Impedance Parameters of Electrical Double Layer I. A Determination Method of Electrolytic Cell Impedance Parameter on the Platinum Electrode

전기이중층의 임피던스 파라미터 I. 백금전극을 사용한 전해쎌 임피던스 파라미터의 결정방법

  • Kum-Sho Hwang (Department of Applied Chemistry, National Fisheries University of Pusan) ;
  • Un-Sik Kim (Department of Chemistry, College of Natural Sciences, Pusan National University)
  • 황김소 (부산수산대학 응용화학과) ;
  • 김은식 (부산대학교 자연과학대학 화학과)
  • Published : 1986.06.20

Abstract

This study is focused on the correct measurement of the equations for the determination of the impedance parameters-the differential capacity of the double layer $C_d$, solution resistance $R_Q$, transfer resitance $R_i$, and adsorption pseudcapacity $C_{\phi}$/ The application of only an imaginary part of complex function of ${\omega}$ at the sinusoidal steady state indicates the following equations of total impedance: at low frequency $|Z_{LF}|=1/{\omega}_1\;C_{\phi}\;{\sqrt{1+{{\omega}_1}^2/{\omega}^2}$, at high frequency $|Z_{HF}|={\omega}_2/({\omega}_1{\omega}_3C{\phi})({\omega}^2+{{\omega}_2}^2)\;{\sqrt{{({\omega}^2+{\omega}_2{\omega}_3)}^2+{({\omega}_2{\omega}-{\omega_3{\omega})^2}}$. The values of the total impedance of cell, phase angle, and cell current that are necessary for the calculations of impedance parameters were experimentally measured from 200 to 6000Hz for the following supporting electrolytes, 0.5M $Na_2SO_4$, 1M NaCl, 19.373% sea water, 1M HCl, 1M $KNO_3$ and for $10^{-2}M$ KI and 60mM DBNA (Di-iso-Butylnitrosoamine) in these supporting electrolytes. The derived equations in this study shows that the values of impedance parameters of $C_d,\;C_{\phi},\;R_i\;and\;R_Q\;are\;15{\sim}40\;{\mu}F/cm^2,\;162{\sim}758\;{\mu}F/cm^2\;11.5{\sim}57.6\;ohm{\cdot}cm^2\;and\;0.5{\times}10^{-2}{\sim}4.1{\times}10^{-2}\;ohm{\cdot}cm^2$ respectively.

본 연구는 임피던스 파라미터(전기이중층 내의 미분용량 $C_d$, 용핵저향 $R_Q$, 전하이동저항 $R_t$,및 흡착유사용량 $C{\phi}$)를 결정하기 위해 정확한 측정식을 얻는데 주력하낟. 정현파가 정상상태에 있을 때 복소수함수 ${\omega}$중의 허수부분만을 으용하여 구한 전체임피던스식은 낮은 주파수에서 $|Z_{LF}|=1/{\omega}_{1C\phi}{\sqrt{1+{{\omega}_1}^2/{\omega}^2}$에, 높은 주파수에서는 $|Z_{HF}|={\omega}_2/({\omega}_1{\omega}_3C{\phi})({\omega}^2+{{\omega}_2}^2){\sqrt{{({\omega}^2+{\omega}_2{\omega}_3)}^2+{({\omega}_2{\omega}-{\omega_3{\omega})^2}}$에 따름을 나타낸다. 이들 임피던스 파라미터의 계산에 필요한 전체임피던수, 위상각 및 쎌전류값을 .5M $NA_2SO_4$ 또는 1M NaCl, 19.373% 해수, 1M HCl, 1M $KNO_3$ 지지전해질과 이들의 지지전해질내에 각각 $10^{-2}M Kl$ 또는 6mM DBNA를 첨가하여 20~60Hz 범위에서 실험적으로 측정하였다. 본 연구에서 유도한 식은 임피던스 파라미터 $C_d,\;C_{\phi},\;R_t$$R_Q$의 값들이 각각 $15{\sim}4{\mu}F/cm^2,\;162{\sim}758{\mu}F/cm^2,\;11.5{\sim}57.6ohm{\cdot}cm^2$$0.5{\times}10^{-2}{\sim}4.1{\sim}10^{-2}\;ohm{\cdot}cm^2$임을 보여준다.

Keywords

References

  1. J. Chem. Phys. v.73 G.M. Torrie;J.P. Valleau
  2. J. Chem. Phys. v.76 G. M. Torrie;J.P. Valleau;G.N. Patey
  3. J. Phy. Chem. v.81 L. Blunn
  4. J. Chem. Phys. v.77 F. Vericat;L. Blum;D. Henderson
  5. J. Chem. Phys. v.78 L.B. Bhuiyan;L. Blum;D. Henderson
  6. J. Phy. Chem. v.86 G.M. Torrie;J.P. Valleau
  7. Electrochim. Acta v.29 I.L. Cooper;J.A. Harrison
  8. Modern Electrochemistry v.2 J. O'M. Bockris;A.K.N. Reddy
  9. Electrochim. Acta v.29 J.A. Harrison
  10. Z. Elecktrochem. v.61 J. Matsuda
  11. Anal. Chem. v.38 J.D. Delmastro;D.E. Smith
  12. Anal. Chem. v.52 D. Britz
  13. Electrochim. Acta v.26 G.P. Power;I. Caldwell
  14. The Chemistry of Electrode Processes I. Fried
  15. Fundamentals and Applications Electrochemical Method, A.J. Bard;L.R. Faulkner
  16. K.S. Hwang;U.S. Kim
  17. Theoretical Aspects Electrochemical Kinetics K.J. Vetter
  18. Electrochemical Systems J.S. Newman
  19. Electroanalytical Chemistry v.4 A.J. Bard
  20. Laplace Transformation W.T. Thomson
  21. Electroanalytical Chemistry v.8 A.J. Bard
  22. Automatic Control System C.K. Benjamin
  23. Electronchemistry, Calculation, Simulation, and Instrumentation J.S. Mattson;H.B. Mark;H.C. Macdonald
  24. An Experimental Approach Interfacial Electochemistry, E. Gileadi;E. Kirowa-Eisner;J. Penciner
  25. J. Electrochem. Soc. v.122 R.W. Powers;S.P. Mitoff
  26. Anal. Chem. v.39 J.K. Frischmann;A. Timnick
  27. Electrochemistry v.1 J. Th. G. Overbeek
  28. Electroanalytical Chemistry v.12 A.J. Bard
  29. Electrochim. Acta v.18 H.P. Dhar;B.E. Conway;K.M. Joshi
  30. J. Electroanal. Chem. v.130 M.V.S. Narayanan;S.K. Rangarajan
  31. J. Electroanal. Chem. v.137 H.R.D. Schuhmann;E. Tronel-Peyroz;P. Vanel
  32. J. Electroanal. Chem. v.136 B. Damaskin;S. Karpov;S. Dyatkina
  33. J. Electroanal. Chem. v.138 M.D. Levi;A.V. Shlepaknov;B.B. Damaskin;I.A. Bagotskaya
  34. J. Chem. Phys. v.73 S.L. Carnie;D.Y.C. Chan
  35. J. Chem. Phys. v.76 J.P. Valleau;G.M. Torrie