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Publications (118)
Onsager made corrections to the Poisson-Boltzmann equation, to more correctly describe interactions in asymmetric electrolytes (those which have different charges, in absolute value, for the cation and the anion). The equations established by Onsager allow the calculation of symmetric total correlation functions, such that hij(r)=hji(r). In this ar...
Various approaches are reviewed that use scaled particle theories to describe dumbbell fluids made of tangent or overlapped hard spheres. Expressions encountered in the literature are written in a form similar to that presented in the thermodynamic perturbation theory introduced by Wertheim for chains and developed in statistical associating fluid...
In this work the conductivity data of three carboxylate surfactant systems: sodium (NaDec), potassium (KDec) and cesium (CsDec) decanoates aqueous solution in the concentration range 10⁻³ − 0.25 mol dm–3, between temperatures 278.15 and 328.15 K, are analyzed by a transport theory in the frame of the mean spherical approximation (MSA). The data in...
Electrolyte theories enable to describe the structural and dynamical properties of simple electrolytes in solution, such as sodium chloride in water. Using these theories for aqueous solutions of charged nanoparticles is a straightforward route to extract their charge and size from experimental data. Nevertheless, for such strongly asymmetric elect...
Electrolyte theories enable to describe the structural and dynamical properties of simple electrolytes in solution, such as sodium chloride in water. Using these theories for aqueous solutions of charged nanoparticles is a straightforward route to extract their charge and size from experimental data. Nevertheless, for such strongly asymmetric elect...
The purpose of this study is to predict the electrical conductivity of some weak electrolytes used in buffer solutions. The acid-base reactions occurring between the different species in solution are evaluated taking into account the activity coefficients. The deviations from ideality necessary to describe the equilibrium and transport properties a...
Understanding the force between charged surfaces immersed in an electrolyte solution is a classic problem in soft matter and liquid-state theory. Recent experiments showed that the force decays exponentially but the characteristic decay length in a concentrated electrolyte is significantly larger than what liquid-state theories predict based on ana...
By considering the solution of the Mean Spherical Approximation (MSA) given by Lesser Blum, we addressed the problem of specificity in aqueous electrolyte solutions. The reference diameter of the cations is defined as the biggest possible diameter of the cation (obtained with the less associating anion). Then the specificity is taken into account b...
We present a model for polyelectrolyte solutions within the binding mean spherical approximation. An approach developed previously, to describe polyelectrolytic chain solutions and on the other hand to describe the association of counterions on spherical polyions is generalized, considering both the polyelectrolytic chain formation and the associat...
An attempt is made to understand the underscreening effect, observed in concentrated electrolyte solutions or melts, on the basis of simple, admittedly crude models involving charged (for the ions) and neutral (for the solvent molecules) hard spheres. The thermodynamic and structural properties of these "primitive" and "semi-primitive" models are c...
Models for mixed-solvent strong electrolytes, using an equation of state (EoS) are reviewed in this work. Through the example of ePPC-SAFT (that includes a Born term and ionic association), the meaning and the effect of each contribution to the solvation energy and the mean ionic activity coefficient are investigated. The importance of the dielectr...
Deviations from ideality in organic electrolyte solutions are described within the Binding Mean Spherical Approximation (BiMSA) theory, in which ions are regarded as charged hard spheres and unlike ions may associate to form an ion pair. Association is modeled within the Wertheim theory (as done in SAFT-type models). The model includes a mass actio...
We study the upscaling or homogenization of the transport of a multicomponentelectrolyte in a dilute Newtonian solvent through a deformable porous medium.The pore scale interaction between the flow and the structure deformation is taken into account.After a careful adimensionalization process, we first consider so-called equilibrium solutions,in th...
Accurate analytic thermodynamic modeling of water and its mixtures with hydrocarbon and oxygenates is difficult even with new and advanced equations of state such as the perturbed-chain statistical associating fluid theory (PC-SAFT). Several attempts have been made in the past by various authors to solve this issue. However, current models generall...
A simple model for charged ring polyelectrolyte is proposed, to describe their thermodynamic properties. Starting from an analytical expressions previously obtained for charged chains within the binding mean spherical approximation, we present a method to determine suitable modifications in order to describe charged rings. It is shown that the elec...
In electrolyte
solutions, an electric potential difference, called the Ionic Vibration Potential (IVP), related to the ionic vibration intensity, is generated by the application of an acoustic wave. Several theories based on a mechanical framework have been proposed over the years to predict the IVP for high ionic strengths, in the case where inter...
