title: The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled.
abstract: An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting.
authors.affiliation: Physics of Complex Biosystems, Physics Department, Technical University of Munich, James-Franck-Strasse 1, D-85748 Garching, Germany. gerland@tum.de.
authors.forename: Tobias
authors.initials: T
authors.lastname: Göppel
authors.affiliation: Physics of Complex Biosystems, Physics Department, Technical University of Munich, James-Franck-Strasse 1, D-85748 Garching, Germany. gerland@tum.de.
authors.forename: Vladimir V
authors.initials: VV
authors.lastname: Palyulin
authors.affiliation: Physics of Complex Biosystems, Physics Department, Technical University of Munich, James-Franck-Strasse 1, D-85748 Garching, Germany. gerland@tum.de.
authors.forename: Ulrich
authors.initials: U
authors.lastname: Gerland