Volume behavior of mixed micelles of dodecyltrimethylammonium chloride and bromide

Densities of aqueous solutions of mixtures of dodecyltrimethylammonium chloride (DTAC) and dodecyltrimethylammonium bromide (DTAB) have been measured as a function of total molality at constant composition and the apparent molar volumes of the mixtures were derived from the density data. The partial molar volumes of monomeric surfactant mixtures, the molar volumes of mixed micelles, and the volumes of formation of mixed micelles were evaluated and are compared with those for decyltrimethylammonium bromide (DeTAB) and DTAB mixtures. The partial molar volumes of monomeric surfactant mixtures and the molar volumes of mixed micelles are observed to depend linearly on the monomer and micelle compositions, respectively. Although the volume of formation of mixed micelles of the DeTAB-DTAB mixture depends on the micellar composition, that of the DTAC-DTAB mixture is observed to be almost independent of the micellar composition. This suggests that the volumes of the counter ions in the micellar solutions are almost equal to those in the monomeric solutions.     

Standard partial molar volumes of alcohols in aqueous dodecyltrimethylammonium bromide solutions

Density measurements of water-dodecyltrimethylammonium bromide (DTAB)-alcohol ternary systems as a function of alcohol and surfactant concentrations were carried out at 25°C. The alcohols were propanol (PrOH), 2-propanol (2-PrOH) and hexanol (HexOH). The apparent molar volume V_,R of alcohols have been calculated and the standard (infinite dilution) partial molar volumes of alcohols V _R at each surfactant concentration were obtained by means of a least squares fit of V_,R vs. the alcohol concentration. The V _R vs. surfactant concentration curves have been rationalized in terms of the partial molar volume of alcohol in the aqueous V _f and the micellar V _b phases and the distribution constant of alcohol between the aqueous and the micellar phases K. The V _b values for PrOH and HexOH together with those of butanol and pentanol previously reported satisfy the additivity rule giving a methylene group contribution of 16.7 cm³-mol^–1 which is identical to that reported in the literature from the study of pure liquid alcohols. No difference between V _b for PrOH and 2-PrOH has been found. From density data of water-alcohol and water-surfactant binary systems and of water-surfactant-alcohol ternary system, the apparent molar volume of the surfactant in the water-alcohol mixed solvent V_,S have been calculated as a function of the surfactant concentration and of the mixed solvent composition. The effect of the alkyl chain length of the alcohols and the effect of isomerization of the alcohols on the V_,S vs. surfactant concentration trends have been analyzed.     

Thermodynamic properties of water-β-cyclodextrin-dodecylsurfactant ternary systems

Densities, heat capacities and conductivities of water-surfactant--cyclodextrin (-CD) ternary systems were determined at 25°C. The surfactants studied were sodium dodecylsulfate (NaDS) and dodecyltrimethylammonium bromide (DTAB). From conductivity data, apparent critical micelle concentrations (cmc^*) and degree of ionization of micelles were obtained at a fixed -CD concentration (m_CD). From the cmc^* value and that in water (cmc) the stoichiometry of the surfactant--CD complex was calculated. At a given m_CD, the apparent molar volume V_,CD and heat capacity C_,CD of -CD in the two surfactants were calculated as functions of surfactant concentration m_S. For both NaDS and DTAB, V_,CD increases with m_S up to about the cmc beyond which it decreases to a constant value at high m_S, the opposite is observed for C_,CD. With NaDS, a jump in the C_,CD vs, m_S trend was detected and ascribed to a structural NaDS micellar transition. The apparent molar volume V_S and heat capacity C_S of NaDS and DTAB in the water--CD mixture 0.017 m were also obtained. From these properties and those in pure water, the volume V_S and heat capacity C_S of transfer of the surfactant from water to water+-CD mixture as functions of m_S were calculated. For both surfactants, the V_S vs. m_S trends increase to the cmc and then decrease in a monotonic manner, whereas C_S increases regularly with m_S in the pre-micellar region and is essentially constant in the post-micellar region. The V_S vs. m_S trends were qualitatively explained in terms of dispersed, complexed and micellized surfactant contributions.     

