Chemical Engineering

Thermodynamics-I
Lecture 4
Prof.Dr.Mahmood Saleem
Institute of Chemical Engineering &
Technology
University of the Punjab, Lahore
Contents
Introduction
Property relations for Homogeneous Phase
Residual Properties
Residual Properties by Equation of State
Property Relations for Two Phase Systems
Thermodynamic Property Diagrams and Tables
Generalized property Correlations for Gases
Extension of Generalized property Correlations
for Gases to Mixtures
Exercises
Introduction
Processing of materials (pure and mixtures) is
key affair in chemical processes
Estimation of many properties (and change)
other than volumetric properties (H,U,s,G etc.)
are required.
How to know complete property set when
volumetric properties are not available
What tools can one use to handle such issues?
Property Relations for Homogeneous Phases
Fundamental Properties



Although equation (6.1) is derived from the special case of
a reversible process, it not restricted in application to
reversible process.
It applies to any process in a system of constant mass that
results in a differential change from one equilibrium state to
another.
The system may consist of a single phase or several
phases; may be chemically inert or may undergo chemical
reaction.
( ) ( ) ( ) nV d P nS d T nU d
dW dQ nU d
rev rev
. .
) (
=
=
(6.1)
Definitions

H = Enthalpy


A = Helmholtz energy


G = Gibbs energy
PV U H +
TS U A
TS H G
(2.11)
(6.2)
(6.3)
Based on one mole (or to a unit mass) of a
homogeneous fluid of constant composition,
they simplified to
Function Change







SdT VdP dG T P G
SdT PdV dA T V A
VdP TdS dH P s H
PdV TdS dU V s U
=
=
+ =
=
.... )......... , (
.... )......... , (
.... )......... , (
..... )......... , (
Maxwells equations
T P
T V
P S
V S
P
S
T
V
V
S
T
P
S
V
P
T
S
P
V
T
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
T P
P T
P
S
T
V
dT
T
G
dP
P
G
dG
dT S dP V dG
T P G
|
.
|

\
|
c
c

|
.
|

\
|
c
c
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
=
.
...... ... ...... ...
) , (
Enthalpy and Entropy as Functions of T and P
Temperature derivatives:






T
C
T
S
C
T
H
P
P
P
P
=
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
Pressure derivatives:
P T
P T
T
V
T V
P
H
T
V
P
S
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
The most useful property relations for the enthalpy
and entropy of a homogeneous phase result when
these properties are expressed as functions of T
and P (how H and S vary with T and P).
dP
T
V
T
dT
C dS
dP
T
V
T V dT C dH
P
P
P
p
|
.
|

\
|
c
c
=
(

|
.
|

\
|
c
c
+ =
(6.21)
(6.20)
Property Relations for Homogeneous
Phases
Internal Energy as Function of P (U(P))
The pressure
dependence of the
internal energy is
shown as

PdV Tds dU =
|
.
|

\
|
c
c

|
.
|

\
|
c
c
=
|
.
|

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

\
|
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
Property Relations for Homogeneous
Phases
The Ideal Gas State
For ideal gas,
expressions of dH
and dS (eq.6.20-6.21)
as functions of T and
P can be simplified as
follows using ideal
gas law:
(6.24)
(6.23)
P
dP
R
T
dT
C dS
dT C dH
P
R
T
V
RT PV
ig
P
ig
ig
P
ig
P
ig
ig
=
=
=
|
|
.
|

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

\
|
c
c
=
(

|
.
|

\
|
c
c
+ =
Property Relations for Homogeneous
Phases
Alternative Forms for Liquids
Relations of liquids
can be expressed in
terms of | and k as
follows:
( )
( )V T P
P
U
V T
P
H
V
P
S
T
T
T
| k
|
|
=
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
1
T P
T V
P S
V S
P
S
T
V
V
S
T
P
S
V
P
T
S
P
V
T
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
c
c
=
|
.
|

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

\
|
c
c
=
(

|
.
|

\
|
c
c
+ =
PdV Tds dU =
|
.
|

\
|
c
c

|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
T P T
P
V
P
T
V
T
P
U
dP dT
V
dV
P
V
V
T
V
V
dP
P
V
dT
T
V
dV
T
P
T P
k |
k
|
=
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
1
1
Property Relations for Homogeneous Phases
Alternative Forms for Liquids
Enthalpy and entropy as functions of T and P
as follows:




| and k are weak functions of pressure for
liquids, they are usually assumed constant at
appropriate average values for integration.
( )
) . ...( VdP
T
dT
C dS
) . ...( VdP T dT C dH
P
P
29 6
28 6 1
|
|
=
+ =
Practice 1
Determine the enthalpy and entropy changes of liquid water for
a change of stage from 1 bar 25C to 1,000 bar 50C.

