Chapter 4
P. (part 3)
The sheets of paper being laid upon their respective feeding-boards, with the fore edges just in contact with the entering drum, a small roller, called the drop-down roller, falls, at proper intervals, down upon the edges of the sheets; the drum and the roller being then removed, instantly carry on the sheet, between the tapes t, downwards to the printing cylinder, and thence upwards to o, o, o, o, where the tapes are parted, and the sheet falls into the hands of the attendant boy. This noble mechanism is so perfectly equipped, that it is generally in full work within four minutes after the form is brought into the machine-room. The speed of König’s machine, by which the Times was formerly printed, was such as to turn out 1800 papers per hour; that of Applegath and Cowper throws off 4200 per hour, and it has been daily in use during eight years.
PRUSSIAN BLUE, and PRUSSIATE OF POTASH, are two important articles of chemical manufacture, which must be considered together. The first is called by English chemists, Ferrocyanodide of iron, the Cyanure ferroso-ferrique of Berzelius; Eisenblausaures eisenoxyd, or eisencyanür + eisencyanid, Germ.; the second is called Ferrocyanodide of potassium, the Cyanure ferroso-potassique of Berzelius; Eisencyanür-kalium, cyaneisen + cyankalium, or Blausaures eisenoxydul-kali, Germ.
Prussian blue (Berliner-blau, Germ.), is a chemical compound of iron and cyanogen. When organic matters abounding in nitrogen, as dried blood, horns, hair, skins, or hoofs of animals, are triturated along with potash in a strongly ignited iron pot, a dark gray mass is obtained, that affords to water the liquor originally called lixivium sanguinis, or blood-lye, which, by evaporation, yields lemon-coloured crystals in large rectangular tables, bevelled at the edges. This salt is called in commerce, prussiate of potash, and has for its ultimate constituents, potassium, iron, oxygen, and hydrogen, (the latter two in such proportions as to form water), and the peculiar compound Cyanogen, the blaustoff of the Germans.
These crystals consist, in 100 parts, of potassium 37·02, iron 12·82, cyanogen 37·40, water 12·76; or, cyanide of potassium 61·96, cyanide of iron 25·28, and water 12·76. They may be represented also by the following composition: 44·58 of potassa, 38·82 of hydrocyanic or prussic acid, and 16·60 of oxide of iron, in 100 parts; but the first appears to be their true chemical constitution. Dry ferrocyanodide of potassium, is a compound of, one atom of cyanide of iron, 54 = (28 + 26), and 2 atoms of cyanide of potassium, 132, = (26 × 2 + 40 × 2); the sum being 186; hydrogen being 1·0 in the scale of equivalents. The crystals of prussiate of potash are nearly transparent, soft, of a sweetish saline and somewhat bitterish taste, soluble in 4 parts of water at 52° F., and in 1 part of boiling water, but insoluble in alcohol. They are permanent in the air at ordinary temperatures, but in a moderately warm stove-room they part with 12⁄4 per cent. of water, without losing their form or coherence, and become thereby a white friable anhydrous ferrocyanodide of potassium, consisting of 42·44 potassium, 42·87 cyanogen, and 14·69 iron, in 100 parts.
This salt is an excellent reagent for distinguishing metals from each other, as the following Table of the precipitates which it throws down from their saline solutions will show:—
Metallic solutions. Colour of precipitate.
Antimony white.
Bismuth white.
Cadmium white, a little yellowish.
Cerium (protoxide) white, soluble in acids.
Cobalt green, soon turning reddish-gray.
Copper (protoxide) white, changing to red.
CoDo.r (peroxide) brown-red.
Iron (protoxide) white, rapidly turning blue.
IDo. (peroxide) dark blue.
Lead white, with a yellowish cast.
Manganese (protoxide) white, turning quickly peach or blood-red.
Manganese (deutoxide) greenish-gray.
Mercury (protoxide) white.
MeDo.ry(peroxide) white, turning blue.
Molybdenum dark brown.
Nickel (oxide) white, turning greenish.
Palladium (protoxide) green (gelatinous).
Silver white, turning brown in the light.
Tantalum yellow, dark burned colour.
Tin (protoxide) white, (gelatinous).
Do. (peroxide) yellow, perdo.
Uranium red-brown.
Zinc white.
No precipitations ensue with solutions of the alkaline or earthy salts, except that of yttria, which is white; nor with those of gold, platinum, rhodium, iridium, osmium, (in concentrated solutions,) tellurium, chromium, tungstenium. All the precipitates by the ferrocyanodide of iron, are double compounds of cyanide of iron with cyanide of the metal thrown down, which is produced by the reciprocal decomposition of the cyanide of potassium and the peculiar metallic oxide present in the solution. The precipitate from the sulphate of copper has a fine brown colour, and has been used as a pigment; but it is somewhat transparent, and therefore does not cover well. The precipitate from the peroxide salts of iron is a very intense prussian blue, called on the continent, Paris blue. It may be regarded as a compound of prussiate of protoxide and prussiate of peroxide of iron; or as a double cyanide of the protoxide and peroxide of iron, as the denomination cyanure ferroso-ferrique denotes. In numbers, its composition may be therefore stated thus: prussic or hydrocyanic acid, 48·48; protoxide of iron, 20·73; peroxide of iron, 30·79; or cyanogen, 46·71; iron, 37·36; water, 15·93; which represent its constitution when it is formed by precipitation with the prussiate of potash or a salt of iron that contains no protoxide. If the iron be but partially peroxidized in the salt, it will afford a precipitate, at first pale blue, which turns dark blue in the air, consisting of a mixture of prussiate of protoxide and prussiate of peroxide. In fact, the white cyanide of iron (the prussiate of the pure protoxide), when exposed to the air in a moist condition, becomes, as above stated, dark blue; yet the new combination formed in this case through absorption of oxygen, is essentially different from that resulting from the precipitation by the peroxide of iron, since it contains an excess of the peroxide in addition to the usual two cyanides of iron. It has been therefore called basic prussian blue, and, from its dissolving in pure water, soluble prussian blue.
Both kinds of prussian blue agree in being void of taste and smell, in attracting humidity from the air when they are artificially dried, and being decomposed at a heat above 348° F. The neutral or insoluble prussian blue is not affected by alcohol; the basic, when dissolved in water, is not precipitated by that liquid. Neither is acted upon by dilute acids; but they form with concentrated sulphuric acid a white pasty mass, from which they are again reproduced by the action of cold water. They are decomposed by strong sulphuric acid at a boiling heat, and by strong nitric acid at common temperatures; but they are hardly affected by the muriatic. They become green with chlorine, but resume their blue colour when treated with disoxidizing reagents. When prussian blue is digested in warm water along with potash, soda, or lime, peroxide of iron is separated, and a ferroprussiate of potash, soda, or lime remains in solution. If the prussian blue has been previously purified by boiling in dilute muriatic acid, and washing with water, it will afford by this treatment a solution of ferrocyanodide of potassium, from which by evaporation this salt may be obtained in its purest crystalline state. When the powdered prussian blue is diffused in boiling water, and digested with red oxide of mercury, it parts with all its oxide of iron, and forms a solution of bi-cyanodide, improperly called prussiate of mercury; consisting of 79·33 mercury, and 20·67 cyanogen; or, upon the hydrogen equivalent scale, of 200 mercury, and 52 = (26 × 2) cyanogen. When this salt is gently ignited, it affords gaseous cyanogen. Hydrocyanic or prussic acid, which consists of 1 atom of cyanogen = 26, + 1 of hydrogen = 1, is prepared by distilling the mercurial bi-cyanide in a glass retort with the saturating quantity of dilute muriatic acid. Prussic acid may also be obtained by precipitating the mercury by sulphuretted hydrogen gas from the solution of its cyanide; as also by distilling the ferrocyanide of potassium along with dilute sulphuric acid. Prussic acid is a very volatile light fluid, eminently poisonous, and is spontaneously decomposed by keeping, especially when somewhat concentrated.
