Drying of ethanol

TABLE 16.14 Boiling Points and Compositions of Azeotropes Appropriate to the Drying of Ethanol ... 

Drying of ethanol by calcium oxide 7 92% Ethanol (21) is boiled under reflux for 24 h with roasted lime (400 g) and then distilled off therefrom. The resulting ca. 99 % ethanol is again treated with lime (70 g), yielding ethanol of more than 99.7 % purity. 

Drying of ethanol by magnesium turnings 5 Magnesium (5 g), iodine (0.5 g), and at least 99 % ethanol (50 ml) are boiled under reflux until the iodine color has disappeared. If a lively gas evolution has not set in by that time, further iodine (0.5 g) is added. The mixture is heated until all the magnesium is converted into ethoxide, then the remainder (900 ml) of the ethanol, containing less than 1 % of water, is added and the whole is heated under reflux for a further 5 h, whereafter the ethanol is distilled off. 

Dissolve I g. of pinacol (preparation, p. 148) in 20 ml. of water, and add 20 ml. of the 5% aqueous sodium periodate solution. After 15 minutes, distil the clear solution, collecting the first 5 ml. of distillate. Treat this distillate with 2,4-dinitro-phenylhydrazine solution A (p. 263). Acetone 2,4-dinitrophenyl-hydrazone rapidly separates from the solution when filtered off, washed with a small quantity of ethanol, and dried, it has m.p. 126-127°, and after recrystallisation from ethanol it has m.p. 128°. 

For the latter purpose, dissolve the crystals in hot ethanol, and then add water drop by drop to the well-stirred solution until a line emulsion just appears then add more ethanol, also drop by drop, until the emulsion just redissolves. ow allow the solution to cool spontaneousK if the emulsion reappears, add a few drops of ethanol from time to time in order to keep the solution clear. Finally the o-nitrophenol separates in crystals, and the well-stirred mixture may now be cooled in ieewvater until crystallisation is complete. Filter, drain and diy either in an atmospheric desiccator, or by pressing between drying-paper. 

Add 10 g. of the crude hydrazobenzene to 80 ml. of ethanol contained in a flask fitted with a reflux water-condenser. Heat the mixture on a water-bath until the ethanol bolls, and then add 10 g. of zinc dust and 30 ml. of 30% aqueous sodium hydroxide solution. Remove the flask from the water-bath and shake the contents vigorously from time to time. After about 10 minutes, replace the flask on the water-bath and boil the contents for 3-5 minutes. Filter the mixture at the pump, transfer the filtrate to a beaker and cool in ice-water with stirring. The hydrazobenzene separates as colourless crystals, which are filtered off at the pump and drained. A portion when dried in a desiccator has m.p. 124°. 

Add 5 ml. (5 g.) of acetophenone, 1-25 g. of finely powdered paraformaldehyde, and 3 5 g. of dry dimethylamine hydrochloride to 8 ml. of absolute ethanol, and then boil the mixture under reflux for 1-5 hours. Filter the solution (which is now almost entirely clear) through a preheated filter-funnel, and cool the filtrate in ice-water with stirring. The propiophenone hydrochloride rapidly separates as white crystals filter oflF the crystals at the pump and recrystallise from a small quantity of ethanol m.p. 155-156°. Yield, 2 5 g. 

Dissolve 10 g. of chloro- 2,4-dinitrobenzenet in 50 ml. of dioxan in a 250 ml. conical flask. Dilute 8 ml. of hydrazine hydrate with an equal volume of water and add this slowly with shaking to the dioxan solution, keeping the temperature between zo " and 25°. Heat under reflux for 10 minutes to complete the reaction and then add 5 ml. of ethanol and heat again for 5 minutes. Cool and filter oflF the orange 2,4-dinitrophenylhydra-zine. Recrystallise the dry product from ethyl acetate m.p. 200° (decomp.). Yield, 7 g. 

