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1. Damping rate measurements and predictions for gravity waves in an air–oil–water system

   https://doi.org/10.1063/5.0078160  

   Rajan, Girish Kumar ( February 2022 , Physics of Fluids)

   Dissipation of standing gravity waves of frequencies within 1–2 Hz is investigated experimentally. The waves are generated in a rectangular tank filled with water, the surface of which is covered with an oil layer of mean thickness, d. Damping rates are measured as a function of d, and compared with results from established theoretical models—in particular, with those from a recently developed three-fluid dissipation model that considers waves in a system of semi-infinitely deep fluids that lie above and below an interfacial fluid layer of finite thickness. Based on a comparison of experimental data with predictions, the oil–water interfacial elasticity, E₂, is empirically determined to be a linear function of d. The theoretical predictions include contributions from the three-fluid dissipation model, which accounts for energy losses due to shear layers at the interfaces, friction in the fluid bulk, and compression–expansion oscillations of the elastic interfaces; and from a boundary-layer dissipation model, which accounts for energy losses due to boundary layers at the tank's solid surfaces. The linear function, [Formula: see text], is used to compute the three-fluid model damping rate. An effective viscosity of the oil–water system is used to compute the boundary-layer model damping rate. The theoretical predictions are, on average, within 5% of measurements for all the wave frequencies considered. The promise shown by the three-fluid model is highlighted, as are the assumptions involved in the analysis and comparisons.

    

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2. Kinetic Experimental and Modeling Evaluations of Asphaltene Morphology and Growth Rate under Varying Temperature and Brine Conditions

   https://doi.org/10.2118/213811-MS  

   Quainoo, Kwamena Ato ; Abdulmohsin, Imqam ; Borecho Bavoh, Cornelius ( June 2023 , SPE)

   The utilization of predictive mechanisms to resolve asphaltene precipitation during oil production is a cleaner and less expensive means than the mechanical/chemical remediation techniques currently employed. Existing models lack predictive success due to opposing views on temperature-asphaltene precipitation interactions. In this study, the effect of varying temperatures (40, 50, 60, 70 80 and 90 °C) and brine concentrations (0 – 5 wt.%) on the long-time kinetics of asphaltene precipitations was evaluated. A series of experiments were conducted using the filtration technique and the confocal microscopy to study asphaltene precipitation on a model oil system consisting of asphaltenes, a precipitant, and a solvent. Furthermore, the Avrami modeling technique was employed to predict the morphology, and growth rate of the precipitating asphaltenes. The experimental results suggested that temperature significantly affects asphaltene precipitation including imparting its precipitation mechanism with a cross-behavioral pattern. Asphaltene precipitation in the system displayed an initial fast kinetics upon increasing temperature. The fast kinetics observed in the early times is due to the increasing dipole-dipole interactions between asphaltene sub-micron particles stimulated by increased temperature. However, the pattern changes into slower precipitations as the time progresses upon continuous heating of the reservoir fluid. The reason is the increased solubility of the asphaltenes imparted into the model oil system upon further increments in temperature. The presence of brine in the model-oil system also enhanced the rate and precipitation of asphaltenes. The experimental data were further analyzed with the Avrami crystallization fitting model to predict the formation, growth, morphology, and growth geometry of the precipitating asphaltenes. The Avrami model successfully predicted the asphaltene morphologies, growth rates and the crystal growth geometries. The growth geometries (rods, discs, or spheres) of the asphaltenes in the model oil systems upon temperature increments, ranged from 1.4 – 3.5. These values are indicative that temperature impacts the growth process of asphaltenes in the model system causing variations from a rod-like sporadic process (1.0 ≤ n ≤ 1.9) to a spherical sporadic growth process (3.0 ≤ n ≤ 3.9). This work precisely emphasizes the impact of temperature on asphaltene precipitations under long kinetic time, thus, providing a clear pathway for developing successful kinetic and thermodynamic models capable of predicting asphaltene precipitation reliably. The accurate prediction of asphaltene precipitation will eliminate the need for the use of harmful remediation solvents like benzene/toluene/ethylbenzene/xylene (BTEX). This study is therefore a critical step in the right direction to achieving accurate predictive model evaluations of asphaltene precipitations.

    

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3. Using a pseudophase model to determine AO distributions in emulsions: Why dynamic equilibrium matters

   https://doi.org/10.1002/ejlt.201600277  

   Bravo‐Díaz, Carlos ; Romsted, Laurence S. ; Losada‐Barreiro, Sonia ; Paiva‐Martins, Fátima ( September 2017 , European Journal of Lipid Science and Technology)

   For decades, explorations with ground state, thermal reactions combined with pseudophase kinetic models and methods for interpreting the results have provided insights into the properties of the different regions of homogeneous association colloids. More recent successful determination of antioxidant (AO) distributions by this approach is providing new insights into AO efficiency in opaque, well‐mixed two‐phase intact emulsions and eliminating the need to separate the phases. The chemical probe reacts with AOs exclusively in the interfacial region of the emulsion, permitting simplification of the kinetic treatment, and determining its distribution between the oil, interfacial, and aqueous regions. AO distributions are obtained from the two partition constants,and, of the AOs between the oil‐interfacial and aqueous‐interfacial regions, respectively.andvalues are obtained by fitting the observed rate constant,k_obs, versus surfactant concentration profiles with an overall kinetic approach or model we call the “pseudophase chemical kinetic method.” However, because emulsions break up and reform, and reactants and other components diffuse at various time scales within and between the oil, interfacial, and water regions,k_obscould also depend on reactant diffusion coefficients. Here we demonstrate that reactant diffusion is generally orders of magnitude faster than most thermal reactions and reactant distributions between the multiple oil, aqueous, and interfacial droplets and regions of emulsions are in dynamic equilibrium throughout the multiphase systems during the time course of the reaction. Thus, kinetic probes are powerful tools for determining structure‐reactivity, for example, the HLB, relationships governing AO distributions and efficiencies in emulsions.

