Solving the discrepancy between the direct and relative-rate determinations of unimolecular reaction kinetics of dimethyl-substituted Criegee intermediate (CH3)2COO using a new photolytic precursor
Literature Information
Jari Peltola, Prasenjit Seal, Niko Vuorio, Petri Heinonen, Arkke Eskola
We have performed direct kinetic measurements of the thermal unimolecular reaction of (CH3)2COO in the temperature range 243ā340 K and pressure range 5ā350 Torr using time-resolved UV-absorption spectroscopy. We have utilized a new photolytic precursor, 2-bromo-2-iodopropane ((CH3)2CIBr), which photolysis at 213 nm in the presence of O2 produces acetone oxide, (CH3)2COO. The results show that the thermal unimolecular reaction is even more important main loss process of (CH3)2COO in the atmosphere than direct kinetic studies have suggested hitherto. The current experiments show that the unimolecular reaction rate of (CH3)2COO at 296 K and atmospheric pressure is 899 ± 42 sā1. Probably more importantly, current measurements bring the direct and relative-rate measurements of thermal unimolecular reaction kinetics of (CH3)2COO into quantitative agreement.
Related Literature
IF 6.222
Efficient one-pot synthesis of alkyl levulinate from xylose with an integrated dehydration/transfer-hydrogenation/alcoholysis processIF 6.367
Ultra-thin NiFeSe nanosheets as a highly efficient bifunctional electrocatalyst for overall water splittingIF 6.367
Back coverIF 6.222
A robust multifunctional ligand-controlled palladium-catalyzed carbonylation reaction in waterIF 6.222
Engineering nanoporous organic frameworks to stabilize naked Au clusters: a charge modulation approachIF 6.222
Carbon and carbon composites obtained using deep eutectic solvents and aqueous dilutions thereofIF 6.222
An improved fluorescent protein-based expression reporter system that utilizes bioluminescence resonance energy transfer and peptide-assisted complementationIF 6.222
An environmentally friendly natural polymer as a universal interfacial modifier for fullerene and non-fullerene polymer solar cellsIF 6.367
CaMoO4 nanosheet arrays for efficient and durable water oxidation electrocatalysis under alkaline conditionsIF 6.222
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.