The Effect of a Background Electrolyte on the Viscosity of Aqueous Dodecyltrimethylammonium Bromide Solutions

Conductometry and viscometry have been employed to study the effect of a background electrolyte (KBr) taken in concentrations of 0.03 and 0.1 M on the critical micelle concentration of dodecyltrimethylammonium bromide (С₁₂ТАB) and the dependence of relative viscosity η/η₀ of С₁₂ТАB micellar solutions on the overall surfactant concentration. It has been found that, as a first approximation, each of these dependences may be represented as the sum of two linear portions. Concentrations c* of С₁₂ТАB micellar solutions, which correspond to the inflections between the two linear portions in the concentration curves of relative viscosity, have been determined. The Einstein equation η/η₀ = 1 + 2.5p (p is the volume fraction of the dispersed phase and 2.5 is a theoretical parameter that takes into account the spherical shape of the particles) has been transformed into a form corresponding to the concentration dependence of the relative viscosity on the overall surfactant concentration to make it applicable to the consideration of low-concentration systems, which are uncomplicated by intermicellar interaction. In particular, the applicability of the above equation for estimating micelle radii has been studied. It has been shown that the (η/η₀–1) = f(c/с₀₁–1) concentration dependences represented in bilogarithmic coordinates (c is the overall С₁₂ТАB concentration and c₀₁ is the critical micelle concentration) are linear in the absence of a significant intermicellar interaction and have slopes equal to unity. This fact may be considered as a criterion for the applicability of the Einstein equation to micellar solutions.     

溴化1-十二烷基-3-甲基咪唑与甲基橙的相互作用

利用电导法和表面张力法,研究了离子液体表面活性剂溴化1-十二烷基-3-甲基咪唑(C12mimBr)与阴离子染料甲基橙(MO)之间的相互作用。 通过分别测定C12mimBr、MO以及C12mimBr与MO混合溶液的电导率,计算了C12mimBr与MO的结合特性。 C12mimBr与MO以等摩尔比结合,在288.1、298.1和308.1 K下的结合常数分别为4.89×105、4.88×104和5.76×103 L/mol,该结合反应属于焓驱动的自发放热反应。 分别测定了C12mimBr与MO等摩尔混合体系及其在NaBr溶液中的临界胶束浓度(cmc),加入MO使C12mimBr的cmc从9.1×10-3 mol/L降低到7.3×10-5 mol/L,显著提高了C12mimBr的表面活性。     

Volumetric and Conductance Studies of Cetyltrimethyl Ammonium Bromide in Aqueous Glycine

Apparent molar volumes (? _v ), apparent molar adiabatic compressions (? _κ) and thermodynamic parameters of cetyltrimethyl ammonium bromide (CTAB) in 0.001, 0.01, 0.05 and 0.1 mol·dm^?3 aqueous solution of glycine in the temperature range 25–40 °C (at an interval of 5 °C) have been determined from density, speed of sound and conductometric measurements, respectively. The above calculated parameters were found to be sensitive to the interactions prevailing in the glycine–CTAB–water system. The analysis of the data was found to suggest that the ? _v and ? _κ values decrease sharply in the pre-micellar region and thereafter the decrease is almost linear at all concentrations of glycine, showing the dominance of hydrophobic interactions and facilitating the process of micellization. The ? _v and ? _κ values of these surfactants are found to be completely consistent with temperature over the entire concentration range. From conductance studies, the value of critical micelle concentration has been calculated, which shows dependence on the concentration of glycine as well as on temperature. A reasonably good qualitative correlation is found to exist with regard to CTAB–glycine interactions obtained from the conductance measurements and those from density and sound velocity measurements. All these observations demonstrate that this amino acid–surfactant system behaves in a different manner as compared to amino acid–electrolyte systems.     

