MAXWELLRELATIONS

7.I

THE MAXWELL RELATIONS

In Section 3.6 we observedthat quantities such as the isothermal

compressibility, the coefficientof thermal expansion,and the molar heat
capacities describe properties of physical interest. Each of these is
essentiallya derivativeQx/0Y)r.r..,. in which the variablesare either
extensiveor intensive thermodynaini'cparameters.with a wide range of
extensive and intensive parametersfrom which to choose, in general
systems,the numberof suchpossiblederivativesis immense.But thire are

azu

azu

ASAV

AVAS

| AT\
- tI a P \
a s) , . * , . * , , . .\ .a: v ) s . N , . & ,

(7.1)

( 7.2)

This relation is the prototype of a whole class of similar equalities known

as the Maxwell relations. These relations arise from the equality of the
mixed partial derivatives of the fundamental relation expressed in any of
the various possible alternative representations.
181

182

Maxwell Relations

Given a particular thermodynamicpotential, expressedin terms of its

(l + 1) natural variables,there are t(t + I)/2 separatepairs of mixed
second derivatives.Thus each potential yields t(t + l)/2 Maxwell relations.
For a single-componentsimple systemthe internal energyis a function
of three variables(t : 2), and the three [: (2 . 3)/2] -arUTaS
purs of mixed
second derivatives are A2U/ASAV : AzU/AV AS,
AN :
A2U/ AN AS, and 02(J/ AVAN : A2U/ AN 0V. Thecompleteserof Maxwell
relations for a single-componentsimple systemis given in the following
listing, in which the first column states the potential from which the

S,V

dU: TdS - PdV + p"dN

,S,N
V,N

UITI: F
dF:

-SdT - PdV + p,dN

T,V
T,N
V,N

U [ P l =H

s,P

dH: TdS + VdP + pdN

s,N
P,N

s,v

u[t']
dUlpl:

TdS - PdV - Ndp

s,p
v,lt

I ar \
- ||r aP\
,s/,,'
\ M)',*:

(!t\

(4\

\ dNls.r,

\ ds/r,r,o

_/ii\

(!L\

\0Nls.v

\0vls.x

('*),,.:

(!t\
\0Tlv.p

- \/ a s \
a *) , . , : (!"*),.

-(#)..:
( '!or),.
(#)"":
(!"^),,.
( # ) " "( ^:e ) " ,
(K),,:
(#)"N

(7.3)
(7.4)
(7.5)
(7.6)
(7.7)
(7.8)

(7s)
(7.10)
(711)

(f),r: -(#), , (712)

-(#),,
(#),.:
(#),.:
(#),,

e 13)
(..t4)

A Thermodynamic Mnemonic Diagram

183

U l T , P l =Q

T,P

- \/ a s \
n), *

dG: -SdT + VdP+ p.dN

T,N

-(r"a),,":( # ) , . ( i r 6 )

ulr, pl
dUlT,pl:

-SdT - PdV

P,N

tav\
\a*),,:

T,V

/ as\
\an),,

T,1t'

(H),,

V,IL

(#).,

,S,P

I ar \
| av\
(1.2r)
\a./".,: \as/"."

(#),.

(ir't)
(7.18)

-Ndt,

u l P ,p l
dUlP,tll:

TdS + VdP + Ndp" S,p

P,p

( # ) , , :- ( # ) " , ( 7 z z )
(fr),,: -(#)"- (723)

