Alcohols ethyl

Ethyl acrylate was negative in most geno-toxic assays. 

Exposure of pregnant rats to 150 ppm 6 hours/day during days 6-15 of gestation caused some maternal toxicity and a slight, but not statistically significant, increase in malformed fetuses at 50 ppm, there was neither maternal toxicity nor an adverse effect on the fetus. 

One drop of the liquid instilled in the eye of the rabbit caused corneal necrosis within 24 hours.  

The odor is detectable below 1 ppm and should serve as a good warning property.  

The 2003 ACGIEl threshold limit value-time-weighted average (TLV-TWA) for ethyl acrylate is 5 ppm (21 mg/m ) with a short-term excursion limit of 15 ppm (61mg/m ) and an A2-suspected human carcinogen designation. 

Ethyl alcohol (ethanol, freezing point -114.1°C, boiling point 78.3°C, density 0.7893, flashpoint 14°C) is also named, industrial alcohol, grain alcohol, and alcohol. Ethyl alcohol is miscible in all proportions with water or with ether. When ignited, ethyl alcohol burns in air with a pale blue, transparent flame, producing water and carbon dioxide. The vapor forms an explosive mixture with air and is used in some internal combustion engines under compression as a fuel such mixtures are frequently referred to as gasohol. 

The next method of manufacture, the esterification/hydrolysis of ethylene, was another method of choice, and an important side product in this electrophilic addition to ethylene was diethyl ether. 

The current process of choice involves the direct hydration of ethylene with a catalytic amount of phosphoric acid (Fig. 1). Temperatures average 300 to 400°C with 1000 psi. 

Only 4 percent of the ethylene is converted to alcohol per pass, but this cyclic process eventually gives a net yield of 97 percent. 

In this direct hydration process, a supported acid catalyst usually is used. Important factors affecting the conversion include temperature, pressure, the water/ethylene ratio, and the purity of the ethylene. Further, some by-products are formed by other reactions taking place, a primary side reaction being the dehydration of ethyl alcohol into diethyl ether  

Methylated spirit contains, in addition to ethyl and methyl alcohols, water, fusel-oil, acetaldehyde, and acetone. It may be freed from aldehyde by boiling with a—3 per cent, solid caustic potash on the water-bath with an upright condenser for one hour, or if larger quantities are employed, a tin bottle is preferable, which is heated directly over a small flame (see Fig. 38). It is then distilled with the apparatus shown in Fig. 39. The bottle is here surmounted with a T-piece holding a thermometer. The distillation is stopped when most of the spirit has distilled and the thermometer indicates 80°. A further purification may be effected by adding a little powdered permanganate of potash and by a second distillation, but this is rarely necessary. The same method of purification may be applied to over-proof spirit, which will henceforth be called spirit as distinguished from the purified product or absolute alcohol. 

Commercial absolute alcohol may be used for the preparations which follow. It Is obtained by distilling crude spirits of wine over quicklime, and usually contains about o 5 per cent, of water. 

Properties.—Pure ethyl alcohol boils at 78 3°, and has a sp. gr. of 0793 at 15. It minces with water in all proportions 

Reaction.—A delicate test for ethyl alcohol is the lodofornt reaction. Pour a few drops of alcohol into a test-tube and add about 5 c.c of a solution of iodine in potassium iodide, and then dilute caustic soda solution until the iodine colour vanishes. Shake up and narm very gently to about 6o°. If no turbidity 01 precipitate appears at once, set the test-tube aside for a time. Yellow crystals of iodoform will ultimately deposit, which have a peculiar odoui, and a characteiistic star shape nhen viewed under the microscope. The same reaction is given with 

Many healthcare facilities use 70% ethyl alcohol as a topical application in local skin disinfection. Consider ethyl alcohol as flammable in all dilutions where vapor may come in contact with an 

Coefficient of cubical expansion Color. Pl Co scale Critical pressure Critical temperature Density at Zi C Dielectric constant at 10 C Dipole moment, px 10  

Electrical conductivity at 1S C Explosive range Fire hazard 

Heat of solution of Water in Ethyl Alcohol) mole fraction of Water 0.640 at 77 C 0.843 at 79.2 C 

Melting point Molecular weight Non-volatile matter 

Specific heat at 20 C Specific tension at 2S C Thermal conductivity, k. at 68 F 

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Chemical methods may be employed if the reagent attacks only one of the components. Thus quicklime may be employed for the removal of water in the preparation of absolute ethyl alcohol. Also aromatic and unsaturated hydrocarbons may be removed from mixtures with saturated hydrocarbons by sulphonation. 

