| Take | Pyrolignous acid | 4 | parts by measure, |
| Alcohol | 1 | part, mix, and add | |
| Nitric acid | 1 | part. |
This mixed liquor is to be applied from 11⁄2 to 15 minutes, according to the depth desired. The nitric acid was employed of the strength of 1·28—the double aquafortis of the shops.
The eau forte or menstruum for copper, used by Callot, as also by Piranesi, with a slight modification, is prepared, with
| 8 | parts of strong French vinegar, |
| 4 | parts of verdigris, |
| 4 | ditto sea salt, |
| 4 | ditto sal ammoniac, |
| 1 | ditto alum, |
| 16 | ditto water. |
The solid substances are to be well ground, dissolved in the vinegar, and diluted with the water; the mixture is now to be boiled for a moment, and then set aside to cool. This menstruum is applied to the washed, dried, and varnished plate, after it has suffered the ordinary action of aquafortis, in order to deepen and finish the delicate touches. It is at present called the eau forte à passer.
ETHER, is the name of a class of very light, volatile, inflammable, and fragrant spirituous liquids, obtained by distilling in a glass retort, a mixture of alcohol with almost any strong acid. Every acid modifies the result, in a certain degree, whence several varieties of ether are produced. The only one of commercial importance is sulphuric ether, which was first made known under the name of sweet oil of vitriol, in 1540, by the receipt of Walterus Cordus. Froberus, 190 years after that date, directed the attention of chemists afresh to this substance, under the new denomination of ether.
There are two methods of preparing it; by the first, the whole quantity of acid and alcohol are mixed at once, and directly subjected to distillation; by the second, the alcohol is admitted, in a slender streamlet, into a body of acid previously mixed with a little alcohol, and heated to 220° Fahr.
1. Mix equal weights of alcohol at spec. grav. 0·830, and sulphuric acid at 1·842, by introducing the former into a large tubulated retort, giving it a whirling motion, so that the alcohol may revolve round a central conical cavity. Into this species of whirlpool the acid is to be slowly poured. The mixture, which becomes warm, is to be forthwith distilled by attaching a spacious receiver to the retort, and applying the heat of a sand-bath. The formation of ether takes place only at a certain temperature. If the contents of the retort be allowed to cool, and be then slowly heated in a water bath, alcohol alone will come over for some time without ether, till the mixture acquires the proper degree of heat. The first receiver should be a globe, with a tube proceeding from its bottom, into a second receiver, of a cylindric shape, surrounded with ice-cold water. The joints must be well secured by lutes, after the expanded air has been allowed to escape. The liquid in the retort should be kept in a steady state of bullition. The ether, as long as it is produced, condenses in the balloon and neck of the receiver in striæ; when these disappear the process is completed. The retort must now be removed from the sand; otherwise it would become filled with white fumes containing sulphurous acid, and denser striæ would flow over, which would contaminate the light product with a liquid called sweet oil of wine.
The theory of etherification demonstrates that when strong sulphuric acid is mixed with alcohol, there is formed, on the one hand, a more aqueous sulphuric acid, and, on the other, sulphovinic acid. When this mixture is made to boil, the sulphovinic acid is decomposed, its dihydrate of carbon combines with the alcohol, and constitutes ether; while the proportion of sulphovinic acid progressively diminishes. Mr. Hennell, of the Apothecaries’ Hall, first explained these phenomena, and he was confirmed in his views by the interesting researches of Serullas. The acid left in the retort is usually of a black colour, and may be employed to convert into ether half as much alcohol again; an experiment which may be repeated several times in succession.
The most profitable way of manufacturing ether has been pointed out by Boullay. It consists in letting the alcohol drop in a slender stream into the acid, previously heated to the etherifying temperature. If the acid in this case were concentrated to 1·846, the reaction would be too violent, and the ether would be transformed into bicarburetted hydrogen (dihydrate of carbon.) It is therefore necessary to dilute the acid down to the density of 1·780; but this dilution may be preferably effected with alcohol instead of water, by mixing three parts of the strongest acid with 2 of alcohol, specific gravity 0·830, and distilling off a portion of the ether thereby generated; after which the stream of alcohol is to be introduced into the tubulure of the retort through a small glass tube plunged into the mixture; this tube being the prolongation of a metallic syphon, whose shorter leg dips into a bottle filled with the alcohol. The longer leg is furnished with a stop-cock, for regulating at pleasure the alcoholic streamlet. The distilled vapours should be transmitted through a worm of pure tin surrounded by cold water, and the condensed fluid received in a glass bottle. The quantity of alcohol which can be thus converted into ether by a given weight of sulphuric acid, has not hitherto been accurately determined; but it is at least double. In operating in this way, neither sulphurous acid, nor sweet oil of wine is generated, while the residuary liquid in the retort continues limpid and of a merely brownish yellow colour. No sulphovinic acid is formed, and according to the experiments of Geiger, the proportion of ether approaches to what theory shows to be the maximum amount. In fact 57 parts of alcohol of 0·83 sp. grav. being equivalent to 46·8 parts of anhydrous alcohol, yield according to Geiger, 331⁄2 parts of ether; and by calculation, they should yield 371⁄4.