Thermodynamic factors for locally non-neutral, concentrated electrolytic fluids

A constitutive framework is created to parameterize the composition-dependent parts of thermodynamic differentials that undergird diffusion driving forces in non-neutral electrolytic fluids. The definition a novel two-ion secondary reference state allows us formulate neutralizable composition basis, which one natural variable replaced by molar excess charge. This basis conjugate set energy descriptors we call core potentials, among Maxwell relations and Gibbs–Duhem constraints take simple forms isolate charge effects. Core potentials derive from intensive measures composition, refinement Kokotov's twin-potential scheme enables applications materials wherein properties vary spatially. Matrix representations are constructed for transformations interconvert Guggenheim (electrochemical), Smyrl–Newman (quasielectrostatic), potentials. These reveal how formalisms can be extended handle charge-imbalanced microscopic equilibria. core-potential naturally parameterized terms conventional electroneutral factors, but also includes an independent new electrostatic colligative account additional equation governing Consistent parameterizations derived electrolytes obey ideal-solution approximation follow Poisson–Boltzmann theory. We explicitly develop equations species electrochemical-potential within chemically nonideal binary solution symmetrical-valence electrolyte satisfies charge–potential relation.