"Distiller" and "Distillery" redirect here. For other uses, see Distiller (disambiguation) and Distillery (disambiguation).

For other uses, see Distillation (disambiguation).

Laboratory display of distillation: 1: A heating device 2: Still pot 3: Still head 4: Thermometer/Boiling point temperature 5: Condenser 6: Cooling water in 7: Cooling water out 8: Distillate/receiving flask 9: Vacuum/gas inlet 10: Still receiver 11: Heat control 12: Stirrer speed control 13: Stirrer/heat plate 14: Heating (Oil/sand) bath 15: Stirring means e.g.(shown), boiling chips or mechanical stirrer 16: Cooling bath.[1] Distillation is a method of separating mixtures based on differences in volatilities of components in a boiling liquid mixture. Distillation is a unit operation, or a physical separation process, and not a chemical reaction. Commercially, distillation has a number of applications. It is used to separate crude oil into more fractions for specific uses such as transport, power generation and heating. Water is distilled to remove impurities, such as salt from seawater. Air is distilled to separate its components notably oxygen, nitrogen, and argon for industrial use. Distillation of fermented solutions has been used since ancient times to produce distilled beverages with a higher alcohol content. The premises where distillation is carried out, especially distillation of alcohol, are known as a distillery.
DISTILLATION, a generic term for a class of chemical operations which all agree in this, that the substance operated upon is heated in a close vessel (" retort," " still") and thereby wholly or partially converted into vapour, which vapour is then condensed, by the application of cold, in another apparatus (the " condenser ") connected with the vessel, and allowed to collect in a third portion of the apparatus, called a " receiver." In most cases the substance is a liquid, or assumes the liquid form previous to emitting vapours, and the product obtained (the "distillate ")is also in greater proportion liquid. The comparatively few and special cases of distillation, wherein solids are converted into vapours which condense directly from the gaseous into the solid form, are designated " sublimations." Thus we speak of the " distillation " of water or of

spirits, while we speak of the " sublimation " of sal-ammoniac. Distillations may be divided into two classesviz., 1st, those which are not, and 2d, those which are, accompanied by chemical changes. The word "distillation," in a narrower sense, is generally understood to apply to the first class only. The second might be called " destructive distillations," if it were not customary to reserve this term for the particular case in which the substance operated on consists of vegetable or animal matter which is being decomposed by the application of heat alone, i.e., without the aid of re-agents. The general object of simple distillation is the separation of substances of different degrees of volatility. The apparatus used varies very much according to the nature of the substance operated on and of the product extracted, and according to the scale on which the operation is carried out. Of the various contrivances used in chemical laboratories, the simplest is a glass retort, the descending neck of which is inserted into, and goes to near the bottom of, a slanting globular flask. The retort serves for the reception of the substance to be distilled, and is heated by means of char-coal or gas fire ; the vapours pass into the flask, which is kept cool by a continuous current of cold water running over it, or, in the case of more volatile substances, by being immersed in ice or some freezing mixture. This somewhat primitive arrangement works satisfactorily only when the vapours are easily condensible, and when the product is meant to be collected as a whole. In the majority of cases, however, the distillate has to be " fractionated," i.e., collected in a number of separate, consecutive portions; and it is then desirable that the apparatus should be so constructed as to enable one at any moment to examine the distillate as it is coming over. For this purpose it is necessary to condense the vapours on their way to, and not within, the receiver, so that the latter can, at any time, be removed and replaced by another. The condenser most generally used in chemical laboratories is that known as Liebig's condenser. It consists of a straight glass or metal tube, 1 to 3 feet long and J to 1 inch wide, fitted co-axially, by means of corks or india-rubber tubes, into a wider tube (made of glass or iron) which communicates at the lower end with a water tap, and at the upper with a sink, so that a stream of cold water can be made to run against the current of the vapour. The condenser tube is fixed in a slanting position, and the vapours made to enter at the upper end. The dimensions of the condenser and rate of water-flow depend on the speed at which the vapour is driven over, and on the temperature of that vapour, and, last not least, on the latent heat of the vapour and specific heat of the distillate. To show the importance of the last-named point, let us compare the quantities of heat to be withdrawn from 1 lb of steam and 1 lb of bromine vapour respectively, to reduce them to liquids at 0 C. We have in the case of water and bromine Water. Bromine. For the temperature of the vapour 100 63 For the latent heat 536 45'6 For the specific heat of the liquids 1 0'106 For the total heats of the vapours 636" 52'3 The withdrawal of 52'3 units of heat from lib of bromine vapour reduces it to liquid bromine at 0 C. By the with-drawal of (-j^- x 52-3 =) 83 units from the steam, as an easy calculation shows, only 0T6S) of liquid water, of even 100, could be producedhence more than 0-84 lb of steam remains uncondensed (at a temperature of about 96 G, assuming the steam to remain saturated, and to have the temperature of the condensed water). But

obviously a condenser under all circumstances is the more efficacious the greater its surface and the thinner its body. It is also obvious, cceteris paribus, that the most suitable material for a condenser tube is that which conducts heat best. Hence a metal tube will generally condense more rapidly than one of glass, and for metal tubes copper is better than tin, and silver better than either. In chemical laboratories glass is the only material which is quite generally appliL A T I O N 261 cable. In chemical works, on the other hand, glass, on account of its fragility, is rarely used; condensers there, wherever possible, are made of metal, usually fashioned into spirals (" worms ") and set in tub-shaped refrigerators Where acids have to be condensed, stoneware worms are generally employed. In the distillation of acetic acid pla-tinum worms, notwithstanding their high price, have been found to work best, and in the long run to be cheapest. The theory and successful execution of the process assume their greatest simplicity when the substances to be separated differ so greatly in their volatility that, without appreciable error, one can be assumed to be non-volatile at the boiling point of the other. A good illustration of this special case is afforded by the customary process used for the purification of water. A natural sweet water may in general be assumed to consist of three parts1st, water proper, which always forms something like 98 per cent, or more of the whole; 2d, non-volatile salts ; 3d, gases. To obtain pure water from such material, we need only boil it in a distillation apparatus, so as to raise from it dry steam, which steam when condensed yields water con-taminated only with the gases. To expel these all that is necessary is to again boil it for a short time; the gases go off with the first portions of steam, so that the residue, when allowed to cool in absence of air, constitutes pure water. To pass to a less simple case, let us assume that the substance to be distilled is a solution of ether in water, and the object is the separation of these two bodies. Ether boils at 35 O, water at 100 C. The elastic force of saturated steam at 35 is 42 mm., = -/^ = ygth of an atmosphere. Assuming now the mixture to be distilled from a flask, what will go on ? Neglecting for the sake of simplicity the small tension of the steam at 35, we should expect that at first the ether would simply boil away, so to speak, from a bath of warm water at 35 C. ; that the vapour would be pure ether, and maintain that composition until all the ether had boiled off ; then there would be a breakthe tempera-ture of the liquid would gradually rise to 100, and the water then distil over in its turn. And so it is approxi-mately, but not exactly. Our theory obviously neglects some important points. Water at 35 has a tension of -j^th atmosphere, ether of one atmosphere; hence the two saturated vapours together should press with a force of l-j5gth atmospherein other words, the mixture should com-mence to boil at less than 35. This, however (as in the majority of analogous cases), is not confirmed by experiment. The mixture commences to boil at a little above 35, and the boiling point rises steadily as the proportion of ether in the liquid decreases. Now, a priori, we should presume that at every given moment the volumes of ether and water in the vapour should be, approximately at least, proportional to the respective vapour tensions at the temperature at which the mixture happens to boil. Thus, for instance, assuming at the first that the liquid boils at 40 O., when the two tensions are equal to 910 and 55 910 mm. respectively, the vapour will contain ^0^rgg = 0 94 of its volume of ether vapour, and 0'06 of its volume of steam, supposing both substances to have the same chances of forming saturated vapour, which, of course, holds only so long as

