Journal of the Korean Electrochemical Society (전기화학회지)

The Korean Electrochemical Society (한국전기화학회)
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A Study on the Computational Simulation of Cyclic Voltammetry using Semi-infinite Diffusion Model

반무한 확산모델을 이용한 순환전위법의 전산모사에 관한 연구

  • Cho, Ha-Na (Department of Chemical Engineering, Kwangwoon University) ;
  • Kim, Tae-Yong (Department of Chemical Engineering, Kwangwoon University) ;
  • Yoon, Do-Young (Department of Chemical Engineering, Kwangwoon University)
  • Received : 2011.07.29
  • Accepted : 2011.08.04
  • Published : 2011.08.31
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Abstract

The transport phenomena of electron and ion around the electrode have been analyzed, herein the computational program to simulate the electrochemical signal of cyclic voltammetry has been implemented. For the dominant mass-transfer system, the governing equation and its boundary conditions are confined to the semi-infinite diffusion model and the reversible reaction at the electrode. In order to obtain the numerical solutions of cyclic voltammetry, MATLAB was used for the explicit finite difference method. Experimental results from the cyclic voltammetry of electrochemical system(10 mM $K_3Fe(CN)_6$ and 0.1M KCl) upon the ITO glass substrate were compared with the numerical solutions. Present program explains the experimental results fairly well, where they approached the simulated ones closely with deceasing the scan rate. Furthermore, the effects of electrode area, electrochemical reaction constants and transfering coefficients in the cyclic voltammetry were discussed quantitatively.

본 연구에서는 순환전위법으로 발생되는 전기화학적 신호를 모사하기 위한 전산프로그램을 구현하여, 전극주변에서 발생하는 전자 및 이온의 전달현상을 해석하였다. 물질확산이 지배적인 계에 대하여 반무한 확산모델과 전극반응만을 고려하여 지배방정식과 경계조건을 설정하였다. 순환전위법의 수치해를 구하기 위하여 양함수 유한차분법을 적용하였으며, MATLAB을 이용하여 프로그램을 작성하였다. 10 mM의 $K_3Fe(CN)_6$와 0.1 M KCl 전기화학계를 이용하여 ITO glass 전극에서 순환전위법을 실시하여 실험의 결과와 수치해를 비교하였다. 본 연구에서 구현된 프로그램은 실험 결과를 전반적으로 잘 예측하고 있으며, 특히 주사속도가 낮을수록 실험결과들이 수치해에 보다 근접하고 있었다. 주사속도에 부가하여 순환전위법에서 전극면적, 전극반응속도상수 그리고 전자이동수의 영향들을 정량적으로 고려할 수 있었다.

Keywords

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