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  • Chemistry  (3)
  • Cavity term  (1)
  • Interaction of mobile and stationary phases  (1)
  • 1
    ISSN: 1612-1112
    Schlagwort(e): Column liquid chromatography ; Reversed-phase capacity factors ; Cavity term ; Molar volumes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Reversed-phase liquid chromatographic capacity factors are well correlated by an equation of the form: $$logk' = (logk')_0 + mV/100 + s\pi ^* + b\beta + a\alpha $$ wheremV/100 measures the cavity term and π*, β, and α are the solvatochromic parameters that measure solute dipolarity/polarizability, hydrogen bond acceptor basicity, and hydrogen bond donor acidity respectively. Liquid molar volume (molecular weight divided by liquid density at 20°C) $$\bar V$$ , and computer-calculated intrinsic (van der Waals) molecular volume, $$\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{V} _I $$ , are compared as measures of the cavity term in a number of correlations. $$\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{V} _I $$ leads to more precise correlations as well as to a “cleaner” dissection of the multiple solute/solvent interactions. The opposing exoergic effect of solvent donor/solute acceptor hydrogen bonding, and endoergic cavity term are the main factors influencing HPLC capacity factors.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    ISSN: 1612-1112
    Schlagwort(e): Column liquid chromatography ; Interaction of mobile and stationary phases ; Linear solvation energy relationships ; Triethylamine
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary The effect of triethylamine (TEA) in the mobile phase on the RPLC retention behavior of small organic solutes has been studied on a conventional polymeric octadecylsilica (ODS) and on a horizontally polymerized ODS. Retention factors for a set of solutes were measured on the two phases with methanol-water mobile phases containing triethylamine at different concentrations and analyzed by use of linear solvation energy relationships (LSER). Variation of the resulting LSER coefficients—v (hydrophobicity),r (polarizability),s (dipolarity),b (hydrogen-bond (HB) donating acidity), anda (HB accepting strength)—were examined to see how TEA affects the intermolecular interaction properties of the mobile and stationary phases and hence the retention of the solutes. Addition of TEA to the mobile phase changes the interaction properties of both conventionally polymerized and horizontally polymerized ODS; the effect is greater for the conventional phase. The HB donating acidity (b) of conventional polymeric ODS is significantly reduced by addition of TEA. For the mobile phases studied the magnitudes of theb andv coefficients for the horizontally polymerized ODS phase are greater than for the conventional phase. The different interaction properties of the two polymeric phases arise mainly as a result of differential adsorption of TEA, because of the very different amounts of surface silanol groups present on the two phases.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 1493-1498 
    ISSN: 0001-1541
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Racemic leucine can be separated into d- and l-isomers by fractional extraction across microporous hollow fibers. In this extraction, an aqueous solution of the racemate is fed to the lumen of the fibers, and an octanol solution of dodecyl-l-hydroxyproline flows countercurrently outside of the fibers. The interface between feed and extractant is stabilized by filling the pores in the hollow-fiber walls with a cross-linked polyvinylalcohol gel which offers negligible resistance to mass transfer. The extraction with dodecyl-l-hydroxyproline deliberately imitates earlier studies, facilitating comparisons of hollow-fiber extraction with other techniques. The results show that the isomer yield per equipment volume of racemic separation is 100 times greater than that in a continuously rotating extractor, and 1,000 times greater than that in a conventional packed tower.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 946-953 
    ISSN: 0001-1541
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: This article demonstrates that even 1% polydispersity in hollow-fiber diameters can increase plate heights by as much as an order of magnitude. The demonstration includes an analytical extension of the Taylor-Aris and the Golay dispersion theories, a numerical solution using the measured polydisperity, and successful predictions of the performance of different hollow-fiber systems over a range of flow rates. All these results show that the effect of polydispersity can dominate column performance, especially in the region where the column efficiency is optimal.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 53 (1994), S. 633-640 
    ISSN: 0021-8995
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: Infrared spectroscopy has been used to provide an independent estimate of dipole orientation in poled films of a side-chain polymer based on poly(methyl methacrylate) with an oxynitrostilbene side group attached via an aliphatic spacer. In particular, we used the dichroism of the absorption band assigned to the NO2 symmetric stretching vibration as a measure of the orientation of the nitrostilbene group. This yields 〈P2(cos θ)〉, where θ is the angle between the transition dipole moment and the symmetry axis of the sample. We then used a Langevin-type model to calculate 〈cos θ〉 from 〈P2(cos θ)〉 and concluded that values of 〈cos θ〉 as high as 0.5 are being achieved. We find, however, that 〈P2(cos θ)〉 obtained by comparison of normal incidence measurements on unpoled and poled films does not agree with 〈P2(cos θ)〉 obtained from tilted-film measurements on poled films. We propose that this discrepancy arises because the local field in a poled sample affects the polarizability of the molecules. To confirm this, we applied high fields to unpoled films in the infrared spectrometer at room temperature. The results clearly show a large reduction in absorbance with the applied field when the infrared electric field vector has a component perpendicular to the plane of the film. A major error therefore occurs as a consequence of the internal field in poled samples if 〈P2(cos θ)〉 is derived from the tilted film measurements, whereas 〈P2(cos θ)〉 derived from normal incidence measurements is essentially correct. © 1994 John Wiley & Sons, Inc.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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