Anhydrous alumina

The aolventa, enumerated under 10 and 11, may contain traces of peroxides. These can be removed either by refiuxing over anhydrous stannous ofiloride (see concluding paragraph of Section VI, 12) or by filtration under slight pressure through a column of activated alumina. 

Anhydrous, monomeric formaldehyde is not available commercially. The pure, dry gas is relatively stable at 80—100°C but slowly polymerizes at lower temperatures. Traces of polar impurities such as acids, alkahes, and water greatly accelerate the polymerization. When Hquid formaldehyde is warmed to room temperature in a sealed ampul, it polymerizes rapidly with evolution of heat (63 kj /mol or 15.05 kcal/mol). Uncatalyzed decomposition is very slow below 300°C extrapolation of kinetic data (32) to 400°C indicates that the rate of decomposition is ca 0.44%/min at 101 kPa (1 atm). The main products ate CO and H2. Metals such as platinum (33), copper (34), and chromia and alumina (35) also catalyze the formation of methanol, methyl formate, formic acid, carbon dioxide, and methane. Trace levels of formaldehyde found in urban atmospheres are readily photo-oxidized to carbon dioxide the half-life ranges from 35—50 minutes (36). 

Anhydrous aluminum chloride, AIQ, is manufactured primarily by reaction of chlorine [7782-50-5] vapor with molten aluminum and used mainly as a catalyst in organic chemistry ie, in Friedel-Crafts reactions (qv) and in proprietary steps in the production of titanium dioxine [13463-67-7] Ti02, pigment. Its manufacture by carbochlorination of alumina or clay is less energy-intensive and is the preferred route for a few producers (19). 

The properties of 1,1-dichloroethane are Hsted ia Table 1. 1,1-Dichloroethane decomposes at 356—453°C by a homogeneous first-order dehydrochlofination, giving vinyl chloride and hydrogen chloride (1,2). Dehydrochlofination can also occur on activated alumina (3,4), magnesium sulfate, or potassium carbonate (5). Dehydrochlofination ia the presence of anhydrous aluminum chloride (6) proceeds readily. The 48-h accelerated oxidation test with 1,1-dichloroethane at reflux temperatures gives a 0.025% yield of hydrogen chloride as compared to 0.4% HCl for trichloroethylene and 0.6% HCl for tetrachloroethylene. Reaction with an amine gives low yields of chloride ion and the dimer 2,3-dichlorobutane, CH CHCICHCICH. 2-Methyl-l,3-dioxaindan [14046-39-0] can be prepared by a reaction of catechol [120-80-9] with 1,1-dichloroethane (7). 

Various catalytic materials promote dehydrochlorination including AlCl (6,91), AICk-nitrohenzene complex (114), activated alumina (3), and FeCl (112). Chlorination in the presence of anhydrous aluminum chloride gives hexachloroethane. Dry pentachloroethane does not corrode iron at temperatures up to 100°C. It is slowly hydrolyzed by water at normal temperatures and oxidized in the presence of light to give trichloroacetyl chloride. 

An abrasive is usually chemically inert, neither interacting with other dentifrice ingredients nor dissolving in the paste or the mouth. Substances used as dentifrice abrasives include amorphous hydrated silica, dicalcium phosphate dihydrate [7789-77-7] anhydrous dicalcium phosphate [7757-93-9] insoluble sodium metaphosphate [10361-03-2], calcium pyrophosphate [35405-51-7], a-alumina trihydrate, and calcium carbonate [471-34-1]. These materials are usually synthesized to specifications for purity, particle size, and other characteristics naturally occurring minerals are used infrequently. Sodium bicarbonate [144-55-8] and sodium chloride [7647-14-5] have also been employed as dentifrice abrasives. 

Butyl Ether. -Butyl ether is prepared by dehydration of -butyl alcohol by sulfuric acid or by catalytic dehydration over ferric chloride, copper sulfate, siUca, or alumina at high temperatures. It is an important solvent for Grignard reagents and other reactions that require an anhydrous, inert medium. -Butyl ether is also an excellent extracting agent for use with aqueous systems owing to its very low water-solubiUty. 

