I.
xiv
What is ther1nodyn
1.2
Definitions
ics?
1.3
T he kilomole
1.4
1.5
More definitions
1.6
Units
I.7
1.8
Temperature scales
6
6
Problems
I0
12
16
Contents
Yl
2.
19
Equations of State
2.1
Introduction
2.1
21
22
2.3
23
2.4
2.5
2.6
An application
Problems
25
27
29
31
3.
3.2
Dissipative work
3.3
3.4
Heat
3.5
Units of heat
3.6
3.7
3.8
40
41
43
Problems
4.
37
3.1
45
46
46
47
48
Heat capacity
4.2
Mayer's equation
4.3
4.4
4.5
Comparison of
4.6
64
SI
53
54
and h
59
61
61
57
35
Contents
5.
VII
5.1
5.2
5.3
6.
69
72
74
80
Introduction
6.2
6.3
lrreversible processes
6.4
Carnot's theorem
6.5
6.6
6.7
Absolute temperature
6.8
7.
67
85
87
88
89
91
94
97
98
I03
I 04
I 07
7.I
7.2
Temperatureentropy diagrams
7.3
7.4
7.S
7.6
7. 7
7.8
Ill
I I0
Ill
113
I 21
1 22
118
Ill
Contents
VIII
8.
Thermodynamic Potentials
81
Introduction
8.1
8.3
8.4
8.5
8.6
8.7
8.8
8.9
Conditions of
Problems
9.
.
.
1 29
1 30
1 31
1 34
1 34
1 16
e equilibrium
1 37
142
1 43
1 46
..
.
.
.
.
.
.
'
...
::
..
. . :.
.
.
..
.
:
. .
. .. .
149
Systems
9. I
9.2
Phase equilibrium
9.3
9.4
Chemical reactions
9.5
Mixing processes
Problems
I 0.
127
15I
ISS
1 57
160
1 62
166
. .:
.
.. .
. .
. .
. . .:
. ...
.< <
. .
.
. .
I 0.2
Methods of cooling
I 0.3
175
I 0.4
178
Problems
1 79
I7I
1 74
... ..
..
. ..
: .
:.
1 69
..:.:.
: : ::;:
: : . : :.:.. .
:.
..
..
. ;
Contents
II.
ix
11 1
11.2
Molecular flux
ll.l
I1.4
Equ
186
188
190
.
'
11.5
I 1.6
II.7
I 1.8
Effusion
191
193
198
10 I
processes
Problems
203
208
213
Statistical Thermodynamics
12.1
Introduction
12.2
Cointossing
ll.l
Assembly of distinguishable
11.4
12.5
12.6
..
..
.
.
..
215
116
es
111
113
215
229
23 I
Problems
13.
183
of enersr
II.9
12.
181
The
..
.
.
..
Classical and
.
.
'
uantum Statistics
I ].1
Boltzmann statisti cs
13.1
13.3
The Boltzmann
1].4
The felstfliDirac
ll.S
The
235
bution
138
ZaiZ
244
136
233
Contents
13.6
13.7
14.
13.9
253
254
2S7
261
14.1
14.2
14.3
14.4
14.5
14.6
Equipartition of energy
14.7
14.8
15.
248
13.8
Problems
246
265
266
268
269
270
271
273
275
15.1
Introduction
15.2
I 5.3
I 5.4
15.5
Electronic excitation
15.6
263
289
287
288
279
282
284
277
Contents
16.
XI
The Heat C
Introduction
16.1
16.3
of a solid
296
305
308
agnet
17.3
Properties of a spinl/2
17.4
Adiabatic demagnetization
17.5
Negative temperature
17.6
Ferromagnetism
Problems
agnetism
307
etism
318
321
325
328
33 I
BoseEinstein Gases
ation
333
18.1
Blackbody
18.2
18.3
BoseEinstein condensation
18.4
18.5
293
30 I
Introduction
17.1
19.
193
The Thermodynamics of
17. I
18.
291
16.1
Problems
17.
of a Solid
338
340
345
347
349
FermiDirac Gases
19.1
19.2
353
355
357
liS
XII
Contents
1 9.4
1 9.5
364
367
370
Problems
20.
36 1
19.3
lnformationTheory
373
20. 1
Introduction
20.2
20.3
Unit of information
20.4
Maximum entropy
20.5
20.6
3 75
375
3 79
381
384
386
20.7
387
388
Problems
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:=:
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=: . :::;:; :::::::
::
:: ::.; :
: :::
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:: .:;:. :;: ::::::.
:
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:=:::;;
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$=:=
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;:=:
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,.v
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z
:::.:.:
:.
:::
;:
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z{!
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Appendices
A.
A. I
Partial derivatives
A.l
39 I
393
3 99
40 I
B.
Stirling's Approximation
C.
D.
Various Integrals
407
403
:
::
xiii
Contents
Bibliography
41 3
Classical thertnodynamics
41 3
4 14
41 4
41 5
Index
424
417
This book is intended as a t ext for a one sem est e r u nder gr aduat e cour se in
t herm al p hysics Its obj ective is to provid e third o r fo urt h year p hysics stu
dent s wit h a solid intr oduct ion to t he cl assical and st at ist ical t heor ies of t her
m ody namics. No prep arat ion is ass umed beyond colle gelevel general phy si cs
and advanced calcul us. A n acquaintance with prob ab il ity and st at i stics is h elp ...
f ul b ut is by no means necessary.
The curr ent pr actice in many coll e g e is to <>ffer a cour se in cl assical
therm odyn am ics with littl e or no ment ion of the st atist ical t heory or vic e
versa. Th e argument is t hat it is in1p ossible to do j ustice t o b ot h in a one
semester cour se. On t he b asis of m y own te ach i ng exp er ience I str ongly dis
agree. The standar d treatment of temperature work, heat entropy, etc. oft en
seems to t he student l ike an endle ss coll ect i<l n of p art ial der ivatives t hat shed
.
..
..
only limited light on the underlying physics and can be abbreviated. The fun
damental concepts
more than half a
understanding
Since
n ot
The p h ysics
XIV
course
why
'I
Preface
XV
ther
modynamics becorne apparertt upon close scrutiny and invite inquiry about a
it
concepts, given no exposure to the related classical ideas first. Not only do clas
si c al and st a tistical the rtn odyn amics in this se11se corr1 plemcnt each oth er, they
also bea u ti fully illustrate the physicist's perpetu al stri vi ng for descriptions of
gr eater power , el egance, uni ver s ali ty, and freedon1 from ambiguity.
Chapters 1 th rough
10
the fu!tdamental la\vs in terms of state variables, qu anti tie s whose differentials
are exact. Accordingly, the sea rch for i nt egr ati ng factors for the differentials of
work and heat is discussed. The elaboration of the first law is follow ed by
chapters on app lic ati ons and consequences. Entrop y is presented both as a
in nature. Calculations are then gi ven of the change in entropy for variclJS
nale for having precisely four such quantities. The conditions for stable
equ i
in Chap ter
con
molecuJar basis of such thermody n amic prop erties of gaes as the tempera
ture, pressure, and thermal energy. It represe11ts, both logically and historically,
the tran sition between classic a l thermodyn am i cs and the s tat istical t heo ry
experiment. The basic concepts are then defined. The statistical interpretation
of a system con taining many molecttles is observed to require a knowledge of
the properties of the in div idua l molecules making up the system. This infor
classical and quantum statistics and the derivation of the particle distribution
functions is based on the method of Lagrange multipliers. A di scussio of tl1e
last chapter introduces the student to the basic ideas of inforn1ation theory
and
Preface
xvi
Throughout the book a serious attempt has been made to keep the level
of the chapters as uniform as possible. On the other hand. the problems are
intended to vary somewhat more widely in difficulty.
In preparing the text, my greatest debt is to my students, whose response
has provided a practical filter for the refinement of the material presented
herein.
A.H.C.
Drew University
ACKNOWLEDGMENTS
In addition to my students at Drew University, I owe .thanks to two colleagues
and friends, Professors Robert Fenstermacher and John OJlom, who have
encouraged me at every turn during the writing of this book. I am indebted to
.
Professor Mark Raizen of the University of Texas at Austin. who reviewed the
manuscript and used it as the text in his thermal physics course: his comments
were invaluable.
1. 1
What Is Thermodynamics?
1.2
Definitions
1.3
The Kilomole
1 .4
1 .5
More Definitions
1.6
Units
I. 7
1 .8
of Thermodynamics
10
Temperature Scales
12
1.1
WHAT IS THERMODYNAMICS?
Thermodynamics is the study of heat in the field of physics. The central con
cept of thermodynamics is temperature. Since temperature is not expressible
in terms of basic mechanical quantities such as mass, length, and time, it is evi
dently a fundamental notion that sets thermodynamics apart from other
branches of physics.
The development of ther1nodynamics provides some of the most fasci
nating chapters in the history of science. It began at the start of the Industrial
Revolution when it became important to understand the conversion of heat
into mechanical work. The experin1ents of Joule, Hirn, and others, and the the
oretical studies of Helmholtz resulted in the principle of the conservation of
energy when applied to therrnal phenotnena. The principle became the first
law of thertnodynamics. Mayer postulated the equivalence of heat and work
and made an estimate of the mechanical equivalence of heat.
The subsequent progress of thermodynamics owes much to the
Frenchman, Sadi Carnot, whose treatise of 1824 led io one of the most far
engines in general.
The concept of entropy began to appear quite early in papers by
Clausius and William Thomson (Lord Kelvin), but it was not until
1865
that
Clausius saw fit to give it a name and a full definition. Later, Nernst and
Planck added a third law, which is a statement about the behavior of thermo
dynamic quantities, including entropy, at the temperature of absolute zero.
In this period classical thermodynamics was worked out in essentially its
present form. It is a phenomenological theory, describing the macroscopic prop
erties of matter, most of which are amenable to direct measurement. No assump
tions are made about the fine structure of material substances. No attempt is
made to explain
Chap. I
...
'.
y;.:..:,.
.
,
:: :
'
.. .
..
::t. '
' .
..
}"'
'J
.
consequence" the theory has the advantages c.>f great s implicit y.. broad gene rality
and a close connection between experimental results and familiar concepts. The
noted experimentalist
different feel from most of the other laws of physics. There is something palpably
verbal about them
Toward. the end of the nineteenth century, \vhen the aton1ic nature of
.,
matter began to be understood .. ways were found to e x pr ess the pressure. tem
perature, and other macroscopic p roper t ies of a gas in terms <)f a ver a ge values
su ch
which Maxwelrs name is closelv asS()Ciated. came to he c<tlled the kinetic the.,
ory of gases.
The kinetic theory eventually expanded int o the f ar more comprehen
sive statistical mechanics (or statistical thermodynamics) of BoJtztnann and
Gibbs, and ultimately encompassed the ideas of quantum mechanics. The statistical approa ch takes account of the molecular C()nstitution of matter and
connection between the classical and statistical theories is associated \Vith the
fact that macroscopic measurem e nt s arc averages of the hehavior of astro
to
include nonequilibrium
processes and even nonlinear effects. At the present time. the re1ationship
Sec. 1.2
Defrnit!ons
more impressive the greater the simplicity of its premises, and the ntore
extended its area of applicability. Therefore, the deep impression which classi
cal thermodynamics made upon n1e. It is the only physical theory of universal
content concerning which I am convinced that, within the applicability of its
1.2 DEFINITIONS
In developing the basic ideas of thermodynamics the originators of the theory
were careful not to be so concise as to render definitions sterile. Tne following
brief definitions will be illustrated by examples in future sections.
in which
temperature is an
properties
to be defined.
net. The system must not interact chemically with the vessel that contains it.
(The behavior of a liquid must not be influenced by the test tube that holds it.)
A system may exchange energy with other systems, which constitute the
roundings
comprtse a
open
sur
untverse.
closed
system cannot exchange mass with its surroundings, but can exchange energy
in other forms. An isolated system cannot exchange mass or energy in any
form with its surroundings; it is completely cut off from other systems.
The quantities we use to describe the macroscopic behavior of a system
are called
properties,
extensive
property is propor
tional to tl1e mass. An example is the volume V: if the mass is doubled, the vol
ume is doubled (assuming that the density remains constant). An
intensive
Chap. I
In this text, we will go back and forth between extensive properties and their
corresponding specific values.
Thus one kilomole of oxygen gas (02) is equal to 32 kg. (The mole is a
unit of mass more familiar to chemists: one mole is equal to the mass in grams.
Thus a mole of oxygen gas is 32 g.)
m3
Sec. 1.5
More Definitions
oceans are examples). State variables are properties that describe equilibrium
states. An equation of state is a functional relationship among the state vari
system passes.
If the pressure .P, the volume V, and the t en1 pe ra t u re Tare the state vari
T)
0.
( 1.1 )
This rel a tions hip reduces the number of independent variables of the system
from three to two. The function f is assun1ed t o be given as part of the specifi
cation of the system. It is customary to represent the state of such a system by
a point in threedimensional p V T space. The equation of state then defines a
surface in this space (Figure 1.2). Any point lying on this surface represen t s a
state in eq uilib rium. In thermodynamics a state automatically means a state in
eq uilibr iu m unless otherwise specified.
The boundary bet\\'een a system and its surroundings th roug h which
changes may be imposed is called a system wall. An adiabatic wall is a boundary
tha t permits no heat interaction with the sttrrou n dings The word comes from
..
Chap. l
T
te
ta
s
m
iu
r
ib
il
u
q
e
,
_
/
f(P. V. T)
v
Surface in P V T
space. Points on the surface
represent equilibrium states of
the system whose equation of
0.
state is f ( P. V. T )
Figure 1.2
I'
ia
ad
is
m
ste
sy
ed
lat
iso
An
...
h
ug
o
r
h
g
t
in
go
t
no
..
ng
ni
ea
m
s.
the Greek adiabato
y
l
ri
e
ssa
c
ne
t
no
is
ll
wa
c
ati
iab
ad
an
th
wi
t
m
s
e
y
s
a
r.
ve
we
Ho
d.
batically containe
isolated. Mechanical interactions can take place th rough adiabatic walls. For
e xample material can be removed or added the volume can change, a mag
ne ti c field can be applied, etc. A diatltert11al rail is a boundary that freely allows
,
cated. Think of panc ake batter stick ing to the griddlt!. or sulfuric acid 1n an
iron ve ssel !
e qu ation of state surface in Figure 1.2. In a c_vclicaiJJrt)cess. the initi al and final
states are the same. A qltasistatic prl)cess is a process in \\'hich. at each instant,
the system departs only infinitesimally fr<)m an equilihrium state. That is.
changes of state are described in te rms of differentials. An example is the
is
ple, a slow lea k in a tire is quasistatic but not reversih1c. A reve rs i ble process
s yst e n1
remains constant. An
is
v ol ume
is
1.3).
Sec. 1.6
Units
,.
p
diathertnal wall
.. .
. .
.. . .
.
.
.
. . .
.
.. .
.
.
. . .. . . .
. . ..
.
.
;t
.
.
, ,
. .
.
0
piston
. . " .
.
..
.
.
.
'
.' .;
..
.: .> :.>.
.
v . .
. .
:0 :
. .
.
.. . .
.. ". .
.
.
.
. . .
.. .... .
. ..
. .
.
.
..
(P;, V,)
v
heat bath
gas
(a)
(b)
Figure 1.3
of infinitesimal changes.
If, instead of
P V plane.
Only the end points can be plotted, representing the initial state and the final
state reached after equilibrium has been eventually reestablished.
1.6 UNITS
The lntertlational System of Units (SI) will be used, almost exclusively. The
system is based Oil the fundamental units of length, mass, and time
the meter
Nm 2
1.01 X
lOS Pa.
133.3 Pa.
The atmosphere and the torr (named after Torricelli) are derived units. The
atmosphere is based on the use of a manometer to measure pressure (Figure 1.4).
Chap. I
10
vacuum
p
h
.
: .
.
\. .
. .
.
.
.
.
> .
.
.
.
.. m crcu rv
.
.
.
.
.
:
..
:
.
.:
.
:
.
.
. . . . . . . .. . ,..,,, :. .. . . . . . . .. . .
.
.
.. . .. ... .:.. . ...... . . . . . . ... . . . . .
. ...
. . . .. .. . . . ... ... . .
.
. . ..
:
. . .
.
:
.
.
.
..
'<
'
'
.,
:..
'
76 em. That
is. P
atm osphe re his the height of the mercury column. pis the density of m ercury
1 atm
(0.76m) 1.36
as
,.
,.
..,
'
__
..,,
, , .
'"'
. ,
7fi0
9 .8
s
1.01
105
Pa.
of 1 mm of mercury:
atm
133.3 Pa.
..s,.,
...
\ \4 ...., ,,
..:';.,
, t.:.
W" '. #t::T "C
. .\IT"'
<('C 'U..2
., ,..
I ..',.TY"
"'E:I
' C\
.
_,,
,.. ._,
,. .._ .....
....
o""...,....__.,.;
"""
:WV
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.
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_..
_..
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,
,
. 7..
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,
, '
.
. "
.
..
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...
..._
'_

;,
'f
..
..
'
'
'
'
o
'
'
r:m
tw.
,.
__.
(J,
::
.,
,
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,
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'4"'
'
">o+.
':oo o ., .... , \oo'.., o
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'ot;'' , .. t oil' _ , ,_ .,. ";,
: '  " :o:,;: , 'YT ;. , ; \, .' ,:.. ' ".J '
..,_.c. r.,.
,.
'
l O"
the pressure
1 t(1ff
kg
.,.,,,.\ ' ,
..
...
..
..._
;."J> 
'
mor e suhtlc property than pre s s u re Its ori gin is the socalled
.
e xpe ri men ts
(as
are all physical laws) and is concerned with properties of systems in thermal
a tl1ird syste111.
(_each consist of a 1nass of flutd in an insulated conas a reference. We choose to describe the state of each
.
*There are some \\'ho hc1icve that this should n)t be dignified by ca11ing it a . Jaw."
.
Sec. 1.7
(a)
II
(b)
thermal
(1.2)
where F1 is some function of the four variables. We assume that this equation
can be solved for Pc:
(1 .3)
Next we place system B and C in thetttlal contact (Figure 1.5(b)). For equilibrium,
(1. 4)
or
(1.5)
Equating Equations (1.3) and (1.5), \Ve obtain the condition under which A
and B are separately in equilibrium \vith C:
(1.6)
But, according to the zeroth l aw A and B are then in equilibrium with each
other, so that
,
(1.7)
Chap. I
11
( 1 .8)
Now, Equation ( 1 .6) can also be solved for PA in p ri ncipl e :
PA = g ( V4 , PB .. VH .. Vc ) .
( 1 .9)
as
ere
wh
les,
iab
var
r
fou
by
ed
1in
ern
P"
det
s
i
t
tha
t
es
t
a
s
.9)
1
(
on
i
at
u
q
E
Equ atio n ( 1 .8) says that it is a fun ctio n of t)nl y thre e. TI1i s can only mea n tha t
the functions f1 and f2 in Equ atio n ( 1 .6) cont ain Vc in such a form that it can
cels out on the two sides of the e qua tion . f<)f e x am p l e
,
!t
f2
<> 1 < PA ..
vA ) ' ( vc )
4J J ( p8 , VH ) ( ( .\1( )
11 ( vc ) ..
+ 7J ( VC )
( 1 . 1 0)
For any system in thermal equili brium with a given system .. we can choose to
w ri t e
( 1. 12)
where we define T as the empirical
e qu a t i on
1 .8 TEMPERATURE SCALES
Sec. 1 .8
Temperature Scales
13
Here
and
Prior to
(1.13)
aT + b.
1954, two
fixed points were used, the ice and steam points of water.
(C
for
1.6, is a practical
1 .7):
a.
0 at
 273.l5C. This
turns out to be true for all gases although the slope of the curve is differ
ent for different gases.
I

capillary
.....
....
:. ,.._,
..
.
. :.
.
"
.
.
.
. .
.. .. .
.
'
.
.. . . .
... .
.
.
rigid
_....,.__ diathermal
wall
. ..:...
.
: : : .
': :
:
.. ..
.
. . :: .
.
. ..
.
..
.
. ,'
0
. .. .. ..... ..
......
.. . .. .
. :: ..: .
: .
.. ... . . ! .
.:.
. .
.
0
. .
'
. . . . ,
. ..;:: . : .;
. . .. .
: ....
.
. . ..
. .
'
; .,.:..:
.
. ...
.
. .
: .: :
.
..
. ..
'
.
. . .
_
_.....
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,,
.
.
o ,
. . .
:
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. : ..
.
.
'
.
.
.
: :
'o
,o.
::
. ..: . :0.. ...
.. . :. .
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.
..;_: ...
..: .. ..
,
0
0
. .
.
....
.
.
.
.
.
.
.
.... :
.
.
. . .>'
: .. : ..
.
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. .. '
.
..
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. ..: .
. .
::::
. .
. . ...
. :
. . . .
.
.
. .... . .
..0
.
.
" '
o
.
.
.
.
.
.
.
p
gas
. < : :
::
.. .. .
.. :. . , .
.. :
.
... ..
::
:_
.
.
:
:
:
.
;:
:. .
.: . : .
. ,.: . ...
:
... .
. ... . . .
. .. .
.
' ... .
. ... . .
 .; ;  ::
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...
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: :.:... : .
.... .....
.
.. .:. ...'...'
.. ,
' .: ..
. .. .
:.
: :.. . .
. . ......
.. .. ... . ..
:..:
=
.
.......... ... .. ,.
. . ... "' .
.
.
: :
\
'::::
:
.
.
:
:
:
.
.
.
.
.
. :: ....
,
.
.
..:. .. ........
. :: .. , : .
.. . .
... ...: .: . :
.. .. .
.
.
.
.
'
. : :.. ':
. . . .. . .. .
. . . .. .......
..
..
.. . . . .
.: :: :.
..:.::::::
.
::::::... :: : :.. .::::::: =:
:
. .., ,:.. . ... '' ... . ..... . . 0
. : :
:: :?: . :_::: :
:
..
.
.
.
.
. ..
.
.
. .
.
. ..
.
.
'
mercury
manometer
..
.
.
.
.
.
.
.
<
.
. .
.
..
.
.
. . .
.
.
..
.
.
. .
.
.
.
.
,.o.
. .
.
.
.
. . .
:.:::
; : :
. .
Chap. I
14
I
_
_
_
_
_
_
_
...._
__.
_
_
_...
.
__.
_
__
;...
Figure 1.7
==
aT
b.
273 . 1 5a
b.
Thus
P
af7 ( c'C )
sca l e such
==
273. 1 51.
( 1 . 1 4)
aT ( K. )
( 1. 1 5 )
Sec. 1 .8
15
Temperature Scales
T(K)

273.16
( 1 . 17)
Prp '
where Prp is the pressure at the triple point. A better definition, taking into
account the convergence of th.e PT curves for gases at low temperature
(Figure 1.8), is
( 1 . 18)
The curves of the figure are constructed in the following way. An amount of
gas in the bulb of a constantvolume gas thermometer is exposed to a cell con
t ai nin g water at the trip le point. The pressure is recorded. With the volume
held constant, the bulb is surrounded with boiling water at atmospheric pres
sure, the gas pressure is measured, and the temperature at the steam point, T5 ,
is calculated usin g Equation ( 1 . 17). Then some of the gas is removed from the
bulb, the lower triple point pressure is measured, and the new values of the
pressure and temperature at the steam poi n t are found. The process is continued and the resulting curve is extrapolated to the ordinate. Although the
curves for different gases have different slopes, they are discovered to inter
sect in the limit as PT P approaches zero. The triple point reference is precisely
reproducible and absolute zero is precisely defined.
373.8
t
373.6
;;;;
;;; ================= He2
H
37 3.0
.....J.."''"'L.
20
Figure 1.8
40
60
80
100
120
Prp(torr)
Chap. I
16
u se.
( 1 .19)
On this scale the ice point is 32F and the steam point is 2 1 2F. The Rankine
scale is derived from the Fahrenheit scale:
( 1 .20)
The Rankine scale is widely used in enginc.!ering: it does not use the ""degree''
symbol.
We shall see later that it is possible t o define the absolute scale of tem
perature independently of the thermometric properties of gases.
. ..
..
..
.. .
.
.
.
'
'
.
.
.
.
P RO B L E M S
(a) A mass of gas in a con tainer \Vith rigid. impermeable. di athe rm a l walls.
(b) A mass of gas in a container \Vith rigid, impermeable. adia b a t i c wa11s.
completely as possible:
(a) The temp e ra t u re of a gas. enclosed i n a cy l i nd e r provided with a frictionless
piston . is slowly increased. The pressur remains constant .
(b) A gas, enclosed in a cyl inder provided with a piston, is slowly ex pande d . The
temperature remains constan t . ll1ert is a force of friction bet,veen the cylin
der wall and the piston .
(c) A gas enclosed in a cylinder provided \Vith a frictionless piston is quickly
compressed.
(d) A piece of hot metal is thro\vn into cold \\'ater. (Assume that the system is
the metal, which n e it h er contracts nor expands. )
(e) A pendulum with a frictionless su pport swings back and forth .
(f) A bullet is s topp ed by a targe t .
13 On a plot of volume versus temperat ure. dra\\' and label l ines indicating the fol
lowing processes.. each pr t)C c c d i n g from t he san1e initial state . ).
Problems
17
14 Estimate the pressure you exert when standing on the floor. Express your answer
in atmospheres, in pascals, and in torr. Repeat the calculation for spiked heels.
1S Let the resistance R of a piece ot wire be a thermometric property for measur
R = aT + b,
where a and b are constants. The resistance of the wire is found to be 5 ohms
when it is at the temperature of melting ice and 6 ohms when it is at the temper
ature at which water boils at atmospheric pressure . If the ice point is taken as
100 and the boiling point as 500 on a particular scale, what is the temperature
5.4 ohms?
on this scale when R
=
16 The following table gives the observed values of the pressure P of a gas in a con
stantvolume gas thermometer at an unknown temperature T and at the triple
1 00
1 27.9
200
256.5
300
385.R
400
5 1 6.0
log R
4.70
3 .92 log T
generate(J when the two j unctions are at different temperatures. When one junc
tion is held at the ice point and the other is at a Celsius temperature of T, the
therntometric function is given by
2
E = aT + bT ,
(a) Consider the linear relationship between the thermometric prop e rty
the temperature T given by
X and
X = aT + b.
Suppose that the ice and steam points are used as fixed points with temper
atures of oo and 100 respectively. Show that
T
100
X  XI
X.( _ XI .
Chap. I
18
(b )
aln .Y
h,
110 At what temperature do the Fahrenheit and Kelvin scales give the same reading?
111 The temperature of the normal boiling point of nitrogen is
77.35
K. Calculate
the corresponding value of the temperature on the (a) Celsius. (b) Fahrenheit,
and (c) Rankine scales.
2. 1
Introduction
21
2.2
22
2.3
23
2.4
25
2.5
27
2.6
An Application
29
19
2. 1 INTRODUCTION
In thermodynamics, we add to the basic dimensions of mass, length and time
the "fourth dimensio n" of temperature. We saw in Chapter 1 that the concept
of temperature is intimately associated with the. notion of systems in thermal
equilibrium. Perhaps the simplest example of a thermodynamic system is a
homogeneous fluid say, a gas or vapor.* Its state, as we have observed , can
be described by an equation of the fottn
f ( P, V , T)
0.
(2. 1)
The equation of state connects the three fundamental state variables, only two
of which are independent. It is an expression of the results of experiments.
Every system has its own equation of state.
We note that the equation of state does not involve time. Classical ther
modynamics deals mainly with systems in thertnal, mechanical, and chemical
equilibrium that is, thermodynamic equilibrium and does not concern itself
with the rate at which a process takes place.
The mechanical variables occur in "canonically conjugate" pairs, one an
extensive variable, the other intensive. Thus the volume V (extensive) is "con
jugate" to the pressure P (intensive). The situation is analogous to that in
mechanics, where the generalized position coordinates qk and the generalized
momenta Pk form canonically conjugate pairs.
In thertnodynamics, the quantity PdV is the differential of work (with
units of energy). We are led to ask if there is an extensive state variable canon
ically conjugate with the temperature whose product has the unit of energy.
This very important question will be addressed in Chapter 6.
* The laws of thennodynamics apply to all forms of matter, but they are most easily formu
lated and understood when applied to gases.
21
Chap. 2
22
Equations of State
(2.2 )
.
where R is a universal constant having the same value for a11 gases:
Since
( 2.3)
PV
nRT.
(2.4)
This equation is called the equation of sta1e of an ideal gas or perfect gas. It
includes the laws of BoyJe't GayLussac Charles.. and Avogadro .. which were
discovered over a period of 200 years.
In 1 8 1 1 Avogadro postulated that at a given temperature and pressure
equal volumes of all gases con tain e.quaJ numbers of molecules. The reason for
this is that the molecules in a gi ven sample of gas have negligible volumes
compared with the volume of the sample itself.
In Equation (2.4) we note that the extensive variable V divided by n the
number of kilomoles of the gas.. is the specific volume v. Thus the equation of
state can be writ ten Pv
RT. The projections of the surface f ( P, v, T) 0
on the Pv plane, the P T plane and the v T plane are sh ow n i n Figure 2. 1 . We
use whatever diagram is most appropriate for the process we are in terested in.
=
==
..
Vz
(a)
Figure l.l
::;
;.__ 
(h)
...._
___.
_
_
_
_
(c)
Sec. 2.3
23
P + 2 ( v  b) = RT,
v
(2 .5)
Pv3  ( Pb + RT) v2 + av  ab
= 0.
(2.6)
The result is a cubic equation in v with three roots, only one of which needs to
be real. In Figure 2.2 some isotherms calculated from the van der Waals equa
tion have been drawn.
constant. The correction
As T increases, the curves approach Pv
terms in the van der Waals equation become less important. For T < Tc , there
is a local maximum and minimum value of P. The transition between the two
types of curves is a curve having an inflection point CP, the socalled critical
curve, T = Tc . Imagine that the volume is decreased by loading a piston con
fining the gas in a cylinder. Suppose one moves along an isotherttl for which
T < Tc . After we reach a maximum of the cJrve, the pressure begins to fall.
This is an unstable region since the pressure no longer increases as the volume
is diminished.
Actually, this portion of the isotherm is not really traversed at all
because the gas undergoes a change of phase. * Assume that the compression
=
liquid to
Chap. 2
14
Equations of State
d
Figure 2.2
Isotherms for a
van der Waals gas.
b ...... a
 +
begi ns at p oi nt a i n the diagram. Part of the gas begins to liquefy at b and the
pressure remains constant as the volume is further decreased as long as the
temperature is held constant. Between b and d. liquid and vapor are in equi
librium. Finally, at d liquefaction is complete. Thereafter the curve rises steeply
because it takes a large increase of pressure to compress a liquid.
The curves with no extrema ( T > Tc ) can have no regions of this kind.
Above Tc it is impossible to liquefy a gas, n<, matter how large the pressure is.
The interface between a liquid and a vapor is not discernible.
The critical values Vc , Tc . and Pc of a st1bstance can be expressed in terms
of the constants a and b that appear in van der Waals' equation. For T Tc .
=
(2.7)
The po i n t at which the tangent to the curve is horizontal is given by
iJP
av
0
= =
RTc

( Vc  b ) 
2a

(2.8)
Vc ,
and the point of inflection is the point at which the rate of change
ts zero:
of the
slope
=
= 0
2RTc
3
( vc  b )
6a
4.
vc
(2.9)
Sec. 2..f
15
Tc
3b,
8a
21Rb '
(2. 10)
Evidently, Pc vc
RTc for a van der Waals gas at the critical point. The rela
tions of Equation (2.10) suggest that the equation of state of a van der Waals
gas can be written in terms of the critical variables, eliminating the constants a
and b. This is indeed the case (see Problem 25).
._._,
,_
CP
...
Jiqui
CP
gas
vapor
Figure 2.3
freezing.

.

._
..,
triple line
_. 
_
_
_
_
_
Chap. 2
16
Equations of State
SL
SL
CP
liquid
CP
liquid
solid
solid
vapor
TP
vapor
TP
T
 T
(a)
(b)
Figure 2.4
( Figure 2.4). The LV curve is the vapor pressure curve, for which the liquid
and vapor phases coexist in equilibrium. It is also known as the hsaturated
,
vapor, or boilingpoint curve. The SL curve is the freezing point curve. and
the
>
between the liquid and the vapor is indiscern i ble. By raising the temperature
a bove Tc then increasing the pressure. and finally reducing the temperature,
one can m ake an "end run" around the critical point. In this way, it is possible
to m ove from a vapor to a liquid without crossing the vapor pressure curve.
No critical point can exist for soJidIiquid equil ibrium (the SL curve).
That is because solids and liquids possess diffe rent symmetry properties. A
normal liquid is isotropic, whereas a solid has a cryst alline structure whose ori
entation defines a particular set of directions. The transition from one sym metry to another is strictly a discontinuous process.
For C02 the critical temperature is
3 l .0C
.
and the critical pressure is
17
Sec. 2.5
v
I
I
I
I
I
I
I
I
t
I
lOOOC
l.S
For H 2 0 the critical point is 374.2C and 207 atmospheres. The triple
3
point is 0.01 oc and 4.6 torr (6.0 X 10 atm ) . Thus the pressure must be
water contracted on freezing, the results would be disastrous, but ice floats.
During a change of state, there is always a change in volume but the tempera
ture and pressure are constant. For example.. at the freezing point of water, the
ture for water. Since v is the reciprocal of the density, it follows that the ma:<i
mum density of water occurs at 4C.
v ( T, P ) .
(2. 1 1 )
Chap. 2
18
Equations of State
dv
ilt'
tiT +
:.=
iiT
clv
\ ri P
tl P.
(2. 12)
(The subscript denotes the q ua ntit y held (:onstant . ) Two important measur
able quantities are defined in terms {)f the pa rti al derivatives. The expansivity.
or coefficient of volume e xp an sion is given by
.
f3
rlV \
.l .
aT ; P
1
=
t'

(2. 1 3)
iJv
(2.14)
i1 P .,.
the fractional change in volume as the pressure change with the temperature
held constant. The negative sign is used since the volume always decreases wi t h
increasing pressure (at consta n t tempera t ure ): that is. the partial derivative is
f3 = p = r
(2. 1 5 )

l'
. RT \

,
P_
(2. 1 6 )
=
{3vd7'
( 2. 1 7 )
I<" Vd P .
..
Sec. 2.6
An Application
29
Integrating, we have
v
dv
{3v0
T
To
dT
KV0
dP,
so that
v0 [1 + {3 ( T
T0 )
K ( P  P0 ) ].
(2.18)
Then, Equation
(2.18) gives
105
T =
(
10)
2
K
101
7.6 X
{3
=
5.2
6.8
107 Pa
680 atm !
2.6 AN APPLICATION
Suppose that we wish to calculate the decrease in pressure of a fluid when it is
cooled from T1 to T2 We know that the equilibrium states of the fluid are
fixed by specifying two of the state variables that are related by some equa
tion of state
f ( P, V, T)
0.
(2 .19)
We assume that the process in which the fluid is changed from an equilibrium
state ( P1 , T1 ) to another equilibrium state ( P2 , T2 ) is isochoric that is, the
P (v T ) .
(2.20)
Chap. 2
30
Equations of State
aP
a t'
c/P =
dv
iJP
aT
(2.2 1 )
dT.
t'
Since we are assuming that the cool i ng takes pl ace at constant volume, the first
term on t he righthand side is zero. Thus
,.
r,
p,
pl
iJ P
,..
ar
T.
'
1.
(2.22)
dT.
Unfo rtuna tely.. the in te gran d is unknown. However.. using the cyclical relation
aP
aT

aP 1 r
,.
dl'
Th us
riP
riT
ar
av
iJ V
a,v
aP

aT
riP

PI
{3
=
( T*\
Tl
( 2. 2 3 )
if {3 and K are i ndependent of T This is negative i f T., < T1 indicating that the
pressure is reduced on cooling. Note that this result could have been obtai ned
immediately from Equation (2. 1 8).
In practice, the cooling would not be reversible because one simply heats
the fluid and lets it cool. The result wou ld be large temperat ure gradients within
the fluid itself and between the fl uid and its surroundings. Thus the intermedi
ate states are no t equilibrium states and the equation of state cannot be applied.
However_ the initial and fi nal states ar equilibrium states, and i t doesn't
matter how we go from state 1 to state 2 to determi ne the change in the state
P2
P, i s independent of the path, bei n g
variable P. This is because a P
deterr11i ned only by the end points. We can choose any convenient path to cal
culate changes in state functions for processes between a pair of eq ui li briu m
states. The most con ve nie nt path is a reversible path.
..
Problems
ll
P RO B L E M S
21 How many kilograms of helium gas are contained in a vessel of I liter volume at
50C if the pressure is one atmosphere? (The atomic weight of helium is 4.)
106 Pa and a
taneously increased so that at every instant P and v are related by the equation
P
A = constant
= Av,
(a) Express A in terms of the pressure P1 , the temperature T1 , and the gas con
stant R.
(b) Make a sketch representing the process in the Pv plane.
(c) Find the temperature when the specific volume has doubled, if T1
200 K.
iJP
av
=
t
'
2S Noting that at the critical point, the three roots of the van der Waals equation .
Chap. 2
ll
v'
vfv" , T'
T/Tc
and
Equations of State
P'
P/Pc .
the van
P'
r .
3
,
..
I

RT
1J
 
.,

Tv
show that
IJ(
)b.
Tc =
Ba
'J 2 1bR
P
c
fZtiR
T2b 3b
t
..
0 and il PI riv2
Substance
He
H,
Q.,
co,
H ., O

..
3.06
J.27
:\.42
J.6)
4.29
RT
v  b
e a/ RTr
show that
a
Pr =  2 2 "
4e b
and find the numerical value of RTc
u la t ed experimenta] values"?
28
(a)
the expansivity f3 of
(b)
/ Pc Vc .
Problem 27.
At h ighe r temperatures and l arge specific vol utnes ( low densities) all gases
a pproxi ma t e an ideal gas. Show that for large values of T and v. the e x pres s ion
for {3 obtained in ( a ) goes over to the corresponding equation for an ideal gas.
ap

aP
dK
aT
0.
Problems
]3
state is
bT2 +
aP
constant.
f3
va
Tv
K =
'
3 ( v  a)
4Pv
4
3'
P (v  a)
where
AT
f3 ::: 0.21
3. 1
Configuration Work
3.2
Dissipative Work
37
40
.
.
'
..
3 .3
3.4
Heat
43
3.5
Units of Heat
45
3.6
46
3.7
46
3.8
47
41
35
y; d X; , i
1, 2, . . n.
(3.1)
'
Here ltW represents the work done by virtue of infinitesimal changes in the
extensive variables X;; 71W is not an exact differential, as indicated by the
notation (see Appendix A). The variables X1, X2, etc. are said to determine
the configuration of the system, and
'
F dx
PA d.t
P dV.
37
Chap 3
38
F=
dx
PA



'
final
level

original level
: 
Fipre 3.1
Expansio.n
of an enclosed gas
against the pressure
produced by an
external force.
TABLE 3.1
Svs tem
Intensive Variable
gas
..
Extensive Variab1e
V (volume)
A (area)
q ( c har ge )
M ( manctization)
P (polarization)
P (pressure)
r (surface te n sio n )
(electromotive force)
8 ( ma g n et i c fi e l d )
E (electric field).
liquid. or solid
film
electrolvtic cell
magnetic material
dielectric material
...
PdV
I'dA
Edq
Bt/M
Ed'P
'
some of which are listed in Table 3.1. For a surface film of liquid._ the reversible
work required to increase isothern1ally the surface area of the film by an
amount
dA
is aW
fd A._ where
electromotive force
I( for
tiP: the
work is
EdP,
where E is the
0. so
PdV
liV
I
I
=:
P(Vh Vn).
(3.2)
Sec. 3.1
Configuration Work
39

Here Va is the initial volume and Vb the final volume. The work done is evidently the area under the curve in a PV diagram. lbis is the shaded rectangle
of Figure 3.2 for the case of an isobaric pr oce ss
For an iscthert11al process, the temperature is constant, the PV curve for
an ideal gas is a hyperbola, and
.
nKT
v, dV
Vo
V,
nRT In V.
(3.3)
(Figure 3.3).
In both the isobaric and the isothermal process, if Vb > Va, the process is
an expansion, and work is done by the system (W > 0). If Vb < V,, the process
is a compression, and work is done on the system (W < 0). This important
sign convention will be followed throughout the text.
Figure 3.3
Work done
in an isothertnal
process involving an
ideal gas.
Chap. 3
40
p
A
I
'
I
I
I
I
VII
the curve, different results are obtained for paths A and B. Thus
a.
aW
* 0.
):::::::=>.::=.:: :;:
. '......
... . ....:
. ....
. . ...
.. ....
. .
. ..
... . . ...
.. ......
, . ..
.
..... ...
. .
....
...
.. ...
. . . ......... . .:.. . .
.
. ..: =:.::.....
'I'' ' :
.: .::.:::::
..
: :
:: : :: : :
:.::::; : :::: :,:: . : :.
:: :::::. ::::::=:=:;::
:(:
:
:::.
:: .::.::: ::.:.
:
: :: ::=
:
:.. .:.::
:,
::
=:{" ::
<
:::x::: :: :::
:: ::": .
.
....
...
3.5).
by
aw
=:

Td8.
(3.4)
Sec. 3.3
.
..
41
. .
,.. .'
.; ;:: ....... ...
. .
.. . .... .
.... :::
.._.,'"'""
.
. . .. .
..
./'../'""'"""'
.
......
:. ......
.
..:.>
. . ... .
.. . . . '
. '. ..
.
..
..
.
..
.
.
.
.
:.
.:. ...
..
.
...., ..
. ..
. :
.
.
::
...
.
..
.
.
.
.
...
,.
. ..
..
.
.<.
.
. .
applied.
I
I
R
Figure 3.6 Electrical
work. A current is
passed through a
resistor.
(3.5)
Here ttW is the work done in time dt on the system comprising the current and
the resistor. Reversing the direction of current flow does not affect the sign of
the work.
Chap. 3
42
Figure 3. 7
Three
different adiabatic
paths representing
processes in which an
isolated system is
carried from state a to
state b.
+
Correspondingly, path
of the path.
"
tJ
lf"''ad
is pathindependent and
from the differentiaL but only if we restrict ourselves to adiabatic work.) It fol
lows that we can define a property of the system, a state variable U, such that
ll
,,
In differential form,
(3.6)
We note that dU is the negative of the adiabatic work done bj' the system, so it
is the adiabatic work done on the system. We define U as the internal energy of
the system. Thus Equation (3.6) states that the increase in internal energy is
Sec. 3.4
43
Heat
equal to the work done on the system in any adiabatic process. Alternatively,
the work done on the system (with no heat flow) results in an increase in its
internal energy.
To summarize, experiments show that an energy function of state can be
defined by the amount of work done in an adiabatically enclosed system. This
is not to say, however, that any two states of a system can be coupled by an adi
abatic path.
3.4 HEAT
We wish now to extend our ideas to processes that are not adiabatic. If the sys
tem is not contai11ed within adiabatic walls, it is nevertheless possible to bring
about a given change of state in quite different ways. "\ beaker of water may
be brought from 20C to l00C by electrical work perforrned on a resistor
immersed in it, or, alternatively, by lighting a Bunsen burner under it. The lat
ter process inyolves no work at all (Figure 3.8).
For any change between given states, d U can always be uniquely deter
mined by carrying out an experiment under adiabatic conditions, for which
dU = llWad If the conditions are not so specialized, then dU =1:  t1Wad' in
general. Instead we may write the equation
dU
7/Q aW,
or
t!Q
ltW  7/Wad.
'
(a)
Figure 3.8
(b)
Chap. 3
44
Then
aQ
==
dU + dW,
(3.7)
which is the first law of therr11odynamics in differential form. In words, the first
law states that
The heat supplied is equal to the increase in intertzal energy of the system
plus the work done by the system. Energy is conserved if heat is taken
into account.
Note that heat is not a property (state variable) of the system; only the inter
nal energy is.
It can be shown that the quantity liQ exhibits the properties that are
commonly associated with heat. These properties are summarized as follows:
1.
2.
3.
dU
0.
That is, in a cyclic process, the change in internal energy is zero so that the
work performed is equal to the heat absorbed by the system.
One useful way of looking at the first law follows from transposing the
terms in Equation (3.7):
dU
71Q aW.
The increase in internal energy of a system equals the heat flow into the
system minus the work done by the system. Think of a bank: aQis a deposit
itW a withdrawal. What's left in the bank is d U. The sign convention for aQ
is 7/Q > 0 for heat flow into a system, and 71Q < 0 for heat flow Ollt of the
system.
Sec. 3.5
Units of Heat
45
A large btock of ice at ooc has far more internal energy than a cup of hot water;
yet when the water is poured on the ice some of the ice melts and the water
becomes cooler, which si
tes that energy has passed from the water to the ice.
Q,
which says that the internal energy change of the body is equal to the heat
transferred to it from the s11rroundings. One definition of heat is:
Heat is energy transferred across the boundary of a system
temperature difference only.
as
a result of a
This definition is not entirely satisfactory, however. Changes of state (e.g., from
ice to water or from water to steam) involve the transfer of heat to or from a
body witlzout any change in temperature. It should also be kept in 111ind that heat
transfer is not the only way to change the temperature of matter: a body that has
work done on it may become hotter as a result, and a body that does work on
something else may become cooler. A more precise definition of heat is:
Since heat is a form of energy, the correct SI unit of heat is the joule (J).
However, the kilocalorie is widely used. It is defined as follows:
1 kilocalorie (kcal)
1 kg of \Vater from
of
14.5C to 15.5C.
4
2.39 X 10 kcal,
1 kcal
4184 J.
The calorie that dieticians use is the same as the kilocalorie and is some
times written "Calorie" to distinguish it from the ordinary, smaller calorie
associated with the cgs S)'Stem of units.
Chap. 3
46
. .
:.:.:_:.
.
.
:.
. ..
..
. .
.
. . ..
'
.
.
'
. .
'
We have noted that if the configuration \York and the dissipative work are
both zero.
or the heat flow in increases the internal energy. Suppose. on the other hand.
that the configuration work is zero and that work is done with a stirrer
immersed in a fluid kept at constant volume and thermally insulated. Then
where Wd is the dissipative work done on the system and is inherently negative.
The righthand sides of the equations in the two examples give rise to the same
change in internal energy. Thus work and heat are .. equivalent'' in this sense.
However, heat and work can be differentiated from a microscopic view
point. When energy is added to a system in the form of heat, the random motion
of the constituent molecules is increased. Consider gas in a cylinder. If heat is
added through diathe1tt1al walls, this increases the random kinetic energy of the
molecules which means a rise irt temperature. Now let the gas be confined in a
cylindrical piston with adiabatic walls. When the piston is pushed in the mole
cules striking the piston are accelerated. in the direction of its travel. However.
any organized motion initially imparted to these m<>lecules is rapidly random
ized by collisions, either with the walls or with other gas molecules. Again the
increase in random kinetic energy appears as an increase in temperature.
2.
3.
dV + aw.
==
dV +
PdV.
Chap. 3
48
( T,,
0 and
T,,)
P ( V,,
V.,) .
Equation (3.8) is especia lly useful for deter m in ing the work done
of copper? We assume that whereas the pressure change is large. the volume
cha n ge is small,
V,,
=::;
V.,
V. Then
aw
KPVtiP
and
,
'
PdP
KV
=
.
. I' .
For copper. K
7.5
lO
( P,,  Po) .
(3.10)
...,
12
__
PROBLEMS
31 Ten kilomoles of an ideal gas are cotnpressed isothermally and reversibly from a
pressure of 1 atmosphere to 10 atmospheres at 300 K. How much work is done?
32 S t e am at a constant pressure of 30 atn1ospheres is adn1itted to the cylinder of a
steam engine. The length of the stroke is 0.5 m and the diameter of the cvlinder
is 0.4 m. How much work is done by the steam per str oke?
.,
Problems
49
7;
reversibly against a piston to a volume equal to onehalf its originai volume. The
temperature of the gas is varied during the compression so that at each instant
the relation P
(a)
(b)
(c)
A V is satisfied, A
constant.
34 Ice at ooc and at a pressure of 1 atmosphere has a density of 916.23 kg m:l,
while water under these conditions has a density of 999.84 kg m:t. How much
work is done against the atmosphere when 10 kg of ice melts into water?
35
(a)
Derive the general expression for the work per kilomole of a van der Waals
gas in expanding reversibly and at a constant temperature T from a specific
volume v1 to a specific volume v2
(b)
Find the work done when 2 kilomoles of steam expand from a volume of
30m
volume
of
60 m'
at
temperature
of
l00C. Take
(c)
to
5.80
==
Vj
is
increased at constant volume until the pressure is doubled. The gas is then
expanded isother1nally until the pressure drops to its original value, where it is
compressed at constant pressure until the volume returns to its initial value.
(a)
(b)
2 kilomoles, P1
2 atm, and V1
4 m.
37 Two kilomoles of a monatomic ideal gas are at a temperature of 300 K. The gas
expands reversibly and isothermally to twice its original volume. Calculate (a)
the work done by the gas; (b) the heat supplied. (Note that for an ideal gas UrxT,
so U
0 in an isothermal process.)
38 A gas is contained in a cylinder fitted with a frictionless piston and is taken from
the state a to the state b along the path acb shown in figure 3.9. 80J of heat flow
into the system and the system does 30J of work.
Figure 3.9 P V
diagram for
Problem 38.
d
v
Chap. 3
50
(a) How much heat flows into the systetn along the path adb if the work done
by the gas is 10 J?
(c) If Ua
0 and Ud
(a)
(b)
(c)
(d)
(e)
At constant pressure.
At constant temperature.
What is the temperature at the end of the process in (a)?
What is the pressure at the end of the process in (b)?
Sketch both processes in the p V plane.
..
103kgm3and6.75
1011Pa1,respectively.
3ll During the ascent of a meteorological balloon its volume increases from 1 m3 to
1.8 m3, and the pressure of the ideal gas inside the balloon decreases from 1 bar
to
bar(1 bar= 105 Pa). The internal energy of the gas is U =BOOT joules,
(a)
(b)
(c)
(d)
AP
B. Find A and B.
'
4.1
Heat Capacity
53
4.2
Mayer's Equation
54
4.3
57
4.4
59
4.5
Comparison of u and h
61
4.6
61
51
Q is
lim
r ....o
Q
T
71Q
.
dT
aQ
(4.1)
'llQ
as an infinitesimally small
system is capable of
holding heat, which it is not; a term connoting the storage of internal energy
would be more appropriate.
The heat required to produce a given temperature change is propor
tional to the mass of the system. We define the specific heat capacity, often
abbreviated to "specific heat," as the heat capacity per unit mass:
c=
1
n
tJQ
dT
(4. 2)
(1)
the heat is supplied at constant volume; and (2) the specific heat
cp,
in which
dT
and
cp
(4.3)
53
Chap.4
54
c,
.l kilomole1
K J
400
200
800
600
1 000
1200
7"( K)
Plots of c,. and cp for copper versus temperature at a
pressure of one atmosphere. (Adapted from Thermodynamics.. Kinetic
Figure 4.1
..
G.L. Salinger.)
The distinction between the two heat capacities is important chiefly for gases
because of the large coefficients of thermal expansion.
In general. the specific heats are functions of temperature and can be
regarded as constants only over limited ranges of temperature. As an example.,
consider the specific heats of a solid such as copper shown in Figure
low temperatures,
Cp
::=
cr
25
10 J kilomole 1 K
4.1. At
c,.
c,.
and
cp
..
tiLt
Since
7/Q Pd..
aq
(4.4)
Pdt'.
(4.5)
Sec. 4.2
Mayer's Equation
55
Pv
RT.
(4.6)
du
au
av
v
d
au
aT
dT.
(4.7)
tlq
au
aT
dT
(4.8)
To obtain cv, we divide this equation by dT and hold the volume constant so
that dv =0. The result, which holds for any reversible process, is
tlq
au
aT
dT
(4.9)
au
av
=0
(4.10)
for an ideal gas. The substitution of Equations (4.9) and (4.10) in Equation
( 4.8) gives
tlq
cvtJT + Pdv.
(4.11)
Pdv
vdP
RdT.
(4.12)
tlq
(ct.
R)dT  vdP.
Now
Cp=
tlq
dT
p'
(4.13)
56
dP
Chap.4
O. Then
llq
=
dT
c,. +
c,. +
R.
c1'1.,
or
Cp
(4.14)
This relation is known as Mayer's equation.* It states that over the range of
variables for which the ideal gas law holds, the two specific heat capacities differ by the constant R.
We introduce the ratilJ of specific heat capacities
Cp
y=
c,.
(4.15)
cp
cp
==
..
i R.
cr
cr
..
and y =
R. andy
c,.
1.67.
1.40. These
is equal to
8.31 x 103 J kilomole I K 1 for a wide range ()f temperatures. For solids
Finally. from the foregoing analysis we can calculate the internal energy
(' v =
since
11
ar
or
T
ll
u0
T
CvdT.
(4.16)
*Julius Robert von Mayer. a German physician. Jiscovercd the equivalence of heat and
( 1842 ).
Sec. 4.3
57
The specific heat capacity at constant volume is nearly constant over a region
of temperature extending from approximately 200 K to 1200 K for most gases.
Thus Equation (4.16) is applicable for many practical problems.
du
aq Pdv
'
so that
I
I
(4.17)
I
.
.
+ Pv.
The quantity h is called the specific enth.1/py. The origin of the word is the
Greek verb thalpein meaning ''to heat." Since
u,
h is also a state variable. (If two variables have exact differentials, their prod
(4.17) becomes
which is to say that the latent heat of transformation is equal to the difference
in enthalpies of the two phases.
Consider now the three possible phase changes. Let 1 denote a solid, 2 a
liquid, and 3 a vapor. Then .
Chap.4
58
I 12
/23
/11
h'"
h'"  h'
'
(vaporization),
Here the first superscript is associated with the .'iecond subscript; that is, dou
ble prime is associated with the subscript 2 denoting a liquid etc. This is
merely a notational convention.
Since enthalpy is a state function..
,
tlh = (.)
the change of enthalpy in a
diagram as in Figure 4.2.
Consider a cyclical process around the triple point and close enough to it
so that only changes in the enthalpy occur during phase transitions. Then
solid
:.
..
dhl
h 2
h3
=:
Here
CP
solid
liquid
Figure 4.2 Pressure
temperature plot for a
substance that contracts on
freezing. The circle denotes a
cycJicaJ process around the
triple point for which the total
change of enthalpy is zero.
ST.Rl'
vapor
/13
I:.2
/21
1r:,
= lr2
Sec. 4.4
TABLE 4.1
substances.
Latent heats of
Mercury
Alcohol
Gasoline
1 atm
538 kcal/kg
63
207
95
Water
59
at Melting Point,
1 atm
80kcal/kg
Water
3
5
77
Mercury
Lead
Aluminum
so
or
(4.18)
(All these latent heats are intrinsically positive.) This is an important result.
Some values are given in Table 4.1. The latent heat of sublimation for water is
538 + 80
618 kcal kg1
=
4184
J
kcal
2.25
106
J
kg
u = u(v, T).
P, v,
v, T
we will find that this choice is a natural one both from an experimental and
mathematical viewpoint. Similarly, the natural choice in the case of the thermodynamic variable
h is
h
h (T, P).
(4.19)
Then the analysis proceeds in a manner exactly parallel to what was done in
the case of the internal energy. Here
aq
h
du + Pdv,
= u + Pv,
(4.20 )
(4.21)
Sec. 4.6
61
h  h0= cpdT = cP ( T
T0)
To
if
(4.29)
::*:::.:=;:::::.:::=:::.:=\:: .::=: ;:::.:.:'::::: :.:::::::::::::.: :::.: :::: :::::::: ': :: :: .:.::::::::::. ::;::.;:.:: ::: :::: :;:::.: :.::: .:.: :::.: :: : ..:::: ;: : ::
4.5 COMPARISON OF
AND h
Table 4.2 summarizes the parallel expressions involving the internal energy
and the enthalpy.
TABLE .2
enthalpy.
Reversible process:
Internal energy u
Enthalpy h
du
dh
Cv
tlq Pdv
dU
dT
Cp
ilq + vdP
ah
llq c"dT
au
0
av r
Ideal gas:
Pdv
ar
h h0
c,.dT
T.,
P( v2  v1), where
v1
(4.30)
We now wish to find the specific work done in an adiabatic process involving
n ideal gas. Setting llq
0 in Equation (4.28), we obtain
=
vdP = cpdT.
.
(4.31)
62
Chap.4
We also have
7/q
which for 7/q
c,.dT + Pdv
0 yields
Ptlv
c,.dT.
(4 32 )
.
vdP
cp

Pdv
y ..


c,.
:__
or
dp
(/1)
.
y
 =
( 4.33)
'l'
jt>
sure and volume for an adiabatic process involving an ideal gas. Since y > 1
it follows that P falls off more rapidly with v for an adiabatic process than it
==
constant).
Ptlv
1C =
vYdv
==
1
(Kv Y)
1)2
. .
1'VI

VI
v,
lV =
For an expansion v2
> v1
..
lV >
1 y
t.
1' = u!
( 4.35)
 r P2L2
),
 PI v IJ1
lt2
==
cr(T1
<Jn

com
Sec. 4.6
Work Done in
an Adiabatic
Process
1 atm. We wish to
find \12, T2, W, and d U. For an ideal monatomic gas, the ratio of specific
heats 1 is
5/3.
(400)=174K.
As the gas expands, the temperature and the pressure drop (no heat flows into
or out of the system).
The work done by the system in the ex pansion is

= 2.74
Finally, since
106 J.
0, dU =  W= 2.74
AU= Cv(T2  T1 ):
3R
(8
=2.74
PtYt 3R
1.01
105
400
X
4) 3
 (174 400)
2;
106 J.
Chap.4
64
PROBLEMS
c,.
T3 Jaw:
c I)
T
=A
0
(a) What is the molar specific heat capacity at constant voll:Jme of NaCI at 10 K
and at 50 K?
(b) How much heat is required to raise the temperature of 2 kilomoles of NaCl
from 10 K to 50 K at constant volume?
(c) What is the mean specific heat capacity at constant volume over this tem
perature range?
c,.
R.
au
(Refer to Equation ( 2.13 ). )
dU
K
= PK'V (cp Cv) .
aP ,
f3
(Refer to Eq uat i ons (2.13) and ( 2.14 ). )
45 When a material is heated .. it cxperiencl!s a very slight increase in mass since
E
me:.. Estimate the fractional change in mass when the temperature of a
block of copper is rai sed from 300 K to 400 K. Take cp for co.pper to be
2.6 x. 104 1 kiJomolc 1 K 1 Its atomic weight is 29.
=
47 The specific heat capacity at constant pressure of a gas varies with the tempera
ture according to the expression
(
( P == tl
+ hT
'
'
2
T

Problems
65
to2T?
48 Show that the following relations hold for a reversible adiabatic expansion of an
ideal gas :
(a) TV1l
(b)
T
ptlh
constant.
consta nt
49 An ideal gas undergoes an adiabatic reversible expansion from an initial state
(T2,
v2).
In
T, \
_::
Tl
( 'Y
1 ) In
v1
v2
(b)
If TJT1
2/5 and
vJv1
the initial state via any adiabatic reversible process involving any known
ideal gas.
410 The equation of state for radiant energy in equilibriunt with the temperature of
the walls of a cavity of volume Vis P
equation is U
(a)
(b)
aT4V.
Show that the heat supplied in an isotherrnal doubling of the volume of the
cavity is (4/3)aT4V.
cv
5R/2
..
sure of 8 atm. Compute the final volume, the final temperature, the work done.
the heat released.. and the change in i_nternal energy for:
0.93 P0VQ.
413 One ki l ogram of ice at 20C is heated to ooc and melted. The resulting water
is heated to l00C, vaporizes, and the steam is furth er hated to 4QO>C. Assume
that all the processes are isobaric. Calculate the c hange in enthalpy in kilocalo
ries and in
joules.
and steam are 0.55, 1.00, and 0.48 kcal kg1, respectively.)
driving the
internal energy change of the air in the tire between pressure measurements?
Assume that air is an ideal gas with a constant specific hea t capacity Cv
and that the internal volume of the tire remains constant at 0.057 m3.
5R/2
Chap. 4
66
415 Shortly after detonation the fireball of
e xpa n sion is adiabatic and that the fireball remains sphe ri c a L estimate the
radius of the ball when the temperature is 3000 K. (Take y =
1.4.)
5.1
69
5.2
72
5.3
74
67
to measure the dependence of the internal energy of a gas on its volume were
made by GayLussac and later by Joule in the middle of the nineteenth cen
tury. The results of the experiments showed that the internal energy is a func
tion of T only and does not depend on the volume v. This, like many other
properties of gases, is on ly approximately true for real gases and is assumed to
hold exactly for ideal gases.
Before describing the experiments, we consider the following arguments.
Using the cyclical and reciprocal relations for partial derivatives given in
Appendix A, we can write
au
iJv
aT

av
dlt
II
aT
(5.1)
,,
(4.9))
au
Ct
aT
...
dU
av
= c
1.
av
(5.2)
ll
69
Chap. S
70
diaphragm
I
as sa
...
mpl
I
.
vl  vo
vo. To

Figure 5.1
vacuum
determine the dependence of the internal energy on the volume. The question
is: how can we keep
11
the
c1
portion of a thermal1y
thern1ometer. When t he
.free eplpansiv11. He re
V0
i s the ini
e xpa n sion
the internal energy is unchanged since no nergy is lost or gain ed . * The fina]
temperature which can he measured. is
u, oT
Vo
av
dv.
u
the internal
e ne rgy
coefficient.
Joule
\\'as
unable
to
measure
any
temperature
change
Joule
for
air.
Subsequent experitnents using various gases ind ica t e that the temperature
d e cr e as es bv at most a verv sn1all amount. Summarizing these resul ts
.
a v.
Although
<
..
Sec. 5.1
71
It can be shown (Problem 53) that for a van der 'aals gas,
in that case:
iJu
'TJ =
dV
= 0
and
(5.3)
(T)
au
T
T aT
dV
+ P dv.
(5.4)
1/T makes
the lefthand side of Equation (5.4) an exact differential, a function of the state
variables
T and v. * If d z
iJN
=
ay
iJx
au
av TaT
a 1 au
aT T av
'
where the subscripts on the partial derivatives have been omitted for conve
nience. Carrying out the differentiation, we have
+
iJ2u
TaTav
1 iJP
+

TaT'
or
au
av
__
iJP
aT
 P.
(5.5)
This fact is intimately associated with the introduction of the concept of entropy. as will
be shown in Chapter 6.
Chap. 5
71
s
a
g
l
a
e
d
i
n
a
r
o
F
RT
..
so that
du
dV
P

dT
RT

RT
(5.6)
0.
==
of
ity
lid
va
e
th
s
on
d
p
n
e
de
f
oo
pr
e
Th
v.
on
nd
pe
This proves that u does not de
the assumption that aq/T is an exact differential and the applicability of the
5.2
constant
low pressure on the other side. The objective is to measure the temperature
difference T2
llq
and
T1
u2  u1
1v =
P1
dv
P1,v1 ..
li l
ex p a n sio n
P2 ti'v
UJ2 =
==
is
P2v2
(5.7)
WiJJiam Thomson became Lord Kelvin at the end of the nineteenth centun.
Sec. 5.2
initial
state
7l
,...____,
__..
porous plug
.. .
final
state
(b)
Figure 5.2
It follows that
or
(5.8)
Thus a throttling process occurs at constant enthalpy.
In the JouleThomson experiment, the pressure and temperature of the
gas before passing through the plug are kept constant and the pressure on the
other side is varied while the corresponding temperature is measured. The results
give a locus of points on a TP diagram representing the isenthalpic state of
the gas (Figure 5.3). The numerical value of the slope of the curve at any point
is called the JouleThomson coefficient , where
aT

aP
(5.9)
The gas is cooling when /L is positive and heating when J.L is negative. The point
0 is called the inversion point.
where JL
=
The experimental result is that for most gases over a reasonably wide
range of temperatures and pressures, the T.P curve is approximately flat and
Chap. 5
74
tnvers1on
po1nt
I
I
I
t
I
I
J
J.L
==
ah
. riP
cp
iJT
aP
11
and
h(T).
(5.10)
iJh
iJv
aP .,.
0.
on
in turn is used to raise the internal energy <>fa heat reservoir. In this case, the
heat out (of the system
the system is unaltered. Examples are stirring heat or the heat generated by
the flow of current through a resistor.
Sec. 5.3
heat reservoir
Q
w

(W
75
machine or sub5tance
Q)
( W < Q)
(a)
(b)
Figure 5.4
Case (b) is the reverse of c.ase (a). Heat is extracted from a reservoir and
is converted to mechanical work by the machine. The question is: can the work
done by the system be equal to the heat in? Can the conversion be 100 percent
efficient? The answer is no. The second law of thermodynamics states unequiv
Q2
heatabsorbed
Qt
uthermal pollution,
Chap. 5
76
The efficiency of the engine 11 is equal to the work done by the system
(the machine or working s ubst ance ) divided by the heat absorbed Q2:*
JW!
=
71
==
,Q
output
input
(5.11)
,
In other words the efficiency is the ratio of \vhat you. get" to what you pay. ..
the syste m
we have
In writing this, we arc mindful of our sign convention in which the heat flow
into the system and the work done b.,v the system are p os i tive q uantit ies..
whereas heat flow out of the system and W()fk done on the system are inher
ently nega tive We assume that the engine operates in a cycle. Since the state
.
(5.12)
Subs t itut in g this
in Equation (5. t 1 )
we
obt a in
(5.13)
process in which the ""working substance'' is an ideal gas. The four steps are an
.,
w
Note that
p dV
=:
"''
* 0: the
W' + w,
work
must
W"
==
p t/V4
dP
0 an d
* The efficiency
#tiV
71 is not to
lV
{}2
0, hut t hi s does
Q1 n1caning "
'
n o t imply that
V are
p dV
state vari
om i ssion of
the
0.
absolute
Sec. 5.3
77
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insulator
insulator
isotherrnal
expanston
adiabatic
expanston
isothermal
compresston
adiabatic
compresston
(a+ b)
(b .... c)
(c+ d)
(d+ a)
Figure 5.6
p
Q.
(adiabat)
r2
(adiabat)
TABLE 5.1
Heat transfer and work for the four steps of a Carnot cycle.
Heat
Process
a
Isothermal expansion
.. c
Adiabatic expansion
d
d+a
c
lsothertnal compression
Adiabatic compression
Q2
>
O(in)
0
Q1 < 0 (out)
0
Work
0 (done by system)
W' > 0 (done by system)
W1 < 0 (done on system)
W" < 0 (done on system)
w2
>
Chap. 5
aQ ttw.
(5.14)
78
Now
b and
l!W. Here Q2
W2 and Q1
W1. Hence
(>
0 since vb >
(<
0 since V:1
=:
(5.15)
< ).
constant. Since P
(5
1 6)
nRT/V we
have
so that Tv;
constant and
(5.17)
If we divide Equation
(5.17) by
y
Tv
I
./, ..
(5.18)
1/(y
l)th
root. we obtain
V,,
v:.

(5.19)
v:,
Ql

Q:
Using this expression in Equation
==
r1
(5.20)
T:..
(5.13) gives
(5.21)

<
< 1.
Sec. 5.3
79
The work perforttted during the adiabatic steps of the cycle can be calcu
lated using Equation (4.35). However, we note that the use of Equations
(5 .11), {5 .15), and (5.21) yields W, the total work done, which is the quantity of
greatest interest. It can be easily shown that this is just the area enveloped by
the curves in the P V diagram delimiting the cyclical process.
It is important to emphasize that a Carnot engine operates between
only two reservoirs and that it is reversible. Also, if a working substance other
than a11 ideal gas is used, the shape of the cunyes in the P V diagram will, of
course, be different. Carnot theorized that the efficiency given by Equation
(5.21) is the maximum efficiency for any engine that one might design. We
note that the efficiency would be 100 percent if we were able to obtain a low
temperature reservoir at absolute zero. However, this is forbidden by the
third law.
A Carnot refrigerator is a Carnot engine in reverse (Figure
5.8). Work is
done on the engine with the result that heat is removed from a low tempera
ture reservoir {the interior of the refrigerator) and delivered to a high temper
ature reservoir {the surrounding room). In this case we define a coefficient of
performance
"what you pay." Because Q1 is positive (heat tlo\v into the system) and W is
negative (work done on the system), we introduce a minus sign in order to
make the coefficient of perfor111ance a positive quantity:
(5.22)
The last step follows from Equation (5.20), which applies to the Carnot refrig
erator as well as to the Camot engine. Since T1 < T2, the coefficient of perfor
mance of a refrigerator, unlike the thermal efficiency of a heat engine, can be
made much larger than unity.
T,
...

Chap.5
80
refrigerant
(heat out to surroundings)
(e.g., freon)
high
pressure
condenser
high
pressure
vapor
liquid
compressor
throttle

low
pressure
low
liquid/
pressure
vapor
vapor
evaporator
long capillary tube
Figure 5.9
Ot
(heat in
PROBLEMS
if l'
=0
ilh
,iJP
0.
h(P . T)
and u
( 1'. T).)
Problems
81
u
(a)
(b)
u0
cv(T  Tv), u0
constant.
S3 The specific internal energy of a van der Waals gas is given by
u0
'
a
cvT  , u(), a constants.
v
Show that JL
RTv
Cp
( V b)
v
Cp
0,
K =
RT
, and p.
0.
54 Show that
(a)
(b)
(c)
5S
iJh
aT
ah
=
v
av
ar
av
Cp 1
=
h
{3p,
JLCp

VK
J.L
 
v(
p,/3  K)
(a)
If the engine receives 1200 kilocalories from the reservoir at 400 Kin each
cycle, how much heat does it reject to the reservoir at 300 K?
(b)
(c)
(d)
57 Fifty kg of water at ooc must be frozen into ice in a refrigerator. The room tem
perature is 20C. The latent heat of fusion of water is 3.33 x lOS J kg1 What is
the minin1um power required if the freezing is to take place in one hour?
S8 W hich gives the greater increase in the efficiency of a Carnot engine: increasing
the temperature of the hot reservoir or lowering the temperature of the cold
reservoir by the same amount?
Cha p. 5
81
the isothermal expa n s ion the volume doubles. The ratio of the final volume to
the initial volume in the adiabatic expansion is 5. 7. The \\ork output of the
engine is 9 x 1 0" J in each cycle . Compute the temperature of the reservoirs
between which the engine ope ra t e s. ( A ssutne
1 kilomole).
510 A h e t engine ha ving two kilotnolcs of an ideal ntonatomic gas as the working
substance under goes a revers ihle cycle of t.>peratio ns n1ade up of the four steps
shown in Figure 5.1 0. Here ( T, V, )
'
( T. ,)
( 400 K. 10m ). ( T. Vl)
.
(a)
( 300 K. 2 m . ) . ( T". V )
'
( 300 K. I 0 m ). Find:
( 400 K. 2 m .)
Q joules
Qj joules
Q. j o u) es
T'
300 K. Q1
1200 J. a n d "'
=
of heat to
=
400 K. T:
rese rvoi r
=
200 K.
200 J. find Q a nd Q.
each cycle the engine e xt racts 6000 J of heat fro m the high temperature reser
voir. rejects 900 J of heat to the lo\\: ten1prature reservoir and per forms 2100 J
513 A heat pump is a device t h at can he used in winte r to \\'arm a house by refriger
a t i ng the ground .. the outdoor a i r or the \\'ater in the mains. A Carnot engine.
op er a t i ng in reverse as a heat pump, extracts heat Q: from a cold re s er voir at
t e m pe rat u re T and delivers heat Q to a reservoir at a higher temperature T: in
.
e ach cvcle .
'"
p
2
..... isotherm
isochore 
Figure 5.10
P V diag ra m for
a fourstep cycle.
/
isochore
isotherm
'
..+
\ .'
Problems
83
p
c
adiabat
Q,
Fig11ae S.ll
....
I
I
I
l
adiabat
a
..
..._
__.
..
___
v,
)l
b.c
a.e
(a)
Assume that the working substance is an ideal gas and show that the effi ..
ciency is given by
'vhere
(b)
2:
r =
5 andy
1.5.
able value is approximately 7. For greater values, the rise of temperature upon
compression is large enough to cause an explosion
before
spark. This is called preignition. For diesel engines preignition is not a problem
and higher compression ratios are possible. This is partly the reason that diesel
engines are inherently more efficient than gasoline engines.
Chap. 5
84
515 Consider the Joule cycle, consisting of two iobars and two adiabats (Figure 5.12).
Assume that the working substance is an ideal gas with constant specific heat
capacities Cp and c, Show that the efficiency is
..
1J=l
pl
()'I
li)'
p,
2..,_
.
_ ..
..
..._
6.1
Introduction
87
6.2
88
6.3
Irreversible Processes
89
6.4
Carnot's Theorem
91
6.5
94
6.6
97
6. 7
6.8
98
103
85
6.1 INTRODUCTION
tion is i n de pen dent of the particular path taken. However, two of the three
quantities appearing in our statement of the first law the work perfottned
and the heat exchanged are inexact differentials. The question arises: Is there
any way in which we can write the first law in terms of state variables only?
A second concern is that our theory emphasizes reversible processes
that is, quasistatic processes in which no dissipative forces such as friction are
present. But reversible processes are idealizations whereas real processes are
irrev
. ersible, and the first law draws no distinction between them. This leads us
to ask: Is there some state variable by which we can distinguish between a
reversible and an irreversible process?
Finally, in Chapter 5 we noted that certain processes are impossible that
are by no means prohibited by the first law. It is not possible to construct a
machine that convet1s all the heat it extracts from a reservoir into useful
mechanical work. It is not possible to transfer heat from a cold body to a hot
body without supplying energy in the forrn of work. The first law says nothing
about these prohibitions, these "principles of impotency," as they have been
called. Is there, then, something missing from our theory? Do we require a sec
ond fundamental law for a complete description of our world as it actually is?
The answer is yes to all of these questions. We will begin by introducing
the concept of entropy as a useful mathematical variable. Phenomenological
observations will give the concept its physical meaning.
87
Chap. 6
88
7/Q
( 6.1)
7/W.
PdV.
=
(6.2)
t/V.
Now.. the volume Vis a state variable and tf\l is an exact differential. By multi
plying llW, by the integrating factor l/ P. \Ve have replaced an inexact differen
tial with an exact one.
Is there an i n tegra t i n g factor for liQ or liQ, that \villlead to an t!Xact dif
ferential? We note that Pis an intensive state
va r
sive variable. The quantity aW,jP is therefore extensive. Also, two of the three
fundamental state variables
P, V,
aQ,
..
( 6.3)
(/ 5.
That is, the reciprocal of the ahsoJute temperature is an integrating factor that
permits the replacement of the inexact differential aQ, by the exact differen
tial dS. Equation
is derived from the Greek word en+ trepei11 for turning,, or Hchanging.
When we substitute Equations (6.2) and (6.3) in Equation (6.1) we obtain
( 6.4)
for a reversible process. Thus we have succeeded in \vriting the first Jaw
entirely in terms of state variables.
There
are
(I)
(6.4)
t wo remaining concerns:
\\'C
processes only. This would seem to indicate that we have replaced a com
pletely general statement of the first law with one that is restricted to a special
case. Both of these problems will be addressed later in this chapter.
Sec. 6.3
Irreversible Processes
89
>
.. . . . .
'.. . .. .. . ...
. . ..
. . . ...
.: : : : ;:
..______,/ I
Figure 6.1
Battery
. . . .'
: :. : : < .
:.:. . ::::.'
. .. :
...
:' : : ;. .
. .. .. . ..
. . ...
. =: : .: .
'. : ; : .
. . . ..
0 . ..
.' : . .
0 .. .
. .
. . .. .
. :: ..
:.0.:.::
. '..=
.
. 0ooo 0 oo
. .. .
) :
::: ':
.. . .. .
....
.. ... . .' .
. . ...
;..::
'
.
.:;
::.:. ..::
. ..... :(...
. .... ... .
... :"%"
. .....
. ..
.:...
vv .
.
.
.
.
..
.
.
...
.......
.  . ..
:( :.
.._ . . .
.. .
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. . ..
:. . >:. .,.. ... ''1' , . . . .. ..
....... .. .. .
. ,...
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, .. , . . . . .... . . ..., ....
,. :. . .
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: : : ::=: : ::=::: ::;=:::::::
: : . : :::: ::::;. :.:;:.: ? :::.:.:::: :;:::::::: :( :_:_; . = : :
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,
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.
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::_;.
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o o
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::>: ):
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o
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<:.<}0
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=o.:oooo.o:
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::
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....:.: .:.;.
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(a)
Fig111e 6.2
:.
(b)
1\vo different gases, (a) before mixing, and (b) after mixing.
Sec. 6.4
Camot's Theorem
91
T
Figure 6.6
Schematic
diagram of a device forbidden
by the KelvinPlanck
Q.
6.4 CARNOT'STHEOREM
We have said that Carnot argued that efficient engines must operate as closely
as possible to a Carnot cycle. Using the Clausius statement of the second law,
we can prove Carnot's theorem which states:
>
11 That is,
(6.5)
The engines are depicted schematically in Figure
6.7.
refrigerator) by the work from M'. We can arrange the position of the adiabats
T,
...
M'
r,
(a)
Fi811re 6.7
(b)
92
Chap. 6
Q,
M'
"'
M
'
so that in one cycle of each engine M uses exactly as much work as M' pro
duces. Thus I WI
I W' 1. The Hcomposite" engine is shown in Figure 6.8. Paying
careful attention to signs we note that
=
W'l1'I,
I  ;Q'IIQ
I
2
and
or
The equality
f WI
or
; W' i, we
see that jQ2 > IQ2'1 and therefore Q11 > Q1'j. We conclude that the compos'
I Q 1 I from the cold reservoir
ite engi1;1e does no work but extracts heat I Q1
and delivers an amount Q2  Q2': to the hot reservoir. This conclusion vio, lates the Clausius statement, so our hypothetical engine cannot exist. It fol
lows
77'.
We can show that if the Clausius statemnt is violated, the KelvinPlanck
statement is also violated. In this sense the two statements are equivalent.
that TJ
>
Sec. 6.4
Carnot's Theorem
93
M'
(a)
(b)
Figure 6.9
Referring to Figure
6.9, we consider
tion of the Clausius statement, extracts heat from a cold reservoir and delivers
the same amount of heat to the hot reservoir (no work is done on the
machine). The Carnot engine M absorbs heat Q2 from
work
ite engine,
no
Q2
extracted from the hot reservoir and an equal amount of work is done. This
violates the PlanckKelvin statement.
Continuing the proof of Carnot's theorem, we have shown that 11 > 11'
Suppose that the hypothetical engine were reversible. Then
TJc
>
(6.6)
1J,,
thetical engine. Since both engines are reversible, the Carnot engine could
have been used to drive the other engine backward (as a refrigerator), attd we
would have the result
1Jc
If both Equations
<
TJr
(6.7)
'Ylr
(6.8)
Chap. 6
94
That is to say, all reversible engines operating between the same reservoirs
have the same efficiency 11 = 1
6.5
5.20):
(6.9)
The quantity Q/T is known as the Carnot ratio. From this we deduced the effi
ciency 'T1 = 1
T1/T2 and proved that the efficiency of all reversible cycles has
this value. Applying the Carnot ratio to an infinitely narrow Carnot diagram
(finite temperature difference but infinitesimally small quantities
of heat
( 6.1 0)
We consider an arbitrary reversible cycle and represent it as
continu
6.10).
(6.10), we obtain
,...._
l!Q,
l!Q, = 0
_._....
( 6.11)
Figure 6.10
P V diagram of a
L.......
Sec. 6.5
95
where the integration is carried out over the whole corttour. The subscript
emphasizes the reversible nature of the cycle. Since the integrand is the differ
ential
S is a state variable.
Consider next an irreversible cycle. An irreversible Camot cycle that
operates between the same temperatures and produces the same work has a
smaller efficiency 11' than the efficiency 71 of a reversible Carnot cycle. That is,
11' < TJ, which implies that
or
(6.12)
For an infinitely narrow Carnot diagram we have
instead of Equation
that for an arbitrary cycle that is partly or wholly irreversible, we must have
'
Q
l!
T
0
.
<
(6.13)
71Q
<
'
inequality
(6.14)
0'
(6.14) is some
ttQ

2aQ
\.
lzt
6.11. Then
Equation
(6.14) gives
Chap. 6
96
p
_,
__
...
I
I
Figure 6.11
An irreversible
change (dashed line) and a
 