T
( C)
P
(bar)
C
p
(Jmol
-1
K
-1
V
(cm
3
mol
-1
)
|
(K
-1
)
25 1 75.305 18.071

256x10
-6

25 1000 18.012

366x10
-6

50

1 75.314 18.234 458x10
-6

50 1,000 18.174 568x10
-6

Constant P
Constant T
1 6 6
1 3
1 1
10 513 10
2
568 458
204 . 18
2
174 . 18 234 . 18
, 50
310 . 75
2
314 . 75 305 . 75
, 1

=
+
=
=
+
=
=
=
+
=
=
K
mol cm V
C T f or and
K Jmol C
bar P For
p
|
( ) ( ) ( )
( )
1 2
1
2
1 2 2 1 2
ln
1
P P V
T
T
C S
P P V T T T C H
p
p
= A
+ = A
|
|
Integrated forms of
equations for change
in Enthalpy and
Entropy
Average value at T1
and T2 at 1 bar
Average value at P1
and P2 at 50 oC
( )
( )( ) | |( )( )
( )( )( )
1 1
6
1
6
13 . 5 93 . 0 06 . 6
10
1 000 , 1 204 . 18 10 513
15 . 298
15 . 323
ln 310 . 75
400 , 3 517 , 1 883 , 1
10
1 000 , 1 204 . 18 15 . 323 10 513 1
15 . 298 15 . 323 310 . 75

= =

= A
= + =

+ = A
K Jmol
S
Jmol
H
( ) ( ) ( )
( )
1 2
1
2
1 2 2 1 2
ln
1
P P V
T
T
C S
P P V T T T C H
p
p
= A
+ = A
|
|
Note that the effect of AP of almost 1,000 bar on H and S of liquid water
is less than that of AT of only 25C.
On substitution of values
Property Relations for Homogeneous Phases
Internal Energy and Entropy as Function of T and V
Useful property relations for T and V as independent
variables are
k
|
=
|
.
|

\
|
c
c

|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
V
V T
V
V
T
P
P
T
P
T
V
U
T
C
T
S
The Partial derivatives dU and ds of homogeneous fluids
of constant composition to temperature and volume are





Alternative forms of the above equations are

dV
T
P
T
dT
C dS
dV P
T
P
T dT C dU
V
V
V
V
|
.
|

\
|
c
c
+ =
(

|
.
|

\
|
c
c
+ =
dV
T
dT
C dS
dV P T dT C dU
V
V
k
|
k
|
+ =
(

+ =
dP dT
V
dV
P
V
V
T
V
V
dP
P
V
dT
T
V
dV
T
P
T P
k |
k
|
=
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
1
1
Property Relations for Homogeneous Phases
The Gibbs Energy
An alternative form of a fundamental property
relation as defined in dimensionless terms:

( )
( )
P
T
T
RT G
T
RT
H
P
RT G
RT
V
dT
RT
H
dP
RT
V
RT
G
d
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=
=
|
.
|

\
|
2
The Gibbs energy when given as a function of T and
P therefore serves as a generating function for the
other thermodynamic properties, and implicitly
represents complete information.
Residual Properties
The definition for the generic residual property is:
ig R
M M M
M is the actual
molar value of
any extensive
thermodynami
cs property: V,
U, H, S, G.
M
ig
= the ideal
gas properties
which are at the
same
temperature and
pressure.
M = the Residual
Molar gas
properties which
are at the same
temperature and
pressure.
Residual Gibbs energy:




Residual volume:

ig R
G G G
( ) 1 =
=
Z
P
RT
V
P
RT
V V V V
R
ig R
PV=ZRT
Fundamental property relation for residual properties
The fundamental property relation for residual
properties applies to fluids of constant composition.




