Complexation of Eu(III), Am(III) and Cm(III) with Dicarboxylates: Thermodynamics and Structural Aspects of the Binary and Ternary Complexes

Thakur, P.; Pathak, P. N.; Gedris, Thomas E.; Choppin, Gregory R.

doi:10.1007/s10953-009-9373-8

Cited by 34 publications

(40 citation statements)

References 31 publications

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“…The high entropic values obtained for U(VI) and Am(III) are in agreement with an expected bidendate coordination mode for the 1 : 1 and 1 : 2 complexes [44,45]. The decreasing entropic term is observed for the successive stepwise reactions probably due to steric reason [46].…”

Section: Discussionsupporting

confidence: 83%

Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry

et al. 2014

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confirmed the formation of the 1 : 1, 1 : 2 and 1 : 3 complexes for U(VI) and Am(III); the formation of the 1 : 1 and 1 : 2 complexes for Np(V) and the formation of only 1 complex for Pu(V). For each complex, the thermodynamic parameters (the Gibbs energy Δ r ( ), the molar entropy change Δ r ( ) and the molar enthalpy change Δ r ( 0 )) were fitted to the experimental data. The effect of the ionic medium was treated using the specific ion interaction theory and the thermodynamic parameters at zero ionic strength were compared to previously published data.

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Section: Discussionsupporting

confidence: 83%

Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry

et al. 2014

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“…This has been shown to occur for actinide and lanthanide complexes of EDTA 4-where the secondary ligand is nitrilotriacetate (NTA), iminodiacetate (IDA), oxydiacetate (ODA) and citrate (see Figure 1). [13][14][15][16] However, few studies have observed the formation of ternary complexes of the actinides or lanthanides with carbonate. 17 Actinide complexes of EDTA 4-can be soluble at both acidic and alkaline pHs, and may be used as a model to understand the migration and speciation of radionuclides in the environment, as well as the behaviour of actinides in various effluents and matrices.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Solution Behavior of Minor Actinides in the Presence of EDTA^4–, Carbonate, and Hydroxide Ligands

et al. 2013

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Citation: GRIFFITHS, T.L. ... et al, 2013. Understanding the solution behavior of minor actinides in the presence of EDTA(4-), carbonate, and hydroxide ligands. Inorganic Chemistry, 52 (7) from approximately 10 to 12 in both systems, there is a sharp decrease from ~3 to ~2 in the binary system and from ~2 to ~1 in the ternary system. This is likely to correlate to the formation of hydrolysed species (e.g. [Am(EDTA)(OH)] 2-(aq) and/or Am(OH) 3(s) ).

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“…Unfortunately, the literature is of little help in understanding the enthalpies of ternary complexation of the trivalent f-elements, as there are few data available and the reported ΔH 111 values range from modestly endothermic to moderately exothermic. [37][38][39] It is not trivial to measure ΔH 111 without knowing K 111 , and we have not been able to clearly identify signatures of M(DTPA)(Lac) 3-complexes in any of our solutions. Nevertheless, one can explore the relationship between the enthalpy and equilibrium constant that would be required to account for the observed heat in order to understand if the reported Q values are small because ΔH 111 is small.…”

Section: Discussionmentioning

confidence: 90%

Do Aqueous Ternary Complexes Influence the TALSPEAK Process?

Leggett

Liu

Jensen

2010

Solvent Extraction and Ion Exchange

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The aqueous speciation of trivalent lanthanide and actinide cations in solutions containing DTPA (diethylenetriamine-N,N,N 0 ,N 0 ,N 00 -pentaacetic acid) and lactic acid were studied under conditions representative of the TALSPEAK process. Spectrophotometric titrations, fluorescence spectroscopy, and thermometric titrations were used to search for indications of ternary metal-DTPA-lactate complexes. The addition of lactate anions to metal-DTPA complexes was undetectable by any of these techniques, even at free lactate concentrations of 0.75 M. Although lactic acid is necessary for the optimal performance of the TALSPEAK process, we find that the fractions of aqueous ternary Ln 3+ /An 3+ -DTPA-lactate complexes are far too low to account for the observed acid dependence of TALSPEAK metal extraction.

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Complexation of Eu(III), Am(III) and Cm(III) with Dicarboxylates: Thermodynamics and Structural Aspects of the Binary and Ternary Complexes

Cited by 34 publications

References 31 publications

Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry

Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry

Understanding the Solution Behavior of Minor Actinides in the Presence of EDTA^4–, Carbonate, and Hydroxide Ligands

Do Aqueous Ternary Complexes Influence the TALSPEAK Process?

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Complexation of Eu(III), Am(III) and Cm(III) with Dicarboxylates: Thermodynamics and Structural Aspects of the Binary and Ternary Complexes

Cited by 34 publications

References 31 publications

Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry

Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry

Understanding the Solution Behavior of Minor Actinides in the Presence of EDTA4–, Carbonate, and Hydroxide Ligands

Do Aqueous Ternary Complexes Influence the TALSPEAK Process?

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Product

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Understanding the Solution Behavior of Minor Actinides in the Presence of EDTA^4–, Carbonate, and Hydroxide Ligands