Alcohols. Physical Properties.

Methyl alcohol, the first member of the series, is a liquid boiling at 65, in contrast to methane which boils at 161. Even ethane, which has almost the same molecular weight as methyl alcohol, boils at 88. The alcohols in general boil at a considerably higher temperature than the saturated hydrocarbons of the same molecular weight. The rise in boiling point of the straight chain primary alcohols with increasing molecular weight is about 18 for each additional CH2 group, as shown by Fig. 37. For a given molecular weight, branching of the carbon chain lowers the boiling point just as it does in hydrocarbons. The boiling points of n-, i-, and t-butyl alcohols are respectively 117, 107, and 83. The boiling point of sbutyl alcohol is 100 indicating that the hydroxyl group acts like a branch as might be expected. The much higher boiling point of water and of alcohols as compared with alkanes of the same molecular weight means that an attractive force, in addition to the transient dipole caused by polarizability, must be operating. This second type of van der Waals force appears between molecules having hydrogen bound to oxygen or nitrogen and molecules containing an unshared pair of electrons on oxygen o nitrogen, and in a few other isolated instances. The hydrogen atom is unique in that it has a single electron surrounding the nucleus. When it is bonded to other elements, the hydrogen nucleus, that is, the proton, is less protected by a cover of electrons than the nuclei of other elements, and it can approach the electron shells of other molecules more closely. The result is than an attractive force can appear between the proton and any concentration of negative charge in another molecule. If the other molecule contains an atom having an unshared pair of electrons and if this atom will share this pair of electrons more nearly equally with the proton than does the atom to which the proton is attached, that is, form a more nearly covalent bond, transfer of the proton from one atom to the other takes place. The usual acid-base reactions are of this type. H3N : + H : CL [H3N+ : H] [Cl-]

If the new bond were less covalent than the original bond, no transfer would take place. Thus there is no tendency for an alkane to transfer a proton to other elements, because hydrogen forms a more nearly covalent bond with carbon than any other element except another hydrogen.

Conceivably an intermediate condition should be possible in which the relative electrical forces are such that the tendency of hydrogen to form covalent bonds with two atoms is equal or nearly so. Then if the molecules approach each other closely enough and in the right orientation for transfer of a proton to take place, there will be a stage where the proton is attracted equally or almost equally by the atoms of two molecules. Under such conditions the proton may or may not transfer from one molecule to the other, and if transfer does take place, it will be reversible. Nevertheless during the time when the molecules are close enough for the transfer to take place, there will be a strong attraction of the proton for both molecules and hence an increased attraction between the molecules. This type of attraction is called proton bonding or hydrogen bond. The former term is more descriptive of the process and avoids confusion with the normal covalent hydrogen bond. The phenomenon also is known as association, and compounds exhibiting proton bonding are said to be associated. On this basis the high boiling point of water as compared with methane is due to the association of water molecules by proton bonding. The high boiling point of the alcohols as compared with the boiling point of alkanes of similar molecular weight may be explained in the same way.

However, the attractive forces between alcohol molecules are not so great as those between water molecules, because the hydrogen atoms of the alkyl groups do not form proton bonds, and the bulk of the alkyl groups decreases the chance that collision of two alcohol molecules will form a proton bond between two hydroxyl groups. In proton bonding, a single proton cannot attract more than two other atoms. Because of the small size of the proton, two water molecules or two alcohol molecules approach each other so closely that a third molecule cannot approach the proton closely enough to be attracted appreciably. However, a proton of a third molecule can bond to one of the oxygen atoms, and this process can be repeated until the attractive forces balance the disruptive forces caused by thermal agitation.

