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P Turq

Publications and source records attributed to P Turq.

16 recordsLinked to original sources
PubMed2006

Determining the radius and the apparent charge of a micelle from electrical conductivity measurements by using a transport theory: explicit equations for practical use.

We propose here a procedure which combines experiments and simple analytical formulas that allows us to determine good estimations of the size and charge of ionic micelles above the critical micellar concentration (cmc). First, the conductivity of n-tetradecyltrimethylammonium bromide and chloride (TTABr and TTACl, respectively) aqueous solutions was measured at 25 degrees C, before and above their cmc. Then, an analytical expression for the concentration dependence of the conductance of an ionic mixture with three species (monomers, micelles, and counterions) was developed and applied to the analysis of the experiments. The theoretical calculations use the mean spherical approximation (MSA) to describe equilibrium properties. Here, we propose new expressions for the electrical conductivity, adapted to the case of electrolytes that are dissymmetric in size, and applicable up to a total surfactant concentration of 0.1 mol L(-1). Moreover, we show that they are good approximations of the corresponding numerical results obtained from Brownian dynamics simulations. Since the analytical formulas given in the present paper involve a small number of unknown parameters, they allow one to derive the size and charge of macroions in solution from conductivity measurements.

Journal Article↗
PubMed2006

Ion dynamics in compacted clays: derivation of a two-state diffusion-reaction scheme from the lattice Fokker-Planck equation.

We show how a two-state diffusion-reaction description of the mobility of ions confined within compacted clays can be constructed from the microscopic dynamics of ions in an external field. The diffusion-reaction picture provides the usual interpretation of the reduced ionic mobility in clays, but the required partitioning coefficient K(d) between trapped and mobile ions is generally an empirical parameter. We demonstrate that it is possible to obtain K(d) from the microscopic dynamics of ions interacting with the clay surfaces by evaluating the ionic mobility using a novel lattice implementation of the Fokker-Planck equation. The resulting K(d) allows a clear-cut characterization of the trapping sites on the clay surfaces and determines the adsorption/desorption rates. The results highlight the limitations of standard approximation schemes and pinpoint the crossover from jump to Brownian diffusion regimes.

Journal Article↗
PubMed2006

Molecular dynamics simulation of hydrogen fluoride mixtures with 1-ethyl-3-methylimidazolium fluoride: a simple model for the study of structural features.

Mixtures of hydrogen fluoride with ionic liquids show unique physicochemical properties, including their ability to form polyfluoride species (pointed out for the first time in this media by von Rosenvinge et al. J. Chem. Phys. 1997, 107, 8012). Among those systems the acidic 1-ethyl-3-methylimidazolium fluoride (EMIF.2.3HF) has been widely studied experimentally since it is the more promising for electrochemical applications. Recent studies (Hagiwara et al. J. Electrochem. Soc. 2002, 149, D1), while yielding many results, raised some questions about structural features of the liquid: absence of hydrogen bonds between the EMI+ ring hydrogen atoms and the fluoride anions, persistence of stacks and layers of cations similar to those existing in the crystal, and interpretation of the X-ray diffraction spectra. To address these questions, we have developed a simple molecular dynamics model. Our simulations are very consistent with experimental results and complete them, providing an atomic scale interpretation.

Journal Article↗
PubMed2006

Diffusion of water in clays on the microscopic scale: modeling and experiment.

Diffusion of water in montmorillonite clays at low hydration has been studied on the microscopic scale by two quasi-elastic neutron scattering techniques, neutron spin-echo (NSE) and time-of-flight (TOF), and by classical microscopic simulation. Experiment and simulation are compared both directly on the level of intermediate scattering functions, I(Q, t), and indirectly on the level of relaxation times after a model of atomic motion is applied. Regarding the dynamics of water in Na- and Cs-monohydrated montmorillonite samples, the simulation and NSE results show a very good agreement, both indicating diffusion coefficients of the order of (1-3) x 10(-10) m(2) s(-1). The TOF technique significantly underestimates water relaxation times (therefore overestimates water dynamics), by a factor of up to 3 and 7 in the two systems, respectively, primarily due to insufficiently long correlation times being probed. In the case of the Na-bihydrated system, the TOF results are in closer agreement with the other two techniques (the techniques differ by a factor of 2-3 at most), giving diffusion coefficients of (5-10) x 10(-10) m(2) s(-1). Attention has been also paid to the elastic incoherent structure factor, EISF(Q). Simulation has played a key role in understanding the various contributions to EISF(Q) in clay systems and in clearly distinguishing the signatures of "apparent" and true confinement. Indirectly, simulation highlights the difficulty in interpreting the EISF(Q) signal from powder clay samples used in experiments.

Aluminum↗
PubMed2005

Frequency-dependent dielectric permittivity of salt-free charged lamellar systems.

