The separation and concentration of various ions have received considerable interest in various fields. The separation process using an ion-exchange resin is simple and advantageous for the concentration of trace ions in dilute solutions. Generally, multivalent ions are prior exchanged onto the ion-exchange resin to monovalent ions. Thus, the selective separation of monovalent ions in the presence of multivalent ions is difficult. To improve the ion-exchange selectivity, various modification processes were examined.Most of these improved a modification of chelate compounds on the anion-exchange resin for the selective collection of the metal cation, 1-3 and of hydrophilic compounds on the ion exchange resin for selective collection of hydrophilic ions. 4,5 In a previous paper, 6 the selective collection of monovalent ion on an anion-exchange resin modified with Demol N (the polycondensation product of naphthalene sulfate and formaldehyde, made by Kao Chemicals Co., Ltd., Tokyo, Japan), anionic polyelectrolyte, was reported.The ionexchange rate of multivalent anion becomes slower than that of monovalent anions. In this work, the influences of the modified condition and structure of polyelectrolyte on the ion-exchange reaction were examined. The modification layer may be controlled by using polystyrenesulfonic acid, due to the more linear polyelectrolyte structure and variation in the polymerization degree. Furthermore, the modified resin was applied to separate the nitrate ion from the sulfate ion in aqueous solution.
Experimental
ApparatusA sample solution was analyzed by ion chromatography composed of a pump (L-6000, Hitachi, Tokyo, Japan), a conductivity detector (L-3720, Hitachi) and a column oven with sample injector (L-5020, Hitachi). The separation column was a Showdex IC I-524A (φ4.6 × 100 mm, Showa Denko K. K., Tokyo, Japan). The analytical signals were recorded and processed with a chromato integrator (D-2500, Hitachi).
ReagentsA gel-type anion exchange resin (Amberlite IRA-400, Organo Co., Ltd., Tokyo, Japan) in a chloride form (0.40 -0.53 mm) was used. Polystyrenesulfonic acid, ps-50 and ps-100 (TOSOH Corp., Tokyo, Japan) were used to form a modification layer on the surface of the anion-exchange resin. The polymerization degrees of polystyrenesulfonic acid polymer were 50 and 100, respectively. All other reagents used were of analytical grade.
Modification of anion-exchange resinThe anion-exchange resin was pretreated with a sufficient sodium hydroxide solution (2 mol l -1 ). The pretreated resin was thoroughly washed with water. Ten milliliters of the anionexchange resin in a hydroxide form were introduced into a 200 ml round-bottomed flask, and 100 ml of 20 wt% polystyrenesulfonic acid solution was added. The mixture was stirred for 8 h at 90˚C in a water bath. Then modified resin was filtered and washed sufficiently with water. The modified resin was kept wet.
Ion exchange procedureTwo milliliters of modified resin were introduced into a 300 ml flask, and several washings were made with water. Aft...