Calorimetric investigation of the interaction between lithium perfluorononanoate and poly(ethylene glycol) oligomers in water

The interaction of lithium perfluorononanoate (LiPFN) with poly(ethylene glycol) (PEG) molecules of different molecular weights (300 < MW < 20000 Da) has been investigated in water at 298.15 and 308.15 K by isothermal titration calorimetry (ITC). Density, viscosity, and conductivity measurements were also performed at 298.15 K. The aggregation process of this surfactant on the PEG polymeric chain was found to be very similar to that exhibited by cesium perfluorooctanoate (CsPFO) and appears to be consistent with the necklace model. ITC titrations indicated that a fully formed LiPFN micellar cluster can be wrapped by a PEG chain having a molecular weight (MW) of approximately 3200 Da, longer than that required by the shorter perfluorooctanoate (MW approximately 2600 Da), and also suggested a stepwise mechanism for the aggregation of successive micelles. Viscosity data indicate that the formation of polymer-surfactant complexes between PEG and LiPFN involves a conformational change of the polymer. The aggregation of preformed micelles of LiPFN or CsPFO or SDS on the PEG polymeric chain always gives rise to further stabilization.     

Aggregation of cesium perfluorooctanoate on poly(ethylene glycol) oligomers in water

The interaction of cesium perfluorooctanoate (CsPFO) with poly(ethylene glycol) (PEG) of different molecular weight (300 < or = MW < or = 20000 Da) has been investigated at 298.15 K by isothermal titration calorimetry (ITC), density, viscosity, and conductivity measurements. Calorimetric titrations exhibited peculiar trends analogous to those already observed for sodium dodecyl sulfate (SDS). Micelles of the perfluorosurfactant, as compared to those of SDS, yield complexes with the polymer of similar thermodynamic stability but are able to interact with shorter PEG oligomers. The average number of surfactant molecules bonded per polymer chain at the saturation is about twice that observed for SDS. ITC data at 308.15 K indicate a larger thermodynamic stability of the aggregates but an almost constant stoichiometry. The peculiar thermal effects and the viscosity trend observed during the titration of an aqueous PEG solution with the surfactant appear consistent with a conformational change of the polymer. The PEG chain would evolve from a strained to an expanded conformation, induced by the growing of the surfactant micellar clusters bonded to the polymer, as suggested in a previous study of the PEG/SDS/H2O system.     

Calorimetric Study of the Aggregation of Lithium Perfluorohexanoate on Poly(ethyleneglycol) Oligomers in Water

The interaction of lithium perfluorohexanoate (LiPFHex) with poly(ethylene glycol) (PEG) of different molecular weights (600 Da≤ MW≤20000 Da) was investigated in aqueous solution at 25.00 °C by isothermal titration calorimetry (ITC). The interaction with one of the PEG polymers (MW=8000 Da) was also followed at the same temperature by viscosity and conductivity measurements. The aggregation pattern of this surfactant on the PEG polymeric chain was very similar to that exhibited by the homologous salts of perfluoroheptanoate, perfluorooctanoate and perfluorononanoate ions. The interaction enthalpies with PEG of this class of surfactants are always endothermic and decrease steeply with the decreasing length of the fluorocarbon chain. Experimental data from calorimetry, viscosity and conductivity consistently indicate a very small tendency of PEG polymers to wrap around the small LiPFHex micellar aggregates. The PFHex ion appears to be the shortest member of the series able to interact with a polyoxyethylenic chain. The same CF₂ contribution to the Gibbs energy of micellization or aggregation on the polymers was found within the series, indicating a common hydrophobic driving force for the two processes.     

Determination of the second critical micelle concentration of benzyldimethyltridecylazanium chloride in aqueous solution by acoustic and conductometric measurements

Density, speed of sound, and conductivity of benzyldimethyltridecylazanium chloride as a cationic surfactant in aqueous solutions have been measured as a function of concentration at atmospheric pressure and at five temperatures (293.15, 298.15, 303.15, 308.15, and 313.15) K. Isentropic compressibility values have also been calculated from the experimental density and speed of sound results. The critical micelle concentration (cmc) values of investigated cationic surfactant were evaluated by using conductivity measurements. The speed of sound, isentropic compressibility and also the conductivity values of the solutions have been employed to determine the second critical micelle concentrations (2nd cmc). The temperature dependence of the speed of sound and isentropic compressibility is shown to be sensitive to the aggregation process. The 2nd cmc values of the surfactant obtained at different temperatures by conductivity, speeds of sound and isentropic compressibility data are in agreement with each other.     

