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

Johan Albrecht Schmidt; Mildrid Kyte; Freja From Østerstrøm; Magnus Joelsson; Hasse Christian Knap; Solvejg Jørgensen; Ole John Nielsen; Tatsuhiro Murakami; Matthew Stanley 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 Albrecht Schmidt^*, Mildrid Kyte, Freja From Østerstrøm, Magnus Joelsson, Hasse Christian Knap, Solvejg Jørgensen, Ole John Nielsen, Tatsuhiro Murakami, Matthew Stanley Johnson

^*Corresponding author af dette arbejde

Kemisk Institut

1 Citationer (Scopus)

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 3.52×10-163.52×10-16 cm3 s−1 at 10 Torr increasing to 7.20×10-167.20×10-16 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(5.3±3.6)×10-15 cm3 s−1 at 296 K and 700 Torr using relative-rate technique

Originalsprog	Engelsk
Tidsskrift	Chemical Physics Letters
Vol/bind	675
Sider (fra-til)	111-117
Antal sider	7
ISSN	0009-2614
DOI	https://doi.org/10.1016/j.cplett.2017.03.005
Status	Udgivet - 2017

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10.1016/j.cplett.2017.03.005

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@article{acb3ba3b4269481188f8d0cd1d0cd06a,

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 O2forming 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 O2may explain the insensitivity of the reaction rate to pressure and O2. We calculate a rate constant of 3.52×10-16 cm3 s−1at 10 Torr increasing to 7.20×10-16 cm3 s−1at 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−1at 296 and 700 Torr using relative-rate technique.",

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

author = "Schmidt, {Johan Albrecht} and Mildrid Kyte and {\O}sterstr{\o}m, {Freja From} and Magnus Joelsson and Knap, {Hasse Christian} and Solvejg J{\o}rgensen and Nielsen, {Ole John} and Tatsuhiro Murakami and Johnson, {Matthew Stanley}",

year = "2017",

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

language = "English",

volume = "675",

pages = "111--117",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier",

}

TY - JOUR

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

T2 - A combined theoretical and experimental study

AU - Schmidt, Johan Albrecht

AU - Kyte, Mildrid

AU - Østerstrøm, Freja From

AU - Joelsson, Magnus

AU - Knap, Hasse Christian

AU - Jørgensen, Solvejg

AU - Nielsen, Ole John

AU - Murakami, Tatsuhiro

AU - Johnson, Matthew Stanley

PY - 2017

Y1 - 2017

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 O2forming 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 O2may explain the insensitivity of the reaction rate to pressure and O2. We calculate a rate constant of 3.52×10-16 cm3 s−1at 10 Torr increasing to 7.20×10-16 cm3 s−1at 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−1at 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 O2forming 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 O2may explain the insensitivity of the reaction rate to pressure and O2. We calculate a rate constant of 3.52×10-16 cm3 s−1at 10 Torr increasing to 7.20×10-16 cm3 s−1at 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−1at 296 and 700 Torr using relative-rate technique.

KW - Computational chemistry

KW - Kinetics

KW - OCS

KW - OH

KW - Relative rate

KW - SOOH

U2 - 10.1016/j.cplett.2017.03.005

DO - 10.1016/j.cplett.2017.03.005

M3 - Journal 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

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