International E-publication: Publish Projects, Dissertation, Theses, Books, Souvenir, Conference Proceeding with ISBN.  International E-Bulletin: Information/News regarding: Academics and Research

Kinetic Investigations of the Hydrogen evolution reaction on Hg electrode: Impedance Spectroscopy studies

Author Affiliations

  • 1Department of Chemistry, K. N. Toosi University of Technology, Tehran, IRAN
  • 2Department of Chemistry, The University of Western Ontario, London, Ontario, CANADA
  • 3Abadan Faculty of Petroleum Engineering, Petroleum University of Technology, Abadan, IRAN
  • 4Department of Chemistry, Sharif University of Technology, Tehran, IRAN

Res.J.chem.sci., Volume 3, Issue (10), Pages 56-63, October,18 (2013)

Abstract

The mechanism and kinetics of the hydrogen evolution reaction (HER) on Hg electrode in 0.1 M H2 SO4solution were studied using steady-state polarization, open circuit potential transient and electrochemical impedance. The simulation of the data obtained from these methods, by nonlinear fitting procedure allowed us to determine the rate constants of the Volmer, Heyrovsky and Tafel steps associated with the hydrogen evolution reaction. The kinetics results indicate that HER mechanism at low negative potentials is a serial combination of Volmer and parallel Tafel and Heyrovsky steps. At high negative potentials where the hydrogen coverage reaches its limiting value, a Tafel line with the slope of -116 mV dec-1 is obtained. In this potential hydrogen evolution follows the Volmer-Heyrovsky mechanism while the Tafel step has negligible contribution. Open circuit potential for Hg at different charging currents show that the higher charging cathodic current, the longer time is required to reach the equilibrium potential.

