Interactions of Glycerol, Diglycerol, and Water Studied Using Attenuated Total Reflection Infrared Spectroscopy

In order to examine the mixing properties of glycerol-water and diglycerol-water solutions, these solutions were measured using attenuated total reflection infrared spectroscopy. The absorbance spectra corrected for 1 µm thickness were subtracted by pure polyols for obtaining water spectra, and by pure water for polyol spectra. Both asymmetric and symmetric CH₂ stretching vibration bands (around 2940, 2885 cm^-1) shifted about 10 cm^-1 to lower wavenumber side (redshifts) with increasing polyol concentrations, especially at higher concentrations. Redshifts of C-O-H rocking bands (around 1335 cm^-1) with increasing polyol concentrations are slightly larger for diglycerol-water (10 > 6 cm^-1) than glycerol-water solutions. C-O stretching bands of CHOH groups (1125 and 1112 cm^-1) shift slightly but in opposite sides for glycerol and diglycerol at highest polyol concentrations (90-100 wt%). These shifts of CH₂ stretching, COH rocking, and CO stretching of CHOH at higher polyol concentrations suggest interactions of outer CH₂ with inner CHOH groups of surrounding polyols. The normalized band area changes with polyol concentrations could be fitted by quadratic polynomials possibly due to mixtures of different interactions between water-water, polyol-water, and polyol-polyol molecules. The OH stretching band for diglycerol 90 wt% shows three humps indicating at least three OH components: long, medium, and short H bond water molecules. Short H bond water molecules are the major component possibly between inner CHOH and outer side CH₂OH groups, while the long H component might loosely bind to outer CH₂OH groups.