An equation of state is a relation between state

variables
It is a thermodynamic equation describing the state of
matter under a given set of physical conditions.
It is a constitutive equation which provides a
mathematical relationship between two or more state
functions associated with the matter, such as its
temperature, pressure, volume, or internal energy.
Equations of state are useful in describing the
properties of fluids, mixtures of fluids, solids, and even
the interior of stars.
Assumption:
1) the gas consists of a large number of molecules, which
are in random motion and obey Newton's laws of
motion;
2) the volume of the molecules is negligibly small
compared to the volume occupied by the gas; and
3) no forces act on the molecules except during elastic
collisions of negligible duration.
PV = RT
1. Van der Waals equation of state
2. RedlichKwong equation of state
3. Soave modification of RedlichKwong
4. PengRobinson equation of state
The van der Waals equation may be considered as the
ideal gas law, improved due to two independent
reasons:
Molecules are thought as particles with volume, not
material points. Thus V cannot be too little, less than
some constant. So we get (V b) instead of V.
We consider molecules attracting others within a
distance of several molecules' radii affects pressure
we get dengan (P + a/V
2
) instead of P.
( ) RT b V
V
a
P
2
=
|
.
|

\
|
+
where V is molar volume
The substance-specific constants a and b can be
calculated from the critical properties P
c
, T
c
, and V
c
as
c
2
c
2
c
2
c
2
P
T R
64
27
P
T R
64
27
a = =
c
c
c
c
P
T R
8
1
P
T R
8
1
b = =
Cubic form of vdW eos
2
V
a
b V
RT
P

=
0
P
ab
V
P
a
V
P
RT
b V
2 3
=
|
.
|

\
|
+
|
.
|

\
|
+
( ) 0 AB Z A Z 1 B Z
2 3
= + +
2
r
r
2 2
T
P
64
27
T R
aP
A = =
r
r
T
R
8
1
RT
bP
B = =
Principle of Corresponding States (PCS)
The principle of Corresponding States (PCS) was stated by
van der Waals and reads: Substances behave alike at the
same reduced states. Substances at same reduced states
are at corresponding states.
Reduced properties provide a measure of the
departure of the conditions of the substance from its
own critical conditions and are defined as follows
c
r
T
T
T =
c
r
P
P
P =
c
r
V
V
V =
The PCS says that all gases behave alike at the same
reduced conditions.
That is, if two gases have the same relative
departure from criticality (i.e., they are at the same
reduced conditions), the corresponding state
principle demands that they behave alike.
In this case, the two conditions correspond to one
another, and we are to expect those gases to have
the same properties.
Reduced form of vdW EOS:
( )
r r
2
r
r
T 8 1 V 3
V
3
P = |
.
|

\
|
+
This equation is universal.
It does not care about which fluids we are talking about.
Just give it the reduced conditions P
r
, T
r
and it will give
you back V
r
regardless of the fluid.
As long as two gases are at corresponding states (same
reduced conditions), it does not matter what
components you are talking about, or what is the nature
of the substances you are talking about; they will behave
alike.
The compressibility factor at the critical point, which is
defined as
c
c c
c
RT
V P
Z =
Z
c
is predicted to be a constant independent of
substance by many equations of state; the Van der Waals
equation e.g. predicts a value of 0.375
Substance Value
H
2
O 0.23
He 0.30
H
2
0.30
Ne 0.29
N
2
0.29
Ar 0.29
Z
c
of various substances
Standing-Katz
Compressibility
Factor Chart
Application of PCS
The RedlichKwong equation is adequate for calculation
of gas phase properties when:
( ) b V V
a
b V
RT
P
+
o

=
c
2
c
2
P
T R
42748 . 0 a=
c
c
P
T R
08662 . 0 b =
c c
T 2
T
P
P
<
2 1
r
T

= o
Cubic form of RK eos
( ) b V V
a
b V
RT
P

=
( ) 0 AB Z B B A Z Z
2 2 3
= +
2
r
r
2 2
T
P
42748 . 0
T R
P a
A
o
=
o
=
r
r
T
P
08662 . 0
RT
bP
B = =
( ) b V V
a
b V
RT
P
+
o

=
c
2
c
2
P
T R
42748 . 0 a=
c
c
P
T R
08662 . 0 b =
( )( ) { }
2
5 . 0
r
2
T 1 15613 . 0 55171 . 1 48508 . 0 1 e e + + = o
( )
r 2
T 30288 . 0 exp 202 . 1 : H or F = o
Cubic form of SRK eos
( ) b V V
a
b V
RT
P

=
( ) 0 AB Z B B A Z Z
2 2 3
= +
2
r
r
2 2
T
P
42748 . 0
T R
P a
A
o
=
o
=
r
r
T
P
08662 . 0
RT
bP
B = =
2 2
b bV 2 V
a
b V
RT
P
+
o

=
c
2
c
2
P
T R
45724 . 0 a=
c
c
P
T R
07780 . 0 b =
( )( ) { }
2
5 . 0
r
2
T 1 2699 . 0 54226 . 1 37464 . 0 1 e e + + = o
Cubic form of PR eos
( ) ( ) ( ) 0 B B AB Z B 3 B 2 A Z B 1 Z
3 2 2 2 3
= +
2
r
r
2 2
T
P
45724 . 0
T R
P a
A
o
=
o
=
r
r
T
P
07780 . 0
RT
bP
B = =
2 2
b bV 2 V
a
b V
RT
P
+
o

=
0 c Z c Z c Z
0 1
2
2
3
= + + +
eos c
2
c
1
c
0

vdW B 1 A AB
RK 1 A B B
2
AB
SRK 1 A B B
2
AB
PR B 1 A 2B 3B
2
AB B
2
B
3

0 c Z c Z c Z
0 1
2
2
3
= + + +
27
c
c K
2
1
2
=
( )
0 1 2
3
2
c 27 c c 9 c 2
22
1
L + =
4
L
27
K
D
2 3
+ =
(determinant)
Calculate:
3 1
D
2
L
M
|
.
|

\
|
+ =
3 1
D
2
L
N
|
.
|

\
|
=
Case 1: D > 0
1 real root and 2 imaginary roots
3
c
N M Z
2
1
+ =
Case 2: D = 0
three real roots and at least two are equal
3
c
N M Z
2
1
+ =
( )
3
c
N M
2
1
Z Z
2
3 2
+ = =
Case 3: D < 0
three, distinct, real roots
( )
3
c
k 120 cos
3
K
2 Z
2
i
+ |
|
.
|

\
|
=
Where k = 0 for i = 1
k = 1 for i = 2
k = 2 for i = 3
( )
( )
(

= |

27 K
4 L
cos
3
2
1
The minus sign applies when B > 0,
The plus sign applies when B < 0.
. . .
V
D
V
C
V
B
1 Z
3 2
+ + + + =
+ + + = =
2
P ' C P ' B 1
RT
PV
Z
RT
B
' B =
( )
2
2
RT
B C
' C

=
( )
3
3
RT
B 2 BC 3 D
' D
+
=
( )
RTV a
RTe b V P

=
Rb 4
a
T
c
=
2 2
c
e b 4
a
P =
b 2 V
c
=
For mixtures, we apply the same equation, but we
impose certain mixing rules to obtain a and b, which
are functions of the properties of the pure components.
We create a new pseudo pure substance that has the
average properties of the mixture.
( ) ( )

o = o
i j
ij j i m
a y y a

=
i
i i m
b y b
( ) ( ) ( )
j i ij ij
a a k 1 a o o = o