Molecular dynamics study of solvation phenomena to guide surfactant design

dc.contributor.advisorRossky, Peter J.en
dc.creatorDalvi, Vishwanath Hailyen
dc.date.accessioned2010-06-02T18:50:15Zen
dc.date.available2010-06-02T18:50:15Zen
dc.date.issued2009-12en
dc.descriptiontexten
dc.description.abstractSupercritical carbon-dioxide has long been considered an inexpensive, safe and environmentally benign alternative to organic solvents for use in industrial processing. However, at readily accessible conditions of temperature and pressure, it is by itself too poor a solvent for a large number of industrially important solutes and its use as solvent necessitates concomitant use of surfactants. Especially desirable are surfactants that stabilize dispersions of water droplets in carbon-dioxide. So far only molecules containing substantially fluorinated moieties e.g. fluoroalkanes and perfluorinated polyethers, as the CO₂-philes have proved effective in stabilizing dispersions in supercritical carbon-dioxide. These fluorocarbons are expensive, non-biodegradable and can degrade to form toxic and persistent environmental pollutants. Hence there is great interest in developing non-fluorous alternatives. Given the development of powerful computers, excellent molecular models and standardized molecular simulation packages we are in a position to augment the experiment-driven search for effective surfactants using the nanoscopic insights gleaned from analysis of the results of molecular simulations. We have developed protocols by which to use standard and freely available molecular simulation infrastructure to evaluate the effectiveness of surfactants that stabilize solid metal nanoparticles in supercritical fluids. From the results, which we validated against experimental observations, we were able to determine that the alkane-based surfactants, that are so effective in organic fluids, are ineffective or only partially effective in CO₂ because the weak C-H dipoles cannot make up for the energetic penalty incurred at the surfactant-fluid interface by CO₂ molecules due to loss of quadrupolar interactions with other CO₂ molecules. Though the effectiveness of purely alkane-based surfactants in carbon-dioxide can be improved by branching, they cannot approach the effectiveness of the fluoroalkanes. This is because the stronger C-F dipole can supply the required quadrupolar interactions and a unique geometry renders repulsive the fluorocarbons' electrostatic interactions with each other. We have also determined the source of the fluoroalkanes' hydrophobicity to be their size which offsets the effect of favourable electrostatic interactions with water. Hence we can provide guidelines for CO₂-philic yet hydrophobic surfactants.en
dc.description.departmentChemical Engineeringen
dc.format.mediumelectronicen
dc.identifier.urihttp://hdl.handle.net/2152/7655en
dc.language.isoengen
dc.rightsCopyright is held by the author. Presentation of this material on the Libraries' web site by University Libraries, The University of Texas at Austin was made possible under a limited license grant from the author who has retained all copyrights in the works.en
dc.subjectCarbon dioxideen
dc.subjectSolventsen
dc.subjectMolecular dynamicsen
dc.subjectSolvationen
dc.subjectSurfactantsen
dc.subjectFluorinated moietiesen
dc.subjectFluorocarbonsen
dc.subjectNanoparticlesen
dc.subjectFluoroalkanesen
dc.titleMolecular dynamics study of solvation phenomena to guide surfactant designen
thesis.degree.departmentChemical Engineeringen
thesis.degree.disciplineChemical Engineeringen
thesis.degree.grantorThe University of Texas at Austinen
thesis.degree.levelDoctoralen
thesis.degree.nameDoctor of Philosophyen

Access full-text files

Original bundle

Now showing 1 - 1 of 1
Loading...
Thumbnail Image
Name:
dalviv36580.pdf
Size:
7.41 MB
Format:
Adobe Portable Document Format

License bundle

Now showing 1 - 1 of 1
No Thumbnail Available
Name:
license.txt
Size:
1.75 KB
Format:
Item-specific license agreed upon to submission
Description: