Alcohols, Estimation

Essential oils (containing tertiary alcohols) - Estimation of free alcohols content by determination of ester value after acetylation... 

Over 50% of the total population (some 100-110 million people) use alcohol in some form for recreational purposes. 250,000 or more people, as of 1972, were dying yearly from alcohol, its illnesses, and related crime. Additionally, there are nine million alcoholics estimated by authoritative sources, undoubtedly going on ten million by now. 

It is recommended to include internal quality controls with each batch of samples to enable an internal check of the reliability of each assay. These controls contain known drugs at known concentrations. Suitable acceptance criteria are required for these controls before results of unknown cases can be accepted and released to a client. Acceptance criteria vary depending on the analyte and application. For example, blood alcohol estimations have acceptance criteria less than 5% while postmortem blood procedures may be 10 to 20%. 

The physical properties of alcohol Production of alcohol Estimation of alcohol content of beverages and monitoring of intake 593... 

Usually prepared by the action of NaCN on benzaldehyde in dilute alcohol. It is oxidized by nitric acid to benzil, and reduced by sodium amalgam to hydrobenzoin PhCHOHCHOHPh by tin amalgam and hydrochloric acid to des-oxybenzoin, PhCH2COPh and by zinc amalgam to stilbene PhCH = CHPh. It gives an oxime, phenylhydrazone and ethanoyl derivative. The a-oxime is used under the name cupron for the estimation of copper and molybdenum. 

Estimate the interfacial tension gradient formed in alcohol-water mixtures as a function of alcohol content. Determine the minimum alcohol content necessary to form wine tears on a vertical glass wall [174] (experimental veriflcation is possible). 

A method of estimating small amounts of water in organic liquids (and also in some inorganic salts) is that of Karl Fischer. The substance is titrated with a mixture of iodine, sulphur dioxide and pyridine dissolved in methyl alcohol. The essential reaction is ... 

Estimation of the Number of Hydroxyl Groups in a given Polyhydric Alcohol or Phenol. 

The excess of unchanged acetic anhydride is then hydrolysed by the addition of water, and the total free acetic acid estimated by titration with standard NaOH solution. Simultaneously a control experiment is performed identical with the above except that the alcohol is omitted. The difference in the volumes of NaOH solution required in the two experiments is equivalent to the difference in the amount of acetic add formed, i.e., to the acetic acid used in the actual acetylation. If the molecular weight of the alcohol is known, the number of hydroxyl groups can then be calculated. 

This method is precisely similar to the previous method used for the estimation of the number of hydroxyl groups in a polyhydric alcohol. A known weight of aniline is heated with a mixture of acetic anhydride and pyridine until acetylation is complete the excess of acetic anhydride remaining is... 

I he methyl iodide is transferred quantitatively (by means of a stream of a carrier gas such as carbon dioxide) to an absorption vessel where it either reacts with alcoholic silver nitrate solution and is finally estimated gravimetrically as Agl, or it is absorbed in an acetic acid solution containing bromine. In the latter case, iodine monobromide is first formed, further oxidation yielding iodic acid, which on subsequent treatment with acid KI solution liberates iodine which is finally estimated with thiosulphate (c/. p. 501). The advantage of this latter method is that six times the original quantity of iodine is finally liberated. 

Amount of material required. It is convenient to employ an arbitrary ratio of 0 10 g. of solid or 0 20 ml. of liquid for 3 0 ml. of solvent. Weigh out 0 10 g. of the finely-powdered solid to the nearest 0 01 g. after some experience, subsequent tests with the same compound may be estimated by eye. Measure out 0-20 ml. of the liquid either with a calibrated dropper (Fig. 11,27, 1) or a small graduated pipette. Use either a calibrated dropper or a graduated pipette to deliver 3 0 ml. of solvent. Rinse the delivery pipette with alcohol, followed by ether each time that it is used. 

Breslow studied the dimerisation of cyclopentadiene and the reaction between substituted maleimides and 9-(hydroxymethyl)anthracene in alcohol-water mixtures. He successfully correlated the rate constant with the solubility of the starting materials for each Diels-Alder reaction. From these relations he estimated the change in solvent accessible surface between initial state and activated complex " . Again, Breslow completely neglects hydrogen bonding interactions, but since he only studied alcohol-water mixtures, the enforced hydrophobic interactions will dominate the behaviour. Recently, also Diels-Alder reactions in dilute salt solutions in aqueous ethanol have been studied and minor rate increases have been observed Lubineau has demonstrated that addition of sugars can induce an extra acceleration of the aqueous Diels-Alder reaction . Also the effect of surfactants on Diels-Alder reactions has been studied. This topic will be extensively reviewed in Chapter 4. 