( )
( )
) . (
T
RT / G
T
RT
H
) . (
P
RT / G
RT
V
) . ( dT
RT
H
dP
RT
V
RT
G
d
P
R R
T
R R
R R R
44 6
43 6
42 6
2

c
c
=
(

c
c
=
=
|
.
|

\
|
) 48 . 6 ( ) ( ) 1 ( ,
) 46 . 6 ( ); 44 . 6 45 . 6 .(
0 ) 45 . 6 ( ) 1 (
) ( ), 43 . 6 .(
0 0
0
0
0 0
0

T const
P
dP
Z
P
dP
T
Z
T
R
S
So
RT
G
RT
H
RT
S
From
P
dP
T
Z
T
RT
H
Eq
RT
G
gas ideal f or
P
dP
Z dP
RT
V
RT
G
RT
G
T const dP
RT
V
RT
G
d Eq From
P
P
P
R
R R R
P
P
R
P
R
P
R
P
P
R R
R R

|
.
|

\
|
c
c
=
=
|
.
|

\
|
c
c
= +
=
|
|
.
|

\
|
= +
|
|
.
|

\
|
=
=
|
|
.
|

\
|
} }
}
} }
= =
Enthalpy and Entropy from Residual Properties
) . ( S
P
P
ln R dT C S S
) . ( H dT C H H ; on Substituti
P
P
ln R dT C S S dT C H H
); . ( and ) . .( Eq of n Integratio
S S S H H H ; S and H to Applied
R
T
T
ig
P
ig
R
T
T
ig
P
ig
T
T
ig
P
ig ig
T
T
ig
P
ig ig
R ig R ig
51 6
50 6
24 6 23 6
0
0
0
0
0 0
0
0
0 0

+ + =
+ + =
+ = + =
+ = + =
}
}
} }
( )
(

+ + + =
+ + + =

+ + =
+ + =
}
}
2
2 1 1 2
2 1
2 1
2
1 2
0 0
0
0 0
2
1
2
1
4
3
53 6
52 6
T T
D
C T T BT A
R
C
) T / T ln(
T
dT
C
C
T T
D
) T T T (
C
BT A
R
C
T T
dT C
C
) . ( S
P
P
ln R
T
T
ln C S S
) . ( H ) T T ( C H H
lm am lm
S
P
T
T
ig
P
S
P
am am
H
P
T
T
ig
P
H
P
R
S
P
ig ig
R
H
P
ig ig

The true worth of the Eq. for ideal gases is now evident.
They are important because they provide a convenient base
for the calculation of real-gas properties.
Practice 2

Calculate H and S of saturated isobutane vapor
at 630 K from the following information:
1. Table 6.1 gives compressibility-factor data
2. The vapor pressure of isobutane at 630 K
15.46 bar
3. Set H
0
ig
= 18,115 Jmol
-1
and S
0
ig
= 295.976
Jmol
-1
K
-1
for the ideal-gas reference state at
300 K 1 bar
4. C
p
ig
/R = 1.7765+33.037x10
-3
T (T/K)
Solution 6.3

Eqs. (6.46) and (6.48) are used to calculate H
R
and S
R
.





Plot (cZ/cT)
P
/P and (Z-1)/P vs. P
From the compressibility-factor data at 360 K (Z-1)/P
The slope of a plot of Z vs. T (cZ/cT)
P
/P
Data for the required plots are shown in Table 6.2.
P
dP
Z
P
dP
T
Z
P
P
P
) 1 (
0 0

|
.
|

\
|
c
c
} }
( )
( )( )( )
( )( )
1 1
1
1 1
4
0
1 4
0
734 5 314 8 6897 0
3 841 2 360 314 8 9493 0
314 8
6897 0 2596 0 9493 0 48 6
9493 0 10 37 26 360 46 6
2596 0 1 10 37 26

= =
= =
=
= =
= =
= =
|
.
|

\
|
c
c
} }
K Jmol . . . S
Jmol . , . . H
K Jmol . R For
. . .
R
S
), . ( . Eq By
. ) . )( (
RT
H
), . ( . Eq By
.
P
dP
) Z ( K .
P
dP
T
Z
R
R
R
R
P
P
P
| |
1 1
1
1 1
1 1
0 1
0 1
1 0
3
3
676 286 734 5 41 15 314 8
300
360
16 105 576 295
5 598 21 2 841 2 300 360 41 105 115 18
51 6 50 6
16 105 314 8 649 12
41 105 314 8 679 12
09 329
300 360
300 360
330
2
360 300
2
10 037 33 7765 1
10 037 33 7765 1

=
(

+ =
= + =
= =
= =
=

=
=
+
=
+
=
+ = + =
+ = + =
K Jmol . . . ln . ) ln( . . S
Jmol . , . , ) ( . , H
) . ( and ) . .( Eq o int Substitute
K Jmol . ) . ( . C
K Jmol . ) . ( . C
K .
) / ln( ) T / T ln(
T T
T
K
T T
T
T . . BT A
R
C
T . . BT A
R
C
S
ig
P
H
ig
P
lm
am
lm lm
S
ig
P
am am
H
ig
P
Residual Properties by Equations of State
Residual Properties from the Virial Equation of
State
The two-term virial eq. gives Z-1 = BP/RT.







