I'H 1-(K MC ll) y N A

MJ(~.'\

BY

ENRICO FERMI

'

..
'
..

..

...

"'"''
u,

.'~'

. - :.,;

. ..
'

: _ : ',.' ~

'

..

'.

-~.

; ...

.
'.',

<

-:~>-

,. .,

''

P,

'
q

...

\.';j

\b.

l.JU V

~"'-~

.t"U n
l'I~W

..

.1.9

L\......l\.~~Vl'l~,

X VK...l'...

.!

ll'IC.
II.A

lh

Copyright 1936 by Enl"ico Fermi.

~--r-<::TT~TT, ~ -..::TWTICT.

All

rights

reserved

~upy 1~11;;11

J.lllO:.:III<:lllVIId.l

under

. .

A1uerican

and

\....oVII VO:.:IILlVII~

Pan

.,

'

'b

oanv, Ltd., 30 Lesmill Road. Don Mills, Toronto

untano.
Published in the United Kinvdom hv C.onstahJ ..
and Company, Ltd., 10 Orange Street, London
li\Tf" 9

...,....._.

."

n. ..

...

.,

"

,_ 1 '

lfir:of.:

unabridged and unaltered r<'puhlication of the work

. .

..

..

ww

..

1937.

Librar"' of Coroness Ca tn Lmr Cmd N

~

l.iiHbt~L'

Dover Publications, Inc.

. .

,,

. ....

New York, N. Y. 10014

57-J./599

ermo-

"An tt.~r u.:s

CBAPTI!llt
L

.J.

1.
~.

.a..a.,

. . .
. . .

. . .
. .
. . . .
.., ..,..... " . . .
. . . . . .

The state of a system and its transformations

. .
. . . . . . . . . .
.!:'"''
........... ....,..., ...
......,
. . . . . .
The statement
. . of the first law of thermodynamics .
states can. be.represented on a (V, p) diagram. . .
. . . .
=
. . . .

PREFACE

. . .
. . .
. .
. . .

~~

.a..u= .._.

.1. llv

":1:,

~U~

i.J,

.1.

J. o;o.J IJ ~

U.l"

3.

VJ.

-..-.-

LIJlUU Ul

llJ. 0 U J."" YY

UllO

IJH~

llCI:l~

UV

...

11

YY

O!_

li:LW LU

19
~~

. . . . . 25
III. THE SECOND LAw OF THERMODYNAMICS . . . .. . 29
llv
Ul IJUv.l.
. ~"
V.l IJUv
-,
8. The Carnot cycle . . . . . . . . . . .
31
6. Adiabatic transformations of a gas
I ,

.1.

OU~I

. .lZ:LW

~~

.
10. Thermal engines
. . . . . . . . . . .
IV. THE ENTROPY .. . . .
. . . . . . . .
Q,
11
-~
.
. . . . . . .
12. The entropy . . . .
. . . . . . .
.....
c:<.
l::l.

--,

lt.t:l

~ 11~

wempo::ittl:>ure .

Ic

. .

,),

1~

J:

.LV'

J.u. UU'-'

LL

~VJ:''""

.1! -'- L
UJ.OOO VJ. UUV '-'UU&VtJJ

Di.J

44
46
AR

48
..t:A
......

14. The entropy of a system whose states can be repre~

VU ""'

r 1 jJ)

L ~Ul

15. The Clapeyron equation ..

.LV.

'\T

.1. Uv

Y <Ul UvJ.

..,

A 1U'Y I"

~<UO

+...

19. The phase rule

1Q

-~

'T"J.

~~

..J.

-~

"J

v\{'

Tlo '

17. The free energy

. . . . ""
. .
.
.
. . . . 63
. . . . . . . . uv

AT.'

. .

. .

77

. . . . .+ ... . . . . . .
v_....
. . . . . . . . . . . . .
. . .
..
,;.

s;-

R:w.-"'
VI. GA
:ll. Chemical equilibna m gases .

77

... ,y, ..

ov

-~~~

Q<)

. . . . . . .

22 'T'hA Vs:o.n't. Hoff '""'""t.inn hnY

86
98

. 1

~~

23. Another proof of the equation of gaseous equilibria . 106

24

Dil'lP.lll'l>:inn of o-a"'"'nlJ>: Pm1ilihril'l. ihP

Chatelier .

. .

. .

...
..

in1P of LP

. . . .

109

CMBR

AMICS OF

.l.ll l-l VU U\.; -

.1

THERMODYNAMICS is mainly concerned with the

~~

~~~

~~

~A~

~~

~~~

vu~

opposite transformations of mechanical work into heat.

Vnly In comparatively recent times nave pll.YSICists recog...,;",..,.l i-ho+ h>n+ ;"' o

.C

,.,.;

.n...-..n,.,.,.., +l- n+ nn

hn nl- n

~nrl

,+,

other forms of energy. Formerly, scient1sts had thought

'(jnali nea'(j was some son 01 nu1u w nose T.Oliat amounli was
inv<>l"'i .. hl.,. <>nrl h<>rl Rirnnhr in

N t.hA hA<>t.ino- nf

.+

<> 'h."rl~~

and analogous processes as consisting of the transfer of this

.
.
..,
..,
1
'
that on the basis of this heat-fluid theory Carnot was able,
.
.
m tne year 1<:5~':1:, liO arrive ali a comparatively clear unaer. . .
. ,.
'.
heat into work, that is, of essentially what is now called the
p

raw 01 l<IH::r. ~-.t.Y~

1R42. onlv Piul-.j.
vears

\.t:lee

..,Jl!t:a J.LLJ.

...:l
In
later. R .T MHver discc
the equivalence of heat and mechanical work, and made the
.
... .
.1'
.
1'
.

.C".

..L

1.

.L

. 1

1'

1.

energy (the first law of thermodynamics).

We know today that the actual basis for the equivalence
. 1
. ... 1....
1.
.1- ...
...1 .J,
. .C 1...
+1-

....

"--'

"-"

mterpretat10n, wh1eh reduces all thermal phenomena to the

.
. U.O.l OU.

.lUV

V.l

..... u.

0.1

.., u .l<:;;;:,

.I.' .l V U.l

lJ .11.10

noint of view. the studv of heat must be considered as a

special branch of mechanics: the mechanics of an ensemble
.1'
V.l

_1.

.1.
CO.U

. .l.l.lVUQ

.1'
V.l

. .L. . 1
}10.1 lJ.l'-'.lvQ

.L

\<:I.'

V.l

. 1
.lU.Vlv-

cules) that the detailed description of the state and the

mot10n loses Importance and only average properties of large
.j. 1 ...1.
.... .1
.c
.-l
.1..C
'. '1"'1- 1
mechanics, called statistical mechanics, which has been deY <:i.lV }J'VU

U.

lJU.l V Uo.l.l

lJUv

YY V.l-".

V.l

, YY 0.1.1,

.IJU.l

'

and Gibbs, has led to a very satisfactory understanding of

the fundamental thermodynamical laws .
.....

ermo ynam1c
1. The state of a system and its trans ormations.

given instant of time if the position and velocity of each mass-

6N variables.
Ind ed to use the
dynamical definition of state would be inconvenient, because

"

the atoms or
impossible to

for thermal equilibrium to set in.

As is well known, the

eter for all' tern erature measurements in order that these

cal datum that is ordinarily given.

It is only in the cases

example, a finely grained substance) that the surface must

the substance contained in the
vo ume, an pressure are no

'
the special properties of the substance.

Any one of the

as a function of the other two b

respec

quantities, p, V, and t .

ties graphically in a rectangular system of co-ordinates.

A

alon
pom

solid.

In this case, besides the temperature t and volume

'
directions
in order to define the state.
owever,

In

'

'

en e ne
y giving e mass,
the state of a re ation the ressure
omogeneous part.

system containing moving parts.

In almost every

that the different parts of the system either are' at rest or are

lected.

If this is not the case

0

It is evident from what we have said that the knowledge

.
.
.
1

ressure is then defined

With increasing time, the system exists successively in all

. '

motion, the system is rapidly passing.

external conditions remain unchanged.

This definition of

Thus, for instance

IS Ill

e uilibrium when its

of the system can be represented on a (V, p) diagram, such a

.
.
onnec xng
the two oints that re resent the initial and final states.

states of equilibrium.

A reversible transformation can be

with a movable piston and shifting the piston outward very

'
would be set up in the expanding gaseous mass, and the

environment very slowly in a sense opposite to that in the

A 1\A'"Tr<

.LU

v ... .._,

.1-"..

CI'V"<

pa-.L ae,_a.pu,

.A'"O

vvc;

-.,

co;;oo

~"

again to its original volume and bring it back to its initial

. .
.
.
s""""""' uy ~:~u.uLutg Lu.c: J:.HbLOu Inwaru very SlOWLy.
.1.ne
compression occurs reversiblv. and the !:!as nasses thrmurh
the same Intermediate states as It did durmg the expansion.
n,.,.;nO""' +~n ..e.
,.t;.-.n t.ht> ~ ,+
<>an
~n .. ....-.
".L:u...
or negative external work; that is, the system can do work
~

system.

.
u1

a.

..

~~

~~

v ..._

<JU

.,._...,

example of this, we consider a body enclosed

. As an.uct.v.1.ug
.
.
a .1uuvauic: J:.l.lbc.uu u1 area c ali one

~:-y

end (Fii:!:Ure 1 ). If 'D is the pressure of the bodv .., """tnst. the
walls of the cylmder, then p:i IS the force
,rl hv t.hP. hoclv on t.hP.

H t.hP.

piston is shifted an infinitesimal distance dh,

------

------

/?\

is performed, since the displacement is paral.

.
1e1 "LO 1one 1orce. .nu"L J::>an IS equa1 "LO -r,ne Increase dV in volume of the svstem. Thus
we may wr~te :

JT

oTT

lt'fa'

,,.,

1''-" r

ULJ

\,;<~)

1 It is nh";,...,., that (3) is ""'""''""\IV ""l;rl no ""' '"'"

what the shanA of
the container may oe. Lions1aer a ooay at tne unuorm pressure p, enc1osee1.
in an
container A (Figure
. irregularly shaped
.
_, . 2)._, Consider now an in:fini-

tainer move from the initial position A to the :final position B, thus permitting the bod:s; inside the container to expand. Let do be !" surface el~ment
~:

~UV

v~u

~u~

ovu

~v

~ '~>'

dtrectwn normal to the surface of the con tamer.

+'!.

+ A.

.1.

J.

+1-

...1

. . u

.~

uow

The work performed on

+l.

...!'

,J.

.+

,<

+1.

eontainer from the situ~tion A to the situatio-; B is obviously p d.,. dn.

The total
1t of
-' oerformed durina: the infinitesimal t1""-" -~
.ion is ou~a1neu uy In~egra~ing ouc auove expression over au ~uc sur. ace.,. 01
the container; since pis a constant, we obtain:
dL
~u ~

~n

~ ~~.,

u.,

~"'

uu~

"'!~' ~

~v

d.u dn.

a,.~u&~u

container is given by the surface integral,

dV =

da dn.

uomparrng tnese two equa1;10ns, we ontain

~ijJ.

v&

_. .,

'"'

ol \

"'
'
--:t:UT--a-nnn;e---Q-

A' ,r-,. T-... "V"T A 1\ A' T ,--;

'""""'
uy

' ~, un:e--wurK ~~~~~

inte~rating

is obtained by

en:

~Ut;; t:~y~v~

equation (3):
8

L=

vdV.

(4)

where the inteural is taken over the entire transformation.

~en tile state of the system can be represented on a

---~

~
/r~

\\

,A

__..-//

\_~
~

77

--

-.;;;::::::

~ VU.HU.IJ~VU

.1. lllt:l Ll

. .
~

{'VH

LLt:U

: L.l.

-.;

JJ\::l

Arf//1rmlI~

rill///////;
/IIIII/II

....

.L<;;_l.JX

w .lll

LUl

_~E

"WhPrP V
<>nrl V. <I.TP t.hP -.rnlumes corresponding to the
. 1
~"'"-'--- A ...J -D
rn1.

-=-x=-c="""15 =r,
and hence the work done, can
uo:;;

represented by a curve conneCT:mg A and B the shape

'"'

.JTT

)VA

OUU 1-'~"

geometrical
representat10n. we cons1<1er a transformation from an initial
state indicated by the point

a,

Ua.>::>

by the point B (Figure 3) .

.
.
.

of which depends on the type

ot transtormauon cons1<1ereo..
ThP urnrk- rlnno ch1rino- t.his
transformation is given by the
"15-

-,

performed during a trans-

. =

'- ' .-

uy

Fig. 3.
l>lll::

~
U..l I;::U.

l";.ll

.llJ.

L.l.lt:.:

figure.
Transtormat1ons which are especially 1mportant are those
for UTh1r>h t.h., 1n1t.i<>1 <>nrl final"'+~+~~"''""' t.h<> .,~~~
'T'l
<>rP
called cyclical transformations or cycles. A cycle, therefore,
;~

+~~~~-~'~~~~+;~~

1-;-1-

1-.-:--~

4-1-.
~

initial state.
UH

i:L

\. Y

> ]J)

'"-

1-..--1~

... _

;+~

If the state of the system canoe represented

:ar.u,

G,Yv .. ..,

Call ue rep

.vv

UlJ.

per or
direction.
D

L-----~~--------c~--1?

'
'
'
'
isochore transformation in this case is a transformation at

t, used so far to a new temperature scale T.

that the readings of different gas thermometers under these

thermometric gas, provided that this gas is far enough from

.
.
that it is

ossible to define this same 'scale of tern eratures T'

difference between the boiling and the freezing points of

as is well known

stance that obeys equation (6) exactly 1s called an ideal

()

-co

~~

~or a gram molecule tor mole) or a g--as- \_unau is, -ror ""
...,,.,..... 1-.a-.. .-.f O"l'".:OTYl"' .-,f ~'~ u-I'I.R P.mHl.l numericallv to its molecular

weight), we have m - M, so that (6) reduces to:

'~~

1:''

"''

,...,,

- '1. ...

+l

'

nf +'h"' .,..., " ;...,

r1~...,~;+~T

terms of the pressure and the temperature:

Mp

(8)

T r - prji

For an isothermal transformation of an ideal gas (transformation at constant "temperauure;, we J.nLvt:.

..
,.

'TT

YT

'

1.

'

.c~

-l.L

.L1.

'n+;.-...-.., .-.f n...,

ideal gas are thus represented by equilateral hyperbolas

lJ.(:I. V J.U5

VUV

-.,

/:'

-~-

We can easily calculate the work performed by the gas

.
0Tr J.
cxp
a urmg an iso"lJller
This is given (making use of (5) and
t.n H. final volume V 2.
(6)) by:
J. VJ.U

Q,J.L

rv ..

ru

Jv1

-riC

pdV

j,

= M
.,.

RT

nrn

,y,

v
m
v2
- 7tii
RT log u
Vt

Pt
P2

1Vi

. v~

,..

wnere Pt anel P2 are vUe I n = auu .Lu=--pr._,~,_,~ ...,

t1m:'\lv.
For one mole of gas, we have:
L

RT log Th.

'

~.I:'

(10)

is ~>'Overncd bv laws very similar

to those which are obeyed by u. chemically nomoge
.1. .11
11 f ]...,-,. ~~~~o"~J '117'1'.<:.<:?/rP. of !l. Pf'ITnOOnent Of a
'<'IT.
-=
mixture of gases the prc:,;~:~urc which this component would
.
.
'-Juu
exert n n. atone
-.~
A

v..-.;~+""'"'

RT lou: V 2

(()\

.-.f

"''""'l'".l

rrnf':8S

Lll~

'
Problems

pressure of 2.34 atmospheres.

3. Calculate the densit

y 10 grams of oxygen

'lne Fust Law ot 'lnermodynamics

3. The statement of the first law or thermodynamics.
""''

ro

~ .t.'t.

..l.

,11

-4-lo

.-1-

-1-

J.

)f the principle of the conservation of energy for thermo-

formation is equal to the amount of energy that the system

receiVe~

IrOIIl

<t:;H v .11

~~l:j

<t:;H\J.

.L.ll

uv 6L' v

v~ '""""'~

a.

p~

c;vJ.o:>O

this Rtat.P.ment it is necessarv to define the

phrases "energy of the system" and "energy that the

rYl<>(:mina t.ro

.+

..].

'

J.

~J

TYHI.t.iron "

In purely mechanical conservative systems, the energy

.- , 1_

'1

J.

1.

J.

lS

and hence is a function of the dynamical state of the system;

because !;O Know l!ne uy
--s~u~t:
u.L IJ.L.Lv ;:;y;:;t.~:::u.L """ll5"
orn1hn.J<>nt. t.ro knowinrr t.hP. noRitinm1 n.nd VelocitieS Of all the
mass-points contained in the system. If no external forces
.
.
'
are acting on Lut: :sy:sLetu, Lue e11er 0 .Y .~.
;t.uHt..
'T'lm"' if A !=!nO B are + ~ successive states of an isolated
system, and U A and UB are the corresponding energies, then

'

.1

.J.

~-

longer be equal to UB. If -Lis the work performed by the

external forces during a tran::'.formatwn from the mitiaT
A

'

~ 1.

.C.

.1

.J.

J.

~"

+ ~ ......

,.,,.,..,.1,

.~"'

.. '""'",.1 "hu

the system), then the dynamical principle of the conserva.

uon 01
o.Y
\Jut: Jul .111.
r r

rr

,, ,

From this eauation it follows that the work, L, performed

during the transformation depcii<I.'> only on the extreme

~ ~ '-~~~~~~

states A and B of the transformation and not on the par+;nn1n-

~nn~r

.;~

+\..~

Tn'h;,..'h

+ --

+"

"1'

.C.

"'-

performed.
v

~~

yy

~~v

.. ...,vv'l

v~v

V.L

interaction among the various mass-points of our dynamical

sy::s~>~Iu.
.Lnen we cannot calculate the energy ot the system
-'"
. .
.
'
. ' '
,...,
,.
~..

equation (11), however, we can nevertheless obtain an

'V U.L.P .L.L .L '-' ao.L

'-'>

~UI;:

. o.Y

Vl

Vlil

O.YOVt:OJ.ll

llll~

.LU

following way:
We consider an arbitrarily chosen state 0 of our system
anrl hv r!,

.~

'"'-.1on t.aJ... o ; t ,

~---~
TT

..

+n. ha

f .,,

(\

We shall henceforth refer to this state as the standard state

ot our system.
vons10er now any other state A ; by applyinP" l'llllt.~hlA Axt."',.'HI.l f

to onr

h:>m

ur<>

t><>.n t.r~..n-o

it from the standard state (in which we assume it to be

0

"

"

11. _ '\

C 1"

".L

. J.

, 1

"

-.,

the system during this transformation ( -L4 is, as before,

the work performed by the external forces on the system).
A.nnl

(11 \ t.n t},;"' +"'""""""""'~'""'"+;,.~

.,~,:!

,~......,1.

11 <l\

we find that
(13)

UA- -LA.
"-1'

~-

'-' a.o vuv .:;.Lup~ .Lva.J.

VJ.

"J..L'C

energy U .a of our system in the state A.

It is obviously necessary, if definition (13) is to have a
"

.L "l

.L

C 'L

"1

, y

A and not on the special way in which the transformation

v~~

'-'

vv

.u.

...., pv> .L '-'>

t:

H~V'C

<loll"t:~U.Y

this property follows from (11). If one found exnerimentally tnat "thiS property did not hold, 1t would mean
Ait.hAr t.hl"'J.

l!'l

nn+ n~-

,rl ;.-, "'"~ "'' .~

- +1-.n+

besides mechanical work, other means of transfer of energy

'" '-'""

_., .u.

......
We shall assume Tor the present that the worK perTormed
~-

....

~~~'hn~;nnl

~ ltom

;!,.,.;,.,,.

t'"""'"-f,.-,rrn!'lf.l()n

nnu

depends only on the initial and final states of the trans-

'

energy.
vv e can
.._

"

1'.

'

' 1.

.
.._

....

"J

UIJI

\,.L.L) .UOJll \,.Lu)

n T l u +u~

(;1,.::;

lVllUvvo.

'R nn.-.

,...,.,rl

c-fnf.no

"l

4>.

lur<>'tTQ

be performed as a succession of two transformations: first a

transformation from 0 to B. Since the system performs

.
-t .u8 u unug
DA i:LHU
t.ne amounts or wvn\..
""' v
t.rl'l.n o;:,f,
Lations the total amount of work nerformed
during the transformation from A to B (which IS maependent

VJ.

]:J"-".L uJ.'-' ..... _...,_.

~J.J.'-'

"'J

...-

formed) is:
L

-LA+ LB.

From (13) ancrt.Ile analogous equatiOn,

'D'

, 1..

vv <> v '-' ~ a.J. .... ..... .,

TT.

T.

TT

which is identical with (11).

We notiCe, finally, that tne aenmtton
~~+ ,..,;+~ ,,...;,... ~

";n,-.n

it.

rl<>n<>n~l"' t~n

\16)

ox 'tne energy i::s

t'h<> nn.rt.irnln.r ~hoice

a
of the standard state 0. If instead of 0 we had chosen
.
.
> V I WI:' ;:oUUUlU Hi:L'Vl:J 'UUU<e "''-''-'- '-"
:-rr 0
aurerent s1;:
different value u'.. for the energy of the state A. It
can be easily shown, however, that u A ana t 1 A altter on1y
r.l

,1--la~ n

1-

nn~n+

..

.-t.

Tnrl.ncul

1.

_.]

1.

+'ha

... .,n.-,fnrTYl<>~;,.-,n

.t:.

0' to A can be put equal to the sum of two transformations:

I::>'

'I::>

The work LA performed by the system in passing from 0' to

Li 1s tnus equaT"GU'.
L.IA

"--'0'0

"--'A 1

'.--rr-<~

>T

~-

where Lo'o is the work pe:fformeaoy the system m gomg

rv

1'.

UT~ h~un

,...~~

UA' = - L'A,

UA = -LA;

so that
UA- UA = Loo,

which shows that the values of the energy oasea on the two
_] e.. ,..._.

..J."

.cc.

.1 h +h~ ~~~n+~,....j- T .

This indeterminate additive constant which appears in the

.U.LVU

v.

~.L

.,

eJ

'
feature of the concept of energy. . Since, . however, .only
. .c::cu liT !J~~:t; Ht;t:: 7 I.Jllt:: l:LUU.LIJ.l.V C
dltterences or energy are c
_1

.L ' -

The only assumption underlying the above empirical

LIJ~VU

V~

U.LLv

. Col

U.U~

.LO

V~V-A

performed by the system during any transformation depends

only on the Initial and nnaT s'Lal."es or '(jfie '(jranswrma'(jion.
W., 1, "~'"' "lr<><=>.rhr nnt.if't>rl t.h <=>+. if t.hiR l'I.Rs:nmntirm lFI

n.-

dieted by experiment, and if we still do not wish to discard

,,

,,

IJ.Ut:: !Jl'lill.a}llt:l Ul

"

1,.111::1

V i:I>IJlUH

LL

. o.Y 7

Vl

vv 'V

.u~uou

admit the existence of other methods, besides mechanical

work, by means of which energy can be exchanged between
+hn "n"+"....... <> nrl ac ., ...... ~~~....
+
Let us take, for example, a system composed of a quantity
~-

.....

' 1.

'
v

atmospheric pressure; let the temperatures of the system in

these tWO StateS be tA ana tB 1 respeCtiVely, Wlth tA < tB.
UT.

~~

+n 1~~

~,,.

'~~

J:.

+~

J5 ;~ +,...,.,.

rlif'f'o,.on-1-

Tnnuo

First way: We heat the water by placing it over a flame

. .

'A

-~

final value tB The external work performed by the

syt:ii.Jt~.tu uuring -.,nis Ll-,
.ul-llll:Ll
is 11 u"'"''
v
z.c.tu. J.u
Lld be exactlv zero if the chan!!:e in temperature were not
accompanied by a change in voTume of the water. Acv

'

'

wv~

t"' to t8 by heating it by means of friction.

To this end, we

Since the water offers resistance to the motion of the paddles,

kee
is an equal amount of negative work performed by the water
er

gomg
way.

is transmitted to the water in the first way in a nonmechaniand mechanical work are equivalent; they are two different
aspeets of the same thing, namely, energy. In what follows
magnetic work as well as mechanieal work.

'

The first two

~~T~

~~

~TTHVn

H">,.Kf'>T"I.TT'T

r.r.1

UT

~T~~

vve ~
-~, now.,v.,r,~wotKcan oe
P.Yf' han O"t>rl hP.~
the svstem and its envir
,.,..,t, (for
example, by enclosing the system in a cylinder with non-

~e

enVIronment.

-l . . ~

.11.

1- +

'"'al-.

""'oTrnl-.1~

~;~+~-

..J\

The exchange of energy between the inside and the outside

-oJ

'

nrincinle of the conservation of enerl!'v it fnllnwR

that the amount of work performed by the system during
~

t,hP.

"-

.+:~~

.J!

'~"'

"'~ln

"'~

final states of the transformation. 2

..

--syffLI:liil

muy.

e~ergy

')

u;y

'-J<V

.+

"',,~

.1.1.

-l

'OJ
'
U as a function of the state of the

~~u...>litll~
~~

- +l.-

:..,:+:-1

..

-r

and define the

.f.h~

\::7 A.

.f.hn.f. ,.,.,..,..,,., ..1 -

. .

urre -vanauton
...

.J!

mation from the state A to the state B, we can write

. .
.
. ,.
.
'J
system, in the form:

..

-;

~-

AU+ L = 0.

(14)

If our system is not thermally insulated, the left-hand side

of ll4) w111 m general be d1tterent lrom zero because there
f'!'l.n t.hP.n t..<~.k-P. nl.<!.P.P. !'l.n P.YP.h$l.TID"P. nf P.TIP.r.rrv -in 1-_},., -l'n-rm n-1'
1 We

-~H . ,~~~l 1nanlat,nra <>V1at,

need onlv mention herA t.hat no
.1nerma1 msuial>IOU canoe oouamea approxtmaue1y, nowever, oy means or
the '!ell-known methods of Calorimetry.

'

content of the preceding sentences as follows:

Exoeriments show that there exist certain substances called thP.rm.n.l
insulators having the following properties: when a system is completely
enclosed in a thermal insulator in such a way that work can be exchan.e:ed
,

_p<OUVUUOU

'-'_.f

OUO

system during a given transformation depends only on the initial and final
-~

~;+'ho.-~o

:.

>+"

lt should be notJCed here that if definition (13) of the energy of a state

A of our system is to be applicable, it must be possible to transform the
mally insulated. We shall show later (see section 13) thatJsuch a tr:.;;_sformation is not alwa"a r.n~oa-.lo win
A.n AXP.h >nno ,...; hoafc
Tn on~'h
~s, nowever, the oppos1te transformatiOn A ->-u can ruways oe performed. The work oerformed bv the svstem durin a thi,.
' -~or.,n,.-fnr~" J ~o sucn cases also.
rr
"" LJA. ' w" ""'"

-,-,.yT"o MrM

<

neat. vve snau

eauation

YY7

"""'...,.

erore replace
!:J..U

,,

A"~~T7'T

~l'.I:J

<

.......

'WY~~

oy tne more general

L = Q,

(15)

where Q is equal to zero for transformations performed on

.L 1

, 11

"

.I

-l

"-

...l

"- L

"

"

different from zero.

.

~can ue IDLerpreLeu puyslCauy as tne amoun11 or energy

t.hat. is
ived bv the svstem in forrnR ot.hP.r t.hl'l.n work.
This follows immediately from the fact that the variation
.
,.j.1
.+ .1
....
+1A TT
~ ~
amount of energy received by the system from its environ"

.....

.j.

,.

.j-

.j-

TT

,....

HencP.

L iH the Fmer"'v receivAd in thP. form of work.

R.nrl

Q stands for the energy received in all other forms.

-l . .t:: . air...-.

Uu

"""'' coh a 11

nruu

,.., 11

.j- h~

.... ~r>nn+

Nl' han+

received by the system during the transformation .

,.

simple form. Since the initial and final states of a cycle are
the same, the vanatwn m energy IS zero: t::.U = 0. Thus,
( 1 ~';;\

(16)

Q.

That is, the work performed by a system during a cyclic

I.ranslOrinauion is cq ua1 LU Lne neaL au:surueu uy Lue ~;;yt;Le~u.
It is imnortant at this noint to establish the connection
between this abstract definition of heat and its elementary

. .

..

calorie, is defined as the quantity of heat required to raise

LUC Lt::u:
UHt:l
gu:UU
tH
VV<:l.Lt:l.l
<:l.L
(;1,1
,.lv
nressure from l4C to l5C. Thus to raise the temJi>erature
of m grams of water from l4UC to l5VC at atmosphenc
~Jt:U:tLUI"t:

U~

,,..,. "'"' r<>nlll'l"<> ,.., ""' 1.

.nf ht><~+

T .t>t.

t\11.

rl,

._

t.hA

variation in energy of one gram of water, and l, the work

.
I.LI. ""
v" .1~<:> ~
"""' "' . lL Ul HJO "Lr<:;;L a~

.10

10

-.,., T

..--.cv-n ..- nr r.

~TT~~~

raisea rrurn ~4-v -r;o ~o v av atmospneriC pressure.

e:rams of water the variation in Pn
anrl t,h<>
are:
...

~~c

.LJc

~~c'

~1- rtrnH>

II<Nc

l,.l/)

Form

...,

......

"~

~-

mation. In order to measure the heat PvnhRn~rPrl

n
the system and the surrounamg bodies, we place the system
in r>nn+

+ ..T;-1- h a >alr.l"i

~~ .... +n;.,.,;.,.,~

,.j.

. .r

initially at 14a c. We choose the mass of the water in such a

.
"'
-.r.temperature of the water is 15C .
pvLL'V\C'I,L.)'
.v,

..

.1!

'

. L~L'-'V'VL

~<>V"

thP.

U-4~

~--~L~U

_.._,

nf

..1

t-'ho "'u"'+""......,

..l

.Ct

.. ;

calorimetric water is thermally insulated during the trans-

.r.

.... .

"'<TT

...

-/

'
The total variation 1n energy
is equal

transformation.

..

..r .

. 1..

TT

"

TT

"W"hP.rP !'iT!. 1<> t.h<> v~.r1~.t:inn ;..,. "'"'

"OJ

~.r +l-

- J

'

>Uv.LL.I.

o>

I'J

...J

..,_.~~

tl.U c is the variation in energy of the calorimetric water.

'~J>

LVL

uuo;:;; uvua..o. wv.o.n.

Wtl lll;t Ytl .

.
T.'\

(1.<1) ..T~ hano

-1-1-..o.~

t:..UR

t:..U

t:..Us

Ls-

-1- Ln -1- T.

()

or. bv (17)

.. .

(t:..U.,

.L'l.

'oJ

~~

L .. )

+ lc).
+ Ls is

-m(t:..uc

But from the definition (15), !iUs

.

1.

..

,.

~u~~,

c;

the aruount of

.'"' ..~~ ' "' :

\LO)

Nm

~TY

-w-e---see--r~u.LU. ~ ~

.....

"6"'

~~

lJIIff

~...,.

'6~~~

is proportional

<Jr

tom.
On the other hand, m calonmetry the fact that m grams of

= "'-

~n 1~~;- ~+-;n

'houa.

1-.~n+~rl "-

1.

1 A

Or< +~

1 J::.0("'"1

means that m calories of heat have been transferred from

..

"'

..

Q.q

.,

..,

has received -m calories, or that

. expressed in calories.
IS equal to -m.
we see also, by companson with '(1~],
+h a+. +.h.,. amnnnt. nf h.,.at. '"''
-'h.. r +.h.,. ..J "' ;,.,,.., (ll'n ;"
proportional to the amount when it is expressed in calories;
',

'

'

"

. 1'

'

'

According to (15), heat is measured in energy units (ergs).

'<5'

IDP~~ured

bv manv

investio-atnr~

. ~~"'

~.......,

-who hnvP. fonnrl t.hRt.

= 4.185 X 107 ergs.

1 calorie

(19)

In what follows we shall generally express heat measure:_ - -

....

--!+-

"''

Equation (15), which is a precise formulation of the

.
.

.,

-J

thermodynamics.
th ... -"" ' la'OO' +n
states can be represented on a (V, p) diagram.
.4

Tlu annl;,-..,. "

.

' 1.

c.

nf

_.._

."

_1

L 1.

..

'"'

We shall

.L

such as a homogeneous fluid, whose state can be defined in

J

'

1" '

~~J

function of the state of the system, as, for example, its

energy, U, will then be a function of the two variables
--'L..!-1... ' - - - - - ' - - - - -

,1...

..

-~- ...

+1-

.......

In order to avoid any misunderstanding as to which are

. .
.
.
.
. .
.
'J:"

'.J

entiate partially, we shall enclose the partial derivative

.
.

-.sy

"llr~

.1-'U.n;;:lJ. vll~t:::::U~ ctHU r

IIUt:

Yl:l.~~i:tU~t;

~~

loU

be held constant in the partial differentiation at the foot

of the naren thP.~i~

'T'hns I

a-u

\'"' .. I v

m<><~n~

t.hP. flf,rivfl.t.ivP. of

--

11"

n. -,-.,.-. n..-

keeping -v C(Jl1S'I
.rl.,.nt. va.riables.

U with respect to '1,

Rl"A +.<>.k-An 51.!': t.hA inrl

'

1\ II" T

r< C<

w J.J.tjJ.J.

I'

.L

Notice that the

au

above expression is in general different from I

rn

I , because

' w'h-11 e m
. the
in the first case the volume is kept constant
.
Llltl P>'
"tl .Li:l .Kt:pll
"'
h-~n;,-1=~ ~~ ~ ..... ~.,... "+
"
,.,1 +~..,..,,.,;,...~...... G.t:inn nf onr
TJI:T~

~-

system, that is, a transformation for which the independent

-'-

.1

't'XT.

to this transformation the first law of thermodynamics as

U.J'

\-'-V}

CY.Ua.~J.V.U

.LHO~'

~~

-~'

~~

-.;,)

must now write dU, dL, and dQ, in order to point out the
. , lJneu,
mhnltesimal nature or tnese quanli"t""ies. vve 01
uu ..... u.u
> T

"

dU

..

U"<!

,...,,

\.WVJ

(21)

vdV =dO.

If we choose T and V as our independent variables, U

" " .L U.H'-' ~J.UU.

V.L

UHvo;:ov

V C.O.J. J.C..JJJ.vO'

/,rr\

"'T

~~

r'\

+ \~V )T dV,

dU = \~T v dT

and (21) becomes:

uv),
dT +
aT v

l +p

( ou

av T

dV

(22)

dQ.

Similarly, taking T and p as independent variables, we have:

-(?l{)
-::;n;
+ p/?V:}
-rn - dT + 7af!)
- + pIa~)
(-

dp

(23)

dQ.

Finallv. taking V and vas indenendent variables we obtain:

--~. "'- dV

{aU\ dTJ-+- -(au_\

... '1:''

The

fl-.n~""'l.n.l r.n.nn.r.1:f11

- ..,,

1'

d()

(?A.)

of "' hnrhr ;., _by rlAfinit.1nn

t.h<> "rotiro.

dQjdT, of the infinitesimal amount of heat dQ absorbed by

~

~~~J

uu

VHv

U><.O>

J.J.J.

"v .

J."

:t::

U.L

r......,

nr

......

-, .-.n.,-,...,r-...T A-, ,.-Tr<N

oy l'nis neau. J.n 0~ -~:at, l'ne

-.cIl'Y
of a bodv will be different accordine: as to whether the bodv
1S heated at constant volume or at constant pressure.
v~ vU'

T .~-1- /"1

nY>rl /"1

h.o. -1-"ha -1-"h~.,..,.,.,.,l nn.,..nn;-1-;.o.o< n+ n~Y>~-i-nY>-1- ..,.~1,,.,.,....,.

and at constant pressure, respectively.

-.-

,. -,

For an infinitesimal transformation at constant volume

a v = u; hence,

Cv

= \~j; }v = \~;, }v.

(25)

Similarly, using (23), we obtain the following expression

A~

p ..

'"

"

"

.....

~-..

P\ar }p

t:p - \dT }p - 1..,,-aT }p +

\20)

The second term on the right-hand side represents the

_,_
. ., . 1.
- ,_
.1
-' _, .
"".
-'
the expansion. An analogous term is not present in (25),
_]!.

AAA

UAA~U

"~~~

UAA"

A~

~A"

A~_,

J:' U

_,_,AA~

AA_,

~~

expansion occurs.
The thermal capacity of one gram of a substance is called
".L!

.1.

. ., ... 1.

.._

1.

....

.l ... 1.

of o~e mole is called the molecular heat.

.1

.<.1

...

The specific and

L"'

are given by the formulae (25) and (26) if, instead of taking
u:ut: gnouu ur
an anJl~>rary an1uUn~> 01 :suu"''
' Wt:
one mole of the substance. resnectivelv.
5. The application of the first law to gases. In the case
o

. .,.,

-.r-

state variables explicitly.

.
V l:l.1"UI,U1t::::S

_.c-

We choose T and
j,Jl U V t::: 111 <> lJ

lJlJ'Ij

as the

. o.Y ....,

function of the temnerature T onlv and does not denend

on the volume V. This, like many other properties of
"'""'"""'

l<>

nn hr

irn<>t.<:.hr

+.rnA

fr.r

r<:.<>.l

assumed to hold exactly for ideal gases.

U.OU.U"v

.UVlH

lJH'Ij

HlVV

Vl

'-'U<Jl

noo""'"

-l'l.n.-1

lQ

In section 14 we
. .)U

VU'V

..........

~TT">~~

~~T

,-..~

-' K

r>. ...... .,.7 .... T

'

6T

~~

ooeys une equa"L~uu.

of state. (7). of an ideal gas must be independent of the
volume V. At th1s pomt, however, we shall giVe an expen~

Ti

........ 1

:-gy-uranyuuuy~rucn

" nf

+},.;., ....,,

""'" tho

it.;n.., ;,..;.,. o

was performed by Joule.

T

<>n+

'

chambers, A and B, connected by a tube (Figure 5). He

nuea 1>ne cnamoer .t:L wnn a gas ana evacua1.ea .v, 1.ne T.WO
chambers havin!:!" first been shut off from Aach other bv ~stopcock 1n the connectmg tube. After thermal equilibrium
1-..-_.i ~~+ ;~

-~ ;~,.J;~n+~rJ 1-.YT n 1-h~-~~~ -'-

+hn

.;1-1-..;~

~ln~nrJ

calorimeter, Joule opened the stopcock, thus permitting

1

.Ll

...

------

~---.-- :._

.
~~

-.

r-l'=

-=-

--==-= -=- ~ - =-

. ---:

"1

nnhr <>

,_

...-

-~

"'liuh+. t>hanu"' in +.hA

reading
'T'h;n

of

~nn~+

the
1-'1-..n+

thermometer.
+1-.n-n

1-..-rJ

,,

'

fnrrnA.-1

"Wit.h

!'l.n

in<=>a.l

there would be no temperature change at all.

~

- - 1 .j.'l-..

J::

ber or vice versa. It is assumed

that if this expenment could be

Fig. 5.

UTn

practically no transfer of heat

,

I.:C::J-

T>

in the container was the same .

.tie then observed that there was

..
1--:

-___,.
-~

~ -=--

-'-

It 1--
~
It ".

--- -

----

....

...

"- 1.

, 1.

...

.,.,.."'

....

Since Q = 0, we have from equation (15) for the system

. .

'.

t::..U + L - 0

where L is the work Performed bv the svstem and AU is the

vanatwn In energy of the system. :Since the volumes of the
+:urn t>h<>TY\1.

A anr'f R ronYY\-nnc;nn- ,-,.,.,.

rlr. .,...,..,J.

~'hn ..... ~~

during the experiment, our system can perform no external

.n

.._

.T

rrn

t:..U = O
'

the energy of the system, and, hence, the energy of the gas.
UU llUL

ment showed, however, that there was no resultant change

.
.
in energy during the process, we must conclude that a

ideal gas:

exactly constant.

