Conductometric studies of hexadecyltrimethylammonium bromide in aqueous solutions of ethanol and ethylene glycol

The effect of cosolvent on micellization of hexadecyltrimethyl ammonium bromide (CTAB) in aqueous solutions was studied. The conductivity of a mixture (cosolvent + water) as function of CTAB concentration was measured at different temperatures. Ethylene glycol and ethanol were used as a cosolvent. The conductivity data were used to determine the critical micelle concentration (CMC) and the effective degree of counterion dissociation of micelle in the temperature range 303.2 to 313.2 K. In all the cases studied, a linear relationship between log([CMC]_mix/mol dm⁻³) and the mass fraction of cosolvent in solvent mixture has been observed. The free energy (ΔG _mic ⁰ ), enthalpy (ΔH _mic ⁰ ), and entropy (ΔS _mic ⁰ ) of micellization were determined using the temperature dependence of CMC. The dependence of these thermodynamic parameters on solvent composition was determined. The standard free energy of micellization was found to be negative in all cases and becomes less negative as the cosolvent content increases. The enthalpy and entropy of micellization are independent of temperature in pure water, while ΔH _mic ⁰ and ΔS _mic ⁰ decrease dramatically with temperature in mixed cosolvents. Furthermore, the entropic contribution is larger than the enthalpic one in pure water, while in the mixed solvents, the enthalpic contribution predominates. The text was submitted by the authors in English.     

Aggregation behaviour and thermodynamics of mixed micellization of 1-hexadecylpyridinium bromide and ionic liquid in ethylene glycol/water binary mixtures

Micellar behavior of binary combinations of ionic liquid, 1-tetradecyl-3-methylimidazolium bromide, with conventional cationic surfactant 1-hexadecylpyridinium bromide was investigated by means of conductometry to study the effect of cosolvent and water content and temperature. The critical micelle concentration and the degree of counterion association were calculated from the conductometry data. Thermodynamic parameters were obtained from the temperature dependence of the critical micelle concentration. The standard Gibbs energy of micellization increased with the increasing percentage of cosolvent as well as the mole fraction of C₁₄mimBr. The standard enthalpy and standard entropy of micelle formation were both decreased with the increasing temperature and the concentration of cosolvent. The entropy contribution was larger than the enthalpic one in pure water, whereas in the ethylene glycol/H₂O mixture the enthalpy contribution was predominant     

Studies on Thermodynamics of Micellization and Solvophobic Interactions of Novel Surfactant–Cr(III) Complexes in Non-aqueous Solvents

The critical micelle concentration (CMC) of surfactant–Cr(III)–dodecylamine complexes of the type cis-α-[Cr(trien)(C₁₂H₂₅NH₂)X]²⁺ (where trien = triethylenetetramine; X = F⁻, Cl⁻, Br⁻) has been studied in n-alcohol and in formamide at different temperatures, by electrical conductivity measurements. From the CMC values as a function of temperature, various thermodynamic properties have been evaluated: standard Gibbs energy changes (Δ_mic G ⁰), standard enthalpy changes (Δ_mic H ⁰) and standard entropy changes (Δ_mic S ⁰) for micellization. Critical micelle concentrations have also been measured as a function of the percentage composition of alcohol added. The solvent composition dependences of these thermodynamic parameters were determined. It is suggested that alcohol addition leads to an increase in formamide penetration into the micellar interface that depends on the alcohol’s chain length. The results are discussed in terms of an increased hydrophobic effect, dielectric constant of the medium, the chain length of the alcohols, and the surfactant in the solvent mixture.     