References

  1. Kim H.K., Yang D.C., Jang I.S., Park C.N., Park C.J. and Choi J., Effects of pretreatment of LM-Ni3.9Co0.6Mn0.3Al0.2 alloy powders in a KOH/NaBH4 solution on the electrode characteristics and inner pressure of nickel-metal-hydride secondary batteries, Int. J. Hydrogen Energy, 34, 9570- 9575 (2009)
  2. Xu Y.H., He G.R. and Wang X.L., Hydrogen evolution reaction on the AB5 metal hydride electrode, Int. J. Hydrogen Energy 28, 961-965 (2003)
  3. Jagadeesh B. Effects of Zinc and Tungsten Additions in Mn-Mo-O Eectrocatalyst for Hydrogen Production from Seawater Electrolysis, Res. J. Chem. Sci., 1, 13-119 (2011)
  4. Liu B.H., Li Z.P. Zhu J.K. and Suda S., Influences of hydrogen evolution on the cell and stack performances of the direct borohydride fuel cell, J. Power Sources 183, 151- 156 (2008)
  5. Lisnyak V.V., Ischenko E.V., Stratiichuk D.A., Zaderko A.N., Boldyrieva O.Yu., Safonova V.V. and Yatsymyrskyi A.V., Pt, Pd Supported on Niobium Phosphates as Catalysts for the Hydrogen Oxidation, Res. J. Chem. Sci., 3, 30-33 (2013)
  6. Huang Y., Wen Q., Jiang J. H., Shen G.L. and Yu R.Q., A novel electrochemical immuno sensor based on hydrogen evolution inhibition by enzymatic copper deposition on platinum nanoparticle-modified electrode, Biosens. Bioelectron. 24, 600-605 (2008)
  7. Islam M.M., Ferdousi B.N., Okajima T., Ohsaka T., A catalytic activity of a mercury electrode towards dioxygen reduction in room-temperature ionic liquids, Electrochem. Commun., 7, 789-795 (2005)
  8. Ralph T.R., Hitchman M.L., Millington J.P. and Walsh F. C., The reduction of l-cystine in hydrochloric acid at mercury drop electrodes, J. Electroanal. Chem., 587, 31-41 (2006)
  9. Rueda M., Compton R.G., Alden J. A. and Prieto F., Impedance voltammetry of electro-dimerization mechanisms: Application to the reduction of the methyl viologen di-cation at mercury electrodes and aqueous solutions, J. Electroanal. Chem., 443, 227-235 (1998)
  10. Caetano J., Homem-de-Mello P., da Silva A.B.F. and Ferreira A.G., Avaca L A, Studies of the electrochemical reduction of atrazine on a mercury electrode in acid medium: An electrochemical and NMR approach, J. Electroanal. Chem. 608, 47-51 (2007)
  11. Montoya M.R., Pintado S. and Mellado J.M.R., Electrochemical reduction of imazamethabenz methyl on mercury and carbon electrodes, Electrochim. Acta, 55, 3164-3170 (2010)
  12. Saha M.S. and Ohsaka T., Electrode kinetics of the O2/O2 -redox couple at Hg electrode in the presence of PVC in aprotic media. Electrochim, Acta, 50, 4746-4751 (2005)
  13. Wisniewski A., Czerwinski W.K., Paklepa P., Wrona P.K. and Orlik M., The convection-driven non-additivity of the faradaic currents for the parallel reduction of some metal and hydrogen cations at the mercury electrode, J. Electroanal. Chem., 623, 120-128 (2008)
  14. Gajek A. and Zakroczymski T. Long-lasting hydrogen evolution on and hydrogen entry into iron in an aqueous solution, J. Electroanal. Chem. 578, 171-182 (2005)
  15. Evard E., Gabis I. and Yartys V. A., Kinetics of hydrogen evolution from MgH2: Experimental studies, mechanism and modeling, Int. J. Hydrogen Energy, 35, 9060-9069 (2010)
  16. Conway B.E. and Bai L., Determination of the adsorption behaviour of ‘overpotential-deposited’ hydrogen-atom species in the cathodic hydrogen-evolution reaction by analysis of potential-relaxation transients, J. Chem. Soc. Faraday Trans.1, 81, 1841-1862 (1985)
  17. Krstajic N.V., Grgur B.N., Mladenovic N.S., Vojnovic M.V. and Jaksic J.M., The determination of kinetics parameters of the hydrogen evolution on Ti---Ni alloys by ac impedance, Electrochim. Acta, 42, 323-330 (1997)
  18. Chen J.S., Diard J.P., Durand R. and Montella C. Hydrogen insertion reaction with restricted diffusion. Part 1. Potential step-EIS theory and review for the direct insertion mechanism, J. Electroanal. Chem., 406, 1-13 (1996)
  19. Danaee I., Jafarian M., Forouzandeh F., Gobal F. and Mahjani M.G. Kinetic Interpretation of a Negative Time Constant Impedance of Glucose Electrooxidation, J. Phys. Chem., B 112, 15933-15940 (2008)
  20. Krishtalik L.I., Charge transfer reactions in electrochemical and chemical processes. New York, Plenum, (1986)
  21. Danaee I., Jafarian M., Forouzandeh F., Gobal F. and Mahjani M.G., Electrochemical impedance studies of methanol oxidation on GC/Ni and GC/NiCu electrode, Int. J. Hydrogen Energy, 34, 859-869 (2009)
  22. Danaee I., Jafarian M., Mirzapoor A., Gobal F. and Mahjani M. G., Electrooxidation of methanol on NiMn alloy modified graphite electrode, Electrochim, Acta, 55, 2093-2100 (2010)
  23. Shan Z., Liu Y., Chen Z., Warrender G. and Tian J., Amorphous Ni-S-Mn alloy as hydrogen evolution reaction cathode in alkaline medium, Int. J. Hydrogen Energy, 33, 28-33 (2008)
  24. Chandran M. and Ramesh Bapu G.N.K., Electrodeposition of Nano Zinc - Nickel Alloy from Bromide Based Electrolyte, Res. J. Chem. Sci., 3, 57-62 (2013)
  25. Danaee I. and Noori S., Kinetics of the hydrogen evolution reaction on NiMn graphite modified electrode. Int. J. Hydrogen Energy, 36, 12102-12111 (2011)
  26. Macdonald J.R., Note on the parameterization of the constant phase admittance element, Solid State Ion., 13, 147–149 (1984)
  27. Danaee I., Kinetics and mechanism of palladium electrodeposition on graphite electrode by impedance and noise measurements, J. Electroanal. Chem., 662, 415-420 (2011)
  28. Lasia A., Rami A., Kinetics of hydrogen evolution on nickel electrodes, J. Electroanal. Chem., 294, 123-141 (1990)
  29. Krstajic N., Popovic M., Grgur B., Vojnovic M. and Sepa D., On the kinetics of the hydrogen evolution reaction on nickel in alkaline solution: Part I. The mechanism, J. Electroanal. Chem., 512, 16-26 (2001)
  30. Shylesha B.S., Venkatesha T.V. and Praveen B.M. Corrosion Inhibition Studies of Mild Steel by New Inhibitor in Different Corrosive Medium, Res. J. Chem. Sci., 1, 46-50 (2011)
  31. Prathibha B.S., Kotteeswaran P. and Bheema Raju V.Study on the Inhibition of Mild Steel Corrosion by Quaternary Ammonium Compound in H2SO4 Medium, Res. J. Rec. Sci., 2, 1-10 (2013)
  32. Manivannan M. and Rajendran S. Corrosion Inhibition of Carbon steel by Succinic acid – Zn2+ system, Res. J. Chem. Sci., 1, 42-48 (2011)
  33. Bai L., Harrington D.A. and Conway B.E., Behavior of overpotential-deposited species in Faradaic reactions-II. ac Impedance measurements on H2 evolution kinetics at activated and unactivated Pt cathodes, Electrochim. Acta, 32, 1713-1731 (1987)
  34. VracÏar L., Burojevic S. and Krstajic N., Unconventional temperature-dependence of Tafel slopes for the hydrogen evolution reaction at Pd-Ni electrode in alkaline solution, J. Serb Chem. Soc., 63, 201 (1998)
  35. Harrington D. A. and Conway B. E., Kinetic theory of the open-circuit potential decay method for evaluation of behaviour of adsorbed intermediates: Analysis for the case of the H2 evolution reaction, J. Electroanal. Chem., 221, 1- 21 (1987)
  36. Conway B.E., Bai L. and Tessier D.F., Data collection and processing of open-circuit potential-decay measurements using a digital oscilloscope: Derivation of the Hcapacitance behaviour of H2-evolving, Ni-based cathodes, J. Electroanal. Chem., 161, 39-49 (1984)