(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 100°, which boils at a constant temperature of 126°, and contains 68% of acid. Hydrochloric acid forms a similar mixture which boils at 110° 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 100% 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.
| Fig. 4. |
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 Pa1b1Q. The horizontal line a1b1 corresponds to the two layers of liquid, and the inclined lines Pa1Qb1 to solutions of B in A and of A in B. The curves Pa4Q, having a minimum at a4, Pa3Q, having a maximum at a3, and Pa5Q, 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 (1) 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.