Is mixing a thermodynamic process?

Abstract

Mixing processes exist with positive entropy change and negative free energy change. However, the idea that the irreversibility of the mixing processes is responsible for the so-called free energy and entropy of mixing is faulty. The mixing, as well as the demixing processes may be associated with either reversible or irreversible phenomena, depending on the particular conditions. For ideal gases, the word ‘‘mixing’’ in the terms ‘‘mixing entropy’’ and ‘‘mixing free energy’’ may sometimes be used descriptively but never causatively. The quantity −∑ Ni R ln Xi, usually referred to as ‘‘mixing entropy,’’ has nothing to do with the mixing phenomenon. Therefore the terms ‘‘mixing entropy’’ and ‘‘mixing free energy’’ are essentially misconceptions. In fact, it is shown that the process of mixing of ideal gases has, by itself, no relevance to any thermodynamic quantity. Therefore, in a thermodynamical sense, it is a nonprocess. The concepts of assimilation and deassimilation are introduced. It is shown that the ‘‘deassimilation process is essentially irreversible.’’ This should replace the traditional principle that ‘‘the mixing process is essentially irreversible.’’