Abstract
The unperturbed molecular dimensions of poly(ethylene glycol) (PEG) samples (of different molecular weights) have been evaluated in aqueous solutions from viscosity measurements at 25, 30, 35, and 40°C. The unperturbed dimension, K~θ~, has been determined from extrapolation methods, i.e., Kurata–Stockmayer–Fixman (KSF), Inagaki–Suzuki–Kurata (ISK), and Berry equations. The hydrodynamic expansion factor, α~η~, as well as the unperturbed root‐mean‐square end‐to‐end distance, 〈r^2^〉, found for the system indicated that the polymer coils contract as the temperature is raised from 25 to 40°C. The long‐range interaction (excluded volume) parameter, B, was also evaluated and a significant decrease was found for the PEG/water system between 25 and 40°C. The theta temperatures, θ, were obtained from the temperature dependence of (1/2 − χ) and the second virial coefficient was detected in the temperature interval of 25–40°C for the system and quite a good agreement with the calculated values evaluated via extrapolation and interpolation methods was observed. The thermodynamic interaction parameter χ was evaluated through the sum of the individual values of enthalpy and entropy dilution parameters, χ~H~ and χ~S~, for PEG samples. All the unperturbed molecular dimensions of PEG/water system were calculated and compared according to M~w~ and M~n~ values of PEG samples. Calculated values were interpreted mainly on the basis of hydrogen‐bond formation between polymer segments and PEG‐water molecules in solution. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 203–216, 2006