7.2 A THERMODYNAMIC MNEMONIC DIAGRAM

A number of the most useful Maxwell relationscan be remembered
convenientlyin terms of a simple mnemonicdiagram.I This diagram,
given in Fig. 7.L, consistsof a squarewith arrowspointing upward along
the two diagonals.The sidesare labeledwith the four common thermodynamic potentials, F, G, H, and U, in alphabeticalorder clockwisearound
the diagram, the Helmholtz potential F at the top. The two cornersat the
left are labeled with the extensiveparametersV and S, and the two
corners at the right are labeled with the intensive parametersT and P.
("Valid Factsand TheoreticalUnderstandingGenerateSolutionsto Hard
of the labels.)
Problems"suggests
the sequence
Each of the four thermodynamicpotentials appearingon the squareis
flanked by its natural independentvariables.Thus {/ is a natural function
of V and S; F is a natural function of V and,T; and G is a natural
function of 7 and P. Each of the potentials also dependson the mole
numbers,which are not indicated explicitly on the diagram.
1This diagram was presented by Professor Max Born in 1929 in a lecture heard by Professor Tisza.
It appeared in the literature in a paper by F. O. Koenig, J. Chem. Phys. 3, 29 (1935), and 56, 4556
(1972). See also L. T. Klauder, Am. Journ. Phys 36,556 (1968), and a number of other variants
presented by a succession of authors in this journal.

t84

Maxwell Relations

FIGURE 7 T

The thermodynamicsquare.

In the differential expressionfor eachof the potentials,in terms of the

differentials of its natural (flanking) variables, the associatedalgebraic
sign is indicated by the diagonal arrow. An arrow pointing away from a
natural variable implies a positive coefficient,whereasan arrow pointing
toward a natural variable implies a negative coefficient. This scheme
becomesevident by inspectionof the diagramand of eachof the following
equations:
dU: TdS- PdV +lp,odNo

(7.24)

dF:

-SdT- PdV+EpodNo

(7.2s)

dG: -SdT+VdP+LpodNo

(7.26)

d H : T d S+ V d P+ E p o d N o

(7.27)

Finally the Maxwell relations can be read from the diagram. We then
deal only with the cornersof the diagram.The labeling of the four corners
of the squarecan easilybe seento be suggestiveof the relationship

I av\ | aT\
(iSl, : t#J"
V r----t
t

iz i

s L___rP

(constant
N"N""')

(7.2s)

r----rT
l

i \i

sL___rP

By mentally rotating the squareon its side, we find, by exactly the same
construction

/ a s \ - \t7a' Y
t , ,\
\aP)r:
s;---,'
i---jv
i z i
i \ i
PL___rT

P r _ _ _ _ tT

(constant N1, N2,. . .)

(7.2e)

Problems

r85

The minus sign in this equationis to be inferred from the unsymmetrical

placementof the arrows in this case.The two remaining rotations of the
squaregive the two additional Maxwell relations

(#)"(#).
(#),-(K).

(7.30)

( c o n s t a nN
t r,lfr,...)

and

( c o n s t a nN
t r, Nr,...)

( 7.31)

These are the four most useful Maxwell relations in the conventional
applications of thermodynamics.
The mnemonic diagramcan be adaptedto pairs of variablesother than
S and V. lf we are interestedin Legendretransformationsdealingwith ,S
and N, the diagram takes the form shown in Fig. 7.2a. The arrow
conneciing N, and F7 has been reversedin relation to that which previously conneciedv and P to ake into accountthe fact that p,, is analogous
to - P. Equations7.4, 7.7, 7.73, and 7.19 canbe read Oiie6tlyfrom"this
diagram. other diagrams can be constructed in a similar iashion, as
indicatedin the generalcasein Fig.7.2b.
Nj

F = UITI

xr

ulP2'J
D

u[Pr, P2]

U l T , t tj l

Ulull
(a)

FIGURE

Itj

x2

UIP]

Pr

(b)

72

PROBLEMS
1.2-1. ln the immediate vicinity of the state ft, uo the volume of a particular
system of 1 mole is observed to vary according to the relationship
u: uo+ a(T - fo) + b(p - po)
calculate the transfer of heat dQ to the system if the molar volume is changed by
a small increment du : u - uo at constant temperature %.

