Uranium example

Here, we use the Bear Creek Uranium example discussed in 6.2 to calculate the acidity of contaminated groundwater and tailings fluids. If the total acidity of groundwater and contaminated sediments, as well as the neutralization capacity of the aquifer matrix are known, the distance that the acid plume will migrate can be estimated based on mass balance. 

The formula is fair for cases, when volume of metal is most less than volume of filling. For example, the volume of uranium makes up a few percents from volume of graphite in uranium - graphite fuel element and Wo 80 %. 

The use of larger particles in the cyclotron, for example carbon, nitrogen or oxygen ions, enabled elements of several units of atomic number beyond uranium to be synthesised. Einsteinium and fermium were obtained by this method and separated by ion-exchange. and indeed first identified by the appearance of their concentration peaks on the elution graph at the places expected for atomic numbers 99 and 100. The concentrations available when this was done were measured not in gcm but in atoms cm. The same elements became available in greater quantity when the first hydrogen bomb was exploded, when they were found in the fission products. Element 101, mendelevium, was made by a-particle bombardment of einsteinium, and nobelium (102) by fusion of curium and the carbon-13 isotope. 

The many possible oxidation states of the actinides up to americium make the chemistry of their compounds rather extensive and complicated. Taking plutonium as an example, it exhibits oxidation states of -E 3, -E 4, +5 and -E 6, four being the most stable oxidation state. These states are all known in solution, for example Pu" as Pu ", and Pu as PuOj. PuOl" is analogous to UO , which is the stable uranium ion in solution. Each oxidation state is characterised by a different colour, for example PuOj is pink, but change of oxidation state and disproportionation can occur very readily between the various states. The chemistry in solution is also complicated by the ease of complex formation. However, plutonium can also form compounds such as oxides, carbides, nitrides and anhydrous halides which do not involve reactions in solution. Hence for example, it forms a violet fluoride, PuFj. and a brown fluoride. Pup4 a monoxide, PuO (probably an interstitial compound), and a stable dioxide, PUO2. The dioxide was the first compound of an artificial element to be separated in a weighable amount and the first to be identified by X-ray diffraction methods. 

The preparation and structure determination of ferrocene marked the beginning of metallocene chemistry Metallocenes are organometallic compounds that bear cyclo pentadiemde ligands A large number are known even some m which uranium is the metal Metallocenes are not only stucturally interesting but many of them have useful applications as catalysts for industrial processes Zirconium based metallocenes for example are the most widely used catalysts for Ziegler-Natta polymerization of alkenes We 11 have more to say about them m Section 14 15... 

Another area where controlled-potential coulometry has found application is in nuclear chemistry, in which elements such as uranium and polonium can be determined at trace levels. Eor example, microgram quantities of uranium in a medium of H2SO4 can be determined by reducing U(VI) to U(IV) at a mercury working electrode. 

Other isotopes can be used to determine the age of samples. The age of rocks, for example, has been determined from the ratio of the number of radioactive atoms to the number of stable gfPb atoms produced by radioactive decay. For rocks that do not contain uranium, dating is accomplished by comparing the ratio of radioactive fgK to the stable fgAr. Another example is the dating of sediments collected from lakes by measuring the amount of g Pb present. 

One of the most significant sources of change in isotope ratios is caused by the small mass differences between isotopes and their effects on the physical properties of elements and compounds. For example, ordinary water (mostly Ej O) has a lower density, lower boiling point, and higher vapor pressure than does heavy water (mostly H2 0). Other major changes can occur through exchange processes. Such physical and kinetic differences lead to natural local fractionation of isotopes. Artificial fractionation (enrichment or depletion) of uranium isotopes is the basis for construction of atomic bombs, nuclear power reactors, and depleted uranium weapons. 

It is not necessary that there be two isotopes in both the sample and the spike. One isotope in the sample needs to be measured, but the spike can have one isotope of the same element that has been produced artificially. The latter is often a long-lived radioisotope. For example, and are radioactive and all occur naturally. The radioactive isotope does not occur naturally but is made artificially by irradiation of Th with neutrons. Since it is commercially available, this last isotope is often used as a spike for isotope-dilution analysis of natural uranium materials by comparison with the most abundant isotope ( U). 