Chang ing the order of integration and the sign of the second
27/
Q
\.
<

term we h ave
F
y
( irrc:vcrsihk)
Thus
or_ in
differential
form.
( 6.15)
i gn
holds for
5'
for
a finite process. We
..,
is
()
aQ
0 an d d5;
0 or
( 6.16)
(isolated system)
conclude that
and is unaltere(i i11 any reversible pr()Cess. This is the principle o.f increas
1ng entropy.
not say that the entropy of part of the system cannot decrease. If. for example.
lower
ofaQA), but
uSA+ 58 will st il l
..
Sec. 6.6
97
adiabatic container
Suniverse
Ssystem + LlSurroundings
>
0.
(6.17)
The fact that the entropy of an isolated system can never decrease in a
p rocess provides
processes can run backward as well as forward. Clearly this is not so; the story
often described as p roviding "the arrow of time'' for the evolution of natural
processes.
e n g i ne
whose efficiency is
less than unity. Suppose that the temp er a ture of a body is T2 and that a
reve rsible engine works between T2 a nd T1, which is tt1e tem perature of a large
reservoir to \Vhich the engine can give up hea t and is also the lowest ten1pera
ture available (Figure 6.13). Then, if the body gives an amount of heat
namely aQ( 1
T1/T2)
aQ
to
mechanical work. If the engine is irreversible, still less work can be obtained.
The available energy is defined to be liQ( 1
energy is T1llQ/T2.
Chap. 6
98
dQ
M
dW
Figure 6.13
Diagram
showing the amount of heat
available to do mechanical
work:ltW
ltQ(l
T1/T2).
=
T1
.,
There exists no process that catz i1zcrease the available energ}' in the universe.
The property of increasing entropy is eqttivalent to saying that energy is
always being degraded into forms that are more and more difficult to use for
the production of work.
The significance of entropy becomes clearer when we consider heat to
be the energy of molecular motion. The lack of complete availability of that
energy for the production of work is due to the randomness of the m olecular
whol e
and so it is impos
sible to extract all the heat energy from a body Thus the property of increas
.
ing entropy means that the molecular motion of an isolated system always
tends to become more random, and the entropy can be thought of as a mea
sure of the Hrandomness" of the internal motion of a system. This connection
between entropy and randomness will be made quantitative by means of sta
tistical thermodynamics.
6.7 ABSOLUTETEMPERATURE
The Carnot c ycle together with Carnots theorem can serve as the basis for
d efin ing an absolute temperature scale. Carnot's theorem shows that the ratio
same temperatures. The special fact about a reversible Carnot cycle is that the
efficiency is independent of the nature of the working substance. It can there
Sec. 6.7
Absolute Temperature
99
compression during which heat Q1 flows out of the system. For the cycle abcda,
a
v
t
6.14 Representation in
the 8 V plane of a Camot cycle
divided into two subcycles.
Bt
""

,._,


L v
e.l
Chap. 6
100
where
Our
chal
Thus
or
only, the
and
Then
<I> is another
Ac/> ( 0)
constant,
( 6. 1 8)
so that
IQ
i
I :
TI

! Q,!
,
 I
T_,
( 6.19)
This ratio is the same as the ratio of the temJ)eratures obtained in our analysis
of the Carnot cycle.. in which the working substance is an ideal as.
Sec. 6.7
but
Absolute Temperature
101
The problem remains to determine the function cP ( (}) . The proof is long,
IS
worth the effort. Using the definition of the entropy, we can write the
ds
l,(du + Pdv).
(6.20)
dtt
au
aT
dT +
v
ds
But also,s
dU
1
=
dT +
T iJT
au
av
dv.
6.8. We take T
u(T, v). Then
(6.21)
(6.20) we have
1
au
dV
+
T
P dv.
(6.22)
ds
It follo,vs from Equations
as
aT
(6.23)
dT +
v
as
iJT
(6.24)
'
v
and
as
au
dV
av
(6.25)
+P.
Now
a
av
as

iJT
a as
aT av
'
Sec. 6.8
101
equal to T; we can then use T to represent both the empirical temperature and
the equivalent thermodynamic temperature. The definition of the Kelvin scale
is completed by assigning to T1 in Equation (6.19) tlte value of 273.16 K .. the
temperature of the triple point of water. For a Carnot engine operating
between temperatures Tand 71, we have
IQf
(6.30)
The smaller the value of Q, the lower the corresponding value T. The smallest
value of
6.8
where
llQ,
71Q,
T dS and 7/W,
ltW,
T dS
(6.31)
P dV,
be written
dU
aQ  aW
aQ,
>
(general).
aQ
(6.32)
can write
llQ,
where
ZIQ
(irreversible),
(6.33)
aQ
aW,
(irreversible).
(6.34)
aW
<
aW,
or
more specifically,
aW
aW,
(irreversible).
(6.35)
This is exactly what we expect: the total work done by the system is the
reversible configuration work (the useful mechanical work) plus the (negative)
Chap. 6
104
dissipative work associated with frictional forces. The latter appears as heat in
==
aQ aw
aQ,
(6.36)
(aW, e).
or
dU
(general).
T dS  P dV
(6.37)
Evidently Equation (6.37) has the same universality as Equation (6.32). Its
just that
7/Q is
and
t1W w i t h PdV
only for
reversible
==
ztQ
==
entropy increases in the process). For adiabatic stirring, aQ 0 but TdS =f. 0
and dS > 0. Also. dV
0 hut aW =f. 0, since stirring work is done.
Equation (6.37) is by far the most important relation in classical thermo
=
==
dynamics.
PROBLEMS
volun1e (c anJ
on
a on
cycle efficiency is 25 percent. Finu the entropy increase of the methane during
the isothertnal expansion.
62 Find the chn!gc in entropy of the system during the follo\ving processes:
(a) i kg of \Vater is heated reversibly by an electric heat1ng coil from 20C to
80 c ( c p
l cal g I c c : =: 4. 1 8 X ] 0 3 J kg  I K I ) .
(
==
..
(b) 1 kg of ice at ooc and 1 atn1 pressure melts at the same temperature and
5
pressure. (The l aten t heat of fusion is 3.34 x l 0 J kg 1.)
(c) 1 kg of steam at lOOoc and 1 atm pressure condenses to \Vater at the same tem
perature and p r e ss u r e (The latent he a t of vaporization is 2.26 x 106 J kg 1.)
.
of
according to
3
kilomole I
K l
.
.
'
Problems
105
(The
atomic
for 1 second. It is initially at 20C. The mass of the resistor is 5 g; cP for the resistor is 850 J kg l K I.
(a)
(b)
(Hint: In the actual process, dissipative \Vork is done on the resistor. I magine a
reversible process taking it between the same equilibrium states.)
66 An inventor claims to have developeq an engine that takes in 108 J at a temper
ature of 400 K, rejects 4 x 107 J at a temperature of 200 K, and delivers 15 kilo
watt hours of mechanical work. Would you advise investing money to put this
engine on the market?
(a)
As a function of
T and V.
68 An ideal monatomic gas undergoes a reversible expansion from specific volume
v1
to specific vo l ume
(a)
(b)
(c)
v2.
(a)
(b) What are the corresponding changes of entropy if the process is a free
expansion?
610
(a)
cv
(b)
T(iJsfiJT)v.
3
bT for
aT +
a metal at low temperatures. Calculate the
Assume that C0
variation of the specific entropy with temperature.
=
(a)
(b)
(c)
Cv
T
dT
+ R In
(V
b)
+ S0
Chap. 6
106
612 When there is a heat flow out of a system during a reversible isothermal process
the entropy of the system decreases. Why doesn't this violate the second law?
==
ca rr ied
Calculate the change in entropy for each leg of the cycle and hence show that
the entropy change for the complete cy cl e is zero.
p
I
isochore r
adiabat
..
..
isobar
7 .I
I 09 .
7.2
TemperatureEntropy Diagrams
I I0
7.3
II I
7.4
I 12
7.5
T he Tds Equations
I 13
7.6
118
7. 7
121
7.8
122
107
aq,
du
(7.1)
Pdv,
or
aq,
T
du
=
T + T
dv
ds.
(7.2)
0, ds
0, s
2
ztq,
1
q,
(7.3)
(7.4)
du
u( v, T)
in general. Since
cvdT. Thus
Sz  St
2
I
Cv
dT
.
109
Chap. 7
110
T2
T1 we have
(7.5)
S. Isobaric process: It is convenient to use the specific enthalpy in an iso
baric process. Since
d/1
du + Pdv + vdP.
(7.2) yields
Substitution in Equation
Assume
==
h(T)
Cp
if
.
.
.
.
Cp
: _ .. , > _
Cp)n
=:
T2
(7.6)
is constant.
dT
.
.
. .
:
.
.
.
state 2 is given by
2
(/,
Ttl,..
This equals the area under a curve in a Ts dtagram. For a reversible iothermal
process Tis a constant and the curve is a horizontal line. For
batic (and isentropic) process. dJ
reversible adia
Consider a Ts diagram for a Carnot cycle (Figure 7.1 ). Recall that a+ b
is an isothermal expansion b
..
compression, and d
an adiabatic expansion. c
an isothermal
gram is a simple rectangle for a Carnot cycle. The area under the curve is
Sec. 7.3
III
Figure 7.1
r)
t

Carnot cycle.
Since f du
T ds
q,2
q,,.
7.2). Thus
dssystem
dssurroundings
==
dsuniverse
But
7lq,
=
T + dT
surroundings
surroundings
( lts ) surroundings
surroundings
T+ dT
Figure 7.2
system
T
dq, > 0
Chap. 7
112
Thus
Ids I surroundings
I tis luniverst!
and
 ! tis ystcm
==
o.
a rev e rs ible
idealized 
processes are reversible; all natural processes are irreversible and entropy is
not conserved in general.
==
ccdT in Equation
(7.2), we have
(7.7)
ds
==
c,.
tlT
T
dv
v
R/v. so
.
+ R In
if
cr
v'"'
(7.8)
if only the volume is varied, the l a rg e r the volume expansion. the greater the
entropy tncrease.
Sec. 7.5
II 3
be a compensating
7.5
Tds
du
Pdv,
(7.9)
''Tds
equations." They
P, v, and T. The
equations are:
(7.10)
av
a
aT
av
The
ferred in
(7.11)
aT
aP
Tds equations
T
and integrating;
(7.12)
dividing by
cJ<
cp
(3)
(1)
K,
be used to deterntine the difference in the specific heat capacities cp and cv;
and
ds
0.
Section 6.7 in the steps leading to Equation (6.26), from which the final result
can easil}' be found. Here we shall derive the second
the derivation of the third as a problem.
Let
du + Pdv.
Chap. 7
114
+ Pv, so that
du
dh  Pdt\  vdP.
Thus
Tds
dh  vdP
rill
=
CIT
dT +
or
ds
With s
ah
iJT
ah
aP
dT
P
dP.
(7.13)
s ( T, P). we have
ds
as
=
dT
aT
as
aP
dP.
(7.14)
1

aT
ah
(7.15)
AT
and
as
iJP
ah
riP
(7.16)
v .
a2 s
as
iJT
p T
aP aT

aT aP
as
iJT
aP
T p
we get
1
a2h
a2h
T iJP aT
av
T aT aP
ah
v.

iJT
aP
Sec. 7.5
liS
ah
=
iJP
T
av
iJT p
v,
(7.17)
(6.26).
cp. Using this and Equation (7.17)
For a reversible process, (ahjiJT)p
=
dP.
Finally, since
(avj iJT) P
v{3, we have
T ds
Tds
cP.T.  vdP
RT
=
dP.
Then
T ds
q, =
P2dP
 RT
P,
J'
 RT In
P2
}'1
Cp dT  Tvf3 dP
Solving for
dT
dT, we get
TJ3
dv
K(Cp  Cv)
cvdT
dv.
(7.18)
Tv/3
dP
(Cp  Cv)
aT
av
dv
P
aT
dP.
aP v
Chap. 7
116
Thus
aT
T{3

and
Tv{3
= ( cP c )
ciT

aP
Solving the first equation for
l'
cp  ell
or
(7.19)
Cp
(aTIaP) l: gives
cv
the quantities on the righthand side of the equation are all positive, showing
that
cP
cP
ct.
c r
9.5
Cp
29
c,.
103 J kilomole l K
1 ..
{3 = 6.5
10
V
n
nz
np
63.6 kg kilomole 1


X 103 kg
8.96
m3
7.1
Hence
Cl,
and
2
101 Pa1 The specific volume in m3 kilomole1 can be found
v =
C1
Cp
= 29
2
Tv{3

103
29
3.2
X 10 
103
( 100()) (7.1
26
 
9.5 x
x
I012
lW J kilomole1 K1
117
Sec. 7.5
This highternperatttre value is very nearly equal to 3R, a result that will be
explored in detail in Chapter 16.
.
Finally, we consider a reversible adiabatic process ds = 0. Equation
(7.12) gives
Cp_dv =  C,J< dP
f3
{3v
(7.20)
'
or

OV
iJP
=K
Cv
Cp
Ks = V
Since 'Y
>
1,
Ks
<
av
aP

(7.21)
c=
1

pK
(7.22)
'
where p is the density of the gas. The adiabatic compressibility is used since the
process of compression and rarefaction takes place very fast; there is no time
for heat to be exchanged with the surroundings.
Using Equation (7.22), we can estimate the speed of sound in air. If air is
c=
:::=:
;;;
1.4,
K ::=
1/P
=:::
1.2 kg m 3 Thus
1.4
l/2

340 ms1
Chap. 7
118
:>
.
.
::::.
.
.
.
.
.
.
.
. .
.
_...;
. ::
allowed to come to thermal equilibrium with the reservoir. The process is irre
versible since there is a finite temperature difference; the process cannot be
reversed by an infinitesimal change. We assttme that the process is isobaric. Then
"IF
u
reversible
in suh a way that the body passes through a series of equilibrium states. Then
llq,
ds =
== c 1,
dT
so that
T.,

bodv
.
.
"'
TJ
...
.
.
. .
Q
T..,

.
.
( 12
.
.
:
.
..
.
.
r, )
>
.
.
..
. .
.
..
.
.
..
.
.
. .
. .
'
.
.
.
. .
.
.
.
.
. ..
..
..
.
.
.
.
. .
.
\ rervoir
surroundings
.
.
==
system
Sec .. 7.6
119
while
cp(T2 T1).
Now
( S ) universe
( S ) body
( S ) reservoif'
or
(7.23)
It is easily seen that the entropy of the universe will always increase, whether
T2
>
T1 or
T2
< T1 Let x
Taking the derivative of f(x) and setting it equal to zero shows that the func
tion has a maximum or a minimum at
x =
ltl the example, the increase in entropy of thf! body is larger than the
decrease in entropy of the reservoir and the entropy of the universe is greater
at the end of the process than at the beginning. In all real changes, the entropy
will always increase; in other words, entropy is created in the process. The addi
tional entropy is an onus that the actual universe must bear. For an indefi
nitely expanding universe, there is no known process that can cause the
entropy to decrease.*
To illustrate the calculation of entropy changes in irreversible processes,
we consider the following examples.
EXAMPLE
Suppose that 0.5 kg of water at 90C is cooled to 20C, the temperature of the
surrounding room. The specific heat capacity at constant pressure of water is
*
However9 a universe that expands without limit is different from a finite. closed system.
There is no final equilibrium state and energy conservation may not apply.
Chap. 7
110
1
4180 J kg1 K The change in entropy of tl1e system (the water) is the change
293K:
(S)system
r aQ,
r!
mer
dT
=
7,
mcp
In
363K to
T,
i
1
The entropy of the system decreases. The change in entropy of the surround
ings is equal to the heat transferred to the room divided by the temperature of
the room, which remains constant. The sign is positive since the heat flows into
the room:
T
nzcr
dT =
mcp
363 293
Therefore
(4s)universe =
(S)system +
(.\')surroundings=
EXAMPLE2
==
TL
Qr

TH
Q,
TL
( s) reservoir H

( s) reser\'oir
4 X l(t5
4 X 105
500
200
 +
= +
/.
1200 J K I .
Note that if the two reservoirs are at tl1e same temperature .. no heat is
exchanged and
(AS)
erse
un i v
0.
Sec. 7.7
Free
Ill
EXAMPLEl
A 5 kg mass falls to the ground from a height of 50 m;The temperature is con
stant at 20C. 'The process is irreversible but we can imagine the mass being
slowly and reversibly lowered by a string and pulley arrangement. Since no
heat exchange is involved,
( 4S)system
0, but
W,
mgh
We note that for the surroundings, which are ttnchanged if the mass is small,
T(S)
Q,
U + Wr
0 + mgh.
0 and llq
0 so
P0
RT0
=
Vo
and
constant or P0v0
the free exp ans i on because P1 is initially zero and the process is irreversible.
vacuum
gas
(a)
Figure 7.4
(b)
Free expansion of an ideal gas: (a) initial state; and (b) final state.
Chap. 7
Ill
ds
Cv
dT
T
+ R
dv
V
' y I
=0
so
( ds)svstem
.
v1
R ln
(7.24)
'
Vo
and
( ds) universe
(7.25)
u1,
Since du
0,
w,
RT0 In
v,
'Vn
q, so that
..
.is
q,
=
Tu
R In
vJ
Vo
In a free expansion no work is done but the change in entropy in the irre
versible process is as if work
were
( P1
=F
7 .8
v = v0[1
first approximation,
(7.26)
Problems
Ill
(7.27)
Setting
av
iJT
'llQ
. {)IJ'
we obtain
Integrating, we have
 voP(P  P0).
s
(7.28)
The entropy increases if the temperature increases and decreases if the press ure Inc reases.
PROBLEMS
71 The latent heat of fusion of ice at a pressure of 1 atm and ooc is
3.348 x 105 J kg1 The density of ice under these conditions is 917 kg m3 and
the density of water is 999.8 kg m J. If 1 kilomole of ice is melted, what will be
72 Ten kg of water at 20C is converted to ice at l0C by being put in contact
with a reservoir at l0C. The process takes place at constant pressure. The
heat capacities at
constant
pressure of water
and
ice
lOS J kg1
73 Calculate the change in the entropy of the universe as a result of each of the fol
lowing processes:
(a) A copper block of mass 0.4 kg and heat capacity 150 JK l at l00C is placed
in a lake at l0C.
Chap. 7
124
(b)
The same block at l0C is dropped from a height of 100m into the lake.
(c) Two similar blocks at 1 ()(r)C and 1 ooc are joined together. (Hint: See
Problem
(d)
78.)
74 Suppose that the specific heat c a pa city cp of the body discussed in Section 7.6 of
the text is 10 J kg1 K 1 and T,
kg.
(a) Calculate the change in entropy of the hody and of the reservoir if
T.,
..
(b)
400 K .
==
100 K.
e x pa
(a) th e gas?
(b) the universe?
76 An ideal gas has a specific heat given by
c,.
==
stants. Show that the change in entropy per kilomo1e in going from state
( o1 T1)
..
to state ( lh T.,) is
..
;ls
A In
t
I
8(1
Td + R In
v,
l' I
'[I
+
1
] \
__
:
2\/T1 T
(b)
Show
th a t
.s > 0 fo r any
finite
temperatures T1 and T.
(Hint:
79 Tw o identical blocks of copper are held at constant vo l um e with a constant hea t
capacit y CF
380 J K 1 One is at an initiat tempe ra ture of 320 K the other at a
temperature of 280 K. The two h1ocks arc thermally isolated and placed in con
=
tact with each other. What is the entropy change of the system?
..
Problems
125
710 (a) Assuming that P and v are independent, show that in a reversible process,
as
Cv
=
aP
iJT
and
iJP
as
av
cp
ar
ri'lJ
(b) Use these results to derive the third Tds equation (Equation (7.12)).
711 Use the first Tds equation to calculate the entropy for a van der Waals gas.
712 Calculate the difference in the spe.cific heat capacities cp  cv of copper
4.9 x 105 K1, K = 7.7 x 1012 Pa1, and v = 7.1 x 103
at 300 K. Take {3
m3 kilomole1 How does your answer differ from the result of Section 7.5?
=
713 (a) Show that the difference between the isothermal and adiabatic compressibilities is
K K.\' =

Cp
riP
dK

iJT
.
p
dV
Cv
iJT
aP
v
cp
(T/3 1).
(c) Using these results,find 11 and 1L for a van der Waals gas and show that both
are zero for an ideal gas.
716 Calculate the velocity of sound in liquid He4 using Equation (7.22). T'.ke
y = 1.48, p = 162kgm3,andK = 9.43 x 108Pa1.
717 (a) The temperature of a block of copper is increased from T0 to T without any
appreciable change in its volume. Show that the change in its specific entropy is
.:1s =
Cp
In T,
vo{32
(T
 T0).
;;.
:;::; ::
.
;
:'...::.::;. .:.;
:
:
;
::
:
::::
:;:.
:; ::::::::
fiX
:;
: :
:
IC
8.1
Introduction
129
8.2
130
8.3
132
8.4
134
8.5
134
8.6
136
8. 7
137
8.8
142
8. 9
143
127
.
.
.
.
.
.
.
.
8.1 INTRODUCTION
In the context of the first law, we have defined two functions of the state vari
ables with the dimensions of energy: the internal energy U and the enthalpy H.
Since neither of these is well suited to the analysis of certain processes, it
will be convenient to introduce two additional functions the Helmholtz
function F and the Gibbs functio11 G. Because of their role in detertttining the
equilibrium states of systems under prescribed constraints, they are known as
(8.1)
TdS  PdV.
and
 P, V.
Note that T and S are thermal variables, whereas P and V are by nature
mechanical variables.
In Equation (8.1) \\'e assume U
dU
au
\ as
U(S, V) so that
dS +
v
au
av
dV.
(8.2)
au
as
=T '
au
av
P.
(8.3)
129
Chap. 8
130
Thermodynamic Potentials
..
d Z ( .r y )
X tl .t + Y d y.
(8.5)
Z xX y},P.
(8.6)
Then
tiM
.\
dX
 v liY.
Since. by Equation (8.5) the first three ter1ns on the righthand side sum to
zero, we have
{/NI
= .r
dX
dY .
(8.7)
a
function of one
pair of variables to the other. Equations (8.5) and (8.7) gi ve recipr(JCity rela
tions as follows:
az
ax
==
az
X.
ay
aM
aM
ax x.
aY
lJne
==
 Y
(8.8)
( 8.9)
N(.r_ Y)
)'Y.
(8.1 0)
Sec. 8.2
Ill
Then
dN
dZ
Y dy  y dY
X dx
dY,
y
(8.11)
X'
aN
aY
=

(8.12)
y.*
The equations of transfortnation, Equations (8.6) and (8.1 0), may look
mysterious at first glance. Howe\'er, they are based on a very sirnple idea: a
curve in a plane can be equally well represented by pairs of coordinates (point
geometry), or as the envelope of a family of tangent lines (line geometry), as
ZN
=
y
0,
*It is note\\'Orthy that in classical mechanics. the transfonnation from the Lagrangian to
the Hamiltonian is
cegendre transfortnation:
Chap. 8
Ill
Thermodynamic Potentials
or
dY  Y dv.
.
Y dj', so
But dZ =
dN
vd}"
.v = 
dN
dY
(}', Z) space to a
8.3
Since
dU
=
TdS
P)dV.
(8. 1 0):
Z=U,
Equations
X=T
t=S.
Y=P.
v==V_
N=H.
Sec. 8.3
Ill
H = U + PV,
dfl=TdS+VdP,
aH
OH
aP
(8.13)
=V
2. Next we replace the thennal variable ..in the function U(S, V) by its
conjugate variable T. This leads to a new potential, the Helmholtz func
tion F. The Legendre transformation is
U(S, V)+ F(T, V).
With the identification
z =U,
P ,
X =V,
y = T,
S,
N =F,
F
dF
OF
U ST,
= P '
av
(8.14)
P dV S dT,
OF
aT
= S.
v
Z = U,
T,
x =
S,
y =V,
Y =  P,
G.
OG
iJT
= S '
P
OG
aP
=V.
r
(8.15)
Thermodynamic Potentials
Chap. 8
134
Tt/S
au
P)dV
riS
au
dS +
dV.
riV

av as
==

av

.:=:
aP
iJS
\'
t.
av
a.s
. .
'
is known as a Maxwell refa1ion. I t s utility lies in the fact that each of the par
tials is a state variable that can be integrated along any convenient reversible
path to obtain differences in values of the fundamental state variables
between given equilibrium states.
A summary of relationships involving the thermodynamic potentials,
including the MaxweJI relations, is presented in Table 8.1.
reve rs ible
......
So> 0.
Sec. 8.5
TABLE 8. I
135
Thermodynamic
Independent
Reciprocity
Maxwell
Potential
Variables
Relations
Relations
T=
S, V
lntemal energy
as
av
aP

as
a2u
=
av
'
au
P
dU = T dS  P d'l
ar
au\

av as
F= U TS
P
dG = SdT + V dP
U TS + PV
as
s
=

riP as
aP
as
aF
ar
av
ar
V=

av
ar
aG
aP

T
av ar
av
as
aG
liP
a2F
aF
=
a2H
aP
S= 
T,P
Gibbs function
=
S dT  P dV
aP
aH
S=
T,V
dF
as
V=
dH = T dS + V dP
U + PV
Helmholtz function
T=
S.P
Enthalpy
av
ar
riH
ar
a2G
aP ar
H  TS
where S is the entropy change of the system and So is the entropy change
of the reservoir. If the reservoir transfers heat to the system, then
So
Q/T and therefore,
=
<
T S,
where the equality sign applies if the process is reversible. If we substitute this
in the first law expressed in the form
.
W
AU +
Q,
we obtain
W
or, since F
<
dU f. T S,
TS,
W
<
(no change in n.
(8.16)
Chap.8
136
Thermodynamic Potentials
the maximum energy that can be freed in an isothermal process and made
available for work.* The function is therefo re often called the HelmJtoltz free
energy. (Elsewhere it is frequently given the symbol A. an abbreviation for the
German word for
work, Arbeit.)
If the system held in thermal cont act with the rese rvoir has a uniform
pressure throughout its volume and the latter is also held constant, then the
work performed will be zero and
(8.17)
(8.18)
where i and f denote the initial and final values, respectively. Hence, if the
Helmholtz function is a minimum, any change in the state of the system would
increase
F,
equilibriun1 in
(8.19)
with Fa minimunz. S ince T and V are the most convenient fundamental state
variables for the purposes <)f statistical Jnechanics, as
we
properties.
wi th
P :!1 v.
Actually. it is not necessary that the temperature remain constant during the process: it is
T.
Sec. 8.7
137
reverstb
_ le.
Co1nbining these expressions, we hav
e
&U + P V
T AS < 0.
Since
G
U + PV TS
'
( AG)r.P
<
0,
(8.20)
or
(8.21)
Spontaneous processes occur in the direction of decreasing
G.
A system in
thettnal contact with a heat and pressure reservoir moves to a state of mini
(8.22)
0.
aG
P).
(8.23)
The decrease in the Gibbs function is equal t<.l the maximum energy that can
be freed in an isothermal, isobaric process and made availabJe for nonmechan
ical work. Again, T and Pneed not be fixed tltroughout the process; they need
only have the same initial and final values.
Table
8.2
processes.
Consider a system consisting of the liquid and vapor phases of some sub
stance in equilibrium at temperature T and pressure P. Let n'{ be the number
of kilomoles in the liquid phase and n'i' the number of kilomoles in the vapor
Thermodynamic Potentials
Chap. 8
138
TABLE 8.2*
processes.
Valid
Valid
Equilibrium
Equation
Inequality
Condition
dU :S 0
dll 0
dF s 0
dG :50
dS 0
L'
Minimum H
finimum f'
Minimum (j
State of System
or Type of
Process
dS
dS
tiT
dT
71Q dU
V constant
Sand P cons ta n t
T and V constant
T and P constant
Sand
==
==
Adiabatic
dV 0
dP 0
dV
0
dP 0
+ P d\1'
=
==
Minimum
MaximumS
___;.
.1
......
.
_
'
.
. . .
____
._...
_....
.: . . . . .. ..
.
.
. . . .
.
.
n.,
..
...
..
.
.
. .. . .
.
.
::._::. . .. . .:.: ..: : . .
.
.
.
..
. . '. 
. : .:.'. .t: . .
.. '
.
' .
.. .
:
.
..
:. . . . :
' . .
.
Figure 8.2
,.
..

. :
;.
.
..
'
'
..
..
. ..
. .
..
.
.
.
.
.
.
. .
'
. .
.
.
. .
. : . .
(a)
(b)
n]', n'(').
}' +
j"
== n
2' .
(8.24)
''
"'
We define g and g as the specific Gibbs functions of the liquid and vapor.
respectively, associated with the particular substance under investigation.
Noting that the Gibbs function is an extensive variable. we have for the two
states:
G1
G2
== 11
' g
,,
=: n
"
+ n
+
tg
"'
,,,
,,,
112 g .
(8.25)
(8.26)
is that
section 4.3: one. t\VO. and three prim es denote the soJid.liquid.
and vapor phases. respectively. Here 1 refers to the initial state and 2 to the final state.
t
The notation
used in
Sec. 8.7
139
liquid
dP
Figure 8.3 Relationship
between temperature and
pressure for a iiquid and vapor
in equilibrium. The derivative
dPIdT is the slope of the
vaporization curve.
vapor
""
dT
Suppose that a reversible transition takes place from state 1 to state 2. Since
( G)r,P
G1
G2. Equating
Equations (8.25) and (8.26) and using Equation (8.24), we find that
g"
g'".
(8.27)
The specific Gibbs function is the same for the two phases. This is true for all
phases in equilibrium, that is, for all points on the curve of the phase transfor
mation (Figure 8.3).
Since at a temperature 1' + dT and a pressure P + dP we still have
equilibrium, it follows that g" + dg''
Equation (8.27), we have
dg"
g"'
dg'" .
Using the expression for the differential previously derived, we can write
s
"
dT +
"
dP
"'
s
dT +
'"
v
dP,
or
"
"
( s '  s ) dT
(v
"'
 v
"
) d P.
Thus
dP

dT
s"'
=

"

"'
 v
"
(8.28)
Chap. 8
140
Thermodynamic Potentials
(8.29)
where t23 is the latent heat of vaporization. Since heat is absorbed as a liquid
becomes a vapor, f23 is positive and
Equation
(8.28) gives
dT 23
"'
> s
'
v"
(8.30)
(liquidvapor).

T ( v"'
This is the famous ClausiusClapeyron equation. It gives the slope of the curve
denoting the boundary between the liquid and vapor phases, that is the vapor
ization curve. Similar expressions hold for the sublimation and fusion curves:
dP
dT
dT

T(v'''
1.1
dP
13
12
v')
f12

"
T ( t'
v')
(solidvapor),
(8.31)
(solidliquid).
(8.32)
The latent heats in these expressions are positive, and the slopes are all posi
tive for substances that expand on melting. A notable exception is water,
which contracts when ice melts into liquid; for this case
( dPI dT) 12
< 0.
curves. A simple example is the vaporization curve describing, say the conver
sion of liquid water to stea m Here
.
dP
dT .,,
:=:
....
(see Chapter
f 2.1
"'
t'
v "'
::::::=
RT

p '
so that
dP
dT
::...:::
t23 P

R T2.
2) and so
Sec. 8.7
141
(8.33)
where
(T0, P0)
T( v"  v')
dT
t12
dP.
T(v"  v')
=
f12
v''
and
v'
gives the change in temperature as the pressure is increased from the low
value at the triple point
(Prp
3.34
liP
Patm  Prp
1.01
105 Pa
610 Pa
::::
1.01
105 Pa.
Then
AT
273(1.00
103
1 . 09
3.34
103) (1.01
lOs
lOS)
..
0.0074 K.
The presence of dissolved air in a mixture of ice, and water further lowers the
temperature at which ice melts by 0.0023 K. The total reduction of temperature
below the triple point of water is therefore 0.0097 K, or approximately 0 01 K.
..
P0 exp
Chap. 8
141
Thermodynamic Potentials
T dS.
namely, T and P:
S(T, P).
Then
dS
as
ar
as
aP
dT +
p
dP.
r
0, and
'
dP.
ap
'
as
riP
iJ\'

 
a1
..
Thus
l/Q,
T
av
iJT
dP.
r
riV
aT
nR

,)
P '
and
p
Pn
Sec. 8. 9
143
If P > Po, the negative sign indicates tltat heat flows out of the system in the
process.
f ( x,
1.
y)
fxx
2. D
>
0,
where
(In
fxy
this
for example,
1.
Suu
2. D
< 0,
Suu Svv
(Suv )2
>
0.
dS
Su dU
Sv dV
I
=
dU +
dV.
T
(8.34)
Thus
Su
1
=
'
Sv
(8.35)
'
T
4th edition, by S.
L.
Salas and
Chap. 8
144
Thermodynamic Potentials
Then
riU
Suu
iiT

r.,
Since
au
Cr
riT ,.
"
it follows that
(8.36)
The temperature Tis always positive. Therefore the first condition for
ity, Suu
<
0 implies that
stabil
..
(8.37)
Now let''s take the
tion (8.35):
Svv dU
Sl't: dV
where D Suv
dT
dP
Cramers rule:
V
d
tiT
f2
(8.38)

D tlV
Svu

T

dP
(S"'u

Suu
P)
dT
"'T
Sec. 8.9
145
Then
iJP
T '
or
D=
Suu
aP
av
Now
av
1
I(
aP
'
and
(8.39)
Since Cv, T, and V are all positive, the second condition for stability, D > 0,
implies that
{8.40)
I(> 0.
Cv
iJV
aP
> 0.
r
Thermodynamic Potentials
Chap.8
146
PROBLEMS
81 A van der Waals gas and an ideal gas are originally at the same pressure, tem
perature .. and volume. If each gas undergoes a reversible isothermal compres
sion.. which gas will experience the greater change in entropy?
(a) f
C0(T
To)
c]
In
To
.
(b) g = c,.(T
T0)
c,.T In
 RT In
Vo .
p
+ RT ln p,
'
soT.
s0T.
83 A cylinder contains a piston on each side of which is one kilomole of an ideal
gas. The walls of the cylinder are diathermal and the system is in contact with a
heat reservoir at a temperature of 0C. The initial volumes of the gaseous sub
systems on either side of the piston are 12 liters and 2 liters. respectively. The
piston is now moved reversibly so that the final volumes are each 7 liters. What
is the change in the Hemhohz potential? (Note that this is the work delivered to
the system by the reservoir.)
(b) Cr
U + T
aF
ar
T
(reversible process)
.
(c) H
G

(d) C,
rJG
aT
a 2G
T
2
ar
p:
(reversible process):
10.)
n2a
=
where J is a function of T only. Derive an expression for the pressure of the gas.
C.
nRT lnP
A + BP
CP2
2
DP3
+ 3 .
Problems
87
147
RT ln
 AP.
Po
88
(a)
(b)
(c)
(a)
A van der Waals gas undergoes an isothetrnal expansion from specific vol
v2
function.
(b)
t't
and v2
using the cyclical and recipirocal relations (Appendix A) and the identity
az
ay
ax
ay I oz
iJx
1.
810
(a)
Prove that
Cp
(b)
811 ln Figure 2.2 depicting the isotherms for a van der Waals gas, the shaded areas
were shown by Maxwell to be equal. The path
along which liquid and vapor are in equilibrium. Prove Maxwell's result by not
ing that Ag
812 The Pv diagram in Figure 8.4 shows two neighboring isotherrns in the region of
a liquidgas phase transition. By considering a Carnot cycle .between tempera
tures T and T + d1. in the region shown, derive the ClausiusClapeyron equa
tion
dP/dT
f23/T(v).
Here
vis the
and liquid.
813 The equations of the sublimation and the vaporization curves of a particular
material are given by
In
In
0.04
0.03
6fT
(sublimation),
4/T
(vaporization),
148
Chap. 8
Thermodynamic Potentials
T
.
. .
.; .
.
. .
. ....
T
Figure 8.4
P v diagram for
dT
.
.
. .:...
. .
. ..
.
= const.
..
.
. . . ..
. : ...: . . .. . ..
.
.
.
.
.#
..
..
.. .
. .
.
.
= const.
'
 
t'
phase is much larger than the specific volume in the liquid and solid
phases . )
e
en
9 .I
lSI
9.2
Phase Equilibrium
ISS
9.3
157
9.4
Chemical Reactions
160
9.5
Mixing Processes
162
149
Until now we have confmed our discussion to closed physical systems, which
cannot exchange matter with their sutToundings. We turn our attention in this
chapter to open systems, in which the quantity of matter is not fixed.
Suppose that
kilomole of added matter has its own internal energy that is released to the
rest of the system, possibly in a chemical reactio11. The added energy is propor
tional to
potential.
The chemical potential is associated with intertttolecular forces. An elec
trically polarized molecule experiences a Coulomb attraction when it is
brought into the vicinity of another such molecule.* 'Ibis force is expressed as
a negative potential energy, a sort of "potential well." As the new particle
approaches its neighbor, it gains kinetic energy while losing potential energy.
The kinetic energy is imparted to other particles through collisions, so the sys
tem gains internal energy in the process.
Consider a motionless molecule infinitely distant from other molecules.
Its kinetic energy and potential energy are both zero. The molecule is moved
into the force field of a second molecule. This can, in principle, be done slowly
so that the kinetic energy is negligibly small. Left by itself, however, the mole
cule picks up kinetic energy equal in magnitude to the depth of the potential
well (Figure 9.1). Quantitatively,
E=K+V (r),
where E is the total energy, K is the kinetic energy, and V(r) is the potential
energy; r is the distance between the molecule and its neighbor. At r = oo,
K=
0, and V
0, so E
0 everywhere. At r = r0,
Chap. 9
152
V(r)
I
I K
I
I
(5.56
7.52
104 J kilomole 1
lnc,T
(5.56
)(7.52
X 10
10')(0.1)
4181.
Since the mass of the water is more than 103 times the mass of the acid .. we can
ignore the heat capacity of the latter. The chemical potentiaL then is
"
,
41X
1())
_
7
4.1 8 x 10 J kilomole
1
_
The sign i s negat i ve because heat is transferred jro111 the acid to the \Vater.
We are interested in the chemical energy per particle, which is essentially
the depth of the potential well. Since a kil()ffiole has 6.02 x 1026 n1olecules.
this value is 6.94 x 10 20 J or 0.43 e\t'. (One electron volt is equal to
1.6
=
Ttl'
P dV
J.Ldn.
(9.1)
Sec. 9.1
Here
153
dn is
the increment of mass added (in kilomoles) and J.L is the chemical
iJS
dS
au
OV
V,n
dV
S.n
U (S, V,
au
dn
n)
and
(9.2)
dn,
S,V
then
iJU
J.L=
an.
(9.3)
s.v
That is, the chemical potential is defined as the internal energy per kilomole
added under conditions of constant entropy and volume.
If there is more than one type of particle added to the system (say
types), then Equation
(9.1) becomes
dU
TdS  PdV +
j=l
J.Li
(9.4)
d nj,
with
(9.5)
The subscript nk means that all other n's except ni are held constant.
Another way of seeing the relationship between U and J.Li is to integrate
Equation
(9.4). This
Af(x, y, z)
(9.6)
at
yay
(9.7)
then
at
f =X
ax
at
.
Z
az
U(S, V,
n1
nm)
Suppose the amounts of all the types of substance, called constituents, in the
system were doubled or halved or, more generally, changed by the factor
without changing any of the fundamental state variables. Then the extensive
variable U would be changed by
Chap. 9
154
au
au
+ v
as
\"
111
rlv
,/l 1
,= 1
s"
iJU
lli
rin,
(9.8)
, v.fl J..
)'
.
V.nJ
iJU
T ..
av
=
I
au
..
s.v.n ..
S.n,
= J.lj .
(9.9)
ST PV +
Jl;n;.
..
(9.10)
r= I
==
ST + PV It is
111
(9.11)
If only one constituent is present .. then G
==
p.11 or JL ==
Equating Equations
Ill
SdT VdP
+
(= I
11;dJ.L,
0..
(9.13)
(9.11) gives
Note that
G(T P n1
..
..
(9.14)
.
.
(9.13)
Sec. 9.2
Phase Equilibrium
155
(9.14)
result
(9.15)
.
.
.
.
.
.
.
.
..
.
.
'
nA
n8
VA
V8
UA
U8
=n = constant
= V =constant
=
constant
(conservation of mass),
(9.16)
(conservation of volume),
(9.17)
(conservation of energy).
(9.18)
The total internal energy is constant, according to the first law, since no heat
flows into or out of the combined system and no work is done. At equilibrium,
the entropy of the combined system will be a maximttm:
SA
S8
dS
(maximun1).
(9.19)
dS.4 + dSB
0.
phase boundary
(9 20)
.
156
Chap. 9
But
(9.2 1 )
and
(9.22)
We can eliminate three infinitesimals by invoking Equations
(9.18):
Combining these ex pressions with Equations (9.21) and (9.22), and substitut
(9.23)

Since Equation
ar b i t ra ry
increments
PA
J.L 11
PH
(thermal equilibrium) ..
T8
(9.24)
J.L B
( diffusive tquilibrium)
(9.25)
(9.26)
Then the entropy of the combined system \l:ill not have reached its max i mum
value bu t will still be increasing:
(9.27)
Consider a state very close to an equilibriurr1 state and differing from it only in
that there is a small excess of mass 'zA(>O) in s ubsystem A over the equ i l ib
rium value
nA,
d11A in subsystem B. As
Sec. 9.3
157
(9.28)
Simultaneously, the entropy change of subsystem B as a result of acquiring the
additional mass will be
(9.29)
or
(9.30)
Thus, in the approach to equilibrium, heat energy must flow from the
hotter to the cooler body, volume will be gained by the body under lower pres
sure at the expense of the other, and mass will tend to flow from the body of
higher chemical potential toward the one of lower chemical potential. All of
these tendencies follow from the second Jaw of thertnodynamics.
We note the
following:
1. Only one gaseous phase can exist because of diffusion .
.
*The symbol
here
with 3.14. .
1r,
158
Chap. 9
Let P.l be the chemical potential of the ith constituent in the yth phase.
According to Equation (9. 1 1) the G i bbs functi on is
(9.31)
where n? is the number of kilomoles of the ith constituent in the yth phase.
For equilibrium
(dG)r.P
1L?
dn?
..,..
0 1 and P fixed.
i=] y=l
(9.32)
It also follows from the GibbsDuhem equation (Equation (9.13)) that for
constant temperature and pressure.
(9.33)
t=J y= I
constituent is transferred from one phase t(> another with the total 1nass of the
constituent unchanged.. then

"
dll?

