Water isotopic enrichment

In TBP extraction, the yeUowcake is dissolved ia nitric acid and extracted with tributyl phosphate ia a kerosene or hexane diluent. The uranyl ion forms the mixed complex U02(N02)2(TBP)2 which is extracted iato the diluent. The purified uranium is then back-extracted iato nitric acid or water, and concentrated. The uranyl nitrate solution is evaporated to uranyl nitrate hexahydrate [13520-83-7], U02(N02)2 6H20. The uranyl nitrate hexahydrate is dehydrated and denitrated duting a pyrolysis step to form uranium trioxide [1344-58-7], UO, as shown ia equation 10. The pyrolysis is most often carried out ia either a batch reactor (Fig. 2) or a fluidized-bed denitrator (Fig. 3). The UO is reduced with hydrogen to uranium dioxide [1344-57-6], UO2 (eq. 11), and converted to uranium tetrafluoride [10049-14-6], UF, with HF at elevated temperatures (eq. 12). The UF can be either reduced to uranium metal or fluotinated to uranium hexafluoride [7783-81-5], UF, for isotope enrichment. The chemistry and operating conditions of the TBP refining process, and conversion to UO, UO2, and ultimately UF have been discussed ia detail (40). 

The only large-scale use of deuterium in industry is as a moderator, in the form of D2O, for nuclear reactors. Because of its favorable slowing-down properties and its small capture cross section for neutrons, deuterium moderation permits the use of uranium containing the natural abundance of uranium-235, thus avoiding an isotope enrichment step in the preparation of reactor fuel. Heavy water-moderated thermal neutron reactors fueled with uranium-233 and surrounded with a natural thorium blanket offer the prospect of successful fuel breeding, ie, production of greater amounts of (by neutron capture in thorium) than are consumed by nuclear fission in the operation of the reactor. The advantages of heavy water-moderated reactors are difficult to assess. 

Tieszen 1991). Water stress, for instance, lowers photo synthetic discrimination against C, resulting in isotopic enrichment. C4 plants are not affected isotopically by environmental parameters although their distributions are (Ehleringer et al. 1997). Under conditions of increasing aridity, the climate variable of most likely importance in African sites, C3 plants should become slightly more enriched on average. Therefore one should be cautious about use... 

Water vapor enriched in oxygen-16 is transported by wind in the atmosphere from the sea to land. When the water vapor condenses and precipitates as rain, snow, or hail, the water becomes rich in oxygen-16. Eventually the oxygen-16 rich water is incorporated into rivers, lakes, glaciers, and polar ice, which are, therefore, also rich in oxygen-16. Thus the isotopic composition of groundwater and the water of rivers, lakes, and glaciers is not the same as in seas and oceans. 

The benefits of using ionic compounds in microwave-enhanced reactions led us to explore the possibility of using ionic solvents i.e. ionic liquids, as donors for both deuterium and tritium. Whilst D20 is now relatively inexpensive and available at high isotopic enrichment, tritiated water is usually employed, for safety reasons, at low isotopic incorporation (we typically use HTO at 5 or 50 Ci mLT1 specific activity corresponding to 0.2-2% isotopic incorporation). This is a serious limitation when there is a need to provide compounds at high specific activity. 

In this method, each gas is produced in a separate compartment so they have high purity. In this process, deuterium oxide, D20, is electrolyzed more slowly so the water becomes enriched in the heavier isotope. The other electrolytic process that produces hydrogen is the electrolysis of a solution of sodium chloride. 

The extraction of deuterium from natural water feed forms an excellent case study of the application of large scale distillation and exchange distillation to isotope separation. The principal historical demand for deuterium has been as heavy water, D20, for use in certain nuclear reactors. Deuterium is an excellent neutron moderator, and more importantly, it has a low absorption cross section for slow neutrons. Therefore a reactor moderated and cooled with D20 can be fueled with natural uranium thus avoiding the problems of uranium isotope enrichment. This was the... 

Isotope Enrichment by Distillation of Nitrous Oxide or Water... 

Figure 2.3 Changes in the heavy isotope content of oxygen and hydrogen in the urine with time after administration of The and 0 are diluted by the formation of H2O from oxidation of fuels and particularly that ingested in food and drink. The 0 in water is diluted from the production of CO2 via the oxidation of the fuels. The difference in the slopes indicates the rate of CO2 production. The label heavy isotope content is actually the isotopic enrichment. Physical activity, for example, increases fuel oxidation (i.e. respiration) and therefore greater dilution of...

This model qualitatively explains the deviation of isotopic compositions away from the Meteoric Water Line because molecular diffusion adds a non-equilibrium fractionation term and the limited isotopic enrichment occurs as a consequence of molecular exchange with atmospheric vapor. It is mainly the humidity which controls the degree of isotope enrichment. Only under very arid conditions, and only in small water bodies, really large emichments in D and are observed. For example, Gonfiantini (1986) reported a 5 0-value of +31.3%c and a 8D-value of +129%c for a small, shallow lake in the western Sahara. 

Grant et al. described an investigation of the ternary complex of ATP and bis(2-pyridyl)amine (MgATP/BPA), using advanced solid-state NMR methods such as Mg REDOR and Mg MQMAS in Mg-isotopically enriched samples. In the 3QMAS spectrum, the authors detected the presence of two Mg sites with close Mg quadrupole parameters. With help of a REDOR experiment, the assignment of these two sets of parameters to Mg ions either coordinated to water molecules or to phosphate oxygen donors was then possible. 

Fluorine compounds from fluorite (fluorspar, CaF2) are used in water treatment (to suppress dental caries) and to make fluoropolymers (such as Teflon), lubricants, and refrigerants. Molten cryolite (Na3AlF6) is essential as a solvent for Al203 in the electrolytic production of aluminum metal, while the isotopic enrichment of uranium for nuclear power reactors is usually achieved by diffusion or gas centrifugation of volatile UF6. 

Since the level of tritium in the atmosphere is presently greater than 10 TU, it is possible to study many physical and chemical processes using this equipment for sample analysis. Since isotopic enrichment is unnecessary for most samples, direct rapid analysis is possible. The equipment is being used presently to analyze water samples from Nevada in a hydrology project. Table IV shows the analytic data. No attempt has yet been made to evaluate these data. What is apparent qualitatively... 

Chemical shifts of bulk and coordinated water differ and as a result, the line width at half-height can be used to calculate the rate of chemical exchange. If reactions are slow, NMR methods can be used directly to determine reaction rates since one need only follow the isotopic enrichment of a complex. 

Evaporation and Evaporative Fractionation of Water. Evaporation from standing water bodies is the principal fractionation mechanism in most hydrological systems. Evaporative isotopic enrichment is a function of numerous factors (e.g., temperature, salinity, and relative humidity) that cause considerable variation in the lsO/ ieO and D/H ratios of natural surface waters. Craig and Gordon (22) evaluated isotopic effects on precipitation and evaporation in the ocean-atmosphere system. Much of what was developed in that work is directly applicable to the freshwater systems discussed here. 

Further information on this system is available from studies directed at photochemical isotope enrichment (16). In this work a mercury resonance lamp containing only Hg19S was used as a source. A flowing mixture of natural mercury and water vapor exposed to the Hg198 fine structure component of the mercury resonance radiation (2537 A.) was found to result in HgO considerably enriched in Hg198. It was concluded that this could only occur if Hg(3Pj) atoms reacted in a primary step to form either a compound which is removed from further contact with the reaction or which itself may react further but must not regenerate free Hg. Either reaction (55) or (56) would satisfy these conditions. If reaction (55) is the primary reaction, the further reaction... 

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