Bible Encyclopedias
Distillation

2. Distillation under Reduced Pressure

This method is adopted for substances which decompose at their boiling-points under ordinary pressure, and, generally, when it is desirable to work at a lower temperature. The apparatus differs very slightly from that employed in ordinary distillation. The "receiver" must be connected on the one side to the condenser, and on the other to the exhaust pump. A safety vessel and a manometer are generally interposed between the pump and receiver. For the purpose of collecting the distillates in fractions, many forms of receivers have been devised. Briihl's is one of the simplest. It consists of a number of tubes mounted vertically on a horizontal circular disk which rotates about a vertical axis in a cylindrical vessel. This vessel has two tubulures: through one the end of the condenser projects so as to be over one of the receiving tubes; the other leads to the pump. By rotating the disk the tubes may be successively brought under the end of the condenser. Boiling under reduced pressure has one very serious drawback, viz. the liquid boils irregularly or "bumps." W. Dittmar showed that this may be avoided by leading a fine, steady stream of dry gas - air, carbon dioxide, hydrogen, &c., according to the substance operated upon - through the liquid by means of a fine capillary tube, the lower end of which reaches to nearly the bottom of the flask. "Bumping" is common in open boiling when the liquid is free from air bubbles and the interior of the vessel is very smooth. It may be diminished by introducing clippings of platinum foil, pieces of porcelain, glass beads or garnets into the liquid. "Frothing" is another objectionable feature with many liquids. When cold, froth can be immediately dissipated by adding a few drops of ether. In boiling liquids its formation may be prevented by adding paraffin wax; the wax melts and forms a ring on the surface of the liquid, which boils tranquilly in the centre.

3. Fractional Distillation

By fractional distillation is meant the separation of a mixture having components which boil at neighbouring temperatures. The distilling flask has an elongated neck so that Wurtz. Linnemann. Le Bel-Henninger. Glynsky.

FIG. 3.

the less volatile vapours are condensed and return to the flask,, while the more volatile component passes over. The success of the operation depends upon two factors: (I) that the heating be careful, slow and steady, and (2) that the column attached to the flask be efficient to sort out, as it were, the most volatile vapour. Three types of columns are employed: (I) the elongation is simply a straight or bulb tube; (2) the column, properly termed a "dephlegmator," is so constructed that the vapours have to traverse a column of previously condensed vapour; (3) the column is encircled by a jacket through which a liquid circulates at the same temperature as the boiling-point of the most volatile component. To the first type belongs the simple straight tube, and the Wurtz tube (see fig. 3), which is simply a series of bulbs blown on a tube. These forms are not of much value. Several forms of the second type are in use. In the Linnemann column the condensed vapours temporarily collect on platinum gauzes (a) placed at the constrictions of a bulbed tube. In the Le Bel-Henninger form a series of bulbs are connected consecutively by means of syphon tubes (b) and having platinum gauzes (a) at the constrictions, so that when a certain amount of liquid collects in any one bulb it syphons over into the next lower bulb. The Glynsky form is simpler, having only one syphon tube; at the constrictions it is usual to have a glass bead. The "rod-and-disk" form of Sidney Young is a series of disks mounted on a central spindle and surrounded by a slightly wider tube. The "pearshaped" form of the same author consists of a series of pear-shaped bulbs, the narrow end of one adjoining the wider end of the next lower one. In this class may also be placed the Hempel tube, which is simply a straight tube filled with glass beads. Of the third type is the Warren column consisting of a spiral kept at a constant temperature by a liquid bath. Improved forms were devised by FIG. 2.

Young.

Kreusler.

F. D. Brown. Kreusler's form is easily made and manipulated. A tube closed at the bottom is traversed by an open narrower tube, and the arrangement is fitted in the neck of the distilling flask. Water is led in by the inner tube, and leaves by a side tube fused on the wider tube. Many comparisons of the effectiveness of dephlegmating columns have been made (see Sidney Young, Fractional Distillation, 1903). The pear-shaped form is the most effective, second in order is the Le Bel-Henninger, which, in turn, is better than the Glynsky. The main objection to the Hempel is the retention of liquid in the beads, and the consequent inapplicability to the distillation of small quantities.