Answer:

/ ,.s \
:
do: r(#),0,
4#),dv: f on

186

Maxwell Relations

7.2-2. For a particular system of 1 mole, in the vicinity of a particular state, a

change of pressure dP at corstant T is observed to be accompanied by a heat flux
dQ : A dP. what is the value of the coefficient of thermal 'expansion of this
system, in the same state?
7.2-3. Show that the relation
d : j

implies thal c, is independentof the pressure

| 0c"\
l-:-l :0
\ O PJ ,

7-3

A PROCEDURE FOR THE REDUCTION OF

DERIVATIVES IN SINGLE.COMPONENT
SYSTEMS

dT:

(#).*0,

(7.32)

and consequently we are interested in an evaluation of the derivative

(aT/ aP) ,.r. A number of similar problems will be consideredin Section

AII first deriuatiues(inuoluing both extensiueand intensiueparamercrs)

can be written in terms of secondderiuatiuesof the Gibbspotential, of whicit
we haue now seen that,cp, a, and Kr constitutea complite independentset
(at constant mole numbersl.
The procedure to be followed in this "reduction of derivatives" is
straightforward in principle; the entropy s need only be replaced by

A Procedurefor the Reduction of Deriuatiues in Single-Component Systems

187

-AG/AT and V must be replacedby 0G/0P, thereby expressingthe

original derivative in terms of secondderivativesof G with respectto r
and P. In practice this procedurecan becomesomewhatinvolved.
It is essentialthat the student of thermodynamicsbecomethoroughly
proficient in the "reduction of derivatives."To that purposewe presenta
procedure,basedupon the "mnemonic square" and organizedin a stepby
step recipe that accomplishesthe reduction of any given derivative.
Students are urged to do enough exercisesof this type so that the
procedurebecomesautomatic.
consider a partial derivative involving constant mole numbers. It is
desiredto expressthis derivativein termsof cp, c, and rcr.we first recall
the following identities which are to be employed in the mathematical
manipulations(seeAppendixA).

tax\
\av),:

'l(#).

I a x \ ( a x \l ( a r \
\av),:\awlzl\aw)z
lax\
\av),:

-ffi).1(K),

(7.33)

(7.34)

(7.3s)

The following stepsare then to be taken in order:

1. If the derivativecontainsany potentials,bring them one by one to the
numerator and eliminate by the thermodynamicsquare(equations7.24 to
7.2t).
Example
Reducethederivative
(0P/0U)o.*.

(#)".:tffi),"]-'

:[.(#)".-,(#),"]-'

(bv7.33)
(by7.2a)

: t-.(
.,(#)..1(#).
#),.l(#)"
"
"]-'

(by7.3s)

_ [ _ r - s ( a T / a p ) s , N +v * r - s ( a r / a p ) r . * + v l - l
-s(a r/a s)P .N
- s( ar /av) P.N
t
l
(by 7.26)

188

Maxwell Relatiow

The remaining expressiondoes not contain any potentials but may

involve a number of derivatives.Choosetheseone by one and treat eacir
according to the following procedure.
2. If the derivative contains the chemical potential, bring it to the
numerator and eliminate by meansof the Gibbs-Duhem relation, dp :
-sdT * udP.
Example
Reduce
(0p./0V)r.*.

-"(
(#),,.:
#),.*,(#),
.

Example
Considerthederivative
(07/0P)r," appearing
in theexample
of stepl:

(#)"":-(#)
..1(#),.

: (#),
.f+,,

(by7.3s)
(by7.2e)

Example
consider the derivative Qs/av) p,N. The Maxwell relation would give
(AS/AV),,N: (AP/ID*," (equation7.28),which would not eliminatethe
entropy. we thereforedo not invoke the Maxwell relation but write

f !q) p.w_ (as/ar)p.N

-_ (N/r)c,
(av/aDp.N evTal r^
\ ovI

(by7 sa)

The derivative now contains neither any potential nor the entropy. It
consequentlycontains only V, p, T (and N).
4. Bring the volumeto the numerator.The remainingderivativewill be
expressiblein terms of a and rc..
Example
Given @T/AP)v,N

-(#)..l(#),*:T
(#)..:

( by7.3s)

r89
- 5. The o{elnallv given derivativehas now beenexpressedin terms of the
four quantities c,, cpt dt and rr. The specificheat at constantvolume is
diminated by the equation
cr:

cp -

(7.36)

T u a z / t e,

This useful relation, which should be committed to memory,was alluded

to in equation 3.75.The readershould be able to derive it as an exercise
(seeProblem 7.3-2).

