1

Thermodynamic
Properties
of Fluids
Chapter 6
Where are we?
S fs
W Q m zg
u
H

+ = + + A ] )
2
[(
2
1st law for open systems
AU + Au
2
/2 + g Az =Q +W
1st law for closed systems
0
) (
) ( > = + + A
G
t
sur cv
fs
S
dt
dS
dt
mS d
m S

2nd law for open systems

0
ln
0
P
P
T
dT
R
C
R
S
T
T
ig
p
=
A
}
Entropy change of a system
PVT relations allow for the calculation/estimation of
these properties
2
Thermodynamic Properties
The first and second laws of thermodynamics allow
us to determine:
Internal energy U
Entropy S
These properties and many other state properties
are often unknown and/or would be difficult to
measure
Hence:
This chapter combines the 1
st
and 2
nd
laws to
develop equations relating these properties to
other measurable properties (e.g. PVT and heat
capacities)
Overview of Chapter 6
Property relations
Residual properties
EOS in residual properties
Generalized property correlations
Two phase systems
Thermodynamic diagrams
Thermodynamic properties tables
3
Thermodynamic Functions
Lets define two new thermodynamic functions:
A U T S Helmholtz energy
G H T S Gibbs energy
From before we had:
H U +PV Enthalpy (first law)
U =Q +W Internal energy (first law)
Gibbs Free Energy
Gibbs Free Energy is the chemical reaction
potential energy of a substance or a system
G H T S
AG represents the energy available for doing
work
AH is equal to the total energy available
TAS is the energy not available for doing work
The change in free energy is represented by:
AG =AH TAS
4
Gibbs Free Energy
Gibbs Free Energy is a thermodynamic quantity which can
be used to determine if a reaction is spontaneous or not
AG <0: the reaction is spontaneous
AG >0: the reaction is not spontaneous
AG =0: the reaction is at equilibrium
e.g. Is the following reaction spontaneous at 25
0
C?
2H
2
(g) + O
2
(g) ----> 2H
2
O(g)
Solution:
We need to compute both AH and
AS for the reaction, get the value of
AG, and see if it is less than zero.
Compound AH
f
0
(kJ/mol) AS
0
(J/mol*K)
H
2
(g) 0.0 130.6
O
2
(g) 0.0 205.0
H
2
O(g) -241.8 188.7
AG = AH - T*AS
AG = -457 kJ/mol
The reaction is spontaneous, since AG < 0
Thermodynamic Functions
Lets define two new thermodynamic functions:
A U T S Helmholtz energy
G H T S Gibbs energy
From before we had:
H U +PV Enthalpy (first law)
U =Q +W Internal energy (first law)
5
Internal Energy Change
Assume a closed system containing homogeneous
phase of n mole:
From the first law:
d(nU) =dQ+dW
For a reversible process: d(nU) =dQ
rev
+dW
rev
Td(nS)
-Pd(nV)
d(nU) =Td(nS) Pd(nV)
For a one mole basis:
dU =TdS- PdV
This equation can be applied to any
process (reversible or irreversible)
Changes in Other Properties
For Enthalpy: d(nH) =dU +d(nPV)
d(nH) =dU +Pd(nV) +(nV)dP
=Td(nS) Pd(nV) +Pd(nV) +(nV)dP
=Td(nS) +(nV)dP
For a one mole basis:
dH =TdS+VdP
These equations
can be applied to
any process
(reversible or
irreversible)
Similarly
For A:
dA =-PdV - SdT
dG =VdP - SdT For G:
6
Enthalpy & Entropy
(as functions of T & P)
Enthalpy & Entropy are the thermodynamic properties
most often needed for engineering applications
we are usually concerned with changes in H & S
To find property relations for changes in H & S of a
homogeneous phase, the most useful relationship would
be based on T & P
dP
P
H
dT
T
H
dH
T P
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
= Consider: H=H(T,P)
C
p
P
T
V
T V
|
.
|

\
|
c
c

dP
T
V
T V dT C dH
P
p (

|
.
|

\
|
c
c
+ =
Enthalpy Change:
Enthalpy & Entropy
(as functions of T & P)
dP
P
S
dT
T
S
dS
T P
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
= Consider: S=S(T,P)
T
C
p
dP
T
V
T
dT
C dS
P
p
|
.
|