( )
) 56 . 6 ( ), 47 . 6 .( int
) 55 . 6 (
/
), 44 . 6 .(
) 54 . 6 ( ,

dT
dB
R
P
R
S
Eq o on Substituti
dT
dB
T
B
R
P
T
RT G
T
RT
H
Eq By
RT
BP
RT
G
So
R
P
R R
R
=
|
.
|

\
|
=
(

c
c
=
=
P
dP
Z
RT
G
P
R
) 1 (
0
=
}
In application is a more convenient variable than V,
PV = ZRT is written in the alternative form.

) . (
d
) Z (
d
T
Z
T Z ln
R
S
), . .( Eq From
) . ( Z
d
T
Z
T
RT
H
); . ( and ) . .( Eq of tion Differenti
T
) RT / G (
T
P
P
Z
RT
H
), . ( and ) . .( Eq From
) . ( Z ln Z
d
) Z (
RT
G
); . .( Eq o int Substitue
Z
dZ d
P
dP
) dZ Zd ( RT dP ), . ( RT Z P
R
R
R R
R
60 6 1 47 6
59 6 1 58 6 57 6
1
42 6 40 6
58 6 1 1 49 6
57 6
0 0
0
2
0

} }
}
}

|
.
|

\
|
c
c
=
+
|
.
|

\
|
c
c
=
(

c
c

|
.
|

\
|
c
c
=
+ =
+ = + = =
The three-term virial equation.
) 63 . 6 (
2
1
ln
) 62 . 6 (
2
1
) 61 . 6 ( ln
2
3
2
). 60 . 6 ( ) 58 . 6 .( int 1
2
2
2
2

|
.
|

\
|
+
|
.
|

\
|
+ =
(

|
.
|

\
|
+
|
.
|

\
|
=
+ =
+ =




dT
dC
T
C
dT
dB
T
B
T Z
R
S
dT
dC
T
C
dT
dB
T
B
T
RT
H
Z C B
RT
G
through Eq o substitued is C B Z
R
R
R
Application of these equations, useful for gases up to
moderate pressure, requires data for both the second and
third virial coefficients.
Residual Properties by Cubic Equations of State
I
dT
dq
T
Z
qI b simplif y To
b b
b d
dT
dq
T
Z
b b
b d
q
b
b d
b
b
b b
b
dT
dq
T
Z
b b
b
q
b
b
Z
b b
b
q
b
Z
Eq V e RT y Eq
=
|
.
|

\
|
c
c
=
+ +
=
|
.
|

\
|
c
c
+ +

=
+ +
|
.
|

\
|
=
|
.
|

\
|
c
c
+ +

=
+ +

=
=
} }
} }
} } }

o c

o c

o c

o c

o c

d
, ) 1 ln(
d
1) - (Z ;
) 1 )( 1 (
) ( d
) 1 )( 1 (
) ( ) (
1
d
1) - (Z
); 60 . 6 ( ), 58 . 6 ( Eqs. of integrals The
) 1 )( 1 (
) 64 . 6 (
) 1 )( 1 ( 1
1
) 1 )( 1 ( 1
1
). 51 . 3 .( by given q as , / 1 substitut and b devides ) 42 . 3 .(
0 0
0 0
0 0 0

The generic equation of state presents two cases.

c|
|
c

o c
c|
o|
c o

|
c
o
c o
o c
+
=
+
= =
|
|
.
|

\
|
+
+

=
= = =
|
|
.
|

\
|
+
+

= =
Z b
b
I
b
Z
Z
I
b
Z
whence
RT
P
Z

a
b
b
I
1
: II Case
) 65 . 6 ( ln
1
RT
bP
Z. of favor in eliminated is When
) 65 . 6 (
1
1
ln
1
: I Case

) 68 . 6 (
ln
) ( ln
) ln(
) 67 . 6 ( 1
ln
) ( ln
1
) 66 . 6 ( ) ln( 1
) 66 . 6 ( ) 1 ln( 1

qI
T d
T d
Z
R
S
qI
T d
T d
Z
RT
H
b qI Z Z Z
RT
G
a qI Z b Z
RT
G
r
r
R
r
r
R
R
R
o
|
o
|

+ =
(

+ =
=
=
Find values for the H
R
and S
R
for n-butane gas at 500 K
50 bar as given by the Redlich/Kwong Eequation.

