Isotope oxidation reactor

Figure 14.17 Schematic diagram of the ThermoElectron liquid chromatography isotope ratio mass spectrometry chemical oxidation reactor...

The homogeneous reactor experiment-2 (HRE-2) was tested as a power-breeder in the late 1950s. The core contained highly enriched uranyl sulfate in heavy water and the reflector contained a slurry of thorium oxide [1314-20-1J, Th02, in D2O. The reactor thus produced fissile uranium-233 by absorption of neutrons in thorium-232 [7440-29-1J, the essentially stable single isotope of thorium. Local deposits of uranium caused reactivity excursions and intense sources of heat that melted holes in the container (18), and the project was terrninated. 

Uranium oxide [1344-57-6] from mills is converted into uranium hexafluoride [7783-81-5] FJF, for use in gaseous diffusion isotope separation plants (see Diffusion separation methods). The wastes from these operations are only slightly radioactive. Both uranium-235 and uranium-238 have long half-Hves, 7.08 x 10 and 4.46 x 10 yr, respectively. Uranium enriched to around 3 wt % is shipped to a reactor fuel fabrication plant (see Nuclear REACTORS, NUCLEAR FUEL reserves). There conversion to uranium dioxide is foUowed by peUet formation, sintering, and placement in tubes to form fuel rods. The rods are put in bundles to form fuel assembHes. Despite active recycling (qv), some low activity wastes are produced. 

Uranium hexafluoride [7783-81-5], UF, is an extremely corrosive, colorless, crystalline soHd, which sublimes with ease at room temperature and atmospheric pressure. The complex can be obtained by multiple routes, ie, fluorination of UF [10049-14-6] with F2, oxidation of UF with O2, or fluorination of UO [1344-58-7] by F2. The hexafluoride is monomeric in nature having an octahedral geometry. UF is soluble in H2O, CCl and other chlorinated hydrocarbons, is insoluble in CS2, and decomposes in alcohols and ethers. The importance of UF in isotopic enrichment and the subsequent apphcations of uranium metal cannot be overstated. The U.S. government has approximately 500,000 t of UF stockpiled for enrichment or quick conversion into nuclear weapons had the need arisen (57). With the change in pohtical tides and the downsizing of the nation s nuclear arsenal, debates over releasing the stockpiles for use in the production of fuel for civiUan nuclear reactors continue. 

Development efforts in the nuclear industry are focusing on the fuel cycle (Figure 6.12). The front end of the cycle includes mining, milling, and conversion of ore to uranium hexafluoride enrichment of the uranium-235 isotope conversion of the enriched product to uranium oxides and fabrication into reactor fuel elements. Because there is at present a moratorium on reprocessing spent fuel, the back end of the cycle consists only of management and disposal of spent fuel. 

The oxidation reactions were performed in a 25 mL ronnd bottom flask. In a typical reaction the catalyst (0.5 % Fe mol) was added to 0.125 M olefin solntion in acetone then dry TBHP (3.5 M in CH2CI2 or in PhCl) was added in one step, and the reaction mixture was stirred and heated in an oil bath at 40°C for 7 h. For the allyhc oxidation of cyclohexene with isotopically labelled oxygen ( 02) the following procedure was carried out the suspension of the catalyst (0.5% Fe mol) in cyclohexene (4 mL, 0.125 M) was frozen and the air in the reactor was evacuated and replaced by an oxygen (21% mol) - argon (79% mol) mixture. Then, the suspension was allowed to warm at room temperatnre and 1.3 mmol of degasified TBHP was added to the solution and the reaction mixtnre was stirred at 40°C for 3 h. 

Xenon fluorides, 77 323-325 binary, 77 335-336 Xenon-gold cations, 77 332 Xenon halides, 77 323-325 Xenon hexafluoride, 7 7 325, 329 uses for, 7 7 336 Xenon ion lasers, 74 685 Xenon isotopes, in fission reactors, 77 375 Xenon oxide difiuoride, 77 326 Xenon oxide fluorides, 7 7 326 Xenon oxides, 77 325-326 Xenon oxide tetrafluoride, 77 326 Xenon testing, in plastics weathering, 79 584-585... 

Now, GC-IRMS can be used to measure the nitrogen isotopic composition of individual compounds [657]. Measurement of nitrogen isotope ratios was described by Merritt and Hayes [639], who modified a GC-C-IRMS system by including a reduction reactor (Cu wire) between the combustion furnace and the IRMS, for reduction of nitrogen oxides and removal of oxygen. Preston and Slater [658] have described a less complex approach which provides useful data at lower precision. Similar approaches have been described by Brand et al. [657] and Metges et al. [659]. More recently Macko et al. [660] have described a procedure, which permits GC-IRMS determination of 15N/14N ratios in nanomole quantities of amino acid enantiomers with precision of 0.3-0.4%o. A key step was optimization of the acylation step with minimal nitrogen isotope fractionation [660]. 

It was detected by Urey, Brickwedde and Murphy in 1932. It occurs in all natural compounds of hydrogen including water, as well as in free hydrogen molecules at the ratio of about one part per 6,000 parts hydrogen. The principal application of deuterium is in tracer studies for measuring rates and kinetics of chemical reactions. It also is used in thermonuclear reactions and as a projectile in cyclotrons for bombardment of atomic nuclei to synthesize isotopes of several transuranium elements. Deuterium oxide, D2O, or heavy water is used as a neutron moderator in nuclear reactors. 

Fluorine is used in the separation of uranium, neptunium and plutonium isotopes by converting them into hexafluorides followed by gaseous diffusion then recovering these elements from nuclear reactors. It is used also as an oxidizer in rocket-fuel mixtures. Other applications are production of many fluo-ro compounds of commercial importance, such as sulfur hexafluoride, chlorine trifluoride and various fluorocarbons. 

Fuel Element. Any material which may undergo the appropriate reaction and be the source of energy in a fusion or fission nuclear reactor is known as nuclear fuel At the present state of technology such fuels are uranium, thorium or plutonium, either as natural materials or enriched or synthesized isotopes of these elements. They are used as solns or as solids (metals, oxides, or carbonates) shaped as plates, rods etc and known as fuel element (fuel plate or fuel rod)... 

In a typical fast breeder nuclear reactor, most of the fuel is 238U (90 to 93%). The remainder of the fuel is in the form of fissile isotopes, which sustain the fission process. The majority of these fissile isotopes are in the form of 239Pu and 241Pu, although a small portion of 235U can also be present. Because the fast breeder converts die fertile isotope 238 U into the fissile isotope 239Pu, no enrichment plant is necessary. The fast breeder serves as its own enrichment plant. The need for electricity for supplemental uses in the fuel cycle process is thus reduced. Several of the early hquid-metal-cooled fast reactors used plutonium fuels. The reactor Clementine, first operated in the Unired States in 1949. utilized plutonium metal, as did the BR-1 and BR.-2 reactors in the former Soviet Union in 1955 and 1956, respectively. The BR-5 in the former Soviet Union, put into operation in 1959. utilized plutonium oxide and carbide. The reactor Rapsodie first operated in France in 1967 utilized uranium and plutonium oxides. 

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