Corrosion inhibitors nitrites

Unfortunately, not all combinations of chemical additives in water-based fluids are completely compatible, and side reactions leading to various byproducts have been noted. The best known of these side reactions is the reaction between the corrosion inhibitor nitrite and the emulsifiers di- and triethanolamine (7) to form N-nitrosodiethanolamine (NDE1A), a nitrosamine reported to have carcinogenic activity (8, 9, 10). In fact, most nitrosamines are carcinogenic, and no animal species which has been tested is resistant to nitrosa mine-induced cancer. Although there is no direct evidence that firmly links human cancer to nitrosamines, it is unlikely that humans should be uniquely resistant. 

Nitrites occur as the simple NO anion. It is formed particularly by biochemical oxidation of ammonia nitrogen or biochemical reduction of nitrates. Some industrial wastewaters are very rich in nitrites, for example those from the production of some dyestuffs or from engineering works employing cutting liquids for cooling of machine tools such liquids contain nitrites as corrosion inhibitors. Nitrites in waters occur with nitrates and ammonia nitrogen only at low concentrations since they are biochemically and chemically labile. In clean ground- and surface waters only trace... 

Uses Rust/corrosion inhibitor for water-based paints/coatings, water-based industrial primers, water-reducible alkyds Features Flash rust/in-can corrosion inhibitor nitrite-free provides belter dried film corrosion protection than water-sol. salts Properties Yel. clear liq. disp. in water sol. in glycol ether, insol. in min. spirits sp.gr. 1.06 dens. 1040 kg/m bulk dens. 8.83 Ib/gal vise. 200 mPa s max. flash pt. > 52 C pH 8.0-10.0 anionic Use Level 0.1 -0.6% (on total formulation wt.)... 

Cyclohexylamine is miscible with water, with which it forms an azeotrope (55.8% H2O) at 96.4°C, making it especially suitable for low pressure steam systems in which it acts as a protective film-former in addition to being a neutralizing amine. Nearly two-thirds of 1989 U.S. production of 5000 —6000 t/yr cyclohexylamine serviced this appHcation (69). Carbon dioxide corrosion is inhibited by deposition of nonwettable film on metal (70). In high pressure systems CHA is chemically more stable than morpholine [110-91-8] (71). A primary amine, CHA does not directiy generate nitrosamine upon nitrite exposure as does morpholine. CHA is used for corrosion inhibitor radiator alcohol solutions, also in paper- and metal-coating industries for moisture and oxidation protection. 

Nitrate and Nitrite. Nitrate is usually present in trace quantities in surface waters but occasionally occurs in high concentrations in some groundwaters. If present in excessive amounts, it can contribute to the illness infant methemoglobinemia. Nitrate is an essential nutrient for many photosynthetic autotrophs. Nitrite is an intermediate in the reduction of nitrate as well as in the oxidation of ammonia it is also used as a corrosion inhibitor in some industrial processes. 

Dissolved mineral salts The principal ions found in water are calcium, magnesium, sodium, bicarbonate, sulphate, chloride and nitrate. A few parts per million of iron or manganese may sometimes be present and there may be traces of potassium salts, whose behaviour is very similar to that of sodium salts. From the corrosion point of view the small quantities of other acid radicals present, e.g. nitrite, phosphate, iodide, bromide and fluoride, have little significance. Larger concentrations of some of these ions, notably nitrite and phosphate, may act as corrosion inhibitors, but the small quantities present in natural waters will have little effect. Some of the minor constituents have other beneficial or harmful effects, e.g. there is an optimum concentration of fluoride for control of dental caries and very low iodide or high nitrate concentrations are objectionable on medical grounds. 

Soldered brass seldom gives trouble. In radiators, antifreeze solutions have been alleged to cause corrosion, possibly because materials such as ethylene glycol sometimes detach protective deposits. Sodium nitrite, valuable as a corrosion inhibitor for other metals in a radiator, tends to attack solders, but sodium benzoate is safe and, in addition, protects the soldered joint against the action of nitrites. In an investigation of other inhibitors in ethylene glycol solutions, 1% borax, either alone or in combination with 0-1% mercaptobenzothiazole, appeared to be satisfactory. 

Sometimes it is possible to add corrosion inhibitors to an aqueous product that is to remain in contact with tinned steel. The normal inhibitors used for protecting steel, e.g. benzoate, nitrite, chromate, etc. are suitable, provided that they are compatible with the product and that the pH is not raised above 10. In a closed container with an air-space, such inhibitors will not protect the zone above the water-line, and possibly not the water-line zone itself, against condensate. Volatile inhibitors have been used to give protection to these areas. 

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. 

Anodic polarization also may occur. Typically, this begins with the formation of a thin, impervious oxide film, chemisorbed at the anode (as on the surface of stainless steels). However, for most metals used in boiler plant systems this chemisorption process must be aided by anodic corrosion inhibitors to reduce corrosion rates to tolerable levels. An example is the application of nitrite-based inhibitors, widely used in HW heating systems. 

