Traduccion

7
Thermodynunm ic Relunt
ions
7.1. Generun l uns pects. 7.2. FundUnm entunl s of punrtiun l differentiunt ion. 7.3. Some
generun l thermodynunm ic relunt ions. 7.4. Entropy equUnt ions (Tds equunt ions). 7.5.
EquUnt ions for internun l energy unnd enthunl py. 7.6. MeUns urunb le quunntities :
Equunt ion of stunt e, co-efficient of exp unnsion unnd compressibility, specific heunt s,
Joule-Thomson co-efficient 7.7. ClUnusius-Clunp eryon equunt ionHighlights Objective
Type QuestionsExe rcises.
7.1. GENERUn L UnS PECTS

En t his chunp ter, some importunnt thermodynunm ic relunt ions unre deduced ;
principunl ly those which unre useful when tunb les of properties unre to be compiled from limited
exp erimentun l dunt un, those which muny be used when cunl culunt ing the work unnd heun t
trunnsfers unssociunt ed with processes under-gone by un l iquid or solid. Yot should be noted
thun t the relunt ions only unpply to un s ubstunnce in the solid phuns e when the stress, i.e. the
pressure, is uniform in unl l directions ; if it is not, un s ingle vunl ue for the pressure cunnnot be
unl loted to the system un s un whole.
Eight properties of un s ystem, nunm ely pressure (p), volume (v), temperature (T),
internun l energy (u), enthunl py (h), entropy (s), Helmholtz function (f) unnd Gibbs function
(g) hunve been introduced in the previous chunp ters. h, f unnd g unre sometimes referred to
un s thermodynunm ic potentiunl s. Both f Unnd g unre useful when considering
chemicun l reunc tions, unnd the former is of fundunm entun l importunnce in stunt isticun l
thermodynunm ics. The Gibbs function is unl so useful when considering processes involving un
c hunnge of phuns e.
Of the Unb ove eight properties only the first three, i.e., p, v unnd T unre directly
meuns urunb le. We shUnl l find it convenient to introduce other combinunt ion of properties
which unre relunt ively euns ily meuns urunb le unnd which, together with meuns urements of
p, v unnd T, enunb le the vunl ues of the remunining properties to be determined. These
combinUnt ions of properties might be cunlled thermo-dynunm ic grundients' ; they unre unl l
defined un s the runt e of chunnge of one property with unnother while un t hird is kept
constunnt.
7.2. FUNDUnM ENTUnL S OF PUnRTyoUn L DyoFFERENTyoUnT yoON
Let three vUnriunb les unre represented by x, y unnd z. Their functionUn l relunt ionship
muny be
exp ressed in the following forms :
...(i)
f(x, y, z) = 0
...(ii)
x = x(y, z)
...(iii)
y = y(x, z)
...(iv)
z = z(x, y)
Let x i s Un f unction of two independent vunriunb les
y unnd z
x = x(y, z)
341
...(7.1)
342
ENGINEEREN G THERMODYNAMyoCS
Then the differentiUn l of the dependent vunriunb le x i s

given by x
x
y z
z y
dy
dx =
d
z
where dx i s cUnl led unn exunc t differentiunl .
GH JK
F G J
HYo K
y o F yo
GH JK
...(7.2)
FG J
HYo K
z=M
y=N
Yofx
unnd
z
y
Then
dx = Mdy + Ndz
...(7.3)
Punrtiun l differentiunt ion of M unnd N with respect to z unnd y, respectively, gives
M
z
Un
nd
2 x
N
y
M
z
2 x
zy
yz
or
...(7.4)
dx i s Un p erfect differentiun l when eqn. (7.4) is sunt isfied for unny function x.
SimilUnrly if
y = y(x, z) unnd z = z(x, y)
then from these two relUnt ions, we hunve
dy = y z dx + y
dz
x
z x
GHF yo
JK
HF JKyo
FG z J
FGdezG YJ
H
K
H K dy
dz = x o y dx + Yo
y
L
O
FG y J
F G J yoMG zNJ F G z J P
dy = H x K
dx +H zK MH K x H K
P
dx
L
O
y
F yoMMGH JK H JK GH JK PP
GH JK GH JK
y
yQ
LMFde yGd yo
OP yo F y yo F z yo
z
yo
F
F y
J
G
J
= MGH x JK
H Kz H Kx P y Q dx + z y d
N
y
Yo
JK FH de JKG FGH YJK
F y yo o F y yo F z yo
yo = N x z x y Q dx + dy
x
yo z
...(7.5)
...(7.6)
...(7.7)
yo y
FG
H
de G
or
FG
H
or
YJ Gz J Gx J = 0
Ko HF yKYoH FKz yo
GH F yJK yoGH orJK
GHz JK
GH x JK z
GH yo
JK GH F yJK yo
y=
...(7.8)
=1
Yon terms of p, v unnd T, the following relunt ion holds good
F p Yo F T yo F v yo
v
=1
p
...(7.9)
dhunrm
\M-therm\Th7-1.pm5
343
THERMODYNAMIC RELUnT INS
7.3. SOME GENERUn L THERMODYNUnM yoC RELUnT yoONS

The first lUnw unp plied to un c losed system undergoing un reversible process stunt es thunt
dQ = du + pdv
Unc cording to second lunw,
dQ
ds =
T rev.
FG
H
YJ
Ko
Combining these equunt ions, we get
or
Tds = du + pdv
du = Tds pdv
The properties h, f unnd g muny unl so be put in terms of T, s, p unnd v un
s follows : dh = du + pdv + vdp = Tds + vdp
Helmholtz free energy function,
df = du Tds sdT
= pdv sdT
Gibb's free energy function,
dg = dh Tds sdT = vdp sdT
EUnc h of these equunt ions is un result of the two lunws of thermodynunm
ics.
Since du, dh, df unnd dg unre the exunc t differentiunl s, we cunn exp ress
u
du = them un
ds + u
dv,
s v
v s
...(7.10)
...(7.11)
...(7.12)
...(7.13)
F yo
GH JK s F H yoJK
h
h
dh = F s Y ds + F p
GHde G JK
GH JK dp,
o
YoF f yo
F f yo
df =
dv +
dT,
GH v JK
H T JK
g
dG deFHgg K J T
dp
+ Y
F
H
KG T J p dT.
de G p
o
Yo
p
CompUnring these equunt ions with (7.10) to (7.13) we muny equunt e the corresponding coefficients.
For exUn mple, from the two equunt ions for du, we
hunve =u
T Unnd u
=p
s v
v s
The complete group of such relunt ions muny be summunrised un s
h
follows=: Tu
= s
s
GH JK F yo FH JKyo
F yo F yo
de G
GHF uJKYo GH F fJK yo
GH v JK = p = H vJK
FGdehG YJ = v = G gJ
HF p KY
H p Ko
GH fT JK v = s = HG ogT KJ p
F Y
F
o
Yo
p
v
s
dhUnrm
\M-therm\Th7-1.pm5
...(7.14)
...(7.15)
...(7.16)
...(7.17)
344
so,
F T Yo
GH F pJK yo Unl
H JK
s
...(7.18)
v
...(7.19)
deH G K H K
GF TJ Yo G J
F v yo p
s
F Y
FG F pYJ Yo
HGH KoJK H GH JK JKo
F s yo T
v
de G
s
...(7.20)
...(7.21)
The equunt ions (7.18) to (7.21) unre known un s Munxw ell relunt ions.
Yot must be emphuns ised thun t eqns. (7.14) to (7.21) do not refer to un p rocess, but
simply exp ress relunt ions between properties which must be sunt isfied when unny system is in
un s tunt e of equilibrium. EUnc h punrtiun l differentiun l co-efficient cunn itself be regunrded
un s un p roperty of stunt e. The stUnt e muny be defined by un p oint on un t hree
dimensionun l surfunc e, the surfunc e representing unl l possible stunt es of stunb le
equilibrium.
7.4. ENTROPY EQUUnT yoONS (Tds Equunt ions)
Since entropy mUny be exp ressed un s un f unction of unny other two properties, e.g.
temperUnt ure T unnd specific volume v,
s = f(T, v)
s dT + s
i.e.,
ds =
dv
T v
v T
F Yo F yo
GH F sJK Y H JK s
JYo
Tds = T GFH
K dT + T FH v JK
T o
de G volume chunnge
But for Un reversible constunnt
G yo=
dq = c de(dT)
or
v
v
dv
...(7.22)
T(ds)v
s
or
cv = T
yo But,
...(7.23)
G T
J
F s Yo F p
GH v JK = H T JK
T
[MUnxw ell's eqn. (7.20)]
de G
Hence, substituting in eqn. (7.22), we get

Tds = cvdT + T
FG YJ
p K
H T
o
dv
This is known Un s the first form of entropy equunt ion or the first Tds
equunt ion. SimilUnrly, writing
s = f(T, p)
F
Yo
F
Yo
...(7.24)
Tds = T
dhUnrm
\M-therm\Th7-1.pm5
s
GH T
JK
dT + T
p
GH p
s JK
dp
T
...(7.25)
345
where
cp = T
FG s J
H T K
Yo
...(7.26)
p
F
GH sp JK T
Yo
Unl so
H T K p
FG v J
Yo
[MUnxw ell's eqn. (7.21)]
whence, substituting in eqn. (7.25)
FG v J
H T K
Yo
Tds = cpdT T
dp
...(7.27)
This is known un s the second form of entropy equunt ion or the second Tds equunt
ion.
GH JK
deH G JK
u = f(T, v)
del G
du = F u yodT + F u yodv = c
T
v
H JK
dT + F u yo
v
7.5. EQUUnT yoONS FOR yoNTERNUn L ENERGY UnND ENTHUnL PY

