Excess molar enthalpies, H-m(E), of binary mixtures containing ethylene glycols and poly(glycols)+ ethyl alcohol were measured by a flow microcalorimeter at 308.15 K and at atmospheric pressure over the whole composition range. Binary mixtures contain ethyl alcohol + ethylene glycol, + di(ethylene glycol), + tri(ethylene glycol), + tetra(ethylene glycol), + poly(ethylene glycol)-200, + poly(ethylene glycol)-300, +poly(ethylene glycol)-400, +poly(ethylene glycol)-600. Effects of the molecular weight distribution (MWD), of the polymer were investigated too, by preparing three additional samples of poly(ethylene glycol) with the same number average molecular weight (M-n approximate to 300), but different MWD. For all mixtures, results were fitted to the Redlich-Kister polynomial. H-m(E) curves are asymmetrical, showing positive values which vary from 280 J mol(-1) (diethylene glycol + ethyl alcohol) to 1034 J mol(-1) (mixture containing PEGs (200 + 400) + ethyl alcohol). Effects of changes in the glycols chain length and in MWD on the molecular interactions among the mixture components are discussed. (c) 2005 Elsevier B.V. All rights reserved.