Some liquids are practically immiscible e.g., water and mercury), whilst others e.g., water and ethyl alcohol or acetone) mix with one another in all proportions. Many examples are known, however, in which the liquids are partially miscible with one another. If, for example, water be added to ether or if ether be added to water and the mixture shaken, solution will take place up to a certain point beyond this point further addition of water on the one hand, or of ether on the other, will result in the formation of two liquid layers, one consisting of a saturated solution of water in ether and the other a saturated solution of ether in water. Two such mutually saturated solutions in equilibrium at a particular temperature are called conjugate solutions. It must be mentioned that there is no essential theoretical difference between liquids of partial and complete miscibility for, as wdll be shown below, the one may pass into the other with change of experimental conditions, such as temperature and, less frequently, of pressure. 

An important application of the critical solution temperature is to the determination of the water content in such substances as methyl and ethyl alcohols. Here the system is usually the alcohol and a hydro carbon, such as -hexane or dicyclohexyl the water is, of course, insoluble in the hydrocarbon. Thus, the methyl alcohol - cyclohexane system has a C.S.T. of 45 -5° and even 0 01 per cent, of water produces a rise of 0-15° in the C.S.T. The experimental details are given below. 

For ethyl alcohol, two volumes of dicycZohexyl are mixed with one volume of the alcohol, a thermometer is introduced, and the mixture heated until it becomes clear. The solution is then slowly cooled, with constant stirring, and the temperature is determined at which the opalescent solution suddenly becomes turbid so that the immersed portion of the mercury thread of the thermometer is no longer clearly visible. This is the C.S.T. The water content may then be evaluated by reference to the following table. 

The procedure whereby a Iktle alcohol is rapidly added to the vessel, supported in the funae chamber and containing some concentrated nitric acid, although generally preceded by a short period of induction, may be extremely dangerous and should not be used. Under no circumstances should concentrated nitric acid be euided to ethyl alcohol—a violent explosion may result. 

Solid carbon dioxide (Dry Ice, Drikold) is employed when very low temperatures are required. If it is suspended in solvents, such as alcohol or a mixture of equal volumes of chloroform and carbon tetrachloride, temperatures down to — 50° can be easily attained. Lower temperatures still are reached if intimate mixtures of solid carbon dioxide and organic solvents are employed with ethyl alcohol, — 72° with... 

The inflammable solvents most frequently used for reaction media, extraction or recrystallisation are diethyl ether, petroleum ether (b.p. 40-60° and higher ranges), carbon disulphide, acetone, methyl and ethyl alcohols, di-Mo-propyl ether, benzene, and toluene. Special precautions must be taken in handling these (and other equivalent) solvents if the danger of Are is to be more or less completely eliminated. It is advisable to have, if possible, a special bench in the laboratory devoted entirely to the recovery or distillation of these solvents no flames are permitted on this bench. 

The use of a ternary mixture in the drying of a liquid (ethyl alcohol) has been described in Section 1,5 the following is an example of its application to the drying of a solid. Laevulose (fructose) is dissolved in warm absolute ethyl alcohol, benzene is added, and the mixture is fractionated. A ternary mixture, alcohol-benzene-water, b.p. 64°, distils first, and then the binary mixture, benzene-alcohol, b.p. 68-3°. The residual, dry alcoholic solution is partially distilled and the concentrated solution is allowed to crystallise the anhydrous sugar separates. 

