Electrochemical impedance spectroscopy (EIS) is a powerful tool to investigate properties of materials and electrode reactions. This Primer provides a guide to the use of EIS with a comparison to other electrochemical techniques. The analysis of impedance data for reduction of ferricyanide in a KCl supporting electrolyte is used to demonstrate the error structure for impedance measurements, the use of measurement and process models, as well as the sensitivity of impedance to the evolution of electrode properties. This Primer provides guidelines for experimental design, discusses the relevance of accuracy contour plots to wiring and instrumentation selection, and emphasizes the importance of the Kramers-Kronig relations to data validation and analysis. Applications of EIS to battery performance, metal and alloy corrosion, and electrochemical biosensors are highlighted. Electrochemical impedance measurements depend on both the mechanism under investigation and extrinsic parameters, such as the electrode geometry. Experimental complications are discussed, including the influence of nonstationary behaviour at low frequencies and the need for reference electrodes. Finally, emerging trends in experimental and interpretation approaches are also described.

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Electrochemical Impedance Spectroscopy

The transformation of the sulfonamide antimicrobial sulfamethazine (SMZ) by a synthetic analogue of the birnessite-family mineral vernadite (δ-MnO2) was studied. The observed pseudo-first-order reaction constants (kobs) decreased as the pH increased from 4.0 to 5.6, consistent with the decline in δ-MnO2 reduction potential with increasing pH. Molecular oxygen accelerated SMZ transformation by δ-MnO2 and influenced the transformation product distribution. Increases in the Na+ concentration produced declines in kobs. Transformation products identified by tandem mass spectrometry and the use of 13C-labeled SMZ included an azo dimer self-coupling product and SO2 extrusion products. Product analysis and density functional theory calculations are consistent with surface precursor complex formation followed by single-electron transfer from SMZ to δ-MnO2 to produce SMZ radical species. Sulfamethazine radicals undergo further transformation by at least two pathways: radical–radical self-coupling or a Smiles-type r...

Transformation of sulfamethazine by manganese oxide in aqueous solution.

Anal. Abatr., 20, 4295 (1970). (537) Walker, R. I., Shipman, W. H., J . Chromatogr., 50, 157 (1970). (538) Wall, R. A., Anal. Biochem., 35, 203 (1970). (539) Wall, R. A,, J. Chromatogr., 60, 195 (1971). (540) Walter, C. W., Korkisch, J., Mikrcchim. Acta, 1971, 81, 137, 158, 181, 194. (541) Watanabe, H., Bunseki Kagaku, 19, 1658 (1970). (542) Webster, P. V., Wilson, J. N., Franks, M. C., J. Znst. Petrol., 56, 50 (1970). (543) Wenzel, E., Oppolzer, R., Schuster, D., Mikrochim. Acta, 1971, 680. (544) Wernet, J., Wahl, K., Fresenius’ Z. Anal. Chem., 251, 373.(1970). (545) Wetterquist, H., Whte, T., Scand. J. Clin. Lab. Invest., 25, 325 (1970); Anal. Abstr., 20, 4146 (1970). (546) White, S. H., Loken, M. R., Shields, C. E., Clin. Chem., 16, 861 (1970). (547) Widtmann, V., Hutn. Listy, 25, 733 (1970); Anal. Abstr., 21, 2601 (1971). (548) Winkler, R., Sansoni, B., Starke, K., Radiochim. Acta, 15, 65 (1971). (549) Wolf, W. J., Thomas, B. W., J . Chromatogr., 56, 281 (1971). (549a) Wolford, J. C., Dean, J. A., Goldstein, G., ibid., 62, 148 (1971). (550) Wong, K. M., Anal. Chim. Ada, 56, 355 (1971). , (551) Woodroofe, G. L., Munro, J. D., Analyst, 95, 153 (1970). (552) Wu, C. M., McCready, R. M., J. Chromatogr., 57, 424 (1971). (553) Yaguchi, M., Perry, M. B., Can. J. Biochem., 48, 386 (1970). (554) Yasuda, K., J. Chromatogr., 60, 144 (1971). (555) Ying-Mao Chen, Fu-Pa0 TSBO, J. Chinese Chem. SOC., (Taipa), 17, 81 (1970). (556) Yoshikawa, Y., Yamasaki, K., Kagaku No Ryoiki, 25, 164 (1971); C.A., 74, 130778~ (1971). (557) Yoshio, M., Waki, H., Ishibashi, N., J. Znorg. Nucl. Chem., 32, 1365 (1970). (558) Zagorodnyeya, A. N., Lebeder, U. D., Ponomarev, V. D., C.A., 74, 1307% (1971). Tr. Znst. Met. Obogashch., Akad. hauk. Kaz. SSR, 1970, 97. (559) Zaharescu, T., Rev. Roum. Chim., 16, 775 (1971). (560) Ziegler, M., Ziegeler, L., Winkler, H., Mikrochim. Acta, 1970, 1312. Zhitenev, V. A., Zh. Prikl. Khim., 42, 1699 (1969). (561) Zhukov, A. I., Kazantsev, E. I., Zhitenev, V. A., Zh. Prikl. Khim., 42, 1699 (1969). (562) Zima, S., Giacintov, P., J. Rad& anal. Chem., 7, 19 (1971). (563) Zlatkis, A., Buening, W., Bayer, E., ANAL. CHEM., 42, 1201 (1970). (564) Zsinka, L., Szirtes, L., Radiochem.

Ion selective electrodes, potentiometry, and potentiometric titrations.

Electrochemical reduction and oxidation of the antibiotic cefepime at a carbon electrode

Utilisation en synthese du cation iminium genere in situ par oxydation electrochimique d'amines tertiaires

Electrochemical oxidation of substituted thiazoles: 2-amino-4-ethoxycarbonyl-5- methylthiazole and N-ethoxycarbonyl-N′- (4-ethoxycarbonyl-5-methylthiazol-2-yl) thiourea

Electrochemical behaviour of heterocyclic amidines I. Anodic oxidation of 2‐amino‐5‐ethoxycarbonyl‐4‐methylthiazole

Thianthrene hydroxylation: first or third order in water?

Current log-transform vs reactant concentration as a tool for chemical reaction order and electrochemical mechanisms determination—I. General theory in steady-state voltammetry and application to electro-oxidation of thianthrene in presence of water

G. Cauquis

Papers

Electrochemical oxidation of substituted thiazoles: 2-amino-4-ethoxycarbonyl-5- methylthiazole and N-ethoxycarbonyl-N′- (4-ethoxycarbonyl-5-methylthiazol-2-yl) thiourea

Electrochemical behaviour of heterocyclic amidines I. Anodic oxidation of 2‐amino‐5‐ethoxycarbonyl‐4‐methylthiazole

Thianthrene hydroxylation: first or third order in water?

Current log-transform vs reactant concentration as a tool for chemical reaction order and electrochemical mechanisms determination—I. General theory in steady-state voltammetry and application to electro-oxidation of thianthrene in presence of water

Anodic behaviour of some para-substituted α-cyano α-carboethoxy thioacetanilides