期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 121, 期 23, 页码 5810-5817出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.7b00971
关键词
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资金
- French National Research Agency (ANR), project ISOTO-POL in the program CESA [009 01]
- Region Pays de la Loire
The relationship between the strength of the intermolecular interaction in liquid and the position-specific C-13 fractionation observed during distillation was investigated. A range of molecules showing different intermolecular interactions in terms of mode and intensity were incorporated in the study. Although it had previously been suggested that during evaporation the diffusive C-13 isotope effect in the thin liquid layer interfaced with vapor is not position-specific, herein we show that this is not the case. In particular, the position-specific effect was demonstrated for a series of alcohols. Our hypothesis is that intermolecular interactions in the liquid phase are the source of position-specific C-13 fractionation observed on the molecule. A clear trend is observed between the C-13 isotope effect of the carbon bearing the heteroatom of chemical function and the relative permittivity, the solvent hydrogen bond acidity, and the solvent hydrogen bond basicity, while only a weak trend was observed when using the C-13 content of the whole molecule. Furthermore, two families of products appeared when using the hydrogen bond acidity parameter for the correlation by distinguishing H-acceptor and H-donor molecules from those H-acceptors only. This strongly reinforces the hypothesis of an important role of the C-13 positioned close to the interaction center.
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