Sodium hydroxide, purification

An alternative method of purification, well adapted for large scale practice, is as follows. Dissolve the crude sulphapyridine in 1-05 mols of 30 per cent. u>/v sodium hydroxide, salt out the sodium derivative with excess of sodium chloride,... 

Merthiolate/T4- )4-< 7 (3), sodium ethyLmercurithiosahcylate, known also as thimersol, is prepared from a 1 1 ratio of ethyhnercuric chloride/7(97-27-. and disodium thiosahcylate ia ethanol. After removal of the sodium chloride by filtration, the free acid is precipitated by acidification with dilute sulfuric acid. Purification is achieved by recrystallization from 95% ethanol, and the product, merthiolate, is obtained by neutralization with a stoichiometric amount of sodium hydroxide. 

In the manufacture of 2-naphthalenol, 2-naphthalenesulfonic acid must be converted to its sodium salt this can be done by adding sodium chloride to the acid, and by neutralizing with aqueous sodium hydroxide or neutralizing with the sodium sulfite by-product obtained in the caustic fusion of the sulfonate. The cmde sulfonation product, without isolation or purification of 2-naphthalenesulfonic acid, is used to make 1,6-, 2,6-, and 2,7-naphthalenedisulfonic acids and 1,3,6-naphthalenetrisulfonic acid by further sulfonation. By nitration, 5- and 8-nitro-2-naphthalenesulfonic acids, [89-69-1] and [117-41-9] respectively, are obtained, which are intermediates for Cleve s acid. All are dye intermediates. The cmde sulfonation product can be condensed with formaldehyde or alcohols or olefins to make valuable wetting, dispersing, and tanning agents. 

The sodium formate process is comprised of six steps (/) the manufacture of sodium formate from carbon monoxide and sodium hydroxide, (2) manufacture of sodium oxalate by thermal dehydrogenation of sodium formate at 360°C, (J) manufacture of calcium oxalate (slurry), (4) recovery of sodium hydroxide, (5) decomposition of calcium oxalate where gypsum is produced as a by-product, and (6) purification of cmde oxahc acid. This process is no longer economical in the leading industrial countries. UBE Industries (Japan), for instance, once employed this process, but has been operating the newest diaLkyl oxalate process since 1978. The sodium formate process is, however, still used in China. 

Essentially no waste products are formed ia the USP process if hydriodic acid and either sodium hydroxide or sodium carbonate are used as reactants. Water results from use of the former a mole equivalent quantity of carbon dioxide is produced from the latter reagents. Higher quaUty grades may require some purification steps which may result ia wastes from the treatment. Disposal of these impurities must then be carried out. 

A large number of patents describe various procedures for the mainly continuous hydrolysis and oxidation processes, as weU as for the purification steps requited to obtain high grade vanillin. Lignin is degraded either with sodium hydroxide or with calcium hydroxide solution and simultaneously... 

Other options for the purification of CA include dissolution in hot water, aqueous ammonia, aqueous formaldehyde, or hot dimethylformamide followed by filtration to remove most of the impurities. The CA is recoverable by cooling the aqueous solution (84), acidifying the ammonium hydroxide solution (85), or cooling the dimethylform amide solution with further precipitation of CA by addition of carbon tetrachloride (86). Sodium hydroxide addition precipitates monosodium cyanurate from the formaldehyde solution (87). 

The base may be purified by steam distillation but distillation under reduced pressure is more satisfactory. The oil is dried over 5 g. of solid sodium hydroxide and distilled in vacuo. I he first portion of the distillate may contain -toluidine and must be carefully separated, as it causes rapid discoloration. The 3-bromo-4-aminotoluene is obtained as a colorless liquid of b.p. i20-i22°/30 mm. or 92-94 /3 mm. It solidifies on cooling and melts at 16-18°. The loss on purification is about 15 per cent of the weight of the crude base. 

Acids that are solids can be purified in this way, except that distillation is replaced by repeated crystallisation (preferable from at least two different solvents such as water, alcohol or aqueous alcohol, toluene, toluene/petroleum ether or acetic acid.) Water-insoluble acids can be partially purified by dissolution in N sodium hydroxide solution and precipitation with dilute mineral acid. If the acid is required to be free from sodium ions, then it is better to dissolve the acid in hot N ammonia, heat to ca 80°, adding slightly more than an equal volume of N formic acid and allowing to cool slowly for crystallisation. Any ammonia, formic acid or ammonium formate that adhere to the acid are removed when the acid is dried in a vacuum — they are volatile. The separation and purification of naturally occurring fatty acids, based on distillation, salt solubility and low temperature crystallisation, are described by K.S.Markley (Ed.), Fatty Acids, 2nd Edn, part 3, Chap. 20, Interscience, New York, 1964. 

