Sponsor
Portland State University. Department of Chemistry
First Advisor
David H. Peyton
Term of Graduation
Fall 1992
Date of Publication
11-18-1992
Document Type
Thesis
Degree Name
Master of Science (M.S.) in Chemistry
Department
Chemistry
Language
English
Subjects
Molecular rotation, Micelles, Nuclear magnetic resonance spectroscopy, Surface active agents
DOI
10.15760/etd.6487
Physical Description
1 online resource (2, xi, 85 pages)
Abstract
The behavior of surfactants in solution has been and still is of scientific, technological, and industrial interest. The micelle forming compounds sodium N-( octyloxycarbonyl)sarcosinate (NaOcSarc), and sodium N-(decyloxycarbonyl)sarcosinate (NaDecSarc) show in aqueous solution two 1H NMR N-methyl peaks arising from a possible cis- or trans-conformation. The relative population of the N-methyl peaks depends mostly on the concentration of surfactant indicating micelle formation. Upon heating the two peaks start to coalesce and finally appear as one single peak. The temperature range in which this phenomenon occurs is from 25°C to 65°C. The primary interest of this study was to determine the activation parameters of rotation about the carbonyl-nitrogen (C-N) bond. Dynamic nuclear magnetic resonance spectroscopy was employed to approach this problem. A complete bandshape analysis was performed in order to calculate the free energy (ΔG‡), enthalpy (ΔH‡), and entropy (S‡) of activation. The effect of a different counter ion (Li+) and sodium chloride salt addition were tested for possible changes of the activation parameters. Studies in nonaqeous solvents were conducted with the free acid form of the mentioned carbarnates. Dimethylsulfoxide and chloroform were chosen as organic solvents for these particular experiments. The critical micellar concentrations of all surfactants were determined, and the assignment of the individual N-methyl peaks to the correspondend conformation could be unambiguously shown by a two dimensional NMR experiment.
The cmc's show strong salt dependence. The effect of a lithium as an alternative counter ion has a less drastic effect. Micellization seems not to occur in the free acid cases.
Interestingly, the surfactants show stronger salt dependence than micellization dependence upon the activation parameters, indicating that solvent exposure occurs at the C-N partial double bond and considerable deformation of the ideal spherical shape.
Rights
In Copyright. URI: http://rightsstatements.org/vocab/InC/1.0/ This Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).
Persistent Identifier
https://archives.pdx.edu/ds/psu/26619
Recommended Citation
Leitner, Dietmar A., "Dynamic NMR Study of Bond Rotational Activation Parameters in Micelles" (1992). Dissertations and Theses. Paper 4603.
https://doi.org/10.15760/etd.6487
Comments
If you are the rightful copyright holder of this dissertation or thesis and wish to have it removed from the Open Access Collection, please submit a request to pdxscholar@pdx.edu and include clear identification of the work, preferably with URL.