Date of Award

11-18-1992

Document Type

Thesis

Degree Name

Master of Science (M.S.) in Chemistry

Department

Chemistry

Physical Description

1 online resource (2, xi, 85 p.)

Subjects

Molecular rotation, Micelles, Nuclear magnetic resonance spectroscopy

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 lH 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 (G++), enthalpy (H++), 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.

Description

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Persistent Identifier

https://archives.pdx.edu/ds/psu/26619

Included in

Chemistry Commons

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