Formation of Organic Acids and Carbonyl Compounds in n-Butane Oxidation via γ-Ketohydroperoxide Decomposition

被引：5

作者：

Popolan-Vaida, Denisia M. ^{[1
,2
]}

Eskola, Arkke J. ^{[3
,4
]}

Rotavera, Brandon ^{[3
,5
,6
]}

Lockyear, Jessica F. ^{[1
]}

Wang, Zhandong ^{[7
,8
]}

Sarathy, S. Mani ^{[7
]}

Caravan, Rebecca L. ^{[3
,9
]}

Zador, Judit ^{[3
]}

Sheps, Leonid ^{[3
]}

Lucassen, Arnas ^{[3
,10
]}

Moshammer, Kai ^{[3
,10
]}

Dagaut, Philippe ^{[11
]}

Osborn, David L. ^{[3
]}

Hansen, Nils ^{[3
]}

Leone, Stephen R. ^{[1
]}

Taatjes, Craig A. ^{[3
]}

机构：

[1] Univ Calif Berkeley, Dept Chem & Phys, Berkeley, CA 94720 USA

[2] Univ Cent Florida, Dept Chem, Orlando, FL 32816 USA

[3] Sandia Natl Labs, Combust Res Facil, Livermore, CA 94551 USA

[4] Univ Helsinki, Dept Chem, Helsinki 00014, Finland

[5] Univ Georgia, Dept Chem, Athens, GA 30602 USA

[6] Univ Georgia, Coll Engn, Athens, GA 30602 USA

[7] King Abdullah Univ Sci & Technol KAUST, Clean Combust Res Ctr CCRC, Thuwal 239556900, Saudi Arabia

[8] Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Anhui, Peoples R China

[9] Argonne Natl Lab, Chem Sci & Engn Div, Lemont, IL 60439 USA

[10] Phys Tech Bundesanstalt, D-38116 Braunschweig, Germany

[11] Ctr Natl Rech Sci CNRS, ICARE, INSIS, F-45071 Orleans 2, France

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2022年 / 61卷 / 42期

基金：

欧洲研究理事会;

关键词：

Autoignition; Hydrocarbon Oxidation; Ketohydroperoxides; Korcek Reaction; Photoionization; LOW-TEMPERATURE OXIDATION; PHOTOIONIZATION CROSS-SECTIONS; LIQUID-PHASE AUTOXIDATION; AUTOIGNITION CHEMISTRY; ELEVATED-TEMPERATURES; CHEMICAL-DYNAMICS; COMBUSTION; PRODUCTS; KINETICS; REACTOR;

D O I：

10.1002/anie.202209168

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A crucial chain-branching step in autoignition is the decomposition of ketohydroperoxides (KHP) to form an oxy radical and OH. Other pathways compete with chain-branching, such as "Korcek" dissociation of gamma-KHP to a carbonyl and an acid. Here we characterize the formation of a gamma-KHP and its decomposition to formic acid+acetone products from observations of n-butane oxidation in two complementary experiments. In jet-stirred reactor measurements, KHP is observed above 590 K. The KHP concentration decreases with increasing temperature, whereas formic acid and acetone products increase. Observation of characteristic isotopologs acetone-d(3) and formic acid-d(0) in the oxidation of CH3CD2CD2CH3 is consistent with a Korcek mechanism. In laser-initiated oxidation experiments of n-butane, formic acid and acetone are produced on the timescale of KHP removal. Modelling the time-resolved production of formic acid provides an estimated upper limit of 2 s(-1) for the rate coefficient of KHP decomposition to formic acid+acetone.

引用

页数：6

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