Chlorine evolution

In many ways the evolution of chlorine is the anodic analog of hydrogen evolution. The overall reaction is  

The two main reaction mechanisms are analogous to the mechanisms for hydrogen evolution. The equivalent scheme to the Volmer-Tafel mechanism is  

Technical electrodes usually consist of a mixture of Ru02 and TiC 2 plus a few additives. They are called dimensionally stable anodes because they do not corrode during the process, which was a problem with older materials. These two substances have the same rutile structure with similar lattice constants, but RuC 2 shows metallic conductivity, while pure TiCU is an insulator. The reaction mechanism on these electrodes has not yet been established the experimental results are not compatible with either of the two mechanisms discussed above [4]. 

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The composition of the mixed metal oxide may well vary over wide limits depending on the environment in which the anode will operate, with the precious metal composition of the mixed metal oxide coating adjusted to favour either oxygen or chlorine evolution by varying the relative proportions of iridium and ruthenium. For chlorine production RuOj-rich coatings are preferred, whilst for oxygen evolution IrOj-rich coatings are utilised. ... 

The major electrochemical reaction at the anode surface is oxygen and chlorine evolution coupled with oxidation of the active carbon to carbon dioxide. Eventually all the carbon is removed from the anode coating and this allows perforation of the copper conductor leading to ultimate anode failure. 

The coating composition is iridium-rich to favour oxygen rather than chlorine evolution, and to assist in reducing the formation of acidic conditions at the anode-concrete interface. 

Activationless and barrierless regions cannot be realized in all reactions. Often or 1 are in regions of potentials where measurements are impossible or extremely difficult (e.g., because of parallel reactions). The crossover to the barrierless region has been demonstrated experimentally for cathodic hydrogen and anodic chlorine evolution at certain electrodes. Clear-cut experimental evidence has not yet been obtained for limiting currents appearing as a result of an activationless reaction. 

Anodic chlorine evolution by electrolysis of concentrated chloride solutions is used for the large-scale industrial production of chlorine. The cathodic reaction, which is the ionization of molecular chlorine, is used in certain types of batteries. 

Because of the considerable corrosivity of chlorine toward most metals, anodic chlorine evolution can only be realized for a few electrode materials. In industry, graphite had been used primarily for this purposes in the past. Some oxide materials, manganese dioxide for instance, are stable as well. At present the titanium-ruthenium oxide anodes (DSA see Chapter 28) are commonly used. 

The mechanism of anodic chlorine evolution has been studied by many scientists. In many respects this reaction is reminiscent of hydrogen evolution. The analogous pathways are possible. The most probable one is the second pathway, in which the adsorbed chlorine atoms produced are eliminated by electrochemical desorption, but sometimes the first pathway is also possible. As a rule the first step, which is discharge of the chloride ion, is the slow step. 

Anodic oxygen evolution (also anodic chlorine evolution, in solutions containing chlorides)... 

Appreciable interest was stirred by the sucessful use of nonmetallic catalysts such as oxides and organic metal complexes in electrochemical reactions. From 1968 on, work on the development of electrocatalysts on the basis of the mixed oxides of titanium and ruthenium led to the fabrication of active, low-wear electrodes for anodic chlorine evolution which under the designation dimensionally stable anodes (DSA) became a workhorse of the chlorine industry. 

It is interesting to note that cobalt cobaltite, C03O4, is a good catalyst, too, for anodic chlorine evolution. In this case, too, a correlation is observed between the reaction rate and the spinel s defect concentration (amount of nonstoichiometric oxygen). 

Oxides of Platinum Metals Anodes of platinum (and more rarely of other platinum metals) are used in the laboratory for studies of oxygen and chlorine evolution and in industry for the synthesis of peroxo compounds (such as persulfuric acid, H2S2O8) and organic additive dimerization products (such as sebacic acid see Section 15.6). The selectivity of the catalyst is important for all these reactions. It governs the fraction of the current consumed for chlorine evolution relative to that consumed in oxygen evolution as a possible parallel reaction it also governs the current yields and chemical yields in synthetic electrochemical reactions. 

