Long-range diffusion in xylitol-water mixtures

J Phys Chem B. 2013 Jun 20;117(24):7363-9. doi: 10.1021/jp401633g. Epub 2013 Jun 10.

Abstract

Dynamic light scattering (DLS) and small-angle neutron scattering (SANS) were employed to study mixtures of xylitol and water. The results were also related to a previous dielectric relaxation study on the same system. In the temperature range of the DLS measurements the viscosity related structural (α) relaxation is too fast to be observed on the experimental time scale, but a considerably slower exponential and hydrodynamic relaxation process is clearly observable in the polarized light scattering data. A similar ultraslow process has been observed in many other types of binary liquids and commonly assigned to long-range concentration or density fluctuations. In some studies this interpretation has been supported by observations of substantial structural inhomogeneities in static light scattering or SANS experiments. However, in this study we observe such an ultraslow process without any indication of structural inhomogeneities on length-scales above 2 nm. Hence, we suggest that our observed ultraslow process is due to long-range diffusion of single xylitol molecules or small clusters of a few xylitol molecules (and perhaps some associated water molecules) which are randomly dispersed and sufficiently small to not be structurally detected in our SANS study. In the q-range of the DLS measurements this ultraslow relaxation process is around room temperature several orders of magnitude slower than the structural α-relaxation. However, if its 1/q(2)-dependent relaxation time is extrapolated to q-values where relaxation times from dielectric spectroscopy and quasielastic neutron scattering are compatible (about 10 nm(-1)), a relaxation time similar to that of the dielectric α-relaxation is obtained. Thus, the large difference in time scale between the two relaxation processes in the q-range of a DLS study is due to the fact that the α-relaxation is cooperative in nature, rather than caused by long-range single particle diffusion, and thus q-independent at low q-values.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Diffusion
  • Water / chemistry*
  • Xylitol / chemistry*

Substances

  • Water
  • Xylitol