Comment: Detailed balance revisited

Literature Information

Publication Date 2009-09-15
DOI 10.1039/B911608G
Impact Factor 3.676
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Abstract

The concept of detailed balance is central to the field of chemical kinetics and provides important constraints on relationships between equilibrium and rate constants. Miller et al. [Phys. Chem. Chem. Phys., 2009, 11, 1128] have recently proposed that having the ratio of forward and reverse rate constants equal to the equilibrium constant—a relationship they equate with detailed balance—is a sufficient condition to guarantee that a chemical system eventually relaxes to equilibrium. This assertion is true, however, only for an isolated system. In a closed system, where energy exchange between the system and the environment occurs, input of energy in the form of an externally driven oscillation of a thermodynamic parameter (e.g. pressure or electric field strength), can maintain a chemical system in a stationary state away from equilibrium even if the ratio of the forward and backward rate constants for each elementary reaction equals the equilibrium constant at every instant. This fact allows appropriately designed molecules to serve as free-energy transducers and molecular machines.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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