The Viscous Properties of Anionic/Cationic and Cationic/Nonionic Mixed Surfactant Systems

The behavior of mixed cationic/anionic and cationic/nonionic surfactants solutions have been studied by viscosimetry. The systems studied were sodium dodecyl sulfate (SDS)/cetyltrimethylammonium bromide (CTAB) and CTAB/Brij (polyoxyethylene lauryl ether, n = 10 and 23) in aqueous and sodium chloride solutions. The relative viscosity of single nonionic surfactant solutions is larger than that of SDS or CTAB solutions. It increases with the number of ethylene oxide groups. In the mixed systems, viscosity deviates from ideal behavior. The deviation results from electrostatic interactions. The surfactant mixture composition affects the self-assembled microstructure and rheology. A new mixed system that forms clear micellar solution above CMC was detected. In CTAB/Brij systems, the experimental data also deviate from ideal behavior due to mixed micelle formation and electroviscous effect. This effect is less pronounced than that of SDS/CTAB system and could be suppressed by adding an electrolyte (NaCl).     

Micellization and catalytic activity of the cetyltrimethylammonium bromide-Brij 97-water mixed micellar system

Surface tension measurements and the kinetic study of the basic hydrolysis of ethyl p-nitrophenyl chloromethyl phosphonate were used to examine the structural behavior and catalytic activity of the cethyltrimethylammonium bromide (CTAB)-polyoxyethylene (10) oleyl ether, C(18)H(35)(OCH(2)CH(2))(10)OH (Brij 97)-water mixed micellar system. Application of the regular solution model to the experimental data yields the value of the interaction parameter beta as -4.6, which indicates an attractive interaction of the surfactants in the mixed micelle and reflects synergistic solution behavior of the mixture. The mixed micellar composition is found to be enriched in the surfactant with the lower critical micelle concentration (cmc). In the kinetic study a nonmonotonic change in the pseudo-first-order rate constant of basic hydrolysis of the substrate is observed with increasing mole fraction of nonionic surfactant. The pseudophase micellar model reveals that the concentration factor mainly contributes to the catalytic effect, while the microenvironmental factor plays a negative role.     

Inhibition Effect of {Cationic Surfactant-Ascorbic Acid} Premicellar Aggregation on the Rate of Hexacyanoferrate(III) Oxidation of Ascorbic Acid: A Kinetic Study

The kinetics of oxidation of ascorbic acid by acidic hexacyanoferrate(III) have been investigated in presence of cationic surfactant viz. cetyltrimethylammonium bromide (CTAB). An inhibition effect of CTAB (below its critical micelle concentration) on the rate of oxidation has been observed. The spectrophotometric and kinetic data support a 1:1 premicellar association between substrate and surfactant. A mechanism has been proposed and a rate law consistent with kinetic results has been derived.     

THE EFFECT OF SURFACTANT MICELLES ON THE ALKALINE HYDROLYSIS OF DIMETHYLFORMAMIDE

The alkaline hydrolysis of dimethylformamide has been studied at 40'C in micellar solutions of single surfactant (CTAB. SDS. Brij 35) with the analog thermoanalytical curve method of thermokinetics. A kinetic equation of micellar catalysis under the condition of highter reactant concentration than micellar concentration ([S]>[M]) has been derived from the pseudophase model of micellar catalysis and some relative assumptions, The kinetic parameters. k_m, k_2mand the association constant of reactant with micelle K₁, have been calculated in this way. the results indicate that these surfactant micelles exhibit catalytic effect on the reaction. This is attributed to the micropolarity and local concentration effect of micelles.     