they both are present in appreciable quantities. We easily see that, as the distillation progresses, the ether vapour must get more and more largely charged with vapour of water, until at last what goes off is steam, con-taminated with less and less of ether vapour. A thermometer placed near the entrance end of the condenser will, of course, record lower than one plunged into the boiling liquid, because the vapour in rising undergoes partial condensation, and the thermometer being bedewed with the condensed vapour will approximately indicate tho boiling point of that dew, i.e., of that which is just going over. The composition of the vapour as above given must not be confounded with the composition by weight of the distillate. To obtain the latter we must multiply each of the two volumes by the density of the respective vapour, or, what comes to the same thing, by its molecular weight as expressed by the chemical formula. In our case the vapour volume ratio water 55 ether 91~0 corresponds to the weight ratio 55 x H2Q 55 x 18 Jl_ 901 xC4H1()0~ 910 x 74 - 68 nearly" This consideration strips of its apparently anomalous character what we observe when vegetable substances con-taining essential oils are distilled with water, when we find that these oils, although boiling far above 100 C, go over with the first fractions of the water. Take the case of lemon oil, which boils at about 174 C. The molecular weight of the oil is 136 = C10H16; its vapour tension at 100 is 70 mm. Hence what goes over at first when lemon, peel is distilled with water should contain oil and water in the proportion Oil of Lemons. Water. Mol. Vap. Mol. Vap. wt tension. \vt. tension. 136 x 70 : 18 x 760 = 12 : 17 (nearly). The oil, although the less volatile substance of the two, being present in small quantity, but finely diffused, is soon completely driven over. No doubt the latent heats of vaporization of the two constituents have some-thing to do with the composition of the vapour formed, as the chance of every particle of the mixture to be" vaporized is obviously the greater the less its latent heat of vaporization. After what has been said it will be clear that in the dis-tillation of a mixture of two substances of approximately equal molecular weight and latent heats of vaporization, supposing neither to predominate overwhelmingly over the other, the one with the lower boiling point will predominate in the early, and the other will gradually accumulate in the later, fractions of the distillate. And similarly with mixtures of three or more bodies. The further the respec-tive boiling points are removed from one another the more complete a separation can be effected ; but in no case is the separation perfect. It is, however, easily seen that the analytic effect of a distillation can be increased by causing the vapour, before it reaches the condenser, to undergo partial condensation, when naturally the less volatile parts chiefly will run back. This artifice is largely employed by chemists, technical as well as scientific. The simplest mode is to let the vapour ascend through a long, vertical tube before it reaches the condenser, and to distil so slowly that a sufficiently large fraction of the vapour originally formed fails to survive the ascent through the cooling influence of the atmosphere. A more effective method is to let the condensed vapour accumulate in a series of small receptacles inserted between flask and condenser, constructed so that the vapour cannot pass through the receptacles without bubbling through their liquid contents, and so that the liquid in the receptacles cannot rise above a certain level, the excess flowing back into the next lower receptacle or into the still. But the

most effective method is to let the vapour ascend through a slanting condenser kept by means of a bath at a certain temperature, which is controlled so that while the liquid in the flask boils rapidly, the dis-tillation only just progresses and no more. The general principles thus stated regarding fractional distillation are liable to not a few exceptions, of which the following may be cited as examples. A solution of one part of hydrochloric acid gas in four parts of water boils (constant) at 110 C.i.e., 10 above the boiling point of water, although the acid constituent is an almost permanent gas. This, however, is easily explained; there can be no doubt that such an acid is a mixture of real hydrates, i.e., does not contain either free water or free hydrochloric acid. A similar explanation applies to the case of aqueous oil of vitriol, which boils the further above 100 the stronger it is, although the vapour may be, and in the case of acids contain-ing less than 84 per cent, of real acid really is, pure steam. The following cases, however, can scarcely be disposed of by the assumption of the interference of chemical action. Propyl alcohol boils at 97 C, water at 100; and yet a mixture of the two, as Pierre and Puchot found, when distilled always commences to boil at 88'5 with formation of a distillate of the approximate composition C3H80 + 2-78H20 ; and this particular aqueous alcohol boils without apparent decomposition at 88-3. Some time later Dittmar and Steuart made a precisely analogous observation with regard to aqueous allyl alcohol. A strong temptation exists to explain these anomalies by the assumption of definite hydrates in the aqueous alcohols, and this hypothesis would serve in the meantime were it not for the curious fact, discovered by the two French chemists named, that amyl alcohol and water (two liquids which do not mix), when distilled simultaneously out of the same retort, go over at a constant temperature less than 100, and with formation of a distillate which, although it is not even a mixture, has a constant composition. The most natural explanation of these phenomena is to assume them to be owing, not to chemical action, but rather to an exceptional absence of chemical affinity between the two components of the mixture, which for once gives the physical forces fair play. DRY (DESTRUCTIVE) DISTILLATION.Of the great number of chemical operations falling under this head, we can notice only those which are carried out industrially for the manufacture of useful products. Of such the most important are those in which wood, coal, shale, and bones form the materials operated upon. But as these processes form so many important industries, which have all special articles devoted to them, we must confine ourselves here to summing up shortly the features common to all. In all cases the " retorts " consist of iron or fire-clay semi-cylinders placed horizontally in a furnace and con-nected by iron pipes with refrigerators, and through these with gas-holders. Within these retorts the materials are brought up, more or less gradually, to a red heat, which is maintained until the formation of vapours practically ceases. Each of the materials named is a complex mixture of different chemical species. Wood consists mainly of cellulose and other carbo-hydrates, i.e., bodies composed of carbon and the elements of water; in coal and shale the combustible part consists of compounds of carbon and hydrogen, or carbon, hydrogen, and oxygen, richer in carbon than the components of wood; bones consist of about half of incombustible and infusible phosphate of lime (bone earth) and half of organic matter, of which the greater part is gelatine (compounds of carbon, nitrogen, hydrogen, and oxygen), and the lesser is fat (compounds of carbon, hydrogen, and oxygen). The chemical decomposi-tion in each case is highly complex. An infinite variety of products is invariably formed, which, however,

always readily divide into three :1st, a non-volatile residue, con-sisting of mineral matter and elementary carbon (" wood charcoal," " coke," &c.) which, in the case of animal matter, contains chemically combined nitrogen; 2d, a part condensible at ordinary temperatures which always readily separates into two distinct layers, viz. :(a) an aqueous portion (" tar-water "), and (b) a semifluid, viscid, oily, or resinous portion (" tar"); and 3d, a gaseous por-tion. The "tar-water" is the one, of all the four products, of which the qualitative composition most directly depends on the nature of the material distilled. In the case of wood it has an acid reaction, from the presence in it of acetic acid, which is associated (amongst many other things) with acetone and methyl alcohol. In the case of coal it is alkaline, from ammonia, present as carbonate, sulphide, sulphocyanide, and in other forms. Alcohols and oxygenated acids are absent. The " tar" is a complex mixture of carbon com-pounds, all combustible, but, although all directly derived from a vapour, not by any means all of them volatile. (Regarding the components, see TAR.) The quantity and quality of the tar naturally depend on the kind of material used, but perhaps yet more on the mode in which the dis-tillation is conducted. Thus, for instance, a coal tar pro-duced at low temperature contains a considerable per-centage of paraffins. If, on the other hand, the dis-tillation is conducted at a high temperature, the paraffins are almost absent, while the proportion of benzols con-siderably increases. A similar remark applies to the gaseous portion, as will readily be understood when we say that all volatile tar constituents, when passed through red hot tubes, are decomposed with formation of hydrogen and gaseous hydrocarbons, which latter again, when submitted to the same operation, are all liable to undergo dissociation into simpler compounds and associa-tion into more complex. DISTILLATION OF WATER.The continual interchange and circulation of water, between oceans and other great reservoirs of water on the one hand and dry land on the other, may be regarded as a process of distillation. Rain is thus a form of distilled water; and when it falls through a pure atmosphere it is found to possess the softness and freedom from dissolved salts characteristic of water artificially distilled. Rain water, however, absorbs a considerable proportion of air and some carbonic acid from the air, and also frequently contains ammonia, salts, and free acids. Water of that purity which can be secured only by dis-tillation is of indispensable value in many operations both of scientific and industrial chemistry. The apparatus and process for distilling ordinary water are very simple. The body of the still is made of copper, with a head and worm, or condensing apparatus, either of copper or tin. The first portion of the distillate brings over the gases dissolved in the water, ammonia, and other volatile impurities, and is consequently rejected, and scarcely two-fifths of the entire quantity of water can be with safety used as pure distilled water. Among the innumerable schemes which have been pro-posed for the production of a potable fresh water from the salt water of the ocean, two or three dependent on simul-taneous distillation and aeration have been found, in practice, to produce most satisfactory results. Of course the simple distillation of sea water, and the production thereby of a certain proportion of chemically fresh water, is a very simple problem; but it is found that water which is merely evaporated and recondensed has a very disagree-able empyreumatic odour, and a most repulsive flat taste, and it is only after long exposure to pure atmospheric air, with continued agitation, or repeated pouring from one vessel to another, that it becomes sufficiently aerated to

