Abstract

Öttinger's recent nontraditional incorporation of fluctuations into the formulation of the friction matrix appearing in the phenomenological GENERIC theory of nonequilibrium irreversible processes is shown to furnish transport equations for single-component gases and liquids undergoing heat transfer which support the view that revisions to the Navier–Stokes–Fourier (N–S–F) momentum/energy equation set are necessary, as empirically proposed by the author on the basis of an experimentally supported theory of diffuse volume transport. The hypothesis that the conventional N–S–F equations prevail without modification only in the case of “incompressible” fluids, where the density ρ of the fluid is uniform throughout, serves to determine the new phenomenological parameter α ′ appearing in the GENERIC friction matrix. In the case of ideal gases the consequences of this constitutive hypothesis are shown to yield results identical to those derived theoretically by Öttinger on the basis of a “proper” coarse-graining of Boltzmann's kinetic equation. A major consequence of the present work is that the fluid's specific momentum density v is equal to its volume velocity v v , rather than to its mass velocity v m , contrary to current views dating back 250 years to Euler. In the case of rarefied gases the proposed modifications are also observed to agree with those resulting from Klimontovich's molecularly based, albeit ad hoc, self-diffusion addendum to Boltzmann's collision integral. Despite the differences in their respective physical models—molecular vs. phenomenological—the role played by Klimontovich's collisional addition to Boltzmann's equation in modifying the N–S–F equations is noted to constitute a molecular counterpart of Öttinger's phenomenological fluctuation addition to the GENERIC friction matrix. Together, these two theories collectively recognize the need to address multiple- rather than single- encounter collisions between a test molecule and its neighbors when formulating physically satisfactory statistical–mechanical theories of irreversible transport processes in gases. Overall, the results of the present work implicitly support the unorthodox view, implicit in the GENERIC scheme, that the translation of Newton's discrete mass-point molecular mechanics into continuum mechanics, the latter as embodied in the Cauchy linear momentum equation of fluid mechanics, cannot be correctly effected independently of the laws of thermodynamics. While Öttinger's modification of GENERIC necessitates fundamental changes in the foundations of fluid mechanics in regard to momentum transport, no basic changes are required in the foundations of linear irreversible thermodynamics (LIT) beyond recognizing the need to add volume to the usual list of extensive physical properties undergoing transport in single-species fluid continua, namely mass, momentum and energy. An alternative, nonGENERICally based approach to LIT, derived from our findings, is outlined at the conclusion of the paper. Finally, our proposed modifications of both Cauchy's linear momentum equation and Newton's rheological constitutive law for fluid-phase continua are noted to be mirrored by counterparts in the literature for solid-phase continua dating back to the classical interdiffusion experiments of Kirkendall and their subsequent interpretation by Darken in terms of diffuse volume transport.

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