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CHAPTER 10: THERMODYNAMIC RELATIONS

Some thermodynamic properties such as P, T, V, and m can be measured directly, but many
others such as h, u, and s cannot be measured directly.
Therefore, it is necessary to develop some relations between these two groups so that the nonmeasurable properties can be evaluated.
The derivations are based on the fact that properties are point functions, and the state of a simple,
compressible system is completely specified by any two independent, intensive properties.

10.1 Two important relations (Some Mathematical Preliminaries):


A) Thermodynamic properties are continuous point functions and have exact differentials.
A property of a single component system may be written as general mathematical function z =
z(x,y). For instance, this function may be the pressure P = P(T,v). The total differential of z is
written as
where

Taking the partial derivative of M with respect to y and of N with respect to x yields

Since properties are continuous point functions and have exact differentials, the following is true

Exact diff. Eqn. condition


University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


B) Now we develop two more important relations for partial derivativesthe reciprocity and the
cyclic relations. Consider the function z = z(x,y) expressed as x = x(y,z). The total differential of x is

&
Now combine the expressions for dx and dz.

Rearranging,

Since y and z are independent of


each other, the terms in each bracket
must be zero. Thus, we obtain the
reciprocity relation that shows that the
inverse of a partial derivative is equal
to its reciprocal.

or

The second relation is called the cyclic


relation.

Chain rule
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


10.2 The Maxwell Relations:

The equations that relate the partial derivatives of properties P, v, T, and s of a simple
compressible substance to each other are called the Maxwell relations.
They are obtained from the four Gibbs equations. The first two of the Gibbs equations are those
resulting from the internal energy u and the enthalpy h. The second two Gibbs equations result from
the definitions of the Helmholtz function a and the Gibbs function g defined as
1) du T ds P dv
2) dh T ds v dP

a u Ts
da du T ds s dT
3) da s dT P dv

(1.b)
(1.a) u f s, v du u ds u dv u T ; u P

s v
v s
s v
v s
h
h
h
h
(2.a) h f s, P dh s ds P dP s T ; P v

(2.b)

a
a
a
a
a f T , v da
dT
dv
s;

P
(3.a)
T v
v T (3.b)
T v
v T
g
g
g
g
g f T , P dg
dT
dP
s;
v

T
P
T
P
(4.a)

g h Ts
dg dh T ds s dT
4) dg s dT v dP (Maxwell Relations)

(4.b)

Compare
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


10.3 The Clapeyron Equation:

The Clapeyron equation enables us to determine the enthalpy change associated with a phase
change, hfg, from knowledge of P, v, and T data alone.
Consider the third Maxwell relation;
During phase change, the pressure is the saturation pressure, which
depends on the temperature only and is independent of the specific
volume. That is Psat = f(Tsat). Therefore, the partial derivative
can be
expressed as a total derivative (dP/dT)sat, which is the slope of the
saturation curve on a P-T diagram at a specified state. This slope is
independent of the specific volume, and thus it can be treated as a
constant during the integration of the third Maxwell relation between two
saturation states at the same temperature. For an isothermal liquid-vapor
phase-change process, the integration yields
During the phase-change process, the
pressure also remains constant.
Therefore, from the enthalpy relation

Now we obtain the Clapeyron


equation expressed as :

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


Example: Using only P-v-T data, estimate the enthalpy of vaporization of water at
45oC. The enthalpy of vaporization is given by the Clapeyron equation as;
SOLN:
Using the P-v-T data from saturated steam
table for water 45oC
3
m
v fg (vg v f )@ 45o C (15.251 0.001010)
kg
m3
15.250
kg

dP

dT

sat

sat , 45 C

50o C 40o C

(12.35 7.385) kPa


kPa

0.4965
10o K
K

dP

dT

h fg Tv fg

Psat @50o C Psat @ 40o C

sat

m3
kPa kJ
(40
(45+ 273.15) K (15.250
)(0.4965
)
kg
K m3kPa
The actual value of hfg is 2394.0 kJ/kg. The Clapeyron equation approximation
kJ
2408.91
2371.1
is low by about 1 percent due to the approximation of the slope of the
kg
o
saturation curve at 45 C.