Dinitrophenylhydra2ones usually separate in well-formed crystals. These can be filtered at the pump, washed with a diluted sample of the acid in the reagent used, then with water, and then (when the solubility allows) with a small quantity of ethanol the dried specimen is then usually pure. It should, however, be recrystallised from a suitable solvent, a process which can usually be carried out with the dinitrophenylhydrazones of the simpler aldehydes and ketones. Many other hydrazones have a very low solubility in most solvents, and a recrystallisation which involves prolonged boiling with a large volume of solvent may be accompanied by partial decomposition, and with the ultimate deposition of a sample less pure than the above washed, dried and unrecrystal-lised sample. 

It is readily prepared by the action of metallic sodium on dry ethyl acetate. The reaction, which occurs only in the presence of a trace of ethanol, is complex, but may be considered (in effect) as a condensation of two molecules of ethyl acetate under the influence of sodium ethoxide, the sodium derivative of the enol form being thus obtained. Clearly, only a trace of ethanol is thus initially... 

If cold saturated ethanolic solutions of the recrystallised tetrahydrocarbazole and of picric acid are mixed and stirred, the chocolate-brown picrate of the carbazole slowly crystallises. After it has been filtered off at the pump, washed with a small quantity of ethanol, and dried, it has m.p. 145-146°. 

Proceed as in (A), using 50 ml. of ethanol, with boiling for 20 minutes. The quinoxaline (III) crystallises readily during the boiling. Cool the mixture, filter off the quinoxaline, and wash it with ethanol. The dry product, of m.p. 220 225", weighs 1 3 g. Recrystallise the quinoxaline from chloroform or acetic acid pale yellow crystals, m.p. 226°. Yield, 0 9-ro g. 

For water insoluble aldehydes or ketones, the following alternative procedure may be used. Reflux a mixture of 0-6 g. of the aldehyde or ketone, 0 5 g. of hydroxylamine hydrochloride, 5 ml. of ethanol and 0 5 ml. of pyridine on a water bath for 15-60 minutes. Remove the alcohol either by distillation (water bath) or by evaporation of the hot solution in a stream of air (water pump). Add 5 ml. of water to the cooled residue, cool in an ice bath and stir until the oxime crystallises Filter off the solid, wash it with a little water and dry. Recrystallise from alcohol (95 per cent, or more dilute), benzene, or benzene - light petroleum (b.p. 60-80°). 

Ethyl n-butyrate. Use a mixture of 88 g. (92 ml.) of n-butyric acid, 23 g. (29 ml.) of ethanol and 9 g. (5 ml.) of concentrated sulphuric acid. Reflux for 14 hours. Pour into excess of water, wash several times with water, followed by saturated sodium bicarbonate solution until all the acid is removed, and finally with water. Dry with anhydrous magnesium sulphate, and distU. The ethyl n-but3rrate passes over at 119 5-120-5°, Yield 40 g. An improved yield can be obtained by distilhng the reaction mixture through an efficient fractionating column until the temperature rises to 125°, and purifying the crude ester as detailed above under methyl acetate. 

The experimental conditions for conducting the above reaction in the presence of dimethylformamide as a solvent are as follows. In a 250 ml. three-necked flask, equipped with a reflux condenser and a tantalum wire Hershberg-type stirrer, place 20 g. of o-chloronitrobenzene and 100 ml. of diinethylform-amide (dried over anhydrous calcium sulphate). Heat the solution to reflux and add 20 g. of activated copper bronze in one portion. Heat under reflux for 4 hours, add another 20 g. portion of copper powder, and continue refluxing for a second 4-hour period. Allow to cool, pour the reaction mixture into 2 litres of water, and filter with suction. Extract the solids with three 200 ml. portions of boiling ethanol alternatively, use 300 ml. of ethanol in a Soxhlet apparatus. Isolate the 2 2- dinitrodiphenyl from the alcoholic extracts as described above the 3ueld of product, m.p. 124-125°, is 11 - 5 g. 

