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Influence of history of solution in crystal nucleation of fenoxycarb: kinetics and mechanisms

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dc.contributor.author Kuhs, Manuel
dc.contributor.author Zeglinski, Jacek
dc.contributor.author Rasmuson, Åke C.
dc.date.accessioned 2015-05-19T12:40:32Z
dc.date.available 2015-05-19T12:40:32Z
dc.date.issued 2014
dc.identifier.uri http://hdl.handle.net/10344/4475
dc.description peer-reviewed en_US
dc.description.abstract Nearly 1800 induction time experiments have been performed on crystal nucleation of fenoxycarb in isopropanol to investigate the influence of solution pretreatment. For each preheating temperature and preheating time, at least 80 experiments were performed to obtain statistically valid results. The relationship between the inverse of the induction time and the preheating time can be reasonably described as an exponential decay having time constants ranging up to days depending on the temperature. This dependence on the preheating temperature corresponds to an activation energy of over 200 kJ/mol. Given sufficiently long preheating time and high temperature, the solution appears to reach a steady-state where the “memory” effect has disappeared. Density functional theory modelling suggests that the molecular packing in the crystal lattice is not the thermodynamically stable configuration at the level of simple dimers in solution, while modelling of the first solvation shell reveals that solute aggregation must exist in solution due to the low solvent to solute molecular ratio. It is thus hypothesized that the dissolution of crystalline material at first leaves molecular assemblies in solution that retain features of the crystalline structure which facilitates subsequent nucleation. However, the longer the solution is kept at a temperature above the saturation temperature and the higher the temperature, the more these assemblies disintegrate, and transform into molecular structures less suited to form critical nuclei. en_US
dc.language.iso eng en_US
dc.publisher American Chemical Society en_US
dc.relation.ispartofseries Crystal Growth and Design;14 (3), pp. 905-915
dc.relation.uri http://dx.doi.org/10.1021/cg4007795
dc.rights This document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in Crystal, Growth and Design, copyright © American Chemical Society after peer review. To access the final edited and published work, see http://dx.doi.org/10.1021/cg4007795
dc.subject crystal en_US
dc.subject fenoxycarb nucleation
dc.title Influence of history of solution in crystal nucleation of fenoxycarb: kinetics and mechanisms en_US
dc.type info:eu-repo/semantics/article en_US
dc.type.supercollection all_ul_research en_US
dc.type.supercollection ul_published_reviewed en_US
dc.date.updated 2014-11-28T18:54:57Z
dc.description.version ACCEPTED
dc.identifier.doi 10.1021/cg4007795
dc.contributor.sponsor SFI en_US
dc.relation.projectid 10/IN.1/B3038 en_US
dc.rights.accessrights info:eu-repo/semantics/openAccess en_US
dc.internal.rssid 1572702
dc.internal.copyrightchecked Yes
dc.description.status peer-reviewed


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