Solution
T
r
= 500/425.1 = 1.176, P
r
= 50/37.96 = 1.317
From Table 3.1:
( )
( )( )
8689 . 3
176 . 1 08664 . 0
42748 . 0
); 54 . 3 .(
09703 . 0
176 . 1
317 . 1
08664 . 0 ); 53 . 3 .(
2 / 3
= =
O
+
=
= = O =
r
r
r
r
T
T
q Eq
T
P
Eq
o
|
Ex. 6.4
( )( )
( )( )
| |
( )( )
1 1
1
546 . 6 ) 78735 . 0 ( 314 . 8
505 , 4 0838 . 1 500 314 . 8 ,
78735 . 0 13247 . 0 ) 8689 . 3 ( 5 . 0 ) 09703 . 0 6850 . 0 ln( : ) 68 . 6 .(
0838 . 1 ) 13247 . 0 )( 8689 . 3 )( 1 5 . 0 ( 1 6850 . 0 : ) 67 . 6 .(
: .
2
1
ln / ) ( ln , ln
2
1
) ( ln
13247 . 0 ln
6850 0
) 09703 . 0 (
09703 . 0
09703 . 0 8689 . 3 09703 . 0 1
1 : ) 52 . 3 .(

= =
= =
= =
= + =
= =
=
+
=
=
+

+ =
+ +

+ =
K Jmol S
Jmol H Thus
R
S
Eq
RT
H
Eq
Then T d T d T T With
Z
Z
I
Then: . . Z yields Eq. this of Solution
Z Z
Z
Z Z
Z
q Z Eq
R
R
R
R
r r r r
o o
|
o| c|
|
| |
These results are compared with those of other
calculation in Table 6.3.
TWO-PHASE SYSTEMS
) . (
Z R
H
) T / ( d
P ln d
or
) . (
Z RT
H
dT
P ln d
Z
P
RT
V But
) . (
V T
H
dT
dP
; vapor to liquid from transition Phase
equation Clapeyron The : ) . (
V T
H
dT
dP
T / H S , Thus
) transition phase of heat latent The ( S T H ); . .( Eq of n Integratio
V
S
V V
S S
dT
dP
, t arrangemen Re
dT S dP V dT S dP V dG dG , G G
l
l sat
l
l sat
l
sat
l
l
l sat
sat
sat
sat sat
74 6
1
73 6
72 6
71 6
8 6
2

v
v
v
v
v v
v
v
o|
o|
o| o|
o| o|
o|
o|
o |
o |
| | o o | o | o
A
A
=
A
A
= A = A
A
A
=
A
A
= A = A
A = A
A
A
=

=
= = =
The Clapeyron eq.
for pure-species
vaporization
Temperature Dependence of the Vapor
Pressure of Liquids
r
.
r
sat
r r
sat
sat
T where
) . (
D C B A
) T ( P ln ; T of function A
B . App , . B Table in given are ts tan cons Antoine
) . (
C T
B
A P ln : . eq Antoine The
T
B
A P ln


+ + +
=
+
=
=
1
77 6
1
2
76 6
6 3 5 1
t
t
t t t t

Corresponding-States Correlations
for Vapor Pressure
:
:
) 81 . 6 (
) ( ln
) ( ln ln
) 80 . 6 ( 43577 . 0 ln 4721 . 13
6875 . 15
2518 . 15 ) ( ln
) 79 . 6 ( 169347 . 0 ln 28862 . 1
09648 . 6
92714 . 5 ) ( ln
) 78 . 6 ( ) ( ln ) ( ln ) ( ln
: /
1
0
6 1
6 0
1 0
sat
r
r
r r
r r
sat
r
r r
r
r r
r r
r
r r
r r r r r
sat
r
n
n
n
n n
P
T
where
T P
T P P
T T
T
T P
T T
T
T P where
T P T P T P
n correlatio Kesler Lee

=
+ =
+ =
+ =
e
e
The reduced normal boiling point
The reduced vapor pressure corresponding to 1 atm
Ex. 6.6
Determine the vapor pressure for liquid n-hexane at 0, 30,
60 and 90C: (a) With constants from App. B.2.
(b) From the Lee/Kesler correlation for P
r
sat
Solution
(a)