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. 

NOTE Sodium nitrite-based corrosion inhibitors are commonly employed as corrosion inhibitors for LPHW systems however, they can be subject to... 

It is not usual for unopened drums of nitrite-based chemical to degrade, and the product should remain in good condition for several years. However, it is possible for tannin-based corrosion inhibitors to degrade, even in unopened drums. Under warm conditions (such as storage in a boil-erhouse) and in the absence of a small amount of suitable microbiocide in the formulation, plastic drums containing tannin products may swell considerably because of microbiological degradation and gas formation. Care is needed to avoid accidents. 

In a similar study, Gray et al. (60) investigated the possible formation of N-nitrosamines in heated chicken frankfurters which been prepared with various levels of nitrite (0-156 mg/kg). As expected, apparent N-nitrosamine levels increased with increasing concentrations of nitrite, but did not exceed 4 yg/kg except for two samples which contained 8 and II yg/kg of NMOR. The presence of these relatively high levels of NMOR was confirmed by mass spectrometry and raised the question as to its mode of formation. It was shown to be due to the morpholine present in the steam entering the smokehouse, as this amine is commonly used as a corrosion inhibitor in steam process equipment ( ). The detectable levels of NMOR in the Canadian study ( ) were also attributed in part to the use of morpholine as an anti-corrosion agent in the steam supply (62). 

The presence of Increased eunounts of NDPA in trlfluralin was observed In a matter 6f days In the tin containers stored at ambient temperatures. No corrosion Inhibitors were added to the tin containers. Container manufacturers use a flux In the tinning process, many contain either nitrite or nitrate salts. Thus, the potential for the nltrosatlng agents exists as part of the metallic film In a seemingly clean tin container. In addition. Archer and Wlshnok (1976) demonstrated the formation of nltrosamlnes from constituents of polymeric liners of metal cans. Container specifications are vital for pesticide formulations prone to be nltrosated. 

Elimination of nitrosating agents in formulations (e.g. soditim nitrite as corrosion inhibitor for metal containers) use of plastic-lined containers. 

The inorganic nitrite used as a corrosion inhibitor in aqueous alkylene glycol or polyoxyalkylene glycol solutions can be replaced with polyoxyalkylene amines [1263,1264]. Such polyoxyalkylene amines impart corrosion inhibition to the liquid in contact with the metal and the metal in contact with the vapors of the aqueous composition. Aqueous compositions containing the glycol and the polyoxyalkylene amine also exhibit a low foaming tendency. 

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. 

There are several routes for nitrosamine contamination in pesticides use of contaminated chemicals during synthesis, side reactions, use of nitrite as a preservative and corrosion inhibitor of metal containers and by reactions with environmental nitrosating agents. Over 300 formulations were shown to be contaminated with nitrosamines however, the main contamination was confined to 2,6-dinitroaniline herbicides, dimethylamino salts of phenoxyalkanoic acid herbicide, diethanolamine and triethanolamine salts of acid... 

Several types of corrosion inhibitors have been investigated in the last 20 years [53-55] these include calcium and sodium nitrites, sodium benzoate, sodium/potassium chromate, sodium salts of silicates and phosphates, stannous chloride, hydrazine hydrate, sodium fluorophosphate, permanganate, aniline and related compounds, alkalis, azides, ferrocyanide, EDTA and many chelating compounds. However, in terms of field practice and research data, nitrite-based compounds occupy a dominant position. 

The most widely used anodic inhibitors are calcium and sodium nitrite, sodium benzoate and sodium chromate. With the exception of calcium nitrite, no other chemical is available in North America as a proprietary product. Nitrites have been used in the USA for more than 14 years and for nearly 40 years in Europe. Calcium nitrite is marketed as a non-chloride accelerator, as well as a corrosion inhibitor. For 25-30% solids in solution, dosage rates range from 2 to 4% by weight of cement depending on the application [50]. Calcium nitrite has been used in bridges, parking and roof decks, marine and other prestressed concrete structures that are exposed to chloride attack. 

Two types of calcium nitrite-based corrosion inhibitors are currently marketed, viz. a set- and strength-accelerating type and a normal-setting type. The former increases the early strength development in concrete. This effect increases with the dosage. Both admixtures are compatible with all types of Portland cements and... 

It is important to ensure that when using corrosion inhibitors with other conventional admixtures, they are added separately, at different times of the mix cycle. Corrosion-inhibiting admixtures which also accelerate the set of concrete may require the combination of a retarding admixture when ambient and mix temperatures exceed 35°C. In like manner, set-retarding corrosion inhibitors may require the addition of an accelerator to offset the retardation of early strength development (e.g. use of sodium nitrite in conjunction with sodium benzoate). 

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