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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)


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.


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