In the framework of irreversible thermodynamics, we show that the sedimentation
current in electrolyte
solutions is mathematically equivalent to the low frequency limit of the ionic vibration current, appearing in the presence of an acoustic wave. This non-trivial result is obtained thanks to a careful choice of the reference frame used to express...
Clay minerals have remarkable adsorption properties because of their high specific surface area and surface charge density, which give rise to high electrochemical properties. These electrochemical properties cannot be directly measured, and models must be developed to estimate the electrostatic potential at the vicinity of clay mineral surfaces. I...
The Binding Mean Spherical Approximation (BiMSA) is used to describe osmotic coefficients of aqueous solutions of salts containing imidazolium cations and bulky anions over the whole concentration range at temperature in the range (25 to 60) °C. A total of 13 salts have been considered altogether. The ion diameters, the permittivity of solution and...
The electric signal induced by an ultrasonic wave in aqueous solutions of charged species is measured and analyzed. A device is developed which measures the raw induced electric signal for small sample volumes (few milliliters) and without any preceding calibration. The potential difference generated between two identical electrodes, called the ion...
Special issue in Honour of Pierre TURQ
Molecular simulations have allowed us to probe the atomic details of aqueous solutions of tetramethylammonium (TMA) and tetrabutylammonium (TBA) bromide, across a wide range of concentrations (0.5 to 3-4 molal). We highlight the space-filling (TMA(+)) versus penetrable (TBA(+)) nature of these polyatomic cations and its consequence for ion hydratio...
We investigate numerically a density functional theory (DFT) for strongly confined ionic solutions in the canonical ensemble by comparing predictions of ionic concentration profiles and pressure for the double-layer configuration to those obtained with Monte Carlo (MC) simulations and the simpler Poisson-Boltzmann (PB) approach. The DFT consists of...
Pierre Turq has made decisive contributions to the theory and to the multiscale simulation of charged systems, such as molten salts, electrolyte solutions and colloidal suspensions, in the bulk, at interfaces and under confinement. His research line focussed on dynamical properties and was characterised by constant efforts to connect his theoretica...
We use a semi-grand canonical version of mean-field density functional theory to determine the total effective interaction energy of a solution of penetrable polyions characterised by a Gaussian charge distribution, in the presence of added salt. We then apply this effective representation of semi-flexible polyelectrolyte chains to investigate the...
We study mutual diffusion of associated electrolyte in water. A theory based on the Smoluchowski equation and on the mean spherical approximation is proposed. It is found to be valid up to molar concentrations. The values of the association constant obtained for ZnSO4 and MgSO4 aqueous solutions are consistent with further methods of measurements....
We used several complementary experimental and theoretical tools to characterise the charge properties of well-defined maghemite nanoparticles in solution as a function of the volume fraction. The radius of the nanoparticles is equal to 6 nm. The structural charge was measured from chemical titration and was found high enough to expect some counter...
Ionic solutions exhibiting multiple association are described within the binding mean spherical approximation (BiMSA). This model is based on the Wertheim formalism, in the framework of the primitive model at the McMillan-Mayer level. The cation and the anion form the various complexes according to stepwise complexation-equilibria. Analytic express...
A model was developed[1] to describe the thermodynamic properties (osmotic and activity coefficients) and degree of association of electrolytes. It is assumed that the cation and the anion can form two different kinds of pairs: a solvent separated ion pair and a chemical pair (undissociated molecule). The model is an extension of the binding or ass...
The effect of ionic strength and of the condensation of divalent ions on the mobility of humic substances have been addressed thanks to conductimetry experiments. The analysis of the experimental data were performed by the use of a Mean Spherical Approximation transport theory, which includes both hydrodynamic and electrostatic interaction effects...
We study phase separation in ionic solutions confined by solid objects carrying surface charges. Within the framework of Density Functional Theory, the Helmholtz free energy of the ionic solution is minimized under canonical constraints on the ionic densities fixing their mean value while ensuring global electroneutrality. The free energy splits in...
This work is aimed at a description of the thermodynamic properties of highly concentrated aqueous solutions of nitric acid salts at 25°C. The predictive capability of the binding mean spherical approximation (BIMSA) was examined. First, Raman spectroscopy was used to study the proportion of associated nitric acid as a function of concentration. Th...
In this study, speciation in aqueous solutions of nitric acid at 25 °C was assessed in two independent ways. First, Raman experiments were carried out and interpreted in terms of free nitrate ions, ion pairs and neutral HNO(3) molecules. In parallel, a model was developed to account for the formation of these two kinds of pairs. It was based on an...
