Thermodynamics of systems of (oxy)alcohols and (poly)ethers

In this work, as a contribution to the study of alkanol-alkane-ether systems, we study the systems containing hydroxyl and ether groups either in separate molecules or in the same molecule. Typical cases are: Pure oxyalkanols, alkanes + oxyalkanols, alkanols + ethers, alkanols + polyethers, and alkanols + monoethers of poly(ethylene glycol). The presence of the hydroxyl and ether groups in these systems gives rise to two types of hydrogen bonds: a self-association, or OH---OH interaction and a cross-association, or OH---O interaction. In the general case these interactions give rise to multiple hydrogen bonding structures or association network structures. Because of this the widely used association theories which invoke the presence of simple association complexes (dimers, trimers, etc.) are not easily applicable to these systems. In this work we discuss the use of a generalized statistical thermodynamic formalism for the hydrogen bonding of molecules having any number of hydroxyl and/or ether groups. It is based on a recently developed equation-of-state type theory of hydrogen bonding networks in fluid systems. This formalism is subsequently reduced to the typical cases mentioned before. Experimental literature data are used for testing both the pure component- and the mixture - formalism.