Solubility behaviour, crystallisation kinetics and pour point : a comparison of linear alkane and triacyl glyceride solute/solvent mixtures

Mixtures of either a hydrocarbon wax in a hydrocarbon solvent or a long chain triacyl glyceride (TAG) in a TAG solvent show complex solubility boundary temperature hysteresis and precipitated crystal network formation leading to gelation. For these industrially-important systems, we show how the equilibrium solubility and its hysteresis, crystallisation kinetics and pour point temperature vary with solute concentration for representative examples of both hydrocarbon (n-tetracosane (C24) solute in n-heptane (C7) solvent) and TAG (tristearin (SSS) solute in tricaprylin (CCC) solvent) mixtures. The behaviour is modelled with good accuracy; thereby providing a useful aid to formulation and process optimisation

A model study of enhanced oil recovery by flooding with aqueous surfactant solution and comparison with theory

With the aim of elucidating the details of enhanced oil recovery by surfactant solution flooding, we have determined the detailed behavior of model systems consisting of a packed column of calcium carbonate particles as the porous rock, n-decane as the trapped oil, and aqueous solutions of the anionic surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT). The AOT concentration was varied from zero to above the critical aggregation concentration (cac). The salt content of the aqueous solutions was varied to give systems of widely different, post-cac oil–water interfacial tensions. The systems were characterized in detail by measuring the permeability behavior of the packed columns, the adsorption isotherms of AOT from the water to the oil–water interface and to the water–calcium carbonate interface, and oil–water–calcium carbonate contact angles. Measurements of the percent oil recovery by pumping surfactant solutions into calcium carbonate-packed columns initially filled with oil were analyzed in terms of the characterization results. We show that the measured contact angles as a function of AOT concentration are in reasonable agreement with those calculated from values of the surface energy of the calcium carbonate–air surface plus the measured adsorption isotherms. Surfactant adsorption onto the calcium carbonate–water interface causes depletion of its aqueous-phase concentration, and we derive equations which enable the concentration of nonadsorbed surfactant within the packed column to be estimated from measured parameters. The percent oil recovery as a function of the surfactant concentration is determined solely by the oil–water–calcium carbonate contact angle for nonadsorbed surfactant concentrations less than the cac. For surfactant concentrations greater than the cac, additional oil removal occurs by a combination of solubilization and emulsification plus oil mobilization due to the low oil–water interfacial tension and a pumping pressure increase

Model Study of Enhanced Oil Recovery by Flooding with Aqueous Solutions of Different Surfactants: How the Surface Chemical Properties of the Surfactants Relate to the Amount of Oil Recovered

© 2016 American Chemical Society. The main aim of this work is to establish how the fraction of oil recovered from an oil-filled calcite powder packed column by injection of aqueous surfactant solution depends on the phase behavior and surface chemical properties of the surfactant system. We have measured the phase behavior, the adsorption of surfactant to the oil-water, calcite-water, and calcite-oil interfaces, tensions, and contact angles for anionic, cationic, and nonionic surfactant/oil/aqueous phase systems. We show how the measured surface chemical properties can be used to approximately predict the fraction of oil recovered as a function of the volume and concentration of the surfactant solutions injected into the column. Measured and calculated plots of %oil recovery versus surfactant concentration show reasonably good agreement for the different surfactant systems. The experimentally validated model for oil recovery provides a sound basis for the rational selection of surfactant type and concentration to achieve maximum oil recovery based on laboratory measurements of the surface chemical properties of candidate surfactants

Adsorption of benzyldimethyldodecylammonium chloride onto stainless steel using the quartz crystal microbalance and the depletion methods: An optimisation study

