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Prediction of Solubility of Solid Organic Compounds in Solvents by UNIFAC
KTH, Superseded Departments, Chemical Engineering and Technology.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Physical Chemistry.ORCID iD: 0000-0003-2673-075X
KTH, Superseded Departments, Chemical Engineering and Technology.
2002 (English)In: Industrial & Engineering Chemistry Research, ISSN 0888-5885, E-ISSN 1520-5045, Vol. 41, no 20, 5114-5124 p.Article in journal (Refereed) Published
Abstract [en]

Predictions of solubility of nine different solid organic fine chemical compounds in water and organic solvents of relevance to industrial processing are examined. UNIFAC interaction parameters are taken from standard reference literature, extracted from liquid-vapor equilibria. For most systems, predicted solubilities deviate more than 15% from experimental values. Deviations are due to uncertainties in the estimation of the activity of the pure solid as well as to deficiencies in the estimation of activity coefficients in the solution. By comparison with results from ab initio quantum chemical calculations of the elecrostatic potential on the molecular surface of the solutes, it can be shown that a key assumption of the UNIFAC approach is not necessarily fulfilled. The properties of a functional group may depend significantly on the properties of the rest of the molecule.

Place, publisher, year, edition, pages
2002. Vol. 41, no 20, 5114-5124 p.
Keyword [en]
Organic compounds, Solvents, Uncertain systems, ab initio calculation, article, calculation, electricity, industry, liquid, molecule, parameter, prediction, processing, quantum chemistry, solid, solubility, solute, standard, vapor
National Category
Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-5294DOI: 10.1021/ie011014wISI: 000178283700025OAI: oai:DiVA.org:kth-5294DiVA: diva2:8344
Note
QC 20100927 NR 20140805Available from: 2005-06-07 Created: 2005-06-07 Last updated: 2017-12-04Bibliographically approved
In thesis
1. Solubility and polymorphism of molecular compounds
Open this publication in new window or tab >>Solubility and polymorphism of molecular compounds
2005 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis deals with the controlled crystallization of small organic molecules and is focused on solubility and polymorphism. The solubility was determined for phenylacetic acid, p-hydroxyphenylacetic acid, p-aminophenylacetic acid, p-hydroxybenzoic acid and ibuprofen in both water and in a range of organic solvents. Data is discussed from the standpoint of molecular aspects of solute – solvent interactions and by estimated solid phase activity. It was shown that better understanding could be acquired by making a qualitative analysis of the molecular interactions in the solution and the crystal structure of the compounds in question.

Solubility predictions that are carried out by the UNIFAC method are not sufficiently accurate to serve as a basis for a reliable design of a crystallization process or selection of a suitable solvent since they deviate more than 15% from experimental values. The reason for the discrepancies are related to uncertainties in the prediction of activity coefficients by UNIFAC, as well as, difficulties in the estimation of the activity of the solid state.

p-Aminobenzoic acid (PABA) has been crystallized from thirteen different solvents either by slow cooling, after which the product is allowed to mature in suspension, or by rapid cooling followed by immediate isolation. Two different polymorphs have been crystallized. The system is found to be enantiotropic with the transition temperature of 25 °C, below which the β-form is the stable polymorph. The α-form was obtained from all solvents by both methods. The β-form is obtained only in carefully controlled conditions from water and ethyl acetate, well below the transition temperature. Often the α-form appears concomitantly.

It is shown in this work that sonication significantly reduces the induction time for nucleation. The β-form crystallizes more reproducibly and at higher cooling rates when controlled sonication is used. In addition sonication is found to selectively favor the appearance of one of the polymorphs. Producing the pure β-form was possible even above the transition temperature where other crystallization techniques were only capable of producing the stable α-form. The α-form structure is based on centro symmetric dimers formed by association of carboxylic acid groups. It is suggested that the preference for nucleation of the α-polymorph is related to the formation of dimers in the supersaturated solution. Only at the condition where the formation of dimers is reduced sufficiently, (i.e. in the polar solvents or when sonication is applied) the nucleation of the β-form is favored.

Place, publisher, year, edition, pages
Stockholm: KTH, 2005. viii, 63 p.
Series
Trita-KET, ISSN 1104-3466 ; 215
Keyword
Chemical engineering, solubility, prediction of solubility, UNIFAC, activity coefficients, activity of the solid phase, polymorphism, controlled crystallization, sonication., Kemiteknik
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-267 (URN)91-7178-077-7 (ISBN)
Public defence
2005-06-17, Sal E3, Lindstedtsvägen 3, Stockholm, 12:00
Opponent
Supervisors
Note
QC 20101014Available from: 2005-06-07 Created: 2005-06-07 Last updated: 2010-10-14Bibliographically approved

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Brinck, Tore

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