Академический Документы
Профессиональный Документы
Культура Документы
Editor:
Project
Nancy Flight
Manuscript Editor:
Veres
Ruth
Head and
Gary A.
Designers:
Renz
Production Coordinator:
Coordinator:
Illustration
Felix
Artist:
Mitchell
Batyah Janotvski
Cooper
Syntax
Compositor:
International
of Congress
Library
H. Smith
Sharon
Frank
Cataloging
in
pat;
Publication
Clmrlcs.
Killcl,
Thermal physics.
Bibliography:p.
index.
Includes
Statistical
!.
Herbert.1928-
536'.?
\302\260
I9B0
Copyright
No pan of
mechanical,
79-16677
by W.
bor.k
may
plioiographic,
H. Freeman and
be reproduced
or electronic
copiedfor
permission
in
Company
by
any
process,or in
phonographic recording,nor
may
it be
a retrieval
in
Pcimcti
this
of a
form
sioreti
ilie
United
State of
America
Kroe/n
Tillc.
II.
aullior.
O-7167-IO8S-9
ISBN
liic
joiiii
1930
QC3H.5.K52
I.
tiicrmodyn;miics.
Charles
at
has
Kiitel
since
Berkeley
1951,
having
in
work
undergraduate
solid
laught
physics
Laboratory
Kroemcr
iferbcrt
is
liliy^ics.
a I'lt.D.
!c received
in Germany
with
Professor
liurhara.
at Santa
California
University.
thesis
of Electrical
Engineering at the
His background
mid
several
nre
training
the University
in
lhc
semiconductor
then
of
University
in solid
of
state
Gulling
transistor.
new
research
labora-
of
Stales. In I96S lie became
in
to
UCStt
at ltic University of Colorado; lie came
[ilixirieul
Engineering
of semiconductors
and technology
1976. His research has been in the physics
and semiconductor devices, including
transistors,
negativehigh-frequency
electron-hole
mass effects in semiconductors, injection lasers,the Gunn
effect,
and
semiconductor
hetcrojunctions.
drops,
laboratories
in
Germany
and
the
United
Professor
Preface
This book
an
gives
simple,
other
no
Probably
and
science
are
methods
the
applications.
account
elementary
powerful,
physical
engineering.
(not
but
original,
not
easily
physics
and
These
generally.
methods
of
students
notably
a concern
stars,
or ituclci.
accessible
elsewhere)
astronomy,
for our
fields
Fermi
with
We develop
that
are
well
suited
methods
where
they
are unnecessary.
parallel.
the
do
We
fundamental
not
use
We
generally
the calorie.
temperature
t by
use
the SI and CGS systems in
to
The kclvin temperatureT is related
r =
kBT,
and
the
conventional
entropy
F.
E.
O'Meara,
Norman
E. Phillips,
B. Roswclt Russell,T. M.
Preface
B.
Sanders.
An
by
in
added
was
the index.
treatment
elementary
atmosphere
Carol
thank
for
Wilde
Professor
Richard
John
Stoeckly,
We
Wichmann.
1994
of the
on page
Muiier.
Bose-Eitistein condensationwas
For instructors who have
solutions
manual
is
available
115, following an
page
on
added
to
adopted
via
greenhouse
the
aioinic
page
suggested
argument
gas experiments
223 in 2000.
on the
classroom
use, a
course
the freeman
atmo-
for
web site
(http:/Avhfreenian.
com/thermaiphysics).
Berkeley
and
Santa
Barbara
Charles
Herbert
K'tttel
Kroemer
Note
to
the
Student
For minimum
of the concepts
the authors
coverage
presented in each chapier,
recommend the following exercises.Chapter 2: 1,2, Chapter
3:
1,2, 3,4,
8,
6: 1,2,3,6,12,
5:
11; Chapter 4: 1,2,4, 5,6, 8; Chapter
6,8;
1,3,4,
Chapter
9:
8:
14, 15;Chapter7: 2,
1,
2,
3,
5,
6,
7;
1, 2, 3;
7,
11;
Chapter
Chapter
12:
13:
3,4.5;
1,2,
Chapter
Chapter 10: 1,2,3; Chapter 11: 1,2,3;Chapter
3;
3,5,6,
15:
2,3,4,6.
Contents
Guide
xiii
to Fundamental Definitions
General
xv
References
Introduction
Chapter
1
States
a Model
System
Chapter 2
Chapter
of
Distribution
Boltzmann
27
and Hdmholtz
Free Energy 55
Chapter4
Thermal
Chapter 5
Chapter
Ideal
Chapter
il
Chapter
Binary
309
Mixtures
Cryogenics 333
Statistics
14
Appendix B
261
275
Transformations
Semiconductor
353
423
Propagation
Some
225
13
Chapter15
Appendix
Phase
1 i
181
Chapter 12
Chapter
87
Distribution
Planck
151
Work
tHeaZahd
Chapter10
Chapter
Gas
Chapter 7
Chapter
and
Radiation
Integrals
Containing
TemperatureScales 445
Exponentials
439
Appendix
Appendix
Poisson
Pressure
AppendixE
Index
465
Distribution
453
459
Negative
Temperature
460
Absolute
activity,
Accessible
Definitions
Fundamental
to
Guide
29
state
Boltzmann constant,
25
ka
Boltzmann
factor,
Boson
183
Chemical
119
/;
Classicalregime,
n
74
\302\253
nQ
31
of systems
Enthalpy, H = U
246
pV
40
Entropy,
1S3
Fermion
free
Gibbs
or grand
Heat
61'
exp\302\243~~ \302\243/t)
potential,
Ensemble
139
exp(/i/t)
sum,
\342\200\224
\\a
\342\226\240%
138
p^
138
63
capacity,
68, 227
Heat, Q
free
HelmhoHz
Landau
G =
energy,
t)/i]
free energy
Multiplicity,g
energy,
\342\200\224
\342\200\224
U
xa
function, FL
Orbital
Partition
function,
61
298
Guide to Fundamental
concentration,
Quantum
Reversible
64
41
62
Thermal
average
Thermal
equilibrium
W
hq
process
Temperature, t
Work,
Definitions
227
39
References
General
Thermodynamics
A. B. Pippard,
of classical
Elements
1966.
M. W.
R. H.
and
Zemansfcy
textbook, 6ih
anil
Heat
DiEEman,
ed., McGraw-Hill,
thermodynamics,
an intermediate
thermodynamics:
198!.
Afcchanics
Sitttisiical
U. K,
and
M. Eisner, Statistical
1988.
Agarwal
mechanics, Wiicy,
Dover
PubticaHit), Statistical mechanics:principlesand selected
applications,
iions, 1987, cl956.
C. Kittct, Elementary
statistical
applications
physics, Wiicy, 1958. Parts 2 and 3 treat
1 has been expanded
ioEo the
Part
to noise and to elemeniary transport Eheory.
T. L.
present Eext.
R.
Kubo,
R, Kubo,
Statistical
M.
mechanics,
N. Hashitsume,
Toda,
Springer,
1985.
L D.
Statistical
K. M. Lifshitz
and
L. P.
1985.
Scientific,
! (Equilibrium),
Springer,
1933,
tables
Mathematical
H. B. Dwight,
Tables
1961. A
3rd cd. by
physics,
1.
Piiaevskii, Pcrgamon, 1980, part
Ma, Statistical mechanics. World
Shang-Keng
M. Toda, R. Kubo, N. Saito,Statisticalphysics
and other
of integrals
ed.,
MacmUton,
collection.
smati
useful
widely
Applications
Asirophysics
R. J. Taylor,
The
S. Weinbcrg,
The first
ed.,
Bainam
structure
their
stars:
three
Cooks,
minutes:
and
evotitiioit.
a modern
v:\\-w
1972.
Springer,
of the
origin
of the
universe, new
1984.
T. L. Hill,
Springer,
Cooperathity
1985.
theory
in biochemistry:
steady stale
and equilibrium
systems,
General Refer,
Cryogenicsand
G. K.
low
J.
D. S.
and
Wilks
. .
Betis,
An
pa.
helium, 2nd
to liquid
introduction
ed , Oxford
Univesity
1987.
Press,
Irreversible
thermodynamics
J. A. McLennan,Introduction
1989.
I.
in low-temperature
techniques
1987, ct979
Press,
University
physics
lempcrature
Experimental
White,
I. Stcngers,
and
Prigogine
Random
to
statistical
non-equilibrium
Order
out
of
mechanics, Prentice-Hall,
man's
chaos:
new dialog
with
nature.
1934.
House,
physics
in the
interstellar medium,
Touiouse, Introduction
Wiley,
phenomena,
H. E.
and
Haasen,
Boundary
the
critical
and
critical
[ihenomena,
Oxford Uni-
1987.
Press,
affoys
Physical
metallurgy,
2nd ed.,
CambridgeUniversity
Press,
1986.
Superb.
value problems
and
J. C. Jaeger, Conduction of heat
H. S- Carslaw
Press,
sily
19S6,ci959.
Semiconductor
group and to
renormalizat'ton
1977.
University
Metais
to
197S.
Wiley,
P. PfeiHy and G.
P.
processes
transitions
Phase
19S9.
in solids,
2nd ed.,
Oxford Univer-
devices
R.
Datven,
Solid
state
physics
C. Kittel, Introduction
to solid
ed.,
Wiley,
1986.
Referred
to ssISSR
Thermal
Introduction
Our approachto
physics
to do
going
structure:
in
in
thermal
the
this
differs
from the tradition followed in beginning
we provide this introduction 10set oul what
we are
that follow. We show the main lines of the logical
all the physics comes from
In order of lhcir
the
logic.
physics
Therefore
courses.
chapters
subject
in our
are the entropy, the temporaiure,
appearance,the leadingcltaracters
story
the Boltzmann
the chemical
factor,
potential, the Gibbs factor, and the disiribu-
functions.
tion
The entropy
A
closed
system
be
in
any
of these
states
quantum
to a
accessible
states and
system.
(we assume)with
probability.
equal
fundamental
is that
ofg,3j.
may
transfer
energy;
energy,
specified
their total
are brought
into thermal
lifted.
the
transfer
product
The
of energy
in
the
one
coniact
comlraints
direction,
or
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
We have
is atiained when
ihe same
for
quantity
in ihermai
value
ihe
o((ca/cU}K_y
the Second
system.
property we
relation
by the
lemperaiure
U)
CUJ
complicated
directly
proportional
to t,
3. i.ti
c, be pjaeed in thermal
reservoir. The loia! energy
.S\"
the
of
sinies,
the
have
fundamental
smali system
with
Uo
energy
assumpiion,
s to
energy
entropy a
g{U0 by
may
definition
the
be dropped.
This
may
~
e)
is Boitzmantt's
\342\200\224
slates
e, the
lo
accessible
e)
B)
exp[<*(f
be
a{Ua)
in a
expanded
o)]
Taylor series:
=
\302\243{ca/tV0)
c(t/0)
- e/r ,
result.
have
wiil
of energy
A) of
g{U0
and
Uo
slate
- c)
numerator
have
gWo)
^@)
:n
The reservoir
wiii
:iml
in
une
it. By
tl
u large
system
reservoirwill
treau-d
factor
Dolt/nvnm
ibe
combined
\342\200\224
\302\243
and
is
temperature
kRa.
with
coniaci
energy
more com-
r; no
low
to
Kelvin
where kB is
Ayr,
entropy
given by
a very MiiipJe csampli? uf
iwn
Miiall sysicm wiih uiily
Now consider
Uiajner
with
ihe
it will foilow'that
5 is
conventional
The
will
energy
is
rclaiion
the
To show its
system
in
substitution
use, we
thermal
calculate
contact
the
with a
expansion
occurs
of C),
the
C)
in the
leaves us
thermal
with
average
reservoir at tem-
t;
E)
we have
where
of the
sum
prob-
probabilities:
P@)
The
derivation
in the
most
The
as energy with
the
as
eqtuti
the
transfer
the
to
For two
sign
systems in
in G)
is chosen to
the
chemicai
high
The Gibbsfactorof
maximum with
the transfer
respect
be
of energy. Not only
must
%\342\226\240
{ca/cU)\\also
be
N
refers
to
must
equal, where
diffusive
ensure thai
ih'w
r,
<=
and
r2
of particle flow
to low chemical
direction
potential
is Hio
coiutiiion
cttii:tiity
contact,
jt1
\\it.
The
as equilibrium
potential.
and
Bolizmann factor
of Ihe
an extension
5 is
Chapter
diffusive and
to
{uwn spevk's.Tin-*
and
thermal
is approachedIs from
(f it/jW)^,.
first
transfer
can
two systems in
For
of
4 as the
that
systems
be a
will
average energy
in Chapter
this
theory is to
reservoir.
ttie
entropy
as
well
of the
extension
thermal contact,
of particles
F)
to find the
immediately
generalized
important
ns well
particles
- 1.
at temperature r, and we do
of the Planck radiationlaw.
oscillator
harmonic
step
be
can
argument
P{e)
is a
treat systems ilia! can transfer particles.The simplestcx:unpie
1 parltcie
with two states, one witli
0 panicles
and 0 energy, and one with
system
The
in
at
e.
a reservoir
and
with
temperature r and
energy
system is contact
chemicalpotential;i. We extend C) for the reservoir entropy:
ailows
us to
tf(f/0
t;HQ
- 1) =
~
By anaiogy
with
D),
we
0(r/o;A'o)
=\302\273
cxp[{/(
ratio ofihe
is readily
(S)
have
- l-{ca/dNo)
+ ^/r.
c/r
o(U0;NQ)
P{U)/P@,Q)
for the
z{ca/dUo)
expressed
\302\243)/r]
is occupied
with
(9)
bv
particle
energy 0. The
at
energy
result (9)after
as
A0)
particularly
the
theory
The classicaldistribution
the limit
is just
The
of the
properties
The HeSmholtzfree
energy
energy
thcnnodyiumic
the
tcxl
illuminate
the
concerns
meaning
Thermal
objects,
and
physics
of
and
the
derivation
in the
F=
low
the relation
\342\200\224
to
appears
{5F/cx)s
once we have
found
out
this
result
as an
\342\200\224
a
offers
how
1:
6.
in Chapter
important computamethod
the easiest
to calculate
from
the
of
3). Other powerful tools for the calculation
arc
the
in
of
functions
reiftaiiuier of
developed the text. Most
that are useful in their own right and that illumiapplications
and utility of the principal thermodynamic functions.
connects
the world
of every iky objects, of astronomic;*!
(Chapter
chemical
and
used
because
computational function,
electron gas at
(Chapter 7).
function
to describe the
and
function
distribution
Fermi-Dirac
of metals
high concentration
and
temperature
in
macroscopic.
biological
It
unites
processes
the two
with
the
world
of moiecular.
micro-
Chapter
of a Model
States
MODEL
BINARY
AVERAGE
Energy
Example:
Function
16
System
Alloy
Sharpness
10
SYSTEMS
Enumeration
Binary
System
of the Multiplicity
VALUES
of ihe
SUMMAItY
22
:\342\226\240
Binary Magnetic
Multiplicity
18
Function
Function
System
for Harmonic
''
--.
Oscillators
-3
24
26
Bul
of a
!: States
Chapter
as a
although,
investigations
development,
in
and becauseit
thermodynamics,
yields
quite
departments
ModelSystei.
outside
results
eminently
and
elegance
and places
old truths
is the more
more different
applicability.
upon me. It
kinds
is ihu
impressive the
only
the
the
greater
it relates,
of things
Therefore
independent
light
in
of thermodynamics,
J.
A theory
to
principles,
a new
in
origin
of its
worthy
simplicity
its
of an
physical
within
theory
simplicity
deep impression
that
classical
of universal
the framework
W.
of
Cibbs
of its
premises, the
extendedits area of
made
thermodynamics
content
which
I am
convinced
concepts.
A.
Einstein
1: States
Chapter
Thermal
is the
physics
Mechanicstells
us
the
are three
heat. There
of
fruit
of work;
meaning
new
in
quantities
ordinary mechanics:entropy,
their definitions
the
in
first
and mechanical
ofslatistica!
union
the
temperature,
principles.
chapters and
three
of a ModelSyster,
thereafter.
Our
of departure
point
of the
of
system
the
for
is defined
entropy
energy
of the
of states
number
of the system
energy
concept
count
we can
the entropy
the temperature,
rhe entropy,
temperature.From
the
on
particles.
know
we
system,
is the
When
system,
(Chapter
2).
the pressure,
Fora
as
such
brevity
in
system
the
energy
we
usually
other
therm odynamic properties of tlie system.
all
a stationary
quantum state, all observable physicalproperties
and the number of particlesare independentofthe time.For
omit the word stationary; the quantum
slates
that we treat
interactions
the
which
Each quantum
said to
has
slate
may be neglected.
a definite energy.
The
level.
Stales
with
multiplicity
of energy
number
as one
shall frequently
levels. We
the
same
deal
must always
energy
levels
is taken
figure
of
hydrogen
at the
are shown
state of lowest
the
energies
arc
or degeneracy of an
the some energy,
nearly
physics, not
over all quantum
in thermal
fti'th
sums
be counted as
two
slates,
level.
identical
prolon
has
a spin
level
of
\\h
and
in
Figure
energy.
is in
has
lewis
and
!.!.
Tlte
parentheses,
uOveia!
alomic
s>^u-ms.
figure we overlook
orientations, parallel
in lite
two independent
of a Model
1; States
Chapter
SyMm
Hydrogen
Boron
Lithium
Low-tying
energiesare
to the
or antiparaliel
of a
the values
An
in electron
given
atom
of
the
multiplicities
of lithium
has three
of
shown
the
two
for atomic
electrons which
orientations
as
the
direction
we should
double
hydrogen,
move
about
the
nucleus,and eachelectronalsointeracts
nucleus.
with
Each
ail
the
Chapter
I: Statesofa Model
Systet
IUpresc
30
Mill
diq
lip liciiy
25
20
4
3
\\
'
15
5 to 3
_
1
Figure
\302\253_,,
jjj,,
1.2
n, ofa
and
Energy levels, multiplicities,
particle confined to a cube.
quanlum
numbers
other electrons.The energiesofthe levels of lithium shown in the figure are the
collective energies of the entire system.
The
leveis shown for boron, which
energy
has five electrons,
are also the energies of the entire
system.
The energy ofa system isthe total energy
ofal!
kinetic plus potential,
particles,
with
account
taken
of interactions
between particles.
to
a cube
of stde
are
\302\243
shown
states
ofa
in Figure
ofa
state
quantum
system
one-pariicie
are
of mass M con-
single particle
1.2. We shall
of the
find
in
Chapter
Chapter
1: State* of a Model
of a
an orbital
that
numbers nf,
quantum
The multiplicities
System
The
n,.
nyi
by
three
integral
positive
is
energy
tn
the
orbitals
The three
figure.
wiih(HJl^>.fi.)equ.iltoD,l,l),(l,4,]),and{l,l,4)ai!l!aveii/ +
the corresponding energy level has
3.
multiplicity
nr2
n.1
18;
the
siaie soTthejV
states
in
any
assigned
the
of
arbitrary
such as
c is
s may
it is
A' particles,
of
\302\243S(N),where
energy
Indices
system.
particle
convenient
theenergy
be
assigned
essemial
of the quantum
lo the quantum
be
index.
same
the
properties of a system
the statistical
To describe
systems
Ej{
binary
found
for
the
model
experiment. What
as we go along.
statistical
general
are of
properties
to any
well
system
that
always
concern will
realistic
agree
become
with
clear
The
model
binary
separate
and
Attached
to
syslern
distinct
each
site
sites
is an
is illustrated
fixed
in
N
shown for convenience on a line1.3.
Figure
in space,
elementary magnet
titat
can
We assume
point
only
there are
up or
down,
\302\261n>.
knowledge
any
yes
plus
and
not
physical
Model
Binary
123456789
10
Number of the
1.3
Ffgure
moment
numbers
The
\302\261m.
sire
each
Mode! system
sites on a
at fixed
magnets
has
Syster
ils own
site
composedof 10elementary
magncric
line, each having
shown arc aflachcd to ihc silcs;
magnet
assume
We
there
are no
magne'ic field.Each
moment
may be oriented in
magnetic
up or down, so ihai there are 210disiincl
of the 10 magnetic moments shown in the
arrangements
arc selectedin a random process,
figure. If ihe arrangements
two
ways,
(he probability
is 1/210.
1.4
Figure
State
of finding
ofa
tile
parking
vacant
shown
in Figure
spaces.
independent
probability
of arrangements
state of
site;
there
state of
2'v states.
10 numbered
with
particular
sites,
each
parking
theO's
by a car;
occupied
This
moment
state is equivalent
nf the
We may
bears
be oriented
of which
may
orientation
of the
lot
shown
arrangement
to
that
(.3.
particular
thai
moment
in two
ways
may
N moments is
The
2 x
2 x
\342\226\240
\342\226\240
\342\200\242
*=
with
total
2\\
nuimrr-
B)
of a
\342\226\240rl:
States
Model Syst
Figure
1,5
s> stem
of two
numbcr4hem
to
We may
are assumed to be arrangedin a definite
order.
ftom
left to right, as we did in Figure1.3.According
sequence
the state {2}also can be wriitcn
as
sites themselves
The
in
convention
this
C)
Both
D)
U)(U
The
is defined
ruie
multiplication
by
ti + till
liXti + li)
(Tt +
UU
denotes
an
T1T3I3
For
one
with
magnetic
of
moment
of
state
example.
of two elementary
possible
states
(Ti + I1KT2+
is not
but
a state
for each
one
terms,
f\302\260r
t\\i
a system
The sum
E)
for each
symbol
independent
''\"
the states
of the
of Figure
side
of listingthe four
of the
system.
(}x
li)by(t2
+ |j)
1.5:
Till
ii)
is a way
left-hand
magnets, we multiply
itTa
possible
F)
I1I2.
of the
states
system.
\342\226\240
\342\226\240
\342\226\240
Model
Binary
function
The generating
the
for
(Ti
of a
slates
system of
magnets up:
Onemagnctup:
None
The
in
is
given
T1I2T3
lihti
tihli
IJ2I3
lilif3
lilils-
up:
be denoted
will
field. The
a magnetic
values
T1T2I3
magnetic moment
states:
S different
T1T1T3
up:
magnets
three magnetsis
+ U)-
IjHTj
li)(?2+
Systems
model system
by Mt
value of M varies
from
of
which we will
to --
Nm
each
magnets
to
relate
Nm. The
of
the energy
set of possible
by
\302\253
Nm,
{N
2)m,
(N -
(N
4>n,
6)m,
\342\200\242
\342\200\242
-A'\302\273i\342\200\242,
G)
possible values of M is obtainedif we start with the state for which all
= Nm) and reverseone at a time. We may reverse iV magnets
magnets
up (M
to obtain
llie ultimate state for which
are down (A/ = - Nm).
al! magnets
There are N + ] possible
of the total moment, whereas there are 2s
values
states.When N \302\273!, we have 2N \302\273N + 1. There are many more states than
states
! 024
distributed
values
of [he total moment. !fW = 10,there are 210=
For
N many
moment.
11
different
values
of
the
total
large
among
magnetic
the
total
moment
ft/.
of
the
the
value
different states of
have
same
system
may
a given value of M.
have
in the next section how many
states
We
will calculate
The
set of
are
Only
state
one
of a
There arc N
is one
sue!
ways
state;
to form
another
a slate
with
M = Nm;that
magnet
is
(S)
-TTTT-
one
state
down:
mt
\342\200\242\342\226\240\342\226\240mt
tin
\342\226\240\342\226\240.\342\226\240tin,
AJ)
is
\"
do)
1: Slates
Chapter
with one
slates
other
the
and
of a Mode!System
magnet down are formedfrom
any single
of
Enumeration
moment
lot.il
have
\302\243!0)
by
reversing
- 2w.
M = Nw
Function
the Multiplicity
and
Stales
and
(S)
It is convenient lo
elementary
magnet.
need a mathematical expressionfor the
\342\200\224
s magnets
number
of states
with W, = {W + s magnets
up and Nl = jN
where
sis
an
When
we
turn
one
from
to
Ihe
down,
integer.
magnet
up [he down
+ s
s goes to jiV ~ 5 + I.
I and
orientation,
{.V + 5 goes to jW
?N
The difference (number up \342\200\224
from 2s to 2a \342\200\224
2. The
number
down)
changes
word
the
use
We
assume that
is an
difference
W,
ihc spin
is called
spin
excess of
left to
from
but
The
excess.
it
will
The productin
D)
may
be written
only
in
many
the order in
of the
magnets
have magnets
sites
which
the
arrows
(ID
the 4 states in
to be
in
\342\200\224
2,
if-
from
are
a state
up or down,
in a
appear
2,0, 0,
1.5 is
Figure
as
symbolically
how
particular
25
appears
(I!}
(T
\342\226\240.
We may
/V,
ft
D)
up or
we
drop
we are
when
interested
labels
in
which
and neglect
(t
II;
further,
(t +
We
find
(I
|)v for
I)' = Itt +
arbitrary
iV
by
binomial
expansion
A2)
We
may
by
With
ihis result
t with
replacing
W,
states
denote
\\N
expression{| +
|)'v
ivv =* y
becomes
tj-v+j
iA-+*
M*V\"J
A4)
of stittes having
s magnets down. This class of
$N + 5 magnets up and N, = i.V
\342\200\224
=
lias
excess
2s and net raagneiic moment 2sm.Let
us
JV,
spin
JVj
the number of states tn this class by g{N,s), for a system of N magnets:
coefficient
=
but equivatem,
different,
a slightly
in
Function
Multiplicity
\342\200\224
s:
ihe symbolic
4-
The
exponents of x and y
write the
form
and the
of Stales
Enumeration
of the term
in
is the number
M*\"'
,n\342\202\254>T
(IS)
Thus
is written
A4)
as
I stJMT^l1\"\"
(I + i)'v=
We
call g(N,s)
shall
llie same
of
value
ihe
states
Note
tn
in a
system:
of an energy level
for our
reason
5. The
deltnttion
a magnetic
of different
of
values
to the
field. Until
\302\260ur
9 is equal
multiplicity
we introduce a magneticfield, all
of the
from
of slates having
when
emerges
field, stales
magnetic
energy, so that
a magnetic
ihe number
it is
function;
multiplicity
A6)
may
be
taken
as zero.
by
'
coin, \"heads\"
down.\"
could
stand
g{Nts) =
A'
for \"magnet
\\Q are
l)-v =
given
upland
in
\"tails\"
(H)
2-v
Figures
could
1.6 and
stattd
1.7. For
for \"magnet
of yf Npi)
tUc spin
stales is
oixss
binomial
of distinct
arrangements
5 ~ 5 spins down.
9's
System
arc taken
h
of
fro
coefficients.
-10
-8
-4
Spin
To illustrate that
the
provision
single
excess
2s
Alloy System
Binary
an
-2
-6
for
exact
an
alternate
1 through
of chemical
species A
sites.
In brass,
vacant
state
of the
nature
with N distinct
alloy
crystal
1.8. Each siteis occupiedby either
chemical species B, with no provicopper and B zinc. In analogy to C),
system\342\200\224an
12 in Figure
of
or an atom
A
alloy system
could
be
can be written
as
A8)
nry
Allay
Sya,m
\342\226\240=
o
20
Number
Figure
were
throw
1,7
An
experiment
NX) times.
thrown
10
23456789
01
of
heads
Was done in
The number of
10 pennies
which
heads
in
each
was recorded.
0\302\25100
3
Fijutc
\302\251
5
chemical
0
6
10
II
012
1.8
A binary
componenls
of a
state
distinct
Every
system on
binary alloy
in the
is contained
sites
(A, +
in
conventionally
N
B2)(A3
+BN) ,
+ Bj)---(A.V
A9)
to
analogy
of
4-
B1)(A3
atoms,
atoms is NB
D).
.v lies
.\\JV. Here
between Oand 1.
The symbolic
expression
is
of
g{i\\\\f)
B on
which
is identical
prediction
of
in A'v\"'
term
of N ~
\302\243
atoms
and
to the
the
spin
model
system, except
for notation.
Function
Multiplicity
have
exceedingly
bharp
function
that
the
from common
know
major
the
of
or states
arrangements
possible
Sharpnessof ihe
usually
The coefficient
N sites:
atoms
We
result A2).
to the
analogous
number
peak
in the
from
away
the steep
of
and
multiplicity function
can show explicitly
the peak. We
defined
by
A5)
thai
us
allows
a very
sharply about
is peaked very
approximation that
variation
for
to examine
the
jV \302\273
\302\253
We cannot
(ook up these
i and
N.
form of g(S,s) versus 5 when
js|
tables of factorials do not go above N = 100, and we
values in tables:
common
may be interested in Af =^ 10'\302\260,of the order of the number of atoms in a soiid
is clearly needed,
felt.
An approximation
specimen
big enoueli to be seen and
to work with
to be
understood
is convenient
logarithms
are
whatever.
log
When
base
where
f-xccpl
log*/,
loy base*?,written
c, but
it
is clearer
you confront a
very,
here
.-ilierwise
as log.
to write
very
specified, till
The international
log when
there is
number
such
large
no
;is
Sharpnessof the
2iV, where
iV
is a
lG:o,it
the logarithm
take
We
With
logx + logy;
4-
\\N
number of magnetsup
and
of a
B2)
s)l ,
product:
~ logy.
log.v
in
N\\
\\N
B2)
down,
=\302\253
A',
5;
{23)
by use
B5)
of die
\302\273
1.
terms
\" \342\226\240
in the
1,A2iV) +
result
This
Stirling approximation,
1
ZjTi'Go
\342\226\240
\342\200\242
,
\342\226\240]
s-t\\Q\\
argument
\\
B6)
N,
large
Appendix A. For sufficiently
may be neglected in comparison with
is derived in
for N
B5)
logW,!.
+ IJ[12N)
BrtN)ti:iNNcxpl~N
B4)
as
appears
logiV,!-
which
.V!
the
N.
the logarithm
take
of
the logarithm
evaluate
accordingto
We
log&N
logarithm
log(.\\-/_v)
logg(N,s) - logW! We
number.
notation
jV, =
for the
Function
obtain
lo
- logfrV + 5)! -
= logN!
\\ogcj(N,s)
Multiplicity
logN!
(N + |) log
2k +
I log
N.
B7)
Similarly
!ogjVt! s
I log
(JV, +
2?r
logN,! s iiog2* +
After
- jV,;
BPJ
J)log.V,
- Nu
B9)
of B7),
rearrangement
log.Y!
(,Vi
JJlogN,
wlK'i'ciwcliaVcuscilW
Ito\302\243B!r/A')
= .V,
'.- f.V,
I-
.Vt.
\\
-V, +
i)logJV
- (.V, +
Nj)
CUf
\\VL-siil>ii;iLl{2S);iiKM2'J)froin{.!U)loobl:iiii
for B5):
tog</ S
ilog(l/2;r,V) -
(.V,
iJlogty./.Y)
(,V, -f
i)Uui(.V,/.V). C1)
This
because
be simplified
may
logOV,/iV) =
~
by
log^l
4-
-iog2
+ Bs/,V)
the
expansion
!og(W,/A')
= logld
of
virtue
2s/jV)
-f-
2s/S)
- I2s2/N2)
x) =
logfl +
+ iog(i
-iog2
.v
C2)
for x
\342\200\242
\342\226\240
jx2 +
valid
-,
\302\253
I.
Similarly,
On subsliiuiion in
C!)
iogg
We write this
-log2 -
- 2s/N) =
B5/N)
Qs2/,\\'!).
C3)
obtain
we
s |logB/;E/V)
Wiog2
C4)
2s!/N.
result as
C5)
C6)
WnH)\"*?1.
Such
of values of sis
a distribution
of C5)
number
caiicda
+ co
integrals
is given
are
by A5)
with
The
distribution.
Gaussian
treated
s =
2*for
in Appendix
0;
integral*
the total
A.
C7\302\273
\342\200\242
The
replacement
errors.
significanl
of a
slim
by
For example,
X s
=--
such as \302\243
by f{_.
{. - \342\226\240)
an iniegrai,
ihc rai io of
i{N2
N)
to
Ts./s
\302\273^o
is equal
io
+ A/N),
which approaches i
.)Js,
usually
'
as N
approaches
co.
= IN2
does
10
\\
1.9
Figure
(he
X.
\"
\\
\342\200\224
plotted
\\
cocfficicnis
iinearscaie. On this
on
distinguish
The
approsimaiion (o
Tlie Gaussian
binomial
ihc
entire
scale
g{!OO,s) plotted on a
ii is not possible io
drawilig
range
the approximation
of s is from
n
y
-10
-20
C6) is
from
vylue
value
is 1.264
at s
a maximum
value.
maximum
of sE0,0)
That
is, when
s/N = A/2NI'2 ,
CS).
the
measure
of g
value
of
the
prediction
well
defined.
fractional
that
the physical
are
50
the
y.
to
ChapterI: Stales
Modal System
of a
AVERAGE VALUES
The averagevalue,
mean
or
function
distribution
of a
vaiue,
is defined
P(s)
as
</> = Z/<*m*),
normalized lo
is nol
we
and
g{N,s)/2s,
D0)
have
If
unity.
\302\243J'($)
D1)
are equally
states
all
that
A7)
\302\253
2W
Zs(iV,5)
and
unity;
!.
\302\243?(*)-
The binomial
to
is normalized
function
distribution
Uic
that
provided
09)
t. Tfic
distribution
be
will
D2)
C6),
we
and +
in
replace
f{s) = s2.In
over
\302\243
the
led to
that
approximation
s by
an integral
\342\200\242
\342\226\240
\342\226\240
ds
between
C5) and
~- co
co.Then
- [2/nNI'3
(jV/2)J'J
J^Jxx^\"'*
= {2/7r,V)\"!{.V/2):i'J
(jt/4)\022
whence
<i-J>
The
quantity
spin
excess
<{2i);>
= iiV;
is the mean
<B,y> =
,V.
D3)
square
is
<B5}2>';J =>yfN
D4)
Sys
<uy Magnetic
2s is
in
fluctuation
as
defined
D5)
The larger N
smaller
is the fractional fluctuation.
This
means
is, the
that the
central peak of the distribution function
becomes
more
relatively
sharply
defined as the size of the system
the
size
measured
increase;,
being
by ihe
number of sites N. For 10:oparticles,
$F
10\0210,which is very small.
the
of
Energy
System
Magnetic
Binary
This is
orientations in
a uniform
the
Ar
H6)
magnet
in
magnetic
ihe
- MB ,
2s/n.In this
or
Following
sections.
The value
^f (he
field ?.;
magnetic
dependence
2s
by
-2,
is,
spacing
for
energy
special
i..ucaka
by wrtitng
bsiween
Ae
the
by
inferact
the
lite
example
moment
adjacent
by
tnodcl,
particular
only
but
is developedm
with
of s.
value
U{s). Reversing a
magnetic
difference
of
feature
ihat
moments
D7)
^ornrfcicly ridennined
by 2mB.The energy
is a
the generality
restrict
not
will
will
is
We shall
discrete.
levels
energy
adjacent
Constant
t.tO.
this feature
ihe
between
is
spectrum
quast-conttnuous
ihe spacing
Figure
of ihe encrcy U
of values
spcclnttn
continuous
M for the
expression
tola! potentialenergy
2smB}=
m,- =Q.
using
two allowed
with
each
mngncts,
elementary
B.
field
the
exicnial
the
This funcitotutl
~2m,
levels is
and
raises
the energy
dcnotcJ by
Ac,
where
DS)
Chopset
UM./mB
s(.)
+ 10'
10
2.30
+ 6
45
3.81
+ 4
120
4.79
+2
210
5.35
252
5.53
210
S.3S
\342\226\240
__2
+2
\342\226\240
log g(
120
-4
4.79
+ 3
-6
45
3.81
+ 4
-8
10
2.30
+5
-10
magnetic nmmersis
are labeled by
Example:
Multiplicity
system is
the
given
by Max
Sludent
problem is given
The quantum
slates
problem is the
solvable
exactly
magnetic
s values,
oscillators.
The problem of tlic
function for harmonic
for which an exact solution for the multiplicity
problem
simplest
known. Another
was originally
m m a
their
in
ofa
Chapter
harmonic
the
quantum
the oscillator.
consider
a system
number of ways
number
The number
of N such
in which
states
is
infinite,
oscillators,all
a given
total
derivation.
energy
The
excitation
of
modern
way
to
eigenvalues
D9)
or
zero,
and
the
the
is
solution
entirely
sho) ,
s is a positive integer
of
this
where
model
function
harmonic
binary
and to is the
angular
multiplicity
same frequency.
energy
We want
of
frequency
to
find
the
can
for
be distributed
tlie
among
e^rher.
pitcitv function fount!
We begin the analysis by
=
forwm'chff(i,\302\253)
we
the
function
multiplicity
the same
as the
spin
g{N,n)
mufti-
numbers,
quantum
a function
need
the
is not
to tlie multiplicity
back
of
want
function
multiplicity
going
ail values
for
is, we
That
oscillators.
the
The oscillator
Af oscillators.
to represent or generate
ihe
scries
E1)
(S3),
but
^CfC
coS\302\260
not appear
t docs
' 's
the
in
a temporary
tool that
result.
The
answer
is
final
Jusl
will
help
us find
the result
(S2)
provided we assume\\i\\
<
|. For
the problem
of JV
oscillators,
the
generating
function is
E3)
becausetlie
of w;iys n term
in which
the
number
number of onSctedwuys
We observe
i\"
can
integer
pftiJuct
sum
is picciscly
ihe
of iV non-iicg.nive
that
tj{N,n)
2) Thus
for the
\342\226\240
\342\200\242
(W
- 1).
E4)
system of oscillators,
ES)
This
result
will be
needed
in
solving
a problem
in the
next
chapter.
1: States
Chapter
of a Mode!System
SUMMARY
1.
The
In
function for a
multiplicity
N, -
N't
limit
ihe
syslem of N
with
magnets
spin
excess
2s =
is
s/N
A'
with
\302\253
1,
\302\273
1,
we
have
the Gaussian
approximation
g[N,s) * {2/rlN)m2xexp{~2s2/\\').
2. Ifal!
of
states
the
mode!
spin system
the
average
value
of
equal
to
52>
in the
3.
The
j''^JsstgtN,s)
Gaussian approximation.
fractional
of s2
fluctuation
is defined
as (s2yll2/N and
is
S/2N\022.
4. The
where
in
is the
magnetic
syslem
in a
siaie of
and
spin excess 2s is
B is
the magnetic
field.
Chapter
and Temperature
Entropy
11
ASSUMPTION
FUNDAMENTAL
PROBABILITY
3'\\
of ;in
Construction
Example:
3-
Ensemble
Most ProbableConfiguration
33
Spin Systems in
Two
Example:
Thermal Contact
3?
39
THERMALEQUILIBRIUM
TEMPERATURE
-\342\226\240!
ENTROPY
41
Floiv
On Heat
45
of Entropy
increase
of
Law
Increase
Entropy
Example:
LAWS OF THERMODYNAMICS
as
Entropy
-iS
50
a Logarithm
Second
Kind
50
SUMMARY
51
PROBLEMS
5:
1.
Entropy
and
52
Temperature
2. Paramagnetism
52
3. Quantum HarmonicOscillator
52
4.
5.
The
Additivity
53
of \"Never\"
Meaning
of
the
Entropy
for Two
6. Integrated
Spin Systems
54
Deviation
Note
we Jo
on problems: The
iitil
cinplusi^e
53
melhoJ of fhis
problem
chapter
soKing dl
lliis
siu
Chapter
2; Entropy
and Temperatui
mix,
the
one
contrary,
\302\260
W10
will
years
recognize that
ff
we
thai
two
wish
there
is
this
to find
of thermodynamics,
in
in a
gases
then again
0.1 liter
separate,
until
a time
rational
we must
then
container,initially
mix again,
unmixed,
and so forth.
long compared
One may
enormously
On
to
the gases.
of
never. . . .
mechanics
principles
and
entropy.
J.
W.
Gibbs
genera}
connection
M. Planck
only
be established
equilibrium
when
We slart
this chapter
that enables us to
a
of
average
physical property
system.We then consider
in thermal equilibrium, the definition of entropy, and the definition
of
systems
The
of
will
as
the
taw
second law
of
temperature.
thermodynamics appear
increase of entropy. This chapter is perhapsthe most abstract
in the book. The
chapters th;it follow wilt apply the concepts to physical problems.
a
with
value
the
define
definition
'
FUNDAMENTAL
ASSUMPTION
fundamental
The
assumption of thermal
of the quantum
states
likely to be in any
arc assumed to
be equally
states
accessible
states
closed
constant
system
volume,
over
of
probability
\"
\342\226\240
-
of a
ttt;tt
a closed
probable\342\200\224there
accessible
other
physicsis
system
accessible
is equally
quantum
to prefer
is no reason
some
states.
will
have constant
and
constant
influence
tmd&N/N
Unusual
the system,
\302\253
I.
properties
of a
system
may
the
sometimes
time
make
the system
it
impossible
is under
for
observation.
at
form of SiO2 are inaccessible
low
or
starts
with
the
that
temperatures
glassy
amorphous
fused
form:
in a low-tcmpcraturc
to quartz in our lifetime
of this type by commonsense.
exclusions
experiment. You will recognize
many
We
treat
are
excluded
all quantum
states as accessible unless they
by the
the
scale
of
the
measurement
of
the
time
specification
system (Figure2.1)and
process.Statesthat are not accessible are said to have zero probability.
Of course,it is possible to specify the configuration of a closedsystem
to a
If we specify that ihe
are of no interest.
point that its statistical properties as such
Fof example,the
states
of
the crystalline
in any observation
silica will not convert
2; Enxropy
Chapter
and Temperature
I imtt
of
of ihe
spcMftcation
sjstcn
2, t
A iwdy symbolic Ji:iKr;ihi:
L-:idi solid s|x'
slate
of a closed sysn
represents an accessible quantum
fundymema!
of statistical pliysics is tliat a
assumption
is equally likely
to be in any
of tlic quantum
si;
system
accessible to it. \"Die empty circles represent some of thi
that
are not accessible because their
do nc
properties
the specification of the system.
vjfju -1 ,-/<_
IlovG
V\\uil-
system
is exactly
in a
is left
aspect
in
the problem.
PROBABILITY
to be tn any
likely
Suppose we have a closed sysiem that we know is equally
of they accessiblequantumstates.Let s be a genera] state label (a\302\273dnot one-half
ihe
in this slate is
ihe spin excess). The probabtHty P(s) of finding
sysiem
P(s) =
if
the
fundamental
dosed,
systems
state
5 is
assumption.
shall
on [/and on
A'.
panicle
A),
consistent
otherwise,
be concerned
(t)
\\fg
but
taier
systems
that
ihe
fun-
are not
number
wilt
with
with
N may
Probubitiiy
sum
The
the
of
\302\243P(s)
the total
because
over alt
probability
probability
that
the
sysiem
_,
states is
is in
equal
always
to
unity,
is unity:
some state
B)
of
tead to ihe definition of the averagevalue
any
physical
properly.
Suppose iliat the physical property X has the value
when
the
is
system in the state s. Here X might denote magnetic moment,
X{s)
of the energy, charge density near a point r, or any
that
square
energy,
property
can be observed wlien the system is in a quaniumstate.Then
of
the
the
average
observations of the quantity X taken over a system
described
by the probaThe
defined
probabilities
probabilities
by (I)
is
I'{s)
This
that
equation
average value.
the
average
of A' is
value
!'
'
>':
/\"i>-'-f
denote
D]
alt g
because
now
average
in D)
likely,
equally
elementary exampleof
we imagineg simitarsyslems, in
is an
what
average;
Such a group of systems
averageof
any
_1_
property.
one
constructed
over
properly
the
alike
ts
may
each
be
P(s) =
an
called
accessible
\\jg.
The
ensemble
stale.
quantum
is catted
group
with
'
\342\226\240'
'\342\200\242\342\226\240>\342\226\240',
.\342\226\240>.
alike.
all consfrueled
is composed of many
systems,
of the
in one
is a replica of the actual system
Each system in the ensemble
If there
are g accessible stales, then
quanium states accessible to the system.
Each system
for
each
stale
there wilt be g systems in the ensemble, one system
to the actual sysiem.
in the ensemble is equivalentfor all practical
purposes
ensemble
An
Each
and
in
sysiem
this
of systems
satisfies
sense
all
external
is \"jus! as
requirements
good\"as
the
actual
placed on the
system.
Every
original system
quantum
stale
Tit
'[!\".;\"*'\342\226\240\342\231\246
'';\"(:!'
-rrrt
\302\273'.\"*
t
:\302\273\":;'\302\273''\342\226\240:
t';t
t: r;jt
:y
'[in
sT'\"\302\273
rn;
/.:Y:t
fit
rft
:t:;Y
i'YY
2.2
l;ij;ure
cuscmbJc
Tliis
of lOspiiw wiih
\302\253
iJirotijiJij
of an
Construction
represent a dosedsystem
each
frequent
in
a magnetic
use
of s
of
field is
as a
Mi
;m
I
;l
2.v
tlie
cusciubl
as
in
is
ensemblefive spins,
implied
or
in
We conslruci
each system with
-mB. |Do
stale index
2.2.
Figure
in the
is represented
Example;
\\
sighificance.
stale,
quantum
Y.
[\\
ilic
|0, so tliut
Hi syML-ins,
spin excess
sy>(cnis
icpresciiis
\\
Tlic
order in which
listed has no
-t
-Sui/Jimd
etwujy
yi
-\342\200\242Tit
;i
'nrt
/[r;i
: t
\342\200\242
\342\200\242
\"U.:'j\\
not
label.)
confuse
!he
Each system
in
spin
2.3
Figure
2s =
excess
use of
in
spin
an
ensctnMe
to
{.The energy of
excess
with our
muliiptes
of
t tl'OutibiC
represents a system
enscmbie
The
2.3
Figure
at tin's
states
Tile 10 systems
If the
have
2s
2s
have
and
2s
= 3;
t
|Q sysiems
has
system
have
2j =
7s
- 5.
- i.
- 5,a singie
ti1Ca\302\273embio.ThiS is
by tlic
I: 10
systems have 2s =
into
contact
-1;
.o!
function
multiplicity
in llie
- -3;
enetcy.Tlic
shown
energy
5 systems
\342\226\240\342\200\242!
t
A' = 5 and
! t
.! I
5 spins
With
R\302\253ute2.4
\342\200\236
| f
with
t'T
f\\
jTIT:
tj
i\\
K.O[ij\\j}U\\iilI0
tomjiriscs
systems
Most ProbableConfiguration
Let
two
systems
transferred
freely
2.5).The
with
net
two
constant
flow
from
systems
ofenergy
of
and
one
in
be
\302\243t
to
tttc
contact
U =. Ut
brought
This
other.
form a
is called
so that energy
(hermnl contact
larger closed
system
& ~
can be
(Figure
Sx +
\302\243z
a
+ U2.
from
one system to another? The answerleadsto the concept
The direction of energy flow js not simply a matter ofwhethef
of the other,
because the
one system
is greater than the energy
energy
of temperature.
the energy
5,
Whai
determines
whether
there
will be
r 2: Entropy
anil
Temperature
closed
Two
eomacl
in
The
ure
systems
u\\
in
of
Establishment
2.5
Figure
in
maximum
the
has
slates of two
systems when
in
contact
order
thermal
two
between
to define
spin
exchange of
and constitution.
two systems.
of
systems,
the energy.
&, and
lotal
energy
constant
of accessible states.
number
model systems
contact.
[wo systems
t6tal
the
energy
between
contact
Micrmal
size
in
+ ut
sulaliiin
accessible
ul
contact
thermal
system
s=
+\342\226\240
f/;
We
1
then
and
solve
first
and
2,
study
in detail
in a niagoetic
We
can be
enumerate
what characterizes
the
the
u N2
different,
and
the values of the spin excess2s,, 2sz may be different rOr the two systems. All
take
have
moment m, Tlie actual exchangeof energy
spins
magnetic
might
place
the
interface
between
via some weak (residual) couplingbetween
near
the
spins
the two systems. We assume
states of the total system & can
that
the quantum
be represented
a
state
of
accurately
any
by combination of any state of 3, with
We
but
the
of
the
excess
are
allowedto
values
constant,
S2.
keep N,, N2
spin
change.Thespin excess of a state of ilie combinedsystem will be denoted by 2s,
is dirccily
where s = sx + sz. The energy of ihe combinedsystem
proportional
to the total spin excess:
s2)
U{s)
The tola]
number of particlesisN
A'(
+ .Vj.
~2inBs.
E)
Most ProbableConfiguration
the energy splittings betweenadjacentenergy
leveh
are equal
so that the magneticenergy
systems,
given
up by system I when
one spin is reversedcan bo taken itp by the reversal of one spin of systctn 2 in
the opposite sense.Any large physical
system will have enough diverse modes of
that
assume
We
to
both
in
7n\\B
The
is always possible.
another
energy exchange with
system
+
is
because
is constant,
but
constant
t
he
total
st
s2
energy
systems are brought into thermal contact a redistributionis
two
the
when
s =
of
value
that
so
storage
energy
permitted
ihe
in
s3 and
of s,,
values
separate
the
in
thus
system
H2(Nj,s where
the
A.15).
The
To see
of s,
range
the
in
5Z by
F)
s,) ,
gx, g2 are
functions
multiplicity
and
5[
systems
to the
related
is
&
Uz.
I/,,
energies
is from
summation
how F) comesabout,considerfirst
that
of the
configuration
combined
systetn has
This
Different
values
one
forms
product
term of
of Uie
configurations
of j{.
suitesof
all
We sum
ihe
sum we
hold
with
s, N,,
to obtain
ofs(
fixed s
states
N2 constant, as
the total
or fixed energy. We
numberof accessible
and
characterized by
system are
combined
over a!!possiblevalues
configurations
part
of
the
combined
of
the
specification
thus
different
number of
obi a in
F),
system. In the
of therma!
contact.
of
ilie
number
of the
products
of s,,
glg1
of states
to
sL,
say
is a
in
it
gxiN1.Sl)g2[Nl.s
form G).
be read
maximum
Such a product\\sill
us
\"st
hat\"
is called the
or
be
\"si caret\".
most probab!e
is
- 5,).
(8)
am! Temper
2: Entropy
Chapter
A*.
Thermal
Sclicmalic
2.6
Figure
coiifiguralioji
!f ihe
are
systems
and Sj.
two syslems.-S,
belwcen
equilibrium
large,
extremely sharp, as in
the maximum
with
to
respect
in Sj will
changes
be
of configurations
will
dominate
the
statistical
of the combined system. The most
properties
alone
will
describe
probable
configuration
many of these properties.
Such
a sharp
of large
maximum
is a property of every realistic type
system
for which exact solutions are available;
that it is a genera! property
we postulate
that'fluctuations
of all largesystemsthe sharpness
From
properly it follows
about the most probable configuration
a
sense
ihat
we will define
in
are small,
The imporlani
result follows l hat the values of the average physicalproperties
of
contact
in thermal
system
large
configuration
for
values
(used
Because
number
the
in either
of the
A relatively
2.6.
Figure
the
in
such
a replacement
(8).
and
the configura-
by an
the
equilibrium
average
average over
of a
average
values.
physical
In the
find
replace
F)
are accurately
is a maximum.Such
thermal
may
system
configuration,
sharp maximum, we
configuration
large
probable
of accessible st3tes
another
with
most
small number
Most Prabahte
Example:
tfiL-
sharpness
functions for(j,(W,.s,)
Ilie muliiplicity
white ?i(Q)denotesjj,(:V,.G)
and
and
ffsf.Vj.Q). We
denotes
^@}
--^This
gives
product*
We
find
the
is,
properly
of
maximum
of statesaccessibleto
is 2s,
and the
spin
excess
replace s,
of ihc first
- *,:
(jo)
-l^iiLj.
system when
combined
the
by
spin syslem
of
product
the
spin
system is 2s,.
the maximum
constant; that
to use
the number
combined system
of the
excess
modd
lUc
We form the
ofiho form of|U5):
^olh
g^i-^J-
ConfiSui
>'{.y).
when
uy
be
if the
a minimuni,
second derivative of
a maximum!
or
the
z point of inflection.
is negative,
function
^~-.
~^T-~
The
so
that
(II)
e\\tr\302\243nuim
is
curve
bends
the
downward.
Ai
the
cxt
where
Equation
* The
product
s are
held
as s, is
constant
A1) U
fund
ion of two
Gaussian
fund
ions
is always a
Gaussian.
c1/csi1o(
the
Tims the
is a maximum.
extremum
is thai for
which
most
configuration
probable
is satisfied:
A2)
t
to interchange ofenergy
when
the fractional
to the fractional spin excess of system
2.
spin excess of system
alt the accessible stales of ttic combined
We prove itiat
nearly
satisfy or very
systems
then A3}
of s, and sj at the maximum,
nearly
satisfy
(U). if s, and 52 denote the values
two
The
arc
systems
in
with
equilibrium
respect
1 is equal
of slates
number
iiic
find
most
the
in
we
configuration,
probjble
insert
A4}
in {9}
A5)
(-25I/N).
To
the
investigate
of
sharpness
of gigl
s, introduce &
that
such
the deviarion
measures
Hcre^
Square
to
j,,ij
s,
of su
<5;
sj
st from
their
in {9} and
A5) to obtain
deviation
from (H)
ii
from
thai
\302\253
V.vi.so
.'.\\'u
s,/jVj
As a numerical
let Ni
values
- 5.
A6)
Su Sx at
the
maximum
o(g,gi.
equilibrium
so
of sialcs
45,^
2Sl
4s2S
slatesin
!ii;it the
the number
number of
of slates
that
2d2
a configuration
is
l(N2J2
\302\253
,V.
s2
number
the
know
fonn
we substitute
which
We
value of
a given
at
to
of
ot
\\
- 3) =
te.ffiU.e
;v~
the fraciionat
devbiion from equilibrium is very smalt,
example in wliidi
= ^00, and the
=
!0:i and 5
10'2; ilia! is, <5/A'i = !O\0210. Tlien,2ii!,'iVi
Thermal
Equilibrium
out lo a value
I0u
of the
probability
of (he order of
Tiits
distribution.
of N, thereby
is the subject of
s or
by N x
including
ihc area
Problem 6. An
tO\"t14 =
extremely
probability
{17} from
under
the
limit
upper
wings
to the
systems
over
sysicm
result
period of lime.
a long
THERMAL
The
is given
probability
integrated
EQUILIBRIUM
for
of accessible
number
ihe
systems
in
in thermal
contact, with
generalized to any two systems
constant toial energy U
extension
of the earlier arguBy direct
U2.
Ul +\342\226\240
is:
the
argument,
g(S, V) of the combiited system
multiplicity
may be
contact
thermal
summed
over all
values of
states of system 1
specified
by ihe
at
in
The
sum
o\\er
Jiicrgy
value of
ofaccesstblcstates
Us < V. Wzxz
Ux. A
:nl configuraiioits
the
is lite
a configuration
gi
itU
%)
is the
number
of accessible
is
of the combined system
The
number
constants
U,Nt, -V2.
coniigiiratioit
with
(.\342\226\240',.
together
g X{N
product gt{N],Ui)()i(Nz,U
~ Ut).
The largest term in the sum in (!S) governs the propertiesof the total system
ill thermal equilibrium. For an extremuni tt is necessary
that ihe differential* of
be
zero
for
an
infinitesimal
of
g{N,U)
energy:
exchange
dg =
(-\342\200\224]
divide
We
g2t!Ul
by glgl
lV, +
9i(^~\\d
result dV2
~tiUx
dU2 -
to obtain the
0.
A9}
thermal
equilibrium conciiiion:
Lflfs
we
which
may
write
as
B0b)
We defitie the quanttiy
a, calledIhe entropy,
a{N,U)
where
a is
the Greek
letter sigm:i.We
by
\\
now
write
B0)
B1)
Ns is held
means
lhai
panial
dcrivalivc
wiih
consiam
respect
in
ihe
to 0,
differttiljalion
is defined
as
o(g,{Nt,U,)
with
tespeel
lo U,.
Thai
is,
ili=
Teutperutute
is the
This
condition
Here
contact.
ant!
Afi
two
for
equilibrium
symbolize
us immediately
to the
/V2 may
on the
constraints
ail
thermal
for
systems
in
thermal
numbers of particles,
but
systems.
TEMPERATURE
know
systems
rule:
everyday
are
leads
B2)
thermal
in
If T
of the
temperatures
two
equal:
be
must
denotes
inverse
the
equilibrium
= t2.
r,
This rule
concept of temperature.We
ttie
so that T
to B2),
equivalent
ahsohite
B3)
must be a function
in ketvin,
temperature
this function
of
V)s.
(ro/f
is simply
iSie
relationship
B4)
The proportionality
L-on^mnt.
As
constant
determined
\302\273
U81
10~\"joulcs/ke1vin
\302\253
1.3X1
10\"Ulcrgs/kelvin.
temperature scale:we
called the
ilott/iiumu
experimentally,
kn
We defer the
constant
;i universal
is
ku
define
the
fundamental
B5)
prefer
temperature
10 use
a more
natural
r by
B6)
This temperaturediffers
from
ihc
Kelvin
temperature
kBT.
by the
2;
C/iapier
and
Entropy
Temperature
be employed
coexist.
Historically,
the
to build
accurate thermometerseven
though
understood.
not
yet
temperatures
thermometers
with
age in
it was
possible
of temperature
to
Even at present, it is still possible to
in kelvin
to a higher
calibrated
which
relation
the
precision
the
than
32 parts
about
as
from an
dates
scale
conventional
accuracy
B.
Appendix
permissible to take
the
of both
reciprocal
sides to
B8)
The iwo
was
B6)
expressions
given as a
determined
U with
of
differentiation
V). The
function of
of
definition
different
respect lo a
with
Eemr^caiufe
is die
oilier
in lhermal
ej.pcrinicnts
same
in
The
other
itrot
\"What
some
in
B6).
the entropy
<r
= a{U,X).Hencei
In B8).
V(a,N),
but
cases,
in
in
as a
\342\204\242
t(U,N).
mpties
both
because
phy.
we
id M
variab]
N consiant
variables.
independent
in
leaning,
diOcrcu
variables U
independent
the same indcpendeiu
have a slightly
the
has
B6)
from
and B8}
of
function
it
is
however,
so that t
expressed
ihc independent
we coniroi
experiments
are
variables.
ENTROPY
Tile quantity
entropy
ts
as
defined
logg
introduced
was
as the
in B1)
logarithm of
is a pure
the
as ihe
number
number.
slates
In classical
accessible
to the
thermodynamics
129)
Entropy
Figure 2.7
than
&
energy
if the
increase
U from
of a positive
system
total
the
condition if
the
cooler
energy
body
established.This
U2+8U
of ihe
value
words,
is
cm ropy.
increasing
Energy transfer
o,(final) +
As a
>
cMXinai)
+ oa(iniiiai)
o^iniiia!)
consequence of B4), we
see
o are
5 and
that
connected by
scale
factor:
130)
We
of
wilt
call
S the
conventional
number of particlesin
may
3)
the
on
depends
the
definition
on the
of the entropy
The
of
the
system.
entropy
energy
variables: the entropy of a gas(Chapter
dependence
independent
of
thermal
... is
limited
by
the physical
physics
author
the
Thus
Britaiiuka,
Encyclopaedia
of entropy
fn
(he volume.
known.
not
the entropy,
the greater
on the
and
system
on additional
depend
entropy.
lih
the
ed.
fact
of the article on
wrote:
A905),
that
\"The
it
does
not
in
thermodynamics
of
utility
correspond
ihe
the
conception
directly
to any
We
An
experimental
Chapter
and
determination
theorctic.il
of the
calcutiition
entropy
is
discussed
in
6.
Consider the
energy All
from
add
the same
when
we
remove
the
more probable
flows from the wanner b
when lhermat contact is
an otamptc
of the Saw of
wiii bt: in a
system
to
2 v.itt
-f a2
a,
entropy
of
amount
to system
is higher
r,
temperature
the transfer
t2,
a positive
amount of
Figure
2.7.
2:
Clmptcr
The
ihe quantiiy in
> r2
t,
so that the
the
from
Tehtjter
change is
tolnl entropy
When
is
urn!
Entropy
system
the
with
is
higher
when
positive
to the
temperature
is positive,
side
the direction
system
of energy flow
lower
the
with
temperature.
Example:
heal
with
fansitiariiy
on heiitjlow.
and specific heat.
increase
Entropy
of
ihc rentier's
previous
a 10-g specimen
of copper at a temperatureof 350 K be placed in thermal
contact
identical specimenat a temporal tire of 290 K. Lei us find the quantiiy of energy
ihe iwo specimens
arc ptaced m contact
and come Lo equilibrium at ihe
transferred when
final temperature
Ttie
of
over
hc;ii
meiaitic
ihe LempcraLure range 15:C
specific
copper
Tf,
to t007C is approxiinaieiy
Lo
a
standard
handbook.
K~l,
O.3S9Jg~!
according
The energy
increase
of the second specimen i> cmiai
Lo the energy loss of ihc first) ihus
the energy increase of ihz second
is, in joules,
specimen
(aj
Let
with an
AV
where
C.89J
ihe tempcraiures
- 290K)
K-'HTV
are
in
Tj
\302\253
|C5O
linat temperature
Ttie
kcMn.
- C.89JK-')C5OK
290JK
after
contact
Tf)
is
= 32OK.
Thus
At/,
\302\253
C.89JK~!)(~3OK)
-11.7 J ,
and
At/3 = -At/,
(b)
What
is the
change of entropy
immediately
after
of
the
initial
two
= U.7J.
specimens
con'act?
when a transfer pf
Notice
that
this
transfer
0.1J has
small
is a
contransfer
transfer as calculated above.Becausethe energy
at their
initial temperawe may suppose the specimens are approximately
of the firsi body is decreased by
350 and 290 K. The entropy
is small,
energy
Lan
second
S2
iotal
Tile
increases
enlropy
AS, +
of the
= 3.45
,7~
of Enlnpy
by
by
10-4JK-' = 0.59
In fundamental,
where
is increased
hody
of Imrrrmc
of entropy
1CTJJK~
*s
Botl/.ma\302\253n
constant.
This resuil mcaaS thai
(lie number
of accessible
tjisihe
- enp@.43x 10l9>.
two systems increases by (he factor exp{M
st;it
can
ihc loial
thai
show
broughi
If (he total energy V
into
systems
arc
thermal
in
contact.
~
ctttrapy
two
V% +
systems
a special
after
;trc
case.
the
is
contact
thermal
when
increases
always
We have
ff(t/)\302\273=
^0,A/^A/
term
t/,)
gi(EAo)i/i(^
C3)
~~
^to^
^or l^e
i-XiiiVd^
niuitiplicuy
before
contact
and
many osher
~~
the
initial
muilipiicity.
(Mi).,,
That
is,
= 9i(O,)gJiU
- 0.)
C4)
2:
Chapter
and Teniperatur
Entropy
with
Ut
= 0
parts and
probable
conftgL
the
presently
con figuration.
rat ions
be very, very
Hie cm ropy
in or
found
increases
or
muhiplicily
ihe
moit
initial
essential
The
value
is lhat
effect
of
for which
Vl
the syslems
states
term
C5)
contacl
after
configuratic
probable
Vl0).
9iiVtMU'~
Here 0s denotesthe
The entropy
probabilhy.
a{U) oflhe
ihe entropy
of energy
will be
syucm
ofincreasirtg
reaches
eventually
may
* U. Exchange
anJ U,
maximum.
iheir
initial
fundamental
The
lake
always
from
place,
assumption
with ali accessible
probable.
eqtutlly
The statement
C6)
fffjnil
of
is a
is removed.The operationofebtabitsliiiig
removal of the constraint that
Vu
Ux
U,
need be
configuration
V2
each
contact
be constant;
u closed
to she
is equivalent
system
sjstem
to ihe
after contact
only
constant.
thermal
iniernul
combined
a certain
system
time. If
we
lowards
separate
ihe
final
ihe two
thermal
equilibrium
Add
energy
molecules
Decompose
Let a
2.9
Figure
(his cotifiguraiion,
reach
intermediate
view
and
energies
the entropy
constraint,
called
Processes
2.9;
Operations
function
(he lime
that lend
the arguments
that follow.
as a
in
we
io increase
lend
thai
will
an
obtain
an intermediate
of
the
lime
of evolution
in
of each
ofa
entropy
intermediate
up
syslcm.
configuration
with
io
entropy. Ii is ihesefore meaningful
tli.i' lias elapsed since removal of the
2.8.
Figure
the
process
ofa
will
system
be
are
developed
shown
in the
in
Figure
chapters
2:
Chapter
For a largesysiem*
occur
never
and Temperature
Entropy
thermal
(in
spontaneously
coniaci
entropy
and ihc
entropy
of ihe
shortly
which
most probable
have
we
afier
implies
that
the nature
changed
we
had
the
of
configuration
the system
prepared
system
macroscopic
of ihe contactbetween
initially
in
two
some
very
systems,
special
way.
never arise
operations
naturally
on the
informed
left
systems
but
undisturbed,
arise from
system.
Consider ihc gas in a room: the gas in one half of the room might
be prepared
wjiti a low value of the average
initially
energy
per molecule, while the gas in ihc
other
half of the room might
be prepared
with a higher value
of
the
initially
average
energy per molecule. If the gas in the two halves is now allowed to
interact
of a partition, the gas molecules will come
by removal
very
quickly'
to a most probable configuration
m which
ihe molecules m both halves of the
to
room have the same average energy. Nothing else will ever be observed
the
We
will
observe
to
leave
most
never
ihe
sysiem
configurahappen.
probable
configuration
and
reappear
later
in the
LAWS
OF
initial
specially
of motion
prepared
of physics
is true
configuration.This
are reversiblein
time
and
do not
THERMODYNAMICS
The
thermodynamics
calculation
of Ihe lime
required
for
Ihe
process
is largely a
problem
in
hydrodyna
Laws
condition B0b)for
of the
(e\\oSgt\\
{~\342\204\242rk
in oilier
words,
r,
comact:
in thermal
equilibrium
of Thtentotiynamks
feioSg3\\
/cloggA
/cloggA
{-furl:
{imX=
{~7urk
= t3
t3 and r3
rj
imply
r2.
heat is.
Second
entropy, applicablewhen
is ill :l
of the
tluit is not
configuration
of
law
(he equilibrium
consequence
will
in successive
instants of time.\"Tins is
wilh Eq.
called
be lhat
have
iniernal
a constraim
used statement
commonly
statements
equivalent
many
statement, which we
the statisiicai
use
shali
are
There
law.
cotiliyitnilton.ilicmosi |>rubnble
system will increase
monoiotiic;ilty
siaicineiil
a looser
ilian
he
one
we gave
C6} above.
The traditional
of
is the Kelvin-Pianck
formulation
is
for
\"it
to
any
cyclic
process
impossible
of heal from a reservoir and the perextraction
statement
thermodynamic
of second iaw
thermodynamics;
occur
statement.
Pianck formulationis a consequence
oflhe statistical
as the
Third
iaw.
The entropy of a system approachesa constant
value
due
zero.
The
ear!
test
of
this
statement
temperature
law,
loNemst, is
approaches
at
that
ihe absolute
zero the entropy difference disappears between all those
iaw follows
is
multiplicity
the
system
g@),
the
in
has
thermal
internal
definition
statistical
the
from
ground stateof
which are
a system
of
configurations
corresponding
zero. Glasses
is essentially
substantial,of
in
real
life is
to
objection
the
order
that curves
must come in
flat
as
affirming
have a
of [he
The third
a weii-defined
equilibrium.
frozen-in
number
of many
r approaches
reasonable
0.
the system is
for
zero. Except
glasses, there
that (j{0) is a small numberand
c{0)
for them o{0) can be
and
disorder,
the
third
law tells us
of atoms N. What
plotted against x
quantities
physical
however,
that
Chapter 2: Entropy
as a
Entropy
and
Logarithm
Several
useful
stales itself.First,
the
ihe definition
from
follow
properties
number of
of the
rithm
Temperature
of
entropy
of as
cad
independent
separateentropies.
Second,
the
the
never meant to
for
that
entirely
imply that
a discrete
tite
practical
purposes\342\200\224-to
We have
defined.
is
exactly, a circumstance
is known
energy
system
of energy
spectrum
ali
insensitive\342\200\224for
with wiiich
6U
precision
is
entropy
eigenvalues would
of
number
the
make
We have
depend erraticallyon ttie energy.
simply not paid
much attention io lhe precision,wlicthcr
ii be determined
by the uncertainly
h, or determined otherwise. Define <0{U)as the number
principle <5U 5{time)
of accessible
srates
unit
per
energy
range; O{U) can be a suilablesmoothed
of
V. Then y{U) ~ i>{UNU is lhe number
accessible
centered
at
average
stales in the range SU al V. The cmropy is
accessible stales
a{U)
of
order
the system
as for
Typieally,
2V.
tola!
lhe
If
particle energy
then
A,
.
Let N
logO(t/)
of N
energy
C(l')
. a{V) =*
~ IO20;A
*\302\273
0.69
\\
C7)
of states
number
total
the
order of N
is of the
times
same
be
of ihc
average
one-
will
2;7jVA. Thus
and 5U
x
\302\273
10^'
10:o
C8)
+ log^C.
--'logNA
Nlog2
IO\021* erg;
a(U)
spins,
-t-
erg.
- 13-82-
2.3.
C9)
We
see
Example:
from
exam pie
of N;
value
this
iiuxion
Perpetual
Early
lion
more energy
in.in
ii
absorbs.
in our
machine,
study
of
a machine
we came
physics
ilui
wjli
gi\\c
to
forth
motion
of the second kind, as it is called, in
Equally impossible is a perpetual
machine
which heat is exiracicd from part of the environment and deliveredto another
of ihc
part
a heat
in temperature
environment the difference
ihus established being usedto power
we
available
for any purpose at no cost to us.In brief,
engine that delivers mechanicalwork
cannot
tlic surrounding
to
ocean lo extract the cnefgy
propel a ship by cooling
necessary
ocean
10 a
transfer
of energy from ihe low temperature
propel ihe ship. The Spontaneous
higher temperature boiler on the ship would decrease ihe total entropy of the combined
and would thus
be in violation
of the law of increase of entropy.
systems
SUMMARY
1. The
fundamental
2,
ifPfi)
is the
a cioscd
that a
probability
system is in
system is equally
s, the
stale
the
to
be
average value
ofa
likely
is
quanliiy
is that
assumption
in any of
ensemble of
alike.
3. An
4. The numberofaccessible
states
the
of
combined
all constructed
systems,
many
1 and
systems
2 is
*
where
5. The
s,
entropy
conventional
= s.
s2
a(N,U)
entropy
6. The fundamental
with
the
conventional
7.
fundamental
entropy
kBa
connects
^'
the
o.
temperature r is defined by
1/t
The relation r
S =
relation
Tiie
to$g{N,U).
,^ ^
= kgT connectsthe
[ca;cV)sx.
fundamental
and
temperature
the con-
temperature.
The
system is removed.
the
when
entropy
a constraint
ofa
closed sysicni
intorn.il lo llic
2:
Chapter
and Temperature
Entropy
thermal equilibriumvalues
the physical
of a system are
properties
accessible when the system is in contact
with
a large system or reservoir.If the first system
also is large, the thermal
of the states in
equilibriumpropertiesare given accurately
by consideration
8. The
as
defined
of
all states
over
averages
alone.
PROBLEMS
1. Entropy
N is
and
is negative.Tliis
{c^a/rU2)*
2.
Find
Ptirtitttagiwtisni.
of
form
the
y( U)
wiiere
CUiNn,
U
thai
*=
{Nt.
C is
(b)
;t
constant
that
Show
equilibrium
ui
ictn|KT;tit:rc
i of
ilie (Vac*
lional mngntrlizalion
M \\'m
sysiem of
of the
spin
is 2s.
excess
as given in
2<s>/N
h' spinseachofmagnetic
momem
in in a magnelic field B. The
the
as
Take
lhe iogarlhilhmof lhc muliipliciiy
g(N,s)
eniropy
A.35):
\302\253
iV.
Him:
Show
that
in
g{U)
wtih
oQ
1og(/{N,0).
this
2s2/N
D0)
approximation
c0-
D1)
U2/2m2B2N,
\\jx
-U/)\302\2732B2N, where
U denotes
3.
Quantum
of frequency
funciion
Replace
Express
hartitonic
m as
exp{/itu/r)
This
!S the
that
does
PSanck result; it
us to
not require
is derived
find
again
ihemuilipiicity
,42)
\342\200\224
1
tn Chapter
function.
4 by a
powerful
method
where
of the
universe
thereforezero
in
approximately
any
operational
of an
sense
the age
of Hamlet is
be typed in
will
The
10\"'64316.
probability
event, so that
the
statement
original
one
mudi less a library,
book,
beginning of this problem is nonsense:
occur
in the total literary produclion of the monkeys.
at the
never
will
5.
is
of
Addith-ity
A', =
ss +
as a
gig2
product
the
I012,
far
entropy
1012spins with
two spin
multiplicity
product
#sj72 is
(a) Compute
(b)
s =
For
to
equal
1O10, by what
Yai9'it^i*5i)9i{^i's
two
jO\02174
s,
s, +
factor must
~
5i)\">
the
lOn and s =
you
\302\247've l^e
^ctor
form
to
value. Use
the
A7) may be
0.
