The desorption of n-hexane from high molar mass polyethylene at 298 K has been studied. The polymer was given different thermal treatments to obtain differences in crystallinity, morphology and composition of the non-crystalline fraction. Crystal contents determined by Raman spectroscopy were always lower than those determined by density measurements. The systems with high crystallinity showed in relative terms a low content of interfacial component. The n-hexane solubilities of the samples were strictly proportional to the volume fraction of penetrable polymer (liquid-like and interfacial components) and the solubility was low in comparison with that of branched polyethylene of the same crystallinity. The Cohen-Tumbull-Fujita free volume theory was numerically capable of describing the desorption process in the polyethylenes studied. One of the methods used assumed that all three non-crystalline components-liquid-like, interfacial liquid-like and interfacial crystal core components-are penetrable by n-hexane and this method yielded data for the geometrical impedance factor and the fractional free volume with physically realistic trends, but the changes in the geometrical impedance factor was not in quantitative agreement with the Fricke model applied to the morphological data. This lack of numerical agreement is tentatively due to the fact that the assessment of crystal shape by transmission electron microscopy of stained sections systematically underestimates the crystal widths, particularly for the low-crystallinity samples with curved and 'twisting' crystal lamellae. (C) 2003 Elsevier Science Ltd. All rights reserved.