Micellar parameters of diblock copolymers and their interactions with ionic surfactants

The interactions of non-ionic amphiphilic diblock copolymer poly（oxyethylene/oxybutylene）(E₃₉B₁₈) with anionic surfactant sodium dodecyl sulphate（SDS） and cationic surfactant hexadecyltrimethylammonium bromide（CTAB） were studied by using various techniques such as surface tension,conductivity,steady-state fluorescence and dynamic light scattering.Surface tension measurements were used to determine the critical micelle concentration（CMC） and thereby the free energy of micellization(△G_mic),free energy of adsorption(△G_ads),surface excess concentration（Γ） and minimum area per molecule（A）.Conductivity measurements were used to determine the critical micelle concentration（CMC）,critical aggregation concentration（CAC）,polymer saturation point（PSP）,degree of ionization（α） and counter ion binding（β）. Dynamic light scattering experiments were performed to check the changes in physiochemical properties of the block copolymer micelles taken place due to the interactions of diblock copolymers with ionic surfactants.The ratio of the first and third vibronic peaks（I₁/I₃） indicated the polarity of the pyrene micro environment and was used for the detection of micelle as well as polymer-surfactant interactions.Aggregation number（N）,number of binding sites（n） and free energy of binding （△G_b） for pure surfactants as well as for polymer-surfactant mixed micellar systems were determined by the fluorescence quenching method.     

Thermodynamics of micellization of ionic surfactant/alkoxyethanol mixed micelles as a function of temperature

Estimates of the thermodynamic parameters of micellization ((_micG°, (_micH°, and (_micS°) have been determined for a series of mixed micelles consisting of ionic surfactants (sodium dodecylsulfate and dodecyltrimethylamonium bromide) and medium chain length alkoxyethanols as the co surfactant. The enthalpies of micellization have been measured directly for the above systems using isoperibol solution calorimetry; the Gibbs energies and entropies of micellization are obtained by application of the mass-action model to the critical micelle concentration values from the calorimetric titration experiments. The thermodynamic properties of mixed micelle formation with alcohol concentration and temperature are in excellent agreement with our previous results. However, there does appear to be some dependence of the thermodynamic properties of mixed micelle formation on the charge of the ionic surfactant. These dependencies are discussed in terms of the manner in which the ethylene oxide group of the alcohol interacts with the ionic head groups and the location of the solubilizates in the micellar interior.     

Studies on Hydrophobic Effect and Micelle Formation of Some Surfactant-Cr(III)-Cetylamine Complexes in Non-aqueous Solvents

Surface active micelle formable surfactant-Cr(III) complexes of the type cis-α-[Cr(trien)(C₁₆H₃₃NH₂)X]²⁺ (where trien = triethylenetetramine; X = F⁻, Cl⁻, Br⁻) have been studied in n-alcohol and in formamide at different temperatures by conductance measurements. Standard Gibbs energy changes (ΔG ^o _mic), enthalpies (ΔH ^o _mic) and entropies (ΔS ^o _mic) of micelle formation have been determined by studying the variation of the Critical Micelle Concentration (CMC) with temperature. Critical micelle concentrations have also been measured as a function of percentage concentration of alcohol added. It is suggested that alcohol addition leads to an increase in formamide penetration into the micellar interface that depends on the alcohol chain length. The results are discussed in terms of an increased hydrophobic effect, dielectric constant of the medium, the chain length of the alcohols and the surfactant in the solvent mixture.     

Micellization of dodecyldimethylethyl- ammonium bromide in aqueous solution

Specific conductivity of aqueous solutions of dodecyldimethylethylammonium bromide has been determined in the temperature range of 15-40°C. The critical micelle concentration (cmc) and ionization degree of the micelles, b, were determined from the data. Thermodynamic functions, such as standard Gibbs free energy, ΔG _m°, enthalpy, ΔG _m°, and entropy, ΔG _m°, of micellization, were estimated by assuming that the system conforms to the mass action model. The change in heat capacity upon micellization, ΔG _m°, was estimated from the temperature dependence of ΔG _m°. An enthalpy-entropy compensation phenomenom for the studied system has been found. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermodynamic studies of interaction between cetylpyridinium bromide and lysozyme by means of calorimetric titrations