Thermodynamic characterization of 3-[(3-cholamidopropyl)-dimethylammonium]-1-propanesulfonate (CHAPS) micellization using isothermal titration calorimetry: temperature, salt, and pH dependence

A systematic investigation of the micellization process of a biocompatible zwitterionic surfactant 3-[(3-cholamidopropyl)-dimethylammonium]-1-propanesulfonate (CHAPS) has been carried out by isothermal titration calorimetry (ITC) at temperatures between 278.15 K and 328.15 K in water, aqueous NaCl (0.1, 0.5, and 1 M), and buffer solutions (pH = 3.0, 6.8, and 7.8). The effect of different cations and anions on the micellization of CHAPS surfactant has been also examined in LiCl, CsCl, NaBr, and NaI solutions at 308.15 K. It turned out that the critical micelle concentration, cmc, is only slightly shifted toward lower values in salt solutions, whereas in buffer media it remains similar to its value in water. From the results obtained, it could be assumed that CHAPS behaves as a weakly charged cationic surfactant in salt solutions and as a nonionic surfactant in water and buffer medium. Conventional surfactants alike, CHAPS micellization is endothermic at low and exothermic at high temperatures, but the estimated enthalpy of micellization, ΔHM0, is considerably lower in comparison with that obtained for ionic surfactants in water and NaCl solutions. The standard Gibbs free energy, ΔGM0, and entropy, ΔSM0, of micellization were estimated by fitting the model equation based on the mass action model to the experimental data. The aggregation numbers of CHAPS surfactant around cmc, obtained by the fitting procedure also, are considerably low (nagg ≈ 5 ± 1). Furthermore, some predictions about the hydration of the micelle interior based on the correlation between heat capacity change, Δcp,M0, and changes in solvent-accessible surface upon micelle formation were made. CHAPS molecules are believed to stay in contact with water upon aggregation, which is somehow similar to the micellization process of short alkyl chain cationic surfactants.     

Apparent molar volumes and compressibilities of electrolytes and ions in γ-butyrolactone

The densities of tetraphenylphosphonium bromide, sodium tetraphenylborate, lithium perchlorate, sodium perchlorate and lithium bromide in γ-butyrolactone at (288.15, 293.15, 298.15, 303.15, 308.15 and 313.15) K and speed of sound at 298.15 K have been measured. From these data apparent molar volumes V_Φ at (288.15, 293.15, 298.15, 303.15, 308.15 and 313.15) K and the apparent molar isentropic compressibility K_S,Φ, at T = 298.15 K of the salts have been determined. The apparent molar volumes and the apparent molar isentropic compressibilities were fitted to the Redlich, Rosenfeld and Mayer equation as well as to the Pitzer and Masson equations yielding infinite dilution data. The obtained limiting values have been used to estimate the ionic data of the standard partial molar volume and the standard partial isentropic compressibility in γ-butyrolactone solutions.     

Excess Volumes of 1-Alcohol + Heptane Mixtures at 298.15 and 308.15 K-Application of An Association Model with Flory Interaction Term

Abstract

The excess volumes of 1-pentanol+, 1-hexanol+, 1-heptanol+, 1-octanol+, 1-decanol+ and 1-dodecanol + heptane mixtures were evaluated at 298.15 and 308.15 K from the density data. The excess volumes were found to decrease with the increase in the carbon chain length of alcohol molecules. The temperature coefficient for the excess volumes was also observed to show a decreasing trend from 1-pentanol + to 1-dodecanol + heptane mixtures. The excess volumes were also calculated by combining the individual physical and chemical contributions, evaluated by combining an association model with Flory's free volume theory. Reasonable agreement between the experimental and calculated excess volumes for all the mixtures at 298.15 and 308.15 K was noted.     

Heat Capacity of Micellization of Lithium Perfluoroalkanoates in Aqueous Solution

Specific heats of aqueous solutions of lithium perfluoroalkanoates, from C₆ to C₉, were determined at 298.15 K at concentrations below and above the critical micelle concentration. Infinite dilution apparent molar heat capacities are compared with literature data for corresponding salts with different counterions. Heat capacities of micellization of these surfactants in water were calculated from the specific heat data and also by measurements of the heat of micellization at two temperatures, 298.15 K and 308.15 K. The data were treated under the assumption of the pseudo-phase separation model. The two series of data agree in the case of perfluorononanoate but diverge for perfluorosurfactants with shorter hydrophobic chains. The results are interpreted in terms of the extent of the applicability of the adopted chemical model. Heat capacities of the micellization process obtained from experimental specific heats compare well with literature values relative to the sodium salts of the examined anions.     

