Physics:Acentric factor

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The acentric factor ω is a conceptual number introduced by Kenneth Pitzer in 1955, proven to be useful in the description of fluids.[1] It has become a standard for the phase characterization of single & pure components, along with other state description parameters such as molecular weight, critical temperature, critical pressure, and critical volume (or critical compressibility). The acentric factor is also said to be a measure of the non-sphericity (centricity) of molecules.[2]

Pitzer defined ω from the relationship

[math]\displaystyle{ \omega = - \log_{10} (p^{\rm{sat}}_r) - 1, {\rm \ at \ } T_r = 0.7 }[/math]

where [math]\displaystyle{ p^{\rm{sat}}_r = \frac{p^{\rm{sat}}}{p_c} }[/math] is the reduced saturation vapor pressure and [math]\displaystyle{ T_r = \frac{T}{T_c} }[/math] is the reduced temperature.

For a series of fluids, as the acentric factor increases the vapor curve is "pulled" down, resulting in higher boiling points. For many monatomic fluids, [math]\displaystyle{ p_r^{\rm{sat}}{\rm \ at \ } T_r = 0.7 }[/math] is close to 0.1, which leads to [math]\displaystyle{ \omega \to 0 }[/math]. In many cases, [math]\displaystyle{ T_r = 0.7 }[/math] lies above the boiling temperature of liquids at atmosphere pressure.

Values of ω can be determined for any fluid from accurate experimental vapor pressure data. The definition of ω gives values which are close to zero for the noble gases argon, krypton, and xenon. [math]\displaystyle{ \omega }[/math] is also very close to zero for molecules which are nearly spherical.[2] Values of ω ≤ -1 correspond to vapor pressures above the critical pressure, and are non-physical.

The acentric factor can be predicted analytically from some equations of state. For example, it can be easily shown from the above definition that a van der Waals fluid has an acentric factor of about −0.302024, which if applied to a real system would indicate a small, ultra-spherical molecule.[3]

Values of some common gases

Molecule Acentric Factor[4]
Acetone 0.304[5]
Acetylene 0.187
Ammonia 0.253
Argon 0.000
Carbon Dioxide 0.228
Decane 0.484
Ethanol 0.644[5]
Helium -0.390
Hydrogen -0.220
Krypton 0.000
Methanol 0.556[5]
Neon 0.000
Nitrogen 0.040
Nitrous Oxide 0.142
Oxygen 0.022
Xenon 0.000

See also

References

  1. Adewumi, Michael. "Acentric Factor and Corresponding States". Pennsylvania State University. https://www.e-education.psu.edu/png520/m8_p3.html. 
  2. 2.0 2.1 Saville, G. (2006). "ACENTRIC FACTOR". A-to-Z Guide to Thermodynamics, Heat and Mass Transfer, and Fluids Engineering. doi:10.1615/AtoZ.a.acentric_factor. 
  3. Shamsundar, N.; Lienhard, J.H. (December 1983). "Saturation and metastable properties of the van der waals fluid". Canadian Journal of Chemical Engineering 61 (6): 876–880. doi:10.1002/cjce.5450610617. https://onlinelibrary.wiley.com/doi/pdf/10.1002/cjce.5450610617. Retrieved 10 August 2022. 
  4. Yaws, Carl L. (2001). Matheson Gas Data Book. McGraw-Hill. 
  5. 5.0 5.1 5.2 Reid, R.C.; Prausnitz, J.M.; Poling, B.E. (1987). The Properties of Gases and Liquids (4th ed.). McGraw-Hill. ISBN 0070517991.