Статья
2020

Effect of Complex Formation on Mass Transfer during Metal Electrodeposition on Rotating Disk Electrode


V. M. Volgin V. M. Volgin , A. D. Davydov A. D. Davydov
Российский электрохимический журнал
https://doi.org/10.1134/S1023193520100134
Abstract / Full Text

The effect of complex formation on the mass transfer during the metal electrodeposition on a rotating disk electrode from the solution containing three types of ions (metal cation, cationic complex, and non-electroactive anion) is studied theoretically. The dimensionless Nernst–Planck equations in the approximation of solution electroneutrality, which take into account the electro-diffusion and convective transfer of all types of ions and the homogeneous reaction of complex formation, are used as the mathematical model. The kinetics of electrochemical reactions is taken into account using the Butler–Volmer equations. In contrast to the known works, the approximations of the Nernst layer, equal diffusion coefficients of all types of ions, and equilibrium complex formation reaction are not used. As a result of numerical solution, the distributions of concentration, potential, and the rate of complex formation reaction are obtained at various parameters of the system under consideration. It is shown that the equilibrium and rate constants of complex formation reaction and the ratio between the diffusion coefficients of complex cation and anion have the strongest effect on the mass transfer.

Author information
  • Tula State University, 300012, Tula, Russia

    V. M. Volgin

  • Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 119071, Moscow, Russia

    V. M. Volgin & A. D. Davydov

References
  1. Survila, A., Electrochemistry of Metal Complexes: Applications from Electroplating to Oxide Layer Formation, Weinheim: Wiley, 2015.
  2. Berezin, N.B. and Mezhevich, Zh.V., Elektroosazhdenie metallov iz vodnykh rastvorov kompleksnykh soedinenii (Electrodeposition of Metals from Aqueous Solutions of Complex Compounds), Kazan: Kazan National Research Technological University, 2015.
  3. Bek, R.Yu., Tsupak, T.E., Borodikhina, L.I., and Nguen, Z.Sh., Peculiarities of the influence of complex formation on migration effect, Electrokhimiya, 1983, vol. 19(8), p. 1149.
  4. Bek, R.Yu. and Tsupak, T.E., Influence of complex formation on migration effects in systems with polyvalent cations and negatively charged ligands, Soviet Electrochem., 1987, vol. 23, p. 519.
  5. Ying, R.Y., Ng, P.K., Mao, Z., and White, R.E., Electrodeposition of Copper-Nickel Alloys from Citrate Solutions on a Rotating Disk Electrode II. Mathematical Modeling, J. Electrochem. Soc., 1988, vol. 135, p. 2964.
  6. Kharkats, Yu.I., Migratsionnye toki v elektrokhimicheskoi kinetike (Migration Currents in Electrochemical Kinetics), Moscow: VINITI, 1991.
  7. Kharkats, Y.I. and Sokirko, A.V., The theory of limiting diffusion-migration currents in partially dissociated electrolytes, J. Electroanal. Chem. Interfac. Electrochem., 1991, vol. 303, p. 17.
  8. Podlaha, E.J., Bonhote, C., and Landolt, D., A mathematical model and experimental study of the electrodeposition of Ni–Cu alloys from complexing electrolytes, Electrochim. Acta, 1994, vol. 39, p. 2649.
  9. Kharkats, Yu.I., Electromigration and complexing in reactions of reduction of cations, Russ. J. Electrochem., 1998. vol. 34, p. 526.
  10. Bek, R.Yu., Tsupak, T.E., Shuraeva, L.I., and Kosolapov, G.V., Effect of complexation on mass transport in solutions containing cadmium complexes and chloride ions, Soviet Electrochem., 1987, vol. 23, p. 1506.
  11. Bek, R.Yu., Tsupak, T.E., and Shuraeva, L.I., Electromigration and interaction between fluxes of discharging ions during electrodeposition of metals from complex electrolytes, Russ. J. Electrochem., 1998, vol. 34, p. 165.
  12. Rode, S., Henninot, C., Vallieres, C., and Matlosz, M., Complexation chemistry in copper plating from citrate baths, J. Electrochem. Soc., 2004, vol. 151, p. C405.
  13. Rode, S., Henninot, C., and Matlosz, M., Complexation chemistry in nickel and copper-nickel alloy plating from citrate baths, J. Electrochem. Soc., 2005, vol. 152, p. C248.
  14. Sedoikin, A.A. and Tsupak, T.E., The role of migration mass transfer in the electrodeposition of nickel from sulfate-chloride and chloride solutions containing succinic acid, Russ. J. Electrochem., 2008, vol. 44, p. 319.
  15. Pleskov, Yu.V. and Filinovsky, V.Yu., Rotating Disk Electrode, New York: Consultants Bureau, 1976.
  16. Levich, V.G., Physicochemical Hydrodynamics, Englewood Cliffs, N.J.: Prentice Hall, 1962.
  17. Moukalled, F., Mangani, L., Darwish, M., The Finite Volume Method in Computational Fluid Dynamics, Cham: Springer, 2016.
  18. Newman, J.S., Electrochemical Systems, Englewood Cliffs, N. J.: Prentice Hall, 1973.
  19. Volgin, V.M. and Davydov, A.D., Ionic transport through ion-exchange and bipolar membranes, J. Membrane Sci., 2005, vol. 259, p. 110.
  20. Volgin, V.M. and Davydov, A.D., Numerical simulation of steady-state ion transfer to rotating disk electrode: Accuracy and computational efficiency, J. Electroanal. Chem., 2007, vol. 600, p. 171.
  21. Volgin, V.M. and Davydov, A.D., Effect of migration on homogeneous redox electrocatalysis at rotating disk electrode, Electrochim. Acta, 2018, vol. 259, p. 56.