Antagonism in (conventional anionic–gemini anionic) mixed micelle catalyzed oxidation of D‐fructose by alkaline chloramine‐T: A kinetic study

The catalytic effect of individual conventional anionic surfactant, namely, sodium lauryl sulfate (NaLS), anionic gemini surfactant, namely, sodium salt of bis(1‐dodecenyl succinamic acid) (NaBDS), and mixed surfactant (NaLS + NaBDS) on the rate of oxidation of D ‐fructose by alkaline chloramine‐T has been investigated. The reaction always showed a first‐order dependence of rate with respect to each fructose, alkali, and chloramine‐T. The rate was proportional to (k′+k″ [surfactant]), where k′ and k″ are the rate constants in the absence and presence of the surfactant, respectively. The binding parameters have been evaluated. The observed catalytic effect of mixed micelle on the rate of oxidation was always less than the algebraic sum of the catalytic effect of two surfactants when they were taken separately, suggesting an antagonism (negative synergism) in mixed micelle. The antagonism has also been confirmed by determining critical micelle concentration and interaction parameter (β^m) of mixed micelle under the experimental conditions of kinetics, that is, in alkaline medium. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 123–132, 2009     

THE EFFECTS OF MIXED MICELLES OF SURFACTANTS ON POLYMERIZATION OF ACRYLAMIDE

The polymerization of acrylamide in mixed micellar solutions of surfactants, initiated by NaHSO₃ has been studied at 20 and 3Q° C with time variable method of thermokinetics for 1. 5-order reaction. The results indicate that the mixed micellar systems of cationic or anionic with zwitterionic surfactants (SLS/ CTAB, SLS/ TTAB, SLS/ SDS) and cationic with nonionic surfactants (Brij 357sol; CTAB, Bri-J35/TTAB, Brij35/ DTAB) have catalytic effect on the polymerization in the order, at 20° C. SLS/ SDS SLS/ TTAB SLS/ CTAB Brij35/ CTAB at 30° C SLS/ SDS SLS/ TTAB≈ / CTAB Bri-j35/ DTAB= sBrij35/ TTAB as Brij35/ CTAB, while Brij35/ SDS mixed micellar system has inhibition. These effects are attributed to the effect of the Stern layer of mixed micelles on the step of initiator (HSOT) to form free radical.     

Effect of cationic micellar aggregates on the kinetics of oxidation of aminoalcohols by N-bromosuccinimide in alkaline medium

The kinetics of oxidation of some aminoalcohols (AA), viz. ethanolamine, diethanolamine, and triethanolamine, by N-bromosuccinimide (NBS) in alkaline medium has been investigated in the absence as well as in the presence of cetyltrimethylammonium bromide (CTAB), a cationic surfactant. The reaction always followed a first-order dependence of rate on NBS, while the order in each AA and alkali was found to decrease from unity to zero at higher [AA] and [OH-], respectively. The reaction is strongly catalyzed by CTAB even before the critical micelle concentration (CMC) of CTAB. However, the observed rate constants attained constancy at higher [CTAB] (>CMC of CTAB). The premicellar kinetics has been rationalized in the light of the Piszkiewicz positive cooperativity model [J. Am. Chem. Soc. 99 (1977) 1550]. The binding constants between the reactants and the surfactant have also been evaluated using the Raghvan and Srinivasan model [Proc. Ind. Acad. Sci. 98 (1987) 199], which is applicable to bimolecular micellar catalyzed reaction and predicts constancy in the observed rate constant at higher [surfactant]. The binding constants obtained by both the models are in good agreement.     

THE EFFECT OF MIXED MICELLES OF SURFACTANTS ON THE ALKALINE HYDROLYSIS OF ESTERS

The alkaline hydrolysis of aromatic and normal aliphatic acid esters have been studied at 25°C In mixed micellar solution of surfactants (Brij35—SDS, Brij35 — DTAB, Brij35—TTAB.Brij35-CTAB. Triton X—100 —CTAB, Triton X— 100 —SDS) with UV spectrophotometry and the method of thermokinetics The critical mice liar concentrations of the corresponding systems have also been measured with UV spectrophotometry in this paper. K_jnln micellar pseudo-phase has been calculated- The ratios of ki.to ki.for all mixed micellar systems Investigated are less than 1. The results indicate that these reactions are inhibited by the mixed micelles and the mixed micelles exhibit a greater effect of Inhibition on the reactions than those do In corresponding single ones. The reason for this is that the micropolarity of the compact Stern layer of mixed micelle is lower, and the micro viscidity Is higher. The Inhibition effect! also depend on the hydrophobic chain length of the surfactants and the hydrophobicity of the substrate.     

