A Dictionary of Arts, Manufactures and Mines / containing a clear exposition of their principles and practice

by Andrew Ure

The cupels are formed in a circular mould made of cast steel, very nicely turned, by which means they are easily freed from the mould when struck. The bone-ash is used moistened with a quantity of water, sufficient to make the particles adhere firmly together. The circular mould is filled, and pressed level with its surface; after which, a pestle or rammer, having its end nicely turned, of a globular or convex shape, and of a size equal to the degree of concavity wished to be made in the cupel for the reception of the assay, is placed upon the ashes in the mould, and struck with a hammer until the cupel is properly formed. These cupels are allowed to dry in the air for some time before they are used. If the weather is fine, a fortnight will be sufficient.

An assay may prove defective for several reasons. Sometimes the button or bead sends forth crystalline vegetations on its surface with such force, as to make one suppose a portion of the silver may be thrown out of the cupel. When the surface of the bead is dull and flat, the assay is considered to have been too hot, and it indicates a loss of silver in fumes. When the tint of the bead is not uniform, when its inferior surface is bubbly, when yellow scales of oxide of lead remain on the bottom of the cupel, and the bead adheres strongly to it, by these signs it is judged that the assay has been too cold, and that the silver retains some lead.

Lastly, the assay is thought to be good if the bead is of a round form, if its upper surface is brilliant, if its lower surface is granular and of a dead white, and if it separates readily from the cupel.

After the lead is put into the cupel, it gets immediately covered with a coat of oxide, which resists the admission of the silver to be assayed into the melted metal; so that the alloy cannot form. When a bit of silver is laid on a lead bath in this predicament, we see it swim about for a long time without dissolving. In order to avoid this result, the silver is wrapped up in a bit of paper; and the carburetted hydrogen generated by its combustion, reduces the film of the lead oxide, gives the bath immediately a bright metallic lustre, and enables the two metals readily to combine.

As the heat rises, the oxide of lead flows round about over the surface, till it is absorbed by the cupel. When the lead is wasted to a certain degree, a very thin film of it only remains on the silver, which causes the iridescent appearance, like the colours of soap-bubbles; a phenomenon, called by the old chemists, fulguration.

When the cupel cools in the progress of the assay, the oxygenation of the lead ceases; and, instead of a very liquid vitreous oxide, an imperfectly melted oxide is formed, which the cupel cannot absorb. To correct a cold assay, the temperature of the furnace ought to be raised, and pieces of paper ought to be put into the cupel, till the oxide of lead which adheres to it, be reduced. On keeping up the heat, the assay will resume its ordinary train.

Pure silver almost always vegetates. Some traces of copper destroy this property, which is obviously due to the oxygen which the silver can absorb while it is in fusion, and which is disengaged the moment it solidifies. An excess of lead, by removing all the copper at an early stage, tends to cause the vegetation.

The brightening is caused by the heat evolved, when the button passes from the liquid to the solid state. Many other substances present the same phenomenon.

In the above operation it is necessary to employ lead which is very pure, or at least free from silver. That kind is called poor lead.

It has been observed at all times, that the oxide of lead carries off with it, into the cupel, a little silver in the state of an oxide. This effect becomes less, or even disappears, when there is some copper remaining; and the more copper, the less chance there is of any silver being lost. The loss of silver increases, on the other hand, with the dose of lead. Hence the reason why it is so important to proportion the lead with a precision which, at first sight, would appear to be superfluous. Hence, also, the reason of the attempts which have, of late years, been made to change the whole system of silver assays, and to have recourse to a method exempt from the above causes of error.