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International
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Publication
pat;
Killcl,
Clmrlcs.
Thermal physics.
Bibliography:p.
Includes
index.
!.
Herbert.1928QC3H.5.K52
ISBN
Statistical
tiicrmodyn;miics.
joiiii
I.
II.
Kroe/n
Tillc.
aullior.
1930
536'.?
7916677
O7167IO8S9
\302\260 this
I9B0
by W. may
H. Freeman and
be reproduced
Company
by
bor.k
plioiographic,
or electronic
process,or in
may
any
form
in
of a
sioreti
a retrieval
copiedfor
permission
system, transmitted, orotherwisc wriiicn or private use, without public from the publisher.
United
phonographic recording,nor
it be
Pcimcti
in
ilie
State of
America
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
the University
in
Gulling
lhc
then
new research
transistor. laboraProfessor
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, negativehighfrequency electronhole 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
physics These
and
generally. notably
fields
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
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 =
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
the index.
greenhouse
page added adopted
elementary was
in
1994
on page
A
115, following an
on to the
suggested
by
Professor
Richard
Muiier.
aioinic page
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,
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
Distribution
and Hdmholtz
Free Energy 55
4 Chapter
Chapter 5
Chapter
Thermal
Radiation
and
Planck
Distribution
87
1 i
Gas
151
Chapter 7
Chapter
181
261
Work
225
Chapter
Chapter10
Chapter
Transformations
275
il
Binary
Mixtures
309
Chapter 12
Chapter
Cryogenics 333
Semiconductor
13
Statistics
353
Chapter
14
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
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!.
and
R. H.
DiEEman,
anil
thermodynamics:
textbook, 6ih
ed., McGrawHill,
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,
Springer,
L D.
physics,
3rd cd. by
1985.
K. M. Lifshitz
and
L. P.
1. Piiaevskii, Pcrgamon, 1980, part Ma, Statistical mechanics. World ShangKeng 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.
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.
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 lowtemperature
pa.
to liquid
and
Betis,
introduction
helium, 2nd
ed , Oxford
Univesity
Press,
1987.
Irreversible
thermodynamics
to
nonequilibrium
statistical
chaos:
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, NorthHolland, 1986, cI976. H. Smith and H. H. Jensen, Transport phenomena,Oxford University Press,
Plasma
19S9.
physics
processes
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.
[ihenomena,
Oxford Uni
University
1987.
Metais
P.
and
affoys
Haasen,
Physical
metallurgy,
2nd ed.,
CambridgeUniversity
Press,
1986.
Superb.
Boundary
value problems
in solids,
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
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
states
accessible
to a
system.
closed
system probability.
be
in
any
of these
quantum
states and
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 ay + o, lhan for two systems
equal
fundamental
is that
ofg,3j.
specified
energy,
into thermal
the one
in
coniact
or
may
transfer
energy;
their total
lifted.
comlraints direction,
transfer
the
product
The
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
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
property we
lemperaiure
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
energy
will
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

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
treaud
:iml
in
sinies,
une
:n
energy
system
with
u large
the
combined
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,
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
substitution
of C),
leaves us
This
is Boitzmantt's
result.
To show its
system
use, we
calculate
the
thermal
average
in
thermal
contact
with a
reservoir at tem
t;
E)
where
probabilities:
we have
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
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
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
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
as equilibrium
The Gibbsfactorof
us to
of Ihe
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)
is occupied
bv
particle
at
energy
with
energy 0. The
result (9)after
is readily
expressed
as
A0)
FermiDirac
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
derivation
the limit
The
properties
of the
because
this
result
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
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
unites
the
macroscopic.
Chapter
States
of a Model
System
BINARY
MODEL
SYSTEMS
10
Enumeration
Binary
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
its of an
origin
to
investigations development,
thermodynamics,
eminently
and
worthy
independent
and because it
departments
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
extendedits area of
thermodynamics
which
deep impression
the framework
upon me. It
is ihu
only
physical
within
of universal of
content
I am
convinced
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,
thermal physics tells us the meaning of that do not thermal physics appear in and free energy. We shall motivate
three
chapters and
Our
point
of departure
concept
of the
of we
particles.
When
we can
count
2).
system,
know
the entropy
of states
of the
system,
the
entropy
is defined
number
(Chapter
the
energy
of the system
energy
rhe entropy,
the temperature,
the pressure,
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 1455. 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
Stales
with
identical
energies
arc
The
multiplicity
energy level is the number of quantum states wiih very it is the number of quantum slates that is important
tlte
number
of energy
levels. We
the
shall frequently
energy
deal
fti'th
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>^ums.
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
is in has
parentheses,
the
prolon
a spin
and
two independent
Chapter
1; States
of a Model
SyMm
Hydrogen
Lowtying
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
as
the
direction
of a
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
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
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 lowlying levels energy
confined
ofa
onepariicie
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
by
three
positive
integral
quantum
numbers nf,
n,.
The
energy
is
The multiplicities
tn
the
figure.
The three
nr2
orbitals
=
n.1
18;
the statistical
of particle
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
any
the
convenient
same
arbitrary
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
the
model
system
well that
to any
realistic with
clear
always
agree
become
general
statistical
properties
are of
concern will
The
Attached
binary and
model distinct
syslern sites
is illustrated fixed
in
Figure
separate
in space,
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
10
1.3
at fixed
sire
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,
of finding
tile
particular
arrangement
shown
Figure
1.4
State
ofa
parking
This
lot
with
10 numbered by a car;
occupied
parking theO's
spaces.
particular
state is equivalent
to
that
in Figure
(.3.
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
ways
The
total
nf the
We may
N moments is
2 x
2\\
state of
site;
there
the orient at ion of the moment oil c:k!i yiviiig for a single use ilio following simplettotation
state of
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 tm; 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,
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)
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
lefthand
is a way
possible
states
system.
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
S different
states:
magnets up:
magnets
T1T1T3
up:
T1T2I3
T1I2T3
lihti
Onemagnctup:
None
tihli
IJ2I3
lilils
lilif3
up:
The
in
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,
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
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
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
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
appears
The productin
may
be written
symbolically
+
as
(T \342\226\240.
if
We may
from
D)
when
we are labels
interested
in
only
in
how
of the
magnets
in
a state
are
ft
up or
we
which
particular
sites
which
have magnets
the
up or down,
appear in a
drop
and neglect
the order in
arrows
(t
II;
further,
(t + )v for
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
tjv+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
magnetic
field, stales
of different
to the
of
energy, so that
field. Until
of an energy level
states
a magnetic
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 =
2v
(H)
A'
\\Q are
given
in
Figures could
1.7. For
coin, \"heads\"
down.\"
could
stand
for \"magnet
upland
\"tails\"
for \"magnet
System
of yf Npi)
oixss
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
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.
10 pennies
in
heads
each
was recorded.
0\302\25100
I
Fijutc
1.8
A binary componenls
\302\251 5
0
6
chemical
10
II
012
Every
distinct
state
of a
binary alloy
system on
sites
is contained
in the
(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 ~
and
B on
N sites:
which
is identical
to the
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 welldefined 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
the steep
thai
variation
for
a very
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
is convenient are
logarithms
log*/,
fxccpl
where
here
.ilierwise
as log.
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)
number.
obtain
log&N
s)l ,
B2)
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]
st\\Q\\
\\
.V!
BrtN)ti:iNNcxpl~N is derived in
argument
+ IJ[12N)
B6)
for N
\302\273 1.
This
result
terms
We
take
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
= .V,
I
.Vt.
\\VLsiil>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
+ co
integrals
treated
s =
is given
by A5)
in Appendix 0;
A.
C7\302\273
\342\200\242
The
replacement
errors.
of a
slim
by
significanl
For example,
.)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
value
of sE0,0)
is 1.264
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
or
mean P(s)
vaiue, is defined
of a
function
as
</> = Z/<*m*),
that
09)
to
unity;
provided
Uic
distribution
function
is normalized
!.
\302\243?(*)
D0)
The binomial
A7)
that
D1)
and
g{N,s)/2s,
is nol
be
normalized lo
and
unity.
If
all
states
are equally
we
have
\302\243J'($)
t. Tfic
will
D2)
f{s) = s2.In
\302\243
the
approximation
that
led to
ds
C5) and
~ co
C6),
we
replace
in
over
s by
an integral
between
and +
co.Then
 [2/nNI'3
(jV/2)J'J
J^Jxx^\"'*
(jt/4)\022
= {2/7r,V)\"!{.V/2):i'J
whence
<iJ>
= iiV;
<B,y> =
,V.
D3)
The spin
quantity excess
<{2i);> is
is the mean
square
<B5}2>';J =>yfN
D4)
<uy Magnetic
Sys
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 inknet energy tn;ty energy ofa single magnetic moment m with a fixed external magnetic field B is
V \302\273 mB.
H6)
This is
the
Ar
magnet
elementary
in
the
field
B. each
mngncts,
with
two allowed
U
orientations in
magnetic
tola! potentialenergy
2smB}=
is
m, =Q.
 MB ,
D7)
example
using
ihe
expression
M for the
2s/n.In this
lite
spcclnttn
continuous
of values
or
of ihe encrcy U
spectrum
adjacent
discrete.
quastconttnuous
between
will levels
ihe spacing
Figure
energy
t.tO.
Constant
will
spacing
restrict
is a
special
feature
of
the
particular
tnodcl,
but
this feature
ihe
not
the generality
m is developed
Following
sections.
The value
magnetic
^f (he
is,
energy
for
moments
inferact
the
only
with
the
exicnial
^ornrfcicly ridennined
by wrtitng
value
of s.
This funcitotutl
raises
dependence
2s
i..ucaka
U{s). Reversing a
moment
by
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
oscillators. The problem of tlic function for harmonic for which an exact solution for the multiplicity problem
binary
model
function
is
solvable
problem is the
need
harmonic
by Max
Sludent
in
solution entirely
way
problem is given
slates
The quantum
derivation.
The
modern
to
ofa
harmonic
energy
eigenvalues
sho) ,
or and of
D9)
zero, the
where
the
quantum a system
number
s is a positive integer
of
angular
frequency
to
of the
the oscillator.
consider
The number
in which
states
is
infinite,
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
back
to tlie multiplicity
quantum
for
ail values
we
of
the
numbers,
need
a function
to represent or generate
scries
E1)
coS\302\260
^CfC
in
' 's
the
(S3),
but
t docs
not appear
will
help
us find
the result
. For
the problem
of JV
oscillators,
the
generating
function is
E3)
becausetlie
number
i\"
can
integer
pftiJuct
sum
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
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
syslem
in a
siaie of
spin excess 2s is
where
in
is the
magnetic
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
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
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
and so forth.
to
a time
enormously
there
recognize that
never. . . .
of
ff
we
wish
to find
in
rational
mechanics
of thermodynamics,
we must
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
physicsis
ttt;tt
a closed
system
is equally
quantum
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
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 lowtcmpcraturc 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
states
the crystalline
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 sx' 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
aspect
is left
in
the problem.
PROBABILITY
to be tn any likely Suppose we have a closed sysiem that we know is equally onehalf 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.
otherwise,
consistent
with that
ihe
fun
fundamental
shall
be concerned
panicle
A),
taier
number wilt
with
systems
are not
dosed,
systems
but
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.
the
average
value
of A' is
/\"i>'f
>':
'
!'
D]
because average
now in D)
alt g
equally what
likely, may
with be
P(s) = an called
\\jg.
The
each
accessible
constructed
alike
ts
averageof
property. An
any
properly
over
the
group
is catted
_1_
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
Uic vuriou^
sy>(cnis
tlie
cusciubl
sighificance. ensemble by one system in a We assume that the ensemble the fundameniat assumption.
is represented
in the
2.2.
quantum
stale,
as
in
Figure is
implied
in
Example;
Construction
of an
of
ensemblefive spins,
represent a dosedsystem
each frequent
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
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
 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
ti1Ca\302\273embio.ThiS is
states
at tin's
enetcy.Tlic
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
two
systems
freely
two
5,
from
systems
and
one
in
\302\243t
be
tttc
brought
other.
into
This
contact
is called
transferred
to
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
exchange of
contact
energy
Figure
2.5
Establishment
of
Micrmal
between
[wo systems
&, and
in
size
constant
lotal
energy
can be
the
t6tal
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
order
to define
the energy.
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]
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
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
This
product
Different
forms
configurations
one
term of
of Uie
system are
ofs(
characterized by
the total
thus
different
values
of j{.
all
We sum
ihe
suitesof
sum we
contact.
to obtain
number of
obi a in
configurations
or fixed energy. We
of of
F),
numberof accessible
and
the the
combined specification
s, N,,
N2 constant, as
of
products
of the
say
form G).
be read
Such a product\\sill
\"st
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
most
probable
configuration,
thermal
the configuraaverage
which
the
number
of accessible st3tes
may
is a maximum. Such
equilibrium
values
(used
in either
values.
Because
of the
sharp maximum, we
(8).
the
average
of a
physical
configuration
In the
find
in
such
a replacement
and
F)
by an
average over
Most Prabahte
ConfiSui
Example:
tfiL
sharpness
Tno 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
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
excess
We
of the
find
combined system
is,
and the
spin
excess
system is 2s,.
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
or
the
function
The
e\\tr\302\243nuim
is
so
that
the
curve
bends
downward.
Ai
the
cxt
where
Equation
s are
held
constant
as s, is
c1/csi1o(
* The
product
fund
ion of two
Gaussian
fund
ions
is always a
Gaussian.
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
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.
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
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
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
result dV2
~tiUx
to obtain the
thermal
equilibrium conciiiion:
Lflfs
which
we
may
write
as
a, calledIhe entropy,
a{N,U)
by
\\
where
a is
the Greek
letter sigm:i.We
now
write
B0)
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
systems
in
thermal
on the
systems.
TEMPERATURE
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
Lon^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
prefer
natural
the
fundamental
temperature
r by
B6)
This temperaturediffers
from
ihc
Kelvin
temperature
by the
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
yet
with
not
understood.
thermometers
temperatures
than
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
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
definition different
is die
variables.
same
The
itrot
cases,
\"What some
but
is
independent
q
other
in lhermal
oilier
ej.pcrinicnts
phy. we
because
variables.
ENTROPY
Tile quantity
entropy
as
logg
was
introduced
in B1)
the
as ihe
ts
defined
as the
logarithm of
is a pure
number
slates
accessible
to the
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
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 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
physics
ed.
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
when
remove
a positive
amount of
Figure
energy All
from
add
the same
2.7.
Clmptcr
2:
Entropy
urn!
Tehtjter
The
tolnl entropy
change is
When
t,
> r2 the
ihe quantiiy in
with
side
is positive,
so that the
is
positive
when
of energy flow
with
from
higher
temperature
system
the
lower
temperature.
Example:
fansitiariiy
Entropy
increase
with
Let
heal
of
ihc rentier's
previous
with an
a 10g 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
after
initial
con'act?
Notice
this
transfer
is a
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
second
hody
is increased
by
S2
,7~
= 3.45
Tile
iotal
enlropy
increases
by
AS, +
In fundamental,
104JK' = 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
can
show
into
thai
thermal
ihc loial
contact.
~
ctttrapy
We have
always
increases
when
two
systems
a special after
;trc
case.
the
V% +
arc
in
thermal
contact
is
ff(t/)\302\273=
^0,A/^A/
t/,)
C3)
~~
term
gi(EAo)i/i(^
^to^
^or l^e
iXiiiVd^
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 welidefinedoperalion. 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
~~
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
ihe
initial
term
9iiVtMU'~
the Here 0s denotes The
Vl0).
C5)
value
of
Vl
for which
after
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,
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
thermal
contact
is equivalent
sjstem to ihe
only
V2
each
be constant; ihe
after contact
thermal
U,
need be takes
constant.
combined
system
lowards
separate
final
equilibrium
a certain
time. If
we
ihe two
Add
energy
Decompose
molecules
Let a
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
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
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
commonly
is ill :l
used statement
will
of the
law
configuration
(he equilibrium
a looser
consequence
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 KelvinPianck 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 weiidefined
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,
objection
to
affirming
frozenin
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
of as
stales itself.First,
entropy
two
independent
of (he cmropy as the iogathe number of accessible systems is liie sum of lhe
ali
entropy
is
entirely
insensitive\342\200\224for
practical
is
purposes\342\200\224to
the
precision
6U
with wiiich
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
 1382
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
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
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.
many
systems,
all constructed
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
temperature
and
the con
7.
The
entropy a constraint
ofa
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
alone.
PROBLEMS
and
1. Entropy N is
CUiNn,
thai
wiiere
U
*=
C is
(b)
;t
constant
{Nt.
Show
that
{c^a/rU2)*
is negative.Tliis
Find
form
of
y( U)
2.
Ptirtitttagiwtisni.
the
equilibrium
ictnKT;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).
U/)\302\2732B2N, where
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 monkeyHamlet {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
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.
Addithity
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
and g2{N2.s
its peak
= s,.ForSj=
value. Use
 ss), the
JV, =s
product
from
the
function:
the
form
A7) may be
(a) Compute
(b)
gigz/{9i9z)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.
malhematfcoiherary
sec'The
Libtary of Babel,\"
by ihe
fascinating Argentine
Clarke in
2001.
explanations
of the
We arc gralcfut to the Population evidence. The cumulative as 2 x 10 s 3nd tl^c number njocti ksi than the'numbcr of
Revcttc for Bureau and to Dr. Rosier Reference number of mansecondsis 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
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
complementary
error
function.
\302\273i,
xp(x2)
(\"\"e
1 +
small terms.
Chapter
Boltzmann
Distribution
and
BOLTZMANN
FACTOR
58
Partition
Function
Two
61
State
System
62
64
PRESSURE
Tlicrmodynaimc
61
identity
;>7
HELMHOLTZ
KttEE
ENERGY
of
6S
the Free
Property
Energy of ;i
69
Relations
from
70
Maxwell Relation
7!