In this study, we have investigated the micellization characteristics of n-cetylpyridinium bromide (CPB) and lysozyme–CPB system using isothermal titration calorimetry (ITC) technique. The ITC operates in a stepwise addition mode, providing an excellent method of determination of critical micelle concentration (CMC) and enthalpy of demicellization (and hence micellization). The micellization characteristics of CPB have been investigated by microcalorimetric technique at 25, 30, 35, and 40 °C in a buffer solution of Tris(hydroxymethyl)aminomethane and pH of 7.3. A scheme to describe lysozyme–CPB interaction has also been proposed on the basis of ITC technique in a buffer solution of Tris(hydroxymethyl)aminomethane at 30 °C, pH of 7.3, 0 mM NaCl, and 1 mM NaCl. The enthalpy changes associated with micelle dissociation were temperature and lysozyme concentration dependent, indicating the importance of hydrophobic interactions. The ΔG _mic was found to be negative, implying that, micellization, as expected, occurs spontaneously once the CMC has been reached. The values of ΔG _mic were found to become more negative with increasing temperature (in case of micellization of CPB) and with increasing the lysozyme concentration (in the case of lysozyme–CPB). The ΔS _mic was also found to decrease with increasing temperature in both cases. The presence of NaCl (1 mM) in the solutions decreased the CMC of CPB.     

Thermodynamic and NMR study of aggregation of dodecyltrimethylammonium chloride in aqueous sodium salicylate solution

The complex aggregation processes of dodecyltrimethylammonium chloride (DTAC) have been studied in dilute solutions of sodium salicylate (NaSal) by isothermal titration calorimetry and electrical conductivity at temperatures between 278.15 K and 318.15 K. A structural transformation that was dependent on the concentrations of DTAC and NaSal was observed. The micellization process in dilute solutions of DTAC has been subjected to a detailed thermodynamic analysis and shown to occur at considerably lower critical micelle concentrations than reported for DTAC in water and NaCl solutions. Gibbs free energy, Δ _mic G ^o, and entropy, Δ _mic S ^o, were deduced by taking into account the degree of micelle ionization, β, estimated from conductivity measurements. From the temperature dependence of the enthalpy of micellization, Δ _mic H ^o, the heat capacities of micellization, D_mic c_p^o {\Delta_{{{\rm mic} }}}c_p^o were determined and discussed in terms of the removal of large areas of non-polar surface from contact with water upon micellization. The process is exothermic at all temperatures, indicating, in addition to the hydrophobic effect, the presence of strong interactions between surfactant and salicylate ions. These were confirmed by ¹H NMR spectroscopy and diffusion NMR experiments. Salicylate ions not only interact with the headgroups but also insert further into the micelle core. At c _NaSal/c _DTAC > 2.5, the structural rearrangements occur even at relatively low concentrations of NaSal.     

A temperature study on critical micellization concentration (CMC), solubility, and degree of counterion binding of α-sulfonatomyristic acid methyl ester in water by electroconductivity measurements

 For a sodium salt of α-sulfonatomyristic acid methyl ester (14SFNa), one of the α-SFMe series surfactants, critical micellization concentration (CMC), solubility and degree of counterion binding (β) were determined by means of electrocon-ductivity measurements at different temperatures (at every 5 °C) ranging from 15 to 50 °C. The phase diagram of 14SFNa in pure water was constructed from the CMC- and solubility-temperature data, in which the Krafft temperature (critical solution temperature) was found around 0 °C. The changes in the Gibbs energy, ΔG ⁰ _m, enthalpy, ΔH ⁰ _m, and entropy, ΔS ⁰ _m, upon micelle formation as a function of temperature were evaluated taking βvalues into calculation. Received: 28 August 1996 Accepted: 5 November 1996     

Investigation of the Thermodynamic Properties of the Cationic Surfactant CTAC in EG + Water Binary Mixtures