Example 2 Calculation of Error with Doubled Sample Weight Repeated measurements from a lot of anhydrous alumina for loss on ignition established test standard error of 0.15 percent for sample weight of 500 grams, noting V is the square of s.e. Calculation of variance V and s.e. for a 1000 gram sample is... 

Benzeneazodiphenylamine (4-phenylazodiphenylamine) [28110-26-1] M 273.3, m 82, pK 1.52. Purified by chromatography on neutral alumina using anhydrous C6H6 with 1% anhydrous MeOH. The major component, which gave a stationary band, was cut out and eluted with EtOH or MeOH. [Hogfeldt and Bigeleisen J Am Chem Soc 82 15 I960.] Crystd from pet ether or EtOH. See Sudan I. 

Conductivity grade benzonitrile (specific conductance 2 x 10" mho) was obtained by treatment with anhydrous AICI3, followed by rapid distn at 40-50° under vacuum. After washing with alkali and drying with CaCl2, the distillate was vac distd several times at 35° before being fractionally crystd several times by partial freezing. It was dried over finely divided activated alumina from which it was withdrawn as required [Van Dyke and Harrison J Am Chem Soc 73 402 7957]. 

Wash with cone H2SO4, then Na2C03 soln, dry with anhydrous Na2C03, and finally pass through a 50cm column of activated alumina before distn. Alternatively, wash with 10% ferrous sulfate soln to remove peroxides, then H2O, dry with CaS04, and dist in vac. Add 0.2% of catechol to stabilise it. VERY TOXIC. 

Peroxides can be removed by refluxing with anhydrous SnCl2 or by passage under slight pressure through a column of activated alumina. Dried with anhydrous K2CO3 and CaS04, filtered and distd, or refluxed with, and distd from NaOH. 

Quinazoline [253-82-7] M 130.2, m 48.0-48.5 , b 120-121 /17-18mm, pK, -4.51 (aq H2SO4, anhydrous dication), pK 2.01 (anhydrous monocation), pK3 4.3 (equilibrium with 3,4-hydrated species), PK4 12.1 (hydrated anion). Purified by passage through an activated alumina column in benzene or pet ether (b 40-60°). Distd under reduced pressure, sublimed under vacuum and crystd from pet ether. [Armarego 7 Chem 1170 1961.]... 

Styrene is difficult to purify and keep pure. Usually contains added inhibitors (such as a trace of hydroquinone). Washed with aqueous NaOH to remove inhibitors (e.g. rert-butanol), then with water, dried for several hours with MgS04 and distd at 25° under reduced pressure in the presence of an inhibitor (such as 0.005% p-tert-butylcatechol). It can be stored at -78°. It can also be stored and kept anhydrous with Linde type 5A molecular sieves, CaH2, CaS04, BaO or sodium, being fractionally distd, and distd in a vacuum line just before use. Alternatively styrene (and its deuterated derivative) were passed through a neutral alumina column before use [Woon et al. J Am Chem Soc 108 7990 1986 Collman J Am Chem Soc 108 2588 1986]. 

Aluminium fluoride (anhydrous) [7784-18-4] M 84.0, m 250°. Technical material may contain up to 15% alumina, with minor impurities such as aluminium sulfate, cryolite, silica and iron oxide. Reagent grade AIF3 (hydrated) contains only traces of impurities but its water content is very variable (may be up to 40%). It can be dried by calcining at 600-800° in a stream of dry air (some hydrolysis occurs), followed by vacuum distn at low pressure in a graphite system, heated to approximately 925° (condenser at 900°) [Henry and Dreisbach J Am Chem Soc 81 5274 1959]. 

Action of anhydrous neutral alumina on gem-difluorocycloalkanes (see section VI) is a convenient general route to cyclic vinyl fluorides. ... 

---