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Discussion aspects of the theory of galvanostatic phase formation

Iurii G. Kryshtop, Vitaliy V. Trofimenko

Abstract


The thermodynamic and kinetic peculiarities of metal nucleation under galvanostatic conditions are considered. The alternative expressions for supersaturation in electrochemical systems in terms of overall overpotential (Kaischew, Budevski, Malev, Polukarov, de Levi at al.) or crystallization overpotential (Fischer, Volmer, Schottky, Vetter, Lorenz, Gerischer at al.) are discussed. It is shown that incorrect use of expression for supersaturation in terms of overall overpotential leads some authors to unreasonable interpretation of experimental data. This leads to negative impact on  electrochemical nucleation theory development. Some kinetic theories (Schottky, Baraboshkin, Kashchiev) take into account changes of supersaturation and atoms consumption by growing nuclei during the current pulse. However this corrections are difficult to identify. Computer modeling of galvanostatic phase formation (Isaev, Baraboshkin, Volegov) correctly describes the time dependence of the main parameters of nucleation. Moreover, applying of this approach in data processing of experimental overpotential transients requires the kinetic and thermodynamic constants of the process determination. Gutsov`s kinetic model is still more suitable for the analysis of experimental overpotential transients, because this theory takes into account the influence of crystallization overpotential on the rate of phase formation.


Keywords


galvanostatic nucleation; supersaturation, crystallization overpotential; adatoms; overpotential transient

References


Kaischew R., Toshev S., Markov I. Processes of new phase formation during electrodeposition of metals. Izv. Otd. Khim. Nauki (Bulg. Akad. Nauk.)., 1969, vol. 2, no. 3, p. 467–477.

Danilov A.I., Polukarov Yu. M. Modern ideas about the processes involving the formation and growth of the nuclei of a new phase under potentiostatic conditions Russ. Chem. Rev., 1987, vol. 56, no. 7, p. 619–632.

Budevski E., Staikov G., Lorenz W. I. Electrochemical phase formation and growth. Advances in Electrochemical Science and Engineering. Weinheim: VCH, 1996, 410 p.

Milchev A. Electrocrystallization. Fundamentals of nucleation and growth. Boston-Dordrecht-London: Kluwer academic publisher, 2002, 265 p.

Fischer H. Elektrolytische Abscheidung und Elektrokristallisation von Metallen. Berlin: Springer, 1954, 514 p.

Vetter K., Bachmann K. I. Crystallization overpotential. Z. Phys. Chem. NF., 1967, vol. 53, no. 1/2, p. 9–28.

Trofimenko V. V. Analytical description of supersaturation during metals electrocrystallization. Ukr. Khim. Zh., 1987, vol. 53, no. 3, p. 272–275.

Gamburg Yu. D. Elektrohimicheskaya kristallizatsiya metallov i splavov. Moscow: Yanus-K, 1997, 384 p.

De Levi R. On the issue of partial overpotentials. Elektrokhimiya, 1999, vol. 35, no. 1, p. 142–144.

Yin K. M. Mathematical model of galvanostatic puls with reverse plating in the presence of a surface blocking agent. J. Electrochem. Soc., 2003, vol. 150, no. 6, p. 435–439.

Vetter K. Electrochemical kinetics: theoretical and experimental aspects. New York: Academic Press, 1967, 807 p.

Fischer H. Electrocrystallization of metals under ideal and real conditions. Angew. Chem., 1969, vol. 81, no. 3, p. 101–114.

Damaskin B. B., Petriy O. A. Vvedenie v elektrohimicheskuyu kinetiku. Moscow: Vyisshaya shkola, 1975, 416 p.

Baraboshkin A. N. Elektrokristallizatsiya metallov iz rasplavlennyih soley. Moscow: Nauka, 1976, 279 p.

Gutzov I. Kinetics of electrolytic phase formation under galvanostatic conditions. Izv. Inst. Fizikokhim., Bulg. Akad. Nauk. 1964, vol. 4, p. 69–87.

Klapka V. To the problem of crystallization overvoltage during electrocrystallization of metals. Coll. Czech. Chem. Commun., 1970, vol. 35, no. 3, p. 899–906.

Trofimenko V. V., Loshkarev Yu. M., Kovalenko V. S. On the issue of separation of crystallization and charge transfer overpotentials during electrolytic phase formation. Dokl. Akad. Nauk SSSR. Ser. Khim., 1976, vol. 227, no. 5, p. 1181–1184.