(b) Eq.(6.78);
From Table B.1,
From Eq.(6.81) e =0.298





The average difference from the Antoine values is about 1.5%.
317 . 224
04 . 2696
8193 . 13 ln
+
=
t
P
sat
03350 . 0
25 . 30
01325 . 1
, 6736 . 0
6 . 507
9 . 341
= = = =
sat
r r
n n
P T
t/C P
sat
/kPa
(Antoine)
P
sat
/kPa
(Lee/Kesler)
t/C P
sat
/kPa
(Antoine)
P
sat
/kPa
(Lee/Kesler)
0
60
6.052
76.46
5.835
76.12
30
90
24.98
189.0
24.49
190.0
Two-Phase Liquid/Vapor System
) 82 . 6 (
: . , , , ,
) 82 . 6 ( ) 1 (
:
1 ) 1 (
:
) (
b M x M M
f orm e alternativ An etc S H U V M where
a M x M x M
equation generic The
x x V x V x V
f raction mass x V x V x V
moles n n n V n V n nV
l l
l v
v l l v
l l
v l l l

v v
v v
v v
v v
v v
A + =

+ =
= + =
+ =
+ = + =
THERMODYNAMIC DIAGRAMS
GENERALIZED PROPERTY
CORRELATION FOR GASES
) 84 . 6 ( ) 1 (
) 83 . 6 (
: ) 48 . 6 ( ) 46 . 6 .( int
,
0 0
0
2

r
r
P
r
r
P
P
r
r
R
r
r
P
P
r
r
c
R
r c r c r c r c
P
dP
Z
P
dP
T
Z
T
R
S
P
dP
T
Z
T
RT
H
and Eqs o substitue
dT T dT T T T dP P dP P P P
r
r
r
r
r
} }
}

|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
=
= = = =
( ) ( )
( ) ( )
) 86 . 6 (
1 : ) 84 . 6 .(
) 85 . 6 (
: ) 83 . 6 .(
1 0
1
1
0
0
1
0
1 0
0
1
2
0
0
2
1 0
1 0

R
S
R
S
R
S
P
dP
Z
T
Z
T
P
dP
Z
T
Z
T
R
S
Eq
RT
H
RT
H
RT
H
P
dP
T
Z
T
P
dP
T
Z
T
RT
H
Eq
T
Z
T
Z
T
Z
Z Z Z
R R R
r
r
P
r
r
P
r
r
P
r
r
P
R
c
R
c
R
c
R
r
r
P
P
r
r
r
r
P
P
r
r
c
R
P
r
P
r
P
r
r
r
r
r
r
r
r
r
r r r
e
e
e
e
e e
+ =
(
(

+
|
|
.
|

\
|
c
c

(
(

+
|
|
.
|

\
|
c
c
=
+ =
(
(

|
|
.
|

\
|
c
c

(
(

|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
+
|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
+ =
} }
} }
Table E.5 - E.12
Analytical correlation of the residual properties at low pressure
) 88 . 6 (
) 87 . 6 (
, ); 56 . 6 ( ) 55 . 6 .(
,
sec
1 0
1
1
0
0
1 0
1 0

|
|
|
.
|

\
|
+ =
(
(
(
(

|
|
|
|
.
|

\
|
+ =
=
|
|
|
|
.
|

\
|
=
+ = + = =

. .
.
.
.
r r
r
R
r
r
r
r r
c
R
r
r
R
r
r r
c
R
r r r c
c
dT
B d
dT
B d
P
R
S
dT
B d
T B
dT
B d
T B P
RT
H
dT
B d
P
R
S
dT
B d
T B P
RT
H
and Eqs
dT
dB
dT
dB
dT
B d
B B
RT
BP
B
f orms n correlatio t coef f icien virial ond d generalize The
e
e
e e
) 90 . 6 (
722 . 0
) 89 . 6 (
675 . 0
) 66 . 3 (
172 . 0
139 . 0
) 65 . 3 (
422 . 0
083 . 0
2 . 5
1
6 . 2
0
2 . 4
1
6 . 1
0

r r
r r
r
r
T dT
dB
T dT
dB
T
B
T
B
=
=
=
=
H
R
and S
R
with ideal-gas heat capacities
R
T
ig
P
ig R
T
ig
P
ig
H dT C H H H dT C H H
1
0
0 1 2
0
0 2
1 2
+ + = + + =
} }
) 92 . 6 ( ln ,
) 91 . 6 (
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 dT C S Similarly
H H dT C H
+ = A
+ = A
}
}
For a change from state 1 to 2:
The enthalpy change for the process, AH = H
2
H
1
Alternative form
) 94 . 6 ( ln ln
) 93 . 6 ( ) (
1 2
1
2
1
2
1 2 1 2

R R
S
ig
P
R R
H
ig
P
S S
P
P
R
T
T
C S
H H T T C H
+ = A
+ = A
A three-step calculational path
Step 11
ig
: A hypothetical process that transforms a real
gas into an ideal gas at T
1
and P
1
.