:=:
0, i
(9.34)
1, 2. . . . k.
'Y = 1
(y
cr,
(9.36)
.
(9.37)
Since the differentials dn1u and in2o are arbitrary, the coefficients must vanish.
Hence
(9.38)
Sec. 9.3
159
In other words, the equality of the chemical potentials for the two phases of
each of the constituents is the condition for equiljbriutn with T and P fixed.
From the conservation of mass it follows that the number of kilomoles of
each constituent is fixed provided no chemical reaction occurs. Thus
(9.39)
where
n1
and
n2
and 2,
. .
(9.40)
(9.41)
Therefore, in our example of k
2, 1r
by four independent variables: T, P, x1a, and x2a. tlowever, since there are two
equilibrium conditions ( Equation (9.38)) , the ttumber of variables is reduced to
two.
The generalization of this specia l case leads to the socalled Gibbs phase
rule. For a multiconstituent, multiphase system with T and P fixed, the condition for equilibrium is
II. Q
ri
ll.f3  ll. y
ri
 ,.,
J.L/r'
1' 2,
k.
( 9 42 )
7T.
(9.43)
xY
l
n;y
i= 1
'
1' 2 ..k;
.
1'
1' 2
...
,,Ir
Thus, there would b k1r k ilomole fractions were it not for the identity
k
x?
i
(9.44)
1,
which subtracts 1r kilomole fractions from the total. Counti ng the two prescribed
auantities. T an d P. there are therefore 2 + k1r
1T
Chap. 9
160
and k ( 1T
==
[2
J)l
or
1r +
(9.45)
==
variable is specified.
Consider the following examples:
1. A homogeneous fluid with one constituent and one phase. Here k
71'
1,
2,
r.
I, f
T, P. and
1,
7T
==
2,
water; specification of either Tor P gives the value of the other variable.
4. Ice, liquid water, and water vapor in equilibrium. Here k
1,
1T =
3,
0. The three phases can coexist in equilibrium onJy for the fixed set
As we have noted, the chemical potential is a measure of the chemical energy per
kilomole that a substance can generate in a reaction. Chemical thermodynam
ics involves, in part, the measurement of th e chemical potentials of compounds.
A chemical reaction is usually described by an equation, such as
(9.46)
Such an equation can be generalized
as
(9.47)
Sec. 9.4
Chemical Reactions
161
which states that a certain number of molecules of the initial reactants will com
bine to yield a certain number of final product molecules. Here the Mi denote
chemical symbols and the vi are socalled stoichiometric coefficients. The coeffi
ciettts are positive or negative integers; negative values represent initial reactants
and positive values correspond to final products. Thus, in the previous example,
and
vn,c)

+ 2.
For a chemica! reaction to occur, more than one substa11ce must be present
either initially or fmally. The number of kilomoles ni of each of the constituents
will change in a manner consistent with the conservation of atomic species. In
the example, for every two kilomoles of hydrogen and one kilomole of oxygen
that disappear, two kilomoles of water will appear. The change in the number of
kilomoles will therefore be proportional to the stoichiometric coefficients:
(dG)r.P
0, so that
where the j's are constants. Finally, since dnioc"i' we can write
(9.48)
This relation can serve as a check on the measured values of the individual p,'s.
Chap. 9
162
interdiffusion
takes place at constant temperature and pressure.. so that the Gibbs function is
again a central concept in the description of the process.
Dalton's law of partial pressures states that the pressure Pj of the jth con
stituent gas of a mixture of gases is given by
(9.50)
where xi is the kiJomole fraction of the jth constituent gas defined in Section 9.3 ..
and Pis the pressure of the mixture.* Equation (9.50) is a definition of the par
tial pressure; the relation foiiO\\IS immediately from the ideal gas law for which
nRT
1
v
:=
nRT
v
since then
l!liaat
. tl
,
p.
J
p
11
'
where gj is the specific Gibbs function for the jth constituent. To calculate the
specific Gibbs function for an ideal gas we start with the first law expressed in
the forrn
Tlls
With
v =
cpdT
vdP.
RT/P, we obtain
ds
= c
dT
T
dP
Rp.
We omit the superscript on the kilomole fraction because there is only one phase in this
process. Here
Ln,
J
n.
Sec. 9.5
Mixing Processes
16]
Integration gives
s
Cp In T  R In P + s0
Since
g
= u
+ Pv
Ts
Ts,
and
it follows that
g
cpT  cpT ln T
Kf In P
Ts0
h0,
or
g
RT(ln P
cp),
(9.52)
(9.53)
where
gli
RT(ln P +
</>1),
Ku
RT(In P +
cPz),
so that
(9.54)
Figure 9.3
: initial state
T,P
T,P
diaphragm
(a)
final state f
T, P
P1
P2
(diaphragm removed)
(b)
Chap. 9
164
Although c/>1 and c/J2 are functions of the same temperature T, the functions
themselves are different because
Cp
with
Since T doesn t change in the mixing process, c/>1 and c/>2 will be the same for
the final state as for the initial state. Using P1
g11
g21
x1P and P2
x2P, we obtain
so
G1
n1RT(In P
(9.55)
==
RTin x.
Then
Comparing this with Eq u ati on (9.11) we see that J.L is the chemical potential!
Since g1 and g2 are characteristics of the constituents, they are the same for the
initial and final states and we can drop the subscripts on gin Equation (9.53),
which becomes
(9.56)
Our final result is therefore
G
G,.  G,
nt (p.1
g,) + n2(J.l2
g2)
or
(9.57)
Sec. 9.5
Mixing Processes
165
==
a(aG)
aT
Hence
(9.58)
Clearly
with
so that
and
LlS
nR In 2 > 0.
(9.59)
Sttppose that the properties of gas 1 approach those of gas 2. The pre\'l
ous result gives a finite entropy increase. However, if the two gases are identi
cal there can be no change in entropy when the diaphragm is removed
( LlS
Chap. 9
166
.
.
'
.c
'
.
.
PROBLEMS
==
TdS
PcJV
dn.
+ 11
==
:::
TS
PV
+ JLn.
J.Ldn or equivalently,
aG
J.l
fin
:
r.P
:
li=
dn
f.\
92 (a) E xpress the chemical pote n t ia l of an ideal gas in terms of the te 1n pe rature T
and the volume V.
J.L
==
crT
<,.1 In T
RJ' 1n V
snT
( r. ): use G
.
+ constant.
TS
Gjn.)
(b) S imilarly. find 1L in terms of T and P. Sho\v that the chemical po1entia1 at the
fixed temperature r v aries with press ur e as
J.1. =
J.L
=
JJ..o +
( p\
RT In P,
\\'here J.Lo is the value of J.l at the rcfc_!rcncc poi n t ( P.,. T). This
ex p res si on
is
93 A con t a i ne r of volurne \t' is divided by p artit i on s into three parts containing one
kiJomole of helium gas two kilomoles of neon gas. and t hree kilomoles of argon
.
gas, respectively. The te m pera t ure of each gas is initiaHy 300 K and the pressure
is 2 atm. The p artit ions arc removed and the gases diffuse into one a n other
(a) Calculate the kilomolc fraction and the partial pre ssure of ea ch gas in the
mtxturc.
(b) Calculate the cha n ge of the Gihhs function and the change of the entropy of
the system in the mixing process.
94 Show that for
p ressure P.
;,p
iV
T dP
==

Problems
167
95 A mixture of gold :1nd thallium can exist in equilibrium with four phases pre
sent: solution, vapor, solid gold, and solid thallium. What is the variance? (This
point is kno\vn as the
eutectic point.)
96 The Gibbs phase rule can be generalized to systems in which there occur
chemical reactions:
f
1T
2.
3
02
+
S03.
dP
v

.
T

H.n
(b) For an ideal gas, the entropy S(H, P, n) has the form
S(H, P, n)
where <I>(H,
nR In
<P(H,n)
P
(a) Wl)at is the nev temperature of the system? l11e new pressure?
(b) What is the change in the Gibbs function of the system?
(c) What is the change in the entropy of the system?
99 (a) Show that for an open system with one component,
dG
SdT
VdP
JLdn.
(b) Using this result. calculate G for a van der Waals gas assuming a fixed
amount of material at a given, fixed temperature. Show that
nRT ln(V
nb)
n2bR
2n2a
V
nb V
C(T),
where the integration constant C(1) is, in general, different for different
temperatures.
Chap. 9
168
d In T
L 1
d In p
L x;dJ..l.;
( 7. P constant)
where
X;
d )n
Xl
dIL2

T.P
(c) Show that for a twocomponent liquid phase whose vapor can be treated as
an ideal gas mixture,
.
d In P...
L
d In
x1
r.P
.. d In
x2
r.t
where P1 and P2 are the partial pressures of the components of the vapor,
and
x1
and
x2
DuhemMargules
q ua tio n )
.
ICS
171
174
175
178
'
169
.
.
.
.
. .
_ .;,
.
.
...
.
.
. .
.
.
.
.
.
LAW
Tf1Q
'+So
S=
0 T
(10 1 )
.
absolute zero. In this short chapter we shall introduce a principle that will enable
us to determine
S0 The
1906, is
makes it possi
ble to calculate the equilibrium constants of a chernical reaction from the ther
mal properties of the reactants.
We have seen that a spontaneous process can occur in a system at con
stant temperature and pressure if the Gibbs function decreases. The Gibbs
function is related to the enthalpy by the equation
reciprocity relation
S =  ( aGI aT) p,
G = H  TS.
Using the
GibbsHelmholtz equation:
aGG=H+T
aT
(10.2)
If this relation is applied to the initial and final states of a system undergoing
an isothermal process, it takes the form
(10.3)
171
Chap. I 0
171

.
L.....
which shows that the change in enthalpy and the ch ange in the Gibbs function
are equal at T
ments, Nernst postulated that as the temperature tends to zero .. not only do
llG and llH become equaL but their temperature rates of change approach
zero as well:
A(G)
lim
rt,
AT
()
ri(H)
lim
iiT
T+0
I'
0.
( 10.4)
.....
iiGl
lim
ac1
il1'
T +0
==
aT
0.
( 1 0.5)
where the subscripts 1 and 2 refer to the initial and fi11al states, respectively.
From the reciprocity re]ation we have
J1jm, ( 5' 1
+I,
5 ) = 0.
( 10.6)
hold for all sy ste ms in equilihrium states. (ll1ere arc certain quantum systems
==
lim
T o
lf(T),
(I 0. 7)
Sec. I 0.1
173
and
I.1m iJG
r.o
Ilffi
aT p
ali
aT
r.o
(10.8)
T dG
iJT
<I>= 0.
(10.9)
<I>
Adding the term
a<I>
and
iJT
0,
0.
(10.10)
d<l>
<I>
, aT p
dH
ar p'
or
a<t>
aT p
<I>
T

ctJfT
aH
aT
lim
r_.o
for
aH
aT p
==
0.
( 10.11)
limit of
(10. 12 )
G
lim .a
r.o aT p
Since
(iJGfiJT)p
0
.
(10.13)
T+0
0.
(10.14)
Chap. 10
174
This statement. stronger than the Nernst theorem. needs qualification. Certain
with disorder. and glass is a disordered structure. The Planck statement can be
shown to be valid for every pure crystalline solid. Quantum statistics is necessary for a complete understanding of the absolute entropy of a system.
Still another statement of the third law is:
It is inlplJSSible
(0
..
'
'
. .
.
.
roundings (with no heat flow in or out) and reduce its temperature in an adia
batic reversible process. Then work is done J,y the system solely at the expense
of its internal energy. This can be accomplished by varying some parameter
such as the magnetic field. The process is called adiabatic demagnetization and
is discussed in Chapter 17.
In the 1970s laser coolitlg was proposed a process in which the decelera
tion of a beam of atoms is accomplished t'y directing
laser beam so as to
oppose the atomic heam. Under the action of the laser beam, momentum is
transferred to an atom by absorpti<>n of a photon. The laser light frequency is
chosen to excite the lowest order at(lmic transition. If the laser frequency is lower
than the atomic resonant frequency and the atom is moving against the laser
beam. the laser frequency in the rest frame of the atom is Doppler shifted
,
toward resonance. The key point is that the laser light pushes on , <>nly those
atoms that are moving into the laser beam.

Following absorption , the atom spontaneously emits the photon in a random direction. This absorption and isotropic reradiation result in an average
driving force in th e direction of the incident light. Since the force is pr(JportionaJ
to the velocitv, the atomic ffi(ltion is slov.'ed and the atoms are therebv cool ed .
liquid or a solid.
Sec. 10.3
I O.l
175
By considering the adiabatic reversible process, we can show in a few teps the
equivalence of two statements of the third law. We assume that absolute zero
is unattainable and prove that in a change from equilibrium state
1 to equilib
rium state 2,
(10.15)
where the naught subscript refers to T
TztQ
So +
(10.16)
Now Cv
(71QfdT)v
and Cp
(71Q/dT)p. We assume
S =So+
T dT
0
(10.17)
CT .
We note that the Debye law for the heat capacity of a solid gives Cva.T3 In
this case, S increases \Vith T according to some power law, as Figure 10.2
reflects. The curve S1 applies to an initial value of the variable parameter and
s2 to some final value.
Figure 10.2
Entropy
temperature diagram for a
hypothetical cooling process in
which S1 < 52 (The entropy
curve for the initial value of
the varied parameter lies
below that of the final value.)
____
L
1
I
I
I
I
l
_
____
____
I
I
I
I
t
I
I
T
Chap. I 0
l76
sl
gtves
(10.18)
dT
(10.19)
()
Now, Cis always positive: if it were negative, a heat gain would result in a low
ering of the temperature.. and the attainment of absolute zero would be triv
ially easy!
( 1 0.20)
where
But
T must be zero if
Equation (10.20) is to hold. Thus absolute zero could be achieved through the
adiabatic change from state 1 to state 2 if 50 > S01 This violates the unattain
ability principle. We conclude that
(10.21)
Thus we need to redraw the 5 T di a gram with S02
abat s2
sl gives Equation
r2
dT C, J1 
<
( 10.22)
say T2"
Sec. I 0.3
177
Figure 10.3
Entropy
temperature diagram for a
hypothetical cooling process in
which sl > s2.
  
I
I
I
I
I
I
I
11.

=
r1
T2" T2
So2 >Sot
(10. 23)
The only way that Equations (10.21) and (10.23) can both be true is if
(10.24)
which is the Nernst postulate. According to Equation (10.24) the curves of
2
and S1 versus T must come together at T 0. The final sketch, Figure 10.4,
nicely illustrates the equivalence of the two statements of the third law. The
curves have been drawn to reflect the Planck statement, though the proof does
not place the entropy at absolute zero.
A series of isothermal and adiabatic processes (demagnetizations) are
represented by the zigzag path in the figure. Each successive process reduces
the temperature. It is clear, however, that because the curves intersect at
Chap. I 0
178
any practical method. This fundamental fact of nature should not be espec i al l y
disquieting, however. given that cry(lgenics has enabled us to get ex t re m ely
close to T
0.
1. Expansivit.'
The expansivity (coefficient of volume expansion) is defined as
av
'


iiT
, (J p
I'
lim
/'_,.()
(J

jp
(1
0.
r
'
T +(l
==
0.
( 10.25)
In con n ect i on with any phase change that takes place at low ten1perature
we can invoke the ClausiusClapeyron cquat !_<)n (Section
tl p

8.7):
==
 
lim 5
T+0
0.
,
Problems
179
dP
.
I1m
T +0 dT
0.
(10.26)
The slope of the boundary between two phases is zero at absolute zero.
This has been verified for all known sublimation curves, for the vaporiza
tion curve of Helium II, and for the fusion curve of solid helium.
1
Experimental results show that for solid helium, dP/dT'XT , which
approaches zero at a very fast rate indeed.
3. Heat Capacity
From the definitions of the heat capacities at constant volume and con
stant pressure, we have
Cv = T
as
Cp = T
ar v'
as
ar p
Integrating, we obtain
T
S S0 =
dT
Cv
,
T
0
S S0 =
0
dT
Cp
T.
The lefthand sides of the equations will remain finite down to absolute
zero, where, by the third law, they will vanish. The righthand sides must
behave in the same way. The integrals show that the heat capacities must
decrease to zero at least as rapidly as T. Othenvise the integrals would
diverge because of the lower limit of T = 0. We conclude that
limCv
T +0
0,
lim Cp
T +0
0.
(10.27)
That is, the heat capacities approach zero as the temperature approaches
absolute zero. With respect to this behavior, extensive experiments pro
vide a full confirmation of the third law.
PROBLEMS
101 Show that the heat capacity at constant volume can be written
Cv
It follows that as T
0, InT
X)
as
=
dInT v.
and S
0, so that Cv
0 as T
0.
0, in confirmation of
Chap. I 0
180
102 Show that. in view of the third law. neither the id e al gas equation nor the van
0.
der Waals e quation can hold at T
=
103 (a) Show that the third Jaw cannot prdict the value of the isothermal com
pressibility K at absolute zero. (It remains finite.)
aP
 v av
Show that
riBlim
T o dT
.....
0.
12
c,.
where
c,.
1r.t
 
0.01 K and T
tJD
such a solid at T
.f(\1).
AU.
Cv OasT o.
107 A lowtemperature physicist \\'ishes
to
BT3 As editor of the journaL should you accept the paper for
ases
183
186
188
190
191
193
198
I 1.8 Effusion
201
203
Ill
Nonetheless, kinetic theory yields far deeper insight into such concepts
an
NA
6.02 x
183
Chap. II
184
Take a volume of 22.4 m3, divide it into cubical cells with one molecule in
each ce)J. The volume of each cell (at
3
22.4 m f6.02
is
STP)
<
2fl
0
1
!!:::;
._
are
12

(11.1)
612""
( 11.1)
fd
2 Lh
1.12..
where
E. To the left of the minimum. the curve is very steep; to the
most of the time traveling freely through space. An ideal gas is a good
10
6
\l(r)i.1E
,

Figure 11.1
Variation of the
intermolecular potential V ( r)
molecules.
()
_.,
'

\.
J.o
1.0
1.4
rltl
l.R
Sec. I 1.1
Basic Assumptions
185
. ideal gas law by iess than 0.1 percent. For high density gases, on the ott,er
hand, it is essential to include the intermolecuiar forces, as
is done in the
collides many million times per second with other moecules of the gas
or with the molecules that make up the walls of the container. 'lltese col
lisions are so brief that in our analysis we entirely ignore their duration.
F urtherrnore, the distance a molecule tnoves between collisions can lie
between zero and thousands of times the molecular diameter. However,
he very short and very long distances are unttsual. The average distance
STP, the
process.
the average molecular speed and the probability distribution of speeds are
unchanging.
v +
f(v )dv
1.
v=
vf( v )dv,
(11.2)
(11.3)
Chap. 'I I
186
v2
'
/
I
udt
'
/
/
.
./
/
/
/
'
dA
,_..,.' . +...
'
.......
.....
/cb
<....
Figure 11.2
\'
Sec. 11.2
Molecular Flux
We define n
187
f ( r) dv
dA. Let the velocity of each molecule be represented by a vector, and imagine
that all the velocity vectors are moved parallel to themselves to a common ori
gin (Figure 11.3). Assumptio11 6 states that the head ends are distributed uni
formly in a spherical shell of radius v and thickness dv. The element of area of
the surface of this sphere is
du
v2 sin8
d8 d</J,
with
sphere
Therefore, the fraction of the total number of molecules with angular distribu
tions 8 to 8 + dO,</> to </J + dcp, is
sinO d8 d<P
du

sphere

41T
du
sin8 d8 dl/>
.
nv f(v)dv cos8dAdt
(11.5)
47T
;:s::
Figure 11.3
(a) Randomly
oriented molecular velocities;
(b) the same vectors referred
to a common ortgtn.
dv
(a)
(b)
188
Chap. II
dA dr
411"
Tr/2
sin8 cos8d8
vf ( v) dv
==
<t>
(11.6)
Substituting Equation
<I>
dN
(11. 7)
()
or
(11.8)
where vis the mean speed, defined in Equation
.
.
.
. .
..
(11.2).
Next we consider a single molecule colliding with a surface. The normal com
ponent of the change of momentum is (Figure
mt' cosO
n1v
cosfJ)
1 1 .4)
2mv cos8.
'
v to
in time dt is
2mv cosO dN
mv
cosfJ
ll1'f(t')dvcos6 dA
dt
sin6 dO dQ>

nmdA
=

27T
1
dt
.,
lf. 
v2f ( v )dv
()
tic/>
sin8cos28 d9
()
From Newton's second law and the defi11ition of the pressure P. we know that
dp
dAdt
P.
189
Sec. 1 J.3
dA
6

'
I
l
I
\
I
\
I
I
m"
mv
'
so that
P
We note that
nm
=a
1
nmif.
(11.9)
3
N m/V. Then
PV
1
=
1Vmv
2
=
(11.10)
Nmv
PV
nRT.
(11.11)
no. 0 f k.l
1 omo 1es
no. of molecules
=
N
_
NA'
PV
NkT,
(11.12)
where
(11.12)
will agree
190
Chap. I f
with Equation (11.10). the result we derived from kinetic theory if we make
the association
NkT
==
I
Nmv2 ..
3
or
(11.13)
Thus, the theory has provided a statistical interpretation of the absolute tem
namely the te m pe ra tu re is proportional to the aver
..
age kinetic energy of a molecule. The r esu lt is one of the great insi ghts given to
temperature, the mean kinetic energies of different gases are all the same.
(11.14)
I>
well"' dis
cussed at the beginning of the chapter There we observed tha t E has a mag
.
eV
to ().05
e V.
==
v2,
vY, vz ) .
Then
v2Y + v2,.
ferred directions, so
2
V
2
== V
::_:
2
V
=
I ,
 V".
3
Thus the mean kinetic energy per molecule aSS(lCiatcd with any one component
the xcomponent, for example
I
is
 nzv.;.X
'\
1
 n1v
..
l
=
kT.
Sec. I 1.4
Equipartition of Energy
191
stnce
mv2
2
3 ,
kr
2 ,
(11.15)
.
It follows that the average translational kinetic energy associated with each
of kT /2.
3.
(2)
of the energy of
expressible in
a molecule corre
molecule 8 is f kT/2. It follows that the internal energy of a gas must be the
total average energy of its N molecules. That is,
(11.16).
..
or
1_RT.
(11.17)
From Equation
au
=
d f__RT
T
2
d
Chap. II
192
TABLE
11.1
values
the velocity of so u nd in the gas.
Gas
Gas
co,
He
1.66
H"'
1.40
Ne
l.M
0"
1.40
NH
Ar
Kr
1.67
1.69
f\.,
co
1.40
1.42
CH_.
Air
Cp
fR
2
R. Hence,
c,. +
j' + 2\
R=
is
y=
For
cp
1.29
1.33
1.30
1.40
Cp
C I'
f.
mo n ato mi c gas,
c,.
= iR.
Cp
:;R.
I
'Y = 1 =
1.67 .
...
These results are in good agreement with mfasured values at tem per atures in
the vicinity of room temperature ( Ta ble 11.1 ).
For a diatomic eas..
'
'Y = 7 =
1.28.
Here the agreement is poor: the number of degrees of freedom is too large.
We try

.f
5.
c,.
= 2_R.
c I'
==
7

..
y =
7

==
1.40.
(Jr
C(lnsidered
Sec. 11.6
193
<
}'
<
1.67,
c.,
and
cr
at low temperatures
when
both must
11.6
physi
v1 to v and the
v2
Vr
v2
v]
(11.18)
v2.
v to
1 and 2 per
dv
tionality.
For tlte inverse collisions, the number wili be a' F ( v' 1) F ( v' 2). Because
the velocity distribution is unchanged by the total of all the elastic collisiorts,
the two rates must be the same. A.lso, the collisions will be completely equiva
lent when viewed in
by
M. Sprackling, A1nerican
a'. T hus
Institute of
Physics. New
Chap. II
194
th
..
(a)
v.,
v,
(a) A binary
molecular collision; (b) the
Figure 11.5
(b)
or
(11.19)
Since kinetic energy is conserved and
.,
.,
==
l v 12
..,
.,
v,
we also have
(11.20)
A exp (
 crv
v),
(11.21)
.
where A and
tion. To obtain a
speed
to
v +
selves with their ends at a common point. Since the directions are random, the
velocity distribution has spherical symmetry. 'Therefore N ( v )dv is the number
Sec. I 1.6
195
of velocity vectors whose tips lie \Vi thin the spherical shell between radii v and
(11.22)
The constants A and a can be found from two conditions. The total number of
particles N is given by
X.
N=
N(v)dv,
(11.23)
0
.
(11.24)
To determine
a we
7.
r
t
a
v4e dv
v2N(v)dv
0
by Equation
is
3kT
(11.24)
v2e avdv
2
1
)
8a
1T
(11.25)
2a
2
1
J
4a

..
tJ(v)dv
1T
(The values of the definite integrals are given in Appendix D.) Thus, a
mj2kT.
N (v)dv
N=
(11.26)
47T A
0
Hence
A=
12
1T
In

2rrkT
!t/2
N.
(11.27)
Finally,
N(v)dv
41TN
21rk T
( 1 1 . 28}
Chap. II
196
N( l')
r,
Graph of the
Maxwell speed distribution for
three temperatures:
T3 > T2 > T1.
Fig11re 11.6
some useful average values. As noted in Section 11.1, the definition of the
mean value of vn is
v"
V11j' ( v) dv,
Three
1.
Mean speed:
..
vN('')tlv

2r.kT
8kT
1Tn1
( 1 I .29)

sqttare speed:
The mean square speed is given
41T 
by
1'11
21TkT
3kT_

nz
2. Root mean
47T 
1

.
.
v4enl'.tlv
Sec. I I .6
197
(11.30)
Vm
d
(v2eav)
dv
a=
"
vm
'
m

2kT.
12
, which yields
1
)
a
1/
(
112
2kT
=
112
kT
1.414 m
(11.31)
: V:
V,ms
=
1.414 : 1.596:
1 : 1.128
(m
4.65
1.732
1.225.
X
(11.32)
K,
vrms
493 ms t, which is slightly greater than the speed of a sound wave in nitrogen
gas. Numerical values of the mean speed and root rnean square speed for vari
ous gases are given in Table 11.2.
N(v)
N
0.6
0.4
 ...
6"' ....
+
o
0
Fi
2.0
0.4
0.8
1.0
1.2
1.6
11.7
Chap. 11
198
TABLE 11.2 Molecular
Speeds at 273 K. in ms 1
Gas
v,ms
1690
1210
570
530
450
420
400
1840
1310
620
580
490
460
430
'
There are other speed distributions of less interest to us one is the num
ber of particles whose tcomponent of velocity lies in th e range
vr f()
v.\
dv,
(11.33)
( Fi g ure 11.8). Clearly
vx
vY
I I. 7
We are interested in ho\\' far the molecules of a gas travel bet\\'cen collisions
and how often they undergo collisi<)ns. These concepts are called .. respectively,
the mean free path ( and the coJJisi<)n frequtncy f ..
Suppose that the radius of
R. Then a collision
a =
nei gh bo ri n g molecules were at rest. the nun1ber <)f molec ules with centers in
this vol ume would be
na vr

.
VI

na vr
nu
This answer is only approximately correct hecause we have used the _mean
speed v for all the molecules instead of performing an inte gration over the
MaxwellBoltzman speed distribution. If that is done, and the most probable
Sec. 11.7
199
N(v_r)
  V
The
( 11 34)
;::= ,
nu
7T==
'
which is the correct expression for the mean free path. The corresponding c<?l
lision frequency is
f 
Vm
(11.35)
Note that the mean free path is independent of the molecular speed and
therefore of temperature. Since the nun1ber of molecules per unit volume
!:! is

directly proportional to the pressure, the mean free path increases as the pressure decreases. For an oxygen molecule, 2R
temperature and pressure,n
:;
2.7 X 1025mandvm
=.;
5 7 x los
.
370ms1.Thus
and
The average time between collisions, the reciprocal of the collision frequettcy,
is approximately 1.5 x 1010 s. Note that f is the order of 300R, validating our
kinetic theory assumption that the separation of molecules is large compared
with molecular dimensions.
Chap. II
200
2R
I.
'
'
Figure 11.9
The actual distance that a molecule \\ill travel between collisions is sub
ject to a large statistical variation, independent of time. Let the probability
that a collision will occur in a distance tlx he
collision will

alLt.
not
adx.
dx
will be 1
before making a
Expanding p(:r
have
dx) in
p(J:)
mole
d p ( .'( )
1 ,J.r
lX
p(.r) aJJ(.t)tlx.
or
clp(x)
 
 
tlx
aJ> ( .r ).
Integrating. we obtain
p(x)
To determine the
f(x)
m ean
I d p( .t) I dxI
"'
1 and
that f( .x )
== e
u n it v
ae
ax,
Sec. 11.8
201
Effusion
1.0
p(x)
N
05
No .

0.5
1.5
1.0
xlf.
x=
xf(x)dx=
so that
(11.36)
The probability p(x) can be interpreted as the ratio N I N0, where N0 is
the initial number of particles in a molecular beam, and N is the number of
particles remaining in the beam after a distance
x. Figure
11.10 is a graph of
this socalled "survival equation." We see that the fraction of molecules with
free paths longer than f is
e t
beam of
11.8 EFFUSION
If a container of gas, surrounded by a vacuum, has a small hole in its wail, the
contained gas will leak through the hole into the surrounding space. If the hole
is sufficiently small, the equilibrium state of the gas in the container will not be
appreciably affected. In that case, the number of molecules escaping through
the hole will be the same as the number that would impinge upon the area of the
hole if the latter were not present. The emergence of molecules through the
hole is a process known as
ion.
How small must the hole be? Molecules move unimpeded through a dis
tance approximately equal to the mean free path f. Thus the density of mole
cules at a given point is maintained by the flow of molecules from the surface
202
Chap. II
2
of an imagined sphere of radius { and a rea 47Tf . If the flow from the area A of
a circular hole is to be cut off \Vithout making much of a difference to the mol'
ecular density at the center of the sphere, then A << 47Tf2. Let the diameter of
2
the hole be D. Then rrD2/4 << 41Tf or /.)2 << 16f2.
2
somewhat arbitrarily as D2 < O.l6f or D ( 0.4f. At
atmospheric pressure, e
if the sta t e of the gas in the container is to remain virtually undisturbed. Since
the mean free path is inversely proportional to the pressure, it follows that
there is an upper limit to the pressure for which effusion occurs. Effusion is
essentially a low pressure phenomenon.
In Section 11.2 we found that the number of molecules with speeds in
the range
to
v +
dr that strike a surface, per unit area and per unit time, is
( 11.37)
Here tz,.tlv is the nun1ber of molecules per unit volume with speeds lJetween
and
v +
( 1 l.38)
Substituting this in Equation ( 11.37 )_we have
mv'!2k
.
T d V.
(11.39)
This is the number of molecules that escape through the hole in the container
wall that have speeds from
t'
to
v +
ble values of
l\
1'
ensure that the weighting function used in calculating the mean value is a true
probability density function. Thus
.::t
vp

V4e nzvj2kTdV
vet> v dv
)':
0
X
cl>vdv
3eV
mn;2kT
dV
"'lJ
1J
(J
==
3 21rkT

111
l,i2
( 11.40)
Sec. 11.9
Transport Process\!s
203
Comparing this with the mean speed v of molecules within the container
(Equation
Ve
31i=
1.18v.
(11.41)
This is because the faster molecules have a greater probability of ''finding" the
used to guide charged particles are not ap pli cable to neutral molecules. ) The
based on the fact that the rate of effusion of a molecule is dependent on its mass.
1j_V/4;
(8kTj1riii)112
NkT,
so
n =
N/V
P/kT
and v
<I>
(11.42)
;::==:::=::: .
21rmkT
I I. 9 TRANSPORT PROCESSES
Transport processes involve the re action of
Chap. t I
204
d
'
. .
\'
z=O


z =d
.
.
._.
.
.
0
.
..
.
.
movin g
collision. Hence as it travels along the next free path, it carries a sample of the
properties of the gas in the vicinity of its previous collision. If there are gradi
ents present the properties in the region of its next collision may differ from
those carried by the molecule. During the next collision the molecule will give
up this difference to the gas in the new region. In their motion from one colli
sion to the next, the molecules will couple the properties of the gas at one
point with those at another. The ultimate resttlt is an equalization of the prop
erties throughout the gas.TI1is is the e s s en ce of transport processes.
Consider a fluid such as a gas between two large parallel plates. The
upper plate is moved horizontally while the lower plate remains at rest
(Figure 11.11 ). Since real fluids are viscous the fluid is pulled parallel with
the moving plate. The magnitude of the 11uid velocity
in the l1orizontal
ll
direction changes from the speed of the upper plate to zero at the stationary
plate. In other words, a velocity gradient d1tldz exists in the z direction. per
pendicular to the plates.
Owing to the gradient .. the molecules that are continually moving from
positive values of z are passing through the z == 0 plane.. transferring their
higher momenta in the xdirection t(> the layer below.. thereby increasing the
average momentum <)f the layer. Similarly the molecules moving from nega
tive values of
through the plane are carrying \\'ith them the lower momenta
corresponding to the region where they last underwent a collision. The net
momentum transfer per unit time through unit area gives the tangential stress
P:.x (the viscous force per unit area) .. \vhich a layer below the t)t plane exerts on
..
(11.43)
s em, called a
Transport Processes
Sec.ll.9
205
z
cos
l
I
f
I
I
I
I
I
I
I
I
dy
X
dx
Figure 11.12 Molecule crossing the z
0 plane after its
last collision at a distance e cos8 above the plane.
=
10 poise.
which
(11.7)
(11.8), we obtain
z=
=

(11.44)

Thus, on the average, a molecule crossing, the xy plane makes its last collision
before crossing at a distance equal to twothirds of a mean free path.
If
u(O)
0,
then at a distance
2
e
3
du
(11.45)
Jean Louis Marie Poiseuille. a French anatomist.. was interested in the physics of the circu
lation of the blood. His work on the flow of liquids through capillaries was published in
1842.
Chap. II
206
Here we assume that the gradient does not vary appreciably over the distance
of a mean free path. The momentum of a molecule with this vei<)City in the
.xdirection is mtt(2f/3) and the total momentum transferred across the plane
per unit time and per unit area by a11 of the molecules crossing from above is
1
r .
 n tn v u (0 )
4=
2 lill
.
;; f
, d
Similarly, the total momentum transporte.d per unit time and per unit area
across the plane by the molecules crossing from below is
1
n1n v
4=
u ( 0)
2 du
.
f
3 (Jz
The net rate of momentum transport per unit area is the difference between
these two quantities, or
l
till
 111n v f
d
3
::

.
e 4 ua l to
TJ
J
.
 111111'{.
1
=
( 11.46)
..
b e w ri t te n
==
H/rrna)
I,

we
see
.
T}
1
:..::.
/1r
6'v
mi'
(11.47)
)
1
(con st T
fT
(11.48)
This result may seem surprising. Intuitively, \VC might expect the viscosity to
decrea se with i ncreas ing temperature and to increase with i n creas i n g collision
cross section. But higher temperatures mean higher molecular speeds and a
small cross section means a large mean free path. B oth factors contribute to a
more effective transfer of momentum from one fluid laver to the next and hence
to a higher viscosity. This behavior differs markedly from that of the viscosity of
..
.,
Sec. 11.9
Transport Processes
207
surface involves interaction forces between molecules on the two sides of the
surface as well as molecular motion across the surface.
An especially useful expression for calculating the viscosity is obtained by
solving for n in Equation ( 11.9) and substituting the result in Equation (11.46).

