Physics:Lee–Kesler method

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Short description: Method to estimate saturated vapor pressure

The Lee–Kesler method [1] allows the estimation of the saturated vapor pressure at a given temperature for all components for which the critical pressure Pc, the critical temperature Tc, and the acentric factor ω are known.

Equations

[math]\displaystyle{ \ln P_{\rm r} = f^{(0)} + \omega \cdot f^{(1)} }[/math]
[math]\displaystyle{ f^{(0)}=5.92714 - \frac{6.09648}{T_{\rm r}} - 1.28862 \cdot \ln T_{\rm r} + 0.169347 \cdot T_{\rm r}^6 }[/math]
[math]\displaystyle{ f^{(1)}=15.2518 - \frac{15.6875}{T_{\rm r}}-13.4721 \cdot \ln T_{\rm r} + 0.43577 \cdot T_{\rm r}^6 }[/math]

with

[math]\displaystyle{ P_{\rm r}=\frac{P}{P_{\rm c}} }[/math] (reduced pressure) and [math]\displaystyle{ T_{\rm r}=\frac{T}{T_{\rm c}} }[/math] (reduced temperature).

Typical errors

The prediction error can be up to 10% for polar components and small pressures and the calculated pressure is typically too low. For pressures above 1 bar, that means, above the normal boiling point, the typical errors are below 2%. [2]

Example calculation

For benzene with

  • Tc = 562.12 K[3]
  • Pc = 4898 kPa[3]
  • Tb = 353.15 K[4]
  • ω = 0.2120[5]

the following calculation for T=Tb results:

  • Tr = 353.15 / 562.12 = 0.628247
  • f(0) = -3.167428
  • f(1) = -3.429560
  • Pr = exp( f(0) + ω f(1) ) = 0.020354
  • P = Pr * Pc = 99.69 kPa

The correct result would be P = 101.325 kPa, the normal (atmospheric) pressure. The deviation is -1.63 kPa or -1.61 %.

It is important to use the same absolute units for T and Tc as well as for P and Pc. The unit system used (K or R for T) is irrelevant because of the usage of the reduced values Tr and Pr.

See also

References

  1. Lee B.I., Kesler M.G., "A Generalized Thermodynamic Correlation Based on Three-Parameter Corresponding States", AIChE J., 21(3), 510-527, 1975
  2. Reid R.C., Prausnitz J.M., Poling B.E., "The Properties of Gases & Liquids", 4. Auflage, McGraw-Hill, 1988
  3. 3.0 3.1 Brunner E., Thies M.C., Schneider G.M., J.Supercrit.Fluids, 39(2), 160-173, 2006
  4. Silva L.M.C., Mattedi S., Gonzalez-Olmos R., Iglesias M., J.Chem.Thermodyn., 38(12), 1725-1736, 2006
  5. Dortmund Data Bank