\
|
c
c
=
Entropy Change:
|
.
|

\
|
c
c

T
V
As can be seen, changes in H & S can be calculated for
specific changes in P & T if heat capacity and and PVT
data are available
For (cV/cT)
p
, we require V as a function of P & T (generally
obtained from PVT data that are fitted to EOS)
7
Enthalpy & Entropy
(as functions of T & P)
dP
P
S
dT
T
S
dS
T P
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
= Consider: S=S(T,P)
T
C
p
dP
T
V
T
dT
C dS
P
p
|
.
|

\
|
c
c
=
Entropy Change:
|
.
|

\
|
c
c

T
V
dP
P
H
dT
T
H
dH
T P
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
= Consider: H=H(T,P)
C
p
P
T
V
T V
|
.
|

\
|
c
c

dP
T
V
T V dT C dH
P
p (

|
.
|

\
|
c
c
+ =
Enthalpy Change:
Internal Energy
(as a function of P)
(cV/cT)
p
& (cV/cP)
T
can be obtained from PVT data that are
fitted to EOS
Consider: U = H - PV
V
P
V
P
P
H
P
U
T T T

|
.
|

\
|
c
c

|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
Differentiate for P at constant T:
P T
T
V
T V
P
H
before From |
.
|

\
|
c
c
= |
.
|

\
|
c
c
:
T P T
P
V
P
T
V
T
P
U
|
.
|

\
|
c
c

|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
8
Internal Energy & Entropy
(as functions of T and V)
Sometimes we may find T & V are more convenient to measure than
T & P
Under such conditions, relationships for changes in U & S as
functions of T & V would be very valuable
V V
T
S
T
T
U
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
From: dU = TdS - PdV
v
V
C
T
U
with = |
.
|

\
|
c
c
P
V
S
T
V
U
T T

|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
We can have:
T
C
T
S
v
V
=
|
.
|

\
|
c
c

V T
T
P
V
S
with |
.
|

\
|
c
c
= |
.
|

\
|
c
c
P
T
P
T
V
U
V T

|
.
|

\
|
c
c
=
|
.
|

\
|
c
c

Internal Energy & Entropy

(as functions of T and V)
dV
V
U
dT
T
U
dU
T V
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
= Consider: U=U(T,V)
v
C
dV P
T
P
T dT C dU
V
v (

|
.
|

\
|
c
c
+ =
Internal Energy Change:
P
T
P
T
V

|
.
|

\
|
c
c
dV
V
S
dT
T
S
dS
T V
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
Consider: S=S(T,V)
T
C
v
dV
T
P
T
dT
C dS
V
v
|
.
|

\
|
c
c
+ =
Entropy Change:
V
T
P
|
.
|

\
|
c
c
9
Property Relations
dP
T
V
T V dT C dH
P
p (

|
.
|

\
|
c
c
+ = dP
T
V
T
dT
C dS
P
p
|
.
|

\
|
c
c
=
T P T
P
V
P
T
V
T
P
U
|
.
|

\
|
c
c

|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
dV P
T
P
T dT C dU
V
v (

|
.
|

\
|
c
c
+ = dV
T
P
T
dT
C dS
V
v
|
.
|

\
|
c
c
+ =
Example Problem
A gas obeys the following equation of state:
The following data are given:
a = 0.00987 m
3
K/(kPa.kmol)
b = 0.080 m
3
/kmol
The specific heat C
p
at 1 bar and 400 K is 33.47
kJ/(kmol.K)
Compute the specific heat C
p
at 1200 kPa and 400 K
T
P
a RT b V P
2
) ( + =
10
Thermodynamic Relationships
(For Liquids)
These equations are no longer restricted to gases because (cV/cT)
p
& (cV/cP)
T
have been
replaced by | & k
Consider the following equations we had from before:
P T
T
V
T V
P
H
|
.
|

