Investigating the Role of Solvent-Solute Interaction in Crystal Nucleation of Salicylic Acid from Organic Solvents.
In previous work, it has been shown that the crystal nucleation of salicylic acid (SA) in different solvents becomes increasingly more difficult in the order: chloroform, ethyl acetate acetonitrile, acetone, methanol, and acetic acid. In the present work, vibration spectroscopy, calorimetric measure...
| Published in: | Journal of the American Chemical Society Vol. 136; no. 33; pp. 11664 - 11674 |
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| Main Authors: | , , , |
| Format: | Article |
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American Chemical Society
8/20/2014
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=98254100&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 98254100 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 8/20/2014 vid: 136 iid: 33 pid: 997 pub: American Chemical Society artinfo: ui: 98254100 10.1021/ja503131w ppf: 11664 ppct: 10 formats: tig: atl: Investigating the Role of Solvent-Solute Interaction in Crystal Nucleation of Salicylic Acid from Organic Solvents. aug: au: Khamar, Dikshitkumar Zeglinski, Jacek Mealey, Donal Rasmuson, Åke C. affil: Materials and Surface Science Institute, Department of Chemical and Environmental Science, University of Limerick, Limerick, Ireland Department of Chemical Engineering and Technology, KTH Royal Institute of Technology, SE-100 44 Stockholm, Sweden su: Nucleation Crystal growth Salicylic acid Solution (Chemistry) Solvent testing Vibrational spectra Calorimetry Density functional theory sug: subj: Nucleation Crystal growth Salicylic acid Solution (Chemistry) Solvent testing Vibrational spectra Calorimetry Density functional theory ab: In previous work, it has been shown that the crystal nucleation of salicylic acid (SA) in different solvents becomes increasingly more difficult in the order: chloroform, ethyl acetate acetonitrile, acetone, methanol, and acetic acid. In the present work, vibration spectroscopy, calorimetric measurements, and density functional theory (DFT) calculations are used to reveal the underlying molecular mechanisms. Raman and infrared spectra suggest that SA exists predominately as dimers in chloroform, but in the other five solvents there is no clear evidence of dimerization. In all solvents, the shift in the SA carbonyl peak reflecting the strength in the solvent—solute interaction is quite well correlated to the nucleation ranking. This shift is corroborated by DFT calculated energies of binding one solvent molecule to the carboxyl group of SA. An even better correlation of the influence of the solvent on the nucleation is provided by DFT calculated energy of binding the complete first solvation shell to the SA molecule. These solvation shell binding energies are corroborated by the enthalpy of solvent—solute interaction as estimated from experimentally determined enthalpy of solution and calculated enthalpy of cavity formation using the scaled particle theory. The different methods reveal a consistent picture and suggest that the stronger the solvent binds to the SA molecule in solution, the slower the nucleation becomes. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2014 holdings: @attributes: islocal: N |
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