Abstract
AbstractThe chemical shift of water was measured as a function of concentration of the detergents cetyltrimethylammonium chloride. CTACl; 3‐N‐dodecyl‐N,N‐dimethylammonio‐1‐propanesulfonate, DDAPS; polyoxyethylene (9.5) octylphenyl ether, Triton X‐100, and the deuterium content of the solvent. The short chain compound butyltrimethylammonium bromide was also studied as a model for CTACl. Graphs of the chemical shifts vs. the mole fractions of the solubilizates were linear in all cases and the slopes were used to calculate the so called “fractionation factor, ϕ” which can be used as a measure of the degree of structure of the water of hydration of the appropriate species (relative to bulk water). The calculated ϕ values indicated that the butyltrimethylammonium ion does not perturb hydrogen bonding of the solvent (ϕ = 0.99), whereas the water in the Stern layer of CTACl is more organized than bulk water ( = 1.06). Zwitterionic DDAPS was found to enhance the structuring marginally (ϕ = 1.02) whereas the nonionic surfactant Triton X‐100 has a structure decreasing effect (ϕ = 0.95).
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