Distillation!

The first evidence of distillation was found in Tape Gowra, Mesopotamia. It consisted of a pot, which held almost 40 liters, and a collecting ring, that had a capacity of about 2 liters. This apparatus dates back to 3600 B.C.. Yet, it wasn't until the beginning of the 19th century that this technique was used in chemistry laboratories. Today, a variety of distillation techniques are used commonly in laboratories.

Steam distillation was invented when Avicenna, an Arabian physician, added water to rose petals and distilled the mixture in the 10^th century. The rose water he collected is considered to be the first modern perfume.

Fractional distillation and vacuum distillation were invented near the end of the 18th century. The first columns invented for fractional distillation were simple open tubes and it wasn't until the period 1900-1930 that vast improvements were made. Vacuum distillation, distillation under low pressure, made its appearance in the laboratory setting in 1869.

There also exists freeze distillation. This involves removal of alcohol from water by subjecting the mixture to temperatures below the freezing point of water. The alcohol can then be separated from the ice and distilled using another technique.

The History of Fractional Distillation

The important technique of distillation was probably discovered by the Greek alchemist, Discorides, after he noticed condensate on the lid of a vessel in which some mercury was being heated. The technique of fractional distillation at reduced pressures was initially used to separate mixtures of fatty acids and esters derived from natural fats. The early distillation apparatus were not very efficient. Thus, natural mixtures were first separated into chemically similar groups prior to distillation.

The earliest laboratory columns were simply open tubes and spiral-type columns, these were introduced by Warren in 1864. The period 1900-1930 was one during which marked advances were made. One of the most important was the development of highly efficient packed columns. Columns containing rotating fractionation sections were introduced later in 1935. The oldest record of a distillation process dates about 3600 B.C., it was probably used to make perfumes. The instrument was 48 cm high and 53 cm in largest diameter. The distillation pot had a capacity of about 40 litres and the distillate collecting ring held about 2 litres.

Distillation apparatus made its appearance in the chemical laboratory in the early part of the 19th century, the invention of the distillation column is attributed to Cellier-Blumenthal and Derosene in France and also to Coffey in England. These bubble-plate towers were used primarily for the commercial distillation of spirits.

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Fractional distillation at reduced pressures was initially used to separate mixtures of fatty acids and esters derived from natural fats. The early distillation apparatus were not very efficient. Thus, natural mixtures were first separated into chemically similar groups prior to distillation.

The oldest record of a distillation process dates about 3600 B.C.. It was found at Tape Gowra in Mesopotamia, the instrument was 48 cm high and 53 cm in largest diameter. The distillation pot had a capacity of about 40 liters and the distillate collecting ring held about 2 liters. It was probably used to make perfumes (Great Chemists, E Farber ed, Interscience, NY 1961). As a science, distillation and fractional distillation had to await the discovery of the physical laws of Dalton (1766-1844) and Raoult (1830-1901). After that, the science of distillation developed at an amazing rate.

Distillation apparatus made its appearance in the chemical laboratory in the early part of the 19^th century, according to Underwood AJV ( Trans Inst Chem Engrs (London) 1932, 10, 112-152). An anonymous publication (Ind Eng Chem, News Ed 1935, 13, 140) attributes the invention of the distillation column to Cellier-Blumenthal and Derosene in France; Thorpe JF (Thorpe's Dictionary of appl Chem, vol 1, 1937) attributes it to Coffey in England. These bubble-plate towers were used primarily for the commercial distillation of spirits. An early laboratory distillation unit used for the fractionation of fatty acid esters is illustrated in Reilly's book (Distillation, Methuen, London, 1936). A similar instrument and its operation are described by Hilditch (The constitution of natural fats, 1940, pp374-6).The earliest laboratory column were simply open tubes and spiral-type column was introduced by Warren in 1864 (Mem Am Acad Arts Sci, 1867, 9, 121). The period 1900-1930 was one during which marked advances were made. One of the most important was the development of highly efficient packed columns. Columns containing rotating fractionation sections were described later by Podbielniak in 1935. This device was modified with a thin metal strip rotates at high speeds (1000-2500 rpm) in the glass column (spinning-band column). Baker (Ind Eng Chem, Anal Ed 1940, 12, 468) described a 18-ft column, 0.6 cm in diameter with a separation efficiency equivalent to 70 theoretical plates. The head pressure was 1 mm Hg. This device was used by Privett OS et al (J Am Oil Chem Soc 1959, 36, 443) to distill several fractions of methyl esters of pork liver lipid. One sample of esters was separated into 38 distillate fractions with chain lengths from C14 to C22. 19 specific fatty acids could be identified and quantified (amounts from 0.2 to 35.4% plus traces of 8 other fatty acids, C10-C15, C17 and C19.

