Two Ligands of Interest in Recovering Uranium from the Oceans: The Correct Formation Constants of the Uranyl(VI) Cation with 2,2'-Bipyridyl-6,6'-dicarboxylic Acid and 1,10-Phenanthroline-2,9-dicarboxylic Acid

Fultz, Erica L.; Bart Jones, S.; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.; Dai, Sheng; Hancock, Robert D.

doi:10.1021/acs.inorgchem.2c00775

Title: Two Ligands of Interest in Recovering Uranium from the Oceans: The Correct Formation Constants of the Uranyl(VI) Cation with 2,2'-Bipyridyl-6,6'-dicarboxylic Acid and 1,10-Phenanthroline-2,9-dicarboxylic Acid

Journal Article · Wed Jun 15 00:00:00 EDT 2022 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.2c00775· OSTI ID:1898996

Fultz, Erica L. ^[1]; Bart Jones, S. ^[1];

^[2];

^[1]

University of North Carolina, Wilmington, NC (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

The ligands BDA (2,2'-bipyridyl-6,6'-dicarboxylic acid) and PDA (1,10-phenanthroline-2,9-dicarboxylic acid) are of interest as functional group types for ion-exchange materials for extracting uranium from the oceans, reported in a previous paper for PDA Lashley, M. A. ( Inorg. Chem. 2016 55 10818 10829). Yang, Y. ( Inorg. Chem. 2019, 58, 6064 6074) have published what they claim to be a more accurate result for the formation of the UO₂²⁺/PDA complex of log K₁ = 22.84 compared with our reported value of log K₁ = 16.5, as well as log K₁ = 21.52 for the BDA complex. The determination of log K₁ for the PDA and BDA complexes with the UO₂²⁺ cation was carried out by Yang et al. using a competition reaction between DTPA (diethylenetriamine pentaacetic acid) and BDA or PDA, monitoring the absorbance due to the BDA and PDA ligands. This competition method using absorbance versus pH titrations was developed for determining the formation constants of the complexes of several polypyridyl ligands plus PDA complexes of metal ions, which were too stable for log K determination by competition with protons. A key feature of such titrations is that in the competition reaction, the displacement of the pyridyl donor ligand (e.g., PDA) by the competing ligand (e.g., DTPA), the absorbance spectrum of the displaced pyridyl donor ligand should be observed. Competing ligands used to date have been EDTA (ethylenediamine tetraacetic acid), DTPA, or the hydroxide ion. In the study of Yang et al., no such displaced PDA or BDA was apparent in the absorbance spectra in their titrations so that their reported log K₁ values have no validity. Their log K₁ values are so much higher than log K₁ for the uranyl DTPA complex (~13.6) that DTPA could not possibly displace BDA or PDA from the uranyl cation, and a competition reaction could not possibly occur. Here, we report the correct value of log K₁ = 15.4 (ionic strength = zero) for the uranyl BDA complex, to illustrate the correct determination of such a constant by a competition reaction between BDA and hydroxide, showing how the characteristic absorbance spectrum for a BDA complex, here the UO₂²⁺ complex, disappears, and the distinctive absorbance spectrum of the free nonprotonated BDA ligand appears as the pH is increased, and BDA is displaced by the hydroxide ion.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1898996

Journal Information:: Inorganic Chemistry, Vol. 61, Issue 26; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Two Ligands of Interest in Recovering Uranium from the Oceans: The Correct Formation Constants of the Uranyl(VI) Cation with 2,2'-Bipyridyl-6,6'-dicarboxylic Acid and 1,10-Phenanthroline-2,9-dicarboxylic Acid

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