Calculation aspects of diffusion coefficients in micellar solutions of ionic surfactants

A method has been analyzed for calculating diffusion coefficients of 1 : 1 ionic surfactants as functions of their micellar solution concentrations within the framework of the quasi-chemical variant of the law of mass action. Relations have been presented for two- (with no allowance for micelles) and three-particle interaction (with allowance for micelles) formalisms. The methods for the introduction of initial calculation parameters and the calculation scheme for an ideal mixture of monomeric ions and micelles, as well as the correction for a deviation from ideality and a change in solution viscosity, have been considered. Numerical assessments have been performed by the examples of aqueous sodium dodecyl sulfate and alkyltrimethylammonium bromide solutions.     

Thermodynamic study of polyethylene-glycols in micellar solutions water+sodium dodecylsulfate

Interactions of a series of polyethyleneglycols (PEG) in aqueous micellar solutions of sodium dodecylsulfate (SDS) were investigated through thermodynamic properties. Volumes, heat capacities and enthalpies of dilution were measured at 25°C. The resulting transfer properties of PEG are reflecting hydrophobic interactions which increase with the polymer length and the hydrophilic interactions occurring in the aqueous polar layer of the micelles. Typically heat capacities clearly evidence various structural changes taking place in the micellar solutions.     

Kinetic micellar effects in tetradecyltrimethylammonium bromide-pentanol micellar solutions

The reactions 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane + OH(-) and 2-(p-nitrophenyl)ethyl bromide + OH(-) were studied in tetradecyltrimethylamonium bromide, TTAB, and TTAB-pentanol micellar solutions. The influence of changes in the surfactant concentration as well as changes in the hydroxide ion concentration on the observed rate constant was investigated. If changes in the cmc and ionization degree provoked by the presence of the different amounts of n-pentanol in the micellar solutions are taken into account, the experimental kinetic data can be rationalized quantitatively by using the PIE model. Assuming that the ion-exchange equilibrium constant, K(OH(-)/Br(-)), for the competition between the bromide and the hydroxide ions in all TTAB and in TTAB-pentanol micellar solutions studied is the same, a good agreement between the theoretical and the experimental kinetic data was found in all the micellar media for the two processes studied. This assumption was checked by experimentally determining the ion-exchange equilibrium constant K(OH(-)/Br(-)) in TTAB and TTAB-pentanol micellar solutions through a spectroscopic method, results showing that the presence of n-pentanol does not affect substantially the value of K(OH(-)/Br(-)). The second-order rate constants obtained from the fittings decrease slightly when the amount of pentanol increases, being greater than that in aqueous solution. This acceleration can be explained considering that micelles accelerate the reactions in which the charge is delocalized in the transition state.     

On the calculation of diffusion coefficients and aggregation numbers of nonionic surfactants in micellar solutions

The calculation of the diffusion coefficients of nonionic surfactants as functions of their concentrations in micellar solutions has been analyzed within the framework of the quasi-chemical version of the law of mass action. The methods of the introduction of initial calculation parameters, calculation scheme for an ideal mixture of monomeric molecules and micelles, and corrections for varying solution viscosity have been considered. Numerical estimations have been performed using aqueous tetraoxyethylene octyl ether, pentaoxyethylene hexyl ether, and octyl-β-D-glucopyranoside solutions as examples.     

Unusual features of micellar diffusion

Diffusion coefficients of tetradecyltrimethylammonium bromide in aqueous solutions have been determined at 25, 95 and 135 °C using the Taylor dispersion technique. The diffusion coefficient exhibits a minimum at a surfactant concentration above the critical micelle concentration (CMC). The results are interpreted in terms of electrostatic coupling and rapid exchange between micelle, surfactant monomer and counterions.     

