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We study the addition of electrolytes to surfactant-free microemulsions in the domain where polydisperse pre-Ouzo aggregates are present. As in previous studies, the microemulsion is the ternary system water/ethanol/1-octanol, where ethanol acts as co-solvent. Addition of electrolytes modifies the static X-ray and neutron scattering, and dynamic light scattering patterns, as well as the position of the miscibility gap, where spontaneous emulsification occurs upon dilution with water. All observations can be rationalized considering that electrolytes are either “salting out” the ethanol, which is the main component of the interface stabilizing the aggregates, or producing charge separation via the antagonistic ion effect discovered by Onuki et al. Amphiphilic electrolytes, such as sodium dodecylsulfate or sodium dietheylhexylphosphate, induce a gradual transition towards monodisperse ionic micelles with their characteristic broad scattering “peak”. In these micelles the ethanol plays then the role of a cosurfactant. Dynamic light scattering can only be understood by combination of fluctuations of aggregate concentration due to the vicinity of a critical point and in-out fluctuations of ethanol. [ABSTRACT FROM AUTHOR]

Surfactants aggregate in water into micelles, and these micelles incorporate organic substances to solubilize them. Hydrotropes are compounds that increase the solubility of hydrophobic substances in water without this form of aggregation. Decreasing the chain length of the classical surfactant Aerosol OT (AOT) from C8 to C5 results in a molecule with intermediate properties. Molecular dynamics simulations and surface tension measurements are performed on this short chain derivative of AOT. This compound shows high solubility and at the same time progressive weak aggregation. The hydration of head groups hinders significant plunging into a hydrophobic core, which leads to well defined liquid chain nanodomains. The transition to bicontinuous aggregates is in the concentration range of 1 mol L -1 . The sulfonate group of the head groups (placed at the water interface of worm-like aggregates) rather than the aggregate-aggregate interaction is responsible for the unusual small angle X-ray scattering pattern.

We use the model system ethanol-dodecane to demonstrate that giant critical fluctuations induced by easily accessible weak centrifugal fields as low as 2000g can be observed above the miscibility gap of a binary liquid mixture. Moreover, several degrees above the phase transition, i.e. in the one-phase region, strong gradients of ethanol concentration occur upon centrifugation. In this case, the standard interpretation of sedimentation equilibrium in the analytical ultracentrifuge (AUC) yields an apparent molar mass of ethanol three orders of magnitude higher than the real value. Notably, these composition gradients have no influence on the distribution gradient of solutes such as dyes like Nile red. The thick opaque interphase formed upon centrifugation does not appear as the commonly observed sharp meniscus, but as a turbidity zone, similar to critical opalescence. This layer is a few millimeters thick and separates two fluids with low compositional gradients. All these effects can be qualitatively understood and explained using the Flory-Huggins solution model coupled to classical density functional theory (DFT). In this domain hetero-phase fluctuations can be triggered by gravity even far from the critical point. Taking into account Jean Perrin's approach to external fields in colloids, a self-consistent definition of the Flory effective volume and an explicit calculation of the total free energy per unit volume is possible.

A microfluidic technique is coupled with X-ray fluorescence in order to investigate the origin of the so-called synergy effect observed in liquid-liquid extraction of rare earth elements (REEs) when special combinations of two extractants - one solvating and one ionic - are used. The setup enables kinetic studies by varying the two phases' contact time. The results obtained are compared with those obtained using a standard batch extraction method at identical contact time. We then determine variations of free energies of transfer for five rare earth elements present in a solution together with a non-target ion (Fe3+) at different pH. Analysis of the effect of temperature and of surface charge density of the coexisting cations allows separating electrostatic effects from complexation effects. We finally show that all non-linear (synergic) effects are quadratic in mole fraction. This demonstrates that in-plane mixing entropy of the bent extractant film, in the first nanometer around rare earth ions, is the determining term in the synergy effect. Surprisingly, even when the third phase is present, free energies of transfer could still be measured in the dilute phase, which is reported for the first time, to our knowledge. We hence show that the extractive power of the dense third phase is stronger than that of conventional reverse aggregates in equilibrium with excess water.