PROBLEMS
73-1. Thermodynamicists
sometimes
referto the "first ?d,s equation,'and the
"secondTd^Sequation";
TdS : Nc,dT + (fa7rcr) aV

(/f constant)

TdS:NcrdT-TVq.dP

(N constant)

Derive theseequations.
7.3-2. show that the secondequationin the precedingproblem leads directly to
the relation

,(#)u:",- ,,"(#)
"

and so validatesequation7.36.

7.3-3. calcularc (aH/av)2iryinterms of the standardquantitiescp, d, K7, T,

and P.
Answer:

(#),.: (ru- t)/r,

7.3-4. Reducethe derivative(0u/0s)r.
7.3-5. Reducethe derivative(0s/0fl,.
7.3-6. Reducethe derivative(0s/ 0flr.
7.3-7. Reducethe derivative(0s/0u)6.

190

Maxwell Relatiorc

7.4 SOME SIMPLE APPLICATIONS

In this section we indicate severalrepresentativeapplications of the
manipulationsdescribedin Sectioni.3.In eachcaseto 6e consideredwe

cp, l, and rc, are assumedknown and if the changesin parametersare

small.
Adiabatic Compression
consider a single-component
systemof somedefinitequantity of matter
(characterizedbythe mole number N) enclosedwithin bn adiibatic wall.

we consider in particular the changein temperature.First, we assume

4he fundamental equationto be known. By diffeientiation,we can find the

A r : r ( s , 4 , N ) - Z ( SP
, ,,N)

(7.37)

If the fundamental equation is not known, but c", a, and K.r are given,
and if the pressure change is small, we have

dT:

(#),*0,

(7.38)

By the method of Section 7.3, we then obtain

dT:

TUA
cP

dP

(7.3e)

Some Simple Applications

191

The change in chemical potential can be found similarly. Thus, for a

small pressure change

d p :( # ) . o '
"

:(,-#)*

(7.40)

(7.4r)

I sothermal Compression
we now consider a systemmaintainedat constant temperatureand mole
number and quasi-staticallycompressedfrom an initial pressurep, to a
final pressurePr. we may be interestedin the prediction of the changesin
the values of U, S, V, and,,r. By appropriate elimination of variables
among the fundamental equation and the equations of state, any such
parametercan be expressedin terms of T, p, and N, and the changein
that parametercan then be computeddirectly.
For small changesin pressurewe flnd

,':(#),.0,
:

(7.42)

-aVdP

(7.43)

$Y).*0,

(7.44)

also

dU:

: (-TaV + pVK) dp

(t.+s)

and similar equationsexist for the other parameters.

one may inquire about the total quantity of heat that must be extracted
from the system by the heat reservoir in order to keep the system at
constant temperatureduring the isothermal compression.First, assume
that the fundamentalequationis known. Then
LQ : rAS : TS(r, P,, N) - TS(7,P,, N)

(7.46)

192

Maxwell

Relations

whereS(U,V, N) is reexpressed
as a function of Z, p, and N in standard
fashion.
If the fundamental equationis not known we consideran infinitesimal
isothermal compression,for which we have,from equation7.43
dQ:

-TaVdP

(7.47)

Finally, supposethat the pressurechangeis large,but that the fundamental equation is not known (so that the solution 7.46is not available).Then,
if c and v areknownas functionsof z and P, we integrateequation7.47
at constant temperature
LQ:

-r

t"ovar

(1.48)

This solution must be equivalentto that given in equation7.46.