In this section we shall always refer to

lar heats at constant volume and at constant pressure,

that the volume is to be kept constant in the derivative in

once,

and we et:
U=CvT+W,

(29)

where W is a constant of integration which represents the

~~

TTY

' " K'"'-T'I."<T"!\.T A "JI"Tr-10

'"""'""

an 1aea1 gas, equa"tion ~:<:iJ.J, w

cAp~
"u"" ... u "'"
law- of t.h
...:~. , ~rn1~s for infinitesimal transformatiOns,
takes on the form:
.t~'or

T"> ..,.

'-''I"'-" .L
'-'

_.._

L'L

. .I.

I'"'

,. .,

~....,.

....

......

.e.

1'7\

"""""'1""

of an ideal gas, we obtain:

pdV

l::;ubstitutmg thlS m

Vdp

= RdT.

;:su), we nna:

.,

-.r

'
() fnr <> +N>'V'I<ofnrTn~.t.1nn
~lTll"t:> rl'Y>
this equation gives us:

Cp

(31)

= ( ~) = Cv

~.t. ~nn!'lt.~.nt.

nrP.F:;!'IllrR

+ R.

(33)

That is, the difference between the molecular heats of a gas

at constant pressure ana at constant volume 1S equal to tne
Q'.R.!'I
"l.nt R.
The same result may also be obtained from (26), (29), and
~

('7\

T . ...1

.c.

...1
}

' .I

'...I

~~~

~u

/:::.n\

ATT

\aT) 11

dT

.1

.....

./!_

1..

~~v~~

.o~~

,.,

~~

~~~~~

(()0\
,_...,./

I :::.v\.

I :::.

\a'i'Jp

\ar p)p

'R ,.,\.

...1
~u~

'R

('7 \
''

1.

.Ln I_L.U), Wtj

n OUIJaln \, .:>.:>).
It can be shown bv an aoolication of kinetic theorv that:
t:lX.t'~

OUUJ::iLlLUt..LUt;;

Cv = -! R for a monatomic gas; and

Cv = i- R for a diatomic gas.
~

~~~~,

..

...~

....

~~

.0'-''-'.....

""6...

(34)

.
LU

>Y.L'-'U

experiment, we deduce from (33) that:

C11 = i- R for a monatomic gas; and

;v

,~~-

"

If we olace
17

Cp

cl" + R

vv

l...iv

\'"' .... .I

R
(.,.'y

'. .,

0 C'l.,..,

. .

wc:lalSO Ou

....

5 .c.

T?'

--.

,,..

rvr.,.

TrT

nf <>. +:1.

i- for a

diatomic gas.
o. Aalaoanc uanstorm.anons ot a gas.
K

-1vn1'1:rn1..-.Rl ,;,-,.ro+o ...... lR R<>lrl -/-,..,

(37)

A transformation
"h.~ ~rin"~J-.~+n"n ~.j! ~.;.

reversible and if the system is thermally insulated so that no

v

'-'U

~VY H

'-'VU

<:O.HU.

~U

.llJi:j

Lu

't:l.l.l V .1.1

during the transformation.

we can expana or compress a gas adiabatically by encloslnO" -it. in

<>.

nnn-nAJ'If.-nro.-n..-lnn+~~~

,-.-,.rlinnP"I" -.xr-it.n

=nll~

n~..:l

piston, and shifting the piston outward or inward very

_, _,._, , . . n .' ,
_,
T.C
: ..

~1

))

-~'

external work, so that L in equation (15 is positive. Since

tne gas 1S tnermauy 1nsu1a"tea., 'cl - u, and, hence, flU must
~

"T'h <>.+. iR t.h lA

.._l'"A

nf

...

an adiabatic expansion.
...
.. 1.
.t..

n-a o

..-l

> cmo

..-1

Since the energy is related to the

tC"ln\

..]

"OJ

means a decrease in the temperature of the gas also .

.....

-..-

..,..., unvvL.L

the change ln temperature and the change m volume

resulting from an adiabatic expansion of a gas, we observe
... t..

...

-Jrt.

1"\

....

CvdT

r~n\

pdV = 0.

Using the equation of state, p V

I

ruin

~.one

auuve

~qua

uu

CvdT

t-

+ -;;

we can eliminate
. RT,
.

dV = 0,

or
dT

R dV

+-;=;

Tr" =

0.

Integration yields:
1

rn

R,
t>v

TT

.L

nn

-r

~T~~~

. uz:
-

TTT

...

~~-u!ll

,.....,,..,..~...--.-.:Tli..T

r,~

t.u

A "K-rr.e<

""' we ge".

- constant.

Tv~v

~ ..... ,

::- """''-' VJ. \ u v 1;

vv v

vv ~ L ~"'

v<Nu

vuo

in the form:

p._'

'-''i~"""~

.
Tvx- 1 = constant.

(38)

This equation tells us quantitatively how an adiabatic

~

ULL'-'

~....

o""~

~~vv

~~

uuv

.,....

in its temperature. If, for example, we expand a diatomic

ga;:;
,ua"Lica.uy "LO 1>wice hs inhia1 vo1ume, we nna rrom
(38) _iassumine: accordin__~!_ to (37). that K - -k) that the
temperature IS reduced in the ratio 1: 2"" = 1: 1.32 .

'1

tion (38) of an adiabatic

'
transformation
'

......... ..........,.
..-rz_K

K-1

Equation (39) is to be_e,

pV

'-''1

..t-'~

in the following
/

com; taut.
n~~~

,,

(40)

wit.h t.hP_emlat-lnn

= constant,

~-

.. L

of an isothermal transformation.
~

VJ. "''

On the (V, p) diagram,

~t:a<>..L

U.)".IJel"

~.

lol1P.

adiabatic lines represented by equation (39) are aualitatively similar to hyperbolae, but they are steeper because
T{"

1.

.....,

Isothermal and adiabatic curves are

.
r>

'

..;

~._....._

represented In
VUv

"'-IJIJI:::L

dotted Jines.
~

...... u-oJ. "'"'" ..u""

<>.uu

JJY

IJlJ~

""~.tLLp.tt1 appucaraon or tne adiabatic

expansion of a gas is the calculation of the d

1n=m,...., nf t.l-.n
Le!llperauure ot the atmosphere on the height above sea
. .
l
~1
'T'l
.

..

VJ.

...

L<:t,-

"T.'T"no

e<.-n

TYT

,.,.,..,..,.

,r,. -r,

.... ,...,.

,._ .. T..-. .....

liure wnn neignli aoove sea 1eve1IS '(;llali linere are convec"LIOn
cu
tts in the tronosohere which
'-inuallv tran
-'air from the lower regions to the higher ones and from the
l-.. -'-

~~~~

+l-

~~~~

un,

.r,

,1

1.

rises to the upper regions of lower pressure, it expands .

. .

-.,.

r
f
d"
.,
transferred to OI" rom the exnan mg: air so that we mav
consider the expansion as taking place adiabatiCally.

.... ,.,."' r.f +l-.,.

l-l-.o +.

r<~~N~~,~~<-1.,

.,.;"; ..... ..., .,;.,. ..:!.

"'""'"'

On the other hand, air from the upper regions of the atmos,.

--..-

-,

increase in temperature, when it sinks to low regions .

.U.l

U.l UOV.l

..,l-,.,.,...,...,...

;...,

\.Ol>..lvU.l,_LOV

U.l.l'V

+,.....,......,.,..,...,+,.,..a

LV

"'""

consider a column of air of unit

~\.

'
'' '
I

'

\\
\ ~

attention on a slab, of height

._.,., u""v .L.l.ll;;

.LU<> .lVVVv.L

-'-""~"'

"""

distance h above sea level. If

p IS line pressure on line wwer
f<'lf'P

'

'

''----

t.hPn t.hP nrP!":!'tllrP. nn t.hP.

upper face will be p

VY .l.l<O .l <:; '-" jJ .LC

..... p vo.>

VU

dp,

'

____
'~
....

----- ---

--

-- _:-:--: v

Fig. 6.

sure which is due to the weight

.
.
or 'tne air con"tamea In line s1au. ~1 g IS Lut::
ao::a ""'
v.t
IITHvit.v ~mn n iR t.hP. ClFm:
of the air then the wei~:rht of the
.
.
.
arr In the slab lS pgdh. Since an increase in height lS
.c . n.

..] 1.

..]

' '-' u. '-' .J

"'

l-

''"'"'"'"' . . . p

'-'""~ ~

"'' .. '-'

'-'

JL

.J.

.L

fA

1\

/0,

'~~

up

E{ T

u.n,

where M is the average molecular weight of air; M

.Luv

u..;:;. v c.ov v"

V.L

'"30V I

'-'~

""' .

28.88.

~~~~

-~

~4

~~~"

K- 1 dp

dT

an

,_ . ..

(A.?\

-s ,

, '

'

.,

9.8 degreesj.kilometer.

= -

dT
dh

.1. .LUl:i

.[(,

.l\.

0 I

K-lgM

dT

~4

ious eaua+.ion

Thif'l. t.oQ"ethflr with thfl

Al::it;U

;w lli:H

11::! l:LU u Ul:Lll V

IJllt: UUI::!t:l- Vt:U

J.a..q~,t:a

"'"' nP

:ature with altit11nP. The dif"'"'' of t

ference is mainly owing to our having neglected the effect
.
. ,,_
..l.'
n

..]

"

.J.

of air.
P.-n'L-1 .

'"'

1. Calculate the energy variation of a system which performs

,'

c.

2 Hnw nuo.nv calories are "'h"'nrbed bv 3 mnlP.R of an -i.-IP.SI.l ~ras

expandmg Isothermally trom the 1mtial pressure ot b atmospheres
t.nt.hP. finSI.l

llrP.

of R Sl.t.mmmhP.rP.!'~

l'l.t. t.hP. t.P.mnP.rl'l.t.llrP. of 08?

3. One mole
of a diatomic ideal gas performs a transformation
. .

UVJ.U

a.u

OOa"O

vJ.

VYUJ.\,U

"<OJ.UjJvo~vUJ.<J

a.UU.

VVLLUUO

""'"'

respectively, 291 K and 21,000 cc. to a final state in which

l""LUlv

auu.

VVlUJ.llv

""J.t"J '-'V'-' L"-

""llU

J.,o<, 1 1VV

formation is represented on the (V 1 p) diagram

.L U lll1U

~111::'

W UU.'i.. jJt::!-1 Ul-.

rl-in+.--..-v-o-i.-.

!:I.HU

o.n.-l<l

O"RR

~HI::'

lltJ:i:LIJ

<o.-1;.,1-.n+;~nlhr

times larger than the initial volume.

-..-

l;\J,

by~

.L llt;::

~ll:l>HI::I-

straight line.

ut::u uy IJllt:: o,y

+.n

<>

"<rnhn-n<>

1.~"

The initial temperature is

ynanucs
7. The statement of the second law of thermo ynarmcs.

impossibility of constructing a machine which could create

another.

Thus, for instance, on the basis of the first law

heat is equivalent to the total amount of work.

. .

'

taken from its environment, into work.

purposes,

sue a mac ne wou

e equ1va-

,
petuum mobile of the second kind.

e poskind.

In order to give a precise statement of this law, we

IS

conauaoneu m sucn a way tna"t u; can excnange nea't DU"t no

work with _its st
mrlinll's is __eallpn 11. l':!mu:-ce_ of t.
""_of_
temperature t. As examples of this, we may consider
1-.~.:~~

.....,

,.]_

...:r.

'd

....

1.

negligible variations of volume.

...:r

.1

~t

rl.

A mass of water which is

heat since its volume rem~ns nrP"t~i'canv c' "".:'tnt

we can now state the second law of thermodynamics in
_th.,. fnll

ur_

A transformation whose only _final result is to transform into

wor1c near; exr-ractea Jrom a source wnich is at the same tem_'Q_erature_ .th:cnualuxtd. _is_ _imr,,..,.,.,-,z,. 1 f'P~ ,.... ~~
Kelvin.)
The experimental evidence in support of this law consists
-1

"

.,

vv

~~~

construct a perpetuum mobile of the second kind .

.d t..-~

..z.

.J.

->

.c.

.2

-.,

from a body at a given temperature to a body at a higher tcmF"' ""'""''"' -i,.,- impossiute. 1._rostU1ate ot Clausius.)
TT.

!I.

perature scale.

--

~-

-r,emIn order to give a _irecise meaninsr to __the_

, .. "'
s., .LU-s., uenne wnat we mean
~~...

v.1 ... u

<='.t-L1plTICa1

_. -:: ---

~
~-.- .:~ "'pos"~ao~ 1s tnat tne transformation
of the heat mto work be the only final result of the process. Indeed it is
>nt. imnn,.RihlA

-"

--

'

, -:r examp1e,_"?e 1sotnermal expansion of an ideal gas that is

kept
in
thermal
contact with a source of heat at the temperature-'7' Sine"
_).
-~ .1.1.
.
_-_
, ~~'-"' ~.. e o;.emperar.ure
d oes not chang~ durmg
the process, we must have !!;. U = 0. From the
:first law, equatwn (15f we obtain t.h ..n T.
n. ,.,..,

-.r - - ,-;- _5_as lS equat to tne heat Q which it ahsorbt~

from the source. There 1B thus a complete transformation of he 11 t Q_..infu
-1

_L

__Thia_

-L

'
fQ'
~~~._. ... -Q.POI%Uiaun,
smce tne transtormatwn o
mto Lis not the only final result of the pro('flAH.
At the end of..the.
H

.
.

>'Uir<r.-..T-r-.

-...-r

r.,-,

01

one ooay Is
a"t a n1gner temperature tnan
another 'body. If we brine: two hnniPI'.l at. d ...,.
+
atures mto thermal contact, heat flows spontaneously by

w u~u

r:sZ:Ly

w~

nn-n..lnr>t; .......

..,.,....,. .... ~

~-

+h.a~,.,.

h.~..:~

...

+1-

+1-

n .

definition, we shall now say that the body away from which

With this understanding, we can now state the nostulate -~f

vJ.aUsiUS as touows:

~J

J~~u

~1:1

~v~~~vuv

J vuu '-" VV'-"Y -"-" vV

~vvfK-1

vv~1:1

.....,,

then a transformation whose only final result is to transfer

n.eaz JTOm D w .rJ. 'l.S 'l.mposstote.

00

-~

"~

~ .... ~-

U4~~

V4

"'-nla+a<>
To do t.hiR WP. RhR.ll
t.hl'l.t. if t.hP.
the Kelvin
Clausius postulate were not valid, the Kelvin postulate

.+ 1-

.1..3

.. .

1.' ...1

...]

..

Let us first suppose that Kelvin's postulate were not

~

only :final result would be to transform completely into

VVVLI>..

a.

lu

.1.

......, "" u

.LJ. V.L.L.L

a.

ov l U '-'"'

at the temperature t1. By means of friction we could then

transform this work into heat again and with this heat raise
, ,
,,
,
.
.

-,J

'

-=

initial temperature, t2 , might have been.

"2

'-'VO.U"'-

uv

u .......

"-'v

In particular, we

..L 44U."''

u . . 'V

vu,y

result of this process would be the transfer of heat from one

ooay ~'tne source a't 'tne tempera'ture r.1) 'tO ano'tner ooay a't a
hi -'-

...

+nrP
4

'l'hiR

f.

1ln h;o.

l'l.

vinl: +

of t.hP

. '

Clausius postulate.
~~~~

.t'~~U

V4

U4AV

VV4

V~

.... ~

two postulates requires first a discussion of the possibilities

.
. .
.
.
or -vransrorrmng nea"t 1n-vo worK. VV e giVe Hl.llS Ul1;:;l:U1:S1:SlU11
.J. ~~,+~~

in t.hP.
Sl

....

Th,. C'a,.nnt .--.,,..1,.

~]n,..A

on.

-lino- t.n K;o.lvin'l'l nnl'l-

tulate, it is impossible to transform into work heat taken

.a. V.LU

a.

i::lV

u vC

<loU <lo

lV. UJ.

P''" <>ov u. v

.., J

"' v

.V4U4<"''

"""

,-

.,...,....

A TT"T

n. T.'l

"1\ II" f"1. T""V"< ro. T A .,. 6 T .f"'IC!

~u vo1veu ~u ~.,, "'"'

une "'.Y"""'
need at least two sources at different temneratures t1 and t2
in order to pertorm such a transformatiOn. l f we nave 'tWO

leave~:> 110 ~

~nn'h

l.Il

~"'

or. 1

~.,.,...

+,...,.

~ ..... +.-.

t.hP

hv

TITn:rlr

following process, which is called a Carnot cycle.

~

1
~

(V. p) diagram, and consider two adiabatics and two isotnermalS correspon<11ng to tine "temperatures tt ana ~2.
'"Pl

fn11 -,.

"''

....

+ P<>.<>n nt.n.,.,. -in

L 1.

. 1.

~~~

~-tA

'

~~-~-

m~=>+ion

~;;

..1

\""'

'1"'1-

L'~

A
..

-1

--'-

:r

:t

~.,.

close our fluid in a cylindrical

v ...,....,

.ua.o

..

LU l > \ r

v ing lateral walls and a non con-

ducting piston at one end, so

-"'-"'

-~

Car-

t>H.liP.rJ H.

.f.' 11

11

~-t:r

-.....

i~

lustrate how a Carnot cycle can

~

,.,

~~

VJVUV

ABn 'A

not cycle.

'h.a...-1-_

nn1nt.~

AC and BD are the two adiabatic lines.

respectively.

+'h 0 +

f,-.,n

Let AB and CD be the

B, C, and D, as shown in Figure 7.

L

tl-u~

._L

1"

'

-"

the other end (the base of the cyli~der), which we take

.

'

---

"

......

u yy v

ov o..u "'"'"'

v'

heat that are so large that their temperatures remain

,.._J
LeU
W llt:lll au,y J.llliiJe aiDOUntiS 0! neat !l.re
added to or subtracted from them. LPt. t.ft h..,. 1..
t.h<>n 1
We assume that initially the volume and the =pressure of
-l-'L

.a.

"..1

'.

,.

J-'./1.'

VV~Y.;_.LJ,

corresponding to the point A in Figure 7. Since this point

. ~ "'u 1-ne 11emperauure t2 ,
-~
. . . ...,..... .,.,~the temperature of the fluid is equal to t .. init.iH.1lv
Tf
"u~::~-~::~uLe, we p1ace 'the cylmcter on the source t2 , no transfer
of heat will occur (FilnlrP. R A) ...K. ~~=~ ..... n .........1: r1
the source t2, we raise the piston very slowly and thus
.
,,
..... uu. ... u ........,
:u Lne vatue
~

-~

,.

cmr''

A "'I"XT

AT."

01\II'"TV"<T,.T

......

1\JI"T..-..N

Ul une Lr
, u.1 .ll.li:;l. ~.o.tun IS represented by the segment AB of the isothermal t,.. The
state ot our system IS now represented by the pomt B in
t' B

\.1:' o

"Ji'i,

o,

.D)

.ll.ll:l

pzu u

We now place the cylinder on a thermal insulator and

,
., . ,
, ,
-, _,
"-

value Vv (Figure 8, D). Since the system is thermally

msulaliea aunng linis process, line process 1s represente<l 1n
li'i~nlrP.

.t. R

7 hv t.hP. <l.ilil'l.h<l.t.il": RP.!

n_

batic expansion, the temperature of

_.
__c 'L
-L
-l LL
-'"
the point D in Figure 7.
~

nn .
the fluid
.

t.hiR

<~.iii .. _

decreases

,_

r--- ---

__ .i. __

-- --

I
I
I

---'--

Insu-1
lotor

t2

t2

Insu-

tl

lator

A1

Fil>". 8.

Placing the cylinder on the source t1, we now compress

.
.
line nu1u very SlOWlY atuug vue l:SOLIH::nua1 .uv ~L'Igure 1 J
nnt:il itR volume has decreased to v n (Fi{nlre 8 C). Finallv.
we place the cylinder on the thermal insulator again and

'J

segment
~llt::

cA.

;:;y

.
--d to t2.
until its temperature has Increase

W.ll.l .llUW

Ue

1:1-IJ

. . .

.LLI::i

.11.11\;.L<;U

l::iiJI::l.lJe

' w

.11:;

friven bv the noint A in Fitrure 7 (Figure 8 A).

Durmg the Isothermal expanswn represented by the
"'

A R

t.hP "'""''t.Pm

from the source t 2

~"'!'~'

;u.

IJ .Y

IJU'V

<>h<~orh"'

<>.n

ornronnt. nf hP<I.t. 0.

During the isothermal compresswn

~

llJ

.LJV 7

IJU'V

<:>_y

""'

IJ'-'

QU

or n.eau ~1 l n ~
rce ~1 ,
i:s, iu gi vc;::; UV
an amount of heat Ql to the source t1. Thus the total
amount of heat absorbed_by the system durmg the cycle IS
lUll"(;

T. 1--a ._ 1-.~

T .o+.

nTV>nn-n+

system during the transformation.

' ,

_,

.1

. 1.

nf

....,.,...,lr

.-1..-...-.a

l,n

4-1-.a

This work is equal to

. , ,..

,.

equation (16), which e:xpresses the first law of thermoaynam1cs tor a cyCle, we nave:
'

'

This equation tells us that only part of the heat that is

aosoroea oy t;ne sysljem trom tne source a1; the higher

temnerature is trHnsfor
_, into work bv the Ca
... ~ . ,,,_
the rest of the heat, Ql, instead of being transformed into
'
~~
~We define the efficiency of the Carnot cycle as the ratio,
(44)

of the work performed by the cycle to the heat absorbed at

~

.....

~.

Since the Carnot cycle is reversible, it can be carried out

in the reverse direction. This can be done by performing
+h~

nll

'

!1

-l

,.j."

-'

.1.

c>

"

When this is done, the cycle absorbs the ,;~rk L

sense.
0

+~n~

~-

-=

~~~y

.J.u:;a.u

Ql at the temperature t1 and gives up the amount of heat

~

CO. lJ

lJUv

~-

a. lJ U.J. v (, 2

As a first application of the Carnot cvcle wA f'lhl'l.ll t>n-rn_

plete the proof of the equivalence of the Clausius and the
T.T. 1

_,_

1.

..1.

-=

L'

.were not valid, Kelvin's postulate would not be valid either.

,

~~

~uuu.L

ouuu t-u "-'

pvouUla't;e,

that it were possible to transfer a certain amount of hP~.t.

~2 .uuJ..U ~:~. <>vu.Lo.ot::: au une temperature t 1 to a source at a
higher temperature t2 in RlH~h Sl. WSl.V t.hS~.t. nn nt.h<>r ,.,.}-,.,.~~~ ;"
the state of the system occurred. With the aid of a Carnot

~2 ann

C<T."r<

1:1.11

J:.ll. \.

lL

,, ,,

'""~

A '[TT

~--:z:::l.

UI

'''I:T"'.T I

'IT~~

""'

Lne source alJ "tne

temoerature t2 receives and lrives uo the same amount of

heat, 1t sutters no final change. Thus, the process JUst
.-:1.

~i-c

il-.orl ..-..rnnlrl h<>'IYO oc

,_~ln ..,:;~

,] -roo11li- -1-"ha

t-~n~"'~"~

mation into work of heat extracted from a source which is

,,

'

. .

to the Kelvin postulate.

The absolute th,

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

..3.

Tn t.hP.

preceding section we described a reversible cyclic engine,

,....

r-.

..1-

.1.

.1.. ,1.,

.+

'"

.1,

.-I'

during each of its cycles by absorbing a quantity of heat Q2

,
, .
0
"'r'
cuH.ntitv of heat , to a source at the lower temoerature t, .
We shall say that such an engme works between the tem...
-~ #
~~..:~ .,
.
Consider now an engine working between the tempera'0

"

'

"

'

....

1.

J. 'L

-1-

"J

'"

formed by the engine during each cycle, and let Q2 and Ql

>Jv

\JUv

"'AUV\.UAUO.:O

VA

"'-'<AoU

1-''-'

......

~J

-~

ture t2 and expelled at the temperature t1, respectively.

This engine need not be a Carnot cycle; the only condition

.-

, ...

.1.

.1.

, ...

.t.

-J.

i-1-

~..:1

it must return to its initial state.

,_~

t- 1-.~

'
performs a positive amount of work, then Q2 > 0 and
1.,1' 1 > u.
LP.t. 11s assume first that 01 < 0. This would mean that
the engine absorbed an amount of heat Q1 from the source tt
'-'

'-' ~

'.J

. .,

_,_

.L

thermal contact and let heat flow spontaneously by con-

UUt;L!Ull

.11-Ull.l

LUt::

ll.VLLI;:a

<>VU.LIJ'IJ

~2

u'-'

until the latter had received exactly the same amount of

heat as 1t had surrendered to the engine uur~% Mlt:: t;ymt::.
~.;.,...,...,. t.ho "'""'"""" f urmtlrl t.hllS
<>in Unaffected, and the
engine would be back in its initial state, the only final result

v .l

1,1 J.L<>

l' .l

"-'""

UU<:J

UA

on

...

~-

r~

,,w,....

~~

'w ... ,....,....

neat aosoroea rrom a singTe source w '

was initiauy aL tJID:f
same tP.rr~nP.r
t., thrnncrhout. Hince this is in contradiction to Kelvin's postulate, we must have Ql > 0.
'l"h~
.J! +1- n+ n
n :-~
.
.1.
Q~~ .~ ~engine reverts to its initial state after the cycle, we have

'

.,...

'

"'

But L > 0 bv assumntion and we have alreadv nroveo

that C~!t > 0; hence, we must have Qz > 0.
UT...,.

nro-no~.-:l,.,..,.

TOroT<Y

~~

~~ .;~~

.1

.1

1-

... ...

.+

same temperatures t1 and tz for which L', Q~ , and Q~ are the

.._,.._,

.1.'

>

,-,.

.,

'

r.

,,

engme. We shall prove the followine: fundamental theorem:

a. If the first engine is a reversible one, 2 then,
<.!2 > ~2

(45)

o'"

b. If the second engine also is reversible, then,

Qz
T~

-~

..._

~\

.c ... 1

....

"ll

Q~
--,

(46)

!.lt

'

the second engine; thus, it may or may not

.whatever. about

If we apply equation (16) (the special form of the first

~a.w ~u.1 ... uytaljJ t.u uu.1 liWO

engines, we see that the work

performed bv each en""ine d11rino- R ..,v..,lP. rn""'t. r.., "'""""' 1 +"'
the difference between the heat received from the .,.source
_, ' '

'

""

have:
L = Q2- Qt,

~~~.,,

YYV

"'
(47)

<OOLLU.

T-'
2

101e

Rv

A "

cyc1e.

~'--'

"on~;

n'

n'

..

'
'

_,

.Lne raiJlO
~q~, 2 f"l, 2
can cer"~Jarnry
oe apprvXl
,.Ju oy a
rational number to as hi2h an accuracv as we mav wish.
We may therefore place

(49)

where Nand N' are positive integers .

.
vv e now cons1uer a process conslSl'lng or J.V cycres or vne
..l en....;,...~ l'!.ncl N .........
~v~les of the first P.nll'ine.
This is a permissible process, since we have assumed that
... ~

.t:

....

'

'

:1-.. 1

"tXT\.

....

,.J

..

+1.

sense, the first engine absorbs an amount of work L during

. .

source t~ and
source t1.
,..,...,

'"'

' .,.

absorbin~

".t"

........

..._.

an amount of heat O, from the

,.f. 1

complex process described above is:

N'L' -

Ltota.l -

NL.

n.

M'n!

7\TD

and the total Rl'Ylount of heat ll'iven un to the source t, is

Ql, total

N'Q~ -

NQ1

From (47) and (48) we obtain immediately:

-LJtotal
T>

/ A .... ~

"-

_1

~2.

~~.

total

total

{\

to:n\

Hence,
Ltotal

= -

Q 1, total

(51)

.Jquatwn (50) states that the complete process produces

nn Avf'h<>n<rA nf' 'h<><>+. <>+. t.'h..,. 'hirr'h t ...,.nnAl"at.ln'A f

,;,_nrl Anna.t.inn

(51) states that the heat absorbed from the source t1

\IV

1, total)

J.<>

\JL

'lO

l'

~'

~ ~m~ co~.upleue process IS composed. ot severa:I ~~c~m;

of each en_gj_ne both em:rin~>>~ will
~ hHf'k_io__thPir iniLlli1
states at the completion of the process. From this \V<~ :-;ee
_l... a+ T.

-"-<l ..... -n

Af

]_,

...

.C.

..

:_j;''

.. l-

'

only final
of the complete process would be the t.r:u1:-;. result
.

J:

.., ' "'""' '

'

. .
.. .

.
from a source which is at the +
1.tnrP. _L _thronl.!"bnui
.out tms would. contramct Kelvin's postulate. !Icn(e, \\"t'
'

..

~"

_ID]_J>'!t. hR.VP."

0.

Ltoto.l ;:S;

Because of equation (51), this inequality is equivalent 1o

"l1, total
~"'.

0;

;;::

,..,_,~;u~ LJut:: ~::xpress1on ror "l 1 total, we oota1n:

I

I
~

If we eliminate N_'_ _and_N_ ;:.

__tb_is.t_
"J_
:H _i,l~
or equation (49), we get, since all the quantities In (-l!l)

_are

rll=

Q2 Q~ ;;:: Q~ Q,

or
I

Q2 ;;:: Q2
""1

....w_hif'h lR irlPnllr><>l,

:tl

(~

In order to compete the proof of our fund amen tal tlwonm,

-'- -1.
,

.. ~
'u .,uuw '-'lU:tlJ u
~ue second. eng1ne also 1s l"Cver:-;ihh,
then the equality sign holds as shmun_i.,., """" ......
/A>\
.u we 11aKe une second. engine to be reversible, we have, ou
interchane:i.n.J:!- t.hP t.urn -==
..J

_
..
_,
...
part (a) of our theorem to the new arrang;ment,
'~-~

Q2 > Q2
-Ll' -

Bot.h t.hiR in<>.n.nnla

.d_ _LA ,_ \

-= .

u . . .__

.P

~.,~lJl

t.

ea:H.'

nT.'\r.,-,.-...-r..-...

-r

YT~

_.,.T.'\

W~

~T~'T

nn

~~

oecause oo1;n engines are revers101e. .tlut tnese two m,.,.....,+ihlP onlv if the eau~litv sirrn 'hnln""
ea1.H1.llt.ies are
We can restate the theorem just proved as follows:
.LJ '"""''"'

.
oov<> ...,~

Vii<:>

'VIu!J~u)

~u~ ~

UJ

u~uu~

~~u

UIC>

reversible overatino around cucles between the same t.empr:ratures t_1 and t2 , all the_ reversible ones h~ve ~he sa~e ejfi-...,

~ ~'

never exceed the efficiency of the reversible engines.

.

We consider first two reversible engines.

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

The fact that

p

'

..... ,

and the definition (44) ~f efficiency.

vv <::>

.J..L

.c.

,h.j. ,; .....

a.

v <>

.L.La.

t~'h""

.L <;

v <; O.LJJc; a.uu. a.

V O.L O.L OJ.L'U

1noe.rn1<> llt.v ( Ll.!'i.\

.. "'

'

Ql ....- Ql
t.l2
~2

'
0.

Q2

Q~.

Comparing this with equation (44), we see that the

IV"

1'

'
~

1.

,_ 1

...1 ......

...

...

..C

the reversible one.

...
...,.
has the same value for all reversible engines that operate
oetween tne same temperatures t1 ana t2 ; 1;na"" is, -.:;nlS ra11io
V'\A..L

.L'

CUU.L

;., 1nn.

r.f

,rloe.nt.

UH'--''V.L '-'U.L

t'h<>
~

.-

>J.L.L'V

i!'!.l

H..,

...

~~

...

iP.R

......

'tj~f

of t.he

enfrine~

provided it is reversible : it depends only on the temperatures

"1 ...........

~2

nv

VH'-'.Lv.L'V.Lv

,...,..,~._..

,.......,

1"'1

Ql

where
t.nrP.i': f.

J~h,

t2)

J \<1,

"2),

1s a universal tunctwn

OI

tne

lJWO

IJ<::ll.LJ:-I<::.La-

Hnr'l f.n

We shall now prove that the function !Ct1 , t2) has the
.LVUV VV .LHO

pL vp .... L

UJ

A\

(53)

where to , t 1 , and t2 are three arbitrary temperatures.

~

""

~.rv

:-'

work between the temperatures to and t1 and to and ts

temperature to during a cycle, then from (52) we have:

Similarly, if A2 absorbs an amount of heat Q~~ at the

~,. ~.
ur neau Vo at. 1.ne
5 ... "'"' u!-' a.u
temner$1.t.nrP ln (aro. <H:'"'ltTY><> -F....,. t.'h~ ~~ l
. .c

.r ,..
' 1
the two engines are so chosen that they give up equal
-..,.

.v

.,..,...,..,.,..,... ... ~

~.c

....

.L

.L 1.

VJ

then,

~ =!(to, tt.).
Dividing this equation by the preceding one, we have:
f(to, t?.)
J \"0' ~IT

....,.

~nnd.-1 ..,.

nn=

.1

~~-

cycle of the engine A 2 and a reverse cycle of the engine A

'T'l.

. v~

-.,

'-'.Y'-'_."',

.Lt; COllSlSl.S

of two separate reversible cycles. Durina: the comnlPv

!-'~
s no neat 1s exchanged at the temperature to, because
the amount. of 'h.oa.f. 0 ,1-.:~1. ;
-'
'
.
"'
A2 a t the temperature to 1s reabsorbed at that temperature
h"'l' f.h.<>

n.,...,...;~~

'

~v

at
the temperature
A
'

,~.

.c:I.Uvv<;:;vcr,

an amount of heat Q 2 is absorbed bv

rv ~ u.~.c ~1 au ~UllOUnt 01 heat Ql lS
expelled by the engine A 1 during the cvdP.. W"'
o

..

t2

TY\

For this en ine we have b

'

from this it follows that we may consider f(to , t) as being a

~ = j(tl ' ~) = (} t2 .

(56)

This equation tells us that !Ct1, t2) is equal to the ratio of a

the function O(t).

Since, however, our scale of tempera-

new temperature scale, using () itself as the temperature,

noticed
; It can
constant factor.

We are therefore free to choose the unit

ressure e ual to

':1:..:;,

J.l.~.LI

.u.&VV

J.

VL'

U.LI

.....,.._,

~ .!.~

properties of any thermometric substance; furthermore, all

.,

Ll~

'

.1

oh~~

.J:

scale of temperature is used.

v n

~._..v

v.uc;ov

TY

.j..'l...:~

~u

'~

":7

" '

perature e coincides with the absolute temperature T intra.

~
,,. :c; witn tne aia OJ a gas ,,.""' ,.o
TXT.

_.,

r\.

.1

.1.

-l

...

:...:J~nl

~nN

Let T1 and T2 be
.,
\'
'.J
!:>'
-""
the two isothermals of the Carnot cycle. (See Figure 7.)
"JJt:U Cl>lJ lJHt:J
-vv-eLIIlSlJ-uai~:r
wne
IUnu OI llt:l:l.!J ~ 2 a1
temperature T2 durine: the isothermal expansion AB.
AppTymg tile mstraw, equatiOn 1T5), to the transformatiOn
'-....:;:
:; . . .
.
.
..
(for simplicity, we take one mole of gas).

-o

-,

-.r:

"J

that belong to the states A and B, we have:

u. . . +LAB =

UB -

Q2'

--nr 1JIIe- worK --perror

--u
~
Llle 1sowner
exoansion and can be calculated with the aid of eauation (10):

-wn:ere- --v.A.B

~ -

..

,.....,.

RTh lno- VB
VA

'

'

'

,.

gas is a function ofT only (see section 5).

'"

oJ

~OVVU<:>~LU<U,

vvo

~HUC!J

H""V"'

Thus, since A and

v A

VB 1 CV OJUU.\i

T7

.n1 2 tog VA_

.uAB -

"=!2

In a similar fashion, we can prove that the amount of heat

-!----

.L

.L1.

ITT

_1

, >

, >

>

represented by the segment DC is:

Ql

RT1log

~D.

Since the two points A and C lie on an adiabatic curve, we

~,

--zrunrWUJ.
J.

1 y c

.L

2 V

'

C1..,-,r'<,..._,.,.....,.

~'

~~

AO

ty,
.L2t'B

.Llt'D

..L..J'J.Y

,,......._.'<7,.,. ...

uJ.u"' vY.U"'" ... vu u;y

.
VU.V Q>J.J.U C.A.ll.l. "'VU.LU.f!>

uu.::; plvvv'

the (K - l)th root. we get:

rrou1

Vn

VB
VA
t:::Lt'

Vo

a.J.J.u

u1.1.v v.A.J:I.I.

J.UP ... v ...

"\',2

we obtain:
Q2

~'

Tz

-=.

.
....

-~

~'-1. ~~.,.~

.,

'

the ratio, T2/T1, of the temperatures of the sources when

tnese "Lempera"Lures are - ...- .-..
uu .., ......., !;;""" ullvl
,u-.. ...
Rcn.lP nf temnerature. But from (56) it follows that Q2/Ql
is also equal to the ratiO of the temperatures ot ~e sources
_,_
.j.) ~ ~
.f.~ ........ ~~~n.f.n.,.<><> <>T'<>
.J
in 11nit.R of the
absolute thermodynamic scale. Hence, the ratio of the two
'
'

''
.J

.1.
~~
texnpcraLures on L.ne "'u"'uu""'
v.-v..
.J
ennnl to that ratio on the gas thermometer scale; that is,
the two temperature scales are proportional. ~ "Lne
.: ... ' .&
~~ .. n+""'" r~ ... hnt.h """'-1"'"' h<tve been chosen equal.
we eonclude that the two scale:::; themselves are equal,
~

'

(57)

T.

J -

we need no longer use two

different. letters to indicate them; hencetorth, we snau
Q;~

<>

iJ

onct '1' .,.,.,.

.'

' '

P.CllHll

~+~

...J

dynamic temperature.
v=rrg-

.L

.... ,

.1:-'

+h.n

/~

oh".-..h,t_<> t.hP.Tmo-

n'

:'L.l.

'

eycle between the temperatures T1 and T2:

Q2

T2

\b

.l 1

(58)

ATlfi

the e1t1Clency

T2

T2

\59)

We have already proved that no

10. Thermal engines.

_,, .

. . . . . .,.. 6-ri'"'<<"'f

or a reversi01e engine lJ

<.. .1:)

'11

..,.. ,.. '""

I"'>.,.,..

"<T"r

'L

.L

...

.....

higher efficiency than a reversible engine working between

tne same lJWo Lt:::llJ.iJt:::n:uun:::~::>. .1.uw:s, <..Dt~) revrt:::~::>enL::s Lne
'h; '
noRsible effi.ciencv that an enuine workinl!' between
the temperatures T1 and T2 can have.
.+

T.

,1

.Ll.

+l,,., 1

.~

'

.+.

..

-~

rrr

:~

+1.-

temperature of the environment, and is thus uncontrollable.

. .. .
,
. ,
. .
.,
-.,
temnerature T., as hil!'h as nossible. Of course we must
always bear m mmd the fact that the actual efficiency IS

..

.~11~

-~~~..t~~n'hl

.j.l..,.,~

~-

4-l.

~~

(59) because all thermal engines are far from being reversible .
,....
, .
,
.
..,
~

'.L"

to extract an amount of heat Ql from a source at the low

.L' J. UJ.H
UJ. W UJ. .1\.. ..U
""' .uJ.!-'""~ a. "
v
1 u .)' "' '-'.., v ~
~ a.u
(43) and (58) we easily deduce that:
U-L

.L

r.
r.

/L~\

'lt

'1 2

. .

'-'~.

Tt

..

..

<:>

using the temperature of the environment as the high

UV

~.1-''-' '<AW'-LL V

..<.

'-..'CU U ' - ' V

,4.>,

V.)' ,_,._...

.J:-'vJ.~~I.Jt:::U

J.J.J.

I.JJ.J.t:::

J. 't::: Vt:::U:St:::

sense could thus be used to extract the heat Ql from a bodv

cooled to a temperature, Tt, lower than the temperature
.I! J.l.

. >-

'

T .L

rrT

'

'

_,

'~ ~'

'
amount of work needed to extract a given quantity
of heat

-""

,..,~

~.,

~u

vuv

....

L ~ VU."-

.L 1

Ut:::l,;;

larger and larger as the temperature T1 of the bodv decreases .

.rus m une case or an oramary tnermal eng1ne, the efficiency
of a refri~Zeratinl!' mRPhinP is cmnsinP.r.,hhr '
-r'han 1-'ho
-ulermodynamical
. efficiency (60) because irreversible proc".7

VV"

~U

L'

~=

Ut::: V J.l.,;t::>:;.

'-'

........... ~

The

~ntropy

11. Some. properties of ,cycles.

.
"'=>'

.L

Let us consider a system

TT~
-~-

"J

~-

that during the cycle the system receives heat from or

surrenders neat to a set ot sources naVIng the temperatures

.,

'

"'
between
the system and these sources be Q 1 , Q 2 , , Q n,
respectively; we take the f.J s positive n they represent neat
-

'

-'1

"-1

.-~o

...J

.t.l.

-~-

.Ll.

We shall now prove that:

f-. Q. < ()
i
. , ... . ,.

i-=1

.,

tn.1 \

.L

.'

..

-;

-.;

reversible.
1n oraer to prove ~tH) we mtroauce, oesiCfestne n sources
li ..t."'rl ""'L
a.nnt.h .... Qf'>lll"f>"'- nf h<>-ot. n+ ..,..,... ..,,.'!--: ... _...,,. ... +om
perature To, and also n reversible cyclic engines (we shall
taKe n ._;arnot cyCles, t:1, L;2, , t:,.) operating between
f.h<> +--~-

1f.111"<><! rr'

temperature To .

-,,

'T'.

,,

f;n~ITr

q'l

n..,rl

+l"'

VVe shall choose the ith Carnot cycle,

~

~~v

V~A~

v ..v

vvll~}'v~

Q,OJl.U v0

.L

.1.

0'

to be of such a size that it surrenders at the temnerature T

the quantity of heat (J;, that 1s, an amount equal to that
_..

~1... ...J 1
'-'.1

""""'"''"'~'"''-"-

.1.1.
'-'H'-'

C1

.J.

.L1.

"'.1"""""u ,._, a.u vue;

uvu.~-z-i

Accordin~

to (58), the amount of heat .fl.bRorhP.n hv C.

trom the source '1 o IS :
Qi. 0

= :;,~ Q,.

(62)

We now consider a complex cycle consisting: of one cvcle

--ur une roy
~ ana one cycle ot each Oftlie -carnot cycles

..,.,,..,..TO>

..

v1, vz, .

ne

~-

...

