Complete Separation of Xylenes and Ethylbenzene by Gas Chromatography

Mass Action and the Natural Path

“…Expressions (1), (2) and (3) analytically represent three empirical approaches to the study of chemical reacting systems. As originally developed the Linear Phenomenological Approach as described by expression (1) was devoid of any mechanistic considerations as befitting a strictly thermodynamic expression, the form in which it is still employed in all fields of study of irreversible processes with the notable exception of chemical reactions.…”

“…As originally developed the Linear Phenomenological Approach as described by expression (1) was devoid of any mechanistic considerations as befitting a strictly thermodynamic expression, the form in which it is still employed in all fields of study of irreversible processes with the notable exception of chemical reactions. For the latter case mechanistic considerations are required, for which case the Mass Action Approach was developed, as described by expression (2).…”

“…However, this flux-force approach has been particularly unsuccessful for describing homogeneous chemical reactions [2,3]. Although / can be readily identified with the reaction velocity v, a spatial gradient X can not be readily identified.…”

“…The results have been uniformly unsuccessful [8,9]. In fact, only by abandoning the linear relationship [expression (1)] altogether and borrowing mechanistic concepts from Mass Action [expression (2)] have irreversible thermodynamicists been able to elucidate any relationship between the reaction velocity and the chemical affinity [10].…”

“…For the past century the conventional study of the velocity of chemical reactions has been based on expression (2), the Mass Action approach. Even when applied to complex reactions involving intermediate steps and transient species this empirical approach so excels in the elucidation of reaction mechanisms that Mass Action might be termed the First Law of Chemical Kinetics.…”