Having expounded the chemical constitution of prussian blue and prussiate of potash, I shall now treat of their manufacture upon the commercial scale.
1. Of blood-lye, the phlogisticated alkali of Scheele. Among the animal substances used for the preparation of this lixivium, blood deserves the preference, where it can be had cheap enough. It must be evaporated to perfect dryness, reduced to powder, and sifted. Hoofs, parings of horns, hides, old woollen rags, and other animal offals, are, however, generally had recourse to, as condensing most azotized matter in the smallest bulk. Dried funguses have been also prescribed. These animal matters may either be first carbonized in cast-iron cylinders, as for the manufacture of sal ammoniac (which see), and the residual charcoal may be then taken for making the ferroprussiate; or the dry animal matters may be directly employed. The latter process is apt to be exceedingly offensive to the workmen and neighbourhood, from the nauseous vapours that are exhaled in it. Eight pounds of horn (hoofs), or ten pounds of dry blood, afford upon an average one pound of charcoal. This must be mixed well with good pearlash, (freed previously from most of the sulphate of potassa, with which it is always contaminated,) either in the dry way, or by soaking the bruised charcoal with a strong solution of the alkali; the proportion being one part of carbonate of potassa to from 1⁄2 to 2 parts of charcoal, or to about eight parts of hard animal matter. Gautier has proposed to calcine three parts of dry blood with one of nitre; with what advantage to the manufacturer, I cannot discover.
The pot for calcining the mixture of animal and alkaline matter is egg-shaped as represented at a, fig. 928, and is considerably narrowed at the neck e, to facilitate the closing of the mouth with a lid i. It is made of cast iron, about two inches thick in the belly and bottom; this strength being requisite because the chemical action of the materials wears the metal fast away. It should be built into the furnace in a direction sloping downwards, (more than is shown in the figure,) and have a strong knob b, projecting from its bottom to support it upon the back wall, while its shoulder is embraced at the arms c, c, by the brickwork in front. The interior of the furnace is so formed as to leave but a space of a few inches round the pot, in order to make the flame play closely over its whole surface. The fire-door f, and the draught-hole z, of the ash-pit, are placed in the posterior part of the furnace, in order that the workmen may not be incommoded by the heat. The smoke vent o, issues through the arched top h of the furnace, towards the front, and is thence led backwards by a flue to the main chimney of the factory. d is an iron or stone shelf, inserted before the mouth of the pot, to prevent loss in shovelling out the semi-liquid paste. The pot may be half filled with the materials.
The calcining process is different, according as the animal substances are fresh or carbonized. In the first case, the pot must remain open, to allow of diligent stirring of its contents, with a slightly bent flat iron bar or scoop, and of introducing more of the mixture as the intumescence subsides, during a period of five or six hours, till the nauseous vapours cease to rise, till the flame becomes smaller and brighter, and till a smell of ammonia be perceived. At this time, the heat should be increased, the mouth of the pot should be shut, and opened only once every half hour, for the purpose of working the mass with the iron paddle. When on opening the mouth of the pot, and stirring the pasty mixture, no more flame rises, the process is finished.
If the animal ingredients are employed in a carbonized state, the pot must be shut as soon as its contents are brought to ignition by a briskly urged fire, and opened for a few seconds only every quarter of an hour, during the action of stirring. At first, a body of flame bursts forth every time that the lid is removed; but by degrees this ceases, and the mixture soon agglomerates, and then softens into a paste. Though the fire be steadily kept up, the flame becomes less and less each time that the pot is opened; and when it ceases, the process is at an end. The operation, with a mass of 50 pounds of charcoal and 50 pounds of purified pearlash, lasts about 12 hours, the first time that the furnace is kindled; but when the pot has been previously brought to a state of ignition, it takes only 7 or 8 hours. In a well-appointed factory, the fire should be invariably maintained at the proper pitch, and the pots should be worked with relays of operatives.
The molten mass is now to be scooped out with an appropriate iron shovel, having a long shank, and caused to cool in small portions, as quickly as possible; but not by throwing it into water, as has sometimes been prescribed; for in this way a good deal of the cyanogen is converted into ammonia. If it be heaped up and kept hot in contact with air, some of the ferrocyanide is also decomposed, with diminution of the product. The crude mass is to be then put into a pan with cold water, dissolved by the application of a moderate heat, and filtered through cloths. The charcoal which remains upon the filter possesses the properties of decolouring syrups, vinegars, &c., and of destroying smells in a pre-eminent degree. It may also serve, when mixed with fresh animal coal, for another calcining operation.
As the iron requisite for the formation of the ferrocyanide is in general derived from the sides of the pot, this is apt to wear out into holes, especially at its under side, where the heat is greatest. In this event, it may be taken out of the furnace, patched up with iron-rust cement, and re-inserted with the sound side undermost. The erosion of the pot may be obviated in some measure by mixing iron borings or cinder (hammerschlag) with the other materials, to the amount of one or two hundredths of the potash.
The above lixivium is not a solution of pure ferroprussiate; it contains not a little cyanide of potassium, which in the course of the process had not absorbed the proper dose of iron to form a ferrocyanide; it contains also more or less carbonate of potash, with phosphate, sulphate, hydrogenated sulphuret, muriate, and sulpho-cyanide of the same base, as well as phosphate of lime; substances derived partly from the impure potash, and partly from the incinerated animal matters. Formerly that very complex impure solution was employed directly for the precipitation of prussian blue; but now, in all well regulated works, it is converted by evaporation and cooling into crystallized ferroprussiate of potash. The mother-water is again evaporated and crystallized, whereby a somewhat inferior ferroprussiate is obtained. Before evaporating the lye, however, it is advisable to add as much solution of green sulphate of iron to it, as will re-dissolve the white precipitate of cyanide of iron which first falls, and thereby convert the cyanide of potassium, which is present in the liquor, into ferrocyanide of potassium. The commercial prussiate of potash may be rendered chemically pure by making its crystals effloresce in a stove, fusing them with a gentle heat in a glass retort, dissolving the mass in water, neutralizing any carbonate and cyanide of potash that may be present with acetic acid, then precipitating the ferroprussiate of potash by the addition of a sufficient quantity of alcohol, and finally crystallizing the precipitated salt twice over in water. The sulphate of potassa may be decomposed by acetate of baryta, and the resulting acetate of potassa removed by alcohol.
