Infrared spectroscopy of methanol-hexane liquid mixtures. II. The strength of hydrogen bonding

The study by Fourier transform infrared attenuated total reflectance spectroscopy at 27 degrees C of methanol (MeOH) and hexane mixtures is presented. In the 0-0.25 and 0.75-1.00 molar fractions, the mixtures form homogeneous solutions, whereas from 0.25 to 0.75, the mixtures are inhomogeneous forming two phases. These mixtures have the near 3300 cm(-1) OH stretch band only slightly displaced throughout the whole concentration range indicating very little variation in the H-bonding condition. This result is very different from that of MeOH in CCl4 where the OH stretch bands are scattered in a wide frequency range. Factor analysis applied to the MeOH/hexane spectra gave seven principal factors (one hexane and six methanol factors) and retrieved their principal spectra and abundances. In the inhomogeneous region, the two phase volumes changed inversely with concentration, but their factor compositions are invariable at 1:3 and 3:1 molar ratios. Five of the six principal methanol factors have the O-H and the C-O stretch bands situated near, respectively, 3310 and 1025 cm(-1) with little displacement in the whole concentration range. The sixth factor observed at 3654 cm(-1) (full width at half height < 40 cm(-1)) was assigned to free methanol OH by Max and Chapados [J. Chem. Phys. 128, 224512 (2008)]. This species concentration is very low but constant at around 0.01M in the methanol range of 0.5-2.5M. The main OH stretch bands (similar to 3300 cm(-1)) were simulated with six Gaussian components that were assigned to different hydrogen-bonding situations. These form reverse micelles at low methanol concentrations and micelles at high concentrations that persist in pure methanol. A very different state of affairs exists in MeOH in CCl4 where free OH groups are formed in almost all mixtures except in pure MeOH. Since hexane is a better model of a lipidic milieu than CCl4, the results for MeOH/hexane give a better representation of the fate of alcoholic OH groups in such a milieu.