4. Distillation with Steam. - In this process a current of steam, which is generated in a separate boiler and superheated, if necessary, by circulation through a heated copper worm, is led into the distilling vessel, and the mixed vapours condensed as in the ordinary processes. This method is particularly successful in the case of substances which cannot be distilled at their ordinary boiling-points (it will be seen in the following section that distilling with steam implies a lowering of boiling-point), and which can be readily separated from water. Instances of its application are found in the separation of orthoand para-nitrophenol, the o-compound distilling and the p- remaining behind; in the separation of aniline from the mixture obtained by reducing nitrobenzene; of the naphthols from the melts produced by fusing the naphthalene monosulphonic acids with potash; and of quinoline from the reaction between aniline, nitrobenzene, glycerin, and sulphuric acid (the product being first steam distilled to remove any aniline, nitrobenzene, or glycerin, then treated with alkali, and again steam distilled when quinoline comes over). With substances prone to discolorization, as, for example, certain amino compounds, the operation may be conducted in an atmosphere of carbon dioxide, or the water may be saturated with sulphuretted hydrogen. Liquids other than water may be used: thus alcohol separates a-pipecoline and ether nitropropylene.

5. Theory of Distillation. - The general observation that under a constant pressure a pure substance boils at a constant temperature leads to the conclusion that the distillate which comes over while the thermometer records only a small variation is of practically constant composition. On this fact depends "rectification or purification by distillation." A liquid boils when its vapour pressure equals the superincumbent pressure (see Vaporization); consequently any process which diminishes the external pressure must also lower the boiling-point. In this we have the theory of "distillation under reduced pressure." The theory of fractional distillation, or the behaviour of liquid mixtures when heated to their boiling-points, is more complex. For simplicity we confine ourselves to mixtures of two components, in which experience shows that three cases are to be recognized according as the components are (I) completely immiscible, (2) partially miscible, (3) miscible in all proportions.

When the components are completely immiscible, the vapour pressure of the one is not influenced by the presence of the other. The mixture consequently distils at the temperature at which the sum of the partial pressures equals that of the atmosphere. Both components come over in a constant proportion until one disappears; it is then necessary to raise the temperature in order to distil the residue. The composition of the distillate is determinate (by Avogadro's law) if the molecular weights and vapour pressure of the components at the temperature of distillation be known. If M 1, M2, and P 1, P 2 be the molecular weights and vapour pressures of the components A and B, then the ratio of A to B in the distillate is M 1 P 1 /M 2 P 2. Although, as is generally the case, one liquid (say A) is more volatile than the other (say B), i.e. P 1 greater than P2, if the molecular weight of A be much less than that of B, then it is obvious that the ratio M 1 P 1 /M 2 P 2 need not be very great, and hence the less volatile liquid B would come over in fair amount. These con-, ditions pertain in cases where distillation with steam is successfully practised, the relatively high volatility of water being counterbalanced by the relatively high molecular weight of the other component; for example, in the case of nitrobenzene and water the ratio is I to 5. In general, when the substance to be distilled has a vapour pressure of only 10 mm. at loo° C., distillation with steam can be adopted, if the product can be subsequently separated from the water.

When distilling a mixture of partially miscible components a distillate of constant composition is obtained so long as two layers are present, i.e. A dissolved in B and B dissolved in A, since both of these solutions emit vapours of the same composition (this follows since the same vapour must be in equilibrium with both solutions, for if it were not so a cyclic system contradicting the second law of thermodynamics would be realizable). The composition of the vapour, however, would not be the same as that of either layer. As the distillation proceeded one layer would diminish more rapidly than the other until only the latter would remain; this would then distil as a completely miscible mixture.

