Effect of the Molecular Structure on the Adsorption Properties of Cationic Surfactants at the Air–Water Interface

The surface activity and thermodynamic properties of adsorption at the air–water interface of two series of cationic surfactants based on isourea: the O-dodecyl-N,N′-diisopropylisourea hydrochloride, hydrobromide, and hydroiodide and the O-tridecafluorooctyl-N,N′-diisopropylisourea hydrochloride and hydrobromide were studied. The effect of structural parameters as the nature of the halide counter ion and the nature of the non-polar chain on the surface activity and thermodynamic properties of adsorption were investigated. The surface parameters, the maximum surface excess concentration (Γ _max), the minimum area per molecule (A _min) at the aqueous solution-air interface, effectiveness of surface tension reduction (π_CMC), and efficiency of surface tension reduction (pC ₂₀) were estimated. The standard Gibbs free energy of adsorption, (ΔG°_ads) change has been calculated at different temperatures.     

Optimization of Dynamic Interfacial Tension for Crude Oil–Brine System in the Presence of Nonionic Surfactants

In this study, interfacial tension (IFT) is measured between brine and crude oil (a sample of heavy oil from an Iranian oil reservoir) in the presence of two nonionic surfactants, KEPS 80 (Tween 80) and Behamid D, at different concentrations in order to optimize the concentrations of the surfactants. The surface response method is used to design the IFT measurement experiments. The experimental design and optimization is performed using the IFT as an objective function and temperature, concentration, and time as independent variables. In addition to the IFT measurement, various experiments such as stability tests of the surfactants in NaCl brine solutions, adsorption experiments on the carbonated rock surface, and phase behavior tests are performed to investigate the behavior of KEPS 80 and Behamid D in the enhanced oil recovery process. At the end, a model using the response surface statistical technique is designed for optimization of the concentrations of the surfactants, and a surfactant molecular migration mechanism is used for explanation of the dynamic IFT variation versus time. In the case of IFT experiments, the effect of surfactant concentration (at 1000, 3000, and 5000 ppm) on the dynamic IFT is investigated. The experiments are performed at four temperatures (25, 40, 50, and 67°C). The results show that the oil–brine IFT values can be reduced to about 4 mN m⁻¹ in the presence of Behamid D and to about 1 mN m⁻¹ in the presence of KEPS 80 at low concentrations.     

Novel Alkyl Ether Sulfonates for High Salinity Reservoir: Effect of Concentration on Transient Ultralow Interfacial Tension at the Oil–Water Interface

The effect of surfactant concentration on the occurrence and detection of transient ultralow interfacial tension (IFT) between crude oil and formation water at 75 °C has been investigated using a series of novel sodium alkyl ether sulfonates having various increasing molecular weights and degrees of ethoxylation. All surfactant systems displayed dynamic interfacial tension (DIT). Transient ultralow DIT (DIT_min) were detected only within an intermediate surfactant concentration. This behavior was attributed to an implicit concentration-related length scale required for the added surfactant to diffuse from the bulk phase to the freshly prepared oil–water interface. In the high surfactant concentration range, this length scale is relatively short and results in an instantaneous (and undetectable) occurrence of DIT_mim in a relatively very short time scale, well beyond the detection limit of the spinning drop tensiometer (~2–3 min). Interestingly, DIT_min were detected only in systems above the surfactant’s critical micelle concentration, suggesting that DIT_min occurs as a result of the diffusion (subsequent to the adsorption) of the oil acidic species from the interface to the bulk phase to form mixed micelles with the added surfactant. Measurements of DITs in the presence of decane showed no evidence for DIT_min, confirming the general belief that DIT_min is indeed due to the interaction of the added surfactant with the oil acidic components. Finally, the effect of surfactant concentration on the equilibrium IFT (γ_eq) showed evidence for relatively low values (~10⁻² mNm⁻¹) for some surfactant systems.     

