Raman spectroscopy of glycerol/D2O solutions

Raman spectra of neat glycerol, neat D2O, and glycerol/D2O solutions with glycerol mole fractions (XG) of 0.00, 0.02, 0.12 and 0.32 and 1.00 are presented. Vibrational assignments are discussed for the bands observed in the 1000–1600 and 2000–3700 cm−1 spectral regions. Upon dilution of neat glycerol with D2O, glycerol hydrogen-bonds with D2O through its oxygen atoms as hydrogen-bond acceptors. With progressive glycerol dilution, D2O breaks the dimers and higher oligomers present in neat glycerol to form glycerol monomers. D2O molecules in the XG 0.02 solution are in an environment similar to that of neat D2O due to minimal perturbation of the D2O network. The absence of bands due to weakly hydrogen-bonded D2O in the XG 0.12 solution suggests that most D2O are more strongly hydrogen-bonded than in neat D2O as would occur in D2O clusters. D2O in XG 0.32 solutions are in a unique environment in that they lose their hydrogen-bonding network completely, mixing into the solution as monomers.