CHAPTER 2 THERMODYNAMIC RELATIONS

2.1 SOME MATHEMATICAL THEOREMS

For elementary materials such as incompressible substances and ideal gases, simple
equations of state provide the relations between the thermodynamic properties. If we
consider complex materials and real systems, simple equation of states are
inadequate to describe the properties. Hence, more mathematical equations are
required to represent the realistic processes. Amongst the various thermodynamic
properties, p, v, T are directly measurable whereas u, h, s are not directly
measurable. This necessitates for developing thermodynamic relations apart from the
equation of states.

The following three theorems are the base for developing the various thermodynamic
relations.

2.1.1 THEOREM-1 If a relation exists among the variables x, y and z , then z may
be expressed as a function of x and y .
or,
z z (2.1)
dz = dx + dy
x y y x
If,
z (2.2)
= M
x y
and

z (2.3)
=N
y
Then,
dz = M dx + N dy (2.4)

where M and N are functions of x and y . Differentiating M partially with respect to

y and N with respect to x ,
M 2 z (2.5)
=
y x x.y
And,

N 2 z (2.6)
=
x y y.x

18
Hence,

M N (2.7)
=
y x x y

This is the condition of an exact (perfect) differential. If x and y are two independent
thermodynamic properties, then z will be also a thermodynamic property provided it
satisfy Eq. (2.7). For example, let us consider the following relation,

dz = p dv + v 2 dp (2.8)

Here, M = p and N = v 2

M N
Now, = 1 and = 2v which does not satisfy Eq. (2.7). Hence z is not a
y x x y
thermodynamic property.

Let us consider another relation,

z = p dv + v dp (2.9)
With similar reasoning it can be easily established that z is a thermodynamic
property in this case.

With more than 3 variables, say x1 , x2 , x3 and z ,

z = ( x1 , x2 , x3 ) (2.10)

z z z (2.11)
dz = dx1 + dx2 + dx3
x1 x2 , x3 x2 x1 , x3 x3 x1 , x2

For dz to be an exact differential,

z z z z z z (2.12)
= , = , =
x1 x2 x2 x3 x3 x1

For k number of variables

k
z (2.13)
dz = .dxi
i =1 xi
or,
z z (2.14)
= , ji
x j xi xi x j

19
2.1.2 THEOREM 2 If a quantity f is a function of x , y , and z , and a relation exists
amongst x , y and z , then f is a function of any two of x , y , and z .
f = f ( x, y , z ) (2.15)

or,
x = x ( y, z ) (2.16)

x = x( f , y) (2.17)

x = x( f , z) (2.18)

If x = x( f , y)
x x (2.19)
dx = df + dy
f y y f
Similarly, if y = y ( f , z )

y y (2.20)
dy = df + dz
f z z f
From Eqs. (2.19) and (2.20), we have

x x y y (2.21)
dx = df + . df + dz
f y y f f z z f
or,

x x y x y
(2.22)
dx = + df + dz
f y y f f z y f z f

If x = x ( f , z ) , then
x x (2.23)
dx = df + dz
f z z f
From Eqs. (2.22) and (2.23),

x x y (2.24)
=
z f y f z f

Eq. (2.24) can be rewritten as

z x y (2.25)
=1
x f y f z f
20
2.1.3 THEOREM 3 Among the variables x , y , and z , any one variable may be
considered as a function of the other two. Thus,
x = x ( y, z ) (2.26)

x x (2.27)
dx = dy + dz
y z z y
Similarly,
z = z ( x, y ) (2.28)

z z (2.29)
dz = dx + dy
x y y x
Hence,

x z z
(2.30)
x
dx = dy + + dy
y z z y x y y x
or,
x x z x z
(2.31)
dx = + . dy + dx
y x z y y x z y x y
or,
x x z (2.32)
dx = + . dy + dx
y x z y y x
Hence,
x x z (2.33)
+ . = 0
y x z y y x
or,
x z y (2.34)
. . = 1
z y y x x z

