This section is from the American Hand Book of the Daguerreotype, by Samuel D. Humphrey. Published S. D. Humphrey, 37 Lispenard Street 1858.
Cyanide of Potassium.--This important article is worthy the undivided attention of every Daguerreotypist. I here give Mr. Smee's process for its preparation. This is from that author's work entitled, "Electro Metallurgy," American edition:
"The cyanide of potassium, so often alluded to while treating of the metallo-cyanides, may be formed in several ways. It may be obtained by heating to a dull redness the yellow ferrocyanate of potash, in a covered vessel, filtering and rapidly evaporating it. The objection to this method, however, is that without great care the whole of the ferrocyanate is not decomposed, a circumstance which much reduces its value for electro-metallurgy. By boiling, however, the ignited residue with spirits of wine this difficulty is said to be overcome, as the ferrocyanate is absolutely insoluble in that menstruum, while the cyanuret, at that heat, freely dissolves, and is as easily re-deposited on cooling.
"There is, however, a much better process by which this salt may be formed, viz. by simply transmitting hydrocyanic acid through potassium. Although the modes of making this acid are very numerous, there is but one which is likely to be employed on a very large scale, and that is its formation from the yellow ferrocyanate by means of sulphuric acid. This process is performed as follows: any given weight of the yellow salt is taken and dissolved in about five times its weight of water; this is placed in a retort, or some such analogous vessel, to which is then added a quantity of strong sulphuric acid, twice the weight of the salt, and diluted with three or four times its quantity of water. A pipe is carried from the neck of the retort to the receiving bottle, which should be kept as cool as possible.
"For small operations, those invaluable vessels, Florence flasks, answer well: a bent tube being connected at one end to its month, the other passing into the second vessel; heat should be cautiously applied by means of an Argand lamp, a little vessel of sand being placed under the flask, which helps the acid to decompose the salt. Prussic acid is then generated and passes through the tube to the recipient vessel, which is to be charged with liquor potassae.
"When the potash is saturated, the operation is completed. The Germans recommend a strong, alcoholic solution of potassa to be used in the second vessel, for in this case, the hydrocyanic or prussic acid combines with the potassa, forming a hydrocyanate of potassa, or, the water being abstracted, the cyanuret of potassium, which spontaneously precipitates, on the saturation of the fluid, the cyanuret, being insoluble in strong alcohol. The ferrocyanate of potash may be considered as containing three equivalents of hydrocyanic acid, two of potash and one of iron; but, unfortunately, we can only obtain half the acid from the salt, owing to the formation of a compound during its decomposition which resists the action of the acid. The decomposition of this salt taking 2 equivalents or 426 grains (to avoid fractions) would afford 3 equivalents or 81 grains of hydrocyanic, or prussic acid, capable of forming 198 grains of cyanuret of potassium, while in the retort there would remain 384 grains or 3 equivalents of bisulphate of potash, and 1 equivalent or 174 grains of a peculiar compound, said to contain 3 equivalents of cyanogen, 1 of potassium, and one of iron (Pereira). It is manifest that, but for this later compound, we might double the quantity of hydrocyanic acid from the yellow salt."
The decomposition just described is the one usually received; but too much reliance must not be placed on its accuracy, for the analysis of the several compounds is too difficult for the results to be fully admitted. The residue left in the retort speedily turns to one of the blues, identical with, or allied to, Prussian blue. This is at best a disagreeable process to conduct, for the hydrocyanic acid formed adheres so strongly to the glass, that, instead of being freely given off, bubbles are evolved suddenly with such explosive violence as occasionally to crack the vessel. This may be remedied as far as possible by the insertion of plenty of waste pieces of platinum--if platinized, so much the better, as that facilitates the escape of the gas. The heat should be applied to every part of the vessel, and the flame should not be allowed to play upon one single part alone. Large commercial operations are performed in green glass or stone-ware retorts.
"Now for one word of advice to the tyro: Remember that you are working with prussic acid; therefore, never conduct the process in a room, the fumes being quite as poisonous as the solution of the acid itself; moreover, have always a bottle of ammonia or chlorine by your side, that should you have chanced to inhale more than is pleasant, it will be instantly at hand to counteract any bad effects. It is stated by Pereira, that a little sulphuric acid or hydroferrocyanic acid passes to the outer vessel, but probably the amount would be of no consequence for electro-metallurgy, otherwise, it might be as well to use a Woulfe's apparatus, and discard the salt formed in the first vessel. To the large manufacturer it may be worth considering whether some other metallo-cyanuret, formed in a similar manner to the ferrocyanuret, might not be more advantageously employed, because the residue of the process last described contains a large quantity of cyanogen which the acid is unable to set free.
"There are other modes of procuring prussic acid, besides the one which has been so tediously described; but these are found to be more expensive. The only one which I shall now notice is the process by which it is obtained from bicyanide of mercury. The bicyanide of mercury itself is formed when peroxide of mercury is digested with Prussian blue, the peroxide of mercury abstracting the whole of the cyanogen from the blue, and leaving the oxides of iron at the bottom of the vessel. The solution may be evaporated to dryness, and one part of the salt dissolved in six of water; one part of muriatic acid, sp. gr. 1.15, is then added, and the solution distilled, when the whole of the hydrocyanic acid passes over, and by being conducted into a solution of potassa, as in the former process, forms cyanuret of potassium. This process, though easier than the first described, is rather given as a resource under peculiar circumstances than as one to be adopted by the large manufacturer. The expense is the only objection, but in a small quantity this cannot be a consideration.
"In giving this very rough outline of the general mode of forming salts, the minutiae necessary for chemical work have altogether been avoided, and those parts alone are entered upon which are more immediately necessary for the electro metallurgist to know and practice for himself. This will account for the long description of the cyanuret of potassium, while the preparation of the equally important and even more used acids, the sulphuric, muriatic, etc., commonly found in commerce, are altogether neglected.
"In using solutions of cyanide of potassium, the workman should not immerse his arms into them, otherwise it occasionally happens that the solution produces very troublesome eruptions over the skin."