Graph Methodology and Principles of Linear Nonequilibrium Thermodynamics in the Theory of Flow-Injection Analysis

摘要

It is shown that chemical, configurational, and informational properties of flow-injection systems can be interrelated with the use of the methodology of the graph theory. The main equation of the theory is derived using a mathematical expression of the transition paths from the analyte to the detection of a product of the analytical reaction. Examples of specific developments are discussed for redox reactions, ligand exchange reactions, and heterogeneous exchange reactions, with due regard to, the hidden peculiarities of their chemical mechanisms that are essential for flow analysis and also for on-line preconcentration by coprecipitation. It is also shown that the conditions obtained in a flow system correspond to the basic postulates of linear nonequilibrium thermodynamics, which provides a basis for a new approach to the theory of flow analysis. An example of a complexation reaction was used for discussing the possibility that a linear interrelation exists between flows and forces in a flow system, which corresponds to the Onsager reciprocal relation.