A Volumetric Study of Water–Decyltrimethylanimonium Bromide–Pentanol Ternary System from 25 to 130°C at 2 and 19 MPa

Density measurements on decyltrimethylammonium bromide (DeTAB)–water and pentanol (PentOH)–DeTAB–water systems as functions of both alcohol and surfactant m _S concentrations were carried out at 2 and 19 MPa from 25 to 130°C. From experimental data for the water–DeTAB binary system, the standard (infinite dilution) partial molar volumes, expansibilities, and compressibilities of DeTAB, and the corresponding properties in the micellar phase are calculated. The trends of the standard partial molar volumes of PentOH V _R ^o in DeTAB micellar solutions as functions of m _S reflect the transfer of PentOH from the aqueous to the micellar phase, except at 130°C and 19 MPa. On the basis of an equation previously used, the distribution constant of PentOH between the aqueous and the micellar phases and the standard partial molar volume of alcohol in the aqueous and the micellar phases are obtained from V _R ^o data. Comparisons with data for PentOH in dodecyltrimethylammonium bromide are made.     

Micelle Formation by Sodium Perfluorooctanoate and Decyltrimethylammonium Bromide in 18-Crown-6 + β-Cyclodextrin + Water Systems

The conductances of sodium perfluorooctanoate (SPFO) and decyltrimethylammoniumbromide (DeTAB) have been determined in 18-crown-6 + water (CR + W). -cyclodextrin + water(CD + W) and in CR + CD + W mixtures with a fixed 0.0151 mol dm^–3 concentration of CR andvarying amounts of CD with overall change in the mole fraction range of CD from 0.0 to 0.5 in CR +CD + W mixtures at 30°C. From the conductivity data, the critical micellar concentration (cmc), thedegree of counter-ion association () the free energy of transfer of the surfactant hydrocarbon chainfrom the medium to the micelle (G _HP ⁰ ), and the free energy of transfer of surface contributions(G _S ⁰ ) of SPFO and DeTAB have been computed. It has been found that the micelles of SPFO arestabilized in CR + W mixtures in comparison to pure water, whereas micelles of DeTAB remain comparatively unaffected upon addition of CR in water. On the other hand, micelles of SPFO andDeTAB are denatured upon addition of CD in CR + CD + W mixtures. The denaturation effect isstronger on the micelles of SPFO in comparison to that of DeTAB.     

Energetics of sodium dodecylsulfate-dodecyldimethylamine oxide mixed micelle formation

Enthalpies of dilution and osmotic coefficients of the sodium dodecyl-sulfate (NaDS)-dodecyldimethylamine oxide (DDAO) mixtures in water have been measured at 25 and 37°C, respectively. From the enthalpies of dilution the apparent molar relative enthalpies L were calculated. The change of the L vs. total molality m_t profiles with the mole fraction reflects the variation of the ionic character of the mixed micelles. From the osmotic coefficients the nonideal free energy G ₂ ⁿⁱ were calculated. By combining G ₂ ⁿⁱ with the partial molar relative enthalpies, the nonideal entropies TS ₂ ⁿⁱ were determined. At a given mole fraction, G ₂ ⁿⁱ and TS ₂ ⁿⁱ values are decreasing and increasing respectively, tending to become constant at high m_t. The excess properties for the mixed micelle formation were evaluated as a function of the mixture composition at some m_t. The profiles are compared with those obtained from thermodynamics of binary liquid mixtures and the regular solution theory.     

The selectivity in MEKC of pseudo-stationary phases based on polyelectrolyte complexes: I. composition of the complex

Polyelectrolyte–surfactant complexes (PSC) of polycarboxylic acids with alkyl-trimethylammonium salts look very promising as a new type of pseudo-stationary phase in micellar electrokinetic chromatography. PSC produce an intramolecular micellar phase, and the morphology of the micelles is significantly different from that of the corresponding typical surfactant micelles. Pseudo-stationary phases based on PSC have unique selectivity. In this paper, the effect of the composition () of the PSC of polyacrylic acid (PAA) M_W 130,000 with dodecyltrimethylammonium bromide (DTAB) and of the PSC of PAA M_W 450,000 with DTAB on the separation of DNS–amino acids and phenol derivatives in these systems was investigated. Relative retention and relative selectivity were used to describe the electrophoretic behavior of the amino acids and phenol derivatives. The main advantage of PSC pseudo-phases is that the nature and the structure of micelle-like units, and hence the selectivity of electrophoretic separation, could easily be modified by changing the composition of the complex.     