To understand the thermodynamic characteristics of cationic surfactants in binary mixtures, the aggregation behavior of hexadecyltrimethylammonium chloride (CTAC) has been investigated in ethylene glycol (EG) + water solvent mixtures at different temperatures and EG to water ratios. The critical micelle concentration (CMC) and degree of counter ion bonding (β) were calculated from electrical conductivity measurements. An equilibrium model for micelle formation was applied to obtain the thermodynamic parameters for micellization, including the standard Gibbs energies of micellization (DG_mic^o)\Delta G_{\mathrm{mic}}^{\mathrm{o}}), standard enthalpies of micelle formation (DH_mic^o)\Delta H_{\mathrm{mic}}^{\mathrm{o}}) and standard entropies of micellization (DS_mic^o)\Delta S_{\mathrm{mic}}^{\mathrm{o}}). Our results show that DG_mic^o\Delta G_{\mathrm{mic}}^{\mathrm{o}} is always negative and slightly dependent on temperature. The process of micellization is entropy driven in pure water, whereas in EG + water mixtures the micellization is enthalpy driven.     

Effect of ethylene glycol on the thermodynamic and micellar properties of Tween 20

The aggregation behaviour of Tween 20 in ethylene glycol-water mixed solvents has been investigated using surface tension, density, static and dynamic light scattering, and fluorescence measurements. Micellar and surface thermodynamics data were obtained from the temperature dependence of critical micelle concentrations in various aqueous mixtures of ethylene glycol. In order to evaluate the influence of the cosolvent, the differences in the Gibbs energies of micellization of Tween 20 between water and binary solvents were determined. This study allowed us to conclude that the ability of ethylene glycol to act as a structure breaker and its interaction with the surfactant hydrophilic group are the controlling factors of the micellization process. From the evaluation of the thermodynamics of adsorption at the solution-air interface, it was determined that the surface activity of the surfactant decreases slightly with increasing concentration of ethylene glycol at a given temperature. Partial specific volume data, obtained by density measurements, indicate that the fraction of solvent molecules interacting with the micelle, via hydrogen bonds, remained roughly constant. The effect of cosolvent on the size and solvation of the aggregates was analysed by means of static and dynamic light scattering measurements. It was found that the aggregation number decreased, whereas the whole micellar solvation increased with the ethylene glycol content. Micellar micropolarity was examined using two different probes, pyrene and 8-anilinonaphthelene-1-sulfonic acid, and was found to increase with ethylene glycol addition, accompanied by an enhanced solvation. Fluorescence polarization measurements found by using coumarin 6 as a hydrophobic probe revealed an increase in the micellar microviscosity. The observed trends in these microenvironmental properties were ascribed to a participation by ethylene glycol in the micellar solvation layer.     

Synergistic behavior of sodiumdodecylsulfate and 1,2-diheptanoyl-sn- glycero-3-phosphocholine in an aqueous medium: interfacial and bulk behavior

The synergistic behavior of sodiumdodecylsulfate (SDS) and 1,2-diheptanoyl-sn-glycero-3-phosphocholine (DHPC) binary mixtures has been studied with interfacial and pyrene fluorescence(I ₁/ I ₃) intensity measurements. From the interfacial data, the interfacial parameters; the maximum surface excess (Γ_max), or the minimum area per molecule (A _min), and the surface pressure at the critical micellar concentration (π_cmc) have been evaluated. The cmc value has been used for evaluating the free energies of micellization (ΔG ^o _m). The mixed micelle formation was evaluated with the help of the Clint equation. The SDS plus DHPC mixed micelles showed negative departure from ideality indicating synergistic interactions between the unlike components. The quantitative analysis of mixed micelle, mixed monolayer and the composition of the mixed micelle was carried out with the help of regular solution approximation. The interaction parameters, β and β^σ, in the mixed micelle as well as in the mixed monolayer, respectively showed negative values indicating synergistic behavior of SDS and DHPC molecules.     