2
of f Calculation
IDEAL
71
LOOK
GAS:
in Af
FIRST
72 72
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.
85
Magnetic
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. OneDimensional
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
to distinguish
in
terms
the thermal
in
we call
mechanical
the
narrower
action and
In
this
chafer
physical
we develop
properties
of the
permit
us to
of
calculate
the values
We a very
have
sysiem
called
&
ihe
[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
external
as
Figure
The
total
energy Uo
=*
U^
is \302\243/j
r,x is
constant. ihe
In
particular,
if the
Ea, tltcn
Uo
energy
of
the reservoir.
Toial sysiem
Constant
energy
Vo
J.I
irOtiiUhcn
loiat sjsieni
syst S.
n decomposed
iisioa
BOLTZMANN
A
FACTOR
of thermal
central
\302\253iil be
problem in a the
physics is
proportional
to
the t,.
probability This
iltai
probability
be in ihe state s, ihe number When we specify that S should number of accessible Slates of the louil sysiem is reduced10the reservoir (H, ai ihe appropriate energy. That is, ihe number
accessible
states
g\302\256t j
of ihe
siaies
of
of cnlropy t la
when ihe
(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
energy
is Uo
is^f/o
in
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
we
have
called
the fundamental
assumption. The
situations
are
shown
in Figure
of the
about
the
the
system
depend
on the
ow
constitution
the
dependence
is only in terms
the large,
temperature
multiplicities
very l.irgcnumbers.
write
B)
of the
E.)
ff\302\253(t/0
C)
Chapters:
Bohzmnnn
Oi
E
01
ergy
yo
(/\342\200\236
',)
', stale
8
Sta
;\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
slate
t, 2. The
reservoir
(b)
slates,
in (a) and
two
states
1, 2
E)
Let
us
expand
the entropies
in D)
in
a Taylor /(x0)
series
is
expansion
about
t)
0)
where
1/t
(S^/cCV^
gives the
is taken
al energy
an
infinitely
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
,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
exp(e,/t)
states
the
system. The
partition
and
is
the
pro
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
results
of
statistical
physics.
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
and
heat
as functions is plotteJ
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;
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
expfs/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
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)
arc calculaied
for a syslem
at a
specified
volume. From
(!?b},
'
A6).
fEY
eXp(E/t)
A8a)
The
In
unils
C, is defined
dimensions
of energy in ]Ilc
per kcivin.
Tim
siicctfic
heat
is drfmed
\\\\\\
us
itio
deal
capacity
per
unil
ri^iimmp
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^XplE/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
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
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
The
mechanical
volume
Kto
\342\200\224
AKappears
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
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
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)
the
stale
of
the
to obtain
written
as p:
B6)
where U
number
<t>.
The
in
entropy
the
We
a is
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
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
Thermodyaamie
Identity
cancel.
interdependent
The
overall
values
entropy change
of dll
da
will
be
zero.
{&V}at
If we
the
denote
entropy
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 kfth;ll)d
side of C1) is
equal
to
ft
whence
Therniodynaniic
and
Identity
differential
B7)
of the
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
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
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.
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,
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
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.
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,
can
from
be obtained
the
by
substituting
for
D5) in
one
D2).
partition
\302\253
function
magnet:
exptniB/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;
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
the
righthand
side of E0)
represent
may
pressure
~(cU/dV)f
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
Maxwell relation* We can now derive one of a group of called Maxwell relations.Form the crossderivauvirscV/^l\" be equat 10 each other. It follows from that D9)
useful
(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 =
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
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*.
thai
a =
cFjcr
\342\200\224
log
Z)fct
logg0 only
a ~
0.
We may
Zand
cxp{f/t);
probability of a
quantum
E6)
the
Boftzmann
factor
(II)
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
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
are
We
system
neglect
is
the spin
of
the
nft
atom,
n:.
so that
a state of
the
entirely
specified
values of nlt
Ideal Cm:
First
Look
The
partiiion
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
F2)
in
ierms
of ihe
concentration
ji
XjV.
Here
F3!
is catted the
quantum
concentration.
It is
the conccnlration
lie
atom
in
cube
of side
equal to
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 ,
F5) If t
=*
kaT,
where
the
kB is
lkHT,
the well
The
equiility
thermal
average
of'a
free particle
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.
to regime
is always
apply,
occupancy
a free
We
that
as defined \302\243\342\200\236
positive
temporarily
many
tiiitil
noniulcmaing
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
system
N limesthat
of free particles with one panicle for one particlein one box.
in each
Figure
3.8
Atoms
of different
species in
iV
distinct
partition =
3.7), the
partition
funciion
is fhe
ZXha*\302\273
Zt{l)Z1B)Zl(N)
,
independent
F6)
state
because ihe
product
on
!he righthand
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
diffrfem,
if
each
ihe
panicles
a faclor
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
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
follows
from
{he
N particle
partition
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
units,
NkuT.
G1)
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 SackurTctrodc 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
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
particle
Jjjexp[~
pI1)/2Mx']dpIdpfilp.
{77}
The thermal
a result
The
similar
to Ft).
be
are
fat \302\261ao
each
component.
Kamiltonian
the
ts generalized
in the
a canonical
component,
coordinate
will
classical be
associated of degree
wilt
homogeneous energy
in
a posilion
average potential
associated
with
that coordinate
also
3 Vibt
^\342\200\224\302\273
lion
T,\302\273s
25
50
75100
250
Temperature.
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
1 we
calculated
atoms
the
number
of possible found
A arid t
atoms B. We
arrangein A.20)
for
the
number
A/i
G3)
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
04
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.
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 twophase 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 mblure 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)
of
and
B crystals
entropies
in the
arc
proportion
positive\342\200\224all
positive\342\200\224so
that
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
A atoms.
Let this
\302\253 t of
atoms.Tlic
a positive
energy is
wlkre
eniropy
(SO) is
approximately
a =
~.\\N\\ogx
(83)
Fix)
N(sU
+ txiog.v)
(84)
which
has
a minimum
when
BFfBx
\302\273
N(U
xiogv
+ 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)
expfe./tJ/Z in a
is the
probabiHty of finding
a system
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
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
close
to
ihe
PROBLEMS
/.
in
Free
energy
function
of
a two
of
energy as a
of
an
expression
for
the
free
states,
one
for
at energy
itnd
0 and one
entropy
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
of
temperature
and
magnetic
model system
magnetization
magnetic
moments
in
a magnetic
the
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.
is
plottcJ
only
the result
as a function
is x
harmonic
ofr
ihe
s
free M/tuu,
energy (c)
and Show
sust;eptibiltty
energy of
an
/Vcc
has
oscillator.
A onedt'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
and
to is
at
tlic classical
the
have
the
zero
harmonic
oscillator
of energy
state
s =
(S7)
Note
that
at
high
temperatures
such ihal
!og(/itu/t).
\302\273 fitu
we
may expand
the argument
(b)
From
entropy
($8}
The
4.
entropy
is
shown
in Figure
capacity in
volume
Figure
3.1i.
Energy
is
fluctuations.
ta thermal
contact
wiiis a
syslcin
mean
square
fluctuation
Z the conventtooai symbol for <e). Hint: Use the partition fitnctwn out the :crm to ihc mean fluctuation. Also, cU/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 umperatufe
frequency
u>.
The
ifiiontal
unncal mlcln iiit iluc
scale is
wilh
units
flE.
\302\253herc 0,
is
Icniperamte. Cv
 kB.ot
'as
in run<iamciiia! c^issic^I
is k^own
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
In our
of the
first
look
at
But
the ideal
molecules
gas we
can
con
particles.
rotate,
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
0, I,2,.. ..
the
The
multiplicity
one
molecule.
makes
Remeniber
a difference,
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 *
C{x), showing
citefgy
behaviors
for
\302\273 ro
0.
it is
7. Zipper pruhh'W.
with that
zipper
h:is N
in
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 ofnvosiraiided unwinding very simplified C. Kittel, Arner. J. Physics 37, 917A969).
iirnii
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
of
he
particle
for which
this
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
independent
sysiems
in
thermal
at a
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 Onedimensional
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
.Ha
The direction of
the
force
is
opposite
to the
pressure.
We
consider
a polymeric
chain
of N
each
link
equally likely to be directedto the right of arrangements that a headioiail give + q(N,s)
and
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 onedimcsisional 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 STEFANEOLTZMANN
KirchhorT
Body
LAW
Absorption:
Black
Law Radiation
96
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
111
111
of the Sun
Earth
111
of Thermal Shields
Radiation
Gas
111
112
112
Photon
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
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
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,
frequency
of
the
of energy e in
....
M. Planck
Planck
Distribution
Fu
PLANCK
DISTRIBUTION
FUNCTION
spectrum
The Planck
in
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
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
positive
integer
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
Figure
4.1
represents
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
field is suggested
figures
electric
and
magnetic
throughout
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,
summed
and
 x), whence
C)
1
exp(tou/T)
Lt* SlefanBohimann
is
The
probability
that
the
system
is in the
given
by the
Bohzntann
factor:
P(s)
exp(
shci/x)
The thermalaverage
value
of
s is
E)
With
>' =
rmhthand
side
has
the
form:
cxptv)/
From C)
and E) we
find
exp(>.)'
F)
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
any
kind of
wave
field
PLANCK
The thermal
AND
STEFANBOLTZMANN
LAW
\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
Ex
ExOitn
wtcos(fiJji.v/L)sin(iiyjij'/L)sin(fi.Jiz/L)
,
,
(9a)
(9b)
ID
Et
sin(fl=Tiz/L)
= E0
Ex
(9c)
the
are
three electric
\302\243lQ,Ey0 not
and
the
independent,because
The three
components are
indepen
A0)
Planck
Law
and
SlcfanBolwtann
Law
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
perpendicular
vector
the
with
components
and
>l, so that
cavity
is a
transversely polarized
as the
direction
of Eo.
For a
polarization
given
triplet
directions,
n. we
mutually modes
perpendicular for
each
iriplei
equation
V'v1
i:y
trJJ.
'.
.(V
wilh
c the
velocity
of light, we
cWnJ
find
4
Hya
n;2)
= w3L2. in terms
\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),
photons in the
cavity
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
=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
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,
a dimensionless
variable.
We set
x =
A8)
becomes
A'J)
The definite
is
found
in good
standard
volume
tables
is
such as Dwight
in the
general
references}. Tlie
\\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 theStefanBoltzmann
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
andSufanBoltzmam
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
Figure1.4
Ploiof.vJ/(c*
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
a.
Chapter
4: Thermal
Radiation
and
Planck
Distribution
gy The
area
v
energy
gy
contained
p in
unit
flux density
and
length
a column
of
of
unit
light
times
the
time.
Thus,
The geometrical
derivation
flux
is (he
The
final
result
the
radiant
energy
is
by
use of
B0) for
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~\".
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
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
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
nonblack 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
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,
of
tnaucr
galaxies,
more
atoms (which are organized lhan before decoupling. complicated radiated by the maiter since lhe decoupling
inlo
heavier
cosmic
botiy radiation.
ELECTRICAL
NOISE
Planck
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
\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
of the
microwave
cosmic
heicr
speclrum ofinlcrslettac
a bulbonborne
neiir
lhe peak,
infrared
Caurlesy of P. L. Richards.
ai frequencies
A/of wave
the
circuit.
edge of
Tlie
voltage
cLvironuignetic
propagation
Nyquist
tlicorcm
gives
a quanlhative.
in
expression
The
generated
any
by a resisior
estimate
thermai
equilibrium.
uccded in
of
Hie iinnting
signaliouoise
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) 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
delivers
to a
which
hi
this
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
voiiagc
fluciuaiion
as in
impedance
of lenglh
a resistance
L and
characthe
R. Thus
sense
in
that
the
ail energy
appropriate
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
propagation
velocity
on the
exp(ftwAJ
Figure 4.8
Transmission
Hue
oficiijjtli
L with
liieorcm.
The
has
ihe
mdamcniai erminai
resistors
are
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
follows
energy
on the
line
range
C2)
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
the
terminal
impedance
is matched
load
rise.
must emit
Thus
energy to the
9 =
but
V
</2>R
\302\273
iA/
C4)
used
2R1,
so that
itt
B8) is obtained.
temperature
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
the
possible
fvee vibrations
as a
to approximation
the
actual
distribution.
The
sonic spectrum
j in
Solids:
Dcbye Theory
square noise \\ o'uge flucluations observed cxperimcn::i))y from a 3 jiO resistorin ihe mixing chamber of a dilution as a function of magnetic refrigerator
Figure
4.9
Mean
icmpcralurc indicated by
tlidrmometer.
and
After
a CMN'
powder
R.
R. GiiTarJ,
Low
li.
A
Webb,
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
in
a solid
is quantized
average
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
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
solid
electromagnetic is bounded.
modes
in
a cavity,
of N atoms,
3A?.
each
with
three
degrees
of freedom,
a
An
elastic
in
wave
contrast
has three
to the
and one
longitudinal,
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)
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
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
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
In conventional units,
D7b)
This
result
h known
as the
in Table
Ex Debye T1 !aw.*
peri
menta! values
results
experimental
are
given
4.1. The
calculated variation of
T\302\273 0
versus
T/6
is
plotted
in Figjrc
TabL*
Problem given 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 
/
Figure5.11
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
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
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
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
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
StefanBoltzmannlaw is
'
15/iV
for the
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
\342\200\224
the Stefan
5.
The
Debye
in
low
temperature
uniis,
limit of
is,
conventional
where
the Debye
temperature 0 s (hvjkB)Fn2$fvy'\\
PROBLEMS
1.
Number
of
thermal
photons.
Show
in
equilibrium
at temporal
ure
a cavity
of photons XXs\")
in
= 2.404n~2K(t/Ac)s.
D8) whence
<r/N
irom 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
constant of the
wavelengths
The
observed
value
and
referred
to the
integrated
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\"
*.
StefanBoltzmann
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
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 Theselfenergy 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
radiates
for
4. Age
lQ;6Js~!
is the
i
total rate at
energy
energy
radiation,
on
Find
he
total
of the Sun
4.0026)
of hydrogen
the reaction
life
(atomic weight
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
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 daynight Earth is ;it a constant jemporiittini dislanwof 5S00K; RQ = 7 x 10locm; and ihe I2arihSun
Pressure
of thermal
variation.
Show for
a photon
gas thai:
(a)
p = (cUfcV),
 ^s/iiiluij/ilV) ,
E0)
l Radiat
and Planck
Oiildbnti,
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
the parlhion
function of a
where
ihe
product
E3)
is over
as
The
Helmholtz
free energy
is found
direclly from
FT][tog[texp(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
the
two
planes
to that plane.
is Jv = aB{Tf
a steady the This
 T*),
energy
where
density
vacuum
be
aB
is the
StefanBoltzmann
constant
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 oncdimcnsional 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
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
in
with
line.
10.
thai
Hcitt
capacity
by
space.
in a
ilic
ralio
of ilic
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}
term
Table
in the
sum. Check
your result by
inserting
4.2.
Heat capacity
temperature
dtelcciric solid
capacity
with
cm ~3. Estimate
the
the
heat
would be
atoms
is
in
Energy fluctuations
in
in
a solid
ai low
the
temperature contact
region with
in which
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
energy
ihe
cm3.
capacity
waves
are
of liquid
in liquid
no
longitudinal
s\"'. There
0.145gcm~3. capacity
The
0.6
transverse
waves
in the
(a) per
Calculate
the Debyc
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
important
excitations
in liquid
4He
liquid.The H. C
Kramers,
experimental
value
has been
experimems
to
f
J. Wiebes,
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.
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
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
temperature
pressure
performs
drop.
and
the
temperature
titat
entropy we know
the
an expatision. (a) Assume that was the radiation from cosmic blackbody 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 lite
The
subscripts
i and
/ refer to
the
initial
and
final
siatcs.
19, Reflective heat shieldand Kircbhoff's Consider (aw. material of absorptivity it, emtssjvtty e, and rcllecttvjty r
a plane
\\ \342\200\224 a. Let
suspended between and parallel with temperaturesru und t,. Show that the net flux
two density
black of
sfieets
also
dewars
black sheetsis (I
black
between the
r)
times
the
flux
density
with
when tiie
a
as
in Probfem
8, which
means
are
often
Mylar
film called
an
alumtntzed
SUPPLEMENT:
GREENHOUSE EFFECT
Effect
The
caused
Greenhouse
describes
by the
interposition
and in clouds,
in and of carbondioxide
the
Earth
as vapor
atmosphere
between
the Sun
and
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 SunEarthdistance.
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
the
(the
smali
subtended by
assume
Sun)
the solar
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 reemits 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 + hns.
where
l\302\243g
E9)
is
the
thermal
Oux from
presenceof
the
perfect
greenhouse
effect.
Because
Earth
the thennal
is
flux
varies
as
T4, the
new temperature
=
T\302\243s
280
K ~
333 K,
K =
F0)
53 K
so
that
the
greeahouse
warming
of the
for
\342\200\242
For
end
1992:
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
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.
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
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
^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
Then
/'I
'
t'l
5,
energy
to
equilibrium. is is
If/(,
negative: negative,
When and
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
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
A0)
use
If
we
the Stirling
fold
factorial,we
approximation for
A\"!
and
assume
tlutt v,e
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
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
concentrationof
of
ths
on their total
we
system
ideal
gas
law p
can
/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
in
units
o! r,
least
at 4.2
nQ,
a ^as
of 
K and 300
^i
at
oulv for
those
is
conditions.
of
liquid
licimin
and
tnolccubr
and
room
icmpcraturc,
unJer we
potentials
ihnt
nfnQ
\302\253 !,
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
Ihe
particles.
