Application of the Flory Theory and of the Kirkwod−Buff Formalism to the Study of Orientational Effects in 1-Alkanol + Linear or Cyclic Monoether Mixtures

Abstract

Orientational effects present in binary mixtures of 1-alkanols with linear or cyclic monoethers have been studied using the Flory model and the Kirkwood−Buff formalism. The alcohols considered are those from methanol to 1-decanol, and the ethers are the following: dimethylether (DME), diethylether (DEE), dipropylether (DPE), dibutylether (DBE), tetrahydrofuran (THF), and tetrahydropyran (THP). In terms of the Flory model, orientational effects have been investigated by analyzing the concentration dependence of the interaction parameter, X12, and comparing the deviations obtained between experimental molar excess enthalpies, HmE, and calculated values with an X12 parameter determined from HmE measurements at equimolar composition. Due to the facts that structural effects are relevant for many of the considered mixtures and their excess molar volumes, VmE, are negative, we have also determined the excess molar internal energies, UV,mE, and X12 parameters from these data. From the X12 variation with the alka...