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


Clapeyron-Clausius Equation
For liquid-vapor and solid-vapor phase-change processes at low pressures, an
approximation to the Clapeyron equation can be obtained by treating the vapor phase
as an ideal gas and neglecting the specific volume of the saturated liquid or solid phase
compared to that of the vapor phase. At low pressures;
v v
g

v fg v g
RT
vg
P

For small temperature intervals, hfg can be treated as a constant at some average
value. Then integrating this equation between two saturation states yields

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


Example: Determine the saturation pressure of water vapor at -600C using the data
available in steam tables.
SOLN:
Tables do not give Psat for temperatures less than -400C. But we can use the
Clapeyron-Clasius equation for that purpose as that;

P2

ln
P1

sat

hig T2 T1


R T2T1

sat

Where;
T2=-400C
P2=0.0129 kPa (wrt T2)
hig=2838.9 kJ/kg (wrt T2)
R=0.46152 kJ/kgK for steam

0.0129

ln
P1

P1

IF T1=-600CP1=?

sat

2838.9 233.2 213.2

0.46152 233.2 213.2

0.0129
P1 0.00109kPa
2.4744
e

2.4744
sat

(Psat at -600C)

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


10.4 Some thermodynamic relations involving h, u, and s:
The changes in internal energy, enthalpy, and entropy of a simple, compressible
substance can be expressed in terms of pressure, specific volume, temperature, and
specific heats alone.
1) Consider internal energy expressed as a function of T and v : u=f(T,)

Recall the definition of


the specific heat at
constant volume

Recall third Maxwell


Relation 3.a

du Tds Pdv 1st law in differential form


v

s
T

s
T

v
P

v 1 s
P
T

v T
v

Cv
v

P T
T

P
v

Maxwell Rel. 3.a


v

P
u u2 u1 Cv dT T

T
v
T
T2

v2

P dv

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


2) Consider enthalpy expressed as a function of T and P : h=f(T,P)

h
dh

h
dT

P
P

dP
T

dh Tds vdP 1st law in differential form


h

S
T

S
T

P
v

P
v

S
T

CP
P

v
P

Maxwell Rel. 4.a

v
dh CP dT v T

dP

v
h h2 h1 C P dT v T

T
P
T
T2

P2

dP

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


3) Two parallel expressions can be derived for the change of s: s=f(T,P) & s=f(T,v)

s f T , P

s f T , v

s
s
ds
dT
dP
T P
P T

s
s
ds
dT dv
T v
v T
Maxwell Rel. 3.a

Maxwell Rel. 4.a

CP
v
ds dT
dP
T
T P
T
dT P v
s s2 s1 CP
dP
T P T P
T
2

Cv
P
ds dT
dv
T
T v
T
dT v P
s s2 s1 Cv
dv
T v T v
T
2

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


10.5 Some thermodynamic relations involving Cp and Cv:
1)

ds

CP
v
dT

T
T

CP / T

2)

ds

T T

Cv
P
dT

T
T

Cv / T

M
N

dP

2v
T

M
N

dv
v

C P

T T

Cv

2P
T

CP
C
v
P
dT
dP v dT
dv
T
T
T P
T v
T P / T v
T v / T P
T
dT
dv
dP dT

C P Cv
C P Cv
v
T P / T v
T v / T P
T
T

&

C P Cv
C P Cv
v P
P v

3) ds

v
C P Cv T

P T

v
T

T
P

Chain rule

v
P

v
T

dv

dP
v

v
P

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


Example: Show that Cv of an ideal gas does not depend upon specific volume.

Solution: For an ideal gas

Therefore, the specific heat at constant volume of an ideal gas is independent of specific
volume.
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


10.6 Volume Expansivity and Isothermal and Adiabatic Compressibility:
The volume expansivity coefficient, p is an indication of the change in volume that results from a
change in temperature while the pressure remains constant (i.e. p =f(T)).

1 V
p

V T

1 v

v T

The isothermal compressibility, T is an indication of the change in volume that results from a
change in pressure while the temperature remains constant (i.e. T =f(P)).

1 V
T

V P

1 v

v P

The adiabatic compressibility, s is an indication of the change in volume that results from a
change in pressure while the entropy remains constant (i.e. s =f(P)).

1 V
1 v
s

V P s
v P

Both p and T are thermodynamic properties of a substance, and for a simple compressible
substance are functions of two independent properties.
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


Example: Determine Cp Cv for ideal gases.
Solution:

v P
CP Cv T

T P v

1 vT P2

T p v
T
T v
2

RT
P
1 v
1 R
1
p


v T P v P T
1 v
1 RT
1
T

v P T
v
P2
P
v

1
vT

vT P2
T
C P Cv

1
T
P

Pv
R
T

The difference Cp Cv is equal to R for ideal gases and to zero for incompressible
substances (v = constant).
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