阴离子表面活性剂和β-环糊精包结作用

环糊精由于其特殊结构可与众多物质(客体分子)形成包结物,这种包结物在化学理论研究、化工工业、农业及医药等领域有广阔的应用前景[1、2],因而受到人们极大的关注.人们用电导法、核磁技术、表面张力法等研究了环糊精与阴离子表面活性剂的相互作用,但这些方法得出的结果很...     

Mixed Micellization Behavior of 12-2-12 Gemini Surfactant with Some Alkyltrimetyl Ammonium Bromide Surfactants

Mixed micellization behavior of dimeric cationic surfactant ethanediyl-1,2-bis (dimethyldodecylammonium bromide) (12-2-12) with a series of monomeric cationic surfactants dodecyltrimethyl ammonium bromide (DTAB), tetradecyltrimethyl ammonium bromide (TTAB), and cetyltrimethyl ammonium bromide (CTAB) has been studied in aqueous and aqueous polyvinylpyrrolidone (PVP) solutions at 298.15, 308.15, and 318.15 K, respectively, using conductometric method. Various thermodynamic parameters like mixed micelle concentration (C_m), micelle mole fraction (X₁), interaction parameter (β), and free energy of mixing (ΔG_ex) of the mixed systems have been determined and analyzed using Rubingh's regular solution theory. The results indicate that in aqueous solutions the binary mixtures of 12-2-12 with DTAB/TTAB behave nonideally with mutual synergism whereas that with CTAB shows almost ideal behavior at 298.15 K. At 318.15 K, all these binary mixtures exhibit antagonistic behavior. The effect of variation in chain length of alkyltrimethyl ammonium bromide surfactants on the interactions with 12-2-12 have also been evaluated and discussed.     

Essential oil deterpenation by solvent extraction using 1-ethyl-3-methylimidazolium 2-(2-methoxyethoxy) ethylsulfate ionic liquid

Taking into account that heat application can have undesirable effects in essential oil properties, liquid extraction comes up as a promising process instead of distillation for citrus oil deterpenation. In this work the suitability of using the ionic liquid 1-ethyl-3-methylimidazolium 2-(2-methoxyethoxy) ethylsulfate as a solvent for the extraction of linalool from citrus essential oil (which has been simulated as a mixture of limonene and linalool) has been analyzed. Liquid–liquid equilibrium data at three different temperatures (298.15 K, 308.15 K and 318.15 K) have been reported and successfully correlated using NRTL model. The best results were achieved using α = 0.1 for the systems at 298.15 K and 308.15 K and α = 0.2 at 318.15 K. The solute distribution ratio has showed values close to one and high values of selectivity have been achieved.     

Apparent molar volumes of lithium nitrate in 1-propanol + water in the temperature range from 288.15 to 318.15 K

Densities of 1-propanol+water+lithium nitrate mixtures have been measured with an oscillating-tube densimeter over a large range of concentrations of the salt and 1-propanol, at 288.15, 298.15, 308.15, and 318.15 K. From these densities, apparent molar volumes of lithium nitrate in 1-propanol+water mixtures have been calculated for each temperature, and apparent molar volumes at infinite dilution have been evaluated. An empirical correlation for partial molar volumes of lithium nitrate in 1-propanol+water mixtures with solvent composition and temperature has been derived.     

Thermodynamics of interaction between sodium bis(2‐ethylhexyl) sulfosuccinae and polymers in aqueous solutions by isothermal titration microcalorimetry

The interactions between sodium bis(2‐ethylhexyl) sulfosuccinae (AOT) and two nonionic water‐soluble polymers, including polyvinyl pyrrolidone (PVP) and polyethylene glycol (PEG) have been investigated by using isothermal titration microcalorimetry in aqueous solutions at 298.15 K. The results show that the critical aggregation concentration, which corresponding to the first turning point in the curve of experimental interaction heat versus concentration of the surfactant, is lower than the critical micellar concentration (cmc), confirming the existence of polymer‐surfactant interactions. The value of cac is not sensitive to the relative amount of polymer in low concentration range of the polymer. The mono‐layer saturated adsorption concentration, which corresponding to the second turning point, rises as the polymer concentration is increased. The interaction between PVP and AOT is stronger than that between PEG and AOT. The results also indicate that the aggregation of AOT in water and polymers solutions is entropically driven. The observed thermal effects have been interpreted in terms of the interactions of the polymer molecules with AOT monomers or the molecular clusters. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 275–283, 2006     