lose its unpleasant taste and smell and become drinkable. The water, moreover, till it is saturated with gases, readily absorbs noxious vapours to which it may be exposed. For the successful preparation of potable water from sea water, therefore, the following conditions are essential:1st, LATION 263 aeration of the distilled product so that it may be immedi-ately available for drinking purposes; 2d, economy of coal to obtain the maximum of water with the minimum expenditure of fuel; and 3d, simplicity of working parts, to secure the apparatus from breaking down, and enable unskilled attendants to work it with safety. Among the forms of apparatus which have most fully satisfied these conditions are the inventions of Dr Normandy and of Chaplin of Glasgow. While these have met with most acceptance in the United Kingdom, the apparatus of Rocher of Nantes, and that patented by Gall! and Mazeline of Havre, have been highly appreciated by French maritime authorities. Normandy's apparatus, while leaving nothing to be desired in point of economy of fuel and quality of water produced, is very complex in its structure, consisting of very numer-ous working parts, with elaborate arrangements of pipes, cocks, and other fittings. It is consequently expensive, and requires for its working the careful attention of an ex-perienced workman. It consists of three essential parts, in addition to any convenient form of boiler from which steam under a certain amount of pressure may be obtained. These parts are called respectively the evaporator, the con-denser, and the refrigerator. These are all closed cylindrical vessels, permeated internally with sheaves of pipes, through which pipes the steam generated percolates, condenses, and is aerated as explained below. The refrigerator is a horizontal vessel above which the condenser and the evaporator are placed in a vertical position. When the apparatus is in operation the refrigerator and condenser are filled with sea water, and a constant current is main-tained which enters by the refrigerator, passes upwards through the condenser, and is discharged by an overflow pipe at a level a little above the top of the condenser. The evaporator is filled only to about two-thirds of its height with water from the condenser, and the admission and regulation of its contents are governed by a stop-cock on the pipe communicating between the two vessels. The vessels being so prepared, superheated steam is admitted by a pipe leading from the boiler into the top of the evaporator, and, passing through the sheaf of pipes immersed in water, is there condensed. The condensed water passes direct from the evaporator into the pipes of the refrigerator, in which it is cooled to the temperature of the surrounding sea water. Here then is produced pure distilled but non-aerated water; and the means by which it is aerated and rendered fit for immediate use may be now traced. The superheated steam in permeating the pipes in the evaporator heats and vaporizes a portion of the water around them. The steam so generated passes into the sheaf of pipes in the condenser, in which, as already explained, a current of water is constantly rising and pass-ing away by the overflow pipe. The condensation of the steam within the pipes, again, communicates a high temperature to the upper stratum of water in the condenser. As water at a temperature of 54-5 C. parts with its dis-solved air and carbonic acid gas, a stream of water is con-tinually rising to the upper part of the condenser at a temperature more than sufficient to liberate these gases, and by means of a pipe these pass over into the upper part of the evaporator, and there mingle with and supersaturate the steam generated in that vessel. Instead, therefore, of it being simply steam which passes from the evaporator to the tubes of the

condenser, it is a mixture of steam and gases, the latter being in sufficient quantity not only to supersaturate the steam with which they are mixed, but also fully to aerate the condensed steam which passed direct from the evaporator into the refrigerator. The super-aerated condensed steam passes from the pipes in the condenser into those in the refrigerator, where it meets the non-aerated water from the evaporator pipes, the course of which has already been traced. Here the two products mingle, cool down to the temperature of the sea, and passing outwards through a filter, may be drawn off as pure aerated water of excellent quality. In Dr Normandy's apparatus the combustion of 1 lb of coal yields from 14 to 20 lb of potable water. The apparatus is extensively adopted in the British navy, the Ounard line, and many other important emigraut and mercantile lines. Chaplin's apparatus, which was invented and patented later, has also, since 1865, been sanctioned for use on emi-grant, troop, and passenger vessels. The apparatus possesses the great merit of simplicity and compactness, in con-sequence of which it is comparatively cheap and not liable to derangement. In addition to a boiler for generating steam from sea water the apparatus consists of an aerator, a con-denser, and a filter. The condenser is a cylinder, usually of cast iron with an internal worm pipe of copper, which is found to be the only really suitable metal for this use, The steam to be condensed is admitted to this worm or coil through the aerator. This part of the apparatusthe aeratoris really the essential feature in the invention, and consists simply of a series of holes perforated around the steam inlet pipe at the point where it enters the con-denser. The steam passing down in a powerful jet draws with it through these holes a proportion of atmospheric air sufficient to properly aerate the water for drinking purposes. The steam and air thoroughly commingled are together condensed as they pass through the coils of the worm,cold sea water passing in to the condenser at its lowest end, and rising upwards and flowing away at the top. After passing through the filter placed directly under the condenser, the aerated water is delivered or stored ready for use, clear, bright, colourless, palatable, and devoid of odour, at a temperature of about 15 C. The cold sea water for condensing may be forced into the condenser by a special steam pump attached to the apparatusa plan usually followed on sailing vesselsor any other convenient pumping arrangement may be resorted to. The steam for condensation is, in steamers, frequently supplied from the engine boilers; but generally it is preferable to employ a special small upright boiler, or to use the boilers attached to steam winches. Chaplin's apparatus has been adopted by many important British and Continental shipping com-panies, among others by the Peninsular and Oriental, the Inman, the North German Lloyd, and the Hamburg American Companies. DISTILLATION OF SPIEITS.Notwithstanding the enormous scale on which this industry is now prosecuted, it is only in modern and comparatively recent times that it has attained to the important position which it now occupies. The art of separating alcoholic spirit from fermented liquors appears, however, to have been known in the far East from the most remote antiquity. It is supposed to have been first known to, and practised by, the Chinese, whence a knowledge of the art gradually travelled westward. A rude kind of still, which is yet employed, has been used for obtaining ardent spirits in Ceylon from time immemorial. The name alcohol indicates that a knowledge of the method of preparing that substance probably came to Western Europe, like much more chemical knowledge, through the Arabs. Albucasis, who lived in the 12th century, is spoken of as the first Western philo-sopher who taught the art of distillation as applied to the

preparation of spirits ; and in the 13th century Baymond Lully was not only well acquainted with the process, but also knew the method of concentrating it into what he denominated aqua ardens by means of potassic carbonate. At the time when Henry II.in the 12th century invaded and conquered Ireland, the inhabitants were in the habit of making and using an alcoholic liquorusquebagh (uisge-bedtha, water of life), a term since abbreviated into whisky, which consequently is synonymous with the classical aqua vitce. It is further a noticeable fact that Captain Cook found, among the inhabitants of the Pacific Islands discovered by him, a knowledge of the art of distilling spirit from alcoholic infusions. The preparation of ardent spirit involves two separate series of operations:1st, the making of an alcoholic solution by means of vinous fermentation ; and 2d, the concentration of the alcoholic solution so obtained by the process of dis-tillation and rectification. All substances in nature which contain sugar in any of its forms are susceptible of undergoing vinous fermentation, and may therefore be used as sources of alcohol. Further, all starchy substances and ligneous tissue, seeing that by various chemical processes starch and cellulose may be converted into grape sugar, may also be used for the pre-paration of alcohol. It is thus obvious that the variety of organic substances, especially of the vegetable kingdom, from which alcohol may be elaborated is almost endless ; and in practice it is found that the sources employed are very numerous. Commercially, distilled alcoholic liquors are manufactured of varying strength, or proportion of alcohol to water, according as the spirit is intended to be used for drinking purposes or for employment in the arts. The standard by which excise duty on alcoholic liquor is charged in Great Britain is proof spirit, in which the alcohol and water are in almost equal proportions by weight, there being in 100 parts 49-24 of absolute alcohol, and 50'76 of water. Distilled spirits are said to be " over proof" when the proportion of alcohol is greater, and " under proof " when there is more water present than is indicated by " proof." Thus a spirit 11 over proof (o.p.) is a compound which requires the addition of 11 volumes of water to every hundred to reduce it to proof strength; and similarly 10 under proof (u.p.) indicates a liquor from every 100 gallons of which 10 gallons of water must be withdrawn to bring it to proof strength. Spirit for drink-ing is seldom sold at more than 11 over proof, from which it varies downward to 25 and more under proof. Bum, however, is manufactured and imported as highly concen-trated as from 10 to 43 over proof. Spirit of wine as used in the arts must be at least 43 over proof, and generally it is sold at from 54 to 64 over proof. The alcoholic liquors enumerated below are those most commonly distilled for drinking or medicinal purposes. Brandy, when genuine, is a spirit chiefly distilled in France from wine. Bum is made from molasses or treacle, and is. distilled in the West Indies, and generally in all countries where the sugar cane is cultivated. From fermented infusions of grain, malted and unmalted, and chiefly from barley, whisky is distilled, and that spirit when " silent " or flavourless is the basis of flavoured spirits, such as gin and factitious or British brandy. Arrack is an Oriental spirit distilled from " toddy," or the fermented juice of certain palm trees, and also from rice, which grain is the source of sak6, the national spirit of the Japanese. Potato brandy is very extensively prepared from the fecula of potatoes in Germany and Russia, and is a spirit much used for fortifying wines, and for making factitious wine, as well as in the arts. Beet root, carrots, Jerusalem artichokes, and several other saccharine roots are also used for the distilla-tion of spirit on a commercial scale. The only example of a spirit drawn from animal sources is the koumiss of the Tartars, which is distilled from the fermented milk of mares.