Interfacial Tension Studies of N,N‐Dialkyl Amides

Abstract

The interfacial tension (IFT) of 1 M solutions of N,N‐dialkyl amide in n‐dodecane against water and nitric acid has been measured at 303 K. Ten amides, namely, dibutyl hexanamide (DBHA), diisobutyl hexanamide (DiBHA), dibutyl octanamide (DBOA), dihexyl hexanamide (DHHA), dibutyl dodecanamide (DBDA), di n‐octyl butanamide (DOBA), diisooctyl butanamide (DiOBA), di n‐octyl isobutanamide (DOiBA), di n‐hexyl octanamide (DHOA), and di n‐octyl hexanamide (DOHA) were synthesized and used. The effect of concentration of DOHA on IFT against 3 M nitric acid was also studied. It was observed that the introduction of branching in an amide on either the acyl or the nitrogen side increases the IFT over its straight chain analogue, as in the case of DiOBA, DOiBA, and DiBHA. Increasing the carbon chain length on the acyl side, keeping the total carbon number constant, was found to increase the IFT considerably. Increasing the concentration of the amide resulted in a decrease in the IFT values, due to the lowering of the concentration of hydrophobic diluent. An increase in the uranium loading of the organic phase in the case of 1 M DOHA, was found to increase the IFT.     

Studies on Surfactant–Ionic Liquid Interaction on Clouding Behaviour and Evaluation of Thermodynamic Parameters

The present study investigates the effect of tetraethyl ammonium tetrafluoroborate [TEA(BF₄)] ionic liquid (IL) on the cloud point (CP) of the following nonionic surfactants in aqueous solution: ter‐octylphenol ethoxylates with 9.5 and 4.5 ethylene oxide groups (abbreviated TOPEO9.5 and TOPEO4.5, respectively), cetyl alcohol ethoxylate with 10 ethylene oxide groups (C16EO10), and sorbitan monolaurate and monooleate both with 20 ethylene oxide groups (SMLEO20 and SMOEO20, respectively) in aqueous solutions. The thermodynamic parameters of these mixtures were calculated at different IL concentrations. The CP of most of the tested nonionic surfactants increased with the increment of IL concentrations with the exception of C16EO10 for which it decreased. The solubility of a nonionic surfactant containing polyoxyethylene (POE) hydrophilic chain was considered as maximum at the CP, hence the thermodynamic parameters were calculated at the same temperature. The results showed that the standard Gibbs free energy (?G_CP⁰), the enthalpy (?H_CP⁰) and the entropy (?S_CP⁰) of the clouding phenomenon were found to be positive for ethoxylated octylphenol and sorbitan esters, whereas ?H_CP⁰ and ?S_CP⁰ were found to be negative for C16EO10. It was found that the overall clouding process is endothermic for ethoxylated octylphenol and sorbitan esters and exothermic for C16EO10. For all the studied systems, ?H_CP⁰ > T?S_CP⁰ indicated that the process of clouding is guided by both enthalpy and entropy. The positive value of standard Gibbs free energy (?G_CP⁰) for the all mixed systems indicated that the process proceeds non‐spontaneously. The ?G_CP⁰ decreased with increasing IL concentration for all the nonionic surfactants; however, it decreased with increasing surfactant concentration for TOPEO9.5, C16EO10, and SMOEO20, and increased with increasing surfactant concentration for TOPEO9.5 and SMLEO20.     

Effect of Diffusion of Coal Pyrolysis Products on the Ignition Characteristics and Conditions of Coal–Water Fuel Droplets

This paper presents a theoretical study of the thermal preparation and ignition of a coal–water fuel droplet under intense radiative-convective heating with diffusion of gaseous pyrolysis products of the solid fuel into the ambient gaseous medium. It has been found that gaseous pyrolysis products are ignited at a distance from the heating surface approximately equal to the radius of the droplet, after which the coke of the main fuel layer is ignited. The time between the ignition of volatiles and the coke residue is less than 0.5 s. Comparison of the ignition delays obtained by mathematical modeling and experimentally has shown satisfactory agreement between theoretical and experimental values.     

