Effect of Non-Hydrocarbon Components:

The natural gases commonly contain hydrogen sulfide (H2S), carbon dioxide (CO2), and Nitrogen
(N2). The presence of nitrogen doesn't greatly affect the Z-factor obtained by methods previously
described; Z-factor increases by about 1% for each 5% of Nitrogen in the gas.
However the presence of hydrogen sulfide and carbon dioxide causes large errors in compressibility
factors obtained by the methods previously discussed. The remedy to this problem is to adjust the
pseudocritical properties to account for the unusual behavior of these acid gases. The equations used
for this adjustment are
= ()

And

= ()
+ ( )

Where; and are used to calculate Tpr and Ppr for acid gases.

is the pseudocritical temperature adjustment factor, which is obtained from figure (6) ((Fig. (3-12)
pp (120) in the reference text book).
The pseudocritical temperature adjustment factor can be calculated through this equation;
. .
= [( + ) ( + ) ] + [ . ] ()

The symbol represents the mole fraction of hydrogen sulfide in the gas.

Example: determine values of pseudocritical temperature and pseudocritical pressure for the gas
given below.
Composition Mole percent
H2S 4.91
N2 0.51
CO2 11.01
C1 57.7
C2 7.22
C3 4.45
i-C4 0.96
n-C4 1.95
i-C5 0.78
n-C5 0.71
C6 1.45
C7 + 8.35
100%
Properties of heptanes plus
Specific gravity 0.807
Molecular weight 142 lb/lb mole

15
Solution:
First, determine value of pseudocritical properties in the usual manner.
Composition yj Tcj, R Pcj, Psia Tcj yj Pcj yj
H2S 0.0491 672.4 1300 33.015 63.830
N2 0.0051 227.5 493.1 1.160 2.515
CO2 0.1101 547.9 1710 60.324 188.271
C1 0.5770 343.3 666.4 198.084 384.513
C2 0.0722 549.9 706.5 39.703 51.009
C3 0.0445 666.1 616.0 29.641 27.412
i-C4 0.0096 734.5 527.9 7.051 5.068
n-C4 0.0195 765.6 550.6 14.929 10.737
i-C5 0.0078 829.1 490.4 6.467 3.825
n-C5 0.0071 845.8 488.6 6.005 3.469
C6 0.0145 913.6 436.9 13.247 6.335
* *
C7 + 0.0835 1157 367 96.610 30.645
1.0000 Tpc=506.24 Ppc=777.63
* Pseudocritical for C7+ from Figure (4) ((Fig. (3-10) pp (116) in the reference text book).
Second, determine the value of and adjust the pseudocritical properties, from figure (6) ((Fig. (3-
12) pp (120) in the reference text book).
= 19.9 R.

Tpc = Tpc = 506.24 19.9 = 486.34 R

Ppc Tpc (777.63)(486.34)
ppc = = = 715 psia
Tpc + yH2 S (1 yH2 S ) 506.24 + 0.0491(1 0.0491)(486.34)

16
Other Equations of State for Real Gases:
Van der Waals Equation of State:
One of the earliest attempts to represent the behavior of real gases by an equation was that of Van der
Waals (1873). He proposed the following equation:

( + ) ( ) = ()

This equation differs from the ideal gas equation by addition of the term a/VM 2 to pressure and
subtraction of the constant (b) from the molar volume. Constants (a) & (b) are characteristic of the
particular gas and when they are zero the ideal gas equation is recovered.
The term (a/VM 2) represents an attempt to correct pressure for the forces of attraction between the
molecules. The actual pressure exerted on the walls of the vessel by real gas is less, by the amount
a/VM 2, than the pressure exerted by an ideal gas.
The constant (b) is regarded as the correction to the molar volume due to the volume occupied by the
molecules.
Equations like the Van der Waals equation often are called two-constant equations of state, although
there are actually three constants: a, b, and R. these equations are also called cubic equations of state.
The Van der Waals equation in cubic form is;

( + ) + () ( ) = ()

The Van der Waals equation is an improvement over the ideal gas equation. However it has limited
use, since it is accurate only at low pressure.
* At high pressures the errors will grow up.
Clausius Equation:
Clausius (1880) proposed that the molecular attraction term is inversely proportional to temperature.

[ + ] ( ) = (3)
( + )2
The addition of the fourth constant, c, enables better agreement with data.
Berthelot Equation:

[ + ( 2
] ( ) = (4)
)

Lorentz Equation:

( + ) ( ) = (5)
2 +

The constants a, b, c in the equations above have different values for different substances. Also, note
that the constants have different values for each of the equations.

