Universal Relation Between Thermodynamic Driving Force and One-Way Fluxes in a Nonequilibrium Chemical Reaction with Complex Mechanism
arXiv:1911.11956 · doi:10.1103/PhysRevResearch.2.033089
Abstract
In nonequilibrium chemical reaction systems, a fundamental relationship between unbalanced kinetic one-way fluxes and thermodynamic chemical driving forces is believed to exists. However this relation has been rigorously demonstrated only in a few cases in which one-way fluxes are well defined. In terms of its stochastic kinetic representation, we formulate the one-way fluxes for a general chemical reaction far from equilibrium, with arbitrary complex mechanisms, multiple intermediates, and internal kinetic cycles. For each kinetic cycle, the logarithm of the ratio of the steady-state forward and backward one-way fluxes is equal to the free energy difference between the reactants and products along the cycle. This fundamental relation is further established for general chemical reaction networks with multiple input and output complexes. Our result not only provides an equivalent definition of free energy difference in nonequilibrium chemical reaction networks, it also unifies the stochastic and macroscopic nonequilibrium chemical thermodynamics in a very broad sense.
2 figures, 6 pages
References in corpus (7)
- The Entropy Production Fluctuation Theorem and the Nonequilibrium Work Relation for Free Energy Differences
- Dynamical Ensembles in Nonequilibrium Statistical Mechanics
- Nonequilibrium Thermodynamics of Chemical Reaction Networks: Wisdom from Stochastic Thermodynamics
- Relationship between Thermodynamic Driving Force and One-Way Fluxes in Reversible Chemical Reactions
- Irreversible thermodynamics of open chemical networks I: Emergent cycles and broken conservation laws
- Generalized Haldane Equation and Fluctuation Theorem in the Steady State Cycle Kinetics of Single Enzymes
- Mathematical Formalism of Nonequilibrium Thermodynamics for Nonlinear Chemical Reaction Systems with General Rate Law