Study on the Interfacial Tensions Between Oils and Alkylbenzene Sulfonate Gemini Surfactant Solutions

Interfacial tensions (IFT) of five alkylbenzene sulfonate Gemini surfactants Ia, Ib, Ic, Id, and Ie at different oils/water systems were measured by a spinning drop interfacial tensiometer. And critical micelle concentration (CMC), the interfacial tension at CMC (γ_CMC), maximum interfacial excess concentration (Γ _max) and the surface area per molecule (A_min) were calculated. The results indicated that the CMC values determined with interfacial tension method were lower than those determined with surface tension method. And γ_CMC for Ie is larger than that for Ia, Ib, Ic, and Id. In addition, the effects of temperature and hydrophobic chains on dynamic IFT were also studied. With the increment of temperature, dynamic IFT is easier to reach a stable value. However, with the increment of hydrophobic chains, dynamic IFT is more difficult to reach a stable value. Each Gemini surfactant produces a minimum IFT when measured against a different n-alkane.     

Determination of Stoichiometric Dissociation Constants of Benzoic Acid in Aqueous Sodium or Potassium Chloride Solutions at 25°C

Equations were determined for the calculation of the stoichiometric (molality scale) dissociation constant K_m of benzoic acid in dilute aqueous NaCl and KCl solutions at 25°C from the thermodynamic dissociation constant K_a of this acid and from the ionic strength I_m of the solution. The salt alone determines mostly the ionic strength of the solutions considered in this study and the equations for K_m were based on the single-ion activity coefficient equations of the Hückel type. The existing literature data obtained by conductance measurements and by electromotive force (EMF) measurements on Harned cells were first used to revise the thermodynamic value of the dissociation constant of benzoic acid. A value of K_a = (6.326 ± 0.005) × 10^-5 was obtained from the most precise conductivity set [Brockman and Kilpatrick] and this value is supported within their precisions by the less precise conductivity set of Dippy and Williams and by the EMF data set measured by Jones and Parton with quinhydrone electrodes. The new data measured by potentiometric titrations in a glass electrode cell were then used for the estimation of the parameters of the Hückel equations of benzoate ions. The resulting parameters were also tested with the existing literature data measured by cells with and without a liquid junction. The Hückel parameters suggested here are close to those determined previously for anions resulting from aromatic and aliphatic carboxylic acids. By means of the calculation method based on the Hückel equations, K_m can be obtained almost within experimental error at least up to I_m of about 0.5 mol-kg_-1 for benzoic acid in NaCl and KCl solutions.     

ATMOSPHERIC OXIDATION OF VITAMIN C AND E IN THE SURFACTANT SYSTEM

The association of ascorbic acid (H₂A, AA) with α-tocopherol (α-T) enhances the antioxidant capability of the two vitamins in a microemulsion formed by water, pentanol and sodium dodecyl sulphate. The comparison of vitamin C oxidation kinetics in the presence and absence of α-T in the system shows that there are no tangible differences in the time of the ascorbic acid decomposition. The main effect is the enhancement of the H₂A oxidation with increased pentanol concentration in the system. Ascorbic anion interacts with surfactant association structures, changing W/O microemulsion towards O/W system. The polar part of H₂A is exposed to aqueous solution and subjected to oxidation.

For the vitamin C to vitamin E weight ratio equal 0.13, ascorbic acid stimulates α-T decomposition as long, as it does in the non-oxidised form. When not all amounts of both vitamins are decomposed their activity is similar to each other in the anionic surfactant system. It means they are both good antioxidants in W/O microemulsions. After some time, when vitamin C is completely decomposed, all these micellar systems become more stable with regard to vitamin E. Vitamin E occurs to be a better antioxidant in O/W microemulsion.     

