On adduct formation and reactivity in the OCS + OH reaction: A combined theoretical and experimental study

Johan A. Schmidt; Mildrid Kyte; Freja F. Østerstrøm; Lars M.T. Joelsson; Hasse C. Knap; Solvejg Jørgensen; Ole John Nielsen; Tatsuhiro Murakami; Matthew S. Johnson

doi:10.1016/j.cplett.2017.03.005

On adduct formation and reactivity in the OCS + OH reaction: A combined theoretical and experimental study

Johan A. Schmidt^*, Mildrid Kyte, Freja F. Østerstrøm, Lars M.T. Joelsson, Hasse C. Knap, Solvejg Jørgensen, Ole John Nielsen, Tatsuhiro Murakami, Matthew S. Johnson

^*Corresponding author for this work

Environment and Geography

Research output: Contribution to journal › Article › peer-review

Abstract

The OCS + OH reaction occurs either via adduct formation or direct S-abstraction. We investigate OH-oxidation of OCS using quantum chemical methods and find that the OC(OH)S adduct reacts rapidly with O₂ forming SOOH + CO₂. SOOH rapidly dissociates under atmospheric conditions regenerating OH. We interpret earlier experimental results based on monitoring OH-loss, and find that OH-regeneration in presence of O₂ may explain the insensitivity of the reaction rate to pressure and O₂. We calculate a rate constant of 3.52×10^-16 cm³ s⁻¹ at 10 Torr increasing to 7.20×10^-16 cm³ s⁻¹ at 700 Torr. In addition we present a new experimental determination of the OCS + OH rate constant of (5.3±3.6)×10^-15 cm³ s⁻¹ at 296 and 700 Torr using relative-rate technique.

Original language	English
Pages (from-to)	111-117
Number of pages	7
Journal	Chemical Physics Letters
Volume	675
Early online date	6 Mar 2017
DOIs	https://doi.org/10.1016/j.cplett.2017.03.005
Publication status	Published - May 2017

Keywords

Computational chemistry
Kinetics
OCS
OH
Relative rate
SOOH

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10.1016/j.cplett.2017.03.005

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@article{168ec87793544bec9803786d8035f66c,

title = "On adduct formation and reactivity in the OCS + OH reaction: A combined theoretical and experimental study",

abstract = "The OCS + OH reaction occurs either via adduct formation or direct S-abstraction. We investigate OH-oxidation of OCS using quantum chemical methods and find that the OC(OH)S adduct reacts rapidly with O2 forming SOOH + CO2. SOOH rapidly dissociates under atmospheric conditions regenerating OH. We interpret earlier experimental results based on monitoring OH-loss, and find that OH-regeneration in presence of O2 may explain the insensitivity of the reaction rate to pressure and O2. We calculate a rate constant of 3.52×10-16 cm3 s−1 at 10 Torr increasing to 7.20×10-16 cm3 s−1 at 700 Torr. In addition we present a new experimental determination of the OCS + OH rate constant of (5.3±3.6)×10-15 cm3 s−1 at 296 and 700 Torr using relative-rate technique.",

keywords = "Computational chemistry, Kinetics, OCS, OH, Relative rate, SOOH",

author = "Schmidt, {Johan A.} and Mildrid Kyte and {\O}sterstr{\o}m, {Freja F.} and Joelsson, {Lars M.T.} and Knap, {Hasse C.} and Solvejg J{\o}rgensen and Nielsen, {Ole John} and Tatsuhiro Murakami and Johnson, {Matthew S.}",

year = "2017",

month = may,

doi = "10.1016/j.cplett.2017.03.005",

language = "English",

volume = "675",

pages = "111--117",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier",

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TY - JOUR

T1 - On adduct formation and reactivity in the OCS + OH reaction

T2 - A combined theoretical and experimental study

AU - Schmidt, Johan A.

AU - Kyte, Mildrid

AU - Østerstrøm, Freja F.

AU - Joelsson, Lars M.T.

AU - Knap, Hasse C.

AU - Jørgensen, Solvejg

AU - Nielsen, Ole John

AU - Murakami, Tatsuhiro

AU - Johnson, Matthew S.

PY - 2017/5

Y1 - 2017/5

N2 - The OCS + OH reaction occurs either via adduct formation or direct S-abstraction. We investigate OH-oxidation of OCS using quantum chemical methods and find that the OC(OH)S adduct reacts rapidly with O2 forming SOOH + CO2. SOOH rapidly dissociates under atmospheric conditions regenerating OH. We interpret earlier experimental results based on monitoring OH-loss, and find that OH-regeneration in presence of O2 may explain the insensitivity of the reaction rate to pressure and O2. We calculate a rate constant of 3.52×10-16 cm3 s−1 at 10 Torr increasing to 7.20×10-16 cm3 s−1 at 700 Torr. In addition we present a new experimental determination of the OCS + OH rate constant of (5.3±3.6)×10-15 cm3 s−1 at 296 and 700 Torr using relative-rate technique.

AB - The OCS + OH reaction occurs either via adduct formation or direct S-abstraction. We investigate OH-oxidation of OCS using quantum chemical methods and find that the OC(OH)S adduct reacts rapidly with O2 forming SOOH + CO2. SOOH rapidly dissociates under atmospheric conditions regenerating OH. We interpret earlier experimental results based on monitoring OH-loss, and find that OH-regeneration in presence of O2 may explain the insensitivity of the reaction rate to pressure and O2. We calculate a rate constant of 3.52×10-16 cm3 s−1 at 10 Torr increasing to 7.20×10-16 cm3 s−1 at 700 Torr. In addition we present a new experimental determination of the OCS + OH rate constant of (5.3±3.6)×10-15 cm3 s−1 at 296 and 700 Torr using relative-rate technique.

KW - Computational chemistry

KW - Kinetics

KW - OCS

KW - OH

KW - Relative rate

KW - SOOH

UR - http://www.scopus.com/inward/record.url?scp=85015788841&partnerID=8YFLogxK

U2 - 10.1016/j.cplett.2017.03.005

DO - 10.1016/j.cplett.2017.03.005

M3 - Article

AN - SCOPUS:85015788841

SN - 0009-2614

VL - 675

SP - 111

EP - 117

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

On adduct formation and reactivity in the OCS + OH reaction: A combined theoretical and experimental study

Abstract

Keywords

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