Free Expansion

septum separating the sections is suddenly fractured the gas spontaneously expandsto the volume of the whole container.We seel to predict
the changein the temperatureand in the various other parameterj of the
system.
The total internal nergyof the systemremainsconstantduring the free
expansion.Neither heat nor work are transferred to the systembv anv
external agency.
If the temperatureis expressedin terms of (J, V, and N, we find

T r - T , : T ( ( r , V r , N )- T ( U , V , , N )

(7.4e)

If the volume change is small

dT=

i?u,*d,

&)*

(7.50)

(7.51)

Some Simple Applications

193

This process,unlike the two previouslytreated,is essentiallyirreversible

and is not quasi-static(Problem4.2-3).
Example
In pr4cticethe processes
of interestrarely are so neatlydefinedas thosejust

considered.No single thermodynamicparameteris apt to be constant in the

processeswill occur readily to the reader,but the generalmethodologyis well

representedby the following particular example.

Solution
we first note that rhe tabulatedfunctions co(T,p), a(7, p), rcr(T,p), and
a(7, P) are redundant. The first three functioirs imply the last, as has already
been shown in the exampleof Section3.9.
Turning to the statedproblem, the equationof the path in the T-v plane is
T:A+ BV;
A:(71V2- T2V)l(V2-Vr);
B:(TrTt)l(Vz-V)
Furthermore, the pressureis known at each point on the path, for the known
function u(7, P) can be inverted to expressp as a function of r and u. and
thenceof u alone
P : P(T,V): P(A + BV,V)
The work done in the processis then

w: tv,
[',r1,e+ BV,v)dv
This integral must be performednumerically,but generallyit is well within the
capabilitiesof even a modestprogrammablehand calculator.
The heat input is calculatedby considerings as a function of r and,v.

d ^ s :/ P q \ s r *' (\ li s/ v\ ) , d v
\orlv--

laP\

ir,dr +\fr ) ,0,

: ( + - n " ' \ a r +L a v

\ I
But on the path, dT : B dV, so that

rcrl

a s : ( N a 2 - B V a 2*
\

.f

K.r

Kr

t)*

r94

Maxwell Relations

Thus the heat input is

O: l q l u n c,-(,t + B V )( BVa-r ) aTtcr ldv

Again the factors in ttre integral must be evaluatedat the appropriatevaluesof p
and 7 correspondingto the point v on the path, and the integral over z must
then be carried out numerically.
It is often convenientto approximatethe given data by polynomial expressions
in the region of interest; numerouspackagedcomputerprogramsfor such "fits"
are available.Then the inte$als can be evaluatedeither numerically or. analytically.
Example
In the P-u plane of a particular substance,two states,A and D, aredefinedby
Pt : 705Pa

ut : 2 x 10-2 rrt/mole

Po : lDa Pa

uo: l0-r m3/mole

and it is also ascertainedthat T,r : 350.9K. If 1 mole of this substanceis initially

in the stateA, and if a thermal reservoirat temperature150 K is available,how
much work can be deliveredto a reversiblework sourcein a processthat leaves
the systemin the stateD?
The following data are available.The adiabatsof the systemare of the form
Pu2: constant

(fors:

constant)

Measurementsof co and a are known only at the pressureof 10s pa.

Co: Bu2/3

( f o r P : t O 5P a ) ;
B : 708/3: 464.2J/mzK

a:

3/T

(for P : 105Pa)

and no measurementsof r, are available.

The reader is strongly urged to analyzethis problem independentlybefore
reading the following solution.
Solution
In order to assessthe maximumwork that can be deliveredin a reversibleprocess
A --+D it is necessaryonly to know z, - un and so - s,q.
The adiabatthat passesthroughthe stateD is describedbypuz: 102pa . m6;
it intersectsthe isobar P : lOs Pa at a point C for which
Pc : 105Pa
uc: 10-3/2m3: 3.16x 10-2 m3

Some Simple Applications

195

As a two-stepquasi-staticprocessjoining A and D we choosethe isobaricprocess

A -, c followed by the isentropic process c -- D. By considering thele two
processesin turn we seekto evaluatefirst a. - un and Jc - J,r and then uo - uc
and s, - s., yieldingfinally uo - u1 and s, - sr.
We first considerthe isobaricprocessA -- C.
tct / 3 r_ r ^\) ^
- P\) d u : / 1
d u : T d s -- P d u :

(ir,

l#

we cannot integrate this directly for we do not yet know (u)

To calculate I(u) we write

lar\
l

\0uJp

ud.