~~~

"' oi neau au eacn or

the sources T 1 T 2. T durin!r the comnlex cvcle is
zero; the source '1 , surrenders an amount of heat Q; to the
J.

' "--'n

Tie1J c:rx
M

o~ro+~...-.

1--.,+ ;+

.Q

c ...

cycle

.,.,..+

,;"~" +'t-.~ M~~~ ~~

r..f

hnn+

+1-

The source To, on the other hand, loses an

,

.
c2 ...

-.

-.,

"Y

absorbed bv the Carnot cvcles Ct.

Cn
'1
'0
surrenders altogether an amount of
Thus, the source
(62))

ho<>+ ..,.,..,,,.,] +n

,.,., ~ Q;

~"'

/'\

... ,..

,_

.1

.L

'"'"'\

.1 .

1'

.L

..

i-1 .L i

i-1

.1 .

.LL

...

.L 1.

'

svstem composed of s and c . C2, ... Cn receives an

'
amount ot heat (Jo trom the source :.t o. .uut we nave
..,].,..anrl~r

t.h<>t.

in

t-rq_ni"

n-uroliro

<>

,Rt.inn

t.hP

'tXTnl'lr

performed is equal to the total heat received by the system.

rnt.

rv

ct

rv

rt

-'-

+ ~ + 1-

~;~ ;~;+;

,1

.+ .+

'

at the end of the complex cycle, the only final result of the
..... ~

-"

-~

~J ~

received from a source at a uniform temperature To. If Qo

were positive, this result would be in contradiction to
< II ,..,..
TT .. 1
'
l
.
1 .L
.C~ll~'"" +hat n
. T+ .Lt. ' r
from (63),
.L

L: ti
;-1

<

T,

o,

which is identical with (61).

. -uy~t:aOliJl<J'
,
,1'L 1
.LI une cycle }JI:::l lVl
VVv va.ll
...... .._
it in the oooosite direction. in which case all the Q; will
change Sign. Applymg (til) to tne reverse cyc1e, we
..]

,\ . + ~;~

f'

,_,

Q; ~ 0.

'

l"'l'

"
~

Qi

i-1

'1. i

-- ...

.1nus, i:r "tne cyCle is rt::vt:JJ.;::;iule, "Gni::> ine-Y.'

."', l::tl:l weu a:s
(61) must be ~,q- .c .:~
This is possible onlv if the eaualitv
s1gn holds. For a reversible cycle, therefore, we must have:
(64)

This completes the proof of our theorem.

.l.J.J.
t:J1::il>
\,.U.l.)
\V":t:)l
Wt:
iiL1::i1::i
IJ.lJ.<:i
svstem exchanges heat with a finite number of sources
'lr, '1 2, , '1 n lt lS Important, however, to COnSider
-1-"h<> """'""" f,...,. ~Tl-.;nl-. -1-"ho a

ovroha~~"""' 1-...-,n-4-

,.j.

tinuous distribution of sources.

.3

/n'\

1.

/DA'\

the e11tire

.1

~,;+h

"'"""'-

In that case, the sums m

.3

1.

'

.1

.l

.3

c~cle.

De11oting by

cf

the i11tegral exte11ded over a cycle and by

dQ, the infillitesimal amou11t of heat received by the system

<U>ll"t"nA nt. t.hP

<=1.

p_

>+11'J'P

'T'

THO

1-. <>TT>:

J. dQ
J
1 . - ,_

, .1

...

,.

-,

'f
wru.cn
12

IS

.L
_,

1.00)

T - u,

vaua on1y Ior reversm1e cycles. 1

Th P.

'T'h p

F!n

'"""'

which is expressed by (66) call also be stated in the following

A

....

.3

1.

...

,,,,_

\VUJ

GUU

\VV~>

we mu~t p01.~.t out that T represents the temperature of the source which
SnrrPnriP.r.. T.h A
dif.V 11f hA<>.f: na <> n ..:1 ;
-~
"
' ~
H
"I;empera1;ure :J. oi 1;ne system (_or ot part of the system) which receives the
he~~:t dQ .. _Indeed, if the cycle is irreversible (relation (65)), T' :;;; T when
and when ,~9--is negative, T' :2: T. If the cycle is r;~ersible howe~~;
(equation l66JJ, we must alwavs have T'
T i'.~nn'"'" an ov ... ha,:"" ~f J.o ...
---.:re-o ' " ' " ' wu
'
"'" '
. ~no oemperatures IS not reversible. In (66)
we may therefore take T to be the temperature of the sonr"" n;..-:1 ,.].,, th"'
"'

-~ ~, ~"~ ...

"uau

~~~

one neat; 0:1,1.

L1ons1a.er a reversime t.ransxorma1iion wrucn taKes tne system

from its initial state A to the fin~.l stat.P. B. Tn
.~. ~n~~~
many reversible transformations from A to B will be pos:t-..1

:.c......

.1

"[;'I

.......

of the system can be repre-

'

'

1:'1

'

continuous curve
...__
ing the two points A and B (repH.nv

//)

.....

.j.l.

..J

: ... :~1

states of the system)

V

-'=~~1

corre-

transformation from A to B .

.....

Consider now the integral:

extended over a reversible transformation from A to B

\_U,~

.1<:; IJU'tj

IUUlJ Vl .llotj(l,IJ i:LI

JJ'tjU .lvV"lli:>.lUl.Y

JJ.Y

\1.1.1\j O.Y

at the temnerature T). We shall nrove that the above

integral is the same for all reversible transformations from
'
.
-.,
'"
.,
'
'
transformation depends only on the extreme
T
~

.t1

U./OlN

!IJ

bft!J

bl <Nt

b<>J VI

..

II

TT

"'"""

.-r-.1-/--___.-/JI

,~hln A

+uu-.

transformations from A to B (in Figure

.LV>

\IUv

0\li:L\It:;O

U.l'tj

.1'<'1-"~~

<t.O

on the transformation itself.

ln order to prove thls theorem, we must
"'h"'"'' +ho+ ;; T n..-..-l

...

J:-''

i:I>UU.

Fig. 10.
\IUv

\11

mations as line1:1 merclv as a visual aid to the nroof). then.

r,.,r,.. dQ_', . - r,.,f" dQ_', ..

urr

(67)

t.hA t:wn 1nt.r>O'r!ll>< "r" t.!l.lan ,1ln.,rT t."h,. n<>+"h<> T

~.nrl

TT

respectively.
l L .r>.

.L .V

.L .L

.a. ,

.L 1.1.10 .l<l

a.

.1~v~.1

uyl.:al:',

formations.

~~-is-

up or

. .

.1~ v~J.;

~.oran:s--

We may therefore aoolv (66) to it, so that

dQ

LWO

.L

..

(I

~)

The second integral in this expression is equal to - ( f

because in the transformation from B to A along II, dQ

-'- . 1

.L ._

1.

-...-

-= -,

transformation from A to B along: II.

lt>'l ), ana tnus prove our theorem.
'T''hP

..J

(~7'1

h"<r

,...,11.,...:1 4-l-.o n~-

-- -

..:J

,....,.,hl~~

.c

' '

Hence we obtain

new function of the state of a system.

~-1-.~~1-. ~~

.1

.L

.+

n,;;, t.n N&>fi,..,.,.

....

""

This function,

thermodynamics, is defined in the following way:

...,
system and call it the standard state. Let A be some other
equilibnum state, and consider the 1ntegral:
~T

S(A) =

'

a~

(68)

taken over a reversible transformation.

..

We have already

A and not on the partic~iar reve;sible transformation

trom u to A. tsmce the standard state 0 1s fixed, however,
we mav

;;;s:~.v

that

(n~n

;., "'

f11nnt.inn nf t.h,. ,.+ ... +~

"",..,1~T

We shall call this function the entropy of the state A . 2

2

The necessity of restricting this definition of the entropy to equilibrium

states only arises from the fact that the transformation from 0 to A must

~u.

; ........

.nenec

it follows from continuity considerations that the initial and final states
0 and A must also be Anni"Hhrin~ ~+ ....
.1n ma:;.Y cases, nowever, it' 1s possible to define the entropy even for
non-equilibrium states. Let us consider for exa~nlo "',.v,.t.<>Tl'1 ~~ -'
~ P~''""' "'"
l>emperal>ures ana pressures.

UV VV

U VY V

<>'-;l l..~~~~ J.Y.J.J.J.

''"

<:UJ.U.

..0.

JJ 1

J.<:; lJ

zt.UU.

S(A) and S(B), respectively, be the entropies of these

s-.;a-.;es. vv e snau snow tJna{l :
~09)

where the mtegral 1s taken over a reversible transformatwn

....

In order to prove this, we note that the integral on the

J.J.OU\J-

>"~U.V

~~

\~V/

U~~

VUV

~~~

~U

~VVV~..:>J..,J.'V

transformations from A to B. We may therefore choose a

panwu1ar 1Jransrorma1.10n consis1.ing or 11wo success1ve
ible transformations: first a reversible transforml'l.t.ion
from A to the standard state 0 and then a reversible

can be written as the sum of two inte~;als:

1J

dQ
--,:p.

(70)

We have by the definition (68):

S(B)

= {"
J"

~;~,...,

i-1-.a +-r<>no-f'n,.Tnot;_......,

frr.TY>

c!fi_,
....

tr.

.;.,

have further:

JA

~ =

I ~ = - S(A).
/o T

Substituting these two values for the integrals on the

nght-nanu slOe or ~IUJ, we ootain ~t>VJ. \.,!.~ . .u.
The f1pfinition (68) of the entr

choice of a standard state 0.

renuircs the arbitrarv

We can easily prove that if,

n ~U~ rhnnn <> ,l;f'tn .. n.nf- c.-/ n~rlo>rl Nj ,fn nt +1- ,n

----------------------------------o.f.~nrl

n-f'

Let each oart however have a u11iform temncrut.ur" ILnd nrcssute. If the
uu'"'-""" P"'""'''"" '" ""'"' o" "'"'" o nou """"' """"'' ~"" "Y""'"' WUJ. ~v.dently not be in cquilihriurn, Hitwc heat will flow from the hotter to the
, ...,.

.1 i:
,,;ff. .
,
.r .
.
"'

..
u
however, we enclose ea<'h part in a thcrmtdlv immlating rigid <'onta.iner, our
'

..

urill h<> in "nnilihrinm

uropy.

'

""

'

"nrl w< RIHlil ho> nhlA t.n ~i ..

>inA it.u .,,..,_

..,.,., ...T,..,.,"D rYn"U"

the new value, ~

........ ~ A rliffers L>_
constant.
rv

.... 1.

T-"

~A),

w~

.1v.1--v.rR:f

'-'l:'J

'-'L

uuo

the old one, S(A), only by an additive

~~

J-t-.,... ~~~' c.+o..-.rl,._r.-1

-are have

M+~+,...

bv

definition,

I ~'

S'(A) =

where the inteiZ!'al is extended over a reversible transformatwn from u to A. ..t:Sy app1ying \0:1 J uu uni.-:; ~u.uo 0~ ""'' wo
~~,.1

+h~+

S'(A) = S(A) -

S(O'),

S(A) -

S(O').

or

S'(A) -

FlJ

line
.u
"'' .....,. .L"'
,
,
,
,
constant (that is, it is independent of the variable state A).
Thus \7I) snows that lill:e airrerence u~:::Lwt::t:a.t ~~ ~:::.ut..tvJJit::::s
nf ~+,...+,... .d ,J..-+~inP.-1 "Wlf,h tWO different Standard StateS, 0
and 0', is a constant .
.u~w

.........
.L 1.1'0

~;:;1

'UL'-"J:'J'

.LU

J..l.
UA

.l.~-

...J

. .J..

f....,,.. o.-. n;Jrlit.imp ,..,...,.,_

'L'

us when we are
stant. This indeterminacy
. will not, trouble
.111 ;:;t", -ver a. p v
,
dealiilg wit:in
:u.JJ.Y
h
r the additive constant in the entropy plays an
important role. We shall see later now tne t.niru 1aw or
L-~uu~;:;

+1. ~~-

.~,..., ,..,.._-.n.-.l~+~M

t.hP rlPfin-~ ... - nf t.hP ~n~

nncl

also enables us to determine the entropy constant (see

~_l.l

Lt:a

l' .L.L.J..),

Both from (68) and from (69) it follows, if we consider an

inhnitesunal revers1o1e uanswrmauion uuring w
Lut::
~ n..;o~ hv $l.n aTnn.,nt. dS and the svstem receives an
amount of heat dQ at the temperature T, that

That
1 o;;

IS,

dS = ""~
T'

(72)

the variation in entropy during an infinitesimal

-~

LV1

.ll:i

IJ

uy u1 v

IJU'V

>

r> .....~T

....

,-u~::u uy une l:i,Yi:llit::l.u oy tne temperature ot tne

o:r nealJ
m.
The entropy of a system composed of several parts is very

fA +1-.a ~"~ "'~ +1-.n

,......,,.,!

p,

.ll ... 1..

.J!

_...

This is true if the energy of the system is the sum of the

..

"

"

..

.-

.t"'

"J

the svstem during a transformation is eaual to the sum of

the amounts ot work performed by all the parts. N otlce
+1-.o"o nnnr1;+;nnco

.f-1- n.f.

...,,;;.~

TlAt

<>>'<>

some cases they may not be fulfilled.

"

~1.-. :~~

~~.-1

;~

Thus, for example,

.f.hn.f.

substances, it will be possible to express the energy as the

V1

-1.

,.j.

IJllv t::UCl e,1<0<>

+1-.o

">r>a

" W V

i:l U

rd' +1-.o.

-.,

hnA "" 1-.o.f.n

-~

.u

l'Y"'

.,.,1-,.,..,..,.

"""u

+1-.o~T

The surface energy can generally be

are m contact.

."

~11 o:::;

V1

onaY'<T"

;..

subdivided; otherwise, it can play a considerable role.

J_Jt:;IJ Ui:> ..COUUL<O lVL

VL ;ouuy

~llv

_,

~11a~

VU.L

"'J'"~v.U.L Q

is composed of only the two partial systems Stand 82. We

suppose tnat tne energy u 01 s 1s equal to tne sum 01 une
iP!'l TT !'l.nd Tl, of -~ !'l.nil .~.

I
~

TT- TT. -1- TT.

nnd that the work L nerformed bv s during a transformation

is equal to the sum of L1 and L2, that 1s, to the sum ot the

-1.

nrl hu o

..,_

cnHI

o.

L1

+ L2.

fnl\ows that the

heat Q received by the system s during a transformation
t.h P!'!P !'l.!'!,.,ll' dion"' n.ncl fmm (1.111 it.

'-

'

n - n.

-1-

n.

received bv the two narts. This

enables us to split the integral (68), which defines the

of t.hP !'l.rr~mmt.,., of hP<lt.

'.

;tralu

T',

vU~LV}'J

UWV

"11'--

p~11.

of two integrals which define the entropies of the two partial

-~

.....

..::1

When the conditions for its validity are fulfilled, this

..

. ..,

~-"

~-

the entropy of a system even though the svstem 1s not 1n a

state ot eq111hhnum. Thls IB possible if we can diVIde the
n-h:r.oon

<>~r.,t_.,..,...,

.+

<1.

TillTYl },.,.yo nf n<> -+~

is in a state of equilibrium.
. 'L

. J!

."

1.

.1

..L

aanh n-r urhinh <>I nTH"

We can then define the entropy

'L

.1

I'

L'

of the total system equal to the sum of the entropies of all

..

~-

-~

-..-.~

two states A and B of a system.

We have from (69):

I.

S(B)- S(A) =

~.

provided the integral is taken over a reversible transforma'

.,
..,.
A to B over an irreversible transformation, the preceding
equation no longer holds. We shall show 1n that case that

WP. h<1.VP. in"'t.P.j:j.cl

T"

'

t.hA inP.nnRlit.v

('7~~

(B dQ

S(B)- S(A) >

.~~

In order to show this WP. +<>1-"' o11r svstem from A to .H along an irreversible

.Y'
Fig. 11.
\ Vv'

~v

".LUO

"

><>+.inn

.,~..::1

'1-.~ ~1

.._

:b ,
a l ong a revers1 le transformation R
-,

";

...,u._. "'"

~VIo;t;

reversible
cycle A I B R A.
.
ll.L<l V<lHHUlt:: cycu::, we OO"taln:
.

.1 U.l.Hl

(see

UU

u-

If we aoolv

u u" ~

ru s<;ate U and the state A of the

total system are gJ.Ven, the corresponding states of the two parts that
comnn~" th" +.nt.~l

~~"
a

..,..\.

systems have been mdi.cated by the same letters 0 and A

4 It can easilv be nroved t.h ... t. ...11 t.h..

:.;

a1~u <;O unlS generanzea aettn1tion.

'

....

1"'\"D"U"

.t

,..

'

\)A ~-)I+ \]8 ~

T R.

;;- =

Since (69) can be applied to the reversible transformation,

.1, 1 J.l-UlH V

.n.,

~V

VVv .Ui:l.Vt:::.

/A Jr.'\

\}s

CJ \.t-i.

T)n

d~J:S).

Substituting this in the preceding inequality, we obtain:

0 >

()A

~)

I-

[S(B) -

S(A)],

so that, for the general case of any type of transformation

'
,....
~

1.

'

rs

).,

_,,...
;;:;, 0\D}

OV:I.J,

which 1s 1aennca1 Wlt;n ~16). '-l~ . .u.

For a comnletelv isolated svstem (7:l) +.<> L-.,.., on ~simple form. 8mce for sueh a sy:::;tem dQ - 0, we now find
1-l-.n+

S(B) > S(A);

(74)

that is, for any transforrnation occurring in an iNolated system,

-,;n;e- er , "1-'Y UJ ~n"' ,,,,._,, .->H.~,,.., cu.{{. .,...,,,<,, -ue-~--r;n:u;n; c.na~ OJ r,n.e
initial state. If t.he tra.n:-;formntion lS rcverHible the
equanty s1gn now:-; 1n ~ 1 "), anu Lnc flystcm. sutlers no ellange
1n

Pn-~-~~~

..

It should be elea.rly un<ler:->t.ood that. the result (74)

.
r 1..,1_
1, . '
.I
'1"
'1
" ~'T""""'"'"'
"' w~~il
'J "
-=FJ:-'
. ' ..... -~ cr.',-...
the aiel of an cxt.Prual :-;y:-;tern to red uee t.he entropy of a

r,

UUU.)'.

.L

uo:;

~::ut-a

''I '.Y

\Jl

' 1

-~

11\J l l l

'"'.Y;, t

-~111:-i

lILIHlll

"oge1.-ncr,

however, eannot. decna:-;e,

when an Isoln.t,efl :-:y:-;1 <~In
An

1:-> n1 t.llc :-:tate of ma.xtmum

f'nn,.,i,.;:tpnt UJit.h if,. <'liPruv if ""'""'+ ,,.,.],.,.,r,. ~""

further tra.n:-;forrnati< lll i>eeau:-;e any t.ntn:-;formatinn \'Vnuld

-~~ .. 1+ ; .. n ,l
.I'
. '1'1 .. " .. .r . . '
' .IL'
'
entropy 1:s llw 111 m;f ~>I ah!t ,-.;/aft for an isnl a ltd sy.~l<'m.. 'J'he
.
.
nu;L v ~ U.H HJIUlllU.IIe(HIH l.nUlHl(ll"lll:t\.!llllH lll an L-;ola'tect
j.

. J

.. J

.~.,-.~~?

system proceed m sucn a ain:a.r~;iuu a:::; Lu--irrm

-,;ne entropy
,...,n hA P.nnvAniP.ntlv ilh1Rtrated bv two siinnle examnleR
.Ai; the first example, we consider the exchange of heat by
1.
1
.J.
.+
1-~+
+-.nn -na ~+n
A
~ ~ ...J
A
.J:
system. Let T 1 and Tz be the temperatures of these two
L

.1:"

,,

,.,..,

.....,.

~L'

,.....,.

-.,

-" '

~onduction

body A

from the hotter body to the colder bodv the

giVes up a quantity ot neat fol which IS absorbed by

+1-.~ -'h~AT?

'1"'1-.,c

+1-.o

~1-.n~~~n

n..f'

n~

kTr

amount Q/Tt, while that of A2 changes by the amount

.
~

_,

. .

..

system is, accordingly,

Q -Q.
~~ .... """

'T'.

t.h tQ ..., .. ,.; .....

....- ,.,.,-_

i!'l ohvirn1"'hr

!.L

;-.reo

cu-.

+1-. n+

the entropy of the entire system has been increased.

A

.1.

.J

by friction.

-~

".Jn~

.j.l..-

'

_...

"

...

1..

This irreversible process also results 1n an

.r oJ

...-

by friction receives a positive amount of heat and its entropy

increases. Since the heat comes from work and not from
.
l,.,.,..
+J..;., ;n<>-rann~ ~J: --+
"'" n..f' +ho
~

.l.

compensated by a decrease of entropy in another part of

'

The fact that the entropy of an isolated system can never

.
.................!'!>
CA>.L.LJ

.,...

LV.L.l..L.LQV.LV.Ll

.LL<>o<:l

i:l.

Y~~-y

J.HIJer-

pretation from the statistical point of view. Boltzmann

has proved that the entropy of a given state of a thermo.J.

. 1

. .L

..L

.1

"L

to the probability of the state.

.J

v~~v

'-'-~

-r

IJ!V L VV <:l<:l.U

LH~

dynamical and thermodynamical concepts of the state of a

;:;y:::;Lt:J.ll. ..LU
tJne uyuamica1 st.alJe, It IS necessary to
have the detailed knowlede:e of the D< ;t;,-,.,... <l.nrl Tnnt:irm nf
arr the molecules that compose the system. The thermo

-'

'

U.J

o~V.lU!;,

T7'-..Tn"IT"> r>.

--

-.....,.r

m par
:..,ers, sucn as-nre Temperature,
nressure. and so forth. It follows t'
~
r.h,._t. t.n t.h<=>
same thermodynamical state there corresponds a large
,; a

~.,~1--..,. ..

~~

,.:j,~n~;~nl

+n+~

T.

.L' .. L

,_

criteria are given for assigning to a given thermodynamical

LJ

".f"

"'V""V'-'0

(See also section 30.) This number 71" iR 11"-llA.lhr PRllPcl t.hP
probabil~ty of the given thermodynamical state, although,
~+ ..;n+lu

o-nnnl.;~,-,.

;.j.

in the usual sense.

;o

~"'hr ~.,.~

.1

,.j.'

.'L

Ll.

.L

.'L " '

The latter
. can be obtained by dividing 71"

-...

".,)

We shall now assume, In accordance with statistical

.
l<t.
Hl
<loU
cLI::U
~~1y unose
'
~y

n~~,..,.j.

"~

+ .. n,.., r

n+;,..,..,~

"'"m'.,.

,.\...~.1

.J.

.1

to states of higher probability, so that the most stable

,
.
..

. .,
..,.
"J
=
consistent with the given total energy of the system.
.
.
YY 1:: ~1::'1:: IJlll:t'-'
~ ~
lJ!L-1V11 t;:~<;al
-aJ par
between the properties of the probabilitv 1r and the entronv
t:i ot our system, anct t11us suggests the existence of a func-

..

..

-!-;,.,...,.,.] >nlotinn<ihin. l

,.j.

nu>n

Q,.nl. n .. ~ln"'-"

t.h<>TYl

,1,;~ ~no

actually established by Boltzmann, who proved that

Wll't:J.-t: /\, liS

s
a

CVll>::iLUHL '"

k: log.

7r

(75)

'

t-He JJvor-<JHoudHO G onst-an~

anu

1::1

enual to the ratio

R

{'7F.\

.,.
Without giving
.
ull(;l (JXlSLCilCC 01 tL

'

a proof of (75), we can prove, assuming

.
. u:sniP oe~,ween o anu 71"
IUHCLlUlltLl .U:.lH
1

t.hRt. t.hP. Pnt.ronv is

t.ional to

t.hP lnO"qrit.hm of t.hP.

probability.
'V

"" P J 0 VvLU V'-UU,t-''-'"''-'""

V~

V"

pa.>

\JO:> l

aUU.

LV V "-' l

"'0

ue lJne entropies ana '11"t ana 71" 2 tne prooao111t1es or lJne

states of thP.RP.
~
We have "CII)

.o2

s1

= f(7r2).

s~

= f(7r,);

But the entropy of the total system is the sum of the two
.L

. .

IJ

.IJ

-'-

.C!

and the probability of the total sygtem is the product of

tne two prooamlltles,
'~

t,l-

T.\.

Pnn .. +.;nn"'

~.

...nil

"-

("r[\

urP

t.hP.

nht.!'ll.;n

following:
..Lilt::

~'

+ f(7r2)-

f(-nytr 2) = f(7rl)

uut:::;:y

~~,_;IJ

"~~t::

~~~~

equation:

f(xy)

+ f(y).

f(x)

(78)

This property off enables us to deteriD!ne 1ts form.

f'7Q\ ;"'
'

'/

+...,,.,.

f(x

+ xe) = f(x) + f(l +

u;y

UUIJH

..Li:L;y~u~-

E) .
l-t::IU

+ xef'(x) =

+ f(l) +

f(x)

For e = 0, we findf(l) = 0.
X} ~X) =
~

...

Hence,

(1) -

'

~~.

7,..

J ,...,,

.l..lliJt::~J:;

Wtj UU

. .
TV .LVf;> -"

J '""'

k,

'T

Then,

all terms of an order hia:her than the first we have:

f(x)

07

"'J

where e is an infinitesimal of the first order.

.l.!or..ll..~

:::lmce

-l!n-r oll -.Yol,.,.., n.t',..,. .,.,...;! '" '"'"" ..-.-.o-.r +ol.o"

e/'(1).

'

.
~

-r;, "''t rn ro

~nu~

'"'""

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

IJ 1), we nnu.uy nu.ve.

C't

'- 1

We ~an nlace the constant of inte~rration eoual t.o 9:P.ro.

This IS permissible because the entropy is indeterminate
-1-'h.o.

+r.

L>~+o.-.1-

obtain (75).
'n

r.-4!

vu~~~v,

~IJ

n"

~r..-.~1-n.-.+

nrlrl;

uo

ouvu~u.

l:li:T,...

.~:y

.t:-.nll.-

.j..'J.,.,.~

IJUI:l.IJ

.-:l'

IJ.Ull)

constitutes no proof of the Boltzmann eauation (75) since

we nave not demonstrated that a lunctwnal relatiOnship
,Q <>rl

'h ...

.;.,.j...,

hnt. h<:>vl>

TYH>-rahr y.-.arlo it

<>

plausible.
14. The entropy of systems whose states can be repre-

J.l::j
:u U.U i:l \ t' , p)
Li:l.IU..
L' U!- w
::>y
t.Jue
s
defined bv anv two of the three variables n. v and T.
If we choose T and V as the mdependent variables (the
"+ot.<> ~,...,,.;.,l-.ln<>\ tho hoot rln
ivt>rl l-..r t'h.o ~m<-,..,m rln-rin<r
'
an infinit.esimal transformation as a result of which T and V
1

""

'

'

1TT

'

1 '""

expression (22)
dQ =

(aU'
-- )
v

t.ht!> n.nrl (7'}.)

H'1

,...,._

.J.. u~~

"VV \_/

.........

'
"WP

.1.

+ v - dV.

-(at~)
---

- ,.

(79)

'

oht.n.in

! {aU\

dQ

./ JJ.

dT

,/'1'

'-.<l.I.!Y

j_

c..\UY/T

.
'-'Ap'..__.,:;.VAK

.._
1
_
\_Ull ~ . . . . H><

1 ,.. (aU\

_l

~-

'H

.:JA

_.,~

"'

fs:tn\

rlTT

.1

.:J Ct ..].' ,...

,._......_ '-""-'

'-UU~

.
._.

We know from the general

one very important re:-;pect.
.
.
tncol'y l,nar, t.rlel'(~ CX!HlS H, IllllGllOU 0 UI wilt: tii.J<tt.e U! Lilt'
><V><l.Pm.
In our ~n.:-;e S will therefore be a funetion of the
variable:-> T and V, whic~h define the state of the system:
-,
'T'l.

.1-" rr,

. 1
' <

.. .

"

...

,_,,,'

>1

. ;,~1.,.1-

1-.n~rl ~;,1..,.

'

\'

.,

.,r ts:un

-io

therefore the diff('rcnt.ial of a function of the t.wo independent

van:u>teH

ann

1 .

,...,.,....,,

..... ,.,.

Tn general, a ainerenvia1 expJ.Vl'l.riables x and 1.1 such as:

dz = M(x, y)dx

--or -,;wu-

llo

N(x, y)dy,

"(82)

is said to be a perfect differential if it is the differential of a

~-

-~

-'-'

-l

TXT.

-1

-'1-'

-'-'-

-'-

fOIY\ ~~ ~

perfect differential of the independent variables T and

.
.
.
~ lJ iiS weu KllOWn
iJ. !.L~ J.~ <:~. _fJtoJ.-J.tlCL . _._._._. _. _,. _
'
and N must satisfv the followine: eauation:
&M(x, y)

&N(x, y)

v.
.tY.L

(83)

v~

"tVhA-n i-.h-i<l

...1-it.-inn ;., f11lfil1Pcl

~+.

;l--.]o i-.n. lnf.Po--r~.f.p

lR

(82) and thus find a function which satisfies that equation.

...

.:r

AL

'-J VUV-L YY

:
I
I
I

I
I
I
I

J.lV

QU.IjJ.l

'<'"'-"

.L U-.L.L'-'

ists, and dz cannot be considered

as oemg vne dltlerential ot some
function of T. anA ?1 +'hAn t.hR integral of (82) along a path con-

/r

JI

-'-"''-'7

-'- ,_

-'-

,\

(_

plane depends not only on these

"w v r \. "tne limits or "tne integral) but also on the path joining: them.
As regards the two differential expressions T79) and (80),
Fig. 12.

"~+

"tVA h5'1.VA 5'1.lrA<'O.rhr nnt:ir>Arl t.'h<>+. .-1.\:l. -i" n

.-:1~-l'l'n

--'-:nl,

If we consider two states A and Bon the (V, p) diagram

. .L

_]

1.

.L

_,_.,

>

II (see Figure 12), and integrate dS along the two paths I

ana .Ll, we get; tne same result In oatil cases, namely,
S(B)
S(A)
If. on t.hP. ot.hAr hon.-l -nm -'oto .:Jn
along these two different paths, we obtain two results,
II

n~-'1

II

~.'h~~'h

'

.1

rru

easily verified by applying the first law of thermodynamics,

'

..

we find that :
Qr"l(;I.f

U(B) -

U(A)

'--' \-'-'I

'--' \.L1/

Lr
J.Jrr

....., .L.L

-=

u H O >

"'

,,-,.,....~T

...

Ulll t:.l~~u~~ U.L !.,

n.nrl

T,

...rA

respectively.

. 1

L'L

l.WU

.--.

.--.
T.

".Uv

, we

- .

01

.,....,..:!

. hu t.'h&> .,,.,.,,., AT l?.l?.' A' A

A TTI?J:?' A' A

Since the difference between these two areas

,
,
AT T>TT

1'

"L

>1

therefore, Qr - Q 11 also, are, in general, different from zero.

1.nus, \OJ) IS nou a penecu aurerenuial, ana no runct.10n ~qt
-~~

of t.hP. st.:1.t.P. of t.hP.

~Rn

hP. fnnnrl

Tt. i":hnnlrl hP.

noticed that if a heat fluid really existed, as had been

..l

..l,
......
..J
.1
"
function Q of the state of the system could be found.
,.
"-

1.

...]

..J

~.

.,

.,

J:'

~~

-~

siderations the exnressions for dO and dS for one mole of an

ideal gas. From (30) we have:
'qG

~"

...,.];...,..;~

pV -

....... :~~

~~

l'~

... a h -1-h,.. n:...:l r..f

'
+l~~

~~,,,._.

~t

~+~+~

RT,
dQ

L;:

CvdT

(84)

dV.

Tlus
. expression
.
18 not a perfect differential, and one can
.
..
.
.
unnwa1ate1y vcruy tnau une cona1l.1vu ~..~~J lt:J nov ru1ntu:~u.
From (81:) ttnd (72) we obtain:
rli~ - tj_(} ~ Cv dT

.,....
Q'

~ + ~-

.] ~

. ~

(Q'l''
\'-

Ulll:!:;,li.~\.lllb

''

~"~"'

'

perfcd. diffpren t.ial.

'-..Ill

;,

\0.1),

-1-

R dV

(85)

r,lf';llor1., th;"'

;., <>

-~

n "' ' " """' u

rn

Dl.

'

T/'

( o.A\

This additive constant

wlwr<' niH a (~OnHt.ant of in t.crrrnt.ion.
rcrn:un:-; undet.enni11cd n1 a<>eonl::mec Wlt.ll the dehnitwn
r~:~n
.r 1,,. ,,.,, ''""'" . f~nn htn\"tvr-t ~0rd.ion ~? )
J

'\Vc can tranHfonn the exprcH:-;ion (Sti) for the entropy of

OllC

Ul

1lll 1UV1U

b<t1"o

llJI

lU

\-1 V\.H~LU

'b

'"

1'

,.,-, -... T....., ..-,. .,-,. ..-,. '< T

>0

va1ue v

rra.'fP oo1,;ainea uorn 1,;ne equation

RPmPrnberin~r

(33)

OI

we obtain:

+a+

S = Cp log T - R log p

(87)

R log R.

Returning to the general case of any substance whose

1..

..1

-~-

..1

rn

1...1

Ll..

1..

..1

TT

.,__... .

the expression (80) for the differential of the entropy .

.
.
.
.1..ne conunaon \.O<>J, wnen appueu t-o t.uis expression, g1 Vt::1:1

'

r-

'-

-aT ._T
-\.._;av +P) _,

av\TaT)

where we have omitted the subscripts V and T because m

o

11 + ho<>o .f,

"<TTO.

1lo"'

Qholl

. .

>lQO

o..-.rl

fT' o:IQ

f.hO.

I we perform the partial differ-

independent variables .

.. .

alTXTO'I:TQ

llJ.

" H <::;

<::; I

'::'

<::; y_ Ul:l.

"-"'

terms we obtain the important result:

(a~) =

"

r(?P)
,~

- v.

(88)

!'l.n !'l.nnlil', . nf fRR) 'W"P ~h!'1.11 n~P it. t.n ~hn"W" t.hRt. t.hP
energy U of a substance which obeys the equation of state
_, _,
.
. J!
nrn
.TT
~A~

.L. ,_

.L".L

.A>;>Q.I-U..LLVY

~-V.I.

. 1 .

.L

UH'V

.a.\1\A.L'C.i

.UVU

depend on the volume. We have already seen that this was

experrmentauy vennea oy Joule; It IS mt.erestmg, nowever,
to obtwin this rP~11lt as a d.- "" l"'nn~Pnn,
of t.hP. P.otHI.+;,..~
of state.
Q. _,_

,........

+1-

Drn ITT "

/00\

.I

that:

( ~ ).

T ::.7'

~)-f!J

- 0,

which proves 6 that U does not depend on V.

T

<'

. 1.

Tn

TT

,....,

TT

5 N,-.t;n., t.hn.t. thiR l'mmlt. ;,. nnt nnit.A inilPnAnilAnT. nf i-.h .. _y,..,J,..

.
.

.+

ctescnt:>ed m sectiOn 5. indeed, the proof of the ident1ty between the gas
thermometer
temoerature T and the thermodvna,...,iro ternnP.r ...t.nrP. fl
in
.
. vu ...., ~~~uc u1 u" ... au1e expenmen1>.
" V'l """'

-.-,,. TrnT"'> r>

~-..r

"""

v<::~.nau.Le::;, we uu

uwo o"tner equations WhiCh are

substantially equivalent to (88). Thus if w~ t.H.k~ T Ann '1)
as tne state variables, de.! IS given by (23). Since dS = dQ/T
1-'

'"

;_, <>

.1".

>-1-

rlit!C

n<TO ooo~lu n.h-1-n;~

.+ia 1

(aU\

(aV\

,ap 1 T

,ap;T

. L.J 7 ""'.n.Lue,

~.:-1-1.

.., .. ._.

.C /0<:>"\

"'(aV\

"""' IJU<O

'

'

,aT 1 p

,j.l- ~ ~ ".-J

, we

.IJ V U.L-.

r-

obtain from (24) and (83) :

T = -(_a~} -+,

-'

{.aT_} _ (ac:) (_aT')

' .r '

I')"\'I.

v-

,.,

"'

~~\'\.

tion. In this section we shall

apply equation {.<:S<:S) to a sat11r;:,f.prl

+h .,t.

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

;_,

t.n

...

:1:'1.-

~~~

system composed of a liquid

.l

\\fd~

We consider a liquid en-

\,'

'.J

piston at one end. The space

between the surface of the
1-"

",.1

"1 1-l-

.c.

.+

-~

,j.J .

'-~d
-~
~

r-

.LI"Vullt:.L-Jllti1;:,> HJl

-...__

...

temperature of the vapor and not on its volume .

.LUt::

TT

.
c

\:-----_ -'=b

TV

ton will be filled with satu._...

I P

'\'

'- '.I:" I

ran\

IJ1l1<"> Hl{U.Lu-vu.pu.L

l:i.)'l::iu<:an H.L

Y,

p)

renresentation are obtained as follows: Keening: the ternperature constant, we increase the volume of the vapor by

. .

"

,.

.,

will evaporate in order to keep the pressure of the vapor

UJ

L!S\JU

.L UU'-"'>

U.i:>

LUll!:>

"""'

~L4Vul~LL

LL\.i ULU

J.;:)

J.vJ. IJ)

O.U

increase in the volume of the system leaves the pressure

unchanged. Theretore, the Isothermal tor a mixture ot a
linnid n.nrl it.s vn.nnr in Pnnilihrinm ;., n. linP nf r.onRt.H.nt.

pressure, and hence parallel to the V-axis, as shown in the

~ <JC,~VU

VY

IJLl'U

U.V'-'\'\COU HUG

~a

.L' ~~U~v

.LVo

does not roduce an increase' in the pressure; instead, some

e vapor con enses an
e pressur
h isothermal .

part of the isothermal will therefore be very steep, as shown

gure.
1
ral isothermals of the kind ust discussed

the length of the horizontal stretch of the isothermal

.
.
.
. .

