Excess molar volumes at 25-degrees, are reported for the system 1,2-di
methoxyethane + water and 12-crown-4 + water across their entire respe
ctive composition ranges. These data have been compared to others take
n from the literature, in an effort to assess the effects of replacing
hydroxy by methoxy groups, of switching linear to cyclic polyethers a
nd of inserting oxyethylene groups. The data sets were analysed using
a segmented composition model in order to obtain a quantitative descri
ption of the composition dependence of the excess molar volumes. Exces
s partial molar volumes of the organic species at infinite aqueous dil
ution were evaluated by means of four segment analyses of the various
excess volume data sets. The effectiveness of the group additivity pri
nciple is nicely demonstrated.