Thorium separation from

Suppose that freshly purified thorium separated from HTGR spent fuel contains 30 Ci Th for every curie of Th. How long must the fuel be stored for the Th activity to decrease to 1.1 times the Th activity Consider only 6.7-year Ra in the decay chain between Th and Th. 

The same chemical separation research was done on thorium ores, leading to the discovery of a completely different set of radioactivities. Although the chemists made fundamental distinctions among the radioactivities based on chemical properties, it was often simpler to distinguish the radiation by the rate at which the radioactivity decayed. For uranium and thorium the level of radioactivity was independent of time. For most of the radioactivities separated from these elements, however, the activity showed an observable decrease with time and it was found that the rate of decrease was characteristic of each radioactive species. Each species had a unique half-life, ie, the time during which the activity was reduced to half of its initial value. 

Assay of beryUium metal and beryUium compounds is usuaUy accompHshed by titration. The sample is dissolved in sulfuric acid. Solution pH is adjusted to 8.5 using sodium hydroxide. The beryUium hydroxide precipitate is redissolved by addition of excess sodium fluoride. Liberated hydroxide is titrated with sulfuric acid. The beryUium content of the sample is calculated from the titration volume. Standards containing known beryUium concentrations must be analyzed along with the samples, as complexation of beryUium by fluoride is not quantitative. Titration rate and hold times ate critical therefore use of an automatic titrator is recommended. Other fluotide-complexing elements such as aluminum, sUicon, zirconium, hafnium, uranium, thorium, and rate earth elements must be absent, or must be corrected for if present in smaU amounts. Copper-beryUium and nickel—beryUium aUoys can be analyzed by titration if the beryUium is first separated from copper, nickel, and cobalt by ammonium hydroxide precipitation (15,16). 

The separation of basic precipitates of hydrous Th02 from the lanthanides in monazite sands has been outlined in Fig. 30.1 (p. 1230). These precipitates may then be dissolved in nitric acid and the thorium extracted into tributyl phosphate, (Bu"0)3PO, diluted with kerosene. In the case of Canadian production, the uranium ores are leached with sulfuric acid and the anionic sulfato complex of U preferentially absorbed onto an anion exchange resin. The Th is separated from Fe, A1 and other metals in the liquor by solvent extraction. 

Measurements of " Th in sediment samples (Aller and Cochran 1976 Cochran and Aller 1979) used much the same approach as outlined above. In this case, the dried sediment sample ( 10 g) was leached with strong mineral acid (HCl) in the presence of a yield monitor (generally Th, an artificial Th isotope resulting from the decay of Th that is produced by neutron capture on Th). Thorium was separated from U and purified by ion exchange chromatography, and electrodeposited onto stainless steel planchets. Counting and determination of " Th activity followed the procedure outlined above. 

Increasingly, new attempts to use basic chemistry to separate substances from radioactive material were meeting with failure. In many cases, two substances which were known to have different radioactive properties and molecular masses simply could not be separated from one another and appeared chemically identical. By 1910, this problem led Soddy to speculate that there were different forms of the same element (Soddy 1910). By 1913 he was confident of this interpretation and coined the term isotope to describe the various types of each element, recognizing that each isotope had a distinct mass and half-life (Soddy 1913b). In the same year he wrote that radiothorium, ionium, thorium, U-X, and radioactinium are a group of isotopic elements, the calculated atomic masses of which vary from 228-234 (a completely accurate statement- we now call these isotopes Th, °Th, Th, Th respectively). Soddy received the... 

From Figs. 1.1 and 1.2 it follows that the main end products of the uranium and thorium series are isotopes of lead (at the time referred to as Pb206.5 and ThO2208.4). The end products are thus isotopes of lead differing by two mass units. This observation became the motivation for the measurement of atomic weights of lead samples separated from thorium and uranium minerals. In his Nobel Lecture, Soddy describes this work as follows ... 

Heating the ore with sulfuric acid converts neodymium to its water soluble sulfate. The product mixture is treated with excess water to separate neodymium as soluble sulfate from the water-insoluble sulfates of other metals, as well as from other residues. If monazite is the starting material, thorium is separated from neodymium and other soluble rare earth sulfates by treating the solution with sodium pyrophosphate. This precipitates thorium pyrophosphate. Alternatively, thorium may be selectively precipitated as thorium hydroxide by partially neutralizing the solution with caustic soda at pH 3 to 4. The solution then is treated with ammonium oxalate to precipitate rare earth metals as their insoluble oxalates. The rare earth oxalates obtained are decomposed to oxides by calcining in the presence of air. Composition of individual oxides in such rare earth oxide mixture may vary with the source of ore and may contain neodymium oxide, as much as 18%. 