Debye–Hückel Contributions to the Gibbs Energy Interaction Parameters for Ternary Electrolyte + Non-Electrolyte + Water Systems

The Debye–Hückel and non-Debye–Hückel contributions to the Gibbs energy interaction parameters are investigated for electrolyte (E) + non-electrolyte (N) + water (W) systems. A method is proposed for calculating the interaction parameters, C _n ^DH,C _n ^N, and C _n ^T, which represent the Debye–Hückel, non-Debye–Hückel, and total contributions, respectively. Four ternary E + N + W systems are chosen and the interaction parameters are computed with different forms of the Debye–Hückel equation. Results show that: (1) the Gibbs energy interaction parameters between E and N can be divided into two parts: the Debye–Hückel contribution and the non-Debye–Hückel contribution, C _n ^T=C _n ^DH+C _n ^N; (2) the signs and magnitudes of the Debye–Hückel contribution to the interaction parameters, C _n ^DH, depend mainly on the change in the dielectric constant of the solvent due to the addition of the non-electrolyte into the solvent; and (3) when the addition of the non-electrolyte only affects slightly the dielectric constant of the solvent, C ₁^DH (indicating the Debye–Hückel contribution to the interaction parameter for E + N) has a very small value and consequently can be neglected. In general, C ₁^DH is large, even larger than C ₁^N. Electronic Supplementary Material The online version of this article () contains supplementary material, which is available to authorized users.     

Re-evaluation of the Thermodynamic Activity Quantities in Pure Aqueous Solutions of Chlorate, Perchlorate, and Bromate Salts of Lithium, Sodium or Potassium Ions at 298.15 K

The Hückel equation used to correlate the experimental activities of dilute alkali metal chlorate, perchlorate or bromate solutions up to a molality of about 1.5 mol⋅kg⁻¹ contains two electrolyte-dependent parameters: B {that is related closely to the ion-size parameter (a ^∗) in the Debye–Hückel equation} and b ₁ (this parameter is the coefficient of the linear term with respect to the molality, which is related to hydration numbers of the ions of the electrolyte). In more concentrated solutions up to 7 mol⋅kg⁻¹, an extended Hückel equation was used, it contains additionally a quadratic term with respect to the molality, and the coefficient of this term is the parameter b ₂. Parameters for the Hückel equations were evaluated from isopiestic data for LiClO₃, LiBrO₃, LiClO₄, NaClO₃, NaBrO₃, NaClO₄, KClO₃, and KBrO₃. In these estimations, the Hückel parameters determined recently for NaCl solutions were used. The resulting parameter values were tested with the vapor pressure and isopiestic data available in the literature for solutions of these salts. Most of these data were reproduced within experimental error by means of the Hückel or extended Hückel equations, at least up to a molality of 3.0 mol⋅kg⁻¹, for all salts considered. Reliable activity and osmotic coefficients for solutions of these salts can, therefore, be calculated by using the new Hückel equations, and they are tabulated here at rounded molalities. The activity and osmotic coefficients obtained from these equations were compared to the values reported in several previous tabulations.     

Hydrophobic effect for anionic dye - cationic surfactant interaction in aqueous and mixed solvent

Abstract

The interaction between anionic dyes [Reactive Orange 122 (R.O 122), Reactive Blue 19 (R.B 19), Reactive Violet 5 (R.V 5) and Acid Green 20 (A.G 20)] with cationic surfactant cetyltrimethylammoniun bromide (CTAB) has been investigated by spectrophotometry and conductance technique. The used dyes are characterized by tautomeric behavior which affects the mechanism of the interaction. Various parameters such as dye structure, surfactant composition, solvent composition, temperature and pH of the medium were studied. The spectral data were applied for calculating the binding constant between dye and surfactant (K_b), fraction of micellization (?_mic), and standard free energy change of binding (ΔG°_b) in 0,10,20 and 30 v/v % acetonitile (AN). Conductance technique was constructed to estimate the ion pairing constant (K_a) at different temperatures and v/v % AN. Thermodynamic parameters (ΔG°, ΔH° and ΔS°) for ion pair formation were evaluated. The role of hydrophobic and electrostatic effect on dye-surfactant interaction was discussed.     