Effect of Polymer and Surfactant‐Polymer Couples on the Acid-Catalyzed Hydrolysis of Phenyl Urea

The mechanism of the hydrolysis decomposition of phenyl urea in acid, polymer, and surfactant‐polymer media was investigated, the addition‐elimination mechanism with rate determining attack of water at N‐protonated substrate having already been studied. This study has introduced the polymer PEG (MW‐400) and (surfactant‐polymer) (ceteyl trimethyl ammonium bromide‐poly ethylene glycol) (CTAB‐PEG), (cetyl pyridinium bromide‐polyethylene glycol) (CPC‐PEG) (sodium dodecyl sulphate‐poly ethylene glycol) (SDS‐PEG), (Triton X‐100‐poly ethylene glycol) (TX‐100‐PEG), and (Brij35‐poly ethylene glycol) (Brij35‐PEG) in acid media. The results indicate that the presence of polymer and surfactant‐polymer enhances the rate of reaction at 80°C in the presence of 0.9 M H₂SO₄. Kinetic studies show that the reaction obeyed first‐order kinetics. The reaction kinetics can be well explained by micellar catalysis models like the PPIE.     

Aggregation behavior and interaction of an amphiphilic drug imipramine hydrochloride with cationic surfactant cetyltrimethylammonium bromide: light scattering studies

The aggregation behavior and interaction of an amphiphilic antidepressant drug imipramine (IMP) hydrochloride with the cationic surfactant cetyltrimethylammonium bromide (CTAB) have been studied using light scattering (both static and dynamic) techniques. Due to rigid tricyclic hydrophobic moiety present in the molecule, the drug shows interesting association behavior. The static light scattering measurements show that the self-association of IMP commenced above a well-defined critical micellar concentration (CMC), which decreases with increasing the mole fraction of the CTAB surfactant. Both the excess Gibbs energy (ΔG(ex)) and the Gibbs energy of micellization (ΔG(M)°) are negative, and decrease with increasing mole fraction of the surfactant. The hydrodynamic diameters (d(h)) of the micellar aggregates were also evaluated using the dynamic light scattering measurements. The data indicate formation of larger aggregates by IMP and CTAB due to mixed micellization and subsequent micellar growth. The results have been analyzed using different models (viz., Clint, Motomura, Rosen, Rubingh, etc.) for mixed micelle formation.     

Spectroscopic studies of interaction of Safranine T with nonionic micelles and mixed micelles

The visible spectra of Safranine T (ST) in micellar solution of Brij 58, Tween 20 and Tween 40 and mixed micellar solution of Brij 58/Tween 20 and Brij 58/Tween 40 indicate formation of 1:1 charge transfer (CT) complex between acceptor ST and donor nonionic micelles and mixed micelles. The experimental CT transition energies are well correlated (through Mulliken's equation) with the vertical ionization potential of the donors. The solvent parameters, i.e. the intramolecular charge transfer energy ET(30) have been determined from the Stokes spectral shift. Variations of ionization potential and micropolarity in the mixed micellar region have been investigated as a function of surfactant composition and the obtained results in mixed micellar medium has been compared to the normal micelles. The critical micelle concentration (CMC) values determined at various surfactant compositions are lower than the ideal values indicating a synergistic interaction. The interaction parameter (beta) and micellar stability has been calculated using regular solution theory.     