::.::: ( v)2,we
get
')")'=>
.,
11
(1.01 X lo'Pa)(5.7 X
Pf
(P
( 11.49)
=
1.01
8
10 m)
(420ms1)
105 Pa,
273K),
14 X
10 Pa s.
This compares with the measured value of close to 19 x 106 Pa s.TI1e discrep
ancy is due to the approxin1ate nature of kinetic theory, which treats the mole
(11.46) is not to be
taken too seriously, because it depends on how various quantities are averaged.
temperature
gradient rather than a velocity gradient in the gas. The themtal conductivity
results from the net flux of molecular kinetic energy across a surface. The aver
age kinetic energy of a molecule is cvT / NA, where cv is the specific heat capacity
Cv
3ve
_
NA
1T

CvV
(11.50)

lVAa.
It is interesting to note that the ratio of the thertnal conductivity to the viscosity is
A
cv

so that
AM= l
1JCv
'
where M is the molecular weight of the gas. Measured values are closer to 2,
Chap. II
208
free path arguments like those used in the discussion of ''iscosity and heat con
ductivity. The result is
v
Since!!=
2 n(T
(11.51)
1
are proportional to T
..
2,
( const) T3 2
at a fixed pressure an d
( CfJnst)
=

.=:
11
t1n1

17
Experimentally. DpfTI l ie s
in
I.
IIIIII
PROBLEMS:
'
11.1 The distribution of particle speeds of a certain hypotheti cal gas is given by
tv' ( l' )d v
where A and
v.)
are constants.
A ne,.
r..
d v..
Problems
209
(a)
Determine A so that f ( v)
(b)
Find v and
i.e.
; .f ( v )dv
V,m.
(c) Differentiate
1. S ketch f ( v) versus v.
in tem1s of v0
f ( v)
with respect to
Vm.
(d) The standard deviation of the speeds from the mean is defined as
 _), 1/"2.
(
u=
vv 
[ v 2  ( v) 2] J :'2
112 At standard temperature and pressure the mean speed of hydrogen molecules is
1. 70 X 1 OJ ms l. What is the particle flux?
113 What is the number density of molecules at a temperature of 77 K in an ultra
high vacuum at 1010 torr?
114 Compute the
11S Compute the mean energy in electron volts and the rms speed in ms t of an elec
tron at 1000 K. At 10,000 K, what fraction of the speed of light is the rrns speed?
116 At what values of the speed does the iax wel l speed distribution have half its
maximum value? Give your answers as a constant time
117
(a)
N ( X) dX
where x
(b)
(kT,Im) 112
4N
1T
xe',. dX,
.,
vfvm.
Show that the number of molecules with speeds Jess than some specified
speed v0 is given by
)_.X.,
where x0
N er/( Xo )
. xoe
1T
.. 1
a
'
;:=
1T
()
u du.
(c) Find the fractional number of molecules with speeds less than
118 Compute
vm.
119
(a)
(b)
Show that the mean speed of a nitrogen molecule at 300 K is 476 ms 1
Chap. II
110
1110 Find the
rms
free path in terms of the mean free path. What is the most probable
1e
.t'tas
1111 For carbon dioxide (molecular weight 44! molecular diameter 4.6 X 10 10m) at
1 atm and 300 K, find the mean free path f using Equation (11.34 ). What is the
ratio of f to the molecular diameter? What is the collision frequency?
1112 The number density of the gas. mainly hydrogen that fiBs interstellar space is
one molecule per cubic centimeter ( W' m l). If the moleci.Ilar diameter is 10
10
m .. what is the mean free path in interstellar space? What is the collision fre
quency of a hydrogen mo1ecule in collisions per century if the tetnperature of
interstellar space is
10 K?
1113 A beam of oxygen molecules start tog e th er The pressure is 1.8 x 1 OJ to rr and
.
the temperature is
3.6
1010 m. How 1ong will half the molecules remain unscattercd? (Assume
that all the particles have a speed equal to the mean speed.)
(a) Estimate the upper limit of the pressure in the container for effusion to
occur through the hole.
at
1115 A vessel is divided into two parts of equal volume by means of a plane partition,
in the middle of which is a very small hole. Initially both parts of the vessel con
tain ideal gas at a ternperature of 300 K and a lo\\ pressure P. The temperature
of onehalf of the vessel is then raised to 600 K while the temperature of the
other half remains at 300 K. Determin the pressure difference in terms of P
between the two parts of the vessel \vhen steadv conditions are achieved .
1116 A vessel has porous walls containing many tiny holes. Gas molecules can pass
through these holes by effusion and then be pumped off to son1e collecting
chamber. The vessel is filled with a dilute gas consisting of two types of mole
cules that have different masses
nz1
and
nl
two different isotopes of the same atom. The concentrations of these molecules
are c1 and c2 respectively. (The concentration
c,
molecules of type ito the total number of molecules.) The concentrations can be
kept constant in the vessel by providing a steady flow of fresh gas through it so
as to replenish any gas that has effused. If
'
c1
and
'
c:
of the l\\'O types of molecules in the collecting chamber. \\'hat is the ratio
c/ Ic1 '?
1117 Diffusion can be regarded as a random walk prohlem in \Vhich the successive
displacements of a gas molecule are statistically independent. In this model. the
distance IJ traveled by a molecule after N displacements is related to the mean
free path ( by the expression L2
tance L is given by t
Problems
211
distance of 5 meters.
1119 The radius of an air molecule is approximately 1.8 x 1010m, its mass is about
4.8 x 1026 kg, and it has 5 degrees of freedom. The molecular weight of air is 29
and its density is 1.29 kg m 3 under standard conditions.
(a) Estimate the values of the coefficient of viscosity TJ, the therrnal conductiv
ity A, and the diffusion coefficient D under these conditions.
Dp
=
11
1.
12.1 Introduction
215
216
221
223
225
229
213
12.1 INTRODUCTION
The union of the energy and entropy concepts led to a science of therttlody
namics that combines great generality with reliability of prediction. Classical
thermodynamics, however, provides little insight into lvhy thermal phenom
ena occur the way they do.
The object of statistical thermodynamics is to present a particle theory
resulting in an interpretation of the equilibrium properties of macroscopic sys
tems. The foundation upon which the theory rests is necessarily quantum
mechanics. Fortunately, a satisfactory theory can be developed using only the
quantum mechanical concepts of quantum states, energy levels, and intermole
cular forces.
The central idea is the probability density function applied to a large col
lection of identical particles. A thermodynamic system is regarded as an
assembly of submicroscopic entities in an enormous nutnber of everchanging
quantum states. The basic postulate of statistical thermodynamics is that all
possible microstates of an isolated assembly are equally probable.
A few new concepts are needed. We shall use the term assembly to
is the number of
particles that occupy the jth energy level. If there are n energy levels, then
n
....
=1
N.
In general, there will be more than one energy state (i.e., quantum state) for
each energy level, a situation called degenerac}' A microstate is the most spe
cific description one can get. In general, there will be many, many different
215
Statistical Thermodynamics
Chap. 12
216
1L'k
A true prob
.n available to the system. For much of what we shall do, the thermodynamic
probability will be adequate.
N  N1
pare a table listing the possible outcomes of the experiment (Table 12.1 )
Each macrostate is defined hy the number of heads and the number of
.
tails. There are five. For each macrostate there are one or more microstates. A
microstate is specified by the state. heads
\)T
( 12.1)
where
'
k=l
1vk
==
16.
( 12.2)
==
in
I or 2. where N1 is the
number of heads and N2 the number <>f tails. Let Njk be the occupati<>n number
for the kth macrostate. Then the average occupation number is
.
N.J
Njkwk

Ltvk
k
Nj*wk

NikPk
(12.3)
CoinTossing Experiment
Sec. 12.2
TABLE 12.1
217
mics.
TherJnoMacrostate
Macrostate
Label
Specification
Microstate
dynamic
True
Probability
Probability
N.
Coin 1
Coin 2
Coin 3
Coin 4
1/16
4/16
6/16
T
H
T
T
H
H
T
H
.;.
T
4
4/16
1/16
16
Similarly, N2
N.
w
configuration.
Suppose now that we want to perform the cointossing experiment with
a larger number of coins. We need a way of computing the thermodynamic
I'
probability without tabulating the actual state of each coin. We assume that we
haveN distinguishable coins and ask: h<>w many ways are there to select from
the N candidates N1 heads and N  N1 tails? The answer is given by the bino
mial coefficient
N
N!
=

Nt!(N N1)!
(12.4)
Chap. 12
218
Figure 12.1
Thermodynamic
probability versus the number
of heads for a cointossing
Statistical Thermodynamics
This result can easily be seen by noting that there are N ways to pick the first
coin, leaving ( N
However, this counts the N1! permutations of the N1 coins separately. The
ordering of the coins is not important, s<) we divide by this factor, giving
Equation (12.4).
If we increase the number of coins from four to eight .. we obtain the plot
12.2. We see that the smallest value of w is again unity, bt its maxi
mum value has grown to 70 the peak has become considerably sharper.
of Figure
'IVmax
8!
=
4!4!
==
70.
==
(12.5)
and the computation becomes much more challenging. Fortunately, for such
large numbers we can use Stirling's remarkable approximation (Appendix B)
and write
ln n! ::::: n In n  n.
Sec. I 2.2
CoinTossing Experiment
219
50 40
Figure U.2
Therm odynamic
t
10 1
N1
Taking the natural logarithm of both sides of Equation {12.5), we then obtain
In
Wmax
693.
But
log10
x =
(log10 e)ln
x =
0.4343 In
x,
so
log 1 o
Wmax
(0.4343)(693)
300.
Thus
Wmax
10300
(The error in using Stirling s approximation here is extremely small: even for n as
'
small
as
For N
Wmax
as n
gets larger )
.
conclude, then, from our cointossing experiments that the peak in our curve
of thermodynamic probability versus the number of heads always occ u rs at
N/2 but grows rapidly and becomes much sharper as N increases. Also, t h e tails
of the curve always terminate at
w =
for ..'honest" coins, we get ever closer to an exact 5050 split between heads
and tails as the number of coins gets larger. In other words, the most probable
con fig uration
always occurs.
.
Statistical Thermodynamics
Chap. 12
220
10300




ordered region
ordered region
I
1000
Wmax
!l
( 12.6)
'lVm",.
tion with respect to N1 and set the result equal to zero. This wi11 give 1 at
10
u'm ax
and hence N2 The outc<Jmes will then be known for the most prob
able state.
For the thermodynamic probJem .. the outcomes' arc the c,ccupation
numbers for each of n
..
Ni ... N,)
..
possibly subject to constraints.. and set its derivative equal to zero. In this way
we wil1 obtain the particular set { ',.} of occupation numbers corresponding to
the most probable ntacrostate. The most probable macrostate is the equilib
rittm state of the assembly. This is the fundamental problem of statistical thernlo
dynamics
11
many ways can N distinguishable objects be arranged if they are divided into
n
groups with N1 objects in the first group N2 in the second. etc.? The answer is
10 =
N!
N!
'
NI'N'
2 Nn
II
N,!
i =I
(12.7)
Sec. 12.3
111
mation sign
Equation
(12.7)
distinguishable objects in
N!
=
N1
We are left with

N1!(N N1)!.


==
w of
._
w=
N!

N, ! (N  N1 ) !
(N
N1 ) !
N2!'A)!
Xl=
N!
N1 ! N2! N3! .

Th.e constituents of the system under study (a gas, liquid, or solid, for exam
ple) are considered to be a fixed number N of distinguishable particles,
occupying a fixed volume V. Vle limit ourselves to isolated systems that do
not exchange energy itt any form with the surroundings. This implies that
the internal energy U is also fixed. The macrostate in which the system finds
itself is defined by
222
Chap. 12
Statistical Therntodynamics
{Ni}
for an equilibrium
state of the system. That is.. we want to determine the number of particles
Ni
with energy ei for all n energy levels of the system, subject to the restrictive
conditions
ll
"""
j =l
Nj
}l
(conservation of particles).
( 12.8)
(conservation of energy)
(12.9)
ll
1\/iei
j=}
among four energy l e ve l s 0 e.. 2e and 3e, such that the total energy is 3e. Thus
,
..
..
.l
'
LN,
LNje;
and
i::. (I
3e.
f =U
The possible microstates and macrostates are listed in Table 12.2. The
occupation numbers are: N0 particles with energy 0, N1 with energy e_ N with
TABLE 12.2
3. U
3,.; with
t:::1
j. j
0, I, 2, 3.
Thermo
Macrostate
Macrostate
Microstate
dynamic
True
Label
Specification
Probability
Probabilitv
0
0
3e
0
3c
0
()
()
_F.
F.
()
2f
2e
k
t
()
2
3
..,
.)
0.
0
0
o'
0.3
2
0
0.6
0.1
Sec. 12.4
123
3e
a
e
0
k
1
1
1
3
0
1
3
2
6
3
1
energy 2e, and N3 with energy 3s. The total number of microstates is 10 and the
number of possible macrostates is 3. For the most probable macrostate,
the number of available microstates is 6. Another way of displaying the results
is given in Table 12.3, where the occupation numbers are listed for each of the
energy levels.
sor
"di
st
mo
the
t
tha
ent
evid
is
it
ll,
sma
are
e
her
s
ber
num
the
ile
Wh
dered" macrostate is the state of highest probability. For the very large nJm
ber of particles in a physically meaningful assembly, this state will be sltarply
defined and will be the observed equilibrium state of the system.
In classical thermodynamics we have seen that as a system proceeds
toward a state of equilibrium the entropy increases, and at equilibrium attains
its maximum value. Similarly, our statistical model suggests that systems tend
to change spontaneously from states with low thertnodynamic probability to
states with high thermodynamic probability (large number of microstates).
Thus the second law of thermodynamics is a consequence of the theory of
probability: the world changes the way it does because it seeks a state of
higher probability!
It was Boltzmann who made the connection between the classical concept of
entropy and the thermodynamic probability. His argument is as follows.
Assume that the entropy is some function of w, that is,
S
f(w).
(12.10)
HereS and ware properties of the state of the system (state variables). To be
physically useful, f ( w) must be a singlevalued, monotonically. increasing
function.
Consider two subsystems, A and B (Figure 12.4). The entropy is an
extensive property; like the volume, it is doubled when the mass or number of
Chap. 12
224
system
Statistical Thermodynamics
system B
particles is doubled. Thus the combined entropy of the two subsystems is sim
ply the sum of the entropies of each subsystem:
or
( 12.11)
However, one subsystem configuration can be combined with the other to give
the configuration of the total system. That is.
(12.12)
This follows from the fact that independent probabilities are multiplicative. To
return to our cointossing experinlent._ suppose that the two subsystems each
consist of two distinguishable coins. The possible configurations of the subsys
tems are listed in Table 12.4. The. probability of two heads in subsystem A is
clearly 1/4, as it is in subsystem B. From Table 12.1, the probability of obtaining
all heads when fottr coins are tossed is 1/16, which is equal to 1/4
><
1/4. Thus
HH
HH
HT
TH
TT
HT
TH
TT
Sec. JlS
225
..
:..
:..
.
.
.:..
 : ,
.:.
: :
.;
'/::::::. ;:
.
..
. .
.
..
..
. t
..
.
..
.::
.
.
;>
..
U.S
Ludwig
Boltzmann's tombstone,
showing his famous equation.
(lnstitut fur Theoretische
Physik der Universitat
Wien/Central Library for
Physics in Vienna.)
.
..
.
 .: ..r
.
. .
f( WA )
f( Wa )
f( WAWB )
(12.14)
The only function for which this statement is true is the logarithm. Therefore
S =kIn
w,
(12.15)
1
12.5
We have tacitly assumed that the energy levels of our assembly of particles fotin
a discrete set rather than a continuum. This is a consequence of the particles'
confinement in a container of finite volume. Only in the case of completely
_#
226
Chap. 12
l
I
_j
Statistical Thermodynamics
!...._
... JI
L.____.l
83 = 5
Figure 12.6
Hfree" particles can a continuous spectrum t.>f energy exist. To understand how
the discreteness arises, we must resort to quantum mechanics.
In quantum theory to each energy level there corresponds one or more
quantum states described by a wave function '}1. For socalJed stationary
states, ')1 will be a function d e pendent on the position coordinates and the
time.* When there are several quantum states that have the same energy the
states are said to be degenerate. The quantum state associated with the lowest
energy level is called the groLlnd state of the system: those that correspond to
12.6).
C<ln side r
As an instructive example..
mechanics, that of
particle of mass
n1
c X :5
L.)
Within the box the particle is free s u bje ct e< i to no forces except those associ
ated with the walls of the container (Figure 12.7).
ll1e timeindependent part of the wave functi<)n 1/J( .r) is
measure of
.P ( .r)
string with both ends fixed. The "'ave function sa ti s fyin g the boundary condi
tions
t/1 ( 0)
0 and
l/1 ( LJ)
0 is
t/l(.r)
A in k.r, 0
<
.r
LJ.
( 12.16)
with
= II
7i
l.
11 =
J 2 3. .
(12.17)
'I'
is constant in time.
Is
Sec. 12.5
127
00
12.7 A one
x=O
x=L
The boundary conditions simply state that the wave function must vanish out
side the box. The probability of finding the particle there is zero.
Now, the de Broglie relation of wave m!chanics is
p
==
1tk,
(12.18)
(12.19)
important result is that the energy is proportional to the square of the quan
tum number.
We can easily extend this result to the case of a threedimen s i onal box
with dimensions Lx, Ly, and Lz, for which the energy becomes
2
7T21i2 nx2
ny2
nl.
+
+
.
2
2
2
2m Lx
Ly
Lz
In this case, any particular quantum state is designated by three qua n tu m num
bers nx, ny, and nr.. If Lx = Ly = L, = L, then
e
J
(n 2+ n 2+ nZ 2)
X
.V
nJ'
.2
(12.20)
ni is the total quantum number for states whose energy level is et The
energy levels depend only on the values of n/ and not on the individual values
of the integers ( n "' n V' n z) .
where
TABLE 11.5
Energy State
Level
j
j
Statistical Thermodynamics
Chap. I 2
228
Ground state
e. =
1
3
3
..,
3
6
9
(Ll.l)
( 1. 1.2 ): ( 1.2J ): ( 2.1.1 )
( L2.2): (2,1.2); (2.2J)
..
(12.21)
This result applies to a container of any shape whose dimensions are large
compared with the de Broglie wavelength
3 and
nx
n_,.
11
This is the ground state. There is only one set of quantum numbers
(n_,
. ..
that has this energy. Thus the lowest level is nondegenerate and g1
dgeneracy for the first three states is shown in Table
12.5. As
increasing j.
1. Then
n\
..
n::)
1. The
a general rule,
!vj.
Returning to our analogy of shelves with boxes on them, the degen eracy gi of
level j is the number of boxes on the jth shelf. The number of particles in any
one box is the number in a particular quantum state. Those particles on any
one shelf are in different states but have the same energy. Our interest is in the
total number of particles in the boxes at the various JeveJs.. that is.. in the occu
pation numbers
n umb e r II;
for a on e li te r vol

iT2
2m
1 054
2(6.65
X
x
==
1 0 m.Alson
1 0 34
27
10 )
==
1.054
x 1034Js.Thus
e1
kT
( 1.38
23
10 ) (293)
4.04
1011 j
::=::=
2.5
102 eV.
Sec. 12.6
e3
'_....._j
81 l
229
83
==
NJ
Nt
8t
Then
nJ
2.5
;;:::!

X 10
1
2 12
=
to21
X 10
Thus, for the vast majority of the molecules of a gas at ordinary temperatures,
the quantum numbers nj are large indeed. In other words, most of the mole
cules occupy highly excited states. This means that the energy levels are very
closely spaced and that the discrete spectrum may be treated as an energy
continuum. That is the subject of the next section .
12.6
Under the conditions that the quantum numbers are large and the energy levels are very close together, we can regard then's and thee's
as
fotrning a con
n2
n X2 +
nY2
ny, nz
( nx, ny, nz )
+ n l2
8mV213
=
h2
aU positive integers
R2
h/2Tr,
and solv
(12.22)
correspond to points
to
de.
( nx, ny, nz ) lie within the infinitesimally thin shell of the octant of a sphere with
radius proportional to the square root of theenergy (Figure 12.10). Evidently,
g(e)de
dn(e)
n(e +de)  n(e) "'"'
de.
de
(12.23)
Statistical Thermodynamics
Chap. 12
130
Figure 12.9
A crosssection
num bers nx
and ny
./ .
R/
"
_,__
_
.,..
________
11.\
retained only the first two terms. Now n (e) is the number of states cont ained
within the octant of the sphere of r a d ius R; that is,
n(e)
1 4
8 3 7T R
.
1T
=
8m
V h2
3/2
.
3/2
e .
( 1 2 24)
.
so that
g(e)de
Equation
dn(e)
=
de
de=
(12.25)
(12.25) is not quite the result w seek. It takes into account the
cles may have spin as well. The result for g ( e )dr, is valid for bosons of zero
spin (bosons are particles witl1 integer spin). For fermions of spin onehalf
(fermions are particles with halfinteger spin) there are llvo sp in states for
(12.25) by a spin
(12.26)
where Ys
For molecules .. states associated with rotation and vibration mav ex ist

231
Problems
..
'
'
..
.
e +de
.
..
..
Figure 12.10
Shell enclosing
quantum states with energies
between e and e + de.
..
.
..
PROBLEMS
121 Suppose that you flip 50 "honest" coins.
(a)
How many microstates are there? Give your answer as a factor of the order
of unity times an integral power of 10.
(b)
(c) What is the true probability of achieving the most probable macrostate?
Note: Use a calculator that gives you n! or a table of gattuna functions
(f(n + 1)
n!). Stirling's approximation will not give you sufficient accuracy.
=
In n!
n In n
n.
>
10, say. Be
creative.) For what value of n is the error less than 2 percent (approximately)?
124 Suppose you flip 1000 coins. We found that the thermodynamic probability of
getting 500 heads and 500 tails is w = lQ'00 Show that for the case of 600 heads
9
is
smaller
by
a
factor
of
400
tails
w
and
10
ll5 For N distinguishable coins the therntodynamic probability is
w=
N!

N1 ! ( N
(a)
N1 ) ! '
(b)
Show that
Wmax
=::
eN1"2.
Chap. 12
232
Statistical Thermodynamics
126 Consider a model thermodynamic assem hly in which the allowed (nondegener
ate) states have energies 0. r.. 2r.. 3r.. 1l1e assembly has four distinguishable
(localized) particles and a total energy U
6e.
(a) Tabulate the nine possible distributions of the four particles among the
energy levels ne where
..
0 1 ......
n =
..
,;v,
L N 1{'/0
J
..
128 Two distinguishable part i cle s are to be distributed an1ong nondegenerate energy
2.
levels 0 e and 2e such that the tota l energy U
(a) What is th e entropy of the assen1hly?
(b) If a di st i ng u i s h abl e part ic l e \\ith zerc energy is added to the system .. show
that the entropy of the assembly is i nc reased by a factor of 1 .63.
=
..
j(xy)
wher e
f(xl
j(y).
C In
"'
==
c ons tan t .
,
L'.
the de g e neracy g( e)
pressure. Calculate
( 3/2) kT
(take y,
ber of atoms N?
..
dSSICd
an
235
236
238
242
244
246
248
253
254
233
(12.9))
(12.8)
,_,Ni
j=l
N,
(13.1)
(13.2)
Here
U are
1.
N
N1
N!

N1! ( N
N1 ) ! .
We ask: in how many ways can these N1 particles be arranged in the first level?
There are g1 quantum states in the first level, so for each particle there are g1
choices. That is, there are (g1)N possibilities in all. (Suppose that g1 = 2 and
N1
23
choices total
(Figure 13.1).)
Thus the number of ways to put N1 particles into a level containing g1
distinct options is
N
N!g1 ,

Nl ! ( N
N1 ) ! .
235
'1
Chap.
236
Stitte b
State a
123
123
3
12
23
31
13
.,
'
23
31
12
.,
For the second energy level .. the situation is the same, except that there are
only ( N  N1) particles remaining to deal with:
 N'.
g /V 'g N,g N3
II
g '".
'
 '
N.
.
'
N
N)'N2'N3'
j=J
j
1
(13.3)
Having developed the statistics 1v8 for the socalled Boltzmann distribution, our
13.2
...
y)
f ( .x y)
..
df
rif
=
ax
dx
at
av
dv
0.
Sec. 13.2
If
237
iJffiJy
= 0.
However, they are not independent but are related by the constraint equation,
which can be differentiated to give
dt/>
iJc/J
dx +
dy
ax
oy
de/>
=
0.
It follows that
iJffiJx
iJcfJfiJx
iJffiJy
iJt/J/!J y
iJf
ax
iJ</J
a
ax
= 0,
iJf
ay
a, we then have
iJtjJ
a ay
(13.4)
= 0.
f +
a called the Lagrange multiplier; it is the price we pay for the constraint.
(13.5)
be subject to the condition
(13.6)
For a maximum, df
iJf
OX
iJc/>
a
dX
'
1, 2, 3
= 0, l =
n.
(13.7)
'
If there are
(13.2)),
two
a.
cP
.p
(13.1) and
(13.8)
(13.9)
Xn ,
Xn ,
Chap. I 3
138
we must introduce two arbitrary multipliers a and {3. In this case.. we have a set of
n
+ 2 equations
at
 + a
dX;
a
f3:il.ri
..
dX1
0,
1 =
2.. 3 . .
(13.10)
. 11.
Thus the problem is fully specified. The multipliers are often called undeter
mined," but they can be found.
Because In
equivalent to maximizing
Equation
u1.
1v
..
maximizing In
is
(13.3) we have
..
"
In
lV
ln.N!
N.
In
I
...,
II
cJ.
'"''
(13.11)
i= l
safely use
can
In
w =
InN!
(13.12)
+
I
(13.13)
where
(13.14)
.
So
aN.J
(13.15)
Sec. 13.3
239
In working out the derivatives, we note that the only terms of the sums whose
j.
derivatives with respect to are other than zero are those for which i
Therefore, Equation (13.15) reduces to
=
(13.16)
=0
Then
or
(13.17)
Equation (13.17) gives, for every energy level of the system, the number of
particles per quantum state for the equilibrium configuration of the assembly.
The result, obtained under the assumption of distinguishable particles, is
called the Boltzmann distribution function.
The constants a and f3 are related to the physical properties of the
assembly. We consider {3 first. If we multiply Equation (13.16) by and sum
over j, we obtain
or
The two terms on the lefthand side appear in the expression for In
Equation (13.12). Making the substitution, we get
ln
In N! + N aN {3U.
SimpJifying, we have
In
w =
C {3U,
of
240
Chap. 13
k In
1v
S0
(13.18)
k{3U,
dU +
riV
as
av
dV,
g1vtng
as
au
From Equation
T.
(13.19)
(13.18),
( 13.20)
It follows that
{3
.
kT
(13.21)
The association of the classical expression with the statistical expression for
the entropy suggests that the temperature is a Lagrange multiplier!* Note that
the partial derivative in Equation
(13.19)
stant. The constancy of V is implied when \Ye write Equation (13 .2 ) , since
e/x v213 as we saw in Chapter
12.
Substituting Equation (13.21) in Equati<>n ( 13.17), we obtain
The value
_
{3
J Ik T. The
Sec. 13.3
241
so that
a
e =
N

'
and hence
=
1
=
gj
T
k
e;/
Ne
(Boltzmann distribution),

(13.22)
where
energy level.
The sum in the denominator has a special significance. It is called the
partition function or sumoverstates (Zustandsumme in Ge1tt1an), and is rep..
resented by the symbol Z:
,,
z
j=!
T
k
i
,
e
e
.
i
(13.23)
f(e)
N(e)
g(e)
T
I<
/
;
Ne

k
)
/
P.
g(e e Tde
(13.24)
Chap.
241
13
.
:: .: : : :=:
::
: .....:: .: : :
: :.:.  ::.:.:.:. .
. ..:.:
::
::..
::
: :..:
 .:...
.: .:
:...
: ...
: . :
.:
.::
:;::
:. ::.:;.:: ...
:::::
: . :.: : :.:...: ..
....
. .
:
:
..
::
:::
.:
:::. : .;
:
:.....
:
.
::
:
:..:. <
:
::;v
:.::.;
:.
:
::1':..: :
.:
:. :. :.. :
::.:
: .:.:
.::
 .
:
.:
:. ..
: :: .
: .:.
..:
:
:.
: :
:...
: ::.
::::::.:.:.:::.
. .:: : ::.. :
::. ..
: :::
;:::..::: .
.:. ::
::
:
:: :.::
:::.: .:...::.. .:.
:: . .:. ::
:
..:.::
::.;;
: :.:
:;
:.::.<.::.
 .:. : : ...:..:. .::
.
::
..
.
.
.
..
.
.
.
.
.
::
:
.:
:
.
.
.
.
..
..
.
.
.
.

..
.
.
.
,
,
.
.
.
.
.
.
.
.
....
:
:
:..
.
.
.:.. ..:
.:
 ::
.. :
.
.
fl)
indistinguishable, and (2) that they obey the Pauli exclusion principle. This
means that no quantum state can accept ffi(>re than one particle, taking spin
into account. Such particles have halfinteger spin and are given the generic
name
fermion.
N;
<
(g1  Ni)
N; of the states
N1
heads and
N  N1
N!
Here
(13.25)
for the jth energy level. The total number of microstates corresponding to an
allowable configuration is simply the product of the individual factors of the
forrtl of Equ_ation
IJ
To maximize
WFo
gI.'.
(13.26)
} th
energy
lever
Figure 13.2
1 l
___
__,) {
f l
) L.
._I
___.lj 1L...,_..Jj
__
e1
NI
 7
gi
Sec. 13.4
143
wFo
(13.27)
'
'
In wro
(g;
InN;+
g;g;
In
N;
N;
[g;
N;)]
'
[g; In g;  N; In N;
(13.28)
'
'
a(In Wfo )

aNJ.
iJf/1
iJc/J
+a
+
aN:.J
aN.J
0,
1, 2, .
n.
lead to

N.ln N +
iJNI.
'
,__
(g;
N;)ln(g;  N;)
'
+a aN
. N; + f3 aN
'
J
(13.29)
.
'
g; In g;
aN.I
0,
since the g;'s are not functions of the N;'s. Working out the derivatives, we obtain
Ni
l
(gi )
\,
I
or
NI
<'
Chap.
244
13
or
(13.30)
As before, we set
{3
 1/kT.
Lagrange multiplier by summing over the N/s doesn't work for this distribu
tion. Provisionally, we associate
kT,
and reserve for later the physical interpretation of this connection. Thus we set
(13.31)
so that
( 13.30) becomes
(13.32)
(13.33)
Not all elementary particles o bey the Pauli exclusion principle; ph<>tons are
the most notable exception. Thus we need st at is tics for indistingtlishable parti
cles, any number of which can occupy a given quantum state. Such particles
have zero or integer spin and are called
bosons.
this case leads to the BoseEinstein distribution, named after its inventors.
Counting microstates here is slightly more complicated than it is for
FerrtliDirac statistics. For the jth energy level there will be g1 quantttm states
containing a total of N1 identical particles with no restriction on the number of
particles in each state. It is convenient to depict the arrangement of the N1 parti
cles among the g1 states by
(g1
jth
energy
level
Fig11re 13.3
NI = 14
e,.
Sec. 13.5
145
Now, we can obtain new microstates b' shuffling the lines and dots while keep
(+gi
W =
(+gj1)!
!(gj 1)!
level. The
(13.34)


of
number
microstates for a
given
macrostate is,
(+gj1)!
}. g}
j=l
In
WsE
(13.35)
(13.35), we have
=
'
'
w8E
[ ( lV;
g;
1) In ( N;
8;  1 )
 ( N;+ 8; 1)  N; In N;
1)+ (g;1)]
[(N;
+ g;
With the constraints taken into consideration, the method of Lagrange multi
pliers gives
a (In
WeE
a NJ.
+a
dc/J
aN.J
J3
iJfi
aN.1
0, j
1, 2, 3, .
n,
which leads to
iJN1.
l.
( N;+g;
1 )In ( N;+g;
1) I
(13.38)
Chap. 13
246
or
g 
N1
N;
g;
This gives
In
NJ + gJ
Q
= a tJej.
N1
With f3
1/kT and
a =

(13.39)
J.lfkT. we have
(BoseEinstein distribution).
(13.40)
..
(13.41)
DISTRIBUTION
Since elementary particles have halfintegral or integral spins.. the particles of
a gas are either fermions or bosons: they are clearly one or the other.
However, it is useful to consider another kind of statistics pertinent to a so
called dilute gas. The word dilute means that for all energy levels.. the occu
pation numbers are very small compared with the available number of
quantum states (most quantum states
N , << ,.
are
for all j.
This condition holds for real gases except at very low temperatures.
(13.42)
Sec. 13.6
247
(13.43)
Wfo=
Now
gj!

(gj )!
l)(gj Nj)!
._
J
N
so that
(13.44)
The approximate value is slightly greater than the exact value since factors
such as (g  1}, (gi 2), etc. are written as Ki
(gi
Ni 1)!
(13.45)
where
(gj
 1)!
(gj
 l)(gj
 2)... (gj
 )(gj 1)!.
terms ahead of
gfj(gj 1)!
i !(gj 1)!
(13.46)
Chap. 13
248
(13.47)
The much larger Boltzmann proba bility includes the pernltltation N! tlf the N
identifiable particles, giving rise to additional microstates.
The distribution of particles among e11ergy levels can be found by the
usu al method of Lagrange multipliers. However, the result can be written
down immediately by obser ving that
'lVMB
and
1.08
the factor N!. Since maximizing the thermo tlynamic probability involves tak
ing derivatives and t he derivative <>f
Boltzmann distribution
Nj
!'""""'
N e
cJ/kT

(Max\vciiB<)Itzmann distribution).
( 13.48)
conditions. It so happens that the cor responding distribution is the same as the
Boltzmann distribution.
Sec. 13.7
149
(13.49)
Since dei 
Nde
}
J
..,
=
dei
.J dX
dX.
Let
Then
dU
edN
1
I
Y dX.
0 and
(13.50)
dU
TdS YdX,
so that
(dU)x
TdS.
(13.51)
Chap. 13
250
Accordingly,
e dN
J
J
T dS and aW,
aQ,
and
(13.52)
The first equation states that heat transfer is energy resulting in a net redistri
bution of particles among the available energy levels. involving no work. In
Figure 13.4 heat added to a system shifts particles from lower to higher energy
levels.
The second part of Equation (13.52) can be interpreted in terms of an
adiabatic reversible process (no heat flow) in which work is done
ott
the sys
tem (note the negative sign). An increase in the system"s internal energy could
therefore be brought about by a decrease in volume with an associated
increase in the e1 's. The energy levels are shifted to higher values with no redis
tribution of the particles among the levels (Figure 13.5 ).
The relationships of the two parts of Equation ( 13.52) provide a deeper
understanding of the fundamental concepts <>f thermodynamics.
'
'
'
'
'
N,

'
'
'
"
, ..... ....
'
'

'
'
'
'
.... .
'
'
'
'
NJ
'
'
'
'
'
'
'

'
'
'
'
Figure 13.5
Work done on a
'
'
'
Sec. 13.7
251
We turn our attention next to the chemical potential, the quantity appear
ing thus far in two of the distribution functions. In Chapter 9 we saw that when
matter is added to or taken from an open system, the change in internal energy is
dU
(13.53)
where 1L is the chemical potential defined on a per particle basis.* Now the
U T S so that
or
dF
Therefore,
JL
iJF
=
aN
(13.54)
T.V
(13.55)
with
Then
k ln
w =
N,.In
g.
J
1
 k
,_..
(13.56)
*Equation (9.1) is dU
T dS P dV
Chap. 13
252
or
==
u
T
Nk ( ln
In
1)
(13.57)
Then
F
Using Equation
U TS
NkT(ln
In N +
1).
(13.58)
 k T ( ln Z In N + 1) +
NkT
N
or
11 =
r
kT
In
N

( 13.59)
For gases, the partition function Zis proportional to the volume as we shall see
in Chapter 14. Thus /J is an increasing function of both the number of particles
per unit volume and the temperature. This makes sense since particles flow from
higher to lower chemical potential and fr{>rn hi gher to lower concentrations. The
difference in chemical potential is a true potential energy: for two systems it is
the potential barrier that will bring the systetns into diffusive equilibrium.
An example is the coexistence of two r>hases of the same substance
say..
9 we observed that
the chemical potentials for two phases of a given constituent must be equal for
the system to be in diffusive equilibrium. This means that there is no net transfer
.
of particles from one phase to the other: the total number of particles/Vis a constant. This is precisely the condition that allowed
us
eLikT
(13.60)


'
e(t, J.t}rkT.
(13.61)
153
Sec. 13.8
I I 18
I IIIIII II 111M
IU
S
N
IO
T
U
IB
R
T
IS
D
E
H
T
F
O
N
O
IS
13.8 COMPAR
Ni
gi
(13.62)

e<e, p,)fkT +
'
where
+ 1 for FD statistics
a =
1 for BE statistics
0 for MB statistics
For
<<
Figure 13.6.
potential in some sense is arbitrary. When particles are being transferred from
one system to another, it is important to establish a common zeroenergy ref
erence point from which all potential energies are measured. The problem is
exactly analogous to defining a reference level for the gravitational potential
in classical mechanics or for a potential well in quantum mechanics. Thus
ei
p,, the thei"mal energy of a particle, is the energy measured relative to the
lowest point of the potential well. If a particle which itself has zero energy is
inserted into a system, the ensuing interactions with its neighbors are most
often attractive, in which case the chemical potential is negative. When
MB
BE

FD
Figure 13.6 Comparison of
the FD, BE and MB
distributions.
3
2
1
X=
0
ei
1

kT
J.'
Chap. I 3
254
systems are not exchanging particles. we can choose any convenien1 reference
level, which is usuallv taken as zero.
.
1. BE curve: y
1/(ex 1 ) :
.t
for
centrate) in regions
curve: y
For .x 
2. FD
\VC
..
..
x,
i=s
ex.
1/(e
only valid for y << 1. This is the dilute gas r egi on : many.. many states are
unoccupied. Note that
g,.
=
g
,

N;
At high temper at ure s
k1r
( cJ
e AI
( E.
c. ,
C'
{.;;)
<
c. r
els.. and the t endency of mechanical systetns to sink to the states of lowest
energy.. resulting in highl y ordered populatir>ns. For a negativ e chemical poten
tial, Equation
(13.60) gives
to
P
kr
JJ.
kT.
\\'e are
assembly of Nparticles with total energy U. whe re both Nand U are fixed. The
assembly is
con si der e d
Sec. 13.9
255
microcanonical ensemble.
In many experiments the system under investigation is not isolated. In
chemical reactions, for example, the reaction vessel is (lften held at constant
temperature by being kept in thertnal contact with a heat reservoir such as a
water bath that absorbs energy generated in the reaction. In this case it is con
venient to consider an ensemble of
large number
say
NA
of identical
1 assemblies.
The reservoir fixes the temperature of the system rather than the energy. The
individual members of this socalled canonical ensemble can exchange heat
and work with the reservoir and hence the energy of the system can fluctuate.
This is in contrast with the microcanonical ensemble in which there is no inter
action with a reservoir at all.
In spite of this difference, the two et1sembles give essentially the same
results. The reason for this coincidence can be seen as follows. The assemblies
of the canonical ensemble are separate macroscopic objects, like distinguish
able particles, and can therefore be assumed to obey Boltzmann statistics, with
the distribution
N.I
N . e;fkT
gIe
' Z
z
(1 3 63)
=:
The corresponding distribution for the ensemble involves the energy states of
a single sample assembly, whicl1 alone has a very large number of states with a
given energy. The allowed values of the energy E are extremely close
together, so that the degeneracy
g(E)dE,
gi
E and E
becomes N(E)j1VA
energy E. Thus
between
+
=
E/kT
ZA
IX
(13.64)
E,
whereas
En; then
(13.65)
The maximum of
Chap.
256
13
is large and increasing at an astronomically high rate and the other is extremely
small and decreasing. As a result
We are interested in
the mean value
P()
In P(U)
dlnP()
dE
E .:.u
. E=U
( U)
2
U) + .
(13.66)
Here
In P(E)
nln
dlnP()

lnP()

d E2
1
kT.

dE
2
d
 EfkT,
:=.
.....
.
2

2j3N k2T2
Using these values and neglecting terms higJ1er than second orderwe find that
(13.67)
where
3
u 2 :::;:  Nk2T2.
2
(13.68)
This is the usual form of the Gaussian distribution in terms of the standard
deviation
u ,which
P(E).
fractional width
1


Thus for a kilomole of an ideal gas. the deviation from the n1ean value
( 13.69)
U is of
the order of one part in 1013 It follows that predictions of the physical proper
ties of a system using the canonical ensemble are virtually identicalwith those
derived from the microcanonical ensemble in which the energy fluctuation is
zero. When fluctuation effects are important, the canonical ensemble yields
Problems
157
N of parti
cles. As a further generalization, \Ve can consider assembl ies with an indefinit e
number of particles. The resulting grand canonical ensemble is a system i n co n
tact with a reservoir with which it can exchange not only energy but particles
as well. In this model only the mean number of particles is fixed. The grand
canonical ensemble is useful when the constraint of a fixed number of parti
cles is too restrictive, as in the problem of chemical equil i b rium among a num
N particles
with fixed total energy U. The independent variables are V, N, and U The cen
tral concept is the distribution Nil N, the fractional number of p art icles occu
pying the jth energy level. The method is the least abstract of the thtee. It is

mathematically the simplest but is completely adequate for solving the prob
,
1 assemblies.
a diathermal wall with a heat reservoir of the remaining NA
The independent variables are V, N, and T, wi1ere Tis the temperature of the

P(E)
N(E)/NA. The
PROBLEMS
131 Use the method of Lagrange multipliers to solve the following problems:
(a) A rectangle has a base x and a height y, where x + y 8. Find the values of
x andy that give the maximum area.
=
(b)
Find the area of the largest rectangle that can be inscribed in the ellipse
X
az
y2
fj
What percentage of the area of the ellipse does the rectangle occupy?
Chap. 13
258
132 Five identical noninteracting particles occupy the kth energy level, which is ten
fold degenerate. How many possible microstates are there if
U'k,
and work
out the average occupation numbers for the various energy Jevels
(a)
(b)
134 Show that for a system of lV particles obeying MaxwellBoltzmann statistics, the
occupation number for the jth energy l eve l is give n hy
e.I
.1.
135 Show that it is poss i bl e to write the the rmodynamic probability in the general
form
where
+
a =
for FD statistics
1 for BE statistics
0 for MB statistics
136 Substitute the MaxwellBoltzmann distribution function into the equation
Le_;dNi
T dS
to obtain
LdN1
0 and dN1 In
N
'
,
d Ni In
lv;/g1 versus e,
for T
0 and for T
138 Show that for a system of a large number N of bosons at very lo"' temperature
(such that they are all in the nondegenerate lowt!st energy state
chemical potential varies with temperature according to
kT
J..L
r4o

0), the
Problems
139
(a)
259
At room temperature (300 K), what is the equilibrium number of bosons
per state (N ilgi) for an energy ei
(1) 0.001 e\' above the chemical potential J.L?
(2) 0.1 eV above the chemica) potential p,?
(b)
At room temperature
1310
(a)
iJN Jv.v
(b)
IJ.
Alnw=k AN.
T
Consider a system with a chemical potential p,
0, e
300k, and e
600k, where k is
(a)
Calculate the partition function, the relative populations of the energy lev
(b)
k
At what temperature is the population of the energy level at 600 equal to
the population of the energy level at 300k?
>
eo
>
0) is popu
(a)
(b)
U
N
and when T
1 +
e!Jle
A
t
P f;
e
de
o,
ljkT.
0,
)lo )0 ,
(d)
Compute
cv
in the limits T
versus e/kT.
:fkT
e
 
kT
(1

e,;/kT)2
cv
rea
263
265
266
268
269
270
271
273
261
13.7
u
=
Nk (ln Z 
NkT(ln
In
Z InN+
p, =  kT( ln Z  In
N)
1),
1),
(14.1)
(14.2)
(14.3)
To these we can add the other thermodynamic potentials and the pressure.
1. Internal energy
Using the MaxwellBoltzmann distribution function, we can write
(14.4)
with
Z=
(14.5)
aT
kT
(14.6)
263
Chap. 14
164
Since
e(V),
V constant
keeping
az
.,
(kT)
aT :
or
2.
a In z
1VkT2
(14.7)
aT
Gibbs function
The calculation of G is trivially simple; in Chapter 9 we saw that
J.LN
NkT(In Z InN).
Enthalpy
The enthalpy is defined
TS
+ PV, so that G
Substituting Equations
H
as
U + PV and
H
TS_ or
G + TS.
U + NkT, or
H
4.
( 14.8)
Nk T 1 + T
a In z
(14.9)
ar
Pressure
A reciprocity relation from Section
8.5 gives
aF
==
av
r
( 14.2)
with respect to
V with
T held
constant gtves
iJ ln Z
NkT
a\'
(14.10)
Sec. 14.2
265
Suppose that gi
1 and we take e0
0. Then
Suppose that the energy levels are far apart. What does Z look like? For low
'
temperatures, with the ei s differing significantly from one another, the expo
nentials in the series get successively smaller quite rapidly, whereas at higher
temperatures the falloff is more gradual (Figure 14.1 ) The partition function is
a measure of the states available to the system and the distribution gives the
occupation numbers, which are proportional to the factors ee/kT. We see that
.
for low T, essentially all the particles are in the ground state; for high T, the
populations of the excited states are sigitificant.
For a sample of gas in a container of macroscopic size, the energy levels are
very closely spaced and many states are available to the system (Figure 14.2).
It follows that the energy levels can be regarded as a continuum and we can
use the result for the density of states derived in Chapter 12. In Equation (12.26)
we use a spin factor l's
t=lkT
e J
\
\
\
'
low T
'
'
'
'
1\
\
high T
'
'
'
,,
,
,_
.... ....
.
. ... ...
,
' ..
., ,
._,_._,_
...... ......
.... .... __
.._.__ ___,_____...
=__
so
el
(a)
Figure 14.1
e2
ej
:
___._____...._,..
_
...._____
_
60
e1
(b)
83
ei
166
Chap. 14
low T
high T
1
'
'
'
I
'
'
.
.
I
I
I
'
'
I
I
'
E
J
(a)
I
I
I
I
I
I
.
I
'
I
)
I
.
'
'
I
'
'
'
I
I
I
I
I
I
e
1
(b)
Figure 14.2
spin 1/2 particles; that is the quantization associated with the spin does not
apply. Thus
g(e)de
27TV
h3

