Determination of interfacial co-ion concentration in ionic micelles by chemical trapping: Halide concentration at the interface of sodium dodecyl sulfate micelles

Iolanda M. Cuccovia, Augusto Agostinho-Neto, Caio M.A. Wendel, Hernan Chaimovich, Laurence Romsted

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Abstract

Products from the spontaneous reaction of a long-chain arenediazonium salt, 2,6-dimethyl-4-hexadecylbenzenediazonium tetrafluoroborate (16-ArN2BF4), in aqueous micellar solutions of sodium dodecyl sulfate (SDS), are used to estimate the local concentration of chloride and bromide ions at the micellar surface. The arenediazonium ion, 16-ArN2+, which is totally bound to the SDS micelle, reacts by rate-determining loss of N2 to give an aryl cation that traps available nucleophiles, i.e., H2O, Cl-, and Br-, to give stable phenol, 16-ArOH, and halobenzene products, 16-ArCl and 16-ArBr, respectively. Product yields, determined by HPLC, are related to local concentrations using calibration curves obtained from independent standards. The local concentrations determined by this method are consistent with co-ion concentrations calculated, using a cell model, by numerical integration of the Poisson-Boltzmann equation (PBE) taking into account salt-induced micellar growth. The salt dependence of the interfacial concentrations of Cl- and Br- are identical, indicating no specific interactions in the interfacial co-ion compartment. PBE calculations predict that, in micellar SDS, increasing the concentration of a particular halide salt (NaX) at constant concentration of another halide (NaY) should result in an increase in the local concentrations of both co-ions. Using this chemical-trapping method, this prediction was demonstrated experimentally.

Original languageEnglish (US)
Pages (from-to)5032-5034
Number of pages3
JournalLangmuir
Volume13
Issue number19
Publication statusPublished - Sep 17 1997

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All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

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