Rate coefficients for cycloalkyl + O reactions and product branching in the decomposition of chemically activated cycloalkoxy radicals: an experimental and theoretical study
Literature Information
Karlheinz Hoyermann, Sven Maarfeld, Frank Nacke, Jörg Nothdurft, Matthias Olzmann, Jens Wehmeyer, Oliver Welz, Thomas Zeuch
The kinetics of cycloalkyl + O reactions were studied with respect to their rate coefficients and the product branching ratios from the decomposition of the chemically activated cycloalkoxy radicals. Rate coefficients for the reactions of cyclohexyl (c-C6H11), cycloheptyl (c-C7H13) and cyclooctyl (c-C8H15) radicals with oxygen atoms were determined with an experimental setup consisting of a discharge flow reactor with molecular beam sampling and REMPI/TOF-MS detection. The following rate coefficients were obtained (units: cm3/mol−1 s−1): k(c-C6H11 + O) = (1.33 ± 0.24) × 1014(T/298 K)0.11 (T = 250–600 K), k(c-C7H13 + O) = (1.85 ± 0.25) × 1014 (T = 298 K), k(c-C8H15 + O) = (1.56 ± 0.20) × 1014(T/298 K)0.66±0.15 (T = 268–363 K). Stable products were determined by quantitative FTIR spectroscopy. The decomposition of the cycloalkoxy radicals leads besides β-C–H bond fission (yields: 24% for c-C6H11O, 20–25% for c-C8H15O) mainly to alkyl radicals by ring-opening via β-C–C bond cleavage. These open-chain alkyl radicals further decompose mainly by β-C–C bond scission. An increase of the total pressure from 4 mbar to 1 bar had no effect on the product distribution for the reaction c-C6H11 + O, whereas for the reaction c-C8H15 + O further decomposition of the ring-opening product is significantly suppressed at 1 bar. The experimental results on the channel branching and its pressure dependence were rationalized with the statistical rate theory. A comparison of the experimental and modeling results indicates a significant influence of hindered internal rotations (HIRs) on the reactions of the ring-opening products. The harmonic approximation to describe these modes was shown to be inadequate, while a treatment as one-dimensional HIRs led to a significantly improved agreement between experimental and modeling results. Implications of our findings for the formation of secondary organic aerosol and high-temperature combustion are discussed.
Related Literature
Shape-dependent magnetic properties of low-dimensional nanoscale Prussian blue (PB) analogue SmFe(CN)6·4H2O
Hao-Ling Sun, Hongtao Shi, Fei Zhao, Limin Qi, Song Gao
DOI: 10.1039/B507240A
Control of dark current in photoelectrochemical (TiO2/I−–I3−) and dye-sensitized solar cells
Seigo Ito, Paul Liska, Pascal Comte, Raphaël Charvet, Peter Péchy, Udo Bach, Lukas Schmidt-Mende, Shaik Mohammed Zakeeruddin, Andreas Kay, Mohammad K. Nazeeruddin, Michael Grätzel
DOI: 10.1039/B505718C
Synthesis of 1,3-dioxo-hexahydropyrido[1,2-c][1,3]diazepine carboxylates, a new bicyclic skeleton formed by ring expansion–RCM methodology
Nicolai Dieltiens, Diederica D. Claeys, Bart Allaert, Francis Verpoort, Christian V. Stevens
DOI: 10.1039/B508663A
Thio[2-(benzoylamino)ethylamino]-β-CD fragment modified gold nanoparticles as recycling extractors for [60]fullerene
Yu Liu, Ying-Wei Yang, Yong Chen
DOI: 10.1039/B507650A
Self-repairing polymers: poly(dioxaborolane)s containing trigonal planar boron
Weijun Niu, Caroline O'Sullivan, Brett M. Rambo, Mark D. Smith, John J. Lavigne
DOI: 10.1039/B504634C
Efficient two-step synthesis of 3-halo-3-enals or 2-halo-2-alkenyl ketones from propargylic bromides via a unique cationic 1,2-aryl or proton shift in electrophilic addition reaction of 2,3-allenols with X+
Chunling Fu, Jing Li
DOI: 10.1039/B508069J
Photostability of a highly luminescent europium β-diketonate complex in imidazolium ionic liquids
Peter Nockemann, Eva Beurer, Kris Driesen, Rik Van Deun, Kristof Van Hecke, Luc Van Meervelt, Koen Binnemans
DOI: 10.1039/B506915G
A new simple synthesis of poly(thiophene-methine)s
Md. Badruz Zaman, Dmitrii F. Perepichka
DOI: 10.1039/B506138E
Chiral azide-bridged two-dimensional Cu(ii) compounds showing a field-induced spin–flop transition
Young Sin You, Jung Hee Yoon, Hyoung Chan Kim, Chang Seop Hong
DOI: 10.1039/B507051A
You might also like
How should waste containing N-Methoxy-N-methyl-1,3-thiazole-5-carboxamide (CAS: 898825-89-3) be handled?