Effect of Polymer on Dynamic Interfacial Tensions of Anionic–nonionic Surfactant Solutions

The dynamic interfacial tensions (IFTs) of enhanced oil recovery (EOR) surfactant/polymer systems against n-decane have been investigated using a spinning drop interfacial tensiometer in this paper. Two anionic–nonionic surfactants with different hydrophilic groups, C₈PO₆EO₃S (6-3) and C₈PO₆EO₆S (6-6), were selected as model surfactants. Partially hydrolyzed polyacrylamide (HPAM) and hydrophobically modified polyacrylamide (HMPAM) were employed. The influences of surfactant concentration, temperature, polymer concentration, and oleic acid in the oil on IFTs have been studied. The experimental results show that anionic–nonionic surfactants can form compact adsorption films and reach ultralow IFT (10^?3 mN/m) under optimum conditions. The addition of polymer has great influence on dynamic IFTs between surfactant solutions and n-decane mainly by the formation of looser mixed films resulting from the penetration of polymer chains into the interface. The compact surfactant film will also be weakened by the competitive adsorption of oleic acid, which results in the increase of IFT. Moreover, the penetration of polymer chains will be further destroyed surfactant/polymer mixed layer and lead to the obvious increase of IFT. On the other hand, polymers show little effect on the IFTs of 6-6 systems than those of 6-3 because of the hindrance of longer EO chain of 6-6 at the interface.     

高盐油藏下两性/阴离子表面活性剂协同获得油水超低界面张力

研究了在高盐油藏中, 利用两性/阴离子表面活性剂的协同效应获得油水超低界面张力的方法. 两性表面活性剂十六烷基磺基甜菜碱与高盐矿化水具有很好的相容性, 但在表面活性剂浓度为0.07%-0.39%(质量分数)范围内仅能使油水界面张力达到10^-2 mN·m^-1量级, 加入阴离子表面活性剂十二烷基硫酸钠后则可与原油达到超低界面张力. 通过探讨表面活性剂总浓度、金属离子浓度、复配比例对油水动态界面张力的影响, 发现两性/阴离子表面活性剂混合体系可以在高矿化度、低浓度和0.04%-0.37%的宽浓度范围下获得10^-5 mN·m^-1量级的超低界面张力, 并分析了两性/阴离子表面活性剂间协同获得超低界面张力的机制.     

DETERMINATION OF LONG-TERM STABILITY OF VITAMIN E EMULSION AND FORMATION OF MICROEMULSIONS BY USING LASER LIGHT SCATTERING AND UV ABSORPTION MEASUREMENTS

This paper presents methods of determining the long-term stability of vitamin E emulsion and formation of microemulsions. Several emulsion systems formed by using anionic, zwitterionic and cationic surfactants have been studied in the presence and absence of NaCI. Several conclusions can be drawn: (1) by using UV absorption and particle size measurements, one may be able to predict the long-term stability of an emulsion or the possibility of forming a microemulsion by measuring the initial properties of an emulsion, (2) in order to form a stable vitamin E emulsion or microemulsion, the initial properties of the emulsion should have the following features : (a) the particle size is ≤ 200 nm, (b) the surfactant system has a saturation value ≥ 1 and (c) the surfactant system can dissolve a substantial amount of vitamin E without causing an increase of the emulsion droplet size and (3) the saturation value and the stability of many vitamin E emulsion systems can be increased by adding an optimum amount of NaCI.     

Solubilization of phospholipid bilayers by C14-alkyl betaine/anionic mixed surfactant systems

The mechanisms governing the solubilizing interactions between zwitterionic/anionic mixed surfactant systems at different molar fractions of the zwitterionic surfactant (X _zwitter) and unilamellar liposomes were investigated. Solubilization was detected as a decrease in static lightscattering of liposome suspensions. Three parameters were regarded as corresponding to the effective surfactant/lipid molar ratios (Re) at which the surfactant system a) saturated the liposomesRe _sat; b) resulted in 50% solubilization of liposomesRe _50%, and c) led to a complete solubilization of these structuresRe _sol. These parameters corresponded to theRe at which light scattering stars to decrease, reaches 50% of the original value and shows no further decrease. From these parameters the surfactant partition coefficients for these three steps (K _sat,K _50% andK _sol) were also determined. The mixed systems were formed byN-tetradecyl-N, N-dimethylbetaine (C₁₄-Bet) and sodium dodecyl sulphate (SDS) in PIPES buffer at pH 7.20. Liposomes were formed by egg phosphatidylcholine and phosphatidic acid (9:1 molar ratio). When the range ofX _zwitter was about 0.4–0.6Re andK parameters showed a maximum, whereas the critical micelle concentration (CMC) of these systems exhibited a minimum. Given that the ability of the surfactant systems to solubilize liposomes is inversely related toRe _sol, this capacity appeared to be directly correlated with the CMC of the systems. The progressive rise ofK during the process indicates that an increasing surfactant partition equilibrium governs the interaction process from the saturation until the solubilization of vesicles, the free surfactant concentration remaining almost constant with similar values to the CMC for each mixed system studied.     