Volumes and compressibilities of pentanol in aqueous dodecyltrimethylammonium bromide solutions at 15, 25 and 35°C

Ultrasonic velocities and densities of the water-dodecyltrimethylammonium bromide (DTAB)-pentanol (PentOH) ternary system were measured at 15, 25 and 35°C as a function of the surfactant and alcohol concentrations. The apparent molar volumes and isentropic compressibilities of PentOH were calculated. The standard partial molar volumes increase with surfactant concentration continuously whereas the standard partial molar isentropic compressibilities show sharp changes in slope at about 0.25 mol-kg^–1 DTAB, which can be ascribed to a micellar structural transition. The volume data for alcohol in micellar solutions were treated by a model reported for the distribution of polar additives between aqueous and micellar phases. In the application of the model to compressibility, the contributions due to the pressure effect on the shift of both the micellization equilibrium and the alcohol distribution constant cannot be neglected. This is in contrast to what is found in the case of heat capacity. The distribution constant and the partial molar volumes and compressibilities of PentOH in the micellar phase have been derived by linear regression. Also, the apparent molar volumes and isentropic compressibilities of DTAB in water-pentanol mixed solvents at fixed composition have been calculated. These properties as a function of the surfactant concentration show maxima depending on the temperature and the mixed solvent composition. The decrease beyond the maximum can be attributed to the extraction of PentOH from the aqueous into the micellar phase, where its concentration tends to zero with the progressive increase of the surfactant concentration. As a consequence, by increasing the surfactant concentration, the apparent molar properties of the surfactant in the mixed solvent shifts towards the value in water.     

Kinetics of the solvolysis oftrans-dichlorotetra-(4-t-butylpyridine)-cobalt(III) ions in water +t-butyl alcohol mixtures

Rates of solvolysis of the complex cation [Co(4tBupy)₄Cl₂]⁺ have been determined in mixtures of water with the hydrophobic solvent, t-butyl alcohol. The solvent composition at which the extremum is found in the variation of the enthalpy H^* and the entropy S^* of activation correlates well with the extremum in the variation of the relative partial molar volume of t-butyl alcohol in the mixture and the straight line found for the variation of H^* with S^* is coincident with the same plot for water + 2-propanol mixtures. A free energy cycle is applied to the process initial state (C ⁿ⁺) going to the transition state [M⁽ⁿ⁺¹⁾⁺...Cl^–] in water and in the mixture using free energies of transfer of the individual ionic species, G _t ^o (i), from water into the mixture. Values for G _t ^o (i) are derived from the solvent sorting method and from the TATB/TPTB method: using data from either method, changes in solvent structure on going from water into the mixture are found to stabilize the cation in the transition state, M⁽ⁿ⁺¹⁾⁺, more than in the initial state, C ⁿ⁺. This is compared with the application of the free energy cycle to the solvolysis of complexes [Co(Rpy)₄Cl₂]⁺ and [Coen₂LCl]⁺ in mixtures of water with methanol, 2-propanol or t-butyl alcohol: the above conclusion regarding the relative stabilization of the cations holds for all these complexes in their solvolyses in water+alcohol mixtures using values of G _t ^o (Cl^–) from either source.     

