Dataset Information

Prediction of Binding Stability of Pu(IV) and PuO₂(VI) by Nitrogen Tridentate Ligands in Aqueous Solution.

ABSTRACT: Plutonium has potential applications in energy production in well-controlled nuclear reactors. Since nuclear power plants have great merit as environmentally friendly energy sources with a recyclable system, a recycling system for extracting Pu from spent fuels using suitable extractants has been proposed. Pu leakage is a potential environmental hazard, hence the need for chemical sensor development. Both extractants and chemical sensors involve metal-ligand interactions and to develop efficient extractants and chemical sensors, structural information about Pu ligands must be obtained by quantum calculations. Herein, six representative nitrogen tridentate ligands were introduced, and their binding stabilities were evaluated. The tridentate L6, which contains tri-pyridine chelate with benzene connectors, showed the highest binding energies for Pu(IV) and PuO₂(VI) in water. Analysis based on the quantum theory of atoms in molecular analysis, including natural population analysis and electron density studies, provided insight into the bonding characteristics for each structure. We propose that differences in ionic bonding characteristics account for the Pu-ligand stability differences. These results form a basis for designing novel extractants and organic Pu sensors.

SUBMITTER: Jeong K

PROVIDER: S-EPMC7216098 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature

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Prediction of Binding Stability of Pu(IV) and PuO<sub>2</sub>(VI) by Nitrogen Tridentate Ligands in Aqueous Solution.

Jeong Keunhong K Jeong Hye Jin HJ Woo Seung Min SM Bae Sungchul S

International journal of molecular sciences 20200417 8

Plutonium has potential applications in energy production in well-controlled nuclear reactors. Since nuclear power plants have great merit as environmentally friendly energy sources with a recyclable system, a recycling system for extracting Pu from spent fuels using suitable extractants has been proposed. Pu leakage is a potential environmental hazard, hence the need for chemical sensor development. Both extractants and chemical sensors involve metal-ligand interactions and to develop efficient ...[more]

PMID: 32316430

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Project description:The bromine-selenite reaction at strongly acidic conditions was investigated by monitoring the absorbance-time traces at the isosbestic point of the bromine-tribromide system at a constant ionic strength (0.5 M adjusted by sodium perchlorate) and temperature. Despite the simplicity of the stoichiometry, the kinetics was found to be very complex. Although the formal kinetic orders of the reactants bromine and selenite are strictly 1, that of the hydrogen ion varies from -2 to less than -3 and notably depends on the initial bromide concentration as well. The bromide ion also inhibits the reaction, making the whole system as a sound example of efficient autoinhibition. We have clearly shown that the inhibitory effect of the bromide ion cannot be explained quantitatively by either exclusively considering the unreactivity of the tribromide ion over elemental bromine or driving the reaction via hypobromous acid formed from the well-known hydrolysis of bromine in aqueous solutions. Instead of that, bromonium ion transfer initiating equilibrium is suggested between the selenium(IV) and bromine species to produce bromide ion and SeO3Br- followed by the hydrolysis of this short-lived intermediate. This hydrolytic transformation was found to be catalytic with respect to hydroxide and bromide ions as well. We have also demonstrated that, among the wide variety of selenium species present in the acidic aqueous solution, the best result can be obtained by considering HSeO3 - as the kinetically active species toward bromine. The proposed mechanism containing 10 acid-base equilibria with known equilibrium constants, the above-mentioned initiating equilibrium, and the hydrolysis of SeO3Br- is able to fit all 49 kinetic absorbance-traces simultaneously, taking into account properly the most important characteristics of the measured data at strongly acidic conditions. Furthermore, this kinetic model was further extended by the direct reactions of hypobromous acid with selenium(IV) species suggested previously with reasonably modified rate coefficients to describe the pH dependence of the apparent second-order rate coefficients over the pH = 1-13 range, providing a useful tool to predict more accurately the kinetic behavior of selenium(IV) species in water treatment process conditions.

Dataset Information

Prediction of Binding Stability of Pu(IV) and PuO₂(VI) by Nitrogen Tridentate Ligands in Aqueous Solution.

Publications

Prediction of Binding Stability of Pu(IV) and PuO<sub>2</sub>(VI) by Nitrogen Tridentate Ligands in Aqueous Solution.

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Dataset Information

Prediction of Binding Stability of Pu(IV) and PuO2(VI) by Nitrogen Tridentate Ligands in Aqueous Solution.

Publications

Prediction of Binding Stability of Pu(IV) and PuO<sub>2</sub>(VI) by Nitrogen Tridentate Ligands in Aqueous Solution.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Prediction of Binding Stability of Pu(IV) and PuO₂(VI) by Nitrogen Tridentate Ligands in Aqueous Solution.