A site-specific and multielement approach to the determination of liquid-vapor isotope fractionation parameters: the case of alcohols

Isotope fractionation phenomena occurring at the natural abundance level in the course of liquid-vapor transformation have been investigated by using the SNIF-NMR method (site-specific natural isotope fractionation studied by NMR) which has a unique capability of providing simultaneous access to fra...

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Veröffentlicht in:Journal of physical chemistry (1952) 1990-10, Vol.94 (21), p.8303-8309
Hauptverfasser: Moussa, Issam, Naulet, Norbert, Martin, Maryvonne L, Martin, G. J
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container_end_page 8309
container_issue 21
container_start_page 8303
container_title Journal of physical chemistry (1952)
container_volume 94
creator Moussa, Issam
Naulet, Norbert
Martin, Maryvonne L
Martin, G. J
description Isotope fractionation phenomena occurring at the natural abundance level in the course of liquid-vapor transformation have been investigated by using the SNIF-NMR method (site-specific natural isotope fractionation studied by NMR) which has a unique capability of providing simultaneous access to fractionation parameters associated with different molecular isotopomers. This new approach has been combined with the determination of overall carbon and hydrogen fractionation effects by isotope ratio mass spectrometry (IRMS). The results of distillation and evaporation experiments of alcohols performed in technical conditions of practical interest have been analyzed according to the Rayleigh-type model. In order to check the performance of the column, unit fractionation factors were measured beforehand for water and for the hydroxylic sites of methanol and ethanol for which liquid-vapor equilibrium constants were already known. Inverse isotope effects are determined in distillation experiments for the overall carbon isotope ratio and for the site-specific hydrogen isotope ratios associated with the methyl and methylene sites of methanol and ethanol. In contrast, normal isotope effects are produced by distillation for the hydroxylic sites and by evaporation for all the isotopic ratios.
doi_str_mv 10.1021/j100384a056
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Chem</addtitle><date>1990-10</date><risdate>1990</risdate><volume>94</volume><issue>21</issue><spage>8303</spage><epage>8309</epage><pages>8303-8309</pages><issn>0022-3654</issn><eissn>1541-5740</eissn><coden>JPCHAX</coden><abstract>Isotope fractionation phenomena occurring at the natural abundance level in the course of liquid-vapor transformation have been investigated by using the SNIF-NMR method (site-specific natural isotope fractionation studied by NMR) which has a unique capability of providing simultaneous access to fractionation parameters associated with different molecular isotopomers. This new approach has been combined with the determination of overall carbon and hydrogen fractionation effects by isotope ratio mass spectrometry (IRMS). The results of distillation and evaporation experiments of alcohols performed in technical conditions of practical interest have been analyzed according to the Rayleigh-type model. In order to check the performance of the column, unit fractionation factors were measured beforehand for water and for the hydroxylic sites of methanol and ethanol for which liquid-vapor equilibrium constants were already known. Inverse isotope effects are determined in distillation experiments for the overall carbon isotope ratio and for the site-specific hydrogen isotope ratios associated with the methyl and methylene sites of methanol and ethanol. In contrast, normal isotope effects are produced by distillation for the hydroxylic sites and by evaporation for all the isotopic ratios.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/j100384a056</doi><tpages>7</tpages></addata></record>
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ispartof Journal of physical chemistry (1952), 1990-10, Vol.94 (21), p.8303-8309
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language eng
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source ACS Publications
subjects 400202 - Isotope Effects, Isotope Exchange, & Isotope Separation
ALCOHOLS
Applied sciences
CARBON ISOTOPES
Chemical engineering
Crystallization, leaching, miscellaneous separations
DATA
ETHANOL
Exact sciences and technology
EXPERIMENTAL DATA
FRACTIONATION
HYDROXY COMPOUNDS
INFORMATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
ISOTOPE EFFECTS
ISOTOPE RATIO
ISOTOPES
MASS SPECTROSCOPY
NUMERICAL DATA
ORGANIC COMPOUNDS
SEPARATION PROCESSES
SPECTROSCOPY
title A site-specific and multielement approach to the determination of liquid-vapor isotope fractionation parameters: the case of alcohols
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