(gijh),,,a!l
multiply
JV, =s
- ss), the
= s,.ForSj=
its peak
from
function:
multiplicity
of
systems
and g2{N2.s
g^x^i)
reduced by
the
for
gigz/{9-i9z)m3X
Given
functtonofsj
Gaussian approximationto
useful.
systems.
functions
fo make
it
nearest order of
the
magnitude.
' j.
Jeans,
htysteriota
utirerst,
Cambridge
Universily
Press,
1930, p. 4. The
slalenuill
is
attributed
to Huxley.
Clarke in
malhematfco-iherary
2001.
explanations
sec'The
of the
average trretrme
m an-seconds ii
study,
Libtary of Babel,\"
by ihe
fascinating Argentine
Revcttc
for
Bureau and to Dr. Rosier
Reference
number of man-secondsis 2 x iO10. if we take ihe
oi
numoc^
of lives as I ^ 10 , i he cumu*ai[\\c
iaken in the problem.
\342\200\242sccondi
(t0\">
monkey
Cliapter2; Entropy
(c)
How
and
Tcmperatur
error
in
the
entropy
when
you
ignore this
factor?
6, Integrated
approximately
the
is 10\"l0
\342\226\2405/JVj
use an
probability
or larger.
calculate
For
deviation.
Take
the
complementary
error
\302\273i,
xp(x2)
(\"\"e
1 +
small terms.
function.
When
Chapter
and
Distribution
Boltzmann
FACTOR
BOLTZMANN
58
61
Function
Partition
Two
State
System
64
PRESSURE
6-1
;>7
identity
Tlicrmodynaimc
Example: Minimum
ParamagneticSystem
6S
ENERGY
KttEE
HELMHOLTZ
of
Property
the Free
70
7!
Maxwell Relation
Calculationof f
IDEAL
GAS:
One Atom
Example;
71
from
72
LOOK
FIRST
72
a Box
in
Af
in a
Atoms
74
Box
76
Energy
Example:
of
Equipartition
Example:
Energy of ;i
69
Relations
Differential
62
77
Energy
7$
Entropy of Mixing
SUMMARY
SO
PROBLEMS
81
1. Free
2.
Magnetic
3. Free Energy
of a Harmonic
4. Energy Fluctuations
5.
Effect
Overhauser
6. Rotation
7.
Zipper
O.ollaior
of DiatomicMolecules
Problem
S. Quantum
Concentration
85
Si
S3
S3
S4
84
S5
S3
9.
auJ
Bol
ChapfcrS:
Partition
10. Elasticity
Function
of
for Two
Polymers
11. One-Dimensional
Gas
lleliiiiioiiz
Systems
Free
Energy
Chapter3; BolRinattn
The
laws
statistical
We
are
of thermodynamics
mechanics,
able
of
to distinguish
which
in
and
Distribution
lleimkoitz
mechanical
we call
mechanical
action and
the thermal
in
the
narrower
Energy
of
cases of mechanicalaction.
Glbbf
Free
this
In
of the
properties
physical
sysiem
called
system
as
particular,
in
of
reservoir.
The system
of
the values
calculate
Figure
3.1.
The
total
temperature.
wiih
equilibrium
a very
energy Uo
We
ihe
The iota!
if the
&
[he
temperature
influences,
us to
permit
a system as a ftinciion
interest
io us is in thermal
of
we develop
chafer
=*
Ea, tltcn
U^
Uo
u!!
external
constant.
is
\302\243/j
ihe
r,x is
have
energy
In
of
the reservoir.
Toial sysiem
Constant
J.I
energy
Vo
irOtiiUhcn
BOLTZMANN
A
central
problem
\302\253iilbe
proportional
to
in a
the
loiat
sjsieni
syst
S.
iisioa
n decomposed
FACTOR
of thermal
specific quantum
Boitzmann
factor.
10 find
siaiu s of energy
physics is
the
probability
t,.
This
ihe system
is propor-
iltai
probability
of
accessible
states
g\302\256t
j
of
of ihe
siaies
fractional effec!
of
laigc TCMivoii
accessibleto (ft
the reservoir
of
Energy
of cnlropy
t la
itie transfer
vil\\
luua
high
A)
for our
because
If the system
to
\302\243,
Ihe
ratio
of Ihe
the
the
system
dependence
Multiplicity
of
<R
at
Multiplicity
of
(ft
at
write
B)
on the
depend
is only
in terms
are
situations
two
ow
system
system is in
is^f/o
is
in
number
of
in Figure
3.2.
\342\200\224 The
\302\243,.
as
\302\243,},
I al
stale
quantum
2 at
state
quantum
energy
energy
assumption. The
about
that the
condition
the
is Uo
energy
.S ,
state of
the
specified
energy
energy
Ei
is
Ihe
two multiplicities:
ts a
result
this
that
probability
probability
have
the
reservoir
\302\243\342\200\236
to the reservoir in
of the
The ratio
is
energy
stales accessible
This
present purposes we
the
large,
of the
shown
constitution
temperature
the
Uo
r.t
\342\200\224
\302\2432
[/q
have
we
ei)
\302\243a(^o
\342\200\224
called
B)
e2)
91s(^'o
the fundamental
in Figure
reservoir.
of the
arc very,
multiplicities
very l.-irgcnumbers.
\302\273
E.)
ff\302\253(t/0
C)
when ihe
(he system.
The
on ihe reservoir
ci\302\253iop>.
Bohzmnnn
Chapters:
Oi
E
ergy
yo
01
-',
stale
En \302\253gy (/\342\200\236
-\302\253,
(/\342\200\236
',)
;\302\260
'='
slates
Ene
Fi\302\273urc3.3
has a,,(U0 id
The
State 2
tc I
Sta
Energy c.
gy\302\253>
system
in
t,},
(b) is in quantum
c,) acccisiblc quanluin
(a),
slate
t, 2. The
slates,
(,\302\273(()\342\200\236
reservoir
in (a) and
(b)
D)
the probability ratio for
two
the
1, 2
states
E)
Let
us
expand
in D)
the entropies
in
a Taylor
/(x0)
series
expansion
about
is
t)
0)
where
1/t
(S^/cCV^
gives the
is taken
al energy
an
infinitely
Therefore
defined
Acr^
-(\302\243,
ofvust
form exp(
the
of
term
It
utility.
ttie
to consider the
ealied the
exp(-e,/t)
in a
system
in
:i
single
for
a!!
We see that
result
(II)
is one
= 1:
ZjZ
\302\243?(\302\243,)
probability
is V
useful
= (e)
oft'j, ~
convergence
\342\202\254)andnolg({/B
difficulties.
partition
p[Et)
and
is
function
(he
results
= X^fo).
of
the
Boltzmann
statistical
pro-
factor
e) because
[he cupansion
physics.
The
or
= T^logZ/ct).
=,
Zh^Zh!A
We expand
is unity.
the sum of all probabilities
of the most
system
is over
system. The
the
5 of
states
A0}
5>p(~Ei/T)
summation
The
function.
partition
gives
system
function
Z(r)
\342\200\242
the
Function
is helpfui
The
This result is
Boltzmann factor.
ratio
to
'
,as 3
known
is
\342\200\224e/t)
the
gives
Partition
(8)
-\302\2432)/T.
expft/r)'
P{ez)
of
limit
E) and C) is
result of
final
in the
vanish
expansion
D) becomes
by
Affffl=
The
liie
of ihc
'
A2)
tatter quanliiyimmcdiatcty
Battvnanti
ChapterS:
Helmholtz
and
Distribution
Free Energy
0.5
0.4
J-\342\200\224\342\200\224
Energy
ystcm
rgy
and
heat
as functions
is plotteJ
capacity of a
ofthe temperature
in units
ol t.
0.1
\342\226\240
The
with
called
for
(e)
refers to
energy
average
reservoir.
The
thermal
the
notation
average
in conformity
those statesof a
with
can
that
system
\342\226\240
) denotes
<\342\226\240
exchange
an average
such
energy
value and is
or ensembie
common
system
-f reservoir.
Exwiiplc?
clc
Energy
uiid
wftli two
Z =
\"fhe average
exp(-G/t) +
exp(~\302\243/r)
-f
A3)
expf-s/t).
energy is
This function
is plotted
in Figure 3.4.
we
shift
iliczcro
If
of energy and lak^: W.c
instead ofas 0 and e, the results appear different
energies
of the
two
as
states
-\\e
and +\\e,
ty. We have
\302\253p(-\302\243/2r)
2cosh(fi/2t)
A5)
Partition
Function
and
A6)
-jctanh(c/2c).
of a
at conslant
syslem
by the
ihermodynamic
as
s x(iajdx)r ,
Cv
which
is defined
volume
below
derived
C4a)
identity
A7a)
is
lo
equivalent
allcmate
the
definition
s (SU/dt)y.
Cr
hold
We
V conslant
volume. From
and
A4)
In
of energy
dimensions
ri^i-immp
in ]Ilc
anomaly. For
for a syslem
at a
specified
-fEY
per kcivin.
A8a)
Tim
siicctfic
pio! of Iicii]cnpiiciiy
\302\273
i, the
eXp(E/t)
A6).
C, is defined
unils
conventional
'
The
arc calculaied
(!?b},
energy
A7b)
versus
heat
is drfmed
\\\\\\
icmpcjiiiurc
us
itio
t'iiHirc3
deal
capacity
\"\342\226\240
is Ciiiic^l
per
^ jLtiOiiKy
A8a) becomes
heat capacuy
Cr^(E/2iJ.
ihat
N'oiicc
lemperaiuie
Cy cc
r\"\":
is small
in
in
ihis
as a-
exponen'.ial
0.
factor
A9)
comparison
Cy ^
The
exp[
\342\200\224rcJuces
r,'t}
unil
limil
\302\253
e we
CO}
{c/lJ^Xpl-E/lX
Cv rapidly
as r
decreases,
ihc
have
because
exp[
~ 1/v) -> 0
Chapter}:
and Hdmhoki
Distribution
Boltzmann
Free
Energy
is reversible if carried
out in such a
to
the
close
equilibrium condition.
infmiiesimally
Forexample,
if the entropy
is a function of the volume, any change
of volume
must be carried out so slowly ihat the entropy at any volume
V is closely equal
lo the equilibrium entropy
is well defined at every
the entropy
Thus,
a{V),
of a reversible
the
of the change the
and
direction
stage
by
process,
reversing
Reversible
Definition:
is always
to its
returned
be
will
system
A process
process,
ihe system
way ihai
reversible
In
condition.
initial
the
processes,
defined
at ail times, in contrast
to irreversible
the
processes,where usually we wilt not know what is going on during
process.
We cannot
10 systems
apply the mathematical methods of thermal physics
is undefined.
condition
whose
volume
the system
leaves
that
change
reversible
exampleof an isentropic
same
state
process,
because
not
the entropy
change.
reversible
processes,
change
the
number
of states
Any
process
in which
process.
and
process.
in
a special
an
If the
state
quantum
is an
between
ensemble
the entropy
But reversible
we shaHhave
zero
be
will
same
the
in
change vanishes is
processes are
interest also in
to
limited
not
an
isentropic
reversible
isothermal
isentropic
pro-
processes.
PRESSURE
Consider a
system in
the
state
quantum
s of
energy e,. We
assume
e, to
be a
t\302\243V
eJ^V) -(dtJdV)bV
&V)~
Consider
work
cube
volume
Kto
from
U(V
\342\200\224
Af)
AKappears
- U(V) .=*
\342\226\240\342\226\240-.
The
B1)
mechanical
in a contraction
as the
At/
-(deJdVyLV.
B2)
\342\226\240\342\200\224-\342\200\224_
t.S
i.O
O.S
Volume,
relative scale
3.5
of energy on volume, for the energy levels of a free
Figure
Dependence
-%- n_\\
-j- . t
particle- connned 10a cube. Ttie curves arc labeled oy m ^\342\200\224
i^
as in Figure t.2. The niuhtpltctties
ch; nge here
g are also given. The volume
^s isolropier
a cub1\" remains
oc of ]tic stat1
& cube,
i he criercy ranfie
represented in
of ilie energy
llu: av cragc
an
ranee
energy
ensemble
of systems
will
increase
in a revcrsibk
ti
is )he
Tigure
cha
3.6
compression
Volume
of a
cliangc
cube.
- AI'
Chapter i;
Free
Ihtmhottz
the energy
V denotes
Here
and
Distribution
Batiziriann
Energy
be
face of ihe
of one
area
the
cube;then
+
A{Ax
if ail
increments
AV
Ay
Az are
psA(&x
so that, on comparisonwith
AV
B3)
taken as
positive in
the
compres-
Ay
Az)
PiAV
B4)
B2),
-thjdv
stale
s.
P,
the
ensemble
the
of
B5)
to obtain
as p:
written
<\302\243>,usually
+ Az)
compression is
in the
done
wotk
compression.
The
=s
Ax
V and
Ay
B6)
where U
The
<t>.
of states
number
we have
in
described.
each remains
in
fhis
a is
entropy
the
We
ensemble
hove
_st:ile
in ihe
in
reversible
the
of systems,
a collection
each
in
ihc
because
compression
some
stme,
and
compression.
mechanic!
of the
picture
pressure on a
only
the
two
variables
U and
the
describe
system.
of
The differential
the entropy is
da[U.V)
B7)
Uu
change of
dV.
th;it
the
Assume
the
two
entropy
Tor
arbitrary
independent
Identity
Thermodyaamie
overall
The
cancel.
of dll
values
interdependent
entropy change
da
be
will
and dV by {W)a
and
zero.
{&V}at
denote
If we
the
entropy
these interchange
will
be zero:
B8)
B9)
)
Bui
\302\273he
ratio
(*5[/)\342\200\236/(<)F),
is
the
wilh respect to
at
o:
constant
s ldU/dV),.
(iV)J(SV),
With
of U
Jerivative
partial
and
this
the dcfiniiion
l/i
C0)
s (So/5!/),.,Eq.B9)becomes
\302\273\342\226\240-<\302\243).-
By B6)
Therniodynaniic
pressure
and
to
equal
-ft
whence
Identity
side of C1) is
the kft-h;ll)d
differential
the
B7)
of the
definition of i to obtain
Ttla
dU
-f pdV.
result for
Chapter3: Bohynaaa
relation
useful
This
variable
will
appear
will be
in
Free
and Helmbohi
Distribution
called the
E.38).
Energy
thcrtnodjnsmk identity,
A simple
with
transposition gives
dU =
process of change of stateof the
If the actual
form
The
TVS
is
system
C4b)
pdV.
reversible,
we can
and
as the work done On
identify xda as the heal addedto the system
-pdV
the
The
of
increase
is
caused
in
mechanical
work and
part
system.
energy
by
in part
as the transfer
of energy be!ween
by (he transfer of heal. Heat is defined
two
brought
systems
into
thermal
HELMHOLTZ FREE
The
contact (Chapter
8).
ENERGY
function
C5)
is called
physics
at
constant
temperature
energy.
that
This
function
the energy
plays the
plays
part in thermal
in ordinary
mechanical
no
because
processes, which arc always understoodto be at constant entropy,
state
are
allowedThe
free
tells
us
how
to
bulance
internal
of
energy
changes
and maximum entiic conflicting demands of a system
for
minimum
energy
The
a
Helnihoitz
free
will
be
a
minimum
for
system S in thermal
entropy.
energy
contactwith a reservoir (R, if the volume of the systemis constant.
r and V.
We
that F is an cxtrcmum in equilibrium
;it constant
first
show
01
to &,
reversible transfer from
for infinitesimal
By definition,
C6)
at constaot
stant
volume.
so that
temperature. But 1/t h {das/cUi)yi
Therefore C6) becomes
dFt
*=
C7)
dUL
respect
we can
to
all variations
calculate
it
from
Free
tfehuitoh:
We can show
Comment.
i',R
\342\226\240
Then
Us
ihe tola!
is a minimum.
extiemum
the
that
- UtfffJtVrivji +
(\302\253*A'^),,v
L/j
Ft
be a
The
hxti'iiplc:
with
o,
mus)
configuraiion.
the
\302\273
Fj
thai
model
ffsiUj).
C3)
in
excess is 2s
respect
the
C9)
I.
A't
<rlk(Lr)
with
when the
constant r, V
respect
is in
system
will
and we
is consiant;
. It follows from
ihc mosi probable
for any deparluce
to Us
increase
Coilsklef tliC
iyswin,
parcmti^nctic
= A1? -+- N^',
Let
N
*uid
down.
Ni
spins
spins
up
is found
in
Tlie
the
SUHiiig
approximmion
W(.
entropy
\\viUi
approximate
D0)
system.-Now
lo Vs
at
system
vf the
property
of tliaptcr
tlicliclpofan
vviiii
of
the
is a maximum
equilibrium
minimum
free energy
Slltthnuiii
sy^tcfn
spin
i/t
- FJx ,
a^a^iV)
D0) lha)
==
becomes
C8)
rewll
is V
energy
that
We know
where
total
eniropy is
* e^U)
so thai
The
Energy
free
energy
tifa
N't
form of A.31}:
,4,,
The
in a magnetic field
Tile fice cncigy
energy
elementary
magnet.
FJjaB)
&
V{s,m
Bis.- 2\\tttfl,
funaion (to
w licrc
be called
m is ilic
ldc
magnetic woniciilofan
lapdau
function
in
elemen-
Chapter
tO) is
io(s),or
D2)
becomes
of Ft{r,*.B) with respeel
io s, this function
cquat
f
because
Thai
free energy
<s> is a function
F[i.B).
is, Jt.<5>,BJ F(r,B),
excess occurs when
of FL with respect io the spin
minimum
Al
ihc
minimum
= 0
= -JmB +
tlog^4-|-
lo the
of z
equilibrium
and B. The
D3)
Thus
in the
or,
on dividing
magnetic
and denominator
numerator
the
volume,
free energy of
however,
The
is
easier,
for
the
D5)
<2s>m/K =
exp(\302\273iB/r)
D6)
Hi\302\273wnh{mB/r).
can
be obtained
the
from
by
D5) in
substituting
function
partition
for
one
\302\253
D7)
2cosh(mB/t).
expt-niB/r)
D2).
magnet:
F =
relation
N magneis.
exp(/\302\273B/r),
Ntanh(mi?/r).
Z
Now use
momeni
If n is the number ofspins
per unit volume.
in thermal equilibrium in the magnetic
field is
magnetizalion
M =
It
Is
excess
,U is the magnetic
The magnetization
unii
by
ofihe spin
\302\273
<2s>
per
equilibrium value
thermal
B lhe
field
Differential Relations
The
is
off
differential
dF =
or,
use
with
of the
dU - xda -
thermodynamic
identity C4a),
dF = -adt
for
oiit,
\342\200\224fdV
\342\226\240
which
D9)
These
relations are
The free
for
an
energy
isvihcnwil
widely used.
F
in
change
the
result
of volume;
=\302\273
-(rf/^K),
acts
as the eilecttvc
B6).
The
energy
result
Calculation of Ffrom Z
may be written
as
' -
what
= U
of F
use
by
we
pressure
~-(cU/dV)f
x(?a/3V)t
is dominant
in gases
\342\226\240
<D,
the
on
terms
call
may
\342\231\246
-($.
right-hand
side of E0)
represent
{Problem
contribution
entropy:
Ihe natve
from
mechanics
must
tell
that
simple
feeling
everything
-JUjdV
about the pressure is seriously incompletefor a process
at constant
temperature,
because the entropy can changein response
to she volume
change even if the
of volume, as for an ideal gas at constant temperature.
is independent
energy
10). The
enlropy
Maxwell
relation*
We can now derive one of a group of
called Maxwell relations.Form
the cross-derivauvirscV/^l\"
be equat
10 each other. It follows from
that
D9)
E!)
*{ep;eT)y
(ca/dV)t
relations
tliermodynamic
must
Hx and ^FfcxcV,which
useful
a relation
is not at all obvious. Other Maxwell
will be derived later at
that
relations
similar
The
of
obtaining thermodyappropriate points, by
arguments.
methodology
L
Chem.
5964
namic relations is discussed
A981).
Phys. 75,
by R. Gtlmore,
from Z
of F
Calculation
Because F =
F
Wo show
thul
this
%a and
U +
equation
a =
i{SF/dt)Vt
is satisfied,
F/x
where
is the
partition
fund ton.
differential
~x2c(F/z)Jcx
\302\253
U.
equation
E2S
by
- -log^ .
On substitution.
E.1)
Chapter3:
This
A2).
by
and Hchniipliz
Distribution
Bollzittnnn
the
F =
+ ar.
is so
temperature
are
log
g{t
Z)fct
We may
the
However,
low
that
the
only
limit logZ
that
In
occupied.
equafion E2).
for Fjx to contain an
possible
appear
-riogZ
logg0 only
if
a ~
state
must
cj0 coincident
that
reduce to \\oggQ
when
the
states at the lowest energy \302\2430
-* logg0~ W*.
s0
thai
a =
-cFjcr
\342\200\224
factor
Boftzmann
the
entropy
a such
constant
additive
0.
Zand
E5)
-riogZ
differential
required
would
It
Energy
that
proves
F=
satisfies
Free
(II)
E6)
cxp{-f/t);
probability of a
quantum
s becomes
E7)
GAS:
IDEAL
One atom
mass
free
free
in
FIRST
a box.
We
move
to
wave
particle
LOOK
calculate
in a
equation
\\p{x,y,z)
cubical box
-{/iJ/2.U)V:^
= Asia(nxitx
of
volume
== ei/i
We
system
are
L)sm{iiyity}L)sin{n.iiz}L)
the partition
1. Negative
Chapter
not give
E8)
,
integers
do
are
neglect
is
the spin
entirely
specified
by the
of
values of nlt
the
nft
atom,
n:.
so that
a state of
the
Ideal Cm:
The
the
Provided
we
partiiion
may
replace
the summations
2] =
The notation a\"
may
be
of adjacent
spacing
&
t!nx
First
Look
energy values
is small in comparisonwiih
t,
by integrations:
\342\200\224
*2{nx2
(/ji,cxp[
dnf
ny2 +
for convenience.
is introduced
Azji2/2A/12t
as ihe
written
'u2)].
F1)
The exponential
F2)
in
of ihe
ierms
concentration
ji
XjV.
Here
F3!
is catted the
atom
in
quantum
cube
concentration.
of side
equal to
It is
the conccnlration
lie
wavelength,
small
F4)
becauseZj\"' exp{-
is (he
eJx)
log^i =
so that for an
the system
probability
\342\200\224
terms
-f-
jlog(I/i)
is in
it. From
state
the
F2),
of t ,
independent
F5)
If t
=*
The
thermal
kB is
where
kaT,
the
of'a
occupancy
average
free particle
lkHT,
the well-
in-
equiility
an upper limit
sets
which
standard
at
atom
helium
regimeto
apply,
is always
positive
temporarily
many
tiiitil
noniulcmaing
utoni
result.
identic!!, of ik
this
of 4 x
a free
must
the
of an
occupancy
and temperature.
concentration
occupancy
for
for
!0\026
be
\302\253
1.
We
note
that
orbital by a
as defined
\302\243\342\200\236
by E9)
atom.
meihod
10 deal with the problem of
in Chapter 6 a powerful
in a
a box. We iitsi ireai an ideal gas of .V aioms
atoms i\302\273
of the
extension
or different isotopes. This is a simple
of different
species
correction
factor that arises when
ail atoms
are
We then discuss the major
same
of
ihe
b.unc
specks.
isotope
ac
develop
identical
Ideal Gas; A
!\342\226\241
\342\226\241
I
Figure
of different
Atoms
3.8
iV
on
in each
':,(!)
3.7), the
f-
sido includesevery
r.^2)
partition
is fhe
funciion
F6)
Zt{l)Z1B)---Zl(N)
indices
of
boxes (Figure
funclioiis:
distinct
!he right-hand
species in
partition
ZXha*\302\273
product
system
N limesthat
because ihe
Look
First
of llic N
state
independent
F7)
\342\200\242\342\200\242\342\200\242r^N)
oUlotm
iV itottmiontciJng
in
ihc
suewssive
aiuiits
boxes. The
all ordilTcrctii
result
F6)
speciesin
iliis
bang
the same
+ M*l
- in a single bos, the siate
lion numbers. For mo hbded particles
\302\251
and
^(O)
and ihe Male \302\243,(\342\200\242)
combiti.tttons
tmibi be counted i\302\253
+ cfrtO|;irc
tlisiinct Mates, and both
Ij Hie
lite
function. Bui for hs'o tdetiitccil
lHc st.iie of energy c, + \302\243*
pitritclcs
pmtiuon
and only one cnlry is to be made in tfte si.ite sum in the p.irtiiioti
idcmicai siate as c^ + \342\202\254\342\200\236
futiciion.
Chapter 3:
If tlicorbiial
entry
occur
slsould
a faclor
Free
ami Hdmhohz
Distribution
BoHzmann
ihe
correct
llic
cniry wilt occur S< limes iti Zts, whereas
are identical. Thus, Z,v ovcrcounisthe Stales by
is
function for N identical
particles
each
diffrfem,
if
Energy
panicles
partition
F8)
\342\226\240mz'\"-*]<\302\273>**\"
classical regime.Here nQ
There isaslep in ihe argitmcni
in ihe
diticrcnt
oEotla's-
It
i\302\243
no
Simple
from F3).
{\\(zi2nk3)yl
whcii we assume iliat ail jV occupied
orbiuis
rnallei lo cvaltsaie o^rccily {lieerror tmrouuecci
arc
always
by
The energy of
Energy,
from
follows
{he
N particle
ih^S
(lie
gas.
the
partition
l/ = T3^l0gZ.v/(}T}=^T
,
with
consistent
{65} for
F =
With
{he
earlier
tionlogN!
c=
result
NlogN
F =
From
the free
gas of
aioms.
one panicle.
The
free
energy
is
- -i]ogZi'v + ilogN!.
-ilogZy
G0)
= (Mr/2n/!2K'i2KandtheStirlingappfoxima-
Zt = naV
\342\200\224we
have
N,
-tNIog[{.Ui/2n/i2K'2K]
+ rNtogN
p -
F9)
-BF/3K), =
PK
Nr,
NxjV
and
xN.
the pressure
{71}
of the
ideal
{72}
G3)
IdtalGas:
is called
which
1>V =
from
-{CF/?z)r
first
Look
units,
G-1)
NkuT.
D9};
W!og[{Afr/2\302\253/r}3';F]
\\N
+ S , G5}
NlogN
G6)
the
for
equation
the entropy
method
that
a direct
through
The energy
argument.
{7!}and {76}we
NjV,
of a
entropy
involves
6 by
Chapter
particle
a quantum
\342\200\224
involves
result
The
concentration
(he
with
have
not
does
explicitly
{69}also follows
from
involve the
U
*=
N\\
or
identical
of
= \\Nr.
Example!
contribution
Equipanlihn
i* from
particle
Jjjexp[~
a result
to Ft).
similar
result
be
ts generalized
in the
of degree2 in
thermal averagekinetic
energy
is homogeneous
hamiltonian
is
average potential
homogeneous
energy
by use
calculated
are
fat
\302\261ao
momentum
with
component.
The thermal
in
a posilion
component,
will
the
wilt
coordinate
that coordinate
of the system
limit of the
if the
Further,
\302\243r.
Kamiltonian
the
associated
of degree
each
{77}
a canonical
associated
pI1)/2Mx']dpIdpfilp.
also
classical
be
component, theihermal
be Jr. The resull thus
3
Vibt
^\342\200\224\302\273
2
lion
T,\302\273s
50
25
250
75100
Temperature.
Figure
the
3.9
gas phase.
applies to ihe
At
arrangementsof
the
and
temperatures
high
Example:
for
harmonic
oscillator
harmonic
for the
A and
number
1 we
calculated
the
A arid t
atoms
number
for the
results
3 and
har-
6, respectively.
3.9,
of possible
atoms B. We
found
arrangein A.20)
of arrangements:
A/i
G3)
is piotied
in Fi^me
with
these
arrangements
logflMf) 3.10for
jV
~ 20.
is
bg,V! This
!og{iV
contribution
r)!
to the
~ logti
G9)
total entropy
of ;tn
alloy
itfcalGas;
A First
lj>ak
\\
4\342\200\224-~
vj
At_x
composition
Alloy
0.S
0.6
0-4
0.2
1.0
Br
as a function
of
ora random binary alloy
Figure 3.10 Nftxing
entropy
ihe proportions or the constituent
atoms A and B. The curve
plotted
for a total of 20atoms. We see that this entropy is a
was calculated
maximum when A and B are present in equal proportions
0.5),
(x \302\273
anci trie entropy is zero For pure A or pure H.
entropy
.viih
result
G9)
be put
may
a more
in
convenient
approximation:
=* NlagN
- N -
- (N
NlogN
= -(,V
The
of mining.
(N
i)\\ag{N
-
!)\\og(N
- t)Iog(l -
//N)
- i) +
t)~~
t ~
rlogt
l\\agl
l Iog(f/jV)
= t/N,
- -v)Iog(I -
-v)
.vlog.v].
treated as a random
of an n'loy A^^B,
(homogives the entropy of mi\\iug
11.
solmx^i.
TIic
in
detail
in
Chapter
(homogeneous} soiici
problem is J^dopjd
of a mixture of A
condition
We ask i Is the homogeneous solid solution ihe equilibrium
of
and
B atoms, or is the equilibrium
a two-phase
ofcrysi2l!::i*s
system, sudi as a miMure
of the science
answer is the basis of much
pure A and crystallitesof pure B?The complete
of metallurgy: the answer
will depend on the temperature
and on the imcniioiTiic ii;;;raction
case iluit tltc iiue faction energies bciw.vn
energies
t/M, f/EB,and UAa. In the special
This
result
F =
which
we
must
Fo
\302\273
is
of
the mixture
always
in
There is a
any
other
tendency
very small
xN is ihe
if a
evert
A atoms.
sutroundiug
Let this
proportion -\\
number of B
\302\253
t of
strong
The
(81)
xlogx]
have
a minimum
atoms.Tlic
.vj
the
of any
eniropy
mixing
(SO) is
dissolve in
atom and ihe
B to
element
between
exists
etlergy
a B
a positive
quantity.
energy is
xi\\U,
approximately
(83)
~.\\N\\ogx
+ txiog.v)
N(sU
If
wlk-re
(84)
= 0 ,
{85}
when
BFfBx
x
This shows there is a
that
(82)
Fix)
has
small proportion
repulsive
a =
which
proportion
positive\342\200\224so
at least a very
for
A,
will
elements.
pure
case.
this special
element
a)
solution
- Fo
+ xF0
x)F0
in the
arc
entropies
positive\342\200\224all
free energy
- .\\)Iog{l -
A't[A
B crystals
and
ofc/yitatlilci of the
with
compare
F =
Tor
Fo
tct(.v)
solid
homogeneous
natural
\302\273
N(U
impurity
+ t)
xiog-v
(86)
exp(~!}exp(-t//T}.
content
in all crystals.
SUMMARY
1. The factor
=
?{\302\243j)
is the
probabiHty of finding
a system
expf-e./tJ/Z
in a
the
system
comaei
is in thermal
particles
the
in
2. The partition
The
3.
is
function
is given by
pressure
~{cUldV)a = x$gIc\\')v.
p =
4.
free
Hejmltoltz
The
is defined
energy
held at
a system
for
equilibrium
6.
ss -tlogZ.Tltisrcsulitsvcry
}\342\226\240
-i?F/dT)y;
such as p
constant i,
ttscru!
in
\302\253
\302\273a.The
N/V
o =
JVt;
state at all
of spin
atoms
zero,
(nQVf/N\\ ,
concentration
quantum
is reversible
process
equilibrium
and ofquuniiiics
incilcuhitiansorf
from F.
o derived
and
pV
mittimum
is a
~{8F/dV)r
ZH =
8.
xa.
V.
\302\273
as F ^ U ~
'
5.
if
r. The numberof
constant.
is assumed
system
ai temperature
reservoir
a large
with
s (A/r/2n/t2K/I.
nQ
W[log(iic/H)
5];
Further,
fW.
close
to
for
the
ihe
PROBLEMS
/.
Free
energy as a
function
of
a two
of
in
of
energy
2.
function
moments
of
for
ihe
tnagiteliAUiou
temperature
in
a magnetic
and
magnetic
one
states,
for
end
function
pitriiiion
tltu
for
io
x
susceptibility
at energy
the energy
itnd
free
0 and one
entropy
3.11.
Figure
expression
expressions
00 Use ihe
susceptibility.
Magnate
expression
From ihe
an
model system
the
method.
of
magnetization
Here
find nn exaci
s ilM/tlB as a
magnetic
is M ~
the
is
particle
Si
Chapter
and
Distribution
Bolizmann
OR 2
tjelinholt;
Free
Energy
0.6
0.4
A/
0.2
ft
Figure
3.12
i.
oscillator
/Vcc
has
as a function
loui macaeiicmoment
is
the
momeni
a
U.icarfunciio
mB/x
r the manicnl Sends 10 salurale.
ofmfl'r.
Notice thai
31 lou
of HiiJ/r,
bul
hiS
Ai
high
of ihe
Plot
the result
is x
sust;eptibiltty
energy of
an
is
plottcJ
as a function
infinite
only
series of
ihe
ofr
\342\200\224
in the
j\302\253\302\273V
harmonic
2.0
1.5
1.0
0.5
oscillator.
ttniit
free
energy
M/tuu,
(c)
and
Show
\302\253
/\302\273B
r.
A one-dt'mcnsian;il
equally spacedenergy
states,
with
liurmonic
=
\302\243,
sho,
oscilwhere
s is a
of frequency
chosen
have
Wu
Enin
3.13
Figure
osciliuSor
and
tlic classical
to is
of energy
the
at
s =
state
oscillator
harmonic
zero
(S7)
Note
at
that
high
such ihal
temperatures
!og(/itu/t).
\302\273
fitu
(b)
we
From
may expand
the argument
entropy
($8}
The
4.
entropy
Energy
is
shown
in Figure
fluctuations.
wiiis a
syslcin
is
mean
square
capacity in
volume
fluctuation
Figure
ta thermal
3.1-i.
contact
Z
the conventtooai symbol for <e). Hint: Use the partition fitnctwn
out
the
:crm
to
ihc
mean
fluctuation.
Also,
c-U/ci
square
multiply
\342\226\240
The temperature t of a system is a quantity
that by delirsiiion does
(\342\226\240
J. Note:
Here
to
U is
relate
3:
Chapter
S\302\273re3.S4
r
harmonic
ifiiontal
wilh
unncal
mlcln
iiit
iluc
capacity
oscillator
of
flE.
Cv
is k^own
mpcratures
'as
Energy
u>.
The
of i/fiw, whkh
is calkd rhc
is
\302\253herc0,
Icniperamte.
- kB.ot
frequency
units
in
Free
IIcIihUoUz
Versus u-mperatufe
Heal
scale is
mJ
Distrihut
Bohzmnn
temperature
miiis. This
V'^Iv:;. i\\i low
in run<iamciiia!
\\\\\\t
c^issic^I
C(- decreases
csponeniially.
1.0
0.5
not fluctuate
attiiude
otltcr
Any
v,\\
value
would
of a system.The energy
do^s
Thus
\\shcn
is
the system
be inconsibletit
in
thermal
with
contact
of the
definition
our
a reservoir.
with
temperature
a system
such
\302\253AtJ>
=> t2/Cv
(90)
but
5.
effect.
Suppose
one
whenever
increase
positive
system
- r=C,.,
Ovcrhaussr
electrical
equal to
that
by a
can
is given by
Rotation
considered
only
of diatomic molecules.
the translationa!
energy
In our
of the
first
look
particles.
at
But
the ideal
molecules
gas we
can
con-
rotate,
with kinetic
of a diatomic
= jlj
ft;}
of e;ich
of
0, I,2,.. ..
a difference,
makes
The
multiplicity
function
Zk(t)
Z is a sum over all
jb) Evaluate ZH(x)
approxi-
the
partition
that
Remeniber
molecule.
one
(92}
l)\302\243o
is any
where;
levels
approximately for
truncating
\302\253
sOl
by
\302\273
by
e0,
of L'(t) nnd
C{x),showing
7. Zipper pruhh'W.
with
units,
in conventional
{or,
approaches
closed
converting
the sum
the
A
citefgy
h:is N
zipper
u siate
0 and
and
has n
state
ii is
which
in
for
behaviors
-\302\273
ro
limiting
open
with
that
can
the
r -*
0.
and
1}
are
it is
tti which
t:. We
energy
zipper
only im/jp from the left end,
mmiher s can only open if all links to jhe left {1,2,.. .,s tn the
(a) Sliow ihat the parution fuiicliotl can be summed
however,
the behavior
Sketch
r \302\273
r.0.lc)
A-,,)\\Uv?n
require,
site link
that
open,
already
form
193}
e \302\273
the average number of
i, find
of
model
lhe
ofnvo-siraiided
unwinding
very simplified
C. Kittel,
Arner. J. Physics 37, 917A969).
{b) In the
5,
iirnii
Quantum
L;
in the
when
one
Consider
concentration.
rai ion in
concern
lhe
effect is n
kineiic
particle
DNA
confined to a
cube of side
of
energy
to the
molecules\342\200\224see
he
particle
for which
temperature r. (At
this
of unity;
ihe
ration
the occupancy of the lowestorbitalis of the order
Show thai
lowest orbital always has a higheroccupancyilian any oilier orbiial.)
the concentration nQ thus defined
is equal to the quantum eoticcntraitonnQ
defined
by {63), wtthtti a facior of ihe orderof utitiy.
concern
9.
Partition
function
for
independent
two
thai
Show
systems.
I and
sysiems
of
ihe
in
thermal
paniUon
the
partition
contaci
at a
funciions
of the
function
common
separate
systems:
Z(I +
2)
Z(I)ZB).
(94)
ChaptcrS:
10.
identity for
a One-dimensional
is
system
dU ~ fdi
zda =
when
Energy
The lhermodyiiamic
of potythevs.
Elasticity
free
Heimhaltz
and
Distribution
Boltzntann
(95)
/ is
line. By
ill is
find
.-Ha-
The direction of
the
force
is
to the
opposite
pressure.
We
a polymeric
consider
of N
chain
\302\253
JV
\\s\\
show
of
/>, with
each
link
is
'
-T-
(kN
(b) For
to the left,
length
+ q(N,s)
q(N,-s)
and
\342\200\224~
4- 5)!
(\302\243N
(97)
s)\\
that
(98)
(c) Show
that
the
/ is
at extension
force
/ = h/Np1.
(99)
because
the
temperature. The forcearises
wants to cur! up: the entropy is higher in a random
coil than iti ati
polymer
uncoiled
a rubber band makesit contract;
a
warming
configuration.
Warming
of
rubber
is
discussed
steel wire makes tt expand.
The
by
theory
elasticity
H. M. James
and E. Guilt, Journal of ChemicalPhysics
II, 455 A943); Journal
of Polymer Science4, 153A949);
seealsoL. R. G. Treloar, Physics of rubber
elasticity, Oxford, 1955.
II. Ouc'dimcmionaigas.
Consideran idea! gas of A' particles, each of mass
at temperaline oflcnath L. Find the entropy
confined
to a one-dimcsisional
M,
The
force
temperaturer.
The
is proportional
pti5tides
to the
have spin
zero.
Chapter
and
Radiation
Thermal
Planck Distribution
PLANCK
DISTRIBUTION
PLANCK
LAW
and
Emission
FUNCTION
AND STEFAN-EOLTZMANN
96
Law
KirchhorT
Absorption:
LAW
Estimation of SurfaceTemperature
Black
Cosmic
Example:
97
Background
Body
Radiation
93
ELECTRICAL NOISE
PHONONSIN SOLIDS:
104
Modes
Phonon
Numberof
102
THEORY
DEBYE
109
Thermal Photons
Number of
Surface
no
110
Ike Sun
of
Temperature
111
Sun
of the Sun
111
111
112
Gas
112
Shields
Heat Capai
ty
HeatCapa'
ty of Solids in
HeatCapai;ty
HeatCapai
of
Photons
High Temperature
Limit
and Phonons
Flux
Energy
113
113
113
113
114
Radiant Object
and
114
Occupancy
Isentropic
Expansion
Reflective
Heat
SUPPLEMENT:
113
Space
tribution of Radiant
D:
of a
Entropy
ol\" intergalactic
Flu>
Energy
Angular
112
Photon
image
111
Earth
Radiation
of Thermal
Pressure
Shield
of Photon
and
GREENHOUSE
Gas
Kirchhoff's
114
Law
EFFECT
115
Chapter's: Thermal
[We
v,
//
Radio
the distribution of
consider]
U is viewed as divisiblewithout
distributionsare possible.We
of the
finite
whole
equal
N oscillators
U among
energy
then
limit,
an infinite
this
however\342\200\224wUl
of frequency
number of
is the
essential point
made up of
consider
calculation\342\200\224Vas
parts,
the
multiplied
by
of energy e in
the common
ergs
frequency
....
M. Planck
of
the
Planck
Fu
Distribution
FUNCTION
PLANCK
DISTRIBUTION
The Planck
distribution describesthe
of
spectrum
radiation
the electromagnetic
thermal
solid.
The word
\"mode\"characterizes a particularoscillation
amplitude
pattern
low = 2nf as the frequency
energy
of frequency w
The
energy
of
\302\243,
may
be
the
state
excited
with
radiationproblemis
only
of the
in units
s quanta
that
is
U)
e,
integer
(Figure
zero point
\\hai.
energy
These
of
positive
of
a mode
quantum of
mode
the
in
in
harmonic
as the energies ofa quantum
to, but there is a difference between the concepts.A
energies
frequency
Figure
4.1
represents
to s
oscillator
harmonic
Stales of an oscillator
a mode of frequency
photons in
the
mode.
that
tu of
an
(-haptcr
4-
modes a and
magnetic
b, of
Distribution
and Planck
Radiation
Thtftjml
and \302\253>t.
The
&>\342\200\236
frequency
field is suggested
in
the
figures
amplitude
for one pliotor
oscillator is a iocasizedosciiiator.whereas
the
an electromagneticcavity
mode
is distributed
and
electric
of
magnetic
energy
the: interior of
throughout
the
(Figure
problems the energy eigenvaluesare integral
of ho, and this is the reason for the similarity
in the thermal physics of
multiples
the two problems.
The
used to describe an excitationis different;
s for
language
the oscillator
is called the quantum number, and s for the quantized
electromode
is called
the number of photons in the mode.
electromagnetic
We
calculate
the thermal
first
average of the number of photonsin a mode,
a reservoir
at a temperature
when these photo ns are in thermal equilibrium
with
t. The partitionfunction
is the sum over the states A):
C.10)
both
For
4.2).
cavity
B)
}{~shia/r}.
This
sum
is of
ihc form
may
TV,
be
with
.\\-
and
summed
exp{-/i<y/0-
Because
.\\-
is smaller
than
1,
-- x), whence
C)
1
-exp(-tou/T)
The
the
that
probability
is in the
system
Slefan-BohimannLt*
is
by the
given
factor:
Bohzntann
P(s)
The thermalaverage
of
value
exp(
\342\200\224
shci/x)
s is
E)
With
>' =
the
has
side
rmht-hand
form:
-cxpt-v)/
From C)
and E) we
find
-exp(->.)'
F)
photons(Figure
4.3)
number of
with
energy
PLANCK
The thermal
in
for
function
a singie
mode of
AND
average
frequency w. Equally,
thermal
the
lo
applies
any
it is
number of
the average
kind of
wave
field
LAW
STEFAN-BOLTZMANN
\342\200\224
)
1*
G)
4: Thermal Radiation
Chapter
Disiribttlio
Planck
and
+
*(\302\253)
as a function
Figure 4.3 Planck distribution
ofihe reduced temperature i./rw. Here <s(w)>
is Hie thermal average of the
of
rmniber
photons in the mods: of frequency en. A plot of
where
O(o)> + i is also given,
$ is the effective
7ciopoint occupancy
of ihc mode; the dashed
line is i!ie classical asymptote.Noie that
we
0.5
/
A
The
high
be
may
exp{frfcj/t)
limit
temperature
0.5
as
approximated
often
is
\302\273
ha)
lna/r 4-
1 4-
limit. Here
the classical
called
*
\342\200\242
whence
\342\226\240,
the
classical
average energy is
^
<\302\243>
There
mode
is an
has
own
conducting cavity
in
frequency
the
form
wn.
of a
For
(8)
modes
of electromagnetic
number
infinite
its
T.
radiation
within
is
cavity.
any
Each
a perfectly
of modes of the
within
confined
a set
form
Ex
ExOitn
wtcos(fiJji.v/L)sin(iiyjij'/L)sin(fi.Jiz/L)
ID
Et
the
independent,because
sin(fl=Tiz/L)
(9a)
(9b)
= E-0
Ex
are
(9c)
the
three electric
The three
corresponding
amplitudes.
the field must be divergence-free:
components are
\302\243lQ,Ey0
not
and
indepen-
A0)
and
\302\243,0\",
the
rhar the
states
This
nx,
components
4- E:Qn:
E^nr
ny
transversely polarized
be
condition
the
find
-. Eo \342\226\240
0n \302\273
A1)
vector
to the
perpendicular
>l, so that
and
Law
Slcfan-Bolwtann
factors, we
ail common
drop
and
Law
Planck
field.The polarization
direction
is defined
in
the
as the
with
is a
cavity
direction
of Eo.
For a
given
n,,
triplet
directions,
polarization
n. we
c the
wilh
velocity
of light, we
if we
\";\342\226\240
\"y
>h<
4-
are of the
iij
independent
by an integral
indices.
That
n;2)
mode
the
is,
over
we set
,,/
photons in the
= w3L2.
in terms
A3)
of Hie triplet
of integers
A4)
,
rta\302\273)\302\273'i
A5)
mrc/L.
is, from
cavity
G),
Hya
form
w.
all
iriplei
define
the frequencies
describe
each
.(V
'.
trJJ.
\302\253)
of
= (rtj[2
\342\200\236
then
perpendicular
for
find
cWnJ
modes
equation
i:y
V'-v1
mutually
integers nx,
ny,
n..
Positive
Chapte
involved.
two
now
the sura
the positive
only
or integral by
a factor
of the electromagnetic
polamations
Thus
modes).
cavity
because
arises
(\302\243K
multiply
independent
setsof
=h
1, = ji ft
hu)n
Jo
with
A5) for
over
a dimensionless
Standard
\302\253\342\200\236.
dnn*
(nVic/L)
\302\273\302\260
is to
practice
We set
variable.
\342\200\224
A8)
ex
transform
x =
nhcn/LT,
A8)
becomes
A'J)
The definite
such as Dwight
in the
(cited
general
is
in good
found
references}. Tlie
standard
the
volume
lional !olhe
of
law
fourth
V =
L1. The
power
oflhe
result that
lemperalure
is
B0)
\\Shs
with
volume
tables
the
radiant
is known
energy
density
is propor-
as theStefan-Boltzmann
radiation.
we
B0) into the spectral
decompose
applications of this theory
as
the energy per unil
of
the
radiation.The
is
defined
density
spectraldensity
We
find \302\273u
from
and is denoted as \302\253\342\200\236,.
can
volume per unit frequency
range,
in terms of w:
(IS) resvritlen
For
many
B1)
U/V
so
that
the
spectral
density
is
B2)
Planck
Law
andSufan-Boltzmam
Law
\\
1.2
1.0
\342\200\224
0.6
0.4
0.2
\\
\\
\342\200\224 \342\200\224
0/
Ploiof.vJ/(c*
is a maximum,
energy density
per
This frequency is directly
proportional
unit
ffequency
so ihe
range.
tempera sure.
of
distribution
This result is the Planck radiation
the frequency
law; It gives
thermal radialion (Figure4.4).Quantum
here.
theory
began
the relation
The entropy of the thermal photonscan be found
from
A34a)
~
at constant volume:da
from
B0),
dUfr, whence
Thus
the entropy is
B3)
The constantofintegration
is zero,
from
a.
4: Thermal
Chapter
gy
flux density
area
and
length
The geometrical
The
by
for
result
final
use of
gy
The
Distribution
Planck
and
Radiation
the
radiant
B0) for
light
the
is (he
time.
of
unit
of
Thus,
The
is often written
result
as
B6)
\302\253
aB s= b2V/60AV
has the
5.670
vahie
10~8
W m~2
as
black
A small
body.
body
the
on
10\"*
K~* or 5.670x
that
a cavity
radiates
whose
walls are
rate
walls
in
is said to radiate
thermal
given
of
K~\".
s~'
cm\022
erg
at this rate
as a blackbody at the
of the physical constitutionof the
is independent
only
in
B6a)
T will radiate
at temperature
depends
hole
unit
is
flux
U/V.
Jv
times
derivation
energy
a column
in
contained
energy
equilibrium
in
B6).
the cavity
The
rate
and de-
temperature.
Emission and
Law
Absorption; Ktrchhoff
to the ability of the
The
of a surface to emit radiationis proportional
ability
surface to absorb radiation. We demonstrate
this relation,
first for a black body
or biack
surface
is defined to
incident
upon
biack if
the
and,
second,
be blacktn
it
hole
for a
surface
with
arbitrary
properties.
An object
electromagnetic radiation
a ho!e
in a cavity is
in that range is absorbed. By this definition
small
incident
the
hole will
is
enough that radiation
through
a given
frequency
range if all
reflect
enough
in the
be absorbed
lo
walls
cavity
with
back
loss
negligible
oj Sutj
The radiant
energy
flux
radiant energy
Jv from
density
emitted
flux
object.
We
the
prove
following:
fraction a of the
non-black object
If a
radiation incidentupon
at
temperature
absorbs
by the
emitted
by a black body at the same
and
e the emisstviiy, where the
flux emitted by the object is e times
it,
the
radiation
flux emitted
whence
e is zero. A perfect
docs not radiate.
reflector
The argumentscanbe generalized
to apply to the radiation at any frequency,
<o and
as betsveen
w + ito. We insert a filter
between
and the hole in
the object
black
outside
this frequency
the
range, and
body. Let the filter reflect perfectly
now
this
The
flux
let it transmit
within
arguments
perfectly
range.
equality
=
for any surface
eM
a(w)
apply to the transmitted spectral band, so that
in thermal equilibrium.
zero,
of
Estimation
Surface
Temperature
One
way
to
estimate
the
surface
temperature
at which
law,
Eq. B2),
as
\342\226\240\342\200\242
0
- 3exp(-x)
= x.
This
be solved
may
equation
and Planck
Radiation
Thermal
4:
Chapter
DiVnfmrion
kca^JkgT = xm
2.82
B?)
Figure 4.4.
as in
is that the
Example:Cosmicblack body background radiation. A major recentdiscovery
universe accessible to us is filicd with cudutian
like
a
thai
of
black
approximately
body
Tor big bang
at 2.9K. Tlic existence
evidence
of lliis radiation
[Figure 4.5) is important
assume
ltw! tli^ unhorse is expanding
and cooling
wiitl liliic.
cosmotogiol modelswhich
so
h;id coo
universe
irucructs
This
Most
lines.
mancr.
Tftcrcafier ihe radiaiion evotved with \302\273mcin a very siinpte way: llic plioion gas
of 2.9 K. Tlic pfioion gas will
al constani cniropy io a icmpcraiure
by expansion
at consent
ihc expastsion
during
cniropy if Ihe frequency of each mode is towered
universe
wilfa llic nuoi^er of pljotons it\\ c>icti mooe Kept con^JunlL We show in ^joj
that ihe entropy
is constant
if lhe number of pholons in each mode is consiant\342\200\224the
cooled
was
remain
of
nimicr
Ihc
ihaf
itic
tnc
below
lhe
After
inlo
ihe eniropy.
Urn evoluiion
determine
occupancies
decoupling
and
stars,
galaxies,
Electromagnelicradiaiion,
is superimposedon the
black
cosmic
sponMucousthermal
called
H. Nyquisi.*
noise,
H. N!jquisi,p!:js
lical jijsus,
ts
4.6. We
\342\226\240
Wiley,
botiy radiation.
shall
R
!
sec
across
that
by J.
property of
lo llic
proportional
<K:)
dimension, we
in one
law
Planck
were discovered
The characteristic
square noisevoltage
by Figure
inlo
more
tn voltage
fluctuations
are
tnaucr
NOISE
ELECTRICAL
which
of
a resistor.
B. Johnsonand
Johnson
value of the
is also
noise
consider the
These fluctuations,
explained
resistance
by
ihc mean*
is that
R,
as shown
Microwave
Interstellar CN
measuremeni
IR
2.9
K Black
body-
Frequency (cm\"!)
4.5
Figure
Experimental
body radiation.
speclrum ofinlcrslettac
oflhe
infrared
a bulbon-borne
wiih
Caurlesy of P. L. Richards.
edge of
Tlie
voltage
A/of
wave
cLvironuignetic
tlicorcm
Nyquist
generated
uccded in
any
gives
by a resisior
estimate
of
neiir
lhe peak,
ai frequencies
the
circuit.
propagation
a quanlhative.
in
thermai
Hie iinnting
cosmic
of the
microwave
heicr
expression
equilibrium.
signal-io-uoise
The
is lhcr^fore
ratio of an experirr.cnial
and Planck
Radiation
Thermal
4:
Chapter
Zl
~
\342\200\242
Carbon
filamen
+ Advance wire
xCuSO, m H,O
vNaCi
RcMblancu
Mil
in
component,
kinds of conductors,including
0.5
0.4
0.3
0.2
0.1
H..O
in
Afiei
electrolytes.
J.B.Johnson.
In ihe
apparatus.
square
original
a
across
voltage
the
form
resistor
states
theorem
Nyqutst
of resistance
in
ft
ihe mean
that
thermal
at
equilibrium
temperature t is given by
B8)
where A/
is
the
frequency*
bandwidth
the
which
within
circuit
the
of Figure
4.7, the
power deliveredto an
'
al
which
'
In
this
maich
section
(R' =
the word
(R + Rf
fluctuations
voltage
are
range
range
it does
resistive
ignored.
delivered
because
load
'
in
R' is
B9)
R) is <1\">/4J!.
frequency
refers
to cycles
per
unit
time,
and not
to
radians
per
unit till
Noise generator
4.7
Figure
which
this
hi
power
enables
Consider
characteristic
as in
impedance
is a maximum wiih
condition
the ioad
At
supply.
us to
the
limit
voiiagc
be
absorbed
circuit is maintained
power
said
at
= R.
when R'
lo the
to bo matched
- (Yi)f4R. The
filter
bandwidth under
[lie bandwidth
10 whicii
the mean
fluciuaiion
applies.
line
Figure 4,8 a losslesstransmission
~
R
terminated
at
eachend
Zc
by
wiihoui
with
to a
frequency
is.
ihal
to R'
respcel
is
&
match,
resistance ft
delivers
cilrrenl
consideration;
square
ciicuii for a
Equivalent
a generatot
sense
the
reficciion
in
that
the
ail energy
appropriate
of lenglh
a resistance
L and
charac-
R. Thus
the
The
entire
t.
temperature
frequency range
C0)
Sf~c'lL,
propagation
velocity
on the
line. Each
exp(ftwAJ
Figure 4.8
Transmission
Hue
has
ihe
heir
The
liieorcm.
theorem
mdamcniai
erminai
L with
oficiijjtli
resistors
resistance
are
same value R.
has ihc
in
is r. It
in
the
that
follows
hw
limit
classical
the
Planck distribution.
to the
according
equilibrium,
with circuits
on the
energy
\302\253
z
so
line
in
the
are
We
range
frequency
concerned
usually
the thermal
that
C2)
line in one
off the
comes
energy
direction is
C3)
The powercoming
off
the
al
line
end is
one
impedance
R at
is matched
9 =
but
2R1,
itt
temperature(hermomctry,
dc current
when
no
when
a dc
iA/
C4)
used
been
{Figure 4.9)
where
in low
it
is
tempera-
{not
con-
more
resistor
appears
current flows.
PHONONS IN SOLIDS;
DEBYE
THEORY
energy to the
regions
temperature
impedance
measure
to
convenient
B8) is obtained.
so that
\302\273
Thus
rise.
terminal
the
terminal
must emit
load
would
</2>R
the
when
the
equilibrium
all absorbed in
decided to
approximationto
the
actual
distribution.
The
the
possible
as a
fvee vibrations
good enough
of a lattice must,
sonic spectrum
j in
Solids:
Dcbye Theory
Figure
Mean
icmpcralurc indicated by
tlidrmometer.
After
R.
C Wheailey, J.
533 A972).
and
J.
a CMN'
R. GiiTarJ,
Low
powder
li.
Tcnir
Physics
100
of course,deviatefront
its soon
its t!ie wavelength becomes comparable to
. .. The only thing which had to be lione was lo
to she fact that every solid ofjunta dimensions
numfrc'r
contains
adjust
ajiuite
atoms
and
a
At
low
has
mint
her
vibrations....
of
therefore
L'uoiujh
finite
of free
and ttt perfect analogy to the radiation htw
temperatures,
of StefanBoltzmann
..., the vibrational energy contentof it solid will be proportional
t/ie
disittuees
this
of the atoms.
P. Dcbye
elastic
;is for
wave in a cavity
magnetic
clastic wave
is calleda
of
wave
in
oj is
is quantized
is quantized.The quantum
thermal
The
phovwn.
frequency
a solid
average
number
of
energy
of an
of pitonons in
given by the
an
of
an
just
photons:
1
We assume
that
t!ie
frequency
ofan
elastic
wjive is independent
C5}
of theamiMttmle
ofthe elastic
sixain.
We
want
to find
the energy
A-
Webb,
6,
account
minimum
contribution
Number
the
from
conduction
each
3A?.
An
wave
elastic
in
Chapter
7.
Modes
of Plionon
of N atoms,
treated
electrons,
three
possible
a finite
modes
in
a cavity,
of freedom,
degrees
has three
electromagnetic
is bounded.
solid
two
transverse
and one
polarizations of an electromagnetic
of the atoms is perpendicular
displacement
a
wave the displacein
wave;
longitudinal
displacement is paraiicl
over
all
to the propagation
direction. The sum of a quantity
modes
3,
may be written as, includingthe factor
longitudinal,
in
two possible
to the
contrast
| JW
of A7). Here n
as for photons. We
by extension
exactly
elasticmodes
ts
to
equal
C6)
in terms
is defined
to
want
<*\302\253(\342\200\242*\342\200\242)
,
find
3JV:
C7)
In the
number
becomes
in\302\273D3
The thermalenergy
of
the
3;V;
phonons
nD =
is, from
FW/7!I'3.
A6),
C8)
,\\umbcr
by C6)
or,
ofPho
and CS),
D0)
with
analogy
By
place
where
limit
of
usually
of A9),
the evaluation
{'in2twf2L)(xL/n!n-)-i
For
ji/irii/Lr.
the
velocity
of sound
written
in
L3 we
J*V*
D1)
\342\200\224~~^
with
Here,
C8),
the upper
is
integration
written as
-
,vfl
where6 is
the
called
Dcbye
0/7
= fcsO/'t .
D3)
temperature:
0 =
The
with
velocity of light r,
of the
(hv/kB)Fn2N/VI \\
D4)
for
D1)
is of
the energy
f\"^
Jo
as earlier.
Thus
proportionalto
T4\302\273
The
heat
__\302\243_-?-
exp.x-
D5)
15
low temperaturelimitis
capacity
is, for
\302\253
kB0
or
\302\253
0,
D7a)
4: Thermal
Chapter
Radiation ami
Distribution
Planck
17.78
-\342\226\240\342\226\240
\342\200\224
a
E 13.33
4.44
Y
\\A
3.99
in
r3,
Figure 4.10
show
TJ10
these
from
Low tempcralure
heat
Ihc cxcettent
daia
is 92
agreement
K. Courlesyof
capaciiy
whh
!tie
5.32
K3
of solid
Debyc
and
L.1 Fincgold
T1 law.
In conventional units,
D7b)
This
h known
result
as the
Debye T1 !aw.*Ex
plotted
Problem
given in
are
given
in Fig-jrc
in Table
4.1. The
13.297 A912):
values
calculated variation of
tiiermodymmiic
4.2
and
14,65 A9K).
are
plotted
in
results
menta!
experimental
peri
Figure
4.12.
T\302\273 0
for
Cv
is
versus
the
a Debyc
T/6
is
of
solid are
subject
Aiimitr
Lu
of
210
Jjg
7.
UJ
UJ
EQ
pT
UJ
<
(J
a.
Photon
Modes
4: Thermal RaJhtion
Chapter
ami
Dim
Planck
25
i
^\342\200\224^\342\200\224
20 -
/
Heal
Figure-5.11
according10ihc
capacity
solid,
The
approximation.
Dcbye
vertical scale is in
Cv of a
J mol~'
K\"'.
The
Jmor1
L\342\200\224
K\021.
0.2
'able
4.2
Values of
C,, S, U,
ai
id F on the
S =
k^o
Debye
0.6
0.4
ihc ory.
0.8
in unlls J
U,0
moI\021
1.0
K\"
IT
Cv
24.943
0.1
24.93
90.70
X
2402
- 666.8
0.2
24.89
73.43
115.6
-251
0.3
24.83
24.75
24.63
63.34
74.2
56.21
53.5
50.70
41.16
24.50
46.22
32.9
27.1
0.4
0.5
0.6
CO
0.7
24.34
0.8
24.16
0.9
23.96
1.0
23.74
42.46
39.22
36.38
33.87
1.5
2
3
22.35
24.49
20.59
18.30
16.53
10.71
4
5
12.55
6
7
9.20
6.23
-87
-60.3
-44.1
-33.5
-26.2
-209
16.82
-17.0:
9.1
5.5
2.36
6.51
1.13
4.08
0.58
2.64
0.323
0.1S7
0.114
2.53
10
1.891
0.643
0.048
15
0.576
0.192
0.0096
-137
19.5
1.22
0.874
3.45
170
22.8
1.77
4.76
1.2
0.073
-7.2:
-3.6.
-1.2
-0.4!
-0.2
-0.1
-0.0
-0.0
-0.0
-0.0
-0.0
Summary
20
0
10
-10
-20
-30
1.5
1.0
0.5
\024\302\2600
FiKiire^.12
Energy
solid, according
of tlic
solid
to tiit
free energy
t/and
theory.
DcbyC
s=
I/-
Tlic Dcbye
roof
temperature
is 0.
SUMMARY
Planck distributionfunction
1. The
for
the thermal
2. The
is
average number of
photons in a cavity
mode
Stefan-Boltzmannlaw is
for the
15/iV
in
a cavity
'
at temperature
t.
of
frequency
3.
Planck
The
and Planck
Radiuiwn
Thermal
4:
Chapter
Distribution
law is
radiation
\302\2533
r2c3
the radiation
for
energy per
unit
volume
The
low
Debye
is,
in
where
limit of
temperature
conventional
unit
per
5.
\342\200\224
exp(/io)/t)
range
\342\200\224
of frequency.
aB is
where
oBTA,
the Stefan-
uniis,
the Debye
temperature
0 s (hvjkB)Fn2$fvy'\\
PROBLEMS
1.
Number
of
thermal
at temporal
equilibrium
Show
photons.
ure
a cavity
in
of photons XXs\")
= 2.404n~2K(t/Ac)s.
in
D8)
whence
<r/N
=s
3.602.
It
is
universe
is 109 larger than the
both
are of
total numberof titiclcons(protons,neutrons).
Because
entropies
the
the order of the respective
of
number
(sec Eq. 3.76),
photons
particles
of the universe,
provide the dominantcontributionto the entropy
although
the particles dominau- ., c total energy.
believe
that
the entropy of the
We
so that Mie entropy of the universeis approxipllotonsis essentially
constant,
approximately
7. Surface
density
with
constant
at
the Earth
constant of the
wavelengths
and
time,
Earth.
referred
The
observed
value
of
the
incident
integrated
total
rays
to the
solar
constant
0.136
J s
D9)
theSunasl.5
thai
body
is T
Sun is 4
10\026 J S\"
<rB =
constant
Stefan-Boltzmann
.the
show
10!3 cm
generation of the
of energy
*.
5.67 x
10l\302\260cm.
of the Sun,
(a) Estimate
by a dimenof magnitude of the gravitationalselfof the
Sun, with AiQ = 2 x !033g and RQ => 7 x 1010 cm. The gravienergy
gravitational
G is 6.6 x iQ\"8 dyne cm2g~2,Theself-energy
constant
be negative
will
referred to atoms at rest at infinite
ihe
total
thermal
Assume
ihat
(b)
separation,
kineticenergy
of the
in the Sun is equal to \342\200\224
atoms
limes
the
gravitational
\302\243
theorem
of mechanics.
Estimate the average
energy. This is the resultof the virial
temperature of ihe Sun. Take the number of particles as 1 x IG*7.This csUmaie
too
low a temperature,
somewhat
because the density of tlie Sun is far
gives
from
\"The range in central temperature for different
uniform.
stars,
excluding
of
of
those
for
which
Saw
matier
the
only
composed
degenerate
perfect gases
and
does not hold (white
those which have excessively sniall average
dwarfs)
and
is between
densities(giants
1.5 and 3.0 x iO7 degrees.\"
supergiants),
B. Lynds, and H. Pillans,Elementary
Oxford,
1959.)
(O. Siruve,
astronomy,
3.
of t/te interior
temperature
or otherwise
(he order
Average
dimensional
argument
4. Age
radiates
energy
for
on
radiation,
of hydrogen
Find
the present
time, (a)
the rough assumptions
(atomic weight
the
the
of
he
Sun. It is
(AAf)c\\
temperature
Surface
us much
renijiates
ihe
that
1.5
(a) to
books
converted
estimate the
universe
by
that
Peebles
is about
and by
over
ihe day-night
Earth is ;it a constant jemporiittini
5S00K;
RQ = 7 x 10locm; and ihe I2arih-Sundislanwof
of the
face
7\"o
ihe
and
4.0026)
IOlJcm.
6.
sin
Use
cycle.
the
on
Earth,
in
conversion
ihe
has been
(b) Use
available
of the Sun
5.
energy
hydrogen
original
=
\302\243
10 x
ofthe
total
L0Q7S)to helium(atomicweight
the
expectancy
total rate at
the reaction
life
is the
lQ;6Js~!
Pressure
(a)
of thermal
variation.
Show for
p = -(cUfcV),
a photon
gas thai:
- -^s/iiiluij/ilV)
,
E0)
and Planck
l Radiat
where s; is the
in the
of photons
number
(b)
Oiildbnti,
dojjfilV
p =
(c)
moJej;
-mjyV;
E1)
U/iV.
E2)
to 3 x (energy density).
with the kinetic pressure of a
(d) Compare pressure
radiation
of t mote cm'3 characteristic of the Sun.
gas of H atomsat a concentration
At
what
the two pressures equal? The average
are
temperature
(roughly)
of
the
Sun
is
believed
to
be
near2 x tOT K. The concentration
is
temperature
at
where the
the
highly nonuniform and rises to near rOQmoiecm.\023
center,
kinetic pressure is considerablyhigher
the
radiation
than
pressure.
radiation
the
Thus
is equal
pressure
of thermal
the
7. Free
energyof a p/iot
where
ihe
the parlhion
that
Show
(a)
gas.
function of a
by
is over
product
direclly from
on
free energy
Helmholtz
The
is found
as
E3)
E4)
F-T][tog[t-exp(-AuiA/T)].
Transform
the sum to an
integral; integrateby
F =
5. Heatshields.
to a
between
black
the
constant
at
plane
two
black
planes
is allowedto come
and T,, and show
presence of this
to
that
net
energy
where
is inserted
temperature
Tu is parallel
at temperature
- T*),
plane
state
a steady
the
plane
third
find
E5)
is Jv = aB{Tf
used in B6). A
to
-n
(nonreflective)
temperature
parls
flux
aB
density
is the
in
vacuum
be-
Stefan-Boltzmann
This
to
9.
L on
transmission line of length
wave
waves satisfy the onc-dimcnsional
electromagnetic
equation
=s c2E/ct2l where E is an electricfield
Find
the heat
v2d2Ef3x1
componentof
the
on
thermal
at
the
w
hen
in
capacity
photons
line,
equilibrium
temperature
which
Photon
gas
in one
dimension.
Consider a
ihe usual
way for
zero amplitude ai
in
proceeds
with
as
line.
10.
Hcitt
radiaiion
by
of ilic
ralio
ilic
thai
in a
atoms
by
space.
of iniergalaciic
capacity
occupied hydrogen
alsooccupied thermal
one dimension:
cacli cud of ilic
10'9.
limit.
Show
lhal in ihe iimil
of solidsin high temperature
a
solid
towards
die
limit
of
capacity
Cy \342\200\224\342\226\240
goes
3A'\302\243B, in
conventional
units.
To obtain higher accuracy when
T is only moderately
can be expanded as a power seriesin 1/T, of
larger than 0, the heat capacity
Heat capacity
//.
T
heal
liie
\302\273
0
the form
E6}
Dcbye
in the
Energy fluctuations
atoms
is
in
from
the
in
ihermal
contact
with
3 to
show
at
ai low
region
in which
a heat
the
that
IF is given by
inserting
dtelcciricsolid
with
the
cm ~3. Estimate
heat
the
to
a solid
in
temperature
Chapter
your result by
sum. Check
4.2.
Heat capacity
/2.
term
Table
capacity
would be
1 K.
temperatures.
ihe Dcbye
Consider a solid of N
Ti
law
is
vaiid.
The
solid
fluctuations
reservoir. Usethe resultson energy
root
mean square fractional energy fluctuation
E7)
T =
that
Suppose
a side;
$F
then
order of uniiy
14.
Heal
longitudinal
p=
0.02.
in liquid
waves
(a)
0.145gcm~3.
transverse
no
are
gram
capacity
per
value
=\342\226\240
0.0204
Calculate
on the
x
T\\tn
= 200K;and N
1O1S for
the fractional
particle of volume
!0\025 K
of liquid
capacity
sound
At
a dielectric
for
s\"'. There
CK
I0~2K;0
the Debyc
waves
0.01cm on
is of
energy
ihe
cm3.
in
fluctuation
1
a particle
in the
The
0.6
of longituvelocity
K is 2.383 x 104cm
liquid. The
is
density
the
heat
Dcbye theory
value
thai
suggests
the
Physica
Distribution
most
Hit;
due
32,
625
to
f
excitations
important
value
experimental
are
experimems
Kramers,
are
phonons
liquid.The
H. C
and Pfanek
Radiation
Thermal
4:
Chapter
in liquid
4He
has been
J. Wiebes,
!957}.
distribution
that
the spectra!
of radiant energy flux, (a) Show
of the radiant energy flux that arrives
in the solid angle i!Q is
0 is the angle
the normal to the unit area makes
with
fuucos0*</n/47r,where
the incident ray, and i^ is the energy
unit
Show
density
per
frequency range, (b)
that
the
sum
of this quamity over all incident rays
is \\aiu.
15.
Angular
density
16.
Image
An on a
lens
an
Use
the hole in
image
cavity
argument
equilibrium
of
area
to relate the
product
to
AuQtl
axial
{al!
parallel
Qtl and
where
AaQ0
from the
as viewed
leas
from
and
small).
angles
cosmic
of photons
<s +
to start
from
is convenient
It
18.
haxiropic
expansion
not changed
l)log<5 + !)
the
and
the
Consider
of photon gas.
temperature
a cube
- <s)log<s).
ES)
function.
partition
in this
argtted
has
radiation
black
the
of volume
pressure
performs
drop.
gas
at
of
temperature
photons
of the
r. Let the
entropy we know
of lite
the
The
iV1'3
titat
subscripts
i and
/ refer to
the
initial
and
final
siatcs.
black sheetsis (I
also
often
are
dewars
film called
Mylar
by the
and in clouds,
alumtntzed
an
of
the wanning
of the surface of
of water,
of an infrared absorbentlayer
describes
interposition
and of carbondioxidein
such
e =
GREENHOUSE EFFECT
the
as
contribute
much
layer,
the
90 percent
as vapor
and
of the warming
of the surface of
temperature
Earth
the
the Sun
between
atmosphere
effect.
Absent
between the
intermediate sheet is
helium
I; r - 0. Liquid
Effect
Greenhouse
caused
with
at tempera-
when tiie
density
means
8, which
maintained
radiation
thermal
of
density
flux
the
times
\342\200\224
a. Let
insulated
SUPPLEMENT:
The
r)
in Probfem
as
black
a plane
\\
sfieets
black
two
is
Earth
the
flux
the
by the requirement of energybalancebetween
incident on the Earth
and
the flux of reradiation
from the
to the fourth power of the temperaEarth; the reradiationflux is proportional
of Problem
temperatureof
the Earth,
as in D.26). This energy balance is the subject
the
where
4.5 and leads to the result Ts \342\200\224
temperature
7'\302\243is
{RsI^seV^Ts,
of the Sun and DSE
of the Earth and Tsis that of the Sun; here/fjis the radius
determined
of solar
primarily
radiation
is the Sun-Earthdistance.