SPECTROPHOTOMETRIC STUDY OF THE THERMODYNAMICS OF COMPLEXATION OF LITHIUM AND SODIUM IONS WITH DIBENZO-24-CROWN-8 IN BINARY DIMETHYLFORMAMIDE-ACETONITRILE MIXTURES USING MUREXIDE AS A METALLOCHROMIC INDICATOR

Abstract

Complexation of Li⁺ and Na⁺ with dibenzo-24-crown-8 has been studied in dimethylformamide-acetonitrile mixtures by means of a competitive spectrophotometric technique using murexide as metal ion indicator. Stabilities of the resulting 1:1 complexes were investigated at various temperatures and enthalpies and entropies of complexation were determined from the temperature dependence of the formation constants. Sodium forms a more stable complex with the crown ether than lithium. There is an inverse linear relationship between log K_f and the mole fraction of DMF in the solvent mixtures. The ΔH°-TΔS° plot of all thermodynamic data, obtained for both crown complexes in different solvent mixtures, shows a fairly good linear correlation, indicating the existence of an enthalpy-entropy compensation effect in complexation.     

Inhomogeneous Distribution of Cationic Surfactants around Anionic Molecular Clusters

An interesting phenomenon is reported when uranyl peroxide nanoclusters U₆₀ (Li_48+mK₁₂(OH)_m[UO₂(O₂)(OH)]₆₀ (H₂O)_n, m≈20 and n≈310) interact with a small number of cationic surfactant molecules. Cationic surfactant molecules do not distribute evenly around the U₆₀ clusters during the interaction as expected. Instead, a small fraction of U₆₀ clusters attract almost all the surfactant molecules, leading to the self-assembly into supramolecular structures by using surfactant–U₆₀ complexes as building locks, and later further aggregate and precipitate based on hydrophobic interaction, whereas the rest of the clusters remained unbounded soluble macroions in bulk dispersion. This phenomenon nicely demonstrates a unique feature of macroion solutions. Considering that Debye–Hückel approximation is no longer valid in such solutions, the competition between the local electrostatic interaction and hydrophobic interaction becomes important to regulate the solution behaviors of macroions.     

On electronic states and bond lengths of the truncated icosahedral C60 molecule

The electronic states and the bond lengths of the truncated icosahedral C₆₀ molecule have been calculated by the Hückel and Coulson-Golebiewski self-consistent Hückel methods. C₆₀ has a stable closed shell with a rather big energy gap (= 0.847β) between the HOMO and the LUMO. We have obtained two kinds of bond lengths r₁ = 1.434 Å and r₂ = 1.403 Å, which correspond to the edges of the regular pentagon and the edge of a hexagon not lying on a pentagon.     

PdII Complexes of [44]‐ and [46]Decaphyrins: The Largest Hückel Aromatic and Antiaromatic,and Möbius Aromatic Macrocycles

Reductive metalation of [44]decaphyrin with [Pd₂(dba)₃] provided a Hückel aromatic [46]decaphyrin Pd^II complex, which was readily oxidized upon treatment with DDQ to produce a Hückel antiaromatic [44]decaphyrin Pd^II complex. In CH₂Cl₂ solution the latter complex underwent slow tautomerization to a Möbius aromatic [44]decaphyrin Pd^II complex which exists as a mixture of conformers in dynamic equilibrium. To the best of our knowledge, these three Pd^II complexes represent the largest Hückel aromatic, Hückel antiaromatic, and Möbius aromatic complexes to date.     

