Additional Arguments for a Correction of the Debye-Hückel, Maxwell-Boltzmann Equations for Dilute Electrolyte Equilibria

Peter Debye and Erich Hückel had developed a theory for the ionic activity coefficients in dilute solutions of strong electrolytes some 95 years ago [1]. Their limiting law still stands and is confirmed as close to reality in many experiments. In a previous article [2], it is shown that these limiting activity coefficients arise because the electrical contribution in the electrochemical potential of ionic species is overestimated traditionally with a factor 2. The smaller value removes inconsistencies in the models and complies better with the basic electrostatic principles. In this article further evidence is given in support of this alternative description. As consequence the dilute activity coefficients become unity, e.g. are removed, which means that the electrochemical potential of ions in dilute solutions is expressed directly in concentration, instead of activity, which simplifies modelling in such dilute solutions.

A Consensus Modeling Approach for the Determination of Stratum Corneum Thickness Using In-Vivo Confocal Raman Spectroscopy

The measurement of stratum corneum (SC) thickness from in-vivo Raman water concentration depth profiles is gaining in popularity and appeal due to the availability and ease of use of in-vivo confocal Raman measurement systems. The foundation of these measurements relies on high-quality confocal Raman spectroscopy of skin and the robust numerical analysis of water profiles, which allow for accurate determination of SC thickness. These measurements are useful for studying intrinsic skin hydration profiles at different body sites and for determining hydration properties of skin related to topically applied materials. While the use of high-quality in-vivo Raman instrumentation has become routine and its use for SC thickness measurement widely reported, there is lack of agreement as to the best method of computing SC thickness values from Raman water profiles. Several methods have been proposed and are currently in use for such computations, but none of these methods has been critically evaluated. The work reported in this paper describes a new method for the determination of stratum corneum thickness from in-vivo confocal Raman water profiles. The method represents a consensus approach to the problem, which was found necessary to apply in order to properly model and quantify the large diversity of water profile types encountered in typical in-vivo Raman water measurement. The methodology is evaluated for performance using three criteria: 1) frequency of minimum fitting error on modeling to a standard numerical function;2) frequency of minimum model error for consensus vs. individual SC thickness values;and 3) correlation with reflectance confocal microscopy (RCM) values for SC thickness. The correlation study shows this approach to be a reasonable replacement for the more tedious and time-consuming RCM method with R2 = 0.68 and RMS error = 3.7 microns over the three body sites tested (cheek, forearm and leg).