The
Sun is
that
of
result
\342\200\224
subtended by
the
Sun)
of roughly
factor
is TE
problem
the solar
reduces
280
the
K, assuming
geometry
T,=\302\273
(the
FC The
5800
smali
solid angle
by
(i/20)*.
defined
as
assume
as
an
an
example
absorbent
lEt^h + h-ns.
where
is
l\302\243g
the
thermal
Oux from
E9)
presenceof
the
perfect
effect.
greenhouse
the
that
greeahouse
flux
as
varies
T4, the
new temperature
is
Earth
T\302\243s
so
the thennal
Because
\302\253=
2\302\273/\302\253rfi A.19)
warming
of the
280
K ~
333 K,
F0)
K =
53 K
for
\342\200\242
For
end
detailed discussions
i. T. Houghton
1992:
ct aJ, editors.
Climate
change
1992, Cambridge
U.P., 1990
Chapter
and
Potential
Chemical
Gibbs Distribution
CHEMICAL
OF
DEFINITION
Barometric
of
Variation
119
POTENTIAL
122
with Altitude
Pressure
Magnetic
Example: ChemicalPotentialof Mobile
\"'\"
in a
Field
Magnetic
Example;
Batteries
Chemical
Potential
120
Gas
Panicles
127
'
\342\226\240
129
131
and Entropy
Thermodymtmic Identity
Numberof
133
134
GIBBS SUM
AND
FACTOR
GIBBS
125
139
Particles
140
Energy
Example:
Occupancy
Example:
Impurity
140
Zero or One
!omz;ition
Atom
in a
Semiconductor
143
SUMMARY
144
PROBLEMS
145
145
1. Centrifuge
5.
Magnetic
6.
Gibbs
7.
States
8.
Carbon
Monoxide
146
146
146
Poisoning
of O2 in a MagneticField
147
147
Fluctuations
Concentration
Ascent
145
11. Equivalent
12.
145
Concentration
9. Adsorption
10.
145
145
Field
Definition of ChemicalPotential
of Sap in
148
148
Trees
13. Isentroptc
148
Expansion
14.
Multiple
Binding
148
of O2
15. ExternalChemical
Potential
....
149
\342\226\240al
Potential
and
Gibbs
Tor
Distribution
free
&
will
assume
and
wiiii
number
equilibrium
with
a minimum,
subject
free
energy
h\\
to N
of the
F2
jV,
- t/( + t/2
+
jV2
the minimum
value
restraints
on the
applies
pp
oiher
N,,.V\302\273
T(ff,
This
in
result
diiTusive
equilib-
ihi5 sysicms
between
A)
<T>)
Because N is constant,She
= constant.
combined system is
(R.
with
equilibrium
of pparticles.
^2, the
F=
Heimholtz
thermal
in
paiii^lc diaiiibution
S,
t!io toial Hchulioltz free energy
.md
between
makes
of
energy
system
single
minimum
with
respect
to
of
Definition
System
Chemical
Potential
.Sj
t*\"Ener\302\260y
exchange\"\"}
conlacl
with each oihcr
Example of Iwo systems,Sx ;mdX., in ihcrmal
and wiih a large reservoir Of, forming a closed total system- I)y opening the take,
contact
wliilc remaining at the common
S{ and ^j can be brouglit in tlillusive
transfer
for a net panicle
tcmpcraiurc r. Ttie arrows at tlm valve liave been drawn
lo S2.
from \302\243j
Figure
5.1
variations
= -5N2.
5Nt
tlF
with
K2, also
K[,
Hutt
at
the
minimum,
- (cFi/cN^^lNi
held constant.
(/F
so
At
With
= 0,
+ lcF2/dN2)sc!N2
(!Nt
~-tlN2,
WG
- (SF2/cNl),yNl
[(cfj/t'iV,),
B)
have
- 0,
C)
cqutlibriuni
- (cF3/cN2)t.
((Tj/oV,),
(\342\226\240\30
DEFINITION OF CHEMICALPOTENTIAL
We
define
the
chemical
potential
I
as
(/;0
I
E)
Chapter 5:
ChemicalPotential
where ji is
Distribution
Gibhs
and
Then
'-
/'I
for ditTusive
when diVt
5j, ihe value of dN \\
ihe condition
expresses
elF will be negative
thai
from
to
5,
free
energy
is
we sec from
C)
are
transferred
panicles
tlN2 is positive. Thus the
If/(,
equilibrium.
is
negative:
When
negative,
and
> ;i2,
^i to &2; ilitit
flow from
us particles
decreases
t'l
particles
of
low
chemical
and
not
a deriva-
from
F(t,V,N)
- F{x.V,N-
(low
's.
F)
1).
between systems
in
which
the
contact,
rcguhucs
important
fully
transfer.
are
Two
ihat can exchange both energy and particles
energy
systems
in combined
thermal
and ditTusive equilibrium when their temperaturesand
chemical
are eqtial: i[ = t2;/i; = ji%.
potentials
of
A difference
in chemical
potential acts as a driving forcefor the transfer
force
for the transfer
particles just as a differencein temperatureacisas a driving
of energy.
has its own chemical potential.
If several chemicalspeciesare present,
each
The
chemical
and
regulates
potential
it is
as
For species
j,
G)
the
wherein
for the
Example:
of
Ihe
differentiation!
TTumbcrs
of
all
particles
are held
constant except
species j.
Chemical
monatomic
potential
of the
Ideal gas. In
C.70}
showed
that
ihe
free
ideal gas is
/logZi
logN!] ,
(8)
of
Definition
is the
for a single
function
partition
Chemical
Potential
A0)
If
which
approximation for
the Stirling
use
we
factorial,we
tlutt v,e
assume
and
A\"!
fold
approaches
log
iV
log
for
large
A\"
[N
llcttcc the
of \\.
values
- 1 = togtf
-1)--
chemical
\342\200\224
potential
(II)
of the
ideal
gas is
=
,<
or,
by
- log.V)
-rUogZ,
(9),
A2a)
where
\342\200\224
NjV
is the
defined
concentration
F{N
From
approximution.
system
volume
(S) we obtain
By use
separately.
The chemicalpotential
composedof
electrons
of
ths
definition
ji
concentrationof
/t
we expect intuitively:
lower concentration.
the
i)froin.{6)as
na
(A/r/2nfi2K
2 ts
the
quantum
by C.63).
Ifweuseji = F{N) -
Stirling
of particles ami
concentration
-i[log2,
particles,
ideal
Ttog(p/tiiti).
gas
we do
af/j,
not
logjV],
not need to
which
on their total
law p
nr
we
can
agtces
use the
with
numheror on
write A2} as
A2b)
This
is what
concent mi ion of particles increases.
chemical
from
to
to
lower
higher
particles
higher
potential,
on
of
an
the
concentration
ideal
gas
dependence
Figure 5.2 shows
the boiling temperature
or of helium atoms, for two temperatures,
increases
as the
flow from
Chapter 5: Chemical
Potential
Figure 5.2
composedof dectroio.jrhelium
regime
with n
\302\253
nQ,
a ^as
at 4.2
atoms,
of -
of
least
at
^i
of an ideal gas
K..To be in the classical
o! r,
units
in
K and 300
oulv for
satisfied
range
Distribution
andGibbs
t. For
electrons this
as in ihe
normal
is
in metals,
satisfied under
those
conditions.
of
and
liquid
pressure, 4.2 K,
lave ncgaiivcchemical
ill atmospheric
licimin
tnolccubr
jtascs aiwjjs
such
ihnt
and
room
unJer
potentials
nfnQ
300 K. Atomic
tciilii^blc
plijiically
soe from A2) iliat
/i is
icmpcraturc,
\302\253
!,
we
ncgaiive.
Internal
and Total
The best
equilibrium
way
in
Chemical Potential
to
understand
Ihe
presence
the
of a
chemical
potential
acts
is to discuss diffusive
on
Ihe
particles.
This
Internal and
Potential
Chemical
Total
Figure 5.3
be
the
potential
charge
has wide
problem
13.
in Chapter
discussed
same
\342\200\224
n
Sx und
systems,
junction
al
&->t
the
equilibriumchemical
difTcrence
potential
the potential
iliat
above
Af[(im'tial)
way to
by
- ^i-
= ;/2
A/j(iimial)
Now
let
such
energy be establishedbetweenthe two systems,
of
each
in
is
raised
energy
by exactly
panicle sysiem
Si
its ininal
value, if Ihe particles carry
one
a charge
qt
simple
in potential
difference
I'
temperature
equilibrium.
hvo
consider
again
semiconductor
the
between
two
a voltage
systems
lhat
such
A3)
the
with
shown
polarity
also can
in Figure
of mass
by
the gravitational
the
height
/i, we
by
sfcp
in
difference
when
we
raise
potential
gravitational
a system
of particles each
where
g is
acceleration.
Once a potentialstepispresent,
this
5.3.
is included
in (he
the
potential
energy
of ihe
patrides produced
system.
Mgurc
5.3 we
/affinal)
= ;(,(initial) -f
of
S2 fiNed, ihe
[,..(initial) -
established
with
i, would be raised by
system
two
between
step
potential
systems of chargedpaniclescan
/i,(inilial)]
A4)
qAY
q >
wild
of negative
with
cespect
was
barrier
the
When
/^(initial)
chemical
difference
equilibrium.
that
barrier
potential
gA
potential
chemical
in
barrier
the
the two
brings
/(i(initial)
The
inserted,
\342\200\224
statement
This
it forms
potential, and
of a
potential
/'
Here
/jtM
is the
internal
be present
electrical,
Pi
the
is
if
chemical potential*
external
the
magnetic,
\342\200\224ca'i
Hi
definedas the
were zero.
potential
A5)
+ft,,;\342\226\240\342\200\236,
energy
potential
parts:
external potential,and
chemical
be expressed
total
the potential
\342\226\240
Gibbs
measures
called
differences
further
chemical
in
fi.
potential
mechanical,
-A
A6)
chemica!
potential
those
of
the
working
semiconductors,
chemical
words
qualifier.
potential
may be
called the
electrochemical
be
equilibriumcondition
and
internal
external
Unfortunately, the distinctionbetween
sometimes is not made in the literature.Somewriters,
particularly
and
with charged particles in the fieldsof electrochemistry
when
use
often mean the internal chemical potential
they
The
nmy
jiial
would
as
Apeil =
potential without a
that
potential
and
.
ihe intrinsic
it,*,
'
if
potential
the
that
potcnsjal. He recognized
term
electro-
a voltmeter
mea-
Chemical Potential
and Total
Internal
SysicmB)
5.4
Figure
A model
of ihe variation
aimcispliericpressure\\>.iih
altitude:
of gas at different
gravitaiiona!
field, jn iherma!
\\olumcs
heights
and
con wet.
System (!)
chemicalpotential is clear
unambiguous,
The
use of \"chemical
potential.\"
we
and
without
potential\"'
avoided
tit
situations
in
which
shall
an
tisc \"total
adjective
chemical
should
be
tis meaningcouldoccur.
The
of the
simplest
example
pressure whhahhutte.
external
is itte equilibrium
sysiems in difTcrcm
potentials
bciwccn
lo be isothermal.
assumed
layers ;lt different llcigliis of ihe Canh'satmosphere,
Tim rcul uimosplicfc
is in imperfect equilibrium: ii is'cunstaiiily
upsa
by Hitititoroloeicut
temperature
processes, faoih in the form of macroscopic air movemems and of strong
We may
from clouii fonn;uion, ;inii becauso
of heal input from liiil ground.
grudiunis
make ;in ;ippro.\\imaic
the dilL-iem
air layers as
model
of the aimosphcrc by KtMliiia
^iih
each oilier, in diHerem
syslemsof idea! gases in ilierilia! and diftusive
eiiuilihrium
of barometric
Example;
Variation
diffusive
equilibrium
exieroul
\\c\\c\\,
(Figure 5.4}.If we place ihe zero of the poieinul energy ai ground
is ihe particle massand g ihe
energy per moleculeai heighi Ji is Afyfi,whcrc.\\f
acceleialion.
The internal chemical potential of ihe parlidesis given
by A2}.
poicnlials
the poiemial
gravitational
The loial
bciwccn
diemical poiemial is
{17}
In
equilibrium,
this
musi be
independent of {he
Tlog[i.(/t)/H0]
and
ihc
conceniralion
\302\253(/t).alhcijjlU
A/y/i
hcidil.
Thus
rlog[ii@)/nQ]
h satisfies
(IS)
in
di!
Chapter 5.-Chemical
and
Potential
Dhtnliution
Gibls
1.0
0.5
\\
0.2
\\
o.i
i
5.5
figure
v-iih
atmosphere
The
of atmospheric
The crosses represent
Decrease
ahiiude.
concerting
as
on rocket
sampled
corresponding lo a
pressure
Ihc average
0.0S
fliyhis.
a slope
lias
Vine
siraight
icmpcraiure T =
K.
227
\\
\342\200\224
20
0-10
Heighi,
The pressure
aullilude
li
lo
llieconcenlration;
40
30
in
50
km
Ihe pressure
therefore
is
p(/i)
=.
= p@)exp(-/i/'iJ-
p@)exp(-.V9li/t)
A9)
Thl^
in an
itio
fatthcr dp,
t\\ictul
11UC.U1-.C
pressure
ll.o
UanhS
iiut
these
Ivavc
LiiiiiO^pticrc
behavior.
iaken
uuromoLrtc
isoihermat
hrgeiy
i>
not
;n;tiir.ittly
jjloi
potnis
f;i!i
pressure
near
iiiiiinspUufc:
see
fine, suggesting
Probicm
1.
a'ttipliaital
4QKiloiMcttrs,
roughfy
iso-
vtl and
Tlie straight
= 1000:1,
behavior.
thermal
range
jj{/ij):pl/i,J
from A9),
so that
of
the
of the
slope
at
temperature
which leads to
is Mg/x,
line
eurve
observed
tltc
T ~
0, p(li),'p{0)
\302\253
227
x,'kB
\302\253
I, is
caused
K. The
non-intersection
by the higher
tempera-
aliiiudes.
lower
Tlic atmosphere
M the
with
consistsof
of
composition
appropriate
p^insiTrii^itic
T *}\\
tiff
than
more
is
fevel
TS pet
tlie
JiiTerences
in mass, ihe
difTcrcnt
nk*c
u\\ /iifrprcnl
n, and
iij
If
particles
a magnetic
in a
moment
are
ill
iltcrti:iM\302\273\302\253:lK-|k-lJ
it. mtht
magnetic
with
vary
out
are
potentials
!t\\:nivs
iintwi'iiittKlfovcrtbtf
\\\\w \\ wlumc
in unlcr
out
5.6).(Tlie
dent
of posiiion,
if there
is free
total
diffusion
to
ut:tintaii)
chemical
of
vo!ui\302\273c^iltcsyslciH.llici-.-:-.vt.ij.H
Mi ,i
unal clicnnt.it i- \342\226\240\342\226\240
j cotiMjisl
Potential and
5: Chemical
Chapter
Dhtribut
G'thhs
---
\342\200\224\342\200\224\"
Iff'
ion (i,
5.6
Figure
pari
in
1GIU
of a gas of magnetic
ofihe chemical potential
values of the magnetic field
concentration, at several
= 2 x iO7 cm\021 for I! ~ 0, ihcn ai a point \302\253here B \342\226\240=
20
Dependence
on ihe
ides
Ifn
intensity.
kilofiauasl2iesb)ihccona:nlraiionwillbe2
species in
have
equilibrium
equal
desired
\302\253,{B)
where
ti@}
is tiie
concentrationat
n{B)
n(B)
The result
magnetic
magnetic
colloidal
Held
such
as
total concentration
a poini
at magnetic
\302\253
n,{B)
n^B) =
ii[ 4field
intensity-
The
at
nt
a point
of
to be:
,
where
the
field
B =
B4)
0. The total
S is
* n{0)M
form of ihc
but is applicable to
fine
exp{-\302\273)B/T)];
4-
^-
panicles
magnetic
fujictionai
B3)
^\302\253@)exp{-)nB/i)
= Jn@)[exp{jHB/T)
ji,(B)
n{0)cosh{mB/T)
;i,01(|).
fay substitution
seen
in{0)exp(mB/t);
orientauons,
solution. Such
\342\200\242
\342\200\242
-Y
to concentrate
result
fecromagncfic
is not
limited
particles
B5)
in
regions
to atoms
of high
wi[h
in suspension
two
in
in the siudy
suspensions are used the laboratory
of superconductorsand fhe domain strucfure of ferromagnetic materials.In
ace used to tcsf for fine structural
cracks in high strength
the suspensions
sfcel,
When
fhese
arc
coated
a
furbine blades and aircraft
with
gear.
landing
ferromagnetic
flux strucfure
engineering,
of {22)and
solutions
!09cm\023.
diemioil poientiais,
lUl)
The
\342\200\242
ciir3
particles
in
of
he magneiic
Internal
and
suspension
fields
intense
ttie
field,
placed in a magnetic
at the edges of the
flic
becomes
concentration
particle
enhanced at
crack.
In
the
If
/'iM
t log
\342\200\224
does
t log \302\273,,)
(\342\226\240=
Oneof
Example; Batteries.
it
not
-f
constanl
on
depend
B6}
of the
concentration
the
puctielcs.
in
of
electrochemical
the
the
both
process
discharge
the positive
most
the
battery,
electrode arc
Pb +
than
two
the
the
PbO.
reactions;'
SO4\"\" -+ PbSO.,+
2e~;
B7a)
electrical currents
If the battery
electrode
the electrolyte
(sec Figure
5.7b).
B7b)
2H2O.
\"
acts as a sink
the sulfafe ions at
electrode
of
PbSO4
for
SO*~
the
surface
ions,
the internal
keeping
of the negative
because of B7b) the
Similarly,
electrode
positive
chemical
ions, keeping the internal
potential
/((H1\") of 'tie
ions lower at the surface of ihe positive electrodethan inside the electrolyte. The
the
tons towards
the electrodes, and they drive the
potential gradients drive
acts as
hydrogen
chemical
and
exactly the
sink
for
the
during
potential
correct
H+
in
not
the
net
electrode,
negative
are depleted
from
the
positive
As
a result,
the
interfaces,
electrode-electrolyte
steps of
to stop
to equalize the chemical potential steps and
the
If an external
the chemical reactions from proceeding further.
steps develop at
magnitude
given are
electrons
connected,
process.
discharge
terminals arc
accumulate
electrochennca!
The
PbSO4, via
+ HjSO- + 2e\"-+
+ 2H+
PbO2
\342\200\242
electrode and
of the negative
sulfate,
electrode:
Positive
electrode
Ie;td
to
electrode:
Negative
lower
Pb
metallic
tlie
converted
reactions.
resume.
reactions
a negligible
The
electron
through
the
electrolyte.
the
clcclrodc
(\342\226\240f)
PbO,
l>b
T
(b).
5.7
5-igurc
parlialiy
two
(ajThekjJ-aciJ
ioni/cd
ions
U^SOj.
plus one
PbSO4 + 2HjO,Lii
before the
and
H*
and
ihe chemical
barrier.
isiirning
Iwo
ciccirons.
development ofimcfiia!
one
convert
(b) The
poltnltai
cicctrotic
into
PbSOt
PbOj
ilnmclsed
moltrcul^ imo
eiectrociiemicaipokntials for
barriers
y(.\\)
thai
after
in
+ 2e~;
\"
SOI
of the
and
Potential
Chemical
Entropy
During
I he
charging
cMornai voiUigc
is ;i}>[i!ied
posilncclcclrodcsrelative
to
negative charges,diffusion
will
2gAK_
of
H+ ions wi!i
the
stop
two polemics
forces);
(electromotive
ions
curry
two
BSaJ
A/i(SO4\"\.")
\302\253
B8b)
A/i(//').
are called
Al'+
and
AK_
suifute
when
+ ^AK+
The
the
when
slop
\342\200\224
DifTusion
ciectroiyie. Because
ihc common
ha!f-cc!i potentials or
half-eeil
EMF's
Aft
-0.4voll;
Tiic lolai
AK =
AK+
developed
\302\273
+1.6volt.
across
one
full
cell
of
ihc bniicry,
is
-
AK_
\302\253
2.0voli.
B9)
This is ihc
live lenninal
Chemical
Potential
and Entropy
of
we defined the chemicalpotentialas a dertvathe
an alternate
relation, needed later:
energy. Here we detivc
In E)
the
Hclmlioltz
free
C0)
This expressesihe raliopi/x
1/r
was
defined
in Chapier
as
2.
a derivative
of ihe
Clmpler5; Chemical
To derive
U, V,
N.
and
Cibbs Distribution
and
Potential
a [unction
as
of the
independent variables
differential
The
cU
<w
C1)
differential
change ofthe entropy Tor arbitrary,
independent
=
and
rfJV.
Let
dV
0
consideration.
for
the
under
</t/,
t/K,
changes
processes
Further,select the ratios of rf<r, c!U, and i/N in such a way that the overall
values
these interdependent
temperature
change dx will be zero. IT we denote
otda, dV, and dN by {&a)t, FU)t and (<5N)rl then dx = 0 when
gives
After
the differential
division
by {5N)r,
C2)
volunie. With
the
definition
original
is (dU/dN),,
D[/),/(JW),
of 1/t,
all at
conslant
we have
C3)
dNj,,
This expresses derivative
at
By
the
original
of the
definition
\023
and on
comparison with
oTderivatives at constantt
U in terms
constant
chemical potential,
C4)
[H,
w.,
we
C3)
obtain
C5)
same
quantity
ft. The
and
difference
C5)
represent
between
two
different
them is
Table 5.1
of liic cm
partial derivatives
a, U, and F
F, witii
energy
relations
of
Summary
expressing
cr, liic
ropy
as
given
am! Entropy
Potential
Chemical
ti-.c temperature
free
U, and liic
energy
of their
functions
itatur.il
variables
independent
o(U.V,N)
, is independent
(IU\\
variable
\\ia)rtl
y,,
function of
of
function
C5)
variables.
same
yields n as a function of
is to
a third
find
we
In C1)
U,
terms
x,
N.
V,
The
assumed a =
quantity
fi
is
that n appears as
that
so
a(U,V,N),
the
in both
same
The object
variables.
of different
N, so
V, and
E)
of Problem1i
for p:
relation
C6)
and in
derive
10 we
Chapter
compilesexpressions
Tor
have their
i,
of
t, p,
and N.
of o, U, and
F.
Table 5.1
forms
All
uses.
identity.
Tlicvmodynamic
dynamic
identity
particles
is allowed
given
We
can
in C.34a)
lo change. As
generalize
lo include
in
the statement
of the Ihermo-
number
of
C1),
C7)
By use
C0)
for
da =
dU/x
relation
pdV/x
C.32)
- pdN/x.
for p/r,
and the
relation
C8)
This
Chemical
5:
Chapter
lo give
be rearranged
may
Distribution
dV = xJs
statement of the
broader
is a
which
to developin
;u|jv
C9)
we were
than
identity
ihermodynamic
able
3.
Chapter
GIBBS SUM
AND
FACTOR
GIBBS
pdV
The Boltzmannfactor,
in
derived
3, allows
Chapter
us lo
of the
ratio
the
give
the
probability
with
contact
reservoir at temperature t:
P(z2)
is
This
contact
of the BoHxmann
of that
much
argument retraces
a very
We consider
presented
large body
number N0.The
is
body
the system
potentialof
the
system
iV
the
reservoir
particles,
are
has Nu
C/o
Chapter
that
to those
energy
(Figure
e.
Uo and
diffusive
constant particle
obtain
<R and
reservoir
large
may exchange
and the chemical
5-8), They
the temperature
oftiie reservoir.When
- M particles; when
\342\200\224
To
factor
Gibbs
and
thermal
3.
contact
assures
equal
in
of two
composed
system
in
with
The
mechanics.
lo a
factor
at temperature
reservoir
with
the best
perhajtls
is thegenecauzauon
ihe
the
system
the statistical
system
lias
energy
has
e,
properties of the
+
on identical copies of the system
accessible
slate of the combination. What
reservoir,
copy
quantum
will be round to conis the
in
a
that
ihc
observation
given
system
probability
N particles
contain
and to be in a stale s of energy \302\243j?
number of panicles.
stale
s is a state of a system
The
some
having
specified
The energye](iV) is the energy of the state s of the A'-particIc
sometimes
system;
When can we wriie ihe energy of a
we write only e,, if ihe meaning
is clear.
A' particles
ihe energy
of one pur tide
in
an
orbital
as -V times
system
having
system,
make
we
observations
one
in
ihat
orbital'.'
the
the
particles
Tor
Only
may
as before
each
so
interactions between Ihe particles are neglected,
be treated as independentofeachother.
when
iit thermal
and diffusive conlacl wiill
of energy anti of panicles.
Tile total system
S is tnsulaicd from the external world, so thai
<H +
ihe
total energy and the total number of particlesare consianl.
The
ofihc
icmperamre
syslcm is equal to tile lempcrature
and
is
oflhc
i lie chemical
reservoir,
potential of the sysiem
to
the chemical potential of Ihe reservoir.
The syslcm
equal
may bs as small as one atom or it may be macroscopic, bui
ihe reservoiris always
lhan
to be thought
of as much
larger
lite system-
A system
Figure
5.8
a large
reservoir
is in
and
the probability the system has
particles
of accessible
to number
a particular stale s. This probabilityis proportional
is exactly
stales of the reservoir when the stateof
specified. That
sysiem
Let P[NtEs}denote
jY
that
the
the
of \302\243,
the
state
the
number
is, ir we specify
the number of accessibleslatesofO?:
\302\273((H+
The
y(<Jl)
us
stales
the
Uo - e,. Because
stalesof
of accessible
of
that
the
system
the
S)
gift)
P{N,i:J
in
is proportional
reservoir.
NtU0
is just
{41)
(H
x 1.
we are
probability
of
states
oraccessible
zt).
a single
and
spiciixd
Ikivc
energy
to Ihe number
5: Chemical
Chapter
fit
Particles
i\\'o
Energy
UQ
Panicles
,V,
\342\200\224
Ft
Enemy
Uo
Energy
Panicles
,VU
Particles
A\\
Energy ,
r,
(b)
(a)
dirTusive
and
to
it. In
stales
number
{b] the
system
is in
quantum state
2, and
with the
contact
the
has g{N0
reservoir
- A'j,
of
Uo
accessible
lhat
other
the
number
one
that
\302\243;
of particles
reservoir.
probabilities,
is in state
the system
on
depends
total
the system
is in
2:
g(N0 --JV,,[/0 -
e,)
D3)
where
g refers
to the
By definition of the
in Figure
5.9.
entropy
s(N0,y0)
so that the
is shown
situation
probability ratio hi
D3)
ejpOfNo.f,,)]
may
be written
D4)
as
D5)
>ffel)
\"
eXp[\"(N\302\253
N\"y\302\260
D6)
Act is the
Here,
eniropy difference:
Ac h a(N0 ~
The reservoir is very
NUUO
approximated
and
\302\243
that
N2,U0
D7)
e2).
lerms
order
firsl
to the
relate
with the
in comparison
large
- a[N0
e,)
system. The
becomes
N,U0
For A<?
defined
~i)
by D7)
D8)
we have,
to the
first
in
order
iVE
\342\200\224
N2
in e,
und
\342\200\224
c->t
E0a)
by our
bin
for
the
reservoir,
(?e'
E0b)
by C0).
D9)
is
(N,
Here
Aa
refers
to the
- Nt)n
(t, -
on
refer
combining
E1)
system. The
and E1):
to the
D6)
central
E2)
5;
Chapter
Potential
Chemical
The
the
is
probability
of particles,is
normalizing
absoluteprobabilities:
that
facior
the
of the
states
overall
converts
.
This is called the Gibbs sum, or the grand
sum,
The sum is to be carried out over all states
particles:
the
of
exp[(A'/i
or the
ASN.
abbreviation
the
defines
this
grand pan
it
for all
system
E3}
E],VJ). r].
function.
ion
numbers of
written e, as eJ(:V,
We have
to
of part
icles .V. That is,
stale on the number
hamiitonian.
The
state
s(N) of ihe exact A'-particie
= 0 must be
N
term
included; if we assign its energy as zero, then ihe first
in ^ w'-' be 1.
term
The absoluteprobability
the
will be. found in a state Nlt e, is
that
system
Gibbs
facior divided by lite Gibbs sum:
by ihe
given
the
emphasize
of the
dependence
of
the
E4}
chemical
temperaturet
result
our
cenlral
ratio of any two P's is consistent
ihe correct
factors.
relative probabilities
E2}
gives
This
applies
a system
lo
lhat is ai
and
E2} for
with
Thus
and
of
jV2,\302\2432.Thesum
of tlte
system
ihe
probabilities
of all
stales
for
al!
p.iiiictiljrl)-
lite Gibbs
stales
the
for
A',,
of par*
numbers
s,
icles
is unity:
f
by ihe
ji. The
poieinial
definition
IicIpM.
of 0-. Thus
The
nuriliod
E4)
us,cil
gives
there
the
correci
to ikme
iibsuime
the Potion
\342\226\240
155)
probability.*
dimibuiion
impends
on
6744s
and Gibbs
Factor
m diffusive
and thermal
contact
Average v;i!ucs over ihe sybiems
are easily found. If X{N,s) ts ilie value
ihe sysiem
of -V when
and
is
in
ihe
slate
then
ihe
thermal
particles
quantum
s,
average of .V
s
N and all
ts
Sum
with
lias N
reservoir
all
over
{56)
Number
the
of
The
particles,
is in diffusive
system
number of particlesin
ihe
contact
with
system
is
been multiplied
can beobtaftied
liie
by
from
of N.
definition
in ihe
term
each
because
average of the
thermal
The
reservoir.
value
appropriaie
the
of panicles
number
lo E6).
according
thermal averages.
to calculate
result
this
use
shiill
We
Gibbs sum
has
of#
whence
<,V>
Tile
J
by
tiicrma!
number
average
use
direct
of E9).
will
We often
be
written
l-ll
we
E9)
= r^-1
is easily found from the
of particles
When no
for </>
confusion arises, we
speak
of the
later
for
interchangeably
,V
or
shall
write
Gibbs sum
jV for
the
occupancy of an orbital,
<.V>.
F0)
where
see from
is called
the absolute
ideal gas ). is
directly
propcrliona!
to ihe
lambda.
We
concentration.
Chapter5: Chcutkul
and Gibbs
Potential
Distribution
F1}
'
A5S
and ihe
is
F2}
is useful, because in
This relaiior.
finding
many
actual
problems
will make
ihat
value
ihe
we determine
/. by
panicles.
thermal
The
Energy,
v -
of the
energy
average
^i
<E>
system is
F3)
E9} and
so that
F3} may
-
Chapter 3
in
terms
Example:Occupancy
occupiedby
may
be
5.10).
A
zero
occupied
single
usually
be
lo give
combined
F5}
toi
that is
of the
zero
molecules
by one
heme
We shall
;r-\302\253
expression
simpler
1/t.
that
Observe
<\302\243>.
for
or one.
A red-blooded
or by one
molecule is the
in
the
of an
example of
heme
group,
syslcm
obtained
in
may be
be vacant or
ihat
which may
Oz molecule\342\200\224and
group occurs
was
calculations
never
by more
5.10
Figure
where c is
ihen
distance,
\302\243~
If energy
in ihe
Theseare itjc
only
possibiliiies.
atom
the
F6)
+;.cxp(-\302\243/r).
lerm
The term t
wilt be negative.
arises from single occupancy.
where Mb denoies
present,
Aexpf-c/i)
Mb 4- O2 or MbO2
17 000.
myoglobin.a protein of molecular
weighi
ihe conceniraiion
versus
of oxygen
occupancy
Experimental results for Ihe fractional
arc show a in Figure 5.t t. We compare ihe observed oxygen saturation curves ofmyoglobin
and
in Figure 5-12. Hemoglobin is ihe oxygen-carrying component
of blood,
hemoglobin
ti is made up of four molecular
wiih ihe single sirand of
identical
each slrand nearly
strands,
ihe classic
myogiobin,and each capable of binding a single oxygen molecule,
Hisiorically,
work on ihe adsorpiionof oxygen by hemoglobin was done by Chilian
Bohr, the father of
Niels Bohr.The oxygen saturation
curve for hemoglobin (Hb) lias a slower rise at low
because ihe binding
of a single O, Io a moleculeof Hb is tower Ihan for
pressures,
energy
Mb. A! higher
lhat
is concave
of
ihe
Hb curve has a region
pressures
upwards,
oxygen
because trie binding
the
first
is
adsorbed.
increases
after
O2
energy
per Oj
The Oj
thai
molecules
chemical
the
on
are
hemes
by
the
exp(/i/i}.
in
potentials
the Oj
find
ihe
the
value
liquid, so
surrounding
and
in
solution:
= ?.{O2)
/(MbO2)
/i(O2);
From Chapter 3 we
in
ihe myoglobin
on
\302\273
of /
in
F7)
of the
icrnis
gas pressure
retalion
A =
We
with
equilibrium
are equal
of Oj
/i(MbO2)
where
assume
Oj
adsorbed
by
a hemc
O;
rctal
10 an Oi al infinite
from ihe site.
sepatuiion
If energy musi be supplied10detacri
llie O3
from ihe heme, then c will be negative.
infinite
of an
Adsorpiion
ihe energy of an
F3)
p/t\302\253Q.
sotulion.
conslant
At
temperature
/(Oj)
is
p.
O^
is found
Ac\302\273pl-t/i)
I
io C), in
applies
n/nQ
/.exp(-\302\243/t)
from {66}to
be
1
'
r'exp(\302\243/t)+
Fg)
reaction o( u
(Mb)
nvyoglobm
may
oxygen
Gj
at a
as
site
Tlie
isotherm
3 Langmujr
follow
be viewed
<{tiitc
molecule
can
accutaiely. Each myoglobin
adsorb one Oj molecule.These curves
show
(he fraction of myogtobin with
adsorbed
O.
as a function of ihe partial pressure of Oj.
are for human myoglobin in
The
curves
solution.
is found in niuidcs;
it is
Mvogiobin
for
the
color
of
slKtfc.
After
A.
responsible
Rosst-Fanellt
and E. Antoiiini.
Archives
of
and
Btoihciittsiry
Biophysics77, 47\302\253
(tySK).
Concentration
curves
Saturation
Fi\302\273ure5-12
lo nijoglobin
bound
of O.
and
iKmoglobtn
(Nib)
(J-ib)
in wmer. The partiat
molccuks in soluiion
pressure of 0. is plotted as the Iiorizonl;i!
Tiie
;t\\is.
the
vertical
molecules
a.\\is gives
of Mb
0, mokcuk, or the
which
ihe fraction of
lus
one
bound
suarnis of
lib which have one bouiid Qt innlcutle.
h;is a much Uirgcr change in
Hunioglabm
cotitem
in ihe pressure range bensecu
oxygen
ttw
nuerks
and the veins. Ihis circumstance
facilitates
ihe aciion
of ihe heart, viewed as :i
The
pump.
curve
for myoglobin
MbO..
of the
ft action
curve for
reaction
has the
Mb
lienio^lobin
+ O2
Itits
\342\200\224\342\200\242
;t
uiiiCicm
O,
lib
and
S. Siminondi,
1961.
Gvm-J
bioJtaniMry.
Wiley,
of O3,
rcbt
as
[he same
is
which
subsiiiute F8)
in
the
with
in
7. We
Chapter
to obtain
F9|
} 4- I
or.
derived
function
distribution
Fcrmi-Dirac
Gtbbs Sut.
and
Factor
G'tbbi
G0}
\302\273iurexp(E/r}
\302\256
jiqtcxp(\302\243/i).
p0
'
+P
Po
whac
G1}
is
!>0
wiih respect
is constant
Example;Impurity
oikn
ionizatian
in a
as impurities
in
Lei / be the
bound
is accessible.Therefore
one
an
with
When
the
with
to
large
and
electrons
ionizalion
can be
electron
semiconductor.
of the impurity
energy
an impurity
atom;
the
system
fanned
with lite
& has
by
the
attached
the electron
rest
semiconductor.
We suppose
atom.
either orientation t or
three allowed states\342\200\224one
with
ionizalion
by
band
systems S in thermal
of the semiconductor:
small
are
atoms
reservoir
energy
electron
conduction
the
In
chemical
numerous
may iose an
crystal-
with
has zero
Suite
result
the adsorptioiiof
without
attached
spin
f, and one
atom is ionized. We choose tiic
electrons, the impurity
other two stales thereforefiave ihc common
energy c =
electron
The
temperature.
of
Atoms
a semiconductor
the semiconductor
of
diffusive equilibrium
and
the
to dcicribc
used
when
be treated
on
but depends
solids.
atom
to prcsfi re,
as the
known
an
electron
zero
an
electron,
with spin
ofenergy
\342\200\224
/. The
].
of &
accessible
below.
number
Description
Electron
detached
Electron alladicd, s
1-kcifoti ijjnjLlicJ.
The
Gibbs
sum is given
by
G2)
The
tliat
probability
&
is ionized
tliat
probability
0) is
\302\253
P(ioaized)
The
\302\273
((V
P(O.O)
$ is
neutral
is just
\342\200\224.
G3)
is
(im-ionized)
= /'(It,-/)
P(neutral)
which
-\342\200\224-1-
\342\200\224
=
+ P(U,~/) ,
G4)
- PtO.O).
SUMMARY
1. The chemicalpotential
found from
/*
equilibrium
if jtx
is
{cUJcN)a
\342\200\224
i{cojvN}v_v.
of two
of
3.
The
Gibbs
have
and
^{Mi'lnh2)*'2
nQ
at chemical
a system
that
N particles
and be
state
a quantum
in
sum
5.
taken
over
The absolute
6. The
The
field of force.
gas ;t(int)
is the quan-
4, TheGibbs
is
mooaiomic
internal.
factor
ideal
an
for
concentration.
bo
also
difl'usive
= }tz.
quantum
as h{t,V,N)
defined
\342\200\224
all states
activity
is
thermal averagenumber
defined
of
of
by
particles
<A')J
particles.
expQi/r).
is
kg
\302\243
PROBLEMS
1.
velocity
angular
j[(r) on the
for
as
an expression
i. Find
temperature
Centrifuge.
radialdisiance
<\342\226\240
from
an ideal
for
the
axis
the ions
about
rotaies
lhe
dependence
axis,
in terms
with
SI
al
the concentraiion
of *i\302\2430)on the axis. Take
of
gas.
wifh
r iiuMstirtiJ
The
integral
ttf (he
diverges
aimosphere cannoi be in
are always escapingfrom
3.
I'ntuiitiul
each of mass
at
tipjwr
flic
limit, so
ihe
R is
here
l-yrih;
the railing of
ihe liarili.
and the
be bounded
cannot
that
Molecules,
equilibrium.
em-i'ity of gas
of
ihc center
from
f75)
</rrJcxp(A/yKV<'0
4nn(K)Cxp(-A/yR/t).Jjti
light molecules,
particularly
atmosphere.
fa
t in
temperature
a uniform
of moms
a column
Consider
Jield.
gravitational
gravitational
field
average
average potential energy per atom.Thethermal
is
of
Find
the
total
heat
density
height.
capacity
independent
total heat capacityis the sum of contributions
from the kinetic
the potential
energy. Take the zero of the gravitational
energy
~ 0 of the column.
= 0 to h ~ oo.
h
h
from
Integrate
thermal
the
Find
y.
kinetic
energy
energy and
at lhe
from
bouom
5.
drawn.
If
= 300K,
particles contain to
shown?
Determine
concentration.
Afaguctic
how many
give
.\"-\342\226\240..\342\226\240
magnetic
the
ratio
m/x for
Bohr magnetonsfiB
concentration
effect
which Figure5.6is
the
eh/Zinc
ivould
of the
magnitude
whh
unoccupied
that
system, (a) Considera system
one
in
either
by
particle
a two level
sum for
Gibbs
6,
energy
= i +
3-
time.
in the
c include
ttuitn
Notice
Our assumption
that
s. Show
the Gibbs
be un-
may
or occupied
zero
of two
sum for
ihis
states,
G6)
;.exp(-E/r).
of
one
is
system
state at
in each
particle
\302\253=
Oasa
particular
the same
state
of a
is
G7)
(c)
Show that
(d)
Find
an
(e) Allow
one
3.
particle
=
for the
expression
I +
1 +
the thermal
Aexp(-\302\243/i)
as
uitd
7, Statesof
negative
diogen atoms;suppose each
tliat
atom
can
Stale
Number
of
-JA
-if)
ion
involve
5,).,
and
replaces
the
O2
lu
luihuning.
ad^oibed
on hanoglohin
eh
by one molecule
CO. Let
J3
U
of
per mom
electrons
be unity.
r.
mtmoxitle
Cmtitm
number
Livci;t^^
hy-
Energy
Posiiivc ion
The condition
X.
electrons
E\\cii<.-d
FioU rlic
a lattice of fixed
exist in four states:
Ground
Negative
G9)
+ Aexp(-e/i)].
/.)[!
Consider
iotuzation.
posttiw
each by
we have
shown,
system.
be occupied
ate may
0 and
A2exp(-\302\253/t>-\302\253
the
of
A'
catbon monoxide
(lib) mulcculcs in
each
energy
fixed
adsorption
ea
home
poisoning the CO
ilic
Wuoil.
To hhnw
a heme may
one molecule O2 or
by
sites
site on
be in equilibrium
be
with
with
Froblcn
O2
field.
Suppose that at most one O2 can be
Problem
and
that when /.{O2)~ iO\025 we have
8),
group (see
90 percent
of the hemes occupiedby Oj. Consider
O2 as having a spin of i
and a magneticmomentof i (ts.How strong
a magnetic
field is needed to chance
T = 300 K.? (The Gibbssumin the limit of zero
the
adsorption
by 1 percental
field
will
differ
from
that
muhiof Problem 8 because there the spin
magnetic
the
was
of
bound
slate
neglected.)
muhiplicity
9. Adsorption
to
bound
ofO2
in
a magnetic
a heme
10. Concentration
fluctuations.
contact
in diffusive
system
We have
a reservoir.
with
is not
of particles
number
The
constant
in
seen that
\342\200\242
re:
<,v>
from E9).
(81)
<lY!>=LLi.
3- ^
The
deviation
mean-square
= <(N
<(ANJ>
(b) Show
<.V\302\2732>
be
of N from
((AWI)
=
is the
diffusive
fi
xvi:
;u>rly
iliis
n-iilt
</V!>
<,V>:;
= tc<,V>/c>
in llio
(83)
liial
mean
by
as
<(A.V)'>
In t'liaptcr
defined
is
- 2<N><N> + (N}'
(N>)
written
<iV>
of an
\\02Q
atoms,
idea! gas
then
in
ihe
Chapter 5:
ChemicalPotential
and
Distribution
Gibbs
fractional
such
a system
be rigorously
contacr
wirh ihe reservoir. When
is allowed
is
<iV)
can be usedin the experimental
determination
of the molecular
103 - [O10;see M. Weissman,
molecules such as DNA
of
MW
andG.
Feher, Proc. Nat. Acad. Sci.73, 2776A976).
diffusive
11.
of chemical
definition
Equivalent
defined
E) as (cF/cN)tiy.
by
An
fi
Prove
resultsC1)
and
C5).
have
we
potential moreoften
a function
as
Schindler,
was
5.1 is
(S5)
(cU/cN)ay.
to
Gtbbs
It will be convenient
for treating {5}as the definition
In
two-fold.
of the
of/i,
we need
practice,
to
ji, is equivalent
define
adopted.
consequence, are
a mathematical
in Table
listed
expression
was used by
reasons
Our
*=
H.
potential*
equivalent
the number of
conslatil because
low, this relation
weight of large
temperature tihanasa
(85) as
the chemical
of
funciion
the
a particle
is added to a system
a process in which
entropy
a
while
the
is
constant
is
more natural
of
the
temperature
system
process
kept
one in which the entropy is kept constant;Adding
a particle
to a system at
shan
a finite temperature
tends
to increase its entropy unless we can keep eachsystem
of the ensemble
in a definite, although new, quantum state.There
is no natural
defmtiton
the
E) or F),
laboratory
process by which this can be done.Hcnee
in
which
the chemical
is
as
the
in
free
expressed
energy
per
change
potential
added particle under conditions of constant temperature,
is operationally
the
~
We point out that
will not give U
(85)
simpler.
/tN on integration,because
is a function
of N; compare with
H{N,c,V)
{9.13}.
a. Operationally,
12.
Ascent
in a
uppermost
0.9. The
concentration
of
in air
are
leaves
maximum
the
lhal
the
containing
to which
height
stand
rools
in a
waier vapor at a
relative humidity
temperature
in the
water
concentration
water.
13.
(a) Show
expansion,
hentropic
as a function only of
show ihat xVin is constant in an
expressed
the
expansion
gas
(b) From
occupancies,
isentropic
idea!
of an
can
be
this result
idea! monatomic
gas.
14.
infinite
of
binding
Multiple
molecules.
Assume
distance.
Oi.
is
the
A hemoglobin
bound
ofeach
absolute
activity
that one
exp(ji/T}
of
the
free Oi (in
ts the
Sketch
moiecule?
hemoglobin
probabiiity
four
Uiui
What
result
also.
15.
chemical potential.
External
N atoms
of mass M
potentialat
value
of the
the
surface
in
volume
of
tola! chemical
Consider a
t.
temperature
with
chemical
the
(a) Prove carefully atid honestly that
V. Let
the earth,
at
system
potential for
identical
system
when
translated
to altitude h is
p(h) =
where
applicable
g is
Mgh
that
Chapter
Ideal Gas
DISTRIBUTION
BOSE-EINSTEIN
153
FUNCTION
DISTRIBUTION
FERMI-DIRAC
157
FUNCTION
CLASSICALLIMIT
Potential
Chemicai
Free
160
161
163
Energy
Pressure
16-\",
Energy
164
Entropy
165
Heat Capacity
165
Testsof
Example:Experimental
Chemtcai
Potential of Ideal Gas
Sackur-Tetrode
the
with
in
Isothermal
Zero
internal
167
Equation
Degrees
\342\226\240
Field
Magnetic
169
of Freedom
J70
17'i
Expansion
IT.t
i \025
SUMMARY
176
PROBLEMS
177
1. Derivative
of Fenni-DiracFunction
2.
of Filled
3.
Symmetry
177
Function
Distribution
177
Double
Occupancy
Relativistic
Particles
4. Energy of Gasof Extreme
for
an
5. Integration of the Thcrmodynamic Identity
6. Entropy of Mining
7. Relation
of Pressure and Energy Densily
8. Time
for a Large Fluctuation
Gas
of Atoms
with Internal Degree of Freedom
<J,
10. Isentropic
Relations
11. Convcelive
\\2.
Ideal
Gas
of
Ideal
isentropic Equilibrium
iit Two
Piitu'itsiuns
Diesel
Engine
Compression
Gas
of
the
177
Statistics
Atmosphere
177
Ideal
Gas
177
17S
i
7S
17S
17')
179
J~0
1^'
1SU
ISO
ISO
Chapter 6: IdealGai
The
is a
gas
of particleslh;it
distribution
the orbital.
function,
An
orbital
is a stale of [he
terns is widely usedparticularly
!fthc
one
only
to approximate
of A' particles
system
particle.
sin
exact
quantum
in
terms
of an
by assigning the
This
between particles
interactions
us
we construct
thai
state
approximate quantum
as /(ej./i),
designated
usually
The thermal
orbital.
an
occupy
panicles
state
approxi-
lo
orbituls,
composed
an
of
each of spin j,
An
aloin
of 4He
odd
so
of
number
must
Hie
that
has one
particles\342\200\2242
have
2 protons,
electrons,
spin and
half-integral
an
even
I neutron-
must be a fermion.
number
of panicles
as
appear
particles
An
can
orbital
be occupied
species,
An orbital
The second
rule
of
occupancies
of any
by any integral
zero.
including
2.
rules:
occupancy
can be
is a
need
occupied by
statement
not be
0 or!
of the
fermion
same species.
of the
Pault exclusionprinciple.Thermalaverages
but
integral or half-integral,
the
the
other
orbital
rule.
occupancies
Distribution
Fa-mt-Dirac
The
different
two
occupancy
there
each orbital:
boson
is
Function
sums
Gibbs
different
values of the
for
occu-
orbital
= 0 or N = !
N
fermion sum in which
Different
only.
Gibbs
sums
lead to different quantum distributionfunctions
for the
/{e.t./i)
thermal average occupancy. Ifconditions are such
\302\253
it
will
notmaitcr
that/
1,
whether the occupancies N = 2, 3,... are excluded
or are allowed.
Thus when
<:<
I
the
and
fermion
functions
must
be
similar.
Thislimit
boson
distribution
/
in which
the orbital
with
unity is c;ii!cd the
occupancy is small in comparison
there
and
A',
occupancy
is a
classical regime.
now
We
occupancy
treat
the Fcrmi-Dimc
of an
orbital by
the
fcrmtonsand
equivalence of the
to treat
two
of famioit
particlesis
bosoti
and
absolutely
in the
functions
the properties of a
gas in
Bose-Einstein
orbital
opposite
thermal
the
for
average
function
distribution
bosotis.
We show the
occupancy, and
we
go
on
Chapter
the properties
for
by
limit of low
limil.-ln
this
in the
g;ises
cruchi
function
distribution
7 we
FERMI-DIRAC DISTRIBUTIONFUNCTION
We
a system
consider
fermion. The
of a
composed
be
may
occupied
by a
is placed
and diffusive contact with a reservoir,
in thermal
A
6.i
and
6.2.
real
Figures
system
may consist of a large numberNo of
call
it the system.
but it is very helpful to focuson one orbitaland
fcrmions,
Our
are
of
as
the
reservoir.
All
other
orbitalsofthe
real system
problem
thought
thus
out. An
is to find the thermal averageoccupancyof the orbital
singled
No
orbital can be occupiedby zero or by one fermion.
other occupancyis
be taken
will
allowed
Pault exclusion
by the
principle. The energy ofthe system
to be zero if the orbital
is occupied
The energy is c if the orbiial
is unoccupied.
one
fermion.
by
5 we have
The Gibbs sum now is simple: from (he definition in Chapter
system
as in
\302\243=
so
that
of the
*= 1 and
1 +
configuration
comes
the energy
(I)
;.exp(~f./r).
when
is e. The thermalaveragevalue
term
in
(he Gibbs
sum
with
of
N
the
occupancy
1 to
the entire
Gibbs sum:
B)
Ideal Gm
6:
Chapter
Occupied
,VQl
Figure
Wo)
6.1
fermion.
energy
log
G,,)
\302\243<*,\342\200\236
We consider
as the
The system is in thermal
of the occupied orbital
confined to
unoccupiedand
JVD
We
be
might
the
Uu
if the
reservoir
ihe
will
contain
system is occupied
JVO
by
one
average oecupancythe
5 that
Chapter
write B) in
the
a! most
by
one
at temperature
of a definite
states
may be
if the
fcrmions
t. The
sysiem is
fermion.
conventional
an
symbol
orbital
that
/(e)
of energy
e:
C)
<.V(\302\253)>.
/. = cxp(/i/i), where
is the
chemical
potential.
form
standard
-,0/r]
\"exp[(\302\243
D)
1\"
result
Tills
gives
O2
be occupied
may
from
We may
UJ _(|\302\243^-t(J^
fie) s
Recaii
*) = a{A'u.
kinetic
The reservoir
for the
introduce
I,
volume-
a fixed
fermions
denotes the
reservoir.
the
i
o(/V0
119261,
iicovcrcd.
general
and
The
itaicmenl
P. A.
M. Dirac, Proceedings
of
i!:c Royal
a'ld
cont
Functlor
Distribution
Fertni-Dhac
System
Figure
6.2
shown
here.
Sclirodinger
parliclc
equation. Ttic
loial
of noninicracling
a system
orbital
thai is a solution of
of
energy
panicles
a
single-
is
the sysiem
JVB
or 1.(b)
is ihc
number
much
Ii is
3- ~ I
Tltc
firsi
arises
scrm
+ Acxp{~ejti
=
occupancy JVH
0, aad
the second
tcnti
arises
;Vq = 1.
from
function
distribution
lies between zero and one.The Fermi-Dirac
is plotted in Figure 6.3.
In the field of solid siaie physics the chemical potential <* is often called the
Th\302\243
on the temperature.
Fermi level. Tlie chemicalpotentialusually
depends
is often written as ef; ihai
of ft at zero temperature
is,
value
of/always
Mi
We call
*
En
ilie
cF
the
Fermi
semiconduUor
Fennt
energy,
liseraiure
level.
- 0) &
not
fi(Q)
to be
ihe symbol
cF
E)
Ef.
confused* uiih
is often
used for
the
;( a! any
Fermi
lempfniurt.-.
level
which
a:-d ef i
6; Ideal Gus
Chapter
\\
A'
\\
1
........
6.3
Figure
of the
Plot
Fermi-Dkac
r. Tlie value
the temperature
function
distribution
Fermi
higher
energy
energy
/t(t).
the
are
occupied
are
unoccupied.
chemicalpotential departs
If there is an orbilalof
orbital
is exactly
by
energy
half-filled,
in
electrons
Consider
ihe
in a
a system
- p in
of
unils
metal,
ji
might
of many independent
temperature
from
/i
versus e
/(e)
the fraction
!he
of
gives
of/(c)
is !he temperaturedependent
orbiials, as in Figure6.4.At
\342\226\240~m.
-4 -3 -2 -1 0
e \342\200\224
of t
ji, in units
-5
_6
-7
Ihe Fermi
equal
to
sense
of
0, ali
7.
in Chapter
(e
*=
//),
the
F)
Orbitalsof
are
lower
less than
energy
are
more
ihan half-filled,
energy
half-filled.
the
Fermi-Dirac
distribution
distribution
function
of non-
-I
Figure
think
6.-1
of
bosons
and
ihe ideal
establish
we
then
convenient
do
with
pictorial
FUNCTION
DISTRIBUTION
boson
not
of
an
We
of the
one
the
consider
all
it
is
as we
osciiiator,
thermal
as
but
conserved,
in
by
particle wtjh
thai an orbital
and
Figure
of the
of photons
to think
did in Chapter 4.
distribution
contact
Let \302\243
denote
function
with
the
bosons
for a system of noninteracting
a reservoir. We assume the bosonsare
of a single orbital when occupied
energy
is N\302\253,
there arc N particles in ihe orbital,the energy
ireat one orbital as the system
and
view all other orbitals
when
6.5. We
value
integral
simpler
diffusive
same species.
particle;
an
way to
composed of independent
not interact with eutli oilier
3 common tcservoir.
limit.
appropriate
BOSE-EINSTEIN
iutecacl
a system
orbitalslliat
but
function
Distribution
Chapter 6: IdealGo:
as pan ofIhe
The Gibbs
reservoir.
sum
taken
for
the orbital
of particles may
number
arbitrary
Any
be in i : orbital
is
G)
The
limit
on
N should
be the
\342\200\224
A\"
provided
inequality;
Gibbs
(8)
;.cxp(-\302\243/t)
< 1. In
that
kcx.p{~t/z)
the
sum by use
of
in the
panicles
orbital is
found
from
ofE.62):
-(\342\226\240)/<]
L\342\204\242-___
__
A0)
Distribution
Bosc-\302\243insicin
Funclio
and
Fenni-Dirac
Comparison of Bose-Einsicin
for
funclions. Tlie classical regimeis aiiafoeii
\342\200\224
\302\273
where
ihe
two
distributions
become
(e
r,
/i)
nearly idciuit
We shall see in Ciiapier 7 that
in the degenerate
regime ai low
Figure 6.6
dislribuiion
chemical
ihe
temperature
potenijai
ft
at
for
high
a FD
distribution
is
lemperaiure.
Et differs
Bosc-Efnstcindistribution
function,
malhcmaticaHy
tnsicad of + i
-1
from the Fermi-Dirac distribution function
having
only
by
can
have
in the denominator.Thechange
very significant
physical consequences,
7. The
as we shall sec in Chapter
two distribution
funclions are comparedin
the two distri6.6. The ideal gas represents the limit e \342\200\224
r in which
/i \302\273
Figure
distribution
are
The
choiceof ihe
functions
approximately
equal, as discussed below.
in any
e is always arbitrary. The particularchoicemade
zero
of ihe energy
This
defines the
wiU affect
problem
ihe
difference e
\342\200\224
has
is discussed
iuriher
in
the
classical
A gas
orbital
is
/;
in
is much
\\a\\uc
to be
B0)
less than
of
dieniic.il
the
independent
/i,
potential
buE
the
of ihe
vaU:e
point
below.
regime
when
the average
number of atomsin
for
a gas
each
at room
6: Ideal
Chapter
and
Gas
Uau iuiu
liicq
reg
imcs
Class
of
parlic
Ic
Regime
___
T!Krma!
it
o CCup.iticy
i*:
ny
\342\200\224
\342\200\224\"~
III
Boson
Aluays
Fcfmioii
Close
10 bul
Boson
Orbital
of
Quantum
much
less
lhan one
lowesi
an occupancy much
greater than
one.
so
that
for occupancies of the order of one or more,
in the dassieai
is lhe
their
are
identical.
The
regime
quantum
regiir.e
equilibrium properties
These characteristic
features are summarized
opposite of the classical
regime.
arise
oniy
6.L
Table
in
LIMIT
CLASSICAL
ideal
An
gas
regime.
acting
is defined
the
within
We develop
box.
the properties
the
use
of the
particles.
functions
where
The Fermi-Dirac
func-
distribution
are
lhe plus
sign is
for
the
FD
distribution.In orderthal/(c)
must have in
this
classical
be
distribution
much
smaller
and
th;m
regime
exp[(e-//)/r]\302\273l.,-
A2)
of ail
of (tt).
orhiiat of energy r.
/. hs
wiih
this inequality
e. When
all
for
denominator
exp(/j/r).
function. !t is
functions when
the
always
be a
occupancy
average
/(i.)
The
limiting
cxp[{/i
result
the
of
A3)
Fcrmi-Dirac
/(s)
occupancy
average
dfstnbulion
and Bosc-Einstein distribution
the classical
is called
is very
small
in
with
comparison
Equation
A3),
unity.
described
by quantum
involves
the
in
is
limit
the
+!
term
the
for
particles
for
or
/.i
h cannot
classical theory.
thermal
entropy,
= Aexp(-r/i) to
of
topics
study
classical
of
the
the
importance:
relation,
terms
of the
properties
function /(r)
distribution
classical
the
use
We
the
in
Chemical Potential
The chemical
of total number
is
potential
of atoms
the
that the
the condition
from
found
equals the
number of atomsknown
distribution
thermal average
to
be
present.
function/(eJ:
N =
A4)
of atoms
in
each
orbital.
We useA3)
rn
A4)
to obtain
AS)
JV-/yexp(-\302\243,/T).
To evaluate
is
just
the
this
partition
sum,
observe
function
that
the summation
Zx for a
single
free
in
volume
V, whence
Chapter 6: Idea!Gils
In
shown that Zt
3 it was
Chapter
where
HqV,
nQ
rs the
(Mrjlnh2K11
quantum concentration.Thus
A'
;.Z,
number
of the
terms
in
density
is
n;nQ
\302\253I.
out to
A7)
j
volume
quantum
of the ideal
potential
=\302\273
T
l/nQ. in the
monatomic
(IS)
tog(n/iiQ)
result
The
may
he written
give
i[)ogN
see
as
log
(IS) for
atoms
\\\\;i\\e
spin
spin ;:iuliipiidiy^S
is JoublcJ; nQ will
an
added
lo sevcra!
be subject
can
examples.
h3\\c
as the concentrationincreasesand
(lie chemica!polentiaf
wifl
A9)
the temperature
(b) If lite
+ *SogBn/i2/A-/)]-
Jiogt
potential increases
increases.
the chemical
that
decreases
(a)
A6)
the
chemical
The
i?/hq
wiih E.12a)
\302\253
We
nftiQ
in
atoms
P
in agreement
exp(/i/T)
of
W/i?QK
Finally,
NJV.
\302\253=
number
to the
is equal
classicalregime
gas is
which
;. =
/.,,QK;
S, the
=.
an energy
of at
\\
ferm -rlog2.
(he
zero
of the
in ihe
sum in(iS)
and
by
Tile tfTctt
kinetic
B0)
il isdiJublcdLlhevalucof
t\\eryw[icre
be replaced
that
+ Tlog(n/nQ).
number of orbiiafs
4- I. For s.pin
A so
e0 = 0, then
2\302\273G,
of
Shi: spin
Ihe
i\302\273
mufliplicd
iheparlition
nght-hand
by ihe
fund ion Z^
side of{18)
on She enSropy is
Srcalcd
below.
fc)
t^e
enter
ihe
iiitern^J
partition
energy
ro^itionaj
potential
-ind
wilt
free
Energy
have
Free
an added
term
Energy
chemical
The
is related to
potential
free
the
= n ,
(CF/dhr)t_y
where
so
the integrand
by
energy
B1)
this,
is found
B2)
\342\200\242\342\226\240\342\226\240],
Mow Jt/.vlog.v
in A9).
brackets
in
[log <V
tJ^N
j*JN}j{N,t,V}
= xlog x
\342\200\224
x,
[hat
- iVi[logW -
Comment:
Thus, from
The
integral
Wr[iog(n/nQ)
concentration
should
in B2)
- Jlogr + JlogBn/iVA')]
fog V
be
strictly
C3)
B-t)
1].
and
decreases
a sum,
because
with
A'
is a
temperature.
discrete
variable.
E.6),
f(N,r,l')
integral
f. log.V
only
in ihc
= Iog(l x 2
lenn
in
log
B5)
Ji(-V)
,V in
A9), for
= iog/V!
\342\226\240
\342\226\240\342\226\240
N)
B6)
ChapM6:UtaICai
the
wHcfg
A1
\302\2433\\e
inic^EiiI
\342\200\224
_V in
log A'
B3).
log,V! ~
may be
Bui for
MogN -
she Stifling
targe
approximation
B7)
as B3).
same
Pressure
The pressure
is relatedto the
With B3)
F we
for
free
by C.49):
energy
ha
Nt/V;
which
is the
pV
in
Chapter
Nz
B9)
3.
Energy
energy U is found
The thermal
U-F
With B3)
for F
we
ta-F~
from
U ~
t(cFi<\"t)|.,\302\273
-t:
C0)
'
CD
have
2t
so that for
or
iff,
an ideal gas
C2)
The
factor
| arises
from
the
exponent
of x
in
because
\302\253Q
the
gas
is in three
dimensions;
if
in Chapter 3.
iiq
were
in one
Heat
has rotational
molecule
polyatomic
and
degrees of freedom,
the
Capacity
average
energy
Enlropy
The
is related
enlropy
to the free
From B3)
for
This is idenlica!
lhiil
so
\\o^n0/n)
for the
equation
C.76).
In the
is positive.
absolute
historically and is
of an ideal gas:
result
earlier
our
with
\302\253
1,
[33)
-(oFJdT)v,K.
the entropy
have
we
energy by
of
entropy
lhe
idea! gas. It is
a monatomic
Siickur-Tflrode
imporiani
in
of chemical reactions. Even
thermodynamics
though the equation containsh, the result was inferred from experiments on
in chemical
rcaclions iong before the
v;ipor pressureand on equilibrium
it was a greal challenge to
quantum-mechanicalbasiswas fuliy understood,
theoretical
unsuccessful
the
essential
physicists
to
attempts
to do
explain
the
Sackur-Tetrode
so were made in
the
equation,
early
years
and
many
un-
of this century. We
of the
size
concentration-
valve is
at constant
system: the entropy islinear in the numberofparticles,
increases
when the
If the gases are not identical,the
entropy
opened (Problem6).
Heat
Capacity
The
heat
capacity
at constant
volume is defined
in
Chapter
3 as
C5)
Chapter6: IdealGos
for
the expression
wlien
derivative
the
calculate
can
We
is
nQ
directly
idea!
gas
out:
wn'tien
IE
From this,
idea!
an
for
gas
C6)
or Cy
be added
must
units.
conventional
The heat
heat
in
%NkB
discussed
p, as
pressure
xda
to
needed
because
C\302\245
expand
in
detail
in
additional
the volume of
8. We
Chapter
the
use
-f pdV to obtain
dU
/eu
C7)
The
of
energy
ideal
an
gas depends
Q. + N
C, =
in
fundamental
or
uniis,
C,
in
capacities
have
as R,
We
units.
conventional
in
the
two
notice
systems
C,
again
of units.
C8b)
Nk,
is
usually
written
The resultsC8a,b)
are
decrees
C8a)
of freedom
of a
for
written
an
ideal gas
c,
= In + n
= |,v
\342\200\224
:N,
so
that
C8c)
Heat
units, or
in fundamental
Cp
units. The
in conventional
Example;
from
found
\302\273
C8d)
$NkB
of the
tests
Experimental
are oflen
entropy
Capacity
Sackur-TeiroJc
gamma.
values
experiment!
letter
Greek
the
ihe
of
of C7)
C9)
Here <j@)
ihe
denotes
at the lowest
entropy
temperature attained
in
rhe
measurements
Enlropy increase on
1.
2.
of thermodynamics
law
solid
healing
Entropy
increase
in ihe
.1.
Entropy
increase
on hearing
4.
Lntropy
increase
in ihe
5.
Enlropy
change
absolufe
from
transformation (discussedin
solid-to-liquid
liquid
from
niching
[mini to ihe
point.
10).
Chapter
boiling point.
liquid-to-gas transformation.
on heating
gas from
the
point
boiling
to ihe
pressure.
There
may
further
of experimental
We
enlropy
I.
be a
lo C4)
corrctiion
slight
and theoretical
values have
comparison
for
for ihe
now
been
nonidcalilyoflhe gas.Comparisons
out for many gases,and
carried
neon,
oflhe conventionalentropy
very
of Clusius.The
=s kua.
M.55 K
The heat capacity of ihe solid was measured from 12.3K to the melting
point
The heat capacily of ihe solid below I2.3K was
under one atmosphereof pressure.
zero of the me^iuceslimaicd
by a Debyc law (Chapier 4) extrapolation to absolute
found
of
ihe
at
is
menlsaboie IJJK.Theeniiopy
solid
the melting point
bj nuir.e.'tcal
of UlTiCp/T) 10be
inlcgralion
5lolid
\342\200\242
A classic
ihe American
=,
Society
i4.29Jmor'K~t.
oxygen
51.2300 A939).
from
12 K to
its
boding
point
,ind
its hiat
of
Chapter 6:
idcutGa:
1
able
xaluaot
wide
uropy ullli c
Enlropy
r.lp,lnK
Gas
Nl-
212
Ar
87.29
Kr
119.93
sul'rce:
hc.it
associated enlropy
The
3.
point
to mc!l
required
inpul
The
of melling
heat
The
mol\021.
associaied
The cxpertmenlal
sphere adds up to
sK3i
The
^.oiid
calculafed
value
14506
labics, 6lh
cd.,
Voi
was
liquid
the
measured
atmosphereof
pressure.
K is observed
lo be 335
J mol\"'.
The
from
&SUvAi
of neon
entropy
the
poim
inching
[o ihe
increase was
The entropy
found
boiling
10 be
- a.SSJmol-'K-1.
of neon
oflheeniropy
ASmelling
value of
ai 24.55
solid
the
is
5g\302\273,
from ihe
96.45
12924
at
to vaporize ihe liquid
enlropy of vaporization is
required
input
96.40
129.75
BonMvin
ASIJ4Uid
4.
Iculalo
Ca
144.56
Lumhh
From
The
E Nperimenia
'K\"
Jmol\"
in
4, pp. 394-399.
Pan
. 2.
boilin
iiosph
96.45
gas a! 27.2K
af a
pressure
same condifions
Jmor'K\021
agreemenl
lo be 1761J
ofoneafmo-
\302\253
96.40Jmor'K\021.
ASViPQliMlion
under ihe
was observed
27.2K
is
,
with
of IdealGas
Chemical Potential
Infernal
with
of FreeJoin
Degrees
of Freedom
Degrees
\302\253
\302\243
en
to
motion of the
problem
rotational
In
classical
oscillator
is the
the transla-
sum of two
regime
of Problem '3.6.
sum for the
1
terms
in
greater
the
be
degrees of freedomand
molecule.
treated
r.n
vibrational
n is
orbital
;.exp(-\302\243fl/t)
The
D1)
of ),
powers
higher
D0)
problem
the Gibbs
\302\243\302\253
where
eifli
center of massofthe
harmonic
the subject
was
energy
the
the
ts
and vibrational
rotational
the
to
refers
einl
the translations!
energy
to
addition
in
the molecule
parts,
independent
where
e of
molecule
Each
molecules.
are omitted
D2)
D3)
The
is
summation
just
the partition
function of the
internal states:
(\024)
which
is
~tlogZ;ol.
related
to the
From D3)
one
molecule
by
/\"in,
the Gibbssum is
D5)
Gas
6: Idea!
Chapter
The probability
the state of
in
the
to
the
that
of
Several
tlie
(a)
the molecule,
sum 3-:
Gibbs
analogous to
n is occupied, irrespective of
is given by the ratio
of the term
orbita!
transtationat
motion
internal
the
for
A3)
\302\253
i. The
/(\302\243\342\200\236)
ease, but
monatomic
results
the
as
earlier
defined
XZinl
now
D6) is entirely
the role of A.
result
plays
for
ideal gas:
polyatomic
Equation
is replaced
for,*
A7)
by
D7}
with
<iq
defined
as before
exactly
ideal gas
monatomic
(We shall
of atoms with
zero
Because
for
e\\p(/i/i)
the
we
have
p. =
(b)
The free
~
r[log(ri/nQ)
energy is increasedby,
for
IogZiol].
D8)
JV molecules.
D9)
(c)
Thecniropy
is increasedby
E0)
The former
Example:
Spin
represcnl
boih
resuU U
enmtpy
\342\200\224
jh'z
10 die
energy alone.
iranslalional
in zero
electronic
applies
of Spin /,
funciion
partition
atom
where /
may
associaied
the
with
is
alone
spin
ZiM =
this
the number
being
of independent
{2/ + t) ,
spin siaics.The
the
entropy
spin
E0).
TheefTec!
of the spin
Isothermal
The
to the
is the
x !0Jcm\\
gas
the
What
The
initial
of D8):
E4)
I)].
pV
at an initial volume of
of 4He
at constant
The temperature is
temperature
constant
maintained
reversible
the
expansion
\342\200\224
S'x
we
see
final
until
by
system
the
thermal
ai
any
is equal
temperature
that
is
pressure.
increase of entropy
an
an
of
ideal
at
entropy
gas
is the
a(V) =
expansion?
constant
A'log
= (ix
4-
constant
on
volume
as
E5)
l0\{0.69?)")
same temperature.
depends
temperature
= jVIog2
slowly
expand
one-half
is found
after expansion?
is twice
the initial volume; the
pressure
volume
final
E3)
logBi
atoms
1022
1) .
Expansion
E2)
1) ,
logB/
}i = T[Iog(n/ii0)-
Reversible
free energy is
is
\302\273,.,
by
to the
contribution
spin
Fial = -tlogB/+
and
E1)
*=
0.069
because
the smaller
the
1033.
E6)
system
h.TS
volume at the
Work
6.7
Figure
is done
by
(he
gas in
an isothermal
work is done by
How much
When
Figure
at
little
the
gas
the
ht the
gas
isothermally,
expands
work done
The
6.7.
a time.
expansion ?
it
work
does
from
directly as4.!4 x
30serg=
W as
the work
\302\253
DJ.4J){0.693)
the work
Thus
43.4J.
done on the
E7),
Ni!og2
We
in
E7)
Ntlog2.
H\\NxjV)dV
pistonis,
as
We evaluate/Vt
a piston,
against
is reversibleentersin
determines
p at
w=
2S.7J.
gas
on the
E8)
E7)
when
we assume
external
piston. From
-jpdV= -28.7J.
agencies.
This
is the
E8),
E9)
ruble
What is the
in ihe
changeof energy
expansion?
of an idea! monatomicgas is U
The energy
an
at constant
expansion
decreases
temperature.
which is the work
by Afilog2,
*=
mt Entropy
Expai
and
jNx
not change
does
in
energy
S.
Chapter
much heal
Q +
seen
have
We
0. Thus
Q =
result
the
from
Reversible
We
the
at Constant
Expansion
expands
insulated container.
reversibly
No heal
to
flow
is constant in a system
The entropy
processis
Entropy
an expansion
above
gas
F0)
E9).
considered
that
28.7 J ,
out
carried
or
isolated
(slowly).
reversibly
is permitted, so that Q = 0.
the reservoir if the expansion
from
of entropy
A process without a cluvnge
the gas
from
is called
adiabaticprocess.
has
is
an isentroplc process or an
the specific meaning that
there
we
simplicity,
stick
shall
term
The
no
heat
transfer
in the
\"adiabalic\"
process. For
wilh\"isentropic.\"
on
volume
the
and ihe
temperature as
constant
remains
at
constant
eniropy
'
Tl3'2f,
for
an
ideal
monatomic
gas.
+ constant)
logK
F1)
if
t3/2K =
constant;
Iogt3/2K=
In an expansion
N{iogT3;I
from
V1
to
V%
constant.
F2)
have
we
= rivlV1
F3)
.