3u

( f o rP :

along the isobar.

Pn)

'(;): i"(;)

and

T : 350.9x(s0u)1/3

(on p : 10spa isobar)

Returningnow to the calculationof u, - un

a, : lia x 350.9x(50)1/3- tot] du = rls du

or

uc- ut:

1 0 5x ( u , - u ) : l . t 6 x 1 0 3J
We now require the differencauo - ur. Along the adiabat we have
up- uc:

f 'r o, P d r :
u

-rc'["'+:fi2[ujL
tr.

- r;t] :

n"

-2.t6x 103J

Finally, then, we have the requiredenergydifference

uo- ut:

- 1 0 3J

We now turn our attentionto the entropydifferences - s,q: Jc _ sr. Along

o
the isobar lC

and

: !nu-,r,
^ : (#)
a,
#a,
"^:
so - st - rc - s,t: iBlryt - uf]:

6.t I/K

Knowing au and, A.r for the process, we turn to the problem of delivering
maximum work. The increase in entropy of the system permits us to extract
energy from the thermal reservoir.

( - Q , . " ) : 4 " , A r : 1 5 0 x 6 . 1: 9 1 6 J
The total energy that can then be delivered to the reversible work source
is
(-Lu) * (-Q,..), or
work delivered : I.92 x 103 J

tF.

196

Maxwell Relations

PROBLEMS
7.4-1. ln the analysisof a Joule-Thomsonexperimentwe may be given the initial
and final molar volumesof the gas, rather than the initial and final pressures.
Expressthe derivative(07/0u)^ in termsof co, e, and rr.
7.4-2. T\e adiabatic bulk modulusis definedbv

Fs:

-,(#)":-v(#),.

Expressthis quantity in terms o-f,?,and r, (do not eliminate cr). what is

",,.a,
the relation of your result to the identity
K,/Kr: cu/co (re,callprobiem 3.9-5)?
7.4-3. Evaluatethe changein temperaturein an inflnitesimal free expansionof a
simple ideal gas(equation7.51).Doesthis result alsohold if the changein volume
is comparableto the initial volume?can you give a more generalargumentfor a
simple ideal gas,not basedon equation7.51?
7.4-4. Show that equation7.46can be written as

Q : U rpf , p l - U J p , p l
so that uIP, trl can be interpretedas a "potential for heat at constant T and,N.,,
7.4'5. A 1% decreasein volume of a systemis carried out adiabatically.Find the
change in the chemical potential in terms of. co, c, and r, (and the state
functions P, T, u, u, s, etc).
7.4-6. Two moles of an imperfect gas occupy a volume of 1 liter and are at a
temperatureof 100 K and a pressureof 2 Mpa. The gas is allowed to expand
freely into an additional volurne,initially evacuated,of 10 cm3.Find the change
in enthalpy.
At the initial conditionsc,:0.8 J/mole. K, Kr = 3 x 10-6Pa-', and c :
0.002K-r.
Answer:

I p - ( r " - p u o )I
:
AH : l;----z---^1
- Tua') l A u 1 5J
(co"r
|
l
7.4-7.Showthat (0c,/0u)r: TGzp/072), andevaluatethis quantityfor a
systemobeyingthevander Waalsequationof state.
7.4-8. Show that

(*),: -ruf,'.(#),1
Evaluate this quantity for a systemobeyingthe equationof state

#):*
"(,*

Problems

r97

7.4'9. one moleof thesystemof problem7.4-gis expanded

isothermally
from an
pr. calculatetheheatflux to the
Po to a final pressure
system
in
t1t1t_ry:*re
rrusprocess.
Answer:

O : -RZh(

i)

2Aef- p,)/r,

7.4-10. A system obeys the van der waals equation of

state. one more of this
systemis expandedisothermallyat temperaturez from an
initial volume u0 to a
final volume ur. Find the heat transfer to the systemin
this
"*pu"rion.

co: 26.20+ t7.49 x 10-3r _ 3.223x t0_6Tz

where co is in J/mole and T is in kelvins.
Answer:
Pt=15x105Pa

7-4'13- calculate the changein the molar internal energy

in a throttling process
in which the pressurechangeis dp, expressingthe reiilt
in terms of standard
parameters.
!.4:14- Assuming that a gasundergoesa free expansionand that the remperature
is found to changeby dr, calcuhtJthe differencedp between
the initial and final
pressure.

198

Maxwell Relations

7.4-16. Assuming the expansionof the ideal van der waals fluid of problem
7.4-15 to be carried out quasi-staticallyand adiabatically, again find the final
temperature|.
Evaluateyour result with the numericaldata specifiedin problem 7.4-15.
7.4'17. It is observedthat an adiabaticdecreasein molar volume of 17oproduces
a particular changein the chemicalpotential p. what percentagechangein molar
volume, carried out isothermally,producesthe samechangein p?
7.4-18. A cylinder is fitted with a piston, and the cylinder contains helium gas.
The sidesof the cylinder are adiabatic,impermeable,and rigid, but the bottom of
the cylinder is thermally conductive,permeableto helium, and rigid. Through this
permeablewall the systemis in contact with a reservoirof constant r and pr""
(the chemical potential of He). calculate the compressibility of the system
in termsof the propertiesof helium (co, u, d., K7t etc.) and
FG/V)(dV/dP)l
'Discuss
thereby demonstrate that this compressibility diverges.
the physical
reasonfor this divergence.
7.4'19. The cylinder in Problem 7.4-18 is initially filled with ft mole of Ne.
Assumeboth He and Ne to be monatomicideal gases.The bottom of the cylinder
is again permeableto He, but not to Ne. Calculatethe pressurein the cylinder
and the compressibility(-[/V)(dv/dp)
as functionsof Z, V, and p,s..
Hint: RecallProblems5.3-1,5.3-L0,and 6.2-3.
7.4'20. A system is composedof 1 mole of a particular substance.In the p-u
plane two states(l and B) lie on the locus Pu2 : constant,so that pnu) : peuzB.
The following properties of the systemhave been measuredalong this locus:
co: Cu,, a: D/u, and rr: Eu, where C, D, and E are constants.Calculate
the temperatureT" in termsof Ta,P,a,u,4,us,
&rrdthe constantsC, D, and E.
Answer:
TB: T,q* (ur - u,q)/D+ 2EpAalD-rln(ur/u")
7.4-21. A systemis composedof 1 mole of a particular substance.Two thermodynamic states, designatedas A and B, lie on the locus pu : constant. The
following propertiesof the systemhavebeenmeasuredalong this locus; co: Cu,
a : D/u2, and r": Eu, where C, D, and, E are constants.Calcullte the
differencein molar energies(u"- u) in terms of Tn,pa,u1,uB, Lrrdthe constants C, D, and E.
7.4-22. The constant-volumeheat capacityof a particular simple systemis
c,: AT3

(l : constant)

In addition the equationof stateis known to be of the form

(u-uo)r:B(r)
where B(Z) is an unspecifiedfunction of T. Evaluatethe permissiblefunctional
form of B(1).