\
|
c
c
= |
.
|

\
|
c
c
T P T
P
V
P
T
V
T
P
U
|
.
|

\
|
c
c
|
.
|

\
|
c
c
= |
.
|

\
|
c
c
P T
T
V
P
S
|
.
|

\
|
c
c
= |
.
|

\
|
c
c
From Chapter 3, we also had the following two definitions:
P
T
V
V
|
.
|

\
|
c
c

1
|
Volume expansivity
T
P
V
V
|
.
|

\
|
c
c

1
k
Isothermal compressibility
V
P
S
T
| =
|
.
|

\
|
c
c
V T
P
H
T
) 1 ( | =
|
.
|

\
|
c
c
V T P
P
U
T
) ( | k =
|
.
|

\
|
c
c
Applying | & k in the above three equations:
Example
(Problem 6.7, SVA)
Estimate the change in enthalpy and entropy when
liquid ammonia at 270 K is compressed from its
saturated pressure of 381 kPa to 1200 kPa. For
saturated liquid ammonia at 270 K, V
l
=1.55110
-3
m
3
/kg and |=2.09510
-3
K
-1
.
11
Example
(Problem 6.4, SVA)
The PVT behaviour of a certain gas is described by the
equation of state:
Where b is constant.
Show that U is a function of T only.
RT b V P = ) (
dV P
T
P
T dT C dU
V
v (

|
.
|

\
|
c
c
+ =
Gibbs Free Energy
For Gibbs free energy we had: dG = VdP SdT
In this equation, G is related to entropy which is often very difficult
to measure
Consider:
( ) dT
RT
G
dG
RT
RT
G
d
2
1
=
Substitute for dG and G (G = H - TS)
( ) dT
RT
TS H
SdT VdP
RT
RT
G
d
2
) (
) (
1
=
dT
RT
S
dT
RT
H
dT
RT
S
dP
RT
V
+ =
2
( ) dT
RT
H
dP
RT
V
RT
G
d
2
= This is no longer dependent on entropy
12
Gibbs Free Energy
(Generating Function)
This equation has a unique practical application:
All the other thermodynamic properties can be related to the above
Given G =H - TS & H =U +PV
T
P
RT G
RT
V
(

c
c
=
) / (
( ) dT
RT
H
dP
RT
V
RT
G
d
2
=
P
T
RT G
T
RT
H
(

c
c
=
) / (
RT
G
RT
H
R
S
=
RT
PV
RT
H
RT
U
=
Once we have G=G(T,P), we can obtain all other properties. As a result
Gibbs Free Energy is also called Generating Function
Residual Properties
Residual property of any extensive thermodynamic
property, is the difference between the actual and ideal gas
properties
Therefore:
P
2
, T
2
P
1
, T
1
AG
T
P
P
ig
M
R
= M - M
ig
H
R
= H H
ig
S
R
= S - S
ig
dT
RT
H
dP
RT
V
RT
G
d
R R
R
2
=
|
.
|

\
|
T
R R
P
RT G
RT
V
(

c
c
=
) / (
P
R R
T
RT G
T
RT
H
(

c
c
=
) / (
RT
G
RT
H
R
S
R R R
=
H = H
R
+ H
ig
S = S
R
+ S
ig
13
Residual Properties
(Functions of Compressibility Factor)
Z and (cZ/cT)
P
will be obtained from PVT data available from the experiment
Consider:
T
R R
P
RT G
RT
V
(

c
c
=
) / (
Residual Volume: V
R
= V - V
ig
P
ZRT
V
P
RT
V
ig
= = & We know:
) 1 ( = Z
P
RT
V
R
dP
RT
V
RT
G
d
R R
=
|
|
.
|

\
|

(constant T)
}
=
P
R R
dP
RT
V
RT
G
0
}
=
P
R
P
dP
Z
RT
G
0
) 1 (
}
|
.
|

\
|
c
c
=
P
P
R
P
dP
T
Z
T
RT
H
0
} }
|
.
|

\
|
c
c
=
P P
P
R
P
dP
Z
P
dP
T
Z
T
R
S
0 0
) 1 (
Estimation of Z
(For Residual Properties)
Zcan also be evaluated using:
Virial EOS
Cubic EOS
Generalized property correlations
The first two approaches involve some mathematical
manipulations of the EOS and equations presented in
previous slides (read Pages 215-217, SVA)
e.g:
(

|
.
|

\
|
+ |
.
|

\
|
=
2
2
1

dT
dC
T
C
dT
dB
T
B
T
RT
H
R
where B & C are virial coefficients:
What will be the above equation if we use two term virial EOS?
14
Summary of Previous Lecture
Residual property of any extensive thermodynamic
property, is the difference between the actual and ideal gas
properties
P
2
, T
2
P
1
, T
1
AG
T
P
P
ig
M
R
= M - M
ig
H
R
= H H
ig
S
R
= S - S
ig
H = H
R
+ H
ig
S = S
R
+ S
ig
) 1 ( = Z
P
RT
V
R
}
|
.
|