We present a new model to analyze dielectric spectroscopy measurements on charged lamellar systems, with the following improvements with respect to the hitherto available models: (i) it does not rely on the hypothesis of local electro-neutrality, and allows to treat the salt-free case; (ii) the chemical exchange governing the partition between free and bound ions is properly taken into account; (iii) a fully analytical solution is provided. The variation of the frequency-dependent dielectric permittivity with both thermodynamic and kinetic characteristics of the free-bound ion equilibrium is presented. In particular, the relative weights of both relaxation modes (exchange and transport), and their characteristic frequencies are discussed. This study opens the way to the analysis of systems for which the usual models are irrelevant, such as salt-free clay gels or membranes.

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PubMed2005

Brownian dynamics investigation of magnetization and birefringence relaxations in ferrofluids.

Brownian dynamics simulations are used to investigate the dynamics of orientational properties of real charge-stabilized ferrofluids, i.e. stable colloidal dispersions of magnetic nanoparticles. The relaxation times of the magnetization and of the birefringence, data accessible by experimental techniques, have been computed at several volume fractions. Besides, the effect of hydrodynamic interactions has been investigated. Equilibrium simulations without field are found to be inadequate to determine the aforementioned relaxation times for the systems under study, the dipolar interaction being too weak. Thus a nonequilibrium simulation procedure that mimics the experimental operating mode has been developed. After equilibrium simulations under a magnetic field, both birefringence and magnetization decays are recorded once the field is suppressed. Birefringence and magnetization decays are markedly impeded as the volume fraction increases, whereas they are barely enhanced when the intensity of the initial magnetic field is increased at a fixed volume fraction. Eventually, hydrodynamic interactions exhibit a slight but systematic lengthening of the relaxation times.

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PubMed2005

An analytical model for probing ion dynamics in clays with broadband dielectric spectroscopy.

A simple two-state model is proposed to explicitly derive the ionic contribution to the frequency-dependent dielectric permittivity of clay. This model is based on a separation of time scales and accounts for two possible solvation modes (inner/outer-sphere complexes) for ions in the interlayer spacing and a possible chemical exchange between both forms. The influence on the permittivity of thermodynamic (distribution constant K(d)) and dynamic (diffusion coefficient, chemical relaxation rate) parameters is discussed. In turn, this model is used to analyze experimental data obtained with Na-montmorillonite for two relative humidities. The values of the parameters extracted from these measurements, and their variation with water content, show that the proposed model is at least reasonable.

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PubMed2005

Analytical theories of transport in concentrated electrolyte solutions from the MSA.

Ion transport coefficients in electrolyte solutions (e.g., diffusion coefficients or electric conductivity) have been a subject of extensive studies for a long time. Whereas in the pioneering works of Debye, Hückel, and Onsager the ions were entirely characterized by their charge, recent theories allow specific effects of the ions (such as the ion size dependence or the pair association) to be obtained, both from simulation and from analytical theories. Such an approach, based on a combination of dynamic theories (Smoluchowski equation and mode-coupling theory) and of the mean spherical approximation (MSA) for the equilibrium pair correlation, is presented here. The various predicted equilibrium (osmotic pressure and activity coefficients) and transport coefficients (mutual diffusion, electric conductivity, self-diffusion, and transport numbers) are in good agreement with the experimental values up to high concentrations (1-2 mol L(-1)). Simple analytical expressions are obtained, and for practical use, the formula are given explicitly. We discuss the validity of such an approach which is nothing but a coarse-graining procedure.

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PubMed2005

Study of individual Na-montmorillonite particles size, morphology, and apparent charge.

Size, morphology, and apparent charge of individual Na-montmorillonite particles of natural MX-80 sodium montmorillonite were investigated in the present study by the use of three coupling methods. In the first part of this work, natural and synthetic montmorillonite clays were studied with atomic force microscopy (AFM) and photo-correlation spectroscopy (PCS). Both techniques exhibit the presence of two clay populations with a high dispersion of the length distribution. Microscopic analysis of the system revealed that clay particles could be reasonably approximated at low concentrations to ellipsoidal tactoids about 1.2 nm high. Average dimensions of the first population were typically 320-400 nm long/250 nm wide and 200-250 nm long/120 nm wide for natural and synthetic clays, respectively. The second population exhibits smaller sizes: 65 and 50 nm long and 35 and 25 nm wide for natural and synthetic clays, respectively. The statistics obtained for natural clay were then verified by PCS experiments on sodium montmorillonite suspensions. Both techniques reveal an important length dispersion. However, the relative proportions of the two kinds of particles could not be established properly because of both lack of statistics and limitations of the employed techniques. In the following part, conductivity measurements were performed on dilute montmorillonite clay suspensions. Raw data were then interpreted with the sizes and morphological information gained in the first part of the present work. The apparent charge of the clay sheets was found to be 8% of the structural charge.

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PubMed2004

Structural properties of charge-stabilized ferrofluids under a magnetic field: a Brownian dynamics study.

