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Violations of Onsager reciprocity?

+ 6 like - 0 dislike
170 views

As far as I understand it, the modern statement of Onsager reciprocity is that the linear-response transport coefficient matrix, when transposed, is equal to that of the time-reversed system (reversed external magnetic field, reversed internal magnetic order, reversed Coriolis forces, and so on). Many consider this to be the fourth law of thermodynamics.

Clifford Truesdell however famously complained of "Onsagerism", which appears to mean the (unjustified) faith in Onsager reciprocity despite what he regarded as shaky foundations: reliance on kinetic theory, and so on. And yet, the foundations of Onsager do not seem so shaky to me: 1) the fluctuation-dissipation theorem and 2) the mathematical fact that fluctuation correlations in a time-reversed system should be, well, time-reversed. Quite general and elegant, really. Might even be worth a Nobel prize.

So, my question: are there real counterexamples to Onsager? I have seen many proposed counterexamples where I thought "OK, you just failed to time-reverse your system properly." (and indeed perhaps the difficulty of proper time-reversal indicates an Onsagerism pitfall). But... is the reciprocity fundamentally flawed?


This post imported from StackExchange Physics at 2016-04-13 09:05 (UTC), posted by SE-user Nanite

asked Apr 5, 2016 in Theoretical Physics by Nanite (40 points) [ revision history ]
edited Apr 13, 2016 by Dilaton
to quote Truesdell "As far as I can learn, the first experimental tests of Stefan's relations were made by Dunlop & Gosting in 1955. As I read the results reported by them and others for eleven different solutions in water, they indicate that for eight systems Stefan's relations hold, that for one they are doubtful, and that for two they clearly do not hold." The reference is to P. J. Dunlop & L. J. Costing, "Interacting flows in liquid diffusion" J. Am. Chem. Soc, 77:5238-5249 A955).

This post imported from StackExchange Physics at 2016-04-13 09:05 (UTC), posted by SE-user hyportnex

1 Answer

+ 3 like - 0 dislike

Onsager got the Nobel prize in Chemistry 1968 ffor the discovery of the reciprocal relations bearing his name, which are fundamental for the thermodynamics of irreversible processes.

His derivation is very general. In case of external magnetic fields or Coriolis fields, the Onsager relations must be modified since the behavior of these fields under time reversal is different. His paper L. Onsager, Reciprocal Relations in Irreversible Processes I, Phys. rev. 37 (1931), 405-426 already contains this caveat.

answered Apr 13, 2016 by Arnold Neumaier (12,355 points) [ no revision ]

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