Mixed Micelles in the Presence of Macrocyclic Additives: A Host–Guest Conductometric Study

The conductances of sodium dodecylsulphate (SDS) + sodium decylsulfate (SDeS) and decyltrimethylammonium bromide (DeTAB) + tetradecyltrimethylammonium bromide (TTAB) over the entire mole fraction range of SDS (_SDS) or DeTAB (_DeTAB) were measured in water, 18-crown-6 ether + water (CR + W) and -cyclodextrin + water (CYC + W) mixtures at fixed 4 mM and 8 mM of CR or CYC in their respective binary mixtures at 30 °C. The conductivity plots for SDS + SDeS mixtures show a single break whereas two breaks are observed at most of the _DeTAB for DeTAB + TTAB mixtures. From the break in the conductivity data, the mixed critical micellar concentration (cmc) and degree of counter-ion association () were computed. The first break corresponds to the classical cmc of TTAB is termed as the first cmc (C₁) and the second break which is observed at concentrations about 4 times the first one, corresponding to the classical cmc of DeTAB and is considered to be the second cmc (C₂). The non-ideality in SDS + SDeS mixtures has been evaluated by using the regular solution theory and it has been observed that the mixture is close to ideal in the absence and presence of additives. The variation in C₁, C₂ and ₁, ₂ for DeTAB + TTAB has been discussed in terms of the mixed micelle formation which are predominantly rich in the TTAB and DeTAB monomers respectively.     

Excess volumes and viscosities of mixtures of dimethylsulfoxide with normal alcohols at 40°C

Excess volumes and viscosities have been determined for DMSO + n-hexanol, + n-heptanol, + n-octanol, and + n-decanol at 40°C. The excess partial molar volumes V ₁ ^E , changes in viscosities , the parameter d of the Grunberg and Nissan expression, and excess Gibbs free energies of activation of flow G _* ^E have been calculated from the experimental data. All the excess volumes are positive over the whole composition range, with V ^E increasing with the length of the alkanol chain. V ^E results are discussed in terms of disruption of alkanol multimers, weakening of interactions between DMSO molecules, influence of interactions between components, and structural effects. The V ^E data have also been analyzed using the Prigogine-Flory-Patterson expression which separates V ^E into three contributions. Correlation is also observed between the sign of and V ^E for all the mixtures studied.     

Volumes and heat capacities of anionic-nonionic surfactant mixtures

Density, heat capacity and surface tension measurements of sodium decylsulfate (NaDeS)-dodecyldimethylamine oxide (DDAO)-water mixtures were carried out as functions of the surfactants total molality m_t at fixed stoichiometric mixture compositions X_NaDeS. From the surface tension data, the critical micelle concentration of NaDeS-DDAO mixtures as a function of X_NaDeS were obtained. From density and heat capacity data, the apparent molar volume V_,2 and heat capacity C_,2 of NaDeS-DDAO mixtures in water were calculated, respectively. At a given mole fraction, V_,2 and C_,2 monotonically increases and decreases, respectively, with increasing mt. However, anomalies were observed at X_NaDeS=0.1 and 0.3 for both V_,2 and C_,2 vs. mt curves. The nonideal contributions to the thermodynamic properties for the formation of surfactant-surfactant mixed micelles in water by mixing aqueous solutions of pure NaDeS and DDAO micelles were calculated at 0.3 mol-kg^–1 for the micellized surfactants mixture. The excess volume V^exc and heat capacity as functions of X_NaDeS are concave and S-shaped curves, respectively. All the properties are compared to those for sodium dodecylsulfate-DDAO mixture. In addition, to clarify the effect of the change in the hydrophobicity of the surfactants mixtures V^exc for the dodecyltrimethylammonium bromide-decyltrimethylammonium bromide mixture were calculated from literature data.     

Adsorption of surfactants on low-charged layer silicates Part II: Adsorption of non-ionic surfactants