The history of fractional distillation of fats and oils may be divided roughly into 2 periods, one preceding and one following the year 1930. Laboratory vacuum distillation was not introduced until 1869 (Dittmar W et al., J Chem Soc 1869, 22, 446; Kekule A et al., Ber 1872, 5, 906). Between 1880 and 1903 Krafft carried out distillations of fatty acids, esters and aldehydes under high vacuum. Separations of pure palmitic and stearic acids for the synthesis of glycerides were reported in 1903 (Krafft F, Ber 1903, 36, 4336) and by Kreiser H et al. (Ber 1903, 36, 2766). A few years later (Haller A et al., Compt Rend 1906, 143, 803) reported the fractional distillation of the methyl esters derived from coconut oil, but without quantification. In 1906, Bull H (Ber 1906, 39, 3570) fractionated methyl esters from cod liver oil and isolated 9-eicosanoic acid. Elsdon GD calculated the composition of coconut oil and palm kernel oil from analytical data obtained by fractional distillation (Analyst 1913, 38, 8-11; 1914, 39, 78). Between 1920 and 1930, analytical fractionation of methyl esters was applied in determining the composition of several oils and fats : peanuts (Jamieson GS et al., J Am Chem Soc 1921, 43, 2696), sunflower (Jamieson GS et al., J Am Chem Soc 1922, 44, 2952), soybeans (Baughman WF et al., J Am Chem Soc 1922, 44, 2947), olives (Jamieson GS et al., J Oil Fat Ind 1925, 2, 40; 1927, 4, 63) etc. In 1923, Brown JB et al. (J Am Chem Soc 1923, 45, 1289) published results of investigations of the unsaturated acids from menhaden oil. The same technique was applied by Brown JB with beef brain lipids (J Biol Chem 1929, 83, 783; 1930, 89, 167).

Following 1930, the objective of ester distillation was to obtain fractions containing "no more than two adjacent homologous saturated and two unsaturated members "(Hilditch Biochem J 1934, 28, 779) and having chain lengths differing by two carbon atoms. Later, with the development of spinning-band columns the objective was to produce fractions of the same chain length irrespective of the degree of unsaturation. This new concept is exemplified by the isolation and identification of 32 compounds from wool wax (Weitkamp AW et al., J Am Chem Soc 1945, 67, 447).
Technical improvements led to molecular distillation of vitamin D (Bills CE et al., J Biol Chem 1938, 126, 241), esters from fish oil (Komori S et al., J Chem Soc Japan, Ind Chem Sect 1951, 54, 225), cholesterol (Hickman KC Ind Eng Chem 1940, 32, 1451) and tocopherols (Hickman Ind Eng Chem 1940, 32, 1451).
Farmer et al (J Soc Chem Ind London 1938, 57, 24) applied molecular distillation to the fractionation of methyl esters from fish oils. They were able to separate DHA in a high state of purity (> 99%). Schuwirth K (Z physiol Chem 1943, 277, 147) distilled the methyl esters of the unsaturated fatty acids of brain phospholipids.

Title page from The Art of Distillation.

Possibly the earliest definitive work on distillation was written by John French in 1651. It's rather snappy title was The Art of Distillation. Or, A Treatise of the Choicest Spagyrical Preparations Performed by Way of Distillation, Being Partly Taken Out of the Most Select Chemical Authors of the Diverse I, Anguages and Partly Out of the Author's Manual Experience Together with, The Description of the Chiefest Furnaces and Vessels Used by Ancient and Modern Chemists also A Discourse on Diverse Spagyrical Experiments and Curiosities, and of the Anatomy of Gold and Silver, with The Chiefest Preparations and Curiosities Thereof, and Virtues of Them All. The work occupied six volumes.

 Today, among the many uses of distillation are the preparation of alcoholic beverages, the refining of petroleum, and the desalination of salt water. In this activity you will distill a mixture of two liquids. That is, you will perform a fractional distillation.

An early drawing of a distillation apparatus.

Miriam the Prophetess is considered the mother of the protoscience of alchemy. Also called “Maria the Jewess,” she is believed to have lived in the first century A.D. Writing 500 years later, the Egyptian alchemist Zosimos credits her with inventing the kerotakis, an early forerunner of the modern still. It had characteristics of what we know as a double boiler, and in France the double boiler is still called a bain-marie—Maria's bath.

Aqua Vitae Recipes

from The Art of Distillation, by John French, 1653

Two very simple recipes for aqua vitae/spirits of wine:
 

        How to make Aqua vitae, and Spirts of Wine out of Wine
Take of whatever wine you please, put it into a copper still, two parts of three being empty, distill it with a worm untill no more spirit come off, then this spirit will serve for the making of any spirits out of vegetables; but if thou wouldst have it stronger distill it again, and half will remain behind as an insipid flegm; and if thou wouldst have it yet stronger, distill it again, for every distillation wil leave behind one moity of flegm or thereabouts; so shalt thou have a most pure and strong spirit of wine.

        How to make aqua vitae out of beer
Take of stale strong-beer or rather the grounds there of, put it into a copper still with a worm, distill it gently (or otherwise it will make the head of the Still fly up) and there will come forth a weak spirit, which is called low wine; of which when thou hast a good quantity thou mayest distill it again of it self, and there will come forth a good Aqua vitae. And if thou distillest it two or three times more, thou shalt have as strong a spirit as out of wine, and indeed betwixt which and the spirit of wine, thou shalt percieve none or very little difference.

The first evidence of distillation was found in Tape Gowra, Mesopotamia. It consisted of a pot, which held almost 40 liters, and a collecting ring, that had a capacity of about 2 liters. This apparatus dates back to 3600 B.C.. Yet, it wasn't until the beginning of the 19th century that this technique was used in chemistry laboratories. Today, a variety of distillation techniques are used commonly in laboratories.

Steam distillation was invented when Avicenna, an Arabian physician, added water to rose petals and distilled the mixture in the 10^th century. The rose water he collected is considered to be the first modern perfume.

Fractional distillation and vacuum distillation were invented near the end of the 18th century. The first columns invented for fractional distillation were simple open tubes and it wasn't until the period 1900-1930 that vast improvements were made. Vacuum distillation, distillation under low pressure, made its appearance in the laboratory setting in 1869.

There also exists freeze distillation. This involves removal of alcohol from water by subjecting the mixture to temperatures below the freezing point of water. The alcohol can then be separated from the ice and distilled using another technique.