2.2 MAXWELL RELATIONS

A pure substance existing in a single phase has only two independent variables. Out
of the eight quantities p, V , T , S ,U , H , F , and G any one may be expressed as a
function of and other two quantities.
For a pure substance undergoing an infinitesimal reversible process
dU = TdS pdV (2.35)

21
 dH = dU + pdV + Vdp = TdS + Vdp (2.36)

dF = dU TdS SdT = pdV SdT (2.37)

dG = dH TdS SdT = Vdp SdT (2.38)

Since, U , H , F and G are thermodynamic properties and exact differentials of the

type dz = Mdx + Ndy (Eq. (2.4)), then from Eq. (2.7),

M N
=
y x x y

Applying this to the four equations (Eqs. (2.35-2.38))

T p (2.39)
=
V S S V

T V (2.40)
=
p S S p

p S (2.41)
=
T V V T

V S (2.42)
=
T p p T
Equations (2.39-2.42) are known as Maxwell relations.
The Maxwell relations need not be remembered. It can be easily found out from the
thermodynamic mnemonic diagram. Construct a square with two diagonals as shown
in Fig. 2.1.

22
 T F V

G U

P H S

Fig. 2.1 Thermodynamic mnemonic diagram

Mark the positions at the middle of the sides as well as at the corners. Write down
the variables G, P, H, S, U, V, F and T starting from the middle of left hand side and
in anti clockwise direction. The relations (Table 2.1) for du , dh, dF and dG can be
easily memorized by using the phrase

Great Physicists Have Studied Under Very Famous Teachers

( G, P, H , S ,U ,V , F , T ) by considering this thermodynamic mnemonic diagram.

Diagonals are then drawn pointing away from the two bottom corners. Now, if an
expression for dG is required (that is located at the middle of the line connecting the
points T and p ), we first form the differentials of dT and dp , and then link the two
with their conjugates as illustrated below:

dG = S ( conjugate of T with the minus sign due to the diagonal pointing towards T )
x dT +V ( that is conjugate of p with the plus sign due to the diagonal pointing away
from p ) x dp

Table 2.1 Maxwell relations

Differential Conjugate Maxwell Remarks

Relation
u du = Tds pdv T, p T p u = u ( s, v )
=
v s
h dh = Tds + vdp T,v T v h = h ( s, p )
=
p s
f df = sdT pdv s, p s p f = f (T , v )
=
v T
g dg = sdT + vdp s, v s v g = g (T , p )
=
p T

2.3 FIRST T dS RELATION

23
Consider,

S = S (T ,V ) (2.43)

S S (2.44)
dS = dT + dV
T V V T
or,
S S (2.45)
TdS = T dT + T dV
T V V T
Now,
dQ = dU + pdV = TdS (2.46)
and,
S (2.47)
CV = T
T V
where CV is the heat capacity at control volume ( kJ/K).
Hence,
S (2.48)
TdS = T dT + CV dV
T V

Therefore, applying the third Maxwell relations,

p (2.49)
TdS = T + CV dV
T V

Equation (2.49) is known as First T dS relation.

2.4 SECOND T dS RELATION

Again, let us consider

S = S (T , p ) (2.50)

S S (2.51)
TdS = T dT + T dp
T p p T
Now,

S (2.52)
Cp = T
T p

where, C p is the heat capacity at constant pressure (kJ/K).

Therefore, applying Maxwells fourth relation,

24
 V (2.53)
TdS = C p dT T dp
T p

This is known as 2nd T dS relation.

2.5 THIRD T dS RELATION

Let,
S = S (V , p ) (2.54)

Hence,
S S (2.55)
TdS = T dV + T dp
V p p V
Now,

V S T (2.56)
=1
S P T p V P

S S T (2.57)
=
V p T P V p
or,
S S T (2.58)
T =T
V p T P V p
Again,
S (2.59)
T = Cp
T p

S T (2.60)
T = Cp
V p V p
Again,
p S T (2.61)
=1
S V T V p V

S S T (2.62)
=
p V T V p V
or,
S S T (2.63)
T =T
p V T V p V
But,

25
 S (2.64)
T = CV
T V
Hence, Eq. (2.63) can be written as
S T (2.65)
T = CV
p V p V
From Eqs.(2.55), (2.60) and (2.65) We obtain,
T T (2.66)
TdS = CV dp + C p dV
p V V p

This is known as the third T dS relation.

