Abstract
The dynamics of hydrogen gas bubble evolution at copper microelectrodes in H2SO4 and HCl solutions of various compositions have been studied by means of galvanostatic polarization experiments and simultaneous video taping. As long as the solution contains acid only, gas evolution is dominated by the growth of a single bubble at the electrode at any one time. The transients in H2SO4 solutions exhibit regular sustained relaxation oscillations that can be distinctly related to events occurring at the cathode. The electrode response in HCl solutions is somewhat noisier and shows much larger cathodic polarization and oscillation frequency and amplitude, presumably due to an interaction between Cl– and the copper surface. Additions of Na2SO4 and NaCl to these solutions promote the nucleation and growth of numerous small bubbles at any one time and the diminishing of the oscillations of the electrode potential. The addition of thiourea to 2.0 m H2SO4 does not destroy the single bubble growth characteristic of acid-only solutions, but increases the cathodic overpotential at all organic levels with a maximum occurring at about 0.13 mm thiourea. Oscillation frequency and amplitude, and bubble departure diameter all show a similar dependence on thiourea concentration to that of overpotential.
Similar content being viewed by others
References
Lord Rayleigh, Philos. Mag. 34 (1917) 94.
B. Kubanov and A. Frumkin, Z. Phys. Chem. 165A (1933) 433.
L. E. Scriven, Chem. Eng. Sci. 10 (1959) 1.
D. E. Westerheide and J. H. Westwater, AIChE J. 7 (1961) 351.
S. Shibata, Bull. Chem. Soc. Japan 36 (1963) 53.
J. P. Glas and J. W. Westwater, Int. J. Heat Mass Transfer 7 (1964) 1427.
R. Lessard and S. A. Zieminski, Ind. Eng. Chem. Fundam. 10 (1971) 260.
M. G. Fouad and G. H. Sedahamed, Electrochim. Acta 18 (1973) 55.
L. Janssen, ibid. 23 (1978) 81.
H. Vogt, ibid. 28 (1981) 1311.
H. Vogt, in `Comprehensive Treatise of Electrochemistry', vol. 6, Plenum Press, New York (1983), p. 445
P. J. Sides and C. W. Tobias, J. Electrochem. Soc. 132 (1985) 583.
P. J. Sides, in `Modern Aspects of Electrochemistry', vol. 18, Plenum Press, New York (1986) p. 303.
J. Dukovic and C. W. Tobias, J. Electrochem. Soc. 134 (1987) 331.
J. A. Leistra and P. J. Sides, ibid. 134 (1987) 2442.
D. Landolt, R. Acosta, R. H. Muller and C. W. Tobias, ibid. 117 (1970) 839.
L. Janssen and J. Hoogland, Electrochim. Acta 18 (1973) 543.
C. Gabrielli, F. Huet and M. Keddam, J. Appl. Electrochem. 15 (1985) 503.
C. Gabrielli, F. Huet, M. Keddam, A. Macias and A. Sahar, ibid. 19 (1989) 618.
C. Gabrielli, F. Huet, M. Keddam and A. Sahar, ibid. 19 (1989) 683.
N. P. Brandon and G. H. Kelsall, ibid. 15 (1985) 476.
R. Lessard and S. A. Zieminski, Ind. Eng. Chem. Fundam. 10 (1971) 260–8.
M. J. Prince and H. W. Blanch, AIChE J. 36 (1990) 1425.
V. S. J. Craig, B. W. Ninham and R. M. Pashley, J. Phys. Chem. 97 (1993) 10192.
Z. A. Jofa, Proceedings of the 2nd European Symposiom on Corrosion Inhibition, Ferrara (1965), p. 100.
J. Crousier and I. Bimaghra, J. Appl. Electrochem. 23 (1993) 780.
M. D. Pritzker, J. Electroanal. Chem. 373 (1994) 39.
R. Agrawal and T. K. G. Namboodhiri, Corros. Sci. 30 (1990) 50.
D. R. Turner and G. R. Johnson, J. Electrochem. Soc. 109 (1962) 803.
L. Cavallaro, L. Felloni, G. Trananelli and F. Pulidori, Electrochim. Acta 8 (1963) 523.
Q. Su, Y. Umetsu and K. Tozawa, J. Mining & Mater. Process. Institute of Japan 105 (1989) 959.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kristof , P., Pritzker , M. Effect of electrolyte composition on the dynamics of hydrogen gas bubble evolution at copper microelectrodes. Journal of Applied Electrochemistry 27, 255–265 (1997). https://doi.org/10.1023/A:1018472511901
Issue Date:
DOI: https://doi.org/10.1023/A:1018472511901