Generali zations: M agnet i c Systems

r99

In terms of the undeterminedconstantsappearingin your functional representation of B(T), evaluated, cD, and rc. as functions of Z and u.
Hint: Examine the derivative'|zs / 0T 0u.
Answer:
cp : AT3 + (73/ DT * .E),whereD and.E areconstants.
7.4-23. A systemis expandedalong a straight line in the p-u plane, from the

C..KT

;:AP
c_

#:

(foru:uo)

B,

(forP:Pr)
Answer:

o : +A(pf- p:) + lB(uf - r3)+ iQo- p)(u:_ uo)

7.4-u. A nonideal gas undergoesa throttling process(i.e., a Joule-Thomson
expansion)from an initial pressurePo to a final pressurepr. The initial temperature is ro and the initial molar volume is uo.calculate the hnal temperatureI if
it is given that
*r: 4 alongthe T : Toisotherm(l > 0)
D"
c : do alongthe T : To isotherm
and
,| alongthe P : Pt isobar
"o:
what is the condition
on 7i in order that the temperaturebe lowered by the
expansion?
7-5

GENERALIZATIONS:

MAGNETIC

SYSTEMS

U : U ( S , V , I ,N )

(7.s2)

Legendre transformationswith respectto s, v, and N simply retain the

magneticmoment I as a parameter.Thus the enthalpy is a function of s,

Maxwell Relations

P, I, and N.
H = U [ p ] : I l + p V : F I ( , Sp,, I , N )
( 7.53)
An analogoustransformationcan be made with respectto the magnetic
coordinate

U l B . l : I J- B " I

(7.s4)

and -this potential is a function of s, v, 8", and N. The condition of

equilildum for a systemat constantexternalfield is that this potential be
mrmmum.
v-ariousother potentialsresult from multiple Legendretransformations,
as depicted in the mnemonic squaresof Fig. 7.3. Maxwell relations and
the relationships-between
potentials can belead from thesesquaresin a
completely straightforwardfashion.
UIB"J

B"

utP,8"1

UI.P]

UTT,
BJ

(#).,
(#).,

UF]

B"

UF,P,B)

UTT,P]

UTN
T

(H)..
(#),,

uIr,BJ

UTB)
FIGURE 7.3

B"

Probletns

20t

The "magnetic enthalpy" IIIP,B"l=

U + pV - B"I is an interesting
and useful potential. It is minimum for systems maintained at constanl
pressure and constant external field. Furthermore, as in equation 6.29 for
the enthalpy, dUIP,B"l:
TdS: dQ at constant p, B;, and N. Thus
the magnetic enthalpy uIP, B"l acts as a "potential for hiat" for systems
maintained at constant pressure and magnetic field.
Example
A particular material obeys the fundamental equation of the "paramagnetic
model" (equation3.66), with To : 200 K and l3l2R : 10 Tesla2trVm2J.Two
moles of this material are maintainedat constantpressurein an external field of
B, = 0.2 Tesla(or 2000gauss),and the systemis heatedfrom an initiar temperature of 5 K to a final temperatureof 10K. what is the heatinput to the system?
Solution

e: N[^o'
*':^G)]
t
-- 218.314x 5 + 10 x 0.04 x 0.11J : 83.22J
(Note that the magnetic contribution, arising from the second term, is small
ompared to the nonmagneticfirst-term contribution; in reality the nonmagnetic
ontribution to the heat capacityof real solids falls rapidly at low remperarures
end would be comparablysmall. Recall Problem3.9-6.)
PROBLEMS
751. calculate the "magneticGibbs potential" uIT,B"l for the paramagnetic
model of equation 3.66. Conoborate that the derivative of this Dotential with
rcspectto B. at constant 7 has its proper value.
?52. Repeat Problem7.5-1 for the systemwith the fundamentalequationgiven
in Problem 3.8-2.

utr,B"l:l*f;,t:

Answer:

lNnrh(k,n2e)

7.$'3. calculate (01/07)" for the paramagneticmodel of equation 3.66. Also

calculate@s/aB)r
what is the relationshipbetweenthesederivatives,as read
from the mnemonicsquare?

I
202

Maxwell Relations

7.5-4. Show that

c,"_C,:#(#),.
and

Ca"
Cr

_ Xr
Xs

where C"" and C, are heat capacities and Xr ffid Xs are susceptibilities:
Xr= Fo(01/08")r.