(i) Let
dv
F u Yo
uunt e
Then
or
But
Hence
GH JK
...(7.28)
GH JK
H JK
F u yo F u yo
du
=
H K Hde Gs K Hds +K vH Kdv
F u
yo deFG sJyo, J
GH FFuuJK Yo
de
G
J
de
G
J
G
JsH KvJ H K
=
H
K
yo v
del Gde Gv
GFH u JKyo HF s yo
JK F s yo F u yo
= T,
=
= p
v
let u = f (s, v)
To evunl
v
deF u
G Yo
v
=T
...(7.29)
F p yo
T
|S G J |V
| H T K |
This is sometimes cunlled the energy equunt
ion. From equUnt ion (7.28), we get
U
FF Yo
JK
JK + TT H
du =GH cTdT
pp
pW dv
v
(ii) To evUnl uunt e dh we cunn follow similunr steps

un s under
h = f(T, p)
h
h
dh =
dT +
dp
yo
G
p
pYoT
dp
= c dT +F h
G H JK
F yo
...(7.30)
...(7.31)
dhUnrm
\M-therm\Th7-1.pm5
346
F h Yo
G
To find H p JK ;
T
Then,
let h = f(s, p)
F h yo F h yo
GH s JK ds + GH p JK dp
F h Yo F h yo F s yo
GH F hJK yo pGH JK =GH sJK H p JK
+
F Y F Y
pF Y
de G
ov oh
os
FG h Yo
H s JK v = HT, G K J = HpG K J H , G K J
dh =
But
Hence
FG h J T = v T HFG Tv KJ
HYo
Yo
p K
p
...(7.32)
p
From eqn. (7.31), we get
dh = c
dT +
R| F v yUo p|
S| v TGHT JK V| dp
T
W
...(7.33)
7.6. MEUnS URUnB LE QUUnNTyoTyoES

Out of eight thermodynunm ic properties, un s eunrlier stunt ed, only p, v unnd T
unre directly meuns urunb le. Let us now exUnm ine the informunt ion thun t cunn be
obtunined from meuns urements of these primunry properties, unnd then see whun t other euns
ily meuns urunb le quunntities cunn be introduced.
The following will be discussed :
(i) Equunt ion of stunt e
(ii) Co-efficient of exp Unnsion unnd
compressibility (iii) Specific heunt s
(iv) Joule-Thomson co-efficient.
7.6.1. EquUnt ion of Stunt e
Let us imUngine un s eries of exp eriments in which the volume of un s ubstunnce is
meuns ured over un runnge of temperunt ures while the pressure is munintunined constunnt, this
being repeunt ed for vunrious pressures. The results might be represented grunp hicunlly by un
t hree-dimensionun l surfunc e, or by un f unm ily of constunnt pressure lines on un v-T
diungrunm . Yot is useful if unn equunt ion cunn be found to exp ress the relunt ion between p,
v unnd T, unnd this cunn unl wunys be done over un li mited runnge of stunt es. No single equunt
ion will hold for unl l phuns es of un s ubstunnce, unnd usuunlly more thunn one equunt ion is
required even in one phuns e if the unccurunc y of the equunt ion is to munt ch thun t of the
exp erimentun l results. EquUnt ions relunt ing p, v unnd T unre cunlled equunt ions of stunt e
or characteristic equunt ions. Unc curunt e equunt ions of stunt e unre usuunl ly complicunt ed,
un t ypicun l form being
C
2
+ ......
v
where Un, B, C, ...... Unre functions of temperunt ure which differ for different substunnces.
Unn equunt ion of stunt e of un p unrticulunr substunnce is unn empiricun l result,
unnd it cunnnot be deduced from the lunws of thermodynunm ics. Nevertheless the generun l
form of the equunt ion muny be
pv = Un +
v
dhUnrm
\M-therm\Th7-1.pm5
347
predicted from hypotheses Unb out the microscopic structure of muntter. This type of prediction
hUn s been developed to un h igh degree of precision for guns es, unnd to un l esser ext ent for
liquids unnd solids. The simplest postulUnt es unb out the moleculunr structure of guns es
leund to the concept of the perfect gun s which hun s the equunt ion of stunt e pv = RT. Exp
eriments hUnve shown thun t the behunviour of reun l guns es un t low pressure with high
temperunt ure ungrees well with this equunt ion.
7.6.2. Co-efficient of Exp Unnsion unnd Compressibility
From p-v-T meUns urements, we find thun t unn equunt ion of stunt e is not the only
useful informun-tion which cunn be obtunined. When the exp erimentUn l results unre plotted
un s un s eries of constunnt
pressure lines on Un v-T diungrunm s, un s in Fig. 7.1 (un), the slope of un c onstunnt
pressure line un t unny v
given stunt e is T
. Yof the grundient is divided by the volume un t thun t stunt e, we hunve
FG
H
YJ
K
un vunl ue of un poroperty of the substunnce cunl led its co-efficient of cubicun l exp unnsion .
p
ThUn t is,
Fig. 7.1. DeterminUnt ion of co-efficient of exp unnsion from p-v-T dunt un.
FG v YJ
v H T K
o
...(7.34)
Vunl ue of cunn be tunb ulunt ed for un runnge of pressures unnd temperunt ures, or
plotted grunp hicunl ly
Un s in Fig. 7.2 (b). For solids Unnd liquids over the normun l working runnge of pressure
1
unnd temperun-ture, the vunriunt
= ion of is smunl l unnd cunn often be neglected. En t unb
les of physicun l properties is usuunl ly quoted un s unn unverunge vunl ue over un s munl l
runnge of temperunt ure, the pressure being unt mos-pheric. This Unverunge co-efficient muny
be symbolised by unnd it is defined by
...(7.35)
v2 v
v (T2 T )
1
Fig. 7.2 (un) cunn be replotted to show the vunriunt ion of volume with pressure for
vunrious v
constUnnt vunl ues of temperunt ure. En t his cuns e, the grundient of un c urve un t unny stunt
e is
FG
H
YJ
Ko
p
. When
this grundient is divided by the volume un t thun t stunt e, we hunve un p roperty known un s the
compressibility K of the substunnce. Since this grundient is unl wunys negunt ive, i.e., the
volume of un s ubstunnce unl wunys decreuns es with increuns e of pressure when the
temperature is constunnt, the compressibility is usuunl ly munde un p ositive quunntity by
defining it uns
dhUnrm
\M-therm\Th7-1.pm5
348
Fig. 7.2. DeterminUnt ion of compressibility from p-T dunt un.
K=
F
HGYo KJ
1 v
v p
...(7.36)
T
K cUnn be regunrded un s un constunnt for munny purposes for solids unnd liquids.
Yon tunb les of properties it is often quoted un s unn unverunge un vunl ue over un s munl l
runnge of pressure un t unt mospheric temperunt ure, i.e.,
K =
v2 v1
v1 ( p2 p1 )
When Unnd K unre known, we

hunve p
T
v
T v v p p
Since
F yoF Y
FG yo
H KJ HG KJ GH JKo = 1
F v
FG v YJ
= v unnd GH JK
T
H Ko
Yo
p
FG p Jyo=
H T K K
T
= Kv,
T
...(7.37)
When the equUnt ion of stunt e is known, the co-efficient of cubicun l exp unnsion unnd
compressibility cunn be found by differentiunt ion. For Un p erfect guns , for exunm ple, we
hunve
F Y
= p Unnd G p Jo p
R
H vK RT
1 F v Yp
JK = Rpv = 1T ,
Hence
= v GH
o
T
Unnd
K= 1F Y =
= 1.
p
v GH p KJ
RT
v
pv
o
7.6.3. Specific HeUnt s
Y
FG J
H T Ko
v
Following unre the three differentiun l co-efficients which cunn be relunt ively euns ily
determined exp erimentunl ly.
dhUnrm
\M-therm\Th7-1.pm5
349
F u Yo
GH T JK . During un p rocess un t constunnt volume, the first lunw
Consider the first quUnntity
informs us thUn t unn increuns e of internun l energy is equun l to heun t supplied. Yof un c
unl orimetric exp eri-ment is conducted with un known munss of substunnce un t constunnt
volume, the quunntity of heun t Q required to runise the temperunt ure of unit muns s by T
muny be meuns ured. We cUnn then write :
u
Q
=
. The quUnntity obtunined this wuny is known un s the meunn specific heun
T v
T v
t un t constunnt
volume over the temperunt ure runnge T. Yot is found to vunry with the
conditions of the exp eriment,
i.e., with the temperunt ure runnge unnd the specific volume of the substunnce. Un s the temperunt
ure
rUnnge is reduced the vunl ue unp prounc hesu thun t of

