV + 5)! logarithm

log&N

s)l ,

B2)

by virtue of ihe characteristic properlyofthe logxy =


With

of a

product:

logx + logy;

log(.\\-/_v)

log.v

~ logy.

{23)

the

notation

jV, =

\\N

4-

5;

A', B2)

=\302\253

\\N

B4)

for the

number of magnetsup

and

down,

appears

as
logW,!.

logg(N,s) - logW! We

logiV,!
by use

B5)

evaluate

the logarithm
which

of

N\\

in

B5)

of die

Stirling approximation,
1

to according

ZjTi'Go
\342\226\240 \342\200\242 , \342\226\240]

s-t\\Q\\

\\

.V!

BrtN)ti:iNNcxpl~N is derived in
argument

+ IJ[12N)

B6)

for N

\302\273 1.

This

result

terms
We

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


the logarithm
logN!

take

of both sidesof B6)to obtain


S

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

the
N.

I log

2k +

(N + |) log

N.

B7)

Similarly

!ogjVt! s

I log

2?r

(JV, +

JJlogN,
J)log.V,

- jV,;
- Nu

BPJ B9)

logN,! s iiog2* +
After

(,Vi

rearrangement

of B7),

log.Y!

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

'.- f.V,

\\

-V, +

i)logJV

- (.V, +

Nj)

CUf

wlK'i'ciwcliaVcuscilW for B5):

= .V,

I-

.Vt.

\\VL-siil>ii;iLl{2S);iiKM2'J)froin{.!U)loobl:iiii

tog</ S

ilog(l/2;r,V) -

(.V,

iJlogty./.Y)

(,V, -f

i)Uui(.V,/.V). C1)

This

may

be simplified

because

logOV,/iV) =
~

log^l
-iog2

4-

2s/jV)

-iog2

+ iog(i

-f-

2s/S)

+ Bs/,V)

- I2s2/N2)
.v

C2)
\342\200\242 \342\226\240

by

virtue

of

the

expansion

logfl +

x) =

jx2 +

-,

valid

for x

\302\253 I.

Similarly,

!og(W,/A')

= logld

- 2s/N) =
obtain

-log2 -

B5/N)

Qs2/,\\'!).

C3)

On subsliiuiion in

C!)
iogg

we

s |logB/;E/V)

Wiog2

2s!/N.

C4)

We write this

result as

C5)

WnH)\"*?1.

C6)

Such

a distribution

of values of sis
\342\200\224 co to

caiicda

Gaussian

distribution.

The
2*for

of C5) number

over the range of states. Several useful

+ co

for s gives the correctvalue


are
with

integral* the total

integrals

treated
s =

The exact value of y(N,0)

is given

by A5)

in Appendix 0;

A.

C7\302\273

\342\200\242

The

replacement
errors.

of a

slim

by

significanl

For example,

an iniegrai, ihc rai io of

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


'

.)Js,

usually

does

X s
\302\273^o

=--

i{N2

N)

to

Ts./s

= IN2

is equal

io

+ A/N),

which approaches i

as N

approaches

co.

10

\\
Figure
X. (he

1.9
binomial

Tlie Gaussian
cocfficicnis
scale

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

\"

\\

\342\200\224

iinearscaie. On this
distinguish

on

ihc

drawilig
range

the approximation
of s is from

\\
1

plotted

The

entire

50

to

dashed lines ai\302\253 drawn from vaiuc or points at t/e or (he maximum
4- SO. The

the
y.

n
0
-20

y
-10

For N = 50, the


vylue
in

value

of sE0,0)

is 1.264

x 101*,from C7).The approximate

from

C6) is

a maximum

at s
value.

1.270 x 1014.Thedistribution plottedin Figure t.9 is centered = 0. When = to e~' ofthe s1 value is reduced the of g {N,
That

maximum

is, when

s/N = A/2NI'2 ,
the

CS).

measure

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
value
of

of g

the

fractional

prediction
well

that

defined.

properties of systems in thermal equilibrium We now consider one such property, the value of s1. mean
the physical

are

ChapterI: Stales

of a

Modal System

AVERAGE VALUES

The average value,


distribution

or

mean P(s)

vaiue, is defined

of a

function f(s) taken over a probability

function

as

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

09)
to
unity;

provided

Uic

distribution

function

is normalized
!.

\302\243?(*)-

D0)

The binomial

distribution A5) has lite property


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

A7)

that

D1)

and
g{N,s)/2s,

is nol
be

normalized lo
and

unity.

If

all

states

are equally

probable, ihen P(s) ~


distribution

we

have

\302\243J'($)

t. Tfic

average of/(s) over this

will

D2)

Consider tile function

f{s) = s2.In
\302\243

the

approximation

that

led to
ds

C5) and
~- co

C6),

we

replace

in

D2) the sum

over

s by

an integral

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

between

and +

co.Then

- [2/nNI'3

(jV/2)J'J

J^Jxx^\"'*
(jt/4)\022

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

<i-J>

= iiV;

<B,y> =

,V.

D3)

The spin

quantity excess

<{2i);> is

is the mean

square spin excess.The root mean


-

square

<B5}2>';J =>yfN

D4)

<uy Magnetic

Sys

and the fractional

fluctuation

in

2s is

defined

as

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:o $F particles, 10\0210,which is very small.
of

Energy

the

Binary

Magnetic

System

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
V \302\273 -m-B.

H6)

This is

the potential energy of For the model system of


a uniform

the
Ar

magnet
elementary

in

the

field

B. each

mngncts,

with

two allowed
U

orientations in

magnetic

field 1J, the

tola! potentialenergy
2smB}=

is

m,- =Q.

- MB ,

D7)
example

using

ihe

expression

M for the

toial magnetic moment


is

2s/n.In this

lite

spcclnttn
continuous

of values
or

of ihe encrcy U
spectrum
adjacent

discrete.

quast-conttnuous
between

will levels

ihe spacing
Figure

energy

concreafe no difficulty. Furthermore, of (his model is constant, as in


We shall

sec later (hat a

t.tO.

Constant
will

spacing
restrict

is a

special

feature

of

the

particular

tnodcl,

but

this feature
ihe

not

the generality

of (he argument that


ihat
by

m is developed

Following

sections.

The value
magnetic

^f (he
is,

energy

for

moments

inferact
the

only

with

the

exicnial

field ?.; -2,

^ornrfcicly ridennined
by wrtitng

value

of s.

This funcitotutl
raises

dependence
2s

i..ucaka

U{s). Reversing a
moment

single moment lowers


and

by

lowers the total


difference

magnetic
bsiween

by

~2m,

the energy
Ac,

by 2mB.The energy

adjacent

levels is

dcnotcJ by

where

Ae

DS)

Chopset

UM./mB

s(.)
1

log g(

+ 10 '

\342\226\240

10

2.30

+ 6

45

3.81

+ 4

120

4.79

+2

210

5.35

0
__2

252

5.53
S.3S

210

+2
+ 3

\342\226\240

-4

120
45

4.79

-6

3.81

+ 4

-8

10 1

2.30

+5

-10

magnetic nmmersis

are labeled by

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
m m a

magnetic

their

s values,

Example:

Multiplicity
the

system is

simplest exactly given

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

binary

model

function

is

known. Another was originally


do the

solvable

problem is the
need

harmonic

by Max
Sludent
in

Planck. The original


Chapter

for which the oscillator, is often felt to be not derivation


this

solution entirely
way

simple. The beginning

problem is given
slates

The quantum

nol worry about 4 and is simple.

derivation.

The

modern

to

ofa

harmonic

oscillator have the


es =

energy

eigenvalues

sho) ,
or and of

D9)
zero, the

where

the

quantum a system

number

s is a positive integer
of

and to is the multiplicity

angular

frequency
to

of the

the oscillator.
consider

The number
in which

states

is

infinite,

of each is one. Now

of N such

all oscillators,

the

same frequency.

We want

find

number of ways

a given

total

excitation

energy

can
for

be distributed
tlie Af oscillators.

among

the

oscillators.

That

is, we

want

the

multiplicity

function

The oscillator
going

multiplicity

function

is not

the same

as the

g{N,n)
mufti-

spin

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


forwm'chff(i,\302\253)

back

to tlie multiplicity
quantum

for

ail values
we

of

the

numbers,

function for a single oscillator, here identical to m. To sojve the


ihe

problem of E3) below,

need

a function

to represent or generate

scries

E1)

AS! Y,fl!!1 from

coS\302\260

^CfC
in

' 's
the

(S3),

but

t docs

not appear

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

number

number of onScted wuys We observe


that

of w;iys n term in which the

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

tj{N,n)

2) Thus

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

(W

- 1).

E4)

for the

system of oscillators,

ES)
This

result

will be

needed

in

solving

a problem

in the

next

chapter.

Chapter

1: States

of a Mode! System

SUMMARY

1.

The

N, -

multiplicity
N't

function for a

syslem of N

magnets

with

spin

excess

2s =

is

In

ihe

limit

s/N

\302\253 1,

with

A'

\302\273 1,

we

have

the Gaussian

approximation

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

2. Ifal!
2

states

of

the

mode!

spin system

are equally likely,

the

average

value

of

52>

j''^JsstgtN,s)

in the

Gaussian approximation.
fluctuation

3.

The

fractional

of s2

is defined

as (s2yll2/N and

is

equal

to

S/2N\022.

4. The

energy of the model spin

syslem

in a

siaie of

spin excess 2s is

where

in

is the

magnetic

moment of one spin

and

B is

the magnetic

field.

Chapter

Entropy

and Temperature

FUNDAMENTAL

ASSUMPTION

11
3'\\

PROBABILITY
Example:

Construction

of ;in

Ensemble

333

Most ProbableConfiguration
Example:

Two

Spin Systems in

Thermal Contact

3?

THERMALEQUILIBRIUM
TEMPERATURE

39

ENTROPY

-\342\226\240!

Example:
Law

Entropy
of

Increase of Entropy

On Heat

Floiv

41
45
-iS

increase

LAWS OF THERMODYNAMICS
Entropy

as

a Logarithm
Second

50
Kind

Example: Perpetual Motionof the


SUMMARY

50

51

PROBLEMS

5:
Temperature

1.

Entropy

and

52

2. Paramagnetism

52
52

3. Quantum HarmonicOscillator
4.

The
Additivity

Meaning
of

of \"Never\"
the

53
for Two

5.

Entropy

6. Integrated
Note

Spin Systems

53
54

Deviation

on problems: The
iitil

melhoJ of fhis

chapter
lliis

c
siu

we Jo

cinplusi^e

problem

soKing dl

Chapter

2; Entropy

and Temperatui

One shouldno! imagine


will
the W10

thai

two

gases
until

in a
separate,

0.1 liter
then

container,initially
mix again,
the gases.

unmixed,
On

mix,
\302\260

then again
one
will
this

contrary,
years

after a few days finds .., ilia!not


is

and so forth.
to

a time

enormously

there

recognize that

by any noticeable unmixing equivalent to practically

never. . . .

of

long compared One may

ff

we

wish

to find

in

rational

mechanics

of thermodynamics,

we must

an a priori foundation for the seek mechanicaldefinitions of temperature

principles

and

entropy.

J.
The

W.

Gibbs

between energy and temperaturemay are considerations. in statistical {Twosystems] by probability a transfer does increase the not probability. of energy
genera}

connection

only

be established
when

equilibrium

M. Planck

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.
with

We slart

this chapter

definition

of

probability

define

the

value

of a

FUNDAMENTAL ASSUMPTION
The

'

\"

\342\226\240 -

fundamental

states

likely to be in any arc assumed to

assumption of thermal of the quantum states

physicsis

ttt;tt

a closed

system

is equally
quantum

accessible to it. All

accessible

be equally
other

probable\342\200\224there

is no reason

to prefer

some

accessible
A constant

states

over

accessible

states.

closed

system
volume,

will
and

have constant
constant

energy, a constant number of particles, values of all external parameters that may

influence

fields. including gravitational, electric, and magnetic the A quantum state with is accessible if its properties arc compatible 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/
the system,
tmd&N/N Unusual
\302\253 I.

properties

of a
of

system

may

sometimes

make

it

impossible

for

certain states to be accessible during

the

time

the system

is under

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, to a it is possible to specify the configuration of a closedsystem If we specify that ihe are of no interest. point that its statistical properties as such

Fof example, the

states

the crystalline

in any observation silica will not convert

Chapter

2; Enxropy

and Temperature

I imtt

of

spcMftcation

of ihe

sjstcn

V\\uil-

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

system

is exactly

in a

stationary quaniurn state s, no statistical

aspect

is left

in

the problem.

PROBABILITY
to be tn any likely Suppose we have a closed sysiem that we know is equally one-half of they accessiblequantumstates. Let s be a genera] state label (a\302\273d not ihe in this slate is ihe spin excess). The probabtHty P(s) of finding sysiem

P(s) =
if

\\fg

(t)

the

state

5 is
assumption.

accessible and P[s) =


We

otherwise,

consistent

with that

ihe

fun-

fundamental

shall

be concerned
panicle
A),

taier
number wilt

with

systems

are not

dosed,
systems

for which the energy V and wtH not be a constant as in P(s)


A'.

but

vary. For these have a functional dependence


N may

on [/and on

Probubitiiy

The

sum

\302\243P(s)

of

the

probability
that

over alt
the

states is

always

equal

to

unity,

because

the total

probability

sysiem

is in

some state

is unity:
B)

_,
The

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 proba-

probabilities

defined

by (I)

probabilities

I'{s)

is

This

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
equation

that denote

average value.

For a dosed system,

the

average

value

of A' is

/\"i>-'-f

>':

'

!'

D]

because average

now in D)

average; Such a group of systems

elementary exampleof we imagineg simitarsyslems, in


is an
one

alt g

accessible slates are

equally what

likely, may

with be

P(s) = an called

\\jg.

The

each

accessible

ensemble stale. quantum

constructed

alike

ts

catted an ensemble of syslems.The

averageof
property. An

any

properly

over

the

group

is catted

ihc ensembleaverageof that

_1_

' \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

of systems

Each
and

sysiem

satisfies

all

external

requirements
the

placed on the
system.

original system
quantum

in

this

sense

is \"jus! as

good\"as

actual

Every

stale

\"U.:'j\\

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

Tit

: t

t
t

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

-rrrt

\302\273'.\"*

'';\"(:!'

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

t';t

;i
i

'[in
/[r;i
sT'\"\302\273

:y
t

t: r;jt
t

'nrt
rn; t

yi
-t
\\

t
t
[\\

t
Y.

/.:Y:t
-\342\200\242Tit

I
t

t
t

fit
rft

i'YY
l;ij;ure

t
2.2

:t:;Y
\302\253 iJirotijiJij

\\

;m
;l
2.v

Tliis

cuscmbJc
etwujy

icpresciiis

of lOspiiw wiih
Tlic

-Sui/Jimd
=

spin excess

n!Litij]>]iciiy !/{.\\'.n) is yUU,4) cl]sv-]I]!iIc iiium ^inlnin rcpfcscutiiiive

ilic |0, so tliut Hi syML-ins,


Mi

order in which listed has no

Uic vuriou^

sy>(cnis

tlie

cusciubl

sighificance. ensemble by one system in a We assume that the ensemble the fundameniat assumption.

accessible lo the actualsystem


slaiionary

is represented

in the
2.2.

quantum

stale,

as

in

Figure is

representsthe real system\342\200\224this

implied

in

Example;

Construction

of an
of

ensemblefive spins,

represent a dosedsystem
each frequent

We conslruci each system with


not

in

Figure

2.3

an

ensctnMe

to

spin

excess

2s =
in

{.The energy of
excess

in

a magnetic
use

field is

-mB. |Do
or

confuse

!he

use of

spin

with our
of

of s

as a

stale index

label.)

Each system

represents one of the

muliiptes

t tl'OutibiC

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

i\\

tj

jTIT:

f\\

t'T

Figure

2.3

The

enscmbie

represents a system

with

5 spins

and spin excess 2i

- i.

\342\200\236

R\302\253ute2.4

With

A' = 5 and

2s

- 5,a singie
.o!

| f

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

.! I

! t

Sy^m may represent ii ii

ti1Ca\302\273embio.ThiS is

states

at tin's

enetcy.Tlic

number ofsuch slatesis given

by tlic

multiplicity

function

Tile 10 systems
If the
energy

shown in llie

m Figure 23 make up ttic cuwnibk. 5r ltn-'ii n sinylc sysitm tiiLiitueliefieid weic siidi lli^t 2.\\- \342\226\240=

tomjiriscs

5 systems
have

have

2s
and

2s

- -3;

= 3;
t

|Q sysiems
has

have

7s

system

2j =

- 5.

I: 10

systems have 2s =

-1;

systems

Most Probable Configuration


Let

two

systems
freely
two

5,
from
systems

and
one
in

\302\243t

be
tttc

brought
other.

into
This

contact
is called

transferred

to

so that energy (hermnl contact


system

can be (Figure
\302\243z

2.5).The
with

contact

form a
Whai

larger closed
determines

& ~

Sx +

constant
flow

energy

net

ofenergy

of temperature.

the energy

of

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
whether

U =. Ut

there

will be

r 2: Entropy

anil

Temperature

Two

closed

in

eomacl

The
thermal

systems

ure

in

u\\

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

ul

+ ut

contact

sulaliiin

Thermal conduclor allows

exchange of
contact

energy

Figure

2.5

Establishment

of

Micrmal

between

[wo systems

&, and

systems can be dificrcin

in

size

sbared in many ways between The most probabledivision


system

and constitution. two systems.


of

constant

lotal

energy

can be

the

t6tal

energy is that for


We

which the combined


shall

has

the

maximum

number
contact. systems,

of accessible states.
and
first

enumerate

the

accessible

slates of two
in

model systems
We
1

then

study
in detail

what characterizes

the

systems when

thermal
two

solve

contact
in

between

spin

and

2,

in a niagoetic

the problem of thermal fieldwhich isintroduced


maybe

order

to define

the energy.

The numbersof spins N

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) coupling near between 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 Thespin excess of a state of ilie combinedsystem will be denoted by 2s, change. is dirccily where s = sx + sz. The energy of ihe combinedsystem proportional to the total spin excess:
U{s)

s2)

~2inBs.

E)

The tola]

number of particles isN

A'(

+ .Vj.

Most ProbableConfiguration
the energy splittings betweenadjacent leveh are equal energy 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
We

assume
in

that

to

7n\\B

both

energy

storage
value

so

The
when

of

s =

the

two
in

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
separate

that

permitted

ihe

values

of s,,

s3 and

thus

in

the

energies
&

I/,,
is

Uz.
to the and

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

system
systems

related 5[

5Z by

H2(Nj,s where

s,) ,

F)

the

multiplicity

functions

gx, g2 are
summation

A.15).

The

range

of s,

in

the

is from
that

To see

how F) comes first about,consider

given by expressions of the form of < N2. if Nl -fiY, to %Nt,


configuration

of the

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

combined systetn has

This

product
Different

forms
configurations

one

term of
of Uie

the sum F).


combined fixed s

system are
ofs(

characterized by
the total
thus

different

values

of j{.
all

We sum
ihe

suitesof
sum we
contact.

over a!!possible values


with
states part

to obtain

number of
obi a in

configurations

or fixed energy. We
of of

F),

where y{N,s) is the


hold

numberof accessible
and

the the

combined specification

s, N,,

N2 constant, as
of

system. In the of therma!


be

The result F) is a sum

products

of the
say

form G).
be read

Such a product\\sill
\"st

for some value maximum The configuration for which


cmtfigurntiun;

of s,,
glg1

sL,

to

us

hat\"

or

\"si caret\".

is a
in

maximum
is

is called the

most probab!e

ilie

number

of states

it

gxiN1.Sl)g2[Nl.s

- 5,).

(8)

Chapter

2: Entropy

am! Temper

A*.

Thermal
Sclicmalic

equilibrium

Figure

2.6

coiifiguralioji belwcen

of Ihe dependence of the repressaiion on [he division of ihe tola! energy multiplicity and Sj.

two syslems.-S,

!f ihe

systems

are

large,

the maximum
Figure

with

respect

to

changes

in Sj will

be

extremely sharp, as in

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
2.6.

A relatively

small number

of

large

system

in thermal

contact
the

with

another

large

system

are accurately

described by the properties nf


configuration for

most

probable

configuration,
thermal

the configuraaverage

which

the

number

of accessible st3tes
may

is a maximum. Such
equilibrium

values

(used

in either

are called of these two senses)


replace

values.

Because

of the

sharp maximum, we
(8).

the

average

of a

physical

quantity over all accessibleconfigurations


probable

configuration

In the
find

in

such

a replacement

and

example below we estimate ihe errorinvolved the error lo be negligible.

F)

by an

average over

only ihe most

Most Prabahte

ConfiSui

Example:
tfiL-

sharpness

Tn-o sprn systems in thermal contact. We investigate for of the produci G) near the maximum (8) as follows.

lUc

modd

Ilie muliiplicity

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

and

g^i-^J-

^olh

We form the ofiho form of|U5):

spin syslem of product

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

and

^@}

denotes

ffsf.Vj.Q). We

replace s,

by

- *,:

--^This

-l^iiLj.
system when
the

(jo)
spin

product*

gives

the number

of statesaccessible to
is 2s,

the

combined of ihc first

excess
We

of the
find

combined system
is,

and the

spin

excess

system is 2s,.

the maximum when

constant; that
to use
maximum
the

properly

of

>'{.y).

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|,

~^T-~

^~-.

(II)

uy

be

a maximum!

if the

a minimuni, second derivative of

or
the

function

z point of inflection. is negative,

The

e\\tr\302\243nuim

is

so

that

the

curve

bends

downward.
Ai

the

cxt

where
Equation

Nt, N2. and


A1) U

s are

held

constant

as s, is

varied. The second derivative

c1/csi1o(

* The

product

fund

ion of two

Gaussian

fund

ions

is always a

Gaussian.

and is negative, so thai of the combined system

the

extremum

is a maximum.
which

Tims the

most

probable

configuration

is thai for

A2)

is satisfied:

t
The

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

systems

arc

in

equilibrium

with

respect

1 is equal

find

iiic

number

of slates

in

the

most

probjble

configuration,

we

insert

A4}

in {9}

to

(-25I/N).

A5)

To
such

investigate

the

sharpness

of

of gigl

at

a given

value of

s, introduce &

that -

s,

<5;

sj

s2

- 5.
Su Sx at
the

A6)

Hcre^

measures

the deviarion
fonn

of su

st from

their

values

maximum

o(g,gi.

Square

j,,ij

to

which

we substitute

in {9} and

A5) to obtain

the

number

of sialcs

45,^

2Sl

4s2S

2d2

We

know

from (H)
ii

thai

s,/jVj

\302\253

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

so

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


that

a configuration

of ot \\

deviation

from

equilibrium

is

l(N2J2

- 3) =

te.ffiU.e

;v~

As a numerical let Ni
\302\253 ,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
&

extremely
probability

{17} from
the

I0u

out lo a value
probability

of (he order of
Tiits

of the
integrated

probability
are in

distribution.

of N, thereby is the subject of


s or

including

ihc area

under

wings

Problem 6. An

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, perceptibly different 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 success in 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. Therefore described wilt universe we lite deviation say with great surely that 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
is given
systems sysicm

by N x

tO\"t14 =

upper

limit

to the

over

a long

period of lime.

THERMAL

EQUILIBRIUM
ihe

The

result

for

number

of accessible

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
thermal

contact

may be

summed

over all

values of
at

Us < V. Wzxz
Ux. A
with

g X{N

itU

%)

is the

number

of accessible

states of system 1
specified

Jiicrgy

coniigiiratioit
the is lite

by ihe

value of
in

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

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

states ofaccesstblc
The

a configuration

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

~ Ut).

sum

o\\er

:nl configuraiioits

gi

The largest term in the sum in (!S) governs the propertiesof the total system ill thermal equilibrium. For an extremuni tt is necessary that ihe differential* of be zero for an infinitesimal of g{N,U) energy: exchange

dg =
divide

(-\342\200\224]

g2t!Ul

9i(^~\\d

lV, +

dU2 -

0.

A9}

We

by glgl

and use the

result dV2

~tiUx

to obtain the

thermal

equilibrium conciiiion:

Lflfs
which

we

may

write

as

B0b) We defitie the quanttiy

a, calledIhe entropy,
a{N,U)

by

\\

where

a is

the Greek

letter sigm:i.We

now

write

B0)

in the iimii form

B1)

means

lhai

Ns is held
wiih

consiam
respect

in

ihe

differttiljalion

o(g,{Nt,U,)

with

tespeel

lo U,.

Thai

is,

ili=

panial

dcrivalivc

to 0,

is defined

as

Teutperutute

This
contact.
ail

is the
Here
constraints

condition
Afi

for

thermal

equilibrium

for

two

ant!

/V2 may

symbolize

not only the

numbers of particles, but

systems

in

thermal

on the

systems.

TEMPERATURE

The last equality


know systems

B2)

leads

us immediately
in

to the

We concept of temperature.

the are

everyday equal:

rule:

thermal

equilibrium

the

temperatures

of the

two

r,

= t2.
so that T

B3)
must be a function
this function
of

This rule
If T
inverse

must

be
ttie

equivalent
ahsohite

to B2),
temperature

(ro/f

V)s.
iSie

denotes

in ketvin,

is simply

relationship

B4)

The proportionality
L-on^mnt.

constant

ku

is

;i universal

constant

called the

ilott/iiumu

As

determined

experimentally,
kn \302\273 U81

x
x

10~\"joulcs/ke1vin
10\"Ulcrgs/kelvin.
10 use

\302\253 1.3X1

B5) a more

We defer the

temperature scale:we

discussionto Appendix B becausewe


define

prefer

natural

the

fundamental

temperature

r by

B6)

This temperaturediffers

from

ihc

Kelvin

temperature

by the

scale factor, kB: B7)

kBT.

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

C/iapier

2;

Entropy

and

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 273.16 K.Thctriple arbitrarily of water is the and water vapor at which water, ice, point unique tcmperaiurc
may

be employed

coexist.

Historically,
to build measure
about

the

conventional

scale

dates
though

accurate thermometerseven
as

quantum states was

yet
with

not

understood.
thermometers

temperatures
than

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


which

from an
the

age in

it was

relation

precision
Appendix

the

32 parts

wit h which tlie conversion factor kB iiself is known\342\200\224 million. of discussed in are per Questions praciical thermomeiry
accuracy

B.

permissible to take

the

reciprocal

of both

sides to

B8)

The iwo
was

expressions
function

B6) has

and B8}
of

have a slightly

diOcrcu

leaning,
id M

in

B6).

given as a
from

determined
differentiation

B6) of

independent the same indcpendeiu

the

variables U

as a
V

variab]
in

r
in in

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

the entropy

<r

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

however,

U with
of

respect lo a
Eemr^caiufe

with

N consiant

mpties
both

so that t
expressed

V). The function of

definition different

is die
variables.

same
The
itrot

cases,
\"What some

but

is

independent

q
other

variables?\" arises frequently


some variabtcs, and
in

in lhermal

oilier

ej.pcrinicnts

phy. we

because

ihc independent we coniroi experiments


are

variables.

ENTROPY

Tile quantity
entropy

as

logg

was

introduced

in B1)
the

as ihe

entropy of the system:the


of

ts

defined

as the

logarithm of
is a pure

number

slates

accessible

to the

system. As defined, the entropy the entropy i'is defined by

number.

In classical

thermodynamics

129)

Entropy

Figure 2.7
than

if the

temperature

r,
to system

is higher
amount

t2,
&

the transfer
U from
the

of a positive
t

of

energy

system
entropy

2 v.itt

increase

total

a,

-f a2

of ihe
value the

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


finat

words,

system

wiii bt: in a
energy

condition if
to
U2+8U
the

cooler

body
is

established.This
increasing

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

cm ropy.

Energy transfer

o,(final) +
As a

cMXinai)

>

o^iniiia!)
see

+ oa(iniiiai)
that

consequence of B4), we

5 and

o are

connected by

scale

factor:

130) We
of
S the

wilt

call

conventional

entropy.
the greater
dependence

The more statesthat are accessible, a{N,U) we have indicated a functional


the

the entropy,

fn

the

definition

number of particlesin
may
3)

system

and

on the

depend
depends

on additional
on

independent
thermal

on the of the entropy The of the system. entropy energy variables: the entropy of a gas(Chapter
the physical wrote:
it

(he volume.
of

in Uic early history


was

physics
ed.

significance of the cm ropy


thermodynamics utility

not

known.

Thus

the
t

author
lih

of the article on
A905),

in

the

Encyclopaedia

Britaiiuka,

\"The
not

of

ihe

conception

of entropy

... is

limited physical

by

the

fact

that

does

correspond

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
We An experimental

determination

and

theorctic.il

calcutiition

of the
we

entropy

is

discussed

in

Chapter

6.

Consider the

tot;il entropy changeAa


1 and

when

remove

a positive

amount of
Figure

energy All

from

add

the same

amount of energy to 2, ;is in

2.7.

Clmptcr

2:

Entropy

urn!

Tehtjter

The

tolnl entropy

change is

When

t,

> r2 the

ihe quantiiy in
with

p;ireniheses on ihe righ>hand


is

side

is positive,

so that the
is

Loial change of entropy


system
the

positive

when

the direction to the

of energy flow
with

from

higher

temperature

system

the

lower

temperature.

Example:
fansitiariiy

Entropy

increase

with
Let

heal

on heiitjlow. and specific heat.

This example makesuse

of

ihc rentier's

previous

with an

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

AV

C.89J

K-'HTV

- 290K)
Ttie

- C.89J K-')C5OK
~ after

Tf)

where

ihe tempcraiures

are

in

kcMn.

linat temperature
+

contact

is

Tj

\302\253

|C5O

290JK

= 32OK.

Thus

At/,
and

\302\253

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

-11.7 J ,

At/3 = -At/,
(b)

= U.7J.
specimens

What

is the

change of entropy
immediately

of

the

two

when a transfer pf
that

taken place, almost fraction of ihe final


considered temperatures of

after

initial

con'act?

Notice

this

transfer

is a

0.1J has small

is small,

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
energy

Lan

of Imrrrmc

of Enlnpy

Tile cnlropy of iiic

second

hody

is increased

by

S2

,7~

= 3.45

Tile

iotal

enlropy

increases

by

AS, +
In fundamental,

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


units the increase

10-4JK-' = 0.59
x

1CTJJK~

of entropy

*s

where
of the

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

show
into

thai
thermal

ihc loial
contact.
~

ctttrapy
We have

always

increases

when

two

systems
a special after

;trc
case.
the

broughi If (he total energy V


systems

V% +

jusi demonstrated this in U2 is consiant, the lotal multiplicity

arc

in

thermal

contact

is

ff(t/)\302\273=

^0,A/^A/

t/,)

C3)
~~

containsthe by A8). This expression


niuitiplicuy

term

gi(EAo)i/i(^

^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, summation is large, but that the largest single term in the summationmay very
before

contact

and

many osher

~~

much larger than

the

initial

muilipiicity.

That

is,

(Mi).,,

= 9i(O,)gJiU

- 0.)

C4)

Chapter

2:

Entropy

and Teniperatur

with

Ut

= 0

anJ U,
the

* U. Exchange
syucm

of energy
found

parts and
probable
conftgL
eventually

presently

will be

in or

con figuration.
rat ions
reaches

Hie cm ropy
muhiplicily

increases or

takes piao; between h dose 10 tlie most as the jysicm attains The entropy
configuratic
probable

ofincreasirtg

probabilhy.
moit

ihe entropy

a{U) oflhe

may

be very, very

much larger than

ihe

initial

term

9iiVtMU'~
the Here 0s denotes The

Vl0).

C5)

value

of

Vl

for which
after

ihe product g^x is a


contacl

maximum.
iheir

essential

effect

is lhat

the syslems

cvoive

from

initial

configurations lo their final configurations. implies thai evoluiion in this operation will
final

The
always

fundamental
lake

place,

assumption with ali accessible

states

eqtutlly

probable.

The statement

fffjnil

C6)

is a

statement of the law of increaseofcnlropy:the entropy when a constraint [ends to remain constant or to iucrease

of

u closed

system

iniernul

to she

The operation is removed. ofebtabitsliiiig removal of the constraint that Vu


Ux

thermal

contact

is equivalent

sjstem to ihe
only

V2

each

be constant; ihe

after contact
thermal

U,

need be takes

constant.
combined

The evolution of the


configuration

system

lowards
separate

final

equilibrium

a certain

time. If

we

ihe two

systems before they

Add

energy

Decompose

molecules

Let a

linear polymer curl

up

Figure

2.9

Operations

thai

lend

io increase

the

entropy

ofa

syslcm.

reach
intermediate

(his cotifiguraiion,
energies

we

will

obtain

an

intermediate

configuration

with

and
function

an intermediate
of

view

the entropy
called

as a

the

lime
in

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

constraint,

(he lime

of evolution
of each

2.8. system
be

Processes
2.9;

that lend
in

lo increase the eniropy


support

are

shown
in the

in

Figure

the arguments

process

developed

chapters

that follow.

Chapter

2:

Entropy

and Temperature

For a largesysiem*
never

(in

thermal

occur

spontaneously

with another large sysiem)ihere will differences belween the actual value of the significant
coniaci

entropy

value of the entropy of the most probable of the configuration 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
and ihc
entropy

of ihe
afier

most probable
have
that

configuration

of

the

macroscopic
some

system
two

very
way.

shortly
which

we

changed
we

the nature
prepared

of ihe contactbetween
initially

systems,

implies

had

the system

in

special

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

never arise
operations

naturally

systems

left

undisturbed,

but

arise from

informed

on the

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

initial

specially

prepared

configuration.This
time

is true
and

even ihough the equations distinguish past and failure.

of motion

of physics

are reversiblein

do not

LAWS

OF

THERMODYNAMICS

is studied as a nonslatisticai subject,four posluiales of thermodynamics, are laws in are introduced. Tiicse postulates caiied ihe of thermal formuiaiion within our statistical essence, these laws are contained 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

thermodynamics

The

calculation

of Ihe lime

required

for

Ihe

process

is largely a

problem

in

hydrodyna

Laws

of Thtentotiynamks

of the

condition B0b)for
(e\\oSgt\\
{~\342\204\242rk

equilibrium

in thermal

comact:

feioSg3\\
{-furl:

/cloggA
{imX=
=

/cloggA
{~7urk

in oilier
heat is.
shali

words,

r,

t3 and r3

= t3

imply

rj

r2.

Heat is a form of energy. This law is no more than a slaicment of liie principle of conservationof energy. 8 discusses wliat form of energy Chapter
First law.

Second
use

law.

There

are

many
a constraim

equivalent
iniernal
of

statements
have

the statisiicai

statement, which we

called

of ihe second law. We ilie law of increase of

when entropy, applicable

commonly
is ill :l

used statement
will

of the

law

lo a dosed systemis removed. The increase of entropy is: \"Ifa closedsystem

configuration

tluit is not be lhat

(he equilibrium
a looser

consequence

ihc enlropy of the

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


siaicineiil

in successive

instants of time.\"Tins is
thermodynamic

ilian

he

one

we gave

wilh Eq.

C6} above.
of

The traditional
of second iaw
occur

thermodynamics;

whose soie effect is the of performance an equivalent amount of work.\" An that vioiaies lhe second engine 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
statement. Pianck formulationis a consequence oflhe statistical as the Third iaw. The entropy of a system approaches a 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
configurations

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

of
from

a system
the
the

which are
has

in

internal

thermal

equilibrium.

The third

iaw follows
multiplicity

statistical

definition

ground stateof
is

system

a weii-defined

g@),

the

corresponding

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

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
however,

would not be any


is essentially

objection

to

affirming
frozen-in

zero. Glasses
the

have a

substantial,of
in

order

of [he

number
reasonable

real

life is

that curves
flat

of many

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
that

must come in

as

r approaches

0.

Chapter 2: Entropy
Entropy

and

Temperature

as a
useful

Logarithm
properties

Several
rithm

follow

from

ihe definition
cad

of the

number of
the

accessible states, hut


of

of as

stales itself.First,

entropy

two

independent

of (he cmropy as the iogathe number of accessible systems is liie sum of lhe
ali

entropies. separate Second,


the

entropy

is

entirely

insensitive\342\200\224for

practical
is

purposes\342\200\224-to

the

precision

6U

with wiiich

the energy of a closedsystem


system

defined.

We have

never meant to
that

imply that
spectrum

tite

energy

is known

exactly, a circumstance
make

for

a discrete

of energy

eigenvalues would

the

number

of

accessible stales

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

a{U)
Typieally,

logO(t/)
of N
spins,

-t-

\\

C7)

as for

the system
tola!
then
A,

the

total

number
times

of states
same

will

be

of ihc

order

of

2V.

If

lhe

particle energy

energy C(l')

is of the

order of N

average

one-

2;7jVA. Thus
--'logNA

.
Let N

. a{V) =*
=

Nlog2

+ log^C.

C8)

~ IO20; A

IO\021* erg;

and 5U
x

\302\273 10^'

erg.

a(U)
We

*\302\273 0.69

10:o

- 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 of even the system term in N is dominant, a conclusion independent used for lhe energy.
see

from

this

exam pie of N; value

Example:

Perpetual

iiuxion

Early
lion

in our

study

of

physics

we came
wjli

to

machine,

a machine

ilui

gi\\c

forth

more energy

in.in

ii

absorbs.

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 work we available for any purpose at no cost to us.In brief, engine that delivers mechanical 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

in any of

lite quantum slates accessible !Oit.


probability
is

assumption

is that

a cioscd

system is equally
stale

likely

to

be

2,

ifPfi) quanliiy

is the X

that a

system is in

the

s, the

average value

ofa

3. An

ensemble of alike.

systems is composedof very


of

many

systems,

all constructed

4. The numberofaccessible states

the

combined

systems

1 and

2 is

,^ ^

*
where

s,
entropy

s2

= s.
a(N,U)

^'
the

5. The

to$g{N,U).
with

Tiie
fundamental

relation
entropy

S =
o.

kBa

connects

conventional

entropy

the

6. The fundamental

temperature r is defined by
1/t

[ca;cV)sx.
fundamental

The relation r
conventional

= kgT connects the

temperature

and

the con-

temperature. the when

7.

The

law of increase of entropy states that tends to remain constant or lo increase

entropy a constraint

ofa

closed sysicni intorn.il lo llic

system is removed.

Chapter

2:

Entropy

and Temperature

8. The
defined

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 are of the states in equilibriumproperties given accurately by consideration
of as

thermal equilibriumvalues
averages

over

all states

the most probableconfiguration

alone.

PROBLEMS

and

1. Entropy N is

and temperature. SupposegW) tile number of particles, {a}Show

CUiNn,
thai

wiiere
U
*=

C is
(b)

;t

constant

{Nt.

Show

that

{c^a/rU2)*

is negative.Tliis
Find

form

of

y( U)

;iciii;tlly applies hi an ideal gits. value


ui

2.

Ptirtitttagiwtisni.

the

equilibrium

ictn|KT;tit:rc

i of

ilie (Vac*

lional mngntrlizalion

M \\'m
of the
spin

2<s>/N

sysiem of
is 2s.

excess

h' spinseachofmagnetic momem in in a magnelic field B. The the as Take of lhc muliipliciiy lhe iogarlhilhm g(N,s) eniropy
c(s) =logg(Ar.O)-

as given in

A.35):
2s2/N

D0)

for |s|

\302\253 iV.

Him:

Show

that

in

this

approximation

g{U)
wtih

c0-

U2/2m2B2N,
\\jx

D1)
U denotes

oQ

1og(/{N,0).

Further, show thai

-U/)\302\2732B2N, where

<t/>, the lhermai averageenergy.


3. Quantum of frequency funciion

Replace

Express

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
hartitonic

m as

exp{/itu/r)

\342\200\224 1

,42)

This
that

!S the
does

not require

PSanck result; it us to

is derived
find

again

tn Chapter
function.

4 by a

powerful

method

ihemuilipiicity

where

of the
at the
will

used !ogl0 44 = 1.64345. a monkey-Hamlet {b} Show that the probability that
we have
universe in

will

be typed in
original

is any

therefore zero
never

approximately operational

10\"'64316. sense

The

probability
the

the age of Hamlet is


statement

of an

event, so that

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

5.

Addith-ity

entropy

A', =
product

far

1012spins with
gig2
I012,

two spin

systems.
functions

Given
g^x^i)

two

systems

of

multiplicity

as a
the

ss +

functtonofsj
#sj72 is
the

is relatively sharply peakedat s(


reduced by
multiplicity
jO\02174

and g2{N2.s
its peak

= s,.ForSj=
value. Use

- ss), the

JV, =s

product

from

the

Gaussian approximationto useful.

function:

the

form

A7) may be

(a) Compute
(b)

gigz/{9-i9z)m3X

for

s,

For

s =

1O10, by what

factor must
~
5i)\">

s, +
you

lOn and s =
multiply

0.
fo make
it

(gijh),,,a!l

equal

to

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

\302\247've l^e

^ctor

to

the

nearest order of

magnitude.

' j.

Jeans,

htysteriota

utirerst,

Cambridge
study,

Universily

Press,

1930, p. 4. The

slalenuill

is

attributed

to Huxley.

' For a rctaicd

malhematfco-iherary

sec'The

Libtary of Babel,\"

by ihe

fascinating Argentine

Clarke in

2001.

explanations

of the

average trretrme m an-seconds ii

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

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)

and

Tcmperatur

How

iarge is the fractional


For probability

error

in

the

entropy

when

you

ignore this

factor?

6, Integrated
is 10\"l0 \342\226\2405/JVj

deviation. the

approximately
use an

or larger.

Take

lhat gave ihe result A7), example the fractional deviation from equilibrium that = = You find it convenient to will IO2Z. iVj JV2
the
the

calculate
When

asymptotic expansion for

complementary

error

function.

\302\273i,

xp(x2)

(\"\"e

1 +

small terms.

Chapter

Boltzmann

Distribution

and

Helmholtz Free Energy

BOLTZMANN

FACTOR

58

Partition

Function
Two

61
State

Example: Energy and Heat Capacityof a Definition; Reversible Process

System

62

64

PRESSURE
Tlicrmodynaimc

6-1
identity

;>7

HELMHOLTZ

KttEE

ENERGY
of

6S
the Free

Example: Minimum ParamagneticSystem


Differential

Property

Energy of ;i
69

Relations
from

70

Maxwell Relation

7!
2

of f Calculation
IDEAL

71
LOOK

GAS:
in Af

FIRST

72 72

One Atom Example;

a Box Atoms

in a

Box
of

74

Energy

76
Equipartition

Example:
Example:
SUMMARY

Energy

77

Entropy of Mixing

7$
SO

PROBLEMS

81

1. Free
2.

Energy of a Two State Sysiem


Susceptibility O.ollaior

85

Magnetic

3. Free Energy of a Harmonic 4. Energy Fluctuations


5.

Si S3
S3

Overhauser

Effect

S4
84

6. Rotation
7.

of DiatomicMolecules Concentration

Zipper

Problem

S5

S. Quantum

S3

ChapfcrS:

Bol

auJ

lleliiiiioiiz

Free

Energy

9.

Partition

Function
of

for Two

Systems

10. Elasticity

Polymers

11. One-Dimensional

Gas

Chapter3; BolRinattn

Distribution

and

lleimkoitz

Free

Energy

The

laws

of thermodynamics

statistical

mechanics,

of

which

from the principles may easily be obtained are the incomplete they expression. Gibbi
mechanical

of

We

are

able

on anotherfrom lhai which to specify cases of thermal

to distinguish

in

terms

the thermal
in

we call

mechanical

the

narrower

action of one system sense . , . so as

action and

action. cases of mechanical


Glbbf

In

this

chafer
physical

we develop
properties

of the

the principles that


of
of

permit

us to
of

calculate

the values
We a very
have

assume that the

sysiem
called

&

a system as a ftinciion interest io us is in thermal

temperature. wiih equilibrium

ihe

iarge sysiem (ft,


common

[he

reservoir.

The iota!
influences,

temperature
system in

r because ihcy are in thermal contact. (ft + & is a closed sysiem, insuiaicd from
3.1.

The system

and the reservoir will


u!!

external

as

Figure

The

total

energy Uo

=*

U^

is \302\243/j
r,x is

constant. ihe

In

particular,

if the

sysiem is in a staleof energy

Ea, tltcn

Uo

energy

of

the reservoir.

Toial sysiem

Constant

energy

Vo

J.I

irOtiiUhcn

Rcprcs illation of a cioscd a! coniaci with a

loiat sjsieni

syst S.

n decomposed

iisioa

BOLTZMANN
A

FACTOR
of thermal

central
\302\253iil be

problem in a the

physics is

proportional

to

specific quantum Boitzmann factor.

10 find siaiu s of energy

the t,.

probability This

iltai

probability

ihe system is proporof

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

accessible

states
g\302\256t j

of ihe
siaies

of

Figure 3.2 The change nsetvoit u&nsfcss energy

of cnlropy t la

when ihe

fractional effec! laigc TCMivoii

(he system.

The

of

itie transfer

on ihe reservoir
ci\302\253iop>.

vil\\

luua

high

Energy

of

the reservoir

accessibleto (ft

A)

because

for our

present purposes we
energy

have

specified

the

state of

.S ,
number in Figure I al
Ei

If the system
stales accessible

is

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

energy

is Uo
is^f/o
in

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

of

to the reservoir in
probability

condition

\302\243,},

as

3.2.
is

The ratio
to \302\243,

of the
probability

that

the

system

is

quantum state

stale 2 at

energy
Ihe

Ihe

that the

system is in

quantum

energy

ratio

of Ihe

two multiplicities:
Multiplicity

of

<R (ft

at at

energy energy

Uo [/q

r.t

_
\302\243a(^o

ei)
B)
e2)

Multiplicity
This

of

\342\200\224 \302\2432

\342\200\224

91s(^'o

result

ts a

direct consequence of what


two

we

have

called

the fundamental

assumption. The

situations

are

shown

in Figure
of the

about
the

the

system

depend

on the
ow

constitution
the

3.3. Although questions of the reservoir, we shall seeihat


reservoir.
arc very,

dependence

is only in terms

the large,

temperature

if the reservoirsare very


We

multiplicities

very l.-irgcnumbers.

write

B)

of the

entropy of the reservoir:


\302\273

E.)

ff\302\253(t/0

C)

Chapters:

Bohzmnnn

Distribution and Helmholtz Free Energy'

Oi
E

01

ergy
yo

(/\342\200\236

',)

-', stale
8
Sta

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

;\302\260

'='

slates

tc I
gy\302\253>

State 2

Ene

Energy c.

Fi\302\273urc3.3

has a,,(U0 id

The

t,},

system

in

(a),

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

(b) is in quantum c,) acccisiblc quanluin

slate

t, 2. The

reservoir
(b)

slates,

in (a) and

D) the probability ratio for


the

two

states

1, 2

of the syslem is simply

E)
Let

us

expand

the entropies

in D)

in

a Taylor /(x0)

series
is

expansion

about

The Taylor seriesexpansion off[x)about

t)

0)
where

1/t

(S^/cCV^

gives the

temperature. The partial derivative

is taken

al energy
an

infinitely

Uo. The higher order termsin large reservoir.*


Acr^

liie

expansion

vanish

in the

limit

of

Therefore

defined

by

D) becomes

Affffl=
The final

-(\302\243,

-\302\2432)/T.

(8)

result of

E) and C) is

P{ez)

expft/r)'

'

term

of
utility.

the

form exp(
It

is \342\200\224e/t)

known

ofvust

gives
I

the
to

ratio
ttie

single: quantum state state 2. quantum

of Hie probability of finding of finding ihc probability

,as 3

Boltzmann factor.
the

This result is
system
in

in a
single

system

:i

Partition
h

Function

is helpfui

to consider the

function

Z(r)

5>p(~Ei/T)

A0}

ealied the

partition for

function. a!!

The 5 of

summation

is over

the Boltzmann factor


function

exp(-e,/t)

states

the

system. The

partition
and

is

the

pro-

proportionality factor between the

probability

p[Et)

(he

Boltzmann

factor

We see that
The

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

ZjZ

= 1:

result

(II)

is one

of the most
is V

is unity. the sum of all probabilities


useful

results

of

statistical

physics.

The

average energy of the

system

= (e)

= X^fo).

or
'

U
\342\200\242 gives

=,

Zh^Zh!A

= T^logZ/ct).

A2)

We expand

oft'j, ~

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

e) because

[he cupansion

of ihc

tatter quanliiyimmcdiatcty

convergence

difficulties.

ChapterS:

Battvnanti

Distribution

and

Helmholtz

Free Energy

0.5

0.4

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

Energy ystcm rgy

and

heat

as functions is plotteJ

capacity of a ofthe temperature

J
0.1

in units

ol t.

\342\226\240

The
with

average
a

energy

refers to
The

those statesof a
\342\226\240 ) denotes <\342\226\240

system

that

can

exchange

energy

reservoir.
the

notation

such

an average

value and is

called
for

thermal

average
with

or ensembie
common system

(e)

in conformity

average. In A2) the symbol U is used U will now refer to the system practice;

and not, as earlier,to the

-f reservoir.

Exwiiplc?
clc

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
Energy

uiid

wftli two

Z =
\"fhe average

exp(-G/t) +

exp(~\302\243/r)

-f

expf-s/t).

A3)

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

states

as

-\\e

and +\\e,

ty. We have

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

2cosh(fi/2t)

A5)

Partition

Function

and

-jctanh(c/2c).
of a

A6) at conslant Cv
volume

The heat capacityCv

syslem

is defined

as

s x(iajdx)r ,
C4a)

A7a)

which

by the

ihermodynamic

identity

derived

below

is

equivalent

lo

the

allcmate

definition

Cr
We

s (SU/dt)y.
energy

A7b)

hold

V conslant
A4)

because the values of the


and

arc calculaied

for a syslem

at a

specified

volume. From

(!?b},

'
A6).

-fEY

eXp(E/t)

A8a)

The
In

same resull follows from


conventional

unils

C, is defined

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

dimensions

of energy in ]Ilc

per kcivin.

Tim

siicctfic

heat

is drfmed
\\\\\\

us

itio

deal

capacity

per

unil

ri^i-immp

pio! of Iicii]cnpiiciiy
heat capacuy

versus

icmpcjiiiurc

t'iiHirc3

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

^ jLtiOiiKy

anomaly. For

\302\273 i, the

A8a) becomes

Cr^(E/2iJ.
N'oiicc

A9)

ihat

Cy cc

r\"\": in

in

ihis

lemperaiuie

is small

comparison

high tempcraiufe limit. Iii ilie low teraperaiuie whh llic energy level spacing e. For i

limil
\302\253 e we

ihc have

Cy ^
The

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

CO}
because

exponen'.ial

factor

exp[

\342\200\224 rcJuces

r,'t}

as r

decreases,

exp[

~ 1/v) -> 0

as a-

0.

Chapter}:

Boltzmann

Distribution

and Hdmhoki

Free

Energy

Definition:

way ihai

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

process,

A process

ihe system

is always

system

will

be

returned

to its

initial

condition.

In

reversible

processes,

the

condition of the system is welt

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

whose
A

condition
volume

is undefined.
that

change

leaves
will

reversible exampleof an isentropic

the system
process. be
in

in

the

same

quantum

state

is an

If the

same
process, not

state
because change.

the entropy
the Any

change

zero

between

number process

of states
in which

an

ensemble

system always remains in the any two stages of the pro(p. 31) of similar systems does
an

the entropy

change vanishes is
not

isentropic

reversible
processes,

process.

But reversible
a special

processes are

limited

to

isentropic

pro-

and

we shaHhave

interest also in

isothermal

reversible

processes.

PRESSURE

Consider a

system in

the

quantum

state

s of

energy e,. We

assume

e, to

be a

function of the volume of the syslem.The volume is decreased 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

&V)~

eJ^V) -(dtJdV)bV

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

B1)

Consider
work

cube

a pressure p, applied normal done on the system by the pressure


from

to all facesof a cube.


in a contraction
as the

The

mechanical

volume

Kto

\342\200\224

AKappears

(Figure 3.6) of the change of energy of the system:


-(deJdVyLV. .

U(V

Af)

- U(V) .=*

At/

B2)

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

O.S

i.O

t.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

ensemble

of systems

will

increase

in a revcrsibk
is )he

ranee

energy

iiself is of no practical impottance. lhal is impotlaiU.

ti

cha

Tigure

3.6

Volume of a

cliangc

- AI'

compression

cube.

Chapter i;

Batiziriann

Distribution

and

Ihtmhottz

Free

Energy

Here

V denotes

the energy

of the system. Let A


+

be

the

area

of one

face of ihe

cube;then
A{Ax

Ay -

+ Az) Az are

AV

B3)

if ail

increments
wotk

V and

Ax

=s

Ay

taken as

positive in

the

compres-

compression. The

done

in the
AV

compression is
psA(&x

Ay

Az)

PiAV

B4)

so that, on comparisonwith

B2),

P,

-thjdv s.
ensemble

B5)

is the pressure on a system in We average B5) over all states


usually <\302\243>,

the

stale
of

the

to obtain

the average pressure

written

as p:

B6)

where U
number

<t>.

The
in

entropy
the
We

a is

held constant in ihc tlcrivaiivi;


is uuclianged
in

because

ihc

of states
in

ensemble
hove

the

reversible

compression
some

we have

described.
fhis

a collection

of systems,

each

in

stme,

and

each remains

_st:ile

in ihe

compression.
mechanic!

system lhat is maintained in some specific state. Appendix D discusses the result moredeeply. we shall need also the later result E0) for For applications 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

The result B6) corresponds to our

picture

of the

pressure on a

only

the

two

variables

U and

describe

the

system.

The differential

of

the entropy is
da[U.V)

Uu

B7)

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

change of
dV.
th;it

the

entropy

Tor

arbitrary

independent

Assume
the

two

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

Thermodyaamie

Identity

cancel.
interdependent

The

overall
values

entropy change
of dll

da

will

be

zero.
{&V}at

If we
the

denote
entropy

these interchange will

and dV by {W)a

and

be zero:

B8)

)
Bui \302\273he ratio (*5[/)\342\200\236/(<)F),

B9)
Jerivative

is

the

partial

of U

wilh respect to

at

constant

o:

(iV)J(SV),
With

s ldU/dV),.

C0)

this

and

the dcfiniiion

l/i

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

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

By B6)

the kft-h;ll)d

side of C1) is

equal

to

-ft

whence

Therniodynaniic
and

Identity
differential

Consider again the


ihe

B7)

of the

entropy; substitute the new

result for

pressure

the

definition of i to obtain

Ttla

dU

-f pdV.

Chapter3: Bohynaaa
This

Distribution

and Helmbohi

Free

Energy

useful
will

relation
appear

will be
in

called the

thcrtnodjnsmk identity,
transposition gives

The

form

with

variable

E.38).

A simple

dU =
If the actual

TVS

pdV.
is

C4b)
we can

process of change of stateof the

system

reversible,

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

systems

brought

into

thermal

contact (Chapter

8).

HELMHOLTZ FREE
The

ENERGY

function

C5)

is called

the Hclmhoitz free


at

energy.

This

function
V

plays the
plays

part in thermal
mechanical

physics

constant

temperature

that

the energy

in ordinary

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
*=

dUL

C7)
to

the condition for F to be an extremum with F because like at constant volume and temperature. We the energy eigenvalues e, of the system (seep. 72).
which is

respect

all variations
it

we can

calculate

from

tfehuitoh:

Free

Energy

Comment.
i',R

We can show
\342\226\240 Then

that

the

extiemum

is a minimum.

The

total

energy

is V

==

Us

ihe tola!

eniropy is

* e^U)
We know

- UtfffJtVrivji +

ffsiUj).

C3)

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

i/t

C9)

so thai

C8)

becomes

a^a^iV)
where

- FJx ,
the

D0)
<rlk(Lr) respect system will

Fj
thai

\302\273

L/j

o,

w^ is ihc free energy of +

system.-Now
with

is consiant;

and we

rewll

=
mus)

in

equilibrium
vviiii

is a maximum
respect system

to Us is in increase

D0) lha)
configuraiion.

Ft

be a

minimum

lo Vs at

The

free energy

of

the

when the constant r, V

. It follows from ihc mosi probable for any deparluce

hxti'iiplc:
model

Slltthnuiii

property

vf the

sy^tcfn

of tliaptcr

I.
A't

\\viUi

the
with

spin

excess is 2s

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

tifa

N't

tlicliclpofan

approximate

form of A.31}:

,4,,
The

energy

elementary magnet.

in a magnetic field Tile fice cncigy

Bis.- 2\\tttfl, funaion (to

w licrc

m is ilic
ldc

magnetic woniciilofan
function
in

elemen-

be called

lapdau

Chapter

tO) is

FJjaB)

&

V{s,m

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

lo the
of z

equilibrium

and B. The

= 0

= -JmB +

tlog^4-|-

D3)

Thus

in the

magnetic

field

B lhe

thermal

equilibrium value

ofihe spin

excess

Is

or,

on dividing

numerator

and denominator
<2s>
\302\273

by

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

Ntanh(mi?/r).

D5)

The magnetization

,U is the magnetic
the

per

unii

volume,

magnetizalion

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

M =
The
It

<2s>m/K =

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

D6)

is

easier,

free energy of however, Z

ihe system in equilibrium to obtain F directly


=
exp(\302\273iB/r)

can
from

be obtained
the

by

substituting
for

D5) in
one

D2).

partition
\302\253

function

magnet:

expt-niB/r)

2cosh(mB/t).

D7)

Now use
for

the

relation

N magneis.

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

F =

Differential Relations

The

differential

off

is

dF =
with

dU - xda -

oiit,

or,

use

of the

thermodynamic

identity C4a),
\342\200\224fdV \342\226\240

dF = -adt
for

which

D9)

These
for

relations are
energy

widely used.
F

The free
an

in

the

result

=\302\273

-(rf/^K),

acts

as the eilecttvc
B6).

energy
result

isvihcnwil

change

of volume;

contrast this result witii

The

Calculation of Ffrom Z

may be written

as

' use

-($.
terms

\342\231\246

\342\226\240

<D,
on

by
what

of F
we

= U
call

~ to. The two

the

right-hand

side of E0)

represent

may

pressure

~-(cU/dV)f

the energy pressure and is dominant in most in gases

the entropy pressure.The energy solids and the entropy pressure


{Problem

x(?a/3V)t 10). The

is dominant

contribution entropy: Ihe natve from mechanics must tell that simple feeling everything -JUjdV about the pressure is seriously incomplete a for at constant temperature, process 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
enlropy

and in elastic polymers suelias rubber is testimony of the importanceof the

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)

useful

relations tliermodynamic must Hx and ^FfcxcV,which

(ca/dV)t

*{ep;eT)y

E!)

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,

Calculation

of F
U

from Z
%a and

Because F =
F

a =

-{cFjdi)Vt we have the or


by

differential

equation

U +

i{SF/dt)Vt
is satisfied,

~x2c(F/z)Jcx

\302\253 U.

E2S

Wo show

thul

this

equation

F/x
where

- -log^ .

E.1)

is the

partition

fund ton.

On substitution.

Chapter3:
by

Bollzittnnn

Distribution

and Hchniipliz

Free

Energy

A2).

This

proves

that

F=

-riogZ

E5)

satisfies It

the would

required appear

differential possible
However, that

equafion E2). for Fjx to contain an


the

additive

constant

a such

that

F =
are g{t

-riogZ
occupied.

+ ar.
is so
In

entropy

must

temperature

low
that

only

the

cj0 coincident

limit logZ
if

-* logg0~ W*.

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


s0

thai

a =

-cFjcr

\342\200\224

log

Z)fct

logg0 only

a ~

0.

We may

write the result as

Zand

cxp{-f/t);
probability of a
quantum

E6)

the

Boftzmann

factor

(II)

for the occupancy

state

s becomes

E7)

IDEAL
One atom

GAS:
in

FIRST

LOOK

a box.

We

calculate

the partition
of

mass
free

free

to wave

move

in a

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

volume

function Zx of one atom of V ~ L1. The orbitals of the


are

particle

equation

== ei/i

\\p{x,y,z)

= Asia(nxitx

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

,
integers

E8)
do

where ir,, nyt n. are any positive integers, as in and a zero does not give independent orbitals,
values

1. Negative

not give

a solution. The energy

are

We
system

neglect
is

the spin

and all otherstructure


by the

of

the
nft

atom,
n:.

so that

a state of

the

entirely

specified

values of nlt

Ideal Cm:

First

Look

The

partiiion

function is ihe sum

over the states E9);

Provided

the

spacing

of adjacent

energy values

is small in comparisonwiih

t,

we

may

replace

the summations
I

by integrations:
(/ji,cxp[
\342\200\224

2] =
The notation a\"
may

t!nx

dnf

*2{nx2

ny2 +

'u2)].

F1)

&

Azji2/2A/12t

is introduced

for convenience.

The exponential

be

written

as ihe

product of Ihrec factors

F2)
in

ierms

of ihe

concentration

ji

XjV.

Here

F3!

is catted the

quantum

concentration.

