Title : Kinetics and thermodynamics of reversible polymerization in closed systems Language : - Author, co-author : Lahiri, S. [Laboratoire de Physico-Chimie Théorique, UMR CNRS Gulliver 7083, ESPCI - 10 rue Vauquelin, Paris, France] Wang, Y. [Laboratoire de Physico-Chimie Théorique, UMR CNRS Gulliver 7083, ESPCI - 10 rue Vauquelin, Paris, France] Esposito, Massimiliano [University of Luxembourg > Faculty of Science, Technology and Communication (FSTC) > Physics and Materials Science Research Unit] Lacoste, D. [Laboratoire de Physico-Chimie Théorique, UMR CNRS Gulliver 7083, ESPCI - 10 rue Vauquelin, Paris, France] Publication date : 2015 Journal title : New Journal of Physics Publisher : Institute of Physics Publishing Volume : 17 Issue/season : 8 Peer reviewed : Yes (verified by ORBilu ) Audience : International ISSN : 13672630 Keywords : [en] Entropy ; Free energy ; Kinetics ; Lyapunov functions ; Polymerization ; Reaction kinetics ; Stochastic systems ; Thermodynamics ; Equilibrium polymers ; Kinetics and thermodynamics ; Kullback Leibler divergence ; Non equilibrium thermodynamics ; Polymer concentrations ; Reversible polymerization ; Stochastic thermodynamics ; Thermodynamic quantities ; PolymersAbstract : [en] Motivated by a recent study on the metabolism of carbohydrates in bacteria, we study the kinetics and thermodynamics of two classic models for reversible polymerization, one preserving the total polymer concentration and the other one not. The chemical kinetics is described by rate equations following the mass-action law. We consider a closed system and nonequilibrium initial conditions and show that the system dynamically evolves towards equilibrium where a detailed balance is satisfied. The entropy production during this process can be expressed as the time derivative of a Lyapunov function. When the solvent is not included in the description and the dynamics conserves the total concentration of polymer, the Lyapunov function can be expressed as a Kullback-Leibler divergence between the nonequilibrium and the equilibrium polymer length distribution. The same result holds true when the solvent is explicitly included in the description and the solution is assumed dilute, whether or not the total polymer concentration is conserved. Furthermore, in this case a consistent nonequilibrium thermodynamic formulation can be established and the out-of-equilibrium thermodynamic enthalpy, entropy and free energy can be identified. Such a framework is useful in complementing standard kinetics studies with the dynamical evolution of thermodynamic quantities during polymerization. © 2015 IOP Publishing Ltd and Deutsche Physikalische Gesellschaft.Permalink : http://hdl.handle.net/10993/26844 DOI : 10.1088/1367-2630/17/8/085008 
[University of Luxembourg > Faculty of Science, Technology and Communication (FSTC) > Physics and Materials Science Research Unit]