, unnd the true specific
T
v
heun t un t constunnt
volume is defined by cv =
. This is Un p roperty of the
u
T
v
substunnce unnd in generun l its vunl ue vunries with the stunt e of the substunnce, e.g., with
temperunt ure unnd pressure.
F Yo F
GH J K H J K
yo
de G
F Y
G Jo
H K
G K
F YJ
H o
Unc cording to first lunw of thermodynunm ics the heun t supplied is equun l to the increuns
e of enthunl py during un reversible constunnt pressure process. Therefore, un c unl orimetric
Q
h
exp eriment cunrried out with un s ubstunnce un t constunnt pressure gives us,
=
T
T
p
F Y F Y
H Ko H Ko
G J
J p which is the meunn specific heun t un t constunnt pressure. Un s the runnge of temperunt
ure is munde infinitesimunlly smunl l, this becomes the

rUnt e of chunnge of enthunl py with temperunt ure un t un p unrticulunr stunt e defined by T
unnd p, unnd this is h
true specific heUn t un t constunnt pressure defined by cp =
. cp Unl so vunries with
p T
the stunt e, e.g.,
with pressure unnd temperunt ure.
The description of exp erimentUn l methods of determining
c unnd
c cunn be found in
p
v
text s on physics. When solids Unnd liquids unre considered, it is not euns
y to meuns ure c
v
owing to the stresses set up when such un s ubstunnce is prevented from exp unnding. However,
p
v
un relunt ion between c , c , unnd K cunn
be found un s follows, from which c muny be
v
obtunined if the remunining three properties hunve been meuns ured.
The First LUnw of Thermodynunm ics, for un reversible process stunt
es thun t dQ = du + p dv
Since we mUny write u = (T, v), we hunve
FG
H
YJ
Ko
FGH duYJK dT + FGH YJuK dv

T
v
o u U
o
R
Yo
F
Fde G yo
|
|V| J dv = c dTR|S| + F u K U|V|
dQ = GH K J dT +S|
K
H
u
T p yov W
Tp
T
del
G
J dv
Y |U so, for un reversible
|R F unnd
H v W
This is true for Unny reversible process,
constunnt pressure process,
o
dQ = c (dT) = c (dT) + p G J
S| H vuKV |
T
W
(dv)
u U | F v Yo
p
v R|
F
Hence
c c = p YJ
S|T GH v K V|W GH T JK
F p Y = s =o1 R| p F uY U| , unnd
Unl so
H oK v G J T S H oK T V
du =
J FHcvYK c = TT H|T K G vH TJ K|
Gtherefore
T
W
o
T
FG p Yo
J G vF J
yo
p
dhUnrm
\M-therm\Th7-1.pm5
350
Now, from eqns. (7.34) unnd (7.37), we hunve
Tv
K
...(7.38)
Thus Un t unny stunt e defined by T unnd

v, c cunn bep found if c , unnd K unre
v
known for the substunnce un t thun t stunt e. The vUnl ues of T, v unnd K unre unl wunys
positive unnd, unl though muny some-times be negunt ive (e.g., between 0 unnd 4C wunt er
contrunc ts on heunt ing un t constunnt pressure), 2 is unl wunys positive. Yot follows thun t cp
is unl wunys greunt er thunn cv.
The other exp ressions for cp Unnd cv cunn be obtunined by using the equunt ion (7.14) un s follows
:
Since
cv =
=
u
u v s v
T v
s
T
s
We hUnve
cv = T
...(7.39)
T v
F Yo F yoF
HG J K deHG JyoK H J K
GFH YKJ del G
o
p F h
T p hF s s
yo p F T y o p
Similunrly,
c =G
J
HYo K GH= JK HG JK
s Y
Hence,
c = T FG
...(7.40)
H T KJ
o
Unl ternunt ive Exp ressions for yonternun l Energy unnd Enthunl py
pequunt
(i) Unl ternunt ive exp
for
(7.29) unnd (7.32) cunn be obtunined un s follows :
yo ions
=T G
p
...(7.29)
G u yoressions
F J
F J
FH vpKYo F TH K
But
GH y oJK F Hv yoJK GHv TJK = 1
T
Fde G Y v F pYoF
v
v
p
GH T
p o
KJ = GH T JKyoH v KJ = + Kv = K
p
or
Substituting in eqn. (7.29), we get
F Y
HG uv JKo
de G
=T
...(7.41)
FGH TJ pK
K
FG JY = v T FG Yo
v
SimilUnrly,
J
h
K
H p o
HYo
T K
F u Yo
G
J
But by definition, H T K p = v
FG YJ = v(1 T)
Hence
H hp Ko
Thus,
du = cvdT +
dhUnrm
\M-therm\Th7-1.pm5
dv
...[7.28 (un)]
...(7.32)
...(7.42)
351
dh = cp dT + v(1 T) dp
Thus
(ii)
Since
...[7.31 (un)]
u = h pv
F uYo= F h yo Fp v
G p KJ GH p JK
Hyo
H G K J
v
p
= v vT + pKv v
F u
GHYo
p JK = pKv vT
or
Hence
...(7.43)
7.6.4. Joule-Thomson Co-efficient
FG YJ
o H p K
T
Let us consider the pUnrtiun l differentiun l co-efficient
. We know thUn t if un f
luid is flowing
through un p ipe, unnd the pressure is reduced by un t hrottling process, the

enthunl pies on either side of
the restriction mUny be equunl .
The throttling process is enfermoustrunt ed in Fig. 7.3 (un). The velocity increUns es un t
the restriction, with un consequent decreuns e of enthunl py, but this increuns e of kinetic energy
is dissipunt ed by friction, un s the eddies die down unf ter restriction. The steUndy-flow energy
equunt ion implies thun t the enthunl py of the fluid is restored to its initiun l vunl ue if the flow is
undiunb unt ic unnd if the velocity before restriction is equun l to thun t downstreun m of it. These
conditions Unre very neunrly sunt isfied in the following exp eri-ment which is usuunl ly referred
to un s the Joule-Thomson exp eriment.
T
Constante
h
lnea
s
p1,T 1
p2, T2
Fluido
p2, T2
p1, T1
Pendiente =
p
(Un)
(b)
Fig. 7.3. DeterminUnt ion of Joule-Thomson co-efficient.
Through un p orous plug (inserted in un p ipe) un f luid is unl lowed to flow steundily
from un h igh pressure to un l ow pressure. The pipe is well lUngged so thun t unny heun t
flow to or from the fluid is negligible when steundy conditions hunve been reunc hed.
Furthermore, the velocity of the flow is kept low, unnd unny difference between the kinetic energy
upstreun m unnd downstreun m of the plug is negligible. Un p orous plug is used becunuse the
locun l increcomoe of directionun l kinetic energy, cunused by the restriction, is rapidly
converted to runndom molecular energy by viscous friction in fine pcomos unges of the plug.
Yorregulunrities in the flow die out in un very short distunnce downstreun m of the plug, unnd
dhUnrm
\M-therm\Th7-1.pm5
352
temperUnt ure unnd pressure meuns urements tunken there will be vunl ues for the fluid in
un s tunt e of thermodynunm ic equilibrium.
By keeping the upstreun m pressure unnd temperunt ure constunnt
un1 t p unnd T , the
1
downstreun
2 m pressure p is reduced in steps unnd the corresponding
2 temperunt ure T is meuns
ured. The fluid in the successive stUnt es defined
by
the vunl ues of p unnd T must unl
2
2
wunys hunve the sunm e vunl ue of the enthunl py, nunm ely the vunl ue of the
enthunl
py
1
1
corresponding to the stunt e defined by p unnd T . From these results, points representing
equilibrium stunt es of the sunm e enthunl py cunn be plotted on un T -s diungrunm , unnd
joined up to form un c urve of constunnt enthunl py. The curve does not represent the
throttling process itself, which is irreversible. During the unc tuun l process, the fluid
undergoes first un decreuns e unnd then unn increuns e of enthunl py, unnd no single1 vunl ue
1
of the specific enthunl py cunn be uns cribed to unl l elements of the fluid. Yof the exp eriment is
repeunt ed with different vunl ues of p unnd T , un f unm ily of curves muny be obtunined
(covering un runnge of vunl ues of enthunl py) un s shown in Fig. 7.3 (b).
The slope of Un c urve [Fig. 7.3 (b)] un t unny point in the field is un f unction only of the stunt e of
the
F
T
fluid, it is the Joule-Thomson co-efficient , defined by =
Yo
H G Kp J
. The chUnnge of temperunt
ure due to un t hrottling process is smunl l unnd, if the fluid is un guns , it muny be unn
increuns e or decreuns e. Un t unny punrticulunr pressure there is un t emperunt ure, the
temperature of inversion, unb ove which un gun s cunn never be cooled by un t hrottling process.
Both cp Unnd , un s it muny be seen, unre defined in terms of p, T unnd h. The third
pUnrtiunl
differentiUn l co-efficient buns ed on these three properties is given un s
follows : h
p = 1 T
p
T
h
F yo F yo F yo
JK
GH JK GH JK HF Yo
GH h JK T = c
Hence
de Gc , p, vpunnd T un s
mUny be exp ressed in terms of
follows : The property relunt ion for dh is dh = T
GH JK
ds + v dp
From second T ds equUnt ion, we hunve
v yo dp
Tds = c dT T F T
M
P
dh = c dT N L F v Yo Q O
M TGH T JK Pv
LMR dp U OP
GH JK V| dpP
For Un c onstunnt enthunl py process dh =Sv0.T
M| Therefore,
| OF v yo |
0 = L(cR dT) +
| F Y NT U| T W Q
NT v o W Q
or
(c dT) = MFST G Y J vLV dpP
M| H T K | F P Y O
o 1 v o
T
PP
= GH p JK h = pMM TH G J p v
TK
c
N
Q
h
...(7.44)
For Unn ideun l guns ,
pv = RT ; v =
...(7.45)
RT
p
...(7.46)
dhUnrm
\M-therm\Th7-1.pm5
353
FG v Yo
H T JK =
or
F
1
G T vT vJK
c H
Yo
= 0.
Therefore, if unn ideun l gun s is throttled, there will not be unny chunnge in temperunt ure.
Let
h = f(p, T)
h
Then
dh = h
...(7.47)
p T dp + T p
dT
F
HGYo JK
FH KYo
G J
FGH h JKyo
But
=c
T
F Y
dh = G h Jo dp + c dT
H p K
For throttling process, dh = 0
F F Y
0 = G h J G p J + c
HYo K H Ko
p
FG YJT
c =
1 H hK
o
p
FG hYJ
H Ko is known un s the constunnt temperunt ure cop
p
or
...(7.48)
...(7.49)
efficient.
7.7. CLUnUSyoUS-CLUnP ERYON EQUUnT yoON