Two-photon absorption in aqueous micellar solutions

Addition of the surfactant sodium dodecyl sulfate at concentrations above the critical micelle concentration increases the fluorescence quantum yield and the two-photon absorption cross-section of charged [2.2]paracyclophane chromophores containing pairs of D-pi-D chromophores. The resulting spectra in the micellar solutions are very similar to those obtained for neutral isostructural analogues in toluene. The measured etadelta values are 1300 GM for 1C and 1920 GM for 2C, which are comparable or larger to those in toluene. These results highlight possible misleading interpretation of two-photon-induced emission for evaluating the concentration of labeled substrates used in two-photon microscopy and provide guidelines for designing molecular structures with optimized two-photon action cross-sections in water.     

Inferences on dynamic water structure in aqueous solutions from diffusion measurements

The dynamic, hydrogen-bonded structure of water can be profoundly affected by addition of solutes as reflected by the resulting solute—solvent interactions. Measurements of diffusion coefficients for the solute species and for water are a useful probe for studying those interactions and changes in the dynamic water structure.

The analysis of transport properties of electrolyte solutions is presently approached both theoretically and experimentally by the use of generalised transport coefficients such as Onsager phenomenological coefficients, velocity correlation coefficients or the closely related distinct diffusion coefficients of Friedman. However, two of these approaches generally use a solvent-fixed frame of reference and thereby exclude the information available from studying the diffusion of the solvent.

The velocity correlation coefficient approach is used here to examine hydrogen-bonding effects in binary solution containing water as one component. We discuss also examples where intra-diffusion data for water in aqueous solutions give important insights into the dynamic structure of aqueous solutions.     

Shear banding structure in viscoelastic micellar solutions

 Theoretically, it has been shown that worm-like micellar solutions of surfactant can, for a shear rate γ˙ greater than a critical value γ˙_c, undergo a transition giving a plateau evolution (σ=σ_c) of the shear stress σ against shear rate γ˙. We report here on a experimental study of the linear and nonlinear rheological behaviour of aqueous CTAB solutions with NaNO₃ as added salt. With this system, it is possible to observe the evolution of the fundamental characteristics of the flow curve, i.e., the shear rate γ˙_1c at which a shear banding structure appears and the second critical shear rate γ˙_2c characterizing the end of the shear stress plateau followed by a new increased shear stress. For the first time, experimentally, we obtained evidence for the existence and the evolution of γ˙_2c against CTAB and salt concentrations and temperature variations. Experimental results are compared to theoretical predictions correlating σ_c, γ˙_1c and G ₀ (the shear modulus) for Maxwellian micellar solutions. Received: 4 July 1996 Accepted: 19 November 1996     

Size distribution of aggregates in micellar solutions

A general expression for the equilibrium size distribution of polydisperse ionic aggregates in micellar solutions is proposed. This expression accounts for the interactions between the micelles. The interaction is modeled via screened electrostatic potential. Asymptotic formulae for nearly monodisperse case and for high polydispersity of the micelles are presented. The results show that the interactions lead to the stabilization of the monodispersity in the first case. In the second case the interactions cause an increase in the polydispersity of the micellar solution.     

Dynamics of molecular oxygen in micellar solutions

Fluorescence quenching by molecular oxygen has been employed to estimate dynamic parameters and solubility characteristics of molecular oxygen in micelle forming detergent solutions. A kinetic model which assumes that oxygen quenching occurs only in the micellar phase is employed to analyze the data.     

The solubilization of alcohols in micellar solutions

The specific conductivities of dodecyldimethylbenzylammonium bromide (C12BBr) have been determined in aqueous butanol and aqueous benzyl alcohol solutions in the temperature range of 5-40°C. From these data the temperature dependent critical micelle concentration (cmc) was determined. The molar fraction of alcohol in the micelle was estimated using the theory suggested by Motomura et al. for surfactant binary mixtures. The thermal properties such as standard Gibbs free energy, enthalpy and entropy of solubilization of alcohols in the micelles were estimated for the phase separation model. The change in heat capacity upon solubilization of alcohol in the micelle has been estimated form the above properties. This revised version was published online in July 2006 with corrections to the Cover Date.     