2. The precipitation of prussian blue.—Green sulphate of iron is always employed by the manufacturer, on account of its cheapness, for mixing with solution of the ferroprussiate, in forming prussian blue, though the red sulphate, nitrate, or muriate of iron would afford a much richer blue pigment. Whatever salt of iron be preferred, should be carefully freed from any cupreous impregnation, as this would give the pure blue a dirty brownish cast. The green sulphate of iron is the most advantageous precipitant, on account of its affording protoxide, to convert into ferrocyanide any cyanide of potassium that may happen to be present in the uncrystallized lixivium. The carbonate of potash in that lixivium might be saturated with sulphuric acid before adding the solution of sulphate of iron; but it is more commonly done by adding a certain portion of alum; in which case, alumina falls along with the prussian blue; and though it renders it somewhat paler, yet it proportionally increases its weight; whilst the acid of the alum saturates the carbonate of potash, and prevents its throwing down iron-oxide, to degrade by its brown-red tint the tone of the blue. For every pound of pearlash used in the calcination, from two to three pounds of alum are employed in the precipitation. When a rich blue is wished for, the free alkali in the prussian lye may be partly saturated with sulphuric acid, before adding the mingled solutions of copperas and alum. One part of the sulphate of iron is generally allowed for 15 or 20 parts of dried blood, and 2 or 3 of horn-shavings or hoofs. But the proportion will depend very much upon the manipulations; which, if skilfully conducted, will produce more of the cyanides of iron, and require more copperas to neutralize them. The mixed solutions of alum and copperas should be progressively added to the lye as long as they produce any precipitate. This is not at first a fine blue, but a greenish gray, in consequence of the admixture of some white cyanide of iron; it becomes gradually blue by the absorption of oxygen from the air, which is favoured by agitation of the liquor. Whenever the colour seems to be as beautiful as it is likely to become, the liquor is to be run off by a spigot or cock from the bottom of the precipitation vats, into flat cisterns, to settle. The clear supernatant fluid, which is chiefly a solution of sulphate of potash, is then drawn off by a syphon; more water is run on with agitation to wash it, which after settling is again drawn off; and whenever the washings become tasteless, the sediment is thrown upon filter sieves, and exposed to dry, first in the air of a stove, but finally upon slabs of chalk or Paris plaster. But for several purposes, prussian blue may be best employed in the fresh pasty state, as it then spreads more evenly over paper and other surfaces.
A good article is known by the following tests: it feels light in the hand, adheres to the tongue, has a dark lively blue colour, and gives a smooth deep trace; it should not effervesce with acids, as when adulterated with chalk; nor become pasty with boiling water, as when adulterated with starch. The Paris blue, prepared without alum, with a peroxide salt of iron, displays, when rubbed, a copper-red lustre, like indigo. Prussian blue, degraded in its colour by an admixture of free oxide of iron, may be improved by digestion in dilute sulphuric or muriatic acid, washing, and drying. Its relative richness in the real ferroprussiate of iron may be estimated by the quantity of potash or soda which a given quantity of it requires to destroy its blue colour.
Sulphuretted hydrogen passed through prussian blue diffused in water, whitens it; while prussic acid is eliminated, sulphur is thrown down, and the sesquicyanide of iron is converted into the single cyanide. Iron and tin operate in the same way. When prussian blue is made with two atoms of ferrocyanide of potassium, instead of one, it becomes soluble in water.
For the mode of applying this pigment in dyeing, see Calico-printing.
Sesquiferrocyanate of potash, is prepared by passing chlorine gas through a solution of ferrocyanide of potassium, till it becomes red, and ceases to precipitate the peroxide salts of iron. The liquor yields, by evaporation, prismatic crystals, of a ruby-red transparency. They are soluble in 38 parts of water, and consist of 40·42 parts of sesquicyanide of iron, and 59·58 of cyanide of potassium. The solution of this salt precipitates the following metals, as stated in the table:—
Bismuth pale yellow.
Cadmium yellow.
Cobalt dark brown red.
Copper (protoxide) red brown.
CoDo.r (peroxide) yellow green.
Iron, protoxide salts of blue.
Manganese brown.
Mercury (protoxide) red brown.
Mercury (peroxide) yellow.
Molybdenum red brown.
Nickel yellow green.
Silver red brown.
Tin (protoxide) white.
Uranium red brown.
Zinc orange yellow.
PUMICE-STONE (Pierre-ponce, Fr.; Bimstein, Germ.); is a spongy, vitreous-looking mineral, consisting of fibres of a silky lustre, interlaced with each other in all directions. It floats upon water, is harsh to the touch, having in mass a mean sp. grav. of 0·914; though brittle, it is hard enough to scratch glass and most metals. Its colour is usually grayish white; but it is sometimes bluish, greenish, reddish, or brownish. It fuses without addition at the blowpipe into a white enamel. According to Klaproth, it is composed of, silica, 77·5; alumina, 17·5; oxide of iron, 2; potassa and soda, 3; in 100 parts. The acids have hardly any action upon pumice-stone. It is used for polishing ivory, wood, marble, metals, glass, &c.; as also skins and parchment. Pumice-stone is usually reckoned to be a volcanic product, resulting, probably, from the action of fire upon obsidians. The chief localities of this mineral are, the islands of Lipari, Ponza, Ischia, and Vulcano. It is also found in the neighbourhood of Andernach, upon the banks of the Rhine, in Teneriffe, Iceland, Auvergne, &c. It is sometimes so spongy as to be of specific gravity 0·37.
PUOZZOLANA, is a volcanic gravelly product, used in making hydraulic mortar. See Cements and Mortars.
PURPLE OF CASSIUS, Gold purple (Pourpre de Cassius, Fr.; Gold-purpur, Germ.); is a vitrifiable pigment, which stains glass and porcelain of a beautiful red or purple hue. Its preparation has been deemed a process of such nicety, as to be liable to fail in the most experienced hands. The following observations will, I hope, place the subject upon a surer footing.
The proper pigment can be obtained only by adding to a neutral muriate of gold a mixture of the protochloride and perchloride of tin. Every thing depends upon this intermediate state of the tin; for the protochloride does not afford, even with a concentrated solution of gold, either a chesnut-brown, a blue, a green, a metallic precipitate, or one of a purple tone; the perchloride occasions no precipitate whatever, whether the solution of gold be strong or dilute: but a properly neutral mixture, of 1 part of crystallized protochloride of tin, with 2 parts of crystallized perchloride, produces, with 1 part of crystallized chloride of gold (all being in solution), a beautiful purple-coloured precipitate. An excess of the protosalt of tin gives a yellow, blue, or green cast; an excess of the persalt gives a red and violet cast; an excess in the gold salt occasions, with heat (but not otherwise), a change from the violet and chesnut-brown precipitate into red. According to Fuchs, a solution of the sesquioxide of tin in muriatic acid, or of the sesquichloride in water, serves the same purpose, when dropped into a very dilute solution of gold.
Buisson prepares gold-purple in the following way. He dissolves, first, 1 gramme of the best tin in a sufficient quantity of muriatic acid, taking care that the solution is neutral; next, 2 grammes of tin in aqua regia, composed of 3 parts of nitric acid, and 1 part of muriatic, so that the solution can contain no protoxide; lastly, 7 grammes of fine gold in a mixture of 1 part of nitric acid, and 6 of muriatic, observing to make the solution neutral. This solution of gold being diluted with 3⁄2 litres of water (about 3 quarts), the solution of the perchloride of tin is to be added at once, and afterwards that of the protochloride, drop by drop, till the precipitate thereby formed acquires the wished-for tone; after which it should be edulcorated by washing, as quickly as possible.
Frick gives the following prescription:—Let tin be set to dissolve in very dilute aqua regia without heat, till the fluid becomes faintly opalescent, when the metal must be taken out, and weighed. The liquor is to be diluted largely with water, and a definite weight of a dilute solution of gold, and dilute sulphuric acid, is to be simultaneously stirred into the nitro-muriate of tin. The quantity of solution of gold to be poured into the tin liquor must be such, that the gold in the one is to the tin in the other in the ratio of 36 to 10.
Gold-purple becomes brighter when it is dry, but appears still as a dirty-brown powder. Muriatic acid takes the tin out of the fresh-made precipitate, and leaves the gold either in the state of metal or of a blue powder. At a temperature between 212° and 300° Fahr., mercury dissolves out all the gold from the ordinary purple of Cassius.
Relative to the constitution of gold-purple, two views are entertained: according to the first; the gold is associated in the metallic state along with the oxide of tin; according to the second, the gold exists as a purple oxide along with the sesquioxide or peroxide of tin. Its composition is differently reported by different chemists. The constituents, according to—
Gold. Tin
oxide.
