Abstract
Infrared OH stretching absorption of HDO isolated in aromatic hydrocarbons have been measured at temperatures of 473 and 523 K and at pressures in the 100–350 bar range. The peak frequencies are dependent on the solvents and their order, benzene>toluene>ethylbenzene>cumene>o-xylene∼m-xylene>mesitylene, is exactly the same as the order for the ionization potentials of the hydrocarbons. Shifts of the frequencies from that of HDO in hexane, which was measured as a reference at the same temperature and pressure, were analyzed using a charge transfer theory for hydrogen bonding. Distances between the water molecule and a solvent phenyl ring were estimated to be 2.8±0.1 and 2.9±0.1 Å at 473 and 523 K, respectively. These values are consistent with a structure of a water–benzene complex determined by a jet-cooled microwave spectroscopy. These facts suggest that the π-hydrogen bond between water and aromatic hydrocarbons exists even at the high temperatures under pressure.
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