Chapter6: IdealGas
idea! gas
the
use
We
V
law pV =
forms. We
alternate
two
obtain
to
Nz
insert
Nxjp into
F4)
r =
insert
we
Similarly,
to obtain
pV/N in F3)
F5)
BothF4)
and
hold
F5)
for
an iscnlropic
monatomic gas.
an ideal gas of
motion {rotations, vibrations). We obtain
to
10
Problem
internal
with
molecules
for a
only
It is ihe subjectof
of
degrees
these
generalize
results for
process
F7)
t.'\"'\"\"'V. =r2\"\"-
Here'/ s
is
Cp/Cy
the
ratio
of the
volume.
constant
With
Tx
- 300K and
Vs/V2
find from
|- we
F3):
\302\253
189
Tt\\k is
ihe
is cooled
in
final
the
expansion
Tt
Expansionat constant
What
is
ihe
change
the
after
temperature
hi energy
300
is
entropy
in ihe
an
\302\243/,=
189 K
at constant
- !!IK.
method
important
G0)
of refrigeration.
expansion?
F9)
by
process
- Tt =
expansion
K.
Cy{x2
the
temperature
r2 -
change
r,) ,
G0). For
an
G1)
fi
or, in
conventional
Expansion
into
units,
ut =ivA-B{ra- r,)
a2-
\302\273i(l
=\302\273
-2.3
10IZ)(j.38
JO\0216ergK\"!){-IHK)
\302\273
-231
108erg
G2)
decreases in an expansion
at constant
entropy. The work done by
to
the
decrease
in
of
equal
energy the gas, which is Ul - U2 = 23 J.
The energy
the
is
gas
Let
Vacuum
gas expand
a Hn:t!vohmicof 2 liters.Thisis an
is opened
a hole
When
in
the
excellent
an
from
of an
cxiimpfe
to
process.
of I liter
irreversible
ihc expansion,
to permit
partition
volume
initial
the first
moms
the hole
through
walls is
there
work
Zero
work
the
is
What
is zero
the
so that the
of all irreversibleprocesses,but
for expansion into a vacuum.
a characteristic
necessarily
after expansion?
temperature
What
the
change
The increase
of entropy
the
in
expansion
at constant
doubled
temperature
is given by E6):
Au
a2
into a
Expansion into a vacuum
For
most
the expansion
probable
(equilibrium)
a,
vacuum
is
- Nlog2 =
2
not
0.069
1023.
G3)
= 0.
a reversible
configuration
process: the
system is not
in
the
'
Gas
Idea!
ChapterS:
Reversible ]
isothermal
t-
y
0
expansion j
I-
A'rtog-
-.Vtlog-^
Nlog^
Reversible
]
]
isentropic
expansion
-J.Vt,I-(\302\243)
L.
\\vi/
Irreversible
\021
into
expansion
y
0
vacuum
Wlog
\342\200\224
'
before removal of the partition and the final conare most probable configuraiions. Al intermediate
configuration
equilibration
the distribution
in concentration
and kinetic energy
of atoms
between
stages
the two regions into which
the
divided
does
is
not
system
correspond to an
distribution.
The central
results of these calculationsare sumequilibrium
the
initial
configuraiion
after
6.3.
in Table
summarized
LAW
GAS
(a) /(e) =
LEADING TO THE
STEPS
SUMMARY:
GAS
MONATOMIC
SPINLESS
FOR
IDEAL
Aexp(-\302\243/r)
of an
Occupancy
limit
classical
(b)
(c)
=\342\200\224-\342\200\224-\342\200\224~~~
Given
e*P(-\302\243nA)
=
-\342\200\224-177x73
Energy
'j
X!CXP(\342\200\224\302\243JT)
\"
this
N,
-[n the
dassical
of a
Ik
'/ii
j
n2
exp(\342\200\224e/t)
Transformation
equation
determines
limit.
free particle
n
number
quantum
volume
(d)
of/(\302\243)
the
in
\302\253
1.
En
orbital
orbital of
in a
cube of
V.
of the
sum to
an
integral.
(e)
X =
N/nQV
(f)
nQ
= {Mi/27rfi2K/2
(d) after
in (b).
. concentration.
(g)
T!og(ll,'!!Q)
(h) F
(i) p
- -icFfcV)t,N-
J(/,V/i(.V,t,K)
1]
NiDog(tr/HU)
Nt/K
PROBLEMS
Show
steeperthe slopeof
2.
Symmetry
as
appears
the
Thus
f{fi
e = /i
Let
orbitah.
to the
ihc
at
evaluated
Fermi
the
that
ap-
/(c)
G4)
is equal
is
orbital
is occupied
is vacant.
level
so
+ 5,
that
probability
\342\200\224cf/vc
function.
Fermi-Dirac
the
that
the lower
Thus
vacant
sometimes
3.
Distribution
of
values
and
siaiist'tcs.
Let us imaginea new
an
are 0, I, and 2. The
of
orbital
occupancies
lo be 0, e,
the energy associated with
are assumed
these
occupancies
It,
which
double
for
function
in
mechanics
occupancy
the allowed
respectively.
(a) Derive
an expression for
system composed of
ensemble
is
orbital
this
at temperature
now
to the
reservoir
the
in
t and chemical
usual quantum
average
thermal
occupancy
contact
and diffusive
with
potential/t.
(b)
for
the
ensemble
occupied
the
4. Energy
particles
have
total
is 2e.
energy
of gas of extreme
p such
momenta
relativistk
that
pc
particles.
\302\273
Me2,
where
Extreme
M
is the
relativistic
parti-
/. =
particle.Thede Broglie
h/p Tor the quantum wavelength continues
to apply.
ideal
that
the mean
energy per particle ofan extreme
nonrclativistic
the
(An interesting
gas is 3t ift S pc, in contrastto ir
problem.
in Notes on Thermoby E. Fermi
variety of relativisticproblems discussed
of
wul
Suiiisiks,
Chicago Press, 1966,paperback.)
University
relation
relativistic
Show
Tor
are
ttynumU-s
5,
Integration
modynamic
of
identity
the
tlwrntodynanric
at constant
identity
for an
number of particleswe
thcr-
have
^.
X
G5,
Gas
6; Ideal
Chapter
6.
if
Relation
pressure
N log
a system
at
G6)
V.
and
of
a system
that
jV
of N atomsof type
diffusive
after
atoms
B at
A is placed
same
the
temperature
of type
is reached
equilibrium
known
in
{A
The difference
is established.
contact
and
pressure
of
(a) Show
density,
energy
contact
in thermal
a system
in
logT
results
the
in
has
been called
7.
Cv
2. The
diffusive
when
entropy
a =
entropy is
as [he entropy
eniropy increase2N log2is
ihe atoms are identical s B), show that there is no increase
by 2N log
increased
ofmixing.
gas the
Suppose
with
contact
ideal
of mixing.
Entropy
diffusive
in
an
a constant, independentof t
crj is
where
for
reservoir
a heat
with
ihat
ihe
average
pres-
is given by
G7)
of
the
(b) Show
system,
that
G8)
-r77
problem.
particles
The
result
or to an
hoids equally
p= WjlV ,
thermal
is the
where
average energy of
to the classical
regime;
long as
nonrelativistic.
8.
they
Time for
cases
in
a 0.1
are
it
holds
liter
container
wiH
We
unmix
equally
a large fluctuation.
G9)
Boitzmann
quoted
only
in a
is
and boson
to ihe
lime enormously
not
limited
particles, as
effect that
two
long compan^
to 10\"
JHe
condition.
We
shall
investigate
a related
For
(c)
system
of
number
for which
states
number of states
ofthe
frequency
(e)
Estimale
are
with
the
of
one-half
in
9. Gasof
atomicgas,
energy
system
iutermil
the atom
an
tdcal
of ideal
in an
gas
isentropic
gas.
an ideal man-
Consider
of freedom.
degree
which
for
[he oiher.
relations
hentropic
of
total number
is Ihe
of the
live
volume
V at
(c)
entropy;
energy;
10-
'
as a crude estimate
system changes.
number
of years you would expectto wait
before
all atoms
the volume,
starting from ihc equilibriumconfiguration.
one
but
A above
volume
We use this
a year?
in
the slate
which
m'th
atoms
in the
what
10lC)s\"',
volume
the
of
one-half
are anywhere
atoms
an atom is %
in the
atoms
all
are in
all atoms
estimate
container,
the
which
for
rate of
collision
the
If
(d)
collisionsof
liter
0.1
the
in
How many
liter.
0.05
of
an
r.
temperature
(t|> pic.^uic;
changes for
process satisfy
(SO)
where
=
these relations apply even
CpjCv\\
of
freedom,
(b)The isentropicand isothermal
degrees
y
BB
Show
for
that
given by
ideal gas of
Here p
//.
the
at
constant
Bs =*
~V{cp!cV)a;
idea!
gas Ba
(Ba/p)\022; ihcre
of
molecules
mass
= yp; B,
is very
M
iittie
= p.
heat
we have
is the massdensity.
Convcaire
of
an
iscntropk
troposphere\342\200\224is
atmosphere\342\200\224the
entropy,
equilibrium of the
not
constant
The
if
bulk
internai
are defined as
have
molecules
the
moduli
(81)
-V(dp/dV)t.
of
velocity
transfer
sound
in a sound
p = pi/M,
so
that
in a gas is
wave. For an
=
(yr/'A/I''
temperature.
\\\\\\
such
equilibrium
p\\\"'
is
Chapter6: IdealGas
gradient is greater than the isentrapic
temperature
be
unstabic
with respect to convection.
may
actual
the
If
atmosphere
in
Gibbi
13.
Chapter
is 3in
an
(b) Find
{a)
V in
diffusive
With
coniact
P(N} =
Hie
expression
a. The
the
(c)
X P(N) = 1
r.
Zs ^
of
help
ideal
there
probability
gas
of
arc
;V
from
(i>QV)sf,\\\\
atoms
identical
atoms
<N/exp(-<N\302\273/N!
temperature is
in
Hie gas
wiih a reservoir is
which
previously as <N) =
N atonis
volume
an
the entropy
for
expression
with
the
potential of an ideal
ihe chemical
Find
(a)
dimensions,
spin is zero,
L2. The
(c) Find
dimensions,
two
gradient,
Confirm
that
and
(82)
Here
<jY> is the
we have
evaluated
C).
{Appendix
volume,
which
<N>.
ideal monatomic
of an
gas ai
gas calculations. Consider one mole
300K and 1atm. First,let the gas expand
and
to
twice
isothermally
revcrstbly
an
let
the initial
Hits be followed by
volume;
second,
iseniropic expansionfrom
io four limes ihe initial volume, (a) How much
heat
is added io
iwice
(in joules)
at ihe end of
the gas in each of these two processes? (b) Whai
is ihe temperature
is replaced
the second process?Supposethe first process
by an irreversible
a
(c) What
expansioninto a vacuum, to total volume twice the initial volume,
in joules per kelvin?
is ihe increase of emropy in ihe irreversible
expansion,
14, Ideal
15, Diesel
engine
in
engine
so
which,
compression.
fuel is
compressed
highly
initial temperature of
maximum
y
diesel
engine
is an
internal combustion
i sen tropically
from an
that the air in the cylindersis compressed
If
ratio
is
what
is the
the
27\302\260C C00
15,
compression
K).
the
is
healed
\302\260C
to
which
air
in
the
by
compression?
temperature
fuel. Assume
Take
1.4.
Chapter
Fermi
183
GAS
FERMI
Slale of
Ground
Density
of Electron Gas
Heal Capacity
FermiGas
IS9
194
Metals
in
Stars
Dwarf
White
185
1S6
Simcs
of
Nuclear Mailer
BOSON
of
Spacing
199
199
Chemical Potential
Example:
19S
CONDENSATION
EINSTEIN
AND
GAS
196
'
and Second
Lowest
Lowest Orbilals
of FreeAtoms
Orbital
201
Versus
Occupancy
202
Temperature
205
Einstein CondensationTemperature
207
\"He
Liquid
Quasiparticles
and
212
*He
Superfluidity,
Phases of
Superfluid
210
of Helium
Relations
Phase
217
3He
SUMMARY
217
PROBLEMS
218
1. Density
2. Energy
3.
Pressure
Versus
Potential
Mass-Radius
for
Relationship
Heat
Energy,
Gas
Boson
219
Fermi Gas
219
Temperature
White
7. Photon Condensation
8.
9.
218
219
as a Fermi Gas
5. Liquid'He
6.
of Degenerate
Entropy
4. Chemical
218
Dimensions
Capacity,
in One
and
Entropy
Dwarfs
219
221
221
222
Dimension
Stars
10. Relativistic White
Dwarf
!!. Fluctuationsin a FermiGas
222
12.
222
Fluctuations
13. Chemical
14.
Two
Orbital
in
222
a Bose.Gas
222
Potentia! VersusConcentration
Boson
System
223
It is
and molecules,areeither
regime
the
which
in
They behave
bosons.
or
fermions
is small
concentration
all particles,
that
theory
in
including
atoms
comparison
the
quantum
concentration,
(i
Whenever n >
the
iiq
gas
\302\253
ifQ
to be
is said
A)
(Mt/2tt/ijK'2.
the
in
regime
quantum
is called a
and
quaniutn
gas.
properties between a quantum gas of
ions
a gas in the classical
lemi
and one of bosons is dramatic, and boih are unlike
A
low
has a high kineticenergy,
low
heal
regime. Fermi
gas or liquid
capacity,
a high
and
exerts
magnetic susceptibility, low interparticle collisionrate,
at
absolute
zero,
A Bose gas or liquid has a
pressure on the container, even
\342\200\224
of
concentration
in the ground orbital, and these particles
high
panicles
Bose
the
called
in physical
difference
The
a superfluid,
as
act
condensate-\342\200\224may
with
practically
zero
viscosity.
For many
important variable.The
is
obtains
regime
quantum
fixed,
is
the temperature
when
the temperature
and
the
is
below
t0 s
n ~
by the
condiiion
is often
said to
be a degenerate gas*.
realized
defined
was
by
Nernst
iiq. A
that
B)
{2nh2/M)n213,
gas
in
theentropy
the
quantum
regime
with r
\302\253
ro
both
fermion
boson
and
theory removes the difficulty:
-+
a
the
i
so
that
0,
gases approach
unique ground stateas
entropy goes to
zero.We say that ilie entropy is squeezed out on cooliuga quantum
(see
gas
3 and S).
Problems
in the classical regime{Chapter6) the thermal
number
of particles
average
as
t -*
in
an
0. Quantum
orbital
of energy
\302\243
h
given
by
appropriateto
this
regime,
J{z)
with
the usual
The
form
assures
D)
<it/nQt which is
is any
fcrniion
spin.
occupancy
low
0 or
of
I,
it is
temperatures
by ihe
zero
the classicalregime.
a half-iniegra!
composite\342\200\224with
all orbitals
energy below
<
with
are
there
which
just
fermitm
one
have
eF will be
e <
occu-
orbital
these limits. Ai
between
anywhere
is always
orbital
average
lowest orbital.
of the
energy
picture of
original
or
orbital. At absolute
I. Here ef is the
in each
with
an
with
D)
occupancy of any
panicle\342\200\224elementary
is limited
fermion
our
with
\302\253!,consistent
the
for
the average
us that
(n/HG)exp(-\302\243/i)
occupied
orbitals
enough
to hold the
number
population only
contain
each excited
and
slowly,
a
of
orbital
orbital\342\200\224any
small number
relaiively
to the
assigned
ofparticles
of particles.
We
higher
energy\342\204\242will
this
discuss
shall
feature,
carefully. Above r = r0 the ground orbital losesits special
becomes much like that
of any
excited orbital.
occupancy
low-lying
Fermi
is called
gas
Fermi
ihe
with
energy.
regime
the
ihe
in
will
Chapter
The
compared
The
most
striking
vacant.
entirely
Fermi
with
gas
the
is said
Fermi
is occupied
orbital
An
to be
energy,
as
no udegenerate
in
the
classical
6.
unportam
applications
conduction
electrons in metals,
matter.
be almost
one fermton.
ishigli
temperature
treated
energy
it contains
when
fully
its
GAS
FERMI
A
point
;md
include
nuclear
energy
level f, for
Fermi
16 eleclrons;in
60
\342\226\240|
gTOUnd
\"a
slalc
Hie
the
(!6orbilals) are
occupied
(a)
(a) The
to a fine of
7.1
Figure
confined
energiesof
spin
down,
n = i,2
10for an etecfron
level correspondsto two orbitafs, one for
The ground siaicof a system
of t6 electrons.
orbhals
the
L. Each
lenglh
(b)
shaded region
in the
vacant
are
Slate.
ground
that
it Is necessary
ground state of the system at absolutezero.Suppose
to accommodate N nomnteracting electronstn a length L in one dimension.
What orbitals will be occupied
in the ground state of the N electron system?
of the
In a one-dtmenstonal
is a positive
form
the
crystal
integer
stn{fJ7ix/L)
number ms
If the
(i
other
Any
filling
we
and
3, 4
1, 2,
fill
higher
tire
with
in,
orbitals
in Figure
then
7.1.
electrons
in
the
ground
and
fiHed,
a higher
from
starting
with
the
in
are
\302\261\302\243
gives
arrangement
orbitals
by
supplemented
it,
the
spin
quantum
spin down.
up or
spin
8 electrons,
has
system
empty.
state
\342\200\224 for
\302\261
j-
of a
number
quantum
it
until
ground
all
the orbttais
state
the orbitais
of higher n are
energy. To constructthe
at
the
botiom,
N electrons
with
and we
ground
continue
are accommodated.
are
Fermi Gas in
in Thtee
G&s
Dimensions
Dimensions
Three
Let
E)
<5)
Here
the
radius
filled
and
is
tiF
separates
of a
to
up
nF determined
of the
system
factor|
in
because
arises
the
n, = {lNfn)ll\\
F)
triplets
only
to be
are
space
ihai
\302\273r)
tty,
an electron
because
2 arises
factor
nx,
N electrons
hold
by
The
integers
to
sphere
We may
is 4nn//3.
then write E) as
This
Fermi
the
relates
so-called \"Fermi
total
The
energy
[/\342\200\236
with
En
with
F),
have
e,
\302\243
2 x
conversion
N/V
n. The
| x
In (8)
471
\\^r
eln n2
eB *= --1
j j
P'
(in
\302\273a
,
(S)
let
21
in the
electron concentration
(h2/2m)(n}t/LJ.
we
to the
energy
(9)
(\342\226\240\342\226\240\342\226\240)->
2(fcX4n)
JdrtirV-)
integral.
Integration
l0m\\L
of
(8)
gives
the total
0 10
40
30
20
60
50
in
Volume,
7,2
Figure
elecirons,
80
70
90 100
cm3
Uo
of one
mole of
volume.
versus
and is f of
The average kinetjcenergy
is UJN
per
particle
the Fermienergy
N the energy increasesas the volume
decreases
cF. At constant
so
the
to the
that
Fermi
a
contribution
(Figure
7.2),
energy
gives
repulsive
in most
metals and in white dwarf and neutron stars
binding of any material;
it is the
most
tends
important
repulsive interaction. That is, the Fermienergy
the volume. It is balanced in metals
to increase
the
Coulomb
iiltraction
by
between decuoos and ionsand in she stars by gniviimicurjS attraction.
using
and F).
E)
Density of States
Thermal
averages
rr denotes
where
the
n; and
orbita!
distribution
orbital
function,
energy
for
independent
the
quantum
problems
particle
orbital;
XR
is
the
have the
value
form
of the
quantity
A'
in
\302\243.
Then
A1)
becomes
A2)
Density of States
where
transformed to an integral by
has been
orbitais
over
sum
the
the
sub-
substitution
(\342\226\240\342\226\240\342\226\240)->
*>(eH'
\342\226\240\342\226\240)\342\226\240
A3)
Jrfs
of orbitais
number
is the
<D(\302\243}^\302\243
N{e)
=>
V. Take
for volume
A4)
(V/in2)BM/h2)il2til2
logN
and take differentials
of
The quantity dN =
log
s=
N and
(iN/lsjdt is
A5)
+ constant,
flogs
loge:
the
number
of
of energy
orbifals
between c
C(e)
is
the
counted
write
density
of
\302\251(e)as
a function
been
can
alone because
JV(\302\243)A
A7)
ZN{t)llt
The
orbitais.
throughout
(V/3n2){2m/h2)y'2F.in
(IS)
becomes
A9i
Chapter
7.3
Figure
of energy,
dimensions.
densiiy
and BaseGm
/(eVD(e)
temperature,
bm
comparison
wiih
the
7: Fermi
occupied
is small
such thai r
in
Energy, e
When
*D(e)
total
multiplied
orbilals
number
*\"\342\226\240
the disiribulion
B0}
described
Fcrmi-Dirac distributionfunction
of
probkms where we know the total number
patiides,
from
ihal
the
total
of
calculated
number
requiring
particles
value.
The total kinetic energy of ihe electrons
is
correct
where
is Ihe
f{t)
If Jhe
sysiem is
which
above
in
they
the
ground
are vacani.
in
we
B0)
Chapier
determine
be
equal
6. In
}t
by
to
Ehe
B1)
stale,
all orbitais
are filled up to
the
energy
\302\24
B2
and
ihe
energy
is
B3)
Heat
Gas
of Eleciron
Capacity
a quanliiaiive
for the
expression
of electrons
in three dimensions. The
derive
We
gas
impressive accomplishment
ideal monalomic gas the
much
lower
agreement
wiih
calcufaiionis
for
The increase
results.
theexperimemal
of N electronswhen
0 10
from
healed
i is
(he
in a
denoted
meial
an
very
agree-
of a
energy
AU
by
im-
For
excellent
gives
total
most
gas.
elecirons
follows
in
Fermi
the
perhaps
are found.
values
Gas
U{x)
system
\342\200\224
L'(Q),
whence
f{c)
is (he
energy
range.
Here
unit
AU
JjVcrfWO:)
N \"
B4)
J0\"<fcrf>(E).
of orbilals
number
the
</e/WW
B5*
J^W
Jo\342\204\242
per
by tf to obtain
{jo
use
We
The
first
electrons
fo rewrite
AU
from
- tr\\n^y0{c)+
Je(b
on
integral
B6)
B4) as
B6)
JJ
- f/dttfiiz).
ifjAttrfteW
side of
the right-hand
ef to the
bring
contributionsto !he
energy
ihe
are
eiecirons
positive.
W)
fW&iz)-
- $0
fc'M*r
The
the
and
\302\243f,
to ef
second
from orbifals
product
integral
gives
f(c)'D{c)de in the
firsi
integral
dc at
The heat
respect
to r.
capacity
of
the
electron
gas is
found on
in
differentiating
B7)
is /(e),
AU
with
whence we
Figure
7.4
of the energy of
dependence
The
fermian gas in three dimensions.
in normalized form as AU/NeT,
Temperature
a noninteracting
is plotted
energy
uhere
N is the
is ploued
\302\243\342\226\240
S; 05
^
as xjtF.
0.4
3
e/A'b,
Figure
Fermi-Dirac
7.5
graph as
the
was
energy
calculated
at which/
in uniis
of 104
for
lempcraiures,
in
ihreedimensions.Th
gas
The chemical
of temperature.
with the help of Eq.B0)and may be read
disiribuiion
= J.
ai
function
each temperature
0.6
various
10 a
Courtesy of
B. Feldman.
Heat
-Region of UcMsieraic
quantum
Capacity of
ElectronGas
gas
Rc\302\253ion
\342\200\224-^
of classic-,
\\
Figure
gas of
7.6
Piol of ihe chemical poiemiai /i versus
noninteraaing fcrmions in ihrcc c!iincisions.
can group
units of
ihc
plotting,
ji
i arc
and
temperature
for
For convenience
a
in
0.763cf.
terms to obtain
B8)
At
(he
that the
approximation
derivative df/dx
to
of interest in
lures
tempera
the
evaluate
is
large
density
integral:
Ccl S
Examinationof
suggests
that
potential ji
constant
the
when t
in
cF. We
the
graphs
\302\253
we
\302\243f
Fermi-Dtrac
B9)
hi
Figures
ignore
the
distribution
function
and
replace ;i
by
the
have then:
C0)
7;
Chapter
thai
;i is
calculated
for the
Gas
of she
potential
gasesin one
meials t/nF
and Bost
with temperature
V&riaiiors
1.1
Figure
chemical
Ftrmi
ji, for
lo cF.Thesecurves
expansions of the
closely equal
from series
number of particles in
ihe
were
integral
system.
We set
x a
follows
and
it
We
may
from
safely
B9) and
C0)
replace the
(e.- e,)/t ,
\"
that
lower limit
by
x = -ef/r
or
more.
The
inicgta!
is not
demciuary,
but
may
p,
ondilTeremhuion
of bsjih
sides uiih
rcspcci
be cvafua^d
-V
lo ihc
if
are
we
The integral*
+ iI
\342\200\242
because
-co
from ihe
it2
parameter a.
the factor
concerned
becomes
Heat Capacity
we have for
whence
when
gas,
\302\253
xf,
C4)
units,
C5)
Ctl
of orbitajs at the
the density
that
found
We
\302\253(\302\243,)
electron
free
for
if
is not
For r
gas,
the temperature
\302\253
xF
Gas
'
- WUEfU.
Cel
In conventional
electron
Electron
of
the
with
xF
eF. Do
06)
not be deceivedby
gas, hut
for r
is degenerate;
gas
= 3iV/2tf
3N/lcf
ofthe Fermi
Fermi energy i,
only
\302\273
if
(he
reference
a convenient
is in the
gas
notation
the
rF:
point.
classical regime.
C7)
in
units
conventional
there
is an
so
that
C8)
C\\,
where
A'flTF
sF. Again,
TF is
but
not an actual temperature,
only
a reference
point.
We can give a
form
of
the
result
those
electrons
in states within
specimen is heatedfrom absolutezero,chiefly
because
an energy range r ofthe Fermi level
are
excited
the FD
thermally,
over
a region
distribution function is affected
of the order of r in width, illusisofthe order
illustrated
electrons
7.3 and 7.5. Thus the number ofexcited
by Figures
r. The
of A'i/\302\243F, and
each
of these has its energy increasedapproximately
by
as
total electronic
thermal energy is thereforeofthe order
of Uci
Ni2/eF. Thus
the electronic contributionto the heat capacityis given
by
C9)
A'r/rF
is directly
which
with
the
experimental
proportional to t,
results.
in
agreement
with
the exact
result C4)
and
Chapter 7:
Bos
and
Fctmi
Cuiculaied
Table l.\\
free
eleciroi
Comiuciion
Fermi
eieclron
concemralion
NiV.
of
1.1
3.S
K
Rb
1.34
0.85
2t
2.4
1.0S
0.79
1.8
0.56
2.1
Cs
Cu
0.73
1.5
8.50
1.56
Ag
5.76
1.38
Au
5.90
1.39
7.0
5.5
5.5
the
4.7
64
6.4
electron per
valence
one
have
gold
the conduction
becomes
electron
valence
the
electron in
the
metal.
concentration
which
lattice
dimensions.
weight or from the crystal
If the conduction electronsact as a free
eF
1.8
8.2
In Metals
atoms,
energy
5.5 x 10J
3.7
2.5
10\"
[. k,
inK
4.6
atom, and
Thus
1.3 x
x 10\"
T., =
in eV
\302\243F,
Na
alkali metals
The
s~'
SV, in cm
cm'3
in
iempcratur
energy
Li
Gas
Fermi
Velocity
Fermi
gas,
the value
of she Fermi
from G):
be calculated
may
fermion
ef = {hl12m)Cn2uI!\\
Valuesof
vF at
velocity
kinetic
the
given in Table
ef are
of
and
is
^ttuy3
where
eFjkB
nt is
for
\302\253
TF
it is
defined so that
HO
.
\302\243f
of (he
Fermi \\emperatureTF ~
\\ab!e;
electron
are of
the
assumption
at
room
and below.
temperature
the sum of
(he
tn
values
The
electron.
metals
ordinary
used
the Fermi
energy
D0)
an
temperatures
many
electronic
the sum
constant
at
metals
and
contribution
a lattice
volume
may be written
as
vibration contribution. At
yi
+ At3
D2)
Na
a functio
Rb
Eleciron
Figure 7.9
TK
After
where
from C7),
capacity
Lien and N.
E. PhiJHps,
A are
Ii is
helpful
10\302\260
in cm~3
concentration,
values
Phys.
characteristic
constants
to
display
as a plot
and
is dominant
the experimental
discussed
at sufficiently
values of the
in
Chapter
jn2N/iF
4, The
iow temperatures.
y + Ax2
The intercept
the points should lieon a straight
line.
the value of y. Such a plot is shownfor potassium
in
7.9.
Figure
of y are given in Tables 7.2 and 7.3.
for then
C/Tv
Rev.
Expcrimcnlalheal
W. H.
and
10\"
D3)
at t
Observed
\342\200\224
0
gives
values
7.2
Table
heat
of monovalent
capacities
eteciron eSecironic
and free
Experiment!
metals
e electron},
Cexp),
mJmol\"'K\"
y/y0
Li
1.63
0.75
2.17
Na
1.38
1.14
1.21
2.08
1.23
Rb
2.41
1.69
1.22
Cu
3.20
0.695
197
2.36
0.50
1.39
Ag
0.646
0.65
Au
0.729
0.65
Cs
1.35
1.00
1.13
oni:
Table
7.3
values of
ExpenmenUt
Li
Be
1.63
0.17
Na
mb
y of
mcials
I Al
1.38 1.3
K
Ca
2.08 2.9
Rb
Sr
Cr
9.26
t.40 9.2
2r
Nb
Mo
2.80
7.79
2.0
Sc
Ti
107
3.35
10.2
\021
Mr
Cs
Ba
La
Ht
T*
2.7
10.
2.16
5.9
1.3
value of y
Cu
0.695
Ni
4.73
Tc
3.6
sOTE;Thc
Si
Gc
As
1.35
2.41
[3.20
7.02
Zn
Cra
0.64
0.596
In
Rh
P<!
Ae
4.9
9.42
0.646
0.638 1.69
Re
lr
Pt
Au
He
2.3
3.1
6.8
0.729
0.19
Tl
1.79 1.47
Sn
Sb
1.78
0.11
jpb
Bi
2.98 o.oos
is in
,s
fuiniihed
White Dwarf
White
dwarf
by R
Phillips
and
N. Pear
Stars
have
slars
masses
comparable
to
that
of
the
mass and
The
Sun.
2.0
x 10!3
g;
Ko = 7.0 x
radii
of white
10'\302\260cm.
O.Oi
order
are
of the
that
of
D4)
gem\023,
exceedingly
Sun. The
like
that
high, of
the
White
are
107gem\023.
oflO'1 to
order
into
ionized
entirely
degenerategas,as
Besselobserved
that
its predicted
2.0 x
3O33
estimated
as 2
radiant
energy
in
shown
below.
the
of the
path
dwarf
white
discovered.
to be
a straight
about
x 109cm by a
flux,
comparison of the
the
using
surface
of thermal
properties
temperature
ts
the
and
4.
Chapter
mass and
The
and
dwarfs
prevalent in white
lincasifithadan
to be
free electrons,
nuclei
The companion
near
be
will
the densities
under
Atoms
Stars
Dwarf
radius of Sirius B
to
lc;id
the mean
density
D5)
This extraordinarilyhigh
following words; \"Apart
reason
particular
times
100
atoms at a
10~6A3peratom.
order of 0.01 A, as
molecule
electrons
form
graviiational
In
the
temperature
the
no
dwarfs
white
has a mean
density
a volume
10\" atoms
The average
per
atom
equal
\\o
iO~30cni3pcratorn
mol\021)
of
of 0.74 A in a
separation
compared with the internuclcar
atomic
the
of hydrogen. Under conditions of such high
density
ionized
are
electrons
The
are no longer attachedto individual
nuclei.
is held togetherby
in
dwarfs
an
electron
matter
the
white
gas. The
which is the binding forcein all stars.
attraction,
the
interior
of white
dwarf stars* the electron gas is degenerate;
The
Fermi
is much
less than the Fermi energy
energy of au
ef.
cr *
discussion
\302\243ood
WinHon,
No. 2
density of 106gcni~3have
'
Other
suspicion.\"
Maanen
=s
(I06molcm\023){6
and
Van
named
the
incredibility
that
by Eddington in 1926 in
of the result, there was
appraised
higher.
Hydrogen
or
the
from
to view
densities;
have higher
was
density
1973.
as
(h2/2i}i){3n2nI13
of while
dwaif siais
is
0.5
given
is given
103Oelcetronscm~3
10~6erg
by W. K
as i
x 10s eV
Rose, Aitropkvsics,
Hotf.
by
,
D6)
characierisiic
Liquid
energy of
Fermi
7.4
\"able
of mailer
Particles
3Hc
atoms
Metal
dwarf stars
While
degenerate fsmiion
values)
Tf, in
0.3
demons
electrons
\302\253
!09
Nuclear
matter
nuctcons
Ncujron
stars
neutrons
tQ1
3 x \302\2730u
3 x 10!I
about 10' higher than in a typieal metal. The Fermi temperature zFikB of the
m the interior
electrons
is =s 3 x 109K, as in Table
7,4. The actual temperature
of a while dwarf
be
order
I0\021
K.
The
is believed
of
the
of
electron
to
gas in the
interior of a white dwarf is highly
because
the thermal energy is much
degenerate
lower
Fermi
the
than
energy.
Are
\302\243Q
This
will
\302\273
A
of
is
energy
effects
me2
* 1.
x I010cins-!):
10\"\"g)C
D7)
same
the
be significant,
is reiativistic.
NuelearMatter
We
which
state
the
consider
matter
nuclear
of matter
within nuclei.
is composed
qualiiaiively. We
estimate
here
of a
contains
A nucleons
that
nucleus
Accordingto
volume
goes
b nuclear
this
relation
as R3,
the
gas, at
fermton
degenerate
of
least
energy of
x Al!\\
x ltT13cm)
average
protons
tbenucleongas;The radius
is given by the empirical relation
the Fermi
A.3
form
The neutronsand
volume
which is proportional to
per particle
A.
The
D8)
is constant,for the
of nucleons
concentration
matter is
?
0.11
x 1039cm-3
D9)
Potential
Chemical
about
Star.Neutrons
the neutronsneed
and
concentration
of
one
protons
not
not
the
Fermi
equal
Absolute
in a
white dwarf
identical
are
Or the
of nudeons
concentration
the
Zero
Near
familiar
relation
E0)
\302\243,=\342\204\242C>r'\302\273)M
let
simplicity
number
of neutrons.
For
from D9)
as obtained
a
cm\023
\302\253\342\200\236\302\253\342\200\236\342\200\236(,\302\253
on dividing
\302\243C.17
\302\243f
x 1039
0.05
'W>n>
2. The
by
Fermi
energy is
Mev.
The average
Fermi
the
{51}
x 10\024erg \302\253
27
10\023>1/3a;0.43
to
E2)
-J
of
ihe
16 Mev
per nucleon.
BOSON
A very
GAS
remarkable
CONDENSATION
EINSTEIN
AND
effect occurs in
transitiontemperature,
of particles the system will
below
gas
of nonintcmcting
a substantial
which
fraction
bosons at a certain
of the total number
called
occupy the single orbital of lowestenergy,
the orbital of second lowest
the
other
orbital. Any
ground
orbital,
including
the
will be occupied by a relatively
same temperature
at
negligible
energy,
be
number
of particles. The total occupancy of all orbitalswill
always
equal to
the specified number of particlesin the system.
effect ts
The ground-orbital
called the Einstein
condensation.
stale
be nothing surprising to us in this result for the ground
would
There
occ
ccupaney if it were valid only below I(T14K.. This temperature is comparable
in a system
whh
orbitals
the energy spacing between the lowestand next lowest
of volume 1 cm3,as we show below. But the Eitistein condensation temperature
of
for
a gas
of fictitious
noninteracting helium atoms at the observeddensity
most
familiar
is the
is very much higher, about 3K. Helium
helium
liquid
example of Einstein condensationin action.
in
Potential
Chemical
The key
to
the
of a boson
system
Near Absolute
Einstein
at
Zero
condensation
low
temperatures.
is the
The chemical
the
stabilization
apparent
We consider
<53)
the occupancy
e obtain
i\342\226\240-+
0 the
When
Here
we
have
dial
know
the total
made
.v, which
in the
use
ground orbital at e =
of the
occupancy
of particles
number
of the
0as
total
system, so ihal
of the
*s
series expansion cxp{\342\200\224
x)
wiih
comparison
be
large.
unity,
From
x +
\342\226\240
\342\200\242
\342\200\242.
We
for otherwise
this result
we
find
E5)
asT
ForN = 1022at
-.0.
T = IK,
we
have
/i
noic
that
fromE5)
E6)
as i
~+
0.
The
chemical
potential
in a
tirar
rhc
occupancy
always
be
of every
lower
in
orbital
Cxampte;Spacingoflonat
where
n,,
n>4
are
\302\273,
integers.
positive
of free
('
of volume
a cube
in
ttrbiiuh
lowest
second
and
orbital
=\302\273
/-1
the
energy
eB1 i)
of one of
set of
the
atoms. The
Zcr
of
energy
an
is
orbital
lowest
ihe
is
E8)
1) ,
+ 1 +
ind
Near Absolute
Potential
Chemical
E9)
+ 1+1).
W
energy of
excitation
lowest
The
is
atom
the
As =*\302\243BH)e(III)
lfA/{4tie}
- 6.6 x lO'^gandi, =
= C){8.4
Ae
In
is extremely
spiining
ijtK,
iO\0211
closer to
/i]/r}
is
\342\200\224
F0)
cm,
= 2.4S x
NT30erg.
F1)
- 1.S0x KT1*K.
small,
tiiRtcuU to
it is
conceive that
and
ntucit
the
orbjia!
ground
closer
io
than
is
function.
distribution
Boltnnann
factor
exp{~A\302\243/i)
exp(-1.8
which is essentially unity.
would
first excited orbit;il
gi\\cs
much
The
(-)
x IO-3!)(9,S6)
in a
part
1
Ae/*8
units,
temperature
This
=*
an
entirely
By D)
vuluti
mK.
x 10-\")
we would
is
s I expeel that
1.S
even
I0\0211
\302\253cilte
if/t
F2)
occupancy
of tlie
the
order
However, ihe nosc-Eiiliit-'itidis.tr ibutioii
ofhii;il:
of ihe first exched
for the occupancy
only be of
dilfctcni
at
of 1.
Ae
because
\302\273
p..
of
the occupation
Thus
the
orbiial
exciied
fust
ai
mK
i:
F4)
so thai
the
5 x 10\" 13t
of
which
is very
is [datively
temperatures
simple
low
called
from
thai
are
in this
the
occupancy
particles
much
very
F2).
lower
in
is
is quiie
in
left
as
orbiial,
in ihe
exciied
be expeciedat
distribution
the atoms
orbital is/.iV
of the first
than would
The Bose-Einstein
in which
situation
are
factor
Boltzmann
cienily
the N
fraction
first
long
condensate
as
iheir
low
oibiialai
from the
sight
strange;
the ground
10i0v 10ir
ii
favors
act quiie
differently
stales.
excited
governed
Orbital Occupancy
We
fora
and
saw
in A9)
VersusTemperature
that the
of atoms
number
sum
of the
have
for
/@,t),
integral
in
F6)
the
ground
F6)
the
separated
the
in
N .
We
ofheliutn-4
is
range
energy
number
gives
sum over
of atoms
in
the
number
into
the
two
parts.
ground
of atoms
\\
\\
\\r
= 0.5
/(\342\200\242.
-\342\200\224\342\200\224
\342\200\224\342\226\240\342\200\224__
o!
7-10
Plot of Ihe boson distribution
particles present to ensure ). a I. The integral
Figure
slates
arc
gives
condensed
the
funciion
wilh sufficient
two temperatures,
of
times the density
distribution
the rest ofthe particles present
orbitals;
on
value
of No is loo large to be shown
for
ofthe
number
N. of particles in exciied
into the ground slate orbital. The
Hie plot.
The
/(e,i) as the Bose-Einstetndistributionfunction.
integral
gives only the
number of atoms in excited
orbttals
and excludes
the atoms in the ground
=
because
0.
the
function
is zero at e
To count the atoms correctly
orbital,
D(t)
we must count separately the occupancyNa of the orbital
with
e = 0. Although
in a gas of
of No may be very
the
value
large
only a singleorbitalis involved,
bosons. We shall call NQ the number of atoms in the condensed
phase and Nt
the number of atoms in the normal
phase. The whole secret of the result wluch
follows
is that
in energy
at low
to the
population
of
the system
into the
of
p to
the
first
excited
the ground
much
orbital
closer
is to the
7:
Chapter
Fermi
and Base
Gases
when
written
e - 0 is
NM=V^~,
where
as
in
E4),
in
all
excited
or, with
will
orbitals
on
depend
for
the
at
orbilal
F7)
the temperature
as tm:
increases
e/z.
zil2 which
of Nc.
dependence
of
in
Ihe
si ale
low
sufficiently
ground
temperatures
particles
a very large number. EqualionF7) tellsus that / must be very close to
wiUbe
/ is very accurately constant, becausea macwhenever
1. Then
unity
No is \302\273
to
be
for the validity
value
of
forces
closeto unity. The condition
/.
macroscopic
;V0
of the calculation is that No \302\273I, and it is not required that Ne\302\253 N, When
to small
g s\302\273
i in the integrand,
deviathe value of the integrandis insensitive
-'
deviations of a from
1 tn F8), although not in F7).
1, so that we can set /.
Ihc
gives
The
temperature
the number
At
infiniic
= U1 10
>\342\226\240
gi
F8)
is, when
). =
1,
it ton
ts
states
excited
Temperature
\\.IO6VB\\H\\3;:i
..
G0)
where
/iQ
N to
(Af r/2rr/i2)a/2
N./N
The
value
We
concentration.
divide
Nf by
orbitals:
excited
2.6l2nqV/N
G1)
2.6l2na,'n.
which
fed to G!) is valid as long as a large
\\/N
are in the ground state. A!I particles
have
to be in some
in an excited orbital or in the ground
The number in
orbital=
or
\342\200\224
of atoms
number
either
orbital,
to small
excited Orbitais is relatively
insensitive
changes in X. but the rest of
this
we must
take /.
tlie particles have to be in the ground orbital.To assure
very close to 1 as long as NQ is a large number. Even 103 is a large numberfor
Yet witliin
ihc occupancyof an orbital.
Ar/rE = 10\"fi of the transition,where
is > !015 a loins
is defined
orbilal
r\302\243
by {72) below, [he occupancy of the ground
at the concentration
of liquid 4He. Thus our argument
is highly
cm\023
accurate
at
Ar/r\302\243
10~5.
Condensation
Einstein
We
Ihe
define
Tcmperaiure
condensation
Einstein
number of aionis in
which the
atoms.
That
is,
A^frJ
\302\253
N.
temperature*
states
excited
Above
ilie
r\302\243
as
i\302\243
for
(cmperaiure
total number of
of the ground orbital is
is macroscopic. From G0)
is equal
occupancy
(he
to (he
not a macroscopicnumber;below
n the occupancy
A7 for Ne we find for the condensation temperature
witli
G2)
M \\2.6I2k
Now
Gt)
rimy
be written
as
G3)
wlicrc
is
v;irtes ;is
ii:2 a I
jV
value
of
tlic
tola!
Atademic
of atoms.
below
Ictuperiitures
T^foralomsof
in,
number
4Hc
The numberofatoms
if;, as
sliown in Figure
in
excited
orNuils
is a=3 K.
dcr W'issenschaficn,
aid
Fermi
7:
Chapter
Hose G:
1.0
\"n
0.8
\\
Superfluid
component'
\\
/
ormal
flui
\\
omponen
/
y
of the
of
ihc
i.o
0.8
Condensed
Figure7\302\273tl
\\|
0,6
0.4
0.2
proportion
No/N
pfoponion
NJN
ofaioms
The
number
of particles
No
that
note
We
N may
the
in
have
phase
said
or the
that
be
the particles in
in the
ground
temperature
VM
is
G4)
even
slightly
is given
k'elvin
the
molar
volume
in cm3
mol\021
mol\021
and
less
than te
M)
where
from {73):
form
superfluid phase.
The condensation
= 0.
{x/x\302\243?ir\\.
- Ne =
N[l
is found
orbital
ground
and
by the
the
condensed
numerical relation
G5)
= 4;
is the
molecular
weight.
thus TE = 3.1K.
Liquid4
Liquid
He
4He
The calculated
of 2.17K
2.5
2.0
\"\302\253,
t.o
0.5
Tempera!
Heat capacity
Figure 7.12
peak near
2.17
K is
of
liquid
evidence of an
*He. The
vanishingly
viscosity
by rate
small,
above
of flow
through
sharp
transition
important
determined
of
the liquid
of normal
merely becauseof
et al.
as
transition
narrow
slits is
2.6
2.4
2.2
tlte
the
often
shape
Chapter It Fermi
is normally not
condensation
The
Gases
Base
twd
in metals. A
different
superconductivity
type
of transition
been observed
has
properties
permitted for
the
in
but
fennions,
of electron
to complex
of fermions
pairs (Cooper
phases
with
pairs)
superflutd
Atoms of
3mK.
below
3He
liquid
pairs
3He have
\\ and
spin
but pairs
We
the
which
is correct.
view
mo!~', as
the
atoms
helium
tn
structure
expanded
distances.
appreciable
responsible
for
the
liquid
4He at
with
compared
of
of
the
27.6 cm3
observed
volume.
of ifie inoiar
expansion
JC__
JJCV
[3.2,
ihose
The
values
Table
temperature\342\200\224see
selvesin
gas
the
at the
liqirid
14.3-
are with
same denstly.
in
an
at
2.SK
at
4.0 K
|16,
for
observed
order
Normal liquids
of
gases
at
room
of magnitude
act
normal
quite
of those
calculated
for
the
differently.
io binding energy.
iemperaliireis dirccliyproportional
(d) The ikjuid is slablc at absolutezero
pressures
25 aim the solid is more stable.
the
ai
muter
25atnt;
nbuvc
'He
Liquid
1
as
g
I
T,
Fi\302\253iire7.13
Comparison
uuder
4He
iiqujd
onset of high
gravify
fluidify
in
K-
of rales of flow
through a fine
and B.M.
3He and
of liquid
hole.
Abraham,
fhc suddcr
Noiice
in \"He. After
or superfluidity
B. Weinsiock,
Osborne,
'lie
r'Hz
\\
D.
Pliys.
W.
Rev.75,
9S8 A949).
2.17
has
K.
quhe
inio
asionishing
which
liquid
4He enters
The viscosity
properlies.
as measuredin
flow
is
zero (Figure 7J3), and the [hernia!
conduciiviiy
is
a
supervery high. We say thai liquid 4He below Ihe [ransilion icmperalure
fluid.
we
More
denole
*He
below
ihe
transiUon
lempcralurc
precisely,
liquid
as liquid
and
He U, and we say llial liquid
He II is a mixlurc of normal Huid
of
Hie
helium
Tlte normal fluid component consisfs
Supcriiuid
coniponcnls.
of
consisis
aloms
excited
in thermally
orbiials, and the superfluid
component
life helium atoms condensed into the
orbital.
It is known lhat liie
ground
tat:e
in Ihe
in liquid 4He does not
radioacljve boson 6He in solution
part
in
3Hc
in solution
supijrflow of the latter; neither, of course,doesthe fermion
4llc kike part in ihe super/low.
We speak of liquid \"Mle
as liquid ik i.
;ihovc
liie
iransilion
leniper^lnrc
Thereis no supcrdnid
in Ikjuid
lie 1, for here the grama! oihii;il
coiliponcnt
of uKiyuiiude as ihe oct.'up:mt;y
is ucgti^ihlc,
order
ot-vupiuicy
being uf l\\ic suim:
experiment*
fliii.ls
ofiliirftciil
Bic.isufi;
is essenlially
visttiMlics,
the .ivct.igc of
K'ii,
sums
i)f 'be
c\\fKfinn:liii
aierjgt*
iiicisuic
lluidiiy.
ifJiraif(Jj;t;
i imnily.
.t\302\273Juliet
l'vjil'Ijjjk'j
Kjurc
7.14
The mcUing
curve of liquid
and
sispcrliow
ptopciiics
as a
consequence of Uic
this gcaph
boiling
curve is
as ii would
pressuic line.After
19,626E950).
C.
in
included
not
[he zcco
wjih
ractgc
Phys. lev.
A. Swenson,
of any other
in which
temperature
liquid
seen. The
we have
as
orbital,
low-iying
He { and
regions of pressureand
in
7,14.
Figure
aloms
among
aloms
[he
that il is [he
show
calculations
cal-
condensed
The
phase
of
diagram
4He
was shown
can be followed
from
any appearance
of the solid. Al
called He I, makes
II.
He
A temperature
Ihe
transit
ion
called
the/
in
Figure
poinl of 5.2 K
crilical
ihe
transilion
to the
The
7.14.
down
to
An tnlercsring
August
by B. Bertram and
in three crysral structures
is given
:xisis
curve
without
liquid,
form wilh superfluid properties,called
who
first solidified
and vapor coexist.Keesom,
the solid* did not existbeiowa pressureof 25alm.Another
can,
zero
Ihe normal
temperature
liquid He ii,
\342\200\242
iiquid-vapor
absoiule
hciium,
triple
R. A.
liquid
He
point
exists
Guyed Scientific Am
ro rhc condili
according
(,
found that
'He
of Helium
/
Solid
\342\226\240i
Liquid
40
Gas
7.15
Figure
Pliase
slopeshown
a
in (a)
'he
lo
for
liquid
In rhc
liquid io
[he
has
soiid
have io add
it. Superfluid
solidify
(a) in
3He,
region of negaiive
ihan
eniropy
higher
heal
diagrams
miKikeivin.
properiics
JHc.
The
appear in(b) in ihc A and B phases of liquid
A phase is double\342\200\224in a magnetic
field [lie phase divides
imo
hvo componenls
wiih opposiie nuclear magnciic
momenis.
at
K:
1.743
He I and
regions
here the
He II.The
of existence
The
of4He.
Figure
negaiive
two
7.15
slope
triple
of He
of
phasediagram
ihe
soiid is in equilibriumwiih
3He
exhibiis
of ihe
poinis
are connecicd
II and He I.
differs
in a
ihe
iwo
by a
liquid
modifications.
line !ha!separatesihe
the importance
explained
in
10, the
Chapter
the
purposes
many
!hc
ground orbila! by
when
only
Ilie
when
supcrfluid
for the
energy,
superfluidhas energy
to tlic
relative
a velocity
is set
superfltiid
of the
atoms
exeitation
superfluid is given
of the
of mass
center
he
No
energy. The
no excitation
has
definition
il behaves as
of liquid helium
component
superfluid
were
it
liquid phase
phase.
a vacuum,
as ifi! were not thereat all.The
are condensed into the groundorbila!and have no
if
of! he
entropy
Qunsipariieies
For
solid
the
of
inlo
to
relative
flow
the laboratory.
component of Na
The condensed
as
flow
the
in tile
cxcitatiosis
ereate
not
does
irregularities
the
The
transitions,
loss
from
can
occur.
of the
wall
the
relationshipof
and the
superfluidity
excitations
free
that
superfluidity
of helium
atoms
the
is
flow
!!. If
resistanceless
not
the
involves
He
in liquid
orbilais of freeatoms,with
so
is,
as no
long
orbitals.
with
irregu-
viseosity so long
!ho excited
and
orbital
ground
occur, are a
if they
with zero
superfluid\342\200\224that
by collisions
caused
be
flow
will
atoms
collisions
such
were
orbitals
excited
the
if
Momentum
and
energy
momentum
of
relation
parliele
= -_(/,/,-)*
l\\.ivi
Mo
momentum
G6)
or /ik
Here
would not be expected.
of an atom,
k =
then
we
can
But
^/wavelength.
atoms
the low energy
the
bceause of the existence of interactions between
but are longitudinal sound
excitations do not resemblefree particle
excitations,
waves, longitudinalphonons(Chapter4).After all, it is not unreasonable that a
in any liquid, even though we have
longitudinal sound wave should
propagate
no
A
of
has
language
many
of superliquids,
experience
previous
grown
These
atoms.
up to
excitations
articles.
particie aspect the states are called
the elementary excitations of liquid He II.
shall
Longitudinal
(jiiasip
We
menial evidence
superfluidity.
This
for
condition
this,
but
will
first
show
we derive
us
superfluid
wiiy
give
and
phonons
the clear-cut
a necessary conditionfor
the
phonon-tfke
behavior
of liquid
system
in their
nature
He II.
are
experisuper-
of the
Quaupanhlts andSuptrJluMty,
V down
velocity
He
Body of mass Mo
a cylinder th;it
at absolute zero.
7. [$
Figure
\342\226\240\342\200\242a
'lie
It
in
Figure
7.16
\\M0V2
where
V is
Furthermore,
a body,
*=
perhaps
|A/0F'2
Ma\\\"
the
hk.
The two
if
G7)
,
\302\243k
be
the
satisfied
process
excitation.
(IS)
at the
is unrestricted.
To show
7; Fermi
Chapter
On multiplication
by
Af0V
we
l/2Af0
G9)
from
+ h2k2
2A/0/iV-k
/V
|A-/K2
subtract
square of boihsides:
M02V2
We
G7) to
= MQ2V'2.
have
k +
\\M0V'\\
G9)
obtain
'
\342\226\240
(SO)
2mTq
V for
this
lowest value of the magnitudeof the velocity
which
will occur
when the direction of k
value
equation can be satisfied.The lowest
is parallel
to that of V. This critical velocity
is given
by
There is a
-h2k2
Vs
The conditionis a
become
very
large,
little
minimum
simpler
of-
(81)
if we let the
to express
for then
(82)
body
with
moving
be zero.
body
a lower
the
velocity than
motion
moving
will be
with
Vc
will
not
be able
to create
higher
velocity
will encounter
excitations
will
appear
resistance
and
Quusipartfctes
*lle
Superfluidity,
from below. The slopeof this line is equal to the critical velocity, if
as for the esciiation of a free atom, [he straight line has zero
h2k2/2M,
the curve
ck
s=
slope
crilical
the
and
Free atoms:
The
Vs
of
energy
is zero:
velocity
a low
minimum
phonon
energy
frequencyregionofsound
is equal to
of sound
velocity
product of vs
Phonons:
The
wavevector
the
times
Vc
He
liquid
the
t'a, or
the
to [he
in
where
waves
= 0.
oUik/2M
product
II is
(83}
=
\302\243k
tui>k =
of wavelcnglh
tusk in [lie
and frequency
= minimum
is
equal
= v,.
offtr^/hk
(84)
Vc is
velocity
Vc
A and k0
where
ions
Charged
\302\253
&/hk0
5 x
conditions
experimental
to the
equal
pressure
and
I03 cm
closely
conditions
motion
the
of
temperature
appear
longitudinal
the
(85)
modes
covered
modes
by
eertain experi-
11 under
vortex rings.
in
helium
liquid
like
almost
s\021
Figure
condi-
experimental
the
by
of
motion
ercation
and
of
do not
7.17.
is more
(84) for a neeessary condition for the critieal
velocity
that
demonstrates
general than the calculation we have given.Our calculation
II
if
He
at
zero
a body
will move whhout resistance through liquid
absolute
at
the velocity V of the body is less than the critieal velocity
Vc. However,
Our
* L.
Meyer
result
and
F. Reif, Phys.
Rev.' 123,727
U96t|;
G. W.
Lcllcrs
16,934
A966).
in
WavevccioT,
Energy ck versus
in liquid helium ai
7.17
Figure
exciiaiioHS
of 50s
units
cm\021
wavevecior i of elementary
t.JJK. The paraboliccurve
from
free
the
3.0
2-0
1.0
and
energy
momentum
wfili
from
iineariy
of the
exciutions.
measured
rising
for
curve
lo
correspond
A smoosh
ihe poinls.
through
lhe origin is
of sound of 237
gives
uniii:
Ttie
line
imxnin
jh\302\253
vdocily,
gi\\e$
appropri^se
in ihcse expcrimenls. After
ofij/A\" over ihe region of k covered
Hcnshaw
Rev. t2l. 1266A960and A. D. B. Woods.
Phis.
a vclodfy
the crmcai
mum
D.G.
femperutures above
wili be a normal fluid
exciied.The
of
the
body.
fluid
The
supcrflow
component
ihrough a
may
remain
aspect
fine
appears first
lube
behind
the
in
in
lhe
that are
thermally
resistance to the motion
in
experiments
which
there
temperature,
excitations
source of
is the
component
Einstein
the
below
of demcnlary
component
normal
while
we
have
the
the
normai
superfluid
given of the
this
V as
with
situation,
the tube;
walls of
the
to
relative
fluid
would be createdabove
the
V( by
and any mechanical irregularity in the walls.
of
Phases
Supcrfluid
Three
phases of liquid
superfluid
to
contrast
3He
liquid
3He
transition
4He\342\200\224with
of electrons
slate
surface form a
[he Fermi
known*
be
to
In
in
Uvo
so
of particlesin
as
known
a diatomic
like
molecule,
pair is qualitatively
is much larger than the average
iniereleciron
mlerparticle spacing in liquid 3He.
but\342\200\224in
a few milhkelvin.
similar to the super-
qualitatively
where pairs
in metals,
7.15b),
(Figure
of only
temperatures
are
pair. Such a
but
spacing
in
a metal
near
orbiials
a Cooper
molecule
or the
average
superconductivity
ihree
thai
orientations
M,
1, 0,
and
both
the
magnetic
magnetic
\302\243nd
been confirmed.
have
properties
The
states.
three
superfluids
superfiuid
are possible,
supcrfiuids
magnetic
~
SUMMARY
1. Comparedto a classicalgas,a
energy,
is zero
in
ground
the
The
ground
state of a free
lota!
kinezic
For
elementary
energy
Wll
roif^s,
Ph
in
the
ut\\
ground
temperature
slate.
' ~
2,
at low
gas
low
and
pressure,
high
Fermi
the Fermigas
orbiial
\342\226\240
v
stale
is
ly/b.
Physics Today, February
p. i
For
Bulletin
29.
5i3A97SJ.
i%sici
R
\\d
Ph
in
the
Chapter 7:
.3. The
Cases
Base
and
Fermi
density of orbitats at
is
r,f
\"D{Cf)
A. The
heat capacity of an
at r
gas
is
\302\253
i>
units.
in fundamental
5. For a Boscgas at r
fi. The
electron
3,V/2c^.
<
rE
of atoms
fraction
the
temperature of a fj;iS
Einstein condensation
__2nftV
excited
in
of
is
orbitiiis
bosons
nuniiitenicthig
Y>
PROBLEMS
i.
of
Density
of orbiiafs of a
hi one
orh'ttah
free
electron
and
O,(e)
where i.
of area
dimensions,
two
(a)
=\302\273
(t,/rc)t2*rt/Aa\302\243I
the density
(86)
in two
thai
Show
that
Show
is
dimension
in une
dimensions,
for a square
A,
\302\251i(e)
^tiii/Tcft2
(87)
independent o(e.
2.
where
of
Energy
in is
refarivistic
the rest
Fentu
For
p is [he momentum.
is of [he
(nh/L),
multiplied
limit, (a)
of
Show [hat
in
this
+ it/
by (n/
form
with
an
energy
is given
by e
volume V = i.3 the
energy
a cube
in
electrons
nonrelativistic
For electrons
gas.
n:2)ll2>
relativistic
extreme
exactly
\302\273
me1,
= pc, where
momentum
as
limit the
for
the
Fermi
by
\302\273
AncCii/n)\025
(88)
Problems
where
the total
N/V.
(/\342\200\236
The general
problem is
and entropy
3. Pressure
electron
In a
gas
Ireaied
the
in
by
the
(S9)
Fermi
gas.
furPhysik47,542({928).
(a) Show
uniform
that
Notice
\"/.
a -*
Chemical
-a
verms
potential
where
different,
the integral
the behavior
electron
Fermi
temperature.
is upward
*D, is
given
in
for
that
Fermi
gas
has
orbital
or
to
in the
i!s energy
(b) Kind
l/f/2|J.
region
\302\253
t>.
Oast-0.
of p. versus t
curvature
of
Use entropy
for
expression
gas is
J,Vef.
decrease
of the volume
of a cube every
The
of
is
raised;
to XjL1
energy an orbital proportional
tin
stale uf ihc
ground
exerts a pressure
stale
ground
of
F.Jutlner,Zeilsduifl
degenerate
of
ener\302\273y
fermion
7.7).
Problem
of particles, and to
the
number
N,
of the integrand betweenzerotemperature
for
consider from
and
a finite
the
graphs
temperature.
5. Liquid 3He as a Fermigas. The atom 3He has spin 1 = \\ and is a fermion.
7.1 the Fermi
(a) Calculate as in Table
sphere parameters vF, ef, and TF for
3He at absolute zero, viewed
as a gas of nan interacting fermions. The density
of the liquid
at low temperatures
is 0.081 g cm\" \\ (b) Calculatethe heat capacity
=
T \302\253TF and compare
as observed
with the experimental value
2.89NfcBT
Cr
W. Reese, and J. C. Wheatley,
Rev.
for T < 0.1K by A. C. Anderson,
Fhys.
7.18.
of
of
495
see
also
Excellent
the
130,
properties
A963);
Figure
surveys
liquid 3He are given
by J. Wilks,
Properties of liquid and solid helium,Oxford,
1967,and by J. C. Whealley, \"Dilute solutions of JHe in \"Heat low temThe
Journal
of Physics 36, 181-210A968).
American
temperatures,\"
principles
of refrigerators
12 on
on
3He-*He
mixtures
are
reviewed
based
in Chapter
to 0.01 K.
down
cryogenics; such refrigerators produce steady
temperatures
in
acting
continuously
6. Mass-radius
operation.
relationship for
where
density
is
constant
within'the
white
of mass
protons
order of magnitude of the gravitational
the gravitational
constant. (If the mass
of radius R, the exact
energy is
potential
dwarfs.
be degenerate
electrons
the
that
G
sphere
is
a white dwarf
Consider
the
but nonrelativistic;
Chapter 7: Fermi
and
Sose
Gases
5.0
SO
20
Temperature,
Figure
3He in
7.18
Heat
liquid
*Hc
the
fegion
theoretical
T. Thus for
pure 3Heis
slight slope. The curve
taken
for
gas in the
a Fermi
of C/T
cufves
percent solution of
3He and of a 5
capacity of liquid
The quansisy plotSed on she vcrSica!
200
$00
in K
at constant
at constant
the solution
axis
is C/T,
and
degenerate temperature
volume
pressure,
of Hie in
are
which
liquid
horizontal.
accounts
4He
fof
indicates
at low
3He sis solution
acts as a Fermi gas; she degenerafe
region
over
to
the
at
temperature goes
higher temperature.
nondegene/ate
region
The
Sine through
she experimental possHsfor the solution
solid
is drawn
if the
hrTf - 0.331K, which agrees with the calculation for free atoms
effective mass is taken as 2.38times
the mass
of an atom of 3He.Curves
J. C. Wlicatley, Amer. J. Physics36 A968).
after
thai she
-3GM2f5R). (b)Showthat
in the
electrons
m is
here
lhai
(;ss
ground
she
gravitational
by ihe
if
order
of magnitude
of the
she mass
required
the
state is
of an clcclrosiand
Mit
is
the
Figure
Eimtcin
mass is equal to
dwarf?
gas
H ss
(e)
of
believed thai
Show
neuUons.
she
Sun
she
of
that
Heal
gas ut
capacity
of
ofa colddegenerate
pulsars ate starscomposed
neutron star Mll3R =s 10!7 g\023ciyi. What is
neutron
star with a mass equal so that of the Sim?
tn km.
resuls
A1.
sions
heat
Energy,
op.idiy,
;mii
to ;i volume
cn[[opy
V.
ami entropy
capacity,
;is ;i function
Put
of tcmpcf.ifun; in
of ;i
the
y;is
del'milc
o\\
of degenerate bosongas.
the
in
region
dim
ex prcs-
,V noniiilcMlcling
imegnil
Find
ens
;tn
cortilam volume.
tot a
that
radius for
B x
7.19
shown
in
dilTcrcnce
7:
Chapter
Gases
and Base
Fermi
9. Bosongasin
dimensional
gas of noninteracting
really be treated by
of
white dwarf
Relativhtk
10.
means
of rest mass m
such that the
great
the
the
that
ground
(The
on a finite
The de
momentum.
is the
does
integral
does
should
problem
each
dwarfs are
A' electrons
white
kinetic
relativislic
extreme
have
electrons
onc-
line.)
for
condensaie
stale
calculation.
over orbitats
a sum
majority
boson
stars.
of
a sphere
in
for Nt{x)
the integral
Calculate
dimension.
one
interactions
of
effect
Broglie relationremains
A1 electrons
of the
ground stale kineticenergy
on the assumption that
pc for ali elecrrons. Treat the sphere as a cube
of equal volume,
viria! theorem argumentto predictthe
(a) Use the standard
of N. Assume
value
that the whole star is ionizedhydrogen,
the
but
neglect
of the
kinetic energy of the protons comparedto that
electrons,
(b) Estimate
the value of N. A careful
treatment
leads not to a single
by Chandrasekhar
value of N, but lo a limil above which a stable while dwarf
cannot
see
exist:
D. D. Claylon, Principlesof stellarevolution
and
McGraw-Hill,
nucleosynthesis,
M1973.
1968, p. 161;
Harwii,Astrophysicat
concepts,
Wi!ey,
).
Inhjp.
2 gives the
Problem
e =
11. Fluctuations
in a
Fcwri gas.
Show
of a
orbisa!
a single
for
fermion
system
that
- <N>A -
<(ANJ>
if
is
\342\226\240GAO
fluciuation
of a
single
orbiial
of
a boson
If
as
</V)
<JV>(I
enough
deep
N ~
in
below
the
the Fermi
<N).
is the
(I!)
<(ANJ> =
(91)
number
of fermions
average
vanishes
for orbitals with
energies
= I. By definition, AN
s
thai
<N>
the
energy so
12. Fluctuationsin a Basegas.
<N\302\273
average occupancy
(92)
<JV\302\273.
are
if fhe occupancy
is large, with <N> \302\273I, ihe fractional
fluctuafions
of the order ofuntty; <(ANJ>/<N>2\302\2531, so mat the actual fluctuations can
Thus
be enormous.It
been
said
that \"bosons
of thrs text has an elementarydiscussion
of
travel
has
13, Chemical
the
potential versusconcentration*
for
flocks.\"
fluctuations
Sketch
(a)
particles
in
boson
The
first
edition
of photons.
carefully
gas in
the chemical
volume
at
icmpcraiure
r. Include
for a syssem
of fermions.
14.
at
orbitals
with
of
boson
orbilai
Two
(he
Consider
systent.
a system of
0 and e.
particle energies
single
temperature is r.
Find
such,
fegimes. (b) Du
The
chemical
the fhefma!
that
is
twice
rE
spin
same
zero,
is
potential
average population
lowest
the
of
bosons
A'
the
e.
at
of
Assume
electronic
is cooled
gas
~ BTTh2iM){Ni2.6\\2VJ/\\
The
law, G3).
she
of
number
sudden
decreased
condcusase;
orbitals.
With
asoms
this
appearance
in excited
sechnique
of
orbitals
is
in
with
agreement
good
she t3
through
rE. The peak comes from
she wings of she line from
light
lighs
scattered
scattered
by
by
atoms
atoms
in
in
excited
the
Chapter
and Work
Heat
OF HEAT
DEFINITION
AND
2-7
WORK
CONVERSION
ENGINES:
HEAT
TRANSFER:
ENTROPY
AND
ENERGY
2IS
OirnOl
2-S
Inequality
Sources of
252
Irrevcrsibiliiy
233
Refrigeraiors
Heat
and
Condiu'oners
Air
255
Pumps
2?6
Carnot Cycle
Example:Carnol
an
for
Cycle
Idea!
of Thermodynamics
242
Gas
245
PRESSURE
245
Ideal
AT CONSTANT
AND WORK
CONSTANT
OR
TEMPERATURE
245
Work
Isothermal
IsobaricHeal
245
Work
and
and Fuel
Elecirolysis
Example:
237
240
240
Work
Irreversible
HEAT
Gas
Law
Cells
Chemical
247
250
Work
Example:
Chemical
Magnetic
Work
Work
and
for an
Ideal Gas
25!
2--
Superconductors
SUMMARY
257
I'UOBLEMS
2?
1.
Heat
2.
Absorption
).
I'lwicm
:::
Pump
4. I leal
2!:<
ReiYigerator
Carnol
6. Room Air
25S
Hnginc
Engine\342\200\224Kel'rigcralor
5. Thermal
Pollution
Condilioner
Cascade
25S
258
258
7. Light
Bulb in a
8. Gcotlierrnal
259
Refrigerator
259
Energy
9.
Cooling
Solid to
of Nonmetallic
10. Irreversible
Expansion
of
a Fermi
T= 0
Gas
259
259
and
Energy
AND
ENERGY
and
of
to a
The
system by thermalcontactwith a
system by a change in the external
The most
the
civilizationis
combustion
physical
conversion
of heat
most
because
The
fundamental
da
transfer
it
reservoir
~ dU/x
is accompanied
in external
of
is a
limitations
the
understanding
com-
of the
much
to
rise
Consider
2. This
of Chapter
made
was
development of thermodynamics.
central applications of thermalphysics
electrical
energy is generated from heat.
difference
between
heal and work is the difference in the
the
which
with
to work.The problem
of the
one
remains
transfer.
entropy
in. a
The
internal
engine, which converts heal to work.
to dominate man as much as It serves
seems
him,
which
conversion
the
volume,
process
important
engine,
transfer
that describe
para meters
by the steam
possible
reservoir.
transfer
is the
Work
we distinguish
reason
The
potential.
we discuss
when
include
may
parameters
gravitational
forms of
different
two
are
to a
system.
TRANSFER:
ENTROPY
work
of energy
energy
Work
DEFINITION
Heat
of Heat and
Definition
Transfer:
Entropy
a reservoir
the energy transfer dtl from
is/in thermal contacl at tcmperaiure
we
transfer- Work,
as
parameters\342\200\224such
t; an
accompanies
by entropy
to a
the
position
argument
and we see
as heal,
above
defined
being energytransfer by
of a
piston\342\200\224does
not
system
entropy
a change
transfer
any
entropy
of
the
lo the
other
processes such
we
heat
processes
in
the
that
constant.Later
are
Let
decreases.
will
which
flow example
us restrict
combined
generalize
the total
in Chapter
2.
ourselves
of
entropy
the discussion
entropy
for
the
present
the interacting
to irreversible
to
reversible
systems remains
processes which
the
CkapterS:Heat
We
Work
and
work. Let
is
the
as the heatreceived
by
of
the
xda
i!Q
process. By the
in the
system
(I)
principleof conservation
energy,
dV
energy
ihe System
t1W =
below.
\342\200\224
we
HEAT
of
~ zda
dV
reversible
the
dW rather
0)
process.
reasons for
Our
ihan dQ and
d\\V
roles
energy
arc
explained
pure work;
sysictn
Then
CONVERSION
INTO WORK
of the
because
consequences
reservoir.
the
(tQ
in
by iftjand
Catnotinequality. Heat
processes
dU ~
B)
partly by
from
the system
have
0,
ENGINES:
HEAT
OF
on
work
+ dQ ,
is caused
change
by heal added to
partly
aw
different
Have
work
and
difference in
in
entropy
conversion
conse-
two
Consider
transfer.
difference:
the
of work are
is zero.
transfer
entropy
ideal
An
electrical
electricalresistance,is device
ideal
electrical
work.
generator
of work
mechanical work into electricalwork. Because forms
to
are
each
convertible, they
thermodynamically equivalent
(o
denotes
mechanical work. The term
equivalent
particular,
mechanical friction or
electrical work into mechanical
without
and into
work
mechanical
into
convertible
freely
motor,
convert
to
converts
An
are
all
other
work
freely
and,
all
types
in
of
work.
(b)
heat
Work
cannot
be
can
be
completely
but docs
the beat,
work from
completely
heal
necessarily
be pennittedto
ultimately
be
removed
pile
up
from
inside
work.
the
with
the
the device.
device
from
from
way
to
do
system
with
A device that
generates
that
has been
the
the converted
indefinitely;
The only
Entropy entersthe
into work.
converted
must
converted
heat
input heat
cannot
Heal\302\243itgines:
of Heat
Conversion
into Work
Entropy
as waste
heat
is given
that only
and outpul
eittropy
ail
the
A
there
input
prohibition
all
the
heat
input
.it which
the
be ejected
need
the entropy
thai
iransfer
heat
reversible
by the temperature
part of the
;t\\\\ay
cany
\\\\ca.t.
BecauseiiQ/ifc = r,
entropy
in any
from
operating
continuously
The
outflow
entropy
the amount
than
heat
input
flow
be some
output
to
work.
To
excess
input
at the
the
lower temperatureio
bctv^^.i
difference
prevent
input
of
ihc accumulation
heal to work!
against
unlimited
entropy
accuniLiiaiion
tn
device
it
does
not
is ultimately
cycles,
and
the
contained
entropy
is
There
the
stroke
intake
the
What
in each
not
is at a
cylinder
of
pile up indefinitely.
of the
fraction
The
engine.
Such a cyclic
is an example:
does
entropy
with time.
periodically
internal
co'rnDiisTion engine
varies
device
the
in
one
during
cyele
at ihe
fixed higher
temperatureth
heal
the
is equal
entropy
be
can
is ak
\342\200\224
To
avoid
Q,fa = QJik ,
Qi
14)
E)
ir,/rh)Qh.
