Ammonium attack

Ammonium ions, NH4, act upon concrete as acids. This is due to their abihty to react with OH, producing NHj and water. Because the NHj formed escapes as a gas, their action is comparable to acids with highly soluble reaction products. Aggressiveness due to NH4 is classified by EN 206 [4] as shown in Table 3.3. 

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Ketones may also be converted into amines, if they are first reacted with ammonium salts ot methoxyamine and then reduced with sodium trihydrocyanoborate at pH 7, where carbonyl groups are not attacked (M.-H. Boutigue, 1973). 

Anhydrous aluminum triduotide, A1F., is a white crystalline soHd. Physical properties are Hsted ia Table 2. Aluminum duotide is spatingly soluble ia water (0.4%) and iasoluble ia dilute mineral acids as well as organic acids at ambient temperatures, but when heated with concentrated sulfuric acid, HF is hberated, and with strong alkah solutions, aluminates are formed. A1F. is slowly attacked by fused alkahes with the formation of soluble metal duotides and aluminate. A series of double salts with the duotides of many metals and with ammonium ion can be made by precipitation or by soHd-state reactions. 

Corrosion. Ammonium bifluoride dissolves in aqueous solutions to yield the acidic bifluoride ion the pH of a 5% solution is 3.5. In most cases, NH4HF2 solutions react readily with surface oxide coatings on metals thus NH4HF2 is used in pickling solutions (see Metal surface treatments). Many plastics, such as polyethylene, polypropylene, unplasticized PVC, and carbon brick, are resistant to attack by ammonium bifluoride. 

Nicotine is used as a contact insecticide for aphids attacking fmits, vegetables, and ornamentals, and as a fumigant for greenhouse plants and poultry mites. Nicotine sulfate is safer and more convenient to handle and the free alkaloid is rapidly Hberated by the addition of soap, hydrated lime, or ammonium hydroxide to the spray solution. Nicotine sprays commonly contain 0.05—0.06% nicotine, and nicotine dusts, 1—2% nicotine. 

Organic compounds normally cause Htde or no corrosion of magnesium. Tanks or other containers of magnesium alloys are used for phenol [108-95-2] methyl bromide [74-96 ] and phenylethyl alcohol [60-12-8]. Most alcohols cause no more than mild attack, but anhydrous methanol attacks magnesium vigorously with the formation of magnesium methoxide [109-88-6]. This attack is inhibited by the addition of 1% ammonium sulfide [12135-76-1] or the presence ofwater. 

The PGM concentrate is attacked with aqua regia to dissolve gold, platinum, and palladium. The more insoluble metals, iridium, rhodium, mthenium, and osmium remain as a residue. Gold is recovered from the aqua regia solution either by reduction to the metallic form with ferrous salts or by solvent-extraction methods. The solution is then treated with ammonium chloride to produce a precipitate of ammonium hexachloroplatinate(IV),... 

In general, polycarbonate resins have fair chemical resistance to aqueous solutions of acids or bases, as well as to fats and oils. Chemical attack by amines or ammonium hydroxide occurs, however, and aUphatic and aromatic hydrocarbons promote crazing of stressed molded samples. Eor these reasons, care must be exercised in the choice of solvents for painting and coating operations. Eor sheet appHcations, polycarbonate is commonly coated with a sihcone—sihcate hardcoat which provides abrasion resistance as well as increased solvent resistance. Coated films are also available. 

Aqueous solutions of ammonium haUdes, like the other ammonium salts of strong acids, are acidic on storage and exposure these solutions tend to become more acidic through ammonia loss. They also have a pronounced tendency to attack ferrous and other metal surfaces, especiaHy those of copper and copper aHoys. 

Carbonyl sulfide reacts with chlorine forming phosgene (qv) and sulfur dichloride [10545-99-0] and with ammonia forming urea and ammonium sulfide [12135-76-1]. Carbonyl sulfide attacks metals, eg, copper, ia the presence of moisture and is thought to be iavolved ia atmospheric sulfur corrosion (27,28). Its presence ia propane gas at levels above a few ppm may cause the gas to fail the copper-corrosion test. 

There are two serious problems associated with continuous tar distillation. Coal tar contains two types of components highly corrosive to ferrous metals. The ammonium salts, mainly ammonium chloride, associated with the entrained Hquor remain in the tar after dehydration, tend to dissociate with the production of hydrochloric acid and cause rapid deterioration of any part of the plant in which these vapors and steam are present above 240°C. Condensers on the dehydration column and fractionation columns are also attacked. This form of corrosion is controlled by the addition of alkaU (10% sodium carbonate solution or 40% caustic soda) to the cmde tar in an amount equivalent to the fixed ammonia content. 

Direct Chlorination of Ethylene. Direct chlorination of ethylene is generally conducted in Hquid EDC in a bubble column reactor. Ethylene and chlorine dissolve in the Hquid phase and combine in a homogeneous catalytic reaction to form EDC. Under typical process conditions, the reaction rate is controlled by mass transfer, with absorption of ethylene as the limiting factor (77). Ferric chloride is a highly selective and efficient catalyst for this reaction, and is widely used commercially (78). Ferric chloride and sodium chloride [7647-14-5] mixtures have also been utilized for the catalyst (79), as have tetrachloroferrate compounds, eg, ammonium tetrachloroferrate [24411-12-9] NH FeCl (80). The reaction most likely proceeds through an electrophilic addition mechanism, in which the catalyst first polarizes chlorine, as shown in equation 5. The polarized chlorine molecule then acts as an electrophilic reagent to attack the double bond of ethylene, thereby faciHtating chlorine addition (eq. 6) ... 