Drying by hydrolysis. The production of extremely dry (99 -9-(- per cent.) ethyl alcohol from commercial absolute alcohol (99-f percent.) is possible by taking advantage of the fact that the hydrolysis of an ester consumes water. Thus if the absolute alcohol is treated with a little sodium in the presence of an ester of high boiling point e.g., ethyl... 

Selection of solvents. The choice of solvent will naturally depend in the first place upon the solubility relations of the substance. If this is already in solution, for example, as an extract, it is usually evaporated to dryness under reduced pressure and then dissolved in a suitable medium the solution must be dilute since crystallisation in the column must be avoided. The solvents generally employed possess boiling points between 40° and 85°. The most widely used medium is light petroleum (b.p. not above 80°) others are cycZohexane, carbon disulphide, benzene, chloroform, carbon tetrachloride, methylene chloride, ethyl acetate, ethyl alcohol, acetone, ether and acetic acid. 

The developer is generally a solvent in which the components of the mixture are not too soluble and is usually a solvent of low molecular weight. The adsorbent is selected so that the solvent is adsorbed somewhat but not too strongly if the solvent is adsorbed to some extent, it helps to ensure that the components of the mixture to be adsorbed will not be too firmly bound. Usually an adsorbate adheres to any one adsorbent more firmly in a less polar solvent, consequently when, as frequently occurs, a single dense adsorption zone is obtained with light petroleum and develops only slowly when washed with this solvent, the development may be accelerated by passing to a more polar solvent. Numerous adsorbat are broken up by methyl alcohol, ethyl alcohol or acetone. It is not generally necessary to employ the pure alcohol the addition from 0 5 to 2 per cent, to the solvent actually used suffices in most cases. 

Absolute diethyl ether. The chief impurities in commercial ether (sp. gr. 0- 720) are water, ethyl alcohol, and, in samples which have been exposed to the air and light for some time, ethyl peroxide. The presence of peroxides may be detected either by the liberation of iodine (brown colouration or blue colouration with starch solution) when a small sample is shaken with an equal volume of 2 per cent, potassium iodide solution and a few drops of dilute hydrochloric acid, or by carrying out the perchromio acid test of inorganic analysis with potassium dichromate solution acidified with dilute sulphuric acid. The peroxides may be removed by shaking with a concentrated solution of a ferrous salt, say, 6-10 g. of ferrous salt (s 10-20 ml. of the prepared concentrated solution) to 1 litre of ether. The concentrated solution of ferrous salt is prepared either from 60 g. of crystallised ferrous sulphate, 6 ml. of concentrated sulphuric acid and 110 ml. of water or from 100 g. of crystallised ferrous chloride, 42 ml. of concentrated hydiochloric acid and 85 ml. of water. Peroxides may also be removed by shaking with an aqueous solution of sodium sulphite (for the removal with stannous chloride, see Section VI,12). 

Absolute ethyl alcohol. Ethyl alcohol of a high degree of purity is frequently required in preparative organic chemistry. For some purposes alcohol of ca. 99 -5 per cent, purity is satisfactory this grade may be purchased (the absolute alcohol of commerce), or it may be conveniently prepared by the dehydration of rectified spirit with quicklime. Rectified spirit is the constant boiling point mixture which ethyl alcohol forms with water, and usually contains 95 6 per cent, of alcohol by weight. Wherever the term rectified spirit is used in this book, approximately 95 per cent, ethyl alcohol is to be understood. 

Extremely dry (or super-dry ) ethyl alcohol. The yields in several organic preparations e.g., malonic ester syntheses, reduction with sodium and ethyl alcohol, veronal synthesis) are considerably improved by the use of alcohol of 99-8 per cent, purity or higher. This very high grade ethyl alcohol may be prepared in several ways from commercial absolute alcohol or from the product of dehydration of rectified spirit with quicklime (see under 4). 

Method 2 (E. L. Smith, 1927). Sodium alone cannot be used for the complete removal of water in ethyl alcohol owing to the equilibrium between the resulting sodium hydroxide and ethyl alcohol ... 