Surfactant-induced electroosmotic flow in microfluidic capillaries

Control of EOF in microfluidic devices is essential in applications such as protein/DNA sizing and high‐throughput drug screening. With the growing popularity of poly(methyl methacrylate) (PMMA) as the substrate for polymeric‐based microfludics, it is important to understand the effect of surfactants on EOF in these devices. In this article, we present an extensive investigation exploring changes in EOF rate induced by SDS, polyoxyethylene lauryl ether (Brij35) and CTAB in PMMA microfluidic capillaries. In a standard protein buffer (Tris‐Glycine), PMMA capillaries exhibited a cathodic EOF with measured mobility of 1.54 ± 0.1 (× 10^?4 cm²/V.s). In the presence of surfactant below a critical concentration, EOF was independent of surfactant concentration. At high concentrations of surfactants, the electroosmotic mobility was found to linearly increase/decrease as the logarithm of concentration before reaching a constant value. With SDS, the EOF increased by 257% (compared to buffer), while it was decreased by 238% with CTAB. In the case of Brij35, the electroosmotic mobility was reduced by 70%. In a binary surfactant system of SDS/CTAB and SDS/Brij35, addition of oppositely charged CTAB reduced the SDS‐induced EOF more effectively compared to nonionic Brij35. We propose possible mechanisms that explain the observed changes in EOF and zeta potential values. Use of neutral polymer coatings in combination with SDS resulted in 50% reduction in the electroosmotic mobility with 0.1% hydroxypropyl methyl cellulose (HPMC), while including 2% poly (N,N‐dimethylacrylamide) (PDMA) had no effect. These results will potentially contribute to the development of PMMA‐based microfluidic devices.     

THE EFFECT OF SINGLE MICELLES OF SURFACTANTS ON POLYMERIZATION OF ACRYLAMIDE

The polymerization of acrylamide in micellar solutions of cationic, anionic, zwitterionic and nonionic surfactants, initiated by NaHSO₃, has been studied at 20 and 30° C with time variable method of thermokinetics for the 1. 5-order reaction in this paper. Reaction mechanism has been suggested and rate equations have been derived. The results indicate that ionic (CTAB, TTABDTAB, SDS) and zwitterionic (SLS) surfactants catalyze the polymerization in the order SDS>SLS>DTAB ≈ TTA≈ CTAB, and nonionic surfactant (Brij35) has slight inhibition effect. These effects are mainly caused by the effect of the formation of micelle- HSO₃ complex on the step of initiator to form free radical.     

Micellar effects on the electrochemistry of dopamine and its selective detection in the presence of ascorbic acid

The electrochemistry of dopamine (3-hydroxytyramine) was studied by cyclic voltammetry at a glassy carbon electrode in the presence of cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) micelles at different pH. The anodic peak potential (E(pa)) and peak current (I(pa)) were found to be remarkably dependent on the charge and the concentration of the surfactant. The E(pa) and I(pa) change abruptly around the critical micellar concentration (CMC) of the surfactants and reach a plateau above the CMC. The E(pa) at the plateau shifts to more positive values in the cationic CTAB micellar solution, e.g. from 180 mV vs SCE in aqueous solution at pH 6.8 to 410 mV in CTAB micelle, whilst it shifts to less positive values in the anionic SDS micellar solution, e.g. 150 mV at pH 6.8. Therefore, the overlapped anodic peaks of dopamine and ascorbic acid in the mixture of the two compounds in aqueous solutions can be separated in CTAB micelles since the micelle shifts the E(pa) of ascorbic acid to less positive values. The two peaks are separated by ca. 400 mV at pH 6.8 in CTAB micelle, hence dopamine can be determined in the presence of 100 times excess of ascorbic acid. In SDS micelle and in the presence of ascorbic acid, the I(pa) of dopamine is greatly enhanced due to the catalytic oxidation of the latter that enables quantitative determination of both compounds.     