Oberkampf, in the purple precipitate, are 39 ·82 60 ·18
violet ditto 20 ·58 79 ·42
Berzelius 30 ·725 69 ·275
Buisson 30 ·19 69 ·81
Gay Lussac 30 ·89 69 ·11
Fuchs 17 ·87 82 ·13
If to a mixture of protochloride of tin, and perchloride of iron, a properly diluted solution of gold be added, a very beautiful purple precipitate of Cassius will immediately fall, while the iron will be left in the liquid in the state of a protochloride. The purple thus prepared keeps in the air for a long time without alteration. Mercury does not take from it the smallest trace of gold,—Fuchs’ Journal für Chemie, t. xv.
PURPLE OF MOLLUSCA, is a viscid liquor, secreted by certain shell-fish, the Buccinum lapillus, and others, which dyes wool, &c. of a purple colour, and is supposed to be the substance of the Tyrian dye, so highly prized in antient Rome for producing the imperial purple. See Dyeing.
PURPURIC ACID, is an acid obtained by treating uric or lithic acid with dilute nitric acid. It has a fine purple colour; but has hitherto been applied to no use in the arts.
PURPURINE, is the name of a colouring principle, supposed by Robiquet and Colin to exist in madder. Its identity is questionable.
PUTREFACTION, and its Prevention. The decomposition of animal bodies, or of such plants as contain azote in their composition, which takes place spontaneously when they are exposed to the air, under the influence of moisture and warmth, is called putrefaction. During this process, there is a complete transposition of the proximate principles, the elementary substances combining in new and principally gaseous compounds. Oxygen is absorbed from the atmosphere, and converted into carbonic acid; one portion of the hydrogen forms water with the oxygen; another portion forms, with the azote, the carbon, the phosphorus, and the sulphur respectively, ammonia, carburetted, phosphuretted, and sulphuretted hydrogen gases, which occasion the nauseous smell evolved by putrefying bodies. There remains a friable earthy-looking residuum, consisting of rotten mould and charcoal. Vegetables which contain no azote, like the ligneous part of plants, suffer their corresponding decomposition much more slowly, and with different modifications, but they are finally converted into vegetable mould. In this process, the juices with which the plants are filled first enter into the acetous fermentation under the action of heat and moisture; the acid thereby generated destroys the cohesion of the fibrous matter, and thus reduces the solids to a pulpy state. In the progress of the decomposition, a substance is lastly produced which resembles oxidized extractive, is soluble in alkalis, and is sometimes called mould. This decomposition of the plants which contain no azote, goes on without any offensive smell, as none of the above-named nauseous gases are disengaged. When vegetable matters are mixed with animal, as in the dung of cattle, this decomposition proceeds more rapidly, because the animalized portion serves as a ferment to the vegetable. Vegetable acids, resins, fats, and volatilized oils, are not of themselves subject to putrefaction.
The object of the present article is to detail the principles and processes, according to which, for various purposes in the arts, the destruction of bodies by putrefaction may be prevented, and their preservation in a sound state secured for a longer or a shorter time.
I. CONDITIONS OF THE PREVENTION OF PUTREFACTION.
The circumstances by which putrefaction is counteracted, are, 1. the chemical change of the azotized juices; 2. the abstraction of the water; 3. the lowering of the temperature; and 4. the exclusion of oxygen.
1. The chemical change of the azotized juices.—The substance which in dead animal matter is first attacked with putridity, and which serves to communicate it to the solid fibrous parts, is albumen, as it exists combined with more or less water in all the animal fluids and soft parts. In those vegetables also which putrefy, it is the albumen which first suffers decomposition; and hence those plants which contain most of that proximate principle, are most apt to become putrid, and most resemble, in this respect, animal substances; of which fact, mushrooms, cabbages, coleworts, &c., afford illustrations. The albumen, when dissolved in water, very readily putrefies in a moderately warm air; but when coagulated, it seems as little liable to putridity as fibrin itself. By this change, it throws off the superfluous water, becomes solid, and may then be easily dried. Hence, those means which by coagulation make the albumen insoluble, or form with it a new compound, which does not dissolve in water, but which resists putrefaction, are powerful antiseptics. Whenever the albumen is coagulated, the uncombined water may be easily evaporated away, and the residuary solid matter may be readily dried in the air, so as to be rendered unsusceptible of decomposition.
In this way acids operate, which combine with the albumen, and fix it in a coagulated state, without separating it from its solution: such is the effect of vinegar, citric acid, tartaric acid, &c.
Tannin combines with the albuminous and gelatinous parts of animals, and forms insoluble compounds, which resist putrefaction; on which fact the art of tanning is founded.
Alcohol, oil of turpentine, and some other volatile oils, likewise coagulate albumen, and thereby protect it from putrescence. The most remarkable operation of this kind is exhibited by wood vinegar, in consequence of the creosote contained in it, according to the discovery of Reichenbach. This peculiar volatile oil has so decided a power of coagulating albumen, that even the minute portion of it present in pyrolignous vinegar is sufficient to preserve animal parts from putrefaction, when they are simply soaked in it. Thus, also, flesh is cured by wood smoke. Wood tar likewise protects animal matter from change, by the creosote it contains. The ordinary pyrolignous acid sometimes contains 5 per cent. of creosote.
In circumstances where a stronger impregnation with this antiseptic oil may be necessary, common wood vinegar may be heated to 167° F., and saturated with effloresced Glauber’s salts, by which expedient the oil is separated and made to float upon the surface of the warm liquid; whence it should be immediately skimmed off; because, by cooling and crystallizing, the solution would so diminish in density as to allow the oil to sink to the bottom; for its specific gravity is considerably greater than that of water. This oil, which contains, besides creosote, some other volatile constituents, may be kept dissolved ready for use in strong vinegar or alcohol. Water takes up of pure creosote only 1⁄4 per cent.; but alcohol dissolves it in every proportion.
The earthy and metallic salts afford likewise powerful means for separating albumen from its watery solution, their bases having the property of forming insoluble compounds with it. The more completely they produce this separation, the more effectually do they counteract putrefaction. The alkaline salts also, as common salt, sal ammoniac, saltpetre, and tartar, operate against putrescence, though in a smaller degree, because they do not precipitate the albumen; but, by abstracting a part of its water, they render it less liable to become putrid. Among the earthy salts, alum is the most energetic, as it forms a subsalt which combines with albumen; it is three times more antiseptic than common salt, and from seven to eight times more so than saltpetre. Muriate of soda, however, may be employed along with alum, as is done in the tawing of sheepskins.
The metallic salts operate still more effectually as antiseptics, because they form with albumen still more intimate combinations. Under this head we class the green and red sulphates of iron, the chloride of zinc, the acetate of lead, and corrosive sublimate; the latter, however, from its poisonous qualities, can be employed only on special occasions. Nitrate of silver, though equally noxious to life, is so antiseptic, that a solution containing only ⁄500 of the salt is capable of preserving animal matters from corruption.
2. Abstraction of water.—Even in those cases where no separation of the albumen takes place in a coagulated form, or as a solid precipitate, by the operation of a substance foreign to the animal juices, putrefaction cannot go on, any more than other kinds of fermentation, in bodies wholly or in a great measure deprived of their water. For the albumen itself runs so much more slowly into putrefaction, the less water it is dissolved in; and in the desiccated state, it is as little susceptible of alteration as any other dry vegetable or animal matter. Hence, the proper drying of an animal substance becomes a universal preventive of putrescence. In this way fruits, herbs, cabbages, fish, flesh, may be preserved from corruption. If the air be not cold and dry enough to cause the evaporation of the fluids before putrescence may come on, the organic substance must be dried by artificial means, as by being exposed in thin slices in properly constructed air-stoves. At temperatures under 140° F., the albumen dries up without coagulation, and may then be re-dissolved in cold water, with its valuable properties unaltered. By such artificial desiccation, if flesh is to be preserved for cooking or boiling, it must not be exposed, however, to so high a degree of heat, which would harden it permanently, like the baked mummies of Egypt. Mere desiccation, indeed, can hardly ever be employed upon flesh. Culinary salt is generally had recourse to, either alone or with the addition of saltpetre or sugar.