Interaction Between 1-Dodecyl-3-Methylimidazolium Bromide and Sodium Carboxymethylcellulose in Aqueous Solution: Effect of Polymer Concentration

Effect of the concentration of water-soluble polyanion (sodium carboxymethylcellulose, NaCMC) on the interaction between a cationic surfactant (1-dodecyl-3-methylimidazolium bromide, C₁₂mimBr) and NaCMC in aqueous solution has been studied by isothermal titration microcalorimetry (ITC), conductivity, surface tension, and rheological measurements. From the surfactant/polymer interacting enthalpy, it can be deduced that the electrostatic attraction between the cationic surfactant and anionic polyelectrolyte causes an endothermic process, and the C₁₂mimBr monomers binding to the NaCMC chains to form micelle-like aggregates through hydrophobic interaction is an exothermic process. Increasing the NaCMC concentration causes the interaction between C₁₂mimBr and NaCMC to decrease, and the characteristic surfactant concentrations, including the critical aggregation surfactant concentration (CAC), the surfactant concentration to form free micelles (C_m), and the saturation concentration of surfactant on the NaCMC chains (C_S) to increase. Because of the strong electrostatic interaction between C₁₂mimBr and NaCMC, the formation of C₁₂mimBr/NaCMC complexes can lead to precipitation or redissolution depending on solution composition, so the critical precipitation concentration (C_P) and the onset of a redissolution concentration (C_R) has been determined by the electrical conductivity. The rheological results reveal a dramatic increase in solution viscosity around the CAC, attributed to interpolymer cross-linking through the formation of mixed micelles involving the carboxylic acid groups of NaCMC and the surfactant.     

离子液体1-烷基-3-甲基咪唑四氟硼酸盐在水溶液中的聚集行为

采用等温滴定量热法、静态荧光猝灭法和电导法系统研究了典型离子液体1-烷基-3-甲基咪唑四氟硼酸盐([Cnmim][BF₄])在水溶液中的聚集行为, 获得了胶束形成的临界胶束浓度(cmc), 摩尔焓变(ΔH_mic), 摩尔吉布斯自由能变(ΔG_mic), 摩尔熵变(ΔS_mic)以及不同浓度时[Cnmim][BF₄]胶束的平均聚集数等基本参数. 发现这类离子液体的聚集为熵驱动, 阳离子的烷基链越长, ΔG_mic越负, 聚集更容易发生. 此外, 结合[C_nmim]X (X=Cl^-, Br^-)的相关研究发现, 阳离子相同时, 体积越大和疏水性越强的阴离子与头基的结合能力越强, 能有效地降低头基之间的静电排斥, 降低cmc, 利于胶束的形成. 对于[C₁₂mim][BF₄], 添加剂β-环糊精(β-CD)的加入可使cmc增大, ΔH_mic和ΔS_mic减小, 而KBF₄则可使cmc和ΔH_mic减小, ΔS_mic增大.     

Physico-chemical Investigation of Mixed Micelle Formation Between Tetradecyltrimethylammonium Bromide and Dodecyltrimethylammonium Chloride in Water and Aqueous Solutions of Sodium Chloride

Conductometric measurements have been employed to gain a detailed insight into the interactions between two cationic surfactants, tetradecyltrimethylammonium bromide (TTAB) and dodecyltrimethylammonium chloride (DTAC), in water and in an aqueous solution of sodium chloride. The experimental data were analyzed according to Rubingh’s model within the framework of the pseudophase separation model. The evaluated values of critical micelle concentration (cmc) were found to be lower than their corresponding cmc ^id values, signifying attractive interactions involving both components in the solutions. The micellar mole fractions (\( X_{1}^{\text{Rub}} \)) of TTAB evaluated by Rubingh’s model were always larger than the ideal values (\( X_{1}^{\text{id}} \)), signifying the higher involvement of TTAB in mixed micelles of TTAB and DTAC. Activity coefficients (\( f_{ 1}^{\text{Rub}} \) and \( f_{ 2}^{\text{Rub}} \)) were always below one in all cases signifying synergism in the mixed micelles. All the outcomes point to synergism and attractive interactions in the mixed systems. Values of excess Gibbs energy were evaluated by employing Rubingh’s model (\( \Delta G_{\text{ex}}^{\text{Rub}} \)) and the \( \Delta G_{\text{ex}}^{\text{Rub}} \) values obtained are negative. The values of \( \Delta H_{\text{m}}^{\text{o}} \) and \( \Delta S_{\text{m}}^{\text{o}} \) reveal that hydrophobic interaction is expected to be the binding force between TTAB and DTAC in aqueous media at lower temperatures, while both hydrophobic interactions as well as exothermic interactions are involved at higher temperatures. The interaction forces between the surfactants were found to be enhanced in the presence of NaCl.     

