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Prediction of Solubility of Solid Organic Compounds in Solvents by UNIFAC
KTH, Tidigare Institutioner, Kemiteknik.
KTH, Skolan för kemivetenskap (CHE), Kemi, Fysikalisk kemi.ORCID-id: 0000-0003-2673-075X
KTH, Tidigare Institutioner, Kemiteknik.
2002 (engelsk)Inngår i: Industrial & Engineering Chemistry Research, ISSN 0888-5885, E-ISSN 1520-5045, Vol. 41, nr 20, s. 5114-5124Artikkel i tidsskrift (Fagfellevurdert) 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.

sted, utgiver, år, opplag, sider
2002. Vol. 41, nr 20, s. 5114-5124
Emneord [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
HSV kategori
Identifikatorer
URN: urn:nbn:se:kth:diva-5294DOI: 10.1021/ie011014wISI: 000178283700025OAI: oai:DiVA.org:kth-5294DiVA, id: diva2:8344
Merknad
QC 20100927 NR 20140805Tilgjengelig fra: 2005-06-07 Laget: 2005-06-07 Sist oppdatert: 2017-12-04bibliografisk kontrollert
Inngår i avhandling
1. Solubility and polymorphism of molecular compounds
Åpne denne publikasjonen i ny fane eller vindu >>Solubility and polymorphism of molecular compounds
2005 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Stockholm: KTH, 2005. s. viii, 63
Serie
Trita-KET, ISSN 1104-3466 ; 215
Emneord
Chemical engineering, solubility, prediction of solubility, UNIFAC, activity coefficients, activity of the solid phase, polymorphism, controlled crystallization, sonication., Kemiteknik
HSV kategori
Identifikatorer
urn:nbn:se:kth:diva-267 (URN)91-7178-077-7 (ISBN)
Disputas
2005-06-17, Sal E3, Lindstedtsvägen 3, Stockholm, 12:00
Opponent
Veileder
Merknad
QC 20101014Tilgjengelig fra: 2005-06-07 Laget: 2005-06-07 Sist oppdatert: 2010-10-14bibliografisk kontrollert

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