Waste containing N-Methoxy-N-methyl-1,3-thiazole-5-carboxamide (CAS: 898825-89-3...
How should N-(4-Biphenylyl)dibenzo[b,d]furan-4-amine (CAS: 1318338-47-4) be stored?
N-(4-Biphenylyl)dibenzo[b,d]furan-4-amine should be stored in a tightly sealed c...
What is the market or research trend for 3-Acetamido-5-amino-2,4,6-triiodobenzoic acid (CAS: 1713-07-1)?
The market for 3-Acetamido-5-amino-2,4,6-triiodobenzoic acid (CAS: 1713-07-1) is...
How should Benzyl 2-O-acetyl-3,4,6-tri-O-benzyl-beta-D-galactopyranoside (CAS: 61820-03-9) be stored?
Benzyl 2-O-acetyl-3,4,6-tri-O-benzyl-beta-D-galactopyranoside (CAS: 61820-03-9) ...
What regulatory guidelines apply to 2-Ethylpiperazine dihydrochloride (CAS: 438050-52-3)?
2-Ethylpiperazine dihydrochloride (CAS: 438050-52-3) is regulated under the Glob...
What regulatory guidelines apply to 1,1'-[1,3-Phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5-dione) (CAS: 119462-56-5)?
1,1'-[1,3-Phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5-dione) (CAS: 11946...
Are there alternatives to 5-Fluoro-2-(1-pyrrolidinyl)pyridine (CAS: 1287217-79-1) in synthesis?
Several alternatives can be used in the synthesis of 5-Fluoro-2-(1-pyrrolidinyl)...
What precautions should be taken when handling 1-((2R,3R,4R,5R)-5-((bis(4-methoxyphenyl)(phenyl)methoxy)methyl)-4-hydroxy-3-methoxytetrahydrofuran-2-yl)-5-methylpyrimidine-2,4(1H,3H)-dione (CAS: 153631-19-7)?
Proper personal protective equipment (PPE) must be worn when handling this compo...
What precautions should be taken when handling 6-Bromoimidazo[1,2-a]pyridin-8-amine (CAS: 676371-00-9)?
When handling 6-Bromoimidazo[1,2-a]pyridin-8-amine, it is important to wear appr...
Are there alternatives to (2S,4R)-4-(4-Nitrobenzyl)pyrrolidine-2-carboxylic acid hydrochloride (CAS: 1049740-22-8) in synthesis?
Alternatives to (2S,4R)-4-(4-Nitrobenzyl)pyrrolidine-2-carboxylic acid hydrochlo...
Source Journal
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.












![[(5-Methyl-1,3,4-thiadiazol-2-yl)sulfanyl]acetic acid structure [(5-Methyl-1,3,4-thiadiazol-2-yl)sulfanyl]acetic acid structure](https://static.chemtradehub.com/structs/509/50918-26-8-4ce8.webp)

![4-[(2-{2-[2-(2-Aminoethoxy)ethoxy]ethoxy}ethyl)amino]-2-(2,6-dioxo-3-piperidinyl)-1H-isoindole-1,3(2H)-dione structure 4-[(2-{2-[2-(2-Aminoethoxy)ethoxy]ethoxy}ethyl)amino]-2-(2,6-dioxo-3-piperidinyl)-1H-isoindole-1,3(2H)-dione structure](https://static.chemtradehub.com/structs/209/2093416-31-8-3162.webp)