PdII Complexes of [44]‐ and [46]Decaphyrins: The Largest Hückel Aromatic and Antiaromatic,and Möbius Aromatic Macrocycles

Reductive metalation of [44]decaphyrin with [Pd₂(dba)₃] provided a Hückel aromatic [46]decaphyrin Pd^II complex, which was readily oxidized upon treatment with DDQ to produce a Hückel antiaromatic [44]decaphyrin Pd^II complex. In CH₂Cl₂ solution the latter complex underwent slow tautomerization to a Möbius aromatic [44]decaphyrin Pd^II complex which exists as a mixture of conformers in dynamic equilibrium. To the best of our knowledge, these three Pd^II complexes represent the largest Hückel aromatic, Hückel antiaromatic, and Möbius aromatic complexes to date.     

Binuclear paddle-wheel platinum(II) and platinum(III) complexes containing 4-methyl-4H-1,2,4-triazole-3-thiol ligand: Synthesis,X-ray studies,and spectroscopic characterization

The complex [Pt₂(μ-mtrzt)₄(mtrzt)₂] (1) was synthesized from the reaction of a mixture of 4-methyl-4H-1,2,4-triazole-3-thiol (Hmtrzt) and ethylenediamine (en) with K₂PtCl₄ in CH₃OH/H₂O (2:1) as solvent. The complex [Pt₂(μ-mtrzt)₄] (2) was synthesized by the same procedure as described for preparation of complex 1 but in the absence of ethylenediamine. Both complexes were characterized by elemental analysis, IR,¹H NMR,¹³C{¹H}NMR, UV-Vis, as well as luminescence spectroscopy and their structures were analyzed by single-crystal X-ray diffraction method. The X-ray structure determinations show that complexes of 1 and 2 have binuclear structures in a paddle-wheel fashion with Pt-Pt distances of 2.6628(7) and 2.7977(16)Å, respectively. In complex 1, each platinum(III) atom has a distorted octahedral coordination geometry with the sulfur atom and the second platinum subunit in axial positions and two nitrogen and two sulfur atoms in equatorial positions. Also, in complex 2, each platinum(II) atom has a distorted square-pyramidal coordination geometry with the second platinum subunit in axial position and two nitrogen and two sulfur atoms in equatorial positions. In addition, intermolecular C?H···N and C?H···S hydrogen bonds in 1 and 2 as well as intermolecular anagostic C?H···Pt and C?H···π interactions in 2 are effective in the stabilization of the crystal packing of these complexes.     

Interfacial Properties,Wettability Alteration and Emulsification Properties of an Organic Alkali–Surface Active Ionic Liquid System: Implications for Enhanced Oil Recovery

Combinatory flooding techniques evolved over the years to mitigate various limitations associated with unitary flooding techniques and to enhance their performance as well. This study investigates the potential of a combination of 1-hexadecyl-3-methyl imidazolium bromide (C₁₆mimBr) and monoethanolamine (ETA) as an alkali–surfactant (AS) formulation for enhanced oil recovery. The study is conducted comparative to a conventional combination of cetyltrimethylammonium bromide (CTAB) and sodium metaborate (NaBO₂). The study confirmed that C₁₆mimBr and CTAB have similar aggregation behaviors and surface activities. The ETA–C₁₆mimBr system proved to be compatible with brine containing an appreciable concentration of divalent cations. Studies on interfacial properties showed that the ETA–C₁₆mimBr system exhibited an improved IFT reduction capability better than the NaBO₂–CTAB system, attaining an ultra-low IFT of 7.6 × 10⁻³ mN/m. The IFT reduction performance of the ETA–C₁₆mimBr system was improved in the presence of salt, attaining an ultra-low IFT of 2.3 × 10⁻³ mN/m. The system also maintained an ultra-low IFT even in high salinity conditions of 15 wt% NaCl concentration. Synergism was evident for the ETA–C₁₆mimBr system also in altering the carbonate rock surface, while the wetting power of CTAB was not improved by the addition of NaBO₂. Both the ETA–C₁₆mimBr and NaBO₂–CTAB systems proved to form stable emulsions even at elevated temperatures. This study, therefore, reveals that a combination of surface-active ionic liquid and organic alkali has excellent potential in enhancing the oil recovery in carbonate reservoirs at high salinity, high-temperature conditions in carbonate formations.     