The distillation of completely miscible mixtures is the most common practically and the most complex theoretically. A coordination of the results obtained on the distillation of mixtures of this nature with the introduction of certain theoretical considerations led to the formation of three groups distinguished by the relative solubilities of the vapours in the liquid components.

(i.) If the vapour of A be readily soluble in the liquid B, and the vapour of B readily soluble in the liquid A, there will exist a mixture of A and B which will have a lower vapour pressure than any other mixture. The vapour pressure composition curve will be convex to the axis of compositions, the maximum vapour pressures corresponding to pure A and pure B, and the minimum to some mixture of A and B. On distilling such a mixture under constant pressure, a mixture of the two components (of variable composition) will come over until there remains in the distilling flask the mixture of minimum vapour pressure. This will then distil at a constant temperature. Thus nitric acid, boiling-point 68°, forms a mixture with water, boiling point loo°, which boils at a constant temperature of 126°, and contains 68% of acid. Hydrochloric acid forms a similar mixture which boils at I 10° and contains 20.2% of acid. Another mixture of this type is formic acid and water.

(ii.) If the vapours be sparingly soluble in the liquids there will exist a mixture having a greater vapour pressure than that of any other mixture. The vapour pressure-composition curve will now be concave to the axis of composition, the minima corresponding to the pure components. On distilling such a mixture, a mixture of constant composition will distil first, leaving in the distilling flask one or other of the components according to the composition of the mixture. An example is propyl alcohol and water. At one time it was thought that these mixtures of constant boiling-point (an extended list is given in Young's Fractional Distillation) were definite compounds. The above theory, coupled with such facts as the variation of the composition of the constant boiling-point fraction with the pressure under which the mixture is distilled, the proportionality of the density of all mixtures to their composition, &c., shows this to be erroneous.

(iii.) If the vapour of A be readily soluble in liquid B, and the vapour of B sparingly soluble in liquid A, and if the vapour pressure of A be greater than that of B, then the vapour pressures of mixtures of A and B will continually diminish as one passes from 100% A to loo % B. The vapour tension may approximate to a linear function of the composition, and the curve will then be practically a straight line. On distilling such a mixture pure A will come over first, followed by mixtures in which the quantity of B continually increases; consequently by a sufficient number of distillations A and B can be completely separated. Examples are water and methyl or ethyl alcohol.

Van't Hoff (Theoretical and Physical Chemistry, vol. i. p. 51) illustrates the five cases on one diagram. In fig. 4 let AB be the axis of composition, AP be the vapour pressure of pure A, BQ the vapour pressure of pure B. For immiscible liquids the vapour pressure curve is the horizontal line ab, described so that aP = QB and bQ=AP. For partially miscible liquids the curve is Pa i b i Q. The horizontal line a l b 1 corresponds to the two layers of liquid, and the inclined lines Pa l Qb1 to solutions of B in A and of A in B. The curves Pa4Q, having a minimum at a4, Pa3Q, having a maximum at a 31 and Pa 5 Q, with neither a maximum nor minimum, correspond to the types i., ii., iii. of completely miscible mixtures.

6. Dry Distillation. - In this process the substance operated upon is invariably a solid, the vapours being condensed and collected as in the other methods. When the substance operated upon is of uncertain composition, as, for example, coal, wood, coal-tar, &c., the term destructive distillation is employed. A more general designation is "pyrogenic processes," which also includes such operations as leading vapours through red-hot tubes and condensing the products. We may also consider here cases of sublimation wherein a solid vaporizes and the vapour condenses without the occurrence of the liquid phase.

