Solution fractional distillation

Fractional crystallization (recrystallization) is a method of purifying a substance by crystallizing the pure solid from a saturated solution while impurities remain in solution. Fractional distillation (See distillation.) Fractional precipitation is a technique in which two or more ions in solution, each capable of being precipitated by the same reagent, are separated by the use of that reagent. 

The ammonium hydrogensulphate is returned to the electrolytic cell. A process such as this yields an aqueous solution containing about 30% hydrogen peroxide. The solution can be further concentrated, yielding ultimately pure hydrogen peroxide, by fractional distillation but the heating of concentrated hydrogen peroxide solutions requires care (see below). 

Since aliphatic hydrocarbons (unlike aromatic hydrocarbons, p. 155) can be directly nitrated only under very special conditions, indirect methods are usually employed for the preparation of compounds such as nitroethane, CjHsNO. When ethyl iodide is heated with silver nitrite, two isomeric compounds are formed, and can be easily separated by fractional distillation. The first is the true ester, ethyl nitrite, C,HiONO, of b.p. 17° its identity is shown by the action of hot sodium hydroxide solution, which hydrolyses it, giving ethanol and... 

Place 80 g, of hydroxylamine sulphate (or 68-5 g. of the hydrochloride), 25 g. of hydrated sodium acetate, and 100 ml. of water in a 500 ml. flask fitted with a stirrer and a reflux water-condenser, and heat the stirred solution to 55-60°. Run in 35 g (42 nil,) of -hexyl methyl ketone, and continue the heating and vigorous stirring for ij hours. (The mixture can conveniently be set aside overnight after this stage.) Extract the oily oxime from the cold mixture twice with ether. Wash the united ethereal extract once with a small quantity of water, and dry it with sodium sulphate. Then distil off the ether from the filtered extract, preferably using a distillation flask of type shown in Fig. 41 (p. 65) and of ca, 50 ml, capacity, the extract being run in as fast as the ether distils, and then fractionally distil the oxime at water-pump pressure. Collect the liquid ketoxime, b.p. 110-111713 mm. Yield, 30-32 g. 

Bromoform. Commercial bromoform should be shaken thoroughly with water, separated, dried over powdered anhydrous sodium sulphate and then fractionally distilled under reduced pressure using a water-condenser. It should be stored in a dark cupboard. It is an excellent solvent, has the advantage of a high Constant, and very seldom causes association of the solute. 

The experimental procedure to be followed depends upon the products of hydrolysis. If the alcohol and aldehyde are both soluble in water, the reaction product is divided into two parts. One portion is used for the characterisation of the aldehyde by the preparation of a suitable derivative e.g., the 2 4-dinitrophenylhydrazone, semicarbazone or di-medone compound—see Sections 111,70 and 111,74). The other portion is employed for the preparation of a 3 5-dinitrobenzoate, etc. (see Section 111,27) it is advisable first to concentrate the alcohol by dis tillation or to attempt to salt out the alcohol by the addition of solid potassium carbonate. If one of the hydrolysis products is insoluble in the reaction mixture, it is separated and characterised. If both the aldehyde and the alcohol are insoluble, they are removed from the aqueous layer separation is generally most simply effected with sodium bisulphite solution (compare Section Ill,74),but fractional distillation may sometimes be employed. 

There are two methods available for aroma recovery. In one method, a portion of the water is stripped from the juice prior to concentration and fractionally distilled to recover a concentrated aqueous essence solution. Apple juice requires 10% water removal, peach 40%, and Concord grape 25—30% to remove volatile flavor as an essence. Fractional distillation affords an aqueous essence flavor solution of 100—200-fold strength, which means the essence is 100 to 200 times more concentrated in flavor than the starting juice. A second method of essence recovery is to condensate the volatiles from the last effect of the evaporator they are enriched in volatile flavor components (18). 

In typical processes, the gaseous effluent from the second-stage oxidation is cooled and fed to an absorber to isolate the MAA as a 20—40% aqueous solution. The MAA may then be concentrated by extraction into a suitable organic solvent such as butyl acetate, toluene, or dibutyl ketone. Azeotropic dehydration and solvent recovery, followed by fractional distillation, is used to obtain the pure product. Water, solvent, and low boiling by-products are removed in a first-stage column. The column bottoms are then fed to a second column where MAA is taken overhead. Esterification to MMA or other esters is readily achieved using acid catalysis. 

Tall oil rosin is a by-product of paper manufacturing. Raw wood chips are digested under heat and pressure with a mixture of sodium hydroxide and sodium sulfide. Soluble sodium salts of lignin, rosin, and fatty acids are formed, which are removed from the wood pulp as a dark solution. The soaps of the rosin and fatty acids float to the top of the mixture, where they are skimmed off and treated with sulfuric acid to free the rosin and fatty acids. This mixture, known as cmde tall oil (CTO), is refined further to remove color and odor bodies fractional distillation separates the tall oil rosin acids from the fatty acids (see Tall oil). 

The ammonia-water absorption system was extensively used until the fifties when the LiBr-water combination became popular. Figure 11-103 shows a simplified ammonia-water absorption cycle. The refrigerant is ammonia, and the absorbent is dilute aqueous solution of ammonia. Ammonia-water systems differ from water-lithium bromide equipment to accommodate major differences Water (here absorbent) is also volatile, so the regeneration of weak water solution to strong water solution is a fractional distillation. Different refrigerant (ammonia) causes different, much higher pressures about 1100-2100 kPa absolute in condenser. 