The adsorption behaviour of benzyldimethyldodecylammonium chloride (C12BDMAC) corrosion inhibitor from aqueous solutions onto a stainless steel surface has been investigated using the quartz crystal microbalance (QCM) technique and the depletion-HPLC method. Three different experimental procedures were used to carry out the adsorption measurements using the QCM. The results revealed that the employed experimental procedure had a marked influence on both of the measured frequency and dissipation energy changes. Additionally, the measured changes in the normalized frequency and dissipation changes were found to be overtone-dependent. The adsorbed amounts determined by QCM were higher than those determined by depletion due to strong contributions from the bulk liquid properties. The direct application of the measured frequency shifts corresponding to the lowest dissipation changes, ?flowestD, in the Sauerbrey equation was effective in minimising these contributions within an acceptable experimental tolerance. A correction procedure, based on the Kanazawa equation, has been proposed and applied successfully to separate the contribution from the bulk effects to the calculated adsorbed mass. The adsorption isotherms obtained from the corrected frequency shifts and the depletion method were perfectly matched over the whole range of concentrations investigated

Dopamine modulates the neural representation of subjective value of food in hungry subjects.

Although there is a rich literature on the role of dopamine in value learning, much less is known about its role in using established value estimations to shape decision-making. Here we investigated the effect of dopaminergic modulation on value-based decision-making for food items in fasted healthy human participants. The Becker-deGroot-Marschak auction, which assesses subjective value, was examined in conjunction with pharmacological fMRI using a dopaminergic agonist and an antagonist. We found that dopamine enhanced the neural response to value in the inferior parietal gyrus/intraparietal sulcus, and that this effect predominated toward the end of the valuation process when an action was needed to record the value. Our results suggest that dopamine is involved in acting upon the decision, providing additional insight to the mechanisms underlying impaired decision-making in healthy individuals and clinical populations with reduced dopamine levels.This is the author's accepted manuscript. The final version is available from the Society for Neuroscience in the Journal of Neuroscience at http://www.jneurosci.org/content/34/50/16856.abstract

How polymer additives reduce the pour point of hydrocarbon solvents containing wax crystals

We have investigated how four different pour point depressant (PPD) polymers affect the pour point transition in mixtures of a single pure wax in a solvent. We used either n-eicosane (C20), CH3(CH2)18CH3, n-tetracosane (C24), CH3(CH2)22CH3 or n-hexatriacontane (C36), CH3(CH2)34CH3 as the wax component with either n-heptane or toluene as the solvent component. For all wax–solvent combinations, the measured variation of wax solubility with temperature is well predicted by ideal solution theory. The variation of pour point temperature as a function of the overall wax concentration is quantitatively modelled using the idea that, for each overall wax concentration, the pour point occurs at a temperature at which a critical volume fraction ϕ* of wax crystals has precipitated. Close to the pour point temperature, extraction and examination of the wax crystals show they consist of polydisperse, irregularly-shaped platelets with axial ratios (h/d, where h is the plate thickness and d is the plate long dimension) in the range 0.005–0.05. It is found that the measured ϕ* values corresponding to the pour point transitions are weakly correlated with the wax crystal axial ratios (h/d) for all wax–solvent–PPD polymer combinations. These results indicate that the pour point transition occurs at a volume fraction larger than the value at which the volumes of rotation of the platelet crystals overlap, i.e., 2.5(h/d) < ϕ* < 11(h/d). PPD polymers work, in part, by increasing the wax crystal axial ratio (h/d), thereby increasing ϕ* and reducing the pour point temperature. Since the PPD's ability to modify the wax crystal shape relies on its adsorption to the crystal-solution surface, it is anticipated and observed experimentally that optimum PPD efficacy is correlated with the difference between the wax and the polymer solubility boundary temperatures. This finding and the mechanistic insight gained here provide the basis for a simple and rapid screening test to identify candidate species likely to be effective PPDs for particular wax systems

