The interactions of Ca(2+) and Mg(2+) with [UO2 (CO3 )3 ](4-) were studied by calcium ion selective electrode potentiometry and spectrophotometry. The stability constants of ternary Ca-UO2 -CO3 and Mg-UO2 -CO3 complexes were determined with calcium ion selective electrode potentiometry and optical absorption spectrophotometry, respectively. The enthalpies of complexation for two successive complexes, [CaUO2 (CO3 )3 ](2-) and [Ca2 UO2 (CO3 )3 ](aq), were determined for the first time by microcalorimetry. The data help to revise the speciation of uranium(VI) species under seawater conditions. In contrast to the previously accepted assumption that the highly negatively charged [UO2 (CO3 )3 ](4-) is the dominant species, the revised speciation indicates that the dominant aqueous uranium(VI) species under seawater conditions is the neutral [Ca2 UO2 (CO3 )3 ](aq). The results have a significant impact on the strategies for developing efficient sorption processes to extract uranium from seawater.

In recent years, the prospective recovery of uranium from seawater has become a topic of interest owing to the increasing demand for nuclear fuel worldwide and because of efforts to find sustainable alternatives to terrestrial mining for uranium. To date, the most advanced and promising method of extracting and concentrating uranium from seawater involves the use of polymeric sorbents containing the amidoxime binding moiety. Among a number of different moieties investigated, glutaroimide-dioxime is the most promising one, forming very stable complexes with U(VI) even in the presence of carbonate. To properly assess the affinity of uranium toward the amidoxime substrates, a comprehensive knowledge of the aqueous chemical equilibria of uranium is required. With this aim, in this paper we review the chemical equilibria of uranium (as UO 2 2+) in seawater, focusing on the solution equilibria leading to the formation of the stable complexes, M m (UO 2 )(CO 3 ) 3 (2m−4) (aq) (M = Ca or Mg, m = 0−2). These binary and ternary species dominate the chemistry of uranium in seawater and have recently been the object of study in several papers in the literature. The solubility equilibria of UO 2 2+ in seawater leading to the formation of the known minerals, including Liebigite, Ca 2 (UO 2 ), and Andersonite, Na 2 Ca(UO 2 )(CO 3 ) 3 •6H 2 O(cr), are also critically reviewed. Newly calculated values of the solubility products (log K 0 s ) for these solid compounds are presented based on the currently proposed speciation model that includes the most recent aforementioned data for the aqueous speciation of UO 2 2+. Based on these data, simulated speciation diagrams are calculated, both at zero ionic strength and in seawater-like media. In combination with the speciation data for uranium with glutaroimide-dioxime, these models provide a better, more comprehensive picture of the chemical equilibria of U(VI) in seawater while also providing useful tools to help assess the feasibility of its recovery through amidoxime-based collection systems.a Total Inorganic Carbon. b Dissolved Inorganic Phosphorus. c From ref 1, p 224.

The development of an efficient and economical system for extracting uranium from seawater could lead to an essentially limitless source of fuel for nuclear reactors. Currently, the most promising technology for recovering uranium from seawater involves the use of polymeric sorbents functionalized with the amidoxime moiety. However, competition of amidoxime sorbents with carbonate for uranium, indiscriminate sorption of other seawater cations, seawater temperature, and sorbent durability affect the efficiency and cost of this technology. Insights from thermodynamic and structural studies have proved to be powerful tools for addressing these issues and aiding the development of more effective sorbents for uranium. We summarize herein the results of these studies and discuss their implications for the extraction of uranium from seawater.

The complex formation between a cyclic ligand glutarimidoxioxime (denoted as HL(III) in this paper) and UO2(2+) is studied by potentiometry and microcalorimetry. Glutarimidoxioxime (HL(III)), together with glutarimidedioxime (H2L(I)) and glutardiamidoxime (H2L(II)), belongs to a family of amidoxime derivatives with prospective applications as binding agents for the recovery of uranium from seawater. An optimized procedure of synthesis that leads to the preparation of glutarimidoxioxime in the absence of other amidoxime byproducts is described in this paper. Speciation models based on the thermodynamic results from this study indicate that, compared with H2L(I) and H2L(II), HL(III) forms a much weaker complex with UO2(2+), UO2(L(III))(+), and cannot effectively compete with the hydrolysis equilibria of UO2(2+) under neutral or alkaline conditions. DFT computations, taking into account the solvation by including discrete hydration water molecules and bulk solvent effects, were performed to evaluate the structures and energies of the possible isomers of UO2(L(III))(+). Differing from the tridentate or η(2)-coordination modes previously found in the U(vi) complexes with amidoxime-related ligands, a bidentate mode, involving the oxygen of the oxime group and the nitrogen of the imino group, is found to be the most probable mode in UO2(L(III))(+). The bidentate coordination mode seems to be stabilized by the formation of a hydrogen bond between the carbonyl group of HL(III) and a water molecule in the hydration sphere of UO2(2+).

Thermodynamic parameters of complex formation between d(10) metal ions, such as Zn(2+), Cd(2+), Hg(2+) and Ag(+), and the macrocyclic thioether 1,4,7-trithiacyclononane ([9]AneS3) or the monodentate diethylsulfide (Et(2)S), in acetonitrile (AN) at 298.15 K, were studied by a systematic methodology including potentiometry, calorimetry and polarography. [9]AneS3 is able to form complexes with all the target cations, Et(2)S only reacts with Hg(2+) and Ag(+). Mononuclear ML(j) (j = 1, 2) complexes are formed with all the metal ions investigated, where the affinity order is Hg(2+) > Ag(+) > Cd(2+) ≈ Zn(2+) when L = [9]AneS3 and Hg(2+) > Ag(+) when L = Et(2)S. Enthalpy and entropy values are generally negative, as a consequence of both metal ion interactions with neutral ligands, the reagents' loss of degrees of freedom and the release of solvating molecules. DFT calculations on the complexes formed with [9]AneS3 in vacuum and in AN are also carried out, to correlate experimental and theoretical thermodynamic values and to highlight the interplay between the direct metal-thioether interaction and the solvation effects. Trends obtained for the stability constants and enthalpies of the 1 : 1 and 1 : 2 complexes in solvent well reproduce the experimental ones for all the divalent metal ion complexes with [9]AneS3 and indicate the release of 3 AN molecules in the formation of each consecutive octahedral complex. In addition, calculated and experimental values for Ag(+) complex formation in solution suggest that in AgL(2) species [9]AneS3 ligands are not both tridentate.