1'2 l/2d
e.
ml e
(14.11)
Then
Z=
(I
.
This gives the partition function for a gas under the assumption that the
energy levels are so closely spaced that they form a continuum:
(14.12)
Sec. 14.3
In Z
= 2" In T
In V
a In
2 In
2mk
h2
'
V
3 1
2 r

PV
NkT
and
a In Z
iJT
av
267
14.1 gives
3
zNkT.
(14.13)
(3/2)NkT in
Equation
V (21TmkT)312
(14.1), we obtain
(14.14)
3
Nk  In T
2
+ In
S0,
(14.15)
where
S0
Recalling that s
Nk
Cv
2
=
In
ln
R, we obtain
R In
so,
cv
Chap. 14
268
therefore now have two different ways of evaluating the entropy <>f an ideal
monatomic gas. From measurements of the heat capacity at various tempera
tures we can make an empirical detertnination and we can also make a theo
retical calculation by using Equation (14.15). Excellent agreement has been
found of the results obtained bv the two methods. We note.. however that
Equation (14.15) is obviously not valid down to absolute zero since S does not
'
approach zero as T
0.
<< gi. How good is this approximation f<>r gases under average conditions?
where
1z0
2 1rm kT
=
312
h2
has the dimension of the reciprocal of the volume (Z is a pure number) .. and is
called the quantzlm ctJncentratiolz of the gas. Thus we can express the Maxwell
Boltzmann distribution as
N}
gj
N
e
'<JJ /k.T
 r
and T
273 K, so that
N
V
1
 e
n0

J
;kT
6.65
><
1027 kg
The quantity N/V, the number of particles per unit volume, can be f<>und from
Avogadro "s Ia\\:
Sec. 14.5
Since
269
ee/kT,
pied. Helium gas is thus highly dilute under normal conditions. When
we say that the gas is in the
Ni
<< gj,
N(e)de
f(e)g(e)de,
where
(14.16)
energies between
and
(14.17)
where, for an ideal gas,
Z=V
2TTmkT
h2

312
(14.18)
(14.19)
for molecules. Combining these equations we obtain
(14.20)
Chap. 14
270
Here
Ci
 mv2
de
=:
mvdv.
and
N(v)dv
4 N
=
r.
n1
(14.21)
21rkT
This is precisely the result derived in Section 11.6 by using a more heuristic
argument. The various averages discussed there need not be repeated here.
i!18881
8(.
1118
(14.22)
where e is the average energy of a molecule and f is the number of degrees of
freedom of its motion. Thus. for a monatomic gas there are three degrees of
freedom one for each direction of the molecu]e ,s translational motion._ and
Nf:
l'x
is to be associated with
we can \Vrtte
(14.23)
where N(z)dz is the number of molecules with parameter
z +
in the range
z to
Sec. 1..4.7
271
e(z)N(z)dz
e(z)

(14.24)
N(z)dz
where the denominator insures that N (z) is a probability density function. We
note in passing that (z) = UIN.
We assttte that e(z) is a quadratic function of z, that is, e(z) = az2,
where a is a constant. This is certainly the case when eo: vx2 Therefore
Equation (14.24) gives
oc
7r
112
Chap. 14
271
Let's examine the problem from the point of view of statistical thermo
That is,
x1
= Nk/R, so that
x2
= 1.
facto r of
au'=
N!
N) .'Nt
.
N!
(14.27)
the number of ways of arranging the N molecules with N1 in one container and
N2 in the other. The correspt)nding entropy change due to mixing is
S
=k ln
=kIn N!  k ln(x1N)!
A1v
k l n(x N ) ! .
or
(14.28)
Noting that Nk
.lS
k
N
In
=x and x2 = 1
x, so that
(I  x)ln(l  x).
To maximize u. we take
du
dx
=0 = In
Thus xj ( 1  x)
+ I
1 and x
1
=
1
_
ln ( I
 x)
.
x
_
=ln
 .\"
fore a maximum when the two gases are present in equal proportions. This is
Sec. 14.8
Maxwell's Demon
273
tossing experiment.
coin
ELL'S DEMON
14.8
0
0
Fi
Chap. 14
274
gas in B. From the molecular point of view, the higher temperature means a
higher average value of the kinetic energy <)f the molecules in A compared
with those in B. Maxwell wrote 4N<lW conceive a finite being who knows the
paths and velocities of all the molecules by simple inspection but who can do
no work except open and close a hole in the diaphragm by means <>f a slide
without mass.'' Maxwell s beitlg is assigned t<l open the hole in the diaphragm
to let through an approaching molecule in A when that molecule has a veloc
ity less than the
rm.s
cule from B is allowed to pass through the hole into A only when its velocity
exceeds the
rms
ried out in such a way that the number of molecules in A and B do not change.
As a result, Hthe energy in A is increased and that in B is diminished; that is,
the hot system has got hotter and the cold colder and yet no work has been
done; only the intelligence of a very observant and neatfingered being has
been employed." In this way the being vi<llates the second law. 'Only
o
o
0
X
0
X
X
o
.I
0
Maxv.etrs
X
X
Demon
X
X
X
Maxwtfi
Demon later
we
Problems
275
can't," added .Maxwell. "not being clever enough." Kelvin immediately gave
the being the name ''demon" by \Vhich it has been knoNn ever since.
several times it has jumped up and taken on a ne\v character after being left
for dead."* Because of its connection with information theory and computer
science, the subject of the demon continues to generate irtterest. We shall
return briefly to it in the last chapter.
PROBLEMS
141 (a) Calculate the entropy S and the Helmholtz function F for an assembly of
distinguishable particles.
(b) Show that the total energy U and the pressure Pare the same for distin
guishable particles as for molecules of an ideal gas while S is different.
Explain why this makes sense.
142 Show that for an assembly of N particles that obeys MaxwellBoltzmann statis
tics, the occupation numbers for the most probable distribution are given by:
where
(kT)Si2

(b) Forei
(3/2)kT, T
300K,P
103 Pa,andm
1026kg,calculategi/hJ.
144 Calculate the entropy of a kilomole of neon gas at standard temperature and
pressure. The mass of a neon atom is 3.35 x 1026 kg.
145 Calculate the chemical potential in electron volts for a kilomole of helium gas at
27
standard temperature and pressure. The mass of a helium atom is 6.65 x 10 kg.
See
Princeton University Press, 1990. This bock contains a chronological bibliography and reprints of
Chap. 14
276
146 A tank contains one kilomole of argon gas at 1 atm and 300 K. The mass of an
argon atom is 6.63 x to:?tt kg.
(a) What is the internal energy of the gas in joules? What is the average energy
of a molecule in e V?
148 An ideal monatomic gas consists of N atoms in a volume V. The gas is allowed to
expand isothern1ally to fill a volume 2V. Show that the entropy change is Nk In 2.
ea
I I
15.1 Introduction
279
279
282
284
287
288
177
..
15.1
0'>
001!1
)')1>
..

INTRODUCTION
n
u
co
en
e
w
m
le
b
ro
p
y
rn
o
t
h
a
e
lv
so
re
n
ca
el
d
o
m
l
ca
ti
is
at
st
e
th
therefore that
s
di
s
s.
ga
c
o
at
di
a
to
s
jc
arr
yn
od
errn
th
l
ca
si
as
cl
of
n
io
at
lic
p
ap
e
t
in
d
re
te
e
th
t
ve
g
to
tls
fa
gy
er
en
of
on
iti
rt
a
i
p
qu
e
cussed in Chapter 11, the pr inciple of
p
re
sc
di
is
th
of
n
io
at
an
pl
ex
e
Th
y.
cit
pa
ca
at
he
c
ifi
ec
sp
observed value of the
e
th
ing
fac
ge
en
all
ch
nt
rta
po
im
st
e
mo
th
be
ll
to
we
ancy was considered by Max
statistical theory. In thi s chapter we shall see how the problem is solved.
15.2
Until now we have confined our attention to systems of particles that have
translational degrees of freedom only. To deal with particles such as diatomic
molecules, we need to investigate socalled
among them is small. This means that each particle can oscillate nearly inde
pendently of the others. We further assume that eaclt oscillator is free to
v.
given by
(15.1)
Note that the energies are equally spaced and that the ground state has "zero
point" energy equal to hv/2. The states are nondegenerate in that
gi
1 for allj.
applies
. The
280
Chap. IS
(gi
>>
N;)
that the great majority of states are unoccupied, a few are occupied
by a single particle, and virtually none have a population greater than one.
Thus, in our treatment of the internal degrees of freedom of diatomic molecules, \Ve can regard the particles
tum states that they occupy.
as
gJe jkT
j'=O
(15.2)
0
JJv
k .
..
eo 2r
(1
eeflT(1
e;r
+ e
e/T +
+ e
2e1r
+ .
(eetr)2
. .
+ ...
The sum in this expression is just an infinite geometric series of the form
I
which equals ( 1
times
(1
+ y
y i .....
2
2 +
y

). Here
.v
z =
atT
1e
B;i
( 15.3)
..
1 is
.Y)
exp( 0/T) so
e,.
or
with
Ni/ N
(15.4)
Sec. I 5.2
281
()
kT
2T
+
(15.4)
Thus Equation ,
.
1 hv
hv
+
]+2 kT
2kT
hv
j kT
j T.
(15.5)
becomes
(15.6)
A sketch of Equation (15.6) for two temperatures shows that the lower the tem
. perature, the more rapidly the occupation numbers decrease withj (Figure 15.1).
At higher temperatures, more particles populate the higher energy levels.
(15.7)
v
Substituting Equation (15.3) in this equation and carrying out the differentiation, we obtain
1.0
1
Nk6  +
2
0.8
8/T
 1
(15.8)
1.0
9
2
0.8
28
0.6
0.6
NJ
N
NJ
N
0.4
0.4
0.2
0.2
1
(a)
(a) T
15.1
=
(b)
Sec. I 5.3
283
or
(15.9)
At very high temperatures T/8 >> 1 or 9/T << 1 and
2
1
T
That is, the heat capacity approaches the constant Nk. In the low temperature
limit, forT/8 << 1 or 8/T >> 1, we have e81T >> 1 and
so that
2
8/T
The rate at which the exponential factor approaches zero as T+ 0 is greater
than the rate of growth of (8/T)2 so that
Cv
as
0,
consistent with the third law. The variation of Cv wit Tis shown schematically
in Figure 15.3.
k
....
..
N

Cv
...,_ _._.
___.__
..
____
28
Chap. 15
284
T c(<
0 or
kT
<<
hv;
the oscillators
(particles) are Hfrozen "" into the ground state., in that virtually none are ther
mally excited at any one time. We have U
Nhv/2
==
and C\.
0. This is the
extreme "quantum limit.'" The discrete quantum nature of the states totally
dominates the phy sical properties.
At the opposite extreme of temperature for which
hv.
>> 8 or
Cv
kT
>>
hv,
do not involve
U on kT is associated
k T.
The depen
NkT/2
question left unanswered by the classical law is: when is a degree of freedom
excited and when is it frozen out?
The total internal energy of a diatomic molecule is made up of four con.
se e n
..
0 1 2 3 . .
..
..
energy is ( 1/2) 1
..
2
w "
I (I + 1)
.
e,
I (I + 1 )
2i .
(15.10)
Sec. I 5.4
285
(15.11)
so
that
(15.12)
Experimental values of 8rot are given in Table 15.1 for several gases; they are
found from infrared spectroscopy, in which the energies required to excite the
molecules to higher rotational states are measured.
The energy levels of Equation (15.12) are deg\!nerate; quantum mechantcs gtves
g,
(2/ + 1)
(15.13)
For all diatomic gases except hydrogen, the rotational characteristic tem
perature is of the order of 10 K or less. Since these gases have liquefied
8rot (K)
H2
0.,
N2
HCI
co
NO
Cl2
85.4
2.1
2.9
15.2
2.8
2.4
0.36
I
Chap. 15
286
(indeed, solidified) at such low ten1peratures it is always true that T >> Brot at
ordinary temperatures. Hence a great many closely spaced energy states are
excited and the sum in Equation
write
dx
l (l + 1) and treat
(21 + 1 )dl. In this approximation,
Z=
[exp( 9roJT)x]
dx
()rot
(15.14)
H2,
02, and N2 For two identical nuclei, two opposite positions of the molecular
axis correspond to the same state of the molecule. This slight modification has
no effect on the thermodynamic properties
(15.15)
Urot
NkT.
(15.16)
and
Cv.rot
T >>(}rot
N k.
(15.17)
us, at significantly high temperatures, the rigid rotator exhibits the eq uipar
3e 2Bro)T
5e

h#J,.,,/T + .
Since the exponential term is small compared with unitv. we can use. the
approximate relation

In ( 1
c)
e,
<< 1
Sec. I S.S
Electronic Excitation
187
Nk ..,..._ __ _
..
____
_
...
,......
_
_
 __ ._.... _ _ __
Cv. rot
Variation with
temperature of the heat
capacity of an assembly of
rigid rotators.
Fig11re 15.4
28rot
JT.
29ro
3e
Hence
a In z
iJT
28roJT
e
61Vk8rot
'
(}rot>>
(15.18)
and
CV,rot
au
aT
3Nk
1'J
._
rot
28 JT
e n .
....
....
... ... T
8 rot//
(15.19)
as a function of temperature.
(15.20)
where g0 and g1 a re respectively. the degeneracies of the gro un d state and the
,
first excited state, and Be is the energy separation of the two lowest states
divided by Boltzmann's constant k. For most gases, the higher electronic states
are not excited (6e

120,000
Chap. IS
288
'
Cv
==
or
C,
Nk 
(15.21)
Table 15.2 gives values for 8,ih for several diatomic gases.
At the lowest temperatures at which the system exists in the gaseous
the
phase,
(3/2)Nk
molecular
(3/2)1zR
motion
is
solely
translationaL
contributing
( 5/2) nR
in the region 8n,1 << T << 8,.; Since room temperature lies within
this range.. this is the value usually given for the heat capacity of a diatomic gas.
 
TABLE
15.1
Characteristic tempera
H1
02
N2
HCl
co
NO
Cl2
8Jtb ( K;
6140
2239
3352
4150
3080
2690
810
Problems
289
'
'
'
'
., 
I
'
I
I
'
.
'
Cv
nR
4
1
(
I
10
50
100
500 1000
8rot Temperature (K)
5000
Figure 15.5
PROBLEMS
151
(a)
quantum states
IS2
/ N
Nil N
(j
0,
1, 2)
of oscillators
in
(b)
Sketch
(a)
k ln
N.J
N .
Chap. 15
190
(b)
(c)
ln Z.
Nk
Using the expressions derived in the text for U and T, prove that
S
where 8
hv/ k.
8/T
==
N k  8IT

 1
 In ( 1
H1'
e 1
T approaches zero.
(a)
(b)
154 (a) In the low temperature approximation of Section 1544 show that the
Helmholtz function for rotation is
Ff(lt
..
e  8"L/T
3 N kT
law.
155 As an alternative evaluation of Zrot to that given in the text, assume that for
T >> 6rot the numbers I in the sum of Equation ( 15.13) are large compared with
unity and replace the summation by integration with respect to I. Show that
Zrot
T/ (Jro1
r0
..
nuclei.. for
(a)
(b)
an H2 molecule
a CO molecule.
157 Consider a diatomic gas near room temperature. Sho\v that the entropy is
S
312
512
7
V T
2 rrn1k
Nk +In
N
2
h2
28rot
lS8 For a kilomole of nitrogen (N2) at standard temperature and pressure. compute
(a) the internal energy U; (b) the Helmholtz function F; and (c) the entropy S.
159 Using the relation
p
==
NkT
In
itV
show that the equation of state of a diatomic gas is the same as that of a
monatomtc gas.
1510 Calculate the specific heat capacity at constant volume for hydrogn (H2) at
T
2GOO K.
=
fj;fY!i?t
= \),: :\?::::,':/"'
..
16.1 Introduction
293
293
296
291
l!!lliill
'
16.1 INTRODUCTION
'
'
'
'
I
'
f
'
e
t
f
o
le
p
m
a
x
a
is
ic
p
to
is
th
,
15
r
te
p
a
h
C
f
o
t
c
je
b
su
e
densed matter. Like th
cs
m
a
ch
e
m
l
a
tc
s
tt
a
st
r
o
d
e
e
n
e
th
d
n
a
ry
o
e
th
c
ti
e
in
k
l
a
ic
ss
a
cl
f
o
shortcomings
nt
ta
ns
co
at
ty
Ci
pa
ca
at
he
c
ifi
ec
sp
e
th
at
th
ed
rv
se
In 1819, Dulong and Petit ob
t K I
e
ol
m
lo
ki
J
10"
X
9
2.4
y
el
at
im
ox
pr
ap
is
s
lid
so
volume of all elementary
the
d
by
ine
pla
ex
be
n
ca
ult
res
is
Th
e.
ur
rat
pe
tem
om
ro
ar
at temperatures ne
a
lin
as
id
sol
the
of
m
ato
ry
eve
g
atin
tre
by
rgy
ene
of
ion
rtit
ipa
equ
of
ple
princi
ear oscillator with six degrees of freedom and then assOCiating an energy of
3R, in agreement
(l/2)kT with each degree of freedom. Then cv = 6 (R/2 )
=
It was Einstein who developed the first reasonably satisfactory theory of the
specific heat capacity of a solid. He assumed that the crystal lattice structure of
a solid comprising N atoms can be treated as an assembly of 3N distinguish
able onedimensional oscilators (three oscillators for each atom since the
atoms of a solid are free to move in three dimensions). From Equation (15.8),
the internal energy of a solid made up of N atoms is
.
293
Chap. 16
294
U
1
3N kfJE 2
1
/
8
e 1 T
v
ar v
3Nk
(16.1)
8
e ' /T
(J
eBEIT
( 16.2)
1 )2
(16.3)
3nR.
Thus the high temperature limit of Einstein's equation gives the value of
Dulong and Petit. The failure of their law becomes evident when we examine
the low temperature limit. For 8F./T >> 1,
( 16.4)
As T approaches zer(l, Cv
a lso
,
( OE/T).
Einstein s theory also explains the lov.' heat capacities of some elements
at mo d erately high temper at ures. Jf an elen1 ent has a large Einstein tempera
will be large even for temperatures well above absolute
l1vj k must be very large
zero and Cv wil l be small. For such an element (JE
8E/T
..
and accordingl y
and
v =
2rr
( 16.5)
stant. corresponding to lighter elements an(l elements that produce very hard
crystals. The theory correctly predicts the failure of the law of Dulong and Petit
(8:
OE/T. When
to the zeropoint term\ i m ply i n g that all the atoms are in the ground state and
th e vibrational degrees of freedom are not excited ( Equation
cific heat remains close to zero since sm all temperature increases are not suffi
When 8E/T is smalL the difference b e t we en e ne rgi es corr espo ndi ng to various
Sec. 16.2
295
vibrational states is small contpared with thettnal energies. Thus the vibra
tional states can be approximated by
an
classical theory. For values of 8JT between the two extremes, there is a transi
tion region of partial excitations.
A consequence of tlte fact that c,,; N depends
only
2.0
t
1.5 .......
1r'
I kilomole1 Kl
cv
Pb
Ag
Zn
6. Cu
1.0 .....
+AI
0.5
'
0.5
1.0
1.5
2.0
2.5
Figure 16.1
2.5
r
2.0
t
Figure 16.2
104
J kilomole1 K1
c, X
0.5
..,_
Statistical Thennodynamics,
Einstein
1972.)
25
50
T(K)
Tl8e
Chap. 16
196
I" 2 .. 3.. .
n =
( 16.6)
Here A is the de Broglie wavelength and /_j is the dimension of the box. Using
the fundamental equation of \vave motion,
tl
2L
=
v.
('
n =
v.
L3, we get
( 16. 7)
(Figure 16.3).
Sec. 16.3
297
dn
n.{
16.3 A shell of
thickness dn of an octant of a
sphere of radius n.
Let
g(v)dv
to
dv.
Substituting Equation
(16.7)
for n, we obtain
(16.8)
In a vibrating solid, there are three types of waves: one longitudinal with
velocity c1 and two transverse with velocity c1 All are propagated in the same
direction. When all three waves are taken into account, Equation (16.8)
becomes
g( v)dv
4n.Y
3
c,
3
c,
v2dv.
(16.9)
Since each oscillator of the assembly vibrates with its own frequency, and
we are considering an assembly of 3N linear oscillators, there must be an
upper limit to the frequency spectrum. The maximum frequency
vm
is deter
3N
(16.10)
Chap. 16
298
(16.11)
Equation (16.10) provides us with some insight into the cutoff frequency and
wavelength. Since
\:
/\mtn
.
1/3
N(e)
l
=
g(e)

e(tp.)/kT
1.
I I
I I
..
g(v)
...
...
..
,,
3N
g(v)
.
.
. . . ..
. . . . . . :. '.
. . .. .
,
:
:
:
:
.
.
. .. . . .
. .
..,
:
.
.
.
...
.
.
.
.
. . . . 2:
:::. ::.
. L
.
.
. : .
;:
.
.
.
.

. : . . .; : . : : . .: ::
. . ...
... .  .
==:::l. ;: . 
..
.
.
.
:'.
.
.
..
.. .
. .
,,
._
(a)
'
:>
:
.
:.
..
. .
:
..
..
: . . .
... .
:
,
>
'
.
.. :
; ; .:
.'
.
.
::
(b)
Figure 16.4
Jl
Sec. 16.3
299
In this expression the chemical potential J.L must be set equal to zero. This is
because the total number N of phonons is not an independent variable but
N is
0. With e
( aF1aN)r,v, it
hv, we have
N(v)dv
g(v)dv
/kT  ,
h
e
1
(16.12)
"
where
N(v)dv=
v<vm
  
(16.13)
>Jim
to
dv
is
hvN(v)dv
9Nh
=JIm 3
v3dv
"m
/kT
hv
e
(16.14)
1.
(We leave out the constant zeropoint energy since this terrn has no effect on
the heat capacity. Its value is calculated in Problem
162.)
(16.15)
That is, the Debye temperature is proportional to the cutoff frequency
Some values are given in Table 16.1
To obtain the heat capacity, we need to differentiate Equation
with respect to the temperature. Now
d
dT
h
fkT
v
e
hv

h,
fkT
e
kT2 ( eh"/kT
.
l )2
"m
(16.14)
300
Chap. 16
80 ( K)
Lead
Mercury
Sodium
Silver
Copper
Iron
Diamond
88
97
172
215
315
453
1860
Thus
Cv
We let
x =
dU
dT
hvjkT and Xm
9Nh2
( 16.16)
v m 3"Tk :!
hvmfkT
have
(16.17)
.
.r
in the denomina
=e
..,
8o J
T
Hence
Cv=9Nk
T 3 1 Oo J
80
3Nk.
This is the law of Dulong and Petit. For low temperatures 00/T is large and we
can let the upper limit of the integral be infinity. Then
( 16.18)
Problems
301
and
T
6o
(16.19)
relation gives a better fit to experimental data at very low temperatures than
the Einstein model, and is valid for
ture is above the De bye temperature, the heat capacity is very nearly equal to
the classical value 3Nk. For temperatures below the Debye tetnperature,
quantum effects become important and Cv decreases to zero. Note that dia
temperature.
Recent work has centered on the behavior of solids at low temperatures.
3
Experiments suggest that amorphous materials do not follow the Debye T
law even at temperatures below 0.0180. There is more yet to be learned.
PROBLEMS
eerJ2T
=
rr'
E
8
of 3N distinguishable oscillators.
(a)
(b)
(c)
Show that the entropy approaches zero as the tem per ature goes to absolute
zero. Show that at high temperatures, S 3Nk[1 + ln(T/9E}]. Sketclt
Sf3Nk as a function ofT/BE.
16l Show that the inclusion o the zeropoint energy in Equation (16.14) gives a
term (9/8)Nk60 that is added to the integral. Since the terrn is a constant, it does
not contribute to the heat capacity.
163
(a)
Referring to Equation (16.14) and Problem 162, show that the internal
energy of the assembly of pbonons can be written
U
where
D(80/T)
Nk00
g
3NkTD
Oo
T
Chap. 16
302
9n
D
T
(b)


For very low temperatures. the upper limit of the integral can be taken to be
infinity. Show that
1=

15
.
rm
te
by
rm
te
g
in
at
gr
te
in
d
an
.r
e
of
s
er
w
by expanding the integrand in po
n.
ow
kn
l
el
w
is
m
se
su
ho
w
s
rie
se
ite
fin
in
an
The result can be expressed as
Note
(c)
that D( x)
0.
11"
r3
r 4
164 (a) The heat capacity can be expressed in terms of the Debye function
x ex
fll, .'T
(ex
J )2

tlx
cor
0.2
0.4
0.6
0.8
1.0
0.117
0.354
0.496
0.608
0.674
ln Z
==
9
,8o
Hp/T
a
x2
Jn( 1
ex)dx.

9Nk7 In( I
8
o1r
e)
3NkTD(00/T).
166 The experimental value of c,. for diamond is 2.68 x 1{)3 J kilomole l K 1 at a
temperature of 207 K. For diamond the Einstein temperature is 1450 K and the
Debye temperature is 1860 K. Calculate c,. at 207 K using the Einstein and
Debye models and compare the results with the experimental value.
Problems
167
(a)
303
The Debye temperature
80 can
un 
1/3
3N
he
'
where
(b)
Show that

00(K) 
2.51
10
2
1/3
c,
= 2.24
l<Y ms1
Calculate
90.
Pv
where
f(v)
= fu,
(b)
Bv
.
CJ<
Show that
y = 1
fBT,
(c)
f
Assun1e that
80 in the
d ln
00
dIn v
v only and
how that
this definition leads to the result of (a). Hint: Use Maxweil's relation
as
av
aP
aT
t'
.::> :
(\l :;;';;
....
::::_:
.;::::::: ::::::::::::::::
ICS
17.1 Introduction
307
17.2 Paramagnetism
308
315
318
321
17.6 Ferromagnetism
325
. .
lOS
.
:::::::,..:::<.;>.>::::.::.. ::
.
:
..: .: .:
:
::
:
 : :
;
.
: .. :.
. /:: :::
::
:  :: : . > .
llliiil
iiiiBBii
818i!B
17.1 INTRODUCTION
Magnetism comprises phy sical phenomena involving magnetic fields and their
effects on rrtaterials. All magnetic fields are due to electric charges in motion.
On an atomic scale, individual atoms can give rise to magnetic fields when
their electrons have a net magnetic moment as a result of their orbital and/or
spin angular momentum.
Each electron of an atom contributes a m.agnetic dipole that experiences
a torque when placed in an external magnetic field. The phenomenon of para
magnetism results from the tendency of unpaired dipole moments to align
themselves parallel to the applied field. Paramagnetism in solids occurs in com
pounds containing transition metal ions that have either incomplete d shells
(the iron, palladium and platinum groups) or incomplete f shells (the lan
thanide and actinide groups). Both the net spin and orbital magnetic moments
may contribute to paramagnetism, but for an ion with an incomplete d shell, the
effective orbital moment may be "quenched" by electrostatic interactions with
its neighboring ions, leading to a predominant spin moment. Paramagnetism is
therefore due mainly to the spin angula momenta of the electrons.
In an external magnetic field, all the orbiting electrons of an atom speed
up or slow down, depending on the direction of the field. In either case, a
change in each e]ectron's magnetic moment is produced antiparallel to tl1e
field. The effect is known as diamagnetism. It is present in all atoms, but is usu
ally much weaker than paramagnetism.
In ferromagnetic materials, each atom has a comparatively large dipole
moment caused primarily by uncompensated electron spins. Interatomic
forces produce parallel alignments of the spins over regions containing large
numbers of atoms. These regions, or domains, have a variety of shapes and
sizes (with dimensiotts ranging from a micron to several centimeters), depend
ing on the material sample and its magnetic history. The domain moments are
generally randomly oriented, so the material as a whole has no magnetic
moment. Upon application of an external field, however, those domains with
moments in the direction of the applied field increase their size at the expense
of their neighbors, and the internal field becomes much larger than the external
307
Chap. 17
308
field alone. When the external field is removed .. a random domain alignment
does not usually occur, and a residual dipole field remains in the sample. This
effect is called hysteresis. The only elements that are ferromagnetic at room
temperature are iron.. nickel, and cobalt. At sufficiently high temperatures.. a
ferromagnet becomes paramagnetic.
The modern quantum mechanical theory of magnetism was to a large
extent developed by J. H. Van V leck. One C)f the trium phs of this theory is the
remarkable agreement between the observed and theoretically calculated
magnetic moments of paramagnetic salts. "These are the magnetic systems of
primary interest in statistical thermodynamics.
17.2 PARAMAGNETISM
is a
statistical process.
basic ideas are the same for other systems as for hydrogen.
mass. Thus
ett
and
<
m1 <
l.
Sec. 17.2
Paramagnetism
309
The analogous expressi ons for the electron's intrinsic angular momen
IPI
s(s + 1),
=KILn
s < ms <
s'
ll
Vj(j + 1)1i,
f fi  sf + 1, ... ll +
the value mili, where the possible values of mi are

s ,
j, j
1, ... j
1, j.
jp.
(17.1)
(17.2)
J can
J(J
1)
S(S + 1)
L(L
+ 1)
use
(17.3)
an effective spin
S' to
describe the magnetic behavior of the lowest group of energy levels. In this case we may write
fl'l
'
g
p.s
S'(S'
1),
w here g', the effective value of g, is close to 2 for many ions with incomplete d shells. However, we
shall continue to use S and g rather than S'
and g'.
Chap. 17
310
l
p.
H
H
p, X
( 17.4)
B.
The magnetic p otential energy when the dipole is in the angular posi t ion 8
(the angle b e tween B and p,) is the work that must be done to rotate the
dipole from its zero energy p os i t ion fJ
NdO
sin Bd8
J.LB
rr/2
TT
B cos e
( 17.5)
By substituting Equation ( 17.2) in this equation, we get
( 17.6)
the magnetic energy of the atom in the state designated by the quantum num
be r
nz. *
n1 =
B) and
in an energy state
e,,
P,11
that an atom is
ing to that energy level (Equation (13.22)). Since the degeneracy is removed
*
classical argument
to derive
hut Equation
( 17.6) is the
same
Sec. I 7.2
Paramagnetism
311
'
(17.7)
where
Z
(17.8)
m=1
It follows that the mean z component of the magnetic moment of the atom is
(17.9)
with
I
T
Jl"'11Bm/k
e
Z=
.
m=J
(17.10)
We can write the expression for J.Lz more compactly as follows. Differentiating
Equation (17.10) with respect to B, we obtain
,
az
aB T
kT m=J
gJLsmeg8Bm/kT.
Then
kT dZ
P
dB T
kT
d In Z
iJB
(17.11)
kT '
and write
J
Z=
eflm.
m= J
(17.12)
312
Chap. 17
Sett ing
e", we have
J
Xm
X J

X J+ 1
X1 I
:c1
m=1
x2J+'
1
Hence
eJTJ
1  e(:!J + 1 >TJ
1
efl

e11

Z=
<1 + 1/2)71
e
''
1;2)'1
e
I"
12
e TJ.
e"
sinh ( J +
! )11
sinh YJ/2
4.
(17.13)
kT
a In Z
aB
kT
(J + ! )cosh(J
sinh(J +
iJ
11
aB
+
a In Z
d1)
1
)11

!)17
a In Z
cosh(71/2)

sinh(71/2)
Therefore,
(17.14)
where
1
1
J + coth J #
2
2
11
 coth 1J
(17.15)
Figure 17.2.
Sec. 17.2
Paramagnetism
313
J
1.0 1
712
J
j
112
'..._
__
_
_
..._
_
.
....
.
..
Let us examine the behavior of 81 ( 11) for large and small values of its
argument. For 1J >> 1, the hyperbolic cotangent approaches unity and
J+
1
2
1

1,
, >> 1,
(17.16)
l11y + y 3; hence
BJ ( , )
Sd
1
J+2
1
J
1
(J+ !)11
1
1 1
1
1
+ J+ TJTJ
2
3
I 1)
1

31
71
+
2 TJ 6
11
11
1
1+,
12
]2 + J +   
J+l
3
,,
, << 1.
(17.17)
(17.18)
kT,
and
'
KILsB <<
k T.
(17.19)
Chap. 17
314
1) B
( 17.20)
3VkT
1 T, * T
300 K and g
8JLsB
kT
5
(86
. 2 X 10 eV/K) (3



102 K)
2 and J
K. with
Cr2(S04)3
K2S04
erties are due solely to the chromium atoms that exist in the crystal as ions. The
chromium ion cr+
t +
netic moment of 3 J.tB Besides the two chrotnium ions there are 4 sulfur atoms,
2 potassium atoms, 40 oxygen atoms, and 48 hydrogen atoms. Hence there are a
total of 94 particles that are nonmagnetic. TI1e magnetic ions are so widely sep
arated in the molecule that the interaction between them is negligibly small. At
the same time. the effect of the orbital motions of the valence electrons is
quenched by the fields of neighboring ions. What remains is a net electron spin.
The configuration of the chromium atom jCr is
5
( Ar) ( 4s) 1 ( 3d) Argon
3d
produce pragnetism.
the
in the
==
3/2
direction is
..
:
( 17.21)
1 T
*The SI unit
kg/ A
of
the magnetic
s2. Also. 1 T
field 8
104 gauss.
is the tesJa
(T):
in terrns
of
fundamental unit
Sec. 17.3
Figure 17.3
The mean
magnettc moment
tn
l15
Uillts of
Note the excellent agreement between the theoretical result and the experi
mental data.
17.3
The simplst paramagnetic system is an atom or ion with a spin1/2 ground state
and zero orbital angular momentum. Then J = 1/2 g = 2, and there are just two
energy levels. The thermodynamic properties of a twolevel system exhibit the
,
same features as those of more complex systems and are easier to calculate.
For this case, the partition function of Equation (17.13) takes the fortn
Z=
sinh 11
11 =

TJ
.h
SID
'
2p,BB
kT
(17.22)
sinh 11 = 2 sinh
1J
'T1
cosh
in the numerator and canceling one of the factors with the denominator, giving
Z = 2 cosh
where
11
==
2 cosh
kT ,
( 1 7 . 23 )
(17.2 4)
Chap. 17
316
This is Equation
(14.7),
iJT
kT
sinh(ker)

cosh ()"
0
so that
U8
Since tanh(O)
Ne tanh
0 and tanh( x )
( 17.25)
k.r .
Ne at T
ter increases without limit as the temperature increases. Here higher tempera
tures produce increased randomization <>f the dipole moments and the
magnetic potential energy goes to zero.
The magnetic contribution to the heat capacity also has distinctive char
acteristics, given by
au8
iJT
H.N
t:
Nk

kT
.,
sech
(17.26)
kT .
This expression can be put in an alternative form from which the limiting
behavior is more readily seen (Problem
17 X):
e2tikT +
kT
(17.27)
()r

0.5
t
 1.0
Fige 17.4
of a spin1/2
Internal energy
paramagnet.
()
'
kT
Sec. 17.3
317
2e
=:;
kT/B
kT
<< 1,
kT/e
For
efkT in
known as a
>> 1.
the v icinity of unity, the heat capacity has a fairly sharp peak
Schottky anomaly
( 17.28)
Substituting Equations (17.23) and (17.25) in this expression, we get
Nk
In 2 cosh
8

kT
e
kT
tanh
e
kT
( 17.29)
kTje.
At low temperatures,
Cs
Nk
H eat capacity of
_
a spin1/2 paramagnet.
Figtre 17.5
kT
e
Chap. 17
318
s
.'Vk
0.6
t
0.4
t
0.2
I
0
Figure 17.6
Entropy of a
spin 1/2 paramagnet.
f
"'__.___....___.._____._
kT
E
and
e
 tanh
kT
kT
so s
e
I

kT
..
().
..
..
"'
...
....;.(
..
.
. ..
*
.
.
<!...
.,
Sec. 17.4
Fi
Adiabatic Demagnet!zation
319
17.7
Entropy versus
temperature for two values of
the magnetic field B1 and 82,
wjth > B1 The spin systeJn
I
I
I
I
I
I
a constant temperature 1j as
the magnetic field is increased.
When the magnetic field is
reduced to its original value
along the adiabatic path from
b to c, theemperature is
lb
I
I
t
I
I
T
netic field acting on the salt is then increased from B1 to B2 under isothermal
conditions at temperature T;. The spins are in a lower energy state so heat is
evolved and the entropy is lowered. At this point the salt is thermally isolated
so that no heat is exchanged with the surroundings and the field is gradually
reduced from B2 to B1. Since the entropy is constant,
At very low temperatures the heat capacity of the spin system is much larger
than that of the crystal lattice, so the final temperature of the paramagnetic
salt is only slightly greater than T1. Temperatures of less than 1 mK have been
achieved with this technique. The reason a final temperature of absolute zero
cannot be reached is discussed in Chapter 10.
dV
dF
SdT MdB.
dF
iJF
=
ar
dT +
OF
aB
dB.
r
MV). With
310
Chap. I 7
Since F is a state
as
()8
riT
(17.30)
( 17.31)
where. a is a pos itiv e constant. Taking the derivative with respect to T while
keeping
B constant, we have
riS

aB

( 17.32)

'
Hence the entropy always decreases with an isothermal increase in the mag
netic fie l d
Figure 17.7, we
dU
Here it is convenient to letS
T dS
or, for
TtiS MdB.
(15
iJ7'
dT
CIS
aB
dB.
reversible process,
T ds
cRdT +
Setting dS
riS
. iJB
dB,
T
field.
(17.33)
Sec. 17.5
Negative Temperature
321
Because thermal motions tend to disalign the tnagnetic dipoles of the para
magnetic material, the magnetization decreases with increasi11g temperature.
Therefore
as
magnetocaloric effect.
17.5 NEGATIVETEMPERATURE
The twolevel case can be used to discuss an extension of the notion of tem
perature. As noted, the energy of the lower lvel (p, paralll to B) is
B
p.
==:'
e1
ts
to
B)
le
ral
B
tpa
ant
el
(p,
lev
p.8 whereas that of the upper
.
80
n
tto
tta
exc
the
,
2e
ts
B
els
lev
of
n
tio
ara
sep
the
t
tha
so
e,
for
be
as
p.8
e
We set
gap. The number of particles in the lower level e is N0 and the number in the
(17.34)
N,
and
IA.YTO
N

T
/k
e
e '
N1
N
=
/kT
:
.
e
(17.35)
2e/kT
e
,
l
=
2e
k In N0 In N1
(17.37)
Chap. 17
322
in the lower energy state are now antiparallel to the field and in the higher
energy state. Conversely, the magnetic moments originally in the higher
becomes negative!
To be sure, after some relaxation time has passed, the moments in the
higher energy state will flop over into the new lowenergy state and a new
state of equilibrium will be established. But immediately after the field is
reversed, the temperature of the spin systen1 will be negative.
ad
temperature vary with the total energy. The entropy of the twolevel system is
S k ln w, where
=
'U.
N!
=
,"'t,! Nl!
(17.38)
N
2
:=;
NE
N,
1 
1Ve
l + Ne .
(17.39)
(17.40)
( 17.3R), we have
N!
!\'

""
1+
1Vc
'
U/.'Vc, (Problem
1710):
( 1 7 .4 1 )
E videntl y x varies from
1 to
1: in this intl!rval
0 (Figure
17.8).
Referring to Equation ( 17.39). we see that when U / N E =  1, l
N,
a nd N1
0. all of the particles occupy the lower energy level. Similarly. when
1, >
N, the upper level is fully occupied. In both
U IN e
0, and N1
with a maximum at x
==
==
cases T
0.
==
When the particles are equally distrihuted between the two levels, the
Sec. 17.5
Negative Temperature
In 2
s
Nk

323
I
J
I
I
J
I
I
I
I
I
I
r
I
I
I
I
I
I
0.5
T>O
T<O

1
0.5
x =
Figure 17.8
Entropy
as a
0.5
u
iVe
T as a function of x by
usin
g a reci
au
as
Then
as
au
as
Ne
ax
2e
In
1
1 +X
(17.42)
(1)
trum of the system must have a finite upper bound, and (3) the system
must be
energetically isolated from states that are at a positive temperature. The sec
rule
ond condition
Chap. 17
324
3
 
I
I
'
'
2,__
I
I
l
I
'
kT


1

t
1
1 ....
 