The reason that proton bonding occurs most frequently between molecules having hydrogen on oxygen or on nitrogen and those having an unshared pair of electrons on oxygen or nitrogen is simply that then the balance of electrical forces is such that proton bonding is possible. The proton is held neither too strongly nor too loosely by oxygen and nitrogen and the negative charge resulting from the unshared pair on oxygen or nitrogen is sufficiently concentrated to be effective. Fundamentally the attraction is not concerned with an unshared pair of electrons. However only when an atom has an unshared pair is the negative charge sufficiently exposed for a proton attached to another oxygen or nitrogen atom in another molecule to get close enough to the electrons for an attractive force to operate. Dodecyl alcohol is the first straight chain alcohol which is solid at room temperature, although the more nearly spherical branched alcohols with fewer carbon atoms, for example t-butyl alcohol, also may be solids at room temperature. There is no evidence for alternation in melting point (Fig. 38) as is exhibited by saturated hydrocarbons.

The alcohols containing three carbon atoms or less and t-butyl alcohol are miscible with water at 20, but n-butyl alcohol is soluble to the extent of only about 8 per cent, and primary alcohols with more than five carbon atoms are less than 1 per cent soluble in water, Solution is nothing more than the intermingling of molecules. Two liquids will not mix if the attractive forces between unlike molecules. Moreover the more closely molecules are related in composition and structure, the more similar will be the attractive and repulsive forces between them. These statements explain the very approximate rule that like dissolves like. Its desirable to have a somewhat clearer picture of the factors producing solubility and insolubility. From the differences in boiling points, it was concluded that the attraction between water molecules is considerably greater than between alcohol

molecules, and it might be predicted that water and methyl alcohol would not mix. However alcohol molecules can form proton bonds with water molecules and vice versa with the result that differences in attractive forces are decreased and intermingling takes place.

As the length of the hydrocarbon chain increases, the attractive forces resulting from the polarizability of the molecule increase until a point is reached at which the association with water molecules is no longer sufficient to prevent alcohol molecules from being attracted more strongly to each other than to water complexes, and two phases result. The separation is not complete, however. Some alcohol-water complexes remain in the water layer, and some remain in the alcohol layer. Thus 100 g. of n-butyl alcohol dissolves 37 g. of water, and 100 g. of water agrees with the fact that it boils lower than n-butyl alcohol, since the higher solubility and lower boiling point are both dependent on the lower attractive forces between t-butyl alcohol molecules. Alcohols of commercial importance Methyl Alcohol. The word methyl, first used by Dumas and Peligot in 1834, was derived from the Greek word methy meaning wine and yle meaning wood or material, and refers to the fact that it is the chief alcohol formed by the destructive detillation of wood. Previous to 1919 it commonly was called wood alcohol or Columbian spirits in the United States. With the introduction of national prohibition of alcoholic beverages and the advent of the speak-easy over which the authorities had no supervisory control, anything called alcohol was used for intoxicating drinks. Since methyl alcohol is highly toxic, the result was an alarming number of deaths and cases of blindness. As one combative measure the use of the Geneva name methanol was urged, and it now largely has displaced the older term. Methyl alcohol now is obtained both by wood distillation and by a synthetic process. In the wood distillation process dried hardwood such as beech, birch, hickory, maple, or oak is discomposed in an oven or retort at a temperature increasing from about 160 to 450. If the wood is dry when placed in the retort, the reaction is exothermic, and heat is supplied only to start the reaction. The products are gases, which are burned as fuel, a liquid condensate, and a residue of charcoal. The liquid condensate separates into an aqueous layer called

