Pyridine-2,6-dicarboxylic acid esters – new ligands for extraction and determination of metals

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Abstract

N,O-Hybrid donor ligands are promising compounds for the isolation and separation of actinides and lanthanides from technological solutions during the processing of spent nuclear fuel. New synthesized N,O-hybrid donor ligands – derivatives of 2,6-pyridindicarboxylic acid – have been studied as extractants and membrane components for potentiometric sensors. The extraction ability of solutions of these compounds in meta-nitrobenzotrifluoride with respect to d- and f-elements from solutions of nitric and perchloric acids has been studied. It has been shown that the replacement of a mide groups with ester groups reduces the extraction ability of ligands. The transition from nitric acid to chloric acid gives a sharp increase in the extraction capacity due to the perchlorate effect. A significant increase in the extraction capacity is also observed when chlorinated cobalt dicarbollide is added to the organic phase: the highest distribution coefficient is obtained with a ratio of the concentrations of the extractant and the additive 1:1. Potentiometric membrane sensors based on new ligands have demonstrated significant sensitivity to Cd2+. The correlation between the behavior of new ligands in extraction and in potentiometric measurements has been studied.

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About the authors

D. А. Kazanina

Khlopin Radium Institute

Author for correspondence.
Email: darinakazanina@gmail.com
Russian Federation, Saint Petersburg, 194021

M. Yu. Alyapyshev

Polymetal Engineering JSC

Email: darinakazanina@gmail.com
Russian Federation, Saint Petersburg, 198216

V. А. Polukeev

Vekton JSC

Email: darinakazanina@gmail.com
Russian Federation, Saint Petersburg, 194021

V. А. Babain

Khlopin Radium Institute

Email: darinakazanina@gmail.com
Russian Federation, Saint Petersburg, 194021

D. O. Kirsanov

Saint Petersburg State University

Email: darinakazanina@gmail.com
Russian Federation, Saint Petersburg, 194021

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Supplementary files

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2. Scheme 1. Structural formulae of the synthesised ligands: (a) DOPDA - dioctyl 2,6-pyridine dicarboxylate, (b) TECDA - methyl 6-(N-4-tolyl)-N-ethylcarbamoyl)-pyridine-2-carboxylate, (c) MPyDA - dioctyl 4-methoxy-2,6-pyridine dicarboxylate, (d) CyPODA - dimethyl 4-(4-cyclohexylphenoxy)-2,6-dicarboxylate.

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3. Fig. 1. Dependence of the Am and Eu distribution coefficient on the composition of the organic phase. Aqueous phase - 1 M HNO3 and indicator quantities of 152Eu and 241Am. Organic phase - TECDA + CDC in F-3; with CDC = 0.02 M.

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4. Fig. 2. Values of metal distribution coefficients during extraction from 3 M HNO3, cMe = 0.0002 M. Organic phase - 0.1 M ligand solution in P-3.

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5. Fig. 3. Dependence of metal distribution coefficients on TECDA concentration in F-3. Aqueous phase - 3 M HNO3, cMe = 0.0002 M.

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6. Fig. 4. Values of metal distribution coefficients during extraction from 3 M HClO4, cMe = 0.005 M. The organic phase is TECDA in F-3.

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7. Fig. 5. Potentiometric response curves in aqueous solutions. (a) - Cs+, (b) - Ca2+.

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8. Fig. 6. Sensor sensitivity to (a) single-charged ions, (b) double-charged ions.

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9. Fig. 7. Load and IHC count plots for GC1 and GC2: (a) sensor count plot based on their transition metal sensitivity, (b) load plot based on transition metal sensitivity of sensors, (c) ligand count plot based on transition metal distribution coefficients, (d) load plot based on transition metal distribution coefficients.

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10. Fig. 8. Sensor selectivity to doubly charged ions.

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