Laser photolysis study on the reaction of nitrate radical with tributylphosphate and its analogues—comparison with sulfate radical

文献情報

出版日 2004-02-10

DOI 10.1039/B315913B

インパクトファクター 3.676

著者

Hui He, Mingzhang Lin, Yusa Muroya, Hisaaki Kudo, Yosuke Katsumura

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要旨

Time resolved laser photolysis was carried out to study the reaction of NO3˙ radical toward a series of organic phosphates (tributylphosphate (TBP) and its analogues) with different length of side alkyl groups such as CH3, C2H5, C3H7, CH(CH3)2 and C4H9 in water, acetonitrile, and the mixtures of water and acetonitrile, respectively. For comparison, a similar investigation on SO4˙− radical was also conducted. The oxidation reaction of NO3˙ and SO4˙− radical with the phosphates was attributed to mainly an H-abstract reaction. The kinetics study shows that the rate constants of the reaction between the two radicals and phosphates increase remarkably with increasing of the length of the alkyl groups, e.g. in the case of NO3˙ radical in acetonitrile, the rate constant increases by almost 4 orders of magnitude from TMP (–CH3) to TBP (–C4H9). The composition of the solvent also greatly affects the reactivity but it exhibits an opposite effect of the two radicals, the rate constant of NO3˙ increases with the mole fraction of acetonitrile while that of SO4˙− decreases. The present study would be helpful for understanding the mechanism of deterioration of TBP in the Purex process.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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.

Laser photolysis study on the reaction of nitrate radical with tributylphosphate and its analogues—comparison with sulfate radical

文献情報

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