We present Brownian dynamics simulations of real charge-stabilized ferrofluids, which are stable colloidal dispersions of magnetic nanoparticles, with and without the presence of an external magnetic field. The colloidal suspensions are treated as collections of monodisperse spherical particles, bearing point dipoles at their centers and undergoing translational and rotational Brownian motions. The overall repulsive isotropic interactions between particles, governed by electrostatic repulsions, are taken into account by a one-component effective pair interaction potential. The potential parameters are fitted in order that computed structure factors are close to the experimental ones. Two samples of ferrofluid differing by the particle diameter and consequently by the intensity of the magnetic interaction are considered here. The magnetization and birefringence curves are computed: a deviation from the ideal Langevin behaviors is observed if the dipolar moment of particles is sufficiently large. Structure factors are also computed from simulations with and without an applied magnetic field H: the microstructure of the repulsive ferrofluid becomes anisotropic under H. Even our simple modeling of the suspension allows us to account for the main experimental features: an increase of the peak intensity is observed in the direction perpendicular to the field whereas the peak intensity decreases in the direction parallel to the field.

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PubMed2004

Relaxation of the electrical double layer after an electron transfer approached by Brownian dynamics simulation.

In this paper, the dynamical properties of the electrochemical double layer following an electron transfer are investigated by using Brownian dynamics simulations. This work is motivated by recent developments in ultrafast cyclic voltammetry which allow nanosecond time scales to be reached. A simple model of an electrochemical cell is developed by considering a 1:1 supporting electrolyte between two parallel walls carrying opposite surface charges, representing the electrodes; the solution also contains two neutral solutes representing the electroactive species. Equilibrium Brownian dynamics simulations of this system are performed. To mimic electron transfer processes at the electrode, the charge of the electroactive species are suddenly changed, and the subsequent relaxation of the surrounding ionic atmosphere are followed, using nonequilibrium Brownian dynamics. The electrostatic potential created in the center of the electroactive species by other ions is found to have an exponential decay which allows the evaluation of a characteristic relaxation time. The influence of the surface charge and of the electrolyte concentration on this time is discussed, for several conditions that mirror the ones of classical electrochemical experiments. The computed relaxation time of the double layer in aqueous solutions is found in the range 0.1 to 0.4 ns for electrolyte concentrations between 0.1 and 1 mol L(-1) and surface charges between 0.032 and 0.128 C m(-2).

Journal Article↗
PubMed2004

Transport coefficients of aqueous dodecyltrimethylammonium bromide solutions: comparison between experiments, analytical calculations and numerical simulations.

We study dynamical properties of ionic species in aqueous solutions of dodecyltrimethylammonium bromide, for several concentrations below and above the critical micellar concentration (cmc). New experimental determinations of the electrical conductivity are given which are compared to results obtained from an analytical transport theory; transport coefficients of ions in these solutions above the cmc are also computed from Brownian dynamics simulations. Analytical calculations as well as the simulation treat the solution within the framework of the continuous solvent model. Above the cmc, three ionic species are considered: the monomer surfactant, the micelle and the counterion. The analytical transport theory describes the structural properties of the electrolyte solution within the mean spherical approximation and assumes that the dominant forces which determine the deviations of transport processes from the ideal behavior (i.e., without any interactions between ions) are hydrodynamic interactions and electrostatic relaxation forces. In the simulations, both direct interactions and hydrodynamic interactions between solutes are taken into account. The interaction potential is modeled by pairwise repulsive 1/r(12) interactions and Coulomb interactions. The input parameters of the simulation (radii and self-diffusion coefficients of ions at infinite dilution) are partially obtained from the analytical transport theory which fits the experimental determinations of the electrical conductivity. Both the electrical conductivity of the solution and the self-diffusion coefficients of each species computed from Brownian dynamics are compared to available experimental data. In every case, the influence of hydrodynamic interactions (HIs) on the transport coefficients is investigated. It is shown that HIs are crucial to obtain agreement with experiments. In particular, the self-diffusion coefficient of the micelle, which is the largest and most charged species in the present system, is enhanced when HIs are included whereas the diffusion coefficients of the monomer and the counterion are roughly not influenced by HIs.

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PubMed2002

Ionic self-diffusion in concentrated aqueous electrolyte solutions.

A self-consistent microscopic theory is developed to understand the anomalously weak concentration dependence of ionic self-diffusion coefficient D(ion) in electrolyte solutions. The self-consistent equations are solved by using the mean spherical approximation expressions of the static pair correlation functions for unequal sizes. The results are in excellent agreement both with the known experimental results for many binary electrolytes and also with the new Brownian dynamics simulation results. The calculated velocity time correlation functions also show quantitative agreement with simulations. The theory also explains the reason for observing different D(ion) in recent NMR and neutron scattering experiments.

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PubMed1989

Counterion diffusion in heparin solutions.

The physiological importance of heparin is due to its strong interaction with bivalent counterions, especially Ca2+. A diffusional approach of this property is presented in this article: the observable is the self-diffusion coefficient of the counterions, as a function of the ratio of the polyelectrolyte over the added salt concentrations. All the results are in agreement with a simple "quasi-chemical model" in which two different states are assumed for the counterions: "free" or "bound." The proportions of these two types of ions are calculated according to the distribution function of the counterions around the polyion. We assume that those of counterions located at a distance closer than a, the characteristic distance, are bound; the others are free. The ionic distribution function is evaluated by a numerical integration of a cell model Poisson-Boltzmann equation. Finally, this model leads to a very good agreement with the experimental results, if the radius of heparin polyion is assumed to be 6 and 10 A.

Diffusion↗