Electrical Conductance and Volumetric Studies in Aqueous Solutions of Nicotinic Acid

Conductivity measurements of nicotinic acid and sodium nicotinate in dilute aqueous solutions were performed in the (288.15 to 323.15) K temperature range. The limiting equivalent conductances of the nicotinate anion, λ⁰(Nic⁻, T), and the dissociation constants of nicotinic acid, K(T), were derived by the use of the Onsager and the Quint and Viallard conductivity equations. Densities of aqueous solutions with molalities lower than 0.2 mol-kg⁻¹ were determined at 5 K temperature intervals, from T = (288.15 to 333.15) K. The measured densities were used to evaluate the apparent molar volumes, V_{2, φ}(m, T), the cubic expansion coefficients, α(m, T), and the changes of isobaric heat capacities with respect to pressure, (∂C_P/∂p)_{T, m}. They were qualitatively correlated with the changes in the structure of water when nicotinic acid is dissolved in it.     

Electrical Conductance and Volumetric Studies in Aqueous Solutions of DL-Pyroglutamic Acid

Conductivity measurements of DL-pyroglutamic acid and sodium pyroglutamate in dilute aqueous solutions were performed in the 288.15–323.15 K temperature range. The limiting molar conductances of pyroglutamate anion, λ^o(pGlu⁻, T) and the dissociation constants of pyroglutamic acid, K(T) were derived from the Onsager, and the Quint and Viallard conductivity equations. Densities of aqueous solutions with molalities lower than 0.5 mol-kg⁻¹ were determined at 5 K intervals from T = 288.15 K to 333.15 K. Densities served to evaluate the apparent molar volumes, V_2,φ(m, T), the cubic expansion coefficients, α (m,T) and the changes of the isobaric heat capacities with respect to pressure, (∂ C_P/∂ P)_T,m. They were correlated qualitatively with the changes in the structure of water when pyroglumatic acid is dissolved in it.     

溴代1-己基-3-甲基咪唑离子液体与丙酮的相互作用

1H and 13C NMR chemical shifts were determined to investigate the interactions of acetone with a room temperature ionic liquid 1-hexyl-3- methylimidazolium bromide C6mimBr at various mole fractions. Changes in chemical shifts of hydrogen nuclei and of carbon nuclei with the acetone concentration indicated the formation of hydrogen bond between anion of the ionic liquid and methyl protons of acetone. The NMR results were in good agreement with the ab initio computational results.     

Wormlike Micelle Formation and Rheological Behavior in the Aqueous Solutions of Mixed Sulfate Gemini Surfactant without Spacer Group and Dodecyltrimethylammonium Bromide

The rheological behavior of the aqueous solutions of mixed sulfate gemini surfactant with no spacer group, referred to as d‐C₁₂S, and dodecyltrimethylammonium bromide (C₁₂TABr) at a total concentration of 100 mmol·L⁻¹ but different molar ratios of C₁₂TABr to d‐C₁₂S (α₁) was investigated using steady rate and frequency sweep measurements. The wormlike micelles were formed over a narrow α₁ range of 0.20–0.27. The viscoelastic solutions exhibited Maxwell fluid behavior. At the optimum molar ratio of 0.25, the zero‐shear viscosity was as high as 600 Pa·s and the length of the mixed wormlike micelle was about 0.45–0.85 µm. The present result provides an example to construct long wormlike micelles by anionic gemini surfactant.     

Effect of L64 on the Phase Behavior of 1-Dodecyl-3-methylimidazolium Chloride/Water System

Phase behavior of ternary system involving surfactant‐like ionic liquid 1‐dodecyl‐3‐methylimidazolium chloride ([C₁₂mim]Cl), water, and nonionic surfactant PEO‐PPO‐PEO block copolymer (Pluronic L64) is investigated at 25°C. Hexagonal (H₁) and lamellar liquid crystal phase (Lα) are found in [C₁₂mim]Cl/H₂O/L64 system by using polarized optical microscopy (POM), small‐angle X‐ray scattering (SAXS) techniques and ²H NMR spectra. The phase structure (H₁ phase), which is formed in [C₁₂mim]Cl/H₂O binary system, is not changed when L64 with a low concentration is added. However, phase transitions will occur from hexagonal to multiphases of H₁ and cubic phases (C), then to Lα+C phases with constant [C₁₂mim]Cl/H₂O ratio and increasing L64 concentration. Moreover, at given L64 (5%, 20%) concentration, the lattice parameter of H₁ or Lα phase decreases with increasing [C₁₂mim]Cl/H₂O ratio. Fourier transform infrared (FTIR) spectra indicate that the H‐bonded network comprising an imidazolium ring, chloride ion and water formed in [C₁₂mim]Cl/H₂O binary system is disrupted upon addition of L64. This is helpful to the phase transition, due to the decreasing of interfacial curvature induced by dehydration of hydrated layer after the addition of PEO block of L64.     

