An ingenious method, somewhat simi lar, but less hazardous, was employed by Dr. Black. He first poured into a strong flint glass bottle six ounces of alcohol; then, by a funnel, the tube of which reach ed to the bottom of the bottle, he poured in two ounces of water, gently, so that it did not mix with the alcohol, but raised it above it ; and, lastly, he poured in four ounces of nitrous acid in the same man ner, so that the small column of water was interposed between it and the alco hol. The phial was set aside for some time in a cool place : the water attracted the alcohol at the one surface, the acid at the other, and thus brought them very gradually together, so as to admit of their reciprocal action without violence. At the end of a few months they were completely mixed, and nitric ether form ed, which floated above, was withdrawn and rectified by distillation.
The theory of the formation of nitric ether is as obscure as that of sulphuric ether. It is ascertained, however, that even from the commencement of the pro cess the acid is decomposed; nitric oxide gas is disengaged; and Pelletier found that the decomposition was complete, ni tric acid not being discoverable, either in the liquor which passed over, or in the residuum.
It is also proved, that in the formation of nitric ether the alcohol suffers decom position, as in the residual liquor oxalic and acetic acids are formed. There is no deposition, however, of carbonaceous mat ter, as there is in the formation of sulphu ric ether, the residual liquor being quite transparent and of a light colour. It ap pears to follow, therefore, from these facts, that in the formation of nitric ether part of the elements of the alcohol com bine with oxygen from the nitric acid, and form oxalic and acetic acids ; carbonic acid gas too is formed and disengaged, as Pelletier found, in considerable quantity, and much of the nitric acid mixed with nitric oxide and nitrogen gases. (Ms moires de Chimie, torn. i. p. 138.) It is difficult, however, to determine in. what manner these facts are to be com bined, so as to give with precision the theory of the formation of nitric ether : nor is it very apparent, whether any of the elements of the nitric acid enter into its composition, or whether they are en tirely disengaged during the process. It might be supposed, that it must contain more carbon than sulphuric ether, as none is deposited during its formation ; but we are not certain what quantity is carried off in the state of carbonic acid.
Nitric ether has some resemblance in its properties to sulphuric ether. Like it, it is light and volatile, and has been said, when highly rectified, to have these qua lities even in a higher degree than sulphu ric ether. It is also inflammable, burns with an enlarged flame, and is said to de posit more charcoal. It is soluble in water and in alcohol. Its odour is strong, though scarcely so agreeable as that of sulphuric ether; in the state, however, of what has been named dulcified spirit of nitre, it is more fragrant. Its colour is usually yellow ; but this, as well pro bably as some of its other qualities, ap pears rather to be owing to the presence of nitric acid, surcharged perhaps with nitric oxide.
Muriatic ether. Pelletier proposes the following process to form muriatic ether : place a retort in a sand-bath, and con nect it with a glass balloon, and two of Woulfe's bottles : put into the bottle 100 parts of muriate of soda, perfectly dry, and into the balloon and bottles the same quantity of alcohol. The joinings being luted;50 parts of sulphuric acid are to be poured on the salt, and the operation is left to proceed in the cold for five or six hours. A moderate heat is then to be gradually applied. The muriatic acid gas passes over, and is condensed by the alcohol. The whole of this liquor is then put into a retort, with twenty parts of oxide of manganese in fine powder ; and there is put into the receiver and bottles a solution of pure potash. It is distilled by a gentle beat : the muriatic ether passes over, and the reaction of any excess of oxymuriatic acid gas upon it, which would change it to oil, is pre vented by the alkali. The ether is then
to be rectified, by mixing it with twice its bulk of water, and distilling it by a very gentle heat.
The properties of muriatic ether have not been properly described, from the difficulty of obtaining it pure. It is said to be light, transparent, volatile, and in inflammable, emitting while burning a pungent odour, and to have a styptic taste.
A process has been given by Boudet for the preparation of phosphoric ether. He mixed liquid phosphoric acid of a thick consistence and alcohol in equal proportions, introduced the mixture into a tubulated retort connected with a re ceiver, and with an Woulfe's bottle, which was filled two-thirds with lime water : heat was applied, so as to cause the mixture to boil ; a portion of un changed alcohol first distilled over ; this was succeeded by a liquor having an ethereal odour, mixed a little with that of garlic : it reddened slightly the syrup of violets: when rectified by distillation, with the addition of carbonate of magne sia, the product was colourless, and had an odour somewhat similar to that of sul phuric ether : it was volatile, and highly inflammable, its combustion not being ac companied with any smoke. It floated on the surface of water, but by agitation with it was dissolved. It dissolved the volatile oils, and also phosphorus. Its specific gravity was inferior to that of al cohol, being as 94 to 100. After its pro duction, when the heat was much raised, a quantity of oily matter was distilled over, and carburetted hydrogen was dis engaged, the residual liquor was of a dark brown colour, and contained a large quantity of phosphoric acid. iAnnales de Chimie, torn. xi. p. 123.) Finnic ether has been said to be form ed by putting fluate of lime, previously ignited and in powder, into a retort, with equal weights of alcohol and sulphuric acid, and distilling to dryness. The pro duct of this distillation was again distilled to one half, and a portion of fluoric acid abstracted from it by a solution of potash, which at the same time precipitated a portion of silex, so as to render the whole gelatinous. This, on being again distill ed, afforded an ether of the specific gra vity of 0.720, which burnt with a blue flame, and had a bitter taste. It is added, that it greatly resembled sulphuric ether; and it is not improbable that it may have been merely this ether disguised. (Ni cholson's Journal, vol. viii. p. 143.) acetic ether has been known for a con siderable time to chemists, Lauragais having given, in 1759, the process for preparing it, by distilling alcohol, with the concentrated acetic acid that is pro cured by the decomposition of acetate of copper by heat. Scheele, as well as other chemists, have been unable to ti,rm it ; but l'elletier has observed that it is procured with certainty by distilling alco hol repeatedly from the acetic acid. The alcohol at first acquires an ethereal odour, but is miscible with water; by returning it on the residual liquor, distilling it, and repeating this for a third time, this be comes stronger: the acid contained in the liquor thus procured was saturated by the addition of carbonate of potash ; and by distillation there was procured from it a pure acetic ether, in quantity about half of the alcohol employed. (" Me moirs de Chimie," torn. i. p. 237.) It was soluble in water in a limited quanti ty, seven measures dissolving three. It has an agreeable odour, ethereal, but in which the smell of acetic acid is also per ceptible. It is very volatile and inflam mable : it burns with a clear light, and leaves a little charcoal.
According to Pelletier, acetic ether may likewise be formed by distillation, from a mixture of sulphuric acid, acetate of cop per, and alcohol ; and according to Lap lanche, it may be obtained froma mixture of sulphuric acid, alcohol, and acetate of lead.