Adsorption of Binary Mixtures of Anionic Surfactants at Water–Air and Poly(Tetrafluoroethylene)–Water Interfaces

Measurements of the surface tension (γ _LV ) and the advancing contact angle (θ) on poly(tetrafluoroethylene) (PTFE) were carried out for aqueous solutions of sodium decyl sulfate (SDS) and sodium dodecyl sulfate (SDDS) and their mixtures. The results obtained indicate that the values of the surface tension and the contact angle of solutions of surfactants on PTFE surface depend on the concentration and composition of the surfactants mixture. On the curves presenting the relationship between the surface tension, contact angle and monomer mole fraction of SDDS (α) in the mixture of SDDS and SDS, there is a minimum at α equal to 0.8 which together with the negative values of the interaction parameters indicate that synergism occurs in surface tension and contact angle reduction almost in the range of concentration corresponding to the saturated monolayer of surfactants at the water–air interface. The results and calculations obtained also indicate that for single surfactants and their mixtures at a given concentration in the bulk phase, the values of surface excess concentration of the surfactants at water–air and PTFE–water interfaces are nearly the same, which suggests that the orientation of SDDS and SDS molecules at both interfaces in saturated monolayer should be vertical to the interfaces. Taking into account the values of the monomer mole fractions of the surfactants in a mixed monolayer at the water–air interface and values of the contact angle of a single surfactant on the PTFE surface, it is possible in a simple way to predict the values of the contact angle of a mixture at a given concentration and composition.     

Micellization and Interfacial Interaction Behaviors of Gemini Cationic Surfactants–CTAB Mixed Surfactant Systems

The interfacial and micellization behaviors of binary mixtures of two gemini cationic surfactants and conventional the cetyl trimethyl ammonium bromide surfactant were studied at various molar ratios. From the equilibrium surface tension measurements, the critical micelle concentrations (CMC) data were obtained as functions of the composition. Values of the CMC were analyzed according to the regular solution model developed by Rubingh for mixed micelles. Two interaction parameters were obtained for each system, the interaction at the interface, and in the micellar phase. The results showed that micellization and adsorption properties of the studied mixed systems depend on the spacer chain lengths of the gemini surfactants and their ratio in the mixed systems.     

Effect of Molybdenum on the Sulfur-Tolerance of Cerium–Cobalt Mixed Oxide Water–Gas Shift Catalysts

As traditional sources of energy become depleted, significant research interest has gone into conversion of biomass into renewable fuels. Biomass-derived synthesis gas typically contains concentrations ranging from ~30 to 600 ppm H₂S. H₂S is a catalyst poison which adversely impacts downstream processing of hydrogen for gas-to-liquid plants and the deactivation of water–gas shift catalysts by sulfur is typical. Novel catalysts are needed to remain active in the presence of sulfur in order to boost efficiency and mitigate costs. Previous studies have shown molybdenum to be active in concentrations of sulfur >300 ppm. Cobalt has been shown to be active as a spinel in concentrations of sulfur <240 ppm. Ceria has received attention as a catalyst due to its oxygen donating properties. In this study, mixed oxide catalysts were synthesized via Pechini’s method into various blends of metal oxide solutions. Activity testing at low steam-to-carbon ratios (1:1) produced near equilibrium conversions at a GHSV of 6,300 h^?1 and over a temperature range of 350–400 °C for a Ce–Co mixed oxide even after an 800 ppm sulfur treatment. The addition of molybdenum to the Ce–Co base had little effect on sulfur tolerance, but it did lead to a reduction in selectivity for methanation. Specific surface areas generally increased following the sulfur treatments and X-ray diffraction patterns confirmed that bulk sulfiding did not occur.     