Effect of glycerol on micelle formation by ionic and nonionic surfactants at 25 degrees C

The effect of glycerol on the micellization of the cationic surfactant cetyltrimethylammonium bromide (CTAB) and of the ethoxylated nonionic surfactant Brij 58 has been investigated by various experimental techniques. For both surfactants the critical micellar concentration (cmc), determined by surface tension measurements, is almost unaffected by the presence of glycerol in the mixture; only at high glycerol concentrations (>/=20% w/w) does the cmc significantly increase. The area per surfactant molecule at the air-solution interface, A, increases with increasing glycerol weight percentage, w(g). Fluorescence quenching measurements indicate that the presence of glycerol induces a lowering of the aggregation number of both surfactants. The glycerol intradiffusion coefficient has been measured by the pulsed-gradient spin-echo NMR technique as a function of glycerol content at constant surfactant concentration. It is almost unaffected by the presence of the surfactants, indicating that no direct glycerol-surfactant interaction occurs in the mixture. The surfactant intradiffusion coefficient has been also measured. In the case of CTAB, it increases with increasing glycerol concentration, a reflection of the decreased aggregation number. For Brij 58, in spite of the lowering of the aggregation number, the surfactant intradiffusion coefficient decreases with increasing glycerol concentration, suggesting an increase of the intermicellar interaction. The experimental evidence shows that for both surfactants the micellization is affected by the presence of glycerol through an indirect, solvent-mediated mechanism. In the case of CTAB, the main effect of glycerol is a lowering of the medium dielectric constant, which enhances the electrostatic interactions in solution. In the case of Brij 58, the results can be interpreted in terms of a salting-out effect according to which glycerol competes with the surfactant for water molecules, causing a dehydration of the surfactant ethoxylic headgroup.     

Micellar effect on the electron transfer reaction of chromium(V) ion with organic sulfides

The rate of electron transfer from organic sulfides to [Cr^V(ehba)₂]⁻ (ehba-2-ethyl-2-hydroxy butyric acid) decreases with a decrease in the polarity of the medium. The anionic surfactant, SDS and the cationic surfactant, CTAB have different effects on the kinetics of this reaction. The micellar inhibition observed in the presence of SDS is probably due to the decrease in the polarity and the electrostatic repulsion faced by the anionic oxidant from the anionic micelle and the partition of the hydrophobic substrate between the aqueous and micellar phases. The micellar catalysis in the presence of CTAB is attributed to the increase in the concentration of both reactants in the micellar phase. This micellar catalysis is observed to offset the retarding effects of the less polar micellar medium and the unfavorable charge-charge interaction between the + charge developed on S center in the transition state and the cationic micelle. This catalysis is contrary to the enormous micellar inhibition observed with IO₄⁻, HSO₅⁻ and HCO₄⁻ oxidation of organic sulfides.     

Effect of self‐assemblies of various surfactants in their single and mixed states on the BZ oscillatory reaction

Micelles of different surfactants are well known to affect chemical equilibria and reactivities by selectively sequestering the reagent substrates through electrostatic and hydrophobic interactions. In this article, the effects of micelles of various surfactants on different parameters of the Ce(IV)‐catalyzed Belousov–Zhabotinsky (BZ) oscillatory reaction at 35°C in nonstirred closed conditions are studied by employing spectrophotometry and tensiometry. Surfactants used in this study are the cationics hexadecyltrimethylammonium bromide (CTAB) and pentamethylene‐1,5‐bis(N‐hexadecyl‐N,N‐dimethylammonium)bromide gemini (Gemini), anionic sodium dodecylbenzene sulfonate (SDBS), and nonionic Brij58, whereas the binary surfactant systems used are cationic–nonionic CTAB+Brij58 and anionic–nonionic SDBS+Brij58. The results revealed that the induction period shows a definite variation with increasing concentration of different surfactants above their critical micelle concentration (cmc). The amplitudes of oscillation and absorbance maxima and minima are enhanced in the presence of micelles of CTAB and Gemini surfactants, whereas micelles of SDBS and Brij58 have almost no effect on the nature of the oscillations. However, mixed micelles of CTAB+Brij58 and SDBS+Brij58 binary mixtures show a quite different effect on the overall behavior of the oscillations. The enhanced effect of CTAB and Gemini surfactants on the overall nature of oscillations has been attributed to the positive charge on the surface of their micelles and to some extent on the presence of nitrogen in their head group. The effect of mixed binary micelles may be attributed to their synergistic nature. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 659–668, 2010     

