Aluminum reaction with sulfuric acid

Degradation of methyl terf-butyl ether by bifunctional aluminum in the presence of oxygen was investigated by Lien and Wilkin (2002). Bifunctional aluminum was synthesized by sulfating aluminum metal with sulfuric acid. When the initial methyl terf-butyl ether concentration was 14.4 mg/L, 90% of methyl ferf-butyl ether degraded within 24 h forming acetone, methyl acetate, tert-hniyX alcohol, and ferf-butyl formate. Carbon disulfide was tentatively identified as a reaction product by GC/MS. Product yields were 27.6% for acetone, 18.4% for methyl acetate, 21% for tert-hniyX alcohol, and 6.1% ferf-butyl formate. When the initial concentration of methyl tert-butyl ether was reduced to 1.4 mg/L, 99.5% of methyl terCbutyl ether reacted. Yields of acetone, methyl acetate, and /erf-butyl alcohol were 54.7,17.2, and 13.2, respectively. 

Other experimental reproducdve effects. Human systemic effects by inhalation respirator ", nose, and eyes. Human mutation data reported. A skin and eye irritant. A sensitizer. Flammable liquid when exposed to heat or flame. Explosive reaction with aniline. Reaction with trichloroethylene forms the explosive dichloroacetylene. Ignition on contact with potassium tert-butoxide. Violent reaction with sulfuric acid or isopropylamine. Exothermic polyTTierization on contact with strong acids, caustic alkalies, aluminum, aluminum chloride, iron(III) chloride, or zinc. When heated to decomposition it emits toxic fumes of Cr. 

SAFETY PROFILE A highly corrosive irritant to the eyes, skin, and mucous membranes. Mildly toxic by inhalation, Explosive reaction with alcohols + hydrogen cyanide, potassium permanganate, sodium (with aqueous HCl), tetraselenium tetranitride. Ignition on contact with aluminum-titanium alloys (with HCl vapor), fluorine, hexa-lithium disilicide, metal acetylides or carbides (e.g., cesium acetylide, rubidium ace-tylide). Violent reaction with 1,1-difluoro-ethylene. Vigorous reaction with aluminum, chlorine + dinitroanilines (evolves gas). Potentially dangerous reaction with sulfuric acid releases HCl gas. Adsorption of the acid onto silicon dioxide is exothermic. See also HYDROGEN CHLORIDE (AEROSOL) and HYDROCHLORIC ACID. 

Production of hydrogen fluoride from reaction of Cap2 with sulfuric acid is the largest user of fluorspar and accounts for approximately 60—65% of total U.S. consumption. The principal uses of hydrogen fluoride are ia the manufacture of aluminum fluoride and synthetic cryoHte for the Hall aluminum process and fluoropolymers and chlorofluorocarbons that are used as refrigerants, solvents, aerosols (qv), and ia plastics. Because of the concern that chlorofluorocarbons cause upper atmosphere ozone depletion, these compounds are being replaced by hydrochlorofluorocarbons and hydrofluorocarbons. 

Methylphenol is converted to 6-/ f2 -butyl-2-methylphenol [2219-82-1] by alkylation with isobutylene under aluminum catalysis. A number of phenoHc anti-oxidants used to stabilize mbber and plastics against thermal oxidative degradation are based on this compound. The condensation of 6-/ f2 -butyl-2-methylphenol with formaldehyde yields 4,4 -methylenebis(2-methyl-6-/ f2 butylphenol) [96-65-17, reaction with sulfur dichloride yields 4,4 -thiobis(2-methyl-6-/ f2 butylphenol) [96-66-2] and reaction with methyl acrylate under base catalysis yields the corresponding hydrocinnamate. Transesterification of the hydrocinnamate with triethylene glycol yields triethylene glycol-bis[3-(3-/ f2 -butyl-5-methyl-4-hydroxyphenyl)propionate] [36443-68-2] (39). 2-Methylphenol is also a component of cresyHc acids, blends of phenol, cresols, and xylenols. CresyHc acids are used as solvents in a number of coating appHcations (see Table 3). 

In the United States, aluminum sulfate is usually produced by the reaction of bauxite or clay (qv) with sulfuric acid (see Sulfuric acid and sulfur trioxide). Bauxite is imported and more expensive than local clay, generally kaolin, which is more often used. Clay is first roasted to remove organics and break down the crystalline stmcture in order to make it more reactive. This is an energy intensive process. The purity of the starting clay or bauxite ore, especially the iron and potassium contents, are reflected in the assay of the final product. Thus the selection of the raw material is governed by the overall economics of producing a satisfying product. 

Reactions other than those of the nucleophilic reactivity of alkyl sulfates iavolve reactions with hydrocarbons, thermal degradation, sulfonation, halogenation of the alkyl groups, and reduction of the sulfate groups. Aromatic hydrocarbons, eg, benzene and naphthalene, react with alkyl sulfates when cataly2ed by aluminum chloride to give Fhedel-Crafts-type alkylation product mixtures (59). Isobutane is readily alkylated by a dipropyl sulfate mixture from the reaction of propylene ia propane with sulfuric acid (60). 

Benzanthrone has been prepared by three general methods, the first of which is generally regarded as the best (i) by heating a reduction product of anthraquinone with sulfuric acid and glycerol,1 or with a derivative of glycerol, or with acrolein. The anthraquinone is usually reduced in sulfuric acid solution, just prior to the reaction, by means of aniline sulfate, iron, , or copper. It has also been prepared (2) by the action of aluminum or ferric chloride on phenyl-a-naphthyl ketone, and (3) from i-phenylnaphthalene-2-carboxylic acid. ... 

Aluminum sulfate Al O + 3HjSO —> Alj(SO )j + SH O. This reaction treats bauxite with sulfuric acid, resulting in aluminum sulfate plus water. Aluminum sulfate is also known as alum, which acts as an astringent to stop a minor flow of blood or dry up blisters (potassium aluminum sulfate is also an alum). 

The acid used in the Ritter reaction is usually sulfuric acid, although other acids such as perchloric, phosphoric, polyphosphoric, formic and sulfonic acids have been used. Lewis acids such as aluminum trichloride and boron trifluoride are also occasionally used. However, high yields are generally best obtained with sulfuric acid. The choice of solvents varies among sulfuric acid, glacial acetic acid, acetic an-... 

The reactions of 1-TMS-cyclohexene oxide are similar (112). Treatment78,82 with sulfuric acid/water (in acetone), concentrated hydrobromic acid, sulfuric acid/ methanol, lithium aluminum hydride afford the corresponding compounds 1,2-di-hydroxy- (113)-, l-bromo-2-hydroxy- (114)-, l-methoxy-2-hydroxy- (115)-, 1-hydroxy-2-TMS-cyclohexane (117). Application of base to 115 yields 1-methoxy-l-cyclohexene (116). Pyrolysis of 112 gives a mixture of 1-trimethylsiloxy-l-cyclo-hexene (118) and 3-trimethylsiloxy-1-cyclohexene (ii9)77 (Scheme 13). 

In addition to the facile aluminum halide and sulfuric acid catalyzed rearrangement routes to noradamantane and substituted noradamantanes discussed above (see Eq. (11) and Scheme 8), a variety of ring closure reactions have also been employed for the preparation of these systems. The most useful reaction for this purpose involves a transannular ring closure of the bicyclo [3.3.1 Jnonyl system. Thus, 7-methyl-3-noradamantanol is obtained 12°) from the treatment of 3-keto-7-methylenebicyclo[3.3.1 jnonane 121) with sodium in moist ether (Eq. (36)). 

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