These alkaline salts abstract water in their solution, and, consequently, concentrate the aqueous solution of the albumen; whence, by converting the simple watery fluid into salt water, which is in general less favourable to the fermentation of animal matter than pure water, and by expelling the air, they counteract putridity. On this account, salted meat may be dried in the air much more speedily and safely than fresh meat. The drying is promoted by heating the meat merely to such a degree as to consolidate the albumen, and eliminate the superfluous water.
Alcohol operates similarly, in abstracting the water essential to the putrefaction of animal substances, taking it not only from the liquid albumen, but counteracting its decomposition, when mixed among the animal solids. Sugar acts in the same way, fixing in an unchangeable syrup the water which would otherwise be accessory to the fermentation of the organic bodies. The preserves of fruits and vegetable juices are made upon this principle. When animal substances are rubbed with charcoal powder or sand, perfectly dry, and are afterwards freely exposed to the air, they become deprived of their moisture, and will keep for any length of time.
3. Defect of warmth.—As a certain degree of heat is requisite for the vinous fermentation, so is it for the putrefactive. In a damp atmosphere, or in one saturated with moisture, if the temperature stand at from 70° to 80° F., the putrefaction goes on most rapidly; but it proceeds languidly at a few degrees above freezing, and is suspended altogether at that point. The elephants preserved in the polar ices are proofs of the antiseptic influence of low temperature. In temperate climates, ice-houses serve the purpose of keeping meat fresh and sweet for any length of time.
4. Abstraction of oxygen gas.—As the putrefactive decomposition of a body first commences with the absorption of oxygen from the atmosphere, so it may be retarded by the exclusion of this gas. It is not, however, enough to remove the aerial oxygen from the surface of the body, but we must expel all the oxygen that may be diffused among the vessels and other solids, as this portion suffices in general to excite putrefaction, if other circumstances be favourable. The expulsion is most readily accomplished by a moderate degree of heat, which, by expanding the air, evolves it in a great measure, and at the same time favours the fixation of the oxygen in the extractive matter, so as to make it no longer available towards the putrefaction of the other substances. Milk, soup, solution of gelatine, &c., may be kept long in a fresh state, if they be subjected in an air-tight vessel every other day to a boiling heat. Oxygenation may be prevented in several ways: by burning sulphur or phosphorus in the air of the meat receiver; by filling this with compressed carbonic acid; or with oils, fats, syrups, &c., and then sealing it hermetically. Charcoal powder recently calcined is efficacious in preserving meat, as it not only excludes air from the bodies surrounded by it, but intercepts the oxygen by condensing it. When butcher-meat is enclosed in a vessel filled with sulphurous acid, it absorbs the gas, and remains for a considerable time proof against corruption. The same result is obtained if the vessel be filled with ammoniacal gas. At the end of 76 days such meat has still a fresh look, and may be safely dried in the atmosphere.
II. PECULIAR ANTISEPTIC PROCESSES.
Upon the preceding principles and experiments depend the several processes employed for protecting substances from putrescence and corruption. Here we must distinguish between those bodies which may be preserved by any media suitable to the purpose, as anatomical preparations or objects of natural history, and those bodies which being intended for food, can be cured only by wholesome and agreeable means.
A common method for preserving animal substances unchanged in property and texture, is to immerse them in a spirituous liquor containing about 65 or 70 per cent. of real alcohol. Camphor may also be dissolved in it, and as much common salt as its water will take up. A double fold of ox-bladder should be bound over the mouth of the vessel, in order to impede the evaporation of the watery portion of the liquid, and its upper surface should be coated with a turpentine varnish. Undoubtedly a little creosote would be of use to counteract the decomposing influence of the alcohol upon the animal substances. With such an addition, a weaker spirit, containing no more than 30 per cent. of alcohol, would answer the purpose.
Instead of alcohol, a much cheaper vehicle is water saturated with sulphurous acid; and if a few drops of creosote be added, the mixture will become very efficacious. A solution of red sulphate of iron is powerfully antiseptic; but after some time it gives a deposit of the oxide, which disguises the preparation in a great degree.
According to Tauffier, animal substances may be preserved more permanently by a solution of one part of chloride of tin in 20 parts of water, sharpened with a little muriatic acid, than even by alcohol.
For preserving animal bodies in an embalmed form, mummy-like, a solution of chloride of mercury and wood vinegar are most efficacious. As there is danger in manipulating with that mercurial salt, and as in the present state of our knowledge of creosote we have it in our power to make a suitably strong solution of this substance in vinegar or spirit of wine, I am led to suppose that it will become the basis of most antiseptic preparations for the future. From the statements of Pliny, it is plain that wood vinegar was the essential means employed by the antient Egyptians in preparing their mummies, and that the odoriferous resins were of inferior consequence.
CURING OF PROVISIONS.
Flesh.—The ordinary means employed for preserving butcher meat are, drying, smoking, salting, and pickling or souring.
Drying of animal fibre.—The best mode of operating is as follows:—The flesh must be cut into slices from 2 to 6 ounces in weight, immersed in boiling water for 5 or 6 minutes, and then laid on open trellis-work in a drying-stove, at a temperature kept steadily about 122° F., with a constant stream of warm dry air. That the boiling water may not dissipate the soluble animal matters, very little of it should be used, just enough for the meat to be immersed by portions in succession, whereby it will speedily become a rich soup, fresh water being added only as evaporation takes place. It is advantageous to add a little salt, and some spices, especially coriander seeds, to the water. After the parboiling of the flesh has been completed, the soup should be evaporated to a gelatinous consistence, in order to fit it for forming a varnish to the meat after it is dried, which may be completely effected within two days in the oven. By this process two-thirds of the weight is lost. The perfectly dry flesh must be plunged piece by piece in the fatty gelatinous matter liquefied by a gentle heat; then placed once more in the stove, to dry the layer of varnish. This operation may be repeated two or three times, in order to render the coat sufficiently uniform and thick. Butcher’s meat dried in this way, keeps for a year, affords, when cooked, a dish similar to that of fresh meat, and is therefore much preferable to salted provisions. The drying may be facilitated, so that larger lumps of flesh may be used, if they be imbued with some common salt immediately after the parboiling process, by stratifying them with salt, and leaving them in a proper pickling-tub for 12 hours before they are transferred to the stove. The first method, however, affords the more agreeable article.
Smoking.—This process consists in exposing meat previously salted, or merely rubbed over with salt, to wood smoke, in an apartment so distant from the fire as not to be unduly heated by it, and into which the smoke is admitted by flues at the bottom of the side walls. Here the meat combines with the empyreumatic acid of the smoke, and gets dried at the same time. The quality of the wood has an influence upon the smell and taste of the smoke-dried meat; smoke from beech wood and oak being preferable to that from fir and larch. Smoke from the twigs and berries of juniper, from rosemary, peppermint, &c., imparts somewhat of the aromatic flavour of these plants. A slow smoking with a slender fire is preferable to a rapid and powerful one, as it allows the empyreumatic principles time to penetrate into the interior substance, without drying the outside too much. To prevent soot from attaching itself to the provisions, they may be wrapped in cloth, or rubbed over with bran, which may be easily removed at the end of the operation.