The bending rigidity of small reverse aggregates involved in liquid-liquid extraction processes has been investigated by molecular dynamics simulations. Simulations of a common extractant (DMDOHEMA) with four hydrophobic chains in explicit solvent (n-heptane) and in vacuum have been performed to determine the effect of solvent penetration on film stiffness. Elastic film bending energy that is needed for mesoscopic modelling of transfer of species between complex fluids is harmonic in terms of curvature (Helfrich formalism) and the packing parameter only if the solvent is explicitly taken into account. In terms of the packing parameter of the real molecular film constituting the reverse water in oil aggregates and taking into account molecular volume, area and film thickness (that is in agreement with Tanford's model), the bending rigidity is calculated to be about 16 k B T per extractant molecule (about 40 kJ mol -1 ), which is smaller than the free energy of transfer from an isolated "monomer" molecule to a weak aggregate, but of the order of magnitude of the free energy of transfer used in liquid-liquid extraction processes.

Quantitative experiments on the evaporation from sessile droplets of aqueous saline (NaCl) solutions show a strong dependence on salt concentration and droplet shape. The experiments were performed with seven decades of initial NaCl concentrations, with various droplet sizes and with different contact angles. The evaporation rate is significantly lower for high salt concentrations and small contact angles than what is expected from the well-accepted diffusion-controlled evaporation scenario for sessile droplets, even if the change of the vapor pressure due to the salt is taken into account. Particle tracking velocimetry reveals that this modification of the evaporation behavior is caused by marangoni flows that are induced by surface tension gradients originating from the local evaporative peripheral salt enrichment. In addition it is found that already very low salt concentrations lead to a pinning of the three phase contact line. Whereas droplets with concentration ≥10(-6) M NaCl are pinned as soon as evaporation starts, droplets with lower salt concentration do evaporate in a constant contact angle mode. Aside from new, fundamental insights the findings are also relevant for a better understanding of the widespread phenomenon of corrosion initiated by sessile droplets.

We show in the case of N,N'-dimethyl-N,N'-dioctyl-2-(2(hexyloxy)ethyl)-malonamide (DMDOHEMA) chosen as a typical oil-soluble extractant with surface activity that the free energy of formation of reverse micelles in the solvent phase strongly depends on the presence of polar solutes. Free energies per molecule vary typically from 0 to 2 kT per molecule (5 kJ mol(-1)), depending on the kosmotropic/chaotropic nature of the anion extracted. Variations of the reverse aggregation free energy introduced by acids and other co-extracted solutes as deduced from the critical aggregation concentrations cannot be neglected while modelling extraction. With typical aggregation numbers of 4-6, the free energy of formation of one reverse aggregate varies up to 20 kJ mol(-1), which is four times the typical difference in free energy of one single cation transfer between a "target" and a non-target ion in practical extraction and stripping industrial processes.

The swelling behaviour of water-oil microemulsions - considering a surfactant layer between oil and water - has been studied using a two level-cuts Gaussian random field approach based on the Helfrich formalism. Microstructures and scattering properties of microemulsions have been calculated for different amounts of oil (and water) for flexible and rigid microemulsions. When the stiffness, the spontaneous curvature of the interfacial film, and the surface to volume ratio of the immiscible fluids are varied, the microemulsion topology and morphology change in order to minimize the microemulsion free energy. Our simulations point out a change in the microemulsion morphology as a function of the surfactant film rigidity and the composition of oil, water and the surfactant. Locally lamellar structures are found for rigid microemulsions, whereas for more flexible ones, the connected-droplet and/or bicontinuous structures are preferred. Furthermore, we show that the microemulsion swelling versus the volume fraction gives a specific signature of the microemulsion microstructure. This allows for discriminating between different types of microemulsions: flexible, frustrated and unfrustrated (close to bi-liquid foams), and connected structures as molten hexagonal and cubic phases. The universal swelling behaviour is compared to different analytic expressions of Disordered Open Connected (DOC) models for the microemulsion swelling versus the volume fraction.

An amphiphilic hexapeptide has been used as a model to quantify how specific ion effects induced by addition of four salts tune the hydrophilic/hydrophobic balance and induce temperature-dependant coacervate formation from aqueous solution. The hexapeptide chosen is present as a dimer with low transfer energy from water to octanol. Taking sodium chloride as the reference state in the Hofmeister scale, we identify water activity effects and therefore measure the free energy of transfer from water to octanol and separately the free energy associated to the adsorption of chaotropic ions or the desorption of kosmotropic ions for the same amphiphilic peptide. These effects have the same order of magnitude: therefore, both energies of solvation as well as transfer into octanol strongly depend on the nature of the electrolytes used to formulate any buffer. Model peptides could be used on separation processes based on criteria linked to "Hofmeister" but different from volume and valency.