This
Internal and
Total
Chemical
Potential
Figure 5.3
potential
step
between
be
two
established
the with
system
i, would be raised by
q > wild
of negative with
cespect
problem
discussed same
has wide
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
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
when
we
raise
a system
of particles each
g is
the
height
/i, we
the gravitational
this
acceleration.
potential
Once a potentialstepispresent,
by
energy
of ihe
patrides produced
system.
sfcp
is included
in (he
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,: pukntuil
If in
Mgurc
5.3 we
S2 fiNed, ihe
/affinal)
= ;(,(initial) f
[,..(initial) 
/i,(inilial)]
A4)
When
the
barrier
\342\200\224
was
inserted,
brings
/^(initial)
/(i(initial)
the two
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
potential
of a
parts:
= iv
+ft,,;\342\226\240\342\200\236,
A5)
Here
is the
/jtM
is
the
potential
energy
potential
external potential,and
potential
nmy
jiial
internal
if
chemical potential*
the
definedas the
were zero.
chemical
that
be
would
be present
electrical,
external
mechanical,
magnetic,
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
term
electro
Gibbs
called
potential
and .
measures
differences
a voltmeter
mea
Internal
and Total
Chemical Potential
SysicmB)
Figure
5.4
A model
of ihe variation
altitude: heights i
\\>.iih aimcispliericpressure
in
and
di!
con wet.
System (!)
we
without
shall
an
tisc \"total
adjective
chemical
should
be
avoided
tit
situations
in
which
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 dilLiem 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 viih
5.5 ahiiude.
Decrease
0.0S
atmosphere
as
on rocket
Vine
fliyhis.
The
concerting
siraight
lias
corresponding lo a
icmpcraiure T =
a slope
227
K.
\\
\342\200\224
010
20
Heighi,
30
in
40
50
km
The pressure
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^erc 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>
iiiiiinspUufc:
see
Probicm a'ttipliaital
1.
11UC.U1.C
UanhS
LiiiiiO^pticrc
not
;n;tiir.ittly
pressure
jjloi
potnis
4QKiloiMcttrs,
roughfy
f;i!i
near
fine, suggesting
iso
vtl and
thermal range
behavior. jj{/ij):pl/i,J
line connecting the data points over an altitude range from ft,
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
nonintersection
observed
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
TS pet
with
M the
appropriate
T *}\\
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 4ii]\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:lKklJ vary
!t\\:nivs
iintwi'iiittKlfovcrtbtf in unlcr
total
diffusion
out
to
ut:tintaii)
j cotiMjisl
(Tlie 5.6).
chemical
of
is free
Chapter
5: Chemical
Potential and
G'thhs
Dhtribut

\342\200\224\342\200\224\"
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
;i,01().
fay substitution
B3)
desired
solutions 
of {22)and
to be:
,
\302\253,{B)
n^B) =
at
^\302\253@)exp{)nB/i)
B4)
where
ti@}
is tiie
concentrationat
n{B)
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
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
but is applicable to
fecromagncfic
in suspension
Internal
suspension
ttie
and fields
the
intense
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}
depend
on
the
concentration
puctielcs.
vivid examples of chemicalpotentials and potential hi the familial leadacidbattery the negative electrode consists of metallic lead, Pb, and the positive electrode is a layer of reddishbrownlead 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
electrode and
the
the
PbO.
of
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
electrode
of
SO*~ surface
ions,
than
inside
the electrolyte
(sec Figure
Similarly,
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+
during
the
discharge
not
process.
connected,
terminals arc
in
electrons
are depleted
from
the As
positive a result,
and
accumulate potential
the
negative
electrode,
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, electrodeelectrolyte 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
through
the
the
electrolyte.
The
reactions
given are
net
reactions.
The
clcclrodc (\342\226\240f)
PbO,
l>b
I
T
(b).
5igurc
5.7 T
(ajThekjJaciJ 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
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
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, Iwiku 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
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
ha!fcc!i potentials or
halfeeil
EMF's
0.4voll;
Aft
developed
\302\273
+1.6volt.
Tiic lolai
across
one
full
cell
of
ihc bniicry,
is

AK_
\302\253 2.0voli.
B9)
live lenninal
the nccaIl drives ihc electrons from opcndrcuitioitage 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
a derivative
of ihe
was
defined
in Chapier
2.
Clmpler5; Chemical
To derive
Potential
and
Cibbs Distribution
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)
D[/),/(JW),
is (dU/dN),,
all at
conslant
volunie. With
the
original
definition
of 1/t,
we have
C3)
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
and
C5)
represent
two
different
ft. The
difference
between
them is
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
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)
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,
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
of
particles
is allowed
lo change. As
C1),
C7)
By use
C0)
for
relation
C.32)
for p/r,
and the
relation
da =
dU/x
pdV/x
 pdN/x.
C8)
Chapter
5:
Chemical
Distribution
This
may
be rearranged
lo give
dV = xJs
pdV
;ujv
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
mechanics.
The
thermal
Gibbs
and
factor
diffusive
is thegenecauzauon
contact
argument retraces
of the BoHxmann
at temperature
lo a
system
3.
in
reservoir
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
58), They
the temperature
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,
\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
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
us
that
we are
The
y(<Jl)
stales
of
the
stalesof of accessible
spiciixd
and
Ikivc
energy
system
the
P{N,i:J
is proportional
to Ihe number
reservoir.
NtU0
zt).
Chapter
5: Chemical
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
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
other
lhat
the system
is in state
2:
e,)
j
D3)
g refers
to the
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
lerms
relate
to the
system. The
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).
D9)
is
(N,
 Nt)n
E1)
system. The and E1):
Here
Aa
refers
to the
refer
central
combining
E2)
Chapter
5;
Chemical
Potential
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
overall
states
of the
facior
that
converts
.
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,
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
the
system
is in diffusive
ihe
contact
system
with
reservoir.
thermal
average of the
number of particlesin
is
according
lo E6).
by
each
term
in ihe
Gibbs sum
has
appropriaie
the
value of#
of N. :
from
definition
whence lll
<,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
speak
of the
,V
occupancy of an orbital,
for </>
will
be
interchangeably
for
or
<.V>.
We often
F0)
where
is called
the absolute
lambda.
We
see from
ideal gas ). is
propcrliona!
to ihe
concentration.
Chapter5: Chcutkul
Potential
and Gibbs
Distribution
F1}
A
'
A5S
and ihe
is
F2}
This relaiior.
finding
is useful, because in
ihat will make
many
actual
problems
we determine
/. by
ihe
value
panicles.
Energy,
The
thermal
average
energy
of the
system is
v 
<E>
^i
F3)
=
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
calculations
was
obtained
in
Occupancy Example:
zero
or one.
A redblooded
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
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
\302\243~
+;.cxp(\302\243/r).
F6)
If energy
in ihe
the
atom
Theseare itjc
Aexpfc/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 512. Hemoglobin is ihe oxygencarrying 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
applies
io C), in p.
O^
sotulion.
At
conslant
temperature
/(Oj)
is
is found
to from {66}
1
be
_
I
Ac\302\273plt/i)
'
r'exp(\302\243/t)+ 1
Fg)
/.exp(\302\243/t)
(Mb)
reaction o( u
oxygen
nvyoglobm
may
be viewed
Gj
as
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 RosstFanellt and E. Antoiiini. Archives of and Btoihciittsiry Biophysics77, 47\302\253 (tySK).
Concentration
of O3,
rcbt
Fi\302\273ure512
Saturation and
curves
of O.
bound
lo nijoglobin
iKmoglobtn (Nib) (Jib) 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
+ 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,
GvmJ
bioJtaniMry.
Wiley,
1961.
G'tbbi
Factor
and
Gtbbs Sut.
which
is
[he same
in
as
the
FcrmiDirac
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
used
to dcicribc
the adsorptioiiof
Example;Impurity
atom
ionizatian as impurities
of
in a
in
semiconductor.
crystalIn
Atoms
of
numerous
chemical
by
a semiconductor
may iose an
the
electron
band
ionizalion
the semiconductor
conduction
the electron
oikn
be treated
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
electrons
and
energy
with lite
semiconductor.
We suppose
Lei / be the
electron
ionizalion
bound
can be
an ^
to
is accessible. Therefore
one
When with
the
& has
an
electron,
electron
has zero
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
1kcifoti 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\2241
\342\200\224.
G3)
The
probability
tliat
$ is
neutral
(imionized)
is
P(neutral)
which
= /'(It,/)
+ P(U,~/) ,
G4)
is just
 PtO.O).
SUMMARY
is
defined v
as h{t,V,N) i{cojvN}v_v.
{cUJcN)a
\342\200\224
also
difl'usive
bo
if jtx
= }tz.
of two
of
The
field of force.
gas ;t(int) is the quan
for
ideal
nQ
mooaiomic
and
^{Mi'lnh2)*'2
concentration.
3.
The
Gibbs
factor
that
a system
in
at chemical state
have
N particles
sum
and be
a quantum
4, TheGibbs
is
taken
over
all states
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
rotaies
about
the ions
axis
with
SI
al
temperature
j[(r) on the
H
radialdisiance
gas.
an expression
<\342\226\240 from
for
lhe
dependence
the
axis,
in terms
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
lyrih;
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
Molecules,
particularly
light molecules,
atmosphere.
fa
I'ntuiitiul
each of mass
thermal
emi'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
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
energy
or occupied
may
of two
ihis
be unstates,
is
system
that
the Gibbs
sum for
= i +
;.exp(E/r).
of
G6)
in each
Our assumption
one
time.
particle
state at
the same
state
Notice
ttuitn
in the
\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
(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)
of
the
system.
ate may
be occupied
each by
3.
1 +
I +
A2exp(\302\253/t>\302\253
/.)[!
+ Aexp(e/i)].
G9)
as
shown,
we have iotuzation.
atom
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
Livci;t^^
number
electrons
per mom
be unity.
The condition
X.
involve
5,).,
and
r.
Cmtitm
the
mtmoxitle
O2
replaces
energy
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
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
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:
<lY!>=LLi.
The
3 ^
<iV>
(81)
is
meansquare
deviation
((AWI)
=
of N from
defined
by

<(ANJ>
= <(N
<.V\302\2732>
(N>)
 2<N><N> + (N}'
</V!>
<,V>:;
(b) Show
be
written
as
<(A.V)'>
= tc<,V>/c>
(83)
liial
In t'liaptcr
fi
xvi:
;u>rly
iliis
niilt
in llio
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
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.
Schindler,
Equivalent
definition
of chemical
An
potential*
was
defined
by
E) as (cF/cN)tiy.
equivalent
expression
in Table
5.1 is
(S5)
fi
*=
(cU/cN)ay.
Prove
was used by
Gtbbs
to
define
ji, is equivalent
of/i,
to
have
adopted.
resultsC1)
and
C5).
Our
reasons
a function
a mathematical
potential moreoften
consequence, are
as
(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
the
maximum
the
height
stand
to which
in a
lhal
rools
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
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.
bound
activity
absolute
of
the
the
probability
that one
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,
tola! chemical
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
FERMIDIRAC
FUNCTION
153
BOSEEINSTEIN
DISTRIBUTION
FUNCTION
157
CLASSICALLIMIT
Chemicai
160
161
Potential
Free
Energy
163
16\",
Pressure
Energy
164
Entropy
165
Heat Capacity
165
the
SackurTetrode internal
Equation Degrees
167
with
of Freedom
\342\226\240
169
J70
Zero
Magnetic
Field
Isothermal
Expansion
17'i
IT.t
i \025
176
PROBLEMS
177
1. Derivative
2.
of FenniDiracFunction
of Filled
Function
177
Symmetry
Distribution
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
function,
designated
as /(ej./i),
one
particle.
This
state
!fthc
interactions
sin in N
between particles
quantum of an lo
approxiorbituls,
state
thai
we construct
orbital a solution of a oneparticle 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 Nparticlc 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 halfintegrai 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
halfintegral
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
even
of panicles
appear
An
as can
occupancy be occupied
zero.
1.
2.
orbital
species,
An orbital
including
can be
is a
occupied by
fermion
same species.
the
The second
of
rule
statement
of the
occupancies
need
not be
occupancies
of any
other
FamtDirac
Distribution
Function
The
two
different
occupancy
is
each orbital:
occupancy
there
there
boson
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 FcrmiDimc
distribution
the
function
BoseEinstein
orbital
for
the
thermal
average
occupancy
of an
orbital by
two
fcrmtonsand
by
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.
FERMIDIRAC DISTRIBUTIONFUNCTION
We
consider
a system
system
composed
of a
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)
configuration
comes
when
so
that
*= 1 and
the energy
is e. The thermalaveragevalue
term
the
occupancy
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
may ihe
be occupied reservoir
a! most
by
one
be
the
kinetic
confined to
the
a fixed
volume
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
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 FenmDirac 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
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
FertniDhac
Distribution
Functlor
System
Figure shown
6.2 here.
(a) Tlic obvious method of viewing The energy levels each refer to an
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\273eorbital 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 parikipossibilities: 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
occupancy JVH
0, aad
the second
tcnti
arises
from
;Vq = 1.
function distribution lies between zero and one.The FermiDirac 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
Chapter
6; Ideal Gus
\\
A'
\\
1
........
7
_6
5
\342\226\240~m. I
Figure
6.3
Plot
of the
FermiDkac
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
/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
Ihe Fermi
equal
is exactly
halffilled,
ihe
sense
of
in Chapter
7.
the
(e
*=
//),
F)
Orbitalsof
are
lower
energy
are
more
ihan halffilled,
energy
less than
halffilled.
FermiDirac
distribution
of non
distribution
function
I
Distribution
function
Figure
think
6.1
of
convenient
pictorial
way to
a system
do
orbitalslliat
but
iutecacl
with
then
we
establish
ihe ideal
bosons
in the
appropriate
limit.
BOSEEINSTEIN
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
integral
of the
not
of
conserved,
an
We
but
it
is
simpler
to think
of photons
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;
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
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
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 FenniDirac Comparison of BoseEinsicin 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
high
lemperaiure.
This
Et differs BoscEfnstcindistribution function, malhcmaticaHy tnsicad of + i 1 from the FermiDirac 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.
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
a gas
at room
isof the order of only 10\026, safely in the temperature and atmosphericpressure classical Differences between fcrmions (halfintegral 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
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
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 FermiDirac and BoscEinstein 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 FermiDirac
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
classical
regime
exp[(e//)/r]\302\273l.,
A2)
for
all
e. When
this inequality
of (tt).
is
denominator
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
of
the
FcrmiDirac /(s)
the
average
occupancy
is very
small
comparison for
with particles
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
= Aexp(r/i) to
topics
study
the
of
importance:
the
the
in
entropy,
relation,
classical
terms
of
chemical potential, heat capacity, the prcssurevolumctemperaiure 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
potential
is
found
from
the condition
that the
distribution
thermal average
to
of atoms
equals the
number of atomsknown
be
present.
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
just
the
partition
function
Zx for a
single
free
in
volume
V, whence
In
Chapter
3 it was
shown that Zt
HqV,
where
nQ
(Mrjlnh2K11
rs the
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
l/nQ. in the
monatomic
P
in agreement
=\302\273 T
tog(n/iiQ)
(IS)
wiih E.12a)
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
(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
4 I. For s.pin
be replaced
il isdiJublcdLlhevalucof
by 2\302\273G,
t\\eryw[icre
Ihe
iheparlition nghthand
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)
iiitern^J
ihe
partition
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)
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].
Bt)
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)
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 
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
in
Chapter
3.
Energy
The thermal
energy U is found
UF
from
U ~
iff,
or
taF~
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
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
so
lhiil
\\o^n0/n)
is positive.
entropy
lhe
SiickurTflrode
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 quantummechanical
the
theoretical
unsuccessful
physicists
to
explain
the
SackurTetrode
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)
can
calculate
the
derivative
directly
wn'tien
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
additional
needed
to
in
expand
detail
p, as
=
discussed
in
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.
capacities
as R,
the
systems
written
is
usually
written
The resultsC8a,b)
decrees
for
an
ideal gas
of freedom
of a
:N,
so
that
c,
= ,v
C8c)
Heat
Capacity
in fundamental
units, or
Cp
in conventional
\302\273
$NkB
C8d)
units. The
the
Greek
letter
gamma.
Example;
entropy
Experimental found
tests from
of the
SackurTeiroJc
values
are oflen
experiment!
of
ihe
of C7)
C9)
Here <j@)
denotes law
ihe
entropy
at the lowest
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 SackurTeirodc 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
point.
Chapter
2.
.1.
increase
in ihe
solidtoliquid
liquid
transformation (discussedin
niching
10).
Entropy
Lntropy Enlropy
increase
increase change
on hearing
in ihe
from
4.
5.
There
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
very
We
enlropy
comparison
neon,
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
=,
\342\200\242
A classic
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. 394399.
. 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
liquid
was
measured
pressure.
from
the
inching
poim
[o ihe
found
boiling
atmosphereof
ASIJ4Uid
The entropy
increase was
10 be
 a.SSJmol'K1.
27.2K
4.
The mol\021.
heat
input
The
required
associaied
was observed
lo be 1761J
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
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
Chemical Potential
of IdealGas
with
Infernal
Degrees
of FreeJoin
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
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
was
the subject
regime
In
classical
the Gibbs
\302\243\302\253
;.exp(\302\243fl/t)
D1)
where
terms
in n
higher
powers
of ),
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
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,
to
the
Gibbs
sum 3:
defined
earlier
as
result
plays
analogous to
Several
A3)
for
the
monatomic
ease, but
now
of
the
results
tlie
polyatomic
ideal gas:
A7)
(a)
Equation
for,*
is replaced
by
D7}
with have
<iq
defined
exactly
as before
(We shall
zero
for
the
monatomic
ideal gas
of atoms with
Because
e\\p(/i/i)
we
p. =
~
r[log(ri/nQ)
IogZiol].
D8)
(b)
The free
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
where /
may
associaied
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
of D8):
E4)
}i = T[Iog(n/ii0)
logBi
I)].