'
can coexist
in equilibrium at a given temperature) decreases
wi
increasing empera ur u i

the substance in the range of very high temperatures become

. .

rn'l::rv

nco -.or

a~

.
..L .U.'V U.V<IUo;:;U. U.U'V H.L

U.L.L'V .L.li:;U..L<:; Q,.L.LU.

=u

UU'V <0.1

~.,

divide the (V, p) plane into four sections: the section

marKeu .LJ, Wnicn corresponus L.O JJne nqtuu S1.a1.e; une secuion
marked L V which corresnonds to the mixture of the liauid
and the saturated vapor; the section V which corresponds
+n.

i-.'ha -n rYnoa-f-,~n-1-arl "<r<>,....n>'" cnrl

i-'ho

u,h~roh

rJ.

sponds to the gas.

~

'

...-yyJ

U~YV

,~~/

Y~

YHV

'"'J'-'"

~'1_~~~-~y~~

represented by region L, V of the (V, p) plane in Figure 13.

.
.
. .
. .
~u. LrH:::; r-egion une pressLtH:: auu ~.>ue uenSILies or
~.>ue uqu1u
and the vanor denend onlv on the temnerature. Letv,and
v2 be the specific vohunes (that IS, the volumes per unit
TYHI.!';R

or t.hA 1nv

of t.hA rlAnRit.iP.R) of t.hP. licmicl l'l.ncl t.hP.

vapor, respectively; and let

~

'VU~y

~U'

U ..

V vv

ov~

and u2 be their specific

'l.l 1
yv

~<& U

"-V '1_ ~~

ties p, v1, v2, u 1, and u2 are all functions of the temperature

, auu rnt
oruy.
~~ TTL 1:::! ullt: LU LtU ll.Hti:;l;:; VI LUe i::ill'"'""
m 2 are the masses of the liquid and vapor parts, respectively,
then,
rn =

rn,

rn .

Similarly, the total volume and the total energy of the

system are:
T/

.... ,,(7'\

-I-

on.. "- (

m,1t,(T)

m2u2(T).

T\

We now consider an isothermal transformation of our

L

-'-"-'-

-~

-"

1.1.

.1

-4-

'

from the liquid state to the vapor state, and which results
In a cnange a v ot tne t.or.::11 vo1ume anu a cnange au or une
total enenrv of the svr;tem. At the end of the tram;formation there will then be present (rn, - dm) grams ot liquid
o-r'rl

(,.-,

rl>Y>l

Cl'l'"'>TYl<:1

.:n i-_J,.,t_

r.-f' "<Tnnnr

t.hA i.nf.!>l VOlllT'nA

will be equal to:

"

,,

.,.,,'

-1-- f, .. (T).

'v~

"/

-~,

?J,(T) \dm.

or
av

jV2l,l)

Vt\1)

~nrn..

\YJ.)

""'

.,..,.~

. .

lt

y, tne total energy wiu cnangel:Yy--an

,

~~

lsn;v

f.nA ~

H'

...

dQ

dU

{21

ArllHI ...._

_,

"WP. 'hauo

pdV

+ p(v2-

= dm{u2- u1

v1)},

or

...dm
~ =

'lh

u2 -

p(V2 -

= :\.

v1)

(93)

Equation (93) is the expression for the amount of heat

,,

.....

1~.

temperature; it is called the latent heat of vanorization A.

The value of l\ IS dltlerent tor dnterent liquids, and it also
rl

,,.:(.,

nn

+~

fh<>

~,.ofnT"o

~~+~ ..

li'n...

~+

+1-.~

hn;1;~~

temperature and standard pressure, A = 540 cal./gm..

a.

rn1\

.J

'"~'

,.

.L

..LL

.....

,.

the ratio dU jdV gives us:

(~_g)
'v r .

'l1.2( T) -

T)

Vl\ .L )

'

11Rina (Q~'\

nT"

(aU\

X
V2

"\OY / T

v~'-~

1.1.1 (

V1

.
'1

_:]

..L

--==

,.

.... .1>
~

'

'ap'
aT v '

,. ......

_, ,

.'L ._,_
~'-'.LI.

w""

..

,.

dT

~YI

p~vo<Sure

~~

IS

..

'

....

rl~

IS called
A:::: Rn ov

........ .,~

Jj

uu "'"''-' ,.... ..,~ ~

Tills

'

T(v2 -

~'!J"J:)

v1)

Utapeyron s equatwn.

..

... :~~
we shall calculate the ratio dpjdT for water vapor at the
=

):''-'

lP. of

t.nP.

n.nn li t>.R+.inn nf l"l.,

............. """ "'

.t-

~ ~~

SU.le.

vv e

u.<:~.

v ov :

~""

--,.

..

1&:."f'"l'o

!=tub~t.itutinQ:'

dp

"""'vv"'

-.::T"RT~.

'r-.~T~

~u

ergsjgm.;

.........

I\ A~

these values in (94). we u:et:

~ A2 'X

104 dvnes/cm. 2 degrees

'

r.r

I"

2.7

I"Tn.

Her/,'

Clapeyron's equation by assuming that v 1 is negligible as

.
&J:-

:\;:U

lJV

'<>

,_.,,., U~UO

IJ .}'

"""'"

lJ.Ul:l.IJ

the vanor satisfies the equation of state of an ideal g:as.

~or one gram or v -r
, we na'-e, Irom equation \ti):
n

pv2 -

}.:[ ~,

(95)

where M is the molecular weight of the vapor.

Equation

'

dv

"AM
7.?:1-P"'

(.['[

d log

1)

-v

"~'"

_,
~-

,___,

XM

,,. I

N,T2"

d'l'
--:1:0r WRuei"

,.

x-Ig""tiCITI].It.:l"!kt.Un,, !Jill~ lUI"

.W-.:;TT{', -.:7

e:ives dv I dT = 3.5ti X 101 ; this is in very good agreement

with the value 0.t>~ X HJ" Ol)t,amect tram the exact cal...,., ].,+;...-,...

If the heat of vaporization A. il:l assumed to be constant

"""UVl:a-= -vv-:a:t:.rV~

r "

u r ~~.,-,

Wv

'Ut.HL

'

ULlJvoL"lJU

,~,..,,

\V'I)

and obtain:
log 11

>..M
um

eon10tant,

or
).M

p = ccm...,t. e

J<T

(98)

This formula. show:-; in a rough way how the vapor pressure

'I:-

011

t-Ilt'

t-t:IIlptTaLun.

,.. ....

,,--,.T>"'<T

.
.
vve nave aerivea \..Aape_y.tu.u ts eq
~ur ~:to .ul!u.tu-vi:~.puJ.
....
but the same formula can be applied to any change
of state of a substance. As an example ot this, we snau
-1~~

'~

r<h.

~~, n+-ir.n

+r. +1-.a TYlal-1-.1,.....,. nf

<:~nli.-:1

<1.

solid subjected to a given pressure melts at a sharply defined

..

p
~

_,

...

_,_,_

solid. Hence for a solid-liquid system the pressure for

which the solid state and the uquid state can coexiSli IIi.
.,...,.,,,.,

,,.,....

-ic

f,,,... ,+"

<>

nf t.hP. +.<>Tn

WP. !':hl'l.ll

h1rA

now use (94) to calculate the derivative of this function.

,

_1

"-

-'-

1..

-L

-'-

.~

fusio~ and the specific volumes of the solid and the liquid,
~.

J.

iVUJ. V VL.)'

"WP. h!'t.Vt"l
= 1.0907 cm. 3 /

Tf urA +a lra t.hA TnAl+:ino- nf ;,...,P. "'"' !'I.Tl P.Y!'I.TY'InlP.

A = 80 cal.jgm. = 335 X 10 7 ergs/gm.,

~

nnn~

I.

..... ,.,.

rn

v1

.., . .

o .. 1..

-;

.... ...

...

+1.

values in (94), we obtain:

~ = -1.35 X 108 dynesjcm. 2 degrees = -134 atm./degrees.

That is, an increase in pressure of 134 atmospheres lowers the
melting point of ice by 1.
T+

~1-.~nl..:l 'h~ ~,-..+~~...:!

-i~

nn~+-i,..,],..,.

+1-.n+ +h.-. -.v.ol+;,......,. ..-.n-in+

of ice decreases with increasing pressure.

-.,

-.,

.In

this respect
,

substances behave; in the majority of cases, the melting

.
.
. .
. .
jJ u

.l.ll tJ

\IV J.

.l.ll" .1 '

~ .1.1

.ll.l" .1

jJ .l "' "'"' Ll.l <:J

..1..1.1.10

behavior of water is due to the fact that ice is less dense than
water, whereas in most other cases the solid is denser than
, ,_. ._,
The fact that the melting point of ice is lowered by pres.., ........ ..., .....,

.
IS

... vv

.........

...

u' O.<.vO

UOv

UUJ.Q

phenomenon
responsible for the motion of glaciers.
vv nen ljne mass or ICe encounliers a rocK: on the g1ac1er bed,
the hiP"h
tre of the ice !'l.!l".fl.in!'lt. t.hP. ro,...,k 1
t.hP.
melting point of the ice at that point, causing the ice to
N

~4~~

~~

~4V

~v~

~V

4VL4V0

.Y

~ p~ "'"':.mre-is-

removec:r. Tn -,;rris way tne mass or ice

is able to flow verv slowlv around ohst.Q"'l"'"'
a1 lJtjl.

equation of an ideal gas represents the behavior of real gases

~

, . ,

, ,

~~

.L

ever, when the temperature and pressure are such that the
gn.s 1s ncar conclem;;ation, 1mportant ctcv1atwns from the
]..,,. .., nf

irl.onl ,.,,..,,,_, <>o n~ .

the
. .Among
,
, .

numerous equations of state that have been

,,
, ,
.
"
,
,
..

Van der Waals

=>p=

"';l

1s

espeeially interesting because of its

"'J ~,k.~ ::=~ (n:o"-.L <OJv>. VU'V

nf TTHH1V'

<:!llh'-'t.n'nf'P._,

lVt-\l'

<> 1.uirlt>

'r!H'HJ'O

Af t.

.1

.....

. , .

.1

..1

.,._nrl

e>t.11'rAQ

pressure:;; .
... '

'.I.V<

. _,

based on kinctie theory, ta.king into aeeount to a first

"PF

<

..

nT"'U"" o

... ,.

= "0

between molecules.
OI l'>UU8LUIH'e)

~ ,

',

substance.

0. ,,,,

. t

I.

Fm a

...>.L

...

:"'

.L ~.H ' - A;

1:-i.

<

~~H~

'"''-'

His equation of sLate (written for one

<

To

\.P"TU/F-J\.
-t.

..-x' ' . . . . . ~

II)

.L

"

'

'

. '-

0, (!HI)

n~duces

'

nc:

-''1

o ...

IL.l

'

to the ehar-

..

. . . !.

't

~~

the ciTed. arising from t.he finite size of the lnolceulm;, and
Lne tenu a; ., - npn:sern.s r.nc mJ.ee1. or t.ne rnoweuw.,r concs1ve
forees.
In Figure 14 some hmtherma.h; cakulnte<l from the Van
'}

'

-~

'1

-~,

_,

....

compare Uwn1 with the iHot.hermah; of Figure 18, we sec

l<UH.\, 1IIC 1,\\"0

t-;(~\.t;

po:,;,,\,;-,N IIHLfi:V

Sllllll1U

H-ILIUre:,;.

.10 1101!1

eases there exists nn iHotlwrma.l havirw n. horizont.u.l noint of

nille<'twn(. Thrs tH 01(~ ('l'ltwallHothPrmaJ; und the point
nr ;nil,. .. +;,.., ; +l.-, ,.,.H ; .. .,J ,,,.;,d. 'J'h<> ;onf-l,,.,.,,....,J . , l .-.~
the crit.i('al !tmpPrat.un~ 1-ilww n :-;imilar behavior m both
"
..
. .

-A

~'

~em-p-era~ure

~~~?

e~

<Iirre-re-nres. Tne van aer vv aaiS

if'lot,hermA.lR l'l,rP.
.,,....,,.. curve"' with a mini-rrmm Rnn a
maximum, whereas the isothermals of Figure 13 have two
____ ,__
_... _ --..J - - ..__,
+1....
1...-~~

~-

~~

~'L

+"h~

Van der Waals isothermals take on their maxima and

. .

The reason for the aualitativelv different behavior of the

two sets of JBothermals m the regwn marked L, V 1n .Figure
1 'l ~~ +'h-+ +'h- ~-~~-1-n - - +'h~ 1-.~~~"---1-n 1 .+
+ >h -+ +1--.n .;<,.,.
thermals in Figure 13 do not correspond to homogeneous

..

.,..,., ..>h

,\__~

,_-

If we compress a nonsaturated

liquid and a vapor part.

p

,.

-=>V

U.UU.U

VY'V

+.h .. <><>+.11-r<>t; ..... .,.., T>>"t><:!<:!11'r<>

and then reduce the volume

-~

~"\
7 ~
~

011

'1.

1"_

part of the vapor generally oc-

---.-T

COOTU

~ ~

'J

>-

.._,_,_.._,,_

U.>-

1n pressure .
LV

l>.lltl

This corresponds
.JJ::SV u.lltll'
.
or .r

-=

re

13. However if we comnress

the vapor very gently and
,
-r

we can reach a pressure con-'

.
u t::
n a.u~.Y
-=
uration pressure before condensation sets in. When this
.
JJ::S ... "'
, we say tnat the vapor 1s supersatu
""~
rated. The sunersaturated Rf.-+-- h
ln 1-.>1~. n~u
slight disturbance
may
.
. produce condensati~n , causin~ th~
Fi.~r.

14

~>

;:;a~>-

<>l".C.

"''-' "'-' >-

u,_y a.

liquid and a vapor part.

u ..........."' ou""u"'"' o::uo
-..,.
"ant, ror our UlSCUSSIOn oecause
they illustrate the possibilitv of the existen"~" nf hr...rnna-<>r><>--uus
in~e regwn of the saturated vapor. We assume
that theSe lA.hilP. Rf.Rf,Pf'l <l.rA
m+arl hu -1-'hn ~--+ Df"'T\ LTD
Of_ tlie 'Van der Waals isothermal ABCDEFG (Figure 15),
v<.;.U .VI'
V!
t>lle UiSCOll'tinUOUS

'

r u-

n.v.n.LJ.L

lSOlJllt:J..

,..,.

. '"'-T'>''<7

1..ne sliaote nqura-v

LL~:>

J.-t:pJ.-

~.t-

states. If it were possible to realize all the labile states on

the van aer w aa1s rsotnermal, one could pass by a con+.;.,....,,...,,.., i ... nt1 o.:ol
.&.
t.ht:> --.ra..-,.,--.-.. .,.,_..,...
+arl "hn
the part FG of the isothermal to the liquid represented
'

7"> A

',_

~Given a Van der Waals isothermal, we may now wish to

aeterm1ne wnali Tone pressure or Tone saliuratea vapor rs wnen
it.<: t.P.mnP.r>'l.t.nrP- lS\ P.CJUa.l to that of t.hP. a-ivAn i<:nt.'~'"'1 nr
geometrically speaking, how high above the V-axis we must
_,

-i-1-

1-

.;. .1

liquid-vapor state.

,.;.

T>....., r-. ......

....,....,.rl h--.r

, . ,_

f'

'

\A

(16) we see that the work

~~~

.. b

'J

f~a.\

.1

and since 1n our

~J ~~~

ca~e

'

1-,

A
!])

'

equal to the heat absorbed

by the system. But for a
:1....1.

.._ ....

TY

=-

_pvv

.L

rln-r_

,.._

ing a reversible isothermal

'J

..J

-~

order to move this

we first show that the work
.1!.

.1-".1..

We shall prove that this distance must

'

~~In

Dli'

,.;.,1-

.........._G

.J.-1.,.

the

Fig.

15

. .,

'

remove 1/T from under the integral sign in (66). Equa"LIOn 1._00) llUW LCH:::; U::l !>lli:LIJ Lll~ UV\H~> uova.u "'':~v >Jv~, ...,,.~,
hrmee the total work done durmg the cycle, IS zero.
We shall now conHider the rever:sibly isothermal cycle

.,

'"'"-

-"-

..J

..J.

c .

this cycle,
VL'JL' .1.

.LJ

1"

0.8

'
measured by its area, rnust vanish .. But
.

U\~<1\.>1 UI\OU

...

'-''

~~

~ ~

area is noHit.ive whereas BCDHB, which is described

. in a
count.ereloel<WIHC cllreet1on, nas a. ncgauve area. ~1uc~:: Lilt:
tntnl Ol"P!l. nf t.hP 'VPk~ nenRFIDifB is zero the absolute
values of the area:-; of the two cycles BCDHB and DEFID
UIUO!>

IJU

'-''-1 Ui:ll

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

...,n

. .

;1-.lo

.1..ne ouJeCuiOn nngnli oe ra1seu agamsu une auvv""

stration that since the area of the isothermal cvcle BCDHB
lS obVIously non-vanishing, It IS not true that the work
,.

rJ, ... ~ .........

rl

zero.

~c,.-,.-f-1-

...

The answer to this objection

T>rt ....... TTT>

l>"<ri>l.o

.;.,

al

that the cycle

IS

In order to see this, we should notice that the point D

on our wagram represents two runerent states, aepenamg
nn -w-hAt.hAr

"W"A

1"'1"\n<:!irlAr -it.

<>.<>

10"

<>. n,..,.; ..... -1- nn t.hA Vs:~.n OAr

Waals isothermal BCDEF or a point on the liquid-vapor

J.l.

.1

T.T T"l. T T:l

_1.

A 1 .. "1.

...1

. 1.

. 1.

represented by D are the same in both cases, in the case of

7 -

~~~

~~.t'~

.v~

Q:eneous state. wl
'" in the ~"'"'~'~"' of the liauid-vanor
ISothermal, D represents a stable nonhomogeneous state
.c .
...1 ~~
l,"
,.;J
.... . un. .....
.-:~
the cycle BCDHB, we pass from th'e state D on the Van
,
_1
TTT . . l

.......

n~...,.......,

_1

.1

isothermal.
~

Since
v~~~

liquid-vapor

the
~~

~~~

~u~u~

state
~

uu~~

.
IS

~u~.t'

-~-

more
~

~~~

versible because it could not occur spontaneously in the

.
opposite direction. Thus, the entire cycle BCDHB IS
.
1 '1
...
...
...1
..1 + l.
'"
The critical data T. , V", and p. of a substance can be
~

-..,.

-rr

the Vander Waals equation of the substance .

..L ll'U

"".u. U<:l.L

<JY,

YY

\ V i1) 7 W HI::.U. jJ UHU ..1.

<:L.L 1::

~.1

V ~::u,

is an equation of the third deQ:ree in V. In general therefore, there are three different roots of V for given values of
rn

_,

rn1.

rn

rn

= V., ; that is,

horizontal point of inflection at p = p., V

u~~

-~

~~~

~~~u~~u

~u

"

""'-' v ...........

... ......

critical isothermal and the horizontal line p = p Hence,

.
.
l!J
wo
l'ne cuuw equauon ror v wnwn lS oota1nea oy
placing p
p., and T - T,in (99) has a
le
.+ V
V
This cubic equatiOn can be written in the form:
J.lcY

\J.IcU

~" ~

c) Y

UY

au

v.

c .L<:>

a.

~.L.LJ:.>Lv

must be of form Pc(V son, 1>nau:

v c-

Pc

V c)

3Vc -

and

pc'

..

"

J'C

~v

27b

2'

. .

vv

<::;AJ:.-'1 <;::;<:><:>

IJllv

..

Hl

lLi;l,~i.,_

p., and Tc, we

~<;::;.L

Pc

Q
~

lJl.LIJll-'i':U

_,

!:".

v.,

If we solve these three equations for

lt:::IL-

~Hij

Hence, we find, by compari-

3Vc- -

IJU1;::>~-"'Y.

.LVUIJ V.L

,......,

ATYV

1:0'1\:

n
\'-'-'"'1

27 Rb'

1H>:;

U.L

~Jlt:::

, ~a.u ~"'

a and b.
lt 1s worth notw1ng that 1f we takeV,.,.'J\,and Tr as the

"

'

'~

the Vander Waals equation assumes the same form for all
.., u. '-'"' YU.Uvv>O

.L

.'
.

auu

use

Pc '
01 \luu;,

vp

tp

"

Vc'

T.'

\Ve ouu:nn trom

'
+ "l.'lJ--)

TT

._,'

\::ICIJ:

,,

\ '"(') - 3':)

= ~ ~r

(101)

Since this equation contains only numerical constants, it is

M"

stances which are defined by the same values of

a,.L<:;

'-'"UCOU

\.<VI I

~J,

<">jJ<II~~I<fj

OHAOh''

<UH&

\.LVL)

Llel

"1'l, and.

~J
;u.

VU><:OH

"Vander Waals' equation of corresponding; t:ltates."

In Rcetion 14 we showed that if a subHtanee obeys the
.
,.
,.
-1
_1
TT
r>rn
1
'~.1

thermodynamically that it.s energy depends on the tern-

J:-''~v'"~

~"J

~"~

"<

""~'

....

<.H.<

""

.,

~,.v

"J v

~~

only for ideal gaseH. For real gases, U depends also on the
VOlUme.
From (99) we deduee that:
R'I'

v - ()

v-

--

--

'

.,

-
thiS together With

) =

( uu

av r

W<J

gtves:

(~I::SJ

L~L

'-"

V2

>-

"'UV

aT V - b

'

.L.LUJ<J5.L

........,,.

.. ~..

V-b

V2

.L.L

"

lJHH:> <J<..J.I

VV.LlJ.LJ. J.'

-:s:- ''-'"

uv

'.I:' ........ f)

...

constant) we obtain:
a

TT

' .r r ,.,,

f1n':l\

;:,;

.J.

.j.

.1.

TT

a in

... . ,. .'I"V\

Ul

) IJ<:UJ.I.J

IJ.ll'tl

1-

1111J'tl!;;J.

.,.j.~ll

,.j.

(Hl!l\

-'-

'ho

uo \;<...,
,a..u. u
f,.,......,.j.;,..,... r.f 'P

<>

.L

t.hP

nf

-'- j Sl.l PTll

J.

uu

Tho

t,hP.

cohesive forces between the molecules.

J('l') cannot be further determmed by means o1 thermorl"u'Tl a.Tn i "'"' a 1nn"' ..

i+... rl ,...-1-

Ul<:~.J:

rl a.t.Sl. nn

Let us assume, for example, that the

,., .

the specific heats.

:v

in <>+inn 'I"Pn 11 ;.,..,."'

>lJil>ll lJ V

<11.1

' '-'v,

.1;::>

T:'L

.1.' .L V.L.LJ.

(25) and (103) we obtain, then,

,.,
~nt.egral:img,

/aU\
\a:L 1 V

we gel:i:
f(T)

wnere w

IS

1'11 ' " "

a constant.
U

CvT

~quat1on

CvT-

w,

(.lU<:SJ

now becomes:

a
v+w.

(104)

With this exor

for the ener~rv. we can PSl.f'lilV calculate the entropy of one mole of a Van der Waals gas. From
\."-n

,-~,,

....

~~-n

~~

,~~~,,

"~

..

~-

dS =

= ~

(dU

1 ( CvdT

pdV)

a dV

-1--

ri'T'
y

-1--

1 (

'
v

-w

.,.

1'

a_\ dV

RT

'

riT/
JU

v-

b'

or, on integrating,

s.

Cv log T

(105)

b) +canst.

R log (V -

IS t;ne
tile similarity ox tnis wrmuta lJO ~,_ oo;, w
ion for the ent
" of an 1rlA~.l e:as.
In section 6 we defined an adiabatic transformation as a

1'1 otiCe
p

<:;; V

<:;;~

<UIJ1<J

'"

,....,u

~44~4 ~4.

"J

~~..,eo

thermallv insulated. Thus, along an adiabatic transformatwn d<J

U, so tnat trom \i"L.), a;:;
av,J :1.
u, or ;::; Pnnd.
'T'h .. t. ;.., if !'!. ~
~llcc.
l'l.n adi5tbatic tr"~~formaFor this reason,
tion, its entropy remains constant.
.._ .

.. '

' .

. 1!

. 11. -l

~-

The equation of an adiabatic transformation of a Vander

Waals gas 1..g Immediately obtamed trom \lUOJ oytaKing tne
L>T,f> -~

'rhi,_,

nr.T><Of.nnf

c~. log-

O"lUP"'"

R log (V -

b) = canst.

or
1l

I.>
./

'1'1 TT

-~

'

..

J:

.Ll

0 V

.1 . 1

flnn~

.. ~., .+

..

.J:

''

-ln~

"\J\Tnnln ~nN ~~

very similar to equation (38) for the adiabatics of an ideal

~"'"'
ri'

"<YY>

'

Ll

. .

.&

1 (\()()

rniHcd from freezing to boiling temperature?

OjR:\.J.UL

11<<~'-'

' f .....

.,..,.,

n'rOTY>'-'

nfnn+n~

.1.

(A;;sumo a constant

,...,~

'.-..~~7'

~-

-_,

.n.

VU<:;,Y <:> ".1.1<::;

cy_ U<LI.dVU
T71

U.l J:> l.><Ll.>C

, \Q,.,, ,

A measurement of its thermal canacitv inside a container having

une consuanv vo1ume 1uu 1uers snows vnav unaer vnese cona1t10ns,
the thermal capacity is constant and equal to 0.1 cal./deg.. Ex-

fc::;J.;,
"

Cllt:re:,.Y

H.llU

.u

L.lltl

-VJ!.Y

Ul

a.t> J.

Llltl <>,Y

uru;

. . ...

Ul

3. The boiling point of ethyl alcohol (C2H60) is 78.3C; the heat

point.

''

,,
'

',

Tnerrnooynamic t"otentiaTs
17. The tree energy.
....

.1

1n a purely mechamcal system tne

,-1,~;~~

..:1

.I!

-~-~~~

"

. ~-~-;,.,..,...

equal to minus the variation, t:.U, of its energy.

L - -ll.U.

systems there
For thermodynamical
,_ . ,_ '
, .
.1.
L

1.

_.{!-

~0

That is,
(107)

no such simple

IS

__

.I

.._ '-

..

in energy because energy can be exchanged between the

auu

"'~

it.;:> 1:::11 v u

~u

~Uv

1U1-Ul Vl

.o.uvv 1

ffl;)

the first law of thermodynamics (15). which we

can write in the form:
~~-~-~ad

L -

-!J.U

+ Q.

(108)

1v1any transtormatiDns- or "Lner

.y .
~Y
vt.;uu.l..-.rhiJo:> t.hA
~"")Q !HP in thf~rmn.l ~ont::~.d. wit.h t.hP. P.nvironment, so that an exchange of heat between the system and

.I

T_

1..

larger or smaller than -D.U, depending on whether the systern absorb~; heat from or gives up heat to the environment .
...

.Lt.

'<'H.

. .

rr

... ,__

-- _,

'4-

.r>4-

with an cnvironm<mt whidt i:-,; n.t a eom;t::mt temperature T

-~

!Jlll-

Ll> 1 i:~UU Wt:

l,;lJll<>H1LL

'"

\>lloll61V11l1'-"lo.I.V1L VL

VU1

"J;Jv~~u

init.inl state A to a final state B. Aunlving the

inequality (73) to this transformatwn, we have:

from n.n

-rr

(!fj :-:;

S(B) - S(A).

Rini"P. t.h,. !'.:v!-:1-.r>m tnr~~ive:-;

heat. onlv from a source whose

we may remove 1 /'I from under
temperature is eon:-;t.a.nt,
,
,

co-

'

I'

.1

1.

o .,

(II
'G>

JA

'""'

J.

I I

t~,

... ,

,
\'

.I

'

',

...

.... "'

"STrl

norvnr;.-...TrnT AT a

an upper
IUlJ.IJ VJ. Ht:::i:;I.IJ
LU LUt:
vve ljfiUS oo"tiam
ive from the environment. If the
whi~h the
can
transformation from A to B IS reversible, the equauty s1gn
1-.~1...:1~ ~~ {"7':1\ ~~..:1

~~

. .C.

.j.l-

(1110\ ale,.,

Tn -1-"h-i"' roa<:!t:> (1()Q\

gives exactly the amount of heat received by the system

:Fr~=m
-

(108) and (109) we obtain. on putting

AU

U(B)

U(A):

L :;;; U(A) -

U(B)

T{S(B) -

S(A) }.

(110)

This inequality places an upper limit on the amount of work

J.L

1..

""-

-1-.J.

..:1

_,

-1-1..

-"

.-1-

.C.

.j.~

If the transformation is reversible, the equality sign holds,

ana -cne worK perrormea lS equa11io tne upper
.
T.o::>t. ,,., <>n
nn= t.h<=~.+. t.hP t.PTnnPr<=~.t.nrPR of t.he initifl.l
and final states, A and B, are the same and equal to the
.
rrr . ..c . _ 1..
...
...
. ur~ ...:~~.f:~~ ~, +~,..,..... 7i'
of the state of the system as follows:
.j.

.......

(111)

F = U - TS.

In terms of this function F, which is called the free energy

UJ.

IJHt::: "'.YCIJvlll.l

VVJ.J.IJv \.l..LV) UJ. IJHv J.VJ.J.U.

Wv I.Oi::UJ.

.LJ

.L' \.L1)

.L'

\.u I

_...,..,.

\..L.L~J

1.n <,_11~), alSo, "tine equauty Sign no10s u une liransiorma-vion

is:
ihle.
The content of equation (112) can be stated in words as

..

. .If. a

system suffers a reversible transformation from an

llllLJ.I:LJ. ;::; LI:L Lt::: .L1 IJU I:L
JJ UVLll UJ. Wllll:ll o::;LaiJe::; Havt:: 1:L
"'
temnerature eaual to that of the environment and if the
system exchanges heat With the envrronment only, dunng
t.hP +~n"l<>fnl"Tn n+~".,..

~1.-

+.h<>

.-ln-n<> h-.T -1-"ho

.-ln-r-in rr

the transformation is equal to the decrease in the free

o.Y

V.I.

VU'V <:>J'<:I"'VJ.llo

_._..

\J

u."' "l.

LVJ. J.Hi

. u.

J.>:;

J.

t::

v :a ;:;u.J J.C,

u!lt:
~~~~ J..U
l>Ht:: J..l t::t;
~ Ll;!;Y UI une ~y~
IS OlllY an
upper limit on the work performed by the svstem. 1
..tSy comparmg \ll~J Wltn \lUI), whiCh lS true for purely
Tno:>,...h a.ni~l'l.l ~'

on lv

~P ~AA

t.h at. t.h<=> fro<> ~~

-in

thermodynamical systems which can exchange heat with

.L1.

...

.1

.1

.1

"

by the energy for mechanical systems. The main difference

1s -unau iu \.J.ut; vllt: t:LJ.U(;l.livy ~ atways no1as, wnereas in
(112) the eaualitv sie:n holds onlv for reversible transformations.
"\li:T~

.,...,..~u

""'~"';.-1.., ..

"'""'+~""'

+'hn+

..l . n~;~nlln

;n

r~~+

thermally) insulated from its environment in the sense

,_

.1.

J!

c1.

-"

1>

-'

1.

the system and its environment is impossible. The system

can then penorm only 1socnore trans1ormat10ns.
Rt.- <l.nv in~t.Rnt. of +

Tf t.hA

fn,. a.ll

;., t.hA

the parts of the system, and work can be performed by the

.ln n

,+

~ ~-l'l'~n+

r.-1' +l><>o

,l 1-..~

.S:.

+ J... ;n

,~~

on the walls, then the system is dynamically insulated when

. .
. .
.
. .
. ..
Otherwise the dynamical insulation might requrre more
complicated deVICes.
Wo:>

<><ll0!11l'YlA

+.hot.

<>lt.'hn11o-h

n11r

'nTYl

.;_,

.rl"<marnir>alhr

insulated, it is in thermal contact with the environment and

"-

-'-

environment.

rn

.._ L

"'

"-

For any transformation of our system, we

'
1\

<'

,- ,

'I

TNR'I
, . J'

1!'(11\
.

or

When a sy~<tenl und.,rp;<>PH ILII it;othennal transformation, the work L

performed hy it can never <JX<'r:'Pd minus the variation, AF, of its free energy;

. .

u ~ ~"l.u~ uv

-~

" ' " ' u ""~'"' ""'"

"

..

Our result is more general beeause it holds not only for isothermal
+.~anof~
+'
1- ,+
.L
~"P hnnfnP~ Hnn<o .-1.,,,;,,. ,..!,;,,], t.IH"
>m
assumes ten1pcratures ,-Jiffenut from T 1n the Intermediate state;;, provH.ied
nnlv t.hn.t. t.hA """h""""" nf ''" t. ''"''"r" Rolelv with the environment whieh
IS a't 'tne "'amo t.empcrnturc 1 \.llr<m~nour..

Of\

o1\ lr".n.T">"'<>'"""T. 1\ I<T,....

.1. lll:l. II .ll:5 1 .11 1:1. o

. 111
.

.Y o

... ,..

'""'""...

T"o.n.<

lll

'II

w llJU r,ne

t::llJ. v l l v.u-

ment at the temperature T and if it is dvnamicallv isolated

m sucn a way "tnatr no external work can t>e pertorme<l or
... ., ..............+.
"'h"'"'1"hP..=t h"<T t.'hP
t.'h"" .j!.,..,..,.
nf f.hA
increase during a transformation.
A

1!

Ll."

1" . . .L

.1.

"

p ~'-

JO.

minimum, the system is in a state of stable equilibrium; this is

so oecause any uransiorma"Lion wou1u prouuce an mcrease

in the free Pn
a.nd thiR wm1ln be in
adiction to
(113). In the case of mechanical systems, stable equilib'~+

~~""'

~-4'

.+

+1-

+" , 1

Q;.,..,..,a

the condition for stable equilibrium of a thermodynamical

.1

_l"

_1

-l'L

.L"

Ll.

.L

perature of the environment is that the free energy be a

m1nnnum, tne tree energy 1s otten cauea. tne tnermoaynl'l:rrri~

.+

1t.is:..l

l'l.t.

~.-.n.,+on+

vnlnTnP"

h,

Nt">+;..,,

that, strictly speaking, the condition for the validity of

(11'2'1

;~

.,.,~.j.

,.,..,.,1,~

+1-n+

+1-.~

~~,,~ ~

,..,. ..

-1-l

'ho

n"

constant but also that no external work be performed by

.

...

L-

-~

ever, the two conditions are equivalent.

We now consider an Isothermal transformat10n, 1, of a
At. t.hP +
+111"P 'P 1".
s:.. .+ +
A +.n A. .,fo+o R
and also an isothermal transformation, II, between two
A f

.J..

.J

...

Df

rn

.:~rn

A I

1. ...

..]

from A by an infinitesimal transformation during which the

.;

work is done. If the system is at a uniform pressure

throughout, this can be realized if the volumes of A and A'
.,.,.,. ,.,.,,., 1

..

(;ct,..,,...'hn;<> +-ra

..c.

,.,+;,.,..... 'I

Q;,.....;J., ...J..,

,rl.,.,.; ........ +'h.c.

infinitesimal transformation from B to B' no work is to be

.1

Let L and L
u~~~u

~~~~

~~

respectively.

~ ~

dL be the maximum amounts of work

~

~~ ~~~

u~~~

~~

~~.

'-'~~~

.._

...u

U.

.._ L

We have, then
L = F(A) L.t

UL

r \.t:t J

F(B)
r

\D),

(114)

.. J

"'

il T.

iJ Ji'( A)

..J TN R\

dT

d'l'

dT

1~::-iP~U~lVCly,

u,uu " ' \.U),

\."1}

\<A

P(A) and P(B') - F(B).

'
..

""

"'""'"' .Y

..1

""

._

,.,,~~

..,...,-,..,..,~-..Tr~~

l"l'T.T'On1\ Ti"YTY'lr""T \ 1\.fTr'"'

~.1:1..

I'

But we have:

F(A) -

TS(A),

{'(A) -

or, taking the d.ifT>renti:tls of both sides,

(I {

., .

\.-'1 }

(.110)

..

A tn A', the :unount of hNt.t ret>iv<d by the system during

,,.,, ' " " " " '

~HU \lll~l'fiL>I<HI"II

h. I

CHT\11Ll111~ loU \li.J),

and, from (72),

givt~s:

Equation (llG) now

dF(A)

/ 1 1 1\

T;'

-."(A) -- --,,- -

dF(n)

- gr 1n __

"

.I

1 te'

'

'
'" \'\Ul'l<'

L.>l

....

\I

\_.l>)

......

U(A)

ft'(A)

--:ih -

F(H)

(!(B)

'

'

.t:

'" d f,
' (Pi;

...

.I ,

'

--

l ' \_,'1}

-r,-

"" ' '

;:-;

\.L.I.I

1111'

Vil.lliLlolUH

'Vll~"!',.Y

Ul

rPsult.ing from t ht~ t ran:-;format.ion from A to B.

(111 ) IS <'H.lll'd
,.,,.f.,J .. ., .. J;, .. , j

t!H~

f,..,u(~/Wrt!

~ tl/1.

of

lDCJuat.iou
anti has many

t 11 no/}

;, ,,,,.

At. this point. W<' slwll d<riv<~ n. usdul expres:-don for the

'\

'

(V,

p)

diagram.

;.

'

'

'

'

'

_,

..

--~

LPt. us C'CJllsidPr an infiuit.<sirna.l, IHO-

nn

"

,,.,. ....... ..,.....,

--

'-'

.... -'-"

........

volUme or -.:;ne ~:~y::n.em oy an amount dV. We can apply to

.
this tran,.formation ea n J'l.+.i ,.,.,... r 1 1 ~\ ~ .. '~- ......
.1-~+
because the transformation is reversible. Since:

IJ

= 1JdV,

and

AF. = (

!~).

dV,

we have, from (112),

-"'~~

IAF'\
\8V /-r

(aF\

'0. v /-r

"''

I
L"

uy givmg -.:;ne expression ror llll~

free energy of one mole of an irlP.<tl u!'!.s. T'his is;
li~t.Plv
obtamed from equnt10ns (111), (29), and (86):
n

"'

wu6

~.L

T+' .,..,"' """'' (Q7\

"'""~

'

"- \,'-'V J.U!:; J.

;.,.._,f.,n.-:1

~+'

.lt. J.V!';

.l.. ..L

I'OC!\

U.J

......

\ .. ,.,.I
.+

,1

formula:
F

= CvT + W-

T(Cp log T - Rlogp +a+ RlogR).

(120)

18. The thermodynamic potential at constant pressure .

"J

and the temperature of the system do not change but,

llll::i

'

\.:lj UUl

l'

LV

lJ~lt:;

IJUt::l

}Jl'l::::l::il::iUH:l l:hllU

ii:I<IJ lU v

of the environment, durine:: the course of the transformation.

Under such circumstances it is possible to define a function
.
.
erty: if the funet.ion
v.

UJ.

IJU'V

p< "'"~>\U

<;;

"'
cp lS

a minimum for a given set of

<. L J. v

<.c; J.J.J. pc;J.

a. IJ UJ. c; 1

"u v "'J' "

IJ<:;J.J.J.

will be in eauilibrium at the given pressure and temperature.

we constder an Isothermal, 1sobanc transtormat1on at tne
+n>1t. f.mTl
. +111A r'f" ~:nCI t.hA ~onsf.Hnf.
ITA 1"1 whir.h
takes our system from a state A to a state B . If V(A) and
\.IJ J

a. v

IJU'-'

J.JJH.a.J.

... ~L><'OL

~L~Lu-..u

~~V~,P~~

~J

~LLV

nn

T<"<

- r~~

rma"Lion

u urmg Lne "Lr

system, tnen tne worK perrur

l!'l
L =
~Since

p[V(B) -

V(A)].

the transtormat1on 1s ISothermal, we may apply

"""""'+;,....,... (11 ')\ +n. -i+ ......... rln-inrr +.h-i<:! ""''"' nht.!'l.ln.
T~V(A)

TIV(B) -

FCA)

:<=;;;

F(B).

We now define a new function <I> of the state of the system

'""~

1:1.~

r.r

rn

TT

.TT

C'f

....... ,

.T7

In terms of <I>. the preceding inequality now becomes:

if?(B) < <f>(A).

(122)

The function .P is called the thermodynamic potential at

'"'

P'

.l.OJ .lVUV\'Vi::> .l.lU.lU

................ ..,._,._.

\.I.'"'~/

'

isothermal transformation of a system, the thermodynamic

potential at constant pressure can never increase.
W P TYI!'l.v t.~
R!'l.v +.h <>+. 1f t.hP. +
merature and the
pressure of a system are kept constant, the state of the system
p

V<

.1. .1.
f.,VI'-'1

..1.1.
<>1'-'

..1.1.
<>10<01 II

-'1.

'U , ...._,,., .....

J'

J.

.J.' .1

.:1\.

,_

~h

state of stalJle equilibrium. The reason for this is that if .P

.
fiTS -en' = ill Llll:l "'"""""' UI vlll:l
1S a mmimum, any spont<...,
woulrl have the effect of increasing <I>: but this would
be in contradiction to the mequality (12~).
IT'l.
.1'._11

.;~N _.i m +"~~

'"' "'h"'""" C!+<>+:"''
can be represented on a (V, p) diagram are sometimes
use1u1.

If we choose T and v as the indeuendent variables and

differentiate (1~1) with respect to p, we nna r,nat:

(a'!'J

a'P, r

( ov

J: _ ooJ +

ap r

T (

ap r

p(

ap

V.

But from the definition of the entropy and from the first
.l<:1<W > Wv UI:I.Vt:: ! U r <t 10:: Vt;:l

(.l,~,t

"~""''''-'":
J. (.1,1:)

UC

"T f'" r '

OA

~ r

~~~~

or, in our case, Ior an isotnermal cnange or pressure:

_,

_,

_,

\.ap)T - '\:ari )T + P \.,_ap )T

Hence, we find that:

l~:L =

(123)

v.