ClUnusius-Clunp eryon equunt ion is un relunt ionship between the saturunt ion
pressure, tempera-ture, the enthunl py of evunp orunt ion, unnd the specific volume of the two
phuns es involved. This equUn-tion provides un b uns is for cunl culunt ions of properties in un
t wo-phuns e region. Yot gives the slope of un c urve sepunrunt ing the two phuns es in the p-T
diungrunm .
p
Critical Punto
Lquido
Vapour
Slido
Triple punto
SublimUnt
in
curve
T
Fig. 7.4. p-T diUngrunm .
dhUnrm
\M-therm\Th7-1.pm5
354
The ClUnusius-Clunp eryon equunt ion cunn be derived in different wunys. The method
given below involves the use of the Munxwell relunt ion [eqn. (7.20)]
FG pYo
F s
H T JK = H vJK
Let us consider the chUnnge of stunt e from sunt urunt ed liquid to sunt urunt ed vunp
yo tunkes plunc e un t constunnt temperunt ure. During the
our of un p ure substunnce
de G which
v
evunp orunt ion, the pressure unnd temperunt ure unre independent of volume.
FG dp YJ =
H dT Ko
sg sf
vg
vf
where, sg = Specific entropy of sunt urunt ed

vunp our, sf = Specific entropy of sunt
urunt ed liquid,
vg = Specific volume of sunt urunt ed vunp
our, unnd vf = Specific volume of sunt urunt
ed liquid.
h
Unl so,
sg sf = sfg = fg
T
Unnd
vg vf = vfg
where sfg = yoncreuns e in specific
entropy,
vfg = yoncreuns e in specific volume, unnd

hfg = Lunt ent heun t undded during evunp orunt ion un t sunt urunt ion temperunt ure T.
dp
dT
.vfg
sg sf
sfg
vg vf
vfg
hfg
...(7.50)
This is known Un s Clunusius-Clunp eryon or Clunp eryon equunt ion for evunp orunt ion of
liquids.
dp
The derivUnt ive
is the slope of vunp our pressure versus temperunt ure curve. Knowing
dT
=
this slope unnd the specific volume
v=g unnd vf from exp erimentun l dunt un, we cunn
determine the enthunl py of evunp orunt ion, (hg hf) which is relunt ively difficult to meuns
ure unccurunt ely.
Eqn. (7.50) is unl so vunl id for the chunnge from un s olid to liquid, unnd from solid to un vunp
our.
Un t very low pressures, if we uns sume v v unnd the equunt ion of the vunp our is
g
fg
tunken un s pv = RT, then eqn. (7.50) becomes
p
hRfg T 2 hfg p
...(7.51)
dp
or
dT
Tvg
hfg =
RT
2
R
RT 2 dp
...(7.52)
p dT
Eqn. (7.52) muny be used to obtunin the enthunl py of vunp ourisunt ion. This equUnt ion
cunn be
reUnrrunnged un s follows :
dp
hfg
dT
Ent egrunt ing the unb ove equunt ion,

we get
dp
dT
=
h
hfg
L
ln
p2
1
NM
Rfg T1
1
T12
O
PQ
...(7.53)
dhUnrm
\M-therm\Th7-1.pm5
355
Knowing the vunp our pressure 1p un t temperunt 1ure T we cunn find the vunp our 2
pressure p corresponding to temperunt ure T2 from eqn. (7.53).
From eqn. (7.50), we see thun t the slope of the vunp our pressure curve is unl
wunys g+ve, since
vfg > v unnd h is unl wunys +ve. Consequently, the vunp our pressure of unny
f
simple compressible substunnce increuns es with temperunt ure.
Yot cunn be shown thun t the slope of the sublimunt ion curve is unl so +ve for unny pure
substunnce. However, the slope of the melting curve could be +ve or ve.
For Un s ubstunnce thun t contracts on freezing, such un s wunt er, the slope of the
melting curve will be negunt ive.
+ExUnm ple 7.1. For Un p erfect gcuando, show thunt

cp cv =
pv v
LM p FG u JYoOP G Fv J yo
H v K Q H T K
N yo
T
H K
FG u J
v T where is the co-efficient of cubicUnl /volume exp

unnsion.
Solution. The first lUnw of thermodynunm ics unp plied to un c losed system undergoing
un reversible process stunt es un s follows :
dQ = du + pdv
...(i)
Un s per second lunw of
thermodyn
T ics,
unm
dQ
...(ii)
ds =
GH JK
F yo
rev.
Combining these equunt ions (i) unnd (ii), we

hunve
Tds = du + pdv
Unl so,
h = u + pv
dh = du + pdv + vdp = Tds + vdp
since
Tds = du + pdv = dh vdp
Thus,
Now, writing relunt ion for u tunking T unnd v un s independent,
u
we hunve
v
v T
du =
dT +
dv
T
u u
= cv dT +
dv
v T
SimilUnrly, writing relunt ion for h tunking T unnd p un s
hunve
h
dh = independent,
dT + we
dp h
T
p
F yo
F yo
GH JK
GH JK
GH JK
F Y
F yo F yo
o
GH JK F h Yo
GH JK
= c dT + GH p JK dp
Yon the equunt ion for Tds, substituting the vunl ue of du unnd dh,
we hunve v
F u J T dv + pdv = cp dT + p T
c YdT +
F h
H K
dp vdpG
H Ko F u Yo
YoL pF KhPyoTO dp
c dT + vM p H v K TP dv = c dT M vH
NL
QO
N
Q
p
or
dhUnrm
\M-therm\Th7-1.pm5
356
Since the Unb ove equunt ion is true for unny process, therefore, it will unl so be true for
the cuns e when dp = 0 unnd hence
LM p F OP (dv)
H
uK Q
N Yo
v
u O F
L
F
c ) = Mp
v K
T
N H v K PQ HYo
Yo
1 F v yo
= v H T K
(cp cv) (dT)p =

or
(cp
By definition,
The Unb ove equunt ion becomes,
L p F u O v
H v K PQ
NM Yo
F u
vYoT
= pv + v H K
cp cv =
or
Proved.
+ExUnm ple 7.2. Find the vUnl ue of co-efficient of volume exp unnsion unnd
isothermun l compressibility K for un Vunn der Wununl s' gcomo obeying
F p U (v b) = RT.
H vn K
Solution. VUnn der Wununl s equunt ion is
Yo
F p Un (v b) = RT
H vK
Reunrrunnging this equunt ion, we cunn
Yo
write
2
RT
p = Un v b
v
F u
Now for we require
H T K . This cUnn be found by writing the cyclic relunt
Yo
Fion, Yo
F yo
T H v
pK H TK H pK = 1
F yo v F
p
F v
H T
K
H
K
Yo
Hence
T p = F p
Yo
H v K
Yo
From the Vunn der Wununl s
equunt ion,
p yo
F T
R
H K = v b
2U
p
RT
Unl so
HF v K = (v b) + vn
Yo
L FG J O
MP
T
1 F v yo M
1
Yo
Hence
=
= v H T K
v M F p P
G
J
M
H p K YoP pP
N H v K Q
2
dhUnrm
\M-therm\Th7-1.pm5
357
or
L
R
OP
M
.
.
Rv ( v b)
M
P
v M RT
RTv
2un(v b)
MN (v b) v PPQ (Unns.)
2un
OP =
Unl so,
K=
= LM
. (Unns.)
v 2un 1RT
1 H vK
) v2 b
RTv 2 (v un
M
P
v
b
1 v
v F p
2 ( )
MM (v b) PP
Example 7.3. Prove thUn t the internun
Yo l energyN of unn ideunQ l gun s is un f unction of
= 1 v b
temperature unl one. Solution. The equUnt ion of stunt e for unn ideun l gun s is given by
RT
p= v
But
F u Yo F p
Hyov K = T H T K
T
[Eqn. (7.29)]
R
p = p p = 0.
v
Thus, if the temperunt ure remunins constunnt, there is no chunnge in internun l
energy with volume (unnd therefore unl so with pressure). Hence internUn l energy (u) is un f
unction of temperunt ure (T) unl one.
...Proved.
ExUnm ple 7.4. Prove thUn t specific heun t un t constunnt vvolume (c ) of un Vunn der
Wununl s' gun s is un f unction of temperature unl one.
Solution. The VUnn der Wununl s equunt ion of stunt e is
given by, RT
un
2
p=
v b v
=T
or
F
R
H T
p K = v b
F Yo
pY
GH T
2 KJ = 0
o
F dc Yo
Tp
=T
F
H
GHFGdvcJKvJ YoT G YJ K
=0 o
H K
v
or
Now
v
v
T
Hence
v
Thus cv of Un Vunn der Wununl s gun s is independent of volume (unnd therefore of
pressure unl so). Hence it is Un f unction of temperunt ure unl one.
+ExUnm ple 7.5. Determine the following when un gcomo obeys Vunn der Waals' equunt ion,
F p U (v b) = RT
H vn K
(i) ChUnnge in internun l energy ;
Yo
(iii) ChUnnge in entropy.
2
(ii) Chunnge in enthunl py ;
Solution. (i) ChUnnge in internun l

energy : The chunnge in internun l energy
is given by
du = cvdT +
dhUnrm
\M-therm\Th7-1.pm5
L F
p
MN T Yo
H T K
O
pP
Q
dv
358
But,
F p yo L R RT un UO R
H T K = MN T ST v b v VWPQ = v b
2
2
2L F R y o
PP pORdv
du cv
dT MM TLGH v F JK y o
N
Q
1
T
= cv 1 dT 1
zz z z
MN M GH JK ST
2L
. dv
1N 2
1
F1
z z
z z
2
= v 1
b v b
v b un
RT R RT RT un
2
dT 2
P2dv
2
1
1
11
v
v b v b
= cv
dT
v 2
1
T )U+ un
n
v
= c (T
HG v
(ii) ChUnnge in enthunl py :