 
{)
I
J
2
.
I
I
I
I
.,._

x =
Figure 17.9
u
Ne
+x
to
x
when more
angular frequency equal to the excitation frequency Zejn. When the magnetic
field was reversed, the investigators detected resonant emission of electro
magnetic energy instead of resonant absorption. indicating a population inver
sion and a resultant negative temperature. The relaxation time necessary to
reestablish thermal equilibrium between the spins and the crystal lattice was
25 minutes, long enogh to demonstrate the existence of the inverted popula
tion. In the experiments only the spin subsystem was affected by the field
.
reversal; the whole crystal remaind at laboratory temperature
In radio astronomy.. negative temperature systems have been used to
amplify very weak radiofrequency signals. Also. the action of a laser depends
on a population inversion, which is sustained by some external influence. In
the case of a ruby laser, the method is optical pumping using light radiation .
Sec. 17.6
Ferromagnetism
315
::: :::::.::
::
::::;:;:;:;:;:::::::::::::::::: :;:::: ::=: .::.::::::::: :::;:::: ::::::::.:::=:: :::: ::=:.::::: =::::
:: :;:: ::::::::::::::: ;:;:::::.; ;:;::::::::: ::.:: : :;::::.::::;:::::;:::;:::::: =:;:: ::::::::::::::::::: :::::;:;:::::>:::;::::
.: :;.;
: :::::::.:::::.::: :::::::::::::;:: ;::.:::
17.6 FERROMAGNETISM
Pierre Weiss was the first to understand that underlying the domain structure
of ferromagnetism is its fundamental atomic nature. The atoms of a ferromag
net have a net magnetic moment and these couple together to forttl the
domains. Much of the previous discussion of this chapter is applicable to ferro
magnetism, with one important modification.
B+B
+AM,
(17.43)
(17.14)
we know that
the magnetization is
NJLz
1/2 and g
(17.44)
2, this becomes
2J.L8B
kT '
TJ =
(17.45)
(17.46)
This can be simplified at once by using the identities
coth 71
cosh,.,
11
cosh 11 +
11
cosh 11 1
sinh 11'
Then
and
M=
Np,B
V
tanh
tsB
kT
(17.47)
Chap. 17
326
(17.48)
From this equation we can Jearn a great deal about ferromagnetic behavior.
To investigate spontaneous magnetization we set B equal to zero in
Equation(17.48) and obtain a transcendental equation jor M:
..
N J.LB
=
tanh
AJL8M
(17.49)

kT
If we set
.
VkT

(17.50)
g = tanh
g"
(II
( 17.51)
Fi gu re 17.10 is a graphical' solution of this equation. Nonzero solutions evid en tly exist for
0 in the range 0
<:
( 1.7 52)
..
1.0
t.
r
'
/
/
'
Figure 17.10
Graphical
solution of Equation ( 17.51 )
The dashed curve is the Jeft
go < I.
O.H
().6
t
tanh ? 0
()
)
fo
(
0.
0.2 .....,._.
o
s;...__
.,_
....__
......_...___
...
...___
0.5
J.O
1.5
0.5
1.0
2.0
Sec. 17.6
Ferromagnetism
At T
317
Np,8fV. As T
increases, Mdecreases, until at the Curie point an abrupt change in the mater
ial properties takes place. This can be seen b}? solving for the temperature in
Equation
(17.49):
(17.53)
Assuming that MV/NILB is small, we can approxim ate the inverse hyperbolic
function using
tanh1x !!! x +
x3
X<<
3'
1,
and write
(17.54)
With a little algebra this becomes
NP,a
M=
We note that as T
Tc,
(17.55)
+
17.11,
1;;, we
tures above the Curie point, the magnetization is small compared with its sat
uration value. Therefore the hyperbolic tangent is small in Equation
(17.48)
and can be set equal to its argument. The resultant approximate expression for
the magnetization is
M
N'
,s2B
Vk(T
(17.56)
Tt)'
corresponding to incipient instability. Here the Curie temperature is the ferromagnetic critical
point and the phase transition consists of an orderdisorder transition of the electron pairs.
Chap. 17
318
1.0
M\l
vJ.J.H
Figure 17.11
Magnetization
of nickel as a function of
temperature. The
+rr
0.8
1
0.6
....,___ ++t\o1
0.4
.,__ '+.t
0.2
1
0 '0
++tt1
'
__._
0.2
_
_
_
.
_
__.
0.4
0.6
0.8
1.0
1/T(
This relation is the WeissCurie law\ which is a modification of Curie s law dis
cussed in Section
Equation
17 .2.
(17 56 ) suggests a method for
.
ture. For a given material measurements are made of the magnetic susceptibil
ity defined as X
( B/JLoM
1)
PROBLEMS
171 Show that the Bohr magncton is given by JJ.H =
in a hydrogen atom moves
that its angu l a r momentum is 1i. The magnetic moment J.L is the product of the
.
electron current and the area swept out by the orbiting electron.
172
(a)
For the hydrogen atom of Problem 171 show that the orbital magnetic
:
dipole moment is ea w/2, \\'here w is the electrons angular velocity.
(b) Show that the torque produced by a n1agne tic field para11el to the plane of
;,
the orbit is ea wB 12.
'
(c) By equating th e Coulomb force and the mass times the cent ripet al acceleration, show that
w=
Problems
(d)
329
Find values for the angular velocity, torque, and orbital magnetic moment
11
m; let B
10X
5.29
=
a
1 T.
for a hydrogen atom, where
=
172
Suppose that the hydrogen atom of Problems 171 and 172 is subjected to a
magnetic field B perpendicular to the plane of the orbit . It can be shown that
llJ.L/JL
173
The paramagnetic salt iron ammonium alum has the magnetic ion Fe+++. The
spin system has S
(L
O).Thus J
5/2
5/2andg
17S
ILl
CcB
T '
176
nal magnetic field of 1 tesla at room temperature. Assume that the electrons of
each atom have zero orbital angular momentum and spin angular momentum of
1/2. Thus J = 1/2 and g = 2.
(a)
(b)
177
178
an
M of
MB/T.)
Consider a twolevel system with an energy 2e separating the upper and lower
states. Assutne that the energy splitting is the result of an external magnetic field
kT
2s
(17.27).
eafkT
Chap. 17
330
179 The energy levels of a localized particle are 0, e and 2e. The middle level is dou
..
a 1n ax i mum
zero, corresponding to equal populations of the two energy levels of the system.
1711 Verify Equation (17.42).. referring to Equation (17.41 ).
1712
(a) For iron find the saturation value of the magnetization. (The atomic weight
of iron is 55.9 and its density is 7880 kg m '.)
1042 K).
(b) Estimate the magnitude of the internal field AM for iron (T,
=
333
338
340
345
347
331
Ni =
N does not
a =
p.fkT):
(18.1)
(18.2)
333
Chap. 18
334
BoseEinstein Gases
it must be doubled in this application because in a photon gas there are two
states of polarization corresponding to the two independent directions of
polarization of an electromagnetic wave. Each photon may be in either polar
( 16.8) becomes
g(v)dv
81rV
1
(18.3)
vdv.
u(v)dv
N(v)dl.'
hv.
(18.4)
But
N(v)
g(v)j(11).
Hence
( 18.5)
Thi is the Plack radiation formula. It gives the sp
ectral distribution of the
.
radtant energy mstde the encJosure. i.e., the energy pe
r unit frequencv.
The blackbody spectrum is often expressed in terms of
the waelength.
Then
li(v)dv ll(A)dA
x
and
dv
c

dA
,
,.\2
or
>._5
ehc/AkT
'
(18.6)
Blackbody Radiation
Sec. 18.1
335
u(A)
Setting x
hcjltkT, we have
aT4'
(18.8)
where
c, to the energy emitted per unit area of the surface per unit
time. The latter is the power per unit area or energy flux. In Chapter 11 we
Chap. 18
336
(vj4)n
=
BoseEinstein Gases
is the
number of particles per unit volume. In a similar way, the energy flux
is
(18.9)
where
(18.10)
Equation
(18.9)
is called the
known as Wien 's displacement law. It can be found by setting the derivative of
With .t
hc/AkT. this
reduces to
( 18.11)
is known.
ehc/AkT
===
1 +
he
AkT.
Sec. i 8.1
Blackbody Radiation
337
Then
u(A)dA
;o.::
81rkT
V
dA..
4
A
(18.12)
u(A)dA
z::
87ThC
5
.
hc/AhT
e
dA
(18.13)
This is Wien's law, valid in the short wavelength regiort (Figure 18.2).
ters (4 GHz). They observed a nonzero value for the radiation in every direc
tion in which they pointed their radio telescope. In 1990 the Cosmic
Background Explorer (COBE) satellite measured the background radiation
u(A)
I
\4
\
RayleighJeans
VJien
Figure 18.2
..,..._Planck
Sketch of
Chap. 18
338
BoseEinstein Gases
energy
density
500
;...
___.,
..._
__._
_
__.__
____
_
___
_
....
...
__,
_
400
200
600
frequency (GHz)
Figure 18.3 Cosmic background measurements by the
COBE satellite. The smooth curve is the theoretical
blackbody spectrum at 2. 735 K. The energy density is in
eV m3 per gigahe rtz (Adapted from The Inflationary
Universe by Alan H. Guth, AddisonWesley, Reading.
.
Massachusetts, 1997.)
at a large number of wavelengths. The data fit the theoretical Planck curve
It is instructive to ask: what is the average value of the ratio hv Ik Tin a volume
Vat temperature T? The number of photons having frequencies between
and
81rV
==
eh,./kT
(18.14)
 
N
where the substitution x
R17.Y
kT
he
,.
x dx
ex
1
(18.15)
2.02
107 T3
V,
(18.16)
Sec. 18.2
339
where Tis in kelvins and Vis in m3 To find the mean energy ofthe photons in the
cavity, we divide the total energy U
7.55 x 1016 T4 V J (Equation (18.8)) by
=
N. The result is
3.74 X
1023 T
=:;
2.7 kT.
v
au
ar
v.
(18.17)
Since this relation holds down to a temperature of absolute zero, it can be used
to determine the absolute entropy:
S=
kT
0
he
45
V.
(18.18)
Thus both the heat capacity and the entropy increase with the third power of
the temperature.
'
dU
TdS  PdV
JLdN.
TS in this
equation gives
dF
(18.19)
Therefore,
J.L=
aF
aN
T.V
(18.20)
(18.21)
Thus, as we discussed in the previous section, the chemical potential JL is zero,
because F does not depend explicitly on N.
BoseEinstein Gases
Chap. 18
340
aF
aV
(18.22)
r.N
The pressure of the photon gas on the walls of the cavity is therefore
(18.23)
=:=
for an ideal
gas of weakly interacting particles (see Chal>ter 11). Equation (18.23) can also
N(e)
(18.24)

g e
..
Our initial concern is determining how the chemical potential J..L varies
with the temperature. We shall adopt the convention of choosing the ground
state energy to be zero. At T
0
there is no restriction on the number of bosons in a given state. Setting e
in Equation (18.24) .. we see that if .f(e) is to make sense J.L must be intrinsi
=
..
Sec. 18.3
BoseEinstein Condensation
341
a dilute
gas,
the Maxwell
(18.25)
From Chapter
14,
1L =
kT
z
ln N ,
(18.26)
where
z =
2TrmkT 312
v.
2
h '
(18.27)
Thus
2TrmkT 312 V
_JL_ =In
kT
(18.28)
As an example, for one kilomole of a boson gas comprising 4He atoms at stan
dard temperature
J.L
kT
=In
27T(6.65
2
10 7) ( 1 38
.
1023) (273)
(6.63 X 1034)2
312
22.4
6.02 X 1()26

= 12.43.
The chemical potential per se is 0.29 eV. In comparison, the average energy
of
an
JL) /kT
1.5 +
gives f ( e ) = 9.2 x 107, confirming
(e
27TinkT
h2
312 V
(18.29)
is a positive number that increases with temperature and decreases with the
use the conservation of particles condition that led to the statistical definition
342
Chap. 18
BoseEinstein Gases
of the chemical potential in the first place. For the continuum appr<>Ximation,
this is
X
N(e)tle
f(e)g(e)de
N.
(] 8.30)
For g(e) we have the result of Equation (12.26) with the spin factory_, equal
to unitv:
.,
g(e )de
4
=
2 7T V
h3
3/2
I /l
e de.
(1 8 3 1 )
.
Thus
e112de
e(ep._t/kT
(18.32)
of Equation (18.30) rather than the sum, the ground state e = 0 is left out. This
terrn, in the sum of particle states at low temperature, is the largest tetm of all. It
is omitted here because the density of states function g (e) depends one' :! which
is zero for the ground state. Under ordinary circumstances this doesnt matter..
since, fore small compared ith kT. the omission of the one term makes a negli
gible difference in the result. But at low temperatures, bosons condense into this
lowest state and its occupation becomes much greater than for any other state.
We can surmount the difficulty in the foJJowing way. The tota1 number of
bosons consists of Nc. in the ground state and Nex in the excited states. Hence
(18.33)
Since the ground state is excluded from Equation ( 1 8.32) the integration only
gives the number of bosons in excited states. Therefore
(18.34)
The integral can be solved numerically to obtain a relationship between J.L the
temperature,. and the particle density. It is n1orc instructive. however.. to note
..
==
1
e
JJ./kT
0 in
Sec. 18.3
BoseEinstein Condensation
343
Then
for N large. (Even for a small macrosc opic system N will be a huge number.)
For low temperatures, then, we can safely put exp( JL/ kT) equal to unity in
Equation (18.34). With the change of variable x
e/kT, we get
(18.35)

0 ex
TT/2. Thus
3/2
(18.36)
N = 2.612V
(18.37)
To=
Jil
2/3
(18.38)
21rmk 2.612V
T8, all the bosons are in excited states. As T falls below T8, an increas
0, all the bosons
ing number of bosons occupy the groltnd state until at T
are in this state and N0 = N. The fractional number of bosons in the ground
For T >
state 1s
(18.39)
No
=1N
T
T8
3/2
(18.40)
Chap. 18
344
BoseEinstein Gases
(18.38)
we find
that
X
l<f3
3
( 2. (}12) ( 22.4 X 10 )
6.02
4.21
2/3
=
0.03 6
K.
0.036 K.
N0/ N and NeJ N versus T jT8 are shown in Figure 18.4. A corre
sponding graph of p,/ kT8, numerically calculated, is shown in Figure 18.5. *The
Plots of
sudden "collapse" into the ground state at very low temperature is called the
BoseEinstein condensation. It is not a condensation in geometrical space but
rather in what might be called momentum spac e.
For many years physicists believed that a BoseEinstein condensate did
not exist in nature. In 1995 researchers created a nearly pre condensate by
1.0
Nn
0.5
Figure 18.4
Variation with
temperature of N0/ N and
NcJ N
Nl'X
N
.N
t
() r.. 
)
1

T
Ts
JJ.
kT8
0.5 ._
1.0
Figure 18.5
boson gas.
*See Problem 1810 for the method of calculating p./ kT8 versus T/TH.
Sec. 18.4
345
K. The
18.4
The bosons in the ground state do not contribute to the internal energy nor to
the heat capacit y. The first term in the sum I si is Noe0 For T < Ta, No may
be large but e0 = 0, and for T > T8, N0
0 in any case.
For temperatures above the Bose temperature, all the bosons are in
excited states and we may expect the internal energy to approach (3/2) NkT as
=
(T < T8),
indicating that U varies as T512 below the Bose temperature. A more nearly
exact result is obtained by noting that
00
U =
eN(e)de.
(18.41)
21TV
2m J/2 oo
h2
e312de
(
)/kT
e ep,
(18.42)
As we have seen, if we choose the energy of the ground state to be zero, the
chemical potential JL of the boson gas is very close to zero for temperatures
below the Bose temperature. Setting p, = 0 and making the substitution
x =
e/kT, we
obtain
'
2
1T
kT
2'1TmkT 3/2
h2
x312dx
0
eX 
(18.43)
'
(1996).
Chap. 18
346
BoseEinstein Gases
the
gamma function
0.770 N kT
3/2
(T
T
'B
<
(18.44)
Tn),
(18.45)
Note that Cv is proportional to T
312
18.6. The
capacity
zero:
(T
(18.46).
T8).
<
U  T S is
3/2
0.51 NkT
T B.
(T
<
T8),
(18.47)
2.0
J

 ..  
......
Cv 1.0
Nk
0.5
Figure 18.6 Variatio with
temperature of the heat
capacity of a boson gas.
t

Ts
Sec. 18.5
347
from which we can deterrnine the pressure, using the reci procity relation
P
3(2
V,
(18.48)
from which
(T
<
T8).
(18.49)
independent of the volume. This is because the bosons in the ground state
e =
behavior in the vicinity of 2 K. Above the critical temperature 4He can't exist
30
p
(atm)
....._
20
10 .,__
solid
He
Aline
liquid
He II
liquid
He I
0 L......J.....+0
1
2
3
2.18 K
CP
4
He gas
6
T(K)
5.25 K
Figure 18.7 Phase diagram of 4He. The two liquid phases are
labeled I and II.
Chap. 18
348
BoseEinstein Gases
equil i b rium with its vapor at any pressure or temperature. Helium has two
triple points. At one of them liquid He I and liquid He II are in equilibrium
with solid helium. At the other, called th e Apoint the two forms of liquid
helium are in equilibrium with the vapor.
The transition between ordinary liquid helium He I and superfluid He II
can take place at any point along the Aline. A graph of the heat capacity ver
sus temperature for the two phases has the general sha pe of the Greek letter ,\
(Figure 18.8). As the figure shows. the heat capacity does not change continu
ously. Its variation with temperature is vastl y different in the two phases.
The properties of l iquid He II are unique. Its viscosit y is virtuall y zero
hence it is called a superfluid. In the twotluid theory of He II it is assumed
that, at temperatures below the Apont.. liquid He 11 is a mixture of a no1n1al
fl uid having viscosity and a superfluid that has no viscosity. The proportion of
the superfluid is zero at the Apoint a n d increases to
u nity
as the temperature
approaches zero.
Since the forces of interaction between atoms are weak in liq ltid helium
we might assume that liquid He ll i s an ideal boson gas, to a first appro xima
tion.* If we identify the Apoint with the Bose temperature, the twofluid model
s uggests
that the supc rfl uid component co n si sts of the ) atoms in 1 he ground
f
I
4
liquid
3

liquid
fIe I
I
.
He II
I.
..
.
c,
Nk
2
I
Jt
i
....
.
_j__
..
__ __
.,
,.,_!
____
""
'
.. r( K)
..
2.1H K
Figure 18.8
apply a
Problems
349
state while the normal component is identified with the Nex atoms in the excited
states. As the temperature falls below T8, an increasing number of atoms popu
late the ground state, and the superfluid component becomes predominant.
Are T8 and the Apoint the same? The volume of a kilomole of liquid 4He
is 27 X 103m3 so that the concentration is
Using the value of 6.65 x 1027 kg for the mass of the 4He atom, we can com
pute T8 from Equation (18.38). The result is
T8
3.1 K,
as compared with 218 K for the Apoint. We conclude that the superfluid prop
erties of liquid He II could be attributed, in part at least, to a BoseEinstein
like condensation at the Apoint. The ideal boson gas model, however, is only
an approximation to act1.1al liquid helium that neglects interatomic interac
tions. The complete picture is considerably more complcated.
\ '
PROBLEMS
18l (a) Calculate the total electromagnetic energy inside an oven of volume 1m3
heated to a temperature of 400F.
(b) Show that the thermal energy of the air in the oven is a factor of approxi
mately 1010 larger than the electromagnetic energy.
18l (a) Calculate Amax for the Earth, assnnting the Earth to be a blackbody.
(b)
183 Assume that the radiation from the Sun can be regarded as blackbody radia
tion. The radiant energy per wavelength interval has a maximum at 480 nm.
(a)
(b)
is approximately 7 X
lei m.)
184 (a) Find the frequency at which the radiant energy per unit frequency interval
of a blackbody is a maximum. How does this compare with the frequency at
(b)
2.7 K.
I
Chap. 18
350
BoseEinstein Gases
(b)
Compare this number with the number of molecules the same volume of an
ideal gas contains at STP.
186 Assume that the universe is a spherical cavity with radius 101n_ m and tempera
ture 2.7 K. How many thermally excited photons are there in the universe?
187 For photons. where there is no restricti<)n on the total number of )Jarticles, the
partition function is independent of N, as are the physical properties of a photon
gas. The partition function
In
ln(1
z =
e h ...
lkT),
ignoring the zeropoint energy. The number of single particle (photon) states in
a volume V in the frequency range
v to
dv is
Therefore, the partition function Z of the photon gas is the sum over states
given
(a)
by
B1rV
he
hvfkT.
In z
87T> k T
45
he
(a)
kT2
iJ In Z
aT
( 18.8):
v.v
(b)
Jl
kT
iJ
tnz
=
riN
V.T
(c)
u
=
+kIn Z
321T5k
45
he
T3V.
Problems
351
(d)
kT
In
<Jl/
v ,
T.N
( 2/3) ( U /V)
T iJP
iJT
u
::s
( 1/3)
u.
1:11;;&
P.
u =
==
18.5 is a plot of/ kT8 versusT /T8. In the region 0 < T /Tn < 1, p,/ kT8 is
essentially zero. ForT/T8 > 1, Equation (18.34) applies, with Nex set equal toN
1810 Figure
p,fkT8, 11
= T /T8,
ejkT8,
..
xl.'2dx
oex "1
(
&.) /
,
18.5).
2T8 is approxi
1811 The chemical potential of a boson gas at a temperature T
mately 0.8 kT8 Deterinine the mean number of bosons f (e) in single particle
=
1812
(a)
(c)
Find the chemical potential of a kilomole of 4He gas at STP. Express your
answer in joules and in electronvolts.
(b)
Use Equation (18.24) to show that the mean occu11ancy of a single particle
state having energy
1813
(a)
107 at STP
An ideal boson gas consists of 4He atoms whose Bose temperature is 0.087 K.
Find the boson concentration, the number of bosons per cubic meter.
(b)
(a)
(b)
(c)
volume
e0
is given by
BoseEinstein Gases
Chap. 18
352
1815 Hydrogen freezes at 14 K and boils at 20 Kat atmospheric pressure. The density
of liquid hydrogen
is 70 kg m).
1816 Show that for temperatures below the Bose temperature of a boson gas,
(a) Cv
( d) P
(5/3) UfT.
(c ) F
(2/3) U,
>
21TV
2m
/,
_, ..
1 '2
e' de
(  )lkT
e t P.
'
d
=
2
where A= h/(21TtnkT)1' is the de Broglie wavelength of the particles' thermal
motion and d
(V I N) 11\ It follows that in the classical limit the average dis
==
tance
355
357
361
364
367
353
m, in a container of volume
N noninteracting fermions,
V held at temperature T.
(19.1)
or
N(e)
(19.2)
(19.2)
is
referred to as the "Fern1i function"; it gives the probability that a single parti
cle s tate
e will
For
JL, f ( e )
<
f (e )
<
1.
0, that
is JL ( 0), is called the Fermi energy. The Fermi energy is also written as eF.
Consider the Fermi function at a temperature of absolute zero.
,
Evidently, at T
0,
(e
JL(O) )/kT
if e <
oo
if e >
p,(O)
(0)
355
FermiDirac Gases
Chap. 19
356
Correspondingly
0 tf E
>
JL(O)
>
( 19.3)
<
the lowest energy states available. The exclusion principle says that only one
fettnion is allowed per state. So all
_ ction at T
with the third law of thermodynamics. The Fermi fun
0 is shown in
m N, and V?
0. We need g(e),
It obviously doesn't depend on the temperature since T
the density of states of Chapter 12 once again. For particles of spin 1/2, such as
Figure
depend on
=
(19.4)
N;.
I
or
:X
N(e)de
0
Substituting Equations
p.,(O)
f(e)g(e)de
N.
(19.5)
()
2n1
N=
p.,(O)
e'ide
87T V
= 
(19.6)
f)
()
2m
/(e)
'
(T
0)
I ,._.____.
t(O)
Sec. I 9.2
357
lt
u
s
e
r
e
h
t
in
a
t
b
o
e
w
,
Solving for #J(0)
h
#J.(O)
2/3
3N
2m
temperature
t
rm
c
F
a
e
c
u
d
o
tr
in
For convenience, we
s
a
n
e
tt
ri
w
e
b
n
ca
is
Th
F.
T
k
p
&
p,(O)
=
(19.7)
TF
such
that
2/3
(19.8)

27Tmk
'
1.504V
(18.38).
p,(T)
2
3/
2m
:o
'
elf2de
+1
0et JL
(19.9)
Let the integral be I in this expression and equate Equation (19.6) with
Equation
e(sp.)jkT + 1.
/(e)
1.0 ......
. (T
  
.
5
0
(19.10)
0.5
1
I
I
I
1.0
0)
T
p,
0.2 TF
0.96#L(O)
e/(0)
358
Chap. 19
f(e)
1.0
0"
FermiDirac Gases
(T =O)
   
T
1 J.L
I
I
1.2 TF
0.45(0)
I

1
.
.
.
0.5
1.0
e/(0)
find a very good infinite series approximation for p,(T) in the following way.
Let
I=
(19.11)
where
')
and
f (e )
1
==
) k r
eF.p._.
+ 1
de
Now F ( oc)
f(s)f (e)
..
F(O)
is i nfin ite
but f ( x)
11
==
Jo\ver limit
F (e)
d_((t;)
de
ll.
so
Sec. 19.2
359
e=
F(e)
in a Taylor series
about p, since the only significant contributions to the integral! will be in the
vicinity of e
(19.12)
The contribution to the integral of the linear term is zero since
df (e) /de
is
symmetric about JL and the areas under the curve to the left and right of p, will
cancel. Thus
(19.13)
Evaluating the derivative
=
I
We set
(e
1
kT
kT
F( e )e<e,u.)J
de
[e(e,u.)/kT + J ]2
(19.14)

F(y)eYdy
.
2
(eY
+ 1)
p.jkT
:G
0 where y
The factor
eY is already negligible
for
e<
Bf,
at
co
(19.12), we
get
*This method of evaluating the chemical potential and the internal energy for low temper
atures is known
as
FermiDirac Gases
Chap. 19
360
7T'2/3.
JL
JL(O)
7T2 kT
kT
2/3
1 + 8
li_
:z:o ,.,., ( Q )
1T2
1L(O)
==
kTF, to obtain
(19.15)
0 at T fTF
1.1 p, (0).
instead of
at T/TF
1.5
1.10
We especially note that J.L is positive for temperatures below the Fertni
TF, more
1.0
0.5
J.L
(0)
0.5
Figure 19.4
Exact and
approximate calculations of
JL/p,(O) versus T/TF.
1.0
....
approximate
t
exact
0.5
'
'
1.5
\
\
\
\
\
\
\
\
\
\
T!TF
Sec. 19.3
Free Electrons in
Metal
361
1
f(O)
_
ep./kT+l
<
2'
JL
kT
or JL
<
<
0'
JL
kT In
(19.16)
with
Z
N
27TmkT
h2
312
.
N
(19.17)
T
>>
on a
mole of 3He gas atoms (which are fermions) at standard temperature and
pressure (Problem
T/TF
is very small, as in the case of an ideal dilute gas obeying the Maxwell
Boltzmann distribution.
with some number of its outer valence electrons, \Vhich can then move freely
about in the metal. There is an electric field due to the positive ions that varies
widely from point to point. Ho\vever, the effect of the field is canceled out
except at the surface of the metal where there is a strong poteittial barrier,
called the work function, tht draws back into the metal any electron that hap
pens to make a small excursion outside. The free electrons are therefore con
fined to the interior of the metal as gas molecules are confined to the interior
Chap. 19
362
FermiDirac Gases
<h
.
,

1.
......
._
Fern1i level
J.L(T)
lr
In this model, the free electrons move in a potential box or well whose
walls coincide with the boundaries of the specimen. They occupy energy states
up to the socalled Fermi level, which is the chemical potential p.(T). The work
(Figure 19.5).
The Fermi level of the free electrons in most metals at room temperature
J.L(O). It is often assumed
is only fractionally less than the Fermi energy eF
that the two are equaL and this leads to confusion. The Fermi level, strictly
speaking, is p,(T), which is an approximation to the Fermi energy valid for
T << TF.
A more realistic picture of the potential well is given in Figure 19.6,
which shows how the potential varies in the vicinity of the positive ions in the
crystal lattice. The periodicity leads to a band structure in the density of quan
tum states, which is the foundation of semiconductor physics.
To get an idea of the magnitude of the quantities in the electron gas

modeL we consider the free electrons in silver\ which is monovalent (one free
I
I
I
I
I
I
'
Figure 19.6
''1..L
Sec. 19.3
Free Electrons in
Metal
363
Since silver is monovalent, this is also the electron concentration. The Ferttti
energy is given by Equation (19.7):
ep
J.L(O)
h2
2/ 3
3N
= 2m
81rV
e F
(6.63
3
2
2/
3 X 5.90 X 10 8
1034)2
X

2 X 9.11
 8.85 X 10
_
1031
_ 19
J X
87T
1 eV
1.6 X 10
19
5.6 eV.
eF
k
5.6 eV
=
8.62
105 eV K1
= 65 '000 K.
T
TF
300
6.5 X 10
= 0.00462.
J.t(T)
0 999eF
.
eF.
The work function tP depends on the metal and the condition of its sur
face and is typically of the order of 34 eV. At very high temperatures, some of
FermiDirac Gases
Chap. 19
364
the free electrons may have sufficient energies to leave the metal. 1his results
in thermionic emission. The condition for their escape is
,
metal
N ( e)d
N(e)de
f(e)g(e)ds,
g( s)
r << TF.
<
behave like
The product of the two curves gives N (e) versus E as shown in Figure 19.8.
The electrons crowd around the Fermi energy because the degeneracy
increases with energy; there are threfore n1ore available quantum states to be
occupied with 0 or 1 electron( s) per state.
(It
distribution that have the best chance of escaping from the metal in the free
electron model.)
/(e)
(T
....,_.
0)
___ 
I
I
'
..__
_
__.;:....
_...
..
..
____
_
(a)
Figure 19.7
F.
(h)
The variation with single particle eergy of (a) the Fermi function._
and (b) the degeneracy function. The curves are sketched for 0 < T << TF.
t;
N(e)
,
,
,'
'
__
...
I
I
I

(T
I
0)
I
Figure 19.8 The energy
distribution of fem1ions for
0 < T << TF.
eN(e)de
ef(e)g(e)de
47TV
3
2
/
2m
h
e312de
oo
e(eJ.L)/kT + 1
3
At T
0, U
2
2
57r T
(3/5)Nc;F;
7T4
(19.18)
occupy the lowest energy states up to the Fermi level. The average energy of a
free electron in silver at T
e(O)
0 is
u (0)
N
5eF
3 .
5 (5.6 eV)
3 4 eV.
.
Note that the mean kinetic energy of an electron, even at absolute zero, is two
orders of magnitude greater than the mean kinetic energy of an ordinary gas
molecule at room temperature.
The electronic heat capacity Ce can be found by taking the derivative of
Equation
(19.18):
e
dT
+ .
(19.19)
For temperatures that are small compared with the Fern1i temperature, we can
neglect the second term in the expansion compared with the first and obtain
Chap. 19
366
1r1
=

FermiDirac Gases
kT
Nk
( 19.20)
BF
t:
5.6eV
2.2 X 10
Nk.
the same
as
for other solids. It was originally believed that their free electrons should
contribute an additional
(dU/dT
electrons near the Fermi level can increase their energies as the temperature is
raised, and there are precious few of them.
At very low temperatures the picture is different. From the Debye the
ory, Cvcx.T3 and so the heat capacity of a metal takes the form
where the first term is the electronic contribution and the second is associated
with the crystal lattice. At sufficiently low temperatures, the former can domi
nate, as the sketch of Figure 19.9indicates.
Whereas we have emphasized free electrons in metals most of our
results apply to any ideal gas of fermions. Using the fact that the reversible
3/v'k
1


          .,17 2 
heat
capa_cuy
Celect onic
Figure 19.9
..
Sec. 19.5
367
c dT'
Therefore
0 at T
Vk
(19.21)
U  TS is
T'
{19.19):
1T2
+ .

7T4
+ .
(19.22)
It is left as Problem
iJF

av
r.N
(19.23)
57r2 T 2
2NkTF
5 v
+ . .
(19.24)
5
Given this tremendous pressure, we can appreciate the role of the surface
potential barrier in keeping the electrons from evaporating from the metal.

Very high pressures, of the order of 1017 atm, exist in the degenerate electron gas
of a white dwarf star. It is this pressure that prevents its gravitational collapse.
A typical star has a hot core with a temperature of the order of
107
K.
The heat energy is supplied by thertnonuclear reactions. The atoms are com
pletely ionized (kT is 900 e V at tttis terr1perature), creating a huge electron
gas. In young stars the electron pressure is sufficient to withstand the weight of
the material pressing on the center, thereby preventing collapse. In old stars,
the hydrogen at the core has run out, fusion has stopped, and the core cools.
However, the loss of gravitational energy results in an increase in the kinetic
FermiDirac Gases
Chap. 19
368
In
t.
fse
of
a
lly
ti
pa
r
is
s
es
oc
pr
g
in
ol
co
e
th
d
an
energy of th e electrons and ions
n
tro
ec
el
e
h
t
by
d
te
e
n
v
p
r
e
is
t
in
po
n
i
a
r
t
a
e
c
nd
e
yo
b
se
white dwarfs the colla p
of
us
di
ra
e
th
d
an
n
Su
e
th
of
s
as
m
e
th
ve
ha
ly
l
gas pressure. White dwarfs typ i ca
the Earth.
=
P
(19.25)
Mass M
Radius R
V o) umc V
==
2.09
::< IO'f' kg
5.57
::<
106m
7. 2 3
::<
1 0 t J
'l
"
'.
io nized
that the number of nucleons in th e star is equal to its mass di vi ded by the mass
of a nucleon. Thus
2.09
==
1 o'u
I . 66 X l ()
'l
..
'
1 . 26
1 a,.


n uc l eons
9. 11 X 1 0
31
kg,
3N
81rV
Then TF
eF! k
3.9
5.33
10<) K. If 7
..
Io141
==
0.33MeV.
satisfied.
To a fair approximation. the ele ct ron gas p ressure is given by Equ a t i on
( 19.25). Thus
5 7.23
100
( 5. 3 3 x l 0
14
1 .8
1 02 Pa
1. 8
1 0 17 atm.
We "d lik e to show that this pressure is sufficient to prevent further collapse.
Sec. 19.S
369
A white dwarf is stable when its total energy is a n1inimum. The energy is
(19.26)
where Ue is the energy of the electron gas and Ugrav is the gravitational energy.
But
3 It
3
81rV
(4/3)1rR3, so
(19.27)
where
(19.28)
The gravitational energy of a solid sphere of mass M and radius
known from classical mechanics to be
U1rav
b
=
'
is
(19.29)
where
(19.30)
Thus
(19.31)
Minimizing this function, we find that
Rmin
2a
=
.
b
(19.32)
FermiDirac Gases
Chap. 19
370
Substituting the values of a and b from Equations (19.28) and (19. 3()), respec
tively, we find that (see Problem 195)
( 19.33)
Since the observed value of the radius of Sirius B is roughly equal to this, we
conclude that the star has contracted down to its stable minimum size and is
truly a white dwarf.
.
White dwarfs are at present viewed as comprising a core of degenerate
reactions have stopped. The star is cooling slowly. The time before it becomes
invisible is estimated to be 1010 years. Since the age of the universe is believed
to be 1.5 X toH> years it follows that very few white dwarfs have had time to
,
become invisible.
The st abi li ty of white dwarfs is but one example of the very extensive use
of quantum statistics in the st udy of st ellar evolution.*
PROBLEMS
of e/ et of (a)
(b)
193
.f ( f; ) of
or a system of n oni nteract i ng electrons. show that the probability f (e) of find
e n e rg y
194 (a) Verify that the average energy per rrmion is ( 3/5 )r.r at absolute zero bv
..
making a direct cal cu la t i on of U (0)/V.
(b)
0 is
l/2)ml:l
neutron stars.
Problems
371
approximately
Ce
where A can
be A
be determined by
AT,.
0.73 J kilomole1 K2 Compare this result to the value obtained from
Equation (19.20). (The atomic weight of gold is 197 and its density is
(a)
(b)
(c)
198
In sodium there are approximately 2.6 x 1028 conduction electrons per cubic
meter, which behave as a free electron gas. Give an approximate value for the
electronic specific heat of sodium at room temperature. (The atomic weight of
sodium is
23.)
199 Derive the expression for the fermion gas pressure, Equation (19.24), using
Equations (19.22) and (19.23).
1910 Calculate the isothermal compressibility of the ferrnion gas consisting of the
free electrons in silver. Compare your answer with the experimental value for
1911 Show that the gravitational energy of a uniformly solid sphere of mass M and
(3/5) GM2/R. (Consider the l?'avitational interaction
radius R is Ugrav
=
.
between a solid sphere (core) of radius rand a surroundmg shell of thtckness dr.)
19U For the white dwarf star Sirius B, do the computation leading to Rmin
:==
7 X lW m.
Use Equations (19.28) and (19.30) with the appropriate parameter values.
1913 Consider the collapse of the Sun into a white dwarf. For the Sun, M
R 7 x lOS m, V 1.4 x 1027 m3
=
(a)
(b)
(c)
2 x 10 30 kg,
the Sun, the collapse continues beyond the white dwarf stage as gravitational
attraction overcomes the electron pressure. The result is a very dense neutron
star that eventually ends in a supernova explosion.)
20.1 Introduction
375
375
379
381
384
386
387
373
20.1 INTRODUCTION
No reasonably uptodate introduction to statistical therrnodynamics would
be complete without some mention of inforn1ation theory. We have seen that
the entropy is a measure of the degree of randomness or disorder of a system.
A system that is in its single lowest quantum state is one in perfect order. On
the other hand, a system that is likely to be in any of a ntltnber of different
states is a disorderly system. The greater the number of states it might occupy,
the greater the disorder. Disorder, in this sense, implies a lack of infoiiitation
regarding the exact state of the system. A disordered system is one about
which we lack complete information. The reason for briefly discussing infor
mation theory is that it casts further light on the meaning of entropy.
20.2
Shannon laid down the foundations of information theory.* It was further devel
oped by Leon Brillouint and applied to statistical thermodynamics by E.T.
Jaynes.* Shannon's single greatest accomplishment was to provide a mathemati
cal measure of inforrnation. The cornerstone of the theory is the observation
that information is a combination of the certain and the uncertain, of the
expected and the unexpected. The first part carries no real inforrnation; the mea
surable infortttation is contained in the second part, the unexpected. The degree
of surprise generated by a certain event
is
.,
375
Information Theory
Chap. 20
376
tells me before I throw it that the same number 3 appears on all six sides, my
uncertainty about the outcome of the experiment is totally removed. I can ask
the question, before I throw the die, how much uncertainty is there about the
outcome? Or. correspondingly. how much information is transmitted by the
actual result?
For a given experiment, consider a set of possible outcomes whose probabilities are p1, p2..
tity H (p1
p11)
represented by the given set of probabilities. Only three conditions are needed
H (p1
increasing function of
p;
n.
= l jn; then
is a monotonic
ble outcomes of
two successive experiments. Let the first subsidiary experiment have two
Pi
p{
2/3
outcomes. We also observe that in the two cases the final outcomes have the..
same probabilities. Thus.. condition 3 requires that
1
H 2'3'6
l/2
single
expenment
l/3
1 1
22
l/2
two
expenments
SUCCCSSI\'C
l/6
(20.1)
l/2
213
l/ 3
l/3
116
Figure ZO.l Decomposition of an experime nt For the first expe rime nt.. the
pro babi liti es of the outcomes are p1
1/2 p
1 /3 .. and P3
1/6. In the
second experiment .. the first subsidiary experiment has probabilities p1
1/2
1/3.
and P2 = 1/2 while the second has probabilities J't' = 2/3 and Pi
.
..
..
Sec. 20.2
377
).
H (Pt
P,)
i=l
(20.2)
1 (p;),
(20.3)
f
n
dn
>
(20.4)
0.