The process of smoking depends upon the action of the wood acid, or the creosote volatilized with it, which operates upon the flesh. The same change may be produced in a much shorter time by immersing the meat for a few hours in pyrolignous acid, then hanging it up in a dry air, which, though moderately warm, makes it fit for keeping, without any taint of putrescence. After a few days exposure, it loses the empyreumatic smell, and then resembles thoroughly smoked provisions. The meat dried in this way is in general somewhat harder than by the application of smoke, and therefore softens less when cooked, a difference to be ascribed to the more sudden and concentrated operation of the wood vinegar, which effects in a few hours what would require smoking for several weeks. By the judicious employment of pyrolignous acid diluted to successive degrees, we might probably succeed in imitating perfectly the effect of smoke in curing provisions.
Salting.—The meat should be rubbed well with common salt, containing about one sixteenth of saltpetre, and one thirty-secondth of sugar, till every crevice has been impregnated with it; then sprinkled over with salt, laid down for 24 or 48 hours, and, lastly, subjected to pressure. It must next be sprinkled anew with salt, packed into proper vessels, and covered with the brine obtained in the act of pressing, rendered stronger by boiling down. For household purposes it is sufficient to rub the meat well with good salt, to put it into vessels, and load it with heavy weights, in order to squeeze out as much pickle as will cover its surface. If this cannot be had, a pickle must be poured on it, composed of 4 pounds of salt, 1 pound of sugar, and 2 oz. of saltpetre, dissolved in 2 gallons of water.
Pickling with vinegar.—Vinegar dissolves or coagulates the albumen of flesh, and thereby counteracts its putrescence. The meat should be washed, dried, and then laid in strong vinegar. Or it may be boiled in the vinegar, allowed to cool in it, and then set aside with it in a cold cellar, where it will keep sound for several months.
Fresh meat may be kept for some months in water deprived of its air. If we strew on the bottom of a vessel a mixture of iron filings and flowers of sulphur, and pour over them some water which has been boiled, so as to expel its air, meat immersed in it will keep a long time, if the water be covered with a layer of oil, from half an inch to an inch thick. Meat will also keep fresh for a considerable period when surrounded with oil, or fat of any kind, so purified as not to turn rancid of itself, especially if the meat be previously boiled. This process is called potting, and is applied successfully to fish, fowls, &c.
Prechtl says that living fish may be preserved 14 days without water, by stopping their mouths with crumbs of bread steeped in brandy, pouring a little brandy into them, and packing them in this torpid state in straw. When put into fresh water, they come alive again after a few hours! Prechtl, Encyclop. Technologisches, art. Faülniss Abhaltung.
Eggs.—These ought to be taken new laid. The essential point towards their preservation is the exclusion of the atmospheric oxygen, as their shells are porous, and permit the external air to pass inwards, and to excite putrefaction in the albumen. There is also some oxygen always in the air cell of the eggs, which ought to be expelled or rendered inoperative, which may be done by plunging them for 5 minutes in water heated to 140° F. The eggs must be then taken out, wiped dry, besmeared with some oil (not apt to turn rancid) or other unctuous matter, packed into a vessel with their narrow ends uppermost, and covered with sawdust, fine sand, or powdered charcoal. Eggs coated with gum arabic, and packed in charcoal, will keep fresh for a year. Lime water, or rather milk of lime, is an excellent vehicle for keeping eggs in, as I have verified by long experience. Some persons coagulate the albumen partially, and also expel the air by boiling the eggs for two minutes, and find the method successful. When eggs are intended for hatching, they should be kept in a cool cellar; for example, in a chamber adjoining an ice-house. Eggs exposed, in the holes of perforated shelves, to a constant current of air, lose about ⁄4 of a grain of their weight daily, and become concentrated in their albuminous part, so as to be little liable to putrefy. For long sea voyages, the surest means of preserving eggs, is to dry up the albumen and yolk, by first triturating them into a homogeneous paste, then evaporating this in an air-stove or a water-bath heated to 125°, and putting up the dried mass in vessels which may be made air-tight. When used, it should be dissolved in three parts of cold or tepid water.
Grain of all kinds, as wheat, barley, rye, &c., and their flour, may be preserved for an indefinite length of time, if they be kiln-dried, put up in vessels or chambers free from damp, and excluded from the air. Well dried grain is not liable to the depredations of insects.
To preserve fruits in a fresh state, various plans are adopted. Pears, apples, plums, &c. should be gathered in a sound state, altogether exempt from bruises, and plucked, in dry weather, before they are fully ripe. One mode of preservation is, to expose them in an airy place to dry a little for eight or ten days, and then to lay them in dry sawdust or chopped straw, spread upon shelves in a cool apartment, so as not to touch each other. Another method consists in surrounding them with fine dry sand in a vessel which should be made air-tight, and kept in a cool place. Some persons coat the fruit, including their stalks, with melted wax; others lay the apples, &c., upon wicker-work shelves in a vaulted chamber, and smoke them daily during 4 or 5 days with vine branches or juniper wood. Apples thus treated, and afterwards stratified in dry sawdust, without touching each other, will keep fresh for a whole year.
The drying of garden fruits in the air, or by a kiln, is a well-known method of preservation. Apples and pears of large size should be cut into thin slices. From 5 to 6 measures of fresh apples, and from 6 to 7 of pears, afford in general one measure of dry fruit, (biffins). Dried plums, grapes, and currants are a common article of commerce.
Herbs, cabbages, &c., may be kept a long time in a cool cellar, provided they are covered with dry sand. Such vegetables are in general preserved for the purposes of food, by means of drying, salting, pickling with vinegar, or beating up with sugar. Cabbages should be scalded in hot water previously to drying; and all such plants, when dried, should be compactly pressed together, and kept in air-tight vessels. Tuberous and other roots are better kept in an airy place, where they may dry a little without being exposed to the winter’s frost.
A partial drying is given to various vegetable juices by evaporating them to the consistence of a syrup, called a rob, in which so much of the water is dissipated as to prevent them from running into fermentation. The fruits must be crushed, squeezed in bags to expel the juices, which must then be inspissated either over the naked fire, or on a water or steam bath, in the air or in vacuo. Sometimes a small proportion of spices is added, which tends to prevent mouldiness. Such extracts may be conveniently mixed with sugar into what are called conserves.
Salting is employed for certain fruits, as small cucumbers or gherkins, capers, olives, &c. Even for peas such a method is had recourse to, for preserving them a certain time. They must be scalded in hot water, put up in bottles, and covered with saturated brine, having a film of oil on its surface, to exclude the agency of the atmospheric air. Before being used, they must be soaked for a short time in warm water, to extract the salt. The most important article of diet of this class, is the sour kraut of the northern nations of Europe, (made from white cabbage,) which is prepared simply by salting; a little vinegar being formed spontaneously by fermentation. The cabbage must be cut into small pieces, stratified in a cask along with salt, to which juniper berries and carui seeds are added, and packed as hard as possible by means of a wooden rammer. The cabbage is then covered with a lid, on which a heavy weight is laid. A fermentation commences, which causes the cabbage to become more compact, while a quantity of juice exudes and floats on the surface, and a sour smell is perceived towards the end of the fermentation. In this condition the cask is transported into a cool cellar, where it is allowed to stand for a year; and indeed, where, if well made and packed, it may be kept for several years.
The excellent process for preserving all kinds of butcher meat, fish, and poultry, first contrived by M. Appert in France, and afterwards successfully practised upon the great commercial scale by Messrs. Donkin and Gamble, for keeping beef, salmon, soups, &c. perfectly fresh and sweet for exportation from this country, as also turtle for importation thither from the West Indies, deserves a brief description.