Dry distillation is extremely wasteful even when definite substances or mixtures, such as calcium acetate which yields acetone, are dealt with, valueless by-products being obtained and the condensate usually requiring much purification. Prior to 1830, little was known of the process other than that organic compounds generally yielded tarry and solid matters, but the discoveries of Liebig and Dumas (of acetone from acetates), of Mitscherlich (of benzene from benzoates) and of Persoz (of methane from acetates and lime) brought the operation into common laboratory practice. For efficiency the operation must be conducted with small quantities; caking may be prevented by mixing the substance with sand or powdered pumice, or, better, with iron filings, which also renders the decomposition more regular by increasing the conductivity of the mass. The most favourable retort is a shallow iron pan heated in a sand bath, and provided with a screwed-down lid bearing the delivery tube. Sidney Young has suggested conducting the operation in a current of carbon dioxide which sweeps out the vapours as they are evolved, and also heating in a vapour bath, e.g. of sulphur.

One of the earliest red-hot tube syntheses of importance was the formation of naphthalene from a mixture of alcohol and ether vapours. Such condensations were especially studied by M. P. E. Berthelot, and shown to be very fruitful in forming hydrocarbons.

Sometimes reagents are placed in the combustion tube, for example lead oxide (litharge), which takes up bromine and sulphur. In its simplest form the apparatus consists of a straight tube, made of glass, porcelain or iron according to the temperature required and the nature of the reacting substances, heated in an ordinary combustion furnace, the mixture entering at one end and the vapours being condensed at the other. Apparatus can also be constructed in which the unchanged vapours are continually circulated through the tube. Operating in a current of carbon dioxide facilitates the process by preventing overheating.

7. Distillation in Chemical Technology. - In laboratory practice use is made of a fairly constant type of apparatus, only trifling modifications being generally necessary to adapt the apparatus for any distillation or fractionation; in technology, on the other hand, many questions have to be considered which generally demand the adoption of special constructions for the economic distillation of different substances. The modes of distillation enumerated above all occur in manufacturing practice. Distillation in a vacuum is practised in two forms: - if the pump draws off steam as well as air it is termed a "wet" air-pump; if it only draws off air, it is a "dry" air-pump. In the glycerin industry the lyes obtained by saponifying the fats are first evaporated with "wet vacuum" and finally distilled with closed and live steam and a "dry vacuum." Two forms of steam distillation may be distinguished: - in one the still is simply heated by a steam coil wound inside or outside the still - this is termed heating by dry steam; in the other steam is injected into the mass within the still - this is the distillation with live steam of laboratory practice. The details of the plant - the material and fittings of the still, the manner of heating, the form of the condensing plant, receivers, &c. - have to be determined for each substance to be distilled in order to work with the maximum economy.

For the distillation of liquids the retort is usually a cylindrical pot placed vertically; cast iron is generally employed, in which case the bottom is frequently incurved and thicker than the sides in order to take up the additional wear and tear. Sometimes linings of enamelled iron or other material are employed, which when worn can be replaced at a far lower cost than that of a new still. Glass stills heated by a sand bath are sometimes employed in the final distillation of sulphuric acid; platinum, and an alloy of platinum and iridium with a lining of gold rolled on (a discovery due to Heraeus), are used for the same purpose. Cast iron stills are provided with a hemispherical head or dome, generally attached to the body of the still by bolts, and of sufficient size to allow for any frothing. It is invariably provided with an opening to carry off the vapours produced. In its more complete form a still has in addition the following fittings: - The dome is provided with openings to admit (I) the axis of the stirring gear (in some stills the stirring gear rotates on a horizontal axis which traverses the side and not the head of the still), (2) the inlet and outlet tubes of a closed steam coil, (3) a tube reaching to nearly the bottom of the still to carry live steam, (4) a tube to carry a thermometer, (5) one or more manholes for charging purposes, (6) sight-holes through which the operation can be watched, and (7) a safety valve. The body of the still is provided with one or more openings at different heights to serve for the discharge of the residue in the still, and sometimes with a glass gauge to record the quantity of matter in the still. For dry distillations the retorts are generally horizontal cylinders, the bottom or lower surface being sometimes flattened. Iron and fireclay are the materials commonly employed; wrought iron is used in the manufacture of wood-spirit, fireclay for coal-gas (see GAS: Manufacture), phosphorus, zinc, &c. The vertical type, however, is employed in the manufacture of acetone and of iodine.

