Inhibitors molybdates

Molybdate s low toxicity to fish and other aquatic life has helped to gain recognition in recent years as a corrosion inhibitor. Molybdate forms its protective film by adsorption on metal surfaces. When chloride and sulfate anions are present in the cooling water environment, they compete for adsorption, and high concentrations of molybdate are needed for effective passivation of the metal surfaces. In order to be able to reduce the molybdate concentration for cost-effective levels, synergistic blends are made up that include other inhibitors such as phosphorates and zinc. 

Molybdate is also known as an inhibitor of the important enzyme ATP sulfurylase where ATP is adenosine triphosphate, which activates sulfate for participation in biosynthetic pathways (56). The tetrahedral molybdate dianion, MoO , substitutes for the tetrahedral sulfate dianion, SO , and leads to futile cycling of the enzyme and total inhibition of sulfate activation. Molybdate is also a co-effector in the receptor for steroids (qv) in mammalian systems, a biochemical finding that may also have physiological implications (57). 

Both molybdate and orthophosphate are excellent passivators in the presence of oxygen. Molybdate can be an effective inhibitor, especially when combined with other chemicals. Orthophosphate is not really an oxidizer per se but becomes one ia the presence of oxygen. If iron is put iato a phosphate solution without oxygen present, the corrosion potential remains active and the corrosion rate is not reduced. However, if oxygen is present, the corrosion potential iacreases ia the noble direction and the corrosion rate decreases significantly. 

The second class of anodic inhibitors contains ions which need oxygen to passivate a metal. Tungstate and molybdate, for example, requke the presence of oxygen to passivate a steel. The concentration of the anodic inhibitor is critical for corrosion protection. Insufficient concentrations can lead to pitting corrosion or an increase in the corrosion rate. The use of anodic inhibitors is more difficult at higher salt concentrations, higher temperatures, lower pH values, and in some cases, at lower oxygen concentrations (37). 

Chemical inhibitors, when added in small amounts, reduce corrosion by affecting cathodic and/or anodic processes. A wide variety of treatments may be used, including soluble hydroxides, chromates, phosphates, silicates, carbonates, zinc salts, molybdates, nitrates, and magnesium salts. The exact amount of inhibitor to be used, once again, depends on system parameters such as temperature, flow, water chemistry, and metal composition. For these reasons, experts in water treatment acknowledge that treatment should be fine tuned for a given system. 

Literature Recent additions to the literature on the principles and practice of inhibition include books concerned with the subject as a whole, and reports of conferences and papers, or reports concentrating on particular aspects of the subject. Books include the volume by the late Professor I. L. Rozenfel d and collected data in the form of references, patents etc. from various sources Conferences include the recent quinquennial events at the University of Ferrara S, each providing substantial contributions to all aspects of corrosion inhibition. The uses of molybdates as inhibitors have been reviewed by Vukasovich and Farr in a paper with 221 references and test methods for inhibitors in a report from the European Federation of Corrosion with 49 references . 

There has been much activity in this field of corrosion inhibition in recent years which appears to have been prompted by health and safety requirements. As with engine coolants, the use of nitrites, particularly where amines may also be present, needs to be considered carefully. Nitrites have been widely used in cutting, grinding, penetrating, drawing and hydraulic oils. Suggested replacements for nitrites and/or amines make use, inter alia, of various borate compounds, e.g. monoalkanolamide borates. Molybdates have also been proposed in conjunction with other inhibitors, e.g. carbox-ylates, phosphates, etc . Water-based metalworking fluids usually contain other additives in addition to corrosion inhibitors, e.g. for hard-water stability, anti-foam, bactericidal proderties and so on. Thus, claims are made for oil-in-water emulsions with bactericidal and anti-corrosion properties. 

The primary types of corrosion inhibitor treatments employed are generally based on inorganic chemicals such as sodium nitrite (together with combinations of borate, silicate, molybdate, and phosphate) and the addition of even 2 to 3 pints (0.95-1.4 liters) to a boiler can immediately raise the TDS in the BW to a level at which priming can occur. Secondary problems include an associated rise in the level of BW suspended solids and sludge. 