Let the substance to be preserved be first parboiled, or rather somewhat more, the bones of the meat being previously removed. Put the meat into a tin cylinder, fill up the vessel with seasoned rich soup, and then solder on the lid, pierced with a small hole. When this has been done, let the tin vessel thus prepared be placed in brine and heated to the boiling point, to complete the remainder of the cooking of the meat. The hole of the lid is now to be closed perfectly by soldering, whilst the air is rarefied. The vessel is then allowed to cool, and from the diminution of the volume, in consequence of the reduction of temperature, both ends of the cylinder are pressed inwards, and become concave. The tin cases, thus hermetically sealed, are exposed in a test-chamber, for at least a month, to a temperature above what they are ever likely to encounter; from 90° to 110° of Fahrenheit. If the process has failed, putrefaction takes place, and gas is evolved, which, in process of time, will cause both ends of the case to bulge, so as render them convex, instead of concave. But the contents of those cases which stand the test will infallibly keep perfectly sweet and good in any climate, and for any number of years. If there be any taint about the meat when put up, it inevitably ferments, and is detected in the proving process. Mr. Gamble’s turtle is delicious.
This preservative process is founded upon the fact, that the small quantity of oxygen contained within the vessel gets into a state of combination, in consequence of the high temperature to which the animal substances are exposed, and upon the chemical principle, that free oxygen is necessary as a ferment to commence or give birth to the process of putrefaction.
I shall conclude this article with some observations upon the means of preserving water fresh on sea voyages. When long kept in wooden casks, it undergoes a kind of putrefaction, contracts a disagreeable sulphureous smell, and becomes undrinkable. The influence of the external air is by no means necessary to this change, for it happens in close vessels even more readily than when freely exposed to the atmospherical oxygen. The origin of this impurity lies in the animal and vegetable juices which the water originally contained in the source from which it was drawn, or from the cask, or insects, &c. These matters easily occasion, with a sufficient warmth, fermentation in the stagnant water, and thereby cause the evolution of offensive gases. It would appear that the gypsum of hard waters is decomposed, and gives up its sulphur, which aggravates the disagreeable odour; for selenitic waters are more apt to take this putrid taint, than those which contain merely carbonate of lime.
As the corrupted water has become unfit for use merely in consequence of the admixture of these foreign matters, for water in itself is not liable to corruption, so it may be purified again by their separation. This purification may be accomplished most easily by passing the water through charcoal powder, or through the powder of rightly calcined bone-black. The carbon takes away not only the finely diffused corrupt particles, but also the gaseous impurities. By adding to the water a very little sulphuric acid, about 30 drops to 4 pounds, Lowitz says that two-thirds of the charcoal may be saved. Undoubtedly the sulphuric acid acts here, as in other similar cases, by the coagulation and separation of the albuminous matters, combining with them, and rendering them more apt to be seized by the charcoal. A more effectual agent for the purification of foul water is to be found in alum. A dram of pounded alum should be dissolved with agitation in a gallon of the water, and then left to operate quietly for 24 hours. A sediment falls to the bottom, while the water becomes clear above, and may be poured off. The alum combines here with the substances dissolved in the water, as it does with the stuffs in the dyeing copper. In order to decompose any alum which may remain in solution, the equivalent quantity of crystals of carbonate of soda may be added to it.
The red sulphate of iron acts in the same way as alum. A few drops of its solution are sufficient to purge a pound of foul water. The foreign matters dissolved in the water, which occasion putrefaction, become insoluble, in consequence of oxidizement, like vegetable extractive, and are precipitated. On this account, also, foul water may be purified, by driving atmospheric air through it with bellows, or by agitating it in contact with fresh air, so that all its particles are exposed to oxygen. Thus we can explain the influence of streams and winds, in counteracting the corruption of water exposed to them. Chlorine acts still more energetically than the air in purifying water. A little aqueous chlorine added to foul water, or the transmission of a little gaseous chlorine through it, cleanses it immediately.
Water-casks ought to be charred inside, whereby no fermentable stuff will be extracted from the wood. British ships, however, are now commonly provided with iron tanks for holding their water in long voyages.
PYRITES, is the native bisulphuret of iron. Copper pyrites, called vulgarly mundick, is a bisulphuret of copper.
PYRO-ACETIC SPIRIT. (Esprit pyro-acétique, Acétone, Fr.; Brennzlicher Essiggeist, Mesit, Germ.) This liquid was discovered and described by Chenevix long before pyrolignous spirit was known. It may be obtained by subjecting to dry distillation the acetates of copper, lead, alkalis, and earths; and as it is formed especially during the second half of the process, the liquor which comes over then should be set apart, separated by decantation from the empyreumatic oil, and distilled a second time by the heat of a water-bath. The fine light fluid which now comes over first, is to be rectified along with carbonate of potassa, or chloride of calcium. As pyro-acetic spirit usually retains, even after repeated distillations, a disagreeable empyreumatic smell, like garlic, a little good bone-black should be employed in its final rectification. According to Reichenbach, pyro-acetic spirit may be extracted in considerable quantity from beech tar. (See the next article.) The spirit thus prepared, is a colourless limpid liquid, of an acrid and burning taste at first, but afterwards cooling; of a penetrating aromatic smell, different from that of alcohol; of the spec. gravity 0·7921 at 60° F., boiling at 132° F., and remaining fluid at 5°. It consists ultimately of—carbon, 62·148; hydrogen, 10·453; oxygen, 27·329; or, of 1 proportion of carbonic acid + 2 prop. of olefiant gas + 1 prop. of water; or, 1 prop. of acetic acid—1 prop. of carbonic acid. According to another view, it is composed of, 51·52 parts of concentrated acetic acid, and 48·488 of oil of wine, being double of the quantity in acetic ether. It is very combustible, and burns with a brilliant flame, without smoke. When treated by chlorine, it loses an atom of its hydrogen, and absorbs 2 atoms of chlorine. It is soluble in water, alcohol, ether, and is not convertible into ether by strong sulphuric acid. It is used for dissolving the resins commonly called gums, with which the bodies of hats are stiffened.
PYROLIGNOUS ACID. In addition to what has been said under Acetic Acid, I shall here describe the process as conducted upon a great scale at an establishment near Manchester. The retorts are of cast iron, 6 feet long, and 3 feet 8 inches in diameter. Two of these cylinders are heated by one fire, the flame of which plays round their sides and upper surface; but the bottom is shielded by fire-tiles from the direct action of the fire. 2 cwts. of coals are sufficient to complete the distillation of one charge of wood; 36 imperial gallons of crude vinegar, of specific gravity 1·025, being obtained from each retort. The process occupies 24 hours. The retort-mouth is then removed, and the ignited charcoal is raked out for extinction into an iron chest, having a groove round its edges, into which a lid is fitted.
When this pyrolignous acid is saturated with quicklime, and distilled, it yields one per cent. of pyroxilic spirit (sometimes called naphtha); which is rectified by two or three successive distillations with quicklime.
The tarry deposit of the crude pyrolignous acid, being subjected to distillation by itself, affords a crude pyro-acetic ether, which may also be purified by re-distillation with quicklime, and subsequent agitation with water.
The pyrolignite of lime, is made by boiling the pyrolignous acid in a large copper, which has a sloping spout at its lip, by which the tarry scum freely flows over, as it froths up with the heat. The fluid compound thus purified, is syphoned off into another copper, and mixed with a quantity of alum equivalent to its strength, in order to form the red liquor, or acetate of alumina, of the calico-printer. The acetate of lime, and sulphate of alumina and potash, mutually decompose each other; with the formation of sulphate of lime, which falls immediately to the bottom.