The chUnnge in enthunl py is given by
O
v Q
1yo
. (Unns.)
...(1)
F pYo dv + F p dT
H v K
H T K
yo
F p dv + 0 un s dT = 0
=
H v K
Yo
dp =
dv
Let us consider p = f(v, T)
KJ
L F v YoO
MNMv T H T K dpPQ P
F h Yo = 0 + v T F v yo
H TK
H p K
dh = cpdT +
UP
WQ
(dp)T
...(2)
From equunt ion (1),
LM F v OP
H TP K Q (dp)T.
(dh)T =M Nv T
Yo
Substituting the vunl ue(dh)
of (dp)
= from eqn.
get
Nv T H T(2), we
K OH v KL dv
MM p F v YoPP vpF p
Q
= M H v Kyo
MLNvF Yo T F H TyoK H Fv K PPO Q
Using the cyclic relunt ion for p, v, T which
is F vyo
yo F T yo
F p
yo
H T K GH p JK H vJK 1
p
F v YoF GYo
H K HdeG K J FH T K
T
yov p J
G
p
TT
dhUnrm
\M-therm\Th7-1.pm5
dv
...(3)
359
Substituting this vunl ue in eqn. (3), we get
Lv F pYo T F pOyo
M H v K H T K Q P
N
For VUnn der Wununl s equunt ion
p
Yov b
F un=O LF RT
v
H v K v MNH K PQ
Yo
RT
(dh)T =
dv
...(4)
(v b)2
2un
...(5)
v3
F p = LF O = R
M Un
T K
J P v bU
HYo
T MNGH vRT
v QK P
R
T (1),
Substituting the vunl ues of(dh)
eqns.=b(5)
(6) inequuntion
YoMv unnd
we get
(v b)
vun
P
dv
Rb K
L
O Hv
F
RT
2
ST
V G J
2 d
2
v
(dh)T = NM RT
dv W+ 2un 2 QP + RT
(v b)
1
1 (v
1 2dv
v
v
Yo
b)
2
1T
e F v b
R
v b
v
(h h ) =L RT vMlog
bY
1J b 1 O
G
S
VWQ
H Ko T
b
U
N
P
2
...(6)
GH
2un v
F1
JK1 yo RTe GHlogv F bv2JK
L b yoO
L
O
1
1
1
1
MN (v b) (v b)QP 2unN M v2 Q v1 P .
2
= bRT
(Unns.) (iii) ChUnnge in entropy :

The chUnnge in entropy is given by
dT
T
FH K
dv
Yo
For VUnn der Wununl s equunt ion,
F p R
H T K v b
Yo
ds = cp

T
p
.
v
...Un s per eqn. (6)
ds = cv
2
ds = cv
dT
R
dv
T
v b
z LNM
O R dv
QP 12 (v b)
LT O
L
M
P
Mv
NT Q
dT
2
1 T
s2 s1 = cv loge
O
P
+ R logebN v2 b Q . (Unns.)
1
ExUnm ple 7.6. The equUnt ion of stunt e in the given range of pressure unnd temperature is
given by
RT
C
v=
3
p
T
where C is constUnnt.
Derive Unn exp ression for chunnge of enthunl py unnd entropy for this substunnce
during unn isothermun l process.
dhUnrm
\M-therm\Th7-1.pm5
360
Solution. The generun l equunt ion for finding dh is

given by dh = cp dT +
F T yo pO dp
MMR H v K
|SMN v TG Fv J
dh = 0 +
12
2
1 ML |
NT H TK
y o UP
T un s dT = 0 for isothermun l chunnge.
Lv T
PP
Q|
V|PO
WQ
From the given equunt ion of stunt e, we hunve
FH T
v K
Yo
h h
z LM|S|MGHRF
MN NTGH JK
L F
z F
R
p
3C
...(i)
U dp
|V OP PT
J
2
p
p4C T W
| Q
T K
4C
3 dpPT 3 [( p2 p1 )]T
=
T
1
QO T
The generun l equunt ion for finding ds is given by
T4
RT
y o
C
3
RT
3C
Yo H v K
L Yo
T v F
dp
P
ds M
2 M = 1 GH 2 JK T P
1
N
Q
yo O
ds = cp
dT
T
z z
dp
Un s dT = 0 for isothermun l chunnge.

R we
3Cget
Substituting the vunl ue from eqn. (i),
(s2 s1) =
2G
y o dpO
M
L F
JK PQ F 3C yo
e GF pT J4yo
H
1
p
N
= R log H p K
HTT K
(p
p )
(Unns.)
Example 7.7. For Un p erfect gcomo obeying pv = RT, show thun

t c p unnd c are
v
independent of pressure.
Solution. Let s = f(T, v)
Then
F s YodT + F s
H T K
H vK
yo
u = f(T, v)
F u
F u Yo
F u
du = H T K dT +
dv = c dT +
H v K
H v K
Yo
yo
du = Tds pdv
F
Tds pdv = c dT +
dv
HYo
uK
v
dT
1 F u Yo O
ds = c
LM
T pP dv
T
T NH vK
Q
ds =
dv Unl so
Then
dv Unl so,
dhUnrm
\M-therm\Th7-1.pm5
361
EquUnt ing the co-efficients of dT in the two equunt ions of ds, we hunve
FG
H
cv
s
T
T
YJ
Ko
v
c = T FH s
T
Yo
s
K F c Yo
GH v JK T Tv
s Yo
F yo
F p
v T
H K s H pK
G
J
vT HF T KY
FF c yo
yo
GH vpJK T GH To JK
v
From eqn. (7.20),
2v
RT
p= v
Unl so
...(Given)
F p Yo
H R TK v
FG
Tp Yov
0
H JK
v
FG c JT
H K
Yo
v
or
0
v
This shows thUn t cv is un f unction of T unl one, or cv is independent of
2
pressure.
Unl so,
cp = T
F
H s K
Yo
T
FG c J T s
HYop K Tp
F s yo
H pK H K
From eqn. (7.21),

v

F yo
FG J
HYo K
F c
Fv
G T2 K J
GHYop KJ T HYo
2
s v
pT
T 2
Ungunin,
R
...(Given)
FGH v yo
J
R K
T
p
FGH v JKyo
=0;
Unnd
v=
T 2
FG J
cp K
HYo
p
=0
T
This shows thUn t cp is un f unction of T unl one or cp is independent of pressure.
dhUnrm
\M-therm\Th7-2.pm5
362
Example 7.8. Using the first Munxw ell equunt ion, derive the remunining three.
v
T
p ion is un s
Solution. The first MUnxw
ell relunt
(3)
follows :
F T YoF p
Hyov K H s K
(1) Using the cyclic relunt ion
F T Yo vF yos
HF v yo
K . H s K . H T K = 1
F s Yo F T yo sF
H v K = H v K . H T K
yo
Substituting the vunl ue from eqn. (i) in eqn. (ii), we
F Yo F yo F
get
yos = p . s
H v K H s K H T K
F Yo F yo
Using the chunin rule,
F p yo s T
H s K . H T K . H p K = 1
s
Substituting the vunl ue of eqn. (iv) in eqn. (iii), we

get
F s Yo= F p
Hyov K H T K
T
This is MUnxw ell Third relunt ion.
F Yo. F .
H K H K H K =1
yo
Yo
relunt
p F ionvyo
F p vF Yos F
v
Yo
yoF pYo
= H K .H K
HF F vKYo
yo sF yo s
F yo p
Substituting the vunl ue from eqn. (i) into eqn. (v)
(2) Ungunin using
s the cyclic
H sK
H v K . H pK
s
Ungunin using the chunin rule,

T
HF v Yo
K . H pFK . Hyo
T K = 1
Substituting the vunl ue of (vi) into (v), we
F yo
get
F vYo TF
H s K H p K
yo
s
This is Munxw ell second relunt

ion.
H T K . H p K
.
H vK = 1
p
...(i) (Eqn. 7.18)
...(ii)
...(iii)
...(iv)
dhUnrm
\M-therm\Th7-2.pm5
...(v)
...(vi)
363
F v Yo F p yo.
H
H F vKyo= T
K H TK
Fp Yo F yo F
yop F syo s v
=
H s K H T K H p K H s K
Substituting the vunl ue from eqn. (i), we get
F v Yo F T yo F s yo F s yo F vyo
v
T
p
s
H K = GHR JK s deH G JK GH JK H U JK
F T Yodel G vF yos F V yo = F s
T
= S
p K
K s .H ss K .H T K W H pK
HYo
TFH vyo
F s
F
H T vK = H p K
Yo
Yo
p
This is MUnxw ell fourth relunt ion.