If, however, the sodium hydroxide is removed by allowing it to react with excess of an ester of high boiling point, such as ethyl succinate or ethyl phthalate, super-dry ethyl alcohol may be obtained ... 

The ethyl alcohol is easily removed from the excess of ester by distillation through a short column. 

The sodium formate is sparingly soluble in ethyl alcohol and therefore separates out. The residual ethyl formate is catalytically decomposed in the presence of sodium ethoxide at the boUing point of the ethyl alcohol, t.e., by refluxing the mixture ... 

One litre of commercial absolute alcohol (or any ethyl alcohol of 99 per cent, purity or better) is treated with 14 g. of clean, dry sodium when the sodium has completely reacted, 40 g. of pure ethyl formate are added. The mixture is refluxed for 2-3 hom , and the dry alcohol is distilled oflF as in Method 2 the first 25 ml. of distillate are discarded. The super-dry alcohol contains about 0 03 per cent, of water. 

If the perfectly anhydrous alcohols are required, the redistilled alcohol may be treated with the appropriate alkyl phthalate or succinate as already detaUed under Ethyl alcohol (5). 

Ethyl acetate. Various grades of ethyl acetate are marketed. The anhydrous comjjound, b.p. 76-77°, is of 99 per cent, purity, is inexpensive, and is suitable for most purposes. The 95-98 per cent, grade usually contains some water, ethyl alcohol and acetic acid, and may be ptuified in the following manner. A mixture of 1 litre of the commercial ethyl acetate, 100 ml. of acetic anhydride and 10 drops of concentrated sulphuric acid is refluxed for 4 hours and then fractionated. The distU-late is shaken with 20-30 g. of anhydrous potassium carbonate, filtered and redistilled. The final product has a purity of about 99-7% and boils at 77°/760 mm. 

Pure pyridine may be prepared from technical coal-tar pyridine in the following manner. The technical pyridine is first dried over solid sodium hydroxide, distilled through an efficient fractionating column, and the fraction, b.p. 114 116° collected. Four hundred ml. of the redistilled p)rridine are added to a reagent prepared by dissolving 340 g. of anhydrous zinc chloride in a mixture of 210 ml. of concentrated hydrochloric acid and 1 litre of absolute ethyl alcohol. A crystalline precipitate of an addition compound (probable composition 2C5H5N,ZnCl2,HCl ) separates and some heat is evolved. When cold, this is collected by suction filtration and washed with a little absolute ethyl alcohol. The yield is about 680 g. It is recrystaUised from absolute ethyl alcohol to a constant m.p. (151-8°). The base is liberated by the addition of excess of concentrated... 

There appear to be at least two zinc chloride complexes of pyridine, one of m.p. 207 and composition 2CsH,N,ZnCh, sind the other of m.p. 152° and probable composition 2C,H,N,ZnClt,HCl. The former is slightly soluble in water and in hot ethyl alcohol the latter passes into the former in aqueous solution, is readily soluble in hot absolute ethanol and can therefore be readily recrystaUised from this solvent. 

Chloroform. The commercial product contains up to 1 per cent, of ethyl alcohol, which is added as a stabiliser. The alcohol may be removed by either of the following procedures —... 

Sodamide should never be stored in a stoppered bottle from which samples are to be removed intermittently, since dangerous mixtures may result when the substance is exposed for 2-3 days to even limited amounts of air at the ordinary temperature. As a safe practice, sodamide should be used immediately after preparation, and should not be kept longer than 12-24 hours unless it be under an inert solvent. Even small amounts of unused sodamide should be removed from the apparatus in which it was made by washing with methyl or ethyl alcohol. In all cases where a yellowish or brownish colour develops, due to the formation of oxidation... 

The anhydrous compound is not appreciably hygroscopic, is readily soluble in acetone and amyl alcohol, and insoluble in benzene, toluene, xylene and chloroform it is also readily soluble in absolute methyl or ethyl alcohol, but a trace of water causes immediate hydrolysis with the formation of an opalescent precipitate. 

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