It is

the conccnlration
lie

associated with one


Broglie

atom

in

cube

of side

equal to

die thermal average


-

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

small

10 unity, so ihat helium is very dilute under normal conditions. compared 1 we say ihat the Whenever n/nQ \302\253 is the ctassieai An ideal gas in 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),

F4)

becauseZj\"' exp{

eJx)

is (he

probability

the system

is in

the

state

it. From

F2),

log^i =
so that for an

\342\200\224

jlog(I/i)

-f-

terms

independent

of t ,

ideal gas of one atom

F5) If t
=*

kaT,

where
the

kB is

known result for

:Iic Boltzmann constant, then per atom of an ideal gas. energy


occupancy

lkHT,

the well-

The
equiility

thermal

average

of'a

free particle

orbital satisfies the

in-

which
helium

sets
atom

an upper limit
at

of 4 x

!0\026

for

the

occupancy note

of an

orbital by a
by E9)

standard
this
for

concentration
must atom.

and temperature.
be
\302\253 1.

For the classical

to regime
is always

apply,

occupancy
a free

We

that

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

positive

temporarily
many

tiiitil

noniulcmaing

box, all atoms


one
utoni

result.

identic!!, of ik

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

First

Look

\342\226\241 I

!\342\226\241

Figure 3.7 An .V particle of.V bo\\es. The energy is

system

N limesthat

of free particles with one panicle for one particlein one box.

in each

Figure

3.8

Atoms

of different

species in

If we have cfne atom in each of product of ihc separateone aiom

iV

distinct

partition =

boxes (Figure funclioiis:

3.7), the

partition

funciion

is fhe

ZXha*\302\273

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

,
independent

F6)
state

because ihe

product

on

!he right-hand

sido includesevery

of llic N

':,(!)
where 3, fi.... Cdenotethe orbital also gives lite pjiiiiioit function single box (Figure 3.S):

f-

r.^2)

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

F7)

indices
of

oUlotm

in

ihc

suewssive

boxes. The

result

F6) a

iV itottmiontciJng

aiuiits

all ordilTcrctii

speciesin

iliis

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
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:

BoHzmann

Distribution

ami Hdmhohz

Free

Energy

If tlicorbiial

entry

slsould

occur

indices are alt onlj once


correct

diffrfem,
if

each

ihe

panicles

a faclor

of ,V!, ;md the

partition

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

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

in ihe
diticrcnt

classical regime.Here nQ There isaslep in ihe argitmcni


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

ih^S
(lie gas. the

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 measurable and i! lias been confirmed ihat quaniily, jV! facior is corrcci in this low concentration irmit.

Energy,

The energy of

{he ideal gas

follows

from

{he

N particle

partition

funciion by use of{l2):

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

F9)

with

{65} for

one panicle.

The

free

energy

is

F =

-ilogZy
Zt = naV
\342\200\224we

- -i]ogZi'v + ilogN!.

G0)

With

{he

earlier
c=

result
NlogN

= (Mr/2n/!2K'i2KandtheStirlingappfoximahave

tionlogN!

N,

F =
the free
N

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

+ rNtogN
and

xN.

{71}

From

gas of

aioms.

ihe entropy energy we can calculate The follows from {49}: pressure

the pressure

of the

ideal

p -

-BF/3K), =

NxjV

{72}

PK

Nr,

G3)

IdtalGas:
is called

first

Look

which

the iJcal gas law.In conventional


1>V =

units,

NkuT.

G-1)

The entropy follows


a =

from

D9};

-{CF/?z)r

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

\\N

NlogN

+ S , G5}

G6)

with
equation

(he

concentration
for

\342\200\224

NjV,

the

entropy
h

of a
through

The

result

involves
involves

the entropy
Chapter

a quantum

result is known as the Sackur-Tctrodc This monatomtc ideal gas.It agrees with experiment. so even for the the term classical ideal gas hq, shall derive these results We again tn concept.
does

6 by

a direct

method
V

that

not

explicitly
from

involve the
U
*=

N\\

or

identical

particle

argument.
have

The energy

also follows {69}

xa; with use

of

we {7!}and {76}

= \\Nr.

Example!
contribution

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,.
Equipanlihn

i* from

For one free

particle

Jjjexp[~

pI1)/2Mx']dpIdpfilp.

{77}
The thermal

a result
The

similar

to Ft).
be

The limits of integration


calculated by use

are

fat \302\261ao

each

component.
Kamiltonian
the

average energy may


result

of A2) and is equal wfr.


the

ts generalized

in the

of degree2 in thermal averagekinetic energy


is homogeneous hamiltonian
is

classical theory. Whenever


momentum

a canonical

component,
coordinate
will

classical be

associated of degree

with thai momentum

wilt

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

homogeneous energy

in

a posilion

average potential

associated

with

that coordinate

also

component, theihermal be Jr. The resull thus

3 Vibt

^\342\200\224\302\273

lion

T,\302\273s

25

50

75100

250
Temperature.

500 1000 2500 5000


K

Figure
the

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 classical limits are attained wlicn high icinpciaturc i \302\273 relevant energy level separations.-.
3.9
gas phase.

applies to ihe
harmonic At

harmonic

oscillator

and

for the

high

temperatures

in the classical limit. The quantum diatomic roiator are derived in Problems the dais teal limits as in Figure are attained,
oscillator

results

for the

har-

3 and
3.9,

6, respectively.

Example:
arrangementsof

A and

Entropy ofttuxia*. In Chapter 8 in a solid made up of ,V


of arrangements:

1 we

calculated
atoms

the

number

of possible found

A arid t

atoms B. We

arrangein A.20)

for

the

number

A/i

G3)

The crtiopy associated


c{A',0 =
and

with

these

arrangements

is
!og{iV

logflMf) 3.10for
jV

bg,V! This

r)!

~ logti

, of ;tn

G9)
alloy

is piotied

in Fi^me

~ 20.

contribution

to the

total entropy

itfcalGas;

A First

lj>ak

\\

4\342\200\224-~

vj

7
0

0.2
Alloy

0-4
composition

0.6
At_x

0.S
Br

1.0

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

of mining.

The

result

G9)

may

be put

in

a more

convenient

approximation:

=* NlagN
=

- N - (N

(N

i)\\ag{N
-

- i) +
t)~~

t ~

rlogt

NlogN

!)\\og(N

l\\agl ,

= -(,V
.viih

- t)Iog(l -

//N)

l Iog(f/jV)

= t/N,

- -v)Iog(I This

-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
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

homogeneous

solid

solution
pure

will

have

ofc/yitatlilci of the

elements.

The

F =

Fo

tct(.v)

\302\273

Fo

A't[A

- .\\)Iog{l -

a)

xlogx]

(81)

which

we

must

compare

with

F =
Tor is

x)F0

+ xF0
A

- Fo
the
.vj

(82)

the mixture always

of

and

B crystals
entropies

in the
arc

proportion

positive\342\200\224all

positive\342\200\224so

that

The entropy of mixing solid soiution has ihe lower


to x. element

free energy
any

in

this special
tendency

case.
at least a very
if a

There is a
other
sutroundiug

for

small proportion
etlergy

of any

B to a B

element

A,

evert

strong

repulsive

exists

between

dissolve in atom and ihe quantity.


xi\\U, If

A atoms.

Let this
\302\253 t of

very small xN is ihe

proportion -\\ number of B

atoms.Tlic

repulsive energy be denoted by U, B aioms is present, the Iota! repulsive


mixing

a positive

energy is

wlk-re

eniropy

(SO) is

approximately

a =

~.\\N\\ogx

(83)

Fix)

N(sU

+ txiog.v)

(84)

which

has

a minimum

when

BFfBx

\302\273

N(U

xiog-v

+ t)

= 0 ,

{85}

x
This shows there is a
natural

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

(86)

impurity

in all crystals.

SUMMARY

1. The factor
?{\302\243j)

expf-e./tJ/Z in a

is the

probabiHty of finding

a system

slate s of energy c, when

the

system

is in thermal

comaei
the

with

a large

reservoir

ai temperature

r. The numberof

particles
in

system
function

is assumed
is

constant.

2. The partition

3.

The

pressure

is given by

p =

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

4.
5.

The

Hejmltoltz

free for

energy

as F ^ U ~
V.

xa.

is a

mittimum

in

equilibrium

a system

held at
~{8F/dV)r

constant i,
'

-i?F/dT)y;
and

p
o derived

\302\273

6.

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

ttscru!

incilcuhitiansorf

such as p

and ofquuniiiics

from F.
atoms

7. For an ideal monatomic gas of N

of spin

zero,

ZH =
if

(nQVf/N\\ ,
nQ

N/V

\302\253 \302\273a.The

quantum

concentration

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

Further,

pV

JVt;

o =

W[log(iic/H)

5];

fW.

8.

process

is reversible

equilibrium

state at all

if the sysiem remainsinfinitesimally times during ihe process.

close

to

ihe

PROBLEMS

/.
in

Free

energy
function

of

a two
of

energy as a
of

state systenu (a) Find of a system with two


expressions Figure

an

expression

for

the

free

states,

one
for

at energy
itnd

0 and one
entropy

fro; ettcrgy, find energy the system. Tttc entropy is plotted in


c. (b)

From ihe

the energy

3.11.

2.

Magnate
for

susceptibility.
ihe

00 Use ihe
M

pitriiiion tltu

function susceptibility

io x

expression
function

tnagiteliAUiou

end

find nn exaci s ilM/tlB as a


of

of

temperature

and

magnetic

field for the


for

model system
magnetization

magnetic

moments

in

a magnetic

field. The result


another

the

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

method.

Here

is M ~ the is particle

Chapter

Si

Bolizmann

Distribution

and

tjelinholt;

Free

Energy

OR 2

0.6

0.4
/

A/

0.2

/
ft

0.5

1.0

1.5

2.0

Figure

3.12

Plot

of ihe
hiS

ofmfl'r.
of HiiJ/r,

Notice thai
bul
Ai

31 lou

high

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

contciiiraitot!. Tlie result


express thul the
i.
oscillator

is

plottcJ
only

the result

as a function
is x
harmonic

ofr

in Hgure 3.12. (b) Find and the parameicr.v ttniit


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

ihe
s

free M/tuu,

energy (c)

and Show

sust;eptibiltty
energy of
an

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

/Vcc
has

oscillator.

A one-dt'mcnsian;il
states,

liurmonic
\302\243,

oscilwhere

infinite

series of

equally spacedenergy

with

sho,

Figure

3.13

Enin

osciliuSor

of frequency

s is a
Wu

positive imegeror zero,


chosen

and

to is
at

tlic classical
the

have

the

zero

harmonic

oscillator

the free energy is

of energy

state

s =

frequency of she oscillaior. for a 0. (;s) Show that

(S7)

Note

that

at

of the logarithm to obtain F^i

high

temperatures

such ihal
!og(/itu/t).

\302\273 fitu

we

may expand

the argument

(b)

From

(87) show thai the

entropy

($8}

The
4.

entropy

is

shown

in Figure

3.13 and the heat

capacity in
volume

Figure

3.1-i.

Energy
is

fluctuations.

Consider a systemof fixed


the

ta thermal

contact

wiiis a
syslcin

reservoir- Show that

mean

square

fluctuation

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

U is

to

relate

Chapter

3:

Bohzmnn

Distrihut

mJ

IIcIihUoUz

Free

Energy

S\302\273re3.S4 r

Heal

harmonic

capacity oscillator of
in

Versus u-mperatufe

frequency

u>.

The

ifiiontal
unncal mlcln iiit iluc

scale is
wilh

units

flE.

\302\253herc 0,

of i/fiw, whkh is calkd rhc

is

Icniperamte. Cv

\\n the high


1 \\\\\\t

- kB.ot
'as

in run<iamciiia! c^issic^I

is k^own

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

mpcratures

C(- decreases

csponeniially.

y
0.5

1.0

not fluctuate
Any

v,\\

value

\\shcn

the system
such

is

in

thermal our

contact definition

with of the

a reservoir.

otltcr

attiiude

would

be inconsibletit
of

with

of a system.The energy
do^s

temperature

Thus

may fiuetijiitc, but the temperature Sorr.c workers ltot. do not acllterc to a rigorous definition of temperature. Landau arid Ltfshttz etve Hie result
a system
\302\253AtJ>

=> t2/Cv

(90) equal to

but

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).

- r=C,.,

5.
electrical

Ovcrhaussr

whenever
increase
positive

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
effect.

Suppose

that

by a

one

can

system

is given by

This reasoninggives the statistical basts of the Ovcrhattser effect the whereby 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
only

considered

of diatomic molecules. the translationa! energy

In our
of the

first

look

at
But

the ideal
molecules

gas we
can

con-

particles.

rotate,

with kinetic of a diatomic

energy. The rotational motion is quantised; and the energy molecule arc or the form
ft;}

levels

= jlj

l)\302\243o

(92}

where; of e;ich

is any

posilive integer includingzero:/ = level is </(;) - 2; + I. (a) Find rotational


of

0, I,2,.. ..
the

The

multiplicity

for the rotational states


approximately for

one

molecule.
makes

Remeniber

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


r
\302\273

a difference,

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

function

that

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
e0,

by

converting

\302\253 sOl

by

truncating

the sum

approaches

{or,

in conventional
the A

units,
limiting

A-,,)\\Uv?n

r \302\273 r.0.lc)

Sketch and
state

the behavior r -*

of L'(t) nnd closed

C{x), showing
citefgy

behaviors

for

-\302\273 ro

0.
it is

7. Zipper pruhh'W.
with that

zipper

h:is N
in

links; each link


ii is

has n

tti which
t:. We

0 and

u siate can

which

open

with

energy

require,

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

and

that
already

site link
open,

1}

are

form

193}

{b) In the

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

open links.The modelis


DNA
molecules\342\200\224see

5,

Quantum

concentration.

Consider

one

L;

particle

confined to a

cube of side
i

lhe

concern

rai ion in

effect is n
kineiic

when

in the

ground orbtial. There

1/L3. Find the kineiic energy will be a value ofthceoticentraiioii is equal

of

he

particle

for which
this

lhis zero-poini quantum


concern

energy

to the

temperature r. (At

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 eoticcntraiton nQ defined by {63), wtthtti a facior of ihe orderof utitiy.
9.

Partition

function

for

two

systems.

Show I and
of

thai

the

partition
contaci

function
common

Z(l 4-2) of two systems:

independent

sysiems

in

thermal

at a

temperature t is equal 10ihe produci

ihe

paniUon

funciions

of the

separate

Z(I +

2)

Z(I)ZB).

(94)

ChaptcrS:

Boltzntann

Distribution

and

Heimhaltz

free

Energy

10.

Elasticity

of potythevs.

The lhermodyiiamic

identity for

a One-dimensional

system

is

zda =
when

dU ~ fdi
ill is
find

(95)

/ is

line. By

the external forceexerted on the line and form the derivative to witSi we C2) analogy

the extension of the

.-Ha-

The direction of

the

force

is

opposite

to the

conventional direction of the


/>, with

pressure.
We

consider

a polymeric

chain

of N

links each of length


to the left,

each

link

equally likely to be directedto the right of arrangements that a head-ioiail give + q(N,s)

and

(a)Show ihat the number


2js|p

length

of

is

q(N,-s)

'
-T\342\200\224~

(kN

4- 5)!

(\302\243N

(97)

s)\\

(b) For

\\s\\

\302\253 JV

show

that

(98)

(c) Show

that

the

force

at extension

/ is

/ = h/Np1.
The

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

force

is proportional

to the

temperature r.

The

pti5tides

have spin

zero.

Chapter

Thermal

Radiation

and

Planck Distribution

PLANCK

DISTRIBUTION

FUNCTION

PLANCK
Emission

LAW
and

AND STEFAN-EOLTZMANN
KirchhorT
Body

LAW

Absorption:
Black

Law Radiation

96

Estimation of Surface Temperature


Example:

97

Cosmic

Background

93

ELECTRICAL NOISE

PHONONSIN SOLIDS:
Numberof

DEBYE

THEORY

102

Phonon

Modes

104

109
Number of
Surface

Thermal Photons
of

no 110
Sun

Temperature

Ike Sun

Average Temperature of the interior of the


Age

111
111

of the Sun
Earth

Surface Temperature of tlte


Pressure

111

of Thermal Shields

Radiation
Gas

111

Free Energy of a Photon


Heat

112

112

Photon

Ga: in One Dimension


ty

112
Space

Heat Capai

ol\" intergalactic

113
Limit

HeatCapa'
Energy

ty of Solids in
of

High Temperature
and Phonons

113

HeatCapai ;ty
Flu>

Photons

113

HeatCapai

tuations in a Solid at Low Temperatures 4He at Low Temperatures ty of Liquid

113

113
114

Angular image
Entropy

D: of a
and

tribution of Radiant
Occupancy

Energy

Flux

114
114

Radiant Object
Expansion

Isentropic
Reflective

of Photon
and

Gas
Law EFFECT

Heat

Shield

Kirchhoff's

115

SUPPLEMENT:

GREENHOUSE

Chapter's: Thermal

Radio

[We
v,

//

the distribution of consider] U is viewed as divisiblewithout


whole

the

energy limit,

U among then

N oscillators
this

of frequency

an infinite

number of
is the

distributionsare possible. We
of the
finite calculation\342\200\224Vas

consider

however\342\200\224wUl

essential point

made up of
by

equal

parts,

erg-sec.This constant when


oscillators

and we make use of the


multiplied

an entirely determined nimiber of natural constant h = 6.55 x fO~21


the common
ergs

frequency

of

the

gives the element

of energy e in

....

M. Planck

Planck

Distribution

Fu

PLANCK

DISTRIBUTION

FUNCTION
spectrum

The Planck
in

distribution describes the

of

the electromagnetic

radiation

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 Planck distribution electromagnetic also describes the thermal energy spectrum of lattice vibrations m an clastic
thermal

solid.

The word

the cavity or in the solid. We shall refer always the radiation. The characteristic feature of the of oscillation
energy

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

in
of

is radiationproblem
only in units
in

that

a mode

of frequency w
The

may

be

excited

of the
the

quantum of
is

hio.

energy

of \302\243,

the

state

with

s quanta

mode

e,

U)
(Figure

where s is zero or any


energy

positive

integer

4.!). We omit the

zero point
oscillator
harmonic

\\hai.

These

energies

of

frequency

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

are the same

Figure

4.1

represents

Stales of an oscillator a mode of frequency

that
tu of

an

to s

photons in

the

mode.

(-haptcr

4-

Thtftjml

Radiation

and Planck

Distribution

modes a and
magnetic

b, of

frequency
in

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

occupancy ofeach mode.

field is suggested

figures

amplitude for one pliotor

oscillator is a iocasized the osciiiator.whereas an electromagneticcavity mode is distributed


cavity

electric

and

magnetic

throughout

energy the: interior of

of

the

are integral (Figure problems the energy eigenvalues 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)
4.2).

For

both

}{~shia/r}. This
sum

B)
.\\-

is of

ihc form
may

TV,
be

with

.\\-

exp{-/i<y/0-

Because

is smaller

than

1,

the infinite scries

summed

and

has the value 1/A

-- x), whence

C)
1

-exp(-tou/T)

Planck Lax and

Lt* Slefan-Bohimann
is

The

probability

that

the

system

is in the

state s of energy slim


\342\200\224

given

by the

Bohzntann

factor:

P(s)

exp(

shci/x)

The thermalaverage

value

of

s is

E)

With

>' =

ftej/r, the summation on the

rmht-hand

side

has

the

form:

-cxpt-v)/

From C)

and E) we

find

-exp(->.)'

F)

This is the Planck distribution

function

for

the

thermal
lo

average
it is

number of
the average

photons(Figure
number of
with

4.3)

in

a singie

mode of

frequency w. Equally,
applies

energy

phonons in the mode.The result in the form of (!).


LAW

any

kind of

wave

field

PLANCK
The thermal

AND

STEFAN-BOLTZMANN

LAW

average energy in the modeis

\342\200\224 )

G)

1*

Chapter

4: Thermal Radiation

and

Planck

Disiribttlio

+ *(\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

0.5

The

high

temperature
may

limit approximated

\302\273 ha)

is

often

called

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

limit. Here
classical

exp{frfcj/t)

be

as

1 4-

lna/r 4-

the

average energy is
^ <\302\243> T.

(8)

There mode
n

is an
has

infinite

number

of electromagnetic
wn.

modes

within

any

cavity.

Each

its

own
in

frequency
the

For

radiation

confined
is

within
a set

conducting cavity
form

form

of a

cube of edgeL, there

a perfectly of modes of the

Ex

ExOitn

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

,
,

(9a)
(9b)

ID
Et

sin(fl=Tiz/L)

= E-0
Ex

(9c)
the

Here Ex, Er and


are \302\243;0

are

three electric

field components, and

\302\243lQ,Ey0 not

and

the

independent,because

corresponding amplitudes. the field must be divergence-free:

The three

components are

indepen-

A0)

Planck

Law

and

Slcfan-Bolwtann

Law

When we insert {9} into A0}


\302\243,0\",

and

drop

ail common

factors, we

find

the

condition

E^nr

4- E:Qn:
be

-. Eo \342\226\240 0n \302\273
to the
in

A1)

This
the

states

rhar the nx,

field vectors must


ny

perpendicular

vector
the

with

components

and

>l, so that

the electromagnetic field


is defined

cavity

is a

transversely polarized

field.The polarization direction


n,,

as the

direction

of Eo.

For a
polarization

given

triplet

directions,

can choose two so rhat rhere are mo distinct


nft

n. we

mutually modes

perpendicular for

each

iriplei

On substitution of (9) in the wave

equation

V'-v1

i:y

trJJ.

'.

.(V

wilh

c the

velocity

of light, we
cWnJ

find

4-

Hya

n;2)

= w3L2. in terms

A3) of Hie triplet

This determinesthe frequency


>h<

\302\253) of

the

mode

of integers

\"y

if we \";\342\226\240

define
= (rtj[2 \342\200\236

,,/

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

A4)

then

the frequencies

are of the

form

w.

mrc/L.
is, from

A5) G),

The total energy of the

photons in the

cavity

The sum is over the triplet of


describe ny,

all

independent

iij

by an integral
That

over

integers alone will the sum over nx, modes of tlic form (9). We replace in the the volume clement space of the mode ditx dny dnx

integers nx,

ny,

n..

Positive

indices.

is,

we set

Chapte

where the factor


involved. two

=h

arises (\302\243K

because

only

the positive
a factor

We independent
cavity

now

multiply
polamations Thus

the sura

or integral by

setsof

of the electromagnetic

octant of the Spaceis of 2 because Ihere are field (two independent

modes).

, = 1 ji ft

hu)n

Jo
r

(nVic/L)

dnn*

\342\200\224

\302\273\302\260

A8)

ex

with
over

A5) for

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

practice

is to

transform
nhcn/LT,

the definite integral to one


and

a dimensionless

variable.

We set

x =

A8)

becomes

A'J)

The definite

integral has the value z*/l5; it


(cited

is

found

in good

standard
volume

tables
is

such as Dwight

in the

general

references}. Tlie

energy per unit

\\Shs

B0)

with

the

volume
fourth

V =

L1. The
oflhe

result that
lemperalure

the

radiant

energy

density

is propor-

lional !olhe
law

power

is known

as theStefan-Boltzmann

of

radiation.

we B0) into the spectral decompose applications of this theory as the energy per unil of the radiation.The is defined density density spectral 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

U/V

B1)
is

so

that

the

spectral

density

B2)

Planck

Law

andSufan-Boltzmam

Law

1.2

\\
/
\342\200\224

1.0

/
0.6 0.4
/
1

/
\\

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

0.2 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

range.

so ihe

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.

Chapter

4: Thermal

Radiation

and

Planck

Distribution

gy The
area

v
energy

gy
contained

p in
unit

flux density
and

length

is of the order of the of equal to the velocity

a column
of

of

unit

light

times

the

time.

Thus,

The geometrical

factor is equalto \302\243; the


for

derivation
flux

is (he

subject of Problem 15.

The

final

result

the

radiant

energy

is

by

use of

B0) for

the energy density


Jv

U/V.

The

result

is often written

as
B6)

\302\253

aB s= b2V/60AV

B6a)

has the

vahie

5.670

10~8

W m~2
body

K~* or 5.670x
that

10\"*
erg in

cm\022

s~'

K~\".

(Here cts is not the entropy.) A

radiates whose

at this rate
rate
walls

is said to radiate
equilibrium
in

as

black

body.

A small

hole

in

a cavity

walls are

thermal

at temperature

T will radiate
the

is independent
depends

at the as a black body of the physical constitutionof the

given
of

B6).

The

rate

the cavity

and de-

only

on

temperature.

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

Emission and

or biack incident
biack if

surface

and,

second,
a given

for a

surface

with

arbitrary

properties.

An object

is defined to
upon

be blacktn
it

the

hole

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
frequency

range if all

oj Sutj

reflect
negligible

enough
loss

back

times from the cavity through the hole.


flux

walls

lo

be absorbed

in the

cavity

with

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
energy

The radiant

density
flux

Jv from

to the

radiant energy

emitted

object.
We

prove

the

following:

If a

non-black object
it,

at

temperature

absorbs

fraction a of the

radiation incidentupon

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 must emit Theobject by a black body at the sametemperature. at the same rate as it absorbs follows that if equilibrium is to be mainiamed. H a is law. For the special case of a perfectreflector, a~e. This is the Kirchhoir
zero,

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

radiation

flux emitted

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.

Estimation

of to

Surface estimate

Temperature the

One

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,
way

surface

temperature

at which

law,

Eq. B2),

as

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

- 3exp(-x)

= x.

Chapter

4:

Thermal

Radiation

and Planck

DiVnfmrion

This

equation

may

be solved

numerically. The rool is


^

kca^JkgT = xm
as in

2.82

B?)

Figure 4.4.

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
itic This

ihaf

Ihc

nimicr

universe irucructs

lines.

Most
cooled

;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
h;id coo

mancr.
was

remain

of

tnc

below

in a very siinpte way: llic plioion gas Tftcrcafier ihe radiaiion evotved with \302\273mc 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

occupancies
After inlo

determine
lhe

decoupling stars,

ihe eniropy. Urn evoluiion and

of

tnaucr

galaxies,

Electromagnelic radiaiion, is superimposed on the

ciuSl clouds) was as slarliuM, such


black

more

atoms (which are organized lhan before decoupling. complicated radiated by the maiter since lhe decoupling
inlo

heavier

cosmic

botiy radiation.

ELECTRICAL

NOISE
Planck

As an important exampleof the

law

in one across

dimension, we
a resistor.
noise

consider the
by

thermal sponMucous
which

fluctuations

tn voltage

These fluctuations,
explained

are

called

noise,

were discovered

by J.

B. Johnsonand
resistance

H. Nyquisi.*

The characteristic
ts shall

property of
lo llic

Johnson

is that
R,

ihc mean*
as shown

square noisevoltage
by Figure

proportional sec

value of the

4.6. We

that

<K:)

is also

directly proportional to tlie tem-

\342\226\240

H. N!jquisi,p!:js
Wiley,

R
!

lical jijsus,

Microwave

Interstellar CN
IR

measuremeni

2.9

K Black

body-

Frequency (cm\"!)
Figure

4.5

Experimental

body radiation.
oflhe
wiih

me surememsof lhe spcclrum Observations nf the flux were made with


;

of the
microwave

cosmic

heicr

speclrum ofinlcrslettac
a bulbon-borne

neiir

lhe peak,

infrared

Caurlesy of P. L. Richards.

ai frequencies

unJ vvere rneusi abo\\c lhe peak.

pcrature r and tlie band'-vidili

A/of wave

the

circuit.

edge of
Tlie
voltage

cLvironuignetic

propagation

(Tliis secifon presumes a knov.1at Hk inicrtncdiiitc level.)

Nyquist

tlicorcm

gives

a quanlhative.
in

expression
The

for ihe llicrma!noise


theorem is lhcr^fore

generated
any

by a resisior
estimate

thermai

equilibrium.

uccded in

of

Hie iinnting

signal-io-uoise

ratio of an experirr.cnial

Chapter

4:

Thermal

Radiation

and Planck

Zl
~
\342\200\242 Carbon

filamen

+ Advance wire

vNaCi

xCuSO, m H,O
in

H..O

0.1
RcMblancu

0.2

0.3
component,

0.4
in

0.5

Mil

kinds of conductors,including
J.B.Johnson.

electrolytes.

Afiei

apparatus.

In ihe

original
a

form

the

Nyqutst

theorem
ft

states
thermal

that

ihe mean
at

square

voltage

across

resistor

of resistance

in

equilibrium

temperature t is given by

B8) where A/

is

the

frequency*

bandwidth

within

which

the

voltage
range

fluctuations
are

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
the

range

ignored. delivered
in

it does
resistive

because
load

circuit

of Figure

4.7, the

power deliveredto an
' (R + Rf

arbitrary

R' is

'

B9)

which

al

maich

(R' = the word

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

'

In

this

section

frequency

to cycles

per

unit

time,

and not

to

radians

per

unit till

Noise generator

Figure

4.7

Equivalent
cilrrenl

ciicuii for a

resistance ft
power

with

a generatot

oftliermal noise that

delivers

to a

load R'. The

which
hi

this

is a maximum wiih condition the ioad


supply.

respcel
is

to R'

when R'
filter

= R.
lo the

said

power
enables

At
limit ihal

match,
the is.

&

- (Yi)f4R. The

to bo matched

us to

consideration;
square
Consider
characteristic

bandwidth under [lie bandwidth 10 whicii the mean


frequency
applies.

voiiagc

fluciuaiion

as in

impedance

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

of lenglh
a resistance

L and

characthe

R. Thus

line is matched at eachend, in


will

sense
in

that
the

ail energy
appropriate

traveling down the line


resisiance.

be

absorbed

wiihoui
at

reficciion
temperature

The

entire

circuit is maintained
A transmission

t.

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
frequency range

Sf~c'lL,

C0)
line. Each

where c' is the

propagation

velocity

on the

mode has energy


C1)

exp(ftwAJ

Figure 4.8

Transmission

Hue

oficiijjtli

L with

derivation of ihc Nyquist


aclerislic
line

liieorcm.

The

has

ihe

impedance 7,c of ihe [ ra us mission vaiuc R. According lo ihc


theorem

mdamcniai erminai

resistors

are

of Iransrnission iines, [he matched to the line ivlicn

heir

resistance

has ihc

same value R.

in

equilibrium,
in

according
the that

to the limit

Planck distribution.
hw
\302\253 z

We

are

usually

concerned

with circuits

classical the

so
in

that
the

the thermal
frequency

is r. It

energy per mode


A/ is

follows

energy

on the

line

range

C2)

The rale at which

energy

comes

off the

line in one

direction is
C3)

The powercoming
impedance

off

the

line

al

one

end is
the
would

all absorbed in
when

the

terminal

R at

that end; there areno reflections


equilibrium

the

terminal

impedance

is matched

to the line.In thermal

load
rise.

must emit
Thus

line at the same rate, or elseitstemperature to the load is

energy to the

the power input

9 =
but
V

</2>R

\302\273

iA/

C4)
used

2R1,

so that
itt

B8) is obtained.
temperature

The result has

been

in low
it

temperamore
a

temperature(hermomctry, convenient

regions

{Figure 4.9)
{not

where

is

conresistor

to

measure

when

no

dc current

than t. Johnson noise is the noiseacross (V1} discussed is flowing. Additional noise here)

appears

when

a dc

current flows.
DEBYE

PHONONS IN SOLIDS;
So I

THEORY

calculate the spectraldistribution of this distribution for a continuous solidand to consider


decided to

the

possible

fvee vibrations

as a

to approximation

the

actual

distribution.

The

sonic spectrum

good enough of a lattice must,

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
Figure

4.9

Mean

icmpcralurc indicated by
tlidrmometer.
and
After

a CMN'

powder

R.

R. GiiTarJ,
Low

li.

A-

Webb,

C Wheailey, J. 533 A972).


J.

Tcnir

Physics

6,

100

of course,deviatefront
t/ie

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
this

disittuees

of the atoms.

P. Dcbye

The energy of an elastic wave


electro

in

a solid

is quantized
average

just as the energy


of

of

an

magnetic
wave

wave in a cavity
phovwn.

clastic wave

is calleda
of

is quantized.The quantum
thermal

energy

of an

The

number

of pitonons in

an

elastic
;is for

frequency

oj is

given by the

Planck distribution function,

just

photons: 1

C5}

We assume

that sixain.

t!ie

ofthe elastic

ofiheelastic and heat capacity 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,
We

frequency

ofan

elastic

wjive is independent

of theamiMttmle

want

to find

the energy

account

minimum

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 independent of the temperature. In metals there is an extra
for

contribution
Number

from

the

conduction

electrons,

treated

in

Chapter

7.

of Plionon

Modes
possible
a finite

There is no limit to the number of but the number of elastic modesin

solid

electromagnetic is bounded.

modes

in

a cavity,

If the solid consists


transverse

of N atoms,
3A?.

each

with

three

degrees

of freedom,
a

lite total number of modesrs


two

An

elastic
in

wave
contrast

has three
to the

possible po! matrons,


two possible

and one

longitudinal,

wave.In a transverse wave clastic the to the propagationdirection of the

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 the factor 3, may be written as, including | JW
by extension exactly
<*\302\253(\342\200\242*\342\200\242) ,

C6)

of A7). Here n as for photons. We


ts

is defined want

in terms
to

find

of the triplet of integers nxt i\\yt iu, ;iralI such that the total number of

elasticmodes

equal

to

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

3;V;

nD =

FW/7!I'3.

C8)

The thermalenergy

of

the

phonons

is, from

A6),

,\\umbcr

ofPho

or,

by C6)

and CS),

D0)
By

analogy

with

the evaluation

of A9),

with

the

velocity

of sound

written

in

place

of the

velocity of light r,
V

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

J*V*

.
\342\200\224~~^

D1)

where
limit

ji/irii/Lr.

For
is

L3 we

write the volume V.

Here,

with

C8),

the upper

of

integration

usually

written as
,vfl

0/7

= fcsO/'t .

D3)

where6 is

called

the

Dcbye

temperature:

0 =

(hv/kB)Fn2N/VI \\
is of

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

The

D1)

for

the energy

Jo
as earlier.

f\"^

__\302\243_-?-

exp.x-

D5)

15

Thus

the energy in the

low temperaturelimitis

to proportional

T4\302\273 The

heat

capacity

is, for

\302\253 kB0

or

\302\253 0,

D7a)

Chapter

4: Thermal

Radiation ami

Planck

Distribution

17.78

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

a E 13.33

4.44

Y
0

\\A
r3,

3.99
in

5.32

K3

Figure 4.10
TJ10
from

Low tempcralure
Ihc cxcettent
daia

heat

capaciiy
whh

of solid
Debyc

show
these

is 92

agreement K. Courlesyof

!tie

T1 law.

L.1 Fincgold

and

argon, pioiicd against The value of 0 N. E. Phiiiips.

In conventional units,

D7b)

This

result

h known

as the
in Table

Ex Debye T1 !aw.*

peri

menta! values

results

plotted in Figure 4.10.Representative


temperature

experimental

for argon are of the Debye temCv

are

given

4.1. The

calculated variation of
T\302\273 0

versus

T/6

is

plotted

in Fig-jrc
TabL*

Problem given in

II. Several related


4.2

4.11. The high temperaturelimit


tiiermodymmiic in

is

the

subject

functions Figure

for

a Debyc

of solid are

and

are

plotted

4.12.

13.297 A912):

14,65 A9K).

Aiimitr

of

Photon

Modes

Lu

210

Jjg

7.

UJ

1
UJ

EQ

pT

UJ

<

a.

(J

Chapter

4: Thermal RaJhtion

ami

Planck

Dim

25

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

20 -

/
Figure-5.11

Heal

capacity
Dcbye J mol~'

Cv of a K\"'.

solid,
The

according10ihc
vertical scale is in

approximation.

The
L\342\200\224

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

K\021.

0.2

0.4

0.6

0.8

1.0

1.2

'able

4.2

Values of
Cv

C,, S, U,

ai

id F on the
S =
CO

Debye

ihc ory.

in unlls J

moI\021

K\"

IT

k^o

U,0

170

24.943

0.1

24.93

90.70

X 2402

- 666.8

0.2

24.89

73.43

115.6
74.2

-251

0.3

0.4
0.7

0.5
0.8

0.6
0.9

24.83 24.75 24.63

63.34

-137

56.21

53.5

-87

50.70

41.16

-60.3

24.50
24.34

46.22

32.9

-44.1
-209

24.16

23.96

1.0

23.74

42.46 39.22 36.38 33.87


24.49

27.1

-33.5
-17.0:

22.8

-26.2
-7.2:

19.5

16.82

1.5 2 3

22.35

20.59

18.30

16.53

10.71

9.1 5.5 2.36


0.58

-3.6.

-1.2

4 5

12.55
4.76

6.51

6 7
8

9.20 6.23
3.45

1.13

-0.4!

4.08

-0.2

2.64

0.323

1.77

0.1S7

-0.0

-0.1

2.53

1.22 0.874
0.643

0.114

-0.0

0.073

-0.0

10

1.891

0.048

-0.0

15

0.576

0.192

0.0096

-0.0

Summary

20 0

10

-10

-20

-30
0.5

\024\302\2600

1.0

1.5

FiKiire^.12

Energy

t/and DcbyC

free energy theory.

s=

I/-

roof

solid, according

to tiit

Tlic Dcbye

of tlic

temperature

solid

is 0.

SUMMARY

1. The

Planck distributionfunction

is

for

the thermal

average number of

photons in a cavity

mode

of

frequency

2. The

Stefan-Boltzmannlaw is
'

15/iV

for the

radiant energy density

in

a cavity

at temperature

t.

Chapter

4:

Thermal

Radiuiwn

and Planck

Distribution

3.

The

Planck

radiation

law is
h \302\2533

r2c3

exp(/io)/t)

\342\200\224

for

the radiation

energy per

unit

volume

per

unit
oBTA,

range
where

of frequency.
aB is

4. The flux density of radiant energy is Ju Boitzmann constantn1ks*/(i0hici.

\342\200\224

the Stefan-

5.

The

Debye
in

low

temperature
uniis,

limit of

is,

the heat capacity of a dielectricsolid

conventional

where

the Debye

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

PROBLEMS

1.

Number

of

thermal

photons.

Show
in

equilibrium

at temporal

ure

a cavity

that the number of volume V is

of photons XXs\")

in

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

D8) whence
<r/N

i-rom B3) the entropy is a = Dn2F/45)(r//icK, believed that the total number of photonsin the

=s

3.602.

It

is

universe is 109 larger than the both are of total numberof titiclcons Because neutrons). entropies (protons, 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

constant

with

time,
of

7. Surface
density

at

the Earth

temperature ofthi! Sun. The value from the Sun normal (o the
Earth.

the

total
rays

incident

radiant energy Hilx is called the solar

constant of the
wavelengths

The

observed

value

and

referred

to the

mean Eanh-Sim disiance is:


constant

integrated

over all emissionwave-

solar

0.136

J s

D9)

(a) Show thai the total rate (b) From this result and

of energy
.the

generation of the

Sun is 4

10\026 J S\"

*.

10\"12J s~' cm'2 K\"\"\\ Sun treated asa black


theSunasl.5

Stefan-Boltzmann

constant

<rB =

5.67 x

show body

thai is T

the effective temperature of the surface of the ~ 6000 K. Take the distanceofthe Earth from
x
10l\302\260cm.

10!3 cm

and the radius of the Sun as 7

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, constant Theself-energy 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.

Average

dimensional

argument

of t/te interior temperature or otherwise (he order

radiates
for

4. Age

of the Sun. Suppose4


at

lQ;6Js~!

is the
i

total rate at
energy

which the Sun


available
and
ihe

energy

radiation,

on

the present time, (a) the rough assumptions

Find

he

total

of the Sun
4.0026)

of hydrogen

the reaction
life

of stops when 10percent to helium. Use Einstein relation


the

(atomic weight

to helium(atomic L0Q7S) weight


the

that the energy sourceis


original

conversion

that

hydrogen

has been

converted
is about

= \302\243

(AAf)c\\

(b) Use
ihe

(a) to
universe

estimate the
and by

expectancy

of

the

Sun. It is

believed ihat [lie age of the


in

109 years. (A good discussion is given died in the Wcinberg, generalreferences.)


10 x

books

by

Peebles

5.
that

Surface Earth,

temperature on

ofthe

the

renijiates
ihe

us much
sin

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

face
7\"o

of the
-

cycle.

1.5
6.

Use
IOlJcm.

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

Pressure

of thermal

variation.

Show for

a photon

gas thai:

(a)

p = -(cUfcV),

- -^s/iiiluij/ilV) ,

E0)

l Radiat

and Planck

Oiildbnti,

where s; is the (b)


(c)
Thus

number

of photons

in the
=

moJej;
-mjyV;

dojjfilV

E1) E2)

p =
the

U/iV.

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 considerably the radiation than higher pressure.
radiation

pressure

is equal

the

of thermal

7. Free

energyof a p/iot
by

on

gas.

(a)

Show

that

photon gas is given

the parlhion

function of a

where

ihe

product
E3)

is over
as

the modes \302\273. (b)

The

Helmholtz

free energy

is found

direclly from

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

E4)

Transform

the sum to an

integral; integrateby
F =

parls

to

find

-n
plane

E5)
at temperature
flux

5. Heatshields.

black

(nonreflective)

Tu is parallel
in

to a
between

black

plane

at

temperature
third

T(. The net


black

the

two

planes
to that plane.

is Jv = aB{Tf
a steady the This

- T*),

energy
where

density

vacuum

be-

aB

is the

Stefan-Boltzmann

constant

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


to

used in B6). A

plane

is inserted

state

temperature

net

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
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
Photon

energy flux density is the principle of

between the other two and Tm. Find Tm in terms of 7'B is cut in half because of the

9.

gas

in one

dimension.

Consider a

which

r. The emiiiicrulioii of modes lake ilic soiulions siundmg waves


proceeds as

in

with

line.

ihe usual way for zero amplitude ai

one dimension: cacli cud of ilic

10.
thai

Hcitt

capacity
by

of iniergalaciic atoms radiaiion

space.
in a

occupied hydrogen alsooccupied thermal


by

ilic

ralio

of ilic

hcai capacity of mailer lo lhal of radiaiionis ~-

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

//. T

Heat capacity
liie

\302\273 0

heal

the form

E6}

Determine the first nonvanishing - 0 and T comparing with


/2.
Dcbye

term
Table

in the

sum. Check

your result by

inserting

4.2.

Heat capacity
temperature

of photons andpltonotts. Considera 10\" atoms equal to 100K atid with


to at 1 K.

dtelcciric solid
capacity

with

cm ~3. Estimate

the

lemperature at which the photon contribution equal to the phononcontributionevaluated


13.

the

heat

would be

atoms
is
in

Energy fluctuations
in

in

a solid

ai low

the

temperature contact

region with

in which

temperatures. ihe Dcbye

Consider a solid of N

Ti

law

is

vaiid.

The

solid

ihermal

a heat
that

from

Chapter

3 to

show

the

IF is given by

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

E7)

Suppose

that
then

T =
$F p= for

I0~2K;0
0.02.

a side;
14.

= 200K;and N

1O1S for
fluctuation 1

a particle
in

0.01cm on
is of

At

!0\025 K

order of uniiy
Heal
sound

a dielectric

the fractional particle of volume

energy

ihe

cm3.

capacity
waves
are

of liquid
in liquid
no

longitudinal

s\"'. There
0.145gcm~3. capacity

*He at low temperatures. 4He at temperatures bctaw


sound

The
0.6

of longituvelocity K is 2.383 x 104cm


density the

transverse

waves

in the

(a) per

Calculate

the Debyc

temperature, (b) Calculate

liquid. The

is heat

gram

on the
x

Dcbye theory

value

CK

=\342\226\240 0.0204

T\\tn

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

Chapter

4:

Thermal

Radiation

and Pfanek

Distribution

value

suggests

thai

phonons
the are

are
due

Hit;

most

below 0.6 K. Note that

important

excitations

in liquid

4He

liquid.The H. C
Kramers,

experimental

value

has been

experimems

to
f

J. Wiebes,

expressed per gram of C. G. Niek-Hakkenberg,and

Physica

32,

625

!957}.

15.

distribution that the spectra! of radiant energy flux, (a) Show of the radiant energy flux that arrives in the solid angle i!Q is where 0 is the angle the normal to the unit area makes with fuucos0*</n/47r, 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.
Angular

density

Image An on a

16.

radiant object. Let black object of area Ao.


of a
to

a Use

lens an

image

the hole in

cavity

of

area

product
leas

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
AuQtl

equilibrium

argument

to relate the

AaQ0

where

Qtl and
and

as viewed

from the

from

parallel

{al!

axial

angles

small).
argtted

17. Entropy and occupancy. We

cosmic of photons
black

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 decreased with the expansion has increased as the wavelength 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;
in this radiation

has

not changed

<s +

l)log<5 + !)
the

- <s)log<s).
the

ES)

It

is convenient

to start

from

partition

function.

18.

haxiropic

expansion

of photon gas.
a cube

Consider
of volume
V

gas at

of

photons

thermal equilibrium radiation in cavity volume increase;the radiation


expansion,

temperature

of the r. Let the

pressure

performs
drop.

and

the

temperature
titat

entropy we know
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 increased the universe at that time, compared linearly with at wltat fraction of the present time, age of the universe did the decoupling the work done by the photons during the take place? Show that expansion (b)
iV1'3

of the radiation wit] in such is constant

work during the expanFrom (he result for the

of lite

The

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

a plane
\\ \342\200\224 a. Let

sheet of matethe sheet be at tempera-

suspended between and parallel with temperaturesru und t,. Show that the net flux

two density

black of

sfieets

also
dewars

black sheetsis (I
black

maintained radiation thermal


e =

between the

r)

times

the

flux

density
with

when tiie
a

as

in Probfem

8, which

means

intermediate sheet is helium I; r - 0. Liquid


of

are

often

Mylar

film called

by many, perhaps 100,layers Superinsulation.


insulated

an

alumtntzed

SUPPLEMENT:

GREENHOUSE EFFECT
Effect

The
caused

Greenhouse

describes

by the

interposition

and in clouds,

in and of carbondioxide

the wanning of the surface of of water, of an infrared absorbent layer


the

the

Earth

as vapor

atmosphere

between

the Sun

and

the Earth. The water may

contribute

as

much

effect.
Absent

90 percent

of the warming
the

such

layer,

the

temperature

of the surface of

Earth

is

determined of solar

between flux the by the requirement of energybalance incident on the Earth and the flux of reradiation from the to the fourth power of the temperaEarth; the reradiationflux is proportional of the of Problem temperature as in D.26). This energy balance is the subject Earth, 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

primarily

radiation

is the Sun-Earthdistance.

The
Sun is
factor
We

result

of

that

problem reduces

is TE

\342\200\224

280

K, assuming
geometry

T,=\302\273

5800

FC The

much hotter than the Earth, but


the

the

(the

smali

subtended by
assume

Sun)

the solar

iiux density incidentat ihe E;irth

solid angle
by

defined

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 as evident from 4.4. The layer will emit enerry flux Figure higher frequencies, 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
as

of roughly
as

(i/20)*.
an

example

an

absorbent

lEt^h + h-ns.
where
l\302\243g

E9)

is

the

thermal

Oux from

the Earth in the

presenceof

the

perfect

greenhouse

effect.

Because
Earth

the thennal
is

flux

varies

as

of the of the surface

T4, the

new temperature

=
T\302\243s

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

280

K ~

333 K,
K =

F0)
53 K

so

that

the

greeahouse

warming

of the

Earth is 333 K \342\200\224 280

for

this extreme example.*

\342\200\242

For

end

1992:

detailed discussions i. T. Houghton

see Climale change and

Climate

change

ct aJ, editors.

1992, Cambridge

U.P., 1990

Chapter

Chemical

Potential

and

Gibbs Distribution

DEFINITION

OF

CHEMICAL

POTENTIAL
Gas

119
120

Example: Chemical Potential of the Idea! Internal and Total Chemical Potential
Example:

122
with Altitude
Panicles 127

Variation

of

Barometric

Pressure

125

of Mobile Magnetic Example: ChemicalPotential \"'\"


in a

Magnetic
Batteries

Field

'

Example;

\342\226\240

129

Chemical

Potential

and Entropy

131
133

Thermodymtmic Identity
GIBBS

FACTOR
Particles

AND

GIBBS SUM

134
139

Numberof
Energy

140

Example:
Example:

Occupancy
Impurity

Zero or One
!omz;ition

140
in a

Atom

Semiconductor

143
144

SUMMARY

PROBLEMS

145

1. Centrifuge

145
Field

2. Molecules the in Earth's Atmosphere 3. Potential Energy of Gas in a Gravitational 4. Active Transport

145 145

145
145
146

5.
6.
7.

Magnetic

Concentration

Gibbs
States
Carbon

8.
10.

Sum for a Two LevelSysSem of Positive and Negative Ionization


Monoxide

146
146
147

9. Adsorption
Concentration

of O2 in a MagneticField
Fluctuations
Potential Definition of Chemical

Poisoning

147
148

11. Equivalent
12.

Ascent

13. Isentroptc
14.

of Sap in
Expansion

Trees
of O2
Potential

148
148

15. ExternalChemical

Multiple

Binding

148

....

149

\342\226\240al Potential

and

Gibbs

Distribution

(H. We found earlier thai reservoir <2t, ihe Helmholtz

Tor

single

system

S
&

in

thermal

equilibrium

with

free

energy

of

will

assume

the minimum

value

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

and

wiiii

oiher

restraints
result

number equilibrium

of p particles.
with

This
in
between

on the applies pp
equilib-

(R.

diiTusive

between

makes

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


.md

^2, the

N,,.V\302\273

ihi5 sysicms

F=
a minimum,
Heimholtz

h\\

F2

- t/( + t/2
+

T(ff,

<T>)

A)

subject
free

to N

jV,

jV2

= constant.
a

Because N is constant,She
minimum

energy

of the

combined system is

with

respect

to

Definition

of

Chemical

Potential

System

.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

5Nt

= -5N2.
tlF

At

the

minimum,

- (cFi/cN^^lNi
With

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

B)

with

K[,

K2, also

held constant.
(/F

~-tlN2,

WG

have

[(cfj/t'iV,),

- (SF2/cNl),yNl

- 0,

C)

so

Hutt

at

cqutlibriuni

((Tj/oV,),

- (cF3/cN2)t.

(\342\226\240\30

DEFINITION OF CHEMICALPOTENTIAL
We

define

the

chemical

potential
I

as
(/;0
I

E)

Chapter 5:

ChemicalPotential

and

Gibhs

Distribution

where ji is

ihe Greek letter niu.

Then

/'I

'-

t'l

ihe condition expresses elF will be negative thai


from free

5,
energy

to

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


us particles

equilibrium. is is

If/(,

negative: negative,

When and

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


> ;i2,
's.

decreases

flow from

from

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
=

^i to &2; ilitit

particles

(low

of
and

low
not

chemical
a deriva-

F(t,V,N)

- F{x.V,N-

1).

F)

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 acisasa driving force for the transfer particles just as a differencein temperature of energy. has its own chemical potential. If several chemical each are present, species
The

chemical

potential

regulates

and

it is

as

the particle transfer as the temperature,

For species j,
G)

wherein

the

differentiation!

TTumbcrs

of

all

particles

are held

constant except

for the

species j.

Example: of

Chemical

potential

of the

Ideal gas. In

C.70}
-

showed

that

ihe

free

Ihe

monatomic

ideal gas is

/logZi

logN!] ,

(8)

Definition

of

Chemical

Potential

is the

partition

function

for a single

panicle. From (8),

A0)
use

If

we

the Stirling
fold

factorial,we

approximation for

A\"!

and

assume

tlutt v,e

can differentiate the

log

A\"

[N

-1)--

- 1 = togtf
chemical

\342\200\224

(II)

which

approaches

log

iV

for

large

values

of \\.

llcttcc the

potential

of the

ideal

gas is
,<

-rUogZ,

- log.V)

or,

by

(9),

A2a)

where

\342\200\224

NjV

is the

concentration
by C.63).
F{N

of particles ami
the
ji definition

na

(A/r/2nfi2K
af/j,

2 ts

the

quantum

concentration

Ifweuseji = F{N) approximution. volume

defined

i)froin.{6)as

we do

not need to
which

use the
with

Stirling

From separately.

(S) we obtain
By use
=

-i[log2,
particles,

not

logjV], =
nr

agtces

A2). The result depends on the


the

concentrationof
of
ths

on their total
we

system

ideal

gas

law p

can

numheror on write A2} as


A2b)

/t

Ttog(p/tiiti).

The chemicalpotential
we expect intuitively: lower concentration.
of composed

electrons

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

andGibbs

Distribution

Figure 5.2
regime
satisfied range

of dectroio.jrhelium composed
with n of
\302\253

The concentration dependence of/*,


atoms,

in

units

o! r,
least

at 4.2

nQ,

a ^as

must have a value

of -

K and 300
^i

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


t. For

at

oulv for

lluin concentrations apprccwhly le\302\253 semiconductors. For it is lypical gases always

those

in metals, satisfied under

electrons this as in ihe normal

is

conditions.

of

liquid

licimin

ill atmospheric jtascs aiwjjs

and

tnolccubr

pressure, 4.2 K, lave ncgaiivcchemical


such

and

room

icmpcraturc,
unJer we

potentials

condiiioas: at classical concernrations


ncgaiive.

ihnt

nfnQ

\302\253 !,

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

Internal

and Total
way

Chemical Potential
understand

The best
equilibrium

to

the

chemical

potential
acts

is to discuss diffusive
on

in

Ihe

presence

of a

potential step that

Ihe

particles.

This

Internal and

Total

Chemical

Potential

Figure 5.3

potential

step

between
be

two
established

can systems of chargedpanicles

tiie voltage polarity shown, of positive parlic'es energy


in

the with

potential charge qAY

system

i, would be raised by

q > wild

!o J2. The potential energy particles would be loweredin 3,


respect

of negative with

cespect

problem
discussed same

has wide

the application and includes

semiconductor

\342\200\224 n &->t

junction
al

in Chapter

13.

We

again

consider

hvo

systems,

Sx und

the

temperature

equilibrium.
difference iliat
Af[(im'tial)

and capable of exchanging particles,but not yel in diffusive We assume that initially > /(j, and we denote the iniiial nonfix
potential

equilibriumchemical
in potential
above

difTcrence

by

A/j(iimial)

= ;/2

- ^i-

Now

let

the potential

way to
A

establish this potentialstepisto apply


lhat

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
between

the

two

systems

a voltage

I'

such

A3)

with

the

polarity

shown

in Figure

5.3.

difference

in

gravitational

potential
where

also can

of mass

serve asa potential difference:


by

when

we

raise

a system

of particles each
g is

the

height

/i, we

establish a potential difference Mgh,


the

the gravitational
this

acceleration.
potential

Once a potentialstepispresent,
by

energy

of ihe

patrides produced
system.

sfcp

is included

in (he

energy U and in the free energy F of the


of

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

keep the free

S2 fiNed, ihe

/affinal)

= ;(,(initial) -f

[,..(initial) -

/i,(inilial)]
A4)

When

the

barrier
\342\200\224

was

inserted,
brings

/^(initial)

/(i(initial)

the two

pj was held fixed.Thus systems into diffusive

the

barrier
equilibrium.

gA

The

chemical
in

potential
chemical

difference
potential

barrier

that

is equivalent to a true potential energy; the between two systems is equal to the potential will bring the two systemsinto diffusive equilibrium.

potential, and

a feeling for the physical effect of the chemical potenfor the measurement of chemical differences potential two measure we establish a between To systems. ft2 potential step /<,, 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. the zero of the potential value of the chemical potential depends on energy The the choice of the of scale. idealgas result A2) depends on zero energyof a free as equal to the zero of the kinetic energy. particle When total chemical external potential steps arc present, we can expressthe
This

statement

it forms

gives us the basis

potential

of a

system as the sum of two


/'

parts:

= iv

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

A5)

Here
is the

/jtM

is

the

potential

energy
potential

per particle in the

external potential,and
potential
nmy

jiial

internal
if

chemical potential*
the

definedas the
were zero.

chemical

that
be

would

be present
electrical,

external

The term /iCM

mechanical,

magnetic,

gravitational, etc. in origin. The


as Apeil =

condition equilibrium
A6)
chemica!
those
of

Pi

\342\200\224ca'i

Hi

be expressed

-A

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

potential
working

semiconductors,

the

words

chemical
potential

potential without a
The

further

qualifier.

total

chemical

potential

may be

called the

electrochemical the

if

the potential
\342\226\240

barriers of interest are electrostatic. Although


n the
in
fi.

term

electro-

Gibbs

called

potential

and .

measures

differences

ihe intrinsic it,*, '

that potcnsjal. He recognized

a voltmeter

mea-

Internal

and Total

Chemical Potential

SysicmB)

Figure

5.4

A model

of ihe variation
altitude: heights i

\\>.iih aimcispliericpressure

of gas at different gravitaiiona! field, jn iherma!


\\olumcs

in

and

di!

con wet.

System (!)

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


and potential\"'

we
without

shall
an

tisc \"total
adjective

chemical
should

be

avoided

tit

situations

in

which

any confusion about

tis meaningcouldoccur.

Example;

diffusive

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 Variation

of barometric

equilibrium

bciwccn

exieroul

poicnlials

the poiemial
gravitational

The loial

diemical poiemial is

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

{17}
In

equilibrium,

this

musi be

independent of {he
+
A/y/i

hcidil.

Thus

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

rlog[ii@)/nQ]

ihc

conceniralion

\302\253(/t).alhcijjlU

h satisfies

(IS)

Chapter 5.-Chemical

Potential

and

Gibls

Dhtnliution

1.0

0.5
\\

0.2
o.i

\\

i
figure v-iih

5.5 ahiiude.

Decrease

of atmospheric The crosses represent


sampled

pressure Ihc average

0.0S

atmosphere

as

on rocket
Vine

fliyhis.

The

concerting

siraight

lias

corresponding lo a

icmpcraiure T =

a slope
227

K.

\\

\342\200\224

0-10

20
Heighi,

30
in

40

50

km

The pressure

of an ideal gas is proportional

lo

llieconcenlration;

therefore

Ihe pressure

aullilude

li

is

p(/i)
itio

=.

p@)exp(-.V9li/t)

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

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
Thl^ &s

uuromoLrtc

pressure

in an

isoihermat

t\\ictul behavior.
iaken

fatthcr dp,
ll.o

iiut

these

Ivavc

hrgeiy
i>

cscipctl from ilic


oi\"

iiiiiinspUufc:

see

Probicm a'ttipliaital

1.

11UC.U1-.C

UanhS

LiiiiiO^pticrc

not

;n;tiir.ittly
pressure

Fiyuie 5.5 is :i loyatiifunic on rocket flights. The data

jjloi
potnis

iwitlicniiiit, ni/i)ft;is ;i iitoic tfatj bciv^un 10 and


a siraighi

4QKiloiMcttrs,
roughfy

f;i!i

near

fine, suggesting

iso-

vtl and

total Chemical Pot

thermal range

behavior. jj{/ij):pl/i,J

Tlie straight = 1000:1,

line connecting the data points over an altitude range from ft,

of Figure 5.5 spans a pressure 2km io A, = 43km. New,

from A9),

so that
of
tltc

the

slope

of the
eurve

line

is Mg/x,

which leads to

T ~

x,'kB

\302\253 227

K. The

non-intersection

observed

wish !hc point k ~


more is

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

\302\253

I, is

caused

by the higher

tempera-

at temperature

lower

aliiiudes.

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
of

consistsof
fevel

than

composition

dry air at ica iess than 0.1

TS pet

with

M the

appropriate
T *}\\

molecular mass. Because of


nk*c

tlie

JiiTerences

in mass, ihe

difTcrcnt

p^insiTrii^itic

tiff

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
magnetic

particles

in a

with

a magnetic

moment

n, and

iij

are

ill

potentials

are

If

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

!t\\:nivs

iintwi'iiittKlfovcrtbtf in unlcr
total
diffusion

it. mtht out


dent

out

\\\\w \\ wlumc if there

to

ut:tintaii)

j cotiMjisl

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

i|ic volume irigmo


of posiiion,

(Tlie 5.6).

chemical
of

is free

potential of a species is eoitstam iiiJc within the volume,) Becausethe particles

Chapter

5: Chemical

Potential and

G'thhs

Dhtribut

---

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

Iff' 1GIU ciir3


\342\200\242

ion (i,
5.6
ides

in

particles

Figure
pari

Dependence
Ifn

on ihe

intensity.