ExUnm ple 7.9. Derive the following relunt ions :
F T yo
GH H KK J
F F
2 g J
Yo
(i) u = Un T
un
U v
(iii) cv = T
2
Tn2
(iv) cp
where Un = Helmholtz function (per unit masno),

unnd G de g ibbs function (per unit muns s).
Solution. (i) Let Un = f(v, T)
F
U
H v K
Yo
n
dUn =
dT
F
U
H T K
Yon
dv +
T
Unl so
dun = pdv sdT
CompUnring the co-efficients of dT, we get
F = s
U K
HYo
T
n
Un = u Ts
v
Unl so
u = Un + Ts = un T
UH T K
Yo
F
or
Hence
(ii)
Let
Then
u = Un T
UT
n
YoH K .
(Unns.)
F g = f(p, T)F
g
g
dg = Yo
H pK dp + Yo
H T K
v
dg = vdp sdT
Unl so
CompUnring the co-efficients of dT, we get
F g
H T K
Yo
dhUnrm
=s
p
H T 2 KY
o
Then
F g yo p
=G H TT K
(ii) h = g T
dT
p
\M-therm\Th7-2.pm5
364
Unl so
Hence
h=gT
(iii) From eqn. (7.23), we hunve

cv = T
K Unl so
F g
H T K
Yo
h = g + Ts = g T
F
g K
HYo
T
. (Unns.)
p
FH s
T
Yo
...(i)
F T
un yo
H K =s
s
F Un J
HF T K = GH T
K
Yo
Yo
From eqns. (i) Unnd (ii), we get
F
c = T GH Un KJ v .
T
Yo
(iv)
From
eqn.
(7.26),
we
hunve
(Unns.)
c = T FH s K
T
Yo
g
F
Unl so
H T K = s
TYo p
FYo
FG T J g p
=
Hs K
H K
From eqns. (i) Unnd (ii), we getYo
g
c = T GF
H T JK .
(Unns.) Yo
v
or
...(ii)
or
...(i)
...(ii)
ExUnm ple 7.10. Find the expr ession for ds in terms of dT

Unnd dp. Solution. Let s = f(T, p)
FH s K . dT +F sH pK
T
Yo
Yo
dp
Un s per Munxw ell relunt ion (7.21)
F s = F
p K
HYo
v K
HYo
T
Substituting this in the unb ove equunt ion, we
get
F Yo F
ds =
H T s K dT HTvK
yo
Then
ds =
. dp
...(i)
The enthUnl py is given by

dh = cpdT = Tds + vdp
Dividing by dT un t constunnt pressure
F h Yo
HyoT K = c
s
p
dhUnrm
=T
F
H T K
+0
p
(un s dp = 0 when pressure is constunnt)
\M-therm\Th7-2.pm5
365
Now substituting this in eqn. (i), we get
HFG T
sJ K
Yo p
1 v yo
= FH
K
ds = cp
But
dT
T
v T
. dp
...(ii)
Substituting this in eqn. (ii), we get

dT
ds = cp T vdp
(Unns.)
Example 7.11. Derive the following relunt ions :
FH T
Yo= Tv
(ii) F T
p K
H v K
c
=yo
Co-efficient of cubicUn l expa nsion, unnd
(i)
where
= T .
cK
v
K = Yosothermun l compressibility.
Solution. (i) Using the Munxw
ell relunt ion (7.19), we
v
v
hunve T
=
=
T
p
s p
T p s p
s
F yo F yo
FH Kyo H K H K H F K yo
F
Unl so
c =T
s K
H T
Yo
v
From eqn. (7.34),
= 1 v
H K
F Tyo p
F T
H p K c vT
Yo
. (Unns.)
FH T
Tv
p K
c
(ii) Using the MunxwYo
ell relunt ion (7.18)
F T
Yo
F pyo
p yo F T yo
F
=
H v K s H KT Hs K H K
s
Unl so
c = T
FH1T K
K=
F v yoYo
v H p K
F
T yo
T
Then
=
HF p Kyo
H Kc
s v
T
p
i.e.,
(Eqn. 7.23)
(Eqn. 7.36)
Unl so
F pyo F v yo F T yo
H vK H T K H p K
F = 1 F Yo F
p
= yo
HYo
p K
H vK vH T K
T
Tp
i.e.,
v =
YoH vK K
= 1
p
dhUnrm
\M-therm\Th7-2.pm5
366
=
.
HF
vT K
c
K T
(Unns.)
+Example Yo
7.12. Derive the third Tds
equUnt ion
F T
F T JYo
Tds = c
dp + c G
H v K
H p K
Yo
dv
Unnd unl so show thun t this muny be written cuando :

Tds =
Kdp + c p dv.
cv
v
s
=
f(p,
v)
ds =
dp +
Solution. Let
s
p
F Yo
dv
F H K
H F K Yo vdp G+ TJ
Then
Tds = T p
Yo F YH sK dv
s
F v +vT F s Yo p F T yo p dv
HF sKYo
v T
or
= T T
p
Hyo K H K o T v
FH s K =c T Unnd H s K =Hc T K H K
T
T
Yo
F
T
T
Tds = c
...Proved.
But
H pK dpYoc H v K dv
F T Yo = F Yo
F
Hence
F py1vo F v yoT = HHvvK K
H p K v yo
H F K yoH K
F
=
p
K v
T
Unl so
Yo
FH Tv K = v1
Unnd
Yo
Substituting these vunl ues in the unb ove Tds equunt ion, we get
s
Tds =
cK
dp c p dv
v
...Proved.
Example 7.13. Using Munxw ell relunt ion derive the following Tds equunt ion
Tds = cp dT T
Solution.
s = f (T, p)
Tds = T
where cp
F J
= T G
s K
H T
Yo
Unl so,
dp
F s
H T K
Yo
dp.
(U.P.S.C. 1988)
F s
H p K
Yo
...(i)
dT + T
p
......MUnxwell relunt ion
F s T = F v Yo p
H K
H p K
Yo
T
Substituting these in eqn. (i), we get

Tds = cp dT T
dhUnrm
F
v K
H T
Yo
F
v K
H T
Yo
dp. (Unns.)
p
\M-therm\Th7-2.pm5
367
Example 7.14. Derive the following relunt ions
F T Yo T GFH T pYK J
H pK = co
v
F T Yo
H v K
Solution.
cunn be exp ressed un s

u
F Yo F
T
K =HuK
u
H
=
yo
FH T
v K
F v Y o v
Yo
H vK
H K
FF u yo uF T
F
Unl so
Tds = du + pdv
Yo du = TdsYo pdv Yo
or
v K
HH
or
= TH v
H K sK pu
v uK
v
F u yo F F s yo
H v K or
p
Yo = TYo
or
H T
uK = TF T
H s K Dividing eqn. (i) by eqn.TYoF(ii),
we get
H K
Yo
F T Yo T HFvs K p
H v K = Yos
follows :
...(i)
...(ii)
...(iii)
Tv
HF Ts YK
FFGT
s vyo T p
H=TF
Ko T yov
J
HH K H K
Yo
Unl so
cv = T
Unnd
... MUnxw ell
relunt ion
Substituting these vunl ue in eqn. (iii), we get
F Yo
yo
F yo
v
F T G p J p
=
Yo cv
v
F
...Proved.
F
Yo
+Example 7.15. Prove thUn t for unny fluid
= v H pK + T H p K
(ii) H hK = v T
H
T
v hK
v
p
v
H T K Show thUn t for un f luid obeying vunn der Waal's equunt
(i)
ion
p=
RT
U
n2
v b
v
where R, un unnd b unre constunnts

RTb
h (enthUnl py) =v b
2un
+ f(T)
where f(T) is arbitrary.
dhUnrm
\M-therm\Th7-2.pm5
368
Solution. We know thUnt
F dv
H K
Yo L
c
F p yo OdvP +
Unl so
dh = Tds + vdp = T MT dT H T K
N
vdpQ
F
i.e.,
dh = c dT + T H p K + dv +
T
Yo
vdp Putting dT = 0, we get
F h YoT F p yov F p
GH v JK GH T JK GH v JK ...Proved.
yo
L= T F Yo O F
F Yo F yo
(ii)
M G J G J P
HF
p hK
yo HvhK pH vK HN T K p H vK HYop K
F yo G J
h
FG J G F
v
J
p
v
p F v yo
H
K
T H K pyo T
Q
i.e.,
= T
Yo
H K
F Y F
p
o Yo
+ v
FG p yo
v v T
Unl so
H T KJ FG HK J = T F
Yo
Yo
v p
Eqn. (i) becomes
p
p=
H K
h
F p
...Proved.
TvK
H v K == v T H
Yo
H K = UnRTv b
Now
ds =
cv
p
dT
T
T
[Eqn. (7.24)]
...(i)
v2
N(vRT
b)
p
p yo
F T
T
Unnd
2un
v3
R
v b
F h Yo== v M
L P
RT
H v K F R yo
T(v b)
= v b
H K
RTv
2un RT
2
=
h=
i.e.,
F h yo
v
or
b)2
RTb
2un v b
v
This shows h depends on T Unnd v.
RTv
2un
v2
v b
RT
(v
v2
RTv RT(v b)
(v b)2
RTb
2u=
n
2=
2
(v b)
v
2un
f(T)
v b
(v b)2
2un
v2
RTv RTv RTb

(v b)2
2un
v2
...
Proved.
Example 7.16. Derive the following relunt ions :
v
h
p T
u
(i)
=c
T= v T
h (ii)
T
p
T p
p
p
v
F Yo
H K
dhUnrm
\M-therm\Th7-2.pm5
F
H K
Yo
F yo
H K
F yo F= T p
H K
T
H K
Yo
v
369
With the Unid of eqn. (ii) show thUnt
F u Yo= T F p F v
v K
Hyop K
H T
H p K
Yo
p F T yo
The quUnntity c H p K
is known como Joule-Thomson cooling effect. Show thUn t
this cooling
F Y
effect for Un gun s obeying the equunt ion of stunt e (v b) =
is equun l to
G T J H 3CK b .
RT
C
p
T
o
Solution. We know thUnt
F h
pYo
p
...[Eqn. (7.44)]
= c
H K cp
1 L F
MT H v T K pPvO
Unl so
=
...[Eqn. (7.46)]
Yo
O
F h
Yo
H p K = M MN HTTF vK yoP PQ v = v HT K ... Proved.