In a typical experiment 105 mg (0.50 mmol) of 3.8c, dissolved in a minimal amount of ethanol, and 100 mg (1.50 mmol) of 3.9 were added to a solution of 1.21g (5 mmol) of Cu(N03)2 BH20 and 5 mmol of ligand in 500 ml of water in a 500 ml flask. -Amino-acid containing solutions required addition of one equivalent of sodium hydroxide. When necessary, the pH was adjusted to a value of 5 ( -amino acids) and 7.5 (amines). The flask was sealed carefully and the solution was stirred for 2A hours, followed by extraction with ether. After drying over sodium sulfate the ether was evaporated. Tire endo-exo ratios were determined from the H-NMR spectra of the product mixtures as described in Chapter 2. 

Syntheses of a,)3-dihalogenoethers can be achieved in various ways the classical method (37), wherein a current of dry gaseous hydrochloric acid, is made to react in an equimolar mixture of ethanol and aldehyde at 20°C first to form the monochloroether (50% yield) and then by the action of bromine, the dibromoether (80 to 90% yield) can be used. The second and simpler method is the direct bromination of ethylvinylether in a chloroformic or dioxane solution if the product is used directly without purification,... 

The development of freeze-drying for the production of blood derivatives was pioneered during World War II (96,97). It is used for the stabilization of coagulation factor (98,99) and intravenous immunoglobulin (IgG iv) products, and also for the removal of ethanol from intramuscular immunoglobulin (IgG im) solutions prior to their final formulation (Fig. 2). 

Gasohol in the United States. Over 90% of the fuel ethanol in the United States is produced from com. Typically, 0.035 m (1 bushel) of com yields 9.5 L (2.5 gal) of ethanol. Ethanol is produced by either dry or wet milling (87). Selection of the process depends on market demand for the by-products of the two processes. More than two-thirds of the ethanol in the United States is produced by wet milling. Depending on the process used, the full cost of ethanol after by-product credits has been estimated to be between 0.25—0.53/L ( 1—2/gal) for new plants (88). Eeedstock costs are a significant factor in the production of fuel ethanol. A change in com price of 0.29/m ( 1.00/bushel) affects the costs of ethanol by 0.08/L ( 0.30/gal). 

To produce highly purified phosphatidylcholine there are two industrial processes batch and continuous. In the batch process for producing phosphatidylcholine fractions with 70—96% PC (Pig. 4) (14,15) deoiled lecithin is blended at 30°C with 30 wt % ethanol, 90 vol %, eventually in the presence of a solubiHzer (for example, mono-, di-, or triglycerides). The ethanol-insoluble fraction is separated and dried. The ethanol-soluble fraction is mixed with aluminum oxide 1 1 and stirred for approximately one hour. After separation, the phosphatidylcholine fraction is concentrated, dried, and packed. 

Favorable rates and yields of DAP prepolymer are obtained by solution polymerisation in CCl —bensene mixtures (68). Bulk polymerisation at 80°C with bensoyl peroxide is advanced to a certain viscosity before addition of ethanol to precipitate the prepolymer that is then dried (69). 

The indicator was prepared by the method of Oiehl and Einhorn. A solution of 5 g of sodium hydroxide in 50 mL of water and 40 ml of ethanol is prepared in a 250-mL Erlenmeyer flask. To this is added a solution of 1.64 ml (0.025 mol, 1.45 g) of acetone in 6.3 mL (0.050 mol, 5.6 g) of freshly distilled cinnamaldehyde (Note 1). This mixture is stirred thoroughly at room temperature for 30 min. The resulting voluminous yellow precipitate is filtered with suction, washed with 100 mL of water, and dried, affording 6.5 g of l,9-diphenylnona-l,3,6,8-tetraen-5-one. Recrystallization from 200 mL of hot 9511 ethanol gives 3.5 g of yellow crystals, mp 142-143 C (lit mp 142°C). This indicator is also available from Aldrich Chemical Co. 

The greater preference of molecular sieves for combining with water molecules explains why this material can be used for drying ethanol and why molecular sieves are probably the most universally useful and efficient drying agents. Percolation of ethanol with an initial water content of 0.5% through a 144 cm long column of type 4A molecular sieves reduced the water content to lOppm. Similar results have been obtained with pyridine. 

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