By Y. Marcus
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Extra info for Critical Evaluation of Some Equilibrium Constants Involving Organophosphorus Extractants
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Data for dilute benzene (65L), xylene (63A), kerosene (60A) and carbon tetrachloride (68M) solutions of S have been reported, from which equilibrium constants have been calculated. The former, unfortunately cannot be correct, since for a fourfold increase in aqueous HA concentration from 1 M to 4 M, corresponding to about a hundredfold increase in a ± „ A , there is only a maximal twofold increase in the distribution coefficient of HA. are unfortunately too sketchy to permit evaluation. The data for kerosene The other two solvents, oo however, yield reasonable results, and the log Q/·-,·, values are shown for xylene and carbon tetrachloride in Table VIII-1.
2 M HC10. 1 M (Na, H)C104· Unfortunately, there are gross discrepancies be tween equilibrium quotients Q,-. ,. reported by different authors for several solvents. Low values of the quotients may be due (69Y) to the presence of more water-soluble impurities, such as the monoalkyl ester. 69). (71K). A similar situation exists with regard to Qr3i» and earlier, low values (66S, 68L) should probably be dis counted in view of later higher values (69Y, 70U and 71L) although the latter by no means agree among themselves.
746 (1964). P. , Radiokhimiya, 6^, 714 (1964). M. , Zh. Neorg. , 1£, 518 (1965). P. , Zh. Neorg. , 1£, 2774 (1965). H. , J. Inorg. Nucl. , 29^, 2615 (1967). , J. Inorg. Nucl. , 31_, 239 (1969). VIII. Solvent: Tri-n-butylphosphate (TBP) , S Ligand: Chloride (Cl~) , A~ Reactions: H + + A~ + S~ = HAS (VIII-1) H + + A" + nH 2 0 + mS" = H I H ^ O J ^ A I T (VIII-2) The hydrochloric acid - TBP system is not very stable chemically, and eventually extensive hydrolysis occurs. Also, the extractability of hydro chloric acid is rather low, so that either high S concentrations or high HA concentrations are required in order to have conveniently measureable concen trations of HA in the organic phase.