Abstract
The oxidation of ferrocene (FeCp2) to ferrocenium cation (FeCp +2 ) (where Cp: cyclopentadienyl anion, C5H5 −) was investigated by means of electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) on either platinum (Pt) or glassy carbon (G-C) electrodes in acetonitrile (ACN), acetone (ACE), and acetonitrile (ACN)/acetone (ACE) binary mixtures with n-tetrabutylammonium hexafluorophosphate (TBAPF6) as background electrolyte at T = 294.15 K. The half-wave potentials (E 1/2), the diffusion coefficients (D), and the heterogeneous electron-transfer rate constants (k s) were derived. The activation free energies for electron transfer (ΔG ≠exp ) were experimentally determined and compared with the theoretical values (ΔG ≠cal ). The electron-transfer process was reversible and diffusion-controlled in all investigated solvent mixtures. The changes on the metal–ligand bond lengths upon electron transfer were almost insignificant. The E 1/2 values were shifted to less positive potentials with the increase of the ACN content. The k s values obtained on Pt electrode were slightly larger compared to k s measured on G-C electrode, while in both cases the k s values were diminished with the enrichment of the mixtures in ACN. The EIS spectra confirmed that the rate-determining step in the whole process is the diffusion of the FeCp2 species and thus the process can be properly characterized as diffusion-controlled.
Similar content being viewed by others
References
Seibold EA, Sutton LE (1955) J Chem Phys 23:1967
Geiger WE (1990) Organometallic radical processes. Elsevier, Amsterdam (and references therein)
Zhu T, Su CH, Lemke BK, Wilson LJ, Kadish KM (1983) Inorg Chem 22:2527
Kadish KM, Su CH (1983) J Am Chem Soc 105:177
Gritzner G, Kuta J (1982) J Pure Appl Chem 54:1527
Diggle JW, Parker AJ (1973) Electrochim Acta 18:975
Saji T, Maruyama Y, Aoyagvi S (1978) J Electroanal Chem 86:219
Bond AM, Henderson TLE, Mann DR, Mann TF, Thormann W, Zoski CG (1988) Anal Chem 60:1878
Pournaghi-Azar MH, Ojani R (1994) Electrochim Acta 39:953
Kadish KM, Ding JQ, Malinski T (1984) Anal Chem 56:1741
Kamau GN, Saccucci TM, Gounilli G, Nassar AEF, Rusling JF (1994) Anal Chem 66:994
Daschbach J, Blackwood D, Pons JW, Pons S (1987) J Electroanal Chem 237:269
Crooks RM, Bard AJ (1988) J Electroanal Chem 243:117
Bond AM, Oldham KB, Snook GA (2000) Anal Chem 72:3492
Wightman RM (1981) Anal Chem 53:1125
Howell JO, Wightman RM (1984) Anal Chem 56:524
Daniele S, Baldo MA, Bragato C (1999) Electrochem Commun 1:37
Zara AJ, Machado SS, Bulhoes LOS, Benedetti AV, Rabockai T (1987) J Electroanal Chem 221:165
Quirk PF, Kratochvil B (1970) Anal Chem 42:535
Hartl F, Mahabiersing T, Le Floch P, Mathey F, Ricard L, Rosa P, Záliš S (2003) Inorg Chem 42:4442
CRC (2003/2004) Handbook of chemistry and physics, 84th ed. CRC Press, Boca Raton, FL
Randles JEB (1948) Trans Faraday Soc 44:327
Comminges C, Barhdadi R, Laurent M, Troupel M (2006) J Chem Eng Data 51:680
Wasserscheid P, Keim W (2000) Angew Chem Int Ed 39:3772
Fischer DW (1964) Acta Cryst 17:619
Nicholson RS (1965) Anal Chem 37:1351
Kanatharana P, Spritzer MS (1974) Anal Chem 46:958
Bond AM, Henderson TLE, Thorman WJ (1986) J Phys Chem 90:2911
Marcus RA (1965) J Chem Phys 43:679
Marcus RA (1968) Electrochim Acta 13:995
Bockris JOM, Khan SUM (1979) Quantum electrochemistry. Plenum Press, New York
Goldfarb DL, Longinotti MP, Corti HR (2001) J Solution Chem 30:307
Reynolds BB, Kraus CA (1948) J Am Chem Soc 70:1709
Bernstein T, Herbstein FH (1968) Acta Cryst B24:1640
Halle JM (1971) Reactions of molecules at electrodes. Wiley, London
Mohran HS (2005) Am J Appl Sci 2:1629
Rashwan F (2005) Am J Appl Sci 2:1595
Kim DJ, Ryu HS, Kim IP, Cho KK, Nam TH, Kim KW, Ahn JH, Ahn HJ (2007) Phys Scr T129:70
Marcus Y (1984) J Solution Chem 13:599
Baur JE, Wightman RM (1991) J Electroanal Chem 305:73
Sharp M (1983) Electrochim Acta 28:301
Moharram YI (2006) J Electroanal Chem 587:115
Kuwana T, Bublitz DE, Hoh G (1960) J Am Chem Soc 82:5811
Sharp M, Peterson M, Edström K (1980) J Electroanal Chem 109:271
Tsierkezos NG (2007) J Solution Chem 36:289
Acknowledgments
The authors would like to thank Mrs. D. Schneider (TU Ilmenau).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Tsierkezos, N.G., Ritter, U. Electrochemical impedance spectroscopy and cyclic voltammetry of ferrocene in acetonitrile/acetone system. J Appl Electrochem 40, 409–417 (2010). https://doi.org/10.1007/s10800-009-0011-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10800-009-0011-3