The modifications of stills or of distilling apparatus used in the preparation of alcoholic liquor are exceedingly i numerous, and many of the later inventions are of most complicated structure. The simple and primitive varieties of apparatus yield only a comparatively weak spirit on the first distillation, while the effect of the complex appliances now generally used is to produce, in one operation, a highly concentrated spirit, and that with a great saving of fuel, time, and labour. All varieties of distillatory apparatus resolve themsel ves under these heads:1 st, stills heated and worked by the direct application of the heat of a fire ; 2d, stills worked by the action of steam blown direct into the alcoholic solution from a steam boiler; and 3d, stills heated by steam passing in coiled pipes through the alcoholic solutions to be acted upon. To the first of these classesstills heated by direct fire belong the earliest and simplest forms of distillatory apparatus; and for producing particular classes of alcoholic liquor, stills very simple in their construction are yet employed. The common still is a flat-bottomed, close vessel of copper, with a high head to prevent the fluid within boiling over. To the top of this head a tube is connected, which is carried in a spiral form round the inside of a tub or barrel (the condenser or refrigerator), filled with cold water, and from its twisted form this tube receives the name of the " worm." The tube terminates at the bottom of the barrel, passing through it to the outside, and is con-ducted into the vessel termed the receiver, a stopcock, or more commonly a vessel termed a "safe," being usuallyplaced on the tube where it leaves the refrigerator. In distilling with an apparatus of this simple construction, it is obvious that at the beginning of the operation, when the wash or liquid to be distilled is rich in alcohol, and its boiling point consequently low, the distillate will pass over at a low temperature and contain a high percentage of alcohol. But as the operation progresses, the boiling point of the mixture in the still rises, the heat has therefore to be forced, and the quantity of watery vapour which passes over with the alcohol is proportionately increased. As the wash or liquid in the still continually weakens, a point is arrived at when the value of the weak distillate produced will not balance the expenditure on fuel for maintaining the heat of distillation. One of the earliest devices for economizing the heat of distillation consisted in interposing between the still and the refrigerator a wash warmer, or vessel charged with liquid ready for distillation. Through this vessel the pipe conveying the hot vapours to the refrigerator coil passed, and the vapours, partly condensing there, heated up the wash, which was thus prepared to pass into the still at an elevated temperature. The " pot" stills, in which the markedly flavoured Irish whisky is made, are of this con-struction. In the great establishment of the Banagher Distillery Company, King's co., Ireland, simple stills of a capacity of 20,000 gallons are erected having a rousing apparatus within them to keep the wash in agitation so as to prevent solid particles from settling on the bottom and burning. Beyond a wash warmer, or intermediate charger interposed between the still and the condenser, there is no other appliance attached to the apparatus. The first dis-tillate from the still is termed " low wines," and passes into the "low wines receiver," whence it passes into No. 1 " low wine still " to undergo a second distillation. The product of the second distillation, under the name of " faints or feints," is caught in the " faints receiver," from which it passes to No. 2 low wines still, and from this it is discharged as Irish whisky. The introduction of another principle into distillatory apparatus is illustrated by Dorn's still, which was intro-duced into Germany in the early part of the century, and is yet much used in smaller establishments in that country. In that apparatus the vessel, of copper, interposed between the

still and the condenser is divided horizontally into two unequal compartments by a diaphragm of copper. The upper and larger portion acts as a wash warmer (German, Vorwdrmer), and through it the pipe from the still body coils, opening into the lower division. For a time the whole distillate condenses in this division, but as the temperature of the wash in the upper division rises, and the heat of the more watery distillate from the still also increases, the condensed liquor in the lower division in its turn begins to boil, and undergoes a second distillation or rectification, the vapours from it passing onwards to be con-densed in the ordinary refrigerator. In many forms of distillatory apparatus two or more such rectifiers are placed between the primary still and the final condenser. The principle of the rectifier is easily understood. Supposing the operation of distilling to commence, the vapours which condense in rectifier No. 1 are much richer in alcohol than the liquid remaining in the still. The boiling point of the condensed liquid is consequently proportionately lower, and the vapour from the still passing into it gradually raises it to the boiling point, so that in its turn rectifier No. 1 distills into rectifier No 2 a liquid of still higher alcoholic richness. The relation of No. 2 to No. 1 is the same as that of No. 1 to the still body, and thus the concentration and redis-tillation might be carried on to any practicable or desired extent. Another principle brought into play in complex stills for the separation of stronger from weaker alcoholic solutions consists of dephlegmation, or the submitting of the vapour to a temperature so regulated that a portion of it, and that of course the most watery, is condensed and separated, running back into the still or into a special vessel, whilst the richly alcoholic vapour passes on to the rectifier or con-denser. In Dorn's still the wide and lofty head attached acts as a dephlegmator, watery vapours condensing on it, and thence falling back into the body; but in the more recent forms of apparatussuch as those of Pistorius and Siemensspecial dephlegmators of an elaborate nature are introduced. Of the second class of stillsthose in which the opera-tion is conducted by the heat of steam generated in a boiler, and forced into the apparatusthe Coffey still may be taken as an example. It is the form most frequently adopted in Great Britain for the manufacture of " silent" spirit, and it is generally recognized as the best and most economical device for preparing a highly concentrated spirit in a single operation. The Coffey still may further be regarded as a type of continuous distilling apparatus, as in it the necessity for withdrawing exhausted solutions and recharging the still with fresh wash is avoided. Beginning, as the Coffey still does, with the steam of pure water, the principle of rectification formerly alluded to is here carried out from the first step. The watery vapour becomes more and more highly charged with alcoholic fumes, till in the end the strongest spirit falls, condensed, into the receiver. In Coffey's apparatus the wash is exposed in a series of shallow chambers, placed one over the other, to the vapour of steam, which rises through the perforated bottoms of each chamber, and carries off the alcoholic vapours into the condenser. This condenser also consists of a series of chambers separated from each other by per-forated plates, and is so contrived that the cold wash passing in pipes through these chambers, in its way to feed the other series of chambers, acts as the condenser to the vapour of the alcohol, the wash being gradually heated thereby, as it passes through the successive chambers. The still, therefore, consists essentially of three separate but connected parts. The first is a large square receiver at the base, which receives the spent wash after it has been deprived of its alcohol by passing through the series of evaporating chambers : the second, a large, square, upright box, termed an " analyzer," contains the series of evaporat-ing

chambers, each communicating with the one below by means of a valved tube, which allows fluid to escape from the upper to the lower chamber only, and having the dividing partition of each chamber perforated with fine apertures, to allow the steam which is admitted from below to pass from chamber to chamber through the shallow layer of wash of each. A safety or escape valve is also fitted to each chamber. The already heated wash enters the upper-most of these chambers in a continuous regulated stream, is gradually deprived of its alcohol by the steam as it passes from chamber to chamber, and at last escapes into the lower large receiver, from which it flows off after attaining a certain depth. The third part of the apparatus also consists of a square upright box, termed a " condenser," divided into compartments by means of finely perforated plates, and in each chamber is a link of the tube which carries the cold wash onwards to supply the evaporating chambers just described. The alcoholic vapours escaping from the upper-most of the evaporating chambers are carried by pipes to the lowermost of these chambers, and are partly condensed by each successive chamber being colder than the one below it, in consequence of the wash entering the pipes from above, and only getting gradually heated by contact with the alcoholic vapour as it advances from chamber to chamber. As in the lowest of these chambers the heat is greatest, the alcoholic vapour or the condensed spirit contains a large amount of water ; but as the chambers are successively cooler, the alcoholic vapour and condensed spirit at last arrive at a temperature only sufficient to con-vert spirit of the strength wished into vapour, and by an adaptation of valves, the substitution of an impervious parti-tion for the perforated plate, and the admission of the alcoholic vapour into the chambers cooled by the passage of the cold wash in its contained pipes, that spirituous vapour is condensed, and the spirit is drawn off at one operation, of the very strength which it ought to have, and of the utmost purity. Flat-bottomed and fire-heated stills are considered the best for the distillation of malt spirit, as by them the flavour is preserved. Coffey's still, on the other hand, is the best for the distillation of grain spirit, as by it a spirit is obtained almost entirely destitute of flavour, and of a strength varying from 55 to 70 over proof. Spirit produced of this high strength evaporates at such a low temperature that scarcely any of the volatile oils on which the peculiar flavour of spirits depends are evaporated with it, hence the reason why it is not adapted for the dis-tillation of malt whisky, which requires a certain amount of these oils to give, it its requisite flavour. The spirit produced by Coffey's still is, therefore, chiefly used for making gin and factitious brandy by the rectifiers, or for being mixed with malt whiskies by the wholesale dealers. As the preparation of alcoholic spirit is the most important industry in which the operation of distillation occupies a prominent place, the establishments in which the manufacture is conducted are known as distilleries. But there are many other important industries in which distillation is an essential feature, being in them employed either for the separation, purification, or concentration of various products. A large proportion of the essential oils are, for example, obtained by the distillation of the substances containing them from water or a mixture of salt and water. The treatment of other bodies in which distillation plays a part will be found under their respective