pyroligneous acid, and a tarry layer. The pyroligneous acid, of which 200 to 250 gallons per cord of wood is obtained, is mostly water but contains 1 to 6 per cent of methyl alcohol, 4 to 10 per cent acetic acid, 0.1 to 0.5 per cent of acetone, and smaller amounts of methyl acetate and a number of other organic compounds. In the oldest process for the separation of the components, the acetic acid is neutralized with lime to produce the nonvolatile calcium acetate, and the mixture is distilled to give a liquid containing 8 to 10 per cent of methyl alcohol and the other volatile constituents. Fractional distillation gives the so-called 82 per cent methyl alcohol containing 82 per cent organic compounds or 60-65 per cent methyl alcohol, 11-14 per cent acetone, and 6-8 per cent methyl acetate. Further fractionation removes the methyl acetate and acetone as low constant-boiling mixtures with methyl alcohol. This mixture is known as methyl acetone and is sold as a solvent without further separation. The next fraction contains 92-95 per cent methyl alcohol. The higher-boiling fractions contain allyl alcohol, n-propyl alcohol, and methyl ethyl ketone. Pure methyl alcohol was obtained through the calcium chloride complex. During the year 1924 the total importation of methyl alcohol by the United States was 48 gallons. This material was of high purity, the import duty of 12 cents per gallon being sufficient to prevent importation of the commercial grade of foreign wood alcohol. During the first five months of 1925, the Badische Company of Germany shipped into the United States almost a quarter of a million gallons of methyl alcohol. Wood alcohol was selling for 88 cents per gallon, but the imported material was being made by a synthetic process perfected in 1923 which could produce methanol at a cost of around 20 cents per gallon. Even raising the import duty to 18 cents per gallon, the maximum permitted by law, was of little help to the wood distillers. Not enough methanol was shipped into the country to drive the price below 57 cents per gallon in 1925, and for some reason the price rose again to 82 cents per gallon in February 1927. However with the advent of synthetic production in the United States, the price became stabilized in 1930 at about 40 cents per gallon. Many of the wood distillation plants survived because of more efficient operation and revision of their procedures, particularly the development of new methods for separating acetic acid by extraction or by special distillation process. The synthetic process starts with carbon monoxide and hydrogen which combine over a zinc oxide catalyst containing other promoter oxides, for example 10 per cent chromium oxide, at a temperature of 300-400 and at pressures of 200 to 300 atmospheres. CO + 2 H2
ZnO-Cr O 2 3

> CH2OH

The synthesis frequently is carried out in conjunction with some other operation such as the symthesis of ammonia, acetylene or hydrogen cyanide. By-product hydrogen from other process, such as the anaerobic fermentation of carbohydrates, or the electrolytic production of chlorine, may be used, but most of the carbon monoxide and hydrogen is produced from natural gas. Some higher alcohols also are produced in the synthetic process. The amount can be increased by modifying the catalyst, for example by adding alkalies or by using an iron base-alkali catalyst, and by raising the temperature ti 350-475. Methyl alcohol is obtained also as one of the products of the controlled air oxidation of natural gas. Other alcohols also are formed as well as aldehydes, ketones, and organic acids. The total production of synthetic methanol in the United States in 1955 was 1.3 billion pounds, or 204 million gallons, exceeding the production of any other synthetic organic chemical. About 45 per cent was used for the manufacture of formaldehyde, 25 per cent for the synthesis of other chemicals, 15 per cent as radiator antifreeze, and 15 per cent as solvent and denaturant for ethyl alcohol. Production of wood alcohol was 2.3 million gallons. Practically all of it was used to denature ethyl alcohol. When pure synthetic methanol sold for 30 cent per gallon, impure wood alcohol sold for 70 cents per gallon, because by law it is a required ingredient of certain formulas for denatured ethyl alcohol. Ethyl Alcohol. Although the suffix yl was used in 1834 by Dumas and Peligot in the word methyl to indicate its derivation from wood, Liebig and Woehler had used the same suffix in 1832 in the term benzoyl in the sense of stuff or material. It is in the latter sense that it ordinary is used. Ethyl means the material which gives rise to ether. One important source of ethyl alcohol is the fermentation of sugars. Fermentation is the decomposition of organic compounds into simpler compounds trough the agency of enzymes. Enzymes are complex organic compounds secreted by living cells. The name enzyme means in yeast and was given because the earliest known enzymes were those secreted by yeast cells. Pasteur, who discovered the nature of fermentation, thought that the living cell was necessary, but this view was disproven by Buchner in 1897. He showed that the juice expressed from yeast cells which had been completely destroyed still was capable of bringing about fermentation. The chief sources of sugars for fermentation are the various starches and the molasses residue from sugar refining. Corn (maize) is the chief source of starch in the US, and ethyl alcohol made from corn commonly is known as grain alcohol. Potatoes are the chief sources of starch in Europe, and rice in Asia. In preparing alcohol from corn the germ first is removed, and the remainder ground