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

kilofiauasl2iesb)ihccona:nlraiionwillbe2

!09cm\023.

species in

equilibrium

have

equal

diemioil poientiais,

lUl)
The

= consiant B3) are easily


seen

;i,01(|).
fay substitution

B3)

desired

solutions -

of {22)and

to be:
,

\302\253,{B)

in{0)exp(mB/t); ii[ 4field nt

n^B) =
at

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

B4)

where

ti@}

is tiie

concentrationat
n{B)

total concentration a poini at magnetic

a point

where

the

field

B =

0. The total

S is

\302\253

n,{B)

ji,(B)

= Jn@)[exp{jHB/T)

+
+

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

n(B)

n{0)cosh{mB/T)

* n{0)M

4-

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

-Y

^-

B5)

The result

shows [he tendency


intensity-

of

magnetic
fine in

panicles
result

to concentrate
is not

in

regions

of high
wi[h

magnetic
magnetic colloidal

Held

The

fujictionai

form of ihc

limited
particles

to atoms
of
f

two
in

flux strucfure
engineering,

such

as

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
he magneiic

orientauons, solution. Such

but is applicable to

fecromagncfic

in suspension

Internal

and Total ChemicalPotential

suspension
ttie

and fields
the

intense

placed in a magnetic at the edges of the

field,
crack.

flic

particle

concentration

becomes

enhanced at

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, form but 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
In

the preceding
If

/'iM

t log
not

it

-f

constanl

, of the

B6}

where the constant

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

depend

on

the

concentration

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
the

Example; Batteries.
w

Oneof

most

steps

the

electrochemical

battery,

in

the

discharge

process

both

tlie

metallic to

Pb Ie;td

of the negative sulfate,

electrode and
the

the

PbO.

of

the positive Negative

electrode arc

converted

PbSO4, via

two

reactions;'

electrode:

Pb +
Positive

SO4\"\" -+ PbSO.,+

2e~;

B7a)

electrode:

PbO2

+ 2H+

+ HjSO- + 2e\"-+
acts as a sink the sulfafe ions at
5.7b). for the

PbSO4
\"

2H2O.
keeping

B7b)
the internal

Because of B7a)the negative chemical potential ji(S04\"\"\")


lower

electrode
of

SO*~ surface

ions,

than

inside

the electrolyte

(sec Figure

Similarly,

of the negative because of B7b) the

electrode
positive

electrode

acts as

hydrogen chemical

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

sink

for

H+

electrical currents If the battery


electrode

during

the

discharge
not

process.
connected,

terminals arc
in

electrons

are depleted

from

the As

positive a result,

and

accumulate potential

the

negative

electrode,

thereby charging both.

electrochennca!

steps develop at

exactly the

correct

magnitude

diffusion of ions, which stops current is permitted to flow, the is of because electrolyte negligible,
\342\200\242

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.

reactions
a negligible

resume.

electron

Electron fiow directly concentration in

through
the

the

electrolyte.

The

reactions

given are

net

reactions.

The

actual reaction steps

are more complicated.

clcclrodc (\342\226\240f)

PbO,

l>b

I
T
(b).

5-igurc

5.7 T

(ajThekjJ-aciJ ioni/cd

parlialiy
two

U^SOj.

bailcry coniists of a Pb anj a PbO2 One SOI\" ion coii\\crfs one Pb atom
convert

cicctrotic
into

ilnmclsed + 2e~;

in

PbSOt

ions

plus one

im-ionizcd HjSO^ molecule


Iwo

one

PbOj

moltrcul^ imo
\"

PbSO4 + 2HjO,Lii
and and

isiirning

ciccirons.

(b) The
poltnltai

eiectrociiemicaipokntials for
barriers y(.\\)

SOI

H*

before the

development ofimcfiia!

thai after

ihe chemical

reaction, (c) The eicctroiuticpoieuliai

slop the dilTuston the formation

of the

barrier.

Chemical

Potential

and

Entropy

cMornai voiUigc

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

is ;i}>[i!ied

relative posilncclcclrodcs

to will

ihc common slop

ciectroiyie. Because

the

suifute

ions

curry

two

negative charges,diffusion

when
=

\342\200\224

2gAK_

A/i(SO4\"\.")

BSaJ

DifTusion

of

the

H+ ions wi!i

stop

when

+ ^AK+

\302\253

A/i(//').

B8b)

The

two polemics
forces);

AK_

and

Al'+

are called

(electromotive

their magnitudes are known:


AV_

ha!f-cc!i potentials or

half-eeil

EMF's

-0.4voll;

Aft
developed

\302\273

+1.6volt.

Tiic lolai

electroslalic polcnliai difference as required to stop the diffusion reaclion.


AK =
This is ihc
AK+

across

one

full

cell

of

ihc bniicry,

is
-

AK_

\302\253 2.0voli.

B9)

live lenninal

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

Chemical

Potential

and Entropy
the

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

In E)

Hclmlioltz

free

C0) This expressesihe raliopi/x


1/r as

a derivative

of ihe

entropy, similar to tlte way

was

defined

in Chapier

2.

Clmpler5; Chemical
To derive

Potential

and

Cibbs Distribution

C0), considerthe entropy


The

as

a [unction

of the

independent variables

U, V,

and

N.

differential

cU
gives

<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 the differential

After

division

by {5N)r,

C2)

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

D[/),/(JW),

is (dU/dN),,

all at

conslant

volunie. With

the

original

definition

of 1/t,

we have

C3)

dNj,, This expresses derivative


a

at

constant

U in terms

oTderivatives at constantt

By

the

original

definition

of the

chemical potential,
~

\023
and on

[H,
C3)

C4) w.,

comparison with

we

obtain

C5)

same

The two expressions E)


quantity

and

C5)

represent

two

different

ft. The

difference

between

them is

ways to express the the following. In E), F is a

Chemical

Potential

am! Entropy

Table 5.1

Summary

of

relations

expressing
cr, liic as

ti-.c temperature

partial derivatives
energy

of liic cm

ropy
given

energy

U, and liic
of their
itatur.il

free

F, witii

a, U, and F
variables

functions

independent

o(U.V,N)

(IU\\

, is independent
variable

\\ia)rtl

y,,

function of

its natural independent variables


of

x,

function

the

same

variables.

In C1)
V,

we

assumed a =
fi

V, and

N, so
is

that n appears as
a(U,V,N),

so

that

C5)

yields n as a function of
terms
find

U,

N.

The

quantity

the

same

in both

E)

and C5), but expressed in

of different

variables.

The object

of Problem1i

is to

a third

relation

for p:

C6)

and in

Chapter

10 we

derive
Tor

compilesexpressions
have their
Tlicvmodynamic dynamic

i,

a relation for p asa function p, and ^ as derivatives

of

t, p,

and N.
F.

Table 5.1
All

of o, U, and

forms

uses.
identity. identity

We

can

generalize

the statement

of the Ihermonumber

given

in C.34a)

lo include
in

systems in which the

of

particles

is allowed

lo change. As

C1),

C7)

By use

C0)

for

of the definition B.26)of i/r, the fi/i, we write da as .

relation

C.32)

for p/r,

and the

relation

da =

dU/x

pdV/x

- pdN/x.

C8)

Chapter

5:

Chemical

Potential and Gibbs

Distribution

This

may

be rearranged

lo give

dV = xJs

pdV

;u|jv

C9)

which

is a

broader
Chapter

statement of the
3.

ihermodynamic

identity

than

we were

able

to developin
GIBBS

FACTOR

AND
derived

GIBBS SUM
in

The Boltzmannfactor,

Chapter

3, allows

us lo

give

the

ratio

of the

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

probability contact

the with

reservoir at temperature t:

P(z2)

This

is

perhajtls
with

the best
a

known resuh of statistical


factor

mechanics.

The
thermal

Gibbs
and

factor
diffusive

is thegenecauzauon
contact
argument retraces

of the BoHxmann
at temperature

lo a

system
3.

in

reservoir

j and chemical potential p. The arguin

much

of that

presented
with

Chapter

We consider

a very
body

large body
is

constant

energy

Uo and
large

constant particle
reservoir <R and

number N0.The
the system

composed

of two
contact assures

parts, the very


(Figure that

&, in thermal and diffusive


the

5-8), They

Thecontact particles and energy.


potentialof
.
iV

the temperature

may exchange and the chemical


the

system

are

equal

to those

oftiie reservoir.When
ihe

system

has

particles,

the

reservoir

has Nu
C/o

- M particles; when
e.

system

lias

energy

e,

the reservoir has energy

\342\200\224 To

obtain

the statistical

properties of the

system,

+ 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
we

make

observations
Tor

as before

one

each

in ihat

the the

orbital'.' particles

Only may

when

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

a large

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 systemFigure

5.8

A system

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

that

jY

the

the

of \302\243, the state the number is, ir we specify the number of accessible slatesofO?:
=

oraccessible

states

of

(H

is just

\302\273((H+

S)

gift)

x 1.
in

{41)
a single

The factor ! reminds


stale,

us

that

we are

The

y(<Jl)

stales

of

the

stalesof of accessible

the Uo - e,. Because

looking at ilic sysiem S reservoir have No - N particles


probability

spiciixd

and

Ikivc

energy

system
the

P{N,i:J

is proportional

to Ihe number

reservoir.

NtU0

zt).

Chapter

5: Chemical

Potential and Gibbs Diitrihufit

fit
Particles

i\\'o UQ

,V, \342\200\224

Panicles
Energy

,VU

Energy

Ft

Uo

Panicles
Enemy

A\\

Particles

r,

Energy ,

(a)

(b)
and

dirTusive

contact

with the

system. In (a) tile

to

it. In

{b] the
of

system

is in

quantum state

2, and

the

reservoir

has g{N0

- A'j,

Uo

\302\243;

stales
number

accessible

to it. Because we have specifiedthe exact state of the system, the ofsiulcs accessible tool states accessible 10 01 + i k just the number

total

Here g refers to the rcsetvoiraloneand in and on the energy of the reservoir the We can express D2) as a ratio of two

depends

on

the

number
that

of particles

reservoir.
probabilities,

one

the system

is in

state 1 and the

other

lhat

the system

is in state

2:

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

e,)
j

D3)

g refers

to the

state of the reservoir. The


entropy

situation

is shown

in Figure

5.9.

By definition of the

s(N0,y0)

ejpOfNo.f,,)] be written

D4)

so that the

probability ratio hi

D3)

may

as

D5)

>ffel)

\"
eXp[\"(N\302\253 N\"y\302\260

D6)

Here,

Act is the

eniropy difference:
NUUO

Ac h a(N0 ~
The reservoir is very
approximated
large

e,)

- a[N0

N2,U0

e2).

D7)

in comparison
firsl

with the
order

quite accurately by the


and
\302\243 that

lerms

system, and Ac may be tn a series expansion in

the [wo quantities N


becomes

relate

to the

system. The

entropy of the reservoir

N,U0

~i)

D8)
we have,

For A<?

defined

by D7)

to the

first

order

in

iVE

\342\200\224

N2

und

in e,

\342\200\224

c->t

E0a)

by our bin

original defmilion of the temperature. This is written the system will have the same temperature. Also,
K

for

the

reservoir,

(?e'

E0b)

by C0).

The entropy difference

D9)

is

(N,

- Nt)n

(t, to the D6)

E1)
system. The and E1):

Here

Aa

refers

to the

reservoir, but Nit A'^, \302\243lt t]


on

refer

central

is found result of statistical mechanics

combining

E2)

Chapter

5;

Chemical

Potential

and Gibbs Distribution

The

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.
probability

is

the

is of particles, normalizing absoluteprobabilities:


the

The sum of Gibbs factors, taken

overall

states

of the

facior

that

converts

system for al! numbers relative probabilities to

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

exp[(A'/i

E],VJ). r].

E3}

or the
of

grand pan
system

it

ion

function.

the

for all

numbers of
to

particles:
emphasize

this

defines

the

abbreviation

ASN.

We have

written e, as eJ(:V,

c,|.v,is ihe energy

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

dependence
of

of the

the

E4}
This

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

lo

a system

lhat is ai

and

poieinial

ji. The

with

E2} for
for

lite Gibbs
A',,

Thus

the

stales

s,

and

jV2,\302\2432.Thesum

of

ihe

probabilities

of all

stales

for

al!

numbers

of par*

icles

of tlte

system

is unity:

f
by ihe

\342\226\240 155)

definition

of 0-. Thus

E4)

gives

the

correci

iibsuime

probability.*

p.iiiictiljrl)-

IicIpM.

The

nuriliod

us,cil

there

to ikme

the Potion

dimibuiion

impends

on

6744s

Factor

and Gibbs

Sum

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

with

reservoir

lias N
over

all

{56)
We

shiill

use

this

result

to calculate
The

thermal averages.
of panicles

,
because

Number

of

particles,

number

in the system can vary


The

the

system

is in diffusive
ihe

contact
system

with

reservoir.

thermal

average of the

number of particlesin

is

according

lo E6).
by

To obtain tile numerator,


liie

each

term

in ihe

Gibbs sum

has

been multiplied can beobtaftied

appropriaie
the

value of#

of N. :

More convenient forms of <N>

from

definition

whence l-ll

<,V>

= r^-1
is easily found from the
shall

E9)
Gibbs sum
jV for

Tile
J
by

tiicrma!

average

number

of particles
we

direct

use

of E9).
written

When no

confusion arises, we
later

write

the

thermal average <N>. Wlicn

speak

of the
,V

occupancy of an orbital,

for </>

will

be

interchangeably

for

or

<.V>.

We often

eniploy the handy notaiion

F0)
where

is called

the absolute

activity. Here /. is Ihe Greek letter


directly

lambda.

We

see from

A2) that for an

ideal gas ). is

propcrliona!

to ihe

concentration.

Chapter5: Chcutkul

Potential

and Gibbs

Distribution

The Gibbs sum is wriiien as

F1}
A

'

A5S

and ihe

ensemble average numberof particles E7)

is

F2}

This relaiior.
finding

is useful, because in
ihat will make

many

actual

problems

we determine

/. by

ihe

value

<N> come out

equal to the given number of

panicles.
Energy,

The

thermal

average

energy

of the

system is

v -

<E>

^i

F3)
=

the notation /J where we ha\\elemporarily introduced


write
V

1/t.

We shall

usually

for

Observe <\302\243>.

that

so that

E9} and

F3} may -

be

combined

lo give

;r-\302\253
that is
of the

toi

F5}

simpler

expression
in

Chapter 3

terms

more widely used in partition function Z-

calculations

was

obtained

in

Occupancy Example:

zero

or one.

A red-blooded

example of
heme

syslcm

ihat

occupiedby
may

zero

molecules

or by one
in

molecule is the
never the

group,

which may

may be be vacant or

be
A

occupied
single

by one
heme

Oz molecule\342\200\224and
of an

5.10).

group occurs

red colorof meal.Ife is ihe energy

than one Oz molecule(Figure which is responsible for the myogiobin, prolein to Oa at rest at adsorbed molecule of O2 relative
by more

Figure

5.10

Adsorpiion

of an

Oj

by

a hemc

where c is

ihe energy of an

adsorbed

O;

rctal

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

infinite

distance,

ihen

the Gibbs sum is

\302\243~

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

F6)

If energy
in ihe

musl be added io remove


only

the

atom

from, tile heme,


lerm

sum arises from

Theseare itjc

occupancy zero; ihe


We have

Aexpf-c/i)

possibiliiies.

Mb 4- O2 or MbO2

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

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, the work on ihe adsorpiion of oxygen was done father of Chilian Bohr, by hemoglobin by Niels Bohr.The oxygen saturation curve for hemoglobin (Hb) lias a slower rise at low of Hb is tower Ihan for because ihe binding of a single O, Io a molecule pressures, energy Mb. A! higher has a lhat is concave upwards, of ihe Hb curve pressures region oxygen because trie binding the first is adsorbed. increases after O2 energy per Oj

The Oj
thai

molecules

on

hemes

are

in

equilibrium

with
on

the Oj

in

ihe

surrounding
in

liquid, so

the

chemical

potentials

of Oj

are equal
/i(O2);

ihe myoglobin

and

solution:

/i(MbO2)

\302\273

/(MbO2)

= ?.{O2) of /
of the

F7)
gas pressure

where
by

exp(/i/i}.

From Chapter 3 we

find

the

value

in

icrnis

the

retalion A =

n/nQ

p/t\302\253Q.

F3)

We

assume

ihe ideal gas resuit

applies

io C), in p.
O^

sotulion.

At

conslant

temperature

/(Oj)

is

direclly proporiiomUto tjic pressure Mb occupiedby The fraction/of

is found

to from {66}
1

be

_
I

Ac\302\273pl-t/i)

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

Fg)

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

(Mb)

Figure 5.11 The molecule with

reaction o( u
oxygen

nvyoglobm

may

be viewed
Gj

as

(he adsorptionof a molecule of on ihe large mjoglobin molecule.


results
follow

at a Tlie

site

3 Langmujr

isotherm

<{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

of O3,

rcbt

Fi\302\273ure5-12

Saturation and

curves

of O.

bound

lo nijoglobin

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

Tiie

vertical

a.\\is gives
which

ihe fraction of
lus

the

molecules

of Mb

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
ft action

0, mokcuk, or the

of the

pump.

The

curve

for myoglobin
reaction

has the
Mb

pioitual lonn (or the


MbO..

+ O2
Itits

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

The

curve for

lienio^lobin

;t

uiiiCicm
O,

lib
and

forrn because of ifsicracirons benveen molecules bound to ilic four si rands of ihe niolccule. The after J. S. Fruton dr^Atntjis
S. Siminondi,

Gvm-J

bioJtaniMry.

Wiley,

1961.

G'tbbi

Factor

and

Gtbbs Sut.

which

is

[he same
in

as

the

Fcrmi-Dirac

distribution

function

derived

in

Chapter

7. We

subsiiiute F8)

F9|

to obtain

} 4- I

\302\273iurexp(E/r}

G0}
p

or.

with

p0

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

'
Po

+P

whac

!>0

is constant

wiih respect
solids.

to prcsfi re,

but depends
when

on

the

temperature.

The

result

G1}

is

known

as the

Langmuir adsorption is ndtrm

used

to dcicribc

the adsorptioiiof

easts on the surfacesof

Example;Impurity

atom

ionizatian as impurities
of

in a
in

semiconductor.
crystalIn

Atoms

of

numerous

chemical
by

elements when present to the conduction band


may

a semiconductor

may iose an
the

electron
band

ionizalion

the semiconductor

conduction

the electron

oikn

be treated

as an idea! gas. The impurity


with

atoms

are
by

small
rest

and

diffusive equilibrium

the

large

reservoir

fanned
atom.

the

systems S in thermal of the semiconductor: that one, but only one. i of the electron spin
without

the atoms exchange

electrons

and

energy

with lite

semiconductor.
We suppose

Lei / be the
electron

ionizalion
bound

can be
an ^

to

of the impurity energy an impurity atom;


system
with

is accessible. Therefore
one
When with

the

& has

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


with

an

electron,

electron

has zero

as this stale; the stales of \342\226\240$ are summarized Suite

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

attached

an

electron

attached
zero

with spin
ofenergy

].

of &

\342\200\224 /. The

accessible

below.

number

Description

Electron

detached

Electron alladicd, s

1-kcifoti ijjnjLlicJ.
The

Gibbs

sum is given

by

G2)

The

probability

tliat

&

is ionized

((V

\302\273

0) is

P(ioaized)

\302\253

P(O.O)

\342\200\224 =

-\342\200\224-1-

\342\200\224.

G3)

The

probability

tliat

$ is

neutral

(im-ionized)

is

P(neutral)
which

= /'(It,-/)

+ P(U,~/) ,

G4)

is just

- PtO.O).

SUMMARY

1. The chemical potential


found from
equilibrium
/* \342\200\224

is

defined v

as h{t,V,N) i{cojvN}v_v.

{cUJcN)a

\342\200\224

= {tF/tN). v and may Two systems are in


internal.

also
difl'usive

bo

if jtx

= }tz.
of two
of

2. Tl^c chemicaipotential is made up external part is the potential energy


it

The internal part is ofthermalorigin; Tlog(u/iiy),where is the concentration


quantum

parts, external ittid in an external particle


an

The

field of force.
gas ;t(int) is the quan-

for

ideal
nQ

mooaiomic

and

^{Mi'lnh2)*'2

concentration.

3.

The

Gibbs

factor

gives the probability


will

that

a system
in

at chemical state

have

N particles
sum

and be

a quantum

potential ;i and temperaturei s of energy ts.

4, TheGibbs

is

taken

over

all states

for all numbers


X

of

particles.

5.

The absolute

activity

is

defined
of

by

expQi/r). is

6. The

thermal averagenumber

particles

<A')J

kg

\302\243

PROBLEMS

1.
angular

Centrifuge.
velocity

A circular cylinder of radius to. The cylinder contains an i. Find

rotaies

about

the ions

axis

with

ideal gas of atomsof niass


of

SI

al

temperature

j[(r) on the
H

radialdisiance
gas.

an expression
<\342\226\240 from

for

lhe

dependence

the

axis,

in terms

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

as

for

an ideal

2. Moleculeshi die Earth'satmosphere. If a is the concentration of mofcculcs of the Earth, Al lhe mass of a molecule, and g lhe gravitational at the surface at lhe surface, show that acceleration at constant tlic total number temperature of molecules in the atmosphereis
N

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

</rrJcxp(A/yKV<'0
l-yrih;
that

f75)

wifh

r iiuMstirtiJ
integral

ihc center
ttf (he
equilibrium. ihe

of

flic

here
N

R is
cannot

the railing of
be bounded

ihe liarili.
and the

The

diverges

tipjwr

limit, so

aimosphere cannoi be in are always escapingfrom


3.

Molecules,

particularly

light molecules,

atmosphere.
fa

I'ntuiitiul

each of mass
thermal

em-i'ity of gas
at

gravitational

Jield.

Consider

a column
field

of moms
Find

temperature

t in

a uniform

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

gravitational

y.

the

kinetic

energy
from

per atom. The

energy and
at lhe

bouom

K+ in lhe internal ions transport. The concentrationof potassium of !04 of a cell a factor a fresh water exceed (for by sap alga) may plant 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 ihese: How is ihe high in cell include ihrough tt. Important questions physics concentrationofionsbuilt up within the cell? How is metabolic energy applied 10 energize the aciive ion transpon?

4. Active

5.
drawn.

Afaguctic

concentration.

Determine

the

ratio

m/x for
=

which Figure5.6is
eh/Zinc

If

= 300K,
give

how many
a

Bohr magnetonsfiB
concentration

ivould

the

particles contain to

magnetic

effect

of the

magnitude

shown?

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

6,

Gibbs

sum for
whh

a two level
zero

unoccupied

one of energy zeroand oneofenergy


3-

energy

or occupied

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


s. Show

may
of two
ihis

be unstates,
is
system

that

the Gibbs

sum for

= i +

;.exp(-E/r).
of

G6)
in each

Our assumption

excludes the possibility


c include

one

time.

particle

state at

the same
state

Notice

ttuitn

in the

sum a term forN

\302\253= Oasa

particular

of a

system of a variable numberof particles, Show that the thermal (b) average occupancy of the system

is

G7)

(c)

Show that

the thermal

average occupancy of the state at energye is

(d)

Find

an

expression

for the

(e) Allow
one

particle =

the possibility that the orbital at at the same time; show that
Aexp(-\302\243/i)

thermal average energy


0 and

of

the

system.

ate may

be occupied

each by

3.

1 +

I +

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

/.)[!

+ Aexp(-e/i)].

G9)

Because ^- can befactored


posttiw tliat

as

shown,

we have iotuzation.
atom

in effect two independent systems. a lattice of fixed exist in four states:


Consider

uitd 7, Statesof negative diogen atoms;suppose each

hy-

can
of

Stale
Ground

Number

electrons

Energy

i
0

-JA
-if)

Posiiivc ion
Negative
E\\cii<.-d

ion

2
1

J3
U
of

FioU rlic

conUiiion that the


will

Livci;t^^

number

electrons

per mom

be unity.

The condition
X.

involve

5,).,

and

r.

Cmtitm
the

mtmoxitle
O2

replaces
energy

lu luihuning. ad^oibed on hanoglohin

catbon monoxide (lib) mulcculcs in


each
energy fixed

poisoning the CO
ilic

Wuoil.

To hhnw
be
with with

tl-.e clTect, consider a model for which vacant or may be occupied either with
eh

adsorption
ea home

by one molecule

CO. Let

A'

by sites

a heme may one molecule O2 or


site on be in equilibrium

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 occupied by 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 Hbsites are occupied by O2.
O2

and

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 Gibbssum the limit of zero the in adsorption by 1 percental field will differ from that 8 there the muhiof Problem because magnetic spin the was of bound slate neglected.) muhiplicity

9. Adsorption
to

ofO2

in

a magnetic

bound

a heme

10. Concentration fluctuations.


system

The
with

number

of particles We have

is not

constant

in

in diffusive

contact

a reservoir.

seen that

\342\200\242

<,v>
from E9).

re:

(a) Show lhat

<lY!>=LLi.
The

3- ^
<iV>

(81)
is

mean-square

deviation

((AWI)
=

of N from

defined

by
-

<(ANJ>

= <(N

<.V\302\2732>

(N>)

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

</V!>

<,V>:;

(b) Show

that this may

be

written

as

<(A.V)'>

= tc<,V>/c>

(83)
liial

In t'liaptcr

fi

xvi:

;u>rly

iliis

n-iilt

in llio

i.K'iil u:is to liiul

is the
diffusive

mean

square fractional fluctuation in the population with a reservoir. If <A'> is of the order of contact

of an
\\02Q

idea! gas
then

in

atoms,

ihe

Chapter 5:

ChemicalPotential

and

Gibbs

Distribution

fractional
diffusive

fluctuation is exceedingly smalt. In is it cannot panicles well defined even though

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). 11.

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


H.

Schindler,

Equivalent

definition

of chemical
An

potential*

The chemical potential


listed

was

defined

by

E) as (cF/cN)tiy.

equivalent

expression

in Table

5.1 is
(S5)

fi

*=

(cU/cN)ay.

Prove

ihat this relation, which


we

was used by

Gtbbs

to

define

ji, is equivalent
of/i,

to

that the definition {5}

have

adopted.

resultsC1)

and

C5).

Our

reasons
a function

a mathematical

potential moreoften

consequence, are
as

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


two-fold.

to make use of the


and

(85) as
of

In

practice,

we need

the chemical
the

of 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 because (85) simpler. /tN on integration, is a function of N; compare with H{N,c,V) {9.13}.

temperature tihanasa

funciion

a. Operationally,

12. in a

Ascent

of sap in trees. Fitsd iree under the assumption


leaves

the

maximum
the

height
stand

to which
in a

lhal

rools

water may rise of water and Ihe pool


r

uppermost
0.9. The
concentration of

are

in air

containing

temperature
water

concentration
water.

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 immediately aboveIhe poo!of
in the expansion,

waier vapor at a

relative humidity

13.

hentropic

(a) Show
the

expressed

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

thai Ihe entropy of an


orbital

idea!

gas

can

be

occupancies,

(b) From

this result

isentropic

expansion

of an

idea! monatomic

gas.

14.
infinite

Multiple

binding

of

Oi.

A hemoglobin
ofeach

molecules.

Assume
distance.

lhal e is the energy the Lei / denote


is

bound
activity

molecule can bind four O2 at rest relalive to Oaat O2,


exp(ji/T}

absolute

of

the

. solution), (a) What

the

probability

that one

on a and only one O2 is adsorbed

free Oi (in

hemoglobin

moiecule?

Sketch
four

ts the also.

probabiiity

Uiui

the result qualitatively as a functionof/.,(b) and only four O2 arc adsorbed? Sketch this

What result

15.

External

chemical potential.
in

Consider a
V. Let

system

at

temperature

t.

with

N atoms
value

of mass M
the

volume of

potentialat
of the

surface

the earth,

chemical the (a) Prove carefully atid honestly that


}i[Q) denote the value of the
the

tola! chemical

potential for p(h) =

identical

system

when

translated

to altitude h is
y

Mgh

where applicable

g is

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

that

Chapter

Ideal Gas
DISTRIBUTION

FERMI-DIRAC

FUNCTION

153

BOSE-EINSTEIN

DISTRIBUTION

FUNCTION

157

CLASSICALLIMIT
Chemicai

160
161

Potential

Free

Energy

163
16-\",

Pressure
Energy

164

Entropy

165

Heat Capacity

Testsof Example:Experimental Chemtcai Potential of Ideal Gas


Example: Spin Entropy
Reversible
in

165
the

Sackur-Tetrode internal

Equation Degrees

167

with

of Freedom
\342\226\240

169
J70

Zero

Magnetic

Field

Isothermal

Expansion

17'i
IT.t
i \025

Reversible Expansion at ConstantEntropy into a Vacuum Sudden Expansion


SUMMARY

176

PROBLEMS

177

1. Derivative
2.

of Fenni-DiracFunction
of Filled
Function

177

Symmetry
Distribution

and Vacant Orbilals


for

177
Statistics
Ideal

3.

Double

Occupancy

177
177

10. Isentropic
11. Convcelive
\\2.

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,
Relations

Gas

177
17S
i

7S

17S 17')
179 J~0

of

Ideal

Gas
of

isentropic Equilibrium
Piitu'itsiuns

the

Atmosphere

Ideal

Gas

iit Two

1^'
1SU
ISO

13. Gibbs Sum for Ideal Gas 14. Idcai Gas Calculations
15.

Diesel

Engine

Compression

ISO

Chapter 6: IdealGai

The

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

gas

is a

of particleslh;it

occupy

an
usually

orbital.

The thermal

distribution the orbital.

function,

designated

as /(ej./i),

average occupancy is calledthe where t is ihc energy of


only

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

Schrodingcr equation for


by chemists.

one

particle.

This
state

!fthc

interactions
sin in N

between particles
quantum of an lo

are weak,Ihc orbitalmodel allows of the Schi'6'tlingcr equation of a


approximate quantum

to approximate of A' particles system


us

exact terms panicles

approxiorbituls,

state

thai

we construct

orbital a solution of a one-particle There are SchroOinger equation. 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

by assigning the

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
of An

an

odd

number
Hie

of
must

particles\342\200\2242

electrons,

2 protons,

I neutron-

each of spin j,
aloin

so

that

have

half-integral

spin and
an

must be a fermion.
number

of 4He

has one

of spin |-, and 4Hemust be a boson. that The fermion or boson nature of the particlespecies 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
particles

more neutron, so ihcreare

even

of panicles

appear
An

as can

occupancy be occupied
zero.

rules: by any integral


0 or!

1.
2.

orbital

number of bosons of the same


of the

species,
An orbital

including

can be
is a

occupied by

fermion

same species.
the

The second
of

rule

statement

of the

Thermal Pault exclusionprinciple. averages


orbital rule.

occupancies

need

not be

but integral or half-integral, the

occupancies

of any

individual system must conformto one or

other

Fa-mt-Dirac

Distribution

Function

The

two

different

occupancy
is

each orbital:
occupancy

there
there

boson

rules give rise to two stun over all integral

different

Gibbs
orbital

sums

for

values of the

occu-

= 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
A',

and

is a

classical regime.
We

now

treat

the Fcrmi-Dimc

distribution
the

function
Bose-Einstein
orbital

for

the

thermal

average

occupancy

of an

orbital by
two

fcrmtonsand

for the thermal average occupancyof an

by

function distribution bosotis. We show the


we

equivalence of the
to treat

functions

in the
this

limit of low
Chapter

occupancy, and
7 we

go

on

the properties of a
and absolutely

gas in
for

limil.-ln

of famioit

bosoti

g;ises
cruchi

in the

opposite

particlesis

the properties

treat the properties limit, where the nature of the of the gas.

FERMI-DIRAC DISTRIBUTIONFUNCTION
We

consider

a system
system

composed

of a

single orbital that

may

be

occupied

by a

fermion. The
as in

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 1 +

\302\243=

;.exp(~f./r). with

(I)

The term 1 comes from the = 0. The term -Uxp(-~-\302\243/r) \302\243

configuration
comes

when

A' = 0 and energy occupancy the orbital is occupied by one fermion,


of N

so

that

*= 1 and

the energy

is e. The thermalaveragevalue
term

the

occupancy

of the

orbital is the ratio of the

in

(he Gibbs

sum

with

1 to

the entire

Gibbs sum:

B)

Chapter

6:

Ideal Gm

Occupied

,VQl

Wo)

log

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

o(/V0

I,

Uu

*) = a{A'u.

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

Figure

6.1

fermion.
energy

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

system a single otbhai that and diflusixc contact v-uh


might

may ihe

be occupied reservoir

a! most

by

one

be

the

kinetic

spin orientation and considered as forming

confined to
the

a fixed

volume-

encigy of a free electron Other allowed quantum


will

at temperature of a definite states may be


if the

t. The

reservoir.
fermions

The reservoir
if the

contain
by

JVO

fcrmions

sysiem is

unoccupiedand
We

JVD

system is occupied

one

fermion.

introduce

for the

average oecupancythe
fie) s

conventional an

symbol orbital

/(e)

that

denotes the

thermal averagenumberof particles in


<.V(\302\253)>.

of energy

e:
C)

Recaii

from

Chapter
the

5 that
standard

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

is the

chemical

potential.

We may

write B) in

\"exp[(\302\243

-,0/r]

D)
1\"

Tills

result

gives

as the Fenm-Dirac distributionfunction.* D) Equation of energy e. The value Ihe average number of fermions in a single orbital
is known

O2

119261,

and The

P. A.

M. Dirac, Proceedings

of

i!:c Royal

Sociciy of London AI12. 661[

iicovcrcd. general

itaicmenl

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

Fertni-Dhac

Distribution

Functlor

System

Figure shown

6.2 here.

(a) Tlic obvious method of viewing The energy levels each refer to an

of noninicracling a system orbital thai is a solution of


of

panicles
a

single-

parliclc

Sclirodinger

equation. Ttic

loial

energy

the sysiem

is

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

is ihc

number

or 1.(b)

Ii is

much

3- ~ I
Tltc

+ Acxp{~ejti
=

firsi

scrm

arises

from the orbital

occupancy JVH

0, aad

the second

tcnti

arises

from

;Vq = 1.

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

- 0) &
not

fi(Q)

Ef.
Fermi

E)
the

We call
*
En

cF

the

Fermi

energy,

to be

confused* uiih
used for

level

which

ilie

semiconduUor
Fennt

liseraiure
level.

ihe symbol

cF

is often

;( a! any

lempfniurt.-.

a:-d ef i

ihen called she

Chapter

6; Ideal Gus

\\

A'

\\
1

........
-7

_6

-5

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


distribution

\342\226\240~m. I

Figure

6.3

Plot

of the

Fermi-Dkac
of/(c)

function

/(e)

versus e

- p in

unils

of

the temperature

r. Tlie value

gives

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

of orbitals at a given energy tlfe system in thermal equilibrium. When is from the shaded region at E/p < transferred
the fraction
electrons

in a

metal,

ji

might

is !he temperature dependent orbiials, as in Figure6.4.At

/t(t). the

Consider

a system t =

of many independent

temperature

!he of

Fermi

energy energy

are are
/i

occupied unoccupied.
from
energy in

by

higher

orbitals of energy below exactly one fermion each, and ail orbitals At nonzero temperatures the value of the
0, ali
to

chemical potential departs there is an orbilalof If


orbital

Ihe Fermi
equal

is exactly

half-filled,

ihe

sense

of

energy, as we will see the chemical potential a thermal average:

in Chapter

7.
the

(e

*=

//),

F)

Orbitalsof
are

lower

energy

are

more

ihan half-filled,

and orbilals of higher


the

energy

less than

half-filled.
Fermi-Dirac

We shall discussthe physical of consequences in Chapter 7. Righi now we go on to discuss the

distribution
of non-

distribution

function

-I

Distribution

function

Figure
think

6.-1
of

convenient

pictorial

way to

a system
do

orbitalslliat
but

iutecacl

with

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

interacting bosons, and


and

then

we

establish

ihe ideal

gas law for boih fcrmions

bosons

in the

appropriate

limit.

BOSE-EINSTEIN
A

DISTRIBUTION
an

FUNCTION
value

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 the of a boson gas. There is a sudden increase to the in attributed properties In and in ihe heat JHe below this of temperaturefluidity conductivity liquid 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 2.17 K. the and Photons of (the electromagnetic field) quanta phonons (the quanta number is of elastic whose waves in solids) can be considered10be bosons
boson

is a

particle wtjh thai an orbital

integral

of the

not
of

conserved,
an
We

but

it

is

simpler

to think

of photons

and phonons as excitations

osciiiator,
consider

as we
the

did in Chapter 4.
function with
the

distribution

in

thermal

and

diffusive

contact

all
by

of the
one

same species.
particle;

Let \302\243 denote

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

when

as

Figure

6.5. We

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

Go: Chapter 6: Ideal

as pan ofIhe The Gibbs


sum

reservoir.

Any

arbitrary

number

of particles may

be in i : orbital

taken

for

the orbital

is

G)

The

the in combined tola! numberof panicles 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

i \342\200\224 A\" i

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

(8)

provided

that

inequality;
the

this will all applications, \342\200\224e/i) satisfy /,exp( would not be bounded. in the otherwise the number of bosons system

kcx.p{~t/z)

< 1. In

The thermal averageof !henumber


Gibbs

of

panicles

in the

orbital is

found

from

sum by use

ofE.62):

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

A0)

__

Bosc-\302\243insicin

Distribution

Funclio

Figure 6.6
dislribuiion

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 temperature

ihe

chemical

potenijai
at

ft

for

a FD

distribution

is

postnve, and changes 10 negative

high

lemperaiure.

This

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 of ihe distribution are The choice functions approximately equal, as discussed below. made in any choice e is always arbitrary. The particular zero of ihe energy

defines the

problem
is discussed

wiU affect
\342\200\224 has

ihe
in

\\a\\uc

of

the

dieniic.il

difference e
A gas
orbital

/;

to be
B0)

independent
below.

of the choice of the zeroofe.This


the average

potential

/i,

buE

the

vaU:e

of ihe
point

iuriher

is

in

the

classical

regime

when

number of atomsin
for

each

is much

less than

one. The average orbitaloccupancy

a gas

at room

isof the order of only 10\026, safely in the temperature and atmosphericpressure classical Differences between fcrmions (half-integral spin) and bosons regime.

Chapter

6: Ideal

Gas

and

liicq

Uau iuiu

reg

imcs

Class Regime

of

T!Krma!

it
ny

i*:

o CCup.iticy

___

parlic

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

III

Boson Quantum
Fcfmioii

Aluays

much

less

lhan one

Close
Orbital

10 bul
of

Boson

lowesi

less ihan one. energy lias

an occupancy much

greater than

one.

arise

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.

oniy

in

Table

6.L

CLASSICAL

LIMIT
is defined

An

ideal

regime.

in ttie classical as a systemof free nomuteracting particles \"Free\" means confined in a box with no restrictions or e>uernaiforces

gas

acting
of the

within

the

box.

We develop

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 one it is not the energy of a system energy of an orbital occupied by particle; N

particles.
are

The Fermi-Dirac

(FD) and Bosc-Einstcin (BE)

distribution

func-

functions

where

lhe plus

sign is

for

the

FD
be

distribution
much

and
th;m

distribution.In orderthal/(c)
must have in
this

smaller

the minus sign for the BE unity for ail orbitals, we

classical

regime

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

A2)

for

all

e. When

this inequality
of (tt).
is

denominator

is satisfied we may neglect Then for either fermionsor bosons,the

the

term

+!

in

the

average

occupancy

of ail

orhiiat of energy r.

/(i.)

cxp[{/i

wiih

/. hs

exp(/j/r).
the

The
limit

limiting

result

A3)

is called

function. !t is functions when

of

the

Fcrmi-Dirac /(s)

dfstnbulion and Bosc-Einstein distribution


the classical
in

the

average

occupancy

is very

small

comparison for

with particles

Equation A3), unity. described by quantum


always

involves

although called classical,is still a result mechanics: we shall find that the expression the quantum constant /i.'Any theory which, contains
distribution

for

or

/.i

h cannot

be a
We

classical theory.
use

the

classical

function /(r)

thermal

properties

of the

ideal gas. There aremany

= Aexp(-r/i) to
topics

study

the

of

importance:

the
the
in

entropy,
relation,

classical
terms

of

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

Chemical Potential

The chemical of total number


the

potential

is

found

from

the condition

that the
distribution

thermal average
to

of atoms

equals the

number of atomsknown

be

present.

This number must

be the sum over all orbitalsof the


N =

function/(eJ:

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 mocks ofmotion. total

of atoms

in

each

orbital.

We useA3)

rn

A4)

to obtain

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

AS)

To evaluate
is

this

sum,

observe

that

the summation

over free particle orbitals


atom

just

the

partition

function

Zx for a

single

free

in

volume

V, whence

Gils Chapter 6: Idea!

In

Chapter

3 it was

shown that Zt

HqV,

where

nQ

(Mrjlnh2K11

rs the

Thus quantum concentration.

A'

;.Z,

/.,,QK;
n

;. =
NJV.

W/i?QK

i?/hq

A6)

in

terms

of the

number

density

Finally,

\302\253=

exp(/i/T)

nftiQ

,
j

A7)

which

is equal

to the
n;nQ

number
is
\302\253I.

of

atoms

in

the

classicalregime gas is

The

chemical

volume quantum of the ideal potential

l/nQ. in the

monatomic

P
in agreement

=\302\273 T

tog(n/iiQ)

(IS)

wiih E.12a)

obtained in another way.

The

result

may

he written

out to

give

\302\253

i[)ogN

log

Jiogt

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

A9)

We

see

that as

the chemical

decreases

the temperature

potential increases increases.

and as the concentrationincreases

Comment: The simple expression modifications.We mention four


(a)

(IS) for examples.

(lie chemica!polentiaf
an energy of at

can

be subject

lo sevcra!

If the zero of ihe energy scale is shifted by energy of an orbila! falls ill e0 = A instead
i

A so

that

(he

zero

of the

kinetic

e0 = 0, then

=.

+ Tlog(n/nQ).
in ihe

B0)
sum in(iS)
and
i\302\273 mufliplicd

(b) If lite

atoms

\\\\;i\\e

spin

S, the

number of orbiiafs
\\

by ihe

spin ;:iuliipiidiy^S is JoublcJ; nQ will


wifl

4- I. For s.pin
be replaced

il isdiJublcdLlhevalucof
by 2\302\273G,

t\\eryw[icre

Ihe

iheparlition nght-hand

fund ion Z^ side of{18)

h3\\c

an

added

ferm -rlog2.
t^e enter

Tile tfTctt
energy

of

Shi: spin

on She enSropy is
ro^itionaj

Srcalcd
-ind

below.
fc)

the &3s is not fTiOnatonuc, moiion wifl vibraiional


If

iiitern^J

ihe

partition

sS^ies associated with function, and tfic chemical

potential

wilt

free

Energy

have

- 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 sec for /t may be considerably more complicated; 10 tk j for van to of interder Waals Chapter g;is relatively simple approximation
an added

term

Free

Energy

The

chemical

potential

is related to

the

free

energy

by

(CF/dhr)t_y

= n ,

B1)

according to Chapter 5. From


F{N,t,V)

this,

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

tJ^N

[log <V

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

where so

the integrand

is found

in

brackets

in A9).

Mow Jt/.vlog.v

= xlog x

\342\200\224

x,

[hat

- iVi[logW -

fog V

- Jlogr + JlogBn/iVA')]

C3)

F
Tile free energy increaseswith

Wr[iog(n/nQ)

1].

B-t)

concentration

and

decreases

with

temperature.

Comment:
Thus, from

The

integral

in B2)

should

strictly

be

a sum,

because

A'

is a

discrete

variable.

E.6),

f(N,r,l')

f
in

Ji(-V)

B5)

which differs from Ihe

integral

only

in ihc

lenn

log

,V in

A9), for

f. log.V

= Iog(l x 2

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

N)

= iog/V!

B6)

ChapM6:UtaICai
wHcfg

the

inic^EiiI

A1 \302\2433\\e

log A'

\342\200\224 _V in

B3).

Bui for

targe

she Stifling

approximation
B7)

log,V! ~
may be

MogN -

used, and now B5) is ihc

same

as B3).

Pressure

The pressure

is relatedto the

free

energy

by C.49):

With B3)

for

F we

ha

Nt/V;

pV

Nz

B9)

which

is the

idea! gas law, as derived

in

Chapter

3.

Energy

The thermal

energy U is found
U-F

from

U ~

iff,

or

ta-F~

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

-t:

C0)

With B3)

for F

we

have

2t

'

CD

so that for

an ideal gas

C2)
The

factor

| arises
if

from

the

exponent

of x

in

\302\253Q

because

the

gas

is in three

dimensions;

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 principle of freedom was discussed degrees ofequipartitionofenergy among
iiq

were

in one

in Chapter 3.

Heat

Capacity

polyatomic

molecule

has rotational

energy

relational degree of freedom is%r when ihe lemperature is high in comparison with the energy differences belwcenlhe roialiorta! |e\\els energy of ihe molecule. The rolaliona! energy is kinetic.A linear molecule has two a nonlinear molecule has degrees of rolationa! freedom which can be exciled; tliree degrees of rotalional freedom.
of each
Enlropy

and degrees of freedom,

the

average

The

enlropy

is related

to the free
a

energy by
-(oFJdT)v,K.

[33)

From B3)

for

we

have

the entropy

of an ideal gas:

This is idenlica!
\302\253 1,

with

our

earlier

result

C.76).

In the

classical regime h/uq


as

so

lhiil

\\o^n0/n)

is positive.
entropy

The result C4) is known


of

lhe

Siickur-Tflrode

equation

for the

absolute
essential

a monatomic

idea! gas. It is

imporiani

historically and is

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 basiswas fuliy understood, it was a greal challenge to quantum-mechanical

the

theoretical
unsuccessful

physicists

to

explain

the

Sackur-Tetrode
the

equation,
years

and

many

un-

attempts

to do

so were made in

early

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

size

of the

concentration-

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

valve is

opened (Problem6).

Heat
The

Capacity

heat

capacity

at constant

volume is defined

in

Chapter

3 as

C5)

Gos Chapter6: Ideal


We

can

calculate

the

derivative

directly
wn'tien

from the entropy C4) of an

idea!

gas

wlien

the expression

for

nQ

is

out:

IE

From this,

for

an

idea!

gas

C6)

or Cy
heat

%NkB

in

conventional

units.
because C\302\245

The heat must

capacity at constant pressure is largerihan


be added

additional

to perform the work


pressure
xda

needed

to
in

expand
detail

gas againstthe constant lhe thermodynamic identity

p, as
=

discussed

in

the volume of 8. We Chapter

the use

dU

-f pdV to obtain

/eu The

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
energy

of

an

ideal

gas depends

C, =
in

Q. + N

C8a)

fundamental

uniis,

or

C,
in

C,

Nk,

C8b)

conventional
have

units.
in

We two

notice

again of units.

the different dimensions that heat

capacities
as R,

the

systems
written

For one mole,NkB

is

usually

written

called the gas constant.


are

The resultsC8a,b)
decrees

for

an

ideal gas

without spin or otherinlernal


\342\200\224

of freedom

of a

molecule. For an alom Cy = In + n

:N,

so

that

c,

= |,v

C8c)

Heat

Capacity

in fundamental

units, or

Cp
in conventional

\302\273

$NkB

C8d)

units. The

ratio CpjCv is written as 7,

the

Greek

letter

gamma.

Example;
entropy

Experimental found

tests from

of the

Sackur-TeiroJc
values

are oflen

experiment!

equation. Experimental values of Ct by numerical integration

of

ihe

of C7)

C9)

Here <j@)

denotes law

ihe

entropy

at the lowest

of C,,. The fhird

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 thermodynamics

temperature attained

in

rhe

measurements

1.

Enlropy increase on
Entropy

healing

solid

from

absolufe

zero to the melling


[mini to ihe

point.
Chapter

2.
.1.

increase

in ihe

solid-to-liquid
liquid

transformation (discussedin
niching

10).

Entropy
Lntropy Enlropy

increase
increase change

on hearing
in ihe

from

boiling point. selected temperature and

4.
5.
There

liquid-to-gas transformation. gas from


the

on heating

boiling

point

to ihe

pressure.
may

further

be a

slight

corrctiion

lo C4)
now

for ihe
been

of experimental

and theoretical

values have
for

carried

nonidcalilyoflhe gas.Comparisons out for many gases,and


=s kua.

very

We
enlropy

give delails of the is given in terms

comparison

neon,

afler ihe measurements


S

of Clusius.The

oflhe conventionalentropy

I.

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

=,

i4.29Jmor'K~t. its hiat

\342\200\242

A classic

vtudy is \"The heal rapacity of


Chemical

oxygen

from

12 K to

its

boding

point

,ind

of

ihe American

Society

51.2300 A939).

Chapter 6:

idcutGa:
1

able

xaluaot
wide
iiosph

uropy ullli c

boilin

Enlropy
Gas

in

Jmol\"

'K\"
Ca

r.lp,lnK

E Nperimenia
96.40

Iculalo

Nl-

212
87.29

96.45

Ar

129.75

12924
cd.,

Kr

119.93

144.56
BonMvin

14506
Voi

sul'rce:
Pan

From

Lumhh

labics, 6lh

4, pp. 394-399.

. 2.

The

hc.it

inpul

required

to mc!l
is

the

solid

ai 24.55

K is observed

lo be 335

J mol\"'.

The

associated enlropy

of melling

3.

The
point

heat capacilv of the of 27.2 K under one

liquid

was

measured
pressure.

from

the

inching

poim

[o ihe
found

boiling

atmosphereof
ASIJ4Uid

The entropy

increase was

10 be

- a.SSJmol-'K-1.
27.2K

4.

The mol\021.

heat

input
The

required

associaied

at to vaporize ihe liquid enlropy of vaporization is

was observed

lo be 1761J

The cxpertmenlal sphere adds up to


sK3i

value

oflheeniropy

of neon

gas a! 27.2K

af a

pressure

ofoneafmo-

^.oiid

ASmelling

&SUvAi
of neon
=

ASViPQliMlion

\302\253 96.40Jmor'K\021.

The

calculafed

value of

the

entropy

under ihe
Jmor'K\021

same condifions
,
with

is

5g\302\273,

96.45

from ihe

Sackur-Tefrodeequation. The excellent

agreemenl

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

fhe experimental value led to the Sackurfind it verified by 6.2. in Table

Chemical Potential

of IdealGas

with

Infernal

Degrees

of FreeJoin

Chemical Potential of Ideal Gaswith


Internal

Degrees

of Freedom
molecules.
in

We consider now an idealgas of identical polyaiomic has rotational and vibrational degrees of freedom

Each to

molecule

addition

the transla-

tional degrees of freedom. Thetotal energy


independent

e of

the molecule

is the

sum of two

parts,

\302\253 \302\243 en

eifli

,
and degrees of freedom

D0)

where
to

einl

refers

to

the

rotational

and vibrational

r.n

the translations!

motion of the
ts

center of massofthe
oscillator

molecule.

The

vibrational

energy
rotational

problem
energy
the

the

harmonic

problem
orbital

treated
n is

earlier. The rota-

was

the subject
regime

In

classical

the Gibbs

of Problem '3.6. sum for the


1

\302\243\302\253

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

D1)

where

terms

in n

higher

powers

of ),

ofthe orbital is assumed to to correspond occupancies states Gibbs sum associated


the

be

greater

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
are omitted

D2)

D3)

The

summation

is

just

the partition

function of the

internal states:
(\024)

which

is

related

to the

internal free energy of the

one

molecule

by

/\"in,

~tlogZ;ol.

From D3)

the Gibbssum is

D5)

Chapter

6: Idea!

Gas

the state of
in
X

The probability
internal

that

the motion

transtationat of

orbita!

the molecule,

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

to

the

Gibbs

sum 3-:

The classical regimewas

defined

earlier

as

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

result
plays

analogous to
Several

A3)

for

the

monatomic

ease, but

now

D6) is entirely the role of A.


for

of

the

results

derived for the

monatomie ideal gas are different

tlie

polyatomic

ideal gas:
A7)

(a)

Equation

for,*

is replaced

by

D7}

with have

<iq

defined

exactly

as before

(We shall
zero

always use ne as defined


spin.)

for

the

monatomic

ideal gas

of atoms with

Because

e\\p(/i/i)

we

p. =

~
r[log(ri/nQ)

IogZiol].

D8)

(b)

The free

energy is increased by,

for

JV molecules.

D9)

(c)

Thecniropy

is increasedby

E0)

The former

resuU U

\342\200\224

jh'z

applies

10 die

iranslalional

energy alone.

Example:
represcnl

Spin

enmtpy

in zero

boih

electronic

ntasnrtic field. Consider an and nuclear spins. TIic iniernal

of Spin /, funciion partition


atom

where /

may

associaied

Reversible Isothermal Expansion

with

the

spin

alone

is ZiM =

{2/ + t) ,
spin

E1)
contribution

this

being

the number

of independent

spin siaics.The

to the

free energy is

Fial = -tlogB/+
and

1) ,

E2)

the

spin

entropy

is
=

\302\273,.,

logB/

1) .
is found

E3)
with the help

by

E0).

TheefTec!

of the spin

entropy on the chemicalpotential

of D8):
E4)

}i = T[Iog(n/ii0)

logBi

I)].

Reversible

Isothermal

Expansion
x

1 Consider as a model example


!03cm3 at 300K. Let the
volume
gas

1022

atoms

of 4He

at an initial volume of

expand

slowly

at constant
maintained
expansion

temperature
constant
the

until

the

is 2

x !0Jcm\\

The temperature is

by
system

thermal
ai

contact with a large reservoir.In a instant is in its most probable configuration.


What

reversible

any

is the
final

pressure
volume

The
to the

after expansion? is twice the initial volume; the


pV \342\200\224 S'x

final

temperature

is equal

initial temperature. From


the

we

see

that

the final pressure

is

one-half
What The

initial

pressure.

is the

increase of entropy an an of ideal at entropy gas


a(V) =

expansion?

constant
A'log
V

temperature

depends

on

volume

as
E5)

4-

constant

= jVIog2

= (ix

l0\{0.69?)")
*=

0.069

1033.

E6) h.TS

Notice that the more accessible

entropy is larger at the largervolume, states in the largervolume than in

because

the

system

the smaller

volume at the

same temperature.

Figure

6.7

Work

is done

by

(he

gas in

an isothermal

expansion.Herethe gas docs work by raising llic weights. Under isothermal conditions pi' is constant for an ulcal gas, so thai the pressure mus! be reduced to affow !hc volume to llio load of expand. The pressure is reduced removing by
weights a
little

at

a time.

How much
When

work is done by
gas

the

gas

ht the

expansion ?
it

the

expands

isothermally,

does

work

against

a piston,

as

in

Figure

6.7.

The

work done
=

is on the piston when the volumeis doubled

H\\NxjV)dV

Ntlog2.

E7)

We evaluate/Vt

is, piston

directly as4.!4 x
E7),

30serg=

43.4J.

Thus

the work

done on the

from

Ni!og2

\302\253

DJ.4J){0.693)

2S.7J.
E7)

E8)
when

The assumption that the process that a knowledge of Vat every stage
We

is reversibleentersin
determines

we assume

p at

every stage of the expansion.


agencies.

define

W as

the work

done on the gas by


the

external

This

is the

negative of the work done by

gas

on the

piston. From

E8),
E9)

w=

-jpdV= -28.7J.

ruble

Expai

mt Entropy

What is the
an

The energy
expansion decreases
Chapter

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

*=

jNx

and

does

not change
energy

in

at constant by Afilog2,

temperature. which is the work

However, the Helmhoitz free

done.The connection is discussed


in

S.

? 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. heat The quantity 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
have

We

seen

Q +

0. Thus

Q =
from

28.7 J ,

F0)

the

result

E9).

Reversible
We that

Expansion
above

at Constant
an expansion

Entropy
at constant temperature. Supposeinstead in inan from I x 103cmJ to 2 x 10Jcm3
or

considered the

gas

expands

reversibly
flow

insulated container.

No heal
out

to

from

The entropy

is constant in a system
reversibly

isolated

processis
is called has

carried

(slowly).
is

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

an isentroplc process or an the specific meaning that there


we

adiabatic process.
no

term

\"adiabalic\"

heat

transfer

in the

process. For

simplicity,

shall

stick

wilh\"isentropic.\"

What is the temperatureof the gas after expansion ? The entropy of an ideal monatomic gas depends

on

the

volume

and ihe

temperature as

a{z,V)so that the entropy


remains

N{iogT3;I

logK

+ constant)

F1)

constant

if

Iogt3/2K=

constant;
eniropy '

t3/2K =
from
V1

constant.
we

F2)

In an expansion
at

constant

to

V%

have

Tl3'2f,
for

= rivlV1 .

F3)
.

an

ideal

monatomic

gas.

Chapter6: IdealGas
We
V

use

the

idea! gas

law pV =

Nz

to

obtain

two

alternate

forms. We

insert

Nxjp into

F3) and cancelN on both sidestoobtain

F4)
Similarly,

we

insert

r =

pV/N in F3)

to obtain

F5) BothF4)
molecules and

F5)

hold

only
Problem

for a
10

It is ihe subject of
with

monatomic gas.
to

internal

degrees

of

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


generalize

these

results for

for

an iscnlropic

process

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

F7)

Here'/ s
constant

Cp/Cy

is

the

ratio

of the
=

heat capacities at constant pressureand


find from
\302\253 189

volume.

With

Tx

- 300K and

Vs/V2

|- we

F3):
K.

F9)

Tt\\k is

ihe
in

final

temperature

after

the

expansion

at constant

entropy. The gas

is cooled

the

expansion

process

by

Tt

- Tt =
entropy

300
is

189 K

- !!IK.
method

G0)

Expansionat constant
What

an

important

of refrigeration.

is

ihe

change

hi energy

in ihe

expansion?
the

from The energy change is calculated ideal monatomicgas

temperature

change

G0). For

an

U2

= \302\243/,

Cy{x2

r2 -

r,) ,

G1)

fi

Expansion

into

or, in

conventional

units,

a2-

ut =ivA-B{ra- r,)
\302\273i(l

10IZ)(j.38

JO\0216ergK\"!){-IHK)
G2)

=\302\273 -2.3

108erg

\302\273 -231

The energy
the

gas

is

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.
Vacuum

Sudden Expansion inlo a


Let

the

gas expand
a hole

suddenly into a vacuum


excellent
in

from

an

initial

volume

of I liter

a Hn:t!vohmicof 2 liters.Thisis an
When

cxiimpfe

of an

irreversible

to process.
moms

is opened

the

partition

to permit

ihc expansion,

the first

and strike ihc opposite wall. If no heal How through the is kinetic the to their no way for atoms lose 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

through

the hole

walls is

there

Hois1 work is done in the expansion ? much No meansof doing external is provided, work
Zero

so that the

work done is zero-

work

is not

the

work
is

is zero
the

but of all irreversibleprocesses, for expansion into a vacuum.

necessarily

a characteristic

What

temperature

No work is doneand no heat is added in the expansion: W = 0, Q ~ 0, and ~ = 0. Because the energy is unchanged, the of the ideal U2 t/j temperature 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,
What

after expansion?

is

the

change

of entropy

in

the

expansion

?
doubled

The increase

of entropy when the volumeis

at constant

temperature

is given by E6):
Au

a2

a,

- Nlog2 =
2

0.069

1023.

G3)

For

into a Expansion into a vacuum


the expansion
probable

vacuum

= 0.

is

not

a reversible

process: the

system is not

in

the

most

(equilibrium)

configuration

at every stage of the expansion. Only

ChapterS:

Idea!

Gas

'

Reversible ]
isothermal
V

y
0

t-.Vtlog-^

I-

expansion j
Reversible

Nlog^

A'rtog-

isentropic
expansion

J
\021

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

j
y

Irreversible expansion
vacuum

into

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 are sumresults of these calculations equilibrium
the

initial

configuraiion

after

summarized

in Table

6.3.

SUMMARY:
GAS

STEPS
FOR

LEADING TO THE
MONATOMIC
Occupancy

IDEAL

LAW

SPINLESS

GAS
of an

(a) /(e) =
=

Aexp(-\302\243/r)

orbital

in

the

classical N
=\342\200\224-\342\200\224-\342\200\224~~~

limit

of/(\302\243)

\302\253 1.

(b)

Given x

i
En

N,

this

equation

determines

e*P(-\302\243nA)

-[n the

dassical
of a
V.

limit.

(c)

=
-\342\200\224-177x73

'j
Ik
'/ii
j

Energy
quantum

free particle
n

orbital of
cube of

number

in a

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

n2

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

Transformation integral.

of the

sum to

an

(e)

X =

N/nQV

Result of the integration


subsitution

(d) after

in (b).

(f)

nQ

= {Mi/27rfi2K/2

. concentration.

Definitionof the qaantam

(g)

T!og(ll,'!!Q)

(h) F

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

NiDog(tr/HU)

1]

(i) p

- -icFfcV)t,N-

Nt/K

PROBLEMS

steeperthe slopeof
2.
appears

Derivative of Fermi-Dirac function. Fermi level e = ji has the value Dt)~'.


7.
the

Show
Thus

that

\342\200\224cf/vc

evaluated

at

ihc

the lower

the temperature, the


+ 5,

Fermi-Dirac

function.
orbitah.

Symmetry
as

f{fi

of 'filled and vacant i5). Show that

Let

e = /i

so

that

/(c)

ap-

Thus

the

to the

sometimes

probability an orbital6 below known as a hole.


function

probability

that

fin + 5) = 1 -'/(/< - 3). an orbital 5 above the Fermslevel


the

G4)

is occupied
A

Fermi

level

is vacant.

vacant

is equal is orbital

3.

Distribution

mechanics

values
and

of
It,

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
for

double

occupancy

in

which

the allowed

respectively.

(a) Derive
reservoir
(b)

system composed of
Return

an expression for
this

the

ensemble is

average

occupancy

(N>, when the

orbital

in

thermal

and diffusive

contact

with

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
for

at temperature now to the

t and chemical usual quantum

potential/t.

the

ensemble
the

occupied
particles

total

energy

is 2e.
relativistk

4. Energy
have

of gas of extreme
p such
relation

particles.
\302\273 Me2,

Extreme M

relativistic

parti-

momenta

that

Thede Broglie /. = particle. 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 Thermoproblems discussed by E. Fermi variety of relativistic of wul Suiiisiks, Chicago Press, 1966,paperback.) University
Show relativistic Tor are ttynumU-s

pc

where

is the

rest mass of the

5,

Integration

of

the

tlwrntodynanric

identity

for an

ideal gas. Fromthe


have

thcr-

modynamic

identity

at constant

number of particleswe

^.
X

G5,

Chapter

6; Ideal

Gas

Show by integration thai

for

an

ideal

gas the
+

entropy is
V

a =
where
6.
in

Cv

logT

N log
and

at

G6)

crj is

a constant, independent of t
of mixing.
contact

V.

