The adsorption equilibria of seven trivalent metal ions (M(3+):  Sc(3+), Y(3+), La(3+), Fe(3+), Al(3+), Ga(3+), and In(3+)) on chelating resins containing iminodiacetic acid groups (-LH(2)) were studied. Adsorption curves, measured under the conditions of metal ions in excess against chelating groups, directly indicated the metal-to-ligand ratio of the complexes formed in the resin phase. Iron and group 13 metal ions were adsorbed as (-L)(2)HM, while group 3 metal ions were adsorbed as (-L)(3)H(3)M and (-L)(2)HM. The adsorption constants for (-L)(2)HM found for all the metal ions were well correlated with the formation constants of iminodiacetate complexes in aqueous solutions. The actual adsorption of group 3 metal ions was significantly enhanced beyond that expected from this correlation because of the formation of (-L)(3)H(3)M. This is why the selectivity in the adsorption of trivalent metal ions differs from that in the complexation of iminodiacetate in aqueous solutions. The effects of anions and the number of iminodiacetic acid groups per unit weight of resins were also discussed.

The water content was determined for five strongly basic anion-exchange resins (trimethyammonium type having different exchange capacities and cross-linking degrees by divinylbenzene) in definite anionic forms (ten singly, three doubly, one triply, and one quadruply charged) dried at 25 °C and at a relative humidity of 50%. Incorporation of the results of the previous research on the conventional resins by X-ray absorption fine structure and diffraction methods indicated that the present method gave the number of intrinsic water molecules strongly interacting with an anion. The hydration numbers of weakly hydrating anions (Cl⁻, Br⁻, and ClO₄⁻) and a small anion (F⁻) were independent of the exchange capacity and slightly decreased with an increase in cross-linking, especially at 8%. The small and strongly hydrating ion F⁻ kept the in-water hydration structure to form a water-separated ion pair in the resins, while the other weakly hydrating ions were appreciably dehydrated to form a contact ion pair. The hydration number of a strongly hydrating ion, H₂PO₄⁻, appreciably decreased with increases in both the exchange capacity and cross-linking degree accompanied by intermolecular hydrogen bonding between the anions. This may be related to other characteristics of the H₂PO₄⁻ form resin, such as a higher concentration required for quantitative exchange, a systematic change in infrared spectra on the degree of exchange, and facile thermal dehydration, giving H₂P₂O₇²⁻. In contrast, multivalent anions were exchanged without dehydration, due to the larger space allowed for in the resins and the stronger interaction with water compared to those of monovalent anions.

The reactions between zirconium(IV)-tetraphenylporphyrin(tpp)-hydroxide complexes ([ZrIV2(OH)4(tpp)2] and [ZrIV(OH)2(tpp)]) in chlorobenzene and various acids (HX: HClO4, HCl, HNO3, CH3COOH) in water were studied. Three species [ZrIV2(OH)3(tpp)2],X, [ZrIV(OH)X(tpp)], and [ZrIVX2(tpp)] were identified, and their stability constants were determined. The extent of formation of each species depends on the coordination ability and lipophilicity of X-. The performance of these complexes was evaluated as a carrier of an anion-selective electrode. The cationic complex [ZrIV2(OH)3(tpp)2],X exhibited selectivity following the Hofmeister series to weakly coordinating anions, while showing a super-Nernstian response to strongly coordinating citrates. The latter suggests the cleavage of the dimeric structure. The dichloro complex [ZrIVCl2(tpp)] was prone to hydrolyze in contact with an aqueous solution and gave drifting potentials. The monochloro complex [ZrIV(OH)Cl(tpp)] was more stable and strongly responded to acetates, which may be ascribed to substitution of a weakly bound chloride. A slow hydrolysis giving [ZrIV(OH)2(tpp)], however, caused gradual deterioration of this strong response to acetates. Conditioning of the membrane in 1 M HCl regenerated the once-deteriorated carrier [ZrIV(OH)Cl(tpp)], while continuous conditioning extended its operating life. This carrier was effectively used to continuously monitor the acetate in a flow system. The dihydroxo complex [ZrIV(OH)2(tpp)] showed lower responses to common anions due to strong Zr-OH bonding and was thus successfully used for selective potentiometry of citrates.

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