2.6 DIFFERENCE IN HEAT CAPACITIES

From the first and second T dS relations we can write,

p V (2.67)
TdS = T + CV dV = C p dT T dp
T V T p
or,

( C p CV ) dT = T VT dp + T Tp dV
(2.68)

p V

or,
V p (2.69)
dT = T dp + T dV / ( C p CV )
T p T V
Again,
T T (2.70)
dT = dV + dp T = T (V , p )
V p p V
or,

V p (2.71)
T dp + T dV
T p T V T T
= dV + dp
( C p CV ) V p p V

Equating the coefficient of dV

p (2.72)
T
T T V
=
V p ( C p CV )

p V (2.73)
C p CV = T
T V T p
Similarly,
V p (2.74)
C p CV = T
T p T V
26
From Theorem 3,
p T V (2.75)
. . = 1
T V V p p T
Hence,
(2.76)
V p
2

C p CV = T
T p V T

Following interpretations can be made from Eq. (2.76)

V p
2

1. Since is always positive and for any substance is always

T p V T
negative, the difference of specific heats ( C p CV ) is always positive.
2. As T 0, C p CV . In other words, C p = CV at absolute zero temperature.
V
3. When = 0, then C p = CV
T p
4. For an ideal gas, pV = mRT
V mR V
= =
T p p T
p mRT
= 2
V T V
Hence, C p CV = mR
or, C p Cv = R

2.7 SOME DEFINITIONS

In a single phase region, where pressure and temperature are independent, we can
think of the volume as being a function of pressure and temperature.
V = V (T , p) (2.77)
or,
v = v(T , p ) (2.78)
Applying the chain rule of the calculus
v v (2.79)
dv = dT + dp
T p p T
v
The derivative represents the slope of a line of constant pressure on V T
T p
a plane. A similar interpretation can be given for the second derivative. These
derivatives are themselves intensive thermodynamic properties, since they have
definite values at any fixed thermodynamic state. The first represents the sensitivity
27
of the specific volume changes in temperature at constant pressure, and the second
is a measure of the change in specific volume associated with a change in pressure
at constant temperature. Isothermal compressibility, isentropic compressibility and
volume expansivity are defined as

1 V
Isothermal compressibility: kT =
V p T

1 V
Volume expansivity: =
V T p

The compressibility factors are frequently tabulated functions of state. The co-
efficient of linear expansion used in elementary strength of materials texts is
3 . Youngs modulus of elasticity is proportional to kT in terms of and kT , Eq.
(2.79) can be written as
dv = vdT kT vdp (2.80)

Usefulness of Eq. arises from the fact that and kT are sometimes slowly varying
functions of T and p . Another term in use is the isothermal compressibility defined
as
1 V (2.81)
ks =
V p s

TV 2 (2.82)
C p CV =
kT
Based on the definitions of isothermal compressibility and volume expansivity, the
specific heat differences can be written as

2.8 RATIO OF HEAT CAPACITIES

At constant entropy S , the two T dS relations become

V (2.83)
C p dTS = T dpS
T T

p (2.84)
CV dTS = T dVS
T V

28
 Cp V (2.85)
=
CV p
2.9 ENERGY EQUATION

For a system undergoing an infinitesimal reversible process between two equilibrium

states, the change in internal energy is

dU = Tds pdV (2.86)

Substituting the first T dS relation,

p (2.87)
TdS = T + CV dV
T V

p (2.88)
dU = CV dT + T dV pdV
T V
p
= CV dT + T p dV
T V

If U = U (T ,V ) , then
U U (2.89)
dU = dT + dV
T V V T

Comparing Eq. (2.88) with Eq. (2.89),

U p (2.90)
=T P
V T T V
Eq. (2.90) is known as the energy equation.

