Abstract
The kinetics of cathodic processes proceeding in the acidic 0.01 M Cu(II) solutions containing gluconic acid and 0.5 M Na2SO4 as the supporting electrolyte is studied. According to the spectrophotometric data, in the moderately acidic solutions, a monoligand complex of CuL+ predominantly forms. Its concentration stability constant is 102.2 M−1. In the cathodic voltammograms, a well-defined plateau of the limiting current is observed. The height of the plateau obeys the Levich equation. The effective diffusion coefficient decreases from 4.2 × 10−6 to 2.5 × 10−6 cm2/s with increasing complexation degree of the system. An analysis of normalized Tafel plots showed that the exchange current density of Cu2+ + e → Cu+ process decreases with increasing concentration of ligand or with increasing pH value. Thereby, the cathodic chargetransfer coefficient remains constant (0.33 ± 0.02). A comparison of the kinetic data with the results of deposit surface examination points to significant surface activity of the ligand. The gluconate chemisorption can be accompanied by the incorporation of the fragments, which were formed as a result of its destruction, into the electrodeposits.
Similar content being viewed by others
References
Sawyer, D.T., Chem. Rev., 1964, vol. 64, p. 633.
Sillen, L.G. and Martell, A.E., Stability Constants of Metal-Ion Complexes. Special Pub. Nos. 17 and 25, London: Chem. Soc., 1964, vol. 1; 1971, vol. 2.
Martell, A.E. and Smith, R.M., Critical Stability Constants, New York: Plenum, 1976, vol. 4.
Alekseev, Yu.E., Garnovskii, A.D., and Zhdanov, Yu.A., Usp. Khim., 1998, vol. 67, p. 723 [Russ. Chem. Rev., (Engl. Transl.), vol. 67, p. 649].
Vasantha, V.S. and Muralidharan, V.S., Proc. Indian Acad. Sci., 1994, vol. 106, p. 825.
Abd El Rehim, S.S., Sayyah, S.M., and El Deeb, M.M., Appl. Surf. Sci., 2000, vol. 165, p. 249.
Abd El Rehim, S.S., Refaey, S.A., Schwitzgebel, G., Taha, F., and Saleh, M.B., J. Appl. Electrochem., 1996, vol. 26, p. 413.
Abd El Rehim, S.S., Mohamed, N.F., Amin, N.H., and Ali, L.I., J. Appl. Electrochem., 1997, vol. 27, p. 135.
Abd El Rehim, S.S., Sayyah, S.M., and El Deeb, M.M., Trans. IMF, 2000, vol. 78, p. 74.
Guaus, E. and Torrent-Burgues, J., J. Electroanal. Chem., 2003, vol. 549, p. 25.
Subramanian B., Mohan S., Sobha Jayakrishnan, Surf. Coat. Technol., 2006. V. 201. P. 1145.
Cannan, R.K. and Kibric, A., J. Am. Chem. Soc., 1938, vol. 60, p. 2314.
Pecsok, R.L. and Juvet, R.S. Jr., J. Am. Chem. Soc., 1955, vol. 77, p. 202.
Pecsok, R.L. and Juvet, R.S. Jr., J. Am. Chem. Soc., 1956, vol. 78, p. 3967.
Sawyer, D.T. and Bagger, J.B., J. Am. Chem. Soc., 1959, vol. 81, p. 5302.
Parke, S.A., Birch, G.G., MacDougall, D.B., and Stevens, D.A., Chem. Senses, 1997, vol. 22, p. 53.
Zubiaur, J., Castano, R., Etxebarria, N., Fernandez, L.A., and Madariaga, J.M., Talanta, 1998, vol. 45, p. 1007.
Barbe, J.C., de Revel, G., and Bertrand, A., J. Agric. Food Chem., 2002, vol. 50, p. 6408.
Zhang, Z., Gibson, P., Clark, S.B., Tian, G., Zanonato, P.L., and Rao, L., J. Solution Chem., 2007, vol. 36, p. 1187.
Escandar, G.M. and Sala, L.F., Can. J. Chem., 1992, vol. 70, p. 2053.
Blomqvist, K. and Still, E.R., Anal. Chem., 1985, vol. 57, p. 749.
Rajan, K.S. and Martell, E., J. Inorg. Nucl. Chem., 1967, vol. 29, p. 463.
Vicedomini, M., J. Coord. Chem., 1983, vol. 12, p. 307.
Kacena, V. and Matousek, L., Collect. Czech. Chem. Commun., 1953, vol. 18, p. 294.
Koryta, J., Progress in Polarography, New York: Interscience, 1962, vol. 1, p. 291.
Survila, A.A., Elektrodnye protsessy v sistemakh labil’nykh kompleksov metallov (The Electrode Processes in the Systems of Labile Metal Complexes), Vilnius: Mokslas, 1989.
Uljanionok, J., Jagminiene, A., and Survila, A., Chemija (Vilnius), 2009, vol. 20, p. 89.
Budene, Yu., Survilene, A., and Survila, A., Elektrokhimiya, 2004, vol. 40, p. 443 [Budiene, J., Surviliene, A., and Survila, A., Russ. J. Electrochem, 2004, vol. 40, p. 394].
Uljanionok, J. and Survila, A., Chemija (Vilnius), 2009, vol. 20, p. 84.
Akilan, C., Thermodynamic and related studies of aqueous copper(II) sulfate solutions. Ph.D. Dissertation. Australia: Murdoch Univ., 2008.
Davies, C.W., Ion Association, London: Butterworths, 1962.
Butler, J.N., Ionic equilibrium (a mathematical approach), Massachusetts: Reading, 1964.
Gluconic Acid and Derivatives. SIDS Initial Assessment Report for SIAM 18, Paris: France, 20–23 April, 2004.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © A. Survila, Z. Mockus, S. Kanapeckaite, J. Pileckiene, G. Stalnionis, 2011, published in Elektrokhimiya, 2011, Vol. 47, No. 2, pp. 139–146.
Rights and permissions
About this article
Cite this article
Survila, A., Mockus, Z., Kanapeckaite, S. et al. Cathodic processes in copper(II) solutions containing gluconic acid. Russ J Electrochem 47, 129–135 (2011). https://doi.org/10.1134/S1023193511020169
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S1023193511020169