Several modes of heating are adopted. In some cases, especially in dry distillations, the furnace flames play directly on the retorts, in others, such as in the case of nitric acid, the whole still comes under the action of the furnace gases to prevent condensation on the upper part of the still, while in others the furnace gases do not play directly on the base or upper portion of the still but are conducted around it by a system of flues (see Coal-Tar). Steam heating, dry or live, is employed alone and also as an auxiliary to direct firing.

The condensing plant varies with the volatility of the distillate. Air cooling is adopted whenever possible. For example, in the less modern methods for manufacturing nitric acid the vapours were conducted directly into double-necked bottles (bombonnes) immersed in water. A more efficient arrangement consists of a stack of vertical pipes standing up from a main or collecting trough and connected at the top in consecutive pairs by a cross tube. By an arrangement of diaphragms in the lower trough the vapours are circulated through the system. As an auxiliary to air cooling the stack may be cooled by a slow stream of water trickling down the outside of the pipes, or, in certain cases, cold water may be injected into the condenser in the form of a spray, w here it meets the ascending vapours. Horizontal air-cooling arrangements are also employed. A common type of condenser consists of a copper worm placed in a water bath; but more generally straight tubes of copper or cast iron which cross and recross a rectangular tank are employed, since this form is more readily repaired and cleansed. Wood-spirit, petroleum and coal-tar distillates are condensed in plant of the latter type. In cases where the condenser is likely to become plugged there is a pipe by means of which live steam can be injected into the condenser. The supply of water to the condenser is regulated according to the volatility of the condensate. When the vapours readily condense to a solid form the condensing plant may take the form of large chambers; such conditions prevail in the manufacture of arsenic, sulphur and lampblack: in the latter case (which, however, is not properly one of distillation) the chamber is hung with sheets on which the pigment collects. Large chambers are also used in the condensation of mercury.

Dephlegmation of the vapours arising from such mixtures as coaltar fractions, petroleum and the "wash" of the spirit industry, is very important, and many types of apparatus are employed in order to effect a separation of the vapours. The earliest form, invented by C. B. Mansfield to facilitate the fractionation of paraffin and coaltar distillates, consisted in having a pipe leading from the inclined delivery tube of the still to the still again, so that any vapour which condensed in the delivery tube was returned to the still. Of really effective columns Coupier's was one of the earliest. The vapours rising from the still traverse a tall vertical column, and are then conveyed through a series of bulbs placed in a bath kept at the boiling-point of the most volatile constituent. The more volatile vapours pass over to the condensing plant, while the less volatile ones condense in the bulbs and are returned to the column at varying heights by means of connecting tubes. The French column is similar in action. The Coffey still is one of the most effective and is employed in the spirit, ammonia, coal-tar and other industries. It consists of a vertical column divided into a number of sections by horizontal plates, which are perforated so that the ascending vapours have to traverse a layer of liquid. Above this "separator" is a reflux condenser, termed the "cooler," maintained at the correct temperature so that only the more volatile component passes to the receiver. The success of the operation chiefly depends upon the proper management of the cooler.

8. Commercial Distillation of Water. - Distilled water, i.e. water free from salts and to some extent of the dissolved gases which are always present in natural waters, 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 still is usually fed continuously by the heated water from the condenser. The first portion of the distillate brings over the gases dissolved in the water, ammonia and other volatile impurities, and is consequently rejected; scarcely two-fifths of the entire quantity of water can be safely used as pure distilled water.

