Kinetic studies of reactions of the nitrate radical (NO3) with peroxy radicals (RO2): an indirect source of OH at night?

Literature Information

Publication Date 2006-07-12
DOI 10.1039/B605569A
Impact Factor 3.676
Authors

Dudley E. Shallcross, Laura Watson


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Abstract

A discharge–flow system, coupled to cavity-enhanced absorption spectroscopy (CEAS) detection systems for NO3 at λ = 662 nm and NO2 at λ = 404 nm, was used to investigate the kinetics of the reactions of NO3 with eight peroxy radicals at P ∼ 5 Torr and T ∼ 295 K. Values of the rate constants obtained were (k/10−12 cm3 molecule−1 s−1): CH3O2 (1.1 ± 0.5), C2H5O2 (2.3 ± 0.7), CH2FO2 (1.4 ± 0.9), CH2ClO2 (3.8+1.4−2.6), c-C5H9O2 (1.2+1.1−0.5), c-C6H11O2 (1.9 ± 0.7), CF3O2 (0.62 ± 0.17) and CF3CFO2CF3 (0.24 ± 0.13). We explore possible relationships between k and the orbital energies of the reactants. We also provide a brief discussion of the potential impact of the reactions of NO3 with RO2 on the chemistry of the night-time atmosphere.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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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.

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