Nonionic surfactants were adsorbed on low-charged layer silicates in the interlayers. After drying, the surfactants were arranged in densely packed double layers. However, in suspension considerably higher basal spacings are measured by x-ray diffraction which indicate that large quantities of non-ionic surfactants are adsorbed. With the aid of calorimetry, enthalpies of displacement were recorded which suggest strong interactions of the non-ionic surfactants with smectites. In analogy to tests on hydrophilic SiO₂, the adsorption of smectites is found to depend on the degree of ethoxylation of the non-ionic surfactant. The adsorption declines with increasing EO content.List of symbols n ^s adsorbed amount of surfactants (mmol/g) - n _max ^s maximal adsorbed amount of surfactants - d _L basal spacing (nm) - d _L interlayer separation because of adsorption - V _M molar volume of surfactant - V _max ^s volume of adsorbed surfactants (cm³/g) - V _int volume between the silicate layers (interlayer volume) (cm³/g) - H enthalpy of displacement (J/g) - h _max max. molar enthalpy of displacement (kJ/mol) Part I: Prog. Colloid Polymer Sci. 84, 206This paper is part of W. Röhl's doctorial dissertation at the Heinrich-Heine University, Düsseldorf     

Densities and Volumetric Properties of Binary Mixtures of Formamide with 1-Butanol, 2-Butanol, 1,3-Butanediol and 1,4-Butanediol at Temperatures between 293.15 and 318.15 K

The densities of binary mixtures of formamide (FA) with 1-butanol, 2-butanol, 1,3-butanediol, and 1,4-butanediol, including those of the pure liquids, over the entire composition range were measured at temperatures (293.15, 298.15, 303.15, 308.15, 313.15 and 318.15) K and atmospheric pressure. From the experimental data, the excess molar volume, V _m ^E, partial molar volumes, and , at infinite dilution, and excess partial molar volumes, and , at infinite dilution were calculated. The variation of these parameters with composition and temperature of the mixtures are discussed in terms of molecular interactions in these mixtures. The partial molar expansivities, and , at infinite dilution and excess partial molar expansivities, and , at infinite dilution were also calculated. The V _m ^E values were found to be positive for all the mixtures at each temperature studied, except for FA + 1-butanol which exhibits a sigmoid trend wherein V _m ^E values change sign from positive to negative as the concentration of FA in the mixture is increased. The V _m ^E values for these mixtures follow the order: 1-butanol < 2-butanol < 1,3-butanediol < 1,4-butanediol. It is observed that the V _m ^E values depend upon the number and position of hydroxyl groups in these alkanol molecules.     

Excess Molar Volumes and Partial Molar Volumes for Binary Mixtures of Water With 1,2-Ethanediol, 1,2-Propanediol,and 1,2-Butanediol at 293.15, 303.15 and 313.15 K

Abstract

From dilatometric method at 293.15,303,15, and 313.15K for binary mixtures of water and 1,2-alkane diols, the excess molar volumes, V^E and the partial molar volumes, V _i of both components at 293.15 K have been obtained as a function of mixtures composition. Excess molar volumes were calculated and correlated by a Redlich-Kister type function in terms of mole fraction. The partial molar volumes have been extrapolated to zero concentration to obtain the limiting values at infinite dilution, V ⁰ _i . All mixtures showed negative values and decreases with the chain length of diols. The values become less negative with increasing temperature. The results are explained in terms of dissociation of the self-associated diol molecules and the formation of aggregates between unlike molecules.     

Physicochemical properties of α, ω-type bolaform surfactant in aqueous solution. Eicosane-1,20-bis(triethylammonium bromide)

The physicochemical properties of the, - type (bolaform) surfactant, eicosane-1, 20-bis(triethylammonium bromide) (C₂₀Et₆), in aqueous solution have been investigated by means of surface tension, electrical conductivity, dye solubilization, and time-resolved fluorescence quenching (determination of average micelle aggregation number). Using electrical conductivity, the critical micelle concentration of C₂₀Et₆ was found to be 6.0×10^–3 mol dm^–3 and the ionization degree of C²⁰Et₆ micelle was found to be 0.42. From surface tension measurments, the molecular area of C₂₀Et₆ at the air-water interface was about twice that of normal type surfactants such as dodecyltrimethylammonium bromide (DTAB). The solubilizing power of micellar solution of C₂₀Et₆ toward Orange OT was 1.0×10^–2 mole of dye per mole of surfactant, i. e., slightly smaller than that of DTAB. The micelle aggregation number,N, was found to be 17±2 by time-resolved fluorescence quenching. C₂₀Et₆ showed a very small temperature dependence ofN, much less than for normal surfactants.     

