Oxidation states liquids

MAG SEP may have difficulty in preferentially removing one metal from a contaminant stream containing several different metals. Some problems have been encountered when the target metal is present in different oxidation states. Liquids with low pH may be difficult for MAG SEP to process. 

When an element has more than one oxidation state the lower halides tend to be ionic whilst the higher ones are covalent—the anhydrous chlorides of lead are a good example, for whilst leadfll) chloride, PbCl2, is a white non-volatile solid, soluble in water without hydrolysis, leadflV) chloride, PbC, is a liquid at room temperature (p. 200) and is immediately hydrolysed. This change of bonding with oxidation state follows from the rules given on p.49... 

Cobalt has an odd number of electrons, and does not form a simple carbonyl in oxidation state 0. However, carbonyls of formulae Co2(CO)g, Co4(CO)i2 and CoJCO),6 are known reduction of these by an alkali metal dissolved in liquid ammonia (p. 126) gives the ion [Co(CO)4] ". Both Co2(CO)g and [Co(CO)4]" are important as catalysts for organic syntheses. In the so-called oxo reaction, where an alkene reacts with carbon monoxide and hydrogen, under pressure, to give an aldehyde, dicobalt octacarbonyl is used as catalyst ... 

Elevated pressures are required to keep water in the Hquid state. Liquid water cataly2es oxidation so that reactions proceed at relatively lower temperatures than would be required if the same materials were oxidi2ed in open flame combustion. At the same time, water moderates oxidation rates by providing a medium for heat transfer and removing excess heat by evaporation. 

Oxidation catalysts are either metals that chemisorb oxygen readily, such as platinum or silver, or transition metal oxides that are able to give and take oxygen by reason of their having several possible oxidation states. Ethylene oxide is formed with silver, ammonia is oxidized with platinum, and silver or copper in the form of metal screens catalyze the oxidation of methanol to formaldehyde. Cobalt catalysis is used in the following oxidations butane to acetic acid and to butyl-hydroperoxide, cyclohexane to cyclohexylperoxide, acetaldehyde to acetic acid and toluene to benzoic acid. PdCh-CuCb is used for many liquid-phase oxidations and V9O5 combinations for many vapor-phase oxidations. 

The use of liquid NH3 to prepare compounds of elements in unusual (low) oxidation states is exemplified by the successive reduction of K2[Ni(CN)4] with Na/Hg in the presence of an excess of CN the dark-red dimeric Ni complex K4[Ni2(CN)6] is first formed and this can be further reduced to the yellow Ni° complex K4[Ni(CN)4]. The corresponding complexes [Pd(CN)4]" and [Pt(CN)4]" can be prepared similarly, though there is no evidence in these latter systems for the formation of the M dimer. A ditertiaiyphosphine complex of Pd° has also been prepared ... 

The versatility of cyanide and bipyridyl ligands has been used to stabilize low oxidation states. By using potassium in liquid ammonia, K3Ti (CN)6 is reduced to K2Ti (CN)4 and TiBt3 - - KCN to K4Ti°(CN)4. With ZrBt3 and M CN (M = K, Rb) in liquid ammonia, ammonolysis occurs and zerovalent Zr is produced ... 

Because they possess an odd number of valence electrons the elements of this group can only satisfy the 18-electron rule in their carbonyls if M-M bonds are present. In accord with this, mononuclear carbonyls are not formed. Instead [M2(CO)s], [M4(CO)i2] and [M6(CO)i6] are the principal binary carbonyls of these elements. But reduction of [Co2(CO)g] with, for instance, sodium amalgam in benzene yields the monomeric and tetrahedral, 18-electron ion, [Co(CO)4] , acidification of which gives the pale yellow hydride, [HCo(CO)4]. Reductions employing Na metal in liquid NH3 yield the super-reduced [M(CO)3] (M = Co, Rh, Ir) containing these elements in their lowest formal oxidation state. 

Besides [Ni(CO)4] and organometallic compounds discussed in the next section, nickel is found in the formally zero oxidation state with ligands such as CN and phosphines. Reduction of K2[Ni (CN)4] with potassium in liquid ammonia precipitates yellow K4[Ni (CN)4], which is sensitive to aerial oxidation. Being... 

Another means of in situ metal-carbene complex formation in an ionic liquid is the direct oxidative addition of the imidazolium cation to a metal center in a low oxidation state (see Scheme 5.2-2, route b)). Cavell and co-workers have observed oxidative addition on heating 1,3-dimethylimidazolium tetrafluoroborate with Pt(PPli3)4 in refluxing THF [32]. The Pt-carbene complex formed can decompose by reductive elimination. Winterton et al. have also described the formation of a Pt-car-bene complex by oxidative addition of the [EMIM] cation to PtCl2 in a basic [EMIM]C1/A1C13 system (free CP ions present) under ethylene pressure [33]. The formation of a Pt-carbene complex by oxidative addition of the imidazolium cation is displayed in Scheme 5.2-4. 