Isocratic and gradient elution in micellar liquid chromatography with Brij‐35

Polyoxyethylene(23)lauryl ether (known as Brij‐35) is a nonionic surfactant, which has been considered as an alternative to the extensively used in micellar liquid chromatography anionic surfactant sodium lauryl (dodecyl) sulfate, for the analysis of drugs and other types of compounds. Brij‐35 is the most suitable nonionic surfactant for micellar liquid chromatography, owing to its commercial availability, low cost, low toxicity, high cloud temperature, and low background absorbance. However, it has had minor use. In this work, we gather and discuss some results obtained in our laboratory with several β‐blockers, sulfonamides, and flavonoids, concerning the use of Brij‐35 as mobile phase modifier in the isocratic and gradient modes. The chromatographic performance for purely micellar eluents (with only surfactant) and hybrid eluents (with surfactant and acetonitrile) is compared. Brij‐35 increases the polarity of the alkyl‐bonded stationary phase and its polyoxyethylene chain with the hydroxyl end group allows hydrogen‐bond interactions, especially for phenolic compounds. This offers the possibility of using aqueous solutions of Brij‐35 as mobile phases with sufficiently short retention times. The use of gradients of acetonitrile to keep the concentration of Brij‐35 constant is another interesting strategy that yields a significant reduction in the peak widths, which guarantee high resolution.     

Effect of Cationic Micelle on the Kinetics of Oxidation of Citric Acid by N-Bromophthalimide in Acidic Medium

Kinetics of the oxidation of citric acid (CA) by N-bromophthalimide (NBP) has been studied in the presence of cationic surfactant cetyltrimethylammonium bromide (CTAB) at 35°C. The CMC value is lower than those given in the literature for aqueous solutions of CTAB without added electrolyte. The reaction is strongly catalyzed by cationic micelle, CTAB with a progressive increase in CTAB concentration the reaction rate increased, at higher concentration constancy in the rate constant was observed. The reaction follows first and fractional order kinetics in NBP and citric acid, respectively. The reaction follows inverse fractional order with respect to perchloric acid. The Arrhenius equation is found to be valid for the reaction. A detailed mechanism with the associated reaction kinetics is discussed. The catalytic role of CTAB micelles is discussed in terms of the Menger and Portnoy model.     

Micellae catalysis of the oxidation of 1,4-dihydro-nicotinamides by methylene blue part 2

The oxidation of 1-R-1,4-dihydronicotinamides (1a: R = benzyl, 1b:R = octyl, 1c:R = cetyl) by methylene blue has been studied in the presence of micelles of cetyltrimethylammonium bromide (CTAB), polyoxyethylene[23]lauryl ether (Brij^® 35) and sodium dodecylbenzenesulfonate (SDBS). In CTAB, a small rate enhancement was observed below the cmc, followed by a gradual decrease above the cmc. Brij 35 has little effect on the reaction rate. The rate vs. concentration profile in SDBS shows a very sharp maximum near the cmc for 1b and 1c, whereas a more moderate increase in rate is observed for 1a. The effects are analyzed in terms of the pseudophase model for micellar catalysis, and it appears that the observed rate enhancements can be completely ascribed to increments of the reactant concentration in the micellar pseudophase. Comparison with rate effects in sodium dodecylsulfate (SDS) micelles reveals that the reaction in SDBS micelles proceeds in a more polar environment. This provides kinetic evidence that the aryl moiety in SDBS allows a deeper penetration of water molecules into the micelle, thus giving rise to a more open surface for SDBS micelles than for SDS micelles.