Behavior of Anionic Surfactants and Short Chain Alcohols Mixtures in the Monolayer at the Water–Air Interface

Measurements of the surface tension of aqueous solution of mixtures of sodium dodecyl sulfate (SDDS) with methanol and ethanol in SDDS concentration range from 10⁻⁵ to 10⁻² M and mixtures of sodium hexadecyl sulfonate (SHS) with methanol and ethanol at SHS concentration from 10⁻⁵ to 8 × 10⁻⁴ M and for methanol and ethanol from 0 to 21.1 and, 11.97 M, respectively, were carried out at 293 K. Moreover, the surface tension of aqueous solution mixtures of SDDS with propanol in the concentration range from 0 to 6.67 M taken from the literature was also considered. The results obtained indicate that it is possible to describe the relationship between the surface tension and molar concentration or molar fraction of alcohol by Szyszkowski and Connors equations. However, the Fainerman and Miller equation allows us to predict the isotherm of the surfactant tension at constant anionic surfactants concentration at which their molecules are present in the solution in the monomeric form if the molar area of surfactants and alcohols can be determined. Based on the surface tension isotherms, the Gibbs surface excess of anionic surfactants and alcohols concentration at water–air interface was determined and then recalculated for Guggenheim-Adam surface excess concentration of these substrates, and next the molar fraction of alcohols and surfactants in the surface layer was determined. These molar fractions were discussed with regard to surfactant and alcohol standard free energy of adsorption at the water–air interface determined from Langmuir and Aronson and Rosen equations. The standard free energy of adsorption determined in these ways was compared to that deduced on the basis of pC₂₀ and Lifshitz van der Waals-components of the anionic surfactant and alcohol tails.     

Effect of Surfactants on Catalytic Activity of Diastase α-Amylase

The enzyme amylase is one of the hydrolyzing enzymes used in detergent formulation in order to remove soil based on polysaccharides. The effectiveness of the enzyme depends on its compatibility with other ingredients of the formulation. Among the studied additives, comprising anionic surfactants sodium dodecyl hydrogen sulfate (SDS) and dioctyl sodium sulfosuccinate, the cationic surfactant cetyl trimethyl ammonium bromide (CTAB), nonionic surfactants polyoxyethylene sorbitan monooleate and polyoxyethylene octyl phenyl ether, carboxy methyl cellulose and sodium sulfate, only the anionic surfactant SDS and cationic surfactant CTAB showed catalytic enhancement of α-amylase. The kinetic parameters, K _m and k _cat, showed an increase in catalytic activity in the micellar pseudophase. The decrease in optimum temperature from 55 to 30 °C and the shift in optimum pH from 5.5 to 7 on the addition of SDS and CTAB for the hydrolysis of starch are very favorable to enhance the washing characteristics.     

A Star-Shaped Anionic Surfactant: Synthesis,Alkalinity Resistance,Interfacial Tension and Emulsification Properties at the Crude Oil–Water Interface

In this research, a star‐shaped surfactant was synthesized through the chlorination reaction, alkylation reaction and sulfonation reaction of triethanolamine, which is composed of three hydrophobic chains and three sulfonate hydrophilic groups. The critical micelle concentration (CMC) of the surfactant was measured by the surface tension method, and the results showed that it had high surface activity with CMC of 5.53 × 10^?5 mol/L. The surfactant was superior in surface active properties to the reference surfactants SDBS and DADS‐C₁₂. The interfacial tension (IFT) of the studied crude oil–water system (surfactant concentration 0.1 g/L, NaOH concentration 0.5 g/L, and experimental temperature 50 °C) dropped to 1.1 × 10^?4 mN/m, which can fulfil the requirement of surfactants for oil displacement. An aqueous solution of the surfactant and crude oil was emulsified by shaking, which formed a highly stable oil‐in‐water (O/W) emulsion with particle size of 5–20 μm. The oil displacement effect was almost 12%.     