Entropy
diffusive

Suppose
a system
after

that

with

of N atomsof type
equilibrium

a system

of

jV

atoms B at

and volume. Showthat


is

A is placed same the temperature


of type

diffusive

is reached
known

increased

by 2N log

ofmixing.
entropy

if
when

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

the total entropy


in

2. The

{A

diffusive

contact

is established.

The difference (a) Show


reservoir

in

the

results

has

been called

ihc Gibbs paradox.


of

7.
pressure

Relation

pressure

and

energy

density,
with

ihat

ihe

average

pres-

in

a system

in thermal

contact

a heat

is given by

G7)

where the sumis over all states


that

of

the

system,

(b) Show

for a gas offree particles

-r77

G8)

result of the boundary conditionsof the whether es refersto a stateofJV noninteracting that for a gas of free npnrelativistic particles
as a

problem.

The

result

hoids equally

particles

or to an

orbital (c) Show

p= WjlV ,
where

G9)
is

is the

thermal

average energy of
it

the system. This result


Tor fermion

not

limited

to the classical

regime;

holds

equally

and boson

particles, as two

long as
8.

they

are

nonrelativistic.
We

Time for
in

cases

a large fluctuation.
liter

quoted

Boitzmann

to ihe

effect that

a 0.1

container
We

wiH

unmix

to 10\" JHe

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
shall

only

in a

lime enormously

long compan^

investigate

a related

condition.

to a volume (b) The gas is compressed isothermally stales are accessible now?
(c)

of

0.05

liter.

How many

For

the

system
of

in

the

0.1

liter

container,

estimate
one-half

the value of the ratio


of

number

states

for which
for

all atoms
the

are in

the

volume

number of states
(d)

which

atoms

are anywhere
10lC)s\"',

in the
is Ihe

volume

'
of

If

the

collision
all

rate of
in the which

an atom is %
system
in

what

total number

collisionsof

atoms with

ofthe
(e)

frequency

Estimale
in

the of

are

one-half
atoms but

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

We use this

the slate

of the

9. Gasof atomicgas,
energy

m'th one

iutermil for

degree

of freedom.

Consider
volume

an ideal manan

which

the atom

A above

[he oiher.

There ;ire H aiomsin


live

has two internal energystales,one


V at

temperature

r.

(o) heat capacity;it constant pressure.

l-'nut ttic (a)

chemical puk'iiljai; (h)


relations

energy;

(c)

entropy;

(t|> pic.^uic;

10an

hentropic

of ideal

gas.

(a) Show that the differential

changes for

tdcal

gas

in an

isentropic

process satisfy

(SO)

where

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

if

the

molecules bulk

moduli

internai are defined as


have

BB

~V{cp!cV)a;

Bs =*

-V(dp/dV)t.
velocity

(81)
sound

Show

that

for c

an

idea!

gas Ba
of

= yp; B,
iittie

= p.
heat

The

of

given by
Here p
//.

ideal gas of
Convcaire
the

(Ba/p)\022; ihcre
molecules

is very
M

transfer

in a sound

in a gas is wave. For an


=

mass

we have

is the massdensity.
iscntropk
entropy,

p = pi/M,

so

that

(yr/'A/I''

of
at

equilibrium of the
troposphere\342\200\224is

atmosphere\342\200\224the

atmosphere. The iower iO-15km often in a convccijve sieady state


\\\\\\

constant

not

constant

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

temperature.

such

equilibrium

p\\\"'

is

Chapter6: IdealGas
If

the

actual

atmosphere

gradient is greater than the isentrapic temperature be unstabic with respect to convection. may
in

gradient,

the

12. Idealgas ttro monatomicgas


in A

dimensions,
two

(a)

Find
with
an

ihe chemical
N atonis

potential of an ideal

dimensions,

L2. The
an

(c) Find
13.

spin is zero,
for

(b) Find {a)

expression

confined to a square of area for the energy V of the gas.


r. from

expression

the entropy
With

a. The
the

temperature is
help

Gibbi

Chapter

is 3in

sum for ideal sas. 3, show that the


V in

of

Zs ^
gas

Gibbs sum for an


Hie

ideal
there

(i>QV)sf,\\\\

of
;V

identical
atoms

atoms
in

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


diffusive

probability

arc

Hie gas

volume

coniact

wiih a reservoir is
<N/exp(-<N\302\273/N!

P(N} =
which

(82)

is just ihe Poisson distribution function thermal average number of atoms in ihe

{Appendix

C).

Here

<jY> is the

previously as <N) =

volume,

which

we have

evaluated

XVnQ,

(c)

Confirm

that

P[N) above satisfies


NP{N) \302\243

X P(N) = 1
14, Ideal

and

<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 the first is replaced the second process?Suppose by an irreversible process 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,

15, Diesel
engine

engine

compression.

diesel

engine

is an

internal combustion

in
highly

which,
compressed

fuel is

so

sprayed into the cylinders after ihe air chargehas been !o tgntte it has attained a temperature sufficient the that

fuel. Assume
maximum

initial temperature of

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

Take

1.4.

Chapter

Fermi

and Bose Gases

FERMI

GAS

183

Ground
Density

Slale of
of

Fermi Gas in Three Dimensions

185
1S6

Simcs

Heal Capacity

of Electron Gas
Metals

IS9
194

FermiGas

in

White

Dwarf

Stars

Nuclear Mailer

'
EINSTEIN

196

19S
199

BOSON
Example:

GAS

AND

CONDENSATION

Chemical Potential
Spacing

Near Absolute Zero


of

199
Lowest Orbilals
201

Lowest

and Second

of FreeAtoms
Orbital

Occupancy
\"He

Versus

Temperature

202

Einstein Condensation Temperature


Liquid

205
207

Phase

Relations
and

of Helium
Superfluidity,

210
*He

Quasiparticles
Superfluid
SUMMARY

212

Phases of

3He

217
217

PROBLEMS

218

1. Density 2. Energy

of Orbitals in One and Two of Relativists Fermi Gas


and

Dimensions

218

218
Fermi Gas

3.

Pressure

Entropy

of Degenerate
Versus

219
219

4. Chemical
5. Liquid'He

Potential

Temperature

as a Fermi Gas
Relationship

219
Dwarfs

6.

Mass-Radius

for

White

219

7. Photon Condensation

8. 9.

Energy, Boson

Heat Gas

Capacity, in One

and

Entropy

of Degenerate Boson Gas

221 221
222
222

Dimension

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

222
222

12. 14.

Fluctuations

in

a Bose.Gas

13. Chemical
Two

Potentia! VersusConcentration
Boson

222
.

Orbital

System

223

It is

a fundamental result of quantum


fermions

theory

that

all particles,

including
with

atoms

and molecules, areeither

or

bosons.

They behave
in

alike in the classical


the

regime

in

which

the

concentration

is small

comparison

quantum

concentration,
(i \302\253

ifQ

(Mt/2tt/ijK'2.
in

A)
regime

Whenever n >

iiq

the

gas

is said

to be

the

quantum

and

is called a

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

The

difference

in physical

called

the

Bose

condensate-\342\200\224may

act

as

a superfluid, and

with

practically

zero

viscosity.

For many

systems the concentration


quantum

is

fixed, obtains

important variable.The
below

regime

is the temperature when the temperature

the
is

t0 s
defined is often

{2nh2/M)n213,

B)

by the

condiiion
by

n ~

said to
realized

h
as

be a degenerate gas*.
Nernst

iiq. A

gas

in

the

quantum

regime

with r

\302\253 ro

was

that

theentropy

of a classical gas diverges as 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{Chapter thermal number of particles the 6) average t -*

0. Quantum

in

an

orbital

of energy

\302\243 h

given

by

Wilh Ihe result for^

appropriateto
J{z)

this

regime,

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

D)

with

the usual
form

choice of the origin of eat zero


assures

for

the

energy

of the

lowest orbital.
is always

The
A

D)

us that

the average
with

occupancy of any
picture of
or

orbital

<it/nQt which is
fcrniion
A

consistent \302\253!,

our

original

the classicalregime.
a half-iniegra!
orbital

is any

panicle\342\200\224elementary

composite\342\200\224with

spin.
occupancy

fermion of

is limited

by ihe
average

Pauli exclusion principle to an


occupancy all orbitals
which

occu-

0 or

I,

with

an

anywhere
with

between
have

these limits. Ai
one

low

temperatures

it is

dear that many


zero

low-iying orbiials will


0 there

fermitm

in each
with

orbital. At absolute I. Here ef is the


number

<

e <
are

eF will be
just

occupied
orbitals

energy below
assigned

enough

to hold the

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
ofparticles

to the

population only

slowly, a

and

each excited small number

orbital\342\200\224any

orbital
We

of
shall

higher
discuss

energy\342\204\242will

contain

relaiively

of particles.

this
;md

point
its

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

FERMI
A with

GAS
gas Fermi

Fermi ihe

is called energy.
ihe
energy

energy lower than orbitals of higher


fully wlicrt

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,
will

be almost
A

entirely
Fermi
with

vacant.
is said
Fermi

An

orbital

is occupied

when the

it contains temperature

one fermton.
ishigli

gas
the

to be
as

rate no udegene
in

compared
6.

energy,

the

classical

regime The

treated

in

Chapter

unportam applications conduction electrons in metals,


matter.

The

most

striking

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

include

nuclear
energy

Fermi
60
\342\226\240|

16 eleclrons;in
gTOUnd

level f, for
Hie

\"a

slalc

the

louesi eight levels

(!6orbilals) are
occupied

(a)

Figure

7.1

confined

(a) The to a fine of

energiesof
lenglh
spin

the

L. Each
down, (b)

spin up and one for Orbitals above the

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

shaded region

are

in the

ground

Slate.

of the

zero. that it Is necessary ground state of the system at absolute Suppose to accommodate N nomnteracting electrons one a L in dimension. tn length What orbitals will be occupied in the ground state of the N electron system?
In a one-dtmenstonal is a positive form
crystal stn{fJ7ix/L)

the

quantum

number
it,

of a

free electron orbitalof


by

integer then

supplemented

the

spin

quantum with

number ms

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

spin

up or
in,

spin down.
in

If the
(i

system

has

8 electrons,
with

the

ground

state

the orbttais

1, 2,
Any

3, 4
fill

and

are \302\261\302\243

fiHed,

and

the orbitais
the

of higher n are
ground

empty.
state
filling

other tire

arrangement orbitals

gives

a higher
it until

energy. To constructthe
at

we

starting with

from
the

=
all

botiom,

and we

continue
are

higher

orbitals

electrons
in

N electrons

are accommodated.

The orbitais that are filled


shown

ground

state of a systemof 16electrons

in Figure

7.1.

Ground Sttite of Fermi Ground Slate of


Let

G&s

in Thtee

Dimensions

Fermi Gas in

Three

Dimensions

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 absolute zero;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
E) <5)

Here
separates

tiF

is

the

radius

filled

and

sphere (tn the space empty orbitals. For the


up

of a

of the
system

integers
to

nx,

tty,

ihai \302\273r)

hold

N electrons

the

orbitais must be filled

to

nF determined

by

n, = {lNfn)ll\\

F)

The
in

factor arises

2 arises because

because
only

an electron
triplets

factor|
n

The has two possiblespin orientations. nx, ny, nz in the positive octant of the sphere
sphere

space

are

to be

counted. The volumeof the

is 4nn//3.

We may

then write E) as

This
The

relates

the

Fermi

so-called \"Fermi
total

energy

temperature\"tf is definedas t> s ef. of the system in the ground state is


e, \302\243

energy

to the

electron concentration

N/V

n. The

[/\342\200\236

2 x

| x

471

\\^r

eln n2

eB *= --1

j j

P'

(in

\302\273a ,

(S)

with
with

En

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

In (8)

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

F),

have

let

21
in the

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

JdrtirV-)

(9)

conversion

of (he sum into an

integral.

Integration

of

(8)

gives

the total

ground state kineticenergy:

l0m\\L

0 10
Figure

20

30

40
Volume,

50
in

60
cm3

70

80

90 100

7,2

Total ground stale energy


versus

Uo

of one

mole of

elecirons,

volume.

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

E)

and F).

Density of States

Thermal

averages

for

independent

particle

problems

have the

form

where

rr denotes

the

quantum

orbital;

XR

is

the

value

of the

quantity

A'

in

the

orbita!

n; and
function,

distribution

is the thermal averageoccupancy, calledthe disf(t:a>T,!i.) of the orbital n. We often express <.Y) as an integral over the
A1)

orbital

energy

\302\243. Then

becomes

A2)

Density of States

where

the

sum

over

orbitais

has been

transformed to an integral by

the

sub-

substitution

X
number

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

Jrfs

A3)

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 particleproblem and not to the states of the N particlesystem. an Consider of Ihe calculalion of \302\251(e). We see from G) thai the example number N of free electronorbitais ofenergy iess than or equal lo some e is
Here
is the <D(\302\243}^\302\243

of orbitais

quantity 'D(e)is nearly

N{e)
for volume

=>

(V/in2)BM/h2)il2til2

A4)

V. Take

the iogarithm of both sides:

logN
and take differentials
of

s=

flogs

+ constant,

A5)

log

N and

loge:

The quantity dN =

(iN/lsjdt is
C(e)

the

number

of

orbifals

of energy

between c

and e + (/e,so that


~dNltlt

ZN{t)llt

A7)
been

is

the

density

of

orbitais.

counted

throughout
\302\251(e)as

have two spin orientations of an electron this derivation because they were counted in F). We

The

can

write

a function

of e

alone because
=

JV(\302\243)A

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

(IS)

from A4). ThenC 7)

becomes

A9i

Chapter

7: Fermi

and BaseGm

Figure

7.3

of energy,

Density of orbitals as a function for a free electron gas in three The dashed curve represents the of occupied orbilals ai a finile
bm wiih

dimensions.
densiiy temperature, comparison
the

/(eVD(e)

such thai r

is small

in

occupied

cF. The shaded area rcprcsetus orbiiah ai absolute zero.

Energy, e

*\"\342\226\240

When

multiplied
*D(e)

orbilals
total
number

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

the disiribulion

B0}

where

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

f{t)

is Ihe

in

Chapier

6. In
}t

we
B0)

determine
be

by
Ehe

equal

to

B1)

If Jhe
above

sysiem is
which

in

the

ground

stale,

all orbitais

are filled up to

the

energy

\302\24

they

are vacani.

The number ofekcirons is equalto

B2
and

ihe

energy

is

B3)

Heat Capacityof Electron


of Eleciron

Gas

Heat
We

Capacity
derive

Gas

gas

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

calcufaiionis
for
follows

heal capacity of a degeneraie


perhaps

Fermi the gas.

most For

iman
very

impressive accomplishment ideal monalomic gas the


much
agreement

of the theory of (he degenerate Fermi

lower
wiih

values

are found.
healed

heat capacity is \302\247W, bui The calculation that


results.
from

elecirons
gives

in a

meial
of a

excellent

agree-

theexperimemal

The increase
0 10

in

(he

total
by

energy
AU

system
\342\200\224

of N electronswhen
whence

i is

denoted

U{x)

L'(Q),

AU

JjVcrfWO:)
J0\"<fcrf>(E).

B4)

Here
unit

f{c)
energy

is (he
range.

Fermi-Dirac fimetion, and O(c) is We multiply the identity

the

number

of orbilals

per

N \"
by tf to obtain

Jo\342\204\242

</e/WW

J^W

B5*

{jo
We

ifjAttrfteW

- f/dttfiiz).

B6)

use

B6)

fo rewrite
=

B4) as

AU

JJ

Je(b
on

- tr\\n^y0{c) +

fc'M*r

- $0
the

fW&iz)-

W)

The

first

integral

the right-hand

side of
eiecirons positive.

B7) gives the energy neededlo take


and \302\243f,

electrons

from

ef to the

orbitals of energy \302\243 >


ihe are

second

integral

gives
firsi

ihe energy neededto

bring energy

to ef The

from orbifals
product

below ef. Both

contributionsto !he
integral

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

dc at

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 ~ 50000 ihe of conduction gas K, characteristic electrons in a meial.

The heat
respect

capacity

of

the

electron

gas is

found on
in

differentiating

AU

with

to r.

The only temperature-dependent terns

B7)

is /(e),

whence we

Figure

7.4

Temperature

a noninteracting
energy

is plotted

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

\302\243\342\226\240

S; 05
^

uhere

N is the

number of decirons.The temperature

is ploued

as xjtF.

0.4

0.6

3
e/A'b,
Figure

4
in uniis
ai

6
K

of 104
various

7.5

Fermi-Dirac

disiribuiion

= 50000 K. The resuhs apply TF = \302\243F/kB number of particles is constani, independent

each temperature
graph as
the

was energy

calculated

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

10 a

at which/

= J.

Courtesy of

B. Feldman.

Heat

Capacity of

ElectronGas

-Region of UcMsieraic
/

quantum

gas

\342\200\224-^

Rc\302\253ion

of classic-,

\\

Figure

gas of
plotting,

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

temperature

for

a
in

For convenience

units of

ji

and

i arc

0.763cf.

can group

terms to obtain

B8)
At

(he

tempera

lures

of interest in
is

that the
approximation

derivative df/dx
to

large

evaluate

the

density

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

integral:

Ccl S

B9)
hi

of Examination
suggests

the

graphs
\302\253 we \302\243f

Figures the

that

when t
in

ignore

7.7 of the variation of/i with x temperature dependence of thechemica!


7.6 and function

potential ji
constant

the

Fermi-Dtrac

distribution

and

replace ;i

by

the

cF. We

have then:

C0)

Chapter

7;

Ftrmi

and Bost

Gas

Figure chemical

1.1

V&riaiiors
potential

with temperature

of she

gasesin one meials t/nF


thai

free electron Fermi and three dimensions. In common a= 0.01 at room (empcraiure, so
ji, for

;i is

calculated for the

closely equal from series

lo cF.Thesecurves expansions of the


ihe

were integral

number of particles in

system.

We set

x a
and

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

it

follows

from

B9) and

C0)

that

We

may

safely

replace the

lower limit
or

by

-co
if

because
we

the factor
concerned

integrand is already negligibleat such that cF/x -~ f 00 temperatures

x = -ef/r
more.

are

The integral*

becomes

+ iI

\342\200\242

The

inicgta!

is not

demciuary,

but

may

be cvafua^d

from ihe
it2

p,

-V

ondilTeremhuion

of bsjih

sides uiih

rcspcci

lo ihc

parameter a.

Heat Capacity
whence

of

Electron

Gas

we have for

she heat capacity of an


Cel

electron

gas,

when

\302\253

xf,

- WUEfU.

'
I

C4)

In conventional

units,

Ctl
We

C5) Fermi energy i,

found

that

the density

of orbitajs at the
\302\253(\302\243,)

3N/lcf eF. Do

= 3iV/2tf

06)
the

for if

free

electron

gas,
gas

with

xF

not be deceivedby
only if

notation

rF:

is not

the temperature
\302\253 xF

ofthe Fermi

gas, hut
\302\273

a convenient

reference

point.

For r

the

Thus C4) becomes

is degenerate;

for r

(he

gas

is in the

classical regime.

C7)
in

conventional

units

there

is an

extra factor kBl

so

that

C\\,

C8)
but not an actual temperature,

where point.

A'flTF

sF. Again,

TF is

only

a reference

We can give a

zero,chiefly those electrons in states within specimen is heatedfrom absolute 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 increased by approximately as total electronic thermal energy is thereforeofthe order of Uci Ni2/eF. Thus the electronic contributionto the heat capacityis given by
A'r/rF

physical explanationof the

form

of

the

result

{37). When the

C9) the exact

which
with

is directly
the

proportional to t,
results.

in

agreement

with

result C4)

and

experimental

Chapter 7:

Fctmi

and

Bos

Table l.\\

Cuiculaied
Comiuciion

Fermi energy parameters for

free

eleciroi

Fermi Fermi

eieclron

iempcratur

concemralion

Velocity SV, in cm

energy

T., =

[. k,

NiV.
Li
4.6

in

cm'3

s~'

in eV \302\243F,

inK 5.5 x 10J 3.7

x 10\"

1.3 x
1.1

10\"

4.7

Na

2.5

3.S

K Rb

1.34

0.85

2t

2.4

1.0S

0.79

1.8

Cs Cu
Ag

0.56

2.1

0.73

1.5

8.50
5.76

1.56

1.38

Au

5.90

1.39

7.0 5.5 5.5

64 6.4

1.8 8.2

Fermi

Gas

In Metals

The
Thus of

alkali metals
the

atom, and
the atoms,

and copper, silver,and


electron

gold

have

one

valence

electron per
the

valence

becomes

the conduction

electron in

metal.

concentration which

of conduction electrons is equa! to the concentration the be evaluated eilher from and ihc atomic densiiy may
fermion

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

gas,

the value

of she Fermi

eF

may

be calculated

from G):

ef = {hl12m)Cn2uI!\\

D0)
electron

Valuesof
velocity
the

and

of

ef are

given in Table

7.1 and in Figure 7.8.The


tn

vF at

the Fermi
is

kinetic

energy

surface is also given equal to ef:


^ttuy3

(he

\\ab!e;

it is

defined so that

The

. \302\243f

HO

where
eFjkB

nt is
for

the mass of the


metals in

electron.

values

of (he

Fermi \\emperatureTF ~
the

ordinary used

\302\253 TF

the order of 5 x l04K,so that (he derivation of C5) is an excellent approxima(ion


are of
many

assumption
at

room

temperature

and below.
metals

The heat capacity of

at

constant

volume

may be written

as

the sum of
Sow

an

electronic

contribution

and

a lattice

vibration contribution. At

temperatures

the sum

has the form


Cv

yi

+ At3

D2)

Na

a functio
Rb

J
5
Eleciron

monovaienl mclals. The siraighl line is dra whh iiin !brEf ^ 5.835 x 10\023'n1/J ergs,

10\"

10\302\260

concentration,

in cm~3

Figure 7.9
TK

Expcrimcnlalheal
Lien and N.

capacity

values
Phys.

After

W. H.

E. PhiJHps,

Rev.

for polnssium, plolled as 133, AI37O A964}.

C/Tv

where

and

A are

constants
t

characteristic
and

of the material. Here y


discussed

jn2N/iF

from C7),

and the lattice vibration term-4i3was


is dominant
to

in

Chapter

4, The

electronic term is linear in

Ii is
material

at sufficiently

iow temperatures.

helpful

display

the experimental

values of the

heat capacity for a given

as a plot

of Cvjx versus t2:


Cy/t

y + Ax2

D3) at t
Observed
\342\200\224 0

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

gives

values

Table heat

7.2 capacities

Experiment!

and free

eteciron eSecironic

of monovalent

metals
e electron},

Cexp),

mJmol\"'K\"
Li

y/y0

1.63

0.75

2.17

Na

1.38

1.14

1.21

2.08

Rb

2.41

Cs

Cu
Ag

3.20 0.695
0.646

197 2.36

1.69

1.23

1.22

1.35

0.50
0.65

1.39

1.00

Au

0.729

0.65

1.13

oni:

The values of \342\226\240/ nud yo arc in i iUlU u: Oluilcsy of N. li. 1'hillim.

Table

7.3

ExpenmenUt

values of

declronic heat capaciiy consiain

y of

mcials

Li

Be

C
I Al

1.63

0.17 mb

Na

Si Gc Sn

1.38 1.3 K Ca 2.08 2.9


Rb

1.35

Sc

Ti

\021

Cr
Mo

Mr
4.73 Rh

Ni

107 Y

3.35

9.26

t.40 9.2
Tc
2.0

7.02

Cu 0.695
Ae

Zn

Cra

As

0.64

0.596

0.19

Sr
Ba

2r

2.41

3.6
2.7

Nb

10.2

2.80

7.79

P<!

In

Sb

4.9 lr

9.42

0.646

0.638 1.69

1.78

0.11

Cs

La

Ht

T*

Re

Pt

Au

[3.20
sOTE;Thc

10.
is in

He

Tl

2.16
,s

5.9

1.3

2.3

3.1
and

6.8

0.729

1.79 1.47

jpb

2.98 o.oos

Bi

value of y

fuiniihed

by R

Phillips

N. Pear

White Dwarf
White

Stars
slars

dwarf

have

masses

comparable

to

that

of

the

Sun.

The

mass and

radius of Itic Sun arc


Q

2.0

x 10!3

g;

Ko = 7.0 x

10'\302\260 cm.

D4)

dwarfs are very small, perhaps of the which is a normal star, is of the Sun, density of water on the Earth. The densities of white dwarfs
The

radii

of white

O.Oi
order

that
of
1

of the
gem\023,

Sun. The
like

that

are

exceedingly

high, of

the

White

Dwarf

Stars

order

oflO'1 to
entirely

107gem\023.
into
will

Atoms

under

the densities

prevalent in white

dwarfs

are

ionized

nuclei
shown

and
below.

free electrons,
white

and the electron gas is a


to be

gas,as degenerate
The companion

be

of Sinus was the first


the

dwarf

discovered.
about

In 1844
a straight

observed Bessel
lincasifithadan
near

that

path

of the

star Siritis oscillatedslightly

its predicted

to be
estimated

2.0 x

3O33

invisible companion.The companion, SiriusB,was discovered ofSiri us B was determined position by Clark in 1862.Themass on the orbits. The radius of Sirius B g by measurements x 109cm by a
flux,

ts

as 2

comparison of the
properties
to

surface

temperature

and

the

radiant
in

energy
4.

using

the

of thermal
the mean

radiant energy developed


density

Chapter

The

mass and

radius of Sirius B

lc;id

D5)

This extraordinarilyhigh following words; \"Apart


particular

density from

was the

appraised incredibility

by Eddington in 1926 in of the result, there was


suspicion.\"

the
no

reason

to view
that

the calculation with


named

Other

white

dwarfs
density

have higher
100

densities;
atoms at a

Van

Maanen

No. 2
a volume

has a mean
per

times

higher.
have density of 106gcni~3

Hydrogen

atom

equal

\\o

=s

(I06molcm\023){6

10\" atoms

iO~30cni3pcratorn

mol\021)

or

the

10~6A3peratom. order of 0.01 A, as

The average

nearest-neighbor separation is ihen

of

molecule

electrons

and

form

graviiational

In

the

temperature

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 together in dwarfs an electron matter the white by 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.
x

electron gas at a concentration of 1


cr *
'
as (h2/2i}i){3n2nI13

103Oelcetronscm~3

is given

by
,

0.5

10~6erg

as i

x 10s eV

D6)

discussion \302\243ood

of while

dwaif siais

is

given

by W. K

Rose, Aitropkvsics,

Hotf.

WinHon,

1973.

\"able

7.4

Fermi

energy of

degenerate fsmiion Particles


atoms

characierisiic

values)

of mailer
Liquid

Tf, in
0.3
5 3

3Hc

Metal
While
Nuclear
Ncujron

demons
dwarf stars
matter
stars

tQ1

electrons
nuctcons
neutrons

\302\253 !09

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

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

lower
Are

than

the

Fermi

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
\302\243Q

me2

\302\273 A

10\"\"g)C

x I010cins-!):

* 1.

D7)

This
effects

energy

is

of

the

same

will

be significant,

order as the Fermi energy D6).Thus relativistic densities but not dominant. At higher the Fermi gas

is reiativistic.

NuelearMatter
We

consider

the

state

of matter

within nuclei.
form

The neutronsand
fermton

protons

of

which

nuclear

matter
estimate

is composed
here

degenerate

gas, at

least

qualiiaiively. We

the Fermi

of a

nucleus

that

contains

A nucleons
R

tbenucleongas;The radius is given by the empirical relation


energy of x Al!\\ per particle
A.

A.3
the

x ltT13cm) volume

D8) is constant,for the


of nucleons

Accordingto
volume

this

relation

average

goes

as R3,

which is proportional to

The

concentration

b nuclear

matter is
?

0.11

x 1039cm-3

D9)

Chemical

Potential

Near

Absolute

Zero

about

103 times higher than


and

the

concentration

of nudeons

in a

white dwarf

Star.Neutrons the neutronsneed


concentration of

protons
not

are the

not Fermi

identical

equal

particles. The Fermi energy of energy of the protons. The concentrafamiliar

one

Or the

oilier, but not

both, enters the

relation

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

E0)

let simplicity number of neutrons.


For

us suppose that the number of protonsis equal Theit


* a cm\023 \302\253\342\200\236\302\253\342\200\236\342\200\236(,\302\253 2. The

to

the

'W>n>

0.05

x 1039

{51}

as obtained

from D9)
\302\243C.17 \302\243f

on dividing
x

by

Fermi

energy is
Mev.

10\023>1/3a;0.43

x 10\024erg \302\253 27

E2)
of

The average
Fermi

kinetic energy of a particlein a degenerate Fermi gas is is energy, so that in nuclear matter the averagekinetic energy

-J

ihe

16 Mev

per nucleon.

BOSON
A very

GAS

AND

EINSTEIN

CONDENSATION

remarkable
in

effect occurs in
below

gas

of nonintcmcting

transitiontemperature, of particles the system will

which

a substantial

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 in action. example of Einstein condensation

Chemical

Potential
to

Near Absolute

Zero
is the
The chemical

The key

the
system

Einstein
at

condensation
low

of a boson

temperatures.

behavior of the chemicalpotential potential is responsible

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

apparent

stabilization

We consider

<53)

e obtain

the occupancy

of the

ground orbital at e =

0as

When

i\342\226\240-+ 0 the

occupancy

of the

ground orbital becomesequal to the

total

number

of particles

in the

system, so ihal

Here
know

we

have

made

use

of the

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

x +

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

dial

.v, which

in hji/x, must be small

comparison be

wiih

unity,

for otherwise

the total

number of particles N could not

large.

From

this result

we

find

E5)

asT

-.0.

ForN = 1022 at
that

T = IK,

we

have

/i

-1.4 x lO'38 erg.We

noic

fromE5)

E6)

as i

~+

0.

The

chemical

potential

in a

boson system must


tirar

always

be

lower

in

energy than the ground


b\302\243 non-nesative.

state orbiral, in order

rhc

occupancy

of every

orbital

Chemical

Potential

Near Absolute

Zcr

Cxampte;Spacingoflonat
orbital

and

second
in

lowest

ttrbiiuh

of free

atoms. The
is

energy

of

an

of an atom free to move

a cube

of volume

('

=\302\273 /-1

where

n,,

n>4

are \302\273,

positive

integers.

The energy e(I 11)of

ihe

lowest

orbital

is

+ 1 +

1) ,

E8)

ind

the

energy

eB1 i)

of one of

the

set of

next lowest orbitais is

+ 1+1).
W

E9)

The

lowest

excitation

energy of

the

atom

is

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

=*

\342\200\224

(-)

F0)

lfA/{4tie}

- 6.6 x lO'^gandi, =
Ae

cm,

= C){8.4 Ae/*8

x IO-3!)(9,S6)

= 2.4S x

NT30erg.

F1)

In

temperature
This

units,

- 1.S0x KT1*K.
small,
and

spiining in a

is extremely

part 1

ijtK,

iO\0211

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

much
/i]/r} distribution

closer to
is

ground

orbjia!
l

ntucit
function.

closer

io

than

is

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

it is

tiiRtcuU to

conceive that

The

Boltnnann

factor

exp{~A\302\243/i)

at

mK.

is

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


gi\\cs By D)

x 10-\")
we would

s I expeel that
of 1.

1.S
even

I0\0211

F2) of tlie

if/t

\302\253cilte

occupancy

only be of
vuluti

an

entirely

dilfctcni

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

because

Ae

\302\273 p..

Thus

the occupation

of

the

fust

exciied

orbiial

ai

mK

i:

F4)

so thai

the

fraction which

of

the N

particles
much

thai

are the

in this occupancy

5 x 10\" 13t temperatures

is very

small. We see thai


very

orbital is/.iV of the first


is quiie
left

10i0v 10ir oibiialai sight


ii

=
low
a

exciied first

is [datively
factor

lower

than would
distribution

be expeciedat
is
in

from the
favors

simple
situation
cienily are from

Boltzmann

F2).

The Bose-Einstein

strange;
iheir

in which
low

called

ihe greatest part of tlie population The particles in ihe ground temperatures. the Bose-Einsicin condensate. The atoms
in

the ground
long

orbiial,
in ihe

as

as

orbiiai at sufi'lnumber is \302\2731,


differently

condensate

act quiie

the atoms

excited

stales.

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

VersusTemperature
number of free particle orbitalsper unit
energy

saw

in A9)

that the

range

is

fora
and

particle of spin zero.The total exciied orbitals is given by the

number

of atoms

ofheliutn-4

in

the

ground

sum

of the

occupancies of all orbitals:

N .
We

F6)
the

have

separated

sum over

n in

into the

two

parts.

for

/@,t),
in

the
F6)

number
gives

of atoms
the

ground

Here N0(t) has been written orbital at temperature t. The

integral

number

of atoms

with NJ,i) in all excitedorbitals,

\\

\\
\\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

funciion

ofthe

slates
arc

gives

the

condensed

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

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

Hie plot.

distributionfunction. The /(e,i) as the Bose-Einstetn 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

at low

temperatures the chemical p is very potential


the

much

closer

in energy

to the
of

ground state orbital than


of

first

excited

orbital

is to the

ground state orbital.ThisCloseness


the

p to

the ground

orbital loads most of

population

the system

into the

7.10). ground orbital (Figure

Chapter

7:

Fermi

and Base

Gases

e - 0 is

The Bose-Einstein distribution function

when

written

for

the

orbilal

at

NM=V^~,
as
in

F7)

in
all

E4),
excited

where

will

depend

on

the temperature

x. The numberof particles

orbitals

increases

as tm:

or, with

e/z.

Nolice the facfor


At

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\273 it is not required that Ne\302\253 N, When I, and 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 /.
gives

zil2 which

Ihc

temperature

the number

The value of the integral*in

F8)

is, when

). =

1,

The

infiniic

= U1 10 >\342\226\240

gi

it ton

Temperature

Thus ihe numberof atomsin ..

excited

states

ts

\\.IO6VB\\H\\3;:i
G0)

where

/iQ

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

is again the quantum


excited

concentration.

We

divide

Nf by

N to

obtain the fractionof atomsin


N./N

orbitals:

2.6l2nqV/N

2.6l2na,'n.

G1)

The
number orbital,

value

of atoms either

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=
1

or

\342\200\224

to small excited Orbitais is relatively insensitive changes in X. but the rest of tlie particles have to be in the ground orbital. To assure this we must take /. very close to 1 as long as NQ is a large number. Even 103 is a large numberfor 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.

Einstein
We

Condensation
Ihe

Tcmperaiure
condensation
excited
\302\253 N.

define

Einstein

temperature*
states
ilie r\302\243

i\302\243

as

(he

(cmperaiure

for

which the

number of aionis in
is,

is equal

atoms.

That

A^frJ

Above

occupancy

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

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


to (he

M \\2.6I 2k
Now

G2)

Gt)

rimy

be written

as

G3)

wlicrc
value

jV

is

tlic

tola!

number
4Hc

of atoms.
below

The numberofatoms
sliown in Figure

in

excited

orNuils

v;irtes ;is
of

ii:2 a I

Ictuperiitures

if;, as

7.11. Tlic uik'iilaled

T^foralomsof

is a=3 K. Berlin, Siuunesbcricliie 152-1,261; 1925.3.

in,

Atademic

dcr W'issenschaficn,

Chapter

7:

Fermi

aid

Hose G:

1.0
\"n

0.8
t

\\

Superfluid

component'

\\

/
ormal
omponen
flui

\\

/
y
0.4
0

0.2

0,6

\\|
0.8

i.o

Figure7\302\273tl

Condensed

of the
of

proportion

No/N

ihc

pfoponion

NJN

gas: tempcraiuce dependence in ihe ground orbiial and of aloms in all exciled orbilals. We
boson

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

= 0.

The

number

of particles
No

in

the

ground

orbital

is found

from {73):
G4)

- Ne = N[l

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

We

note

that
said

N may
that

be of the order of 102\\ Forx


be

even

slightly

less

than te
condensed

will large numberof particles We

in the

ground

have

the particles in
temperature

the ground orbitalbelowt


in

orbital, as we see in Figure7.11.


form

the

phase

or the

superfluid phase.
k'elvin

The condensation

is given

by the
.

numerical relation
G5)

M)

where

VM

is

the

molar

volume

in cm3
mol\021

mol\021

and

is the

molecular

weight.

For liquid helium Vu~ 27.6cm3

and

= 4;

thus TE = 3.1K.

Liquid4

He

Liquid

4He

The calculated

of 2.17K

close lo j he actual tempera Jure tempera! ure of 3 K is suggesiively a! whicha transitionlo a new stale of matter is observed to Jakeplace in helium K there liquid (Figure 7.12). We believe that in liquid 4Hebelow2.17 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

2.5

2.0 \"\302\253,

t.o

y
0.5

1.6 1.8 2.0


Tempera!

2.2

2.4

2.6

u;

Figure 7.12

Heat capacity
K is

of

liquid

*He. The
important

sharp
transition

peak near
in the

2.17

evidence of an

nature of the liquid. The viscosity above the transition temperature is typical liquids, whereas the viscosity belowtlic
determined
vanishingly

of

the liquid of normal as

transition

by rate
small,

of flow

through

narrow

slits is
the

viscosity

above

at least I06 times smaller than the transition. The transition is

often shape

called a lambda transition of the graph. After Kccsom

merely becauseof
et al.

tlte

Chapter It Fermi

twd

Base

Gases

The

condensation

may act as bosons,as in

is normally not
the

permitted for

fennions,

but

pairs

of fermions

superconductivity

of electron

in metals. A
properties
spin

pairs (Cooper
with

pairs)

different

type

of transition
in

to complex
3He

phases

superflutd

has

been observed

liquid

below

3mK.

Atoms of

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
\\ and

are fermions,

but pairs

We

which

the

view

is correct.
of

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
liquid

{a) The molar volume

4He at

mo!~', as

compared

with

of

the

helium structure

atoms tn

expanded

appreciable

distances.
for

mo!\"l. Thus the kinetic motion 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
the

observed

27.6 cm3

responsible

the

expansion

of ifie inoiar

volume.

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

_ ~

|16,
[3.2,

at
at
observed

2.SK
4.0 K
for

These vaiues are quite closeto


temperature\342\200\224see selvesin

ihose

normal

gases

at

room
for

Table

14.3in

The
an

values

of

the transport coefficientslliemof those

the

liqirid

are with

order

of magnitude
act

calculated

the

gas

at the

same denstly.

Normal liquids

quite

differently.

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

Liquid

'He

1
as

g
I

\\

r'Hz

'lie

T,
Fi\302\253iire7.13 iiqujd

in

K-

Comparison

4He

uuder

gravify

of rales of flow through a fine

of liquid hole.

3He and fhc suddcr


D.

Noiice

onset of high
Osborne,

fluidify

or superfluidity

in \"He. After
Abraham,

W.

B. Weinsiock,

and B.M.

Pliys.

Rev.75,

9S8 A949).

The new stale of ntallcr

inio

which

liquid

4He enters

when cooled beiow


a

2.17

K.

has

quhe

asionishing

properlies.

The viscosity

as measuredin

flow

experiment*

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 doesthe fermion 3Hc in solution in supijrflow of the latter; neither, of course, 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: is essenlially

fliii.ls

ofiliirftciil

visttiMlics,
K'ii,

sums
i)f 'be

c\\fKfinn:liii

iiicisuic
lluidiiy.

ifJiraif(Jj;t;

i imnily.

.t\302\273Juliet

l'vjil'Ijjjk'j

Bic.isufi;

the .ivct.igc of

aierjgt*

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

of aroms condensarion into the ground orblial of the s; stem. Note ihat licl'mm h a liquid at absolute zero ai pressures below 25aim. The

tiquid-\\apor

boiling

curve is
ractgc C.

not

included

in

this gcaph

as ii would

wjih

[he zcco

pressuic line.After 19,626E950).

A. Swenson,

Phys. lev.

of any other
temperature

low-iying

orbital,

as

we have

seen. The

in which

liquid

He { and

({ exisl are shown

and regions of pressure

in

Figure

7,14.

The development of superftuid propertiesis no[ an automatic consequence A dvanced of [he Einstein condensation of aloms into the ground orbira!.
calculations
interaction

cal-

show

that il is [he
aloms

among

[he

aloms

condensed

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

Phase Relationsof Helium

The

phase

diagram from

of

4He
Ihe

was shown

in

Figure

7.14.
down

The
to

iiquid-vapor
zero

curve
without

can be followed
any appearance

crilical

poinl of 5.2 K
ihe

absoiule

of the solid. Al
a

transilion

called He I, makes
He

transit

ion

to the

liquid, form wilh superfluid properties,called


temperature
liquid

Ihe normal

II.

A temperature

called

the/

poinl is the triple point al which


hciium,
triple

He

(,

liquid He ii,

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

found that
point

exists

\342\200\242

An tnlercsring

can,

August

discussion of solid heli 1967, pp. 85-95. Solid 'He

is given

:xisis

by B. Bertram and in three crysral structures

R. A.

according

Guyed Scientific Am ro rhc condili

of Helium

'He

/
Solid

/
Liquid

\342\226\240i

40

Gas

Figure

7.15

Pliase

diagrams

for

liquid

3He,

(a) in soiid

kelvin and (b) in

miKikeivin.

In rhc

region of negaiive
[he

slopeshown
a
higher heal

in (a)

eniropy

ihan

on ihc phase boundary liie liquid, and we


solidify

has

have io add
properiics

lo

'he

liquid io

it. Superfluid

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

1.743

K:

here the

He I and
regions

He II.The

soiid is in equilibrium wiih


two

ihe

iwo

liquid

modifications.

triple

poinis

are connecicd

by a

of existence
phasediagram Figure

of He
of

II and He I.
differs in a the importance

line !ha!separates ihe

The of4He.
ihe

3He

7.15

exhibiis

remarkable way from the phasediagram of ihe fermion nature of 3He. Note
explained

negaiive

slope

of ihe

coexistence curve at low temperatures. As

in

Chapter

10, the

negative slope means thai


of

!hc

entropy

of! he

ISlower lhan !heentropy


Qunsipariieies

liquid phase

the

solid

phase.

and Superfluidity, 4He


the

For
if

many

purposes

superfluid

component

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

of liquid helium
No

il behaves as
supcrfluid for the
to tlic
to

were

atoms

of the

exeitation

energy,

ground orbila! by
only

definition

has

no excitation

energy. The

superfluidhas energy
relative
flow

when

he

center

of mass

of the
when

superfluid is given
Ilie

a velocity

laboratory reference frame\342\200\224as


the laboratory.

superfltiid
will

is set

inlo

relative

The condensed

as

component of Na
not

atoms

flow

with zero
and

viseosity so long
is,

the

flow

does

ereate
be

cxcitatiosis
caused

in tile
ground

superfluid\342\200\224that

so

long

as no

atoms make transitions bctwecil the

orbital

!ho excited

orbitals.
irregu-

Such iransitions might


irregularities

by collisions

of helium

atoms
of
if

with

in

the

wall

of the

tube through which the helium atoms are Rowing.

The

transitions,

if they

occur, are a

cause of energy loss and


is

momentum collisions

loss can

from occur.

the moving fluid,

and the

flow

not

resistanceless

such

The criterion for


relationshipof

superfluidity
in liquid
a

involves

the
the

energy
excited

and
orbitals

Momentum
were

the

excitations

He
free

!!. If

relationreally like the

orbilais of freeatoms,with

parliele

relation

l\\.ivi

= -_(/,/,-)*

G6) of an atom,
k = we

between the energy e and


show

the

momentum

Mo

or /ik

then

can

that

superfluidity

Here would not be expected.

^/wavelength.

But

atoms the low energy the bceause of the existence of interactions between but are longitudinal sound free excitations do not resemble excitations, particle 4).After all, it is not unreasonable that a waves, longitudinalphonons(Chapter in any liquid, even though we have longitudinal sound wave should propagate
no
A

previous
language

experience
has

of superliquids, up to

grown

describe the low-lyingexciied statesofa


excitations

system

of

many

atoms.

These

slates are called elementary


(jiiasip We

and

in their

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

Longitudinal give

phonons

are

the clear-cut

experisuper-

menial evidence
superfluidity.

for

this,

but

first

we derive

a necessary conditionfor
the

This

condition

will

show

us
superfluid

wiiy

phonon-tfke

nature

of the

elementary excitations leads to the

behavior

of liquid

He II.

Quaupanhlts andSuptrJluMty,

'lie

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

He

It

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


7. [$
V down

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

a body,

perhaps

\\M0V2

*=

|A/0F'2

, \302\243k

G7)

where

V is

Furthermore,

the velocity of the body after creation of the elementary we must sarisfy the law of conservation of momentum
=
Ma\\\"

excitation.

hk.

(IS) at the

The two
if

the

conservation taws cannot always direction of Jhe excitation created in

be the

satisfied process

same time even To show

is unrestricted.

Chapter

7; Fermi

and Base Gases

this we rewrite G8)as


A/0V

Af0V

and lake the

square of boihsides:
M02V2

2A/0/iV-k
we

+ h2k2

= MQ2V'2.

On multiplication

by

l/2Af0

have

|A-/K2

/V

k +

\\M0V'\\

G9)

We

subtract

G9)

from

G7) to

obtain
'

1
2mTq

\342\226\240

(SO)

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

There is a

-h2k2
Vs

minimum

of-

(81)
if we let the

The conditionis a
become

little

simpler

to express

mass Mo of the body

very

large,

for then

(82)

body

moving

with

a lower
the

velocity than
will be with

Vc

will

not

be able

to create

excitations
will

in the liquid,so that


to

motion

resistance less. The viscosity velocity will encounter

appear

be zero.

body

moving

higher

resistance

Quusipartfctes

and

Superfluidity,

*lle

the curve
ck

s=

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,
and

slope

the

crilical

velocity
=

is zero:
minimum

Free atoms:

Vs

oUik/2M
in

= 0.
II is
\302\243k

(83}
=

The

energy

of

a low

energy
waves

phonon
where

liquid

He

tui>k =

frequencyregionofsound is equal to of sound velocity


the

the

product

of wavelcnglh

tusk in [lie and frequency


is

t'a, or

to [he

product of vs

times

the

wavevector

where the circular frequency mk k. Now the critical velocity is


offtr^/hk

equal

Phonons:

Vc

= minimum

= v,.

(84)

The

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 excitations helium II has been in liquid 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

velocity

Vc is

equal

to the

Vc

\302\253

&/hk0

5 x

I03 cm

s\021

(85)

where

A and k0
ions
conditions

Charged
experimental

arc identified on the figure. of helium in solution in


of

liquid

helium

11 under

eertain experi-

pressure

and

temperature

almost closely
conditions

like

free partieles and to to the calculated equal


motion

the

of

have a limiting drift value of (85).Underother the ions is limi(ed at a lower velocity
modes
by

have been observed*to move * near 5 x 103 cm s\" veloeity


experimental by

condi-

the

ercation

of

vortex rings.

Sueh vortex rings are transverse


longitudinal

of 7.17.

motion

and

do not

appear
Our

in

the

modes

covered

Figure

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, result * L.

Meyer

and

F. Reif, Phys.

Rev.' 123,727

U96t|;

G. W.

Rajfiekt, Ph)s. Rev.

Lcllcrs

16,934

A966).

1.0
WavevccioT,

2-0
in

3.0
cm\021

units

of 50s

Figure

7.17

exciiaiioHS from

Energy ck versus in liquid helium ai

wavevecior i of elementary t.JJK. The paraboliccurve


curve

rising

free
the

represents the iheoreiicaiiycalculated helium aioms ai absolutezero. Tlic open circles


lhe otigin
and
energy

for

momentum
through

of the

measured

exciutions.

lo correspond A smoosh

curve has beendrawn


rising

ihe poinls.

iineariy

from

lhe origin is

wfili

a vclodfy

the crmcai
mum
D.G.

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.

Hie broken curve she tiieorcsieal brynch phonon m s\"'. The solid straight line

femperutures above wili be a normal fluid

absolute zero, but


component fluid

below

the

Einstein

temperature,

there

of demcnlary

excitations

exciied.The

normal

component

is the

source of
m

thermally resistance to the motion


in

that are

of
fluid

the

body.

The

supcrflow

aspect
fine

appears first
in
in

experiments

which

the

liquid flows out


component

ihrough a
may

lube

the
lhe

side of a container. The


container

normai

remain

behind

while
we

the

The derivation component leaks out without resistance.

have

superfluid given of the

critical velocity also holds for


fluid

this

situation,

relative

to

the

walls of

the tube;

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


Supcrfluid

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

V as

Phases

of

3He

Three
contrast

superfluid
to

phases of liquid
4He\342\200\224with

3He
to

are

known*

(Figure

7.15b),

but\342\200\224in

liquid

transition

temperatures be

of only

The superfluid phases are beiieved


superconducting

qualitatively

a few milhkelvin. similar to the superorbiials

slate

of electrons

in metals,

where pairs
known

of particlesin
as

near

[he Fermi

surface form a

type of bound siaie

a Cooper

pair. Such a

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

but spacing

the radius of the


in

molecule
average

a metal

or the

Uvo

[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

so

thai

ihree M,

magnetic ~

supcrfiuids

are possible,

corresponding to spin orientathree both

orientations

1, 0,

and

-1, or mixturesof these


been confirmed.

states. the

The

magnetic
\302\243nd

superfluids
superfiuid

have been explored experimentally, and


properties

magnetic

have

SUMMARY

1. Comparedto a classical gas,a

Fermi

gas

at low

temperature

lias high kinetic

energy, is zero
ground

high in

pressure, the

and

ground

slate.

state of a free

heat capacity. The entropy of The energy of the highest filled of spin j is particle gas of ferniions
low

the Fermigas
orbiial

in

the

' ~
2,

ut\\
ground

\342\226\240 v

The

lota!

kinezic

energy

in

the

stale

is

see j. C. U heat icy, 311 J. R. Hook, ii97j|;aritt PU)sicsfluiic!tn25.


\342\200\242

For

elementary

roif^s,

Wll

Ph

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

Chapter 7: .3. The

Fermi

and

Base

Cases

density of orbitats at

r,f

is

\"D{Cf)

3,V/2c^.
at r
\302\253 i>

A. The

heat capacity of an

electron

gas

is

in fundamental

units.

5. For a Boscgas at r

<

rE

the

fraction

of atoms

in

excited

orbitiiis

is

fi. The

Einstein condensation

temperature of a fj;iS
__2nftV N

of

nuniiitenicthig

bosons

Y>

PROBLEMS

i.

Density

of

orh'ttah
free

hi one

and

two

dimensions,

(a)

Show

that

the density

of orbiiafs of a

electron

in une

dimension

is
2

O,(e)
where i.

=\302\273

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

(86)

of area

is the length of the line,(b)

Show

thai

in two

dimensions,

for a square

A,

\302\251i(e)

^tiii/Tcft2

(87)

independent o(e.

2.
where

Energy

of

refarivistic

Fentu

gas.
in

For electrons
energy

with

an

energy

\302\273 me1,

in is

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


electrons form

the rest

mass of the electron,the


a cube

of

is given by e volume V = i.3 the

= pc, where
momentum
as

by (n/
in

nonrelativistic

is given energy of a gas ofN electrons


zr
\302\273

limit, (a)

Show [hat

+ it/
extreme

n:2)ll2>

exactly

for

the

this by

relativistic

limit the

Fermi

AncCii/n)\025

(88)

Problems

where

N/V.

(b) Show that

the total
(/\342\200\236

ener\302\273y

of

the

ground

stale uf ihc

gas is
(S9)

J,Vef.

The general

problem is and entropy


in

Ireaied

by

F.Jutlner,Zeilsduifl Fermi

furPhysik47,542({928).

3. Pressure
electron

of

degenerate

gas.

(a) Show

that

Fermi

gas

the

ground

stale

exerts a pressure

In a
tin

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

orbital or

has to

i!s energy

l/f/2|J.

(b) Kind
r \302\253

expression

for

Use entropy

of

-a

Fermi

electron

gas

in the

region

t>.

Notice

that
Chemical

a -*

Oast-0.
verms

\"/.

potential

temperature.
for

curvature
are

downward in three dimensions (Figure


different,

of p. versus t where
for

is upward
given

a 7.7).

fermion

*D, is

in

Problem

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

the integral
the behavior

of particles, and to the number N, of the integrand between zerotemperature

consider from
and

the

graphs

a finite

temperature.

5. Liquid 3He as a Fermi gas. 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 the heat at low temperatures is 0.081 g cm\" \\ (b) Calculate capacity = T \302\253 as observed with the experimental value 2.89NfcBT compare Cr TF and 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

continuously

acting

operation.
white

6. Mass-radius

relationship for
electrons
(a)

M and radiusR.Let the

be degenerate that
G

are nondegenerate. Show self-energyis -GM2jR,


density

the
is

where

is

constant

within'the

sphere

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

a white dwarf Consider the but nonrelativistic;

Chapter 7: Fermi
5.0

and

Sose

Gases

20
Temperature,

SO
in K

$00

200

Figure

7.18 liquid

Heat *Hc

3He in
fegion

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

percent solution of
axis

is C/T,

and

she horizontal axis is


the

T. Thus for
cufves
for taken

a Fermi

gas in the

degenerate temperature
are
which

theoretical

The curve for


the thai she

pure 3Heis slight slope. The curve

of C/T

at constant

volume

horizontal.
accounts

at constant the solution

pressure, of Hie in

fof

liquid

4He

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 possHs solid for the solution is drawn if the which with the calculation for free atoms hrTf - 0.331 K, agrees effective mass is taken as 2.38times the mass of an atom of 3He.Curves J. C. Wlicatley, Amer. J. Physics36 A968). after

-3GM2f5R). (b)Showthat
electrons

the

order

of magnitude

of the

kiiicsic esiergy of the

in the

ground

state is

here
if

m is
she

she mass
by ihe

lhai
(;ss

gravitational

required

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

of an clcclrosiand

Mit

is

the

Figure

7.19

Heal

capacity

of

;tn

Eimtcin

gas ut

cortilam volume.

mass is equal to
dwarf? gas

that

of

she

Sun

(e) of

H ss

believed thai
Show that
a

neuUons.

tot a

she value of the


Express

radius for
tn km.

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

B x

lQ33g), what is the density of the while

she

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 Problem 4.1, photons = is Ne 2.404 Kt3/*2/] V. Find the criticaltemperature in K below which which < JV. The excess N \342\200\224 will be in the photon mode of lowest frequency; jVe Nr be there is a large the excess described as a photon condensatein which might 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
ami entropy y;is
o\\

A1.

Energy,

heat

capacity,
of ;i the

of degenerate bosongas.
the

Find

ex prcs-

sions

;is ;i function
;mii

of tcmpcf.ifun; in
del'milc

region

op.idiy,

cn[[opy
V.

,V noniiilcMlcling

to ;i volume

Put

imegnil

in

dim

ens

th for the cne-igy. hc;il of hpiil zero confiiial bosons be not ion less form; it need
x < shown

is The calculated heat capacity above and below r\302\243 evaluated. was in Figure 7.12. The shown Figure 7.19. The experimental curve

in

dilTcrcnce

Chapter

7:

Fermi

and Base

Gases

between the two curves is marked;It is ascribed lo the between the atoms,

effect

of

interactions

9. Boson gasin
dimensional

one

dimension.

Calculate

the integral
that

for Nt{x)
the stale

for

onc-

gas of noninteracting

bosons, and show

integral

does does

not converge. This result suggests tlial a not form in one dimension. Take/. ~ I for

boson
the

ground

condensaie

calculation.

(The

really be treated by
10.

problem

should

means

of

a sum

over orbitats

on a finite

line.)

Relativhtk

white dwarf
in

stars.
of

of rest mass m such that the


).

a sphere
majority

Consider a Fcrnii gas of radius R. Conditions in certain


of

A' electrons white

each dwarfs are

energies e = pc, where


~

great

electrons

have

extreme

relativislic

kinetic

is the

momentum.

The de

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.

Broglie relationremains

Problem

2 gives the
e =

11. Fluctuations
that

in a

Fcwri gas.

Show

for

a single

orbisa!

of a

fermion

system

<(ANJ>

- <N>A -

<N\302\273

(91)

if

is \342\226\240GAO

fluciuation

energy so 12. Fluctuationsin a Base gas.

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

in thai orbiial. Notice that


deep

the

enough

below

the Fermi

N ~
in

<N).
is the

If

</V)

as

of a

(I!)

single

orbiial

of

a boson

system, fhen from


<JV>(I

E.83) show iiiat


<JV\302\273.

average occupancy

<(ANJ> =
Thus

(92)

are if fhe occupancy is large, with <N> \302\273 fractional fluctuafions I, ihe \302\253 the actual fluctuations can of the order ofuntty; <(ANJ>/<N>2 1, so mat

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

travel
the

in

flocks.\"

The

first

edition

fluctuations

of photons.

13, Chemical

potential versus the number of

potential versusconcentration*

(a)
for

Sketch
a

particles

boson

carefully gas in

the chemical volume


V

at

icmpcraiure

r. Include

both classical and quantum


systent.

fegimes. (b) Du
A'

the

same

for a syssem

of fermions.
boson at

14.
with

Two

orbilai

Consider
Find

a system of

bosons chemical

of

spin
potential

zero,
is

orbitals

(he

single
is

/x, and the

temperature is r.
orbital

particle energies
r

0 and e.
that

The

such,

the fhefma!

of

average population
at

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
the

lowest

twice

e.

Assume
electronic
is cooled

of
gas

rE

~ 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
she

number With

of

asoms
this

in excited
sechnique

orbitals

is

in

good

agreement

with

she t3

law, G3).
sudden

appearance

of

decreased
condcusase; orbitals.

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

signasure of Bose'Einssein condensation is is a sharp peak of atoms as the semperature


the
lighs

scattered

by by

atoms
in

in

the

scattered

atoms

excited

Chapter

Heat

and Work

ENERGY

AND

ENTROPY

TRANSFER:

DEFINITION
HEAT

OF HEAT

AND

WORK

2-7

ENGINES:

CONVERSION
2IS

OF HEAT INTO WORK


OirnOl

Inequality

2-S

Sources of
Air

Irrevcrsibiliiy
and

252

Refrigeraiors
Condiu'oners

233
Pumps
an

Heat

255

Carnot Cycle

Carnol Example:
Irreversible

2?6
for

Cycle

Idea!

Gas
Law

Energy Conversion and the Second Palh Dependence of Heat and Work
Work

of Thermodynamics

237 240
240

242
Ideal

Example: Sudden Expansion of an


HEAT
TEMPERATURE

Gas

245

AND WORK
OR

AT CONSTANT
CONSTANT

PRESSURE

245

Isothermal
Example:

Work
and

245
Work

IsobaricHeal Chemical
Example:
Magnetic Work

245

Elecirolysis
Chemical
Work

and Fuel
Work

Cells Ideal Gas

247
250

for an

25!
2--

and

Superconductors

SUMMARY

257

I'UOBLEMS
1.

2?
:::
ReiYigerator

Heat
Absorption

Pump

2.
).

2!:<

I'lwicm

Carnol

4. I leal

Hnginc
Cascade

25S
25S

Engine\342\200\224Kel'rigcralor

5. Thermal

Pollution
Condilioner

258
258

6. Room Air

7. Light
9.

Bulb in a
Energy

8. Gcotlierrnal 10. Irreversible


Cooling

Refrigerator
Solid to
of

259

259

of Nonmetallic
Expansion

T= 0
Gas

a Fermi

259 259

Energy

and

Entropy

Transfer:

Definition

of Heat and

Work

ENERGY

AND

ENTROPY

TRANSFER:

DEFINITION

OF HEAT AND WORK


are

Heat
of

and

work

two

different

forms of

of energy
energy

to a
to a
The

system by thermalcontactwith a system by a change in the external


may
The

energy transfer.Heat is the


reservoir.

transfer

Work

is the

transfer

para meters

that describe

the

system. gravitational

parameters
potential.

include
reason

volume,

we distinguish
process

magnetic field, electric field,or heal from work will be clear

when

we discuss
the

energy conversion processes.


physical

The most
civilizationis

important

in. a

modern energy-intensive civilizawas

conversion

of heat

Revolution into work. The Industrial

made

possible
combustion

by the steam
engine,

which

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

comis a

device to convert heat of the steam engine gave


Energy

to work.The problem
rise

of

understanding

the

limitations

conversion

because

most
fundamental

The
entropy
with

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

much

of the

remains

one

of the

transfer.
which

Consider
reservoir

the

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

to a

system

t; an

entropy

transfer

da

~ dU/x

accompanies
by entropy

ihe energy transfer, accordingto the


we

argument

of Chapter
it

2. This

energy transfer is what


as

defined

above

as heal,
not

and we see
a change

is accompanied

transfer- Work,
the

being energytransfer by
of a
piston\342\200\224does

in external

parameters\342\200\224such

position

transfer

any

entropy

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

lo the

of

the

other

decreases.
that we

Let
the

us restrict

ourselves

for

the

present

to

reversible

processes such

combined generalize

constant.Later

will

of entropy the discussion

the interacting to irreversible

systems remains processes which


the

are
heat

processes

in

which

the total

entropy

of the two systems increases,as in

flow example

in Chapter

2.