Step 1
ig
2
ig
: Changes in the ideal-gas state from (T
1
,P
1
)
to (T
2
,P
2
).




Step 2
ig
2: Another hypothetical process that transform
the ideal gas back into a real gas at T
2
and P
2
.
R ig R ig
S S S H H H
1 1 1 1 1 1
= =
) 96 . 6 ( ln
) 95 . 6 (
1
2
1 2
1 2
2
1
2
1

P
P
R
T
dT
C S S S
dT C H H H
T
T
ig
P
ig ig ig
T
T
ig
P
ig ig ig
= = A
= = A
}
}
R ig R ig
S S S H H H
2 2 2 2 2 2
= =
Ex. 6.9
Estimate V, U, H and S for 1-butane vapor at 200C, 70 bar
if H and S are set equal to zero for saturated liquid at 0C.
Assume: T
c
=420.0 K, P
c
=40.43 bar, T
n
=266.9 K, e=0.191
C
p
ig
/R=1.967+31.630x10
-3
T-9.837x10
-6
T
2
(T/K)
Solution

1 3
1 0
8 . 287
70
) 15 . 473 )( 14 . 83 ( 512 . 0
512 . 0 ) 142 . 0 ( 191 . 0 485 . 0
; 4 . 3 . ) 57 . 3 .(
731 . 1
43 . 40
70
127 . 1
0 . 420
15 . 273 200

= = =
= + = + =
= = =
+
=
mol cm
P
ZRT
V
Z Z Z
E and E Table and Eq
P T
r r
e
Step (a): Vaporization of saturated liquid 1-butane at 0C


The vapor pressure curve contains both





The latent heat of vaporization, where T
r
n
=266.9/420=0.636:

) 75 . 6 ( ln
T
B
A P
sat
=
11 . 699 , 2 126 . 10 ,
0 . 420
43 . 40 ln int;
9 . 266
0133 . 1 ln int;
= =
=
=
B A Whence
B
A po critical the
B
A po boiling normal the
( )( )( )
1
137 , 22 9 . 266 314 . 8 979 . 9
979 . 9
636 . 0 930 . 0
) 013 . 1 43 . 40 (ln 092 . 1
930 . 0
) 013 . 1 (ln 092 . 1

= = A
=

=
A
Jmol H
T
P
RT
H
lv
n
r
c
n
lv
n
n
1 1
1
38 0
38 0
84 79
15 273
810 21
810 21
368 0
350 0
137 22
13 4
1
1
650 0 420 15 273 15 273

= =
A
= A
=
|
.
|

\
|
= A
|
|
.
|

\
|

=
A
A
= =
K Jmol .
.
,
T
H
S
Jmol ,
.
.
) , ( H
) . ...(
T
T
H
H
From
. / . T K . at heat latent The
lv
lv
.
lv
.
r
r
lv
n
lv
r
n
Step (b): Transformation of saturated vapor into an ideal
gas at (T
1
, P
1
).








T
r
= 0.650 and P
r
= 1.2771/40.43 = 0.0316
) 88 . 6 (
) 87 . 6 (
1 0
1
1
0
0

|
|
|
.
|

\
|
+ =
(
(
(
(

|
|
|
|
.
|

\
|
+ =
r r
r
R
r
r
r
r r
c
R
dT
B d
dT
B d
P
R
S
dT
B d
T B
dT
B d
T B P
RT
H
e
e
) 90 . 6 (
722 . 0
) 89 . 6 (
675 . 0
) 66 . 3 (
172 . 0
139 . 0
) 65 . 3 (
422 . 0
083 . 0
2 . 5
1
6 . 2
0
2 . 4
1
6 . 1
0

r r
r r
r
r
T dT
dB
T dT
dB
T
B
T
B
=
=
=
=
1 1
1
1
1
88 . 0 ) 314 . 8 )( 1063 . 0 (
344 ) 420 )( 314 . 8 )( 0985 . 0 ( ,

