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  The ozonolysis of isoprene in a cryogenic buffer gas cell by high resolution microwave spectroscopy

Porterfield, J. P., Eibenberger, S., Patterson, D., & McCarthy, M. C. (2018). The ozonolysis of isoprene in a cryogenic buffer gas cell by high resolution microwave spectroscopy. Physical Chemistry Chemical Physics, 20(28), 16828-16834. doi:10.1039/c8cp02055h.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0001-F89F-5 Version Permalink: http://hdl.handle.net/21.11116/0000-0004-4D85-0
Genre: Journal Article

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 Creators:
Porterfield, Jessica P.1, Author
Eibenberger, Sandra2, 3, Author              
Patterson, David4, Author
McCarthy, Michael C.1, Author
Affiliations:
1Harvard-Smithsonian Center for Astrophysics, Harvard University, Cambridge, USA , ou_persistent22              
2Department of Physics, Harvard University, 17 Oxford Street, Cambridge MA 02138, USA , ou_persistent22              
3Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              
4Department of Physics, University of California Santa Barbara, Santa Barbara, USA , ou_persistent22              

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 Abstract: We have developed a method to quantify reaction product ratios using high resolution microwave spectroscopy in a cryogenic buffer gas cell. We demonstrate the power of this method with the study of the ozonolysis of isoprene, CH2=C(CH3)–CH=CH2, the most abundant, non-methane hydrocarbon emitted into the atmosphere by vegetation. Isoprene is an asymmetric diene, and reacts with O3 at the 1,2 position to produce methyl vinyl ketone (MVK), formaldehyde, and a pair of carbonyl oxides: [CH3CO–CH=Cv + CH2=OO] + [CH2=O + CH3COO–CH=CH2]. Alternatively, O3 could attack at the 3,4 position to produce methacrolein (MACR), formaldehyde, and two carbonyl oxides [CH2=C(CH3)–CHO + CH2=OO] + [CH2=O + CH2=C(CH3)–CHOO]. Purified O3 and isoprene were mixed for approximately 10 seconds under dilute (1.5–4% in argon) continuous flow conditions in an alumina tube held at 298 K and 5 Torr. Products exiting the tube were rapidly slowed and cooled within the buffer gas cell by collisions with cryogenic (4–7 K) He. High resolution chirped pulse microwave detection between 12 and 26 GHz was used to achieve highly sensitive (ppb scale), isomer-specific product quantification. We observed a ratio of MACR to MVK of 2.1 ± 0.4 under 1 : 1 ozone to isoprene conditions and 2.1 ± 0.2 under 2 : 1 ozone to isoprene conditions, a finding which is consistent with previous experimental results. Additionally, we discuss relative quantities of formic acid (HCOOH), an isomer of CH2=OO, and formaldehyde (CH2=O) under varying experimental conditions, and characterize the spectroscopic parameters of the singly-substituted 13C trans-isoprene and 13C anti-periplanar-methacrolein species. This work has the potential to be extended towards a complete branching ratio analysis, as well towards the ability to isolate, identify, and quantify new reactive intermediates in the ozonolysis of alkenes.

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Language(s): eng - English
 Dates: 2018-03-302018-05-312018-05-312018-06-28
 Publication Status: Published in print
 Pages: 7
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 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1039/c8cp02055h
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Title: Physical Chemistry Chemical Physics
  Abbreviation : Phys. Chem. Chem. Phys.
Source Genre: Journal
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Publ. Info: Cambridge, England : Royal Society of Chemistry
Pages: - Volume / Issue: 20 (28) Sequence Number: - Start / End Page: 16828 - 16834 Identifier: ISSN: 1463-9076
CoNE: /journals/resource/954925272413_1