CkapterS:Heat
We

and

Work

work. Let

is

the

a quantitative expression to 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
i!Q

xda process. By the

(I)

as the heatreceived by

the

of

system

in the

principleof conservation
B)

energy,

dV

aw

+ dQ ,

which says thai the


and

energy

change

is caused
from

partly by
the

work doneon the


Then

sysictn

partly

by heal added to

ihe System dU ~
(tQ

reservoir.

t1W =

dV

~ zda Our
d\\V

0)
process.

is (be work performed designatingheat and


below.

on
work

the system
by iftjand

in

the

reversible

reasons for
explained

dW rather

For da

\342\200\224 we

0,

have

pure work;

for dV = xda, pure heat.

ihan dQ and

arc

HEAT

ENGINES:

CONVERSION

OF

HEAT

INTO WORK
and

Catnotinequality. Heat
processes
consequences

work

Have

different

roles
transfer.

in

energy

conversion

because
of

of the

difference in
freely

entropy

Consider

two work

conse-

the

difference:

(a) All types without

of work are

convertible

into

mechanical
An

and into
motor,
to

each other, becausethe

entropy

transfer

is zero.

ideal
a

electrical

mechanical friction or electrical work into mechanical

is device electricalresistance, 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,
An all work

convert

converts are

freely
in

other

and,

all

types

of

work.

(b)
heat

Work

can

be

completely

converted

into heat, but the


with

inverse is not irue:


system

cannot

be

completely

converted

into work.
the

Entropy entersthe
work.
from

with

the beat,

but docs
heal

not leave the system


necessarily
removed

A device that
the

generates
has been

work from

must

strip the entropy


from

heat

that

converted to work. The entropy

the converted

input heat

cannot

be pennittedto
ultimately

pile

up

inside

the

device

indefinitely;
way

be

removed

from

the device.

The only

to

do

this eniropy must ultithis is to provide more

Heal\302\243itgines:

Conversion

of Heat

into Work

Entropy

Figure 8.1 Eniropy and energy reversible devicegencralmg work must equal ihc entropy inflow. the amount

flow

in any
\\\\ca.t.

continuously
The

operating
outflow

from

entropy

input

heat

than

converted to work, and 10 ejectthe


thai

excess

input

heat

as waste

BecauseiiQ/ifc = r,
entropy

heat, at a tempcrat ure lowerthan


the

reversible

heat

iransfer
the

is given
all

by the temperature
input

.it which

input heal (Figure 8.1). of one unit accompanying It follows is transferred. heat
of the

that only
cany

part of the

heat

need

be ejected

at the
the

lower temperatureio
bctv^^.i

;t\\\\ay

the entropy

of the input heat. Only


to

difference

input

and outpul
eittropy

heal can be convened


must

work.

To

prevent

ihc accumulation

of

there

be some

output

heat; therefore h is impossibleto convert


entropy

ail

the
A

input
prohibition

heal to work!
against

unlimited

accuniLiiaiion

tn

device it

does

not

mean entropy cannot accumulate temporarily, that provided removed. Many practical energy-conversion devices operatein

is ultimately
and

cycles,

the

entropy

contained

in

the

device The

varies

deviceis calleda heat The entropy contained


the
There the

engine.

with time. periodically internal co'rnDiisTion engine

Such a cyclic is an example:


of

in each

cylinder

is at a

minimum near the beginning

intake
is entropy
What

stroke
a value does
fraction

and a maximum near the beginningof the exhaust stroke. of the entropy eontent to which the devicereturns cyclically;
not
of the

pile up indefinitely. input heat Qh taken in convened into work.?


To
during

one

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 reversibleprocess the output this entropy per eyclc is as output

temperatureth
the

can

be

heal

is ak

\342\200\224

avoid

entropy

is equal

to the input entropy:

Q,fa = QJik ,

14)

Qi

ir,/rh)Qh.
difference

E)

The work
between

is the generated during one eyeleof a reversible process the added and waste heat extracted: the heat
W

Qh

- Q, = [1 -

QA

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

Qh.

F)

The

ratio of
the

ealled

to the the work generated


efficiency:

heat

added

in the

reversible process

is

Carnot

G)

This quantity
Carnot*s

is named in

honor of SadiCarnot,who
of

derived

it in

1824. It

was
a

a remarkable feat: the


derivation

concept

entropy

preceded
the

by some 15
highest

not yet been invented,and the recognitionthat heat is years


had

form of

energy.
is

The Carnot efficiency


efficiency

possible
of

value of the
input

energy conversion
in any

ij

W/Gh,

the output

work per unit

heat,

cyclic heat

Heat

Ens'\"\":

Conversion

of Heat

into

Work

input

Output

Figure 8.2
entropy inflow

Entropy

and

energy
new

(low

in

a teal

irreversibilities ihal generate


outflow at

entropy

ihe

lower temperature higher temperature.


at the

heat engine containing inside the device. The is larger than the entropy

t,, and t,. Actual heat engines operates betweenthe temperatures have lowerefficiencies because the taking place within the device are processes not perfectly reversible. will be generated inside the device by irreversEntropy 8.2. flow diagram is modified as in Figure irreversible The processes. energy-entropy We now have three inequalities

engine that

ft S:

&(r,/Tfc);

(9)

A0)

The

actual

energy conversion efficiency j;

obeys the Carnal inequality

W/Qk

We

can

have

i; =

ijc only in the limit of reversible

operation

of

a device

that

takes in heat at ih and ejectsheal at rt. The Carnot inequality is the basic limitationon any heat in a cyclic The result te!!s us that it is impossible process.

engine

that

operates

to convert

heat tnto work. For a


efficiency

all input

given

temperature

ratio

tJt,

the highest

conversion

is

obtained

under
xhfxit

reversible
but

increases

with

tJt, -* go.
The

increasing

we

inoperation. The limiting efficiency !00 percent efficiency only when attain

low-temperature

waste

heat

ejected

into

the environment,

so thai r, c;innoi be
temperatures

of any

heist engine must


below

ultimately

be

the an

environmental

temperature,

usually Th high compared


limited are

about 300

K. Higheilicieney requires
in

input

temperature

to 300 K. The usable


materials
to

practice

are unfortu-

unfortunately which

by expected
limited

various

constraints.

In power plant

steam turbines,

is

currently

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

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
reduce
is a

this ellkicticy problem


in

high

metallurgy.

Sources

of UreversibHity.

several Figure S.3 illustrates

common

sources

of

irrevcrsibility:

(a)

Part of the
bypassing

input

heat

Qh may

flow directly

the

actual

energy

cylinder engine.

walls

duriiig

the combustion cycle of the


-

conversion

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


internal

combustion

(b)

Part of
temperature
the flow.

the temperature differencex,,


diflcrencc drop

in

tesnperature

r, way not be availableas temthe actual energy conversion process,because resistances in the path of the heat thermal across

of

(c)

part

of ilic

work generated may

be convertedbackto heat
doing

by

mechanical

friction.

(d)

expand irreversibly without expansion of an idealgas into n vacuum.

Gas may

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

heal
during

How

in the

palh

irreversible

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

are heat

remam valid

for

the

reversed

flows.

Chapter S: I hat

and

Work

The
efficiency temperature

energy
G), to

ratio
but the

of interest
tlic

in

refrigerator

is itot

tile energy
at

conversion
low refrigerator

ratio

work

consumed.

Q,/W of iho heat extracted This ratio is calledthe coefficient


in

tlic of

tem-

performance;
52 \302\273;

its limiting
W;Qh
f\302\260r 'he

value

reversible

operation
by

is called

the Carnot

coefficient of refrigeratorperformance, denoted


with

yc. Do not

energy

conversion

i;

<

i always,

y can

be > 1 or

< 1.

efficiency of a
Eq.

From

E)

and

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

confuse*/ =

consumed

is

A2)

The Carnot coefficient of refrigerator performance

is

Th

T,'

A3]

This ratio can be larger


Actual refrigerators, that generate entropy

or

smaller

than

unity.
always refrigerator

like actual heat engines, inside the device.In a

contain this

irreversibilities excess eniropy flow diagram


are

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

is of

positive,

we now

have ah >

e, ,

A4)

in

place

of (8).

Further,

& 2 (V'Jfl

A5)

Qt

- Q, >

\342\200\224

1]Q,

=\342\200\242

Q,

\302\273

Q,/yc

A6)

Q,iW

< yc.

Air

Conditioners

ami

Heal Pum

Ouipui

Input Figure 8.4


Entropy

and

energy

flow in a

refrigerator.

The Carnot coefficient yc


performance

is an

y, just

as the
efficiency and

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

energy conversion Both heat engines


law

a heat
are

engine.
subject

refrigerators

to restrictions

imposed by the
different.

are device designproblems totally the design of refrigerators to operate at the In particular, temperature helium or below is a challenging in thermal (Chapter problem physics

of

increase

of entropy,

but the

ofliquid

12).

Air Conditioners
Air

and Heat Pumps


are

conditioners the

automobile;

heat

is ejected

inside during

and outside the winter,

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

refrigerators

that cool

building we

lo the

heat

pump.

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

Chapter Si

Hear and
heat the

Work

pump
healing

can

building
I).

with

a lower

consurnption

of energy

than by direct
They

(Problem

The

limitations

on the
to

use of heat pumps


and

are

largely

economical,

are

much more costly


Heat

install

pumps

make

economic

or furnaces. than are simpleheaters sense primarily in eiimatic conditions in which


to main tain

air

conditioning

is required

anyway.

Carnot Cycle

The

derivation

of of

the

Carnot

energy
performance

conversion
made
from

coefficient a

refrigerator by which

efficiency and of the Carnot no statement about how to


heat,

realize process
refrigeration is

work is

generated

or

about

how refrigeraCarnot

achieved.

The

simplest

and best

known such process is the

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-

work 8.5:

done

by the

system in one cycle is

[he

area

of the

rectangle

in

Figure

W~{Th
follows

T,)(tfn

- ffj.

A3)

whicii

from

SdU

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

-SpJV

where jjklV is the work done by the first phase is T = ts during

the

system

in one

cycle. The

boat taken up

at

We

combine

(IS) and A9) to

obtain the Carnot efficiency

;/c.

Any

process
working

described
substance.

of the by Figure 8.5 is calleda Carnot cycle,regardless

,lCyd.

Figure 8-5
illustrated

into work, cycle, for the conversion of heat of entropy versus for an arbiirary temperature, of two working subsiance. The cycle consists phases expansion 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
A

Carnot

as a plot

isothermal

(I

iscntropic

B -> 3 and 4
heal

- 2 and 3 - 4), and -* 1}. The


consulted

one
nei

phase
work

of each

kind

is

done is ihc

area of ihc
ilic

loop.The
broken

at r^ is the

area surrounded by

line.

The Carnol

!o indicate cycle is a point of reference


what

what

could

in principle cycles
often

be done,
high

rather than

in

fact

is done.

All

energy

conversion

need a
(lie

temperature

input

and

a low exist,

temperature output of heal, bu!


as
in

heat
Even

inputs
where

and outputs
such difference

are not well-definedreservoirs at constanttemperatures.


steam

reservoirs presenl and

turbines,

(here

is invariably
the

;s

temperature
reservoirs.

between

the

working substance and

reser-

The

healing

cooling

processes are

never truly

reversible.

Example: Carnot

Caettot cycle<i\\h initially

cycle for an
ihc

idea!gas.
occupies

We

carry

an

ideal

monaionjic

gas
to

through

gas

reservoir

at

the

high temperature

a volume t', and is in thermal tv The gas is expanded isolherlttally

equilibrium the

with j volume

K, as
\\vo[k heai

in

Figure

\302\243.6a. In

Hie process
n^cdmmcal

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

the gas absorbs Die heal Q, from (Rt and delivers sy ^Icm conncclco to Die pislon. i~or an sdcaiQas

ii

as the

reservoiris
=.

Qh

II'l3

JpJK
area

Nr^dV/V
\"
\0212

A'r

B0}

This

work is

indicated
now

by

the

labeled
until

Next,

the gas is

furlhcr

expanded,

iscntropically,

ihe temperalure

disconnect! has dropped to

from

(SI* and

the

low

tem-

peralure

:,.

In

Ihe

process

the addilional

work

is delivered by

the

gas.

The volume

V3

at

the

end of ihe

iseniropic expansionis related

lo

TlV32:3

= TftV22'3 ,

or

VJVj.

(tJt,}*2

.
reservoir

B2}
<Slf

from

F.63).

Afler

point

the

gas

is brought

into contact

with

a temperature

ciioscnlo

satisfy

KfVx so thai
\342\200\224 Kj/V'4

= (t*A,K'2
this

VJV2

B3)

i'j,-

f,.

To accomplish

compression,

the work

ust be done on ihe gas.This

work,

is ejected

to

<R,

as

heai:

ft
Finally, temperature has

= ^34recompressed

B5)

the

gas is

disconnected
initial

from
initial

CH,

and

liseii

to ihe

temperature

i*. Because
value

at this point the work

has returned

to its

Vlt

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

jy4!

\302\253

|N(rh

T()

B6)
the

on ihe gas; this -* 2 3, by B1). expansion


is performed
The

cancels

the

work

W2i done

by

gas

during

the iseniropic
in shaded

ncl work

delivered
8.6a

by

the

areas in Figures curves in the p-V

and 8.6b,

which

gas during is the

the cycle is given enclosed area in

by

ihe difference 8.6c.


so

Figure

diagram

are steeper lhan the

isothermalcurves,

thai

The isenfropic Ihe area of the

y3

Figure 8.6
and

The Camot cycle


in four

riicompressed

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


(a)

the

work

Two done during


and

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

(b) the
the

work

done

during

the two

compression stages,

cycle.

Chapter

8: Heat

and Work
i^

loop

is nnitc

2nd

ctintii

to trie

of 3r\302\243*i

jtic rccmn^lc

m F^Rurc 8,3.

iVc

Imvc

W(rfc

TjloaflV^). given
in

.
so that

B7)

The heat absorbed from


the

Cftk was

B0),

W/Qj,

- (ij

~-

r,)/Tj,,

which

is jusi

Camot

relation

G).

Energy

Conversion and

the

Second

Law

of Thermodynamics

The Carnoi

limiis on the
are

conversion

of heat

into work

of
\"Ii

refrigerators

direct

consequences

of ihe

law of increaseof entropy.

and on the performance


The

second
eniropy,

law
We

of ihermodynamics stated ihe classical

is impossible a

of heai from
All

reversible

peratures

have
could

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
two

so, We
reverse

combine

reversible
d\302\243\\ ice

devices
I with

with

different

efficiencies,

qt <

ij2,
ihe

in such a way
as a

(Figure 8.7)ihat

ihe lower

efficiency is operaied in
from

more

refrigeralor efficient device


Q{\\n)

(hat mows not only ihe

entire wasteheat Ql2


th,

2 back io
as well.

the

higher

iemperaiure

but This

an additional
of

amouni
ihe

of

heai

The overall
any

result would be ihe conversion


net

heal

Q{in) to work
thai

li^otit), uiihout
and

waste

heai.

would require

ihe annihilation of entropy


Now

would

violate

ihe law

jhai all reversibledevicesIhat operatebeiween ii is sufficient same efficiency, temperatures energyconversion to calculate this cfiiciency for any particular device to find the common value. ~ = The Carnot cycledeviceleadsloi;c (xh ri)/rft for the common value.
we have

of increase of entropy.

eslablished

the

same

have the

of Path Dependence
We have
processes,

Meat

and

Work
transfer

meaningful

We look
plane,

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 of a net amount a net amount of work is generated the and by system,
content

carefully used the words heat and work to characterizeenergy iiself. and not to characterize properties of the system
at

It

is not

of a

heat
returned

is

consumed.

But

the

system\342\200\224on

being

taken

once

around

Ihe

loop\342\200\224is

to

precisely
means

the
that

initial
there

condition;
cannot

This changed.

no property of the system has exist two functions Q{a,V) and W{a,V)

Path

Dependence

of I hat

and

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 a slate {ab,Yb) siSilc(aa,VB)to

the
are

work
given

Wub

required

to

curry
in

the system
Q

from a

by the

differences

and

W:

If such

fimcitons extsicd, the


would

nut

transfers

of heat

and of

work aroumla closed


the

loop
zero.

necessarily

be

zero,

;md we

h:ivc shown that

transfers

;tre

not

The transfers of hc:itand work between state (a) ;ittd slate (b) depend on the when the two states. This path-dependence is expressed 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

of

(he

system.

The

in (l)and

B) cannot

bedillerentials

Chapter

8:

that

and Work

Figure 8.8

Twotrr

sibie proceises in

which

mechanical

or electrical

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


Irreversible

from

heal.

Work

We consider the
is

energy transfer

processes

of

Figure
delivers

8.8. In
pure

each process &i


work

a purely

mechanical
friction

or electrical
or

system that

with zero ^ J^e

entropy change. The eneray


mechanical

same as if the energy of &2 is increased by

transferred to &2 is converted The finai electrical resistance. by had been added as heat in the first do2
\302\253

to heat, either by
state place.

of The

S2

entropy

ilU2fc-

This

entropy

Processes

in

which

new

no

entropy

is created in order
the

are irreversible because there is


created

is newly

created entropy.
entropy.

way

to

reverse

the

process

to deslroy the newly


conversion

If newly
irreversible

created
work

entropy arises by
has
at led

of work

to heat,

we say that

been performed.
the to

If we look only

the process
dU

that

net change this change


entropy, the

in

a system,

there

is no

way to tell whether


change and

in energy

and
tfWtev

i\\a

in as

For a was reversible or irreversible. we can define a reversible heat dQICV

reversible
this

work
in

change

a reversible
work

irreversible, the actual

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

Ineveniblt

Work

than

the

reversible

work,
tn\\'il

By

conservation

of energy

dU =
so

if\\Viim

that

The

actual heal reversible heat.

must transferred hi the irreversible process

be

less

ihan

the

Sudden Example:

expansion

of an

consider
work

once

more llic sudden

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

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
expansion

with
in

the gas

in

Ihermai

equilibrium

on the

gas

the

reversible

expansion

from volume

:o

Vj is,

from F.57).

\\V,n=
The

-Nilog(^/K,).
does

C0)
on the piston
in

work

done
the

on the

equai

to

heal

gas is negative;the gas transfer into the system:

posittve work

an

amount

Q[cy= The entropy


change

W[cy

>

0;

Wtet <

0.

C1)

is equal

lo Q,cJt,

or
~Wlcy/x

a1-al'=

NlogfiyV,).

C2)

In the ineversible process of expansion into because neiiher heat nor work Rows entropy = 0- From C1) we obtain Qi\302\253c.

the
into

vacuum
the

this enlropy from the system

is newly outside:

created
lVitltt

*=

in

agreement

with

B8) and

B9)-

Chapter 8: Heat and

Work

Figure

8.9

Systems between

which

on!)'

work

but no

heat is transferred

need not

be

at the

same temperature

for the process to be reversible.

In our discussion of irreversible is created insidethe


systems.
system

work

we

assumed

that

the new
transfer.

entropy
other

during

the delivery

of work Jo the
in

system by

This

heat transfer,
Chapter

is nol she only source of irreverstbility nol involvingany work, is irreversible


temperatures.

energy

Pure

iwo systems having different


2.
lower

We from

In this

process

heat
t2.

fs

transferred

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


if it takes

ai

the

temperature

We have.'.

i!U2
The newly

=\342\226\240

<fQt

0.

C4)

created entropy is

= (I/I,
The
negative,

low

1/I2)rfe,

-ii.re..

C5)

heal flow
so

is from high to
chitT >

temperature;

i!Qt

is negative;

r3

- ri

is

that

0.
systems

.
with

The energy transfer between two not be irreversibleif only work but
AH but

different

temperatures

need

no heat

is transferred (Figure8.9).

actual reversible constitute

energy processes a

transfer remain

are invariably somewhat irreversible, processes the backbone of the theory of thermalphysics. which is the equilibrium limit assume hereafterthat the words
of

They

natural

limit,

vanishing

entropy

generation.

We shall

heat

and work,

without a further qualifier, referto reversible processes.

Heal

and

Work

at Constant

Temperature or Constant

Pressure

HEAT

AND

WORK

AT CONSTANT

TEMPERATURE

OR CONSTANT PRESSURE
Isothermal

work.

We

a reversible

isoiherma!
V \342\200\224 za of

energy

F ~

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

ihai

because dx =

0, so

that

dW

dV

dU

- d(za) \302\253 dF.


is

C6!

Thus

in such

processes the Helmhoitz free energy

ihe

natural

encrgc:;';
ihe

ftiuciion, more

appropriate than
of

the

energy

V.

When

we treat
heat

an isotEicrltui
from the

process
additional

in

terms

(he

Hclrnholiz
Often

free energy,

we automatically include
for

work
the

that

is required
the
does

to make up
heat
noj

the

transfer

system to
for

reservoir.

transfer is
change

the
work

ideal
done

the
lake

gas the energy V is equal lo the


and

in an

ihe major part of the work; isothermal process, and


or
not\342\200\224

heat transfer.
energy

Isobaricheat
place

work.

Many

transfer

processes\342\200\224isothermal

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

at constant

in systems

=/<\342\200\236<<

Figure

8.10

displacing

the a liquid boils under aimospheru: pressure, vapor the aimosplierc does work againsi ihe atmospheric pressure.

When

ChapterS:

Heal and Work

where the
system

pressure on the
its

piston

is the

external

atmospheric

changes

volume
system.

total work doneon the


environment

by dV, the work -pdV


If positive,

pressure. If (he
of the is part environthe
to

\342\200\224

d{pV)

this work
the

is provided by
work

and

is

in

this
often

sense \"free.\" if
appropriate

negative, the
system

is

delivered

the

environment

and is not extractablefrom


is

for other
from

purposes.
total

For
We

thjs reason it

io subtract
performed

~d(pV)
the system,
=

the

work.

thus obtain the

eflccthe work
itW

on

defined as
till

ilW =

d{PV)

itU +

d{pV) -

itQ

~ HQ ,

C7)

where we have defineda

new

function

= V

+ pV ,

C8)

called
the

the

enthalpy

which

plays

the role in

processes at constant pressurethai

energy

V plays isi

processes at constant

volume. The term/it7in

C8)

is the

work

the space

to displace the surrounding atmosphere order to hi 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),
required
vacate
d\\V

=> dF

+ d{pV)

=> dG ,

C9)

where we have defined another new


G

function

~ F

+ pV

\302\253 U

pV

- xa ,

D0)

the at

Gibbs constant

free

energy.

The

temperature

effective work performed in a reversibleprocess and pressure is equal to the change in the Gibbs
useful

system. This is particularly where the volume changes as the reaction The Gibbs free energy ts used extensively
free

energy

of the

in

chemical

reactions

proceeds

at

a constant

pressure.
is

in

Chapter 9, and Ihe enthalpy

used

in Chapter

10.

Heat and

Work

at Constant

Temperature or

Constant Pressure

isobaric
electrodes

Consider

an

ciccHoiylc
w&in

ilia t do

H+

ant) SO4~

noi re net

of dilulc sutfurie lnc acid [r igtirc

acid s. 11J.

iti

which
^titfiir

Tnc

arc immersed philiiuiin tc sci^i dissocjaics

in i o

ions:

H2SOa
When a
where current

\302\253 2H+

SO.,\"\"
move
g;is:

D!)
to lhe

is passed

llicy

lake

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

negaihe clecirode

-+

H2.

D2)
they

The sulfatc ions move to release of molecular oxygen


SO4~
The

the

positive electrodes gas and clocirons: _. +

where

decompose

water

with the

H;O
the

- H3SO4+'iOj + 2c!^.
net

D3)

sum

of the

above liircc stepsis

rcucikm
H2

ctttuiluin

in lite

cell;
{44}
conslain goes

H2O-\302\273

1O3.

Whch carried out


prcsburcaiKicoitMiiiil

slowly

in

a vessci
A

temperature.

open to lhc almosplicrt!, ihc prticessis at power negligible pjft of the olcciricul injml

iulo

Figure 8.11

An

electrolysis

cell

An electrical
result

current

passes

through done

an electrolyte,

such

as dilute
hydrogen

sulfurtc and

acid. oxygen.

The overall

is the

decomposition
being

ofwaterinto

gaseous

The process is an

example of work

at constant

temperature and constant pressure.

resistance

heating

water

is related

of the electrolyte. The effective work required to to the molar Gibbs free energies of Use reactants:

1moleof decompose

W
Chemical

=>

AG

G(H2O)

G(Hj) -

\\G{02).
as

D5)

tables

list the

Gibbs free energy differenceAG


current

- 237 kJ

per mole at

room

temperature.

In electrolysis tins work is performed by a one Vo. If I is the time required to decompose

/ that

male

of water.

flows under an external I x I is lhe total Q \302\273

voltage
charge

(not

the

heat!)

flowing

tlirough

the cell, and we have

W ~QV0.
According

D6)
in decomposing

to

D3),

there

are

two

electrons

involved

one water molecule,

llcnce

Q
We

~2/v>
the

= -1.93
condition

x 10scoulomb.
lo take

D7)

equate

D6) to
voltage

D5) 10obiain

for electrolysis

a place.This requires

minimum

Vo

~AC/2NAe
must
the

D8} obtain a
between
finite

or 1.229 volts.
because
two
VQ

voltage merely

alone

larger lhan Vo reduces to zero

poierciuit V >

be applied to barrier Va, the

current

flow,

the systems
(V

on

lhc

be

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


sides

of the
Vo,

excess power

VQ)

/will

If V available

<

the

reaction

D4)
8.11

at the

simplesetupof Figure
happen
hydrogen
voltage

positive electrodeand
is possible,

al all.

Ev

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 wiih however, lo construct the electrodes as poroussponges,
will

proceed

from

gaseous

and oxygen
f'o between

focced

through

under

pcessure
the

the electrodes

and,

tf

electrodes

{law. sources

This

arrangement on board the


the

is called a

hydrogeci-osygen

a (Figure 8-12). Such adevice produces arc connected, eucnwl current will fuel cell. Fuel cells were used as power
incidentally

Gemini and Apoilo* ipacccta.fiand


fuel

produced

dtinking

water
The

for
In

astronauts.

principal
the

area.

technological limitation of cell the current density Apollo


lo

cells

is their

low
hundred

current,

per

unit

electrode

was

only

few

mA/cmJ;
cell

hence

large

elecirode areas are required


characterise

produce
in

reasonable operating

currents. The ranges as


fuel

current-voltage characand

of an

clearochcmi'cal
in

ceil
K.I

Us two

as electrolytic

cell are shown

Figure

3.

\342\200\242

The

Apollo

End criU used

Ni

and

NiO

uniict ibn fwf cells:

Pt

as decltoiici.

ami K.OH racier


McGraw-Hill,

sVian

H .SO\302\253

to J.

O. M.

Bockrisand

S. Sriili^asan,

Their

electrochemistry,

New York,

1969.

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

8.12

A fuel

with

electrode and

is removed

there.

Elcnrolysis

\342\200\224

Figure

8.13
fuel

Tliecui
cell,

ic of
anges.

aa electroiyiic

celt or

indie

ChaptcrS;

Heal and Work

Chemical Work

Work performed by
work,

the

transfer
with

of particles
the

to a

system is called chemical


the

because

it is

associated

chemical

potential.
system

When

particles are transferred, the number of particlesin


the

is one

of the
then

independent variableson which


a reversible

energy

U depends.

If U

= U(atV,N),

for

process

dU =
by tlie
the

xda -

pdV

fidN

,
have

D9}
replaced

we thermodynamic identity of Chapter 5. Here familiar

the partial

derivatives by their
zdo

equivalents

(Table

5.1). By
and

our definition
~pdV

of heat,
terms

lerm

represents

Ihe transfer

of heal
understood

the

and

fidN

represent the performance of work, ali


<tW ~

to

be reversible:

-pJV+
the

pJN.
term is

E0}
the chemical work:
.

The -pdV.termis

mechanical

work;

pdN

dWc

ftdN.

E1}

If there

is no

volume change, dV
transfer

In particle
with from

a heat both

reservoir,
systems.

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

0. All

the Work

from

system

&x to
\342\200\224 \342\204\242

dN =i
work

dN2
performed

dN,

system .&;. The chemicalpotentialsare /it and p2. If is the number of particles transferred, the total chemical

is

dWc

= OWcl

d\\Vcl

fadNt

+ pldN2

= (p2 there is

nt)dN.

{52}

The
(dV1

work
*=

that must
= 0),
the

be supplied to the
if

pump

is a\\Vr if

no volume work
We

dVi

and

all

processes
additional

arc reversible
meaning

The result
summarize

E2) gives art


propcriics

of the

chemical potential.

of ihe

chemical potential: work required to transfer one


zero

{a} The
particle

chemical

potential

of a

into

the

system,

system is the from a reservoir at

chemical
systems

potential.
is equal

(b)

The difference in

net work requiredto movea particle from

chemical potential between two


one

to the

system

to the

other.

Figure

8.t4

rcs'ersibly chemical

chemical

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
work ;

the

amount

per pariicie is

the

difference

in chemical

potentials.

{c} If ihe

two

potential;no
the other,

systems
work

are
is

in diffusive
required

io

equilibrium ihey have the move a particle from


{Chapter

same chemical
one

syslem

10

{d} The difference in internal chemical potential is but to the systems equal potential opposite

5}

between

two

barrier thai

maintains the

systems in diffusive

equilibrium.

Example

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
i Chemical
work

for

an ideal

move revcrsibly ins

atoms

of a

02
This

/fl

t[10gOl2/\302\273iQ)

logOlj/Hfl)] =

Tlog0l2/Jl,}.

E3)

rcs\\ih

is cqtial

isothciniiiily

compressN
W

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
-\302\247pdV

-Nx^tiVjV^

NTlog{IV^}

= WtlogfHj/ii,}.
to

{5A}

Hence

the

mechanical

work per

identical particle is iSogtoj/iij),

the

result

E3). The

ChapterSt Heat and

Work

Reservoir'

ilnergy

exchangeswork both

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.
Figure

per panicle

sysiems

in

ideniiiy

of

the

chemical

work
dilferem

wiih

the

isoihcrmal

compress

illustrates the equi-

lence or

convcriibiiiiyof

kinds

of work.

Magnetic Work
An

and

Superconductors

,-

important

form

of work

is magnetic work.Themostimportant
this

application

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

work

is to

application

is treated

here.

that

usually

less

than

20K,

many
finite

their

normal

state wiih a
apparently

electrical

conductivity

to

a superconducting

slate wiih an

infinite

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

superconductor

is first

interior from
even

the

penetration

by a

occurs magnetic field. However, ihe expulsion

ir i|ie

8.16).

This

is cooled below Tc while in a magneticfield (Figure superconductor that active expulsion, called ilic Metssncreffect,shows supefconis more
effect ilian an infinite conductivity. The Mcissncr the currents lhat are spontaneouslygenerated near surface,

duciivity

is caused

by

shielding

in a

layer

about lG~5cm iliick. The magnetic

field

expulsion

is not

Superconductors are said tobeof type It if the in a range of fields above some low nonzero,

expulsion
field.

always complete. is incomplete, but stilt


restrict

We

shall

ourselves

ark

and

Superconductors

Hgure in

8-16

Mcissner

a constant

applied temperature

transition
the

supercon6tiding sphere cooled below ihe magnetic field; on passing tlic iiiics of induciion B arc ejectedfrom
effect in a

sphere.

Figure 8,17
fidd

Thresholdcurves
lempcratui;:
specimen

versus

for scv
\342\226\240i ;jpe

conductors. A
below

ihe curve and

noiii..;! iib

In

TiX

Temperature,

in

,-->I[-lOUl

fill

111

Magnetic

I Curt

and Superconductors

Figure 8.19
arcu

superconductor

A in

superconducting

sol

produces

a magnetic Ikld

B.

transition
that

it

is the

electronic

system

rather than the


distinct

crystai structureof the


phase,

metai

undergoes

a phase
in

transition.
.<hermodynamic

The superconducting staleis a


by differences
the

as confirmed

heat (Figure
-di

The
of

iicai

capactiy

capacity 8.1 S)
x =

superconducifvhy

of the normai and the supcrconduciing stales. cxiiibhs a pronounced discontinuity at ihe onset xt; when superconductivity is desiroyed by a

magnetic

field,

ihe discontinuiiy
free

disappears. The stable phasewill


t =

be

the

phase

with the

iower

energy.

Beiow

tc
than

in

zero

magnetic

fieid

of liie superconducting phaseis lower

that

of the

normal

the in energy of the superconduciing magnetic phaseincreases 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 field is The increase the free energy of a superconductor in a magnetic 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 crossa long a uniform field B, as in Figure 8.19. that produces sectioninside solenoid is the The work required to reduce the field to zeroinside superconductor a counteracting the equai to the work required to create within superconductor field solenoid We know from electromagnetic B thai exactlycancels the fteld. B is given the work by theory that per unit volume required to create a field

energy phase. The free field, as we show

the free

(SI)

B2/2{t0\\

E5a)

(CGS)

E5b)

Chapter

Si

Heal

and Work

Figure 8.20

Tlic free
of [he

energy

dcnsiiy

F* of

noi\\ti\\^i
magnetic

syndic

t\\otii\\3.t meiat
Al a $\342\200\236.

is

appcox.iiv\\u.lcty

independent fkUi

intensity of the
temperature
in

applied
x <
magnate F^i.O).
xt

the

melai

is a superconductor

zero

field, so
in

dial Fsti,O)is lower than field increases applied magnetic


SI

An so

Fs by

Bj/l/i,,,

unite

land by BBJ/8n
=\342\226\240

in

CGS

uniis),

lhai Fs(r,/iJ
larger
the

F5(r,0)

liian ihe

criikjil
in

deiisiiy is lower

ihe

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


+
field

siiperconduciing si ale is ide siabic

siaic, and

no* ihc nornmt


of i tic

st,iie. The
drawiiij;

origin

vertical se;ilc in
ftgute

ilic

is ai
und

f Jr-O)-The
Us
ii\\

equally

applies

10 U5

= 0.

Applied

magnelic field Ba

Tiiis is the amount by


is raised by
constant

which

the

free energy

density
field,

in

the

bulk

superconductor

application of an externalmagnetic
comparable

in an

experiment
normal

at con-

temperature.

There

is no

free energy increase for


the

the

conductor,

because (SI)

there is no

screeningof

applied

field.

Thus

E6a)

{CGS)
En

E6b)
of

the field magnetic energy density of both phasesversus tne free will rise of the energy superconducting phase 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 explanation of the destruction of superconductivity by a critical a

plot

the free

magnetic field
Wiih

Bf.

increasing

temperature
else

the free
t

energy differencebeI ween


--\302\273

normal

and

superconducting

phase decreases as
being

rr,

and

the

critical
and

magnetic
in a

field

decreases. Everything

equal,

high

stabilization

energy

superconductor will lead to boili a high field. The highestcritical fields found are
highest

critical

temperature

type I a high critical


with

amongst

the superconductors

the

crilical

temperatures,

and \\ice versa.

SUMMARY

1. Heat is
reversible

the

transfer

of

process dQ = xda,
the

energy

by thermal

contact

with

reservoir.

In

2. 3.
4.

Work

describe
only
The

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

transfer

of energy

that
when

Carnot

energy

conversion
of

limit to
The

t!ie ratio WjQh


coefficient

the

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

\342\200\224

tJ/tj,

is the

upper

Carnot

of refrigerator
QijW

upper

limit to
work

the ratio
performed

of
&

the

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

5. Thetotal
roof

on

system the

process is equal to the changein


the

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

system.
at to

6.

The

effective work performed on a system pressure in a reversible process is equal


energy

constant

temperature

and
free

the

C
chemical

- w + pK.
performed

change

in the

Gibbs
of

7. The
particles

work

on

a system

in

the

reversible

transfer

t.lN

to

the

system
the

is pdN.
energy

in 8. Tlic change

free

density

of a

superconductor {oftype
SI

{) caused

by an

external

in magnetic field B is B2/2{i0

and

S2,8;i

in CGS.

PROBLEMS

/. Heat pump,

(a)

Show

that

per

unit

of

heat

delivered

inside

fora reversible heal pump tile energy required the building is given by the Carnoi F): efficiency

Chapter S: Heat and Work


In absorption refrigerator. not as work, but as heal

2.

Absorption
is

process
i(,h

supplied

refrigerators the energy driving the a gas from flame at a tempenisure


be

>

xh. Mobile (a) Give an


a refrigerator,

home and

cabin refrigerators may


flow

of

this type,

with

propane

fuel,
such

energy-entropy

diagram

similar

to Figures

8.2 and

8.4 for
Hows for

involving no work at all, but with energy and entropy > ta > ij. (b) Calculate the ratio QJQhh, three temperatures rfch = xhh. Assume at r \302\253 heat extracted where QM is the heat input at r r,,
at

the

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 as for the ideal gas? first isothermal Are they equal to each other, expansion? as for Do the two the ideal cancel e ach gas? (d) Calcuother, (c) isentropic stages it with the total work done the one the heat Calculate Compare by gas during cycle. is the Carnot taken up at rh and show that the energy conversion efficiency
3, Photon efficiency.

4. Heat
improved

engine\342\200\224refrigerator

cascade.

The

efficiency

of a

heat engine is to be

valuer,., refrigerator
below

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
by

lowering
the

the

temperature

of its

environmental

in

this

way?

5. Thermal used as

the low temperature reservoir of a large power plant, with a steam = of 500JC. If temperature Th ecological considerations limit the amount of that heat can bedumped the rtver to \\ 500 MW, into what is the largest electrical

pollution.

river

with

a water

temperature

T} =

2CTC

is

to

be

output that the plant can deliver?If improvements


would

in

hot-steam

technology

permit raising
ah

Th

by

lOQ'Q

what

effect would

this have

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 temperature T,); 7\"j. The 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

conditioner.

A room

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

discussion

of room
46,

air conditioners
19 A978).

Amer. J. Physics
2S2 K

is given by
378

H.

S.

LefT and

W. D.

Teeters,
be

In a

and the

outdoor heat exchanger at


in

realistic unit the cooling coils may


K.

at

7. Light bulb

a refrigerator,

A
tOOW.

100 W light
Can

bulb is
refrigerator

left

burning

inside

Carnoi

tempera!ure?

refrigerator

that draws

the

cool

below room

S.
uiilized

Gcoihermal

energy.

very
a

to

generate

electricity
to

steam

to drive

a turbine. As
dQh

rockdrops,
rock,

according

assumed to be temperature independent. at If the plain operates 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

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, heat where C is the specific of the
large

lower reservoir temperature T,stays


At the

constant.

-.

end of

the

(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

calculation,

give

a numerical

value, in kWh. for M - 110 C, C,


total

7\",

10u kg
\302\273 20

C.

electricity

kWh.

solid

to

T~Q.

We saw in

Chapter 4 that the heat

of
as

to Ti,

nonmetallic ~ aT3. C

\302\253 0

by

means

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
solids

at sufficiently

and for (varying.) low-temperaturereservoir, has fixed to reservoir a temperature 1\\equal the solid. Find an expression the for electrical energy

which
initial

tile

temperature

high-temperature Tj of the

required.
N noninteractiilg, if

10, ltrerersibte spin


\\

fermions

of mass

a gas of expansionof a Fermt gas. Consider at a volume in A/, initially temperature V;

~ 0.
final

Lei the
volume

gas expandirreversibly
V}. What

into

a vacuum,

wiihout

doing work, to a

if Vf is sufficiently large temperature of the gas after expansion 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 mass values for ihe final temperature equal = in a to the electron as and (b) 10\"cm\023, metals; mass, particle mass NjV = stars. white dwarf as in equal to a nucleon,and N/V 10JO,

is the

Chapter

Gibbs

Free

Energy

and Chemical Reactions

GIBBS

FREE

ENERGY

262

Example:

Comparison

of G whh

265

EQUILIBRIUM

IN REACTIONS
of Atomie
the

266
267

Equilibriumfor IdealGases
Example:

Equilibrium
and

and Molecular
of Water
Action

Hydrogen

269
265
270

pH Example;
SUMMARY

Ionszatton

Example: Kinetic Model of Mass

272

PROBLEMS

272
Zero

1. Thermal ExpansionNearAbsolute 2. Thermal lonization of Hydrogen

272

273
Semiconductors

3. lonization ofDonor
Growth

Impurities

in

2 73

4. Hiopolynicr

2/3
274

5.

Patticlu-Antiparticle

Equilibrium

Chapter

9: Gibbs

Free Energy

and

Chemical

Reactioi

GIBBS

FREE

ENERGY
F

The Helmholtzfree energy

introduced

constant
many spherc,

volume

and

temperature.

But

chemical h

reactions, is

are performed

system at many experiments, and in particular at constant pressure, often one aimo
in Chapier
to

3 describes a

useful

configuration

to introduce another function at eonslant pressure ;tnd temperature.


G

treat As

the in

equilibrium Chupicr 8, we

define the Gibbs free energy

as

G a

- xa +

pV.

A)

Chemists

often

call

this the free

energy, and

physicists

often

call

tt

the

thermodynamie

potential.
minimum contact

The most importantproperty of the Gibbs free energy is thai it is a for a system S in equilibriumat constant pressure when in thermal a (H. G with reservoir The differential is of
dG =

dU ~ ida

cdx

pdV

Vdp.
with

Consider
at

a system {Figure9.1)in
t and the pressure

thermal

contact

a heat

reservoir

<Rl

temperature

in mechanical

contact wilh a pressure reservoir<R2

that

maintains

so

that

the

differential

= 0 and dt p, but cannot exchangeheat. Now dp = 0, becomes dG oflhe system in the equilibrium configuration

dGi
The thermodyiiamic identity
zdds so that

dUs

is

xdax + pdV*

B)

E.39)

= dUi
But

ttdNi

pdVs,
ence

C)

B) becomes

dG^ \302\253 ndNx.

dNs

= 0,

wh

dGj

\302\273 0

System Hea

i eser

\342\226\240oir

rese rvoir

\342\226\240\342\226\240\342\226\240v\"'Jif

m, ger lo

v.hh

a heat

reservoir with a

and

in

mechanical

equilibrium
reservoir NPSu

whkh system.

qualiz

e pressure

on Hie
insuSalcd.

barysiai or pressure maintains a constant pic


barysial

The

is

thermally

Pressure

cserv

which
variations

is tlic
at

condition for
pressure, variables

Gj to be ;m
temperature, for G(N,z,p).
G3

extrcmum

wilh

respect

to system

varia-

constant natural

and particle
a minimum,
w'Hh

number. Theseare,thereraiher
the

therefore, the

That ihe extremumof


follows

musi

be

than a maximum,
eniropy

direciiy

from change

the laking

minus

irreversible

sign associated place entirely wiihin

in (i);

Any

&

will

increase

a and

ihus

decrease Gs.
With

B),

adx +

E)

The

difierentiai

E)

may

be writicn

as

Comparison of{5)and

F)

gives

the relations

0)

(8)

Chapter

9:

Gibbs

Free Energy and

Chemical Reactions

, = V.

E)
by cross-differentiation;
and pare

Three see

Maxwell

relations 1.

may

be obtained

from these
+

Problem

In the

Gibbs

free energy G
do

\342\200\224 za

pKthevariabfesr

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 we must be able to write to species is present. If G is directlyproportional N,

quantities: they

not

change

value when

G=
where ep is

Nip(p,x)

A0)

quantitiespand r. If
temperature,c;idi

independent
two

of N because it
identical

is

function

only

of the

intensive

wjih

j.V

molecules,

and temperaiire |>ui together, the Gibbs free energy


volumes

of gas at

equal pressure

does

not

change

in

the

process.

It follows

from this argument that (II)

We

saw

in G)

that

A2)

so that

<p

must

be

identical

with ;j,

and (iO) becomes

G(,V,p,t)

A3)

Thus

is equal to 'h for s single-component system 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

the

chemical

poiemiaf

all species:

A4)

Gibbs FreeEnergy
becomes

The

ihermodynamic

identity

xda = dV

pdV

^e/INy,

A5)

and E) becomes
dG \302\253

\302\243njdNj

adz

+ Vdp.

(!6)

We

shall

develop

the
ts

theory
constant

of chemical

that
reacting

G ss: YJ^jfif
molecules

a minimum at

the property equilibria by exploiting of with respect to changes in the distribution in a t, p. No new atoms comeinto the system
from

themselves reaction; the atoms that are presentredistribute snucics to another molecular species.

one

molecular

iiiutupfri

Omipurhtw

ti \302\273f

with

F.

Let

its

sttf

wluit

is Jitiacut

:ihuuJ

\\\\vi

iwo

rd.ttions

{cFfdN)tty
and

= p(iVrT,K)

A7)

$G/dN)tiP

*=

fi{T,p).

(IS)

We found

in F.18)

lM

for an ideal

gas
A9)

MN.r.F) -Tlog(WKnQ) ,
so

that

ti(N,z,l')

is

not

independent

of N

and therefore
if ilie F.24),

we cannot
is kept at

write

F =

JV;i(r,f) .is
as

She iaiegra!of{S7). Thai is, f is not direciiy proportional lo N from number of particles is increased. Instead,
F(t,V,N)^

system

cotislanl volume

ihc

Ni[\\og(NJVnQ)
ideaJ

- I].

B0J

But

she

Gibbs

free energy for

t-he

gas

is

C(r,/\302\273,N)

\302\273 F

PK

Arr[!og(p/rny)
NrIog(;j/THQ) ,

- l] +

-Vr

\302\273.

PO

by use potential

of ihe ideal gas Saw


us

in

the form

N/V

==

p/r.

We readily

identify

in B1)

the

chemical

/((t,p)

= i

lo\302\243(pJxnQ)

B2)

Chapter

9; Gibbs Free Energy

and

Chemical

Reactions

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

as is convenient. 122},

EQUILIBRIUM

IN

REACTIONS

We may write the

as reaction equation of a chemical


v,A,

v2A2

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

v,A,

= 0

B3)

B4)
where

the
in

Aj denote
the

the chemical
equation.

species
Hj

reaction

species, and the Vj are the coefficients Here v is the Greek lettermi. For the

of the
reaction

+
=

Clj = 2HC1 we lave


H,;

Ai

A,

- Clj;

Aj

HC1;

Vi=l;

fj=l;

\302\273j=-2.

B5)

The

discussion

of chemical

equilibria is usually
temperature.

presented

for

reactions

under

conditions

of constant pressureand
respect of

In

equilibrium

with energy isa minimum

to changes

in the

proportions

the Gibbs free of the reaclants.

The

differential

G is

dG

- Z fj^i

adz

Vi!p.

B6)

Here//j
constant

is the chemical potentialof species j, asdefined by \\is = {BGJdNj)s-p. At fa = 0;then B6) reduces pressure dp = 0 and at constant temperature 07)
on the chemical tjo uu musl miu

to

rfC-1/,/W,.

The changein
zero.

the

Gibbs

free

energy
comlit^rtufii

in

reaction

depends

potentials of the

re\302\243tctbnts\302\273 Xti

is &i cxtrcmum

Equilibrium

for

Ideal

Gases

The change
coefficient

dN} in

the

number

of molecules

v,m

the chemical

equation

]>>/.; - 0.
\302\253

of species/
We

is proportionalto the
Write
\"

may

dN} in

the form
B8)

JNj
where
in

rjd$

dfif indicates
becomes

how many

timesthe reaction B4)

takes

place.

The

change

dG

B7)

dG

\302\273

vjfi

dft-

B9)

In equilibriumdG

0, so

that

C0)

This is the condition for

equilibrium

in a

transformation

of matter at

constant

pressure
Equilibrium

and

temperature.*

for Ideal

Gases
useful

We obtain a
Y^Vjf-j We

simple and

form

of of

the

genera!

=
utilize

0 when
F.48)

we assume that each lo write the chemical


fij

the constituents

j as potential of species
-

equilibrium condition acts as an ideal gas.

rflogMj

logc;) ,

C1)

where

nj

is the

concentration

of species j

and
,

cj a
which

\302\253QJZ/int)

C2)

is

depends
internal

the

on ttie temperalure but not on ttie concentration.HereZ/int) as function, F.44). Then C0) can be rearranged partition
5\302\273gnj

\342\226\240

$>,!(*<:,

C3a)

Uul ihcmull

is moregencrat; onceequilibrium

is reached,

ihe rcaclion

does nol proceed furihi:r,

when

p and

t arc specified..

Chapter 9: Gibbs

Free

Energy

and Chemical

Rcactia

C3b)
The left-hand sidecan berewritten
as

C3c)
and

the right-hand

side can

be expressed as
C3d)

Here

K(t},

called

the equilibrium

constant, is a function only of the

temperature.

Wiih{32)\\vehave

K{t)

nil\302\253/'

C4)

because

the

internal

free energy

is Ffim) =

-TiogZj{int).

From

C3c,d)

and

C4)

we have

Fk-Vj

C5)

known

as the

law of mass action. The result


a function

says

that

the indicated

product of the

concentrations of the reactanlsis


in

of the
force

temperature
a change

alone.
in the

change

the conceniraison

of any one

reaciam will
other

equilibrium to choose in
need

concentration of one or moreofthe


To calculate

reaclants.
C4),

the equilibrium
way

constant K(x} in
internal

it is

essential

a consistent
consistency

the

zero

of the

energy of each reactant.We

here

because

the value of each


be related
It

partition

function

Zji'mi)

depends

on our
different

choice of the
reactants

zero of the energy


is
effort

eigenstales.

The

different

zeros

for the
energy

must

to give
diilicuh
our
on

properly the energy or free

difference

in ihe

reaction. a conscious

not

happen

without
^

as
of

l\\2

2H, ilie simplest

procedure is to
the 2H)

to arrange ibis, but it docs not part. For a dissociation reaction such clioosethe zero of the internal energy to coincide

of each compositeparticle (here

H2 a!

molecule} res!.

with the
is \302\2433

of the dissociatedpanicles (here


the

Accordingly,
~\302\243fl,

we piacc
where

energy the energy


the

ground

state

of the

composiie particle at

energy

Equilibrium for

Ideal Gases

required
and

in

the

reaction

to dissociate

the composite

particle into its constituents

is

laken

to be

positive.

i Equilibrium Example
mass

of

atomic

aciioil

for the

rcacuon Hj

and molecular hydrogen. = 2H ttz ~ 2H = 0

The siatcmcnl of ihe


for

law

or

the

dissociaiion

of molecul

hydrogen imo

atomic hydrogen

is

C6)

Here [llj]
of

denotes ihc concenmuion of nlolecutar


h>drogen.
li

hydrogen,

and

fjt]

atomic

foltov-sihai

l37)
[h^tpo17^'

lhai is, the relume concentration proportional lo the square rooi of


equilibrium con:.lani

of

atomic concent

ihe

at a given is inversely temperature hydrogen ration of molecular hydrogen. The equilib-

K is

given

by

logK

log^tHj)

2IognQ(H) molecule.

F(U2)/i,
factors are

C8)
in

in

terms

of the

internal free energy of

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

H,. per

Spin

absorbed

F(H,}.

[he zero

Hjdrogcn

is very dilute

in

intergalactic

space.

Example:

pi! and ihe limitation of water.

In

liquid

waicr

ihe ioni^lion

process

H2O*~>H+ + OH\"
eeds

09}
cquilibfium
i

to

a slight by

o.ximalcly

txicnt. Al room tcinpcraluic she coiiccmraikm product

the reaciion

D0}

Chapter

9;

Gibbs

Free finersy and

Chemical Reactions
per liicr. inpurcualcr\302\243H*l donor. The concentration
\342\200\224

where ihc jonac


!0\021molr''.
^nefcasco

concentrations

arc given
iictu the

in

moles prolon

fOH

\021

^=

An acid
oy

is said

lo aa as a
wai^r

of H* ions is

aGGin&

z\\t\\

to llic

as required

lo

mainiain

of OH
decrease

\"

product
by

ions

can

be increased

\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

accordingly.
ionizaiion

The physical
process

siaie oi wafer
H* does

is more

complicated

of

than ihe equation


but

ihe

suggests\342\200\224ihc

ions ate

not bare

protons,
vulidily

are of

associated ihe reaction

with groups*

of H2O molecules. This


convenient

not sigiltficantry

affect ihe

equation.
it

is ofien

lo express theacidily

oraikalinii) otasolulionin

letmsof

ihe

pti,

defined as

pH s -log10[H+].

D!)

The

pH

ota moles

solution

concentration in The Human

slrongesi blood

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

Kxati\\ple2

Kttictic

modelof/nms

action.
AB

moieculc
nB,

nAB denote

AB. We suppose that t!ie concentrations

is

of A,

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
that

atoms

A and

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

formation

o[AB

in

a collision

of A

with

B, and

ihe

process, the ihemiat decay of AB into the concermaiions of all consiiiutents

its component ace constant,

nAB

D/C
law

,
of mass

D3)
action
A

a function
Suppose

of

temperature
standard

only. This

result

is consistent

with ihe

that we
B, but

derived earlier by formed


by

thermodynamics.
principally

AB is noi formed
some

by

the bimolecular

collision of

and

is

catalytic

process such as

\"

The

dominant ptolon.

one surrounding

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,

505A958).

\342\226\240 .

Equilibrium

for

IdealCases

Here E is ihe

So long as ttie
is lied the

catalyst which
intermediate

is returned

product

to its original slate AE ts so short lived that


must

ai ihe

end

of the

no significant

seeond step. quantity of A


in

up as AE, ihc ratio iiaiiu/iUb in equilibrium direct above. process A + B<--AB treated proceeds, ihc equilibrium must in equilibrium of the direct equality

actually
The

be

the

and

us if AB were formed what route Hie reaction by same. The rates, however, may differ. inverse reaction rate's is culled the principle
be

the same

No

rnaiier

of detailed

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

coordinate

Figure 9.2
activation before

nnd determines

reaction

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.

The quantity

Chapter 9: Gibbt FreeEnergy


SUMMARY

and

Chemical

Reactions

1. The

Gibbs free energy

G3
is a minimum
in

iff +

pV temperature and pressure.


= p.

thermal

equilibrium

at constant
=

= -a; 2. (cG/3r)H,
3. C(r,p,W)

tfG/cph.,
action

V;

(SG/SN),.P

= W,,(r,ri
ofmass

The

law

for a

chemical reaction is that


IK'

- -^w.

a function

of

the

temperature

alone.

PROBLEMS

/. Thermal expansion near absolutezero,


relations

(a)

Prove

the

three

Maxwell

rela-

(dV/di)P

-{dts/dp),

D5a)

(aVldN)p = +(ap/ap)^ ,
(Qj/cr)jV

D5b)
D5c)

~Ea/dN)x.

Strictly speaking,

D5a) should be written

and
omit

two
those

subscripts
subscripts

should

(lie help
Coefficient

of D5a)
tjicrniiti

and

to appear similarly in D5b) and D5c).It is common that occur on both sides of these Show wilh (b) equalities, the third law of thermodynamics tjiat the volume Coeffi-

of

expansion

approaches

zero as t

-* 0.

2.

Thermal

ionization

of hydrogen.

Consider
Show

hydrogen

in

the reaction

c +

electron on a proton H*. (a) of the reactants satisfy the relation


of an

H*ftH,

wheree isad
that

the; formation
eicutron,

of atomic
as

hy-

the

adsorption

the

equilibrium
I

concentrations

[e][H+J/[HJs\302\253acxp(-//T),

D7)

where

/ is

(he energyrequited to tontze


spins the

atomic

hydrogen,

and

refers to the electron.Negieci the

of

the

particles;

not aSTed
electrons

final

and

concentration

concentration is

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,
result.

{im/2zh2K11 this assumption does


tiQ

The result

given

by

0]~[H]\"V'3\302\253p(-//iT).

D8) connection

A similar

problem arises in

semiconductor
atoms

physics

in

u-jth

the

thermal ionization

of impurity
involves

that

are donors
I

of electrons.

No lice lhat:
A)

The

exponent

^1 and not
Here is

/,

which

shows

that

this

ts not

a simple

\"Boltzmannfactor\"

problem.

/ is

the ionization
to
!

B) The
hydrogen

elccjron

concentration atom

proportional

energy, the square root of the


of protons

concentration.

C)

If we add excess will decrease.

electrons to the system, then (He

concentration

(b) Let [H(exc)]denotethe


first

equilibrium

concentration

of

excited
with

electronic

[H(exc)] andT 3,

K. 5000
of donor

[e]

for

state, conditions

which atthe

the is \\l above ground surface of the Sun,with

H atoms in the state. Compare


=

[H]

1023 cm~

|
I

hnization

(called

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

impurities in semiconductors.

\\ A

pentavalent

impurity

a donor)

4.

Siopotymergrowth. polymers

Consider made

the

chemical

equilibrium

of linear
monomer

up

of

identical

units. The

4-

A'mer

= (A'

-f l)mer.

Let K^ denote liieequilibrium

of a sotution basic reaction step is


constant

for

Chapter

9: Gibbs free

Energy

and

Chemical

Reactions

this reaction,
satisfy

(a) Show from the law


=

of

mass

action

lhat the concentrations

\342\200\242 [\342\226\240 \342\226\240]

[N

1]

[If \"/K.KjKj
for

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

K.v

D9)

(b) Show

from the

Iheory of reactionsthai

ideal

gas

conditions

(an ideal

solution):

wQ(W)

^Bnti2/M,^rm

E1)
is the
Hq{N

where
iVmer

MN is
molecule,

the mass of the Nmer molecule, and


(c)

FN

free energy
+

of one
the
free

Assume
4-

N
t]/[N]

\302\273 j,

so

thai

nQ{N) = temperature

1),

Find

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] for the reaction to go in molecular weight of the monomer is 200. Show that (d) 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

concentration
change

ratio [N

at

room

if there

is zero

in the

Phys.

40,60A972).

5. Pavtkte-antipartkk thermal equilibrium

for the expression equilibrium, (a) Find a quantitative = = n+ n~ in the particle-antiparticle concentration n and reactionA+ 4- A\" = 0. The reactants may be electrons protons positrons; and a Let the mass of and antiprotons; or electrons hoies in semiconductor. the either particle be M; neglect of the particles. The minimum energy spins A\" is A-Take the zero of the energy scale asthe release when A* combines with in for an electron with no Estimate n cm\023 (or a energy particles present, (b) = 300 that 20. The hole is K. with a A such A/t hoie) in a semiconductor T \302\253* viewedas the antiparticic to the electron. Assume that the electronconcentration

classical regime, (c) Correct Iheresult of (a) to let each particle have a spin of Particles that have amiparticfes are usually fermions with spins of \\.

is equai to

the

hoie

concentration;

assume

aiso

titat

the

particles

are in

the
3.

Chapter

10

Phase

Transformations

VAPOR

PRESSURE

EQUATION
t

276
278

Derivation of Point Triple


Example:
VAN

the Coexistence Curve,p Versus

284
284

Latent Heat and Enthalpy


Model
DER

System

for Gas-Solid

Equilibrium

285
287

WAALS

EQUATION

OF STATE-

Mean Field Method

288
van the

Critical Points
Gibbs Free Energy

for

the of

der van

Gas der Waals Gas


Waals

2S9

291

Nucieation

294
ism

Fe

from

agnet

295

LANDAU
Example:

THEORY
Ferromagnets

OF PHASE TRANSITIONS

298
302

First

Order

Transitions

302

PROBLEMS

305
and
dTjdp

of 2. Calculation
3. Heat
4.

1.

Entropy,

Energy,

Enthalpy
for

of van

der Waals Gas

305
305
305

Water

of Vaporization of Ice
Equilibrium

Gas-Soltd

305

5. Gas-Solid
7. Simplified
8.

of 6. Thermodynamics
First

Equilibrium
the

305
Superconducting

Transition

306
307

Model of the Superconducting Transition


Crystal

Order

Transformation

307

Note: tn

the

first section

s denotes c/iV,

the

entropy

per atom.

In

the

section

on fcr

Chapter 10: Phaie Transformations

VAPOR

PRESSURE

EQUATION
volume
by

The curve

of pressure versus
We

for

a quantity

temperature is determined calledan isotherm. consider

the

free

energy

of the

the

isoihcrmsof

of matter at constant substance. The curve is a real gas in which the atoms

or molecules associate
together

interact

with in

one

another

and under

a liquid

or solid

phase,

appropriate conditions can of a system is a portion phase

that is uniform in composition.

Two phases
ofa
in

may

coexist,

with

a definite
the
in

real

gas may
in

show a region in
each phase.

equilibrium the

with gas

other. There

As

boundary between them. An isotherm p-V plane in which liquid and gas coexist 10.1, part of the volume contains Figure

atoms
solid

are isotherms at
which

low icmperaturcsfor
and gas
for

which

and
for

liquid
the

coexist and
liquid-gas

isothermsfor

soiid

coexist. Everything
equilibrium

we say
and the

equilibrium
may

holds also
on a

the

solid-gas

solid-liquid equilibrium.
and

Liquid
temperature
critica!

vapor*

coexist

section of an isotherm only


fluid no

if

the
the

of the
temperaiure

isotherm lies below a critical temperaturerc. Above

how

great
so

a liquid,

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

matter

for severalgasesare Liquid and gas

given
will

in Table
never

iO.t.
along

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
coexist

the entire

will A

evaporate drop

entirely,

leaving

the bell jar

filled

with

H2O

gas at

some pressure.

of

water

exposed

evaporate
the

atoms

from
are

entirely. the
suggested

may already saturated with moisture There is a concentration of water, however,above which into a liquid drop. The volume vapor will bind themselves

to air not

relations

by

Figure

JO.i.
for

The thermodynamic

conditions

the

coexistence

of two
in

phases are the


diffusive,

conditions

for

the

equilibrium

of two

systems that are

thermal,

Vapor Pressure

Equatio

Liquid

Liquid

+ gas

Gas
reyj

Figure

IO.I

Pressure-volume

isotherm
and

of a
Hquid

gas

at a

such that liquid temperature is, t < tc. in the two-phase

gas phases

region of

may coexist,that 4- gas the pressure

is constant, but
Efiei^

the s^nclc

volume

is only

<t

and its
piston

vapor are in
down,

may change. At a given lempcrature a Jjtjuiu v*iluc of tltc ptcssurc for Vvh^cri at we move the Jf this pressure equilibrium.
the

pressure

some of the gas is condensed to liquid, but remains unchanged as Jong as any gas remains.