and cooked to give the mash. Malt (sprouted barley), or a mold such as Aspergillus oryzae, containing the enzyme diastase is added, and the mixture kept at 40 until all of the starch has been converted into the sugar maltose. This solution is known as the wort.

The wort is cooled to 20, diluted to 10 per cent maltose, and a pure yeast culture added, usually a strain of Saccharomyces cerevisiae (or ellipsoidus) . The yeast cells secrete two enzymes, maltase, which converts the maltose into glucose, and zymase, which converts the glucose into carbon dioxide and alcohol.

Heat us liberated, and the temperature must be kept below 32 by cooling. After 40 to 60 hours, fermentation is complete, and the product is run through beer stills to remove the alcohol from solid matter. The distillate is fractionated by means of an efficient column of the bubble cap type. A small amount of acetaldehyde (b.p. 21) distills first and is followed by 95 per cent alcohol. Fusel oil is withdrawn from the center of the column. The fusel oil consist of a mixture if higher alcohols, chiefly n-propyl, i-butyl, i-amyl (3-methyl-1-butanol), and active amyl (2-methyl-1-butanol). The exact composition of fusel oil varies considerably, being dependent particulary on the type of raw material that is fermented. These higher alcohols are not formed by fermentation of glucose but arise from certain amino acids derived from the proteins present in the raw material and in the yeast. Industrial alcohol is ethyl alcohol used for nonbeverage purposes and usually is not produced from starch. Previous to the development of efficient synthetic processes, the chief source of industrial alcohol was the fermentation of blackstrap molasses, the noncrystallizable residue from the refining of sucrose (cane sugar). It contains about 50 per cent of sucrose. Malt is unnecessary in the fermentation, since yeast contains an enzyme, sucrose (invertase), capable of converting sucrose into glucose and fructose, both of which are fermentable by zymase.

The black-strap molasses is shipped from the islands of the Caribbean Sea by tankers to plants located on the Atlantic and Gulf coasts. It is diluted with water to give a sucrose concentration of 14 to 18 per cent, and the solution is weakly acidified with sulfuric acid to prevent the growth of harmful organisms. After the addition of yeast, the process is the same as for the production of alcohol from starch. Plants may have fermenter of a half million gallons capacity, which are enclosed to collect the carbon dioxide for recovery of alcohol vapors and for the condensation of the carbon dioxide to the liquid or solid form. Storage capacity for molasses may be as high as 6,000,000 gallons. The waste liquors from the production of wood pulp by the sulfite process contain a low concentration of fermentable sugars and can yield about 20 gallons of alcohol per ton of wood pulp produced. Numerous plants utilizing waste sulfite liquors are operated in the Scandinavian countries and in Germany, and in 1954 two plants were operating in Canada and one in the US. Glucose formed by the hydrolysis of wood cellulose also is a possible source of carbohydrate for fermentation which has been utilized in Germany. Experimental plants have been built in the US, but they have not been able to compete with other processes under normal economic conditions. The flowers of Bassia latifolia and other species have a high content of glucose and fructose and are used extensively for the production of alcohol in India. Several processes for the synthesis of ethyl alcohol are possible. The first synthesis was reported by Hennel in 1828, the same year in which Woehler reported the synthesis of urea. In 1826 Hennel had reported the isolation of potassium ethyl sulfate from a sample of sulfuric acid which had absorbed 80 volumes of ethylene, and which had been given to him by Faraday for investigation. In 1828 Hennel reported the hydrolysis of potassium ethyl sulfate to ethyl alcohol. Hennels discovery was overlooked, however, and the synthesis was rediscovered in 1855 by Berthelot, who absorbed the ethylene from coal gas in concentrated sulfuric acid, and diluted and distilled the solution.

