The A ← X ABSORPTION SPECTRUM OF 2-NITROOXYBUTYL PEROXY RADICAL

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Presentation transcript:

The A ← X ABSORPTION SPECTRUM OF 2-NITROOXYBUTYL PEROXY RADICAL Nathan C. Eddingsaas, Kana Takematsu, Mitchio Okumura 64th OSU International Symposium on Molecular Spectroscopy

NO3•: The Primary Nighttime Atmospheric Oxidant Concentrations: Night time [NO3]: 100s of ppb Daytime [OH]: < 1 ppt NO3 + R=R R(NO3)-R O2 R(NO3)-ROO NO2 HO2 R(NO3)-ROOH NO RO2 R(NO3)-ROH, R(NO3)-RHO, etc. R(NO3)-ROONO2 k (298) with cis-2-butene OH : 5.6 x10-12 NO3•: 3.5 x 10-13 O3: 1.2 x 10-16 Alkene k (298) cm3 molec-1 s-1 Ethene 2.05 x 10-16 Propene 9.49 x 10-15 cis/trans-2-butene 3.52/3.90 x 10-13 α-pinene 6.16 x 10-12 Atkinson, R.; Arey J. J. Chem. Rev. 2003, 103, 4605.

A←X Absorption Spectra of sec-Butyl Peroxy Radical 45 cm-1 conformer splitting Origin of conformer A Origin of conformer B C-O-O bend of A O-O stretch of A ppm cm-1 Weak cross section ~ 10-20 cm2. Bound-bound transition with well defined structure. Can distinguish between different isomers and conformers. Glover, B.; Miller, T. J. Phys. Chem. A 2005, 109, 1191.

Effect of Electron Withdrawing Group on A←X Transition 0-0: 6656 cm-1 0-0: 7383 cm-1 Pushkarsky, et. al. J. Chem. Phys. 2000, 112, Zalubovksy, et. al. Chem. Phys. Lett. 2001, 335, 298. - 727 cm-1 CH3O2 CF3O2 (red shift) Addition of NO3 to peroxy radical should red shift the absorption bands.

CRDS Experimental Setup 10 % cis/trans-2-butene in N2 P: 3-5 Torr NO3 from N2O5 ~1.5 torr oxygen carrier gas ~150 torr Pump Press. readout heating tape (42°C) Ringdown mirror (99.99% reflective) thermocouple Total pressure in cell ~ 170 torr Residence time ~ 4 sec.

Initial Reactions Within Cell At 42 °C and 170 torr, nitrooxybutyl peroxy radical should dominate.

CRDS of Reactents: 2-butene and NO3• 300 200 Absorbance (ppm) 100 7000 7100 7200 7300 7400 7500 7600 Wavenumbers (cm-1) For more information on NO3• see Kana’s talks: WJ11 and RD02.

Reaction of 2-butene, NO3•, and O2 600 7120 cm-1 Reaction products 2-butene 500 400 7166 cm-1 Absorbance (ppm) 300 Origin of sec-butyl peroxy radical (7560 cm-1) 200 100 7000 7100 7200 7300 7400 7500 7600 Wavenumbers (cm-1) New peaks observed.

Identification of New Peaks Tentatively assigned to the origin of A←X transition of 2-nitrooxybutyl peroxy radical. Peaks 440 cm-1 redshifted from unsubstituted peroxy. 46 cm-1 separation (45 cm-1 observed from sec-butyl peroxy radical). Shows some pressure dependency. 7100 7200 200 300 400 500 600 Absorbance (ppm) Wavenumbers (cm-1) 7150 7050 7250 7120 cm-1 7166 cm-1

Computation of Nitrooxyethyl Peroxy B3LYP/6-31+G(d,p) * transition freq of A← X transition ~ 7458.264 cm-1 (-133.736 cm-1 from ethylperoxy) * Shown by the Miller group to model peroxy radicals very well.

Computation of Nitrooxyethyl Peroxy Forced into Cs symmetry Transition freq~ 7285.666 cm-1 -76.33429 cm-1 from ethylperoxy. -172.598 cm-1 from C1 transition (-230cm-1 for ethyl peroxy radical). Modeled electronegative CF3O2• with similar difficulties.

CRDS of Region of O-O Stretch CRDS of reaction of 2-butene with NO3• and O2 125 NO3• 100 75 Absorbance (ppm) 50 25 8000 8050 8100 8150 8200 8250 Wavenumbers (cm-1) Peroxy radical O-O stretch typically observed ~ 1000 cm-1 from origin.

Normalized Intensity (au) No unidentified structure observed. New Feature From HNO3 1.0 Sum NO3+Butene NO3 2-Butene HNO3 Normalized Intensity (au) 0.5 8000 8050 8100 8150 8200 8250 Wavenumbers (cm-1) No unidentified structure observed.

Normalized Intensity (au) Effect of Temperature 8000 8050 8100 8150 8200 8250 0.5 1.0 Normalized Intensity (au) Wavenumbers (cm-1) NO3+ Butene 115 °C NO3 2-Butene HNO3 Sum * New peak ~1100 cm-1 from 7120 cm-1 peak. Typically O-O stretch in peroxy radical is ~1000 cm-1 from origin.

2-nitrooxybutyl peroxy radical Summary CRDS of reaction of 2-butene with NO3• has been observed. Peaks at 7120 cm-1 and 7166 cm-1 have been tentatively assigned to A-X origin of nitrooxybutyl peroxy radical. Preliminary computation of nitrooxyethyl peroxy radical show red shift of substituted peroxy. Possible observation of O-O stretch of nitrooxybutyl peroxy radical. 7100 7200 200 400 600 Absorbance (ppm) Wavenumbers (cm-1) 7150 7050 7250 2-nitrooxybutyl peroxy radical

Follow up and Future Work Use higher flow rate to minimize secondary chemistry. Confirm assignment of nitrooxybutyl peroxy radical by chemical means. Addition of NO Using deuterated butene. Obtain better computational simulations of model compound and exact compound. Extend system to other alkenes and dienes. Pulsed photolysis source to study kinetics. Look at products from reactions of alkenes with other oxidants such as OH• and O3.

Acknowledgments Prof. Mitchio Okumura Kana Takematsu Sigrid Barklund Funding: Camille & Henry Dreyfus Postdoctoral Program in Environmental Chemistry EPA STAR Graduate Fellowship (Kana) NASA UARP