headings. (w. D.j. PA.) DISTRESS is one of the few cases in which the law still permits an injured person to take his remedy into his own hands. Other instances mentioned in the text-books are self-defence in the case of a personal assault, the reseizure of property wrongfully taken away, the abatement of nuisances, &c. Distress differs from these as being a remedy for what is really a breach of contract, and it is the only case of the kind in which such a remedy is given. It is the right which the landlord has of seizing the personal chattels of his tenant for non-payment of rent. Cattle damage feasant (doing damage or trespassing upon a neighbour's land) may also be distrained, i.e., may be detained until satisfaction be rendered for the injury they have done. The cattle or other animals thus distrained are a mere pledge in the hands of the injured person, who has only power to retain them until the owner appear to make satisfaction for the mischief they have done. Distress for rent was also at one time regarded as a mere pledge or security; but the remedy, having been found to be speedy and efficacious, was rendered more perfect by enactments allowing the thing taken to be sold. Blackstone notes that the law of distresses in this respect " has been greatly altered within a few years last past." The legislature, in fact, converted an ancient right of personal redress into a powerful remedy for the exclusive benefit of a single class of creditors, viz., landlords. Now that the relation of landlord and tenant in England has come to be regarded as purely a matter of contract, the language of the law-books seems to be singularly inappropriate. The defaulting tenant is a " wrong-doer," the landlord is the " injured party ;" any attempt to defeat the landlord's remedy by carrying off distrainable goods is denounced as " fraudulent and knavish." The operation of the law has, as we shall point out, been mitigated in one important respect by a recent Act, but it still remains an almost unique specimen of one-sided legislation. At common law distress was said to be incident to rent service, and by particular reservation to rent charges ; but by 4 Geo. II. c. 28 it was extended to rent seek, rents of assize, and chief rents (see BENT.) It is therefore a general remedy for rent certain in arrear. All personal chattels are distrainable with the following exceptions :1, things in which there can be no property, as animals ferce naturw ; 2, things in actual use ; 3, things delivered to a person following a public trade, as a horse sent to be shoed, &c; 4, things already in the custody of the law; 5, money, unless placed in a sealed bag; 6, things which cannot be restored in as good a plight as when distrained; 7, fixtures; 8, beasts of the plough and instruments of husbandry; 9, instruments of a man's trade or profession. These excep-tions, it will be seen, imply that the thing distrained is to be held as a pledge merelynot to be sold. They also imply that in general any chattels found on the land in question are to be available for the benefit of the landlord, whether they belong to the tenant or not. This principle worked with peculiar harshness in the case of lodgers, whose goods might be seized and sold for the payment of the rent due by their landlord to his superior landlord. Now, however, by the Lodgers' Goods Protection Act (34 and 35 Vict. c. 79), where a lodger's goods have been seized by the superior landlord the lodger may serve him with a notice stating that the intermediate landlord has no interest in the property seized, but that it is the property or in the lawful possession of the lodger, and setting forth the amount of the rent due by the lodger to his immediate landlord. On payment or tender of such rent the landlord cannot proceed with the distress against the goods in ques-tion. And originally the landlord could only seize things actually on the premises,-so that the remedy might be defeated by the things being taken away. But by 9 Anne c. 14, and 11 Geo. II. c. 19, he may follow things

fraudu-lently or clandestinely removed off the premises within thirty days after their removal, unless they have been in the meantime bona fide sold for a valuable consideration. The sixth exception mentioned above was held to extend to sheaves of corn; but by 2 Will, and Mary c. 5, corn, when reaped, as well as hay, was made subject to distress. Excessive or disproportionate distress exposes the distrainer to an action, and any irregularity formerly made the proceedings void ab initio, so that the remedy was attended with considerable risk. The statute 11 Geo. II. c. 19, before alluded to, in the interests of landlords, protected distresses for rent from the consequences of irregularity. In all cases of distress for rent, if the owner do not within five days replevy the same with sufficient security, the thing distrained may be sold towards satisfaction of the rent and charges, and the surplus, if any, must be returned to the owner. To " replevy " is when the person distrained upon applies to the proper authority (the registrar of the county court) to have the thing returned to his own possession, on giving security to try the right of taking it in an action of replevin. Duties and penalties imposed by Act of Parliament are sometimes enforced by distress.

Answer: Distillation is a widely used method for separating mixtures based on differences in the conditions required to change the phase of components of the mixture. To separate a mixture of liquids, the liquid can be heated to force components, which have different boiling points, into the gas phase. The gas is then condensed back into liquid form and collected. Repeating the process on the collected liquid to improve the purity of the product is called double distillation. Although the term is most commonly applied to liquids, the reverse process can be used to separate gases by liquefying components using changes in temperature and/or pressure.

History
See also: Distilled beverage

Distillation apparatus of Zosimus, from Marcelin Berthelot, Collection des anciens alchimistes grecs (3 vol., Paris, 18871888).

The first clear evidence of distillation comes from Greek alchemists working in Alexandria in the first century AD.[2] Distilled water has been known since at least ca. 200 AD, when Alexander of Aphrodisias described the process.[3] Arabs learned the process from the Egyptians and used it extensively in their chemical experiments[citation needed]. Clear evidence of the distillation of alcohol comes from the School of Salerno in the 12th century.[2][4] Fractional distillation was developed by Tadeo Alderotti in the 13th century.[5] In 1500, German alchemist Hieronymus Braunschweig published Liber de arte destillandi (The Book of the Art of Distillation)[6] the first book solely dedicated to the subject of distillation, followed in 1512 by a much expanded version. In 1651, John French published The Art of Distillation the first major English compendium of practice, though it has been claimed[7] that much of it derives from Braunschweig's work. This includes diagrams with people in them showing the industrial rather than bench scale of the operation.

A retort

Distillation

Old Ukrainian vodka still As alchemy evolved into the science of chemistry, vessels called retorts became used for distillations. Both alembics and retorts are forms of glassware with long necks pointing to the side at a downward angle which acted as air-cooled condensers to condense the distillate and let it drip downward for collection. Later, copper alembics were invented. Riveted joints were often kept tight by using various mixtures, for instance a dough made of rye flour.[8] These alembics often featured a cooling system around the beak, using cold water for instance, which made the

condensation of alcohol more efficient. These were called pot stills. Today, the retorts and pot stills have been largely supplanted by more efficient distillation methods in most industrial processes. However, the pot still is still widely used for the elaboration of some fine alcohols such as cognac, Scotch whisky, tequila and some vodkas. Pot stills made of various materials (wood, clay, stainless steel) are also used by bootleggers in various countries. Small pot stills are also sold for the domestic production[9] of flower water or essential oils. Early forms of distillation were batch processes using one vaporization and one condensation. Purity was improved by further distillation of the condensate. Greater volumes were processed by simply repeating the distillation. Chemists were reported to carry out as many as 500 to 600 distillations in order to obtain a pure compound.[10] In the early 19th century the basics of modern techniques including pre-heating and reflux were developed, particularly by the French,[10] then in 1830 a British Patent was issued to Aeneas Coffey for a whiskey distillation column,[11] which worked continuously and may be regarded as the archetype of modern petrochemical units. In 1877, Ernest Solvay was granted a U.S. Patent for a tray column for ammonia distillation[12] and the same and subsequent years saw developments of this theme for oil and spirits. With the emergence of chemical engineering as a discipline at the end of the 19th century, scientific rather than empirical methods could be applied. The developing petroleum industry in the early 20th century provided the impetus for the development of accurate design methods such as the McCabe-Thiele method and the Fenske equation. The availability of powerful computers has also allowed direct computer simulation of distillation columns.

Applications of distillation
The application of distillation can roughly be divided in four groups: laboratory scale, industrial distillation, distillation of herbs for perfumery and medicinals (herbal distillate), and food processing. The latter two are distinctively different from the former two in that in the processing of beverages, the distillation is not used as a true purification method but more to transfer all volatiles from the source materials to the distillate. The main difference between laboratory scale distillation and industrial distillation is that laboratory scale distillation is often performed batch-wise, whereas industrial distillation often occurs continuously. In batch distillation, the composition of the source material, the vapors of the distilling compounds and the distillate change during the distillation. In batch distillation, a still is charged (supplied) with a batch of feed mixture, which is then separated into its component fractions which are collected sequentially from most volatile to less volatile, with the bottoms (remaining least or non-volatile fraction) removed at the end. The still can then be recharged and the process repeated. In continuous distillation, the source materials, vapors, and distillate are kept at a constant composition by carefully replenishing the source material and removing fractions from both vapor and liquid in the system. This results in a better control of the separation process.

