Excess molar volumes V m E at 25°C and atmospheric pressure over the entire composition range for binary mixtures of 1-hexanol with n-polyethers: 2,5-dioxahexane, 3,6-dioxaoctane, 2,5,8-trioxanonane, 3,6,9-trioxaundecane, 5,8,11-trioxapentadecane, 2,5,8,11-tetraoxadodecane, and 2,5,8,11,14-pentaoxapentadecane are reported from densities measured with a vibrating-tube densimeter. Systems containing 2,5-dioxahexane, 2,5,8-trioxanonane, 2,5,8,11-tetraoxadodecane or 2,5,8,11,14-pentaoxapentadecane are characterized by V m E > 0, probably due to predominant positive contributions to V m E from the disruption of H bonds of 1-hexanol and to physical interactions. In contrast, mixtures with 3,6-dioxaoctane, 3,6,9-trioxaundecane, and 5,8,11-trioxapentadecane are characterized by V m E < 0, indicating that the negative contribution to V m E from interstitial accommodation is more important.

Excess molar volumes VmE at 298.15 K and atmospheric pressure for 1-propanol + 2,5-dioxahexane, 3,6-dioxaoctane, 2,5,8-trioxanonane, 3,6,9-trioxaundecane or 5,8,11-trioxapentadecane have been calculated from densities measured with an Anton-Paar DMA 602 vibrating-tube densimeter. All the excess molar volumes are negative over the whole mole-fraction range, nearly symmetrical for mixtures with diethers and slightly skewed towards the region of high mole fraction of 1-propanol for mixtures with triethers. The value of VmE decreases as the n-alkyl chain end length of the diethers or the triethers increases. When the n-alkyl chain end of the polyethers is the methyl group (CH3), VmE is very small in absolute value and similar for the diethers and triethers, whereas when the end group is larger than the methyl group, the value of VmE is more negative for the diethers than for the triethers. These results, together with previously published excess molar enthalpies, suggest the formation of hydrogen bonds between the functional group OH of the 1-alkanol and the O atoms of the polyethers.