2.9.1 APPLICATION OF ENERGY EQUATION TO AN IDEAL GAS

For an ideal gas in a closed system, equation of state is

(2.91)
nRT
p=
V

p
(2.92)
nR p
= =
T V V T

U p (2.93)
= T. p = 0
V T T
29
U does not change with V at constant temperature.
Further, applying Theorem 2,

(2.94)
U p V
p V U = 1
T T T

Hence,
U p U (2.95)
p V = V = 0
T T T
p
Since, 0
V T
U (2.96)
=0
p T
From Eqs.(2.93) and Eq. (2.96) it is clear that U is neither a function of V nor a
function of p at constant temperature. Only possibility is that internal energy is a
function of temperature only.

For an open system

dH = Tds + Vdp (2.97)

From T ds relation,

V (2.98)
Tds = C p dT T dp
T p
Now,
V
(2.99)
dH = C p dT + V T dp
T p
Let, H = H (T , p )
Hence,

H H (2.100)
dH = dT + dp
T p p T

Comparing Eq. (2.99) and Eq. (2.100),

H V
(2.101)
p = V T T
T p
Now,

30
 H p V (2.102)
p V H = 1
T T T
For an ideal gas

V V (2.103)
=
T p T
Hence,
H (2.104)
p = 0
T

H does not change with p while temperature remaining unchanged.

H p V H
From, = 1 we can infer that =0
p T V T H T V T
H does not change with V while temperature remaining unchanged.

2.9.2 APPLICATION OF ENERGY EQUATION FOR THERMAL RADIATION IN

EQUILIBRIUM WITH THE ENCLOSURE WALLS
U
Let, u = energy density = = f (T )
V

p = radiation pressure exerted by a black body in an enclosure ( from electro

u
magnetic theory)=
3
Blackbody raditation is thus specified by the pressure, volume and temperature of
radiation.
U = uV (2.105)

u (2.106)
p=
3

U (2.106)
=u
V T

p 1 du (2.107)
=
T V 3 dT
Energy Equation is
U p (2.108)
=T p
V T T V
31
Substituting in energy equation

T du T du u (2.109)
u= p=
3 dT 3 dT 3

du dT (2.110)
=4
u T

On integration,
u = bT 4 (2.111)
where b is a constant.

Eq.(2.111) is known as Stefan-Boltzmann equation.

Since,

U = uV = VbT 4 (2.112)

x (2.113)
y = CV = 4VbT
4

V
And,
p 1 du 4 3 (2.114)
= = bT
T V 3 dT 3
From first T dS relation,

p 4 4 (2.115)
T dS = CV dT + T dV = 4VbT dT + bT dV
3

T 3

For a reversible isothermal change of volume, the heat is to be supplied reversibly to

keep temperature constant [TdS = Q ] .
4 (2.116)
Q = bT 4 V
3
For a reversible adiabatic change of volume,
4 4 (2.117)
bT dV = 4VbT 3dT
3
[Q = 0]
or,
dV dT (2.118)
= 3
V T
or,
VT 3 = constant (2.119)

32
If the temperature is one half of the original temperature, the volume of the blackbody
radiation is to be increased adiabatically 8 times its original volume so that the
radiation remains in equilibrium with the matter at that temperature.

2.10 JOULE KELVIN (JOULE-THOMPSON) EFFECT

2.10.1 THROTTLING DEVICES
A throttling device is the generic name of any device or process that simply dissipates
pressure energy by irreversibly converting it into thermal energy. Unlike nozzles and
diffusers, throttling devices provide no form of useful energy recovery. They merely
convert pressure energy into thermal energy through dissipative viscous flow
processes. A throttle need not have same inlet and outlet flow velocities, and,
therefore, it may have a significant specific kinetic energy changes across it.
Throttles may or may not be insulated, but they are usually such small devices and
have such high flow rates that the residence time of the fluid in them is too short for
significant heat transport of energy to occur. Consequently, a throttling device is
commonly taken to be adiabatic regardless of whether it is actually insulated or not.

