TY - JOUR
T1 - Solvent Polarity of Cyclic Ketone (Cyclopentanone, Cyclohexanone)
T2 - Alcohol (Methanol, Ethanol) Renewable Mixed-Solvent Systems for Applications in Pharmaceutical and Chemical Processing
AU - Duereh, Alif
AU - Guo, Haixin
AU - Honma, Tetsuo
AU - Hiraga, Yuya
AU - Sato, Yoshiyuki
AU - Lee Smith, Richard
AU - Inomata, Hiroshi
PY - 2018/6/6
Y1 - 2018/6/6
N2 - Kamlet-Taft (KT) parameters were measured for four nonaqueous hydrogen bond donor (HBD)-hydrogen bond acceptor (HBA) solvent-pair mixtures: methanol-cyclopentanone, methanol-cyclohexanone, ethanol-cyclopentanone, and ethanol-cyclohexanone to define their solvent polarity as a function of composition. KT mixed-solvent polarities differed greatly from molar average property values. The preferential solvation (PS) model was used to correlate solvent polarity and showed that local compositions of 1:1 (HBD-HBA) complex molecules were highly asymmetric. Trends of KT parameters of both cyclohexanone and cyclopentanone mixtures were similar, although the specific hydrogen bonding interactions of HBD-HBA complex molecules in cyclohexanone mixtures were stronger than those of cyclopentanone mixtures according to density functional theory calculations, infrared spectroscopy, and solution macroscopic properties. Application of the PS model to pharmaceuticals showed that the solvent-pair mixtures have wide-working composition ranges (∼0 < xHBA < ∼ 1) for aspirin, ibuprofen, niflumic acid, p-amino-benzoic, p-hydroxy-benzoic and salicyclic acid, limited composition ranges (ΔxHBA ≈ 0.7) for benzoic acid and temazepam, and narrow composition ranges (ΔxHBA ≈ 0.3) for others. By comparing mixed-solvent polarity with polarity of solvents being used for material, petroleum, and biomass processing, it can be concluded that cyclic ketone-alcohol mixtures have many applications.
AB - Kamlet-Taft (KT) parameters were measured for four nonaqueous hydrogen bond donor (HBD)-hydrogen bond acceptor (HBA) solvent-pair mixtures: methanol-cyclopentanone, methanol-cyclohexanone, ethanol-cyclopentanone, and ethanol-cyclohexanone to define their solvent polarity as a function of composition. KT mixed-solvent polarities differed greatly from molar average property values. The preferential solvation (PS) model was used to correlate solvent polarity and showed that local compositions of 1:1 (HBD-HBA) complex molecules were highly asymmetric. Trends of KT parameters of both cyclohexanone and cyclopentanone mixtures were similar, although the specific hydrogen bonding interactions of HBD-HBA complex molecules in cyclohexanone mixtures were stronger than those of cyclopentanone mixtures according to density functional theory calculations, infrared spectroscopy, and solution macroscopic properties. Application of the PS model to pharmaceuticals showed that the solvent-pair mixtures have wide-working composition ranges (∼0 < xHBA < ∼ 1) for aspirin, ibuprofen, niflumic acid, p-amino-benzoic, p-hydroxy-benzoic and salicyclic acid, limited composition ranges (ΔxHBA ≈ 0.7) for benzoic acid and temazepam, and narrow composition ranges (ΔxHBA ≈ 0.3) for others. By comparing mixed-solvent polarity with polarity of solvents being used for material, petroleum, and biomass processing, it can be concluded that cyclic ketone-alcohol mixtures have many applications.
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U2 - 10.1021/acs.iecr.8b00689
DO - 10.1021/acs.iecr.8b00689
M3 - Article
AN - SCOPUS:85047087956
VL - 57
SP - 7331
EP - 7344
JO - Industrial & Engineering Chemistry Research
JF - Industrial & Engineering Chemistry Research
SN - 0888-5885
IS - 22
ER -