Abstract
Perchlorate ion-selective PVC membrane electrode responsive to $10^{-6}M$ was developed by incorporating the ion-pair complex of perchlorate with the quaternary ammonium salts as a active material. The effect of chemical structure, the content of active material, the kinds of plasticizers, and the membrane thickness on the electrode characteristics such as the linear response range and Nernstian slope of the electrode were studied. With the results, the useful pH range and the selectivity coefficients to various interfering anions were compared and investigated. It was obtained that the effect of the chemical structure of an active material on the electrode characteristics was improved with increasing the alkyl chain length of the quarternary ammonium salts in the ascending order of Aliquat 336P, TOAP, TDAP, and TDDAP. The electrode characteristics was improved with the decrease of the active material content below the optimum membrane composition, and DBP was the best as a plasticizer. The optimum membrane composition was 9.09wt% of TDDAP, 30.3wt% of PVC, and 60.6wt% of ptasticizer(DBP). And the optimum membrane thickness was0.45mm at this composition. Under the above condition, thelinear response ranger was $10^{-1}~1.2 {\times} 10^{-6}M$, and the detection limit was $5.1{\times}10^{-7}M$ with the Nernstian slope of 57mV/decade of activity of perchlorate ion. The electrode potential was stable within the pH range from 4 to 11. The selectivity coefficient was as shown below : $SCN^->I^->NO_3^->Br^->ClO_3^->F^->Cl^->SO_4^{2-}$
감응물질로 제4급 암모늄염을 사용하여 PVC를 지지체로 과염소산이온의 농도 $10^{-6}M$까지 측정가능한 이온 선택성 전극을 제작하였다. 감응물질의 화학적 구조와 함량, 가소제의 종류 및 막 두께에 따른 선형응답 범위와 Nernst의 기울기 등 전극특성을 검토하여, 최적 막조건을 구한 다음 측정가능 pH범위와 여러 방해이온에 대한 선택계수를 비교 검토하였다. 과염소산 이온선택성 전극에서 감응물질의 화학적 구조 즉, 알킬기의 탄소고리수가 증가할수록 선형응답 범위 등 전극 특성은 Aliquat 336P, TOAP, TDAP 및 TDDAP의 순서로 좋아졌다. 가소제는 DBP가 가장 좋았고, 감응물질의 양은 최적 함량 이상에서 적을수록 좋았다. 최적 막 조성은 TDDAP 9.09, PVC 30.3 및 DBP 60.61wt%이었고, 막두께 0.45mm이었다. 이 조건에서 선형응답 범위 $10^{-1}~1.2 {\times} 10^{-6}M$, 검출한계 $5.1{\times}10^{-7}M$ 및 Nernst기울기 $57mV/pClO_4$이었다. 막전위는 pH 4~11 범위에서 pH의 영향을 받지 않았으며, 선택계수 서열은 다음과 같았다. $SCN^->I^->NO_3^->Br^->ClO_3^->F^->Cl^->SO_4^{2-}$