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Title: Onsager’s reciprocal relations in electrolyte solutions. I. Sedimentation and electroacoustics

In the framework of irreversible thermodynamics, we show that the sedimentation current in electrolyte solutions is mathematically equivalent to the low frequency limit of the ionic vibration current, appearing in the presence of an acoustic wave. This non-trivial result is obtained thanks to a careful choice of the reference frame used to express the mass fluxes in the context of electroacoustics. Coupled transport phenomena in electrolyte solutions can also be investigated in a mechanical framework, with a set of Newtonian equations for the dynamics of charged solutes. Both in the context of sedimentation and of electroacoustics, we show that the results obtained in the mechanical framework, in the ideal case (i.e., without interactions between ions), do satisfy the Onsager’s reciprocal relations. We also derive the general relation between corrective forces accounting for ionic interactions which must be fulfilled so that the Onsager’s reciprocal relations are verified. Finally, we show that no additional diffusion term needs to be taken into account in the flux of solutes (far from the walls), even if local concentration gradients exist, contrarily to what was done previously in the literature.
Authors:
; ;  [1] ;  [1] ;  [2]
  1. Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire PHENIX, Case 51, 4 Place Jussieu, F-75005 Paris (France)
  2. (Netherlands)
Publication Date:
OSTI Identifier:
22493521
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 6; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABUNDANCE; ACCOUNTING; CONCENTRATION RATIO; DIFFUSION; ELECTROLYTES; IONIC CONDUCTIVITY; ONSAGER RELATIONS; SEDIMENTATION; SOLUTES; SOLUTIONS; SOUND WAVES; THERMODYNAMICS