Effects of additional salts on the interfacial tension of crude oil/zwitterionic gemini surfactant solutions

Zwitterionic gemini surfactants, which have the advantages of both zwitterionic and gemini surfactants, have been widely used in various disciplines. Sulfobetaine-type zwitterionic gemini surfactants consisting of 1,2-bis[N-methyl-N-(3-sulfopropyl)-alkylammonium]ethane (2C_nSb with 6, 8 and 10 carbon atoms) were evaluated for their interfacial activities at the water/crude oil interface. The 2C₁₀Sb molecules showed a remarkable ability to decrease the interface tension (IFT) of water/crude oil, and the degree of decrease was much greater than those in either zwitterionic or gemini surfactant systems by at least two orders of magnitude. Furthermore, the effects of salts (NaCl, CaCl₂, and MgCl₂) on the IFT of the 2C₁₀Sb system were thoroughly investigated. Interestingly, the delicate balance between the effects of additional cations and the intramolecular interactions of 2C₁₀Sb molecules played crucial roles in the interfacial arrangements of 2C₁₀Sb molecules, which were mainly dependent on the bonding abilities of the cations. Moreover, a zwitterionic surfactant and a cationic gemini surfactant were employed in control experiments to verify the proposed mechanisms.     

Development of surface treated nanosilica for wettability alteration and interfacial tension reduction

The present study examines and compares the effect of surface treatments of nano-silica using internal olefins sulphonates (IOS_20–24 and IOS_19–23), anionic surfactants. The effect of surface modification on colloidal stability, wettability alteration and oil-water interfacial tension reduction were analyzed. Silica nanoparticles were characterized using Field Emission Scanning Electron Microscope (FESEM) and integrated energy-dispersive X-ray spectroscopy (EDX) before and after surface treatment. Using Turbiscan classic, the optimal nanosilica concentration and inspection of the coated particles dispersion stability with the help of light transmission behavior through the nanofluid was carried out. The stability was found to be enhanced as the mean light transmission declined only after surfactant treatment in both IOS coated nano-silicas but IOS_19–23 O-342 coated dispersions proved to be more stable among all three. RAME-HART Goniometer was used to perform interfacial tension (IFT) and contact angle measurements. IFT was found to be reduced by 48% after the surfactant treatment in case of IOS_19–23 O-342 coated nanosilica. Both surface treatments of nanosilica and increasing silica concentration caused significant reduction and altering wettability towards more water wet. The results revealed that IOS coatings improved the efficiency of NPs dispersion in terms of altered wettability and reduced IFT that mimics their potential for EOR applications.     

Characterization and traceability of two generations of standard reference material for the measurement of vitamin K1(phylloquinone) at endogenous concentrations in human plasma and serum

Vitamin K is an essential micronutrient required for blood coagulation, regulation of vascular calcification and bone mineralization. Plasma and serum measurements of vitamin K₁(phylloquinone, K₁) made using high-performance liquid chromatography with fluorescence detection, or tandem mass spectrometry are used clinically and in population studies to assess vitamin K status. Standard reference materials provide a validation tool for laboratories, helping assure clinical diagnosis and the comparability of data from different populations. We manufactured two K₁ standard reference materials, in 2009 (KEQAS SRM-001) and in 2019 (KEQAS SRM-002). The target concentrations of K₁ were assigned to each SRM using the All Laboratory Trimmed Mean of results reported by selected laboratories enrolled in the Vitamin K External Quality Assurance Scheme (KEQAS). The assigned concentrations of K₁ for KEQAS SRM-001 and SRM-002 were 0.25 and 0.36 μg/L respectively. In 2019 KEQAS SRM-001 was re-analysed simultaneously with KEQAS SRM-002 to provide traceability between the two standards, therefore aiding comparability of analysis performed using these materials. Both standards were stored as aliquots at −80°C in the dark; annual re-analysis of the materials indicated that K₁ is stable for at least 12 years in these conditions.