Reversible
Isothermal
Expansion
x
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
reversible
any
is the
final
pressure
volume
The
to the
final
temperature
is equal
we
see
that
is
onehalf
What The
initial
pressure.
is the
expansion?
constant
A'log
V
temperature
depends
on
volume
as
E5)
4
constant
= jVIog2
= (ix
l0\{0.69?)")
*=
0.069
1033.
E6) h.TS
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
=
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
define
W as
the work
external
This
is the
gas
on the
piston. From
E8),
E9)
w=
jpdV= 28.7J.
ruble
Expai
mt Entropy
What is the
an
The energy
expansion decreases
Chapter
*=
jNx
and
does
not change
energy
in
at constant by Afilog2,
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
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
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
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
these
results for
for
an iscnlropic
process
t.'\"'\"\"'V. =r2\"\"
F7)
Here'/ s
constant
Cp/Cy
is
the
ratio
of the
=
volume.
With
Tx
 300K and
Vs/V2
 we
F3):
K.
F9)
Tt\\k is
ihe
in
final
temperature
after
the
expansion
at constant
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
temperature
change
G0). For
an
U2
= \302\243/,
Cy{x2
r2 
r,) ,
G1)
fi
Expansion
into
or, in
conventional
units,
a2
ut =ivAB{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
the
gas expand
a hole
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
is not
the
work
is
is zero
the
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
at constant
temperature
is given by E6):
Au
a2
a,
 Nlog2 =
2
0.069
1023.
G3)
For
vacuum
= 0.
is
not
a reversible
process: the
system is not
in
the
most
(equilibrium)
configuration
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\224177x73
'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
(d) after
in (b).
(f)
nQ
= {Mi/27rfi2K/2
. concentration.
(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
Show
Thus
that
\342\200\224cf/vc
evaluated
at
ihc
the lower
FermiDirac
function.
orbitah.
Symmetry
as
f{fi
Let
e = /i
so
that
/(c)
ap
Thus
the
to the
sometimes
probability
that
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
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
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 ttynumUs
pc
where
is the
5,
Integration
of
the
tlwrntodynanric
identity
for an
thcr
modynamic
identity
at constant
number of particleswe
^.
X
G5,
Chapter
6; Ideal
Gas
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
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
2. The
{A
diffusive
contact
is established.
in
the
results
has
been called
7.
pressure
Relation
pressure
and
energy
density,
with
ihat
ihe
average
pres
in
a system
in thermal
contact
a heat
is given by
G7)
of
the
system,
(b) Show
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
p= WjlV ,
where
G9)
is
is the
thermal
average energy of
it
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 onehalf 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
onehalf
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
onehalf
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.
temperature
r.
energy;
(c)
entropy;
(t> pic.^uic;
10an
hentropic
of ideal
gas.
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
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
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
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
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
expression
expression
the entropy
With
a. The
the
temperature is
help
Gibbi
Chapter
is 3in
of
Zs ^
gas
ideal
there
(i>QV)sf,\\\\
of
;V
identical
atoms
atoms
in
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
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
FERMI
GAS
183
Ground
Density
Slale of
of
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
199
Lowest Orbilals
201
Lowest
and Second
of FreeAtoms
Orbital
Occupancy
\"He
Versus
Temperature
202
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
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.
MassRadius
for
White
219
7. Photon Condensation
8. 9.
Energy, Boson
Heat Gas
Capacity, in One
and
Entropy
221 221
222
222
Dimension
222
222
12. 14.
Fluctuations
in
a Bose.Gas
13. Chemical
Two
Potentia! VersusConcentration
Boson
222
.
Orbital
System
223
It is
theory
that
all particles,
including
with
atoms
or
bosons.
They behave
in
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
is
fixed, obtains
important variable.The
below
regime
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
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
appropriateto
J{z)
this
regime,
(n/HG)exp(\302\243/i)
D)
with
the usual
form
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 halfiniegra!
orbital
is any
panicle\342\200\224elementary
composite\342\200\224with
spin.
occupancy
fermion of
is limited
by ihe
average
occu
0 or
I,
with
an
anywhere
with
between
have
these limits. Ai
one
low
temperatures
it is
fermitm
in each
with
<
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 tiierfiy. Abo\\crfall 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 halfintegers. 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
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 lowlying
FERMI
A with
GAS
gas Fermi
Fermi ihe
is called energy.
ihe
energy
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
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
(!6orbilals) are
occupied
(a)
Figure
7.1
confined
energiesof
lenglh
spin
the
L. Each
down, (b)
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 onedtmenstonal is a positive form
crystal stn{fJ7ix/L)
the
quantum
number
it,
of a
integer then
supplemented
the
spin
quantum with
number ms
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.
ground
in Figure
7.1.
G&s
in Thtee
Dimensions
Fermi Gas in
Three
Dimensions
be a eube of sideL and volume V = L3. The orbilais have the of C58) 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
of a
of the
system
integers
to
nx,
tty,
ihai \302\273r)
hold
N electrons
the
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
is 4nn//3.
We may
then write E) as
This
The
relates
the
Fermi
socalled \"Fermi
total
energy
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)
F),
have
let
21
in the
(\342\226\240\342\226\240\342\226\240)> 2(fcX4n)
JdrtirV)
(9)
conversion
integral.
Integration
of
(8)
gives
the total
l0m\\L
0 10
Figure
20
30
40
Volume,
50
in
60
cm3
70
80
90 100
7,2
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
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
N{e)
for volume
=>
(V/in2)BM/h2)il2til2
A4)
V. Take
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
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)
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
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 FcrmiDirac 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.
B2
and
ihe
energy
is
B3)
Gas
Heat
We
Capacity
derive
Gas
gas
calcufaiionis
for
follows
most For
iman
very
lower
wiih
values
are found.
healed
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.
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 righthand
side of
eiecirons positive.
electrons
from
ef to the
second
integral
gives
firsi
bring energy
to ef The
from orbifals
product
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 FermiDirac 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.
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
is ploued
as xjtF.
0.4
0.6
3
e/A'b,
Figure
4
in uniis
ai
6
K
of 104
various
7.5
FermiDirac
disiribuiion
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
potential ji
constant
the
FermiDtrac
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
free electron Fermi and three dimensions. In common a= 0.01 at room (empcraiure, so
ji, for
;i is
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
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
electron
gas,
when
\302\253
xf,
 WUEfU.
'
I
C4)
In conventional
units,
Ctl
We
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
is degenerate;
for r
(he
gas
is in the
classical regime.
C7)
in
conventional
units
there
is an
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
form
of
the
result
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
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,
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
64 6.4
1.8 8.2
Fermi
Gas
In Metals
The
Thus of
alkali metals
the
atom, and
the atoms,
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
vF at
the Fermi
is
kinetic
energy
(he
\\ab!e;
it is
defined so that
The
. \302\243f
HO
where
eFjkB
nt is
for
electron.
values
of (he
Fermi \\emperatureTF ~
the
ordinary used
\302\253 TF
assumption
at
room
temperature
and below.
metals
at
constant
volume
may be written
as
the sum of
Sow
an
electronic
contribution
and
a lattice
vibration contribution. At
temperatures
the sum
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.
C/Tv
where
and
A are
constants
t
characteristic
and
jn2N/iF
from C7),
in
Chapter
4, The
Ii is
material
at sufficiently
iow temperatures.
helpful
display
the experimental
values of the
as a plot
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:
Table
7.3
ExpenmenUt
values of
y of
mcials
Li
Be
C
I Al
1.63
0.17 mb
Na
Si Gc Sn
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
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
gas,as degenerate
The companion
be
dwarf
discovered.
about
In 1844
a straight
observed Bessel
lincasifithadan
near
that
path
of the
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
Chapter
The
mass and
radius of Sirius B
lc;id
D5)
density from
was the
appraised incredibility
the
no
reason
to view
that
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
The average
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
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
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
A.3
the
x ltT13cm) volume
Accordingto
volume
this
relation
average
goes
as R3,
which is proportional to
The
concentration
b nuclear
matter is
?
0.11
x 1039cm3
D9)
Chemical
Potential
Near
Absolute
Zero
about
the
concentration
of nudeons
in a
white dwarf
protons
not
are the
not Fermi
identical
equal
one
Or the
relation
\302\243,=\342\204\242C>r'\302\273)M
E0)
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
which
a substantial
fraction
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 groundorbital 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.
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 BoseEinstein 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
total
number
of particles
in the
system, so ihal
Here
know
we
have
made
use
of the
x +
dial
.v, which
comparison be
wiih
unity,
for otherwise
the total
large.
From
this result
we
find
E5)
asT
.0.
ForN = 1022 at
that
T = IK,
we
have
/i
noic
fromE5)
E6)
as i
~+
0.
The
chemical
potential
in a
always
be
lower
in
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
a cube
of volume
('
=\302\273 /1
where
n,,
n>4
are \302\273,
positive
integers.
ihe
lowest
orbital
is
+ 1 +
1) ,
E8)
ind
the
energy
eB1 i)
of one of
the
set of
+ 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 IO3!)(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
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 noscEiiliit'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
is very
=
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 BoseEinstein
strange;
iheir
in which
low
called
ihe greatest part of tlie population The particles in ihe ground temperatures. the BoseEinsicin condensate. The atoms
in
the ground
long
orbiial,
in ihe
as
as
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 BoscEinstein 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
number
of atoms
ofheliutn4
in
the
ground
sum
of the
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
integral
number
of atoms
\\
\\
\\r
= 0.5
/(\342\200\242.
\342\200\224\342\200\224 \342\200\224\342\226\240\342\200\224__
o!
710 Plot of Ihe boson distribution particles present to ensure ). a I. The integral
Figure
funciion
ofthe
slates
arc
gives
the
condensed
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 BoseEinstetn 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
much
closer
in energy
to the
of
first
excited
orbital
is to the
p to
the ground
population
the system
into the
Chapter
7:
Fermi
and Base
Gases
e  0 is
when
written
for
the
orbilal
at
NM=V^~,
as
in
F7)
in
all
E4),
excited
where
will
depend
on
the temperature
orbitals
increases
as tm:
or, with
e/z.
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
F8)
is, when
). =
1,
The
infiniic
= U1 10 >\342\226\240
gi
it ton
Temperature
excited
states
ts
\\.IO6VB\\H\\3;:i
G0)
where
/iQ
(Af r/2rr/i2)a/2
concentration.
We
divide
Nf by
N to
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
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
T^foralomsof
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
even
slightly
less
than te
condensed
in the
ground
have
the particles in
temperature
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.
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
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
transition
by rate
small,
of flow
through
narrow
slits is
the
viscosity
above
often shape
merely becauseof
et al.
tlte
Chapter It Fermi
twd
Base
Gases
The
condensation
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
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 zeropoint 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
ihose
normal
gases
at
room
for
Table
14.3in
The
an
values
of
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 zeropoml 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 liquid hole.
Noiice
onset of high
Osborne,
fluidify
or superfluidity
in \"He. After
Abraham,
W.
B. Weinsiock,
and B.M.
Pliys.
Rev.75,
9S8 A949).
inio
which
liquid
4He enters
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 otvupiuicy 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
A. Swenson,
Phys. lev.
of any other
temperature
lowiying
orbital,
as
we have
seen. The
in which
liquid
He { and
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.
The
phase
diagram from
of
4He
Ihe
was shown
in
Figure
7.14.
down
The
to
iiquidvapor
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
Ihe normal
II.
A temperature
called
the/
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
is given
:xisis
R. A.
according
of Helium
'He
/
Solid
/
Liquid
\342\226\240i
40
Gas
Figure
7.15
Pliase
diagrams
for
liquid
3He,
(a) in soiid
miKikeivin.
In rhc
region of negaiive
[he
slopeshown
a
higher heal
in (a)
eniropy
ihan
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
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
The of4He.
ihe
3He
7.15
exhibiis
remarkable way from the phasediagram of ihe fermion nature of 3He. Note
explained
negaiive
slope
of ihe
in
Chapter
10, the
!hc
entropy
of! he
liquid phase
the
solid
phase.
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
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
orbital
!ho excited
orbitals.
irregu
by collisions
of helium
atoms
of
if
with
in
the
wall
of the
The
transitions,
if they
occur, are a
momentum collisions
loss can
from occur.
and the
flow
not
resistanceless
such
superfluidity
in liquid
a
involves
the
the
energy
excited
and
orbitals
Momentum
were
the
excitations
He
free
!!. If
orbilais of freeatoms,with
parliele
relation
l\\.ivi
= _(/,/,)*
G6) of an atom,
k = we
the
momentum
Mo
or /ik
then
can
that
superfluidity
^/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
system
of
many
atoms.
These
and
in their
articles. particie aspect the states are called the elementary excitations of liquid He II. shall
Longitudinal give
phonons
are
the clearcut
experisuper
menial evidence
superfluidity.
for
this,
but
first
we derive
a necessary conditionfor
the
This
condition
will
show
us
superfluid
wiiy
phonontfke
nature
of the
behavior
of liquid
He II.
Quaupanhlts andSuptrJluMty,
'lie
Figure
\342\226\240\342\200\242a velocity
He
It
a steel ball or a neutron, of with V mass down a column of liquid helium aJ rest at falling Mo velocity absolute zero,so that initially are excited, if the no excitations elementary Jhere will be a damping nioliou of the body generates excitations, elementary forceon Jhe body, in order to generate an elementary excitation of energy ck alid momentum hk, we must satisfy the law of conservationof energy:
We consider
in
Figure
7.16
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
be the
satisfied process
is unrestricted.
Chapter
7; Fermi
Af0V
square of boihsides:
M02V2
2A/0/iVk
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
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
motion
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 =
the
product
of wavelcnglh
t'a, or
to [he
product of vs
times
the
wavevector
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
liquid
helium
11 under
eertain experi
pressure
and
temperature
almost closely
conditions
like
the
of
have a limiting drift value of (85).Underother the ions is limi(ed at a lower velocity
modes
by
condi
the
ercation
of
vortex rings.
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.
Lcllcrs
16,934
A966).
1.0
WavevccioT,
20
in
3.0
cm\021
units
of 50s
Figure
7.17
exciiaiioHS from
rising
free
the
for
momentum
through
of the
measured
exciutions.
lo correspond A smoosh
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
below
the
Einstein
temperature,
there
of demcnlary
excitations
exciied.The
normal
component
is the
source of
m
that are
of
fluid
the
body.
The
supcrflow
aspect
fine
appears first
in
in
experiments
which
the
ihrough a
may
lube
the
lhe
normai
remain
behind
while
we
the
have
this
situation,
relative
to
the
walls of
the tube;
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
qualitatively
slate
of electrons
in metals,
where pairs
known
of particlesin
as
near
[he Fermi
surface form a
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
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,
orientations
1, 0,
and
states. the
The
magnetic
\302\243nd
superfluids
superfiuid
magnetic
have
SUMMARY
Fermi
gas
at low
temperature
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
For
elementary
roif^s,
Wll
Ph
ly/b. Physics Today, February p. i For Bulletin 29. 5i3A97SJ. i%sici R \\d Ph
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
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
the rest
of
= pc, where
momentum
as
by (n/
in
nonrelativistic
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.
the total
(/\342\200\236
ener\302\273y
of
the
ground
stale uf ihc
gas is
(S9)
J,Vef.
The general
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/2J.
(b) Kind
r \302\253
expression
for
Use entropy
of
a
Fermi
electron
gas
in the
region
t>.
Notice
that
Chemical
a *
Oast0.
verms
\"/.
potential
temperature.
for
curvature
are
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
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, 181210A968). 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. Massradius
relationship for
electrons
(a)
be degenerate that
G
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.
Chapter 7: Fermi
5.0
and
Sose
Gases
20
Temperature,
SO
in K
$00
200
Figure
7.18 liquid
Heat *Hc
3He in
fegion
percent solution of
axis
is C/T,
and
T. Thus for
cufves
for taken
a Fermi
gas in the
degenerate temperature
are
which
theoretical
of C/T
at constant
volume
horizontal.
accounts
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
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
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
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 cneigy. 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
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
a sphere
majority
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 McGrawHill, 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
number of fermions average vanishes for orbitals with energies = I. By definition, AN s thai <N>
the
the
enough
below
the Fermi
N ~
in
<N).
is the
If
</V)
as
of a
(I!)
single
orbiial
of
a boson
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 versusconcentration*
(a)
for
Sketch
a
particles
boson
carefully gas in
at
icmpcraiure
r. Include
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
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 magnetooptical 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 steadystate 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
scattered
by by
atoms
in
in
the
scattered
atoms
excited
Chapter
Heat
and Work
ENERGY
AND
ENTROPY
TRANSFER:
DEFINITION
HEAT
OF HEAT
AND
WORK
27
ENGINES:
CONVERSION
2IS
Inequality
2S
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
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
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
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
Heat
of
and
work
two
different
forms of
of energy
energy
to a
to a
The
transfer
Work
is the
transfer
para meters
that describe
the
system. gravitational
parameters
potential.
include
reason
volume,
we distinguish
process
when
we discuss
the
The most
civilizationis
important
in. a
conversion
of heat
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
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
argument
of Chapter
it
2. This
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
are
heat
processes
in
which
the total
entropy
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
(I)
as the heatreceived by
the
of
system
in the
principleof conservation
B)
energy,
dV
aw
+ dQ ,
energy
change
is caused
from
partly by
the
sysictn
partly
by heal added to
ihe System dU ~
(tQ
reservoir.
t1W =
dV
~ zda Our
d\\V
0)
process.
on
work
the system
by iftjand
in
the
reversible
reasons for
explained
dW rather
For da
\342\200\224 we
0,
have
pure work;
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:
of work are
convertible
into
mechanical
An
and into
motor,
to
entropy
transfer
is zero.
ideal
a
electrical
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
cannot
be
completely
converted
into work.
the
Entropy entersthe
work.
from
with
the beat,
but docs
heal
A device that
the
generates
has been
work from
must
heat
that
the converted
input heat
cannot
be pennittedto
ultimately
pile
up
inside
the
device
indefinitely;
way
be
removed
from
the device.
