Hydrogen cathodes materials

Batteries. Many batteries intended for household use contain mercury or mercury compounds. In the form of red mercuric oxide [21908-53-2] mercury is the cathode material in the mercury—cadmium, mercury—indium—bismuth, and mercury—zinc batteries. In all other mercury batteries, the mercury is amalgamated with the zinc [7440-66-6] anode to deter corrosion and inhibit hydrogen build-up that can cause cell mpture and fire. Discarded batteries represent a primary source of mercury for release into the environment. This industry has been under intense pressure to reduce the amounts of mercury in batteries. Although battery sales have increased greatly, the battery industry has aimounced that reduction in mercury content of batteries has been made and further reductions are expected (3). In fact, by 1992, the battery industry had lowered the mercury content of batteries to 0.025 wt % (3). Use of mercury in film pack batteries for instant cameras was reportedly discontinued in 1988 (3). 

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. 

A simple electrochemical flow-through cell with powder carbon as cathodic material was used and optimized. The influence of the generation current, concentration of the catholyte, carrier stream, flow rate of the sample and interferences by other metals on the generation of hydrogen arsenide were studied. This system requires only a small sample volume and is very easily automatized. The electrochemical HG technique combined with AAS is a well-established method for achieving the required high sensitivity and low detection limits. 

Nevertheless, water is decomposed with evolution of hydrogen but under controlled conditions and with a reasonable reaction rate. With water as the active cathode material, the battery system—used in military underwater applications—can be designed as (-) Li / KOH / H20 (+) [19]. The... 

The nature of the cathode material is not critical in the Kolbe reaction. The reduction of protons from the carboxylic acid is the main process, so that the electrolysis can normally be conducted in an undivided cell. For substrates with double or triple bonds, however, a platinum cathode should be avoided, as cathodic hydrogenation can occur there. A steel cathode should be used, instead. 

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. 

This technique is applied to mixtures of metal ions in an acidic solution for the purpose of electroseparation only the metal ions with a standard reduction potential above that of hydrogen are reduced to the free metal with deposition on the cathode, and the end of the reduction appears from the continued evolution of hydrogen as long as the solution remains acidic. Considering the choice of the cathode material and the nature of its surface, it must be realized that the method is disturbed if a hydrogen overpotential occurs in that event no hydrogen is evolved and as a consequence metal ions with a standard reduction potential below that of hydrogen will still be reduced a classic example is the electrodeposition of Zn at an Hg electrode in an acidic solution. 

Further evidence for surface effects upon the stereochemistry of electrochemical reduction of ketones comes from the discovery that the nature of the cathode material may effect stereochemistry. Reduction of 2-methylcyclo-hexanone affords pure trans-2-methylcyclohexanone at mercury or lead cathodes, a mixture of cis and trans alcohols (mostly trans) at nickel, and pure cis alcohol at copper 81 >. Reduction could not be effected at platinum presumably hydrogen evolution takes place before the potential necessary for reduction of the ketone can be reached. 

A further argument for the choice of the cathode material may be the catalytic activity for hydrogenation reactions. Vice versa, this is also important if the cathode is the counter electrode - usually evolving hydrogen - where hydrogenation reactions are undesired. 

Cathode Iron is a very cheap cathode material with a relatively low hydrogen overvoltage (e.g. [25]). It is of interest for industrial applications. In order to avoid corrosion during interruption of the current, stainless steel may be suitable, especially in laboratory cells where the increased electrical resistance and hydrogen overvoltage are irrelevant. 

The stereochemical outcome of cathodic hydrogenation of acetylenes to the corresponding aUcenes changes strongly with the reaction conditions, such as supporting electrolyte, solvent, and cathode material. 

Mercury, lead, cadmium and graphite are commonly used cathode materials showing large overpotentials for hydrogen evolution in aqueous solution. Liquid mercury exhibits a clean surface and is very convenient for small-scale laboratory use. Sheet lead has to be degreased and the surface can be activated in an electrochemical oxidation, reduction cycle [3, 22], Cadmium surfaces are conveniently prepared by plating from aqueous cadmium(ii) solutions on a steel cathode. 

Platinum and carbon are frequently used as counter electrode materials for both anode and cathode. Platinum is resistant to corrosion while carbon is cheap and can be discarded after use. Nickel is a suitable counter cathode material in aqueous solution because of the low overpotential for hydrogen evolution. Titanium coated with platinum and then over coated with mthenium dioxide is a stable counter anode material with a low overpotential for oxygen evolution. 

The electrolyte consisted of anhydrous hydrogen fluoride with 0.1 M sodium fluoride. The anode was a platinum grid (3 cm2), the cathode material was also platinum and the reference electrode was Cu/CuF2. The electrolysis of 1-bromopropane was carried out at a potential of 1.65 V. The products were 2-fluoropropane(20%), 1, l-difluoropropane(30 %), and l-bromo-2-fluoropropane (40 %), as well as lesser amounts of 1,2-dibromo-3-fluoropropane, 2-bromo-l, 1 -difluoropropanc, 1,2-dibromopropane, and 1,3-dibromopropane. 

In nonaqueous, aprotic media, the hydrogen overvoltage does not play any role. Commonly used cathode materials are lead, aluminum, copper, titanium, steel, and carbon of all kinds. 

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