\
|
c
c
=
P
P
R
P
dP
T
Z
T
RT
H
0
}
=
P
R
P
dP
Z
RT
G
0
) 1 (
} }
|
.
|

\
|
c
c
=
P P
P
R
P
dP
Z
P
dP
T
Z
T
R
S
0 0
) 1 (
Estimation of Z
(For Residual Properties)
Zcan also be evaluated using:
Virial EOS
Cubic EOS
Generalized property correlations
The first two approaches involve some mathematical
manipulations of the EOS and equations earlier (read
Pages 215-217, SVA)
15
Generalized Correlations
(For Residual Properties)
Generalized property correlations were previously used
(Chapter 3) to estimate compressibility factor (Z)
We can also apply these property correlations to obtain
values of H
R
and S
R
So, similar to before, the idea is to relate Z to T
r
, P
r
, & e
i.e. Z = f (T
r
, P
r
, e)
or Z = Z
0
(T
r
, P
r
) + e Z
1
(T
r
, P
r
)
T
r
=T/T
c
P
r
=P/P
c
Lee/Kesler Approach
(For Residual Properties)
Following the mathematical manipulations described on
pages 230 & 232 (SVA):
c
R
c
R
c
R
RT
H
RT
H
RT
H
1 0
) ( ) (
e + =
R
S
R
S
R
S
R R R 1 0
) ( ) (
e + =
Lee/Kesler correlations
for residual enthalpy
Lee/Kesler correlations
for residual entropy
Tables E-5 through E-12
Appendix E (SVA)
16
Lee/Kesler Correlation
Generalized Correlations
(For Residual Properties)
At low pressure, we can use the generalized second
virial coefficient correlation
where: BP
c
/RT
c
= B
0
+ e B
1
(
(

|
|
.
|

\
|
+ =
r
r
r
r r
c
R
dT
dB
T B
dT
dB
T B P
RT
H
1
1
0
0
e
|
|
.
|

\
|
+ =
r r
r
R
dT
dB
dT
dB
P
R
S
1 0
e
Hence:
1.6
r
0
T
0.422
0.083 B =
2.6
r r
0
T
0.675

dT
dB
=
4.2
r
1
T
0.172
0.139 B =
5.2
r r
1
T
0.722

dT
dB
=
17
Generalized Correlations
(For Residual Properties)
When to use Lee/Kesler values?
P
r
Z
0
1
Fig. 3.14 SVA
0.8
T
r
=4
T
r
=2
T
r
=1
2
Lee/Kesler
(non-linear)
2
nd
Virial
(linear)
Example Problem
Determine H
R
and S
R
for chlorine gas at 155 bar and
500 K using Lee/Kesler approach
18
Example Problem
Determine H
R
and S
R
for chlorine gas at 155 bar and
500 K using Lee/Kesler approach
Estimating Real Gas Properties
Given the fact that Enthalpy or Entropy are
always estimated in relative values:
H = H
R
+ H
ig
S = S
R
+ S
ig
) ( ln
) (
1 2
1
2
1 2
2
1
2
1
R R
T
T
ig
P
R R
T
T
ig
P
S S
P
P
R
T
dT
C S
H H dT C H
+ = A
+ = A
}
}
( )
) ( ln ln
) (
1 2
1
2
1
2
1 2 1 2
R R ig
P
R R ig
P
S S
P
P
R
T
T
C S
H H T T C H
+ = A
+ = A
For constant C
p
:
P
2
, T
2
P
1
, T
1
AH
AS
T
P
P
ig
T
ig
19
Example Problem
Work on:
Example 6.3 (page 214 SVA)
Example 6.8 (page 229 SVA)
Example
(Problem 6.50, SVA)
Propane gas at 1 bar and 35 C is compressed to a final
state of 135 bar and 195 C. Estimate the molar volume
of the propane in the final stage and the enthalpy and
entropy changes for the process. In its initial state,
propane may be assumed an ideal gas.
20
Gas Mixtures
For mixture of gases, the procedures for determining
the thermodynamic properties are similar
Critical parameters (e.g. T
c
, P
c
, V
c
, & e) can be
approximated by:
i
i
i
y e e

