0000000000083241
AUTHOR
Julio Pellicer
THE GOLDMAN CONSTANT FIELD ASSUMPTION - SIGNIFICANCE AND APPLICABILITY CONDITIONS
Ionic transport phenomena in simple, porous membranes can be approximately represented by the Nernst-Planck flux equations and Poisson's equation. In order to solve this set of equations for each particular case, the Goldman constant field assumption is one of the most widely used. In the present paper the significance and the applicability conditions of the above hypothesis is critically examined. and the particular situations where it is exact are shown. These conditions are later verified by solving numerically the electrodiffusion equations. The analysis carried out shows that some of the earlier studies based on asymptotic expansions and numerical solutions should be partially revised.
Generalization of a finite-difference numerical method for the steady-state and transient solutions of the nernst—planck flux equations
Abstract A generalization of the numerical method of Brumleve and Buck for the solution of Nernst—Planck equations when convective flux and electric current are involved has been developed. The simulation procedure was applied to a specific case: transport of strong electrolytes in a wide-pore membrane with simultaneous diffusion, convection and electric current. Good agreement was found between experimental data and computed results.
IONIC TRANSPORT ACROSS POROUS CHARGED MEMBRANES AND THE GOLDMAN CONSTANT FIELD ASSUMPTION
Starting from a simple theoretical model based on Nernst-Planck flux equations and the Donnan equilibrium relationship, the ionic transport across a porous, charged membrane is analysed and conditions are given which make exact the so-called “constant field assumption”. The validity of the reported results is later verified in the case of a well-known problem: the ionic transport across a cation-exchange membrane under bi-ionic conditions.
Ion conduction in the KcsA potassium channel analyzed with a minimal kinetic model.
We use a model by Nelson to study the current-voltage and conductance-concentration curves of bacterial potassium channel KcsA without assuming rapid ion translocation. Ion association to the channel filter is rate controlling at low concentrations, but dissociation and transport in the filter can limit conduction at high concentration for ions other than ${\mathrm{K}}^{+}$. The absolute values of the effective rate constants are tentative but the relative changes in these constants needed to qualitatively explain the experiments should be of significance.
Validity of the electroneutrality and goldman constant-field assumptions in describing the diffusion potential for ternary electrolyte systems in simple, porous membranes
Abstract Three numerical algorithms capable of simulating transport processes through simple, porous membranes in the steady state have been employed in order to study the change in the diffusion potential with the membrane thickness and the ionic concentrations for the ternary systems NaClHClH20 and CaCI2NaC1H 2 O. The first simulation procedure uses Poisson's equation, the two others replace this equation by the electroneutrality and Goldman constant-field approximations respectively. From the results presented here, conditions for the applicability of the electroneutrality and constantfield assumption to ternary electrolyte systems are given.
Deviations from equilibrium at the interface of a charged membrane
The local equilibrium assumption commonly employed for the transport through the interface of a charged membrane has been analysed from a simplified electric double layer model. This layer is characterized on the basis of a surface potential arising from a non-zero surface charge density placed on the membrane surface. The dependence of deviations from local equilibrium on the characteristic parameters of the problem is shown. Connection with the classical treatment by Donnan is discussed. Although the complexity of the problem calls for a number of simplifications, the results obtained appears to be significative. Thus, the analysis carried out displays not only that deviations from equili…
Thermodynamics of Rubber Elasticity
A thermodynamic study of an isotropic rubber band under uniaxial stress is presented on the basis of its equation of state. The behavior of the rubber band is compared with both that of an ideal elastomer and that of an ideal gas, considering the generalized Joule's law as the ideality criterion.
Influence of shear rate and concentration ratio on viscous synergism. Application to xanthan—Iocust bean gum— NaCMC mixtures Influencia de la velocidad de cizalla y la relación de concentraciones en la sinergia viscosa. Aplicación a mezclas de xantana-garrofín-CMCNa
A method is described that allows the development of an empirical approach to quantify synergistic interactions and their variations with shear rate. The approach is based on the definition of a viscous synergism index, Iv. The method is applied to xanthan-locust bean gum gels, and an equation is developed for relating the synergism index to shear rate, γ, and the locust bean gum/xanthan gum concentration ratio, z. The value of at which that function has a maximum, IMV, is calculated. This value of z provided an estimation of the proportion of gums at which maximum synergism occurs. A decreasing exponential dependence of these IMV on γ is shown. The influence of the addition of a fixed pro…
Calculation of the wetting parameter from a cluster model in the framework of nanothermodynamics
The critical wetting parameter ${\ensuremath{\omega}}_{c}$ determines the strength of interfacial fluctuations in critical wetting transitions. In this Brief Report, we calculate ${\ensuremath{\omega}}_{c}$ from considerations on critical liquid clusters inside a vapor phase. The starting point is a cluster model developed by Hill and Chamberlin in the framework of nanothermodynamics [Proc. Natl. Acad. Sci. USA 95, 12779 (1998)]. Our calculations yield results for ${\ensuremath{\omega}}_{c}$ between 0.52 and 1.00, depending on the degrees of freedom considered. The findings are in agreement with previous experimental results and give an idea of the universal dynamical behavior of the cluste…
Gibbs' Dividing Surface between a Fixed-Charge Membrane and an Electrolyte Solution. Application to Electrokinetic Phenomena in Charged Pores
The Gibbs model for the boundary between two phases consists of replacing the finite interfacial region, where the properties of the system change gradually, by a dividing surface which acts as a third phase of zero volume in which some magnitudes change abruptly. This thermodynamic concept was recently applied to a planar interface between a fixed charge membrane and an electrolyte solution.1 The continuous decrease of counterions with the distance from the charged surface is replaced by a step function, so that the diffuse double layer is ideally represented by a charged region depleted of all co-ions. Here the cylindrical geometry is analyzed, and the planar case is revisited by proposin…
Microcanonical foundation of nonextensivity and generalized thermostatistics based on the fractality of the phase space
We develop a generalized theory of (meta)equilibrium statistical mechanics in the thermodynamic limit valid for both smooth and fractal phase spaces. In the former case, our approach leads naturally to Boltzmann-Gibbs standard thermostatistics while, in the latter, Tsallis thermostatistics is straightforwardly obtained as the most appropriate formalism. We first focus on the microcanonical ensemble stressing the importance of the limit $t \to \infty$ on the form of the microcanonical measure. Interestingly, this approach leads to interpret the entropic index $q$ as the box-counting dimension of the (microcanonical) phase space when fractality is considered.
