Aqueous solutions of poly(ethylene glycol) (PEG) exhibit some remarkable properties, among which is the small changes in water activity compared to the volumes occupied by the PEG: For example, the water in a 20% mass fraction solution of 6000 Da PEG has an activity of 0.9939. We have investigated PEGs with molecular weights 200, 400, 1000, 2000, 4000, and 8000 Da in the concentration range 1% to 17% mass fraction at neutral pH and with added KCl concentrations of 10 mmol L-1 in aqueous solutions-conditions near those for promoting protein crystallization. These solutions exhibit a structural change at around 6% mass fraction as seen in the solution viscosities, compressibilities, and infrared spectra. Raman spectroscopy shows that the PEGs remain in the same structural form over the concentration range, and the infrared spectra indicate that the change must be due to a local shift in the water structure. Modeling of the results from small-angle neutron scattering (SANS) on the solutions suggests that the structures of the PEGs in the molecular mass range 2000 Da to 8000 Da are paired in the solution, and the separation distance decreases with increasing PEG concentration. From the structure, it becomes clear that the small effect on water activity occurs because of screening by the more weakly bound outer layers. From the bulk measurement of a(w) and with reasonable assumptions, a free energy Delta G degrees can be assigned to each of the fourth, third, and second hydration layers. (C) 2012 Elsevier Ltd. All rights reserved.