Although the possibility of industrial synthesis by this process was discussed in the following year and a claim made in France in 1862 that the cost of synthetic alcohol was about one-third that of fermentation alcohol, the first continuously successful process was not operated until 1930 in US. The ethylene used as the raw material is produced by the cracking of hydrocarbons. It is absorbed in concentrated sulfuric acid at 100 to give a mixture of ethyl hydrogen sulfate and ethyl sulfate. Dilution with water brings about hydrolysis to ethyl alcohol, which is removed by distillation. The dilute sulfuric acid is concentrated for reuse. Since 1949 ethyl alcohol has been manufactured also by direct hydration of ethylene in the vapor phase. The conditions reported are a large excess of water, high temperature (300) and pressure (1000-4000 p.s.i.), and a solid catalyst such as phosphoric acid on a carrier, hydrogen fluoride-treated clays, or promoted tungsten oxide. By 1940, the synthetic process accounted for 25 per cent of the total US. production of industrial alcohol and in 1955 for 80 per cent. Ethyl alcohol also is one of the products of the butyl alcohol fermentation of starch, of the Fischer-Tropsch synthesis of liquid hydrocarbon fuels and of the controlled oxidation of natural gas. Various grades of ethyl alcohol are produced. Ordinary alcohol is 92-95 per cent ethyl alcohol by weight, the remainder being chiefly water. Anhydrous alcohol cannot be obtained by simple distillation because a constant-boiling mixture (also called an azeotrope) containing 95.6 per cent alcohol by weight boils lower (78.15) than pure alcohol (78.3). In the distillation three types of binary mixtures are recognized. In type I, the boiling of all compositions lies between those of the two components. In type II, there is some particular composition at which the boiling point is lower than that of either component. In type III, there is a particular composition at which the boiling point is higher than that either component. Figure 39 gives typical boiling points diagrams for the three types. With reference to the diagram for type I, curve L represents the boiling point of the liquid for different mixtures of components A and B. Curve V represents the composition of the vapor phase when its in equilibrium with the liquid. If a mixture has the composition x, the instantaneous boiling point of the liquid will be t, and the composition of the vapor in equilibrium with the liquid at this temperature will be xI. In other words the vapor phase contains a higher concentration of the lower-boiling constituent than the liquid phase from which it distilled. If this vapor is condensed and redistilled, the new vapor phase will have the composition x. Hence it is possible by fractional distillation or by the use of a fractionating column, which is a device for providing continues fractional distillation, to separate the mixture into its pure components.

In types II and III the vapor and liquid curves touch at some particular composition. In other words, at this composition of the liquid the vapor coming from it has the same composition as the liquid. Hence no separation can occur on distillation, the liquid phase retains a constant composition, and the mixture boils at a constant temperature. In these types the mixture behaves like a binary mixture of type I, consisting of the constant-boiling mixture and one of the pure components. For example referring to the diagram for type II, if the mixture has compositions x, distillation will concentrate the constant-boiling mixture C in the distillate, and component B in the still; if the mixture has composition y, the constant-boiling mixture again will concentrate in the distillate, and component A will concentrate in the still. For mixtures of type III, either component A or B will concentrate in the distillate and the constant-boiling mixture, which boils higher than either component, remains in the still.

