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Optimal determination of the vapor pressure critical exponent
Author(s) -
Walton Clifford W.,
Mullins Joseph C.,
Holste James C.,
Hall Kenneth R.,
Eubank Philip T.
Publication year - 1978
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.690240609
Subject(s) - vapor pressure , exponent , curvature , scaling , maxima and minima , range (aeronautics) , mathematics , thermodynamics , power law , boiling point , statistical physics , mathematical analysis , chemistry , physics , statistics , materials science , geometry , linguistics , philosophy , composite material
Correlations producing thermodynamic property tables employ the concepts of scaling with increasing frequency in the vapor‐liquid critical region. One of the important concepts is that the vapor pressure equation should provide infinite curvature and finite slope ψ c at the critical point. The vapor pressure critical exponent θ describes the divergent curvature in a power law expression. This paper provides an extensive study of θ. We have determined an optimal value of θ by two general approaches: a curve fit method (CFM) which employs least‐squares analyses, and a numerical derivative method (NDM). The CFM is interpolative but requires a vapor pressure equation, while the NDM is extrapolative but is independent of the vapor pressure equation. The vapor pressure equations, which satisfy scaling concepts most closely, exhibit a very flat minima for the CFM. As a result, the values of θ which provide reasonable correlations vary over an appreciable range (depending upon the compound, form of the equation, and the temperature range). The NDM did not present any particular difficulties. Our overall weighted average for θ is 0.199 with a standard deviation of 0.052, while the overall numerical average was 0.225 with a standard deviation of 0.045; the final recommended value of θ is 0.22 ± 0.04.