Kinetics and Products of the Reaction of the First-Generation Isoprene Hydroxy Hydroperoxide (ISOPOOH) with OH

The Journal of Physical Chemistry. a
Jason M St ClairPaul O Wennberg

Abstract

The atmospheric oxidation of isoprene by the OH radical leads to the formation of several isomers of an unsaturated hydroxy hydroperoxide, ISOPOOH. Oxidation of ISOPOOH by OH produces epoxydiols, IEPOX, which have been shown to contribute mass to secondary organic aerosol (SOA). We present kinetic rate constant measurements for OH + ISOPOOH using synthetic standards of the two major isomers: (1,2)- and (4,3)-ISOPOOH. At 297 K, the total OH rate constant is 7.5 ± 1.2 × 10(-11) cm(3) molecule(-1) s(-1) for (1,2)-ISOPOOH and 1.18 ± 0.19 × 10(-10) cm(3) molecule(-1) s(-1) for (4,3)-ISOPOOH. Abstraction of the hydroperoxy hydrogen accounts for approximately 12% and 4% of the reactivity for (1,2)-ISOPOOH and (4,3)-ISOPOOH, respectively. The sum of all H-abstractions account for approximately 15% and 7% of the reactivity for (1,2)-ISOPOOH and (4,3)-ISOPOOH, respectively. The major product observed from both ISOPOOH isomers was IEPOX (cis-β and trans-β isomers), with a ∼ 2:1 preference for trans-β IEPOX and similar total yields from each ISOPOOH isomer (∼ 70-80%). An IEPOX global production rate of more than 100 Tg C each year is estimated from this chemistry using a global 3D chemical transport model, similar to earlier estimates. Fin...Continue Reading

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Citations

Dec 17, 2015·The Journal of Physical Chemistry. a·Kelvin Hamilton BatesPaul O Wennberg
May 18, 2016·Proceedings of the National Academy of Sciences of the United States of America·Yingjun LiuScot T Martin
Jul 29, 2016·Environmental Science & Technology·Matthieu RivaJason D Surratt
Dec 16, 2016·The Journal of Physical Chemistry. a·Torsten BerndtMarkku Kulmala
Mar 11, 2017·The Journal of Physical Chemistry Letters·Kelley C BarsantiJoel A Thornton
Apr 12, 2017·Journal of the American Chemical Society·Alexander P TengPaul O Wennberg
Jun 24, 2017·Molecular Biology and Evolution·Mingai LiClaudio Varotto
Jul 3, 2018·Atmospheric Chemistry and Physics·Jingqiu MaoLarry W Horowitz
Jan 1, 2016·Atmospheric Measurement Techniques·Jason M St ClairThomas F Hanisco
Jan 1, 2016·Atmospheric Chemistry and Physics·Katherine R TravisXianliang Zhou
Dec 20, 2017·Proceedings of the National Academy of Sciences of the United States of America·Eric PraskePaul O Wennberg
Feb 22, 2018·Physical Chemistry Chemical Physics : PCCP·Zhen LiuJozef Peeters
Aug 5, 2021·The Journal of Physical Chemistry. a·Victoria P BarberJesse H Kroll
Aug 2, 2017·The Journal of Physical Chemistry. a·Martta ToivolaTheo Kurtén
Sep 4, 2015·The Journal of Physical Chemistry. a·Rebecca H SchwantesPaul O Wennberg
Mar 10, 2018·Chemical Reviews·Paul O WennbergJohn H Seinfeld
Jan 30, 2018·Environmental Science & Technology·Yuanlong HuangJohn H Seinfeld
Nov 13, 2019·The Journal of Physical Chemistry. a·Kristian H MøllerHenrik Grum Kjaergaard
Oct 12, 2019·Environmental Science & Technology·Eleni DovrouFrank N Keutsch
Jul 12, 2018·The Journal of Physical Chemistry. a·Hannah M AllenPaul O Wennberg
Oct 5, 2017·The Journal of Physical Chemistry. a·Ivan R PileticLibero J Bartolotti
Dec 1, 2018·Environmental Science & Technology·Santino J StropoliMatthew J Elrod
Dec 15, 2018·The Journal of Physical Chemistry. a·Eric PraskePaul O Wennberg
Jan 8, 2019·The Journal of Physical Chemistry. a·Kristian H MøllerHenrik G Kjaergaard
Oct 8, 2021·Environmental Science & Technology·Kelvin H BatesTran B Nguyen
Dec 1, 2021·The Journal of Physical Chemistry. a·Victoria P Barber, Jesse H Kroll

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