The Mechanism of Hydrogen Evolution at Nickel Cathodes in Aqueous Solutions

Hydrogen overpotential at nickel cathodes has been measured under very pure conditions in aqueous solutions of hydrogen chloride (0.001N − 1.0N) and in aqueous sodium hydroxide (0.001N − 0.2N). The measurements have been made in the current density range 10−8 − 10−1 amp/apparent cm2, and in the temperature range 0°—50°C. Observations were also made of the buildup and rate of decay of overpotential and of the capacity of the electrode/electrolyte interface. Direct measurements were made of the number of acts of the rate‐determining step associated with one act of the over‐all hydrogen evolution reaction (i.e., the stoichiometric number μ). The application of μ has been extended to hydrogen overpotentials greater than about − 20 millivolts. The experimental data were treated statistically and show that the most probable mechanism of hydrogen overpotential at nickel cathodes is that of a rate‐determining discharge step followed by a recombination of hydrogen atoms. The discharge probably takes place from hyd...

[1]  J. Bockris,et al.  Cathodic Evolution of Hydrogen at Very High Current Densities , 1950, Nature.

[2]  E. Rideal,et al.  On overpotential and the photovoltaic process at polarized electrodes , 1949, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[3]  Bockris Jo.  Recent developments in the study of hydrogen overpotential. , 1948 .

[4]  J. Horiuti.  A METHOD OF STATISTICAL MECHANICAL TREATMENT OF EQUILIBRIUM AND CHEMICAL REACTIONS. , 1948 .

[5]  B. Conway,et al.  LABORATORY AND WORKSHOP NOTES: Preparation and Maintenance of Electrodes in a Hydrogen Atmosphere , 1948 .

[6]  D. Grahame.  The electrical double layer and the theory of electrocapillarity. , 1947, Chemical reviews.

[7]  A. Wheeler,et al.  Catalytic activity, crystal structure and adsorptive properties of evaporated metal films , 1940, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[8]  K. Laidler,et al.  Application of the Theory of Absolute Reaction Rates to Overvoltage , 1939 .

[9]  S. Robin.  Étude de la perturbation des raies spectrales par la pression jusqu’à 1200 Kg/cm2 , 1952 .

[10]  R. Parsons.  General equations for the kinetics of electrode processes , 1951 .

[11]  B. Conway,et al.  Some aspects of the measurement of hydrogen overpotential , 1950 .

[12]  E. Rideal,et al.  The adsorption of hydrogen by tungsten, and the mechanism of the parahydrogen conversion at tungsten surfaces , 1950 .

[13]  B. Conway,et al.  Studies in hydrogen overpotential. The effect of catalytic poisons at platinized platinum and nickel , 1949 .