The removal of thermally aged films of triacylglycerides by surfactant solutions

Thermal ageing of triacylglycerides (TAG) at high temperatures produces films which resist removal using aqueous surfactant solutions. We used a mass loss method to investigate the removal of thermally aged TAG films from hard surfaces using aqueous solutions of surfactants of different charge types. It was found that cationic surfactants are most effective at high pH, whereas anionics are most effective at low pH and a non-ionic surfactant is most effective at intermediate pH. We showed that the TAG film removal process occurs in several stages. In the first ‘‘lag phase’’ no TAG removal occurs; the surfactant first partitions into the thermally aged film. In the second stage, the TAG film containing surfactant was removed by solubilisation into micelles in the aqueous solution. The effects of pH and surfactant charge on the TAG removal process correlate with the effects of these variables on the extent of surfactant partitioning to the TAG film and on the maximum extent of TAG solubilisation within the micelles. Additionally, we showed how the TAG removal is enhanced by the addition of amphiphilic additives such as alcohols which act as co-surfactants. The study demonstrates that aqueous surfactant solutions provide a viable and more benign alternative to current methods for the removal of thermally aged TAG films

Jupiter's Temperature Structure: A Reassessment of the Voyager Radio Occultation Measurements

The thermal structure of planetary atmospheres is an essential input for predicting and retrieving the distribution of gases and aerosols, as well as the bulk chemical abundances. In the case of Jupiter, the temperature at a reference level—generally taken at 1 bar—serves as the anchor in models used to derive the planet's interior structure and composition. Most models assume the temperature measured by the Galileo probe. However, those data correspond to a single location, an unusually clear, dry region, affected by local atmospheric dynamics. On the other hand, the Voyager radio occultation observations cover a wider range of latitudes, longitudes, and times. The Voyager retrievals were based on atmospheric composition and radio refractivity data that require updating and were never properly tabulated; the few existing tabulations are incomplete and ambiguous. Here we present a systematic electronic digitization of all available temperature profiles from Voyager, followed by their reanalysis, employing currently accepted values of the abundances and radio refractivities of atmospheric species. We find the corrected temperature at the 1 bar level to be up to 4 K greater than the previously published values, i.e., 170.3 ± 3.8 K at 12°S (Voyager 1 ingress) and 167.3 ± 3.8 K at 0°N (Voyager 1 egress). This is to be compared with the Galileo probe value of 166.1 ± 0.8 K at the edge of an unusual feature at 6fdg57N. Altogether, this suggests that Jupiter's tropospheric temperatures may vary spatially by up to 7 K between 7°N and 12°S

Hyperspherical partial wave theory applied to electron hydrogen-atom ionization calculation for equal energy sharing kinematics

Hyperspherical partial wave theory has been applied here in a new way in the calculation of the triple differential cross sections for the ionization of hydrogen atoms by electron impact at low energies for various equal-energy-sharing kinematic conditions. The agreement of the cross section results with the recent absolute measurements of R\"oder \textit {et al} [51] and with the latest theoretical results of the ECS and CCC calculations [29] for different kinematic conditions at 17.6 eV is very encouraging. The other calculated results, for relatively higher energies, are also generally satisfactory, particularly for large $\Theta_{ab}$ geometries. In view of the present results, together with the fact that it is capable of describing unequal-energy-sharing kinematics [35], it may be said that the hyperspherical partial wave theory is quite appropriate for the description of ionization events of electron-hydrogen type systems. It is also clear that the present approach in the implementation of the hyperspherical partial wave theory is very appropriate.Comment: 16 pages, 9 figures, LaTeX file and EPS figures. To appear in Phys. Rev.

Extensive air showers with TeV-scale quantum gravity

One of the possible consequences of the existence of extra degrees of freedom beyond the electroweak scale is the increase of neutrino-nucleon cross sections ($\sigma_{\nu N}$) beyond Standard Model predictions. At ultra-high energies this may allow the existence of neutrino-initiated extensive air showers. In this paper, we examine the most relevant observables of such showers. Our analysis indicates that the future Pierre Auger Observatory could be potentially powerful in probing models with large compact dimensions.Comment: 7 pages revtex, 5 eps fig