Mixing behaviour of a conjugated molecular wire candidate and an insulating fatty acid within Langmuir–Blodgett films

The conductivity, weight loss and A.C. impedance studies were carried out to establish the influence the presence of neutral copolymer (Vinyl pyrrodlidone/Vinyl acetate copolymer) with anionic surfactant (Disodium laurethsulfosuccinate) in cyclohexane propionic acid (CHPA) on the corrosion behaviour of carbon steel. The protection efficiency (P%) of AS in the absence and presence of polymer increases with increase in AS concentration until it reaches a maximum constant value near the CMC of AS and decreases with increase in solution temperature. The protective efficiency of AS can be enhanced and its critical micelle concentration shifts to low value by adding of 0.05 g/l of polymer. The critical micelle concentration of AS in the absence and presence of polymer increases with increase in temperature. The calculated thermodynamic parameters of micellization (ΔG_mic), (ΔH_mic) and (ΔS_mic) in the presence of neutral copolymer molecules with AS show that these processes are spontaneous and exothermic in nature and indicate the association between AS and neutral copolymer molecules.     

Thermodynamics of micellization of tetradecyltrimethylammonium bromide in ethylene glycol–water binary mixtures

The aggregation behaviour of tetradecyltrimethylammonium bromide in ethylene glycol–water mixtures across a range of temperatures has been investigated by electrical conductivity measurements. The critical micelle concentration (cmc) and the degree of counterion dissociation of micelles were obtained at each temperature from plots of differential conductivity, (κ/c) _{T , P} , versus the square root of the total concentration of the surfactant. This procedure not only enables us to determine the cmc values more precisely than the conventional method, based on plots of conductivity against total concentration of surfactant, but also allows straightforward determination of the limiting molar conductance and the molar conductance of micellar species. The equilibrium model of micelle formation was applied to obtain the thermodynamics parameters of micellization. Only small differences have been observed in the standard molar Gibbs free energies of micellization over the temperature range investigated. The enthalpy of micellization was found to be negative in all cases, and it showed a strong dependence on temperature in the ethylene glycol poor solvent system. An enthalpy–entropy compensation effect was observed for all the systems, but whereas the micellization of the surfactant in the solvent system with 20 wt% ethylene glycol seems to occur under the same structural conditions as in pure water, in ethylene glycol rich mixtures the results suggest that the lower aggregation of the surfactant is due to the minor cohesive energy of the solvent system in relation to water. Received: 13 December 1998 Accepted in revised form: 25 February 1999     

Study of an Alcohol’s Influence on the CMC and Thermodynamic Functions of Anionic Surfactants in DMA/Long-chain Alcohol Solutions Using a Microcalorimetric Method

The power-time curves for the micelle formation process were determined for two anionic surfactants, sodium laurate (SLA) and sodium dodecyl sulfate (SDS), in mixed alcohol + N,N-dimethylacetamide (DMA) solvent using titration microcalorimetry. From the data of the lowest point and the area of the power-time curves, their critical micelle concentration (CMC) and ΔH _m^o were obtained. The other thermodynamic functions of the micellization process (ΔG _m^o and ΔS _m^o) were also calculated with thermodynamic equations. For both surfactants, the effects of the carbon number (chain length) of the alcohol, the concentration of alcohol, and the temperature on the CMC and thermodynamic functions are discussed. For systems containing identical concentrations of a different alcohol, values of the CMC, ΔH _m^o and ΔS _m^o increased whereas ΔG _m^o decreased with increasing temperature. For systems containing an identical alcohol concentration at the same temperature, values of the CMC, ΔH _m^o,ΔG _m^o and ΔS _m^o decrease with increasing carbon number of alcohol. For systems containing the same alcohol at the same temperature, the CMC and ΔG _m^o values increase whereas ΔH _m^o and ΔS _m^o decrease with increasing alcohol concentration.     

