Monomer Concentrations in Simple Micellar Systems from NMR Relaxation Times and C‐13 Chemical Shifts

Abstract

The monomer concentrations for some simple micelle forming surfactants, octylammonium bromide (OTAB), sodium decyl sulphate, SDecS, and dodecyltrimethylammonium bromide (DTAB) were determined from the NMR‐paramagnetic relaxation enhancement experiment (the NMR‐PRE) on the H‐1 spin lattice relaxation times for the surfactant protons as a function of the surfactant concentration above and below the critical micelle concentration (cmc region). The NMR relaxation times, determined from the inversion recovery method, decrease steadily as the concentration of the surfactant is increased above the cmc value. A second, simple method is proposed whereby the p‐value of the surfactant in the micelle is determined from the two‐site model via extrapolation of the observed relaxation rate data to high concentrations. The p‐values and the calculated monomer concentrations are compared to each other and to those obtained using the mass‐action and phase separation models. In most cases, the monomer concentrations appear to remain constant at concentrations up to 2–3 times the cmc value, and then begin to decrease thereafter. These results are compared to the trends in monomer concentrations obtained from other NMR experiments in other surfactant systems.

Keywords:

• Micelles
• surfactants
• NMR spectroscopy
• relaxation times chemical shifts
• monomer concentrations

The financial support of NSERC (research grant, D. G. M) and the StFX University Council for Research is greatly appreciated. M. J. D. acknowledges the grant of a StFX University Council for Research Award.