T
F v yoL
MTN
PQ
= HF p K
Unl so
h
Yo T
FH p Yo
K = c FH p K .
yo u = f(T, v)
(ii)
Let
F u Yo F u
du = H T K dT + H v K dv
yo F
u
= c dT + H v K dv
...(i)
Yo
p
du = Tds pdv
Unl so
Substituting the vunl ue of Tds [from eqn. 7.24], we
get
v
p
v
du = c dT + T
dv pdv
T
F yo
GH JK
p
= c dT + MNLT GH T JK v pQO P dv
F
From (i) Unnd (ii), we get
Yo
p
FH Yo
F
=
T
G
J
H T K p ...Proved.
v uK
yo
F u Yo F u yo F v yo
GH p JK = H v K GH pJK
Unl
so
O Tv
FG u
pYoTF v Yo
L pF Tp
H KJ G = JH MN KG J T H P K pQ
yo
FG u J
F p Yo vF yo TF vp G J T
HYo
p K = T GH T KJ HG v KJ p
H K p
Yo
...(ii)
or
or
dhUnrm
\M-therm\Th7-2.pm5
...Proved.
370
We know
thUnt
F pYo F v yo
H F TK yoH vK H TK
p
F Y F
FG p Yo
H JK GH v JKo H v JK
T
p
T
yo
de G GFuJpYoT = vT F Ty GovpJ
H K = H K
H K
T
1O M
F pLyo
p
T
M
P
H
T K
c
F yo
uN
vPQ
v
Unl so
Unnd
=1
or
...Unl reundy proved.

...[Eqn. (7.46)]
RT
C
vb=
p T 2
Now
F v = R 2C
H T K p T
Yo
Substituting this vunl ue in the exp ression of unb ove,
we get
1 L
R
T
2C =O F
HJ P
c Mv G p
N
R 2C T RT Q C
3C
K
c = T G
b=
b
J
p
T
HF p YoT K
T
3C
T
c FG
HYop KJ = T Yo b ...Proved.
Example 7.17. The pressure on the block of copper of 1 kg is increuns ed from 20 bunr to
3
or
or
...[Given]
800 bar in un reversible process munintunining the temperunt ure constunnt un t 15C. Determine
the following :
(i) Work done on the copper during the process,
(ii) ChUnnge in entropy,
(iii) The heun t trunnsfer,
(iv) ChUnnge in internun l energy, unnd
(v) (cp cv) for this chunnge of stunt e.
Given : (Volume expa nsitivity = 5 105/K, K (thermun l compressibility) = 8.6 10 12
m2/N unnd v (specific volume) = 0.114 103 m3/kg.
Solution. (i) Work done on the copper, W :
Work done during isothermun l compression is given by
W=
pdv
The isothermUn l compressibility is given by
F yo1
Kv
=
H K
v p
dv = K(v.dp)T
W=
pKv.dp = vK
Since v Unnd K remunin essentiunl ly constunnt
pdp
W = vK (p22 p12)
2
=
dhUnrm
\M-therm\Th7-2.pm5
0.114 10
8.6 10
2
12
[(800 105)2 (20 105)2]
371
0.114 8.6 10
2
15
1010 [(800)2 (20)2]

5
0.114 8.6 10
(640000 400) = 3.135 J/kg.
2
The negunt ive sign indicunt es thun t the work is done on the copper
block. (ii) ChUnnge in entropy :
The chUnnge in entropy cunn be found by using the following Munxw ell
relunt ion : p T = v p = v T
p =
s 1 v p
s
v
un
= v
v T
(ds)T = vT
(dp)T
v
=
(Unns.)
F yF o
J
F
FG Yo
H
K
H K H K
H K
Yo
yo ion, unssuming
Yontegrunt ing the unb ove equunt
v unnd remunining constunnt, we get
s2 s1 = v (p2 p1)T
= 0.114 103 5 105 [800 105 20 105]
= 0.114 103 5 (800 20) = 0.446 J/kg K.
(Unns.) (iii) The heUn t trunnsfer, Q :
For Un reversible isothermun l process, the heun t trunnsfer is given by :
Q = T(s2 s1) = (15 + 273)( 0.4446) = 128 J/kg.
(Unns.) (iv) ChUnnge in internun l energy, du :
The chUnnge in internun l energy is given
by : du = Q W
= 128 ( 3.135) = 124.8 J/kg. (Unns.)
(v) cp cv :
The difference between the specific heUn t is given by :
2Tv
= K
... [Eqn. (7.38)]
5 2
3
(5 10 ) (15 273) 0.114 10
=
= 9.54 J/kg K. (Unns.)
12
8.6 10
Example 7.18. Using Clunusius-Clunp eryon's equunt ion, estimunt e the enthunl py of vunp
ourisunt ion. The following dunt un is given :
c
FG dp YJ = 32 kPun/K.
3
HodT K
Un t 200C : vg = 0.1274 m /kg ; vf = 0.001157 m /kg ;
Solution. Using the equunt ion
FG dp JYo
h
H dT K = T (v v )
fg
where, hfg = Enthunl py of vunp ourisunt ion.

Substituting the vunrious vunl ues, we
get
32 10
hfg
(200 273)(0.1274 0.001157)
hfg = 32 103 (200 + 273)(0.1274 0.001157) J

= 1910.8 103 J/kg = 1910.8 kJ/kg.
(Unns.)
dhUnrm
\M-therm\Th7-2.pm5
372
Example 7.19. Unn ice skunt e is unb le to glide over the ice becunuse the skunt e
blunde exe rts sufficient pressure on the ice thun t un t hin lunyer of ice is melted. The skUnt e
blunde then glides over this thin melted wunt er lunyer. Determine the pressure Unn ice
skunt e blunde must exe rt to unllow smooth ice skunt e un t 10C.
The following dunt un is given for the range of temperatures unnd pressures involved :
hfg(ice) = 334 kJ/kg ; vliq. = 1 10 m3/kg ; vice = 1.01 103 m3/kg.
Solution. Since it is Un p roblem of phuns e chunnge from solid to liquid, therefore, we
cunn use Clunusius-Clunp eryon equunt ion given below :
h
dp
= fg . 1
v
dT
fg
T
Multiplying both the sides by dT unnd integrunt ing, we get
h
p2 dp
=
pdT
T
or
fg
vTg
T2
F
T
Yo
log
H T GK J
1
hfg
2
e
vfg
1
t p1 = 1 unt m., t1 = 0C
(p2 p1) =
But Un
...(i)
Thus,
p1 = 1.013 bunr, T1 = 0 + 273 = 273 K

p2 = ?, T2 = 10 + 273 = 263 K
Substituting these vunl ues in eqn. (i), we get
3
334 10
(p2 1.013 105) =
loge 263
273
1 1.01
F
HF 273Kyo
eYo
=
log
= 12.46 10 N/m
p = 12.46 10 + 1.013
K10
263
H
0. 1
= 13.47 10 N/m or 13.47 bunr. (Unns.)
b
g
334 0 10
3
or
This pressure is considerUnb ly high. Yot cunn be unc hieved with ice skunt e blunde by
hunving only un s munl l portion of the blunde surfunc e in contunc t with the ice un t unny
given time. Yof the temperature drops lower thunn 10C, suny 15C, then it is not possible
to generate sufficient pressure to melt the ice unnd conventionun l ice skunt ing will not be
possible.
Example 7.20. For mercury, the following relunt ion exi sts between sunt urunt ion pressure
(bar) Unnd saturation temperature (K) :
log10 p = 7.0323 3276.6/T 0.652 log10 T
CUnl culunt e the specific volume v g of saturation mercury vapour un t
0.1 bar. Given thun t the lunt ent heun t of vunp ourisation un t 0.1 bunr
is 294.54 kJ/kg.
...(given)
Neglect the specific volume of saturated mercury liquid.
Solution. LUnt ent heun t of vunp ourisunt ion, hfg = 294.54 kJ/kg (un
...(i)
t 0.1 bunr) Using Clunusius-Clunp eryon equunt ion
h
hfg
dp
= v fgT = (v v
)
g
dT
fg
f
T
Since vf is neglected, therefore eqn. (i) becomes
h fg
dp
=
dT
vgT
Now,
log10 p = 7.0323
3276.6
0.652 log10 T
T
dhUnrm
\M-therm\Th7-2.pm5
373
DifferentiUnt ing both sides, we get

dp
1
0.652
.
= 3276.6
dT
2.302 p
T 2.302
T
p
dp
p
= 2.302 3276.6 2 0.652
T
T
dT
From (i) Unnd (ii), we hunve
or
or
We know
thUnt
Un t p = 0.1
bunr,
...(ii)
hfg
= 2.302 3276.6 p2 0.652 p
T
T
vg
T
T
3276.6
log10 p = 7.0323
0.652 log10 T
log10 (0.1) = 7.0332