The work
between
ratio of
The
ealled
the
Qh
- Q, = [1 -
Carnot
QA
-\302\261\342\200\224>-
F)
Qh.
in the
added
heat
difference
reversible process
is
efficiency:
G)
is named in
This quantity
form of
derivation
of
concept
entropy
by some 15
preceded
derived
it in
1824. It
was
energy.
honor of SadiCarnot,who
ij
W/Gh,
is
the
the output
highest
value of the
possible
of
input
heat,
energy conversion
in any
cyclic heat
Heat
Ens'\"\":
Conversion
of Heat
into
Work
input
Output
Figure 8.2
Entropy
and
entropy
inflow
at
ihe
energy
(low
new
in
entropy
lower temperature
higher temperature.
at the
a teal
engine that
ft S:
&(r,/Tfc);
(9)
A0)
actual
The
W/Qk
i; =
have
can
We
efficiency
with
increases
increasing
tJt, -* go.
The
waste
usually
Th high compared
limited
which
are
is
by
materials
an
in
temperatures
constraints.
the
below
all input
conversion
be
ultimately
environmental
input
temperature
are unfortu-
practice
In power plant
steam turbines,
operate
continuously for years, the upper temperature
willi
the strength
to about
and corrosion
600 K\"by
problems
300 K and Th = 600 K, the Carnot efficiency
is i;c =
$, or
limited
of steel.With
=
r,
50 percent. Lossescausedby unavoidable
irreversibiliiies
to
40
about
eilicicncies
T
oobtain
typically
percent.
Higher
reduce
is a
this ellkicticy
problem
in
high
metallurgy.
temperature
Sources
operates
to
expected
currently
K. Higheilicieney
requires
various
to convert
that
of any
heat
that
engine
the highest
tJt,
so thai r, c;innoi be
about 300
temperature,
we
but
the environment,
into
unfortunately
reversible
xhfxit
low-temperature
ejected
temperature
given
under
obtained
ratio
a device
of
operation
of UreversibHity.
common
sources
of
irrevcrsibility:
(a)
Part of the
bypassing
cylinder
the
heat
input
actual
walls
Qh may
energy
duriiig
flow directly
conversion
combustion
internal
engine.
(b)
Part of
temperature
the
diflcrencc
tesnperature
drop
of
flow.
(c)
part
of ilic
be convertedbackto heat
by
mechanical
friction.
(d)
Gas may
doing
work,
as in Ihe
irreversible
Irreversible
wfthout
expansion
or
work
heal
bypass
8.3
irreversible
heal
How
in the
palh
during
expansions.
Refrigerators
to move
work
consume
engines in reverse.Refrigerators
low temperature r, to a higher temperature
the energyConsider
rA.
no
in
8.1. Because
entropy flow diagram of a reversibleheat engine
Figure
its operaiion
can be reversed, with an
enlropy is generatedinsidethe device,
e*act reversal of the energy
and
Ot>-\\i.
F)
Equations
D)
ihrough
entropy
Refrigerators
i'^ai from a
remam valid
are heat
for
the
reversed
flows.
Chapter S: I hat
The
but
G),
to
temperature
of interest
ratio
energy
efficiency
Work
and
the
ratio
tlic
work
value
reversible
in
with
i;
<
i always,
consumed
f\302\260r
'he
W;Qh
y can
be > 1 or
of
tem-
low
refrigerator
the Carnot
confuse*/ =
0,/W
heat engine;although
W = Qh - Qh the work
yc. Do not
efficiency of a
conversion
energy
by
conversion
tlic
at
is called
operation
coefficient of refrigeratorperformance,
denoted
52
\302\273;
tile energy
is itot
refrigerator
consumed.
its limiting
performance;
in
< 1.
From
E)
Eq.
and
is
A2)
is
Th
or
smaller
than
A3]
T,'
unity.
always
irreversibilities
contain
as
in the
ejected at the higher temperature,
ettcrgy-entropy
that all energy and entropy flows
Figure 8.4.With the convention
we now
place
are
positive,
have
ah >
in
is
of
excess eniropy
flow diagram
this
refrigerator
of (8).
e, ,
Further,
& 2 (V'Jfl
A4)
Qt
- Q, >
\342\200\224
1]Q,
Q,iW
=\342\200\242
< yc.
A5)
Q,
\302\273
Q,/yc
A6)
Air
ami
Conditioners
Heal Pum
Ouipui
Input
Figure 8.4
energy conversion
Both heat engines
refrigerator.
efficiency
and
flow in a
energy
is an
as the
y, just
performance
and
Entropy
a heat
refrigerators
are
engine.
subject
to restrictions
imposed by the
but the
of
of entropy,
increase
Air Conditioners
Air
automobile;
inside
during
the
ofliquid
12).
are
conditioners
different.
heat
and outside
the winter,
refrigerators
is ejected
that cool
building
lo the
we
heat
pump.
\342\200\224\302\253
r\302\273
Hear and
Chapter Si
heat the
can
pump
Work
on the
limitations
The
air
a lower
with
of energy
consurnption
than by direct
I).
(Problem
healing
building
and
install
to
economic
make
pumps
is required
conditioning
are
economical,
largely
They
are
anyway.
Carnot Cycle
The
of
coefficient
refrigerator
realize process
refrigeration
is
Carnot
the
of
derivation
by which
achieved.
The
energy
conversion
made
performance
work is
generated
and best
simplest
from
heat,
or
about
how refrigera-
Carnot
cycle.
~
The
\302\260h
&I1
\"
\302\260L-
done
work
by the
W~{Th
of the
rectangle
in
\342\226\240\342\226\240=
0 =<\302\243uta
combine
described
substance.
T,)(tfn
- ffj.
A3)
from
follows
SdU
We
area
8.5:
Figure
whicii
[he
the
system
-SpJV
in one
cycle. The
boat taken up
;/c.
Any
process
working
at
,lCyd.
Figure 8-5
into
work,
cycle, for the conversion of heat
of entropy
versus
for
an
arbiirary
temperature,
working subsiance. The cycle consistsof two expansion
phases
4 and 4 -+ 1).
(t -* 2 and 2-<3) and wo compression
phases <J \342\200\224\302\273
Cjnc of the expansion
ano one of ihc compressionolsascs
iire
B -> 3 and 4
iscntropic
loop.The
rather than
Even
and outputs
such
where
reservoirs.
The
Carnot
healing
Caettot
Example:
cycle-
reservoir
<i\\h
initially
at
is
kind
done is ihc
area surrounded by
area of ihc
ilic
the
energy
conversion
need a
cycles
gas
as
exist,
cooling
cycle for an
ihc
All
in principle
could
what
(lie
often
and
is done.
fact
a low
and
reservoirs
difference
temperature
in
what
input
temperature
inputs
of each
phase
work
The Carnol
be done,
at r^ is the
consulted
heal
one
nei
line.
broken
heat
(I
isothermal
high
Carnot
as a plot
illustrated
between
steam
the
occupies
We
carry
is invariably
(here
turbines,
processes are
idea!gas.
high temperature
in
never truly
an
ideal
;s
reser-
the
reversible.
monaionjic
gas
equilibrium
to
through
the
with j
volume
K, as
\\vo[k
heai
in
Qh
This
work is
furlhcr
:,.
Ihe
In
is delivered by
now
Afler
F.63).
ciioscnlo
=.
the addilional
The volume
gas.
\"
V3
the
the
at
from
(SI* and
low
tem-
lo
the
VJVj.
into contact
(tJt,}*2
B2}
a temperature
with
reservoir
<Slf
satisfy
\342\200\224
f,.
i'j,-
Kj/V'4
the
gas is
initial
has returned
this
from
CH,
ncl work
areas in Figures
curves in the p-V
delivered
value
initial
8.6a
cancels
by
the
and 8.6b,
diagram
as
<R,
heai:
= ^34-
and
jy4!
the work
B5)
recompressed
i*. Because
temperature
is performed
to
B3)
VJV2
compression,
is ejected
work,
to its
= (t*A,K'2
To accomplish
disconnected
to ihe
liseii
at this point
the work
The
end of ihe
or
ft
temperature
has
B0}
disconnect!
has dropped to
ihe temperalure
is brought
gas
Finally,
as
the
work
= TftV22'3 ,
point
A'r
the gas is
Next,
\0212
until
iscntropically,
Nr^dV/V
labeled
KfVx
so thai
JpJK
area
the
process
the
ii
reservoiris
by
TlV32:3
from
n^cdmmcal
II'l3
indicated
expanded,
peralure
Hie process
\302\243.6a.
In
Figure
*jj 10 ^n c\\lern>ii
absorbed from (he
the
Vlt
|N(rh
work
gas during
is the
which
\302\253
B6)
T()
W2i done
by
the
gas
by
during
ihe difference
8.6c.
Figure
isothermalcurves,
the iseniropic
so
thai
in shaded
The isenfropic
Ihe area of the
y3
Figure 8.6
and
> r,}.
\342\226\240t,(xk
(a)
the
work
riicompressed
for
in four
Two
done during
compression stages,
and
two expansion
stages,
the
net work done during
(c)
the
(b) the
the
work
cycle.
done
during
the two
2nd
is nnitc
loop
and Work
8: Heat
Chapter
i^
to trie
ctintii
relation
Camot
the
of
We
of heai from
reversible
All
have
peratures
so, We
ihe
~-
is jusi
which
r,)/Tj,,
of
Q{\\n)
devices
ihe lower
I with
d\302\243\\
ice
different
with
2 back io
the
The
li^otit), uiihout
would
and
any
qt <
efficiencies,
ij2,
efficiency is operaied in
iemperaiure
higher
The overall
as well.
heai
Q{in) to work
heal
- (ij
into work
of ihe
reversible
(Figure 8.7)ihat
refrigeralor
efficient device
amouni
of heat
consequences
as a
more
W/Qj,
of Thermodynamics
Law
conversion
two
combine
could
in such a way
reverse
so that
B0),
B7)
is impossible
\"Ii
of ihermodynamics
stated
ihe classical
law
eniropy,
in
Second
the
direct
are
refrigerators
second
given
Imvc
iVc
G).
limiis on the
The Carnoi
m F^Rurc 8,3.
jtic rccmn^lc
TjloaflV^).
Cftk was
Conversion and
Energy
W(rfc
of
3r\302\243*i
but
ihe
from
an additional
violate
waste
ihe law
heai.
This
of
would require
of increase of entropy.
we have
thai
Now
the
have the
same
of
Path Dependence
We have
processes,
and
Meat
Work
We look
plane,
returned
It
is not
meaningful
heat
transfer
is
content
of a
around
Ihe
at
But
consumed.
to
precisely
changed.This
means
the
system\342\200\224on
the
initial
that
there
being
once
loop\342\200\224is
condition;
cannot
taken
Path
and
of I hat
Dependence
Work
8.7
If uvo
to work.
If such
loop
the
are
necessarily
would
be
nut
zero,
work
given
Wub
by the
transfers
;md we
to
required
differences
of heat
the system
curry
and of
in
from a
W:
and
the
;tre
not
zero.
inlrtnsic
atlributes
in (l)and
of
B) cannot
(he
system.
The
bedillerentials
8:
Chapter
and Work
that
Twotrr
Figure 8.8
sibie proceisesin
or electrical
mechanical
which
potemial
For
this reason we designated
of mathematical functions Q(a,V)and \\V(o,Vy
the increments by dQ and d\\V, rather than by itQ and dW. Without
the
path
not
exist
that
of heat and work there would
dependence
cyclical
processes
Irreversible
We consider the
is
heal.
from
energy transfer
or electrical
mechanical
a purely
of
processes
8.8. In
Figure
system that
delivers
or
friction
Processes
no
way
to
If newly
irreversible
the
reverse
to heat, either by
that
dU
reversible
this
change
work
in
in order
process
the
at
led
and
in energy
entropy
tfWtev
the
S2
The
^ J^e
entropy
created entropy.
place.
is newly
entropy
is created
of
state
of work
created
to heat,
entropy.
we say that
been performed.
has
work
If we look only
This
ilU2fc-
entropy arises by
created
the process
\302\253
do2
new
which
in
transferred
to &2 is converted
The finai
electrical
resistance.
by
had been added as heat in the first
with zero
work
pure
to
i\\a
net change
this change
in
entropy,
as
the
a reversible
work
in
a system,
there
is no
change
and
Work
Ineveniblt
the
than
reversible
work,
tn\\'il
of energy
conservation
By
dU =
if\\Viim
that
so
actual heal
reversible heat.
The
Example:Sudden
is transferred,
so thai ttU
that refills from a reversibleisothermai
with a reservoir. The work
IV,,, done
work
i\\
:o
Vj is,
equai
to
the
heal
change
is equal
W[cy
lo Q,cJt,
a1-al'=
agreement
in
Ihermai
expansion
equilibrium
from volume
with
B8) and
B9)-
C0)
posittve work
does
>
Wtet <
0;
on the piston
in
an
amount
0.
C1)
or
~Wlcy/x
in
reversible
the
-Nilog(^/K,).
on the
Q[cy=
The entropy
in
from F.57).
done
work
gas
the gas
with
expansion
on the
\\V,n=
The
the
ihan
less
be
of an
expansion
once
consider
the
into
C2)
NlogfiyV,).
this enlropy
from the
system
vacuum
the
is newly
outside:
created
lVitltt
*=
Work
Systems between
8.9
Figure
heat is transferred
need not
which
be
at the
but no
work
on!)'
same temperature
systems.
heat transfer,
work
ai
In this
2.
lower
the
process
heat
t2.
temperature
transferred
fs
= (I/I,
is from high to
heal flow
so
but
actual
reversible
They
entropy
energy
other
Pure
transfer.
place between
out an example in
worked
a system a! rt to a system
if it takes
=\342\226\240
that
chitT >
low
0.
<fQt
C4)
remain
processes
constitute
generation.
natural
i!Qt
temperature;
is negative;
r3
- ri
is
transfer
energy
C5)
-ii.re..
1/I2)rfe,
0.
system by
created entropy is
The newly
negative,
from
in
entropy
We have.'.
i!U2
The
of work Jo the
We
temperatures.
the new
that
assumed
the delivery
during
system
we
systems
no heat
with
different
need
is transferred (Figure8.9).
limit,
We shall
temperatures
of
heat
vanishing
and work,
Pressure
TEMPERATURE
AT CONSTANT
WORK
AND
HEAT
Temperature or Constant
at Constant
Work
and
Heal
OR CONSTANT PRESSURE
isoiherma!
F ~
energy
We
work.
Isothermal
a reversible
\342\200\224
za
of
because dx =
0, so
that
dW
in
additional
system to
terms
of
work
that
the
the
work
(he
done
dU
Hclrnholiz
is required
reservoir.
the
ideal
for
appropriate than
ftiuciion, more
process
dV
- d(za) \302\253dF.
in such
Thus
ihai
Often
Isobaricheat
and
work.
Many
the
the
energy
When
V.
free energy,
to make up
heat
does
noj
is
C6!
ihe
natural
we treat
encrgc:;';
an isotEicrltui
we automatically include
for
transfer is
the
heat
transfer
ihe
from the
in an
change
heat transfer.
energy
transfer
processes\342\200\224isothermal
or
not\342\200\224
take
place
pressure, particularly those processes that
is
said
to be
the
A
to
at
constant
pressure
open
atmosphere. process
an isobaricprocess.
A
is the boiling of a liquid as in Figure
8.10,
example
simple
lake
place
at constant
in systems
Figure
displacing
8.10
=/<\342\200\236<<
ChapterS:
where the
pressure on the
its
changes
system
environment
If positive,
system.
sense \"free.\" if
this
in
is
and
thjs reason it
is
appropriate
eflccthe work
ilW =
itW
the
the
energy
enthalpy
which
V plays isi
itU +
d{pV)
for other
~d(pV)
the system,
=
itQ
the
from
of the
is part
environthe
to
delivered
is
work
system
d{pV) -
\342\200\224
the
purposes.
For
work.
We
total
defined as
~ HQ ,
till
C7)
function
new
called
the
on
performed
d{PV)
is provided by
this work
io subtract
pressure. If (he
atmospheric
negative, the
environment
often
external
volume
is the
piston
plays
= V
+ pV ,
the role in
processes at constant
C8)
is the
C8)
work
vacate
required
the space
d\\V
=> dF
the
at
Gibbs
constant
free
energy.
temperature
~ F
+ pV
+ d{pV)
used
energy
\302\253
U
pV
10.
- xa ,
D0)
The
of the
in Chapter
C9)
function
=> dG ,
in
useful
proceeds
in
at
chemical
a constant
reactions
pressure.
is
Heat and
isobaric
an
Consider
electrodes
ant) SO4~
H+
ciccHoiylc
noi re net
ilia t do
w&in
of dilulc sutfurie
lnc acid [r igtirc
where
s. 11J.
\302\253
2H+
positive electrodes
gas and clocirons: _.
+
the
net
H2O-\302\273
An
sulfurtc
and
in
slowly
a vessci
temperature.
prcsburcaiKicoitMiiiil
hydrogen
move
electrolysis
acid.
oxygen.
cell
The overall
to lhe
negaihe clecirode
g;is:
D2)
water
decompose
they
with the
- H3SO4+'iOj + 2c!^.
H;O
of the
Figure 8.11
in i o
H2.
where
the
SO4~
as dilute
^titfiir
D!)
ions
through the ceil lhe hydrogen
up electrons and form molecular hydrogen
lake
sum
Tnc
SO.,\"\"
-+
The
which
iti
is passed
current
llicy
acid
ions:
H2SOa
When a
Constant Pressure
Temperature or
at Constant
Work
rcucikm
H2
ctttuiluin
in lite
D3)
cell;
{44}
1O3.
An electrical
result
The process is an
is the
current
passes
decomposition
example of work
being
through
goes
an electrolyte,
ofwaterinto
done
conslain
gaseous
at constant
iulo
such
resistance
heating
is related
water
AG
G(Hj) -
G(H2O)
\\G{02).
list the
tables
Chemical
=>
decompose1moleof
- 237 kJ
as
D5)
per mole at
room
temperature.
(not
the
of water.
male
voltage
charge
tlirough
flowing
heat!)
/ that
current
W ~QV0.
to
According
are
there
D3),
in decomposing
involved
electrons
two
D6)
llcnce
Q
We
D5) 10obiain
D6) to
equate
minimum
because
VQ
merely
If V
<
reaction
the
Vo,
the
simplesetupof Figure
al all.
happen
Ev
8.11
is possible,
and oxygen
hydrogen
f'o between
voltage
arrangement
on board the
sources
for
water
The
focced
to J.
under
through
and,
tf
Apollo
O. M.
1969.
(V
VQ)
lhc
/will
pcessure
the
electrodes
hydrogeci-osygen
technological limitation of
cell the current density
Apollo
the
\342\200\242
excess power
on
dtinking
produced
incidentally
astronauts.
the
of an
characterise
Va, the
flow,
the systems
gaseous
principal
In
V >
current
finite
between
from
proceed
is called a
The
will
the electrodes
This
obtain a
poierciuit
is
right to Icfl provided gaseoushydrogen
at lhc negative electrode. In lhe
oxygen
will
the gases are permitted to escape,and
for V < Vo nothing
however, lo construct the electrodes as poroussponges,wiih
D4)
positive electrodeand
at the
available
D8}
be applied
to
barrier
must
reaction equationD4).When.
dissipaicd as heat in trie electrolyte.
area.
place.This requiresa
~AC/2NAe
larger lhan Vo
reduces to zero
voltage
alone
Vo
of the
sides
{law.
lo take
for electrolysis
D7)
voltage
or 1.229volts.
be
condition
the
two
x 10scoulomb.
= -1.93
~2/v>
lo
ceil
clearochcmi'cal
in
K.I
Figure
Bockrisand
produce
Ni
in
was
only
few
current,
hundred
currents. The
reasonable
Us two
low
is their
cells
fuel
operating
ranges as
fuel
per
unit
electrode
hence
mA/cmJ;
large
current-voltage characcell
and
as electrolytic
3.
and
NiO
S. Sriili^asan,
uniict ibn
fwf cells:
Pt
Their
as decltoiici.
electrochemistry,
sVian
H .SO\302\253
New York,
Porous electrodes
ecl! is an electrolysis cell operated in
and oxygen supplied as fuels. The
reverse,
hydrogen
fuels arc forced under prow tin: through
dmroOes
porous
an
The
and
oxygen rea
electrolyte
hydrogen
sqwratcJ by
Tree
is
delivered
to
form
the
excess
Gibbs
waicr;
energy
Water
forms at the positive
outside as electrical
energy.
Figure
A fuel
8.12
with
electrode and
is removed
there.
Elcnrolysis
Figure
8.13
celt or
fuel
Tliecui
ic of
indie
anges.
cell,
\342\200\224
aa electroiyiic
ChaptcrS;
Chemical Work
Work performed by
it is
because
work,
for
then
chemical
the
derivatives by their
lerm
zdo
xda -
familiar
represents
The -pdV.termis
mechanical
the
transfer
reservoir,
both
from
systems.
system
&x to
dN2
\342\200\224
\342\204\242
dN =i
dN,
*=
(dV1
= 0),
The result
summarize
{a} The
particle
(b)
and
~pdV
of heat,
fidN
terms
be reversible:
to
E0}
pJN.
pdN
term is
ftdN.
0. All
d\\Vcl
and
if
all
chemical
into
fadNt
processes
the
be supplied to the
that must
dVi
our definition
E1}
the Work
= OWcl
dWc
work
the
and
the partial
replaced
is
performed
The
have
is chemical,
arc usually
two systems involved, both in contact
there
is the sum of the contributions
and the total chemicalwork
In the arrangement of Figure 8.14a pump
transfers
particles
In particle
a heat
= U(atV,N),
If U
D9}
understood
-pJV+
work;
volume change, dV
is no
is one
system
5.1). By
of heal
dWc
work
fidN
(Table
equivalents
Ihe transfer
<tW ~
from
pdV
If there
the
U depends.
energy
by tlie
with
potential.
process
dU =
the
the
with
When
of the
associated
to a
of particles
transfer
the
additional
of ihe
propcriics
potential
the
system,
The difference in
+ pldN2
pump
= (p2 -
is a\\Vr if
{52}
nt)dN.
there is
no volume work
arc reversible
meaning
of the
chemical potential.
We
chemical potential:
system is the
from a reservoir at
of a
zero
one
systems
system
potential.
is equal
to the
other.
to the
8.t4
Figure
chemical
chemical
{c} If ihe
from
rcs'ersibly
work
two
the
amount
potential;no
in diffusive
are
systems
is
work
per pariicie is
required
the
in chemical
difference
io
potentials.
same chemical
one
syslem
10
the other,
systems in diffusive
5}
{Chapter
barrier thai
two
between
maintains the
equilibrium.
Example
i Chemical
02
This
rcs\\ih
isothciniiiily
compressN
W
work
/fl
the
of a
t[10gOl2/\302\273iQ)
logOlj/Hfl)] =
E3)
Tlog0l2/Jl,}.
io lite n\\cch:tnit;tl
work
per particle required io compress the gas
from the concentration \302\253j
to the concern mi ion
ux. Tltc work
required io
of
ideal
from
an
initial voluitw i\\ to a littal volume ''. is
an
particles
g;ts
is cqtial
=
-\302\247pdV
Hence
an ideal
for
atoms
mechanical
-Nx^tiVjV^
work per
NTlog{IV^}
particle is iSogtoj/iij),identical
= WtlogfHj/ii,}.
to
the
result
{5A}
E3). The
Work
Reservoir'
ilnergy
exchanges-
8.15
Isothermal
diemiciit work. The amount of chemical
does not change
if the process is performed isoihermally with
thermal equilibrium wiih a common
targe reservoir.
work
Figure
work
chemical
the
ideniiiy
of
lence or
convcriibiiiiyof
Magnetic Work
An
and
form
important
the
wiih
kinds
dilferem
Superconductors
of work
isoihcrmal
,-
is magnetic work.Themostimportant
is to
conductivity
to
in
compress
that
electrical
per panicle
sysiems
of work.
superconductors, and
Below some critical temperature Tc
is
electrical conductorsundergo transition
from
work
of magnetic
both
a superconducting
this
application
their
than
less
usually
application
here.
is treated
state wiih a
normal
slate wiih an
many
20K,
finite
infinite
apparently
conductivity.
superexpel magnetic fields from their interior. If the
into a
cooled below the critical temperatureand ihen inserted
would shield the
the
infinite
magnetic field, we might expect that
conductivity
Superconductors
is first
superconductor
interior from
even
8.16).
ir i|ie
This
duciivity
shielding
the
penetration
by a
occurs
magnetic field. However, ihe expulsion
is more
field
expulsion
field.
by
in a
layer
is not
expulsion
is caused
We
always complete.
is incomplete, but stilt
shall
restrict
ourselves
ark
and
Superconductors
8-16
Hgure
in
a constant
transition
the
Mcissner
applied
temperature
sphere.
Thresholdcurves
Figure 8,17
fidd
versus
lempcratui;:
conductors. A
below
In
TiX
Temperature,
in
specimen
for scv
\342\226\240i
;jpe
noiii..;! iib
,-->I[-lOUl
fill
111
and Superconductors
I Curt
Magnetic
Figure 8.19
arcu
A in
produces
transition
that
it
electronic
is the
The superconductingstaleis a
by differences
The
of
iicai
in
the
with the
field,
iower
capacity
8.1 S)
-di
superconducifvhy
magnetic
heat
(Figure
capactiy
superconductor
sol
superconducting
a magnetic Ikld
B.
metai
x =
energy.
distinct
.<hermodynamic
phase,
as confirmed
ihe discontinuiiy
free
transition.
a phase
undergoes
system
Beiow
tc
than
in
zero
magnetic
that
of the
fieid
normal
be
the
phase
the free
energy
phase. The free
field, as we show
(CGS)
B2/2{t0\\
E5a)
E5b)
Figure 8.20
Tlic free
noi\\ti\\^i
t\\otii\\3.t meiat
syndic
melai
energy
Al a
$\342\200\236.
fkUi
magnetic
and Work
dcnsiiy
F* of
is
in
x <
zero
SI
unite
land by BBJ/8n
lhai Fs(r,/iJ
larger
=\342\226\240
deiisiiy is lower
ihe
in
siiperconduciing
si ale is ide siabic
vertical se;ilc in
ftgute
equally
so
uniis),
Ba3/2j@. If Bu is
BM ihe free energy
siaic than in
normal
field
st,iie. The
ilic
Bj/l/i,,,
Fs by
CGS
siaic, and
the
An
F^i.O).
F5(r,0)
criikjil
liian ihe
in
the
xt
magnate
field, so
in
applied
temperature
is a superconductor
appcox.iiv\\u.lcty
intensity of the
of [he
independent
Heal
Si
Chapter
of i tic
f Jr-O)-The
is ai
drawiiij;
10 U5
applies
origin
und
ii\\
Us
= 0.
magnelic field Ba
Applied
which
free energy
the
density
application of an externalmagnetic
the
in
bulk
in an
field,
superconductor
experiment
at con-
temperature.
There
because
is no
comparable
there is no
screeningof
the
normal
conductor,
Thus
field.
applied
the
(SI)
E6a)
{CGS)
E6b)
the
field
magnetic
energy density of both phasesversus
tne
free
will
rise
of
the
energy
superconductingphase
ultimately
{Figure 8.20),
above
that of the normal phase,sothat in high fields the specimen will be in the
normal phase, and the superconducting
is no longer the stable phase
phase
This is the explanationof the destruction
of superconductivity
by a critical
En
plot
of
the free
magnetic field
Wiih
Bf.
increasing
superconducting
decreases. Everything
the free
temperature
phase decreases as
else
being
equal,
crilical
temperatures,
rr,
and
high
critical
amongst
the
stabilization
temperature
critical
normal
magnetic
energy
and
and
field
type I
a high critical
the superconductors
in a
with
the
SUMMARY
1. Heat is
contact
by thermal
energy
process dQ = xda,
reversible
2.
of
transfer
the
only
by a change in theexEerna!
parameters
the system. The entropy transfer in a reversibleprocessiszero
is performed and no heat is transferred
work
The
Carnot
the
is
Work
of energy
transfer
that
describe
3.
limit to
4.
limit to
upper
of
5. Thetotal
work
the
efficiency,
j;c = (zH
to the
work generated
the ratio
on
performed
the
of
QijW
&
roof
6.
the
the
Hclmholtz
is the
upper
system.
The
energy
7. The
tJ/tj,
in a reversible
temperature
free energy F se U - ro-
at constant
system
\342\200\224
when
heat added.
~
- r,), is the
performance, -,'c t,/(ta
heat extracted
to the work consumed
of refrigerator
coefficient
Carnot
The
conversion
energy
In
reservoir.
with
to
particles
the
8. Tlic changein
by an
external
the
to
change
- w + pK.
work
chemical
constant
at
system
the
on
performed
free
a system
in
the
reversible
and
temperature
in the
Gibbs
transfer
of
free
t.lN
is pdN.
energy
density
of a
superconductor {oftype
in
magnetic field B is B2/2{i0
SI
and
S2,8;i
{) caused
in CGS.
PROBLEMS
/. Heat pump,
per
unit
of
heat
(a)
Show
delivered
that
inside
2.
In absorption
refrigerator.
not as work, but as heal
Absorption
process
is
fuel,
supplied
home and
xh. Mobile
>
i(,h
(a) Give an
cabin refrigeratorsmay
energy-entropy
flow
be
diagram
this type,
of
similar
to Figures
with
propane
8.2 and
such
Hows
the
at
8.4 for
for
ihe
reversible
operation.
efficiency.
4. Heat
The
cascade.
engine\342\200\224refrigerator
of a
efficiency
heat engine is to be
tow-temperature reservoirto a
temperature
r,, by means of a refrigerator. The
consumes
of the work produced
part
by the heat engine.Assume
that
both
tlie heat engine and the refrigerator operatereversibly.Calculate
the
ratio
of the net (available)
work to the heat Qh supplied
to the heat engine at
temperature ift. Is it possible to obtain a higher net energy conversionefficiency
valuer,.,
refrigerator
below
in
this
the
lowering
by
improved
the
of its
temperature
environmental
way?
5. Thermal
pollution.
a water
with
river
temperature
T} =
2CTC
is
to
be
used as
permit raising
Th
by
what
lOQ'Q
in
effect would
hot-steam
this have
technology
on the plant
capacity?
air conditioner operatesas a Carnot
cycle
between an outside temperature Th and a room at a lower temperarefrigerator
\342\200\224
this heat
room gains heat from the outdoors at a rate A[Th
temperature7\"j. The
T,);
is P.
T
he
to
the
unit
the
air
is removed by
condilioner.
cooling
power
supplied
(a) Showthat the steady state temperature of the room is
6.
Room
ah
A room
conditioner.
T,
\302\253
(Th
PjlA)
[<Tfc
4-
P/2AJ
T,,2]1'2.
(b) ir the outdoorsis at 3VC and the room is maintained at 17\302\260Cby a cooling
A of the room
in W K\021.A good
power of 2kW, find the heat losscoefficient
Amer. J. Physics
2S2 K
air conditioners
of room
discussion
and the
7. Light bulb
Carnoi
In a
19 A978).
46,
is given by
a refrigerator,
in
that draws
S.
Gcoihermal
to
generate
to drive
steam
energy.
electricity
rockdrops,
to
according
dQh
W. D.
Teeters,
bulb is
100 W light
Can
tOOW.
be
at
the
left
inside
burning
below room
cool
refrigerator
very
a turbine. As
LefT and
K.
378
tempera!ure?
uiilized
S.
refrigerator
H.
large
lower reservoirtemperature
T,stays
end of
At the
the
calculation,
give
-.
constant.
a numerical
to Ti,
\302\253
0
as
by
means
solid
to
We saw in
T~Q.
solids
spin
\\
fermions
C.
electricity
kWh.
at sufficiently
7\",
total
10u kg
\302\273
20
nonmetallic
~ aT3.
C
of
which
initial
tile
required.
a gas
of
expansionof a Fermtgas. Consider
at
a
volume
in
A/, initially
temperature
V;
of mass
gas expandirreversibly
into
a vacuum,
wiihout
high-temperature
Tj of the
temperature
N noninteractiilg,
if
doing work, to a
~ 0.
final
Lei the
volume
large
temperature of the gas after expansionif Vf is sufficiently
for the classicallimit
to apply?
Estimate
the factor by which the gas should be
value.
Give
numerical
for its temperature
to settle to a constant final
expanded
in kelvin
for two cases: (a) a particle massequal
values for ihe final temperature
=
mass
to the electron
as in metals;
and
(b) a particle
10\"cm\023,
mass,
NjV
=
stars.
white
dwarf
equal to a nucleon,and N/V
10JO,as in
V}. What
is the
Chapter
Gibbs
Free
Energy
FREE
GIBBS
Example:
262
ENERGY
Comparison
of G whh
265
266
IN REACTIONS
EQUILIBRIUM
Equilibriumfor IdealGases
Example:
of Atomie
Equilibrium
Example;pH
and
the
Ionszatton
267
and Molecular
of Water
Hydrogen
269
265
270
Action
SUMMARY
272
PROBLEMS
272
1. Thermal ExpansionNearAbsolute
2. Thermal
lonization of Hydrogen
3. lonizationofDonor
Impurities
4. Hiopolynicr
5.
Patticlu-Antiparticle
Growth
Equilibrium
in
Zero
272
273
Semiconductors
2 73
2/3
274
Free Energy
9: Gibbs
Chapter
constant
and
volume
chemical
many
introduced
are performed
system at
many experiments, and in particular
at constant pressure, often one aimo
thermodynamie
- xa +
the
treat
As
in
equilibrium
Chupicr
8, we
A)
pV.
energy, and
call
to
as
G a
often
3 describes a
in Chapier
useful
configuration
Chemists
Reactioi
But
temperature.
reactions,
is
spherc,
Chemical
ENERGY
FREE
GIBBS
and
often
physicists
call
potential.
dG =
a system {Figure9.1)in
Consider
at
temperature
so
that
t and
the
differential
The thermodyiiamicidentity
zdds
B) becomes
cdx
pdV
contact
Vdp.
with
contact
minimum
a heat
reservoir
<Rl
that
= 0 and
dt
p, but cannot exchangeheat. Now
dp = 0,
becomes
dG oflhe system in the equilibrium configuration
dGi
so that
thermal
in mechanical
the pressure
maintains
the
tt
dUs
B)
C)
is
E.39)
= dUi
dG^ \302\253ndNx.
xdax + pdV*
But
dGj
ttdNi
dNs
\302\273
0
= 0,
pdVs,
wh
ence
i eser
System
rese rvoir
Hea
\342\226\240oir
\342\226\240\342\226\240\342\226\240v\"'Jif
m,
a heat
v.hh
NPSu
qualiz
Pressure
whkh
reservoir
ger lo
on Hie
e pressure
and
reservoir
in
mechanical
barysiai or pressure
maintains
a constant pic
with a
equilibrium
system.
The
is
barysial
insuSalcd.
cserv
is tlic
which
condition for
at
constant
therefore, the
natural
variations
irreversible
change
G3
sign associated
place entirely wiihin
laking
respect
w'Hh
&
to system
varia-
number. Theseare,thereraiher
a minimum,
be
musi
wilh
and particle
minus
the
from
direciiy
extrcmum
temperature,
for G(N,z,p).
pressure,
variables
Gj to be ;m
the
will
than a maximum,
eniropy
in (i);
increase
a and
Any
ihus
decrease Gs.
With
B),
The
difierentiai
E)
may
Comparison of{5)and
be writicn
F)
gives
adx +
E)
as
the relations
0)
(8)
thermally
Chemical Reactions
Gibbs
9:
Chapter
, = V.
Three
see
Maxwell
relations
from these
be obtained
may
E)
by cross-differentiation;
1.
Problem
In the
Gibbs
free energy G
\342\200\224
za
pKthevariabfesr
and pare
intensive
are
two identical systems
pui together.
But U, a, V, and G are linear in the number of particlesA':their value
doubles
We
when
effects,.
two identical
interface
systems are put togeiher,apart from
one particle
say that V, a, V, A7 and G are extensive quantities. Assume that
only
species is present. If G is directlyproportionalto N, we must be able to write
quantities: they
not
do
value when
change
G=
ep is
where
quantitiespand r. If
wjih
temperature,c;idi
does
not
of N because it
independent
identical
molecules,
j.V
in
change
two
the
A0)
Nip(p,x)
is
function
only
of the
intensive
process.
of gas at
It follows
equal pressure
We
in G)
saw
that
A2)
so that
<p
must
be
identical
with ;j,
G(,V,p,t)
A3)
is equal
to 'h
for s single-componentsystem
I or
G for an ideal gas, sec B1) below.
Gibbs free energy per particle,G'/A'.
If more than one chemical species is present, A3) is replacedby a sum ov
Thus
the
chemical
poiemiaf
all species:
A4)
Gibbs FreeEnergy
The
becomes
identity
ihermodynamic
xda = dV
pdV
A5)
^e/INy,
and E) becomes
shall
We
the
develop
G ss: YJ^jfif
that
ts
reacting
\302\243njdNj
(!6)
+ Vdp.
adz
of chemical
the property
equilibria by exploiting
with respect to changes in the distributionof
in a
t, p. No new atoms comeinto the system
theory
a minimum
at
molecules
\302\253
dG
constant
themselves
reaction; the atoms that are presentredistribute
snucics to another molecular species.
ti
\302\273f
Omipurhtw
iiiutupfri
Let
F.
with
sttf
its
is Jitiacut
wluit
molecular
one
from
:ihuuJ
\\\\vi
rd.ttions
iwo
= p(iVrT,K)
{cFfdN)tty
A7)
and
*=
$G/dN)tiP
We found
lM
in F.18)
for an ideal
(IS)
fi{T,p).
gas
MN.r.F) -Tlog(WKnQ) ,
so
that
ti(N,z,l')
is
not
and therefore
of N
independent
She iaiegra!of{S7).
Thai
is, f is not direciiy proportional lo N
number of particles is increased. Instead,from
F(t,V,N)^
But
she
Gibbs
C(r,/\302\273,N)
t-he
\302\273
F
if ilie
system
we cannot
is kept at
PK
gas
potential
in
the form
cotislanl volume
ihc
as
B0J
is
N/V
- l] +
Arr[!og(p/rny)
==
p/r.
-Vr
PO
NrIog(;j/THQ)
JV;i(r,f) .is
- I].
\302\273.
by use
F =
write
F.24),
Ni[\\og(NJVnQ)
ideaJ
A9)
We readily
identify
in B1)
the
chemical
us
/((t,p)
= i
lo\302\243(pJxnQ)
B2)
Chapter
Reactions
Chemical
and
G \302\253
in sit.V) in
We see [hat N appears
by reference to the result
iVjih.pV
unavoidably
but not in /j(t,p)
in B2). The chemical potential is the Gibbs
free energy per particic,
A9),
but
il isnol
ihcHctnihoHz
free energy
Of course, we are free lo wrile p its cilher
pet panicle.
A9) or
122},as is convenient.
IN
EQUILIBRIUM
REACTIONS
equation of a chemicalreactionas
v,A,
v2A2
= 0
\342\226\240
- \342\226\240
v,A,
B3)
B4)
species
Hj
in
the
reaction
equation.
of the
reaction
+
=
Ai
the chemical
Aj denote
the
where
- Clj;
A,
H,;
Aj
fj=l;
Vi=l;
HC1;
\302\273j=-2.
B5)
of chemical
discussion
The
conditions
of constant pressureand
The
differential
of
respect
constant
presented
In
temperature.
in the
to changes
for
equilibrium
proportions
reactions
under
G is
dG
Here//j
equilibria is usually
- Z fj^i
adz
Vi!p.
B6)
to
07)
rfC-1/,/W,.
The changein
the
potentials of the
zero.
Gibbs
free
re\302\243tctbnts\302\273
Xti
energy
comlit^rtufii
in
reaction
depends
is &i cxtrcmum
on the chemical
tjo
uu musl
miu
for
Equilibrium
The change
coefficient
dN} in
the
the chemical
v,m
of species/
of molecules
number
equation
]>>/.; - 0.
We
may
Ideal
Gases
is proportionalto the
dN} in
Write
the form
\"
JNj
dfif indicates
where
in
how many
\302\253
rjd$
B8)
timesthe reactionB4)
takes
place.
The
change
dG
becomes
B7)
dG
In equilibriumdG
0, so
\302\273
dft-
vjfi
B9)
that
C0)
pressure
and
for Ideal
0 when
utilize
We
F.48)
nj
is the
concentration
which
is
the
depends
internal
Uul ihcmull
when
p and
genera!
the constituents
equilibrium condition
acts as an ideal gas.
potential of speciesj as
of species j
logc;) ,
C1)
and
\302\253QJZ/int)
C2)
of
rflogMj
cj a
the
of
form
useful
where
constant
Gases
simple and
We obtain a
Y^Vjf-j
of matter at
temperature.*
Equilibrium
transformation
in a
equilibrium
is moregencrat; onceequilibrium
t arc specified..
\342\226\240
$>,!(*<:,
is reached,
ihe rcaclion
C3a)
Chapter 9: Gibbs
Free
and Chemical
Energy
Rcactia
C3b)
The left-hand sidecan berewritten
as
C3c)
side can
the right-hand
and
be expressedas
C3d)
Here
the equilibrium
called
K(t},
temperature.
Wiih{32)\\vehave
K{t)
free energy
internal
the
because
C4)
nil\302\253/'
is Ffim) =
-TiogZj{int).
From
and
C3c,d)
we have
C4)
C5)
Fk-Vj
as the
known
of any one
the conceniraison
To calculate
a consistent
on our
choice of the
without
happen
l\\2
a conscious
is
It
effort
not
on
the
of the dissociatedpanicles(here
2H)
of
the
ground
state
of the
change
equilibrium
it is
essential
to choose in
partition
function
The
depends
Zji'mi)
different
need
zeros
for the
energy
diilicuh
our
procedure is to
of each compositeparticle(here
C4),
eigenstales.
to give
be related
reaction.
in ihe
difference
as
must
reactants
different
in the
internal
a change
reaclants.
other
because
consistency
alone.
temperature
force
constant K(x}in
of the
zero
the
way
here
of the
a function
reaciam will
product of the
the indicated
that
says
H2
a!
molecule}
res!.
to coincide
we piacc
Accordingly,
composiie particle at
~\302\243fl,
with the
where
is
\302\2433
energy
the energy
the
energy
Equilibrium for
required
in
to be
laken
is
and
positive.
Examplei Equilibrium
of
atomic
rcacuon Hj
for the
aciioil
mass
hydrogen imo
the composite
to dissociate
reaction
the
Ideal Gases
atomic hydrogen
or
the
dissociaiion
law
of molecul
is
C6)
Here [llj]
atomic
of
li
h>drogen.
hydrogen,
and
fjt]
foltov-sihai
l37)
[h^tpo17^'
equilibriumcon:.lani
given
logK
in
of the
terms
of
atomic
ihe
concent
at a given
is inversely
temperature
hydrogen
ration of molecular hydrogen. The equilib-
by
log^tHj)
2IognQ(H) -
H,. per
molecule.
Spin
F(U2)/i,
factors are
C8)
absorbed
in
F(H,}.
is H,, the
of energy is laken for an H atom at rest. The more lightly
bound
is Kt leading
of Hj in ihe
10 a higher
more negative is F{Ht), and ihe higher
proportion
al absolute zero.
eV per molecule,
mixture.
The energy to dissociate Ht is 4-476
be said lhai ihe dissociationof molecular
into atomic hydrogen is an
It may
hydrogen
of
dissociaiion:
The
En
associated
wiih ihe decomposition
example entropy
gain
entropy
[he
It is believed
of Hj into two independent
in
loss
particles compensates
binding
energy.
reaction
in
not
The
that
most
the
is
H
and
of
Ht:
intergalactic
hydrogen
space
present as
in the direction
of H by the low values of ilie concentration of Hj.
equilibrium is thrown
Here
[he zero
Hjdrogcn
is very dilute
Example:
in
intergalactic
space.
In
liquid
waicr
ihe ioni^lion
process
09}
H2O*~>H+ + OH\"
eeds
to
o.ximalcly
txicnt. Al room
tcinpcraluic
she coiiccmraikm product
a slight
by
the reaciion
cquilibfium
D0}
aGGin&
oy
lo
as required
can
ions
decrease
of
z\\t\\
iictu
ionizaiion
be increased
\342\200\224
fOH
^=
\021
of H* ions is
wai^r
\302\273^ntJ
ihe concentration
of C3i 1 tons wtll decrease
constant. Similarly, ihe concentration
[H*][O!!']
*
a hase lo ihe water,
and ihe H
concentration will
adding
by
siaie oi wafer
The physical
process
prolon
product
is more
ions ate
H*
suggests\342\200\224ihc
of H2O molecules.This
with groups*
moles
in
lo aa as a
to llic
the
accordingly.
ihe
is said
mainiain
\"
of OH
arc given
concentrations
An acid
!0\021molr''.
Chemical Reactions
Gibbs
9;
Chapter
protons,
affect ihe
not sigiltficantry
does
complicated
not bare
associated
are
but
of
ihe reaction
letmsof
ihe
vulidily
equation.
it
convenient
is ofien
lo express theacidily
oraikalinii) otasolulionin
pti,
defined as
pH s -log10[H+].
The
pH
concentration
in
The
solution
ota
moles
slrongesi
blood
Human
Kttictic
Kxati\\ple2
nB,
action.
modelof/nms
moieculc
nAB denote
is
AB
of A,
the
B combine to form a
collision of A and B. Let ha,
formed in a biaiomic
of nAB is
B, and AB respectively. The rale of change
Suppose
formation
a function
of
temperature
derived earlier by
Suppose
\"
The
by
o[AB
some
ptolon.
505A958).
catalytic
in
a collision
of A
result
is consistent
law
ihe
its component
ace constant,
D3)
D/C
with ihe
B, and
with
only. This
action
of mass
that we
thermodynamics.
AB is noi formed
dominant
one
surrounding
standard
A and
atoms
that
nAB
formed
D!)
principally
by
the bimolecular
collision of
and
B, but
is
process such as
species present
A [cvie* is given
is
most
by
molecules
surroundlikely it*1 4HjO, acomplc*of4 water
P(oc_ Roy. Soc tLondon) A147.
M. Eigcn and L. Dc Macycr,
\342\226\240
.
Here E is ihe
So long as ttie
catalyst which
intermediate
is returned
product
is lied
the
actually
The
of detailed
be
the
and
ai ihe
end
IdealCases
for
Equilibrium
seeond step.
quantity of A
of the
no significant
us if AB were formed
what
route Hie reaction
by
same.
The rates, however, may differ.
inverse reaction rate's is culled the principle
must
No
be
the same
in
rnaiier
balance.
Schematic
AH measures
ihe energy evolved in the reaction
the equilibrium concentration ratio [A][B]/[C]. The
barrier to be negotiated
is the height
of the potential
energy
the
reaction
it
determines
the rate at which
the
can proceed, and
takes place.
Figure 9.2
The quantity
nnd determines
activation
before
reaction
coordinate
Reactions
Chemical
and
SUMMARY
1. The
G3
is a minimum
thermal
in
2. (cG/3r)H,= -a;
= W,,(r,ri
ofmass
law
for a
action
of
the
pV
temperature and pressure.
V;
= p.
(SG/SN),.P
a function
iff +
at constant
equilibrium
tfG/cph.,
3. C(r,p,W)
The
- -^w.
alone.
temperature
PROBLEMS
(a)
the
Prove
three
Maxwell
rela-
relations
(dV/di)P
-{dts/dp),
(aVldN)p = +(ap/ap)^ ,
(Qj/cr)jV
two
omit
(lie help
Coefficient
of
subscripts
of D5a)
tjicrniiti
approaches
D5c)
should
subscripts
those
~Ea/dN)x.
D5b)
Strictly speaking,
and
D5a)
and
expansion
zero as t
-* 0.
2.
Thermal
ionization
in
hydrogen
c +
wheree isad
H*ftH,
the
that
Show
of atomic
the; formation
Consider
of hydrogen.
the reaction
the
as
eicutron,
concentrations
equilibrium
I
D7)
[e][H+J/[HJs\302\253acxp(-//T),
/ is
where
not aSTed
and
electrons
concentration
atomic
of
spins
and
the
{im/2zh2K11
this assumption does
hydrogen,
particles;
tiQ
concentration is
The result
result.
final
the
by
given
D8)
0]~[H]\"V'3\302\253p(-//iT).
problem arises in
A similar
thermal ionization
semiconductor
of impurity
The
is
electronic
excited
[H(exc)]
andT -
with
[e]
/ is
a simple
the ionization
proportional
energy,
the square root of the
to
!
state,
conditions
for
ts not
this
that
shows
which
concentration.
atom
/,
Here
problem.
concentration
elccjron
If we add excess
will decrease.
C)
^1 and not
involves
\"Boltzmannfactor\"
hydrogen
the
exponent
B) The
u-jth
connection
of electrons.
are donors
that
atoms
in
physics
No lice lhat:
A)
hy-
adsorption
which
atthe
of
concentration
equilibrium
the
is \\l above
ground
surface of the Sun,with
5000K.
of protons
concentration
H atoms in the
state. Compare
[H]
1023 cm~
|
I
3,
of donor
hnization
impurities in semiconductors.
\\ A
pentavalent
impurity
atom
in crystalline
silicon
introduced in place ofa tetravalent
the role of
in free space, but with
silicon acts likea hydrogen
atom
e2/e
playing
e2 and an effective
mass
m* playing
the role of the electron mass m in the
state
of the
of *hc kmizalion energy and radius o( the
ground
description
the
diclctltic
consta.t\\t
free
silicon
electron.
For
impurity atom, and alsofor the
e ~ 11.7 and, 0pproxima!e!y,
m*
=0.3
m. U there are 10\" donors p^r
cmJ,
K.
100
electronsat
cent
ration
of
conduction
estimate
the con
(called
4.
a donor)
monomer
polymers
4-
the
Consider
Siopotymergrowth.
of linear
A'mer
made
= (A'
up
of
chemical
identical
-f l)mer.
of a sotution
basic reaction step is
equilibrium
units. The
constant
for
Chapter
9: Gibbs free
this reaction,
Reactions
Chemical
and
Energy
mass
of
\342\200\242
[\342\226\240
\342\226\240]
action
satisfy
[N
from the
(b) Show
1]
[If \"/K.KjKj
Iheory of reactionsthai
\342\200\242
\342\200\242
\342\226\240
K.v
ideal
for
gas
D9)
conditions
(an ideal
solution):
where
iVmer
MN is
^Bnti2/M,^rm
wQ(W)
molecule,
(c)
Assume
ratio [N
concentration
4-
N
t]/[N]
\302\273
j,
at
so
thai
room
FN
E1)
is the
nQ{N) =
Hq{N
free energy
+
if there
temperature
1),
of one
Find
is zero
the
free
Phys.
in the
change
40,60A972).
for the
expression
equilibrium, (a) Find a quantitative
=
=
n+
n~ in the particle-antiparticle
concentration n
reactionA+ 4- A\" = 0. The reactants may be electronsand positrons;
protons
Let the mass of
and antiprotons;
or electrons and hoies in a semiconductor.
the
either particle be M; neglect
of the particles. The minimum
energy
spins
A\"
is A-Take
the zero of the energy scaleas the
release
when A* combines with
with
no particles
energy
present, (b) Estimate n in cm\023 for an electron (or a
300
that
K. with a A such
A/t = 20. The hole is
hoie) in a semiconductor T \302\253*
viewedas the antiparticic
to the electron.
Assume that the electronconcentration
5. Pavtkte-antipartkk
thermal
equilibrium
is equai to
the
hoie
concentration;
assume
aiso
titat
the
particles
are in
the
3.
10
Chapter
Transformations
Phase
PRESSURE
VAPOR
276
EQUATION
Derivation
of
Point
Triple
278
284
Example:
System
WAALS
DER
VAN
284
for Gas-Solid
285
Equilibrium
287
OF STATE-
EQUATION
CriticalPoints
288
the
for
van
der
the
van
of
2S9
Gas
der Waals Gas
Waals
291
Nucieation
Fe
from
agnet
295
298
OF PHASE TRANSITIONS
THEORY
LANDAU
302
Ferromagnets
Example:
First
294
ism
Order
302
Transitions
305
PROBLEMS
1.
2. Calculationof
3. Heat
4.
and
Energy,
Entropy,
for
dTjdp
Gas-Soltd
7. Simplified
Note: tn
305
305
Water
Order
the
305
305
Equilibrium
305
Equilibrium
of
6. Thermodynamics
First
of Vaporization of Ice
5. Gas-Solid
8.
of van
Enthalpy
the
Superconducting
306
Transition
first section
307
307
Transformation
s denotes c/iV,
the
entropy
per atom.
In
the
section
on fcr
PRESSURE
VAPOR
of pressure versus
The curve
EQUATION
by
together
and under
or solid
a liquid
in
energy
another
one
with
interact
of matter at constant
substance. The curve is
a real gas in which the atoms
of the
isoihcrmsof
the
We
or molecules
associate
free
the
a quantity
for
volume
temperature is determined
calledan isotherm. consider
phase,
Two phases
real
ofa
in
atoms
the
in
and
solid
we say
As
There
are isotherms at
in
isothermsfor
and gas
soiid
which
holds also
equilibrium
liquid-gas
low icmperaturcsfor
for
the
which
coexist. Everything
equilibrium
solid-gas
solid-liquid equilibrium.
and
on a
coexist
may
vapor*
the
the
phase\342\200\224exists,
only a single phase\342\200\224the
the pressure. There is no more reason to cali this phase a gas than
we avoid the issueand callit a fluid. Values of the critical temperature
great
so
no
fluid
temperaiure
a liquid,
if
of the
temperature
how
the
other.
coexist and
the
Liquid
critica!
phase.
gas
liquid
for
and the
each
with
a definite
show a region in
gas may
equilibrium
with
coexist,
may
for severalgasesare
Liquid and gas
iO.t.
in Table
given
matter
extent of an isotherm
a
to
from zero pressure
infinite
along
they coexist at most only
pressure;
of atoms,
fixed number
section
of the isotherm. For a fixed
and
temperature
the
there will be a volume above which all atoms present are in
gas
phase.
at
room
bell
an
sealed
A small drop ofwater placedin
evacuated
temperature
jar
will
A
water
of
entirely.
the
evaporate
the
from
atoms
relations
are
by
suggested
for
the
the entire
along
filled
with
gas at
H2O
some pressure.
may
already saturated with moisture
There is a concentration of water, however,above which
into a liquid drop. The volume
vapor will bind themselves
exposed
The thermodynamic
conditions
coexist
never
leaving
entirely,
evaporate
drop
will
to air not
Figure
JO.i.
conditions
equilibrium
for
of two
the
coexistence
of two
in
thermal,
diffusive,
Vapor Pressure
IO.I
Figure
is constant, but
Efiei^
is only
and its
<t
the
s^nclc
vapor are in
of a
isotherm
Pressure-volume
and
Gas
+ gas
Liquid
Liquid
gas phases
region of
Hquid
reyj
gas
at a
may coexist,that
4- gas the pressure
volume
down,
piston
pressure
of
gases
Tt, in
in
He
5.2
H2
Nc
414
N.
Ar
151
210
Oj
Kr
Xc
289
CO,
33.2
126.0
1543
647.1
the
.W.2
Equatio
10: Phase
Chapter
Transformations
or,
18\\
Ml
the
phases
pressure
temperature
the
general point in the p-x plane
alone is stable, and if
liquid
phase
At a
Metastablephases
may
may
phase
have
a lower
by
occur,
which
that
dp;iQ
the
divides
It is a
pl
and
liquid
A)
phases.
gas
in the
species
Note
that
the
B)
/ijl
two
ns
phases
<
Pi
do not
or superheating.
supercooling
metastable
a
chemical potential.
temperaturez0.Suppose
Pa
p2;
for which
temperature
has
fit
/l,(p,T)
the
t2:
The chemical
coexist.
common
and
Pi = Pg
/Jj,;
tj
and gas,
liquid
*j
equal
that
+ rfi.Thecurve
p, t plane into a
the
two
two
in thep.T
Versus
phases,
phases
liquid and
also coexist
phase diagram, as
given
in
Figure
phasescocxist
10.2
for H2O.
condition of coexistencethat
C)
D)
dt).
We
relationship betweendp
a series expansion of each sideof D) to
C) and
Equations
make
D) give a
and
dx.
obtain
-.
E)
ion
Cot
ojthc
Figure
10.2
relationships
the
jiB in
and
shown.The phase
here
boundary
bciwcen
ice
-100
100
200
Temperature,in
In
the
limit
as dp
300
375.
400
\302\260C
by
C)
which
and
E). This
result may
is the differential
be rearrangedto give
curve
equation of the coexistence
or
vapor
pressure
curve.
in terms ofquantities
accessible
to
measurement.
occur
In the
may be
expressed
treatment of the Gibbs
in G)
free
With
9 we
in Chapter
energy
the definitions
s
the volume
for
relations
the
found
per moleculein
and entropy
1 (cG\\
5 =
V/N,
o/W
(9)
each
we have
phase,
(dp\\
)JJ
Then
for
G)
becomes
dp/dt
01)
~
Here
sa
st is
moleculefrom
of entropy
the increase
the
gas, and
the
to
liquid
the
of
ihc
is
t\\
vg
we transfer one
increase of volume
when
system
\342\200\224
of the system
we
when
to coexist.The number
varied, subject only
The
be
of
to
of molecules
numbers
quantity
added
sa
to the
one molecule
transfer
the
s, is
when
decrease
added
in the
the
system
as
vary
Here
constant.
moiecule
is
volume
the
Ns and
outside
in the
is transferred
reYersibly
the
of
temperature
from
molecule
one
transfer
(Va
the
are
system
from
constant.
process, the
must
that
the liquid
(If heat is
temperature
of
will
heat
transfer is
l1Q ~
by virtue
will
sysfern to
the
A\\
phase
and
not addedto
+ Na
N,
in
in each
molecules
\"
TE*
of the connectionbetween
5'}'
and
heat
A2)
the
change
of entropy in a
tEs
A3)
of the
Dcritaiion
Coexistence
measured
Cur
by
elementary
calonmetry.
We let
A*\302\253
the change
denote
to
she
We
gas.
of volumewhen
combine
A1), U3),
A4}
i-g-v,
is transferred
molecule
one
from the
liquid
A5)
This
phaseis
replace
as the
much
very
larger
in the
than
pressure
atmospheric
(b)
so
that
may
Av by vg:
A6)
may
the ideal
written as
that
assume
We
i'9/i;( ^
be
approximation is very
Av
With these
{16)
vt/yr
Avsva=
At
we
Ngz
applies
to the
good.
gas phase,
A7)
zip.
of temperature,
molecule. Given L as a function
curve.
this equation
may be integrated to find the coexistence
the
the
heat L is independent of temperature over
latent
if, in addition,
Thus
the
of interest, we may take L = l.,Q outside
integral.
range
temperature
when we integrate (IS) we obtain
where
is the
latent
heat per
r
/dp
(lv
A9)
10: Phase
Chapter
logp
Traasfortnat
\342\200\224Z-0/i+
where p0 is a constant.We
one
where
LQ as
defined
to one
instead
refers
If Lo
nioiecuie.
) =
constant;
p0CXp(-L0/T)
the latent
heat of vaporization of
mole, then
is the
versus 1/T.
gas constant,
R =
substantial
-Crit
ca! p
with
consistent
regions,
the
Jin.
\\
id
wa
er
X 103 \342\200\224
1 atm
pressure
Vapor
ofwaier
and of
\\
\342\226\240-
102
\"
is 1/T.
The
ice
iine.
\\
10
Si*\"
vc
\\ s
\342\200\242Ice
\\
1.5
2.0
2.5
in
K~\302\273
4.5
5.0
Tcmperamre,
Figure
3
in
10.4
eial.. Journal of
A959)-
10-4,
vapor pressure of 4He, plottedin Figure
of temperatures
between I and 5 K.
The phasediagram
of 4He
at low temperatures was shown in Figure 7.14.
Notice
tUat
the liquid-soHd
eoexistence curve is closely horizontal below 1.4K.
We
infer
from
this and (I!) [hat the entropy of the liquid
is very
nearly equal
to the entropy of the solidin this region.
It is remarkable that the entropies
a normal
should be so similar,
because
liquid is much more disordered than a
of a normal liquid is considerably higherthan
that
solid, so that the entropy
result
approxmiate
is widely
used
in
the
B0). The
measurement
10: Phase
Chapter
Transformations
3He,
the
slope
is a
4He
the
of
quanhim
liquid-solid
(Figure
region the
in this
and
7.15),
of the
solid. The
Triple
point.
The
poin!
triple
of
is that
a substance
point p,, t,
in
She
p~z
The
of
of
pressure
vapor
both
temperature
point
iriple
at
substance
She
phases.
the
For
the
water
defined
that
such
Latent
the
point, of
triple
ofa
and enthalpy.
heat
the liquid
of the
temperature;
melting
pressure
point
triple
two
phases
difference
of
enthalpy.
The
at
constant
-f
pV
= dU -f
L
Values
of//
at coiisnint
are
\302\253
tAa
tabulated;
dV
-f- pdV
//,. Thus
\302\273
At/
phases, where H is
Hr-
difference
When
called
the
we cross the
applies:
\342\200\224-
Vtlp.
\302\273
Ml
B2)
jt,)dN
at constant
pressure:
pdV
(}tg
pAV
from
the entropy
t times
B.
as
transformation,
phase
to
The
pressure.
the
two
between
is dH
differential
is the
lemperaSure
point
temperatures depend
meiSing temperature
Melting
pressure.
atmospheric
pressure
Ha
- llt.
by integrationof the
B3}
heat
capacity
of the
Derivation
Coexistence
Curve, p
Ver
B5)
jc,,
gas-sotidequilibrium.
We
construct
a simple model
can
derive ihe
easily
a
to
apply
liquid.
io de-
as in Figure 10-5.
vapor
Roughly the same model would
of N atoms, each bound as a harmonic
oscillator
of freImagine the solid to consist
u to 3 fixed
ol force. The binding
center
oleach
atom in ihe ground siaicis
frequency
energy
that
is, ihe energy of an atom in its ground
to a free atom at rest.
\302\243fl;
state is \342\200\224
co referred
\342\200\224where
The energy states of a single oscillator arc ntioi
h
a
or zero
is
r.o,
positive integer
in o:.e
we suppose itial each ntom can oscillaiconly
(Figure 10.6). For the sake of simplicity
dimension. The result for oscillators in [hrce dimensions
is left as a problem.
ol a single oscillaior in llie solid is
The
Junction
pariiiion
describe
pressurecurve
Z, =
for
ihis
with
a gas,
We
model.
\302\243\302\253p[-(n/10>
= expOWt)
eo)/r]
=
\302\243\302\253p(--,,Aa./T)
B6)
The Ziee energy
F, is
F* = u* ~
The Gibbs free
energy
in the
Gs
Tff,
B7)
-tlogZ,.
\302\253
Vt
to-, +
pt',
=>
Fs
pvx =
//,.
Figure
10.S
wiih
aionis
pressureis a
energy ol the
in
than
aioms
in a
Aloms
in the
in
cqmSibn
function
The
solid phase is
in [he
atoms
ihe
solid
gas
lo be
lends
in
higher
the
at
may
temperature
high
be
in ihe
iIk
atoms
all ot
gas.
\\
lanpemSurc most of
lo
;src in ll
most of
ihe a
ihe
Chapter
(u. The
lor of frequency
ssumed 10 be % below that
in!he
o(a
gas phase.
bound
The pressure
volume
i>i
per
in
in ihe
that
o[
smaller
but Uie
which il is in contact,
atom
in [he
the volume vt per
\342\226\240
If we
the
is equal to
solid
the
atom
pv, we have
(or
the chemical
potential of
,/t) =
[hesolidp, S
We
to be
'
with
equilibrium
we
insert
nQ from
gas
phase,
and we
C0)
\302\253q
The gas is in
B9)
the ideal
make
atom
whence
\342\200\236
exp(-logZJ
<stp(-to/i)[l -
the
the solid
t\\
'\"a
when
inQexp(-E0/t)[l
).f
or
).\342\200\236
- exp(-/1<0/t)].
C1)
C.63J:
C2)
(j^j
The
mode!
simplest
interactions
the
he was
below,
ideal
the
modified
van
the
as
known
- Nb) = Nx ,
+ N2a/V2)(V
der Waals
b is
had
gas
at
repulsion
To
we
now
add a
volume
-NT{log[)fQ(V
correction
a is
between
two
repulsion
range
=
properlics of the model
relation p
general
V,
be treated
can
distances
but
the
this
in
constant
for
the
C4|
+ i].
-NT[log(na/n)
in C4) by
atoms
F.24),
free
approximately as
volume
the concentration
therefore
short
tlic
the ihcrmodynamic
short
not the
available
for
transition.
F(idealgas)
if
C33
the
a, b are interactionconstantsto be defined;
of the long range attractivepart
the
of
mieraeiion
a measure
give
form
V. The
volume
of State
Equation
OF STATE
VAN
Waats
Der
Van
when
Sb,
n
N/V
have
- Nb)/N] +
intermolecular
C5}
1}.
attractive
forces.
Figure 10.7
The
iiucraaion
energy
between
The
repulsion plus a long range aiiracHou.
short
range repulsion can be described
that each molecule
by saying
approximately
coie.
Chapter
Mean Field
Method
There exists
taking
the effect
particles
system.The most
gases and to ferromagnets.Let
of two atoms separated a distance
of a
known
widely
tp(r)
is n,
gas
the
atom
interactions
potential
for
the
among
method are to
energy of interaction
the concentration
r. When
method,
of the
applications
the
denote
by
the
called
method,
approximate
simple
account
inio
of atoms in
on
atoms
C6)
value
the
of
ihe
We exclude the
convention.
useful
is
volume
constant
approximation.
of concentration
in
we
language
energy
say
the
\"
molecules.
interacting
From
regions
thaS
it follows
C6)
of a
that
The
factor
exact
s MJ =
is
Heimholu
free
of a
energy
F(vilW) =
The
pressure
*=
obiain
the
the
free
C7)
-N2a/V.
it arranges
problems;
only once in
-\\BNna)
is counted
molecules
of bonds
number
is,
V by
volume
j is common to self-energy
\"bond\"between two
is
\342\226\240
the interactions
gas of N moleculesin
AF
field
we ignore the increase
concentration
uniform
of strong
attractive
potential energy. In modern
mean field method neglectscorrelationsbetween
assuming
By
the
we
der
v;m
approximate
Waais
that an
interaction
approximation
for the
yas:
-.Vi{log[\302\273u(l'r
Sh)/N~\\
+ 1}
- Nza/V.
0$)
is
C9)
'\342\226\240-^\302\253'\027^5-F
the
Figure
suggests
pressure
be
used
of intermolecular
near ihe boundary
Y. The van dci Waats argument
lhal ihcse forces contribute art internal
Nxa!Vl which Is lo be addedlo ihe
10.8
forces that
of a volume
Direciions
on molecules
ad
as ihe
pressure
in
gas taw.
the
o
o
of volume Khas N
not
b.
The volume
molcculcSi
V
S'b.
Intuition
by molecules is
occupied
suggests that iHis fece volume should be used in
V.
llic gas law in place
of the coiiiaincr Volume
Figure
each
O
0
O
o
(p
Waals
10.8
and
coniainer
of volume
\302\251
der
Hie
10.9
+ N2a/V2){V
equatum of
~ Nb)
\302\253
A'l
D0)
and
b arc
interpreted
in
10.9.
Points
ne the
quantities
der
Gas
Waals
pc ^ a!21b2\\
Vc
3Nb;
xc
^ 8a/27b.
D1)
Chapter
10:
Phase
Trans/or,
. -
0.95tt
P/Pc
Figure
In termsof
these
der Waals
Tile van
10.10
critical
the
van der
the
quantities
equation of
Waals equation
\\(V
f7HJAH
stal
Courtesy of R. Cahn.
temperature.
Figure
may
10-10
be
l\\
8t
3/
3t/
for
written
becomes
D2)
near the
temperatures
in terms of the dimensionless
several
variables
ps
9sVfV.\\
pjPc\\
e t/tc ,
D3)
D4)
This
si!
gases
result
!ook
ts
known
alike\342\200\224if
as the
they
correspondingstates. In termsof p, V, t,
the van der Waals equation. Valuesof a
law of
obey
Free
Gibbs
usually obtained
and b are
Realgasesdo
one
At
same p,
at the
substances
not
the
obey
P~V
curve
phases.
and
coincide,
At a
horizontal
corresponding
local
the
Here
and
tc the critical
Above
tt
of the
van
der
gives
N.
of pressure
function
as
a function
we
cannot
by
gas
of
Nt{log[\302\273u(K
V,
t,
N;
It is
want
Nb)/N]
the natural
put G
conveniently
(9.13).
the characteristics
With G = F + pV,
of
exhibits
pressure.
instead ofvolume.We
relation
Waals
-^
-\342\200\224^
This equation
p, t, Unfortunately
Vet
Gas
constant
pc,
\342\226\240-
Waals
der
G(x,VtN)
respectively.
exists.
The Gibbs
liquid
9 = 1;i 1. We call
critical volume,and criticaltemperature,
p = 1;
by D4) if
pressure,
separation
Energy
of the
@i-
no phase
Free
Gibbs
and minimum
maximum
f has
constant
at
satisfied
are
conditions
ihe subsiances.
there
aThese
states of
pc and
observed
Gas
M'aah
(let
van
to high accuracy.
equation
the critical
point,
called
Vy x are
the
to
fitting
by
of the
Energy
variables
into an
G(z,p,N)
+ 1],
analytic
because
we
D6)
for G are
form
we can
as
temperature
represent
unstable
ft,
in Figure
then
fig. The
phases.
The pressure
transition
between
Results
V2- This
is equal
to the
shaded area
10;
Chapter
Phase
Ttansfo
-0.40
t\342\200\224
--
rasure
,-Vapor[
/
\\
Figure 10.11
der
Waals
equaiion
(b) Gibbs
free energy
versus
stale;i = %..
above
the
To see
line.
have
difference
dG
versus
pressure
i = 0.95tc. Courtesy
pressure
of
for van
R.
Cahn.
Waals equation of
ihis, consider
dG
We
energy
Vdp at
\302\253
~adx
Vdp +
of G between V\\
and
D7)
pdN.
of
particles.
The
V1 is
G,-G,=
fWp,
D8)
1
~p
0.95
nqb =
LiqutaS^
\302\273bic
G/Nrc
'
0.990
0.988
0.986
0.984
\342\226\240
't/t,
(a)
Figure
versus temperature
of A. Manoliu.
10.12a
of slale a! p
for
van
der Waals
=
p
nqb
equalio
1.0
\\
\\
\\oas
-2.70
0.90
I.OO
1.10
1.05
t/t,
(b)
Figure
of slate
10.12b
a! the
Gibbs
crilical
free energy
pressure
pc.
der
Waais
cquatiO!
Chapter
Id: Phase
Transformations
conslan
- ^Liquid
-Cocx
\\
fir
Stetice
<\302\243
as
|\\
s.
v.t
10.13 Isotherm
of van
lemperafure belowliie critical
Figun e
less
than
above
lliegas
phase exisls. Between
in stable equilibrium lies along the
line
and is
liquid
and
liquid
and
volumes
bul ihe
When
equals
the volume
/^{r,p)along
Hie
we require
Nuclcatiou.
of the
magnitudes
j.tg
Let
that
and
V2
coexistence
is available.
shaded
areas,
areas are
equal,
line
coexistence
horizontal
Vx
an inhomogencousmixture
of two phases. The
gas phases coexist. The proportion of liic
be such
lhai ihe sum of fheir
gas phases must
volumes
only
Kj
Ihe system
volumes
For
!hc liquid
Vt only
der Waalsgasat
lempcralure.
one
G?(t,/>)
drawn
in
negalive
the
figure.
In equilibrium
/*,.
Aji
\342\200\224 \342\200\224be
;i,
ftg
ihe
chemical
potential
difTerence between
G,
=
G9
-{
+ 4nR2y
D9)
Ferromagtutism
the surface
y is
where
drop
will
grow
when
An
Gr
0 =
ti&G/dR
This
is the
fend
to
critical radius
R tlie
larger
drop
will
to
tend
E1)
that
because that,
drop
will
energy.
too, will
At
lower
free energy.
the
must
that
energy barrier (Figure10.14)
fluctuation in order fora nucleusto grow
beyond
in
E1) D9):
The free
(&G)C
to
free
the
Jower
will
spontaneously
grow
R the
At smaller
a drop-
of
because
spontaneously
evaporaie
E0)
\302\2532y/H,A/i.
nuclcation
for
when
+ SnRy ,
-4nR2iii&n
Rc
The liquid
is attained
of AG
maximum
unstable
tension.
surface
or
area,
If we
assume [hat
express
Aji as
the
vapor
for
-r
Kcrro
300 K
at
water
and p
E2)
like an
behaves
p is
pressure
by a ihcrni.i!
substitution
of
by
overcome
R,. is found
(lenPW/nMl*I}.
Aft
where
be
tlog{p/peq)
the
gas
co).
phase
and
use
We
pe<l
72erg
the
equilibrium
cm\022 to
vapor
estimate Rt
x !0~6cm.