Surface activity—thermodynamic properties and light scattering studies for some novel aliphatic polyester surfactants

The preparation of 12 new polyester surfactants based on aliphatic amines and different ethylene oxide content is described. These surfactants were characterized by determining their molecular weights and polydispersity by gel permeation chromatography (GPC) and nitrogen content. Drop volume tensiometry (DVT) was used to measure the surface tension at 25, 35, 45 and 55°C. The surface tension isotherms were used to determine critical micelle concentration (CMC), maximum Gibb's adsorption (Γ_max), minimum area per molecule (A_min), the effectiveness of surface tension reduction (π_cmc) and the efficiency (pC₂₀). The thermodynamic parameters of micellization (ΔG_mic, ΔH_mic, ΔS_mic) and of adsorption (ΔG_ad, ΔH_ad, ΔS_ad) were calculated and the data showed that these surfactants favor micellization to adsorption. The static scattered light intensity measurements provide the calculation of the molecular weight of micelle and the aggregation number (N°), while the dynamic light scattering provide the hydrodynamic radius of micelle (R_H) and the diffusion coefficient at different surfactant concentrations. The hydrodynamic radius of micelle (R_H) at different surfactant concentrations could be used also to determine the CMC giving results that are comparable to those obtained by surface tension measurements. All the data are discussed regarding the chemical structure of the polymeric surfactants. Copyright © 2004 John Wiley & Sons, Ltd.     

Micellization of triblock copoly(ethyleneoxide/tetrahydrofuran/ ethylene oxide)

 The association behaviour of triblock copoly(ethylene oxide/tetrahydrofuran/ethylene oxide), in particular E₁₀₀T₂₇E₁₀₀, in aqueous solutions has been investigated by means of static and dynamic light scattering, nuclear magnetic reso-nance (NMR) and surface tension techniques. On raising the polymer concentration at room temperature, the copolymer aggregates to form micelles with an aggregation number of about 105 (R _G, mic≈15 nm and R _H, mic≈13 nm, as revealed by light scattering and FT-PGSE NMR measurements, respectively). The micelles are kinetically quite stable, the micellar lifetime is shown to be more than 1 h. The residence time of a single unimer in a micelle is more than 140 ms. The apparent radius of gyration R _G, mic is fairly independent of concentration, but large effects are observed on varying the temperature. Raising the temperature initially results in an increase of the apparent micellar size, followed by a maximum at an intermediate temperature (≈45 °C). At higher temperatures a contraction of the micelles is observed. The shape of the micelles also appear to vary in this temperature interval. The interactions responsible for these phenomena are discussed in terms of, e.g., the temperature-dependent solubility of the alkylene oxide segments in water and polydispersity effects. Received: 29 January 1996 acccepted : 4 November 1996     

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     

A microcalorimetric titration study on the micelle formation of alkanediyl-α,ω-bis(dimethylalkylammonium bromide) surfactants at a 283.15–343.15?K temperature range

The aim of this study was to investigate the self-assembly process for m-8-m gemini surfactants, for m?=?8 and 12, in water, using the microcalorimetric titration method within the temperature range of 283.15?C343.15?K. The enthalpy of micellization (?H _mic) and critical micelle concentration (c.m.c.) have been calculated by using modified sigmoidal Boltzmann equation. Other thermodynamic parameters ?G _mic, ?S _mic, and ?C _p,mic, associated with micellization process were determined on the basis of the calorimetric results by applying the pseudo-phase separation model. The c.m.c. and ?H _mic values strongly depend on the temperature and the alkyl chain length. The enthalpy of micellization decreases and then changes its sign and becomes negative when temperature increases. The temperature dependence of the c.m.c. for the surfactants investigated exhibits typical U-shape. The results obtained are compared with literature data for other gemini cationic surfactants with a different alkyl chain length. The differences are analyzed in terms of differences in the hydrophobic interactions between the hydrocarbon chains.