10.7 Variation of h, u, s, Cp, and Cv for the Ideal gases: Pv=RT

v
1) dh CP dT v T

P
2) du Cv dT T

3) ds

CP
v
dT

T
T

RT
R
dP

C
dT

dP dh CP dT
P

P
P

RT
R
P dv Cv dT T
dv du Cv dT

v
v

dP

CP
R
dT
dP
T
P

P
T
P
dT
dP
s s2 s1 C P
R
C Pav ln 2 R ln 2
T
P
T
P
T1
P1

4) ds

T2

Cv
P
dT

Cv
R
dT
dv
T
v

dv
v

T
v
dT v dv
s s2 s1 Cv
R
Cvav ln 2 R ln 2
T
v
T
v
T1
v1
T2

v
5) C P Cv T

RT
R 3T 2
R3
R
T
2 2 2 2 C P Cv R
v
P v
R
P

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


In discussing the accuracy of the ideal gas equation of state, we introduced the compressibility
factor, Z as a useful and important parameter in expressing the non-ideality of gases;
Pv
Z=1 always for an ideal gas

RT

Z<1 for all real gases


Another useful parameter in describing the behavior of a real gas relative to the ideal gas is the
residual volume, ;
=0 always for an ideal gas
RT

>0 for all real gases

The Joule-Thomson coefficient, J was also defined previously as that;


J=0 always for an ideal gas
T

J><0 for all real gases

10.8 Behavior of real gases: Pv=ZRT

PC Critical pressure
TC Critical temperature
vC Critical specific volume
Table A.1 ENGEL
Table A.6 Von WYLEN

Pr

P
Re duced pressure
PC

Tr

T
Re duced temperature
TC

v
vr
Re duced specific volume
vC

Z from
Generalised
Compressibility Chart
Fig.A-30a&Fig.A-30b ENGEL
Fig.A.5 Von WYLEN

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

A vapor is a gaseous species below its


critical temperature.
A gas is a species above its critical
temperature at a pressure low enough for
the species to be more like a vapor than a
liquid.

The highest temperature at which a


species can coexist in two phases (liquid
and vapor) is the critical temperature of that
species, Tc and the corresponding pressure
is the critical pressure Pc.
A substance at Tc and Pc is said to be at its
critical state.

CHAPTER 10: THERMODYNAMIC RELATIONS


GENERALZED COMPRESSIBILITY CHART

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


10.9 Equations of state:
An equation of state is an analytical representation of P-v-T behavior of gases.
Many different eqn. of states have been developed in literature. Three well-known classifications of
eqn. of state can be identified as, namely, generalized, empirical, and theoretical.
1) The best known of generalized eqns. of state is also oldest, namely, the van der waals
equation(1873);
RT
a

vb

v2

where a and b are evaluated from the general behavior of gases.


Redlich and Kwong eqn. of state (1949) is more accurate than van der waals eqn. of state.

RT
a

v b v v b T 1 / 2

2) One of the best known empirical eqns. of state is the Beattie-Bridgeman equation (1928);

RT

2 3 4
v
v
v
v

3) A different approach to this problem is from the theoretical point of view. The theoretical eqn. of
state, which is derived from kinetic theory or statistical thermodynamics, is written here in the form
of a power series in reciprocal volume;

Pv
B (T ) C (T ) D (T )
1

..........
RT
v
v2
v3

where B, C, D are temperature dependent and are called as virial coefficients.


University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


Example: Propane gas flows steadily through a pipe. The inlet state is 407 K, 5.21
MPa, and the exit state is 370 K, 4.26 MPa. Determine the heat loss from the propane to
the surroundings per unit mass of propane.

Conservation of mass

1 m
2 m

Conservation of energy

E in E out
m 1h1 Q out m 2 h2
Q out m ( h1 h2 )

Now, we approximate the enthalpy difference by using


the real gas analysis and determine the heat transfer
per unit mass as

Use Tables to obtain properties of propane; Tcr = 370 K,


Pcr = 4.26 MPa, Cp0 = 1.6794 kJ/kgK.

T1 407 K
P
5.21 MPa

11
. , PR1 1
12
.
Tcr 370 K
Pcr 4.26 MPa
T
370 K
P
4.26 MPa
TR 2 2
10
. , PR 2 2
10
.
Tcr 370 K
Pcr 4.26 MPa
TR1

Compressibility chart yields;

Zh1 145
. ,

Zh 2 2.5

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

CHAPTER 10: THERMODYNAMIC RELATIONS


If we assumed propane to be an ideal gas

The error in assuming propane is ideal


is

% Error

qout , real qout , ideal


qout , real

100%

135.37 62.14
100%
135.37
54.1%

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II