Counterion condensation and release in micellar solutions

Counterion condensation and release in micellar solutions are investigated by direct measurement of counterion concentration with ion-selective electrode. Monte Carlo simulations based on the cell model are also performed to analyze the experimental results. The degree of counterion condensation is indicated by the concentration ratio of counterions in the bulk to the total ionic surfactant added, alpha< or =1. The ionic surfactant is completely dissociated below the critical micelle concentration (cmc). However, as cmc is exceeded, the free counterion ratio alpha declines with increasing the surfactant concentration and approaches an asymptotic value owing to counterion condensation to the surface of the highly charged micelles. Micelle formation leads to much stronger electrostatic attraction between the counterion and the highly charged sphere in comparison to the attraction of single surfactant ion with its counterion. A simple model is developed to obtain the true degree of ionization, which agrees with our Monte Carlo results. Upon addition of neutral polymer or monovalent salts, some of the surfactant counterions are released to the bulk. The former is due to the decrease of the intrinsic charge (smaller aggregation number) and the degree of ionization is increased. The latter is attributed to competitive counterion condensation, which follows the Hefmeister series. This consequence indicates that the specific ion effect plays an important role next to the electrostatic attraction.     

Acid-base and tautomeric equilibria of fluorescein dyes in water micellar solutions of zwitterionic sulfobetaine surfactant

Ionization constants of fluorescein and six its derivatives in water micellar solutions of zwitterionic surfactant, N-cetyl-N,N-dimethyl-3-ammonium-1-propanesulfonate were evaluated spectrophotometrically. On the basis of absorption spectra of dyes conclusions concerning the tautomerism of molecular and ionic forms were made and the relationships between the pK _a values were explained.     

Thermal analysis of aqueous micellar solutions

A micro differential temperature scanning calorimeter was used to characterize the structural changes between different types of micelles in aqueous solutions of ionic surfactants: anionic — sodium dodecylsulfate (SDS) — and cationic — hexadecyltrimethyl ammonium bromide (CTAB). Moreover, this technique allowed to confirm the existence of peculiar types of complexes between surfactants and selected solutes. In SDS solutions containing polyethylene glycols (PEG), the presence of complexes formed by small micelles adsorbed along the chains of the polymers was evidenced in the case of long enough polymer chains. In CTAB-phenol solutions, due to strong interactions between the polar heads of surfactant and phenol, molecular complexes of a composition of 1:1 molar ratio have been characterized. Depending on the ratio [phenol]/[CTAB], the rheological behaviour was found to change from fluid to viscoelastic and gel-like solutions, owing to the growth of elongated rod-like micelles. With entangled worm-like micelles, the important role of kinetics to reach the thermodynamic equilibria was shown.     

Microfluidic flows of wormlike micellar solutions

The widespread use of wormlike micellar solutions is commonly found in household items such as cosmetic products, industrial fluids used in enhanced oil recovery and as drag reducing agents, and in biological applications such as drug delivery and biosensors. Despite their extensive use, there are still many details about the microscopic micellar structure and the mechanisms by which wormlike micelles form under flow that are not clearly understood. Microfluidic devices provide a versatile platform to study wormlike micellar solutions under various flow conditions and confined geometries. A review of recent investigations using microfluidics to study the flow of wormlike micelles is presented here with an emphasis on three different flow types: shear, elongation, and complex flow fields. In particular, we focus on the use of shear flows to study shear banding, elastic instabilities of wormlike micellar solutions in extensional flow (including stagnation and contraction flow field), and the use of contraction geometries to measure the elongational viscosity of wormlike micellar solutions. Finally, we showcase the use of complex flow fields in microfluidics to generate a stable and nanoporous flow-induced structured phase (FISP) from wormlike micellar solutions. This review shows that the influence of spatial confinement and moderate hydrodynamic forces present in the microfluidic device can give rise to a host of possibilities of microstructural rearrangements and interesting flow phenomena.     