The throttling phenomenon, also known as Joule Kelvin /Joule Thompson effect,
may be demonstrated by considering a steady-state, steady flow (SSSF) process
across a restriction, with a resulting drop in pressure. The restriction can be a porous
plug, an orifice plate, a butterfly valve, any type of flow or pressure control valve.
Even a geometry like sudden contraction or sudden expansion may give the desired
effect [ Fig.2.2].

p1 p<p p1 p<p
2 1 2 1

(b)
(a)

p p< p p
1
2 1 1
p<p
2 1

(d)
(c) p < p1
2
V1 V1
p1 p>p p1
2 1
V2 < V1 V2 > V1
(e) (f)

Fig: 2.2 (a) Orifice plate, (b) Porous plug, (Butterfly/throttle Valve ), (d) Any type of flow or
pressure control valve (e) sudden expansion, (f) Sudden contraction

33
The pressure and temperature of the fluid upstream and down stream of the
restriction are measured with suitable manometers and thermometers [Fig. 2.3].

ti V a lv e tf

p
p f
i
In s u la t io n

Fig. 2.3 Joule Thompson effect

Let pi and Ti be the arbitrarily chosen pressure and temperature before throttling and
let us assume that they are constant. By operating the restriction (say, a valve) the
fluid is throttled successively to different pressures and temperatures
p f 1 , T f 1 ; p f 2 , T f 2 ; p f 3 , T f 3 and so on. These are then plotted on the T p plane [Fig.2.4].

States after
f4 throttling
f3

f2
T

f5

f6 f1 State before
throttling
f7
i

h=C

Fig. 2.4 Isenthalpic states of a gas

All the points on this curve represent equilibrium states of some constant mass of the
fluid. The curve passing through all these points is an isenthalpic curve or isenthalpe.
The initial pressure and temperature of the fluid ( pi , Ti ) are then set to new values
and the fluid is throttled by controlling the restriction. Thus by throttling to different
states we can have a family of isenthalpes for the fluid [Fig. 2.5]. The curve passing
through the maxima of these isenthalpes is called the inversion curve.

34
 Inversion curve ( = 0)
j

T
Constant enthalpy
curves

Critical point

Saturation curve
Liquid Vapour
region

Fig. 2.5 Inversion and saturation curves on T-s plot

The numerical value of the slope of an isenthalpe on the T-p diagram at any point is
called the Joule Thompson coefficient j .
T (2.120)
j =
p h
Locus of all points at which j is zero is the inversion curve. The region inside the
inversion curve where j is negative is called the heating region and where j is
positive is called the cooling region.

The difference in enthalpy between two neighboring equilibrium states is

dh = Tds + vdp (2.121)
and the second T dS relation (per unit mass)
v (2.122)
Tds = C p dT T dp
T p

v (2.123)
dh = C p dT T v dp
T p

The second term in the above equation stands only for a real gas, because for an
ideal gas dh = C p dT .
1 v (2.124)
T
j = = T v
p h C p T p

For an ideal gas:

pv = RT (2.125)

35
 v R v (2.126)
= =
T p T T
1 v
j = T. v = 0
Cp T

There is no change in temperature when an ideal gas is made to undergo a Joule-

Thompson expansion.
For an incompressible fluid:

v (2.127)
=0
T p
Tv
j =
Cp

Thus an incompressible fluid is heated while undergoing throttling process.

Application of Joule-Thompson effect:

1. Vapor compression refrigeration system

2. Production of dry ice or solid CO2 for low temperature refrigeration

Example:
Joule-Kelvin coefficient J is a measure of the temperature change during a throttling
process. A similar measure of temperature change produced by an isentropic change
of pressure is provided by the coefficient S where
T
S =
p S
V
Prove that: S J =
Cp
Solution: The Joule Kelvin coefficient J is given by

V
T V
T p
J =
Cp

36
 S
Cp = T
T p
Maxwells Relations

V S
=
T p p T

S
T
p T V
J =
S Cp
T
T p
S T p V
=
p T S p T S C p
S T p
= 1
p T S p T S
T V
J = J =
p S C p
V
J = S
Cp
V
S J =
Cp

37