The study of electrolyte solutions by neutron scattering is an example of the large range of possibilities of the technique. Structure and dynamics at different time and length scales, discrimination of global from local motions, separation of coherent from incoherent contributions are necessary to embrace the complexity of a subject where charge a...
The binding mean spherical approximation (BiMSA) is used to describe osmotic coefficients for aqueous solutions of salts containing alkylammonium cations or bulky anions. A total of 35 salt solutions is accurately described at 25 °C over the whole concentration range, up to very high concentrations such as 20 mol·kg–1 for methylammonium chloride or...
The development of simple, primitive model descriptions for electrolyte solutions is usually carried out by fitting the system parameters to reproduce some experimental data. We propose an alternative method, that allows one to derive implicit solvent models of electrolyte solutions from all-atom descriptions. We obtain analytic expressions for the...
A model of the extraction of uranyl nitrate, nitric acid and water from aqueous solution to the organic phase with tributyl phosphate (TBP) was developed. It is based on the model developed by Naganawa and Tachimori (H. Naganawa, S. Tachimori, Bull. Chem. Soc. Jap. 70, 809, (1997)), which successfully describes extraction of nitric acid and water w...
Experiments were carried out on the partitioning of uranyl nitrate in nitric acid solution extracted by 30 vol.% of tributyl phosphate (TBP) in dodecane at 25 °C. The model proposed by Naganawa and Tachimori (Bull. Chem. Soc. Jap. 70, 809, (1997)) for the case of aqueous solutions of nitric acid was used to additionally describe the extraction equi...
The size and the charge of humic substances are key parameters to access their transport properties and their potential ability of complexation in the soil. The purpose of this paper is to show that high precision conductimetry coupled to a suitable transport theory give access, at various pH, to the size and charge of reference humic and fulvic ac...
The mean activity (γ±) and osmotic (Φ) coefficients for binary and ternary aqueous solutions of trivalent electrolytes (mainly made up of lanthanide salts) are described in the framework of the primitive model of ionic solutions, using the binding mean spherical approximation (BiMSA). This model, based on the Wertheim formalism, accounts for (chemi...
We present a method to derive implicit solvent models of electrolyte solutions from all-atom descriptions; providing analytical expressions of the thermodynamic and structural properties of the ions consistent with the underlying explicit solvent representation. Effective potentials between ions in solution are calculated to perform perturbation th...
Fluorescence confocal laser scanning microscopy (CLSM) has been applied to quantify pH distribution in a coaxial flow microreactor. The methodology consists of utilizing a micromolar concentration of the common dye fluorescein, whose fluorescence in solution strongly increases above pH 6.2, in order to map the pH changes in the central jet stream w...
The purpose of this study is to predict the electrical conductivity of an electrolyte solution containing several simple ionic species. Explicit equations of the MSA-transport theory for the electrical conductivity in this complex solution are given. The theoretical conductivity of simple salts is first compared to experimental results of the liter...
Electrical conductivity has been used at different temperatures to study three micellar systems: tetradecyltrimethylammonium chloride (TTACl), dodecyltrimethylammonium chloride (DTACl), and decyltrimethylammonium chloride (DeTACl). A phenomenon of premicellization is observed for DeTACl and DTACl below the critical micellar concentration (CMC). Ass...
Résumé — Description des propriétés thermodynamiques de solutions aqueuses ioniques dans l'approximation sphérique moyenne — Les propriétés thermodynamiques de solutions aqueuses ioniques sont décrites dans l'approximation sphérique moyenne (MSA). Le modèle MSA original et celui avec association (BiMSA) ont été complétés de façon à inclure les effe...
The capability of the MSA–NRTL model to describe heat effects for binary aqueous electrolyte and nonelectrolyte solutions, with a relatively reduced number of parameters, is examined. The thermodynamic properties described include the osmotic coefficient, ϕ, the apparent relative molar enthalpy, ΦL, and the apparent molar heat capacity, ΦCP. The MS...
Acoustophoresis consists of applying an ultrasonic wave to a charged solution and measuring the induced electric field, originating from the local separation of charges. This effect, predicted by Debye in 1933, has been studied for electrolytes (Ionic Vibration Potential, IVP) and for colloids (Colloidal Vibration Potential, CVP).
In the first part...
We focus here on the effective charge of ionic micelles in aqueous solutions. First, we show that this quantity may be obtained by using an analytical transport theory based on the continuous solvent model to fit the experimental electrical conductivity of micellar solutions. In particular, we demonstrate the robustness of the fitting procedure on...
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 w...
Actinide elements and their chemistry have a significant number of applications. Bringing together contributions from the leading experts in the field, Recent Advances in Actinide Science covers six main topics: * Analysis, the environment and biotransformations * Coordination and organometallic chemistry * Heavy elements * Nuclear fuels, materials...