Apparatus for the economic production of a potable water from sea-water is of vital importance in the equipment of ships. 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 disagreeable 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, the following conditions are essential: - Ist, aeration of the distilled product so that it may be immediately available for drinking purposes; 2nd, economy of coal to obtain the maximum of water with the minimum expenditure of fuel; and 3rd, simplicity of working parts, to secure the apparatus from breaking down, and enable unskilled attendants to work it with safety. The problem is a comparatively old one, for we find that R. Fitzgerald patented a process in 1683 having for its purpose the "sweetening of sea-water." A history of early attempts is given in S. Hales's Philosophical Experiments, published in 1739. Among the earlier of the modern forms of apparatus which came into practical adoption are the inventions of Dr Normandy and of Chaplin of Glasgow, the apparatus of Rocher of Nantes, and that patented by Gall& and Mazeline of Havre. Normandy's apparatus, although economical and producing water of good quality, is very complex in its structure, consisting of very numerous working parts, with elaborate arrangements of pipes, cocks and other fittings. It is consequently expensive and requires careful attention for its working. It was extensively adopted in the British navy, the Cunard line and many other important emigrant and mercantile lines. Chaplin's apparatus, which was invented and patented later, has also since 1865 been sanctioned for use on emigrant, troop and passenger vessels. The apparatus possesses the great merit of simplicity and compactness, in consequence of which it is comparatively cheap and not liable to derangement. It was adopted by many important British and continental shipping companies, among others by the Peninsular & Oriental, the Inman, the North German Lloyd and the Hamburg American companies.

The modern distilling plant consists of two main parts termed the evaporator and condenser; in addition there must be a boiler (sometimes steam is run off the main boilers, but this practice has several disadvantages), pumps for circulating cold water in the condenser and for supplying salt water to the evaporator, and a filter through which the aerated water passes. The evaporator Viii. I I consists of a cylindrical vessel having in its lower half a horizontal copper coil connected to the steam supply. The cylindrical vessel is filled to a certain level with salt water and the steam turned on. The water vaporizes and is led from the dome of the evaporator to the head of the condenser. The water level is maintained in the evaporator until it contains a certain amount of salt. It is then run off, and replaced by fresh sea-water. The condenser consists of a vertical cylinder having manifolds at the head and foot and through which a number of tubes pass. In some types, e.g. the Weir, the condensing water circulates upwards through the tubes; in others, e.g. the Quiggins, the water circulates around the tubes. Various forms of the tubes have been adopted. In the Pape-Henneberg condenser, which has been adopted in the German navy, they are oval in section and tend to become circular under the pressure of the steam; this alteration in shape makes the tubes self-scaling. In the Quiggins condenser, which has been widely adopted, e.g. in the "Lusitania," the steam traverses vertical copper coils tinned inside and outside; the coils are crescent-shaped, a form which gives a greater condensing surface and makes the coils self-scaling. The aeration of the water is effected by blowing air into the steam before it is condensed; as an auxiliary, the storage tanks have a false bottom perforated by fine holes so that if air be injected below it, the water is efficiently aerated by the air which traverses it in fine streams. After condensation the water is filtered through charcoal. The filter is either a separate piece of plant, or, as in the Quiggins form, it may be placed below the coils in the same outer vessel. In this plant the aeration is conducted by blowing in air at the base of the condenser. After filtration the water is pumped to the storage tanks. Many types of distilling plant are in use in addition to those mentioned above, for example the Rayner, Kirkaldy, Merlees, Normand; the United States navy has adopted a form designed by the Bureau of Engineering.

BIBLIOGRAPHY. - The general practice of laboratory distillation is discussed in all treatises on practical organic chemistry; reference may be made to Lassar-Cohn, Manual of Organic Chemistry (1896), and Arbeitsmethoden fiir organisch-chemische Laboratorien (1901); Hans Meyer, Analyse and Konstitutionermittlung organischer Verbindungen (1909). The theory of distillation finds a place in all treatises on physical chemistry. Of especial importance is Sidney Young, Fractional Distillation (1903). The history of distillation is to be studied in E. Gildemeister and F. Hoffmann, Die ¢therischen Ole (Berlin, 1899; Eng. tr. by E. Kremers, Milwaukee Press, 1900). The technology of distillation is best studied in relation to the several industries in which it is employed; reference should be made to the articles COAL-TAR, GAS, PETROLEUM, SPIRITS, NITRIC ACID, &c. (C. E.*)