Overvoltage, Hydrogen

A conductor with a hydrogen overvoltage exceeding that of smooth platinum can be used for the cathode. 

Mercury Cells. The cathode material ia mercury cells, mercury [7439-97-6] Hg, has a high hydrogen overvoltage. Hydrogen evolution is suppressed and sodium ion reduction produces sodium amalgam [11110-32-4J, HgNa. 

Chlorine—hydrogen ha2ards associated with mercury cells result from mercury pump failures heavy-metal impurities, particularly those with very low hydrogen overvoltage, ie. Mo, Cr, W, Ni excessively low pH of feed brine low NaCl concentrations in feed brine and poor decomposer operation, which leads to high sodium amalgam concentrations in the cell. 

An interesting field of application is the protection of tantalum against hydrogen embrittlement by electrical connection to platinum metals. The reduction in hydrogen overvoltage and the shift of the free corrosion potential to more positive values apparently leads to a reduced coverage by adsorbed hydrogen and thereby lower absorption [43] (see Sections 2.1 and 2.3.4). 

It has been suggested that the role of nickel (as NiAlj) is to provide sites of low hydrogen overvoltage, where cathodically liberated hydrogen may be liberated without disrupting the protective oxide . The distribution of such sites is apparently critical however, since high corrosion resistance is associated with a fine dispersion of the second phase, while the electronic conductivity of the film is probably also important . 

Cathodic inhibitors are passivating inhibitors they raise the hydrogen overvoltage, thus impeding the reduction of hydrogen ions at the cathode. They are suitable for inhibiting sulfuric or phosphoric acids. Examples are benzotriazole (at low concentrations) and alkylamines. 

Heterogeneous rate constants, 12, 113 Hofmeister sequence, 153 Hybridization, 183, 185 Hydrodynamic boundary layer, 10 Hydrodynamic modulation, 113 Hydrodynamic voltammetry, 90 Hydrodynamic voltammogram, 88 Hydrogen evolution, 117 Hydrogen overvoltage, 110, 117 Hydrogen peroxide, 123, 176... 

In the past, elevated voltages in electrolysis cells (a cell overvoltage) had been attributed mainly to polarization of the hydrogen evolution reaction. Hence the term hydrogen overvoltage became common for this kind of polarization. 

Historically, electrocatalytic science developed from investigations into cathodic hydrogen evolution, a reaction that can be reahzed at many metals. It was found in a number of studies toward the end of the nineteenth century that at a given potential, the rate of this reaction differs by severaf orders of magnitude between metals. In one of the first theories of hydrogen evofution, the recombination theory of hydrogen overvoltage, the rate of this reaction was finked directfy to the rate of the catalytic... 

Frumkin AN. 1961. Hydrogen overvoltage and adsorption phenomena. Part I. In Delahay P, Tobias CW. editors. Advances in Electrochemistry and Electrochemical Engineering. Volume 1. New York Interscience. 

The different factors responsible to influence the hydrogen overvoltage for a metal are ... 

Current density the hydrogen overvoltage increases linearly with the current density. 

Temperature the hydrogen overvoltage decreases with increasing temperature. It can be zero at higher temperatures. For example, the hydrogen overvoltage on nickel is zero at 90 °C. 

Pressure at elevated pressures, the value of the hydrogen overvoltage changes only very slightly but at lower pressures, it increases sharply on certain metals, as for example in the case of copper, nickel, and mercury cathodes. 

Cathode material the hydrogen overvoltage value varies from one cathode material to another. It can be quite high at certain electrodes made of lead and tin. 

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