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Onsager reciprocity as a consequence of Maxwell reciprocity for 'equidiffuse' fluids

機譯：由于“等擴散”流體的麥克斯韋互易性，Onsager互易性

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Linear irreversible thermodynamics (LIT) principles are used to show, in the hypothetical "equidiffuse" case where all of the various phenomenological diffusion coefficients appearing in the linear near-equilibrium constitutive laws governing the diffuse transport of energy, multicomponent species, entropy, and volume (although not necessarily including momentum) are taken to be equal, that the Onsager reciprocal relations pertinent to non-equilibrium thermodynamics follow automatically from Maxwell's reciprocal relations governing equilibrium thermodynamics. As such, this constitutes a purely macroscopic proof of Onsager reciprocity, the first of its kind. Although the equality of diffusion coefficients required in the equidiffuse limiting case does not represent a realistic possibility in the case of most mixtures, its adoption as a foil in uniting reversible and irreversible thermodynamics neither violates nor conflicts with any known physical law. Indeed, in some idealized sense such equality represents a perfection of the well-known analogy between these distinct physical transport phenomena. Moreover, as shown for mixtures of chemically similar dilute gases of comparable molecular weights (e.g., consecutive members of a homologous series) the equidiffuse assumption is generally quite good. As a bonus, our analysis - by virtue of its accord with all known precepts of macroscopic physics - constitutes a satisfactory resolution of the long-standing criticism of Coleman and Truesdell [B.D. Coleman, C. Truesdell, On the reciprocal relations of Onsager, J. Chem. Phys. 33 (1960) 28-31] centered on the possibility that Onsager symmetry might be nothing more than a tautology (derisively referred to in the literature as "Onsagerism").
機譯：在假設(shè)的“等擴散”情況下，線性不可逆熱力學(xué)（LIT）原理用于顯示在控制能量，多組分種類，熵和體積的擴散傳輸?shù)木€性近平衡本構(gòu)律中出現(xiàn)的所有各種現(xiàn)象學(xué)擴散系數(shù)。 （雖然不一定包括動量）是相等的，但與非平衡熱力學(xué)有關(guān)的Onsager倒數(shù)關(guān)系會自動遵循麥克斯韋控制平衡熱力學(xué)的倒數(shù)關(guān)系。因此，這構(gòu)成了Onsager互惠的純宏觀證明，這是同類中的第一個。盡管在大多數(shù)情況下，等擴散極限情況下所需的擴散系數(shù)相等并不代表現(xiàn)實的可能性，但在將可逆和不可逆熱力學(xué)統(tǒng)一起來的過程中，采用箔作為箔片既不會違反也不會與任何已知的物理定律發(fā)生沖突。確實，在某種理想化的意義上，這種平等代表了這些獨特的物理傳輸現(xiàn)象之間眾所周知的類比的完美。此外，如對于具有可比較分子量的化學(xué)相似的稀氣體的混合物（例如，同源系列的連續(xù)成員）所示，等擴散假設(shè)通常是相當(dāng)好的。作為獎勵，我們的分析-符合宏觀物理學(xué)的所有已知準(zhǔn)則-構(gòu)成了對Coleman和Truesdell長期批評的滿意解決方案。 Coleman，C. Truesdell，關(guān)于Onsager的對等關(guān)系，J。Chem。物理33（1960）28-31]集中討論了Onsager對稱性可能只是重言式的可能性（在文獻(xiàn)中被稱為“ Onsagerism”）。

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