The only
to
do
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
excess
input
heat
as waste
BecauseiiQ/ifc = r,
entropy
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
difference
input
and outpul
eittropy
work.
To
prevent
ihc accumulation
of
there
be some
output
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 energyconversion devices operatein
is ultimately
and
cycles,
the
entropy
contained
in
the
device The
varies
engine.
in each
cylinder
is at a
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
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
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
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
concept
entropy
preceded
the
by some 15
highest
form of
energy.
is
possible
of
value of the
input
energy conversion
in any
ij
W/Gh,
the output
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
entropy
ihe
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. energyentropy We now have three inequalities
engine that
ft S:
&(r,/Tfc);
(9)
A0)
The
actual
W/Qk
We
can
have
i; =
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
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
lowtemperature
waste
heat
ejected
into
the environment,
so thai r, c;innoi be
temperatures
of any
ultimately
be
the an
environmental
temperature,
about 300
K. Higheilicieney requires
in
input
temperature
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
high
metallurgy.
Sources
of UreversibHity.
common
sources
of
irrevcrsibility:
(a)
Part of the
bypassing
input
heat
Qh may
flow directly
the
actual
energy
cylinder engine.
walls
duriiig
conversion
combustion
(b)
Part of
temperature
the flow.
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
be convertedbackto heat
doing
by
mechanical
friction.
(d)
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
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.
tlic of
tem
performance;
52 \302\273;
its limiting
W;Qh
f\302\260r 'he
value
reversible
operation
by
is called
the Carnot
yc. Do not
energy
conversion
i;
<
i always,
y can
be > 1 or
< 1.
efficiency of a
Eq.
From
E)
and
confuse*/ =
consumed
is
A2)
is
Th
T,'
A3]
or
smaller
than
unity.
always refrigerator
contain this
as in the ejected at the higher temperature, ettcrgyentropy 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
and
energy
flow in a
refrigerator.
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
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
conditioners the
automobile;
heat
is ejected
inside during
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.
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
are
largely
economical,
are
install
pumps
make
economic
air
conditioning
is required
anyway.
Carnot Cycle
The
derivation
of of
the
Carnot
energy
performance
conversion
made
from
coefficient a
refrigerator by which
realize process
refrigeration is
work is
generated
or
about
how refrigeraCarnot
achieved.
The
simplest
and best
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
[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
the
system
in one
cycle. The
boat taken up
at
We
combine
;/c.
Any
process
working
described
substance.
,lCyd.
Figure 85
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
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
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,
heat
Even
inputs
where
and outputs
such difference
turbines,
(here
is invariably
the
;s
temperature
reservoirs.
between
the
reser
The
healing
cooling
processes are
never truly
reversible.
Example: Carnot
cycle for an
ihc
idea!gas.
occupies
We
carry
an
ideal
monaionjic
gas
to
through
gas
reservoir
at
the
high temperature
equilibrium the
with j volume
K, as
\\vo[k heai
in
Figure
\302\243.6a. In
Hie process
n^cdmmcal
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
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
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
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
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
cancels
the
work
W2i done
by
gas
during
the iseniropic
in shaded
ncl work
delivered
8.6a
by
the
and 8.6b,
which
by
Figure
diagram
isothermalcurves,
thai
y3
Figure 8.6
and
riicompressed
the
work
an ideal gas, as a pV 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)
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
second
eniropy,
law
We
is impossible a
of heai from
All
reversible
peratures
have
could
usually is formuiaiedwiihom memion of KelvinPlanck 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
2 back io
as well.
the
higher
iemperaiure
but This
an additional
of
amouni
ihe
of
heai
The overall
any
heal
Q{in) to work
thai
li^otit), uiihout
and
waste
heai.
would require
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: pV 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.
the
are
work
given
Wub
required
to
curry
in
the system
Q
from a
by the
differences
and
W:
If such
nut
transfers
of heat
and of
loop
zero.
necessarily
be
zero,
;md we
transfers
;tre
not
The transfers of hc:itand work between state (a) ;ittd slate (b) depend on the when the two states. This pathdependence 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
from
heal.
Work
We consider the
is
energy transfer
processes
of
Figure
delivers
8.8. In
pure
a purely
mechanical
friction
or electrical
or
system that
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
is newly
created entropy.
entropy.
way
to
reverse
the
process
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
in
a system,
there
is no
in energy
and
tfWtev
i\\a
in as
reversible
this
work
in
change
a reversible
work
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
be
less
ihan
the
Sudden Example:
expansion
of an
consider
work
once
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
posittve work
an
amount
W[cy
>
0;
Wtet <
0.
C1)
is equal
lo Q,cJt,
or
~Wlcy/x
a1al'=
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
is newly outside:
created
lVitltt
*=
in
agreement
with
B8) and
B9)
Work
Figure
8.9
Systems between
which
on!)'
work
but no
heat is transferred
need not
be
at the
same temperature
work
we
assumed
that
the new
transfer.
entropy
other
during
the delivery
of work Jo the
in
system by
This
heat transfer,
Chapter
energy
Pure
We from
In this
process
heat
t2.
fs
transferred
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).
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,
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
C6!
Thus
in such
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
in an
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:
where the
system
pressure on the
its
piston
is the
external
atmospheric
changes
volume
system.
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
for other
from
purposes.
total
For
We
thjs reason it
io subtract
performed
~d(pV)
the system,
=
the
work.
eflccthe work
itW
on
defined as
till
ilW =
d{PV)
itU +
d{pV) 
itQ
~ HQ ,
C7)
new
function
= V
+ pV ,
C8)
called
the
the
enthalpy
which
plays
the role in
energy
V plays isi
processes at constant
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)
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
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
acid s. 11J.
iti
which
^titfiir
Tnc
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
where
decompose
water
with the
H;O
the
 H3SO4+'iOj + 2c!^.
net
D3)
sum
of the
rcucikm
H2
ctttuiluin
in lite
cell;
{44}
conslain goes
H2O\302\273
1O3.
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
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
 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.
voltage
charge
(not
the
heat!)
flowing
tlirough
W ~QV0.
According
D6)
in decomposing
to
D3),
there
are
two
electrons
involved
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
poierciuit V >
current
flow,
the systems
(V
on
lhc
be
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
is called a
hydrogeciosygen
a (Figure 812). Such adevice produces arc connected, eucnwl current will fuel cell. Fuel cells were used as power
incidentally
produced
dtinking
water
The
for
In
astronauts.
principal
the
area.
cells
is their
low
hundred
current,
per
unit
electrode
was
only
few
mA/cmJ;
cell
hence
large
produce
in
reasonable operating
currentvoltage characand
of an
clearochcmi'cal
in
ceil
K.I
Us two
as electrolytic
Figure
3.
\342\200\242
The
Apollo
Ni
and
NiO
Pt
as decltoiici.
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;
Chemical Work
Work performed by
work,
the
transfer
with
of particles
the
to a
because
it is
associated
chemical
potential.
system
When
is one
of the
then
energy
U depends.
If U
= U(atV,N),
for
process
dU =
by tlie
the
xda 
pdV
fidN
,
have
D9}
replaced
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
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
of the
chemical potential.
of ihe
{a} The
particle
chemical
potential
of a
into
the
system,
chemical
systems
potential.
is equal
(b)
The difference in
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
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
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
the
result
E3). The
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
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
ir iie
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
field
expulsion
is not
Superconductors are said tobeof type It if the in a range of fields above some low nonzero,
expulsion
field.
We
shall
ourselves
ark
and
Superconductors
Hgure in
816
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
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
metai
undergoes
a phase
in
transition.
.<hermodynamic
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
be
the
phase
with the
iower
energy.
Beiow
tc
than
in
zero
magnetic
fieid
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
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
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
siaic, and
st,iie. The
drawiiij;
origin
vertical se;ilc in
ftgute
ilic
is ai
und
f JrO)The
Us
ii\\
equally
applies
10 U5
= 0.
Applied
magnelic field Ba
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
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
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
amongst
the superconductors
the
crilical
temperatures,
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
the
\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
system.
at to
6.
The
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
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
2.
Absorption
is
process
i(,h
supplied
>
home and
of
this type,
with
propane
fuel,
such
energyentropy
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
towtemperature 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
in
hotsteam
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
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
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
7\",
10u kg
\302\273 20
C.
electricity
kWh.
solid
to
T~Q.
We saw in
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.) lowtemperaturereservoir, has fixed to reservoir a temperature 1\\equal the solid. Find an expression the for electrical energy
which
initial
tile
temperature
hightemperature Tj of the
required.
N noninteractiilg, if
fermions
of mass
~ 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
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
272
PROBLEMS
272
Zero
272
273
Semiconductors
3. lonization ofDonor
Growth
Impurities
in
2 73
4. Hiopolynicr
2/3
274
5.
PatticluAntiparticle
Equilibrium
Chapter
9: Gibbs
Free Energy
and
Chemical
Reactioi
GIBBS
FREE
ENERGY
F
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
treat As
the in
equilibrium Chupicr 8, we
as
G a
 xa +
pV.
A)
Chemists
often
call
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
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
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.
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
musi
be
than a maximum,
eniropy
direciiy
from change
the laking
minus
irreversible
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
Chemical Reactions
, = V.
E)
by crossdifferentiation;
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,
of gas at
equal pressure
does
not
change
in
the
process.
It follows
We
saw
in G)
that
A2)
so that
<p
must
be
identical
with ;j,
G(,V,p,t)
A3)
Thus
is equal to 'h for s singlecomponent 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
the
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
in
the form
N/V
==
p/r.
We readily
identify
in B1)
the
chemical
/((t,p)
= i
lo\302\243(pJxnQ)
B2)
Chapter
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
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
+
=
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
to changes
in the
proportions
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)sp. At fa = 0;then B6) reduces pressure dp = 0 and at constant temperature 07)
on the chemical tjo uu musl miu
to
rfC1/,/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
takes
place.
The
change
dG
B7)
dG
\302\273
vjfi
dft
B9)
In equilibriumdG
0, so
that
C0)
equilibrium
in a
transformation
of matter at
constant
pressure
Equilibrium
and
temperature.*
for Ideal
Gases
useful
We obtain a
Y^Vjfj We
simple and
form
of of
the
genera!
=
utilize
0 when
F.48)
the constituents
j as potential of species

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
when
p and
t arc specified..
Chapter 9: Gibbs
Free
Energy
and Chemical
Rcactia
C3b)
The lefthand sidecan berewritten
as
C3c)
and
the righthand
side can
be expressed as
C3d)
Here
K(t},
called
the equilibrium
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
FkVj
C5)
known
as the
says
that
the indicated
product of the
of the
force
temperature
a change
alone.
in the
change
the conceniraison
of any one
reaciam will
other
equilibrium to choose in
need
reaclants.
C4),
the equilibrium
way
constant K(x} in
internal
it is
essential
a consistent
consistency
the
zero
of the
here
because
partition
function
Zji'mi)
depends
on our
different
choice of the
reactants
eigenstales.
The
different
zeros
for the
energy
must
to give
diilicuh
our
on
difference
in ihe
reaction. a conscious
not
happen
without
^
as
of
l\\2
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
H2 a!
molecule} res!.
with the
is \302\2433
Accordingly,
~\302\243fl,
we piacc
where
ground
state
of the
composiie particle at
energy
Equilibrium for
Ideal Gases
required
and
in
the
reaction
to dissociate
the composite
is
laken
to be
positive.
i Equilibrium Example
mass
of
atomic
aciioil
for the
rcacuon Hj
law
or
the
dissociaiion
of molecul
hydrogen imo
atomic hydrogen
is
C6)
Here [llj]
of
hydrogen,
and
fjt]
atomic
foltovsihai
l37)
[h^tpo17^'
of
atomic concent
ihe
K is
given
by
logK
log^tHj)
2IognQ(H) molecule.
F(U2)/i,
factors are
C8)
in
in
terms
of the
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 4476 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:
In
liquid
waicr
ihe ioni^lion
process
H2O*~>H+ + OH\"
eeds
09}
cquilibfium
i
to
a slight by
o.ximalcly
the reaciion
D0}
Chapter
9;
Gibbs
Chemical Reactions
per liicr. inpurcualcr\302\243H*l donor. The concentration
\342\200\224
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
ihe
suggests\342\200\224ihc
ions ate
not bare
protons,
vulidily
are of
with groups*
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
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 75; slightly plasma pH
Kxati\\ple2
Kttictic
modelof/nms
action.
AB
moieculc
nB,
nAB denote
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
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
thermodynamics.
principally
AB is noi formed
some
by
the bimolecular
collision of
and
is
catalytic
process such as
\"
The
dominant ptolon.
one surrounding
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
ai ihe
end
of the
no significant
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
and
Chemical
Reactions
1. The
G3
is a minimum
in
iff +
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
 ^w.
a function
of
the
temperature
alone.
PROBLEMS
(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,
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 +
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
atomic
hydrogen,
and
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.
The result
given
by
0]~[H]\"V'3\302\253p(//iT).
D8) connection
A similar
problem arises in
semiconductor
atoms
physics
in
ujth
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
concentration.
C)
concentration
equilibrium
concentration
of
excited
with
electronic
[H(exc)] andT 3,
K. 5000
of donor
[e]
for
state, conditions
which atthe
[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.
for
Chapter
9: Gibbs free
Energy
and
Chemical
Reactions
this reaction,
satisfy
of
mass
action
[N
1]
[If \"/K.KjKj
for
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,
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).
for the expression equilibrium, (a) Find a quantitative = = n+ n~ in the particleantiparticle 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 ATake 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
284
284
System
for GasSolid
Equilibrium
285
287
WAALS
EQUATION
OF STATE
288
van the
Critical Points
Gibbs Free Energy
for
the of
der van
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
305
305
305
Water
of Vaporization of Ice
Equilibrium
GasSoltd
305
5. GasSolid
7. Simplified
8.
of 6. Thermodynamics
First
Equilibrium
the
305
Superconducting
Transition
306
307
Order
Transformation
307
Note: tn
the
first section
s denotes c/iV,
the
entropy
per atom.
In
the
section
on fcr
VAPOR
PRESSURE
EQUATION
volume
by
The curve
of pressure versus
We
for
a quantity
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,
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 pV 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
liquidgas
isothermsfor
soiid
coexist. Everything
equilibrium
we say
and the
equilibrium
may
holds also
on a
the
solidgas
solidliquid equilibrium.
and
Liquid
temperature
critica!
vapor*
coexist
if
the
the
of the
temperaiure
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
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
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
conditions
for
the
equilibrium
of two
thermal,
Vapor Pressure
Equatio
Liquid
Liquid
+ gas
Gas
reyj
Figure
IO.I
Pressurevolume
isotherm
and
of a
Hquid
gas
at a
gas phases
region of
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.
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
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
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 px plane alone is stable, and if liquid phase
may
two
ns
phases
<
Pi
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
Versus
which the
two two
phases, phases
z0.Suppose temperature
Pa
dp;iQ
+ rfi.Thecurve
in thep.T
divides
the
p, t plane into a
phase diagram, as
Figure
10.2
for H2O.
It is a
dt).
D)
Equations
C) and
We
make
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, 4i 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
by
C)
and
E). This
result may
be rearrangedto give
which
is the differential
or
vapor
pressure
curve.
which The derivatives of the chemical potential
occur
in G)
in terms ofquantities
accessible
to
measurement.
In the
may be
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
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
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
that
must
added
to the
sysfern to
system
one
moiecule of
reYersibly
from
the liquid
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
heat
added
in the
transfer is l1Q ~
\"
TE*
A2) the
by virtue
of the connectionbetween
heat
and
change
of entropy in a
tEs
A3)
Dcritaiion
of the
Coexistence
Cur
measured
by
elementary
We let
A*\302\253
igv, molecule
A4} is transferred
denote
the change
gas.
of volumewhen
A1), U3),
one
from the
to
liquid
she
We
combine
A5)
This
ClausiusClapcyron 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
we
may
Av by vg:
Avsva=
At
{16)
to the
atmospheric
pressure
i'9/i;( ^
(b)
We
A6)
assume
may
that
be
so
that
Ngz
applies
gas phase,
A7)
zip.
With these
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\224Z0/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 iiqufdgas 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.
substantial
regions,
consistent
with
the
Crit
ca! p
Jin.
\\
id
wa
er
Vapor
pressure
and of
iine.
ice
\342\226\240
\\
102
is 1/T.
The
\"
10
\\
Si*\"
vc
\\ s
V
\\
\342\200\242Ice 1
1.5
2.0
2.5
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
104, 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 liquidsoHd 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
is a
quanhim
3He,
(Figure
the
slope 7.15),
of and
the
liquidsolid
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
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
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
lemperaSure
is the
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
B.
heat
and enthalpy.
at
ofa
to
phase
transformation,
as
from
the liquid
t times
of the
difference enthalpy.
two
constant
f
of The
pV
the entropy
difference
called
the
differential
= dU f
pdV
Vtlp.
When
we cross the
dV
~
f pdV
//,. Thus
+
(}tg
jt,)dN
B2)
at constant
\302\273 Ml
pressure
Ha
L
Values
\302\253 tAa
\302\273 At/
pAV
 llt.
heat
B3}
capacity
of//
are
tabulated;
by integrationof the
at coiisnint
pressure:
\342\200\224
Hr
Derivation
of the
Coexistence
Curve, p
Ver
jc,,
B5)
describe
gassotid equilibrium.
with
We
construct
We
as in Figure 105. 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.
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
Gs
\302\253
to, +
pt',
=>
Fs
pvx =
//,.
Figure
10.S
Aloms
in a
solid
in
cqmSibn
wiih
aionis
in the
atoms
function
The
solid phase is
in
lo
\\
in
aioms
gas lo be lends
ihe
the
ihe
lanpemSurc most of
at
may high
iIk
atoms
;src in ll
temperature be
all ot
most of
ihe a
in ihe
gas.
