Reciprocal Relations in Irreversible Processes. I. Export

@article{citeulike:1626398, abstract = {Examples of coupled irreversible processes like the thermoelectric phenomena; the transference phenomena in electrolytes and heat conduction in an anisotropic medium are considered. For certain cases of such interaction reciprocal relations have been deduced by earlier writers; e.g.; Thomson's theory of thermoelectric phenomena and Helmholtz' theory for the e.m.f. of electrolytic cells with liquid junction. These earlier derivations may be classed as quasi-thermodynamic; in fact; Thomson himself pointed out that his argument was incomplete; and that his relation ought to be established on an experimental basis. A general class of such relations will be derived by a new theoretical treatment from the principle of microscopic reversibility. ({\S}{\S}1-2.) The analogy with a chemical monomolecular triangle reaction is discussed; in this case a a simple kinetic consideration assuming microscopic reversibility yields a reciprocal relation that is not necessary for fulfilling the requirements of thermodynamics ({\S}3). Reciprocal relations for heat conduction in an anisotropic medium are derived from the assumption of microscopic reversibility; applied to fluctuations. ({\S}4.) The reciprocal relations can be expressed in terms of a potential; the dissipation-function. Lord Rayleigh's "principle of the least dissipation of energy" is generalized to include the case of anisotropic heat conduction. A further generalization is announced. ({\S}5.) The conditions for stationary flow are formulated; the connection with earlier quasi-thermodynamic theories is discussed. ({\S}6.) The principle of dynamical reversibility does not apply when (external) magnetic fields or Coriolis forces are present; and the reciprocal relations break down. ({\S}7.)}, author = {Onsager, Lars}, citeulike-article-id = {1626398}, citeulike-linkout-0 = {http://dx.doi.org/10.1103/PhysRev.37.405}, citeulike-linkout-1 = {http://link.aps.org/abstract/PR/v37/i4/p405_1}, citeulike-linkout-2 = {http://link.aps.org/pdf/PR/v37/i4/p405_1}, day = {15}, doi = {10.1103/PhysRev.37.405}, journal = {Physical Review}, keywords = {irreversible, thermodynamics}, month = {February}, number = {4}, pages = {405+}, posted-at = {2009-01-14 16:52:27}, priority = {2}, publisher = {American Physical Society}, title = {Reciprocal Relations in Irreversible Processes. I.}, url = {http://dx.doi.org/10.1103/PhysRev.37.405}, volume = {37}, year = {1931} }

TY - JOUR ID - citeulike:1626398 L3 - citeulike-article-id:1626398 N2 - Examples of coupled irreversible processes like the thermoelectric phenomena; the transference phenomena in electrolytes and heat conduction in an anisotropic medium are considered. For certain cases of such interaction reciprocal relations have been deduced by earlier writers; e.g.; Thomson's theory of thermoelectric phenomena and Helmholtz' theory for the e.m.f. of electrolytic cells with liquid junction. These earlier derivations may be classed as quasi-thermodynamic; in fact; Thomson himself pointed out that his argument was incomplete; and that his relation ought to be established on an experimental basis. A general class of such relations will be derived by a new theoretical treatment from the principle of microscopic reversibility. (§§1-2.) The analogy with a chemical monomolecular triangle reaction is discussed; in this case a a simple kinetic consideration assuming microscopic reversibility yields a reciprocal relation that is not necessary for fulfilling the requirements of thermodynamics (§3). Reciprocal relations for heat conduction in an anisotropic medium are derived from the assumption of microscopic reversibility; applied to fluctuations. (§4.) The reciprocal relations can be expressed in terms of a potential; the dissipation-function. Lord Rayleigh's "principle of the least dissipation of energy" is generalized to include the case of anisotropic heat conduction. A further generalization is announced. (§5.) The conditions for stationary flow are formulated; the connection with earlier quasi-thermodynamic theories is discussed. (§6.) The principle of dynamical reversibility does not apply when (external) magnetic fields or Coriolis forces are present; and the reciprocal relations break down. (§7.) IS - 4 JF - Physical Review TI - Reciprocal Relations in Irreversible Processes. I. PB - American Physical Society VL - 37 SP - 405 KW - irreversible KW - thermodynamics AU - Onsager, Lars PY - 1931/02/15/ UR - http://dx.doi.org/10.1103/PhysRev.37.405 ER -