... , 
Using Equation
1
1
1
1
=H , .
H  , ... ,   H , . ..,
11
n
s
s
rs
1
rs
(20.5)
(20.3) we obtain
1
rf 
Let R
1/r and S
sf
1

rsf
1
TS
(20.6)
f(R)
R
Setting g(R)
5f(S)
1
f(RS)
.
RS
(20.7)
g(RS).
If we differentiate this equation first with respect to R and then with respect to
S, we obtain
Chap. 20
378
g'(R)
Sg'(RS)
g'(S)
Rg'(RS)
Information Theory
and
(20.8)
Sg'(S).
Since R and S are independent variables, the only way in which Equation (20.8)
can be satisfied is for both sides to be equal t<l the same constant:
Rg'(R)
(.A
constant)..
(C
constant).
or
g( R)
A In R
In
r +
C
r
If the probability is
C
0, so
nf
A ln
ll
(20.9)
n.
A/n >
1/p we obtain
positive, and writing n

..
f ( p)
K p h1 p.
(20.10)
Using this result in Equation (20.2), we obtain the expression for the uncer
tainty we have been seeking:
"
p;
i =I
ltl p;.
(20.11)
Sec. 20.3
Unit of Information
379
1
2 1
+ ll
2
3'3

K(0.346  0.346)
K

( 0.270 0 366 )
.
l.OlK.
K In
n. It follows that
=
=
P1
In
P1  P2 In P2
Pt
In
Pt
(1 
of
(20.12)
Pt ) ln( l  Pt)
llDl
X0
( )
V (X )
u x
'
ltm
(x )
.
'
v (x )
X+0
liere
lim(x In
X+0
In x
.
ltm
1
X+0
1.1m
1
i
X+0
0.
2
x
p;
K In
n.
We need to choose a value for K so that H has some convenient unit. Consider
the simplest possible experiment with equally likely outcomes
or the binary digits 0 or 1. Then
heads or tails,
Information Theory
Chap. 20
380
HIK
Figure 20.2
Uncertainty
1'
____.
___ ___
0.5
0.5
()
Pl and P2
H

1
1
1
1
 In    In
2
2
2
2
In 2.
==
1 we obtain
1. Decimal digit
Here
0 hits.
3. Coin flipping
Flip a coin three times. The information will be three times that associ
ated with one flip of the coin. Thus H
3 1og2 2
==
*The ubit'' was coined by the statistician John Tukey during a lunchtime discussion at
AT&T Bell Laboratories.
Sec. 20.4
Maximum Entropy
381
TABLE 20.1
Known probabilities
of occurrence for
symbols in the
English alphabet.
Symbol
P;
blank
E
T
0
A
0.200
0.105
0.072
0.065
0.063
J,Q,Z
0.001
written H
of information.
4. English alphabet
a
=
H (Pt
Pn)
K
i= I
p; In p;,
(20.13)
vhere K > 0. In Section 20.5 it will be shown that, apart from the constant,
his is just the expression for the entropy in statistical thermodynamics.
.
Chap. 20
382
Information Theory
chambers by a partition. Initially there is gas on one side of the partition and
none on the other. Suppose the partition is suddenly removed so that the gas
expands to fill the whole container. We know from our study of the free expan
sion of a gas that the internal energy is unchanged but the entropy increases.
When the molecules of the gas are all in one of the two chambers, the
entropy is less than when they are distributed throughout the container. Our
knowledge of the possible positions of the molecules is greater when they are
all on one side of the partition than when they are somewhere in the entire
container. The more detailed our knowledge is concerning a physical system,
the less uncertainty we have about it .. and the less the entropy is. Conversely,
more uncertainty means greater entropy.
To make inferences based on only partial information. it is necessary to
determine the probability distribution that has maximum entropy subject to
what is already known. Suppose that we know the mean value of son1e partic
ular variable x that can assume the discrete values .xi, i
1" 2, .
..
n. The
mean
value is
..
.t
(2().14)
PiX,.
II
:
(20.15)
{p,, P2 ... Pn} consistent with the infortnation given Our problem is to deter
mine that distribution which maximizes the uncertainty (i.e. the entropy). We
..
introduce the Lagrange multipliers a and {3 and follow the procedure we used
in Chapter 13. We write
(20.16)
where
(20.17)
I
and
(20.18)
Sec. 20.4
Maximum Entropy
383
Then
_,;
P; In P;
a
+a
apj
'
or
 K In Pi  K
Pi
+a +
Pi
f3xi = 0.
or
We can determine the new Lagrange multipliers A and p, from the constraints.
Equation (20.17) gives
eA
1
=

so that
Pi=
(20.19)
(20.20)
Then
(20.21)
and
A In Z.
(20.22)
Chap. 20
384
Information Theory
we have
1 az
z dJ.L
a
 In Z.
i}J.L
(20.24)
(20.25)
U;=
N!

..
(20.26)
Sec. 20.5
385
=:;
N InN N
N1
J\j [lnN
In
N;]
N1
Then
(20.27)
Imagine that the system is in perfect order, meaning that all the particles
are in the lowest quantum state. Then
N1
1 and
N3
N2
=
Nn
0,
and the sum in Equation (20.27) reduces to one term equal to zero. Hence the
entropy is zero for the perfectly ordered state.
A disordered system would be Jikely to be in any number of different
quantum states; the larger the number of states available to it, the greater the
disorder. If
N;
states, then
N
kN
kN In N
(20.28)
If we associate
kN
Pi I n Pi
kN
=
H.
(20.29)
Chap. 20
...
386
Information Theory
e
th
d
an
s
ic
am
yn
od
m
er
th
al
ic
ist
at
st
of
Apart from a constant, the entropy
lly
fu
e
in
rm
te
de
to
pt
m
te
at
e
w
If
e.
m
sa
e
th
e
entropy of information theory ar
e
th
en
th
n,
io
at
rm
fo
in
al
rti
pa
ly
on
n
ve
gi
e
ar
t
bu
the macrostate of a system
k
lac
r
ou
of
re
su
ea
m
a
be
d
ul
wo
in
ga
d
ul
wo
expected amount of information we
is
it
,
ng
ssi
mi
is
on
ati
m
m
inf
the
e
us
ca
Be
.
tem
sys
e
th
of
te
e
sta
th
of knowledge of
the
,
ver
we
Ho
.
ure
rat
lite
the
in
y
rop
ent
neg
or
py
tro
en
ve
ati
neg
led
cal
s
sometime
constant of proportionality between Sand H in Equation (20.29) is positive.
The Boltzmann distribution for nondegenerate energy states is
ee,/kT
N
j

'
where
=
.
Thus
Sm
,.
+ N k ln Z.
This expression has exactly the same form as Equation (20.25). Hence the
internal energy plays the role of a variable whose mean value is known.
"Partial information'' in this case is knowledge of the energy of the system.
Sec. 20.7
387
Accordingly, some in vesti g ators have attempted to show that the fundamental
equations of equilibri un1 thermodynamics can be de ri ved from infottnation
theory. In classical ther modynamics heat, temperature, and work are taken as
primary concepts, while energy and entropy are derivative ideas. The informa
tion theory treatment inverts the procedure. Heat is introduced without the
need to define it in terms of reservoirs, adiabatic walls, etc. Information theory
is free from all artificial constructs such as heat baths or Camot engines.The
zeroth, first, second, and third laws become consequences rather than
premises. The third law, for example, is true by definition since, for a perfectly
ordered state at absolute zero, there i s no missing information (S
0).
text. Suffice it to say that its fa r rea ching consequences unify our understand

\vas
suggested
that the uncertainty principle might play a role in the prob lem: later it \vas
shown that this would not be the case for heavy molecules at reasonably low
pressures.
tion, and routing activities. Demers and Brillouin (194451) called attention to
the fact that in an isolated enclosure it would be impossible for the demon to
see
the individual molecules.To make the molecule.s visible against the back
ground blackbody radiation, the demon 'Nould have to use a flashlight. The
entropy produced in the irreversible
ope ration
whether it is coming or going, much less whether the molecules are coming or
Information Theory
Chap. 20
388
IS
"'
...
would not have caused as much consternation. Perhaps not. but the language of statistical thermodynamics is beginning to permeate fields as diverse
science, complexity theory biology, and animal behavior.
as computer
Maxwell's demon may be exorcised, but the ideas that conjured him up live on .
:,..:.. .. :?
: '....;,.
.
.::
...... . .
.. .: =" ::: ..... ....., ..... . .. ..:v;, . .. .......... .. .. .
....
'.
 "<" x:  ..
_,
...
.. . ... .
..
..
..
. ..
. . . .. . .
. ... .. . . .. . .
.... .. ..
.
. .... ... .
.
.
. . ... ....
. . . . .. . .
. .. . .
. . 
PROBLEMS
201 Refe rri ng to thecompound experiment of Section 20.2 show explicitly that
=H
Il

:?
..
1
.,
4
1
2 I
+H
2
3' 3 .

p1
==
n.
i= 1
203 Make a table of the logarithn1s to thl! base 2 of the numbers from 1 to 10. In
adjoining columns list the logarithms to the base e and to the base 10 .
ew
of Computation
A Revie\\
1969.
Problems
389
Note that
204 Consider a loaded die. Let the probabilities of throwing the numbers 1, 2, 3, 4 , 5,'
and 6 be 0.1, 0.1, 0.1, 0.1, 0.1, and 0.5, respectively. Calculate the un certait1ty H in
bits for a throw of the die. What would H be if the die were "honest"?
205 A perfect shuffle of a deck of 52 playing cards is one in which all of the possible
orderings of the cards are equally probab le.
(a) How much information h1 bi ts is there in a perfect shuffle?
(b) HO\\' many times do you have to cut and interleave a deck in order to
achieve something approximating a perfect shuffle?
PH(2)
l;
p10(4)
0.2;
p1 ( 6)
0.1; Po.t( 3)
0.1.
207 Consider a substitution cryptogram in which, for each letter of the alphabet,
some other letter is substituted. The number of possible keys is 26!. The cryp
togram can be viewed as a compound experiment consisting of two parts: x, the
communication of the clear text, andy, the choice of a key from one of the 26!
possibiliti es. Thus the total information associated with the compound e"peri
ment is
H ( x)
be solved. What does this imply about the maximum information in bits per let
ter of an English messag e ?
208 Imagine that system 1 has probability p}1> of being forced into a state j and sys
tem 2 has probability p2> of being forced h1to state k. Then
H0>
K pf0 In
pfl) H<2>
K pk<2> In P
k
2>
<
c .
Each state of the composite system consisting of systems 1 and 2 can then be
labeled by the pair of numbers j, k. Let the probability that the composite sys
tem is found in this state be P;k Then
K Pjlc In Ppc
j
k
If the two systems are only weakly interacting, so that they are statistically inde
pendent, then Pik
flO>
H < 2>
209 P.T. Landsberg (Thermodynamics and Statistical Mechanics, Dover, New York,
1990) draws a distinction between entropy and disorder. For a system of
tinguishable states, he defines the disorder D(n) as
n dis
Chap. 20
390
D(n)
Here
5'(n) is the
entropy and
S(n)
.:
ln
Information Theory
be found by diff ere ntiating this equation with respect to the time. Show that
.
D(n)
.
S( n)
S (n)
n l
JD(n).
ln
Here the dots denote time derivatives. Since the second term in the brackets can
conce iv ably be greater than the first tem1 the result suggests that it is possible
to have decreasing disorder even though the entropy increases. The expression
has a possible application to the growth of biological systems.
A. I PARTIAL DERIVATIVES
f (x, y, z)
0.
(A.l)
ax
dy
ay z
ax
az
dz,
x(y, z)
and
(A.2)
and
dy
ay
=
ax ..
dx
....
ay
dZ
dz.
(A.3)
The subscripts denote the variables that are held constant in the differentia
tion and are often omitted. Substituting Equation (A.3) in Equation (A.2), we
obt a n
391
Appendix A .
392
ax
dx
If we choose
..
ay
av
.. ax \
ay
dx +
ax :
ay
az
ax
az
dz.
(A.4)
0 and dx * 0. we have
1
iJ.x
av
..
(A.5)
dV
..
"'
...
a.x
...
dX


av
..
..
...
az
az
"
(A.6)
ri.r
\'
rlV ..
..
Equation
1.
(A.7)
...
A function
lt
only two variables when they are related through Equation (A.l), that is.. when
only two variables are independent. Thus
li = ll ( X,
y)
(A.8)
(A.9)
.X(ll, v) .
Then
dx
rlX
au
du
\'
ax
+
av
..
dv.
.,
(A.lO)
Sec. A.l
193
ax
az
ay
ax
ay
dZ
(A.ll)
(A.12)
dz
dz
dz
+
b
dz 
dz
M(x, y)dx
0.
(A.l3)
dz
a), we have
N(x, y)dy.
(A.l4)
aN
dxdy
ax
A
=
c
iJ
N
dxdy
ax
=
c
y
d
 ....



A.l Contour C
enclosing the rectangular
area A.

 
I
I
I
I
a
l
I
I
\
b
(A.15)
Appendix A
394
N(x, y)d)'
clockwise direction:
N(x, y)dy
N(b, y)tiy
N(a, y)dy
+
d
[N(b,y) N(a,y)]dy.
(A.l6}
The contribution along the horizontal segments of the .Path are zero since
dy = 0 there. Combining Equations (A.15} and (A.l6) gives
aN
dxdy
A
dX
Ndy.
(A.17)
aM
dxdy
ay
Mdx.
(A.l8)
(Mdx
N dy)
aN
aM
 dxdy.
ax
ay
d., 
.(.
(A.l9)
It follows that the condition under which the integral of dz around a closed
path is zero is
aM
aN
ax
iJv
"'
(A.20)
d 
a;.
. d.,'(
(A.21)
and
.
av a.r

.,
ayiJx
exact.
az

axay
az
ax ay
Sec. A2
395
M(;:)dx
z =
N(y)dy.
(A.22)
Mdx,
u
y
 iJufay depends on
aN
ax
aN
a au
ax ay
d.X
a a
Mdx
ay ax y
aN aM
= 0.
ay
ax
z=u+
LV
au
dy
ay
au
dv
Nay
.Y
Mdx + g(y).
(A.23)
This gives us a recipe for finding z: carry out the integration indicated in
Equation (A.23), take the differential dz including the tertn
(x + y)dx + (x + 2y)dy.
(A.24)
Appendix A
396
Then
(x + y)dJ. + g(.Y)
z =
So
dz
+.
..
g'(y )d)'
(x + .v)dx + (x + g'(}')jdv.
g(y)
2
y
g' (y)
2y, so that
C. Therefore
"'
x
==
+ .r v + .y +
.;
(A.25)
C.
.
"
Ntl_v
(A.26)
h(x)
dz
which doesn't satisfy Equation
that
=:
vdx
(A.20)
..
xdv_
dz
vtlx

.rdv.
.
2
1/y
..
vdx
dz

.,

.,
yThe term
1/ v2
..
is known as an
XlfV
.,
..,
X

v
.
...
Sec. A.2
397
ILliZ
tMdx + p,Ndy.
(A.27)
If dw s exact, then
or
iJt
oM
M + p,
ay
ay
iJL
=
ax
N + p,
iJN
ax
In general, this cannot be solved for J.L However, suppose that J.L is
of x only. Then <Jp,/ ay
function
0, and
aM
J.L ay
dp.
dx
J.L
iJN
ax'
or
d t

aM
1
=
aN

ay
a.:r
dx.
p,
exp
iJkl
!.J
ay
iJN
ax
dx .
(A.28)
Note that if the differential is exact to begin with, the integral is zero and
1.
In pr actice the formal integration of Equation (A.28) is unnecessary, as
we can see from the following example. Let
IL
dz
sinydx
cosydy.
Appendix A
398
Then
For exactness
a
(J,siny)
av
iJ
=
ax
(tcosy).
or
rl
ay
If JL
JL(X), iJL/iJy
= 0, and
diL/JL
==
ax
d:c, or p,
cosy.
=ex.
Thus
which is exact. If we choose to select JL = Jl.(y), then J.L = 1/sin..v and
dw
Thus we have obtained two integrating factors; usuaiJy one is easier to calcu
late than the other.
From this analysis it is evident that the differential
dz
Md:c + Ndy is
1.
aM

aN
=
ox
dV
"'
2.
dz
(A.29)
3.
a
Sec. A2
399
PROBLEMS
Al Test the following differentials for exactness. For the cases in which the differen
tial is exact find the function z(x, y).
(a) dz
(b) dz
(c) dz
A2
=
=
2x lnydx
(x2jy)dy.
(y  l)d x + (x  3)dy.
(2y3 3x)dx  4xydy.
(a) Show that dz ydx + (x + 2y)dy is exact and int egrat e it to find z(x, y).
(b) Show that az xdx + (x + 2 y)dy is inexact.
(c) Integrate the two previous differentials counterclockwise around the trian=
gle whose vertices are the three points (0,0), (1,1), and (0,1) .
xdy.
.,
z (x, y).
(b)
Find z
(c)
(0. l)
( 1 1)
8
c
Paths of
integration for Problem A3.
Flgure A.l
(0,0)
(1. 0)
Appendix A
400
A4 In the following cases show that liz is not an exact differential. Find an integrat
ing factor such that dw = JL71Z is an exact differential and check that t his is so.
(a) i1z
2y dx + 3x dy.
=
(b) az
(c) llz
y dx + (2x
(x4 + y4)dx
y2)dy.
xy3dy.
(ycos3x
1 )dx
,.uJz, where
i.
.
'
. . :.
.. ... ::
.
.
.
.
.
.
.
.
'
.
: . . : :.  .
, ,
. ... . : .
.  ; . ..
...
..
; ' .
' .
.. : :
'
:: ::::
'
'
: . >,
: . ".
.
.:
'.
'
. : :
. :::
.
.
: . .
..
.
' 
 
.
.
.
.
.
  . . . ' '.
: ;
 :
..
'
'
_.
'
..
.
2) 1.
(B.l)
(B.2)
it follows that 1 ! = 0! = 1.
We are interested in the natural logarithm of n! when n is a very large
number. From Equation
In tz! = In 1 + In 2 + In 3 +
'
Equation
(B.3)
+ Inn =
Ink.
(8.3)
k=t
is clearly the area under the step curve shown by the dashed
lines between n = 1 and n = n in Figure B.l. The rectangles all have unit
width; the height of the first is In 2, that of the second is In 3, etc. This area is
approximately equal to the area under the smooth curve y = Inn between the
limits 1 andn ifn is large. For small values ofn the area under the step curve is
appreciably different from and exceeds that of the smooth curve. As
401
402
Appendix 8
Stirling's Approximation
=Inn
"
v
"'
ln6 ......
In 5
In 4
rI
1
ln3 .....
In 2 .....
I
I
I
I
I
I
I
I
I
r
1
I

I
I
I
I
I
I
I

I
I
I
I
I
I
I
I
I
..___
___
...__
_
""""'_
_.__
_
........_
__._
Figure B.l
Graph of In n versus
___
n.
increases, the smooth curve flattens out and the difference becomes negligibly
small. Thus we can approximate Equation {8.3) by
Inn!
= n Inn  n + 1.
Inn dn = (n Inn  n)
=' n
Inn  n.
(B.4)
This is Stirling's approximation, valid for large n. For n = 10, Equation (B.4)
gives a value low by 1 3.8 percent and. for
:.
/:
'
, ...
:':
.
'
'
.
.
'
.
. . .. '
 :.
. _ '. . .
. . .
:
:
:: :
<
'
. ..

..:
. >::.
.
: .
_
'
..
.
...:
.
'
: .
.
: 
_ . ': '
. ;)
: ' \:
. : :_ . _ .
'
. ..
I
ann
(C.l)
N
J
Ki
ex
e!Je'
(C.2)
. . A..I '
1Yn

 
Nl ' . . . N'
(C.3)
and
(C.4)
403
404
Appendix C
We also assume, initially at least, that the energy levels are equally spaced. We
wish to make a minimal change in the given configuration while holding Nand
N1
and U
N_,e1.
is then
w,
N!
;! Nk! N,!

Nl !
Nn!

N, !
( N,
N!
I )_! ( Nc + 2) ! ( N,

I) !
Nn! '
so
or
J!
N,!
(N1l)! (fVt1)!


:=
e, 
'
1
Ek 1
F.i t
Figure C.l
levels.
*Here N
system.
Adjacent energy
405
or
(C.6)
(C.7)
Now, if the levels are not equally spaced, but are given by
(s1
sk)
(ek  ei)
p
=
q'
so that
or
406
Appendix C
Again, we would have found equalities like this if we had used i,j, k instead of
j, k, I, etc. Thus the function must be a constant
N1
or
or
(C.8)
which is the result we have been seeking. The Boltzmann distribution and the
MaxwellBoltzmann distribution are identical.
..
  . :.
. .:
:
..
.
.
.
.
.
_, ,
+co
_2
r
e  a dx
11'
1/2
oo
(D.l)
(0.2)
oo
+'lO
x2n+leax2dx
0.
(D.3)
oo
00
xneaxdx
0
n!
.
.
l
+
an
(0.4)
sld
X
X
e 0
s >
0.
0, 1, 2, 3 .... )
(0. 5)
407
408
Appendix D
t
J;xn exdx.
f(n
1) nf(n)
Various Integrals
11!,
wherenisapositiveinteger.
r(t) = r(2) = 1.
1T.
:X
a
n=l
l(3/2) = 2.612.
,(1) = oo.
(( 2 )
((3)
7T2/6
l(5/2). = 1.341.
1.645.
1.202.
((7/2) = 1.127.
((9/2) = 1.055.
3dX


2
)
1
(ex
(0.6)
(D.7)
15
=
(0.8)
1.
(D.9)

eXdx
x(ex+l) ..
X
.,


(0 .10)
409
Note that
smce
an integer,


r
ea dx,
> 0.
so that
 (il+f>
e a
dxdy.
dxdy
rdrd6.
r
ea rdrd8
MID
0
=
7T

il
ea rdr
1T
2 0
2a
(D.ll)
410
Appendix 0
Various Integrals
 'Tr e ar
_
4a
1T
I=
(0.12)
Xne uxdx,
'
.,
t 2 3
'
'
'
dl

da
x2e'xdx
t)
v; a.;.:.
J'"'
and
da
()
(0.2).
x2 For example,
xe
J=
ax
dx
eaydv
..
411
1
=
2a
e
00
1

2a.
Then
dJ

da
With successive differentiations, we can generate the general for1nula
(0.13)
CLASSICAL THERMODYNAMICS
C.J. Adkins, Equilibrium Thermodynamics, 3rd edition, Cambridge University Press,
Cambridge, 1983.
W.P. Allis and M.A. Herlin, Thermodynamics and Statistical Mechanics, McGrawHill,
414
Bibliography
C. Kittel and H. Kroemer. Thermal Physics, 2nd edition, Freeman, San Francisco. 1980.
R. Kubo, Tl1ermodvnamics, John Wilev and Sons, New York, 1960.
P.T. Landsberg. T hermodynamics and Statistical Meclzanics, Dover, New York, 1990.
D.F. Lawden, Principles ofThermodynamics, Wiley, New York, 1987.
M.C. Martin, Elements of Thermodynamics, PrenticeHall. Englewood Cliffs, New
Jersey. 1986.
P.M. Morse, Thermal Physics, 2nd edition, Benjamin. New York. 1969 ..
A.P. Pippard, The Elements ofClassical Thermodynamics, Cambridge University Press,
Cambridge, 1987.
..
Massachusetts, 1972.
: .
::
.:
'
': .
. :
STATISTICAL MECHANICS
R. Bowley and M. Sanchez. Introductory Statistical Mechanics, Clarendon Press,
Oxford, 1996.
T. Grenault Statistical Physics 2nd edition, Chapman and Hall Londo 1995.
.
Bibr
415
'
SPECIAL TOPICS
P. Coveney and R. Highfield, The Arrow of Time, W.H. Allen, London, 1990.
J.S. Dugdale, Entropy and Its Physical Meaning, Taylor and Francis, London, 1996.
J.D. Fast, Entropy, McGrawHill, New York, 1962.
M . Goldstein and I.F. Goldstein, The Refrigerator
Press, Cambridge, Massachusetts, 1993.
Chapter 1
11
(a)
closed;
(b)
12
(a)
(b)
(c)
(d)
(e)
(f)
isolated;
(c)
open.
lS
260.
16
348.65 K; 75.50C.
17
4.00 K.
18
a=
110
574.
111
0.5 mV/C;b
loJ mV/(,C)2; T =
430.3C.
Chapter 2
104kg.
11
1.5
Z.Z
(a)
0.308 kilomole;
(b)
9.86 kg;
(c)
3.96
l<t Pa;
(d)
0.277 kilomole.
417
418
23
(c) 800K.
2.67.
27
Chapter
31
3.69.
3
5.74
7
10 J.
3Z
1.91
33
(b) T1/4;

lfr' J.
(c)
(3/8) nRT1
92 1.
.
35
10 J.
37
(a) 3. 45
106 J;
38
(a ) 601;
(b) 70J;
39
(a) 3.12
3to
9.71 x
311
(a) A= 1.6 x
(d) 3.6 X 1 0 J.
Chapter
(b) 3.45 X 1 06 J.
(c) 50J,lOJ.
105 J;
(c) 150K;
(d) 1.25
105 Pa.
to2 J.
to)m1Pa 1.8
2.6mJ;
(b) 270K;
(c) 6 x l04J:
41
4S
l01 approximately.
46
(a) 8.3 1 x 1 06 J;
47
Q = n[aT

t.
7400 J kilomole
1 K 1;
..
411
(a) 1 m, flU
4.48 X 1 Q J.
413
3.66
106 J.
414
4.28
10' J.
4lS
696 m.
(3/2)bT2  cj2T].
=
0,
5 62
.
x lOi J
Chapter 5
53
S6
(a)
57
340 watts.
900kcal
(b) 1600kcal
RTvj (v
(c) 300kcaL400kcal;
b);
(d) 25/o,3.
19
59
71 K, 227 K.
510
511
200J, 1200J.
513
(a) T,j(T2
514
HfJ, 2.49
20.3%.
106J, 8.02
HfJ;
(b) 55.3%.
Chapter6
61
294 JK.
62
63
127JK1
0, 0.893JK1
65
(a) 19 K; (b)
69
(a) 5.76
610
(b) aT
10"1JK1,0;
(b) 5.76
1()JK1,5.76
lfr'JK1
+ bT3/3.
Chapter?
71
7l
660JK1
73
74
75
(a) 9.13
77
(a) 4.9
79
1.7 JK1
711
Cv
712
664Jkilomole1K1
713
(b) 0.4/P.
716
331 ms1
717
(b) 12.5Jkg1K1
X
X
1Q1JK1;
lfr JK1;
In T + R ln( v
b)
o;
lfrlJK1
(b) 4.9
11 JK1;
s0
81
83
1.62
nKT +
10'J.
BP
CP2
+ DJ>'.
let'JK1
(d) 5.73
(b) 9.13
ChapterS
1()1 JK1;
(c) 16.4JK1
(e) 0.
410
88
(a)  RT
813
(a) 200 K;
v.,
ln
+ a
v,
l

v1
(c) 2R.

v2
(b)
v1
1

Chapter 9
93
(b)  1 50
95
0.
96
2.
98
(a)
107 15
10
JK1
(b) 1.56
(c)
lOfl J:
5.19
lOJ JK 1
Chapter 10
104
2.38
105
Chapter 11
111
112
113
114
(b/3)(T3
T03).
2.45
(c)
(a) Nj
2
v0 ;
1.14
1Q28 m  2s  1
1.25
101J m 3.
1
ms ,
112
(b)
517
ms
v0,
1
v0;
v0;
(d) 1.41'V.
215 ms 1
11S
116
0.682
117
(c)
118
394 ms
119
(b) 1.50.
1110
v2e, zero.
0.427.

1,
445 ms
1,
2571
1111 3.86
108m_ 83.9,
1112 2.00
1113 4.0
6.16
109 s 1
"'
toss.
(b) 975 s.
1115 0.485 P.
112
2
1
)
m
m
1116 ( c2/c1 ) ( /
1117 About 10 days.
1118 2.80
10 tom.
105 Pa
7.39
103 Jm
1s'K1 8.53
106
2
m s 1
Answers
to
Selected Problems
421
Chapter 12
121
(a)
1.13
1015;
(b)
1.26
101 4 ;
(c)
0.112.
122
(a)
1.27
10:;
(b)
1.01
1029;
(c)
0.0796.
U3
49.
1?6
127
(c)
336,798;
1'8
(a)
1211 8.66
12U 5.6
(d)
In 3.
1 07
letc;2, lcY6
Chapter 13
131
(a)
4,4;
13l
(a)
2002;
133
(a)
139
(a)
25.3,0.0211;
1310
(b) lQc;.
1311
(a)
(b) 2ab,64o/o.
(b)
252.
(b)
(b)
1, 1, 1, 1, 0, 0, 0.
0.980, 0.0202.
2.78, 1:1.10:0.675,265
k; (b)
587 K.
Chape
t r 14
141
143
(b)
144
1.44
145
 0.29eV.
146
(a)
(d)
147
2.66
108
l(}c; JK1
3.74
106J,0.0388e\l;
2.22
108
(b) 6.06
10"1;
(c)
0.417eV;
4NkT,NkTfV,Nk[5 + ln(aVT4,f.V)].
Chapter 15
ts1
(a)
153
(a)
865,117,16;
154
156
(a)
7.53
toll
158
(a)
5.67
106 J;
1510 2.48
(b)
m;
(b)
656 k 6.
(b)
11.2
4.34
x
X
1011
107 J;
m.
(c)
1.79
105 JK1
422
Chapter 16
166
167
(b)
Kt
(Einstein) 2.68
1oJ J
kilomole t K I (Debye).
293 K.
Chapter 17
1
1016 s 9. 24
4.13 X
172
(d)
173
2.12 x to6
174
175
1.87
176
(a)
0.212 JT1:
1712
(a)
7.87 ?<
1713
507 Am1
104 JKT2
(b)
92.7 JT1
1550T.
Chapter 18
X
105 J.
181
(8) 3.89
18 2
(a)
183
184
(a)
(b)
5800 K.
(b)
1.58 X 1011Hz.
1
1
x
1
0 1
(b) photons/molecules= .7

1014:
(a) 4.1 x
18S
'
'
Approximately 107
186
1811
(a)
2.032:
1812
(a)
(b)
1.092:
(c) 0.685;
(d)
0.327;
(e)
0.176.
.
1813
(a)
1814
(a)
8.59 X 1 06 K;
(b) 96/o.
(c)
242 .
Chapter 19
191
(a)
0.134
(b)
192
(a)
0.070
K; (b)
0.116;
(c)
0.0997;
(d)
0.0735.
196
 experimental value.
1.88 eV;
(c) 1.89 x 1 oJ 1
197
(a)
198
kiJomoJe l K
ce/3R
0.046.
1912
1913
7.2 x 1 06 m
(a)
0.21
109 K;
(c)
2 x
1
lOS ms ;
(d)
0.39 kg m3.
413
Chapter20
206
1.33 bits.
207
2.5 bits/letter.
Appendix: A
Al
(a)
(b)
Z =
x2
lny +
y (X
C.
3)
X +
C.
(c) Inexact.
Al
(a)
z =
xy + y2 +
C.
(c) 0, 1/2.
A3
A 4
AS
(b)
2
z = x y  3x + C.
(c)
(a)
2
lf
y
3
1
1
o
r
x
(b)
y.
(c)
x.
(a)
Absolute zero, 14
unattainability of. 17 4
Adiabat, 22
Adiabatic boundary, 7
6162
Adiabatic process, 8, 62
253254
254257
Boson. 230.244246
Arrow of time, 97
Boson gas
Assembly, 215,221223
Atmosphere (unit) 9
energy, 345346
Atmospheric pressure 9
entropy, 346
Avogadro's number, 6
pressure.347
'
414
Index
425
Boundary, 78
of thermal conductivity,207
Boyle's law,22
of viscosity,204208, 211
Brillouin functicn,312315
Bulk modulus,180
Calorie (unit), 45
Canonical ensemble,255
Camot cycle,7479
()opressibuuty
adiabatic,117
of ideal gas, 28
efficiency,76,9194
isothertnal,28
Compression ratio, 83
temperatureentropy diagram,110111
Concentration,252
Condensation, 23,340345
Condition of integrability,31
Configuration,215
Camot refrigerator,7980
Configuration work,3740
Carnot's theorem,9194,98100
Conservation of energy, 40
Chain
rule of differentiation,393
.
. Change of phase,7, 23,2 6, 137141
Characteristic temperature
Constituents, 153,157160
Constraints, 237,238
Cooling
De bye,180,299
laser, 174
Einstein,294
magnetic,174,318321
Charles' law, 22
Critical point,2325,27
Critical pressure,2425
Chemical potential,151155,244,251252
Critical temperature,2325
Cross section,198200
Curie constant,329
Curie law,314
Curie temperature,326
Cutoff frequency,297
Classical limit,247
Cycle
Carnot, 7479,98100
Joule,84
Otto,83
Closed system, 5
Cyclical rule,392
Coefficient
binomial. 217
of diffusion, 208
of expansion
of performance,79
Index
416
Debye temperature, 180, 299
296301
Electrolytic cell,38
Degeneracy, 215
Degeneracy function, 229230
Electromotive force, 38
Degrees of freedom
internal, 279
rotational, 191,279,284287
translational. 19 1 , 279
Energy
conservation of.. 40
equipartition of. 190191, 270271
Ferrni, 364
318321
Density, 5, 10
frc e. 1 36
gravitationaL 369
heat. 53
of ideal gas, 56
internal, 42 263
Diatomic molecules
levels, 215,225229
magnetic. 310
states,225229
Dielectric polarization. 38
Dieterici equation of state. 32
Differentials
ze ro
poi nL 279
Enthalpy
definition, 57, 132133
exact, 42,393400
Diffusion, 208
of ideal gas. 60
JouleThomson experiment. 60
Entropy
Distribution function
Boltzmann, 238241,403406
BoseEinstein 244246,253254
Fern1iDirac, 242244,253254
MaxwellBoltzmann, 246248.253254
speed. 1 9J 1 98
velocity, 194
reversibilitv, 88 95,109110
..
.,
second law 97
Index
Dieterici, 32
ideal gas. 22
liquid or solid, 29
mechanical,145,156
stable, 143145
state,7
thermal, 1012,145,156
thermodynamic, 145
Equipartition of energy, 190191,270271
Error function,209
Euler's theorem, 153
Eutectic point, 157
Exact differential, 42,393 400
Exclusion principle, 242, 356
427
Free expansion, 70,104, 121122
Freezing, 26
Fusion, 26,140,148
Gamma function, 231,408
Gas constant, 22
GayLussac law, 22
GibbsDuhem equation, 154
Gibbs function, 136137
chemical potential, 154155
of dilute gas, 264
of ideal gas, 146
open systems, 151165
phase transitions, 137139
thi rd
law, 171173
of ideal gas, 28
Gradient, 9,204
Extensive variable, 5
Heat
definition, 4345
inexact di fferential, 44
Fermjon, 230,242244
Fernlion gas
latent, 57,140
mechanical equivalent of, 46
energy,364
entropy, 367
free electrons in a metal, 361364
units of,45
Heat capacity, 53,191193
pressure,367
FIXedpoint temperature, 14
Fluctuations, 255256
ux,186188,202203,205,336
Free energy
Gibbs, 136137
Helmholtz, 134136
Index
428
of a spin1/2 paramagnet, 317
definition 42
..
Heat of transfortnation
Inversion point, 74
..
Heat pump. 82
di ssipat i ve w ork , 40 41
definition, 133 .. 1 34 1 36
Isobar, 22
Isobaric process, 8
H y steresis.. 308
Isochore. 22
Isochoric process, 8
Ice point. 13
Isotherm, 22
Ideal gas
critical, 2324
adiabatic process. 62
com pr essibility, 28
diatomic, 56
Joule (unit), 45
energy. 56
e n thalpy. 60
Joule cvcle. 84
entropy, 112113
JouleThomson coefficient, 73
e quation of state. 22
..,.
expansivity, 28
internal energy. 56
90
Joule coefficient, 71
Kilocalorie (unit). 45
Increase of entropy, 96 9 7
Kilomole fraction, 1 59
assumptions, 183185
Informati on
bit, 380
entropy, 381
Lambda li ne 348
uncertainty. 375379
Lase r cooli ng .. 17 4
Latent heat 57. 140141 (see also Heat of
transformation)'
Intensive variable, 5
Law s of thermodynamics
Internal energy
Index
first, 44, 46
second,9697
third,171179
zeroth,1012
419
Microstate, 215,217
Microstates, sum over, 216,241,263264
uing,l62165,271273
Molecular diameter, 184
Loschmidt's number, 6
Macrostate, 215,217
Otto cycle,83
energy, 310
Curie constant,329
325328
energy, 316
entropy,317318
spin1/2 system,315318
spontaneous, 325
chain rule,393
work,38
cyclical rule,392
Manometer, 910
MaxwellBoltzmann distribution, 248,
253254,403406
MaxwellBoltzmann speed distribution,
193198,269270
reciprocal relation,392
Partial pressure, 162
Partition function,241,263264
De bye solid,302
dilute gas, 265266
MaxwellBoltzmann statistics,248
linear oscillator,280
rotational,285286
194
vibrational,280
Pascal (unit),9
Maxwell's demon,273275,387388
Path,7
Mayer's equation,5456
dependence,30
independence, 30
Performance,coefficient of,79
ean speed,l85,196,202203
(see also
Phase transforntation)
Phase diagram
helium,347
Melting,26
Microcanonical ensemble,255
Index
430
water, 26
intensive, 5
Phase equilibrium,2527,140141,155157
P1' diagram, 22 .. 26
Pvdiagrarn,22.. 24
Pv T surface, 25
P honon 298
energy, 335
entropy, 339
Quasistatic process. 8
heat capacity,339
Helmholtz function,339
Radiation, blackbody,333338
pressure,340
Planck curve,335,337,338
Polarization, dielectric. 38
Reduced variables, 32
Resistance thermometer. 17
Pressure
critical,2426
Reversiblc processes.. 8
entropy change, 10911 0, 111112
ideal gas, 22
Rigid rotator,224285
partial, 162
radiation, 340
units ot 9
Saturated liquid. 26
Saturation,magnetic,313,314
Process, 8
adiabatic, 8
Clausius statement, 90
cyc li ca l ,
increase of entropy, 97
KelvinPlanck statement 90
isentropic,112113
Selfdiffusion. 208
isobaric 8
isochoric, 8
..
isothermaL 8
quasistatic, 8
potential)
Solid. 25
reversible, 8, 109110
throttling, 7274
equation of state, 29
Property, 5
extensive, 5
431
Index
7
2
5
,
e
2
S
a
h
p
d
li
o
S
359
sion,
expan
ld
mrner
fe
So
117
gas,
in
d
spee
Sound
.
also
(see
93
1911
53,
ty,
capac
i
beat
c
Specifi
Heat capacity)
,
6
1
1
,
4
5
3
5
,
e
r
u
s
s
e
r
a t constant p
19119 3
3
9
1
1
9
1
,
6
1
1
,
4
5
3
5
,
e
at constant volum
9
3
1
1
19
,
6
5
4
5
s,
a
g
i
a
e
of an id
Mayer's equation, 5456
ratio, 56, 65, 192193
6
e,
b
l
a
v
ari
e
v
si
n
te
x
e
n
a
f
o
e
lu
a
Specific v
Spectral density,334
Speed
average,185,196
distribution, 193198,269270
mean,185, 196
mean square,185,196
most probable, 1 97
root mean square,186, 196197
of sound in gas, 117
Superfluid, 348
Surface film, 38
97
,
s,
5
g
undin
Su1ro
Survival equation, 201
8
2
3
,
c
i
t
e
n
g
a
m
,
y
t
li
i
Susceptib
System
closed, 5
isolated, 5
open, 5, 151 165
and surroundings, 5, 9 7

thermodynamic, 5
Bose,343
Celsius, 13, 16
characteristic, 280, 285
critical, 23
Debye, 180,299
Einstein, 294
Fahrenheit, 16
therntal, 145
thermodynamic, 145
Standard deviation, 209
State variable,7
Statistical entropy, 223225
Stltistics
Boltzanann, 235236
BoseEinstein, 244246
classical, 248
FermiDirac, 242
MaxweliBoltztnann, 248
Steam point, 13
Fernti, 357
fixed point, 14
ice point,13
Kelvin, 14
negative, 321324
Rankine, 16
steam point, 13
thermodynamic, 1012,103
triple point, 14
Temperatureentropy diagram, 110111
Temperature scale, 1216,103
absolute, 14, 103
linear, 1314
logari tlunic, 18
Thern1al conductivity, 207
Theranal equilibrium, 1012,145,156
Thertual stability, 145
Thermionic emission, 364
Thermocouple,17
Thermodynamic coordinates, 5
Stress, 204
Boltzmann, 235236
Index
432
BoseEinstein. 244246
specific, 6
state. 5
FermiDirac. 242
Variance, 160
MaxwellBoltzmann, 248
Velocitv
.,
Thertnodynamic system. 5
distribution" 194
gradient. 204
Thermometer
l='ernti, 370
fluid, 204
resistance, 17
Viscosity 204208
thermocouple, 17
Volume
critical, 24
expansivity. 2R
specific 27
v1, diagram, 22
Water
Torr (unit), 9
critical point 27
heat of fusion. 59
heat of vaporization, 59
ice point 13
pressuretemperature diagram, 26
specific heat capacity, 65
steam point 13
viscosity.. 204208
Triple line. 25
Triple point, 14.58
of carbon dioxide. 26
of water, 14, 15
Work
configuration, 3740
dissipative.. 4041
.,
177
electrical.. 41
isobaric. 48
isothermaL 47
pathdependent. 40
pathindependent (adiabatic). 42
sign convention for. 37
equation of state. 23
stirring. 4041
extensive, 5
intensive. 5
"'
Zustandsunune, 241
CONVERSION FACTORS
QUANTITY
Length
Mass
CONVERSION
1m= 100
em
3.281 ft
39.37 in
1 kg= 10 g
= 2.205lbm
Volume
=
103 liter
35.31 ft'
')
Force
1 N = 1 kg m s 2
10 dyne

= 0.2248lbr
Pressure
1 Pa = 1 N m2
=
10 dyne cm2
9.872 x 106atm
10
..
'
bar
Energy
lJ=lNm
=
=:
=:
107 erg