Chapter
o(a
in!he
gas phase.
aloui
The pressure
in
the
solid
is equal to
that
o[
volume
If we
i>i
per
atom
in ihe
than
\342\226\240
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
phase,
and we
'
\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
OF STATE
simplest
modified the
ideal
interactions
below,
he was
liquidgas 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 liquidgas For an ideal gas we have, from
the a, b are interactionconstantsto be defined; of the long range attractivepart the of mieraeiion
atoms
in
a is
constant
between
two
short
range
repulsion
tlic
the ihcrmodynamic
transition.
F.24),
relation p
F(idealgas)
NT[log(na/n)
distances
+ i]. be treated
free
C4 approximately as
V
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
coie.
Chapter
Mean Field
Method
a
There exists
taking
simple
approximate
method,
called
method,
among
for
inio
account
the effect
the
particles system.The most Let gases and to ferromagnets. of two atoms separated a distance
of a
known denote
applications the
potential
by
r. When
the concentration
of atoms in
atoms
the
gas
is n,
the
atom
on
C6)
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
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 selfenergy
molecules
it arranges
that an
as N2.
interaction
\"bond\"between two
exact
is counted
only once in
we
number
of bonds
is
approximate
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'\027^5F
the
Figure
10.8
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.
and
b arc
interpreted
in
Points ne the
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)
\\(V
1010 be
8t
f7HJAH
Figure may
3/
for
3t/
several
written
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
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
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
constant
the
local
maximum
and minimum
of the
liquid
P~V
phases.
curve
coincide,
and
At a
horizontal
aThese
@iby D4) if
conditions
are
satisfied
and Above
tc the critical tt
no phase
pc,
Vet
respectively.
exists.
Waals
der
Gibbs
Free
Energy
van
der
Gas
Waals
The Gibbs
gas
exhibits
the !iquicigas at phase transition have from C8) and C9) the result
=
\342\200\224^
constant
pressure.
of
we
G(x,VtN)
^
a function cannot
of
Nt{log[\302\273u(K
Nb)/N]
+ 1],
D6)
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
(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
=
fig. The
unstable
phases.
The pressure
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 pV 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
is equal
to the
shaded area
Chapter
10;
Phase
Ttansfo
0.40
t\342\200\224
,Vapor[
rasure
/
\\
Figure 10.11
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
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
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.
der
Waais
cquatiO!
of slate
a! the
Chapter
Id: Phase
Transformations
conslan
 ^Liquid
Cocx
Stetice
fir
\\
<\302\243
a
\\
as
s.
v.t
der Waalsgasat
lempcralure.
a
volumes
and
For
Vt only only
!hc liquid
volumes
Vx
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
shaded
areas,
one
G?(t,/>) in
negalive
the
magnitudes
Hie
of the
areas are
equal,
line
/^{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
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
express
Aft
r
tlog{p/peq)
where
p is
pressure
for
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
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
each
of spin
an
exact
result
for the
= HjitanhOiB/t). this
E4)
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 lefthand side of Hq. E6) is piolicd as a straight line in
Figure
10.15
The righthand 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
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
0.94
intercept
moments
moves up to
are
l.so
that all
magneiic
iined
up at
absolute zero.
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)
and
left
sides
of
equation
separately
the
in
Figure
10.15. The
ts
I,
versus
x obtained
in ihis
way reproduce
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
experimental
resuiis, as
shown
in
Figure
to
10.16 at z
decreases magnetization
LANDAU
smoothly
zero
THEORY
OF
PHASER
TRANSITIONS
of the
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
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 AB 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,
(\"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($0,t)
FL(\302\243r)
if
* \302\243
Co
E8)
have
for \302\243
constant
r, ilic
first order
We
more
determines
equilibrium the
state.
In a
lowest
minimum
as
restrict
ourselves
in \302\243
to systems absence
function
ferroelectric
of
systems
the
of
are
exam
of
pies of
that \302\243
this.
it
also
assume
that
F 1(^,1) is a
sufficiently
\302\243\342\200\224
wellbehaved function
something
can
for
be expanded
granted.
in a
power series in
function of
that
should
not be
taken
For
an even
as \302\243,
assumed,
The
entire
temperature
ga\\
dependence of
coefficients
FL(\302\243,x)
is
contained
for
in the
experiment
expansion
or theory.
coefficients
g2,gx,
g6 These
are matters
when changes sign at ^(x) example of a phase transitionoccurs a temperature i0, with y4 positive and the higher terms negligible.For simplicity
The simplest
take
we
g2(t)
linear
in i:
<72(r)
(r
 to)* .
as
F0)
constant
over Witli
the these
temperature idealizations,
range
of interest,
and we take g4
in that
range.
The
certainly
form F0)
fails is not
and cannot be accurateover a very wide temperature range, on tembecause such a linear dependence at low temperatures consistent
with
it
temperature
the is \302\243
third
law. at the
The
equilibrium
value of
found
minimum of
FL{$
;t)
with
respect
which
has the
roots
f~Q
and
= (to
 r)(a/g4).
F3)
Chapter
iff;
Phase
Transformations
With a
energy
0 corresponds
to the
F1)
at temperatures
above i0;
J=Xt) =
0g(l).
F4)
(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:
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
which
to
zero
as the
temperature
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
by
of the minimum
Figure
10.19
Spontaneous
for
polarization
versus
a secondorder low
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
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 selfenergy
problems.
The
entropy
M2J2nn2
F7) unit
regime
in
which
\302\253
n/j.
Thus
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 liquidgas 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
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
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.
10.21}
in
does
second
not go
order
These
differ from
to
those
the
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
two
phases
must
satisfy tiic
where
L is
An
is the
volume
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
is a minimum
with respect to
is
in
thermal
equilibrium.
5,
A first
order
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
terms o, h.
2. Calculation of
equation
(IT{dp
water.
Calculate
the
value
of elT/dp
heat of vaporizational
of
near p
~ 1 atm
the vapor
Jg\021.
for
the
100Xis 2260
pressure
Hquidvypor
Express
of in
3. Heat of vaporization
Hgal
of vaporization 4.
ice.
The
of water
Jmol\"'
~2=C
ice
and 4.58
at
~l\302\260C.
of vaporiza
Gassolid
equilibrium.
a version
three
we
let the
osciSiators in the
soiid move in
the
which
the
high temperatureregime (t
vapor
pressure
is
the
latent
heat
per atom
is tQ
\342\200\224
\\i.
GaS'SoU'd
extreme
temperature
of interest.
the gassolid 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
monatomic.
Make the
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
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
vapor
pressure.
Thermodynamics
of the
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,
Show
that
Cs and
CN, the
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
the i dependences of
of
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.
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
at
have
in of
the lower
If the
the the
thermal excitationsin
/J phase is lower than vx in the clastic moduli for /?, then the
the
phase
will
larger
the
thermal
excitation,
Soft
systems
tend
to be
by the
is
the (a) Show from Chapter 4 that phonons in a solid at a temperature much at
low.
contributed
taken
given
by
~rc2r'i/3Oi;3/i3,
in the
Show
velocity of
all phonons.(b)
as the
temperature
>v.').
(84) trans
a finite
<
iv
actual
transformations
is
defined
as the
thermal energy
Show
must
be
that
the
latent
L = 4[U,@)In
t/,@
(85)
(84)
and
(85), U
Chapter
11
Binary
Mixtures
SOLUBILITY GAPS
ENERGY
310
OF
AND
ENTROPY
MIXING
311
318 319
320
wrth Interactions NearestNeighbor 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
330
PROBLEMS
330
1. Chemical
2.
3.
Mixing
Segregation
330
330
331
331
of
Impurities
Alloy
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
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
are called
the
constituents
and not
moleatomic
is called
mixture
is homogeneous
scale
contains
to form
two
a single
or
when
it
expression
\"oii
phases, such as oil and their and water do not niix\" means [hat
more
distinct
water.
The
everyday
mixture
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
Consider
a goldsilicon
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 lowmelting AuSi microscopic compound: a two mixture of almost phase investigation of the solidified mixtureshows
pure
Au
side
by
side
with
almost
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 goldsilicon 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 lowestmelting AuSi mixture, the 800 times. The composinon given eutectic a later socalled 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
the
homogeneous
mixture:
the
mixture miMure
hclerogeneous
melt at
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
We
will usually
simply speak of
energy.
discuss
compounds
welldefined 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
and
mixtures
atoms,
mixture
is called
is homogeneous
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
melting
Heterogeneous
and
solidification
properiies may
mixtures
a
melt
alloy:
Consider goldsilicon
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
AuSi
a
properties
of pure
substances. The
the result
compound: phase
microscopic
two
mixture
of almost
with
pure
Au
side
by
side
with
almost
they
such
properties
are common,
determines
mixture?
and
points.
are
of practical
importance
precisely because
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
Heterogeneous goldsiliconalloy. 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 towesimelting AiiSi mixiure, ihc eulectk: mixture, a concept explainedtater socalled 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
rather
than
We
the Gibbs
discuss
free energy G. We
mixtures each
simply
speak
of the free
alloys.
energy.
of constituents
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
in
iermsof
the fraciion
x of B aioms;
B}
x
Suppose
\302\273
A'b/N;
\302\273
jVa/N.
the sysiem
given
an
average
free energy
per atom
by
C)
Figure
Suppose
this curve
further
that/(.\\)
lias
the functional
ihe
11.2.
Because
derivative
points, we
at wilt
energy
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
the homogeneoussystem.
Proof
The
free
energy
of a
F
=>
j$ is
NfJ\\xfi)
.
phasesa
E)
and
where ,V,
and
Nfi are
the total
numbers of atoms in
ji, respectively.
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
thefx
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
Chapter
II:
Binary Mixtures
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 (wopointtangent 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
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
constituents is
u
(uANA
+ vsyn)/N
the
nA
4
(\302\253B
uA)x ,
A0)
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
range
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
interchange of two
mixing
of different
of the
is the
related
in this
Consider
now the
quantity
u[x)
(a
ffjtf
A3)
which
is the
free energy
the
mixing
entropy
contribution.
The
is usually nearly the same for (he an, nonmixing 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
per
atom
fQ is the
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
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
Chapter
11:
Binary Mixtures
We conclude that the AB 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
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 nearestneighbor 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 AA, AB, and BB. 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
of A and x is the
Chapter
tO. Similarly, =
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^
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
< 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 oiloil
moment bonds.
molecules.
This attraction
that leads to a strong electrostatic attraction which are only is absent in wateroil bonds,
between about
as
strong
as
the
weaker
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 fultscale extending plot diagram mixture
of gold and
structure
Chapter
11;
Binary
Mixture
\\/
Figure
11.6
Tree
energy versus
which
for homogeneousmisiures
mixture
crystallize
in ^ilfcrem
crystal
Two
differe
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
..,.,...
;.,,
SIU*
He m*.Uuivi
at W
tanpcraiures.
ilie two iiefium
The
moat
interesting
liquid mixof
with
a solubility
gap is the
miMuniof
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
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
to
the
aclual
form of
but
the
underlying
principles
are ihesamc.
Chapter
II;
Binary Mlxtur
Slabk
Dec omposilion
1
\\
1
1 1
Uns
for
a binary
below
system
tlic
with
a solubility
oCcomposition
x will
i if
the point
will
(*,i)
Tails
ai
then
form two
for
temperature
r. The
stability
curve
calculated quantitatively
fo{x).
for
the
system
of Figure lt.5,
a parabolic
PHASE
EQUIUBRIA
BETWEEN
LIQUID
a small
fraction
of a
composition
of
the
is almost always
understood
different
from
that
is phenomenon
mixtures.
We
consider
a simple
of the liquid.
The
the free
energies for
Phase
Equilibria
Solid Mixtures
gap.
(b) The
melting
temperature
constituenl
We
ta or pure
is
lower
Jhan
consider
a SemperaSure
per
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
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
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, germaniumsilicon. 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
homogeneity
''frozen
in
\"
indcnniieiy.
\342\200\242
The
slandard
iabutatlons
Constitution
binary
arc
by
M.
Hansen,
Coitsilxatlon of binary
supplement,
allays,
McGrawHill.
1958;
Shunfc,
R. P.
Edioti,
Constitution
of
McGrawHill,
1965; R
A.
McGrawHill, 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 iie 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 GcSi 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,
highernwiliiig lowermching
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;
binary
systems
in which
the
down
to
temperatures
The
significantly
go!dsi!icon
constituents.
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 twobranch 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 solidAuSi 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!dsiljcon alloys.The
37OX
consisisof
and
composiiion
iempctaiure indicaie
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
so
that
to energy of the liquid reachesbelow the common tangent phase curves. We can draw two new twopoint 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
phase
diagram
(bj in a
At
theeulecltc
temperature
t, Jhe
free energy
eutcctic
to
the
common
tangent
above
to f^
and fps, as in
although
the
Figure
The
composition.
at
free
of
energy fL
iies
(he
tangent,
a homogeneous
solid.
A mixture
of composition equal to
composition
solidifies
and
meits at a
pure
substance.
The solidification
of
Mixtures
Figurel!.!3
FiCe energies
in
a euseclic
system at t
, andati
< xr.
compositions
and and
away
From
ends ends
at at
euieciic
composition
starls at a
temperature.
melting
temperature
of eutectics
is widely
device
a large
role
in
semiconductor
tech
welding of electrical contact wires madeofgoldtosilicon devices. Leadtin 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 PbSti 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 AuSi system decreasing temperature, with is an example: The relative concentration of Au in solid Si ill equilibrium of only an AuSi 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 PbSn
of [he
Jackson.
diagram of the PbSn 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
compositions
xlS
and
xfiS.
In some
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
energy
of the
homogeneous
mixture.
2, The
in
mixing
entropy
when
atoms
of different
position.
For
the alloy
A} _IBI,
we have
3. The mixing
energy
for
nearestneighbor
=
interactions

is
uBB)]
uM
px(l
x)[uAB
j(uAA +
for
p nearest
Hquidus
neighbors.
is
4. The
the
composition
curve
a
with a solid.
.xL versus
for
liquid
Xs
phase
versus
in i
phase in equilibriumwith
with
liquid.
are
minimum
called
eutectics.
The
eutectic
temperature.
PROBLEMS
L Chemicalpotentialsm twophase
equilibrium.
Show
and
that
B of
die two
by
atomic species A
intercepts
potwo
112
the
oFthe twopoint
the vertical
Mixing
3He4He
=0
tangent
Figure
and
\342\200\224 1.
energy
mixtures
andPbSn mixtures. The phasediagram of 3He Figure 11.8 shows that the solubility
oF
liq
in 4He
> 0.
Similarly,
the
PbSn
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 nonmixing 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
4.
Solidification
range
of a
binary
alloy.
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
to
she
gold
will
penetrate
into the
(b)
silicon crystal.
the estimate
The
densities
of Au
and Si
Redo
for
800\302\260C.
Chapter
12
Cryogenics
COOLING BY EXTERNAL
IN
WORK
AN
EXPANSION
the
ENGINE
JouleThomson
Effect
334
Effect
van
337
Example: JouleThomson
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
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
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
a force
or
the
gas of 3Hc
paramagnetic
substance.
We laboratory
discuss
in
the
order
in which
they occur
proceeds
in
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
(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 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
the
compressor
via
the
heat
exchanger.
imposed
the
cooling
requirements
important
im
on
engine.
by
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
into
the expansion
engine is the
iruernat energy U^
compressor,
leaving
p2
plus
Vx
the displacement
refer
boih
fij and
with
to
a given
mass of
of
The
energy
engine to move
V% required
gas
work
by ihe engine
W
is the difference
4 PlVt)
{Ul
 {Uz +
Nr
PlV1)
Hs
H2.
\\Nx.
B)
The
gas
j=
and
pV =
Nr, hence H =
performed
on the
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
JouleThomson
eontain
stage,
two
discussed more
below.
liquefiers
temperatures,
or
expansion
expansion
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
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
JouleThomson
Effect
down
to about
hnvc
multistage
units
temperatures
down
So 135K
Gas
achieved.
Liquefaction
by the
JouleThomson 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 JouleThomsonliquefaction.
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
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
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.
engine
that extracts
JouleThomson
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 JouleThomson
the
eflccl.A
gas is
gas
is pushed
the
done against
initially
the
intermolecuhtr
below
a certain
will cool
on JouleThomson 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
191
JHe
3.20
A290)
893
8.18
6.82
34.4
66
621
5.57
205
0.90
0082
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
mosphcric
pressure.
poinl
of natural gas, which is liquefied in huge and niirogen are separaied iu lhe liquefaction ei isotope 4Hc and for 3He.
fuel.
boih
on the depends change during a JouleThomson 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:
JouleThomson
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
b are
terms
corrections caused by
corrections
short
long sign
range at
atiraction.
have
opposite
signs. The
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
Gas Liquefaction by
i a
the
JoutcThot
fixed lemperamre
inio
work
done by the
the
lempcraluie
ioIccuIcs penetrate
farther
lhe repulsive
Linde
a counlerflow
iscombined wilh litjueficrs the JouleThomson 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
JouleThomson
combining
expa
a countcrflow
Iieatexchanger.
vaJv. JT expansion
Liquefied
gas
Figure
12.4
as a
fund
ion ofihe
litjueficrs
for
operating
by the
Liude cycle,
ihe
an
ouiput
pressure
= toad
of 1 aim and

input
temperature.
at 4.2
The solid
QiM (he
curvesgive
tfDUl
coefficient
The broken
coid helium
cunes give
K
if
Hia, ihe
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&mWLdcryo&mcs
p. 1S7.
Evaporation Coaling;
PumpedHelium,
is ;i
to 0.3
The
comhimtiion
X
hc;\302\273
exchangerexpansion enter
valve Hie
consimu
suppose
combination;
liquefied.
Constant
=
cniluilpy
+
requires lhat
\302\243!
