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Generalized Correlations For Gases (Lee-Kesler)

The document discusses generalized correlations for estimating thermodynamic properties of nonpolar gases using corresponding states methods. It presents the Lee-Kesler correlation, which uses three parameters to estimate the compressibility factor Z as a function of Pitzer's acentric factor and two correlation parameters. It also discusses using the virial equation up to the second and third virial coefficients as approximations of Z, and provides an example problem comparing methods for determining the molar volume of n-butane at various conditions.

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amir lolo
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396 views10 pages

Generalized Correlations For Gases (Lee-Kesler)

The document discusses generalized correlations for estimating thermodynamic properties of nonpolar gases using corresponding states methods. It presents the Lee-Kesler correlation, which uses three parameters to estimate the compressibility factor Z as a function of Pitzer's acentric factor and two correlation parameters. It also discusses using the virial equation up to the second and third virial coefficients as approximations of Z, and provides an example problem comparing methods for determining the molar volume of n-butane at various conditions.

Uploaded by

amir lolo
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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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
Bˆ  B 0   B 1
V 1490.706167cm3/mol
0 0 . 422
B  0 . 083 
T r1 . 6
1 0 . 172
Here, Excel was used to calculate B  0 . 139 
the volume using second virial
coefficient equation.
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.

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