The stepwise solvation-equilibrium model of Stokes and Robinson is used for a description of departures from ideality in ionic solutions. It is shown how to construct a thermodynamically consistent model including solvation effects. Simple expressions are derived for the mean ion solvation number. The model is applied to strong electrolyte solution...
This work is aimed at a description of the thermodynamic properties of highly concentrated aqueous solutions of uranyl nitrate at 25 degrees C. A new resolution of the binding mean spherical approximation (BIMSA) theory, taking into account 1-1 and also 1-2 complex formation, is developed and used to reproduce, from a simple procedure, experimental...
The Fuoss-Onsager continuity equations are solved with a Green's function technique in order to get the laws of variation of transport coefficients with concentration. Any kind of equilibrium pair correlation function can be used for this purpose, those of the MSA (mean spherical approximation) leading to explicit expressions for the variation of t...
conférence invitée présentée par P. Turq
conférence orale de Serge Durand-Vidal
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...
Originally based on semiphenomenological equations, the transport properties of ions in electrolyte solutions can now be understood in terms of the Brownian motion. Thanks to the Smoluchowski equation or the mode-coupling theory (MCT) applied with the help of the mean spherical approximation (MSA), it is possible to describe the various transport q...
Osmotic coefficients of aqueous solutions of lanthanide salts are described using the binding mean spherical approximation (BIMSA) model based on the Wertheim formalism for association. The lanthanide(III) cation and the co-ion are allowed to form a 1-1 ion pair. Hydration is taken into account by introducing concentration-dependent cation size and...
A new combination of the non-random two liquid (NRTL) model with the mean spherical approximation (MSA) is introduced in the context of current research on the description of electrolyte properties. Existing problems in electrolyte theory and possible strategies for future research are also discussed.
A previous model, developed to describe the thermodynamic properties of associating electrolytes within the binding mean spherical approximation (BIMSA), is modified on the basis of a better representation of the pair. The ions are represented as charged hard spheres interacting through a sticky point potential, leading to the creation of pairs. In...
Osmotic coefficients of a series of 16 aqueous electrolyte solutions are described at concentrations up to about 1 M with the help of HNC calculations and solvent-averaged potentials of charged hard spheres with an additional necessary dispersion potential, omitted from all earlier treatments. The adjusted ionic radii and excess polarizabilities ha...
The mean spherical approximation is used to describe the vapor pressure over aqueous solutions containing an electrolyte and carbon dioxide. Three electrolytes have been studied: NaOH, NaCl, and acetic acid. A good representation is obtained with a reduced number of parameters as compared to previous models. These parameters account for the concen...
The derivation criticized by Felderhof in the preceding Comment is clarified. The result is not changed. The connection with Brownian dynamics simulation is also examined.
The effect of an added electrolyte on the kinetics of fluorescence quenching of the uranyl ion by chloride anion is investigated. Various electrolytes have been used up to a maximum concentration of 9 mol dm−3. The description of the experimental results is examined using theoretical results of previous work and a new expression derived in this pap...
The mean spherical approximation (MSA) approach for electrolyte solutions is combined with a modified non-random two-liquid (NRTL) approach. The resulting model is suitable for a description of the thermodynamic properties of electrolyte-multisolvent systems. The ability of this MSA-NRTL model is investigated by examining activity and osmotic coeff...
An expression for the mutual diffusion coefficient of electrolyte solutions on the Smoluchowski level is proposed and is used in Brownian dynamics simulations. In particular, the divergence of this diffusion coefficient due to the long range of hydrodynamic interactions is solved by introducing explicitly the solvent-fixed frame of reference. The r...
Ion association is incorporated into the restricted-primitive model electrolyte to account for the strong attraction between unlike ions. Two methods are investigated within the McMillan-Mayer framework: first is the binding mean-spherical approximation (BIMSA) based on the Wertheim Ornstein-Zernike integral equation formalism; and the second is th...
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...
The mutual diffusion coefficients of electrolytes are calculated in the primitive model with the Mean Spherical Approximation (MSA). The influence of association is taken into account for 2-2 electrolytes in aqueous solutions, with a chemical model. The mutual diffusion coefficients of the salts are represented in terms of their individual ionic di...
Transport coefficients of dissociated electrolytes in aqueous solution are studied in the framework of the primitive model of ionic solutions in which the solvent is a dielectric continuum. Simple explicit expressions are obtained by using a combination of Smoluchowski equation for the dynamics and the mean spherical approximation (MSA) for the equ...