Interfacial and aggregation properties of some anionic/cationic surfactant binary systems II. Mixed micelle formation and surface tension reduction effectiveness

Mixed micelle formation and surface tension reduction effectiveness (γ_cmc) were investigated for the following systems: triethanolammonium dodecylpoly(oxyethylene)sulfate (TADPS, containing about two ethylene oxide units)/dodecyltrimethylammonium bromide, TADPS/hexadecyltrimethylammonium bromide and TADPS/hexadecylpyridinium chloride. For all these anionic/cationic systems, the mixed critical micelle concentration (cmc) values reflect a strong synergism in mixed micelle formation, with β^M values ranging from −13.8 to −18.3. The mixed micelle composition is mixing-ratio dependent and, for equimolar mixtures, the mixed micelle is richer in the surfactant with the lower cmc. Precipitation is inhibited to a certain extent, thanks to the presence of ethylene oxide groups in the anionic species. The conditions for synergism in γ_cmc, differently expressed in the literature, can be derived from the surface tension equations established in our previous article. They can be conveniently described by a few characteristic constants: Γ _i ^∞ (saturated Gibbs excess), K _i (constant in the Szyszkowski equation), the cmc of the individual surfactants and the interaction parameters, β^S and β^M, of their mixtures. Excellent agreement between theoretically predicted and experimental results is obtained. With the increase in surfactant chain length, the β^M values decrease faster than the β^S ones and this can result in the loss of synergism in γ_cmc. Received: 11 June 2000 Accepted: 4 September 2000     

Volumetric Studies on Aqueous Solutions of Dodecyltrimethylammonium Bromide and 1-Dodecyl-3-methylimidazolium Bromide

The densities of aqueous solutions of mixed surfactants of dodecyltrimethylammonium bromide and 1-dodecyl-3-methylimidazolium bromide (DTAB/C₁₂mimBr) were measured at various compositions. The concentration dependent apparent molar volumes of these mixed surfactants were calculated and used to deduce the critical micelle concentrations (cmc) and the apparent molar volumes in the micelles and the continuous phase. The one-parameter Margules equation was applied to correlate the composition dependent cmc values and to obtain the activity coefficients and mole fractions of these surfactants in the mixed micelles, which were further used to calculate the excess Gibbs energies and the excess volumes. It was found that the excess Gibbs energies and the excess volumes of the mixed micelles are all negative, indicating that these mixed micelles are more stable and packed more tightly than their corresponding pure micelles.     

Thermodynamic study on the adsorption and micelle formation of long chain alkyltrimethylammonium chlorides

The surface tension of aqueous solutions of tetradecyl-trimethylammonium chloride (TTAC) and decyltrimethylammonium chloride (DeTAC) were measured as a function of temperature at concentrations below and above the critical micelle concentration under atmospheric pressure. The entropy and energy of adsorption from the monomeric state and from the micellar state and also the entropy and energy of micelle formation for TTAC were evaluated and compared with those of dodecyltrimethyl-ammonium chloride (DTAC). The values of Δ^M _W s and Δ^M _W u for TTAC and DTAC systems show that the micelle formation is driven by the entropy at low temperatures and by the energy at high temperatures. Received: 9 December 1997 Accepted: 4 March 1998     

Thermodynamic properties of naphthalene and uric acid in ethylene glycol-water mixtures

The solubility of naphthalene and uric acid was measured as function of temperature (5–45°C) in water(W)-ethylene glycol(EG) mixtures over the entire composition range. The molar solubility data were used to calculate transfer Gibbs energies G _tr ⁰ (WW-EG) (from water to water-ethylene glycol mixtures) and the temperature dependence of G⁰ was used to compute the corresponding transfer enthalpies and heat capacities. The thermodynamic quantities are interpreted in terms of two contributions; a cavity term which is estimated using the scaled particle theory (SPT) and a solute-solvent interaction term. The latter is inferred from comparisons involving the SPT results and the naphthalene data, or the data for naphthalene and uric acid. The solvation effects in W-EG mixtures are discussed with reference to thermodynamic properties of the solvent mixtures available from previous work.