Dependence of the dielectric constant of electrolyte solutions on ionic concentration - a microfield approach

We present a novel microfield approach for studying the dependence of the orientational polarization of the water in aqueous electrolyte solutions upon the salt concentration and temperature. The model takes into account the orientation of the solvent dipoles due to the electric field created by ions, and the effect of thermal fluctuations. The model predicts a dielectric functional dependence of the form $\varepsilon(c)=\varepsilon_w-\beta L(3\alpha c/\beta),\quad\beta=\varepsilon_w-\varepsilon_{\rm ms}$, where $L$ is the Langevin function, $c$ is the salt concentration, $\varepsilon_w$ is the dielectric of pure water, $\varepsilon_{\rm ms}$ is the dielectric of the electrolyte solution at the molten salt limit, and $\alpha$ is the total excess polarization of the ions. The functional form gives a remarkably accurate description of the dielectric constant for a variety of salts and a wide range of concentrations.Comment: Accepted for publication in Physical Review

Mathematical modelling of the catalyst layer of a polymer-electrolyte fuel cell

In this paper we derive a mathematical model for the cathode catalyst layer of a polymer electrolyte fuel cell. The model explicitly incorporates the restriction placed on oxygen in reaching the reaction sites, capturing the experimentally observed fall in the current density to a limiting value at low cell voltages. Temperature variations and interfacial transfer of O2 between the dissolved and gas phases are also included. Bounds on the solutions are derived, from which we provide a rigorous proof that the model admits a solution. Of particular interest are the maximum and minimum attainable values. We perform an asymptotic analysis in several limits inherent in the problem by identifying important groupings of parameters. This analysis reveals a number of key relationships between the solutions, including the current density, and the composition of the layer. A comparison of numerically computed and asymptotic solutions shows very good agreement. Implications of the results are discussed and future work is outlined

Adiabatic stability under semi-strong interactions: The weakly damped regime

We rigorously derive multi-pulse interaction laws for the semi-strong interactions in a family of singularly-perturbed and weakly-damped reaction-diffusion systems in one space dimension. Most significantly, we show the existence of a manifold of quasi-steady N-pulse solutions and identify a "normal-hyperbolicity" condition which balances the asymptotic weakness of the linear damping against the algebraic evolution rate of the multi-pulses. Our main result is the adiabatic stability of the manifolds subject to this normal hyperbolicity condition. More specifically, the spectrum of the linearization about a fixed N-pulse configuration contains essential spectrum that is asymptotically close to the origin as well as semi-strong eigenvalues which move at leading order as the pulse positions evolve. We characterize the semi-strong eigenvalues in terms of the spectrum of an explicit N by N matrix, and rigorously bound the error between the N-pulse manifold and the evolution of the full system, in a polynomially weighted space, so long as the semi-strong spectrum remains strictly in the left-half complex plane, and the essential spectrum is not too close to the origin