Hydrogen bonding in supercritical methanol studied by infrared spectroscopy

We report the first Fourier transform infrared spectroscopic studies of the hydrogen-bonding interactions in supercritical methanol and methanol/methanol-d1 mixtures. At 523 K and below ∼0.3 mol/l, methanol chiefly existed in a monomeric form. However, at 523 K and between ∼0.3 and 2 mol/l, in the r...

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Bibliographic Details
Published in:The Journal of chemical physics 2002-02, Vol.116 (5), p.1995-2003
Main Authors: Bulgarevich, Dmitry S., Otake, Katsuto, Sako, Takeshi, Sugeta, Tsutomu, Takebayashi, Yoshihiro, Kamizawa, Chiyoshi, Shintani, Daisuke, Negishi, Akira, Tsurumi, Chikao
Format: Article
Language:English
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Summary:We report the first Fourier transform infrared spectroscopic studies of the hydrogen-bonding interactions in supercritical methanol and methanol/methanol-d1 mixtures. At 523 K and below ∼0.3 mol/l, methanol chiefly existed in a monomeric form. However, at 523 K and between ∼0.3 and 2 mol/l, in the regions of O–H, C–O, and C–H stretching vibrations, there were clear indications of methanol monomer–dimer equilibrium. The effect of temperature on the equilibrium constant was also investigated. As a result, the partial molar volume difference and enthalpy of the dimerization were estimated and correlated with the behavior of the methanol isothermal compressibility. It was also concluded that at 523 K and density higher than ∼15 mol/l, the hydrogen-bonding equilibrium started to shift toward larger aggregates.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.1431585