Because phenols are weak acids, they can be freed from neutral impurities by dissolution in aqueous N sodium hydroxide and extraction with a solvent such as diethyl ether, or by steam distillation to remove the non-acidic material. The phenol is recovered by acidification of the aqueous phase with 2N sulfuric acid, and either extracted with ether or steam distilled. In the second case the phenol is extracted from the steam distillate after saturating it with sodium chloride (salting out). A solvent is necessary when large quantities of liquid phenols are purified. The phenol is fractionated by distillation under reduced pressure, preferably in an atmosphere of nitrogen to minimise oxidation. Solid phenols can be crystallised from toluene, petroleum ether or a mixture of these solvents, and can be sublimed under vacuum. Purification can also be effected by fractional crystallisation or zone refining. For further purification of phenols via their acetyl or benzoyl derivatives (vide supra). 

The use of potassium hydroxide rather than sodium hydroxide is dietated by solubility characteristics which make purification of the sodium alkoxide difficult. 

For purification the acid is crystallized from about 150 cc. of glacial acetic acid, using an acid-resistant filter for the hot solution (Note 7). Aconitic acid separates as small, colorless needles weighing 50-60 g., and about 10 g. more can be secured by concentrating the mother liquor under reduced pressure to one-third of its volume. The material is dried in the air and then in a desiccator containing sodium hydroxide in order to remove all traces of acetic acid. One crystallization usually is sufficient to bring the point of decomposition to 198-199° (Note 6). 

Alternatively cellulose is produced from wood via wood pulp. A number of processes are used in which the overall effect is the removal of the bulk of the non-cellulosic matter. The most widely used are the sulphite process, which uses a solution of calcium bisulphite and sulphur dioxide, the soda process using sodium hydroxide and the sulphate process using a solution of sodium hydroxide and sodium sulphide. (The term sulphate process is used since sodium sulphate is the source of the sulphide.) For chemical purposes the sulphite process is most commonly used. As normally prepared these pulps contain about 88-90% alpha-cellulose but this may be increased by alkaline purification and bleaching. 

Commercial tetrahydrofuran (Matheson, Coleman and Bell) is washed several times with 40% aqueous sodium hydroxide to remove peroxides and organic stabilizers and then dried over solid sodium hydroxide. The clear supernatant liquid is used without further purification. 

Other industrial applications of electrolysis include extraction/purification of metals from ores, electroplating, and the manufacture of certain chemicals such as sodium hydroxide. In the latter, sodium chloride solution when electrolysed is converted to sodium hydroxide to produce chlorine at the anode and hydrogen at the cathode. Both of these gaseous by-products are collected for industrial use chlorine is used in the production of bleach and PVC hydrogen is used as a fuel, to saturate fats, and to make ammonia. 

At the alumina plant, the bauxite ore is further crushed to the correct particle size for efficient extraction of the alumina through digestion by hot sodium hydroxide liquor. After removal of "red mud" (the insoluble part of the bauxite) and fine solids from the process liquor, aluminum trihydrate crystals are precipitated and calcined in rotary kilns or fluidized bed calciners to produce alumina (AljOj). Some alumina processes include a liquor purification step. 

This crude product is dissolved in 100 ml of dilute hydrochloric acid, the acid solution is extracted with ether, and the aqueous layer is made basic with sodium hydroxide solution (3N) in the presence of ether (approximately 250 ml). The ether layer Is separated, dried over potassium hydroxide and evaporated to a white solid. Additional purification by repeating the formation of the hydrochloric acid salt and reprecipitation of the base is carried out. When purified in this manner, followed by drying at 80°C in vacuo over phosphorus pentoxide, 2-chloro-11-(4-methyl-1-piperazinyl)dibenz[b,f] [1,4]oxazepine, li/IP 109° to 111°C, is obtained. 

