Linear Free Energy Relationships in Extraction of Rare Earths by Acidic Organophosphorus Extractants

The correlation relationships of apparent extraction equilibrium constant (1gK(ex)) with the electronic effect parameter( Sigma sigma(Phi)) and the steric effect parameter ( Sigma upsilon ) of the substituents in extractant molecules are investigated by linear regression analysis in the extraction of rare earths by various classes and structures of monoacidic organophosphorus extractants. The results indicate that in Linear free energy relationship formula 1gK(ex) = rho Sigma sigma(Phi) + psi Sigma upsilon + h generally follows for this kind of extraction systems. Accordingly, the quantitative structure-behaviour relationships of extractants are discussed. These relationships can be preliminarily applied to predict the 1gK(ex) values of rare earth extraction with definite structures of this class of extractants, and thus can provide some directions for the design of new RE extractants.

Linear free energy relationships between reaction rate constants and equilibrium constants of complex compounds——III. Kinetics and mechanisms of ternary complex formation between (5-X-1, 10-phenanthroline)copper(II) and threonine

The kinetics of ternary complex formation involving Cu(5-X-1, 10-phen) and threonine (CuAL, A=5-X-1, 10-phen; L=threonine or represented by O-N; X=NO_2, Cl, H, CH_3) has been studied by temperature-jump and stopped-flow methods. The formation rate constants, k_f(M^(-1).s^(-1)), for the complexation reaction, CuA + LCuAL, are as follows; X=NO_2, 8.68×10~8; X=Cl, 7.13×10~8; X=H, 6.12×10~8; X=CH_3, 5.42×10~8. The rate constants for zwitterion attack are nil within experimental error. It has been found that a linear free energy relationship exists between the stability(logK_(CuAL)^(CuA) of the complexes CuAL and log kf as follows: IogK_(CuAL)^(CuA)=0.13 + 0.83 logk_f, r=0.99. It suggested that the formation rate governed the stability of the ternary complexes. The rates of formation of the ternary complexes increased with decreasing electron-donating property of the substituents. A linear relationship was found to exist as expressed by the following equation: log(k_f^R/k_F^O) = 0.097σ, r=0.96. A mechanism involves a rapid equilibrium between CuA and L followed by a slow ring closure of L.