Similarly, differentiating (121) with respect to T, we can

'-'U~

YT

UH'-"

/;lm\

\oT}p
~ 0-'.

.,.Tnnlr

tT

-~.H.~ U~

,.

IJ.Ue U~<:a UH~t:;"'"' V~

-it. fA r:J.,,..;.,,> (""'1,

!JUt:;

1''

onn~+~~

'"'

LIJUU

"">

.,

VVt:; <lUCU.I.

Tn"h>nh .,..,., lH>U<>

already derived in section 15 by a different method.

TTJ"

'('

~>

,.

,,

,.

rated vapor enclosed in a cylinder and kept at a constant

,._~

.... ~~~'-'

... ~ '-'

.l:'~"'""~v

1 1 '-' 2 1 '"-'1 1 "-'" 1

.1. 7

are the energies, entropies, and volumes of the liquid and

V
l:Lrt::: LUt::
Lllt:: vapor par~,s, respecdvt:ay, anu u, o,
corresnondin~:r ouantities for the total svstem then

u
s

=
=

u1 + u2
s. + s2
>

RO

.,

(121)

that.. "-

<I?

Cl?t

<1?2 '

where <P. and <l>2 are the potentials of the liquid and vapor

'

Let m. and
VC.OJ:"'V.L

pw~u,

m2

be the masses of the liquid part and the

~'COOpvvU.I.V'V.I..)')

a,uu.

~vU

<Nl'

<>1)

Vl)

CA>UU.

'f'l

'""uu.

u 2 , s 2 , V2 , and cp 2 be the specific energies, entropies, volumes,

ana. tnermoaynam1C pot.entlalS or tne uqma. ana. "tne vapor.
We h.a.ve. thP.n
i1?1
'*'2

mt<Pt
'ffb2

<,02.

l"nT~TTO'"O,..rr.T""'>"'<T.,.T

-vv t~ .KJ.luw

uu111

-n.'"'

A ".rTr<

~-

:at .1-'~ UIJt:a ~,ies

HlC .,

or

sat:ura~ed

vapors

that all the specific auantities Ut u. .<~. .<In " l'l.nc1 1Jn
n.nd the pressure p are functwns of the temperature only.
UAnt><.>

'"

<:>Tlrt ' "

<ll'A

~-..J

fnnr>+lr.YHO! nf 'T' ,..,.,...1 ..

<I> = mt'Pt(T)

... ..

m.2cp2(T).

We start with the system in equilibrium and perform an

.
. - ~JUt: .(Jh:o;:oiSUI"C COllS"Lan"L
lHUU l>> O.U"'>'-I>Ula.l.>lVllJ .n.o;o,;:.J:"
0
so that only tJh and m2 can vary. Let rn 1 be increased bv an
amount am1 as a result ot tJus transformatiOn. Then,
.

~"'U

...,;,...,,...,. ->.

drn1
L\

....l

,...,

.,t_

r>nY'I

,...,

urill ..1

?n

h. .. n~ n~

'nn"

"

~-'-

The thermodynamic potential will now be given by

..... '
~.

t.~

. .
-
ri~.-

_l

..1

{,

.\

ri .

-"'-

.1

'

"

Sinee the system was initially in a state of eauilibrium. <I>

muHt nave Deen a mm1murn Iniuauy. .li'rom th1s and from
t.hP. nhove conation it follows that
'Pl

<P2'

or
\U2

,...,. . ,..,.

d ,

.L

'

\~2

~I

... '

J l.

rl

ti1

Ut)

,.

J'\tl2

J7l

'

.C..

But

..1

.l.l.

.L

~'

.1

'T

v.

Vt)

'

'

ll'l

'I

d7.'

\V2

.
'1 dT -

dT

VtJ

-r p dT \V2

V1)

u.

+ P dT .

Hence, the preceding cctua.tion reduces to:

- (.~2 (.~2
. But
. .
'1

JlS

St)

~'f. (v2 -

v,) = 0.

- s 1) is the va.rin.t.ion in entropy when one gram of

.

'li

"I

,U,\OU

'"'

\\HI"\i<ll\

IJvulpt::li.tiJUl<:::,

U<OU'-'<='>

liJ

.LO

~,...

or une
equal to >..j'l', where A. 1s the neat or vaponz
.,,1- + "'""
W., t."hn<> ,].,.;.tin t.hP. (;]n
eauation:
"A

dp

.u.vvv

HC

TiV

..1..

......

~~.t'

for one mole of an

the equation of state,
11rP

THTI

(I

vu~

From (121), (120),

_, ,..,..,,
. .
-L L

ideal gas.
m

u.vu

~+~.,..,t.-ia.l .. .t.... rm>::t.Rnt.

rl "UTI a rn-i"
TT

vv~vv

Vl)

'l~v2

a'l

'l'(r'_ lna T

R lno-

+-

'l'l

n. -1-

....

TXTL

}OQ' R~.

~~+~

~~

(125~
~~

J.,.

single hom~geneous substance, it is said to consist of only

.
one pnase. H a heterogeneous system lS composea 01
<>1 nar+.<> .,.,.,..}, nf nrht(>h i<> hnmn1
ml>:: in itself thP.
system is said to consist of as many phases as there are
1..

,J_

...

..J

-1-1-

As an example of a system composed of only one phase,

. we
.
"J
=
.,_
'"
-_,
chemicallypure substance; solutions may also be considered),
a homogeneous solid, or a gas.
rr'1-

.f-. 11.

~ ~ ~

-~~~~~~

~.f ~~~~~~

+1--n+

n~~~ic.+

of two phases: a system composed of water and water vapor;

....

'I

salt present; a system composed of two immiscible liquids;

i:L.LJ.U <lU

~U~

IJH.

~u

!Jll~

u~

<>LJ

lJJ~I:)l

I.Jll~

LWU

(;1,~1;;.

_t-

""

liauid phase composed of water and a ~raseous phase

composed of the water vapor. In the second example, the
,_

'

'

'

'

In the third example, the two phases are the two liquids.
~.u.L

uu-..

"'.1:-

p upv ucoo v> a.

\ uH<l.I.J

~"''

._,u !Jll<;;

p vp-

erties referred to a unit mass of the substance constituting

tne pnase: ror example, tne a.ens1ty, the spec1hc heat, and
so L -';h) ..l.
,,-l on t.hP. t.P.
'5'l.t.llrP 'T' t."hP
nrP 7l
and the chemical constitution of the phase .
~

-~~

~~

V.L.L~

. uu. uvu

V.L

a, ..-

' vv"'

,....., -..II" r . ..,..,..,.r.,._,.- > .,. ,

g1 v~

or eacn cnenucaTiy aefined substance present in the nhase.

~tnctly speakmg, one could state that if the percentage of
1L

Lll~

peL \.a:::u'

fr>r>lln+;..,.~

,,.,_,}, l"hATY\lroOl AlATY\>Tlf-

.j.J.,

.L

,.ol.

.1

1'

-'-'

element, both free and chemically bound to other elements)

L 1.

'

-r

that could be formed with the given elements would be

determineu oy tne given temperature 1' and pressure p of
t.hP nhRRP..
TniiPPil it. i>: w-All 'kn
+l-.~ 1~ ... ~ ~.c
chemistry that for any given temperature, pressure, and
P

'1

..

....

....

'

-"'

'~

'

-,

~-

chemical equilibrium will always be reached within the

TTT

"

--=- ""'

.., -p

~"

"

1
lTV\lH'Irl"
mixture of all the DORl'lihle f"'"
which can be formed from the chemical elements present in
~reneous

.j.\. ~

>Q

~h~~~

~~rl

-f-1, .,...

-1-l

.1'

.1.

.1

present is completely determined by T, p, and the relative

'

,.

1l

-.

Consider, for example, a gaseous phase consisting of

vv

''-'

v.

v~uu

A.J '-"' . =

""

.._... VA:Y I:; 1::> 1.l i:1. tJ <:1.

I:;L

V \::: U

temperature and pressure. 'The most abundant molecules

formed from hydrogen and oxygen are H2, 0 2 , and H20
I"

+I

..!'

.1..

.1

H, 0, 03' and H202).

.._

-1

'

The number of water molecules

'

U.<>. U Y

'-'

"'U

<A>

O~ V

'-'U

temperature and presi::lure is uniquely determined, and hence

T.ne euust.it.>ut.iuu ut ~.>ue gaseout-; H.Lixuure alSo, oy tne concentrationi::l of the hvdro!!en and the oxvuPn nnlv
Rt.ri ... t.lv
speaking, we may therefore say that the independent com'

I"

'

- . -

the phase (each element is to be counted as an independent

. .
. .
.
t::Ulll.t

tv w 11<::: vll<.::L .lv L"' JJ''-'"'-"H u u1 L'-'"'

lLttiy

~U!"lll

Ul" 111

chemieal combination with other elements). However it is

known from chcmwal cont:nderatwns that under certam condi+inn" Tn<>nv rh<>rnironl r>nn1lihrin.

n.rP

rpf-1!;.,...,,.1 nnlu ofttxr

<>

1nr1

of time that ii::l exceedingly long as compared to ordinary time

.
.vUl'\::: VL .1..1.2
'-"2
v ~~"
~.u.,u

W<>.UU.>v~~~

00

.. .

alJ norma11Jempera-.;ure ana pressure, cnemiCal equHionuinlli

reached when a lare:e amount of the hvdroe:en and the
oxygen combine to form water vapor. But the reaction

-,

.._ . . n.

no combination of hydrogen and oxygen takes place in a

reasonau1y suorlJ periou or uime. vr course, une reac~>ion
ln t.R.kA nl<><'A much more ranidlv if thA t,.
rature
were high enough or if a suitable catalyzer were present.
UT,

J:.

.L 1-

_.'

,J'

+1-

'

. .

.C.

11

.L '

. .

which we have a chemical compound that is formed or dis-

'

.,

comnound itself (and not its constituent elements) as a

practically mdependent component of the phase. lf, for
a~n..,....~l.o.

~> "hn~Ta

~ncoL>~'''"'

~"hnoa

n~~

:~n

~.C

hurl

oxygen, and water vapor at such a low temperature that

_,_ . 11.

. , 1.

,.

.1

_,.

,_

.,

~ay that our phase contains the three independ~nt comJ_J~~V~~U .....

'-"Z)

~~-

~~-'-'

'""'UY.

~~'-"U

'-'UJ

UU.V

UYYV

ponents hydrogen and oxygen); the chemical constitution

of the phase is then determined by the masses of 0 2 , H 2 ,
.J LT A

~.._

.LL

.L

It is clear from the above considerations that the number

. "'

~"'

~~

~~

c'-'

.......

'-'

than the total number of chemical elements present. In the

pr"' v
l:lXa
wl:l uau ~>nree muepenaen-.; componenLs
(H. 0. and H.O) instead of onlv
(H Rno 0)
On t.lw
other hand, if water vapor alone is present, we can neglect
. .
.. .
.
f-_,.,
. .
p h ase as consiStmg o only one component, the water, and
.L

"C>'

.UUlJ U.L

".J 0 '

lJWU.

Consider now a svstem comnosed of f nhases and of n

mdependent components. Let mw be the mass of the kth
tP.nt,

<P.nt, -in t.hA .,:t.h nh<><>P

'T'h<>n i-.hP rl' '- ih,+inn

of the components among the various phases can be con-

-noll ' -vn;-21 '

. . ..

.. ..

'11'[;/1

. . . . ............ .
.,

At. .,

'

equilibrium of our system

.1-'

'"'

a.

IS

that the thermodynamic

.J.. l.U.>:>

L LlUU.

~U

g1 V l[jl:j r-Jl:jl[j

i:L

set of relations among the quantities (126).

vve snau assume that the surface energy of our system
nAo-liaih}A

,::n t.h<>f. cb ..-.<>n h<> n.nt .,,..,,.,1 t,-,. tJ...o .,,.,.....

IS
tho

r..f

thermodynamic potentials of all the phases:

<t> - -wl -,=-<1>2 T

. . .T

<I>I

(127)

The functiOn <f>; depends on T, p, and the masses mn,

......,,

.,.,..,,

~~~

r.-1' tl-.a "'""'";"'""'

;~

+'h~ ~'+l-.

~1-.~M~

(128)

The form of this function depends on the special prop0::::1 Ll<J>:>

Vl

LUI::

vl1

YY o;:;

HULlt.:ot; 1

HUW<t;VI[j!

Hli:LL

''; >

considered as a function of the n variables mil m-c 2

m,n , 1s homogeneous of the first degree. Indeed, if we

...

' o

T~

.,

alter the constitution of our phase (since it depends only on

.L

OJUOO>

> .VO

VA

VUv

110

.0),

OJU.U

phase by the factor K.

tne same tact or A.
Tf n11r

~--~+,.rn

.LUvA<;;O.OOO>

UUv

VVUQ<A

>

UU<J

Thus, cl>, becomes multiplied by

io::: t.n hP. in ,:.rtni1ihrinrn <>.t. n. O'lVPn t.Prn-

perature and pressure, <I> must be a minimum.

J

V.L

t-

J '

'

This means,

'J

transformation at constant temperature and pressure, the

.
. .
.
. . vv e
. ler a
resun.1ng vanauon In q> musT. v
transformation as a result of which an amount om (to be
consRfercu as an infirutetumal of the first order) of the kth
~~

d ;u +>"nn

~.f'<>rNcH-l

.f',,,.,. ....... 1ha "'th tn +ha ,;t}.. T'>h<IQO

<>11

the other components and phases remammg unaffected.

orn,

<:~.uu

Ujk

n;k

-r urn.

~~

r~

Thus, we

Tn the variation of <P, only ct>, and <P; wur cnange.

nht.<1.in <1<:1 t.h"' Tl"'inimnm ~nnrlH:inn

a<~>.

IJ<I>i
am;k

am.k

----- .

tl:.::Y;

Om;k

am.k

..

Since a similar equation must hold for any two phases and
~

. .

'

n(f - 1) equations of equilibrium:

(1<1>2

U'T/011

U'Tf021

--

8m12

aw1

...

8<1>1

Vlf0/1

.....

--- am22

_____:_f_

am,2

. . .

a<t>,

8<1>2

oif?1

ar~

U'Ffbln

r .,,.\

dm1,.

..

vve not1ce tnat tnese equations aepend only on the

r.'air.<1.l r.nnRt.itution of """""h nh<~<:tP <l.n~ nnt. nn t.hP i.nf.!1.l
amount of substance present in the phase . Indeed, sin~e
1'1 <')0\

1.

&.

....

.&

"- 1.

L'

-~

_1

1.

m's, its derivative with respect to any one of the m':-; iR

..,.

.
'

wv

~V"

'-'-"-~.L

'<>oU.L

'-''-'

~'-'l"HU.

only on the ratios of mil , m .. 2 , , m;,.. . From the array

(126), we see that there are (n - 1 )f such ratios (the n - 1
_ h ... ;-~

.&

.l-1.

1..1

...

...]

determine the constitution of one phase).

'
(130).

.,.,

' a
We thus have

"

.1

'"""'''

Besides these

. ""-' .L<~'-'L"'O

..1.

<U'-.L

jJ

UL

total of 2 + (n - 1 )f variables.
J.Ht:

, v, ue~wco:;u. 1:.nis numoer an<1 the number,

n ( f - 1). of eauations (130) is the nnmhPr of t.hP fn - 1 I f
+ .2 . vanables
. which can be chosen arbitrarily, the re....
'-'J VU'V "''f UUVLVU>:>
o
~

-~v.-.

......
~ l~U).

. 'hPr

vv e t.trererore cau v r.ne aegree oJ vanaOWff;y or tine

of d
~R (;{ frf'.Pilom of thA 0 ""+.-.~
WP hl'tVP.

(n -

l)f

( f - l)n,

2 -

or

.. .

phase rule.
U,

_,

'.

........

,,

-,
-

,_

It says that n. system composed off phases and

JUUC p'l;UU'C:U l

l'Vlllpvu'-'H

2 + n - f.

u~

a.

,1..1.a,~

U<0!5.I. 'V<J

Vl

'"J

V <::U

Bv "degree of variability" is meant the

numtwr ot vann.blcs (we taKe as our vanables '1, p, ana "tne

'tm-ri~hl""' t.hn.t. r1~tn-n-i-r,P. t.hP. c~on~t.lt.nf.ion>:: of ,..11 t.hP. nh"'"'"'"')

that ean be ehoscn arbitrarily.

.

.J. l1 H \ UIU J1Ui.,11lle I p1 -'' VU.V.I.'-''"' l

VUv OUVU.I.U.

UV ll.l.'-'v

"J

the comnosit.ion and not the total amount of each phase is

eonsHlered, t)eeau::;e -ulennoaynamlC equlllbnum oer.ween
t " ' " nhn...:n.:.: tlln~,nr1..,

nnlv OTI t.hP.

~On>::f.it.nt.ionR l'l.TIO T\Ot On

the total amounts of the two phases present, as shown by

,

~'''

I'.

~11

'11-

-L

1..

.L

L'L

.1..

~nl.o.

is to he applied.
A sy::;tem composea ot a cnemicauy ueJ
h.
r<~nnnll"' -n.,;.-1
Vif(\ hn.vP. onlv onP. nh"""~ (f
1) and
one compmwnt. (n - I). li'rom (131) we obtain, then,
1<.-';rample 1.

'

""

"'

;t.

n ..

,.'t

~-

~-;nhl.a<>

1' and p, arbitrarily; but. we then htwe no further.possibility

.
'lll

'<.u

.J""S '"'" <><h.l1 ' " .. ~ .... , -~-

eallv dditHd eompound.

-.

.,

(N ot.iee that the total amount of

sub:-;t mHe, as we have alrcn.dy stated, i~ not counted as a

,
~ "
'

lt'.rample :!.
\:11<'1111\'illl,~

A homnp;eneous sy:.,;tem composed of two

\l\'IIIHC\l

fo',<~-~~

'

''

'

awl two irul<p('IHient. components (n -

J;C

'

2).

From (131) it
follows tllat. u
;:S.
.liH.tetu, we rnay Irec1y c1
.L 1 ,,.,u
iJ.t> l'!d ;n nf i.hP f.v..o I'OlllPfl111lllt~ that determineS the COIDpo:-;ition of the rnixttue.
.1

'

'"',....

.........

<

~~

M'Tr-<

vapor. J:iere we nave "two pnases, 1iqul<:r allCl vapor, ana

onlv onP.
so that f
2 Rnd n
1. Thus we
must have v - 1. We can choose only the temperature
.h:+-~-

:1

~"'

+h~

...:1

~.;n

-1-"~-~-

~-~

~~ .... 1

+~

+t~

pressure of the saturated vapor for the given temperature .

.
. -.,
. -.,
-,
freedom of choice in the composition of the two nhases.
Notice also m thiS example that for a given temperature
~--

~n"'

1-.n~.-.

or.,;Ja._... ;,~

--~'

1.

-~

n""''"'""'""~

~~

water and water vapor provided the pressure is equal to the

o

"r"r

' '

"

water vapor are not counted as degrees of freedom.

D
';)< ~
<b

<ti

----- -~

-----------/
~
\
; 0 or

....

~r.
p

T
-g

bl,

-7

'

vv

...

compound in three different ph~ses: solid, liquid, and vapor,

,,
~pv, ~"""'
vv ""'""'~' a.uu wa"ter vapor.
we nave
here one component and three phases: n - 1 f
w,
~
therefore find from (131) that v - 0. This means that

.j. h

"'""' ; n

-C.

-l

."

_,

<WLLo

UUv

three phases can coexist only for a fixed value of the tern

~L~V .._,..._

VLL'--

J:-H ''""" U~

vo

ThiS fact can be

. Illustrated with the aid of the rl1q.o-r~rn 1n
.._._._o._..."' .Lu, ll.L w
~empera"tures and pressures are plotted
as abscissae and ordinates
... ;, ~lv
rne curve AH represents the pressure of the saturated
'
.
.... vv nen tne
.L

u~v

v~-~~

oi J. ana p ~.:urr~.,..,.l:'~poinli on 'thlS curve, walier

and water vanor can coexist. If keen-inu the.._
rature
constant, we mcrease the pressure, equilibrium between the
~n-1-o...

nn~~~ ~~ 1~~~~-

.,.,...rl -1-'ho.

-'-

condenses into the liquid phase.

,

'

n..-.rl nll

.j.'J.. ~

~. . 1-

.+~~~~

If, instead, we decrease the

'
-.r-

.,

above the curve AB we have water. and for points below it

we have vapor, as IndiCated 1n the tigure.
'T'l-.o

A f" ;., an<>lr.n-n11Q +r. -" R

t>111"'l.T""

,rJ.,

hnt. ;t.

t.n

the pressure of the saturated vapor in contact with ice and

' 1.

~1

A 1

A rt

and below it vapor is stable.

on the diagram corresponding to the values of T and p for
_,_.

,_.

...

.l

.L

+1

\..

that this point coincide 'vith the point of

IH,

u~~

~~

,,.,_.

-.o

--

+l-

inter"

'

three phases can coexist only for a definite value of

1Jt:Ill!Jt:1

i:t.~uu:;

uuu OJuo:;

,.j.

th~

_l.Jl o.:;;:,;:;u1 o:;;.

The uoint A is called the trivle voint because it is the

intersection not only of the water-vapor curve and the ice'

rnt.

-~

three curves divide the T, p plane into three regions that

'-'Uv

ltl_l.Jl\J""-'U\J

lU.H!",CO

,_.

'"'-'<H.IUll'.J

'-"

~~

the triple point is at the boundary of the three regions.

The tnple po1nt or wntcr 1s at 1 - v.vu' i l v <ulu p
11 nnf:n? ... t.m
Rinr-P. t.lw --~~c;nrP !1.t. the trinle noint is less
than atmoHpheric prcHsurc, the horizontal line p - 1 atm.
\ VU'-' '""''''U ,.,_.

''b'

'I

ice, liquid, and vapor. The intersection of the dotted line

wltn t.ne curve .11 JJ corresponu;,; "LO .::.~; '"':::ut~"a """""' "''i uu.L vv
t.hl" fri"'P.'7.ino- nnint r of water at atmospheric pressure (0C).
The interseetion I> with the curve Al:S corresponds to t.ne
1-

:1;

(100(').

+ '~~~~~<,,.~
J

'

'

..

~f

"'nlo,..

oi-

Rf.TYlORnhRri~

tre

r.

~~

r~~~Y'T

r~~

'T~~

~~

su os1<ances -r;ne
on-e- a1
e. --:f!lJl'
dotted hrizontalline corresnondinf!' to atmosnheric nressure
lies below the triple pomt and passes, therefore, directly
o

-~-

+1...- ~-1~-l +~ +l-~ ~Y~~~- -~~~~~ ~-~+h~n+

liquid region.
o

(I

atmospheric pressure these substances

,

.At

ni-;~.-.. i-J~n

-1-

..

"'

.. .

-.;

-r

sublimation) : thev can exist in the liouid phase only at

sufliClently h1gh pressures.
20. Thermodynamics of the reversible electric cell .
. 11

..c

-1-.

-1- 1.

.c ... 1.

In

-l

have generally considered systems that could perform only

'

.;

'T

3. mechanical and electrical work obev the same thermodynarmcal laws; they are thermodynamically eqmvalent .
.f~~ +J...;" ;., +J....-.+

...PJ...o

n~~ ~~~--~~~~~ ouh;roJ... ronn

fl.

transform mechanical work

_, .

completely

into

electrical

As an example of a system which can perform eleetrical

'

4J

'
lytic cell.

By .a "reversible electrolytic cell"' we mean a eell

suCli that a reversal of the direction of the current flowing
+J...~~n~h ;+

nn""""" -1-1.-~ ~J...-~;~n1 ____ .._;

. . .

proceed in the opposite sense.

:;-

. .

..

'

-1-.1

IJ~

UUv v><Oi'-'

OJ~ U.LLLVU~

V v

~.l.

-1- ...

'

current through it.

<I

A reversible cell can alway:.,;

'ol

''-' u

.LV.L ..:;<:; U.L

IJU<::: o.:;c.LI.

-=

..1. L.L\0: U1tH.; ll1C<.U

work performed by the cell when we nermit an amount e of

electricity to flow through it is:
L-ev.
'-" ~

'-' v

u..L

o<:> ,

" u <:>

'-'"' .1.1

" " " ..,

.l-'~;;::11

v 1uu:;

IJH

(132)
IUUL UI

>YOrK

only if we keep just a very small amount of current flowinrr

IJITr e. -n-, -,;nat is, u we make sure that the process oceurs
reversiblv. Oth
iRP.
Rnl'Y>D .,.,...
ur111 },., t ... ., .... .,f.--.rYYHu1
m~one~!' msi.Ue the cell as a result of the Joule effect.
. .
E>J
'-' - '-'" u t.Jv
Q,U.Y <:::JO;;o.:; Ll UOll.Y
' /

~.--

"l'TJ"G'TY1\ ll"r'>-n."U"T ' ,._ lr"Tr-1

A T

r\~

on1y
on the temperature because we assume that the volume of
our ceu 1s pr::wuen.uy Invanable ~that It IS an Isochore cell),
onr'l r>
'. lllf~nt,lv nP<Tlt>r>t. nn-v
ihlP. .~. +., ~xrhinh t.h ..
pre:ssure may have on the energy.
.
-.-.T
. .~ '- 1.
..<.
.<.
. -"1.
,11
.1"
-"<vre-

l!Ut:i 1HJW~u Gu~ vu~,;u. Jt,.

LTIR\,

J ue .1:'

~ 1.

'

electri<'ity has flowed through it. The flow of electricity

.
.
.
. .
~nrougu 1.11u ceu re::;tur,::; 111 cer~>aln
c.
WliJlllU
t.he cell and the amount of substance which is chemicallv
transformed IS proport.wnnJ to e. Thus, the energy of the
.11 .,.;11

~n lnn~n

hn

n~nol

+~

'-

.11

.L

,.,;11 ho nhonn-arl hu

Denoting by U(T, e) the new

an an1ount proportional to c .
1"

TTf'T'\ 'h11t.

.LL

=~

_,

TTifTI

(fTT\

r rtrn\

r "" "'

where u(T) is the decrease in the energy of the cell when a

umt quant.1ty ot electnmty tlows througn It.
u.Tt.. nf'H'l' nnnlv t.hP Vnn't. Hoff i~O(~hcne (117) to the isothermal transformation from the initial state before any

. ,...

'

' ..

_]

-'I.

.L-1.

.11 (,

.<. L

--~

... '"

TTffTT\ \

+~

through
the final state after the atnount e has flowed
,
,
letwr~y gl\'en
ny \1~~)). J.1 rOm ~-r;y:>) Wt:: Hi:I<Vt:: J.U.l. 1...11'1:}
variation in cnerrrv:
~

l:l. ( 1

.I

.1' ,".1'

I_ lllK

L'lll11LI11 >11 7

"' rlv

W llJl'll

Jl-;

f1

-. dT

"

~ubstitutmg 111
nht.,in

hy (1:32).

' t . ; . I , l..- ,

'

-m1(T)

giw~n

The work JWrforme<l is

/11 '"7\

IOU,lll'll

111\.J

~'1 <v~vv~v

"J

~~

.,

2A\

'
m;tablishPs a relationshi n hct.ween the electromotive force v
and the erwrgy 11. We not. we t,IHl.L 11 no neau were tJX.h., "'~, .. 1 l.nl """'" t hn , .,11 '""I it:-; ~n vir<llnnent we should
u. 'l'hn extra. t.crm TdvjdT m (1;)4)
expec~t. to find 1' '

'

rr.

''

' t.

\.

'

<-l ,.

'

'

< ;.., "hnrht:>rl

'

( n.r criv<>n

out.) l>y the cell frotn t.he en viroun1en t when the electric
eurrent Jlows.

.......

',,.,...

rr.o

vve can a1so ootam ~~64) arrect1y Wltnout

tJut:
Van't Hnff iRn~hore. Let us ~nn .+ the cell to a variable
condenser having a capacity C. The amount of electriCity
.h~

--1-

..:I l-

. ..

-I

+l-

e = Cv(T).

We now consider C and T as the variables which define the

Slialie or Tine system composea or Tine ceu ana Tine conuenser.
Tf "WP.

l'!n~.nO"P.

t.hP.

P-RnR

nf t.hP.

~rmrl,

hv ,:).n amount

dC by shifting the plates of the condenser, the system

,.
.
..... .....

-1. '1.. -'1.between the plates.

This amount of work is 2 :

= !

dL

dCv2(1').

Tne energy ot our system 1s tne sum ot tne energy

~166)

rr.f t.l-1 ........11

U(T) -

eu(T) =

U(T) -

Cv(T)u(T),

From the first

and the energy of the condenser, !Cv 2 ( T).

-l~ ....

1 .... ~ ..... ~ +1-

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

(1

.,.,.

e;:\

+1- ...... +h"" ..._,.,...,.;. ..,1-

-~=:~...:~

.h .... rl

by the system in an infinitesimal transformation during

.
.
w
IUllL::> a.L anu av r:s.
uy
1. anu '-'
.>flo

.7TT

.7T

,,...,,

rv lrn'

.7 fTT/I'T'f'

, "" 2/ ' " "

_7.rv

2/'"'

'

'dU
._dT

du
dT

dv

dv-

dT

dT_

'T"h 0

rl ; .~

rJ.D

.J..j., 1

,..,; +h,.,.

rlT- rlTJ

T _dT

.J..

-s:- oJ

;"

...

L'

.& .

f L

'

'

rl?J.

rJ.,

dT

dT

rln~

dT_

rlr!
I

L'

'J

This formula is obtained as follows: The energy of an isolated condenser is !e2/G. If we change G, the work done is equal to minus the varia'"'J'
'
_,/1 e 2 \
e ->rt
.1T

'"' 'v/

"'"

" ; .. ln>nt. ""n~t..,nt. h"""""" t.h<> '"'"..!" '""

we oo1;am 1;ne rormUia used 1n tne text.

;, ;, ,] +

rl

>::11

rt.

'

11\lff""\T'\Vl\.T A 1\lfTr< "Dr

-~

~~~~w

~~

1-'

ilTT

i/.,

fJ dT
::.7'

. dT

n"'

l T C'l

1 VY "' ll<> V "'

,./,.

,:{,

'"'"dT

~~dT'

fJ
,fli

'1'

'll- uv .

If we perform the differentiations indicated and remember

V

u. 1

<>UU 1/ i:UC::O i Ulll.l

.L

Ui

UlllY 1

we

.y

r.h+a;n (1 ~.1.'1

Problems
1. With the aid of the phase rule discuss the equilibrium of a

dorl

>:olnt.inn $1.ntl t.hP >:olitl nf t.hA

.-1:

- 1

.J ,.,,-

,,..,.

2. How many degrees of freedom has the system composed of a

<o

.-..f

1ua

+oP

<on rl a

r>oP+

a; n

r.f

0 ;~?

ru

the rare gases and the carbon dioxide contained in air.)

"''"'""vuvo.v"' >VH>v v
function of the temperature, is:
"'

.LUO

0.924

+ 0.0015 t + 0.0000061 t
.

rl

'"v"'"'"''"'
2

"'"'"'

.... ..

' ,

..

volts,
,

..1

cell when one coulomb of electricity flows through it isother~ally

' 1

oo r<

''

Gaseous Reactions
eous system composed of a mixture of

y rogen, oxygen,

ollow-

The symbol :P: means that the reaction can proceed from

of chemistry that for any given temperature and pressure a

. .

such that the reaction indicated above

at

vapor from the system after equilibrium has set in, the

fr

We write the equation of a chemical reaction in the

genera orm:
135)

r<

n~f'I.TTC'<

nn

T'>"D A r-1..-nTr>. ....TC<

are Lilt: ;:,;;y

Ior une mOleCUles
reacting on one side and B 1 B 2 . . . B. the
1hnll'l for
"tnose reactmg on the other Sld.e. The quantities n1, n2,
. . . nn.r1 """ """
=n;
"''""" +-ho ;....,.
reaction. We shall designate the concentrations of the
w u"a v

..n1,

n. 2, ,

..ti.,.

~~

. 1"1'1"

1 .

the symbols [A 1J. [A 2J: , and [Btl. fB2J.

now suat.e t.ne law OJ mass actwn as touows:
'"~'~

~''1"""'"'

"""""

~~~-~-

ov

.j.~ n

~-~"

..,

We can

v"'~vo,

o,.v

expresswn
[Adn' [A2r 2 [A.]"r
. . . . a
. ,
, .

... .. .. .
.

K(T)

.
v

(136)

+-. "<ro 1,,.,.,

'T'h"' nnant.it.v k"('T'\ r><>n ''"""'"TYlo Nllit.o r!;A".

In some cases it will be very

different chemical reactions.

.J

. 11

J.t .

:1: 'l

,f',..,.

:n

.'l~.C.

'l

.J

.J

- _1..

'1..

hand side; that is, when equilibrium has been reached~ for

..

~~v

~. ~~,

~~~~

~~

right-hand side are much larger than those of the molecules

.
on the left-hand side. If, instead, K(T) lS large, the
~

..

....

....

It is instructive to give a very simple kinetic proof of the

.,
aetion (135) might conveniently be called "kinetic equilib. . .
. .
'

-~

'

_,

LIJlUU;:, .11<1. VIJ

rnnu, oecuuse C'\ en ~t.IL.t.:L Lut: t:Ll u1uuu u1u.
been realized reactions among: the molecules continue to
the number of
ta.ke plaee. At equilibrium, however,
.
.
.

'

""

b.

>

k.

=f

(135) is equal to the num cr ta mg pace per umt t1me rom

l'Jl:!,11l

IJU 1t:lL, "'U

IJllU.lJ

lJll'V

IJWU

UJJ.oc

<Jllvvll<>

<p

"""'

each other. We shall therefore calculate the number of

rcaetwns that oceur per umt t1me trom lett to ngnt and set
th;.., Anllul t.r. t.hP

(~eeding

rlino- n11mhPr nf

rRl'l.r-.f-~~"1!'l nro-

in the opposite direetion .

.l1 l'VU.viJlVU

llUUl

lv>IJ

\IV

~>oU\1

"'"'u

V'-''-'\.U.

""~

ow

V"4

....

...... ,...

_...

.-...-,r..TT,....

..-,.,-, >

"~~

murtiple cou.ision involving n1 m01ecuTeg --:71, 1'h2

An .... n. rnnlP~ules A~.
The freatlAncv of Auch multinle
collisions is obviously proportional to the n1th power of
... _ ... 1-_ +-1-.
fA 1 ~ +-"!-.~ ~ 1-1.
~-1' fil_l
[A,.], that is, to the product:
~

~s:

[Ad" 1 [A2rz [A,.]".

Thus, the frequency of reactions from left to right must

'L

_,
.._.._.

perature determines the velocities of the molecules, the

1

_1'

r'<'

UJ

a.

'n

uuv

' "
temperature. For the frequency
of reactions from left to
.
.
.
-:r:rgm, we OD"{iam, 1;nen, 1;ne ~:::.11.p~
.
.t'

J~

'~J',

'

~v~

.l\.: ~ :r J [.fi.1J

[.fi.2J

u.u.v

, J'

~~"'-:1.

v~

LA,.J
uuo

~uuw

~u

<;:<:1,1,;

t-nt::

~~-

site dlrection, we find:

K"(T) [BJ"' fB2rz [B.Jm _

At equilibrium these two frequencies must be equal:

K'(T) [AJ" 1 [A2l"' [A.t,. = K"(T) [Bd"'' [B2J"'a [B.]m,

or
l.tilJ

l.ti 2J

LA.J

f R.lmt f R_pno . . . fR 1"' -

K"(T)
77/rrn\

This is identical with the law of ma.'lR .. - ... -

( 1 ~A\ ;f

T<T<>

..-.1 <>no

---

K"(T)

'

K'(T).

argumenlJ gives us no Information

about the function K(T). WA Rhl'l.ll ,.,..,,'" .,,.._..,.,, -n,~-1- l-.n
applymg thermodynanncs to gaseous reactions we can not
nnlv
t.hP l<>UT r.f rna"'"' a.-.+;r..., ;..,...J
-'
considerations, but can also determine the dependence of
.l.ll~O

:L~I,;

L1

...... , ... J

v.u.

u.uo

""'~i-

,.

oox. .t ne eq ria o-r

bP. t.rP.fl.ted thermodvnflrn1callv bv as;uming the eXIStence of ideal semipermeable membranes en;t.;t.. Tne van 'T
ouR 'rP.l'l.~tions can

..:1 al-. .j-1-,~ .t~ll.

..:~.

,...

+u"'' .,..,.,.,

~-~~:

i\

(1 \

,].,..

..

semipermeable to the gas A is completely impermeable to

'

-~-

the e:as A separates two volumes, each containing a mixture

of A and some other gas, the gas A 11ows througn une
+'ha ....,..,;~+nrA lYl u:rhit>.h it., .,..,..,..,t.ial

.....,.o.....-.'h.-ro-no "

11TF!

is

higher to the one in which its partial pressure is lower.

~

., .,

_,_

"-

.J:

... ,_

gas A .on both s1des of the membrane have become equal.

,
't'

"J

of lower total
pressure toward a region of higher total pressure, provided
L.
.-1' <-J..
+-J.. ~+
.~~ +l-.-~ -1- +'ha
3,

.Ll.

. . . . . 1

-.

membrane is higher in the region of lower total pressure

'15"

.......

,..,

'

membrane semipermeable to hydrogen separates a box con-

. .

.g

.UYU~

=-

Cl.lo

VUQ

C..\>"U"O_tJUv~V

V~

_tJ~"'-0"'\.&.~'-'

~' VU.~

containinl! oxvgen at two atmospheres, hydrogen will flow

through the membrane even though the total pressure on

'

'

1.

We should notice, finally, ~that in reality no ideal semi. .

