Excess volumes of mixtures of glymes with normal, branched and cyclic alkanes

The molar excess volume VE has been obtained trough the concentration range at 298.15 K for 41 systems composed of the series of glymes (oxaalkanes), CH3–O–(CH2–CH2–O)m–CH3 with m=1 to 4 with normal, branched and cyclic alkanes. With literature values, a comprehensive view is given of (a) the change of equimolar VE with the molecular sizes of the components and with alkane structure and (b) concentration dependences which are S-shaped for certain systems. Equimolar HE were obtained at 303.15 K for 43 of the systems and used in applying the Prigogine–Flory (PF) theory to successfully predict the VE features. Evidence for association (Hydrogen bonding) in the pure glymes is reviewed. This accounts for discrepancies between PF theory and experiment which are minor for VE, but major for dVE/dT and CpE as seen through a consideration of literature values of these quantities.