Abstract

Raman spectra of benzophenone (BP) have been measured in methanol, ethanol, and cyclohexane under various thermodynamic conditions including the supercritical states. The CO stretching band of BP shifted to higher frequencies with an increase in the solvent temperature from room temperature (RT) at constant pressure. Under the isothermal condition above the critical temperature of the solvent, the CO stretching band shifted to lower frequencies with a decrease in the solvent density. On the other hand, the ring stretching band shifted to lower frequencies with an increase in the solvent temperature from RT to ca. 530K, while it slightly shifted to higher frequencies under the supercritical conditions with decreasing density. We have calculated the acceptor number of supercritical alcohols in reference to the linear correlation established for normal solvents between the acceptor number of the solvent and the CO stretching frequency (Fujisawa et al., J. Phys. Chem. 112 (2008) 1914). The results are discussed in relation to the hydrogen bonding between the solute and the solvent.

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