Radical-molecule reaction dynamics studied using a pulsed supersonic Laval nozzle flow reactor between 53 and 188 Kelvin

Persistent Link:
http://hdl.handle.net/10150/280633
Title:
Radical-molecule reaction dynamics studied using a pulsed supersonic Laval nozzle flow reactor between 53 and 188 Kelvin
Author:
Mullen, Christopher
Issue Date:
2004
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
A pulsed supersonic Laval nozzle flow reactor has been employed to investigate a variety of neutral-radical reaction processes at temperatures between 53 and 188 Kelvin. These supersonic flows simulate the conditions found in the Earth's upper atmosphere as well as certain environments in the interstellar medium and outer planetary atmospheres and thus provide direct information on the chemistry and physical processes occurring in those environments. Studies of this type, in the limit of 0 Kelvin, coupled with modern astronomical observations of planetary atmospheres and dense molecular clouds provide for a global understanding of chemistry in cold environments. With this in mind, the flow reactor was used to conduct fundamental studies involving the reactivity of hydroxyl (OH) and imidogen (NH) radical species with a variety of partners. More specifically, the reactions of OH+HBr and all of the H/D isotopic variants were explored between 53 and 135 K, with the goal of elucidating the kinetic isotope effects, both primary and secondary, for a reaction system occurring over a potential energy surface without an appreciable barrier, that demonstrates inverse temperature dependence. While not of direct astronomical importance, the reaction of OH+HBr does affect the partitioning of Br in the Earth's atmosphere, and knowledge of kinetic isotope effects helps one understand the chemistry leading to H/D fractionation observed in a variety of interstellar environments. The reactions of NH radical with NO, saturated, and unsaturated hydrocarbons were also studied between 53 and 188 Kelvin in the Laval nozzle flow reactor. These species were chosen as most are important constituents in the atmosphere of Titan, which is known to possess a rich organic chemistry. The reactions of NH with the unsaturated hydrocarbons are found to display negative temperature dependence over the window investigated, and are thought to proceed through an addition mechanism. Finally, the flow reactor was also coupled to a tunable vacuum and extreme ultraviolet frequency source based on four wave frequency mixing to allow for studies of radical species with their first electronic transitions in this frequency range. A discussion of the development, implementation, and future directions is included.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Chemistry, Physical.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Graduate College; Chemistry
Degree Grantor:
University of Arizona
Advisor:
Smith, Mark A.

Full metadata record

DC FieldValue Language
dc.language.isoen_USen_US
dc.titleRadical-molecule reaction dynamics studied using a pulsed supersonic Laval nozzle flow reactor between 53 and 188 Kelvinen_US
dc.creatorMullen, Christopheren_US
dc.contributor.authorMullen, Christopheren_US
dc.date.issued2004en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractA pulsed supersonic Laval nozzle flow reactor has been employed to investigate a variety of neutral-radical reaction processes at temperatures between 53 and 188 Kelvin. These supersonic flows simulate the conditions found in the Earth's upper atmosphere as well as certain environments in the interstellar medium and outer planetary atmospheres and thus provide direct information on the chemistry and physical processes occurring in those environments. Studies of this type, in the limit of 0 Kelvin, coupled with modern astronomical observations of planetary atmospheres and dense molecular clouds provide for a global understanding of chemistry in cold environments. With this in mind, the flow reactor was used to conduct fundamental studies involving the reactivity of hydroxyl (OH) and imidogen (NH) radical species with a variety of partners. More specifically, the reactions of OH+HBr and all of the H/D isotopic variants were explored between 53 and 135 K, with the goal of elucidating the kinetic isotope effects, both primary and secondary, for a reaction system occurring over a potential energy surface without an appreciable barrier, that demonstrates inverse temperature dependence. While not of direct astronomical importance, the reaction of OH+HBr does affect the partitioning of Br in the Earth's atmosphere, and knowledge of kinetic isotope effects helps one understand the chemistry leading to H/D fractionation observed in a variety of interstellar environments. The reactions of NH radical with NO, saturated, and unsaturated hydrocarbons were also studied between 53 and 188 Kelvin in the Laval nozzle flow reactor. These species were chosen as most are important constituents in the atmosphere of Titan, which is known to possess a rich organic chemistry. The reactions of NH with the unsaturated hydrocarbons are found to display negative temperature dependence over the window investigated, and are thought to proceed through an addition mechanism. Finally, the flow reactor was also coupled to a tunable vacuum and extreme ultraviolet frequency source based on four wave frequency mixing to allow for studies of radical species with their first electronic transitions in this frequency range. A discussion of the development, implementation, and future directions is included.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectChemistry, Physical.en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorSmith, Mark A.en_US
dc.identifier.proquest3145107en_US
dc.identifier.bibrecord.b47210369en_US
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