The above keto-nitrile (15 grams) was methylated with a solution of diazomethane in ether. (The diazomethane solution was prepared using 20 grams of N-nitrosomethylurea.) The ether and excess diazomethane were evaporated on the steam bath and the oil dissolved in ethanol (50 ml). To this was added a solution of guanidine in ethanol (100 ml) (prepared from 8.1 grams of the hydrochloride). The solution was refluxed for 5 hours, the alcohol removed and the residue treated with 5N sodium hydroxide. The insoluble material was then filtered. After purification by precipitation from dilute acetic acid with sodium hydroxide and by recrystallization from ethanol the product formed clear colorless needles (8.0 grams), MP 218°-220°C as described in U.S. Patent 2,602,794. 

The products of this electrolysis have a variety of uses. Chlorine is used to purify drinking water large quantities of it are consumed in making plastics such as polyvinyl chloride (PVC). Hydrogen, prepared in this and many other industrial processes, is used chiefly in the synthesis of ammonia (Chapter 12). Sodium hydroxide (lye), obtained on evaporation of the electrolyte, is used in processing pulp and paper, in the purification of aluminum ore, in the manufacture of glass and textiles, and for many other purposes. 

To a solution of 130 g. (0.6 mole) of arsanilic acid (Org. Syn. 3, 13) in 600 cc. (0.6 mole) of normal sodium hydroxide is added 52 g. (0.62 mole) of sodium bicarbonate and 70 g. (0.75 mole) of chloroacetamide (Org. Syn. 7, 16). The mixture is heated 011 a water bath to 90-1000 and a steady evolution of carbon dioxide occurs. At the end of two hours, when gas evolution has practically ceased, the mixture is cooled to 40° C., stirred vigorously and 150 cc. of 1 1 hydrochloric acid poured in rapidly. /i-Arsonophenylglycinamide crystallizes at once and, after cooling to room temperature, is filtered by suction and washed once with 2 per cent hydrochloric acid (Note 1), then with cold water. The crude product thus obtained is contaminated with some arsanilic acid and possibly other products. These are removed during purification. The crude product is suspended in about 400 cc. of water and with vigorous stirring, treated carefully with 25 per cent aqueous sodium hydroxide until solution is just complete. At this point the mixture is still acid to litmus and an excess of sodium hydroxide is to be avoided to prevent decomposition of the product. About 15 g. of boneblack... 

As a general rule, the requirements for attemperation spray water are the same as those for steam purity. In some cases boiler FW is suitable however, additional purification frequently is required. In all cases, the spray water should be obtained from a source that is free of deposit-forming and corrosive chemicals such as sodium hydroxide, sodium sulfite, sodium phosphate, iron, and copper. The suggested limits for (attemperator) spray water quality are ... 

To a stirred solution of the alkynylsilane (20 mmol) and triethylbenzyl-ammonium chloride (0.7 mmol) in MeCN (15 ml) cooled to 0°C was added aqueous sodium hydroxide (15 ml, 12m). After 5-10min, the mixture was diluted with ether and extracted with ether/dichloromethane. Drying, concentration and suitable purification gave the free alkyne (80-90%). 

The cyclic oligomers are only slightly soluble in water and dilute solutions of caprolactam. They tend to separate out from die extracted waste during die process of concentration and chemical purification of die caprolactam. The cyclic oligomers tend to form on the walls of the equipment used in die process equipment. 6-Aminocaproic acid or sodium 6-aminocaproate may also be found in die oligomeric waste, especially if sodium hydroxide is used to initiate die caprolactam polymerization. 

Dichlorodibenzo-p-dioxin was prepared from isotopic potassium 2,4-dichlorophenate uniformly labeled with Ullman conditions gave a 20.5% yield. Small amounts of dichlorophenoxy chlorophenol were removed from the product by extraction with sodium hydroxide before purification by fractional sublimation and recrystallization from anisole. Chlorination of 2,7-dichlorodibenzo-p-dioxin in chloroform solution containing trace amounts of FeCls and 12 yielded a mixture of tri-, tetra-, and pentachloro substitution products. Purification by digestion in boiling chloroform, fractional sublimation, and recrystallization from anisole was effective in refining this product to 92% 2,3,7,8-tetrachloro isomer, which also contained 7% of the tri- and 1% of the penta-substituted dibenzo-p-dioxin. Mass spectroscopy was used exclusively to monitor the quality of the products during the synthesis. 

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