Hydrogen bonding in the gas phase: the thermodynamic properties of hydrogen fluoride-ether complexes and their far infrared spectra

Abstract

The equilibrium constants of gas-phase complexes of HF with dimethyl, methyl ethyl and diethyl ether have been measured at several temperatures using the Benesi-Hildebrand approximation on the absorption band of the HF stretching vibration in the complex. From these, values of $\Delta $H of -43, -38 and -30 kJ mol$^{-1}$ respectively, have been determined. They are interpreted in terms of conformational rearrangements of the ethers when they form hydrogen bonds. The far infrared spectra of the complexes with both HF and DF have also been recorded and in each case a band observed at around 180 cm$^{-1}$ which is assigned to the intermolecular stretching mode of vibration. For the complex between HF and dimethyl ether a rotational contour has been observed at about 10 cm$^{-1}$.