Where water softening is provided and there is no reduction in system water TDS, treatments are primarily based on inorganic corrosion inhibitor blends (nitrite, molybdate, etc.). Under these circumstances, there is no benefit in using an expensive organic oxygen scavenger to keep the TDS level low, and a common chemical such as catalyzed sodium sulfite may be used. 

Anodic inhibitor programs These programs are based on ingredients such as nitrite, silicate, and molybdate chemistries and usually are formulated as light-duty multifunctional programs in HW heating and LP steam boiler systems. 

Anodic inhibitor programs are generally single-drum, multifunctional products and commonly include nitrite and molybdate in addition to other inhibitors and ingredients. The inhibitors provide a corrosion stifling effect resulting from a buildup of corrosion products and by-products on the metal surface. 

Apart from nitrite and molybdate, silicate is commonly employed in anodic inhibitor programs, although seldom as the primary inhibitor. Both silicates and molybdates provide benefits of synergistic inhibition and also help to reduce corrosion risks through softer waters and multimetal systems. 

Molybdate is always used in conjunction with other anion inhibitors, not only to reduce the cost of the inhibitor program, but also because, through synergism, much-improved barrier films are produced when coupled with nitrite or silicate. 

Molybdate also functions as an effective inhibitor by slowing down pitting corrosion through a mechanism of adsorption onto the pit wall. 

For larger, more complex LPHW systems and for LP steam heating systems, silicates are seldom used alone but are formulated with nitrite or molybdate inhibitors to provide synergistic corrosion protection. 

Although azoles are commonly thought of as only yellow metal inhibitors, they are, in fact, used for corrosion inhibition in a wider range of metals such as steel and aluminum. They also are often incorporated in molybdate-based programs to both provide some synergism and reduce the level of molybdate required. Azoles also are employed in many types of organic-based formulations, where they improve the overall protection of steel and reduce the risk of corrosion of yellow metals due to the corrosive action of some common phosphonates. 

As a consequence, it is not possible to devise a single class of anodic inhibitor formulation that satisfies all water treatment requirements. Rather, there several types of formulations, and some formulators may offer each of these products in different strengths, with or without oxygen scavengers and indicator dyes in their blends. As examples, a nitrite/sUicate formulation and a molybdate/nitrite formulation are provided here ... 

The most common corrosion inhibitors, which may form protective films on the metal surfaces, are borates, molybdates, nitrates, nitrites, phosphates, silicates, amines, triazoles, and thiazioles (e.g., monoethanolamine, urotropin, thiodiglycol, and mercaptobenzothiazole). The addition of such inhibitors does not effectively protect against corrosion [137]. Some corrosion inhibitors are shown in Figure 14-3. 

Figures 11(a) and 11(b) [112] show the variation of Ni-Ge-P deposition rate and Ge content as a function of aspartic acid and Ge(IV) concentration, respectively. A relatively low P content, ca. 1-2 at%, was observed in the case of films exhibiting a high concentration of Ge (> 18 at%). Like other members of its class, which includes molybdate and tungstate, Ge(IY) behaves a soft base according to the hard and soft acids and bases theory (HSAB) originated by Pearson [113, 114], capable of strong adsorption, or displaying inhibitor-like behavior, on soft acid metal surfaces. In weakly acidic solution, uncomplexed Ge(IV) most probably exists as the hydrated oxide, or Ge(OH)4, which, due to acid-base reactions, may be more accurately represented as [Gc(OH)4 nO ] ".

Oxyanions also affect the coordination chemistry of the metal center (84). Molybdate and tungstate are tightly bound noncompetitive inhibitors (Ki s of ca. 4 (iM) (85). These anions bind to the reduced form of the enzyme, changing the rhombic EPR spectrum of the native enzyme to axial (Figure 1) and affecting the NMR shifts observed (84,85). Comparisons of the ENDOR spectra of reduced uterofenin and its molybdate complex show that molybdate binding causes the loss of iH features which are also lost when the reduced enzyme is placed in deuterated solvent (86). These observations suggest that molybdate displaces a bound water upon complexation. 