1-正丁基-3-甲基咪唑溴化物离子液体TGA-FTIR研究

利用TGA-FTIR技术,研究了空气及氮气气氛下1-正丁基-3-甲基咪唑溴化物的热性能.结果表明,在不同的气氛下,在离子液体的沸点附近,存在一定的蒸汽压,随着温度的升高,1-正丁基-3-甲基咪唑溴化物主要以蒸气的形式汽化.在离子液体汽化过程中,未观察到离子液体发生明显的分解现象.在受热过程中,离子液体可能发生碳化作用,在空气气氛中,离子液体可能发生氧化作用,并且,离子液体的碳化速率与氧化速率基本接近.随着温度的升高,离子液体的氧化及碳化产物被进一步深度氧化.     

Thermophysical and Spectroscopic Studies of Pure 1-Butyl-3-methylimidazolium Tetrafluoroborate and Its Aqueous Mixtures

Intermolecular interactions in the aqueous mixtures of the room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF₄]), have been studied. The thermophysical properties: density ρ, speed of sound u, specific conductivity κ and refractive index n _D have been measured over the whole composition range at different temperatures (293.15–323.15 K) and are discussed. The results from thermophysical measurements are explained with the help of spectroscopy. In order to interpret the nature of molecular interactions occurring between [BMIM][BF₄] and water molecules, as well as to identify the moieties in which interactions are taking place, ¹H, ¹³C NMR and FT-IR spectra of the solutions have been studied. Excess molar volume V ^E, excess molar isentropic compressibility $ K_{S}^{\text{E}} $ , partial molar excess volume $ V_{i}^{\text{E}} $ , partial molar excess isentropic compressibility $ K_{S,i}^{\text{E}} $ , deviation in specific conductivity ?κ, and deviation in refractive index ?R have also been determined and analyzed to have a better understanding of the interactions taking place between the different components. Additionally, the excess ultrasonic speed u ^E and excess isentropic compressibility $ k_{S}^{\text{E}} $ , in terms of volume fractions, have been calculated and analyzed. It has been observed that temperature has a significant effect on the thermophysical properties of the studied system. Spectroscopic measurements confirm the disruption of ion-pair interactions of [BMIM][BF₄] and hydrogen-bonded network of water in the aqueous mixture of [BMIM][BF₄].     

Studies on Volumetric Properties of Concentrated Aqueous Solutions of the Ionic Liquid BMIBF4

In order to test the mole-fraction composition-based models as applied to aqueous solutions of an ionic liquid, the densities of aqueous 1-methyl-3-butylimidazolium tetrafluoroborate (BMIBF₄) were measured using a Westphal balance in the concentration range of about 0.2 to 0.85 mole fraction at temperatures from 283.2 to 323.2 K. Values of the apparent molar volumes of concentrated aqueous BMIBF₄ solutions were calculated from these densities and were represented with the Pitzer–Simomson and the Pitzer–Simomson–Clegg equations. The values of Pitzer–Simomson parameters and Pitzer–Simomson–Clegg parameters were obtained by fitting to experimental data with small standard deviations.     

The Adsorption of Dodecyltrimethylammonium Bromide on Mica in Aqueous Solution Studied by X-Ray Diffraction and Atomic Force Microscopy

The adsorption of dodecyltrimethylammonium bromide (DTAB) onto natural muscovite mica and a synthetic expandable mica (EM) in aqueous solution has been investigated using both microscopic and macroscopic surface characterization techniques. The electrokinetic properties of the surfaces were monitored as a function of the concentration of DTAB using atomic force microscopy and microelectrophoresis. The adsorption isotherm of DTAB on EM was measured up to a solution concentration just below the critical micelle concentration of the surfactant. The thickness of the adsorbed layer on EM was determined using X-ray diffraction. Results indicate that the adsorbed layer consists of molecules lying quite flat on the mica surface at low concentrations and adsorbed in interleaved aggregate structures at concentrations approaching the critical micelle concentration of the surfactant in solution. Copyright 2001 Academic Press.     

