중성운반체를 이용한 K<SUP>+</SUP> 이온선택성 PVC막 전극

김용렬; 조경섭; 강안수

Journal of the Korean Industrial and Engineering Chemistry, Vol.9, No.5, 734-741, October, 1998

Export Citation

중성운반체를 이용한 K⁺ 이온선택성 PVC막 전극

K⁺ Ion-Selective PVC Membrane Electrodes with Neutral Carriers

김용렬, 조경섭, 강안수

초록

본 연구에서는 전극전위 분석법을 사용하여 중성운반체로 dibenzo-18-crown-6(D18Cr6)와 valinomycin(Val)을 이용하여 K⁺이온선택성 PVC막전극의 막과 용액계면에서의 전극특성을 검토하였다. PVC막에서 감응물질(운반체)에 기본전해질의 혼입 (doping)여부, 감응물질의 종류와 함량, 가소제, 막두께 및 이온의 활동도변화에 따른 전극의 기울기, 선형응답범위 한계측정농도 및 방해이온에 따른 선택계수 등 전극특성을 검토하였다. 중성운반체로 D18Cr6, Val을 K⁺이온으로 착체형성하여 사용하였고, 가소제로 dibutylphthalate(DBP), dioctyl sebacate(DOS) 및 dibutyl sebacate(DBS)를, 혼입제인 기본전해질로 potassium tetraphenylborate (KTPB) 및 용매로 THF를 지지체로 PVC를 이용하여 막을 제조하였다. 운반체의 최적 함량은 D18Cr6와 Val의 경우 3.23 wt%이었고, 가소제는 DBP가 가장 적절한 가소제이었다. 막두께에 대한 영향은 최적 막두께 이상에서는 막두께가 얇아질수록 전극특성이 좋아졌으나, 막두께가 이 이하로 얇아지면 운반체의 용출, 막의 강도 등이 작용하여 전극특성이 나빠짐을 알 수 있었다. D18Cr6의 경우 K⁺이온에 대한 혼합용액법에 의한 선택계수 서열은 다음과 같았다. : NH₄⁺>Ca²⁺>Mg²⁺>Na⁺.

Electrode characteristics were studied in the interface between sample solutions and K⁺ ion selective PVC membrane electrodes containing neutral carriers, dibenzo-18-crown-6(D18Cr6) and valinomycin(Val). The effect of doping of base electrolytes, the chemical structure and the content of carrier, variation of plasticizer, membrane thickness, and concentration variation of sample solution on the response characteristics of electrode such as the measured Nernstian slope, the detection limit, the linear response range, and potentiometric selectivity coefficients, were studied. In order to synthesize the membrane D18Cr6 and Val as neutral carriers were used, and complex between the carrier and K⁺ ions were used as active materials. PVC membrane electrodes were made of plasticizers (DBP, DOS, and DBS), the base electrolyte[potassium tetraphenylborate(KTPB)], and solvent(THF). The chemical structure of carrier D18Cr6 was best for electrode and ideal electrode characteristics were appeared especially in case of doping of TPB. The optimum carrier content was about 3.23 wt% in case of D18Cr6 and Val. DBP was best as a plasticizer. As membrane thickness decreased the electrode characteristics was improved. But its characteristics were lowered below the optimum membrane thickness because of the elution of carrier, deterioration of membrane strength, etc. In the case of D18Cr6, the selectivity coefficients by the mixed solution method for the K⁺ ion were in the order of NH₄⁺>Ca²⁺>Mg²⁺>Na⁺.

Keywords:K⁺-ion Selective PVC Electrode;Dibenzo-18-crown-6;Valinomycin;AC Impedance Spectrum;Ion-exchange Current Density;Warburg Impedance

[References]

