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期刊论文

A Study of Depletion Layer Effects on Equivalent Circuit Parameters Using an Electrochemical Quartz Crystal Impedance System

谢青季Qingji Xie* Jin Wang Anhong Zhou Youyu Zhang Hongwei Liu Zhinian Xu Yu Yuan Maoying Deng and Shouzhuo Yao

Anal. Chem. 1999, 71, 4649-4656,-0001,():

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摘要/描述

An electrochemical quartz crystal impedance system (EQCIS) was used to investigate depletion layer effects on equivalent circuit parameters of piezoelectric quartz crystal resonance in electrochemical processes of CoSO4 aqueous solutions containing 0.4mol/L ethylenediamine +0.5mol/L Na2SO4, 0.2mol/L 1,10-phenanthroline +0.5mol/L Na2SO4 and K3Fe(CN)6, or K4Fe(CN)6 aqueous solutions containing 1.0mol/L KCl in potential cycling experiments, respectively. The impedance data were analyzed according to Martin's model. For the former two systems, motional resistance R1, series resonant frequency fs, and motional inductance L1 changed reversibly with potential, and the observed values of △R1, △L1, and△fs roughly satisfied equations reflecting liquid loadingeffects, suggesting that changes in these parameters mightbe mainly governed by local variations in solution densityand viscosity near the electrode surface. For the latter two systems, reversible changes in R1 with potential coincided well with the simulated results from variations in solution density and viscosity near the electrode surface; however, besides reversible changes of △L1 and △fs with potential, rising drifts of fs and decreasing drifts of L1 were found at oxidation potentials. The drifts of fs and L1 observed are believed to result from mass changes of the gold electrode, and cyanide and chloride corrosion of the gold electrode at oxidation potentials may play an important role for the drifting phenomena. It is concluded that quantitative analyses of △R1, △L1, and △fs obtained from the EQCIS provide the possibility for differentiating the net depletion layer effect with the change in electrode mass, and the ¢R1 response may be well used for evaluating local changes in liquid loading inside the depletion layer compared with responses of △fs and △L1.

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