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SECTION II.. _of_ Silver.

Elements of the Theory and Practice of Chymistry, 5th Ed. · Pierre Joseph Macquer — chapter 19 of 43 · ~1,972 words · public domain

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Of SILVER.

Next to Gold, Silver is the most perfect metal. Like Gold it resists the utmost violence of fire, even that in the focus of a burning-glass. However, it holds only the second place among metals; because it is lighter than Gold by almost one half; is also somewhat less ductile; and, lastly, because it is acted upon by a greater number of solvents.

Yet Silver hath one advantage over gold, namely that of being a little harder; which makes it also more sonorous.

This metal, like Gold, begins to flow when it is so thoroughly penetrated by the fire as to appear ignited like a live coal.

While this metal is in fusion, the immediate contact of the vapour of burning coals deprives it almost entirely of its malleability, in the same manner as we observed happens to Gold: but both these metals easily recover that property by being melted with nitre.

The nitrous acid is the true solvent of Silver, and being somewhat dephlegmated will very readily and easily take up a quantity of Silver equal in weight to itself.

Silver thus combined with the nitrous acid forms a metallic salt which shoots into crystals, called by the name of Lunar Crystals, or Crystals of Silver.

These crystals are most violently caustic: applied to the skin they quickly affect it much as a live coal would; they produce a blackish eschar, corroding and entirely destroying the parts they touch. Surgeons use them to eat away the proud fungous flesh of ulcers. As Silver united with the nitrous acid hath the property of blackening all animal substances, a solution of this metallic salt is employed to dye hair, or other animal matters, of a beautiful and durable black.

These crystals flow with a very moderate heat, and even before they grow red. Being thus melted they form a blackish mass; and in this form they are used by Surgeons, under the title of Lapis Infernalis, Infernal Stone, or Lunar Caustic.

Silver is also dissolved by the vitriolic acid: but then the acid must be concentrated, and in quantity double the weight of the Silver; nor will the solution succeed without a considerable degree of heat.

Spirit of salt and aqua regis, as well as the other acids, are incapable of dissolving this metal; at least in the ordinary way.

Though Silver be not soluble in the acid of sea-salt, nor easily in the acid of vitriol, as hath just been observed, it doth not follow that it hath but a weak affinity with the latter, and none at all with the former: on the contrary, it appears from experiment that it hath with these two acids a much greater affinity than with the acid of nitre: which is singular enough, considering the facility with which this last acid dissolves it.

The experiment which proves the fact, is this. To a solution of Silver in the nitrous acid, add the acid either of vitriol or of sea-salt, and the Silver will instantly quit its nitrous solvent to join with the superadded acid.

Silver thus united with the vitriolic or the marine acid is less soluble in water than when combined with the nitrous acid; and for this reason it is, that when either of these two acids is added to a solution of Silver, the liquor immediately becomes white, and a precipitate is formed, which is no other than the Silver united with the precipitating acid. If the precipitation be effected by the vitriolic acid, the precipitate will disappear upon adding a sufficient quantity of water, because there will then be water enough to dissolve it. But the case is not the same when the precipitation is made by the marine acid; for Silver combined therewith is scarce soluble in water.

This Precipitate of Silver, procured by means of the marine acid, is very easily fused, and when fused changes to a substance in some measure transparent and flexible, which hath occasioned it to be called by the name of Luna Cornea. If it be proposed to decompound this luna cornea, that is, to separate the marine acid from the Silver with which it is united, the luna cornea must be melted along with fatty and absorbent matters, with which the acid will unite, and leave the metal exceeding pure.

It must be observed, that if, instead of the marine acid, sea-salt in substance be added to a solution of Silver in the nitrous acid, a Precipitate is also produced, which by fusion appears to be a true luna cornea. The reason is, that the sea-salt is decomposed by the nitrous acid, which seizes its basis, as having a greater affinity therewith than its own acid hath; and this acid being consequently disengaged and set at liberty unites with the Silver, which, as has been shewn, has a greater affinity with it than with the nitrous acid. This is an instance of decomposition effected by means of one of those double affinities mentioned by us in our seventh proposition concerning Affinities.

From what hath been already said it is clear, that all these combinations of Silver with acids may be decompounded by absorbent earths and by fixed alkalis; it being a general law with regard to all metallic substances. We shall not therefore repeat this observation when we come to treat of the other metals; unless some particular occasion require it.

With regard to Silver I must take notice that, when separated by these means from the acids in which it was dissolved, it requires nothing but simple fusion to restore it to its usual form; because it does not, any more than Gold, lose its Phlogiston by those solutions and precipitations.

