Alkali Electrolysis

Silicic acid,1 in a form which is soluble and chemically pure, can be obtained by employing a divided cell with alkali silicate in the anode compartment. Perforated electrodes are fitted against the diaphragm wall, and during electrolysis alkali diffuses into the cathode compartment whilst silicic acid remains in the anode compartment. Hydrated silica is thus separated in a pure form specially suitable for stabilising colloids. 

Whilst cations such as Fe +, Co +, Mn and Pb lower the yield in the Kolbe electrolysis, alkali and alkylammonium ions have no effect and are therefore preferably used as counterions for the carboxy-late. 

Kolbe reaction The pre >aration of saturated or unsaturated hydrocarbons by the electrolysis of solutions of the alkali salts of aliphatic carboxylic acids. Thus, ethanoic acid gives ethane,... 

Graphite reacts with alkali metals, for example potassium, to form compounds which are non-stoichiometric but which all have limiting compositions (for example K C) in these, the alkaU metal atoms are intercalated between the layers of carbon atoms. In the preparation of fluorine by electrolysis of a molten fluoride with graphite electrodes the solid compound (CF) polycarbon fluoride is formed, with fluorine on each carbon atom, causing puckering of the rings. 

English, potash - pot ashes L.. kalium, Arab qali, alkali) Discovered in 1807 by Davy, who obtained it from caushc potash (KOH) this was the first metal isolated by electrolysis. 

Uranium can be prepared by reducing uranium halides with alkali or alkaline earth metals or by reducing uranium oxides by calcium, aluminum, or carbon at high temperatures. The metal can also be produced by electrolysis of KUF5 or UF4, dissolved in a molten mixture of CaCl2 and NaCl. High-purity uranium can be prepared by the thermal decomposition of uranium halides on a hot filament. 

Anode Applications. Graphite has been used as the primary material for electrolysis of brine (aqueous) and fused-salt electrolytes, both as anode and cathode. Technological advances, however, have resulted in a dimensionally stable anode (DSA) consisting of precious metal oxides deposited on a titanium substrate that has replaced graphite as the primary anode (38—41) (see Alkali and chlorine products). 

Electrochemical processes require feedstock preparation for the electrolytic cells. Additionally, the electrolysis product usually requires further processing. This often involves additional equipment, as is demonstrated by the flow diagram shown in Figure 1 for a membrane chlor-alkali cell process (see Alkali AND chlorine products). Only the electrolytic cells and components ate discussed herein. 

There have been a number of cell designs tested for this reaction. Undivided cells using sodium bromide electrolyte have been tried (see, for example. Ref. 29). These have had electrode shapes for in-ceU propylene absorption into the electrolyte. The chief advantages of the electrochemical route to propylene oxide are elimination of the need for chlorine and lime, as well as avoidance of calcium chloride disposal (see Calcium compounds, calcium CHLORIDE Lime and limestone). An indirect electrochemical approach meeting these same objectives employs the chlorine produced at the anode of a membrane cell for preparing the propylene chlorohydrin external to the electrolysis system. The caustic made at the cathode is used to convert the chlorohydrin to propylene oxide, reforming a NaCl solution which is recycled. Attractive economics are claimed for this combined chlor-alkali electrolysis and propylene oxide manufacture (135). 

These facts would suggest that die electrolysis of molten alkali metal salts could lead to the inuoduction of mobile elecU ons which can diffuse rapidly through a melt, and any chemical reduction process resulting from a high chemical potential of the alkali metal could occur in the body of the melt, rather than being conhned to the cathode volume. This probably explains the failure of attempts to produce tire refractoty elements, such as titanium, by elecU olysis of a molten sodium chloride-titanium chloride melt, in which a metal dust is formed in the bulk of the elecU olyte. 

A complication of tire extension of tire electrolysis route for metal production, is tlrat in the case of the alkali metals, there is a significant solubility of the metal which would be produced by electrolysis in tire molten chloride. The dissolved metal provides very mobile electrons to tire melt, thus reducing the salt resistance, and dissipating the increased cuiTent, at a given applied potential, without the production of metal. To describe this phenomenon in... 