Idealized distillation model

The boiling point of a liquid is the temperature at which the vapor pressure of the liquid equals the pressure in the liquid, enabling bubbles to form without being crushed. A special case is the normal boiling point, where the vapor pressure of the liquid equals the ambient atmospheric pressure. It is a common misconception that in a liquid mixture at a given pressure, each component boils at the boiling point corresponding to the given pressure and the vapors of each component will collect separately and purely. This, however, does not occur even in an idealized system. Idealized models of distillation are essentially governed by Raoult's law and Dalton's law, and assume that vapor-liquid equilibria are attained. Raoult's law assumes that a component contributes to the total vapor pressure of the mixture in proportion to its percentage of the mixture and its vapor pressure when pure, or succinctly: partial pressure equals mole fraction multiplied by vapor pressure when pure. If one component changes another component's vapor pressure, or if the volatility of a component is dependent on its percentage in the mixture, the law will fail. Dalton's law states that the total vapor pressure is the sum of the vapor pressures of each individual component in the mixture. When a multi-component liquid is heated, the vapor pressure of each component will rise, thus causing the total vapor pressure to rise. When the total vapor pressure reaches the pressure surrounding the liquid, boiling occurs and liquid turns to gas throughout the bulk of the liquid. Note that a mixture with a given composition has one boiling point at a given pressure, when the components are mutually soluble. An implication of one boiling point is that lighter components never cleanly "boil first". At boiling point, all volatile components boil, but for a component, its percentage in the vapor is the same as its percentage of the total vapor pressure. Lighter components have a higher partial pressure and thus are concentrated in the vapor, but heavier volatile components also have a (smaller) partial pressure and necessarily evaporate also, albeit being less concentrated in the vapor. Indeed, batch distillation and fractionation succeed by varying the composition of the mixture. In batch distillation, the batch evaporates, which changes its composition; in fractionation, liquid higher in the fractionation column contains more lights and boils at lower temperatures. The idealized model is accurate in the case of chemically similar liquids, such as benzene and toluene. In other cases, severe deviations from Raoult's law and Dalton's law are observed, most famously in the mixture of ethanol and water. These compounds, when heated together, form an azeotrope, which is a composition with a boiling point higher or lower than the boiling point of each separate liquid. Virtually all liquids, when mixed and heated, will display azeotropic behaviour. Although there are computational methods that can be used to estimate the behavior of a mixture of arbitrary components, the only way to obtain accurate vapor-liquid equilibrium data is by measurement.

It is not possible to completely purify a mixture of components by distillation, as this would require each component in the mixture to have a zero partial pressure. If ultra-pure products are the goal, then further chemical separation must be applied. When a binary mixture is evaporated and the other component, e.g. a salt, has zero partial pressure for practical purposes, the process is simpler and is called evaporation in engineering.

Batch distillation
Main article: Batch distillation

A batch still showing the separation of A and B. Heating an ideal mixture of two volatile substances A and B (with A having the higher volatility, or lower boiling point) in a batch distillation setup (such as in an apparatus depicted in the opening figure) until the mixture is boiling results in a vapor above the liquid which contains a mixture of A and B. The ratio between A and B in the vapor will be different from the ratio in the liquid: the ratio in the liquid will be determined by how the original mixture was prepared, while the ratio in the vapor will be enriched in the more volatile compound, A (due to Raoult's Law, see above). The vapor goes through the condenser and is removed from the system. This in turn means that the ratio of compounds in the remaining liquid is now different from the initial ratio (i.e. more enriched in B than the starting liquid). The result is that the ratio in the liquid mixture is changing, becoming richer in component B. This causes the boiling point of the mixture to rise, which in turn results in a rise in the temperature in the vapor, which results in a changing ratio of A : B in the gas phase (as distillation continues, there is an increasing proportion of B in the gas phase). This results in a slowly changing ratio A : B in the distillate. If the difference in vapor pressure between the two components A and B is large (generally expressed as the difference in boiling points), the mixture in the beginning of the distillation is highly enriched in component A, and when component A has distilled off, the boiling liquid is enriched in component B.

Continuous distillation
Main article: Continuous distillation Continuous distillation is an ongoing distillation in which a liquid mixture is continuously (without interruption) fed into the process and separated fractions are removed continuously as output streams as time passes during the operation. Continuous distillation produces at least two

output fractions, including at least one volatile distillate fraction, which has boiled and been separately captured as a vapor condensed to a liquid. There is always a bottoms (or residue) fraction, which is the least volatile residue that has not been separately captured as a condensed vapor. Continuous distillation differs from batch distillation in the respect that concentrations should not change over time. Continuous distillation can be run at a steady state for an arbitrary amount of time. For any source material of specific composition, the main variables that affect the purity of products in continuous distillation are the reflux ratio and the number of theoretical equilibrium stages (practically, the number of trays or the height of packing). Reflux is a flow from the condenser back to the column, which generates a recycle that allows a better separation with a given number of trays. Equilibrium stages are ideal steps where compositions achieve vaporliquid equilibrium, repeating the separation process and allowing better separation given a reflux ratio. A column with a high reflux ratio may have fewer stages, but it refluxes a large amount of liquid, giving a wide column with a large holdup. Conversely, a column with a low reflux ratio must have a large number of stages, thus requiring a taller column.

General improvements
Both batch and continuous distillations can be improved by making use of a fractionating column on top of the distillation flask. The column improves separation by providing a larger surface area for the vapor and condensate to come into contact. This helps it remain at equilibrium for as long as possible. The column can even consist of small subsystems ('trays' or 'dishes') which all contain an enriched, boiling liquid mixture, all with their own vapor-liquid equilibrium. There are differences between laboratory-scale and industrial-scale fractionating columns, but the principles are the same. Examples of laboratory-scale fractionating columns (in increasing efficiency) include:

Air condenser Vigreux column (usually laboratory scale only) Packed column (packed with glass beads, metal pieces, or other chemically inert material) Spinning band distillation system.

Laboratory scale distillation

Laboratory scale distillations are almost exclusively run as batch distillations. The device used in distillation, sometimes referred to as a still, consists at a minimum of a reboiler or pot in which the source material is heated, a condenser in which the heated vapour is cooled back to the liquid state, and a receiver in which the concentrated or purified liquid, called the distillate, is collected. Several laboratory scale techniques for distillation exist (see also distillation types).

Simple distillation

In simple distillation, all the hot vapors produced are immediately channeled into a condenser that cools and condenses the vapors. Therefore, the distillate will not be pure its composition will be identical to the composition of the vapors at the given temperature and pressure, and can be computed from Raoult's law. As a result, simple distillation is usually used only to separate liquids whose boiling points differ greatly (rule of thumb is 25 C),[13] or to separate liquids from involatile solids or oils. For these cases, the vapor pressures of the components are usually sufficiently different that Raoult's law may be neglected due to the insignificant contribution of the less volatile component. In this case, the distillate may be sufficiently pure for its intended purpose.

Fractional distillation
Main article: Fractional distillation For many cases, the boiling points of the components in the mixture will be sufficiently close that Raoult's law must be taken into consideration. Therefore, fractional distillation must be used in order to separate the components well by repeated vaporization-condensation cycles within a packed fractionating column. This separation, by successive distillations, is also referred to as rectification.[14] As the solution to be purified is heated, its vapors rise to the fractionating column. As it rises, it cools, condensing on the condenser walls and the surfaces of the packing material. Here, the condensate continues to be heated by the rising hot vapors; it vaporizes once more. However, the composition of the fresh vapors are determined once again by Raoult's law. Each vaporizationcondensation cycle (called a theoretical plate) will yield a purer solution of the more volatile component.[15] In reality, each cycle at a given temperature does not occur at exactly the same position in the fractionating column; theoretical plate is thus a concept rather than an accurate description. More theoretical plates lead to better separations. A spinning band distillation system uses a spinning band of Teflon or metal to force the rising vapors into close contact with the descending condensate, increasing the number of theoretical plates.[16]

Steam distillation
Main article: Steam distillation Like vacuum distillation, steam distillation is a method for distilling compounds which are heatsensitive.[17] The temperature of the steam is easier to control than the surface of a heating element, and allows a high rate of heat transfer without heating at a very high temperature. This process involves bubbling steam through a heated mixture of the raw material. By Raoult's law, some of the target compound will vaporize (in accordance with its partial pressure). The vapor mixture is cooled and condensed, usually yielding a layer of oil and a layer of water.

Steam distillation of various aromatic herbs and flowers can result in two products; an essential oil as well as a watery herbal distillate. The essential oils are often used in perfumery and aromatherapy while the watery distillates have many applications in aromatherapy, food processing and skin care.

Dimethyl sulfoxide usually boils at 189 C. Under a vacuum, it distills off into the receiver at only 70 C.

