Abstract
We build a rigorous nonequilibrium thermodynamic description for open chemical reaction networks of elementary reactions. Their dynamics is described by deterministic rate equations with mass action kinetics. Our most general framework considers open networks driven by time-dependent chemostats. The energy and entropy balances are established and a nonequilibrium Gibbs free energy is introduced. The difference between this latter and its equilibrium form represents the minimal work done by the chemostats to bring the network to its nonequilibrium state. It is minimized in nondriven detailed-balanced networks (i.e., networks that relax to equilibrium states) and has an interesting information-theoretic interpretation. We further show that the entropy production of complex-balanced networks (i.e., networks that relax to special kinds of nonequilibrium steady states) splits into two non-negative contributions: one characterizing the dissipation of the nonequilibrium steady state and the other the transients due to relaxation and driving. Our theory lays the path to study time-dependent energy and information transduction in biochemical networks.Received 23 February 2016DOI:https://doi.org/10.1103/PhysRevX.6.041064Published by the American Physical Society under the terms of the Creative Commons Attribution 3.0 License. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Research AreasChemical kinetics, dynamics & catalysisNonequilibrium & irreversible thermodynamicsNonequilibrium statistical mechanicsStatistical PhysicsNonlinear DynamicsNetworksInterdisciplinary Physics
Highlights
Thermodynamics of chemical reactions has a long history
Following a strategy reminiscent of stochastic thermodynamics, we systematically build a nonequilibrium thermodynamic description for open driven chemical reaction networks (CRNs) made of elementary reactions in homogeneous ideal dilute solutions
Our theory embeds the nonequilibrium thermodynamic framework of irreversible processes established by the Brussels School of Thermodynamics
Summary
Thermodynamics of chemical reactions has a long history. The second half of the 19th century witnessed the dawn of the modern studies on thermodynamics of chemical mixtures. These studies played an important role during the first decade of the 21st century for the development of stochastic thermodynamics, a theory that systematically establishes a nonequilibrium thermodynamic description for systems obeying stochastic dynamics [14,15,16,17], including chemical reaction networks (CRNs) [18,19,20,21,22] Another significant part of the attention moved to the thermodynamic description of biochemical reactions in terms of deterministic rate equations [23,24]. We show the relation between the minimal chemical work necessary to manipulate the CRNs far from equilibrium and the nonequilibrium Gibbs free energy Our theory embeds both the Prigoginian approach to thermodynamics of irreversible processes [5] and the thermodynamics of biochemical reactions [23]. A result similar to the latter was independently found in Ref. [51]
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