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Correlation of thermodynamic properties of amine‐water solution with molecular structure
Author(s) -
Davison R. R.,
Hood D. W.,
Harris W. D.
Publication year - 1964
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.690100412
Subject(s) - amine gas treating , thermodynamics , correlation , chemistry , materials science , organic chemistry , mathematics , physics , geometry
The solutions of amines and water are in several respects among the most interesting that have been studied. They give some of the most perfect examples of lower consolute temperatures with fast breaking, almost flat solubility curves near the critical solution point. Their heat and entropy of solution are very high, and with few other solutions do the thermodynamic properties show greater sensitivity to molecular structure. The activity coefficients for these solutions are inordinately difficult to fit with equations such as the Margules, Redlich‐Kister, etc., requiring as many as six constants. It has been found however that some of the properties can be correlated in terms of structural parameters which are measures of the steric and inductive contribution of the substituent groups. A very good correlation of the heat of solution at infinite dilution of amines in water is given. An equation of the Margules type employing orthogonal polynomials is given for which the constants are similarly correlated. Five six‐carbon atom amines at 10°C. are included in the latter correlations, and the activity coefficients of all of these are represented in terms of two structural parameters.