Trofimenko V. V., Kovalenko V. S., Loshkarev Yu. M., Zhitnik V. P. Kinetics of nonstationary nucleation under galvanostatic conditions. Elektrokhimiya, 1983, vol. 19, no. 7, p. 887–893.

Baraboshkin A. N., Isaev V. A., Chebotin V. N. Crystal nucleation under galvanostatic conditions. Mathematic modeling. Elektrokhimiya, 1981, vol. 17, no. 4, p. 483–487.

Isaev V. A., Volegov A. V., Baraboshkin A. N. Kinetics of phase formation in the melts under galvanostatic conditions. Elektrokhimiya, 1989, vol. 25, no. 5, p. 85–87.

Kondrashin V. Yu. On the issue of overpotential summand of electrode process. Elektrokhimiya, 1998, vol. 34, no. 2, p. 160–165.

Instruction and terminology for physicochemical quantities and units. Appendix III. Electrochemical nomenclature. Elektrokhimiya, 1975, vol. 11, no. 2, p. 1780–1797.

Trofimenko V. V. Features of analysis electrocrystallization metals stages by galvanostatic transient of potential method. Ukr. Khim. Zh., 1997, vol. 64, no. 8, p. 117–120.

Shahvorostov А. V., Trofimenko V. V., Loshkarev Yu., M. Features of using galvanostatic method in the study of crystallization of metals. Elektrokhimiya, 1997, vol. 33, no. 9, p. 1023–1027.

Trofimenko V. V., Kovalenko V. S., Loshkarev Yu. M. Zh., 1987, vol. 53, no. 5, p. 504–508.

Volmer M., Weber A. Nucleation in supersaturated systems. Z. Phys. Chem., 1926, vol. A119, no. 3/4, p. 277–301.

Tomfor G., Volmer M. Nucleation under the influence of electric charges. Ann. Phys. Chem., 1938, vol. 33, no. 5, p. 109–131.

Trofimenko V. V., Loshkarev Yu. M. Crystallization overpotential of a new phase nucleation. Izv. Sib. Fil. Akad. Nauk SSSR, Khim. Nauk., 1986, vol. 6, no. 7, p. 17–22.

Polukarov Yu. M. The initial stages of metals electrocrystallization. Itogi nauki i tehniki. Elektrohimiya, 1979, vol. 15, p. 3–61.

Kahlweit M. About kinetics of phase formation in condensed systems. 1 The precipitation of soluble heavy electrolyte from aqueous solutions. Z. Phys. Chem., 1960, vol. 25, p. 1–25.

Schottky W. F. Electrolytic nucleation of silver on metal electrodes. Z. Phys. Chem. NF., 1962, vol. 31, no. 1/2, p. 40–70.

Mierke G., Schottky W. Electrolytic nucleation of silver on metal electrodes. Ber. Bunsenges. Phys. Chem., 1967, vol. 72, no. 5, p. 516–526.

Baraboshkin A. N., Kosihin L. T., Saltyikova N. A. Study of crystals nucleation during electrolysis of molten salts. 1. The deposition of silver from nitrate melts. Tr. Inst. Elektrokhim., Ural. Nauchn. Tsentr, Akad. Nauk SSSR, 1964, vol. 5, p. 89–100.

Baraboshkin A. N., Kosihin L. T., Saltyikova N. A. Study of crystals nucleation during electrolysis of molten salts 2. Electrolysis of pure molten silver nitrate. Tr. Inst. Elektrokhim., Ural. Nauchn. Tsentr, Akad. Nauk SSSR, 1965, vol. 7, p. 47–58.

Trofimenko V. V., Zhitnik V. P., Kovalenko V. S., Loshkarev Yu. M. Influence of adsorption of organic additives on the phase formation under galvanostatic conditions. Ukr. Khim. Zh., 1986, vol. 52, no. 8, p. 839–843.

Kashchiev D., Milchev A. Kinetics of the initial stage of electrolytic deposition of metals. I. General theory. Thin Solid Films, 1975, vol. 28, no. 2, p. 189–200.

Kashchiev D. Kinetics of the initial stage of electrolytic deposition of metals. III. Galvanostatic conditions. Thin Solid Films, 1975, vol. 29, no. 2, p. 193–209.




DOI: http://dx.doi.org/10.15421/081414

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