Group Contribution Values for the Thermodynamic Functions of Hydration at 298.15 K, 0.1 MPa. 3. Aliphatic Monoethers, Diethers, and Polyethers

Abstract

A compilation of experimental values of the infinite dilution partial molar Gibbs energy, enthalpy, and heat capacity of hydration, together with partial molar volumes in water at 298.15 K and 0.1 MPa is presented for aliphatic monoethers, diethers, and polyethers. These data are treated in the framework of the first- and second-order group additivity methods. However, third- and higher-order effects (i.e., interactions expressed beyond the nearest neighbors) are clearly present in aqueous ethers. The effects can be accounted for by the introduction of a number of corrections. For the second-order group contribution method, numerical values are determined for the following groups: C−(C)2(H)(O)ether, C−(C)3(O)ether, O−(C)2, C−(H)2(O)2, C−(C)(O)2(H), and corrections: a “ethoxyalkane” correction, {CH3−CH2−O−CH2}, and a “diether” correction, {O−(CH2)2−O}. For the first-order group contribution method, in addition to the “ether” O group, a large number of corrections appears to be necessary for accurate repr...