The deviations from ideality arise when different molecules exert an attraction for each other which differs from the attractive forces between like molecules. Maxima and minim in physical phenomena occur when more than one factor influences a property and when these factors vary in opposite directions with charge of a third factor. The various attractive forces between molecules play an important part in determining the extent of deviation from ideality and whether maxima or minima will arise in the distillation curves as the composition of the liquid changes. Absolute alcohol (anhydrous, 99.9+ per cent) usually is prepared in the laboratory by removing the water by chemical means, for example by heating with calcium oxide, which reacts with the water, and distilling the dried alcohol from the calcium hydroxide. The 5 per cent water in ordinary alcohol has a marked effect on its solvent properties, and there is a considerable large-scale demand for the anhydrous product. One commercial method of dehydration makes use of the fact that a ternary mixture consisting of 18.5 per cent alcohol, 74.1 per cent benzene, and 7.4 per cent water by weight boils at 64.85. Since the ratio of water to alcohol in the ternary mixture is 1:2.5, enough benzene can be added to remove all of the water in the low-boiling distillate, and anhydrous alcohol can be withdrawn from the

still pot. A binary mixture containing 80.2 per cent of benzene and 19.8 per cent of ethyl alcohol, and boiling at 68.2, permits complete removal of any excess benzene. The ternary distillate separates into two layers. The upper layer comprises 84.7 per cent of the total and consist of 11.6 per cent alcohol, 85.6 per cent benzene, and 2.8 per cent water. The lower layer amounts to 15.3 per cent and consists of 51.3 per cent alcohol, 8.1 per cent benzene, and 40.6 per cent water. Redistillation of the upper layer removes all of its water as the ternary mixture, and the residue is returned to the main still. Redistillation of the lower layer removes all of its benzene as the ternary mixture and leaves a dilute alcohol which is rectified to 95 per cent alcohol and returned to the main still. By the use of four stills the process can be made continuous, with 95 per cent ethyl alcohol entering the system and absolute alcohol and water being withdrawn. Other substances such as 2,2,4-trimethylpentane, trichloroethylene, or ethyl ether may be used as entrainers instead of benzene. Since all countries have derived a sizeable portion of their revenue by taxing alcohol for beverage purposes, ethyl alcohol for industrial use first must be converted into denatured alcohol if the payment of tax is to be avoided. Denaturing is the addition of substances which render the alcohol unfit to drink. Many formulas are available to the manufacturer in order that he may choose one suitable for his purpose. Only denatured alcohols containing obnoxious mixtures that are difficult to remove may be sold to the general public without payment of tax. On January 1, 1940, the price of tax-free denatured alcohol was 31 cents per gallon, compared with $4.55 per gallon for taxed grain alcohol; on January 1, 1956, the prices were 40 cents and $20.35 respectively. The difference in each case is approximately the tax per gallon. The US tax is based on 100 U.S. proof alcohol, which contains half of its volume of absolute alcohol. Since there is a contraction in volume on mixing alcohol and water, one volume of proof spirits contains 0.537 volumes of water. Proof spirits is 42.5 per cent alcohol by weight. Ordinary socalled 95 per cent alcohol is 190 proof. One volume contains 0.95 volume of alcohol and .062 volume of water and is 92.4 per cent alcohol by weight. The term proof spirit has its origin in an old method of testing whiskey by pouring it on some gunpowder and lighting it. Ignition of the gunpowder after the alcohol burned away was considered proof that the whiskey did not contain too much water. The economics of industrial alcohol has changed often and markedly since 1930. Previous to 1931 the price of industrial alcohol was governed by the price of molasses. In 1929 with molasses at 12 cents per gallon, alcohol sold at 48 cents per gallon. In 1931 with molasses at 7 cents, alcohol sold at 27 cents. Since 1931, synthetic alcohol has been made in US. from ethylene and has controlled the price of alcohol. After a slight rise to 30 cents in 1932, the price of alcohol dropped regularly due to improvements and expansion in synthesis until it reached 20 cents