Volumetric Behaviour of Acrylic Esters (Methyl-, Ethyl-, and Butyl Acrylate) + 1-Alcohol (Heptanol,Octanol, Decanol and Dodecanol) at 298.15 K and 308.15 K

Abstract

New experimental data on densities and excess volumes (V^E) for methyl acrylate (MA)+, ethyl acrylate (EA)+, or butyl acrylate (BA)+1-heptanol, +1-octanol, +1-decanol and +1-dodecanol are reported at (298.15 and 308.15) K. The excess volumes were fitted to Redlisch-Kister type equation. The variations in excess volumes with the alkyl chain length of both the components are explained in terms of molecular interactions.     

水-正已烷-乙醇体系的液液平衡研究

近年来,超临界合成进展迅速。钟炳等人在超临界状态下利用正己烷、环已烷等液体介质,将一氧化碳合成甲醇[1],效率已达90%以上。作为基础工作,刘建国等人研究了水-正己烷-甲醇体系的液液平衡[2];冯耀声等人研究了水-丙烷-乙醇体系的相平衡[3];Letcher等人研究了水-正庚烷-醇体系     

Density,viscosity and refractive index for ethyl tert -butyl ether + 2-butoxyethanol mixtures

Densities (ρ) at 293.15, 298.15, 303.15, 308.15, and 313.15 K, viscosities (η) at 293.15, 298.15, and 303.15 K and refractive indexes (n) at 298.15 K of binary mixtures of ethyl tert-butyl ether (1) + 2-butoxyethanol (2), are reported. The excess molar volumes (V ^E) and the viscosities, and refractive index deviations (Δln η and Δn) were calculated from these experimental data. The results are discussed in terms of intermolecular interactions.     

Mixed micelles formed by n-octyl-beta-D-glucopyranoside and tetradecyltrimethylammonium bromide in aqueous media

Speed of sound, density, conductivity, and fluorescence spectroscopy experiments were run to analyze the mixed aggregation process of a nonionic-cationic surfactant system in aqueous media at 298.15 K. The mixed system comprises a nonionic surfactant, n-octyl-beta-D-glucopyranoside (OBG), and a cationic surfactant, tetradecyltrimethylammonium bromide (C14TAB), with 8 and 14 carbon atoms on the hydrophobic tails, respectively. From these data, the total and partial critical micellar concentrations, the total and partial aggregation numbers, apparent molar volumes and isentropic compressibilities, hydration numbers, and the corresponding changes in the latest properties due to the mixed aggregation process were determined. Pure and mixed micelles were analyzed from a geometrical point of view by determining the packing parameter of the aggregates. Furthermore, the experimental characterization of both the monomeric and micellar phases was completed with a theoretical study of the mixed micellization phenomena studied herein, by means of some of the most relevant theoretical models.     

Thermochemical study of aqueous solutions of lithium diclofenac at 293.15–318.15 K

The enthalpies of solution and dilution of aqueous solutions of lithium diclofenac (LiDC) are measured in the concentration range of 0.002–0.047m at 293.15, 298.15, 308.15, and 318.5 K using an isoperibolic calorimeter. The heat capacity of solid LiDC in the temperature range of 273.15–373.15 K is determined using a DSC 204 F1 Phoenix differential scanning calorimeter (NETZSCH, Germany). The virial coefficients of the enthalpy characteristics of a water-LiDC solution are derived in terms of the Pitzer model to calculate a wide range of thermodynamic properties of both the solution and its components. Changes in these characteristics as a function of concentration and temperature are discussed.     

Thermodynamic properties of solutions in the system <Emphasis Type="Italic">o</Emphasis>-xylene–di-2(ethylhexyl)phosphoric acid

The saturated vapor pressure in the temperature range of 298.15–308.15 K and the density of solutions in the o-xylene–di-2(ethylhexyl)phosphoric acid system at 298.15 K are measured. The activity coefficients of o-xylene in the above temperature range are calculated on the basis of the resulting data. The parameters of the thermodynamic model UNIQUAC are determined and analytical relationships are proposed to describe the bulk properties of the solution.