Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Effect of High Pressure on Polarographic Parameters of Metal Complex Ion

金屬錯이온의 폴라로그래피的 파라미터에 미치는 壓力의 影響

  • Heung Lark Lee (Department of Chemistry, College of Natural Sciences, Kyungpook National University) ;
  • Zun Ung Bae (Department of Chemistry, College of Natural Sciences, Kyungpook National University) ;
  • Jong Hoon Yun (Department of Chemistry, College of Natural Sciences, Kyungpook National University)
  • 이흥락 (慶北大學校 自然科學大學 化學科) ;
  • 배준웅 (慶北大學校 自然科學大學 化學科) ;
  • 윤종훈 (慶北大學校 自然科學大學 化學科)
  • Published : 1987.10.20
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Abstract

The dependence of polarographic parameters on the pressure for the reduction of copper(II), cadmium(II), and zinc(II) complex ions with ethylenediamine, propylenediamine, and diethylenetriamine has been studied. In this study the dropping mercury electrode, the mercury pool electrode, and helix type of platinum wire were used as the working, the reference, and the auxilary electrode, respectively. With increasing the pressure from 1 atmosphere to 1,500 atmospheres, the reduction half-wave potentials of metal complex ions are shifted to the negative values and the diffusion currents become considerably larger, in keeping with the theory on the change of the physical properties of the electrolytic solution such as the density, the viscosity, the dielectric constant, and the electrical conductance, etc. The slope values of the logarithmic plot are increased with increasing the pressure, which indicates the more irreversible reduction. The temperature coefficients of diffusion current observed over the range of the temperature from 25$^{\circ}$C to 35$^{\circ}$C are about two percentage with increasing the pressure, therefore the polarographic reduction under the high pressure is controlled by diffusion. The linear relationships between diffusion current and concentration of metal complex ions are established over all pressure range.

에틸렌디아민, 프로필렌디아민 및 디에틸렌트리아민의 구리(II), 카드뮴(II) 및 아연(II)착이온의 桓元에 대하여 압력에 따른 폴라로그래피적 파라미터의 依存性을 조사하였다. 水銀滴下電極, 고인수은전극 및 나선형 백금선을 각각 作業電極, 基準電極 및 補助電極으로 사용하였다. 압력이 1기압에서 1,500기압으로 증가함에 따라 금속착이온의 還元半波電位는 陰電位 쪽으로 이동하였으며, 擴散電流는 상당히 커졌다. 이러한 현상은 전해질용액의 물리적 성질 곧 密度, 粘性度, 誘電常數, 電氣傳導度 등이 압력이 증가함에 따라 커지기 때문이다. 압력을 증가시키면 log plot의 기울기 값이 커지므로 환원반응의 可逆性은 나빠지고 있다. 25$^{\circ}$C ~ 35$^{\circ}$C의 온도범위에서 측정한 확산전류의 溫度係數가 압력을 증가시켜도 2%정도이므로 高壓下에서 폴라로그래피적 환원반응은 擴散支配的이다. 또 실험압력 범위내에서 금속착이온의 확산전류와 농도 사이에는 線形關係가 성립하였다.

Keywords

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