M. Kestner, of Thann, in Alsace, obtains, in his manufactory of pyrolignous acid, 5 hectolitres (112 gallons imperial, nearly,) from a cord containing 93 cubic feet of wood. The acid is very brown, much loaded with tar, and marks 5° Baumé; 220 kilogrammes of charcoal are left in the cylinders; 500 litres of that brown acid produce, after several distillations, 375 of the pyrolignous acid of commerce, containing 7 per cent. of acid, with a residuum of 40 kilogrammes of pitch. For the purpose of making a crude acetate of lead (pyrolignite), he dries pyrolignite of lime upon iron plates, mixes it with the equivalent decomposing quantity of sulphuric acid, previously diluted with its own weight of water, and cooled; and transfers the mixture as quickly as possible into a cast-iron cylindric still, built horizontally in a furnace; the under half of the mouth of the cylinder being always cast with a semicircle of iron. The acetic acid is received into large salt-glazed stone bottles. From 100 parts of acetate of lime, he obtains 133 of acetic acid, at 38° Baumé. It contains always a little sulphurous acid from the reaction of the tar and the sulphuric acid.
The apparatus represented in figs. 929. and 930. is a convenient modification of that exhibited under acetic acid, for producing pyrolignous acid. Fig. 929. shows the furnace in a horizontal section drawn through the middle of the flue which leads to the chimney. Fig. 930. is a vertical section taken in the dotted line x, x, of fig. 929. The chest a is constructed with cast-iron plates bolted together, and has a capacity of 100 cubic feet. The wood is introduced into it through the opening b, in the cover, for which purpose it is cleft into billets of moderate length. The chest is heated from the subjacent grate c, upon which the fuel is laid, through the fire-door d. The flame ascends spirally through the flues e, e, round the chest, which terminate in the chimney f. An iron pipe g conveys the vapours and gaseous products from the iron chest to the condenser. This consists of a series of pipes laid zigzag over each other, which rest upon a framework of wood. The condensing tubes are enclosed in larger pipes i, i; a stream of cold water being caused to circulate in the interstitial spaces between them. The water passes down from a trough k, through a conducting tube l, enters the lowest cylindrical case at m, flows thence along the series of jackets i, i, i, being transmitted from the one row to the next above it, by the junction tubes o, o, o, till at p it runs off in a boiling-hot state. The vapours proceeding downwards in an opposite direction to the cooling stream of water, get condensed into the liquid state, and pass off at q, through a discharge pipe, into the first close receiver r, while the combustible gases flow off through the tube s, which is provided with a stopcock to regulate the magnitude of their flame under the chest. As soon as the distillation is fully set agoing, the stopcock upon the gas-pipe is opened; and after it is finished, it must be shut. The fire should be supplied with fuel at first, but after some time the gas generated keeps up the distilling heat. The charcoal is allowed to cool during 5 or 6 hours, and is then taken out through an aperture in the back of the chest, which corresponds to the opening u, fig. 929., in the brickwork of the furnace. About 60 per cent. of charcoal may be obtained from 100 feet of fir-wood, with a consumption of as much brush-wood for fuel.
Stoltze has ascertained, by numerous experiments, that one pound of wood yields from 6 to 7⁄2 ounces of liquid products; but in acetic acid it affords a quantity varying from 2 to 5, according to the nature of the wood. Hard timber, which has grown slowly upon a dry soil, gives the strongest vinegar. White birch and red beech afford per pound 7⁄3 ounces of wood vinegar, 1⁄3 ounce of combustible oil, and 4 ounces of charcoal. One ounce of that vinegar saturates 110 grains of carbonate of potassa. Red pine yields per pound 6⁄2 ounces of vinegar, 2⁄4 ounces of oil, 3⁄4 ounces of charcoal; but one ounce of the vinegar saturates only 44 grains of carbonate of potassa, and has therefore only two-fifths of the strength of the vinegar from the birch. An ounce of the vinegar from the white beech, holly oak (Ilex), common ash, and horse chesnut, saturates from 90 to 100 grains of the carbonate. In the same circumstances, an ounce of the vinegar of the alder and white pine saturates from 58 to 60 grains.
PYROLIGNOUS or PYROXILIC SPIRIT, improperly called naphtha. This is employed, as well as pyroacetic ether, to dissolve the sandarach, mastic, and other resinous substances, which, under the name of gums, are used for stiffening the bodies of hats. I have already described, in the article Pyrolignous Acid, how this spirit is obtained. Berzelius has found that the crude spirit may be best purified by agitating it with a fat oil, in order to abstract the empyreumatic oil; then to decant the spirit, distil it, first with fresh calcined charcoal, and next with chloride of calcium. The pyrolignous spirit, thus purified, is colourless, and limpid like alcohol; has an ethereous smell, somewhat resembling that of ants. Its taste is hot, and analogous to that of oil of peppermint. Its specific gravity, by my experiments, is 0·824. It readily takes fire, and burns with a blue flame, without smoke. It combines with water in any proportion; a property which distinguishes it from pyroacetic ether and spirit.
It is not easy to say what is the real chemical nature of pyroxilic spirit. There is no ultimate analysis of it that can be depended upon. The properties of the spirit examined by MM. Marcet and Macaire, differ from those of our spirit, in refusing to combine with water, like alcohol. The article on sale in this country readily unites with water, and in all proportions with alcohol.
PYROMETER, is the name of an instrument for measuring high degrees of heat above the range of the mercurial thermometer. Wedgewood’s is the one commonly referred to by writers upon porcelain and metallurgy; but a better one might be easily contrived.
PYROPHORUS, is the generic name of any chemical preparation, generally a powder, which inflames spontaneously when exposed to the air.
PYROTECHNY. See Fire-works.
PYROXILINE, is a name which I have ventured to give to a substance detected in pyroxilic spirit, by Mr. Scanlan, while residing in Dublin, and therefore called by him Eblanin. I am indebted to that ingenious chemist for the following facts.
If potash water be added to raw wood-spirit (pyrolignous), as long as it throws down any thing, a precipitate is produced, which is pyroxiline, mixed with tarry matter. This precipitate is to be collected on a filter cloth, and submitted to strong pressure between folds of blotting-paper; it is next to be washed with cold alcohol, spec. grav. 0·840, in order to free it from any adhering tarry matter; when the pyroxiline is left nearly pure. If it be dissolved in boiling alcohol, or hot oil of turpentine, it crystallizes regularly on cooling, in right square prisms, of a fine yellow colour, that look opaque to the naked eye, but when examined under the microscope, have the transparency and colour of ferroprussiate of potash. Its turpentine solution affords crystals of a splendid orange-red colour, having the appearance of minute plates, whose form is not discernible by the naked eye, but when examined by the microscope, they are seen to be thin right rectangular prisms. The orange-red colour is only the effect of aggregation; for when ground to powder, these crystals become yellow; and under the microscope, the difference in colour between the two is very slight. Its melting point is 318° F. It sublimes at 300° in free air; heated in a close tube in a bath of mercury, it emits vapour at 400°; it then begins to decompose, and is totally decomposed at 500°. Sulphuric acid decomposes it, producing a beautiful blue colour, which passes into crimson, as the acid attracts water from the atmosphere, and it totally disappears on plentiful dilution with water, leaving carbon of a dirty-brown colour. Its alcoholic or turpentine solution imparts a permanent yellow dye to vegetable or animal matter.
Pyroxiline consists, according to the analysis of Drs. Apjohn and Gregory, of—carbon, 75·275; hydrogen, 5·609; oxygen, 19·116, in 100 parts.