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  • 1
    ISSN: 1040-7685
    Keywords: Phase behavior ; supercritical fluid chromatography ; supercritical fluid extraction ; modifier ; propylene carbonate ; critical parameters ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The phase behavior (P-T-x) of propylene carbonate was studied using a variable volume view cell for the regions applicable to supercritical fluid chromatography (SFC) and extraction (SFE). Type 5 phase behavior was observed. Phase separation was shown to significantly alter retention and selectivity in the analysis of coal extracts by capillary SFC. Propylene carbonate was found to have limited use as a modifier in capillary SFC. With 5.1 mol% propylene carbonate at 60°C, a single phase is maintained only at pressures above 250 atm.Twenty-two methods used to estimate critical pressure (Pc), twenty-seven methods used to estimate critical temperature (Tc), and thirty methods used to estimate critical volume (Vc) were evaluated for various modifiers employed in supercritical fluid chromatography (SFC). None of the methods could predict Pc, Tc, or Vc to within a 5% relative error for all of the modifiers tested. However, several of the methods were successful in predicting Pc, Tc, or Vc to within 5% for select chemical classes of compounds.Four methods used to estimate the vapor-liquid critical loci of binary mixtures not only failed to accurately predict vapor-liquid separation, but failed to predict the type of phase separation occurring. None of the above methods could reliably estimate the critrical parameters of propylene carbonate or the critical parameters of the mixture.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 20 (1985), S. 115-121 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The positive ion-molecule reactions of OCS have been investigated in an ion cyclotron resonance spectrometer. A variety of reactions in OCS/hydrocarbon mixtures have been investigated for various C1—C4 hydrocarbons - alkanes, alkenes and alkynes. The formation of organosulfur ions is found in reactions in OCS/hydrocarbon (Cn) mixtures with n 〈4. Formation of organosulfur ions is observed from hydrocarbon ions reacting with OCS and [OCS]+· and S+· reacting with the hydrocarbons. The proton affinity of OCS has been determined to be 688.7±8 kJ mol-1 while that of CS2 is measured to be 712.1±8 kJ mol-1. Comparison with the proton affinity of CO2 shows that the proton affinity increases as sulfur is substituted for oxygen.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
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