=
Reduced properties are then estimated by:
pc
pr
pc
pr
T
T
T
P
P
P = =
ci
i
i pc
P y P

=
ci
i
i pc
T y T

=
i j ij
i j
B y y B =

PV
Z 1 BP
RT
= = +
The Virial EOS:
Two Phase Systems
During the phase transition (i.e. crossing any of
the curves in PT diagram) under constant
pressure and temperature
Significant changes will take place in molar and
specific values of the thermodynamic properties
(molar/specific volume, entropy, )
T
P
Vapour
Solid
Liquid
The exception on this would be for Gibbs Free Energy
G does not change during a phase transition
V
&
L
Consider a system containing pure liquid in
equilibrium with it vapour
With small changes resulting in some
liquid to evaporate @ constant P & T
d(nG) = nVdP - nSdT
0
0
d(nG) = 0 dG = 0
21
Two Phase Systems
Consider a system of two phases (vapour & liquid)
that coexist in equilibrium
dG
o
= dG
|
o (liquid) & | (vapour)
Given the original expressions for dG
dT S dP V dT S dP V
sat sat | | o o
=
Clapeyron equation
o |
o |
V V
S S
dT
dP
sat

=
o|
o|
V
S
A
A
=
Changes in S & V when
unit amount of pure
chemical is transferred
from o to |
We had: dH = TdS + VdP
0
AH
o|
= TAS
o|
o|
o|
V T
H
dT
dP
sat
A
A
=
lv
lv sat
V T
H
dT
dP
A
A
=
Vapour Pressure & Temperature
Clapeyron equation relates the vapour pressure to the
temperature of a two phase system
More accurate for wider range
of temperature
Antoine Equation
lv
lv sat
V T
H
dT
dP
A
A
=
Two other equations relating P
sat
to T:
) ln ( ln
C t
B
A P or
T
B
A P
sat sat
+
= =
r
sat
r
T
D C B A
P =

+ + +
= 1
1
ln
6 3 5 . 1
t
t
t t t t
Wagner Equation
sat
vap
P
T R
H
ln
1
=
|
|
.
|

\
|
A

Clausius-Clapeyron Equation
Assuming vapour as ideal gas:
22
Two Phase Liquid/Vapour Systems
For systems consisting of saturated
liquid/vapour under saturation
M = (1-x
v
)M
l
+ x
v
M
v
where M represents H, S, U, & V
Also:
M = M
l
+ x
v
AM
lv
Example
(Problem 6.37, SVA)
Steam at 2000 kPa containing 6% moisture is
heated at constant pressure to 575 C. How
much heat is require per kilogram?
23
Thermodynamic Diagrams
We have already used PVT (PV and PT)
diagrams
Also, we have learned about Mollier diagram
(relating H, S, T, & P)
Other diagrams of great importance and use
Pressure enthalpy (P-H) diagram
Temperature entropy (T-S) diagram
PVT Diagram
24
Mollier Diagram
P-H Diagram
25
P-H Diagram
Entropy-Pressure diagram for ethylene
T-S Diagram
26
Thermodynamic Diagrams
Each of these make solving certain problems
very convenient
Mollier (H-S) diagram is useful for problems
involving turbines and compressors
Pressure enthalpy (P-H) diagram is useful
for solving refrigeration problems
Temperature entropy (T-S) diagram is used in
the analysis of engines and power and
refrigeration cycles
Example
(Problem 6.43, SVA)
Steam entering a turbine at 4000 kPa and 400 C
expands reversibly and adiabatically,
a) For what discharge pressure is the exit stream a
saturated vapour?
b) For what discharge pressure is the exit stream a wet
vapour with quality of 0.95?