Elements of the Theory and Practice of Chymistry, 5th ed.

by Pierre Joseph Macquer

To combine Fat Oils with Fixed Alkalis. Hard and soft Soap. The Decomposition of Soap.

Take a lixivium of Alicant kelp made more caustic by lime, as we shall shew when we come to speak of Alkalis. Evaporate this lye till it be capable of bearing a new-laid egg. Divide it into two parts; and to one of these put just water enough to weaken it so, that a new-laid egg will not swim in it, but fall to the bottom. With the lye thus weakened mix an equal quantity of fresh-drawn Olive Oil. Stir and agitate the mixture well, till it become very white. Set it over a gentle fire, and continue stirring it incessantly, that the two ingredients of which it is compounded may gradually combine together, as part of the water evaporates. When you perceive they begin to unite, pour into the mixture thrice as much of the first strong lye as you took of Olive Oil. Continue the coction with a gentle fire, always stirring the matter, till it becomes so thick that a drop of it fixes, as it cools, into the consistence that Soap ought to have. By dissolving a little of this Soap in water, you will discover whether or no it contains more Oil than ought to be in the composition. If it dissolves therein wholly and perfectly, without the appearance of the least little drop of Oil floating on the water, it is a sign that it doth not contain too much Oil. If, on the contrary, you perceive any of these little globules, you must pour into the vessel, containing your matter, a little more of the strong lye, to absorb the redundant Oil. If there be too much of the Alkali it may be discovered by the taste. If the Soap leave on your tongue the sensation of an Alkaline Salt, and produce an urinous savour, it is a sign that there is too much Salt in proportion to the Oil. In this case a little Oil must be added to the mixture, to saturate the super-abundant Alkali. An excess in the quantity of Alkali discovers itself likewise by the Soap's growing moist in the air, on being exposed to it for some time.

OBSERVATIONS.

Fixed Alkalis, even when resolved into a liquor, that is, when loaded with much water, unite easily with Fat Oils, as appears from the experiment just recited, and require but a moderate heat to perfect that union. This combination may even be completely effected without the aid of fire, and by the heat of the sun only, provided sufficient time be allowed for that purpose; as Mr. Geoffroy found upon trial. It only requires the mixture of the Oil and Alkali to be kept five or six days in digestion, and stirred from time to time. A lixivium of pure Alkali, not acuated by lime, may also be used to make Soap: but it is observed, that the combination succeeds better, and that the Alkali unites sooner and more perfectly with the Oil, when it is sharpened by lime.

The Oil is first mixed with a weaker and more aqueous lye, to the end that the combination may not take place too hastily, but that all the particles of the two substances to be compounded together may unite equally. But as soon as the Alkali begins to dissolve the Oil gradually and quietly, the dissolution may then be accelerated; and that is done by adding the remaining lye, which is stronger and less diluted than the other.

Soap made with Olive Oil is white, hard, and hath not a very disagreeable smell: but as that Oil is dear, others, even the fat and oils of animals, are sometimes substituted for it. The Soaps made with most of these other matters are neither so hard, nor so white, as that made of Olive Oil: they are called Soft Soaps.

Oils thus associated with Fixed Alkalis are by that means rendered soluble in water; because the Alkaline Salts, having a great affinity with water, communicate part thereof to the Oils with which they are now incorporated. Yet the Oil is not for all that rendered thoroughly miscible with water, or perfectly soluble therein; for the water in which Soap is dissolved hath always a milky cast: now there is no other criterion of a perfect solution but transparency.

Alkalis also lose part of their affinity with water, by the union they thus contract with Oils: for, when the combination is properly made, they no longer attract the moisture of the air, nor doth water dissolve them in such quantities as before. The composition of Soap is plainly a saturation of an Alkali with an Oil; and, in order to make perfect Soap, we are forced, as was said in the process, to grope, in a manner, by repeated trials, for this point of saturation; just as when we prepare a Neutral Salt by saturating an Alkali with an Acid. The union which the Oil contracts with the Alkali makes it lose, in part, the readiness with which it naturally takes fire; because the Salt is not inflammable: the water also, which enters in pretty considerable quantities into the composition of Soap, as we shall presently see, contributes a good deal to hinder the accension of the Oil.

Soap may be decompounded either by distilling it, or by mixing it with some substance that hath a greater affinity than Oil with Alkalis.

If we decompound it by distillation, a phlegm, or transparent spirit, of a somewhat yellowish colour, first comes over. This liquor is the aqueous part of the Soap, quickened by a little of its Alkali, which gives it an acrid taste. It is followed by a red Oil, which at first is pretty thin and limpid, but thickens as the distillation advances, grows black, and has a very disagreeable empyreumatic smell. This Oil is soluble in Spirit of Wine.