Kinetics and products of the reaction of the first-generation isoprene hydroxy hydroperoxide (ISOPOOH) with OH

Jason M. St. Clair; Jean C. Rivera-Rios; John D. Crounse; Hasse Christian Knap; Kelvin H. Bates; Alex P. Teng; Solvejg Jørgensen; Henrik Grum Kjærgaard; Frank N. Keutsch; Paul O. Wennberg

doi:10.1021/acs.jpca.5b06532

Kinetics and products of the reaction of the first-generation isoprene hydroxy hydroperoxide (ISOPOOH) with OH

Jason M. St. Clair, Jean C. Rivera-Rios, John D. Crounse, Hasse Christian Knap, Kelvin H. Bates, Alex P. Teng, Solvejg Jørgensen, Henrik Grum Kjærgaard, Frank N. Keutsch, Paul O. Wennberg

Department of Chemistry

70 Citations (Scopus)

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. Finally, following addition of OH to ISOPOOH, approximately 13% of the reactivity proceeds via addition of O2 at 297 K and 745 Torr. In the presence of NO, these peroxy radicals lead to formation of small carbonyl compounds. Under HO2 dominated chemistry, no products are observed from these channels. We suggest that the major products, highly oxygenated organic peroxides, are lost to the chamber walls. In the atmosphere, formation of these compounds may contribute to organic aerosol mass.

Original language	English
Journal	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume	120
Issue number	9
Pages (from-to)	1441–1451
Number of pages	11
ISSN	1089-5639
DOIs	https://doi.org/10.1021/acs.jpca.5b06532
Publication status	Published - 10 Mar 2016

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10.1021/acs.jpca.5b06532

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St. Clair, J. M., Rivera-Rios, J. C., Crounse, J. D., Knap, H. C., Bates, K. H., Teng, A. P., Jørgensen, S., Kjærgaard, H. G., Keutsch, F. N., & Wennberg, P. O. (2016). Kinetics and products of the reaction of the first-generation isoprene hydroxy hydroperoxide (ISOPOOH) with OH. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 120(9), 1441–1451. https://doi.org/10.1021/acs.jpca.5b06532

Kinetics and products of the reaction of the first-generation isoprene hydroxy hydroperoxide (ISOPOOH) with OH. / St. Clair, Jason M.; Rivera-Rios, Jean C.; Crounse, John D. et al.
In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 120, No. 9, 10.03.2016, p. 1441–1451.

Research output: Contribution to journal › Journal article › Research › peer-review

St. Clair, JM, Rivera-Rios, JC, Crounse, JD, Knap, HC, Bates, KH, Teng, AP, Jørgensen, S , Kjærgaard, HG, Keutsch, FN & Wennberg, PO 2016, 'Kinetics and products of the reaction of the first-generation isoprene hydroxy hydroperoxide (ISOPOOH) with OH', Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, vol. 120, no. 9, pp. 1441–1451. https://doi.org/10.1021/acs.jpca.5b06532

@article{29dc70637f6648359777b5e57b12481b,

title = "Kinetics and products of the reaction of the first-generation isoprene hydroxy hydroperoxide (ISOPOOH) with OH",

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. Finally, following addition of OH to ISOPOOH, approximately 13% of the reactivity proceeds via addition of O2 at 297 K and 745 Torr. In the presence of NO, these peroxy radicals lead to formation of small carbonyl compounds. Under HO2 dominated chemistry, no products are observed from these channels. We suggest that the major products, highly oxygenated organic peroxides, are lost to the chamber walls. In the atmosphere, formation of these compounds may contribute to organic aerosol mass.",

author = "{St. Clair}, {Jason M.} and Rivera-Rios, {Jean C.} and Crounse, {John D.} and Knap, {Hasse Christian} and Bates, {Kelvin H.} and Teng, {Alex P.} and Solvejg J{\o}rgensen and Kj{\ae}rgaard, {Henrik Grum} and Keutsch, {Frank N.} and Wennberg, {Paul O.}",

year = "2016",

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doi = "10.1021/acs.jpca.5b06532",

language = "English",

volume = "120",

pages = "1441–1451",

journal = "Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory",

issn = "1089-5639",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Kinetics and products of the reaction of the first-generation isoprene hydroxy hydroperoxide (ISOPOOH) with OH

AU - St. Clair, Jason M.

AU - Rivera-Rios, Jean C.

AU - Crounse, John D.

AU - Knap, Hasse Christian

AU - Bates, Kelvin H.

AU - Teng, Alex P.

AU - Jørgensen, Solvejg

AU - Kjærgaard, Henrik Grum

AU - Keutsch, Frank N.

AU - Wennberg, Paul O.

PY - 2016/3/10

Y1 - 2016/3/10

N2 - 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. Finally, following addition of OH to ISOPOOH, approximately 13% of the reactivity proceeds via addition of O2 at 297 K and 745 Torr. In the presence of NO, these peroxy radicals lead to formation of small carbonyl compounds. Under HO2 dominated chemistry, no products are observed from these channels. We suggest that the major products, highly oxygenated organic peroxides, are lost to the chamber walls. In the atmosphere, formation of these compounds may contribute to organic aerosol mass.

AB - 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. Finally, following addition of OH to ISOPOOH, approximately 13% of the reactivity proceeds via addition of O2 at 297 K and 745 Torr. In the presence of NO, these peroxy radicals lead to formation of small carbonyl compounds. Under HO2 dominated chemistry, no products are observed from these channels. We suggest that the major products, highly oxygenated organic peroxides, are lost to the chamber walls. In the atmosphere, formation of these compounds may contribute to organic aerosol mass.

U2 - 10.1021/acs.jpca.5b06532

DO - 10.1021/acs.jpca.5b06532

M3 - Journal article

C2 - 26327174

SN - 1089-5639

VL - 120

SP - 1441

EP - 1451

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 9

ER -

Kinetics and products of the reaction of the first-generation isoprene hydroxy hydroperoxide (ISOPOOH) with OH

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