17
Equations of State at Critical Point:
The critical temperature isotherm on a pressure-volume diagram for a pure substance has a horizontal
point of inflection as it passes through the critical pressure. Figure below shows this case;

2
( ) =0 ( ) =0 (6)
2

This experimental observation can be used to derive equation for constants a & b in terms of the
critical temperature and critical pressure of the substance.
As an example, consider the Van der Waals equation of state. At the critical point these three
equations apply:

( + ) ( ) = ()

( ) = + = ()
( )

( ) = = ()
( )

18
Combination of these three equations results in;

27 2 2 3
= = = (10)
64 8 8
Equations for the constants of the other equations of states can be determined in a similar manner.
This technique will only work for pure substances.

The Redlich-Kwong Equation of State:

The Redlich-Kwong proposed an equation of state which take in to account the temperature
dependencies of the molecular attraction term similar to Clausius.

[ + 1 ] ( ) = (11)
2 ( + )

Soave suggested that (a/T1/2) be replaced with a temperature dependent term, aT.

[ + ] ( ) = (12)
( + )
The fact that aT varies with temperature is not inconvenient since most applications of this equation
are at constant temperature.
= (13)
Where ac is the value of aT @ the critical temperature and is a non-dimensional temperature
dependent term which has a value of 1.0 @ the critical temperature. This modification is often called
the Soave-Redlich-Kwong (SRK) equation of state.
Setting the first and second derivatives of equation (12) equal to zero at the critical point results in

2 2
= 0.42747 = 0.08664 (14)

The units of b and ac depend on the units of the selected value of R.
Values of are obtained from
1
1/2 = 1 + (1 2 ) (15)

= 0.48 + 1.574 0.1762 (16)

Where is the Pitzer acentric factor. The Pitzer acentric factor is defined as
= (log + 1) @ = 0.7 (17)
Where pvr is the reduced vapor pressure, evaluated @ Tr = 0.7. Thus the acentric factor is a constant
for each pure substance. Values are tabulated in (Appendix A (table A1 pp (493) in the main reference
text book).

19
Peng-Robinson Equation of State:
Peng-Robinson proposed a slightly different form of the molecular attraction term.

[ + ] ( ) = (18)
( + ) + ( )
The term aT is temperature dependent as in the Soave-Redlich-Kwong equation of state; however it
doesnt have exactly the same values. The coefficients are calculated as follows.

2 2
= 0.45724 = 0.0778 (19)

=
1
1/2
= 1 + (1 2 )

= 0.37464 + 1.54226 0.269922 (20)

Mixing Rule:
The following mixture rules are recommended for use with both the Soave-Redlich-Kwong and the
Peng-Robinson equations of state.

= = (21)

Where;
1
2
= (1 ) ( ) (22)

That is:
1
2
= (1 ) ( ) (23)

The term ij are binary interaction coefficient, which are assumed to be independent of pressure and
temperature. Values of the binary interaction coefficients must be obtained by fitting the equation of
state to gas-liquid equilibria data for each binary mixture. The binary interaction coefficients have
different values for each binary pair and also take on different values for each equation of state.
Example: a laboratory cell with volume of 0.008829 ft3 (250 cc) contains 0.007357 lb mole (79.28 g)
of gas. The composition of the gas is given below. The temperature is to be raised to 709.6 R (250
F). Use the SRK equation of state to calculate the pressure to be expected.
Component Composition Mole Fraction
Methane 0.65
Ethane 0.25
n-Butane 0.10
1.00
Use values of 0.02 for binary interaction coefficient between methane and n-butane, 0.01 between
ethane and n-butane, and 0.0 between methane and ethane.
20
Solution:
First, calculate the constants aj and bj for each component.

2 2
= 0.42747 = 0.08664

= 0.48 + 1.574 0.1762

1
1/2 2
= 1 + (1 )

Comp. yj pcj, (psia) Tcj, R bj acj j mj j aTj

C1 0.65 666.4 342.9 0.4784 8687 0.0104 0.4964 0.6120 5316.44
C2 0.25 706.5 549.5 0.7232 21042 0.0979 0.6324 0.8349 17569
n-C4 0.10 550.6 765.2 1.2922 52358 0.1995 0.7870 1.0591 55452.1
1.00

Second, calculate the mixture constants, b and aT.

= = (0.65)(0.4784) + (0.25)(0.7232) + (0.10)(1.2922) = 0.621
1
2
= ( ) (1 )

aT = (0.65)(0.65)(5316.44x5316.44)1/2(1-0.0) + (0.65)(0.25)(5316.44x17569)1/2(1-0.0)
+ (0.65)(0.10)(5316.44x55453)1/2(1-0.02) + (0.25)(0.65)(17569x5316.44)1/2(1-0.0)
+ (0.25)(0.25)(17569x17569)1/2(1-0.0) + (0.25)(0.1)(17569x55453)1/2(1-0.01)
+ (0.1)(0.65)(55453x5316.44)1/2(1-0.02) + (0.1)(0.25)(55453x17569)1/2(1-0.01)
+ (0.1)(0.1)(55453x55453)1/2(1-0.0) = 10.773
Third, calculate pressure.
VM= 0.008829/0.007357 = 1.2 ft3/lb mole,

[ + ] ( ) = = 8223
( + )

21