Morf WE, "The Principles of Ion Selective Electrodes and of Membrane Transport," Elsevier Sci., New York (1981)
Cattrall RW, Chin-Poh P, Anal. Chem., 47, 93 (1975)
Baker AS, Smith R, J. Agr. Food Chem., 17, 1284 (1969)
Hassan SKAG, Moody GJ, Thomas JDR, Analyst, 105, 147 (1980)
Shinbo T, Kamo N, Kurihara K, Kobatake Y, Arch. Biochem. Biophys., 187, 414 (1978)
Beg MA, Nabi A, J. Membr. Sci., 9, 197 (1981)
Buck RP, Ion-Sel. Elec. Rev., 4, 3 (1982)
Mikhelson KN, Sens. Actuator, 18-19, 31 (1994)
Moody GJ, Oke RB, Thomas JDR, Analyst, 95, 910 (1970)
Griffiths GH, Moody GJ, Thomas JDR, Analyst, 97, 420 (1972)
Barton AFM, "CRC Handbook of Solubility Parameters and Other Cohesion Parameter," CRC Press. Inc. (1985)
Armstrong RD, Nikitas P, Electrochim. Acta, 30, 1627 (1985)
Rechnitz CA, Eyal E, Anal. Chem., 44, 370 (1972)
Morf WE, Simons W, Helv. Chim. Acta, 69, 1120 (1986)
Pure Appl. Chem., International Union of Pure and Applied Chemistry, Analytical Chem. Div., "Recommen-Dations for Nomenclature of ion-Selective Electrodes,", 48, 127 (1976)
Massachusetts Institute of Tech., "Laboratory Techniques Manual," Vol. 1, 31-11, Dept. of Chem. M.I.T. Press (1979)
영인과학, "Orion 이온선택성 전극," 제품 catalogue (1995)
Buck RP, Ion-Sel. Elec. Rev., 4, 3 (1982)
Koryta J, Electrochim. Acta, 29, 445 (1984)
안형환, 김용렬, 강현춘, 강안수, 멤브레인, 3, 126 (1993)
Liu L, Masuda Y, Sekido E, Analyst, 115, 1089 (1990)
Hulanicki A, Maj-Zurawka M, Anal. Chim. Acta, 98, 151 (1978)
Birch BJ, Cockcroft RN, Ion-Sel. Elec. Rev., 3, 1 (1981)
김용렬, 박사학위논문, 명지대학교 (1997)
Xie SL, Cammann K, J. Electroanal. Chem., 229, 249 (1987)
Lee D, Thomas JDR, Talanta, 41, 901 (1994)
Umezawa Y, "CRC Handbook of Ion-Selective Electrode: Selectivity Coefficients," CRC Press, Boca Raton (1990)

[1] Morf WE, "The Principles of Ion Selective Electrodes and of Membrane Transport," Elsevier Sci., New York (1981)

[2] Cattrall RW, Chin-Poh P, Anal. Chem., 47, 93 (1975)

[3] Baker AS, Smith R, J. Agr. Food Chem., 17, 1284 (1969)

[4] Hassan SKAG, Moody GJ, Thomas JDR, Analyst, 105, 147 (1980)

[5] Shinbo T, Kamo N, Kurihara K, Kobatake Y, Arch. Biochem. Biophys., 187, 414 (1978)

[6] Beg MA, Nabi A, J. Membr. Sci., 9, 197 (1981)

[7] Buck RP, Ion-Sel. Elec. Rev., 4, 3 (1982)

[8] Mikhelson KN, Sens. Actuator, 18-19, 31 (1994)

[9] Moody GJ, Oke RB, Thomas JDR, Analyst, 95, 910 (1970)

[10] Griffiths GH, Moody GJ, Thomas JDR, Analyst, 97, 420 (1972)

[11] Barton AFM, "CRC Handbook of Solubility Parameters and Other Cohesion Parameter," CRC Press. Inc. (1985)

[12] Armstrong RD, Nikitas P, Electrochim. Acta, 30, 1627 (1985)

[13] Rechnitz CA, Eyal E, Anal. Chem., 44, 370 (1972)

[14] Morf WE, Simons W, Helv. Chim. Acta, 69, 1120 (1986)

[15] Pure Appl. Chem., International Union of Pure and Applied Chemistry, Analytical Chem. Div., "Recommen-Dations for Nomenclature of ion-Selective Electrodes,", 48, 127 (1976)

[16] Massachusetts Institute of Tech., "Laboratory Techniques Manual," Vol. 1, 31-11, Dept. of Chem. M.I.T. Press (1979)

[17] 영인과학, "Orion 이온선택성 전극," 제품 catalogue (1995)

[18] Buck RP, Ion-Sel. Elec. Rev., 4, 3 (1982)

[19] Koryta J, Electrochim. Acta, 29, 445 (1984)

[20] 안형환, 김용렬, 강현춘, 강안수, 멤브레인, 3, 126 (1993)

[21] Liu L, Masuda Y, Sekido E, Analyst, 115, 1089 (1990)

[22] Hulanicki A, Maj-Zurawka M, Anal. Chim. Acta, 98, 151 (1978)

[23] Birch BJ, Cockcroft RN, Ion-Sel. Elec. Rev., 3, 1 (1981)

[24] 김용렬, 박사학위논문, 명지대학교 (1997)

[25] Xie SL, Cammann K, J. Electroanal. Chem., 229, 249 (1987)

[26] Lee D, Thomas JDR, Talanta, 41, 901 (1994)

[27] Umezawa Y, "CRC Handbook of Ion-Selective Electrode: Selectivity Coefficients," CRC Press, Boca Raton (1990)