in 1939. Since molasses is a by-product of sugar manufacture, it had to be sold at a price permitting competition of fermentation with synthetic alcohol, and in spite of general economic recovery, its price dropped to 5 cents per gallon in 1939. Then a demand developed for black-strap molasses for animal feed, and it no longer needed to be sold at distress prices. At the end of 1947 molasses sold for 31 cents per gallon, and since 2.5 gallons are required to make one gallon of alcohol, it no longer was a low-cost raw material. With the increase in requirements during World War II and the decrease in the importation of molasses because of submarine warfare, it became necessary to revert to the use of grain (corn and wheat) as a source of industrial alcohol with resulting increase in cost. While price controls were in effect, alcohol sold for around 60 cents per gallon. After the removal of control it rose to over $1 per gallon in 1947 despite the low cost of making synthetic alcohol, simply because the supply was not able to meet the demand. Failure of the manufacturers of synthetic alcohol to expand sufficiently to bring the price back in line with their costs undoubtedly was due to several factors. Probably the most important ones were the high cost of building new plants and the shortage of materials, and the uncertainty concerning the future because of the possibility that alcohol formed as a by-product in the synthesis of gasoline would become more than sufficient to meet the entire needs of the country. This last threat has not materialized and synthetic manufacture expanded sufficiently to bring the price down to 30 cents per gallon in 1954. Production in 1940 was 128 million gallons but rose to 606 million gallons in 1944. In 1955 it was 217 million gallons, of which 80 per cent was made by synthesis from ethylene and only 20 per cent by fermentation of carbohydrates. The sharp rise during World War II was due to its use for the synthesis of butadiene for the manufacture of synthetic rubber. This use required about 55 per cent of the total production. In 1954 about 45 per cent was used for the synthesis of acetaldehyde and 26 per cent for solvent purposes. The remainder was used for the synthesis of other chemical and for miscellaneous purposes. Higher Alcohols. Previous to World War I the chief source of higher alcohols was fusel oil from which n-propyl, i-butyl, i-amyl, and active amyl alcohols were separated by distillation. Since then many other alcohols have become available. n-Butyl alcohol is made by a special bacterial fermentation process. Corn mash or black.strap molasses is inoculated with a pure culture of one of several strains of Clostridium acetobutylicum in closed tanks under anaerobic conditions. The products of fermentation are n-butyl alcohol, acetone, and ethyl alcohol in proportions varying from 60:30:10 to 74:24:2. The evolved gas contains hydrogen and carbon dioxide in the ratio of 1 volume: 2 volumes. The process was developed during World War I as a source of acetone when the supply from the

decomposition of calcium acetate from pyroligneous acid was insufficient to meet the requirements of the British for the production of cordite. At that time there was no large-scale use for n-butyl alcohol, and huge stocks accumulated. Since then uses for n-butyl alcohol have been developed, and now it is the most valuable product, and acetone has become the by-product. n-Butyl alcohol is manufactured also by a synthetic process starting with acetaldehyde. Since acetone also is made by synthesis, the ability of the fermentation process to compete economically depends on the price of corn and molasses. In 1955 the total US. production of nbutyl alcohol was 225 million pounds of which about one third was produced by fermentation and two thirds by synthesis. The chief uses of n-butyl alcohol are as a solvent, for the manufacture of esters, and for the synthesis of n-butyraldehyde and n-butyric acid. Higher branched chain primary alcohols result when normal primary alcohols are heated with the sodium alkoxide in the presence of a nickel catalyst (Guerbet reaction).

2-Methyl-1-pentanol is made commercially in this way from n-propyl alcohol and 2-ethyl-1-hexanol from n-butyl alcohol. The reaction has not been used much in the laboratory because complex mixtures frequently are obtained. Secondary and tertiary alcohols are manufactured on a large scale from the lower olefins obtained by the cracking of saturated hydrocarbons.

Similarly amylenes (pentenes) are converted into secondary and tertiary amyl alcohols. Some of the higher alcohols are obtained also as co-products of methanol synthesis, the Fischer-Tropsch synthesis, and the controlled air oxidation of natural gas. Other methods for synthesizing alcohols are considered after the structures of the compounds from which they are derived have been discussed.