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Use of ab initio quantum mechanics calculations in group contribution methods. 2; Test of new groups in UNIFAC

Journal Article · · Industrial and Engineering Chemistry Research; (United States)
DOI:https://doi.org/10.1021/ie00053a011· OSTI ID:7282367
;  [1]
  1. Dept. of Chemical Engineering, Univ. of Delaware, Newark, DE (US)
In this paper the authors show that functional groups identified previously from ab initio molecular orbital calculations lead to better UNIFAC predictions of vapor --- liquid equilibrium, especially for mixtures involving molecules in which proximity effects are important. The authors also find that, for the functional groups we have defined, in many cases it is generally not necessary to distinguish between subgroups. This reduces the total number of main groups and subgroups that must be considered. For some hydrogen-bonding mixtures, neither the new nor the old functional groups lead to satisfactory excess Gibbs free energy predictions. This is in agreement with our previously reported supermolecule calculations which showed that hydrogen-bonding energies did not satisfy group additivity and therefore could not be accounted in group contribution methods.
OSTI ID:
7282367
Journal Information:
Industrial and Engineering Chemistry Research; (United States), Journal Name: Industrial and Engineering Chemistry Research; (United States) Vol. 30:5; ISSN IECRE; ISSN 0888-5885
Country of Publication:
United States
Language:
English