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Abstract
The authors show that chemical affinities evolve in time to minimize the sum of the entropy production and the exchange entropy for chemical reactions taking place in a continuous-flow stirred tank reactor.
Highlights
Far from equilibrium systems make up for most of the applied and natural processes and the formation of structural order in energy dissipative systems [1,2,3]
Consider first the hybrid entropy production and exchange for the enantiomeric pathway pair E16, E17. These are expressed as weighted sums over the partial entropy productions and/or exchanges associated with each individual transformations as indicated; the fractional weights follow from stoichiometric network analysis [13]
Stoichiometric network analysis (SNA) applied to a reaction network, in a system possessing input and output matter fluxes, yields the inequality for, Eq (31), that is, the statement that the change in σ + σe with respect to the time derivatives of the affinities A is such as to lower the value of dS/dt and which is zero in a stationary state
Summary
Far from equilibrium systems make up for most of the applied and natural processes and the formation of structural order in energy dissipative systems [1,2,3]. We derive a thermodynamic inequality governing the rate of change of the entropy for far from equilibrium chemical reactions driven by continuous open flow This inequality generalizes the Glansdorff-Prigogine GEC and states that the chemical forces (the affinities A) must necessarily evolve so as to lower the temporal change in the system entropy. The chemical forces (i.e., the affinities) acting along each individual reaction pathway must evolve so as to lower the rate of change in the net system entropy (dS/dt ) This pathway criterion is validated, and its physical significance revealed, for an enantioselective autocatalytic model [15], which has chiral nonequilibrium stationary states that exist off the thermodynamic branch (racemic states) and is relevant in chemical evolution scenarios for explaining the prebiotic origin of biological homochirality
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