Perkin triangle distillation setup 1: Stirrer bar/anti-bumping granules 2: Still pot 3: Fractionating column 4: Thermometer/Boiling point temperature 5: Teflon tap 1 6: Cold finger 7: Cooling water out 8: Cooling water in 9: Teflon tap 2 10: Vacuum/gas inlet 11: Teflon tap 3 12: Still receiver

Vacuum distillation
Main article: Vacuum distillation Some compounds have very high boiling points. To boil such compounds, it is often better to lower the pressure at which such compounds are boiled instead of increasing the temperature. Once the pressure is lowered to the vapor pressure of the compound (at the given temperature), boiling and the rest of the distillation process can commence. This technique is referred to as vacuum distillation and it is commonly found in the laboratory in the form of the rotary evaporator. This technique is also very useful for compounds which boil beyond their decomposition temperature at atmospheric pressure and which would therefore be decomposed by any attempt to boil them under atmospheric pressure. Molecular distillation is vacuum distillation below the pressure of 0.01 torr.[18] 0.01 torr is one order of magnitude above high vacuum, where fluids are in the free molecular flow regime, i.e. the mean free path of molecules is comparable to the size of the equipment. The gaseous phase no longer exerts significant pressure on the substance to be evaporated, and consequently, rate of evaporation no longer depends on pressure. That is, because the continuum assumptions of fluid dynamics no longer apply, mass transport is governed by molecular dynamics rather than fluid dynamics. Thus, a short path between the hot surface and the cold surface is necessary, typically by suspending a hot plate covered with a film of feed next to a cold plate with a line of sight in between. Molecular distillation is used industrially for purification of oils.

Air-sensitive vacuum distillation

Some compounds have high boiling points as well as being air sensitive. A simple vacuum distillation system as exemplified above can be used, whereby the vacuum is replaced with an inert gas after the distillation is complete. However, this is a less satisfactory system if one desires to collect fractions under a reduced pressure. To do this a "cow" or "pig" adaptor can be added to the end of the condenser, or for better results or for very air sensitive compounds a Perkin triangle apparatus can be used. The Perkin triangle, has means via a series of glass or Teflon taps to allows fractions to be isolated from the rest of the still, without the main body of the distillation being removed from either the vacuum or heat source, and thus can remain in a state of reflux. To do this, the sample is first isolated from the vacuum by means of the taps, the vacuum over the sample is then replaced with an inert gas (such as nitrogen or argon) and can then be stoppered and removed. A fresh collection vessel can then be added to the system, evacuated and linked back into the distillation system via the taps to collect a second fraction, and so on, until all fractions have been collected.

Short path distillation

Short path vacuum distillation apparatus with vertical condenser (cold finger), to minimize the distillation path; 1: Still pot with stirrer bar/anti-bumping granules 2: Cold finger bent to direct condensate 3: Cooling water out 4: cooling water in 5: Vacuum/gas inlet 6: Distillate flask/distillate. Short path distillation is a distillation technique that involves the distillate travelling a short distance, often only a few centimeters, and is normally done at reduced pressure.[19] A classic example would be a distillation involving the distillate travelling from one glass bulb to another, without the need for a condenser separating the two chambers. This technique is often used for compounds which are unstable at high temperatures or to purify small amounts of compound. The advantage is that the heating temperature can be considerably lower (at reduced pressure) than the boiling point of the liquid at standard pressure, and the distillate only has to travel a short distance before condensing. A short path ensures that little compound is lost on the sides of the apparatus. The Kugelrohr is a kind of a short path distillation apparatus which often contain multiple chambers to collect distillate fractions.

Zone distillation
Zone distillation is a distillation process in long container with partial melting of refined matter in moving liquid zone and condensation of vapor in the solid phase at condensate pulling in cold area. The process is worked in theory. When zone heater is moving from the top to the bottom of the container then solid condensate with irregular impurity distribution is forming. Then most pure part of the condensate may be extracted as product. The process may be iterated many times by moving (without turnover) the received condensate to the bottom part of the container on the place of refined matter. The irregular impurity distribution in the condensate (that is efficiency of purification) increases with number of repetitions of the process. Zone distillation is a distillation analog of zone recrystallization. Impurity distribution in the condensate is described by known equations of zone recrystallization with various numbers of iteration of process with replacement distribution efficient k of crystallization on separation factor of distillation. (Literature: Kravchenko, A.I. Zone distillation: a new method of refining // Problems of atomic science and technology, 2011. N. 6 Series: Vacuum, pure materials, superconductors (19). P. 24-26. [in Russian]. [1])

Other types

The process of reactive distillation involves using the reaction vessel as the still. In this process, the product is usually significantly lower-boiling than its reactants. As the product is formed from the reactants, it is vaporized and removed from the reaction mixture. This technique is an example of a continuous vs. a batch process; advantages include less downtime to charge the reaction vessel with starting material, and less workup. Catalytic distillation is the process by which the reactants are catalyzed while being distilled to continuously separate the products from the reactants. This method is used to assist equilibrium reactions reach completion. Pervaporation is a method for the separation of mixtures of liquids by partial vaporization through a non-porous membrane. Extractive distillation is defined as distillation in the presence of a miscible, high boiling, relatively non-volatile component, the solvent, that forms no azeotrope with the other components in the mixture. Flash evaporation (or partial evaporation) is the partial vaporization that occurs when a saturated liquid stream undergoes a reduction in pressure by passing through a throttling valve or other throttling device. This process is one of the simplest unit operations, being equivalent to a distillation with only one equilibrium stage. Codistillation is distillation which is performed on mixtures in which the two compounds are not miscible.

The unit process of evaporation may also be called "distillation":

In rotary evaporation a vacuum distillation apparatus is used to remove bulk solvents from a sample. Typically the vacuum is generated by a water aspirator or a membrane pump. In a kugelrohr a short path distillation apparatus is typically used (generally in combination with a (high) vacuum) to distill high boiling (> 300 C) compounds. The apparatus consists of an oven in which the compound to be distilled is placed, a receiving portion which is outside of the oven, and a means of rotating the sample. The vacuum is normally generated by using a high vacuum pump.

Other uses:

Dry distillation or destructive distillation, despite the name, is not truly distillation, but rather a chemical reaction known as pyrolysis in which solid substances are heated in an inert or reducing atmosphere and any volatile fractions, containing high-boiling liquids and products of pyrolysis, are collected. The destructive distillation of wood to give methanol is the root of its common name wood alcohol. Freeze distillation is an analogous method of purification using freezing instead of evaporation. It is not truly distillation, but a recrystallization where the product is the mother liquor, and does not produce products equivalent to distillation. This process is used in the production of ice beer and ice wine to increase ethanol and sugar content,

respectively. It is also used to produce applejack. Unlike distillation, freeze distillation concentrates poisonous congeners rather than removing them.

Azeotropic distillation
Main article: Azeotropic distillation Interactions between the components of the solution create properties unique to the solution, as most processes entail nonideal mixtures, where Raoult's law does not hold. Such interactions can result in a constant-boiling azeotrope which behaves as if it were a pure compound (i.e., boils at a single temperature instead of a range). At an azeotrope, the solution contains the given component in the same proportion as the vapor, so that evaporation does not change the purity, and distillation does not effect separation. For example, ethyl alcohol and water form an azeotrope of 95.6% at 78.1 C. If the azeotrope is not considered sufficiently pure for use, there exist some techniques to break the azeotrope to give a pure distillate. This set of techniques are known as azeotropic distillation. Some techniques achieve this by "jumping" over the azeotropic composition (by adding an additional component to create a new azeotrope, or by varying the pressure). Others work by chemically or physically removing or sequestering the impurity. For example, to purify ethanol beyond 95%, a drying agent or a (desiccant such as potassium carbonate) can be added to convert the soluble water into insoluble water of crystallization. Molecular sieves are often used for this purpose as well. Immiscible liquids, such as water and toluene, easily form azeotropes. Commonly, these azeotropes are referred to as a low boiling azeotrope because the boiling point of the azeotrope is lower than the boiling point of either pure component. The temperature and composition of the azeotrope is easily predicted from the vapor pressure of the pure components, without use of Raoult's law. The azeotrope is easily broken in a distillation set-up by using a liquid-liquid separator (a decanter) to separate the two liquid layers that are condensed overhead. Only one of the two liquid layers is refluxed to the distillation set-up. High boiling azeotropes, such as a 20 weight percent mixture of hydrochloric acid in water, also exist. As implied by the name, the boiling point of the azeotrope is greater than the boiling point of either pure component. To break azeotropic distillations and cross distillation boundaries, such as in the DeRosier Problem, it is necessary to increase the composition of the light key in the distillate.