Titanium dioxide is a catalytically inactive but rather corrosion-resistant material. Ruthenium dioxide is one of the few oxides having metal-like conductivity. It is catalytically quite active toward oygen and chlorine evolution. However, its chemical stability is limited, and it dissolves anodically at potentials of 1.50 to 1.55 V (RHE) with appreciable rates. A layer of mixed titanium and ruthenium dioxides containing 1-2 mg/cm of the precious metal has entirely unique properties in terms of its activity and selectivity toward chlorine evolution and in terms of its stability. With a working current density in chlorine evolution of 20 to 50mA/cm, the service life of such anodes is several years (up to eight years). 

XPS has been used by several authors to identify the surface and bulk composition of ruthenium based, valve metal stabilized DSA electrodes for chlorine evolution. Augustynski et al. [45] investigated the composition of Ru02-Ti02 electrodes before and after electrochemical treatment. They found a surface composition which deviated significantly from that of the bulk. The Ru/Ti ratio corresponded to 0.15 at the surface while in the bulk 0.28 was measured. Similar results were obtained by De Battisti et al. [46] for Ru02-Ti02 electrodes with different composition ratios on Ti substrates. Fig. 10 shows the Ru/Ti ratio for different solution compositions as a function of the depth. 

Janssen and Hoogland (J3, J4a) made an extensive study of mass transfer during gas evolution at vertical and horizontal electrodes. Hydrogen, oxygen, and chlorine evolution were visually recorded and mass-transfer rates measured. The mass-transfer rate and its dependence on the current density, that is, the gas evolution rate, were found to depend strongly on the nature of the gas evolved and the pH of the electrolytic solution, and only slightly on the position of the electrode. It was concluded that the rate of flow of solution in a thin layer near the electrode, much smaller than the bubble diameter, determines the mass-transfer rate. This flow is affected in turn by the incidence and frequency of bubble formation and detachment. However, in this study the mass-transfer rates could not be correlated with the square root of the free-bubble diameter as in the surface renewal theory proposed by Ibl (18). 

To summarise, AC methods have proved most successful where the system is straightforward and can be modelled analytically. By measurement over a wide range of frequencies the constants for the reaction steps constituting the model can be established and, particularly if adsorbed species are involved, AC methods have proved very powerful indeed, with a major area of application being in the study of metal passivation, as discussed in detail elsewhere in the book. An example of this behaviour in practice is provided by the work of Conway s and Hillman s groups on chlorine evolution at platinum. Several mechanisms for this reaction have been proposed, including both Volmer and Heyrovsky types ... 

On the basis of Tafel slope studies and potential relaxation transients, mechanism (1) has been suggested for Cl2 evolution at Pt, whereas chlorine evolution at the technically hydrated Ru02/Ti02 electrode appears to proceed by (3) or, possibly, (4). 

Even before the Flade potential the dissolution of iron is a complex process which has been thoroughly investigated by Epelboin and coworkers with AC impedance. The starting point is the same basic scheme as that proposed for chlorine evolution ... 

Krinhe, H.M. and Tributsch, H., Oxygen and chlorine evolution on ruthenium iron disulfide mediated by low energy photons, Ber. Bunsen. Phys. Chem., 88,10,1984. 

Dr T V Bommaraju 68 Dolphin Drive, Grand Island, NY 14072, USA. Deactivation of Thermally Formed RuO2 + Ti02 Coatings During Chlorine Evolution Mechanisms and Reactivation Measures. E-mail tilak ibm.net... 

Deactivation of Thermally Formed Ru02 + Ti02 Coatings During Chlorine Evolution Mechanisms and Reactivation Measures... 

Anodic polarisation behaviour of fresh and deactivated Ruffi oxide electrodes during chlorine evolution... 

Tafel slope for the chlorine evolution reaction follows an electrochemical desorption-type mechanism, it can be expressed [36, 37] in terms of the electrode surface coverage by the adsorbed Cl intermediates, 0aa, as ... 

At low coverage, the Tafel slope will be 2RT/3F or c. 40 mV, as observed on high at.% Ru electrodes. As the at.% Ru decreases, the number of Ru sites decrease, resulting in more coverage of the active Ru sites by 0ac]. Hence 0ad will approach 1 and the Tafel slope will tend to reach values of 2RT/F or 120 mV, thus potentially explaining the results in Fig. 5.3. Alternatively, this change in the Tafel slope may arise from an increase in the electrical resistivity of the low at.% Ru electrodes, during the course of the chlorine evolution reaction [35]. 

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