Thermodynamics based on the principle of least abbreviated action: Entropy production in a network of coupled oscillators
We present some novel thermodynamic ideas based on the Maupertuis principle. By considering Hamiltonians written in terms of appropriate action-angle variables we show that thermal states can be characterized by the action variables and by their evolution in time when the system is nonintegrable. We propose dynamical definitions for the equilibrium temperature and entropy as well as an expression for the nonequilibrium entropy valid for isolated systems with many degrees of freedom. This entropy is shown to increase in the relaxation to equilibrium of macroscopic systems with short-range interactions, which constitutes a dynamical justification of the Second Law of Thermodynamics. Several e…
Correct thermodynamic forces in Tsallis Thermodynamics: connection with Hill Nanothermodynamics
The equivalence between Tsallis Thermodynamics and Hill Nanothermodynamics is established. The correct thermodynamic forces in Tsallis thermodynamics are pointed out. Through this connection we also find a general expression for the entropic index $q$ which we illustrate with two physical examples, allowing in both cases to relate $q$ to the underlying dynamics of the Hamiltonian systems.
Kinetic modeling of ion conduction in KcsA potassium channel.
KcsA constitutes a potassium channel of known structure that shows both high conduction rates and selectivity among monovalent cations. A kinetic model for ion conduction through this channel that assumes rapid ion transport within the filter has recently been presented by Nelson. In a recent, brief communication, we used the model to provide preliminary explanations to the experimental current-voltage J-V and conductance-concentration g-S curves obtained for a series of monovalent ions (K(+),Tl(+), and Rb(+)). We did not assume rapid ion transport in the calculations, since ion transport within the selectivity filter could be rate limiting for ions other than native K(+). This previous wor…
A finite-difference method for numerical solution of the steady-state nernst—planck equations with non-zero convection and electric current density
Abstract A computer algorithm has been developed for digital simulation of ionic transport through membranes obeying the Nernst—Planck and Poisson equations. The method of computation is quite general and allows the treatment of steady-state electrodiffusion equations for multiionic environments, the ionic species having arbitrary valences and mobilities, when convection and electric current are involved. The procedure provides a great flexibility in the choice of suitable boundary conditions and avoids numerical instabilities which are so frequent in numerical methods. Numerical results for concentration and electric potential gradient profiles are presented in the particular case of the t…
Coupling theory for counterion distributions based in Tsallis statistics
It is well known that the Poisson-Boltzmann (PB) equation yields the exact counterion density around charged objects in the weak coupling limit. In this paper we generalize the PB approach to account for coupling of arbitrary strength by making use of Tsallis q-exponential distributions. Both the weak coupling and the strong coupling limits are reproduced. For arbitrary coupling we also provide simple analytical expressions which are compared to recent Monte Carlo simulations by A. G. Moreira and R. R. Netz [Europhys. Lett. 52 (2000) 705]. Excellent agreement with these is obtained.
Viscous Synergism in Carrageenans (κ and λ) and Locust Bean Gum Mixtures: Influence of Adding Sodium Carboxymethylcellulose
Se han estudiado las interacciones sinergicas entre la goma de garrofin (LBG) y dos tipos de carragenanos (kappa y lambda). Para cada mezcla se obtuvo el indice de sinergia viscosa, Iy, en funcion de la relacion de concentraciones, z =c'LBG/c'car, y de la velocidad de cizalla. Los valores de estos indices disminuyeron al aumentar la velocidad de cizalla en ambos sistemas binarios. En las mezclas de LBG + K, I, presento un maximo para una relacion de concentraciones z = 60/40, que puede considerarse como la optima proporcion de estas gomas en la mezcla. Sin embargo, en los sistemas LBG + A, I, aumento con z en todo el intervalo considerado, es decir, la mayor sinergia correspondio a las meno…