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Reciprocal Relations in Irreversible Processes. II. Export

Physical Review, Vol. 38, No. 12. (15 December 1931), 2265.

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irreversible thermodynamics

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A general reciprocal relation; applicable to transport processes such as the conduction of heat and electricity; and diffusion; is derived from the assumption of microscopic reversibility. In the derivation; certain average products of fluctuations are considered. As a consequence of the general relation S = k  log W between entropy and probability; different (coupled) irreversible processes must be compared in terms of entropy changes. If the displacement from thermodynamic equilibrium is described by a set of variables α 1 ;⋯;α n ; and the relations between the rates α̇ 1 ;⋯;α̇ n and the "forces" ∂ S / d α 1 ;⋯;∂ S / d α n are linear; there exists a quadratic dissipation-function; 2Φ(α̇;α̇)≡Σρ j α̇ ij α̇ i = dS / dt = S ̇(α;α̇)≡Σ(∂ S / d α j )α̇ j (denoting definition by ≡). The symmetry conditions demanded by microscopic reversibility are equivalent to the variation-principle S ̇(α;α̇)-Φ(α̇;α̇)=maximum; which determines α̇ 1 ;⋯;α̇ n for prescribed α 1 ;⋯;α n . The dissipation-function has a statistical significance similar to that of the entropy. External magnetic fields; and also Coriolis forces; destroy the symmetry in past and future; reciprocal relations involving reversal of the field are formulated.


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