= l.J^tobel
ism
magnet
means
a magnetic
has a spontaneous magneticmoment,which
field approxithe mean
moment even in zero applied magneticfield.We develop
defined
as the
of ihe magnetization,
approximation
SO the
temperature
dependence
each
moment
niagnelic
magnetic
per unit volume. Tlie centra! assumptionis that
alom experiences
an effective fieid BE proportional to she magnetization:
A ferromagnet
BE
where
I is
a conslans. We
take
the
\302\253
AM
external
E3)
applied
field as
zero.
Chapter
10:
Phase
Tram/or
barn
Critical
*\"
or
t for growH,
3n nuclei
cortdcnsut
fx
'
ondensation
\\
nuclei
__
evaporate
\342\226\240'\342\226\240\342\226\240-
Figure 10.14
of
function
Excessfree
drop
radius
energy
of drop
relative lo
gas, as
gas
is
supersaturated
this
curve
as drawn,
barrier.
a system with
Consider
a concentration h of magneticatoms,
and of
approximation
an
found
each
exact
of spin
E3)
Me
.
\342\226\240\"\342\226\240_\342\226\240_\342\226\240
this
for a
becomes,
n/nanh(/dMA)
for the
result
= HjitanhOiB/t).
E4)
ferromagnet,
'..
'.
E5)
Fcrromu^cth,
1.0
0.8
0.6
0.4
0.2
soiuiion of \302\243q.
for the
Graphical
E6)
reduced magnetization ,,i as a function
of temperature.
The reduced magnetization is defined as m = M/n/t. The
left-hand
side
of Hq. E6) is piolicd as a straight
line in
10.15
Figure
versus
curve for
in
the
2 intersects
m s= 0,
t =
(or
this
it) is
murks
ictnpetalure
for
Curve
lo
tangent
i =
0.5 is in
-\342\200\242
0 the
magneiic
we write it
temperature
iiie
tn
f
line
moments
are
Figure
and
10.15. The
versus
shall
We
M.
left
of
sides
and
n/i. As
0.94
l.so
that all
absolute zero.
see that
E6)
ianh{Hi/r).
this
equation
separately
curvesof
up at
iined
in
region
s=
\302\273i
whence
z/n[i2X,
ferromagnciic
in at about
moves up to
hi
as
the suatght
Sine m at ihc origin;
ilic onset of fcrroiiiagnetisiu.The
nonzero
with
region (iherc
curve for / = i
paramagnetic
The
fieid).
intercept
al
in only
iine
straight
x obtained
in ihis
temperature
ts
way reproduce
the
I,
10;
Chapter
Phase
Transformation
of
Figure 10.16 Saiuration magnetization
as
a
nickel
function of temperature,together
with
ihc theoretical
curve fci spin \\ on ihe
resuiis, as
experimental
in
shown
magnetizationdecreases
smoothly
OF
THEORY
LANDAU
consider
free
to
applicable
at
systems
F =
energy
with
minimum
\302\243,
system,
electrons
bonds
have
can
a certain
be indepaideally
mean
field theory
the
It isnot helpful
system
can
to
all possible
consider
by a single order
be described
in ait
value
alloy
c,
specified,
AB. In thermal
cc{c).
In
FL(\302\243.x)
(\"unction
energy
of phase transi-
xi, which
Greek
bondstotola!
will
to what variables?
dielectric
superconducting
of the
parameter the
TRANSITIONS
a large
respect
variables. We
the
at z
zero
PHASER
formulation
10.16
Figure
to
E7)
order
value
has
parameter
\302\2430{t)is
the
value
the
of
Landau
Transitions
of Phase
Theory
c, that
F(t)
Plotted as a function
than one minimum.
\302\273
Fl($0,t)
of
for
\302\243
r, ilic
constant
function
ferroelectric
are
systems
exam
well-behaved function
something
this.
We
that
\302\243
it
can
not be
lowest
In a
state.
equilibrium
the
becomes
more
as
minimum
Landau (\"unction
is an even
applied fields. Most ferromagneticand ferro-
pies of
of
should
that
of
absence
the
in
\302\243
the
have
to systems
ourselves
E8)
Co-
minimum
restrict
*
\302\243
determines
first order
We
if
FL(\302\243r)
free energy
taken
also
that
assume
be expanded
for
For
granted.
F 1(^,1) is a
in a
sufficiently
power series in
\302\243\342\200\224
function of
an even
as
\302\243,
assumed,
entire
The
dependence of
temperature
coefficients
g6- These
g2,gx,
ga\\
FL(\302\243,x)
is
are matters
coefficients
in the
contained
for
expansion
or theory.
experiment
changes
sign at
^(x)
example of a phase transitionoccurswhen
a temperature i0, with y4 positive and the higher terms negligible.For simplicity
The simplest
take
we
linear
g2(t)
in i:
~
<72(r)
the
over
these
Witli
The
temperature
The
which
of interest,
F0)
and we take g4
as
in that
constant
range.
idealizations,
form F0)
certainly
range
temperature
- to)* .
(r
fails
is not
and
cannot be accurateover a very wide temperature
range,
on tembecause such a linear dependence
at low temperatures
consistent
equilibrium
has the
with
value of
the
is
\302\243
law.
third
found
it
at the
minimum of
FL{$
;t)
with
respect
roots
f~Q
and
= (to
- r)(a/g4).
F3)
Phase
Chapter
iff;
With a
energy
function
Transformations
above i0;
at temperatures
F1)
0 corresponds
J=Xt) =
of
FdZ'J-)
as
of F(r) with
in Figure
ihe
for
\302\243:
temperature
is
F4)
0g(l).
temperature
of
a function
Figure 10.18,and
shown
(a/gj(to
at temperatures
function
The variation
to the
in Figure
10.19.
elergoes
to
continuously
Figure
for an
zero
as the
in
which
temperature
10.17
Temperature dependence of (he free energy
of the second order.
ideatized phase t ransition
Figure
10.18
free energy
Landau
function
As the
reprcscniaLivc
temperatures.
the equilibrium
value of \302\243
gradually
posiiion
of the minimum
Figure
10.19
temperature,
curve is not realisticat
use Of Eq. F0): the third
thatdf/rfr
increases,
polarization
a second-order
->0asi-*0.
at
\302\2432
by
t0
the
Spontaneous
for
versus
low
law
versus
requires
Chapter
10: Phase
\342\200\224
Transformations
at t
is continuous
dFfdz
temperature f0.
Such
Transitions
nonzero
with
latent
The real
is no
there
latent
heat at the
transition
transition
them presently.
discuss
= rQ,so that
best
the
superconductors.
Example:
Landau
which
V(M) =
j iscommon to self-energy
ihe factor
where
F6)
-\302\261
regime
in
FL{M) ~
At
transition
Ihe
which
\302\253
n/j.
Thus
constant -
temperature
\\M2(/.'~
the coefficient of M*
with
First Order
Transitions
latent
lion
order
at
heat
constant
transitions
in metals
transformations
the
discussion
F7)
fursciion
\342\200\224A+
entropy
M2J2nn2
i0
in agreement
The
problems.
per
lermsof
vanishes,
unit
volume
higher
is
order.
so ihat
F9}
\302\273}i2>.,
following
F8)
E6).
characterizes
a first order
is
negative
and
gb Is
positive.
We
consider
first
l(K20
Figure
first
Landau
free energy
at representative
function has equal minima
For t below rf the
as shown.
\302\243
order
versus
function
transition,
i1
temperatures.
Order
Transitions
m a
At
xc
at a
is
minimum
finite
absolute
is
a
there
iatger values of ^; as r passes
through
tc
in the position
of the absolute
disconimuouschcinge
minimum.
The
artows
mark the minima.
the Landau
The extrema of
this
function
are
given
by
at
\302\243
0 and
the roots
FigureJ0.20:
G1)
-
Either
\302\243
0 or
G2)
At
with
transition
the
c,
0 and
temperature
with the
rc the
root c^O.
The
value
of
be
xc will
equal
for
not be
the phases
equal to r0,
Chapter
Phas
10;
and the
order parameter\302\243
(Figure
weui
earlier, where \302\243
transformation
show
may
those
differ from
results
These
xc.
at
continuously
as in supercooling
zero
to
hysteresis,
hysteresis exists in
t0 -
L is
the two
2.
The
van
heat L
order
transfor-
but
supcrsaturation,
no
is the
An
two
phases
must
satisfy tiic
der
Waais
volume
difference per
pV is the
the energy
'
is a minimum
of state
(P +
atom between
necessarily
V +
enthalpy.
is
-
N2a!V2){V
Nb) =
Nx.
function
energy
and entropy
not
value \302\243,,
where
equation
free
Landau
- Hlt
~ H,
4. In the
first
phases.
latent
3. The
tf.
or
1. The
where
continuously to zero at
phase transition treated
transition.
order
a second
rrt in K
order
second
the
in
not go
does
10.21}
-20
-40
_60
are
the
taken
when
thermal
with respect to
when
\302\243
the
system
is
in
thermal
equilibrium.
A first
5,
order
Intent
heal
and
that
the
by
hysteresis.
PROBLEMS
/,
dcr
van
ofthe
entropy
and
energy,
Entropy^
(c)
the
enthalpy//
//(r./>)
arc
results
given
2. Calculationof
equation
U =
INi.-
= U
+ pV
|Nt
-jNr +
to first order
near p
the
for
G6)
terms o, h.
\\V;ials correction
the vapor
from
Calculate
G5)
2N2ajV\\
2NuPfx.
der
van
~ 1 atm
G4)
i%
NhP
the
in
heat of vaporizational
wmcr. The
G3)
N2.ii!V.
+ N2bx/V
water.
for
(IT{dp
of elT/dp
value
the
en-
+ 1}.
Nb)JN]
N[log[nQ(V
H{i,V)
All
Show
is
energy
the
thai
Show
(a)
gas is
Waats
o(b) Showthat
IVaah gas.
of van der
enthalpy
Hquid-vypor
100Xis 2260
Express
Jg\021.
pressure equaof
in
equilibrium
the
result
keivin/atm.
3. Heat of vaporization
Hgal
of
vaporization
ice
4.
Gas-solid
we
let the
at
ice.
of
the
latent
soiid move in
\302\273
haS)
heat
the
range
the heat
Jmol\"'
of vaporiza-
of interest.
of the exampleB6}-C2)
in
dimensions,
three
vapor
per atom
pressure
is tQ
which
the
is
\342\200\224
\\i.
Consider
equilibrium.
that the entropy
assumption
GaS'SoU'd
temperature
a version
Consider
equilibrium.
osciSiators in the
of water
pressure
~l\302\260C.
high temperatureregime(t
5.
The
and 4.58
~2=C
10: Phase
Chapter
Transformatio
of ihe
energy
system
minimum
of
ihe
+ F,
number
total
the
the
independent
container,
thai the
(a) Show
volume
of the much
total HeimhoHzfree
is
F = F,
where
that the
the approximation
Make
monatomic.
free energy
\"
that in ihe
G8)
(b) Find
constant,
is
Ng
to N^show
respect
- I] ,
N,r[!og(N,/l'il0)
N = N,
of atoms,
with
-Ufa
the mini-
equilibrium condition
09)
vapor
6.
of the
Thermodynamics
pressure.
th
2/i0
SI
units
for Be. Because Bc decreases with
side is negative. The superconducting
phase
temperature,
increasing
has
(SO)
[i0 ih
in
that
the
lower
entropy:
it
the
right
is the
more
that
Show
Cs and
CN, the
volume,
are
by
(81)
Figure S.iS is a
than
linearly
dominated
plot of Cj'T
with
by Cs.
T1
vs
decreasing
Show that
and
r, while
Hiis
implies
shows
that
Cs decreases
Cs decreasesas yz.
For
much
\302\253
tc>
faster
AC
is
_-
-0.2
X. Normal
.1
Superconductor
*STC=1.180K
0.5
lure.
Temper;
of
Experimental values of the Tree energy as a function
in the superconducting state and in the normal
stale. Below the transition
is lower
temperature
T, = 1.180 K (he free energy
in !he
transition
slate.
The
(wo
curves
at
the
supcrcondtiding
merge
heat
is second order {(hereis no laient
tempcra(ure, so thai the phase transition
a! Tc). The curve
and
of transiiion
in
zero
is
measured
FN is
magnetic field,
Fs
normal
slaie.
measured
in a magnetic
to
in
(he
field suftkien!
pu! the specimen
Figure 10.22
temperature
Tor aluminum
Courtesy of
N.
E. Phillips.
7, Simplified
superconductors
Bt(i)
that
Cs
linear in r,
as for
Assume
and plot
calculate
heat
8.
crystal
of
order
two.structures,
siable
form
low
of the
than linearly as
(Chapter
7}. Draw
gas
the i dependencesof
Fermi
of
the transition.
temperalure
substance.
separated atomsat
form
by a
and
he
then
(83}
also
t -* 0.
on the resultsof
the two
heat capacities,
Cs(rc)/Cv(r(}= 3.
crystal that
can existin
'hat
and /?. We suppose
the /J structure is the stable high
the
energy
6 to
Problem
the
energy
Cs is
that
Assume
entropies,
Consider.'!
two
Show that
transformation.
denoted
most
d/r(}2].
faster
vanishes
a
Bt0[l
of
scale
density
is
taken
eilher
is the
a slrucmre
semperalure
as the
1/@) at r
==
stale of
uill
be
Chapter 10:
Pha:
velocity of sound ve
U?@).
to lower values
phase, corresponding
thermal excitationsin
phase.The
!he
energy.
the
larger
Soft
free
by the
is
thermal
excitation,
tend
systems
the
of
the
-~rc2r'i/3Oi;3/i3,
by
given
velocity of
all phonons.(b)
Show
value of U{0);thus
to be
low.
in the
the lower
have larger
the larger
will
phase
in
the
(a) Show from Chapter 4 that
phonons in a solid at a temperature much
at
systems
the
have
\342\200\224
0 will
If the
<
Ux@)
at
free
energy
density
Debye approximation
that
at the transformation
with
will
a finite
actual
is
transformation
defined
<
transformations
as the
trans-
thermal energy
(85), U
that
must
the
that
L = 4[U,@)and
(84)
Show
(84)
as the
iv
In
taken
temperature
>-v.-').
There be
ofa classof
contributed
t/,@
be
latent
to carry the
heal for this model is
supplied
(85)
11
Chapter
Mixtures
Binary
310
SOLUBILITY GAPS
OF
ENTROPY
AND
ENERGY
MIXING
wrth
Interactions
Nearest-Neighbor
Example: Binary Alloy
of
Structures
Mixture
Two
Solids
with
Different
Crystal
Example:
Low
3Hc-\"He
Mixturesat
Temperatures
Example: Liquid
for Simple Solubility Gaps
Phase Diagrams
PHASE
EQUILIBRIA
AND
SOLID
BETWEEN
31-1
318
319
320
321
LIQUID
322
MIXTURES
325
SUMMARY
330
PROBLEMS
330
1. Chemical
2.
3.
Mixing
Segregation
Coefficient
of
Impurities
Alloy
330
330
331
331
33i
11:
Chapter
Mixtures
Binary
and
Many
or more
two
have
effects
physical
Mixturesarc
of
systems
Mixtures
to form
three
and
mixtures
are called
four constituents
\"oii
expression
or
more
mole-
and not
arc atoms,
constituents
a single
two
contains
with
the
species.Birjury
is homogeneous
mixture
scale
situations.
an ailoy.
is called
mixture
the
simple
different chemical
or more
two
two constituents.
only
from
drawn
examples
GAPS
SOLUBILITY
have
that
distinct
The
water.
atomic
when
it
everyday
mixture
a single homogeneousphase.
Thepropertiesof
differ
mixtures
solidification
and
melting
Heterogeneous
Consider
mixtures
may
a gold-silicon
from
the properties
ofmixturesareofspeciai
at lower temperatures than
properties
melt
alioy: pure Au
melisat
lO63cCand
substances. The
of pure
interest. Heterotheir
pure
constituents.
Si at
I404X,
Au
side
by
side
with
almost
with
such
because
and they are of practicalimportance
precisely
of their lowered
melting points.
What
determines
whether
two substances
form a homogeneous or a heteroare
in equilibrium
mixture?
What
is ihe composition of ihe phaseslhat
heterogeneous
can be
of mixtures
with each osher in a heterogeneous mixture?The properties
at a fixed semperaiure will
underslood
from the principle that any system
evolve
to the
of minimum free energy. Two subsiances wiil
configuration
is the configuradissoive
in each oilier and form a homogeneous mixtureif that
will
free energy accessible to the components. The subsiances
of
iowest
configuration
properties
are common,
Gaps
Solubility
SO/tm
When
a mixture
of 69 pci Au and 31 pet
Figure II.I Heterogeneousgold-silicon
alloy.
Si is melted and then solidified,
the mixture
Au
a
into
segregaies
pure
phase of almost
\302\253iih
a
almost
coexistent
of
Si
aboui
phase
(Sight phase)
pure {darkphase).Magnified
is that of the lowest-melting Au-Si mixture,
the
800 times. The composinon given
eutectic
a
later
so-called
mixture, concept explained
in she text. Photograph
courtesy
ofStephan Justi.
a
form
side by side is
phases
if [he
tnixlure
heterogeneous
the
mixture
miMure
hclerogeneous
free energy of
combined
of
the
Uvo
the
separate
mixture:
homogeneous
a solubility
melt at
gap.
a lower [cmperalurethan
the
separate
substances
work,
and
if I he
the appropriate
discuss
compounds
the
energy
free energy is
G.
We
tire
will usually
HelmhoUz
free
the
pressure
involve
F rather
energy
simply speak of
com-
free
energy.
well-defined
binary mixtures of constituents Ihat do no! form
with each other. Our principal interestis in binary
Consider
alloys.
Chapter H: Binary
Altitun
or more
two
have
concerned
are
biophysics,
materials
of
applications
Many
phases
coexistence.
in
Beauiiftil,
that
and important
unexpected,
Ihe fundamentals
physical
systems.
in this chapter, with examples drawn from simplesituations.
We treat
in such
occur
effects
and
of
the
subject
SOLUBILITYGAPS
are
Mixtures
or more
of two
systems
molecules,
A
is homogeneous
mixture
Binary
species.
four constituents
and
three
are
constituents
an alloy.
when its constituents
is called
mixture
the
chemical
different
constituents. Mixtureswith
ternary and quaternary mixtures.If the
atoms,
arc intermixedon an
melting
solidification
and
mixtures
may
an
of 69
alloy
from
the
properties
side
by
alloy:
pet Au
side
are common,
properties
of their loweredmelfing
What
heterogeneous
determines
mixture?
and
evolve
dissolve
configuration
of
with
they
two
compound:
phase
mixture
almost
and
Au-Si
are
of practical
importance
microscopic
of almost
with
such
precisely because
points.
whether two substances form a homogeneousor 3 heteroWhat is the composition of the phasesthat
are
in equilibrium
be
other in a heterogeneousmixture?Theproperties
ofmixtures
can
wiil
from the principle that
at
a
fixed temperature
any
system
to the configuration
of minimum free energy. Two substanceswill
in each other and form a homogeneousmixture
if that
is the configurawill
lowest
to
the
free energy accessible
components. The substances
with each
understood
substances. The
of pure
of mixtures
are of special interest.Heterolower temperatures than their constituents.
Si at 1404\302\260C,
pure Au melts at 1063\302\260C and pure
31 pet Si melts (and solidifies}
at 370\302\260C This is not
form
at
melt
the result
pure
everyday
does iiot
properiies
Consider gold-silicon
but
The
it
phase.
homogeneous
atomic
is heterogeneous when
to form
scale
mixtures
are called
and not mole-
Solubility
10/mi
H.I
Figure
jure 11.1
Siisn
is melted
ofSiephanJusii.
mixture
if the combined free energy of the two
separate
is
free
of
the
lower than the
by side
phases
homogeneous mixture:
energy
we say that
the mixture exhibiis a solubility gap.
then
A hcierogeneous
mixture
will melt at a tower temperature than the separate
comif the
free energy of the homogeneous melt is lowerthan
ilie
substances
free
of the two separate solid phases.
combined
energies
Ihis
we assume for simplicity that the external pressure
Throughout
chapter
and we set pV ~ 0. Then volume changesdo not involve
be
neglected,
may
a heterogeneous
form
side
and
work,
than
the
appropriate
We
compounds
discuss
free eneryy
free energy G. We
the Gibbs
binary
wiih
each
mixtures
will
of constituents
other. Our
simply
speak
rather
of the free
energy.
principal interest is in
binary
alloys.
Consider
Chapter Hi
a mixture
Binary
Mixtures
of
aloms
JVA
We express
x
the sysiem
Suppose
per atom
in
\302\273
A'b/N;
Suppose
further
curves
shape.
B}
jVa/N.
an
average
free energy
with
C)
two
homogeneous
Any
respect
to
two
separate
<
at
points,
in
derivative
second
ihe
x, <
is unstable
\302\273
form shown
the functional
lias
that/(.\\)
cause this
x of B aioms;
= F/N.
energy
the fraciion
iermsof
Free
B.Thetotal
by
given
this curve
NB atoms of substance
A and
ofsubsiance
is
atoms
of
number
in the
we
wilt
Figure
11.2.
Because
d2f/dx2 is negative,
x = xx and x \342\204\242
x^.
see
later what
composition range
D)
xp
phases of
may
is
that ihe average free energy per atomof the
mixture
segregated
a
the
i\"
line
and
in
ihe
on
the
Thus
the straight
given by
connecting
points
[}.
point
a lower
has
free energy than
entire composition range D) the segregatedsystem
shall
show
the homogeneoussystem.
Proof
The
free
energy
of a
F
where ,V,
Nfi are
and
=>
the total
NfJ\\xfi)
numbers of atoms in
j$ is
E)
.
phasesa
and
ji, respectively.
which may
be
solved
for .V,
and Ny.
0)
Gaps
Solubility
Figure
with
E) we
From
a solubility
obtain
fjix)
(S)
JV
for
the
free energy
straight line
through
the
the point i
in
thef-x
points
of the
two
plane.
a and
system.
phase
If we
/?. Thus/
set
in
.v.
(he
is linear in x and is a
v,c
see (hat the line docsgo
A'3 or.v^,
result
This
between
interval
p.
.y4 and
xfi
is given
by
Binary Mixtures
II:
Chapter
made useof
(he
that
assumption
(he straight
line is tangentto
3 and /J, and therefore our result holds for any straight
line
points
two points 2 and/Jin commonwith/(.v).
Bui
fora
given vaiue of x, (he
lowest free energy is obtainedby drawing
(he lowest
possible straight line that
has (wo points in common
on opposite sides of a-. The lowest
wiih/(-v),
possible
line
the
is
shown.
The
and
straight
(wo-pointtangent
x3
compositions
x? are
f{x)
the
at
that has
potentials
/*a> =
We show
the
two
/jB
are
(9)
Pb*-
given
by (he
of the two-
intercepts
plot at x
edges of thc/(x)
vertical
*=
and
a ~
1,
MIXING
OF
ENTROPY
AND
ENERGY
jja and
i that
Problem
in
Pb\302\273
/*\302\253;
The Heimhoitz free energy F ~ U ~ to has contributions from Ihe energy and
from
the
A and B on
We treat the effect of mixing two
components
entropy.
both terms. Let uA and \302\273a
be the energy
per atom of the pure substancesA and B,
referred
atoms
to separated
at
Tlie
infinity.
energy
average
constituents is
u
(uANA
+ vsyn)/N
the
per
mixture
atom
separate
homogeneous
of
the
homogeneous
constituents.
is
niixture
u~x
nA
4-
(\302\253B
A0)
uA)x ,
plane.
of
the homoge-
constituents.The
of mixing.
If (he re term in the free energy is negligible,asat 1 = 0,a positive
mixing
mixture
not
will
that
a
is
stable.
mixture
means
such
energy
homogeneous
Any
in the
the \342\200\224ia
then separate into two phases. But at a finite temperature
term
free energy of the homogeneous
the
tends
to
lower
mixturealways
free energy.
a contribution,
the
ofa
called
mixturecontains
entropy of mixing,
Theentropy
of the separate components. The mixing
that is not present in (he entropies
the
different
arises
when
of
atoms
species are interchangedin position;
entropy
of such interthis
a different state of (he system.Because
operation
generates
energy
excess
is called
\342\200\224
the energy
and Entropy
Energy
11,3
Figure
in a
sysicm
Energy
with
per atom
a positive
as a function
of composition
energy.
mixing
of Mixing
simple
for which
states
a mixture has more accessible
and hence the mixturehas the higher
entropy.
In C.80) we calculated the mixing entropy
A, ^B,. to find
changes
two
tlie
than
erM
of
separate
substances,
a homogeneous
alloy
(ID
as
plotted
in Figure
11.4. The
N dx
which
goes
to
+ co
as x
curve of aM
range
composition
X)
x has
versus
bgx
-+ 0 and to \342\200\224
co as
- ioj
x -*
I.
A2)
Chapter II:
Binary
Mixtures
da^/elx
Ffgure
11.4
Mixing entropy.
interchange of two
atoms
Tn
Consider
is the
slate
in this
related
slates
way
of the
is the
entropy.
now the
quantity
u[x)
which
mixture
any
of different
\342\200\224
X
free energy
(a
the
A3)
ffjtf
mixing
entropy
contribution.
The
entropy
curves
dependence
to fo(x),
~-zaM/N
in
Figure
of/0(.v)
we obtain at
11.5. In drawing
itself,
because
the
for
Energy
Free energy
temperatures.The curve
Figure 11.5
per
atom
fQ is the
versus composition,
free energy per atom
und
Entropy
of Mixing
at three
without
the
a parabolic
mixing entropy contribution. For ilHistraiion
composition
dependence is assumed, and the temperaturedependence
of/0 is
The tliree solid curves represcnl the free energy
neglected.
including
the mixing
for the temperatures
0.8 rM, 1.0 tM, and 1.2 rM,
entropy,
where
there
is a solubility
rw is the maximum temperature for which
gap.
our
The
this is
argument
construction
separation
phase
at 0.8 rw
is apparent.
follow
irrelevant. Three importantdeductions
of the/(x)
from
the
curves:
(b)
(c)
Above Ty
(a)
At
all
finite
temperatures
because
the
of the
curve
has
a positive
Binary Mixtures
11:
Chapter
widens with
composition
only
range
solubility of A
in
B and
as t -*
of B
in
The
0.
At
A,
a result
finite
any
energy
gap
edgesof
there
temperature
earlier
obtained
exhibii
of the
will
range
composition
the gap
but
temperature,
decreasing
mixing
positive
in
the
finite
is a
3. The
Chapter
below
Positive
is that the mutual solubility is limited only
tw.
We now discuss three examples.
mixing energies arise in different
ways.
new result
Consider
an alloy A^jB,
with nearest-neighbor interact'ionSi
in
than
the attractive
interinteraction between unlike atoms is weaker
interaction between
as bonds. There are
like atoms. For simplicity we speakof the interactions
be
ihe potential
three
different
bonds:
energies of
A-A, A-B, and B-B. Let uAA) uAB and uBB
each bond.These binding energies will usually be negativewith respect to separated aloms.
We assume the atoms are randomly distributed among the lattice sites.The average
of ihe bonds surrounding
an A alom is
energy
Binary
Example:
alloy
(he attractive
which
uA
of A and x is the
The
factor^
can be written
ip[(l
Figure
mixing
II.5.
proportion of B.This
for B atoms,
X)HAD
result
is wiiucn
in ihe
over
both
A5)
N\"UD.
atom
types. Ifeach
atom has
p nearest
is
xJUAA
2jcA
- *Kb +
the
two
atoms
A6)
*3\302\253db]-
it
The
connects.
result A6)
as
u =
is the
A4)
tO. Similarly,
Chapter
\"a
xuAa
x)uAA
energy.
On this
ip[(l
model
the
x)uAA
mixing
xum]
energy
as a
+ uM.
function
A7)
ofx
is a
parabola, as
in
Energy
A solubility gap
< 0, that
= -2P[fAB
^r
and
Entropy
of
Mixing
is, when
i(\302\253AA
B0)
O3-
From A2),
x{l -
N dx2
The
sign holds
equal
for
,x =
$. Wilh
T*i
x)
these results{19)yields
M\302\253ab
iO'AA
+ ^a)]
B2)
as die lower
carry a large
water
strong
electric
molecules.
as
the
moment
dipole
This attraction
weaker
oil-oil
between
about
as
bonds.
solids
with different
crystal structures.
Consider a homoge-
mixture
of gold and
structure
Chapter
11;
Binary
Mixture
\\/
Figure
11.6
Tree
energy versus
homogeneousmisiuresfor
mixture
crystallize
which
in ^ilfcrem
crystal
are involved,
one
Two
structures.
for each
differe
crystal structure
vs^~7cz:\":\"s'.\".r:'~
Exampk:
mixture
with
Liquid
SIU-*
a solubility
-..,.-,...
-\342\226\240\342\226\240\342\226\240
---\342\200\224.-.\342\200\224
--...-..
...
\342\226\240\342\200\242\342\226\240-\342\226\240->\342\226\240\342\226\240-\342\226\240\342\226\240\342\226\240-\342\226\240\342\200\224
He m*.Uuivi
gap is the
at W
miMuniof
liquid mix-
tanpcraiures.
The
moat
interesting
;-.-,,
of
tiie Toruicr
30
20
10
40
Phaie
Diagrams for
50
60
.70
SimpleSolubility
80
Gaps
100
90
\342\226\240\"
Atomic
Figure
11.7
Liquid
percent
mixtures of
JHe and
He
pure
\342\226\240'He
4Hc.
kinetic
energy. Almost trie entire
energy of the mixture is contribuicd by t!ie
which
are
fermions.The
of a degenerate Fermi
atoms,
energy
per atom
gas increases
v,ilh concentration
7. This energy has a negative secondderivative
as n1'*,as in Chapter
kinetic
zero
3He
Pltase
Diagrams
Tor Simple
Solubility Gaps
phase
mixtures
form of
diagram
represents
with solubility
the temperature
according
gups may be more complex,
but
the
underlying
principles
to
the
aclual
are ihesamc.
II;
Chapter
Binary Mlxtur
Slabk
Decomposilion
\\
1
1
1
Uns
temperature
the point
will
curve
boundary
system
PHASE
(*,i)
a solubility
be unstable
stability boundary
tlic
ai
form two
for
with
temperature
r. The
stability
calculated quantitatively
a parabolic
BETWEEN
EQUIUBRIA
with
x will
below
Tails
of Figure lt.5,
system
oCcomposition
then
given by
curve with the horteontal
compositions
a binary
for
the
for
fo{x).
LIQUID
When
of
the
fraction
phenomenonis
mixtures.
of a
the
homogeneous liquid mixturefreezes,
is almost always
readily
understood
consider
a simple
different
from
that
composition
of the liquid.
The
the free
energies for
Phase
constituenl
is
melting
temperature
ta or pure
between
fs{x)
atom,
per
(b) The
gap.
Solid Mixtures
the melsing
Jhan
lower
a SemperaSure
consider
We
Equilibria
in Figure
qualitatively
internal
equilibria:
(a) When
in
system
is a
equilibrium
homogeneous
liquid.
a
system in equilibrium consistsof two phases,
solid phase of composition xs and a liquid phaseof composition
xL.
x > xs the system in equilibriumjs a homogeneous
When
solid.
(c)
a
arc
The
and
of
and
a
so!id
in
compositions
xs
xL
liquid
equilibrium
phase
of the
temperature dependent. As ihc temperature decreasesthe free energy
solid decreases more rapidly
tlKll of the liquid. The Ungctitiai points in
than
Figure 11.9amove to the Icfi, Tliis behavior is rcprcscnScdby a phase diagram
stinihlr to the earlier representationof the equilibrium
curves for
composition
(b)
When
mixtures
xL<
with
xs, the
x <
In Figure
separation.
phase
for
xL
is called
the
curve.
Hquidus curve; the curve for xs is the soltdus
have been determined experimentallyfor vast numbers
The
phase diagrams
of binary mixtures. Those for most
of the possible binary alloys are known.*
For
Figure
phase diagrams are more complicatedthan
for
a
11.9b,
simple system,
germanium-silicon.
When
is lowered in a binary liquid mixturewith
the
the temperature
phase
of Figure lj.9b, solidification takes placeover
a finite
diagram
temperature
a liquid with
the
range, not just at a fixed temperature.To see this, consider
is lowered,
initial
composition
xiL shown in Figure 11.10.As the temperature
\342\200\224
of the solid formed is given
solidification begins at t
composition
x,. The
is changed.
'hat
of
the
In the
so
the
remaining liquid
by
xtsi
composition
the
example xiS > xiL, so that the liquid moves towards lowervaluesof x, where
if
solidification
is lower. The temperature has to be lowered
temperature
the
of
the
moves
solidification
is to continue. The composition
along
liquid
=
at
t
The
solid
formed
the
curve
until
solidification
is
compleied
tA.
liquidus
metal
most
homogenizeafterward
in
for
a long
slandard
Constitution
iabutatlons
of
binary
arc
by
solids
many
M.
in
atomic
solid
may homoge-
temperature remains
is too slow, and the
if lhe
diffusion
\"
indcnniieiy.
Hansen,
Constitution
Edioti,
for
''frozen
The
equilibrium.
particularly
diffusion,
time. But
remains
\342\200\242
The
atomic
by
homogeneity
R. P.
and is not in
in composition
is nonuniform
high
the
alloys
was drawn
which
Coitsilxatlon of binary
supplement,
allays,
McGraw-Hill,
McGraw-Hill, 1969. .
McGraw-Hill.
1965; R
A.
1958;
Shunfc,
11.9
Figure
ihis example
Phase
equilibrium
neither phase
cxhibhs
btiwccn
liquid
a solubiliSy
and
solid
mixtures.
In
gap. We assume
tA
x < xlt.
<
I412\"C
7\342\204\2425i
324
Phase
Figure
Mosi
11.10
Scmperalurc,
but
liquid
over
higher-nwiliiig
consiiluenl
lower-mching
consliSucnt
solidification
lemperalure
Advanced Treatment;
mixiuresdo
a finite
not
temperature
liquid
at a
range
from
and Solid
Mixtm
sharp
t,
'o ta.
The
in ihc
down
Liquid
solidify
compositions
Between
Equilibria
to
temperatures
constituents.
31 pet
starts at a
binary
The
Si starts to
in which
systems
the
below the
alloy is such a
significantly
go!d-si!icon
solidify at
higher temperature.When
370\302\260C.
we
At
plot
other
the
of alloy
oflhe onset of solidificationas a Function
composition,
obtain
Mixtures
with two
we
the two-branch liqutdus
curve
in Figure
11.11.
temperature
solidification
minimum
temperature
liquidus branchesare calledcutectics.The
is She eutectic
is the eutectic SemperaSure,where She composition
composition.
is a two phase solid, wiih
The solidifiedsolid at the eutecticcomposition
nearly pure gold sideby side wiih nearly pure silicon, as in Figure 11.1.In the
solidAu-Si mixture shcre h a very wide solubility gap. The low mching
point
oFthe
for
the
free
occurs
eutectic composision becausethe
homogeneous
energy
melt is lower than the free energy of the two
for
at
solid,
temperatures
phase
or above She cutectie
temperature.
Such behavior is common among systems thai exhibita solubilitygap ill the
solid
but not in the liquid. The behavior of eutccjj'cs
can
be understood
from the
free energy plotsin Figure11.12a.
We
for the solid as in Figure 11.6,
assuine_/^(.\\\")
11:
Chapter
Mixtures
Binary
1600
404\302\260
1400
1200
1063\302\260
1000
/
\\
/
\\
0\302\260
1/
-31
Pure
11.11
Figure
Au
Euieciic
and
range
Figure
but
II.12a
below
10
iempctaiure
indicaie
37OX
complcic
80
90
100
Pure Si
silicon
percent
go!d-siljconalloys.The
to difTcrcnt
corresponding
temperature
diagram of
ihe experimcnial
composiiion
constituents.
phase
60
50
40
Atomic
30
20
10
Hquidus
iwo
consisisof
T, = 37O;C.The horizonial
ihai ihroughoul the eniirc
iis solidificalion
unlit
ihe
euieciic
crystal structures a and ^ for the two pure confor a temperature above the cutectic
is constructed
the melting
so
that
to
energy of the liquid reachesbelow the common
tangent
phase curves. We can draw two new two-point tangents tltat give even lower free
energies. We now distinguishfive different
ranges:
composition
is a
(a) and (e). For x < xaS or x > x^, the equilibrium state of the system
solid. In the first range
the solid
will have the crystal structure a;
Homogeneous
in
the
second
the
structure
is
range
($.
(c). For xlL < x < XpL, the equilibrium state is a homogeneousliquid.
and
For
is in
a liquid
(b)
(d).
x^ < x < xaL or x^L < x < Xp$,
phase
equilibrium with a solid phase.
the
As
is lowered, faS and fa decreasemorerapidly
than/L,
temperature
and
of
the
the range
H.12b
homogeneous liquid becomesnarrower.
Figure
shows
the corresponding
the
two
curves.
solidus
phase diagram, including
tUe free
the solid
At
to
the
theeulecltc
common
t, Jhe
temperature
tangent
to f^
energy fL
a homogeneous
A mixture
meits at a
above
(he
and fps, as in
tangent,
free energy
(bj in a
diagram
phase
Figure
eutcctic
although
11.13.
The
composition
At x < xt, the
composition.
at
free
of
solid.
of composition equal to
the
eutectic
pure
composition
substance.
solidifies
The solidification
and
of
Mixtures
FiCe energies
Figurel!.!3
compositions
away
From
and
ends
at
the eutecttc
and
ends
at
a higher
in
a euseclic
system at t
, andati
< xr.
starls at a
higher temperature
at
the
starts
eulectic
temperature. Melting
temperature
the
euieciic
composition
temperature.
melting
a large
temperature
role
in
of eutectics
semiconductor
is widely
device
tech-
technology:
eutectic
the
cutectie
temperature
permits
-2L2\"Cof
low temperature
the H2O~NaC!
eutecttcat 8.17moipet
NaO.
The
in character,
solfdus
curves of eutectic systems vary
for the
greatly
die
ioclt
Pb-Sti system (Figure Il.M) die solid phases
in equilibrium
with
contain
:tn appreciable fraction of tltc minority
const
[merit, and this fraction
in
other
increases with decreasing
systems this fraction may be
temperature,
small or may decrease
with
or both. The Au-Si system
decreasing
temperature,
with
is an example:
The relative concentration of Au in solid Si ill equilibrium
of only
an Au-Si melt reaches a ma\\imum value
2 x !G~6s.-ound i 300\" C, and
it drops off rapidly at lower temperature.
In our discussionof the free energy curves of Figures 31.12 and 11.13we
assumed
the
lite composition
tltat
at which the liquid phasefree energy
touches
10
\020
20
pure Sn
30
40
Atomic
50
60
percent
lead
70
90
100
pure Pb
10/tm
Figure
of [he
Jackson.
11.14
Pb-Sn
{a} Ptiasc
eutmic,
S29
11:
Chapter
Mixtures
Binary
solid phase
tangent
to the
In some
and
were
fL
iti Figure
interchanged
interval,
Such
.\\2a.
and
compositions
xlS
as
and/t
if either/aS
arc caiied
systems
xfiS.
or/flS
peritectic
systems.
SUMMARY
1.
phases
separate
the combinedfreeenergy
gap when
a solubility
exhibits
mixture
free
the
of the
energy
two
of
homogeneous
mixture.
2, The
in
the alloy
For
position.
3. The mixing
for
energy
uM
for
p nearest
4. The
5. Mixtures
minimum
we have
A} _IBI,
px(l
is
interactions
nearest-neighbor
=
of different
atoms
j(uAA +
uBB)]
.xL versus
x)[uAB
neighbors.
is
Hquidus
equilibrium
for a solid
when
arises
entropy
mixing
the
curve
composition
with a solid.
for
phase in equilibriumwith
in
phase
liquid
Xs
versus
liquid.
with
The
eutectics.
called
are
eutectic
temperature.
PROBLEMS
L Chemicalpotentialsm two-phase
the vertical
Mixing
3He-4He
energy
die two
by
the
intercepts
B of
and
oFthe two-point
=0
and
the chemical
an equilibrium
tangent
mixtures
in
in
the
Similarly,
solubility
oFPb
11-2
Figure
-> 0.
potwo
\342\200\224
1.
in 3He~*He
that
Show
equilibrium.
atomic species A
Pb-Sn
in solid
phase
oF
liq-
in 4He
diagram
of
Sn with decreasing
t.
do
What
such
residual
finite
solubilities
about
inipty
the
Form
of the
Function
u(.x)?
3.
Segregation
In
4.
of impurities.
coefficient
of a
range
Solidification
binary
alloy.
binary
of the
that,
regardless
diagram of Figure.' 11.10.Show
B
in component
initial
the melt will always become fully
composition,
depleted
ion
the
id i Seas
the
time
remnant
That
sol
the
last
of
the
meit
solidifies.
is,
by
will not be complete until
the
has dropped
to TA.
temperature
alloy
5.
wish
Alloying
the phase
of gold
hto
silicon,
(a) Suppose a
and
onto a Si crystal,
subsequently
diagram, Figure 11.11,estimate how
silicon crystal.
the estimate
The
for
densities
800\302\260C.
of Au
heated
deep
and Si
1000A
to
she
400\302\260C-
gold
layer
From
will
of Au
the
is evaporated
Au-Si
phase
penetrate
into the
(b)
Redo
12
Chapter
Cryogenics
COOLING BY EXTERNAL
IN
AN
Gas Liquefactionby
WORK
334
ENGINE
EXPANSION
for
Effect
337
Effect
Joule-Thomson
the
Example: Joule-Thomson
van
der
Waals
Helium,
Pumped
Cooling:
to 0.3
HeliumDilution Refrigerator;
341
342
Miilidegrees
DEMAGNETIZATION:
ISENTROPIC
QUEST
333
339
Liride Cycle
Evaporation
Gas
346
ZERO
FOR ABSOLUTE
NuclearDemagnetization
348
SUMMARY
350
PROBLEMS
350
1. Helium
2. Ideal
as a
van
der
Waals
359
Gas
35i
Carnot Liquefier
3. Claude
Cycle
4. Evaporation
Helium
35!
Liquefier
352
Cooling Limit
for
5. Initial Temperature
Demagnetization
Cooling
352
is the
Cryogenics
discuss
We
lowest
the
to
down
cooling
a gas
of
temperatures.
The dominant
by kiting it do work
be a conventional
may
against
is the
lOmK
to
down
a force
gas
employed
or
the
discuss
We
laboratory
to the
Household
cooling
evaporation
liquid helium
below its
COOLING
BY
In the
method
boiling
EXTERNAL
EXPANSION
AN
in
the
they occur
in which
order
in
from
proceeds
1 ;iK.
sometimes
lowest laboratory temperatures,usually
lOmK,
and automobile air conditioners utilize the
cooling
appliances
same
IN
gas of 3Hc
substance.
paramagnetic
there
virtual
that
temperature,
is used
in
the
to about
for
laboratory
1
cooling
K.
WORK
ENGINE
isentropic expansion
of a monatomicidealgas
from
to a
pi
pressure
to
(i)
by F.64).
temperature
working
process
the
from
are
partial
compounded
Actual
expansion
expansion
parts
of
itisng
by
Work in on
External
Heal
{Expansion
ejection
Expansion
ngine
Working\342\200\224
volume
gas ts
Simple expansion refrtgeraior.A working
is
the
heat
of
into
the
compressed;
compression ejected
environment.
The compressed room temperature
gas is
heat
counleriiow
further in the
exchanger. It then
precooled
to a
does work in an expansion engine, where it cools
volume.
Afkr
extracting
temperature below that of the working
hea{ from the working
the gas returns to the compressor
volume,
FEgure
via
{he
I2.I
heat
exchanger.
Ens
Chapter 12:
Cryogenics
separated.The compressionis
exchanger by contact
flow heat
temperatureof
the
in
cooling
the
on
the
expansion
of the
design
The
work
done the
The total
by
She
{Ul
on the
performed
important
fij and
the expansion
work p{Vl
gas.
the displacement
plus
gas
into
flowing
difference
enthalpy
Vx
a given
to
refer
mass of
is the energy
U2
the
the gas against
pressurep2-
with
engine
the gas
of
the
gas
work
The
is the difference
the
of
boih
to move
V% required
p2
by ihe engine
extracted
exchangeris as
is the
engine
expansion
where
leaving
energy
im-
requirements
cooling
and output
compressor,
by
the
iruernat energy U^
engine is the
heat
the
via
compressor
expansion engine.
extracted
the input
between
the
the
reduces
engine.
counter-
in a
precooled
return
gas stream at the low
cooled to itslowesttemperature
a low friction turbine.The cold gas extracts
exchanger.
imposed
usually
temperature
gas is then
the cooling
from
room
near
room
above
cold
the
with
The
load.
engine,
expansion
heat
as
the
or
at
performed
- {Uz +
4- PlVt)
gas
j=
pV =
and
|Nr
PlV1)
Hs
~~
B)
H2.
Nr, hence H =
The
\\Nx.
\302\273
|N{t,
C)
r2).
enginescauses
mechanical
is
usually
Joule-Thomson
liquefiers
usually
temperatures,
with
multiple
The principle of
to
the
electron
potential
potentials.
cooling by
gas
in
or
more
stage
expansion
expansion
of an
below.
exchangers.
isentropic
semiconductors.
When
ideal gas
electrons How
is applicable
from
semi-
semiconductor wuh
electron
heat
final liquefaction
discussed
stage,
two
eontain
The
difficulties.
operating
with
a lower
Gas Liquefaction by
down
to about
So 135K
Gas
Liquefaction
units
multistage
12.2.The work
~plt(Vj doneon
Here
dVt
the
is
in
gas
pushing
it through
is negative
11
\342\204\242
ideal
\\Nr,
so
that
down
\342\200\224in
ts
r2
of
al! gases.
causes
significant
will condense.
gas
lower
pressure
p2,
the displacement
and
{he expansion valve
work
engine
sec this,
that extracts
effect.
Joule-Thomson
There is
the expansion.
the
enthalpy.
At
are
interactions
the
between
difference
{he
work
displacement
temperatures
pressure p, is forcedthrough
an expansion
called
constriction
as in Figure
Gas at
is simple.
implementation
practical
Effect
Joule-Thomson Effect
The
Joule-Thomson
achieved.
been
hnvc
the
zero coolingeffect
for
an
gas.
|2,2
The Joule-Thomson
done against
initially
will cool
the
below
The sign
the
eflccl.A
the
the
gas
is pushed
gas is
forces.
If the
on Joule-Thomson expansion-
internal
of the temperature
temperature is
inversion temperature, riB,, the gas
intermolecuhtr
a certain
of
because
valve
Expansion
Figure
occurs
12:
Chapter
Cry
Liquefaclion dala
U.I
Table
n.
CO,
195
cm
112
902
77.3
20.4
o,
N,
H,
\342\200\242He
4.SS
JHe
3.20
the
The las
liquid.
Jrti
T( ano\" oot
T,,.,
Tt,
(jas
lo
for
U/mol
304
B050)
25.2
191
A290)
155
126
33.3
5.25
3.35
umn,
measured
em'/mol
223
66
6.82
67
621
5.57
205
0.90
28.1
34.6
28.6
51
B3)
0-082
320
0.025
50.8
n walls
pressure.
mosphcric
der Waais
effect for
have
ran
\302\253=
JWt
corrections caused by
corrections
opposite
the
short
is
0.14
for
signs. The
the critical
far
li'aab
gas.
{S2fV){bx
b are
positive
initial
such
poinl
fuel.
boih
Liquid
for ihe
temperature.
an expansion
for common
== lab
in
found
gases
A0.75)
that
D)
constants. The
the
= 2/rt,
We
- 2a)
where xc
0.7!
12.1.
Table
Joule-Thomson
a van
8.7
'
H
for
45
be la'ken up
can
thai
on the
depends
change during a Joule-Thomsonexpansion
All gases have an inversiontemperature
below
which
TIn,
above
which
heals
(he
it
cools,
gas. inversion
temperatures
Example:
314
893
in
Mite
34.4
are listed
wall
8.18
tndkai
Atl/V,
V,.
AH,
long
sign
range
at
last
two
atiraction.
arc the
The correc-
terms
the temperature
E)
at fixed
For t < iin, the enthalpy
here in expansion the work done against the
increases;
temperature increasesas the volume
In a process at consiant enihafpy
attraciive interactions between molecules
is dominani.
this increase
is compensated by a decrease of the \\Nt ierm, that is, by cooling
the gas. For
The
temperature
Gas Liquefactionby
i a
ioIccuIcspenetrate
farther
lhe repulsive
Joutc-Thot
fixed lemperamre
inio
the
work
done by the
lempcraluie
the
regio
wilh
litjueficrs the Joule-Thomsonexpansioniscombined
heat exchanger, as shown in Figure J2.3.The combination
is
a cycle in 1895
to
called
a Lindc cycle, aficr Carl von Linde who
used
such
air starting from room temperature.In our discussion
we
assume
that
liquefy
is
ihe
same
the expanded
the
heat
at
from
exchanger
gas returning
temperature
as the compressed
it. We neglect any pressure differencebetween
gas entering
the output of the heat exchanger
and the pressure above the liquid.
Linde
cycle.
In gas
a counlerflow
To
and
from
comprcs
Figure
by
12.3
The Lindecycle.Gas
combining
a countcrflow
JT expansionvaJv.
Liquefied
gas
Joule-Thomson
expa
Iieatexchanger.
Figure
as a
Performance of helium
inpui pressure,
12.4
fund
ion ofihe
ihc
ii^uciicrand
ihc
ihe
heal
through
See Problem
Plenum,
still
exchanger
A. J.
1971.
p. 1S7.
if
gas boiledoff
rather
Croft
cunes give
at 4.2
coid helium
3. Afier
The solid
in
than
boiled
QiM
(he
=
toad
curvesgive
tfDUl
A&mWL-dcryo&mcs
ihe
Hia, ihe
is placed
by lhc load
oiT into
Liude cycle,
of 1 aim and
pressure
ouiput
temperature.
The broken
coefficient
liquefaciion
input
an
by the
operating
litjueficrs
for
inside ihe
is relumed
liie atmosphere.
(C. A. Baiiey, ed.),
Evaporation Coaling;
The
comhimtiion
hc;\302\273
fraction
is
Constant
liquefied.
Hla
lhe input
of
heat
the
and
output
peraturc
enthalpy
ihat the
suppose
J)H9Ui'
\302\243!
lhe enthalpy
tfHl) is
exchanger-
consimu
\302\2436}
mo!c
of
llou, = H(Tin.pBJare the enlhalpies
per
both
at
lhe
common
pressures,
upper temperature
H(TiMp-a) and
gas at
combination;
to 0.3
requires lhat
cniluilpy
=
Here
Hie
enter
//;\342\200\236 -IWii,
is ;i
valve
exchanger-expansion
PumpedHelium,
From
F)
its
at
boiling
lcm-
the fraction
we obtain
17)
called
the
coefficient.
liquefaction
when
lakes place
Liquefaction
>
//\342\200\236\342\200\236,
Hia;
> H{Tia,p-J.
HiT^J
the
Only
Joule-Thomson
will
take place.
with
rapidly
If
known
are
G)
calculated
coefficient
coefficientdrops
numerator
expansion
(8)
at the input
enthalpies
the
is, when
thai
Tiat
increasing
decrease of the
of the
because
Coofing:
Evaporatfon
from
Starting
evaporation
latent
and
G)
heat
liquid
the
helium, by
cooling
of
the
of vaporization
liquid Iteltum
ihc
:itonu'c
ihc
forces
of the
increase
that
cnuscJ
further
cooling:
helium
staie
is
pumping
is extracted
work
io liquefy in
a gas, while in
lieiium
away
along
is done
the
first
evaporation
vapor,
with the
y
'
vap,-..
hi JouL-
cooling
the
17:
Chapter
Table
Cryogenics
12.2
3Hc reach
Tempera turds,
in
which
kctvifi.at
1 he
vapor
of 4He and
pressures
values
specified
p(lorr)
The
lowest
in
helium
0.79
0.28
0.36
vacuum
1.27
1.74
2.64
0.47
0.66
1.03
1-79
cooling of
by evaporation
technology
pressure
vapor
gas and
0.98
liquid helium
14). As the ternperalure drops,the
(Chapter
(Table 12.2} and so docsthe raie ai which
can
be extracted
from the liquid helium
accessible
tempcralure
isa problem
equilibrium
0.66
drops
bath.
cooling
Evaporation
Helium
in
such a5
Dilution
classical
K io
of
pressure
refrigeration
principles
0.0! K. is
dominated
evaporation refrigeratorin a
We saw in Chapter 7 that
cooling
everyday
ait
conditioners.
Militdegrees
Refrigerator:
cooling principle
devices
The
dominant
ts the
lose their
by
very
clever
dropped to
I0\023
torr,
range
utility. The temperaiure
dilution
helium
the
3He has
liquid
from
which is an
refrigerator,
disguise.*
quantum
are bosons, while
of 3He-4He mixtures in
diagram
the range labeled unstable wil!
atoms
11.7.
Figure
A mixture
decomposeinto
two
with
in
composition
whose
phases
separate
area.
that
are given by the two brandies of the curve enclosing
compositions
3He phase.
3He phase floats on top of the dilute
The
concentrated
3He
to about
3He
in
As T -\302\273
the
concentration
of
the
dilute
drops
0,
phase
6 pet, and the phaserich in 3He becomes
essentially
pure 3He. Consider a liquid
Physics
techniques
below
methods
Scientific
American
221,26
(t%9).
\342\226\240
Wheatley.
Am-1
J. Huiskamp
Experimental
accoun!
and
principles
Phys.
O. V.
and
Is O. V. Lounasmaa,
.
12.5
Figure
dilution
Cooling principle of ilm helium
wiih a JHc-4He nmiure. When
from
ihc pure ]He fluid
and
Hlc is in equilibrium
mixiure, sHe evaporaics
3He-4He
these
refrigerator.
Liquid
is added io the
absorbs
heat in ihc
4He
a temperature
temperatures
in the
almost
millidcgree
all the 4He
comparedto
that
of
the
the
remaining
ground
state
orbital.
3He atoms,
consider
iHc
3He liquid.Coolingwill
result.
be
a cyclic process the 3He-4He mixturemust
again.
separated
is
tile
different
common
method
Tile most
distillation,
equilibrium
using
by
12.6
shows
a
schematic
3He
and
*Hc
of
12.2).
(Table
Figure
vapor pressures
on these principles. The diagram is highly
built
diagram of a refrigerator
In
in
actual
refrigerators titehcat exchangerbetween
oversimplified.
particular,
An
alternate
chamber
and the still has an elaborate multistagedesign.
the
mixing
of 4He
method*
to separate
the. 3He--4He mixture utilizes tile superfluidity
of
reasons
it is less commonly used,
below 2.17 K. For a variety,
practical
To
obtain
although
Us
performance
is excellent.
\342\226\240
.
Chapter
12:
Cryogenics
3He pump
loop
Key:
Liquid
\342\226\240
I 'lie
Dilution Refrigerator:
Helium
AtitliJegre
Figure
a countcrfiow
mixture
a useful
3He evaporation and circulation
selectively, and is pumped olf.To obtain
heat
must be added to the still, 10 raiseUs temperature
to about 0.7 K, at which
rate,
vapor pressure is ssiH much smaller. Thus, the 4He does not
a nearly stationary
appreciable extent; ihe *Hc moves
riirough
JHe is returned to ihe system and is condensed
background of 4Hc.The pumped-off
in a condenser
that is cooled to about I K by contact with a pumped
4He bath. The
constriction below the condenser takes up the excess pressuregenerated
by the
the *He
temperature
lo any
circulate
circulation
in rhe
first
the
chamber.
The helium
design
there is
SmK
below
Temperatures
of Figure
2.6,
mixingchamberdrops
removed from
The
dilution
the
off the
3He
incoming
its
below
be ncltievcu by
can
we shut
sleady
itself,
state
and
value,
of the
ihe temperature
until
has
3He
all
in
been
chamber.
refrigerator
is not the
oniy cooiingmethodin
the
inillikelvin
known
the peculiar propertiesof JHe.An alternate
method,
in Figas Pomcranchsik cooling, utilizes the phasediagramof 3He,as shown
and
between
Figure 7.15,
with
its negative
liquid
slope of the phase boundary
ant!
solid 3He, The interested reader is referredto the reviews
by Huiskamp
Lounasmaa, and by Lounastnaa, citedearlier.
that utilizes
range
'
N.
H.
Pcnnings,
84, 102A976}.
R. de
Bruyn
Ouboicr,
K. \\V. Tacoois.
Phjiica 8
and
Physiea
DEMAGNETIZATION:
ISENTROPIC
Below
doniimim
K the
cooling process
is the isciitropic(adiabaiic)
dcm;ig-
iictizatioii
3.
and
We first apply a
will
magnetic field
a value
attain
without
will
then
flow
remain
t2
into
to the
appropriate
reducedto B2
the
changing
the
tj-
the spin
specimen
system only
of
value
entropy
means
which
unchanged,
<\342\226\240<
When
at constant
Bt
temperature
ij. The spin excess
If the magnetic field is then
Bj/tj.
the
of
spin system,the spin excess
that B2/z2
will
is demagnetized
from
the
system
#i/ri-
equa'
12.7-
can
vibrations, as in
of interest the
the temperatures
At
Bi,
isentropically,entropy
of lattice
entropy of the
will
be
usually negligible; thus the entropy ofthe spin system
during isentropie demagnetization of the specimen.
Figure
\302\253
HBz
lattice
essentially
constant
\\Latttce
Total
Spin
Lattice
Time\342\200\224-
Before
Time
Figure
12.7
cooling
of
Time\342\200\224\342\200\242
Before
Time
New
equilibr:
at which
magnetic field
js removed
field
removed
isentropie
equilibrium
at which
magnetic
is
New
Fig-
vibrations
initial
is
Quest for
Demagnetization:
lsentropic
Zer
Absolute
as a function of Icmpcralure.assum
Entropy fora spin \\ sysiem
of
field
100
Bx
gauss. The specimenis magnetiz
magnetic
Thu cxlcrna! ntagnctit
insulated
isothermaiiy
ihcrmaMy.
along ah, and is then
field
is 1 timed
on a reasonable
off along/>c. Ill order to keep the figure
sculc
llic initial temperature
tlie
field
are
lower
woi
and
external
than
magnetic
Tj
12.8
Figure
inicrna!
an
used
in
The
random
practice.
steps
out in the
carried
field is
applied at temperaturetx
the
the
with
giving
surroundings,
{At? ~ 0)
insulated
with
the
specimen
isothermal
in
thermal
in good
gas with
The
the
contact
constant
ai
is
t,
by removing the
a pump.
population
of a
contact
path
entropy
12.8. The
Figure
population
spin.
distribution;
The
spin-system
hence the
only
entropy
of
ntB/x,
is a
function
only
where
only
oimBjx.
localinteractions
is theeffeclive field that corresponds to thediverse
among
temperature
r2 reached in an
spins or ofthe spins with the lattice, the final
If SA
the
(9}
rt the initial temperature.Results
which
as CMN,
Figure IZ9 for the paramagnetic salt known
.
.
magnesium nitrate,
where
is the
initial
field and
are
denotes
shown
in
cerous
Final
Figure 12.9
removed
as
cniirciy,
and
fields
iiiiiial
field
magaclic
bul
0.6
0.5
in K
temperature,
Bf versus
In fhese
nil rale.
After
Final
0.4
0.3
0.2
0.1
final
field
was
not
m tfic
only
icmpcraiurcs
cilcd
1109A957).
The processdescribed
so
into a cyclicprocess thermally
is
far
a single
shot
disconnecting,
by
demagnetized
working substance from
at t,, and repeating the process.*
converted
process. It is easily
in one
way
or
it to
the load, reconnecting
the
another,
the
reservoir
Nuclear
Dcmagnelizalion
nuclear
Because
much
are
weaker
paramagnet.
\342\200\242
C.
similar
lhan
100 limes lower with a nuclear
paramagnet
in
The initial temperature of the nuclearstage
temperature
C. B.
V. Hctr.
Rosenblum,
lhan
moments
magnetic
W.
Barnes,and
A. Slcyerl.
and i.
Daunt.
J.
G.
A.
Barclay.
OHgcnics
electron
with
an
nuclear
spin-
W. p. PraH,
S. S.
t\\'uc!ear Demagnetization
Iniiial magnetic
0.6
in
Held
KG
Initial
B/T'm
\\QS
G/K
Figure
I2J0
in
nuclei
the
metal,
-1.1902!1959).
must
be lower
than in an
cooling
=
=
lfwestartatB SOkGandT, 0.01
10 percent
decrease on magnetization
is
experimen!
over
This is
to
sufficient
ihe
overwhelm
T2 ss 10\027K.The
temperature
first
the
B\302\261
moments
of
3.1
the
and
I0~6K.
reached in this experimen!was 1.2
so
line
of Ihe form of (9): 7\\ = T|C.1/B)
Bin
wilh
^auss,
of the magnetic mointeraction
field
gauss. This is the ciTcctive
Cu nueiei.
nuclei
Temperatures
cooling
first
The
cooling.
demagneltzallon
load was
The motivation
conduction
at
below
the
electrons
temperature
1//K
for
have been
using
help
of the
first
nuclei
ensure
in a
rapid thermal
contact
stage.
achieved in experiments in
results
The
in an insulatoris that
of lattice
from a
starting
metal,
lowest temperature
in Figure 12-10fil a
llial
was carried
experiment
cooling
in
particulatly
in
which
experiments
the
that were
nuclear
resonance
magnetic
experiments.*
SUMMARY
1. The
dominant
two
a gas
of
cooling
of the
principles
by letting
work
do
it
production
against
substance.
paramagnetic
is done
work
cooling is an irreversible process in which
interatomic
forces
in
a
It
is
used
as
last
the
attractive
against
gas.
cooling
Joule-Thomson
2.
stage
in
gases.
low-boiling
liquefying
the
5.
dilution
helium
of magnetic
system
moments,
an
when
external
moments
may
magnetic
nuclear
moments,
temperatures
using
devices
cooling device in
which
4He.
lowering of the
utilizes the
The
strength.
By
evaporation
household
of
cooling
laboratory
demagnetization
Isentropic
is an
refrigerator
basis
the
forces,
Using different
phase.
gas
4. The
interatomic
the
magnetic
temperature
of
field is
reduced
be electronic or nuclearmoments.
in the microkelvin range may
a
in
be
achieved.
PROBLEMS
L Helium
for
as a
helium
Use
of
the
and
liquid
data
in
it as
such
in
helium
Table
for
\342\200\242See,
example,
der
van
Waals
849A970).
(a) Estimate
H'aafcgas.
by treating
coefficientsa
volume
der
van
M. Chapcllier,
Hi(q
M. Goldman,
AH
4- f(rin
V.
H. Chau
xliH)
A0)
and A.
-.-._...\342\226\240
Abragara,
Appl.
Phys-41,
2. Ideal
one
of vaporization.Show
that
under
gas
gas
these
\\VL thai
iiqticfier
To.
be required to
operated
rcversibiy.
the same
and
under
would
is removed,
1 atmosphere.
typically
and A// the latent
at this pressure,
conditions
Let
heat
A1)
To derive A1) assumethat the gas is first cooled at fixed pressure p6 from
To
the fixed
between
to Tfc, by means
of a reversible refrigeratorthat
operates
upper temperature Tb ~ To attd a variable lower temperatureequalto the gas
~ 1\\.After reaching
Tb the
Initially
temperature.
T, = To, and at the end T,
at
the
lower
the
latent
heat
of
fixed
extracts
temperavaporization
refrigerator
of
temperature Tb.
(b) Insert
To = 300 K and values for Tb and AH characteristic
liter
of liquid
helium.
helium. Re-express the result as kilowatt-hours
per
Actua! helium liquefiersconsume5 to lOkWh.
liter.
1 mols\021
in which
cycle helium Hqucfier. Considera heliumliquefier
enters the Lrnde stage at T(o = 15 K and at a pressure pla = 30 aim.
all the
in liter hr\"'. Suppose that
liquefied
(a) Calculate the rate of liquefaction,
helium is withdrawn to cool an externalexperimental
the
releasing
apparatus,
load
in
boiled-off
helium vapor into the atmosphere. Calculate the
cooling
the
the
it
is
this
watts sufficient to evaporate
heliumat
rate
liquefied. Compare
if the liquefier is operated as a closed-cycle
with
the
load obtainable
cooling
the apparatus into the liquid collectionvesselof the
refrigerator
by placing
the
heat
so
lhat
the
still
cold boiled-off helium gas is returnedthrough
liquefier,
and
ex(b) Assume that the heat exchangerbetween
exchangers,
compressor
ideal
that
return
is
the
(Figure
12.1)
sufficiently
expanded
gas
expansion engine
the same temperature Tc as the
that
leaves
it with pressure
is at essentially
pout
compressedgasenteringit with pressure pc. Show that under ordinary liquefier
must extract the work
operationthe expansion
engine
3.
Claude
of gas
Te -
TJ ,
A2)
Chapter
12:
per mole
Cryogenics
pin,
pBUt, and
have
the
same
meaning
as in ihe
Carnot
iimit.
Chapter
14.
to be I Bohr
ion
the magnetic momentofa paramagnetic
By signifimagneton.
0.1
of
the
initial
we
to
understand
temperature.
cooling
may
cooling
significant
13
Chapter
Statistics
Semiconductor
ENERGY
FERMI
BANDS;
LEVEL;
355
AND HOLES
ELECTRONS
358
ClassicalRegime
of
Law
362
Action
Mass
362
363
/r-TVPE AND
Donors
Fermi
SEMICONDUCTORS
P'TYVE
363
and Acceptors
364
Semiconductors
Extrinsic
in
Level
365
Semiconductors
Degenerate
368
Impunly Levels
Occupationof Donor
369
Levels
Example:
Gallium
Semi-Insulating
Arsenide
373
p-n JUNCTIONS
Reverse-Biased
p-n
NONEQUIUBRIUM
SEMICONDUCrORS
Abrupt
377
Junction
Quasi-Fermi
Drift and
Flow:
379
Diffusion
Example:Injection
381
Laser
Example:
Carrier
379
379
Levels
Current
372
Recombination
383
SUMMARY
385
PROBLEMS
387
1. Weakly
2.
Intrinsic
387
Doped .Semiconductor
and
Conductivity
Minimum
Conductivity
387
387
5. Electron
387
and
Hole
Concentrations
in InSb
8.
Einstein
Relation
for
High
Electron
Concentrations
387
3S7
388
388
13:
Chapter
Ha
ht
n,
Carrier
conduct
v\302\273'ilti
conccnlration
= cffcciivc
=
effective
38S
Lifetime
388
Pair Generation
Electron-Hole
iiiiiiui^zny
388
Laser
9. Injection
10. Minority
11.
Statistics
Semiconductor
of holes
hoics^ donors
*inu
3cccplovs.
I he
c^uantiiEn
conccnlnU/on
for condudion
quamum
coiKcntralion
for
ctccirons;
holes.
densities
of states for the conduction
In the semieonductoi tileralurc
n,. and % ate called ihe effective
and valence bands. Notice
iKal we use ;i fo( tin; chemical
potential or Fcimi level, and we use Ji foi
cai-iicr mobilities.
ENERGY
The
is
FERMI LEVEL;
BANDS;
ELECTRONS
HOLES
AND
of semiconductorsand
treat
devices
semiconductor
of the physics
thermal physics.
of the physics of
those
below
thus
aspects
are parts of
that
assume
We
eleclrons
the
reader
in
temperature.
A
semiconductor
band
t
and
0 al!
is a
system
with
electron
orbitats
grouped
into two
energy
energy
gap (Figure 13.1). The lower band is the valence
at
the upper band is the conductionband.* In a pure semiconducior
valence band orbitats are occupied
and
alt conduction
band orbitals
bands separatedby
an
are empty. A full band cannot carry any current, so that a pure
in a semiconductor
at r = 0 is an insulator.Finite conductivity
semiconductor
follows either
in the conduction
from the presence of electrons,catled
conduction
electrons,
orbitats
in the valence band, called notes.
band or from unoccupied
Two different
electrons and holes:
mechanisms
rise to conduction
give
of electrons
from the vatencc band to the conduction band,
Thermalexcitation
of
or the presence
that change the balance between the number
impurities
of electrons
available
to fill them.
of orbitats
in the valence band and the number
and
the energy
the
band
We denote
valence
the energy of the top of
by \302\243,.,
rence
of the bottom of the conductionband
by e{. The differed
as single
does
semiconductors
Because
t ^
Eg
is between
1/40 eV at
boih
may
room
be groups
Statistics
Empiy
band
Conduction
Energy
atr =0
gap
Filled
air =0
t3.1
Figure
Energy
Air =
conduct
the
structure of
band
orbilajs occur in
a puic semiconductor
bands
\\vhjch
we usually
nt
ihe
denote
concentration of
insulator.
exlerid
gap.
energy
temperature,
or
The electron
the
pure semiconductorthe
ii, =
electrons and
two
about
for selected
gaps
energy
needed
of conduction
concentration
holes. In a
with a
wiH
nh
the
con-
be equal:
B)
\302\253*.
if the
\342\226\240temperature.
positively
tiiat
Impurities
charged
in the
give
an
have
ionized
electron
been
In the
inteniionaiiy
doped with
semiconductor
to the
crystal
(and
that
at room
become
accept
Bands; Fermi
Energy
data
structure
Band
13.1
Table
Lml; Elec
Energy
ions and
c Idea
at
gaps
300 K
itions
effective
olcs
li
free
1300K
\",.
eV
'
2.7 x 10
Cc
0.67
1.0 x !O 9
GaAs
1.43
Let
4.6 X
!he
\302\253j+be
'
10
10\"
0.58
11.7
0.35
0.71
0.42
0.07
0.073
15.8
13.13
12.37
0.39
0.015
concentration
charged acceptors.
An
ts called
1.06
0.56
17.S8
the
in
charged
acceptors.
of negatively
concentration
to
vacuum
ilia
10\"
6.9 x 10'*
6.2x 10\"
the valence
are called
process)
relative
cicctr on mass
x to'a
1.5 x
4.9 x 10 '
from
electron
an
1.1 x
5-2
4.6 x 10 '
0.18
of the
t.[4
1.35
masses,
constants
in/ftn
Si
,,p
InSb
units
in
Dielectric
f-statcs
Dcnslty-
i concentr
antun
/[/
The difference
C)
na~
the
na~
condition
becomes
which
specifies
The electron
distribution
the difference
concentration
[i is
electrons. In semiconductor
theory
the
Fermilevel.
called
Further,
almost
level
always
reserved
is designated
of a meia!
which
in
ihe
limil
r -*
by ef
we
for ihe
or
by
at
The
electrons.
To
\302\243.
theory
temperature.
confusion
avoid
as cf
our
and
with
the
the Fermi
Fermi
energy
previous
usage
to
is always
potential
is
the character
fi
chemical
semiconductor
e refers
subscript
designated
any
E)
/
electron
the
in
0, we shall maintain
chemicalpotential
D)
no~~t
exp[(e where
\342\200\224
Hj*
6:
of Chapter
function
An
of the
level
;i and
Given
the distribution
The
of
number
[l
\302\243
- /.(*)]
= I
ftU).
V)
VI!
VB
is overall valenceband
the summation
summing
is
holes
*\\ =
where
by
Here
orbitals.
we have
introduced
the quantity
which
that an orbital
probability
the unoccupied
orbital is \"occupiedby
the
is
ne{y) and
dependences
nh{y}.
Classical Regime
We
assume
that
by the
defined
regime
concentrations are
and hole
electron
both
requirements
that
\302\253
1
fr
and
fh
in
as
\302\253
I,
the
classical
in Chapter
This will be true if, as in Figure 13.2, the Fermi level lies insidethe energy
and ts separated from both band edgesby energies
that
large
enough
-
exp[-(\302\243c
To
few
satisfy
times
inequalities
are
satisfied
(9) both
larger
(9)
\342\200\224
place
n)
(gc
than
in many
/i)/t]
\302\253
1;
and
(/t
exp[-0*
eu)
to
have
ej/t]
\302\253
1.
be positive
6.
gap
(9)
and al
least a
The
a semiconductor is callednondegenerate.
and
limits on the electron and hole concentrations
t. Such
upper
applications.
With
distributions:
(9)
the
two
occupation
probabilities
Classical
':.-\"-\\~'\\
Regi
Conduciion
I
band
Figure
We
use
F)
and
exp[-(e
A0) to
write
=>
the
total
number
cxp[-(,,
of conduction
A0)
electrons in the
form
N,
A1)
Statistics
13: Semiconductor
Chapter
where we define
N, \342\200\224
\302\243
is
\302\243c
Here
band
the
A2)
ej/r].
of a
energy
\302\243exp[~(s
Cfl
conduction
the
ec as origin.
edge
lias
the maihematical
fomt of a partition function
a similar
conduction band. In Chapter3 we evaluated
sum denoted there by Zlt and we can adapt
that rcsuil lo the prescuJ problem
with
an
for
modificalion
band siructure effects. Because of the
approximate
rapid decrease of cxp[-{\302\243 - e()/i] as c increases above its minimum value
for
one
at ee,only
Nc
in the
electron
ihe
of orbitals
distribution
within
range
of a few
above
cc really
sum
in ihe
for Z%.