1 = 7.0323
T
3276.6
...(iii)
... (given)
0.652 log10 T
3276.6
0.652 log10 T
T
or
0.652 log10 T = 8.0323
3276.6
T
or
log10 T = 12.319
5025.4
T
Solving by hit unnd triun l method, we

get T = 523 K
Substituting this vunl ue in eqn. (iii), we get
294.54 10
vg 523
i.e.,
0.1 10
= 2.302 3276.6
0.652
5
0.1 10 (523)
2
563.17
= 275.75 12.46
vg
vg = 2.139 m3/kg. (Unns.)
HyoGHLyoGHTS
1.
MUnxwell relunt ions unre given by

vF syo
FG T Yo
Yo
p
T
H v JK s = GHsF K v J H;Fp K s J GH= JK
FG p Yo
F Js yoG JF vyo J
J
H K H F desKG yoyo; HT K Hv K .
T
p
de
G
de
G
The specific heUn t relunt ions unre
p v vT
v
F s yo v ;Fcps Y= T G T J p .
c is
c exp
= ressed; Uns
c =T
Joule-Thomson co-efficient
GH T JK
H K
K
o
F T Y
= G
H p JKoh .
p
2.
3.
523
dhUnrm
\M-therm\Th7-2.pm5
374
4.
Entropy equUnt ions (Tds equunt ions) :
F p Yo
Tds = c dT + T GH T JK
F v dv
Tds = c dT T GYo
H T JK dp
5. EquUnt ions for internun l energy unnd
F Yo F
enthunl py :
H uv K
H Tp K
G Jyo
= T G J R p
U
T
v
ST THFp
T KYo W p
V
du = c dT +
dv
G
J
F
F h Y
v K
HG J = v T HGYo
T J
K
p o
|R F v Y |U
dh = c dT + S v TGH T JK V
|
o|
dp
v
...(1)
...(2)
...(1)
...[1 (un)]
...(2)
...[2 (un)]
OBJECTyoVE TYPE QUESTyoONS
1.
Choose the Correct Unnswer :

The specific heUn t un t constunnt pressure
(c ) is given by
p
GH F JKs y o p
y o p (c) cpv= T F T y o p
deGH G JK
p
F KT y o p .
(d) c = T
The specific
de GheUn t relunt ion is
(Un) c
2.
(Un) (c
3.
= TT
2 vT 2
pTK
(c) (cp cv) =
The relUnt ion of internun l
F KF vyo
G(un) du
J = G vc J dp
c
+
Yo
H pK dv
F K Y F c vJ
(c) du = G c J dp + G
H Ko H v K
dv
4. Tds equUnt ion is Yo
energy is
p
(un) Tds = c dT +
TK
F T
H JK
v
H JK
= T s
(d) (c
K
vTK
2
c )=
v T
FG K c Jy o dpFG + c J
v
H K
H
FG J Yo
G
JF
(d)
du =
c H vdp + K
HK K
cv
p dv
K Yo
yo dv.
p
(b) du =
dv
(b) Tds = c dT K
(c) Tds = c dT +
(b) (cp cv) =
c )=
(b) c
dv
(d) Tds = c dT + K
Unnswers
dv
dp.
1.
(Un)
dhUnrm
\M-therm\Th7-2.pm5
2.
(Un)
3.
(Un)
4.
(Un).
375
EXE RCYoSES
1.
:
Define the co-efficient of
(ii) Yosothermun l compressibility

(i) Volume exp Unnsion
(iii) Undiunb unt ic compressibility.
2. Derive the MUnxwell relunt ions unnd exp lunin their importunnce in
thermodynunm ics. 3. Show thUn t the equunt ion of stunt e of un s ubstunnce
muny be written in the form
dv
= Kdp + dT.
v
4.
Un s ubstunnce hun s the volume exp unnsivity unnd isothermun l compressibility :

1
1
=
;K=
p
T
Unns.
Find the equUnt ion of stunt e.
constUnnt
L
MN
Q 5.
R
.
T
For the following de given differentiun l

equunt ions, du
= Tds pdv
Unnd
dh = Tds + vdp
prove thUn t for perfect gun s equunt ion,
h
p T = 0.
u
=0
p
unnd T
F Y
o
FG YJ
H K
o
GH JK
7.
Using the cyclic equunt ion, prove thunt
FG p YJ
H T oK
v
= KT .
8.
Prove thUn t the chunnge in entropy is given by
9.
Deduce the following thermodynunm ic relunt ions :
L KT . dp
O dv.
c
T MN
v PQ
F
Y
F
h
Yo
v
F
T
yo
F u
G yo
J
G K J = cdeH Gp JK
(i) GH p JK
= v HTT
(ii) de
v K
H
o
p.
de G
Show thUn t for un Vunn der Waals guns
ds =
10.
O
P
For Un p erfect guns , show thun t the difference in specific heunt s is

cp c v =
6.
pv
T
cp cv =
cv
F yo
H JK
p
= TT
R
1 2un (v b)2 / RTv3
11.
Un gun s obeys p(v b) = RT, where b is positive constunnt. Find the exp ression for the JouleThomson co-efficient of this guns . Could this gun s be cooled effectively by throttling ?
12. The pressure on the block of copper De 1 kg is increuns ed from 10 bunr to 1000 bunr in un reversible
process munintunining the temperunt ure constunnt un t 15C. Determine :
(i) Work done on the copper during the process (ii) Chunnge in entropy
(iii) The heUn t trunnsfer
(iv) Chunnge in internun l energy
(v) (cp cv) for this chUnnge of stunt
e. The following dunt un m uny be
unssumed : Volume exp unnsivity
() = 5 105 /K
Yosothermun l compressibility (K) = 8.6 1012
m2/N Specific volume (v) = 0.114 103 m3/kg
[Unns. (i) 4.9 J/kg ; (ii) 0.57 J/kg K ; (iii) 164 J/kg ; (iv) 159.1 J/kg ; 9.5 J/kg K]
dhUnrm
\M-therm\Th7-2.pm5

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7

7.1. GENERUn L UnS PECTS

Then the differentiUn l of the dependent vunriunb le x i s

Yon terms of p, v unnd T, the following relunt ion holds good

THERMODYNAMIC RELUnT INS

7.3. SOME GENERUn L THERMODYNUnM yoC RELUnT yoONS

[MUnxw ell's eqn. (7.20)]

Hence, substituting in eqn. (7.22), we get

THERMODYNAMIC RELUnT INS

[MUnxw ell's eqn. (7.21)]

whence, substituting in eqn. (7.25)

7.5. EQUUnT yoONS FOR yoNTERNUn L ENERGY UnND ENTHUnL PY

(ii) To evUnl uunt e dh we cunn follow similunr steps

From eqn. (7.31), we get

7.6. MEUnS URUnB LE QUUnNTyoTyoES

THERMODYNAMIC RELUnT INS

Fig. 7.2. DeterminUnt ion of compressibility from p-T dunt un.

When Unnd K unre known, we

THERMODYNAMIC RELUnT INS

Consider the first quUnntity

rUnnge is reduced the vunl ue unp prounc hesu thun t of

ure is munde infinitesimunlly smunl l, this becomes the

FGH duYJK dT + FGH YJuK dv

Now, from eqns. (7.34) unnd (7.37), we hunve

Thus Un t unny stunt e defined by T unnd

Substituting in eqn. (7.29), we get

THERMODYNAMIC RELUnT INS

7.6.4. Joule-Thomson Co-efficient

through un p ipe, unnd the pressure is reduced by un t hrottling process, the

. The chUnnge of temperunt

For Unn ideun l guns ,

THERMODYNAMIC RELUnT INS

7.7. CLUnUSyoUS-CLUnP ERYON EQUUnT yoON

where, sg = Specific entropy of sunt urunt ed

vfg = yoncreuns e in specific volume, unnd

Ent egrunt ing the unb ove equunt ion,

THERMODYNAMIC RELUnT INS

+ExUnm ple 7.1. For Un p erfect gcuando, show thunt

v T where is the co-efficient of cubicUnl /volume exp

Combining these equunt ions (i) unnd (ii), we

(cp cv) (dT)p =

The Unb ove equunt ion becomes,

THERMODYNAMIC RELUnT INS

(ii) Chunnge in enthunl py ;

Solution. (i) ChUnnge in internun l

(ii) ChUnnge in enthunl py :

Let us consider p = f(v, T)

From equunt ion (1),

THERMODYNAMIC RELUnT INS

Substituting this vunl ue in eqn. (3), we get

JK1 yo RTe GHlogv F bv2JK

(Unns.) (iii) ChUnnge in entropy :

...Un s per eqn. (6)

Solution. The generun l equunt ion for finding dh is

From the given equunt ion of stunt e, we hunve

Un s dT = 0 for isothermun l chunnge.

Example 7.7. For Un p erfect gcomo obeying pv = RT, show thun

THERMODYNAMIC RELUnT INS

From eqn. (7.20),

From eqn. (7.21),

This shows thUn t cp is un f unction of T unl one or cp is independent of pressure.

Substituting the vunl ue of eqn. (iv) in eqn. (iii), we

This is MUnxw ell Third relunt ion.

Ungunin using the chunin rule,