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An Investigation of the Thermal and Photochemical Reactions of Ozone with Alkenes Using Matrix Isolation

Rakestraw, Bridgett
http://rave.ohiolink.edu/etdc/view?acc_num=ucin1337287427

Abstract Details

2012, PhD, University of Cincinnati, Arts and Sciences: Chemistry.
The matrix isolation technique combined with infrared (IR) spectroscopy and theoretical calculations has been used to investigate the thermal and photochemical reactions of ozone with propene, 2,3-dimethyl-2-butene (DMB), styrene, and Z-3-methyl-2-pentene (MP). In the DMB and styrene twin jet systems, upon annealing to 35 K and 68 K (respectively) several bands were assigned to the primary ozonides, elusive Criegee intermediates, and secondary ozonides. The twin jet annealed MP system yielded assignments to the primary and secondary ozonides. For DMB, the wavelength dependence of the photo-destruction of these product bands was explored with irradiation from λ = 220 to = 580 nm. A recently developed concentric jet method was also utilized to increase yields and monitor the concentration of intermediates and products formed at different times by varying the length of mixing distance (d = 0 to -11 cm) before reaching the cold cell for spectroscopic detection. For the reaction of ozone with propene, initial twin jet deposition upon annealing to 35 K yielded no visible changes in the IR spectra. Merged jet deposition led to the observation of ¿¿¿¿¿¿¿¿¿¿¿¿¿¿later¿¿¿¿¿¿¿, more stable products of this reaction for each alkene. Irradiation of the twin jet systems for all alkenes in this study were dominated by ozone decomposition and subsequent O atom reaction with the alkene. Identification of intermediates and products formed during the ozonolysis of these alkenes were further supported by 18O and labeling experiments as well as theoretical density functional calculations at the B3LYP/6-311G++(d,2p) level.
Bruce Ault, PhD (Committee Chair)
Thomas Beck, PhD (Committee Member)
Allan Pinhas, PhD (Committee Member)
David Smithrud, PhD (Committee Member)
121 p.
Physical Chemistry
Photochemical; Alkenes;

Recommended Citations

Citations

  • Rakestraw, B. (2012). An Investigation of the Thermal and Photochemical Reactions of Ozone with Alkenes Using Matrix Isolation [Doctoral dissertation, University of Cincinnati]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1337287427

    APA Style (7th edition)

  • Rakestraw, Bridgett. An Investigation of the Thermal and Photochemical Reactions of Ozone with Alkenes Using Matrix Isolation. 2012. University of Cincinnati, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=ucin1337287427.

    MLA Style (8th edition)

  • Rakestraw, Bridgett. "An Investigation of the Thermal and Photochemical Reactions of Ozone with Alkenes Using Matrix Isolation." Doctoral dissertation, University of Cincinnati, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1337287427

    Chicago Manual of Style (17th edition)

ucin1337287427
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© 2012, all rights reserved.
This open access ETD is published by University of Cincinnati and OhioLINK.