Issue 30, 2016

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.

Graphical abstract: The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled

Article information

Article type
Paper
Submitted
15 feb. 2016
Accepted
26 apr. 2016
First published
28 apr. 2016
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2016,18, 20135-20143

The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled

T. Göppel, V. V. Palyulin and U. Gerland, Phys. Chem. Chem. Phys., 2016, 18, 20135 DOI: 10.1039/C6CP01034B

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