Effect of Surfactants and Temperature on Adsorption Behavior of Metal Ions on Organic–Inorganic Hybrid Exchanger,Acrylamide Aluminum Tungstate

The adsorption behavior of a thermally and chemically stable hybrid ion-exchange material, acrylamide aluminum tungstate was explored in cationic (CTAB) and anionic (SDS) surfactants and acidic solvents. Critical micellar concentration (CMC) appears to be an important parameter in determining the adsorption behavior of metal ions. Equilibration time and temperature studies on the distribution coefficient of metal ions were studied. On the basis of the distribution coefficient, this material was successfully used for quantitative separations of some binary synthetic mixtures of metal ions by the column method. Hg(II) ion was selectively determined quantitatively in synthetic mixture. The material appears to be promising for separating toxic metal ions in a real matrix (industrial effluents and waste water) and can be utilized as a packing material in HPLC and GC columns for faster and more efficient separation.

Interfacial interactions in calcium carbonate–polypropylene composites. 2: Effect of compounding on the dispersion and the impact properties of surface-modified composites

This study was carried out to investigate the influences of compounding process and surface treatment on calcium carbonate (CaCO₃) filled polypropylene. The compounding process is discussed with reference to a twin-screw extruder and an internal mixer. The calcium carbonate filler was surface-treated with a liquid titanate coupling agent (LICA 12) and stearic acid. Composites of different weight fractions were prepared by both compounding processes, and their impact properties were evaluated. The notched Izod impact strength increased with CaCO₃ content up to a maximum at about 10 vol%, and then decreased. Surface treatment of CaCO₃ filler generally yielded composites of higher impact strength than untreated system. Though LICA 12 was more effective than stearic acid in modifying the filler, the low-cost stearic acid proved to be more effective when dealing with the impact properties of composites. Moreover, the composites from a Brabender Plasti-corder exhibited better gross uniformity than that from the twin-screw extruder. However, good filler dispersion and uniform microscopic morphology, as revealed by SEM microscopy, was observed in the samples from the twin-screw extruder. Polym. Compos. 25:451–460, 2004. © 2004 Society of Plastics Engineers.     

Effect of Ionic Strength on Freeze–Thaw Stability of Glycosylated Soy Protein Emulsion

This study used Soy Protein Isolate (SPI), Soy Protein Isolate Hydrolysates (SPH) and Dextran (D) as raw materials. Covalent compounds were prepared by grafting soy protein isolate and soy protein isolate hydrolysate with dextran by water-heating method, which were SPI-D and SPH-D, respectively. The effect of ionic strength (0–500 mM) on the freeze–thaw stability of SPI, SPI-D, and SPH-D emulsions was investigated. Fourier transform infrared analysis and Fluorescence emission spectroscopy analysis indicated that the structure of the protein changed. In this study, it was found that with the increase of ionic strength, the zeta potential of the three samples presented a downward trend and the surface hydrophobicity first decreased and then increased. The addition of ions effectively improved the freeze–thaw stability of the emulsions. The particle size of the emulsions changed little after freeze–thaw cycles, and coalescence degree, creaming index, and oiling off significantly decreased. Especially when the ionic strength reached 300 mM, the degree of coalescence was 248.46%, 170.92%, and 167.77%, respectively, and the oiling off was also reduced by 68.52%, 68.25%, and 59.92%, respectively. The creaming index of the SPI emulsion was 48.49% lower than the creaming index without ions. However, when the ionic strength exceeded 300 mM, the coalescence degree, creaming index, and oiling off of the emulsions increased. Optical microstructures also found that at ionic strength of 300 mM, the oil droplets produced by the three kinds of emulsion after freeze–thaw were smaller than those without ions.     

How the Influence of Different Salts on Interfacial Properties of Surfactant–Oil–Water Systems at Optimum Formulation Matches the Hofmeister Series Ranking