A second source of plutonium, dispersed more locally, is liquid effluent from fuel reprocessing facilities. One such is the fuel reprocessing plant at Windscale, Cumbria in the United Kingdom where liquid waste is released to the Irish Sea(6). Chemical analysis of this effluent shows that about one percent or less of the plutonium is in an oxidized form before it contacts the marine water(7). Approximately 95 percent of the plutonium rapidly adsorbs to particulate matter after discharge and deposits on the seabed while 5 percent is removed from the area as a soluble component ). Because this source provided concentrations that were readily detected, pioneering field research into plutonium oxidation states in the marine environment was conducted at this location. 

The sampling of solution for activity measurement is carried out by filtration with 0.22 pm Millex filter (Millipore Co.) which is encapsuled and attached to a syringe for handy operation. The randomly selected filtrates are further passed through Amicon Centriflo membrane filter (CF-25) of 2 nm pore size. The activities measured for the filtrates from the two different pore sizes are observed to be identical within experimental error. Activities are measured by a liquid scintillation counter. For each sample solution, triplicate samplings and activity measurements are undertaken and the average of three values is used for calculation. Absorption spectra of experimental solutions are measured using a Beckman UV 5260 spectrophotometer for the analysis of oxidation states of dissolved Pu ions. 

The above information was used to develop conceptual flowsheets for the extraction of all of the actinides (U, Np, Pu, Am, and Cm) from high-level liquid waste from PUREX processing using 0.4 M 0fuel using 0.8 M DHDECMP in DEB. In both flowsheets, no oxidation state of Pu is necessary since the III, IV, and VI state extract into the organic phase. 

The bisphosphonate - upon reduction with lithiumaluminum hydride in ether at 0°C - produced the amide functionalized primary bisphosphine (1) in good yields [45]. This reaction proceeded to reduce the amide group in 1 to produce the amine functionaUzed primary bisphosphine (2) in <5% yields. The amido bisprimary phosphine 1 is an air stable crystalline solid whereas the amine compound 2 is an oxidatively stable liquid. Separation of 1 and 2 in pure forms was achieved using coliunn chromatography. The amidic bisprimary phosphine 1 was crystallized from chloroform and exhibits remarkable stability not only in the solid state but also in solution as well. The crystal structure of the air stable primary his-phosphine 1 as shown in Fig. 1 is unprecedented to date. 

The common oxidation states for gold in the dithiocarbamato complexes are + 1 and + 3. Like for the silver compounds the oxidation state + 2 is observed in diluted liquid and solid solutions only. 

Table 8.53 shows the main features of XAS. The advantages of EXAFS over diffraction methods are that the technique does not depend on long-range order, hence it can always be used to study local environments in amorphous (and crystalline) solids and liquids it is atom specific and can be sensitive to low concentrations of the target atom (about 100 ppm). XAS provides information on interatomic distances, coordination numbers, atom types and structural disorder and oxidation state by inference. Accuracy is 1-2% for interatomic distances, and 10-25 % for coordination numbers. 

The changes that occur after the heat processing of food systems are often monitored by different parameters, such as total carotenoid content (and therefore isomerization and oxidation are underestimated), individual carotenoids (overall changes may be missed), and CIELAB color parameters (no information on carotenoid degradation mechanism). The data given in Table 12.3 reflects the influence of matrix composition, food state (liquid or solid), and measured parameter on the carotenoid degradation kinetics. 

Russian scientists (Avrorin et al., 1981, 1985) have reported that reactions of complex mixtures of radon, xenon, metal fluorides, bromine pentafluoride, and fluorine yield a higher fluoride of radon which hydrolyzes to form RnO. However, efforts to confirm these findings have been unsuccessful. In similar experiments which have been carried out at Argonne National Laboratory (Stein, 1984), it has been found that radon in the hydrolysate is merely trapped in undissolved solids centrifugation removes the radon from the liquid phase completely. This is in marked contrast to the behavior of a solution of XeO, which can be filtered or centrifuged without loss of the xenon compound. Hence there is no reliable evidence at present for the existence of a higher oxidation state of radon or for radon compounds or ions in aqueous solutions. Earlier reports of the preparation of oxidized radon species in aqueous solutions (Haseltine and Moser, 1967 Haseltine, 1967) have also been shown to be erroneous (Flohr and Appelman, 1968 Gusev and Kirin, 1971). 

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