Heated zirconium is readily chlorinated by ammonium chloride, molten stannous chloride, zinc chloride, and chlorinated hydrocarbons and the common chlorinating agents. It is slowly attacked by molten magnesium chloride in the absence of free magnesium, which is always present in the KroU process. 

Zirconium is readily attacked by acidic solutions containing fluorides. As Httle as 3 ppm flouride ion in 50% boiling sulfuric acid corrodes zirconium at 1.25 mm/yr. Solutions of ammonium hydrogen fluoride or potassium hydrogen fluoride have been used for pickling and electropolishing zirconium. Commercial pickling is conducted with nitric—hydrofluoric acid mixtures (see Metal surface treatments). 

Dehalogenation of monochlorotoluenes can be readily effected with hydrogen and noble metal catalysts (34). Conversion of -chlorotoluene to Ncyanotoluene is accompHshed by reaction with tetraethyl ammonium cyanide and zero-valent Group (VIII) metal complexes, such as those of nickel or palladium (35). The reaction proceeds by initial oxidative addition of the aryl haHde to the zerovalent metal complex, followed by attack of cyanide ion on the metal and reductive elimination of the aryl cyanide. Methylstyrene is prepared from -chlorotoluene by a vinylation reaction using ethylene as the reagent and a catalyst derived from zinc, a triarylphosphine, and a nickel salt (36). 

The concept and use of free radical attack on pyrimidines has been little developed. However, pyrimidine does react slowly with p-nitrobenzenediazonium chloride to yield some 2- and 4-p-nitrophenylpyrimidines (51JCS2323) in addition, 2,4-and 4,6-dimethyl-pyrimidine are converted by hydroxymethylene radicals (from ammonium peroxydisul-fate/methanol) into 6- and 2-hydroxymethyl derivatives, respectively (77H(6)525). Certain bipyrimidine photoproducts appear to be formed from two similar or dissimilar pyrimidinyl radicals (see Section 2.13.2.1.4). 

The classical structures of pyrrole, furan and thiophene (31) suggest that these compounds might show chemical reactions similar to those of amines, ethers and thioethers (32) respectively. On this basis, the initial attack of the electrophile would be expected to take place at the heteroatom and lead to products such as quaternary ammonium and oxonium salts, sulfoxides and sulfones. Products of this type from the heteroaromatic compounds under consideration are relatively rare. 

Copper alloys are attacked at high pH. However, attack is usually caused not by elevated pH alone but because of copper complexation by ammonia or substituted ammonium compounds. In fact, copper resists corrosion in caustic solutions. For example, corrosion rates in hot caustic soda may be less than 1 mil/y (0.025 mm/y). 

Aluminum alloys are corroded at both high and low pH. Not all compounds that increase pH cause severe attack. Ammonium hydroxide only moderately increases corrosion rates. Wastage actually decreases above a pH of 12 in ammonium hydroxide solutions (see Fig. 8.1). A caustic solution causes corrosion rates to increase substantially as pH rises. The Al ion reacts vigorously with OH to produce A102. ... 

Copper alloys are attacked hy ammonium hydroxide, but corrosion rates increase only moderately with caustic concentration. 

Compounds such as hydrogen sulfide and cyanides are the most common metal surface poisoners occurring in process units subject to aqueous-phase hydrogen attack. In many process units, these compounds can be effectively eliminated and hydrogen diffusion stopped by adding ammonium polysulfides and oxygen to the process streams which converts the compounds to polysulfides and thiocyanates, provided the pH is kept on the alkaline side. 

Since there are two available sites for electrophilic attack in an enamine, the electrophile can add to the nitrogen atom to form an ammonium salt, or it can add to the position to form an immonium salt. 

Minisci reactions have also been applied to these compounds. formation by exposure to w-CPBA and O-methylation with Meerwein s reagent converted 54 into 55. Nucleophilic attack of the hydroxymethyl radical, generated with ammonium sulfate, provides an alternate route to 2-hydroxymethyl pyridines 56. 

In aqueous solutions, the prevailing process is the primary attack of the unsubstituted nitrogen atom of alkylhydrazines at the terminal carbon atom of diacetylene with predominant formation of l-alkyl-5-methylpyrazoles (18) (73DIS). The content of isomeric l-alkyl-3-methylpyrazoles is less than 10% (GLC). In the authors opinion, this different direction of the attack at diacetylene in aqueous media is related to the hydration of alkylhydrazines and the formation of ammonium base RN" H2(0H) NH2, in which the primary amino group becomes the major nucleophilic center. 

A direct attack on the oxazirane ring occurs with ferrous salts. Oxaziranes are decomposed by aqueous solutions of ferrous ammonium sulfate even at room temperature. The reaction follows a radical-chain mechanism because le.ss than stoichiometric amounts of the ferrous salt cause the decomposition, 2-icrt-Butyl-3-phenyloxazirane (9) and 1 equivalent of ferrous salt give ferf-butylbenzamide in 98%... 

Nitric acid is one of the most used chemicals. The 1994 U.S. production was approximately 17.65 hillion pounds. It is a colorless to a yellow liquid, which is very corrosive. It is a strong oxidizing acid that can attack almost any metal. The most important use of nitric acid is to produce ammonium nitrate fertilizer. 

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