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Investigation of interaction parameters in mixed micelle using pulsed field gradient NMR spectroscopy
H Gharibi1, S Javadian, B Sohrabi
1Tarbiat Modarres University, Department of Chemistry, P.O. Box 14155-4838 Tehran, Iran. gharibi@irandoc.ac.ir
Abstract:
Pulsed field gradient NMR spectroscopy was used to determine the partitioning of surfactant between monomeric and micellar forms in a mixed CTAB (hexadecyltetramethylammonium bromide) and Triton X-100 [p-(1,1,3-tetramethylbutyl)polyoxyethylene] system. In addition, potentiometric and surface tension measurements were used to determine the free concentration of ionic surfactant and the critical micelle concentration (CMC) of mixtures of n-alkyltrimethylammonium bromide (C(n)TAB, n=12, 14, 16, 18) and Triton X-100. Regular solution theory cannot describe the behavior of the activity coefficient and the excess Gibbs free energy of mixtures of ionic and nonionic surfactants. To overcome these shortcomings, we developed a new model that combines Van Laar expressions and the theory of nonrandom mixing in mixed micelles. The Van Laar expressions contain an additional parameter, rho, which reflects differences in the size of the components of the mixture. Nonrandom mixing theory was introduced to describe nonrandom mixing in mixed micelles. This effect was modeled by a packing parameter, P*. The proposed model provided a good description of the behavior of binary surfactant mixtures. The results indicated that head group size and packing constraints are important contributors to nonideal surfactant behavior. In addition, the results showed that as the chain length of the C(n)TAB molecule in C(n)TAB/Triton X-100 mixtures was increased, the head group size parameter remained constant, but the interaction and packing parameters increased. Increase of the temperature caused an increase in the interaction parameter beta and a decrease in the packing parameter (P*).
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