It is possible to prepare very heavy elements in thermonuclear explosions, owing to the very intense, although brief (order of a microsecond), neutron flux furnished by the explosion (3,13). Einsteinium and fermium were first produced in this way they were discovered in the fallout materials from the first thermonuclear explosion (the "Mike" shot) staged in the Pacific in November 1952. It is possible that elements having atomic numbers greater than 100 would have been found had the debris been examined very soon after the explosion. The preparative process involved is multiple neutron capture in the uranium in the device, which is followed by a sequence of beta decays. Eor example, the synthesis of EM in the Mike explosion was via the production of from followed by a long chain of short-Hved beta decays,... 

In general, the absorption bands of the actinide ions are some ten times more intense than those of the lanthanide ions. Fluorescence, for example, is observed in the trichlorides of uranium, neptunium, americium, and curium, diluted with lanthanum chloride (15). 

MIBK is a highly effective separating agent for metals from solutions of their salts and is used in the mining industries to extract plutonium from uranium, niobium from tantalum, and zirconium from hafnium (112,113). MIBK is also used in the production of specialty surfactants for inks (qv), paints, and pesticide formulations, examples of which are 2,4,7,9-tetramethyl-5-decyn-4,7-diol and its ethoxylated adduct. Other appHcations include as a solvent for adhesives and wax/oil separation (114), in leather (qv) finishing, textile coating, and as a denaturant for ethanol formulations. 

Nuclear Applications. Powder metallurgy is used in the fabrication of fuel elements as well as control, shielding, moderator, and other components of nuclear-power reactors (63) (see Nuclearreactors). The materials for fuel, moderator, and control parts of a reactor are thermodynamically unstable if heated to melting temperatures. These same materials are stable under P/M process conditions. It is possible, for example, to incorporate uranium or ceramic compounds in a metallic matrix, or to produce parts that are similar in the size and shape desired without effecting drastic changes in either the stmcture or surface conditions. OnlyHttle post-sintering treatment is necessary. 

Intrusive Deposits. Deposits included in the intmsive deposit type are those associated with intmsive or anatectic rocks of different chemical composition, eg, alaskite, granite, monzonite, peralkaline syenite, carbonatite, and pegmatite. Examples include the uranium occurrences in the porphyry copper deposits such as Bingham Canyon and Twin Butte in the United States, the Rossing Deposit in Namibia, and Ilimaussaq deposit in Greenland, Palabora in South Africa, and the deposits in the Bancroft area, Canada (15). 

Phosphorite Deposits. Sedimentary phosphorites contain low concentrations of uranium in fine-grained apatite. Uranium of this type is considered an unconventional resource. Significant examples of these uranium ore types include the U.S. deposits in Elorida, where uranium is recovered as a by-product, and the large deposits in North African and Middle Eastern countries (16). 

Collapse Breccia Pipe Deposits. The primary occurrence of coUapse breccia pipe deposits is in circular, vertical pipes fiUed with down-dropped fragments. Uranium is concentrated in the permeable breccia matrix and in the accurate fracture zones enclosing the pipe. An example of... 

Volcanic Deposits. Uranium deposits of volcanic deposits type are strata-bound and stmcture-bound concentrations in acid volcanic rocks. Uranium is commonly associated with molybdenum, fluorine, etc. Examples are the uranium deposits in Michelin, Canada Nopal I in Chihualiua, Mexico Macusani in Pern and numerous deposits in China and the CIS (16). 

Meta.soina.tlte Deposits. Included in the metasomatite deposit grouping are uranium deposits in alkah metasomatites, eg, albitites, aegirinites, and alkah—amphibole rocks, commonly intmded by microcline granite. Examples are the deposits in Espinharasin, Brazil, and Ross Adams, Alaska, as well as the Zheltye Vody deposit in Krivoy Rog area in Ukraine (16). 