Apparatus and procedure Closely similar to the preparation of tert.-Ci,H3MgCl, cyclohexyl-MgCl and cyclopentyl-MgCl (see Exp. 2). The yield (estimated from the results obtained from reactions with this reagent) is at least 90%. Here, too, it is essential to use M-butyl chloride which is free from butyl alcohol. 

Worldwide furfuryl alcohol capacity in 1993 was estimated to be 110,000 metric tons (38). As with furfural, new capacity in developing countries is replacing older capacity in developed countries. China and South Africa have become significant producers of furfuryl alcohol. New plants have been built in Asia and Indonesia as well. Consumption of furfuryl alcohol is spread over the globe the largest use is in the foundry industry which is increasingly moving away from heavily industrialized countries. 

Uses. Furfuryl alcohol is widely used as a monomer in manufacturing furfuryl alcohol resins, and as a reactive solvent in a variety of synthetic resins and appHcations. Resins derived from furfuryl alcohol are the most important appHcation for furfuryl alcohol in both utihty and volume. The final cross-linked products display outstanding chemical, thermal, and mechanical properties. They are also heat-stable and remarkably resistant to acids, alkaUes, and solvents. Many commercial resins of various compositions and properties have been prepared by polymerization of furfuryl alcohol and other co-reactants such as furfural, formaldehyde, glyoxal, resorcinol, phenoHc compounds and urea. In 1992, domestic furfuryl alcohol consumption was estimated at 47 million pounds (38). 

Ma.nufa.cture. Most butanediol is manufactured in Reppe plants via hydrogenation of butynediol. Recendy an alternative route involving acetoxyiation of butadiene has come on stream and, more recendy, a route based upon hydroformylation of allyl alcohol. Woddwide butanediol capacity has climbed steadily for many years. In 1990 it was estimated to be 428,000 metric tons (141), as compared to a Htde more than 70,000 metric tons in 1975... 

Alcohol Production. Studies to assess the costs of alcohol fuels and to compare the costs to those of conventional fuels contain significant uncertainties. In general, the low cost estimates iadicate that methanol produced on a large scale from low cost natural gas could compete with gasoline when oil prices are around 140/L ( 27/bbl). This comparison does not give methanol any credits for environmental or energy diversification benefits. Ethanol does not become competitive until petroleum prices are much higher. 

Fig. 2. Estimated primary alcohol distributions for (H) Ethyl Corporation-modified Ziegler and (+) Vista Corporation Ziegler, at 4.0 moles ethylene per...

Methyl /-Butyl Ether. MTBE is produced by reaction of isobutene and methanol on acid ion-exchange resins. The supply of isobutene, obtained from hydrocarbon cracking units or by dehydration of tert-huty alcohol, is limited relative to that of methanol. The cost to produce MTBE from by-product isobutene has been estimated to be between 0.13 to 0.16/L ( 0.50—0.60/gal) (90). Direct production of isobutene by dehydrogenation of isobutane or isomerization of mixed butenes are expensive processes that have seen less commercial use in the United States. 

Titanium Alkoxides. Titanium alkoxides are made from titanium tetrachloride and the corresponding alcohols in the presence of ammonia. Higher titanium alkoxides are manufactured from lower alkoxides by alcoholysis. Titanium isopropoxide and -butoxide are commercially available in barrels. Annual production of titanium alkoxides is estimated at 3000—4000 metric tons at an average price of about 4/kg. 

The ease of hydrolysis of metal alkoxides makes metal analysis a comparatively simple task. In many cases, the metal may be estimated by hydrolysis of a sample in a cmcible, and ignition to the metal oxide. Alternatively, the metal ion may be brought into solution by hydrolysis of a sample with dilute acid, followed by a standard analytical procedure for a solution of that particular metal. If the alcohol Hberated during the hydrolysis is likely to cause interference, it may be distilled from the solution by boiling. 

The estimation of alkoxy groups is not such a simple task. One method (26,68) involves hydrolysis and oxidation of the Hberated alcohol with excess standard potassium dichromate solution. The excess may then be estimated iodometrically. This method is suitable only for methoxides, ethoxides, and isopropoxides quantitative conversion to carbon dioxide, acetic acid, and acetone, respectively, takes place. An alternative method for ethoxides is oxidation followed by distillation, and titration of the Hberated acetic acid. 

For the higher alkoxy groups, standard carbon and hydrogen analysis may be used, although careful sample preparation is required because of the ease of hydrolysis. Quantitative vapor-phase chromatography of alcohol Hberated during hydrolysis may also be used, but care must be taken in this case to ensure that hydrolysis is complete before the estimation is carried out. 

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