.1-'"'...
fL""

.J:' ...
such a membrane is a hot palladium foil, which behaves
like a sem1permeao1e memurane 1ur nyur =
Tn
...1
t.ro ,t.11f1v the eauilibrium conditions for the
chemical reaction (135), we shall first describe
a process
by
,

.,
...1
T

reversibly. This can be done with the aid of the so-called

van li non re:
uox.
This box is a larrre container in which great quantities of
the gases A 1 , A 2 , and li 1 , .J:J 2, are in c

... ,.,,;law;,,..... o+ H"'' +

.t.nrP T. On one side of the box
(the left side in Figure 17) is a row of r windows, the kth
-.,.

;Ao

-.:iu-

lJH~

r<

1;;1:1.;:;

.r.l..]G I

en:,,

VV ..U.U.~ U.U

"D

rvr.,T ,-,..,. T n

.
1s

~~-

lJH'O U lJ.l.l'O.I.

U.l

Figure 17, where we have assumed that r = 8 - 2)

a
row or s wmaows sennpermeao1e m tne same oraer uo tne
gases B. B. . . . B. On the outside of these window-!'!
are attached some cylinders With movable pistons, as shown
;.,.., +ha f:,.,..,,..a

We shall now describe a reversible, isothermal trans~

'V~~

~J~V~~

~ '~

U..LL

<=>'-' U.l..)'

U U

'-'.I. .n.

.L.J

performed by the system during this transformation .

. LJU l,llt:: r
. ~,, novv~::vt:a, umUS'(j oe
ll,l:! U.l oo::;.._,
eaual to the free enere:v of the initial state minus that of
the tinal state of the transformatiOn. By companng these
'
, P.Yn'
ionR for l~ W"P. l'lhl'l.ll oht.::~.in t. 'h"" ..:r .. .:J ,.,.,.,,H.
. We start with our system initially in a state for which the

..,

'.J

I Al

,.

'

A.,,

'''

'

Bl

''

'-JL

T
I

'

.. ..,,
I

UUOJ

I
Fig .. 17.

-uux l:l.n:: iu cunuacu wiun une winuows, so -ula~-ulese cylinders

have zero volumes, while the pistons in the r cvlinderR A

on ljfie 1en; are m sucn a positiOn that the kth cylinder

contains n ... molP.l'l of t.hP. Vl'l.l'l A (,..,.,. li';~, ...a 1 Q\ n+ n ~~~
centratwn equal to the concentration, [Ak], of this gas inside
i-'ha

h~~- +h~ ~n,..+;n1

.. ,

.1:'

,t-

~~

,,C +1.
vv

~~

o"'

"

.. ,

UJ.

'

Ll1t:l

semipermeable membrane are therefore equal, and a state of

'-1.'

..........

The reversible transformation from the initial to the finl'l.l

;:;
ua.ll ue p-onormea In ljfie rouowing two steps:
Stev 1. Startin~:r from the init.i::~.l ~+n+n fli';~, ..."' 1 Q\
shift the p1stons m the cylinders on the left-hand side of the
hoY
Rlnurlv inur.l"rl 11nt.il <>.11 t.h<> n-a~-::~ ~--+-:
..:r .1.1
cylinders have passed through the semipermeable mem.
..
u.1 l,.[llJS PJ. v'-'~::ss, '(jne
o~ ~"""'"

~?~

~~V

VU<:;

"'1\0

OJ'"'V.:J.A..L.L

'-'v

YYU.L

.U.L

<-Uv

Figure 18.
n e <:LS:::;ume vnaL 'Lne convenL or vne 1arge oox IS so great
that the relative chan!:!e in ~nnr><>nt..... t.irm!'l TAfmlt.inu ..
this mtiow of gases is negligible. The concentrations of the
"'"'""''"'

..:~.,.,.;,..,,...

11

+~.;.

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

th

,,,

constant and equal in order to [Ad, [A2J [Ar]

l-'"'""I
formed by the system
I
I
aunng vnls Svep IS ev1
clent.lv n,
"-ive beP.A.ns;e
work must be done on
..... .U'V

.,

'-'.L .L>.

.I.J

th<> T1>i<>+nnQ OO"aiYH:+

tho

pressures of the gases.

~.I.J. " .L1..::; .... J. "' "

\,j

;y

;1"" th.o

uAhnvu> ..,.;

tho

cylinder changes from

Lll~

!I

TT

I
,,

J_'

,/

.L

..L

----~.

'

----

'

'

----~

'
:1---

- - j !'

'

Intermediate ..state
---T.,
_ __,:

.r---~

z .,

"+.

of the P.ons;t.ant
pressure p 1 and the vari

ir---

Y 1 LV

the final volume 0. The

work IS equal to tne
rlu

"u v

pressure remains constant ana. equal to tne

n2.rt.ial
;sure v, of the
gas A 1 inside the box,
.~

.11.

.....

P1(0 -

+ J.

,1

V1) -

l l"'"rz ~ 11---

+ '

p1V1.

.
.
Ft'nal .state
Dlnce vne cy
, lHFig. 18.
itiallv.
contained n1
moles, we nave, trom tne cquat.Ion or SLave, P1" 1
.,.l.._.,.L
'rh,. u1tYrl..- ;,.. t.lnw Annn.l tn .n RT. Summing the work for
all the cylinders on the left, we obtain:
Lr = - UT 2..;

ni .

i=l

.Step

2.

Starting from Lhe intermediate state, we now

.

........ ,

,...~,...T~.-..

..-.~

..-..~T.

-or t.ne oox t.. tney are initiauy in cont.ac-,;- Wll;ll~e winaows)
verv slowlv 01
~rd
~in~P. the t. ....... lTn of t.hP. kth cvlinder
counting from the top down, is semipermeable to the gas
+-1-..~N ~~~1~~..:1~-~~11

~1.

+l-~

.1-..

..].

.Lt.~

-~~

and its concentration in the cylinder will be equal to that of

. .

-=

C>

~T

-r

--,

"IG~

the nistons outward until the cvlinders in the order from

the top one down, conta:tn m1, m2, , m. moles of the

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

"'R

"'R:

"'" .+-.

"hr

We
thus reach the final state of our transformation shown
.,
. ...,...
.. .
.
.
..

"
pistons touching the windows so that their volumes are
~V'

.U..U..:O

UU'V

}''-"'

'r'r

.u..L

VUV

C1:>

V,J

--r;;IC

OV

-"

kt.h ...vr ..:~

~nnnt.in 0' Trnm t.l-.o +.n,., A
+o>n<>
m.,. moles of the gas B.,. at a concentration equal to the
t.h <=l.t. t. r. P.
....

B1, B2,

.._.

rn

-" _.._,_

.L

._,

"

,...,,

,B. in the .cylinders and box are thus in equilibt:o

'~

~~~

-or

~~v

.o.

-.:>rrV '-' ,J

The work performed by the system during this second

.
. .
~:>lJO::::J:.I

vv J..U vuv ~uuo~y uo ..-

.vo::::.

This work Lrr can be calculated in the sam.P. wav

Stepl. We find:

1'1.R

in

Ln = RT Lmi.
-~

The total work performed during the entire transforma~ ~J. ... u ..... ~u

-~

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

L = RT \ ;:rz:aol
~

mt -

~
... -1

'

n:J.

(137)

This work is equal to the difference between the free

~:o~

'~

~u...,uv

._..... .._.

VU<A>U

V.L

IJUO

i:jlJI:f.lJI;:l.

~u

calculate this difference, we note that the content of the

11:.1.r~u uox is une
e in tne rmt.Ia.t ana tina! states. Indeed,
in e:oing: from one state to the othP.r ...,."' ~

-,],,,...,.rl .;Tl+.n
tlie .large
box n1 moles of A 1 , n2 moles of A 2 , , nr moles
,;:.
-.r
v
..Ul 1 '111-2
'

-/

~v~~

~.o.

V.I.

ui D2, , rns
u.t Ds. .ou1.r accorumg to "line cnem1ca1
eauation (135) the substances introduced into the 1....,.o-.,.
box are eqmvalent to the substances withdrawn. More"'.;,...,.."" i-ho +crn.,....o-rci-n ..<> a-n.rl

.not

. .

~r,-,.lnTV>o ~,; i-~ ~ 1

1-

..l.

change, the chemical equilibrium of the gases in the

-..

. ..

-..,

final states of these gases are identical. The onlv difference

between the mitial and. nnal states ot the system IS in the
.r>r..n-'-

nf

+.l-. o

n-.rli-n ,-l

..

'T"ho-rof ,..,....,.

'

i-'h <>

r1 ;=

n~

'h~

tween the free energies of the two states is equal to the

,. ....

..

'

in the cylinders A in the initial ;tate and the free energy of

(initial state) can be calculated as follows: The volume

-'

1.

- .

_,

inverse of the concentration [A d.

.._, ..

.4.Ll

.L'-'

'-'U'-'L.L

.LL'VLU

'-J~

'

' '

The free energy of one

\.L.LoJJ

~J

...,..._,._,o;;>..,.L'

.~

.U.A

that equation 1/[A 1l for the volume V of one mole. Since

we uave n1 mo.tes OI ..t1.1 , t..ne 1ree energy or ~:.uis gas Is:
ndCnT

Wt -

where CVl , W 1 , and

a-n.rl

a1

T(CVl log T - R log [Ad

are the molecular heat and the energy

,,-,..,....,+a..-.-1-c.

notations for A

2 ,

~ n.: (Cv.:T
i-1

+ a1),

f,.,..,..

i-l-.o

'""""'

TT,;,..,...

o;'""';ln~

. . . . A" r, .we find for

.. .the free energy of .the
,

+ W.:-

T(Cv.: log T - R log [A,]+ a.)}

The free energy of the gases B in the cylinders B at

~ m; \t:v;1
:=1

where C~; ,

w; ,

w;

and

1'\t:v;

a;

log '1

J(,

lOg lli;J

a;)!,

are the molecular heat and the

r..n

~~~~-~

~~

.....

Tne amerence between these two expresswns must ne

P.nlll'l.l t.n t.hP.

/t-- -

el.r T.

'f- ' \

~fTTI

,i-1

f..

i-t

"Wo t."hn"' h~.VP.

hv (1 :l7)

r.r. . fTTo

i""'"'l

/TI(rl

TJ"T

fTT

'

8
.. ., .LVE,

L~"-

>J

'""i ) I

lfOj \ '-'VfL

i-1

Wf

rr, lOg l.Ojj

:.n.liv; lOg '1'

,,

11-.<>'<

Dividing by RT and passing from logarithms to numbers,

11nis equa11ion reauces "to:
r
B .z; m;CR+O 'v,

[At]" 1 [A2J"' [Ar]"r

L.OtJ - L.D2J

'

a' j)

i-1

.::E

n;CR+ov;

a.:)

i-1

l.l5 eJ
/

X T

R\,""" ''Vi"

-1

.- ~-

"\
Vi~i)

i-1

~ n.:W,:-}; 'fflJW'J
1

RT

Xe
~ne

fl-::to\

ngn1j-nana s1ae ot tn1s equatwn 1s a functwn of '1

onlv. _ThnR P.nna+:ion (l~Un not...onl.:-iL

'"' t.h,. l.:nxr nf~
action (136), but it also gives the form of the function
vtrn\,.,

',. ~-~-1

We shall
. discuss the formula (139) in section 24.

.,.

~~ u~

J:'

~~

VJ.

UUv

In the

.LV.L.

23. Another proof of the equation of gaseous equilibria.

T~

+'h;.,

.....

.1- .11 ..J

'".-.~,

,
~

result obtained in. section 17 that the states of equilibrium

v
"""""
which the free energy is a minimum.
"'

re or line gases At, , Ar and

B 1, ... B. at the temoerature__7"_en_cln<>on in ~- ~nnt.~.1~
J:ixed volume V and reacting chemically in accordance with
-~

~~~v-~

.LV.L

...

...

'

'

"1'

V&VJ

UUv

IJU<:J

N"'"" r>. T TN

r1

;r.-

,-,. T70

com
Lu.K.t::s pan in "Lne cnenuca1 reaction, -c-ne conr.entrations of the various..,..,..,.,.""
... r.hRn~FP.""Rl'l n. rP.l'lnlt.
of this, the free energy of the mixture changes also. We
~h+n~~

_\. .11

:1:\.

+1-

-l~'-

~-

.Ll..

reaction by making the free energy a minimum.

~fa.' "-ure of

VA~

A~A

VAA~

.1.

.1

To do
oJ

AA~~

of .-.;~ra"r> r.0n1
+ n.t.ionR
Dalton's law (see section 2) states that the pressure of a

.~

...

/.",1

tJ'(>OO'-"

.1"\

-~

"-'-

. .t." .1

.1.

of the components of the mixture (the partial pressure of a

J:''

..

'.!:"'~

V . . AU

...........

exert if it alone occupied the total space occupied by the

.
.
mlX"tUre). .L IllS 1aw mawates t.na"t eacn componen"t lS
.J

e.

1..

.J!

"-'-

,,_

.1..

..]

retains its own properties in the mixture .

...,

......

~J

....,...,...,.

v . . ....,v

We shall now
......

.v .... ...,

...,.

ideal gases the energy and the entropy also are equal to
tne sums or "tne energies ana entropies 1.,pan1a1 energ1es ana
nH.rt.in.l f-mt.roniP.~) -whir~h P.nr,h
tP.nt. would J...,. """ if it.
alone occupied the total volume occupied by the mixture
.
,,_
... pv u.uun.- "''-" .Ll.
J! ... 1..
u.u uuv
v uuv uuAv'-' '-'
From the definitions (111) and (121) of the free energy
ana tl1e tt1ermo<tynamiC potential at constant pressure, 1t
~ nnW" i
foP
tPrlln.t.Plv t.h~1.t. for !'!. rnixt.nrP. of idt>n.l P"l'1.":P.l"'
these quantities are equal, respectively, to the sum of the
....

. 1

"-

.]

"

.L 1

.... ' 1

.L

. l.

dynamic potentials at constant pressure of the components

ot. the IniXture.
inn"' '\uP f"!ln n.n'W'

w;+h t.h""'" """'"

",A CJoUTn

t.ht>

pression for the free energy of our n1ixture of gases .

~

PV-

The
.1

preceding seet.ion, by the expression:

CvtT + Wt -

T(Cvt log T -

R log [At] +at).

Since the eonecntration of A1 in the volume V is [A 1J,

uV.Lv

'"''-'

.P''-'''~uu

._._,~

0 0uu0

L~~

lJ

u~~

t:>~~

~~

,....

'"'"'

Tne partial tree

,...,-,,.-,.TTN

en~::q;;y 01

T>T71.

~'y~

"{;nis

nen-,;-or-uur

re Is,

th~refore

V[A 1]{CnT + W1- T(Cvtlog T - R log [A1]

a1)}.

The free energy of the total system is obtained by summing

_._,_

~-

..._ 1

..c

.11

... 1.

...

mixture. On doing this, we obtain for the total free energy

"{;De expression:
r

-v

fl' -

!-.,_lAd ! C.:vil
i-1

:.n.l.:v JOg '1

vL
[Bi] { c~iT + w; i=l

1:(,

log LA J + a,) J

T(C~; log T - R log [B;] +a;)} (140)

We consider now an infinitesimal reaction of the type

~~6<>) ~unali is, a reacu10n m wn1cn an mnnitesrma! amount or
sub~+~ ........, if'~ +~~~ .
-n lf t.he r<:>at>t.inn
_,
f
the left to the right of (135), infinitesimal amounts of the
..,.nooa

rl~an

. -' .

n~.-:1

: . . .C:.

:...

of the gases B1, B2, , Ba are formed.

'

,.

...

''

.1

-'-

The fractions of
.
.I:' 1:"

'

proportional to the coefficients n1, n2, , n., respectively;

and the fractions of moles of the gases B1, B2, , Bs that
S>.r<>o
,,...,rl .,., a
,1-f._ nf t.'ho ...
-~+:~~ ~-~
tional to the numbers m1, m2, , m., respectively. Con1

..LJ

Ll.

.L"

.. . ,

;.

[B2J, undergo the variations:

-E?h, -

wnere e

IS

E?22 1

L'

.. ,

em1, E?122, , em.,

Enr;

the llltinitesrmal constant of proportionality.

lf Ji' if'~ t.o h<>o

<=l.

+-h~ ~~~:~+:~

minhrnnn fnr nnr <Ot.<>+""

r;T

resulting from the infinitesimal reaction must vanish.

,_
. .....
_,
C~:-~~

... 1..

- 1

.1

'

. .

differential, we have:
oF

- af~~]

en1 -

~ oF
"L

8 ~~ 21 e122
"-rna .l

...

...

__!

aF

- aTA J

aF
VL-'-'J

--

en.

... .

aF
.'ifR:l

Eml

~-

~~.

1'\'\

~~~

vivil
1:;nis eq1
n oy E v , ana. -reo ~acing 1:;ne ueri vaLi vel:5
bv t.heb; values as cA.lculated from (140) we obtain the
following equat10n:

-1

n,

{Uv;'l

+ w,

'1' ~ C..:v;

+ a;) + li,'l'l

H. log LAd

log '1

+ 2: m1 {C~iT + w;- T(C~i log T - Rlog [B 1] +a~)+ RT}

=0.

It is immediately evident that this equation and equation

\. .L 6<:!1) (;1,1'" :~~

_.._ 11\:l ~

~Y.'

'Vl:W-1.

".....,

IJ"'

nht.ained at once in the same wav as in the preceding section.

?.d.

ni!':Ct1C!dnn

From (136) and (139) we can ootam the

Le Chatelier.
vAi)lll.'.o.v

vaseous eauilibria: the nrincinle of

nf

................ v

vu"

-r-r'
"
[K(T) is sometimes called the

~-

rie:ht-hand side of (136).

constant oJ tne taw OJ mass action, oi ~..;uLU::;~::, ~" io:s I:L ~;u1
..,
nnhr H the temnerHt.ure is constant.]
Comparing (136)
and (139), we obtain:
'

}'; (R+cv, ai) n..:

fJ.'j)fl'lJ
~ (n+c~vi
ii' ,J-1
' _,
i=l
'

1{

XT
....... v

'

..,.
r

,,_1
'

,.......

~.. C..''v m;\

,~,

/('

t{
'
-

~"

,..

'

..

mJW';'

nW
'
1,

T.' / " "

_,

\.141)

_,

.._,__

-~

temperature, we first define the heat of reaction H of the

cnemica1 reaeLiun 1,.-Lv<J;. .. "" '-'""'' ... ~~... ~
CTns<>~ A and B at eom.,;tant volume and at a fixed temperature.
Let these gases react a~eonling to equation (135), so that

,. ' - '

""

'
speetivcly, intcraet
and give ri:-;e to
OI 'Lilt: ~at><::;::> v 1 , ~J 2 ,

, J ,

'

~0.

. m2 , , m.. moles
.,..,.

m.1 ,
:

.,

rleveloned bv the svstem during this isothermal process is

Called the heat Of TCaCtUI'n aC Consr.an~ V(v f.t;. .1.11\:: J.C"''-' vvu
;0 "'nirl tn hn <>-rnfhtrnJ.rtl or cndothcnnal, depending on whether
syKtcm wnen tne
heat lH g1ven out or absorbed by the

.
.
.
.
rc u.e t. H 111 l" '><"''"",;, , , ,.
,,0~\

.., 1\

omce the reactwn takes place at constant volume, no

--'

l!'!

)P.il ~

-"

t.hA

'T'"h

RVP+

haa+.

__b

.J'

absorbed by the system ( = -H) is equal, according to the

,..

1'

~~ ~\

.._

'1-

,...,. .

!:!.U.

Remembering that the enere:v of one mole of A, for

examp1e, 1s equa1 -r;o t.;v1:L + w 1 , and that the numbers of
moles n-F t.hP. 17l'l"''"'' A
A

.<1
n~-1 "R
"R
'Q
increase by the amounts -n1, -n2, , -nr and m1 ,
.

-.

'
find
. that the variation in energy associated with (135)
c

. .,

IS

..

liU = ~ mi(C~i T
;-1

+ w;) - L

n;(Cv; T

i-1

+ W;).

The heat of reaction is thus :

H = . ;, n;(Cv;T

W.) -

L-

mt(C~iT

+ w;).

(142)

Taking the logarithmic derivative of (141), we obtain:

r

.,
dT

_t__c.
-

*"
+

~ rr'

dl.

-~

~~

ITT

RT

RT2

J!'rom this equation and (142), we now find that:

UJOgAI,.:L'J _

dT

_!!

(143)

Rr2

It is clear from this eau.,.._

__W_hit>h
,1,._..
...J
'1
.nellllUOltz, that .K('l'J is an increasing or a decreasing
function nf 'T' r!.
,r!h, ~ ~
.
.1- +1..
-,
positive or negative; K(T) increases with the temperature
UTQ<::!

~'"

.Lt..

.1

temperature for endothermal reactions.

VV

~ "U

.LUO.OH:l

This equation can also be derived directly bv a.nnlvinu t.h., v.

.
, ~ ........... 1n semaon :.<::.<:.
~

-~~u

~~

.. . = ""

as

in which a change in the external conditions tends to shift

followin :
Ij the external conditions of a thermodynamical system are

direction as to oppose the change in the external conditions.

statement clear.

We have already shown that if the reac-

equation (135).

Since the reaction from left to right is

left results in the absorption of heat by the system and thus

of the reaction (135).

We notice that if the reaction (135)

,
aseous s stem chan e:::; if
(144)

. '

c:

.l..l.Ll

IVUO

VIce
versa.

10

From Le Chatelier's principle we must expect,

~Ua.

'V.LV.L 'V l

.l.

"'.L.L

.L.L.L'-'.L'

.P.L 'VOO U..L 'V

UU'V

.L.L.L

V.L

U..L

'V U.:>

rrrixture will shift the eauilibrium toward the left. that is. in
such a direction as to oppose the increase in pressure. (In
,
-,

in to:twh

3.

cr

.,, , . ,

.-

..-

-.
"""' the nnmher of moleto: in the
-

ato: t.o dl"'

,+'

'I., .

system, and vice versa.)

This result
obtained
. ,, " can be
,
..
.,
-"'
"
If we increase the pressure of our system
while keeping the
temperature constant, the concentrations ot the components

..

,.

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

.
num

; ....

'"'" .

T~

f. "ho ,..1.

~,..,

a;"h.

were not affected, the concentrations of all the

components would be mcreased by the same factor, and,

(1AA\ .,_

1.

,l..J

of (136) to decrease.
.

\~<>UJ

UJ.

lOt, d

l3.Se.

.1.

.l..J

... .L 1..

.~.L

..J .

..J

1.

But since the expression on the right-

>lJa.lllJ 1

LUI:J

li:JIV

l:ilUI:J

Hence. the em1ilihri11m mm:t. hP. to:hift.P.d

toward the left in order to keep the left-hand side of (136)

>l.ii:L.U L ,

W P.

mSI.V ~onclnr1P.

t.hiR RP.I"'+; ......,., hv

Rt.~.t.inu

t.hl'l.t. in

o-PnP.r~.l

low pressures favor dissociation processes while high

.

.1:"

....

1. For a chemical reaction of the

.L

2A = A2
the equilibrium constant K(T) of the law of mass action at the
~

-r-

~--~~

~~

~~~~~

~--~

~~v~

.t"'vuv~~

vu~

gaseous mixture is 1 atmosphere. Find the percentage of dis.,....,..,.

~"'"'"
2

Kno

' IV

t.hl'l.t. t.hP. hAA.t. nf -..oon+.inn fnr t.hP .,.,., ..L'

..J.

..J

in problem 1 is 50,000 cal./mole, find the degree of dissociation

.... JU..L..

~~-

.L.L

'l'he l'hermodynarrucs of Dilute Solutions

ZS. Dilute solutions. A solution is said to be dt'lute
.
..
'
'" '
of solvent. In this section we shall-rdevelop the fundamen"Lal principles oi 'tne tnermoaynamics ot auute solutions.
_.._

.L'L

"r

11

''

Joe

and N 1 , N 2 , , N 0 moles of the several dissolved subS'tances .tt 1 , .tt 2 , , Au , respectively. .11 our solutiOn 1s

;J:J,fo

nco....-.Hc.f hnuo

(145)
Nt No; N2 No; ; Nu No.
Our first problem will be to find the expressions for the
.
energy, l.ill'=' v011
, "Lne enLrupy, anu :su .1Urlin, ur our ...... ~ .... ~....,
.,..,.1,,+;~

....

A ,.,f,..,.;..,.l,.+"

oTrl

!:Inn!'

Af

t:hr.>

+.J..o~......,n-

dynamic equations will then yield all the other properties

._....

v .. ~~4o

.vv

VU'-'

We consider first the energy U of our solution. Let u

be the energy ot a tractwn ot tne solUtion contammg one
.1.

.&

'-'

..,

..... ._... .,.

.1

""

'1"'1-

&.

..L 44.LU

.1-~~
~v~.

~.r +\.,. ....,

... ~~1 .. 4-;~~

;n

...... ;~

N d No moles of the solute A 1, N 2/ No moles of the solute

A2, , N 0 / No moles of the solute A 0 lts energy will
1..

.c.

.._.

.&

..:I l-l-

fTI

~ .. ..,~4-;4-;..,,..

l\T

I "AT

i\T. !i\T

. . . , Na/No; that is,

u

u( T, p,

'

Nt N2
Jo.r '

No

'7\.r' '"hl'
'u

~;,..roo +ho t:>n+.1r<> <J:nl11l-.ir.n f'r.nt.l'l.inl'l

(146)

UF

N" TnnlPl'l nf l'lnlvPnt. it.!'!

energy U is No times lurger than (146); that is,

(

U = Nou T, p,

lV 1

N',,

lV 2

lV o ) .

Y\f;, , N: .

(147)

We now make use of the fact that, since our solution is

dilute, the ratios Nt/No, lV2/No, , Na/No are very
~~

_1_ "fA

.
... ., ""''"'"
, -r;nererore, -r;nat 1t lS possible to aevelop
the function (146_l in no
_of_ t."~_ra.tios ::~.nd__Lo__nFurlP~
au powers auove tne nrst. If we do this, we obtain:
'>T

UoV,

+ No'l-l<}.(T, p) + +

PJ +No U1\.L, p)

N:

U 0 (T,

p).

ouu1:n'~"u l~ t..uis expresswn m (147), we nnd t11at:

, ..
T<

.1...1 1-

.1.

_]

~~,

.L
-"'

~~

w ~- ---~

u ~ "'

expression (148) for U are formally quite similar, the first

:
--- o-- uu"'.._. ...,....._ Llltl U t..lltl.H:I -~..LUJSe OI 1<De
ineoualities (145)
.tly a similar process of reasoning, we can show that, to
t.h.a

C!Q

m.o

--l

,.j:

as:
u -u,

..t--.

'"'

'!.I_.

'

4o . V > \ 4

'1'1

-r ... --r

1V

aVo\.L'

PJ

,.Lin.

'

-'

TIT:,.~--~_ ~~ ~ln,
'"'ssion ror '{;Ile entropy of our
solution. To do this, we cons"ider an infinit,,.., uU..xe.
.i.hk
ion uuring wmcn "1 and p change by the infinitesimal amounts dT and ..dn. mh;Jo. .1
""-" .,.,
J.V 1 , , J.V a d.o not vary.
The change in entropy resulting
LV.L

.,:, ""

t.his.

,+n-rrn

d8

-;

dQ

T1 (,_-1 T r

'
I

-1T7'

1'"".

(ISO)

u-~
;.UIJv~La~e tnese pertect differentials, We obtain a
set of functions s..sJ....T n) ..s.d.'I'.. ....71l _.,_ _f_ri!_ --'....L
:
.L.L

VV'O

du.

pdv-

'T">l\6

~1

W~

HUW

A ,.KTr'<C'I

~'~~~

".,..,

.,.-,.T-

1,.1ou;, we oouam line express1on lor

the entropy:

" N,s,(T, p) +
?:

S =

C(No, N1, , Nu).

(152)

The constant of integration C, which is constant only with

'.1:'

.,

.'

in (152). We can deter

constant as follows:

evii!P.nr.P.
C!."

~~

.... ..-.. ; .......... h.-.c. l-

~~

J::'

VU>C>

the valnP. of

~1.-.~~.-:t

+l-

which T and p may vary, the expression (152) for S

,
,
,

. .

s-~l~tion, including all the solutes, vapori;es.

w ll.J.
"-'"'
vv_y
ol-r.oarl"<r h-nn-w- t.hAt. t.h,P

'"""> a.. .u

0 .

l!'l

t.hiR

.
still
.

Our system

"'"'-'-''-'

a. <=>:t oUv.LLl we;

+.n t.h.,.

AI"'1Hl1

i'lllTY'I

nf 1-'ho

partial entropies of the component gases (see section 23).

,.-,.

-~

1.

p.;. and having the molecular heat CP, is (see equation (87)):
l:p, 10g :1. 1-r, wg P -r a, -r 1(, wg 1(,,
~l:>.j)
(, .
. ....
..... '1
"0".
&.
.&
l-<-lpressure p; of the substance A,' is equal to pN;J(No
J.V 0 ), wnere p 1s une l..O"Lal pressure):
(I

-o

- L
i-0

'I

7\.T

~ JV ; \ t.,p;

i:j

+ ... +

wg

.1.

Ll.

Jog -p -

- -

-t-

Ui

-t-

+ -- + Nu
+ a, + R log B)
L: N, log--+
- R
No

N,(C,,; log T- R log p

----

i-o

Nn

fi

wg

1L }
1

1'1-

-~-+---.

--

If we compare this with (152), which applies to our

Ull <:t '-'
gaseous mix~ure an.;o, we

rt

1.

rp

1~,

..L

n .

..L

R lron- T?

and
C(No, N1, , No) = -R

But the constant C (No , N

.L

.L\>0

va.LUV

\.LV.LJ

z=; N; log--No+

;-o
1 ,

vu~~~

'-----.

N"

(154)

N ,J does not depend on

~1-~

. .,

......

.... c.

> "'6Tr'<.-o

-.-,.TT

~~

~~

ous mix-.;ure, out a1so uo -.;ne original solUtiOn.

7152) ,.
mes:

f:_ N,s,(T

D) -

N,

N, log

It. is conu<>Tl~OTJt. t.o simnlifv the lR~t.

taking the inequalities (145) into account.

.ttence,

. ..

(155)

. w

nf ( 1 fi.l'\) hv

.L

By neglecting
'1--AA

N 1, N

2 ,

N (/ , we find that:
No

No log

No log

+ No + ... +

No

-No( _N1_N2 _ ... _N~)

.,
... N
N ..
N1

and that:
~v

N, log No+ N1

+ + Na

N;. log

lV;.

No

(fori > 1).

Hence,
S = Noso(T, p)

+L
-1 Ni(s,(T, p) + R}

!:

N
R . ::. N, log .N.,.

Instead of the functions s, we now introduce the new

.

..

O"n(T

'lJ)

Sn(T.

'lJ)

o-l(T, p) = S!(T, p)
o-2(T, p) = s2(T, p)
o"ri(T, p) = Sa(T, p)

+
+
+

R
R
R.

(156)

vve nave, tnen:

.:=:,

-0

lV.;o-;Vl, pJ

ft ~

,_1

N, log]/.
0

(157)

\l'lotwe tne auterence m the limits of the two summations.)

A1.L1.

-1.

,,

.A

'

., . ,

._,, "'uA'-'v.r

......
mg, Tunc'tions oi :1 ana JY, --.-m:
in v
-au
resm'tinu
"aria
in thP. nressure are verv small in ~reneral
so that u,, v,, u;,, for all practiCal purposes, can be con1"_

..]

1..

.&.

'1T

. .... -- -.&

"'~ lu 1

In the theorv of dilute solutions we shall always make use

of these approximatiOns.
We shall therefore wnte 1l4~.''
.
~-;

..

,.

"/'

'

'

.,..
~

v
S =

"

N,v,('l')

i-=0

~
....t

N, u, ( T ) - R

~)'

...J

N log"-Vi
u .

(158)

U. V and S we can irnmediately write down the formulae for the free energy Jl' and
w;Fh +.'-

.Lt.

.Lt.

(121)).

--- fnr

..1.

....

;.,1

if>

foc.a.

a.,..,,., ... ~ .....,...., (111\

anrl

We have:

lll:!n\

No

.:-1

j.(T)

u.(T) -

(160)

Tu,(T);

To consider v; as being independent of p is equivalent to neglecting

the smalr compressll:nllty ot liquios.
"J, u.; -n.- ,._,. ........!:,. '
pendent of p; indeed, if we compress a. liquid isothermally, we know from
1

.& 1..

'

...

..J

-1

..J

'T'ho

also is negligible because of the small change in volume. lt follows,

then from the first law. that the variation in energy is very small. In

1;0 Buuw

"-''"'" Ui "'"'u o l ' '

'"

.J

with the aid of (156) and (151), that:

Since u; and V; are pract1ca11y

-~
'" u1 .P UJ:l<:O'.~ .u~~~ ~
nn +.hA ri<rht-hand side a.re nee:ligible. Hence, (Bu;/Bp) is very small, and
<r; mus ae..
. ..
'Y uu ...

> 1\ Jl" ,-,. T"Y'<

"'110

r-... ,.-

1\. .- T r<C<

"\. T."

T""\ T T

.--,.-..TC!

co,-,.T

ana
...fl.....

.. '"

'

''

b_Ni\f;.l..'l')
~-o

'

+ pV.;I..:t')t +

N,
=No

...!!-.

,.

i-1

-?-!N.;log N.
~-1
o

1(,'1

~101)

In dealing with solutions, we

shall call a sermpermeable membrane a membrane that IS
26. Osmotic nressure.
>hlo

+..-.. +ho o..-..1-.ron-1- anrl

ooa 'hlo

+n +.'ho Qnlnt.o:><:

Semipermeable membranes for, aqueous solutions are often

. .
,
,
.
"

'

A very convenient

cells are very often semipermeable.

QJ.

,.

"'"'

-..-

. ""u'-'

irl"' iTnh.,.rlrl"'rl
.1.

h
..

. L. 1 .

.t-'~.L~

~~.L

~~.L~

~~

1~---=-- ..;._

___.. .::.:-::--------:

~V.L

~'1."

',

insert-~ vertical tube, as shown in Figure 19,

Fig. 19.
.,

.L

-Into a co~tainer with semipermeable walls

we place a solution of sugar In water.
,..,.,
,
,
,
.

1- :

tion :_

~-L-----..J-;-

~'-' . t ' .t''-'.L

..,..

-,~

___..

v.L

TnRf.Pl";>'l.l

This can be shown by the following simple

o u-

.Lao,y

11<1

.. .

-...
-cu~: S I --

~,...-:-

.L

~.L.L~

__!__
-;..,- 1

""

difference of pressure between the solution

;
.--

.L"'

("If

When a solution is separated from the pure

...

;Tl !.\. "tll7<l.l1

.L.t''-''

U.L.LV

>'-'.LV

'-'.L

YY O..L.LO

UUv

.L.L<A>

."

indicated by dotted lines. The height of the meniscus in

wniS "{;Uoe serves 1iO Inaica-r,e -r,ne pressure oi "tne solU"LIOn
inside the P.OTit.fl.lTIP.r. WP. nnw nin t.hP.
... ~.inP.r in "' h>'l.t.h
of pure water, and observe that the meniscus inside the tube

that some water has passed from the bath into the solution.
.. . .
.
.
.
.c.~y_u.J.J.J.LI>

J.l::> .L'-'-'-'11.\JU

it.:UI:::\ 111 Lilt: uUUt: J.::> <:Lu 1;1,

WH\J.U ulltJ

certain height h above the level of the water bath showin!!"

that the pressure m the solutiOn IS higher than the pressure
in t.hP. ntll'P. "Wl'!.t.P.r.
osmotic pressure of
~.L.L.~.L

~~u

~~~

'T'hr:o, iliff,

'""' in

the solution.
""~

'~J

V.L

'111"<>

;"'

.... .,

ll<>rl +- h<>

If we neglect the small

yy "'~"-'~

.......,

-J

VJ.

l'"nTT.,-,"TYn. /l"r....--..""<7"-T A.,._ ii"Tr"<N

r....-;,

N/">T TTrn-rr..,._.,-,...

..-,.TT

.n.

. pn::;:;;,;ure

equal lJO line _JJn:::::;l:lure

exerted bv the liauid column h and is e:iven bv the nroduct:
Lne

~::>u1

~ne

1s

Height, h, X Density X Acceleration of Gravity.

To obtain the expression for osmotic pressure thermo

...J.

.n.

.u.

.c

.1-

.1

.1 ..................

work done by a system during an isothermal reversible

. .
. .
.
LJ..

~-lll<:tLlVH

l;::i t:L)_ U<:I.J.

l>U

LJ.lt

V <:t1

U.L

l>llt: 1 Ct:e

enere:v. We consider the svstem renresented in Fie:ure 20.

A cylindncal contamer IS divided Into two parts by a semi.nl-.1~

,h.,~.,..~

of the container.
.C' 11

. ' ,_

_,

.1.

"li'li'

~~~nll~l

+~

+"!-.~

"hnnnn

A 7:2

n~...J

I"Yn

The part of the container on the left is

'.

"7"

1'

_,

...

"

- -

Nn moles of several dissolved substances.

The right-hand part of the
(!

N1 N2

t>I"\TlT

o -in <>1" ~"

with
. 1.

N~

...

""'"""'"'1o+o luf;llarl

moles

of

.A

pure

"-'

Since the membrane sep.

. permea
.!:"
b le
t h e contamer
IS
to the pure solvent, there
:11 1-

-1'1.

..f

..

..., ' ~ ' '-" "

I
I
I

Pure

<". I

.I-

-.;'

Flg. 20

+1-

solvent through the membrane Ill both directions.

-,

-...

.,.

"When
.

equilibrium, and there will then be a difference of pressure

Ut: L W t:t::ll

Lllt::

tt:a L-

J!<:l.l L Vl

uuv .._ .._e,._.u

IJUC

hand nart. This difference of pressure Pis equal to the

osmotic pressure.
.

1.1

.1..

movable, and we consider an infinitesimal transformation of

VUl

O.YOL<J.Ul ULUUl!::.

uuv

VV

...,u._,

~.

tesimal distance toward the right, so that the volume on.the

left Increases by an amount a v ana r,ne vo
on une 1 ~
riPf'l"<>''"''"'" hv t.h<> ~RmA nmount.
Since the nressure exerted
on the left face of the membrane by the solutiOn IS larger
.., .Y .........

.L

UU"-'

!-"~'-'~~~

.-=.

"

.... ,.,

; nn

oi line memorane by the pure solvent, the work done by the

s ~+~ ~ is PdV.
During the motion of the membrane, a certain amount
~1

f-'11\T

,\

.J:

"-'

.c.

-1

_,

of. the
. container into the solution on the left-hand side, thus

. .

"~

~A

V.I.

<IUv

DV.I.U<I.I.V~

and the uure

.n+;~alv. nrin'r -t.n +'h<> +.-o~ "
t10n are, according to the second of equations (158):
. 1.

v -Novo+
y

.._._ .no

NtVt + ... + Nut'u

J.Vovo.

'-' y

~~4~

~-

ot.

~10:.1:)

uu ... u.1..v

<:W..1

o,

w~

nave Irom t;ne nrs1.

"'""" a-t.1.nn2

dV

VndNn'

and the work done by the system is ther

PvodNo.

(163)

The free energy of the solution is riven by (159) and is

equal to:
Nofo

+ Nt/1 +

+ N,du + RT(Ndog~1 +

+Naiog ~~)-

The free ener2:v of the oure solvent i!'l oht.... J

IormUia oy replacmg No by N 0 and putting N1
...

N.

Tl-,;., ....;.,TOO:

- N2

The total free enerQ"v of m1r

these two:

= (No+ N~)fo +

t.hiR

7\.T' J"

N1J1

+ + Nufu +

Since N~ decreases bv an amount dN.

ngeu.

;., .,...,.,.,1 +n. -1-ho .,..,....,

"""'

RT

N,Iog_i' .
ln.

.:.,;;;j_

1-.o~~ 1/TTI

ri'AT

'

.~

oince

J.V o ana J.V o

um

tus a1v 0

uy

~ctivelv.

as a result of the transformation

in F is given by
dF

=
-

VL

oNo

dN 0 -

RT

f.

N0

U,LY

VL

aNfJ

"f'

tiN.

the.,,.,....;.,+;~.,...

f, tiN.

t=l

J.ne negaurve or unit:! quant,ny Inut:lL ue equa1

(163) hP.r.ansP. the transformation is reversihlP.
RT

...!--.

No

i=l

u vu'

-a.J.V 0 ,

dN 0

N.

~ LY

ana

...

-~~

~J

'{,0

une worK
Thus

~~

.1:-"~~~

solvent, differs very little from the volume V of the dilute

solution (see (145) and the first of equations (162)). Neg'

"

.1-L'

.11

.a

-l'L.,..

-l

.1.

"

1..

1\T

T7

'

(164), we obtain:
PV

..!!..

llT?,:: N;,

(165)

or
(166)

The above exoression for the osmotic nressure of a solution bears a very elo:sc rescrnblanee to the equation of state
.~

V'.

..+"

(1gg\

"

1-

ol-

r'l

'.rnll.

terms containmp; the squares of the eonecntrations of the solutes, and

t.1

.&.

IS
<>nnl'li,t.mlt. urit.h n.ll i.h<' !Ullll'tlYimH.t.ions n.lr.,n.rlv nm.1IE> in t.hP. t.hf>nrv

ot auute sotuttons.

ana
<

consider a container divided into two parts by a semiSince the solvent can pass freely through the semipermeable

'
be the same.

Now let us dissolve some substances in one

e pressure on

impacts against it of the molecules of the dissolved sub-

'

which move about with a velocity that depends on T.

The

the molecules of the dissolved substances are not affected by

'
ties that they would have if they
were in a gaseous state.
'

of the molecules of the

in both cases are therefore equal.

(166), it is necessary to know the total number of moles of

,.,.-,-r.n

,...,...YY"Q"D"1\,-r>.TV"T"T

.---.,-, ..,...,..,.,-

........

<"'< _,-,. T

cu.u'
~
or t:>oiuLe per 1ner or waLer, nas, a-.:; .urv,
an osmotic pressure :
p

R X 288.1

"

2 _4 X 1 0 1 dynes

2R 7

..

T.

.L

.1

~.hn

...

1!

'

... . 1 .

place when a sub,tance is dissolved, so that the number of

.
.
mo1es 01 Ll1~ suu8Lance 1n t.ne SOlULIOn neeu noL ue -vue same
as the number of moles before the substance is dissolVf~d
The most Important example of this is that of an electrolyte
.1"

' '1 ,rl ; n

..

"'XTl-

.l

of'.

1\..T .. r"l

-1'

"

,].

.-1

in water, almost all the NaCl molecules dissociate into Na+

.
.
. .
thus about twice the number one would exnect to find if no
dissoc1atwn occurred. :::Some electrolytes, of course, dis1

_,...,,

n-'01

;.,tr.

cron;ato

-rnnn

+hon +"'"

li'r.,.

;ron"'

cr nlnnf,.nlutoc

the dissoein.tion IS practically complete even when the

.
. 1. ...
.1:1
'D
. 1.
1!
. 1.
.1
...

.-

lytes, on the other hand, chemical equilibrium sets ln

~~~

~~-

....

