Conservation Laws and Work Fluctuation Relations in Chemical Reaction Networks

Abstract

We formulate a nonequilibrium thermodynamic description for open chemical reaction networks (CRN) described by a chemical master equation. The topological properties of the CRN and its conservation laws are shown to play a crucial role. They are used to decompose the entropy production into a potential change and two work contributions, the first due to time dependent changes in the externally controlled chemostats concentrations and the second due to flows maintained across the system by nonconservative forces. These two works jointly satisfy a Jarzynski and Crooks fluctuation theorem. In absence of work, the potential is minimized by the dynamics as the system relaxes to equilibrium and its equilibrium value coincides with the maximum entropy principle. A generalized Landauer's principle also holds: the minimal work needed to create a nonequilibrium state is the relative entropy of that state to its equilibrium value reached in absence of any work.

arXiv commentrevtex format: 30 pages (25 + 5 for appendices), 9 figures, 3 tables. v2: published version

References in corpus (37)

• A nonequilibrium equality for free energy differences
• Stochastic thermodynamics, fluctuation theorems, and molecular machines
• The Entropy Production Fluctuation Theorem and the Nonequilibrium Work Relation for Free Energy Differences
• Entropy production along a stochastic trajectory and an integral fluctuation theorem
• Colloquium. Quantum Fluctuation Relations: Foundations and Applications
• Second law and Landauer principle far from equilibrium
• Ensemble and Trajectory Thermodynamics: A Brief Introduction
• Nonequilibrium Thermodynamics of Chemical Reaction Networks: Wisdom from Stochastic Thermodynamics
• Thermodynamics with continuous information flow
• Fluctuation theorem for currents and Schnakenberg network theory
• Stochastic thermodynamics of chemical reaction networks
• A fluctuation theorem for currents and non-linear response coefficients
• Irreversible thermodynamics of open chemical networks I: Emergent cycles and broken conservation laws
• Stochastic thermodynamics of single enzymes and molecular motors
• Entropy fluctuation theorems in driven open systems: application to electron counting statistics
• Thermodynamics of Error Correction
• Nonequilibrium Equalities in Absolutely Irreversible Processes
• Thermodynamic Limit of a Nonequilibrium Steady-State: Maxwell-Type Construction for a Bistable Biochemical System
• Comparison of work fluctuation relations
• Conservation Laws shape Dissipation
• Brownian duet: A novel tale of thermodynamic efficiency
• The thermodynamics of computational copying in biochemical systems
• Thermodynamically Consistent Coarse Graining of Biocatalysts beyond Michaelis--Menten
• Product-form Poisson-like distributions and complex balanced reaction systems
• Thermodynamic limits to information harvesting by sensory systems
• Fundamental costs in the production and destruction of persistent polymer copies
• Thermodynamics of accuracy in kinetic proofreading: Dissipation and efficiency trade-offs
• Nonequilibrium Thermodynamic Formalism of Nonlinear Chemical Reaction Systems with Waage-Guldberg's Law of Mass Action
• Chemical Boltzmann Machines
• Conservation laws and symmetries in stochastic thermodynamics
• Dissipation in noisy chemical networks: The role of deficiency
• Exact fluctuation theorem without ensemble quantities
• Identification of conserved moieties in metabolic networks by graph theoretical analysis of atom transition networks
• Fluctuating Currents in Stochastic Thermodynamics II. Energy Conversion and Nonequilibrium Response in Kinesin Models
• Cycle/cocycle oblique projections on oriented graphs
• Nonequilibrium thermodynamics and information theory: Basic concepts and relaxing dynamics
• Glucans monomer-exchange dynamics as an open chemical network

Cited by in corpus (40)

• Theory of nonequilibrium free energy transduction by molecular machines
• Stochastic Thermodynamics of Non-Linear Electronic Circuits: A Realistic Framework for Computing around kT
• Thermodynamic Efficiency in Dissipative Chemistry
• Large deviations and dynamical phase transitions in stochastic chemical networks
• Thermodynamics of Chemical Waves
• Nonequilibrium Thermodynamics of Non-Ideal Chemical Reaction Networks
• Macroscopic Stochastic Thermodynamics
• Detailed Fluctuation Theorems: A Unifying Perspective
• Nonequilibrium thermodynamics of light-induced reactions
• Information Geometric Inequalities of Chemical Thermodynamics
• Stochastic thermodynamics of all-to-all interacting many-body systems
• Thermodynamics of Concentration vs Flux Control in Chemical Reaction Networks
• Thermodynamics of Non-Elementary Chemical Reaction Networks
• Methods and Conversations in (Post)Modern Thermodynamics
• Nonequilibrium Thermodynamics of Non-Ideal Reaction-Diffusion Systems: Implications for Active Self-Organization
• Trade-offs between number fluctuations and response in nonequilibrium chemical reaction networks
• Effective thermodynamics of two interacting underdamped Brownian particles
• Linear Stochastic Thermodynamics
• Open Questions on Nonequilibrium Thermodynamics of Chemical Reaction Networks
• Stochastic approach to entropy production in chemical chaos
• On non-ideal chemical-reaction networks and phase separation
• Second Law of Thermodynamics without Einstein Relation
• A chemical reaction network implementation of a Maxwell demon
• Optimal control of protein copy number
• Characterizing the Conditions for Indefinite Growth in Open Chemical Reaction Networks
• Strong current response to slow modulation: a metabolic case-study
• Universal dynamic scaling in chemical reactions at and away from equilibrium
• Deficiency, Kinetic Invertibility, and Catalysis in Stochastic Chemical Reaction Networks
• Prevalence of multistability and nonstationarity in driven chemical networks
• A [3]-catenane non-autonomous molecular motor model: geometric phase, no-pumping theorem, and energy transduction
• Thermodynamics of Growth in Open Chemical Reaction Networks
• Gears in Chemical Reaction Networks: Optimizing Energy Transduction Efficiency
• Dissipation in Hydrodynamics from Micro- to Macroscale: Wisdom from Boltzmann and Stochastic Thermodynamics
• Random walks on modular chains: Detecting structure through statistics
• Dynamical equivalence classes for Markov jump processes
• Nonequilibrium thermodynamic signatures of collective dynamical states around chimera in a chemical reaction network
• Modified Jarzynski equality in a microcanonical ensemble
• What is a chemostat? Insights from hybrid dynamics and stochastic thermodynamics
• Coarse Graining Photo-Isomerization Reactions: Thermodynamic Consistency and Implications for Molecular Ratchets
• Energy Transduction in Complex Networks with Multiple Resources: The Chemistry Paradigm