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dc.contributor.authorDavis, Gwen Marieen_US
dc.date.accessioned2014-03-14T20:44:49Z
dc.date.available2014-03-14T20:44:49Z
dc.date.issued2003-08-27en_US
dc.identifier.otheretd-09052003-100910en_US
dc.identifier.urihttp://hdl.handle.net/10919/34927
dc.description.abstractReactions of strongly oxidizing pollutants with unsaturated hydrocarbon surfaces are important to many areas of scientific interest. For example, reactions of unsaturated hydrocarbons on the surface of tropospheric aerosols could have a great effect on the oxidizing capacity of the troposphere while the reaction products could be involved in the formation of clouds and smog. These reactions are also important in understanding the toxic effect inhalation of these pollutants have on the pulmonary surfactant of the lung, the only amicable air-water interface of the body. The fatty acids of this surfactant are as much as 30% unsaturated, and exposure to oxidizing pollutant is known to alter both the composition and function of the surfactant. Understanding the reaction mechanism will further the knowledge of how this toxicity occurs. While the reactions of strongly oxidizing pollutants, such as ozone and nitrogen dioxide, with alkenes in the gas and solution phases are well known, the interfacial reaction mechanisms of these species is not fully understood. The goal of this study is to determine the reaction mechanism when an unsaturated hydrocarbon monolayer at the gas-surface interface is exposed to gas phase nitrogen dioxide. An olefin-terminated thiol was synthesized and a self-assembled monolayer on Au(111) made and characterized using Reflection-Absorption Infrared Spectroscopy (RAIRS). This unsaturated surface was then exposed to NO2 at a pressure of 1x10-4 mbar in a UHV (Ultrahigh Vacuum) chamber. Time-resolved RAIRS was preformed in situ to monitor the reaction during exposure. X-ray Photoelectron Spectroscopy and RAIRS determined the surface reaction product as an aldehyde. While the mechanism can not be precisely determined, two mechanisms involving either the hydrogen abstraction or radical addition of the NO2 to yield an aldehyde are proposed.en_US
dc.publisherVirginia Techen_US
dc.relation.haspartThesis.pdfen_US
dc.rightsI hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to Virginia Tech or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.en_US
dc.subjectreaction mechanismen_US
dc.subjectnitrogen dioxideen_US
dc.subjectultrahigh vacuumen_US
dc.subjectself-assembled monolayersen_US
dc.subjectunsaturated surfaceen_US
dc.titleInterfacial Reaction of an Olefin-Terminated Self-Assembled Monolayer Exposed to Nitrogen Dioxide: An Investigation Into the Reaction Rate and Mechanismen_US
dc.typeThesisen_US
dc.contributor.departmentChemistryen_US
dc.description.degreeMaster of Scienceen_US
thesis.degree.nameMaster of Scienceen_US
thesis.degree.levelmastersen_US
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen_US
thesis.degree.disciplineChemistryen_US
dc.contributor.committeechairMorris, John R.en_US
dc.contributor.committeememberCrawford, T. Danielen_US
dc.contributor.committeememberAnderson, Mark R.en_US
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-09052003-100910/en_US
dc.date.sdate2003-09-05en_US
dc.date.rdate2004-09-18
dc.date.adate2003-09-18en_US


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