Electrolysis demonstration

Note You may have seen electrolysis demonstrated in class or shown on a videodisc or on a CD-Rom. This is often used to show the 2 1 mole ratio of hydrogen gas to oxygen gas that is produced. ... 

Apart from these theoretical investigations and experiments on static models, investigators have studied dynamic gas evolving electrodes. Hine and co-workers,62 in early work on bubble resistance in chlor-alkali electrolysis, demonstrated the effect of electrode orientation on ohmic losses. Hine et reported the... 

Solutions of nitric acid in 100% sulphuric acid have a high electrical conductivity. If nitric acid is converted into a cation in these solutions, then the migration of nitric acid to the cathode should be observed in electrolysis. This has been demonstrated to occur in oleum and, less conclusively, in concentrated acid, observations consistent with the formation of the nitronium ion, or the mono- or di-protonated forms of nitric acid. Conductimetric measurements confirm the quantitative conversion of nitric acid into nitronium ion in sulphuric acid. ... 

A fused-salt electrolysis process has been demonstrated (30). Carbon dioxide is introduced to the cathode area of a melt of 60 wt % LiCl—40 wt % Li2C02 at 550°C. The carbon dioxide reacts with hthium oxide which is produced by electrolysis. Oxygen is released at the anode and carbon plates onto the cathode. The reaction requites a potential of 4.5 V. The reactions ate as follows ... 

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. 

Faraday is better known in chemistry for his laws of electrolysis and in physics for proposing the relationship between electric and magnetic fields and for demonstrating the principle of electromagnetic induction. 

Coulometric measurements demonstrated the formation of the thioether with an electricity consumption of one Faraday per mole. However, the thioether yield was only of the order of 50% and, in addition, the presence of sulphinate ion in the electrolysis solutions was shown by methylation with CH3I, when methyl phenyl sulphone was formed and determined. 

Wurster, R. Water Electrolysis and Solar Hydrogen Demonstration Projects 27... 

Recently it was demonstrated that a platinum black-PTFE electrode, originally designed for a fuel cell, is excellent for the chlorination of double bonds and, depending on the other electrolysis conditions, it was possible to isolate the dichlorocompound or the chlorohydrin (Danger and Yurchak, 1970). Moreover, if a chlorine cathode is used, the overall process occurs with a net output of energy, i.e. the cell may do external work and the procedure has been named electrogenerative chlorination . 

Faraday, in 1834, was the first to encounter Kolbe-electrolysis, when he studied the electrolysis of an aqueous acetate solution [1], However, it was Kolbe, in 1849, who recognized the reaction and applied it to the synthesis of a number of hydrocarbons [2]. Thereby the name of the reaction originated. Later on Wurtz demonstrated that unsymmetrical coupling products could be prepared by coelectrolysis of two different alkanoates [3]. Difficulties in the coupling of dicarboxylic acids were overcome by Crum-Brown and Walker, when they electrolysed the half esters of the diacids instead [4]. This way a simple route to useful long chain l,n-dicarboxylic acids was developed. In some cases the Kolbe dimerization failed and alkenes, alcohols or esters became the main products. The formation of alcohols by anodic oxidation of carboxylates in water was called the Hofer-Moest reaction [5]. Further applications and limitations were afterwards foimd by Fichter [6]. Weedon extensively applied the Kolbe reaction to the synthesis of rare fatty acids and similar natural products [7]. Later on key features of the mechanism were worked out by Eberson [8] and Utley [9] from the point of view of organic chemists and by Conway [10] from the point of view of a physical chemist. In Germany [11], Russia [12], and Japan [13] Kolbe electrolysis of adipic halfesters has been scaled up to a technical process. 

Non-Kolbe electrolysis may lead to a large product spectrum, especially when there are equilibrating cations of about equal energy involved. However, in cases where the further reaction path leads to a particularly stabilized carbocation and either elimination or solvolysis can be favored, then non-Kolbe electrolysis can become an effi-yient synthetic method. This is demonstrated in the following chapters. 

Electrolysis in molten salts obeys Faraday s laws, although the demonstration of their validity is sometimes very difficult, as mentioned earlier. In fact, often during the electrolysis of molten electrolytes there are considerable and not readily avoidable losses in the current efficiency. Some of the causes of such losses are (i) evaporation or distillation of metal separated in the molten state (ii) secondary reactions between the separated molten metal and the materials with which it comes into contact and (iii) the solubility of the metal in the electrolyte. The latter cause appears to be the main one leading to a loss in current efficiency. 

R. Clausius (1857) demonstrated the presence of ions in solutions and verified the validity of Ohm s law down to very low voltages (by electrolysis... 

For HCI electrolysis the cathodic reaction product is water, which is easily drained through the ODC without affecting the membrane water content. Consequently, the ODC can be attached directly to the membrane and pressure compensation is not necessary. The cell concept, which was developed in another co-operation with DeNora, could not be simpler - the basic cell principle is shown in Fig. 4.6. Initial laboratory tests conducted in 1994 at Bayer on the basis of old GE developments [4] demonstrated the feasibility of HCI electrolysis with ODC and the potential for a reduction of the cell voltage to about one-third of present values. 

Owing to the fact that nearly all the heat generated by this type of electrolyser has to be dissipated via the anolyte flow, for the full industrial-scale demonstration electrolyser with an element size 2.5 m2 it was decided to use the bubble jet system [3], which was successfully tested previously with the chlor-alkali method. For FIC1 electrolysis, which from the material side is optimised to an approximate operation temperature of 60°C, an intense vertical temperature-profile flattening is essential to reduce the external flow rates and to allow rather low anode-side inlet temperatures. The intensive vertical mixing with the bubble jet proved to be suitable for this purpose. 

Fig. 4.8 The demonstration plant for HCI electrolysis with ODC at start-up on 4 January 2000.

---