Partial molar enthalpies in “inverted micellar” solutions of water and sodium octanoate in decanol

Summary The relative molar enthalpy of solutions with three constant molar ratios of water to sodium octanoate in the isotropic decanol-rich solution phase, L₂, of the system water — sodiumn-octanoate -n-decanol have been determined by means of calorimetry at 2° C. A method of calculating the relative partial enthalpies of the components from these data is described. It is the thermic interaction of the sodium octanoate that dominates the properties throughout the extent of the phase studied. Where the decanol content is highest, the partial enthalpies of the sodium octanoate and the water increase sharply while the partial enthalpy of the decanol remains relatively constant throughout the extent of the phase. This agrees well with the general view that aggregation into inverted micelles takes place as a continuous process and that the properties of the aggregates remain constant.

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Zusammenfassung Die relative molare Enthalpie von Lösungen mit drei konstanten Molverhältnissen Wasser/Natriumoktanoat in der isotropen dekanolreichen Lösungsphase, L₂, in dem System von Wasser-NatriumN-Oktanoat —N-Dekanol wurde kalorimetrisch bei 25°C bestimmt. Außerdem wurde ein Verfahren angegeben, um die relativen partiellen Enthalpien der Komponenten aus diesen Daten zu berechnen. Die thermische Wechselwirkung des Natriumoktanoates bestimmt die Eigenschaften der untersuchten Phase. Wo die Dekanolgehalte am größten sind, nehmen die partiellen Enthalpien von Natriumoktanoat und Wasser noch zu, während die partielle Enthalpie von Dekanol relativ konstant bleibt, Das stimmt gut überein mit der allgemeinen Auffassung, daß die Aggregation zu inverted micelles durch einen kontinuierlichen Prozeß geschieht und daß die Eigenschaften der Aggregate konstant bleiben.

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With 5 figures and 3 tables     

Fast dynamics of wormlike micellar solutions

We present the first measurements of the fast dynamics of cationic wormlike micelles (WLM) using neutron spin echo (NSE). The comparison with theory [Zilman, A.; Granek, R. Phys. Rev. Lett. 1996, 77, 4788. Granek, R. J. Phys. II 1997, 7, 1761]1,2 enables coarse grained parameters to be identified. We propose and validate a calibration procedure to extract the bending constant kappa from NSE measurements.     

Scattering theory for threadlike micellar solutions

Association-dissociation equilibria and the static scattering function were formulated using precise thermodynamic functions for nonionic surfactant solutions including long, stiff, threadlike micelles. The present theory is applicable for micellar solutions with the surfactant concentration much higher than the critical micelle concentration and containing highly growing threadlike micelles. The scattering function formulated was compared with experimental light scattering data for aqueous solutions of a nonionic surfactant, penta(oxyethylene glycol) n-decyl ether (C12E5), at different surfactant concentrations and also temperatures.     

SANS-measurements on micellar solutions of perfluoro-detergents

Small-angle-neutron-scattering-(SANS)-measurements were carried out with soulutions of Tetramethylam-moniumperfluoroctanesulfonate (TMAFOS) and Diethylammoniumperfluorononanoate (DEAFN) in pure D₂O and in mixtures of D₂O and H₂O. For the TMAFOS-solutions the experimentally observed scattering functions, i.e. the coherent scattering intensity as a function of the scattering angles, could be fitted very well for large scattering angles with the theoretically calculated scattering function for rodlike particles and the dimensions of the rods could be evaluated from these fits. The radius of the rods was independent of the detergent concentration and equal to the double length of a detergent molecule. For small scattering angles the scattering function showed a maximum which was due to nearest neighbour order between the aggregates resulting from the intermicellar interaction. From this maximum a mean distance between the aggregates and hence the lengths L of the rods could be calculated.For the DEAFN-solutions the observed scattering function showed no maximum what clearly indicates the absence of nearest neighbour order between the aggregates. The experimentally observed scattering functions could not be fitted on the basis of rodlike aggregates, but agreed rather well with the theoretically calculated scattering functions for disclike aggregates and also for vesicle-like double layers. The dimensions for the discs could be evaluated from the fits.