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Refractive index in relation to solvent effects on the amphiphilic association of n-alkylammonium carboxylates

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Abstract

Measurements of the refractive index of isotropic solutions of n-alkylammonium carboxylates [CH3(CH2)7 +NH3 −O2CR, R = H, n-tridecyl, n-heptadecyl, and 9-anthryl] display concentration dependence related to the degree of surfactant association in pure and mixed solvents of static relative permittivity in the range εr = 2.28–110 at 298 K. Results for n-octylammonium formate comply with: (i) small reverse micelle type aggregates in low εr ≤ 10 solvents, e.g., benzene; (ii) monomers and/or small association complexes in solvents of intermediate relative permittivity (εr ∼ 15–45, e.g., methanol, and acetone:water (50:50 v:v)); and (iii) charged normal micelles in high εr ≥ 78 solvents, e.g., water, and N-methylformamide. In water, the critical micelle concentration (cmc) of n-octylammonium formate (0.27–0.29 mol dm−3) is an order of magnitude higher than in benzene. A large anion group does not inhibit micellization in the case of n-octylammonium 9-anthracene carboxylate in chloroform. Refractometry, along with measurements of the electric conductance of some solutions, yield concordant information on micellar parameters and equilibrium processes compared to results from NMR and dielectric measurements. The solubility and Hamaker constants of n-octylammonium carboxylates in different solvents (εr = 1.8–182) are described, and experimental data are considered in the context of a micelle transition model.

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Acknowledgments

The author wishes to thank Dr. S. Walker (Professor Emeritus; Department of Chemistry, Lakehead University) and Professor J.H. Calderwood (while at the Department of Electrical Engineering, University of Salford) for their guidance and support for the research and to Mr. B.K. Morgan (Lakehead University) for technical assistance. Gratitude is expressed to Mr. V. Desando for computer hardware and software used in the preparation of this work for publication. The reviewers are also thanked for their helpful suggestions and comments.

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  1. Michael A. Desando

    Present address: , 26 Crown St., Thunder Bay, ON, P7B 3J6, Canada

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    Based on research by the author at the Department of Chemistry, Lakehead University, Thunder Bay, Canada, and the Department of Electrical Engineering, University of Salford, Salford, England.

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    Desando, M.A. Refractive index in relation to solvent effects on the amphiphilic association of n-alkylammonium carboxylates. Colloid Polym Sci 294, 1789–1805 (2016). https://doi.org/10.1007/s00396-016-3924-5

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