MetamorphicDeposits. Uranium deposits belonging to the metamorphic class occur in metasediments or metavolcanics generally, without direct evidence of post-metamorphic mineralization. Examples include the deposits at Eorstau, Austria (16). 

Lignite. Deposits generally classified as unconventional uranium resources occur in lignite and in clay or sandstone immediately adjacent to lignite. Examples are uraniferous deposits in the Serres Basin, Greece, North and South Dakota in the United States, and Melovoe in the CIS (17) (see... 

The amount of HEU that becomes avadable for civdian use through the 1990s and into the twenty-first century depends on the number of warheads removed from nuclear arsenals and the amount of HEU in the weapons complex that is already outside of the warheads, ie, materials stockpdes and spent naval reactor fuels. An illustrative example of the potential amounts of weapons-grade materials released from dismanded nuclear weapons is presented in Table 7 (36). Using the data in Table 7, a reduction in the number of warheads in nuclear arsenals of the United States and Russia to 5000 warheads for each country results in a surplus of 1140 t of HEU. This inventory of HEU is equivalent to 205,200 t of natural uranium metal, or approximately 3.5 times the 1993 annual demand for natural uranium equivalent. 

The high cost of isotope separation has limited, the use of separated isotopes in nuclear reactors to specific cases where substitutes that do not involve separated isotopes are not available. The most important example is that of uranium-235 [15117-96-17, the most abundant naturally occurring... 

Chemical Separation. A reprocessing facility typically utilizes multiple extraction/reextraction (stripping) cycles for the recovery and purification of uranium and plutonium. For example, a co-decontamination and partitioning cycle is followed by one or more cycles of uranium and plutonium purification. The basic process is illustrated in Figure 3. 

The determination of critical si2e or mass of nuclear fuel is important for safety reasons. In the design of the atom bombs at Los Alamos, it was cmcial to know the critical mass, ie, that amount of highly enriched uranium or plutonium that would permit a chain reaction. A variety of assembhes were constmcted. Eor example, a bare metal sphere was found to have a critical mass of approximately 50 kg, whereas a natural uranium reflected 235u sphere had a critical mass of only 16 kg. 

A number of pool, also called swimming pool, reactors have been built at educational institutions and research laboratories. The core in these reactors is located at the bottom of a large pool of water, 6 m deep, suspended from a bridge. The water serves as moderator, coolant, and shield. An example is the Lord nuclear reactor at the University of Michigan, started in 1957. The core is composed of fuel elements, each having 18 aluminum-clad plates of 20% enriched uranium. It operates at 2 MW, giving a thermal flux of 3 x 10 (cm -s). The reactor operates almost continuously, using a variety of beam tubes, for research purposes. 

Radioactivity occurs naturally in earth minerals containing uranium and thorium. It also results from two principal processes arising from bombardment of atomic nuclei by particles such as neutrons, ie, activation and fission. Activation involves the absorption of a neutron by a stable nucleus to form an unstable nucleus. An example is the neutron reaction of a neutron and cobalt-59 to yield cobalt-60 [10198 0-0] Co, a 5.26-yr half-life gamma-ray emitter. Another is the absorption of a neutron by uranium-238 [24678-82-8] to produce plutonium-239 [15117 8-5], Pu, as occurs in the fuel of a nuclear... 

PoUowing further development (38), a two-cycle process has been adopted by industry. In the first concentration cycle, the clarified feed acid containing 100—200 mg/L U Og [1334-59-8] is oxidized, for example, with hydrogen peroxide or sodium chlorate [7775-09-9] to ensure that uranium is in its 6+ valence state is not extracted. Uranium is extracted with a solvent composed of 0.5 Af D2EHPA and 0.125 Af TOPO dissolved in an aUphatic hydrocarbon diluent. 

Tetrakis-Cp uranium complexes are readily prepared via metathesis of UCl and KCp in refluxing benzene. These complexes are a relatively rare example of a pseudotetrahedral complex with four Tj -Cp rings, (rj-ring) (25). The Cp derivative has been shown to react with CO and CO2 to give acyl and carboxylato complexes. This complex also reacts with alkyl haUdes to afford the U(IV) complex, Cp UX (X = halide). 

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