전위차 적정법을 이용한 인산형 양이온교환수지의 특성 계산

김태일; 손원근

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.6, 871-875, October, 1999

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전위차 적정법을 이용한 인산형 양이온교환수지의 특성 계산

The Characteristic Calculation of a Phosphoric Acid Ion Exchanger using the Potentiometric Titration

김태일, 손원근

초록

인산형 양이온교환수지 특성 계산과, 이온교환수지의 전위차 적정곡선의 형태에 따른 정확한 이온교환용량을 결정할 수 있는 방법을 알아보았다. 이온교환수지는 divinylbenzene 4%로 가교화된 polystyrene 공중합체를 인산화한 것으로 이온교환용량이 5.7 meq/g이다. 인산형 양이온교환수지는 직선의 식으로 설멸할 수 있었고, 직선 기울기로부터 적정시 zero중화와 완전중화사이의 평형상수 음의 대수(pK) 값의 차인 DpK의 값을 구할 수 있었으며, c=0.5에서 얻어진 실험 및 이론의 pK값이 잘 일치하는 것을 알 수 있었다. 이온교환수지의 전위차 적정곡선은 NaOH나 Ba(OH)₂로 적정할 때 c의 변화에 따른 pK의 실험 값과 계산 값이 잘 일치하는 것을 알 수 있었다. 전위차 적정곡선의 변곡점은 원자가가 1가인 이온보다는 2가 이온이 크게 변화되는 것을 알 수 있었으며, g 값과 도함수 ∂pH/∂g의 관계를 Lorentz함수로서 나타내어 더욱 정확한 이온교환용량을 결정할 수 있었다.

We calculated the characteristics of a phosphoric cation exchanger and studied on an accurately computable method to determine the ion exchange capacity for type of potentiometric titration curve. The ion exchanger was prepared by phosphorylation of a styrene-divinylbenzene copolymer with 4% crosslinking. The ion exchange capacity is 5.7 meq/g. The experimental pK values versus χ in phosphoric cation exchanger can be expressed as a linear equation. The ΔpK values were obtained from the slope of linear equation. The ΔpK values are the differences of antilogarithms(pK) values of the apparent equilibrium constant at complete and zeroth neutralization of the ion exchanger. Also the experimental pK values at χ=0.5 were accorded well with theoretical data. And when it is titrated with NaOH and Ba(OH)₂ solutions, a good agreement between experimental and theoretical pK values for various χ was seen in all the potentiometric titration curves. We knew that the inflection point of potentiometric titration curve in the case of divalent ions are changed much large that that for monovalent ions. If the relation between gvalues and pH/g was plotted to the Lorentz distribution curve, ion exchange capacity can be accurately evaluated.

Keywords:ion exchanger;phosphoric ion exchanger;potentiometric titration;equilibrium constant

[References]

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Goupil JM, Hemidy JF, Cornet D, Zeolites, 2, 47 (1982)
Toshima N, Asanuma H, Yamaguchi K, Hirai H, Bull. Chem. Soc. Jpn., 62, 563 (1986)
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Soldatov VS, Dokl. Akad. Nauk. USSR, 314(N3), 664 (1990)
Soldatov VS, React. Polym., 19, 105 (1993)
Soldatov VS, Ind. Eng. Chem. Res., 34(8), 2605 (1995)

[1] Kaneko K, Ozeki S, Inouye K, Nippon Kagaku Kaishi, 1351 (1985)

[2] Goupil JM, Hemidy JF, Cornet D, Zeolites, 2, 47 (1982)

[3] Toshima N, Asanuma H, Yamaguchi K, Hirai H, Bull. Chem. Soc. Jpn., 62, 563 (1986)

[4] Tuenter G, van Leeuwen WF, Leo JM, Ind. Eng. Chem. Prod. Res. Dev., 25, 633 (1986)

[5] Yoshkado S, Solid State Ion., 9-10, 1305 (1983)

[6] Yoshkado S, Solid State Ion., 40-41, 142 (1992)

[7] Gustafson L, Fillius HF, Kunin R, Ind. Eng. Chem. Fundam., 9, 221 (1970)

[8] Kunin R, Fisher S, J. Phys. Chem., 66, 2275 (1962)

[9] Soldatov VS, J. Phys. Chem. USSR, 1(42), 2287 (1968)

[10] Soldatov VS, Nauka Tech. Minsk, 162 (1972)

[11] Kim TI, Hwang TS, Son WK, Choi DM, Oh IS, Soldatov BC, Polym.(Korea), 23(5), 747 (1999)

[12] Soldatov VS, Dokl. Akad. Nauk. USSR, 314(N3), 664 (1990)

[13] Soldatov VS, React. Polym., 19, 105 (1993)

[14] Soldatov VS, Ind. Eng. Chem. Res., 34(8), 2605 (1995)