Ethyl alcohol, determination

Table III. Rate Constants for the Reaction of Hydroxyl Radicals with Methanol and Ethyl Alcohol Determined by Competition Kinetics...

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. 

Drop 1 g. of sodium into 10 ml. of ethyl alcohol in a small flask provided with a small water condenser heat the mixture until all the sodium has dissolved. Cool, and add 1 g. of the ester and 0-5 ml. of water. Frequently the sodium salt of the acid will be deposited either at once or after boiling for a few minutes. If this occurs, filter oflF the solid at once, wash it with a little absolute ethyl alcohol (or absolute methylated spirit), and convert it into the p-bromophenacyl ester, p-nitro-benzyl ester or S-benzyl-tso-thiuronium salt (for experimental details, see Section 111,85). If no solid separates, continue the boiling for 30-60 minutes, boil oflF the alcohol, allow to cool, render the product just neutral to phenolphthalein with dilute sulphuric or hydrochloric acid, convert the sodium salt present in solution into a crystalline derivative (Section 111,85), and determine its melting point. 

Method 1. Treat 2 0 g. of the mixture of amines with 40 ml. of 10 per cent, sodium hydroxide solution and add 4 g. (3 ml.) of benzenesulphonyl chloi de (or 4 g. of p-toluenesulphonyl chloride) in small portions. Warm on a water bath to complete the reaction. Acidify the alkaline solution with dilute hydrochloric acid when the sulphonamides of the primary and secondary amines are precipitated. Filter off the solid and wash it with a little cold water the tertiary amine will be present in the filtrate. To convert any disulphOnamide that may have been formed from the primary amine into the sulphonamide, boil the solid under reflux with 2 0 g. of sodium dissolved in 40 ml. of absolute ethyl alcohol for 30 minutes. Dilute with a little water and distil off the alcohol filter off the precipitate of the sulphonamide of the secondary amine. Acidify the filtrate with dilute hydrochloric acid to precipitate the derivative of the primary amine. Recrystallise the respective derivatives from alcohol or from dilute alcohol, and identify them inter alia by a determination of the m.p. 

Dissolve 2-3 g. of methyl p-toluenesnlphonate in 10 ml. of dry benzene, add 1 g. of the amine, and boU the mixture for 20-30 minutes. Cool, and filter the precipitated quaternary salt. Recrystallise by dissolving the solid in the minimum volume of boiling ethyl alcohol and then adding ethyl acetate until crystallisation commences. Filter the cold mixture, dry rapidly on a porous plate, and determine the m.p. immediately. 

Alcoholometer. This hydrometer is used in determining the density of aqueous ethyl alcohol solutions the reading in degrees is numerically the same as the percentage of alcohol by volume. The scale known as Tralle gives the percentage by volume. Wine and Must hydrometer relations are given below. 

Water solubiHty sometimes is important in determining whether water can be used to dilute or flush away flammable Hquids. However, a water solution of flammables can give off sufficient vapors to bum, eg, a 30 vol % solution of ethyl alcohol in water (60 proof) has a flash point which is only 16.6°C above that of pure ethyl alcohol (29.4°C vs 12.8°C). 

Solution Viscosity. Solution viscosity is determined in solvent blends of toluene, ethyl alcohol, and ethyl acetate. The solvent blend and concentration of CN varies according to the viscosity and nitrogen content of the CN being tested. Viscosities are measured at 25°C by the falling-hall method. The results are ordinarily expressed in terms of seconds required for a 2.4 mm diameter steel ball to fall a distance of 5.08 cm through the... 

FIG. 2-10 Enthalpy-concentration diagram for aqueous ethyl alcohol. Reference states Enthalpies of hquid water and ethyl alcohol at 0 C are zero. NOTE In order to interpolate equilihrium compositions, a vertical may he erected from any liquid composition on the hoihug hue and its intersection with the auxihary hue determined. A horizontal from this intersection will estahhsh the equihhrium vapor composition on the dew hue. (Bosnjakovic, Techuische Thermo-dynamik, T. Steinkopff, Leipzig, 1935. )... 