Breaking an azeotrope with unidirectional pressure manipulation

The boiling points of components in an azeotrope overlap to form a band. By exposing an azeotrope to a vacuum or positive pressure, it's possible to bias the boiling point of one component away from the other by exploiting the differing vapour pressure curves of each; the curves may overlap at the azeotropic point, but are unlikely to be remain identical further along

the pressure axis either side of the azeotropic point. When the bias is great enough, the two boiling points no longer overlap and so the azeotropic band disappears. This method can remove the need to add other chemicals to a distillation, but it has two potential drawbacks. Under negative pressure, power for a vacuum source is needed and the reduced boiling points of the distillates requires that the condenser be run cooler to prevent distillate vapours being lost to the vacuum source. Increased cooling demands will often require additional energy and possibly new equipment or a change of coolant. Alternatively, if positive pressures are required, standard glassware can not be used, energy must be used for pressurization and there is a higher chance of side reactions occurring in the distillation, such as decomposition, due to the higher temperatures required to effect boiling. A unidirectional distillation will rely on a pressure change in one direction, either positive or negative.

Pressure-swing distillation
Further information: Pressure-Swing Distillation (section on the main Azeotrope page) This section may be confusing or unclear to readers. Please help clarify the section; suggestions may be found on the talk page. (May 2009) Pressure-swing distillation is essentially the same as the unidirectional distillation used to break azeotropic mixtures, but here both positive and negative pressures may be employed.[clarification
needed]

This has an important impact on the selectivity of the distillation and allows a chemist[citation needed] to optimize a process such that fewer extremes of pressure and temperature are required and less energy is consumed. This is particularly important in commercial applications. Pressure-swing distillation is employed during the industrial purification of ethyl acetate after its catalytic synthesis from ethanol.

Industrial distillation

Typical industrial distillation towers Main article: Continuous distillation Large scale industrial distillation applications include both batch and continuous fractional, vacuum, azeotropic, extractive, and steam distillation. The most widely used industrial applications of continuous, steady-state fractional distillation are in petroleum refineries, petrochemical and chemical plants and natural gas processing plants. Industrial distillation[14][20] is typically performed in large, vertical cylindrical columns known as distillation towers or distillation columns with diameters ranging from about 65 centimeters to 16 meters and heights ranging from about 6 meters to 90 meters or more. When the process feed has a diverse composition, as in distilling crude oil, liquid outlets at intervals up the column allow for the withdrawal of different fractions or products having different boiling points or boiling ranges. The "lightest" products (those with the lowest boiling point) exit from the top of the columns and the "heaviest" products (those with the highest boiling point) exit from the bottom of the column and are often called the bottoms.

Diagram of a typical industrial distillation tower Industrial towers use reflux to achieve a more complete separation of products. Reflux refers to the portion of the condensed overhead liquid product from a distillation or fractionation tower that is returned to the upper part of the tower as shown in the schematic diagram of a typical, large-scale industrial distillation tower. Inside the tower, the downflowing reflux liquid provides cooling and condensation of the upflowing vapors thereby increasing the efficiency of the distillation tower. The more reflux that is provided for a given number of theoretical plates, the better the tower's separation of lower boiling materials from higher boiling materials. Alternatively, the more reflux that is provided for a given desired separation, the fewer the number of theoretical plates required. Such industrial fractionating towers are also used in air separation, producing liquid oxygen, liquid nitrogen, and high purity argon. Distillation of chlorosilanes also enables the production of high-purity silicon for use as a semiconductor.

Section of an industrial distillation tower showing detail of trays with bubble caps Design and operation of a distillation tower depends on the feed and desired products. Given a simple, binary component feed, analytical methods such as the McCabe-Thiele method[14][21] or the Fenske equation[14] can be used. For a multi-component feed, simulation models are used both for design and operation. Moreover, the efficiencies of the vapor-liquid contact devices (referred to as "plates" or "trays") used in distillation towers are typically lower than that of a theoretical 100% efficient equilibrium stage. Hence, a distillation tower needs more trays than the number of theoretical vapor-liquid equilibrium stages. In modern industrial uses, a packing material is used in the column instead of trays when low pressure drops across the column are required. Other factors that favor packing are: vacuum systems, smaller diameter columns, corrosive systems, systems prone to foaming, systems requiring low liquid holdup and batch distillation. Conversely, factors that favor plate columns are: presence of solids in feed, high liquid rates, large column diameters, complex columns, columns with wide feed composition variation, columns with a chemical reaction, absorption columns, columns limited by foundation weight tolerance, low liquid rate, large turn-down ratio and those processes subject to process surges.

Large-scale, industrial vacuum distillation column[22] This packing material can either be random dumped packing (13" wide) such as Raschig rings or structured sheet metal. Liquids tend to wet the surface of the packing and the vapors pass across this wetted surface, where mass transfer takes place. Unlike conventional tray distillation in which every tray represents a separate point of vapor-liquid equilibrium, the vapor-liquid equilibrium curve in a packed column is continuous. However, when modeling packed columns, it is useful to compute a number of "theoretical stages" to denote the separation efficiency of the packed column with respect to more traditional trays. Differently shaped packings have different surface areas and void space between packings. Both of these factors affect packing performance. Another factor in addition to the packing shape and surface area that affects the performance of random or structured packing is the liquid and vapor distribution entering the packed bed. The number of theoretical stages required to make a given separation is calculated using a specific vapor to liquid ratio. If the liquid and vapor are not evenly distributed across the superficial tower area as it enters the packed bed, the liquid to vapor ratio will not be correct in the packed bed and the required separation will not be achieved. The packing will appear to not be working properly. The height equivalent of a theoretical plate (HETP) will be greater than expected. The problem is not the packing itself but the mal-distribution of the fluids entering the packed bed. Liquid mal-distribution is more frequently the problem than vapor. The design of the liquid distributors used to introduce the feed and reflux to a packed bed is critical to making the packing perform to it maximum efficiency. Methods of evaluating the effectiveness of a liquid distributor to evenly distribute the liquid entering a packed bed can be found in references.[23][24] Considerable work as been done on this topic by Fractionation Research, Inc. (commonly known as FRI).[25]

Multi-effect distillation

The goal of multi-effect distillation is to increase the energy efficiency of the process, for use in desalination, or in some cases one stage in the production of ultrapure water. The number of effects is proportional to the kWh/m3 of water recovered figure, and refers to the volume of water recovered per unit of energy compared with single-effect distillation. One effect is roughly 636 kWh/m3.

Multi-stage flash distillation Can achieve more than 20 effects with thermal energy input, as mentioned in the article. Vapor compression evaporation Commercial large-scale units can achieve around 72 effects with electrical energy input, according to manufacturers.

There are many other types of multi-effect distillation processes, including one referred to as simply multi-effect distillation (MED), in which multiple chambers, with intervening heat exchangers, are employed.

Distillation in food processing

Distilled beverages
Main article: Distilled beverage Carbohydrate-containing plant materials are allowed to ferment, producing a dilute solution of ethanol in the process. Spirits such as whiskey and rum are prepared by distilling these dilute solutions of ethanol. Components other than ethanol, including water, esters, and other alcohols, are collected in the condensate, which account for the flavor of the beverage.

Gallery
Chemistry on its beginnings used retorts as laboratory equipment exclusively for distillation processes.

A simple set-up to distill dry and oxygen-free toluene.

Diagram of an industrial-scale vacuum distillation column as commonly used in oil refineries

A rotary evaporator is able to distill solvents more quickly at lower temperatures through the use of a vacuum.

Distillation using semi-microscale apparatus. The jointless design eliminates the need to fit pieces together. The pear-shaped flask allows the last drop of residue to be removed, compared with a similarly-sized round-bottom flask The small holdup volume prevents losses. A pig is used to channel the various distillates into three receiving flasks. If necessary the distillation can be carried out under vacuum using the vacuum adapter at the pig.

Distillation is defined as:

a process in which a liquid or vapour mixture of two or more substances is separated into its component fractions of desired purity, by the application and removal of heat. Distillation is based on the fact that the vapour of a boiling mixture will be richer in the components that have lower boiling points. Therefore, when this vapour is cooled and condensed, the condensate will contain more volatile components. At the same time, the original mixture will contain more of the less volatile material. Distillation columns are designed to achieve this separation efficiently. Although many people have a fair idea what distillation means, the important aspects that seem to be missed from the manufacturing point of view are that:

distillation is the most common separation technique it consumes enormous amounts of energy, both in terms of cooling and heating requirements it can contribute to more than 50% of plant operating costs The best way to reduce operating costs of existing units, is to improve their efficiency and operation via process optimisation and control. To achieve this improvement, a thorough understanding of distillation principles and how distillation systems are designed is essential.

tep 1: heat the solution to the boiling point of the product you're trying to remove by distillation-if you're making fine liquor, you raise the temperature to 173 degrees, the boiling point of ethanol. Maybe a bit higher, but not much. Care is called for. (Many guys who make moonshine raise the temperature until the still starts thumping, causing more than just ethanol to boil off-these extra alcohols are one reason moonshine can kill you. Well, that and some moonshiners like to use car radiators as condensers, causing the shine to contain both lead and antifreeze-NOT good! Stay away from moonshine!) Step 2: capture the steam and recondense it into a liquid.