Micelle formation of ionic surfactants. Tracer self-diffusion studies and theoretical calculations for sodium p-octylbenzenesulfonate

Lindman, Bjoern; Puyal, Marie Claude; Kamenka, N.; Brun, Bernard; Gunnarsson, Guðmundur

doi:10.1021/j100206a045

Cited by 99 publications

(47 citation statements)

References 8 publications

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“…This evidence can be ascribed to a change in the surfactant molecules' hydration due to their micellization (35). The evaluation from our data of the surfactant hydration number in the premicellar and micellar composition range would require many assumptions concerning, for example, the counterions' intradiffusion coefficients, the counterion hydration number, and the change of this value due to the micellization; these assumptions would make the results questionable.…”

Section: Solvent Intradiffusion Coefficientmentioning

confidence: 73%

Transport Properties of Aqueous Solutions of Alkyltrimethylammonium Bromide Surfactants at 25°C

D’Errico

Ortona

Paduano

et al. 2001

Journal of Colloid and Interface Science

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Section: Solvent Intradiffusion Coefficientmentioning

confidence: 73%

Transport Properties of Aqueous Solutions of Alkyltrimethylammonium Bromide Surfactants at 25°C

D’Errico

Ortona

Paduano

et al. 2001

Journal of Colloid and Interface Science

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“…Lindman and coworkers have, in an extensive series of reports, shown that Pb can be obtained from self-diffusion studies [26][27][28]. Unfortunately, for SDS Pb has not been determined at concentrations corresponding to our shift measurements.…”

Section: Resultsmentioning

confidence: 95%

On the determination of micellar aggregation numbers from the concentration dependence of13C NMR chemical shifts

Söderman

Guering²

1987

Colloid & Polymer Sci

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Abstract:The assumptions underlying the extraction of micellar aggregation numbers by means of applying the mass action law to the concentration dependence of i3C Nuclear Magnetic Resonance (NMR) shift data are discussed. Such data are presented for sodium dodecylsulfate and it is shown that the extracted aggregation numbers are far too small. It is argued that this is in part due to a failure of the mass action law to describe the micellization process but also due to covariance in the parameters of the mass action law. We also suggest a way to analyse 13C shifts from surfactant systems that is void of artefacts due to changes in volume magnetic susceptibilities and other "unwanted" artefacts. Finally, we point out that by combining 13C shifts with the fraction of micellized surfactant (as measured by for instance self diffusion coefficients) it should be possible to monitor changes in micellar shapes as the conditions are changed.

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“…(1) for a cationic surfactant with a counterion, X = halide. It is sufficient to consider contributions to the chemical shift of water from free halide ion, C>xr' and micelle, C>M' because the concentration of monomeric surfactant is small (relative to its total concentration) and decreases as a function of increasing mole fraction of the surfactant, N Surf [28]. In pure H 20, Xo = 0, and Eq.…”

Section: Discussionmentioning

confidence: 99%

Proton NMR Studies on the Structure of Water at Interfaces of Aqueous Micelles. Part 4: Effects of Cationic and Zwitterionic Headgroups

Seoud¹,

Blaskó

Bunton

1995

Ber Bunsenges Phys Chem

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Fr.actionation factors, rpM' of interfacial water at surfaces of cationic and zwitterionic surfactants were determined from the dependence of the 1H chemical shift of water on the isotopic composition of the solvent (H°p lus O 2°) .~alue~of rpM are greater than unity, showing that interfacial water is more structured than bulk water who.se fractionation factor = 1, by defin.itio.n. The structuring increases with increasing bulk of the headgroup: but IS unaffected by the length of the catiomc surfactant hydrophobic tail. The effect of zwitterionic sulfobetaine s~r~actants on the structure of their water of hydration is less than that of cationic surfactants that have otherwise slm.ll~r .headgrou~s. Values of rpM for cationic micelles are: cetyldimethylphenylammonium chloride, 1.08; cetylp~ndln1Um chlonde, 1.06; and dodecyltrimethylammonium bromide, 1.06. Values of QlM for sulfobetaine micelles are: 3-N-tetradecyl-N,N-di-n-butylammonio-I-propane sulfonate, 1.07, and 3-N-tetradecyl-N,N-diethylammonio-I-propane sulfonate, 1.03.7]. These methods often involve hydrophobic solutes whose (average) solubilization site in the micellar pseudophase is a matter of discussion, and they may perturb aggregate structure [8, 9]. In the present work, we examine effects of the nature of surfactant headgroups on the structure of interfacial water by measuring the deuterium solvent isotope effect on the 1H chemical shift of the solvent (H 20 plus D 20). Isotopic substitution in the solvent involves minimum perturbation of the micellar system. The resulting secondary isotope effect is, however, small, but 1H NMR spectroscopy is a very sensitive technique and is, therefore, suitable for measurement of such small effects [10][11][12][13][14][15][16].It is convenient to describe isotope effects in terms of fractionation factors, rp, defined for a micelle, M, as:That is, for a micelle in H 20-D20, the fractionation factor for interfacial water, rpM, describes the isotopic composition at the aggregate/water interface relative to that in bulk solvent [14][15][16].We are interested in exploiting the value of rpM to probe effects of the charge and nature of headgroups on the degree of structure of interfacial water. To date, effects of micelles of various ionic, zwitterionic and nonionic surfactants have been examined [14][15][16]. In the present work we examine effects due to aromatic or bulky alkyl headgroups in cationic and zwitterionic sulfobetaine micelles, as well as variation in the length of the surfactant hydrophobic tail.Earlier results showed that hydrophobic headgroups (phenyl or n-butyl) enhance the structure of interfacial water; electrostriction by the charged interface and hydrophobic hydration of the bulky group being the main factors.

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Micelle formation of ionic surfactants. Tracer self-diffusion studies and theoretical calculations for sodium p-octylbenzenesulfonate

Cited by 99 publications

References 8 publications

Transport Properties of Aqueous Solutions of Alkyltrimethylammonium Bromide Surfactants at 25°C

Transport Properties of Aqueous Solutions of Alkyltrimethylammonium Bromide Surfactants at 25°C

On the determination of micellar aggregation numbers from the concentration dependence of13C NMR chemical shifts

Proton NMR Studies on the Structure of Water at Interfaces of Aqueous Micelles. Part 4: Effects of Cationic and Zwitterionic Headgroups

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