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 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 ortho- and 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 -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 ); 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 (1) 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 M1, M2, and P1, P2 be the molecular weights and vapour pressures of the components A and B, then the ratio of A to B in the distillate is M1P1/M2P2. Although, as is generally the case, one liquid (say A) is more volatile than the other (say B), i.e. P1 greater than P2, if the molecular weight of A be much less than that of B, then it is obvious that the ratio M1P1/M2P2 need not be very great, and hence the less volatile liquid B would come over in fair amount. These conditions 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 1 to 5. In general, when the substance to be distilled has a vapour pressure of only 10 mm. at 100° 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 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.

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.