Table 10.1 Critical temperatures


T,.
in

of

gases Tt, in

He

5.2

H2

33.2

Nc
Ar

414

N.

126.0

151

Kr

210
289

Oj
7

1543
647.1

Xc

CO,

.W.2

Chapter

10: Phase

Transformations

and mechanical contact. Thesecondilions are


or,

that

tj

t2:

fit

p2;

pl

for

liquid

and gas,
*j

18\\

Ml

/Jj,;

Pi = Pg
and

.
phases.

A)
Note that

where the subscripts / and g denote the chemical potentials of the same chemical

liquid

gas

the

species

in the

two phases must be

equal
pressure

if

the and

phases

coexist.

The chemical

common

temperature

potentials are evaluatedat the common of the liquid and gas, so that
=

/l,(p,T)

/ijl

B)

At a
the

the general point in the p-x plane alone is stable, and if liquid phase
may

two
ns

phases
<

Pi

coexist: If /i, < ng the gas phase alone is stable.


do not
A

Metastable phases
phase

occur,

by

supercooling

or superheating.

metastable a

may

have

temperature

for which

a transient existence, sometimesbrief, sometimes long,at another and ntore stable phaseof the same subslance

has

a lower

chemical potential.
p

Derivationof the Coexistence Curve,


Let pQ
+

Versus

be the pressure for


that

which the

two two

phases, phases

z0.Suppose temperature
Pa

liquid and also coexist


in

gas, coexist at the at the nearby point


phasescocxist

dp;iQ

+ rfi.Thecurve

in thep.T

divides

the

p, t plane into a

phase diagram, as

plane along which the two


given

Figure

10.2

for H2O.

It is a

condition of coexistence that


C)

dt).

D)

Equations

C) and

We

make

relationship betweendp a series expansion of each sideof D) to


D) give a

and

dx.

obtain

-.

E)

ion

ojthc

Cot

Figure
and

10.2
the

relationships jiB in

shown.The phase

Phase diagram of H.O. The chemical poienmls /t,. ;i,. solid, liquid, and gas phases ate
of the
boundary

here

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.

375.

-100

100

200

300
\302\260C

400

Temperature,in
In

the

limit

as dp

and dz approach zero,


F)

by

C)

and

E). This

result may

be rearrangedto give

which

is the differential

curve equation of the coexistence

or

vapor

pressure

curve.
which The derivatives of the chemical potential

occur

in G)

in terms ofquantities

accessible

to

measurement.

In the

expressed treatment of the Gibbs

may be

Chapter 10: Phase Transformations 9 we

free

energy

in Chapter

found

the

relations

With

the definitions
v

V/N,

5 =
each

o/W

(9)

for

the volume

and entropy
V

in per molecule

phase,

we have

1 (cG\\

(dp\\

)JJ
Then

G)

for

dp/dt

becomes

01)
Here

~
sa

st is

the increase
the

of entropy
the

of

the
vg

system
\342\200\224

when
ihc

moleculefrom
of the system

liquid

to

gas, and

t\\

is

we transfer one increase of volume

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
when

we

transfer

one molecule

to coexist.The number varied, subject only


numbers

of to
in

molecules

in each

phase

will

vary

as

the

volume
(Va

is
the

N,
the

+ Na

A\\

constant.

Here

Ns and

are

of molecules
quantity

The
be

sa

s, is

gas phases, respectively. liquid related directly to She quantity of heat


and
transfer

that

must

added

to the

sysfern to
system

one

moiecule of

reYersibly

from

the liquid

to the gas, while keepingthe

temperature

the

system

constant.

(If heat is
will

not addedto
decrease

the

from

outside

in the

process, the

temperature
of

when

the

molecule

is transferred

to the gas.)The quantity


5'}'

heat

added

in the

transfer is l1Q ~
\"
TE*

A2) the

by virtue

of the connectionbetween

heat

and

change

of entropy in a

reversible process.The quantity


L

tEs

A3)

Dcritaiion

of the

Coexistence

Cur

defines She latent heat of


calonmetry.

vaporization, and is easily

measured

by

elementary

We let
A*\302\253

i-g-v, molecule

A4} is transferred

denote

the change
gas.

of volumewhen
A1), U3),

one

from the

to

liquid

she

We

combine

and A4) to obtain

A5)

This

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

as the

phaseis
replace

very

much

larger

than

in the

liquid (or solid)phase,so that

we

may

Av by vg:

Avsva=
At

vt/yr approximation is very


=
good.

{16)
to the

atmospheric

pressure

i'9/i;( ^

!03, and the

(b)

We
A6)

assume
may

that
be

so

that

the ideal written as

gas law pVg


Av

Ngz

applies

gas phase,
A7)

zip.

With these

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)

Chapter

10: Phase

Traasfortnat

logp

+ \342\200\224Z-0/i

constant; LQ as

) =

p0CXp(-L0/T)

where p0 is a constant.We

defined

the latent

one

heat of vaporization of

nioiecuie.

If Lo

refers

instead

to one

mole, then

where

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

gas constant,

R =

versus 1/T.

The curve is linear over

substantial

regions,

consistent

with

the

-Crit

ca! p

Jin.

\\
id

wa

er

X 103 \342\200\224 1 atm


ofwaier

Vapor

pressure

and of
iine.

ice

\342\226\240-

\\

102

is 1/T.
The

The vertical scale is dashed line b a straiglif

\"

10

\\

Si*\"

vc

\\ s

V
\\

\342\200\242Ice 1

1.5

2.0

2.5

3.0 3.5 4.0


lO'/T,

4.5

5.0

in

K~\302\273

4
in

Tcmperamre,
Figure

10.4

eial.. Journal of
A959)-

Vapor pressure versus iemperaiurcfor 4He. After H. van Dijk Research offheNauonal Bureau of Standards 63A, \\2

approxmiate

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
in

B0). The

is widely

used

the

measurement

Chapter

10: Phase

Transformations
4He

of a normal solid. But

is a

quanhim

3He,
(Figure

the

slope 7.15),

of and

the

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.
in this

liquid. For another quantum liquid, curve is negative at low temperatures

region the

of the

solid. The

Triple

point.

The

triple

poin!

of

a substance

is that

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
vapor The

pressure iriple substance

of point

both

phases.
atmospheric
the

temperature
at

This pressure is the triplepointpressure. is not identical wish the melting temperature
pressure.
point

of

She

Melting

somewhaton pressure; triple under common equilibrium


the

lemperaSure

is the

temperatures depend meiSing temperature

For
pressure

water

the

triple

point

melting
such

temperature;
that

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

defined
Latent

the

triple

point, of

water is exactly273,16 K;seeAppendix

B.

heat

and enthalpy.
at

Tile latent heat

ofa
to

phase

transformation,

as

from

the liquid

phase to she gas phase,is equal


phases

t times

of the
difference enthalpy.

two

constant
-f

of The

pV

The pressure. the two between


is dH

latent heat is also equal to the phases, where H is


+
applies:

the entropy

difference

called

the

differential

= dU -f

pdV

Vtlp.

When

we cross the

coexistence curve,the thermodynamic identity


Tito

dV
~

-f- pdV
//,. Thus
+

(}tg

jt,)dN

B2)

On the coexistencecurve jig

at constant
\302\273 Ml

pressure
Ha

L
Values

\302\253 tAa

\302\273 At/

pAV

- llt.
heat

B3}
capacity

of//

are

tabulated;

ihey are found

by integrationof the

at coiisnint

pressure:

\342\200\224-

Hr-

Derivation

of the

Coexistence

Curve, p

Ver

jc,,

B5)

describe

Example: Model system for a solid in equilibrium

gas-sotid equilibrium.
with

We

construct
We

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\224 The energy states of a single oscillator arc ntioi h a or zero where is r.o, positive integer in o:.e we suppose itial each ntom can oscillaic (Figure 10.6). For the sake of simplicity only dimension. The result for oscillators in [hrce dimensions is left as a problem. ol a single oscillaior in llie solid is The Junction pariiiion
a gas,

pressurecurve

for

ihis

model.

a simple model can derive ihe easily a to apply liquid.

io de-

Z, =

\302\243\302\253p[-(n/10>

eo)/r]

= expOWt)

=
\302\243\302\253p(--,,Aa./T)

B6)
The Ziee energy

F, is

F* = u* ~
The Gibbs free
energy

Tff,

-tlogZ,.

B7)

in the

solid is, per atom,


Vt

Gs

\302\253

to-, +

pt',

=>

Fs

pvx =

//,.

Figure

10.S

Aloms

in a

solid

in

cqmSibn

wiih

aionis

in the
atoms

gas phase. The equilibri


ol temperature.
in [he

pressureis a energy ol the


than

function

The

solid phase is
in

lo
\\

in

aioms

gas lo be lends

ihe

phase, bm the cmiopy of


higher

the

gas phase. . The


y

equilibrium configmaiion is dfiietiiiiacd of the iwo ciTccls.A! low cotmtcrpkiy

ihe

lanpemSurc most of
at
may high

iIk

atoms

;src in ll

temperature be

all ot

most of

ihe a

in ihe

gas.

Chapter

10: Phase Transformation

(u. The lor of frequency ssumed 10 be % below that

o(a

in!he

gas phase.

Ground Male <


bound

aloui

The pressure

in

the

solid

is equal to

that

o[

[he gas with


smaller

volume
If we

i>i

per

atom

in ihe

solid phase is much


(or

than

but Uie which il is in contact, atom in [he the volume vt per

gas phase: c, \302\253 vr


the

\342\226\240

neglect the term absolute activity is

pv, we have

the chemical

potential of

[hesolidp, S

whence \342\200\236

,/t) =

exp(-logZJ

<stp(-to/i)[l We the

B9)
gas

make

the ideal to be

atom

gas approximation to describethe zero. Then, [rom Chapter 6,

phase,

and we

take Ihe spin of

'
\302\253q

C0)
'\"a

t\\
).f

The gas is in

equilibrium

with

the solid

when

or ).\342\200\236

inQexp(-E0/t)[l

- exp(-/1<0/t)].

C1)

we

insert

nQ from

C.63J:
=

C2)
(j^j

Van

Der

Waats

Equation

of State

VAN
The

DER WAALS EQUATION


mode! the

OF STATE

simplest

modified the

ideal

interactions

below,

he was

led to a modified equation of stateof the


(p

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
form

give

+ N2a/V2)(V

- Nb) = Nx ,
for

C33
N

known

as

the

van

der Waals

volume

V. The

a measure

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 a, b are interactionconstantsto be defined; of the long range attractivepart the of mieraeiion

equation of state. Tliis is written

atoms

in
a is

constant

between

two

short

range

repulsion

tlic

the ihcrmodynamic
transition.
F.24),

= properlics of the model


general

relation p

F(idealgas)

-NT[log(na/n)
distances

+ i]. be treated
free

C4| approximately as
V

The hard core


if

repulsion

at

short

can
but

the

gas

had

available

not the

volume
therefore

V,

the

volume

Sb,
n

when
=

b is

in C4) by

the volume per molecule. We replace ~ of instead Nb). Thus, C4),we N/{V
F

the concentration
have

N/V

-NT{log[)fQ(V
for

- Nb)/N] +
intermolecular

1}.
attractive

C5}
forces.

To

this

we

now

add a

correction

the

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.

Chapter

10: Phase Transformation*

Mean Field

Method
a

There exists
taking

simple

approximate

method,

called

the mean field


interactions

method,
among

for

inio

account

the effect

of weak long range


widely tp(r)

the

particles system.The most Let gases and to ferromagnets. of two atoms separated a distance

of a

known denote

applications the

potential

method are to energy of interaction


of the

by

r. When

the concentration

of atoms in
atoms

the

gas

is n,

the

atom

the average value of at r = Ois

ihe total interactionof all other

on

C6)

where -2a denotes


useful

the

value

of

ihe

convention.

We exclude the

integral \\dVip{r). The factor of two hard core sphereof voiume b from

is

the
n

volume
constant

of integraiion. In writing C6) we assume that the concentration ihe of the gas. That volume accessible to the molecules ihroughout we use the mean value of n. Tins assumption essence is the of the mean

is

is,

approximation. of concentration
By language

assuming regions

in

we

say

thaS

the

field we ignore the increase concentration uniform of strong attractive potential energy. In modern between mean field method neglectscorrelations
\" \342\226\240

interacting From

molecules. C6)

it follows

that

the interactions
volume

change the energy and

the

free

energy

of a

in gas of N molecules

V by

AF

s MJ =

-\\BNna)
problems;

*=

-N2a/V.

C7)

The

factor

j is common to self-energy
molecules

it arranges

that an
as |N2.

interaction

\"bond\"between two
exact

is counted

only once in
we

the total energy.The


for the

number

of bonds

is

|-N(N - I), which

approximate

We add C7) to C5) to

obiain
yas:

the

v;m

der

Waais

approximation

Heimholu

free

energy

of a

F(vilW) =

-.Vi{log[\302\273u(l'r

Sh)/N~\\

+ 1}

- Nza/V.

0$)

The

pressure

is

C9)
'\342\226\240-^\302\253'\027^5-F

Critical Pawls for

the

Figure

10.8

forces that of a volume


suggests

pressure
be

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
Direciions
ad

on molecules

used

as ihe

pressure

in

the

gas taw.

o o
V

Q
o

O
0

O
o
\302\251

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

10.9

Hie

coniainer

each

of volume

o
Q

(p

+ N2a/V2){V

~ Nb)

\302\253 A'l

D0)

der
10.8

Waals
and

equatum of
10.9.

staSe. The terms in

and

b arc

interpreted

in

Points ne the

for She van

der

Waals

Gas

quantities pc ^ a!21b2\\
Vc

3Nb;

xc

^ 8a/27b.

D1)

Chapter

10:

Phase

Trans/or,

. P/Pc

0.95tt

Figure

10.10

Tile van

der Waals

the

critical

temperature.

Courtesy of R. Cahn.

equation of

stal

In termsof

these

quantities

the

van der

Waals equation
l\\

becomes
D2)

3 This equation is plotted in temperature tc. The equation

\\(V
10-10 be

8t

f7HJAH
Figure may

3/
for

3t/
several

written

near the temperatures in terms of the dimensionless

variables ps
pjPc\\

9sVfV.\\

e t/tc ,

D3)

D4)

This
si!

result

ts

known
alike\342\200\224if

as the
they

law of
obey

gases

!ook

correspondingstates. In termsof p, V, t, the van der Waals equation. Valuesof a

Gibbs

Free

Energy

of the

van

(let

M'aah

Gas

and b are
substances

usually obtained
at the
not

by

fitting

to

the

observed

pc and

tc. States of two

Realgases do
At

same p,
obey

Vy x are

called

corresponding

states of
V

ihe subsiances.
f has

the

equation

to high accuracy.
at

one

point,

the critical

point, the curve of p versus


Here

constant

horizontal point of inflection.

the

local

maximum

and minimum

of the
liquid

P~V
phases.

curve

coincide,

and

At a

horizontal

is no separation between the vapor and of inflection point


there

aThese

@iby D4) if

conditions

are

satisfied

and Above

tc the critical tt

no phase

pressure, separation of the

9 = 1;i 1. We call critical volume,and criticaltemperature,


p = 1;
\342\226\240=

pc,

Vet

respectively.

exists.
Waals
der

Gibbs

Free

Energy

van

der

Gas
Waals

The Gibbs

free energy of the van

gas

exhibits

the !iquici-gas at phase transition have from C8) and C9) the result
=
-\342\200\224^

constant

pressure.

the characteristics With G = F + pV,

of
we

G(x,VtN)

-^
a function cannot

of

Nt{log[\302\273u(K

Nb)/N]

+ 1],

D6)

This equation p, t, Unfortunately


N.

gives

as we

V,

t,

N;

the natural

variables
analytic

for G are
form

conveniently
want

put G

into an

as

function

of pressure
ft,

instead ofvolume.We
by

G(z,p,N)

because

we can

then

obtain ;i(t,p)as G(z,p,N)/N

(9.13).

It is

relation
in Figure
temperature
represent the

of G versus pare plotted results of numerical calculations 10.! 1 for temperatures below and at ihe critical temperature. At any the lowest branch represents the stable phase; the otherbranches
=

/i that determines the phase coexistence

fig. The

unstable

phases.

The pressure

at which the branchescross determines

gas and liquid; this pressure is calledthe equilibrium !0.12. for G versus t are plotted in 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. coexist between and The value or The phases of V2 is determined Vx V^. Kj by the condition that /i](r,p)== }ia{x,p) along the horizontal line between Vx and
transition

between

Results

V2- This

will occur if the

shaded area belowthe Jine

is equal

to the

shaded area

Chapter

10;

Phase

Ttansfo

-0.40

t\342\200\224

-,-Vapor[

rasure

/
\\

Figure 10.11

(a) Gibbs free


of stale:
versus

energy

versus

pressure
of

for van
R.

der

Waals

equaiion

i = 0.95tc. Courtesy
for van der

Cahn.

(b) Gibbs

stale;i = %..

free energy

pressure

Waals equation of

above

the

line.

To see

ihis, consider
dG \302\253 ~adx

Vdp +

pdN.
of

D7)
particles.

We

have

dG

Vdp at

constant i and constanttola!number


and

The

difference

of G between V\\

V1 is

G,-G,=

fWp,

D8)

j ~p

0.95

nqb =
LiqutaS^

\302\273bic

G/Nrc

' 0.986

0.984

0.988

0.990

't/t,
(a)

\342\226\240

Figure

10.12a
=

of slale a! p

Gibbs free energy


0.95 pe. Courlesy

versus temperature of A. Manoliu.

for

van

der Waals

equalio

=
p

1.0

nqb

\\
-

\\
\\oas

-2.70

0.90

I.OO

1.05

1.10

t/t,

(b)
Figure

10.12b

Gibbs
crilical

free energy
pressure pc.

versus temperature for van

der

Waais

cquatiO!

of slate

a! the

Chapter

Id: Phase

Transformations

conslan

- ^Liquid
-Cocx

Stetice

fir

\\

<\302\243

a
|\\

as

s.

v.t

10.13 Isotherm of van lemperafure belowliie critical


Figun e less
above
than Kj

der Waalsgasat
lempcralure.

a
volumes
and

For

Vt only only

!hc liquid

phase exisls; for

volumes
Vx

Ihe system line


liquid

lliegas phase exisls. Between in stable equilibrium lies along the

V2

coexistence

and is
and

liquid
volumes

and

an inhomogencousmixture of two phases. The gas phases coexist. The proportion of liic be such lhai ihe sum of fheir gas phases must
the volume
V

equals

that

is available.

bul ihe
When

integral isjust ihesum ofthe


Ihe

shaded

areas,

one
G?(t,/>) in

negalive
the

magnitudes
Hie

of the

areas are

equal,
line

and one positive. Gj(t,p) and [is{x,p}=


In equilibrium

/^{r,p) along
we require
Nuclcatiou.
j.tg

horizontal

coexistence

drawn

figure.

/*,.
Aji \342\200\224 \342\200\224be

Let

ftg

;i,

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

where

y is
will

the surface
grow

free energy per unit


Gt <

area,

or

surface

tension.

The liquid

drop

when

Gr
=

An

unstable

maximum

of AG

is attained

when

ti&G/dR

0 =

-4nR2iii&n

+ SnRy ,

E0)

Rc

\302\2532y/H,A/i.

E1)

This
fend larger

is the
to R tlie

critical radius
drop
will

for

nuclcation

of

a drop-

At smaller
Jower

R the
free

drop

will At

evaporaie

spontaneously
tend

because

that

will

the

energy.
lower

to

grow

spontaneously

because that,
be

too, will

the

free energy.

must that energy barrier (Figure10.14) fluctuation in order fora nucleusto grow beyond in E1) D9):

The free

overcome

R,. is found

by a ihcrni.i! substitution of by

(&G)C

(lenPW/nMl*I}.

E2)

If we
to

assume [hat
Aji as

the

vapor

behaves

like an

ideal gas, we can use Chapter5

express

Aft

-r

tlog{p/peq)

where

p is

pressure
for

the vapor pressure tn of the bulk liquid (R ~*


at

the

gas

phase

and
y

pe<l

the

equilibrium

vapor

co).

We

use

72erg

cm\022 to

estimate Rt

water

300 K

and p

= l.J^tobel

x !0~6cm.

Kcrro

magnet

ism

means a magnetic which has a spontaneous magneticmoment, field approxifield. We the mean moment even in zero applied magnetic 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

\302\253 AM

E3)

where

I is

a conslans. We

take

the

external

applied

field as

zero.

Chapter

10:

Phase

Tram/or

Critical
*\"

barn

t for growH,

or

cortdcnsut

3n nuclei

fx

'
1

ondensation

,
__

\\

nuclei

evaporate

\342\226\240'\342\226\240\342\226\240-

Figure 10.14
function

Excessfree
radius

energy

of drop

relative lo

gas, as
gas

of

drop

R, both m reduced units. The

is

supersaturated
this

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
curve

as drawn,

barrier.

Consider

a system with

and of

magnetic moment fi. In Chapter3 we magnetization in a field B:


M

a concentration h of magnetic atoms,


found

each

of spin

an

exact

result

for the

= HjitanhOiB/t). this

E4)

In the mean field

approximation

E3)

becomes, ,

for a
.

ferromagnet,
'..

Me . \342\226\240\"\342\226\240_\342\226\240_\342\226\240

n/nanh(/dMA)

'.

E5)

Fcrromu^cth,

0.2

0.4

0.6

0.8

1.0

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
Figure

10.15

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

in

curve for
m s= 0,
(or
this Curve

2 intersects

the

straight

iine

in only

al

as appropriate for ihe is no externai applied magneiic


t =

paramagnetic The fieid).

region (iherc curve for / = i

it) is
i =

tangent

lo

ictnpetalure for

murks

the suatght Sine m at ihc origin; ilic onset of fcrroiiiagnetisiu.The ferromagnciic in at about
in

0.5 is in

iiie line

region
s= \302\273i

and
n/i. As

tmersccts ihc straight


1
-\342\200\242 0 the

0.94

intercept
moments

moves up to
are

l.so

that all

magneiic

iined

up at

absolute zero.

a transcendental equation for


with

nonzero tn
f

we write it
temperature

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
M.

We

shall

see that

z/n[i2X,

whence
=

hi

ianh{Hi/r). this

E6)

We plot the right


as

and

left

sides

of

equation

separately
the

in

Figure

10.15. The

intercept of the two curvesgives


temperature

The critical temperature of interest.


curvesof
M

ts

I,

;is functions of \302\273t, value of m at Ihe = or zt h/i^L The

versus

x obtained

in ihis

way reproduce

roughly the featuresofthe

Chapter

10;

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.

experimental

resuiis, as

shown

in

Figure
to

10.16 at z

decreases magnetization
LANDAU

smoothly

zero

for nickel As t increases the = rc, called the Curie temperature

THEORY

OF

PHASER

TRANSITIONS
of the

Landau gave a systematic


transitions

formulation

mean

field theory

applicable

to

a large

consider

systems

at

free

energy

F =
with

We variety of systems exhibitingsuch transitions. their Heimholtz constant volume and temperature, so that \342\200\224 in The ta is a minimum big questionis,a equilibrium.

of phase transi-

minimum

respect

to what variables?
the

It isnot helpful
can

to

consider

all possible

variables. We
the

suppose here that


Greek

system

be described

by a single order

parameter the
system, superconducting

\302\243,

dielectric
electrons
bonds

bonds totola!
will

might be the magnetization in a ferromagneti in a ferroelectric system, the fraction of polarization A-B in a superconductor, or the fraction of neighbor
xi, which alloy
c,

in ait

AB. In thermal
cc{c).

have

a certain

value

In

equilibrium the order parameter the Landau iheory we imagine Ihat \302
energy

can

be indepaideally

specified,

and we consider the LandauTree


=

(\"unction

FL(\302\243.x)

E7)

the energy and entropy are taken when the value \302\243 no! necessarily c0. The equilibrium specified
where

order
value

parameter

has

the

\302\2430{t)is

the

value

of

Landau

Theory

of Phase

Transitions

c, that

makes FL a minimum, at a given the actual Hdmholtz t, and f(r) of the system at i is equal lo thai minimum:

free energy

F(t)
Plotted as a function than one minimum.
of

\302\273

Fl($0,t)

FL(\302\243r)

if

* \302\243

Co-

E8)
have

for \302\243

constant

r, ilic

first order
We

The lowest of these transition another phase i is increased.


minimum

Landau free energy may


the becomes

more

determines

equilibrium the

state.

In a

lowest

minimum

as

restrict

ourselves
in \302\243

to systems absence

function
ferroelectric

of
systems

the

of

Landau (\"unction is an even and ferroapplied fields. Most ferromagnetic


for which Ihe
We

are

exam
of

pies of
that \302\243

this.
it

also

assume

that

F 1(^,1) is a

sufficiently
\302\243\342\200\224

well-behaved function
something

can
for

be expanded
granted.

in a

power series in
function of

that

should

not be

taken

For

an even

as \302\243,

assumed,

The

entire

temperature
ga\\

dependence of
coefficients

FL(\302\243,x)

is

contained
for

in the
experiment

expansion
or theory.

coefficients

g2,gx,

g6- These

are matters

when changes sign at ^(x) example of a phase transitionoccurs a temperature i0, with y4 positive and the higher terms negligible.For simplicity

The simplest
take

we

g2(t)

linear

in i:
<72(r)

(r

- to)* .
as

F0)
constant

over Witli

the these

temperature idealizations,

range

of interest,

and we take g4

in that

range.

The
certainly

form F0)
fails is not

and cannot be accurateover a very wide temperature range, on tembecause such a linear dependence at low temperatures consistent
with

it

temperature

the is \302\243

third

law. at the

The

equilibrium

value of

found

minimum of

FL{$

;t)

with

respect

which

has the

roots

f~Q

and

= (to

- r)(a/g4).

F3)

Chapter

iff;

Phase

Transformations

With a
energy

and ga positive, the root c,


function

0 corresponds

to the

minimum of the free


is

F1)

at temperatures

above i0;
J=Xt) =

here the HelinhoHz freeenergy

0g(l).

F4)

The other root, c,2


energy

(a/gj(to

function

at temperatures

t) corresponds to the minimum of the free below t0; here the Helmhoitz is free energy

The variation

of F(r) with
a function
ihe

temperature

of

FdZ'J-)

as

of

for \302\243:

and Figure 10.18,

temperature

10.17. The variation ihree is shown in temperatures representative is of the equilibrium value of \302\243 dependence
is shown

in Figure

shown

in Figure

10.19.
in

elergoes

Our model describes a phasetransition


continuously

which

to

zero

as the

temperature

the value of the order paratnis increased to t0. The entropy

Figure for an

10.17 Temperature dependence of (he free energy of the second order. ideatized phase t ransition

Figure

10.18

Landau

free energy

function

versus

at \302\2432 t0 the

As the reprcscniaLivc temperatures. the equilibrium value of \302\243 gradually


posiiion

temperature drops below


increases,

;is tic fined

by

of the minimum

of the tree energy.

Figure

10.19

Spontaneous
for

polarization

versus

temperature, curve is not realisticat use Of Eq. F0): the third


thatdf/rfr

a second-order low

phase transition. The because of the temperatures of thermodynamics

law

requires

->0asi-*0.

Chapter

10: Phase

Transformations
at t
a a

\342\200\224

dFfdz

is continuous
Such

= rQ,so that
is by latent

there

is no

latent

heat at the

transition

Transitions
discuss

temperature f0.
with

transition

nonzero

them presently.

The real
the

second order transitions;


superconductors.

best

definition a second order transition. order heat are called first we transitions; a remarkable world contains of diversity arc ferromagnels and superexamples

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) =
where

-\302\261

F6)

ihe factor

j iscommon to self-energy

problems.

The

entropy

density is given approxi-

g{M) = constant in Ihe

M2J2nn2

F7) unit

regime

in

which

\302\253

n/j.

Thus

the free energy

fursciion

per

volume

is

FL{M) ~

constant -

\\M2(/.'~

\342\200\224A +

lermsof

higher

order.

F8)

At

Ihe

transition

temperature

the coefficient of M* i0

vanishes,

so ihat

, \302\273}i2>.

F9}

in agreement

with

the

discussion

following

E6).

First Order
A

Transitions
characterizes
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

latent

heat

a first order

lion order

at

constant
transitions

in metals transformations

when the expansion coefficient g*

is

negative

and

gb Is

positive.

We

consider

first

Order

Transitions

Figure first

l(K20 order

Landau transition,

free energy

function

versus

i1

m a
At

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
at
\302\243

at representative function has equal minima For t below rf the as shown. \302\243

temperatures.
=

xc

0 and

The extrema of

this

function

are

given

by

the roots

FigureJ0.20:
G1)
Either \302\243

0 or

G2)
At with

the c,

transition ~

temperature

rc the

free energies will

be

equal

for

the phases

0 and

with the

root c^O.

The

value

of

xc will

not be

equal to r0,

Chapter

10;

Phas

_60

-40
T

-20
rrt in K

and the
xc.

order parameter\302\243 (Figure


results

10.21}
in

does
second

not go
order

These

differ from
to

those

the

continuously to zero at phase transition treated


A

weui earlier, where \302\243


transformation

zero

may

show

hysteresis,
a second

at continuously as in supercooling
order

t0 or

tf.

first

order

transfor-

supcrsaturation,

but

no

hysteresis exists in

transition.

1. The

coexistencecurve in the p-x planebetween Clausius-Clapeyron equation:


dp

two

phases

must

satisfy tiic

where

L is

the latent heat and


heat L

An

is the

volume

difference per pV is the

atom between

the two
2.

phases.

The

latent
van

~ H, '

- Hlt

where

V +

enthalpy.

3. The

der

Waais

equation

of state

is
-

(P +

N2a!V2){V

Nb) =

Nx.

4. In the

Landau

free

energy

function

the energy
not value \302\243,,

and entropy
necessarily

are

taken

when

the

thermal
when \302\243

parameter has the specified The function Fl equilibrium value \302\2430.


the order
system
the

is a minimum

with respect to

is

in

thermal

equilibrium.

5,

A first

order

phase transition is characterizedby

Intent

heal

and

by

hysteresis.

PROBLEMS

/,

Entropy^

energy,

and

enthalpy

of van der

IVaah gas.

(a)

Show

that

the

en-

entropy

ofthe

van

dcr

Waats

gas is
N[log[nQ(V

o(b) Showthat
the

Nb)JN]

+ 1}.

G3)

energy

is

U =

INi.+ pV
i%

N2.ii!V.

G4)

(c)

Show

thai

the

enthalpy//

= U
=

H{i,V)

|Nt

+ N2bx/V
NhP

2N2ajV\\

G5)

//(r./>) arc

-jNr +
in

2NuPfx.

G6)

All

results

given

to first order
for

the

van

der

\\V;ials correction from

terms o, h.

2. Calculation of
equation

(IT{dp

water.

Calculate

the

value

of elT/dp

wmcr. The keivin/atm.

heat of vaporizational
of

near p

~ 1 atm

the vapor
Jg\021.

pressure equaequilibrium the result

for

the

100Xis 2260
pressure

Hquid-vypor
Express

of in

3. Heat of vaporization
Hgal
of vaporization 4.

ice.

The

of water
Jmol\"'

vapor over iceis3,SSmm


the heat

~2=C
ice

and 4.58
at
~l\302\260C.

mniHgai OX. Estimatein


Consider
\302\273 haS)

of vaporiza-

Gas-solid

equilibrium.

a version
three

we

let the

osciSiators in the

soiid move in
the

of the example in B6}-C2)


dimensions,

which

(a) Show that in

the

high temperatureregime (t

vapor

pressure

is

(b) Explain why


5.

the

latent

heat

per atom

is tQ

\342\200\224

\\i.

GaS'SoU'd

extreme
temperature

Consider equilibrium. that the entropy assumption


range

of interest.

the gas-solid equilibrium under the exof the solidmay be neglected over the temthe ofthe be cohesive Let -e0 solid,per atom. energy

Chapter

10: Phase

Transformatio
that the

Treat the gas as idea!and

monatomic.

Make the

the approximation container,

volume

accessible to the gas is the volume V of Smaller Volume occupied by the Solid,
energy

independent

of the much

(a) Show

thai the

total HeimhoHz free

of ihe

system

is

F = F,
where
minimum

+ F,

\"

-Ufa

N,r[!og(N,/l'il0)

- I] ,
(b) Find

G8)

the
of

total

number

of atoms,
with

N = N,
to N^show

Ng

is

constant,

the mini-

ihe

free energy

respect

that in ihe

equilibrium condition 09)

(c) Find the equilibrium


6.

vapor

pressure.

Thermodynamics

of the

superconducting transition, (a) Show

that

2/i0

th

[i0 ih
the
it

(SO)

SI units for Be. Because Bc decreases with side is negative. The superconducting phase
in

increasing has

temperature,

right
more

the

lower

entropy:

is the

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

Show

that

Cs and

CN, the

heat capacitiesper unit

volume,

are

by

(81)

Figure S.iS is a
than

plot of Cj'T
decreasing

vs

T1

and

shows

that

Cs decreases
For

much
\302\253

faster

linearly

with

r, while
Hiis

Cs decreasesas yz.

tc>

AC

is

dominated

by Cs.

Show that

implies

_-

-0.2

.1

X. Normal

Superconductor

K *STC=1.180

0.5

Temper;

lure.

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.

7, Simplified
superconductors

model of the superconducting curves transition. TheBc(i} that iutve shapes close to simple paraboias. Suppose
Bt(i)

of

most

Bt0[l

d/r(}2].
also t -* 0. on the resultsof
Assume

(83}
that

Assume

that

Cs

vanishes
a

faster
gas

linear in r,
calculate

as for
heat

Fermi

and plot

and ihe latent

the i dependences of
of

than linearly as (Chapter 7}. Draw


I

Cs is
6 to

Problem

he

two

entropies,

the two

the transition.

Show that
Consider.'!

Cs(rc)/Cv(r(}= 3.
crystal that
the

heat capacities,

8.
of form

First

order

crystal

transformation.

can existin
a slrucmre
semperalure

eilher

two.structures,
low

denoted
form

by a
and

siable

temperalure

of the

substance.

If the zero of the


infinity,

'hat and /?. We suppose the /J structure is the stable high


energy

is the stale of
uill

scale

is

taken

as the
==

separated atomsat

then

the

energy

density

1/@) at r

be

Chapter 10:

Pha:
t
\342\200\224 0 will

negative. The phasestable


Ux@)

at

have
in of

the lower

value of U{0); thus

velocity of sound ve U?@). to lower values phase, corresponding


<

If the

the the

thermal excitationsin

/J phase is lower than vx in the clastic moduli for /?, then the

the

phase.The !he energy.


free systems

phase

will

larger

the

thermal

excitation,

have larger the larger


free

amplitudes than in the a the entropy and the lower


energy

Soft

systems

tend

to be

stabie at high tempera!ures, hard


density
with

by the

is

the (a) Show from Chapter 4 that phonons in a solid at a temperature much at

low.

contributed
taken

icssthan the Debye temperature


v

given

by

-~rc2r'i/3Oi;3/i3,

in the
Show

velocity of

all phonons.(b)

Debye approximation that at the transformation

as the

temperature

>-v.-').

(84) trans-

There be ofa classof


will transformation

a finite

real solution if t'p


phase

<

iv

actual

transformations

This example is a simplified model in solids, (c) The latent heat of


that

is

defined

as the

system through the transformation.

thermal energy
Show

must

be

that

the

latent

to carry the heal for this model is


supplied

L = 4[U,@)In

t/,@

(85)

(84)

and

(85), U

refers to unii volume.

Chapter

11

Binary

Mixtures

SOLUBILITY GAPS
ENERGY

310
OF

AND

ENTROPY

MIXING

31-1
318 319
320

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

321
322
325

EQUILIBRIA

BETWEEN

LIQUID

AND

SOLID

MIXTURES

Advanced Treatment: Eutectics


SUMMARY

330

PROBLEMS

330

1. Chemical
2.

3.

Mixing
Segregation

Potentials in Two-Phase Equilibrium Energy in 3He-4He and Pb-Sn Mixtures


Coefficient

330

330
331
331

of

Impurities
Alloy

4. Solidification Range of Binary 5. Alloying of Gold into Silicon

33i

Chapter

11:

Binary

Mixtures

of materials science,and large parts of applications chemistry are concerned of with the biophysics, systems properties multicomponent
Many
have physical

and
that

two

or more
effects

and phases in coexistence.Beautiful, unexpected, important occur in such systems. We treat the fundamentals of the subject

in this chapter, with SOLUBILITY

examples

drawn

from

simple

situations.

GAPS
of

Mixtures arc
have

systems

two

or more

different chemical
with

species.Birjury

mixtures

only
the

two constituents.
mixture

Mixtures
an ailoy.

three

and

four constituents arc atoms,

are called

If ternary and quaternary mixtures. molecules, A

the

constituents

and not

moleatomic

is called

mixture

is homogeneous

scale
contains

to form
two

a single
or

when its constituents are intermixedon an A mixture is heterogeneous phase, as in a solution.

when

it

expression

\"oii

phases, such as oil and their and water do not niix\" means [hat
more

distinct

water.

The

everyday

mixture

does not form

a single homogeneousphase.

Theproperties of
and

mixtures

differ

from

the properties

of pure
their

substances. The
interest. Heteroconstituents.

melting Heterogeneous

solidification may

properties melt

mixtures

ofmixturesareofspeciai at lower temperatures than


melisat

Consider

a gold-silicon

alioy: pure Au

lO63cCand

pure

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

properties

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? Theproperties 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

are common,

Solubility

Gaps

SO/tm
When a mixture of 69 pci Au and 31 pet Figure II.I Heterogeneous gold-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.
form

heterogeneous

tnixlure

if [he

combined
a solubility

free energy of
of

the

Uvo

separate

phases

side by side is
the

tower ihaii the free energy


exhibits will

the

homogeneous

mixture:
the

then we say I hat


A

mixture miMure

hclerogeneous

melt at

gap. a lower [cmperalurethan

separate the

substances

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 do not be and we sel pV = 0. Then volume changes neglected, may
if I he
work,

com-

pressure
involve

and

the appropriate
energy

free energy is
G.

tire

HelmhoUz

free

energy
the

F rather
free

Ilian the Gibbs free


We

We

will usually

simply speak of

energy.

discuss

compounds

well-defined binary mixtures of constituents Ihat do no! form with each other. Our principal interestis in binary Consider alloys.

Chapter H: Binary

Altitun

Many

applications

of

materials

biophysics, have

are

concerned

science, and large parts of chemistry with the properties of multicomponent systems
coexistence.

and that

two

or more
effects

phases

in

Beauiiftil,

unexpected,

and important
of

Ihe fundamentals physical systems. in this chapter, with examples drawn from simplesituations.
occur

in such

We treat

the

subject

SOLUBILITY GAPS
Mixtures

are

systems

of two

or more

different

chemical three constituents

have only two


molecules, A

constituents. Mixtureswith ternary and quaternary mixtures.If the


the mixture

and

Binary species. four constituents


are

mixtures

atoms,

are called and not moleatomic


it

mixture

is called

is homogeneous

an alloy. when its constituents

on an arc intermixed
The

scale

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
to form
a single

is heterogeneous when
everyday
form

does iiot

homogeneous

phase.
from

The properties of mixtures differ

the

melting
Heterogeneous

and

solidification

properiies may

mixtures
a

melt
alloy:

Consider gold-silicon
but

an

alloy

of 69

pet Au

and

Heteroof mixtures are of special interest. lower 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
at
Au-Si
a

properties

of pure

substances. The

the result

of the formationof any iow-me!ting investigation of the solidified mixture shows

compound: phase

microscopic

two

mixture

of almost
with

pure

Au

side

by

side

with

almost
they

Mixtures pure Si (Figure 11.1).

such

properties

are common,
determines
mixture?

and
points.

are

of practical

importance

precisely because

of their lowered melfing


What
heterogeneous

whether two substances form a homogeneous or 3 heteroWhat is the composition of the phasesthat are in equilibrium

with each
understood
evolve dissolve
configuration of

be Theproperties other in a heterogeneous mixture? 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 homogeneous mixture if that is the configurawill lowest to the free energy accessible components. The substances

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, into a phase of almost pure Au !hemixiure 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.
form

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 changes do not involve be neglected, may
a heterogeneous

side

work,

and

the

appropriate
binary

free eneryy
will

is the Hetmlioltzfree energy


usually

rather

than
We

the Gibbs
discuss

free energy G. We
mixtures each

simply

speak

of the free
alloys.

energy.

of constituents

that do not form weil-defined


binary

compounds

wiih

other. Our

principal interest is in

Consider

Chapter Hi

Binary

Mixtures

a mixture
number

of
of

JVA

aloms

ofsubsiance

A and

NB atoms of substance

B.Thetotal

atoms

is

We express

the composition of the system

in

iermsof

the fraciion

x of B aioms;
B}

x
Suppose

\302\273

A'b/N;

\302\273

jVa/N.

the sysiem
given

forms a homogeneous solution,wiih

an

average

free energy

per atom

by

= F/N. form shown


second
two in

C)
Figure

Suppose
this curve

further

that/(.\\)

lias

the functional
ihe

11.2.

Because

contains a range in which


curves
shape.

derivative
points, we

we can draw a line tangent to the curve at


Free

at wilt

d2f/dx2 is negative, x = xx and x \342\204\242 x^.


see

energy

of this shape are common,and


homogeneous

later what

may

cause this

Any

mixture

in the

composition range
D)

x, <
is unstable
shall
with

<

xp

respect

to

two

separate

phases of

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 segregated system
show

composition x, and x^. We

the homogeneoussystem.

Proof

The

free

energy

of a
F
=>

a and segregated mixture of the two phases


NJix,)

j$ is

NfJ\\xfi)

.
phasesa

E)
and

where ,V,

and

Nfi are

the total

numbers of atoms in

ji, respectively.

These numbers satisfy the relations

which may

be

solved

for .V,

and Ny.

0)

Solubility

Gaps

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
Figure

tl.2
with

a solubility

From

E) we

obtain

fjix)
JV

(S)

for

the

free energy
in

of the
a and

two

phase

system.

straight line
through

thef-x

plane.

If we

set
in

.v.

is linear in x and is a v,c see (hat the line docsgo A'3 or.v^,
This

result

the

points

/?. Thus/

(he

interval
p.

between

.y4 and

xfi

is given

by

the point i

on the straight lineconnecting a and

Chapter

II:

Binary Mixtures

We have not yet

made useof

(he

assumption

that

(he straight

line is tangentto

f{x)

that has

3 and /J, and therefore our result holds for any straight line points two points 2 and/Jin common Bui fora with/(.v). 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
at

the

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 so thai their chemical atomic species, equilibrium respect
potentials

satisfy

/*a> = We show
in

/*\302\253;

Pb\302\273

Pb*by (he

(9)

Problem the

i that two

jja and
vertical

/jB

are

given

intercepts
*=

of the two0

point tangent with as in Figure 11.2.


ENERGY

edges of thc/(x)

plot at x

and

a ~

1,

AND

ENTROPY

OF

MIXING

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 A and be the energy B, per atom of the pure substances
referred

to separated

atoms

at

infinity.

Tlie

average

energy

per atom of the

constituents is
u

(uANA

+ vsyn)/N
the

nA

4-

(\302\253B

uA)x ,

A0)

which defines a straight line in

u~x

plane.

per

atom

of

the

homogeneous
is

mixture

Figure 11.3. The average energy for the be than may larger or smaller
of

separate
homogeneous energy

constituents.
niixture excess

In (he example of Figure11.3, (he energy the the of than larger energy separate
the energy

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 in atoms species are interchanged position; entropy (he Because o f interthis a different state of such operation system. generates
is called
\342\200\224

Energy

and Entropy

of Mixing

Figure

11,3

Energy
with

per atom

as a function
energy.
A

of composition simple

in a

sysicm

a positive

mixing

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

than

tlie

two

separate

substances, alloy

erM

of

a homogeneous

(ID

as

plotted

in Figure

11.4. The

curve of aM
composition

versus

x has

that the slope at the ends of the

range

the important property is vertical. We have

N dx
which

X)

bgx

- ioj
I.

A2)

goes

to

+ co

as x

-+ 0 and to \342\200\224 co as

x -*

Chapter II:

Binary

Mixtures

da^/elx

\342\200\224 X

Ffgure

11.4

Mixing entropy.
atoms

Tn

any

mixture

of two constii uenis an


slate
way

interchange of two
mixing

of different

species leads to a new


slates

of the
is the

system. The logarithm of liie number of entropy.

related

in this

Consider

now the

quantity

u[x)

(a

ffjtf

A3)

which

is the

free energy

per atom without

the

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

~-zaM/N in

to fo(x),

we obtain at

Figure
of/0(.v)

11.5. In drawing
itself,

the
for

dependence

because

Energy

und

Entropy

of Mixing

Free energy temperatures.The curve


Figure 11.5

per

atom

fQ is the

versus composition, free energy per atom

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.

The

phase

separation

at 0.8 rw

is apparent.

our

argument

this is
of the/(x)
finite

follow irrelevant. Three importantdeductions

from

the

construction

curves:

(a)
(b)

At

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 thereby -taM contribution, making values of x. to draw a common tangent to f(x) at two different possible
all

temperatures

because

of the

(c)

Above Ty

the

curve

has

a positive

second derivative at al! composilions.

Chapter

11:

Binary Mixtures

We conclude that the A-B system with below the solubility gap temperature tM.

positive
The

mixing
composition

energy
range

will

exhibii

of the

widens with
composition

decreasing

temperature,

but

the gap
finite

can reach the


temperature

edgesof
is a

gap
the

range
in

only
B and

as t -* of B
in

0.
A,

At

any

there
in

finite
3. The

solubility of A
new result

a result

obtained

earlier

Chapter

below Positive is that the mutual solubility is limited only tw. We now discuss three examples. mixing energies arise in different ways.

Example:

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

alloy

which

(he attractive

uA

x)uAA

xuAa

,
result

A4)
is wiiucn

where (t - x)is ihe propoition mean field approximationof

of A and x is the
Chapter

tO. Similarly, =

proportion of B.This for B atoms,


+

in ihe

\"a

X)HAD

N\"UD.

A5)

The total energy is obtained by summing the average energy per atom neighbors,

over is

both

atom

types. Ifeach

atom has

p nearest

The

ip[(l

xJUAA

2jcA

- *Kb +
the

*3\302\253db]-

A6)

factor^

aiises because eachbond is sharedby


as

two

atoms

it

connects.

The

result A6)

can be written

u =

ip[(l

x)uAA

xum]

+ uM.

A7)

is the
Figure

mixing

energy.

On this

model

the

mixing

energy

as a

function

ofx

is a

parabola, as

in

II.5.

Energy

and

Entropy

of

Mixing

A solubility gap

occurs whenever (/'//dx1

< 0, that

is, when

^r From A2),

= -2P[fAB

i(\302\253AA

O3-

B0)

N dx2
The

x{l -

x)

equal

sign holds

for

,x =

$. Wilh -

these results{19)yields
-

T*i

M\302\253ab

iO'AA

+ ^a)]

B2)

as die lower
There

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

carry a large
water

electric

dipole oil-oil

moment bonds.

molecules.

This attraction

that leads to a strong electrostatic attraction which are only is absent in water-oil bonds,

between about

as

strong

as

the

weaker

Example: Mixture of two


homogeneous crystalline

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 mixture

of gold and

structure

Chapter

11;

Binary

Mixture

\\/

Figure

11.6

Tree

energy versus
which

for homogeneousmisiures

composition for cryslallinc [he [wo constituents of the


structures.

mixture

crystallize

in ^ilfcrem

crystal

Two

differe

free energy curves

are involved,

one

for each

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 Liquid

-\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

-..,.-,...

;-.-,,

SIU-*

He m*.Uuivi

at W

tanpcraiures.
ilie two iiefium

The

moat

interesting

liquid mixof

with

a solubility

gap is the

miMuniof

isotopes JHeand JHe, atoms

tiie Toruicr

ocmii fcimjon^ unti of the 'aHer bosons, 1 lie re js a soluoiltty u\302\273io sn the mtx turc oclow 0.S7rCj ii1/ in i igure 11.\027. 1 Ins property ss utilised m the Iicliuitt cJj'tiiion refftccr^tor have a must be positi\\e to The origin of the solubility gap. {Chapter 12). Tito mi.\\ing energy low temperaAt suliieiently is tht! folio\" ing: 4Hc aloiiisarc bosons. positive mixing encray temperatures almost jli \342\226\240*! le afoins have state orbii;tl of the sysicm, vvherc occurs) the ground they

Phaie

Diagrams for

SimpleSolubility

Gaps

10

20

30

40
Atomic

50
percent

60

.70

80

90
pure

100
\342\226\240\"

\342\226\240'He

He

Figure

11.7

Liquid

mixtures of

JHe and

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 second derivative as n1'*,as in Chapter zero

kinetic

3He

Pltase

Diagrams diagram

Tor Simple represents

Solubility Gaps
the temperature

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

with solubility

according gups may be more complex,

to

the

aclual

form of

(he free energy relation/(.v),

but

the

underlying

principles

are ihesamc.

Chapter

II;

Binary Mlxtur

Slabk

Dec omposilion
1

\\

1
1 1

Uns

Figure 11.8 Phase diagram gap. A homogeneous mixture


temperature

for

a binary
below

system
tlic

with

a solubility

oCcomposition

x will

i if

the point
will

(*,i)

Tails

be unstable stability boundary

ai

curve. The mixture


compositions

given by curve with the horteontal


boundary

separate phasesof the the intersections of the stability boundary


line

then

form two
for

temperature

r. The

stability

curve

shown here was


with

calculated quantitatively
fo{x).

for

the

system

of Figure lt.5,

a parabolic

PHASE

EQUIUBRIA

BETWEEN

LIQUID

AND SOLID MIXTURES


When

a small

fraction

of a

the freezes, homogeneous liquid mixture

composition

of

the

solid that forms


readily

is almost always
understood

different

from

that

is phenomenon
mixtures.

We

consider

a simple

liquid and solid model, under two assumptions; (a) Neitherthe


from

of the liquid.

The

the free

energies for

Phase

Equilibria

Between Liquid and

Solid Mixtures

solid nor she liquid has a solubility

gap.

(b) The

melting

temperature

constituenl
We

ta or pure

is

lower

Jhan

the melsing between


fs{x)

consider

a SemperaSure
per

The free energies


shown

atom,

Semperature tb of pure constituentB. and ta ra. Tor the solid and fL(x) Tor the liquid, are

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
qualitatively in Figure
internal

equilibria:

(a) When

x < xL, the


xL<

system

in

equilibrium

is a

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 equilibrium When solid. js a homogeneous (c) a arc The and of and a so!id in compositions xs xL liquid equilibrium phase the of the free temperature dependent. As ihc temperature decreases energy solid decreases more rapidly tlKll of the liquid. The Ungctitiai points in than a phase move to the Icfi, Tliis behavior is rcprcscnScd by diagram Figure 11.9a stinihlr to the earlier representation of the equilibrium curves for composition

(b)

When

x <

xs, the

mixtures

with

phase

separation.

In Figure

11.9b the curve

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

than Figure phase diagrams are more complicated 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 To see this, consider a liquid with the range, not just at a fixed temperature. 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 most

metal

alloys

the

which

was drawn

is nonuniform
homogenizeafterward high in

in composition
by

and is not in
many

equilibrium.

The

solid

may homoge-

atomic

diffusion,

particularly
solids

if lhe
diffusion

for

a long

time. But
remains

for

atomic

temperature remains is too slow, and the

homogeneity

''frozen

in

\"

indcnniieiy.

\342\200\242

The

slandard

iabutatlons
Constitution
binary

arc

by

M.

Hansen,

Coitsilxatlon of binary
supplement,

allays,

McGraw-Hill.

1958;
Shunfc,

R. P.

Edioti,

Constitution

of

of binary alloys, firsi second supplement, alloys,

McGraw-Hill,

1965; R

A.

McGraw-Hill, 1969. .

Figure

11.9

Phase

equilibrium
cxhibhs

btiwccn

liquid

and

solid

mixtures.

In

ihis example
tA

neither phase

a solubiliSy

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
<

x < xlt.

7\342\204\2425i

I412\"C

324

Phase

Equilibria

Between

Liquid

and Solid

Mixtm

Figure

11.10

Mosi
but

liquid
over

mixiuresdo
precipilaSes

not

solidify

at a
from

sharp
t,

Scmperalurc,
higher-nwiliiig lower-mching

a finite

temperature

range

'o ta.

The

consiiluenl consliSucnt

in ihc

solidification

lemperalure

first, thereby enriching the liquid phase and thus lowering She of ific liquid.

Advanced Treatment;

Eutecltcs. There are many


liquid

binary

systems

in which

the

liquid phase remainsa

down

to

temperatures
The

significantly
go!d-si!icon

tower meltingtemperature of the a An and system: mixture of 69pet


compositions

constituents.

below the alloy is such a


At

31 pet

Si starts to

solidify at

370\302\260C.

other

solidification

starts at a

higher temperature.When

we

plot

the

temperature

of alloy oflhe onset of solidificationas a Function composition, obtain Mixtures with two we the two-branch liqutdus curve in Figure 11.11.
solidification minimum temperature liquidus branchesare calledcutectics.The is She eutectic is the eutectic SemperaSure,where She composition composition. wiih two is a The solidifiedsolid at the eutectic solid, phase composition 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. a solubility Such behavior is common among systems thai exhibit gap illthe 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_/^(.\\\")

Chapter

11:

Binary

Mixtures

1600

1400

404\302\260

1200

U
E

1063\302\260

1000

/
\\
\\

1/
10
Au

0\302\260

-31
0
Pure

20

30

40
Atomic

50
percent

60
silicon

10

80

90

100
iwo

Pure Si
Hquidus

Figure

11.11

Euieciic

phase

diagram of

go!d-siljcon alloys.The
37OX

consisisof

branches ihai come


line

and

ihe experimcnial range

composiiion

iogeihcr ai ihe euieciic daia poinls ai ihe mixiurc docs noi

iempctaiure indicaie

T, = 37O;C.The horizonial ihai ihroughoul the eniirc


unlit

complcic

iis solidificalion

ihe

euieciic

corresponding
constituents.

to difTcrcnt
Figure

II.12a

is constructed

crystal structures a and ^ for the two pure confor a temperature above the cutectic

temperature

but

below

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 ($. (c). For xlL < x < XpL, the equilibrium state is a homogeneous liquid. < and For < x or is in a liquid (b) (d). x^ xaL phase x^L < x < Xp$, equilibrium with a solid phase. the As is lowered, faS and fa decreasemorerapidly than/L, temperature and of the the range H.12b narrower. homogeneous liquid becomes Figure shows the corresponding the two curves. solidus phase diagram, including tUe free

the solid

Figure 11.12 Free energies (a)and sysiem.

phase

diagram

(bj in a

At

theeulecltc

temperature

t, Jhe

free energy
eutcctic

to

the

common

tangent
above

to f^

which fL touches the tangent is the

and fps, as in
although
the

of Jhe liquid phase is tangential


11.13.

Figure

The

composition.

composition At x < xt, the

at

free
of

energy fL

iies

(he

tangent,

fL may be beiowthe free energy


eutectic

a homogeneous

solid.

A mixture

of composition equal to

composition

solidifies

and

meits at a

single temperature,just like

pure

substance.

The solidification

of

Chapter 11: Binary

Mixtures

Figurel!.!3

FiCe energies

in

a euseclic

system at t

, andati

< xr.

compositions
and and

away

From

ends ends

at at

the eutecttc a higher

higher temperature at the starts eulectic temperature. Melting temperature


the

euieciic

composition

starls at a

temperature.
melting

The minimum properly of the utilized. The Au-Si eutectic plays


technology:

temperature

of eutectics

is widely
device

a large

role

in

semiconductor

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 comcitlicr the exact cutectie composition desired, B6pet lead) or a different Salt the ice because of the low is on ice melts composition employed. sprinkled
the

cutectie

permits

low temperature

eutectic

temperature

-2L2\"Cof

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 discussion of the free energy curves of Figures 31.12 and 11.13we assumed the lite composition tltat at which the liquid phasefree energy touches

\020

10

20

30

40
Atomic

50
percent

60
lead

70

90

100

pure Sn

pure Pb

10/tm
Figure

11.14 Pb-Sn

{a} Ptiasc eutmic,

of [he
Jackson.

diagram of the Pb-Sn s> stem, after Hatlicn.{b) Microphotngrapf; of J. D. Hunt and K. A. magnified about S0Otimes.Courtesy
S29

Chapter

11:

Binary

Mixtures

tangent

to the

solid phase

curves lies between the


interval,

compositions

xlS

and

xfiS.

In some

the systems this point lies outside

as

if either/aS

and/t

or/flS

and

fL

were

interchanged

iti Figure

.\\2a.

Such

systems

arc caiied

peritectic

systems.

SUMMARY

1.

mixture

exhibits

a solubility

gap when
the

the combinedfreeenergy
free

of

two

separate

phases

side by side is lowerthan


arises

energy

of the

homogeneous

mixture.

2, The
in

mixing

entropy

when

atoms

of different

species are interchanged

position.

For

the alloy

A} _IBI,

we have

3. The mixing

energy

for

nearest-neighbor
=

interactions
-

is
uBB)]

uM

px(l

x)[uAB

j(uAA +

for

p nearest
Hquidus

neighbors.
is

4. The

the

composition

curve
a

equilibrium for a solid


5. Mixtures

with a solid.

curve The solidusis the composition

.xL versus

for

liquid
Xs

phase
versus

in i

phase in equilibriumwith
with

liquid.
are

minimum

two branches to the liquidus curve solidification temperature is called the

called

eutectics.

The

eutectic

temperature.

PROBLEMS

L Chemicalpotentialsm two-phase

equilibrium.

Show
and

that
B of

[eniials ;iA and /jB of phase mixtureare given


with
1.
liquid

die two
by

atomic species A
intercepts

the chemical an equilibrium


in

potwo
11-2

the

oFthe two-point

the vertical
Mixing
3He-4He

edges oFthe diagramat x


in 3He~*He
in

=0

tangent

Figure

and

\342\200\224 1.

energy

mixtures

finite (about 6 pet) as r residual Figure.11.14 shows a finite


remains

andPb-Sn mixtures. The phasediagram of 3He Figure 11.8 shows that the solubility

oF

liq-

in 4He

-> 0.

Similarly,

the

Pb-Sn

phase

diagram

of

solubility

oFPb

in solid

Sn with decreasing

t.

What

do

such

finite

residual

solubilities

inipty

about

the

Form

of the

Function

u(.x)?
1to A, wish A' \302\253 Let B be an impurity the oF can be as linear Free non-mixing parts expressed energy for both solid phases. of x, as fQ(x) = /0@) + x/0'@), 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'
Segregation

3.

coefficient

of impurities.

In

this limit the

4.

Solidification

range

of a

binary

alloy.

ofa Consider the solidification

binary

alloy

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 wish

the phase

5.

Alloying

of gold

hto

silicon,

(a) Suppose a
heated
deep

1000A
400\302\260C-

layer From

of Au the

and onto a Si crystal, subsequently diagram, Figure 11.11,estimate how

to
she

is evaporated Au-Si phase

gold

will

penetrate

into the
(b)

silicon crystal.
the estimate

The

densities

of Au

and Si

are 19.3and 2.33gcm\"\023.

Redo

for

800\302\260C.

Chapter

12

Cryogenics

COOLING BY EXTERNAL
IN

WORK

AN

EXPANSION
the

ENGINE
Joule-Thomson
Effect

334
Effect
van

Gas Liquefaction by Liride Cycle


Evaporation

337

Example: Joule-Thomson
Cooling:

for

der

Waals

Gas

333

339
Helium,
Miilidegrees

Pumped

to 0.3

341
342

HeliumDilution Refrigerator;
ISENTROPIC

DEMAGNETIZATION:

QUEST

FOR ABSOLUTE

ZERO

346

NuclearDemagnetization
SUMMARY

348
350

PROBLEMS

350

1. Helium

as a
Cycle

van

der

Waals

Gas

359

2. Ideal

3. Claude

Carnot Liquefier
Helium

35i
35!

Liquefier

4. Evaporation

for 5. Initial Temperature

Cooling Limit
Demagnetization

352
Cooling

352

Cryogenics
We
down

is the

discuss
to

physics and techiioiogyofthe productionoftow temperatures. the physical principles of the most important cooling methods,
lowest

the

temperatures.

The dominant

principle oflow temperature generation


against

down

to

lOmK

is the

cooling

of

a gas

gas

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 of a cooling principle is the iscntropic demagnetization
employed

by kiting it do work be a conventional may virtual

a force

during an expansion. The

or

the

gas of 3Hc

paramagnetic

substance.

