Anode passivation

Acid Coolers. Cast Hon trombone coolers, once the industry standard (101), are considered obsolete. In 1970, anodically passivated stainless steel sheU and tube acid coolers became commercially available. Because these proved to have significant maintenance savings and other advantages, this type of cooler became widely used. Anodic passivation uses an impressed voltage from an external electrical power source to reduce metal corrosion. 

Anodic passivation and its appHcation to sulfuric acid equipment such as stainless steel acid coolers and carbon steel storage tanks has been weU studied (102—104). More recently, sheU and tube coolers made from Sandvik SX or Saramet have been installed in several acid plants. These materials do not requHe anodic protection. 

Precipita.tingInhibitors. As discussed earlier, the localized pH at the cathode of the corrosion cell is elevated due to the generation of hydroxide ions. Precipitating inhibitors form complexes that are insoluble at this high pH (1—2 pH units above bulk water), but whose deposition can be controlled at the bulk water pH (typically 7—9 pH). A good example is zinc, which can precipitate as hydroxide, carbonate, or phosphate. Calcium carbonate and calcium orthophosphate are also precipitating inhibitors. Orthophosphate thus exhibits a dual mechanism, acting as both an anodic passivator and a cathodic precipitator. 

Two areas of passivity are located in Fig. 2-2 where Fe has a very low corrosion rate. In contrast to cathodically protected metals in groups I and II, the corrosion rate of anodically passivated metals in groups III and IV cannot in principle be zero. In most cases the systems belong to group IV where intensified weight loss corrosion or local corrosion occurs when U > U" There are only a few metals belonging to group III e.g., Ti, Zr [44] and A1 in neutral waters free of halides. 

There are basically three main types of inorganic inhibitors used in industry anodic passivating inhibitors, cathodic inhibitors and cathodic precipitators. 

Anodic passivation also allows titanium to be employed as a Jig for aluminium anodising baths ", because the protective anodic film formed on titanium allows passage of electronic current to the metal contact while virtually suppressing flow of ionic current through the anodically-formed surface film. This aspect is discussed in more detail in relation to special applications. 

Because of its good performance in mineral acids, there is little need or incentive to invoke anodic passivation techniques for zirconium. The metal can be anodised in sulphuric acid, but, again in contrast to the behaviour of titanium, it does not form a stable anodic film in chloride solutions, and even in neutral sodium chloride, zirconium rapidly corrodes if an anodic potential of 2 V is applied. 

Tests have indicated failure to form PbO rapid deterioration, although at 100 Am it slows down after several weeks. Increasing silver content results in some improvement ". Anode passivated in 0-163 ohm m water continues to operate whilst PbO, is undamaged "". ... 

The use of the potentiostatic method has helped to show that the process of self-passivation is practically identical to that which occurs when the metal is made anodically passive by the application of an external current" . The polarisation curve usually observed is shown schematically in Fig. 19.37a. Without the use of a potentiostat, the active portion of the curve AB would make a sudden transition to the curve DE, e.g. along curve AFE or AFD, and observation of the part of the curve BCDE during anodic polarisation was not common until the potentiostat was used. 

Subsequent deposition and dissolution of lithium at the anodically passivated electrode by CV in the range -1000 mV to 6000 mV versus Li was successful, showing that the passivating film at the electrode is only impermeable for the anions, but not for lithium ions however, the amount of lithium deposited decreases, with cycle number. 

In these simpler types of boiler plants, corrosion protection generally is provided solely by the use of chemical treatments containing anodic passivators and alkali. Under conditions in which the (oxygen-containing) MU water requirement is expected to be very low, no specific oxygen scavenger is typically employed. This is often not the case in practice, however, for various reasons such as inadequate preventative maintenance, poor BD practice, the infiltration of air or oxygen, or other such reason. 

As an anodic passivating agent, nitrite enhances the formation of magnetite film and produces reducing conditions. It is simple to detect and test, but the high feed level and reserve requirement limit this product to small LPHW and LP steam boiler heating systems. 

Figure 5. Thickness of the anodic passivating film formed on iron at various potentials.6 9 Lbl and Lr, are the thicknesses of the barrier layer and the precipitated layer, respectively. Temperature is 25°C. , in a 150 mol m 3 phosphate buffer solution at pH 1.85 O, in a 300 mol m 3 borate buffer solution at pH 8.2. (From N. Sato, K. Kudo, and T. Noda, Z Phys. Chem. N. F. 98,271,1975, Fig. 5, reproduced with permission and N. Sato, K. Kudo, and R. Nishimura, / Elec-trochem. Soc, 123,1420,1976, Fig. 1. Reproduced with permission of the Electrochemical Society, Inc.)...

Peter studied in detail the growth of anodic CdS films on the Cd electrode in similar solutions [31], as well as the processes that occur at the Cd/solution and CdS/solution interfaces [32], According to the linear sweep voltammetry, three characteristic regions could be distinguished revealing the essential features of the anodic passivation of cadmium in alkaline sulfide solutions (a) the monolayer... 

Using the unique four-electrode STM described above, Bard and coworkers (Lev, 0. Fan, F-R.F. Bard, A.J. J. Electroanal. Chem.. submitted) have obtained the first images of electrode surfaces under potentiostatic control. The current-bias relationships obtained for reduced and anodically passivated nickel surfaces revealed that the exponential current-distance relationship expected for a tunneling-dominated current was not observed at the oxide-covered surfaces. On this basis, the authors concluded that the nickel oxide layer was electrically insulating, and was greater than ca. 10 A in thickness. Because accurate potential control of the substrate surface is difficult in a conventional, two-electrode STM configuration, the ability to decouple the tip-substrate bias from... 

Anodically colored electrochromic inorganic films, 6 579-580 Anodic cleaning, 9 783, 785 Anodic (passivating) corrosion inhibitors, 26 144... 

An illuminated area on n-type Si is anodically passivated in alkaline solutions for potentials in excess of PP, whereas an area kept in the dark is not passivated and is therefore etched with the OCP etch rate. 

Anodic passivation can be observed easily and clearly with iron group metals and alloys as shown in Fig. 11-10. In principal, anodic passivation occurs with most metals. For instance, even with noble metals such as platinum, which is resistant to anodic dissolution in sulfuric acid solutions, a bare metal surface is realized in the active state and a superficial thin oxide film is formed in the passive state. For less noble metals of which the affinity for the oxide formation is high, the active state is not observed because the metal surface is alwa covered with an oxide film. 

In a recent review, Tao etal. [34] describe the partial fluorination and the perfluorination of organics with particular emphasis on medically important compounds and pharmaceuticals. The selective electrofluorination (SEF) of olefins and active methylene groups is reviewed by Noel et al. [35] In the case of heterocycles, nuclear fluorination is known to be the predominant process. However, in aromatic compounds, nuclear substitution as well as addition proceeds simultaneously, leading to the formation of a mixture of products. The influence of solvents, supporting electrolytes, and adsorption on product yield and selectivity is summarized and evaluated. Dimethoxyethane is found to be a superior solvent for SEF processes. Redox mediators have been employed to minimize anode passivation and to achieve better current efficiencies. 

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