This solution is then cooled and made slightly acid by adding about 275 cc. of 50 per cent acetic acid (Note 4). Salt is added if necessary to cause the ester to separate. The ester layer is separated, dried over calcium chloride and fractionally distilled under reduced pressure from a modified Claisen flask (Org. Syn. 1, 40). 

The solution of sodium methyl sulfide in absolute alcohol is transferred to a 3-I. three-necked flask, which is placed on a steam bath and fitted with a dropping funnel, a reflux condenser, and a mechanical stirrer. The solution is heated until the alcohol begins to boil. Heating is then discontinued and 302 g. (3.7s moles) of ethylene chlorohydrin (Note 5) is added dropwise with efficient stirring over a period of about two hours (Note 6). The reaction mixture is concentrated by distilling as much of the alcohol as possible on the steam bath. The mixture is then allowed to cool and the sodium chloride removed by filtration. The flask is rinsed, and the sodium chloride washed with three loo-cc. portions of 95 per cent alcohol. The combined filtrate and washings are concentrated on the steam bath under reduced pressure until no further distillate passes over. The residue is then transferred to a modified Claisen flask (Org. Syn. Coll. Vol. i, 125) and fractionally distilled under reduced pressure. The yield is 238-265 g. (74-82 per cent of the theoretical amount based on the sodium used) of a product boiling at 68-7o°/20 mm. 

Hydrolysis of the ester is achieved by refluxing in aqueous N or 2N NaOH solution until the insoluble ester dissolves. The solution is then cooled, and the alcohol is extracted into a suitable solvent, e.g. ether, toluene or alcohol-free chloroform. The extract is dried (CaS04, MgS04) and distilled, then fractionally distilled if liquid or recrystallised if solid. (The p-nitrobenzoic acid can be recovered by acidification of the aqueous layer.) In most cases where the alcohol to be purified can be readily extracted fi-om ethanol, the hydrolysis of the ester is best achieved with N or 2N ethanolic NaOH or 85% aqueous ethanolic N NaOH. The former is prepared by dissolving the necessary alkali in a minimum volume of water and diluting with absolute alcohol. The ethanolic solution is refluxed for one to two hours and hydrolysis is complete when an aliquot gives a clear solution on dilution with four or five times its volume of water. The bulk of the ethanol is distilled off and the residue is... 

It is not advisable to store large quantities of picrates for long periods, particularly when they are dry due to their potential EXPLOSIVE nature. The free base should be recovered as soon as possible. The picrate is suspended in an excess of 2N aqueous NaOH and warmed a little. Because of the limited solubility of sodium picrate, excess hot water must be added. Alternatively, because of the greater solubility of lithium picrate, aqueous 10% lithium hydroxide solution can be used. The solution is cooled, the amine is extracted with a suitable solvent such as diethyl ether or toluene, washed with 5N NaOH until the alkaline solution remains colourless, then with water, and the extract is dried with anhydrous sodium carbonate. The solvent is distilled off and the amine is fractionally distilled (under reduced pressure if necessary) or recrystallised. 

The ester is hydrolysed by refluxing for l-2h with 1-5% of barium carbonate suspended in water or with aqueous sodium carbonate solution. The solution is cooled and extracted with diethyl ether, toluene or chloroform. It is then acidified and the acid is collected by filtration or extraction, and recrystallised or fractionally distilled. 

The phenol (Imol) in 5% aqueous NaOH is treated (while cooling) with benzoyl chloride (Imol) and the mixture is stirred in an ice bath until separation of the solid benzoyl derivative is complete. The derivative is filtered off, washed with alkali, then water, and dried (in a vacuum desiccator over NaOH). It is recrystalUsed from ethanol or dilute aqueous ethanol. The benzoylation can also be carried out in dry pyridine at low temperature ca 0°) instead of in NaOH solution, finally pouring the mixture into water and collecting the solid as above. The ester is hydrolysed by refluxing in an alcohol (for example, ethanol, n-butanol) containing two or three equivalents of the alkoxide of the corresponding alcohol (for example sodium ethoxide or sodium n-butoxide) and a few ca 5-10) millilitres of water, for half an hour to three hours. When hydrolysis is complete, an aliquot will remain clear on dilution with four to five times its volume of water. Most of the solvent is distilled off. The residue is diluted with cold water and acidified, and the phenol is steam distilled. The latter is collected from the distillate, dried and either fractionally distilled or recrystalUsed. 

These can be converted to their uranyl nitrate addition compounds. The crude or partially purified ester is saturated with uranyl nitrate solution and the adduct filtered off. It is recrystallised from -hexane, toluene or ethanol. For the more soluble members crystallisation from hexane using low temperatures (-40°) has been successful. The adduct is decomposed by shaking with sodium carbonate solution and water, the solvent is steam distilled (if hexane or toluene is used) and the ester is collected by filtration. Alternatively, after decomposition, the organic layer is separated, dried with CaCl or BaO, filtered, and fractionally distilled under high vacuum. 

Liquid carboxylic acids are first freed from neutral and basic impurities by dissolving them in aqueous alkali and extracting with diethyl ether. (The pH of the solution should be at least three units above the pKg of the acid, see pK in Chapter 1). The aqueous phase is then acidified to a pH at least three units below the pK of the acid and again extracted with ether. The extract is dried with magnesium sulfate or sodium sulfate and the ether is distilled off The acid is fractionally distilled through an efficient column. It can be further purified by... 

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