Silver unites with sulphur in fusion. If this metal be only made red-hot in a crucible, and sulphur be then added, it immediately flows; the sulphur acting as a flux to it. Silver thus united with sulphur forms a mass that may be cut, is half malleable, and hath nearly the colour and consistence of Lead. If this sulphurated Silver be kept a long time in fusion, and in a great degree of heat, the sulphur flies off and leaves the Silver pure. But if the sulphur be evaporated by a violent heat, it carries off with it part of the Silver.

Silver unites and mixes perfectly with Gold in fusion. The two metals thus mixed form a compound with properties partaking of both.

Metallurgists have hitherto sought in vain for a perfectly good and easy method of separating these two metals by the dry way only: (this term is used to signify all operations performed by fusion): but they are conveniently enough parted by the moist way, that is, by acid solvents. This method is founded on the above-mentioned properties of Gold and Silver with respect to acids. It hath been shewn that aqua regis only will dissolve Gold; that Silver, on the contrary, is not soluble by aqua regis, and that its proper solvent is the acid of nitre; consequently, when Gold and Silver are mixed together, if the compound mass be put into aqua fortis, this acid will take up all the Silver, without dissolving a particle of the Gold, which will therefore remain pure; and by this means the desired separation is effected. This method, which is commonly made use of by Goldsmiths, and in Mints, is called the Parting Assay.

It is plain, that if aqua regis were employed instead of aqua fortis, the separation would be equally effected; and that the only difference between this process and the former would consist in this, that now the Gold would be dissolved, and the Silver remain pure. But the operation by aqua fortis is preferable; because aqua regis does take up a little Silver, whereas aqua fortis hath not the least effect on Gold.

It must be observed, that, when Gold and Silver are mixed together in equal parts, they cannot be parted by the means of aqua fortis. To enable the aqua fortis to act duly on the Silver, this metal must be, at least, in a triple proportion to the Gold. If it be in a less proportion, you must either employ aqua regis to make the separation, or, if you prefer the use of aqua fortis, melt the metalline mass, and add as much Silver as is necessary to make up the proportion above-mentioned: and hence this Process is called Quartation.

This effect, which is pretty singular, probably arises from hence, that when the Gold exceeds or even equals the Silver in quantity, the parts of both being intimately united, the former are capable of coating over the latter, and covering them so as to defend them from the action of the aqua fortis; which is not the case when there is thrice as much Silver as Gold.

There is one thing more to be taken notice of with regard to this process; which is, that perfectly pure aqua fortis is rarely to be met with, for two reasons; first, it is difficult in making it wholly to prevent the rising of the medium employed to disengage the nitrous acid; that is, a little of the vitriolic acid will mix with the vapours of the aqua fortis: secondly, unless the salt-petre be very well purified it will always hold some small portion of sea-salt, the acid of which, we know, is very readily set loose by the vitriolic acid, and consequently rises together with the vapours of the aqua fortis. It is easy to see that aqua fortis mixed either with the one or the other is not proper for the Parting Process; because, as has just been said, the vitriolic and the marine acid equally precipitate Silver dissolved in the nitrous acid; by which means, when they are united with that acid, they weaken its action upon the Silver, and hinder the dissolution. Add, that aqua fortis adulterated with a mixture of spirit of salt becomes an aqua regis, and consequently is rendered capable of dissolving Gold, in proportion as its action upon Silver is diminished.

In order to remedy this inconvenience, and free aqua fortis from the vitriolic or marine acid with which it is tainted, Silver must be dissolved therein: by degrees as the metal dissolves, those heterogeneous acids lay hold of it, and precipitate with it in the form of a white powder, as we observed before. This precipitate being wholly fallen, the liquor grows clear; after which, if it be found capable of dissolving more silver, without turning milky, it may be depended on as a perfectly pure aqua fortis. Then filtre it, dissolve more Silver in it, as long as it will take up any, and you will have a solution of Silver in a very pure aqua fortis. By means of this solution may other aqua fortis be purified: for pour a few drops thereof into a very impure aqua fortis, and immediately the vitriolic or marine acid, with which that aqua fortis is contaminated, will join the Silver and fall therewith to the bottom. When the solution of Silver, prepared as above, does not in the least affect the transparency of the aqua fortis, it is then very pure, and fit for the purposes of Quartation.

This operation of purifying aqua fortis by a solution of Silver is called the Precipitation of Aqua Fortis, and aqua fortis thus purified is called Precipitated Aqua Fortis.

When Silver is dissolved in aqua fortis it may be separated therefrom, as hath been shewn, by absorbent earths and fixed alkalis.

We shall see by and by that there are other means of effecting this: but whatever way it be separated from its solvent it recovers its metalline form, as Gold does, by being simply fused without any additament.

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