.,
~

~ .. , I

~- ~-

~.J

~~

~~

~~

Yoo~

recornbination of these ions. The dissociation in this case,

therefore, iH generally incomplete.

27. Chemical equilibria in solutions.

.
1

"

..

We have already

..

reaetions taking plaee in gaseous syHterns.

\.H:a

lll

> <.:; <>

~.-

'"VU L> . .<"

.LV~

We shall now

.J.v-'-'

'-'

~~.u~s

fiolu t.ion:::;.
Let .:1 o rC'prcRcnt a molecule of the solvent and A

...

.1

... A

1,

1.

'

\V e assn me that. a ehcrnieal reaction defined by the equation:

lloAu

n,A

can take pltwo

.,...h,,..,nl

,,]~n

.. .

mnon~

jql~~~

'llrAr < >

-m,JJ,

+ ... +

those su hst.ances.

lf nu

;;6

..,.-,,+in +hn ,.,,,,dinn ,..,'hPr<<1' if

only the solut.Ps na<'l. among tll<'mselves.

1n. n. (167)

.JU:-il, <LK Jll '>lTll\111

->,

\\l,

'>lliLll >l'ljllll\"

l,lliLl

0, the
()

WJ1Clll'lll."1l1lt:iL1

'" A"r>-.-,.TY-..T

"10A

r>,., ..,-.,...-,-

"8Tr.N

>

TT~~

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

.-.,-,...-

N'

>

.. .

oe a
.
equu.1onum IS r
, Lne Iree
.-g.Y
The free enere:v of the solution is 2:iven accordine: to (159).
by:
F = foNo

+ .?.;
j.N, +
i-=1

~ j~Ni
i=l

t-'
r

-1- R'T'

N .. lno-

I_Z=.L

_...

~~

r'1

~~~

-Vh~

""f'

-1-

:=

-1',~~-r;~~~

N'. lnu

~-"

U)

-~"~~

fTT

(16R)

+1-.~

,-l;.,.,nhrorl

substances A, and B; which correspond to the functions

...

.,.,,

'""

-=

-_so- . .-

-..

'

'

'T

'

'T

'

N 1 are the numbers of moles of the solvent and the dis.Cl. i

.+inn

i::IU.L V'tlU

T, .,-r ''"' .;..,

.L> j 1 J.' . ._- ''-' UJ. V O;:::.L.Y

-nYa nn-nY ,.....,,..,.,;,-1,,,,,

')~

o-n

.;.,...,:;..,.;+_oQlTY>al

of the type (167) as a result of which

isothermal reaction
,.,.
,.,.
...
. . . -.-rl
'
1

'

'

-eno

}-'VA.

..

. .. em

em,

-en~

an infinitesimal constant of pro-

E IS

...........'-''-'

...

-en,

respectively, where

,Tf

..., "'

av

v'i_'

.LU'-'

vanat10n must vanish when the system is in a state of

equilibrium. We thus have:

oF

-eno

dl'

aNa

n,;

-1

dl'

oN(

+eLm;
i-1

dl'l

oN.;

= 0.

Dividing by e and calculating the derivatives with the aid of

.,..

'/

''

'of

do not vary during an isothermal transformation), we find,

on neglecting all terms proportional to the small quantities
7\.L I 7\.T

r'l 71.T 1 171. T

....

1'

.
r

'

r>rn

run

1.

No

i=l

T
4 ~Since

N,'

f-..: m;
z-1

/'

1J i

7\T''

Lid.

.n.L

.tug

No

the var1at10ns 1n volume of a solution are always very small, 1t is

lTY>rnat.<>ria 1

-'-

"-

Wf'!

iiiPr t.h .. "nnilihrinrn PnnrfiHnn

votume or ali cons1;an1; pressure.

At.

,i:

VJ.

\No}

\No} \No}
/-.. I m /-..T'' m
.\No) \N~)

log

"'' m

...

\.N~)

~ m;(f;

~ n;(f>

RT) -

RT) -

nofo

RT
..LJ.Jt::l

.l.l~J.J.l,-

t:::Y. U<l.L.LUll
log: K ( T) K

~ll.l<S

Ul

<:.1. .l Ullt::

.1~

.L

U.l

onlv. If we place it eaual to

beine: a convenient
tunctwn ot the temperature, we :tinaily obtam:
'

'

'.

N m, ... (NriT)
( ~/)

m.

This equation is the expression of the law of mass action for

..
..
.
..
cnemiCal equuiona In so1ut10ns.
The r11scussion of (169) for the rol'I~P. where the so]
tt rlnP.~
not take part in the reaction (that is, when n 0 = 0 in (167))

+-'1-

...:!'

+-'1-

.-1' +-l-

.-1'

..L"

4'.

~4

gases (see section 24). It follows, m particular, from

. \. .l 0~) lJllU.t, II. We UHUl,e
.
.
. .. .
eq
Lile ~011
, LUC e q UlllUHUIIl
is shifted in the direction of increasing: dissociation. Of
course, In this case we have no simple way ot determmmg
1-ho 4'.

r..f

""' uro rli,1 in thn.

1<'{'1'\

>"><!.<>

nf

<Y<><U>C!

~"' l.rnnnT

only that K(T) is a function of the temperature.

'

'

.fi<S i;:l. .l-'<1.1 l,ll'lilU.J J.Y .LJJJ}IUJ lU.JllJ ot:.l\.i:t.lll}llt:l U.l

~JJt:l

.LUJ.

,_

the solvent participates in the <'hemieal reaction, we consider

tne react1on :
I

''

t.haJ. is the dissoeiation of water into hvdrouen and hvdroxvl

ions (the hydrolysis of water). Let [H J and LOH -J be the
"'"'""""ntr<:>tinn<>

r.f

tho

'hurll'niTt~n

UJ

W<tlt.:a >

\'VL'

UiLYt>

lV

t.hn

'hurl

"1

1nn<>

If we com;icler a. cubic centi-

(numbers of moles per ce.).

.lllt::L<eJ

<>nrl

, <'lt!

' 1t. 11" r> .,-.,. u-.."T

Ll.li:J .U

"

Ul

6 T ,-, N

Ul

lLl

,-,. T.1

,.-,. T T

LVL1

l:t.UU

r.. -..Teo

,-,.T

LU

Llll::l .UUlllUI:a

Vl

moles of water are, respectively, 18[H+J and 18[0H-].

Applymg equatiOn ~lo~J to the react1on (..l'IUJ, we r.nus
finrl

1
~0

l~~

1<(

. j l 'V'~.L

'1',

........
1

rH+HoH-1
whP.rP. K'(T) is::

J'l.

(171)

K'(T)

' .'
nP.-w fnnl"'t.inn of t.hP. +

1nP.rl'l.t.11rP. on lv.

We see from this equation that the product of the con-

,..,.....,+,..,+;.-.,..,., .... ~

-1-h.o

'hu~-

nn~

.j.J..,,. 'hu~

.,] :;,..,,..,.., ;.,.., nr<>f.Ar

At room

is a constant when the temperature is constant. 5

.
.
.
"':aHJ..'-'-'-i:l>"lll"''

1y

a, 1;,; <::t.ppr

"111;,; p1

"'4Ui2>1 "u

~v

when the concentrations are expressed in moles per liter;

that IS,
rf"'>TT' . ,

1A

,,..,.,\

-U

In pure water the concentrations of H+ and OH- are

equal, so that tor thiS case we have from (172):
[H.,..] = [Oir] = 10-1.

we auu
-.:;o -.:;ne wa-.:;er, r.nere IS an 1ncr'
u1
fH+]. and, since the product. (172) must remain constant a
correspondmg decrease of lU.tl..J.
Tt. ;.,
'T'hA
i t.A Ot>t>llr., if <> h<> "'"' ;., <> rl rl Prl +..-. f-.h"' nr<> t.Pr
usual to indicate the acidity of a water solution by the
J.I

t.. .1 .
"'.Y ...... ,_. v

..,,::r

( 1 '7::n

.T.",.. f1'1'+1

(Log stands for the logarithm to the base 10 fH 11 is expressed as before In moles per liter.) Thus, p.tl = 7 means a
D J:<'rom the I_aw of mass actwn applied to the :eaetwn (171), on? would
expect. the ra~10 [H+]_[OH-]/ [H 2 0] to be a furtctwn of T only. Smce the

be a function of T only in accordance with equation (171).

+1-

. .o.

""'"

form.

_,_

.1

...

-~

We
. .sec thus

uou v~ ,.,. "'"'" uvu,

jJ~~

-.....

L~Y

~uu.~vU.VO:::i:!

l:WlU J,J.LL

.?

indicates a basic reaction .

.Lne l;J.,uOvt: uiscussion OI cnemlCru. equumna m sotutaons IS
incomnlete since no account has been +.<> 1-Pn of t.he el
stat1c forces between 1ons. lt has been shown by Debye and
T.:T;;nlrnl

+l-.<>+.

.,,., .-..fton .-..f ;~~~...1-n~~~ n~:.:. ~n~

Rllnh "

A discussion of

affect the chemical reaction considerably.

- ..

.
~

Let A and B be two immiscible liquids (as, for example,

YV'-"V'-'

~-.~

vu

"""'"'I

~vu

stance soluble both in A and in B.

'-'"

"''"'"'-'

If we diRsolve a certain

short time, C will be m solution in both liquids.

.'

'.

.,

The

and the concentration of C in A will decrease until equilib~~uu'-''

~""",""" vuv

~~~~

Let N A and N 8 be tho numbers of moles of the two

SOlverlLI:i

n_

.v,

auu

auu "'"

~1

auu

uo

HJ

vue

LUvLi:!

VL

moles of the solute C diR:-;olved in A and B, respectively.

The thermodynnmie pot.elltial, <P, of our system will be the
'

,.

.1.

1.

We have first a solution of N, moles of C dissolved in N 11.

1

..

constant pressure of thi:-; t-mlution iR, aeeording to (161):

J:C'l'N 1

lOg

VV J 0 1 J 1 >
wnere J.l, J 1, 1'A, anu v, l:u'''-'"1~
the e:eneral formula (lGl ).
Seeond, we have a :-;olutton wllH'h eontams

~I

niH

ml 1< ,,.,]

l\{

nH,ln' nf tllf

',1, ,+

{"!

N A,

VO)

U.UU

1Vn

motes OI

Tt,R

dynamic potential is given by:

'i'/1

H /J lJihA I

I""'.

.
J

'

'

I .

" J l\

'

Vl VL

N~

~1-

-- --where the quantities JB,

r.

~J.

-f.

cP =

For a

g~ven

Vl

LU

'-'VL L <;; _...-

of (1 fH)

RTin 1J

of the complete system

The thermodynamic potential

ana

VB,

Jl,

~,T,....

<"<"T

+ .;[>B

.;[>A

(176)

temperature and pressure, the equllibrium

We consider an infinitesimal transformation of our system

a::; a

!"I:O:I:lUlu Ul

au

llJ U.LV 1

VL

.1.-'

.L.LV.LU

vuv

liauid B into the liouid A. N1 and N~ will change by

amounts dN1 and -dN1, respectively, and the variation in
W 'tXTlll h.O m"<T.OT> h"'T'

T"

1_

.:~ 1\T

84>

.:11\ T

OlVt

'

'

oil>
iJNt

.
.

...... .

....

Dividing by dN, we thus obtain the equation:

a<P

;J\7 =

a<I>
,7\T' .

(177)

Using (176), (175), and (174), we obtain the equilibrium

condition:
fx(T)

+ PVt(T) + RT log N--:. +LIT

=

f~(T)

+ pv~(T) +

RT log;:

RT,

or
'T
Hl

It '(T)-ft(T)+p [vl '(T)-vl(T)]

N-t

,,

RT

.\

( ' 1'70\

1V 1

NR

where the function K(T, p) depends only on the temperature

'

...-

Equation (178) expresses the following law:

When two dilute solutions of the same solute in two different

.

UV<V~<OUQ

'-"' <:-

'-'''-'

VVIO"'-"'-'~

(..ld<-l"'

<-t v'f_

'

Hi,t:;

I U,HU

1"01\;fr.T'>~Y'

A,.. .. Tr-1<'<

OJ ~ne cmbce ruHU'IUS UJ ~ne

and vressure is constant.

,._.,

T>

'T

"''""""
at a g-wen

~wo sotu~tons

temperature

A nroblem analogous to the nrecerlina onfl iR thP. followin~r

A solutwn ot a gas dissolved m a liquid is in contact with

~"h;.. ~'"" ~T<!nlf

+n. Mnrl +l-.a ...ola+~~~~l-

l- .+

+1-

of the gas and the concentration of the solution for which

IJ~~O

O::f'

~<> ~u

vy_

.. .

H.

~~V<:::U.

""'-' i:L

LOll~~Jta~:~,t,u.to.

Let No and N 1 be the numbers of moles of the liauid solvent and the gaseous solute m the solutiOn, respectively;
oT>rl

7\T

lo+

h~ th"' T\llTnhor

Af

'YYlnlao

~ ..... +l-.o

r..f! none.

n'O<!t:>r\1H:>

Since variations In volume of the solution are

phase.
.._.

_,..

. 11 .

!L.l

~-

. .

1.

.1.

of the gaseous phase, we can neglect the term p V in the

expresswn tor the thermodynamiC potential ot the solutiOn
a-nrl

-irlont.ifv t.hi..,

solution.

n+i.,J

"rith

nf t.h.,.

+h<> fro<:>

According to (159), this is:

Nofo(T)

Ntf,(T)

RTN1log

!f._

(179)

ne Lill:li'
ty HUlllll: J.lULI:lllLHLl Ul Llll:: ~
IUb r
~i:>
obtained from (125) bv multiplying it by the number, N1.
of moles of gas :
.1.

N~ [CPT

+W

T(C, log T -

R log p

R log R)].

(180)

Adding (179) and (180), we obtain the thermodynamic

1
"
1
.
.1.
J."
pu'-'vAiLHU ' l ' Ul Lll<::: LOL<.U M.Y"'Lt:Ul.
o.l U"'IJ Ui:> J.U v l l v }!"'''
problem, we obtain equation (177) as the condition for
eqmllbrmm. tiut>Htitutmg tile cxpncn expressiOns ror "Lne
T.

-'I.

i"at;'""' ill (177\

'''" nhl .,in ""' t.hP c>onclit.ion for P.Clltili-

brium the following equation:

f,(T)-+- RT1nrrN 1 -+- UT =
"

C 1'

n'

I\\11\J~L

'~ HJ~

""

-"" IVfO, L"/'

or, UIVlamg oy
we finn that
1 N

.tt:J.'

ana passing trom 1ogantnms to numoers,

UpT+W-T(

1 _

a,

.o

log T+a+R log R)-fr( T)-RT

RT

(lSI)

K(T)

Equation (181) expresses the following law:

'l'he concentratwn of a solution of a gas dzssolvea 1n a

],;r.o,,;ri nf n

+~

I ~n

'"

~,1 1~ lh.o

,.,.,..,.

nf

the gas above the solution.

It can be proved in a similar fashion that if there is a
=

~~~

'1.'

~,

each gas in solution is proportional to its partial pressure in

uut: HJ.lXuurt: I:Luvvo;:; lJDe nquiu.
1.ne
iJJanu u1 .1-'~ --"'
tionality in each case depends on the temperature as well as
on the nature of the solvent and of the particular gas
ronn Qi r1 >'f'<>rl.

29. The vapor pressure, the boiling point, and the freezing point of a solution. The vapor pressure, the boiling

...

.J

~-

- 'L

.L

"

. 1

.L

l..

L-

as for the pure solvent.

.1:"

~"

This fact is very important from a

,

~~~~~~~,

~~

..

~~

..

section, the changes in the boiling and freezing points, at

1ea:su rur uuulJe SOlU"LlOns, are proponwna1 "LO lJne mowcu1ai
concentration!'~ of thP. Rolnt.P.s
T'hP. o'
rntion of these
changes affords, therefore, a very convenient method of
o

We shall assume that the solutes are nonvolatile.

I>UUI>

I>Ht:

V -r

Ul

uUv

>:;UJ.U~lUH

WJ.lJ.

CUlJ.~UJ.ll

In
pu~c:;

vaporized solvent. We shall assume further that when

the solutiOn freezes, only the pure solidified solvent separates
011t. lP<tvino-

<I

11 t.hP "'n1llt.P "'t111 lTI <:n11'

We can now show, from very simple considerations, that

' " """TV'<Y"'O.T

'"'y,

~ ~Tr'<C"t

........

-.;na-.; ror -.;ne pure SOlVent a~~e same ternnerature. To this end. we ~nnf'l1r'll'r thP <>nn<>r<~t.,., <>h
in
Figure 21. lt consists of a rectangular-shaped tube I l l

-u:fWtJr

h~nl...

~h~ ~,~~

~.-1

~~~

~~.:1

~]..

'1-

+.

_]

each other on the lower side by a semipermeable membrane

>

solution resnectivelv. will not be at the s<~m<> hl'inht. hnr~<uJs>

I'

of the osmotiC prcsure; the level C of the solution will be

1...~ -'L

rJ;o~l.rc><l

Q;.,..,..n +l.n

..

"" lwt n n

.... : 1
<

'

- l

'

'

region in the tube above A and C will be filled \Vith the

. '.

-.r:-

>

We first wait until equilibrium. is established; t.hc vapor

--prviOOU~'V ~U 1.>!1<::

~,;11

UlHU~'UIU.lv

+1-.a.,., h<> +1-.<>+

~f

"

""-"!;1lUUIT!UUU

"".--.tn>-<lfurl

unnn.

in equilibrium \Vith it.:-:; liquid phase,

. ..

Vapor of .solvent:

.,

-.-

<JT \7lTC Jiilllll:-:ieUH ,1

>

.. -

that of a saturated vapor in equilib--rru~U

' ' lt-U

,,_IHll.HJll,

.L l

,,~

'

\ " ' ' ' " 1.>

that the prcsHurcs at A and at. C are

not equal, s1ncc .tl ano c. are tu <111.t. hP;rrhi" 1n i lH

"-

R; 1 \1'1'

nnt

"l.'!>

>

('

lies higher than A, the vapor pnsstuc

---....-v v

><J" " l

!>:>

ll " " J

" .-.' '"'''' "'

l lli " '

A ....

t lu

SOlUtlOll

vapor

pnss11n~

"'"1.

lS

lOWer

tllUll lllC

,..._ .D

I -..

... -

~-....

abo\"(~

..

the prcs:mre of Lhe vapor

...

.....

,<

Flg. 21.
:1.110\'( ~

t.I1D

pllrt~

To calculn.ic this diffpnncn in prPsHHn, i:l.p, qwmt i1n t h.-1:<-,

'

. .

--w-e-!lVl>H'l- 'llliU. ll l

. 1

\C\fllil!

of vapor of h\'ight h.
g lS tne aeeewratlon

l<P l 111-

If p' is
o1

f'":,

'"'l!l\-\~,'o;!. { ' f l' l l l l l l l l

tltt~

d<'llHi t y of tl11 va pnr, and

WI' navP:

grant~.

'

On

the other hand,

t.IH~

jlrt'S:-\ll)'(' PXP rt

d lv t lu lilfllitl

C01Ull111 (.'J) lS (~qual t.o til( OHtiHit IC' Jli'P:-:Hlii'P

I' or tIll' :--:ol111 IIIII.

11111'1' '-'lllYnlli ,. ... ] , . " ... r.... II ...

osmotic prcs:-n1rP (111'1-d<'l't ing t ht. , Ii !Tt rt 11 t I ut \\'t'l'll
t ''
UvUoCl>VJ' \.1> (tl\~ ' ' " " " ' ' " ' < ' l l ' l
l i J \ }Jlll\ ,'!JI'\\'111 > <IIlli ;\1:'()
Tf

i>: t.lH\ d .. nsif.v nf 1 ),,-.

\J><t\

'"

..........

,,. ,.-r-,

,. ,.. -r r<'"'

neg1eC1jing line aensiliy

the liauid)

...... -r -r

,-,. -r..

.-.,-,.-r

ljne vapor as

01

"-'TC<

tpareu

Ul

1M

hg.

Dividing the first equation by the second, we obtain:

=j}' =

I!_

~'

or
p

where

pu.u:::

I.JHt:;

and

Vo

Vo

I::SU~ Vt:l.ll~

.... ;,.,"" l..r ( +h

<>

Vo

Ap = P-

p-,,
Vn

are the volumes occupied by one mole of

.l.ll

~~.u:;

t-
.,' <> ..-o ;.,., .. :

~.u

llY,l.UU.

+ ; "'

<>.,., rl

I.J.l.lt:>

v a.pv.t ~,
..L_;r.Y><>l +.r.

>hr ...-. ... r.

p and p', respectively). Replacing the osmotic pressure

,
,
,
'.
.'

--~-

'

simplicity, that there

LV~V.ll'

W'V

,
18

..

'

P
JO

only one solute present in the

VUVGW-U.

R'P M.
I

'-'-1'

\~Uioo/

No

Vo

which is the expression for the difference between the vapor

'1 .....
.... .
l' .. l.:I ... l- ... .c 4-l.I
The fact that the vapor pressure for a solution is lower
r

"J

that the boiling point of a solution is higher than that of

I.JHt:;

pun:::

.LH~

1:5Ul Vt::lllJ.

.L

ur

. .

I.J n.u:; 11:5

lJ 11 u lJ

..

lJ .u t::

noint is the -temnerature at which the vanor nressure is

equal to one atmosphere. Consider a pure solvent at the

..

. ..

-~-

~-

-..

-~-

If we now dissolve some substance in this solvent, keeping

..

V.L.L'V

La.VUJ.C

>~a.ui.J,

l.<.l.lv va.pu.1

.t'~~"'u.Lv

w~.u

~a.u

'W

one atmosphere. Hence in order to bring: the oressure back

to 1ts Original value of one atmosphere, we must raise the
t.,

1.f.11rP. nf t.hA Rnh1t.i nn

Wit.h t.hA .,_;.-J of P.l'llHI.t.inn

(182) and Clapeyron's equation, one can easily derive an

v

.. v ...........,

V.t

VUV

o ..

LV V.L

""'

,,.,..~

.........

'

uomg
'trus, nowever, we snau catcUla'te oo'tn "tne
decrease in the vanor
"''nrP. H.nd t.hP. in,
,...,. in the hn;l_
mg pomt of a solution by a direct method.
u1ts1

oi

'UTa

..,,....,...o~...:J~~

...:1;1.

,1,

,.j.

,.4-

...1

.1 .

'i\ T

..c

solvent and N 1 moles of a solute in equilibrium with the

.lll . the

n
~

I
u

of solvent contamed
vanor nhase. From (148)
~14HJ, ~loo), and (121), we obtain for the thermodynamic
.t.; "1 m

...

,...; +'ho

....

.,.,_],,+~..-- ......

lrn

1\T

_,

.,..,.

rrn

-orn-..r

-'-

N1

.V 0

urhP,..,.

<t>o(T v) =

Tun

Un -

and"''

'DVn

Tu,

u, -

vv,.

Let cp~(T, p) be the thermodynamic potential of one mole

~~

"".t-:"'~

v~

vuv

""-'~

v .., ..... u.

..L LJ.<:i

..1::''-'U"'"-'U.La.

-.,

V~

the N~ moles of the vapor phase is, then:

<Pvap

No<po (T, p);

ana 'tne 'tnermoa.ynamiC potential ot 'tne total system 1s :

.P

tPaol

+ N1cp1(T, p) + RTN1log -;:

+ N~'P~(T, p). (183)

.PV>Lp = Nocpo(T, p)

.1.11e equlliurium conunaon is lJnav '*' ue a minimum tt.IJ

constant +
rature and nressure. We must therefore
have di:b - 0 for an infinitesimal, isothermal, isobaric
-1-

.I!

.... .

T+' ri7\T u
~

,],

~~.

.+' -1-1-

1.

.-1.~

~~

-1- ~
~

...I!

...1

from the vapor phase to the solution as a result of such a

. .
.
"~

dNo and -dNo

\I

.L<::> 7 .U. .LV 0 a,.u.u. .L\' 0

V a,.L

.Y

OJ

.Y

UUv

respectively), then we must have:

d<l> - d N 8<1>
8<1>
n - - dNnvnu

or
ac~~
t.IHQ

8<1>
O!Vo

ru.uu<::>

-.~A

r..T:>

,..-,..,. Jrr....-..u-...T A " JrT.r<N

.,-,.yT

Nr..T

TTrrl~

r..-...Tn

equauon oy -vnerr
.n.ep!acmg une aenvaljlves
ln
-'icit exnressions as calculated from (183) we obtain:

,,~(T

R'T'

'1l) -

Nl - ,,,~('T' 'nl

"'"
.,....,4 '

~ llJ.;::j

"'Y.'

N.

.,.-u,4,

J:'/

.1:'1

..IJ

.
"'AI.JJ

l>H~

.l t;.Ll.l.'

,4~4/

No"
uo;; 11 w

~o;;u.

~.>.u~

~.>o;;.L.u-

neratw-e and the vapor nressure of our solution.

Let Po be the pressw-e of the saturated vapor of the pure
d.nl"P 'T'

+ ...t. t.hP t.PTYl

<>nl

'T' <l.n.-1

urill

'Yl.

<><~+.i<>fv

Pnll<l .

tion (184) if we place N 1 = 0 in that equation, because in

.J..lV
lJ.L.LQ"
= .J:-1.1
'" .1..
.L.LU.O

trn

1 trn

....

I<"'"''

When N 1 moles of solute are dissolved in the solvent, the

pressure p of the vapor becomes:
.1.

.
_t-

,11
~

J:'U

.... '

p.

-~-~-~-

.u .. u,J

.-l"

-1-1.
~

uu~

1 ..1'-1- l~~4

.-l

4~~-

-~

side of (184), in powers of t::.p up to terms of the first order,

we

Mll:liL

,..,.
Lf/.1

No

<Po~ .1

Po)

<Pol..l , PoJ

un

Ap

apo

'
= 11p
Rin~P.

O<,Oo~ :L,

Po) _ Ocpo ~ '1 ', Po)

!'ln.

'

, ''

-----

opo

l'l'Yl.

"' i<> t.hP t.hPrrnnrlvn <I.TYllP nnt.Pnt.i,.] nf nn~'> rnnlt:> nf

,,
--- "1'
/

(186)
T'\llrc>

solvent, we obtain from (123):

ocpo~ '1

, Po) _

l'lTI.

Vo,

where vo is the volume of one mole of solvent; and, similarly,

ocp~( T, po)
UJIO

> .,. r '"'- -,-,. "'<

:r-.. T

.,. ,r T _..,

-~

"-''V..UU

L.I.V.L'IIo:::i

l.uD

w .u.~.L"' vo

is tine vmume or one mole of vapor of the pure

solvent. Substitut.in"" t.1.
; ,..,....,..,
1'1 , "''

RT Nt
.6..p
( 1 0'7'\

'U

Since the volume Vn of OnP. mnlA nf ... r.,,... . 1

line volUme, Vo, of one mole of liquid solvent fl.p is negative
1.
'
r
-~
. .,.
V.L IJUI:> SOlUtilOn IS
lower than that of the pure solvent. If vo is ne0'11rn'hlP. R.R
. w"' l:tts;:)umea "to be the case in the
vv
~
,.,u '-'V vo, w
derivation of eouation (1R2'1 Amu.t.in.n r1 Q7\ t.
went1ca1 with ( 182). (The minus sign means that the vapor
= .n.f +.h.o <>nl.+ _i,;,_ 1.
+t.
~
r
solvent.)
IJUI:J vApession I or line aecrease m the
vapor pressure from eouation (1R4)
Wi't.h t.ho. n;rt ~i! +ho
same equation and by a method analogous to the one just
I

L 1.

"'

n"'AO

,.

.LLQ " " '

..,.,..., .,].,,.,.

ro1>.lr>1~ +'ho nhn~~~

1.

,.

....

~~

of a solution.
TXT.

_,~,],

.1

. 1

.....

the pressure p of its vapor is equal to one atmosphere. Let

:1. o oe line botling pomt ot tne pure solvent and T - To + fl.T
the_hoilino nf t.hP._SO}ut.1rm
~in.-.o ~~~at the boiling point is equal to the atmospheric pressure, p,
.L

',..j.

.C.-11

Ll..

<"

CL

temperature To is equal to p.

'

~,

'~UAA

UAA~

_,,.,( T,., 7))

cl.

Since Nt

~~'-'A

.... ~~~/'

,~('T'r.

0 for the pure

VU~U o

.,)

()

(lsu:l)

Applying (184) to the solution, we obtain;

cpo(To

ilT, p) -

cp~(To

+ .6..T, p)

N1

= RT u.

Developing the left-hand side of the preceding equation

.
.L.L.L IJVW'V.LO U.L /.J,..L J l:tUU U.Lvp:
~U IJ<:li~ i:LIJVV'O IJJ.:I:J Ui;:)IJ> W<:;
obtain__.. with the aid of _(18~ the followmg ~uatlon:
I\

ocpo(To, p)

'I'
\.

V..LQ

ocp~(To, p)l
V..L U

.J

RT, Nt

..... ,..

..li'rom

we have:

(1~4)

a..po~.L

o, PJ

= _

uo.

aTn

o, P_!_

a<po~.t

'

aT,

G'Q'

where uo and u~ are the entropies of one mole of solvent in the

ilquiu ana vapor pnases, respeClilVeiy. 11 rom t.ne precectmg

...

'

'1\.T
.... .L

G'Of

.u.L

o No"

\,lOY)

Let A be the heat of vaporization of one mole of solvent.

~

<'V">..

~ ,,f: .j.J...~

'" . '

~ ~

1.

L 1.

.;.., t.'ho ,..'h.,.,....,....,. ~ ...

''-

'

1::1'.

To

uu

uu

To"

. ,uuing ~Juis In equalj10n

>.;:ll.l

\,1(")1:1),

we obt.am:

f).T _ RTo N1

(190)

~_M

. -Fnr t.~ _di#, roo. J-..n-1This is the

.t.l.
boiling point of the solution and the boiling point of the
.,., ,.

'

.+

a:

rn

"'

--

tion is higher than that of the pure sol;;nt. We see also

rrom the equation that the change in the boiling point is
..-1-:

Hl.l

f.n t.hA_m_olc.nnlo-.. ,..;.,

.....

..& .t.l

--1

As an example, we shall apply the above equation to a

-'-"

1"

--

solution, we have:
N1- 1;

No-

1000 .

_11.. -

n4o v

~vv~.

.
'

~o

,_, U'-JH i:1.

l.R~

.&: '-'L

"J- .l.

.L>.

...

ann Am calones m

(We can express both R

"'- L ~~ ...... n+~~ ~~

~~"

equation (190)

'"~"'..-.1~"~

,hr A"

~-

.\

~11 'L

..L".J. . .

+.-

ing these values in equation (190), we find that:

.L l.J.I::l

~V~U.~ULQ

degrees.

0.51

1'1
\.LUVJ

'-'~~~

W'VV

of Sl. ~olnt.ir.-n
The onlv
difference is that, instead of having a vapor phase, we have a
..;h., .............

~ .....

-f.,..,..,.,.;.,cr

t.'h<>

"

1t.

'

-"-'-

,_

.J.

'L

-L

..1

by one mole of the solvent in passing isothermally from

u!le

. .

llqUlU

IJV

IJHI::l

i::>VHU

""u

i::>IJ<:l.IJv

uu"'

~.L'

heat is negative and equal to -A', where A' is the heat of

fuswn or one mole of the solvent. ~or the case 01 ueezing,
A

\.'

- 1

'I

RT~N1

...

...

A'
.L 1..

No
.J.

..C

. ...

.1!.

.L L

, ___

'1.

solution is lower than that of the pure solvent; the decrease

IS

propu~

IJV

l,Uv

.VLVV'-L.L'-".L

S<olnt.ion.
In the case of a normal solution in water, for which
N o-18",
- TOUU".

N1= 1 .'

A' = 80

X 18 calories;

To = 273.1,

R= 1.986 calorieH;

we tind that:

.....

or< .J .

.L

.U..L

.~~

~~e. ~v~-

ht.A 7\T. rAnresents the actual number of moles of substance present. in

1

- 1 ..1

IJ.U<:;; i::>VLU.,Lvuo

...

..1

J- '1

.J.

.;,..,

-~

11

i- 'h .ao.a

.,

"

..

11

.'1.

must be considered as an independent molecule. Thus, for

the case ot very strong "'..'"' :LI"Ul.Y "c;"' 1.11<:1. v ~ue. <:1. ~
. "'"' v.L
;!;~n~n;ot.ion) N", li"l oht,pinArl hv multiplying the number Of
moles of solute by the number of Ions . mto which
a smgle
.
UJ.

IJHv

"'"'

U .LOP'-'

.L """.L"

" .L.L.L

Tile -Entropy Constant

have
, __ , already seen that the
_, 30...The N
. .ernst
. theorem.. We

- ro1

o-

- o]

rA
0\_.ti)

-I

'

}o

.:~r.

T'

where 0 is an arbitrarily chosen initial state, is incomplete

""'"'

IJUv

<l.L IJLIJJ. <l.L

J.J.L

IJLL<J

VJ.

IJUv

"IJQ,IJV

introduces an undetermined additive constant in the definition. A.S Tong as we deal only with differences of the
L

1_

-1

..
that cases arise (for examnle
"TTT.

.1!

-'-

--.;-

-.r-7

1.

alreadv found however

in
dealing with gaseous equilibria, Chapter VI) for which the
1

.-

---.::::.-

.....

chapter we shall introduce and discuss a principle that will

. ~ lJJR:l-.:17 1ve- const.am; ap:.,. ring in
----enaure us- t;U--a:e-ter
t.lu"' rlAfinit.inn nf t.h.<> <:>n-'-

'T'hi"" nrinf'inlA

urhi "h

lJ<T!:IQ

discovered by Nernst, is often referred to as the third law of

-.
t-nfjrm;aaynuim~cs or as lV ernst s "lneorem.
Tn t.h<:>

in urhi,.,.h

-it-~-

.nrio-inA.llv !'lt. _..

..J

hv N,

this theorem applied only to condensed systems, but it has

.t-' _t- .J

"J

. .

We may state this theorem in the following form:

The entropy of every system at absolute zero can always be
tii!Cen equa--z to zero.

we nave aennea on1y amerences

or enr,ropy oetJween

an..,r

+"<nn Q+n+~N

nf

''"

t-'h.,. a 1

"'+-<>+AmAnt. nf N,

__._,,.,

theorem must be interpreted physically as meaning that all

...

~J

,t-

the same entropy. It is therefore obviously convenient to

cnoose one Of t:ne states Of tile system at '.1 = u as the

stanaara state u introaucea in section 1~; tnis wiu permit us

to set the .+
of the .+ <l~.rrl sta.te emm.l to zero.
The entropy of any state A of the system is now defined,

+ t-

..:~

'1

..:1..-J :..

....

+ 1-

1-

.j.

...

''

~,

_,

w.uere '"ue in11egra1 is vaKen a1ong a reversime vra

.J..ll<:H~u.u
'"anv state at T
0 (1,
limit.) to t.he st.ate A
In this book we shall assume Nernst's theorem as a pos... 1. +

.&.

_,

+ 1-

~...

1 1.

1-

will serve to demonstrate its plausibility.

. .

-.,

'J

not. a !Olh<>-rT)lv defined state of the svRtP.m be~ause it corresponds to a large number of dynamical states. This
._.

..:~

..:~

+l-

.1+

.1

S = k log

where

?r,

is called the probability of the state.

ri"Tr::.\.

....

'

..,.

"J

Strictly

'

the number of dynamical states that correspond to the given

thermodynamical state. This seems at first sight to give

...

..:J~a::

.1+

~:~ ~~

+1.

------..:1------

.1

state corresponds to an infinite number of dynamical states.

. .

'J

",J

the following device:

.Lilt:

uy.

l:il!l:I.Lt:l:i

UJ.

i:l.

l:iYl:ilit:.LH

!Ul'lU

tt.ll

00

<:uAtt.y,

where f is the number of de!!:rees of freedom of the svstem

each state can therefore be represented by a point in a

.-.

-.,

- .C"

system.
l:ilJI:LLt:,

.. .

. 1

1:"

..,

Instead of an exact representation of the dynamical

.
. .

llUWt:l Yt:l.L-,

W.

IJt:l

!:,.1 Yt:l.l.L

JJY

l!Ut:l

nrecise nosition in the nhase snace of the noint renresentinl!:

the state, the followmg approXImate representation IS
>n-'-

4nf'<>rl :

The phase space is divided into a number of very small

Ttl.):!; J:!jl'l

.L nvr

\ ..AJJ.." u

.L

..

A "f

then characterized by specifying the celT to wbicn tne

rrlo,,"
co+Qt.A!:: WhOSe& representative points all lie in the same cell are not considered
''

"'""

. 1

'

'-

.J-t.-

.1!

.,+ .. +~ ~.r.

1.

s:.-

.v~"

system would evidently become exact if the cells were made

.I .

........ ~~..... nf tl-.t:>

nvn"'rnical states of a system

introduces a discontinuity in the concept ot the st.are O.L a
_"'
'

- -' -+~
- 'h
t.'h"" mP.thods of
aid of the
combinatory analysis, and, hence, with
. .c.
, ....
. , Clthe
~-t- +l-.o
,11

r'T"t.

o
..
It should be noticed, however, that the value of r,
""~""'

..L>VJ.'

~,

entropy.
ana tnerefore tOe
'

"

,t.

ValU~---ui" IJH<:;--.:::=u-~.v_pJ

~.r. .n,,.

_.,.11.,

.. ,

--r

i,..;~..,.P.d one finds that, if

11,

the volume of the cells is made vanishingly

we change-r,

1r

~.

..

'h

-1

1.

is altered by a factor.
A

" ' .LO'JS

l 0

.....

_..

But from the Boltz'- 1

oo

ootn 1r
t.h1-t if

.J

~ . . . .,..-:~

.l.

factor in 1r gives rise to an undetermined additive

constant
,
.
',
l l l ;:},
We see IrOill LHt:: .t~ .. vo ~
"'"""';<>,.1 ..:t ...t.i..:t.i~al mechanics cannot lead to a determination of the entropy constant.
. Cl 1-l
~ ..... .-'! t.l-with

--r.uv

.....

.v.

the entropy
also, in the classical picture can be... . _removedrrl,:o
by
.
ID.a
U~l:> V.L IJ.L.L<:; ~
~
.
d
-rP.ason for this is that the quantum theory mtro uces a
discontmuity quite na-r;ur1:1ou,y J.J.J.uvo v. ,....

d-;,~""YY>;n.-.1 "'+"+"" nf a svstem (the discrete quantum states)
without having to make use of the arbitrary diVISion OI tne
A

.r

"'~

~l ----~ +'hat. t.hi!Ot

'-

''

ili..:<>on-

tinuity is equivalent, for statistical purposes, to the division

of "tne p
tsP""""' .......... v
,.
-=
6.55
X I0- 2 7 cm. 2
+"" hi -where h is Planck's constant (h
gm.. sec. 1) and f IS tne n
u.t
__.
. w.,. ~~ note here, without entering into the
details, which lie outside the scope ot ~ uUUK",
....... ~

~
n.~m~~+,rn+~

-.

.1

__ ,..,,

St.lt

o1

1An

0':(.1..1

"f":' .

IJt:J:

J'

,-.,,.-,.

.lL.lUJ..l
. U.l

.ll.l (,Ilii:J

A -.,.T,.,...

l'll:l.l u .lll:l .lJ..l lJ .llll:l

'lr;

definition of the entropy also, disappears.

Accoramg to tne .tlonzmann relation, tne vatue or
w-hi,-,h

0 i !': ,..

'il ,o: t.n S:f

1r

Rt.$l.t.i,o:t.i,-,l'l.lhr int.Pr-

preted, therefore, Nernst's theorem states that to the

- .7 . .
...
.r
... J.. ,7, ..
L
responds only one dynamical state, namely, the dynamical
. br(5 'bnr:;
UJ
'-''Y'
structure or state of aoareaation of the sustem.
The only crrcumstances under which .Nernst's theorem
.. L

;],

v~~~~"

Tn;rrh+ "ho ;n

~~"!JY

~~

o.,.....J'Yr a-..<>

"J:''".:;~U~t:;

~vu.v

f.hr>C!<> .fn-.. ..,..,'h;ro'h

dynamical states of lowest energy.

+1.

,1.-

.c

.1.

1:1vv~v

....

...

+'ha-..o .OV';<:!f

Tn<>TY"<T

But even in this case,

...

1.

.1

1.

_,

~.c

deviations from the theorem are to be appreciable. AI. no1; 1;neore'(;lCauy

unougn n. IS
nnposs1me '(;0 conceive or sucn a
~ ........ s
s ... m it seems extremelv unlikelv t.h o:~.t. such
actually eXIst in nature. We may therefore assume that
;,_, O'.OTH>-r<>lh.r

'N.0-rT\<:lt-.'"' t-.'h

'\Ta

J.j.rl

We shall now develop some of the consequences of

,..T

~~

.LL

.n

, . IS

. o:;.u...L

Dl

. .

l:U

l'Yt:l

solid body which is heated (at constant pressure, for example) until Its temperature mcreases from the absolute
, t.n

'!'1.

T ,Pt.

,.,.,.,.+.<>.in V$l.hlP T

f!('T''i

hP it.!': t.h

1$ll """"'""ihr

(at constant pressure) when its temperature is T.

'1.
...
...
... ..3171
.1..
1..
.1
1

.c

Then,
:n

-"

absorb an amount of heat dQ = C(T)dT. The entropy of

une ooay au 1;ne 1;empera1;ure J. IS 1;nererore given tsee
eauation (192)) bv:
(

.'l

JO

C(T)

rl'T'

(10':1.\

.L

.
~

from equation (193): we

...

~,-..;,

"'~

'ur tne oraer ore' , wnere

'L~~V

1v

observe that if the thermal

~'-'~~

V.~~'V

'-"~U~~VL~OJ

~L<JLLL

L''-'LV'

1s tne numner or moleCules 1n tne system.

.o.u""'5"' a.J.

VAA'-'

YV VUJ.U

\J. v<))

u.J.

Vt:rgt: al.J

"{;Ile

lOWer

llTnlT..

vv e

must therefore have:

C(O) = 0.

(194)

Th1s result is in agreement with the experiments on the

,nn.r~ ~ ~

l-.

.l'

.1 ..:l

We shall limit ourselves here, for the sake of simplicity,

. li:lolJ~V.U
.
.
. t:J.Cn~elll.JS, anu per.Lu~~
" " ' V.U'V vU.
v~
the calculations for one gram atom of the element. Figure
~:.::; lS a graphical representatiOn o! the general way m w.tuch
t.hP

<>+~~

hoat.<.! rof <:!nl1..1,.. rl,

tlf'

found empirically.
"+ ~

1-

.j.

,.j.

orl ron tho +

>-rahn<>

"-"'

One can see from the figure that the

11

,\-

.j.

>.

1.

,.j.

.j.

1- rl-. ~~

temperatures, C(T) approaches a limiting value which is

very neany 1;ne same 10r au
(;;
elements and which lies verv c T
close to the value 3R. tlince
t.'h;"' 11Tn'i+'

... T.,1,., ;,..

~... ,,..t;_...,.nv

attained at room temperature,

.L. .

. 1

.l'

3R

the well-known law of Dulong

ana. ..t"et1t, wrucn can oe ""<:l.""'u.
as follows

T
Fig. 22.

All solid elements at room temperature have the same atomic

neat, wntcn 2.8 equa~ ~,o o.n. \Ofbl.b~ ~.,, ~, ..... 1
~*
cc .,b. ,.,hf is the same for all solids and is equal to 3R)
v

A theoretical formula for the specific heats of solid elements which is in very good agreement ~'Tt;n exp~....
'"
-1' . ;J 1- n ..l-.uo nn Hu> h<>.Ri>: of the auantum theory.
The Debye expression can be written in the torm:

~),

C(T) = 3RD

(195)

isti~ constant of the substance, which

has the dimensions of a temperature; It IS c . ~.>uc ~~ v~
-'-

;"' "'

<>h<>.rl' .._

,,

.!'.

n+;nn

A ...TIT'

re

~ s

jo

x dx
e"'- .L

J;

e--

.. .

f10I'i)

.
~

.1 ..
1'" 1
it follows from (195) that the atomic heat for high tem-

, .. ,

~~

rc

~-~'

1:-h:on:L 1> un::l:5

IJV

IJ.Uv

ULIJ'

..1 ~"-1 ~

0.;:::)

""J

,.,,1~~~-~~..-l ""D~+~+

For small values of ~'we may replace the upper lim1t ot

'

f<nr"

1..

~n~r

.1

'"'-

.....,,.,

.1

+l-.o

. ..&

second term in that expression because .that .term

. becomes
,
,

....

~~

of ~-

For

~ ~

~J

0, we therefore obtain:
nft'l

JU

x 3 dx

roo

> 1 ?.1:3

4'71"" J;a

(197)

.L

nr t'l 'tVA _..._.._~~~ t.hP.

following expression for the atomic heat in the limit of low
D.

.... 'L

.... .... ,

m~~~

-~'~

'
4

12'71"" R

f'llrTT'

........,.

'

..

YV t:: l:lt::t:: 11-UllJ. IJJ.U>:> vA

m3

tl'

..

l:LIJ

hn!Ot\

....
,...., ... "'u
...... '-'"'

1
..&V yy

J..\.

atomic heat is proportional to the cube of the temperature.

This consequence ot the lJebye ""'Uleory 1s m gooa agr
"Wit.h
1ent...
Using the Debye formula, we can calculate the entropy
.S:

.S:

.L

(193).
.c::

.'1.

.L

,\.~+~++~ .... ~

~~

On doing this, we find that:

{7' C(T) rl.T

...
JU

u~~1~n~~~

nr i:\

~1?

1'7' nfT\ dT
JU

~~

'\.'-'/

/100\

t..

,.!..

~1? J e nft) di;

JU

L
~ ....

~~

: .j.

The following integral formulae are used:

.:u-.

rw nrt) dl,;
J

1?.

r~
JO

.-.2

,~.... r~ :t?d:c _ ~ f"'

...
JO
JO

(100)

l;

find that2:
2

{101'::.\

e
~

...

-~

.,.....CTT.'

3R 4""
=

"'~

T.' ...

3R log T

... ,..

r1 fY" T C't ,.., -.. T......,

rT x 3 dx

log

e-~)

(I

+ 4R - 3R log e + . . . .

e,

where the last formula is valid for T

.~

A~

that
~A

(200)

in the

IS,

....u....

Petit holrl~
With the aid of Nernst's theorem, we shall now discuss
.j.].

-~

.j.

+"

another.

,,: ~

..&

~-

.1! .

11."

As an example, we shall consider the transforma. .

. .

=-

"J

"J

A~~

~u

low temperatures and white tin is stable at high tempera. .

.
.1. Ut:: l!.l"
l!u.n::ti.
l!t::U.J.A
a.l!un::, .L o , 1::; equa1 110
LJ or
.t~

')(l<")O"U""

The transformation of tin from one of these allotropic

.
.
=

melting of a solid.
J.ti i:H..OtiU.l Ut::U

-r

Thus, for example, a certain amount of

,Y

I_, .lit::

I_,.Lll. .UJ. ..1:"

.l.l U.lll

1_,UO:::

g.1 t::,Y

I!V

1!110:::

white form. This heat of transformation, Q, is equal to

ai5a ca10nes per gram-atom at tne t.ransnwn "temperature.
A lt.honuh
~

t.-in

1~

t.hP "'t.<'l.hlP

ht>lo"OO" t.hA +.. .,.....,.,1f.1.-.n

temperature, white tin can exist in a labile form down to the

.lVWt::CtJ

A-

.a.tJI.4A~~

.LV

C<;:;.lV.l<:;

J.,;:)

A-

LJ.J.lv

I_,V

.l.l.l<:;Q,;:>u...L<:;

the specific heats of both grey and white tin all the way from
-.:;ne 1owes-.:; ,;empera-r,ures ,;o -r,ne -r.ransn10n -r.empera-.:;ure.
i~

'T'hP. "'""

hP<'l.t.!'l nf t.hP. +

~-

l'l.rP. nnt. P.Cllll'l.l thP.

n+

,.;~

or, interchanging the order of integration in the double integral, and introductng 1/~ as a new vanable 1n the second 1ntegral, we obtam:
1
1
,.,

"' DW _:,
!;

}o

"'
12 }o

e"' -1

~ d~
2

+ 12 Jl

e"- 1

1;2 d!;

}o

{"id x 3 dx

}o
For

lara<>

valueR of"' we

nht... ;n

("'

JO

dl;
~

4-

....\.

Jn.,.

}!:.

,+otic exoression:

the followiniZ

D( ~)- -

e~

'"'

-1-

...

e"'-1

-\}

146

THE ENTROPY CONSTANT

heat of grey tin at a given temperature is less than that of

~r"ha.a

,+,~n

-tin o-t -tho oonr..a +

The transformation from white to grey tin is nonreversible

-'-

.L

_,

"

'.L'

.L

'

.L

,,.

the grey form is stable below the transition temperature, a

lJl~

l::ljJUH

LUI~~u~OU

C<:I.Il Ut.:CUI"

ll~UJ.ll

"J

lJHt:>

W .u.LUv

to the e:rey form). At the transition temperature, however, tne transtormat10n between the two forms lS reversime.
Tf ,r;;:, JT"'\ $1.nCI i;;;J,.fT. \ .,_,...,. t.h.,.
<>+. t.hA t.ransition
temperature of one gram-atom of grey and white tm,
. 1-.r + 1-ihlo .;.,,...t.hAr.,.
' . "" fRO\ +.n +ho
mal transformation from grey to white tin, we obtain:
Wnite

S2CTo) - St(To) =

dQ
7jl

(201)

7jl.

If we indicate the atomic heats of grey and white tin by

'-'1\-'- l

auu. '-'2\.L),

lt:>l::ljJO::'-'lJlVt:>ly,

WO::

U<Ul

.,.

""""' .Ul\.L 0)

c.u~

S2(To), with the aid of equation (193), as follows:

{To Cl(T)

St(To)

..

JU

WA t.hns

1.in

,"J...+

~-.

'1'. <

dT;

S2CTo)

{')()1 \

t.hP

(202)

...

JU

Pn11nt.irm

{To Ct(T) tl'T''

To C2(T) tl'T'

\.J u

C2(T) dT.

JU

(203)

t.hA
process in terms of the transition temperature To and the

,.,]-,;,..]-,

tho<>

"1-

...