//;\342\200\236 IWii,
J)H9Ui'
\302\2436}
Here
Hla
H(TiMpa) 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
at
its
boiling
lcm
peraturc
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,pJ.
the
enthalpies
the
JouleThomson
maHer. lemperalure of lhe heat exchanger at this temperature cools the gas, liquefaction
If
will
take place.
are
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 onethirdof 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
liquid
evaporation latent
heat
away
lieiium along
vapor,
y '
with the
vap,..
cooling:
work
is done
the
:itonu'c
forces
that
cnuscJ
ihc
helium
staie
is
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
179
The
equilibrium
lowest in
tempcralure vacuum
accessible technology
isa problem
helium
vapor
pressure
drops
gas and
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
cooling principle
in
everyday ait
cooling
conditioners.
Helium
Refrigerator:
Militdegrees
pressure
of
liquid
3He has
dilution
dropped to
I0\023
torr, from
refrigeration
principles
lose their
by
K io
0.0! K. is
dominated
the
helium
refrigerator,
which is an
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 3He4He mixtures in diagram the range labeled unstable wil!
Figure
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
Wheatley.
Am1 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
dilution Cooling principle of ilm helium wiih a JHc4He nmiure. When from ihc pure ]He fluid and
4He
3He4He
a temperature
in the almost
temperatures
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 gaslike 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 3He4He 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. 3He4He 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 JHcJf1cmixed cvaporaiion underneath. phase
Figure
12.6
The quastgas of JH atoms dissolvedin liquid *He then diffuses through heat exchanger into 3 still. There the JHe is disiilledfrom the 3Hc4Hc
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 pumpedoff 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
the
still. The liquified JHe is cooled further, heat exchanger, beforereentering 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 quasigas phase of 3Hepersists down to t = 0, However, phase, gas ihe heat of quasivaporization 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
below
SmK
2.6,
can
ihe
design
of Figure
we shut
there is
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
and
Physiea
84, 102A976}.
ISENTROPIC
DEMAGNETIZATION:
doniimim
0.01
K the
cooling process
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
Figure
12.7
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
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
insulated
entropy
6c, ending up at temperature t2. The thermal contact is broken helium provided by gas, and the thermal
path
is
by removing the
of
gas with
The
a pump.
population
population
of a
only
ntB/x,
function
where
only
The
spinsystem
entropy
is a
distribution;
hence the
If SA
the
localinteractions is theeffeclive field that corresponds to thediverse among temperature r2 reached in an spins or ofthe spins with the lattice, the final
(9}
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
field
was
not
removed
iiiiiial
cniirciy,
and
only
m tfic
fields
icmpcraiurcs
After
as
cilcd
indicated values. The were idcnliait in all inns. S. Still and J. H. Milncr.
1109A957).
is
a single
shot
process. It is easily
in one
way
converted
the reservoir
disconnecting,
or
another, the
Nuclear
Because
are
Dcmagnelizalion
nuclear
much
magnetic lhan
moments similar
weaker
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
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 spincooling 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 1210fil 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\\ = TC.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
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
achieved in experiments in
particulatly
which
in
experiments
that were
nuclear
magnetic
resonance
experiments.*
SUMMARY
1. The
cooling
two
dominant
principles
of the
it
production
against
of
a gas
by letting
do
work
paramagnetic
JouleThomson
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
lowboiling
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
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
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
in
of
the
Use
liquid in
helium Table
data
Hi(q
AH
4 f(rin
A0)
for \342\200\242See,
example,
M. Chapcllier,
M. Goldman,
V.
H. Chau
and A.
Abragara,
Appl.
Phys41,
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.
gas gas
is removed,
that
under
these
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. Reexpress the result as kilowatthours 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 boiledoff 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 closedcycle with the load obtainable cooling the apparatus into the liquid collectionvesselof the refrigerator by placing the heat so lhat the still cold boiledoff 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 pressuretemperature 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
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
362
363
SEMICONDUCTORS
/rTVPE 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
SemiInsulating
Gallium
Arsenide
372
pn JUNCTIONS
373
pn
ReverseBiased
NONEQUIUBRIUM
Abrupt
Junction
377
SEMICONDUCrORS Diffusion
Through an Impurity Level
379
379
QuasiFermi
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. Builtin 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
ElectronHole
Pair Generation
388
iiiiiiui^zny
conduct v\302\273'ilti
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
caiiicr mobilities.
ENERGY
BANDS;
AND
FERMI LEVEL;
HOLES
ELECTRONS
The
is
of the FermiDirac disiribution to eiecirons in semiconductors application central to the design and operation of all semiconductor and devices,
treat
thus
below
those
of semiconductors and
We
semiconductor
devices
that
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 altimportant concentrations of conduction electronsand of holesupon the concentration and the impurity
assume
that
the
reader
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
does
be groups
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
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
Energy
Bands; Fermi
Lml; Elec
Table
13.1
Band
structure
data
Dcnslty
fstatcs
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
52
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
'
10\"
0.07
0.073
11.7
15.8
17.S8
13.13
0.015
0.39
charged
12.37
an
electron
the valence
in
the
process)
are called
\302\253j+be
acceptors.
concentration
Let
!he
na~
the
concentration
of negatively
charged acceptors.
An
The difference
C)
/[/
na~
ts called becomes
condition
An
Hj*
\342\200\224
no~~t
D)
which
distribution
exp[(e where
E)
/
[i is
electrons.
The
subscript
e refers
to
electron
chemical theory
semiconductor
always
reserved
for ihe
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
ihe
limil
r *
0, we shall maintain
at
previous
of 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
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
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 temperaturedependent 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
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
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 densifyofsfates 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
formally
by wriiing,
analogy
A3),
Nc *= 2(mSz/2nti2K'2V
,
electrons.
A5)
Experimasses
where
Experimental
me*
is
called arc
the given
values
of effective
it
is more
than
a formality.
In the theory
of
electrons
in crystals
is
shown
that
Classical Regime
holes,
under
is
that
of particles
the
free electron
Ihe densityofstaJes
We
different
from
define
the
quantum
conduction
eleclrons
as
nc =
NJV 
A6)
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
for
holes
as
NJV
2{in^z/2jihi)m.
where
wk*
is
llns
dcnsityofsJaJcs
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
terms
of
(he
positionof
quantum
con
the
Fermi
nu
level
is
relative the
edge.
of the
Law
(he
semiconductor band.
literature
called
valeuce
of Mass
Action
is
The productn^nh
are
independent
of the
concentrations
in the
classical regime.
Then
'V'k = 'WexpffE,.
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
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
then
write
B2a) as
B2c)
The
mass
value
of
the
product
depends
only on
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 righthand
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
that
is usually
small.
wTYPE
Donors
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\273itype; a semiin devices
or holes.
semiconductor with
n and electrons is called ptype.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,
exactly fit
one
electron
into
the
filled
than the
These
with
extra
some
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.
semiconductors,
example
GaAs.
lhat
each
donor
fill
enter
the conduction
band or
one
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
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
+ V]1''2
 An],
B7b)
Most
concentration,
often
the so
doping that
concentration
is Urge
larger
either
nr or
ft*
is much
\\An\\
\302\273
nt.
This
can
Condition
defines an
B7)
then
be expanded:
[(AnJ +
An*]\"*
^[i
+ (hj&nJ]1'2
ln*l\\bt\\.
In
m +
B9)
an ntype
semiconductor
nt
B7) becomes
** n^/An
\302\253 n,.
=x
A/i
+ nffAn
An;
nh
C0)
In a
ptypc semicondiiclor
An
is negative
and B7)
becomes
^
Ji. ^
The
n?/\\An\\
\302\253 n,;
nk ^
{A/i +
extrinsic
h;V1A*i1
jAffj.
C1)
majority
the
limit
B8)
is nearly
equal to
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.
A7) or
B1) for/c
Degenerate
Scum
Figure
various
13.3
doping
silicon
as a function
of lempcraturc,
wiih
for
The Fernifleveis
of liic energy
Ic
the
band edges.
sniaii
decrease
gap
has
been negieaed.
We may
An.
to
find
ft as
a function of
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,
quan
for
iliiit
carrier. of the
The calculation
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!
Chapter
IS:
Semiconductor
Statistics
densily
of stales
is
C4)
number
of orbitals
in
the
energy
interval
+ (\302\243,e
ck).
To
iV
n,V;
in
semiconductors
we
replace
Lei x
s (e 
er)/r
and
ij
(fi
et)/t. We
of
J(c to
obtain
C6)
C6)
is known
as the
FermlDirac 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 JoyceDixon approximation:*
In semiconductors the
\342\226\240 \",/\"\342\200\236
C8)
\302\253\342\200\224iSf) t3.4
Figure
compares
the exact
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
1Q6.'
Dtgcncnitt
Slmicomlitct
6
5
4
3 2
I
i)
(.
 i,)h
above
conduciion
band
icrm
of ihc
JoyccDixon approximation
C8).
Chapter
13:
Semiconductor
Sta
When
neisno
Ihe
expression
of the
mass action
ask
ihe
reader
io show
ihat
C9) If
the
gap
will
Itself
depend
depends
on
on the
of
n, to
be used
here
concentration.
Impurity
Levels
semiconductor
moves
some
orbitals
from
the
Ihe
as
P
energy
gap,
where the
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
magnitude
lower,
mostly
because
the binding
paniy
because
of
mass
in
column
V donors
donor
corresponds
of the static dielectric constant, and for 132 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
is
one
set
of bound
orbitals
for
every
A parallel from
Orbiials are off holes and acceptors. split For each acceptor atom there is one 13.5.
energy
an
ionization
Asa ~
\342\200\224 Ea
\302\243,,,ofthesameorder
Aej. Ionization
are
listed
in Table
13.2.
Some
for
all
column
VI donors
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
with not
the same
nt
orbitals
independe
each
other;
the
electron,
the donor
opposite
spin.
As a
result, the
occupation probability
donor
is not
distribution but function, by a function given by the simple FcrmiDirac 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
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
haveeithcrspin
up or
is representedtwice in the Gtbbs sum for the acceptor, by Hence the thermalaverageoccupancy is
A
'
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
be
visualized
by a
level
logarithmic
(Figure
as
func
of
the
position
four
of the
terms
Fermi
D6);
The
four dashed
sum
lines
of
represent the
positive For
in
the two
aii
charges.The actual
total
level
occurs
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 ittype semiconductor with no acceptors.
jio~
\302\273
nh
as
in
Figure
13.6, the
^
Occupation of
DonorLetch
Figure
13.6
Graphical
determinaiion
an n1ypc
sciniconducior
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
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
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
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
example,
in
that
=s 0M5nc
Ae,j
t.74r E4)
from
0.0!nf,
Eq.
predicts
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:
StuMitiiHtuting
pn
Junctions
However, ic
with
is possible
high ttiat
concentra
lions (tOi5IO17
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 semiinsulating GaAs and is used extensively to to10 il cm\\ substrate as a tiijjhresisiivity for GuAs devices. A similar [!0a prodoping procedure is possible in inP, with iron ihe taking place of chromium.
impurities
near tnerinste carrier Cm3) of oxygen impuriiy levels near the middle
to achieve
concentrations
and
in GaAs by together,
doping
chromium
two impu
As site
pn JUNCTIONS
Semiconductors
used
are almost never uniformly doped. An underan semidoped requires understanding of nonuniformiy of structures called pn junctionsin which the doping semiconductors, particularly We to ntype 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 spacedpn junctions, ofthe sequence or n~pn. pi\\~p in the builtin 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
The step
required to equalize the total chemical are intrinsic chemical potentials unequal,
two
when ihc
as
discussed
in Chapter
5.
A pn junclion. (a) Dopingdislribulion.!l is assumed 13.7 the that from doping changes abruptly ntype to ptype. The two levels arc usually different, doping (b) Electrosiaiic poteniiat. The
Figure buitlin 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
buitlin
dipolc
required
to
generate the
voltage
to
shift
the
energy
bands.
We assume that
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
=z vd\\
nh
s:
na,
E6)
one on
from \302\261
the
Jij,
side
and
the other
on thep
band
superscripts
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)
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
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
space
than
charge donor
on
the
side
means
that
the electron
the
concentration,
indeed,
as the
conduction
Chapter
13:
Semiconductor
Statistics
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:
\\dxj
At
F5)
the
interface
x =
0 we assume that'
F6)
where
Vn is
that
part of
occurs
on
the n side.
The exponential
on the righthandsideofF5)can
be
neglected,
and
we obtain
E for the
v
[peii,/c)(K,
field E
*/e)Vn
F7)
component
ofthe
electric
\302\243=[{2eMB/\342\202\254)(^t/e)]\022,
potential drop part of ilie builtinelectrostatic 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)
rseBiasedAbrupt
The
from
p~n
Junction
field E
lite
is the Sameas if On
to a
the
iitype
side all
electrons had
been depleted
junction
distance
(Vw2r/f)
, G0)
with
no
depletion
at
\\x\\
>
\\vK.
The
distance
wa is
depth
of penetration
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.
ReverseBiased
Let
Abrupt
pn
Junction
a voltage
be
applied
to a
pn junction,
which
voltage
the raises
p side the
is at
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
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
builtin
were
increased
by the
applied voltage,Figure
The
field
at
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
Reversebiased
p?i
junaion,
showing
tfic cjuastFcrmi
by
G4)
In the
semiconductor
field
device liierature we
approximations
often
find
G3)
have
beea
charge and
correct
distribution;
we
have
solved
the Poisson
equation
with
the
electron
distribution
F2).
Currtrni
Flow:
Drift
and Diffus
NONEQUILIBRIUM
SEMICONDUCTORS
QuaslFcrmi Levels
When
semiconductor
is illuminated
raised
with
light
of
quantum
from
the valence
concentrations created by iliumination arc larger than their equilibrium concentrations. Similarnonequiiibrium conconcentrations arise when a forwardbiased pn junction injects a electrons inio semiconductor. The semiconductor or holes into an eiectric iitype 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 FermiDirac 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 quasiequilibrium 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
7\021\"
+exp[(t\342\200\236\342\200\236)/,]\342\200\242
QuasiFermi
levels
are used
extensively
in
the
analysis
of semiconductor
devices.
and
Diffusion
band quasiFermi 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
positiondependence
quasiFermi
level.
Chapter
15; Semiconductor
Statistics
that the
density
weak,
we
may
assume
conis
of
conduction
electrons
to ihe
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)
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
n,
the
\302\253 nf
G9)
cottduclion
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
a gradient
in the
electrostatic
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,
final
form
 eptntE 4
grad
(84)
by
an
electric
gradient.
one for
results apply
in the
to holes,with
difference. holes,
The but
valence
band quasihole
is the
chemical potential
current carry
electrous
valence b;ind.
io the right
is really an
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
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
quasiFernii
distributions
G5)
this
condition
(88)
Figure
13.9
Doubleheterostructtirc
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. quasiFermi levels lie inside ihe band at least one of the quasiFermi 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 widergap 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 ptype region,and barrier of electrons that prevents the outflow an opposiic barrier ihat prevents ihe outflow of hoies to thentype region. poieniial
gap. The
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 quasiFermi 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 ofquasiequilibf 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
by an capture
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
Electronhole
recombination
ihrough
recombination
gap
Chapter
13;
Semiconductor
Statistics
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
ignore
spin
muitipiiciiy
for/,
equilibrium
FcnniDirac
we have
A /,)//,
Thus
= exp[~{^~e,)/r].
(92)
(91)
becomes
=
^
where
^exp[~fc\342\200\236)/!]\302\273\"\302\243.
(93)
ne' is
electron
conceniralion
wjlh
lhal would
be present if
ihc
equilibrium
level
and
ft
in
A7)
coincided
net
the
recombination
(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
of holes
by
ihe
limit
and
definiiion,
ah* With
nBexp[(\302\243,
ej/i]
;i,V\302\273.*
C96>
these substiiutioiis
rale rccombiiiation
is
Iiisteady
=
W'i.
Hft
R.Equations /, to
find
194)
eiiminalc
(9S)
This
is the
recombination HailSiiockleyRead
iheory.'
Applications
are developed
Problems
10 and
I).
SUMMARY
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
energy e is governed
ihe
FermiDirac
distribution
function
Here
3. The
\\i
is
the
chemical
potential
of ihe
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
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.
Rev.S7.
S35{!952).
. In
ihe classical
regime
are the
energies of
conduction
and
valence
6. The
stales
that
in 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.
called
dominate;
conduction carriers
Jitype when negative charge it is called ptype when sign of dominant ionized
The
dominate.
sign
to opposite
S,
A
of the
pn
junction
transition
fields even in the absence of an appliedvoltage. Foran field at the pn interfaceis
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
electric
current
densities
due
to electron
given
JB =
e/yi,E + eDegmdne,
ephnkE
Jp ~
.
ePsgrad
nh,
Here
% and
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
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 ntype; b) if the crystal is ptype? 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
ntype
InSb at
4.6
1016cm\"\"J the
energy
nor
gap,
is
the
nondegsnerate
C9).
applicable.
equation
Use
for
iont'zation
the generalized
nc by
o/
mass action
Solve
transcendental
iteration or
deep
graphically.
the fraction of ionized
6. incomplete
if the
donor
is larger
t }og(nJ8nd) by
impurity
substances
with
large
tonization
remain
insulators,
even if impure.
Chapter
13 s Semiconductor
Statistics
7. Builtin
and
builtin
profile.
Suppose
that
in
a .Ptype
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
npn
transistors.
The
builtin
field
aids
in
driving
the
relation
injected
for
across the
base.
Use the JoyceDixon of the ratio DJfic for electron
8.
Einstein
high
give
concentrations.
expansion itc,
series
exceeding
9. Injection laser. Use the JoyceDixon at T = to calculate approximation 300 K the electronhole pair concentration in GaAs the inversion that satisfies
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
independentof
ditt
both pair generation. Inside a reversebiased pn junction electrons and lides have been swept.out. (a) Calculate the elccironholepair 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\253type 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.