= =
= =
K Jmol S
Jmol H So
R
R
Step (c): Changes in the ideal gas state






T
am
= 373.15 K, T
lm
= 364.04 K,
A = 1.967, B = 31.630x10
-3
, C = -9.837x10
-6

AH
ig
= 20,564 J mol
-1
AS
ig
= 22.18 J mol
-1
K
-1

1
2
1
2
1
2
1 2
1 2 1 2
2
1
2
1
96 6
95 6
P
P
ln R
T
T
ln C
P
P
ln R
T
dT
C S S S : ) . .( Eq
) T T ( C dT C H H H : ) . .( Eq
S
ig
P
T
T
ig
P
ig ig ig
H
ig
P
T
T
ig
P
ig ig ig
= = = A
= = = A
}
}
Step (d): Transformation from the ideal gas to real gas
state at T
2
and P
2
.
T
r
= 1.127 P
r
= 1.731
At the higher P; Eqs.(6.85) and (6.86) with interpolated
values from Table E.7, E.8, E.11 and E.12.






1
1 3
1 1
1
1 1
2
1
2
2
2
218 , 32
10
) 8 . 287 )( 70 (
233 , 34
18 . 14 18 . 22 ) 88 . 0 ( 84 . 79
233 , 34 485 , 8 564 , 20 ) 344 ( 810 , 21
18 . 14 ) 314 . 8 )( 705 . 1 (
485 , 8 ) 0 . 420 )( 314 . 8 )( 430 . 2 (
705 . 1 ) 726 . 0 )( 191 . 0 ( 566 . 1
430 . 2 ) 713 . 0 )( 191 . 0 ( 294 . 2

= = =
+ = A =
= + = A =
= =
= =
= + =
= + =
Jmol
barJ cm
PV H U
K Jmol S S
Jmol H H
K Jmol S
Jmol H
R
S
RT
H
R
R
R
C
R
Extension to Gas Mixtures
) 101 . 6 ( ) 100 . 6 (
) 99 . 6 ( ) 98 . 6 ( ) 97 . 6 (
Pr Pr


pc pc
i
ci i pc
i
ci i pc
i
i i
P
P
P
T
T
T
P y P T y T y
= =


e e
These replace T
r
and P
r
for reading entries from the table of
App. E, and lead to values of Z by Eq.(3.57), and H
R
/RT
pc

by Eq.(6.85), and S
R
/R by Eq.(6.86).
Ex. 6.10
Estimate V, H
R
, and S
R
for an equimolar mixture of
carbon dioxide(1) and propane(2) at 450 K and 140 bar by
the Lee/Kesler correlations.

Solution
From Table B.1,
41 . 2
15 . 58
140
335 . 1
0 . 337
450
,
15 . 58 ) 48 . 42 )( 5 . 0 ( ) 83 . 73 )( 5 . 0 (
0 . 337 ) 8 . 369 )( 5 . 0 ( ) 2 . 304 )( 5 . 0 (
188 . 0 ) 152 . 0 )( 5 . 0 ( ) 224 . 0 )( 5 . 0 (
2 2 1 1
2 2 1 1
2 2 1 1
= = = =
= + = + =
= + = + =
= + = + =
pr pr
c c pc
c c pc
P T Whence
bar P y P y P
K T y T y T
y y e e e
( )
1 1
1
1 0
1 3
1 0
56 . 8 ) 029 . 1 )( 314 . 8 (
029 . 1 ) 330 . 0 )( 188 . 0 ( 967 . 0
: ) 86 . 6 .( ; 12 . 11 .
937 , 4 762 . 1 ) 337 )( 314 . 8 (
762 . 1 ) 169 . 0 )( 188 . 0 ( 730 . 1
169 . 0 730 . 1
: ) 85 . 6 .( ; 8 . 7 .
7 . 196
140
) 450 )( 14 . 83 )( 736 . 0 (
736 . 0 ) 205 . 0 )( 188 . 0 ( 697 . 0
; 4 . 3 .

= =
= + =
= =
= + =
=
|
|
.
|

\
|
=
|
|
.
|

\
|
= = =
= + = + =
K Jmol S
R
S
Eq with E and E Table From
Jmol H
RT
H
RT
H
RT
H
Eq with E and E Table From
mol cm
P
ZRT
V
Z Z Z
E and E Table From
R
R
R
pc
R
pc
R
pc
R
e