The first instruments used by police to determine BrAc were developed in the 1930s. Until about 1980, the standard method involved adding K O , which reacts chemically with ethyl alcohol. Potassium dichromate has a bright orange-red color, whose intensity fades as reaction occurs. The extent of the color change is a measure of the amount of alcohol present. 

In addition to meeting the foregoing requirements, a good internal standard will be easy to add uniformly and precisely, and (preferably) no appreciable amount of the element St (free or combined) will be present in the sample before the addition. Cope29 provides an excellent illustration of these points. He found that yttrium nitrate dissolved in ethyl alcohol could be added to a powdered uranium mineral in a mortar, whereupon grinding immediately to dryness dispersed the internal standard (yttrium) so uniformly that uranium could be satisfactorily determined in certain minerals. But the mineral euxenite is an exception, for it contains both yttrium and uranium, and this complicates the uranium determination with yttrium as internal standard. 

The free oil can be determined by an ion exchange HPLC technique. A solution of the sample in ethyl alcohol is analysed by high-performance ion exchange chromatography using a specially prepared ion exchange resin stationary phase, ethanol mobile phase, and differential refractive index detection. 

LaClair (43) has employed the dehydrohalogenation reaction to determine the gamma isomer of benzene hexachloride in the technical product and in dust mixtures. Two identical samples are dissolved in 95% ethyl alcohol and treated with 1 N ethanolic potassium hydroxide at 0° C. for 15 and 50 minutes, respectively. The 15-minute period is sufficient to dehydrochlorinate most of the alpha and the delta isomers without appreciably affecting the gamma. In 50 minutes the gamma isomer is also dehydrochlorinated. The beta isomer does not react under these conditions, and usually the epsilon isomer is present in quantities too small to interfere seriously. 

Cristol et al. (17) have based a method for the determination of p,p -DDT in technical DDT on the fact that the p,pf isomer is almost insoluble in 70% aqueous ethyl alcohol and the o,p isomer is soluble. The method has not been tried with mixtures of the other chlorinated hydrocarbons. 

Kearns, Weinman, and Decker determined the dosages of a number of the chlorinated compounds, dissolved in 95% ethyl alcohol, required to produce a 50% mortality of the housefly (7). The values obtained, expressed as micrograms of toxicant per gram of fly weight, are listed in Table V. 

The disappearance of the faint yellow color of triiodide ion was used to determine the end point of the titration with sodium thiosulfate. This gave better results than were obtained when the solution was diluted with sufficient water to use the starch triiodide end point in the presence of ethyl alcohol. 

The metabolic fate of chlordan was studied in rabbits by analysis of the relative chlorine content of chlordan added to normal rabbit s urine and of the chlorine content of the urinary excretory product. The method of analysis was similar to the one previously used (, 4) In addition, hydrolysis of chlordan and of the urinary excretory products was carried out by adding solid sodium hydroxide to saturation to a 10-ml. solution of these substances in hot absolute ethyl alcohol. The mixture was refluxed for 3 hours in a round-bottomed flask immersed in boiling water and the amount of inorganic chlorine determined. Hydrolysis was similarly carried out with solutions of the respective substances in aqueous sodium hydroxide. 

Another important use of solubility parameters is in interpreting the effects of different solvents on the rates of reactions. In a chemical reaction, it is the concentration of the transition state that determines the rate of the reaction. Depending on the characteristics of the transition state, the solvent used can either facilitate or hinder its formation. For example, a transition state that is large and has little charge separation is hindered in its formation by using a solvent that has a high value of S. The volume of activation is usually positive for forming such a transition state which requires expansion of the solvent. A reaction of this type is the esterification of acetic anhydride with ethyl alcohol ... 

Extraction of mustard agent from the samples was realized with ethyl alcohol. The remains of the toxic substance in samples were determined with the spectrophotometer SPECOL according to the thymolphtalein reaction [1, 2] with preliminarily made calibration curve. 

Commercially available kits allow for the determination of compounds such as ethyl alcohol, glucose, lactic acid and lactose. 

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