Study of Salt Effects on the Micelle-Monomer Exchange Process of Octyl-, Decyl-, and Dodecyltrimethylammonium Bromide in Aqueous Solutions by Means of Ultrasonic Relaxation Spectroscopy

Spreading of a tiny macroscopic droplet of a nonvolatile, completely wetting liquid over a flat solid is considered. A liquid in creeping is subjected to capillary forces and long-range molecular forces. The droplet may be surrounded with a precursor wetting film. This paper deals with the problem of determining of the microscopic parameter that influences the interface shape near the apparent line of wetting; this is regarded as the inverse problem in the hydrodynamics of wetting. If the system includes a precursor film, the microscopic parameter coincides with the maximum thickness of the film. A series of inverse equations for the microparameter is obtained, which relate it to, first, the current geometric parameters of the macroscopic drop part and, second, the spreading time. A method for determining how the microparameter depends on the wetting line speed is proposed. The theory expands the opportunity to perform macroscopic measurements and reveals additional parameters. The inverse relations may be used to experimentally study the growth of the maximum thickness of a precursor film during drop spreading. Copyright 2000 Academic Press.     

I>D-甘露醇在正丙醇和异丙醇水溶液中的体积性质

使用石英振荡管密度计精确测定了298.15 K温度下不同浓度的甘露醇-正丙醇-水和甘露醇-异丙醇-水三元溶液的密度. 计算了甘露醇的表观摩尔体积V_Φ和极限偏摩尔体积, 得到了其由纯水溶剂转移至混合溶剂中的迁移偏摩尔体积. 结果表明, 正丙醇在溶液中对甘露醇体积性质的影响较异丙醇显著. 从溶质-溶剂分子间相互作用及丙醇同分异构体中羟基位置的不同对体积性质的变化规律进行了讨论.     

Volumetric Properties of Aqueous Solutions of Cyclohexylsulfamic Acid

The mean apparent molar volume of cyclohexylsulfamic acid has been determined from the density data of aqueous solutions up to a molality of 0.540 mol⋅kg⁻¹ and at 293.15, 298.15, 303.15, 313.15, and 323.15 K. The mean apparent molar volume of the acid was divided into contributing ionic and molecular apparent molar volumes. The limiting apparent molar volume of the molecular acid amounts to (131.69± 0.02) cm³⋅mol⁻¹ and the limiting apparent molar expansibility to (0.130± 0.003) cm³⋅mol⁻¹⋅K⁻¹ at 298.15 K. From the limiting ionic and molecular apparent molar volumes the limiting volume change of ionization of cyclohexylsulfamic acid was calculated. A value of −7.76 cm³⋅mol⁻¹ was evaluated at 298.15 K. The temperature dependence of the volume change of ionization amounts to −(0.018± 0.009) cm³⋅mol⁻¹⋅K⁻¹. From the density data the coefficient of thermal expansion of the investigated solutions was calculated and from this the mean apparent molar expansibility of cyclohexylsulfamic acid was derived.     

Volumetric and Viscometric Studies on an Aqueous Urea Solution

Of late there has been a renewed inerest in the thermodynamics and other investigations on the behaviour of urea (denaturants) in aqueous solution which induce changes in structure and properties of proteins including their solubility, denaturation, dissociation into subunits and the activity of enzymes. With this in view, density and viscosity of aqueous urea solutions were determined as a function of concentration at 35, 40, 45, 50 and 55C, respectively. The apparent molal volume $(phi _v )$ of urea was found to be linear function of solute concentration. From the $phi _v$ versus molality ( m ) plot the apparent molal volume at infinite dilution, $phi _v^o$ (taken to be equal to partial molal volume, $bar V_2^o$ ) was determined. Viscosity coefficients B and D were calculated on the basis of the viscosity of the solutions and the solvent concerned using the Jones-Dole equation. The activation parameters for viscous flow $(Delta G^{ne} , ,Delta S^{ne} {rm and }Delta H^{ne} )$ were also calculated by means of the Eyring equation. The data were interpreted in terms of the structure making behaviour of urea in water at 35-55C temperature range.