Acoustic and electroacoustic spectroscopy of water-in-diluted-bitumen emulsions.

Water-in-oil emulsions of Athabasca bitumen diluted with toluene have been studied using the latest advances in acoustic and electroacoustic spectroscopy. From the sound attenuation spectra of emulsions, the water droplet size distribution is measured. The electrical surface charge density of the water droplets is obtained from the colloid vibration current. In the case of freshly prepared water-in-oil emulsions, the droplet size increased while the surface charge density decreased with time. The time-dependent relaxation of the surface charge ranges from several hours to 3 days, and it is probably due to the slow adsorption/desorption kinetics of bituminous components at the water-oil interface. This study illuminates the contribution of the electrostatic interactions to the stability of water-in-oil emulsions.

Adsorption of bituminous components at oil/water interfaces investigated by quartz crystal microbalance: implications to the stability of water-in-oil emulsions.

Silica-gel-coated QCM crystals oscillating in a thickness shear mode are used to measure adsorption of bituminous components in water-saturated heptol (1/1 vol ratio of a heptane/toluene mixture) at the oil/water interface. In addition to the viscoelasticity of the adsorbed film, the effects of the bulk liquid density and viscosity as well as the liquid trapped in interfacial cavities are taken into account for the calculation of adsorbed mass. Asphaltenes in heptol adsorb continuously at the oil/water interface, while resins (the surface-active species in maltenes) show adsorption saturation in the same solvent. For Athabasca bitumen in heptol, two adsorption regimes are observed depending on concentration. At low concentrations, a slow, non-steady-state, and irreversible adsorption takes place. At high concentrations, a steady-state adsorption with limited reversibility results in a quick adsorption saturation. The threshold concentration between these adsorption regimes is 1.5 wt % and 8 wt % for oil/water and oil/gold interfaces, respectively. The threshold concentration, the total adsorbed amount, and the flux of non-steady-state adsorption depend on the resin-to-asphaltene ratio. The threshold concentration is related to the earlier reported critical bitumen concentration characterizing the rigid-to-flexible transition of the interfacial film. We propose a new mechanism based on the change of the effective resin-to-asphaltene ratio with dilution to explain both the adsorption behavior and emulsion stability.

Adsorption isotherms of associating asphaltenes at oil/water interfaces based on the dependence of interfacial tension on solvent activity.

In the Gibbs adsorption equation, the application of solvent activity for the calculation of the surface/interfacial excess is proposed for nonideal or associating or pseudocomponents such as asphaltenes. For the aforementioned systems, only the mass-based phenomenological interfacial excess can be determined based on interfacial tension versus activity data. The use of the mole fraction is compared to the use of the activity when the adsorbed amount of associating asphaltenes is calculated at a water/toluene interface. Langmuir-type isotherms describe the adsorption of asphaltenes at toluene/water interfaces. Asphaltenes were treated to remove the resins and natural surfactants using cyclic precipitation and dissolution of asphaltenes at a fixed aliphatic/aromatic ratio. Different fractions of asphaltenes were obtained by changing the aliphatic/aromatic ratio of the precipitating solvent. The limiting molar masses of asphaltenes measured by vapor pressure osmometry are different for fractions precipitated at different heptane to toluene ratios. The mass-based adsorbed amounts at the water/toluene interface, at a 0.1 asphaltene-to-toluene mass-ratio, varied in the range of 0.8-2.8 mg/m(2), depending on the molar mass of asphaltenes.

Emulsion stability based on phase behavior in sodium naphthenates containing systems: gels with a high organic solvent content.

Addition of heptane to a sodium naphthenates/toluene/water system at 25 degrees C reduces the lamellar liquid-crystal phase range and increases the microemulsion phase range. Both of these effects result in the extension of the composition range where emulsions have low stability. This effect is even stronger at 40 degrees C. Heptane addition also results in the formation of very stable emulsions within the overlapping phase-existence ranges of aqueous (L1) and organic (L2) phases. Stable non-birefringent gel observed in equilibrium with L1 and L2 phases contains only a small percentage of water and sodium naphthenates. The swelling behavior of an unstable gel, an emulsion previously compressed by centrifugation, appears to be due to a stepwise thickening of the thin liquid films between the droplets.

Sandwich structures at oil-water interfaces under alkaline conditions.

Equilibrium liquid crystal (LC) layer on an interface between crude oils and water was observed at high pH. This layer is composed mainly of sodium naphthenates produced in situ at the water/oil interface. Transient LC layer was also evolved at the interface of aqueous phase of sodium hydroxide solutions and oleic phase of naphthenic acid (NA) solutions as result of a chemical reaction between NaOH and NA. This chemical reaction causes transport process resulting in a disturbance of the interface. Optical observation of this interface disturbance reviled that the interface covered with LC shows considerably lower flexibility as compared to LC free interface. The LC layer eventually dissolves in the water phase at low oil-to-water ratio, while at high oil-to-water ratio it can form an equilibrium phase, which spreads spontaneously at the oil-water interface.

Liquid Crystals in Aqueous Solutions of Sodium Naphthenates.

The phase diagram of the sodium naphthenates (SN)/water system was determined between -5 and 95 degrees C. Oil, isotropic water solution, and birefringent gel phases were observed. The appearance of the oil phase was caused by the hydrolysis of SN. After the system was allowed to stand for 3 weeks, a lamellar liquid crystal (LLC) phase separated from the rest of the system at 25 degrees C. This phase was always observed together with other phases. This phase behavior is attributed to different partition coefficient values of the individual constituents of sodium naphthenates between the phases. The partition coefficient difference also caused the appearance of a clear LLC and a turbid gel phase. Under the influence of agitation, the LLC phase with isotropic water solution transformed to giant vesicles; however the equilibrium state of the LLC is of parallel stacked layer structure. Macroscopic dislocations of the liquid crystal were observed, and they were anchored to the interface of the isotropic solution and the liquid crystal phases. These dislocations are similar to screw-type dislocations. The solubilization curve of toluene by SN is analogous to that of hydrophobic materials by a hydrotrope. Copyright 2001 Academic Press.

The Hydrotrope Action of Sodium Xylenesulfonate on the Solubility of Lecithin.

The activity of sodium xylenesulfonate in aqueous solution was determined by vapor pressure measurements, the results of which were transformed to mean activities. In addition, surface tension, conductivity, and partial molar volume were determined to obtain complementary information about potential association structures. No sudden change was observed, indicating the association to take place in the concentration range where the increased solubility of lecithin was observed, contrary to the case of surfactant micellization. The solubilization of lecithin in the aqueous solutions of sodium xylenesulfonate showed the association to be cooperative between the two amphiphiles. A model is proposed for the interpretation of the catastrophic incorporation threshold concentration observed in the solubility curve of lecithin. Copyright 2001 Academic Press.