Hydrolysis of uranium

Hydroxides. The hydrolysis of uranium has been recendy reviewed (154,165,166), yet as noted in these compilations, studies are ongoing to continue identifying all of the numerous solution species and soHd phases. The very hard uranium(IV) ion hydrolyzes even in fairly strong acid (- 0.1 Af) and the hydrolysis is compHcated by the precipitation of insoluble hydroxides or oxides. There is reasonably good experimental evidence for the formation of the initial hydrolysis product, U(OH) " however, there is no direct evidence for other hydrolysis products such as U(OH) " 2> U(OH)" 2> U(OH)4 (or UO2 2H20). There are substantial amounts of data, particulady from solubiUty experiments, which are consistent with the neutral species U(OH)4 (154,167). It is unknown whether this species is monomeric or polymeric. A new study under reducing conditions in NaCl solution confirms its importance and reports that it is monomeric (168). 8olubihty studies indicate that the anionic species U(OH) , if it exists, is only of minor importance (169). There is limited evidence for polymeric species such as Ug(OH) " 25 (1 4). 

Bostick WD, McCulla WH, Pickrell PW. 1985. Sampling, characterization, and remote sensing of aerosols formed in the atmospheric hydrolysis of uranium hexafluoride. J Environ Sci Health, Part A A20 369-393. 

Grenthe, L, Bidoglio, G., and Omenetto, N. (1989) Use of thermal lensing spectroscopy (TLS) for the study of mononuclear hydrolysis of uranium(lV). Inorg. Chem.,... 

Rush, R.M. and Johnson, J.S. (1963) Hydrolysis of uranium(VI) absorption spectra of chloride and perchlorate solutions. J. Phys. Chem., 67, 821-825. 

Rush, R.M., Johnson, J.S., and Kraus, K.A. (1%2) Hydrolysis of uranium(Vl) ultracentrifugation and acidity measurements in chloride solutions. Inorg. Chem., 1, 378-386. 

The hydrolysis of the uranyl(VI) ion, UO " 2> has been studied extensively and begins at about pH 3. In solutions containing less than lO " M uranium, the first hydrolysis product is the monomeric U02(OH)", as confirmed using time-resolved laser induced fluorescence spectroscopy. At higher uranium concentrations, it is accepted that polymeric U(VI) species are predominant in solution, and the first hydrolysis product is then the dimer, (U02)2(0H) " 2 (154,170). Further hydrolysis products include the trimeric uranyl hydroxide complexes (U02)3(0H) " 4 and (1102)3(OH)(154). At higher pH, hydrous uranyl hydroxide precipitate is the stable species (171). In studying the sol-gel U02-ceramic fuel process, O nmr was used to observe the formation of a trimeric hydrolysis product, ((U02)3( -l3-0)(p.2-0H)3) which then condenses into polymeric layers of a gel based on the... 

The last reaction cited above as shown is very effectively catalyzed by bacterial action but is very slow chemically by recycling the spent ferrous liquors and regenerating ferric iron bacterially, the amount of iron which must be derived from pyrite oxidation is limited to that needed to make up losses from the system, principally in the uranium product stream. This is important if the slow step in the overall process is the oxidation of pyrite. The situation is different in the case of bacterial leaching of copper sulfides where all the sulfide must be attacked to obtain copper with a high efficiency. A fourth reaction which may occur is the hydrolysis of ferric sulfate in solution, thus regenerating more sulfuric acid the ferrous-ferric oxidation consumes acid. 

The sol-gel-entrapped microbial cells have shown excellent tolerance to different alcohols [99], The immobilized E. coli cells followed the Michaelis-Menten equation when quantified with the (3-glucosidase activity via the hydrolysis of 4-nitrophenyl-(3-D-galactopyranosdie [142], The sol-gel matrices doped with gelatin prevented the cell lysis, which usually occurs during the initial gelation process [143], Microorganisms are now widely used in the biosorption of different pollutants and toxicants. Bacillus sphaericus JG-A12 isolated from uranium mining water has been entrapped in aqueous silica nanosol for the accumulation of copper and uranium [144], Premkumar et al. [145] immobilized recombinant luminous bacteria into TEOS sol-gel to study the effect of sol-gel conditions on the cell response (luminescence). The entrapped and free cells showed almost the same intensity of luminescence (little lower), but the entrapped cells were more stable than the free cells (4 weeks at 4°C). This kind of stable cell could be employed in biosensors in the near future. 

Alkoxide gels, 23 60 Alkoxide gels, in optical fiber manufacturing, 11 145 Alkoxide initiators, 14 259 Alkoxide ligands, thorium, 24 770 Alkoxides, 12 190 25 72-86 controlled hydrolysis of, 23 56 iron, 14 533 mixed-metal, 25 100 titanium, 25 82 uranium complexation with,... 

As a result of its four oxidation states, its tendency to complex with anions and the polymeric ions formed as a result of hydrolysis, the aqueous chemistry of uranium is complex. In aqueous solutions uranium salts exhibit acidic properties as a result of hydrolysis which increases in the order U3+ < UO + < U4+. In the case of UO + at 25° the principal hydrolised species are U020H+,(U02)2 (OH) + and (UO fOHj. 

Bismuth hydroxide is used as an absorbent and in the hydrolysis of ribonucleic acid. It also is used in the isolation of plutonium from irradiated uranium. 

A few salts of composition (Et4N)2[MvOX5] (Mv = Pa, X = C1, Br MV = U, X = F) are known the uranium(V) compound is obtained from the dihydrate under vacuum, and the protactinium(V) chlorocompound is prepared by hydrolysis of the hexachloro complex salt in methyl cyanide containing 0.5% water. Salts of composition (Et4N)[Pa(OEt)2X4j (X = Cl, Br) are also known. 

Berthet, J.C., Nierlich, M., Miquel, Y., Madic, C., Ephritikhine, M. 2005. Selective complexation of uranium(III) over lanthanide(IH) triflates by 2,2 6, 2"-terpy ridine. X-ray crystal structures of [MfOTf fterpy ] and [M(OTf)2(terpy)2(py)][OTf](M = Nd, Ce, U) and of polynuclear (x-oxo uranium(IV) complexes resulting from hydrolysis. Journal of the Chemical Society, Dalton Transactions 2 369-379. 

Carboxylic acids formed by the hydrolysis of nitro compounds have been identified as complexing uranium(VI) (79, 139). 

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