Methyltri-n-octylammonium chloride (Aliquat 336) is sparingly soluble in water but is readily soluble with a 2-fold excess of micellized cetylpyridinium chloride (CPyCl), and the mixtures show breaks in plots of surface tension or electrolytic conductance against concentration indicative of a critical micelle concentration slightly lower than that of CPyCl. Micellization markedly increases 35Cl and 14N NMR line widths of CPyCl, but addition of NaCl reduces the 35Cl line width and addition of Aliquat increases it. Mixing Aliquat and CPyCl has little effect on their 14N line widths. Ion pairing in alcohol mixtures also increases 35Cl line widths. In water these mixed assemblies behave similarly to micelles of CPyCl as regards effects on rates and equilibria of interconversion of tri- and tetraperoxomolybdate ions, and oxidation of thioanisole by the latter, although it is slightly slower than in micelles of CPyCl. Despite differences in the hydrophobic regions,andrelationships between amphiphilic structuresandmorphologies of association colloids, assemblies of CPyCl and Aliquat behave very much like CPyCl micelles in their physical properties and effects upon reactivity. Geometrical optimization indicates that Aliquat can adopt conformations that allow intercalation with CPyCl micelles

Oxidation of Thioanisole by Peroxomolybdate in Assemblies of Cetylpyridinium Chloride and Methyltri-n-octylammonium Chloride

CERICHELLI, GIORGIO;
2004

Abstract

Methyltri-n-octylammonium chloride (Aliquat 336) is sparingly soluble in water but is readily soluble with a 2-fold excess of micellized cetylpyridinium chloride (CPyCl), and the mixtures show breaks in plots of surface tension or electrolytic conductance against concentration indicative of a critical micelle concentration slightly lower than that of CPyCl. Micellization markedly increases 35Cl and 14N NMR line widths of CPyCl, but addition of NaCl reduces the 35Cl line width and addition of Aliquat increases it. Mixing Aliquat and CPyCl has little effect on their 14N line widths. Ion pairing in alcohol mixtures also increases 35Cl line widths. In water these mixed assemblies behave similarly to micelles of CPyCl as regards effects on rates and equilibria of interconversion of tri- and tetraperoxomolybdate ions, and oxidation of thioanisole by the latter, although it is slightly slower than in micelles of CPyCl. Despite differences in the hydrophobic regions,andrelationships between amphiphilic structuresandmorphologies of association colloids, assemblies of CPyCl and Aliquat behave very much like CPyCl micelles in their physical properties and effects upon reactivity. Geometrical optimization indicates that Aliquat can adopt conformations that allow intercalation with CPyCl micelles
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11697/11943
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