The effects of anions (P(V), P(III), P(I), Se(IV), OH(-), F(-), Cl(-), SCN(-), S(IV), and CH(3)COO(-)) on the adsorption of trivalent metal ions (Fe(3+), Al(3+), Ga(3+), In(3+), and Sc(3+)) to three strongly acidic cation-exchange resins (-S)(-) of different types (porous or gel) and different exchange capacities (4.55, 3.91, and 0.96 mmol g(-1)) were studied systematically. All these metal ions showed coadsorption of OH(-), irrespective of the resins. In contrast, coadsorption of P(V), P(III), P(I), and Se(IV) was observed on the resins of the higher exchange capacities but not on the resin of the lowest exchange capacity. Stoichiometric analyses and spectroscopic (Mossbauer and infrared) studies for Fe(3+) demonstrated the presence of the coadsorbed species: [(-S)(2)Fe(OH)] and [(-S)(2)(Fe-O-Fe)(S-)(2)] for OH(-), [(-S)(2)Fe(HPO(4))Fe(S-)(2)] for P(V), and [(-S)(2)FeX](j) (X(-) = H(2)PO(3)(-), H(2)PO(2)(-), HSeO(3)(-); j > 1) for P(III), P(I), and Se(IV). No coadsorption was observed for the other anions. These findings indicate that the bridge bonding of anions between the metal ions adsorbed on the resins of the higher exchange capacities plays a crucial role for the coadsorption. Some analytical implication was also discussed.

Aliphatic polydithiourethanes (PDTUs) were successfully synthesized from diisothiocyanates and dithiols having different values of the carbon atom number. The thermal properties and hydrogen-bonding behavior of PDTUs were studied in detail by using differential scanning calorimetry, thermal gravimetric analysis, temperature dependence nuclear magnetic resonance, Fourier transform infrared-attenuated total reflection, and density functional theory and semiempirical molecular orbital methods. In this work, we demonstrated that the thermal decomposition of PDTUs happened from the cleavage of the C–S bond of the dithiocarbamate moiety in the main chain and also that the active isothiocyanate and thiol groups were reprepared in the terminal of the decomposed polymer (i.e., oligomer). Furthermore, we found that the thermal depolymerization of PDTUs and the repolymerization of dithiourethane oligomers at room temperature proceeded repeatedly a few times.

The spaces (voids) available for cations in the five exchange resins with varying exchange capacities and cross-linking degrees were estimated, on the basis of the additivity of molar volumes of the constituents. Tetraalkylammonium ions (NR(4)(+); R: Me, Et, Pr) may completely exchange potassium ion on the resin having a larger void radius. In contrast, the ratio of saturated adsorption capacity to exchange capacity of the resin having a smaller void radius decreased with an increase in size of NR(4)(+) ions, due to the interionic contacts. Alkali metal ions could be exchanged quantitatively. While the hydration numbers of K(+), Rb(+), and Cs(+) were independent of the void radius, those of Li(+) and Na(+), especially Na(+), decreased with a decrease in void radius. Interionic contacts between the hydrated ions enhance the dehydration. Multivalent metal ions have the hydration numbers, comparable to or rather greater than those in water. A greater void volume available due to exchange stoichiometry released the interionic contacts and occasionally promoted the involvement of water molecules other than directly bound molecules. The close proximity between ions in the conventional ion-exchange resins having higher exchange capacities may induce varying interactions.

Several anions were found to penetrate into a strongly acidic cation-exchange resin by the aid of complexation with Fe3+ ion to give dimeric species, such as [(–S)2Fe(A)Fe(S–)2] (–S: benzenesulfonate bound to polymer network; A2−: HPO42−, HPO32−), and species having a composition of (–S):Fe:A = 2:1:1 (A−: OH−, H2PO2−).