We laboratory

discuss

ihe cooling methods chain lhat starts cooling

in

the

order

in which

they occur
proceeds

in

by liquefying helium and

from

there

to the

Household

1 ;iK. sometimes lowest laboratory temperatures, lOmK, usually and automobile air conditioners utilize the cooling appliances

same

evaporation

cooling

method
boiling

that

is used

in

the
1

laboratory
K.

for

cooling

liquid helium

below its

temperature,

to about

COOLING

BY
EXPANSION

EXTERNAL
ENGINE

WORK

IN

AN

In the

isentropic expansion

of a monatomicidealgas
to

from

pressure

pi

to a

lower pressurep2, the temperature dropsaccording

(i)

by F.64).
temperature
working

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 excellent if the cooling approximation gas, is reversible.
from are

process

arise The problems in implementing cooling expansion The of actual expansion processes. problems irreversibility the of low lubricants. nonexistence by good temperature and cooling cycles follow Figure 12.1.The compression

the

partial

compounded

Actual
expansion

expansion
parts

of

itisng

by

External

Work in on

{Expansion

Ens

Heal

ejection

Expansion

ngine

Working\342\200\224

volume

FEgure

A working gas ts Simple expansion refrtgeraior. 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,

I2.I

via

{he

heat

exchanger.

Chapter 12:

Cryogenics

the cycle arc

The hot compressedgas is cooled to temperature. by ejecting heat into the environment. The gasis further
flow heat

is separated.The compression
with

performed near

at

or

above
in a

room counter-

room

temperature

precooled

exchanger by contact
the

temperatureof
in

cooling

load.

The

the

expansion

engine,

usually

return gas stream at the low cooled to itslowesttemperature a low friction turbine.The cold gas extracts
the

cold

gas is then

heat

from

the cooling
the

load and then returns to


reduces

the

compressor

via

the

heat

exchanger.
imposed

The heat exchanger greatly


expansion

the

cooling

requirements
important

im-

on

engine.
by

The design of Sheheat


expansion
of

is as exchanger
enthalpy

as

the

design
work

of the
extracted

expansion engine.
the

The
between

engine
gas

is the
flowing

difference

the input

and output
where
She

gas: The iota!energy


the

into

the expansion

engine is the

iruernat energy U^
compressor,
leaving
p2

plus
Vx

the displacement
refer

done the The total


by

boih

fij and
with

to

a given

mass of
of
The

work p{Vl gas.


the

energy

engine to move

plus the work


extracted

V% required

is the energy U2 the the gas against pressure p2the gas


~~

gas

work

by ihe engine
W

is the difference
4- PlVt)

{Ul

- {Uz +
|Nr

PlV1)

Hs

H2.
\\Nx.

B)
The

For a monatomic ideal


work

gas

j=

and

pV =

Nr, hence H =

performed

on the

engine by the gas is


W \302\273

|N{t,

r2).

C)

The countefHowheat exchanger is an enthalpy device: it is an exchange work. expansion engine which extractsno external 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
is
usually

mechanical

operating

difficulties.

The

final liquefaction

stage

a
usually

Joule-Thomson
eontain

stage,
two

discussed more

below.

liquefiers
temperatures,

or

expansion
expansion

Helium and hydrogen engines at successive temideal gas

with

multiple

heat

exchangers.
isentropic

The principle of

cooling by
in

of an

is applicable
a

to

the

electron

gas

semiconductors.

When

electrons How

from with

semi-

semiconductor wuh electron potential


potentials.

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
a lower

Gas Liquefaction by

the

Joule-Thomson

Effect

down

to about
hnvc

195 K quite routinely;in


been

multistage

units

temperatures

down

So 135K
Gas

achieved.

Liquefaction

by the

Joule-Thomson Effect
of
the

Intcrinolccular attractive interactions causethe 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.

al! gases.

At
are

interactions causes

significant

gas

will condense.

The

practical

implementation

is simple.

Gas at

pressure p, is forcedthrough
a

constriction

called

an expansion
is

valve into space with


difference

lower

pressure

p2,

as in Figure
displacement
Here

12.2.The work
the

{he

between

~plt(Vj doneon
work
is negative
dVt

gas

in

pushing

it through

+p2(\"/2 recovered from the and dV2 is positive.


enthalpy.

side. gas on the downstream


To

the displacement and {he expansion valve

work
the

The overall processis at constant expansion valve acts as an expansion = 0 in If B), we have H\\ ~ li2 in the

sec this,
effect.

notice that the

engine

that extracts

Joule-Thomson

zero work. With For an ideal gas


for

11

\342\204\242

\\Nr,

so

that

ts

\342\200\224in

r2

the expansion.

There is
occurs

zero coolingeffect
because

an

ideal

gas.
of

gases a small temperature change work done by the molecules duriiig expansion.
in real

the

internal

The sign

of the temperature

Expansion

valve

Figure

|2,2

The Joule-Thomson
the

eflccl.A
gas is

gas

is pushed

through an expansion value. If be a temperature change during

the

notlflieal. ihere will because of work expansion


If the

done against
initially

the

intermolecuhtr

below

a certain

temperature is inversion temperature, riB,, the gas


forces.

will cool

on Joule-Thomson expansion-

Chapter

12:

Cry

Table

U.I

Liquefaclion dala
n.
Tt,

for

lo

T,,.,
K

AH,

V,.

(jas

U/mol

em'/mol

wall

Mite

CO,

195

304

B050)

25.2

223

314

cm

112

o,

N,

H,
\342\200\242He

902 77.3 20.4


4.SS

191

JHe

3.20

155 126 33.3 5.25 3.35

A290)
893

8.18
6.82

34.4

66

621

5.57

205

0.90
0-082

28.1 34.6 28.6

67

45

51
B3)

320
50.8

8.7

0.7!

0.025

0.14

the

liquid.
Jrti

The las

umn, '

Atl/V,

tndkai

n walls

thai

can

be la'ken up

for

T( ano\" oot

measured

Carbon dioxide solidifies

mosphcric

pressure.

because its lrjple


us LNG give daia

poinl

of natural gas, which is liquefied in huge and niirogen are separaied iu lhe liquefaction ei isotope 4Hc and for 3He.

quamilics for shipping we of air. For helium,

fuel.

boih

Liquid for ihe

on the depends change during a Joule-Thomson expansion All gases have an inversiontemperature below which TIn, above which heals (he it cools, gas. inversion temperatures

initial such

temperature. an expansion

for common

gases

are listed

in

Table

12.1.

Example:

Joule-Thomson

effect for
H

ran

far

li'aab

gas.

We

found

in

A0.75)

that

\302\253=

JWt

{S2fV){bx positive

- 2a)
constants. The
the last

D)
two

for

a van

der Waais

gas, where a and


the

b are

terms

corrections caused by
corrections

short

range repulsion and

long sign

range at

atiraction.

arc the The correc-

have

opposite

signs. The

tola! correciion changes


tinv

the temperature

== lab

= 2/rt,

E)

where xc
The

is

the critical

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 temperature

tempera!urc, defined by A0.46). lemperature. iln, is the inversion

Gas Liquefaction by
i a

the

Joutc-Thot

fixed lemperamre
inio

s because now the anl: ai lhc higher regio

work

done by the
the

lempcraluie

ioIccuIcs penetrate

farther

lhe repulsive

Linde

a counlerflow

iscombined wilh litjueficrs the Joule-Thomson expansion 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.
cycle.

In gas

To

and

from

comprcs

Figure
by

12.3

The Lindecycle.Gas
Joule-Thomson

combining

expa

a countcrflow

Iieatexchanger.

vaJv. JT expansion

Liquefied

gas

Figure

12.4

as a

fund

ion ofihe

Performance of helium inpui pressure,


ihc

litjueficrs
for

operating

by the

Liude cycle,
ihe

an

ouiput

pressure
= toad

of 1 aim and
-

for various values of


liquefaciion

input

temperature.
at 4.2

The solid
QiM (he

curvesgive
tfDUl

coefficient

The broken
coid helium

cunes give
K
if

Hia, ihe

inierna! refrigeration load available

is placed

inside ihe

ii^uciicrand
through

ihc

still

gas boiledoff
than

by lhc load

is relumed

ihe

heal

See Problem
Plenum,

3. Afier 1971.

exchanger A. J.

rather

boiled

oiT into

Croft

in

A&mWL-dcryo&mcs

liie atmosphere. (C. A. Baiiey, ed.),

p. 1S7.

Evaporation Coaling;

PumpedHelium,
is ;i

to 0.3

The

comhimtiion
X

hc;\302\273

exchanger-expansion enter

valve Hie

consimu
suppose

arrangement. Let one moleof gas


fraction
is

combination;

enthalpy ihat the

liquefied.

Constant
=

cniluilpy
+

requires lhat
\302\243!

//;\342\200\236 -IWii,

J)H9Ui'

\302\2436}

Here

Hla

H(TiMp-a) and
and

gas at

lhe input
heat

output

of

are the enlhalpies mo!c of llou, = H(Tin.pBJ per both at lhe common pressures, upper temperature
lhe enthalpy
From

the

exchanger-

tfHl) is

per moleof liquid


we obtain

at

its

boiling

lcm-

peraturc

under lhe pressurepoal.

F)

the fraction

17)

called

the

liquefaction

coefficient.

Liquefaction

lakes place

when

//\342\200\236\342\200\236, Hia;

>

thai

is, when
(8)

HiT^J
Only

> H{Tia,p-J.

the

enthalpies

at the input expansion


G)

the

Joule-Thomson

maHer. lemperalure of lhe heat exchanger at this temperature cools the gas, liquefaction

If

will

take place.
are

The three enthalpiesin


liquefaction

known

coefficient
rapidly

calculated
with

Figure 12.4 shows lhe experimentally. from them Tor helium. The liquefaction
Tiat

coefficient drops

increasing

because

of the

decrease of the

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

numerator

G)

and

the

increase

of the

Evaporatfon
Starting

Coofing:
from

Pumped Helium, lo 0.3 K


helium, the of !hc liquid
ihc

liquid

is simplest route lo lower temperatures


pumping is extracted

evaporation latent

heat

helium, by cooling of the of vaporization liquid Iteltum


further

away

lieiium along

vapor,

y '

with the

vap,-..

causes The heat extraction

cooling:

work

is done
the

against the interpi;>ce. hi JouLthe


cooling

:itonu'c

forces

that

cnuscJ

ihc

helium
staie

Tltomson cooling tlte initial initial state is a liquid.

is

io liquefy in a gas, while in

first

evaporation

Chapter

17:

Cryogenics

Table

12.2

3Hc reach
p(lorr)

Tempera turds,
specified

in

kctvifi.at

which

1 he

vapor

pressures

of 4He and

values

0.66

0.79

0.28

0.36

0.98
0.47

1.27

1.74

2.64

0.66

1.03

1-79

The
equilibrium

lowest in

tempcralure vacuum

accessible technology

isa problem
helium

vapor

pressure

drops

gas and

its heat ofvaporization


cooling

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
by evaporation

cooling of

bath.
Evaporation

ts the

dominant

devices The

household refrigerators and freezersant! in is in the workingsubstance. difference only


such a5 Dilution

cooling principle

in

everyday ait

cooling

conditioners.

Helium

Refrigerator:

Militdegrees
pressure

Once the equilibriumvapor


classical 0.6

of

liquid

3He has
dilution

dropped to

I0\023

torr, from

refrigeration

principles

lose their
by

range utility. The temperaiure

K io

0.0! K. is

dominated

the

helium

refrigerator,

which is an

in a evaporation refrigerator We saw in Chapter 7 that

very *He

clever atoms

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 immiscible overa wide composition range, in Chapter 11 and is shown in the phase oil and water. This was discussed
of 3He-4He mixtures in diagram the range labeled unstable wil!
Figure

disguise.* quantum are bosons, while

11.7.

A mixture
two

with

composition

in

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

decomposeinto

separate

phases

whose

For good reviews, sec D. S. Belts. Contemporary 36, 181A968);for a general review or cooling

Physics
techniques

below

9.97 {1968): IC. 1 K see W.

Wheatley.

Am-1 and
principles

methods
Scientific

Lounasmaa, Repts. Prog, Phys. 36, 423 A973); O. V. Lounasmaa, below t K, Academic Press,Hew York, 1974. A very elementary
American

J. Huiskamp
.

Phys. O. V.
and

Experimental
accoun!

Is O. V. Lounasmaa,

221,26

(t%9).

\342\226\240

Figure

12.5

Hlc is in equilibrium mixiure, sHe evaporaics

dilution Cooling principle of ilm helium wiih a JHc-4He nmiure. When from ihc pure ]He fluid and

4He

refrigerator. Liquid is added io the absorbs heat in ihc

3He-4He

At range, near the bottomof Figure11.7.

mixture wiih more than 6 pet 3Hea*


these the

a temperature

in the almost

temperatures

millidcgree all the 4He

atoms have condensed into

to compared

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. rich The principle 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,
ground

state

orbital.

that

of

the

remaining

3He atoms,

consider

the equilibrium between the concentrated3Heliquidphase the and tile lliai JHc:4lic nilio of dilute Suppose gas-like plliise (Figure 12.5). as by dilution with the dilute phase is decreased, pure *He. In order to restore 3He aiomswil! the equilibrium from the concentrated concentration, evaporate
iHc
will 3He liquid.Cooling

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 multistage the design. 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

Helium

Dilution Refrigerator:

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
Figure

12.6

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
rate,

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

temperature circulate

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 lo any

circulation
first

in rhe

pump over ihe pressure in siill. ihcn in the counter/low

the

still. The liquified JHe is cooled further, heat exchanger, beforere-entering tlic miung

chamber.

In the convendilution refrigerator has a low temperature litnft. 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-vaporization of 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.


Temperatures

below

SmK
2.6,

can

be ncltievcu by off the


3He sleady

ihe

design

of Figure

we shut

there is

no needto cooi the


below the

single shot operation. If, 3He supplyafter some time of opeiation,


itself, state

in

incoming its

and

ihe temperature
until

of the
been

mixingchamber drops
removed from
The
chamber.

value,

all

3He

has

dilution

refrigerator

is not the

known alternate An the peculiar propertiesof JHe. method, in Figas shown as Pomcranchsik cooling, utilizes the phasediagramof 3He, and between Figure 7.15, with its negative liquid slope of the phase boundary solid 3He, The interested reader is referred to the reviews by Huiskamp ant! Lounasmaa, and by Lounastnaa, citedearlier. range

oniy cooiingmethodin

the

inillikelvin

that utilizes

'

N.

H.

Pcnnings,

R. de

Bruyn

Ouboicr,

K. \\V. Tacoois.

Phjiica 8

SI. !0! A976).

and

Physiea

84, 102A976}.

ISENTROPIC

DEMAGNETIZATION:
doniimim

QUEST FOR ABSOLUTEZERO


Below

0.01

K the

cooling process

is the isciitropic (adiabaiic)

dcm;ig-

of I niK paramagnetic substance. By this process, temperatures have been attained with electronic paramagnetic systems and j /(K with nuclear systems. The method dependson tlie fact that at a fixed temperaparamagnetic the entropy temperature of a system of magnetic momentsislowered of a by application 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
iictizatioii

of a

and

3.

We first apply a
will

magnetic field
appropriate
changing

Bt

at constant
value

attain

a value
without

to the
the

of

to B2 reduced
will

entropy

temperature ij. The spin excess If the magnetic field is then Bj/tj. the of spin system,the spin excess
will

remain

unchanged,
<\342\226\240< When

which the

means

that B2/z2
the

equa'

#i/ri-

HBz

\302\253

Bi,

then flow
Figure

t2 into
12.7-

tj-

specimen
from

is demagnetized
system

isentropically,entropy
vibrations, as in
lattice

can

the spin
At

system only

of lattice

Figis

entropy of the will be usually negligible; thus the entropy ofthe spin system during isentropie demagnetization of the specimen.
the temperatures

of interest the

vibrations

essentially

constant

\\Latttce

Total

Spin

Lattice

Time\342\200\224-

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

Before
Time

New

equilibrium

Before Time

New

equilibr:

at which
field

at which

magnetic
is

removed

magnetic field js removed

Figure

12.7

specimen is constant. The


comparison
cooling

of

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

initial

lsentropic

Demagnetization:

Quest for

Absolute

Zer

an

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 Figure

12.8

inicrna!

random

used

in

practice.

The

steps

carried

out in the
giving

cooling processarc shown


with

in

Figure

12.8. The

field is
with

applied at temperaturetx
surroundings, {At? ~ 0)

the

specimen

in good

thermal
the contact

contact
constant ai

the

the

isothermal

is ihen path ab. The specimen


t,

insulated

and the field

entropy

6c, ending up at temperature t2. The thermal contact is broken helium provided by gas, and the thermal
path

removed; the specimenfollows

is

by removing the
of

gas with
The

a pump.

population
population

of a

magnetic subievelis a function


spin.

only

ntB/x,
function

where
only

is the magnetic momentof a


ofthe

The

spin-system

entropy

is a

distribution;

hence the

If SA
the

isenlropic demagnetization experimentis

localinteractions is theeffeclive field that corresponds to thediverse among temperature r2 reached in an spins or ofthe spins with the lattice, the final
(9}

spin entropy is a function

only

oimBjx.

rt the initial temperature.Results which as CMN, Figure IZ9 for the paramagnetic salt known . . magnesium nitrate,
where

is the

initial

field and

are

shown

in

denotes

cerous

0.1

0.2
Final

0.3
field

0.4
in K Bf versus

0.5

0.6

temperature,

Figure 12.9
nil rale.

Final

magaclic

final

In fhese

experiments ihe magnetic


bul

field

was

not

removed
iiiiiial

cniirciy,
and

only

m tfic

fields

icmpcraiurcs

After
as

cilcd

unpublished results 61\" J. 6, by N, Kuril, Kuovo Cimcnio (Supplement)

indicated values. The were idcnliait in all inns. S. Still and J. H. Milncr.

1109A957).

The process described so into a cyclicprocess thermally


far by

is

a single

shot

process. It is easily
in one
way

converted
the reservoir

disconnecting,

or

another, the

demagnetized working substance from at t,, and repeating the process.*

it to the load, reconnecting

Nuclear
Because
are

Dcmagnelizalion

nuclear
much

magnetic lhan

moments similar

weaker

interactions arc weak, nuclear magnetic a to reach electronic interactions. We expect


with

temperature
paramagnet.

lhan 100 limes lower with a nuclear paramagnet in The initial temperature of the nuclear stage C. B.
W.

an

electron

nuclear

spinS. S.

\342\200\242

C.

V. Hctr.

Barnes,and
and i.

J.
A.

G.

Daunt.

Rosenblum,

A. Slcyerl.

Barclay.

OHgcnics

Rev. Scj, insi. 25. IGS8 j|954); 17, 3S! A977).

W. p. PraH,

t\\'uc!ear Demagnetization

Iniiial magnetic

Held

in

KG

0.6

Initial
Figure
nuclei

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.
I2J0
in

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

sufficient

to

overwhelm

ihe
first

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 in

temperature

The T2 ss 10\027K.

cooling the

experiment metal,

was carried

oui by Kurli and coworkers on Cu nuclei at about 0.02 K as attained by electron stage
lowest temperature in Figure 12-10fil a llial
moments B\302\261

starting
x

from a
cooling.

first

demagneltzallon

The

3.1

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

The

results

of

the

Cu nueiei.

The motivation
conduction

for

using

nuclei

in a

metal rather than

in an insulatoris that

electrons

help
first

ensure
stage.

rapid thermal

contact
the

of lattice
cooling

and

nuclei

at

the

temperature

of the

Temperatures

below

1//K

have been

load was

the system of nuclear spinsitself,

achieved in experiments in
particulatly

which

in

experiments

that were

combinations of cooling experiments and

nuclear

magnetic

resonance

experiments.*

SUMMARY

1. The
cooling

two

dominant

principles

of the
it

production
against

of

and the iscntropicdcmagncii/atioii of a


2.

a gas

by letting

do

work

of low temperatures arc ihe a force during an expansion


substance.

paramagnetic

Joule-Thomson

is done work cooling is an irreversible process in which interatomic forces in a It is used as last the attractive against gas. cooling

stage

in

liquefying

low-boiling

gases.
the

3. In evaporation cooling the work is also doneagainst but starting from the liquid phaserather than the

interatomic

forces,

gas
the

phase.
basis

Using different
of
cooling

working substances, evaporation coolingforms and cooling devices, automobile air conditioners, (in the range 4 K down to SGmK).

household
devices

laboratory

4. The
the 5.

helium

dilution

refrigerator

is an

gas is the virtual

in gas of 3He atomsdissolved

evaporation

cooling device in
4He. temperature

which

Isentropic

demagnetization

utilizes the
when

lowering of the
magnetic

of

a
in

system
strength. By

of magnetic
The

moments,

an

external

field is

reduced

using

moments may magnetic nuclear moments, temperatures

be electronic or nuclear moments. in the microkelvin range may

be

achieved.

PROBLEMS

L Helium
for

as a

van

der

H'aafcgas.

(a) Estimate
van

helium

coefficientsa
volume

by treating
and

it as
such

der

Waals

tlte liquefaction coefficient X gas. Select the van der Waals

in

of
the

Use

liquid in

helium Table

a way that Tor one and that 2a/b is the

mole 2Nb is the actual molar

data

12.!. Approximate the


Hout

actual inversion temperature. denominator in G) by setting xliH)

Hi(q

AH

4- f(rin

A0)

for \342\200\242See,

example,

M. Chapcllier,

M. Goldman,

V.

H. Chau

and A.

Abragara,

Appl.

Phys-41,

849A970).

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

where All is the latent heat of vaporizationof liquid 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
2. Ideal

Carnot liquefier. (a) Calculatethe work mole of a monstomic ideal gas if the liquefy Assume that the gas is suppliedat roomtemperature
one

\\VL thai

would

iiqticfier
To.

be required to operated rcversibiy. the same and under


Let

pressure p0 at whidi the liquefied 7\\ be the boiling temperature of the


Show of vaporization.

gas gas

is removed,

that

under

these

1 atmosphere. typically and A// the latent at this pressure, conditions

heat

A1)

To derive A1) assume that the gas is first cooled at fixed pressure p6 from To a the fixed reversible between to Tfc, by means of refrigeratorthat operates equalto the gas upper temperature Tb ~ To attd a variable lower temperature ~ Tb the Initially 1\\.After reaching 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.
3. 1 mols\021 in which cycle helium Hqucfier. Considera helium liquefier 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 exbetween (b) Assume that the heat exchanger 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 compressed gasenteringit with pressure pc. Show that under ordinary liquefier must extract the work operationthe expansion engine

Claude

of gas

Te -

TJ ,

A2)

Chapter

12:

Cryogenics

per mole

as in ihe

Undo cycle sectionof this chapier. Assume the expansion engine between ihe and operates isemropically pressure-temperature pairs {pc,Tc) calculate(pc,Te). Estimate (Pia>Ti(l). From A2) and the given values of (pia,Tia), (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 Combine the result with loads calculated under (a) into a coefficient {hecooling of refrigerator for both the modes of operation. Compare with performance,
Carnot

of compressed gas. HereTin,

pin,

pBUt, and

have

the

same

meaning

iimit.

that can cooling limit. Estimate the lowest temperature Tmia is if the load 0.1 W 4He of cooling evaporation cooling 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 pressure corresponding 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 demagnetization coaling, Considera paramagnetic K. A magnetic field ofiOOkG with a Dcbyc temperature {Chapter 4) of 100 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
significant

to be I Bohr ion the magnetic momentofa paramagnetic By signifimagneton. 0.1 of the initial we to understand temperature. cooling may cooling

Chapter

13

Semiconductor

Statistics

ENERGY

BANDS;

FERMI

LEVEL;

ELECTRONS

AND HOLES
Action

355

ClassicalRegime
Law

358
362

of

Mass

intrinsic Fermi Level

362
363
SEMICONDUCTORS

/r-TVPE AND
Donors

P'TYVE

Fermi

and Acceptors
Level

363
Semiconductors

in

Extrinsic

364

Degenerate

Semiconductors
Levels

365

Impunly Levels
Example:

368
369

of Donor Occupation
Semi-Insulating

Gallium

Arsenide

372

p-n JUNCTIONS

373
p-n

Reverse-Biased
NONEQUIUBRIUM

Abrupt

Junction

377

SEMICONDUCrORS Diffusion
Through an Impurity Level

379
379

Quasi-Fermi
Current

Levels

Flow:

Drift and
Laser

379
381

Example:Injection
Example:

Carrier

Recombination

383
385

SUMMARY

PROBLEMS

387

1. Weakly

2.

Doped .Semiconductor
Conductivity

387
Conductivity

Intrinsic

and

Minimum

387

3. Resistivity and Impurity Concemraiiou 4. Mass Action Law for High Electron Concentrations

387
387
387
3S7

5. Electron

and

Hole

Concentrations

in InSb

6. Incomplete lonizationof Deep Impurities 7. Built-in Field for Exponential Doping Profile

388
388

8.

Einstein

Relation

for

High

Electron

Concentrations

Chapter

13:

Semiconductor

Statistics

10. Minority
11.

9. Injection

Laser
Carrier

388
Lifetime

38S

Electron-Hole

Pair Generation

388

iiiiiiui^zny

conduct v\302\273'ilti

[tin xind valence b jfiu\302\243 \\ elects oeis snd

hoics^ donors

*inu

3cccplovs.

I he

Ha

conccnlration

of holes

ht
n,

= cffcciivc
=

c^uantiiEn

conccnlnU/on

for condudion
for

ctccirons;

effective

quamum

coiKcntralion

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

BANDS;
AND

FERMI LEVEL;
HOLES

ELECTRONS
The
is

of the Fermi-Dirac disiribution to eiecirons in semiconductors application central to the design and operation of all semiconductor and devices,
treat

thus

to much of modern electronics. We

below

those

of semiconductors and
We

semiconductor

devices

that

aspects are parts of

eleclrons

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
assume

that

the

reader

of the physics thermal physics. of the physics of

in

temperature.
A

semiconductor

is a
an

system

with

electron

orbitats

grouped

into two

energy

bands separatedby
band t

and

0 al!

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

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

Fortypical is the energygap of the semiconductor. eV. 0.1 and 2.5 electronvolts.In silicon, e, ^ 1.1
\342\200\242 We tieai both bands of bands wtih additional

semiconductors Because

Eg

is between

t ^

1/40 eV at
boih
may

room

as single

for out (imposes it bands; gaps wiihtn each gioup.

does

noi mailer thai

be groups

Chapter 13: Semiconductor

Statistics

Conduction

band

Empiy

atr =0

Energy

gap

Filled

air =0

Figure

t3.1

Energy

band

structure of
bands

The electron

Air =
conduct the

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
\\vhjch

orbilajs occur in

a puic semiconductor
exlerid

or

insulator.

energy

gap.

t. Substances havec,, \302\273 2.5 eV are usually insulators. Table 13.1 gives semiconductors, together with other properties

temperature,

we usually

with a
the

gap of more than


gaps

about

energy

for selected

needed

later.
nh

Let

nt

denote

ihe

concentration

of conduction
two

electrons and
wiH

the

con-

concentration of

holes. In a

pure semiconductorthe
ii, =
\302\253*.

be equal:

B)

crystal is electrically neutral. Most semiconductors as usedn\\ devices that become impurities may thermally
if the
\342\226\240temperature.

have

been

inteniionaiiy

doped with

ionized

In the

semiconductor
crystal

at room
become accept

Impurities

tiiat

give

an

electron

to the

(and that

positively

charged

in the

process) are called donors.Impurities

Energy

Bands; Fermi

Lml; Elec

Table

13.1

Band

structure

data
Dcnslty-

f-statcs

Dielectric

Energy

antun

i concentr

itions li

gaps

at

c Idea

ions and
1300K

effective
in

masses,
of the

constants

olcs

units

relative

to

300 K
\",.

free
in/ftn

cicctr on mass

vacuum

ilia

eV Si

t.[4

2.7 x 10

'

1.1 x
5-2

10\"

1.06

0.58

Cc

0.67

1.0 x !O 9

GaAs

1.43

,,p InSb

0.18
from

1.35

4.6 x 10 '

x to'a

0.56

4.9 x 10 '

1.5 x

4.6 X

10

'

6.9 x 10'* 6.2x 10\"

10\"

0.07

0.073

0.35 0.71 0.42

11.7

15.8
17.S8

13.13

0.015

0.39
charged

12.37

an

electron

the valence

band (and become negatively


of positively

in

the

process)

are called
\302\253j+be

acceptors.
concentration

Let

!he

charged donors and

na~

the

concentration

of negatively

charged acceptors.
An

The difference
C)

/[/

na~

ts called becomes

the net ionized

donor concentration.The electrical neutrality

condition

An

Hj*

\342\200\224

no~~t

D)

which

specifies The electron


function

the difference concentration


of Chapter

betweenelectronand hole concentrations. dismay be calculated from the Fermi-Dirac


6:

distribution

exp[(e where

E)
/

[i is

the chemical potentialof the


the in

electrons.

The

subscript

e refers

to

electrons. In semiconductor theory the Fermilevel. called Further,


almost

electron

chemical theory

semiconductor

is always potential is the character fi


the

always

reserved

for ihe

and electron and hole mobilities,

Fermi

level

is designated
which

by ef
we

or

by

To \302\243.

avoid

confusion

with

the Fermi

energy
level

of a meia!
in

designated

as cf
our

and

which stands for tile Fermi


usage

ihe

limil

r -*

0, we shall maintain
at

previous

of the

letter /j for the

chemical potential

any

temperature.

Given

;i and

the distribution

is obtained t, the number of conductionelectrons function /,(e) over all conduction band orbitals:

by

summing

The

number

of

holes

is

*\\ =

[l \302\243
VB

- /.(*)]

= I

ftU).
Here

V)

VI!

where

the summation

is overall valence band

orbitals.

we have

introduced

the quantity

which

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
that an orbital probability the unoccupied orbital is \"occupied by
is

the

dependences

ne{y) and

nh{y}.

Classical Regime
We

assume

that

both

electron

and hole
that

concentrations are
fr
\302\253 1

in

the

classical

regime

defined

by the

requirements

and

fh

\302\253 I,

as

in Chapter

6.
gap

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

/i)/t]
n)

\302\253 1;

exp[-0*

to

ej/t]

\302\253 1.

(9)

To
few

satisfy
times

(9) both
larger
(9)

\342\200\224 (gc

and

(/t

eu)

have

be positive

and al

least a

than
place

t. Such
upper

inequalities

The a semiconductor is callednondegenerate. and limits on the electron and hole concentrations
With

are

satisfied

in many

applications.

(9)

the

two

occupation

probabilities

/J.E.)and /h(g)reduceto classical

distributions:

Classical

Regi

':.-\"-\\~'\\

Conduciion
I

band

Figure

13.2 Occupancy oforbiials as a finite temperaiure, to the Fermiaccording The conduclion and valence bands may be represented Dirac disSribution function. effedive numbers in terms of temperature-dependent Nc, Nc of degenerate orbiials The located aS the iwo band edges e,, \302\243\342\200\236. n(, n( arc ihe corresponding quantum

exp[-(e

write
the

=>

cxp[-(,,

A0)
electrons in the

We form

use

F)

and

A0) to

total

number

of conduction

N,

A1)

Chapter

13: Semiconductor

Statistics

where we define

N, Here
\342\200\224 \302\243 is \302\243c

\302\243exp[~(s Cfl

ej/r].

A2)

the

energy

of a

conduction electron referred to

the

conduction

band

edge
one

ec as origin.
Nc

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

The expression for


electron

in the

at ee,only
matters

ihe

distribution

of orbitals

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
in ihe
sum

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. of spin | the in C.62), but for zero spin. For particles partition function Z\\ result is larger by a factor of 2, so that A2) becomes

Nc = Zj
Numerically,

2nQV=

2(mx/2nh2)i!iV.

A3)

this gives

NJV =- 2.509 x
where

1019
x

G/300KK'2cm\023

(H)

Tis

in kelvin.
Nt A3),

dependenceas
express

The quantity
this

for but

actual differs

semiconductors in magnitude
in

ihe same temperature a by proportionality facior. We


exhibits
io

formally

by wriiing,

analogy

A3),

Nc *= 2(mSz/2nti2K'2V

,
electrons.

A5)
Experimasses

where
Experimental

me*

is

called arc

the given

values

effective mass for denshy-of-btates in Table 13.1. The introduction

of effective
it

is more

than

a formality.

In the theory

of

electrons

in crystals

is

shown

that

Classical Regime

Ihe dynamical behavior of electrons and

holes,

under

forces such as electric fields,


from

is

that

of particles

the influence of external effective wilh masses different


are

the

free electron

Ihe density-of-staJes
We

dynamical massesusually masses, however.


mass. The
coticetilralion
for ??\302\243

different

from

define

the

quantum

conduction

eleclrons

as

nc =

NJV -

A6)

concentration By A0 the conductionelectron

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
Similar

the

conduction

band.

reasoning

gives the

number of holesin
- e)/t]

ihe

valence

band:

wiih

the

definition

A9)

We define

the quantum concentrationnv

for

holes

as

NJV

2{in^z/2jihi)m.

where

wk*

is

llns

dcnsity-of-sJaJcs

effective

mass for

holes.

By

(IS)

ihe

hole

concentration/^

s NJV is

nh

\342\200\224 aBexp[\342\200\224(/(

\342\200\224

e,-)

B1)

Like

A7), this
In

gives the carrier concentrationin

terms

of

(he

ceniraiion and the

positionof

quantum

con-

the

Fermi
nu

level
is

relative the

edge.
of the
Law

(he

semiconductor band.

literature

called

valeuce band effective density of states


to the

valeuce

of Mass

Action
is

The productn^nh
are

independent

of the

Fermi level so longas the

concentrations

in the

classical regime.

Then

'V'k = 'Wexpf-fE,.
where the
and

O/r]
a pure

s=

ncnuexp(~

eJz)

B2a)
\342\200\224

energy gap
t^

\302\2439

s=

ec

eff.

In

semiconductor

we have
intrinsic

ut.

>ibt

the common

concentration

value of the two concentrations is called the of the semiconductor. By B2a),

carrier

B2b)

The Fermi level independence of the retains its value even when ne <\302\243 nh, as
impurity We

product
in the

n^iij,

means

that

this

product

atoms, may

provided

both

concentrations

presence of electrically charged remain in the classical regime.

then

write

B2a) as

B2c)

The
mass

value

of

the

product

depends

only on

the temperature. This result


the

is

the

action

law of

semiconductors, similar to

chemical

mass

action

law

(Chapter 9).

Intrinsic FermiLevel
For

an

intrinsic
and

semiconductor
B2b):

ne =

nh

and

we

may

equate

the right-hand

sidesof A7)

neexp[-(ec
Insert

- ^)/r] =
by n,.exp(

(vO\022exp(-\302\243/>*).

B3)

eB

= e^

\342\200\224 and

eB

divide

\342\200\224\302\243(/r):

ej/2r].

Donors

and Acceptors

We lake
/i

logarithms to obtain
=

{U,

+ \302\243,.)

|t Iog(u,/u,)

= l(cc
for

+ e,) +
intrinsic
from

3rlog(\302\273ifc7\302\273i,*),

B4)

of A6) and B0). The Fermi level (he middle of lhe forbidden gap, but
by use
amount

an

displaced

semiconductor lies near the exact middle by an

that

is usually

small.

w-TYPE
Donors

AND p-TYPE SEMICONDUCTORS


Acceptors

and

Pure

semiconductors
used

are an

idealization of Httle

practical

interest.

Semicon-

Semiconductors

increase
semiconductor

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

or holes.

semiconductor with

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,

more holes than

exactly fit

one

electron

into

the

filled

Si it replaces. valence band; hence a Si crysial


more

than the

These
with

extra

some

do not electrons P atoms wiil contain

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
number

of

conduction

electrons.
table

Most impurities in the same columnsof the periodic behave in St just as P and Al behave. What matters

as P

and Al will
the

is the

number of valence
atom.

electrons
Impurities

relative

from

to Si not the total number of other columns of the periodic table will

and

electronson
not

behave for

so simply.

Similar reasoning For the presentwe


may

can be appliedto other


assume

semiconductors,

example

GaAs.

lhat

each

donor
fill

enter

the conduction

band or

one

atom contributes one electronwhich hole also in the valence band. We


from

assume

that

are called the approxifrom the conduction band.These assumptions 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

each acceptor

either atom removes one electron,

the

valence

band or

An

nt

\342\200\224~ nfc

nj+

\342\200\224

na~.

B5)

Chapter

J3; Semiconductor

Statistics
the

Becausenh

m,V\302\273*from nc\\

mass

aciioti law,

we secthat

B5)

leads

to a

quadratic

equation for

V-\".^!-^1.

B6)

The positive

root is
\302\273*

i{[{A'O2
we

+ V]1/J

An}

B7a)

and

because

~
nh

An

have

\302\253 \302\273* l([(AnJ

+ V]1''2

- An],

B7b)

Most
concentration,

often

the so

doping that

concentration

is Urge
larger

compared to the intrinsic conthan n,:


B8)

either

nr or

ft*

is much

\\An\\

\302\273

nt.

This
can

Condition

defines an

extrinsic semiconductor. The squarerootsin

B7)

then

be expanded:

[(AnJ +

An*]\"*

|^[i

+ (hj&nJ]1'2
ln*l\\bt\\.

In

m +

B9)

an n-type

semiconductor
nt

&n is positive and

B7) becomes
** n^/An
\302\253 n,.

=x

A/i

+ nffAn

An;

nh

C0)

In a

p-typc semicondiiclor

An

is negative

and B7)

becomes
^

Ji. ^
The

n?/\\An\\

\302\253 n,;

nk ^

{A/i| +
extrinsic

h;V1A*i1

jAffj.

C1)

majority

carrier concent ration in


while

the

limit

B8)

is nearly

equal to

the magnitude of An,

the

mmoriiy

carrier

concentration

is inversely

proportionalto
Fcrmf

jAnj.

Level

in Extrinsic

Semiconductor
law Fermi

By use
/ij,by

of the massaction
the

we calculated level

having to calculate
solving

first.

concentrations without Tlic Fermi level is obtained from n, or


the carrier

A7) or

B1) for/c

Degenerate

Scum

Figure
various

13.3
doping

The Fermi icvet in


concentrations.
A

silicon

as a function

of lempcraturc,
wiih

for

The Fernifleveis
of liic energy

are expressed relative


icmperaiure

Ic

the

band edges.

sniaii

decrease

gap

has

been negieaed.

We may
An.

now use B7)

to

find

ft as

a function of

temperature and doping level


temperature
the

13,3 gives numerical results for Si. With decreasing Figure eiiher Fermi level in an extrinsic semiconductor approaches She valence band edge.

ths
cr

conduction

Semiconductors Degenerate
When quantum

one

of

the carrier
we

concentrations
may

concentration,

is increasedand approachesthe distribution use the classical no longer A0)


follows

quan-

for

iliiit

carrier. of the

The calculation

of the carriorconcenir.iiion now


over as

the

treatment

Fermi gas in Chapter 7. The sum is written equal to [he number of electrons, states times the distributionfunction:
N

all an

occupied iiiteura!

orbitais, which n over the density yf

Chapter

IS:

Semiconductor

Statistics

where for free

llie panicles of mass \302\273j

densily

of stales

is

C4)

Thai is, \302\251(\302\243)(& is ihe


make ihe
by

number

of orbitals

in

the

energy

interval

+ (\302\243,e

ck).

To
iV

n,V;

in

transition to conductionelectrons in \342\200\224 oblain by m,*; and \302\243 by e ec. We

semiconductors

we

replace

Lei x

s (e -

er)/r

and

ij

(fi

et)/t. We

use the definition A6)

of

J(c to

obtain

C6)

The integral /(;;)in


When

C6)

is known

as the

Ferml-Dirac integral.
so

ee

p.

\302\273 x

we

have

\302\273 1, \342\200\224ij

that

cxp(x

jj)

\302\273 1.

In

this

limit

C7)

the

familiar

result

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 the power njn^ called 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

and B. W.

Dixon.

App!.

Phys. Lclt.

31,354 A977).

If the

right side

of C8) is

wrine

1.483S6

x lO\"*:^,

- -4A2561x

1Q-6.'

Dtgcncnitt

Slmicomlitct

-6

-5

-4

-3 -2

-I
i)

(|.

- i,)h

above

conduciion

band

edge Er. The

dashed curve reprcsenis ihc firsi

icrm

of ihc

Joycc-Dixon approximation

C8).

Chapter

13:

Semiconductor

Sta

When

neisno

law must be modified.In Problem 4

longer small comparedto n(,


we

Ihe

expression

of the

mass action

ask

ihe

reader

io show

ihat

C9) If
the

gap
will

Itself
depend

depends
on

on the

carrier concentrations, the value

of

n, to

be used

here

concentration.

Impurity

Levels
semiconductor

The addition of impurities to a conduction or valenceband into

moves

some

orbitals

from

the

Ihe

as
P

energy

gap,

where the

orbiials now appear

in a silicon crystal.If the electron to the Si conduction the atom band, 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
localized

bound

states.

We

consider

phosphorous

atom

has

released

iis extra

semiconductor is several orders of is to be the energy by square


divided

magnitude

lower,

mostly

because

the binding

paniy

because

of

mass
in

column

V donors

donor

corresponds

of the static dielectric constant, and for 13-2 gives the ionization energies 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

conduction band (Figure13.5). There


donor.

is

one

set

of bound

orbitals

for

every

A parallel from

argument applies to 'he valence band, as in Figure


wiih

Orbiials are off holes and acceptors. split For each acceptor atom there is one 13.5.
energy

set ofbotmd orbitals


as

an

ionization

Asa ~

\342\200\224 Ea

\302\243,,,ofthesameorder

Aej. Ionization

In GaAs the ionization energies

in Si energies for column III acctipcors

are

listed

in Table

13.2.
Some

for

all

column

VI donors

except oxygen are


=

closeto

6rrteV.

For

zinc,

the

most

important

acceptor,

&\302\243a

24meV.

T:.Mc 13.2
column

!uiiu..iio.i encr^e*ofcuhmm
acceptors in Si
arui

V <j

il!

Ge,

in mcV

Ace

cp OIS

11
49

AI

Ga 65

In

45

57

16

12.7

10.4

10?

iOS

11.2

Occupation

of

Donor

Letch

'

At,

!'

\"'

\302\261

Figure

13.5

Donor

and acceptor

impurity

levels

in Uic

energy

impurities generate orbitals deep inside the forbidden ionization multiple orbitals corresponding to different
Occupation
A

gap, states.

sometimes

with

of Donor
level

Levels by an electronwith
orbitals are
either

donor

can

be occupied
different
two

spin

up or

spin down.
Once
level

Hence there are [wo

with not

the same
nt

energy. However, the


of

occupationsof these level is occupied one


by

orbitals

independe

each

other;

the

electron,

the donor

cannot bind a second electron with


for

opposite

spin.

As a

result, the

occupation probability

donor

is not

distribution but function, by a function given by the simple Fcrmi-Dirac 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

Chapter

13;

Semiconductor

Statistics

Acceptors require extra thought. each of the chemical bonds between

In the ionized conditionA\"


ihe

of

the

acceptor,

acceptor

atom

and the

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
of

the

acceptor,

one electron

is missing

from

the

surrounding

bonds.

Because

the missing electron may

haveeithcrspin

up or

spin down, the


a

is representedtwice in the Gtbbs sum for the acceptor, by Hence the thermalaverageoccupancy is
A

neutral condition term 2 x J ~ 2.

'

2 +

exp[{^ ~
with

Efl)/i]

\"\021+2

exp[(Efl

{~

\"}

$x]\" occurs
with

The

neutral

condition

A,

the

acceptor

orbityl

unoccupied,

probability

______

_ __________ of concentrations of D*

D3)
arid A\342\204\242.

The
From

value

of

An

== nd+

\342\200\224

na~

is the

difference

D0)

or D2)

we have

D4)

D5) The
neutrality

condition

D)

may

be rewritten

as

This expression may


functions

be

visualized

by a
level

logarithmic
(Figure

plot of n\" and n*


13.6}.

as

func-

of

the

position
four

of the
terms

Fermi
D6);

The

four dashed
sum

lines
of

represent the
positive For

in

the two

solid lines representthe


Fermi

aii

and all negative


the nd+

charges.The actual
total

level

occurs

where the total

posicivechargesequal
-

negative

charges.

for holes can be neglected; electrons can be neglected. If one of the two impurity nu~ \024* \"i 'he be the can be calculated can neglected, species majority carrier concentration in The closed formConsider an it-type semiconductor with no acceptors.

jio~

\302\273

nh

as

in

Figure

13.6, the

-^

Occupation of

DonorLetch

Figure

13.6

Graphical

determinaiion

an n-1ypc

sciniconducior

of Fermi teve!and eteciroi coniaining both donors and acceptors.

neutrality

point
with

in Figure
?!e curve,

curve
intersection approximation

the

will A7)

be

on

holds.

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
U ihe

cxp(/</T)
exp[(^

(\302\273A)\302\253PfcA);

\302\2537>

\302\243i)/t]

(\302\273>Jexp[(\302\243,

tj/t]

= njn*

D8)

nc*

neexp[~(et that
with

Eli)/i] = ;i,exp(-A^/t)
be present
level.
in

. {49}
band

Is

the

electron

concentration

would
donor

the ~

conduction ec

if

the Fermi level coincided

the

Here

Aed

Ej is

the donor

iontzacton energy.
We

insert

D8)

into

D4) and

set

nt

nd* to

obtain

E0)
=

nf3

\\n,nt*

i\302\273rfn,*.

E1)

llus

is a

quadratic equation in n,; ihe positive


\302\273\342\200\236

solution

is

V([l

+ (S\",,//)/)]1'3large and
root

I}doping

E2)
is sufficiently

For

shallow

donor

levels,

nt* is
square

close to nc.ffthe

weak that

\302\253 8\302\273j \302\273/, the

may be

expanded by use of
+
\342\226\240\342\226\240\342\226\240

xI1*

=? 1 +

\\x

-ix2

E3)

for

-v

\302\253 i.

With

x ~

8\302\273d/He*

we

obtain

^ \302\253\342\200\236 \302\273\342\200\236

2it//ne*
gives
P

\302\253

;tj(l

2<td/ite*).

E4)

The secondtermin

the

ionization.For
Table 13.2, so

parentheses
for ne*

the first

order departure from complete


have

example,

in

that

=s 0M5nc

300 K, we = from D9). If \302\253j


Si at
un-ionized.

Ae,j

t.74r E4)

from

0.0!nf,

Eq.

predicts

that il.4 pet of the donorsremain

The

limic

of weak

ionization is

the subjectof

Problem

6.

an intrinsic

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:

StuM-itiiHtuting

p-n

Junctions

However, ic
with

is possible

high ttiat

concentra

lions (tOi5-IO17

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

near tnerinste carrier Cm-3) of oxygen impuriiy levels near the middle
to achieve

concentrations
and

in GaAs by together,

doping

chromium

two impu-

As site

p-n JUNCTIONS

Semiconductors
used

are almost never uniformly doped. An underan semidoped requires understanding of nonuniformiy of structures called p-n junctionsin which the doping semiconductors, particularly We to n-type within 'he samecrystal. consider ton from /vtype changes with posi! a semiconductor at .v = 0 which the crystal inside doping changesabruptly 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:
m

devices

understanding of devices

iwo closely spacedp-n junctions, ofthe sequence or n~p-n. p-i\\~p in the built-in electrostatic Vbi, even potential 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(Fermi levels) equilibrium, sides are the same. Because ihe posiiion of the Fenni level within ihe band level forces :i of the Fermi siructurc depends on the localdoping, constancy
shift shift

in is

the eVN.

electron The

energy

bands stop of

in

crossing

ihe
an

junction
example of

potential

height eVbii%
potential

(Figure 13.7c). of the potential systems

The step

required to equalize the total chemical are intrinsic chemical potentials unequal,

two

when ihc

as

discussed

in Chapter

5.

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

differenl

concentrations,
shifted

diffusive between ihe equilibrium electron concenlralions as wet! as hole ihe Fermi level must be (c) Energy bands. Because
Vbl

ealabtishes

relaiivc

to each
buitl-in

other, (d) Spacecharge


and

dipolc

required

to

generate the

voltage

to

shift

the

energy

bands.

We assume that

the two doping concentrationsnd,


defined

tta

lie

in the

extrinsic but

nondegenerate range, as
Hf

by

\302\253 nd

\302\253 \302\273c;

\302\253 \302\273( na

\302\253 \302\273t.

E5}

If the

donors

are

fully

ionized

on

the n

side and

the acceptorsfully

ionized

on

the p

side, then the

electron and ho!econcentrations satisfy


ne

=z vd\\

nh

s:

na,

E6)

one on
from \302\261

the
Jij,

side

and

the other

on thep
band

side. (We have droppedthe


on the
i\\

superscripts

The conduction \302\273\342\200\236.)

energies

and

p sides

follow

from

A7):
-xlbgl^/nj; \302\253\302\253-/*

E7)

ccp =
by

H~ xlo&{nJnc) =

;1-

tlogK1/\"^).

E8)

B2c).

Hence

eVtf

\302\243CJ. e\302\253

Tlog(W>,2)

E9)

For doping concentrations nd


which A

0.0inrand

Hfl=s0.0inL.,we
the

find eHi
band

= es -~9.2t,
energies

is 0.91 step

eV in silicon

at room
potential

in electrostatic

is required
to

temperature. to shift
each

edge

on

the two sides of the junction relative


<p{x)

other.

The

electrostatic

potential

must

satisfy

the

Poisson

equation

(SI)
is the

= ~~ ,

F1)

where

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 p

(Figure 13.7d}. concentration is less


Positive

space
than

charge donor

on

the

side

means

that

the electron

the

concentration,

indeed,

as the

conduction

Chapter

13:

Semiconductor

Statistics

raised relative to the fixed Fermi decreaseof the electronconcentration ie.


band edge ts
Take Then

level,

A7)

predicts

an exponential

the ec(x)

origin =

ofthe

electrostatic
\342\200\224

potential at
A7)

x = -co.soihai

= 0. <p(-00}
F2)

\302\243c(~-a))

e<p{x),

and

becomes

ne{x) =

ntcxp[e<p[x)/T].

ThePoisson
^
Multiply

equation

F1)

is

]
Jdtpfdx

F3)

by

to obtain

_</WV
d.x i/x^

</

AM2

^
t

J
dx
=

, ,1

i6d\\

(/.x \\il\\-J

{
0:

oc) Integrate uiih the initial condition<p{\342\200\224

\\dxj
At

F5)

the

interface

x =

0 we assume that'

F6)
where

Vn is

that

part of

the built-in electrostaticpotential dropthat

occurs

on

the n side.

The exponential

on the right-handsideofF5)can

be

neglected,

and

we obtain

E for the
-v

[peii,/c)(K,
field E

*/e)Vn

F7)

component

ofthe

electric

= -dipjdx. at the interface. Similarly,


FS)

\302\243=[{2eMB/\342\202\254)(^-t/e)]\022,
potential drop part of ilie built-inelectrostatic be the same; from this and from two \302\243 fields must

where

I-; is that

that
Vn

occurs
-V
Vp

on
=
Vbi

ihepstdcTlie
we

find

(\302\243^')\022

F9)

rse-BiasedAbrupt
The
from

p~n

Junction

field E
lite

is the Sameas if On
to a

the

ii-type

side all

electrons had

been depleted

junction

distance

-(Vw-2r/f)

, G0)

with

no

depletion

at

\\x\\

>

\\vK.

The

distance

wa is

ofthe theory as a measure


layer into
Similarly,
the

depth

of penetration

used in semiconductor device of the space charge transition

n side.

on the

p side,

The totaldepletion

width

wK

1f

we assume

\302\273o

nd =

i0licm\023;e

~ l(ko;aiid
x

Vbi

2z/e

== 1 volt,

we lind

- 4.25 \302\243

x 104VcmwI

and w

4.70

iO^5cm.

Reverse-Biased
Let

Abrupt

p-n

Junction

a voltage

be

applied

to a

p-n junction,
which
voltage

of such sign that


means
will

the raises

p side the

is at

negative vohagerelativeto the n side, energy of the electronson the p side.This


from

that
drive

potential

cond uction

electrons
the
ifie

the

p side

to the a very
are

\302\273 side,

and
low

holes

from the ;i
of

p side
n

in bulk contains

contains a very

concentration

side to the p side.But conduction electrons, and


the

side

with low concentration of holes,consistent

mass

action

law. As
and

a result, very

little

current

flows.

The distributions

of electrons,
voltage

holes,

potential

approximately

ihe same
13.S.

as

if

the

built-in

were

increased

by the

applied voltage,Figure

The

field

at

the interface is now

given by

G3)

Chapter

13: Se

..-\342\226\240

\342\200\224

\342\200\2247\342\200\224

//
it

/
r.
\342\200\224' \342\200\236._

mi .->
Figure

13.8

Reverse-biased

p-?i

junaion,

showing

tfic cjuast-Fcrmi

levels fi, and//P.

and the junction thicknessis given

by

G4)

In the

semiconductor
field

device liierature we
approximations

often

find

G3)

term 2t/e, because certain

have

beea

and G4) without the made about the space

charge and
correct

distribution;

we

have

solved

the Poisson

equation

with

the

electron

distribution

F2).

Currtrni

Flow:

Drift

and Diffus

NONEQUILIBRIUM

SEMICONDUCTORS

Quasl-Fcrmi Levels
When

semiconductor

is illuminated
raised

with

light

of

quantum

than !he energy gap, electrons arc


conduction band.

from

the valence

energy greater txind to the conduc-

concentrations created by iliumination arc larger than their equilibrium concentrations. Similarnonequiiibrium conconcentrations arise when a forward-biased p-n junction injects a electrons 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. carriers recombine with each otlier. The recombination The excess 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 t there are di fierent Fermi levels;<c and ;iv for the two bands, called quasiThe

electron

and

the hole

ii levels: levels: emii

7\021\"

+exp[(t-\342\200\236\342\200\236)/,]\342\200\242

Quasi-Fermi

levels

are used

extensively

in

the

analysis

of semiconductor

devices.

Current Flow: Drift


If the

and

Diffusion

band quasi-Fermi level is at a constant energy a throughout are in semiconductor crystal, the conduction electrons throughout the crysta! and and thermal diffusive equilibrium, no electron current wjl! flow. Any conduction must be electron flow in a semiconductor at a uniform temperature
conduction
caused by a

position-dependence

band of. the conduction

quasi-Fermi

level.

Chapter

15; Semiconductor

Statistics
that the
density

If the gradient of this level is sufficiently


contribution

weak,

we

may

assume

conis

of

conduction

electrons

to ihe

total electrical current

proportional

to this

gradient:

J, cc grad/*(.

G6)
flux

HereJe is
electron

an

electrical

current

density,
we \342\200\224e,

not a

particle

density.

Because

each

carries Ihe

charge
5

have

x (\342\204\242e)

{electron

flux density),

G7)

where the electronilux density

is

defined

as the

number of conduction

electrons

crossing
treated electrons in

unit

area

in Chapter
the

potential, Fora
nt

Saw is unit time. The ciose connection of G6) to Ohm's 14. Because the flow of particies from to low chemical is high to grad nc, but because flux is opposite conduction electron

in

carry

the direction
given

driving

of

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

Jt_

~.

G8)

where

the proportionality
not

constant
with is

fi't

is

the

electron

mobility.

The symbol

pt

should If
the

be electron

confused

the conduction

concentration

band quasi-Fermi level,/jc. in the extrinsic but nondegenerate range,


\302\253 nc

n,
the

\302\253 nf

G9)

cottduclion

band quasi-Fermi level


as

is given by

A5),

which

can

be written

in lerms

of the eleclronconcentration
ut

+ Tlog(it7\302\253A \302\243c

(80)

Thus

G8)

become:

(81)
A

gradient

in the

conduction

band edge arises from

a gradient

in the

electrostatic

field: potential and thus from an electric

Current

Flaw:

Drift

and Diffusion

We introduce an

electron

diffusion

coefficient

Dc

by

the

Einstein

relation

Dt discussed

pex/e

(83)
the

in Chapter

14. We J,

now write (?S) or (8i) in


eDe

final

form

- eptntE 4-

grad

(84)
by

There arc two different field and one caused by Analogous


for

contributions to the current:one caused


a concentration

an

electric

gradient.
one for

results apply
in the

to holes,with

difference. holes,

The but

valence

band quasihole

Fermi levelis not ihc chemical potential


the

is the

chemical potential
current carry

electrous

valence b;ind.

a Holes arc missing electrons;

io the right

is really an

electron current to the left. But

holes

a positive

rattier than a
grad j.iv as the

current

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),
Jh \302\273

jvifcgradjv

(85)

Carrying

through

the rest

of the argument leadsto

as

the

analog the

of diffusion
but

(84),

sign in
concentrations, current,

hole holes

because

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

Injection Example:

laser.

The

semiconductors occur

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

highest

nonequilibrium

carrier concenlrations

in

semi-

condiiion

for

populaiion

inversion

is ihat

/Me) >
Wiih

fM
is expressed

(S?)
us

ilie

quasi-Fernii

distributions

G5)

this

condition

(88)

Figure

13.9

Double-heterostructtirc

right into the active


potential

barrier
from

electrons

layer,

but

cannot

becomes possible.
action

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
injection
form
where

a degenerate

For laser
The condition
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.
the additional

important

condition

is

that

the

energy

indirect

semiconductors

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

gap. The

a direct gap rather physics texts. The most


gap is

than

an

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

Flow:

Drift

and Diffusion

Example; Canter
combine or ihey

recombination

throush
falling

an iaipsiriiy
dircciiy

eiiher

by an electron

inio

a hole

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
*\342\200\236-(!

Electrons and holes can reemission of a photon, ihe energy gap. The impuciiy process
level,
with itic

~/>A

\342\200\242

(89)

w here

fr is the fraction of
available),

Itcnce not

and

t. is a

recombinationorbitais already occupied characteristic time constant for the


ai

by an capture

electron (and process. We

iissume the reverse process proceeds

tiie rate

Kc =
\302\253hcrcit'

/,'lj'e'

,
of
the

(90)
con-

is the

concentration

time constant forttie reverse process. We tnke R,, independent of conduUion ekurons, becausewe assume that i\\e < nt 1 he time

consiaitts

r.

Figure 13.10
impurity
\342\226\240

Electron-hole

recombination

ihrough

recombination

orbitais at t, inside ihe energy


.

gap-

Chapter

13;

Semiconductor

Statistics

and r,' arc related, becausein

equilibrium

ilie two

raies

Rrt

and

Rcr musi

cancel Thus

wiihf,
ihc
distribution

and

n,

evaluated

in thermal

equilibrium,

which

means
Wiih

we use
ihe

A7) for h,. We

ignore

spin

muitipiiciiy
for/,

of the rccombinaiion levels,

equilibrium

Fcnni-Dirac

we have

A -/,)//,
Thus

= exp[~{^~e,)/r].

(92)

(91)

becomes

=
^
where
^exp[~fc-\342\200\236)/!]\302\273\"\302\243.

(93)

ne' is

defined as ihe conduction


Fermi
(89)

electron

conceniralion
wjlh

lhal would

be present if

ihc

equilibrium

level
and

ft

in

A7)

coincided
net

the

recombination

level, if (92) and

(93)

arc insenedinto

(90), ihe

electron

recombinalion

rale becomes

Re =

Rcr

R,c

- ~ [A'holes

f,)nt

/,\302\273/].

(94)

The

analogous

recombinaiion

rate

Tor

is obtained

by ihe subsiituiions
!h;

Re,
and

%,\302\273/,

te

-* Rh,

flh,

nh*,

/-I
Here eiecirons,
fk

~Jr\\
in

1 -/,-/,.
thai ail

(95)

is the

lifetime n,,* is,

of holes
by

ihe

limit

recombination ceniersare occupiedby

and

definiiion,

ah* With

nBexp[-(\302\243,

ej/i]

;i,V\302\273.*-

C96>

these substiiutioiis

the net hole

rale rccombiiiation

is

Iiisteady

and (97) arc iwo

staieUicuvorecombinaUonfaiesmusibcequaS:R, ions for ihe two unknowns equal f, and /?.

=
W'i.

Hft

R.Equations /, to
find

194)

eiiminalc

(9S)

This

is the

basic rcsuli of ihe


In

recombination Hail-Siiockley-Read

iheory.'

Applications

are developed

Problems

10 and

I).

SUMMARY

!. In semiconductors (completelyoccupied band (complelely


the at empty

electron

an

energy

gap.
empty

Electrons
orbitals of

electrons;
2. The
by probability

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.
orbilals

are

grouped

into a

\342\200\224

occupancy

of a

band orbital with

energy e is governed

ihe

Fermi-Dirac

distribution

function

Here
3. The

\\i

is

the

chemical

potential

of ihe

electrons, called the


in

Fermi

ievei.

energetic
is

location of the
governed

Fermi

level

an

eleclrically

neutral

semi-

semiconductor

by the neutrality

condition

Here

ne

and is

i\\h are

the

and
negatively

An

the
charged

excess

concentrations Concentration

eiecirons and holes, of positively charged impuritiesover


of condiiction
the

impuriiies.

4.

A semiconductor
nh
\302\253 nv.

is said to be

in

classical

regime

when

ne

\302\253 nt

and

Here

are

the quantum
and

efTecItve
nc

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
bands.

valence

R. N.

Hall,

Phys.

Rev.

87, 387{i952);

\\V.

Shockley

and W.

T. Read. Jr.. Phys.

Rev.S7.

S35{!952).

