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Péter L Simon

Publications and source records attributed to Péter L Simon.

5 recordsLinked to original sources

Electrolyte diodes with weak acids and bases. I. Theory and an approximate analytical solution.

Until now acid-base diodes and transistors applied strong mineral acids and bases exclusively. In this work properties of electrolyte diodes with weak electrolytes are studied and compared with those of diodes with strong ones to show the advantages of weak acids and bases in these applications. The theoretical model is a one dimensional piece of gel containing fixed ionizable groups and connecting reservoirs of an acid and a base. The electric current flowing through the gel is measured as a function of the applied voltage. The steady-state current-voltage characteristic (CVC) of such a gel looks like that of a diode under these conditions. Results of our theoretical, numerical, and experimental investigations are reported in two parts. In this first, theoretical part governing equations necessary to calculate the steady-state CVC of a reverse-biased electrolyte diode are presented together with an approximate analytical solution of this reaction-diffusion-ionic migration problem. The applied approximations are quasielectroneutrality and quasiequilibrium. It is shown that the gel can be divided into an alkaline and an acidic zone separated by a middle weakly acidic region. As a further approximation it is assumed that the ionization of the fixed acidic groups is complete in the alkaline zone and that it is completely suppressed in the acidic one. The general solution given here describes the CVC and the potential and ionic concentration profiles of diodes applying either strong or weak electrolytes. It is proven that previous formulas valid for a strong acid-strong base diode can be regarded as a special case of the more general formulas presented here.

Acids↗

Electrolyte diodes with weak acids and bases. II. Numerical model calculations and experiments.

This is the second part of our work dealing with electrolyte diodes with weak acids and bases. In the first part an approximative analytical solution was derived for the steady-state current-voltage characteristic (CVC) of a reverse-biased diode (a quasi-one-dimensional gel connecting an acidic and an alkaline reservoir), applying either strong or weak electrolytes. An approximative analytical solution is compared here with a numerical solution free of any approximations and with CVCs measured experimentally with both strong and weak electrolytes. It is shown that the deviations between the numerical and analytical solutions are mostly due to assumptions made for the fixed charge concentration profiles. The concept of optimal analytical solution is introduced which does not use such assumptions and applies only the quasielectroneutrality and quasiequilibrium approximations. It is proven that the slope of the CVC based on the optimum analytical solution can be calculated without the complicated derivation of that solution itself. The calculation of that slope is based on the fact that in the optimum analytical solution all currents are inversely proportional to the length if the boundary conditions are held constant and realizing that in the middle part of the gel the only mobile counterions of the fixed ionized groups are hydrogen ions. In the experimental part the apparatus and the preparation of the gel are described together with the CVCs measured with strong and weak electrolytes. From these CVCs the fixed ion concentration in the middle part of the gel can be determined. That fixed ion concentration is 1.96 x 10(-4)M measured with weak electrolytes and 3.48 x 10(-4)M measured with strong electrolytes. The deviation indicates that the strong base causes some hydrolysis of the gel. Finally, possible applications of weak acid-weak base diodes are discussed.

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Electrolyte diodes and hydrogels: determination of concentration and pK value of fixed acidic groups in a weakly charged hydrogel.

Current-voltage (CV) characteristics of polyvinyl alcohol (PVA)-glutardialdehyde hydrogel cylinders were measured in aqueous KCl solutions. To this end a new special apparatus was constructed where the gel cylinder connects two electrolyte reservoirs. The measured quantities are the electric current flowing through the gel and the potential difference between the two reservoirs. Concentration polarization near the gel-liquid interfaces is decreased considerably by applying an intense mechanical stirring in both reservoirs. Under these conditions below 1 V concentration polarization is negligible, and the CV curves are nearly straight lines. It was found that the gel applied here is a weakly charged anionic hydrogel. Concentration of fixed anions was determined from the slope of these lines measured in 0.001 and 0.01 molar KCl solutions. Fixed anion concentration of the same piece of gel was measured also with a different method, when the gel was used in an acid-base diode. In this case one reservoir contained 0.1 molar HCl, and the other 0.1 molar KOH. From the results of the two measurements, the concentration (4.45 x 10(-3) M) and the pK value (4.03) of the fixed acid groups responsible for the anionic character of the gel was calculated. The pK value is compatible with fixed carboxylic acid groups contaminating the PVA gel. Furthermore, concentration polarization phenomena in the boundary layers nearby the gel were studied in 0.001 M KCl solutions, measuring the diodelike CV characteristic of a gel cylinder, when stirring was applied only at one side of the gel. Boundary layers facing the cathode or the anode responded in a different way to stirring. The difference cannot be explained completely with the hypothesis of electroconvection suggested previously.

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Isothermal flame balls: effect of autocatalyst decay.

The steady, spherically symmetric solutions to the reaction-diffusion equations based on a simple autocatalytic reaction followed by the decay of the autocatalyst are considered. Three parameters-the orders with respect to the autocatalyst in the autocatalysis p and in the decay q and the rate of decay of the autocatalyst relative to its autocatalytic production K-determine the steady concentration profiles. Numerical integrations for a fixed value of the order of the autocatalyst show that the concentration profiles have different forms depending on whether q /=p. In the former case, there is a critical decay rate K(crit) for solutions to exist, with multiple solutions for K<K(crit). In the latter case, there is a single solution for each value of K. This difference in the nature of the solution is confirmed by an analysis for p large. The temporal stability of the isothermal flame balls is examined, with temporally stable solutions being possible, provided that the ratio of the diffusion coefficient of the autocatalyst to that of the reactant is sufficiently small. The change in stability appears only when there are multiple solutions and is through a subcritical Hopf bifurcation.

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Isothermal flame balls.

The existence of steady, spherically symmetric wave fronts ("isothermal flame balls") in chemical reaction systems exhibiting autocatalysis is demonstrated. Such solutions require relatively high kinetic orders p with respect to the autocatalytic species, with p>5, but occur even with equal diffusion coefficients. The flame balls are unstable, but have relevance as they indicate the minimum size for a perturbation to initiate a propagating front. A flame ball radius R(b) is identified and the dependence of this quantity on the autocatalytic order is determined. This shows R(b) tending to infinity as p-->5(+) and as p--> infinity, with a minimum for p approximately 6.71. Numerical computations are confirmed by asymptotic analysis appropriate for p-->5(+) and for systems with p large.

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