Nc = Zj
this gives
Numerically,
NJV =- 2.509 x
where
Tis
1019
x
dependenceas
this
Nt
A3),
formally
for
but
semiconductors
actual
differs
by wriiing,
in magnitude
in
io
analogy
A3),
Nc *= 2(mSz/2nti2K'2V
where
Experimental
is more
(H)
G/300KK'2cm\023
in kelvin.
The quantity
express
A3)
2(mx/2nh2)i!iV.
2nQV=
me*
is
values
than
called
the
arc
given
a formality.
In the theory
of
electrons
A5)
,
electrons.
Experi-
of effective
masses
in crystals
it
is
shown
that
Classical Regime
the
from
Ihe density-of-staJes
We
the
define
that
is
holes,
the influence
of external
effective
wilh
masses different
under
of particles
dynamical massesusually
masses, however.
mass. The
quantum
coticetilralion
for
??\302\243
eleclrons
conduction
from
different
are
as
NJV -
nc =
A6)
By A0 the conductionelectronconcentration
ne
NJV
becomes
A7)
Jo the assumption
The earlier assumption (9) is equivaleni
that n,. \302\253
nc, so
that the conduction
electrons act as an ideal gas. As an aid to memory, we may
level at ;i. IVanriiuj:
think
as
wiili
the Fermi
of Ne
arising from N( orbilalsat \302\243\302\243,
In
is invariably
called
the effective density of
the semiconduclor
literature
nt
statesof
conduction
the
Similar
reasoning
band.
gives the
number of holesin
valence
ihe
band:
- e)/t]
wiih
the
definition
A9)
We define
where
wk*
concentration/^
is
llns
NJV
dcnsity-of-sJaJcs
for
holes
as
2{in^z/2jihi)m.
effective
mass for
holes.
By
(IS)
ihe
hole
s NJV is
nh
\342\200\224
aBexp[\342\200\224(/(
\342\200\224
e,-)
B1)
A7), this
Like
positionof
edge.
In
of the
valeuce
is
of the
independent
energy gap
the common
concentration
t^
concentrations
Then
classical regime.
in the
valeuce band
effective density of states
Action
The productn^nh
are
the
called
con-
quantum
to the
band.
of Mass
Law
is
nu
(he
of
terms
relative
level
Fermi
literature
semiconductor
(he
the
s=
\302\2439
ec
eff.
In
O/r]
s=
ncnuexp(~
we have
semiconductor
a pure
B2a)
eJz)
\342\200\224
>ibt
ut.
carrier
intrinsic
B2b)
impurity
We
then
may
both
provided
product
in the
concentrations
means
n^iij,
this
that
product
B2a) as
write
B2c)
The
mass
of
value
action
the
depends
product
law of
only on
semiconductors, similar to
chemical
the
mass
action
is
the
law
(Chapter 9).
Intrinsic FermiLevel
For
an
intrinsic
sidesof A7)
and
semiconductor
eB
= e^
nh
and
we
may
equate
the right-hand
B2b):
neexp[-(ec
Insert
ne =
\342\200\224
and
eB
divide
- ^)/r] =
by n,.exp(
(vO\022exp(-\302\243/>*).
\342\200\224\302\243(/r):
ej/2r].
B3)
and Acceptors
Donors
logarithms to obtain
We lake
/i
{U,
+
\302\243,.)
= l(cc
|t Iog(u,/u,)
is usually
that
amount
Pure
an
semiconductor
lies near
the exact middle by an
intrinsic
from
displaced
B4)
3rlog(\302\273ifc7\302\273i,*),
small.
w-TYPE
and
Donors
for
+ e,) +
Acceptors
are an
semiconductors
idealization of Httle
Semicon-
interest.
practical
to
usually have impurities intentionally added in order
semiconthe concentration of either conductionelectrons
A
more
with
conduction
electrons
than holes is called \302\273i-type; a semiin devices
used
Semiconductors
or holes.
increase
semiconductor
n and
electrons is called p-type.The letters
p
and
in
carriers.
Consider
a
silicon
positive
signify negative
majority
crystal
atoms.
which some of the Si atoms have
been
substituted
by phosphorus
hence each P has
Phosphorus is just to the right of Si in the periodic
table,
semiconductor with
fit
into
the
Si it replaces.
valence band; hence a Si crysial
filled
than the
more
electron
one
exactly
do not
electrons
P atoms wiil contain
extra
These
some
with
more conduction electronsand, by the law of muss action, fewer holes than \302\253
Si crystal
Next consider aluminum atoms. Aluminum
is just
to the left
pure
of Si in the periodic
fewer
than
the Si
table, hence Al lias exactly one electron
it replaces.
As a result, Al atoms
increase
of holes and decreasethe
the number
of
number
electrons.
conduction
electrons
relative
from
Impurities
Similar reasoning
For the presentwe
may
enter
assume
that
is the
to
Si
not the total number of
other columns of the periodic table will
and
assume
band or
the conduction
each acceptor
fill
one
and Al will
number of valence
electronson
behave
not
for
semiconductors,
donor
each
as P
table
the
atom.
so simply.
example
GaAs.
the
from
valence
are
called
the approxifrom the conduction band.Theseassumptions
all impurities when ionized are either
approximation of
posiimpurities:
fully ionized
A\".
donors
D+ or negatively charged acceptors
positively
charged
electrical
The
condition
D) told us that
neutrality
band or
An
nt
\342\200\224~
nfc
nj+
\342\200\224
na~.
B5)
J3; Semiconductor
Chapter
Becausenh
Statistics
aciioti law,
mass
the
m,V\302\273*from
equation for
we secthat
B5)
to a
leads
quadratic
nc\\
B6)
V-\".^!-^1.
root is
The positive
i{[{A'O2
\302\273*
because
and
nh
\302\253
\302\273* l([(AnJ
Most
the
often
+ V]1''2
- An],
nr or
either
is much
ft*
[(AnJ +
an n-type
An*]\"*
=x
A/i
+ nffAn
p-typc semicondiiclor
Ji. ^
The
majority
n?/\\An\\
proportionalto
Level
Fcrmf
By use
An
the
B9)
ln*l\\bt\\.
B7) becomes
nh
An;
** n^/An
and B7)
is negative
\302\253
n,;
while
extrinsic
the
carrier
mmoriiy
C0)
becomes
{A/i| +
nk ^
\302\253
n,.
h;V1A*i1
limit
B8)
C1)
jAffj.
is nearly
concentration
equal to
is inversely
jAnj.
in Extrinsic
of the massaction
having to calculate
the
solving
m +
/ij,by
B7)
+ (hj&nJ]1'2
|^[i
semiconductor
nt
In a
B8)
nt.
In
than n,:
larger
be expanded:
then
can
B7b)
extrinsic semiconductor.
The squarerootsin
defines an
Condition
B7a)
\302\273
\\An\\
This
An}
is Urge
concentration
doping
that
so
concentration,
have
we
An
+ V]1/J
A7) or
Semiconductor
law
Fermi
concentrations without
Tlic Fermi level is obtained from
n, or
we calculated
level
B1) for/c
first.
the carrier
Scum
Degenerate
Figure
various
the
13.3
doping
band edges.
sniaii
silicon
as a function
The Fernifleveis
concentrations.
decrease
of liic energy
of lempcraturc,
are expressed
relative
gap
wiih
icmperaiure
for
Ic
has
been negieaed.
We may
to
find
ft as
a function of
ths
temperature
An.
the
cr
conduction
DegenerateSemiconductors
one
When
quantum
of
concentration,
carrier.
the carrier
we
The calculation
is increasedand approachesthe
use
the classicaldistribution
no longer
A0)
concentrations
may
of the carriorconcenir.iiion
now
over
as
follows
all
occupied
an
iiiteura!
the
quan-
for
iliiit
treatment
orbitais, which n
over the density yf
IS:
Chapter
Statistics
Semiconductor
llie
panicles of mass \302\273j
is
of stales
densily
C4)
in
n,V;
Lei x
of orbitals
number
in
the
transition to conductionelectronsin
\342\200\224
oblain
by m,*; and \302\243
by e
ec. We
s (e -
and
er)/r
ij
(fi
et)/t. We
interval
energy
+
(\302\243,e
we
semiconductors
of
To
ck).
iV
replace
obtain
J(c to
C6)
ee
p.
as the
is known
C6)
\302\273
x
we
have
\302\273
1,
\342\200\224ij
Ferml-Dirac integral.
so
that
cxp(x
jj)
\302\273
1.
In
this
limit
C7)
the
result
familiar
for
the ideal
gas.
several
limes
electron concentrationrarely
exceeds
the quantum concentration nc.The deviation
between
the value
of/i from C5)
and the approximation
then can be expanded into a rapidly
C7)
converging
=
series
the
r
of
ratio
power
njn^ calledthe Joyce-Dixon
approximation:*
In semiconductors the
\342\226\240
\",/\"\342\200\236
C8)
\302\253-\342\200\224i-S-f)
t3.4
Figure
compares
the exact
the
approximations
C7)
and
C8).
\342\200\242
W.
B. Joyce
1.483S6
and B. W.
x lO\"*:^,
Dixon.
App!.
- -4A2561x
Phys. Lclt.
1Q-6.'
31,354 A977).
If the
right side
of C8) is
wrine
Slmicomlitct
Dtgcncnitt
-6
-5
-4
-3 -2
-I
i)
above
conduciion
band
Joycc-Dixon approximation
C8).
(|.
- i,)h
icrm
of ihc
When
Sta
Semiconductor
13:
Chapter
neisno
ask
we
Ihe
ihe
of the
expression
io show
reader
mass action
ihat
C9)
If
the
Itself
gap
here
will
on
depend
Impurity
on the
depends
localized
atom
be used
n, to
concentration.
Levels
as
of
Ihe
where the
gap,
energy
from
orbitals
some
moves
semiconductor
the
iis extra
released
has
consider
We
states.
bound
semiconductoris severalordersof
the
energy is to be
by
square
paniy
column
V donors
donor
corresponds
in
the binding
effects. Table
mass
of
because
because
mostly
lower,
magnitude
divided
is
one
set
orbitals
of bound
for
every
donor.
argument applies to
'he valence band, as in Figure
A parallel
from
set ofbotmdorbitals
as
Aej. Ionization
ionization
an
wiih
6rrteV.
For
zinc,
T:.Mc 13.2
column
energy
Asa ~
\342\200\224
il!
the
all
for
most
acceptor,
!uiiu..iio.i encr^e*ofcuhmm
acceptors
in Si
arui
Ge,
are
listed
VI donors
column
important
\302\243,,,ofthesameorder
Ea
in Si
energies for column III acctipcors
closeto
&\302\243a
24meV.
V <j
in mcV
Ace
11
AI
13.2.
cp OIS
Ga
In
16
49
45
57
65
12.7
10.4
10?
iOS
11.2
Some
of
Occupation
'
\"'
!'
At,
Letch
Donor
\302\261
Donor
13.5
Figure
and acceptor
Occupation
A
level
donor
can
different
occupationsof these
level is occupied one
two
by
spin.
opposite
gap,
energy
with
sometimes
states.
Levels
be occupied
As a
in Uic
levels
impurity
orbitals
electron,
result, the
by an electronwith
with
orbitals
are
not
the donor
either
spin
nt
spin down.
the same
independe
up or
of
each
other;
Once
the
occupation probability
for
donor
level
is not
but
function,
by a function
given by the simple Fcrmi-Diracdistribution
is vacant,
the
the
orbital
treated in Chapter 5. We write
that
donor
probability
so that the donor is ionized, in a form slightly different
from
E.73):
the origin
to
singly occupied donor orbital relative
that
of the energy. The probability
the donor
orbital is occupied by an electron,
the
is
is
so thitt
donor
neutral,
given by E.74):
Here
Ed
is
the
energy
of a
Statistics
Semiconductor
13;
Chapter
Acceptors
require extra thought.
each of the chemical bonds between
ihe
atom
acceptor
of
and the
the
acceptor,
surrounding
of
one electron
acceptor,
is missing
the
from
up or
haveeithcrspin
bonds.
surrounding
condition
neutral
The
exp[{^ ~
2 +
A,
the
with
\"\021+2
Efl)/i]
exp[(Efl
orbityl
acceptor
Because
neutral condition
term
2 x J ~ 2.
\"}
{~
$x]\"
unoccupied,
occurs
with
probability
______
The
of
value
From
An
\342\200\224
== nd+
or D2)
D0)
_ __________
is the
na~
difference
D3)
of concentrations of D*
arid
A\342\204\242.
we have
D4)
D5)
The
condition
neutrality
This expressionmay
of
functions
the
position
represent the
positive
four
visualized
be
in
posicivechargesequal
by a
Fermi
of the
terms
be rewritten
may
D)
D6);
logarithmic
level
(Figure
the two
charges.The actual
total
the
negative
as
The
level
as
four dashed
occurs
sum
func-
lines
of
aii
charges.
nd+
-^
jio~
\302\273
nh
as
in
Figure
13.6, the
Occupation of
Figure
13.6
intersection
approximation
with
will
A7)
the
be
in Figure
point
neutrality
curve
determinaiion
Graphical
sciniconducior
an n-1ypc
DonorLetch
?!e curve,
on
holds.
U ihe
cxp(/</T)exp[(^
\302\243i)/t]
\302\2537>
(\302\273A)\302\253PfcA);
(\302\273>Jexp[(\302\243,
tj/t]
= njn*
D8)
nc*
Is
electron
the
neexp[~(et
the
with
be present
would
that
concentration
Eli)/i] = ;i,exp(-A^/t)
donor
level.
nd* to
the
in
Here
if
conduction
band
the donor
ec
Aed
. {49}
Ej is
iontzacton energy.
insert
We
set
D4) and
into
D8)
nt
obtain
E0)
nf3
is a
llus
shallow
weak that
donor
8\302\273j\302\253
\302\273/, the
for
-v
\302\253
i.
x ~
With
large and
=? 1 +
xI1*
we
8\302\273d/He*
ionization.For
Table 13.2, so
the
for
the subjectof
Problem
-ix2
;tj(l
gives
P
=s 0M5nc
ne*
expanded by use of
\302\253
2it//ne*
parentheses
example,
that
\\x
is sufficiently
doping
\342\226\240\342\226\240\342\226\240
E3)
obtain
^ \302\253\342\200\236
\302\273\342\200\236
The secondtermin
E2)
I}-
close to nc.ffthe
may be
root
square
is
solution
+ (S\",,//)/)]1'3-
V([l
nt* is
levels,
E1)
i\302\273rfn,*.
For
\\n,nt*
in
the first
300 K, we
=
from D9). If \302\253j
Si at
un-ionized.
E4)
2<td/ite*).
The
have
Ae,j
0.0!nf,
limic
Eq.
of weak
t.74r
E4)
from
predicts
ionization is
6.
an intrinsic
StuM-itiiHtuting
p-n
However, ic
with
is possible
concentra
high
near tnerinste
carrier
Cm-3) of oxygen
impuriiy levels near the middle
to achieve
lions (tOi5-IO17
in GaAs by
concentrations
and
Junctions
chromium
doping
two impu-
together,
have iticir
of ihe energy gap. Oxygen enters
an
and is a donor in GaAs,
as expecicd
from the posiiion of O in the periodic
Cable
relative to As; the energy
is an acceptor
v> i'h an
level* is about 0.7 eV belowts. Chromium
level
about
Q.S4eV
below
energy
et.
a GaAs
Consider
boih
and chromium. The ratio of liiS two
crysiai doped with
oxygen
conceniraiions
is not critical; anything
with
an O:Cr raiio between abouc 1:10and
10:1
will do. If the conccitiraiions of all olher
are small compared with those of O and
impurities
Cr, (he position of ihc Fermi level will be governed
by ihe equilibrium betweenelm -ons
on O and holes on Cr. The
of Figure
construction
t3.6 applied io tliis system
shows
that
over the indicated concentration raiio rangedie Fermi
is pinned io a range between
level
t.5i
above
the O fevel and l.5r below (he Cr level.
With
ihe Fermi level pinned near the
imrinsic
middle of the energy gap, the crysiai must act as nearly
Gallium
arsenide doped in this way is called semi-insulating GaAs and is used extensively
to to10 il cm\\ substrate
as a tiijjh-resisiivity
for GuAs devices. A similar
[!0a
prodoping
procedure
is possible
in inP, with
iron
ihe
taking
place of chromium.
impurities
ttiat
As site
p-n JUNCTIONS
Semiconductors
are almost
never uniformly doped. An underan
semidoped
requires
understanding of nonuniformiy
of structures called p-n junctionsin which
the doping
semiconductors, particularly
to n-type within 'he samecrystal.We consider
ton from /vtype
changes with
posi!
a semiconductor
at
.v = 0
which
the doping changesabruptly
crystal inside
from a uniform
donor
concentration
nd to a uniform acceptor concentration
as in Figure
i3.7a. This is an exampleof a p~i\\ junction.
More complicated
na,
a
device structures are made up from
simple
bipolar transistor h.-is
junctions:
used
devices
understanding of devices
in
the
shift
is
eVN.
electron
The
energy
potential
bands
stop of
in
ihe
crossing
height eVbii%
an
junction
example
potential
as
discussed
of
two
(Figure 13.7c).
of the potential
systems
in Chapter
5.
The
step
when ihc
buitl-in
two
voltage
sides
wilh
concentrations,
shifted
relaiivc
generate the
diffusive
between ihe
equilibrium
electron concenlralions as wet! as hole
level must be
(c) Energy bands. Becauseihe Fermi
Vbl
ealabtishes
differenl
to each
buitl-in
voltage
and
to
shift
the
dipolc
energy
required
bands.
to
We assume that
nondegenerate range, as
defined
Hf
are
If the
donors
the p
\302\253
nd
\302\253
\302\273c;
\302\253
\302\273(
na
the n
side and
on
the
from
\302\261
side
Jij,
\302\253
\302\273t.
E5}
the acceptorsfully
on
ionized
ne
one on
extrinsic but
by
ionized
fully
in the
lie
tta
and
the other
on thep
band
The
conduction
\302\273\342\200\236.)
s:
nh
E6)
na,
energies
i\\
p sides
and
superscripts
follow
from
A7):
E7)
\302\253\302\253-/*-xlbgl^/nj;
H~ xlo&{nJnc) =
ccp =
by
eVtf
is 0.91
eV in silicon
in electrostatic
step
E8)
must
satisfy
the
at room
temperature.
to shift
is required
potential
Poisson
to
other.
each
find eHi
band
the
The
= es -~9.2t,
edge
electrostatic
energies
on
potential
equation
(SI)
Hfl=s0.0inL.,we
0.0inrand
E9)
Tlog(W>,2)
\302\243CJ. e\302\253
tlogK1/\"^).
Hence
B2c).
which
;1-
= ~~ ,
F1)
of the semiconductor.
space charge density and e the permittivity
varies.
must
be
whenever
In
the
vicinity of the junction
<p
Space charge
present
material.
the
carriers
no Songer neutralize the impurities as in the bulk
charge
the
h side and negative on the p side
on
The space charge must be positive
where
is the
(Figure 13.7d}.
concentration is less
Positive
space
than
the
charge
donor
on
the
concentration,
side
means
indeed,
that
as the
the electron
conduction
Statistics
Semiconductor
13:
Chapter
Take
Then
ofthe
origin
=
ec(x)
electrostatic
\342\200\224
and
e<p{x),
\302\243c(~-a))
ne{x) =
ThePoisson
potential at
x = -co.soihai
</
d.x i/x^
(/.x \\il\\-J
dx
=
x =
i6d\\
, ,1
0:
F5)
\\dxj
interface
F3)
AM2
oc)
Integrate uiih the initial condition<p{\342\200\224
the
F2)
to obtain
_</WV
At
<p(-00}= 0.
ntcxp[e<p[x)/T].
]
Jdtpfdx
by
an exponential
becomes
A7)
^
Multiply
predicts
A7)
is
F1)
equation
level,
0 we assume that'
F6)
Vn is
where
the n side.
part of
that
The exponential
on the right-handsideofF5)can
be
on
occurs
and
neglected,
we obtain
E for the
-v
ofthe
component
[peii,/c)(K,-
electric
field E
F7)
*/e)Vn
\302\243=[{2eMB/\342\202\254)(^-t/e)]\022,
where
ihepstdcTlie
we
potential
drop
part of ilie built-inelectrostatic
be the same; from this and from
two \302\243
fields
must
I-; is that
that
Vn
on
occurs
-V
Vp
Vbi
find
(\302\243^')\022
F9)
rse-BiasedAbrupt
is the Sameas if On
field E
The
lite
from
to a
junction
the
Junction
been depleted
electrons had
side all
ii-type
p~n
distance
, G0)
-(Vw-2r/f)
no
with
at
depletion
>
\\x\\
theory as a measureofthe
layer into
on the
p side,
The totaldepletion
width
1f
we assume
- 4.25
\302\243
\302\273o
wK
nd =
i0licm\023;e
and w
x 104VcmwI
Reverse-Biased
Let
of penetration
depth
a voltage
be
4.70
the
to a
applied
p side
n
to the
p side
in bulk
contains
side
law. As
action
holes,
and
increased
\302\273
side,
contains a very
a very
by the
are
2z/e
== 1 volt,
we lind
iO^5cm.
p-n junction,
holes
and
low
which
means
voltage
raises
p side
the
cond uction
drive
will
the
of
concentration
little
current
approximately
applied voltage,Figure
ihe same
13.S.
The
as
if
built-in
the
field
at
electrons
The distributions
flows.
is at
potential
from the ;i
a result, very
potential
Vbi
Junction
p-n
Abrupt
~ l(ko;aiid
n side.
the
Similarly,
wa is
distance
The
\\vK.
the
the
ifie
mass
of electrons,
voltage
were
given by
G3)
Chapter
13: Se
..-\342\226\240
\342\200\224
\342\200\2247\342\200\224
//
it
/
\342\200\224'
\342\200\236._
r.
mi .->
13.8
Figure
Reverse-biased
p-?i
tfic cjuast-Fcrmi
showing
junaion,
by
G4)
In the
semiconductor
device liierature we
charge and
correct
field
electron
distribution;
distribution
approximations
we
F2).
have
often
have
solved
find
beea
G3)
the Poisson
equation
with
the
Currtrni
Flow:
Drift
and Diffus
SEMICONDUCTORS
NONEQUILIBRIUM
Quasl-Fcrmi Levels
When
is illuminated
semiconductor
with
light
from
raised
of
energy greater
txind to the conduc-
quantum
the valence
and
electron
The
the hole
ii levels:
levels:
emii
7\021\"
levels
Quasi-Fermi
are used
and
+exp[(t-\342\200\236\342\200\236)/,]\342\200\242
extensively
in
the
analysis
of semiconductor
devices.
Diffusion
caused
conduction
by a
position-dependence
quasi-Fermi
level.
15; Semiconductor
Chapter
Statistics
contribution
conduction
to this
proportional
we
weak,
that the
to ihe
electrons
assume
may
gradient:
current
electrical
an
carries Ihe
electron
we
\342\200\224e,
x
(\342\204\242e)
potential,
electrons
the
density.
Because
each
have
flux density),
{electron
as the
defined
G7)
number of conduction
electrons
Fora
given
driving
conduction
is
charge, the associated electricalcurrent density
force for this current.
of grad fic. We view grad jj\302\243
as the driving
the
current
is
force,
density
proportional to the concentration
electrons.
Thus we write
a negative
carry
the direction
constant
the proportionality
where
should
If
not
the
be
confused
with
fi't
in lerms
is
\302\253
nf
of the eleclronconcentration
ut
G8)
the
electron
mobility.
The symbol
pt
n,
cottduclion
is
the conduction
concentration
electron
G8)
~.
Jt_
Thus
flux
in
area
unit
the
particle
in Chapter
treated
of
is
G6)
is
unit time. The ciose connection of G6) to Ohm'sSaw
14. Because the flow of particies
from
to
low
chemical
is
high
to grad nc, but because
flux is opposite
conduction
electron
crossing
nt
not a
density,
charge
5
in
is
density
J, cc grad/*(.
HereJe is
con-
\302\253
nc
G9)
is given by
A5),
which
can
be written
as
+ Tlog(it7\302\253A
\302\243c
(80)
become:
(81)
A
gradient
in the
conduction
a gradient
in the
electrostatic
Flaw:
Current
electron
We introduce an
diffusion
coefficient
Dt -
- eptntE 4-
J,
There arc two different
field and one caused by
Analogous
a concentration
in the
electrous
the
io the right
valence b;ind.
is really an
grad
eDe
form
final
the
(84)
by
an
electric
gradient.
to holes,with
(83)
results apply
relation
Einstein
the
pex/e
14. We
in Chapter
discussed
by
Dc
and Diffusion
Drift
one
for
The
difference.
holes,
but
valence
is the
chemical potential
band quasi-
carry
holes
hole
current
a positive
rattier than a
j.iv as the
grad
current
Jh
as
the rest
through
Carrying
the
of
analog
sign in
diffusion
the
but
concentrations,
hole
holes
because
current,
(84),
Example:Injection
laser.
\302\273
(85)
jvifcgradjv
The
highest
nonequilibrium
carrier concenlrations
in
semi-
semiconductors occur
condiiion
for
populaiion
inversion
is ihat
/Me) >
Wiih
ilie
quasi-Fernii
distributions
G5)
this
(S?)
fM
condition
is expressed
us
(88)
13.9
Figure
Double-heterostructtirc
potential
electrons
layer,
but
from
cannot
injection
form
where
a degenerate
becomespossible.
For laser
to
An
which
The condition
important
the
additional
condition
is
that
the
energy
than
an
state
distinction is treated
in solid
important
direct gap are GaAs and inP.
The population
in the double hcterostructtire
of Figinversion is most easily achieved
Figure 13.9;
two wider-gap
semiconductor
here ihe lasing semiconductor is embeddedbetween
In such a structure
is GaAs embedded in A!As.
regions of opposite doping.An example
there is a potential
to the p-type region,and
barrier
of electrons
that prevents the outflow
an opposiic
barrier ihat prevents
ihe outflow of hoies to then-type region.
poieniial
indirect
gap. The
semiconductors
with a
for
the current
rent
Example; Canter
eiiher
combine
recombination
an iaipsiriiy
throush
by an electron
falling
inio
dircciiy
Flow:
Drift
and Diffusion
a hole
with itic
or ihey
*\342\200\236-(!
w here
fr is the fraction of
Itcnce not
and
available),
(89)
recombinationorbitais already
occupied
characteristic time constant for the
ai
by an
capture
electron (and
process. We
tiie rate
Kc =
\302\253hcrcit'
\342\200\242
t. is a
concentration
~/>A
/,'lj'e'
(90)
is the
Figure 13.10
impurity
Electron-hole
recombination
recombination
ihrough
\342\226\240
gap-
of
the
con-
consiaitts
r.
Statistics
Semiconductor
13;
Chapter
wiihf,
ihc
and
in thermal
evaluated
n,
distribution
we use
ihe
Wiih
cancel Thus
ignore
Fcnni-Dirac
equilibrium
we have
for/,
(91)
Rcr musi
and
Rrt
means
which
equilibrium,
= exp[~{^~e,)/r].
A -/,)//,
Thus
raies
muitipiiciiy
spin
ilie two
equilibrium
(92)
becomes
=
^
ne' is
where
Fermi
equilibrium
arc insenedinto
and
(89)
in
ft
coincided
A7)
Rcr
Re,
Tor
%,\302\273/,
te
f,)nt
-* Rh,
flh,
(94)
/,\302\273/].
by ihe subsiituiions
is obtained
holes
ihc
(93)
rale becomes
recombinalion
- ~ [A'-
be present if
recombination
the
wjlh
electron
R,c
rate
recombinaiion
analogous
net
lhal would
conceniralion
electron
(90), ihe
Re =
The
(93)
^exp[~fc-\342\200\236)/!]\302\273\"\302\243.
!h;
nh*,
and
Here
fk
is the
lifetime
and
n,,* is,
eiecirons,
of holes
by
these substiiutioiis
Iiisteady
in
ihe
limit
thai ail
(95)
definiiion,
ah*
With
1 -/,-/,.
~Jr\\
/-I
nBexp[-(\302\243,
ej/i]
rccombiiiationrale
is
staieUicuvorecombinaUonfaiesmusibcequaS:R,
ions for ihe two
unknowns
equal
f, and /?.
C96>
;i,V\302\273.*-
=
W'i.
Hft
eiiminalc
R.Equations
/, to
194)
find
(9S)
is the
This
are developed
recombination
Hail-Siiockley-Read
10 and
Problems
In
Applications
iheory.'
I).
SUMMARY
!. In semiconductors
(completelyoccupied
band (complelely
empty
Electrons
gap.
energy
electrons;
orbitals
empty
2. The
by
of
probability
Here
3. The
\\i
is
Here
ne
An
is
negatively
4.
\302\253
nv.
efTecItve
and
valence
R. N.
energy e is governed
level
in
an
ievei.
Fermi
neutral
eleclrically
semi-
condition
concentrations
Concentration
impuriiies.
is said to be
in
the
classical
regime
when
ne
\302\253
nt
and
Here
and
concentratioi)s for electrons
holes;
hi/ and \302\253?/arc
for eiecjrons and Ijoles. In the semiconductorHteralure,
masses
the effective densities
of states for the conduction;:nd
are
called
\302\273\342\200\236
the quantum
are
nc
the
excess
A semiconductor
nh
the
Fermi
by the neutrality
i\\h are
charged
of ihe
potential
governed
and
function
location of the
energetic
semiconductor
and
distribution
chemical
the
is
of a
occupancy
Fermi-Dirac
ihe
grouped
\342\200\224
at
an
into a
valence band
and a conduction
0 in a pure semiconductor)
r
al
x = 0 in a pure semiconductor), separated by
in the conduction band are calledconduct:-:1'
in the valence
band are called holes.
are
orbilals
electron
the
Hall,
bands.
Phys.
Rev.
87, 387{i952);
\\V.
Shockley
and W.
Rev.S7.
S35{!952).
ihe classical
. In
regime
where \302\243\302\243
and
eu
are the
energies of
valence
and
conduction
bands.
6. The
in the
that
stales
\"\302\273\302\273*
'I.-1
is
The
The intrinsicconcentration
intrinsic
( \342\200\224
pure)
dominate;
electrons)
the
sign
sign of
dominant
ionized
The
dominate.
(wholes)
oppositeto
of the
impurities.
structure
is a rectifying semiconductor
from p-typc to n-typi. A p-n junction
junction
p-n
transition
Here
is
the
concentrations,
9. The
electric
permittivity,
and
current
| V\\
and
nu
Vbi
are
densities
JB =
Jp ~
Here
% and
ihe
are
\302\243\342\200\236
electron
Mj are
and
the
due
ionized
applied
to electron
and donor
and hole
the
con-
ePsgrad
electric
junction
abrupt
are
e/yi,E + eDegmdne,
ephnkE
internal
internal
acceptor
and the
nn
with
contains
semiconductor.
called
is
semiconductor
carriers
an
energy gap.
conduction
S,
in
quantity
is the
A
nh
product
'M'uexp(-\302\243a/i)
impurity concentration.
value of n{ and
common
the
is
n,
7.
of the
independent
nh,
mobilities, and
\342\226\240
given
by
diffusion coefficients.
and hole
electron
ihe
are
PROBLEMS
1.
concentration,
\302\253
nt.
jAnj
Intrinsic
2,
concentration
donor
net
the
when
Caiculale
semiconductor.
doped
Weakly
tjons
and
conductivity
ininimuni
conduc-
electrical
The
conductivity.
\342\226\240
-.
conductivity is
+ njh)
e{ntpe
(99)
where Jit
ph are
and
the electron
3.
concentration.
A manufacturer
impurity
specifies the
=
Ge
of
a
as
20
ohm
cm.
Take
3900 cm2 V\021
resistivity
I/a
p
crystal
pc
and
V\021
s~l.
What
is the net impurity concentration a) if
/Zk=s 1900cm1
is n-type; b) if the crystal is p-type?
crystal
and
Resistivity
5.
of Ihe
is the
law for high electron concentrations. DeriveC9),which
no
is
small
law of mass aclionwhen
longer
ne
compared to ne.
InSb at
concentrations
hole
and
Electron
n-type
narrow
\342\200\224
4.6
nc
Use
applicable.
transcendental
for
equation
the generalized
nc by
6. incomplete
iont'zation
donor impurities
doi
if the
than
t }og(nJ8nd) by
large
impurity
tonization
o/
donor
iteration or
gap,
energy
nor
\302\253
Calculate
in InSb.
ne
the
action
Mass
4.
form
res\021
is
the
Saw
\342\200\224
for
Et
C9).
approximation
Ihe tran-
Solve
graphically.
Find
imparities.
tontzalton energy fs large
/i
= ne.
nondegsnerate
mass action
deep
energies
and
Because of the
is not
hole concentration
1016cm\"\"J
the
nc, nh,
explains
insulators,
substances
even if impure.
is larger
with
Statistics
13 s Semiconductor
Chapter
7. Built-in
eiecuic
= I0~
103 and Xj \342\200\224
X[
as this occur in the base
aids
8.
in
driving
Einstein
that
in
the
relation
electrons
injected
for
C8)to
approximation
concentrations
region of
approaching
series
a
or
n-p-n
across the
transistors.
The
the
/!s//ii
built-in
such
field
base.
Use the Joyce-Dixon
of the ratio DJfic for electron
concentrations.
electron
high
give
many
a .P-type
<- \302\273%
\302\253
at x = xt is \302\273\342\200\236\"
\302\273\342\200
=
=
n2 \302\273
ns at X
x2. What is
~
Give
values
for
to a value na~
interval (xtlJCj)?
nurnerica!
5 cm. Assume T = 300K.
distributions
Impurity
off exponentially
field in the
falls
built-in
Suppose
profile.
expansion
exceeding
itc,
10.
Minority
independentof
carrier
lifetime.
are raised
ditt
Electron-hole
14
Chapter
Kinetic
Theory
GAS LAW
IDEAL
THE
OF
THEORY
KINETIC
392
MaxwellDistribution of Velocities
394
Verification
Experimental
Collision
Cross Sections
TRANSPORT
PROCESSES
Particle
391
395
397
399
Diffusion
Thermal Conductivity
40!
Viscosity
402
404
Forces
Generalized
406
Einstein Relation
KINETICSOF
407
BALANCE
DETAILED
TREATMENT;
ADVANCED
TRANSPORT EQUATION
BOLTZMANN
Particle
409
Diffusion
4!0
Distribution
Classical
4!
Fermi-Dirac Distribution
LAWS
OF RARF.FIED
Flowof
Molecules
of
Speed
413
GASES
414
a Hole
Through
Example: Flow
413
Conductivity
Electrical
408
Through a LongTube
4!6
417
a Pump
SUMMARY
419
I'KOIiUCMS
1.
Mean
Speeds
in a
Maxwcllian
Distribution
in a Beam
2. Mean KineticEnergy
to
ElectricalConductivity
3. Ratio of Thermal
4.
Thermal
5.
Boitzmann
Conductivity
Equation
Thermal
420
420
420
of Metals
and
419
Conductivity
421
Chapter14: Kinetic
6.
Flow
Theory
421
a Tube
Through
421
7. Speedof a Tube
ant
conscious
of time.
of being
But if still
the theory
only an individual
remains
in
my
power
of gases is againreviled,not
struggling weaklyagainstthe
to contribute
too
much
in
such
a way
will have to be
L, Betiynann
stream
thai, when
rediscovered.
Kinetic
Ideal
of the
Theory
Ga>
!n
this
chapter
of velocities
of transport
is difficult.
KINETIC
THEORY OF THE
the kinetic
We apply
~
law, pV
container. Let v,
as
in
Nx.
14.1.
Figure
from the
GAS
IDEAL
method to obtain an
molecules
Consider
the
denote
If a
velocity
molecule of
LAW
of the
derivation
elementary
that strike a
area
normal
to
the
component
unit
mass M
is
of
wall, the changeof momciitum
the
reflected
the
of
ideal gas
wall of a
specularly
is
molecule
\342\200\224
A)
2A/|i-x|.
This
gives an
pressureon
_ /momentum
\\
second
law of
motion. The
is
wall
the
Newton's
by
per
cliangc\\/number
molecule
)\\
unit
of molecules strikmgN
area
per
unit
lime
pj
. Let a(vI)ilv1
of
that
the
totai
pressure
is
= M f\"
p = JO
{a>2Mv1la{t\\)dv1
J-a
The integralon the right
so that p ~ Afn<yI2>,
is
The
the
thermal
average
C)
v.la{vMv..
the
by
concentration,
equipartition
of
change
ily
of momentum of a
is reftecied from
v which
ntaincris
~-2M\\vz\\.
3). Thus
(Chapter
energy
p=
is
the pressure
iiAf<ps2>
= (NfV)z;
'it
D)
result.
assum
ption
What
comes
We now
must go
back,
with
immaterial
it is
same
the
to the
distribution,
of Velocities
Distribution
Maxwell
reflection is convenient,but
t!:e surface
into
equilibrium is to be maintained.
if thermal
classical velocity
say
of specular
as
\"velocity\",
In Chapter 6 we
this
is the
found
the
tradition
when we
Often
function.
distribution
in
physics
function
distribution
of
function
when
of an
an
ideal
gas
ideal gas to be
Ati =
is
where/(cn)
tltc
E)
of occupancy
probability
into a
of an orbital of energy
\342\200\242
ui\\l
in a
number
cube of volume
between
probability
it and
V
n
Li,
+
The average
tin is
in
the
positive
octant of a sphericalshellof
product is
{{nn2dn)f{zK)=
the spin
take
We
To obtain
a
find
connection
the
consider
from
with
G)
and
the desired
G)
&/.n*exp(-\302\243jz)dn.
of
distribution
probability
the quantum
between
atoms
whence
of a
We
of t'ekctlies
is ^Dnn2)(Int
tin
thickness
MaxwellDistribution
classical
The
\302\243\342\200\236.
the classical
number
kineticenergy
and
velocity, we must
the
classical
\\Mvz is
velocny
related to the
be the number
of
particles in volumeV.Let NP{i)ili}
in
velocity magnitude, or speed, the range dv at v. This is evaluated
,!>: - (iln/ilijib - (\\lL/hn)il\302\273.
We
have
(8) by setting
a system
of N
W(*/i>
{-n;ji!exp(-\302\243./T)*i/\302\273
(9)
ii.;/^Yi.2cxp(-A/o:1/2i),/i..
From
Chapter 6 we know
of
that
}.
n/\302\273Q
(.V/L^^lnt^fMTK'2,
so that
the
v1 becomes
Thus
(ll)
\342\226\240!n(A//2j[i)lV<:.\\p(-A/rV2r).
Tin's
is the
P(i
Mr
of the
Table
!.
is (lie
root
!4.I,
\\
\\
Figure t-l.2
function of
speed
probable
speed tm(,
arc the
mean speed
velocity
of
in units
shown
mean square
loot
ttie
\\
most
the
* {2t/A/I\". Also
c and
as
\\
i-AK1.
1/
Table
4.1
Gas
ofcculat \342\226\240
*e!ocilies
31273
?
\".\342\200\236,
16.9
Oi
4.6
13.1
12.1
Ar
4.3
H,n
6.2
5.7
2.86
Ne
5.8
53
Kr
Xe
N,
4.9
4.5
in
below;
14.3
Figure
theagreement
of atoms
distribution
from
the
of an
distribution
velocity
in
those
at
\342\200\242
P. M.
low
velocity.
Marcus and
Press, 1959.
to thetr
In proportion
J. H. McFee,Recent
research
\342\226\240\"\342\226\240
by
lhetawsofbydrodynamic
Marcus
and
McFee.*
an extra
involves
by
of potassium
the
compares
is excehent.
factor, the
The exit beam is weighted favor of atoins
ho^e
1013.
of atoms
velocity
2.63
2.09
1100.
distribution
velocity
40
2.27
Free electron
The
the slit
from
The curve
the
4.2
18.4
exit
different
\342\226\240\342\226\240,.,
He
verification.
of A2)
Gas
H,
Experimental
which
10*01115\"'
iin
K,
Bow and
not
by
the oven,
component
of high
watt.
in molecular
through
to the
fceanw,
ed.
}. Esterman,
atoms
Academic
i SecUtms and Me
10
9
>?
-?*
zj
Measured
14.3
Maxwell transmission
an oven al
traiistnissio\302\273
curve for
a temperature
U 12 13
time
Tiansit
figure
10
and
points
potassium
that exit
is Ihe
axis
homontal
E?\302\260C.The
calculated
atoms
from
transit
is in arbitrary
utoms iransmiitcd. The inicnsity
units;
the curve attd fhe points are normalized to the same maximum
value.
After Marcus and McFce.
of the
lime
slow
ihan
atoms
Ihe walls.
strike
The weightfactor
is
the
and
wiih
dv deftnes
v +
P,,(,Iwett given
ihe quantity
by (H).
We
can
estimate
aioms of
eachother.
From
has traversed
The distributionA2)
Figure
will
of
ihe
transmission
through
distribution
ihe collision
diameter d
where
PbciJ,v)iSv,
transmission
Cross Sections
Collision
normal
ucosf?
component
velocity
collide
14.4
rates of
if their
we see
centers
thai one
as
rigid
spheres.
Two
collision will
occur
when
an atom
an averagedistance
A3)
(a) Two
Figure
14.4
if their
centers pass
cacliother,
travels
(b) An
a long
K'tnaic
14:
Chapter
rigid spheres
arom of
distance L
collide
will
d of
a distance
within
Theory
each
diameter d which
will
oul
sweep
where
>i
the
is
freepath:it is
result
We
diameter
the
d is
at=
of the
velocity
the
estimate
2.2 A
The coiicenEration
volume.
unit
traveled
as for
Tiie
by an
/is called
length
If tlie atomic
crosssectionac
[ielium, then die collision
C.14)B.2 x KT'crnJ
of moleculesofan
idea!
gas
the mean
target atoms.
of magnitude
order
nit2 =
per
distance
average
the
neglects
of atoms
number
\302\253=
15.3
atO:Cand
is
lO-i6cm2.
atm
A4)
is given
by the
Losclimidt number
=
m0
The
volume
Avogadro
is the
number
number
is
the
2.69
A5)
x IOi9atumscnrJ.
divided
number
by the
molar volume at
of molecules in
combine
a ad
molar
A5) to obtain
Processes
Transport
free path
mean
the
tttz
\342\200\2243\342\200\224
This
is about
length
= 2M *
1\302\260\"i Cm'
lO*7\"\"\"\"^
2\\rT9
]7pT6
atom. The
of an
diameter
the
^16a'
associated collisionrateis
At
path
in
small
is
a system
Consider
a constant
with
we may create a
opposite endsin
system
the
steady
is
at
the
gradient
the
in
There
is
directly
the
through
a
linear
proportional
specimen
in
region
to the
s=
flux
most
noiogicai
law,
of
the
flux density
transport
(coefficient)
3A
law for
as Ohm's
of a
quantity
= flux density
system by placing
will
How
direction
tempera'
the
through
will
increase
quantity
is trans-
flux
is
driving force;
in this
flow
steady
For example,
at two different
is the
system
in a
energy
temperature,
higher
otUer.
the
to
large reservoirs
with
total
transported
apparauis,
a nonequilibrium
in
condition
noncquilibrium
contact
thermal
If reservoir
tures.
the
laws of rarefiedgases.
PROCESSES
TRANSPORT
state
dimension of
the relevant
with
comparison
section on
in the
except
I0~6atm
of
pressure
of
x (driving
force) ,
relation
is called
A7}
a linear
phenome-
Thedefinition
the conduction of electricity.
is:
net
quantity
unit area in
oM transported
unit
time.
across
(IS)
Table 14.2
Summary
of
laws
transport
phcnomenologica!
Flux of
particle
Effect
Number
Diffusion
Coefficient
Gradient
property
J,
DifTusmty/)
dz
Viscosity
Transverse
Thermal
Energy
conductivity
ictricai
Electrical
Charge
conductivity
n
dv.
M ~~
\342\200\224
= Ct
\"
-~
a:
Thermal
\"z
JB
K
conductiviiy
Conductiviiy
E,
xx number
of panicles per unit volume
= <Ji'J>
Z = mtan thermal
speed
/ \342\226\240=
free path
mean
C|- heat capacity per unit volume
thermal
pu \302\253=
energy per unit volume
*2- shear
force per unit area
Fx/A
bols:
i;
Viscosity
ip *=\302\273
elccirosuiicpolcniial
E = electricfield intensity
q = elcciticchdrgt;
M
p
^=
mass
\342\200\224
mass
p ^
of parucle
per unit volume
momentum
J.
The net
direction
one
opposiie direction.Varioustransportlaws
Particle
In
14.5 we
consider a
reservoir
at chemical
reservoir
at chemical potentialft2.
is at the higher
chemical
1 to
reservoir
entropy
Consider
particle
by
H-
the
particles
2 -f
the
when
first
system.
difference
urea
a'uait
taken
contact
with
diffusive
contact
with
If
is constant.
wili flow through
flux
reservoir I
the system
the
increase
will
of chemical
Tile
concentration.
in particle
diffusive
reservoir
temperature
then
2. Particle
diffusion,
difference
The
potential,
reservoir
of reservoir 1
total
caused
summarized
are
the
Diffusion
Figure
from
the transport in
in Table 14.2.
minus
density
potential is
Jn
is the
in unit
as thc\"gradicnt
system;
-,)n =
The relation ts
called
Fick's
law;
-Dgradti.
here D
ts
the
A9)
putt
tele
diffusion
constant
or
diffusivity.
travel
freely
Figure 14.5
contact
over distances
\342\226\240
Opposite
with reservoirs
ends
diffusive
and/ij.
The
Kinetic
14i
Chapter
flux density
Theory
is the averageoverail
of
a hemisphere
on
directions
B0)
to
want
We
ts the
value of cjg
the average
express
is
average
are
forward
c.
and
path,
it =
of?/.
Here
is the
projection
IcosO
of the
of a hemisphere,
likely. The eletnent of surface area
the surface
over
taken
equally
is 2xs'm0i}9.
terms
tn
\342\200\224
?cos<?
Thus
B1)
B2)
On
with A9)
comparison
The particle
particle
we
with
are
of charge
tile
by
in
particles;
processes
Let
pA
density of A
in
the
has
(i';)
is the
value for
same
tile
conductivity
with
the
with
the
describe
that
D,
A.
molecules,
the
thermal
viscosity
If A
is a
then
quantity
the flux
p;irtidcs in
a similar
\342\226\240>/
(-\342\200\242')
e,<\302\273,>.
all
In
problems.
is
z direction
j;
ulierc
transport
by particles.
by
transport of particles;in
in electrical
and
particles;
other
for
model
of energy
the transport
is given
diiTusivtty
with the
coneerncd
transport of momentum by
transport
the
dilTusioii
conductivity
we see that
that
tlie
depends
z directioii.'!
on the
lie drift
velocity of
expression;
IaPa<v.)
B5)
Thermal Conductivity
The
exact
value o(fA
magnitude of the orderof unity.
the
of
A
on
and
be
calculated
the
method
depends
dependence
velocity
may
by
of the Boltztnann
transport equation treated at the end of this chapter. For
we
set
with A9) for particle
simplicity
fA~lin this discussion.
By analogy
the
law
for
the
of
A
is
diffusion,
phenomenologt'cal
transport
a factor with
fA is
where
126)
with
diffusjvity D given
the particle
by B2).
Thermal
Conductivity
faw
Fourier's
Ju
describes
density Ju
\342\200\224
B7)
^Cg
transport of
additional
The
is transported
energy
under the
not
but
energyt
flux
^o,i> is
within
diffusion
K and
conductivity
that
assumes
form
there
is a
of particles.
Another
by means
of particle
in the z
density
flow,
as
addi-
flow
electrons
v,hen
nci
direction is
JJ
valid
thermal
influence of an eiectricfield.
energy
where
the
of
terms
in
the mean
velocity;
of the
factor
equation,
drift
=s
128)
/>\342\200\236<!\342\200\242->
,
pu
is the
energy density.
This result is
analogy
with
the
-DdpJAx = -D(tV,/cr)(i/t/i/x).
Reservoir
Reservoir
Figure 1-1.6
conijci
reservoirs
wiih
system
at lempcratures
arc in thermal
r, and ij.
B9)
Theory
per
unit
of energy. Now
the diffusion
describes
This
denoted
volume,
by
-Ju
on comparison with
is just
dpjet
the heat
capacity
Cy. Thus
-
-.DCYgradr;
C0)
is
C1)
at very
low
conductivity of a gas is independentof pressureuntil
of the apparapressures the mean free path becomeslimited by the dimensions
are
low
than
collisions. Until very
apparatus, rather
pressures
by intermolecular
attained
there is no advantageto evacuating
a Dewar
vessel, because the heat
The thermal
as C1)
long
applies.
Viscosity
and transverseto
the
velocity
viscosity coefficient tj
of
gradient
in the .x direction,
is
of momentum
diffusion
with
the
defined
by
the
Slow
parallel
a gas with
z direction.
flow
The
C2)
Here
vx
is
the
x component
of momentum;
component
by the gas
on a unit
to
normal
direction. By Newton's
if the plane receives
plane
tlte z
acts on the xy
a net flux density
of x momentum
J:{ps), because this flux density
rate of change of the momentum of the plane,per unit area.
second law
of
motion
a shear
.v
stress X.
measures
the
diffusion
the particle
the mean
flux
density
in the
-Dp
z direction
daJds
-n
C3)
Thus, with
by B3),
given
rj
The
free
mean
n is
and
path
the con
is / =
Dp
= y-c!
from
\\jnd2n
of viscosity
where d is the
A3),
rt
may
be
molecular diameier
expressed
as
htcfiml1
Tlie
pressurp.
gas
unit
CGS
The
C4)
C5)
independence
fails at
molecules
pressures
when
the
pressures
when
path
is
longer
than
the
at
dimensions
very
very
high
low
of the
apparatus.
Robert
the
of
independence
1660
In
Boyle
reported
of a
damping
an early
pendulum
in
Experiment
the
Pendulum
included
We observd
continud
With
understood.
implausible, this result is readily
btit
decreasing
pressure the rate of momentum-transfer collisionsdecreases,
each
the
comes from farther away. The largerthe distance,
colliding
particle
collision
larger the momentum difference; the increasingmomentumtransfer
per
cancels
the decreasing collision rate.
It is easierto measurethe viscosity
than
the diffusivity. HD = r\\jp as predicted
by C4), then K is rclaiedto jj by
at
Although
first glance
The observed
of
values
higher
Improved
than
the
calculations
value
of
- nCyfp.
C6)
ratio
Kp/rjCy
given in Table
Tabie
Gas
but
Theory
Experimental
K,
in
K~l
mWcm\"'
He
1.50
0.18
0.158
Hi
1.82
1.28
N,
0.26
Oj
0.27
at
0rC
and
2.40
2.49
210.
1.91
84.
1.91
167.
have
1.90
189.
neglected;
l atm
we.
;\302\273poise
186.
we
effects
/, in
incm*sM
D,
Ar
difficult,
Kp/tjCy
in
the
general
references.
The
Comment,
of
dilTusivity
gas
atoms
of a parliclc
Tlie quaniily
Comment,
to ihe
Reynold'snumber
be equal
tj/p
D. The
diffusii-ify
raiio
for taminar
criierion
kinemaiic viscosiiy;if
is caJlcdrlIie
i\\/p
eiiicrs
into
C4)
iiotds,
v should
iiydrodynamic
flow.
Generalized Forces
of
any
transport
from
process.
We
one
of a
pars
and of energy. By
identity at constant volume,
flux
density
of particles
da = -c\\Vwe write
the entropy
current
density
Ja
with
analogy
}~
(IN
the
thcrmodynaniic
C7)
as
C8)
of
rate
net
of continuity,
C9)
divjo.
cajdt
o(
change
volume
is equal
to the
element the net rate of appearanceof entropy
rate of productionga minusthe loss - div Jo attributed to the transportcurrent.
In
In
unit
a transfer
the energy
density u
The
N are conserved.
U and
process
is
\342\226\240=
D0)
-divju;
the equation
for
of continuity
equation
particle concentrationti
is
{41)
Let us
divJa
Let C7)
to
obtain
refer to
the
net
unit
+ Ju-grad{l/t)
div
(tt/x)
take
we
volume;
rate
C8);
of entropy
~~
ct
use
D0H43)
to
D2)
grader).
a partial
1 cu
i\\
t ci
tot'
C9) in a
rearrange
\342\226\240
time
change:
dd
We
- Jn
Ja
form
en
D3)
suggestive
of
the
ohntic
power
dissipation:
3. = J.
Here
Fu and
Fa are
grailUM
W)
F, = grad(-;</r).
D6)
generalized forcesdefined
F.
s grad(Vr);
\342\226\240
J,
gradi-;</r)
by
14:
Chapter
In an
Kinetic
Theory
Fn
lit terms
Fn =
==
n,Rt
potential
the
grad/jjni
q gradtp
-gE]
the mobility,
as
D9)
of
coefficients
be
an
D8)
written
terms,
-i>ngrad\302\253 4- uflE
p. is
and
for
qE.
= {r'n)gradn;
\342\200\224
\302\273
Thus
-UAJO^gradn
>=
dtfTusjvity
that
so
<=
gfad^\302\2431,
3\302\253
where D, is the
as
potential,
D7)
xlog{n/nQ),
flux density
particle
or,
{-I/t)grad/i
-\"{i/t
Fn
How
==
gradn
so that
equal,
velocity per
is Djnp. in D9)
E0)
a classical
Comment.
irreversible
processes,
processes. We
Onsager
diffusivity
and the
mobility
gas.
We gain an advantage,for
if we
use
FM
FH in
and
reasons
relalcd
D6) as
the
to the
driving
thermodynamics of irrevers-
forces
linear transport
for the
write
Ju
The
ihe
between
relation
relation
=\342\200\242
Z,aiF,
of irreversible
Jn =
L12FB;
t2tF,,+L22F,
E1)
thermodynamics is that
L^B)
Lj,i-B)
E2)
=
where 8 is the magneiic
For E2) to hold,
field intensity. If B = 0, then
L;J
Ljf always.
are perfcclly
the driving
forces
F must be defined as in D6). Other definitions of the forces
L that
valid, such as the pair grad i and grad n, but do not necessarily lead lo coefficients
cited
see the book by Landau and Lifshiiz
saiisfy the Onsagcr relation.For a derivation
in the general references.
of Detailed
BALANCE
DETAILED
OF
KINETICS
Bohr.
Consider a system whh two states, one at energy A and one at energy -A. In
an ensemble of N such systems,N* are at A and N\" are al \342\200\224A,
with
\\ ==
N*
+ N\". To establish thermal equilibrium there must
sonic
exbt
mechanism
Consider
the rate equaiion
whereby syslems can pass belwecnihe two stales.
for transitions into and out of the upperstate:
=
dN+/(lt
wherea,
/J
ts directly
transition
rate
of the
functions
be
may
-1-
\342\200\224
is
to
\342\200\224
the
in
\342\200\224
to
transi-
The
state.
to the
proportional
directly
E3)
proportional
from
- PK+ ,
uN~
state.
4-
thermal
In
afp =
the Boltzmann
<N
result
expresses
mechanism
oscillator
-+
s +
1)
__
W
W
\342\200\224J
\302\253
<*\342\200\242>
<*>
so thai, with
=
\302\243
<sy
W
W
\342\200\242
<sy
exp(e/r)- P
2A to
I)e;
In
the
derived
result
the
from
=
+ i =
+
of energy
(s
to (s \342\200\224
i)e.
that
is shown
it
the excitation
with
proceeds
the excitation
texts on
\342\200\224
that
/J(t)
transitions. As
in the
assists
se to a state
goes from se
oscillator
Prob{s
__
a relation
that
E4)
exp(~2A/r)
of energy
state
* +
inverse process
the
mechanical theory of the
quantum
only if
be satisfied
can
+ -+
transition
in the
for
>/<N\">
This
factor.
be satisfied
must
= 0, which
(i/JV*/i/i)
equilibrium
exp(e/t)
most
distribution;
Planck
exp(E/T)
in
'
conserve energy,
aft -
<5>/<s
1)
exp(-2A/r).
E5)
thermal
principle
equilibrium
balance
of detailed
the
Chapter14t Kinetic
Theory
the rate
exactly
equal
from
leads
state.
the
One
ADVANCED TREATMENT:
TRANSPORT
BOLTZMANN
theory of
classical
The
equation.
v. Tiie
velocity
transport processesis
Tlie
Boltzmann
the
flowline
dt
absence
the
+ i!t,r -+
us
that
following argument.
function.
distribution
if we
We
consider
The Liouville
follow a volumeelementalong
tle,\\ +
dt.T
d\\) =
tk.v
E7)
/(f.r.v) ,
With collisions
of collisions.
fit +
on
the
E6)
is conserved:
distribution
f(t
in
by the
is derived
equation
displacement
mechanics
rells
theorem of classical
transport
of particles in drdv.
= number
of a time
effect
the Boltzmann
distribution
classical
f{t,\\)thdv
the
on
based
the six-dimensional
in
work
We
EQUATION
dv)
- f(t,r.v) =
E8)
dt(ff/ct\\mijoni,
Thus
dt(cf/c!)
a denote
Let
+ dr-
cflct +
This
In
is the
many
of
introduction
gradv/ = (/t(f//^)Mu-
gradr/+(/v
\342\226\240
grad,
/+
E9)
ihen
\342\226\240
gradv
F0)
\302\253
{df/ct)tM.
a relaxation
the
collision
lerm (cf/ct)eolJ
may be treatedby
the equation
the
introduc-
ParticleDiffusion
is the
Here/0
with
time
relaxation
for
of
distribution
The decay
distribution
velocities
up by external forceswhieh
is set
- f0)
we
if
note
that
dfo/dt
has the
equation
are
= 0 by
Do not confuserc
a noncquilibrium
removed.
suddenly
(torn
obtained
f ~fo
definition of the
as
F1)
F2)
distribution.
equilibrium
This
solution
F3)
ft
is
We combine
iu
the
that xc may
exeluded
not
E6), \302\24360),and
time
relaxation
be a
to obtain
F1)
r and
of
function
v.
the Boitzmanu
transport equa
approximation:
F4)
In the
Particle
definition.
by
Diffusion
Consider an isotliermalsystem
The steady-stateBoltzmann
approximation
of the particle
in the relaxation
a gradient
with
equation
transport
concentration.
time approxi-
becomes
F5)
-(/-/0)/i{,
v.dffdx*
along
x direciion.
the
F6)
^fo-vsMJx,
/\302\273
where
we have
solutions
when
replaced cf/'dxby
desired.
Thus
necessary
for
the
vj^lfjdx
/\342\200\236
treatment
can
iterate
order solution
the second
We
dfojJx.
to obtain
higher order
is
-f vxlr*tllfalilx\\
of nonlinear
effects.
F7)
Kinetic
14:
Chapter
Theory
Distribution
Classical
in
/0 =
as
in
linear
in
function
/ and f0.
exp[(/* -
e)/i],
F8)
We
6.
Chapter
distribution
ijmil:
classical
the
the
take
can
We
is
equation
iransport
as in
normalization
the
for
normalization
than
rather
\302\24368)
as in
E6). Then
solution
order
first
for the
F6)
/ = /o The
flux density
particle
(ilfofduWtifdx)
in the
ifoh){dn/dx)
F9)
(^J0/x)(dti/dx).
x directionis
G1)
J/-$vxff>ie)de,
is the
\342\226\240Dfc)
where
density
of orbitals
energy
range:
G2,
\302\273,
as
in G.65)
for a
J/
The first
integral
particle of spin
=
Thus
zero.
JuI/01D(\302\243)f/E
vanishes
because
idn/dx)
v3 is
G3)
jiuJxJohM^k
an odd
function
and
fQ is
an even
func-
function
of
vx. This
distribution
flux
vanishes
for
the equilibrium
Fermi'DiracDistribution
The
as
be written
may
integral
i JV/oO(E)<fe= ~j
fi
equation
*=
the
with
of the
|nt
density
particles. Here
-{z(z/M)(dn/(lx)
G5)
is
\302\253
-{nxJKtyiflnldx)
+ constant.
xlagn
,n/M
J(iMi'!)/0O(e)\302\253fe
G6)
of
form
the
diffusion
diffustvity
= Vr/A/.=
G7)
K\022>V
time
is that it is inversely
Another possibleassumptionabout the relaxation
~
as in rc
l/v, where the meanfreepalh 1isconstant.
proportional to the velocity,
Instead
of
we have
G4)
J* =
G8)
~(dft/dx)(l/T)j(vx2/v)focD(\302\243)dB
and
now the
J
where
c is the
\302\273
-i(^\302\273A)W/V^)
G9)
~\\mdn/dx)
(80)
is
=
\302\243>
Fermt-Dlrac
J.x
and t!:e diffusivity
i>ic
(81)
lie.
Distribution
The distributionfunction
is
- ^_
;XP[(\302\243
WAJ +
'
(82)
\342\200\242
\342\226\240
Kinetic
14:
Chapter
Theory
dfo/dx as in
To form
the derivative
need
we
F9)
x 6{e-'y)
'tfJdH
at low temperaturesr
a general
for
property
large for
ft.
function
the integral
consider
Now
=^ n
and
F[c)
lhat
bciow
argue
(83)
Dirac delta
that
At low
F{c){dfOl'dii)j\302\243.
j\302\243
ts smail
near n we may
varying
5 is the
Here
\302\253
dfo/dfi. We
take F{e)outside
the
dfQ/dfi is very
temperatures
F(\302\243)is
with
integral,
very
the value
rapidly
Fin):
(85)
where we
used
have
dfo/dn
=*
temperatures /@) =
At low
consistent
the
with
1;
fiux
particle
density
is, from
S(e
also used
side
right-hand
approximation.
dfoftlx
The
the
thus
function
delta
have
We
~df0/dz.
= co.
f0 = 0 for \302\243
of (85) is just F[}i),
Thus
- v)d[i/dx.
(86)
Giy
(87)
wheret{ is
has
integral
by
defines
use
the
at the
surface e
M3n/2cf)
time
relaxation
the Vaiue
nlm
zero ii@)
Jlt/ilx
G.!7),
\302\253
-(m,;i\302\273)Jii!Jx.
JM'
At absoluie
(88)
~ 3;i/2ef at absolulczero,from
velocity
vf ort the Fermi surface.Thus
of Q([t)
tile
= /( of the Fermisphere.The
{h2j2in)Cji2n}2
where
zF =
\\mvF2
(S9)
J, whence
= {ilftV-mKJii')''1/\"\021}''\"/*
5(\302\243r/\302\273),/ii.V/.v,
(90)
Laws
Gaits
of Rartfitd
//=
The diffusivity
~Bxt/3m)t:Fdn/dx
is the coefficientotdn/dx:
-
closely similarin
time is
classicaldistributionofvelocities.
to be taken at the
Fermi
applies,
Electrical
energy.
Fermi-Dirac
distribution
approximation
applies.
the
Conductivity
The isothermalelectricalconductivity
we
when
difiusivity
the
replace
cfdq>fdx
electric
field intensity.
ihe
~-<j\302\243i of
dji/dx of the
external
follows
the particle
muliiply
gradient
potential,
The electriccurrentdensity
J,
(92)
see we
We
and
\\vF\\
the resuh
to
form
relaxation
{92} the
In
(91)
~\\ve\\dnfdx.
H\\/'\302\273)E;
time
relaxation
from
follows
xc. For
gradient
of the
{76}:
(93)
uqhjni
the Fermi-Dirac
distribution,
(89},
J,
Thus
far
this
in
free path
apparatus.
At
pressure
gas
ofa molecule
system conneciionmay
free path. We may usefully
1
10~6atm
10~6kgcm~2
region
of
discussion
as high
pressures
or
*=
of
the order
draw
a line
The
is understood
dimensions
of a
diameter
of 25 cm, thus
of
the
of the
free
mean
vacuum
mean
laboratory
order
the
of ihe
(94)
nq'xjm.
GASES
the
chapter
mean
molecular
path
RAREFIED
OF
LAWS
(nq2xc/m)E;
is approximately0.1Nra\021
to be the regionin
of the
than
the
which
apparatus.
mean
knowledge
or
Knudsen
free path
of
the
of gases
behavior
this
in
is important
region
pressure
use
the
in
vacuum
of high
The
of torr,
terms
where
here
1333dynecm~3;
American
;= 1 mm
torr
bar
Then:
torr
iO~3-i(T6
vacuum
high
3O~6-3O~9 torr
below
torr.
3G~9
Flow of
in ilic Knudsen
we
regime
to get
in order
moleculesdo
strike
of
solve a hydrodynamic
flow
problem
because the
to
the
calculate
rale Jfl at
have merely
molecules
through
a hole,
time. We
per unit
of surface
area
unit
gas
We
other.
each
sec
not
need to
do not
molecules
which
recommended
terminology
in
tlie
for
find
flux
density
(95)
where
is
(95),
prove
the
and c is the
cube containing
concentration
consider
a unit
strike unit
unit
time,
Each
molecules.
so thattn
strikes
molecule
unit time^nc,
molecules
require the
average of
area.
solve
We
per
cos#
for ?, in
terms of c. Becausec. *=
c cos
0, we
a hemisphere:
over
2*
=
J^2
~2n
Therefore
?,
the basis
\302\253
\\c,
for many
and
(95) is
of gas
(96)
1'
[\"\\\\aedf
obtained. The
calculations
\"\"
expression (95)for
flow in vacuum
the
flux
forms
regime.
If
is
the
area
moleculesper
unit
of the
time,
hole,
the
iota!
particle
flux,
which
is the
number of
is
nS ,
(97)
Flow
S =
The conductances
of
the hole,
through
conductance
is usually
moleculeat T
10cm
the
with
is defined
hole
the
expressed in
Molecules
300
diameter,
K we
have c
a Hols
(98)
as the
liters
For
second.
per
x 4.7 x
lQ4cms~';
leads
a
to conductanceof 917
(98)
=>
Through
l-ic.
taken
volume
of
for
lime
the
flowing
gas. The
the average
air
hole
of
circular
roughly
liter/sec,
1000
liter/sec.
For a
hole
a given
with
the concentration
Here-
we
have
or,
the total
conductance
~ m,
p
because
to the
particle
flux
is
proportional
pressure p:
the quantity
defined
A00)
Q~pS,
A01)
Thecondition
for
zero
net
flux is
equal
requires
pressures
to
gas
a higher
will
flow
pressure
from
the
on the hot
Knudsen
regime
equal
pressures
side.
on the
...
Kinetic
!4:
Chapter
Theory
- t2, Eq.A01)can
Eft,
be
\\
- p2)S =
-(p,
~AQ
C03)
where
Example; Flow
We assume
molecules
which strike the inner
is
is, the reflection at [he surface
assumed
to be diffuse. Thus when
there
is a net momentum transfer to
is a net flow
there
the tube, and we must provide a pressure head to supply the momentum transfer. Let u be
the velocity component
of the gas moiecuicsparallel
to the waii before striking
the wall.
We estimate the momentum
that
transfer
to the waii
on the assumption
every collision
wiih
the wall transfers
monicmurn Af <n). The rate of ttow down the tube is (M<\302\273>. where
A is the area ofilie opening.The rafe
at which
molecules strike ihe wall is, from (95)
of
wail
through
tube
the
tube.
a hns
are rc-emittcd
in
ali
that
must
diameter
L the
and'
equal
to the
of the
length
for tile
solve
flow velocity
(u) to
A05)
momentum transfer to
the
tube
&p:
=* AAp.
{nLMcM(u}
We
lube. The
differential
pressure
\\nld)ic
whered is the
the
that
directions;
A06)
obtain
A07)
<u>--\302\243w:ln\302\260'\302\245mr
The net
flux
is
AO
- n(u)A
Ap
\342\200\224
A0$)
wher
S =
A09)
tA\302\253/Ap=
\342\200\224j-
is the
conductance
analogously
to the
conductance
of a hole, Eq.(97).
of a
Speed
detailed
more
with averages
calculation,
lo a
arefully, leads
conductance
differing
xAi
of a tube
conductance
The
This
ratio
that
every
will be larger
molecule hits
valid we must
compared to uniiy,
to be
than
for
unity
1L <
that
the
of a
that
4d.
In
bole
with
A06)
writing
the
area. From
same
tioi
we assumed
implicitly
for a
be true
means
which
A12)
\302\273id.
our earlier
Using
tube
1 meter
Speed
of a
Pump
The speedofapump
is defined
as the
is defined
it
S/3*:
by
take
distribution
velocity
a factor
2t\302\253/J
suppose
over the
from A09)
Pump
pump.
to thecOnductancoofaholeorofa
similarly
volume pumped
The
per
same
unit
time,
symbol
with
S is
the
tube;
taken at the
volume
(H3)
just
as
Proof:
denote
of two
i!ie conductance
for
Let
pE
denote
[lie puntp
the
pressure
tube.
Continuity
let
p2
of
Theory
SO that
^i
to
equivalent
connections
A13) for
than
the
between
speed
to Eq.
pump
=
p V
be
connecting
ihc connecand of
as short
lube makes
be
cannot
poor
larger
aperture.
effective
with
a volume VI From
of pump speedanalogous
S evacuate
speed
find
we
(99)
of its awn
narrow
and
the speed
Further,
pump.
does a
rapidly
to be evacuatedmust
pump
the conductance
How
SJ),
vacuum systems
in high
why
explains
Scft
(ll5)
\\Sp
A13).
relation
The
S,W^
ScS[
Pi
iP^^E^Q^Pl
of
pressure,
A16)
di
dt
this
W0-^0)cxp(-(/io);
to
differential
\302\253
A17)
V/S.
of! 00 litersconnected
to pump with a speed of 100 liter/sec,the
e
should
decrease
second.
pressure
per
of a
the
of
user
vacuum
technology soon discovers
pumpdown
Any
For
a volume
by
that
vacuum system
than
regions
on the
expected
more
in the high and ullrahigh vacuum
slowly
The
volume.
basis ofpumping speedand system
orders of
gas predominates\342\200\224often
by many
as fast
emits
adsorbed
molecules
gas. The surface
molecules from Uie volume.
ofsurface
desorption
over
proceeds much
volume
evacuates
SUMMARY
1. The
probability
that
P(v)dv
the
Maxwell
velocity
an
atom
has velocity in
\302\273
4;:{.Vf/27rrK'Vexp{~Mi>V2
distribution.
do at
is
magnitude\342\200\224
as
the
pump
2. Diffusion is described
by
=
Jn
wiiere t is the
mean
and
speed
3. Thermal
is
conductivity
(V
5.
the
to
According
path.
by
K = iC,,ff/ ,
-Kgradr;
is given
by
mass density.
p is the
where
%cl ,
volume.
to unit
refers
I is
described
Ju =*
where
D =
-Dgradtr,
of detailed
principle
Boltzmann
The
6.
of
gmd,
is
-Lzh.
/-
gas is
a Fermi
a
the relaxation
\342\226\240
/+
gradY
7. The electricalconductivity
xc is
o( the
jf
where
the rate
exactly
equal
the
\342\200\224
nqixjm
time.
PROBLEMS
/.
Mean
speeds
velocity
square
<\302\273*>m
\302\253n\302\253
Because
follows
<>3>
<Pjt2>
distribution,
Maxwellian
is
vtaa
In a
<w,:>
root
mean
\302\273
<\302\273/>
(MS)
f3t/M)!'2.
and
<^a>
<\302\273/>
<fI2),
it
fol-
that
(_Vx3ylS
(t/M)\023
\302\273
V^JV'1.
A19)
value
the
speed
ideal
most
probable
as a
distribution
gas. (b)
is
vmP
- BT/MI'*.
vmp
By
c
The mean speed may
j^dvvP(v)
i>mp
Maxwell
lhal the
(c) Show
v,mi.
as <juj>. The
written
be
<
= (8T/rcAf)m.
\302\253
also
A20)
speedc is
Show
that
ratio
velocity of an
A22)
?., the
mean
A21)
v,mJZ~ J.0S6.
fd)
3 for
in Chapter
the expression
from
directly
an
of
z component
the
of
of the
is
atom,
\"
?,
2. Mean
thai
velocity
the
moiccuies
component
energy? Continent:
thermal
equilibrium
Ratio
particles
of
thermal
in
by a
pass through
A23)
{2t/jiA/)\"\\
[he
Find
(a)
hole
collimated
that
The moiecuiesin
at temperature
fast
lo
heat
to electrical
the
moiecuies,
flowing
ihe
The
oven.
ihc
and
residua!
Ehe
the walls
s'u (iirough
Show
conductivity.
is
collide and
do not
beam
after they
kinetic
mean
oven
an
3.
$\302\243
'
a small
that
so
(\\v:{>
for
mean
kinetic
are not in
real
of the oven.
classical
of
gas
of charge q that
K/ra - 3/2q2,
in conventional
units for
or
K/Ta
as
3/:s2/2^2
the
Wiedemann-Franz
\342\226\240
A24)
ratio.
at
or copper
4. Thermal conductivity of metals. The thermal
conductivity
carried
room temperature is largely
electrons, one per atom.
by the conduciion
The mean free path of the electrons at 300K is of the orderof 400x 10~8cm.
electron
concentration
is 8 x 102Ipercm3. Esiimaiefa)
to the heat capacity; (b) the electroniccontribution
contribution
conductivity;
(c) the electrical conductivity. Specify units.
conduction
The
thermal
5.
the
to
electron
Boltzinaun
the
Boltzmann
find
the
a medium with
Consider
conductivity.