Among molybdate salts, sodium and ammonium molybdates have commercial applications. The normal salt, sodium orthomolyhdate, Na2 M0O4, is used in pigments. It also is used as a corrosion inhibitor and as an additive to soil. Lead molybdate, Pb M0O4, occurs in nature as mineral ulfenite, from which molybdenum metal is recovered. 

Anodic inhibitors such as nitrites, chromates and molybdates are strong oxidizing passivators. They strengthen the protective oxide layer over the steel which otherwise would break down in the presence of chloride ions. The mechanism involves a redox reaction in which the chloride and nitrite ions engage in competing reactions the inhibitor is reduced and steel becomes oxidized to iron oxide as follows ... 

Although molybdate compounds have been advocated for corrosion inhibition purposes they have not been used as inhibitors in concrete practice. Experiments to ascertain the synergistic effect of a calcium-nitrite- sodium-molybdate combination (4.5 parts to 1 part) on corrosion of steel in concrete [64] showed that at the inhibitor-chloride ratio of 1 11 the combined admixture protected steel from corrosion and that it was more effective than when calcium nitrite was used alone. 

Phosphates, molybdates, and (at high pH) silicates act as anodic inhibitors much as do alkalis, except that the iron oxides/hydroxides formed on anodic sites then contain some PO43-, M0O42-, or Si044- ( basic iron phosphates, etc.). These inhibitors require the presence of 02 to produce basic iron(III) phosphate, molybdate, or silicate films, whereas oxidizing anions such as chromates and nitrites oxidize Fe2+ (aq) rapidly to insoluble iron(III) oxides on anodic sites. Dianodic inhibitors combine complementary inhibition mechanisms for example, sodium triphosphate may be used with sodium chromate, or sodium molybdate with NaN02. 

Utility systems for equipment and space heating and cooling frequently use heavy metal corrosion inhibitors in their heat transfer fluids. Chromate compounds are among the best corrosion inhibitors available. Nonchromate inhibitors that have proved to be feasible substitutes include polyphosphates, organophosphates, zinc, molybdates, and aromatic azoles. Some of these compounds have their own environmental impacts, however. Azoles, for instance, can be quite dangerous to human health. 

Molybdate - [COLORANTS FORPLASTICS] (Vol 6) -lead detection [LEAD] (Vol 15) -role m H202 decomposition [HYDROGEN PEROXIDE] (Vol 13) -use as corrosion inhibitor [CORROSION AND CORROSION CONTROL] (Vol 7)... 

Restriction of the molybdenum intake by young rats in a synthetic purified casein diet results in a decreased level of tissue, particularly small intestinal, xanthine oxidase. The enzyme levels arc rest tired to normal by the inclusion of sodium molybdate and other molybdate compounds. Sodium tungstate is a competitive inhibitor of molybdate, and dietary intakes of tungstate greatly reduce the molybdenum and xanthine oxidase concentrations in tissues. 

Effects of inhibitors. All activities tested were inhibited by molybdate (33, 37), citrate (118), oxalate (118), and other metal-binding agents (119, 120), L-cysteine (48, 114, H9, 120), dithiothreitol (46, 114), and phlorizin (101). Where determined, Kt values calculated for the inhibition of the various activities by a given compound agreed closely (101, 118-120). 

Offline passivation involves treatment of equipment currently out of service. Treatment levels are typically higher consequently, passivation is completed more quickly. Passivation of nonchromate treatment generally uses either a polyphosphate, zinc, molybdate or other nonchromate-based inhibitor in combination with various surface-active cleaning agents. The passivation solution should be disposed of after the pretreatment stage, rather than dumped back into the cooling system where the potential for fouling can exist due to the precipitation of pretreatment compounds such as zinc or phosphate. Table 8.1 outlines both online and offline pretreatment procedures. 

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