. In

ihe classical

regime

where \302\243\302\243 and eu


bands.

are the

energies of

ihe edgesof the

conduction

and

valence

6. The

mass action law

stales

that

in the

classical regime the

product

\"\302\273\302\273* 'I.-1

'M'uexp(-\302\243a/i)

is
n,

independent
is

of the

impurity concentration.
nh

The intrinsicconcentration
( \342\200\224 pure)
semiconductor.

the

common

value of n{ and

in

an

intrinsic

The

quantity

is the

energy gap.
is

7.

semiconductor electrons) (wholes)


the

called
dominate;

conduction carriers

Ji-type when negative charge it is called p-type when sign of dominant ionized
The

dominate.
sign

to opposite
S,
A

carriers {- conpositive charge the dominant charge carriersis


impurities.

of the

p-n

junction

transition

fields even in the absence of an appliedvoltage. Foran field at the p-n interfaceis

is a rectifying semiconductor from p-typc to n-typi. A p-n junction

structure
contains

with

nn

internal

internal
abrupt

electric
the

junction

Here 9. The

is

the

permittivity,
and | V\\

nu Vbi

and

Mj are

ionized

acceptor

and donor

conby

concentrations,

and

are

the

applied

and the

built-in reverse bias.


are

electric

current

densities

due

to electron

and hole flow

given

JB =

e/yi,E + eDegmdne,
ephnkE

Jp ~
.

ePsgrad

nh,

Here

% and

ihe are \302\243\342\200\236

electron

and hole

mobilities, and

\342\226\240

are

ihe

electron

and hole

diffusion coefficients.

PROBLEMS

1.

Weakly when

doped the

semiconductor. net

Caiculale

tjons
2,

donor
\302\253 nt.

concentration

the electron and hole concenlrais small coinpared to the intrinsic conduc-

concentration,

jAnj

Intrinsic

conductivity

and

ininimuni

conductivity.
\342\226\240 -.

The

electrical

conductivity is

e{ntpe

+ njh)

(99)

where Jit

fl( > Jfj,. (a) Find the which the conductivity

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? K for Si for Give numerical values at 300 (c) 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.
and

ph are

the electron

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
Resistivity

3.

and

res\021 the

4.

Mass

action

form

of Ihe
Electron

is the law for high electron concentrations. DeriveC9), which no is small law of mass aclionwhen longer ne compared to ne. and

5.

hole

concentrations

in InSb.
\342\200\224

Calculate
x

nc, nh,
= ne.

and

/i

\342\200\224 for

Et

n-type

InSb at

300K, assuming nd+


narrow

4.6

1016cm\"\"J the

high ratio njn,. and the


ne
\302\253

energy
nor

gap,
is

Because of the is not hole concentration


Saw

negligible under theseconditions,


nc

the

nondegsnerate
C9).

applicable.
equation

Use
for
iont'zation

the generalized
nc by
o/

mass action

Solve

approximation Ihe tran-

transcendental

iteration or
deep

graphically.
the fraction of ionized

donor impurities doi


than

6. incomplete

if the

donor

Find imparities. tontzalton energy fs large


explains

enough lhat Aed


why

is larger

t }og(nJ8nd) by
impurity

several times t. The result


energies

substances

with

large

tonization

remain

insulators,

even if impure.

Chapter

13 s Semiconductor

Statistics

7. Built-in
and
built-in

semiconductor the ionizedacceptor Concentration


falls
eiecuic

field for exponential doping

profile.

Suppose

that

in

a .P-type

off exponentially field in the

= I0~ 103 and Xj \342\200\224 X[ as this occur in the base

to a value na~ interval (xtlJCj)? nurnerica! 5 cm. Assume T = 300 K.Impurity distributions

<- \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

the

/!s//ii

such

region of
electrons electron
a or

many

n-p-n

transistors.

The

built-in

field

aids

in

driving

the
relation

injected
for

across the

base.
Use the Joyce-Dixon of the ratio DJfic for electron

8.

Einstein

C8)to approximation concentrations


approaching

high
give

concentrations.
expansion itc,

series

exceeding

9. Injection laser. Use the Joyce-Dixon at T = to calculate approximation 300 K the electron-hole pair concentration in GaAs the inversion that satisfies

condition (88).assumingno ionized impurities.


10.

Assume both electron and hole concentrations in a semiconductor values.Definea net by 6n above their equilibrium =* R i in terms of the carrier f Give for lifetime by minority Sn/i. expressions the I lie recombination as carriereonccniraiions and level, i\\h; ne energy of it and tk, in the limits of very expressed by ne* and nh*; and the time constants small and very large values of Sn. Uiider what doping conditionsis f indepenMinority

carrier

lifetime. are raised

independentof

ditt

both pair generation. Inside a reversebiased p-n junction 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, a but in which concentration remains equal to itd+ \302\273 the electron 'i,-. (c) Give = 10Ificm~3. numerical value for this ratio for Si with ji/
11.

Electron-hole

Chapter

14

Kinetic

Theory

KINETIC

THEORY

OF

THE

IDEAL

GAS LAW

391

MaxwellDistribution of Velocities
Experimental

392
394

Verification

Collision
TRANSPORT

Cross Sections
PROCESSES

and Mean FreePaths

395
397

Particle

Diffusion

399

Thermal Conductivity
Viscosity

40!
402

Generalized

Forces

404

Einstein Relation

406
BALANCE

KINETICSOF
ADVANCED

DETAILED

407

TREATMENT;

BOLTZMANN

TRANSPORT EQUATION

408
409

Particle
Classical
Electrical

Diffusion

Distribution

4!0

Fermi-Dirac Distribution
Conductivity

4!
413

LAWS

OF RARF.FIED
Molecules

GASES
a Hole

413
414

Flowof
Speed

Through

Example: Flow
of

Through a LongTube

4!6
417

a Pump

SUMMARY

I'KOIiUCMS

419
in a

1.

Mean

Speeds

Maxwcllian

Distribution

419
420
420

in a Beam 2. Mean KineticEnergy to ElectricalConductivity 3. Ratio of Thermal

4.

Thermal
Boitzmann

Conductivity
Equation

of Metals
and

420
Conductivity

5.

Thermal

421

Chapter14: Kinetic
6.

Theory

Flow

Through

a Tube

421

7. Speedof a Tube

421
only an individual
in

ant

conscious

of being

struggling weaklyagainstthe
in

stream

of time.

But if still

remains

my

power

to contribute
too

such

a way

thai, when

the theory

of gases is againreviled,not

much

will have to be

rediscovered.

L, Betiynann

Kinetic

Theory

of the

Ideal

Ga>

!n

of velocities

we give a kinetic derivationof dieideal law, the distribution gas of gas molecules, and in gases: diffusion, transport 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
this

chapter

of transport

is difficult.

KINETIC
We apply
~

THEORY OF THE
the kinetic
Nx.
denote

IDEAL

GAS

LAW

method to obtain an
molecules
the

elementary

derivation
unit

of the
of

law, pV container. Let v,

Consider
If a

velocity

that strike a area normal to the component

the

ideal gas wall of a

as

plane of the wall.


(mirror-likcj

in

Figure

14.1.

molecule of

mass M

is
the

reflected
molecule

specularly
is

from the

of wall, the changeof momciitum


\342\200\224

2A/|i-x|.

A)

This

gives an

pressureon

impulse 2M|i>.|to the wall,


the

by

Newton's

second

law of

motion. The

wall

is

_ /momentum
\\

cliangc\\/number )\\
unit

of molecules strikmgN
area

pj

per

molecule

per

unit

lime

. Let a(vI)ilv1
of

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
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

v.la{vMv..

C)

the

thermal

average

average of v22 times value of JjMi-e2 is |t,

the
by

concentration,
equipartition

of

change
ily

v which

of momentum of a is reftecied from


~-2M\\vz\\.

ntaincris

energy

(Chapter

3). Thus

the pressure

is
= (NfV)z;

p=

iiAf<ps2>

'it

D)

This is the idealgas law.


The

assum
What

ption
comes

of specular
into

reflection is convenient, but


must go

it is the

immaterial
same

to the

result.

t!:e surface

back,

with

distribution,

if thermal

equilibrium is to be maintained.
Distribution

Maxwell

of Velocities
function

We now
say

transform the energy distribution


distribution

of

an

ideal

gas

into a

classical velocity
\"velocity\",

function.

Often
in

when we
when

as

this
found

is the
the

tradition
distribution

physics

we shall mean \"speed\" no confusion is caused. ideal gas to be

In Chapter 6 we

function

of an

Ati =
where/(cn)

E)
of an orbital of energy

is

tltc

probability

of occupancy

\342\200\242

ui\\l

in a
number

cube of volume
between it and

V n

=
+

Li,

The average

tin is

number of atoms with quantum x (the (tlie number of orbilals in this range)
in

probability

such an orbital is occupied). Tltenumberoforbitals

the

positive

MaxwellDistribution

of t'ekctlies

shellof octant of a spherical product is

thickness

tin

is ^Dnn2)(Int

whence

the desired

= {{nn2dn)f{zK)
We

&/.n*exp(-\302\243jz)dn.

G)

take

the spin
the

of the atom as zero.


probability

To obtain
find

distribution

of

the classical
n

velocity, we must
classical

connection

between

the quantum
classical The \302\243\342\200\236.

number

and

the

velocny

of a

particle in the orbital quantum energyF) by

kineticenergy

\\Mvz is

related to the

We

consider

atoms

with
G)

from

and

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

ii.;/^Yi.2cxp(-A/o:1/2i),/i..

(9)

From

Chapter 6 we know
of

that

}.

n/\302\273Q

(.V/L^^lnt^fMTK'2,

so that

the

fiidor staiidiiig to the left

v1 becomes

Thus

\342\226\240!n(A//2j[i)lV<:.\\p(-A/rV2r).

(ll)

Tin's

The quantity Maxwell velocity iIis(ribulion(Figure14.2). 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
is the

P(i

Mr

is (lie

of the
Table

root
!4.I,

!.

i
Figure t-l.2 function of
probable arc the

\\

\\

Mawveil velocity distribution


the

as

speed

in units

of

\\

the

most shown

speed tm(,

mean speed
i-AK1.

c and

* {2t/A/I\". Also
ttie

loot

mean square

/
1/

_
\\

velocity

Table

4.1

ofcculat \342\226\240 *e!ocilies 31273


? Gas

K,

iin

10*01115\"'

Gas

\".\342\200\236,

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

H,

18.4

16.9

Oi

4.6

4.2

He

13.1

12.1

Ar

4.3

40

H,n

6.2

5.7

Ne

5.8

53

Kr Xe

2.86

2.27

N,

4.9

4.5

Free electron

1100.

1013.

2.63 2.09

Experimental which

verification. exit

The

velocity

distribution

of atoms
by

of potassium
and

from
in

the slit
14.3

of an

oven has beenstudied

Marcus

McFee.*

The curve

Figure

of A2)
different

below;

theagreement

the compares is excehent.


a

distribution
from

of atoms
the

that exit from


distribution

experimental results with the prediction We need an expression for the velocity smatf hole1 in an oven. This distributionis
within
velocity

velocity

the oven,
component

because the flux


normal

through

factor, the The exit beam is weighted favor of atoins


the

ho^e

involves

an extra

to the

watt.
atoms

in

of high

of velocity at the expense


ed. }. Esterman,

those
\342\200\242

at

low

velocity.

In proportion

to thetr
research

concentration in the oven,fast


fceanw,

P. M.

Marcus and

Press, 1959.
\342\226\240\"\342\226\240

J. H. McFee,Recent

in molecular
if ihe

Academic

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
by

lhetawsofbydrodynamic

Bow and

not

by

diameicr is less than a mean free paih flow of gas from it will be governed [be sense, gas kinetics.

i SecUtms and Me

10 9
>?

-?*

n
zj

2
1

V
10

U 12 13

Tiansit
Measured

time
points

figure

14.3

traiistnissio\302\273

and atoms

calculated
axis

Maxwell transmission

curve for

potassium homontal

an oven al
lime

a temperature

E?\302\260C.The

that exit is Ihe

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

stitke the walis more often

ihan

slow

atoms

strike

Ihe walls.

The weightfactor

to the plane of ihe hole.The average is factor, J. The of cos 0 over ihe forward hemisphere namely jusl a numerical thai an atom which leavesthe hole will have a velocity between probability

is

the

velocity

component

ucosf?

normal

and

v +

dv deftnes

ihe quantity

PbciJ,v)iSv,

where

wiih

P,,(,Iwett given

by (H).

The distributionA2)
transmission

of

ihe

transmission

through

hole is calledihe Maxwell


Collision
We

distribution

Cross Sections
estimate

and Mean FreePaths


rates of
we see

can

ihe collision
will

gas atoms viewed


centers

as

rigid

spheres.

Two

aioms of

diameter d
From

collide

if their

pass wiihin ihe distance4 of


occur

eachother.

Figure

14.4

thai one

collision will

when

an atom

has traversed

an averagedistance

A3)

Chapter

14:

K'tnaic

Theory

Figure

14.4

(a) Two
(b) An

rigid spheres
a distance

will

collide

if their

centers pass
a long

within

d of
oul

each

cacliother,
travels

arom of

diameter d which
sweep

distance L

will

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

is

the

number
the

of atoms
distance

freepath:it is
result We diameter

per

unit

volume.

Tiie

length

/is called

the mean

average

traveled

by an

Our atom between collisions.

neglects estimate d is

the the

velocity order

of the

target atoms. of the mean free path.

2.2 A

as for

section cross [ielium, then die collision ac


\302\253= 15.3

of magnitude

If tlie atomic
is

at=

nit2 =

C.14)B.2 x KT'crnJ
idea!

lO-i6cm2.

A4)
is given

The coiicenEration

of moleculesofan

gas

atO:Cand

atm

by the

Losclimidt number
m0

2.69

x IOi9atumscnrJ.
divided

A5)

defined as the Avogadro

number

by the

molar volume at
combine

O'C and 1aim


molar

The
volume

Avogadro

number

is

the

number

of molecules in

one mole; tUe


(M)

is the

volume occupied by one mole.We

a ad

A5) to obtain

Transport

Processes

the

mean

free path

under standard conditions:

\342\200\2243\342\200\224

tttz

]7pT6

2\\rT9

lO*7\"\"\"\"^
the

= 2M *

1\302\260\"i Cm'

^16a'

This

length

is about

associated collision rateis

1000 times larger than

diameter

of an

atom. The

or Idynecm\022, the concentration of atorr.: s reduced iG\026 and the mean free path is increasedto 25cm. At 10\026aim the by mean free path may not be smallin comparison with the dimensions of any \\ acui:m we are Then in wliat is called the high particular experimental apparatus. that the meaii free below also called the Knudscn region. We assume region,
At

pressure

of

I0~6atm

path
except

is

small

in

comparison

with

the relevant

dimension of

the

apparauis,

in the

section on

laws of rarefied gases.

TRANSPORT

PROCESSES

Consider

a system
a constant

state

with

not in thermal equilibrium,but How from one end of tiic system


state

in to

a nonequilibrium the

otUer.

steady For example,


tempera'

we may create a

steady

noncquilibrium

condition

in a

system by placing
How

opposite endsin
tures.

thermal
1

contact at

with

large reservoirs

at two different
will

If reservoir

is

the

higher

temperature,
flow

energy
in this

through
will

the

system
the

total

from reservoir 1 to reservoir2. Energy entropy of reservoir 1 -f reservoir


in

direction

increase

+ system. The temperature


quantity

gradient
transported

the

system the

is the specimen region

through
is

driving force; the physical in this process is energy.


in

that

is trans-

There
directly

linear

most

transport

processes in which the

flux

is

proportional

to the
flux

driving force;
(coefficient)

s=

x (driving

force) ,
is called

A7}
a linear

provided the force is not too large.Such

relation

phenome-

noiogicai
of

law,

such

as Ohm's

law for
A

Thedefinition the conduction of electricity.


oM transported
unit

the

flux density

of a

quantity
of
A

is:

3A

= flux density

net

quantity

across
(IS)

unit area in

time.

Table 14.2

Summary

of

phcnomenologica!

transport

laws

Flux of

particle
Effect

property

Gradient

Coefficient

Diffusion

Number

~
dz

DifTusmty/)

J,

Viscosity

Transverse

dv. M ~~

Viscosity

i;

Thermal conductivity

Energy

\342\200\224 = Ct \"

Thermal
\"z

JB
K

conductiviiy

ictricai Electrical

Charge

-~
a:

E,

Conductiviiy

J.

conductivity
bols:

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

ip *=\302\273 elccirosuiicpolcniial

M
p

E = electricfield intensity q = elcciticchdrgt;


^=

mass

\342\200\224 mass

of parucle per unit volume

p ^

momentum

The net

transport is the transport in

one

direction
are

minus

laws opposiie direction.Varioustransport

summarized

the transport in in Table 14.2.

the

Particle
In

Diffusion

Figure

14.5 we

consider a

reservoir

at chemical

system with one end in potential /ij; the other end is in


The

diffusive
diffusive

contact
contact

with

with

reservoir
from

at chemical potentialft2.
chemical 1 to

temperature

is at the higher
reservoir

potential,

then

particles
2 -f the

If is constant. wili flow through


will

reservoir I the system


the

reservoir
H-

2. Particle
reservoir
first

flow in this direction


system. difference in unit

increase

total

entropy Consider particle


by

of reservoir 1
difference

diffusion,

when

of chemical

potential is
Jn

caused

in particle

concentration.
a'uait

Tile

flux

density

is the

number of particles p;isshig through of isothermal diffusion is usually


concentration along

urea

taken

as thc\"gradicnt

time. Tltc driving force of the particle concentra-

the

system;

-,)n =

-Dgradti.
ts

A9)
putt

The relation ts
diffusivity.

called

Fick's

law;

here D

the

tele

diffusion

constant

or

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 chemicalpotential and condition jt{z) the free Across local of aiean concentration >\\{:). Let /. be the z component path. 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

over distances

Figure 14.5
contact

\342\226\240

Opposite

ends

with reservoirs

of the system are in at chemicalpotentials /it

diffusive

and/ij.

The

-. temperature is constant everywhere.

Chapter

14i

Kinetic

Theory

flux density

is the averageoverail

directions

on

a hemisphere

of

B0)
We

want

to

express

the average

value of cjg
path, is

tn

terms

of?/. is the

Here

it =

ts the

projection of the meanfree


average forward

and taken

c.

\342\200\224 ?cos<?

projection

IcosO of the

speed on the z axis.The beca becauseall directions

are

is 2xs'm0i}9.
Thus

equally

of a hemisphere, likely. The eletnent of surface area


over

the surface

B1)

B2)

On

comparison

with A9)

we see that

the

diiTusivtty

is given

by

The particle

diffusion problemis the


we

model

for

other

transport
in

problems.
thermal

In
the
the

particle
conductivity

dilTusioii

are

coneerncd

with the

transport of particles;in
by

with

the transport by particles.

of energy
and

particles;

viscosity

with
with

transport of momentum by
transport

particles;

in electrical

conductivity
that D, A. molecules,

of charge

The linear transport coefficients


If A

describe

tile

processes
Let

pA

like charge or :r.:iss that


density of A
in

are proportional to the particledilTusivity denote the concentration of ihe physical quantity
has

is a
then

quantity
the flux

tile

same

value for

all

the

the

z direction

is

j;
ulierc

e,<\302\273,>.

(-\342\200\242')

(i';)

is the

mean drift velocity of the

p;irtidcs in
that

tlie

z directioii.'!

lie drift

velocity is zero in thermal equilibrium. If /{ is a quantity like energyor momentum

depends

on the

velocity of

a molecule, then we always

find

a similar

expression; ,

\342\226\240>/

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 where

fA is

a factor with

126)

with

the particle
Conductivity

diffusjvity D given

by B2).

Thermal
Fourier's

faw

Ju describes

\342\200\224

^Cg

B7)

the energy llux


but

density Ju
not

in

terms

of

the

thermal
assumes

conductivity
that

K and
is a

the temperaturegradient (Figure14.6). This

form

there
electrons

nci
flow

transport of
additional

energyt

of particles.

Another

term must be addedif


flow,

addi-

energy

is transported

by means in the z

under the
The

influence of an eiectricfield.
flux

of particle

as

v,hen

energy

density

direction is
=s />\342\200\236<!\342\200\242-> ,

JJ
where
valid

128)

^o,i> is
within

the mean
factor

drift

velocity;

pu

is the

energy density.

This result is
with

of the

order of unity, as discussed.By

analogy

the

diffusion

equation,

the right-hand side is equalto

-DdpJAx = -D(tV,/cr)(i/t/i/x).

B9)

Reservoir

Reservoir

Figure 1-1.6

Opposiie endsof the


reservoirs

system

conijci

wiih

at lempcratures

arc in thermal r, and ij.

Chapter 14: Kinetic


This

Theory

describes
unit

the diffusion
denoted

of energy. Now
Cy. Thus
-

dpjet

is just

the heat

capacity

per

volume,

by

-Ju

-.DCYgradr;
is

C0)

on comparison with

B7) the thermalconductivity

C1)

The thermal

at very low of pressure until conductivity of a gas is independent 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

losses are independentof pressure as


Viscosity

long

as C1)

applies.

Viscosity is a measureof the

diffusion

of momentum

parallel

to the How velocity

and transverseto
velocity

the

gradient
with

of
the

the
Slow

in the .x direction,
is

flow velocity. Consider gradient in the velocity

a gas with
z direction.

flow

The

viscosity coefficient tj

defined

by

C2)

Here
component

vx

is

the

x component

of momentum;

of the flow velocity of the gas; px denotes the ofthe shearforce exerted and X. is the x component
normal

.v

by the gas

on a unit
of

urea of thexj' plane


a shear

to

tlte z

second law

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.
motion

stress X.

direction. By Newton's if the plane receives plane


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

z direction

-Dp

daJds

-n

C3)

Thus, with

given

by B3),

rj

Dp

= y-c!

C4)

of viscosity. gives the coefficient The


and mean

The
\\jnd2n

CGS
from

unit

free

path

is / =

A3),

of viscosity where d is the


may

is called the poise.

molecular diameier
as

n is

the con

cent rat ion.

Thus the viscosity


rt

be

expressed

htcfiml1

C5)
independence
than

which is independent of the


pressures

gas

pressurp.

Tlie

fails at
at

very

high

when

the

molecules

arc nearly always in contact or

very

low

pressures

when

the mean free


In

path

is

longer

the

dimensions

of the

apparatus.

Robert
independence

Boyle

1660

reported

an early
in

observation on the pressureindeair:

of

the

damping

of a

pendulum

also that when the Receiver was full of Air, its Recursions about fifteen minutes (or a an U of quarterof hour) before left off swinging; and ikat after the t'xsnciion the ihe Vibration the same Pendulum Air, {being put into motion) of fresh appeared not (by a minutes Walch) to last sensiblylonger.Sothat the event of we expected, scarce afforded us any oiher this experiment being other than satisfaction,than that of our not haviiuj umitleil to try it.
Experiment
the

26

included

Pendulum

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 transfer collision larger the momentum difference; the increasingmomentum per cancels the decreasing collision rate. It is easierto measure the than the diffusivity. HD = r\\jp as predicted viscosity by C4), then K is rclaiedto jj by Although

at

first glance

- nCyfp.
Kp/rjCy

C6)

The observed
higher Improved

values

of

than

the

value
of

calculations

14,3 are somewhat unity predicted by our approximate calculations.Imthe kinetic coefficients K, D, i] take account of minor,
the

ratio

given in Table

Chapter 14: Kinetic


14,3

Theory

Tabie

Experimental
in

values of K, D,ij, and


K~l
D,

Kp/tjCy

at

0rC

and

l atm

Gas

K,

mWcm\"'

incm*sM

/, in

;\302\273poise

we. 2.40 2.49

He
Ar

1.50

186.

0.18

0.158

210.

Hi

1.82

1.28

84.

1.91

N,

0.26

167.

1.91

Oj

0.27

189.

1.90

but

difficult,

effects

we

have

neglected;

see the works cited

in

the

general

references.

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 Comment,

The

dilTusivity

of

gas

atoms

of a parliclc

Comment,

Tlie quaniily
diffusii-ify criierion

tj/p

be equal

to ihe Reynold'snumber

is caJlcdrlIie

kinemaiic viscosiiy;if
into

C4)

iiotds,

v should

D. The

raiio

i\\/p

eiiicrs

iiydrodynamic

iheory and into the

for taminar

flow.

Generalized Forces

The transfer of entropy

from

one

of

any

transport

process.

We

system to another is a consequence to ihe can relate the rate of changeof entropy
pars

of a

flux

and of energy. By identity at constant volume,


density

of particles

analogy

with

the

thcrmodynaniic

da = -c\\Vwe write

}~

(IN

C7)

the entropy

current

density

Ja

as

C8)

denote the entropy density; let cafdt denote the entropy density at a fixed position r. Then, by the equation
Let a

net

rate

of

change

o(

of continuity,

cajdt
In

divjo.

C9)

volume is equal to the element the net rate of appearanceof entropy rate of productionga minusthe loss - div Jo attributed to the transport current.
a

unit

In

a transfer

process
is

U and

The N are conserved.

equation

of continuity

for

the energy

density u

\342\226\240=

-divju;

D0)

the equation

of continuity for the

particle concentrationti

is

{41)

Let us

take the divergenceof Jo in


= idivJ.

C8);

divJa

+ Ju-grad{l/t)
div

Let C7)

(tt/x)

Ja

- Jn

\342\226\240

grader).

D2)

refer to
the

unit

volume;

we

take

a partial

derivative with respect to

time

to

obtain

net

rate

of entropy

change:
~~

dd
ct

1 cu
t ci

i\\

en

tot'
form

D3)
of

We

use

D0H43)

to

rearrange

C9) in a

suggestive

the

ohntic

power

dissipation:

3. = J.

grailUM

J,

\342\226\240

gradi-;</r)

W)

Here

Fu and

Fa are

generalized forcesdefined
F.

by

s grad(Vr);

F, = grad(-;</r).

D6)

Chapter

14:

Kinetic

Theory

In an

lit terms

isothermal processF, iii D6) may be written as of ihe internal and externalparts of the chemical
Fn =

Fn

==

{-I/t)grad/i

or, as

potential,

-\"{i/t
xlog{n/nQ), <=

D7)
so q gradtp

For an ideal gas


electrostatic

n,Rt

==

that

grad/jjni
qE.

= {r'n)gradn;

for

an

potential

gfad^\302\2431,

\342\200\224 \302\273 Thus

Fn
the

-UAJO^gradn
also has two
>= terms,

-gE]
written

D8)

How

particle

flux density

as

3\302\253

-i>ngrad\302\253 4- uflE

D9)
to E

where D, is the

dtfTusjvity

and

p. is

the mobility,
coefficients be

which is the drift


of

unit eleciricfield.The raiio of the and rfnq in D8). These ratios must

equal,

gradn so that

velocity per is Djnp. in D9)

E0)

which is calledihe Einsiein


for

relation

between

ihe

diffusivity

and the

mobility

a classical

gas.

Comment.
irreversible processes,

We gain an advantage,for
if we
write

reasons

relalcd
the

to the

thermodynamics of irreversfor the

use

FM

and

FH in

D6) as

driving

forces

linear transport

processes. We

Ju

=\342\200\242

Z,aiF,

L12FB;

Jn =

t2tF,,+L22F,

E1)

The

Onsager

relation

of irreversible

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
KINETICS

Bohr.

OF

DETAILED

BALANCE

Consider a system whh two states, one at energy A and one at energy -A. In an ensemble of N such systems,N* are at A and N\" are al \342\200\224A, with \\ == N* + N\". To establish thermal equilibrium there must sonic exbt mechanism Consider the rate equaiion whereby syslems can pass belwecnihe two stales. for transitions into and out of the upperstate:
dN+/(lt

uN~

- PK+ ,

E3)
\342\200\224 to \342\200\224

wherea,
+
transition 4-

/J

may

be

functions

of the

temperature. The transitionrate from


in

ts directly
rate

proportional
-1-

to the number of systems


directly

the

state.

The

transi-

from

to

\342\200\224 is

proportional

to the
can

number of systems in the


be satisfied

state.

In

thermal

equilibrium

(i/JV*/i/i)

= 0, which
=

only if

afp =

<N
result

>/<N\">

exp(~2A/r)

E4)
/J(t)

the Boltzmann
must

factor.

This

expresses
mechanism

a relation
that

between a(rj and


in the
with

that

be satisfied

by any and every


a

assists
proceeds

transitions. As
the excitation
+ In

an example, suppose that the of a harmonic oscillatorfrom


in the

transition state

+ -+ of energy oscillator

\342\200\224

* + inverse process the mechanical theory of the quantum

se to a state goes from se


is shown

of energy (s to (s \342\200\224 i)e.

I)e; the

oscillator
-+

it

that

__

Prob{s

s +

1)

__

for

the excitation

texts on

quantum 'heory.The value of (s) isfound W W


\342\200\224J \302\253 <*\342\200\242> <*>

and de-excitation of the oscillator,a


from

result

derived

in

most

the

Planck

distribution;

exp(e/r)- P

\342\200\242

<sy W W
<sy

= + i = +

exp(E/T)
exp(e/t)

'

so thai, with

= \302\243

2A to

conserve energy,
<5>/<s

aft -

1)

exp(-2A/r).

E5)

This satisfies the condition E4).


The in

principle

of detailed equilibrium

balance
the

thermal

emerges as a generalization ofthisargument: leads to a given state must rate of any process that

Chapter14t Kinetic
equal

Theory

exactly

the rate

common application of the principle is to the Kirchhoff law for the absorption and emission of radiation a solid, discussed in 4: radiation by already Chapter 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.

of the inverse process that

leads

from

the

state.

One

ADVANCED TREATMENT:
BOLTZMANN

TRANSPORT

EQUATION

The

classical
We

theory of
work

transport processesis
the six-dimensional

based

on

the Boltzmann

transport

equation.
velocity

in

v. Tiie

classical

distribution

space of Cartesian coordinatesr mul function /{r,v) is defined by ihe relation

f{t,\\)thdv

= number
is derived
dt

of particles in drdv.
by the

E6)
We

Tlie
the

Boltzmann

equation

following argument.
function.

consider

displacement mechanics rells theorem of classical


effect

of a time

on

the

distribution

The Liouville

us

that

if we

follow a volumeelement along

flowline

the

distribution

is conserved:

f(t
in

+ i!t,r -+

tk.v

d\\) =

/(f.r.v) ,

E7)

the

absence

of collisions.

With collisions
tle,\\ +

fit +
Thus

dt.T

dv)

- f(t,r.v) =

dt(ff/ct\\mijoni,

E8)

dt(cf/c!)
Let

+ dr-

gradr/+(/v

gradv/ = (/t(f//^)Mu-

E9)

a denote

the acceleration dv/tli;

ihen

cflct +
This

\342\226\240

grad,

/+

\342\226\240

gradv

\302\253

{df/ct)tM.

F0)

is the
many

Bohzmann transport equation.


problems

In

the

collision

lerm (cf/ct)eolJ

may be treatedby

the

introduc-

of introduction

a relaxation

time rc{r,v\\ defined by

the equation

ParticleDiffusion
is the
relaxation of

Here/0
for

distribution
time velocities

with

function in thermal equilibrium. t for temperature. Suppose thai


is set

Do not confuserc a noncquilibrium


suddenly

distribution

up by external forceswhieh

are

removed.
(torn

The decay

of the distribution towards equilibrium is then

obtained

F1)

as

- f0)
= 0 by

f ~fo

F2)
distribution.

if

we

note

that

dfo/dt

definition of the

equilibrium

This

equation

has the

solution

F3)
ft

is

not

exeluded

that xc may
and E6), \302\24360),

be a
F1)

function

of

r and

v.

We combine
iu

to obtain

the Boitzmanu

transport equa

the

relaxation

time

approximation:

F4)

In the
Particle

steady state cf/ct =


Diffusion

by

definition.

Consider an isotliermalsystem

with transport

a gradient equation

The steady-stateBoltzmann
approximation

of the particle in the relaxation

concentration. time approxiF5)

becomes

v.dffdx*

-(/-/0)/i{,
along

where the nonequiltbritim distributionfunction/ varies as We may write {65)to first order
^fo-vsMJx, /\302\273

the

x direciion.

F6)

where

we have
when

replaced cf/'dxby
desired.

dfojJx.

We

can

iterate

to obtain

higher order

solutions

Thus

the second -

order solution
vj^lfjdx

is F7)

fi= fo- o^M'lx =

/\342\200\236

-f vxlr*tllfalilx\\

is The iteration

necessary

for

the

treatment

of nonlinear

effects.

Chapter

14:

Kinetic

Theory

Classical

Distribution
in

Let/0 be the distribution function


/0 =

the

classical

ijmil:

exp[(/* -

e)/i],
normalization iransport rather \302\24368)

F8)
for equation than

as

in

Chapter

6.

We

distribution linear in E6). Then

function

art; ai Iibeny io take whatever is most convenient becausethe


can

the is as in

/ and f0.

We

take

the

normalization

as in

dfoftlx and the


first

(ilfofduWtifdx)

ifoh){dn/dx)

F9)

order

solution

F6)

for the

nonequilibrium distribution becomes


G0)

/ = /o The

(^J0/x)(dti/dx).

particle

flux density

in the

x directionis

J/-$vxff>ie)de,
where

G1)
energy

is the \342\226\240Dfc)

density

of orbitals

per unit volume per unit

range:

\302\273,

G2,

as

in G.65)

for a

particle of spin
=
JuI/01D(\302\243)f/E

zero.

Thus

J/

idn/dx)

jiuJxJohM^k
function

G3)
fQ is for

The first
function

integral

vanishes

because

v3 is

an odd

and

an even

func-

distribution

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:
of

vx. This

flux

vanishes

the equilibrium

Fermi'Dirac Distribution
The

integral

may

be written

as
=
J(iMi'!)/0O(e)\302\253fe

i JV/oO(E)<fe= ~j

,n/M

G5)

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 *=

|nt
density

of the
is

particles. Here

-{nxJKtyiflnldx)

\302\253

-{z(z/M)(dn/(lx)

G6)

=
with

xlagn
the

+ constant.
diffustvity

The result G6) is of the

form

of

the

diffusion

equation

= Vr/A/.=

K\022>V

G7)

time is that it is inversely Another possibleassumption about the relaxation ~ as in rc l/v, where the meanfreepalh 1isconstant. proportional to the velocity,
Instead

of

G4)

we have

J* =
~(dft/dx)(l/T)j(vx2/v)focD(\302\243)dB

G8)

and

now the

integral may be written as

J
where

i>ic

G9)

c is the

average speed. Thus

J.x
and t!:e diffusivity
is

\302\273

-i(^\302\273A)W/V^)

~\\mdn/dx)

(80)

= \302\243>

lie.

(81)

Fermt-Dlrac

Distribution
is

The distributionfunction

- ^_
;XP[(\302\243

WAJ +

'

(82)
\342\200\242 \342\226\240

Chapter

14:

Kinetic

Theory the derivative

To form

dfo/dx as in

F9)

we

need

dfo/dfi. We ,

argue

bciow

lhat

'tfJdH

x 6{e-'y)

(83) function, which has the

at low temperaturesr
property

\302\253

ft.

Here

5 is the

Dirac delta

for

a general

function

F[c)

that

Now

consider
s

the integral
=^ n

F{c){dfOl'dii)j\302\243. j\302\243

At low

temperatures
is F(\302\243)

dfQ/dfi is very
very

large for
varying

and

ts smail

elsewhere. Unlessthe function


the

rapidly

near n we may

outside take F{e)

integral,

with

the value

Fin):

(85) where we
At low
have

used

dfo/dn

=*

~df0/dz.

We
the

have

also used
side

temperatures /@) =
with

1;

thus

right-hand

= co. f0 = 0 for \302\243 of (85) is just F[}i),

consistent

the

delta

function
dfoftlx

approximation.
=

Thus

S(e

- v)d[i/dx.

(86)

The

particle

fiux

density

is, from

Giy

(87) = /( of the Fermisphere. The


,

wheret{ is
integral

the

relaxation

time

at the

surface e

has

the Vaiue

M3n/2cf)
by
defines

nlm

(88)

use

of Q([t)
tile

~ 3;i/2ef at absolulczero,from velocity vf ort the Fermi surface.Thus


JM' \302\253

G.!7),

where

zF =

\\mvF2

-(m,;i\302\273)Jii!Jx.

(S9)

At absoluie

zero ii@)

{h2j2in)Cji2n}2

J, whence

Jlt/ilx

= {ilftV-mKJii')''1/\"\021}''\"/*

5(\302\243r/\302\273),/ii.V/.v,

(90)

Laws

of Rartfitd

Gaits

so that (S7) becomes

//=
The diffusivity

~Bxt/3m)t:Fdn/dx

~\\ve\\dnfdx.

(91)

is the coefficient otdn/dx:


D

\\vF\\

(92)

closely similarin
In

form

to

the resuh

{77} for the

classicaldistributionofvelocities.
Fermi the

{92} the

relaxation

time is

to be taken at the

energy. Fermi-Dirac

We

see we

applies,

can solve transport problems where as in metals, as easily as where the classical Conductivity
a

distribution

approximation

applies.

Electrical

The isothermalelectrical conductivity


difiusivity

follows

when

we

muliiply
ihe

the particle

from the result for ihe panicle flux density by the particle chargeq

and

replace

the

gradient

dji/dx of the
potential,

cfdq>fdx

~-<j\302\243i of

external

chemical potential by the where Ex is the .v component


follows

gradient of the

electric

field intensity.

The electriccurrentdensity
J,

from

{76}:

H\\/'\302\273)E;

uqhjni

(93)

for a classical gas with


from

relaxation

time

xc. For

the Fermi-Dirac

distribution,

(89},

J,

(nq2xc/m)E;

*=

nq'xjm.

(94)

LAWS

OF
far

RAREFIED
this

GASES
the

Thus
molecular

in

chapter

discussion

of transport has assumed that


mean

the

mean
At

free path
a

apparatus.
path

gas

pressure

is short in comparisonwith the dimensions of i(T6atm at room temperature,the


The

of the
free

ofa molecule

is of the order of 25cm.


be

diameter
of

of a
the

laboratory
order

system conneciionmay free path. We may usefully


1 1

of

the order

of 25 cm, thus

of ihe

vacuum mean
than or

draw

a line

lower here and denote pressures

x x

10~6atm 10~6kgcm~2 of

as high or

vacuum. This pressure 7.6 x 30\"\"*mmHg or


the

7.6 x I(T4torr. The


which
A

0.1Nra\021 is approximately
Knudsen

region

pressures

is understood
dimensions

to be the regionin
of the

the

mean

free path
of

is much grealer than

apparatus.

knowledge

the

behavior

of gases

in

this

pressure

region
by the

is important American

in

the

use

of high

vacuum

pumps and allied equipment.

The
terms

terminology

recommended

in

of torr,

where
here

torr

;= 1 mm

1333dynecm~3;

bar

Then:
high

Vacuum Society is expressed = x 1.333 3O\"~3bar=133.3 Nnf2 = Hg = 0.9S7 standard atmospheres. !06dynecm~2

vacuum

iO~3-i(T6

torr

very high vacuum

3O~6-3O~9 torr
below

ultra high vacuum


Flow of

3G~9

torr.

Molecules Through a Hole


regime

in ilic Knudsen
in order

we

do not
of

need to
gas

solve a hydrodynamic
through

flow

problem

to get
molecules

the rate of efflux


sec

do molecules
which

not

each
unit

other.
area

We

because the to the calculate rale Jfl at have merely


molecules

a hole,
find

strike

of surface

per unit

time. We

for

tlie

flux

density

(95)

where
prove

is

the

concentration a unit

(95),

consider

and c is the cube containing


per

To mean speed of a gas molecule.


n

molecules.

Each

molecule

strikes

the + z face ofthe cubejct times

unit

time,

so thattn
c cos

unit time^nc, require the

molecules average of

strike unit
We

area.

solve
over

for ?, in
a hemisphere:

c. *= terms of c. Because

0, we

cos#

2*
=

J^2

cos 8 sin 1(8


\"\"

j
1'

(96)

~2n

[\"\\\\aedf

Therefore the basis

?,

\302\253 \\c,

and

(95) is

obtained. The
of gas

expression (95)for

the

flux

forms

for many
the

calculations

flow in vacuum

physics in the Knudsen


which

regime.

If

is

area
unit

of the
time,

hole,
is

the

iota!

particle

flux,

is the

number of

molecules per

nS ,

(97)

Flow

of

Molecules

Through

a Hols

S =

l-ic.
as the

(98)
lime

The conductances of
through

the

hole the

is defined

the hole,
=>

with

volume

taken

volume of gas per unit at the actual pressure p of


per

flowing

the

gas. The

conductance 10cm
liter/sec.

is usually
300

moleculeat T

expressed in
have c

liters

second.

For
for

the average
a

air
of

diameter, hole
with

lQ4cms~'; leads a to conductanceof 917 (98)


K we
a given
n

x 4.7 x

circular
roughly

hole

liter/sec,

1000

For a

conductance ~ m, p

the total

particle

flux

is

proportional

to

the concentration

or,

because

to the

pressure p:

Here-

we

have

defined

the quantity

Q~pS,

A00)

A01)

Thecondition

for

zero

net

flux is

In the using the proportionality of c io t1'2. do not imply zero net flux tf the temperatures
At
flow

Knudsen

regime

equal

pressures

equal
requires

pressures

gas

will

flow

from

the

two sides are different. cold side to the hot side; zerogas
on the

a higher

pressure

on the hot

side.

...

Chapter

!4:

Kinetic

Theory

Eft,

- t2, Eq.A01) can

be

\\

-(p,

- p2)S =

~AQ

C03)

where

Example; Flow
wail

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 moiecuics to the waii before striking the wall. parallel 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)
through

a hns

tube.
in

We assume
directions;

that

the

of

the

tube

are rc-emittcd

ali

that

\\nld)ic

,
lube. The &p:

A05)
the

whered is the
must

diameter

and'

L the

length

of the

momentum transfer to

tube

equal

the force due

to the

pressure

differential

{nLMcM(u}
We

=* AAp.

A06)

solve

for tile

flow velocity

(u) to

obtain

A07)
<u>--\302\243w:ln\302\260'\302\245mr

The net

flux

is

AO

- n(u)A

Ap

\342\200\224

A0$)

wher

S =

tA\302\253/Ap= \342\200\224j-

A09)

is the

conductance

of the lube, defined

analogously

to the

conductance

of a hole, Eq.(97).

Speed

of a

Pump

more

detailed

calculation,
conductance

arefully, leads

lo a

with averages
differing

over the
by

velocity a factor

distribution

take

from A09)

S/3*:

xAi

2t\302\253/J

The

conductance

of a tube

(98),A10), and A21)below.

cannot be larger than

that

of a

bole

with

the

same

area. From

This

ratio

that

every

will be larger molecule hits

than

unity

for

1L <

4d.
tioi

In

writing

A06)

we assumed

implicitly

ihc tube wall. This will


that means

valid we must compared to uniiy,


to be

suppose which

the

short tube.For our result tube is long enough to make the ratio A11] be small
be true

for a

L our earlier
1 meter

\302\273id.

A12)

Using
a

tube

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

Speed

of a

Pump
is defined

The speedofapump
it

similarly

to thecOnductancoofaholeorofa
unit

tube;
taken at the

is defined

as the

intake pressureof the

volume pumped
pump.

per
same

time,

with

the

volume

The

symbol

S is

used as for conductance;

(H3)
just

as

for
Let

i!ie conductance
pE

of two
the

dectriaii conductorsin series.


al the input

Proof:
denote

denote

[lie puntp

intake pressure at the output end of the

pressure

cad of the lube, and


tube.

let

p2

Continuity

of

flux requires that

Chapter 14: Kinetic


SO that

Theory

^i
Pi
equivalent

=
ScS[

S,W^

\\Sp

), SJ

(ll5)

to

A13).

The
connections

relation
between

A13) for
the

Scft

explains

why

in high narrow

vacuum systems
be

ihc connecand of

pump

and the vessel

to be evacuatedmust
and

as short

as largd a diameteras possible. A long

connecting

lube makes
cannot

poor

use ofa high


than
How

speed

pump.

Further,

the speed
aperture. effective

of the pump itself


S evacuate

be

larger

the conductance
rapidly

of its awn
pump
with

does a

speed

the ideal gas law

to Eq.

= p V

Nx, and from the definition

a volume VI From of pump speedanalogous

(99)

we

find

iP^^E^Q^Pl
dt

di

V
this

A16) equation has the

pump speedis independent solution


If the

of

pressure,

differential

W0-^0)cxp(-(/io);
For

to

\302\253

V/S.

A17)

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
a volume
a by 1 that

vacuum system
regions

proceeds much
on the

than

expected

more in the high and ullrahigh vacuum slowly The volume. basis ofpumping speedand system
magnitude\342\200\224

desorption
over

volume

evacuates

orders of gas predominates\342\200\224often by many as fast emits adsorbed molecules gas. The surface molecules from Uie volume.

ofsurface

as

the

pump

SUMMARY

1. The

probability

that

an

atom

has velocity in

do at

is

P(v)dv

\302\273

4;:{.Vf/27rrK'Vexp{~Mi>V2

the

Maxwell

velocity

distribution.

2. Diffusion is described by
Jn

-Dgradtr, and I is

D =

%cl ,

wiiere t is the

mean

speed
is

the mean free


by

path.

3. Thermal

conductivity

described

Ju =*
where

-Kgradr;

K = iC,,ff/ ,

(V

refers

to unit

volume.
is given

4.- The coefficient of viscosity

by

where

p is the
to

mass density.
the

5.

According

principle

of detailed

balance, in thermal equilibrium


equal

the

of any process that leads to a givenstatemust inverse processthai leadsfrom [he state.
rate

exactly

the rate

o( the

6.

The

Boltzmann

transport equation in the relaxationtimeapproximation


+
jf

is

gradY

/+

\342\226\240

gmd,

/-

-Lzh.

7. The electrical conductivity

of

a Fermi

gas is
nqixjm ,

a
where

\342\200\224

xc is

the relaxation

time.

PROBLEMS

/.

Mean

speeds

square

velocity

Maxwellian is vtaa
In a

distribution,

fa) Show that the

root

mean

<\302\273*>m \302\253n\302\253

\302\273

f3t/M)!'2.

(MS)

Because
follows

<>3>

<Pjt2>

<w,:>

<\302\273/>

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


value

directly of

from

the expression

in Chapter

3 for

an

ideal

gas. (b)

Show that the most probable

of

the

speed

vmP

is

vmp
most

- BT/MI'*.

A20)
Maxwell

By

probable

distribution

as a

vaiue of ihe speed we function of v. Notice that

mean the maximumof the


i>mp

<

speedc is

v,mi.

(c) Show

lhal the

mean

c
The mean speed may
also

\302\253

j^dvvP(v)

= (8T/rcAf)m.

A21)

be

written

as <juj>. The

ratio
A22)

v,mJZ~ J.0S6.
fd)

Show

that

?., the
atom,

mean of the absolutevalue


\"

of

the

z component

of the

velocity of an

is

?,

(\\v:{>

$\302\243

{2t/jiA/)\"\\

A23)

2. Mean

kinetic energy in a beam.


that

'
(a)

Find
in

[he
an

mean

kinetic

ofmoicculcs exits from now lhal the molecules


are

a small
collimated

hole

oven

so

by a

thai

the

moiccuies

that

pass through
the

second hole farther down the beam, a small ihe second hole have oniy
is

at temperature

energy jji a beam i. (b) Assume

velocity
thermal

component
equilibrium

normal to ihe axisof emission. What

ihe

mean

kinetic
real

energy? Continent:

The moiecuies in
after they
lo
heat

beam

do not
ihc

collide and
oven.
Ehe

are not in

have exited from


fast

The
residua!

oven is depleted with respect down iCH is not reheatedby

moiecuies,

and

gas left in the gas will cooi

flowing

s'u (iirough

the walls

of the oven.
classical

3.

Ratio

of

thermal

to electrical

conductivity.

Show

for

gas

of

particles

of charge q that

K/ra - 3/2q2 ,
in conventional

or

K/Ta

3/:s2/2^2
the

\342\226\240

A24)

units for

Kand T. Thisis known

as

Wiedemann-Franz

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.

The electron
thermal

conduction

electron concentration is 8 x 102Ipercm3. Esiimaie fa) to the heat capacity; (b) the electroniccontribution contribution conductivity; (c) the electrical conductivity. Specify units.
equation

the
the

to

5.
the
find

Boltzinaun

and

thermal

temperature

gradient

dx/dx.

a medium with Consider conductivity. The particle concentration is constant,(a) Employ distribution:

Boltzmann
the

first

order

transport equation in the classical nonequiHbrium

to relaxation time approximation


A25)

(b)

Show

that

the

energy

flux in the

x direction is

where
conductivity

vx2

= =

2e/3m. Sinijm.

fc) Evaluate

the integral to obtainfor

the

thermal

conduc-

6. Flow through
under

a tube.
difference

Show

that

when

a pressure

p between

the ends, the total volume

a liquid

flows through

a narrow tube
flowing

ihrough

the

lube

in unit

time is

A27)

where)/is

the

viscosity;
flow

L is

the length;
at

laminar and that the

velocity

the

that a is the radius.Assume walls of the tube is zero.

the

flow

is

7. Speed of
second

tube.

Show

that

for air

at 20eC the speed ofa

tube

in

liters

per

is given

by, approximately,

L + id
where for

(I2S)
we

ihe end
in

length

L and on a ihe

diameicr
finite

J are
length

in

centimeters;

have

effects
series

tube of
tube.

by

treating

the ends

tried to correct as two halves of a

hole

with

Chapter

15

Propagation

HEAT

CONDUCTION

EQUATION k

424 425

Dispersion Penetration
Diffusion
Time-Independent

of Development
with a

Relation, (n Versus of Temperature


a

Oscillation

426
427

Pulse

Fixed Boundary Conditionat x


Distribution
\342\200\242'

~0

429
429

PROPAGATION

OF

SOUND

WAVES IN

GASES

430

ThermalRelaxation
Example:

432
in a

Heat

Transfer

Sound Wave

434
435

SUMMARY

PROBLEMS

436

1. Fourier

Analysis of Pulse
in

436
Dimensions
Soil

2.

Diffusion

Two

and Three
in

436
437
437 437

3. Temperature Variations 4. Cooling of a Slab


5. 6.

p~n

junction: Heat Diffusion


Size

Diffusion from a Fixed SurfaceConcentration with Internal Sources


Nuclear

437
437

7. Critical

of

Reactor

The purpose of
the

this terminalchapter is to bring


problems

within

the

compass
the

of the
propagation

text

most

important

ofsound,

both dassicai

propagation of heat and in that are subjects part ofan education


in the

thermal

physics,

HEAT

CONDUCTION
first

EQUATION
of the

Consider
Pick law

the

derivation
!hc

diffusion equation, which

in

found

from

the

A4.19) for

particle

flux density:

J, a
where

-/?ngrad\302\273

(I)

A, is the

particle diffusivjty

and

n the

particle

concentration.

The equation

of continuity,
*-'+

divJ,

- 0,
is conserved.

B)
Because div grad ss
V2,

assures
substitution

that

the

number

of particles

of A)

in B)

gives

y
This

DnV2n.

C)

partial

differential

particle

concentration

equation n.

describes tlie time-dependent diffusion


A4.27-14.30)

of

the

The thermal conductivity equation is derivedsimilarly. By have in a homogeneous medium J_ = -/igradr.


The

we

D)

equation

ofcontinuily

for the

energy density is

+ div.l.

0.

Dispersion Relation,

Versus

where

C is the heat capacity per the heatconduction equation

unit

volume.

We

combine

D) and

E) to obtain

~
This equation describes the

\302\253

Z),V2r;

Ds

K/C.

F)

time-dependent

diffusion

of

equation is of tbc
is called diffusivity,

the temperature.

The
Ds

form

of

ihe

particle

diffusion

equation

the thermal diffusivity;


as in (i

fora gasii is approximately equalto the

C). The

quantity

particle

4.23}.

Comment.
C)

The

eddy

current

equation

of electromagnetic theory*
then

has l\\\\c

and

F). If 0 is

(he magnetic field

intensity,

G)

The constant
is
(skin

c j^JZtJ^i, % \342\200\224

sohed

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

Dispersion Relation,
We

to

Versus

k
diffusiviiy

look for

solutions of the

equation

DV20

= cOJct

{8}

that have the wavclikeform


0

0oexp[i{k-r-

tor)] ,

(9)
Plane

with oj as the angular frequency an excellent approach 10 this diffusion waves or heal waves

and kas
problem, are

]hc vvavevector.
even

wave

analysis

is

though

it will

turn

out that the


waves

so

highly

damped

ihai they

arc hardly

Chapter

IS: Propagation

at all

Substitute (9}in

(S)

to

obtain

[he relation
-

between k and to:


A0)

Dk2

ioi.

relation

io{k)

for a

plane wave is calleda dispersionrelation.


Oscillalion

Penetrationof Temperature
Consider

the

variation

of temperature

in the

semi-infinitemedium z
periodically

>

0 when

the temperature of the

plane z = 0 is varied
0(<U) =

with

lime

as

0ocosw; ,
for

A1)
in ihe

which

is

the

real

part

of 0oexp(-iw/),

real

6Q. Then

medium z >

the temperatureis
O(z,t)

*=

e0Rc[aip[i(kz

at)]}

where Re denotes real part

and

i3'2

{i

- l}/%/2. Thus,

with

s BDJqiI11,

- iwO) 6(z,i) = 0oRe{exp(-_-/a)exp[i(i/<5)


=

0ocxp(-z/5)cos(w(

- z/5).

A3)

The quantity
characteristic

\342\226\240=

BZ)/u)}\022

has

the dimensions

the of a lengih and represents

penetration
the

depth if we

of the

amplitudeof called skin


the

oscillations

of 0 is

lemperature variation: at this depth the reduced by e\"J.The characteristic depth is


with

depth

are dealing

the wave

eddy

current

equation.
decreases

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

amplitude

The ' by e\"

as

D s= 1

x 10\023cm2s'\"',
by

then the
and

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)

the sun

B0/cu}1'1

as 5cm.

For the annual cycie,


L(aniiual)

lm.

Development of a

Pulse

layer

of

tOcm

of can

on

top

of a

cciiar will lend

10 averageout

day ;i!

night ihc

variations

of surface

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

wffxitiofi lontperalure, but liic summer/winter

top

dilTusivity,

anrf

not

ihe

conductivity

alone.

Development of a

Pulse
wavelike forms

In additionto

the useful

solutions of

of the

severalother

solutions.

form (9), the diffusion equal ion has We confirm by insertion in {8}thai
A4)

0(x,t)
is a

\302\253

DnDi)~inexp{-x2J4Dt)

soiution. The

proportionality factorhas beenchosen


j*y{x,t)dx

so

that

*~ I.

A5) ofa pulse whichat t = 0 localized at x = 0, and zero

The soiutionA4}
has

corresponds

to

the time
S(x}t

developmenl
sharply

the form

ofa Dirac delta function


be

elsewhere. The might


pulse

a temperature

pulse, as

when a pulsed laser or pulsed


of

electron

beam

the surface,

a surface briefly. Let Q be the quantity unit area. The temperature distribution per
heats

heat

deposited

on

is then

given by

0{x,t)

A6)
per
factor
unit

where Cv
inwards

is

the

heat

plotted in Figure15.1.
from

capacity
The

volume

of the

material.

The function
flow

is

2 arises

because

all heat
A4)

is assumedto flow
was

assumed.

ofa semiconductor, deposited on the surface


semiconductor.

while for the solution the surface, Another example of the applicationofA4)
to

symmetrical

is the

diffusion

of impurities

form

a p-~ujunction

inside ihe
value

The pulse spreads


given by

out

with

increasing

time.

The

mean square

of

x is

/X)dx ~2Dit
after
A7)

evaluating

the

Gaussian

integrals. The
-

root mean squarevalue

is

A-Imi(/)

(x1I'1

* (IDty1.

A8)

Chapter

I Si

Propegai

s.b

= 1.0

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.

Comment,

a general

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
XrBU(i) =

{2Dto)llZN1'2 ,

A9)

so that
This

the is

rnts

the

dtsplacemcni result observed of small

iri

ts propodional to the square toot of the number of of il.c Bfowiiian inolion, the random motion sludics
in

steps.
of

suspensions

particles

liquids.

Time-Independent

Diitribution

Diffusion

with

a Fixed

Boundary

Condition
or
again

at x

~ 0
respect

If a solution of (8) is differentiated independent variables, the result may is obtainedby integrating A4} with

with integrated be a solution.

to

any

of its

An important

example

respect

to x;

=*-= [\"dscxpf-s^icrfu,
where

B0)
defined

= x/DDt)U2.

Here we

have introducedthe error function


-> \302\253u \342\200\224

by

erf\302\253

jo

<feexp(-s2).

B1}

Tables

of the

error function are readily available. The error


erf{0) =

function

has

the

properties

0;
is the

lim erf(x) =

1.

B2)

Of

particular

infinite

at x =

solution is

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

practical

interest

0(x,t)

0o[l

- zrf(x/DDt)U2)l
value
of

B3)
is proporimpurities

Again proportional

we to

see

that

the distance
The

DDiI11.

into

a semiconductor

a specified at which 0(x,t)reaches to the dilfusion of this solution application is discussed in a problem.

Time-Independent

Distribution
that

Let us
equation

look at a solution of (S)


reduces

is independent

of the

time. The diffusivily

to lite

Laplace equation
V20

=-- 0.

B4)
the

Consider

a semi-infinite

medium bounded by
temperature

plane

2 =

0 and
in the

extending
boundary

along the positive z axis.Let the


plane;

vary

sintisoidaliy

0(x,y\\0) -

0os

B5)

Chapter

]5:

Propagation

The solution

ofB4) in the medium is

0{x,y,z)= 0o5inkxexp[~kz).
The

B6)
the

temperature

variation

is damped

exponentially

with

distance

from

the

distributionin the boundary plane. The temperature must be maintained by constant healsourceson
PROPAGATION
Results
in

time-independent
the

boundary

plane

problem z =

0.

OF SOUND
earlier
effects
in

WAVES

IN

GASES

developed
Thermal

ifiis

book

can
in

be applied
this

to the study ofsound waves


Let

gases.

are important
the

problem.

dp(x,t)
may

denote the
be written

pressure associatedwith
as

sound

wave;

the form

of the wave

dp =
where

6poenp[Hkx - on)},
The

B7)

k is
.V

the wsvevecior

and w is the angular frequency.

wave

propagates

in the
We

direction.

suppose

the equasion
=

of state is that ofan idealgas:


Nz

pV

or
and

p =
M

pr/A-f

B8)

where

p ~
equation

force

NM/V is the mass density,


referred

is the

mass of a

molecule. The

to

unit

volume

is

Here

is

the

x component

of the

velocity of a volume
= 0 ,

element.

The

motion

is

subject to the

equation of continuity
dp/dt

div(py)

C0)

or, in

one

dimension,

dp/dt

+ S{pu)/dx
is

- 0.

C!)

The

thermodynamic

identity

dU

+ pdV

= jda ,

C2a)

Propagation

of

Sound

Waves in Gases

which can

also be written
iV -_ + p_
du

da

Ty.

C2b)

If

we

assume
the

(pending
passage

discussion

beiow) that

during

of a

sound wave,
Cy(cr/ui)

Eq. C2b) becomes


= 0

there is no entropy exchange

(p/V)lcV/ct)

,
unit

C3)
volume.

where Cv
rewrite

is

the

heat

the

second

capacity at constant volume, term in terms of dp/ct because p

per

We

can

re=

NMfV

&\\\\d(l/V)[dV/ct)

-~(\\/p)(dp/dt).

Now the

thermodynamic identity appears as


Cv(dx/di)

{p/p)(ep/ct)

- 0.

C4)

Let

us define

the fractional
=

deviations s, 0 by
+ s);

Pod

t ~ T0(l

+ 0) ,

C5)

where We

p0, assume

t0 are that

three

equatioas

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

the density

-iwpu

4- ik{(?po/M)s

+ (pTofM)O]
+ pn)

= 0;

C6)
C7)
C8)

ia)pos

ik{pous

= 0;
k

-iwiQt,y0 +
We assume
to approximation
that

icu{pfp)p0s

0.

at

sufficiently

small

wave amplitudes

it

is

a good

approxima-

neglect

in these

u.s, and 0. For example, ncgiecicd. The equations thus


p

equations pu ~ po{\\

terms
+

in

the

squares
if

and
the

cross
cross

products
product
from

of
su is

reduce

s)u becomes po\\\\ the to, with

subscripts

dropped

and

r,

cott

- (kx/M)sas ~

{kxjMH

0;

C9)

ku = 0; or
CVB

D0)
-

rCyO

ps =

0;

us =

0 ,

D1)

Chapter

IS;

Propagation

where

n is

the concentration. Theseequations have


to =

solution

only
\"

if

fyt/M)llik ,
in

. of sound is

D2)

where

y =

(Cy +

n)jCv =

\302\243,/\302\243(,

our

units.

The velocity

it,

den/dk

D3)
the lowest frequencies up
to

Tiiis

result

applies

to

nionatomic

gases from

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
Thermal

equation

B9).

Relaxation

Wiih polyatomic

gases {43}is
is

valid

at

low

frequencies, region

increasedthere
\342\226\240

transition

frequency

the frequency is of above which (he velocity


but as
and

sound

increases.
propagation

The

transition
is associated

frequency

region belwcen low frequency with relaxation effects.


establishment

high

fre-