~~~y"

"

~.L

...
"L
VU'-'

h<>at

.....

uo"V

'

t ..-ar..-"

nf

.O."V.L.O..L-'-0

ootinn

nf

" .

V.O.

V.O..L.Lo

In order to test the validity of equation (203), we shall

~.1..

U 'o'Y V

vU'V

.LU \J<:Oe.L '-'

....., .,. .......Y

, UCU

results of the numerical integrations are:

rTo C2(T) dT

12.30

To

)o

omce

:.to

cal.

:.:::~:.::;,

Cl(T) ,,...
'1'

~~

cal.
degrees

we oo;;am uom t._:..::u.:s;:

...

-'-""

-~~~

'1"1.

::.::\::1::.:: (.1:.:::-3U- 10.53) -

""-

mental value, Q .

517 cal.

535 calories, can be taken as strong

o~ppv>

.LU.

..

J.~t:aU~'- ~

Ul

l't::Lll

.L Ll'V

difference between the two values can be accounted for by

'-Ht:::
unen-.;at errors.
- ...
In section 14 we

32. The entropy constant of gases.

- 1

-,

... "'

equatiOn (86)) and found that:

8

'""'.1

-L ..... ,

-~~

,;,....., ;., .no llarl

~

Cv log T

. .eve-

.
+h

+ R log V + a.
.
a wmcn ap_...

~~~~-

.l'

- ~ .LLI.

+L

If we could apply Nernst's theorem directly to

.1

'~"''

' 1

- ..-..; 1

the

-~

from the condition that the entropy S must vanish at

n '-'

-u:'O uLUi:>l L.lUVV'VV'VLI

~v

VV'V oc;oc;;

" u

-.::rrro<:.O

term Cv log T on the right-hand side of (86) becomes

. , <:loilu wt::: u .......~ an innnh;e vatue ror -r;ne entJropy
constant.
The reason for this apparent failure of Nernst's theorem
"

.,

"

'

_...

' ....

of an ideal gas, that the specific heat Cv is a constant; we

. .
.
"

~~

oo~

..,~...,. n ....._

\ ''"'

uut::

.l

"11""

1-".1. ""' '-' .....

section) that this is incompatible with Nernst's theorem.

vne way OUli or -r;nlS olthculty could be sought m the fact
that no TP.l'l.ll'lnhstR.n~P. hP.ha~r&><:!
"'--. .,,_t.,.hr 111.-., o-r1o
ideal gas in the neighborhood of absolute zero: all gases

..

. -~

.
-"'
~
physically not permissible to apply (86) to a gas
=

LUU.l

U.l

'-"~=

Ill

the

v.

.L

But quite apart from this consideration it follows from

quantum mecharucs that, even for an ideal gas (defined as a
P'l'l.l'l

=hnsP. mniP.cmiP.R h~ <> nA<Tiia-ihl&> <:!l'7.A anr'l r'ln nn+.

'

forces on each other), the specific heat at very low tem.1-''-'

~u

~~

ao n WJ "'"'

~._,

..._. uu..:;, .L.L<:>.

"''

-u-ornooa. or
R.'-

'.1.

- u.

Tnus, even xor an R:rear gas as a.ennect

be R.nnl-iPrl onlv if t.hP. ...
t.nTP. il'l nnt.

(Rfi) ~an

too low.
n.

- --

....

.........

'

.1

..l

.... 1-

..l

1-

.1 .

.I.

_,_

' p

'

application of Nernst's theorem, it is possible to calculate

~II:'

.J

,.

{.I~ f))
t.alz-"'"' t.hP. ~
limit of hi!!h temneratures the
with the constant a, instead of being undetermined, ex.J

n~

-t.,~~;~~

~_,

-4-1- ~

,1

,]_

-1- . .1.

molecular constants of the gas.

.J .1.1-

. ,.
'

the entropy of one mole is given by:

3
~

.,.... .

--'

3,
l:l

II

( 21r M R) '2"we"2"
haA4

T'

L 1.

. .1.1-

. --'

,_

.'

(= 6.55 X 10-27 C. G. S . units); A is Avogadro's number

. , .... ~ J '.
w
o
---:u:> '-' '
"u"'

'statistical weight of the ground state of the atom.

.
.
.
~.._,

~u

The value of
w J.uJ.- uJ.u~n:JHIJ (:1,1
H:i uutJalneu 1rom 'tne quan"tum "tneory;
we shall a:ive the value of w for all thP .ov-qmnlP.!': ~nnf"-irl
..]
here. e is the base of the natural logarithms.
~

'

'V

~J

.._,

.Y.A o

In order to show that (204) can be put in the form (86), we

.
. Ao 'tlll~,
. we oul'ain
.
.UJ.UC"
\, 0'1:)
J.U IJU
VH ti'
LIJ
for the entropy constant of one mole of a monatomic !!'as
the expressiOn :
3

_ R l

a-

og

- R(

( 21r M R)2 we-z

1-.3.<14

.'') fl.'') -1-

3 loP" M

'
We can also write the entronv of nn
form corresponding to (87):
R

R 5 1orr T
v

-L- 1.-..-. ,_.'\

(?nO::'\

ic].,.al rnn""''

lno-,.., -1- lno- (21rM)"'AR'2"we'2"

H.n.

llr> <r<;> -"'

-in a

f?nl'.\

1Af'\

vv e canno"t g1ve a proot or tnese rormmae m thiS oooK; we

<>'hq.ll t.h
i!
limit
lves to
o~n
1 >>:: sh
. U:! the
applications of these formulae. As a first example, we shall
,1-..1

-~-~

....:~

.~

.1

......

.j..

~~

...

.,

solid monatomic substance.

r
.r
"" T. Keeoine:
perature
the temperature (and the pressure)
constant, we vaporize one mole of the substance by 1ncreas~ ..........

+h.a

un.h, ........ .,. uo~u ~l,.,.~,hr

n,~;~

.... +]...;.,

+ho hrvlu

absorbs from the environment an amount of heat, A, equal

'

.- .

.....

u-

'

the vaporization of the one mole of substance occurs

.1.

<> v

<:;.I.

IJH<:;;

.LU

~..,

v.L.L IJ.L V jJ .Y

U U.L .1..1..1.!;!,

VU'V

IJ.L

.~.~-

t.inn ;.,

SvAn<>r -

Ssolid

= -

Using the approximate expression (200) for the entropy of

the solid and the tormula (~Uti) tor the entropy ot tne vapor,
W'P.

n ht.l'l.in
3

,.5
.cr,

2 wg

:J.

IOg p

-j-

lOg

:5

(27rM)~R~we~
., IL

h8A4

- 4R

wg

:J.

3R loge

T'

or, passing trom logantnms to numbers,

p=

(21rM)~ R"we

RT

-~---~e

e2h3A4

(207)

..1.

.
'

obtained from Clapeyron's equation .

\_.:JVI)

c:>.L.LO'VO

.lrV.lU

VUr

Ui':I.VU.l~

. The

., '

factor 1/viT in
IJ

'-l.Lt;:;

Uv-

Pendence of the heat of vaoorization on the temoerature.

We see that the factor of proportiOnality, which remained
nn,.:lo+~~

-l

-in (Q~'\

1nJ .+ -lv

lu>O! nnnr 1.

..:I.

.J

in (207) by the use of Nernst's theorem and the Sackur.LviJ.LVUv .LV.L.L.L.LUJ. ... J.V.L

".L.Lv vHIJJ.V.f.J.Y

V.I.

<>-

oc:><>

~'"'

~~~~

~~

~~~T.-.~

~T~

-s'mce in many case--s-w~l;lJ

witn "tne vaporization
nf "' lirmin 11.nn not of a solid (207) cannot be used in !!eneral.
As an example of the vaporizat10n of a liquid, we shall
-

:--+~-~

....... _ -

1-..-----

-.C -~- ~-1- -.C ~

this element has a monatomic vapor.

..

--r

'.J

the vanor nressure of saturated mercurv vanor at 630K is

equal to one atmosphere.
~-~ ~-l~nln+n +l-.n n~+

-TIT- nl-..nll

and
-. 630K
.

at T
.

p
.

-..-

Method 1.

.=

"'f ""~~ ~-1~ "'f ~

1 atmosphere by two different

The Sackur-Tetrode formula (206) applied to

-vv

-ourv=~

-.::n-

n:;-ury '""" ..vv. v) 1;;.1. v "'"'

"'
JIA' ~# z.

-~

.........

n+-~+

TITn

{jJ

absolute zero.

~n

n~+'J...

-~-

~-ln

n.C nnl:rl

~n

n-+

according to Nernst's theorem,

..Its .entropy,
.,. ,.
. . -=
oJ }

s:

the pressure equal to one atmosphere, until its temperature

,.,
.... .... -=..,.
......-z.-. ........ ..................... 5
.v,
meltjng
this process the entropy of the mercury increases; its value
forT = 234.2K can be calculated with the aid of (193):
\)~~

~~

SsoUd

..L

(243.2) =

"'C\l'JdT
T
'

where C(T) is the atomic heat at constant pressure of

'o

"J

v~v~~vv~

cally by using the experimentally determined values of

TJ(T). On doing this, we obtain:
,:,solid~:<:'!:;:>.:.:)

....

~<> U

"-'

bV.\J X
L '-' UJ.

V J.

'V

lU'.

J'

<:1. 1J

l.l. v

_ ""

pressure. During this process, the body absorbs reversiblv

-an
~eat. equal to the heat ot tuswn for one mole of
mercurv (2R30 )( 107 P.ril"R/Tnnl~)
'rhP. ~hl=l.no-P. 1n
.
resu!t1ng from this 18 therefore obtained by dividing the
.

'J

=.I:'

'

~<>

UUv

'"'

J..l..l.

total entrop

of the mole of mer

Sliquid(243.2)

= 59.9 X 107

+ 9.9

X 10 7

= 69.8 X

n ra1se
oint to the boilin

from the

s empera ure

is the atomic heat at constant pressure.

integral numerically.

Its value is 26.2

Suquict(630) = 69.8 X 10 7

'
finally obtain for the entro
a

26.2 X 107

x
=

101.

10 7

Using
Adding

96.0 X 101.

we
of the mole of

an experimental proof of the expression for the entropy of a

'

'

10n1zabon of a gas: the thermionic effect.

am.ple, a reaction in which only monatomic gases take part.

. .

..

We

shall

therefore consider the followin

heated to a very high temperature, some of its atoms

If, for example, we denote by

'

the reaction :
Na

any

E)

Na+

g~ven

+e.

(208)

emperature, t

In sodium vapor at very high t~mperatures, we actually

Ions,

gas; we may therefore apply the general results, in partie-

'

,..,

"L,,..,.,......"[")"'\"[")"(7

'<"'\ ....T-<~ o

........

'T~

"<:> ''-'I.J
ul.lt:; -very --snraiT Ulllt:rence
'
betv.'een the masses of sodium atoms and sodium ions. so
tnali we may atso ptace JV.L equa1 "LO ljfie atomic wmght of the
"'"rl inm ions.
The atrnni<> WP.t!Z"ht. of t.hn r->1<>. -"'"' { t"h a+ .;.,
the mass of the electrons divided by r\r of the mass of
_,
1
.c
. 11.
-~ ,\
:n Jl,f'
1.
Trr
T .4-

-w

v~

4.91 X 10-

( =
I.Jl.lt::

.LU

""

""

ergs/mole) the energy needed to ionize all

12

V.L

U.U.v

"'

TF

'"RULUH

nr

UT

TF

vve

<tJ?Ol",

nave,

YH

'
~?

1\'lakinl?" all the ncce~:">sary substitutions in eauation (139)

we nnally obtam, as t!1e conc1Itl0n tor thermal equilibnum
1n t.hP. t.'

ionization of t'(orlh1m -..m.rv-....

tfl,l

+.h ... fnP

\0"

equation:
nA

rNa+
_l_l;i-hiP

.. T 2' c H.T .

-~
~

This formula can be put into a more convenient form as

T6ITows: Let x De t-he degree ot IOnizatiOn, tT1at 1s, the
frn~t.ion of atoms that are ionized
---

LNuj

..

--

''T
L

''T .

'
-,

sodium (atoms

'

'

i<_ms).

[Na+]

..

+
-

- -- --

LNa.+J

'

.
~~

u~~'-'

We have, then,
[Na] = n(l -

u:r;

l_,llt;;L <J .L" \ } U V .L\Jlli'L.Y

lOll,

[Na+]
..

x).
Lt. .lU.l'

U.LLIJ C.L'Uv u.L U.LL }Jl.

we have:
~~

[<-!

= n:r.

[Nu +]

and we finally obtain:

J'

..

"
( 21r ]'If.. R)!!.

1-

ne

-..;c 6

ee

or

..~-

11'' A.

J.

::UJ X 1U

..
'1

.
20 nno

lU

----

'

(ZOQJ

io nizaLion can oe eacutaljea rrom tnis rormuta.

1,.. A

'

-,_,

~~v

~~~.LY'-'U.

'-'.]

......

.._,

has found several important applications in the ~~sics of

uu

..,..

As a further application of the ~ .. ~knr-'1'1

-lA f.
11la.
we snail ot>tam the express10n for the density of an electron
O"Q.!'! "arh>nh

'"'-i-n

~-4-1.

ON11;);l-,

\.

.1

.-4-

.J!.

'T'rn

a metal is heated to a sufficiently high temperature_... it gives

,_,...,. u. ""'...._"~u.vuo .,.,~
u.1 c:aec ... rons.
.1r we nea-.:; a otock or
metal contajnino- a caT~+
the -1
l!'!
Yinu ~-1-.ho
metal will till the cavity until a state of equilibrium is
l"<><>t>horl

-nr'ho-.-.

no

.1.

'11

1.

.1.

..1.

'

unit time by the metal as are emitted.

...1..1

,
~

v~ ~

-~ ~~

We propose to
V.L

VU'V

~~v

; IJJ.

VUi::>

inside the cavitv as a_fitnflt,ion of t.hP. +

+11r<>
Let N be the number of moles of electrons inside the
na

~~

,1

TT

IT'll.

-'-

'"

obtained, from
(204)
. _.,_,._
. . by multiplying that expression by N
_]_

.._

'-'J

'

r f.LY

.LC

VU<:>

occupied by one mole of the electron gas. Making_ use of

. 10r line energy or tne elecr,rons:
U- N(J;RT

wnere w

IS

"

~~-~-

j-,h.,.

+ W),

the energy needed to extract one mole of electrons

.1.

For the free energy of the electron gas, we now obtain the

Fet = N(JRT + W) -

v
NRT !log T +log -u
(<)_

7111'

3
,;>\'!!' n

5
'!!'

) '

LLle a-.:;ormc weignt Of the

electrons, and w for the electrQllS_ - .2
.1 ne tree energy Jf' of our complete system is the sum of
.;.1.

~~~~

yY<;;

.u.a.v.;; puu .<r.L.,

1,880

~~

. _ ...... -'-" -'-" '-' ... .._ "'-J.... ... '-' -..; .1., "-' .L n..J.'I .L
Ti'

Ji'u -1. N

s R'T'

...1.

R'T'

3.

ln..,. '1'

.LUtl

1.

1 -- TJ'

1\T

'-

+ log 2(2rM.R)~ e . (210)

. .n
. . -- "
2

'T''ho ,.../'\'1'\rl;+;n.,...

.j:',._ ~,.,,:1:

,.j.

giVen temperature and volume.

UH.& '-'

.tJ'

o=

u
dN

v~

RT

IJUU;:) VIJ'

.LV 7 VV'V

+W

Assuming that

- RT 1~ log T

r;t

+ log V

lS

- log N
3

log.....,,~,.,.

FM

..... e .... ,
h3A4

15

+ RT.

"'

Passing from logarithms to numbers, we obtain the equation:

3

2(2rM.R)1' rn-!

v
wrucn
CI"<H'

n~

g~ves,

--;;;;;

,., nn

~-Q

-*

IV

'

',-

.,

as requued, the concentratiOn of the electron

1rr;+~__l..,

nnu:-1- ... ,

. .
.
'.
"".1 _, .... "
'
-r
temperature of 4,000 K and a pressure of 1 em. of mercury.
"
.
_~.LaKe mJJu
mt not on1y tne pressure aue to the sodium atoms,
but also the contribution of the ions and the el ... ts.)
2. Find the relation between the Debye temperature 9 and
~

LL

. ....

equal to 3R/2.
3

- '- . ,_

ll.

ft

..

(Apply graphical or numerical methods.)

The experimental basis for this assumption is that the electrons inside a.

'''I

,_.,

,-~

"

_.._

.._,

'-" . '

-"

"

eompletely accounted for by the motion of the atoms.

; .<:

.1! .. '

F.or a r1gorous
.

.L!Illt X

A
A

1.-

onl o~n

'

Conditions of equilibrium, 56, 57,

........

Absolute temperature, 8
Absolute thermodvnamic temperau~

~,

VVJ

"%~

Constant:

compared with gas thermometer

~

o-'-'~

-~

+"

'
for an ideal
gas, 26

J:.,

33
+~on

'

A~"-it."n'"u

"' ~'J.

Constant temperature transformations 78 79

vun ~Ullll"LY, ?I State, 1:);:! 1 ti4, IU, ~, l
Corre~~ondmg states, equation of,

"~

Arbitrary additive constants:

of energy, 13, 14
~J:I_J,

ooo

Constant pressure transformations,

for a Van der Waals gas, 75

A.-li.-.'h<>tin

,.,. <>.-1.-liHuo

aaa1t1ve constants
Boltzmann's 57

Acidity of a solution, 126, 127

Arl"ohoHn

R~

80.

vonserva "LIOn ot energy, prmc1p1e

of, 11

Atmospheric pressure, 27

~~itica~ isothermal, 64, 69

Avogadro, 8

Critical pressure, 64
Critical volume 64
'-'.l:_"'""' v
Carnot, see Carnot cycle

'""

,,. !:.7
B

Boiling ~oint of a solution,

13

:i_l

_:_

nn

lao; 135,

uv ......... ., .. , "" , ...\}

n.

constant, 57
.1

-,-_

"J

Dalton's law of partial pressures, 10

'
.

'-'"'U.)'

">

J.'tO

'.

formula for specific heats, 143, 144

"

~.;.

Degree of freedom or variability of a

. system, 91

Carnot cyelc, 31
cflieicnev. -34
propcr"ttes, qo
Chemicnl content of a phase, 86, 87,

!!."'"' "'

.LJOOU<I'~.Y Vl . . . .

Description of a phase, 86
lL
,..., """
.
.
-"
law, 20
Dilute solutions 113
Dissociation of a solute in solution,
122, 123, 125,
126, .127
.
.

Chemical equilibrilt:
in """-"'"0""' Rvst.Plll"' 98 109
in solutions, 123
Chemic1tll v homoe:eneous fluid 1
vuemienuy no
owuu, ...
5;hemically homogeneous systems, 1

~-

v
0

'6 p

'V

&"!!

p,_omt~. a~~d V~er pressure of

effect of on osmotic pressure, 123

Distribution of a solute:
"""""'"" o. ."!.""'"'"u" auu "" "'!"""
phase, 129, 130
.
,...
.,
'
128

Clausius's postulate, 30
Comnon<>nt.R nf n. sv"tcm 86 87 88
\ Omprcsstblltty:
adiahatie, 26, 27, 32, 33

..

of a 1 iquid, 64
~

.....

"11::0

.-

- '

~-~~

J..'

Dynamical state of a system, I, 3

First law of thermodynamics, 11

in ditierential"fo~, 20
statement of. 10

E
Ri'F, ,,.__t

.~

on chemical equilibria, l11, 112

on freezing point of water, 68
.
equilib~'ia, 110, l11

~ Lt;;"' :-' . . w ~f I

{'!

Gas constant, 8
Gaseous reactions, 98, 109

'

_2&

~J~

"'

l'!a,._T

.tl

Clapeyron's, 63, 66, 68, 84

.I'

"'"'

a., ow ..emperat.ures,
. 144

""~

!;"'"'>
n

constants, 99, 106, 109, 130

a~~

u'd

<>

&>A

0'>

or liquid and vapor, 68, 64, 92, 93

of one component in two phases,
f

'

'

equation, 95

Homogen~ous
.;

.l:!.;quivalence of the gas thermometer

temperature and the absolute
.
""'"Ulc 1
42, 43

systems, 1, 2

<;ctl

14<S,

work and, analogy between, 14, 15

capacity, 20
engines, ;j5, 44
TT_, s~urces, 29

of solid and vapor, 92, 93

,.+.. +

!'l:.<:,

"'

V<7

' - - - . ' uv, uv

_nf_linn;..-1

'
' 21
molecular,
of fnRion 109. 110
of reaction, 109, 110
of transformation of solid_!!_haAeA
~-~ .
.
66
o f vaporization,
c~a~iflP. 21

...~

of state, 2
of an ideal gas, 8

!:!

Heat, 15, 17

of a solid, 145
of a Van der Waals e:as 75
statistical interpretation, 57, 141
Entropy constant, 52_, 139, 14L 148

..l.

"

Gram-molecule, 9

Equilibrium:

~lbos, ~I

~ ~~

u,y

Gas thermometer, 8

Entropy, 46, 48, 139, 140, 144

.Ad.dithdt.v' ~
as a pertect _<lilferential, 60
definition, 50

en1;ropy, IH, ~<HS

free energy, 82
.-~ ~~

of an ideal gas, 23
of a Vander Waals e:as, 74

_,.

'._..~_""

adiabatic transformation, 25.

16

J_

1Q'Z_

. reezmg pom" 01 a soiutLOn, 130, 137

definition:
for dynamical systems, 12

""'

-'

..]

na rHo 1

J<

o /l5

of a solution, 117

Electrolyte in solution, 137

Endothermal r""'-"Hnn,. 109
..l!<nergy:
additive constant of, 13, 14

'~

::;,-

-~

..

and equilibrium conditions, 79, 80

."'!~~.

Inflection, point of, 64, 69

Tnni7.a+'

al

1.;1 __u;o::,_

7
,tsobanc transtormations,
Isochore of Van't Hoff. 81
..v uu" e ec ~nc ceu, "'"

.....

...

'
entropy constant, 148, 149
vanor
.. ~o 14.Q

Isoentropic transformation', 7f)

Isothermal:

..

critical,

64"69'u
.'...
....

Isothermals of a saturated vapor, 63

57
Nernst'stheorem 139
<>pp~~cu

.. ~ ... ~

~~p~

.... ~ ....

' ""'

1? 1

1 ?.?.

122
idenl gas, 122
of an electrolyte, 123

'

Law:
Avogadro's, 8

='nu'a !1'tons,
"' ",'
r:l,
o~

.T

10

Partial entropy, 107

occa~'o

o . ; ... 1 ... ,.,..

' .Petit, 143

Vulong and

r"l,

'

. 1.

~~

1 ""

1 1 1

Lowering of vapor pressure of a

solution 134

pressure of, 8, 9
Perpetuum mobile of the second
Phase, 86
chemica~!
~~,.,

content 86-88

...

spncc, 140
T>l.

uc ~>JOn.
.~.

for gaseous cquilibri!t, 99

for solutions, 12f)
>~ystnm

''

...

.,

..

Point:
critical
64
.
. 69

constant, 109

Maxim.um. work thu.t n

nerform 78

on"'"""" 1 n7

rartml pressure, 1:1

Dalton's law of, 10

as applied to chemical equilibl'ia,

111, 112

'

.,

of mass action:
1u1 gaseou" Cll,!-llliorium,
for solutions, 125
T

'

One-phase systems, 91
Osmotic pressure, 118, 121

K1netw proof of the law of rnnss

action 99

J.'O

<'hemicnl

Kinetic interpretation of osmotic

11 ,...

~'t,

Nonreversible engmes and cycles,

36 37

Kelvin's postulate, 30
Kinetic eQuilibriwn of
'

:J

~~

"u .,.

applted to sol ids, 142

Joule effect 94

' " 11111"l'"llJII 0 O"t,

_ triple, 93
U., .1 . 1 . " ,_,

enn

:~s

<

1 '1

u:
<L

.L

state, 57, 141

related to the entropy, 57, 141

Q
'

sen1ipermeable for Aolut iom-:, 11){

Mixture of gaR<-'R. 10

n.
!Lilli

in

speeifie hents, 143

r~>lt.inn t.o t:l-.;. o~>nt.rnnv <>nn-

1r>n.

T''

=~

--";

Debye, 143

Ratio _of specific heats, 24, 25

"'"-"' thpr~n~~+~r S!.

endothermal and exothermal, 109

gaseous, 98
+~~

vvr

,~,

~~'::

'

'

~ ~an-hln6

AA

Reversible cycles, l:S:I:

Reversible
. electric cell 94
,

~o;:;vo;:;

v~,

nerma1 eng1nes, ....

!~erma! ~ns~la t_?rs, !6
J.

-n

Thermionic effect, 151, 155

Thermodynamical potentials, 77

~:~.,?,tion box of Van't Hoff, 101

'n

"'

'

at constant volume, 80 . .

Qv 1 ..,v

140
Thermodvnamical state of a system,

s
Sackur-Tetrode formula, 148
applied to the calculation of the
applied to the calculation of vapor
oressure of a monatomic solid.
~

. , ....

~~~r~~dy~~~!cal s~.stems,_ 1

1'>0

Transformations, 4
adiabatic, 25

Saha, N. M., 154

constant ten1perature, 78, 79

isothermal~ of; 63
~eco~;,t law of thermodvnamics 29

isobaric, isochore, isothermal, 7

reversible, 4

_,.

for solutions, 118

Solutions:

a :~lif.u~t 'fow temperatures,

c.

-"

'

., .......-gy, ......

'j,) y'

65,, 84 ...

~:>tate;

dynamical, 1, 3, 57, 141

:~

thermodynamical, 1, 3
Statistical interpretation

'
u

Vander Waals:
equa t~wn o f.,.
correspon d"1ng s t ates,
73.

vu v """'""'
-.r. .. = .a ..
~-

isothermals, 70

~~

isochore, 81
reaction box, 101
v a pur pressure:
formula, 67, 149

for energy, 12
for entropy, 50

theory of dilute, 113, 114, 115

vanor nressure of 130 132 135
Specific heat, 21
Debye formula for, 143, 144

O!J"'-'U~"

tin, 145
'I'rinle noint of water 93

membranes:

1111

of

.L 01, i>U

S~mipermeable

-'

.<!

_,

.+

nn

,.,,~

10"

Variables of state, 4
of

en-

Statistic;i;,;eight of a state, 148

Sublimation 94
. . uv v1ng part;s, .,
"--'.Y"'~ems

Work, 5

....

. +'

.1

.r "

performed by an 1d eal gas,

\:!

'T'

-=-

Temperature:
;

-ln+.<> +1-,.,rmoil~o~;.-. !t!'

crnlCal, o"t

<11

Zero. n.hRolut"'

, en"'u!-'.Y,

s~a~e

ul,

~"'

'v, '

VI'

-A ._ A lA ~-a -.AA 'A

I

...
I

[I

1. .

v '

-= ~

...

'

il

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Illustrations. xi + 712pp. 61/a x 91/4.

Paperbound

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