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Helmholtz free energy
Helmholtz free energy

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Chap-12A_Basic-Thermo-and-Laws
Chap-12A_Basic-Thermo-and-Laws

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Extremal principles in non-equilibrium thermodynamics

Energy dissipation and entropy production extremal principles are ideas developed within non-equilibrium thermodynamics that attempt to predict the likely steady states and dynamical structures that a physical system might show. The search for extremum principles for non-equilibrium thermodynamics follows their successful use in other branches of physics. According to Kondepudi (2008), and to Grandy (2008), there is no general rule that provides an extremum principle that governs the evolution of a far-from-equilibrium system to a steady state. According to Glansdorff and Prigogine (1971, page 16), irreversible processes usually are not governed by global extremal principles because description of their evolution requires differential equations which are not self-adjoint, but local extremal principles can be used for local solutions. Lebon Jou and Casas-Vásquez (2008) state that ""In non-equilibrium ... it is generally not possible to construct thermodynamic potentials depending on the whole set of variables"". Šilhavý (1997) offers the opinion that ""... the extremum principles of thermodynamics ... do not have any counterpart for [non-equilibrium] steady states (despite many claims in the literature)."" It follows that any general extremal principle for a non-equilibrium problem will need to refer in some detail to the constraints that are specific for the structure of the system considered in the problem.
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