Generalized Correlations for Gases

(Lee-Kesler)

By:
The Generalized Correlation for Gases

 The generalized Pitzer’s correlation is a three-parameter corresponding

states method for estimating thermodynamic properties of pure, nonpolar
fluids . For the compressibility factor Z, it takes the form

Z = Z0 + ω Z1
where,
Z0 = Compressibility factor for fluids of nearly spherical molecules,
ω = Pitzer's acentric factor, and
Z1 = Corrects for nonspherical intermolecular forces.

 Appendix E provides values of Z0 and Z1 (Lee-Kessler correlations), from

which Z can be calculated and, hence, the molar volume can be computed.
 Virial equations
The Virial equation (up to the second Virial coefficient) provides an
approximation of Z and the equation is:
Cont……

The virial equation (up to the Third coefficient) also provides an approximation of
Z. Such virial equation is:
Example Problem
Determine the molar volume of n-butane at 510 K and 25 bar by each of
the following:
a) The ideal-gas equation,
b) The generalized compressibility-factor correlation,
c) Generalized correlation for using eq. 3.61,
d) Equation 3.68 the third virial coefficient equation.
A. By the Ideal Gas equation:
B. From the values of Tc and Pc given
in Table B.1 of App. B
 C. Using the Second Virial Equation
BP
P
T
25bar
510K Z  1
Pc 37.96bar RT
Tc
Pr
425.1K
ˆ BP c
Tr
0.658587987
1.199717713
B 
ω 0.2 RT c
B0 -0.232344991 Bˆ P r
B1 0.058943546
-0.220556282
 Z  1
Tr
Z 0.878925087

R 83.14cm3bar/molK
V 1490.706167cm3/mol
Here, Excel was used to calculate
the volume using second virial
coefficient equation.
Bˆ  B 0   B 1
0 0 . 422
B  0 . 083 
T r1 . 6
1 0 . 172
B  0 . 139 
T r4 .2
D. Using Second and Third Virial coefficient
P 25bar
T 510K
Pc 37.96bar
Tc 425.1K

Z
Pr 0.658587987 Z (Guess) (Calculated)
Tr 1.199717713 1 0.889316
ω 0.2 0.889316 0.876994
0.876994 0.875453
B0 -0.232344991 0.875453 0.875258
B1 0.058943546 0.875258 0.875233
-0.220556282 0.875233 0.87523
0.87523 0.875229
C0 0.03312865 0.875229 0.875229
C1 0.006760336 0.875229 0.875229
0.034480717 0.875229 0.875229
0.875229 0.875229
0.875229 0.875229 This is the third coefficient
R 83.14cm3bar/molK 0.875229 0.875229
virial equation for the same
V 1484.438039cm3/mol 0.875229 0.875229
problem. Again Excel was used
0.875229 0.875229
0.875229 0.875229 to obtain the solution. The
solution is again very close to
the value obtained by the Lee-
Kesler method.
Where the Virial Equation Applies
 The second coefficient
virial equation works at
low pressures where Z is a
linear function. It is used
when an approximation of
a non ideal gas is needed,
but at non extreme
temperatures and
pressures.
 The third virial coefficient
equation provides another
correction to the virial
equation.

This graph shows the difference obtained for

the Z0 value for the Lee/Kesler correlation vs.
the virial coefficient equation.