Thorium complexes solubility

Thorium. Experimental and theoretical studies of thorium speciation, solubility, and sorption in low-ionic-strength waters are described by Langmuir and Herman (1980), Laflamme and Murray (1987), Osthols et ai (1994), Osthols (1995), and Quigley et al. (1996). Langmuir and Herman (1980) provide a critically evaluated thermodynamic database for natural waters at low temperature that is widely used. However, it does not contain information about important thorium carbonate complexes, and the stability of phosphate complexes may be overestimated (US EPA, 1999b). 

Table Xl-3 Equilibrium constants for thorium complexes with carbonate relevant in solubility studies with dried or aged Th02(am, hyd) at 22-25°C. (Uncertainties are given as 2a).

This paper contains no quantitative information on thorium complexes. The authors note that solubility experiments on hydrous thorium oxide did not reach equilibrium after 2 months and that the only experimental data they have obtained refer to a quasisolubility curve obtained after equilibration for ten days. There is no other useful information for this review. 

Rubidium metal alloys with the other alkaU metals, the alkaline-earth metals, antimony, bismuth, gold, and mercury. Rubidium forms double haUde salts with antimony, bismuth, cadmium, cobalt, copper, iron, lead, manganese, mercury, nickel, thorium, and 2iac. These complexes are generally water iasoluble and not hygroscopic. The soluble mbidium compounds are acetate, bromide, carbonate, chloride, chromate, fluoride, formate, hydroxide, iodide. 

Coordination Complexes. The coordination and organometaHic chemistry of thorium is dominated by the extremely stable tetravalent ion. Except in a few cases where large and stericaHy demanding ligands are used, lower thorium oxidation states are generally unstable. An example is the isolation of a molecular Th(III) complex [107040-62-0] Th[Tj-C H2(Si(CH2)3)2]3 (25). Reports (26) on the synthesis of soluble Th(II) complexes, such as... 

On the basis of these facts, it was speculated that plutonium in its highest oxidation state is similar to uranium (VI) and in a lower state is similar to thorium (IV) and uranium (IV). It was reasoned that if plutonium existed normally as a stable plutonium (IV) ion, it would probably form insoluble compounds or stable complex ions analogous to those of similar ions, and that it would be desirable (as soon as sufficient plutonium became available) to determine the solubilities of such compounds as the fluoride, oxalate, phosphate, iodate, and peroxide. Such data were needed to confirm deductions based on the tracer experiments. 

Thorium generally exists as a neutral hydroxide species in the oceans and is highly insoluble. Its behavior is dominated by a tendency to become incorporated in colloids and/or adhere to the surfaces of existing particles (Cochran 1992). Because ocean particles settle from the water column on the timescale of years, Th isotopes are removed rapidly and have an average residence time of = 20 years (Fig. 1). This insoluble behavior has led to the common assertion that Th is always immobile in aqueous conditions. While this is generally true in seawater, there are examples of Th being complexed as a carbonate (e.g.. Mono Lake waters, Anderson et al. 1982 Simpson et al. 1982) in which form it is soluble. 

The principal abiotic processes that may transform thorium compounds in water are complexation by anions/organic ligands and hydroxylation. The increase in the mobility of thorium through the formation of soluble complexes with CQs, humic materials, and other anions or ligands and the decrease in the mobility due to formation of Th(OH)4 or anionic thorium-hydroxide complexes were discussed in Section 5.3.1.2. In a model experiment with seawater at pH 8.2 and freshwater at pH 6 and pH 9, it was estimated that almost 100% of the thorium resides as hydroxo complexes (Boniforti 1987). 

Physical and Chemical Properties. Some of the physical and chemical properties (i.e., K°w K°<= and Henry s law constant) that are often used in the estimation of environmental fate of organic compounds are not useful or relevant for most inorganic compounds including thorium and its compounds. Relevant data concerning the physical and chemical properties, such as solubility, stability, and oxidation-reduction potential of thorium salts and complexes have been located in the existing literature. 

In the environment, thorium and its compounds do not degrade or mineralize like many organic compounds, but instead speciate into different chemical compounds and form radioactive decay products. Analytical methods for the quantification of radioactive decay products, such as radium, radon, polonium and lead are available. However, the decay products of thorium are rarely analyzed in environmental samples. Since radon-220 (thoron, a decay product of thorium-232) is a gas, determination of thoron decay products in some environmental samples may be simpler, and their concentrations may be used as an indirect measure of the parent compound in the environment if a secular equilibrium is reached between thorium-232 and all its decay products. There are few analytical methods that will allow quantification of the speciation products formed as a result of environmental interactions of thorium (e.g., formation of complex). A knowledge of the environmental transformation processes of thorium and the compounds formed as a result is important in the understanding of their transport in environmental media. For example, in aquatic media, formation of soluble complexes will increase thorium mobility, whereas formation of insoluble species will enhance its incorporation into the sediment and limit its mobility. 

The bicarbonate ion, HC03, is a prevalent species in natural waters, ranging in concentrations up to 0.8 X 10 3. As was indicated previously, carbonate ions have the ability to form complexes with plutonium. Starik (39) mentions that, in an investigation of the adsorption of uranium, there was a decrease in the adsorption after reaching a maximum, which was explained by the formation of negative carbonate complexes. Kurbatov and co-workers (20) found that increasing the bicarbonate ion concentration in a UXi (thorium) solution decreased the amount of thorium which formed a colloid and became filterable. This again was believed to be caused by the formation of a soluble complex with the bicarbonate. 

The possibility of dissolving the mixed hydroxide in HNOs and obtaining direct extraction of thorium (and uranium) from the nitrate solution has been studied [155,156], but does not seem to be too promising, possibly due to the partial oxidation of tripositive cerium to the tetrapositive state. Kraitzer [157] was able to separate thorium from the mixed hydroxide cake by extracting the cake with sodium carbonate buffer at pH 9.5—10. Thorium was found to form a soluble carbonate complex and a recovery of better than 99% of thorium was claimed after only four extractions. 

Thorium has the oxidation state of (IV) in all of its important compounds. Its oxide, ThCL. and its hydroxide are entirely basic. The nature of the 10ns present in a number of solutions of the soluble compounds is not known with certainty. Complex ions involving sulfate are suggested by the increased solubility of the sulfate in solutions of the acid sulfates. Similarly, other complex ions are suggested by the solubility of the carbonate in excess alkali carbonate and of the oxalate in ammonium oxalate. Such ready complex ion formation is consistent with the high positive charge of the thorium-flV) ion. 

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