Free energy levels and entropy production associated with biochemical kinetic diagrams

"Basic" and "gross" free energy levels are defined for the discrete states of a macromolecular biochemical kinetic system such as a free energy transducing enzyme (e.g., myosin or Na,K-ATPase). Basic free energy level differences are related to the first-order rate constants for transitions between states while gross free energy differences, along with the corresponding fluxes, determine the rate of entropy production in the system. In muscle contraction the analysis is complicated by the possibility of the system doing external mechanical work. The question of the sign of the flux or of the gross free energy level change in a given transition is examined for both single-cycle and multi-cycle models. More definite statements can be made in single-cycle cases. Some numerical examples are included. The more complicated cases are reserved for a subsequent paper.