In this work, we present the effects of salts on sodium dodecyl benzene sulfonate micellization and on the interfacial performance of a sodium dodecyl benzene sulfonate–heptane–brine system at optimum formulation, i.e., hydrophilic–lipophilic deviation (HLD) = 0. In order to do that, interfacial tension and dilational interfacial rheology properties of surfactant–heptane–water systems at optimum formulation are measured using an interfacial spinning drop tensiometer with an oscillating velocity, which can accurately measure interfacial rheology properties at both low and ultralow interfacial tensions. The brines used contain one of the following salts: MgCl₂, CaCl₂, NaCl, NH₄Cl, NaNO₃, CH₃COONa, or Na₂SO₄. We performed a one-dimensional salinity scan with each of these salts to achieve an optimum formulation. In relation to the Hofmeister series, we found that, at optimum formulation, systems with chaotropic ions (NH₄⁺, NO₃⁻) present interfaces with ultralow interfacial tensions, very low dilational modulus, and a low phase angle, whereas kosmotropic ions (Mg²⁺, Ca²⁺, SO₄⁻²) generate high interfacial tension and high rigidity monolayers. Intermediate ions in the Hofmeister series (Na⁺, CH₃COO⁻, Cl⁻) present interfaces with intermediate properties. Furthermore, according to the Hofmeister series, interfaces can be respectively ordered from higher to lower rigidity for surfactant counterions Mg²⁺ > Ca²⁺ > Na⁺ > NH₄⁺ and coions SO₄²⁻ > CH₃COO^– > Cl⁻ > NO₃⁻, which correspond to a salting-out (highest rigidity) and salting-in (lowest rigidity) effect. We observed that counterions have a more significant effect on surfactant–oil–water system properties than those that act as coions.     

Synergism and Interfacial Property Study of Sodium Lauryl Ether Sulfate and Polysorbate 80 at the Air–Water Interface

Adsorption and micellization behavior of sodium lauryl ether sulfate (SLES) and Polysorbate 80 (PS80) was investigated using equilibrium and dynamic surface tension and foaming measurements. Critical micelle concentration (CMC) was determined using surface tension and dye (Sudan red III) solubilization method with the help of the Wilhelmy plate method and ultraviolet–visible spectroscopic method, respectively. The strength of the interaction for micellization and adsorption between the mixtures are calculated using the β interaction parameter. The SLES-PS80 mixture shows synergistic interaction with β = −8.0. The dynamic and foaming behavior at constant bulk concentration showed a higher t ^* value with lowest foaming at 50% mole fraction of SLES. The emulsification index (EI) of pure SLES, pure PS 80, and 1:1 SLES-PS 80 composition was studied using neem, karanja, and sunflower oils. Karanja and sunflower oils show a higher EI for mixture than the pure surfactants, whereas neem shows a lower EI for mixture than pure surfactants.     

Accurate Prediction of the Surface Tensions of Ionic Liquids–Amines–Water Mixtures Regarding CO2 Recovery and Sequestration Processes

A support vector machine (SVM) model is presented concerning accurate prediction of the surface tension of the complex mixtures of ionic liquids (ILs)–amines–water using the most important types of amines employed in the gas sweetening plants, such as monoethanolamine, diethanolamine, and methyldiethanolamine. Different ILs, such as [bmim] [BF₄], [bmim] [DCA], [mmim] [dmp], [emim] [dep], [bmim] [BF₄], [bmim] [Br], [bmim] [BF₄], and [bmim] [Br], are considered in the presented model. The effects of most important influencing parameters, such as temperature and mass fraction of amines and ILs, on the surface tension of the aqueous mixtures of ILs and amines are well represented. A comparison of the presented model and the most important models reveals that the suggested SVM model has better performance in terms of accuracy and generalizability. The percentage average absolute deviation between the predicted and experimental surface tensions is about 0.44% suggesting the superiority of the presented model over wide ranges of temperatures and species concentrations.     

The Effect of Sulphur and Water Treatments on the Performance of Pd/��-Zeolite Diesel Oxidation Catalysts

Sulphur, sulphur-water, and water pretreatments were done to find out the effect of these compounds on a diesel oxidation Pd/??-zeolite catalyst and ??-zeolite washcoat. After pretreatments, the samples were analysed by BET, XRF, TEM-SEM, and XPS. In addition, the activity of fresh and pretreated Pd/??-zeolite catalysts was studied utilizing the by Gasmet FT-IR in production gas analysis. Sulphur compounds (SO₂ or ?SO₄) were found to have a deactivating effect on the activity of the studied Pd/??-zeolite catalyst.