Since tire alkali and alkaline metals have such a high affinity for oxygen, sulphur aird selenium they are potentially useful for the removal of these iron-metallic elements from liquid metals with a lower affinity for these elements. Since the hairdling of these Group I and II elements is hazardous on the industrial scale, their production by molten salt electrolysis during metal rehning is an attractive alternative. Ward and Hoar (1961) obtained almost complete removal of sulphur, selenium and tellurium from liquid copper by the electrolysis of molten BaCla between tire metal which functioned as the cathode, and a graphite anode. 

Stress corrosion can arise in plain carbon and low-alloy steels if critical conditions of temperature, concentration and potential in hot alkali solutions are present (see Section 2.3.3). The critical potential range for stress corrosion is shown in Fig. 2-18. This potential range corresponds to the active/passive transition. Theoretically, anodic protection as well as cathodic protection would be possible (see Section 2.4) however, in the active condition, noticeable negligible dissolution of the steel occurs due to the formation of FeO ions. Therefore, the anodic protection method was chosen for protecting a water electrolysis plant operating with caustic potash solution against stress corrosion [30]. The protection current was provided by the electrolytic cells of the plant. 

EEC Directive on mercury (chlor-alkali electrolysis industry)... 

The scheme of the interaction mechanism (Equation 88) testifies to an electro-affinity of MeFe" ions. In addition, MeFe" ions have a lower negative charge, smaller size and higher mobility compared to MeF6X(n+1> ions. The above arguments lead to the assumption that the reduction to metal form of niobium or tantalum from melts, both by electrolysis [368] and by alkali metals, most probably occurs due to interaction with MeF6 ions. The kinetics of the reduction processes are defined by flowing equilibriums between hexa-and heptacoordinated complexes. 

A mercury cathode finds widespread application for separations by constant current electrolysis. The most important use is the separation of the alkali and alkaline-earth metals, Al, Be, Mg, Ta, V, Zr, W, U, and the lanthanides from such elements as Fe, Cr, Ni, Co, Zn, Mo, Cd, Cu, Sn, Bi, Ag, Ge, Pd, Pt, Au, Rh, Ir, and Tl, which can, under suitable conditions, be deposited on a mercury cathode. The method is therefore of particular value for the determination of Al, etc., in steels and alloys it is also applied in the separation of iron from such elements as titanium, vanadium, and uranium. In an uncontrolled constant-current electrolysis in an acid medium the cathode potential is limited by the potential at which hydrogen ion is reduced the overpotential of hydrogen on mercury is high (about 0.8 volt), and consequently more metals are deposited from an acid solution at a mercury cathode than with a platinum cathode.10... 

The alkali metals are the most violently reactive of all the metals. They are too easily oxidized to be found in the free state in nature and cannot be extracted from their compounds by ordinary chemical reducing agents. The pure metals are obtained by electrolysis of their molten salts, as in the electrolytic Downs process (Section 12.13) or, in the case of potassium, by exposing molten potassium chloride to sodium vapor ... 

Foreign cations can increasingly lower the yield in the order Fe, Co " < Ca " < Mn < Pb " [22]. This is possibly due to the formation of oxide layers at the anode [42], Alkali and alkaline earth metal ions, alkylammonium ions and also zinc or nickel cations do not effect the Kolbe reaction [40] and are therefore the counterions of choice in preparative applications. Methanol is the best suited solvent for Kolbe electrolysis [7, 43]. Its oxidation is extensively inhibited by the formation of the carboxylate layer. The following electrolytes with methanol as solvent have been used MeOH-sodium carboxylate [44], MeOH—MeONa [45, 46], MeOH—NaOH [47], MeOH—EtsN-pyridine [48]. The yield of the Kolbe dimer decreases in media that contain more than 4% water. 

A mixture of water/pyridine appears to be the solvent of choice to aid carbenium ion formation [246]. In the Hofer-Moest reaction the formation of alcohols is optimized by adding alkali bicarbonates, sulfates [39] or perchlorates. In methanol solution the presence of a small amount of sodium perchlorate shifts the decarboxylation totally to the carbenium ion pathway [31]. The structure of the carboxylate can also support non-Kolbe electrolysis. By comparing the products of the electrolysis of different carboxylates with the ionization potentials of the corresponding radicals one can draw the conclusion that alkyl radicals with gas phase ionization potentials smaller than 8 e V should be oxidized to carbenium ions [8 c] in the course of Kolbe electrolysis. This gives some indication in which cases preferential carbenium ion formation or radical dimerization is to be expected. Thus a-alkyl, cycloalkyl [, ... 

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