Cecil E. Higgins

Interactions between tributyl phosphate, phosphoric acid and water

Abstract The distribution co-efficient for phosphoric acid between tributyl phosphate (TBP) and water increased with the acid concentration in the inorganic phase and correlated with the water behaviour in the organic phase. Water accompanying the acid into the TBP was salted out after the ratio 3 TBP·H 3 PO 4 ·6 H 2 O was reached but levelled off at one water per TBP regardless of the phosphoric acid concentration over the range 1–4 moles H 3 PO 4 per mole TBP. Evidence for a high degree of association in solutions of anhydrous H 3 PO 4 and TBP was obtained from ebullioscopic molecular weight determinations in ether and the viscosity of undiluted solutions. The maximum viscosity occurred at the 3 H 3 PO 4 to 1 TBP ratio and was about three times that of anhydrous, super-cooled H 3 PO 4 .

Complexes of dibutyl phosphoric acid

Abstract Highly associated complexes have been formed between dibutyl phosphoric acid and the cations: Cu(II), UO 2 (II), Fe(III), Y(III), Al(III), and Th(IV). 32 P-labelled dibutyl phosphoric acid was used to assist in the analysis of the compounds. Metathesis of the solid Th(IV) complex with aqueous sodium hydroxide was complete, suggesting a practical method for removing the complexes from solvents and equipment.

The preparation of cesium lanthanide hexafluoroacetylacetonates by cation exchange

Abstract CsEu( hfa ) 4 and CsLa( hfa ) 4 ·H 2 O, where hfa is the hexafluoroacetylacetone anion, have been prepared in > 80% yield by cation exchange column procedures. The rare earth was fixed on Dowex 50 in either the cesium or hydrogen form; in the latter case the excess acid form resin was converted to the cesium form before the rare earth was eluted with 0·4 M Cs hfa in 50% ethanol. The earth can be loaded with insignificant loss onto the resin even from solutions ∼ 1 M in HCl. This presents an advantage when starting with the rare earth oxide since it precludes the formation of the oxychloride.