Thorium sulfate, being less soluble than rare earth metals sulfates, can be separated by fractional crystallization. Usually, solvent extraction methods are applied to obtain high purity thorium and for separation from rare earths. In many solvent extraction processes, an aqueous solution of tributyl phosphate is the extraction solvent of choice. 

Finely-ground monazite is treated with a 45% NaOH solution and heated at 138°C to open the ore. This converts thorium, uranium, and the rare earths to their water-insoluble oxides. The insoluble residues are filtered, dissolved in 37% HCl, and heated at 80°C. The oxides are converted into their soluble chlorides. The pH of the solution is adjusted to 5.8 with NaOH. Thorium and uranium are precipitated along with small quantities of rare earths. The precipitate is washed and dissolved in concentrated nitric acid. Thorium and uranium are separated from the rare earths by solvent extraction using an aqueous solution of tributyl phosphate. The two metals are separated from the organic phase by fractional crystallization or reduction. 

Aqueous biphasic systems offer the potential for highly selective and low-cost separations. Aqueous biphasic extraction for soil decontamination is based on the selective partitioning of either dissolved solutes or ultrafine particulates between two immiscible aqueous phases. Both soluble and particulate uranium contaminants can be separated from soil using this technique. Aqueous biphasic extraction may also have application for separation of plutonium and thorium from soil or waste. 

It is also possible, if the proper conditions are set, to dissolve selectively the rare earth hydroxides which are more basic than thorium hydroxide, see the right hand column of Figure 9. In such a case, the mixed hydroxide water slurry is brought to a pH of 3.4 by a slow and careful addition of hydrochloric acid. The undissolved thorium hydroxide is then separated from the solution by filtration. 

Hahn obtained an experimental value of only two years. Hahn therefore assumed that there must exist between thorium and radiothorium an unknown rayless product, mesothorium, which can easily be separated from thorium in the purification process. 

Uranium and thorium are actinide elements. Their chemical behavior is similar under most conditions. Both are refractory elements, both occur in nature in the +4 oxidation state, and their ionic radii are very similar (U+4 = 1.05 A, Th+4 = l.lOA). However, uranium can also exist in the +6 state as the uranyl ion (U02 2), which forms compounds that are soluble in water. Thus, under oxidizing conditions, uranium can be separated from thorium through the action of water. 

The common-lead method looks at the isotopic evolution of lead in systems with U/Pb and Th/Pb ratios similar to or less than the ratios in bulk solar system materials. The original formulation, by Holmes and Houtermans, is a single stage model that accounts for the isotopic composition of any sample of common lead in terms of primordial lead plus radiogenic lead produced in the source up to the time that lead was separated from uranium and thorium. Multistage models that more accurately describe the evolution of natural systems have been developed. The common-lead method is used in cosmochemistry primarily to study the time of differentiation and reservoir evolution in differentiated bodies... 

Moore, F.L. Liquid-liquid extraction of uranium and plutonium from hydrochloric acid solution with tri(iso-octyl)amine Separation from thorium and fission products, Anal. Chem. 30(1958) 908-911. 

Scandium can also be separated from the rare earths by using methyl acetate containing 10 per cent (v/v) water and 5 per cent (v/v) nitric acid (d 142) as solvent. The strip is subjected to a solvent run of 25 cm. Scandium is then found in a narrow strip (RF 0-17), but thorium forms a more diffuse band. 

Separation. Cerium and thorium salts are precipitated in Group IIIA. They may be separated from the other metals of the group by dissolving the precipitate in dilute HC1 and adding oxalic acid solution, when the oxalates of both metals are precipitated. The thorium and cerium may be separated (a) by dissolving the thorium oxalate in a mixture of ammonium acetate solution and... 

Since the chemistry of actinium is confined to the Ac + ion, it can readily be separated from thorium (and the lanthanides, for that matter) by processes like solvent extraction with thenoyltrifluoroacetone (TTFA) and by cation-exchange chromatography. The latter is an excellent means of purification, as the Ac + ion is much more strongly bound by the resin than its decay products. 

During the geological formation of major lead deposits the lead is separated from the parent uranium and thorium, and the isotopic composition of the lead so separated depends on the geochemical history of the source materials, specifically on the U/Pb and Th/Pb ratios and the timing of any variations in these ratios including the time of the final separation of lead. In theory, it is possible for each lead deposit in the world to have its own unique isotopic composition. 

---