Bhayana, Brijesh
(2007)
Experimental and Theoretical Investigations in Solid Phase<br /> Reaction Kinetics and Noncovalent Interactions in Water.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
Factors affecting reaction rates in polystyrene beads used in solid phase organic synthesis have been studied. The role of diffusion and reagent partitioning has been examined theoretically and experimentally. Both of these factors have been found to influence the reaction kinetics of common solid phase organic synthesis reactions. A mathematical model to analyze a simple bimolecular reaction inside a bead has been developed and successfully applied to the experimental data to obtain quantitative information on the influence of diffusion and reagent partitioning on the reaction rates. The effects of diffusion generally increase with the size and decreased swelling of the beads. Under many common reaction conditions, however, these effects may not be very significant. General guidelines to identify these conditions have been developed.<br /> A water-soluble torsion balance to study noncovalent interactions in aqueous media has been synthesized. The folding energies of new balances were found to be higher in water than in organic solvents. This increase can be partially attributed to hydrophobic forces. Aggregation and micelle formation were found to increase folding in water, indicating differences between microscopic and mesoscopic hydrophobic effects. The experimental data have been analyzed in the context of the Lum, Chandler and Weeks theory of hydrophobicity and evidences in its favor have been found. The hydrophobic response of a fluoromethyl group was found to be similar to a methyl group in two complementary torsion balances.<br />
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Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
| Title | Member | Email Address | Pitt Username | ORCID |
|---|
| Committee Chair | Wilcox, Craig | | | | | Committee Member | Johnson, Karl | | | | | Committee Member | Weber, Stephen | | | | | Committee Member | Chapman, Toby | | | |
|
| Date: |
20 June 2007 |
| Date Type: |
Completion |
| Defense Date: |
19 February 2007 |
| Approval Date: |
20 June 2007 |
| Submission Date: |
18 March 2007 |
| Access Restriction: |
5 year -- Restrict access to University of Pittsburgh for a period of 5 years. |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
| Degree: |
PhD - Doctor of Philosophy |
| Thesis Type: |
Doctoral Dissertation |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
diffusion; hydrophobic; noncovalent; reaction |
| Other ID: |
http://etd.library.pitt.edu/ETD/available/etd-03182007-205859/, etd-03182007-205859 |
| Date Deposited: |
10 Nov 2011 19:32 |
| Last Modified: |
15 Nov 2016 13:37 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/6523 |
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