Electronhole
Chapter
14
Kinetic
Theory
KINETIC
THEORY
OF
THE
IDEAL
GAS LAW
391
MaxwellDistribution of Velocities
Experimental
392
394
Verification
Collision
TRANSPORT
Cross Sections
PROCESSES
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
FermiDirac 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
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
Consider
If a
velocity
the
as
in
Figure
14.1.
molecule of
mass M
is
the
reflected
molecule
specularly
is
from the
2A/ix.
A)
This
gives an
pressureon
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
v.la{vMv..
C)
the
thermal
average
the
by
concentration,
equipartition
of
change
ily
v which
ntaincris
energy
(Chapter
3). Thus
the pressure
is
= (NfV)z;
p=
iiAf<ps2>
'it
D)
assum
What
ption
comes
of specular
into
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
of
an
ideal
gas
into a
classical velocity
\"velocity\",
function.
Often
in
when we
when
as
this
found
is the
the
tradition
distribution
physics
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
the
positive
MaxwellDistribution
of t'ekctlies
thickness
tin
is ^Dnn2)(Int
whence
the desired
= {{nn2dn)f{zK)
We
&/.n*exp(\302\243jz)dn.
G)
take
the spin
the
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
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
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 tl.2 function of
probable arc the
\\
\\
as
speed
in units
of
\\
the
most shown
speed tm(,
mean speed
iAK1.
c and
* {2t/A/I\". Also
ttie
loot
mean square
/
1/
_
\\
velocity
Table
4.1
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
Marcus
McFee.*
The curve
Figure
of A2)
different
below;
theagreement
distribution
from
of atoms
the
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
through
ho^e
involves
an extra
to the
watt.
atoms
in
of high
those
\342\200\242
at
low
velocity.
In proportion
to thetr
research
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
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
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
distribution
Cross Sections
estimate
can
ihe collision
will
as
rigid
spheres.
Two
aioms of
diameter d
From
collide
if their
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
neglects estimate d is
the the
velocity order
of the
2.2 A
as for
of magnitude
If tlie atomic
is
at=
nit2 =
C.14)B.2 x KT'crnJ
idea!
lOi6cm2.
A4)
is given
The coiicenEration
of moleculesofan
gas
atO:Cand
atm
by the
Losclimidt number
m0
2.69
x IOi9atumscnrJ.
divided
A5)
number
by the
molar volume at
combine
The
volume
Avogadro
number
is
the
number
of molecules in
is the
a ad
A5) to obtain
Transport
Processes
the
mean
free path
\342\200\2243\342\200\224
tttz
]7pT6
2\\rT9
lO*7\"\"\"\"^
the
= 2M *
1\302\260\"i Cm'
^16a'
This
length
is about
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
TRANSPORT
PROCESSES
Consider
a system
a constant
state
with
in to
a nonequilibrium the
otUer.
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
direction
increase
gradient
transported
the
system the
through
is
that
is trans
There
directly
linear
most
transport
flux
is
proportional
to the
flux
driving force;
(coefficient)
s=
x (driving
force) ,
is called
A7}
a linear
relation
phenome
noiogicai
of
law,
such
as Ohm's
law for
A
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
mass
\342\200\224 mass
p ^
momentum
The net
one
direction
are
minus
summarized
the
Particle
In
Diffusion
Figure
14.5 we
consider a
reservoir
at chemical
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
reservoir
H
2. Particle
reservoir
first
increase
total
of reservoir 1
difference
diffusion,
when
of chemical
potential is
Jn
caused
in particle
concentration.
a'uait
Tile
flux
density
is the
urea
taken
as thc\"gradicnt
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
diffusive
and/ij.
The
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
and taken
c.
\342\200\224 ?cos<?
projection
IcosO of the
are
is 2xs'm0i}9.
Thus
equally
the surface
B1)
B2)
On
comparison
with A9)
we see that
the
diiTusivtty
is given
by
The particle
model
for
other
transport
in
problems.
thermal
In
the
the
particle
conductivity
dilTusioii
are
coneerncd
with the
transport of particles;in
by
with
of energy
and
particles;
viscosity
with
with
transport of momentum by
transport
particles;
in electrical
conductivity
that D, A. molecules,
of charge
describe
tile
processes
Let
pA
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
p;irtidcs in
that
tlie
z directioii.'!
lie drift
depends
on the
velocity of
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)
density Ju
not
in
terms
of
the
thermal
assumes
conductivity
that
K and
is a
form
there
electrons
nci
flow
transport of
additional
energyt
of particles.
Another
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
analogy
the
diffusion
equation,
DdpJAx = D(tV,/cr)(i/t/i/x).
B9)
Reservoir
Reservoir
Figure 11.6
system
conijci
wiih
at lempcratures
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
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
long
as C1)
applies.
diffusion
of momentum
parallel
and transverseto
velocity
the
gradient
with
of
the
the
Slow
in the .x direction,
is
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
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.
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
flux
density
in the
z direction
Dp
daJds
n
C3)
Thus, with
given
by B3),
rj
Dp
= yc!
C4)
The
\\jnd2n
CGS
from
unit
free
path
is / =
A3),
molecular diameier
as
n is
the con
be
expressed
htcfiml1
C5)
independence
than
gas
pressurp.
Tlie
fails at
at
very
high
when
the
molecules
very
low
pressures
when
path
is
longer
the
dimensions
of the
apparatus.
Robert
independence
Boyle
1660
reported
an early
in
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 momentumtransfer 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
Theory
Tabie
Experimental
in
Kp/tjCy
at
0rC
and
l atm
Gas
K,
mWcm\"'
incm*sM
/, in
;\302\273poise
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;
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 StokesEinstcinrebiion 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
diffusiiify 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
for taminar
flow.
Generalized Forces
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
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
equation
of continuity
for
the energy
density u
\342\226\240=
divju;
D0)
the equation
particle concentrationti
is
{41)
Let us
C8);
divJa
+ Jugrad{l/t)
div
Let C7)
(tt/x)
Ja
 Jn
\342\226\240
grader).
D2)
refer to
the
unit
volume;
we
take
a partial
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
n,Rt
==
that
grad/jjni
qE.
= {r'n)gradn;
for
an
potential
gfad^\302\2431,
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
unit eleciricfield.The raiio of the and rfnq in D8). These ratios must
equal,
gradn so that
E0)
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
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,iB)
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
ts directly
rate
proportional
1
the
state.
The
transi
from
to
\342\200\224 is
proportional
to the
can
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
that
be satisfied
assists
proceeds
transitions. As
the excitation
+ In
transition state
+ + of energy oscillator
\342\200\224
I)e; the
oscillator
+
it
that
__
Prob{s
s +
1)
__
for
the excitation
texts on
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)
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.
leads
from
the
state.
One
ADVANCED TREATMENT:
BOLTZMANN
TRANSPORT
EQUATION
The
classical
We
theory of
work
transport processesis
the sixdimensional
based
on
the Boltzmann
transport
equation.
velocity
in
v. Tiie
classical
distribution
f{t,\\)thdv
= number
is derived
dt
of particles in drdv.
by the
E6)
We
Tlie
the
Boltzmann
equation
following argument.
function.
consider
of a time
on
the
distribution
The Liouville
us
that
if we
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
ihen
cflct +
This
\342\226\240
grad,
/+
\342\226\240
gradv
\302\253
{df/ct)tM.
F0)
is the
many
In
the
collision
lerm (cf/ct)eolJ
may be treatedby
the
introduc
of introduction
a relaxation
the equation
ParticleDiffusion
is the
relaxation of
Here/0
for
distribution
time velocities
with
distribution
up by external forceswhieh
are
removed.
(torn
The decay
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
by
definition.
Consider an isotliermalsystem
with transport
a gradient equation
The steadystateBoltzmann
approximation
becomes
v.dffdx*
(//0)/i{,
along
where the nonequiltbritim distributionfunction/ varies as We may write {65)to first order
^fovsMJx, /\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)
/\342\200\236
f vxlr*tllfalilx\\
is The iteration
necessary
for
the
treatment
of nonlinear
effects.
Chapter
14:
Kinetic
Theory
Classical
Distribution
in
the
classical
ijmil:
exp[(/* 
e)/i],
normalization iransport rather \302\24368)
F8)
for equation than
as
in
Chapter
6.
We
function
the is as in
/ and f0.
We
take
the
normalization
as in
(ilfofduWtifdx)
ifoh){dn/dx)
F9)
order
solution
F6)
for the
/ = /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
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
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
J
where
i>ic
G9)
c is the
J.x
and t!:e diffusivity
is
\302\273
i(^\302\273A)W/V^)
~\\mdn/dx)
(80)
= \302\243>
lie.
(81)
FermtDlrac
Distribution
is
The distributionfunction
 ^_
;XP[(\302\243
WAJ +
'
(82)
\342\200\242 \342\226\240
Chapter
14:
Kinetic
To form
dfo/dx as in
F9)
we
need
dfo/dfi. We ,
argue
bciow
lhat
'tfJdH
x 6{e'y)
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
rapidly
near n we may
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
righthand
consistent
the
delta
function
dfoftlx
approximation.
=
Thus
S(e
 v)d[i/dx.
(86)
The
particle
fiux
density
is, from
Giy
wheret{ is
integral
the
relaxation
time
at the
surface e
has
the Vaiue
M3n/2cf)
by
defines
nlm
(88)
use
of Q([t)
tile
G.!7),
where
zF =
\\mvF2
(m,;i\302\273)Jii!Jx.
(S9)
At absoluie
zero ii@)
{h2j2in)Cji2n}2
J, whence
Jlt/ilx
= {ilftVmKJii')''1/\"\021}''\"/*
5(\302\243r/\302\273),/ii.V/.v,
(90)
Laws
of Rartfitd
Gaits
//=
The diffusivity
~Bxt/3m)t:Fdn/dx
~\\ve\\dnfdx.
(91)
\\vF\\
(92)
closely similarin
In
form
to
the resuh
classicaldistributionofvelocities.
Fermi the
{92} the
relaxation
time is
to be taken at the
energy. FermiDirac
We
see we
applies,
can solve transport problems where as in metals, as easily as where the classical Conductivity
a
distribution
approximation
applies.
Electrical
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
gradient of the
electric
field intensity.
The electriccurrentdensity
J,
from
{76}:
H\\/'\302\273)E;
uqhjni
(93)
relaxation
time
xc. For
the FermiDirac
distribution,
(89},
J,
(nq2xc/m)E;
*=
nq'xjm.
(94)
LAWS
OF
far
RAREFIED
this
GASES
the
Thus
molecular
in
chapter
discussion
the
mean
At
free path
a
apparatus.
path
gas
pressure
of the
free
ofa molecule
diameter
of
of a
the
laboratory
order
of
the order
of 25 cm, thus
of ihe
vacuum mean
than or
draw
a line
x x
10~6atm 10~6kgcm~2 of
as high or
0.1Nra\021 is approximately
Knudsen
region
pressures
is understood
dimensions
to be the regionin
of the
the
mean
free path
of
apparatus.
knowledge
the
behavior
of gases
in
this
pressure
region
by the
is important American
in
the
use
of high
vacuum
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~3i(T6
torr
3O~63O~9 torr
below
3G~9
torr.
in ilic Knudsen
in order
we
do not
of
need to
gas
solve a hydrodynamic
through
flow
problem
to get
molecules
do molecules
which
not
each
unit
other.
area
We
a hole,
find
strike
of surface
per unit
time. We
for
tlie
flux
density
(95)
where
prove
is
the
concentration a unit
(95),
consider
molecules.
Each
molecule
strikes
unit
time,
so thattn
c cos
molecules average of
strike unit
We
area.
solve
over
for ?, in
a hemisphere:
c. *= terms of c. Because
0, we
cos#
2*
=
J^2
j
1'
(96)
~2n
[\"\\\\aedf
?,
\302\253 \\c,
and
(95) is
obtained. The
of gas
expression (95)for
the
flux
forms
for many
the
calculations
flow in vacuum
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 =
lic.
as the
(98)
lime
The conductances of
through
the
hole the
is defined
the hole,
=>
with
volume
taken
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
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,
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 rcemittcd
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
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
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
that
of a
bole
with
the
same
area. From
This
ratio
that
every
than
unity
for
1L <
4d.
tioi
In
writing
A06)
we assumed
implicitly
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
volume pumped
pump.
per
same
time,
with
the
volume
The
symbol
S is
(H3)
just
as
for
Let
i!ie conductance
pE
of two
the
Proof:
denote
denote
[lie puntp
pressure
let
p2
Continuity
of
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
to be evacuatedmust
and
as short
connecting
lube makes
cannot
poor
speed
pump.
Further,
the speed
aperture. effective
be
larger
the conductance
rapidly
of its awn
pump
with
does a
speed
to Eq.
= p V
(99)
we
find
iP^^E^Q^Pl
dt
di
V
this
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
path.
3. Thermal
conductivity
described
Ju =*
where
Kgradr;
K = iC,,ff/ ,
(V
refers
to unit
volume.
is given
by
where
p is the
to
mass density.
the
5.
According
principle
of detailed
the
of any process that leads to a givenstatemust inverse processthai leadsfrom [he state.
rate
exactly
the rate
o( the
6.
The
Boltzmann
is
gradY
/+
\342\226\240
gmd,
/
Lzh.
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,
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)
directly of
from
the expression
in Chapter
3 for
an
ideal
gas. (b)
of
the
speed
vmP
is
vmp
most
 BT/MI'*.
A20)
Maxwell
By
probable
distribution
as a
<
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,
of
the
z component
of the
velocity of an
is
?,
(\\v:{>
$\302\243
{2t/jiA/)\"\\
A23)
2. Mean
'
(a)
Find
in
[he
an
mean
kinetic
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
velocity
thermal
component
equilibrium
ihe
mean
kinetic
real
energy? Continent:
The moiecuies in
after they
lo
heat
beam
do not
ihc
collide and
oven.
Ehe
are not in
The
residua!
moiecuies,
and
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
as
WiedemannFranz
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
(b)
Show
that
the
energy
flux in the
x direction is
where
conductivity
vx2
= =
2e/3m. Sinijm.
fc) Evaluate
the
thermal
conduc
6. Flow through
under
a tube.
difference
Show
that
when
a pressure
p between
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
velocity
the
the
flow
is
7. Speed of
second
tube.
Show
that
for air
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
hole
with
Chapter
15
Propagation
HEAT
CONDUCTION
EQUATION k
424 425
Dispersion Penetration
Diffusion
TimeIndependent
of Development
with a
Oscillation
426
427
Pulse
~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
p~n
437
437
7. Critical
of
Reactor
The purpose of
the
within
the
compass
the
of the
propagation
text
most
important
ofsound,
both dassicai
thermal
physics,
HEAT
CONDUCTION
first
EQUATION
of the
Consider
Pick law
the
derivation
!hc
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.
of
the
we
D)
equation
ofcontinuily
for the
energy density is
+ div.l.
0.
Dispersion Relation,
Versus
where
unit
volume.
We
combine
D) and
E) to obtain
~
This equation describes the
\302\253
Z),V2r;
Ds
K/C.
F)
timedependent
diffusion
of
equation is of tbc
is called diffusivity,
the temperature.
The
Ds
form
of
ihe
particle
diffusion
equation
C). The
quantity
particle
4.23}.
Comment.
C)
The
eddy
current
equation
of electromagnetic theory*
then
has l\\\\c
and
F). If 0 is
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}
0oexp[i{kr
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
so
highly
damped
ihai they
arc hardly
Chapter
IS: Propagation
at all
Substitute (9}in
(S)
to
obtain
[he relation

Dk2
ioi.
relation
io{k)
for a
Penetrationof Temperature
Consider
the
variation
of temperature
in the
semiinfinitemedium z
periodically
>
0 when
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)]}
and
i3'2
{i
 l}/%/2. Thus,
with
s BDJqiI11,
0ocxp(z/5)cos(w(
 z/5).
A3)
The quantity
characteristic
\342\226\240=
BZ)/u)}\022
has
the dimensions
penetration
the
depth if we
of the
oscillations
of 0 is
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
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.
lm.
Development of a
Pulse
layer
of
tOcm
of can
on
top
of a
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
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
so
that
*~ I.
The soiutionA4}
has
corresponds
to
the time
S(x}t
developmenl
sharply
the form
a temperature
pulse, as
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.
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
out
with
increasing
time.
The
mean square
of
x is
/X)dx ~2Dit
after
A7)
evaluating
the
Gaussian
integrals. The

is
AImi(/)
(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).
pulse
whh
= 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
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.
TimeIndependent
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
to
any
of its
An important
example
respect
to x;
=*= [\"dscxpfs^icrfu,
where
B0)
defined
= x/DDt)U2.
Here we
by
erf\302\253
jo
<feexp(s2).
B1}
Tables
of the
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.
TimeIndependent
Distribution
that
Let us
equation
is independent
of the
to lite
Laplace equation
V20
= 0.
B4)
the
Consider
a semiinfinite
medium bounded by
temperature
plane
2 =
0 and
in the
extending
boundary
vary
sintisoidaliy
0(x,y\\0) 
0os
B5)
Chapter
]5:
Propagation
The solution
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
timeindependent
the
boundary
plane
problem z =
0.
OF SOUND
earlier
effects
in
WAVES
IN
GASES
developed
Thermal
ifiis
book
can
in
be applied
this
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
wave
propagates
in the
We
direction.
suppose
the equasion
=
pV
or
and
p =
M
pr/Af
B8)
where
p ~
equation
force
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)
(p/V)lcV/ct)
,
unit
C3)
volume.
where Cv
rewrite
is
the
heat
the
second
per
We
can
re=
NMfV
&\\\\d(l/V)[dV/ct)
~(\\/p)(dp/dt).
Now the
{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
equations pu ~ po{\\
terms
+
in
the
squares
if
and
the
cross
cross
products
product
from
of
su is
reduce
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
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
sound
increases.
propagation
The
transition
is associated
frequency
high
fre