   Practical applications:The analysis presented here demonstrates that one of the basic assumptions of the pseudophase chemical kinetic model that we have developed has a solid foundation in the properties of emulsions. That is, we can determine the distributions of reactants between oil (O), interfacial (I), and aqueous (W) regions of the emulsions because the diffusivity coefficients of reactants within emulsions are orders of magnitude greater than the rate of the reaction between the antioxidant and the 4‐hexadecylbenzenediazonium probe. Consequently, we can use the same kinetic model in emulsions as we have used in homogeneous microemulsions. The method permits determination of the partition constants of many antioxidants between the O‐I and W‐I regions of the emulsions and from them their distributions. The method provides new insights into the relationships between antioxidant hydrophobic‐lipophilic balance (HLB) and its efficiency in emulsions and a natural explanation for the cut‐off effect observed with increasing antioxidant HLB.

   Interpreting chemical reactivity in emulsions requires that reactive componentsAandBbe in dynamic equilibrium, that separate second order rate constants,kdefined for the oil, interfacial, and aqueous regions, subscripts O, I, and W, and for simplicity, the volume of each region depends on the added volumes of oil, surfactant, and water.

    

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4. Affinity of small-molecule solutes to hydrophobic, hydrophilic, and chemically patterned interfaces in aqueous solution

   https://doi.org/10.1073/pnas.2020205118  

   Monroe, Jacob I. ; Jiao, Sally ; Davis, R. Justin ; Robinson Brown, Dennis ; Katz, Lynn E. ; Shell, M. Scott ( December 2020 , Proceedings of the National Academy of Sciences)

   Performance of membranes for water purification is highly influenced by the interactions of solvated species with membrane surfaces, including surface adsorption of solutes upon fouling. Current efforts toward fouling-resistant membranes often pursue surface hydrophilization, frequently motivated by macroscopic measures of hydrophilicity, because hydrophobicity is thought to increase solute–surface affinity. While this heuristic has driven diverse membrane functionalization strategies, here we build on advances in the theory of hydrophobicity to critically examine the relevance of macroscopic characterizations of solute–surface affinity. Specifically, we use molecular simulations to quantify the affinities to model hydroxyl- and methyl-functionalized surfaces of small, chemically diverse, charge-neutral solutes represented in produced water. We show that surface affinities correlate poorly with two conventional measures of solute hydrophobicity, gas-phase water solubility and oil–water partitioning. Moreover, we find that all solutes show attraction to the hydrophobic surface and most to the hydrophilic one, in contrast to macroscopically based hydrophobicity heuristics. We explain these results by decomposing affinities into direct solute interaction energies (which dominate on hydroxyl surfaces) and water restructuring penalties (which dominate on methyl surfaces). Finally, we use an inverse design algorithm to show how heterogeneous surfaces, with multiple functional groups, can be patterned to manipulate solute affinity and selectivity. These findings, importantly based on a range of solute and surface chemistries, illustrate that conventional macroscopic hydrophobicity metrics can fail to predict solute–surface affinity, and that molecular-scale surface chemical patterning significantly influences affinity—suggesting design opportunities for water purification membranes and other engineered interfaces involving aqueous solute–surface interactions.

    

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5. Precipitant Effects on Aggregates Structure of Asphaltene and Their Implications for Groundwater Remediation

   https://doi.org/10.3390/w12082116  

   Hammond, Christian B. ; Wang, Dengjun ; Wu, Lei ( August 2020 , Water)

   Asphaltenes generally aggregate, then precipitate and deposit on the surfaces of environmental media (soil, sediment, aquifer, and aquitard). Previous studies have recognized the importance of asphaltene aggregates on the wettability of aquifer systems, which has long been regarded as a limiting factor that determines the feasibility and remediation efficiency of sites contaminated by heavy oils. However, the mechanisms/factors associated with precipitant effects on asphaltene aggregates structure, and how the precipitant effects influence the wettability of surfaces remain largely unknown. Here, we observe the particle-by-particle growth of asphaltene aggregates formed at different precipitant concentrations. Our results show that aggregates for all precipitant concentrations are highly polydisperse with self-similar structures. A higher precipitant concentration leads to a more compacted aggregates structure, while precipitant concentration near to onset point results in a less compact structure. The well-known Smoluchowski model is inadequate to describe the structural evolutions of asphaltene aggregates, even for aggregation scenarios induced by a precipitant concentration at the onset point where the Smoluchowski model is expected to explain the aggregate size distribution. It is suggested that aggregates with relative high fractal dimensions observed at high precipitant concentrations can be used to explain the relatively low Stokes settling velocities observed for large asphaltene aggregates. In addition, asphaltene aggregates with high fractal dimensions are likely to have high density of nanoscale roughness which could enhance the hydrophobicity of interfaces when they deposit on the sand surface. Findings obtained from this study advance our current understandings on the fate and transport of heavy oil contaminants in the subsurface environment, which will have important implications for designing and implementing more effective and efficient remediation technologies for contaminated sites. 

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