Ion flotation processes involve the use of bubbles in order to separate ionic species from a mixed solution. Due to bubble interfaces we may assume null curvature at the molecular scale, where selective ion adsorption might be more easily investigated than with liquid-liquid extraction. In contrast to a classical flotation set-up, where bubbles are introduced via a glass frit, we use here a controlled sono-device generating cavitation bubbles which are initially absolutely clean. Moreover we have a faster process with a smaller device. The liquid phase resulting from the coalescence of the overflowing foam is enriched in some ions versus the initial brine. We show here that this effect follows the Hofmeister series and can be attributed to a weak adsorption of hydrated ions at the surfactant-water interface. The selectivity of alkali metals physisorbed at interfaces is analysed through the concentrations of competing ions remaining in solution by inductively coupled plasma optical emission spectrometry. Cationic selectivity, which is independent of the method for obtaining a foam, is discussed via the Gibbs free energy difference for bulk to hydrated surfactant monolayer. Relative values of effective adsorption energies are determined versus sodium ions taken as reference and correspond to 1-3% of the total hydration free energy.

The behaviour of a di-block molecule associating a diamide group and a non-ionic surfactant (C(i)E(j)) is determined in a ternary surfactant/water/oil/system. Its properties are compared to the ones of a parent non-ionic surfactant C(i)E(j) through the limits of boundaries in the phase prisms. The existence of a stable microemulsion single phase in a defined temperature and concentration range is demonstrated. The extension of the microemulsion domain is limited by the presence of a gel, containing lyotropic liquid crystals as gelling agents. Temperature dependence is observed for the curvature below the temperature of zero spontaneous curvature, but the ternary system cannot produce reverse microemulsion as observed with classical C(i)E(j). The decrease of the mean curvature with temperature is inhibited by the presence of the diamide as a grafted complexing group. Liquid-liquid extraction processes with this type of surfactant are possible, but will require the presence of at least a fourth component to enlarge the water in an oil microemulsion domain.

In the present paper, it is shown that in malonamide extractant/dodecane mixtures, change in the shape of the extractant aggregate may promote phase demixion. This phenomenon is known as the 3rd phase formation in extractant systems. The shape of the aggregates is dictated by the length of the alkyl chains stabilizing the reverse microemulsion by steric repulsion. Small angle scattering experiments are used to investigate the aggregation states of diamide extractant molecules, namely N,N'dimethyl-N,N'dibutyl-tetradecyl malonamide (DMDBTDMA) and N,N'dimethyl-N,N'dibutyl-pentyl malonamide (DMDBPMA), in dodecane. The results are described in a consistent way by the packing parameter concept and by expressing steric repulsion versus Van der Waals inter-aggregate interactions, both curvature dependants. Non-monotonous change in the extractant Critical Micellar Concentration (CMC) as a function of the extractant alkyl chain length is rationalized by comparing Van der Waals attraction between the alkyl chains of both the extractant and the solvent.

We have investigated the activity of counter-ions at 60 degrees C through the osmotic coefficient K in solutions of anionic and cationic polyelectrolyte complexes of variable compositions. For excess of polyanion in the complexes (molar fraction of polycation f < 0.5), K increases as the polyanion is neutralized by the polycation (f getting closer to 0.5). By contrast, for an excess of polycation (f > 0.5), K stays constant or even slightly decreases as the polycation is getting neutralized by the polyanion. This asymmetric behavior depending on the charge of the complexes indicates that the globally negatively charged complexes are homogeneous and can be treated as a single polyelectrolyte of reduced linear charge density. On the other hand, the positively charged complexes show a micro-phase separation between neutral fully compensated microdomains and domains where the excess polycation is locally segregated. These two different microstructures are reminiscent of the coacervation and segregation regimes observed at higher concentrations and salinities, and also of polyelectrolyte complexes with oppositely charged surfactants. This interpretation is supported by two simple predictive models.