Tributyl phosphate, solvent effect

The effect of irradiation on the extractability of sulfoxides towards plutonium, uranium and some fission products were studied by Subramanian and coworkers . They studied mainly the effect of irradiation on dihexyl sulfoxide (DHSO) and found that irradiation did not change the distribution coefficient for Ru, Eu and Ce but increases the distribution coefficient for Zr and Pu. When comparing DHSO and tributyl phosphate (TBP), the usual solvent for the recovery and purification of plutonium and uranium from spent nuclear fuels, the effect of irradiation to deteriorate the extraction capability is much larger in TBP. Lan and coworkers studied diphenyl sulfoxides as protectors for the gamma radiolysis of TBP. It was found that diphenyl sulfoxide can accept energy from two different kinds of excited TBP and thus inhibits the decomposition of the latter. 

Solvent extraction by tributyl phosphate (TBP) (13, 96), dithizone (20, 71, 72), cupferron (89), thenoyl trifluoroacetone (TTA) (55), diiso-propyl ketone (26), mesityl oxide (92), tri-n-benzylamine and methyl di-n-octylamine (99), diisopropyl and diisobutyl carbinol (100) have all found some application on the trace scale. Acetylaeetone and methyl isobutyl ketone extract milligram amounts of polonium almost quantitatively from hydrochloric acid, but the stable polonium-organic compounds which are formed make it difficult to recover the polonium in a useful form from solutions in these ketones (7). Ion exchange (22, 115, 119) and paper chromatography (44, 87) have also been used for trace scale separations of polonium, but the effects of the intense alpha-radiation on organic com-... 

Raman spectral studies of the species [MX ]("-2)- (n = 2-4 M = Zn, Cd or Hg X = Cl, Br or I) in anhydrous tributyl phosphate have been reported.1001 For the MX2 molecules, sufficient metal dihalide-solvent interaction exists to suggest bent X—M—X species with Cjv rather than D< h symmetry. The effect appears most marked for zinc(II) and least marked for mercury(II)... 

Tripathi, S.C., Sumathi, S., Ramanujam, A. 1999. Effects of solvent recycling on radiolytic degradation of 30% tributyl phosphate- -dodecane-HN03 system. Sep. Sci. Technol. 34 (14) 2887-2903. 

Solvent extraction of indium(m) thiocyanate, In(SCN)3, with tributyl phosphate in hexane is markedly enhanced by the presence of background NaClOi.- it was concluded that this is due chiefly to a salting-out effect.564... 

However, even the precipitation of 99.8 pure ceric salts does obviously not remove all the cerium from the solution, and additional steps are necessary. A very effective way is air oxidation and solvent extraction. It has become apparent that TBP (tributyl phosphate, see also in Sect. 4.2.3.1) is the best extractant for large scale operations (Gupta and Krishnamurthy 2005). 

In the last decades of evaluation of the physical network density of SPU was done on samples swollen to equilibrium in two solvents. Swelling of SPU in toluene practically does not affect hard domains. Swelling of SPU (based on oligoethers diol) in a tributyl phosphate (a strong acceptor of protons) results in full destruction of the physical network with hard domains. The effective network density was evaluated for samples swollen to equilibrium in toluene according to the Cluff-Gladding method. Samples were swollen to equilibrium in TBP and the density of the physical network was determined from equar tion ... 

The Mossbauer parameters of the tin halides show that in these systems the correlation between the isomer shifts and the donicity values is by no means as clear as for antimony pentachloride. The isomer shifts of tin tetrachloride agree, within experimental error, in frozen dimethyl sulphoxide, dimethylformamide and tributyl phosphate solutions, and those of tin tetraiodide agree in dimethyl sulphoxide, dimethylformamide and ethanol solutions. The Gutmann donicities of these solvents lie in the range 20-30. For both tin compounds, a further decrease in the donicity of the solvent causes an increase in the isomer shift, which indicates an increase in the electron density at the tin nucleus. This effect appeared in acetonitrile solution with tin tetrachloride, and in tributyl phosphate and carbon tetrachloride solutions with tin tetraiodide. (It must be emphasized that the last two solvents have low relative permittivities, whereas that of acetonitrile is high.)... 

Barnard, K.R. and Turner, N.L. (2011) The effect of temperature on hydroxyoxime stability in the LIX 63 - Versatic 10 - tributyl phosphate synergistic solvent extraction system under synthetic nickel laterite conditions Hydrometallurgy 109 245-251... 

Quite spectacular solubility enhancement can sometimes be obtained in this way. For example Wong and Johnston [5] obtained a hundred-fold enhancement of the solubility of cholesterol in compressed CO2 using 9% methanol as entrainer and Kumik and Reid [6] have reported an even greater effect on the solubility of hydroquinone using 2% tributyl phosphate as entrainer. They also found that the solubility of phenanthrene increased by factors of between 2 and 3 in the presence of naphthalene. Larson and King [7] found that a ten-fold increase occurred in the solubility of a typical steroid in compressed CO2 at 350 bar and 40°C when 5% methanol was added to the solvent, though an amino acid which they tested remained virtually insoluble. Kim et al. [8] found that the solubility of benzoic acid in CO2 at 35°C and 200 bar is approximately doubled when 8 wt% SO2 is added to the solvent. There are many other examples of this type. 

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