The particle concentration is constant,(a) Employ
thermal
and
equation
dx/dx.
gradient
temperature
to
relaxation time approximation
transport
equation in the
classical
nonequiHbrium
distribution:
order
first
the
A25)
(b)
where
vx2
conductivity
the
that
Show
the
Show
a tube.
a liquid
when
that
p between
difference
a pressure
lube
conduc-
thermal
the
Sinijm.
6. Flow through
under
fc) Evaluate
2e/3m.
x direction is
flux in the
energy
a narrow tube
flows through
ihrough
flowing
time is
in unit
A27)
where)/is
the
L is
viscosity;
flow
7. Speedof
Show
tube.
is given
second
the length;
velocity
that
at
the
that
a is the radius.Assume
walls of the tube is zero.
for air
ihe
for
end
hole
in
L and
length
effects
series
in
flow
liters
is
per
by, approximately,
(I2S)
L + id
where
tube
the
on a
with
diameicr
tube of
ihe
tube.
finite
J are
length
in
by
centimeters;
treating
we
tried to correct
as two halves of a
have
the ends
15
Chapter
Propagation
CONDUCTION
HEAT
Relation, (n Versus
of Temperature
Dispersion
Penetration
Developmentof
Diffusion
424
EQUATION
with a
425
426
Oscillation
427
Pulse
Time-Independent
Distribution
PROPAGATION
OF
~0
\342\200\242'
SOUND
WAVES IN
429
GASES
Example:
430
432
ThermalRelaxation
in a
Transfer
Heat
429
Sound Wave
434
SUMMARY
435
PROBLEMS
436
1. Fourier
2.
in
Diffusion
Two
and Three
3. TemperatureVariations
4. Cooling of a Slab
5.
6.
436
Analysis of Pulse
junction:
Heat
Diffusion
p~n
7. Critical
Size
in
Dimensions
Soil
Nuclear
437
437
of
436
Reactor
437
437
437
The purpose of
the
most
both dassicai
ofsound,
Consider
first
Pick law
A4.19) for
!hc
of the
A, is the
propagation
thermal
physics,
in
found
the
from
flux density:
particle
J, a
where
the
text
EQUATION
derivation
the
of the
compass
CONDUCTION
HEAT
the
in the
problems
important
within
particle diffusivjty
n the
and
(I)
-/?ngrad\302\273
concentration.
particle
The equation
of continuity,
*-'+
assures
that
of A)
substitution
in B)
partial
particle
differential
concentration
C)
DnV2n.
equation
n.
equation
V2,
gives
y
This
B)
is conserved.
of particles
number
the
- 0,
divJ,
ofcontinuily
for the
A4.27-14.30)
of
the
we
D)
energy density is
+ div.l.
0.
Dispersion Relation,
where
\302\253
equation is of tbc
is called
as in (i
Comment.
and
particle
The
eddy
F). If 0 is
diffusion
E) to obtain
D) and
combine
F)
K/C.
the temperature.
of
diffusion
time-dependent
ihe
equation
C). The
The
Ds
quantity
diffusivity,
C)
of
form
Ds
Z),V2r;
We
volume.
unit
Versus
particle
4.23}.
current
of electromagnetic theory*
equation
intensity,
has l\\\\c
then
G)
The constant
is
may
be called
c j^JZtJ^i,
% \342\200\224
(skin
sohed
Dispersion Relation,
We
look for
to
Versus
solutions of the
equation
diffusiviiy
DV20
= cOJct
{8}
and kas
problem,
are
so
(9)
tor)] ,
0oexp[i{k-r-
]hc vvavevector.
even
highly
though
damped
Plane
it will
ihai they
wave
turn
analysis
is
arc hardly
waves
Chapter
IS: Propagation
at all
Substitute (9}in
Dk2
relation
io{k)
for a
[he relation
obtain
to
(S)
ioi.
A0)
Penetrationof Temperature
Oscillalion
the
Consider
in the
of temperature
variation
plane z = 0 is varied
0(<U) =
which
is
the
real
with
periodically
lime
>
0 when
as
0ocosw; ,
of 0oexp(-iw/),
part
semi-infinitemedium z
in ihe
6Q. Then
real
for
A1)
medium z >
the temperatureis
*=
O(z,t)
e0Rc[aip[i(kz
i3'2
and
at)]}
- l}/%/2.Thus,
{i
with
s BDJqiI11,
- iwO)
6(z,i) = 0oRe{exp(-_-/a)exp[i(i/<5)
=
The quantity
characteristic
\342\226\240=
amplitudeof
called
skin
the
the
has
BZ)/u)}\022
depth
penetration
if we
A3)
the
of a lengih and represents
the dimensions
of the
of 0 is
oscillations
depth
- z/5).
0ocxp(-z/5)cos(w(
are dealing
the
with
in ihe medium\342\200\224the
wave is highly
damped
in a distance equal to a \\vave!ength/2jr.
of soil is taken
If the
thermal
diffusely
wave
amplitude
D s= 1
as
current
eddy
B0/cu}1'1
lm.
decreases
x 10\023cm2s'\"',
equation.
as 5cm.
by
The
'
by e\"
then the
the sun
and
Development of a
of can
tOcm
of
layer
on
10 averageout
of a
top
night
day
of surface
variations
;i!
Pulse
ihc
top
dilTusivity,
ihe
not
anrf
Development of a
Pulse
In additionto
the
wavelike
severalother
useful
soiution. The
solutions.
of
forms
of the
solutions
0(x,t)
is a
alone.
conductivity
\302\253
A4)
DnDi)~inexp{-x2J4Dt)
j*y{x,t)dx
The soiutionA4}
the form
has
elsewhere.
The
might
beam
the surface,
A5)
ofa pulse whichat t = 0
localized
at x = 0, and zero
developmenl
S(x}t
sharply
pulse, as
a temperature
be
pulse
electron
the time
to
corresponds
that
so
of
heat
on
deposited
is then
given by
A6)
0{x,t)
where Cv
is
heat
the
per
capacity
plotted in Figure15.1.
because
from
inwards
assumed.
material.
of the
volume
2 arises
factor
The
unit
to
all heat
The function
is assumedto flow
is the
diffusion
of impurities
inside ihe
a p-~ujunction
form
was
flow
symmetrical
A4)
is
semiconductor.
out
with
increasing
time.
The
mean square
of
value
x is
given by
/X)dx ~2Dit
after
the
evaluating
Gaussian
A-Imi(/)
integrals. The
-
(x1I'1
* (IDty1.
A7)
is
A8)
Chapter
I Si
Propegai
= 1.0
s.b
o.s
,^\\
0.8
\"^
0.6
=4.0
\342\200\224^
0.4
Figure 15.1
from
Eq.
A6).
pulse
whh
= 1,
function.
This result shows thai the width of tile distribution increases as t\022t which is
It is
and
random
walk problems in one dimension.
characteristic of diffusion
a
medium
a
wave
is
unlike
the
molion
of
in
a
which
medium,
quile
pulse
nondisperstve
<o =
motion
for which
rfc, where v is the constant
velocity.The connection with Brownian
the
of
of
a
random
or
random walk problem
each step
follows
if we let t0 be die duration
that
walk; then r = Ni0. Mscre .\\' is the number of iteps. it follows
Comment,
a general
XrBU(i) =
so that
This
the
is
suspensions
the
rnts
dtsplacemcni
result observed
of small
iri
particles
{2Dto)llZN1'2 ,
liquids.
A9)
steps.
of
Diitribution
Time-Independent
Diffusion
a Fixed
with
at x
Condition
Boundary
or
~ 0
with
integrated
be a solution.
again
to
respect
of its
any
An important
example
to x;
respect
=*-= [\"dscxpf-s^icrfu,
= x/DDt)U2.
where
Here we
erf\302\253
of the
defined
->
\302\253u
\342\200\224
by
B1}
<feexp(-s2).
jo
Tables
B0)
the
has
function
properties
erf{0) =
Of
lim erf(x) =
0;
1.
B2)
into
an
diffusion of heat or of particles
solid from a surface at x \342\200\224
the fixed boundary condition 0 = 0o
0, with
~
=*
0 and 0 0 at x co. (For [ < 0 we assume 0=0 everywhere.)The
infinite
at x =
is the
interest
practical
particular
solutionis
0(x,t)
Again
we
proportional
to
into
see
that
DDiI11.
Let us
equation
The
to lite
that
of
is proporimpurities
a semi-infinite
of the
is independent
Laplace equation
V20
Consider
value
Distribution
B3)
the distance
a semiconductor
Time-Independent
- zrf(x/DDt)U2)l
0o[l
=-- 0.
medium bounded by
B4)
the
vary
temperature
plane
2 =
sintisoidaliy
0 and
extending
in the
boundary
plane;
0(x,y\\0) -
0os
B5)
]5:
Chapter
Propagation
The solution
0{x,y,z)= 0o5inkxexp[~kz).
The
is damped
variation
temperature
exponentially
OF SOUND
PROPAGATION
Results
in
developed
earlier
in
Thermal
effects
are important
gases.
pressure associatedwith
sound
the
this
in
boundary
plane
the
problem
z =
0.
problem.
the form
wave;
from
distance
time-independent
the
be applied
can
book
ifiis
the
with
GASES
IN
WAVES
B6)
Let
dp(x,t)
of the wave
denote the
be written
may
as
dp =
where
k is
in the
.V
We
p ~
force
is
one
The
Nz
referred
the
to
x component
unit
and
volume
of the
p =
or
subject to the
or, in
wave
propagates
the equasion
equation
The
direction.
pV
Here
B7)
the wsvevecior
suppose
where
6poenp[Hkx - on)},
pr/A-f
is the
B8)
mass of a
molecule. The
is
velocity of a volume
element.
The
motion
is
equation of continuity
dp/dt
dp/dt
+ S{pu)/dx
div(py)
= 0 ,
C0)
- 0.
C!)
dimension,
thermodynamic
is
identity
dU
+ pdV
= jda ,
C2a)
of
Propagation
which can
also be written
-_ + p_iV
du
assume
we
If
the
during
of a
passage
is
us define
We
p0,
t0 are
that
assume
three
equatioas
neglect
and
&\\\\d(l/V)[dV/ct)
NMfV
C4)
t ~ T0(l
+ s);
+ 0) ,
C5)
at
ia)pos
equations
pu ~ po{\\
+ pn)
ik{pous
icu{pfp)p0s
terms
+
reduce
in
the
= 0;
C6)
= 0;
C7)
C8)
0.
wave amplitudes
small
sufficiently
in these
+ (pTofM)O]
4- ik{(?po/M)s
re-
can
- 0.
{p/p)(ep/ct)
-iwiQt,y0 +
that
We
volume.
unit
the density
to
approximation
per
C3)
deviations s, 0 by
Pod
-iwpu
We assume
the fractional
where
= 0
(p/V)lcV/ct)
Cv(dx/di)
Let
sound wave,
+
C2b)
Ty.
Now the
-~(\\/p)(dp/dt).
da
heat
the
second
the
rewrite
beiow) that
discussion
(pending
Cy(cr/ui)
where Cv
Waves in Gases
Sound
it
squares
is
a good
and
if
the
approxima-
cross
cross
subscripts
of
products
product
dropped
su is
from
r,
cott
- (kx/M)sas ~
rCyO
ps =
0;
{kxjMH
C9)
0;
ku = 0;
or
CVB
D0)
-
us =
0 ,
D1)
IS;
Chapter
Propagation
n is
where
y =
n)jCv =
(Cy +
Tiiis
result
to
applies
fyt/M)llik ,
in
\302\243,/\302\243(,
it,
D2)
.
of sound is
The velocity
units.
our
den/dk
D3)
the lowest frequenciesup
gases from
nionatomic
if
only
\"
to =
where
solution
to
high
should
wavelength
frequencies
only by the requirementthai the acoustic
atoms.
This
of the
be much larger than the mean free path
requirement is the
of she hydtodynamic
criterion for the appHcabiiiiy
approach embodied m the
limned
force
B9).
equation
Relaxation
Thermal
gases {43}is
Wiih polyatomic
increasedthere
\342\226\240
sound
is
is associated
propagation
Thermal relaxationdescribesthe
system.
coolinghalf-ejcle
in
polyatomicgases
LetthehealcapacityCi
states, while Cy
and
t =:
of
are
period
of the
the
freedom
fre-
in
equilibrium
not at ihesame
system
with
high
lime
of the
heating and
required
for
system. In
there
conditions
between the
states.
translation
external
the
and
is comparable
degrees
of energy
transfer
Hie
in
the
when
different
standard
under
of 10~5s
molecule
strongest
wave
sound
the
between the
heat exchange
is
and
thermal
of
establishment
results when
dissipation
Energy
the frequency is
of
above which (he velocity
but as
frequencies,
region
frequency
transition
The
increases.
frequency
transition
low
at
valid
becomes
Ct(dxt/dt)
or, in
of
pSacc
thai
the
characteristic
(p/p)(dp/ci)
= 0 ,
D4)
- 0.
D5)
QS),
-kotoCiQi
Suppose
(cz/ct)
\\
the
transfer
tune
ia>x0CvO
of energy
delay
tQ
such
ioj{p/p)pQs
between ihe
that
t)/t0
D6)
koO, = @
t0 is
Here
tiie relaxation
called
- 0,)/!Q.
be
D7)
relaxation
separate
times for
,48,
where
Cp refer
CV,
(otQ
I
\302\253
to the
-^-i\342\200\224i
ftj*(A//r)
the
the low frequency limit
of
Ct). The low frequency limit of the
y0 is
where
4-
11,@)=
In
the high
\302\273
1
refers
yM
stales
not
of sound
is
are
y\302\273
frequency
limit
only
excited
of y0
of sound
and
E1)
w2(A//yxt).
are given in
C\\)/
is
E0)
to the
by
ratio [C^ +
heal capacity
velocity
D9)
(Vqt/A/)\022.
*,(cc) =
Values
low
\342\226\240
w^Af/vor)
total
J =
Here
the
and
k2 =
(O
limit
of
E2)
G*t/Af)\022.
Table 15.1;if
no
the velocity
stales
internal
at all
are excited,
The wave
is ai(enua(ed when k
pressure
absorption per
a.
coefficient
attenuation
wavelength
is
From
when
occurs
the imaginary
complex;
by
C.
~
Cp
,,,.
C,
Cy
Cv
-f
Chapter IS:
Propm
Ralio
15.1
Table
Cp Cy
Gas
for gascS
\342\226\240;
CC
Temperature,
Air
1.403
17
1.324
100
HjO
1.410
15
H2
1.450
-LSI
Oa
1-401
15
1.396
200
1.303
2000
CO,
15
1.304
Ar
15
1.668
He
kois:
For
tof
3nd
as
ftf
tic.
and Hj
for Oj
C,!Ct- =
high
9/7 -
at
lo
1.2S6,
frequencies. For
in agreement
Heat transfer
1.667,
in peruiurc
a!
ni^ii
very
frequency
high
is appftcabk.
Example:
Ic
ai levnperalufcs
room
(cmpe^aturci
excite also the v?branooal
motion,
as for O, aj 2000=C.The values
given
Eo sound
waives
to slslic processes
miti
CO2 gas
absorption,
- S/J =
Idea! gai,C,/Cr
roi a qj^equuc q&$ sJ 2
imoniiomic
suAicicr\302\273tly
For
1.660
-180
in
with
in about
1/e
standard
under
20kHz
of
wavelengths\342\200\224a
conditions
massive
theory.
Have.
a sound
Equation {33)expressesthe
iserttropic
assump-
which
ncglecis ihe thermal conduciivity
gives rise to some transfer of
thefniat
Within ihc sound wsvc betweensuccessivewsrm and cool half cycles. The
energy
0 musi be modified lo lake account
of heal (low. The heat conduction
assumpiion thai da \302\253=
F) may be wtiuen as
equaiion
assumption:ihe
equation
Kch/cx2
where 8 is
edict
E4)
- Ktfh/dx2) ,
lpfp)idpjdt)
icaps
-Ktk28.
E5)
we use
When
K/ai. At
With
essentiallythe
of the
length
of
place
low
dispersion
Wk* is
The
wavcveclor
lj{1.) becomes
relation
much Smaller
lhan
Cy,
so thai
attenuation
and
is
X is
by
low frequency
is that
* =
Ce refers lo unit
where
the
/ \302\253
}., where
condiiion
{4\\\\,
frequencies
sound wave.
of the
pan
imaginary
in
this
f/o ~
E7)
l)pK<a2j2i\\3Cp
volume.
SUMMARY
that
equation is the partial differential
equation
when the phenomenologicaitransport equation(here the Fourier
1. The
heat conduction
combined
with
the
D,
D,V2r;
iavv)
is
We obtain
of continuity.
equation
follows
K/C.
2. The
Hterature.
3. Frequently H is useful
of plane waves of the
solutions
to construct
the
in
of superpositions
form
form
0^
-tot)}.
0oexp[/(k-r
The differential
the
relation
between
<y
and
k, called
the
of
depends on the rate of exchange
between
the translation^!, rotaUonal, and vibrationai motionsof a
energy
not
and
moiecuie.
A low frequency
sound wave is describedby isentropic,
result
that seems paradoxical
at first sight.
isothermal,
parameters\342\200\224a
4. The
propagation
of
sound
waves
in gases
IS;
Chapter
Propagation
PROBLEMS
/\342\226\240
Fourier
1= 0
form
ihc
Consider
of pulse.
of a Dirac delta
analysts
has
0{x,0)=
Ik f\"
0{x,t)
D[x,t) =
the
Evaluate
distributionis
The
f{x,0),
time
by the
then
development
at
A4}.TSms
dk exp{ikx
- Dk2t).
F0)
This is a
in
ma
distribution
any
/(x,0)
of 5{x
- x') is
x',t)
at r ~
given
D7i/)f)^
Jdx'f(x',0)S(x
\302\273
distribution
and
be
0. If
extended
to
the distribu-
- x').
exp[-(.v
F1)
- x'J/4Dt]
F2)
{4nDi)~{
fdx'f{x\\0)cxp[-(x
F3)
x'J/4Dtl
solution-
general
powerful
2. Diffusion
the result
t the
time
fix,!) =
in two
E9)
J^
development of
0(x by
- a)!)},
\342\200\224
to obtain
integral
the time
describe
dktxp[i(kx
\342\200\242)-\"\342\226\240\"
of A0),
use
by
E8)
^~j^<!kcxp{ikxl
At later
or,
Six)
three dimensions,
tlte
diffusion
(C2/!)exp{-~r2/4Dt)
equa
[ion
F4)
o,F -
{C3/iin)tsp{~r/4Di);
F5)
constants
C2 and C3. These solutionsare
ihc evoltiuon of a delta function
at t = 0.
the
Evaluate
(b)
and describe
to
analogous
C4)
3. Temperature variations
in soil.
a hypothetical
Consider
climate in which
boih
ihe duiiy and the annual variationsofthe
temperatureare purely sinusoidal,
wiih amplitudes
0d =* IOC. The mean annual temperature0a s= 1OX. Take
x IO~3 cm1 s\021. What
is Uic minimum
[lieihcrmaidifTusivityofthesoiltobel
at
which
water
shouldbe
buried
depih
in
this
climate?
pipes
2a
and
uniform
initial
of a slab. Suppose a hot slab of thickness
of
water
0o < 0u
temperature 8t is suddenly immersed into
temperature
the
the
slab
to
at
the
surface
of
temperature
thereby reducing
80 and
abruptly
in the slab in a Fourier series. After
keeping it iherc. Expandthe temperature
some
time all but the longest wavelength Fouriercomponent
ofihe temperature
will
have
and
becomes
then the temperature distribution
sinusoidal.
decayed,
After
what
lime
will the temperature
difference between the centerof Uie slab
~
and
its surface decay to 0.0! of the initial
difference
0O?
0s
4* Cooling
from
diffusion
junction:
p~-n
a fixed
ihe lime?
i5. Heat
present,
the
with
diffusion
internal
equation
continuity
internal
When
sources.
E) must be
modified to read
C~ + divju =
ct
gu
Ffi)
7,
gu
is
Critical
the
heat
of
size of
nuclear reactor.
problem to
particle diffusion,
rate
is proportional
i/B
that
and
to the
Extend
the
assume
thai
considerations
there
is a net
of
the preceding
particle generalion
\342\200\224
n/t0,
\302\253
here
Chapter
nuclei;
IS:
Propagal
if no
surface losses
took place,the
neutron
concentration
would
grow
k:L are
F7)
multiples
integer
of n.
depen-
for at least
klt ky, k. and r0, and show that
time
one of the solutions of the form F7) the neutron concentration grows with
of Dn and @. In
if L exceeds
a criltcal value Ltli(. ExpressLc,-n as a function
because
the neutron
actual nuclear reactors (his increaseis ultimately
halted
dependence
of
generation
the
net
rate
time constant
gn
decreases
i\"; on
with
increasing
temperature.
Appendix
Some
Integrals
Containing
Exponentials
THE GAUSS
INTEGRAL
Let
J -
The
trick is
following
<x>
(i)
JO
(i)
of a
terms
in
different
integration variable:
-
B)
/\342\200\236
j'~mp(-y')cly.
Multiply (i)
V -
and B) and
convert
ihe
to a
result
double integral:
J_>^exp(-xa)*cJ_*\"exp(-.y2)<fy
j\"
J_*Jexp
- (x1 +
y')ilxdy.
C)
is
This
tp,
as
dx dy
an
in Figure
shown
becomes
entire *->\342\226\240
Convert
to polar coordinates r and
plane.
= r1, and the area element dA
=
A.S. Then, x1 \342\200\242}\342\200\242
y1
over the
integral
dA
ritnltp:
= 2i
'\302\2602
Jo
[j\020<=^-r')r'lr\\dif
Becauseof d[exp{~r2)] =
- 2exp(-
the
r2)rjr,
V - -n Jf4exp(-r2)]
integral
over r
is elementary:
\"
- n.
\302\273
-fnexpl-r1)]'
L
J'-\302\260
D)
C iFitc\302\243r@'5 LOfl
area
element
iU =
rrfrtltp.
GAUSS
GENERALIZED
AND
Integralsof
function
not
need
- 2
be an
JoVexp(-x2)(k,
integer, may
The integral
in
\\alues of
F)
>dy
may
be viewed
y,
V(n
2dx
E)
-1)
tabuiatcd
widely
gamrna
y~idy:
- l
(m
I),
0 <
0 from
T{z)
to reduce
possible
z <
the
satisfies
It is
interval
>
for
F)
positive
nonititeger
r.
The gammafunction
is
(m
be reducedJo the
~
V{:), by the substitutions x2
Im
it
INTEGRALS
form
the
Im
where
INTEGRALS,
FUNCTION
GAMMA
!.
to
rdalion
recursion
F)
by
negative
F{z)
for
integration
values
arbitrary
by
parts,
of z. By
argument
and
it
is
used
to
value
in
the
The
= 0,11
Form
is
Urn
even
an
Approximation
Stirling
integer,
a half-integer, and
the
aid of (8), that
0, n is
\342\200\224
21 >
i! ~ 1
\342\200\224
},
then
we find
h,
= ry +
/,
in is
an odd
(/
(i -
i) x
j)
\342\200\242
\342\226\240
\342\200\242
x
x
\302\247
= HI)
JoV'<0'
Jo*.xexp(-*!)ifc
integer,
the aid
with
similarly,
(9)
x u\"!.
l.ii -0:
Form -
If
j)
in
2i H- I >:
1, n
is
an
integer,
~ 1.
n = /
A0)
2: 0, and we find
of A0),
'lit i - 2 JoV*lexp(-x')J.\\-
= HI
The gamma
for
function
the
preceding
integer
THE
STIRLING
For large
values
1)
I x
is simply
argument
integer
positive
(HI
1)
(I-
ihe factorialof
the argumeni.
APPROXIMATION
of\302\253, n!
be approximated
can
by
A2a)
logn! *
Here
the
0{i/\302\2732)
term
slands
lj\\og2n
1/12/? is
for
omitted
the
(n
first
higher
J)logH
term
of
+
j\342\200\224
nn expansion
order terms
in
this
by powers
expansion,
of
and
!.'\302\273,
of order
l/\302\273
Some
or higher.
is to
Exponential*
Containing
Integrals
In practice,even
the
on
check
is usually
I/I2n
of the
approximation.
a
only
change below the desired
accuracy
introduces
correction
lerm
the
accuracy,
ihe
entire
To
derive
we
A2)
in accordance
write,
\"!
with
A1),
\"
\342\200\242
J0\"exP[/(x>]'h
jo\302\260x\"e\"llx
A4)
/(x)=)ilogx-x
We make the
A3>
substituiion
x=
yii*
= n(l
dx - rfdy.
+ j'lr1) ,
A5)
Then
J{X)
= I! lOgl!
9(y) =
With
It
S(j')
npog
A7)
these,
exP[/(-v)]= irV-'e
(IS)
A9)
The
function
expansionof
g(y) has
the
(.y2/\"I'2.
0;
g@) =
logarithm,
log(l
with
its maximumat
+ s)
= s
we expand
- is' + Js1-
|s\"
B0)
g{y):
B0
The
tile limit n
In
-\342\226\272
a},
integral in A9)
~ 0,
the
If B2)
term
correction
the
for
B1)
and the
vanish,
= On)'11 ,
J\"exp(-j.72)rfi.
of D).
aid
in
becomes
/
with
term
first
Approximation
Stirling
is insertedinto A9)
is a
Its derivation
1/I2n.
to A2a)
is identical
result
the
bit
We
tedious.
B2)
work
except
with
log/ii = {login +
If we
h by n
replace
Iog(n
+
(\302\253
logn!
B3a)
- 1,
- ^Iog2n +
1)!
sublracl
\342\200\224
\302\260(i)-
(n
We
- ii +
iltog'i
B3b) from
B3a):
- log(n
- 1I
<23b>
\\n
ii
log
loS\"
jj-^-jT;
= (n + J)logn
terms
omitted
where
all
can be
combined:
If this
is
inserted
into
are now
(ii
5)log(il
- 1) -
two
terms
in A
B4), we find
4 = (n-i)iog
B6)
Some
Containing
Integrals
For large
the
Exponentials
logarithm
may
be expanded
according io B0),with
+
\342\200\224
\\/n:
B7)
\302\260i
B8)
If this is
We
such
inserted in B6)
are
that
often
the
interested
relative
not
error
decreases with
neglecting all terms in
true value
we see that
in
n\\
but
\\/\\2.
that
Iogu!
in Iog/i!,
oniy
between an
increasing
(I2b)
approximate
an
\302\273.
Such
increase
=s
if
and only to an
log
approximation
less rapidly
ii
value
of
accuracy
Iog/i!
and
is obtained
than linearly
with
the
by
n:
B9)
Appendix
Scales
Temperature
DEFINITION OF THE
SCALE
KELVIN
in terms
of the
temperature*-1 are not expressedin practice
fundamental temperature r, whose
unit
is the unit of energy, but on the (absolute)
scale
is the
thermodynamic
temperature
T, the Kelvin scale, whose unit
kclvin,
as ihe
symbol K. The kelvin was defined in 1954 by international
agreement
fraction 1/273.16of the temperature
T, of the iriple point of pure water.Henr;,
this
s
K above
273.16
is O.GI
the
definition,
by
K, exactly.This temperature
T,
ice poini),
(the
atmospheric-pressure
To ~ 273.15 K.
freezing point of water
Numerical
values of
The triple
point
more
is
and accurately
easily
reproducible
The
Celsius
The
temperature
on
Temperatures
Temperature
The
are
scale
this
differences
have
conversion
factor
/ is
scale
a
in
until
poini.
vessel
all of
not
ice, liquid
the
of
but
part
solid
terms
ice
evacuaied
Kelvin
water,
scale, by
- 273.15K.
value on
the
between
(I)
in degrees
expressed
liie same
kB
defined
the
than
clean
both
Kelvin
fundamental
Tem-
scales.
Celsius
i and the
temperature
Kelvin temperature,
t =
*
1
We
The
appreciate
ullimale
ihe assisiance of
survey of the slale
in ihe preparation
E. Phillips
of precise lempcralure
of development
ipks of various
(962- Pc/liapsthc
methods
of tcm
of this
appendix.
measurement
is Ihe
try.
r; Rcitihold,
B)
Norman
kBT
19-10.
*ii
Tfic
This
c becauseof
letiis. Vol.
its
4 C
tiitroduLioty
pans): H.
nfcU
JisfUiiion uf
H. Plumb,
edilor;
is
called
the
experimentally;
The value
A.350662
numerical
x
of the BolUniannconstant
whose
is
of k8
determination
(a) Idealgas.
are the
C)
simple
and
fundamental
Examples
the aid
with
determined
states,
The
determined
10~t6ergK\"\\
sufficiently
quantum
=\342\226\240
be
is
\302\261
0.000044)
mode!syslcms
structures
are
the energy distributionof !he
funclion of the energy, a = a(li).
of Ihe energy is i(U) (ca/cU)~l.
must
value
one can
that
it the
from
lemperalure
of mode!
syslems
of certain
calculate
entropy as a
as a function
used
in
!he
following:
the
of low
limit
involves the
Avogadro
constanl
body radiation.
dislributionof black body
(A) Black
NA,
can
We
tici>/kBT,
obtain
of known
radialion
independently
known.
spectral
P!;mck
~
4). Because this law involves t through ihe ralioIioj/x
this dcterminalion
requires the independent knowledgeof Planck's
law (Cliapler
constant.
Spinpammagnetistn.
moment
\342\200\242
E. R.
M of
a syslem of
the limit
In
in
.V
J.
Phys.
Chem.
a magnetic
Reference
Dam 2,
No. 4 A973).
temperature as conventionalKeivin
When expressing
fundamental
than
t,
temperature
it
is
measurable
accurately
Any
transfer and
heat
entropy transfer
E}
THERMOMETERS
SECONDARY
AND
D)
\302\253=
TtlS.
dQ
PRIMARY
entropy
reversible
between
xda
the Bohzmann
absorb
5,
s ksa.
The relation$Q
then becomes
rather
7\"
temperature
to
customary
Thermometers
and Secondary
Primary
property
physical
A'
value
whose
is an
accurately
known
ofthe
function
A' *= X{T],
temperature,
parameter10
of ihc
the
measure
defined
thermometers listed in Table 13.2are called
thermometers,
secondary
as thermometers
whose temperature dependenceX(T)
must
be calibrated
with another thermometer whose calibrationis
by comparison
empirically,
known.
The
of all secondary ihcrmonieicrs must ultimately
calibration
already
be
traceable
to a primary thermometer. But
once
thercalibrated,
secondary
arc
thermometers
easier
to use and arc more reproduciblethan
the
therprimary
thermometersavailable at the sametemperature.
of the
calculable
that can be used to determinethe value
model
Any
system
constant
Boltzmann
model
(TableB.I).
systems
The
at
times
different
uncertainty
AT
of thermometers
same
on
based
in
measurements
For
their
useful
secondary
helium
example,
range
have
thermometers
vary greatly.
Precision is
the thermometer
which
Secondarythermometers
achieve a precision of 1 part
mechaniea!pressure
pressures.
AT observed
the
with
with
as a
the most
are
accuracy
variation
the
by
used
be
ean
above
and
precision
expressed
kB
diseussed
vapor
I05.
reproduces
electrical
The
is
resistance
precision
much
poorer,
of thermometers
particularly
may
based on
at low
pres-
iower end of
of
Table
B.I
Principles of the
Model
a|
b)
thermomete
utilised
gas
Static pressure ai
of sound
Speed
constam voliim
Magnetic susccplib'iljtyof
spin
primary
sysicm and
propeny
Idea!
mosl important
noninteractm,
sjsii;m
Eiccironic spins
b) Nuclear.spins
a)
Black
body
radiaiion
and
diluted
CMNii
the
Thcrtt'oJyttanuc
B,2
Table
of
Principles
most
the
Thet
secondary
important
thermometers
Useful
Thermoelectric
400-1400
thermocouples*
votlageof
Thermal
expansion ofliquid
in
200-400
glass
resistance
Electrical
14-700
metals*
0.05-77
semiconductors (germaniumI
0.05-20
resistors'
carbon
commeEciai
Vapor
4
range
taK
Physical property
1-5.2
He
0.3-3.2
p
limits.
ltimate
\342\200\242
'
Used
Widely
as interpolating
instrument in the
used
as cryogenic laboratory
be individually
must
As
1K,
and about
1 part
1 part
give
above
104
0.01
100 K,
about
of simple
three
without
transfers.
around
can
be determined
is hot
The: method
examples.
103
in
relying
mode! systems, by
(a) Carnot
unknown
1 part
K,
thermometry
primary
properties
We
hy
THERMOMETRY
It is possiblelo perform
relationE).
in
near
102
in
THERMODYNAMIC
theoretically known
is limited
thermometers
primary
different
by residual variations between
precision
of
rough estimate, the present-day accuracy primary
is about
thermometers
of
and
poor
relatively
thermometers.
1PTS.
ihernion
by measuring
tem-
a known
between
of entropy
conservation
\302\253
The
\\\\\\o
Qt/Tv
Q2/T2.
unhem
very practical.
is initially at a
substance
(b) Magneticcabriinetry. Suppose paramagnetic
known temperature
in a magnetic
field B{. Let the substance be cooled
a
by
7\\,
isentropic
demagnetization
to the
unknown
known
Scales
Temperature
smaii
conservation
Entropy
requires
cIS =
From
the
dQ/T2
\302\253
SG,,Bi)
identity
thermodynamic
= &S/cB)TdB.
5G,,^,)
for the
Hclmholtz
-SdT
- MilB ,
F)
a magnetiz-
magnetizable
substance,
dF
one obtains,
usual
the
by
G)
relation
the Maxwell
cross-differentiation,
(cS/dB)T= {dM/3T)B.
F) to
(8) into
insert
We
the
find
72 The
quantities
at
of M
derivative
no assumptions
therefore
been
7\"
T2anddBzlT
JS =
and
T,
about the
[he
of
ideality
at low
used extensively
with
pressure
Chapter10:
The
AV is
been
temperature
method
substance,
paramagnetic
and
Tm of
temperature
melting
makes
it
has
a sub-
A0)
TmAV/&H
the
The
measured.
p according
dTJdp
where
Tt are known,and
temperatures.
thermometry.
varies
(9)
B, is easily
(c) Clausim-Clapeyron
substance
temperature:
UTQ/<lB)(dM/dT)B.
\342\200\224
at
<fQ
the unknown
for
expression
(8)
melting,
and
AH
as functions
measured
heat of
of pressure, A0) can
the latent
be integrated;
7*2/7,
If 7, andp,
temperature
are
known,
a measure
(U)
cxpJPl(AK/AH)rfp.
men!
T2 is the equilibrium
melting
of the
pressure
temperature
p%
at
which
permits
the unknown
calculation
of
Practical
International
to magnetic
low
strong
method
the
^He,
at
thermometry
the
of
Scale
{IPTS)
dependence of the
temperature
lias been used as an alternative
temperatures.
TEMPERATURE
PRACTICAL
INTERNATIONAL
Temperature
SCALE (IPTS)
known
Many
the accuracy
than
precisely
equilibrium
phase
can be
temperatures
their
which
with
reproduced
more
far
scale
facilitate practical thermometry,
location
exact
on the Kelvin
can be
To
by primary
thermometry.
a number of
have been
phase
temperatures
reproducible
equilibrium
determined as accuratelyas possible have been assigned
best values to
define an InternationalPractical
Scale
On the IPTS the
(IPTS).
selectedequilibrium
are
treated
as if their temperatures
were known to be
are
determined
exactlyequalto theirassignedvalues.Intermediate
is chosen
to reproduce
the
by a precisely specified interpolation procedure
true Kelvin scale as accuratelyas possible. present
version
of the scale is
IPTS68, adopted 1968 by international
covering temperatures
agreement,
the
of
tlte
triple
point
hydrogen {13.81K) upward.* Table B.3
determined
easily
and
Temperature
points
temperatures
that
The
in
from
gives
for IPTS68.
temperatures
assigned
antimony,
the
range
from
a platinum-piatinum/rhodiuni
body radiation
903.89
K,
thermometer
resistance
platinum
instrument.In
and
which
melting point of
as the interpolating
is the
is used
903.89
K. to
of
gold,
black
is used.
Below 13.81
K.
no
precisely
defined
procedure
has been
of
scales based on the vapor
pressure
down
to
are in practical
use.
Below 5.21 K, the critical point of 4Hc(
hydrogen
used as de facto
are
about
0.3 K, the 1958 and 1962 helium
scales*
widely
extensions of 1PTS68.
The
1958
4He scale relates the vapor pressure of 4Heto
the
T; the 1962 3He scale uses the vapor pressureof 3He.
temperature
As
of primary
the
accuracy
temperature measurements improves, errors in
to revision
scales
such as IPTS become uncovered, leadingeventually
practical
to exist in
of the practical scales. Table B.3 lists someerrors
now
believed
5.2
between
K.
and
13.S1K.
various
IPTS68.
\342\200\242
Sec,
Hcaf,
e Scales
Tempera
of lhe
lnternalional
I96S
poinl
Substance
Type
in K
in K
13.81
6 B50lorr)
17.042
20.28
27.402
54.361
90.188
\342\200\242>
273.16
exact
373-15
0.025
505-tISI
0.044
692.43
0.066
1235.08
1337.58
point ot
boiling
tti
and
lhe
freezing
errors
known
(Dec.
1976).
\342\200\242
Alt
second
data
from lhe
American
1972;
3rded., McGraw-Hill.
ediior.
luxituie
Seciion
of Phyws handbook,
4: Heat, M. W. Zcmansky,
Appendix
Poisson
Distribution
ThePoisson
law
distribution
is a
result of
famous
in
design and analysis of countingexperiments
physics,
biology,
w
e
and
The
statistical
m
ethods
have
research,
operations
developed
engineering.
tend themselves
to an elegant derivationof the Poisson
is concerned
law, which
with
the
of small numbers of objects in randomsampting
occurrence
processes,
it is also called the law of small numbers.
If on
the average
there is one bad
will be found in
in a thousand,
what is ihe probability that N bad pennies
penny
was
first
a given sample of one hundred
considered and
The problem
pennies?
the rote of luck, in criminal and civil law
solved in a remarkablestudy
of
trials
In France
in the early nineteenth century.
We
derive
ihe Poisson
distribution
taw with the aid of a mode* system
that
in tUe
Is useful
and diffusive
large number R of independentlatticesitesin thermal
a
wilh
Each
site may adsorb
lattice
gas. The gas servesas a reservoir.
of a
consists
contact
zero or oneatom.We
that a total of 0,
given
to
want
!, 2,....
find
N,....
Ihe probabilities
are
atoms
adsorbed
the average
ou
the R sites,
v/e
if
are
of similar
ensemble
an
systems.
term
! is
probability
is
proportional
proportional
ihat ihe site
the probability
to
actual
the
The
set
the binding
is
distribution
Gibbs
sum is
the
absolute
Is occupiedis
J ~
The
to
for
value of /, is delermined
by
{>
1
ihe
-r
/.\"
condition
of the
gas in the
reservoir,
Distribution
Polsson
for diffusive
because
of
evaluation
ideal gas
for an
/.(gas)
was
6.
in Chapier
given
we must have
the reservoir
and
lattice
Then
siics.
independent
(<*)
argument used in
By the
{O +
\302\251)Bor
which
occupied,
/ for
term
site
Each
sites.
lhal
know
1 we
Chapter
once
counts once and only
has two alternative states, namely
+ /.)*
(!
corresponds
in
the
Gibbs
of Ihe
stale
every
O
vacant
for
to the term
sum
expansion of
the binomial
for
system of
or
\302\251
for
X\302\260
and
the
)}.
\302\253
1
we
fR-
have
s /.,whence
},R
E)
atoms.
average total number of adsorbed
concerned with this low-occupancy
limit.We can
is the
Poisson
The
now
write
distribution
is
D) as
F)
Next we
number
average
concerned
we
let
with
the
number
of sites R
have
exp<N>
JM = exp<N>=
Ttie
last step
\302\253p(;j!)
exponential
G)
(}R)N
(8)
I\342\200\224-
funclion
in a
power series.
The term
in
'/!\"
occupied. With
of large l(:
are
limit
in
lo the
is proportional
3\"^,
normalisation
we ha\\c
sites
.V
the
in
C)
or, because/.K
<A'> from
E),
A0)
'
interest
is occupied.
From A0)
attaches
we
P@) =
law.
find,
=
<N>\302\260
is simply
occupancy
0! =
1 and
logP(O)
exp(-<N\302\273;
zero
of
with
of
none
the
sites
I,
(II)
-<
the
for
suggests a simpleexperimental
procedure
determination
of <N>: just count the systems
no adsorbed
atoms.
that
have
Values of P(A') for several
in
CM.
Plots
are
values
Table
of <N> are given
C.I for <N> = 0.5,1, 2, and 3.
given in Figure
(N)
of occupied
Table
C.l
Values
0.1
sites. This
of the
Poisson
0.3
disiIribution
ft inction
PIN)
<N>
\302\253p(-W
>)
N!
0.5
0.7
0.9
0.9048
0.740S
0.6065
0.4966
0.4066
0.3679
0.1353
0.0498
0.0183
0.0067
PW
0.0905
0.2222
0.3033
0.3476
0.3659
0.3679
0.2707
0.1494
0.0733
FB)
0.0045
0.0333
0.0758
0.1217
0.0337
0.0842
FC)
0.0002
0.0033
0.0126
0.0003
0.0016
f@)
W)
0.0002
P{5)
PG)
0.0003
0.00050.0120 00504
0.0001
F(9)
1
0.1465
0.140
0.1954 0.175
0.1954
0.1563 0.17
0JO42
0.0216
0.0595
0.0O09
0.0081 0.0298
0.0002
0.0027
O.OI32
0.0008
0.0053
0.0034
0.14
0.10
0.06
0.03
0.0S
Tisttibuti
0.6
=
(N>
<,V> = I
0.5
gO.4
0.4
0.2
0.2
0
)
s
)
\302\2430.2
LLjl
Example:Incorrectand
correct
counting
Jwi = 1
of states,
+
)}
+ -I3
4- - '
for
the
R sites is nai
' + )*.
{12}
noi?
Why
(b)
suns is
Thccorrcci
A3)
Ji!
[R - W N!
is
lilc
system for a
given
Example: Elementary
number
Nolc
cocflicicm.
binomial
of
demotion
dish
of P@).
is viewt
I.ei a Iota! of
j as a syslen: of
R
many
states
independent
is a
bacteria
siles
of Ihe
be distribulcd
10 which
at
a bacterium
PohsonDhtributior.
dishes represent an
aiiach.TlieL
may
per dish is
of bacieria
ensemble of Lidcnticalsyslems.
The
number
average
<N> \342\200\224
R/L.
a bacleriumis distributed, ihe
Each time
The probability
is t/L
bacterium
[he
receive
not
will
dish
a given
that
probability
dish
given
{14}
will
the bacterium
receive
thai
is
A5)
The probability
in R
tries lhat
the
dish
given
will receive
~~Y
/><0)
no baderia is
A6)
(l
the
because
(i 5)
faaor
eniers on eachtry.
Wemay\302\253ri(e(l6)as
(.7,
lW-(l
by
use
of<.V>
= R/L.
We know iliai
-<\302\243>)'.
Hie
in
lirail
of large R,
rap(-<N\302\273= limfi
!>y
llie
of Ihc
Jcrmilion
in aercemcni
wjih
A8)
-\342\200\224)
\302\273
I and
\302\273
I we
have
A9)
cxp(-<N\302\273
(U).
PROBLEMS
/.
Random pulses.
counteda!
an
average
radioactive
rate
of Oiie
none
source
emus
alpha
{b}are
not
identical.
What
particles
is
the
which arc
probability
1 s?{c)
of
Of counting
2.
Approach
to Gaussian
\342\226\240(N>'\"'exp{ \342\200\224<W)}/A'!
large
(A'>.
That
distribution.
approaches
closely
Showthat
a Gaussian
k closeto <;V>
Aexpt-tyS
the
Poisson
function
function
P{N) ~
in form,
for
thai
- (N}I] ,
where
Appendix
Pressure
Let a pressureps
be
liquid in quantum
to ihe
normal
applied
state s.
mechanics
elementary
By
3} the
{Chapter
or
a gas
wilh
pressure
is equal to
Pl~ -dUJdV ,
where
Vs
is tlie
of the
energy
{1}
also
can
write
the pressure
as
Plwhere
ihe
denotes
(dU/,tV),
expcciaiton
volume
y. Ii
is important that
volume
with
no
we
about
ambiguity
~(dUJdV\\ ,
can
B)
dUfdV over the siatc
p by {2} which is at a
value\" of
calculate
selected
state
s at
fixed
5. whereas
V + dVt with
Kand
some
two
volumes.
following the state through
doubt
whether the state remains ihe same.The ensemble
average
in
is
the
of
over
the
states
the
ensemble:
p
average
p,
represented
(!) involves
possible
pressure
C)
f>W--(Wl,>
Because
the
so that
number
of states
the derivative
in the
ensemble is constant,
is at constant entropy.We
may
the entropy
therefore
is constant,
write
as V(a,V,...};
that is,
D) uses the energy of the system
expressed
a
V
a\342\200\224not
the
function
of
the
volume
and
the
r. It is
as
temperature
entropy
be held constant
to
in
the entropy and not the temperaturethat
is
the
The result
differentiation.
\342\200\242
The
equivalence
of (t)
to a parameter
p. 1192of C. Cohen-Tannoudji,
E. Merzbacher,Quantum
resped
and
X are
B)
is an
example
of
quantur
=>
be found
o
The derivation may
dVfdX
<|A*7<*A|).
and F. Laloc. Quamum
mechanic*,
Wiley, [977; see als
2nd ed., Wiley, 1970; p. 442.
related
by
B. Diu,
mechanics,
Appendix
Temperature
Negative
The
energy
which
in
2.2 for
Problem
of
result
field
magnetic
is negative
Ca/cV)s
condition
Figure
is plotted
(Figure E.2).Negative
the population
than
greater
the
we say that
r means
of the
of the
a function
as
Notice
the
that
in
region
the population
population is inverted, as
illustrated
this
in
E.3.
\\
\342\226\240
\\
jr
Figure E.1
The
scparaiion
\\
r = -0\\
= +0
0.2
Entropy
of the
0.6
0.4
as
funciion
0.8
1.0
siaiea is c ~
Negmlrt
Temp,,
+6
+ 5
+4
/
+3
+2
K
-f
Migy
.\342\200\224\342\200\224
\302\2610
\302\247
5
o 2
0.6
1
-\342\226\240
0\342\200\224\342\200\224
0
^1
-1
-3
!/
-4
_5
E.2
Figure
Noiice
but
is 3
Temperature
stale system.
Ihe two
Here
tiiai ihe
at
x ~
+ x,
ture:
the
nuclear
spiu
in a
orientalion
temperature.
The
ordinary
have an entropy
translations!
and
vibrational
degrees
of freedom of a
body
increases
without
limit as
Negative
Temperature
E.3
Possible
spirt distributions for various positive and
fietd is direcied upward. The
negative tempera!ures.The magneiic
Jasi indefinitely
because of weak
negative spin temperaturescannot
coupting betweenspins and the lattice. The lattice can oniy be at a
level spectrum
is unbounded
positive temperature becauseils enefgy
=
on top. The downward-directed
i
turn
over one
as
at
spins,
\342\200\224r^,
Figure
by one,
hereby
equilibrium
nuclear
over a
spin
time
releasing
energy
the lattice
a! a
of
minutes
or hours;
negative temperaturesmay
an unbounded
to
the
lattice
and
approaching
common posiiivctemperature.
at
system
negative temperature may reiax qutie
with
spectrum)
will
during
be carried
iead
always
this
time
experiments
slowly,
at
out.
to an
equilibrium
configuration in
are
which both systems
at a positive temperature.
than
Negative temperatures correspondto higher
energies
temperapositive
a
temperatures. When
a system
at a negative temperature is brought into contact with
at
the
a positive temperature, energy will be transfused
from
system
negative
to
the
hotter
are
temperature
positive temperature.Negative
temperatures
than positive temperatures.
H- go
The temperaturescalefrom coid to hot runs + 0 K,.... 4- 300 K,...,
K,
-03K
-300 K,..., -OK. Notethat if a system at -300K b brought
into thermalcontactwith an idem teal system at 300 K, the final equilibrium
is not 0 K, but is \302\261
co K.
temperature
to negative
and
electron
Nuclear
temperatures
spin systemscanbepromoted
is
resonance
by suitable radio frequency techniques.If a spin
experiment
out on a
carried
spin
at
system
temperature,
negati\\e
as
an
absorption.*
in radio
rf amplifier
resonant
emission of
negative
temperature
amplified.
and Proctor*
into
contact,
if
common negative temperature on being
thermal
brought
at
the
at
other
a negative temperature,
prepared one a positive temperatureand
on mixing,
warmer than the
then an intermediate temperaturewas attained
the
initial
initial positive temperature and coolerthan
negative
tempcraiure.
REFERENCES
FURTHER
ON NEGATIVE TEMPERATURE
N.
F.
temperature,\"
Physical
M. J.
Review
103,
temperature,\"
M. Puicelland
A. Abragam
R. V. Pound,
20A956).
Klein, \"Negativeabsolute
\342\200\242
E.
1
and statistical
\"Thermodynamics
Ramsey,
Physical
Physical
Review
81,279 A951).
and W. G. Proctor,Physical
Review
106.16Q(l<>57);
Review
104, 5S9
109,1441 A958).
(i956).
Index
Abraham, B.
Absolute
463
350,
H..
Abragam,
Hiack
139
activity,
Bolununn
97
Acceptor,
357, 363
Bolutiminn
Born, M..
Accessible state, 29
Activation
reactions,
energy,
Active
Air
Sun, Hi
gold
in
system,
A.
Anderson,
Atoms,
velocity
Average
199
205
a box,
one
222
222
dimension,
279
P. W.,
Bridgman,
Carbonmonoxidepoisoning,i46
Camot coefficient,
126,145,179
Atmosphere,
in
C, 219
142
E..
Amonini,
gas,
331
silicon,
Camot
394
distribution,
value, 22
cycle, 236
Camot
efficiency, 230
Camot inequality,
Carnot
Barnes,C. B.,345
Barometric
pressure,
Bertram,
Carrier
electrochemical,
B., 210
Binomial
BiopoJynwr
22
14
growth,
273
scate,
temperature
Centrifuge,
systems, 10
distribution.
expansion.
Catalyst. 271
Celsius
16,310.331
alloy,
Binary model
362
3SS
lifetime.
232
228,
Jiqucfier, 351
Carrier concentration,intrinsic.
125
equation, 126
Battery,
449
thcrmomctry,
Ihermodynamic
345
I A.,
234
performance,
refrigerator
74
Barclay,
202
Condensate,
Bose-Einstein
fluctuation,
331
!6, 310.
binary,
403, 42!
degenerate, 221
235
258
room,
equation.
tOfi
condensation,
conditioners,
Alloy,
transport
446
Bose-EinStcin
Boson
Age,
4i, 45,
Boson,152
145
transport,
constant,
98
body radiation,
Bockris,J. O. M.,248
M.. 209
4-15
145
348,
Chauikasekhar limit,
222
Characteristic
atmosphere,
Cliau,
V. H.,
height,
350
448
\\26
van
reaction,
Chemical
work,
DNA
281
234
4!3, 421
electrical,
thermal, 401,421
probable, 33, 35
equilibrium, 179
Cooling, demagnetization, 352
.
259
Critical
magnetic
isenttopic, 346
nuclear, 348
Density
of orbitals,
Density
testates,
187,218
186
360
in semiconductors,
360
mass,
407
84
180
engine,
boundary,
heat,
437
429
internal
heat
particle,
399,409
Dilution
98
radiation,
253
120
428, 437
helium,
refrigerator,
399,
Dispersion
290
437
sources,
relation,
law of,
field,
365
352
cooling,
Demagnetization,
DtlTustvity,
355.
437
p-n junction,
Diffusive equilibrium,
of slab, 437
Cooper pair, 250, 257
Cosmicbackground
Degeneratesemiconductors,
Diffusion
387
states,
219
!82
Differential relations, 70
electrons,
Corresponding
gas,
Diesel
semiconductors,355
solid,
Fermi gas,
Degenerate
54
Deviation, integrated,
Diatomic molecules, rotation,
nonmctallic
105
Detailed balance,kinetics,
principle of, 271
415
34t
evaporation,
external
work, 334
348
Degenerate
effective
416
most
Configuration,
Convectivc
isentropic
G,
effective,
303
hole,
S3
molecule,
phase,
intrinsic,
298
Dcbyetemperature,
351
Cohen-Tannoudji, C.,459
Collision cross sections, 395
Collision rates, 395
Concentration
fluctuations, 147
Conductivity,
319
mixture,
160
Cohen, E. R.,446
Conduction
307
transformation,
Daunt, J.
Closed system, 29
Coefficient,
refrigerator performance,
viscosity, 402
Coefficient,
Coexistence
278
curve,
tube,
333
Crystalline
410
Ciausius-Clapeyron
equation,
Clayton, D. D.,222
Conductance,
340
A. J.,
250
liqucfier,
Condensed
276
Curie temperature,
Cycle, Carnot, 236
size,
Crystal
J6J
function,
Critical
2%9
295
nucleation,
nuclear
reactor, 437
Cryogenics,
266
Classicallimit,
radius,
Croft,
Critical
Crilical temperature,
gases,277
12-4
J22,
internal,
291
point,
dcr
WaaJs gas,
Critical
342
425
Distribution, classical,161,410
Base-Einstein,
Fennt-Dirac,
158
154,411
Dixon,R. W.,
366
356, 363
Donor,
and
Donor impurities,
Doping profile,
375
270
lapse rate,
now, 44
heat
Earth,
law
mass,
Effective
Carnot,
Eigen,
M., 270
Einstein
Electrical
406
388
84
polymers, 86
413,
conductivity,
98
Electrochemical
battery,
247
Electrolysis,
380
mobility,
R.
EHiott,
323
P.,
degenerate
113
83,
259
334
engine,
gas, 259
Fertitt
irreversible, 175
264
quantities,
particles, 117
rdativtstic
Extreme
Extrinsic semiconductor,364
420
mixing, 314, 330
kinetic,
thermal
227
gas,
systems,
der
305
31,62
32
31
Waals
gas,
Irreversible
liquid
Ensemble, average,
Enthalpy, 246,
155, 183
183
222
ground slate,
355
construction,
Fermi
fluctuations,
62
gap,
148
Fermi energy,
system,
state
G.,
Feher,
140
average,
transfer,
van
341
cooiing,
352
252
magnetic,
mean
Energy
Euteclic, 325
Extensive
ideal gas, 76
two
77
429
function,
isothermal.171
gas, 185
geothermal,
268
conversion
fluctuations,
291
constant,
Equipartition of energy,
limit,
equiparijtion,
330
pressure,
vapor
Evaporation
Etnissivity, 97
Fermi
reactions,
Error
excitations, 212
Elementary
274
266
Equilibrium
gas-solid,285, 305
two phase,
129
287, 289
269
hydrogen,
Equilibrium,
panidc-anttpartide,
421
Waais,
322
phase,
Electrical noise,
424
205
solids,
gas, 305
of continuity.
Equation
199
temperature,
Elasticity of
52
227
230
114
transfer,
relation,
178, 314
78,
temperature,
246
condensation,
Einstein
50
and occupancy,
and
temperature,
54
increase,
of mixing,
362
360
EfTcctivc work,
Efficiency,
of
as logarithm,
361
of stales,
density
valence band.
2j9
gas,
165
fr\302\253energy.
Sun, 111
from
distance
131
poicniiai.
degenerateFermi
383
adiabatic
Dry
chemical
conventional, 45
degenerate bosongas, 221
273
tonization,
concentrations,
Doping
229
accumulation,
levels,'369
185
expansion.
hdium-3,
259
219
metals. 194
relativistic,
218
level, 155,357
intrinsic, 362
Fermi
284
gas, 305
extrinsic semiconductor,364
411
177,
153,
(unction,
distribution
Fetmi-Dirac
Fcrnfi-Dirac
366
integral,
152
FcrmtOil,
Fer to magnet
First
law,
First
order
302
295,
ism,
Pick's law,
399
49
302
transition,
Grand partition
hole, 415
through
through
tube, 416, 421
speed, 422
Bose
Fluctuations,
gas. 222
Flow,
Grand
138
138
function,
138
sum,
147
concentration,
83, 113
energy,
time
Flux
178
Ha|I-Shockley-Read
theory,
law, 401
163
energy,
262
246,
Gibbs,
harmonic oscillator, 82
paramagnetic
system,
photon gas, i
12
Free
69
8i
energy
function,
J. S., 142
Landau,
298
247, 248
Fundamental assumption, 29
Fundamental temperature, 41
Gallium arsenide, semt-tnsulating,
Gamma function
integral,
critical
electron
372
440
277
boson, 221
Fermi, 219
86
potential
energy,
145
quantum,
182
Gauss
two
state
Helium
system,
integral, 439
dectron-hoic
Geothermal
energy,
259
t67
134,
counter Row,
336
34S
dilution
pair, 3S8
Heinegroup,
refrigerator,
dec eneray,
6S
140
Hemoglobin.141
D. G., 216
Heitshaw,
vacuum region,
Hill, J. S., 34S
High,
I3S
424
115
Helmholu
20
Giauque,W.,
62
Generation,
U3
113
reflective,
equilibrium
Gibbs factor,
intergalactic
space, N3
113
liquid helium-4,
and
photons
phononS,
Hecr, C. V.,
430
Gaussiandistribution,
221
Heat flow, 44
Heat transfer, sound wave, 434
Heat pump, 235, 257
Heat shield, 112
rarefied, 413
waves,
gas,
189
Heat exchanger,
337
liquefaction,
Gas-solid
gas,
Heat conduction
equation,
230
Heat engine,
228,
refrigeratorcascade,258
182
one-dimensional,
sounii
boson
degenerate
72
ideal,
63, 165
capacity,
solids,
temperatures,
degenerate
degenerate
Heat
ice, 305
of
vaporization
'
Gas constant,166
degenerate,
isobartc, 245
path dependence,240
...
Fuel cell,
Gas,
227
definition,
24
function,
multiplicity
Harwit, M, 219
Heat, 44,68, 237, 240
Helmholu.68
Fmlon,
383
Fourier's
Free
131
Half-cell potentials,
Hall, R. N.. 385
397
density,
397
342
Hobdcn.M. V.,349
415
concentration, 361
Hook,J. R.,217
James, H. M, 86
}., 342
Huiskamp,
W.
Hydrogen,
equilibrium, 269
H.
305
vaporization,
van
251
work,
Kelvin
76
Kinetic
446
Kirchhoir
law, kinetic
theory,
therm
Impurity
177
atom
Increase
Lambda
of entropy,
law
of,
Landau
45
Landau theory,
Carnot, 232
Internal chemicaipotential,
International
Scale, 451
Fermi level,
donor
362
3S8
143
45
increaseof entropy,
of mass action, 268, 362,
of rarefied gases, 413
Laws
Lcln,
A. J.,
W.
H-,
217
195
339
Liouville theorem, 40S
232
sources,
Irreversible thermodynamics,406
Irreversiblework, 242
346
Iscntropic
expansion,
114, 148
Iscntropic
helium
11, 209
rclalioos,
phases,
supcrliuid
Isentfopic process,173
Liquid
Liquid heIium-3,
Isemropicdemagnetization,
ideal
290
Liquid
hdium-4,
Liquid
3He-4He
217
217
207
gas.
179
mixing energy,
382
48, 49
of thermodynamics,
Linde cycle,
269
Irreversibilily,
states,
corresponding
Legged,
thermal, 273
water,
of
Leff, H. S-,259
273
alum,
45
of entropy,
vaporization,2SI
Laws
deep impurities,
impurities,
impurily
increase
Law
336
temperature,
3S8
284
284
enthalpy,
Law
conductivily,
381,
heat, 281,
298
isotherm, 145
Law of
387
Intrinsic
lonization,
113
124
122,
Practical Temperature
Intrinsic
Inversion
Laser,injection,
Laiem
heat capacity,
space,
Intergalaciic
439
264
298
transitions,
phase
Langmuir adsorption
exponentials,
comaining
Intensive quantises,
210
poinl.heIium-4,
Laudau
383
348, 349
143
ionization,
recombination,
Inequalily,
N-,
Kuril\",
C, 114
180
carrier
397,413
regime,
Kramers, H.
identity,
odynamic
two dimensions,
96, 115
law,
Knudsen
243
expansion,
270
391
86
one-dimensional,
mass action,
model,
Kinetictheory,
ideal
gas law, 391
Kinetics, detailed balance,407
77
sudden
41
temperature,
Kinematic viscosity,404
179
of freedom,
degree
Kelvin,
366
approximation,
scale, 445
Gibbssum, 180
internal
gas, 338
366
8-,
JQttner, F.,219
W.
Joyce-Dkon
cycle, 237
energy,
effect, 337
Waais
dcr
Joyce,
ISO
calculations,
Carnot
167
L.,
Joule-Thomson
of
heat
98
Johnson noise,
IPTS,451
Ideal gas,
B., 98
J.
Jfohnson,
Johnston,
Ice,
143
adsorption,
Langmuir
conductance,
quantum
276
Isotherm,
177,355
Hots,
mixlute,
330
320
Uquiduscurve,
323
Lounasmaa,
O,
Low
orbital
free
Low
temperature
semiconductor, 358
Nonequiiihrium semiconductors,379
Normal phase, 203
Nuclear demagnetization, 348
Nondegenerate
201
atoms,
448
thermometry,
Magnetic
concentration,
Magnetic
difliisivHy,
145
437
425,
253
energy,
Magnetic
Nuclear matter,
198
Nuclear reactor,critical
Nucieatton, 294
critical radius, 295
394
J. H.,
McFee,
G., 114
N'iels-Hakkenbcrg.C.
ill
B.,
Lyncis,
-Never,\"
342
V.,
Mapiciic field,
81
susceptibility.
Magneticsystem,
23
252
work.
Magnetic
oS^ZlZl^
distribution
Maxwell
relation,
Maxwell
transmission
of velocities,
272
71,
distribution,
distribution
393
velocity
288
method,
Maxwell
Mean field
Mean free path, 395
Mean speeds,Maxweilian
Mean value, 22
Mdssner effect, 252
Merzbachcr, E., 459
Metastable phases, 278
Ovcrhauser efTeci,K4
362, 387
270,
268,
Maxwell
392, 419
395
Paramagnetic system, 69
52, 446
Paramagnetism,
Particic-antipartide
equilibrium,
Particle diffusion, 399, 409
Partition
function, 61
two systems, 85
Pascal
(Pa), back endpaper
240
Path dependence,
419
distribution,
Minority
carrier
Mixing,
energy,
Penetration, temperalure
Pcnnings, N. H., 345
Peritectic systems, 330
Perpetual motion, 50
320
equilibria,322
322
normal,
relations
Molecules,Earth's
probable
Multiple
Multiplicity,
Multiplicity
harmonic
-
Myoglobin,
binding
7
configuration,
of Oa, 148
helium,
210
321
superconducting,306,307
Phenomcnologicailaws,398
254
Phillips, N. E-, 195,196,
33, 35
102
beat capacity,
mode, 104
\"
Phonon,
function,
oscillator,
140,
of
145
atmosphere,
Monkey-Hamlet,53
Mosl
203
Phase diagram,
380
electron,
Mobility,
203
condensed,
equilibria,
phase
426
Phase,267
319
liquid 3He-4He,
oscillation,
pH, 269
578,314
274
152
principle,
336
effect,
Peltier
lifetime, 3S8
3S4, 330
78,
entropy,
exclusion
Pauli
L-, 215
J. H., 34S
Meyer,
Milaer,
369
levels,
253
in superconductors,
MaSn\302\253ic
Occupation<W
170
entropy
93
theorem,
Nyquist
437
size,
147
of Oj,
adsorption
460
temperature,
53
Negative
142
15, 18
'
'
24
\342\226\240
\342\200\242
'.
\342\226\240'
'.
.
solids,
102
113
'\342\226\240
\342\226\240
;
Carnot
Photon,
258
engine,
heal
Read,
thermal, HO
Photon gas, 112, 114
Reese,
one dimension.
89,
function,
91
403
balance, 271
30
463
Proctor,
sound
waves,430
Propagation,
Sackur-Tetrodeequation.77, 165
Semiconductor. 353
degenerate,358,365
donor
73, 85
concentration,
36!
n~ and
JS2
gas,
Quantum
icgime, 182
Radiant
object, 114
fiux,
Shockley.W..
F. A.,
gallium arsenide.
385
323
114
R., 425
W.
Smythe,
Soilj temperature
Radiation
background,
98
thermal
thermal, 111
Solar
Ramsey, N. R, 463
Rarefied
379
Semi-insulaiing
Shunk,
energy
358
nonequihbrium,
212
gases,
Reaction,chemical,
laws of,
266
143
p-type, 363
nondegenerate,
379
Radiant
iontzation,
atom
impurity
Quantum
273
impurities,
extrinsic, 364
holes,36!
body
304
331
coefficient,
Segregation
conduction electrons,
black
63
240
Quasi-Feimilevel,
167
tests,
148
law, 49,
Second
speed. 457
Quasipanicte,
molecules, 84
diatomic
Schotiky anomaly,
457
Quantum
34S
142
A.,
experimental
427
development.
Pump,
S. S.,
Schindler, H.,
253
I(J7
K.,
ill
jadiation.
W. G.,
Pulse,
64
gas. 2!9
of detailed
Probability,
process,
expansion. 171
air conditioner.
Rotation,
Fermi
thermal
Principle
Reversible
Rossi-Fanctti,
377
junction,
isotherm^
Roionbliiiii.
34g
degenerate
222
58
Rose,W.
460
inversion.
W. P..
433
Reversible
Room
86
elasticity.
21
gas,
dwarfs.
Reverse-biasedp-n
25S
86
Population
Pratt,
Fermi
white
Resistivity. 387
455
tlicnniil.
Potjmer,
Relativistic
Relativistic
Reservoir,
equation, 375
Pollution,
Rcif. F.,215
time,
138.453
Poisson distribution.
law,
342
in, 259
bulb
reverse-biased,377
distribution
234
helium dilution.
light
Planck distribution
Planck law, 91, 95
p-n junction, 373
234
coefficient.
coefficient,
112
H-, 111
Poision
W., 219*
Carnol
expansion, 114
iscntropic
Poise.
3S5
T.,
Refrigerator performance.
II2
energy,
Pillans.
W.
113
capacity,
free
raw, 371
Reaction
condensation, 321
413
variations, 437
diffusivity,
constant,
427
110
Soiidificaiionrange, 331
Soljduscurve,
Solubility
gap,
323
310, 311
372
Soliduscurve,
323
phase diagram,
Sound
32 i
Thermal
434
430
propagation,
Spin excess, 14
Thermal
Thermal
96
Stefan-Bo!tzjaann
constant,
Stefan-Boltzmann
law. 91,
Stcycrt,
19, 441
Stirling approximation,
Stokes-Ein
stein
O.,
Stmve,
Sudden
94
A., 343
W.
404
relation,
Jl
ideal gas,
expansion,
243
175
vacuum,
Thermal
relaxation,
temperature,
aad radius,
I j
Thermodynamic
Thermodynamic
identity,
Tliermodynamic
tbermometry,
449
superconducting
Thermodynamics,
306
447
Torr,4J4
1 iO
temperature,
transition,
Superconducting
Superconductor, 252
nugnelic,
8!
Teelers, W.
345
v.
critical, 276
van
Earth's surface,
JU
97
4!
enthalpy,
305
helium,
oscillation,426
Joule-Thomson
445
350
effect,
338
Sun's average,
I! 1
Sun's
HO
surface,
in
2S9
305
negative, 461
variations
413
355
band,
4!
fundamental,
106
Karman.T.,
energy,
of surface,
estimation
of, 110
:erse, entropy
Valence
41
Temperature,
62
capacity,
Vacuum physics,
259
D.,
licat
Un
446
B. N.,
62, SI
system,
free energy, 81
Tacoais,K. W.,
stale
Two
19
Susceptibility,
S6
R. G.,
L.
Treioar,
Superheating, 278
Superinsulation.
processes, 397
Transport
212
Superfluidity,
distiibutton.
395
Maxwell,
217
phases,
Supctfiuid
302
order,
304
second order,
Transmission
278
Supercooling,
first
Transitions,
306
252
work,
magnetic
scales,
177
133,
67,
relations 71,272
Throughput, 415
Ji
surface
Kelvin,
432
Third law, 49
interior
Taylor,
J J J
Thermal
Thermometers,
I i i
mass
272
110
photon,
transition,
Sun
age,
272
expansion,
37. 52
248
Srinivasan, S.,
36
values,
10,
36, 39
Thermal equilibrium,
aclditivity, 53
Spinsystem,
425
427
soil,
170
entropy,
33, 37
contact,
Thermal diflusivity,
lube, 422
Spin
401, 42j
421
Thermal
62
average,
Thermal conductivity,
metals,
63
heal,
Specific
426, 437
Jieal transfer,
wave,
oscillation, penetration,
Temperature
311
gap, 310,
Solubility
soil,
Vapor
pressure
Vaporisation,
437
ice, 305
291
equation, 276,
latent
heat,
231
281
theorem,
A. D.
Woods,
Sll
Work,
Viscosity, 402
227,
chemical,
constant
calculation
of dT/dp,
ionization,
269
305
Wheatley, J.C.,
While
dwarf
star,
mass-radius
J., 114
J.,
219
240
dependence,
196
relationship, 2!9
Wilks,
path
217
222
relalivislic,
Wiebes,
245
magnetic, 252
148
M.,
245
isothermal,
227
irreversible,242
isobaric,
A., 103
245
temperature,
definition,
Water
R.
251
kinematic, 404
Webb,
B., 216
240
Zemanskv,
Zerolh law,
Zipper
M. W.,
48
problem,
Zucca, R.,
373
85
279, 45
Ga
ZJ6'\"Y
Unit conversions
Energy
leal
I
cV
kWh
lO'erg
B 4.1S4J
=
1 BTU
hp
kcal
a 1055J
l<r'2crg = 23.061
10'J
3.6 x
Power
I = 1 Js\021
-
= 1.60219 x
x IO'\"J
1.60219
746
s 1
=
550
lO'trgs\021
ft
lbs\021
O.Oi
mbar
7.501
Pressure
1 Pa
= 1 N m~2
10\023 bar
s;
=s 10 dyn
cm\022
10\"JmmHgorlorr
~ 750 mm Hg
a 10'dyn cm\021 \342\200\242=
10'Nm\022
1 raraHgsa 1 iorr= 133.3Nm\023=
1333dyn cm\023
i bar
1 aim
\342\200\242
Al 0'C
760 mm
1,013
where ihs
Hg = 1.013x
x 10s dyn
cm\022
accelerationof gravity
10s
Nm\021
1.013 bar
has
Ihc standard
value 9.8066S in
s\021.
mol'
Table
Quantity
of Values
of light
CGS
Value
Symbol
T1S~1'
2.997925
I0l0ci
Proton cbarge
J. 60219
__\342\226\240
4.80325
[Q-1Q
esu
Planck's constant
io-1T
ergs
10\"iV
ergs
Velocity
number
Avogadro's
mass
Alomic
mass
Proton resl
mass
Proton
consiani
e1/mc2
Electron Compton
radius
h^/me1
Rydberg
1O-\"JS
10\"*\"
137.036
10~27
kg
10-\"ks
lo-\"kg
\342\200\224
\342\200\224
r.
2.81794
10\021;'cm
3.86159
10\"\0211
r0
5.29177
10\"9
1'*
9.27408
10\021 lergG~'
10\0234JT*
R^ or Ry
2.17991
10\"' 'erg
10~18J
cm
10-** m
10\"IJm
hjmc
wavelength
Bohr
IQ-l*Js
hefe*
radius
Eieclron
1-67265
l/\302\253
}0~2i S
1836-2
fine structure
Reciprocal
. 10\"\"
9JO953
108ms-'
!0IJmor
1,66057
mass
mass/electron
6.02205
amu
m
unit
rest
Electron
hj2n
6.62618
1.05459
St
meij2hl
cm
10\"\"m
13.6058 eV
I eieclron volt
Boitzmann consiani
of free
Permittivity
Permeability
Molar
gas
Molar volume
TQ
= 273-15
po =
1.60219
eV/ft
2.41797x l0uHz
eV/?,c
8.06548
eVA-fl
1.16045
k.
1.38066
10\"' *erg
10* K
e0
space
of freespace
constant
eV
\342\226\240
\342\200\224
fo
Nka
l0*c;
iCl'm-'
\342\200\224
\342\200\224
10\"\"'
sergK-'
|0-..,ri
iO'/^nc2
x
4\302\253
103c
22.41383
lO^rn'mo]
K,
= laliTl
10132SNm\"I
Source: E. R. Cohen
and
B. N.
Taylor,
Journal
of Physical
10\"
107c
8.31441
ideal gas, at
10\"J
\342\200\224
and Chemical
ReferenceData 2D),663
A973).